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for Water Quality Monitoring in Cape Cod Bay 2012 – 2013

1. Description Field Required Data type amp format Field Identifier of sampling event EVENT ID Y alphanumeric maximum survey 10 characters Identifier for station STAT ID Y alphanumeric maximum 10 characters Latitude measured at each station LATITUDE Y number 7 decimal visit decimal degrees places Longitude measured at each LONGITUDE Y number 7 decimal station visit decimal degrees places Depth to bottom in meters DEPTH TO Y number 2 decimal measured by echo sounder BOTTOM places Station arrival date and time STAT ARRIV Y date local time LOCAL Sample identifier SAMPLE ID Y alphanumeric maximum 15 characters Code for type of gear used to GEAR CODE Y alphanumeric maximum collect sample 12 characters Depth of sample from water DEPTH Y number 2 decimal surface to bottom of sample in places m Depth of water sample from DEPTH TOP number 2 decimal water surface to top of sample in places m Date and time sample was taken SAMPLE DATE _ Date local time TIME LOCAL Sample depth type code SAMPLE DEPTH Y alphanumeric maximum A near surface E near bottom CODE 2 characters Z zooplankton net tow Volume of sample as collected SAMP VOL number e g calculated tow volume for zooplankton tows Unit of volume measurement SAMP VOL alphanumeric maximum UNIT CODE 3 characters Comments for a given station COMMENTS alphanume
2. 0 6726 NaHCO FW 84 01 Deionized Water Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 37 Dissolve 128 5 g of sodium chloride 28 5 g of magnesium sulfate and 0 672 g of sodium bicarbonate in about 3 liters of deionized water Dilute to 4 liters with deionized water These reagents must be high quality reagent grade to avoid excessive nutrient or trace metal contamination 10 Sampler Wash See Operating Notes 11 Startup Shutdown Solution Deionized Watetz 5 eene RH Dated deus 1000 ml Detetoent uenis esee it urere x doe trei eer ta 2 4ml Add 2 to 4 ml of TX 10 to 1000 ml of deionized water Mix well 12 Open Tubular Cadmium Reactor OTCR The Astoria analytical cartridge uses an Open Tubular Cadmium Reactor coil to reduce nitrate to nitrite Nitrogen is used to segment the analytical stream to prevent a pH increase due to reaction between oxygen in ambient air and cadmium Contact with oxygen will also deactivate the OTCR A OTCR Activation The OTCR API p n 303 0500 24 is a coiled cadmium tube 24 that has been cleaned of manufacturing oils inside and coated with plastic outside The outside diameter is 0 090 inches with an inside diameter of 0 050 inches and a wall thickness of 0 020 inches Short lengths of 0 034 ID polyethylene are sleeved to the reactor coil to allow installation of the reactor in the manifold
3. 0 1410 5000 10 1 QSP 2300L 1 5 2 1 3 Representativeness The representativeness of the sampling program design is detailed in the Outfall Monitoring Plan MWRA 1997 and defined by the results collected since 1992 Representativeness will also be ensured by proper handling storage and analysis of calibration samples so that the materials analyzed reflect the collected material Deviations from the data collection procedures described in this QAPP will be documented in the survey logbook and described in the survey report 1 5 2 1 4 Completeness The navigation software system outputs navigation positions at an interval of 1 second The software system will display all position fixes and save these fixes in an electronic file during hydrocasts and sampling operations The project time interval requirement for obtaining positions during sampling is one 1 minute Thus even if a few bad data streams from the dGPS navigation system to the computer are experienced the software will provide enough position fixes within each 1 minute period for 100 data collection Because hydrographic data are acquired electronically and monitored in real time no loss of data is expected Stations will not be occupied if CTD measurements and navigation coordinates at a minimum cannot be obtained If instrument malfunctions occur and operations are modified or suspended during any survey day a decision on modification of activitie
4. Description Field Required Data type amp format Field Identifier of sampling EVENT ID Y alphanumeric maximum event survey 10 characters Sample identifier SAMPLE ID Y alphanumeric maximum 15 characters Identifier for bottle BOTTLE ID Y alphanumeric maximum 15 characters Code for parameter PARAM CODE Y alphanumeric maximum measured 20 characters Result for parameter VALUE number Value qualifier VAL QUAL alphanumeric maximum 4 characters Code for unit of UNIT CODE alphanumeric maximum measurement 20 characters Code for method METH CODE alphanumeric maximum 13 characters Code for instrument used INSTR CODE alphanumeric maximum 10 characters Comments on this result COMMENTS alphanumeric maximum 150 characters d Plankton measurement data Description Field Required Data type amp format Field Identifier of sampling event EVENT ID Y alphanumeric maximum 10 survey characters Sample identifier SAMPLE ID Y alphanumeric maximum 15 characters Subsample bottle identifier BOTTLE ID Y alphanumeric maximum 15 characters Code for species SPEC CODE Y alphanumeric maximum 17 characters Taxonomic name for species DESCR Y alphanumeric maximum 80 characters Qualifier for species code SPEC QUAL alphanumeric maximum 4 including sex and or life stage characters codes Default null for when sex or life stage is unknown or not relevant Count of cells for that species VALUE Y number Value qualifier VAL QUAL alph
5. F Reduction Efficiency and Stabilization of the OTCR In the OTCR nitrate is reduced to nitrite However under some conditions reduction may proceed further with nitrite being reduced to hydroxylamine and ammonia These reactions are pH dependent NO 2 2 NO gt H20 1 4 NO NOH H O 2 8 2 3 At the buffered pH of reactions equation 1 predominates However if cadmium surface is overly active equation 2 will proceed sufficiently to give low results If the cadmium surface is insufficiently active there will be a low recovery of nitrate as nitrite This latter is defined as poor reduction efficiency To determine the reduction efficiency run a high level nitrite calibrant followed by a nitrate calibrant of the same nominal concentration A reduction efficiency range of 90 110 is acceptable The reduction efficiency is calculated as follows Peak Height NO3 x100 9 efficiency Peak Height NO gt If the response of the nitrite is as expected but the reactor efficiency is poor it may be necessary to repeat the activation procedure However if the nitrite response is much less than expected it is an indication that the nitrite is being further reduced and stabilization of the OTCR is necessary G Stabilization When an OTCR is first activated it may be necessary to stabilize the activity of the reactor In order to stabilize
6. Larvaceans Molluscs Cyphonautes Gammerid Amphipods Hyperiid Amphipods Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay Fish Eggs Fish Larvae Euphausiids Zoea Late larval crustaceans Mysids Urchin larvae Veligers Medusae Salps Ctenophores Pteropods Cliones Ostracods Other COMMENTS Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 88 APPENDIX Guidance Protocol on the Interaction with Whales Specifically Northern Right Whales for Vessels Operated Contracted by the Commonwealth of Massachusetts Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 89 Guidance Protocol on the Interaction with Whales Specifically Northern Right Whales for Vessels Operated Contracted by the Commonwealth of Massachusetts Introduction The northern right whale is the most endangered large whale in the world In the western north Atlantic the population is estimated to be about 300 animals Massachusetts coastal waters are part of the range of the northern right whale and Cape Cod Bay has been designated a critical habitat for the whale under the federal Endangered Species Act because of its high use by the species in the late winter and early spring for feedin
7. Field Sample Filtration Generally two replicate samples are filtered from each water sample within 2 hours of sample collection If filtration cannot take place immediately after sample collection water samples must be refrigerated In subdued light water samples are filtered through 0 7 um glass fiber filters Whatman GF F Individual filters are folded in half wrapped first in blotting filters for example a piece of white paper towel or white coffee filter and then in squares of aluminum foil These foil packs are then placed in a Whirlpak labeled with the following information location date amount of water filtered The filters are kept frozen until just prior to extraction and analysis Lights must be kept off during analysis and preparations Lighting should be the minimum that is necessary to read instructions and operate fluorometer Extraction Procedure A glass fiber filter through which has been filtered a known aliquot of water is placed in a glass 16 x 150 mm test tube containing 10 ml of 90 acetone The vial is capped shaken vigorously and allowed to steep 18 24 hours at 4 deg C Prior to analysis the rack of vials is brought to room temperature Instrumentation Turner Trilogy Laboratory Fluorometer Calibration The fluorometer is calibrated at the beginning of each monitoring season with 2 liquid pure chlorophyll a standards and reagent blanks following the manufacturer s instructions At the time of calibration a
8. Brij 35 30 w v API p n 90 0710 04 Deionized Water ASTM Type I or Ethanol 200 Proof FW 46 07 Optional See Operating Notes Low Nutrient Seawater LNSW Magnesium Sulfate MgSO4 7H20 FW 246 48 Nitrogen gas source o phthaldialdehyde C8H602 FW 134 1 CAS 643 79 8 Sodium Bicarbonate NaHCO3 FW 84 01 Sodium Chloride NaCl FW 58 44 Sodium Sulfite Na2SO3 FW 126 0 Sodium Tetraborate 2 4 7 10H20 FW 381 37 See operating notes for information on matrix choices Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 52 NOTE Chemicals should be of ACS grade or equivalent F Reagent Preparation 1 Stock Sodium Sulfite Solution 250 ml Sodium Sulfite corio acco 26 2503 FW 126 0 Deionized Water Dissolve 2 g sodium sulfite in approximately 200 ml of deionized water contained in 250 ml volumetric flask mix well and dilute to the mark Store in a sealed container This solution is stable for 1 month 2 Borate Buffer Solution 1 L 15a eroi ede entend de 306 Na2B407 10H20 FW 381 37 Deionized Water Dissolve 30 g of sodium tetraborate in about 900 ml of deionized water contained in a 1 L volumetric flask Dilute to the mark with deionized water and mix well Keep tightly closed Stable for several months 3 OPA Working Reag
9. enne ente te nsns seen tenen nass esee tete rena aset 27 3 2 REPORTS TO MANAGEMENT 5 sire cetera vetet tr EU cots ee Les Ue teenies eU RE T e ure e De Ver eR 27 DW eec cC EE DATA VALIDATION AND USABILITY M 27 4 1 DATA REVIEW VALIDATION AND VERIFICATION REQUIREMENTS 0 0002020 0000 27 4 2 VALIDATION AND VERIFICATION METHODS 21 12 2 1 10000000000000000000000000000 28 4 3 RECONCILIATION WITH USER 6 01220 00000010100000000 28 uper PIE REFERENCES m 29 APPENDIX A sie 555 n 31 P 76 5 80 ZOOPLANKTON COUNT 522225 4 416100 ae oo naa eae a e degna eu en aae rua 85 Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay Page ii of iii LIST OF TABLES TABLE
10. entities counted per sample minimum tally To increase precision of the abundance estimates for the most abundant taxa when practical at least 75 entities of each of the three most abundant taxa will be counted in each sample The overall goal then is to enumerate a minimum of 400 entities total and the 3 most abundant taxa to at least 75 entities each An additional data quality procedure will be performed on the whole water phytoplankton samples A subset of samples will be counted in duplicate by a different taxonomist or as a blind recount by the same taxonomist to provide an estimate of the variability in the analysis and ensure the accuracy and comparability of the results One whole water sample from the surveys in February April June August and October will be analyzed in duplicate This range of samples should cover the major taxonomic groupings and various levels of abundance The results as relative percent difference RPD will be included in the data submission as an estimate of the variability in the analysis The RPD for total and the most dominant species should be lt 20 If the RPD is greater than 20 a second aliquot will be counted and the three results used to calculate the relative standard deviation RSD which should be lt 20 Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 20 2 5 2 2 2 Zooplankton Zooplankton samples will be either sub sampled with a Wildco Henson Stemple pipe
11. 9 Place all lines in a clean beaker of DI water for 10 minutes 10 Place reagent lines in Startup Shutdown solution sample probe in sample wash pot and wash line into DI water and allow to pump for at least 20 minutes 11 Change all pump tubes and polyflow tubing 12 Inspect all injection fittings sample splitter s debubblers sample probe and reagent lines on the cartridge for debris If necessary clean appropriately or replace with clean parts 13 Clean all reagent bottles with the bleach solution and rinse thoroughly followed by 1N rinse thoroughly before adding reagents This step is only needed if the same bottle is continuously used for the reagent 14 Clean all platens using a tissue moistened with isopropyl alcohol or methanol 15 Wipe the pump rollers using a tissue moistened with isopropyl alcohol or methanol Try to remove any debris or particulates around the pump rollers and bushings 16 Pump Startup Shutdown solution for 5 to 10 minutes until you have obtained good flow through the system The Open Tubular Cadmium Reactor OTCR will be cleaned with 1 followed by a DI rinse every 2 weeks Auxiliary pump tubing will be replaced every 6 months Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 21 2 6 2 Maintenance for Turner Trilogy Fluorometer 1 month or more frequently as needed At least once a month or more frequently as needed the sample chamber
12. at least 3 times inside and out with DI water 9 Air dry inverted 10 After drying store with either parafilm or aluminum foil across the top or with caps loosely attached Plasticware Cleaning Procedures Do not soak in acid bath 1 Empty non hazardous contents of bottles down the drain and hazardous contents into appropriate waste containers Remove labels This is expedited by soaking bottles in tap water Wash in soapy water Liqui Nox Rinse with tap water at least 3 times Rinse thoroughly at least 3 times inside and out with DI water Air dry inverted QU des Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 34 Standard Operating Procedure 003 Nitrate Nitrite Analysis Date Nov 2007 Revision 2 Primary Method EPA 353 4 A Scope and Application This method is used for the determination of nitrite or nitrate plus nitrite in seawater and is applicable to many ranges B Summary of Method Nitrate is reduced quantitatively to nitrite by cadmium metal in the form of an open tubular cadmium reactor OTCR The nitrite thus formed plus any originally present in the sample is determined as an azo dye at 540 nm following its diazotization with sulfanilamide and subsequent coupling with N 1 naphthylethylenediamine These reactions take place in acidic solution Nydahl provides good discussion of nitrate reduction by cadmium metal while the specific details of OTCR s
13. audits will be used to objectively and consistently determine whether the data are useable for the purposes of this project 4 2 Validation and Verification Methods To assess the quality and usability of the data several methods of data validation and verification are used throughout the data collection analysis and reporting process and overseen by the QA Officer Sample containers are pre labeled to ensure completeness and accuracy of sample collection Manual entry of field sampling data is verified for correctness and completeness by comparing the field survey log book to the post survey report Data downloaded directly from instrumentation are date and time stamped and can be cross referenced to the field survey log book Manual data entry of laboratory data e g zooplankton and phytoplankton will be verified by 100 double keypunching and using the computer to check for differences All other laboratory data is downloaded directly from the instrument Calculations performed on the data e g plankton concentration will be done in Excel and verified manually at a frequency to ensure that formulas are correct appropriate and consistent and that calculations are accurately reported Additional data validation is achieved by following the protocols for holding times instrument calibration and maintenance quality control sample results and other criteria for data quality requirements as outlined in this QAPP 4 3 Reconciliation w
14. wait for a stable baseline autozero the detector and run the samples again The peaks seen are due to the refractive index disturbance 5 As stated above the system is optimal when the sample matrix is carried over into the sampler wash solution and the standards If this is not possible i e if deionized water is used for the sampler wash and or calibrants it is advisable to check for refractive index disturbance effects This can be accomplished by running without the NED present After the initial sample run is finished place the data collection in pause replace the NED reagent with deionized water wait for a stable baseline autozero the detector and run the sample again The peaks that are seen are due to the refractive index disturbance 6 If bubbles are sticking in a debubbler cleaning the debubbler will allow bubbles to escape smoothly out the debubble line Bubbles sticking in the debubbler can cause a loss in the overall precision of the peak height To clean soak the debubbler for 2 3 hours in a mixture of 20 30 Contrad NF API p n 80 0007 04 and hot tap water Rinse thoroughly 7 Ifthe flowrate of the sample pump tube is lt 226 a blk blk pump tube a helper line must be added when the cartridge is run alone See Section 9 of the Astoria Analyzer Operation Manual for information on how to add a helper line NOTE Ifthe sample line is debubbled a helper line is not necessary 8 Cover all reagents and
15. 1 1 CONTACT INFORMATION FOR WATER QUALITY MONITORING PROGRAM IN CAPE COD BAY n TABLE 1 2 SAMPLING LOCATIONS OF THE WATER QUALITY MONITORING STATIONS cccsessesecececeesesseceeeeeeseserseaeeeeees TABLE 1 3 ROUTINE MEASUREMENTS TO BE CONDUCTED AT THE THREE 5 8 2000 0 TABLE 1 4 SAMPLING SCHEDULE FOR CCB AND SBNMS WATER QUALITY MONITORING eere nennen TABLE 1 5 ACCURACY AND PRECISION OF INSTRUMENT SENSORS TABLE 1 6 DESIRED PRECISION ACCURACY AND MDL FOR EACH PARAMETER BASED ON QUALITY OBJECTIVES TABLE 2 1 SAMPLE COLLECTION AND STORAGE ccsessssesececsesessececececsesessececeecceeseaeaeeeeecseseaaeseecceceenssaeeeecceceessasaeeees TABLE 2 2 METHODS OF DETECTION FOR ANALYTES TABLE 2 3 DATA QUALITY OBJECTIVES ccscssssccccecsessssececccecsesssseceeccecsesessasecececsesesuaeeeecceesessaaeeeeceeesenaaeceeeceeeessaaeaeeecs TABLE 2 4 LABORATORY ANALYTICAL QC NUTRIENTS NITRATE NITRITE ORTHO PHOSPHATE AMMONIA SILICATE TN AND TABLE 2 5 LABORATORY ANALYTICAL QC CHLOROPHYLL A TABLE 2 6 SPECIFICATIONS FOR DATA SETS iiscsscsscccseisadscdeseascseveetvedscsucevucviedseasssesseesecedsedessecsiessdeavesveseceeieessduvdeeiectees es Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay Page iii of iii LIST OF FIGURES FIGURE 1 1 O
16. BP166 100 or BP166 500 are acceptable There are special considerations when running seawater samples on any flow system A Standards Primary standards should be prepared from the best grade of chemicals available Certificates of Analysis are available from the chemical manufacturer These should be consulted to identify impurities Standard material should be oven dried for two hours at 110 C before weighing Itis advisable to periodically verify the concentrations of the working standards This can be done by running standards against standards from an outside source matrix of the standards should be consistent with that of the samples If deionized water standards are used it becomes important to determine the salt effects of each individual test See number 2 under Operating Notes NOTE First move the stannous chloride reagent line to startup solution for 5 minutes before moving the other reagent lines This will allow the stannous chloride line to rinse out before the tartaric acid is removed J 11 12 13 14 References Truesdale V W C J Smith The Formation of Molybdosilicic Acids from Mixed Solutions of Molybdosilicic Acids from Mixed Solutions of Molybdate and Silicate Analyst March 1975 vol 100 Pg 203 212 Armstrong F A J Stearns and J D Stickland 1967 The measurement of upwelling and subsequent biological processes by means of the Technicon AutoAnalyzer and associated equipme
17. Bay 72 Magnesium neu ed Pena 28 5 g 5 7 2 246 48 Sodium Bicarbonate o t RE REN 0 672 g NaHCO3 FW 84 01 Deionized Water Dissolve 128 5 g of sodium chloride 28 5 g of magnesium sulfate and 0 672 g of sodium bicarbonate in about 3 liters of deionized water Dilute to 4 liters with deionized water These reagents must be high quality reagent grade to avoid excessive nutrient or trace metal contamination 10 Sampler Wash See Operating Notes G Calibrants Specific Stock and Working Calibrant preparation instructions can be found on the back of the flow diagram Be sure to use the flow diagram which covers the concentration range you wish to analyze Working calibrants may be prepared to cover alternate ranges by adding the appropriate volumes of stock or intermediate calibrant to 100 ml volumetric flasks that contain approximately 80 ml of sampler wash solution Dilute the solution to 100 ml with sampler wash solution and mix well The following formula can be used to calculate the amount of stock or intermediate calibrant to be used C2V2 Where desired concentration in mg L of working calibrant to be prepared final volume in ml of working calibrant to be prepared generally 100 ml C2 concentration in mg L of stock or intermediate calibrant V2 volume in ml of stock or intermediate calibrant to be used Rearranging the eq
18. Leeney RH Stamieszkin K Jaquet N Mayo CA Osterberg D Marx MK 2008 Surveillance monitoring and management of North Atlantic right whales in Cape Cod Bay and adjacent waters Final Report submitted to the Division of Marine Fisheries Commonwealth of Massachusetts Libby PS Fitzpatrick MR Buhl RL Lescarbeau GR Leo WS Borkman DG Turner JT Oviatt CA 2010 Quality assurance project plan QAPP for water column monitoring 2010 Tasks 4 9 and 13 Boston Massachusetts Water Resources Authority Report 2010 02 105 p Turner JT Borkman DG Pierce RW 1995 Should Red Tide Dinoflagellates be Sampled Using Techniques for Microzooplankton Rather than Phytoplankton Pp 737 742 in P Lassus et al Eds Harmful Marine Algal Blooms Lavoisier Paris France 30 SOP 001 SOP 002 SOP 003 SOP 004 SOP 005 SOP 006 SOP 007 SOP 008 SOP 009 SOP 010 APPENDIX A Standard Operating Procedures General Laboratory Safety General Labware Cleaning Procedure Nitrate Nitrite Analysis Ortho Phosphate Analysis Ammonia Analysis TN and TP Analysis Chlorophyll a Analysis Phytoplankton Analysis Zooplankton Analysis Silicate Analysis 31 Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 32 Standard Operating Procedure 001 General Laboratory Safety Date Nov 2007 Revision 2 Purpose and Description Provide guidance on appropriate lab safety protocols Lab complies with
19. Phytoplankton and Nutrients in Buzzards Bay Massachusetts 1987 1988 M S Thesis University of Massachusetts Dartmouth Dartmouth MA 203 pp Borkman D RW Pierce JT Turner 1993 Dinoflagellate blooms in Buzzards Bay Massachusetts Pp 211 216 in Smayda T J and Y Shimizu Eds Proceedings of the Fifth International Conference on Toxic Marine Phytoplankton Elsevier Guillard RRL 1973 Division rates Pages 289 311 In J R Stein Ed Phycological Methods Cambridge Univ Press Libby PS Gagnon C Albro C Mickelson M Keller AA Borkman D Turner JT Oviatt CA 2002 Combined work quality assurance plan for baseline water quality monitoring 2002 2005 Boston Massachusetts Water Resources Authority Report ENQUAD ms 074 79 p Libby PS Gagnon C Albro C Mickelson M Keller A Borkman D Turner J Oviatt CA 2005 Combined work quality assurance plan for baseline water quality monitoring 2004 2005 Boston Massachusetts Water Resources Authority Report ENQUAD ms 074 Version 1 76 pp apps Libby PS Mansfield A Buhl R Lescarbeau G Leo W Keller AA Borkman DG Turner JT and Oviatt CA 2006 Combined work quality assurance project plan QAPP for water column monitoring 2006 2007 tasks 4 5 6 7 8 11 Boston Massachusetts Water Resources Authority Report 2006 03 119 p Libby S Fitzpatrick M Buhl R Lescarbeau G Leo W Borkman D Turner J Oviatt CA 2009b Quality assurance project plan QAPP for water quali
20. Section 2 4 2 1 5 2 1 Navigational and Hydrographic Data 1 5 2 1 1 Precision and Accuracy Manufacturer precision and accuracy objectives for navigation and hydrographic sampling are presented in Table 1 5 Navigational accuracy of 10 m is required for this program 1 5 2 1 2 Comparability All sampling positions will be comparable to positions obtained by previous MWRA monitoring activities The station locations are targets and sampling will be conducted within 300 m of the targets as visualized on the Northstar 952XD navigation display The electronic measurement instruments that will be used during the water quality monitoring surveys are similar to the instruments that have been used by MWRA contractors since 1992 Table 1 5 Accuracy and precision of instrument sensors Sensor Model Units Range Accuracy Precision Navigation Northstar Degree World 4m 4m 952XD Surface PAR Biospherical 0 1410 5000 10 1 QSR 2100 Pressure Seabird SBE Decibars 0 to 1000 0 1 0 1 19plus V2 Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 7 Sensor Model Units Range Accuracy Precision Temperature Seabird SBE C 5 to 35 0 001 0 01 19plus V2 Conductivity Seabird SBE mS cm 0 to 70 0 03 0 01 19plus V2 Dissolved Seabird SBE 43 mg L 0 to 15 0 50 0 05 Oxygen Fluorometer WET Labs ug L 0 01 to 125 0 01 0 01 Chl a ECO FL PAR Biospherical
21. Water Quality Monitoring in Cape Cod Bay 16 e For nitrate nitrite analysis nitrate in the sample is reduced quantitatively to nitrite by cadmium metal in the form of an open tubular cadmium reactor OTCR The nitrite thus formed plus any originally present in the sample is determined as an azo dye at 540 nm following its diazotization with sulfanilamide and subsequent coupling with N 1 naphthylethylenediamine These reactions take place in acidic solution For analysis of ortho phosphate the ortho phosphate in the sample reacts with molybdenum VI and antimony in an acidic medium to form a phosphoantimonylmolybdenum complex This complex is subsequently reduced by ascorbic acid to a heteropolyblue with an absorbance maximum at 880 nm For analysis of ammonia The sample is mixed with o phthaldialdehyde and sodium sulfite in a borate buffered solution at 75 C After sufficient mixing the sample concentration is measured by fluorescence spectroscopy using 360nm excitation and 420 470nm emission wavelengths The increase in fluorescence is directly proportional to the ammonia concentration e For analysis of silicate silicomolybdic acid is formed by the reaction of silicate with molybdic acid The silicomolybdic acid is reduced by stannous chloride to form molybdenum blue with an absorbance maximum at 820 e For analysis of total nitrogen and total phosphorous an alkaline persulfate digestion oxidizes all forms of inorganic an
22. are given by Patton The information concerning mechanisms and kinetics of the color forming reactions can be found in References 3 and 4 C Sample Handling and Preservation All samples will be filtered using 0 4 um Nucleopore filters Samples must be kept frozen until analysis Holding time should not exceed 28 days D Raw Materials Required NOTE Chemicals should be of ACS grade or equivalent Ammonium Chloride NH4Cl FW 53 50 Chloroform CHCl FW 119 38 Cupric Sulfate Pentahydrate CuSO4e5H O FW 249 69 Deionized Water ASTM Type I or II Detergent TX 10 API p n 90 0760 04 Hydrochloric Acid Concentrated FW 36 46 Imidazole C3H4N2 FW 68 08 Low Nutrient Seawater LNSW Magnesium Sulfate MgSO4e7H2O FW 246 48 N 1 naphthylethylenediamine Dihydrochloride Ci2Hj4N2e2HCl FW 259 18 Potassium Nitrate KNO FW 101 11 Sodium Bicarbonate NaHCO FW 84 01 Sodium Chloride NaCl FW 58 44 Sodium Nitrite NaNO FW 69 0 Sulfanilamide CeHgsN2O S FW 172 21 See Operating Notes for information on matrix choices Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 35 E Reagent Preparation 1 Copper Sulfate Solution 2 1 L C pric Sul tate d oot chs 206 CuSO4e5H O FW 249 69 Deionized Water Dissolve 20 g of cupric sulfate in approximately 900 ml of deionized water contained in a 1 L volumetric fla
23. if an entire chamber is not counted an exact volume can still be determined Typical volumes counted are one row of the chamber 50 1 cells 1 20 of 1 ml The volume of sample examined is dependent on number of cells encountered and how long it takes to reach cut offs of 75 entities unicellular forms colonies or chains of each of the top 3 taxa and 400 entities total Calculation of abundance also accounts for the concentration factor used in the settling process Normally the volume processed is 800 ml of whole water sample settled to 50 ml of concentrate for a 16 1 ratio Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 17 The following equation results in the abundance estimate for cells counted C Vs Vc 1000 cells L where C cells counted Vs Volume of concentrated sample Vc Volume of sample examined Vror Original volume 2 4 2 4 Zooplankton The zooplankton are identified and counted by trained individuals Sub samples to be counted are taken by 1 suspending the sample in a known volume of water and taking a subsample of at least 250 organisms to count and identify using a Wildco Hensen Stemple pipette with plunger 2 first splitting the sample with a Folsom plankton splitter and then continuing with the steps in 1 or 3 counting and identifying all organisms in the sample should sub sampling be impossible The results of the counts are expres
24. in a 1 L volumetric flask Dissolve 10 8 g of ammonium molybdate in the acidic solution Dilute the solution to the mark with deionized water and mix it well Filter to 0 45 um Store the reagent in a plastic container Do not refrigerate this reagent Discard the solution if it becomes blue 3 Working Molybdic Acid Reagent 100 ml Stock Molvbdie AGI 100 ml SES 15 2 6 WW 4 drops Mix together 100 ml of ammonium molybdate and 4 drops of SLS Prepare daily the quantity sufficient for the day s run 4 Tartaric Acid 20 w v 1 L Tartari Acid Acestes dnt 200 g H2C4H406 FW 150 09 Deionized Water COP OOM 2 drops Dissolve 200 g of tartaric acid in approximately 700 ml of deionized water contained in 1 L volumetric flask Dilute the solution to the mark with deionized water and mix it well Filter to Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 71 0 45 um Add 2 drops of chloroform Store the reagent in a plastic container and refrigerate it at 2 8 C Filter every 10 days 5 Stock Stannous Chloride 100 ml SlAMNOUS C MOoELIde ueste tuit rese 50 06 SnC12 2H20 FW 225 65 Hydrochlone i 5
25. in which it is stable for 1 month at 4 C 7 Ammonium Chloride Solution ommo nam e TOT Te 306 NH Cl FW 53 49 Ultrapure water Dissolve 30 0 g of ammonium chloride in approximately 800 ml of ultrapure water in a 1000 ml volumetric flask Dilute to mark and store at room temperature for up to 1 month 8 Ammonium Chloride Buffer Ammonium chloride solution sein ae era dads tiled 50 mL TIM ape Waban c eee a sese ne ecu deut 100 mL Amonum by OT ORT cs pata pub pop et aati ts ta ot 250 uL NH4OH FW 35 05 ND 1 5 mL Mix ammonium chloride solution ultrapure water ammonium hydroxide and TX 10 in a 250 ml flask Prepare day of sample analysis F Sample Preparation Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 59 Alkaline persulfate digests are prepared by dispensing samples and digestion reagent into 45 mL screw cap borosilicate glass vials Type 1 class in the volume ratio of 4 1 i e 20 000 mL sample 5 000 mL digestion reagent All tubes are capped tightly and mixed thoroughly by manual inversion The capped tubes are placed in a room temperature DI water bath The level of the bath should reach approximately inch below the level of the liquid in the sample vials With the lid closed the water bath is heated to at least 100
26. m to near bottom 3 5 m from seafloor Salinity and density sigma t will be calculated from the conductivity temperature and depth data Sea surface PAR and time will be recorded concurrently with the hydrocast measurements 2 2 1 2 Water Collection and Plankton Net Tows Near surface 0 5 1 5 m from surface and near bottom 3 5 m from seafloor samples for each suite of analytes are collected in PVC Niskin bottles The Niskin bottle will be lowered by hand to the designated depth On deck water from the Niskin bottle will be subsampled for analysis of dissolved inorganic nutrients total nutrients chlorophyll All sample bottles are acid washed prior to use in the field and rinsed three times with sample water before filling The sample bottles and analytes are shown in Table 2 1 Surface water will be collected for phytoplankton identification and enumeration whole water and an oblique net tow will be conducted to collect zooplankton for identification and enumeration Because we will be following similar protocols as carried out in previous years for phytoplankton identification and enumeration all information in this QAPP pertaining to phytoplankton collection analysis and quality control was taken from Libby et al 2010 with only slight modifications The following describes the optimal order of operations for water and plankton collections e CTD will be secured at the surface to let sensors equilibrate Niskin will be lowered
27. of DI water in a 500 mL volumetric flask Dilute this solution to the mark with DI water and mix it thoroughly by manual inversion and shaking Transfer the stock digest check solution to a 500 mL Pyrex media bottle in which it is stable for 6 months at 4 C 5 Glucose Digest Check Stock Solution CHIC OSS 1 564 g FW 1 80 2 Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 58 Ultrapure Water Dissolve 1 564 g glucose in about 400 mL of DI water in a 500 mL volumetric flask Dilute this solution to the mark with DI water and mix it thoroughly by manual inversion and shaking Transfer the stock digest check solution to a 500 mL Pyrex media bottle in which it is stable for 6 months at 4 C 6 Mixed Digest Check Solution Glycerine digest check stock 1 mL Glycerophosphate digest check stock 002 2 2 2 2 0 1 mL Glucose digest check stock solution sse 10 mL Ultrapure Water Dispense 1 mL each of glycine and glycerophosphate stock digest check solutions 10 mL of the glucose digest check stock solution into a 250 mL volumetric flask that contains about 200 mL of DI water Dilute the contents of the flask to the mark with DI water and mix it thoroughly by manual inversion and shaking Transfer the mixed digest check solution to a 250 mL Pyrex media bottle
28. other solutions to avoid interference due to dust and other particulates This will also help prevent contamination of the solutions from absorbance of analytes in the air I References 1 Standard Methods for the Examination of Water and Wastewater Centennial Edition 21 Ed 2005 American Public Health Association Washington D C Method referenced Automated Cadmium Reduction 4500 NO3F pp 4 125 4 126 F Nydahl Talanta 23 Pages 349 357 1976 Patton C J Doctoral Dissertation Michigan State University 1982 Page 87 121 Fox J B Anal Chem 51 1493 1979 Automated Nutrient Analysis in Seawater Technical Report Brookhaven National Laboratory Whitledge Veidt et al 1986 6 Methods and Guidance for Analysis of Water 1999 Office of Water Environmental Protection Agency USEPA Cincinnati OH Method referenced 353 3 phe pe ACKNOWLEDGEMENTS Astoria and FASPac are trademarks of Astoria Pacific Inc Clackamas Oregon Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 44 Parafilm is a registered trademark of American National Can Norwalk CT Contrad NF and Neutrad are registered trademarks of Decon Labs Inc Bryn Mawr Pennsylvania Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 45 Standard Operating Procedure 004 Ortho Phosphate Analysis Date Nov 2007 Revision 2 P
29. solid secondary standard is also analyzed and the formula for calculating chlorophyll a in samples is determined That solid standard is analyzed with each batch of samples When sample concentration is calculated an allowance for instrument drift is made using the daily batch readings of the solid standard Blanks of 90 acetone and an unused filter extracted with 90 acetone are set up with each rack of samples Cuvettes 12x35 mm glass test tubes Fluorometer Operation 1 Make sure Trilogy is off 2 Insert the Chlorophyll acidification Optical Application Module 3 Close lid and turn power on Use the touch screen to identify the type of Optical Application Module installed Procedure 1 The fluorometer should be on with Home screen displayed 2 Select Chl A chlorophyll acidification Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 61 In raw fluorescence mode measure a blank 90 acetone and the secondary standard Record on data sheet On the screen select Mode to switch to the calibration mode Use stored calibration select the most recent stored calibration Samples After the 24 hr extraction is complete be sure cap is tightly sealed and invert test tube several times to mix contents Work in dim light wear surgical gloves to keep acetone from your hands Remove cap poor 5 ml into sample cuvette Check cuvette to be sure there are no finger prints on glass polish
30. sp group 1 length F lt 10 microns Unid micro phytoflag sp group 2 length F gt 10 microns Ciliatea aloricate Mesodinium rubrum Tintinnidae hyaline Tintinnids aglomerate Chl Pediastrum spp Chl Scenedesmus spp Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 85 Zooplankton Count Sheet Cruise I D Date of Cruise Date Counted Counter Initials Station Net sfc obl Settled Volume Container Volume Counted Volume Sample Volume Total Zooplankton Lo d Ld LLL dL Calanus finmarchicus C1 C2 C3 C4 C5 C6 F C6M Early C1 to C4 Late C5 amp C6 Centropages spp typ ham typ ham typ ham typ ham typ ham typ ham Early C1 to C4 C5 C6 F C6 M Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay Late C5 amp C6 gt Early gt Late Pseudocalanus spp Para Clausocalanus Pseudo Early C1 to C4 Pseudo Late C5 amp C6 COPEPODS Temora longicornis Tortanus discuadatus Acartia spp Eurytemora spp Oithona spp Metridia spp Paraeuchaeta spp harpacticoids other unidentified copepods OTHER ZOOPLANKTON Cyprids Nauplii Chaetognaths Cladocera Polychaetes
31. whale and or damage to the vessel Also record the name of any other vessels in the area that may have witnessed the incident or can provide information about circumstances A copy of the vessel s log for the entire trip should be submitted to the Director of the Division of Marine Fisheries the Director of the Division of Law Enforcement the Secretary of Environmental Affairs and the National Marine Fisheries Service Northeast Region in Gloucester If after hitting the whale the animal is incapacitated or appears to have life threatening injuries and the vessel is safe and secure immediately call the Center for Coastal Studies entanglement hotline at 800 900 3622 or via their pager at 508 803 0204 and the Massachusetts Environmental Police Communications Center at 800 632 8075 or 617 727 6398 Stay with the whale until the Coast Guard or Center for Coastal Studies arrives on scene Entanglements If the vessel come upon or entangles a right whale immediately notify the Center for Coastal Studies entanglement hotline at 800 900 3622 or via their pager at 508 803 0204 and the Massachusetts Environmental Police Communications Center at 800 632 8075 or 617 727 6398 Do not attempt to remove any debris from the whale stay on station with the whale or follow at a safe distance As relocating an entangled whale can be extremely difficult staying on station or following the animal is very important However if following the whale 1s not possible co
32. 0 Artificial seawater does not need to be used Salted water NaCl is sufficient as sampler wash solution The refractive index is small regardless of what salinity the sampler wash is but a salinity of 35 provides the best results J References 1 K rouel R et al Marine Chemistry 57 265 275 1997 2 Holmes R M et al Canadian Journal of Fisheries and Aquatic Sciences 56 1801 1808 1999 3 Jones R et al Journal of Limnology and Oceanography 36 814 819 1991 4 Automated Nutrient Analysis in Seawater Technical Report Brookhaven National Laboratory Whiteledge Veidt et al May 1986 5 Methods for Chemical Analysis of Water and Wastes March 1984 EPA 600 4 79 020 Nitrogen Ammonia Method 350 1 Colorimetric Automated Phenate STORET NO Total 00610 Dissolved 00608 ACKNOWLEDGMENTS Astoria and FASPac are trademarks of Astoria Pacific Inc Clackamas Oregon Brij 35 is a registered trademark of ICI Americas Wilmington Delaware Contrad NF and Neutrad are registered trademarks of Decon Labs Inc Bryn Mawr Pennsylvania Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 56 Standard Operating Procedure 006 TN and TP Analysis Date Feb 2012 Primary Method Oviatt and Hindle 1994 A Scope and Application This method is used for the determination of Total Nitrogen and Total Phosphorous in seawater and is applicable to many ranges B Summar
33. 0 microns length Din Gymn Gyrodinium sp group 2 21 40 microns width 21 50 microns length Din Gymn Gyrodinium spirale Din Heterocapsa rotundata Din Heterocapsa triquetra Din Protoperidinium bipes Din Protoperidinium claudicans Din Protoperidinium depressum Din Protoperidinium pallidum Din Protoperidinium pentagonum Din Protoperidinium quinquecorne Din Protoperidinium sp group 1 10 30 microns width 10 40 microns length Din Protoperidinium sp group 2 31 75 microns width 41 80 microns length Din Protoperidinium sp group 3 76 150 microns width 81 150 microns length Din Prorocentrum micans Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 84 Din Prorocentrum minimum Din Prorocentrum scutellum Din Prorocentrum triestinum Din Thecate dinoflagellate F Calycomonas wulffii F Coccolithophorida Cryptomonas sp group 1 length lt 10 F microns Cryptomonas sp group 2 length gt 10 F microns F Dictyocha formosa F Dictyocha speculum F Dinobryon spp F Ebria tripartita F Eutreptia Eutreptiella spp F Paulinella ovalis F Phaeocystis pouchetii Pyramimonas sp group 1 10 20 microns F length Unid micro phytoflag
34. 0 ml concentrated FW 36 46 Deionized Water While stirring cautiously add 50 ml of hydrochloric acid to 30 ml of deionized water contained in a plastic volumetric flask Dissolve 50 g of stannous chloride in the acidic solution Heating may be necessary to obtain complete dissolution Dilute to 100 ml with deionized water and mix well Store the stock solution in a tightly closed plastic container and freeze it at less than 10 C 6 Hydrochloric Acid 1 2 N 1 L Hydrochloric Acid ais o te ER HERO e tA Eg 100 ml concentrated FW 36 46 Deionized Water Cautiously while stirring add 100 ml of hydrochloric acid to approximately 800 ml of deionized water contained in a 1 L volumetric flask Dilute the solution to the mark with deionized water and mix it well Filter to 0 45 um Store the solution in a plastic container 7 Working Stannous Chloride Reagent Stock Stannous Chloride od RI Fed aee neta 2 0 ml Hydrochloric Acid 2N qu od n deb d mapa aoe 100 ml Mix together 2 0 ml of stock stannous chloride and 100 ml of 1 2 N hydrochloric acid in a plastic container Prepare the reagent fresh daily 8 Startup Shutdown Solution Add 2 ml of 15 SLS per 100 ml of deionized water 9 Artificial Seawater ASW 4 L Sodium Chlorides anii tend mbar uat 128 5 g NaCI FW 58 44 Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod
35. 13 WN132 3 19 2013 WN133 4 9 2013 WN134 5 14 2013 WNI35 6 18 2013 WN136 7 23 2013 WNI137 8 20 2013 WN138 9 3 2013 WN139 10 22 2013 Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay Figure 1 2 Sampling locations in CCB and SBNMS Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 1 5 Quality Objectives and Criteria for Measurement Data The parameters measured and the concentration reporting units are listed in Table 2 3 1 5 1 Quality Objectives Data quality objectives are as follows e To determine if the eutrophication status of Cape Cod Bay has a long term response to nutrients from the MWRA outfall and or to other regional forcing e To ensure that the sample results are representative of the location sampled e To ensure that the sample results are accurate 1 5 2 Measurement Performance Criteria The first objective will be met by examining data collected during these 9 surveys to measure water column parameters quantify nutrients and chlorophyll and document changes in phytoplankton and zooplankton community structure The second objective will be met by repeated measurements collected at the same locations over time to quantify the variability of results at each station The third objective will be met by analyzing laboratory replicates to ensure reproducibility of results Definitions of quality control samples are provided in
36. 3 times f Stock Imidazole Buffer Fill the OTCR with Stock Buffer The reactor should be stored with stock buffer when not in use D Installation of the OTCR The analytical cartridge is provided with a jumper of 0 034 ID polyethylene sleeved at both ends in the position where the OTCR is to be installed 1 With the N 13 nipple in place pump reagents segmented with nitrogen until a stable flow is established NOTE working buffer must be the cartridge before the OTCR is installed 2 Turn the pump off and disconnect the N 13 in the jumper connection 3 Install the OTCR in the jumper attaching each free end with one N 13 nipple 4 Resume pumping and wait until a stable bubble pattern is established before proceeding with the determinations E Removal of the OTCR 1 Before the reagent lines are removed from the reagents stop the pump remove the OTCR and reconnect the N 13 nipple in the jumper connection 2 Resume pumping Place the reagent lines in Startup Shutdown solution and pump until the cartridge has been thoroughly rinsed 3 Attach the syringe to the N 13 nipple on the OTCR Draw 10 to 15 ml of Stock Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 39 Buffer through the OTCR Leaving buffer in the OTCR remove the syringe and join the tubing ends with the N 13 nipple NOTE Do not leave any air in the OTCR It must be stored filled with Stock Buffer
37. C and sample vials are boiled gently for 15 minutes After 15 minutes the vials are cooled to room temperature overnight in the water bath with the cover remaining on Note that the tightly capped digests can be stored at room temperature for several days before their nitrogen and phosphorous concentrations are determined as described in SOPs for nitrate nitrite and ortho phosphate G Operation Procedure Follow procedure described in SOPs for nitrate nitrite and ortho phosphate with one exception the imidazole buffer used in the nitrate nitrite analysis should be replaced with an ammonium chloride buffer H References 1 Ameel J J Axler and C J Owen 1993 Persulfate Digestion for Determination of Total Nitrogen and Total Phosphorous in Low Nutrient Waters American Environmental Laboratories 10 8 10 2 Green L 2006 Standard Operating Procedure 016 Total Phosphorous and Nitrogen Analysis University of Rhode Island Watershed Watch 3 Oviatt C A and Hindle 1994 Manual of Biological and Geochemical Techniques in Coastal Areas MERL Series Report 1 Third Edition Section 1 6 pp 88 91 Total Dissolved and Total Particulate Nitrogen and Phosphorous The University of Rhode Island Kingston Rhode Island Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 60 Standard Operating Procedure 007 Chlorophyll a Analysis Date Nov 2007 Revision 2 EPA Method 445 0
38. CQUISITION 8 10 2 1 SAMPLING PROCESS DESIGN EXPERIMENTAL DESIGN ceci nennen rennen 10 2 2 SAMPLING METHODS REQUIREMENTS ccce een enne ee eth nares nette te esed esset 11 2 3 SAMPLE HANDLING AND CUSTODY 6 4021 02 1010000 00 000000000000000000000 14 24 ANALYTICAL METHODS 8 2 22 220020000 002 00000000000000001000000000000 15 25 QUALITY CONTROL REQUIREMENTS cccsssscccssssececsesceceesneeecsesaececeeseeceesaeeecsesaececeeseeesesaeeeceesaececseseeseeaeeeenges 17 2 6 PREVENTIVE MAINTENANCE PROCEDURES AND 6 5 6 20 2 7 CORRECTIVE ACTION CONTINGENCIES ccccsesssssececececsesssseceecceceesnsueceeceecseeaasceeececseseeaeeeeecsesesnsaeeeeeceeeeneanees 22 2 8 INSPECTION ACCEPTANCE OF SUPPLIES AND CONSUMABLES 22 2 9 DATA ACQUISITION REQUIREMENTS NON DIRECT MEASUREMENTS scseccesseecssecseesecseeeceaeeeeeaecateaeeneeerenee 23 2 10 DATA MANAGEMENT 25555 n dose loner eost 23 mc cc ASSESSMENT OVERSIGHT t 27 3 1 ASSESSMENTS AND RESPONSE 8 1 1 7 7
39. H20 FW 1235 95 Chloroform FW 119 38 Deionized Water ASTM Type I or II Hydrochloric Acid concentrated FW 36 46 Low Nutrient Seawater LNSW Magnesium Sulfate MgSO4 7H20 FW 246 48 Sodium Bicarbonate NaHCO3 FW 84 01 Sodium Chloride NaCI FW 58 44 Sodium Hexafluorosilicate Na2SiF6 FW 188 06 Sodium Lauryl Sulfate SLS CH3 CH2 10CH20SO3Na FW 288 38 Stannous Chloride SnClI2 2H20 FW 225 65 Sulfuric Acid concentrated H28O4 FW 98 08 Tartaric Acid H2C4H406 FW 150 09 See Operating Notes for information on matrix choices NOTE Chemicals should be of ACS grade or equivalent Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 70 Reagent Preparation 1 Sodium Lauryl Sulfate SLS 15 w w Sodium Lauryl eius 156 CH3 CH2 10CH20SO3Na FW 288 38 Deionized Walter x eo S eee eie de ete noted eese toe Sixes 85 ml Dissolve 15 g of sodium lauryl sulfate in 85 ml of deionized water contained in 250 ml Erlenmeyer flask It may be necessary to warm the mixture in a water bath to dissolve 2 Stock Molybdic Acid 1 L Ammonium Molybdate eerte teda in 10 8g NH4 6M070O24 4H20 FW 1235 95 SULU AGIA c n Stack 2 8ml H2S04 concentrated FW 98 08 Deionized Water While stirring cautiously add 2 8 ml of sulfuric acid to approximately 900 ml of deionized water contained
40. NMFS Right Whale Early Warning System Coordinator who manages the Clearinghouse and her numbers are 508 495 2264 work 508 495 2393 fax and pager 508 585 8473 Please report your name agency and phone numbers at which you can be contacted The vessel s name the date time and location of the sighting the numbers of whales sighted and any other comments that may be of importance If a camera or video camera is available please take some photographs These photographs should be provided to Pat Gerrior or Dan McKiernan Massachusetts Division of Marine Fisheries They will in turn send copies to the New England Aquarium for comparison to the Right Whale Photo Identification Catalog Please remember that Massachusetts has Right Whale Conservation Regulations 322 CMR 12 00 which establishes 500 yard buffer zone surrounding a right whale Vessels shall depart immediately from any buffer zone created by the surfacing of a right whale Physical Contact with a Whale Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 90 If a vessel owned by the Commonwealth of Massachusetts or under contract with the Commonwealth of Massachusetts comes into physical contact with any whale it should be noted in the vessel s logbook The vessel s logbook should include the time and location of the incident weather and sea conditions vessel speed the species of whale struck if known the nature of any injures to crew and or the
41. Quality Assurance Project Plan QAPP for Water Quality Monitoring in Cape Cod Bay 2012 2013 Massachusetts Water Resources Authority Environmental Quality Department Report 2013 09 Citation Costa A Larson E Stamieszkin K 2013 Quality Assurance Project Plan QAPP for Water Quality Monitoring in Cape Cod Bay 2011 2012 Boston Massachusetts Water Resources Authority Report 2013 09 90 p Combined Work Quality Assurance Project Plan QAPP for Water Quality Monitoring in Cape Cod Bay 2012 2013 Prepared by Amy Costa Elizabeth Larson Karen Stamieszkin Provincetown Center for Coastal Studies Hiebert Marine Laboratory 5 Holway Avenue Provincetown MA 02657 508 487 3623 February 1 2012 Combined Work Quality Assurance Project Plan QAPP for Water Quality Monitoring in Cape Cod Bay Prepared by Provincetown Center for Coastal Studies 5 Holway Ave Provincetown MA 02657 Program Laboratory and Database Manager Dr Amy Costa Director Cape Cod Bay Monitoring Program Provincetown Center for Coastal Studies 508 487 3623 Field Coordinator Date Capt Marc Costa Marine Operations Provincetown Center for Coastal Studies 508 246 1387 Laboratory Quality Assurance Date Elizabeth Larson QA Coordinator Provincetown Center for Coastal Studies 508 487 3623 Date Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay Dist
42. RGANIZATIONAL CHART FOR WATER QUALITY MONITORING IN CAPE COD FIGURE 1 2 SAMPLING LOCATIONS IN CCB AND Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 1 0 Project Management 11 Project Organization Figure 1 1 presents the project management structure for the Water Quality Monitoring Program in Cape Cod Bay for MWRA This plan details the project organization sample handling sample analysis and data loading for this program Executive Director PCCS Rich Delaney Program Manager Lab Manager Database Manager Amy Costa QA Officer Elizabeth Larson Field Coordinator Marc Costa Figure 1 1 Organizational Chart for Water Quality Monitoring in Cape Cod Bay Dr Amy Costa is the PCCS Director of the Cape Cod Bay Monitoring Program and will fill a number of roles including Program Manager Laboratory Manager and Database Manager As Program Manager she will oversee all aspects of the project that incorporate the monitoring program including fiscal management project objectives data uses and program changes As Laboratory Manger she will perform lab analyses according to QAPP and ensure correct procedures are used holding times are met and adequate documentation is provided As Database Manger she will maintain the data systems for the program perform oversee data entry and check entries
43. These sleeves are joined by a N 13 N 2 nipple B Reagents for OTCR Activation 1 Stock Imidazole Buffer 2 Copper Sulfate Solution 3 1 0 N Hydrochloric Acid 100 ml Hydrochloric Acid concentrated Gate tem tated asus 8 3 ml FW 36 46 Deionized Water Add 8 3 ml of concentrated hydrochloric acid to about 70 ml of deionized water contained in a 100 ml volumetric flask Dilute to the mark with deionized water C Procedure NOTE Do not introduce air into the cadmium tube during this process Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 38 1 Detach one end of the polyethylene tubing from the N 13 N 2 nipple 2 Using a 10 cc plastic syringe fitted with 0 040 ID PVC tubing and a short 0 034 ID polyethylene extension flush the OTCR with the described solutions using the following procedure a Deionized Water b 1 0 N Hydrochloric Acid CAUTION The hydrochloric acid may cause pitting of the cadmium reactor interior surface if left in the OTCR for longer than a few seconds After the flush proceed quickly to Step C c Deionized Water d 2 Copper Sulfate Slowly flush the OTCR with 10 cc of 2 copper sulfate Repeat Precipitated copper may be observed exiting the reactor black particles e Deionized Water Flush with deionized water until no more precipitated copper is flushed from the reactor This requires a forceful flush Repeat 2
44. a analysis activities data will be archived electronically and backed up online Hard copies of field and lab notebooks will be archived in the vault located the basement of the Hiebert Marine Laboratory Hard copies of data will be kept for at least one year following the termination of the contract 1 7 1 Document Control PCCS will maintain documents relevant to laboratory analysis activities and data entry A copy of the most current analyses SOP is kept in the lab area where the analysis is being performed This document references the SOP number without the revision number All members of the project team will inform the PCCS QA Officer of the need for SOP revisions Document Control is the responsibility of the Program Manager Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 10 1 7 2 Laboratory Analyses Records All data will be recorded initially into bound laboratory logbooks onto established data forms Appendix B or onto electronic file where applicable 1 7 3 Records Retention and Storage All data will be archived electronically and backed up online Recent hard copies of field and lab notebooks will be kept in the designated file cabinet in the Coastal Ecology Lab in the Hiebert Marine Laboratory Archived records will be stored in the data vault located in the basement of the Hiebert Marine Laboratory for at least one year following the termination of the contract 1 7 4 T
45. and cuvette holder will be cleaned with a water dampened cotton swab or soft cloth All components will be dried thoroughly before reassembling 2 6 3 Maintenance for Direct Q3 The Direct Q3 is used to produce Milli Q water referred to in Section 2 2 1 2 1 and recommended in section H of the SOP for Ammonia At least once a year or more frequently as needed the SmartPak filter cartridge and final filter will be replaced and the system and tank will be sanitized with 30 Hydrogen Peroxide solution 2 6 4 Maintenance for Plankton Collection and Analysis Equipment 2 6 41 Plankton Collection Equipment The chamber inside the General Oceanographic Environmental flowmeters are filled with fresh water before every research cruise so that minimal air is left inside the chamber they are also checked for ease of rotation and corrosion The nets used for zooplankton collection are checked for holes before each research cruise Small holes are filled using a glue product called Zap a gap The cod ends on the zooplankton collection nets are checked for holes in the mesh before every research cruise Should a hole be found the mesh is replaced if the mesh starts to separate from the plastic it is glued back down using PVC cement 2 6 4 2 Plankton Analysis Equipment Fluorettes are checked for holes in the mesh or separation of the mesh from the plastic before every research cruise If holes are found the mesh is replaced if the mesh is separati
46. and the formula for calculating chlorophyll a in samples is determined The solid secondary standard is analyzed with each batch of samples Blanks of 90 acetone and an unused filter extracted Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 18 with 90 acetone are set up with each rack of samples 2 5 1 4 Net and Flowmeter The net used for zooplankton collection and the flowmeter will be rinsed with fresh water and inspected for damage following each survey Additionally the flowmeter will be calibrated annually to attain the most accurate correction constant possible 2 5 2 Data validation reporting and verification 2 5 2 1 Analytical Methods Data Evaluation Both the Laboratory Manager and the QA Officer will review data to determine if it meets the quality assurance objectives Table 2 3 Decisions to qualify or reject the data will be made by the Laboratory Manager and the QA Officer and if required corrective actions will be implemented as outlined in Table 2 4 and Table 2 5 Table 2 3 Data quality objectives Range 80 120 recovery for QC std and lab 0 1 uM if less than 0 5 uM or 20 0 05 0 10 fortified matrix RPD if more than 0 5 Ortho M 100210 3 80 120 recovery for std and lab 0 05 uM if less than 0 1 uM or 20 Phosphate H fortified matrix RPD if more than 0 luM _ 80 120 recovery for QC std and lab 0 1 uM if less than 0 5 uM or 20 ene fortified mat
47. anumeric maximum 4 characters Code for the unit of UNIT CODE alphanumeric maximum 12 measurement characters Code for method METH CODE alphanumeric maximum 13 characters Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 27 Description Field Required Data type amp format Field Number assigned by the LAB SAMPLE ID alphanumeric maximum 35 laboratory to the sample characters Comments on the record COMMENTS alphanumeric maximum 150 characters 3 0 Assessment Oversight 3 1 Assessments and Response Actions 3 1 1 Performance Audit The QA Officer will conduct an initiation audit and as needed laboratory and field inspections to ensure that laboratory analyses and data recording and entry are carried out in accordance with this QAPP Deviations from the QAPP will be reported directly to the Program Manager and the appropriate corrections will be made All deviations will be noted in the respective field notebook lab notebook or electronic file and tracked by the QA Officer 3 1 3 Corrective Action All field and laboratory personnel share responsibility for identifying and resolving problems encountered in the routine performance of their duties The Program Manager will be responsible for identifying and resolving any problems that have not been adequately addressed by technical personnel as well as any problems that require changes in this QAPP and or
48. ase contrast optics Phytoplankton abundance is calculated by dividing the number of cells counted by the volume examined in a gridded Sedgwick Rafter chamber The theoretical maximum possible volume that would be examined would be an entire Sedgwick Rafter chamber 1 ml The grid subdivides the chamber into ul divisions so that if an entire chamber is not counted an exact volume can still be determined Typical volumes counted are one row of the chamber 50 1 cells or 1 20 of 1 ml The volume of sample examined is dependent on number of cells encountered and how long it takes to reach cut offs of 75 entities unicellular forms colonies or chains of each of the top 3 taxa and 400 entities total Calculation of abundance also accounts for the concentration factor used in the settling process Normally the volume processed is 800 ml of whole water sample settled to 50 ml of concentrate for a 16 1 ratio The following equation results in the abundance estimate for cells counted Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 64 C Vs Vc 1000 Vror cells L where C cells counted Vs Volume of concentrated sample Vc Volume of sample examined Original volume Final abundance estimates will be reported in units of 10 cells per liter Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 65 References Borkman D 1994
49. ation 1 Sodium Lauryl Sulfate SLS 15 w w Deionized Water o oen dot DP EUR dudum qu eed 85 ml Sodium Lauryl 65 2 hie atic 156 2 gt 5045 FW 288 38 Dissolve 15 g SLS in 85 ml deionized water contained in a 250 ml Erlenmeyer flask Gentle warming may be needed for complete dissolution 2 Sulfuric Acid 5 N 1000 ml CAUTION Mixing sulfuric acid with water generates a great amount of heat Sulfuric Acid concentrated 2 20000000 00000000 140 ml H5SO FW 98 08 Deionized Water Cautiously add 140 ml concentrated sulfuric acid to 600 ml deionized water contained in a 1000 ml Erlenmeyer flask Cool to room temperature and transfer to a 1000 ml volumetric flask Dilute to the mark with deionized water 3 Antimony Potassium Tartrate 50 ml Antmiony seco ode tag taedet 0 15g KoSb2CgH4O12 3H20 FW 667 87 Deionized Water Dissolve 0 15 g antimony potassium tartrate in 40 ml deionized water contained in a 50 ml volumetric flask Dilute to the mark with deionized water Store at 2 8 C in a dark bottle 4 Ammonium Molybdate 150 mI Ammonium Molybdate eoe ett ee e ed ote b EAM es 6g NH 4 6Mo7024 4H20 FW 1235 86 Deionized Water Dissolve 6 g ammonium molybdate in 75 ml deionized water Add deionized water to final volume of 150 ml and mix well Store at 2 8 C in a polyethylene bottle 5 Ascorbic Acid 300 ml Provi
50. available Disadvantages 1 The chemical factors may be different than in salt solution salt effect Artificial Seawater Solution and or Deionized Water Sodium Chloride Solution Advantages 1 Salt effects on the chemical factors are minimized 2 Sodium chloride solution is easy to prepare and is not expensive Disadvantages 1 Ammonium impurity is quite large in sodium chloride 2 Large quantities of sodium chloride are sometimes required Low Nutrient Seawater Advantages 1 Salt effects are eliminated 2 In certain regions of the ocean it is easily obtained Disadvantages 1 Italways contains some nutrients 2 f not used immediately it must be filtered to remove any particulate matter 3 Often it is difficult to obtain when working in eutrophic waters 4 Storage is difficult so large quantities are not easily obtained 4 stated above the system is optimal when the sample matrix is carried over into the sampler wash solution and the standards If this is not possible i e if deionized water is used for the Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 43 sampler wash and or calibrants it is advisable to check for refractive index disturbance effects This can be accomplished by removing the sodium hypochlorite reagent After the initial sample run is finished place the data collection in pause replace the hypochlorite reagent with deionized water
51. baseline 9 Load the sampler tray with calibrants blanks samples and QC or monitor samples 10 Select the appropriate parameters for the detector and sampler See Flow Diagram 11 Begin analysis 12 At the end of analysis place all reagent lines in startup solution and turn off heat bath Pump startup solution for 20 to 30 minutes to flush all of the reagents out of the cartridge and to allow the heat bath to cool Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 54 13 Release pump platens and turn off the power to all units 14 Close the nitrogen pillow I Operating Notes See Nitrate Nitrite Analysis SOP for information on sample matrices 1 Prepare ammonia free water by passing distilled water through a mixture of strongly acidic cation and strongly basic anion exchange resins 5 2 To prevent ammonia contamination from the air segment the analytical stream with nitrogen or draw air through a 5 N sulfuric acid solution 3 If bubbles are sticking in a debubbler cleaning the debubbler will allow bubbles to escape smoothly out the debubble line Bubbles sticking in the debubbler can cause a loss in the overall precision of the peak height To clean soak the debubbler for 2 3 hours in a mixture of 20 30 Contrad NF API p n 80 0007 04 and hot tap water Rinse thoroughly 4 If the flowrate of the sample pump tube is lt 226 ul minute a blk blk pump tube a helper line must be added w
52. bias of the applied analytical method External standard USGS Standard Reference Nutrient Samples Table 2 5 Laboratory Analytical QC Chlorophyll a Method SOP Measurement QC Frequency QC Acceptance Corrective Responsible for P rform nc Number un Action Corrective Criteria Action ius 1 per set of 20 lt MDL pru Lab Manager lt MDL 1 per set of 20 lt MDL ipae Ls Lab Manager lt MDL 0 Laboratory lt 20 RPD Qualify Lab Manager lt 20 RPD Duplicate samples External 90 110 90 110 Standards 1 per set of 20 ERY Qualify Lab Manager coer Internal standard a known amount of a standard added to a test portion of a sample and carried through the entire determination procedure as a reference for calibrating and controlling the precision and bias of the applied analytical method External standard either a liquid primary chlorophyll a standard provided by Turner Designs or a solid secondary standard 2 5 2 2 Plankton Analyses 2 5 2 2 1 Whole Water Phytoplankton Counts of 400 phytoplankton cells will provide a precision of 10 of the mean Guillard 1973 Therefore a minimum of 400 entities solitary single cells chains or colonies will be tallied for each sample Unicellular forms e g Cryptomonas spp microflagellates aggregate forms e g Phaeocystis pouchetii and chained forms e g Skeletonema spp will each count as one entity towards the 400
53. cate Total phosphorous Nucleopore filter freeze filtrate in 100 ml whirl pak until analysis 28 days Pass sample through Whatman GF F Wrap filter in foil 28 days and freeze until analysis 2 2 2 Sampling Measurement System Failure Response and Corrective Action Process Ortho phosphate HDPE bottle Chlorophyll a Phaeophytin Preserve with Uterm hl s solution Phytoplankton Whole Water Wide mouth HDPE bottle volume dependent on zooplankton density Wash into jar Fix with formalin to 10 solution Zooplankton Net Tow Dependent on zooplankton density Corrective action in the field may be necessary when the sampling schedule is disrupted due to weather or other logistical difficulties or when sampling procedures or field analytical procedures require modification due to unforeseen circumstances Any corrective measures taken must be approved by the Program Manager It is the responsibility of the Program Manager to ensure that the corrective measure has been implemented Corrective actions will be documented in the field logbook Corrective action in the laboratory may occur at one of several phases of the analytical process Conditions such as broken or contaminated sample containers may be identified during sample login or prior to analysis The Laboratory Manager will identify the need for corrective action and consult with Provincetown Center for Coastal Studies QAPP Water Qualit
54. d Estuarine Zooplankton of the Gulf of Maine Region Freeport Freeport Village Press 2000 Johnson WS and Allen DM Zooplankton of the Atlantic and Gulf Coasts Baltimore Johns Hopkins University Press 2005 Smith DL and Johnson KB A Guide to Marine Coastal Plankton and Marine Invertebrate Larvae Dubuque Kendall Hunt Publishing Company 1996 Todd CD Laverack MS and Boxshall GA Coastal Marine Zooplankton Cambridge Cambridge University Press 1996 Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 69 Standard Operating Procedure 010 Silicate Analysis Date Sep 2002 Primary Method EPA 366 A Scope and Application This method is used for the determination of silicate in seawater and is applicable to many ranges B Summary of Method Silicomolybdic acid is formed by the reaction of silicate with molybdic acid The silicomolybdic acid is reduced by stannous chloride to form molybdenum blue with an absorbance maximum at 820 nm C Interferences Interference from orthophosphate and tannin is eliminated by the use of tartaric acid Filter turbid samples before determination Color absorbing at the analytical wavelength will interfere D Sample Handling and Preservation Collect samples in plastic containers Analyze samples as soon as possible Refrigerate samples at 2 8 C 1f immediate analysis is not possible E Raw Materials Required Ammonium Molybdate NH4 6M070O24 4
55. d or frozen in subsample containers depending on the analyte for storage until analysis Plankton samples are preserved on board vessel See Table 2 1 for a summary of storage methods and holding times 2 4 22 Analytical Methods Table 2 2 summarizes the methods used for sample analysis The analyses will be conducted as described in the SOPs listed with are based on literature references or EPA methods Table 2 2 Methods of detection for analytes Parameter Instrument SOP Analysis Method Total nitrogen SOP 004 USGS 03 4174 Asteria SOP 001 353 4 Autoanalyzer SOP 003 EPA 350 1 Total phosphorous SOP 004 USGS 03 4174 Chlorophyll a ug L Turner Trilogy SOP 005 Modified EPA 445 0 Phaeophytin Olympus BH 2 mi ENE ith Borkman 1994 Borkman et al Phytoplankton Whole Water 1993 Turner et al 1995 phase contrast optics 3 Leica L2 2 4 2 1 Dissolved and Total Inorganic Nutrients The analysis of dissolved inorganic nutrients is based on the cited EPA Dissolved inorganic nutrient concentrations are determined for samples that have been passed through a 0 4 um pore size membrane filter in the field The concentrations of nitrate nitrite ortho phosphate ammonia silicate total nitrogen and total phosphorous are measured colorimetrically on an Astoria 2 Autoanalyzer This instrument automates standard manual techniques for analysis of nutrients Provincetown Center for Coastal Studies QAPP
56. d organic nitrogen to nitrate and hydrolyzes all forms of inorganic and organic phosphorous to ortho phosphate After digestion samples are analyzed as described for nitrate nitrite and ortho phosphate 2 4 2 2 Chlorophyll a and Pheophytin Samples for chlorophyll a phaeophytin are processed according to EPA method 445 0 using a Turner Trilogy Fluorometer Samples are filtered in the field as soon as possible after collection and the filters stored at 10 C All handling steps are performed in subdued light The chlorophyll a phaeophytin is extracted from the cells retained on the GF F filter by a 16 24 hour steep in 90 acetone at 4 C The extract is analyzed using a fluorometer 150 uL of 0 1 N HCl is added to the extract and the extract is remeasured after 90 seconds to determine phaeophytin concentrations 2 4 2 3 Whole Water Phytoplankton Uterm hl s preserved whole seawater samples will be prepared for analysis by concentrating the sample by gravitational settling as described by Borkman 1994 Borkman et al 1993 and Turner et al 1995 Samples will be settled in graduated cylinders with no more than a 5 to 1 height to width ratio Phytoplankton abundance is calculated by dividing the number of cells counted by the volume examined in a gridded Sedgwick Rafter chamber The theoretical maximum possible volume that would be examined would be an entire Sedgwick Rafter chamber 1 ml The grid subdivides the chamber into ul divisions so that
57. d verify a stable baseline Once the reagent baseline is satisfactory add the OTCR into the cartridge flow Always connect the inlet first and the outlet second It is important to avoid the introduction of air into the coil during this procedure Once the OTCR is on line run for 5 10 minutes and then re verify the bubble pattern and baseline stability Make any necessary adjustments Load the sampler tray with calibrants blanks samples and QC or monitor samples Select the appropriate parameters for the detector and sampler See Flow Diagram at the end of methodology Begin analysis At the end of analysis remove the OTCR from the cartridge Disconnect the outlet first then the inlet Flush the OTCR with buffer which contains no surfactant TX 10 Place all reagent lines in startup solution Pump for 5 to 10 minutes to flush all of the reagents out of the cartridge Turn off the power to all units and release pump platens H Operating Notes 1 OTCR may be conditioned by running a mid scale standard through the manifold for 10 15 minutes Life expectancy of the OTCR varies and is difficult to predict It is recommended that a nitrite standard of the same nominal concentration as the high scale standard be run as a check on column reduction efficiency There are special considerations when running seawater samples on any flow system A Standards Primary standards should be prepared from the best grade
58. dense the process is repeated Sample Enumeration and Identification Once the desired subsample is in the watch glass it is placed under a Leica L2 dissecting microscope Light source and zoom adjustments are dependent on the personal preferences of the individual counting and identifying the organisms An Interface Systems 20 channel digital counter is used to enumerate the organisms as they are identified A number of keys and guides to Gulf of Maine zooplankton are used see zooplankton identification references 35 types of organisms are identified to a particular taxonomic level and some are staged see zooplankton lab datasheet for details As the individual identifying and enumerating counts an organism he or she moves it aside so that no organism is counted more than once If organisms are floating they can be removed and then counted after the rest of the sample has been finished for ease of accurate enumeration and identification Once all organisms in the subsample have been identified enumerated and recorded with the digital counter and paper should there be more than 20 taxa identified the data on the digital counter are recorded onto the zooplankton lab datasheet If less than 200 organisms have been found to make up the subsample another 5 ml subsample is taken processed and added to the previous subsample counts this may be done as many times as necessary unless the volume of the sample being subsampled is no long
59. e farfield stations selected by MWRA as part of their on going program to monitor for possible impacts of the MWRA outfall on areas downstream These stations have been monitored since 1992 giving both 9 years of baseline data and 9 years of post outfall data Although no statistically significant changes in water quality at these stations can be linked directly to Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay the outfall it is necessary to continue to monitor these stations Furthermore continued monitoring of CCB and SBNMS is important because these stations being in the farfield place the contribution or lack thereof of the outfall to such trends in a larger spatial context The continued monitoring and assessment of conditions in these areas is important to the conservation of right whales and to our understanding of the influential patterns of change to which the outfall may be contributing This study includes 3 sampling locations in the farfield Figure 1 2 sampled nine times a year Water quality monitoring at these stations includes measurements of surface PAR temperature salinity dissolved oxygen fluorescence PAR nutrient concentrations dissolved and total nitrogen and phosphorous silicate phytoplankton biomass chlorophyll a and phaeophytin and phytoplankton and zooplankton identification and enumeration Sampling locations are listed in Table 1 2 samples collected at
60. each location are listed in Table 1 3 and proposed sampling schedule is outlined in Table 1 4 Table 1 2 Sampling locations of the water quality monitoring stations Station Id Description Target latitude Target longitude Average water depth m F01 East CCB 41 85083 70 4533 26 2 F02 West CCB 41 90817 70 2283 32 8 F29 South SBNMS 42 11667 70 29 64 7 Table 1 3 Routine measurements to be conducted at the three stations Type of measurement Depth Parameter Surface PAR Hydro profile From near surface approximately Temperature 0 5 1 5 m to near bottom 3 5 m Salinity from bottom Profiling at 0 5 m Dissolved oxygen intervals Depth of sensor Chl fluorescence PAR Water chemistry Two depths Nitrate nitrite Near surface Ammonia Near bottom Ortho phosphate Silicate Total nitrogen Total phosphorus Phytoplankton Near surface Extracted chl Enumeration Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay Zooplankton Oblique net tow identification Enumeration Identification Table 1 4 Sampling schedule for CCB and SBNMS water quality monitoring Survey Proposed sampling 2012 WNI121 2 7 2012 WN122 3 20 2012 WNI123 4 10 2012 WNI24 5 15 2012 WNI25 6 19 2012 WN126 7 24 2102 WN127 8 21 2012 WN128 9 4 2012 WN129 10 23 2012 2013 WNI3I 2 5 20
61. echnical Workshop The results of the year s monitoring will be presented at the MWRA s annual technical workshop conducted in the spring The technical workshops are typically scheduled for March or April and conducted in Duxbury Woods Hole or Boston Following the completion of the workshop MWRA will be provided with a digital copy of the Power Point slides and a two page abstract describing the major results of the year 2 0 Measurement Data Acquisition 2 Sampling Process Design Experimental Design 2 1 4 Scheduled Project Activities Including Measurement Activities The CCB and SBNMS surveys will be performed on an ongoing basis as specified in this QAPP These stations have been sampled since 1992 with only slight changes in sampling frequency It is anticipated that this project will include 9 surveys per year between February and November 2 1 2 Design Rationale The objective of this project is to continue to monitor for changes in water quality in CCB and SBNMS since the transfer of wastewater discharges offshore to Massachusetts Bay The evaluation of water quality changes due to the transfer of discharges offshore will be assessed through the measurement of nutrient and chlorophyll concentration and changes in plankton assemblages among others 2 1 3 Design Assumptions Since Cape Cod Bay is generally well mixed in cold months and has a well defined pycnocline throughout the warmer months samples collected near surface and nea
62. ed water These reagents must be high quality reagent grade to avoid excessive nutrient or trace metal contamination 6 Startup Shutdown Solution e 1 2 ml Deionized water Add 1 2 ml Brij 35 to 1 L of deionized water Mix well G Calibrants See Nitrate Nitrite Analysis SOP for information on calibrant preparation H Operation Procedure 1 Set up the cartridge as shown in the flow diagram Check all tubing and connections Replace if necessary 2 Place reagent lines in startup solution 3 Turn on power to all units including heat bath Latch platens to begin liquid flow Open nitrogen pillow 4 Verify that the bubble size and spacing is consistent throughout the cartridge If the bubbles are splitting up as they enter or exit a coil or heat bath check and replace any suspect fittings The bubbles should flow smoothly without dragging If dragging is observed add more Brij 35 to the startup solution 5 Check all reagent containers on the instrument for particulate matter Be sure all containers are properly labeled and filled before pumping reagents Filter to 0 45 um if necessary 6 After heat bath has reached desired temperature and a stable baseline has been verified using startup solution place reagent lines in appropriate reagent containers 7 Open data collection software and set up the appropriate sample table 8 Allow reagents to run for 10 to 15 minutes and verify a stable
63. ent 250 ml o phthaldialdehyde Teac di ten i c Ete 0 2g C8H602 FW 134 1 Borate buffer s lution s dune ole 250 ml Sodium sulfite solutioti 1 onset 0 5 ml Add 0 2 g o phthaldialdehyde to about 125 ml of borate buffer solution contained in a 250 ml Erlenmeyer flask and add a magnetic stir bar Stir solution using a stir plate until OPA is dissolved Transfer solution to a 250 ml graduated cylinder Add 0 5 ml of sodium sulfite solution Dilute to the 250 ml mark with buffer solution and mix well Add 1 ml of Brij 35 Prepare as needed See Operating Note 79 for alternate preparation instructions 4 Sampler Wash Solution Artificial Seawater See Operating Note 13 CAUTION o phthaldialdehyde is light sensitive Avoid prolonged exposure to light 5 Artificial Seawater ASW 4 L See Operating Notes Sodium nies 128 56 NaCl FW 58 44 Magnesium Sulfate iocis ec 28 56 Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 53 MgS04 7H20 FW 246 48 Sodium 1 ecole 0 6726 NaHCO3 FW 84 01 Deionized Water Dissolve 128 5 g of sodium chloride 28 5 g of magnesium sulfate and 0 672 g of sodium bicarbonate in approximately 3 L of deionized water Dilute to 4 L with deioniz
64. er enough in which to completely submerge the pipette chamber If this occurs the individual enumerating must begin again When taking additional subsamples no water or organisms can be added to the total sample being subsampled Upon counting 200 organisms or more the recorded subsample volume counted is adjusted to reflect the number of ml counted After the count has been completed and recorded the entire sample is transferred back into a fluorette and then back into the sample jar Formalin is added in a volume dependent on the sample far size Table 1 and water is added to fill the sample jar to the top The point of contact between the sample jar and sample lid is wrapped in Parafilm and the sample is archived Zooplankton Density Calculations The following formula is used for calculating the org m from the oblique net tow count data Org m x V V o x ms Cy Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 68 Where is the counted organisms is the total sample volume Vc is the counted sample volume mz is the flow meter end reading ms is the flow meter start reading and Cy is the net constant Table 1 Sample jar volume and volume of formalin added for sample archiving Jar size ml Formalin added ml 40 3 75 80 6 175 12 310 325 22 Zooplankton Identification References Gerber RP An Identification Manual to the Coastal an
65. er to a final volume of 1 L 2 2 1 2 5 Zooplankton Zooplankton samples are collected using a standard 60 cm diameter 333 um mesh conical net fitted with a General Oceanics helical flow meter A vertical oblique net tow will be conducted at each station to sample for zooplankton Collections will be initiated by vertically dropping the net on station When the net has dropped the full 19 meters the net will be pulled obliquely through the water column by the boat until a mark on the rope reaches the surface indicating that the net is now horizontal at the surface of the water column At this point the net will be retrieved Once on board the samples will be washed Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 13 from the nets carefully with a sea water hose concentrating the sample into the bottom of the net to the collection bucket From there it will be concentrated further into a 333 um mesh fluorette This concentrated sample will be rinsed into a sample jar and preserved with 10 buffered formalin Samples will be placed in a cooler until transferred to the lab Table 2 1 Sample collection and storage Maximum Holding Time to Analysis Analytical Sample Parameter Volume per analyte Sample Container Sample Processing Decant into 30 mL polypropylene bottle and freeze until analysis Total Nitrogen 28 days Total Phosphorus Nitrate Nitrite Pass through Ammonia Sili
66. es after adding the other reagents This will allow the tartaric acid to reach the cartridge first If using data collection software set up the appropriate sample table Allow reagents to run for 5 to 10 minutes and verify a stable baseline Load the sampler tray with calibrants blanks samples and QC or monitor samples 15 Select the appropriate parameters for the detector and sampler See Flow Diagram 16 Begin analysis 17 At the end of analysis place all reagent lines in startup solution Pump startup solution for 10 to 15 minutes to flush all of the reagents out of the cartridge 18 Turn off the power to all units and release pump platens I Operating Notes 1 The use of glass containers should be avoided Prepare all reagents and calibrants in plastic containers or transfer all reagents and calibrants to plastic containers immediately following preparation Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 74 2 The powdered stannous chloride SnCI2 2H20 should be stored frozen atless than 10 C Allow to come to room temperature before opening Prepare fresh working stannous chloride if unstable baselines poor peak shapes or reduced sensitivity are experienced PolyFlow tubing APIp n303 2674 01 1s used for transmission tubing on this cartridge to help achieve smooth flow and reduce carryover High quality SLS is important Fisher catalog numbers 02674 25
67. et al May 1986 ACKNOWLEDGEMENTS Astoria and FASPac are trademarks of Astoria Pacific Inc Clackamas Oregon Dowfax 2A 1 is a trademark of Dow Chemical USA Contrad NF and Neutrad are registered trademarks of Decon Labs Inc Bryn Mawr Pennsylvania Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 51 Standard Operating Procedure 005 Ammonia Fluorometric Date Nov 2011 Revision 1 Primary Method EPA 350 1 A Scope and Application This method is used for the determination of ammonia in seawater The applicable range of this method is 0 05 to 5 uM B Summary of Method The sample is mixed with o phthaldialdehyde and sodium sulfite in a borate buffered solution at 75 C After sufficient mixing the sample concentration is measured by fluorescence spectroscopy using 360nm excitation and 420 470nm emission wavelengths The increase in fluorescence is directly proportional to the ammonia concentration C Interferences Inorganic salts can have a depressive effect1 Copper 6 gt 300ug L Iron 0 5 1 3mg L Mercury 5 10mg L Sulfide 2 3 gt 10uM Particulate matter should be removed or centrifuged to prevent clogging in the system D Sample Handling and Preservation Samples should be analyzed directly Samples should be frozen as soon as possible if not analyzing immediately E Raw Materials Required Ammonium Sulfate NH4 2SO04 FW 132 15
68. for accuracy against field and lab forms Capt Marc Costa is the Field Coordinator for this project He is responsible for the general coordination of monitoring activities on the water Ms Elizabeth Larson is the QA Officer She is responsible for developing directing and coordinating the quality assurance quality control QA QC program regarding the collection and analyzing of water samples She is also responsible for reviewing laboratory practices and procedures to ensure compliance with quality assurance and safety standards Contact information is provided in Table 1 1 Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay Table 1 1 Contact Information for Water Quality Monitoring Program in Cape Cod Bay Name Title Role Location Email Address Phone Richard Delaney Executive Director PCCS delaney coastalstudies org 508 487 3622 Amy Costa Program Manager PCCS acosta coastalstudies org 508 247 7743 Marc Costa Field Coordinator PCCS mcosta capecod com 508 246 1387 Elizabeth Larson QA Coordinator PCCS elarson coastalstudies org 310 916 6634 f Project Manager Harbor and David Taylor Outfall Monitoring MWRA david taylor mwra state ma us 617 788 4952 12 Communication Plan Amy Costa will be the primary contact for this project Email or telephone calls will be the day to day method of communication Significant technical issues should be documented in e
69. forts will be comparable to data sets of previous years Collection A Niskin bottle will be used to collect surface water at a depth of 1 2 meters at each station A portion of the water from the Niskin sampling bottle 800 mls will be measured with into a clean graduated cylinder that has been thrice rinsed with the sampling bottle water The sample will be mixed with Uterm hl s solution 1 ml Uterm hl s per 100 ml water sampled in a 1 L HDPE bottle and stored in a cooler until it can be further processed in the lab Uterm hl s solution is prepared as described in Guillard 1973 100 g potassium iodide 50 g iodine and 50 g sodium acetate each are dissolved incrementally in distilled water to a final volume of 1 L Sample Preparation At the laboratory the Uterm hl s preserved whole seawater samples will be prepared for analysis by concentrating the sample by gravitational settling as described by Borkman 1994 Borkman et al 1993 and Turner et al 1995 Samples will be settled in glass graduated cylinders with no more than a 5 to 1 height to width ratio The preserved samples are stored at ambient temperature and in the dark until analysis Prior to analysis the 800 ml of seawater will be settled to 50 ml and decanted by low vacuum aspiration Counting and Abundance Estimates One ml of the concentrate will be examined and phytoplankton counted in a gridded Sedgwick Rafter chamber using a Olympus BH 2 research microscope with ph
70. g The Great South Channel east of Cape Cod has also been designated critical habitat because of its importance to the right whale as a feeding area It has been determined that the most significant human induced causes of mortality are ship strike and entanglements in fishing gear Purpose The purpose of this protocol is to give guidance to the vessels owned by the Commonwealth and those operating under contract to the Commonwealth as to proper operational procedures if the vessels should encounter whales i e sighting and reporting procedures and entanglement and carcass reporting protocol Applicability This protocol will apply to all vessels owned by the Commonwealth of Massachusetts and or contracted out by the Commonwealth of Massachusetts Geographic Scope Operational Scope This protocol applies to all applicable vessels operating in or adjacent to Commonwealth waters When vessels are operating in the designated critical habitat areas Cape Cod Bay or the Great South Channel heightened operation is applicable especially during the late winter and spring when the right whales are expected to be located in these areas Sightings of Right Whales The Executive Office of Environmental Affairs and the National Marine Fisheries Service is interested in receiving reports from individuals who observe right whales during vessel operations Reports should be made to the National Marine Fisheries Service Clearinghouse Patricia Gerrior
71. grade solvents Solutions must be assigned an expiration date of 1 year e Distilled water must be collected into cleaned containers and refreshed prior to each survey e Laboratory reagents must be at least reagent grade Dry reagents must be assigned an expiration date of no more than 5 years be stored in a clean dry environment away from light and be traceable to receipt and certificate of analysis Reagent solutions must be assigned an expiration date of no more than 1 year and be stored appropriately The laboratory must maintain a chemical tracking inventory e Laboratory standards must be certified as at least 96 pure or the lot specific analysis purity must be incorporated into calculation of the standard concentration Standards must be assigned an expiration date as received based on the manufacturer s expiration date or a date consistent with laboratory SOPs and stored as recommended by the manufacturer supplies and consumables are purchased from Fisher Scientific Sigma Aldrich or Astoria Pacific Chlorophyll standards are purchased once a year from Turner Designs Nutrient standards are purchased Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 23 yearly from Astoria Pacific Nutrient samples for inter laboratory comparison and internal quality control are purchased twice a year spring and fall from USGS as part of the Standard Reference Sample Program http bqs usgs g
72. group 1 lt 10 microns D p length Pennate diatom sp group 2 10 30 D p microns length Pennate diatom sp group 3 31 60 D p microns length Pennate diatom sp group 4 61 100 D p microns length Pennate diatom sp group 5 gt 100 microns D p length D p Pleurosigma spp D p Pseudonitzschia delicatissma complex D p Pseudonitzschia pungens D p Rhabdonema minutum D p Striatella unipunctata D p Synedra spp D p Thalassionema nitzschioides Din Dino Dinophysis acuminata Din Dino Dinophysis fortii Din Dino Dinophysis norvegica Din Dino Dinophysis tripos Din Dino Phalacroma rotundatum Din Alexandrium fundyense Din Gony Alexandrium spp Din Amylax triacantha Din Gony Ceratium furca Din Gony Ceratium fusus Din Gony Ceratium lineatum Din Gony Ceratium longipes Din Ceratium macroceros Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 83 Din Gony Ceratium tripos Din Gony Gonyaulax spp Din Gony Scrippsiella trochoidea Din Gymn Akashiwo sanguinea Din Gymn Amphidinium crassum Din Gymn Amphidinium spp Din Gymn Gymnodinium sp group 1 5 20 microns width 10 20 microns length Din Gymn Gymnodinium sp group 2 21 40 microns width 21 50 microns length Din Gymn Gyrodinium sp group 1 5 20 microns width 10 2
73. h the water column by the boat until a mark on the rope reaches the surface indicating that the net is now horizontal at the surface of the water column At this point the net is retrieved Once on board the samples are washed from the nets carefully with a sea water hose The sample is concentrated into the bottom of the net to the collection bucket From there it is concentrated further into a 333 um mesh fluorette PVC piping with 333 micron mesh at one end 11 5 cm inside diameter 9 5 cm length This is rinsed into a sample jar and preserved with 10 buffered formalin Samples are then placed into a cooler for the remainder of the cruise Subsampling the zooplankton net samples If the sample is sparse enough the entire sample is enumerated Usually the sample will have to be subsampled To enumerate and identify the zooplankton in a net sample that is to be subsampled all zooplankton are poured into a small fluorette PVC piping with 333 micron mesh at one end 5 cm inside diameter 12cm length and rinsed with fresh water to remove excess formalin Once well rinsed the entire sample is rinsed with fresh water in a squirt bottle into a glass beaker The goal is to subsample 200 organisms in 5 ml of sample so an appropriately sized beaker is approximated depending on the density and size of the organisms in the sample Water is added to increase the volume of the entire sample to a known volume read off the beaker Again this volume is a
74. hen the cartridge is run alone See Section 8 of the Astoria Analyzer Operation Manual for information on how to add a helper line 5 Cover all reagents and other solutions to avoid interference due to dust and other particulates This will also help prevent contamination of the solutions from absorbance of analytes in the air 6 The OPA reagent can be made by an alternate procedure The instructions are as follows OPA stock solution Dissolve 2 g of OPA in 50 ml of pure ethanol 200 proof The stock solution needs to be stored refrigerated in an amber glass bottle The stock is stable for 2 months To 250 ml of borate buffer add 5 ml of OPA solution 0 5 ml sodium sulfite solution Add 10 drops of Brij 35 and mix thoroughly Transfer to an amber glass bottle and let stand approximately 24 hours Working solution can be stored in the dark for 1 month 7 f there is a significant drop in peak height even after making fresh reagent remake the sodium sulfite solution then add it to the prepared OPA reagent 8 Due the ease of contamination it is necessary to fill wash cups directly from the sampler wash container The transfer should be performed in one step rather than multiple steps 1 large pipette 9 It is highly recommended that 16x100mm plastic test tubes are used for sampling They help Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 323 reduce outside contamination 1
75. ignment of sensors and a loop edit function is used to remove data collected during a cast in which the CTD either decelerates or travels backwards loops due to rolling of the vessel Finally depth potential temperature and salinity are derived from pressure temperature and conductivity data respectively and density sigma t is calculated based on temperature salinity and pressure 2 10 2 Field Data data from field notebooks will be manually entered into the appropriate database format 2 10 3 Laboratory Data All laboratory data will either be electronically transferred from the instrument or manually read from the instrument display or optical field of a microscope and entered onto a standard data form Forms used for data entry are included in Appendix Data in laboratory notebooks will be manually entered when necessary All data reduction will be performed electronically either by the instrument software or in a spreadsheet and will be validated according to procedures described in Section 4 0 Laboratory replicates will be reported as mean sample values field replicates will be reported as individual sample values The format for final data submission to MWRA is shown in Table 2 6 Data will be submitted electronically as Microsoft Excel spreadsheets Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 24 Table 2 6 Specifications for data sets a Samples
76. ith User Requirements A key step in the evaluation of the validated data to determine if it meets the user requirements is the presentation of the results at the MWRA s annual technical workshop in the spring This will provide a means for peer review of the data and interpretation of results Data collected for this project will also be compared with data collected during the on going Cape Cod Bay Monitoring Program and Right Whale Habitat Program conducted by PCCS A synthesis of the data collected from these programs will provide a context from which to evaluate nutrient loading and the possible effects on the food chain from phytoplankton to right whales Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 29 5 0 References Borkman D 1994 Phytoplankton and Nutrients in Buzzards Bay Massachusetts 1987 1988 M S Thesis University of Massachusetts Dartmouth Dartmouth MA 203 pp Borkman D Pierce RW Turner JT 1993 Dinoflagellate blooms in Buzzards Bay Massachusetts Pp 211 216 in Smayda T J and Y Shimizu Eds Proceedings of the Fifth International Conference on Toxic Marine Phytoplankton Elsevier Costa AS 2010 Laboratory quality assurance plan Provincetown Center for Coastal Studies Final draft submitted to Massachusetts Department of Environmental Protection Guillard RRL 1973 Division rates Pages 289 311 In J R Stein Ed Phycological Methods Cambridge Univ Press
77. led with sample water The container will be stored in a cooler until it can be transferred to the lab and frozen within 8 hours 2 2 1 2 3 Chlorophyll a and Phaeophytin Samples for chlorophyll a phaeophytin determination will be processed according to PCCS SOP for chlorophyll a phaeophytin 1000 ml of sample water will be filtered through Whatman 4 7 cm diameter GF F using a vacuum pump at a vacuum no greater than 6 in Hg The final volume should result in a light green brown residue on the filter Using forceps the filter will be removed from the filter holder folded in half and blotted on acid free blotting paper to remove excess moisture The folded filter will then be placed in a foil packet and stored in a cooler in a pre labeled whirl pak until it can be transferred to the lab and frozen within 8 hours 2 2 1 2 4 Whole Water Phytoplankton Water from the near surface Niskin sampling bottle will be poured into a graduated cylinder that has been cut at the 850 mL mark Before filling the cylinder to 800 ml it is rinsed three times with water from the Niskin sampling bottle The filled cylinder is then poured into a 1 L bottle containing 8 mL of Uterm hl s solution preservative The preserved samples are stored at ambient temperature and in the dark until analysis The Uterm hl s solution is prepared as described in Guillard 1973 100 g potassium iodide 50 g iodine and 50 g sodium acetate each are dissolved incrementally in distilled wat
78. mail or memoranda summarizing the key discussions and actions taken Dave Taylor will be notified immediately regarding any issues or deviations from the project plan including if project surveys are not carried out as planned or samples are missing Annual project meetings are held in the spring of each year to review and update the project plan including updating information on sample scheduling sampling locations and frequency analytical methods and staffing 1 3 Project Definition and Background The public and regulators have recently raised concerns that MWRA s outfall in Massachusetts Bay poses a long term threat to the health of CCB and SBNMS This project will continue ambient water column monitoring of three farfield stations instituted by MWRA in 1992 by adding these stations to PCCS s ongoing Cape Cod Bay monitoring program Two of these stations are located in Cape Cod Bay CCB and one in Stellwagen Bank National Marine Sanctuary SBNMS PCCS has been conducting marine mammal and habitat research in CCB and SBNMS for over 30 years The monitoring to be conducted as part of this project will allow PCCS to better understand and protect the ecology of CCB and SBNMS and the whales that use the two areas It will also provide water quality data at the same three locations that MWRA needs to monitor in CCB and SBNMS to meet its NPDES permit requirements 1 44 Project Description and Schedule PCCS will continue to monitor thre
79. most OSHA requirements for worker safety Lab Safety Officer Amy Costa Emergency Numbers Hazardous Materials Hotline 800 3 19 2783 Provincetown Fire Department 508 487 7023 Provincetown Health Center 508 487 9395 General Health and Safety Information 1 Eye protection gloves and lab coats are available and required when working with chemicals Closed toed shoes are required 3 Locations of accident and safety equipment a First aid kit is located on wall to right of sink b Eye wash station is located to the right of the sink c Shower is located downstairs d Spill pads are located under sink 4 Report any accidents immediately to Amy Costa and or Rich Delaney 5 Nearest Medical Facility is the Provincetown Health Center located at 49 Harry Kemp Way 6 liquid chemicals must be stored below eye level 7 chemicals must be properly labeled and stored at all times Hazardous labels must indicate what harm the chemical represents 8 MSDS sheets are located in the file cabinet in folder labeled MSDS 9 Laboratory must comply with local building fire codes 10 Wastes must be properly stored in their own container i e acetone waste in container labeled Acetone Waste acid waste in container labeled Acid Waste etc 11 Disposal of hazardous waste will be done through Barnstable County s Cape Cod Cooperative Extension Hazardous waste generator status very small quantity generator limited primarily to coppe
80. ncetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 47 Ascorbic FNCU Qa uou 5 46 FW176 13 Deionized Water Dissolve 5 4 g ascorbic acid in 150 ml of deionized water Add deionized water to a final volume of 300 ml and mix well Stable for 10 days if stored at 2 8 C 6 Color Reagent 100 ml S lf r Acidi S N de tee ete ee dads 50 ml Antimony Potassium ee dote 5 ml Ammonium Molybdate re i tieni Ee 15 ml Ascorbic Acid eo n o esent o oen tbe aci 30 ml Add reagents in the order stated and mix after each addition Add 3 5 ml SLS and filter to 0 45 um Prepare reagent daily re Artificial Seawater ASW 4 L See Operating Notes Sodium E 128 56 NaCl FW 58 44 Magnesium Sulfates de Rss 28 56 MgSOq 7H20 FW 246 48 Sodium Bicarbonate aee oett toten Waste Mae le dte tere Waele Nees 0 672 g NaHCO FW 84 01 Deionized Water Dissolve 128 5 g sodium chloride 28 5 g magnesium sulfate and 0 672 g sodium bicarbonate in about 3 liters of deionized water Dilute to 4 liters with deionized water These reagents must be high quality reagent grade to avoid excessive nutrient o
81. ng from the plastic it is glued back down using PVC cement The Hensen Stempel pipettes are cleaned once per year or more frequently if needed They are soaked in warm soapy dish soap water and then soaked in fresh hot water They are them thoroughly rinsed to remove all soap and set aside to dry The Folsom plankton splitter is cleaned once per year or more if necessary It is scrubbed with dish soap and then thoroughly rinsed with hot water until all soap is removed It is then set aside to dry The microscopes are cleaned once per year The lenses in the eyepieces and eyepiece tubes are wiped clear of dust using Kimwipes The lens over the light condenser is also wiped clean After every use the microscope is unplugged and covered with a dust cover The multi channel digital counter used in the enumeration of zooplankton is regularly cleaned using compressed air The area under the buttons is flushed of dust and dirt Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 22 27 Corrective action contingencies If results from any analyses of QC checks are unacceptable corrective actions will be taken as described for each SOP above Whenever possible analyses will be re run with new QC checks If results are still unacceptable the instrument will be re calibrated according to manufacturer s instructions The Lab manager is responsible for all corrective actions The QA Officer must also be con
82. nt Deep Sea Res 14 3 381 389 Atlas E L W Hager L I Gordon and P K Park 1971 A practical manual for use of the Technicon AutoAnalyzer in seawater nutrient analyses revised Technical Report 215 Oregon State University Dept of Oceanography Ref No 71 22 48 pp Gordon L I J M Krest and A A Ross in preparation Continuous Flow Analysis of silicic acid in seawater Reducing sensitivity to laboratory temperature fluctuations Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 75 15 Automated Nutrient Analysis in Seawater Technical Report Brookhaven National Laboratory Whitledge Veidt et al May 1986 Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 76 APPENDIX B Data Forms Field Data Sheet Survey Data Field Data Sheet Station Data Lab Data Sheet Chlorophyll Lab Data Sheet Phytoplankton Lab Data Sheet Zooplankton Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 77 Survey Data VESSEL Alert Seaway Shearwater Date High Tide Low Tide Weather Sea State Wind Time Begin End Comments Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 78 Station Data Trip Station Time Depth CTD Secchi Turb Nutrients Depth Sample Surface Depth Chl a Pr
83. ntact the Coast Guard and or the Center for Coastal Studies and note the last direction the animal was heading and any other pertinent information that would assist in relocating the whale Stranded Whales For a stranded right whale please notify the Stranding Network immediately call Connie Merigo or Howard Krum New England Aquarium Central Wharf Boston MA 02110 The standing Network s hotline is 617 973 5247 pager or as a second resort call 617 973 5246 6551 QUICK REFERENCE Sightings amp Photographs Patricia Gerrior NMFS Right Whale Early Warning System Coordinator manages the Clearinghouse and her numbers are 508 495 2264 work 508 495 2393 fax and pager 508 585 8473 Photographs Dan McKiernan Massachusetts Division of Marine Fisheries 19th Floor 100 Cambridge Street Boston MA 02202 617 727 3193 ext 369 Entanglements or Injured whales Center for Coastal Studies entanglement hotline at 800 900 3622 or pager at 508 803 0204 Massachusetts Environmental Police Communications Center at 800 632 8075 or 617 727 6398 Stranded Animals The standing Network s hotline is 617 973 5247 pager or as a second resort call 617 973 5246 6551 Massachusetts Water Resources Authority Charlestown Navy Yard 100 First Avenue Boston MA 02129 617 242 6000 http www mwra state ma us
84. of chemicals available Certificates of Analysis are available from the chemical manufacturer These should be consulted to identify impurities Standard material should be oven dried for two hours at 110 C before weighing It is advisable to periodically verify the concentrations of the working standards This can be done by running standards against standards from an outside source The matrix of the standards should be consistent with that of the samples If deionized water standards are used it becomes important to determine the salt effects of each individual test See number 2 under Operating Notes Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 42 B Matrix Optimal system performance can be expected if the sample matrix is carried over into the sampler wash solution and the standards Care should be taken when using deionized water wash solution with seawater standards Many investigators recommend segregating the samples by salinity and running as a group to make corrections easier There are many options with respect to the matrix of the calibrant and sampler wash solutions The relative merits of several types of material are presented here 7 Deionized Water Advantages 1 The quality of the water is usually well known 2 The quality of the water is usually not highly variable 3 The prepared standards are relatively stable with time 4 Large volumes of water are easily
85. ole Buffer 500 ml Stock BUIfer ui esata tad e 500 ml Detergent EX 10 Dm dels 40 drops Add 40 drops 10 to each 500 ml of Stock Buffer required Mix well 6 NED Reagent 1 L N 1 naphthylethylenediamine Dihydrochloride 1 06 CiH44N5 e2HCI FW 259 18 Deionized Water Dissolve 1 0 g N 1 napthylethylenediamine dihydrochloride in about 800 ml deionized water contained in a 1 liter volumetric flask Dilute to the mark with deionized water Filter to 0 45 um Store ina brown bottle and refrigerate when not in use Reagent is stable for several months Discard if colored Ts Stock SAN Reagent 1 L Plat ate 10 06 C6HsN202S FW 172 21 10 Dissolve 10 0 g of sulfanilamide in about 800 ml of 10 contained a 1 L volumetric flask Dilute to the mark with 10 HCl and mix well Filter to 0 45 um Stable at room temperature but may be refrigerated 8 Working SAN Reagent Stock SAN Reagent aote 250 ml D tersentDX 10 core us aD IO E ERO tease 30 drops Add 30 drops TX 10 to 250 ml of stock SAN reagent and mix well 9 Artificial Seawater ASW 4L c bee i astridse er 128 56 NaCl FW 58 44 M gnesium SOAS itu o Saleh ar had arent Paha 28 5 g MgSO4 7H 0 FW 246 48 Sodium Bicarbonate
86. on 2 Alkaline Persulfate Digestion Reagent Potassmim sash di pede i epe pata 25 02 5 FW 270 33 Datel 175 mL BONC AC ca c aseo ad at Woes a de mus 15 06 H3BO3 FW 61 83 Ultrapure Water Add 25 0 g of potassium persulfate 15 0 g of boric acid and 175 mL of 1 0 N sodium hydroxide solution to about 250 mL of DI water in 1000 mL Pyrex media bottle Cap the bottle swirl its contents and place it in an magnetic stirrer dissolution is complete about 10 minutes Remove the bottle from the magnetic stirrer and pour solution into 500 ml volumetric flask Add ultrapure water to the 500 ml mark Prepare this reagent day of sample digestion 3 Glycine Digest Check Stock Solution Ha edie 3 98 g C2HsNO2eHCl FW 111 5 Ultrapure Water Dissolve 3 98 g glycine in about 400 mL of DI water in a 500 mL volumetric flask Dilute this solution to the mark with DI water and mix it thoroughly by manual inversion and shaking Transfer the stock digest check solution to a 500 mL Pyrex media bottle in which it is stable for 6 months at 4 C 4 Glycerophosphate Digest Check Stock Solution Glyeerophospliale ee eee tend ada Ute 1 976 g C3H O0gPNa5 e 5H O FW 306 1 Ultrapure Water Dissolve 1 976 g glycerophosphate in about 400 mL
87. ov srs 2 9 Data Acquisition Requirements non direct measurements Data from previous and on going monitoring conducted by MWRA and PCCS will be utilized to assess the state of CCB and SBNMS Other possible data from non direct measurements that may be used include satellite imagery and mooring data These secondary data are used as received and not censored 2 10 Data Management 2 10 1 Hydrographic Data The hydrographic data generated during the survey consists of rapidly sampled high resolution measurements of conductivity temperature depth DO fluorescence and PAR Data will be logged internally and downloaded using Seabird SeaTerm software For surface PAR data are logged directly onto a computer using LOGGER 2100 software supplied by Biospherical Instruments Inc SBE Data Processing Software from Seabird will be used to process the raw data from the instrument Using this software data are first converted from the raw data to scientific units 1 e conductivity temperature Only data from the downcast are used In order to match the response of the temperature and conductivity sensors the data have to be filtered A low pass filter of 0 5 seconds is used to match the time constants of temperature and salinity A second low pass filter of 2 seconds is applied to pressure readings to separate data that are collected at a less than minimum descent rate Temperature and conductivity are advanced 0 5 seconds to account for misal
88. ovincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay Lab Data Sheet Chlorophyll Lab Name Date Extracted Time Extracted Lab Analyst Secondary Standard Date Measured Acetone Blank Time Measured Calibration Used Sample Sample Volume Volume Location Date Filtered Solvent Notes Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 80 Lab Data Sheet Phytoplankton Cf Bacteriastrum spp Centric diatom sp group 1 diam lt 10 microns Cerataulina pelagica Chaetoceros atlanticus Chaetoceros borealis Chaetoceros compressus Chaetoceros debilis Chaetoceros decipiens Chaetoceros didymus Chaetoceros laciniosus Chaetoceros laciniosus Chaetoceros lauderi Chaetoceros lorenzianus Jo Chaetoceros socialis Chaetoceros sp group 1 diam lt 10 microns Chaetoceros sp group 2 diam 10 30 microns Chaetoceros subtilis Corethron criophilum Coscinodiscus oculus iridis Coscinodiscus radiatus Coscinodiscus sp group 2 diam 40 100 microns Coscinodiscus sp group 3 diam gt 100 microns Dactyliosolen blavyanus Dactyliosolen fragilissimus Detonula confervacea Ditylum b
89. pproximated to get at least 200 organisms in 5 ml of sample The lowest total volume used is 125 ml to prevent poor subsampling A Hensen Stempel Pipette is used to first stir the contents of the beaker suspending and equally distributing the sample throughout the beaker and then to subsample 5 ml of the sample from the middle of the beaker The 5 ml 1s transferred directly into a glass watch glass and the pipette s sample chamber is rinsed with fresh water from a squirt bottle into the watch glass to ensure that no organisms from the subsample are lost The sample is now ready to be enumerated and identified Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 67 Sample Splitting If the zooplankton net sample is too large to be sub sampled in such a way that there will be approximately 200 organisms per 5 ml of sample the sample must be split for this a Folsom plankton splitter is used First the splitter is leveled by adjusting its legs The sample is poured from a glass beaker see steps above for transferring the sample into the glass beaker into the opening in the main part of the splitter oriented so that when it is rotated downward the sample is split and exits the holes in the splitter into the holding chambers As the splitter is rotated a squirt bottle is used to be sure that all organisms are included Half of the split sample can now be put back into a beaker If the sample is still too
90. proper filtration procedures for the reagents and samples will reduce the frequency of this occurring 2 To prevent the accumulation of background contamination forming in the color reagent keep the reagent bottle covered at all times Baseline drift may also be reduced by placing the color reagent in an ice bath during analysis 3 Ifincreased carryover and drift are experienced make sure the ascorbic acid and ammonium molybdate solutions are fresh 4 If bubbles are sticking in a debubbler cleaning the debubbler will allow bubbles to escape smoothly out the debubble line Bubbles sticking in the debubbler can cause a loss in the overall precision of the peak height To clean soak the debubbler for 2 3 hours in a mixture of 20 30 Contrad NF API p n 80 0007 04 and hot tap water Rinse thoroughly 5 For chronic carryover and drift problems the following cleaning solution can be used to flush the analytical cartridge and flowcell Potassium Iodide Cleaning Solution 55 ml Potassium LOGI ed lg KI FW 166 00 5 Sulfuric Acid See Reagent 25 ml H2SO4 FW 98 08 Deionized he bens ns 30 ml Add 1 g KI to about 25 ml 5 N sulfuric acid Stir vigorously until a strong yellow orange color has formed This may take at least one hour Add about 30 ml deionized water The solution will darken over time and is usable for one month Pump
91. r bottom will accurately characterize the vertical variation It is assumed that the spatial scales of variation are large enough that the sampling locations selected for this region are representative of water quality for this region It is also assumed that since surveys are conducted independent of tidal influence and weather that the annual survey frequency is high enough that fluctuations in conditions due to weather or tide will not result in biased results Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 11 2 1 4 Procedures for Locating and Selecting Environmental Samples All sample locations are identified using GPS coordinates Error of 10 m is considered acceptable to allow for error in the GPS readout 2 1 5 Classification of Measurements as Critical or Non critical All measurements collected as part of this survey are considered critical due to the requirement in MWRA s discharge permit to conduct the measurements described in the Ambient Monitoring Plan 2 22 Sampling Methods Requirements 2 2 1 Sample Collection Preparation Decontamination Procedures 2 2 1 1 Hydrocasts and Sensor Measurements At each station a hydrocast will be conducted with a SBE 19plus V2 conductivity temperature depth CTD system equipped with various sensors dissolved oxygen chlorophyll fluorescence PAR Sensor measurements will be collected during the downcast from near surface approximately 0 5 1 5
92. r sulfate required for nitrate nitrite analyses and activation of cadmium coil and acetone Hazardous Wastes Requiring Special Disposal Acetone Copper Sulfate Acid Wash 10 Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 33 Standard Operating Procedure 002 General Labware Cleaning Procedure Date Nov 2007 Revision 2 Purpose and Description Outline appropriate techniques for cleaning labware and sampling containers Only glass sample containers will be reused Whirl paks and disposable polypropylene tubes will be discarded Clean labware and sampling containers are required to ensure that results for the assays analyzed in the laboratory are accurate Method Description All labware is washed in non phosphate detergents i e Liqui Nox stored under the sink in a 1 gallon container Glassware is soaked in a bath of dilute hydrochloric acid 10 kept in labeled glass tub Glassware Cleaning Procedure 1 Empty non hazardous contents of bottles down the drain and hazardous contents into appropriate waste containers 2 Remove labels This is expedited by soaking bottles in tap water 3 Wash in soapy water Liqui Nox 4 Rinse with tap water at least 3 times 5 Soak glassware for at least 24 hours in tub of 10 HCL Make sure glassware is completely submerged 6 Rinse with DI water 7 Fill with DI water and allow glassware to soak for at least 1 2 hours 8 Rinse thoroughly
93. r trace metal contamination 8 Startup Shutdown Solution 100 ml Deionized Walter xe ede eet ee cune eee aeq edet gae 100 ml ie a teu de ui ed 2 9 Sampler Wash Solution See Operating Note 1 F Calibrants See Nitrate Nitrite Analysis SOP for information on calibrant preparation Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 48 G Operation Procedure 1 10 11 12 13 Set up the cartridge as shown in the flow diagram Check all tubing and connections Replace if necessary Place reagent lines in startup solution Turn on power to all units including heat bath and latch pump platens to begin liquid flow Verify that the bubble size and spacing is consistent throughout the cartridge If bubbles are splitting up as they enter or exit a coil or heat bath check and replace fittings if necessary The bubbles should flow smoothly without dragging If dragging occurs add more SLS to the startup solution Check all reagent containers on the instrument for particulate matter Reagents should be filtered weekly Be sure all containers are properly labeled and filled before pumping reagents After the heat bath has reached the desired temperature and a stable baseline has been verified on the startup solution place reagent lines in reagent bottles If using data collection software set up the approp
94. require consultation with MWRA The Program Manager is also accountable to MWRA for overall performance of this monitoring program Issues regarding scheduling e g synoptic sampling with MWRA s Massachusetts Bay monitoring consultant will be reported to MWRA and dealt with under their guidance 3 2 Reports to Management A survey report detailing the sampling that was conducted will be submitted to MWRA within a week after the survey has been completed Additionally quarterly reports will be submitted to MWRA which will include the hydrographic data and laboratory data nutrients phytoplankton zooplankton collected during the surveys conducted in the respective quarter data collected during the year will be presented at the MWRA annual technical workshop held each spring Following the completion of the workshop MWRA will be provided with a digital copy of the Power Point slides and a two page abstract describing the major results of the year 4 0 Data Validation and Usability 41 Data Review Validation and Verification Requirements No data will be used until they are validated and verified as described in 4 2 The adherence to the data quality objectives Table 2 3 and laboratory QC s Table 2 4 Table 2 5 RPD s of duplicate plankton Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 28 counts notations in field and laboratory notebooks cross checks of data entry and the results of the
95. riate sample table Allow reagents to run for 5 to 10 minutes and verify a stable baseline Load the sampler tray with calibrants blanks samples and QC or monitor samples Select the appropriate parameters for the detector and sampler See Flow Diagram Begin analysis At the end of analysis place all reagent lines in startup shutdown solution and turn off the heat bath Pump startup shutdown solution for 20 to 30 minutes to flush all of the reagents out of the cartridge and to allow the heat bath to cool Turn off the power to all units and release pump platens H Operating Notes See Nitrate Nitrite Analysis SOP for information on sample matrices If the flowrate of the sample pump tube is lt 226 ul minute a blk blk pump tube a helper line must be added when the cartridge is run alone See Section 9 of the Astoria Analyzer Operation Manual for information on how to add a helper line Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 49 NOTE Ifthe sample line is debubbled a helper line is not necessary 1 Low sensitivity and noise in the baseline can be caused by debris in the flowcell Particulate matter from the reagents and samples can become lodged in the flowcell restricting the amount of light that is passed through the flowcell Flushing the flowcell with approximately 10 ml of sampler wash solution with a syringe will dislodge any debris in the flowcell Following
96. ribution List Distribution List Amy Costa PCCS Program Manager Richard Delaney PCCS Executive Director Charles Mayo PCCS Plankton Studies Elizabeth Larson PCCS QA Coordinator David Taylor MWRA Project Manager Cape Cod Bay Monitoring Environmental Quality Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay Page i of iii TABLE OF CONTENTS 1 20 mem PROJECT MANAGEMENT taste 1 ld PROIECPORGANIZATION a eere tee ec eee eet te e PEE E E 1 1 2 COMMUNICATION PLAN sonin reete eee o er E t b Ped eom eive ve eei 2 1 3 PROJECT DEFINITION AND 22 2 0 1 00000000000000000000000000000000000 AE asse EEE rena assent 2 1 4 PROJECT DESCRIPTION AND SCHEDULE RN 2 1 5 QUALITY OBJECTIVES AND CRITERIA FOR MEASUREMENT DATA 00 0 0 1 6 1 6 SPECIAL TRAINING REQUIREMENTS AND 0 2 000000000 000010000000000000000 0 9 1 7 DOCUMENTATION 8 eee aded 9 pi me H MEASUREMENT DATA A
97. ric maximum visit and sample 150 characters b Hydrographic measurement data Description Field Required Data type amp format Field Identifier of sampling event survey EVENT ID Y alphanumeric maximum 10 characters Identifier for station STAT ID Y alphanumeric maximum 10 characters Station arrival date and time Local Time STAT ARRIV Y Date LOCAL Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 25 Description Field Required Data type amp format Field Depth in meters decibars at which data were DEPTH Y number 2 decimal places collected Date and time when data were collected Local PROF DATE Date Time TIME LOCAL Code for parameter measured PARAM CODE Y alphanumeric maximum 20 characters Result for parameter VALUE Number Value qualifier QUAL alphanumeric maximum 4 characters Code for the unit of measurement UNIT_CODE alphanumeric maximum 12 characters Code for method METH_CODE alphanumeric maximum 13 characters Code for instrument used INSTR_CODE alphanumeric maximum 10 characters Comments for the sensor measurement COMMENTS alphanumeric maximum 150 characters Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 26 c Nutrient measurement data
98. rightwellii Eucampia cornuta Guinardia delicatula Guinardia flaccida Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 81 D C Guinardia striata D C Lauderia annulata D C Leptocylindrus danicus D C Leptocylindrus minimus D C Lithodesmium undulatum D C Melosira nummuloides D C Paralia sulcata D C Porosira glacialis D C Pseudosolenia calcar avis D C Proboscia alata D C Rhizosolenia hebetata D C Rhizosolenia setigera D C Skeletonema costatum D C Stephanodiscus spp D C Stephanopyxis turris D C Thalassiosira anguste lineata D C Thalassiosira nordenskioeldii D C Thalassiosira rotula Thalassiosira sp group 1 diam 20 D C microns Thalassiosira sp group 3 10 20 microns D C length D p Amphora spp D p Asterionella formosa D p Asterionellopsis glacialis D p Bellerochea malleus D p Cocconeis scutellum D p Cocconeis spp D p Cylindrotheca closterium D p Grammatophora marina D p Gyrosigma spp D p Isthmia nervosa D p Licmophora spp D p Odontella aurita D p Odontella sinensis Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 82 D p Odontella spp Pennate diatom sp
99. rimary Method EPA 365 5 A Scope and Application This method is used for the determination of ortho phosphate dissolved reactive phosphate in seawater The applicable range of this method is 0 02 3 0 uM phosphate However this method is also applicable to other ranges B Summary of Method Ortho phosphate reacts with molybdenum VI and antimony IID in an acidic medium to form phosphoantimonylmolybdenum complex This complex is subsequently reduced by ascorbic acid to a heteropolyblue with an absorbance maximum at 880 nm C Sample Handling and Preservation All samples will be filtered using 0 4 um Nucleopore filters Samples must be kept frozen until analysis Holding time should not exceed 28 days D Raw Materials Required NOTE Chemicals should be of ACS grade or equivalent Ammonium Molybdate NH4 6Mo7O24 4H20 FW 1235 86 Antimony Potassium Tartrate K2Sb2CsH4012 3H20 FW 667 87 Ascorbic Acid CeHgOg FW 176 13 Deionized Water ASTM Type I or Type II Low Nutrient Seawater LNSW Magnesium Sulfate MgSO47H5O FW 246 48 Potassium Dihydrogen Phosphate KH PO FW 136 09 Sodium Bicarbonate NaHCO FW 84 01 Sodium Chloride NaCl FW 58 44 Sodium Lauryl Sulfate Ci2H2sO4SNa FW 288 38 Sulfuric Acid Concentrated 5 FW 98 08 See operating notes for information on matrix choices Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 46 E Reagent Prepar
100. rix RPD if more than 0 5 M 80 120 recovery for std and lab 0 05 uM if less than 0 1 uM or 20 fortified matrix RPD if more than 0 1 uM 0 Total Nitrogen um 05 0 30 80 120 recovery for QC std and lab Rpp fortified matrix Total 80 120 recovery for QC std and lab Phosphorous DA ere fortified matrix 2 0 uM if less than 15 ug l or 25 Chlorophylla ug l 0 02 0 50 75 125 recovery for QC std RED more Manis ugi Table 2 4 Laboratory Analytical QC Nutrients Nitrate Nitrite Ortho Phosphate Ammonia TN and TP Method SOP Heron Measurement Frequency Corrective Responsible for QC QC Acceptance Performance Number ae Action Corrective M Limits Criteria Action Menos 1 per set of 20 lt MDL Re run Lab Manager lt Blank 2 1 per set of 20 lt MDL Re run Lab Manager lt MDL Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 19 0 Laboratory 10 01 lt 20 RPD Re run Lab Manager lt 20 RPD Duplicate samples 0 0 S d 1 per set of 20 2 Re run Lab Manager Sm External 90 110 90 110 Standards 1 per set of 20 Eoin Re run Lab Manager rebovery Internal standard a known amount of a standard added to a test portion of a sample and carried through the entire determination procedure as a reference for calibrating and controlling the precision and
101. s instrument duplicates standards MDL method detection limit The actual MDL may be updated periodically MDLs are based on the target sample volumes shown in Table 2 1 Relative Percent Difference RPD replicate 1 replicate 2 x 2 replicate 1 replicate 2 100 gt Percent Difference PD true concentration measured concentration true concentration x 100 1 5 2 2 5 Completeness It is expected that 100 of samples collected for analysis will in fact be analyzed However a sample loss of 1096 will not compromise the objectives of the project 1 6 Special Training Requirements and Certification Field Monitoring Sample collection requires no non routine field sampling techniques field analyses laboratory analyses or data validation Specialized training is therefore not required Field personnel are experienced in using the equipment identified within this QAPP Laboratory Analyses Nutrient and chlorophyll measurements use routine laboratory analyses or data validation therefore specialized training is not required Lab personnel are experienced in standard protocols specified in PCCS s Laboratory Quality Assurance Plan for handling storing and preparing samples for analysis Laboratory personnel are also experienced in using the equipment identified within this QAPP 1 7 Documentation and Records PCCS will maintain all documents relevant to sampling laboratory analysis and dat
102. s for that survey will be made with consultation and agreement of MWRA whenever possible 10 loss of hydrographic and navigation data over the entire program is not expected to compromise the objectives of the program 1 5 2 2 Water Sampling and Analysis 1 5 2 2 1 Precision and Accuracy Precision and accuracy of laboratory procedures are ensured by the analysis of quality control QC samples including procedural filter blanks prepared standards standard reference samples SRS where available laboratory control samples laboratory replicates and field replicates as applicable Table 1 6 lists the desired precision accuracy and detection limit goals for each parameter to be measured QC samples to be analyzed in the laboratory to assess precision and accuracy are listed in Table 2 4 and Table 2 5 Method procedural blanks for parameters that use blank correction are the batch average uncorrected method procedural blanks Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 1 5 2 2 2 Comparability Data will be directly comparable to results obtained previously at the same or similar sites in Massachusetts and Cape Cod Bay by PCCS and or MWRA because field program design and analytical procedures are similar or identical In addition use of written standardized procedures ensures that sample preparation and analyses will be comparable throughout the project and with other projects 1 5 2 2 3 Repre
103. scence of sample after acidification Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 62 Vsolvent Volume of solvent used to extract sample Vwater Volume of water filtered Interpolation equation used in end calculation of chlorophyll a and pheophytin concentrations Fsamp B Fotank Fstanati B Fotank Interp A Cotanapi Fsamp Folank Fstanati B 7 Fotank End calculation for corrected chlorophyll and pheophytin a Chlorophyll a concentration Fm Fm 1 Interp s Interp A Visoiven V water Pheophytin a concentration Fm Fm 1 Fm Interp Interp p Vsotvent Vwater References EPA Method 445 0 Standard Methods for the Examination of Water and Wastewater Centennial Edition 21st Ed Method 10200H pp 10 19 10 26 2005 Turner Designs Trilogy Laboratory Fluorometer User s Manual www turnerdesigns com t2 doc manuals TrilogyUsersManual pdf Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 63 Standard Operating Procedure 008 Phytoplankton Collection and Analysis The following methods for the collection identification and enumeration of phytoplankton species are similar to those described in Libby et al 2002 2005 2006 and 2010 and have been used in Massachusetts Water Resources Authority Harbor Outfall Monitoring Projects HOM3 through HOM6 Thus data from current ef
104. sed in organisms per cubic meter organisms m derived from the flow meter correction constant flow meter change during the tow the area of the mouth of the net volume of the sample and volume of the sub sample that was counted 2 5 Quality Control Requirements 2 51 Calibration Procedures 2 5 1 1 Hydrographic Instruments All hydrographic instruments and sensors are sent to the respective manufacturers Seabird WET Labs Biospherical annually for calibration 2 5 1 2 Nutrients nitrate nitrite ortho phosphate ammonia TN and TP At least 6 working calibrants for each chemistry will be prepared from certified standards to cover the concentration range of the samples to be analyzed The calibrants are run at the beginning of the analyses and a calibration curve is fitted If the correlation lt 0 995 new calibrants will be prepared and calibration will be re done See SOPs for more detail Standards are supplied from Astoria Pacific Each standard is labeled with concentration and expiration date Standards are stored at room temperature Working calibrants of concentrations gt 100 uM are prepared weekly and stored at 4 C Working calibrants of concentrations 100 uM are prepared daily 2 5 1 3 Chlorophyll and Pheophytin The laboratory fluorometer is calibrated at the beginning of each monitoring season with 2 liquid pure chlorophyll a standards and reagent At the time of calibration a solid secondary standard is also analyzed
105. sentativeness Representativeness is addressed in sampling design The sampling practices and laboratory measurements that will be performed during the water quality monitoring have already been used in many systems to characterize eutrophication and or microbiological effects on the water column and are therefore expected to yield data representative of the study area Representativeness will also be ensured by proper handling storage including appropriate preservation and holding times and analysis of samples so that the material analyzed reflects the material collected as accurately as possible Deviations from the analytical scheme described in this QAPP will be noted in the laboratory records associated with analytical batches in the QA statements 1 5 2 2 4 Sensitivity Sensitivity is the capability of methodology or instrumentation to discriminate among measurement responses for quantitative differences of a parameter of interest The method detection limits MDLs provide the sensitivity goals for the procedures as outlined in Table 1 6 Data users should be aware that precision and accuracy generally degrade as analyte concentrations decrease While numerical results are being reported down to the MDL results below the lowest calibration standard will often have precision and accuracy that don t meet the data quality objectives for the project Table 1 6 Desired precision accuracy and MDL for each parameter based on quality objec
106. sk Dilute the solution to the mark with deionized water and mix well Stable at room temperature 2 Stock Ammonium Chloride Copper Sulfate 1 L Ammonium Chloride Rae aA ina 2506 NH4CI FW 53 50 Copper Sulfate Solution 2 2 5 ml Deionized Water Dissolve 250 g of ammonium chloride in 900 ml of deionized water contained in a 1 L beaker Add 2 5 ml of 2 copper sulfate solution Transfer the solution to a 1 L volumetric flask and dilute to the mark with deionized water Store refrigerated at 2 8 C 3 10 HCI 2 L Hydrochloric Acid Concentrated esses 200 ml FW 36 46 Deionized Water Carefully add 200 ml of hydrochloric acid to about 1000 ml of deionized water Cool and dilute to 2000 ml 4 Stock Imidazole Buffer 2 L Indazoles Caos e vete 6 86 C3H4N2 FW 68 08 Stock Ammonium Chloride Copper 30 ml 10 HG L axis as needed Deionized Water Dissolve 6 8 g imidazole in about 1500 ml deionized water Add 30 ml of stock ammonium chloride copper sulfate solution Adjust the pH to 7 8 7 85 with 10 Dilute to 2000 ml with deionized water and mix well Filter to 0 45 um Stable at room temperature Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 36 5 Working Imidaz
107. sulted corrective actions will be documented in the lab notebook 2 8 Inspection Acceptance of Supplies and Consumables Prior to use supplies and consumables will be inspected and tested to ensure that they conform to the required level of quality Any defective material will be replaced before the sampling event or before analysis begins Supplies and consumables consist of sample containers whirl paks polypropylene sample vial filters Whatman GF F Nucleopore 0 4 um filtration apparatus syringe and Swinlok filter holder preservation solutions formalin Utermohls solution distilled water laboratory reagents and standards chlorophyll and nutrient e Sample containers are either cleaned by the laboratory or purchased new Containers must be cleaned according to SOPs prior to use and must be rinsed three times with station water prior to being filled with sample Field blanks assess potential contamination of containers and sampling equipment e filtering equipment the syringe and filter holder are cleaned prior to use The equipment gets a 10 rinse in the followed by a triple rinse of distilled water Between stations the equipment gets rinsed with distilled water and a triple rinse with station water e Filters for chlorophyll and dissolved nutrients are used directly from the manufacturer and are not cleaned or treated e Preservation solutions must be prepared using at least reagent grade chemicals HPLC
108. t in use logbooks will be stored in the laboratory Each logbook cover must be labeled with the project name and the range of survey dates included in the logbook Information will be entered in the logbook in pencil or waterproof ink initialed and dated with no erasures made If corrections are required the information will be crossed out with a single line and initialed by the sampler Sample containers will be pre labeled with the following information Survey number vessel designation and trip number site and depth S for near surface D for near bottom SW765 F01 S All other information relevant to the sample time date depth etc can be cross referenced in the field logbook samples except phytoplankton samples will be collected and analyzed by the PCCS Hiebert Marine Laboratory Phytoplankton samples will be shipped directly to David Borkman for analysis other samples are hand delivered from the boat via cooler to the laboratory for processing All information specific to the samples or errors made during sample collection or delivery e g sample spilled flowmeter broken etc will be written in the field logbook Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 15 samples covered by this QAPP will be analyzed PCCS following its SOPs Appendix 2 4 Analytical Methods Requirements 2 41 Preparation of Samples All analytes are pre processed filtered an
109. the OTCR pump a mid or high calibrant continuously and record the steady state signal Continue the steady state until a drift is no longer observed Return the sampler probe to wash and proceed with determinations when the baseline has stabilized An alternate procedure for stabilizing the OTCR is to pump a more concentrated nitrate solution through the column for 5 10 minutes but do not attempt to monitor the signal F Calibrants Specific Stock and Working Calibrant preparation instructions can be found on the back of the flow diagram Be sure to use the flow diagram which covers the concentration range you wish to analyze Working calibrants may be prepared to cover alternate ranges by adding the appropriate volumes of stock or intermediate calibrant to 100 ml volumetric flasks that contain approximately 80 ml of sampler wash solution Dilute the solution to 100 ml with sampler wash solution and mix well Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 40 The following formula can be used to calculate the amount of stock or intermediate calibrant to be used 1 Where desired concentration in mg L of working calibrant to be prepared final volume in ml of working calibrant to be prepared generally 100 ml concentration in mg L of stock or intermediate calibrant volume in ml of stock or intermediate calibrant to be used Rearranging the equa
110. the cleaning solution through all lines in the cartridge for 10 to 15 minutes followed by startup shutdown solution 6 Acid washed glassware should be used for all reagents and calibrants Commercial detergents containing phosphorus should never be used to clean glassware used in phosphorus determination Wash the glassware with 1 1 hydrochloric acid and rinse it thoroughly with deionized water Store the glassware filled with deionized water If the glassware is reserved for use only in phosphorus determination treatment with hydrochloric acid is necessary only occasionally Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 50 I References 1 Standard Methods for the Examination of Water and Wastewater Centennial Edtion 21 Ed 2005 American Public Health Association Washington D C Method referenced Automated Ascorbic Acid Reduction 4500 P F pp 4 155 4 156 2 Methods for Chemical Analysis of Water and Wastewater March 1984 EPA 600 4 79 020 Sample Preservation p xvii Environmental Monitoring and Support Laboratory Office of Research and Development U S Environmental Protection Agency Cincinnati OH 45286 3 Methods and Guidance for Analysis of Water 1999 Office of Water Environmental Protection Agency USEPA Cincinnati OH Method referenced 365 5 4 Automated Nutrient Analysis in Seawater Technical Report Brookhaven National Laboratory Whiteledge Veidt
111. tion to solve for V2 yields C2 For example to prepare a 1 0 mg L working calibrant from a 1000 mg L stock calibrant use 0 1 ml 100 ul of the stock calibrant in 100 ml final volume V5 1 0 mg L 100 ml 1000 mg L V5 0 1 Add this amount of stock calibrant to the volumetric flask and then dilute to volume with the sampler wash solution G Operation Procedure 1 Set up the cartridge as shown in the flow diagram Check all tubing and connections Replace if necessary 2 Place reagent lines in startup solution 3 Turn on power to all units and latch platens to begin liquid flow 4 Verify that the bubble size and spacing is consistent throughout the cartridge If bubbles are splitting up as they enter or exit a coil check and replace fittings if necessary The bubbles should flow smoothly without dragging If dragging occurs add more TX 10 to the startup solution 5 Check all reagent containers on the instrument for particulate matter Reagents should be filtered Be sure all containers are properly labeled and filled before pumping reagents 6 After a stable baseline has been verified on the startup solution place reagent lines in reagent bottles Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 41 10 11 12 13 14 15 16 If using data collection software set up the appropriate sample table Allow reagents to run for 5 to 10 minutes an
112. tives Field se Blank Parameter WI Lab Precision Accuracy Precision Cleanliness M 3096 RPD lt 10 RPD for 15 PD based Method procedural blank Nitrate Nitrite for field iuittum n duplicated on recovery of 55 x MDL 0 05 uM duplicates standards Field Blank lt 5 x MDL lt 30 RPD 15 PD based Method procedural blank 1096 RPD for Ammonia for field istrument duplicates on recovery of 55 x MDL 0 05 uM duplicates standards Field Blank lt 5 x MDL 0 0 Ortho lt 30 RPD lt 10 RPD for 15 PD based Method procedural blank for field duplicates on recovery of lt 5 x MDL 0 02 uM duplicates standards Field Blank lt 5 x MDL lt 30 RPD 15 PD based Method procedural blank Silicate for field m on recovery of lt 5 x MDL 0 05 uM duplicates P standards Field Blank lt 5 x MDL Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 9 lt 30 RPD 6 15 PD based Total nitrogen for field 510 RPD for on recovery of Field Blank lt 5 x MDL 1 07 uM laboratory duplicates duplicates standards lt 30 RPD 15 PD based Total for field Sy eee on recovery of Field Blank lt 5 x MDL 0 23 uM phosphorus duplicates laboratory duplicates standards Chlorophylla lt 50 RPD lt 15 RPD for 15 PD based and for field laboratory on recovery of Filter Blank lt 5 x MDL 0 02 ug L Phaeophytin duplicate
113. to the near surface depth targeting 1 m with a window of 0 5 to 1 5 m depending on sea conditions and triggered to collect the water sample CTD will be lowered at a velocity of approximately 0 5 m per second to within 3 5 m of the seafloor where it will remain for 5 10 seconds and then retrieved Niskin will be lowered to within 3 5 m of seafloor and triggered to collect water sample Zooplankton tow will be initiated Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 12 e Water samples from Niskin bottles will be processed 2 2 1 2 1 Dissolved Inorganic Nutrients Water will be sucked up from a transfer bottle 1 L polypropylene container using a 60 mL syringe The syringe will then be used to push the sample water through an in line filter Nuclepore 47 mm diameter 0 4 um membrane filter and into a 100 mL pre labeled Whirl Pak At the start of each survey day the 60 ml syringe is rinsed with 10 solution then with Milli Q Additionally the syringe 18 rinsed with Milli Q between each station The sample processing begins with the syringe receiving a triple rinse with site water The sample will be stored in a cooler until it can be transferred to the lab and frozen within 8 hours 2 2 1 2 2 Total Nutrients Water from a transfer jar will be decanted into a sterile pre labeled 30 ml polypropylene container This container will receive a triple rinse with site water before being fil
114. tte or split with a Folsom plankton splitter and an aliquot of at least 250 animals will be counted If the total count in an aliquot is less than 250 animals additional aliquots will be counted until either the targeted number of organisms is reached or the entire sample is counted One sample from each survey in February April June August and October will be analyzed in duplicate The results as RPD will be included in the data submission The RPD for total and the most dominant species should be lt 20 If the RPD is greater than 20 a second aliquot will be counted and the three results used to calculate the relative standard deviation RSD which should be lt 20 2 6 Preventive maintenance procedures and schedules 2 6 1 Maintenance for Astoria 2 Autoanalyzer The Astoria 2 Autoanalyzer will be cleaned and maintained no less than once a month as described in the following procedure 1 Place all lines including autosampler wash line in DI water and pump for 10 minutes 2 Place all lines in CHEMWASH or equivalent for 5 to 10 minutes 3 Place all lines in a clean beaker of DI water for 5 to 10 minutes 4 Place all lines in a 5 to 10 Bleach solution for 5 to 10 minutes 5 Place all lines in a clean beaker of DI water for 5 to 10 minutes 6 Place all lines in a 2 Neutrad solution for 5 to 10 minutes 7 Place all lines in a clean beaker of DI water for 5 to 10 minutes 8 Place all lines in IN for 5 to 10 minutes
115. ty monitoring 2008 2009 Revision 1 Boston Massachusetts Water Resources Authority Report 2008 02 92 p Libby PS Fitzpatrick MR Buhl RL Lescarbeau GR Leo WS Borkman DG Turner JT Oviatt CA 2010 Quality Assurance Project Plan QAPP for water column monitoring 2010 Tasks 4 9 and 13 Boston Massachusetts Water Resources Authority Report 2010 2 105 p Turner JT DG Borkman RW Pierce 1995 Should Red Tide Dinoflagellates be Sampled Using Techniques for Microzooplankton Rather than Phytoplankton Pp 737 742 in P Lassus et al Eds Harmful Marine Algal Blooms Lavoisier Paris France Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 66 Standard Operating Procedure 009 Zooplankton Collection and Analysis Collection At each station zooplankton is collected from the upper 19 meters of the water column Samples are collected using standard 333 micrometer um mesh conical nets fitted with General Oceanics helical flow meters The flow meters are calibrated at the beginning of each year to attain the most accurate correction constant possible The 333 um mesh has been experimentally determined to represent the filtering ability of right whale baleen however any mesh size can be used to sample with these protocols Water column collections are initiated by vertically dropping a 60 cm diameter net on station When the net has dropped the full 19 meters the net is pulled obliquely throug
116. uation to solve for V2 yields V2 CIVI C2 For example to prepare a 1 0 mg L working calibrant from a 1000 mg L stock calibrant use 0 1 ml 100 ul of the stock calibrant in 100 ml final volume V2 1 0 mg L 100 ml 1000 mg L V2 0 1 ml Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 73 Add this amount of stock calibrant to the volumetric flask and then dilute to volume with the sampler wash solution H Operation Procedure Set up the cartridge as shown in the flow diagram Check all tubing and connections Replace if necessary Place reagent lines in startup solution Turn on power to all units and latch pump platens to begin liquid flow Verify that the bubble size and spacing is consistent throughout the cartridge If bubbles are splitting up as they enter or exit a coil check and replace fittings if necessary The bubbles should flow smoothly without dragging If dragging occurs add more SLS to the startup solution Check all reagent containers on the instrument for particulate matter Reagents should be filtered Be sure all containers are properly labeled and filled before pumping reagents After a stable baseline has been verified on the startup solution place reagent lines in reagent bottles Due to the lower amount of SLS in the reagents the flow and bubble pattern may drag slightly NOTE Leave the stannous chloride reagent line in the startup solution for 5 minut
117. with a Kimwipe if necessary Open the lid and insert the test tube Close the lid Touch Measure Fluorescence to commence measurement The sample will be measured for 6 seconds and report the average reading for the sample Remove sample add 0 15 mL of 0 1 N cover and mix well Wipe cuvette again with Kimwipe Wait 90 sec and read a second time Record chlorophyll a and pheophytin a values on data sheet When finished measuring samples switch to raw fluorescence mode and measure bland and secondary standard again Record on data sheet Dispose of all acetone in Acetone Waste container Rinse with tap water Soak all test tubes and stoppers in soapy water Liqui Nox for 24 hours Rinse well with tap water and soak in DI water for 24 hours Rinse 3 times with DI water and dry in test tube rack Calculations When in direct concentration mode the following calculations will be use to calculate corrected chlorophyll a and pheophytin values Variables stored during calibration phase of fluorometer Concentration of standard 1 Fblank Fluorescence of Blank value F stana 1 8 Fluorescence of standard 1 before acidification FsanatijA Fluorescence of standard 1 after acidification Fm Acidification Ratio Fstanapi A Fotank Variables required from the sample analysis phase Fluorescence of sample before acidification Fsamp a Fluore
118. y Monitoring in Cape Cod Bay 14 the Laboratory QA QC officer These corrective actions are performed prior to the release of the data from the laboratory The action will be documented in the laboratory notebook The occurrence of a practice or incident that is inconsistent with the established quality assurance and quality control procedures of the laboratory must be formally addressed with a corrective action response Examples of situations requiring initiation of the corrective action process include mishandling of a sample or its documentation or use of unapproved modifications to an analytical method Upon the initiation of a corrective action the problem is documented and a corrective action plan is developed and then approved by the Laboratory Manager and QA manager After required corrective action has been taken the information is documented and verified to be effective and sufficient by the Laboratory Manager and QA Manager information is maintained in the Corrective Action Logbook 2 3 Sample Handling and Custody Requirements 2 3 1 Sample Custody Procedure Field logbooks will be used to record field activities performed during the survey Upon arriving at each station date and time of sampling sample depth Secchi depth wind conditions sampler s initials and any other relevant information will be documented such as site specific environmental conditions including presence of wildlife floatables algae etc When no
119. y of Method Alkaline persulfate digestion oxidizes all forms of inorganic and organic nitrogen to nitrate and hydrolyzes all forms of inorganic and organic phosphorous to ortho phosphate After digestion samples are analyzed as described in SOPs for nitrate nitrite and for ortho phosphate with the exception of substituting the imidazole buffer with an ammonium chloride buffer described below C Sample Handling and Preservation Samples must be kept frozen until analysis Holding time should not exceed 28 days D Raw Materials Required NOTE Chemicals should be of ACS grade or equivalent Sodium hydroxide NaOH FW 40 0 Potassium persulfate K2S20g FW 270 33 Boric acid H3BO3 FW 61 83 Glycine CoH5NO eHCI FW 111 5 Glycerophophate C3H70 PNaze5H20 FW 306 1 Glucose FW 180 2 Ammonium chloride NH4Cl FW 53 49 Ammonium hydroxide NH4OH FW 35 05 Detergent TX 10 API p n 90 0760 04 E Reagent Preparation 1 Sodium Hydroxide 1 0 N Sodium oe Dea Gla dea GE 10 06 NaOH FW 40 00 Ultrapure Water Dissolve 10 0 g of sodium hydroxide in about 180 mL of DI water in a 200 mL volumetric flask Caution When NaOH dissolves in water heat is released After dissolution is complete allow Provincetown Center for Coastal Studies QAPP Water Quality Monitoring in Cape Cod Bay 57 the resulting solution to cool and dilute it to the mark with DI water Make day of sample digesti

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