In Reply Refer To: September 18, 1985 WGS-Mail Stop 412 Memorandum QUALITY OF WATER BRANCH TECHNICAL MEMORANDUM NO. 85.19 Subject: PROGRAMS AND PLANS--National Water-Quality Networks: Fiscal Year l986--October 1, 1985, to September 30, 1986 Program status and protocol for operation of the National Stream Quality Accounting Network (NASQAN) and the Hydrologic Bench-Mark Network (HBMN) in fiscal year (FY) 1986 are outlined in this memorandum. The contents of this memorandum should be read and understood by all personnel responsible for collecting samples for NASQAN or HBMN. Most problems associated with Networks data collection can be traced to personnel not being adequately informed of changes in sample collection and processing procedures, and other aspects of networks operations. After detailed evaluation of anticipated funding resources, District funding needs, and the impending impact of the new National Water-Quality Assessment Program (NAWQAP) on a probable redesign of NASQAN, it was decided to operate the National Networks program pretty much unaltered for FY 1986. The additional funding that is expected to be made available to the program will be used to (1) make up a projected deficit in the program relative to originally proposed funding and (2) do a detailed evaluation of stations, parameter coverage, and sampling frequency. This evaluation is to be done by a team of District and Headquarters personnel. NETWORKS OPERATIONS, FY 1986 District personnel should be aware of the following policies and procedures applicable to both NASQAN and HBMN for FY 1986. Field Incremental Analysis for Alkalinity As discussed in (1) Quality of Water Branch Technical Memorandum 84.16 and (2) the March 14, 1985, memorandum from the Assistant Chief Hydrologist for Operations to District Chiefs and Regional Hydrologists (subject: PROGRAMS AND PLANS-Federal Collection of Basic Records Program, Fiscal Year 1986), effective October 1, 1985 all NASQAN and Bench- Mark samples are to be analyzed for the following constituents and entered into the WATSTORE Water-Quality File. o Carbonate alkalinity, electrometric incremental field titration (code 99430) o Dissolved carbonate, electrometric incremental field titration (code 99445) o Dissolved bicarbonate, electrometric incremental field titration (code 99440) o Alkalinity, fixed end-point field titration to 4.5 pH (code 00410) o Hydroxide, electrometric incremental fieid titration (code 99830) There has been some concern about the need for field incremental titrations. On a theoretical basis, significant differences can occur between fixed endpoint results and incremental endpoint results. A recent comprehensive study was done to compare analytical results for (1) Gran plot, (2) second derivative, and (3) fixed endpoint titrations. The results of the study clearly indicate that whereas there are no statistical differences between the Gran plot and second derivative incremental procedures, there are, however, statistically significant differences between both incremental procedures and the fixed endpoint procedure. It is hoped that with the advance notice over the past year of implementation of incremental field titration, Districts have established adequate training and quality-assurance programs for these field measurements to assure accurate data. Districts are, of course, strongly encouraged to maintain a quality-assurance program which includes monthly measurement of alkalinity reference samples by field personnel. Alkalinity reference samples are available from the Ocala Water-Quality Service Unit. Field personnel should be aware of the need to record all titration information on water-quality field sheets. Particular attention should be given to properly define the titration curve in the area of the equivalence points, especially for samples with low initial pH values. If the equivalence point is in doubt, field personnel should not hesitate to double check the results by doing another titration. Because WATSTORE parameter codes above 90000 are not recognized by STORET, a request has been made to EPA for appropriate STORET codes corresponding to 99430, 99445, 99440, and 99830. The field offices will be notified when the new codes are available. Concentrations of all 5 constituents can be determined from the same titration. For the purpose of the NASQAN and Bench-Mark programs, if the concentration of hydroxide is zero, field personnel need not enter the value into the Water-Quality File. The same rule applies to carbonate (code 99445). District personnel should refer to Quality of Water Branch Technical Memorandum 84.16 which lists the pertinent references regarding background information and analytical procedures for these determinations. The analytical procedure for alkalinity by fixed-endpoint titration is given in TWRI Book 5, Chapter Al. The analytical procedure for incremental titration of carbonate alkalinity, bicarbonate, and carbonate is given in Quality of Water Branch Technical Memorandum 82.05. Incremental titration for bicarbonate using the Hach digitai titrator is discussed in the WRD Bulletin (see the October-December, 1981 issue). To provide a uniform framework for comparison between samples and stations, samples for field analysis of aikalinity and its components are to be filtered, in the same manner as for common dissolved inorganic constituents. Field personnel will most likely do the titrations using either a buret or the Hach digital titrator. The primary advantage of the digital titrator is its durability and the ability to add uniform, small incremental volumes of titrant, thereby easily determining the titration endpoint and computing concentrations. Because of the inherent difficulty in adding uniform incremental volumes of titrant with a buret, use of the Hach titrator should be both faster and more accurate than the buret. Per discussions with Hach chemists, the normality of the titrants is typically plus or minus 0.5%. Each titrant cartridge contains enough acid to typically do 100 titrations. Based upon stability tests done by Hach, the normality of both the 1.600 and 0.1600 normal (N) cartridges will increase by 0.8% per year, due to loss of solution through the cartridge walls. The loss can be kept to a minimum by storing the cartridges in areas of high humidity. The date of preparation of the cartridges can be determined from the lot code stamped on each cartridge. The 1.600 N cartridge has an alphanumeric lot code, and is considered by Hach to be good for 2 years. Ocala will provide the date of preparation for these cartridges. The 0.1600 N cartridge has a 4-digit lot code, and is considered by Hach to be good for 1-2 years; the first digit is the year of preparation and the following 3 digits are the day of the year (for example, January 1 = 001 and December 31 = 365). The National Networks program has entered into an agreement with the Ocala Water-Quality Service Unit (WQSU) for a quality-assurance program for the titrant cartridges used with the digital titrator. The Ocala Water-Quality Service Unit will supply the titrant cartridges to the Districts and verify the normality of the cartridges. Both the 1.600 and 0.1600 N sulfuric acid titrant cartridges can be ordered from Ocala (approximately $6.00 each). The Ocala WQSU also has a limited quantity of digital titrators which the Districts can purchase for approximately $85.00. Ocala will check the normality of a selected number of both 1.600 and 0.1600 N titrant cartridges from each lot. If the normalities are acceptable, the titrant cartridges will be made available for purchase by the Districts. At 30-day intervals, Ocala will check the normality of all lots being used by the Districts, using the original test cartridges for each lot. If a significant change is detected, a comparison will be made between the original test cartridge from that particular lot, and several "new" cartridges from the same lot. This will provide a comparison of factory sealed cartridges with those which are "in use". Based upon the results of this quality-assurance program, Districts will be notified, via the continuum "QWTALK" (formerly SPECS and now an open meeting to all personnel), which cartridges should be discarded. Because Ocala will provide quality assurance for the cartridges it supplies, Districts are encouraged to order all titrant cartridges from Ocala. Ocala also maintains a considerable stock of alkalinity reference samples. We strongly encourage Districts to use them to afford quality assurance of field measurements. Districts can order the titrant cartridges from Ocala via phone FTS 946-7255) or Prime E-Mail. When using E-Mail, submit orders to "OCALACO@LGADRV". Be sure to include the following information: number of cartridges, the normality, account number to be billed, the date needed by, the "ship- to-address", the name of a person to contact if there are any questions about the order, and the FTS phone number of the contact person. Sulfuric acid (H2SO4) for field titrations with a buret can be ordered from any reputable chemical-supply source such as Fisher Scientific, Von Water and Rogers, or Arthur H. Thomas. As a general rule, solutions of titration acid should be discarded after six months, or the normality verified by titration with a primary standard solution of sodium carbonate. Computer programs have been developed by District personnel to compute concentrations of alkalinity components. A computer program to do this, written by Steve Sober of the Colorado District, is available via SOFTEX. Yvonne Wray of the Texas District has updated Steve's program to allow computations based upon either (1) buret ml readings or (2) Hach digital titrator values. Her program is also available on SOFTEX. The National Networks program recommends the Districts use the Texas program. The Texas program will be further modified to allow computation of concentrations based upon either the second derivative or the Gran plot method. The following references, all of which should be available in each WRD office, provide background and methodology information regarding the principles of incremental titrations for analysis of alkalinity and its components. References 3 and 4 include additional references on this subject. 1. Quality of Water Branch Technical Memorandum 80.27 (Subject: WATER QUALITY--New parameter codes for pH, alkalinity, specific conductance, and carbonate/ bicarbonate). 2. Quality of Water Branch Technical Memorandum 81.04 (Subject: WATER QUALITY--Assignment of parameter codes of pH, alkalinity, specific conductance, and hydroxide/ carbonate/bicarbonate data). 3. Quality of Water Branch Technical Memorandum 82.05 (Subject: WATER QUALITY--Provisional method for carbonate, dissolved; bicarbonate, dissolved; and carbonate alkalinity, dissolved; electrometric titration, incremental, field). 4. Incremental field titration of bicarbonate: WRD Bulletin, October-December 1981, p. 8-13. 5. Quality of Water Branch Technical Memorandum 82.06 (Subject: PU8LICATIONS--Policy on publishing constituents with both field and laboratory values). Stable Isotope Investigation Districts should continue to collect additional samples for the ongoing investigation to study seasonal and regional variation of stable isotope composition at the NASQAN and HBMN stations selected by Tyler Coplen. At these stations, collect a 2-ounce filtered sample during each routine sampling during the 1986 water year. Each sample should be composited with a churn splitter as usual, filtered, poured into a 2-ounce glass bottle, and preserved with one HgCl2 tablet; no chilling is needed. Each sample should include a small amount of air space in the bottle. Each bottle should be labeled with the station number, sample date and time. No other paperwork is necessary. Samples can be shipped immediately or in batches every six months to: Stable Isotope Laboratory, U.S. Geological Survey, 431 National Center, Reston, Virginia 22092. To prevent sample freezing and possible breakage during shipment, samples should not be forwarded to Reston for analysis during the winter months. Samples are analyzed at no cost to the Districts for (1) deuterium/protium (hydrogen-2/ hydrogen-l), ratio per mil, WATSTORE code 82082 and Central Laboratories code O3OO; and (2) oxygen-l8/oxygen-l6, ratio per mil, WATSTORE code 82085 and Central Laboratories code 0489. The stable isotope laboratory will enter all analyses into the WATSTORE Water- Quality File. Because of the anticipated delay in sample shipment, analysis, and processing, Districts are not required to publish the analyses in annual water resources data reports. Collection of Representative Samples There is continued concern that field personnel utilize uniform, approved procedures to ensure collection of representative samples. Numerous aspects must be assessed to determine the correct procedures needed to collect a representative sample. Cross-section surveys (depth and width) of water temperature, pH, specific conductance, dissolved oxygen, and suspended sediment should be done at the sampling location during various seasons and surface- water discharges to document the general cross-sectional variation of water quality. Such information is essential to determine how many samples in the cross section are necessary to ensure a representative composite sample. Field personnel often collect water-quality samples from a minimum number of cross-section verticals without adequate documentation of the degree of homogeneity in water quality at the cross section. The results of such cross-section surveys should always be recorded in the appropriate station-analysis file and entered in WATSTORE. When entering such data, be sure to enter the cross-section location utilizing WATSTORE code 00009 (cross- section location, feet from left bank looking downstream). Based upon the cross-section measurements, also be sure to enter a discharge-weighted value for each constituent or characteristic determined at these multiple cross-section verticals for the time and instantaneous surface-water discharge given for the Central Laboratory data. Another common error observed during technical reviews of District water-quality activities is that samples to be analyzed for common ions or nutrients are not collected in the same manner as suspended-sediment samples. Field personnel should assess the proper sample-collection methodology necessary to collect a representative sample, and then use that methodology for all samples, as applicable. Field personnel should be thoroughly familiar with the recommended compositing procedures. See Quality of Water Branch Technical Memorandum 76.17, and Techniques of Water Resources Investigations, Book 3, Chapter C2, entitled: Field methods for measurement of fluvial sediment. Field personnel should also ensure that field measurements and suspended- sediment samples are collected at the same time as samples for common ions, nutrients, trace metals, etc. These data should also be stored in WATSTORE. 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). 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 l76 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 are given in Appendix A under the right-hand side heading "PROBABILITY (%) THAT SPECIFIC CONDUCTANCE WILL BE EQUAL TO OR GREATER THAN 2,000 US/CM." These values represent the overall probability that a sample collected during FY 1986 will require schedule 177 in lieu of schedule 176. Only schedule 176 is authorized for stations with zero probability of the specific conductance exceeding 2,0OO uS/cm. Because of the uncertainty involved in predicting the number of samples during FY 1986 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. It is to be clearly understood, however, that the actual number of usages authorized between schedules 176 and 177 is four, not eight, for both HBMN and NASQAN. District Water-Quality Specialists have the authority and responsibility to request schedule 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: (1) a field specific conductance measurement is absolutely necessary whenever schedule 176 or 177 is to be utilized; and (2) the specific conductance of the sample should be determined with a meter that has been properly calibrated. 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 U.S. Geological Survey Central Laboratories with appropriate Central Laboratory unique numbers. The necessary computer program documentation to retrieve unique numbers is given in Quality of Water Branch Technical Memorandum 79.15. New unique numbers are established at the beginning of 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 either Central 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. It is to the benefit of each District, therefore, to be sure that the proper unique numbers are being used, and to periodically make retrievals of the unique numbers. 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, Bench-Mark), etc., are helpful to both Central Laboratories 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 should be done for each sample; there are no exceptions to this rule. The National Networks program is currently assessing the coverage of field measurements for all active NASQAN and HBMN stations. This assessment will be done on a District-by-District basis. Districts will be notified of the results for the stations in their District (through their Regional Hydrologist). Particular attention will be given to assess the coverage of instantaneous surface-water discharge for NASQAN and HBMN samples. Analytical Schedules Central Laboratories analytical schedule 86 (nutrients) will be revised, effective FY 1986, for both NASQAN and HBMN. Schedule 86 will incorporate the additional analysis of (1) total ammonia nitrogen and (2) dissolved nitrite nitrogen. The bottle requirements for schedule 86 will remain the same. For the convenience of District personnel, all Central Laboratories analytical schedules for NASQAN and HBMN are given in Appendix B: their frequency of use at each station is given in Appendix A. NASQAN DATA-COLLECTION PROGRAM NASQAN stations to be operated during the period October 1, 1985, through September 30, 1986, are listed in Appendix A. No stations have been added. Two NASOAN stations will be relocated: The Aroostock River at Caribou, ME (01017100) will be relocated to the Aroostock River at Ft. Fairfield, ME (01017500); and the Amite River at 4-H Camp near Denham Springs, MS (07378510) will be relocated to the Amite River at Port Vincent, MS (07381020). Six NASQAN stations will be dropped: 06109500, Missouri River at Virgille, MT 08078000, Chocolate Bayou near Alvin, TX 10254970, New River at International Boundary, Calexico, CA 10353500, Quinn River near McDermitt, NV 10237000, Beaver River at Adamsville, UT 15056100, Skagway River at Skagway, AK NASQAN Sampling Schedule for FY 1986 There will be one station sampled monthly, 228 NASQAN stations sampled quarterly, and 266 NASQAN stations sampled bimonthly (see Appendix A). Please notify the Quality of Water Branch if the District responsible for collection of samples for any NASQAN or HBMN station has changed recently and is subsequently given incorrectly in Appendix A. NASQAN Sampling Schedule (Quarterly Stations) 4 per year - Field measurements: Instantaneous discharge (WATSTORE Code 00061) Specific conductance (WATSTORE Code 00095) Water temperature, "C (WATSTORE Code 00010) Barometric pressure (WATSTORE Code 00025) pH (WATSTORE Code 00400) Carbonate alkalinity, incremental titration (WATSTORE Code 99430) Dissolved carbonate, incremental titration (WATSTORE Code 99445) Dissolved bicarbonate, incremental titration (WATSTORE Code 99440) Alkalinity, fixed end-point titration to 4.5 pH (WATSTORE Code 00410) Hydroxide, incremental titration (WATSTORE Code 99830) Dissolved oxygen (WATSTORE Code 00300) Fecal coliform bacteria (WATSTORE Code 31625) Fecal streptococcal bacteria (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 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) 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 (Monthly Station) 12 per year - Field measurements (same as quarterly) 12 per year - Suspended sediment (same as quarterly) 12 per year - Nutrients, lab schedule 86 8 per year - Physical properties and common dissolved inorganic constituents: lab schedule 1904 (not used when schedule 176 is used) 4 per year - Physical properties, and common and trace dissolved inorganic constituents: lab schedule 176 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 1986 are indicated in Appendix A by listing a "2" under the heading "SCHEDULE 1703 RADIOCHEM". Fifty-two NASQAN stations comprise the network as in the past. One sample should be collected at high-flow and one sample should be collectd at low-flow as before. 2 per year - Radiochemicals, lab schedule 1703 HYDROLOGIC BENCH-MARK NETWORK Hydrologic Bench-Mark Network stations to be operated in FY 1986 are listed in Appendix A. Bimonthly water-quality sampling is being initiated at the existing Bench-Mark stations, Little River above Townsend, TN (03497300) and the Cossatot River near Vandervoort, AR (07340300). These stations were previously funded for daily surface-water discharge only, A new Bench-Mark station is being initiated at the Sagehen Creek near Truckee, CA (10343000). At 3 HBMN stations, only surface water discharge data are to be collected: these are also given in Appendix A. Of the 56 stations to be sampled for water quality during FY 1986, forty-four (44) HBMN stations will be sampled quarterly, 10 HBMN stations 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. Analysis of trace metals at the 56 water-quality Bench-Mark stations will be increased to a quarterly basis. The analytical schedules remain the same. Analysis of radiochemicals at the 56 water-quality Bench-Mark stations will be increased to 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. Hydrologic Bench-Mark Network Sampling Schedule (Quarterly Stations) 4 per year - Field Measurements: Instantaneous discharge (WATSTORE Code 00061) Specific conductance (WATSTORE Code 00095) Water temperature, "C (WATSTORE Code 00010) Barometric pressure, mm Hg (WATSTORE Code 00025) pH (WATSTORE Code 00400) Carbonate alkalinity, incremental titration (WATSTORE Code 99430) Dissolved carbonate, incremental titration (WATSTORE Code 99445) Dissolved bicarbonate, incremental titration (WATSTORE Code 99440) Alkalinity, fixed end-point titration to 4.5 pH (WATSTORE Code 00410) Hydroxide, incremental titration (WATSTORE Code 99830) Dissolved oxygen (WATSTORE Code 00300) Fecal coliform bacteria (WATSTORE Code 31625) Fecal streptococcal bacteria (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 Bench-Mark 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 Bench-Mark 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. PROGRAM ACTIVITIES AND PRODUCTS In addition to the ongoing data-collection program, diverse groups of activities are being supported by the National Networks program. Some of these activities are discussed in more detail below, not only as a source of information for WRD personnel, but also as an incentive for interested parties to provide constructive criticism and suggestions for new activities. District personnel are encouraged at all times to submit project proposals for funding by the National Water-Quality Networks program. Project proposals will be evaluated and ranked. Funding will be based on project ranking and availability of funds. o Bob Gilliom, Richard Alexander, and Richard Smith interpreted all historical data from the former cooperative USGS/EPA Pesticide Subnetwork of NASQAN: Water-Supply Paper 2271 will be available in FY 1986. o The Wisconsin District has prepared a report on the streamflow characteristics at each HBMN station. The statistical summary will be done in both tabular and graphical formats on a station-by-station basis. Circular 941 covers all available streamflow data collected through the 1981 water year, and will be available in FY 1986. o The Pennsylvania District completed a project in which two HBMN drainage basins were selected to: (1) determine the spatial variability of stream acidity within small upland watersheds for selected flow conditions: (2) define the relationship between streamflow and acidity; (3) evaluate how well pH data at a gaging station represent upstream conditions; and (4) develop an information base for evaluation of temporal trends of acidity within watersheds. Water Resources Investigations report 85-4025 will be available in FY 1986. o The North Dakota District evaluated available water-quality data for evidence of snowmelt enrichment in atmospherically-derived trace constituents for HBMN drainage basins receiving more than 12 inches of snow. Specific objectives of this project include: (1) identify enrichments in trace constituents at HBMN drainage basins occurring on the rising limb of the spring snowmelt hydrograph; (2) compare the enrichments with data on atmospheric emissions; and (3) identify relationships among the magnitude of trace constituent enrichments observed, if any. Water Resources Investigations report 85-4104 will be available during FY 1986. o Streamflow data from HBMN stations in the Pacific Northwest and California regions were studied by the Pacific Northwest District to identify stations where temporal trends in streamflow exist and to determine if the trends are man induced or climatically caused. A final report is expected at the beginning of FY 1986. o Interpretive reports will be available in FY 1986 for projects initiated by the NASOAN program to detail the variability of water quality within NASQAN drainage basins relative to the composite picture provided by the NASQAN stations, which are generally located at the downstream end of U.S. Geological Survey/Water Resources Council hydrologic accounting units. A major concern of the WRD Ad Hoc Committee convened to evaluate the NASQAN program was that many people erroneously assumed or believed that water quality at NASQAN stations accurately reflect water-quality variability throughout the entire upstream drainage area. Although NASQAN was never intended, nor should it be expected, to reflect upstream variability, an understanding of the spatial and temporal variability of water quality within a NASQAN drainage basin is a logical adjunct to the objectives of NASQAN and should contribute significantly to our ability to plan and conduct better water-quality monitoring programs. Each of the eight projects has the following objectives: (1) describe, on both a spatial and temporal basis, the surface- water quality throughout the hydrologic accounting unit upstream of the NASQAN station; (2) relate the water-quality variability, on both a spatial and temporal basis, to general causes such as selected basin characteristics including land and water use; (3) assess the ability of water-quality data collected at the NASQAN station to represent, on both a spatial and temporal basis, the water quality of the hydrologic accounting unit upstream from the station; (4) if water-quality data at the NASQAN station do not represent water quality throughout the hydrologic accounting unit, describe the minimum data-collection program necessary to do so; and (5) assess the usefulness of daily values versus periodic water-quality data for the above four objectives. The NASQAN basins studied are: WRD Region River Basin Northeastern Region West Branch Susquehanna River Northeastern Region Upper Mississippi River Northeastern Region St. Croix River Northeastern Region Potomac River Southeastern Region Peace River Southeastern Region Green River Southeastern Region Tennessee River Central Region Trinity River Central Region San Juan River Western Region Umpqua River Western Region Yakima River o Trend analysis of NASQAN and HBMN data is, and will continue to be, an important element of the research component of the National Water-Quality Networks program. The Seasonal Kendall tau trend test developed by Branch staff and the WRD Systems Analysis Group is being used to detect and evaluate trends for 36 constituents at 364 NASQAN and HBMN stations. The trend analysis research is currently being directed separately at data from the HBMN and NASQAN networks. Trends in sulfate, nitrate, bicarbonate and four major cations concentrations at HBMN stations are being examined on a station-by-station basis along with available soils information in an attempt to provide a geochemical interpretation of chemical changes at each station. Also, historical changes in atmospheric sulfur emissions are belng compared to long-term records of sulfate transport rates at HBMN stations. Some of the results of trend studies with HBMN data will be included in a report to be published by the National Academy of Sciences. In the case of NASQAN stations, data on basin characteristics such as land use, population, point and non-point sources of pollution, etc., are being used to help explain water-quality trends in a large number of constituents. Results of these studies will appear in journal articles and in the National Water Summary. o An investigation is underway by headquarters personnel to study the relation of instantaneous surface-water discharge values for NASQAN and HBMN samples to flow-duration characteristics. The investigation will determine if NASQAN and H8MN samples are biased in relation to the distribution of surface-water discharge. A report is expected to be available during FY 1986. o NASQAN and HBMN data are increasingly being used by other Federal agencies. The Economic Research Service of the U.S. Department of Agriculture is using NASQAN data to assess possible relationships between water quality and effects from agricultural production areas. As part of a U.S. Forest Service multi-phase investigation to develop and test prototype multivariate statisticai procedures that can be used in regional and national assessments that predict abundances of selected riverine fish, the Oak Ridge National Laboratory (ORNL) is compiling a data base of water-quality data as input into the predictive model. ORNL is utilizing NASQAN data for this work element, and is particuiarly interested in using the Seasonal Kendall tau trend analysis results. In addition, the Strategic Assessment Branch of the National Oceanic and Atmospheric Administration is utilizing NASQAN data to define major physical, chemical, and biological characteristics of the Nation's estuaries as part of their National Estuarine Inventory project which will include an atlas entitled "National Atlas on the Use and Health of United States Coastal Waters". o John Turk and Don Campbell of the Colorado District are evaluating the hypothesis that observed trends in surface- water quality of HBMN stations are caused by atmospheric emissions and deposition. Approximately twenty HBMN stations were chosen for detailed anaiysis. Mass-balance comparisons will be made between precipitation and surface water. Surface-water constituent loads not accounted for by precipitation will be accounted for by a geochemical model to check for agreement with likely weathering reactions of the basins' mineralogy. This is an important step in detecting significant geologic sources of sulfate and other constituents. Alternate explanations for apparent acidification trends will be explored. Natural variability of stream chemisty, systematic error due to changes in analytical technique, and short-term changes in climate or other environmental factors will be considered. Given that the hypothesis of stream acidification remains plauslble, the watershed will be examlned to verify assumptions of no change in land use. Avaliable data on local and regional emissions will be compiled from published literature and regulatory records, and prevailing wind patterns will be delineated. Emissions will be separated geographically and compared to synoptic concentrations of important constituents in lakes and streams near the HBMN stations to estimate local versus regional acid loading. Results for individual HBMN stations will then be analyzed within and among regions, and compared to data from other sources to evaluate the extent of deposition impacts and the response of stream chemistry on a regional basis. o Methods for the direct determination of total metals in bottom and suspended sediments have been developed and approved for use in the Central Laboratory System. The first method uses a fusion to digest the sample and permits quantification of iron, manganese, magnesium, aluminum, silica, sodium, potassium, and calcium. The second method employs a mineral acid digestion and permits the determination of iron, manganese, aluminum, titanium, magnesium, sodium, potassium, calcium, copper, zinc, lead, nickel, cobalt, lithium, strontium, cadmium, and chromium. The former method requires 200 milligrams, and the latter method requires 250 mil1igrams. A method for total mercury has also been developed and submitted for approval. This method also requires a 250 milligram sample. A method for the concentration of suspended sediment, after sampling, has been developed; final approval of the procedure is pending. This will permit the direct analysis of suspended sediment for total or total recoverable metal concentrations. Particle sizing techniques have been investigated and recommendations have been submitted to the Quality of Water Branch. Additional work is in progress for quantitating metals when very limited amounts of sample are available (e.g., <50 mg) and to determine sediment- chemical partitioning (how and where metals are held by sediments). o Doyle Stephens of the Utah District has developed a software system and documentation on the use and utility of cluster analysis procedures for analysis of NASQAN phytoplankton data. A U.S. Geological Survey computer contribution series report will be available in FY 1986. o The National Networks data base consisting of the NASQAN and HBMN water-quality data and daily-values data will be put on a Quality of Water Branch disk pack on the Reston QVARSC Prime minicomputer. Initially, the water-quality data set will be stored in the Prime Midas Plus format designed by the Kansas District for the interim water- quality data processing system (NWIS.85). The daily-values data set will conform to the format established for the interim Automated Data Processing System (ADAPS). Eventually the data will be converted to the National Water Information System (NWIS.9O) format. o In addition to the raw data files, the Headquarters staff has implemented the National Water-Quality Networks Station Information File (SIF) using INFO software. Work is continuing to enter the station information provided by the Districts as requested in the June 10, 1982, memorandum to the Districts. All other data and publications available at Headquarters are also being utilized to enter needed data into SIF. The file, in conjunction with the file management capabilities of the INFO software has aiready provided a flexible and powerful tool for generating information reports on the operation of National Networks stations. The DATAGRAF software system discussed below wlll allow National and state maps to be generated in conjunction with data available from SIF. Stations can be plotted based upon a large combination of different selection criteria available through SIF. Full use of the file will not be possible, however, until data entry is complete. Districts which did not complete and return questionnaires forwarded to them in 1982 will be requested by memorandum to provide selected information for entry into the file. o As an aid in maklng use ot the NASQAN and HBMN data, Headquarters staff have been actively involved in the acquisition of the DATAGRAF software system that provides user-friendly interactive access to the data for statistical and graphical analysis and tabular presentation of the data. Districts are encouraged to use the system and make recommendations for new procedures or modifications of old procedures. A draft user's manual for DATAGRAF is available from the Quailty of Water Branch. DATAGRAF is available for use or the QVARSC Prime. DATAGRAF will be distributed to interested Districts on a six-month free trial basis in the near future, but it has been decided to delay the distribution until the Districts are all running PRIMOS 19.4. DATAGRAF will have to be tested under PRIMOS 19.4 before it is distributed. Until then potential users should contact Gail Kalen at FTS 928-7955 to become a registered user on QVARSC. o A large number of published reports have been prepared which are either directly or indirectly relevant to the WRD National Water-Quality Networks Program. A list of these publications, including those in Preparation, has been compiled and is presented in AppendiX C. This listing is to be continually updated, and all parties are encouraged to report errors or omissions to the National Water-Quality Networks Coordinator in the Quality of Water Branch. District and Subdistrict Chiefs are requested to ensure that all personnel in their various offices (especially field offices) responsible for collect1ng water-quality samples for NASQAN and HBMN read and understand the contents of this memorandum. Should there be any questions concerning the operation of these networks, please contact me or Mike Yurewicz (FTS 928-6834). James C. Schornick WRD Distribution: A, S, FO, PO Key Words: Water quality, networks, project activities, sampling, NASQAN, Bench-Mark, FY 1986. This memorandum does not supersede any previous memorandum.