In Reply Refer To: September 30, 1991 WGS-Mail Stop 412 OFFICE OF WATER QUALITY TECHNICAL MEMORANDUM NO. 91.11 Subject: PROGRAMS AND PLANS--National Water-Quality Networks: Fiscal Year 1992--October 1, 1991 to September 30, 1992 This memorandum contains an outline of Program status and protocol for operation of the National Stream Quality Accounting Network (NASQAN) and the Hydrologic Benchmark Network (HBMN) for fiscal year (FY) 1992. All personnel responsible for collecting NASQAN or HBMN samples should read this memorandum. Network data collection can be significantly enhanced when personnel responsible for field data collection are informed of changes in sample collection and processing procedures. NETWORK OPERATIONS, FY 1992 Changes in Networks operations have, or will, be made in response to the concern about the quality of the USGS's trace element data. The most significant change that will be made in 1992 is that the following elements will be dropped from schedules 176 and 177: arsenic, beryllium, cadmium, chromium, copper, lead, mercury, and zinc. Office of Water Quality Technical Memorandum 91.10 addresses the trace element issues in detail. A copy can be obtained through the TECH_MEMO program on QVARSA or from your District Water-Quality Specialist. Other changes in operations are expected during FY 1992 and will be announced by memorandum and in the QWTALK continuum. Operation during FY 1992 of both NASQAN and HBMN will have few changes in stations. Stations are listed in Appendix A. Sampling frequencies at all stations remain unchanged at this time, but one of the samples at many bimonthly sites will be dropped during the year. When this happens, funding to the districts involved will be adjusted accordingly. Districts will be advised individually of proposed adjustments to the bimonthly schedule. Adjustments will not affect sampling dates when schedules 176 or 177 are to be used. NOTES for FY 1992: 1. Field Alkalinity Review of field techniques and experience in training courses has shown that clarification of the Hach titrator method for determination of alkalinity in the field is needed. The method is documented in Appendix C. All individuals collecting Network samples should be familiar with the method. 2. Sediment Samples Suspended-sediment concentration and sand-fine split are required for all NASQAN and Benchmark samples. Samples for sediment analysis are to be collected in a separate set of bottles (to be composited at the sediment lab) and are NOT to be taken from the churn splitter. See Open-File Report 86-531 (Field Methods for Measurement of Fluvial Sediment by Edwards and Glysson) for details on collection of sediment samples. 3. Samplers All samplers being used for the collection of trace element samples are to be painted with epoxy paint which can be obtained from St. Anthony Falls Hydraulic Laboratory. The entire sampler is to be coated with paint with no bare metal left exposed. Painting the samplers is intended to reduce potential contamination of samples by covering metal surfaces handled by field personnel. 4. Barometric Pressure Barometric pressure is to be measured with a pocket altimeter- barometer and the value recorded on the field sheet and stored in the data base (parameter code 00025). Barometric pressure can be read and reported to the nearest 1 mm Hg, unless the barometer that is used is not that accurate. The barometers that are currently available from HIF are accurate to +/- 0.5 mm Hg. Make sure that the barometer is properly calibrated using the UNCORRECTED or STATION pressure that is obtained from the nearest National Weather Service office. Note that the pressure reported on radio and television is corrected to sea level. 5. Recording Field Measurement Information The times that individual field measurements are made, the location of the measurements (from churn, side of stream, center of flow, point sample, depth-integrated sample), and the method used should be recorded on the field sheets. Since field measurements are often made some time before or after the chemical-quality sample is collected, it is important to note the time(s) (although it(they) won't be able to be stored in the NWIS I data base). Note that dissolved oxygen should be measured at the center of flow whenever possible. 6. Bacteria Every effort is to be made to obtain bacteria counts in the ideal range. Keeping records of flow, volumes filtered, and counts in the field folder and referring to them each time bacteria samples are processed should help in obtaining ideal counts most of the time. If counts are consistently low, and sediment does not interfere, volumes greater than 100 mL can be filtered. 7. Storing Sampler Type in Data Base Contamination from the D-77, solenoid-activated sampler was documented in OWQ Technical Memorandum 90.07. There is reason to believe that other samplers being used for water-quality work may also be affecting samples. An Office of Water Quality-sponsored study is being conducted by Larry Shelton (California District) to determine which samplers (surface water and ground water) may be contributing contamination to samples. The results of this study will be distributed as soon as they are available. In light of these concerns, it is very important that the type of sampler used be known. This information can be provided by storing SAMPLER TYPE under parameter code 84164. Currently-available values for this code are given below. Additional values are being added and will be available with the next revision of NWIS (92.1, scheduled for release in January, 1992). Because of the limitations of NWIS I, only the type of sampler used for the sample collected for chemical analysis needs to be stored. 100.00VAN DORN SAMPLER 110.00SEWAGE SAMPLER 3001.00Sampler, US DH-48 3002.00Sampler, US DH-59 3003.00Sampler, US DH-75P 3004.00Sampler, US DH-75Q 3005.00Sampler, US DH-76 3006.00Sampler, US D-43 3007.00Sampler, US D-49 3008.00Sampler, US D-49AL 3009.00Sampler, US D-74 3010.00Sampler, US D-74AL 3011.00Sampler, US D-77 3012.00Sampler, US P-46 3013.00Sampler, US P-50 3014.00Sampler, US P-61-A1 3015.00Sampler, US P-63 3016.00Sampler, US P-72 3017.00Sampler, US U-59 3018.00Sampler, US U-73 3019.00Sampler, US PS-69 3020.00Sampler, US PS-69TM 3021.00Sampler, US CS-77 3022.00Sampler, US PS-82 3023.00Sampler, US BMH-53 3024.00Sampler, US BMH-53TM 3025.00Sampler, US BM-54 3026.00Sampler, US BM-54TM 3027.00Sampler, US BMH-60 3028.00Sampler, US BMH-60TM 3029.00Sampler, US RBM-80 4080.00PERISTALTIC PUMP 8010.00OTHER 8. Storage of Sampling Method in Data Base Data analysis requires as much knowledge about a sample as possible. Information on the method used to collect the sample is very useful. SAMPLING METHOD is to be stored under parameter code 82398. Values for this code are given below. Additional values for this code are being added and will be available with NWIS revision 92.1. 10.00EQUAL WIDTH INCREMENT (EWI) 20.00EQUAL DISCHARGE INCREMENT (EDI) 25.00TIMED SAMPLING INTERVAL 30.00SINGLE VERTICAL 40.00MULTIPLE VERTICALS 50.00POINT SAMPLE 60.00WEIGHTED BOTTLE 70.00GRAB SAMPLE (DIP) 90.00DISCHARGE INTEGRATED, CENTROID 120.00VELOCITY INTEGRATED 8010.00OTHER 9. Storing Sample Purpose Code in Data Base A value for parameter code 71999 (Sample Purpose Code) is to be stored with all NASQAN and HBMN samples. The following values are to be used: 20.00 = NASQAN 30.00 = Benchmark Use of this code will allow identification and retrieval of Network samples for data analysis. If samples are collected at NASQAN or Benchmark stations for purposes other than National Network operations, the sample purpose code should not be 20.00 or 30.00. 10. Preservative Order Per Office of Water Quality Technical Memorandum 90.01, preservatives are to be added in the following order: Nitric acid to the FA bottle Mercuric chloride to the RC and FC bottles Be sure each bottle is capped and stored before going to the next preservative. Handle ampoules carefully and dispose of them according to the method outlined in memo 90.01. This will help reduce potential sample contamination. 11. Shipping Samples Bottles for nutrient analyses (RC and FC -- brown bottles) are to be shipped to the National Water Quality Laboratory in a separate cooler from other sample bottles. No other sample types are to be placed in the cooler. The cooler should be lined with a plastic bag that is then tied or sealed closed at the top to prevent leakage. The nutrient samples are to be shipped to the lab as soon as possible after sample collection, preferably from the field, by overnight delivery or priority mail. The Analytical Services Request Form for schedule 86 should be sealed in a zip-lock bag and included with the nutrient sample bottles. A postcard requesting the arrival date and temperature of the sample can be placed in the zip-lock bag. Lab personnel will fill out the information and return the postcard to the District. This will enable you to determine how long it takes samples to arrive at the lab and will document whether they have been properly chilled. The reasons for handling nutrient bottles separately from other bottles are: 1) to prevent contamination of other sample types by the mercuric chloride preservative used in the nutrient samples; 2) to help decrease the turn-around time for the analyses; and 3) to save on shipping costs which will be paid directly in FY 1992. Small coolers can be used for one or two sets of nutrient bottles. Be sure that the cooler used is large enough to hold a sufficient amount of ice to keep the sample bottles chilled to 4 degrees Celsius until they reach the lab. Coolers used for nutrient samples should be dedicated for nutrient samples only to prevent possible subsequent contamination of other sample types. All other samples can be shipped unchilled in a cooler or box. Make sure that each container contains a separate Analytical Services Request Form (ASR) or a copy (marked COPY) of the ASR. Beginning on October 1, 1991, shipping charges will be paid by the Districts, either directly or billed by the laboratory. Information on shipping samples is contained in a memorandum dated September 17, 1991, from the Assistant Chief for Operations. A copy can be obtained from your District administrative officer. 12. Bottle Types Following is a list of bottle types and the analyses that are done from each. Individuals processing Network samples should be aware of this information as means of preventing sample contamination. Note that the FAM bottle will not be required this year. Schedule 86 - Nutrients FC - 250 mL, brown poly, filtered, preserved with 1 mL mercuric chloride, chilled to 4' C Nitrogen, dissolved, NO2 + NO3 as N (00631) Nitrogen, dissolved, NH4 as N (00608) Nitrogen, dissolved, NO2 as N (00613) Phosphorus, dissolved, ortho as P (00671) Phosphorus, dissolved as P (00666) RC - 250 mL, brown poly, preserved with 1 mL mercuric chloride, chilled to 4' C Nitrogen, total, NH4 + organic as N (00625) Nitrogen, total, NH4 as N (00610) Nitrogen, total, NO2 as N (00615) Nitrogen, total, NO2 + NO3 as N (00630) Phosphorus, total as P (00665) Phosphorus, total, ortho as P (70507) Schedule 1703 - Radiochemicals RUR - 2 L poly, acid rinsed, untreated Gross alpha, suspended, as U natural (80040) Gross-B, suspended, as CS-137 (03516) Gross-B, suspended, as SR-90 (80060) Gross alpha, suspended, LF, as TH230 (00000) FAR - 2 L poly, acid rinsed, filtered, treated with 2 mL nitric acid (or amount necessary to obtain pH <2) Gross alpha, dissolved, as U natural (80030 Gross-B, dissolved, as CS-137 (03515) Gross-B, dissolved, as SR-90 (80050) Radium-226, dissolved (09511) Uranium, dissolved, ext, LIP, FF (22703) Gross alpha, dissolved, LF, as TH230 (00000) Schedule 176 - Physical properties, common and trace dissolved inorganic constituents FA - 250 mL poly, filtered, treated with 1 mL nitric acid (or amount necessary to obtain to pH <2) Aluminum (01106) Molybdenum (01060) Barium (01005) Nickel (01065) Calcium (00915) Potassium (00935) Cobalt (01035) Selenium (01145) Iron (01046) Silver (01075) Lithium (01130) Sodium (00930) Magnesium (00925) Strontium (01080) Manganese (01056) Vanadium (01085) FU - 500 mL poly, filtered, untreated Silica (00955) Sulfate (00945) Fluoride (00950) Chloride (00940) ROE at 180 C (70300) LC00050 - 125 mL poly, untreated Turbidity, NTU (00076) RU - 250 mL poly, untreated pH, laboratory (00403) Specific conductance, laboratory (90095) Alkalinity, total, laboratory (00417) Schedule 177 - Physical properties, common and trace dissolved inorganic constituents FA - 500 mL poly, filtered, treated with 2 mL nitric acid (or amount necessary to obtain to pH <2) Aluminum (01106) Molybdenum (01060) Barium (01005) Nickel (01065) Calcium (00915) Potassium (00935) Cobalt (01035) Selenium (01145) Iron (01046) Silver (01075) Lithium (01130) Sodium (00930) Magnesium (00925) Strontium (01080) Manganese (01056) Vanadium (01085) FU - 500 mL poly, filtered, untreated Silica (00955) Sulfate (00945) Fluoride (00950) Chloride (00940) ROE at 180 C (70300) LC0050 - 125 mL poly, untreated Turbidity, NTU (00076) RU - 250 mL poly, untreated pH, laboratory (00403) Specific conductance, laboratory (90095) Alkalinity, total, laboratory (00417) Schedule 1904 - Common constituents FA - 250 mL poly, filtered, treated with 1 mL nitric acid (or amount necessary to obtain pH <2) Calcium (00915) Magnesium (00925) Sodium (00930) Potassium (00935) FU - 500 mL poly, filtered, untreated Silica (00955) Chloride (00940) Sulfate (00945) Fluoride (00950) ROE at 180 C (70300) RU - 250 mL poly, untreated pH, laboratory (00403) Specific conductance, laboratory (90095) Alkalinity, total, laboratory (00417) LC0050 - 125 mL poly, untreated Turbidity, NTU (00076) 13. Water-Quality Field Techniques References Below is a list of Office of Water Quality Technical Memoranda and additional references that describe the techniques that are to be used in the collection and processing of water-quality samples. These references should be available to all people collecting water- quality samples. Office of Water-Quality Technical Memoranda Number Date Subject 70.07 11-28-69 Quality control of water analyses: water-quality service units and mobile laboratories 71.04 1-13-71 Methods for collection and analysis of water samples for dissolved minerals and gases (TWRI book 5, Ch. A1) 71.05 3-18-71 Sampling and analysis of water-quality constituents associated with suspended solids 71.09 6-22-71 Guidelines for sampling and analysis of water- quality constituents associated with solids 72.04 11-08-71 Instructions for use of sediment samplers for the collection of samples to be analyzed for organic substances 72.09 1-05-72 Preservation of water samples for chemical analysis (superceded by 80.26) 72.13 2-28-72 Computations of fluvial-sediment discharge (TWRI book 5, Ch. C3) 73.02 9-11-72 Field determinations (superceded by 82.06) 73.07 10-26-72 Teflon sample splitters and plastic sleeves 73.16 4-23-73 Sampling procedures and problems in determining pesticide residues in the hydrologic environment 74.11 2-28-74 Field instruction for NASQAN 75.09 12-26-74 Acceptable methods for collection of water-quality data 75.15 3-13-75 Publication of water temperatures 75.25 6-19-75 Guidelines on sampling and statistical methodologies for ambient pesticide monitoring 76.03 10-14-75 Water-quality field instrumentation 76.17 5-12-76 Sampling mixtures of water and sediment in streams 76.24-T 8-16-76 Sample splitter for water-sediment samples 77.01 12-13-76 Sample splitter for water-sediment samples (cleaning instructions) (supplements 76.24T) 77.03 1-17-77 DH-75 suspended-sediment sampler 77.07 4-06-77 Guidelines for application of Helley-Smith bedload sampler 77.08 5-06-77 Relationship of sediment discharge to streamflow 78.03 1-17-78 Churn splitters (supplements 76.24T and 77.01) 78.06 4-05-78 Field filtering of water samples for chemical analyses 78.13 7-10-78 Microbiological monitoring for water-quality assessment 79.06 12-11-78 Shipment of hazardous material 79.08 3-07-79 Modification of the field chamber for the YSI dissolved oxygen meter 79.10 3-14-79 Recommended procedures for calibrating dissolved oxygen meters 79.15 9-11-79 Data networks; unique number identification for federally funded stations 79.16 9-28-79 Quality assurance of temperature measurements 79.17 10-02-79 Use of Helley-Smith bedload sampler 80.03 11-19-79 Samplers-- P-61 and P-63 point-integrating sediment samplers 80.06 1-24-80 Color-coded nozzles for sediment samplers 80.07 2-05-80 Use of Helley-Smith sampler 80.16 6-02-80 Quality assurance program for sediment laboratories 80.17 7-03-80 New sample splitter for water-quality samples (cone splitter) 80.18 6-13-80 Samplers-- problems with installation of plastic nozzles on samplers 80.26 9-19-80 Preservation of nutrient samples by addition of mercuric chloride 80.30 9-23-80 Significance of bottom material data in evaluating water quality 81.02 10-16-80 Operation and availability-- D-77 water-quality sampler 81.08 2-10-81 Electrodes for pH measurement in low-conductivity waters 81.11 5-08-81 New tables of dissolved oxygen saturation values 82.01 10-27-81 Collecting water samples for stable isotope analysis 82.05 12-11-81 Provisional method for carbonate, dissolved; bicarbonate, dissolved; and carbonate alkalinity, dissolved; electrometric titration, incremental, field 82.06 1-22-82 Policy on publishing constituents with both field and laboratory values 84.04 11-30-83 Technical information: briefing paper on mercury 84.18 9-28-84 Preservation and shipment of water samples for determination of mercury 87.03 2-12-87 pH measurement in low conductivity waters 90.01 10-03-89 Sample preservation and ampuole disposal 90.07 2-02-90 Contamination from D-77 sampler equipped with solenoid-actuated valves 91.01 10-29-90 "Methods for collection and analysis of aquatic biological and microbiological samples," by L.J. Britton and P.E. Greeson, editors, Techniques Water-Resources Investigations (TWRI), Book 5, Chapter A4 91.02 12-05-90 "Methods for collection and processing of surface- water and bed-material samples for physical and chemical analysis," by Janice R. Ward and C. Albert Harr, editors, Open-File Report 90-140 91.04 2-08-91 Office of Water Quality electonic memorandum system 91.08 8-07-91 "A primer on sediment-trace element chemistry" (second edition), by Arthur J. Horowitz 91.09 8-27-91 "Filtration of water-sediment samples for determination of organic compounds," by Mark W. Sandstrom Additional References Barnes, Ivan, 1964, Field measurement of alkalinity and pH: U.S. Geological Survey Water-Supply Paper 1535-H, 17 p. Britton, L.J., and Greeson, P.E., eds, 1989, Methods for collection and analysis of aquatic biological and microbiological samples: U.S. Geological Survey Techniques of Water Resources Investigations, book 5, chap. A4, 363 p. Busenberg, Eurybiades, and Plummer, L.N., 1987, pH measurement of low-conductivity waters: U.S. Geological Survey Water-Resources Investigations Report 87-4060, 22 p. Edwards, T.K., and Glysson, G.D., 1988, Field methods for measurement of fluvial sediment: U.S. Geological Survey Open-File Report 86-531, 188 p. Guy, H.P., and Norman, V.M., 1970, Field methods for measurement of fluvial sediment: U.S. Geological Survey Techniques of Water Resources Investigations, book 3, chap. C2, 59 p. Hem, J.D., 1985, Study and interpretation of chemical characteristics of natural water: U.S. Geological Survey Water-Supply Paper 2254, 263 p. Stevens, H.H., Jr., Ficke, J.F., and Smoot, G.F., 1975, Water temperature--influential factors, field measurement, and data presentation: U.S. Geological Survey Techniques of Water Resources Investigations, book 1, chap. D1, 65 p. Sylvester, M.A., Kister, L.R., and Garrett, W.B.,eds, 1990, Guidelines for the collection, treatment, and analysis of water samples--U.S. Geological Survey Western Region field manual: U.S. Geological Survey, Western Region, internal report, 144 p. Ward, J.R., and Harr, C.A., eds, 1990, Methods for collection and processing of surface-water and bed-material samples for physical and chemical analyses: U.S. Geological Survey Open- File Report 90-140, 71 p. Wells, F.C., Gibbons, W.J., and Dorsey, M.E., 1990, Guidelines for collection and field analysis of water-quality samples from streams in Texas: U.S. Geological Survey Open-File Report 90- 127, 79 p. Wood, W.W., 1976, Guidelines for collection and field analysis of ground-water samples for selected unstable constituents: U.S. Geological Survey Techniques of Water Resources Investigations, book 1, chap. D2, 24 p. Yurewicz, M.C., 1981, Incremental field titration of bicarbonate: U.S. Geolgical Survey Water Resources Division Bulletin, October-December 1981, (for WRD use only), p. 8-13. Collection of Representative Samples As in past years, the Office of Water Quality and the NASQAN/Benchmark staff remind all field personnel that the collection of a representative sample is of utmost importance. Procedures for the collection of a representative sample are well documented. As part of this effort, cross-section surveys (depth and width) of water temperature, pH, specific conductance, dissolved oxygen, and suspended sediment have been required activities at each site in the two networks. Over a period of years the data base of such data should include observations for various seasons and surface water discharges. Cross-section surveys should include a discharge measurement so that each measured constituent can be associated with a weighted discharge value. The results of cross-section surveys should be stored in the WATSTORE/NWIS Water-Quality File. When entering such data, be sure to enter the cross section location - WATSTORE code 00009, CROSS-SECTION LOCATION, FEET FROM LEFT BANK, LOOKING DOWNSTREAM. Contamination of trace-element samples in the field has become a critical issue as laboratory methods continue to improve and reporting limits are lowered. Therefore, all individuals who are collecting water-quality samples need to be aware of the importance of keeping equipment and field vehicles clean and of using proper care when collecting and handling samples. Sample water should be poured carefully into the churn so that the water does not come into contact with hands or the cover of the churn. The churn is to be kept covered, except when water is being poured into it. Sample processing should be done inside the vehicle and away from dust and exhaust. All bottles are to be stored in clean areas and uncapped bottles (other than the untreated bottles) should be discarded. Untreated bottles are to be rinsed with the water that will be going into them (filtered water for filtered samples and unfiltered water for unfiltered samples). Disposable gloves are to be worn when handling preservatives and when processing bacteria samples. Periods for Sample Collection The table below indicates the time periods for sample collection for stations sampled quarterly (four times per year) and bimonthly (six times per year). Sample collection frequencies for each site remain the same in FY 1992 as they were in FY 1991, although this may change later in the year. In order for the data to meet the objectives of the NASQAN and Benchmark programs, it is important that the sampling schedules be adherred to. QUARTERLY STATIONS BIMONTHLY STATIONS first sample OCTOBER-NOVEMBER-DECEMBER OCTOBER- NOVEMBER second sample JANUARY-FEBRUARY-MARCH DECEMBER- JANUARY third sample APRIL-MAY-JUNE FEBRUARY- MARCH fourth sample JULY-AUGUST-SEPTEMBER APRIL-MAY fifth sample ------------------------- JUNE-JULY sixth sample ------------------------- AUGUST- SEPTEMBER Use of ICP Use of the inductively-coupled plasma (ICP) procedure for the analysis of selected dissolved common and trace inorganic constituents will continue to be utilized to decrease analytical costs. The ICP procedure is not to be used whenever the specific conductance is greater than 2,000 uS/cm because the detection limits become greater. Schedule 177 will be used in lieu of schedule 176 whenever the specific conductance is greater than 2,000 uS/cm. Based upon historical specific conductance data for each NASQAN and HBMN Station, the percentage of samples with specific conductance values equal to or greater than 2,000 uS/cm was computed and is given in Appendix A under the right-hand heading "PROBABILITY (%) THAT SPECIFIC CONDUCTANCE WILL BE EQUAL TO OR GREATER THAN 2,000 US/CM." These probabilities indicate the expected frequency of use schedule 177 will get at each site over a long period of time. Determination of specifically which schedule to request for a sample is based on the specific conductance value measured at the time of sampling. Only schedule 176 is authorized for stations with zero probability of the specific conductance exceeding 2,000 uS/cm. Because of the uncertainty involved in predicting the number of samples that will exceed 2,000 uS/cm, both schedule 176 and 177 are authorized for four uses at NASQAN and HBMN stations where the value given in the right- hand column of Appendix A is greater than zero. The actual number of usages authorized between schedules 176 and 177 is however four, not eight, for both HBMN and NASQAN. District Water-Quality Specialists have the authority and responsibility to request schedules 176 versus schedule 177. Because use of schedule 176 versus 177 is dependent solely upon the specific conductance of the sample, District Water-Quality Specialists should ensure that all field personnel are aware that a field specific conductance measurement is absolutely necessary whenever schedule 176 or 177 is to be utilized. Unique Numbers Districts are reminded that all samples (excluding suspended- sediment samples which are analyzed in District sediment laboratories for particle size and concentration) are to be sent to the U.S. Geological Survey National Water-Quality Laboratory in Arvada, CO, with appropriate National Laboratory unique numbers. Unique numbers are described in Quality of Water Branch Technical Memorandum 79.15 and can be obtained by station number through the SPN system on DCOLKA. New unique numbers are established at the beginning of the each water year and are to be used until September 30 of each water year. Personnel collecting NASQAN or HBMN samples should keep a current listing of the unique numbers in their field folder. Any National-Networks sample processed by the National Laboratory without a unique number will result in the analytical costs being billed to the District default account instead of the appropriate National-Networks account. Correcting such billing errors after they occur requires a memorandum to the Coordinator, National Water- Quality Networks. Analytical Services Request Form Although the unique number, date, and time are all that are required on the Analytical Services Request Form, additional information such as station name, special sampling conditions, National-Networks program (NASQAN, Benchmark), etc., are helpful to the National Laboratory personnel and District personnel processing the analytical results. All information coded in the comments section of the Analytical Services Request Form is stored in the Water-Quality File. Uniform Data-Collection Program Districts are reminded of the importance to ensure that all NASQAN and HBMN samples be analyzed for the same measurements as specified later in this memorandum. In particular, all field measurements specified have to be done for every sample. Analytical Schedules Schedules 86, 1703, and 1904 remain unchanged in FY 1992. Schedules 176 and 177 no longer include arsenic, beryllium, cadmium, chromium, copper, lead, mercury, or zinc. NASQAN DATA COLLECTION PROGRAM NASQAN stations to be operated during the period October 1, 1991 through September 30, 1992 are listed in Appendix A. The network will have 410 stations. There will be one NASQAN station sampled monthly, 244 NASQAN stations sampled bimonthly, and 165 NASQAN stations sampled quarterly. NASQAN Sampling Schedule for FY 1992 Please notify the Office of Water Quality if the District responsible for collection of samples for any NASQAN station has changed recently and is therefore incorrectly listed in Appendix A. Changes in locations of sampling sites must be approved by the National Networks Coordinator. NASQAN Sampling Schedule (Quarterly Stations) 4 per year - Field measurements: Instantaneous discharge (WATSTORE Code 00061) Specific Conductance (WATSTORE Code 00095) Water temperature, oC (WATSTORE Code 000010) Barometric pressure (WATSTORE Code 00025) pH (WATSTORE Code 00400) Carbonate, water, dissolved, mg/L (WATSTORE Code 00452) Bicarbonate, water, dissolved, mg/L (WATSTORE Code 00453) Alkalinity, water, dissolved, as CaCO3, mg/L (WATSTORE Code 39086) Hydroxide, water, dissolved, mg/L (WATSTORE Code 71834) Dissolved oxygen (WATSTORE 00300) Fecal coliform bacteria, 0.7 um (WATSTORE Code 31625) Fecal streptococcal bacteria, 0.45 um (WATSTORE Code 31673) 4 per year - Suspended sediment: Concentration (WATSTORE Code 80154) Percent finer than 0.062 mm, sieve diameter (WATSTORE Code 70331) 4 per year - Nutrients, lab schedule 86 4 per year - Physical properties, common and trace dissolved inorganic constituents: lab schedule 176 (specific conductance <2,000 uS/cm) or lab schedule 177 (specific conductance >2,000 uS/cm) Cross-section surveys (depth and width) of temperature, pH, specific conductance, dissolved oxygen, and suspended-sediment concentration as needed to document cross-section homogeneity. NASQAN Sampling Schedule (Bimonthly Stations) 6 per year - Field measurements (same as quarterly) 6 per year - Suspended sediment (same as quarterly) 6 per year - Nutrients, lab schedule 86 2 per year - Physical properties and common dissolved inorganic constituents: lab schedule 1904 (not used when schedule 176 or 177 is used) 4 per year - Physical properties, and common and trace dissolved inorganic constituents: lab schedule 176 or 177 Cross-section surveys (depth and width) of temperature, pH, specific conductance, dissolved oxygen, and suspended-sediment concentration as needed to document cross-section homogeneity. NASQAN Radiochemical Subnetwork NASQAN Radiochemical Subnetwork Stations for FY 1992 are the same as those in FY 1991. Stations are indicated in Appendix A by listing a "2" under the heading "SCHEDULE 1703 RADIOCHEM". There are 46 stations. 2 per year - Radiochemicals, lab schedule 1703 HYDROLOGIC BENCHMARK DATA COLLECTION PROGRAM Hydrologic Benchmark Network stations to be operated in FY 1992 are unchanged from FY 1991, and are listed in Appendix A. Changes in locations of sampling sites must be approved by the National Networks Coordinator. At 3 HBMN stations, only surface-water discharge data are to be collected: these are also given in Appendix A. Of the 55 stations to be sampled for water quality during FY 1992, 43 HBMN stations will be sampled quarterly, 10 will be sampled bimonthly, and 2 will be sampled monthly. All HBMN samples will be analyzed for the same properties and constituents as NASQAN samples. The field measurements and analytical schedules used for the HBMN program are therefore the same as for the NASQAN program. Trace metals samples will be collected at the 55 water-quality Benchmark stations on a quarterly basis. The analytical schedules remain the same. Analysis of radiochemicals at the 55 water-quality Benchmark stations will be on a semiannual basis (1 high-flow and 1 low-flow sample). The specific conductance is likely to exceed 2,000 uS/cm at only one HBMN station - the Bear Den Creek at Mandaree, ND (06332515). Therefore, this station may require schedule 177 for analysis of quarterly dissolved common and trace inorganic constituents. All other stations will require use of schedule 176 for analysis of these constituents. HBMN Sampling Schedule for FY 1992 Please notify the Office of Water Quality if the District responsible for collection of samples for any HBMN station has changed recently and is therefore incorrectly listed in Appendix A. Hydrologic Benchmark Network Sampling Schedule (Quarterly Stations) 4 per year - Field Measurements: Instantaneous discharge (WATSTORE Code 0006l) Specific conductance (WATSTORE Code 00095) Water temperature, oC (WATSTORE Code 00010) Barometric pressure, mm Hg (WATSTORE Code 00025) pH (WATSTORE Code 00400) Carbonate, water, dissolved, mg/L (WATSTORE Code 00452) Bicarbonate, water, dissolved, mg/L (WATSTORE Code 00453) Alkalinity, water, dissolved, as CaCO3, mg/L (WATSTORE Code 39086) Hydroxide, water, dissolved, mg/L (WATSTORE Code 71834) Dissolved oxygen (WATSTORE 00300) Fecal coliform bacteria, 0.7 um (WATSTORE Code 31625) Fecal streptococcal bacteria, 0.45 um (WATSTORE Code 31673) 4 per year - Suspended sediment: Concentration (WATSTORE Code 80154) Percent finer than 0.062 mm, sieve diameter (WATSTORE Code 70331) 4 per year - Nutrients, lab schedule 86 4 per year - Physical properties, common and trace dissolved inorganic constituents: lab schedule 176 2 per year - Radiochemicals, lab schedule 1703 Cross-section surveys (depth and width) of temperature, pH, specific conductance, dissolved oxygen, and suspended-sediment concentration as needed to document cross-section homogeneity. Hydrologic Benchmark Network Sampling Schedule (Bimonthly Stations) 6 per year - Field measurements (same as quarterly) 6 per year - Suspended sediment (same as quarterly) 6 per year - Nutrients, lab schedule 86 4 per year - Physical properties, common and trace dissolved inorganic constituents: lab schedule 176 (specific conductance <2,000 uS/cm) or lab schedule 177 (specific conductance >2,000 uS/cm) 2 per year - Physical properties and common dissolved inorganic constituents: lab schedule 1904 (not used when schedule 176 or 177 is used) 2 per year - Radiochemicals, lab schedule 1703 Cross-section surveys (depth and width) of temperature, pH, specific conductance, dissolved oxygen, and suspended-sediment concentration as needed to document cross-section homogeneity. Hydrologic Benchmark Network Sampling Schedule (Monthly Stations) 12 per year - Field measurements (same as quarterly) 12 per year - Suspended sediment (same as quarterly) 12 per year - Nutrients, lab schedule 86 4 per year - Physical properties and common and trace dissolved inorganic constituents: lab schedule 176 8 per year - Physical properties and common dissolved inorganic constituents: lab schedule 1904 (not used when schedule 176 is used) 2 per year - Radiochemicals, lab schedule 1703 Cross-section surveys (depth and width) of temperature, pH, specific conductance, dissolved oxygen, and suspended-sediment concentration as needed to document cross-section homogeneity. If any information in this memorandum prompts questions or comments, please call Kathy Fitzgerald whose current number is 959-6902 (FTS) or (703) 648-6902 (Commercial). David A. Rickert Attachments This memorandum does not supersede any previous memorandum. Distribution: A, B, S, FO, PO Key Words: water quality, networks, sampling, NASQAN, Benchmark, FY 1992 APPENDIX A This appendix contains the listing by District of all NASQAN and HBMN stations. Specific information for each site includes sampling frequency and laboratory schedules. Sampling frequency and have not been changed from FY 1991, although a change in the frequency at the bimonthly stations will be made later in the year. Laboratory schedules 86, 1703, and 1904 remain unchanged, but schedules 176 and 177 have had arsenic, beryllium, cadmium, chromium, copper, lead, mercury, and zinc dropped from them. Copies of the appendix may be retrieved via computer by the following command: FTR NASQAN>APPENDIX.A.92 FTS_DEPOT>== -SS QVARSA You may then access the Appendix file in your FTS_DEPOT. APPENDIX B NUTRIENTS SCHEDULE 86 WN OWNER:NQ COST: 81.73 CALCULATED LAB WATSTORE CODE CODE INCLUDED PARAMETERS 0084 00625 A NITR. NH4+ORG AS N T 0123 00610 B NITR TOT NH4 AS N 0128 00666 B PHOSPHORUS, DIS. 0129 00665 B PHOSPHORUS, TOTAL 0160 00613 B NITR DIS NO2 AS N 0162 00671 B PHOS DIS ORTHO AS P 0228 00631 B NITR DIS NO2+NO3 -N 0301 00608 B NITR DISS NH4 AS N REQUIRES 0250 ml OF FC 0250 ml OF RC RADIOCHEMICALS SCHEDULE 1703 WR OWNER:NQ COST: 338.00 FIXED LAB WATSTORE CODE CODE INCLUDED PARAMETERS 0444 80030 A GROSS ALPHA DIS U-NA 0445 80050 A GROSS-B, DIS SR-90 0446 80040 A GROSS ALPHA SUS.U-NA 0447 80060 A GROSS-B, SUSP. SR-90 0455 03515 A GROSS-B, DIS CS137 0456 03516 A GROSS-B, SUSP. CS137 0794 09511 B RADIUM-226, DISS. RN 1386 22703 E U.DIS,EXT,LIP,FF 1393 00000 A G.ALPHA,DIS,LF,TH230 1395 00000 A G.ALPHA,SUS,LF,TH230 REQUIRES 0002 liters OF FAR 0002 liters OF RUR PHYSICAL PROPERTIES, COMMON AND TRACE DISSOLVED INORGANIC CONSTITUENTS SCHEDULE 176 WI OWNER:NQ COST: 222.00 FIXED LAB WATSTORE CODE CODE INCLUDED PARAMETERS 0027 70300 A ROE, DISS. AT 180 C 0050 00076 A TURBIDITY (NTU) 0054 00935 B POTASSIUM, DISSOLVED 0068 00403 A PH (LABORATORY) 0069 90095 A SP. CONDUCTANCE LAB 0070 90410 A ALK TOT LAB. CACO3 0087 01145 A SELENIUM, DISSOLVED 0641 01005 C BARIUM, DISSOLVED 0644 01035 C COBALT, DISSOLV. 0645 01046 D IRON, DISSOLV. 0648 01056 C MANGANESE, DISSOLVED 0649 01060 A MOLYBDENUM, DISS. 0652 01080 B STRONTIUM, DISSOLVED 0653 01085 B VANADIUM, DISSOLVED 0659 00915 D CALCIUM, DISSOLVED 0663 00925 C MAGNESIUM, DISSOLVED 0664 01130 B LITHIUM, DISSOLVED 0667 00955 D SILICA, DISSOLVED 0675 00930 C SODIUM, DISSOLVED 1284 01106 E ALUMINUM-DIS-DCP 1552 01075 F SILVER GFAA DIS 1562 01065 F NICKEL GFAA DIS 1571 00940 J CHLORIDE DIS IC 1572 00945 G SULFATE DIS IC 1573 00950 E FLUORIDE DIS IC REQUIRES 0250 ml OF FA 0250 ml OF RU 0125 ml OF LC0050 0500 ml OF FU SCHEDULE 177 WI OWNER:NQ COST: 275.86 CALCULATED LAB WATSTORE CODE CODE INCLUDED PARAMETERS 0007 01005 B BARIUM, DIS. 0012 00915 C CALCIUM, DISSOLV. 0027 70300 A ROE, DISS. AT 180 C 0039 01130 A LITHIUM, DISSOLV. 0040 00925 B MAGNESIUM, DISSOLV. 0042 01056 A MANGANESE, DISSOLV. 0050 00076 A TURBIDITY (NTU) 0054 00935 B POTASSIUM, DISSOLVED 0056 00955 C SILICA, DIS. 0059 00930 B SODIUM, DIS. 0062 01080 A STRONTIUM, DIS. 0068 00403 A PH (LABORATORY) 0069 90095 A SP. CONDUCTANCE LAB 0070 90410 A ALK TOT LAB. CACO3 0087 01145 A SELENIUM, DISSOLVED 0110 01060 B MOLYBDENUM, DISSOLV. 0172 01046 C IRON, DIS. 1210 01085 D VANADIUM, DIS. AUTO. 1284 01106 E ALUMINUM-DIS-DCP 1552 01075 F SILVER GFAA DIS 1556 01035 F COBALT GFAA DIS 1562 01065 F NICKEL GFAA DIS 1571 00940 J CHLORIDE DIS IC 1572 00945 G SULFATE DIS IC 1573 00950 E FLUORIDE DIS IC REQUIRES 0500 ml OF FA 0250 ml OF RU 0125 ml OF LC0050 0500 ml OF FU COMMON CONSTITUENTS SCHEDULE 1904 WI OWNER:NQ COST: 93.59 CALCULATED LAB WATSTORE CODE CODE INCLUDED PARAMETERS 0012 00915 C CALCIUM, DISSOLV. 0027 70300 A ROE, DISS. AT 180 C 0040 00925 B MAGNESIUM, DISSOLV. 0050 00076 A TURBIDITY (NTU) 0054 00935 B POTASSIUM, DISSOLVED 0056 00955 C SILICA, DIS. 0059 00930 B SODIUM, DIS. 0068 00403 A PH (LABORATORY) 0069 90095 A SP. CONDUCTANCE LAB 0070 90410 A ALK TOT LAB. CACO3 1571 00940 J CHLORIDE DIS IC 1572 00945 G SULFATE DIS IC 1573 00950 E FLUORIDE DIS IC REQUIRES 0125 ml OF LC0050 0250 ml OF FA 0250 ml OF RU 0500 ml OF FU APPENDIX C ALKALINITY - INCREMENTAL TITRATION METHOD Hach Titrator INTRODUCTION Alkalinity is a measure of the buffering capacity of water against acid. Degasification, precipitation, and other chemical and physical reactions may cause the concentrations of carbonate and bicarbonate to change substantially within several hours or even minutes after sample collection. Consequently, field values for carbonate and bicarbonate or alkalinity usually are more reliable than values obtained in the laboratory (Wells and others, 1990). Particulates can take up some strong acid by dissolution, adsorption, or ion exchange and, thereby, cause anomalously high measurements. For this reason, filtration through a 0.45 micron pore-size filter is required In order to prevent contamination by wind-borne dust and loss of carbon dioxide due to warming by the sun, the analysis should be done in an enclosed vehicle (Branch of Water Quality Technical Memorandum 82.05). APPARATUS 1. pH meter with combination pH probe or equivalent. 2. Hach digital titrator. 3. Titrant acid cartridges (0.16 and 1.6 N) with straight- or bent- tube delivery tubes. (NOTE: Clear delivery tubes are now available from Hach) 4. Magnetic stirrer. 5. Deionized water. 6. 50 mL and 100-mL volumetric pipets. METHOD 1. Select the appropriate strength titrant, 0.1600 Normal (N) or 1.600N sulfuric acid, and sample volume from the following table, based on the expected alkalinity. Record the acid normality and sample volume on the field sheet. Expected Alkalinity Sample Volume Acid Normality <20 100 0.1600 20-50 50 0.1600 50-150 100 1.600 >150 50 1.600 NOTE: The volumes and acid normalities in the above table are guidelines only. Inflection points will be better defined by using the 0.1600 N acid. 2. Assemble the digital titrator: a) Insert the appropriate cartridge into the titrator and turning it 1/4 turn to lock it in position. b) Remove the vinyl cap and insert a delivery tube into the cartridge tip. Delivery tubes cannot be interchanged between different normality cartridges and should be identified to avoid cross-contamination. c) Flush the tube by turning the delivery knob to release some of the titrant into a waste container. Make sure that a sufficient amount is released to assure that there are no bubbles or water in the tube. d) Gently blot any droplets that adhere to the end of the tube and set the digital counter reading to ZERO. 3. Use a clean volumetric pipet or cylinder, rinse with sample water, and measure the appropriate sample volume into a clean beaker containing a Teflon-coated stirring bar. 4. Place rinsed pH probe (previously rinsed with sample water) into the sample and place the beaker on a magnetic stirrer. 5. Turn on stirrer and adjust stirring rate to LOW. Sample should be GENTLY stirred throughout the titration. Turn on pH meter, allow reading to stabilize and then read and record the initial pH value. 6. If sample pH is less than 8.3, then skip the next step (7). 7. If sample pH is greater than 8.3, add sulfuric acid by small increments (1 to 3 digital counts at a time) until the pH is less than 8.0. The tip of the delivery tube should be below the sample surface (keep the tube clean to avoid contamination of the sample). Allow 15-20 seconds for equilibration between incremental additions of acid. Record pH and digital counter reading after each addition of acid. 8. Titrate rapidly to pH 5.0 (5.5 for alkalinities of <20 mg/L). The tip of the delivery tube should be below the sample surface (keep the tube clean to avoid contamination of the sample). Allow 15-20 seconds for equilibration and record the digital counter reading. 9. From pH 5.0 (5.5) to 4.0, add acid by small increments (1 to 3 digital units at a time). Allow 15-20 seconds for equilibration between incremental additions of acid and record pH and digital counter reading after each addition of acid. 10. Calculations: (a) Calculate the change in pH and the change in counter numbers and record these values on the field sheet. (b) Divide each change in pH by the change in the counter numbers and record the results on the field sheet. (c) The endpoints are the counter numbers where the maximum rates of change in pH per counter number increments occur. If a tie for the end point occurs, choose the last one (the one with the lower pH). (d) Calculate carbonate (00452). CO3 (mg/L as CO3) = A x F1/mL sample (e) Calculate bicarbonate (00453). HCO3 (mg/L as HCO3) = [B - 2(A)] x F2/mL sample (f) Calculate total alkalinity (39086). Total Alkalinity = B x F3/mL sample where: A = digital count from initial pH to endpoint near 8.3 B = digital count from initial pH to endpoint near 4.5 0.1600N 1.600N F1 12.0 120 F2 12.2 122 F3 10.0 100 OR Use the Texas Alkalinity Program if it is available on your District PR1ME. After completing the titration, remove the cartridge from the titrator and replace the vinyl cap immediately to avoid exposure of the contents to the air. Rinse the delivery tube with distilled water and blow out the remaining water with a syringe to avoid starting the next titration with water. Store the delivery tubes in a clean plastic bag. REPORTING Report total alkalinity, carbonate, and bicarbonate concentrations as follows: less than 1,000 mg/L, to whole numbers; 1,000 mg/L and above, three significant figures. REFERENCES Barnes, Ivan, 1964, Field measurement of alkalinity and pH: U.S. Geological Survey Water-Supply Paper 1535-H, 17 p. Quality Water Service Unit, 1990, Water-quality field techniques: U.S. Geological Survey, Florida District, internal document, 164 p. Sylvester, M.A., Kister, L.R., and Garrett, W.B., eds, 1990, Guidelines for the collection, treatment, and analysis of water samples--U.S. Geological Survey Western Region field manual: U.S. Geological Survey, Western Region, internal document, 144 p. Wells, F.C., Gibbons, W.J., and Dorsey, M.E., 1990, Guidelines for collection and field analysis of water-quality samples from streams in Texas: U.S. Geological Survey Open-File Report 90- 127, 79p. Branch of Water Quality Technical Memorandum 82.05: December 11, 1981.