In Reply Refer To: September 21, 1993 WGS-Mail Stop 412 OFFICE OF WATER QUALITY TECHNICAL MEMORANDUM NO. 93.14 Subject: PROGRAMS AND PLANS--National Water-Quality Networks: Fiscal Year 1994--October 1, 1993 to September 30, 1994 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 (HBN) for fiscal year (FY) 1994. All personnel responsible for collecting NASQAN or HBN samples should read and have their own copy of 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 1994 The following elements will continue to be excluded from schedules 176 and 177 in FY 1994: arsenic, beryllium, cadmium, chromium, copper, lead, mercury, and zinc. In addition, NWQL has discontinued analyses for ammonia, nitrite, nitrite + nitrate, and orthophosphorus in unfiltered samples. These changes have been made in the lab schedules. NWQL expects to make changes in the radiochemistry schedule 1703 during FY 1994. These changes will be announced by memo and in the QWTALK and LABNEWS continuums. Beginning on October 1, 1993, the protocol for cleaning sampling equipment, which is outlined in appendix D of this memo, is to be used. During FY 1994, the new sample collection and processing protocol for inorganics could be implemented on a station-by-station basis if individual districts want to do that. The Office of Water Quality (OWQ) can provide technical assistance; however, financial assistance is not available. If available, D-77 and/or DH-81 samplers should be used as soon as possible at NASQAN and HBN stations where sampling conditions permit. Sampler contamination studies have shown that all other samplers are unacceptable for most trace-element sampling. Office of Water Quality Technical Memorandum 91.10 addresses trace-element issues in detail and additional memos on cleaning procedures and the results of the sampler testing are being prepared. Copies of all technical memos can be obtained through the TECH_MEMO program on QVARSA or from your District Water- Quality Specialist. As a result of increasing station operation costs and a significant decrease in the budget for network operation, a large number of NASQAN stations are discontinued as of October 1, 1993. Additional stations may be discontinued during FY 1994. The discontinued stations are listed below: STN STATE 02466031 BLACK WARRIOR RIVER BL WARRIOR DAM NR EUTAW AL Alabama 02479560 ESCATAWPA RIVER NEAR AGRICOLA MS Alabama 15024800 STIKINE R NR WRANGELL AK Alaska 09471000 SAN PEDRO R AT CHARLESTON, AZ Arizona 09508500 VERDE R BELOW TANGLE CR, ABOVE HORSESHOE DAM, AZ Arizona 07265450 MISSISSIPPI RIV NR ARKANSAS CITY, ARK. Arkansas 10356500 SUSAN R AT SUSANVILLE CALIF California 11187000 KERN RIVER AT KERNVILLE CALIF California 11218500 KINGS RIVER BL NF NR TRIMMER CALIF California 11458000 NAPA RIVER NEAR NAPA CALIF California 11532500 SMITH RIVER NEAR CRESCENT CITY, CALIF. California 08251500 RIO GRANDE NEAR LOBATOS, CO. Colorado 09163500 COLORADO RIVER NEAR COLORADO-UTAH STATE LINE Colorado 09251000 YAMPA RIVER NEAR MAYBELL, CO. Colorado 01122610 SHETUCKET R AT SOUTH WINDHAM, CT Connecticut 02248000 SPRUCE CREEK NR SAMSULA, FLA. Florida 02256500 FISHEATING CREEK AT PALMDALE, FLA. Florida 02288900 TAMIAMI CANAL OUTLETS, 40-MILE BEND TO MONROE, FLA Florida 02329000 OCHLOCKONEE RIVER NR HAVANA, FLA. Florida 02368000 YELLOW RIVER AT MILLIGAN, FLA. Florida 02228000 SATILLA RIVER AT ATKINSON, GA. Georgia 16229300 KALIHI STREAM AT KALIHI, OAHU, HI Hawaii 16713000 WAILUKU RIVER AT HILO, HAWAII, HI Hawaii 12413500 COUER D'ALENE R AT CATALDO, ID Idaho 13317000 SALMON RIVER AT WHITEBIRD, IDAHO Idaho 03345500 EMBARRAS R AT STE. MARIE, IL Illinois 05570000 SPOON R AT SEVILLE, IL Illinois 06810000 NISHNABOTNA RIVER ABOVE HAMBURG, IOWA Iowa 06856600 REPUBLICAN R AT CLAY CENTER, KS Kansas 03215000 BIG SANDY R AT LOUISA, KY Kentucky 07367640 OUACHITA RIVER AT COLUMBIA, LA. Louisiana 07369500 TENSAS RIVER AT TENDAL, LOUISIANA Louisiana 07375050 TCHEFUNCTA RIVER NEAR COVINGTON, LA. Louisiana 08012150 MERMENTAU RIVER AT MERMENTAU Louisiana 01049265 KENNEBEC RIVER AT NORTH SIDNEY, ME Maine 01059400 ANDROSCOGGIN RIVER AT BRUNSWICK, ME Maine 01618000 POTOMAC R AT SHEPHERDSTOWN, WV Maryland 01636500 SHENANDOAH RIVER AT MILLVILLE, W. VA. Maryland 04045500 TAHQUAMENON RIVER NR TAHQUAMENON PARADISE, MICH. Michigan 04059500 FORD RIVER NR HYDE, MICH. Michigan 04135000 THUNDER BAY RIVER NR ALPENA, MICH. Michigan 04159010 PIGEON R NEAR CASEVILLE, MI Michigan 04014500 BAPTISM RIVER NEAR BEAVER BAY, MN Minnesota 05112000 ROSEAU RIVER BELOW STATE DITCH 51 NR CARIBOU, MN Minnesota 07292500 HOMOCHITTO RIVER AT ROSETTA, MS Mississippi 06918070 OSAGE RIVER NEAR SCHELL CITY MO Missouri 06930800 GASCONADE RIVER ABOVE JEROME, MO Missouri 06130500 MUSSELSHELL RIVER AT MOSBY, MT. Montana 06214500 YELLOWSTONE RIVER AT BILLINGS MT Montana 06308500 TONGUE RIVER AT MILES CITY, MT. Montana 12363000 FLATHEAD RIVER AT COLUMBIA FALLS, MT. Montana 06792000 CEDAR R NR FULLERTON, NE Nebraska 06882000 BIG BLUE R AT BARNSTON, NE Nebraska 09419515 MUDDY R AB LAKE MEAD NR OVERTON, NV. Nevada 10301500 WALKER R NR WABUSKA, NV Nevada 01409815 WEST BRANCH WADING R AT MAXWELL NJ New Jersey 01411500 MAURICE R AT NORMA NJ New Jersey 08370500 RIO GRANDE AT FORT QUITMAN, TEXAS New Mexico 08382650 PECOS R AB SANTA ROSA LAKE, NM New Mexico 08481500 RIO TULAROSA NEAR BENT, NM New Mexico 09364500 ANIMAS RIVER AT FARMINGTON, NM New Mexico 01304000 NISSEQUOGUE RIVER NEAR SMITHTOWN NY New York 01305000 CARMANS RIVER AT YAPHANK NY New York 04213500 CATTARAUGUS CREEK AT GOWANDA NY New York 02091500 CONTENTNEA CREEK AT HOOKERTON, N. C. North Carolina 03453500 FRENCH BROAD RIVER AT MARSHALL, N. C. North Carolina 06340500 KNIFE RIVER AT HAZEN, ND North Dakota 06349000 HEART RIVER NR MANDAN, ND North Dakota 03245500 L MIAMI R AT MILFORD OH Ohio 04212200 GRAND R AT PAINESVILLE OH Ohio 07152500 ARKANSAS RIVER AT RALSTON, OK Oklahoma 07175500 CANEY R NR RAMONA, OK Oklahoma 07243500 DEEP FORK NR BEGGS, OK Oklahoma 07305000 NORTH FORK RED RIVER NR HEADRICK, OK Oklahoma 14128910 COLUMBIA RIVER AT WARRENDALE,OREG. Oregon 14301000 NEHALEM RIVER NEAR FOSS, OREG. Oregon 01562000 RAYSTOWN BRANCH JUNIATA R AT SAXTON Pennsylvania 03085000 MONONGAHELA RIVER AT BRADDOCK, PA. Pennsylvania 50092000 RIO GRANDE DE PATILLAS NR PATILLAS Puerto Rico 02136000 BLACK RIVER AT KINGSTREE, S.C. South Carolina 06360500 MOREAU R NEAR WHITEHORSE SD South Dakota 06471000 JAMES R AT COLUMBIA SD South Dakota 03495500 HOLSTON RIVER NEAR KNOXVILLE, TENN. Tennessee 03535912 CLINCH RIVER AT MELTON HILL DAM (TAILWATER),TENN Tennessee 07308500 RED RIVER NR BURKBURNETT, TX Texas 08080500 DMF BRAZOS RIVER NEAR ASPERMONT, TEX. Texas 08106500 LITTLE RIVER AT CAMERON, TEX. Texas 08147000 COLORADO RIVER NR SAN SABA, TEX. Texas 08158000 COLORADO RIVER AT AUSTIN, TEX. Texas 08164000 LAVACA RIVER NEAR EDNA, TEXAS Texas 08189500 MISSION RIVER AT REFUGIO, TEXAS Texas 08377200 RIO GRANDE AT FOSTER RANCH NR LANGTRY, TEXAS Texas 10039500 BEAR R AT BORDER WY Utah 10141000 WEBER RIVER NR PLAIN CITY UTAH Utah 02049500 BLACKWATER R NR FRANKLIN, VA Virginia 02052000 MEHERRIN RIVER AT EMPORIA, VA Virginia 02075500 DAN RIVER AT PACES VA Virginia 12040500 QUEETS RIVER NEAR CLEARWATER, WASH. Washington 12200500 SKAGIT RIVER NEAR MOUNT VERNON, WASH. Washington 12500450 YAKIMA R ABV AHTANUM CR AT UNION GAP, WASH. Washington 04027000 BAD RIVER NEAR ODANAH, WI Wisconsin 05401050 TENMILE CREEK NR NEKOOSA, WI Wisconsin 06265000 BELLE FOURCHE RIVER BELOW MOORCROFT, WY Wyoming Five Hydrologic Benchmark Network stations have been discontinued because they no longer meet the objectives of the Network. One HBN station has been put on inactive status, and one NASQAN station has been changed to a HBN station. These stations are listed below: STN STATE DISCONTINUED: 02197300 UPPER THREE RUNS NR NEW ELLENTON South Carolina (development in upper part of basin; high fecal coliform counts) 02212600 FALLING CREEK NR JULIETTE Georgia (feldspar plant in headwaters; high fluoride, chloride, sulfate) 03276700 SOUTH HOGAN CREEK NE DILLSBORO Indiana (pig farms,sewage bypass station; high nitrate, phosphorus,chloride) 05376000 NORTH FORK WHITEWATER RIVER NR ELBA Minnesota (80% farmland; 3 small communities and wastewater treatment plants) 06897950 ELK CREEK NR DECATUR CITY Iowa (row crops; factory; high bacteria counts; high nitrate) INACTIVATED: 16717000 Honolii Stream nr Papaikou, Hawaii Hawaii CHANGED FROM NASQAN TO HBN: 16618000 Kahakuloa Stream nr Honokohau, Maui Hawaii Active stations and sampling frequencies are listed in Appendix A. Sampling frequencies at all stations remain at the level designated in the memorandum from the Chief of the Office of Water Quality, dated January 27, 1992. Thus many (but not all) bimonthly stations will continue to collect five samples only in FY 1994. Beginning in FY 1995, the goals of NASQAN will be changed to emphasize transport of constituents between major river basins and off the continent. Thus, stations measuring large drainage areas will be important. Because of the change in goals and continuing financial constraints, major changes to the NASQAN network and operation will occur in FY 1995. NOTES for FY 1994: 1. Field Alkalinity The results of the National Field Quality Assurance proficiency tests show that field personnel continue to have problems determining alkalinity in the field, especially with the Hach titrator. The Hach titrator method for determination of alkalinity 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. If NAWQA samples are being collected at the same time as NASQAN or HBN samples, and a cone splitter is being used, the sediment sample can collected from the cone 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 Tests of existing samplers to determine their acceptability for collection of trace-element samples have shown that all samplers, except the D-77 (with a teflon or polypropylene bottle and/or a teflon or Reynolds oven bag) and the DH-81 (with a teflon or polypropylene bottle), contaminate samples at levels that are significant at the microgram per liter (parts per billion) level. OWQ realizes that these two samplers cannot accomodate all environmental conditions; the Instrumentation Committee (ICOM) has formed an ad hoc sampler committee that will recommend development of additional, non-contaminating samplers. Plans for the frame-type bag sampler are available from Kathy Fitzgerald (edoc to KKFITZ). This sampler is documented in OWQ Technical Memorandum 83.08. All samplers being used for the collection of trace-element samples (including weighted-bottle samplers) are to be painted with epoxy paint which can be obtained from the Corps of Engineers Waterways Experiment Station in Vicksburg, Mississippi. The phone number is 601-634-3735. The HIF has tested several paints in order to select one that will not be a source of contamination. Therefore, please do not use paint obtained from other sources. The entire sampler is to be coated with paint; no bare metal should be 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 sufficiently 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. Because field measurements are often made some time before or after the chemical-quality sample is collected, it is important to note the time(s) (even though it cannot be stored in the NWIS I data base). Dissolved oxygen should be measured at the center of flow whenever possible. Use of the National Field Forms is recommended. They are available from the QW Service Unit in Ocala (edoc to OCALAMAN). 6. Bacteria Every effort should 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. See TWRI Book 5, Chapter A4 for correct methods for calculating bacteria counts. 7. Storing Sampler Type in Data Base In light of the concerns about potential contamination from samplers, 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. Because of the limitations of NWIS I, only the type of sampler used for collecting chemical samples needs to be stored. 84164 100.00VAN DORN SAMPLER 84164 110.00SEWAGE SAMPLE 84164 120.00VELOCITY INTEGRATED SAMPLE 84164 125.00KEMMERER BOTTLE 84164 3001.00Sampler, US DH-48 84164 3002.00Sampler, US DH-59 84164 3003.00Sampler, US DH-75P 84164 3004.00Sampler, US DH-75Q 84164 3005.00Sampler, US DH-76 84164 3006.00Sampler, US D-43 84164 3007.00Sampler, US D-49 84164 3008.00Sampler, US D-49AL 84164 3009.00Sampler, US D-74 84164 3010.00Sampler, US D-74AL 84164 3011.00Sampler, US D-77 84164 3012.00Sampler, US P-46 84164 3013.00Sampler, US P-50 84164 3014.00Sampler, US P-61-A1 84164 3015.00Sampler, US P-63 84164 3016.00Sampler, US P-72 84164 3017.00Sampler, US U-59 84164 3018.00Sampler, US U-73 84164 3019.00Sampler, US PS-69 84164 3020.00Sampler, US PS-69TM 84164 3021.00Sampler, US CS-77 84164 3022.00Sampler, US PS-82 84164 3023.00Sampler, US BMH-53 84164 3024.00Sampler, US BMH-53TM 84164 3025.00Sampler, US BM-54 84164 3026.00Sampler, US BM-54TM 84164 3027.00Sampler, US BMH-60 84164 3028.00Sampler, US BMH-60TM 84164 3029.00Sampler, US RBM-80 84164 3030.00US DH-48 TM 84164 3031.00US DH-48 TM W/ TEFLON GASKET AND NOZZLE 84164 3032.00US DH-59 TM 84164 3033.00US DH-59 TM W/ TEFLON GASKET AND NOZZLE 84164 3034.00US DH-76 TM 84164 3035.00US DH-76 TM W/ TEFLON GASKET AND NOZZLE 84164 3036.00US D-74 TM 84164 3037.00US D-74 AL-TM 84164 3038.00US D-74 AL-TM W/ TEFLON GASKET AND NOZZLE 84164 3039.00US D-77 TM 84164 3040.00US D-77 TM MODIFIED TEFLON BAG SAMPLER 84164 3041.00US P-61 AL-TM 84164 3042.00US P-61 84164 3043.00US P-61 TM 84164 3044.00US DH-81 84164 3045.00US DH-81 WITH TEFLON CAP AND NOZZLE 84164 3050.00TEFLON BAG SAMPLER 84164 3060.00WEIGHTED-BOTTLE SAMPLER 84164 3070.00GRAB SAMPLE 84164 4010.00THIEF SAMPLER 84164 4020.00OPEN-TOP BAILER 84164 4025.00DOUBLE-VALVE BAILER 84164 4030.00SUCTION PUMP 84164 4035.00CENTRIFUGAL PUMP 84164 4040.00SUBMERSIBLE PUMP 84164 4041.00SUBMERSIBLE HELICAL ROTOR PUMP 84164 4045.00SUBMERSIBLE GEAR PUMP 84164 4050.00SQUEEZE PUMP 84164 4060.00GAS RECIPROCATING PUMP 84164 4070.00GAS LIFT 84164 4075.00PISTON PUMP 84164 4080.00PERISTALTIC PUMP 84164 4090.00JET PUMP 84164 4095.00LINE-SHAFT TURBINE PUMP 84164 8000.00NONE 84164 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. 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 HBN 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 beginning to add the next preservative to the remaining bottles. Handle ampoules carefully and dispose of them according to the method outlined in OWQ Tech Memos 90.01 and 92.11. This will help reduce potential sample contamination. 11. Shipping Samples Bottles for nutrient analyses (RC and FC -- 125 mL 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 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. 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 has a separate Analytical Services Request Form (ASR) or a copy (marked COPY) of the ASR. The latest revision of the ASR is in tablets with a blue cover. Books (of 50) forms can be obtained by sending edoc to DENSUPPL. There is no charge for the forms. Older versions of the ASR should not be used. Shipping charges are 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 Hydrologist 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 - 125 mL, brown poly, filtered, preserved with 0.5 mL mercuric chloride, chilled to 4 degrees 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 - 125 mL, brown poly, preserved with 0.5 mL mercuric chloride, chilled to 4oC Nitrogen, total, NH4 + organic as N (00625) Phosphorus, total as P (00665) 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 statistica 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 91.10 9-30-91 Dissolved trace element data 92.01 12-20-91 Distilled/deionized water for District operations 92.02 12-20-91 Field preparation of containers for aqueous samples 92.04 3-20-92 Revised statement regarding dissolved trace-element data production 92.05 3-20-92 Quality of existing dissolved trace-element data 92.06 3-20-92 Report of committee on sample shipping integrity and cost 92.08 3-27-92 Nutrient sample size reduction 92.10 7-13-92 Phosphorus methods and the quality of phosphorus data 92.11 7-16-92 Return of spent mercury and dichromate ampoules to the National Water Quality Laboratory 92.12 7-17-92 Trace-element concentrations in deionized water processed through selected surface-water samplers: Study results and implications 92.13 7-17-92 Trace-element contamination: Findings of studies on the cleaning of membrane filters and filtration systems 93.01 10-05-92 National Water-Quality Networks: Fiscal year 1993--October 1, 1992 to September 30, 1993 93.03 10-29-92 Dissolved trace-element data 93.04 12-02-92 Discontinuation of the NWQL determinations for "total" nitrite, "total" nitrite plus nitrate, "total" ammonia, and "total" orthophsphate (using the four-channel analyzer) 93.05 1-21-93 Evaluation of capsule filters 93.06 2-19-93 Trace-element contamination--Findings of study on the cleaning of sampler caps, nozzles, bottles, and bags for trace-element work at the part-per-billion level 93.09 4-16-93 Sample splitting devices 93.10 4-91-93 (1) Disposal of petri dishes containing bacteria media, and (2) aspergillus 93.11 7-15-93 Implementation of the protocol for collecting and processing surface-water samples for low-level inorganic analyses 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. Geological 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 an important 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. All sampling equipment is to be thoroughly cleaned (the cleaning procedures are described in detail in Appendix D of this memo). Churn splitters and other equipment are to be stored in sealed plastic bags after they are cleaned and until they are used. 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, when water is not being added to it. In order to keep dirt off the outside of the churn, and dust from getting into the churn, it should be kept in a plastic bag which is opened only to allow access to the churn for emptying the sampler bottle. The "clean hands/dirty hands" technique is suggested where the "clean hands" person wears disposable gloves and handles only the sample bottle and the "dirty hands" person handles the sampling equipment (metal part of the sampler, reel, etc.) The "clean hands" person is careful not to touch metal objects or anything that could contaminate the sample, and changes gloves whenever this type of contact occurs. Sample processing should be done inside the vehicle and away from dust and exhaust. Best results are obtained when samples are processed in a clean, metal-free chamber (a glove box or chamber built from wood and plexiglass). 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 sample water (filtered water for filtered samples and unfiltered water for unfiltered samples), as described in OWQ Technical Memorandum 92.02. Disposable gloves are to be worn when handling preservatives (and changed between different types of 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 (five or six times per year). Sample collection frequencies for each site remain the same in FY 1994 as they were after January 1992. 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. For the stations that are sampled five times a year, the sample that will not be collected is one of the two samples where schedule 1904 is collected for bimonthly stations. The District Water-Quality Specialist should select the season with the least historical variation in water quality. 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 The inductively-coupled plasma (ICP) procedure is used for the analysis of selected dissolved common and trace inorganic constituents. 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 HBN 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 HBN 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 HBN 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 HBN samples should keep a current listing of the unique numbers in their field folders. 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 HBN 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 Schedule 1904 remains unchanged in FY 1994. Schedules 176 and 177 do not include arsenic, beryllium, cadmium, chromium, copper, lead, mercury, or zinc. Total ammonia, total nitrite, total nitrite + nitrate, and total orthophosphorus have been dropped from Schedule 86. Note also that the RC and FC bottles are 125 mL, with 0.5 mL mercuric chloride instead of 250 mL with 1 mL mercuric chloride. NASQAN DATA COLLECTION PROGRAM NASQAN stations to be operated during the period October 1, 1993 through September 30, 1994 are listed in Appendix A. The network will have 281 stations. There will be 91 NASQAN stations sampled bimonthly, 81 sampled five times a year, and 109 sampled quarterly. The NASQAN station Kahakuloa Stream near Honokohau, Maui, Hawaii (16618000) will become a HBN station. NASQAN Sampling Schedule for FY 1994 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) 5 or 6 per year - Field measurements (same as quarterly) 5 or 6 per year - Suspended sediment (same as quarterly) 5 or 6 per year - Nutrients, lab schedule 86 1 or 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 1994 are the same as those in FY 1992. Stations are indicated in Appendix A by listing a "2" under the heading "SCHEDULE 1703 RADIOCHEM". There are 39 stations. 2 per year - Radiochemicals, lab schedule 1703 HYDROLOGIC BENCHMARK DATA COLLECTION PROGRAM Hydrologic Benchmark Network stations to be operated in FY 1994 are listed in Appendix A. As a result of a review of the Benchmark stations John Turk and Alisa Mast (Colorado District), 5 stations have been discontinued. One station, Honilii Stream near Papikou, Hawaii, Hawaii (16717000) has been put on inactive status. The NASQAN station, Kahakuloa Stream near Honokohau, Maui, Hawaii (16618000) will become a HBN station. Rain gages have been or are being installed at a number of stations for operation beginning in FY 1994. Guidelines for operation of the gages and publication of the data will be distributed during the next few months. Changes in locations of sampling sites must be approved by the National Networks Coordinator. At 3 HBN stations, only surface-water discharge data are to be collected: these are also given in Appendix A. Of the 50 stations to be sampled for water quality during FY 1994, 39 HBN stations will be sampled quarterly, and 11 will be sampled bimonthly. The two stations that were sampled monthly previously will be changed to bimonthly. These are McDonald's Branch in Lebanon State Forest, New Jersey (01466500) and Upper Twin Creek at McGaw, Ohio (03237280). All HBN samples will be analyzed for the same properties and constituents as NASQAN samples. The field measurements and analytical schedules used for the HBN program are therefore the same as for the NASQAN program. Trace constituent samples will be collected at the 50 water-quality Benchmark stations on a quarterly basis. The analytical schedules remain the same. Analysis of radiochemicals at the 50 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 HBN 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. HBN Sampling Schedule for FY 1994 Please notify the Office of Water Quality if the District responsible for collection of samples for any HBN 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, degrees C (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. If any information in this memorandum prompts questions or comments, please call Kathy Fitzgerald whose current number is (703) 648-6902. David A. Rickert Attachments This memorandum supersedes OWQ Technical Memorandum 93.01. Distribution: A, B, S, FO, PO Key Words: water quality, networks, sampling, NASQAN, Benchmark, FY 1994 APPENDIX A This appendix contains the listing by District of all NASQAN and HBN stations. Specific information for each site includes sampling frequency and laboratory schedules. All sampling frequencies remain unchanged from FY 1993. Laboratory schedules 1703 and 1904 remain unchanged, but analyses for ammonia, nitrite, nitrite + nitrate, and orthophosphorus on the unfiltered (RC) sample have been dropped from schedule 86; schedules 176 and 177 continue to exclude arsenic, beryllium, cadmium, chromium, copper, lead, mercury, and zinc. NWQL may make changes to schedule 1703 during FY 1994. These changes will be announced by memo and in the QWTALK and LABNEWS continuums. Copies of the appendix may be retrieved via computer by the following command: FTR NASQAN>APPENDIX.A.94 FTS_DEPOT>== -SS QVARSA You may then access the Appendix file in your FTS_DEPOT. APPENDIX B NUTRIENTS SCHEDULE 86 WN OWNER:NQ COST: 69.00 CALCULATED LAB WATSTORE CODE CODE INCLUDED PARAMETERS 1688 00625 A NITR. NH4+ORG AS N WWR 1685 00666 B PHOSPHORUS, DIS. JKA 1686 00665 B PHOSPHORUS, TOTAL JKA 0160 00613 B NITR DIS NO2 AS N 0162 00671 B PHOS DIS ORTHO AS P 0301 00608 B NITR DISS NH4 AS N 0228 00631 B NITR DIS NO2+NO3 -N REQUIRES 0125 ml OF FC 0125 ml OF RC RADIOCHEMICALS SCHEDULE 1703 WR OWNER:NQ COST: 387.00 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: 237.00 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: 311.50 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: 106.00 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 (Office 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 Ocala) 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: (initial calculations should be done in the field) (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. APPENDIX D CLEANING PROCEDURES FOR EQUIPMENT TO BE USED FOR COLLECTION AND PROCESSING OF WATER-QUALITY SAMPLES FOR SUBSEQUENT DETERMINATION OF INORGANIC CONSTITUENTS BACKGROUND Rationale for In-Office Cleaning Procedures New and/or previously used and stored equipment is likely to contain, or have adhering to it, a wide variety of potential contaminants. The purpose of the universal cleaning procedure is to ensure that these are removed prior to using the equipment. This procedure is applicable for equipment that will be used for collection and processing of samples for subsequent trace-element analysis. This is a four (4) step procedure using detergent, tap water, dilute acid, and deionized water. The detergent is used in conjunction with scrubbing with brushes to remove any adhering material such as sediment or algae. Most of the detergent residue will be removed with tap water rinses. Any remaining organic films and detergent residues will be removed with the acid. Finally, any acid residues will be removed with deionized water rinses. This procedure must be applied to all sampler bottles and bags, with the exception of Reynolds Oven Bags. In the case of the oven bag, the detergent step is omitted because it will be almost impossible to scrub the bag and completely remove detergent residues. Rationale for Field Cleaning Procedures Field experiments (see OWQ Technical Memorandum 92.13) have shown that cross- contamination between sites can occur if the sampling and processing equipment are not adequately cleaned before they are reused. The field-cleaning procedures to eliminate between-site cross-contamination are less rigorous than the initial office cleaning procedures because the equipment has not had a chance to dry out and thus, material has not had a chance to strongly adhere to the various components. This field cleaning procedure was used effectively to eliminate cross-contamination between a highly polluted acid mine drainage site (Fe = 50,000 g/L, Mn = 5,000 g/L, Zn = 5,000 g/L, Cu = 400 g/L, Co = 125 g/L) and a nearly pristine rural/agricultural site where the trace-element concentrations were at or near current (ppb) reporting limits with no apparent cross-contamination. This procedure should be carried out at the first sampling site when the equipment is still wet, before driving to the second site. The procedure involves two steps using a combination of dilute acid and DIW. Because of the hazards and disposal problems associated with using acid in the field, it is highly recommended that sufficient equipment be purchased and/or trips arranged so that field cleaning will not be necessary. Deionized Water Large amounts of deionized water (DIW) will be required both in District and field offices, as well as in the field. Requirements for District DIW units, and where they can be obtained, are discussed in OWQ Technical Memorandum 92.01. Bear in mind that the quality of the DIW (conductance < 1 uS/cm), and the requirement for monthly low ionic strength specific conductance tests outlined in 92.01 are also a requisite for any DIW used to follow the procedures detailed in this protocol. Experience with many of these units indicates that they come without a final, in-line filter after the DIW passes through the deionizing columns. It has been shown that many of the systems lacking a post- column, in-line filter, have a tendency to permit some of the deionizing resins to pass out with the DIW. Initially (with a new set of columns), DIW residues containing these beads may contribute to the major ion content of a sample. After some use, the beads may also contribute other cations, possibly trace elements, which were removed from the water during passage through the columns. Therefore, it is strongly recommended that a 0.45-um post-column filter be added to any District deionizing system to prevent the inclusion of these beads with the DIW. Finally, as stated in 92.01, District DIW is not to be used for equipment and/or field blanks. Choice Of Acid For The Various Cleaning Procedures Hydrochloric acid (HCl) will be used for all cleaning procedures. HCl was chosen over nitric acid to limit the chances for contamination of nutrient samples. Appropriate volumes of dilute (5 percent by volume) HCl will be made up as needed from concentrated HCl (12N, specific gravity 1.19, trace element- free grade) which, because of DOT shipping requirements, cannot be supplied by the Water Quality Support Unit and must be purchased by the Districts directly from an appropriate vendor. Working with acid will require safety precautions such as gloves, safety glasses, aprons, availability of a spill kit. Used and/ or excess acid must be disposed of appropriately. The District Safety Officer should have information on the rules and regulations that are specific to each State. PROCEDURE 1: IN-OFFICE EQUIPMENT CLEANING Requisite Supplies 1. DIW (see OWQ Technical Memorandum 92.01). 2. Concentrated, trace element free (HCl) acid (Baker Instra-Analyzed, or equivalent). Aliquots must be diluted with DIW to 5 percent (50mL/L, V/V) and stored in a non-contaminating container. 3. Assorted, safety-labeled wash bottles for DIW and dilute acid. 4. Liquid detergent, such as Liquinox, which does not contain phosphates or NTA, diluted with warm tap water to 2 percent or less depending on the hardness of the tap water. 5. Disposable, non-powdered vinyl gloves. 6. Non-contaminating, non-metallic clear/uncolored polypropylene/high density polyethylene basins (minimum of four) sufficiently large to immerse all parts of the sampling and processing equipment-- sampler nozzles, caps, and bottles; filtration equipment (if plate filter is used); pump tubing; and lid from the churn splitter. The churn splitter and paddle will be cleaned by filling the churn with the different solutions. 7. Various non-contaminating (non-metallic, white or clear) brushes. 8. Assorted sealable plastic bags for storage and transport after cleaning. Procedure 1. Before cleaning the equipment, clean the basins and wash bottles; label each basin with a waterproof marker. Each item must be cleaned with: a) detergent, b) tap water, c) dilute acid, and d) DIW. Read through this procedure and follow the appropriate steps for the basins and bottles, as if they were part of the sampling/ processing equipment, before beginning to clean the equipment itself. 2. Disassemble all equipment (sampling and processing), including any pump tubing you will be using, and immerse them in the detergent solution in the non-contaminating basin. 3. Allow the equipment to soak in the detergent for at least 30 minutes. 4. Put on a pair of disposable gloves and, using the appropriate brushes, thoroughly scrub all the equipment with the detergent. 5. Once scrubbed, place the cleaned items in a second pre-cleaned, non- contaminating basin. 6. Partially fill the churn splitter with liquid detergent and thoroughly scrub it. Pay particular attention to the paddle and the area around the nozzle. Ensure that the valve, nozzle, and cappable funnel (if used) are cleaned as well. 7. Change gloves. 8. Thoroughly rinse the scrubbed items with warm tap water until there is no sign of any detergent residue-- until the soap bubbles all disappear. Fill the churn through the cappable funnel (if used) with tap water and swirl it to remove any detergent residues. Make sure to allow some of the water to pass through the spigot. Force tap water through the pump tubing to thoroughly rinse it. If necessary, use a wash bottle filled with tap water to clean out any hard-to-reach places, including the inside of the sampler nozzle. 9. Change gloves. 10. Place the tap water-rinsed items in a pre-cleaned, non-contaminating basin. Immerse the equipment in the dilute (5%) acid and let it soak for at least 30 minutes. Fill the churn splitter with dilute acid and allow it to soak for the same amount of time. 11. At the end of the soak, put on new gloves, remove the equipment from the acid, and place qit in a pre-cleaned, non-contaminating basin. Drain the acid from the churn splitter through the spigot. The acid should be drained into a container for later disposal or into a sink that is equipped with a neutralization system 12. Change gloves. 13. Fill the basin and the churn splitter (through the cappable funnel, if used) with DIW. Using either a DIW faucet, and or a wash bottle; thoroughly rinse all equipment with DIW. Swirl the DIW in the churn splitter and drain it through the spigot. 14. Repeat step 14 two (2) more times. 15. Reassemble all equipment and put it inside two (2) sealable plastic bags. The pump tubing should be sealed in double plastic bags. Double bag the churn splitter and place it inside the churn carrier. PROCEDURE 2: FIELD RINSING OF EQUIPMENT PRIOR TO SAMPLING Requisite Supplies 1. Deionized water (DIW), see OWQ Technical Memorandum 92.01 2. Assorted, safety-labeled wash bottles for DIW 3. Disposable, non-powdered vinyl gloves Procedure 1. Put on a pair of disposable gloves. 2. Thoroughly rinse the sampler and churn splitter with DIW. Pour at least 3 L of DIW into the churn through the cappable funnel, if used; swirl the DIW in the churn splitter making sure all surfaces are covered, and drain some of the rinse through the spigot prior to discarding the remaining rinse water. 3. Rinse the sampler bottle, cap, and nozzle by collecting sufficient quantities of native water with the sampler to completely fill the sampler bottle. Discard the water. 4. Collect a second aliquot (3L) of native water with the sampler and pour it into the churn through the cappable funnel, if used. Swirl the water in the churn making sure all surfaces are covered, drain some of the water through the spigot, and discard the remaining water. PROCEDURE 3: FIELD CLEANING TO PREVENT CROSS-CONTAMINATION BETWEEN SITES Requisite Supplies 1. Deionized water (DIW), see OWQ Technical Memorandum 92.01 2. 5% HCl 3. Assorted, safety-labeled wash bottles for DIW and dilute acid 4. Disposable, non-powdered vinyl gloves 5 Sealable plastic bags Procedure 1. Put on a fresh pair of disposable gloves. 2. Disassemble the sampler so that all of the parts (bottle cap, nozzle) can be thoroughly wetted with the various rinses. Where appropriate, vigorously agitate the fluid inside the container (sampler bottle, churn splitter) to facilitate cleaning and rinsing. 3. Thoroughly rinse the sampler parts with DIW; use a stream of DIW from the appropriate wash bottle, if required. 4. Thoroughly rinse the sampler parts with dilute acid; use a stream of dilute acid from the appropriate wash bottle, if required. (NOTE: the used acid must be placed in an appropriate storage container and disposed of properly.) 5. Thoroughly rinse the sampler parts with DIW; use a stream of DIW from the appropriate wash bottle, if required. 6. Repeat step 5. Repackage the equipment in double plastic bags. 7. Remove the churn splitter from its plastic bags and discard the bags. Thoroughly rinse the churn splitter with DIW. Fill the churn through the cappable funnel, if used; swirl the DIW in the churn splitter, and drain some of the rinse through the spigot prior to discarding the remaining rinse water. 8. Thoroughly rinse the churn splitter with dilute acid. Pour 2-3 L of acid into the churn through the cappable funnel, if used; swirl the dilute acid in the churn splitter making sure all surfaces are covered, and drain some of the acid rinse through the spigot. (NOTE: the used acid must be placed in an appropriate storage container and disposed of properly.) 9. Thoroughly rinse the churn splitter with DIW. Pour at least 3 L of DIW into the churn through the cappable funnel, if used; swirl the DIW in the churn splitter; and drain some of the rinse through the spigot prior to discarding the remaining rinse water. 10. Repeat step 9. 11. Repackage the churn splitter in two (2) new plastic bags, seal the bags, and place the entire unit back inside the churn carrier. The following steps are required only if a plate filtration system was and will be used to process samples. 12. Open the filtration system inside the processing chamber and carefully remove the used membrane filter. Try to keep handling to a minimum so as not to dislodge any of the sediment from the filter and transfer the used filter to a sealable plastic bag. Remove the used filter, inside the plastic bag, from the processing chamber. 13. Place the filtration system over the sink or a waste bottle in the bottom of the processing chamber and, using a wash bottle filled with DIW, thoroughly wash all the parts of the system. Pay particular attention to grooves or crevices, 'O' rings, and support structures for the filter, where sediment or organic matter might be trapped in the system. 14. Reassemble the system and attach a short piece of tubing to the filtration outlet and place the tubing inside the sink or waste bottle in the bottom of the processing chamber. 15. Pass one (1) liter of dilute acid through the system using the same pump and pump tubing used to filter the sample. Force the acid solution to cover and rinse the entire filtration system by alternately squeezing and releasing the short piece of tubing attached to the system outlet. 16. Pass two (2) liters of DIW through the system using the same pump and pump tubing used to filter the sample. Force the DIW to cover and rinse the entire filtration system by alternately squeezing and releasing the short piece of tubing attached to the system outlet. 17. Remove the pump tubing from the hole in the processing chamber and repackage it in double plastic bags. 18. Discard the processing chamber bag and replace it with a new one. 19. Discard the last preservation chamber bag. Do not replace it until ready to preserve additional samples at the next sampling site. 20. Proceed to the next sampling site. The following steps are required only if a capsule filter was and will be used to process samples. 12. Place the end of the pump tubing, which normally connects to the capsule filter, inside the sink or waste bottle in the bottom of processing chamber. 13. Pass one (1) liter of dilute acid through the system using the same pump and pump tubing used to filter the sample. 14. Pass two (2) liters of DIW through the system using the same pump and pump tubing used to filter the sample. 15. Remove the pump tubing from the hole in the processing chamber and repackage it in double plastic bags. 16. Discard the processing chamber bag. 17. Discard the last preservation chamber bag. Do not replace it until ready to preserve additional samples at the next sampling site. 18. Proceed to the next sampling site.