Chloride - Ozarks Environmental and Water Resources Institute
Contents
1. ID Chloride Revision 2 November 2013 Page 3 of 13 Identification of the test method Operation of the accumet excel XL25 dual channel pH lon meter for chloride concentration determination Applicable matrix or matrices This method is suitable for the determination of chloride concentrations in potable surface and waste waters The accument excel XL25 meter has an operating range of 1 x 10 to 100 ppm chloride Detection limit The practical detection limit is 0 1 ppm Scope of the test method This standard operating procedure provides Missouri State University MSU laboratory personnel protocol for determining chloride concentration in water samples Summary of test method A water sample is combined with an ion strength adjuster to create a uniform background ionic strength which provides more accurate and reproducible measurements with the ion selective electrode ISE used for these determinations The chloride electrode is introduced to the sample and the electrode s sensing membrane develops an electrical potential which is proportional to the activity of the chloride anion inthe sample The sample activity is compared to the activity of the range of standards used to calibrate the instrument and chloride concentration is calculated Definitions 6 1 Analytical batch The set of samples processed at the same time 6 2 Calibration standard A solution prepared from the primary dilution standard solution or stock standa2. 9 1X 11 6 Thermo Scientific Orion ISE lonic Strength Adjuster Fisher Cat No 13 641 852 Use 2 ml 100 ml sample to produce a uniform background ionic strength Sample collection preservation shipment and storage 12 1 Refer to the Water Sampling SOP for appropriate collection procedures SOP 1040R01 Water Sampling doc 12 2 Samples are stored on ice for transport to the laboratory and are refrigerated immediately upon transfer to the laboratory Chloride samples do not require any preservation solution addition 12 3 There is a 28 day holding time for chloride EPA 600 4 79 020 however samples should be analyzed as soon as possible Quality control 13 1 Quality control program The minimum requirements of the quality control program for this analysis consist of an initial demonstration of laboratory capability and the periodic analysis of laboratory reagent blanks and other laboratory solutions as a continuing check on performance The laboratory must 13 2 13 3 13 4 ID Chloride Revision 2 November 2013 Page 6 of 13 maintain performance records that define the quality of the data that are generated a Analyses of laboratory blanks are required to demonstrate freedom from contamination Analyze one LRB for every 10 samples analyzed The laboratory shall on an ongoing basis demonstrate through calibration verification and analysis of the ongoing precision sample that the analysis system is in control Eac
3. Standard Operating Procedure for accumet excel XL25 Dual Channel pH lon Meter for Chloride Concentration Determination Chloride R02 doc Missouri State University and Ozarks Environmental and Water Resources Institute OEWRI Prepared by Date OEWRI Quality Assurance Coordinator Approved by Date OEWRI Director MISSOURI STATE UNIVERSITY Missouri State U VS ie e a E A i Ozarks Environmental and Water Resources Institute ID Chloride Revision 2 November 2013 Page 2 of 13 Table of Contents 1 Identification of the test method ccccccssseeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeseneeeeeeeeeeeseeeseneseennees 3 2 Applicable matrix or MatriC sS ccceseeeeeeeeeeeeeeeeeeeeeeeeeeeeeseeeeeeeeeeeeeeeaseeeeeeeeeeeeeeeenneees 3 3 Detection limit sni eniin a elena Shad aa ae aai ne elect aao aia aatinaa adL aoaia 3 4 Scope of the test method wiisnicveciced cect setecctecieet eens eacdiecieetitn ete nnmnnn nnana 3 5 Summary of test method siseasi le dewecenteekenteccececenswchenteeces ined ceeiexesssuceeinewebecteseeees 3 6 Baiil ET AT A AT TT 3 7 Mie EEN E S A r araa aea a ea E EE Aaaa aaa aAa aara cies Set ed Aaea aaea EERS 4 8 Health and SATOUY occ fica ssces coed cca sane dean seais iiet arao sedenredetanazes sve ceeedeeatciedcdguendviaisaxsaccceness 4 9 Personnel qualifications ci cassis ci decicece dete cc ts dectee ta cececcpedacndede decade lexseetedadencpedeesdsendadeess 4 10 Equipment and sup
4. as outlined in the accument excel XL25 operator s manual Calibration Solutions Preparation a Prepare the Blank 0 00ppm by using a 40 ml aliquot of HPLC water only Prepare Standard 1 10 ppm by removing a 4 ml aliquot of Spex CertiPrep 100 ppm Standard Stock Solution from the standard bottle with a pipette and clean tip and combine it with 36 ml HPLC in a clean beaker Prepare Standard 2 50 ppm by removing a 20 ml aliquot of Spex CertiPrep 100 ppm Standard Stock Solution from the standard bottle with a pipette and clean tip and combine it with 20 ml HPLC in a clean beaker Prepare Standard 3 100 ppm by removing a 40 ml aliquot of Spex CertiPrep 100 ppm Standard Stock Solution from the standard bottle with a pipette and clean tip and transfer it to a clean beaker 15 e ID Chloride Revision 2 November 2013 Page 8 of 13 Remove 0 8 ml of the ionic strength adjuster solution from the bottle with a pipette and clean tip and transfer it to each standard and the blank 14 6 Calibration Procedures a b C Add a clean stir bar to each standard and the blank Rinse the electrode with HPLC water and blot with paper towel Place the Blank on the stir plate and turn dial to 6 Immerse electrode into the blank solution but DO NOT allow the stir bar to touch the electrode Press Standardize on the lon Measure screen to access the standardization screen Press Clear if necessary to remove a previous standardiza
5. ecision values are calculated for pairs of duplicate analyses The desired precision is 10 RPD 20 3 Accuracy values are calculated for standard checks analyzed within and at the end of the batch The desired accuracy is 10 RPD 20 4 The desired detection limit is 0 1 mg CI L 20 5 All completed bench sheets are reviewed by the OEWRI QA QC manager Corrective actions for out of control or unacceptable data 21 1 The results for precision accuracy and blank data are compared to acceptable values for these analyses 10 RPD and 0 1 mg CI L respectively 22 23 24 ID Chloride Revision 2 November 2013 Page 11 of 13 21 2 If a blank value exceeds 0 1 mgCl L during batch analysis then the analyst should immediately re analyze the blank and if the blank continues to exceed the MDL contact the QA QC manager 21 3 If data are unacceptable for any reason the analyst should review their analytical techniques prior to conducting these analyses again 21 4 The batch may be re analyzed as QA QC dictates 21 5 The meter may require trouble shooting techniques if the data are unacceptable beyond regular maintenance including cleaning the electrode changing the reference solution or replacing the electrode All maintenance and repairs must be recorded in the instrument log book Waste management The waste generated in this method are not hazardous The quantities generated are small and waste can be discarded in the laboratory si
6. eviation s for the analyte The value of X should be within 10 of the true value The standard deviation should be less than or equal to 10 of the average value Duplicate reproducibility 14 d ID Chloride Revision 2 November 2013 Page 7 of 13 Measure the sample and a separate aliquot of the same sample LD The relative percent difference RPD between the two values should be lt 10 of their average value Use equation 1 to calculate RPD Equation 1 RPD A B x100 A B 2 Where A first measurement and B duplicate measurement Analyze one set of duplicates for every 10 samples analyzed Calibration and standardization The accumet excel XL25 chloride meter will be calibrated prior to every batch analysis 14 1 14 2 14 3 14 4 14 5 Calibration employs a standard curve derived from plotting electrical potential or the activity produced from the standard solutions including the reagent blank versus known chloride anion concentration in the standards The data is fit to a linear equation using the software associate with the meter and concentration is presented on the screen The chloride electrode will always be stored in the Chloride Electrode Storage Solution 98 4 HPLC H20 1 KHP and 0 6 KCI 98 4 ml H20 1 g KHP and 0 6 g KCI or will be cleaned drained and stored within the original box when not in use for extended periods of time Clean and perform routine maintenance
7. f analytes or interferences are present in the laboratory environment or the apparatus 6 8 Method detection limit MDL The lowest level at which an analyte can be detected with 99 percent confidence that the analyte concentration is greater than zero To calculate the MDL a Analyze seven aliquots of HPLC water including all sample processing steps prior to the determination b Calculate the standard deviation s C The multiplier used to derive the MDL is from a table of a one sided t distribution where the value of tfor 7 1 6 degrees of freedom at the 99 level was selected This value is 3 14 d The product 3 14 times s is the desired MDL 6 9 Relative Percent Difference RPD calculated as the difference between a sample and duplicate results divided by the average of the sample and duplicate results multiplied by 100 6 10 Standard Check Standards analyzed as samples to monitor instrument shift or analyst error Interferences Cyanide thiosulfate and ammonia are potential interferences to the chloride electrode and could significantly influence electrode response Samples should be free of sulfide as it destroys the electrode surface Wastewater samples should be screened for sulfide and ammonia content prior to being exposed to the electrode associated with this meter Health and safety This analysis involves handling freshwater samples that may contain live microorganisms and therefore pose some threat of i
8. h standard used to calibrate the instrument is re analyzed at the end of the batch or after every 20 samples and at the end of the batch to verify calibration and quantify instrument drift A laboratory duplicate is analyzed for every 10 samples analyzed to quantify precision The laboratory should maintain records to define the quality of data that is generated Demonstration of capability a new analyst should Read this standard operating procedure Demonstrate to a previously trained analyst that the procedures outlined here are being followed and Successfully report data collected using these procedures to the QA QC manager Initial demonstration of performance The following must be satisfied before the analytical procedure may be used for samples a Method Detection Limit MDL To establish the ability to detect the analyte the analyst shall determine the MDL by carrying through 7 or more separately prepared reagent blank solutions through the analytical procedure The average value X and the standard deviation of the values s shall be calculated The MDL is equal to 3s 3 x standard deviation The MDL and average value X must both be less than 0 10 mg CI L Initial Precision and Recovery To establish the ability to generate acceptably precise and accurate results the operator shall perform 10 replicates of a mid range standard Using the results of the replicates compute the average value X and the standard d
9. nfection Laboratory personnel who are routinely exposed to such water samples are encouraged to protect themselves from water borne illnesses by wearing clean disposable gloves and washing their hands frequently Personnel qualifications Laboratory personnel shall have a working knowledge of this analytical procedure and will have received training from an MSU employee knowledgeable of the proper sample analysis procedures Prior to the first batch of sample analyses the analyst will complete a demonstration of capability exercise as described below in the Quality control section 10 11 12 13 ID Chloride Revision 2 November 2013 Page 5 of 13 Equipment and supplies 10 1 Fisher Accumet Excel XL 25 with Chloride ISE Electrode 10 2 Fisher Scientific stir plate 10 3 100 ml Griffin Beakers Fisher Cat No 863242 10 4 Stir bars Fisher Cat No 14 513 58SIX 10 5 1000 uL pipette and tips Fisher Cat No 21 377 146 10 6 10 uL pipette and tips Reagents and standards 11 1 Chloride Electrode Storage Solution 98 4 H20 1 KHP and 0 6 KCI 98 4 ml H20 1 g KHP and 0 6 g KCl 11 2 DI water For rinsing electrode between samples 11 3 Fisher Accumet Chloride ISE Electrode Filling Solution Fisher Cat No 13 620 432 Reference solution for electrode 11 4 HPLC Fisher Cat No W5 4 For mixing standards 11 5 Spex CertiPrep lon Chromatography Chloride Standard Solution 100mg l Fisher Cat No AS CL
10. nk References 23 1 Accumet Excel User Manual 2004 Fisher Scientific Tables diagrams flowcharts and validation data 24 1 There are no tables diagrams or flowcharts for this method 24 2 The following page contains the chloride bench sheet The analyst should copy this form and use one for each batch of samples analyzed Analyst Missouri State University Ozarks Environmental and Water Resources Institute Chloride Bench Sheet Date analyzed Projects COCs associated with Analysis Sample Data Data reviewed by Sample Date Sample Chloride Chloride Identification Collected Concentration mg l Concentration mg l Blank Oppm Std 1 10ppm Std 2 SOppm Std 3 100ppm Comments Chloride Bench Procedures Make Label bench sheet Set samples out to warm up to room temp Make blank standards for calibration H20 IA Blank Oppm 40 0 mL Std1 10ppm 39 2 mL Std2 50ppm 36 0 mL Std3 100ppm 32 0 mL Read blank standards o Standardize clear standardize blank wait confirm o Standardize standard enter wait confirm Samples Samples Rinse between each probe reading If any samples read under range write that down LD every 12 samples Run standards again after samples
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12. rd solutions The calibration standards are used to calibrate the instrument response with respect to analyte concentration 6 3 Chain of Custody COC Used to describe the written record of the collection possession and handling of samples Chain of custody forms should be completed as described in the Chain of Custody SOP 1030R01 Chain of custody COC forms are located on a board in Temple Hall 125 6 4 Field Duplicate FD Two samples taken at the same time and place under identical circumstances and which are treated identically throughout field and laboratory procedures Analysis of field duplicates indicates the precision associated with sample collection preservation and storage as well as laboratory procedures 6 5 lonic Strength Adjuster ISA Buffer solution added to the samples and standards to create a uniform background ionic strength for increased accuracy and precision ID Chloride Revision 2 November 2013 Page 4 of 13 6 6 Laboratory Duplicate LD Two aliquots of the same environmental sample treated identically throughout a laboratory analytical procedure Analysis of laboratory duplicates indicates precision associated with laboratory procedures but not with sample collection preservation or storage procedures 6 7 Laboratory Reagent Blank LRB An aliquot of HPLC water that is used to calibrate the instrument at the beginning of the analysis and is analyzed within the batch analysis sequence to determine i
13. screen press Log Data and record the concentration on the chloride bench sheet Remove the electrode from the sample and rinse with HPLC water Repeat procedures 15 1 15 9 until all samples are analyzed Use a separate 40 ml aliquot of one of the samples to produce a Laboratory Duplicates LD for every 10 samples analyzed Record the sample number and LD on the bench sheet when recording the concentration of the laboratory duplicate Use the original standards and blank to check the calibration and instrument drift by analyzing each solution after every 20 samples and at the end of the batch Repeat procedures 15 1 15 9 for each standard and blank treating them as samples so the original calibration is used throughout the analysis Record Standard 1 Standard 2 Standard 3 and Blank concentrations on the bench sheet Data acquisition calculations and reporting 16 1 Data Exporting Procedures a Press View in the mV setup screen b Press Export View and Header to save data in HTML format C Press SD Card and name the file using the alphanumeric keypad at the bottom of the screen The file name should include Chloride Data the date of analyses the project names and date of sample collection associated with the COCs completed during the analysis d Press OK in the upper right corner of the Save As screen e Close all applications prior to SD card removal f Press gently down on
14. the card to unlock it and when the card disengages and pops up pull it from the expansion slot g Data can be viewed using Windows Explorer 1 Press Setup and then View 17 18 19 20 21 ID Chloride Revision 2 November 2013 Page 10 of 13 2 Data is listed inversely of analysis sequence 16 2 The software associated with the meter calculates all concentrations base on the initial batch calibration 16 3 Reporting results Results should be reported to the 0 1 mg CI L precision Computer hardware and software 17 1 Word This document and attached bench sheet are prepared using Microsoft Word 17 2 Excel Quality control charts are created using Excel Method performance 18 1 The desired performance criteria for this measurement are Detection limit 0 1 mg CI L Precision 10 RPD Accuracy 10 RPD Minimum Quantification Interval 0 1 mg CI L aO TD 18 2 The applicable range for the method is 0 1 to 100 mg CI L and may be extended by dilution Pollution prevention 19 1 All wastes from these procedures shall be collected and disposed of according to existing waste policies within the MSU Geography Geology and Planning Department 19 2 Volumes of reagents made should mirror the number of samples being analyzed These adjustments should be made to reduce waste Data assessment and acceptable criteria for quality control measures 20 1 The analyst should review all data for correctness 20 2 Pr
15. tion Proceed when the screen reads Not standardized Press Blank A beaker icon labeled blank will be displayed on the lon Measure screen Remove the Blank from the stir plate rinse the electrode and blot with a paper towel Place Standard 1 on the stir plate and immerse the electrode in the standard Press Standardize and then Standard The screen will flash each standard icon once and then a numeric keypad will appear Input the value of the standard and press Enter The screen will illustrate the value of the standard solution in the flashing beaker Wait until Stable appears on the screen and press Confirm once to confirm the standardization Repeat procedures 14 6 i k with Standard 2 and Standard 3 Sample Analysis 15 1 Thoroughly shake sample in sample bottle and measure 40 ml into a clean labeled beaker 15 2 Remove 0 8 ml of the ionic strength adjuster solution from the solution bottle with a pipette and clean tip and transfer it to the sample 15 3 Add a clean stir bar to each sample 16 15 4 15 5 15 6 15 7 15 8 15 9 15 10 15 11 15 12 ID Chloride Revision 2 November 2013 Page 9 of 13 Rinse the electrode with HPLC and blot with paper towel Place the sample on the stir plate and turn dial to 6 Immerse the electrode in the stirring sample but DO NOT allow the stir bar to touch the electrode Press Measure to begin the analysis of the sample Wait until Stable appears on the
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