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Implementing Regional Air Monitoring Programs

1. 8 3 2 2 Stage Il Activities 8 3 2 3 Stage 8 3 3 TECHNICAL 8 Sit Selection 8 3 2 Analyte SelectlOn Ve 10 3 3 Physical State of the Analyte 10 3 4 Sampling and Analytical Protocol Selection 11 3 4 LOGISTICAL 85 0 200222 13 3 5 DATA QUALITY FACTORS 0222 22 14 2 02 GOST FAC TORS ans eher eni editas 14 Only the Sections in Bold are included as excerpts in this document EPA Excerpt Sampling and Analysis of Toxic Organic Compounds in Ambient Air 15 3 7 COMPILATION AND EVALUATION OF AVAILABLE INFORMATION 14 3 7 1 Assessment of Available Air Quality Data 14 3 7 1 1 National Air Toxics Information Clearinghouse NATICH Data cia xii ee des 16 3 7 1 2 Air Toxics Monitoring Data 16 3 7 2 Assessment of Toxic Organic Air Pollutant Sources 17 3 7 3 Assessment of Mete
2. 7 5 2 Instrument Calibration and Maintenance 7 5 3 Quality Control Sample Analysis 7 6 DATA MANAGEMENT EPA Excerpt Sampling and Analysis of Toxic Organic Compounds in Ambient Air 77 3 1 3 2 5 1 5 2 5 3 6 1 6 2 APPENDIX APPENDIX APPENDIX APPENDIX APPENDIX LIST OF TABLES COMPONENTS OF THE DATA QUALITY OBJECTIVE PROCESS 9 QUALITY ASSURANCE QA ACTIVITIES TO BE SPECIFIED IN PROGRAM nere a 28 COMMONLY USED GC 59 USEFUL DUAL GC DETECTORS COMBINATIONS EEE 62 HPLC DETECTORS cn sata METHOD FOR THE ANALYSIS OF TOXIC ORGANIC AIR POLLUTANTS INAMBIENT AIR einen 70 SAMPLING AND ANALYTICAL METHODOLOGIES FOR SELECTED TOXIC ORGANIC AIR 72 LIST OF APPENDICES COMPOUNDS SUBJECT TO REGULATION UNDER THE PROPOSED CLEAN AIR ATTAINMENT ACT OF 1987 REFERENCE METHODS FOR TOXIC ORGANIC AIR POLLUTANTS GLOSSARY EQUIPMENT INSTRUMENT VENDORS CALIBRATION GAS STANDARDS EPA Excerpt Sampling and Analysis of Toxic Organic Compounds in Ambient Air 78 3 2 DATA QUALITY OBJECTIVES The first step in any planning process is the identification of objectives E
3. A Summary of Key Probe Sitting Criteria for Air Monitoring T QA QC Activities to be Specified in Program Typical Sampling Analysis Frequencies for QC Samples Calibration Requirements for Sampling and Analysis Instrumentation Ranges of Unit Cost Estimates for Equipment and Supplies and Laboratory Analysis for Regional Air Monitoring Programs 345 nae ed Ce ee eas Example Range of Cost Estimates for Implementing the Case I Short Term VOCs Air Monitoring Study see ________________ ns Example Range of Cost Estimates for Implementing Case II Long Term Regional Air Monitoring Program for VOCs and Metal Particulate Elements to Plan and Implement a Regional Air Toxics Monitoring Getting a Monitoring Program Key Elements of a Plan for Regional Air Toxics Monitoring Program Selecting Monitoring Key Elements of Network Operation Field Instrumentation Operation and Typical Chain or Custody POI de beamed ae Key Elements of QA QC for R
4. 33 6 2 Interpreting the Results 35 6 3 Re evalua ng 1 35 6 4 Reporting Results and Conclusions 36 6 5 Optional Use of Results in Model Validation 36 6 6 Kelern oS alia eagle Sad SA hase cae ace be Ae esas 37 7 0 Estimating Program 39 7 1 Unit Costs of Equipment Supplies and Analyses 39 7 2 Program Scenario Costs bc usw e Me 39 3 5 3 6 3 7 3 8 5 1 5 2 5 3 7 2 7 3 1 1 2 1 3 1 3 2 4 1 4 2 4 3 5 1 5 2 6 1 6 2 Tables Recommended Program Sampling Duration and Frequency and Program Length by Objectives An Overview of Air Toxics Monitoring Sampling Techniques er rat een A Summary of Time Integrating Monitoring Techniques for Organics and Inorganics in Air Comparisons of Regional Air Monitoring Techniques Recommended System Accuracies and Recommended Response Characteristics for Meteorological 0 Guidance for Selecting the Number and Locations of Monitoring Stations for Regional Air Monitoring Programs
5. 404 072 AQEL eas 0 ON pe 01 6 8 Aususyuj U S EPA Compendium Method T014 1988 146 SOOA 123135 OL ASNOdS3Y WOIdAL 9 104 0 2 91981 995 0t St be 61 4191 51 008 4 L 0 4 5 U S EPA Compendium Method 014 1988 147 TIME gt a Certified Sampler TIME b Contaminated Sampler FIGURE 17 EXAMPLE OF HUMID ZERO AIR TEST RESULTS FOR A CLEAN SAMPLER a AND A CONTAMINATED SAMPLER b 148 U S EPA Compendium Method T014 1988 1000 1000 900 900 800 _ 800 700 700 60 X 600 S 500 2 500 IE 400 400 amp 300 Mn 7 lt gt 200 lt 200 100 100 0 0 0 1 2 3 4 56 6 7 8 9 10 2220 1 2 3 4 5 6 7 8 9 10 Concentration ppbv Concentration ppbv FIGURE 18 NONLINEAR RESPONSE OF FIGURE 18 b NONLINEAR RESPONSE OF TETRACHLOROETHYLENE ON THE ECD CARBON TETRACHLORIDE ON THE ECD 1000 160 900 orm 14 5 5 gt 120 x e 600 e 100 400 o e 69 E E 200 id 100 20 0 0 01 2 3 4 5 6 7 8 9 10 01 23 4 5 6 7 8 9 10 Concentration ppbv Concentration ppbv FIGURE 18 c NONLINEAR RESPONSE OF FIGURE 18 d LINEAR RESPONSE OF HEXACHLOROBUTADIENE ON THE ECD CHLOROFORM ON THE ECD FIGURE 18 RESPO
6. 55 EPA PUBLICATION NUMBER MONTH OF PUBLICATION TECHNICAL ASSISTANCE DOCUMENT FOR SAMPLING AND ANALYSIS OF TOXIC ORGANIC COMPOUNDS IN AMBIENT AIR b m ATC Inc 1635 Pumphrey Ave Auburn Alabama 36830 Contract No 68 02 4566 EPA Project Officer Howard Crist Environmental Monitoring Systems Laboratory U S Environmental Protection Agency Research Triangle Park North Carolina 27711 ENVRONMENTAL MONITORING SYSTEMS LABORATORY U S ENVIRONMENTAL PROTECTION AGENCY __ RESEARCH TRIANGLE NORTH CAROLINA 27111 EPA Excerpt Sampling and Analysis of Toxic Organic Compounds in Ambient Air 73 ABSTRACT This Technical Assistance Document TAD was initially published in June 1983 and has been updated to reflect the advances that have been made in sampling and analysis of toxic organic compounds in ambient air The primary users of this document are expected to be regional state and local environmental protection personnel who are faced with the need to determine ambient air quality for regulatory or information gathering purposes The TAD consists of the following seven chapters 1 OP Introduction Regulatory Issues Concerning Toxic Organic Monitoring Guidelines for Development of a Monitoring Plan Overview of Sampling Methods Overview of Analytical Methods Methods for Specific Compounds and Compound Classes Quality Assurance EPA Excerpt Sampling and Analysis
7. B SAMPLING INFORMATION TEMPERATURE PRESSURE INTERIOR AMBIENT MAXIMUM MINIMUM CANISTER PRESSURE SAMPLING SYSTEM CERTIFICATION DATE QUARTERLY RECERTIFICATION DATE C LABORATORY INFORMATION DATE RECEIVED RECEIVED BY INITIAL PRESSURE FINAL PRESSURE DILUTION FACTOR ANALYSIS GC FID ECD DATE GC MSD SCAN DATE GC MSD SIM DATE RESULTS GC FID ECD GC MSD SCAN GC MSD SIM SIGNATURE TITLE ATTACH DATA SHEETS FIGURE 10 CANISTER SAMPLING FIELD DATA SHEET U S EPA Compendium Method T014 1988 141 INTENSITY TIME gt a SCAN analysis INTENSITY TIME gt b SIM analysis FID analysis INTENSITY INTENSITY TIME gt d ECD analysis FIGURE 11 TYPICAL CHROMATOGRAMS OF A VOC SAMPLE ANALYZED BY GC MS SCAN SIM MODE AND GC MULTIDETECTOR MODE 142 U S EPA Compendium Method T014 1988 Cryogen Exhaust 4 Insulated Shell Cylindrically Wound Tube Heater 250 watt Trap Bracket and Cartridge Heaters 25 watt Cryogen in Liquid Nitrogen FIGURE 12 CRYOGENIC TRAPPING UNIT 143 U S EPA Compendium Method 014 1988 Log Sample In Sectlon 10 4 1 2 Check and Record initia Pressure Sectlon 10 4 1 3 83 12 psig Optional Pressurize with No To 138 kPa 20 psig Preparation of GC MS SCAN SIM with Optional FID
8. 13 3 5 Defining Meteorological Requirements 16 3 6 Designing the Network 5 5 s DEN 17 3 7 Selecting Contractors for Sampling and Analysis 20 3 8 on ab i eet ca eee 21 4 0 Operating the Network et nb mete dus oeque ake ae ee 23 4 1 Selecting and Training Personnel leer 23 4 2 Procuring Equipment and Supplies 24 4 3 Operating and Maintaining the Field Instrumentation 24 4 4 Recordkeeping 25 5 0 Implementing Quality Assurance Quality Control 00 27 5 1 Defining Quality Assurance Quality Control QA QC Requirements 27 5 2 Performing Routine QA QC 28 5 3 Implementing Periodic QA QC Checks 29 5 4 Executing Laboratory QA QC 30 5 5 Implementing Data Management QA QC Checks 30 5 6 iin 3 2 ec typ grec 30 6 0 Managing and Evaluating the 33 6 1 Storing and Summarizing the
9. 2 21 295 peuged poquiessesiq juauoduio U S EPA Compendium Method T014 1988 152 1 0 2 0 3 0 APPENDIX A AVAILABILITY OF AUDIT CYLINDERS FROM UNITED STATES ENVIRONMENTAL PROTECTION AGENCY USEPA PROGRAMS REGIONAL OFFICES STATE AND LOCAL AGENCIES AND THEIR CONTRACTORS Availability of Audit Cylinders 1 1 The USEPA has available at no charge cylinder gas standards of hazardous organic compounds the ppb level that may be used to audit the performance of indoor air source measurement systems 1 2 Each audit cylinder contains 5 to 18 hazardous organic compounds in a balance of gas Audit cylinders are available in several concentration ranges The concentration of each organic compound in the audit cylinder is within the range illustrated in Table A 1 Audit Cylinder Certification 2 1 All audit cylinders are periodically analyzed to assure that cylinder concentrations have remained stable 22 Stability analyses include quality contro analyses of ppb hazardous organic gas standards pre pared by the National Bureau of Standards for USEPA Audit Cylinder Acquisition 3 1 USEPA program regional offices state local agencies and their contractors may obtain audit cylin ders and an audit gas delivery system if applicable for performance audits during RCRA Hazardous Waste Trial Burns For PHOC s and Ambient Indoor Air Measurement of Toxic Organics 3 2 The au
10. E hh sr M ce od Db tener ped COMPENDIUM METHOD 0 14 THE DETERMINATION OF VOLATILE ORGANIC COMPOUNDS VOCs IN AMBIENT AIR USING SUMMA PASSIVATED CANISTER SAMPLING AND GAS CHROMATOGRAPHIC ANALYSIS lt 205 74 SU SZ L prote AGENCY gt QUALITY ASSURANCE DIVISION ENVIRONMENTAL MONITORING SYSTEMS LABORATORY U S ENVIRONMENTAL PROTECTION AGENCY RESEARCH TRIANGLE PARK NORTH CAROLINA 27711 MAY 1988 91 vo Be r were ratara ve un mun I E r E ELM Pp eun See w gt M wes t 22 2 2 utt METHOD T014 DETERMINATION OF VOLATILE ORGANIC COMPOUNDS VOCs IN AMBIENT AIR USING SUMMA PASSIVATED CANISTER SAMPLING AND GAS CHROMATOGRAPHIC ANALYSIS OUTLINE 1 0 Scope 2 0 Applicable Documents 3 0 Summary of Method 4 0 Significance 5 0 Definitions 6 0 Interferences and Limitations 7 0 Apparatus 71 Sample Collection 711 Subatmospheric Pressure 7 1 2 Pressurized 72 Sample Analysis 7 2 1 GC MS SCAN Analytical System 7 2 2 GC MS SIM Analytical System 7 2 3 GC Multidetector Analytical System 7 3 Canister Cleaning System 7 4 Calibration System and Manifold 8 0 Reagents and Materials 9 0 Sampling System 9 1 System Description 9 1 1 Subatmospheric Pressure Sampling 9 1 2 Pressurized Sampling 9 1 3 All Samplers 9 2 S
11. The percent difference between the air concentrations measured at collocated samplers is di 100 G 1 2 Where di The percent difference between the concentration of air toxic constituents measured by col located monitoring station and the concentration of air toxics constituent Xi measured by the monitoring station reporting the air quality The average percent difference dj for the monitoring period is j n 220 n j G 2 Where dj percent difference defined above n number of samples collected during the monitoring period The standard deviation S for the percent differences is Sj The 95 percent probability limits for precision are Upper 95 Percent Probability Limit dj 1 96 Sj 2 G 4 Lower 95 Percent Probability Limit dj 1 96Sj 2 6 5 The accuracy is calculated for the monitoring period by calculating the percent difference dk between the dicated parameter from the audit concentration flow rate etc and the known parameter as follows Ak Bk dk gt 100 1 Bk Where Ax monitor s indicated parameter from the kth audit check known parameter used for the Ath audit check These results should be compared with the QA QC criteria stipulated in the monitoring plan to determine data validity 178 Other Related Documents CMA as part of its ongoing technical education and communication efforts developed this docu
12. same compounds that the laboratory is performing analysis Blank samples contain only inert compounds e g nitrogen In addition a quarterly onsite audit is recommended for the air monitoring program The audit should consist of the following Inspecting sampling stations for general physical condition and operability Re evaluating the source activities e Evaluating the technical performance and record keeping procedures These are compared to the specifications in the monitoring plan and appro priate Standard Operating Procedures e Auditing the air monitoring equipment e Auditing the meteorological equipment Additional routine QC checks are summarized in Tables 5 2 and 5 3 5 4 EXECUTING LABORATORY QA QC PROGRAM Laboratory analytical techniques must properly iden tify the sample components and accurately and precisely measure concentrations This generally requires the pre concentration and or storage of air samples Therefore methods chosen for time integrated monitoring usually involve a longer analytical time period more sophisti cated equipment and more rigorous QA procedures Canister sampling includes replicate analyses and dupli cate canisters to assess analytical and sampling precision Exchanging samples with other laboratories is desirable to check analytical performance Laboratory QC methods for the regional air monitoring project should include the following elements replicates sp
13. 6 3 RE EVALUATING THE PROGRAM The regional air monitoring program should be re evaluated quarterly The program review should focus on determining whether program objectives are being attained Specifically among the factors that should be evaluated during the initial program review and quarterly thereafter are the following e Program accomplishments versus objectives e Adequacy of data quality Adequacy of detection levels Occurrence of sample contamination e Sample matrix interference problems e Acceptable data recovery e Performance of personnel and equipment In addition subsequent annual program reviews should consider the following factors e Representativeness of data to characterize typical long term and worst case short term air toxics conditions in the region e Changes in population distribution e Changes in the type or amounts of airborne pollutants released in your region Changes in needs of the program sponsors e Cost effectiveness of the program e Changes in public perception of regional air airborne concentrations and or potential exposure opportunities e Emerging regulatory issues e Availability of improved sampling analytical methods and equipment Based on the above factors you can determine whether program modifications are needed or whether the monitoring should be discontinued 6 4 REPORTING RESULTS AND CONCLUSIONS Generally the public and media are int
14. Simple collection equipment interferences H2504 IMPINGER SAMPLER AND ANALYZED BY Standard analysis method IC HC IN AMBIENT AIR IS COLLECTED WITH NaOH NIOSH 7903 0 14 14ng m3 2096 1096 Simple collection equipment Interferences IMPINGER SAMPLES AND ANALYZED BY IC Standard analysis method H2S IN AMBIENT AIR AND COLLECTED ON NIOSH 296 15 ng m3 80 10096 15 Portable sample media Limited holding time from sampling MOLECULAR SIEVE THERMALLY ADSORBED AND Proposed Minimal interference to analysis ANALYZED BY GC FID Reproducibility of results may vary with each sample collected TABLE C 11 SUMMARY OF SAMPLING AND ANALYTICAL METHODS FOR NEAR REAL TIME AMBIENT AIR MONITORING DEVELOPING TECHNOLOGIES Method Detection i i s 1 2 Sampling and Analysis Approach Designation Precision Advantages Disadvantages MOBILE MASS SPECTROMETER MS MS Compound identificationin complex Expensive MS MS MS OR GC MS mixtures Skilled operators Direct sampling Low sensitivity Field operation LONG PATH FT IR Remote Optical Volatile Direct field measurements Applicable for source Emissions Recorder Laser source transmitted Minimum time requirement characterization across contaminated area Onsite Fourier Does not provide low detection Transform analyis of reflected laser beam provides limits organic contaminant analysis by Infrared Provides concentration integrated Spectorometry o
15. 165 83 121 1 19 0 127 18 4 Chlorobenzene Phenyl chloride CgHs5C 112 56 132 0 45 6 108 90 7 Ethylbenzene 5 2 5 106 17 136 2 95 0 100 41 4 m Xylene 1 3 Dimethylbenzene 1 3 CHa oCeH 106 17 139 1 47 9 p Xylene 1 4 Dimethylxylene 1 4 CH3 2CsH4 106 17 138 3 13 3 Styrene Vinyl benzene CgH5CH CH 104 16 145 2 30 6 100 42 5 1 1 2 2 Tetrachloroethane CHCloCHClo 167 85 146 2 36 0 79 34 5 o Xylene 1 2 Dimethylbenzene 1 2 CHa oCeH 106 17 144 4 25 2 1 3 5 Trimethylbenzene __ Mesitylene 1 3 5 CH3 3CgHg 120 20 164 7 44 7 108 67 8 1 2 4 Trimethylbenzene Pseudocumene 1 2 4 CH3 3CgHe 120 20 _ 169 3 43 8 95 63 6 m Dichlorobenzene 1 3 Dichlorobenzene 1 3 4 147 01 173 0 24 7 541 73 1 Benzyl chloride a Chiorotoluene CgH5CH5CI 126 59 179 3 39 0 100 44 7 o Dichlorobenzene 1 2 Dichlorobenzene 1 2 ClaCgH 147 01 180 5 17 0 95 50 1 p Dichlorobenzene 1 4 Dichlorobenzene 1 4 2 147 01 174 0 53 1 106 46 7 1 2 4 Trichlorobenzene 1 2 4 Cl3C6H3 181 45 213 5 17 0 120 82 1 U S EPA Compendium Method T014 1988 TABLE 2 ION ABUNDANCE AND EXPECTED RETENTION TIME FOR SELECTED VOCs ANALYZED BY GC MS SIM Compound Freon 12 Dichlorodifluoromethane Methyl chloride Chloromethane Freon 114 1 2 Dichloro 1 1 2 2 tetrafluoroethane Vinyl chloride Chloroethene Methy bromide Bromomethane Ethyl chloride Chloroethane Freon 11 Trichlorofluoromethane Vinylidene chloride 1 1 D
16. The NIOSH manuals contain a wealth of information on sampling and analytical procedures for a wide range of toxic organic and inorganic species Although primarily directed at determination of worker exposure levels these methods can quite often be applied with minimal modifications to the measurement of ambient concentration levels of con cern in perimeter and offsite monitoring 8 N J DEP October 1987 Ambient Air Monitoring at Hazardous Waste and Superfund Sites Division of Environ mental Quality Air Quality Management and Surveillance New Jersey Department of Environmental Protection Trenton New Jersey 08625 67 10 11 12 13 14 15 16 17 18 This document contains a master table for sampling and analytical methods for ambient air monitoring listed by com pound name Key information on species includes recommended sampling and analytical methods the applicability of each method performance data and reference information South Coast Air Quality Management District SCAQMD October 1985 Guidelines for Implementation of Rule 1150 1 South Coast Air Quality Management District Engineering Division El Monte California 91731 This document contains standard operating procedures for the collection of ambient air samples at landfill perimeters and for instantaneous landfill surface monitoring as well as analytical procedures for a wide range of toxic volatile organic compounds U S EPA Apr
17. Thompson G Richter A Cryogenic Preconcentration Direct FID PDFID Method for Measurement of NMOC in the Ambient Air EPA 600 4 85 063 U S Environmental Protection Agency Research Triangle Park NC August 1985 18 R A Rasmussen and J E Lovelock Atmospheric Measurements Using Canister Technology J Geophys Res 83 8369 8378 1983 R A Rasmussen and M A K Khalil Atmospheric Halocarbons Measurements and Analysis of Selected Trace Gases Proc NATO ASI on Atmospheric Ozone BO 209 231 Dave Paul Dayton and JoAnn Rice Development and Evaluation of a Prototype Analytical System for Measuring Air Toxics Final Report Radian Corporation for the U S Environmental Protection Agency Environmental Monitoring Systems Laboratory Research Triangle Park NC 27711 EPA Contract No 68 02 3889 WA No 120 November 1987 U S EPA Compendium Method T014 1988 120 TABLE 1 VOLATILE ORGANIC COMPOUND DATA SHEET MELTING CAS Hexachlorobutadiene 1 1 2 3 4 4 Hexachloro 1 3 butadiene 121 MOLECULAR BOILING COMPOUND SYNONYM FORMULA WEIGHT POINT C NUMBER Freon 12 Dichlorodifluoromethane CloCF2 120 91 29 8 158 0 Methyl chloride Chloromethane CH3Cl 50 49 24 2 97 1 74 87 3 Freon 114 1 2 Dichloro 1 1 2 2 tetrafluoroethane CICF2CCIF2 170 93 4 1 94 0 Vinyl chloride Chloroethylene CH 62 50 13 4 1538 0 75 01 4 Methyl bromide Bromomethane CH3Br 94 94 3 6 93 6 74
18. will address the manner in which data from the two activities are to be treated and vali dated during the reduction process Because TOAP monitorin data can be collected over an extended period of time and may involve several parties it is important that the QA plan ad dress procedures for transferring and storing raw and intermediate data Finally the data re duction component of the QA program will set up data validation procedures so that appro priate data validation reports can be prepared 7 7 REPORTING QUALITY ASSURANCE The report represents the final output of a TOAP monitoring program The QA plan will therefore incorporate appropriate review procedures to ensure that the report properly sum marizes the results of the study The report must be reviewed by individuals capable of recognizing technical ddeficiencies and QA inconsistencies The report should also be reviewed by project personnel who were involved in data generation Finally the report should be reviewed for editorial content to minimize ambiguities EPA Excerpt Sampling and Analysis of Toxic Organic Compounds in Ambient Air 87 APPENDIX E CALIBRATION GAS STANDARDS Cylinder gas standards of selected hazardous organic compounds at the ppb level are available through the USEPA for use in auditing the performance ambient air and stationary source measurement systems Calibration standard ranges are 5 ppb and up Information can be obtained by contacting Ro
19. 3700 GC equipped with J amp W Megabore DB 624 Capillary Column 30 m X 0 53 I D mm using helium carrier gas 128 U S EPA Compendium Method T014 1988 TABLE 9 GC MS SIM CALIBRATION TABLE 18 Jan 86 7 54 am 5 00 Absolute Minutes 0 40 Absolute Minutes 0 00 Multiplier 1 000 Last Update Reference Peak Window Non Reference Peak Window Sample Amount 0 000 Uncalibrated Peak RF Ret Time Pk Signal Descr Amt pptv Lvl Area Pk type Partial Name 5 008 T Mass 85 00 amu 13620 1 72974 1 FREON 12 5 690 2 Mass 50 00 amu 12720 1 36447 1 METHYLCHLORIDE 6 552 3 Mass 85 00 amu 8380 1 81251 1 FREON 114 6 709 4 Mass 62 00 amu 8050 1 20118 1 VINYLCHLORIDE 7 831 5 Mass 94 00 amu 12210 1 28265 1 METHYLBROMIDE 8 431 6 Mass 64 00 amu 12574 1 16149 1 ETHYLCHLORIDE 9 970 7 Mass 101 00 amu 12380 1 80088 1 FREON 11 10 929 8 Mass 61 00 amu 7890 1 38954 1 VINDENECHLORI 11 209 9 Mass 49 00 amu 12760 1 43307 1 DICHLOROMETHA 11 331 10 Mass 41 00 amu 12650 1 1945 1 ALLYLCHLORIDE 11 595 11 Mass 151 00 amu 7420 1 40530 1 3CHL3FLUETHAN 12 502 12 Mass 63 00 amu 12710 1 61595 1 1 1DICHLOETHA 13 403 13 Mass 61 00 amu 12630 1 50900 1 c 1 2DICHLETH 13 747 14 Mass 83 00 amu 7670 1 40585 1 CHLOROFORM 14 387 15 Mass 62 00 amu 9040 1 33336 1 1 2DICHLETHAN 14 623 16 Mass 97 00 amu 8100 1 38503 1 METHCHLOROFORM 15 038 17 Mass 78 00 amu 10760 1 69119 1 BENZENE 15 183 18 Mass 117 00 amu 8340 1 42737 1 CARBONTETRACH 15 829 19 Mass 63 00 amu 12780 1 38875 1 1
20. High sensitivity HIGH VOLUME GLASS FIBER FILTER AND XAD 2 TO 4 80 120 Can analyze broad range of modification compounds more efficient than extracted and analysis completed using GC MS PUF Easy to clean Good retantion of compounds 0 2 200 ng m3 LOW VOLUME PORTABLE SAMPLES WITH PUF 85 100 Basically the same as for TO 14 0 01 50 ug m3 CARTRIDGE Compounds are analyzed with above GC ECD Detection Limit Advantages Disadvantages Subject to interferences Limited sensitivity Desorption of some compounds difficult Blank contamination possible Artifact formation on adsorbent High humidity reduces collection efficiency Possibility of contamination Loss of organics during storage Disadvantages Can loose volatile compounds in storage Possibility of contamination Possible contamination Loss of organics during storage Basically the same 1 Accuracy The Agreement of an analytical measurement with a true or accepted value Values this table are expressed as Percent Recovery Measured Value True Value x 100 2 Precision The reproducibility of repeated measurements of the same property usually made under prescribed conditions Values in this table are expressed as Relative Percent Difference RPD Range Mean x 100 c9 TABLE C 7 SUMMARY OF SAMPLING AND ANALYTICAL METHODS FOR TIME INTEGRATED AMBIENT AIR MONITORING BENZO a PYRENE
21. Insert a new tape in the recorder Record the displayed number to determine weekly data s location on the tape This number will be entered at the next week s visit to copy only the data collected during the week Depress the record play buttons on the recorder The cassette tape should advance past the blank leader and stop The system is now on line for data collection REMOVING THE CASSETTE TAPE The cassette tape should advance recording all of the residual data in the data logger output buffer After the data dump remove the tape CASSETTE TAPE COPY Insert a new tape in the recorder advance the tape past the blank leader Change this number to the number recorded during the previous week s visit Depress the button to dump last week data on the tape as per manufacturer specifica tions Remove the tape Bi Weekly Zero Span Checks Pre Checks Every two weeks prior to changing the chart paper the Field Technician should perform zero span checks for wind speed WS wind direction WD and temperature TEMP and fill out a Meteorological System Checklist Form These checks should be done according to manufacturer specifications For all parameters checked WS WD TEMP record the values obtained with the chart reading and the data logger reading on the Zero Span Check Form field log book and the chart paper Examples of the checks are as follows 1 Wind Speed a Set the designated switch in the position
22. Signature Date Sampled _ Time Sampled Hours Type of Process Producing Waste Field Information Sample Receiver 1 Name and address of organization recieving sample 2 3 Chain of Possessions 1 Signature Title Inclusive Dates 2 Signature Title Inclusive Dates 3 Signature Title Inclusive Dates 26 y 5 0 IMPLEMENTING QUALITY ASSURANCE QUALITY CONTROL QA QC Regional air monitoring programs for airborne pollu tants consist of complex activities using monitoring equip ment and laboratory analysis techniques This approach is necessary to accurately quantify concentrations of airborne pollutants in ambient air Therefore it is criti cal that you ensure and maintain a high quality pro gram by implementing the appropriate QA QC pro gram elements Figure 5 1 outlines the sections described in this chapter Section 5 1 provides an overview of the QA QC elements implemented during the operation phase of the air quality program Section 5 2 discusses the routine QA QC checks and Section 5 3 addresses periodic QA QC checks Elements of the laboratory QA QC program are outlined in Section 5 4 Section 5 5 provides a discussion of data management QA QC including the type of validity checks to be performed FIGURE 5 1 KEY ELEMENTS OF QA QC FOR REGIONAL AIR MONITORING PROGRAMS DEFINING QA QC REQUIREMENTS Section 5 1 PERFORMING ROUTINE QA QC CHECKS Section 5 2 IMPLEMENTING PERIODIC QA QC CHECKS Sect
23. An internal reference material ICM is developed by a laboratory for its own internal use A certified reference material CRM is a reference material issued by an organization recog nized by practicing professionals as technically competent to do so A Standard Reference Material SRM is a certified reference material issued by the National Institute of Standards and Technology NIST All three types of reference materials are integral components of ef fective QA programs for TOAP monitoring projects SRM s are particularly important be cause they are traceable to national standards and if used as primary standards allow meaningful comparisons of data generated by different laboratories or by different sampling and analytical procedures EPA Excerpt Sampling and Analysis of Toxic Organic Compounds in Ambient Air 83 SRM s for toxic organic air pollutants at sub PPM and PPB levels were unavailable until re cently Within the past two years SRM s for several TOAP s at the 5 ppb level have been de veloped as multi component mixtures Information concerning these materials is provided in Appendix E Whenever possible these SRM s should be Incorporated into the QA program for a TOAP monitoring project 7 3 5 Quality Audits Quality auditing tasks are similar to quality control tasks and in some instances may be identical The significant difference between quality auditing and quality control tasks is that the former are administered b
24. Analytical System Initial Preparation and Tuning Humid Zero Ak Test Initia Three 3 Point Static Calibration Additional Five 5 Point Static Calibration for Nonlinear Compounds Additional Three 3 Point Static Calibration for Nonlinear Compounds GC MS SCAN SIM with Optional FID Analytical System FIGURE 13 FLOWCHART OF GC MS SCAN SIM ANALYTICAL SYSTEM PREPARATION WITH OPTIONAL FID SYSTEM U S EPA Compendium Method T014 1988 144 Log Sample In Section 10 4 1 2 83 kPa 12 psig Optional Check and Record initial Pressure Section 10 4 1 3 Record Final Pressure Sectlon 10 4 1 5 4 Calculate Dilution Factor Preparation of GC FID ECD PID Analytical System initial Preparation Humid Zero Test and Retention Time Window Test Routine Preparation Humid Zero Test and Retention Time Window Test Initial Three 3 Point Statle Calibration Daily One 1 Point Standard Calibration Additional Five 5 Point Static Calibration for Nonlinear Compounds Additional Three 3 Point Static Calibration for Nonlinear Compounds GC FID ECD PID Analysis for Primary Quantitation FIGURE 14 FLOWCHART OF GC FID ECD PID ANALYTICAL SYSTEM PREPARATION 145 U S EPA Compendium Method 014 1988 SOOA AALLOAIAS OL 5 1VOIdAL 9 4 ZE 9E SE bE 0 6 86 ce ze 92 52 yz
25. B a P AND OTHER PAHS Sampling and Analysis Approach D Meroe Detection Limit Disadvantages esignation HIGH VOLUME QUARTZ FILTER AND XAD 2 OR TO 13 100 pg m3 80 12096 1596 Effective for broad range of Possible contamination PUF CARTRIDGE SAMPLER WITH GC WITH FLAME compounds Loss of volatile organics during IONIZATION FI AND MS Easy to preclean and extract storage Low blanks HIGH VOLUME QUARTZ FILTER AND XAD 2 OR TO 13 lt 100 pg m3 95 105 1596 Effective for broad range of Possible contamination PUF CARTRIDGE SAMPLER Samples are solvent compounds extracted and analyzed using HPLC Easy to clean Loss of organics during storage Broad data base Good retention of compounds TABLE C 8 SUMMARY OF SAMPLING AND ANALYTICAL METHODS FOR TIME INTEGRATED AMBIENT AIR MONITORING FORMALDEHYDE ALDEHYDES AND KETONES Sampling and Analysis Approach Method be ection Limit Disadvantages Designation SORPTION ON SILICA GEL CARTRIDGE COOLED TO 11 1 20 ppb gt 80 10 Low detection limit Possible background contamination WITH ACIDIFIED DNPH Compounds are analyzed e Simple collection equipment Interferences by HPLC TABLE C 9 SUMMARY OF SAMPLING AND ANALYTICAL METHODS FOR TIME INTEGRATED AMBIENT AIR MONITORING VOLATILE INORGANICS Sampling and Analysis Approach Detection Limit Advantages Disadvantages HIGH VOLUME GLASS FIBER FILTER AND PUF 1 5 ng m3 25 10 Wide range of application
26. Sorption onto PUF using low volume or high volume pump TO 9 and high resolution Gas Chromatography High Resolution Mass Spectrometry HRGC HRMS Sorption onto PUF using low volume sampler and Gas Liquid TO 10 Organochlorine pesticides Chromatography coupled with ECD Sorption onto prepacked silica gel cartridge coated with TO 11 Formaldehyde acidified dinitrophenylhydrazine DNPH using low volume TO 13 Benzo a pyrene B a P and other polynuclear aromatic hydrocarbons pump and High Performance Liquid Chromatography Volatile nonpolar organic e g aromatic hydrocarbons HPLC Sorption to a combination of quartz filter and a XAD 2 or chlorinated hydrocarbons having boiling points of 30 C to about 215 C PUF cartridge using high volume sampler and GC with Flame Non methane organic compounds Collection of accurately known volume of air into cryogenically cooled trap in the field and GC FID or ECD analyses ionization Ft or MS detection or HPLC ORGANIC COMPOUNDS WHOLE AIR SAMPLERS Whole air samples are collected in a SUMMA passivated stainless steel canister and high resolution GC coupled with mass specific spectrometer GC MS SIM or GC MS SCAN Whole air samples extracted directly from ambient air and analyzed using cryogenic preconcentration and direct flame ionization detector PDFID or air samples are collected ina canister and analyzed by PD
27. an additional calibration step is performed An evacuated stainless steel canister is pressurized with calibration gas at a nominal concentration of 8 ppbv The sample is then diluted to approximately 3 5 ppbv with zero air and analyzed The instrument response factor ppbv area of the ECD for each of the three compounds is calculated for the 3 5 ppbv sample Then both the 3 5 ppbv and the 8 ppbv response factors are entered into the ECD calibration table The software for the Hewlett Packard 5880 level 4 GC is designed to accommodate multilevel calibration entries so the correct response factors are automatically calculated for concentrations in this range 12 3 Method Modification 12 3 1 Sampling 12 3 1 1 The sampling system for pressurized canister sampling could be modified to use a lighter more compact pump The pump currently being used weighs about 16 kilo grams 35 Ibs Commercially available pumps that could be used as alternatives to the prescribed sampler pump are described below Metal Bellows MB 41 pump These pumps are cleaned at the factory however some precaution should be taken with the circular 4 8 cm diameter Teflon and stainless steel part directly under the flange It is often dirty when received and should be cleaned before use This part is cleaned by removing it from the pump manually cleaning with deionized water and placing in a vacuum oven at 100 C for at least 12 hours Exposed parts of the pump head are also
28. boundary and at actual offsite receptor locations Regional air monitoring stations located at the above locations should provide data to characterize offsite con centrations of airborne pollutants Designing a Network for Model Validation Upwind downwind ambient air monitoring networks provide concentrations of airborne pollutants at the point of monitoring relative to the facility or industrial complex under consideration Each air sample collected is classified as upwind or downwind based on the wind conditions for the sampling period By comparing down wind concentrations to those measured at upwind points you can determine the relative contribution of release from the facility to ambient concentrations of air pollutants This is generally accomplished by subtracting the upwind concentration which represents background conditions compared to the facility contribution from the concurrent downwind concentrations In many cases you can directly compare these monitoring results to concentration increments for a specific source based 20 on dispersion modeling calculations and accurate source emission data The locations of air monitoring stations for model validation applications should be based on local wind patterns Air monitoring stations should be placed at the following strategic locations Upwind of the facility to characterize background air concentration levels based on the expected pre vailing wind flow during
29. canister and the canister is transported to a predetermined laboratory for analysis Upon receipt at the laboratory the canister tag data is recorded and the canister is attached to the analytical system During analysis water vapor is reduced in the gas stream by a Nafion dryer if applicable and the VOCs are then concentrated by collection in a cryogenically cooled trap The cryogen is then removed and the temperature of the trap is raised The VOCs originally collected in the trap are revolatilized separated on a GC column then detected by one or more detectors for identification and quantitation The analytical strategy for Method T014 involves using a high resolution gas chromatograph GC coupled to one or more appropriate GC detectors Historically detectors for a GC have been divided into two groups non specific detectors and specific detectors The non specific detectors include but are not limited to the nitrogen phosphorus detector NPD the flame ionization detector FID the electron capture detector ECD and the photo ionization detector PID The specific detectors include the mass spectrometer MS operating in either the selected ion monitoring SIM mode or the SCAN mode or the ion trap detector The use of these detectors or a combination of these detec tors as part of an analytical scheme is determined by the required specificity and sensitivity of the application While the nonspecific detectors are less expe
30. 201 16 096 20 Mass 130 00 amu 8750 1 30331 1 TRICHLETHENE 16 956 21 Mass 75 00 amu 4540 1 17078 1 c 1 3DICHLPRO 17 492 22 Mass 75 00 amu 3380 1 13294 1 t 1 3DICHLPRO 17 610 23 Mass 97 00 amu 12690 1 32480 1 1 1 2CHLETHAN 17 862 24 Mass 91 00 amu 10010 1 88036 1 TOLUENE 18 485 25 Mass 107 00 amu 6710 1 33330 1 EDB 19 012 26 Mass 166 00 amu 7830 1 43454 1 TETRACHLETHEN 19 729 27 Mass 112 00 amu 7160 1 44224 1 CHLOROBENZENE 20 195 28 Mass 91 00 amu 12740 1 127767 1 ETHYLBENZENE 20 407 29 Mass 91 00 amu 25400 1 200973 1 m p XYLENE 20 806 30 Mass 104 00 amu 12390 1 38332 1 STYRENE 20 916 31 Mass 83 00 amu 11690 1 64162 1 TETRACHLETHAN 20 921 32 Mass 91 00 amu 11085 1 90096 1 o XYLENE 22 528 33 Mass 105 00 amu 12560 1 108747 1 4 ETHYLTOLUEN 22 648 34 Mass 105 00 amu 12620 1 83666 1 1 3 5METHBENZ 23 179 35 Mass 105 00 amu 12710 1 70833 1 1 2 4METHBENZ 23 307 36 Mass 146 00 amu 12650 1 57409 1 m DICHLBENZEN 23 317 37 Mass 91 00 amu 7900 1 50774 1 BENZYLCHLORID 23 413 38 Mass 146 00 amu 12390 1 58127 1 p DICHLBENZEN 23 885 39 Mass 146 00 amu 13510 1 52233 1 o DICHLBENZEN 26 714 40 Mass 180 00 amu 15520 1 18967 1 1 2 4CHLBENZE 27 680 41 Mass 225 00 amu 7470 1 43920 1 HEXACHLBUTADI 129 U S EPA Compendium Method T014 1988 TABLE 10 EXAMPLE OF HARD COPY OF GC MS SIM ANALYSIS Data files DATA SYR2AOZA D File type GC MS DATA FILE Name Info SYR 1 Misc Info Operator JDF Date Jan 87 10 02 am a Ingtrment 5_
31. 3 Because the GC MS analytical system employs a Nafion permeable membrane dryer to remove water vapor selectively from the sample stream polar organic compounds may permeate concurrent with the moisture molecule Consequently the analyst should quantitate his or her system with the specific organic constituents under examination Apparatus 71 Sample Collection Note Subatmospheric pressure and pressurized canister sampling systems are commercially avail able and have been used as part of U S Environmental Protection Agency s Toxics Air Monitoring Stations TAMS Urban Air Toxic Pollutant Program UATP and the non methane organic compound NMOC sampling and analysis Program 7 1 1 Subatmospheric Pressure See Figure 2 Without Metal Bellows Type Pump 7 1 1 1 Sampling inlet line stainless steel tubing to connect the sampler to the sample inlet 7 1 1 2 Sample canister leak free stainless steel pressure vessels of desired volume e g 6 1 with valve and SUMMA passivated interior surfaces Scientific Instrumenta tion Specialists Inc P O Box 8941 Moscow ID 83843 or Anderson Samplers Inc 4215 C Wendell Dr Atlanta GA 30336 or equivalent 7 1 1 3 Stainless steel vacuum pressure gauge capable of measuring vacuum 100 to 0 kPa or 0 to 30 in Hg and pressure 0 206 kPa or 0 30 psig in the sampling system Matheson P O Box 136 Morrow GA 30200 Model 63 3704 or equivalent Gauges should be tested clean an
32. 5 2 4 Photometric DEVICES o3 525 SGUMAIN abere eus eq AGIS Ri 53 EPA Excerpt Sampling and Analysis of Toxic Organic Compounds in Ambient Air 76 SECTION 6 SECTION 7 5 3 LABORATORY SCREENING TECHNIQUES 5 3 1 Colorimetric 2 2 14 44 5 3 2 Infrared Spectroscopy IR 5 3 3 Fluorescence 5 3 4 Low Resolution Mass Spectrometry 8 5 4 COMPOUND SPECIFIC TECHNIQUES 5 4 1 Gas Chromatrography GO 1 0 94 1 1 Column TYDES MM 941 2 Detector 5 4 1 3 Injection Systems nn 5 4 2 Gas Chromatography Mass Spectrometry 5 5 4 2 1 Instrumentation DEN 9 4 2 8 ADDICAUON een 5 4 3 High Performance Liquid Chromatography HPLC 5 4 4 Thin Layer and Column Chromatrography 5 4 5 Spectroscopic SPECIFIC SAMPLING AND ANALYTICAL QUALITY ASSURANCE PROCEDURES 71 QUALITY ASSURANCE EXPECT
33. 8 C per minute Upon sample injection onto the column the MS is signaled by the computer to scan the eluting carrier gas from 18 to 250 amu resulting in a 1 5 Hz repetition rate This corresponds to about 6 scans per eluting chromatographic peak Primary identification is based upon retention time and relative abundance of elut ing ions as compared to the spectral library stored on the hard disk of the GC MS data computer The concentration ppbv is calculated using the previously established response factors see Section 10 2 3 2 as illustrated in Table 5 Note If the canister is diluted before analysis an appropriate multiplier is applied to correct for the volume dilution of the canister Section 10 4 1 4 The optional FID trace allows the analyst to record the progress of the analysis 10 4 3 GC MS SIM Analysis With Optional FID System 10 4 3 1 10 4 3 2 10 4 3 3 10 4 3 4 When the MS is placed in the SIM mode of operation the MS monitors only preselec ted ions rather than scanning all masses continuously between two mass limits As a result increased sensitivity and improved quantitative analysis can be achieved Similar to the GC MS SCAN configuration the GC MS SIM analysis is based on a combination of retention times and relative abundances of selected ions see Table 2 and Table 5 These qualifiers are stored on the hard disk of the GC MS computer and are applied for identification of each chromatographic
34. 8 1 8 3 8 4 8 5 8 6 8 7 8 8 compounds of interest vinyl chloride vinylidene chloride 1 1 2 trichloro 1 2 2 trifluoroethane chloroform 1 2 dichloroethane benzene toluene Freon 12 methyl chloride 1 2 dichloro 1 1 2 2 tetrafluoroethane methyl bromide ethyl chloride Freon 11 dichloromethane 1 1 dichloroethane cis 1 2 dichloroethylene 1 2 dichloropropane 1 1 2 trichloroethane 1 2 dibromoethane tetrachloroethylene chlorobenzene benzyl chioride hexachloro 1 3 butadiene methyl chloroform carbon tetrachloride trichloroethyiene cis 1 3 dichloropropene trans 1 3 dichloropropene ethylbenzene o xylene m xylene p xylene styrene 1 1 2 2 tetrachloroethane 1 3 5 trimethylbenzene 1 2 4 trimethylbenzene m dichlorobenzene o dichlorobenzene p dichlorobenzene 1 2 4 trichlorobenzene The cylinder s should be traceable to a National Bureau of Standards NBS Standard Reference Material SRM or to aNBS EPA approved Certified Reference Material CRM The components may be purchased in one cylinder or may be separated into different cylinders Refer to manufacturer s specification for guidance on purchasing and mixing VDCs in gas cylinders Those compounds purchased should match one s own target list Cryogen liquid oxygen bp 183 0 C or liquid argon bp 185 7 C best source Gas purifiers connected in line between hydrogen nitrogen and zero air gas cylinders and system inlet line to remove mo
35. 83 9 Ethyl chloride Chloroethane CH3CH2Ci 64 52 12 3 136 4 75 00 3 Freon 11 Trichlorofluoromethane 137 38 23 7 111 0 Vinylidene chloride 1 1 Dichloroethene 96 95 31 7 122 5 75 35 4 Dichloromethane Methylene chloride CHoClo 84 94 39 8 95 1 75 09 2 Freon 113 1 1 2 Trichloro 1 2 2 trifluoroethane CF3CICCISF 187 38 47 7 36 4 1 1 Dichloroethane Ethylidene chloride CH3CHCl gt 98 96 57 3 97 0 74 34 3 cis 1 2 Dichloroethylene CHCI 96 94 60 3 80 5 Chloroform Trichloromethane CHCl 119 38 61 7 63 5 67 66 3 1 2 Dichloroethane Ethylene dichloride gt 98 96 83 5 35 3 107 6 2 Methyl chloroform 1 1 1 Trichloroethane CH4CCla 133 41 74 1 30 4 71 55 6 Benzene Cyclohexatriene 78 12 80 1 5 5 71 43 2 Carbon tetrachloride Tetrachloromethane CCl 153 82 76 5 23 0 56 23 5 1 2 Dichloropropane Propylene dichloride 112 99 96 4 100 4 78 87 5 Trichloroethylene Trichloroethene CICH CCl 131 29 87 73 0 79 01 6 cis 1 3 Dichloropropene cis 1 3 dichloropropylene 110 97 76 trans 1 3 Dichloropropene cis 1 3 Dichloropropylene CICH2CH CHCI 110 97 112 0 1 1 2 Trichloroethane Vinyl trichloride CHaCICHCl 133 41 113 8 36 5 79 00 5 Toluene Methyl benzene 5 92 15 110 6 95 0 108 88 3 1 2 Dibromoethane Ethylene dibromide BrCH2CH2Br 187 88 131 3 9 8 106 93 4 Tetrachloroethylene Perchloroethylene
36. Benzene Carbor tetrachloride 1 2 Dichloropropane Trichloroethylene cis 1 3 Dichloropropene trans 1 3 Dichloropropene 1 1 2 Trichloroethane Toluene 1 2 Dibromoethane EDB Tetrachloroethylene Chlorobenzene Ethylbenzene m p Xylene Styrene 1 1 2 2 Tetrachloroethane 4 Ethyltoluene 1 3 5 Trimethylbenzene 1 2 4 Trimethylbenzene p Dichlorobenzene 1 2 4 Trimethylbenzene m Dichlorobenzene Benzyl chloride p Dichlorobenzene o Dichlorohenzene 1 2 4 Trichlorobenzene Hexachlorobutadiene 125 Response Factor ppbv area count 0 6705 4 093 0 4928 2 343 2 647 2 954 0 5145 1 037 2 255 0 9031 1 273 1 363 0 7911 1 017 0 7078 1 236 0 5880 2 400 1 383 1 877 1 338 1 891 0 9406 0 8662 0 7357 0 8558 0 6243 0 7367 1 888 1 035 0 7498 0 6181 0 7088 0 7536 0 8912 0 7536 0 9643 1 420 0 8912 1 004 2 150 0 4117 Expected Retention Time minutes 9 01 5 64 6 55 6 71 7 83 8 43 9 87 10 93 11 21 11 60 12 50 13 40 13 75 14 39 14 62 15 04 15 18 15 83 16 10 16 96 17 49 17 61 17 86 18 48 19 01 19 73 20 20 20 41 20 80 20 92 20 92 22 53 22 65 23 18 23 41 23 18 23 31 23 32 23 41 23 88 26 71 27 68 U S EPA Compendium Method 014 1988 Operator JDP Sample Info SRY 1 Misc Info TABLE 6 GC MS SIM CALIBRATION TABLE External Standard Integration File DATA SYR2AO2A I sequence Index 1 Last Update Reference Peak Window N
37. Calibration frequencies e Acceptable calibration quality e A statement of the appropriate environment in or conditions for which the sampling equipment can be used Provisions for proper record keeping of calibration data The QA plan will also address appropriate maintenance activities and frequencies for sam pling equipment to ensure that it operates as planned Additionally the QA plan will address procedures to document performance of maintenance activities on schedule 7 4 3 Routine Quality Control Sample Collection A QA plan for a TOAP monitoring project will include a provision for the collectin of a variety of quality control samples Qualty control samples to check overall system performance may include replicate or split samples spiked samples standard reference materials blanks and backup snipes e g series impingers or resin cartridges Split or replicate samples are use ful checks on sampling and analysis precision and should be included with each group of samples Field blanks in which the sampling activity is duplicated exactly except that no air is sainpled should also be routinely collected Backup samples should be collected whenever the recovery performance of a particular sampling medium has not been documented or is subject to wide variations depending on ambient conditions Spiked samples should be in cluded whenever an accurate spiking prcedure is available provided that the spiked material reasonably si
38. Decision Step 3 Definition of Environmental Data Use Step 4 Definition of Consequences of an Incorrect Decision Attributable to Inadequate Environmental Data Step 5 Description of Available Resources Stage Il Clarification of the Information Needed for the Decision Responsibility Senior Program Staff Step 1 Fragmentation of Decision into Decision Elements Step 2 Specification of Required Environmental Data Step 3 Definition of Decision Domain Step 4 Definition of Result to be Derived from Environmental Data Step 5 Definition of Desired Performance Step 6 Evaluation of the Need for New Environmental Data Step 7 Establish the DQO s Stage Ill Design of the Data Collection System Responsibility Technical Staff Step 1 Development of Viable Data Collection Plans That Meet the Criteria and Constraints Established in Stages and Il 3 9 QUALITY ASSURANCE PLANNING The term quality assurance QA refers to an overall system design to monitor document and control the technical performance of a program While the need for good QA protocols is widely recognized the design and implementation of them are frequently treated as seconda ry parts of the overall monitoring program If the QA protocols for a monitoring program are to serve a useful purpose they must a be readily implemented within the cost and time con straints of the program and b be well understood by the project personnel Preparation of the QA plan for a monitoring p
39. Electronic Timer Thermostat JUUOOU 134 gem BAD LE amma r IS A sane nn ALTERNATIVE SAMPLER CONFIGURATION FOR PRESSURIZED CANISTER SAMPLING U S EPA Compendium Method T014 1988 Carrier 0 32mm x 50m Low Dead Volume Tee Optional N Li eave PAGO Eee Flow Restrictor Optional Mass Spectrometer In SCAN or SIM Mode Purifiers ee eef Flamelonization eo t Detector FID FIGURE 4 CANISTER ANALYSIS UTILIZING GC MS SCAN SIM ANALYTICAL SYSTEM WITH OPTIONAL FLAME JONIZATION DETECTOR WITH THE 6 PORT CHROMATOGRAPHIC VALVE IN THE SAMPLE DESORPTION MODE 135 U S Compendium Method 014 1988 JUON AIdWVS JHL NI 3A1VA DiHdVHOOLVINOHHO 1 04 9 AHL WALSAS 3 4 09 5 529 uaDoJuN Ome anssad Doone Lad 014 1029104 pio a T 93 NEN Q eunided uona peag zuanuoy Q Ome er sojeinBay 5 9 puno z uwy cun 01155914 asaid uuo yun Be 520 curo oc 5 5 Budde uaBokig dn onenw L AO ujuy S4 sa SUBD uaDouyN lt gt 021 m SPL PIN uuy Op 110 Ome ssaoxq MOU S
40. FREON 11 VINDENECHLOR DICHLOROMETH ALLYLCHLORID SCHL3FLUETHA 1 1DICHLOETH c 1 2DICHLET CHLOROFORM 1 2DICHLETHA METHCHLOROFO BENZENE CARBONTETRAC 1 2DICHLPROP TRICHLETHENE c 1 3DICHLPR t 1 3DICHLPR 1 1 2CHLRTHA TOLUENE EDB TETRACHLETHE CHLOROBENZEN ETHYLBENZENE m p XYLENE STYRENE TETRACHLETHA o XYLENE 4 ETHYLTOLUE 1 3 5METHBEN 1 2 4METHBEN m DICHLBENZE BENZYLCHLORI p DICHLBENZE o DICHLBENZE 1 2 4CHLBENZ HEXACHLBUTAD 126 Area 12893 4445 7067 2892 2401 2134 25069 5034 4803 761 5477 9052 4761 9327 5009 6656 8332 5888 3283 4386 2228 1626 2721 14417 4070 6874 5648 11084 17989 3145 4531 9798 7694 6781 7892 3046 3880 6090 2896 562 6309 8 Jan 87 10 02 am Amount 4011 pptv 2586 pptv 1215 pptv 1929 pptv 1729 pptv 2 69 pptv 6460 1700 pptv 2348 8247 1672 pptv 1728 pptv 1970 pptv 1678 pptv 2263 pptv 2334 pptv 2167 1915 pptv 1799 pptv 2109 pptv 987 3 pptv 689 2 pptv 1772 pptv 2733 1365 pptv 2065 1524 pptv 1842 pptv 37909 pptv 1695 1376 pptv 2010 14811 1705 pptv 2095 119 1006 2164 1240 pptv 767 1 pptv 1789 TABLE 7 TYPICAL RETENTION TIME MIN AND CALIBRATION RESPONSE FACTORS ppbv area count FOR TARGETED VOCs ASSOCIATED WITH FID AND ECD ANALYTICAL SYSTEM FID ECD Response Response Peak Compound Retention Fac
41. Integrated Risk Information System IRIS which is EPA s database for health risk assessment values This database is accessible via computer e National Library of Medicine Network specific databases such as TOXLINE TOXNET Hazardous Substance Data Base HSDB This network is available through Dialogue and can be accessed via computer e TheU S EPA Health Effects Assessment Summary Tables First Quarter FY 89 and updates Please note that not all of these databases are peer reviewed Therefore readers should search and review original studies and individual sources The health oriented levels shown in the examples that follow are based on the assumption of chronic exposure to an individual contaminant In the following examples RfD s EPA reference doses will be used for non carcinogens and a multiple of the inhalation RsD and or NOEL will be used for compounds that are animal carcinogens These types of calculations can include all constituents under consideration Calculating CRI for Non Carcinogens Assuming Chronic Exposure The following examples illustrate calculations of CRIs for non carcinogens These examples use calculated annual concentrations derived by a dispersion model TOXLINE TOXNET and DIALOGUE are registered trademarks of the National Library of Medicine 53 Example 1 The RfD value for lead is 1 5 g m Assume calculated annual average lead concentration in the communit
42. PID Auto Calibration from integral Gas Cylinder Photovac PID 0 1 ppb Benzene 2 Dual Column Column operates at ambient temp Standard Automatic UV Light with signal to Manual Auto STD in lab then to field at Computer Auto Comp noise ratio 4 1 Injection diff temp Communication Good for Column Cond Can t inject liquid sample aromatics Pre flush Light fractions interferer Auto Dial Modes Photovac Tip 0 2000 ppm 0 05 ppm Benzene TABLE 3 PORTABLE GAS CHROMATOGRAPH SAMPLING SHEET DATE ____________ TIME CHROMATOGRAPHIC CONDITIONS COLUMN 1 COLUMN TYPE I D mm LENGTH mm FLOW mL min COLUMN 2 COLUMN TYPE 0 mm LENGTH mm FLOW mL min INJ NO INJ VOL COLUMN NO SETTING LOCATION SITE PLAN indicate sampling locations DATE SIGNATURE 161 U S EPA Compendium Method T014 1988 TABLE B 4 SYSTEM PERFORMANCE CRITERIA FOR PORTABLE GC Test Acceptable Suggested Criteria Compound Range Corrective Action PID Response Trichloroethylene gt 108uV sec ng Re tune or replace lamp Elution Time styrene 2 65 0 15 min Inspect for leaks adjust carrier flow Resolution Benzene Trichloroethylene gt 1 4 Replace column on analysis of a vapor mixture of benzene styrene and trichloroethylene Define by 2d W W3 where distance between the peaks W peak width at base TABLE B 5 ESTIMATED LIMITS OF DETECTION LOD FOR SELECTED VOCs C
43. Peak Once the GC MS SIM has identified the peak a calibration response factor is used to determine the analyte s concentration The individual analyses are handled in three phases data acquisition data reduction and data reporting The data acquisition software is set in the SIM mode where specific compound fragments are monitored by the MS at specific times in the analytical rum Data reduction is coordinated by the postprocessing macro program that is automatically accessed after data acquisition is completed at the end of the GC run Resulting ion profiles are extracted peaks are identified and integrated and an internal integration report is generated by the program A reconstructed ion chromatogram for hardcopy reference is prepared by the program and various parameters of interest such as time date and integration constants are printed At the completion of the macro program the data reporting software is accessed The appropriate calibration table see Table 9 is retrieved by the data reporting program 2 U S EPA Compendium Method T014 1988 11 from the computer s hard disk storage and the proper retention time and response factor parameters are applied to the macro program s integration file With reference to certain pre set acceptance criteria peaks are automatically identified and quantified and a final summary report is prepared as illustrated in Table 10 10 4 4 GC FID ECD Analysis With Optional PID System 10
44. Poyan Detection sponse Calibration Service Lack of Monitor Principle Time s Accessories Techniques Rate Response 550 551 FID 0 200 0 1 ppm at lt 5 Bag sampling Umbilical cord too short 8 hrs 4 300 555 580 FID 0 2000 0 200 ppm Ditigal readout hard to read AID Inc 0 10 000 e Flame out frequentty OVA 108 FID 0 10 0 2 ppm 2 Thermal Desorbers Hand Space e Battery failure 8 hrs 6 300 128 0 100 Model 128 available Direct Injection e Sample line kinks Century Systems Inc 0 1000 0 5 ppm 2 Optional GC available Bag Sample Compounds containing 0 2 Foxboro 0 10 000 Model 108 give low response 0 100 000 Negative Response to CO CO 2 F1 101 0 1 pm 5 Three lamps available External Gas Cyl Three lamps may miss 10 hrs C1 hydrocarbons MMU Systems Inc Low molecular 9 5 aromatics Bag Sample something CH4 weight aromatics 10 2 2 4 compounds 11 7 halocarbons TLV Sniffer Catalytic 2 0 ppm 5 Bag Sample Bacharach combustion Head Space Catalytic Bag Sample Change in gas Ecolyzer 400 combustion 1 15 temperature humidity Energistics Science affects response Miran IA ppm to 96 1 ppm 1 4 10 Foxboro and 40 Miran 1B ppm to 12 500 Foxboro Scentor GC EC 0 01 ppb C1 Preconcentration Internal gas cycle 12 950 Sentex Argon organics for Thermal Preconcentrator lonization Desorption GC Columns GC Column
45. VOCs for Identification and Quantitation FIGURE 20 FLOWCHART OF ANALYTICAL SYSTEMS PREPARATION Daily One 1 Static Calibration Additional Three 3 Point Static Calibration for Nonlinear Compounds 151 U S EPA Compendium Method T014 1988 5131545 SNOIHVA GALVIDOSSV SALUALLOV 20 VO TOHLNOI 5 ALIIVND WILSAS CZ 0t 20128 41 esuodsag 9589 9jugu Qg ones Wo Bun 2 01 1211915 2 01 16 04 gt 5 64645 01295 Busy eux 0497 401820918 1 2 01 22 01 2 5 949 9 Buung 29 aN 2 01 2 5 5 29 5 99 euguquiayy 9885 uoji3es pebDo 50 02 5 uyay 42942 einsseig p49pugjG 529 22711 0205 AY 2 wajshs
46. a broad range of participants so that study results can be credibly communicated and be accepted by the various publics Funding for the program may come entirely from industry or from other sponsors regulatory agencies community groups or environmental trust funds Responsibilities for planning and implementing tasks are outlined in Figure 1 1 These tasks are discussed in detail in Chapters 3 0 7 0 Once program objectives are defined and the management structure is established and operating your management group must develop a monitoring program plan Even after the monitoring program plan is written your management team must continue to follow the plan implementation to ensure that the program s objectives are met Note that all of the individual items in Figure 1 1 will come into play at some point during the project Be aware that if you do not continue to follow the plan throughout the project its data and results may not be defensible ghe tte ELI E hts e E 405 eas 3 0 DEVELOPING THE MONITORING PLAN AND METHODOLOGIES The monitoring plan provides the detailed design regional air toxics monitoring program It is the design that sets the boundaries for the program by defining the elements involved through a well thought out process By developing a monitoring plan you will answer the f
47. adjustments with either the compounds of interest or detector with a reference compound Upto Nolibrary for retention times 20 compounds can be processed at any ume APPENDIX D BIBLIOGRAPHY OF AIR MONITORING STANDARD OPERATION PROCEDURES 65 ere APPENDIX D BIBLIOGRAPHY OF AIR MONITORING STANDARD OPERATION PROCEDURES 1 APCA May 1987 Proceedings of the 1987 EPA APCA Symposium on Measurement of Toxic and Related Air Pollutants VIP 8 Air Pollution Control Association Pittsburgh Pennsylvania 15230 These proceedings cover a wide range of topics on recent advances in measurement and monitoring procedures for toxic and related pollutants found in ambient and source atmospheres 2 APHA 1977 Methods of Air Sampling and Analysis American Public Health Association APHA Cincinnati Ohio This manual is a comprehensive compilation of standardized methods for sampling and analysis of ambient and workplace air adopted by the APHA Intersociety Committee on Methods of Air Sampling and Analysis 3 ASTM 1980 Sampling and Analysis of Toxic Organics in the Atmosphere American Society for Testing and Materials STP 721 Philadelphia Pennsylvania This publication resulted from the fourth biennial Boulder Colorado Conference on environmental monitoring of air quality sponsored by the ASTM The conference was structured to highlight several major areas of concern to env
48. analyst can then proceed to GC MS SIM The GC MS SIM is used for final quantitation of selected VOOs Polar compounds however cannot be identified by the GC MS SIM due to the use of a Nafion dryer to remove water from the sample prior to analysis The dryer removes polar compounds along with the water The analyst often has to make this decision incorporating project objectives detection limits equipment availability cost and personnel capability in developing an analytical strategy Figure 20 outlines the use of the GC FID ECD PID as a screening approach with the GC MS SCAN SIM for final identification and quantitation This procedure may involve hazardous materials operations and equipment This method does not purport to address all of the safety problems associated with its use It is the user s responsibility to establish appropriate safety and health practices and determine the applicability of regulatory limita tions prior to the implementation of this procedure This should be part of the user s SOP manual 117 U S EPA Compendium Method T014 1988 12 5 Quality Assurance See Figure 21 12 5 1 Sampling System 12 5 1 1 12 5 1 2 12 5 1 3 12 5 1 4 12 5 1 5 12 5 1 6 Section 9 2 suggests that a portable GC system be used as a screening analysis prior to locating fixed site samplers pressurized or subatmospheric section 9 2 requires pre and post sampling measurements with a certified mass flow controll
49. and 2 copies of the work must include a cover page bearing CMA s notice of copyright and this notice Copies of the work made under the authority of this license may not be sold by any party other than CMA References to registered trademarks are not intended as endorsements of the products by the Chemical Manufacturers Association Chemical Manufacturers Association 1990 Table of Contents Section Page Executive SUMMA Dre ee we Ele es vii EU recat hcc ER ond tet wide a aw ee tase oa ere ee ee 1 1 1 Organization of the 1 Why Conduct an Air Toxics Monitoring Program 2 2 0 Getting a Monitoring Program Started 5 21 Defining 5 2 2 Involving Others in the Program 6 2 3 Establishing a Management Structure 7 3 0 Developing the Monitoring Plan and 9 3 1 Overview of Plan 9 3 2 Selecting Constituents Of Interest 10 3 3 Selecting Duration and Frequency of Monitoring 11 3 4 Selecting Sampling and Analytical Methods
50. and reporting costs range from 237 000 to 286 000 This results in an estimated first year total cost range of 313 000 to 391 000 These costs could be adjusted to account for changes in the program For example by eliminating the PM 10 metal sampling and analysis program first year total costs could be reduced by about 73 000 to 88 000 r9 unl nur sobre E APPENDIX A LIST OF TOXIC AIR POLLUTANTS FOR REGIONAL MONITORING PROGRAMS 45 He zug m APPENDIX A LIST OF TOXIC AIR POLLUTANTS FOR REGIONAL MONITORING PROGRAMS This appendix includes a list of airborne pollutants for regional air monitoring programs The list consists of two tables Table A 1 includes the list of VOCs quantified in the EPA Toxic Air Monitoring Stations TAMS program and Table A 2 includes the EPA Urban Air Toxics Monitoring Program Compound List Table A 3 includes the list of chemicals analyzed under the Houston Regional Monitoring HRM pro gram In addition you may want to consider other air borne pollutants particularly those on the list identi fied in the Community Right to Know Act otherwise known as the list in Title III Section 313 of the Superfund Amendments Reauthorization Act SARA of 1986 The lists included in this appendix contain pollutants for which an analytical method is readily availab
51. ases ME ys 1 so LEE 4 0 OPERATING THE NETWORK Good operation of the air monitoring network is criti cal to high quality data collection and analysis There fore it is imperative that staff assigned to the program be well trained in various phases of network operation This will help ensure that the operation and monitoring plan requirements are met This chapter discusses of the elements associated with network operations Figure 4 1 outlines these elements Properly trained in house personnel involved with the program is an important ingredient for its successful implementation Section 4 1 provides a discussion on the selection and training of project personnel Procuring equipment is also an important element in the program implementation Section 4 2 provides a dis cussion of the steps of the procurement process Once the equipment is procured installed and tested operating and maintaining the field instrumentation starts This subject is discussed in Section 4 3 Recordkeeping requirements including various man uals logs information sheets chain of custody forms and other records are discussed in Section 4 4 441 SELECTING AND TRAINING PERSONNEL In house staff should be involved with regional air monitoring programs at various levels For example they may direct and manage the program while imple mentation is provided by a contractor Or they may con duct one or more t
52. available from previous moni toring programs in the monitored region These data would identify potential air toxics constituents and their estimated concentrations Use such data with caution because changes in demographics may have occurred after these data were collected Sec tion 3 8 contains several references on previous monitoring programs 2 3 e Results of air dispersion modeling Such results provide information on calculated levels of air toxics at different locations within the community relative to their releases e Lists contained in state and local air toxics policies and procedures Constituents Ranking Index CRI values These can provide important information for establishing priorities for air toxics constituents as a part of the selection process The ranking process is explained in Appendix B The CRI is the ratio of a constituent s calculated or measured air concentration to a health oriented number derived from animal experimental data The derived ratios are used to rank the constituents as explained in Appendix B Other ranking methods are availabie for the selection of the list of target constituents Examples include The Modified Hazardous Air Pollutant Prioritization System MHAPPS and Source Category Ranking System Using these factors together with the results of the air toxics survey monitoring can provide you the basis for determining whether your regional air toxics program will
53. available immediately Can be cost effective for high Provides information on temporal concentration Laboratory costs can be expensive for numerous samples e Short term temporal concentration variations not defined Equipment is complex Number of sampling constituents limited Accuracy can be impaired by interferences High detection levels e Matrix interferences a major problem disadvantages of alternative monitoring techniques A list of references and tables which provide additional guidance on regional air monitoring methodologies is presented in Appendix C Tables C 2 through C 10 sum marize time integrated sampling and analysis techniques for organic and inorganic air pollutants These methods are recommended for regional air monitoring Table C 11 in Appendix C includes information on emerging technologies for regional air monitoring These technologies are not recommended for use in regional air monitoring at this time but are applicable to some special purpose studies This section along with the data included in Appendix C provides useful guidance in the selection process for regional air monitoring techniques 3 5 DEFINING METEOROLOGICAL REQUIREMENTS The number of meteorological stations associated with regional air monitoring programs depends on specific local conditions such as topography land water inter face the distanc
54. chromatographic valve Seismograph Service Corp Tulsa OK Seiscor Model VIII or equivalent Chart recorder optional compatible with the detector output signals to record optional FID detector response to the sample Electronic integrator optional compatible with the detector output signal of the FID and capable of integrating the area of one or more response peaks and calcu lating peak areas corrected for baseline drift GC MS SIM Analytical System See Figure 4 7 2 2 1 7 2 2 2 The GC MS SIM analytical system must be capable of acquiring and processing data in the MS SIM mode All components of the GC MS SIM system are identical to Sections 7 2 1 2 through 7 2 1 16 GC Multidetector Analytical System See Figure 5 and Figure 6 7 2 3 1 7 2 3 2 7 2 3 3 Gas chromatograph with flame ionization and electron capture detectors photoion ization detector optional capable of sub ambient temperature programming for PN the oven and simultaneous operation of all detectors and with other generally standard features such as gas flow regulators automatic control of valves and inte grator etc Hewlett Packard Rt 41 Avondale PA 19311 Model 5880A with oven temperature control and Level 4 BASIC programming or equivalent Chart recorders compatible with the detector output signals to record detector response to the sample Electronic integrator compatible with the detector output signals and capable of
55. cleaned with swabs and allowed to air dry These pumps have proven to be very reliable however they are only useful up to an outlet pres sure of about 137 kPa 20 psig Neuberger Pump Viton gaskets or seals must be specified with this pump The factory direct pump is received contaminated and leaky The pump is cleaned by disassembling the pump head which consists of 116 U S EPA Compendium Method T014 1988 12 3 1 2 12 3 2 Analysis 12 3 2 1 12 3 2 2 12 4 Method Safety three stainless steel parts and two gaskets cleaning the gaskets with deionized water and drying in a vacuum oven and remachining or manually lapping the ing surfaces of the stainless steel parts The stainless steel parts are then cleaned with methanol hexane deionized water and heated in a vacuum oven The cause for most of the problems with this pump has been scratches on the metal parts of the pump head Once this rework procedure is performed the pump is considered clean and can be used up to about 240 kPa 35 psig output pressure This pump is utilized in the sampling system illustrated in Figure 3 Urban Air Toxics Sampler The sampling system described in this method can be modified like the sampler in EPA s FY 88 Urban Air Toxics Pollutant Program This particular sampler is des cribed in Appendix C see Figure 19 Inlet tubing from the calibration manifold could be heated to 50 C same tempera ture as the calibration manifo
56. computer calibration table is updated with this information as illustrated in Table 6 Routine Calibration The GC MS system is calibrated daily and before sample analysis with a one point calibration The GC MS system is calibrated either with the dynamic calibration procedure see Figure 8 a or with 6 L SUMMAS passiv ated canister filled with humid calibration standards from the calibration manifold see Section 10 2 3 2 After the single point calibration the GC MS analytical sys tem is challenged with a humidified zero gas stream to insure the analytical system returns to specification less than 0 2 ppbv of selective organics 10 3 GC FID ECD System Performance Criteria With Optional PID System See Figure 14 10 3 1 Humid Zero Air Certification 10 3 2 10 3 3 10 3 1 1 10 3 1 2 10 3 1 3 Before system calibration and sample analysis the GC FID ECD analytical system is assembled and checked according to manufacturer s instructions The GC FID ECD system is first challenged with humid zero air see Section 12 2 2 and monitored Analytical systems contaminated with less than 0 2 ppbv of targeted VOCs are acceptable GC Retention Time Windows Determination See Table 7 10 3 2 1 10 3 2 2 10 3 2 3 10 3 2 4 10 3 2 5 Before analysis can be performed the retention time windows must be established for each analyte Make sure the GC system is within optimum operating conditions Make three inject
57. describe and document the following activities in their laboratory 1 assembly calibration leak check and operation of the specific portable GC sampling system and equipment used 2 preparation storage shipment and handling of the portable GC sampler 3 purchase certification and transport of standard reference materials and 4 all aspects of data recording and processing including lists of computer hardware and software used 10 1 2 Specific stepwise instructions should be provided in the SOPs and should be readily avail able to and understood by the personnel conducting the survey work 157 U S EPA Compendium Method T014 1988 10 2 Quality Assurance Program 10 2 1 Reagent and materials control The carrier gas employed with the portable GC is zero air containing less than 0 1 ppm VOCs System performance mixtures are certified standard mix tures purchased from Scott Specialty Gases or equivalent Sampling protocol and chain of custody Sampling protocol sheets must be completed for each sample Specifics of the sample with regard to sampling location sample volume analysis conditions and supporting calibration and visual inspection information are detailed by these documents An example form is exhibited in Table B 3 10 2 2 10 2 3 Blanks Duplicates and System Performance Samples 10 2 3 1 10 2 3 2 Blanks and Duplicates Ten percent of all injections made to the portable GC are blanks where
58. electronics data logger and a chart recorder Air samples will be collected once every sixth day at the three sites for a total of 198 VOCs canister samples and 198 filter samples QA QC samples will include 34 samples collected at the collocated VOCs and particulate metal samp lers add 17 field blanks and 17 trip blank samples for particulate metals only This results in a total of 68 VOC canister samples and 34 filter samples The monitoring plan will include a detailed air dispersion modeling study reflected in the upper range startup cost No adjustment was made to the cost to account for discounts on the large volumes of samples to be analyzed A cost adjustment could be 10 to 20 per cent depending on the arrangements made with the laboratory Site preparation costs e g for electrical power and fencing are not included 43 Table 7 3 provides the cost estimates for a long term regional air monitoring study measuring VOCs and metals particulates These cost estimates do not include the short duration survey If you choose to adopt a two phase program a short duration survey and then long term fixed monitoring study the costs must be adjusted to avoid double counting expenses In particular adjust ments will be needed for capital and startup costs Capital costs range from 50 000 to 64 000 dollars Startup costs range from 26 000 to 41 000 Estimated annual operating costs as well as data management
59. in Section 10 2 which insure the samples collected represent the indoor environment Range and Limits of Detection The range and limits of detection of this method are highly compound dependent due to large differ ences in response of the portable GCs photoionization detector to the various target compounds Aromatic compounds and olefinic halogenated compounds will be detected at lower levels than the halomethanes or aliphatic hydrocarbons The concentration range of application of this method is approximately two orders of magnitude 158 9 5 EPA Compendium Method T014 1988 TABLE B 1 ESTIMATED LIMITS OF DETECTION LOD FOR SELECTED VOCs BASED ON 1 uL SAMPLE VOLUME Compound LOD ng LOD ppb Chloroform 2 450 1 1 1 Trichloroethane 2 450 Carbon tetrachloride8 2 450 Benzene 006 2 1 2 Dichloroethaneb 05 14 Trichloroethyleneb 05 14 Tetrachloroethylene 05 14 1 2 Dibromoethane 02 2 p Xylene 02 4 02 4 o Xylened 01 3 Styrene 01 3 aChloroform 1 1 1 Trichloroethane and Carbon tetrachloride coelute on 0 66 m 3 SP2100 b1 2 Dichloroethane Tricholroethylene and Tetrachloroethylene coelute on 0 66 m 3 SP2100 Cp Xylene and m Xylene coelute on 0 66 m 3 SP2100 dStyrene and o Xylene coelute on 0 66 m 39 SP2100 159 U S EPA Compendium Method T014 1988 091 TABLE B 2 COMMERCIALLY AVAILABLE PORTABLE VOC DETECTION INSTRUMENTS sample Waste L m 1 5 0 5 8861 101
60. integrated Limited list of organic compounds by chemical species Historical integrated Most organics but not by chemical species Realtime continuous Various organics and inorganics for a specific chemical species 4 E Historical integrated Historical integrated Semi volatile chemical species Historical integrated TABLE 3 3 A SUMMARY OF TIME INTEGRATED MONITORING TECHNIQUES FOR ORGANICS AND INORGANICS IN AIR EPA Technique 1 Method Number Type of Compounds ORGANIC COMPOUNDS TRAPS Volatile nonpolar organic e g aromatic hydrocarbons chlorinated hydrocarbons having boiling points in the range of 80 to 200 C in gas or vapor phase Sorption onto Tenax GC Packed Cartridges using low volume pump and GC MS Analysis Highly volatile nonpolar organics e g vinyl chloride vinylidene chloride benzene toluene having boiling points in the range of 15 to 120 C in gas or vapor phase Sorption onto Carbon Molecular Sieve packed cartridge using low volume pump and GC MS analyses Volatile nonpolar organics having boiling points in the TO 3 range of 10 to 200 C in gas or vapor phase Sorption onto polyurethane PUF using high volume TO 4 Organochlorine pesticides and PCBs sampler and GC ECD analysis Sorption onto Thermosorb N packed cartridges using TO 7 N Nitrosodimethylamine in gas phase low volume pump GC MS analysis
61. of Toxic and Related Air Pollu tants May 1987 APCA Publication VIP 8 EPA 600 9 87 010 J D Pleil Automated Cryogenic Sampling and Gas Chromatographic Analysis of Ambient Vapor Phase Organic Compounds System Design EPA Contract No 68 02 2566 Research Triangle Park NC Northrop Services Inc Environmental Sciences 1982 K D Oliver and J D Pleil Analysis of Canister Samples Collected During the CARB Study in August 1986 EPA Contract No 68 02 4035 Research Triangle Park NC Northrop Services Inc Environmental Sciences 1987 J D and D Oliver Measurement of Concentration Variability of Volatile Organic Compounds in Indoor Air Automated Operation of a Sequential Syringe Sampler and Subsequent GC MS Analysis EPA Contract No 68 02 4444 Research Triangle Park NC Northrop Services Inc Environmental Sciences 1987 J F Walling The Utility of Distributed Air Volume Sets When Sampling Ambient Air Using Solid Adsorbents Atmospheric Environ 18 855 859 1984 J Walling J Bumgarner J D Driscoll M Morris A Riley and H Wright Reac tion Products Desorbed From Tenax Used to Sample Ambient Air Atmospheric Environ 20 51 57 1986 Portable Instruments User s Manual for Monitoring VOC Sources EPA340 1 88 015 U S Environmental Protection Agency Office of Air Quality Planning and Standards Washington DC June 1986 F McElroy V
62. on the wind speed card Mark Chart paper as WS zero check and leave the switch Zero position for two minutes Record data logger reading 172 b Set the designated switch in the position on the WS card Mark chart paper as WS span check and leave the switch in position for two minutes Record data logger reading c Return the switch to Operate position 2 Wind Direction NOTE Crossarm must be connected for this check a Set the first designated switch in the Zero position and the second switch in the Zero Cal position on the WD card Mark the chart paper as WD zero check and leave the two switches in their respective positions for 028 two minutes Record data logger reading b Set the first designated switch in the position and leave the second switch in the Zero position on the WD card Mark chart paper as WD span check 3500 and leave both switches in their respective positions E for two minutes Record data logger reading Bi Weekly Retrieval Replacement of Chart Paper The Field Technician should retrieve and replace the chart paper after completion of the bi weekly zero span checks as per manufacturer specifications Bi Weekly Zero Span Calibration Adjustments If any of the chart readings or data logger readings during the bi weekly zero span checks were not within the specifications shown in the calibration log adjustments sh
63. peer review It is important that other industries government agencies and the public be involved to gain credibility for the program viii 1 0 INTRODUCTION Before starting a monitoring project industry must establish a clear understanding of the overall goal objec tives and driving forces behind ambient air toxics moni toring This includes identifying community concern and regulatory requirements This document has been developed for the Chemical Manufacturers Association CMA by NUS Corporation Its ultimate objective is to guide planning and implemen tation of regional air toxics monitoring programs The specific objectives of this document are e To provide a basic yet comprehensive guide for planning and implementing regional air toxics monitoring programs To allow flexibility in tailoring regional programs to meet specific local needs e To provide a framework that will ensure consistency between the various regional programs which will allow the development of a useful data base provide a systematic process for the decision maker usually the facility or plant manager within a region to ensure the development and implementation of successful regional air toxics monitoring programs Those interested in monitoring air toxics levels in com munities where they operate will find this document useful It primarily addresses how to plan and operate regional monitoring networks for volatile organic c
64. program is complete detailed documentation of field and labora tory activities The required documentation should include the following Personnel Training Records e Monitoring Equipment Manuals Monitoring Plan Field Logs e Sample Information Sheets Chain of Custody Forms e Laboratory Logbook e Sample Analysis Sheets including support documentation QA QC Data Audit Checklist e Maintenance Records Personnel training records for key staff members should be maintained by the group responsible for con ducting the air monitoring program The Monitoring Plan document should encompass the air monitoring program network configuration and independent station designs This record should consist of a topographical map showing station locations a set of drawings including a site plan with the monitoring locations identified and a diagram of the sampling equipment for each station Vendor manuals should also be included in the document The field operator should use a Field Log to maintain a record of sample numbers dates deployed and sam pling conditions The operator should note equipment condition sampling problems or equipment failures observed weather conditions and unusual site activities in the field log The field operator should also complete Sample Infor mation Sheets for each sample The recorded information should be similar to that required for Field Log Entries However the S
65. sam ple air stream Further experience has shown that inlet lines and surfaces sometimes build up or accumulate substantial concentrations of organic materials under stagnant zero flow rate condi tions Therefore such lines and surfaces need to be purged and equilibrated to the sample air for some time prior to the beginning of the actual sample collection period For this reason the sampler includes dual timers one of which is set to start the pump several hours prior to the specified start of the sample period to purge the inlet lines and surfaces As illustrated in Figure C 1 sample air drawn into the canister passes through only four components the heated inlet line a 2 micron particulate filter the electron flow controller and the latching solenoid valve Summary of Method 2 1 2 2 2 3 In operation timer 1 is set to start the pump about 6 hours before the scheduled sample period The pump draws sample air in through the sample inlet and particulate filter to purge and equilibrate these components at a flow rate limited by the capillary to approximately 100 cm min Timer 1 also energizes the heated inlet line to allow it to come up to its controlled temperature of 65 to 70 degrees C and turns on the flow controller to allow it to stabilize The pump draws additional sample air through the flow controller by way of the normally open port of the 3 way solenoid valve This flow purges the flow controller and allows it to achieve
66. selected you must prepare them to accept the monitoring instruments The equipment used for VOC and particulate sampling has its own housing and does not require special instrument shelters If you want to monitor for gaseous criteria air pollutants SO NO CO 4 you need a temperature controlled shelter at each site You must prepare platforms for mounting the VOC samplers and particulate samplers if required These platforms are needed to keep samplers at a proper height above the ground You must also build a tower foundation for the instal lation of the meteorological station The size of the foun dation can vary based on the type of tower employed and the type of soil involved Meteorological stations usually are provided with their own housing for the electronics and data logger and in general do not require additional shelters An integral part of the site preparation includes the supply of reliable electricity In general the electricity supply requirements are 110 volt AC and 15 20 amperes Finally the monitoring site should be fenced and lighted at night for security reasons If it is located on res idential property on the roof of a building or property which is otherwise secure these requirements may not apply Use of Models to Select Monitoring Sites You can also use atmospheric dispersion models to assist in designing a regional air monitoring program Modeling results can identify areas of high
67. show 2 9 00 for 9 00 AM Monday Note indicates AM and indicates The CLOCK button is pressed Display should show If an error is made EE EE is shown on the display The CLEAR button is pressed and the above steps are repeated The selector switch is turned to AUTO or MAN to verify correct time setting 166 U S EPA Compendium Method T014 1988 5 3 ON and OFF Entry 5 4 The selector switch is turned to SET The ON and OFF program is entered in the following order day number time AM or ON or OFF Example To turn ON at 12 00 AM on day 5 Thursday 5 1200 AM ON is entered Example To turn OFF at 11 59 PM on day 5 Thursday 5 11 59 PM OFF is entered If the display indicates an error E the timer is reset The selector switch is turned to AUTO ON and OFF Verification 541 The selector switch is turned to REVIEW The number of the scheduled sample day is pressed ON is pressed The display should show the time of the beginning of the sample period for example 5 12 00 indicates ON is pressed again The display should show 5 indicating no other ON times are programmed 5 4 2 OFF is pressed The display should show the time of the end of the sample period for example 5 11 59 PM is indicated by the mark before the time OFF is pressed again The display should show 5 indicating
68. stations Each will inlcude a VOCs sampler and a high volume PM 10 sampler to collect particulate matter samples for metals analysis One of the sites will include meteorological station and additional collocated VOCs and PM 10 samplers The following assumptions apply to this cost example e The network will include three fixed stations e The network will operate for one year e The network will include four time integrated whole air canister samplers four time integrated high volume PM 10 metals samplers one 10 meter meteorological station and auxiliary equipment and supplies The meteorological station will consist of wind speed wind direction sigma theta and ambient temperature sensors mounted on a crank up 10 m TABLE 7 3 EXAMPLE RANGE OF COST ESTIMATES FOR IMPLEMENTING CASE LONG TERM REGIONAL AIR MONITORING PROGRAM FOR VOCs AND METAL PARTICULATE Operation Cost Data Management and Reporting VOC Air Monitoring O Capital Cost 4Time integrated whole air canister samplers 22 000 30 000 Metals Air Monitoring De Werorogeammoniome _ _ 4 Time integrated high volume PM 10 samplers 17 000 18 000 e Supplies and samples shipment 11 500 12 500 Laboratory analysis for 232 canister samples and 173 000 199 500 266 filter samples Interpretation and reporting Total after the first year 271 100 360 400 tower supporting
69. the blank is reagent grade nitrogen gas This is the second injection in each sampling location An additional 10 of all injections made are duplicate injections This will enhance the probability that the chromatogram of a sample reflects only the composition of that sample and not any previous injection Blank injections showing a significant amount of contaminants will be cause for remedial action System Performance Mixture An injection of the system performance mixture will be made at the beginning of a visit to a particular sampling location i e the first injection The range of acceptable chromatographic system performance criteria and detector response is shown in Table B 4 These criteria are selected with regard to the intended application of this protocol and the limited availability of standard mixtures in this area Corrective action should be taken with the column or PID before sample injections are made if the performance is deemed out of range Under this regimen of blanks and system performance samples approxi mately eight samples can be collected and analyzed in a three hour visit to each sampling location 10 3 Method Precision and Accuracy 10 4 The purpose of the analytical approach outlined in this method is to provide presumptive informa tion regarding the presence of selected VOCs and SVOCs emissions In this context precision and accuracy are to be determined However quality assurance criteria are described
70. the field but should not be used to collect ambient samples Ideally deploying field blanks should coincide in time and location with the collocated sampling Analysis of the field blanks for contamination should indicate the acceptability of sample handling and decontamination operations This procedure is not necessary for VOC canisters Canisters must be certified as being clean and free of contamina tion before sample collection Additional routine QA QC checks are summarized in Tables 5 2 and 5 3 5 3 IMPLEMENTING PERIODIC QA QC CHECKS Periodic QA QC checks should be implemented to supplement the routine checks They should include monthly spiked samples quarterly audits of program performance and quarterly calibration of measurement and control devices such as flow controllers timers and meteorological equipment You can routinely check the accuracy of sample analysis by submitting spiked and blank gas samples as part of the laboratory analysis package Spiked samples should contain a known concentration s of some of the TABLE 5 3 CALIBRATION REQUIREMENTS FOR SAMPLING AND ANALYSIS INSTRUMENTATION o Device Parameter Calibrated _ Method of Calibration Approximate Frequency SAMPLING INSTRUMENTATION Sampling flow rate measurement device Sample volume measurement device usually a dry test meter ANALYTICAL INSTRUMENTS Column performance and response retention time for each analyte Chromatographic i
71. the wide variety of compounds of interest and the lack of standardized sampling and analytical procedures While there are numerous procedures for sampling and analyzing VOCs SVOCs in ambient air this method draws upon the best aspects of each one and combines them into a standard ized methodology To that end the following individuals contributed to the research documentation and peer review of this manuscript 118 U S EPA Compendium Method T014 1988 Topic Sampling System Analytical System GC FID GC FID ECD GC FID ECD PID GC MS SCAN SIM Canister Cleaning Certification and VOC Canister Storage Stability Cryogenic Sampling Unit U S EPA Audit Gas Standards Contact Mr Frank McElroy Mr Vince Thompson Dr Bill McClenny Mr Joachim Pleil Mr Tom Merrifield Mr Joseph P Krasnec Mr Vince Thompson Dr Bill McClenny Mr Joachim Pleil Ms Karen D Oliver Dave Paul Dayton JoAnn Rice Dr Bill McClenny Mr Joachim Pleil Mr John V Hawkins Mr Vince Thompson Dr Bill McClenny Mr Joachim Pleil Dave Paul Dayton JoAnn Rice Dr R K M Jayanty Mr Lou Ballard Mr Pete Watson Mr Joachim Mr Bob Lampe Address U S Environmental Protection Agency Telephone No 919 541 2622 Environmental Monitoring Systems Laboratory 919 541 3791 MD 77 Research Triangle Park N C 27711 U S Environmental Protection Agency 919 541 3158 Environmental Monitoring
72. trichloroethane isovaleraldehyde benzene methylcyclopentene carbon tetrachloride cyclohexane isoheptane 2 3 dimethyl pentane cyclohexane 2 pentanone 1 2 dichloropropane 3 methylhexane 1 butanol valeraldehyde 3 pentanone trichloroethylene bromodi chloromethane 1 heptene 2 2 4 trimethylpentane 1 4 dioxane Butyl Mercaptan 3 heptene n heptane 2 heptene bichloromethyl ether 2 4 4 trimethyl 1 pentene methylcyclohexane cis 1 3 dichloropropene 2 9 4 trimethyl 2 pentene methylisobutylketone 2 5 dimethylhexane 2 chloroethyl vinyl ether trans 1 3 dichloropropene 1 1 2 trichloroethane 2 3 4 trimethylpentane 2 methyithiophene toluene 3 methylthiophene 1 methyicyclohexene dibromochloromethane 3 5 5 trimethylhexene TABLE A 3 Cont LIST OF COMPOUNDS INCLUDED IN THE HOUSTON REGIONAL MONITORING HRM PROGRAM FOR AIR TOXICS CAS Compound Name CAS Compound Name 589 81 1 112 3 methylheptane 872 05 9 146 1 decene 66 25 1 113 hexanal 106 46 7 147 p dichlorobenzene 110 01 0 114 tetrahydrothiophene 538 93 2 148 isobutylbenzene 3522 94 9 115 2 2 5 trimethylhexane 124 18 5 149 n decane 111 66 0 116 1 octene 526 73 8 150 1 2 3 trimethylbenzene 127 18 4 117 tetrachloroethylene 95 50 1 151 o dichlorobenzene 111 65 9 118 n octane 99 87 6 152 p isopropyltoluene 7642 04 8 119 cis 2 octene 496 11 7 153 indan 541 31 1 120 isopentyl mercaptan 95 13 6 154 Indene 108 90 7 121 chlorobenzene 138 86 3 155 limonene 100 41 4 122 ethylb
73. 0 115 AC 2 BLACK MAGNELATCH SOLENOID VALVE C2 BEN 40 10 450 V p COMPONENTS Capactor and C2 40 ut 450 VDC Sprague TVA 1712 er equivalent Resine anc R2 05 watt 5 mierance and 02 3000 PRV 25 RCA SK 2081 er equivalent a Simple Circuit For Operating Magnelatch Valve 01 TIMER 2 AED SWITCH o oo 02 MAGNELATCH CK 115 AC SOLENOID AC 127K 27K VALVE BRIDGE RELAY RECTIFIER coi WHITE COMPONENTS 20 uf Brage Recther 200 PRV 15 RCA SK 3105 or equivalent 400 Voit Dy and 02 1000 25 BK 3081 equivalent NON POLARIZED Capechor C4 200 ut 250 VDC Sprague TVA 1528 or equivalent Capec or Co 20 ut 400 Mon Polarized Sprague 1652 or equivalent 10 000 ohm coil 3 5 AMF Poner and KCP 5 equivalent R and R2 05 wan 5 tolerance b Improved Circuit Designed To Handle Power Interruptions FIGURE 9 ELECTRICAL PULSE CIRCUITS FOR DRIVING SKINNER MAGNELATCH SOLENOID VALVE WITH A MECHANICAL TIMER 140 U S EPA Compendium Method T014 1988 CANISTER SAMPLING FIELD DATA SHEET A GENERAL INFORMATION SITE LOCATION ue SHIPPING DATE SITE ADDRESS an 2 rep i CANISTER SERIAL NO SAMPLER ID OPERATOR SAMPLING gt 40 CANISTER LEAK CHECK DATE
74. 0 For automatic operation the timer is wired to start and stop the pump at appropriate times for the desired sample period The timer must also control the solenoid valve to open the valve when starting the pump and close the valve when stopping the pump The use of the Skinner Magnelatch valve avoids any substantial temperature rise that would occur with a conventional normally closed solenoid valve that would have to be energized during the entire sample period The temperature rise in the valve could cause outgassing of organic compounds from the Viton valve seat mat erial The Skinner Magnelatch valve requires only a brief electrical pulse to open or close at the appropriate start and stop times and therefore experiences no tempera ture increase The pulses may be obtained either with an electronic timer that can be programmed for short 5 to 60 seconds ON periods or with a conventional mechanical timer and a special pulse circuit A simple electrical pulse circuit for operating the Skinner Magnelatch solenoid valve with a conventional mechanical timer is illustrated in Figure 9 a However with this simple circuit the valve may operate unreliably during brief power interruptions or if the timer is manually switched on and off too fast A better circuit incorporating a time delay relay to provide more reliable valve operation is shown in Figure 9 b 8 3 cm3 min The connecting lines between the sample inlet and the canister should
75. 1 1 17 Heater thermostat automatically regulates heater temperature Elmwood Sensors Inc 500 Narragansett Park Dr Pawtucket RI 02861 Model 3455 RC 0100 0222 or equivalent Fan for cooling sampling system EG amp G Rotron Woodstock NY Model SUZAI or equivalent Fan thermostat automatically regulates fan operation Elmwood Sensors Inc Pawtucket RI Model 3455 RC 0100 0244 or equivalent Maximum minimum thermometer records highest and lowest temperatures during sampling period Thomas Scientific Brooklyn Thermometer Co Inc P N 9327H30 or equivalent Nupro stainless steel shut off valve leak free for vacuum pressure gauge Auxiliary vacuum pump continuously draws ambient air to be sampled through the inlet manifold at 10 L min or higher flow rate Sample is extracted from the mani fold at a lower rate and excess air is exhausted Note The use of higher inlet flow rates dilutes any contamination present in the inlet and reduces the possibility of sample contamination as a result of contact with active adsorption sites on inlet walls Elapsed time meter measures duration of sampling Conrac Cramer Div Old Saybrook CT Type 6364 P N 10082 or equivalent Optional fixed orifice capillary or adjustable micrometering valve may be used in lieu of the electronic flow controller for grab samples or short duration time integrated samples Usually appropriate only in situations where screening
76. 1986 Ambient Air W T Winberry and Y Tilley Supplement to EPA 600 4 84 041 Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air EPA 600 4 87 006 U S Environmental Protection Agency Research Triangle Park NC 1986 W A McClenny J J W Holdren and N Smith Automated Cryogenic Preconcentration and Gas Chromatographic Determination of Volatile Organic Compounds Anal Chem 56 2947 1984 J D Pleil and K D Oliver Evaluation of Various Configurations of Nafion Dryers Water Removal from Air Samples Prior to Gas Chromatographic Analysis EPA Contract No 68 02 4035 Research Triangle Park NC Northrop Services Inc Environmental Sciences 1985 D Oliver and J D Automated Cryogenic Sampling and Gas Chromatographic Analysis of Ambient Vapor Phase Organic Compounds Procedures and Comparison Tests EPA Contract No 68 02 4035 Research Triangle Park NC Northrop Services Inc Environmental Sciences 1985 W A McClenny and J D Pleil Automated Calibration and Analysis of VOCs with a Capillary Column Gas Chromatograph Equipped for Reduced Temperature Trapping Proceedings of the 1984 Air Pollution Control Association Annual Meeting San Francisco CA June 24 29 1984 W McClenny J D T A Lumpkin and D Oliver Update on Canister Based Samplers for VOCs Proceedings of the 1987 EPA APCA Symposium on Measurement
77. 231 Office of Air Quality Planning and Standards Research Triangle Park North Carolina 27711 dU vn ee t E Kamin eor menn wen 4 6 0 MANAGING AND EVALUATING THE DATA Obtaining and evaluating data from your regional air monitoring program is your key objective Steps to handle process and report data are discussed in this section Section 6 1 provides guidance to store and summarize meteorological and air quality data including the type of summaries recommended The format of the database however is not provided in this document Currently is in the process of developing a consistent format for regional air monitoring data After your data is summarized the interpretation pro cess starts Section 6 2 discusses how to interpret the results Section 6 3 addresses the steps associated with re evaluation of program progress 6 1 STORING AND SUMMARIZING THE DATA The recommended process for managing and evaluat ing data from a regional air monitoring program is sum marized in Figure 6 1 The first step in the process of summarizing and evalu ating the data includes developing a way to handle the data usually using a computerized data base Each meteorological monitoring station should be equipped with an automated data processor that provides hourly average values for each parameter These data should be in a dig
78. 3 5 13 0 Section 10 3 1 requires the GC FID ECD analytical system prior to analysis to be certified clean less than 0 2 ppbv of targeted VOCs through a humid zero air certification Section 10 3 2 requires that the GC FID ECD analytical system establish retention time windows for each analyte prior to sample analysis when a new GC column is installed or major components of the GC system altered since the previous determination Section 8 2 requires that all calibration gases be traceable to a National Bureau of Standards NBS Standard Reference Material SRM or to a NBS EPA approved Cer tified Reference Material CRM Section 10 3 2 requires that the retention time window be established throughout the course of a 72 hr analytical period Section 10 3 3 requires both an initial multipoint calibration three levels plus humid zero air and a daily calibration one point of the GC FID ECD analytical system with zero gas dilution of NBS traceable or NBS EPA CRMs gases Note Gas cylin ders of VOCs at the ppm and ppb level are available for audits from the USEPA Environmental Monitoring Systems Laboratory Quality Assurance Division MD 778 Research Triangle Park NC 27711 919 541 4531 Appendix outlines five groups of audit gas cylinders available from USEPA The determination of volatile and some semi volatile organic compounds in ambient air is a complex task primarily because of
79. 4 4 1 10 4 1 2 10 4 4 3 10 4 4 4 10 4 4 5 10 4 4 6 10 4 4 7 10 4 4 8 10 4 4 9 10 4 4 10 10 4 4 11 The analytical system should be properly assembled humid zero air certified see Section 12 2 and calibrated through a dynamic standard calibration procedure see Section 10 3 2 The FID detector is lit and allowed to stabilize Sixty four minutes are required for each sample analysis 15 min for system initiali zation 14 min for sample collection 30 min for analysis and 5 min for post time during which a report is printed Note This may vary depending upon system con figuration and programming The helium and sample mass flow controllers are checked and adjusted to provide correct flow rates for the system Helium is used to purge residual air from the trap at the end of the sampling phase and to carry the revolatilized VOCs from the trap onto the GC column and into the FID ECD The hydrogen burner air and nitrogen flow rates should also be checked The cryogenic trap is connected and verified to bc operating properly while flowing cryogen through the system The sample canister is connected to the inlet of the GC FID ECD analytical system The canister valve is opened and the canister flow is vented past a tee inlet to the analytical system at 75 cm3 min using a 0 500 cm3 min Tylan mass flow controller During analysis 40 cm3 min of sample gas is pulled through the six port chromato graphic valve
80. 5970 Inlet GC Sequence index 1i Als bottle num Replicate num TIC pf DRTR EYE2RB2Rh D 2900 1880 n 15 DE M ES 1466 Aw ga e wv ow Sp a no 15 NS bart ren TIn pred BBB E gt em 7 EM SDG H G 51 m m Ving tp Tim gt gt lige rare Am 3 175 s 206 14 Ft nn amp 5 16 1 2 25 _ it Integration Farameters FALSE Shoulder Detection Enabled is 0 020 s Expected Feak Width Min 11 Initial Feat Detection Threshold 4 000 THRESHOLD 2 000 4 000 WIDTH 0 200 9 800 FEAK WIDTH 0 060 130 U S EPA Compendium Method T014 1988 TABLE 10 EXAMPLE OF HARD COPY OF GC MS SIM ANALYSIS cont Operator JDP Sample Info SRY 1 Misc Info Integration File Name DATA SYR2A02A Sequence Index 1 Last Update Reference Peak Window Non Reference Peak Window Sample Amount 0 000 Uncalibrated Peak RF Peak Int Ret Signal Num Type Time Description 1 1 PP 5 020 Mass 85 00 amu 2 1 PP 5 654 Mass 50 00 amu 3 1 BP 6 525 Mass 85 00 amu 4 1 PB 6 650 Mass 62 00 amu 5 1 BP 7 818 Mass 94 00 amu 6 1 BB 8 421 Mass 64 00 amu 7 1 BV 9 940 Mass 101 00 amu 8 1 BP 10 869 Mass 61 00 am
81. 7 09 PDE Chemicals in the Community Implementing Regional Air Monitoring Programs Prepared for the Chemical Manufacturers Association NUS Corporation 1990 Chemical Manufacturers Association Legal Notice This document identifies methods used to implement regional air monitoring programs Knowledgeable profes sionals prepared this document using accepted information There is no representation expressed or implied that these methods are suitable for any given application The intended user of this document is the technical professional and the regional decision maker Neither CMA nor this document can replace the necessary professional judgment needed to recommend specific procedures or methods on how to proceed Each reader must analyze the particular circumstances tailor the information in this document to those circumstances and get appropriate technical and legal assistance CMA does not assume any lia bility resulting from the user or reliance upon any information procedures conclusions or opinions contained in this document This document may be copied in its entirety and distributed freely as provided below This work is protected by copyright The Chemical Manufacturers Association CMA owner of the copyright hereby grants a nonexclusive royalty free license to reproduce and distribute this workbook subject to the following limitations 1 The work must be reproduced in its entirety without alterations
82. A method number and the type of compounds detected are included in Table 3 3 Additional details are included in Appendix C U S EPA considers canisters for collecting whole air samples on a time integrated basis as the method of choice but not the only acceptable method for sampling volatile organic compounds It is the recommended method for regional air monitoring programs Sorbent tubes and Tedlar bags should be considered as second and third choices respectively for collecting volatiles on a time integrated basis You should be aware of the limi tations associated with these methods They include a short holding time from sampling to analysis and a higher risk of sample losses and contamination Near real time air toxic monitoring techniques are a second choice alternative to time integrated methods These techniques can provide reasonably accurate infor mation in ppbs on ambient air quality of organic com pounds in the gas phase They also use a combination of air sampling and a near real time analytical analysis without the use of offsite laboratory facilities The analysis is performed with field portable gas chroma tograph GC systems see examples in Table 3 2 Limitations of the near real time methods included in the following TABLE 3 2 AN OVERVIEW OF AIR TOXICS MONITORING SAMPLING TECHNIQUES TIME INTEGRATED Gas Phase Particulate Phase High volume samplers with glass fiber filter and pol
83. AN SIM System Performance Criteria 12 5 3 GC Multidetector System Performance Criteria 13 0 Acknowledgements 14 0 References APPENDIXA Availability of Audit Cylinders from U S Environmental Protection Agency USEPA to USEPA Program Regional Offices State Local Agencies and Their Contractors APPENDIX Operating Procedures for a Portable Gas Chromatograph Equipped With Photoionization Detector APPENDIX C Installation and Operating Procedures for Alternative Air Toxics Samplers 94 U S EPA Compendium Method T014 1988 METHOD T014 DETERMINATION OF VOLATILE ORGANIC COMPOUNDS VOCs IN AMBIENT AIR USING SUMMA PASSIVATED CANISTER SAMPLING AND GAS CHROMATOGRAPHIC ANALYSIS 1 0 Scope 2 0 3 0 1 1 1 2 1 3 This document describes a procedure for sampling and analysis of volatile organic compounds VOCs in ambient air The method is based on collection of whole air samples in SUMMA passivated stainless steel canisters The VOCs are subsequently separated by gas chromatography and meas ured by mass selective detector or multidetector techniques This method presents procedures for sampling into canisters to final pressures both above and below atmospheric pressure respectively referred to as pressurized and subatmospheric pressure sampling This method 15 applicable to specific VOCs that have been tested and determined to be stable when stored in pressurized and subatmospheric pressure canisters Numerou
84. AND ANALYTICAL METHODS FOR TIME INTEGRATED AMBIENT AIR MONITORING VOLATILE OXYGENATES Method T 1 2 i Sampling and Analysis Approach Designation Detection Limit Accuracy Precision Advantages Disadvantages 90 110 10 Low cost 90 110 20 High sensitivity Positive compound ID SUMMA PASSIVATED CANISTER AND GC FID EC TO 14 0 5 20 ppb OR GC PID EC OR GC MS Whole air samples are TO 3 0 5 20 ppb collected in an evacuated stainless steel canister Calibration time consuming Compound identification is not absolute Low sensitivity Expensive VOCs are concentrated in the laboratory with cryogen trap VOCs are revolatized separated on a GC column and passed to one or more detectors for identification and quantitation AIR SAMPLE DRAWN THROUGH DINITROPHENYLHYDRAZINE IMPINGER SOLUTION USING A LOW VOLUME PUMP The solution is TO 5 1 5 ppbv 80 120 10 analyzed using HPLC with a UV detector AIR STREAM DRAWN THROUGH TENAX TO 1 1 5 ppbv 75 125 15 20 CARTRIDGE AND ADSORBED IT Desorption from Tenax is by thermal desorption to GC MS or GC FID COLLECTION OF WHOLE AIR SAMPLES IN SUMMA TO 14 1 ppbv PASSIVATED STAINLESS STEEL CANISTERS VOCs are separated by GC methods and measured by MS or multi detector techniques 1 Accuracy The Agreement of an analytical measurement with a true or accepted value Values in this table are expressed a
85. ATIONS 7 2 QUALITY ASSURANCE AND QUALITY CONTROL 7 3 QUALITY ASSURANCE MANAGEMENT 7 3 1 Quality Assurance System Design 7 3 2 Document Control 7 3 3 Data Evaluation and 7 3 4 Standard Reference Materials 7 3 5 Quality 7 3 5 1 Performance 7 3 5 2 System 7 3 6 Quality Assurance Reports 7 3 7 Corrective Action 7 3 8 Training EDER REN Um 7 4 SAMPLING QUALITY 7 4 1 Site 7 4 3 Routine Quality Control Sample Collection 7 4 4 Sample Labeling Preservation Storage and Transport 7 4 5 Chain of Custody Procedures 7 5 ANALYTICAL QUALITY 65 7 5 1 Method Validation
86. C is used to deliver zero air Procedure 9 1 Instrument Setup 9 1 1 The portable gas chromatograph must be prepared prior to use in the ambient survey sampling The pre sampling activities consist of filling the internal carrier gas cylinder charging the internal power supply adjusting individual column carrier gas flows and stabilizing the photoionization detector 9 1 2 The internal reservoir is filled with zero air The internal 12V 6AH lead acid battery can be recharged to provide up to eight hours of operation A battery which is discharged will automatically cause the power to the instrument to he shut down and will require an overnight charge During AC operation the batteries will automaticaily be trickle charged or in a standby mode 156 U S EPA Compendium Method T014 1988 9 13 The portable GC should be operated using the internal battery power supply at least forty minutes prior to collection of the first sample to insure that the photoionzation detector has stabilized Upon arriving at the area to be sampled the unit should be connected to AC power if available 9 2 Sample Collection 9 2 1 After the portable gas chromatograph is located and connected to 110V the carrier gas flows must be adjusted Flows to the 1 22 meter 5 SE 30 and 0 66 meter 3 SP2100 columns are adjusted with needle valves Flows of 60 cm3 min 590 SE 30 and 30 cm3 min 3 5 2100 are adjusted by means of a calibrated rot
87. Calibration Log Form should be completed by the Field Technician whenever the bi weekly zero span checks or quarterly calibrations are conducted Field Log Book A Field Log Book will be used by the Field Technician to maintain a record of sampling conditions equipment condi tion and calibration data The information included will be similar to that required for the Meteorological System Check list Form and Calibration Log Form The Field Log is considered a backup documentation source and presents informa tion on a chronological basis Meteorological Charts The meteorological charts should be retained by the Program Director These charts could be used to supplement large periods of missing digital data on an ad hoc basis Staff Training Record Permanent training records should be maintained for the staff relevant to the air monitoring program 174 APPENDIX G DATA VALIDATION CRITERIA AND PROCEDURES 175 APPENDIX DATA VALIDATION CRITERIA AND PROCEDURES TABLE G 1 SUGGESTED METEOROLOGICAL DATA SCREENING CRITERIA U S EPA JUNE 1987 Meteorological Screening Criteriaa Variable 3 Wind Speed Flag the data if the value is less than zero or greater than 25 m s does not vary by more than 0 1 m s for 3 consecutive hours does not vary by more than 0 5 m s for 12 consecutive hours is less than zero or greater than 360 degrees does vary by more than 1 degree for more than 3 consecu
88. Exhaust Exhaust KK n e Flask BRD A Vent Shut N Off Valve Trap Zero Off Valve til Cryogenic Pressure Trap Cooler Met Regulator Liquid Argon Humidifier Trap Cryogenic Trap Cooler Liquid Argon Vacuum Shut 7 Vale Flow Control Vacuum Gauge Valve Shut Oti Valve 2 x Manffold Vent Shut amp mn Valve Optional Isothermal Oven FIGURE 7 CANISTER CLEANING SYSTEM 138 U S EPA Compendium Method 1014 1988 SGHVGNVLS H34SNVHL HALSINVD 2 ANV WALSAS HALSINVD ONILSAL 9 WALSAS TVOLLATVNV HOA GIOJINVW ANV WALSAS NOLLVHAIIVD JILVINAHOS 8 3un9l4 Puepueis woos o 5 191sjue3 pL pazunssaJd 40 4 wonog punoy KL M JajoujuoQ 552 fuo a N YX PIOJUCWY f e uyw 05 0 ______ MN 0115594 4 SEX SIN OD 40 Qid G93 dl4 09 lt U S EPA Compendium Method T014 1988 139 TIMER RED M SWITCH Cy oc 450 DC 100K
89. FID TO 12 Modified TO 3 or TO 14 5 E 8 Whole air samples are collected in Tedlar bags and subject TO 14 or TO 3 Compounds to GC FID or ECD analysis or high resolution GC compiled with MS SIM or MS SCAN ORGANIC COMPOUNDS LIQUID IMPINGERS Dinitrophenylhydrazine Liquid Impinger sampling using a low volume pump and High Performance Liquid Chromatography UV analysis Aldehydes and Ketones Aniline liquid impinger sampling using a low volume pump Phosgene and HPLC analysis Sodium Hydroxide Liquid Impinger sampling using a TO Cresol Phenol low volume pump and HPLC analysis INORGANIC COMPOUNDS FILTER SAMPLERS High volume sampler and Atomic Absorption AA or 40 CFR Part 50 Metais in particulate phase Inductive Coupled Plasma ICP Appendix B PM 10 High Volume sampler and AA or ICP 40 CFR Part 50 Inhalable metals in particulate phase up to 10 microns in Appendix J diameter High volume sampler 40 CFR Part 50 Total suspended particulate TSP Appendix B PM 10 High volume sampler 40 CFR Part 50 Inhalable particulate up to 10 microns in diameter Appendix J Additional details are included in Appendix C For sampling methodology only 14 The list of chemical species that can be accommo dated is shorter than the one handled by a fully equipped offsite laboratory Only an uncomplicated matrix of chemical spe
90. Initial Column Temperature Initial Hold Time Program Final Hold Time Mass Spectrometer Mass Range Scan Time EI Condition Mass Scan Detector Mode FID System Optional Hydrogen Flow Carrier Flow Burner Air Hewlett Packard OV 1 crosslinked methyl silicone 50 m x 0 31 mm I D 17 um film thickness or equivalent Helium 2 0 cm3 min at 250 C Constant 1 3 uL Splitless 50 C 2 min 8 C min to 150 C 15 min 18 to 250 amu 1 sec scan 70 eV Follow manufacturer s instruction for selecting mass selective detector MS and selected ion monitoring SIM mode Multiple ion detection 30 cm minute 30 cm minute 400 cm3 minute TABLE 4 4 BROMOFLUOROBENZENE KEY IONS AND ION ABUNDANCE CRITERIA Mass 50 75 95 96 173 174 175 176 177 lon Abundance Criteria 15 to 40 of mass 95 30 to 60 of mass 95 Base Peak 100 Relative Abundance 5 to 9 of mass 95 lt 2 of mass 174 gt 50 of mass 95 5 to 9 of mass 174 gt 95 but lt 101 of mass 174 5 to 9 of mass 176 124 U S EPA Compendium Method T014 1988 TABLE 5 RESPONSE FACTORS ppbv area count AND EXPECTED RETENTION TIME FOR GC MS SIM ANALYTICAL CONFIGURATION Compounds Freon 12 Methyl chloride Freon 114 Vinyl chloride Methyl bromide Ethy chloride Freon 11 Vinylidene chloride Dichloromethane Trichlorotrifluoroethane 1 1 Dichloroethane cis 1 2 Dichloroethylene Chloroform 1 2 Dichloroethane Methyl chloroform
91. LPR 1 1 2CHLRTHA TOLUENE EDB TETRACHLETHE CHLOROBENZEN ETHYLBENZENE m p XYLENE STYRENE TETRACHLETHA o XYLENE 4 ETHYLTOLUE 1 3 5METHBEN 1 2 4METHBEN m DICHLBENZE BENZYLCHLORI p DICHLBENZE o DICHLBENZE 1 2 4CHLBENZ HEXACHLBUTAD Area 12893 4445 7067 2892 2401 2134 25069 9034 4803 761 5477 5052 4761 5327 5009 6656 8332 5888 3283 4386 2228 1626 2721 14417 4070 6874 5648 11084 17989 3145 4531 9798 7694 6781 7892 3046 3880 6090 2896 562 6309 Amount 4011 pptv 2586 1215 pptv 1929 pptv 1729 2 69 pptv 6460 pptv 1700 pptv 2348 pptv 8247 pptv 1672 pptv 1728 1970 pptv 1678 pptv 2263 pptv 2334 pptv 2167 1915 pptv 1799 pptv 2109 987 3 pptv 689 2 pptv 1772 pptv 2 33 1365 pptv 2065 pptv 1524 pptv 1842 pptv 3 909 pptv 1695 pptv 1376 pptv 2010 14811 pptv 1705 pptv 2095 pptv 1119 1006 pptv 2164 1249 pptv 7671 pptv 1789 pptv U S EPA Compendium Method T014 1988 Log Sample In Section 10 4 1 2 Check and Record Initial Pressure Section 10 4 1 3 lt 83 kPa 12 psig Optional Pressurize with No To 138 kPa 20 psig Record Final Pressure Section 10 4 1 3 Calculate Dilution Factor Section 10 4 1 4 _ GC FID ECD PID Section 10 4 2 Section 10 4 3 Section 10 4 4 FIGURE 1 ANALYTICAL SYSTEMS AVAILABLE FOR CANISTER VOC IDENTIFICA
92. Laboratory Analytical Methods EPA 600 4 83 040 NTIS PB 84 126929 Office of Solid Waste Washington D C 20460 This volume provides bench level guidance for the preparation of hazardous waste water soil sediment biological tissue and air samples and methods that can be used to analyze the resultant digests extracts of 244 of the substances listed in the RCRA permit regulations U S EPA February 1986 Measurement of Gaseous Emission Rates from Land Surfaces Using an Emission Isolation Flux Chamber User s Guide EPA 600 8 86 008 Environmental Monitoring Systems Laboratory Las Vegas Nevada 89114 U S EPA December 1987 Development of Collection Methods for Semivolatile Organic Compounds in Ambient Air EPA 600 4 87 042 Environmental Monitoring Systems Laboratory Research Triangle Park North Carolina 27711 U S EPA July 1983 Standard Operating Procedures for the Preparation of Standard Organic Gas Mixtures in a Static Dilution Bottle RTP SOP EMD 012 Environmental Monitoring Systems Laboratory Research Triangle Park North Carolina 27711 U S EPA November 1981 Standard Operating Procedures for the Preparation of Tenax Cartridges Containing Known Quantities of Organics Using Flash Vaporization RTP SOP EMD 011 Environmental Monitoring Systems Laboratory Research Triangle Park North Carolina 27711 68 19 20 21 22 23 25 26 27 28 29 U S EPA November 1981 Standard Operating Pro
93. N GC FID EC 0 1 ppbv 90 110 15 100 mi sample Known volume of air iscollected accurately onto a cryogenically cooled trap Carrier gas transfers the TO 2 1 200 pptv 70 9596 t 10 40 20 ml sample biased low condensed sample to a GC column Adsorbed compounds are eiuted from the GC column and B TO 14 0 1 4 ppb 90 110 measured by FID or EC detectors 1 Accuracy The Agreement of an analytical measurement with a true or accepted value Values this table are expressed as Percent Recovery R Measured Value True Value x 100 2 Precision The reproducibility of repeated measurements of the same property usually made under prescribed conditions Values in this table are expressed as Relative Percent Difference RPD Range Mean x 100 Moisture levels in air can cause freezing problems Difficult to use in field Expensive Collects wide variety of volatile organic compounds Standard procedures are available Contaminants common to adsorbent materials are avoided Low blanks CARBON MOLECULAR SIEVE ADSORPTION AND G MS or GC FID Selected voiatile organic compounds are captured on carbon molecular sieve adsorbents Compounds are thermally desorbed and analyzed by GC MS techniques Trace levels of volatile organic compounds are collected and concentrated on sorbent material Atmospheric moisture not collected Some trace levels of organic s
94. NITORING SEMI VOLATILE PHENOLICS Sampling and Analysis Approach Method Designation 4 6 dinitro 2 methyl phenol 50 1600 specific to class of compounds Good stability Detect non volatile as well as volatile compounds SODIUM HYDROXIDE LIQUID IMPINGER AND HPLC UV Ambient air is drawn through 2 midget impingers Phenols are trapped as phenolates in NaOH solution and analyzed by HPLC TO 8 1 ppb 75 125 20 ADSORPTION AND GC FID OR GC MS TO 1 1 200 ppt 70 9596 10 40 Good QA QC data base Ambient air is drawn organic polymer sorbent Wide range of application where certain organic compounds are trapped Easy to use in field The cartridge is transferred to the laboratory for analysis Compounds are desorbed by heating HIGH VOLUME AND PUF SAMPLER AND GC ECD TO 4 0 2 2 ng m3 60 100 20 Wide range of application Sorption onto PUF followed by solvent extraction Easy to use low blanks Excellent collection and retention efficiencies TABLE C 6 SUMMARY OF SAMPLING AND ANALYTICAL METHODS FOR TIME INTEGRATED AMBIENT AIR MONITORING SEMI VOLATILE PESTICIDES PCBs Method Detection Limit Designation Sampling and Analysis Approach HIGH VOLUME GLASS FIBER AND PUF CARTRIDGE SAMPLER AND GC ECD Compounds solvent extracted and analyzed using GC ECD 0 2 200 ng m3 28to 85 10095 Broad range of application Low blanks Easy to use Reusable
95. NSE OF ECD TO VARIOUS VOCs 149 U S EPA Compendium Method T014 1988 4 bo ET di ldWvs SNOILO3NNOO LAINI AIdWVS 40 OILVIN3HOS AON3OV NOLLO3ilOHd 1VIN3ANOHIAN3 SN 6L dunold jeuojido 610009 cit 191 01309 3 uod z V uod T Dujqn 9915 Gar a 1 lt _ 559485 weg 19915 __ 559141815 b t 1946 7 559 5 L Pu 21 10MOd ejduies m 1 nn Nene jeuotido SS b b 9017 ejduies U S EPA Compendium Method T014 1988 150 Record Sample Canister In Dedicated Logbook Pressurtze with No to 15 20 psig Calculate Dilution Factor Record initialFinal Pressure GC FID ECD snd CCMS Sample Anatysis GC FID ECD PID Analytical Preparation Initial Three 3 Point Dally One 1 Point Dynamic Calibration Dynamic Calibration Additional Five 5 Point Dynamic Additional Three 3 Point Dynamic Calibration for Noniinesr Compounds Calibration for Nonfnear Compounds GC FID ECO PID Screening Analysis initia Three 3 Point Static Additional Five 5 Point Sisuc Calibration for Nonfinsar Compounds GC MSD SCAN identification and Semi quantitation of VOCs GC MSD SIM Selected
96. Note On a daily basis or more often if necessary the cryogenic traps should be purged with zero air to remove any trapped water from previous canister cleaning cycles 11 1 4 The vacuum and vacuum pressure gauge shut off valves are closed and the zero air shut off valve is opened to pressurize the canister s with humid zero air to approximately 206 kPa 30 psig If a zero gas generator system is used the flow rate may need to be limited to maintain the zero air quality 11 1 5 The zero shut off valve is closed and the canister s is allowed to vent down to atmospheric pressure through the vent shut off valve The vent shut off valve is closed Steps 11 1 3 through 11 1 5 are repeated two additional times for a total of three 3 evacuation pressurization cycles for each set of canisters 11 1 6 At the end of the evacuation pressurization cycle the canister is pressurized to 206 kPa 30 psig with humid zero air The canister is then analyzed by a GC MS or GC FID ECD analyt ical system Any canister that has not tested clean compared to direct analysis of humidified zero air of less than 0 2 ppbv of targeted VOCs should not be used As a blank check of the canister s and cleanup procedure the final humid zero air fill of 100 of the canisters is analyzed until the cleanup system and canisters are proven reliable less than 0 2 ppbv of targets VOCs The check can then be reduced to a lower percentage of canisters 11 1 7 The canist
97. ON 91155944 ee 8 gc Q Q HL Ome 5 gU 21155944 U S EPA Compendium Method T014 1988 136 AGOW NOlLdHOS3Q AIdINVS NI JAVA DIHAVHDOLVINOHHD LHOd 9 JHL WALSAS IVOILAIVNY Gld Q93 Cdl3 909 AHL QALVIDOSSV NOILVENDIANOO WALSAS 9 9 essei Sex usbonin 4 E 4012819q WM pug 94055944 picis did J9p4099H 1911956 023 40199129 Poxld 0 4 1775 Ome Sex p 941559143 wog yun 9 po vz9 aq J9jSjue2 II 45 SEO 194 J c ssaoxg OH SSEW 2 91155944 24040 Sey Hp man ro mei 191014 03 JUNG 552 sey 941055944 U S EPA Compendium Method T014 1988 137 Pressure 3 Port Regulator Vent Gas 2 00 Valve Valve Ct gt Tr Zero Ar Vacuum Pump Supply B Shut Off Valve Valve Check Valve 4 7 D Vacuum
98. PA has embraced the process of establishing Data Quality Objectives DQO s as a mechanism for ensuring that the quality of environmental data collected under a given program is consistent with the in tended use of that data The DQO process is a three stage process that places emphasis on defining the regulatory objectives of the environmental monitoring program the decision that will be made regarding the data collected and the possible consequences of the decision be ing incorrect Experimental design based on DQO s rather than on collection of the best possible data is intended to ensure that the information needed to make a decision is ob tained rather than ensuring that each individual measurement obtained is the best possible Data quality objectives are statements of the level of uncertainty that a decision maker is willing to accept from results derived from environmental data when the results are going to be used in a regulatory or programmatic decision such as establishing the need for a new regulation setting or revising a standard or determining compliance with an existing stand ard Complete data quality objectives must be accompanied by clear statements of e The decision to be made e Why environmental data are needed How the environmental data will be used e Time and resource constraints on data collection e Descriptions of the environmental data to be collected Specifications regarding the domain of the
99. Setupequipmentinthefield _ Trainin house personnel canister samplers Laboratory analysis 38 500 42 500 Option 2 three near real time portable GC analyzers Calibration supplies and other expendabies and Reporting interpretation and reporting Total Cost Option i Monitoring 84 500 106 500 58 500 78 000 Option 2 Monitoring Numbers are rounded to the nearest 500 41 canister samplers is 84 500 to 106 500 The range of estimated costs for Option 2 three near real time portable field GC analyzers is 58 500 to 78 000 The main difference between the two options can be attrib uted to the large laboratory analysis cost under Option 1 However using the second option could mean less accu rate results because of some of the limitations of port able field GC analyzers You should weigh these factors when selecting one of the two options Case Il Long Term Study In this example the purpose is to establish a long term regional air monitoring program to measure both VOCs and metals in a region with several large industrial facili ties The objective of this study is to establish ambient levels of VOCs and metals at several locations within the community over a period of a year or more The data obtained will be used to evaluate the VOCs and metals concentrations contributed by the industrial facilities The monitoring program will include three fixed mon itoring
100. Systems Laboratory 919 541 4680 MD 44 Research Triangle Park N C 27711 Anderson Samplers Inc 4215 C Wendell Drive Atlanta GA 30336 Scientific Instrumentation Specialists Inc Box 8941 Moscow Idaho 83843 U S Environmental Protection Agency 1 800 241 6898 208 882 3860 919 541 3791 Environmental Monitoring Systems Laboratory MD 77 Research Triangle Park N C 27711 U S Environmental Protection Agency 919 541 3158 Environmental Monitoring Systems Laboratory 919 541 4680 MD 44 Research Triangle Park N C 27711 Northrop Services Inc Environmental Sciences P O Box 12313 Research Triangle Park N C 27709 Radian Corporation P O Box 13000 Progress Center Research Triangle Park N C 27709 U S Environmental Protection Agency 919 549 0611 919 481 0212 919 541 3158 Environmental Monitoring Systems Laboratory 919 541 4680 MD 44 Research Triangle Park N C 27711 Research Triangle Laboratories Inc P O Box 12507 Research Triangle Park N C 27709 U S Environmental Protection Agency 919 544 5775 919 541 3791 Environmental Monitoring Systems Laboratory MD 77 Research Triangle Park N C 27711 U S Environmental Protection Agency 919 541 3158 Environmental Monitoring Systems Laboratory 919 541 4680 MD 44 Research Triangle Park N C 27711 Radian Corporation P O Box 13000 Progress Center Research Triangle Park N C 27709 Resear
101. TION AND QUANTITATION 132 U S EPA Compendium Method 7014 1988 To AC REES RR Enclosure Vacuum Pressure Gauge inlet Manifold a JR Um pe FREE US Ue Beute EN Ie SN 7 he LES YS h 4 ER 47 NN nS baad 22 Ja X 29 TREE ss T l 4 2 EE lt B SDN mr C NS ni EDEN bia N n 4 6 lee gt eee SA 4 CAN suma UM NS w WIND MA voe aive janaa i Na n SS ie em IS VU 1 6 Meters 4 e IY Ay 5 ww 1 f 4 D 5 ft X KURRE IE b gt ws tenu Magnelatch Valve Ground Level Vent Mass Flow PUMP Control Unit Thermostat A Canister Heater FIGURE 2 SAMPLER CONFIGURATION FOR SUBATMOSPHERIC PRESSURE OR PRESSURIZED CANISTER SAMPLING 33 U S EPA Compendium Method T014 1988 1 1 6 Meters 5 ft gt D GP de a Level FIGURE 3 Heated Enclosure Vent inlet Manifoid lt 88 ae Auxiliary Vacuum 8 Vacuum Pressure Gauge Pressure au pause Mechanical ZN Flow Regulator ROO Sees i Le i Vent ALA as Magnelatch Valve
102. Table 3 and calibrated for accurate VOC determination The mass flow controllers are cheched and adjusted to provide correct flow rates for the system The sample canister is connected to the inlet of the GC MS SCAN with optional FID analytical system For pressurized samples a mass flow controller is placed on the canister and the canister valve is opened and the canister flow is vented past a tee inlet to the analytical system at a flow of 75 cm3 min so that 40 cm3 min is pulled through the Mafion dryer to the six port chromatographic valve Note Fiow rate is not as important as acquiring sufficient sample volume Sub ambient pressure samples are connected directly to the inlet The GC oven and cryogenic trap inject position are cooled to their set points of 50 C and 160 C respectively As soon as the cryogenic trap reaches its lower set point of 160 C the six port chromatographic valve is turned to its fill position to initiate sample collection A ten minute collection period of canister sample is utilized Note 40 cm3 min x 10 min 400 cm sampled canister contents After the sample is preconcentrated in the cryogenic trap the GC sampling valve is cycled to the inject position and the cryogenic trap is heated The trapped analytes are thermally desorbed onto the head of the OV 1 capillary column 0 31 mm 1 0 x 50 m length The GC oven is programmed to start at 50 C and after 2 min to heat to 150 C at a rate of
103. U S EPA Compendium Method 014 1988 TABLE 8 TYPICAL RETENTION TIME minutes FOR SELECTED ORGANICS USING GC FID ECD PID ANALYTICAL SYSTEM Retention Time minutes Compound FID ECD PID Acetylene 2 984 1 3 Butadiene 3 599 3 594 Vinyl chloride 3 790 3 781 Chloromethane 5 137 Chloroethane 5 738 Bromoethane 8 154 Methylene Chloride 9 232 9 218 trans 1 2 Dichloroethylene 10 077 10 065 1 1 Dichloroethane 11 190 Chloroprene 11 502 11 491 Perfluorobenzene 13 077 13 078 13 069 Bromochloromethane 13 397 13 396 13 403 Chloroform 13 768 13 767 13 771 1 1 1 Trichloroethane 14 151 14 153 14 158 Carbon Tetrachloride 14 642 14 667 14 686 Benzene 1 2 Dichloroethane 15 128 15 114 Perfluorotoluene 15 420 15 425 15 412 Trichloroethylene 17 022 17 024 17 014 1 2 Dichloropropene 17 491 17 805 17 522 Bromodichloromethane 18 369 trans 1 3 Dichloropropylene 19 694 19 693 19 688 Toluene 20 658 20 653 cis 1 3 Dichloropropylene 21 461 21 357 21 357 1 1 2 Trichloroethane 21 823 Tetrachloroethylene 22 340 22 346 22 335 Dibromochloromethane 22 955 22 959 22 952 Chlorobenzene 24 866 24 861 m p Xylene 25 763 25 757 Styrene o Xylene 27 036 27 030 Bromofluorobenzene 28 665 28 663 28 660 1 1 2 2 Tetrachloroethane 29 225 29 227 29 228 m Dichlorobenzene 32 347 32 345 32 342 p Dichlorobenzene 32 671 32 669 32 666 o Dichlorobenzene 33 885 33 883 33 880 Varian
104. a better under standing of the impact of air toxics emissions This knowledge is of particular importance in regions with large industrial complexes Results of well designed and implemented air moni toring programs provide a ground truth for what is happening in the area or region of interest In this respect such programs can be viewed as proactive measures to obtain data from communities The public industry and regulators can use these data as one input to evaluating the impact that various sources have on the public health Regional air toxics studies benefit both the public and industry participants These efforts provide industry regulators and the public a unique opportunity to work together to find answers to difficult questions These data can provide the technically sound basis for decision making processes This section has provided an overview of the rationale for conducting an air toxics monitoring program Other factors that could affect the decision for conducting an air toxics monitoring program are driven by region specific factors It is therefore imperative for you to carefully review this document and define your specific totivations for conducting air toxics monitoring programs Lim ts nea cde zone 2 0 GETTING A MONITORING PROGRAM STARTED The most critical phase of your regional air monitor ing program is pla
105. a stable controlled flow at the specified sample flow rate prior to the sample period At the scheduled start of the sample period timer 2 is set to activate both solenoid valves When activated the 3 way solenoid valve closes its normally open port to stop the flow controller purge flow and opens its normally closed port to start flow through the aldehyde sample cartridges Simul taneously the latching solenoid valve opens to start sample flow into the canister At the end of the sample period timer 42 closes the latching solenoid valve to stop the sample flow and seal the sample in the canister and also de energizes the pump flow controller 3 way solenoid and heated inlet line During operation the pump and sampler are located external to the sampler The 2 4 meter 8 foot heated inlet line is installed through the outside wall with most of its length outside and terminated externally with an inverted glass funnel to exclude precipitation The indoor end is terminated in a stainless steel cross fitting to provide connections for the canister sample and the two optional formaldehyde cartridge samples Sampler Installation 3 1 The sampler must be operated indoors with the temperature between 20 32 68 to 90 F sampler case should be located conveniently on a table shelf or other flat surface Access to a source of 115 vac line power 500 watts min is also required The pump is removed from the sampler case and located re
106. address all the constituents included in Appendix A add more constituents or reduce the list to fit your speci fic regional situation The selected list of constituents should be specific to each study area 3 3 SELECTING DURATION AND FREQUENCY OF MONITORING Recommendations for sampling duration frequency and length of the monitoring program are summarized in Table 3 1 by program objectives Primary program objectives include air toxics survey monitoring and long term monitoring to establish community concen trations of air toxics Other program objectives include for example short or long term effect studies compli ance studies or permitting studies Actual sampling duration frequency and monitoring program length will depend on your specific project objectives and on your available project resources A representative number of air samples must be collected during the monitoring program to provide a reasonable data base The number of representative samples depends on many factors A simple statistical analysis may not provide a good basis for determining this number The recommendations specified in Table 3 1 are based on the following factors Frequencies usually adopted in monitoring grams for criteria air pollutants involving the use of time integrated samplers A minimum of one sample every six days is collected to provide ran dom weekday and weekend sampling Use of continuous monitoring for program
107. adian Corporation U S EPA August 1988 Source Category Ranking System EPA Contract No 68 02 4330 Work Assignment 51 prepared by Radian Corporation U S EPA February 1983 Quality Assurance Handbook for Air Pollution Measurements Sys tems Volume IV Meteorological Measurements EPA 600 4 82 060 Office of Research and Development Research Triangle Park North Carolina 27711 U S EPA July 1986 Guidelines on Air Quality Models Revised EPA 405 2 78 027R NTIS PB 86 245248 Office of Air Quality Planning and Standards Research Triangle Park North Carolina 27711 U S EPA May 1987 Ambient Monitoring Guidelines for Prevention of Significant Deterioration PSD EPA 450 4 87 007 Office of Air Quality Planning and Standards Research Triangle Park North Carolina 27711 U S EPA June 1987 On Site Meteorological Program Guidance for Regulatory Modeling Appli cations EPA 450 4 87 013 Office of Air Quality Planning and Standards Research Triangle Park North Carolina 27711 U S EPA December 1979 Industrial Source Complex ISC Dispersion Model Users Guide EPA Report No 450 4 79 030 Office of Air Quality Planning and Standards Research Triangle Park North Carolina 27711 d or ET m 8 roseo M ree mim ur war Dre ew emt er norme mtt an aS LIE am
108. ak Time min 1 1 2 Trichloroethane Vinyl trichloride Toluene Methyl benzene 1 2 Dibromoethane Ethylene dibromide Tetrachloroethylene Perchloroethylene Chlorobenzene Benzene chloride Ethylbenzene m p Xylene 1 3 1 4 dimethylbenzene Styrene Vinyl benzene 1 1 2 2 Tetrachloroethane Tetrachloroethane o Xylene 1 2 Dimethylbenzene 4 Ethyltoluene 1 3 5 Trimethylbenzene Mesitylene 1 2 4 Trimethylbenzene Pseudocumene m Dichlorobenzene 1 3 Dichlorobenzene Benzyl chloride Chlorotoluene p Dichlorobenzene 1 4 Dichlorobenzene o Dichlorobenzene 1 2 Dichlorobenzene 1 2 4 Trichlorobenzene Hexachlorobutadiene 1 1 2 3 4 4 Hexachloro 1 3 butadiene 123 97 100 83 90 61 82 91 100 92 57 107 100 109 96 27115 166 100 164 74 131 60 112 100 77 62 114 32 91 100 106 28 91 100 106 40 104 100 78 60 103 49 83 100 85 64 91 100 106 40 105 100 120 29 105 100 _ 120 42 105 100 120 42 146 100 148 65 111 40 91 100 126 26 146 100 148 65 111 40 146 100 148 65 111 40 180 100 182 98 184 30 225 100 207 66 2231 60 17 61 17 86 18 48 19 01 19 73 20 20 20 41 20 81 20 92 20 92 22 53 22 65 23 18 23 31 23 32 23 41 23 88 26 71 27 68 U S Compendium Method T014 1988 TABLE 3 GENERAL GC AND MS OPERATING CONDITIONS Chromatography Column Carrier Gas Injection Volume Injection Mode Temperature Program
109. al phase of a regional air monitoring program see Table 5 1 include QA QC management sample QA QC analytical QA QC and data reduction QA QC QA management involves implementing project speci fic administrative procedures to control QA QC func tions The potential for and types of quality problems vary depending on the activity sampling analytical and data reduction Therefore the individual QA QC requirements must be developed for each of these activities Comprehensive QA QC recommendations applicable to regional air monitoring programs are available in a number of documents Generic air monitoring QA QC recommendations are included in the Technical Assistance Document for Sampling and Analysis of Toxic Organic Compounds in Ambient Air Monitoring method specific QA QC recommendations are covered in documents issued by the U S EPAQ3 45 and NIOSH Air quality monitor ing QA QC recommendations are included in Quality Assurance Handbook for Air Pollution Measurements and Ambient Monitoring Guidelines for Prevention of Significant Deterioration PSD TABLE 5 1 QA QC ACTIVITIES TO BE SPECIFIED IN PROGRAM PLAN QA QC Management QA QC System Design Document Control Data Evaluation Audit Procedures Corrective Action QA QC Reports to Program Management Training Sample QA QC Instrument Calibration and Maintenance Collection of Routine Quality Control Samples Data Recording Sample Labeling Preser
110. alysis Data Files Storage of Raw and Intermediate Data Data Validation Preparation and analysis of sample blanks at some appropriate frequency will ensure program integrity Type of Sample Field Blanks Laboratory Blanks Spiked Samples Collocated Parallel Samples Instrument Calibration Standards Reference Samples Series Backup Samples Ten percent of the total samples collected is considered as a minimum amount for sample blanks After the sam TABLE 5 2 TYPICAL SAMPLING ANALYSIS FREQUENCIES FOR QC SAMPLES Typical Frequency Each sample set at least 10 percent of total number of samples Not necessary for VOC canisters Daily at least 10 percent of total number of samples Each batch of samples 2 28 FIGURE 5 2 REGIONAL AIR MONITORING QA QC STRATEGY Fo IMPLEMENT ON SITE METEOROLOGICAL PROGRAM GUIDANCE TECHNICAL QA RECOMMENDATIONS FOR METEOROLOGICAL MONITORING IMPLEMENT TECHNICAL ASSISTANCE DOCUMENT TAD TECHNICAL QA RECOMENDATIONS FOR AIR TOXIC MONITORING MPLEMENT METHOD SPECIFIC QA CRITERIA IF MORE STRINGENT _ THAN TAD IMPLEMENT SUPPLEMENTAL TECHNICAL QA RECOMMENDATIONS BASED ON OTHER AVAILABLE REFERENCES AS WARRANTED IF NOT ADDRESSED ABOVE PROGRAM SPECIFIC AIR MONITORING QA QC PROGRAM pling media are prepared for field use one of each type of medium should be randomly selected as a field blank They should be deployed in
111. ameter Switching between the two columns is accomplished by turning the valve located beneath the electronic module During long periods of inactivity the flows to both columns should be reduced to conserve pressure in the internal carrier gas supply The baseline on the recorder integrator is set to 20 full scale 9 2 2 Prior to analysis of actual samples an injection of the performance evaluation mixture must be made to verify chromatographic and detector performance This is accomplished by with drawing 1 0 mL samples of this mixture from the calibration cylinder and injecting it onto the 3 SP2100 column The next sample analyzed should be a blank consisting of reagent grade nitrogen 9 2 3 Ambient air samples are injected onto the 3 SP2100 column The chromatogram is developed for 15 minutes Samples which produce particularly complex chromatograms especially for early eluting components are reinjected on the 5 SE 30 column Note In no instance should a syringe which has been used for the injection of the calibrant system per formance mixture be used for the acquisition and collection of samples or vice versa 9 24 Samples have generally been collected from the ambient air at sites which are near sus pected sources of VOCs and SVOCs and compared with those which are not Typically selection of sample locations is based on the presence of chemical odors Samples collected in areas without detectable odors have not shown significa
112. ample Information Sheets are sample specific and are considered the primary sample collection documentation The Field Log is a backup document and presents information on a chronological basis A Chain of Custody form should travel with each sample from preparation until the analysis is complete Along with sample identification tags the Chain of Custody form is used as a definitive basis to record each sample s preparation deployment and analytical history A Laboratory Notebook should also be maintained This document should contain information regarding the time and date of sample analysis as well as notes on the equipment and analytical methods being used The laboratory should make copies of this notebook and for ward it to the appropriate personnel along with the lab oratory results Laboratory technicians should routinely use Sample Analysis Sheets to document analysis results These Sheets contain a record of detected compounds and amounts for each run as well as any pertinent informa tion such as sample recovery rates Program staff should develop a standard Audit Check list to standardize and document quarterly audits see Section 5 3 The checklist should contain a succinct list of program requirements It is a useful resource to indi cate compliance status FIGURE 4 3 TYPICAL CHAIN OF CUSTODY FORM Sample Number Shipper Name Address Number Street City State Zip Collector s Name Telephone
113. ampling Procedure 10 0 Analytical System 10 1 System Description 10 1 1 GC MS SCAN System 10 1 2 GC MS SIM System 10 1 3 GC Multidetector GC FID ECD PID System 10 2 GC MS SCAN SIM System Performance Criteria 10 2 1 GC MS System Operation 10 2 2 Daily GC MS Tuning 10 2 3 GC MS Calibration 10 2 3 1 Initial Calibration 10 2 3 2 Routine Calibration 10 3 GC FID ECD System Performance Criteria With Optional PID 10 3 1 Humid Zero Air Certification 10 3 2 GC Retention Time Windows Determination 10 3 3 GC Calibration 10 3 3 1 Initial Calibration 10 3 3 2 Routine Calibration 10 3 4 GC FID ECD PID System Performance Criteria 10 4 Analytical Procedures 10 4 1 Canister Receipt 10 4 2 GC MS SCAN Analysis With Optional FID System 10 4 3 GC MS SIM Analysis With Optional FID System 10 4 4 GC FID ECD Analysis With Optional PID System 93 U S EPA Compendium Method T014 1988 11 0 Cleaning and Certification Program 11 1 Canister Cleaning and Certification 11 2 Sampling System Cleaning and Certification 11 2 1 Cleaning Sampling System Components 11 2 2 Humid Zero Air Certification 11 2 3 Sampler System Certification With Humid Calibration Gas Standards 12 0 Performance Criteria and Quality Assurance 12 1 Standard Operating Procedures SOPs 12 2 Method Relative Accuracy and Linearity 12 3 Method Modification 12 3 1 Sampling 12 3 2 Analysis mE 12 4 Method Safety 12 5 Quality Assurance _ 12 5 1 Sampling System 12 5 2 GC MS SC
114. ance Technical Review of Report Editorial Review of Report A series of volumes entitled Quality Assurance Handbook for Air Pollution Measurement Sys tems 10 serves as a useful detailed guidance document in the QA area In particular Volume Principles and Volume Ambient Air Specific Methods may be useful in the field of toxic organic monitoring Specific guidance for preparation of QA plans is provided in another EPA document 11 QA practices are also discussed in Methods of Air Sampling and Analysis 6 6 Methods of Air Sampling and Analysis M Katz ed 2nd Edition American Public Health As sociation Washington D C 1977 10 Quality Assurance for Air Pollution Measurement Systems U S Environmental Protection Agency Research Triangle Park North Carolina January 1976 V I Principles EPA 600 9 76 005 V Il Ambient Air Specific Methods EPA 600 4 77 027a 11 Interim Guidelines and Specifications for Preparing Quality Assurance Project Plants QAMS 005 80 U S Environmental Protection Agency Washington D C December 29 1980 EPA Excerpt Sampling and Analysis of Toxic Organic Compounds in Ambient Air 81 SECTION 7 QUALITY ASSURANCE 71 QUALITY ASSURANCE EXPECTATIONS As the discussion of Data Quality objectives in Section 3 indicates the environmental data used in a decision process must be 1 technically sound and defensible and 2 of sufficient quality to support the decision proce
115. and routed through the trap at the appropriate time while the extra sample is vented The VOCs are condensed in the trap while the excess flow is exhausted through an exhaust vent which assures that the sample air flowing through the trap is at atmospheric pressure The six port valve is switched to the inject position and the canister valve is closed The electronic integrator is started After the sample is preconcentrated on the trap the trap is heated and the VOCs are thermally desorbed onto the head of the capillary column Since the columm is at 50 C the VOCs are cryofocussed on the column Then the oven temperature programmed increases and the VOCs elute from the column to the parallel FID ECD assembly The peaks eluting from the detectors are identified by retention time see Table 7 and Table 8 while peak areas are recorded in area counts Figures 15 and 16 illus trate typical response of the FID and ECD respectively for the forty 40 targeted VOCs Note Refer to Table 7 for peak number and identification The response factors see Section 10 3 3 1 are multiplied by the area counts for each peak to calculate ppbv estimates for the unknown sample If the canister is diluted before analysis an appropriate dilution multiplier DF is applied to correct for the volume dilution of the canister see Section 10 4 1 4 Depending on the number of canisters to be analyzed each canister is analyzed twice and the final concentra
116. ane trans 1 3 dichloropropylene toluene n octane n octane trans 1 3 dichloropropylene cis 1 3 dichloropropylene 1 1 2 trichloroethane tetrachloroethylene dibromochloromethane chlorobenzene ethylbenzene m p xylene styrene o xylene bromoform 1 1 2 2 tetrachloroethane m dichlorobenzene p dichlorobenzene o dichlorobenzene CAS 74 85 1 74 86 2 74 84 0 115 07 1 74 98 6 74 99 7 74 87 3 75 28 5 75 01 4 75 07 0 115 11 7 106 98 9 106 99 0 106 97 8 74 93 41 624 64 6 74 83 9 463 82 1 107 00 6 590 18 1 75 00 3 67 56 1 75 71 8 563 45 1 78 78 4 123 38 6 67 64 1 75 69 4 109 67 1 75 08 1 503 17 3 64 17 5 563 46 2 109 66 0 78 79 5 75 05 8 75 35 4 646 04 8 60 29 7 627 20 3 513 35 9 75 09 2 67 63 0 75 83 2 78 84 2 142 29 0 691 37 2 287 92 3 156 60 5 79 29 8 73513 42 5 691 38 3 674 76 0 71 23 8 AA TABLE A 3 LIST OF COMPOUNDS INCLUDED IN THE HOUSTON REGIONAL MONITORING HRM PROGRAM FOR AIR TOXICS Compound Name C 2 VOC ethylene acetylene ethane C 3 VOC propylene propane propyne chioromethane isobutane vinyl chloride acetaldehyde isobutene 1 butene 1 3 butadiene n butane methyl mercaptan trans 2 butene bromomethane neopentane 1 butyne cis 2 butene chloroethane methanol dichlorodifluoromethane 3 methyl 1 butene Isopentane propionalydehyde acetone trichlorofloromethane 1 pentene ethyl mercaptan 2 butyne ethanol 2 methyl 1 butene n p
117. asis considering region specific factors project objectives resources and budget constraints Some of region specific factors that could increase the number and locations of your monitoring stations are e Type of sources involved Simple sources consist usually of well defined emission points and include several stacks that do not have nearby obstructions Complex sources involve large numbers of sources scattered over a wide area and or sources that do not have well defined emission points Complex sources have emissions from roof monitors vents valves and other components and are defined as fugitive sources These sources also include irreg ular structures that exist near emission locations Complex sources will require more monitoring sta tions than simple sources e Size of the region involved and community locations Topography coupled with wind flow and land water interface together with wind flow conditions will require additional monitoring stations at locations of anticipated high concentrations e Areas of high traffic density and locations of major arteries could require additional monitoring stations e Locations of community commercial and light industry activities could require additional monitor ing stations TABLE 3 6 RECOMMENDED RESPONSE CHARACTERISTICS FOR METEOROLOGICAL SENSORS Meteorological Variable Wind Speed Wind Direction Temperature Dew Point Temperature Source Appli
118. asks of the program while a contractor performs the remaining tasks FIGURE 4 1 KEY ELEMENTS OF NETWORK OPERATION SELECTING AND TRAINING PERSONNEL SECTION 4 1 PROCURING EQUIPMENT AND SUPPLIES SECTION 4 2 OPERATING AND MAINTAINING THE FIELD INSTRUMENTATION SECTION 4 3 FIGURE 4 2 RECORDKEEPING REQUIREMENTS SECTION 4 4 23 In any case all staff involved with the program should thoroughly understand the program s objectives and specific elements Staff in management roles should have prior experience with regional air monitoring programs In particular management personnel should have exper ience with managing and communicating with contractors including laboratories be sensitive to the health risk perception implications of the resulting air monitoring data and use skill when relating with agency person nel the media and the general public Program managers must also maintain a high commitment to developing and implementing quality assurance quality control pro grams which meet the needs of their project For staff who may be involved in field activities or other technical roles prior air monitoring experience is a valuable asset Their commitment to QA QC programs is also critical Health and safety personnel already may be qualified to participate in the air monitoring operations How ever those unfamiliar with the low detection levels parts per billion or micrograms per cubic meter which are t
119. be as short as possible to minimize their volume The flow rate into the canister should remain relatively constant over the entire sampling period If a critical orifice is used some drop in the flow rate may occur near the end of the sample period as the canister pressure approaches the final calculated pressure As an option a second electronic timer see Section 7 1 1 6 may be used to start the auxiliary pump several hours prior to the sampling period to flush and condition the inlet line 104 U S EPA Compendium Method T014 1988 9 1 3 6 Prior to field use each sampling system must pass a humid zero air certification see Section 12 2 2 All plumbing should be checked carefully for leaks The canis ters must also pass a humid zero air certification before use see Section 12 1 22 2 Sampling Procedure 9 2 1 9 2 2 9 2 3 9 2 4 9 2 5 9 2 6 9 2 7 9 2 8 9 2 9 9 2 10 9 2 11 9 2 12 9 2 13 The sample canister should be cleaned and tested acordi to the procedure in Section 12 1 A sample collection system is assembled as shown in Figure 2 and Figure 3 and must meet certification requirements as outlined in Section 12 2 3 Note The sampling system should be contained in an appropriate enclosure Prior to locating the sampling system the user may want to perform screening analyses using a portable GC system as outlined in Appendix B to determine potential volatile organ ics present and pote
120. bert L Lampe USEPA Environmental Monitoring Systems Laboratory Quality Assurance Division MD 77B Research Triangle Park NC 27711 Phone Commercial 919 541 4531 FTS 629 4531 Group Compounds Group IV Compounds Carbon tetrachloride Acrylonitrile Chloroform 1 3 Butadiene Perchloroethylene Ethylene oxide Vinyl chloride Methylene Chloride Benzene Propylene oxide Group Compounds Trichloroethylene 1 2 dichloroethane 1 2 dibromoethane ortho xylene Group V Compounds Carbon tetrachloride Acetonitrile Chloroform Trichlorofluoromethane Freon 11 Perchloroethylene Dichlorodifluoromethane Freon 12 Vinyl chloride Bromomethane Benzene Methyl ethyl ketone 1 1 1 trichloroethane Group Compounds Vinylidene chloride 1 1 2 trichloro 1 2 2 trifluoro ethene Freon 113 1 2 dichloro 1 1 2 2 tetrafluoroethane Freon 114 Acetone 1 4 Dioxane Toluene Chlorobenzene Trichloroethylene 1 2 dichloroethane 1 2 dibromoethane Methylene chloride Trichlorofluoromethane Bromomethane Toluene Chlorobenzene 1 3 Butadiene ortho xylene Ethyl benzene 1 2 dichloropropane Freon 11 EPA Excerpt Sampling and Analysis of Toxic Organic Compounds in Ambient Air 88 APPENDIX F EXAMPLES OF STANDARD OPERATING PROCEDURES SOPs SOPs FOR OPERATING VOCs CANISTER SAMPLER U S EPA COMPENDIUM METHOD 7014 1988 SOPs FOR METEOROLOGICAL STATION OPERATIONS AND CALIBRATION 89 ex EPIS
121. bromofluorobenzene and check that all key ions criteria are met If the criteria are not achieved the analyst must retune the mass spectrometer and repeat the test until all criteria are achieved 10 2 2 4 The performance criteria must be achieved before any samples blanks or standards are analyzed If any key ion abundance observed for the daily 4 bromofluorobenzene mass tuning check differs by more than 10 absolute abundance from that observed during the previous daily tuning the instrument must be retuned or the sample and or calibration gases reanalyzed until the above condition is met GC MS Calibration See Figure 13 Note Initial and routine calibration procedures are illustrated in Figure 13 10 2 3 1 Initial Calibration Initially a multipoint dynamic calibration three levels plus humid zero air is performed on the GC MS system before sample analysis with the assistance of a calibration system see Figure 8 The calibration system uses NBS traceable standards or NBS EPA CRMs in pressurized cylinders containing a mixture of the targeted VOCs at nominal concentrations of 10 ppmv in nitrogen Section 8 2 as working standards to be diluted with humid zero air The contents of the working standard cylinder s are metered 2 cm3 min into the heated mixing chamber where they are mixed with a 2 L min humidified zero air gas stream to achieve a nominal 10 ppbv per compound calibration mixture see Figure 8 This nominal 10 ppb
122. canister to a GC FID ECD analytical sys tem at 75 cm3 min so that 40 cm3 min is pulled through the six port valve and routed through the cryogenic trap see Section 10 2 2 1 at the appropriate time while the extra sample is vented Note The exit of the sampling system without the canister replaces the canister in Figure 4 After the sample 400 mL is precon centrated on the trap the trap is heated and the VOCs are thermally desorbed onto the head of the capillary column Since the column is at 50 C the VOCs are cryo focussed on the column Then the oven temperature programmed increases and the VOCs begin to elute and are detected by a GC MS see Section 10 2 or the GC FID ECD see Section 10 3 The analytical system should not detect greater than 0 2 ppbv of targeted VOCs in order for the sampling system to pass the humid zero air certification test Chromatograms of a certified sampler and contaminated sampler are illustrated in Figures 17 A and b respectively If the sampler passes the humid zero air test it is then tested with humid calibration gas standards con taining selected VOCs at concentration levels expected in field sampling e g 0 5 to 2 ppbv as outlined in Section 11 2 3 11 2 3 Sampler System Certification with Humid Calibration Gas Standards 11 2 3 1 Assemble the dynamic calibration system and manifold as illustrated in Figure 8 11 2 3 2 Verify that the calibration system is clean less than 0 2 ppbv of ta
123. cations 9 Sensor Specification s Starting Speed lt 0 5 m sec Distance Constant lt 5m Starting Speed lt 0 5 m sec 10 Deflection Damping Ratio 0 4 to 0 7 Delay Distance lt 5m Time Constant lt 1 minute Time Constant lt 30 minutes Operating Temperature Range 30 C to 30 C U S EPA On Site Meteorological Program Guidance for Regulatory Modeling TABLE 3 7 GUIDANCE FOR SELECTING THE NUMBER AND LOCATIONS OF MONITORING STATIONS FOR REGIONAL AIR MONITORING PROGRAMS Source Type Simple Sources Complex Sources Minimum Number of Monitoring Location Stations 1 2 at downwind locations preferably in residential areas where high concentrations are anticipated with a reasonable frequency of occurrence at upwind location from the sources preferably in a residential area 3 4 at downwind locations with similar characteristics as for simple sources 1 2 at upwind locations from the sources preferably in residential areas 1 For sources near topographical features add two stations to each of the above cases at locations of anticipated high concentrations with high frequency of occurrence plume impaction at high terrain location with drainage flow preferably in residential areas 2 For sources near bodies of water add two stations to each of the first cases at locations of anticipated high concentrations with high frequency of occurrence plume fumigation region preferabl
124. cedures for the Preparation of Clean Tenax Cartridges RTP SOP EMD 013 Environmental Monitoring Systems Laboratory Research Triangle Park North Carolina 27711 U S EPA January 1984 Standard Operating Procedures for Sampling Gaseous Organic Air Pollutants for Quanti tative Analysis Using Solid Adsorbents RTP SOP ESMD 018 Environmental Monitoring Systems Laboratory Research Triangle Park North Carolina 27711 U S EPA July 1985 Draft Standard Operating Procedures No FA112A Monitoring for Gaseous Air Pollutants Using the Giliam LFS Model 113 Dual Mode Air Sampling Pumps Environmental Monitoring and Compliance Branch Environmental Services Division Region VII Kansas City Kansas 66115 U S EPA June 1984 Standard Operating Procedures for the GC MS Determination of Volatile Organic Compounds Collected on Tenax RTP SOP SEMD 021 Environmental Monitoring Systems Laboratory Research Triangle Park North Carolina 27711 U S EPA August 1983 Development of Protocols for Ambient Air Sampling and Monitoring at Hazardous Waste Facilities Methods Summary Report Office of Solid Waste Land Disposal Branch Washington D C 20460 U S EPA 1984 Field Standard Operating Procedures for Air Surveillance FSOP No 8 Office of Emergency and Remedial Response Washington D C 20460 U S 1983 Air Pollution Training Institute Course 435 Atmospheric Sampling 450 2 80 004 Environmental Research Center Research Triang
125. ch Triangle institute P O Box 12194 Research Triangle Park N C 27709 NuTech Corporation 2806 Cheek Road Durham N C 27704 U S Environmental Protection Agency 919 481 0212 919 541 6000 919 682 0402 919 541 4680 Environmental Monitoring Systems Laboratory MD 44 Research Triangle Park N C 27711 U S Environmental Protection Agency 919 541 4531 Environmental Monitoring Systems Laboratory MD 77B Research Triangle Park N C 27711 119 U S EPA Compendium Method T014 1988 14 0 REFERENCES 1 10 11 12 13 14 15 16 17 19 20 D Oliver J D Pleil and W McClenny Sample Integrity of Trace Level Volatile Organic Compounds in Ambient Air Stored in SUMMA Polished Canisters Atmospheric Environ 20 1403 1986 W Holdren and D L Smith Stability of Volatile Organic Compounds While Stored in SUMMA Polished Stainless Steel Canisters Final Report EPA Contract No 68 02 4127 Research Triangle Park NC Battelle Columbus Laboratories January 1986 Ralph M Riggin Technical Assistance Document for sampling and Analysis of Toxic Organic Compounds in Ambient Air EPA 600 4 83 027 U S Environmental Protection Agency Research Triangle Park NC 1983 Ralph M Riggin Compendium of Methods for the Determination of Toxic Organic Compounds in mbient Air EPA 600 4 84 041 U S Environmental Protection Agency Research Triangle Park NC
126. cies can be analyzed e As field techniques these methods lack the ability to comply with the comprehensive quality assurance quality control QA QC procedures used by a cer tified offsite laboratory Screening air monitoring techniques such as total hydrocarbon analyzers colorimetric gas detection tubes and industrial hygiene methods are generally inexpen sive but are only successful for measuring relatively high detection levels i e in the ranges of parts per million for gaseous contaminants and milligrams per cubic meter for particulates Frequently screening air monitoring techniques provide near real time results in the field Alternative survey level techniques are presented in Table 3 2 Screening techniques are quite limited in the number of constituents that can be evaluated concur rently Hence these techniques are most effective for air monitoring near the source to confirm the presence of an air release and to provide information to support the development of specifications for a more refined moni toring program Screening techniques are not recom mended for use in regional air monitoring programs Base your selection of air monitoring methods and equipment on a number of factors including the following Physical and chemical properties of compounds e Relative and absolute concentrations of compounds e Relative importance of various compounds in pro gram objectives e Method performance c
127. commended that meteorological sensors be placed 10 meters above ground for wind and stability data and instruments for measuring para meters such as ambient temperature and precipitation be placed 2 meters above ground The use of a portable meteorological system mounted on a tripod 15 possible for certain applications such as short duration studies Siting constraints including power availability site access nearby obstructions and site security are inte gral parts of the monitoring site selection process In most monitoring applications a reliable external power source is critical Therefore if power is unavail able a candidate site should be excluded from further consideration Easy access to the site is required to ensure proper pro gram implementation An access road should be pre pared if required Or a second candidate site should be used if it is more accessible Avoid selecting a monitoring site in the vicinity of nearby obstructions that block air flow such as buildings or tall trees this is particularly important in urban areas Site security 15 an important factor in protecting the integrity of the program Sites should have fences and lights If possible equipment should be placed in instru ment shelters In addition monitoring sites could be located on residential properties where owners can pro vide some protection for the equipment Site Preparation Requirements Once monitoring sites have been
128. concentration relative to actual receptor locations These high concen tration areas which correspond to actual receptors are priority locations for siting air monitoring stations However modeling applications are limited by the amount quality and representativeness of the input data Meteorological data are a key input for developing dispersion or dilution patterns Unfortunately the results of standard dispersion models do not accurately represent most complex terrain applications 1 the results can be off by greater than a factor of 10 Air dis persion models require emission characterization infor mation as key input However the spatial variation of chemical emissions in complex industrial areas may not be well known Therefore modeling may not be appro priate if adequate input data are not available The recommended model to evaluate the dispersion of airborne pollutants for many industrial sources located in areas of flat or gently rolling topography is the Industrial Source Complex ISC Dispersion Model 10 The use of this model is not difficult and it is available for use on a personal computer Other approved models included in the EPA Guidelines for Air Quality Models are also recommended for use depending on the application under consideration If sufficient representative data are available you can use dispersion modeling to identify the area of maxi mum long term concentration levels at the property
129. ctivities of the organization Strategic QA program planning will obviously require an organizational structure conducive to effective QA management Appropriate considerations for organizational structure include personnel assignments and communication Effective QA is accomplished by a separate individual or group within the organization The individual s responsible for QA will have written job descriptions and the corresponding duties responsibilities and authority to perform their job functions in a manner that satisfies the QA program requirements EPA Excerpt Sampling and Analysis of Toxic Organic Compounds in Ambient Air 82 Although individuals associated with the QA functions are removed from the routine opera tions they are responsible for assessing they are by no means totally isolated form those rou tine operations Open lines of communication and established communication practices are necessary to ensure interaction between QA personnel personnel generating data and per sonnel assimilating the data Effective communication is therefore adequately reflected in data output 7 3 2 Document Control Because of the volume of written information associated with a TOAP monitoring program it is necessary to establish procedures for document control consisting of written procedures for inspection review revision and archival of monitoring program documents Document control procedures are generally applicable to the followin
130. ctivity to unit operating conditions and mete orological conditions sampling periods and times back ground levels and other air emission sources and interferences that may complicate data interpretation Also include data recovery for all parameters Statistical summaries of air monitoring data should be presented monthly seasonally as well as annually and for the entire monitoring period In addition to concen tration means and extremes these summaries should present any other information useful for interpretation especially if monitoring results are below analytical detection limits Also present data recovery information to evaluate data representativeness A minimum data recovery target should be 80 percent 62 INTERPRETING THE RESULTS When interpreting the results of the program the air monitoring data should be compared to some consti tuent specific health criteria applicable state local air toxics guideline or ambient air standards It is important that the monitoring results be compared to the appropri ate health based criteria For instance the maximum 35 observed values if collected over a one hour period or less should be compared only to acute health based criteria such as an EEGL Emergency Exposure Guide line Limits or IDLH Immediately Dangerous to Life and Health or some short term criteria Conversely if potential oncogenic hazard is being evaluated the average air value should be the basis fo
131. d leak tight 7114 Electronic mass flow controller capable of maintaining a constant flow rate 10 over a sampling period of up to 24 hours and under conditions of changing temperature 20 40 C and humidity Tylan Corp 19220 S Normandie Ave Torrance CA 90502 Model FC 260 or equivalent 7 1 1 5 Particulate matter filter 2 um sintered stainless steel in line filter Nupro Co 4800 E 345th St Willoughby OH 44094 Model SS 2F K4 2 or equivalent 7 1 1 6 Electronic timer for unattended sample collection Paragon Elect Co 606 Park way Blvd Box 28 Twin Rivers WI 54201 Model 7008 00 or equivalent 7117 Solenoid valve electrically operated bi stable solenoid valve Skinner Magnelatch Valve New Britain CT Model V5RAM49710 or equivalent with Viton seat and O rings 7 1 1 8 Chromatographic grade stainless steel tubing and fittings for interconnections Alltech Associates 2051 Waukegan Rd Deerfield IL 60015 Cat 8125 equiva lent All such materials in contact with sample analyte and support aids prior to analysis should be chromatographic grade stainless steel 7 1 1 9 Thermostatically controlled heater to maintain temperature inside insulated samp ler enclosure above ambient temperature Watlow Co Pfafftown NC Part 04010080 or equivalent U S EPA Compendium Method T014 1988 99 7 1 1 10 7 1 1 11 7 1 1 12 7 1 1 13 7 1 1 14 7 1 1 15 7 1 1 16 7
132. d of 90 days using two sampling systems with an additional collocated system for a total of three systems The samplers will be moved mid program so that a total of four sampling locations are used The monitoring equipment will be leased during the 90 day study Samples will be collected over a period of 24 hours on every third day Fifteen samples will be collected at each of the four sampling locations for a total of 60 samples QA QC samples for the first option will include 25 samples collected over the 90 day period by the collocated samplers QA QC samples for the second option will include 15 canister samples Site preparation costs e g for electric power and fencing are not included Table 7 2 provides the cost estimates for a short dura tion VOCs monitoring survey The range of estimated costs for Option 1 three time integrated whole air TABLE 7 2 EXAMPLE RANGE OF COST ESTIMATES FOR IMPLEMENTING THE CASE SHORT TERM VOCs AIR MONITORING SURVEY ee V Option 1 3 Time integrated whole air canister 4 500 6 000 samplers OCs Air Monitoring e 3 Time ai Option 2 3 Near real time portable field GC 13 500 15 500 analyzers Meteorological Monitoring One portable system on a tripod with a chart 1 000 2 500 recorder or a datalogger Startup Cost Develop monitoring plan 22 2 Lease equipment and initial check out 21 500 27 500
133. decision e The calculations statistical and otherwise that will be performed on the data in order to arrive at the result The DQO process is interactive consisting of three multi step stages The first two stages result in proposed DQO s with accompanying specifications and constraints for designing the data collection system In the third stage potential designs for the data collection program are evaluated The various stages and steps associated with the DQO process are summa rized in Table 3 1 3 2 4 Stage I Activities This stage is the responsibility of the decision maker He she states an initial perception of what decision must be made what information is needed why and when it is needed how it will be used and what the consequences will be if information of adequate quality is not avail able Initial estimates of the time and resources that can reasonably be made available for the data collection activity are presented 3 2 2 Stage 1 Activities This stage is primarily the responsibility of the senior program staff using guidance and oversight from the decision maker and input from technical staff The information from Stage 115 carefully examined and discussed with the decision maker to ensure that senior program staff understand as many of the nuances of the program as possible After this interactive process senior program staff discuss each aspect of the initial problem exercising their pre rogative to reconsider key
134. dit cylinders may be acquired by contacting Robert L Lampe U S Environmental Protection Agency Environmental Monitoring Systems Laboratory Quality Assurance Division MD 77B Research Triangle Park NC 27711 919 541 4531 U S EPA Compendium Method T014 1988 153 Group Compounds Carbon tetrachloride Chloroform Perchloroethylene Vinyl chloride Benzene Group Ranges 7 to 90 ppb 90 to 430 ppb 430 to 10 000 ppb TABLE A 1 AVAILABLE USEPA PERFORMANCE AUDIT CYLINDERS Group Compounds Trichloroethylene 1 2 dichloroethane 1 2 dibromoethane Acetonitrile Trichlorofluoromethane Freon 11 Dichlorodifluoromethane Freon 12 Bromomethane Methyl ethyl ketone 1 1 1 trichloroethane Group Ranges 7 to 90 ppb 90 to 430 ppb Group Ill Compounds Pyridine pyridine in Group III cylinders but certified analysis not available Vinylidene chloride 1 1 2 trichloro 1 2 2 trifluoroethane Freon 1 13 pales 1 2 dichloro 1 1 2 2 tetrafluoroethane Freon 114 Acetone 1 4 Dioxane Toluene Chlorobenzene Group Ill Ranges 70 to 90 ppb 90 to 430 ppb Group IV Acrylonitrile 1 3 butadiene Ethylene oxide Methylene chloride Propylene oxide O Xylene Group IV Ranges 7 to 90 ppb 430 to 10 000 ppb Group V Carbon tetrachloride Chloroform Perchloroethylene Vinyl chloride Benzene Trichloroethylene 1 2 dichloroethane 1 2 dibromoethane 1 1 1 trichloroethane Methylene chloride Trichlorofluorom
135. document and is summarized as follows Chapter 2 0 Getting a Monitoring Program Started discusses the motivation and philosophy behind such programs who should be involved in the program public regulatory agencies other industries and why and what management factors should be considered in designing and implement ing a regional air toxics monitoring program Chapter 3 0 Developing the Monitoring Plan and Methodologies describes the process for develop ing monitoring program plans Key features include selecting constituents to be monitored selecting program duration and frequency selecting sampling and analytical methods defin ing meteorological program requirements designing elements of the network and selecting contractors for sampling and analysis e Chapter 4 0 Operating the Network describes the process for selecting and training personnel procuring equipment operating and maintaining field instrumentation and keeping records e Chapter 5 0 Implementing Quality Assurance Quality Control provides guidance for routine and periodic field laboratory and data manage ment QA QC requirements Chapter 6 0 Managing and Evaluating the Data describes the process of storing reducing proces sing validating analyzing interpreting report ing and using data Chapter 7 0 Estimating Program Costs provides estimates for unit costs of equipment and 1 tory analysis as well as estimate
136. document as part of its Chemicals in Community series Other documents in this and related series include CHEMICALS IN THE COMMUNITY Series includes Methods to Evaluate Airborne Chemical Levels May 1988 A resource document presents two general approaches for placing emission levels in context data base driven and model driven Using these two approaches 8 methods are described to evaluate the health impact of air borne releases Member price 8 00 Non member price 12 00 Implementing Regional Air Monitoring Programs February 1990 A manual to assist companies establish regional air monitoring programs This document covers both the policy issues and the technical details of setting up a regional air monitoring project Member price 20 00 Non member price 40 00 Understanding Environmental Fate in preparation IMPROVING AIR QUALITY Series includes Guidance for Estimating Fugitive Emissions from Equipment January 1989 A guidance manual of fugitive emission testing for plants that want to conduct accurate leak rate estimations This manual includes the EPA protocol with notations for implementation by the chemical industry Member price 20 00 Non member price 30 00 Fugitive Emission Workshop Videotapes These videotapes cover some of the topics plant personnel ask about when setting up a testing program for equipment leak detection and repair Minutes Member Price Non Member Price Tape I O
137. e CRI for lead is less than the CRI for mercury Using the examples for carcinogens the CRIs for trichloroethylene and carbon tetrachloride are greater than the CRI for dichloromethane After this process the reader can evaluate the project s priorities and select the list of constitutents for the community air toxics monitoring Value used is NAAQS APPENDIX C REGIONAL AIR MONITORING METHODS AND EQUIPMENT 55 NOMENCLATURE USED IN THIS APPENDIX GC Gas Chromatograph FID Flame lonization Detector PID Photoionization Detector ECD Electron Capture Detector FPD Flame Photometric Detector MS Mass Spectroscopy HRGC High Resolution Gas Chromatography HRMS High Resolution Mass Spectroscopy GC MS SIM Gas Chromatography Mass Spectroscopy Selected lon Monitoring GC MS SCAN Gas Chromatography Mass Spectroscopy full SCAN mode PDFID Preconcentration and Direct Flame lonization Detector HPLC High Performance Liquid Chromatography AA Atomic Absorption ICP Inductive Coupled Plasma FT IR Fourier Transform Infra Red Hi Vol High Volume GFF Glass Fiber Filter GFA Graphite Furnace Atomization MCEF Mixed Cellulose Ester Filter Membrane Filter ISE lon Selective Electrode Fl Flame lonization DNPH Dinitrophenylhydrazine IC lon Chromatography 56 10 11 12 13 14 APPENDIX REGIONAL AIR MONITORING METHODS AND EQUIPMENT TABLE C 1 LIST OF AIR TOXIC MONITORING REFERENCES U S EPA June 1983 Technica
138. e between individual monitoring sta tions and program objectives A meteorological station located next to each air sampling station is recom mended However you could modify this recommenda tion depending on your specific local conditions For example one meteorological station could be sufficient if the following conditions exist a flat or gently rolling topography with no air water interface no major obstruction interferences short distances between sta tions a mile or less and no major emphasis on the determination of upwind and downwind concentrations Classes of meteorological monitoring parameters for regional air monitoring applications include Primary parameters including wind direction wind speed sigma theta i e the horizontal wind direc tion standard deviation which is an indicator of atmospheric stability and solar radiation e Secondary parameters including temperature pre cipitation humidity and atmospheric pressure Primary parameters represent regional dispersion con ditions and should be included in all meteorological monitoring programs Secondary parameters represent emission conditions Currently the use of sigma theta in determining atmospheric stability is an EPA acceptable method EPA is considering the use of the vertical temperature differ ence delta T in conjunction with net solar radiation to determine atmospheric stability Once EPA makes delta T a part of the method for dete
139. e collected from four sites The result ing data will be used to provide a preliminary assessment of the industrial source contributions to ambient air quality within the region TABLE 7 1 RANGES OF UNIT COST ESTIMATES FOR EQUIPMENT AND SUPPLIES AND LABORATORY ANALYSIS FOR REGIONAL AIR MONITORING PROGRAMS EPA Sampling ac 7 Monitoring and Analysis Laboratory Method 6 Analysis 8 Purchasing Leasing Sample Unit Unit Month TIME INTEGRATED AIR MONITORING VOC Gas Phase Canister sampler 2 450 650 450 50009 Tenax sampler 3 pra 350 450 300 35011 Modified TO 3 3 800 2 5 A 10 Tedlar bag sampler 2 350 400 300 350 10 Carbon molecular 4 000 3 12 PCB Particulate PUF sampler TO 4 250 300 250 3003 3 400 www e High Volume PM 10 5 14 sampler 5 400 450 200 25019 Part 50 11 Appendix B NEAR REAL TIME AIR MONITORING VOC Gas Phase 15 2 1 500 1 700 Not applicable METEOROLOGICAL MONITORING Portable system on a tripod 3 800 Portable system on a tripod 7 300 Cranked up 10 meter tower 4 500 Assumed no Cranked up 10 meter tower 8 000 Assumed no 1 Includes 3 canisters 2 Includes 30 bags 3 Includes 30 tubes 4 Includes 30 plugs and 100 fiber glass filters 5 Includes 100 quartz filters 6 See Appendix C for more details 7 Price range is for one unit Discou
140. e column detection with back flush capability for shorter analytical time constant column temperature for method precision and accuracy and multidetector PID ECD and FID capability for versatility Many of those newer features address the weaknesses and interferences mentioned above Apparatus 7 1 7 2 Gas chromatograph A GC Photovac Inc 739 8 Parks Ave Huntington NY 11743 Model 10510 10550 or equivalent used for surveying ambient air environments which could employ a multi detector for sensing numerous VOCs compounds eluting from a packed column at room tempera tures This particular portable GC procedure is written employing the photoionization detector as its major sensing device as part of the Photovac Model 10510 portable GC survey tool Chromatograms are developed on a columm of 3 SP 2100 on 100 120 Supelcoport 0 65 m x 3 2 mm 1 0 with a flow of 30 cm3 min air GC accessories In addition to the basic gas chromatograph several other pieces of equipment are required to execute the survey sampling Those include gas tight syringes for standard injection alternate carrier gas supplies high pressure connections for filling the internal carrier gas reservoir and if the Model 10S10 is used a recording integrator Hewlett Packard Avondale PA Model 3390A or equivalent Reagents and Materials 8 1 8 2 8 3 8 4 8 5 Carrier gas Zero air lt 0 1 ppm total hydrocarbon THC is used as the carr
141. e con densed on the trap surface while No 0 and other sample components are passed to the pump After the organic compounds are concentrated the valve is switched and the trap is heated The revolatilized compounds are transported by helium carrier gas at a rate of 4 cm3 min to the head of the Megabore OV 1 capillary column 0 53 mm x 30 m Since the column initial temperature is at 50 C the VOCs and SVOCs are cryofocussed on the head of the column Then the oven tem perature is programmed to increase and the VOCs SVOCs in the carrier gas are chromatographically separated The carrier gas containing the separated VOCs SVOCs is then directed to two parallel detectors at a flow rate of 2 cm3 min each The detectors sense the presence of the speciated VOCs SVOCs and the response is recorded by either a strip chart recorder or a data processing unit Typical chromatograms of VOCs determined by the GC FID ECD analytical system are illustrated in Figures 11 c and 11 d respectively Helium is used as the carrier gas 4 cm3 min to purge residual air from the trap the end of the sampling phase and to carry revolatilized VOCs through the Megabore GC column Moisture and organic impurities are removed from the helium gas stream by a chemical purifier installed in the GC see Section 7 2 1 11 After exiting the OV 1 Megabore column the carrier gas stream is split to the two detectors at rates of 2 cm3 min each Gas scrubbers con
142. e ground e Horizontal spacing from obstructions and obstacles Unrestricted air flow e Spacing from roads Site accessibility Power availability Site security Table 3 8 includes a summary of the key criteria asso ciated with these siting factors for air monitoring stations You should use the information included in Table 3 8 as part of the monitoring network design This will ensure that the monitoring program provides representative and unbiased data However site specific constraints could make it very difficult for you to meet all siting criteria For example the occurrence of buildings around a can didate monitoring site would make siting very difficult Therefore you should use the information in Table 3 8 coupled with a balanced evaluation by an experienced air quality and meteorology specialist The following paragraphs discuss key principles you should consider when siting air monitoring and meteorological stations For a monitoring site area with no major obstructions and obstacles the air sampler intake should be at the breathing zone height of about 2 3 meters above ground For a site with nearby roadways however intake placement should take into account the effects of road dust re entrainment and vehicular emissions To ensure a representative exposure the meteorological 19 stations should be located at distances of at least 10 times the heights of any nearby obstructions In most cases it is re
143. e method validation pro cess Finally method validation procedures such as the recovery of spiked samples should be integrated into the daily sampling and analysis program SRM s IRM s or CRS s are appro priate for this form of method validation 7 5 2 instrument Calibration and Maintenance Proper calibration of analytical instrumentation is fundamental to the success of a TOAP monitoring program The QA plan for a TOAP monitoring program will therefore include a calibration plan for the various analytical systems used on the project The calibration plan will include 1 A statement of the maximum allowable time between multipoint calibrations and cali bration checks 2 statement of the minimum quality of calibration standards e g standards should have four to ten times the accuracy of the instruments that they are being used to cali brate A list of calibration standards should be provided 3 Provisions for standard traceability e g standards should be traced to NBS SRM s or commerical Certified Reference Materials CRM s if available 4 Provisions for written procedures to help ensure that calibrations are always performed in the same manner The procedures should include the intended range of validity 5 Statement of proper environmental conditions to ensure that the equipment is not sig nificantly affected by its surroundings 6 Provisions for proper record keeping and record forms to ensue t
144. e pressure vacuum is recorded on the sampling field data sheet Pressure should be close to desired pressure Note For a subatmospheric sampling system if the canister is at atmospheric pressure when the field final pressure check is performed the sampling period may be suspect This information should be noted on the sampling field data sheet Time of day and elapsed time meter readings are also recorded U S EPA Compendium Method T014 1988 105 9 2 14 The canister valve is closed The sampling line is disconnected from the canister and the canister is removed from the system For a subatmospheric system a certified mass flow meter is once again connected to the inlet manifold in front of the in line filter and a practice canister is attached to the Magnelatch valve of the sampling system The final flow rate is recorded on the canister sampling field data sheet see Figure 10 Note Fora pressurized system the final flow may be measured directly The sampler is turned off 9 2 15 An identification tag is attached to the canister Canister serial number sample number loca tion and date are recorded on the tag 10 0 Analytical System See Figures 4 5 and 6 10 1 System Description 10 1 1 GC MS SCAN System 10 1 1 1 10 1 1 2 The analytical system is comprised of a GC equipped with a mass selective detec tor set in the SCAN mode see Figure 4 All ions are scanned by the MS repeatedly during the GC run The system i
145. econcentration of VOCs with subsequent GC analysis using a 0 32 mm 1 0 column because excess accumulated water can cause trap and column blockage and also adversely affect detector precision In addition the improvement in water removal from the sampling stream will allow analyses of much larger volumes of sample air in the event that greater system sensitivity is required for targeted compounds 106 U S EPA Compendium Method T014 1988 10 1 1 3 10 1 1 4 The packed metal tubing used for reduced temperature trapping of VOCs is shown in Figure 12 The cooling unit is comprised of a 0 32 cm outside diameter O D nickel tubing loop packed with 60 80 mesh Pyrex beads Nutech Model 320 01 or equivalent The nickel tubing loop is wound onto a cylindrically formed tube heater 250 watt A cartridge heater 25 watt is sandwiched between pieces of aluminum plate at the trap inlet and outlet to provide additional heat to eliminate cold spots in the transfer tubing During operation the trap is inside a two section stainless steel shell which is well insulated Rapid heating 150 to 100 C in 55 s is accom plished by direct thermal contact between the heater and the trap tubing Cooling is achieved by vaporization of the cryogen In the shell efficient cooling 120 to 150 C in 225 s is facilitated by confining the vaporized cryogen to the small open volume surrounding the trap assembly The trap assembly and chromatographic valve are
146. egional Air Monitoring Programs Regional Air Monitoring QA QC Strategy Summarize and Evaluate Results ae ea a a a Example Wind Rose 18 18 28 28 29 41 42 10 23 25 26 27 29 33 34 Bw gt PTj Appendices Page List of Toxic Air Pollutants for Regional Monitoring Programs 45 Hazard Index Methodology 51 Air Toxic Monitoring Methods and Equipment 55 Bibliography of Air Monitoring Standard Operating Procedures 65 Excerpt from Technical Assistance Document for Sampling and Analysis of Toxic Organic Compounds in Ambient Air U S EPA June 1983 Revised 1990 71 Examples of Standard Operating Procedures 89 SOPS for Operating VOCS Canister Samples ee 91 U S EPA Compendium Method 7014 1988 SOPS for Meteorological Station Operations and 169 Data Validation Criteria and 175 Other Related Documents CMA as part of its ongoing technical education and communication efforts developed this
147. egulators automatic control of valves and integrator etc Flame ionization detector optional Hewlett Packard Rt 41 Avondale PA 19311 Model 5880A with oven temperature control and Level 4 BASIC programming or equivalent Chromatographic detector mass selective detector Hewlett Packard 3000 T Hanover St 9B Palo Alto CA 94304 Model HP 5970 MS or equivalent equipped with computer and appropriate software Hewlett Packard 3000 T Hanover St 9B Palo Alto CA 94304 HP 216 Computer Quicksilver MS software Pascal 3 0 mass storage 9133 HP Winchester with 3 5 inch floppy disk or equivalent The GC MS is set in the SCAN mode where the MS screens the sample for Enea Hon and quan titation of VOC species 100 U S EPA Compendium Method 014 1988 7 2 2 7 2 3 7 2 1 4 7 2 1 5 7 2 1 6 7 2 1 7 7 2 1 8 7 2 1 9 7 2 1 10 7 2 1 11 7 2 1 12 7 2 1 13 7 2 1 14 7 2 1 15 7 2 1 16 Cryogenic trap with temperature control assembly refer to Section 10 1 1 3 for com plete description of trap and temperature control assembly Nutech Corporation 2142 Geer St Durham NC 27704 Model 320 01 or equivalent Electronic mass flow controllers 3 maintain constant flow for carrier gas and sam ple gas and to provide analog output to monitor flow anomalies Tylan Model 260 0 100 cm3 min or equivalent Vacuum pump general purpose laboratory pump capable of drawing the desired sample volume t
148. elements from a technical or policy standpoint The outcome of their work once explained to and concurred upon by the decision maker leads to the genera tion of specific guidance for designing the data collection program The products of Stage Il include proposed statements of the type and quality of environmental data required to sup port the decision along with other technical constraints on the data collection activity that will place bounds on the search for an acceptable design Stage Ill These outputs are the pro posed DQO s EPA Excerpt Sampling and Analysis of Toxic Organic Compounds in Ambient Air 79 3 2 3 Stage 111 Activities This stage is primarily the responsibility of the technical staff but involves both the senior program staff and the decision maker to assure the outputs from Stages and ll understood The objective of Stage Ill is to develop data collection plans that will meet the teria and constraints established in Stages and ll All viable options should be presented to the decision maker It is the prerogative of the decision maker to select the final design that provides the best balance between time and resources available for data collection and the level of uncertainty expected in the final results TABLE 3 1 COMPONENTS OF THE DATA QUALITY OBJECTIVE PROCESS Stage Decision Definition Responsibility Decision Maker Step 1 Decision Description Step 2 Description of Information Needed for
149. eneral detector verification to identify compounds However interfer ence due to nearly identical retention times can affect system quantitation when using this option Due to the low concentrations of VOCs encountered in urban air typically less than 4 ppbv and the majority below 1 ppbv along with their complicated chromatograms Method TO 14 strongly recom mends the specific detectors GC MS SCAN SIM for positive identification and for primary quantita tion to ensure that high quality ambient data is acquired For the experienced analyst whose analytical system is limited to the non specific detectors Section 10 3 does provide guidelines and example chromatograms showing typical retention times and calibration response factors and utilizing the non specific detectors GC FID ECD PID analyti cal system as the primary quantitative technique 4 0 Significance 4 1 4 2 VOCs enter the atmosphere from a variety of sources including petroleum refineries synthetic organic chemical plants natural gas processing plants and automobile exhaust Many of these VOCs are acutely toxic therefore their determination in ambient air is necessary to assess human health impacts Conventional methods for VOC determination use solid sorbent sampling techniques The most widely used solid sorbent is Tenax An air sample is drawn through a Tenax filled cartridge where certain VOCs are trapped on the polymer The sample cartridge is transf
150. entane isoprene dimethylsulfide acetonitrile 1 1 dichloroethylene trans 2 pentene diethyl ether cis 2 pentene 2 methyl 2 butene methylene chioride 2 propanol neohexane isobutyraldehyde cyclopentene 4 methyl 1 pentene cyclopentane trans 1 2 dichoroethylene 2 3 dimethylbutane isohexane cis 4 methyl 2 pentene Trans 4 methyl 2 pentene 1 propanol 48 CAS 123 72 8 96 14 0 78 93 3 763 29 1 592 41 6 760 21 4 110 54 3 _ 7642 09 3 67 66 3 625 27 4 4050 45 7 7688 21 3 N A 96 37 7 107 06 2 108 08 7 71 55 6 590 86 3 71 43 2 27476 50 2 56 23 5 110 82 7 31394 54 4 565 59 3 110 83 8 107 87 9 78 87 5 589 34 4 71 36 3 110 62 3 96 22 0 79 01 6 75 27 4 592 76 7 540 84 1 123 91 1 109 79 5 592 78 9 142 82 5 592 77 8 107 39 1 108 87 2 10061 01 5 107 40 4 108 10 1 592 13 2 110 75 8 10061 02 6 79 00 5 565 75 3 554 14 3 108 88 3 616 44 4 591 49 1 124 48 1 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 79 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 Compound Name butyraldehyde 3 methylpentane butanone 2 methyl 1 pentene 1 hexene 2 ethyl 1 butene n hexane cis 3 hexene chloroform 2 methyl 2 pentene trans 2 hexene cis 2 hexene c 3 methyl 2 pentene methylcyciopentane 1 2 dichloroethane 2 4 dimethylpentane 1 1 1
151. enzene 141 93 5 156 m diethylbenzene 106 42 3 123 p xylene m xylene 104 51 8 157 n butylbenzene 108 3 3 105 05 5 158 p diethylbenzene 100 42 5 124 styrene 821 95 4 159 1 undecene 95 47 6 125 o xylene 1120 21 4 160 n undecane 79 34 5 126 1 1 2 2 tetrachloroethane 91 20 3 161 naphthalene 75 25 2 bromoform 75 34 3 162 1 1 dichloroethane 124 11 8 127 1 nonene 74 82 8 163 methane 2198 23 4 128 4 100 52 7 164 benzaldehyde 638 02 4 129 2 5 dimethylthiophene 107 13 1 165 acrylonitrile 111 84 2 130 _ n nonane 156 59 2 166 cis 1 2 dichloroethylene 98 82 8 131 isopropylbenzene 108 94 1 167 cyclohexanone 80 56 8 132 a pinene 106 93 4 168 1 2 dibromoethane 95 49 8 133 o chlorotoluene 110 02 1 169 thiophene 108 41 8 134 m chlorotoluene 564 02 3 170 2 2 3 trimethylpentane 106 43 4 135 p chlorotoluene 126 99 8 171 chioroprene 103 65 1 136 n propylbenzene 67 72 1 172 hexachloro Ethane 620 14 4 137 m ethyltoluene 74 88 4 173 methyl lodide 622 96 8 138 p ethyltoluene 75 56 9 174 propylene Oxide 111 44 4 139 dichloroethyl ether 593 60 2 175 vinyl bromide 108 67 8 140 1 3 5 trimethylbenzene 1634 04 4 176 methy t butyl ether 611 14 3 141 o ethyltoluene 98 87 3 177 benzal chloride 127 91 3 142 b pinene 100 44 7 178 benzyl chloride 98 06 6 143 t butylbenzene 75 21 8 179 ethylene oxide 95 63 6 144 1 2 4 trimethylbenzene 87 61 6 180 1 2 3 trichlorobenzene 541 73 1 145 m dichlorobenzene 120 82 1 181 1 2 4 trichlorobenzene These compounds may be m
152. er for flow verification of sampling system section 11 1 requires all canisters to be pressure tested to 207 kPa 14 kPa 30 psig 2 psig over a period of 24 hours Section 11 1 requires that all canisters be certified clean containing less than 0 2 ppbv of targeted VOCs through a humid zero air certification program Section 11 2 2 requires all field sampling systems to be certified initially clean containing less than 0 2 ppbv of targeted VOCs through a humid zero air certification program Section 11 2 3 requires all field sampling systems to pass an initial humidified calibration gas certification at VOC concentration levels expected in the field e g 0 5 to 2 ppbv with a percent recovery of greater than 90 12 5 2 GC MS SCAN SIM System Performance Criteria 12 5 2 1 12 5 2 2 12 5 2 3 Section 10 2 1 requires the GC MS analytical system to be certified clean less than 0 2 ppbv of targeted VOCs prior to sample analysis through a humid zero air certification section 10 2 2 requires the daily tuning of the GC MS with 4 bromofluorobenzene 4 BFB and that it meet the key ions and ion abundance critera 10 outlined in Table 5 Section 10 2 3 requires both an initial multipoint humid static calibration three levels plus humid zero air and a daily calibration one point of the GC MS analyt ical system 12 5 3 GC Multidetector System Performance Criteria 12 5 3 1 12 5 3 2 12 5 3 3 12 5 3 4 13 5
153. er is reattached to the cleaning manifold and is then reevacuated to 0 05 mm Hg and remains in this condition until used The canister valve is closed The canister is removed from the cleaning system and the canister connection is capped with a stainless steel fitting The canister is now ready for collection of an air sample An identification tag is attached to the neck of each canister for field notes and chain of custody purposes 11 1 8 As an option to the humid zero air cleaning procedures the canisters could be heated in an isothermal oven to 100 C during Section 11 1 3 to ensure that lower molecular weight com pounds C2 C8 are not retained on the walls of the canister Note For sampling heavier more complex VOC mixtures the canisters should be heated to 250 C during Section 11 1 3 7 Once heated the canisters are evacuated to 0 05 mm Hg At the end of the heated evacuated cycle the canisters are pressurized with humid zero air and analyzed by the GC FID ECD system Any canister that has not tested clean less than 0 2 ppbv of targeted compounds should not be used Once tested clean the canisters are reevacuated to 0 05 mm Hg and remain in the evacuated state until used 11 2 Sampling System Cleaning and Certification 11 2 1 Cleaning Sampling System Components 11 2 1 1 Sample components are disassembled and cleaned before the sampler is assembled Nonmetallic parts are rinsed with HPLC grade deionized water and dried in a vacuu
154. erested in obtaining results from regional air monitoring pro grams Therefore consider presenting these results dur ing a meeting with representatives from these audiences During these meetings it is imperative to communicate effectively CMA in collaboration with risk communi cation experts prepared a resource document entitled Risk Communication Risk Statistics and Risk Compar isons CMA 1988 9 For your use the basic CMA communication strategy includes the following rules e Accept and involve the public as a legitimate partner e Plan carefully and evaluate your performance e Listen to your audience Be honest frank and open to ideas Coordinate and collaborate with other credible sources Meet the needs of the media e Speak clearly and with compassion When writing a summary report for the regional air monitoring program consider including the following topics Introduction and objectives e Executive summary Monitoring program operations Network configuration Meteorological monitoring sample collection and analysis 36 e Monitoring results Meteorological conditions Air sampling results Quality control e Data interpretation Meteorological conditions and representativeness Air concentrations vs health environmental criteria Program performance QC and audit results The report should provide sufficient details about the methodologies employed in sample c
155. errain or coastal areas separate wind roses should be prepared to characterize daytime conditions and night time conditions A summary wind rose based on all wind observations during the monitoring period should also be developed A suggested format for wind rose data is illustrated in Figure 6 2 Data recovery of a portion of acceptable data out of the total database information should also be presented to allow for an evaluation of data representativeness As mentioned above EPA currently requires for permit ting purposes a minimum meteorological data recovery target of 90 percent Air Monitoring Data Summaries Air monitoring data summaries should include a list ing of sequential concentrations measured by station and monitoring period that indicates concentrations of all constituents for which monitoring was conducted The listing should indicate method detection limits for those cases where a constituent is not detected as well as upwind downwind exposure classification when appli cable and monitoring station operation data 2 sampling flow rates station number and sampling start end times FIGURE 6 2 EXAMPLE WIND ROSE FORMAT NENNEN WIND DIRECTION FREQUENCY PERCENT APRIL 720 OSS Ew MEAN WIND SPEED MI HR It is recommended that you report a concentration of a constituent that is below method detection limit as ND not detected and to use half the detection limit value for statistical calcu
156. erred to a laboratory and analyzed by GC MS 97 U S EPA Compendium Method T014 1988 50 43 VOCs can also be successfully collected in stainless steel canisters Collection of ambient air samples in canisters provides 1 convenient integration of ambient samples over a specific time period e g 24 hours 2 remote sampling and central analysis 3 ease of storing and shipping samples 4 unattended sample collection 5 analysis of samples from multiple sites with one ana lytical system and 6 collection of sufficient sample volume to allow assessment of measurement precision and or analysis of samples by several analytical systems However care must be exercised in selecting cleaning and handling sample canisters and sampling apparatus to avoid losses or contamination of the samples Contamination is a critical issue with canister based sampling because the canister is the last element in the sampling train gt 4 4 Interior surfaces of the canisters are treated by the SUMMA passivation process in which a pure chrome nickel oxide is formed on the surface This type of vessel has been used in the past for sam ple collection and has demonstrated sample storage stability of many specific organic compounds 4 5 This method can be applied to sampling and analysis of not only VOCs but also some selected semivolatile organic compounds SVOCs The term semivolatile organic compounds is used to broadly describe organic compou
157. erview 42 75 00 112 50 Tape II Screening 58 75 00 112 50 Tape III Bagging 38 75 00 112 50 All Three Tapes 225 00 337 50 All tapes are available in and 34 inch formats POSSEE Software Plant Organizational Software System for Emissions from Equipment POSSEE is a software data entry system for fugitive emissions testing designed exclusively for CMA POSSEE can help you set up a testing program enter data and develop estimates of the fugitive emissions at your plant Member price 150 00 Non member price 225 00 A Guide to Estimate Secondary Emissions In Publication A guidance manual for estimation emissions from secondary air sources for SARA 313 reporting ee Member price 40 00 Non member price 60 00 PAVE Software In Development To order these documents please refer to order form on the last page of this publication 180 ORDER FORM Member Non member Price Price Quantity Cost CHEMICALS IN THE COMMUNITY Methods to Evaluate Airborne Chemical Levels 8 00 12 00 Implementing Regional Air Monitoring Programs 20 00 40 00 Understanding Environmental Fate in Preparation TBA TBA TBA IMPROVING AIR QUALITY Guidance for Estimating Fugitive Emissions from Equipment 20 00 30 00 Fugitive Emission Workshop Videotapes All tapes are available in and inch formats Minutes Tape I Overview 42 75 00 112 50 34 H Tape II Screening 58 75 00 112 50 34 if Tape Bagging 38 75 00 112 50 34 if All T
158. esult of trapped water thus eliminating the need for a Nafion9 dryer in the analyti cal system The Megabore column has sample capacity approaching that of a packed column while retaining much of the peak resolution traits of narrower columns i e 0 32 mm 1 0 7 2 3 10 Vacuum pressure gauges 3 refer to Section 7 2 1 9 for description 7 2 3 11 Cylinder pressure stainless steel regulators standard two stage cylinder regula tors with pressure gauges for helium zero air nitrogen and hydrogen gas cylinders 7 2 3 12 Gas purifiers 4 used to remove organic impurities and moisture from gas streams Hewlett Packard Rt 41 Avondale PA 19311 P N 19352 60500 or equivalent 7 2 3 13 Low dead volume tee used to split 50 50 the exit flow from the GC column Alltech Associates 2051 Waukegan Rd Deerfield IL 60015 Cat 5839 or equivalent 7 3 Canister Cleaning System See Figure 7 7 4 7 3 1 7 3 2 7 3 3 7 3 4 7 3 5 7 3 6 7 3 7 7 3 8 7 3 9 Vacuum pump capable of evacuating sample canister s to an absolute pressure of 0 05 mm Hg Manifold stainless steel manifold with connections for simultaneously cleaning several canisters Shut off valve s seven 7 on off toggle valves Stainless steel vacuum gauge capable of measuring vacuum in the manifold to an absolute pressure of 0 05 mm Hg or less Cryogenic trap 2 required stainless steel U shaped open tubular trap cooled with
159. eted VOCs at nominal concentrations of 10 ppmv in nitrogen Section 8 2 as working standards to be diluted with humid zero air The contents of the working standard cylinders are metered 2 cm3 min into the heated mixing chamber where they are mixed with a 2 L min humidified zero air stream to achieve a nominal 10 ppbv per compound calibration mixture see Figure 8 This nominal 10 ppbv standard mixture is allowed to flow and equilibrate for an appropriate amount of time After 110 U S EPA Compendium Method T014 1988 10 3 3 2 the equilibration period the gas standard mixture is sampled and analyzed by the GC MS system see Figure 8 a The results of the analyses are averaged flow audits are performed on the mass flow controllers used to generate the standards and the appropriate response factors concentration area counts are calculated for each compound as illustrated in Table 5 Note GC FIDs are linear in the 1 20 ppbv range and may not require repeated multipoint calibrations whereas the GC ECD will require frequent linearity evaluation Table 5 outlines typical calibration response factors and retention times for 40 VOCs After the GC FID ECD is calibrated at the three concentration levels a second humid zero air sample is passed through the system and analyzed The second humid zero air test is used to verify that the GC FID ECD system is certified clean less than 0 2 ppbv of target compounds Routine Calibration A one po
160. ethane Freon 11 Bromomethane Toluene Chlorobenzene 1 3 Butadiene o xylene Ethyl benzene 1 2 dichloropropane Group V Ranges 1 to 40 ppb U S EPA Compendium Method T014 1988 154 1 0 2 0 3 0 4 0 5 0 6 0 APPENDIX B OPERATING PROCEDURES FOR A PORTABLE GAS CHROMATOGRAPH EQUIPPED WITH A PHOTOIONIZATION DETECTOR scope This procedure is intended to screen ambient air environments for volatile organic compounds Screening is accomplished by collection of VOC samples within an area and analysis onsite using a portable gas chromatograph integrator Photovac Models 10510 10S50 or equivalent This procedure is not intended to yield quantitative or definite qualitative information regarding the substances detected Rather it pro vides a chromatographic profile of the occurrence and intensity of unknown volatile compounds which assists in placement of fixed site samplers Applicable Documents 2 1 ASTM Standards E260 Recommended Practice for General Gas Chromatography Procedures E355 Practice for Gas Chromatography Terms and Relationships 2 2 Other Documents Portable Instruments User s Manual for Monitoring VOC Sources EPA 34011 86 015 U S Environ mental Protection Agency Washington DC June 1986 Summary of Method 3 1 An air sample is extracted directly from ambient air and analyzed on site by a portable GC 3 2 Analysis is accomplished by drawing an accurate volume of ambient air through a samplin
161. f chemicals of concern to the community Not all airborne pollutants are measurable using existing techniques To aid the reader the lists of pollutants that are on the U S Environmental Protection Agency EPA lists of volatile organics quantified in the Toxic Air Monitoring Stations TAMS program and the Urban Toxics Monitoring Program are provided in Appendix A These lists include all of the compounds which EPA considers to be amenable to analysis EPA uses this list extensively in its air monitoring programs Appendix A also includes the Houston Regional Monitor ing HRM list of air pollutants This list includes the compounds analyzed under the HRM program To confirm the presence of the chemicals in Appendix A in your region it is recommended that you consider conducting a short term air monitoring survey to collect a limited number of samples and analyze them for all the constituents included in this appendix These results will provide preliminary insight on the presence and magni tude of the detected constituents FIGURE 3 2 SELECTING MONITORING CONSTITUENTS COMPOUNDS OF CONCERN TO THE COMMUNITY AIR TOXICS SURVEY RESULTS AiR TOXICS RELEASE INVENTORY AIR TOXICS POLICIES AND PROCEDURES PREVIOUS AIR MONITORING DATA CONSTITUENT RANKING INDEX SEE APPENDIX AIR MODELING RESULTS SELECTED LIST OF CONSTITUENTS 10 The Superfund Amendments Reauthorizatio
162. f the objectives and scope of the program e Laboratory certifications Following the evaluation of proposals you may want to conduct further negotiations with one or more bidders To simplify management of the project we recommend that one contractor be given overall responsibility for the conduct of sampling and analytical activities whether or not the laboratory is a part of this organization or is an independent laboratory In this latter case the labora tory would be a subcontractor 3 8 REFERENCES 1 U S EPA December 1988 FY 88 Annual Report on the Operations and Findings of the Toxic Air Monitoring Stations TAMS and subsequent updates Internal Report Atmospheric Research and Exposure Assessment Laboratory Office of Research and Development Research Triangle Park North Carolina 27711 2 Houston Regional Monitoring Corporation July 1988 Volatile Indicator Measurement Results from the Houston Regional Monitoring Network August 21 10 18 1987 through March 18 1988 and subsequent updates Prepared by Radian Corporation Austin Texas 78720 U S EPA January 1988 National Ambient Volatile Organic Compounds VOCs Data Base Update and subsequent updates EPA 600 3 88 010 A Contract No 68 02 4190 pre pared by G2 Environmental Inc U S EPA May 1987 The Modified Hazardous Air Pollutant Prioritization System MHAPPs EPA Contract No 68 02 4330 Work Assignment No 12 prepared by R
163. g e Sampling procedure Calibration procedure e Antlytical procedure e Data analyses validation and reporting procedure Performance and system audit procedure Preventive maintenance procedure The QA program plan plans for specific projects e Laboratory record notebooks Data sheets 7 3 3 Data Evaluation The intent of a QA program is to maintain data continuously within pre determined quality limits This objective will not be achieved if information applicable to a QA management activ ity is not received reviewed and or acted on in a timely manner An effective QA program will therefore establish what information is required by QA management personnel how it will be used when it will be required when it will be reviewed and when control actions necessiated by unacceptable data will be implemented 7 3 4 Standard Reference Materials The fundamental requirements for producing reliable data are appropriate methodology and properly calibrated instrumentation used according to established procedure The quali ty of generated data can be assessed by incorporating reference materials into the sampling and analytical processes A reference material is a substance for which critical properties are sufficiently well estab lished for the reference material to be used to calibrate an analyzer or validate a measure ment process Generally speaking there are three types of reference materials in common use
164. g port and into a concentrator then the sample air is transported by carrier gas onto a packed column and into a PID resulting in response peak s Retention times are compared with those in a standard chroma togram to predict the probable identity of the sample components Significance 4 1 VOCs are emitted into the atmosphere from a variety of sources including petroleum refineries syn thetic organic chemical plants natural gas processing plants and automobile exhaust Many of these VOC emissions are acutely toxic therefore their determination in indoor air is necessary to assess human health impacts 4 2 Conventional methods of VOC determination use solid sorbent and canister sampling techniques 43 Collection of indoor air samples in canisters provides 1 convenient integration of embient samples over a specific time period e g 24 hours 2 remote sampling and central analysis 3 ease of stor ing and shipping samples if necessary 4 unattended sample collection 5 analysis of samples from multiple sites with one analytical system and 6 collection of sufficient sample volume to allow assessment of measurement precision and or analysis of samples by several analytical systems 4 4 The use of portable GC equipped with multidetectors has assisted air toxics programs by using the portable GC as screening tool to determine spots potential interferences and semiquantitation of VOCs SVOCs prior to locating m
165. generated VOCs 11 2 3 8 At the end of the sampling period normally same time period used for anticipated sampling the sampling system canister is analyzed and compared to the reference GC MS or GC multidetector analytical system to determine if the concentration of the targeted VOCs was increased or decreased by the sampling system 11 23 9 A recovery of between 90 and 110 is expected for all targeted VOCs 115 U S EPA Compendium Method T014 1988 12 0 Performance Criteria and Quality Assurance 12 1 Standard Operating Procedures SOPs 12 1 1 SOPs should be generated in each laboratory describing and documenting the following activities 1 assembly calibration leak check and operation of specific sampling systems and equipment used 2 preparation storage shipment and handling of samples 3 assembly leak check calibration and operation of the analytical system addressing the specific equipment used 4 canister storage and cleaning and 5 all aspects of data record ing and processing including lists of computer hardware and software used ET 12 1 2 Specific stepwise instructions should be provided in the SOPs and should be readily avail able to and understood by the laboratory personnel conducting the work 12 2 Method Relative Accuracy and Linearity mene 12 2 1 Accuracy can be determined by injecting VOC standards see Section 8 2 from an audit cylinder into a sampler The contents are then analyzed for the com
166. grammed from scratch for each sample The correct current time of day is re entered to reprogram the timer Any program in the timer s memory is erased by resetting the timer pressing the reset button The timer is set by the following 1 pressing the reset button 2 entering the correct day number and time of day 3 entering the ON and OFF times for the sample period and 4 verifying that the ON and OFF time settings are correct 51 Timer Reset The timer reset button is pressed which is recessed in a small hole located just above the LED light emitting diode indicator light A small object that will fit through the hole such as a pencil match or pen is used to press the timer After reset the timer display should show 1 10 00 Note The timers may operate erratically when the batteries are discharged which happens when the sampler is unplugged or without power for several hours When the sampler is again powered _ UD several hours be required to recharge the batteries To avoid discharging the batteries the battery pack should be disconnected from the timer when the sampler is unplugged 5 2 Date and Time Entry The selector switch is turned to SET and the number button corresponding to the day number is pressed For example 2 is pressed for Monday The current time of day 15 entered For example if the time is 9 00 AM 900 is pressed AM or PM is pressed as applicable Display should
167. han the samples to be analyzed An example of a static calibration would be injecting a small volume of a high concentration standard directly onto a GC column bypassing the sample extraction and pre concentration portion of the analytical system 98 U S EPA Compendium Method T014 1988 6 0 7 0 5 13 Subatmospheric sampling Collection of an air sample in an evacuated canister at a final canister pressure below atmospheric pressure without the assistance of a sampling pump The canister is filled as the internal canister pressure increases to ambient or near ambient pressure An auxiliary vacuum pump may be used as part of the sampling system to flush the inlet tubing prior to or during sample collection Interferences and Limitations 61 Interferences can occur in sample analysis if moisture accumulates in the dryer see Section 10 1 1 2 An automated cleanup procedure that periodically heats the dryer to about 100 C while purging with zero air eliminates any moisture buildup This procedure does not degrade sample integrity 6 2 Contamination way occur in the sampling system if canisters are not properly cleaned before use Additionally all other sampling equipment e g pump and flow controllers should be thoroughly cleaned to ensure that the filling apparatus will not contaminate samples Instructions for cleaning the canisters and certifying the field sampling system are described in Sections 12 1 and 12 2 respectively 6
168. haracteristics Potential interferences present at the monitoring site Time resolution requirements Cost restraints Organic and inorganic constituents are monitored by different methods Various methods may also be required for monitoring either organics or inorganics depending on the constituents and their physical chemical properties Whether a compound occurs primarily in the gaseous phase or is found absorbed to solid particles or aerosols also affects your choice of monitoring techniques Sampling methodologies for PCBs and other semi volatile organic constituents as well as for inorganics in the form of particulates are also included in Table 3 2 Laboratory analytical techniques must provide for the positive identification of the components and the accur ate and precise measurement of concentrations This generally means that the preconcentration and or stor age of air samples are required Therefore methods chosen for time integrated monitoring usually require a longer analytical time period more sophisticated equip ment and more rigorous quality assurance QA procedures Table 3 4 presents a comparison of advantages and TABLE 3 4 COMPARISONS OF REGIONAL AIR MONITORING TECHNIQUES Time Integrated complex Near Real time sampling frequency variations Simple to use Inexpensive Sampling equipment not Standard approach used for monitoring air pollutants Results
169. hat adequate docu mentation of calibrations is available for use in internal data validation and in case the data are used in enforcement actions EPA Excerpt Sampling and Analysis of Toxic Organic Compounds in Ambient Air 86 7 Documentation of qualifications and training of personnel performing calibration The QA plan will also address appropriate maintenance activities and frequencies for analyti cal equipment Additionally the QA plan will include procedures to document performance of maintenance activities on schedule 7 5 3 Quality Control Sample Analysis A QA plan for a TOAP monitoring project will include provisions for the analysis of a variety of quality control samples Quality control samples for evaluating analytical performance should include blanks spiked process lanks spiked samples standard reference materials and replicate or split samples Standard reference materials and replicate or split samples should generally be included as part of field QA and need not be additionally included at the analysis stage However additional blanks spiked process blanks and spiked samples should be included since this practice allows matrix effects to be distinguished from analyti cal losses 7 6 DATA MANAGEMENT The QA plan for a TOAP monitoring program will include procedures designed to ensure that required sampling and analytical data are captured and maintained securely and effi ciently Data recording procedures tha
170. he calculated annual average tri chloroethylene concentration in the community as determined from dispersion modeling is 10 g m Then the CRI for trichloroethylene is CRI trichloroethylene Concentration 10 0 17 reference value 60 Example 5 The reference value NOEL 100 for carbon tetrochloride is 60 g m3 Assume the calculated annual averge carbon tetrachloride concentration in the community as determined from dispersion modeling is 10 g m Then the CRI for carbon tetrachloride is CRI carbon tetrachloride Concentration 10 reference value 60 0 17 54 Conclusion Once the CRI calculations are completed the sets of CRIs for carcinogens and non carcinogens are ranked from highest to lowest The resulting prioritized list should blend carcinogens and non carcinogens in the ranking To achieve this blending it is recommended that for ratios based upon the RsD the RsD should be multiplied by 100 corresponding to 103 upperbound estimate of risk NOEL an appropriate fraction of a NOEL must be evaluated to appropriately compare compounds If NOEL s are consistently used for all compounds the fraction is immaterial since the relative comparison will be valid However if the reader mixes health criteria a NOEL 100 is recommended to be consistent with the RfD For direct acting genotoxic carcinogens NOEL 1000 has also been recommended Using the examples above for non carcinogens th
171. hree Tapes 225 00 337 50 34 Hn A Guide to Estimate Secondary Emissions in Publication 40 00 60 00 POSSEE Software 150 00 225 00 PAVE Software in Development TBA uut TOTAL Please make check or money order payable to Chemical Manufacturers Association Price includes third class shipping and handling Allow 3 weeks for delivery Send order form to Chemical Manufacturers Association Publications Fulfillment 2501 M Street Washington D C 20037 Name Telephone Company Address
172. hrough the cryogenic trap Thomas Industries Inc Sheboygan WI Model 107BA20 or equivalent Chromatographic grade stainless steel tubing and stainless steel plumbing fittings mE refer to Section 7 1 1 8 for description Chromatographic column to provide compound separation such as shown in Table 5 Hewlett Packard Rt 41 Avondale PA 19311 GV I capillary column 0 32 mm x 50 m with 0 88 um crosslinked methyl silicone coating or equivalent Eu Stainless steel vacuum pressure gauge optional capable of measuring vacuum 101 3 to 0 kPa and pressure 0 206 kPa in the sampling system Matheson P O Box 136 Morrow GA 30200 Model 63 3704 or equivalent Gauges should be tested xa clean and leak tight Stainless steel cylinder pressure regulators standard two stage cylinder regula tors with pressure gauges for helium zero air and hydrogen gas cylinders Gas purifiers 3 used to remove organic impurities and moisture from gas streams Hewlett Packard Rt 41 Avondale PA 19311 P N 19362 60500 or equivalent Low dead volume tee optional used to split the exit flow from the GC column Alltech Associates 2051 Waukegan Rd Deerfield IL 60015 Cat 5839 or equivalent Nafion dryer consisting of Nafion tubing coaxially mounted within larger tubing Perma Pure Products 8 Executive Drive Toms River NJ 08753 Model MD 125 48 or equivalent Refer to Section 10 1 1 2 for description Six port gas
173. ical requirements Designing the network Selecting contractors for sampling and analysis OPERATING THE NETWORK CHAPTER 4 0 Selecting and training personnel Procuring equipment and supplies Operating and maintaining field instrumentation Keeping records ESTIMATING PROGRAM COSTS CHAPTER 7 0 Identifying unit costs of equipment supplies and analysis Providing example program scenarios Fill data gaps regarding concentrations of air borne pollutants in the community Respond to local state or Federal regulatory requirements Provide data to evaluate the impacts of airborne chemicals Identify contributors of toxic air pollutants in the community Contributors can include mobile Sources commercial chemical and residential chemical users and industrial chemical processes and long range transport of air pollutants Public awareness of toxic chemical emissions from industrial and other sources and their effects on public health and the environment has increased since the enactment of the Right to Know Act under the 1986 Superfund Amendments and Reauthorization Act SARA Federal state and local jurisdictions have enacted regulations or policies that require consideration of air emissions when issuing permits for both new and existing sources Regional air monitoring programs can provide infor mation about air quality These data can address public and industry concerns and can provide
174. ichloroethylene Dichloromethane Methylene chloride Freon 113 1 1 2 Trichloro 1 2 2 trifluoroethane 1 1 Dichloroethane Ethylidene dichloride cis 1 2 Dichloroethylene Chloroform Trichloromethane Bickl rsth ne Ethylene dichloride Methyl chloroform 1 1 1 Trichloroethane Benzene Cyclohexatriene Carbon tetrachloride Tetrachloromethane 1 2 Dichloropropane Propylene dichloride Trichloroethylene Trichloroethene cis 1 3 Dichloropropene trans 1 3 Dichloropropene 1 3 dichloro 1 propene eee continued 122 lon Abundance amu base peak 85 100 87 31 50 100 521 34 85 100 135 56 87 33 62 100 27 125 64 32 94 100 96 85 64 100 29 140 271140 101 100 103 67 61 100 96 55 63 31 49 100 84 65 86 45 151 100 101 140 103 90 63 100 27 64 65 33 61 100 96 60 98 44 83 100 85 65 47 35 62 100 27 70 64 31 97 100 99 64 61 61 78 100 77 25 50 35 117 100 119 97 63 100 41 90 62 70 130 100 132 92 95 87 75 100 39 70 77 30 75 100 39 70 77 30 Expected Retention Time min 5 01 5 69 6 55 6 71 7 83 8 43 9 97 10 93 11 21 11 60 12 50 13 40 13 75 14 39 14 62 15 04 15 18 15 83 16 10 16 96 17 49 U S EPA Compendium Method T014 1988 TABLE 2 ION ABUNDANCE AND EXPECTED RETENTION TIME FOR SELECTED VOCs ANALYZED BY GC MS SIM cont lon Abundance Expected Retention Compound amu base pe
175. ier gas This gas is con veniently contained in 0 84 m3 30 ft3 aluminum cylinders Carrier gas of poorer quality may result in spurious peaks in sample chromatograms A Brooks Type 1355 00F 1AAA rotameter or equivalent with an R 215 AAA tube and glass float is used to set column flow System performance mixture A mixture or three target compounds e g benzene trichloroethylene and styrene in nitrogen is used for monitoring instrument performance The approximate concentra tion for each of the compounds in this mixture is 10 parts per billion ppb This mixture is manufac tured in small disposable gas cylinders at 275 kPa 40 psi from Scott Specialty Gases or equivalent Reagent grade nitrogen gas A small disposable cylinder of high purity nitrogen gas is used for blank injections Sampling syringes Gas tight syringes without attached shut off valves Hamilton Model 1002LT or equivalent are used to introduce accurate sample volumes into the high pressure injectors on the portable gas chromatograph Gas syringes with shut off valves are not recommended because of memory problems associated with the valves For samples suspected of containing high concentra tions of volatile compounds disposable glass syringes e g Glaspak or equivalent with stainless steel Teflon hub needles are used High pressure filler An adapter Photovac SA101 or equivalent for filling the internal carrier gas reservoir on the portable G
176. ifying the air emissions of the specific pollutant a critical input to the dispersion model can be difficult Such factors should be considered as a part of the design of a model validation program 37 6 6 REFERENCES 1 U S EPA 1978 Guidelines on Quality Models Revised EPA 405 2 78 027R NTIS PB86 245248 Office of Air Quality Planing and Standards Research Triangle Park North Carolina 27711 Chemical Manufacturers Association 1988 Chemi cals in the Community Methods to Evaluate Air borne Chemical Levels Washington D C 20037 Chemical Manufacturers Association 1988 Risk Communication Risk Statistics and Risk Compari sons A Manual for Plant Managers Washington D C 20037 American Meteorological Society 1981 Air Quality Modeling and the Clean Air Act Recommendations to EPA on Dispersion Modeling for Regulatory Applications Boston Massachusetts U S EPA October 1979 Procedures for Evaluating the Performance of Air Quality Simulation Models EPA 450 4 79 033 Office of Air Quality Planning and Standards Research Triangle Park North Carolina 27711 reed ver 5 9 errs wre 22 um 7 0 ESTIMATING PROGRAM COSTS One of the key questions you will ask is How much does it cost to implement a regional air monitoring pro gram This chapter provides both unit costs and overall estimated costs for two scenari
177. iked samples control charts blanks canisters certifi cation and cleanup internal standards zero and span gases quality control samples surrogate samples cali bration standards and devices and reagent checks The laboratory performance in implementing these elements should be considered as a part of the laboratory selection process Specifications for implementation of these laboratory QC checks are summarized in Tables 5 2 and 5 3 In addition the analytical methods selected for program application generally include specific labor atory QA QC checks IMPLEMENTING DATA MANAGEMENT QA QC CHECKS Raw monitoring data should be checked for validity before they are used as a part of the data base for site decision making These validity checks are an integral part of the QA QC program for monitoring activities A 5 5 30 qualified person who is not directly involved with the laboratory activities should validate the data Elements of the data validation include evaluation of the quality of the raw monitoring data against the field and laboratory QA QC data and verification of the calculations of ambient concentrations Meteorological Data Validation The validity of raw meteorological data should be checked using equipment calibration audit and perfor mance data Comprehensive technical recommendations for meteorological data validation are presented in On Site Meteorological Program Guidance for Regulatory Modeling App
178. il 1984 Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air and Subsequent Updates EPA 600 4 84 041 Office of Research and Development Research Triangle Park North Carolina 27711 This document contains details for Methods TO 1 through TO 6 U S EPA September 1986 Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air Supplement and Subsequent Updates EPA 600 U 87 006 Office of Research and Development Research Triangle Park North Carolina 27711 This document contains details for Methods TO 7 through TO 9 U S EPA June 1988 Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air Second Supplement and Subsequent Updates EPA Revised June 1988 Office of Research and Development Research Triangle Park North Carolina 27711 This document contains details for Methods TO 10 through 14 U S EPA September 1983 Characterization of Hazardous Waste Sites A Methods Manual Volume II Available Sampling Methods EPA 600 4 83 040 NTIS PB 84 126929 Office of Solid Waste Washington D C 20460 This volume is a compilation of sampling methods suitable to address most needs that arise during routine waste site and spill investigations Twelve methods are presented for ambient air soil gases and vapors and headspace gases U S EPA September 1983 Characterization of Hazardous Waste Sites A Methods Manual Volume ITI Available
179. industrial participants It is also true that these publics are much more likely to accept results if they have been actively included in all stages of the project Therefore at the start each party with a significant interest in the program must be involved This involve ment will ensure that the results are useful Hence you must consider the following questions Who should you involve All interested parties must be involved Their objec tives once agreed upon should be incorporated into the project planning stages to help create a focused program effort Some typical parties include the general public governmental bodies industrial groups and Chambers of Commerce These relationships to the involvement process are described in the paragraphs below Identifying who in the general public should partic ipate in the monitoring program is not easy In general you need to involve those groups or individuals whose acceptance of the study results would be most credible among other members of the public For example prime candidates for inclusion are public interest or environ mental advocacy groups or neighborhood coalitions in areas where exposure levels are considered to be high Responsibility for air toxics regulations or policies generally resides with Federal state or local air pollution control agencies To add credibility to your program consider involving or at a minimum informing key agency staff in the regi
180. ing See Figure 2 With Metal Bellows Pump 9 1 2 1 9 1 2 2 Pressurized sampling is used when longer term integrated samples or higher volume samples are required The sample is collected in a canister using a pump and flow control arrangement to achieve a typical 103 206 kPa 15 30 psig final can ister pressure For example 6 liter evacuated canister can be filled at 10 cm3 min for 24 hours to achieve a final pressure of about 144 kPa 21 psig In pressurized canister sampling a metal bellows type pump draws in ambient air from the sampling manifold to fill and pressurize the sample canister 9 1 3 All Samplers 9 1 3 1 9 1 3 2 9 1 3 3 9 1 3 4 9 1 3 5 A flow control device is chosen to maintain a constant flow into the canister over the desired sample period This flow rate is determined so the canister is filled to about 88 1 kPa for subatmospheric pressure sampling or to about one atmosphere above ambient pressure for pressurized sampling over the desired sample period The flow rate can be calculated by PxV T x 60 where F flow cm min P final canister pressure atmospheres absolute P is approximately equal to kPa gauge 1 1012 7 where V volume of the canister cm3 T sample period hours For example if a 6 L canister is to be filled to 202 kPa 2 atmospheres absolute pressure in 24 hours the flow rate can be calculated by _ 2 x 6000 24 x 6
181. int calibration is performed daily on the analytical sys tem to verify the initial multipoint calibration see Section 10 3 3 1 The analyzers GC FID ECD are calibrated before sample analysis using the static calibration procedures see Section 10 2 3 2 involving pressurized gas cylinders containing low concentrations of the targeted VOCs 10 ppbv in nitrogen After calibration humid ner zero air is once again passed through the analytical system to verify residual VOCs are not present 10 3 4 GC FID ECD PID System Performance Criteria 10 3 4 1 10 3 4 2 10 3 4 3 10 3 4 4 As an option the user may wish to include a photoionization detector PID to assist in peak identification and increase sensitivity This analytical system is presently being used in U S Environmental Protection Agency s Urban Air Toxic Pollutant Program UATP Preparation of the GC FID ECD PID analytical system is identical to the GC FID ECD system see Section 10 3 Table 8 outlines typical retention times minutes for selected organics using the GC FID ECD PID analytical system 10 4 Analytical Procedures 10 4 1 Canister Receipt 10 4 1 1 10 4 1 2 10 4 1 3 10 4 1 4 The overall condition of each sample canister is observed Each canister should be received with an attached sample identification tag Each canister is recorded in the dedicated laboratory logbook Also noted on the identification tag are date received and initia
182. integrating the area of one or more response peaks and calculating peak areas cor rected for baseline drift U S EPA Compendium Method T014 1988 101 7 2 3 4 Six port gas chromatographic valve Seismograph Service Corp Tulsa OK Seiscor Model VIII or equivalent 7 2 3 5 Cryogenic trap with temperature control assembly refer to Section 10 1 1 3 for complete description of trap and temperature control assembly Nutech Corpora tion 2142 Geer St Durham NC 27704 Model 320 01 or equivalent 7 2 3 6 Electronic mass flow controllers 3 maintain constant flow for carrier gas nitro gen make up gas and sample gas and to provide analog output to monitor flow anomalies Tylan Model 260 0 100 cm min or equivalent 7 237 Vacuum pump general purpose laboratory pump capable of drawing the desired sample volume through the cryogenic trap see 7 2 1 6 for source and description 7 2 3 8 Chromatographic grade stainless steel tubing and stainless steel plumbing fittings refer to Section 7 1 1 8 for description 7 2 3 9 Chromatographic column to provide compound separation such as shown in Table 7 Hewlett Packard Rt 41 Avondale PA 19311 OV 1 capillary column 0 32 mm x 50 m with 0 88 um crosslinked methyl silicone coating or equivalent Note Other columns e g DB 624 can be used as long as the system meets user needs The wider Megabore column i e 0 53 mm 1 0 is less susceptible to plugging as a r
183. ion 5 3 EXECUTING LABORATORY QA QC PROGRAM Section 5 4 IMPLEMENTING DATA MANAGEMENT QA QC CHECKS Section 5 5 27 DEFINING QUALITY ASSURANCE QUALITY CONTROL QA QC REQUIREMENTS Many people confuse the terms quality assurance and quality control QA QC Both activities are concerned with maintaining consistent and verifiable quality in each element of the program Strictly speaking quality con trol QC applies to measures taken on an ongoing basis by personnel involved in producing the primary output of the program These actions are taken to main tain performance parameters within acceptable levels An example of quality control activity is a routine zero span calibration check of a monitoring instrument by the responsible operating technician 5 1 Quality assurance on the other hand refers to checks or tests performed by personnel other than the primary operators to verify that the performance parameters have in fact been maintained within acceptable limits Examples of quality assurance activities are performing a quarterly audit of monitoring instruments and checking output data for out of limits values In the discussion which follows QA QC is used as a general term to encompass both QA and QC activities A rigorous QA QC effort is necessary during the operation of the regional air monitoring program to meet monitoring objectives Major QA QC elements that you should implement during the operation
184. ion Limit Accuracy Precision 2 Advantages Disadvantages Designation 0 01 1 ppb 80 100 2096 Moisture is not collected Large sample volume can be concentrated Documented standard procedures TENAX GC ADSORPTION AND GC MS OR GC ECD Ambient air is drawn through a cartridge containing Tenax where certain volatile organic compounds are adsorbed Compounds are transferred by programmed thermal desorption into a GC and detected by MS or ECD Contamination problems possibie Artifact formation problems Rigorous cleanup required No possibility of multiple analyses available with extensive QA QC data Low breakthrough volumes for base some compounds Practical for field use Low detection limits CARBON MOLECULAR SIEVE ADSORPTION AND 70 95 10 40 GC MS OR GC ECD Ambient air is drawn through a cartridge containing carbon molecular sieve where highly volatile compounds are adsorbed Compounds are thermally desorbed to a GC where they are quantitatively measured using MS or EC detectors 1 200 pptv 20 ml sample TO 3 0 1 ppbv 100 ml sample TO 14 0 1 4ppb 90 110 1 Accuracy The Agreement of an analytical measurement with true or accepted value Values in this table are expressed as Percent Recovery R Measured Value True Value x 100 2 Precision The reproducibility of repeated measurements of the same property usually made under prescribed conditions Values in
185. ions Quality Control QC activities complement QA activities QC activities address sampling procedures sample integrity analysis methods calibration procedures equipment mainte nance procedures and data production QC procedures are also performed by individuals involved in the normal routine operations 7 3 QUALITY ASSURANCE MANAGEMENT A QA program is essentially a management tool used to ensure that data collected is con tinually consistent with predetermined quality limits The major elements of an effective QA program included in a TOAP monitoring program are discussed in the following subsections 7 3 1 Quality Assurance System Design Three fundamental elements comprise an effective QA program First QA policy and quantitative quality goals or objectives must be defined in a written QA plan Secondly organizational structure must accommodate a QA function through job assignments and communication mechanisms Third individuals associated with the QA function must have written job descriptions duties responsibilities and authority commensurate with their in tended function Each of these vital QA program components is discussed below Before a QA program can be developed it is necessary to establish a QA policy and estab lish the objectives of the QA program Once these fundamental tasks have been accom plished aQA program can be written to address the strategy for achieving definitive quality objectives relevant to the a
186. ions of the standard containing all compounds for retention time window determination Note The retention time window must be established for each analyte every 72 hours during continuous operation Calculate the standard deviation of the three absolute retention times for each single component standard The retention window is defined as the mean plus or minus three times the standard deviation of the individual retention times for each standard In those cases where the standard deviation for a particular standard is zero the laboratory must substitute the standard deviation of a closely eluting similar compound to develop a valid retention time window The laboratory must calculate retention time windows for each standard see Table 7 on each GC column whenever a new GC column is installed or when major compo nents of the GC are changed The data must be noted and retained in a notebook by the laboratory as part of the user SOP and as a quality assurance check of the analyt ical system GC Calibration Note Initial and routine calibration procedures are illustrated in Figure 14 10 3 3 1 Initial Calibration Initially a multipoint dynamic calibration three levels plus humid zero air is performed on the GC FID ECD system before sample analysis with the assistance of a calibration system see Figure 8 The calibration system uses NBS traceable standards or NBS EPA CRMs in pressurized cylinders containing a mixture of the targ
187. ironmental scientists namely sampling for toxic organics in ambient workplace and source related atmos pheres analyzing for important classes of pollutants such as polychlorinated biphenyls PCBs polynuclear aromatic hydrocarbons PAHs and polycyclic organic matter POM and measuring exposure to toxic organics in the workplace 4 California Air Resources Board CARB February 1985 Toxic Ambient Air Monitoring Operation Procedures Cal ifornia Network Aerometric Data Division California Air Resources Board Sacramento California 95814 5 CARB December 1986 Testing Guidelines for Active Solid Waste Disposal Sites Stationary Source Division Toxic Pollutants Branch California Air Resources Board Sacramento California 95814 These guidelines present standard operating procedures for the sampling and analysis of ambient air collected in Tedlar bags Analytical procedures are primarily for halogenated volatile organics and benzene 6 Draeger May 1985 Detector Tube Handbook Draegerwerk AG Lubeck Federal Republic of Germany This handbook presents procedures for the use of colorimetric detector tubes for a wide range of organic and inor ganic compounds Data is provided on standard ranges of measurement precision and accuracy measurement princi ples and cross sensitivity 7 NIOSH February 1984 NIOSH Manual of Analytical Methods NTIS PB85 179018 National Institute of Occupa tional Safety and Health Cincinnati Ohio
188. ister is connected to one of the short lengths of 1 8 inch O D stainless steel tubing from port B solenoid valve of the sampler The canister valve is left closed The Swagelok fitting on the canister must not be cross threaded The connection is tightened snugly with a wrench 4 1 4 The end of the other length of stainless steel tubing from port B solenoid valve is connected with a Swagelok plug 4 1 5 If duplicate canisters are to be sampled the plug is removed from the second 1 8 inch O D stainless steel tubing from port B solenoid valve and the second canister is connected The canister valve is left closed 4 1 6 The ON button of timer 42 is pressed The flow through the flow controller should be stopped by this action 4 1 7 flow controller switch is turned to READ and the zero flow reading is obtained If this reading is not stable wait until the reading is stabilized 4 1 8 The flow controller switch is turned to SET and the flow setting is adjusted to the algebraic SUM of the most recent entry on Table C 1 and the zero reading obtained in step 4 1 7 If the zero reading is negative SUBTRACT the zero reading from the Table C 1 value Be sure to use the correct Table C 1 flow value for one or two canisters as appropriate Note If the analytical laboratory determines that the canister sample pressure is too low or too high a new flow setting or settings will be issued for the sampler The new flow setting sh
189. isture and organic impurities from gas streams Alltech Associates 2051 Waukegan Road Deerfield IL 60015 or equivalent Deionized water high performance liquid chromatography HPLC grade ultrahigh purity for humid ifier best source 4 bromofluorobenzene used for tuning GC MS best source Hexane for cleaning sampling system components reagent grade best source Methanol for cleaning sampling system components reagent grade best source Sampling System 9 1 System Description 911 Subatmospheric Pressure Sampling See Figure 2 Without Metal Bellows Type Pump 9 1 1 1 In preparation for subatmospheric sample collection in a canister the canister is evacuated to 0 05 mm Hg When opened to the atmosphere containing the VOCs to be sampled the differential pressure causes the sample to flow into the canister This technique may be used to collect grab samples duration of 10 to 30 seconds or time integrated samples duration of 12 to 24 hours taken through a flow restrictive inlet e g mass flow controller critical orifice 9 1 1 2 With a critical orifice flow restrictor there will be a decrease in the flow rate as the pressure approaches atmospheric However with a mass flow controller the sub atmospheric sampling system can maintain a constant flow rate from full vacuum to within about 7 kPa 1 0 psi or less below ambient pressure U S EPA Compendium Method T014 1988 9 1 2 Pressurized Sampl
190. ital format that is directly computer compatible Air sampling information and results need to be tran scribed from hardcopy records to computer files Monitoring data summaries should be prepared using the validated data bases as input By using these meteor ological and air monitoring data summaries program managers can readily identify airborne concentrations at various locations The main reason to perform regional air monitoring is to collect high quality credible data Therefore data from air monitoring and meteorological stations must meet data recovery requirements Cur rently for permitting purposes EPA requires data recovery rates total number of valid observations divided by the total number of possible observations of 80 percent for air quality data and 90 percent for meteor ological data Any regional air monitoring system estab lished should plan to meet or exceed these requirements to ensure credibility of the results Meteorological Data Summaries Meteorological data summaries should include at the least the following 33 FIGURE 6 1 SUMMARIZE AND EVALUATE RESULTS VALIDATED AIR METEOROLOGICAL DATA GENERATE COMPUTER DATA BASE FILES METEOROLOGICAL FILES AIR MONITORING FILES SUMMARIZE DATA DATA LISTINGS STATISTICAL SUMMARIES AIR MONITORING SUMMARIES METEOROLOGICAL SUMMARIES DATA INTERPRETATION SUMMARY REPORTS e Listing of hou
191. l Assistance Document for Sampling and Analysis of Toxic Organic Compounds in Ambient Air and Subsequent Updates EPA 600 4 83 027 NTIS PB83 239020 Office of Research and Development Research Triangle Park North Carolina 27711 U S EPA April 1984 Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air and Subsequent Updates EPA 600 4 84 041 Office of Research and Development Research Triangle Park North Carolina 27711 U S EPA September 1986 Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air and Subsequent Updates EPA 600 4 87 006 NTIS PB87 168696 Office of Research and Devel opment Research Triangle Park North Carolina 27711 U S EPA June 1988 Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air Second Supplement TO 10 through TO 14 and Subsequent Updates EPA Revised June 1988 Office of Research and Development Research Triangle Park North Carolina 27711 U S EPA 1977 Quality Assurance Handbook for Air Pollution Measurement Systems EPA 600 4 77 027a Volume Section 2 2 High Volume TSP Samplers Section 2 11 High Volume PM 10 Samplers Quality Assurance Division Environmental Monitoring Systems Laboratory Research Triangle Park North Carolina 27711 NIOSH February 1984 NIOSH Manual of Analytical Methods NTIS PB85 179018 National Institute for Occupational Safety and Health Cincin
192. lations This procedure is often done in the technical community For example if the detection limit for benzene is 1 part per billion ppb and labora tory analysis indicates concentrations below method detection limit then the value will reported as ND 1 0 ppb However for statistical calculations a value of 0 5 ppb will be used If more than 30 percent of the values are below the detection limit no statistical calculations should be attempted Air concentrations should be expressed in g m3 or ppb Raw data used to derive the concentration are also useful to list in supplemental tables Such data would include sampling start and end times constituent content in the sample in g volume of air sampled over the sampling period in m3 and temperature and pressure conditions during sampling time in F and mm Hg respectively Summary tables of constituent specific concentrations measured for each monitoring station should include the following minimum and maximum concentrations QA QC concentrations including blanks duplicates and others detection limits frequency above and below detection limits number of samples number of occur rences of air concentrations exceeding selected values e g health and safety criteria and odor thresholds and when applicable upwind downwind concentration summaries A narrative discussion of sampling results should indi cate the problems encountered the relationship of the sampling a
193. ld to prevent condensation on the internal walls of the system The analytical strategy for Method TO 14 involves positive identification and quanti tation by GC MS SCAN SIM mode of operation with optional FID This is a highly specific and sensitive detection technique Because a specif c detector system GC MS SCAN SIM is more complicated and expensive than the use of non specific detectors GC FID ECD PID the analyst may want to perform a screening analysis and preliminary quantitation of VOC species in the sample including any polar compounds by utilizing the GC multidetector GC FID ECD PID analytical system prior to GC MS analysis This system can be used for approximate quantita tion The GC FID ECD PID provides snap shot of the constituents in the sample allowing the analyst to determine Extent of misidentification due to overlapping peaks Whether the constituents are within the calibration range of the anticipated GC MS SCAN SIM analysis or does the sample require further dilution and Are there unexpected peaks which need further identification through GC MS SCAN or are there peaks of interest needing attention If unusual peaks are observed from the GC FID ECD PID system the analyst then performs a GC MS SCAN analysis The GC MS SCAN will provide positive identifi cation of suspect peaks from the GC FID ECD PID system If no unusual peaks are identified and only a select number of VOCs are of concern the
194. le The SARA 313 list contains pollu tants for which new sampling and analytical methods are needed TABLE A 1 LIST OF VOLATILE ORGANICS QUANTIFIED IN THE EPA TOXIC AIR MONITORING STATIONS TAMS PROGRAM Compound Name 1 dichlorodifluoromethane Freon 12 2 methyl chloride 3 vinyl chloride 4 trichlorofluoromethane Freon 11 5 dichloromethane 6 3 chloropropene 7 1 1 2 trichloro 1 2 2 trifluorethane Freon 113 8 1 2 dichloroethane 9 1 1 1 trichloroethane 10 benzene 11 carbon tetrachloride 12 trichloroethene 13 toluene 14 tetrachloroethene 15 chlorobenzene 16 ethylbenzene 17 m p xylene 18 styrene 19 o xylene 20 4 ethyl toluene 21 1 3 5 trimethyibenzene 22 1 2 4 trimethylbenzene 23 benzyl chioride 24 1 2 4 trichlorobenzene 47 TABLE A 2 EPA URBAN AIR TOXICS MONITORING PROGRAM COMPOUND LIST OAR WN S mb Q0 4 ND PD N A 2 O0 0 141001 00 I0 Compound Name acetylene propylene 1 3 butadine vinyl chloride chloromethane chloroethane bromomethane methylene chloride trans 1 2 dichloroethylene 1 1 dichloroethane chloroprene bromochloromethane chloroform 1 1 1 trichloroethane carbon tetrachloride 1 2 dichloroethane benzene 1 2 dichloroethane benzene trichloroethylene 1 2 dichloropropane bromodichlorometh
195. le Park North Carolina 27711 U S EPA November 1980 Ambient Monitoring Guidelines for Prevention of Significant Deterioration PSD EPA 450 4 80 012 NTIS PB 81 153231 Office of Air Quality Planning and Standards Research Triangle Park North Carolina 27711 U S EPA June 1983 Technical Assistance Document for Sampling and Analysis of Toxic Organic Compounds in Ambient Air EPA 600 4 83 027 NTIS PB 83 239020 Office of Research and Development Research Triangle Park North Carolina 27711 U S EPA 1977 Quality Assurance Handbook for Air Pollution Measurement Systems Volume II Ambient Air Specific Methods EPA 600 4 27 027a Environmental Monitoring Systems Laboratory Research Triangle Park North Carolina 27711 U S GSA 1987 Code of Federal Regulations Title 40 Part 50 Appendices A G and J Office of the Federal Register Washington D C 20402 The listed appendices to 40 CFR 50 contain EPA Reference Methods for the sampling and analysis of SO TSP CO O NO Pb and PM 10 in ambient air 69 25 gt APPENDIX E EXCERPT FROM TECHNICAL ASSISTANCE DOCUMENT FOR SAMPLING AND ANALYSIS OF TOXIC ORGANIC COUS EPA IN AMBIENT AIR S EPA Previously published in June 1983 as EPA document 800 4 83 027 Revised by ATC Inc Auburn Alabama EPA Excerpt Sampling and Analysis of Toxic Organic Compounds in Ambient Air 71 25
196. lications A summary of applicable meteorological data screening criteria is presented in Appendix G Air Monitoring Data Validation Similarly the validity of air monitoring data should use equipment calibration audit and performance data in a manner similar to that recommended for meteoro logical data A qualified chemist who is familiar with both the data validation requirements and the process should validate the analytical results Validation of analytical results for one sample could take from 15 minutes to more than an hour depending on the type of analysis used the num ber of air toxic constituents involved interference con tamination and other factors Raw air quality data received from portable GC ana lyzers or other continuous instruments must be checked for validity The performance of the analyzer calibration information and QA results should be considered Air monitoring data validation efforts should include statistical analysis considering collocated sample results and audit results to determine data precision and accuracy A recommended statistical procedure is pre sented in Appendix G 5 6 REFERENCES 1 U S EPA June 1983 Technical Assistance Docu ment for Sampling and Analysis of Toxic Organic Compounds in Ambient Air and subsequent updates EPA 600 4 83 027 NTIS PB83 239020 Office of Research and Development Research Triangle Park North Carolina 27711 2 U S EPA April 1984 Compe
197. liquid oxy gen or argon to prevent contamination from back diffusion of oil from vacuum pump and to provide clean zero air to sample canister s Stainless steel pressure gauges 2 0 345 kPa 0 50 psig to monitor zero air pressure Stainless steel flow control valve to regulate flow of zero air into canister s Humidifier pressurizable water bubbler containing high performance liquid chromatography HPLO grade deionized water or other system capable of providing moisture to the zero air supply Isothermal oven optional for heating canisters Fisher Scientific Pittsburgh PA Model 349 or equivalent Calibration System and Manifold See Figure 8 7 4 1 7 4 2 Calibration manifold glass manifold 1 25 cm 1 0 x 66 cm with sampling ports and internal baffles for flow disturbance to ensure proper mixing Humidifier 500 mL impinger flask containing HPLC grade deionized water 102 U S EPA Compendium Method T014 1988 7 4 3 Electronic mass flow controllers one 0 to 5 L min and one D to 50 cm min Tylan Corpora tion 23301 TS Wilmington Ave Carson CA 90745 Model 2160 or equivalent 7 44 Teflon filter s 47 mm Teflon filter for particulate control best source 8 0 Reagents and Materials Gas cylinders of helium hydrogen nitrogen and zero air ultrahigh purity grade best source 8 2 Gas calibration standards cylinder s containing approximately 10 ppmv of each of the following 9 0
198. ls of recipient The pressure of the canister is checked by attaching a pressure gauge to the canister inlet The canister valve is opened briefly and the pressure kPa psig is recorded Note If pressure is 83 kPa 12 psig the user may wish to pressurize the canisters as an option with zero grade nitrogen up to 137 kPa 20 psig to ensure that enough sample is available for analysis However pressurizing the canister can introduce additional error increase the minimum detection limit MDL and is time consuming The user should weigh these limitations as part of his program objectives before pressurizing Final cylinder pressure is recorded on canister sampling field data sheet see Figure 10 If the canister pressure is increased a dilution factor DF is calculated and recorded on the sampling data sheet DF Ya mum abere Canister pressure kPa psia absolute before dilution Ya canister pressure kPa psia absolute after dilution After sample analysis detected VOC concentrations are multiplied by the dilution factor to determine concentration in the sampled air U S EPA Compendium Method T014 1988 10 4 2 GC MS SCAN Analysis With Optional FID System 10 4 2 1 10 4 2 2 10 4 2 3 10 4 2 4 10 4 2 5 10 4 2 6 10 4 2 7 10 4 2 8 10 4 2 9 10 4 2 10 10 4 2 11 The analytical system should be properly assembled humid zero air certified see Section 12 3 operated see
199. m oven at 50 C Typically stainless steel parts and fittings are cleaned by placing them in a beaker of methanol in an ultrasonic bath for 15 min utes This procedure is repeated with hexane as the solvent 11 2 1 2 The parts are then rinsed with HPLC grade deionized water and dried in a vacuum oven at 100 C for 12 to 24 hours 11 2 1 3 Once the sampler is assembled the entire system is purged with humid zero air for 24 hours 114 U S EPA Compendium Method 014 1988 11 2 2 Humid Zero Air Certification Note In the following sections certification is defined as evaluating the sampling system with humid zero air and humid calibration gases that pass through all active components of the sampling system The system is certified if no significant additions or deletions less than 0 2 ppbv of targeted compounds have occurred when challenged with the test gas stream 11 2 2 1 The cleanliness of the sampling system is determined by testing the sampler with humid zero air without an evacuated gas cylinder as follows 11 2 2 2 The cal bration system and manifold are assembled as illustrated in Figure 8 The sampler without an evacuated gas cylinder is connected to the manifold and the zero air cylinder activated to generate a humid gas stream 2 L min to the calibra tion manifold see Figure 8 b 11 2 2 3 The humid zero gas stream passes through the calibration manifold through the sampling system without an evacuated
200. ment as part of its Chemicals Community series Other documents in this and related series include CHEMICALS IN THE COMMUNITY Series includes Methods to Evaluate Airborne Chemical Levels May 1988 A resource document presents two general approaches for placing emission levels in context data base driven and model driven Using these two approaches 8 methods are described to evaluate the health impact of air borne releases Member price 8 00 Non member price 12 00 Implementing Regional Air Monitoring Programs February 1990 A manual to assist companies establish regional air monitoring programs This document covers both the policy issues and the technical details of setting up a regional air monitoring project Member price 20 00 Non member price 40 00 Understanding Environmental Fate in preparation IMPROVING AIR QUALITY Series includes Guidance for Estimating Fugitive Emissions from Equipment January 1989 A guidance manual of fugitive emission testing for plants that want to conduct accurate leak rate estimations This manual includes the EPA protocol with notations for implementation by the chemical industry Member price 20 00 Non member price 30 00 Fugitive Emission Workshop Videotapes These videotapes cover some of the topics plant personnel ask about when setting up a testing program for equipment leak detection and repair LDAR Minutes Member Price Non Member Price Tape I Ov
201. ments for status reports and review meetings invoicing and other administrative items As part of the contractors response you should ask them to identify and present the qualifications of any subcontractors that they propose to use for the project In general allow three to four weeks to permit bidders to present compre hensive proposals You must consider several key factors when evaluating contractor capabilities and quotations for ambient air toxics monitoring This list is not all inclusive Develop your evaluation criteria before contractor bids are returned so you have an unbiased yardstick to judge the contractors equitably e Experience of assigned personnel on similar projects Educational background and training of assigned personnel Perceived ability of assigned individuals to work harmoniously and effectively with the sponsor s management and field personnel Cost including rate levels and basis mark up per centages and overtime provisions In house laboratory capability or established rela tionship with an outside laboratory QA QC policy and practices Range of methods employed by the laboratory Mode of communications and management mech anisms between sampling and analytical personnel Flexibility of approach e g availability of leased vs purchased equipment e Contract terms and conditions e Proximity and availability of assigned personnel e Understanding o
202. methods the meteor ological monitoring requirements associated with each air monitoring program are important A discussion of these requirements is included in Section 3 5 Next comes the design of the network which is des cribed in Section 3 6 This section covers the number and locations of monitoring stations the siting of air monitoring and meteorological stations the use of models to select monitoring sites and network design for dispersion model validation Finally the selection of contractors for performing air sampling and analysis is discussed in Section 3 7 Also the elements associated with such a selection process are included in this section FIGURE 3 1 KEY ELEMENTS OF A REGIONAL AIR TOXICS MONITORING PROGRAM SELECTING CONSTITUENTS Section 3 2 Figure 3 2 Appendices A and B SELECTING DURATION AND FREQUENCY OF MONITORING Section 3 3 Table 3 1 SELECTING SAMPLING AND ANALYTICAL METHODS Section 3 4 Tables 3 2 and 3 3 Appendices C and D DETERMINING METEOROLOGICAL REQUIREMENTS Section 3 5 Tables 3 4 and 3 5 DESIGNING THE NETWORK Section 3 6 SELECTING CONTRACTORS FOR SAMPLING AND ANALYSIS Section 3 7 3 2 SELECTING CONSTITUENTS OF INTEREST Once a decision has been made to conduct a regional air monitoring program you have to establish a list of constituents to be analyzed Figure 3 2 outlines the process for selecting constituents The starting point is the list o
203. more than one detector Portable GC analyzer utilizing 0 1 to several ppb About 5 10 depending Real time continuous Similar to the ones mentioned Similar to the ones mentioned above photoionization detector PID with a depending on the on compound involved above with the exception that it with the addition of range of 5 different energy lamps to number of compounds high reproducibility uses only one detector provide selectivity for different chemical involved and the mix Isothermal oven control is up to groups isothermal oven control for the 50 C This GC cannot operate at multi capillary column Up to higher temperatures This 25 compounds can be processed at any reduces the range of volatile time Include four libraries of organics that can be analyzed 25 compounds each Calibration is by Useful mainly for high volatile injecting standard calibration gas organics Cannot use detectors other than the PID Portable GC analyzer can use either a PID 0 1 to several ppb Not readily available but Real time continuous Similar to the ones above Similar to ones listed for the portable or FID Includes isothermal temperature depending on the expected to be in the GC with a ECD with the addition of control of up to 300 C for one model and number of compounds same range as above Similar to the ones above with the up to about 200 C for another Calibrate involved and the mix exception that it uses only a PID temperature
204. motely from the sampler connected with a 1 4 inch O D extension tubing and a suitable electrical extension cord U S EPA Compendium Method 014 1988 164 3 2 Electrical Connections Figure C 1 3 3 3 2 1 The sampler cover is removed The sampler is not plugged into the 115 vac power until all other electrical connections are completed 3 2 2 The pump is plugged into its power connector not already connected and the battery con nectors are snapped onto the battery packs on the covers of both timers 3 2 3 The sampler power plug is inserted into a 115 volts ac line grounded receptacle The sampler must be grounded for operator safety The electrical wires are routed and tied so they remain out of the way Pneumatic Connections 3 3 1 The length of 1 16 inch stainless steel tubing is connected from port A of the sampler on the right side of the flow controller module to the air inlet line 3 3 2 The pump is connected to the sampler with 1 4 inch O D plastic tubing This tubing may be up to 7 meters 20 feet long A short length of tubing is installed to reduce pump noise All tubing is conveniently routed and if necessary tied in place 4 0 Sampler Preparation 4 1 4 2 Canister 411 The sample canister is installed no more than 2 days before the scheduled sampling day 4 1 2 With timer 1 ON the flow controller is allowed to warm up for at least 15 minutes longer if possible 4 1 3 An evacuated can
205. mounted on a baseplate fitted into the injection and auxiliary zones of the GC on an insulated pad directly above the column oven when used with the Hewlett Packard 5880 GC Note Alternative trap assembly and connection to the GC may be used depending upon user s requirements The carrier gas line is con nected to the injection end of the analytical column with a zero dead volume fitting that is usually held in the heated zone above the GC oven A 15 cm x 15 cm x 24 cm aluminum box is fitted over the sample handling elements to complete the pack age Vaporized cryogen is vented through the top of the box As an option the analyst may wish to split the gas stream exiting the column with a low dead volume tee passing one third of the sample gas 1 0 mL min to the mass selective detector and the remaining two thirds 2 0 mL min through a flame ionization detector as illustrated as an option in Figure 4 The use of the specific detector MS SCAN coupled with the non specific detector FID enables enhance ment of data acquired from a single analysis In particular the FID provides the user e Semi real time picture of the progress of the analytical scheme e Confirmation by the concurrent MS analysis of other labs that can provide only FID results and Ability to compare GC FID with other analytical laboratories with only GC FID capability 10 1 2 GC MS SIM System 10 1 2 1 10 1 2 2 The analytical system is comprised of a GC eq
206. mples cover the operation and maintenance of the canister VOCs sampler and meteorological equipment FIGURE 4 2 FIELD INSTRUMENTATION OPERATION AND MAINTENANCE MONITORING PLAN SECTION 3 0 SELECTING AND TRAINING PERSONNEL SECTION 4 1 TECHNICAL ASSISTANCE DOCUMENT APPENDIX STANDARD OPERATING PROCEDURES APPENDIX 0 OPERATION AND MAINTENANCE SECTION 4 3 OTHER TECHNICAL REFERENCES RECORDKEEPING REQUIREMENTS SECTION 4 4 SAMPLING ANALYSIS INSTRUMENTATION CALIBRATION TABLE 5 3 QC SAMPLING ANALYSIS FREQUENCIES TABLE 5 2 INPUT TO STANDARD OPERATING PROCEDURES SOPs APPENDIX F The subjects that are addressed in the SOPs generally include but are not limited to the following Purpose e Applicability Definitions e Manufacturers instructions and specifications Summary of methods including limitations e General requirements for optional operating performance e Operating procedures Operating schedule Sample handling handling in the field communi cation issues packaging and storage sample track ing chain of custody shipment and other issues e Sample holding time e Sample analysis e Routine equipment calibration and maintenance e Program audits Record keeping Program responsibilities 25 4 4 RECORDKEEPING REQUIREMENTS A key factor in a regional air monitoring
207. mulates the physical and chemical state of the native material 7 4 4 Sample Labeling Preservation Storage and Transport The data obtained from a TOAP monitoring program will be meaningless if samples are im properly labeled or if preservation storage or transport procedures are inappropriate for the required analyses Sample labeling preservation storage and transport procedures will therefore be specified in the QA plan and these procedures should be carefully explained to field personnel prior to sampling to ensure proper implementation Sample labels pre pared in advance should include sufficient information to associate a given sample with a particular data sheet as well as with the overall program record notebook In general each sample should be given a unique identification number with a prefix describing the type of sample EPA Excerpt Sampling and Analysis of Toxic Organic Compounds in Ambient Air 85 7 4 5 Chain of Custody Procedure Chain of custody procedures are used to document the movement of a sample from col lection until analysis to ensure sample integrity Formal chain of custody requirements place a substantial burden on both field and laboratory personnel Chain of custody proce dures must be documented in the QA plan for a TOAP monitoring project and reviewed with the personnel who will use them to ensure that the data is fundamentally legaliy defensible 7 5 ANALYTICAL QUALITY ASSURANCE The QA pla
208. n Act SARA 313 list contains some components that are very difficult to measure For some components new samp ling and analytical methods are needed In fact for some pollutants the monitoring difficulties are cost prohibitive If the monitoring results for a large number of the measured constituents are below the detection limits you can reduce the list of constituents to be monitored Otherwise one may choose to continue monitoring all constituents listed in Appendix A Since the primary goal of the program is to identify concentrations of air pollutants in the community the selected list of constituents for monitoring should reflect local concerns and issues To meet this objective it is recommended that you evaluate the following Community concerns regarding certain types of air toxics This should be a key factor in the selection process of constituents to be monitored e Air toxics release inventories filed under the requirements of the Toxic Chemical Release Reporting Community Right to Know 40 Part 372 subpart D EPA has computerized these inventories and these data are accessible to the public Such data will provide information on air toxics releases to the atmosphere from reporting industries You can obtain additional release infor mation from Federal and state agencies In addi tion EPA has information on estimates of air toxic constituents emitted from mobile sources e Air monitoring data
209. n for the analytical component of a TOAP monitoring program will address method validation requirements instrument maintenance and calibration quality control sample analysis and data recording Each of these aspects is discussed in the subsections that follow 7 5 1 Method Validation Many TOAP monitoring program will require the development of new or modification of ex iting sampling and analytical protocols It will be necessary to establish the performance characteristics of these procedures prior to their use in TOAP monitoring programs Per formance characteristics will include determination of precision accuracy detection limit and specificity through the analysis of laboratory standards and whenever possible repre sentative samples The validation requirements should be appropriate The incorporation of SRM s in the method validation process will prove cost effective and minimize the time re quired to bring a new method on line is important to validate the method in a manner that approximates as closely as possible the conditions that will exist when actual samples are col lected Performance critria for existing well documented methodologies must also be validated when a procedure is used for the first time by the test team Validation of this type will require the development of a data base sufficient to establish critical statistical parameters such as the coefficient of variation Again SRM s are a key component of th
210. nati Ohio 45226 U S EPA September 1983 Characterization of Hazardous Waste Sites A Methods Manual Volume Il Available Sampling Methods EPA 600 4 83 040 NTIS PB84 126929 Office of Solid Waste Washington D C 20460 U S EPA September 1983 Characterization of Hazardous Waste Sites A Methods Manual Volume lll Available Laboratory Analytical Methods EPA 600 4 83 040 NTIS PB84 126929 Office of Solid Waste Washington D C 20460 U S 1986 Test Methods for Evaluating Solid Waste 3rd Edition EPA SW 846 GPO No 955 001 00000 1 Office of Solid Waste Washington D C 20460 ASTM 1982 Toxic Materials in the Atmosphere ASTM STP 786 Philadelphia Pennsylvania 19103 ASTM 1980 Sampling and Analysis of Toxic Organics in the Atmosphere ASTM STP 721 Philadelphia Pennsylvania 19103 ASTM 1974 Instrumentation for Monitoring Air Quality ASTM SP 555 Philadelphia Pennsylvania 19103 APHA 1977 Methods of Air Sampling and Analysis American Public Health Association Washington D C 20005 ACGIH 1983 Air Sampling Instruments for Evaluation of Atmospheric Contaminants American Confer ence of Governmental Industrial Hygienists Cincinnati Ohio 45211 57 8S TABLE C 2 SUMMARY OF SAMPLING AND ANALYTICAL METHODS FOR TIME INTEGRATED AMBIENT MONITORING VOLATILE OPRGANICS Sampling and Analysis Approach Detection Limit Disadvantages CRYOGENIC PRECONCENTRATIO
211. ncement in sensitivity more specific than the multidetector GC GC MS SCAN positive compound identification e lower sensitivity than GC MS SIM e can identify all compounds greater sample volume required than for multidetector GC somewhat greater equipment cost than multidetector GC e less operator interpretation can resolve co eluting peaks The analytical finish for the measurement chosen the analyst should provide a definitive identifi cation and a precise quantitation of volatile organics In a large part the actual approach to these two objectives is subject to equipment availability Figure 1 indicates some of the favorite options that are used as an analytical finish The GC MS SCAN option uses a capillary column GC coupled to a MS operated in a scanning mode and supported by spectral library search routines This option offers the nearest approximation to unambiguous identification and covers a wide range of com pounds as defined by the completeness of the spectral library GC MS SIM mode is limited to a set of target compounds which are user defined and is more sensitive than GC MS SCAN by virtue of the longer dwell times at the restricted number of m z values Both these techniques but especially the GC MS SIM option can use a supplemental general non specific detector to verify identify the Presence of VOCs Finally the option labelled GC multidetector system uses a combination of retention time and multiple g
212. nces on the non specific detectors can still cause error in identifying a complex sample The non specific detector system GC NPD FID ECD PID however has been used for approximate quantitation of relatively clean samples The nonspecific detector system can provide a snapshot of the constituents in the sample allowing determination of Extent of misidentification due to overlapping peaks Position of the VOCs within or not within the concentration range of anticipated further analysis by specific detectors GC MS SCAN SIM if not the sample is further diluted and Existence of unexpected peaks which need further identification by specific detectors On the other hand the use of specific detectors MS coupled to a GC allows positive compound identification thus lending itself to more specificity than the multidetector GC Operating in the SIM mode the MS can readily approach the same sensitivity as the multidetector system but its flexibility is limited For SIM operation the MS is programmed to acquire data for a limited number of targeted compounds while disregarding other acquired information In the SCAN mode however the MS becomes a universal detector often detecting compounds which are not detected by the multide tector approach The GC MS SCAN will provide positive identification while the GC MS SIM proced ure provides quantitation of a restricted target compound list of VOCs The analyst often must decide whether
213. ncludes a computer and appropriate software for data acquisition data reduction and data reporting A 400 cm air sample is collected from the canister into the analytical system The sample air is first passed through a Nafion dryer through the 6 port chromatographic valve then routed into a cryogenic trap Note While the GC multidetector analytical system does not employ a Nafion dryer for drying the sample gas stream it is used here because the GC MS system utilizes a larger sample volume and is far more sensitive to excessive moisture than the GC multidetector analytical system Moisture can adversely affect detector precision The Nafion dryer also prevents freezing of moisture on the 0 32 mm 1 0 column which may cause column blockage and pos sible breakage The trap is heated 160 C to 120 C in 60 sec and the analyte is injected onto the OV 1 capillary column 0 32 mm x 50 m Note Rapid heating of the trap provides efficient transfer of the sample components onto the gas chroma tographic column Upon sample injection onto the column the MS computer is signaled by the GC computer to begin detection of compounds which elute from the column The gas stream from the GC is scanned within a preselected range of atomic mass units amu For detection of compounds in Table 1 the range should be 18 to 250 amu resulting in a 1 5 Hz repetition rate Six 6 scans per eluting chromatographic peak are provided at this rate The 10 15 la
214. ndium of Methods for Determination of Toxic Organic Compounds in Ambient Air and subsequent updates EPA 600 4 87 006 NTIS PB87 168696 Office of Research and Development Research Triangle Park North Carolina 27711 U S EPA September 1986 Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air and subsequent updates EPA 600 4 87 006 NTIS BB87 168696 Office of Research and Development Research Triangle Park North Carolina 27711 U S EPA June 1988 Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air Second Supplement TO 10 through TO 14 and subsequent updates EPA Revision 6 88 Office of Research and Development Research Triangle Park North Carolina 27711 U S EPA June 1987 On Site Meteorological Program Guidance for Regulatory Modeling Appli cations EPA 450 4 87 013 Office of Air Quality Planning and Standards Research Triangle Park North Carolina 27711 31 6 NIOSH February 1984 NIOSH Manual of Analytical Methods NTIS PB85 179018 National Institute of Occupational Safety and Health Cincinnati Ohio 45226 U S EPA February 1983 Quality Assurance Handbook for Air Pollution Measurements EPA 600 4 82 060 Office of Research and Devel opment Research Triangle Park North Carolina 27711 U S EPA May 1987 Ambient Monitoring Guide lines for Prevention of Significant Deterioration PSD EPA 450 4 87 007 NTIS PB81 153
215. nds that are too volatile to be collected by filtration air sampling but not volatile enough for thermal desorption from solid sorbents SVOCs can generally be classi fied as those with saturation vapor pressures at 25 C between 101 and 107 mm Hg VOCs are gener ally classified as those organics having saturated vapor pressures at 25 C greater than 107 mm Hg NM Definitions Note Definitions used in this document and in any user prepared Standard Operating Procedures SOPs should be consistent with ASTM Methods 01356 E260 and E355 All abbreviations and symbols within this method are defined at point of use 51 Absolute canister Pressure Pg Pa where Pg gauge pressure in the canister kPa psi and barometric Pressure see 5 2 5 2 Absolute pressure Pressure measured with reference to absolute zero pressure as opposed to atmospheric pressure usually expressed as kPa mm Hg or Psia 5 3 refrigerant used to obtain very low temperatures in the cryogenic trap of the analytical system A typical cryogen is liquid oxygen bp 183 0 C or liquid argon bp 185 7 C 5 4 Dynamic calibration Calibration of an analytical system using calibration gas standard concentra tions in a form identical or very similar to the samples to be analyzed and by introducing such stan dards into the inlet of the sampling or analytical system in a manner very similar to the normal sam pling or analytical process 5 5 Ga
216. ng ozone formation studies when the period between 6 00 a m to 9 00 a m is very critical Apply the 3 hour sampling duration to cover meteor ological events such as nighttime thermal inversions or on shore breezes or unusual events associated with the operation of industrial facilities The 3 to 8 hour samp ling periods also are important when sorbent tubes are used and breakthrough of constituents trapped in the tubes could occur Breakthrough could be a factor when Tenax tubes are used in the sampling program The recommended program lengths in Table 3 1 pro vide a reasonable data base that can be used in the appli cation under consideration For most of the program objectives in Table 3 1 you should obtain a minimum of 30 samples If the program lasts less than a year this will result in an increased sampling frequency For model validation study 24 hour integrated sam ples are generally suitable Short term samples such as 1 hour averages can closely track effects of variability in wind direction However these advantages are frequently offset by the need to deploy more samplers to increase the likelihood of sampling in the contaminant plume and by increased laboratory cost for more samples When the program lasts less than a full year identify any reasonable worst case period for the monitoring program This period is characterized by high ground level concentrations of air toxic releases from industrial and no
217. ng prevailing upwind conditions and the others representing prevailing downwind stations The number of monitoring stations can be re evaluated after one year of operation The number of meteorological stations established depends on local specific conditions such as topo graphy the distance between individual monitoring stations and program objectives In general a mete orological station should be located next to each air sampling station However this recommendation could be modified depending on local specific conditions e Use the SUMMA passivated canister for sampling of volatile organic compounds VOCs and gas chromatography mass spectrometry GC MS for subsequent analysis Estimated costs for setting up and operating a monitoring network are included in this document For example the estimated first year cost for installing and operating a regional air toxics monitoring network consisting of four canister samplers each operating every sixth day at three sites plus one meteorological station ranges between 300 000 and 400 000 Procurement and start up costs comprise about 25 percent of these costs with the remainder allocated to operation analysis and data management expenses The emphasis of a regional air monitoring program must be on quality to ensure credibility The quality of the pro gram depends directly on quality management and quality contractors The data collected during the program must be impeccable to withstand
218. nindustrial sources Use air emission release rate models and atmospheric dispersion models to identify reasonable worst case exposure conditions i e to quantitatively account for the above factors For a worst case application limit the modeling effort to a screening sensitivity exercise to obtain relative results for a variety of sources and meteorological scenarios Consider only those meteor ological parameters of greatest significance e g tem perature wind speed and stability Cost is a major consideration in selecting the fre quency and duration of the sampling program Overall c TABLE 3 1 RECOMMENDED PROGRAM SAMPLING DURATION AND FREQUENCY AND PROGRAM LENGTH BY OBJECTIVES Sampling Duration Sampling Frequency Program Length Every Once in 3 Oncein Oncein Oncein 3 days 6 days 6 days OTHER OBJECTIVES Once in Once in Once in T f Every Once in Once in ori 1 2 Once in Oncein Oncein Every in Oncein Once in 3 Permitting for industry Future Oncein Oncein DailyG Expansion 3 days 6 days e Emergency Release Evaluations __ o Je _ pro p R Recommended O Optional Program Objectives I PRIMARY OBJECTIVES Survey Studies Establish Community Concentrations Validation Studies 0 Applicable to ozone precursor studies 2 Applicable t
219. nning In this phase the direction and priorities of the program are set the relationships and ground rules among the participants are established and a foundation of cooperation and credibility is built To start a regional air monitoring program you must take three steps Define your objectives Involve others in the program Establish your management structure Figure 2 1 illustrates these three key steps 2 1 DEFINING YOUR OBJECTIVES Clearly identify all of the potential objectives for the program in the beginning of the project so that the prior ities for the study can be agreed upon The overall goal of any regional air monitoring pro gram is to gather information about the presence and levels of airborne pollutants in the community High quality data are needed even if the results are used only to infer the effect of exposures to airborne pollutants These data are essential for sound risk management Within these overall objectives you will need to con sider the characteristics of the region where monitoring FIGURE 2 1 GETTING A MONITORING PROGRAM STARTED DEFINING YOUR OBJECTIVES e Why are you monitoring e What questions do you wish to answer with this program e What are the intended uses of the monitoring data INVOLVING OTHERS IN THE PROGRAM Who other industries regulatory agencies public do you involve Why e g end users of final data users of detailed data QA QC partici
220. no other OFF times are programmed The selector is switched to AUTO If anything is incorrect the timer is reset and reprogrammed TABLE C 1 NET FLOW CONTROLLER SETTING DATE 1 CANISTER 2 CANISTERS U S EPA Compendium Method T014 1988 167 Heated Inlet Line 220202 2 27 2 77 DNPH Coated Funnel Sonn Formaldehyde 27 Cartridges Toggle Fiter Oritice Assembly X DH To ppm 3 Way Prog Solenoid Timer Vacuum Valve 1 Rellef Vent Nr NC Pump Activated Prior To Sample Period Vacuum NO Pro To Purge Pump Ti g imer Inlet Lines 22 m d Capillary Latching Solenoid Valve i Particulate Filter NU Coritroller N lt 3 5 min FIGURE C 1 Sample Canister U S ENVIRONMENTAL PROTECTION AGENCY UATP SAMPLER SCHEMATIC OF SAMPLE INLET CONNECTIONS 168 U S EPA Compendium Method T014 1988 STANDARD OPERATING PROCEDURE FOR METEOROLOGICAL STATION OPERATIONS AND CALIBRATION 169 wenn eee eee STANDARD OPERATING PROCEDURE FOR METEOROLOGICAL STATION OPERATIONS AND CALIBRATION PURPOSE The purpose of this document is to provide Standard Operation Procedures SOPs for implementation of meteorologi cal station calibration and operations APPLICABILITY This Standard Operation Procedures SOPs section is applicable to operation calibration
221. nsive per analysis and in some cases more sensitive than the specific detector they vary in specificity and sensitivity for a specific class of compounds For instance if multiple halogenated compounds are targeted an ECD is usually chosen if only compounds containing nitrogen or phosphorus are of interest a NPD can be used or if a variety of hydrocarbon compounds are sought the broad response of the FID or PID is appro priate In each of these cases however the specific identification of the compound within the class 95 U S EPA Compendium Method T014 1988 is determined only by its retention time which can be subject to shifts or to interference from other nontargeted compounds When misidentification occurs the error is generally a result of a cluttered chromatogram making peak assignment difficult In particular the more volatile organics chloro ethanes ethyltoluenes dichlorobenzenes and various freons exhibit less well defined chromato graphic peaks leading to misidentification using non specific detectors Quantitative comparisons indicate that the FID is more subject to error than the ECD because the ECD is a much more selec tive detector for a smaller class of compounds which exhibits a stronger response Identification errors however can be reduced by a employing simultaneous detection by different detectors or b correlating retention times from different GC columns for confirmation In either case inter fere
222. nstruments Response and retention time Same as for other chromatographic for each analyte instruments Mass spectral resolution and Introduction of perfluoro compound directly into MS 5 Injection of tuning standard tuning parameters Total volume Wet test meter or any appropriate volume standard Continuous monitors e g Response Use standard concentrations FID PID FPD etc Injection of standard using the same Daily or more frequently Standard composition should be process as for sample injection e g weekly monthly etc Flow rate Wet or dry test meter or appropriate Depends on sampler flow rate transfer standard Depends on sampler Must be determined at known e g weekly monthly atmospheric pressure and temperature Flow rate should be similar to that used for sampling Daily or more frequently Test atmosphere should be if required referenced to a primary standard e g NIST SRM Flow pressure conditions should duplicate sampling process checked against primary standards if available if required Same as for other chromatographic instruments Same as for other chromatographic instruments Selection of tuning standards will be dependent on type of analysis being performed e g bromofluoro benzene into GC NIST National Institute Standardization Technology SRM Standard Reference Material CRM Certified Reference Material
223. nt PID responses Therefore sampling efforts should be initially concentrated on suspect environments i e those which have appreciable odors The objective of the sampling is to locate sources of the tar get compounds Ultimately samples should be collected throughout the entire location but with particular attention given to areas of high or frequent occupation 9 3 Sample Analysis 9 3 1 Qualitative analysis Positive identification of sample components is not the objective of this screening procedure Visual comparison of retention times to those in a standard chroma togram Figure B 1 are used only to predict the probable sample component types 9 3 2 Estimation of levels As with qualitative analysis estimates of component concentrations are extremely tentative and are based on instrument responses to the calibrant species e g ben zene trichloroethylene styrene the proposed component identification and the difference in response between sample component and calibrant For purposes of locating pollutant emission sources roughly estimated concentrations and suspected compound types are considered sufficient 10 0 Performance Criteria and Quality Assurance Required quality assurance measures and guidance concerning performance criteria that should be achieved within each laboratory are summarized and provided in the following section 10 1 Standard Operating Procedures 10 1 1 SOPs should be generated by the users to
224. ntial hot spots The information gathered from the portable GC screen ing analysis would be used in developing a monitoring protocol which includes the sampling system location based upon the screening analysis results After screening analysis the sampling system is located Temperatures of ambient air and sampler box interior are recorded on canister sampling field data sheet Figure 10 Note The following discussion is related to Figure 2 To verify correct sample flow a practice evacuated canister is used in the sampling sys tem Note For a subatmospheric sampler the flow meter and practice canister are needed For the pump driven system the practice canister is not needed as the flow can be measured at the outlet of the system A certified mass flow meter is attached to the inlet line of the manifold just in front of the filter The canister is opened The sampler is turned on and the reading of the certified mass flow meter is compared to the sampler mass flow con troller The values should agree within 10 If not the sampler mass flow meter needs to be recalibrated or there is a leak in the system This should be investigated and corrected Note Mass flow meter readings may drift Check the zero reading carefully and add or subtract the zero reading when reading or adjusting the sampler flow rate to compensate for any zero drift After two minutes the desired canister flow rate is adjusted to the
225. ntial of the molecule Generally all species with an ionization potential less than the ionization energy of the lamp are detected Because the ionization potential of all major components of air 02 CO CO and H20 is greater than the ionization energy of lamps in general use they are not detected The sensor is comprised of an argon filled ultraviolet UV light source where a portion of the organic vapors are ionized in the gas stream A pair of electrodes are contained in a chamber adja cent to the sensor When a positive potential is applied to the electrodes any ions formed by the absorption of UV light are driven by the created electronic field to the cathode and the current proportional to the organic vapor concentration is measured The PID is generally used for compounds having ionization potentials 108 U S EPA Compendium Method 014 1988 less than the ratings of the ultraviolet lamps This detector is used for determina tion of most chlorinated and oxygenated hydrocarbons aromatic compounds and high molecular weight aliphatic compounds Because the PID is insensitive to methane ethane carbon monoxide carbon dioxide and water vapor it is an excel lent detector The electron volt rating is applied specifically to the wavelength of the most intense emission line of the lamp s output spectrum Some compounds with ionization potentials above the lamp rating can still be detected due to the presence of small quantitie
226. nts 34 4 2 1 3 Carbon Adsorbents 34 4 2 2 Whole Air Gollecti n au nnt uit rh RD D e p rr oe exer e 36 42241 Glass Sampling 9 sn Ree in 37 42 2 2 Gas Sampling cse devo so tern air 37 4 2 2 3 Summa Polished Canisters 37 42 3 Oyogenic accused eek 38 42 4 Impinger Eee ia eo nv t 40 4 2 5 Derivatization 40 4 2 0 Passive Samples seen ee 41 424 Direct ANAlVSIS 41 43 METHODS FOR PARTICULATE AND PARTICLE BOUND COMPONENTS 41 49 1 TIUTAlOD euere 42 4 3 2 Centrifugal Collection and Impaction 43 4 3 3 Electrostatic Precipitation eese eese nee 44 44 GAS AND SOLID WASTE PHASE DISTRIBUTION ANALYSIS 44 SECTION 5 OVERVIEW OF ANALYTICAL METHODS eee 46 51 CHEMICAL AND PHYSICAL PROPERTIES 46 5 2 FIELD SCREENING nne 47 5 2 1 Colonmeltrie Detection 48 52 2 ODOClrOSCODIC nee 50 5 2 3 lonization Devices x icto ee 50
227. nts are available for volume purchasing 8 Price range is for one sample Discounts are available for volume analysis 9 Method TO 14 analysis detection limit of about 1ppb and canister regeneration 10 Method TO 3 or TO 14 analysis detection limit of about 1ppb 01 Method TO 1 analysis detection limit of about 1ppb and tube regeneration 12 Method TO 2 analysis detection limit of about 1 and tube regeneration 13 Method TO 4 analysis detection limit of about 1 2ug m3 4 Atomic absorption Inductive Coupled Plasma analysis detection limit of about 1 2ug m3 15 Includes portable field GC systems 16 System includes wind speed wind direction sigma theta and ambient temperature sensors lightning protection spare parts and calibration kits upper range cost 17 Costis based on system described under Note 16 without calibration kits 08 Also includes chart recorder as a backup to the data logger 9 Meets requirements specified in Reference 8 in Section 5 6 450 4 87 007 and Reference 5 in Section 5 6 EPA 450 4 87 013 40 The following assumptions apply to this cost example Two air monitoring equipment options could be used 1 time integrated VOCs monitoring using whole air canister samplers with subsequent labor atory analysis or 2 near real time portable field GC analyzers The survey will include a portable meteorological station The survey will be conducted for a perio
228. ny problems and the means of mitigating them An integral part of the network operation is commun ication with the laboratory selected to analyze field samples Close communication with the designated con tact at the laboratory is critical to ensure that the shipped samples are received and analyzed on time and that any technical issues that develop are handled promptly A number of options are available to train project per sonnel who need to supplement their prior training and experience These include reviewing documents devel oped specifically for this program such as the program operations plan and conducting one on one meetings with the operations contractor laboratory contact or other industry personnel who have conducted regional air monitoring activities Outside resources such as U S EPA training courses or workshops are available Publications such as the references listed in Section 3 8 are also useful for training purposes Finally staff may obtain vendor literature or attend training sessions offered by suppliers of air monitoring instruments 42 PROCURING EQUIPMENT AND SUPPLIES After a monitoring plan is developed and the program fully designed procure equipment and supplies Procurement involves developing specifications for equipment and supplies and making a list of qualified vendors evaluating vendors bids and selecting the suc cessful vendor s expediting delivery of equipment and supplies perfo
229. o diurnal effects studies 3 Multiple samples during each day Operating costs for a program are in large measure directly proportional to the numbers of samples collected Section 7 0 illustrates the effects that the program s duration and sampling frequency can have on costs Select sampling periods in a way that will satisfy regu lations and public opinion This kind of scheduling will help avoid criticism that sample periods do not represent industrial practices or other activities in the community Address the potential problem by adopting a random schedule with the minimum practical advance notice Also consider collecting more samples than are needed for the data base and then decide at a later time which samples will be analyzed See Section 3 4 for a discus sion of sample holding time limitations 3 4 SELECTING SAMPLING AND ANALYTICAL METHODS Alternative air toxic monitoring techniques for regional air monitoring programs are classified as follows e Time integrated techniques Near real time techniques Screening level techniques Time integrated air monitoring methods are appli cable when high quality data are required and the short term temporary variability of concentrations is not important In fact these methods are the most suitable for regional air monitoring programs Table 3 2 presents a listing of typical time integrated monitoring tech niques A brief description of these techniques the EP
230. o that the pump will be on whenever either timer is on Thus the pump will run if timer 2 is ON even if timer 1 is OFF 4 2 3 The elapsed time meter is set to 0 43 Sampler Check 4 3 1 The following must be verified before leaving the sampling site 1 Canister s is are connected properly and the unused connection is capped if only one canister is used 2 Canister valve s is are opened 3 Both timers are programmed correctly for the scheduled sample period 4 Both timers are set to AUTO 5 Both timers are initially OFF 6 Both timers are set to the correct current time of day and day number 7 Elasped time meter is set to 0 44 Sampler Recovery Post Sampling 4 4 1 The valve on the canister is closed 4 4 2 canister is disconnected from the sampler the sample data sheet is completed and the canister is prepared for shipment to the analytical laboratory 4 4 3 If two canisters were sampled step 2 4 2 is repeated for the other canister Timer Setting Since the timers are 7 day timers the days of the week are numbered from 1 to 7 The assignment of day numbers to days of the week is indicated on the timer keypad 1 Sunday 2 Monday 3 Tuesday 4 Wednesday 5 Thursday 6 Friday and 7 Saturday This programming is quite simple but some timers may malfunction or operate erratically if not programmed exactly right To assure correct operation the timers should be reset and completely repro
231. objec tives that require short sampling durations e The resource requirements for laboratory analysis for organic and inorganic compounds Quality assurance quality control requirements such as collocated field and trip blank samples and spike samples Samples taken over a very short period of time a few minutes or so do not represent average concentrations of airborne pollutants High variability could occur over short periods of time Samples taken during regional air monitoring surveys should be averaged over at least one hour and preferably over a longer period of time You should tailor the general guidance presented in Table 3 1 to your specific applications 11 In most cases the 24 hour sampling duration is highly recommended for long term monitoring for both organic and inorganic constituents Use the 8 hour sampling duration for compliance studies acute health effects studies or preliminary survey studies For com pliance and health studies this duration is used to main tain consistency with the 8 hour TLV values Sampling for air toxicity monitoring survey studies is done for periods of 8 hours to provide more data points during a short period of time Use a 12 hour sampling duration for determining the effect of daytime and nighttime meteorology on air toxic concentrations This sampling duration covers nighttime thermal inversions Apply the 3 hour sampling duration to several objec tives Use it duri
232. of meteorological station and the collection of meteorological data DEFINITIONS There is no specialized terminology used in these procedures that requires definition beyond the conventional meaning of the terms REFERENCES Manufacturers Operation and Maintenance Manuals DISCUSSION The station will be operated on a full time basis The meteorological data at the location are representative of overall site conditions The weather station also includes an automated data processor which provides 15 minute and 1 one hour data averages The averaged data is recorded on cassette tapes Realtime instantaneous data is also recorded on a strip chart recorder as a backup Data from this system include wind speed WS wind direction WD standard deviation of horizontal wind direction Sigma and ambient temperature Temp RESPONSIBILITIES e The Field Service Coordinator is responsible for installing the meteorological station and training field staff to operate the meteorological monitoring station e The Auditor is responsible for conducting the semi annual audits and calibration of the meteorological monitor ing station The Program Director is responsible for air monitoring program operations e The Field Technician is responsible for field support to the meteorological monitoring station operations as directed by the Program Director EQUIPMENT The following equipment is needed for the meteorological station calibra
233. of 500 to 700 A PM 10 calibration kit costs between 100 to 350 As mentioned above when more than one sampler is purchased cost adjust ment should be made to exclude the cost of more than one calibration kit 7 2 PROGRAM SCENARIO COSTS Two cases were developed as examples for program cost scenarios These can guide the development of other cost scenarios However it should be emphasized that the cost estimates developed can be used only for budget ary and planning purposes Refinements should be made based on written quotes from equipment manu facturers and suppliers analytical laboratories and contractors Case I Short Duration Survey In this example the objective for this short duration survey is to monitor VOCs in a region that includes sev eral large industrial facilities This survey could stand alone or serve as Phase I of a two phase program In the case where the short duration survey is Phase I of a larger program the survey purpose is to collect data at several locations within the community during a season where meteorological conditions are conducive to high ground level concentrations of air pollutants Then this survey will serve as a basis for a long term monitoring study The survey study is scheduled to occur over a 90 day period Two sampling systems are planned with an additional system as a collocated unit In the middle of the program the two sampling stations will be relocated This way data ar
234. of Toxic Organic Compounds in Ambient Air 74 SECTION 1 SECTION 2 SECTION 3 TABLE OF CONTENTS NOTIGE e P 22022022222222020022022 a iii PREFACE LIST OF TABLES viii LIST OF APPENDIGCBES viii INTRODUCTION SEIEN 1 REGULATORY AND RELATED ISSUES CONCERNING TOXIC ORGANIC MATERIALS 3 2 1 GENERAL ee nee 3 2 2 BISKASSESSMENT nun anne 3 2393 REGULATORY NEEDS sin an v una FR RF ora 4 2 3 1 Resource Conservation and Recovery 4 2 3 2 Community Right to Know 4 2 3 3 Toxic Substances Control 4 2 9 4 Cleamn AIT ds cov ERO ES 5 2 3 4 1 Technology Based Standards 5 2 3 4 2 Health Based Standards 5 2 4 EMERGENCY SITUATIONS AND NUISANCE COMPLAINTS 6 2 5 AIR POLLUTION RESEARCH 6 GUIDELINES FOR DEVELOPMENT OF A MONITORING PLAN 7 31 GENERAL Serena 7 3 2 DATA QUALITY 7 3 2 1 Stage
235. of airborne pollutants commonly known as air toxics Fill data gaps regarding concentrations of airborne pollutants in the community e Respond to local state or Federal regulatory requirements e Provide data to evaluate the impacts of airborne chemicals e Identify contributors of toxic air pollutants in the community Contributors can include mobile sources com mercial and residential chemical users and industrial chemical processes In addition long range transport of air pollutants may contribute chemicals to the community Toxic air pollutant monitoring may be needed as part of ozone precursor studies emergency release evaluations and source receptor relationship studies including model validations Regional monitoring programs benefit both community and industry participants These programs provide unique opportunities for cooperative efforts involving industry regulators and the community Ambient data collected can be of great value to all parties These data provide a technically sound basis for regulatory decision making and public policy formation The purpose of this document is to provide information to those individuals responsible for deciding if and how an air toxics monitoring program should be undertaken This document is directed to industry representatives who are interested in monitoring levels of toxic air pollutants in regions where they operate It provides a framework for organizing and participa
236. oint project of USEPA s Office of Air Quality Planning and Standards the Environmental Monitoring Systems Laboratory and the participating state air pollution control agencies The purpose of UATP is to provide analytical support to the states in their assessment of potential health risks from certain toxic organic com pounds that may be present in urban atmospheres The sampler is described in the paper Automatic Sampler for Collection of 24 Hour Integrated Whole Air Samples for Organic Analysis to be presented at the 1988 Annual Meeting of APCA Dallas Texas June 1988 Paper No 88 150 3 The sampler is based on the collection of whole air samples in 6 liter SUMMA passivated stainless steel canisters The sampler features electronic timer for ease accuracy and flexibility of sample period programming an independently setable presample warm up and ambient air purge period protection from loss of sample due to power interruptions and a self contained configuration housed in an all metal portable case as illustrated in Figure C 1 The design of the sampler is pumpless using an evacuated canister to draw the ambient sample air into itself at a fixed flow rate 3 5 controlled by an electronic mass flow controller Because of the relatively low sample flow rates necessary for the integration periods auxiliary flushing of the sample inlet line is provided by a small general purpose vacuum pump not in contact with the
237. ollection and analysis data management and QA QC procedures Data summaries should include the type of information dis cussed under Section 6 1 The availability of raw data that can be used to arrive at the calculated air concentra tions as discussed in Section 6 1 is critical Sponsors of the program should agree on ground rules for making the raw data available to outside parties Data should be interpreted based on the discussion in Section 6 3 Emphasis should be placed on relating sources to receptors by using wind direction data associ ated with measured concentrations In addition risk assessment calculations should be performed at least within the framework outlined in Appendix B Other methodologies can be used depending on the applications involved and the quality of the experimental animal data Volume of data does not result in better interpreta tion Instead valid interpretations require high quality data that is representative of the ambient concentrations in the region Hence in the summary report it is impor tant that you provide detailed clearly stated assumptions or qualifications related to data interpretation 6 5 OPTIONAL USE OF RESULTS IN MODEL VALIDATION Model validation is not easy However results of ambient air measurements can be used to validate models provided that the design for the monitoring program includes considerations for such validation Section 3 6 discusses key program design factor
238. ollowing key questions e What constituents will be monitored How many monitoring stations will be involved and where will they be located What 15 the sampling duration and frequency and the program length What sampling and analysis methods will be employed Who and what will be the resource requirements involved Answers to these questions early in the program save time and money by streamlining the process eliminating unneeded steps and avoiding pitfalls 3 1 OVERVIEW OF PLAN ELEMENTS A good monitoring plan consists of several steps including those shown in Figure 3 1 A brief discussion of each of these steps occurs in the following paragraphs In developing a monitoring plan first select the consti tuents to be monitored Section 3 2 discusses factors to be considered in developing this list Secondly define the duration and frequency of moni toring to meet specific program needs Section 3 3 provides a discussion of this subject Table 3 1 provides general guidelines for program length sampling duration and frequency by program objectives Third a key element of the monitoring plan is the selection of sampling and analysis methods most suitable for your program This selection is based on the program objectives resources and constraints Section 3 4 pro vides a discussion of sampling and analysis methodolo gies Details are provided in Appendices C and D In addition to the air monitoring
239. om pounds VOCs However monitoring for other consti tuents such as metal particulates are covered in a more condensed manner The document includes specific recommendations for establishing a regional air toxics monitoring network These recommendations can be modified as needed from One region to another Those industries interested in establishing monitoring networks should consider a joint program with regulators and the public These networks can provide technically sound information to participat ing sponsors the public and regulatory and planning agencies The document provides guidance in the following areas Involving regulators the public and other inter ested parties e Structuring the management of a regional air toxics program Developing a monitoring program plan Implementing sampling and analysis activities e Ensuring the quality of collected data e Organizing and reporting monitoring results Estimating costs of monitoring programs 1 1 ORGANIZATION OF THE DOCUMENT This document is intended to be both a management and technical level planning tool which can be useful as a guide for directing CMA member staff and contractor activities in regional air toxics monitoring programs Program elements associated with the planning and implementation of regional ambient air toxics monitor ing are shown in Figure 1 1 This figure includes six key elements Each represents a chapter in this
240. ompound LOD ng LOD ppb Chloroform 2 450 1 I Trichloroethane 2 450 Carbon tetrachloride 2 450 Benzene 006 2 1 2 Dichloroethane 05 14 Trichloroethylene 05 14 Tetrachloroethyleneb 05 14 1 2 Dibromoethane 02 2 p Xylene 02 4 m Xylene 02 4 o Xylened 01 3 Styrene 01 3 aChloroform I Trichloroethane and Carbon tetrachloride coelute on 0 66 m 3 SP2100 61 2 Dichloroethane Trichloroethylene and Tetrachloroethylene coelute on 0 66 m 3 SP2100 Cp Xylene and m Xylene coelute 0 66 m 3 SP2100 dStyrene and o Xylene coelute on 0 66 m 3 SP2100 162 U S EPA Compendium Method T014 1988 Peak Assignments For Standard Mixture Peak No Compound s 2 Benzene Chloroform 1 1 1 Trichloroethane 3 5 Carton Tetrachioride 2 1 2 Dichioroethane Trichloroethylene 3 Tetrachlorgethyiene 1 2 Dibromoethane 4 Ethyibenzene Xylene Q Xylene Styrene 4 6 Toluene not listed elutes between peaks 1 and 2 2 Time FIGURE 1 TYPICAL CHROMATOGRAM OF VOCs DETERMINED BY A PORTABLE GC 163 U S EPA Compendium Method 7014 1988 APPENDIX C INSTALLATION AND OPERATION PROCEDURES FOR U S ENVIRONMENTAL PROTECTION AGENCY S URBAN AIR TOXIC POLLUTANT PROGRAM SAMPLER 1 0 Scope 2 0 3 0 1 1 1 2 1 3 The subatmospheric sampling system described in this method has been modified and redesigned specifically for use in USEPA s Urban Air Toxic Pollutant Program UATP a j
241. on Reference Peak Window Sample Amount 0 000 Uncalibrated Peak RF Peak Num Type int Type h oL o lA cL LA I IR oL lA lA Ll ll L4 lA l ll Lll l L4 L l l LA LA l ho Ret Time 5 020 5 654 6 525 6 650 7 818 8 421 9 940 10 869 11 187 11 223 11 578 12 492 13 394 13 713 14 378 14 594 15 009 15 154 15 821 16 067 16 941 17 475 17 594 17 844 18 463 18 989 19 705 20 168 20 372 20 778 20 887 20 892 22 488 22 609 23 114 23 273 23 279 23 378 23 850 26 673 27 637 Signal Description Mass 85 00 amu Mass 50 00 amu Mass 85 00 amu Mass 62 00 amu Mass 94 00 amu Mass 64 00 amu Mass 101 00 amu Mass 61 00 amu Mass 49 00 amu Mass 41 00 amu Mass 151 00 amu Mass 63 00 amu Mass 61 00 amu Mass 83 00 amu Mass 62 00 amu Mass 97 00 amu Mass 78 00 amu Mass 117 00 amu Mass 63 00 amu Mass 130 00 amu Mass 75 00 amu Mass 75 00 amu Mass 97 00 amu Mass 91 00 amu Mass 107 00 amu Mass 166 00 amu Mass 112 00 amu Mass 91 00 amu Mass 91 00 amu Mass 104 00 amu Mass 83 00 amu Mass 91 00 amu Mass 105 00 amu Mass 105 00 amu Mass 105 00 amu Mass 146 00 amu Mass 91 00 amu Mass 146 00 amu Mass 146 00 amu Mass 180 00 amu Mass 225 00 amu Bottle Number 2 8 Jan 86 8 13 am 5 00 Absolute Minutes 0 40 Absolute Minutes 0 00 Multiplier 1 667 Compound Name FREON 12 METHYLCHLORIDE FREON 114 VINYLCHLORIDE METHYLBROMIDE ETHYLCHLORIDE
242. on meteorological measurements can be obtained from a number of U S documents 7 8 9 TABLE 3 5 RECOMMENDED SYSTEM ACCURACIES AND RESOLUTIONS Meteorological Variable System Accuracy Wind Speed 0 2 m sec 5 of observed Pressure 3 mb 0 3 kPa U S Onsite Meteorological Applications 9 Source Program Guidance for 16 Regulatory Modeling 3 6 DESIGNING THE NETWORK Number and Location of Monitoring Stations Consider the following key factors when selecting the locations and the number of monitoring stations for regional air monitoring programs e Results of air dispersion modeling for the region using an atmospheric dispersion model applicable to the sources and the region under consideration Receptor characteristics population centers resi dential communities sensitive receptors such as hospitals and schools and environmental loca tions locations of calculated high concentrations of airborne pollutants e Environmental characteristics e g meteorology and topography Meteorological variables affecting monitoring network design include wind direction wind speed and atmospheric stability Use these parameters to define prevailing wind patterns and to characterize local dispersion conditions con sidering source receptor relationships Consider conditions such as nighttime thermal inversions and downhill drainage flow that are conducive to high g
243. onal monitoring program area Other governmental bodies such as regional planning commissions may also have a stake in the monitoring results and should be considered for participation In addition other industry groups or the local Chambers of Commerce are potential participants because results of the monitoring program may impact their activities What does being involved mean Involvement really begins with defining program objectives as discussed in Section 2 1 If no one agrees on the goals for its program the results will be of little use Therefore you should consult the program partici pants on key decisions such as selecting the constituents to be included in a preliminary survey and or the the final monitoring agreeing on the sampling schedule and selecting the number and location of monitoring sites Being involved means having enough information on a timely basis about the progress problems and results of the program to judge whether or not it is meet ing its objectives How are participants kept involved Involvement is largely a matter of your establishing relationships and maintaining communications Once the participants are identified make every effort to maintain continuity of personnel so that working rela tionships and credibility are established and maintained Send participants information regularly and on a timely basis Furthermore in the planning phase and at key points throughou
244. oncentrations Sampler should be placed at a distance of 5 25m from the edge of the nearest traffic lane on the roadway depending on the vertical placement of the sampler inlet which could be 2 15m above ground 18 After you have collected analyzed and assessed one year s worth of data you can expand the regional air monitoring network to accommodate some of the region specific factors addressed above Siting Air Monitoring and Meteorological Stations It is likely that one main reason to perform regional air monitoring is to collect high quality data for use in decision making Therefore the placement of both air monitoring and meteorological stations is critical to obtain data that meet data recovery requirements Cur rently for permitting purposes EPA requires data recovery rates of 80 percent for air quality data and 90 percent for meteorological data Any regional air moni toring system established should plan to meet or exceed these requirements to ensure credibility of the results Placement of air monitoring and meteorological sta tions must conform to a consistent set of criteria and guidance Correct placement ensures data comparability and compatibility A detailed set of probe siting criteria for ambient air monitoring and meteorological pro grams is given in EPA Ambient Monitoring Guidelines for Prevention of Significant Deterioration 9 Key siting factors include the following Vertical placement abov
245. onitoring program the results of follow up investigations concern ing corrective action recommended and effectiveness of the data validation procedures Quality Cost Reports summarize the costs associated with each element prevention apprais al and failure of a Quality Cost System for a TOAP monitoring program Instrument and or Equipment Downtime Reports summarize information concerning instrument and or equip ment failures failure courses repair time and total downtime Control Charts are graphical representations of QA data Finally interlaboratory Comparison Summary Reports are pub lished by EPA and are applicable only to specific analytes and methodologies 7 3 7 Corrective Action In many cases data review or audit procedures will result in the need for corrective action This may involve reporting certain aspects of the work or simply providing more detailed doc umentation for work already performed In either case QA management will be responsible for documenting the need for type of and implementation of corrective action 7 3 8 Training An important component of a QA program will involve personnel training Trained person nel are necessary to ensure that the data they produce are complete and of high quality Training can be accomplished on the job or by trainees attending courses relevant to the em ployees job functions The effectiveness of training must be documented to establish and maintain the integrity of the
246. ore difficult to analyze Validation cannot be assured at this time Deen armen tem rer p 4 inr d 4 ne er VA APPENDIX B HAZARD INDEX METHODOLOGY 51 is men ame ET APPENDIX B HAZARD INDEX METHODOLOGY This appendix outlines methods for ranking and selec ting constituents in the regional air monitoring program This ranking procedure is designed to help the user deter mine which constituents from a large list of constituents to include in the regional air monitoring program Generally the reader must select compounds before determining what equipment and analytical methods are used during the regional air monitoring study The process detailed in this appendix involves calcu lating a Constituent Ranking Index CRI for each con stituent included in Appendix A The CRI index uses the expected annual average concentration for a compound e g from air dispersion modeling or monitoring and compares these expected levels to some criteria that estimates the potential impact on human health The human health criteria used in the ranking process should be widely available and should reflect an appropriate measure of potential impact Among the various references used to obtain health values are e The EPA s
247. ore traditional fixed site samplers Definitions Definitions used in this document and in any user prepared Standard Operating Procedures SOPs should be consistent with ASTM Methods D1356 and E355 Abbreviations and symbols pertinent to this method are defined at point of use Interferences 6 1 The most significant interferences result from extreme differences in limits of detection LOD among the target VOCs Table B 1 Limitations in resolution associated with ambient temperature chromatography and the relatively large number of chemicals result in coelution of many of the target components Coelution of compounds with significantly different PID sensitivities will mask compounds with more modest sensitivities This will be most dramatic in interferences from benzene and toluene 155 U S EPA Compendium Method 7014 1988 7 0 8 0 9 0 6 2 6 3 A typical chromatogram and peak assignments of a standard mixture of target VOCs under the pre scribed analytical conditions of this method are illustrated in Figure B 1 Samples which contain a highly complex mixture of components and or interfering levels of benzene and toluene are analyzed on a second longer chromatographic column The same liquid phase in the primary column is contained in the alternate column but at a higher percent loading Recent designs in commercially available GCs Table B 2 have preconcentrator capabilities for sampling lower concentrations of VOCs pr
248. orological 18 3 7 4 Assessment of Relevant Sampling and Analytical Methodologies 5 veio e 3 8 SELECTION OF SAMPLING AND ANALYSIS METHODS 20 3 8 1 Analytical Methodology Considerations 21 3 8 2 Sampling Methodology Consideration 23 3 8 3 Selection of Sampling 24 3 9 QUALITY ASSURANCE PLANNING 26 3 10 DEFINITION OF DATA REPORTING FORMAT 27 3 11 SAFETY 8 27 312 MANPOWER eren nnne nnne nnn 29 SECTION 4 OVERVIEW OF SAMPLING METHODS mI 30 41 PHYSICAL AND CHEMICAL 30 4 1 1 Volatile Organic Compounds eee 30 4 1 2 Semi volatile Organic Compounds 31 4 1 3 Nonvolatile Organic Compounds 32 4 2 METHODS FOR GAS PHASE 32 421 SONG ASdOr DOMS ee 32 4 2 1 1 Organic Polymeric Adsorbents 32 4 2 1 2 Inorganic Adsorbe
249. os of regional air monitor ing programs Cost estimates this chapter should serve as a guidance for budgetary purposes only These estimates July 1989 are based on conversations with equipment manufacturers suppliers analytical laboratories contractors and or the author s experience implement ing various phases of air monitoring programs Program costs will vary across the country depending on the availability of equipment manufacturers and suppliers analytical laboratories and contractors Program managers should get firm quotes to identify the costs specific to your regional air monitoring program needs Section 7 1 discusses the unit costs for air quality and meteorological monitoring equipment and supplies as well as for laboratory analysis Section 7 2 provides cost estimates for two program scenarios one for a 90 day survey and one for a 1 year study 71 UNIT COSTS OF EQUIPMENT SUPPLIES AND ANALYSES Cost estimates for equipment supplies and labora tory analyses for regional air monitoring programs are included in Table 7 1 Key assumptions made in develop ing these estimates are provided as notes to this table Monitoring equipment is divided into three groups time integrated air monitoring equipment near real time air monitoring equipment and meteorological monitoring equipment The equipment selected for inclusion in Table 7 1 is based on the sampling and analysis methods discussed in Section 3 5 and Appendi
250. ould be recorded in Table C 1 and used until superseded by new settings 4 1 9 Timer 2 is turned OFF to again start the flow through the flow controller With the pump timer 1 ON and the sampling valve timer 2 OFF the flow controller is turned to READ and the flow is verified to be the same as the flow setting made in step 4 1 8 If not the flow setting is rechecked in step 4 1 8 and the flow setting is readjusted if necessary 4 1 10 The OFF button of timer 1 is pressed to stop the pump 4 1 11 The canister valve s are fully opened Timers 4 2 1 Timer 2 is set to turn ON at the scheduled ON time for the sample period and OFF at the scheduled OFF time See the subsequent section on setting the timers Normal ON time 12 00 AM on the scheduled sampling day Normal OFF time 11 59 PM on the scheduled sampling day The OFF time is 11 59 PM instead of 12 00 AM so that the day number for the OFF time is the same as the day number for the ON time Be sure to set the correct day number U S EPA Compendium Method T014 1988 165 5 0 4 2 2 Timer 1 is set to turn ON six 6 hours before the beginning of the scheduled sample period and OFF at the scheduled OFF time for the sample period same OFF time as for timer 2 See the subsequent section on setting the timers Normal ON time 06 00 PM on the day prior to the scheduled sampling day Normal OFF time 11 59 PM on the scheduled sampling day Note The timers are wired s
251. ould be made per the procedures found in the manufacturer s specifications Meteorological System Checklist Form The meteorological checklist form should be filled out by the Field Technician after completing the daily activities at the meteorological monitoring station A separate section has to be filled out at the completion of the weekly and bi weekly activities Preventive Maintenance Preventive maintenance of the meteorological station consists mainly of visual inspection of the individual components for signs of wear or malfunction and performance of the bi weekly zero span checks Emergency Maintenance In the event of an equipment failure the Field Service Coordinator FSC should be contacted as to the disposition of the equipment Emergency maintenance will be based on the use of spare units as available with malfunctioning units being sent back to the factory for repair or replacement Periodic Calibration Once every six months the FSC should conduct a calibration of the meteorological monitoring station per procedures outlined in the appropriate Sections of this SOP RECORDS mu Meteorological System Checklist Meteorological System Checklist Forms should be completed daily for the meteorological station by the Field Tech nician The information submitted addresses as observed equipment conditions and system operation status 173 Zero Span Check Form and Calibration Log Form The Zero Span Check Form and
252. pants monitoring program designers and program operators involve them What personnel resources are required and or available What are your budget resources and constraints What are the logistical requirements for implementing each of the program elements Figure 1 1 How should you interact with equipment vendors outside laboratories and with outside contractors in implementing one or more phases of the program will be conducted to set specific objectives for the pro gram You may want to consider for example the following questions e In terms of industry and or population is this a growth area or not e Is there a natural home for this monitoring network Do you have to organize an industry coalition What are the public concerns in the region How environmentally active are the citizens groups What are the particular regulatory issues in the region e Are new regulations being developed What factors such as climate topography indus trial operating schedules and public activity patterns could affect exposures to airborne pollutants e Are there particular areas in the region which are suspected of having high ambient levels of airborne pollutants Do they contain sensitive subpopulations e Where do these sensitive subpopulations live What kind of data e g short or long term do you want e What studies have been conducted previously in your region and
253. pecies are difficult to recover from the sorbent TENAX GC ADSORPTION AND GC MS OR GC FID 1 Ambient air is drawn through organic polymer sorbent where certain compounds are trapped The cartridge is transferred to the laboratory for analysis Using GC MS or GC FID 0 01 1 ppbv 20 ml sample Good volume of air can be sampled Water vapor is not collected Wide variety of compounds collected Standard procedures available Highly volatile compounds and certain polar compounds are not collected Breakthrough of compounds could become a major issue for sampling period exceeding 8 hours SUMMA PASSIVATED CANISTER AND GC FID ECD OR GC MS Whole air samples are collected in evacuated stainless steel canister VOCs are concentrated in the laboratory with cryogen trap VOCs are revolatilized separated on a GC column and passed to one or more detectors for identification and quantitation Best method for broad speciation of unknown trace volatile organics Simple sampling approach Sample components may be adsorbed or decompose through interaction with container walls Condensation may be a problem at high concentrations ppm e Complex equipment preparation required 6S TABLE C 3 SUMMARY OF SAMPLING AND ANALYTICAL METHODS FOR TIME INTEGRATED AMBIENT MONITORING VOLATILE HALOGENATED HYDROCARBONS Method Sampling and Analysis Approach Detect
254. ponents contained in the audit canister Percent relative accuracy is calculated Relative Accuracy x 100 Where Y Concentration ofthe targeted compound recovered from sampler X Concentration of VOC targeted compound in the NBS SRM EPA CRM audit cylinders 12 2 2 If the relative accuracy does not fall between 90 and 110 percent the field sampler should be removed from use cleaned and recertified according to initial certification procedures out lined in Section 11 2 2 and Section 11 2 3 Historically concentrations of carbon tetrachloride tetrachloroethylene and hexachlorobutadiene have sometimes been detected at lower con centrations when using parallel ECD and FID detectors When these three compounds are present at concentrations close to calibration levels both detectors usually agree on the reported concentrations At concentrations below 4 ppbv there is a problem with nonlinearity of the ECD Plots of concentration versus peak area for calibration compounds detected by the ECD have shown that the curves are nonlinear for carbon tetrachloride tetrachloroethylene and hexachlorobutadiene as illustrated in Figures 18 a through 18 c Other targeted ECD and FID compounds scaled linearly for the range 0 to 8 ppbv as shown for chloroform in Figure 18 d For compounds that are not linear over the calibration range area counts generally roll off between 3 and 4 ppbv To correct for the nonlinearity of these compounds
255. proper value as indicated by the certified mass flow meter by the sampler flow control unit con troller e g 3 5 cm3 min for 24 hr 7 0 cm3 min for 12 hr Record final flow under CANISTER FLOW RATE Figure 10 The sampler is turned off and the elapsed time meter is reset to 000 0 Note Any time the sampler is turned off wait at least 30 seconds to turn the sampler back on The practice canister and certified mass flow meter are disconnected and a clean certified see Section 12 1 canister is attached to the system The canister valve and vacuum pressure gauge valve are opened Pressure vacuum in the canister is recorded on the canister sampling field data sheet Figure 10 as indicated by the sampler vacuum pressure gauge The vacuum pressure gauge valve is closed and the maximum minimum thermometer is reset to current temperature Time of day and elapsed time meter readings are recorded on the canister sampling field data sheet The electronic timer is set to begin and stop the sampling period at the appropriate times Sampling commences and stops by the programmed electronic timer After the desired sampling period the maximum minimum current interior temperature and current ambient temperature are recorded on the sampling field data sheet The current read ing from the flow controller is recorded At the end of the sampling period the vacuum pressure gauge valve on the sampler is briefly opened and closed and th
256. r comparison This average should include detected values at some fraction of the detection limit e g detection limit 2 if the majority of values are detected In no case should a significant risk be inferred from values that are not detected for example by using the detection limit for not detected values then inferring a significant risk at the detection limit but from values which are not detected It is recommended that the Constituent Ranking Index CRI approach discussed in Section 3 2 and Appendix B can be used for this comparison The CRI value can be considered as the ratio of the air con centration based on monitoring results to the appropri ate health criterion If any calculated CRI exceeds unity i e 1 then additional evaluation or assessment is needed to determine whether a health criterion is exceeded CMA under another project published a companion resource document to aid in this evaluation This document is entitled Chemicals in the Com munity Methods to Evaluate Airborne Chemical Levels Copies of this book are available from CMA publication fulfillment by asking for Community Exposure Evaluation booklet Monitoring results can also be used as direct input to standard risk assessment models This alternative data interpretation approach can be used to quantify the total population risk and maximum individual risk associated with ambient concentrations of airborne pollutants
257. rgest peaks are chosen by an automated data reduction program the three scans nearest the peak apex are averaged and a background subtraction is performed A library search is then performed and the top ten best matches for each peak are listed A qualitative characterization of the sample is provided by this procedure A typical chromato gram of VOCs determined by GC MS SCAN is illustrated in Figure 11 a A Nafion permeable membrane dryer is used to remove water vapor selectively from the sample stream The permeable membrane consists of Nafion tubing a copolymer of tetrafluoroethylene and fluorosulfonyl monomer that is coaxially mounted within larger tubing The sample stream is passed through the interior of the Nafion tubing allowing water and other light polar compounds to permeate through the walls into a dry air purge stream flowing through the annular space between the Nafion and outer tubing Note To prevent excessive moisture build up and any memory effects in the dryer a clean up procedure involving periodic heating of the dryer 100 C for 20 minutes while purging with dry zero air 500 cm3 min should be implemented as part of the user s SOP manual The clean up procedure is repeated during each analysis see Section 14 reference 7 Recent studies have indicated no substantial loss of targeted VOCs utilizing the above clean up procedure 7 This cleanup procedure is particularly useful when employ ing cryogenic pr
258. rgeted com pounds by sampling a humidified gas stream without gas calibration standards with a previously certified clean canister see Section 12 1 11 2 33 The assembled dynamic calibration system is certified clean if less than 0 2 ppbv of targeted compounds are found 11 2 3 4 For generating the humidified calibration standards the calibration gas cylinder s see Section 8 2 containing nominal concentrations of 10 ppmv in nitrogen of selected VOCs are attached to the calibration system as outlined in Section 10 2 3 1 The gas cylinders are opened and the gas mixtures are passed through 0 to 10 cm3 min certified mass flow controllers to generate ppb levels of calibration standards 11 2 3 5 After the appropriate equilibrium period attach the sampling system containing a certified evacuated canister to the manifold as illustrated in Figure 8 a 11 2 3 6 Sample the dynamic calibration gas stream with the sampling system according to Section 9 2 1 Note To conserve generated calibration gas bypass the canister sampling system manifold and attach the sampling system to the calibration gas stream at the inlet of the in line filter of the sampling system so the flow will be less than 500 cm3 min 11 2 3 7 Concurrent with the sampling system operation realtime monitoring of the calibra tion gas stream is accomplished by the on line GC MS or GC multidetector analyti cal system Figure 8 b to provide reference concentrations of
259. rly averages of all meteorological parameters for the air sampling periods This includes average wind speed wind direction wind vector ambient temperature and atmospheric stability Recommended units are miles per hour mph for wind speed degrees relative to north for wind direction with this designation indicating the direction from which the wind is blowing and ambient temperatures in F Summary wind roses including daytime and night time wind roses for complex terrain sites and those located near large water bodies Tabular summaries of means and extremes for temperature and other meteorological parameters e Data recovery summaries for all parameters stat ing percent recovery Generally meteorological listings should generally be presented on a sequential hourly basis A 1 hour time frame is sufficient to account for any short term temporal variability of the data The presentation of data for periods less than 1 hour long unduly complicate the data evaluation process In addition these shorter term list ings would be voluminous For those cases where multi ple meteorological stations are used at a single network it is desirable to list the data in adjacent columns to facilitate meteorological data comparisons Statistical summaries for the meteorological data should be calculated monthly seasonally annually and for the entire monitoring period For sites with diurnal wind patterns e g at complex t
260. rming equipment checks and preparing the equipment for field installation Listed below are items that can be used as a basis for developing vendor specifications Type of equipment and basic source requirements Number of pieces necessary for the program List of spare parts e List of necessary supplies Equipment instruction manuals and other documentation Warranties Delivery time Equipment calibration and repair services e List of clients and number of units sold e Equipment costs e Reference methods or other third party specifica tions which must be met 24 The bids should be evaluated based on a selected set of criteria including the following Quality and performance of equipment Supplier performance and track record Delivery schedule e Supplier responsiveness Support services e Cost This evaluation should be made for each piece of air monitoring equipment that is a part of the program including meteorological equipment Laboratory and consulting services shouid also be evaluated After you select the successful vendor order the equip ment and make sure it is delivered to the group that will install it Before using the equipment you should check it for proper operation and calibration if necessary In addi tion it should be inventoried to allow easy tracking All supplies should be checked and stored at a location con venient for the field operato
261. rmining atmospheric stabil ity it should be integrated in meteorological stations for regional air monitoring Recommended meteorological monitoring system accuracies resolutions and sensor response characteris tics are summarized in Tables 3 5 and 3 6 respectively Field equipment used to collect meteorological data can range in complexity from a very simple analog or mechanical pulse counter data logging system to a microprocessor based data logging system Combine these approaches for your regional air monitoring pro gram This recommendation is not expensive and facili tates the convenient collection of meteorological hourly averaged data that can be easily processed using per sonal computers PCs Chart recorders provide a low cost backup system if the digital data are not available You should conduct a meteorological survey i e short term data collection to support air monitoring network design Exceptions to this practice would include areas that have historical onsite meteorological data or flat terrain areas where representative offsite data are available The duration of the meteorological survey should range from 2 to 6 weeks depending on the objectives and the design elements of the monitoring program In many cases for planning purposes you may use historical offsite data to estimate seasonal effects if the air monitoring program is scheduled to last for more than a few months Additional recommendations
262. rogram should be undertaken after the sampling strategy and the sampling and analysis methods have been defined An effective QA plan for a TOAP monitoring program must address five basic areas a quality assurance management b sampling quality assurance c analytical quality assur ance d data reduction qaulity assurance and e reporting quality assurance Specific con siderations for quality assurance activities in each of these five key areas are summarized in Table 3 2 Each of these topics is addressed thoroughly in Section 7 EPA Excerpt Sampling and Analysis of Toxic Organic Compounds in Ambient Air 80 TABLE 3 2 QUALITY ASSURANCE QA ACTIVITIES SPECIFIED IN PROGRAM PLAN Quality Assurance QA Management QA System Design Document Control Data Evaluation and Storage Audit Procedures Corrective Action QA Reports to Program Management Training Sampling Quality Assurance Site Selection Instrument Calibration and Maintenance Collection of Routine Quality Control Samples Data Recording Sample Labeling Preservation Storage and Transport Chain of Custody Procedures Analytical Quality Assurance Method Validation Requirements Instrument Calibration and Maintenance Quality Control Sample Analysis Data Recording Data Reduction Quality Assurance Merging Sampling and Analysis Data Files Storage of Raw and Intermediate Data Data Validation Reporting Quality Assur
263. round level concentrations of the toxic chemicals released from the facility or industrial sources involved Topographical effects on plume dispersion include valley flow and plume dispersion in complex terrain Nearby water bodies could introduce land water interface and associated onshore flow breeze effects Number and locations of sources and their charac teristics Source characteristics include emission rate type of source point area volume or line type of emissions fugitive or not and nearby structures that could cause wake and plume down wash effects These factors can be formulated and incorporated into a dispersion modeling scheme to calculate ground level concentrations of airborne pollutants for the receptor grid of interest Results of the dispersion model ing provide locations of calculated high short term up to 24 hour average concentrations frequency of occur rence and locations of maximum long term monthly seasonal and annual average concentrations The compiled modeling results together with the factors listed above serve as the primary basis to deter mine the number and locations of monitoring stations You should also account for the available resources and the constraints of the program Table 3 7 provides general guidance for selecting the minimum stations for regional air monitoring and their locations The actual number and locations should be determined on a case by case b
264. rs Preparation of a good inventory management system ensures a mechanism to replenish supplies on time Selecting air monitoring sites and providing access site security 110 volt power lighting and platforms if needed are critical elements of the program that should be completed at the same time as equipment procure ment Typical site preparations include grading prepar ing a platform for the instruments and building a foun dation for the meteorological tower 43 OPERATING AND MAINTAINING THE FIELD INSTRUMENTATION Field and analytical operations of the air monitoring program should be conducted in accordance with the monitoring plan developed for the program see Chapter 3 0 Successful implementation of the monitoring plan requires adequate field staff program management and attention to QA QC factors Therefore program man agers should consider applying the operational approach illustrated in Figure 4 2 to regional air monitoring pro grams Developing Standard Operating Procedures SOPs for each type of air monitoring equipment involved with the program is important Appendix D includes a bibliography of Air Monitoring Standard Operating Procedures Appendix E includes an excerpt of QA QC protocols from the U S EPA Technical Assistance Document for Sampling and Analysis of Toxic Organic Compounds in Ambient Air Examples of SOPs that are pertinent to regional air monitoring programs are included in Appendix F These exa
265. s Percent Recovery Measured Value True Value x 100 2 Precision The reproducibility of repeated measurements of the same property usually made under prescribed conditions Values in this table are expressed as Relative Percent Difference RPD Range Mean x 100 Specific for aldehydes and ketones Good stability for derivative compounds formed Low detection limits Sensitivity limited by reagent priority Potential for evaporation of liquid over long term Collect and concentrate large volume sample with trace concentration Moisture is not a problem Broad use reference methods Low detection limit Easy to use in field Blank contaminants may be a problem Single analysis per sample Artifact formations with time Must calibrate separate detectors Compound identification not positive Lengthy data interpretation Does not differentiate targeted compounds from interfering compounds GC multi detector lower cost than GC MS GC MS Positive compound identification More sensitive than MS Operator skill level important Problems may exist with the collection of ethylene oxide and butadiene Complex equipment preparation required L9 CARTRIDGE SAMPLER Compounds are solvent bor di 5 SUMMARY OF SAMPLING AND ANALYTICAL METHODS FOR TIME INTEGRATED AMBIENT AIR MO
266. s Possible interferences CARTRIDGE SAMPLER Particulates are removed Standard methods from air stream with a GFF or PUF filter dissolved Low detection limits 1 5ng m Standard methods Possible breakthrough High sensitivity High blanks data base available Interferences Specific method for each metal 1 5 ng m Standard methods for each metal Potential interferences and analyzed by spectrometric methods including 1 Accuracy The Agreement of an analytical measurement with a true or accepted value Values in this table are expressed as Percent Recovery Measured Value True Value x 100 2 Precision The reproducibility of repeated measurements of the same property usually made under prescribed conditions Values in this table are expressed as Relative Percent Difference Rance Mean x 100 VAPOR PHASE METALS Sb As Pb Ni Se Ag Hg IMPINGER Collection of vapor phase metals on sorbents and in impinger solutions and analyzed by AA ICP TO 8 ISE or EPA Method 335 1 or 335 3 VAPOR PHASE CN MCEF and Sodium Hydroxide Liquid Impinger 69 TABLE 10 SUMMARY OF SAMPLING AND ANALYTICAL METHODS FOR TIME INTEGRATED AMBIENT AIR MONITORING AMMONIA HYDROGEN CHLORIDE AND HYDROGEN SULFIDE Method T 1 2 Sampling and Analysis Approach Designation Detection Limit Accuracy Disadvantages AMMONIA IN AMBIENT AIR COLLECTED WITH NIOSH 6701 1ppm 20 10
267. s compounds many of which are chlorinated VOCs have been successfully tested for storage stability in pressurized can isters 1 2 However minimal documentation is currently available demonstrating stability of VOCs in subatmospheric pressure canisters The organic compounds that have been successfully collected in pressurized canisters by this method are listed in Table 1 These compounds have been successfully measured at the parts per billion by volume ppbv level Applicable Documents 2 1 2 2 ASTM Standards D1356 Definition of Terms Related to Atmospheric Sampling and Analysis E260 Recommended Practice for General Gas Chromatography Procedures E355 Practice for Gas Chromatography Terms and Relationships Other Documents U S Environmental Protection Agency Technical Assistance Document 3 Laboratory and Ambient Air Studies 4 17 Summary of Method 3 1 3 2 3 3 3 4 Both subatmospheric pressure and pressurized sampling modes use an initially evacuated canister and a pump ventilated sample line during sample collection Pressurized sampling requires an addi tional pump to provide positive pressure to the sample canister A sample of ambient air is drawn through a sampling train comprised of components that regulate the rate and duration of sampling into a pre evacuated SUMMA passivated canister After the air sample is collected the canister valve is closed an identification tag is attached to the
268. s of capital and operating costs for example program scenarios FIGURE 1 1 ELEMENTS TO PLAN AND IMPLEMENT A REGIONAL AIR TOXICS MONITORING PROGRAM GETTING A MONITORING PROGRAM STARTED CHAPTER 2 0 Defining your objectives e involving others in the program Establishing a management structure IMPLEMENTING QUALITY ASSURANCE QUALITY CONTROL CHAPTER 5 0 Defining QA QC requirements Performing routine QA QC checks Implementing periodic QA QC checks Executing laboratory QA QC Program Data management MANAGING AND EVALUATING THE DATA CHAPTER 6 0 Storing and analyzing the data Interpreting the results Re evaluating the program Reporting the results Using the results 1 2 WHY CONDUCT AN AIR TOXICS MONITORING PROGRAM Several reasons drive the need for regional air toxics monitoring programs They include corporate positions regulatory requirements and public concerns Com munities have become very aware of the presence of chemicals in the air and are demanding credible informa tion about the levels sources and effects of chemicals to which they may be exposed Industry is increasingly motivated to Determine ambient concentrations of airborne pollutants commonly known as toxics DEVELOPING THE MONITORING PLAN AND METHODS CHAPTER 3 0 Selecting constituents Duration and frequency of monitoring Selecting sampling and analytical methods Defining meteorolog
269. s of more intense light A typical system configuration associated with the GC FID ECD PID is illustrated in Figure 6 This system is cur rently being used in EPA s FY 88 Urban Air Toxics Monitoring Program 10 2 GC MS SCAN SIM System Performance Criteria 10 2 1 GC MS System Operation 10 2 2 10 2 3 10 2 1 1 Prior to analysis the GC MS system is assembled and checked according to manu facturer s instructions 10 2 1 2 Table 3 0 outlines general operating conditions for the GC MS SCAN SIM system with optional FID 10 2 1 3 The GC MS system is first challenged with humid zero air see Section 11 2 2 10 2 1 4 The GC MS and optional FID system is acceptable if it contains less than 0 2 ppbv of targeted VOCs Daily GC MS Tuning See Figure 13 10 2 2 1 At the beginning of each day or prior to a calibration the GC MS system must be tuned to verify that acceptable performance criteria are achieved 10 222 For tuning the GC MS a cylinder containing 4 bromofluorobenzene is introduced via a sample loop valve injection system Note Some systems allow auto tuning to facilitate this process The key ions and ion abundance criteria that must be met are illustrated in Table 4 Analysis should not begin until all those criteria are met 10 2 2 3 The GC MS tuning standard could also be used to assess GC column performance chromatographic check and as an internal standard Obtain a background correc tion mass spectra of 4
270. s to ensure adequate data quantity and quality for model val idation These factors include 1 the number of moni toring stations considering the topography or nearby large water bodies 2 the location of upwind and down wind stations 3 sampling frequency and duration 4 number of samples to be collected and 5 the quality of sampling and meteorological data including accuracy and precision Model validation requires the identification of a can didate model and the development of a reasonable emission inventory Then monitoring data can be used in model validation The American Meteorological Society s 1981 document entitled Quality Model ing and the Clean Air Act provides a variety of steps that can be used as a measure of the model performance These include e The bias average of the difference observed minus predicted values e The variance of the difference noise The gross variability gross error of the difference In addition measures of correlations can be per formed in time space or both Details of the methodol ogies are outlined in documents produced by the Ameri can Meteorological Society and the U S EPA In certain cases model validation for industrial sources emitting toxic chemicals can be difficult This is because many of the dispersion models currently used are not capable of handling reactive volatile organic compound emissions in the atmosphere Furthermore quant
271. samples are taken to assess future sampling activity 7 1 2 Pressurized Figure 2 With Metal Bellows Type Pump and Figure 3 7 1 2 1 7 1 2 2 7 2 Sample Analysis Sample pump stainless steel metal bellows type Metal Bellows Corp 1075 Provi dence Highway Sharon MA 02067 Model MB 151 or equivalent capable of 2 atmospheres output pressure Pump must be free of leaks clean and uncontami nated by oil or organic compounds Note An alternative sampling system has been developed by Dr R Rasmussen The Oregon Graduate Center 18 19 and is illus trated in Figure 3 This flow system uses in order a pump a mechanical flow regu lator and a mechanical compensating flow restrictive device In this configuration the pump is purged with a large sample flow thereby eliminating the need for an auxiliary vacuum pump to flush the sample inlet Interferences using this conigura tion have been minimal Other supporting materials all other components of the pressurized sampling sys tem Figure 2 with metal bellows type pump and Figure 3 are similar to compo nents discussed in Sections 7 1 1 1 through 7 1 1 16 721 GC MS SCAN Analytical System See Figure 4 7 2 1 1 7 2 1 2 7 2 1 3 The GC MS SCAN analytical system must be capable of acquiring and processing data in the MS SCAN mode Gas chromatograph capable of sub ambient temperature programming for the oven with other generally standard features such as gas flow r
272. ss Achievement of DQO s is ultimately accomplished through a Quality Assurance QA program An effective QA program for inclusion in a TOAP monitoring program will consist of planned and systematic activities necessary to establish consistency of the program output with the needs for which the program was established Program needs can ultimately be understood in terms of acceptable uncertainty associated with the data a QA program ensures that the limit of uncertainty is within the acceptable boundaries of the data collection program The limit of uncertainty will vary with the sampling and analytical procedures Consequent ly there is no universal QA performance standard applicable to all TOAP monitoring prog rams is therefore important to establish QA performance standards consistent with both the intended use of the data and the performance characteristics of the sampling analysis procedures Failure to reconcile discrepancies that exist between intended data use and QA performance characteristics of the sampling and analytical protocol will undermine the TOAP monitoring program 7 2 QUALITY ASSURANCE AND QUALITY CONTROL QA is essentially a management program that addresses delegation of program responsibilities to individuals documentation data review and audits The objective of QA procedures is to permit an assessment of the reliability of the data QA activities are typically performed by personnel involved in normal routine operat
273. t should be specified in the sampling QA plan include a periodic reading of the temperature flow volumes and other parameters b documenta tion meteorological conditions at appropriate time points c documentation of instrument operating variables d documentation of any upset conditions such as sudden leakage or pressure surges and e documentation of calibration or maintenance activities A logbook for the overail sampling program in which sampling descriptions meteorological data and upset conditions are documented should be maintained data sheet should also be pre pared for each set of samples or analytical procedure for which relevant raw data should be recorded Certain measurements such as filter numbers and weights or impinger volumes which are required for analytical purposes can be recorded on a separate sheet with provi sions for recording subsequent analytical data on the same sheet Separate maintenance and calibration logbooks should be maintained for each instrument In most cases specific sampling data forms for a given program must be prepared because of differences in the sampling design between programs The QA program for a TOAP monitoring project will address various steps in the data re duction process including e Merging sampling and analytical data e Storage of raw and intermediate data e Data validation Since sampling and analytical data processing occurs independently in most cases the QA
274. t the project you should meet with participants regularly to discuss key issues review results or solve problems encountered The public at large and opinion leaders can be kept informed via open meetings and press releases In this regard you should designate a project participant as the program s com munications coordinator 2 3 ESTABLISHING MANAGEMENT STRUCTURE A regional air toxics monitoring program is acomplex undertaking Depending on program objectives a pro gram can last from several days to many years Costs of the program can be considerable see Section 7 0 It is necessary then for you to establish a program manage ment structure to make decisions regarding the monitor ing program implement them and administer funds to accomplish the program objectives A number of mech anisms are available to administer the monitoring program including e A management committee composed of represen tatives of contributing sponsors e A corporation formed specifically to run the program as was done in the Houston Regional Monitoring Project e An outside party such as a Chamber of Com merce which could collect and disburse funds with management direction coming from a com mittee of representatives of contributing sponsors Typically final decision making power regarding allocation of resources resides with those who are financing the study However as described in Section 2 2 you should closely consult with
275. t to determine the reason for the flag and whether the compound should be reported as found While this adds some subjective judgment to the analysis computer generated identification problems can be clarified by an experienced operator Manual inspection of the quantitative results should also be performed to verify concentrations outside the expected range A typical chromatogram of VOCs determined by GC MS SIM mode is illus trated in Figure 11 b 107 U S EPA Compendium Method T014 1988 10 1 3 GC Multidetector GC FID ECD System with Optional PID 10 1 3 1 10 1 3 2 10 1 3 3 10 1 3 4 10 1 3 5 10 1 3 6 10 1 3 7 10 1 3 8 The analytical system see Figure 5 is comprised of a gas chromatograph equipped with a capillary column and electron capture and flame ionization detectors see Figure 5 In typical operation sample air from pressurized canisters is vented past the inlet to the analytical system from the canister at a flow rate of 75 cm3 min For analysis only 35 cm3 min of sample gas is used while excess is vented to the atmosphere Sub ambient pressure canisters are connected directly to the inlet The sample gas stream is routed through a six port chromatographic valve and into the cryogenic trap for a total sample volume of 490 cm3 Note This represents 14 minute sampling period at a rate of 35 cm3 min The trap see Section 10 1 1 3 is cooled to 150 C by controlled release of a cryogen VOCs and SVOCs ar
276. taining Drierite or silica gel and 5A molecular sieve are used to remove moisture and organic impurities from the zero air hydrogen and nitrogen gas streams Note Purity of gas purifiers is checked prior to use by passing humid zero air through the gas purifier and analyzing according to Section 12 2 2 All lines should be kept as short as practical All tubing used for the system should be chromatographic grade stainless steel connected with stainless steel fittings After assembly the system should be checked for leaks according to manufacturer s specifications The FID burner air hydrogen nitrogen make up and helium carrier flow rates should be set according to the manufacturer s instructions to obtain an optimal FID response while maintaining a stable flame throughout the analysis Typical flow rates are burner air 450 cm3 min hydrogen 30 cm3 min nitrogen 30 cm3 min helium 2 cm3 min The ECD nitrogen make up gas and helium carrier flow rates should be set accord ing to manufacturer s instructions to obtain an optimal ECD response Typical flow rates are nitrogen 76 cm3 min and helium 2 cm3 min The GC FID ECD could be modified to include a PID see Figure 6 for increased sensitivity 20 In the photoionization process a molecule is ionized by ultraviolet light as follows hv gt R where R is the ionized species and a pho ton is represented by hv with energy less than or equal to the ionization pote
277. the monitoring period Downwind of the facility at offsite receptor loca tions which are expected to have the greatest impact from the releases considering prevailing wind flows e Additional locations at complex terrain and coastal sites associated with pronounced secondary air flow paths e g downwind of the facility for both primary daytime and nighttime flow paths You should select the above locations prior to initial monitoring based on your evaluation of available repre sentative meteorological data 37 SELECTING CONTRACTORS FOR SAMPLING AND ANALYSIS This document was designed to present information to develop specifications for obtaining competitive bids from sampling and analysis contractors You can iden tify potential contractors from a review of reference doc uments open literature personal experience and professional contacts By reviewing contractor literature and publications and by interviewing contractor repre sentatives you can compile a short list of organiza tions to receive request for proposal on monitoring activities You may wish to include a questionnaire concerning contractor capabilities in this process Your request for proposal should specifically describe a scope of work schedule deliverables methods and procedures to be used and other terms and conditions so that quotations can be compared on an equal basis Also you should advise the potential contractors of any specific require
278. this table are expressed as Relative Percent Difference RPD Range Mean x 100 Efficient collection of polar Water collected and can deactivate compounds adsorption sites Wide range of application Thermal desorption of compounds Highly volatile compounds may be difficult adsorbed Easy to use in field CRYOGENIC TRAPPING AND GC ECD Vapor phase 90 11096 t 10 organics are condensed in a cryogenic trap Carrier gas transfers the condensed sample to a GC column Adsorbed compounds are eluted from the GC column and determined by MS or EC detectors Large data base Moisture condensation Excellent long term storage Integrated sampling is difficult Wide applicability Allows multiple analyses Best method for broad speciation of unknown VOCs Easy sample collection Consistent recoveries SUMMA PASSIVATED CANISTER AND GC FID ECD 10 OR GC MS Whole air samples are collected in an evacuated stainless steel canister VOCs are concentrated in the laboratory with cryogen trap VOCs are revolatilized separated on a GC column and passed to one or more detectors for identification and quantitation Best method for broad speciation of Sample components may be unknown trace volatile organics adsorbed or decompose through Simple sampiing approach interaction with container walls Condensation may be a problem at high concentrations ppm Complex equipment preparation required 09 TABLE C 4 SUMMARY OF SAMPLING
279. ting in regional air monitoring programs This guidance allows flexibility in tailoring the program to meet specific local needs It also emphasizes the cooperative nature of such projects and the steps needed to involve the public and regulators during the program planning process The document also provides specific technical recommendations for conducting an air toxics survey followed by longer term regional air monitoring These recommendations are Perform air toxics survey monitoring study for preliminary determination of community concentrations as follows Program duration should be 30 to 90 days Samples are to be collected for 3 to 24 hours every other day or once in 3 days depending on the study s specific objectives The number of monitoring stations established depends on specific local conditions and program objec tives A minimum of two monitoring stations should be implemented in this type of study portable meteorological station should be used vii e Perform regional air toxic monitoring to establish regional community concentrations as follows Program duration should be one year or more Samples are to be collected for 24 hours every sixth day or less The number of monitoring stations established depends on specific local conditions For flat or gently rolling topography with no land water interface the network should contain a minimum of three moni toring stations with one station representi
280. tion and operation Digital Volt Ohm Meter DVOM with certified calibration PROCEDURES j This section describes the daily weekly and bi weekly duties of the Field Technician 171 Routine Operation and Maintenance Daily Time Marking of Analog Charts and Data Logger Check Each day upon arrival at the meteorological monitoring station the Field Technician should fill out a Meteorological System Checklist Form and verify the correct time on the data logger 1 Mark the chart paper with a ballpoint pen or felt tip marker by making a line across the bottom of the exposed area of the chart paper Write down the date month year day and time 24 hour clock Central Standard Time and indicate with an arrow that this date and time correspond with the line drawn 2 Compare the time indicated on the chart paper with the actual time and the data logger time If they do not coin cide adjust the chart time as necessary 3 Obtain data logger readings and record on checklist for wind speed and direction 4 If adjustments were made remark the chart paper with time and date as before Weekly Retrieval Replacement of Data Cassettes On a weekly basis the Field Technicians shall retrieve the cassette tape from the data logger make a backup tape of the one week of data and install a new tape to collect data for the next week All new tapes must be wound past the blank leader prior to start of data collection INSERTING NEW TAPE
281. tions for each analyte are the averages of the two analyses However if the GC FID ECD analytical system discovers unexpected peaks which need further identification and attention or overlapping peaks are discovered elimi nating possible quantitation the sample should then be subjected to a GC MS SCAN for positive identification and quantitation 11 0 Cleaning and Certification Program 11 1 Canister Cleaning and Certification 11 1 1 canisters must be clean and free of any contaminants before sample collection 113 U S EPA Compendium Method T014 1988 11 1 2 All canisters are leak tested by pressurizing them to approximately 206 kPa 30 psig with zero air Note The canister cleaning system in Figure 7 can be used for this task The initial pres sure is measured the canister valve is closed and the final pressure is checked after 24 hours If leak tight the pressure should not vary more than 13 8 kPa 2 psig over the 24 hour period 11 1 3 A canister cleaning system may be assembled as illustrated in Figure 7 Cryogen is added to both the vacuum pump and zero air supply traps The canister s are connected to the manifold The vent shut off valve and the canister valve s are opened to release any remaining pressure in the canister s The vacuum pump is started and the vent shut off valve is then closed and the vacuum shut off valve is opened The canister s are evacuated to lt 0 05 mm Hg for at least one hour
282. tive hours does not vary by more than 10 decrees for 18 consecutive hours Wind Direction is greater than the local record high islessthan the local record low The above limits could be applied on a monthly basis is greater than a 5 C change from the previous hour does not vary by more than 0 5 C for 12 consecutive hours Temperature is greater than 0 1 C m during the daytime is less than 0 1 C m during the nighttime is greater than 5 0 C m or less than 3 Temperature Difference Dew Point is greater than the ambient temperature for the given time Temperature period is greater than a 5 C change for the previous hour does not vary by more than 0 5 C for 12 consecutive hours equals the ambient temperature for 12 consecutive hours Precipitation is greater than 25 mmin 1 hour isgreater than 100 mm n 24 hours e isless than 50 mm in 3 months The above values can be adjusted based on alocal climate Pressure is greater than 1 060 mb sea level isless than 940 mb sea level The above values should be adjusted for elevations other than sea level changes by more than 6 mb in 3 hours a Some criteria may have be changed for a given location 177 Air Monitoring Data Validation Procedure Air monitoring data validation efforts should include evaluating collocated station results and audit results to determine data precision and accuracy as follows
283. to use specific or non specific detectors by considering such factors as project objectives desired detection limits equipment availability cost and person nel capability in developing an analytical strategy A list of some of the advantages and disadvan tages associated with non specific and specific detectors may assist the analyst in the decision making process Non Specific Multidetector Analytical System Advantages Disadvantages e Somewhat lower equipment cost than GC MS Multiple detectors to calibrate e Less sample volume required for analysis e Compound identification not positive e More sensitive e Lengthy data interpretation one hour each for ECD may be 1000 times more sensitive than analysis and data reduction GC MS e nterference s from co eluting compound s e Cannot identify unknown compounds outside range of calibration Without standards e Does nct differentiate targeted compounds from interfering compounds 96 U S EPA Compendium Method T014 1988 Specific Detector Analytical System GC MS SIM Advantages Disadvantages positive compound identification can t identify non specified compounds ions e greater sensitivity than GC MS SCAN somewhat greater equipment cost than less operator interpretation than for multidetector GC multidetector GC greater sample volume required than for multidetector GC can resolve co eluting peaks universality of detector sacrificed to achieve enha
284. tor RF Factor RF Number Time RT ppbv area ppbv area minutes count count x 10 5 1 Freon 12 3 65 3 465 13 89 2 Methyl chloride 4 30 0 693 3 Freon 114 5 13 0 578 22 32 4 Vinyl chloride 5 28 0 406 5 Methyl bromide 6 44 26 34 6 Ethyl chloride 7 06 0 413 7 Freon 11 8 60 6 367 1 367 8 Vinylidene chloride 9 51 0 347 9 Dichloromethane 9 84 0 903 10 Trichlorotrifiuoroethane 10 22 0 374 3 955 11 1 1 Dichloroethane 11 10 0 359 12 cis 1 2 Dichloroethylene 11 99 0 368 13 Chloroform 12 30 1 059 11 14 14 1 2 Dichloroethane 12 92 0 409 15 Methyl chloroform 13 12 0 325 3 258 16 Benzene 13 51 0 117 17 Carbon tetrachloride 13 64 1 451 1 077 18 1 2 Dichloropropane 14 26 0 214 19 Trichloroethylene 14 50 0 327 8 910 20 cis 1 3 Dichloropropene 15 31 21 trans 1 3 Dichloropropene 15 83 22 1 1 2 Trichloroethane 15 93 0 336 23 Toluene 16 17 0 092 24 1 2 Dibromoethane EDB 16 78 0 366 5 137 25 Tetrachloroethylene 17 31 0 324 1 449 26 Chlorobenzene 18 03 0 120 27 Ethylbenzene 18 51 0 092 28 m p Xylene 18 72 0 095 29 Styrene 19 12 0 143 30 1 1 2 2 Tetrachloroethane 19 20 9 856 31 o Xylene 19 23 32 4 Ethyltoluene 20 82 0 100 33 1 3 5 Trimethylbenzene 20 94 0 109 34 1 2 4 Trimethylbenzene 21 46 0 111 35 m Dichlorobenzene 21 50 36 Benzyl chloride 21 56 37 p Dichlorobenzene 21 67 0 188 38 o Dichlorobenzene 22 12 0 188 39 1 2 4 Trichlorobenzene 24 88 0 667 40 Hexachlorobutadiene 25 82 0 305 1 055 Refer to Figures 15 and 16 for peak location 127
285. training program Training effectiveness can be evaluated by written tests proficiency evaluations and or interviews EPA Excerpt Sampling and Analysis of Toxic Organic Compounds in Ambient Air 84 7 4 SAMPLING QUALITY ASSURANCE The purpose of sampling is to collect unbiased samples that are representative of the sys _ tem being monitored The sampling program should be planned and documented in all de tails QA for sampling includes site selection number of samples to be collected frequency of sample collection sampling times instrument calibration and maintenance Quality Con trol sample collection data recording sample labeling sample preservation sample storage sample transport and chain of custody procedures 7 4 1 Site Selection Site selection planning is discussed thoroughly in Section 3 3 The QA plan for a TOAP monitoring program should specify factors which could result in modification of the siting plan during the monitoring effort procedures for approving such modification and provisions for documenting sampling site modifications 7 4 2 Instrument Calibration and Maintenance Calibration of sampling equipment is as vital as calibration of analytical equipment if meaningful data concerning ambient concentrations of TOAP s are to be obtained A QA plan for a TOAP monitoring program will therefore address calibration of sampling equipment Typically the QA plan will include e Written calibration procedures
286. u 9 1 BP 11 187 Mass 49 00 amu 10 1 PP 11 223 Mass 41 00 amu 11 1 BP 11 578 Mass 151 00 amu 12 1 BP 12 492 Mass 63 00 amu 13 1 VP 13 394 Mass 61 00 amu 14 1 PH 13 713 Mass 83 00 amu 15 1 BP 14 378 Mass 62 00 amu 16 1 PB 14 594 Mass 97 00 amu 17 1 VP 15 009 Mass 78 00 amu 18 1 VP 15 154 Mass 117 00 amu 19 1 BB 15 821 Mass 63 00 amu 20 1 BB 16 067 Mass 130 00 amu 21 1 PB 16 941 Mass 75 00 amu 22 1 BP 17 475 Mass 75 00 amu 23 1 BB 17 594 Mass 97 00 amu 24 1 BV 17 844 Mass 91 00 amu 25 1 PB 18 463 Mass 107 00 amu 26 1 PH 18 989 Mass 166 00 amu 27 1 PB 19 705 Mass 112 00 amu 28 1 BP 20 168 Mass 91 00 amu 29 1 PB 20 372 Mass 91 00 amu 30 1 BV 20 778 Mass 104 00 amu 31 1 BH 20 887 Mass 83 00 amu 32 1 BP 20 892 Mass 91 00 amu 33 1 VV 22 488 Mass 105 00 amu 34 1 VB 22 609 Mass 105 00 amu 35 1 BB 23 114 Mass 105 00 amu 36 1 BV 23 273 Mass 146 00 amu 37 1 VV 23 279 Mass 91 00 amu 38 1 VB 23 378 Mass 146 00 amu 39 1 BP 23 850 Mass 146 00 amu 40 1 BB 26 673 Mass 180 00 amu 41 1 27 637 Mass 225 00 amu 131 8 Jan 87 10 02am Bottle Number 2 8 Jan 86 8 13 am 5 00 Absolute Minutes 0 40 Absolute Minutes 0 00 Multiplier 1 667 Compound Name FREON 12 METHYLCHLORIDE FREON 114 VINYLCHLORIDE METHYLBROMIDE ETHYLCHLORIDE FREON 11 VINDENECHLOR DICHLOROMETH ALLYLCHLORID 3CHL3FLUETHA 1 1DICHLOETH c 1 2DICHLET CHLOROFORM 1 2DICHLETHA METHCHLOROFO BENZENE CARBONTETRAC 1 2DICHLPROP TRICHLETHENE c 1 3DICHLPR t 1 3DICH
287. uge pressure Pressure measured above ambient atmospheric pressure as opposed to absolute pressure Zero gauge pressure is equal to ambient atmospheric barometric pressure 5 6 MS SCAN The GC is coupled to a MS programmed in the SCAN mode to scan all ions repeatedly during the GC run As used in the current context this procedure serves as a qualitative identifica tion and characterization of the sample 5 7 MS SIM The GC is coupled to MS programmed to acquire data for only specified ions and to dis regard all others This is performed using SIM coupled to retention time discriminators The GC SIM analysis provides quantitative results for selected constituents of the sample gas as programmed by the user 5 8 Megabore column Chromatographic column having an internal diameter 0 greater than 0 50 mm The Megabore column is a trademark of the J amp W Scientific Co For purposes of this method Megabore refers to chromatographic columns with 0 53 mm 1 0 5 9 Pressurized sampling Collection of an air sample in a canister with a final canister pressure above atmospheric pressure using a sample pump 5 10 Qualitative accuracy The ability of an analytical system to correctly identify compounds 5 11 Quantitative accuracy The ability of an analytical system to correctly measure the concentration of an identified compound 5 12 Static calibration Calibration of an analytical system using standards in a form different t
288. uipped with an OV 1 capillary column 0 32 mm x 50 m and a mass selective detector set in the SIM mode see Figure 4 The GC MS is set up for automatic repetitive analysis The system is programmed to acquire data for only the target compounds and to disregard all others The sen sitivity is 0 1 ppbv for a 250 cm air sample with analytical precision of about 5 relative standard deviation Concentration of compounds based upon a previously installed calibration table is reported by an automated data reduction program A Nafion dryer is also employed by this analytical system prior to cryogenic precon centration therefore many polar compounds are not identified by this procedure SIM analysis is based on a combination of retention times and relative abundances of selected ions see Table 2 These qualifiers are stored on the hard disk of the GC MS computer and are applied for identification of each chromatographic peak The retention time qualifier is determined to be x 0 10 minute of the library retention time of the compound The acceptance level for relative abundance is determined to be 15 of the expected abundance except for vinyl chloride and methylene chloride which is determined to be 25 Three ions are measured for most of the forty compounds When compound identification is made by the computer any peak that fails any of the qualifying tests is flagged e g with All the data should be manually examined by the analys
289. v standard mixture is allowed to flow and equilibrate for a minimum of 30 minutes After the equilibration period the gas standard mixture is sampled and analyzed by the real time GC MS system see Figure 8 a and Section 7 2 1 The results of the analyses are averaged flow audits are performed on the mass flow meters and the calculated concentration compared to generated values After the GC MS is calibrated at three concentration levels a second humid zero air sample is passed through the system and analyzed The second humid zero air test is used to verify that the GC MS system is certified clean less than 0 2 ppbv of target compounds 109 U S EPA Compendium Method T014 1988 10 2 3 2 As an alternative a multipoint humid static calibration three levels plus zero humid 10 2 3 3 air can be performed on the GC MS system During the humid static calibration analyses three 3 SUMMA passivated canisters are filled each at a different con centration between 1 20 ppbv from the calibration manifold using a pump and mass flow control arrangement see Figure 8 c The canisters are then delivered to the GC MS to serve as calibration standards The canisters are analyzed by the MS in the SIM mode each analyzed twice The expected retention time and ion abun dance see Table 2 and Table 5 are used to verify proper operation of the GC MS system A calibration response factor is determined for each analyte as illustrated in Table 5 and the
290. vation Storage and Transport Chain of Custody Procedures Analytical QA QC Method Validation Requirements Instrument Calibration and Maintenance Quality Control Sample Analysis Data Recording The references are included in Section 5 6 Using the approach illustrated in Table 5 1 you should evaluate these to identify those appropriate for your program specific QA QC requirements Summaries of typical sampling and analysis frequencies QA QC requirements and calibration requirements for sampling and analysis instrumentation are presented in Tables 5 2 and 5 3 respectively 5 2 PERFORMING ROUTINE QA QC CHECKS The regional air monitoring program should incorpor ate the following four component approach for routine quality control and assurance checks e Use collocated samples for precision checks e Use blank samples for accuracy checks e Use analytical standards and equipment calibra tions for accuracy checks e Perform data review for internal consistency During each regional air monitoring program one sta tion with two sets of collocated air samplers should be used in accordance with Section 4 5 siting criteria The goal should be to obtain at least 10 percent of collocated samples for each monitoring network The analytical results from the collocated samplers should be used to compare and evaluate the integrity of the samples and the adequacy of laboratory procedures Data Reduction QA QC Sample and An
291. ver a path and cannot easily be used in air quality assessment a Accuracy The Agreement of an analytical measurement with a true or accepted value Values in this table are expressed as Percent Recovery R Measured Value True Value x 100 2 Precision The reproducibility of repeated measurements of the same property usually made under prescribed conditions Values in this table are expressed as Relative Percent Difference RPD Range Mean x 100 v9 TABLE C 12 SUMMARY OF NEAR REAL TIME AMBIENT AIR MONITORING ORGANIC COMPOUNDS Portable GC analyzer utilizing Argon 0 1 to several ppb About 5 10 high Real time continuous Near real time continuous Can analyze only a limited number of ionization electron capture detector depending on the reproducibility concentrations of air toxic air toxic constituents at a time ECD with optional photoionization number of compounds constituents detector preconcentrator and aheated involved and the mix Subject to inaccuracies introduced by column with temperature adjustable to Good accuracy and low detection field conditions and field operators 140 C Up to 16 different compounds limit for a field technique can be processed at any time Library is up to 100 compounds Ongoing Eliminates inaccuracies associated calibration is by injecting standard with the handling of samples calibration gas obtained by integrator samplers that have to be shipped for laboratory analysis Has an option for
292. verview 42 75 00 112 50 Tape II Screening 58 75 00 112 50 Tape III Bagging 38 75 00 112 50 All Three Tapes 225 00 337 50 All tapes are available in and inch formats POSSEE Software Plant Organizational Software System for Emissions from Equipment POSSEE is a software data entry system for fugitive emissions testing designed exclusively for CMA POSSEE can help you set up a testing program enter data and develop estimates of the fugitive emissions at your plant Member price 150 00 Non member price 225 00 Guide to Estimate Secondary Emissions In Publication A guidance manual for estimation emissions from secondary air sources for SARA 313 reporting Member price 40 00 Non member price 60 00 PAVE Software In Development To order these documents please refer to order form on the last page of this publication vi Executive Summary As responsible members of the communities in which they operate industries are increasingly motivated to partici pate in efforts to measure concentrations of chemicals in the community Publics e g community concerned citizens groups business and Federal state and local regulatory agencies have become very aware of the presence of chemicals in the air These audiences are rightfully demanding credible information about levels sources and effects of chemicals to which they may be exposed They are expecting information to Determine ambient concentrations
293. what gaps remain in the existing data base e What is the quality of past data and how defensible are they What technical resources are available to perform or assist in the program What financial resources are required and or avail able for this program In addition you may have other objectives for your monitoring program These can include permitting for facility expansion model validation studies and emer gency release evaluations Other issues you need to address in the beginning are how the information generated by the program will be used and who will have access to it Ground rules must be set early to avoid future misunderstandings among project participants Participants will expect to access results and possibly ongoing operations data Nonpar ticipants can also inquire about the availability of and access to data However there is always a danger that raw data can be misinterpreted Resources for programs are always limited Available resources should be concentrated on the highest priority objectives so that the quality of results is not diluted The issues posed above and other considerations specific to your needs will help you make decisions on the scope of your program and the methods to be used 2 2 INVOLVING OTHERS IN THE PROGRAM The results of a regional air monitoring program will not be of value unless they are accepted as being valid by the general public and regulators as well as the
294. x C When applicable the EPA designated sampling and analysis method is listed in this table Two types of equipment and supply costs are provided in Table 7 1 One is for purchasing and the other is for equipment leasing The leasing cost is based on recover ing the purchase price over a period of 1 year Table 7 1 also includes cost estimates for laboratory analysis Additional assumptions that were made in developing the costs presented in Table 7 1 are The cost of a canister sampler includes three can isters at total cost of 1 350 to 1 500 Three canisters are included with each sampler to ensure continuity of the sampling program while the analysis is performed e The cost of sorption tube samplers Tenax and carbon molecular sieve includes 30 tubes at a total cost of 1 000 00 to 1 500 00 39 e The cost of the Tedlar bag sampler includes a supply of 30 bags at a total cost between 800 00 to 950 00 e The cost of a polyurethane foam PUF sampler includes brushes 60 PUF plugs and 100 fiberglass filters at a total cost of 300 to 500 Each PUF calibration kit costs between 100 to 400 When more than one monitoring station is considered for the network only one calibration kit should be purchased Hence a cost adjustment should be made to exclude this cost of having more than one calibration kit The cost of the high volume 10 sampler includes brushes and 100 quartz filters at a total cost
295. y as determined from dispersion modeling is 0 2 g m Then the CRI for lead is Annual Concentration 0 2 Example 2 The RfD value for mercury is 0 5 g m Assume the calculated annual average mercury concentration on the community as determined from dispersion modeling is 0 1 g m Then the CRI for mercury is Annual Concentration 0 1 CRI mercury RfD 05 0 2 Caiculating the CRI for Carcinogens The following are examples for calculating the CRI for carcinogens These examples use calculated annual concentrations derived by a dispersion model Example 3 The reference value RsD X100 for dichloromethane is 200 g m Assume the calculated annual average dichloromethane concentration in the community as determined from dispersion modeling is 4 g m3 Then the CRI for dichloromethane is Concentration 4 CRI dichloromethane teferencevalus 7 200 02 l The RfD inhalation is a benchmark dose derived from the NOAEL Observed Adverse Effect Level by consistent application of order of magnitude uncertainty factors If an inhalation RfD is not available it can be calculated as 10 unit risk number g m The RsD is the dose corresponding to 10 0 upperbound on risk Another measure which has been used is the ED jo value the estimated dose corresponding to a 10 tumor incidence in animals Example 4 The reference value RsD X100 for trichloroethylene 15 60 g m Assume t
296. y in residential areas TABLE 3 8 A SUMMARY OF KEY PROBE SITTING CRITERIA FOR AIR MONITORING STATIONS Vertical spacing above ground Horizontal spacing from obstruction and obstacles Unrestricted airflow Spacing from roads Representative of the breathing zone and avoiding effects of obstruction obstacles and roadway traffic Height of probe intake above ground is in general 2 3m and 2 15m in the case of nearby roadways About 1m or more above the structure where the sampler is located Minimum horizontal separation from obstructions such as trees is 220m from the dripline and 10m from the dripline when the trees act as an obstruction Distance from sampler inlet to an obstacle such as a building must be at least twice the height the obstacle protrudes above the sampler If a sampler is located on a roof or other structures there must be a minimum of 2m separation from walls parapets penthouses etc There must be sufficient separation between the sampler and a furnace or incinerator flue The separation distance depends on the height and the nature of the emissions involved Unrestricted airflow must exist in an arc of atleast 270 degrees around the sampler and the predominant wind direction for the monitoring period must be included in the 270 degree arc The sampler must be located far enough away from nearby roadways to avoid the effect of dust re entrainment and vehicular emissions on the measured air c
297. y individuals who are not directly involved with the measure ment process 7 3 5 1 Performance Audits Performance audits are incorporated into a TOAP monitoring program to quantitatively as sess the quality of the data being generated by a measurement system Performance audits include the evaluation of recovery of reference materials through the sampling and analytical equipment and the review of results when test data are entered into a data processing system 7 3 5 2 System Audits System audits are incorporated into a TOAP monitoring program to qualitatively assess the quality of data being generated by the measurement system System audits focus on opera tional aspects of the measurement process There aspects include adherence to a estab lished sampling and analytical procedures b sample shipment and receipt procedures c equipment maintenance schedules and d quality control and quality audit schedules 7 3 6 Quality Assurance Reports A variety of QA reports should be prepared periodically by the QA personnel and submitted to the TOAP monitoring program manager The frequency and type of report equae will be specified by the QA project plan Data Quality Assessment Reports address the precision and accuracy of program data Performance and System Audit Reports summarize the results of audits performed during the course of the TOAP monitoring project Data Validation Reports summarize questionabie data collected during the m
298. ypically employed in regional air monitoring may need training Therefore staff involved with field and other technical air toxics monitoring projects should be air quality specialists with relevant ambient air monitoring experience Regardless of the individuals backgrounds they must have a thorough knowledge of or receive training in the equipment and methods to be employed Their familiarity with computerized database manage ment techniques would also be beneficial Field personnel in particular must be well trained in e Understanding the operation of the sampling equipment Performing the preventive maintenance actions recommended by the manufacturer Conducting timely equipment checks and calibrations Maintaining the required logs and records to docu ment pertinent field activities These activities must be clearly documented for future reference Carefully handling collected samples to avoid con tamination or loss of materials This includes docu menting in detail every sample sent for laboratory analysis to maintain the correct chain of custody Carefully maintaining the program schedule for sampling and analysis Carefully checking regenerated equipment cani ster traps plugs etc that are returned by the laboratory Consistently collecting QA QC samples e Maintaining communications with other project personnel and management to ensure that they are kept apprised of a
299. yurethane foam NEAR REAL TIME SCREENING Gas Phase Particulate Phase Polyurethane foam PUF plug is designed to collect semi volatile organic gases Tedlar is a registered trademark of E I DuPont de Nemours and Company Technique OP 4 Detection Monitoring Sampling Classification Category of Monitoring Sampling Method Compounds Detected Traps sorbents and cryogenics and laboratory analysis S Ond Many organic compounds by chemical species Historical integrated Fraction of a TM e Whole air samplers canisters and bags and laboratory analysis ppb to ppb Many organic compounds by chemical species Historical integrated Liquid impingers Aidehydes ketones phosgene cresol phenols Historical integrated ppb to ppb High volume samplers with glass fiber filter membrane fiiter or foie inorifariics Historical integrated Teflon filter PCBs and other semi volatile organic species Portable field GC analyzers with constant temperature oven Field GC laboratory Total Hydrocarbon THC Analyzers Colorimetric gas detection tubes and monitors Electrochemical alarm cells Portable pumps with filters Portable pumps with filters and special plugs ppm Various organics for a specific chemical species Realtime continuous mg m3 Most inorganic compounds Historical integrated Limited list of organic compounds by chemical species Historical

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