In Reply Refer To: September 13, 1984 EGS-Mail Stop 412 QUALITY OF WATER BRANCH TECHNICAL MEMORANDUM NO. 84.16 Subject: PROGRAMS AND PLANS--National Water-Quality Networks; Fiscal Year 1985--0ctober 1, 1984 to September 30, 1985. 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) 1985 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 data collection for these networks result when involved personnel are not adequately informed of changes in sample collection and processing procedures, and other aspects of networks operations. NETWORKS OPERATIONS, FY 1985 The NASQAN and HBMN data-collection programs will be operated essentially the same in FY 1985 as in FY 1984. District personnel should be aware of the following policies and procedures applicable to both NASQAN and HBMN for FY 1985. 1. As discussed in (1) each of the four Water Resources Division regional Prime continuums for District Water-Quality Specialists, and (2) the March 8, 1984 memorandum from the Assistant Chief Hydrologist for Operations to Regional Hydrologists and District Chiefs regarding the Federal Collection of Basic Records Program, alkalinity is to be analyzed in the field for the NASQAN and HBMN programs starting October 1, 1984. Field alkalinity as given herein refers to alkalinity, WATSTORE code 00410, in mg/L as CaC03, with fixed-endpoint titration to a pH of 4.5, immediately after the sample is collected. This change is being implemented to minimize the possibility of indeterminant changes in the concentration of alkalinity between time of collection and time of analysis. Laboratory alkalinity, WATSTORE code 90410, mg/L as CaC03, will continue to be analyzed by both Central Laboratories for each NASQAN and HBMN sample as part of Central Laboratories analytical schedules 176, 177, and 1904. At the end of FY 1985, a statistical comparison will be made with FY 1985 field and laboratory alkalinity data to determine if significant differences occur in the concentration of field and laboratory alkalinities. Sulfuric acid (H2S04) for field titrations can be ordered from the Denver Central Laboratory during FY 1985. Because it is so difficult to make exactly 0.01639 normality (N) H2S04, most H2S04 ordered from the Denver Central Laboratory will not be 0.01639 N. If the normality is not exactly 0.01639, a conversion factor will be included to correct to 0.01639 N when computing the alkalinity. Sulfuric acid obtained from the Denver Central Laboratory should be discarded after six months and fresh acid ordered. Furthermore, effective at the beginning of FY 1986, the following additional constituents are to be determined in the field for both NASQAN and HBMN: (1) carbonate alkalinity, electrometric incremental field titration; (2) dissolved carbonate, electrometric incremental field titration; and (3) dissolved bicarbonate, electrometric incremental field titration; (WATSTORE codes 99430, 99445, and 99440, respectively). Concentrations of these three constituents as well as the fixed-endpoint field alkalinity can all be computed from the same incremental titration. Analysis of the individual alkalinity components will allow increased utility of NASQAN amd HBMN data. In anticipation of this change in FY 1986, Districts should ensure that field personnel responsible for NASQAN and HBMN sampling are properly trained and equipped to determine these constituents in the field. To this end, it is suggested that Districts voluntarily initiate analysis of these three constituents during FY 1985 to ensure accurate analyses by the beginning of FY 1986. 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--parameter codes for 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: PUBLICATIONS--Policy on publishing constituents with both field and laboratory values). 2. The National Networks Program has agreed to provide additional samples for a National Research Program investigation to study seasonal and regional variation in the stable isotope composition at NASQAN and HBMN stations. The data-collection program will involve the collection of a 2 ounce filtered sample during each routine sampling for the next 2 years at selected NASQAN and HBMN stations. Each sample should be composited with a churn splitter as usual, filtered, poured into a 2 ounce glass bottle, preserved with one HgCl2 tablet, and capped. No preservation other than HgC12 is needed. Each sample should include a small amount of air space in the bottle. Tyler Coplen, project chief of the investigation, will select and notify the Districts of the NASQAN and HBMN stations where samples are to be collected. All of the necessary 2 ounce bottles for the selected stations will be purchased and forwarded to the Districts as soon as possible, along with any additional necessary information. Each bottle should be labeled with the station number and sample date and time. No other paperwork is necessary. Samples collected from each office 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 bottle breakage during shipment, samples should not be forwarded to Reston for analysis during the winter months. Samples will be anlayzed at no cost to the Districts for (1) deuterium/protium (hydrogen-2/hydrogen-1), ratio per mil, WATSTORE code 82082, Central Laboratories code 0300; and (2) oxygen-18/oxygen-16, ratio per mil, WATSTORE code 82085, 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 should not publish the analyses in the annual water resources data reports. The assistance of the Districts for this effort is appreciated. The Quality of Water Branch encourages the use of stable isotope hydrology within the Water Resources Division. This investigation will benefit Districts and the National Research Program by providing a national data base of stable isotope composition for surface water. 3. The National Water-Quality Networks program will consider authorizing funding for increased sampling frequencies at NASQAN or HBMN stations if an interpretive water resources investigation (1) is initiated by a District in a NASQAN or HBMN basin and (2) is mutually beneficial to both the District and the National Water-Quality Networks program. Funding will be authorized only at NASQAN or HBMN stations and will be considered on an individual basis. Districts should submit written requests for funding of increased sampling frequency to the National Water-Quality Networks Coordinator, with copies to their Regional Hydrologist and the Chief of the Operations Section in Reston. Even if Districts do not request funding for increased sampling frequencies, they are requested to inform this office of any water resources investigation being conducted which may be of interest to the National Water-Quality Networks program. 4. 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 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-weighed 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 waterquality 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 (and therefore stored in WATSTORE) at the same time as samples for common ions, nutrients, trace metals, etc. 5. 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 6. 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 procedure (schedule 176) will be used only for those constituents for which the ICP detection limit is at least as good as the atomic-absorption procedure. An exception is made for dissolved cobalt, which has a detection limit of 3 ug/L for the ICP procedure and 1 ug/L for the present atomic-absorption procedure. The ICP procedure is not to be used whenever the specific conductance is greater than 2,000 umho/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 umho/cm. The WATSTORE codes for schedules 176 and 177 are the same; however, the analytical procedures and, therefore, the laboratory codes are different for selected constituents. Based upon all 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 umho/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 2000 UMHO/CM". These values represent the overall probability that a sample collected during FY 1985 will require schedule 177 in lieu of schedule 176. Only schedule 176 is authorized for stations with zero probability of the specific conductance exceeding 2,000 umho/cm. Because of the uncertainty involved in predicting the number of samples during FY 1985 that will exceed 2,000 umho/cm, both schedule 176 and 177 are authorized for four uses at NASQAN stations where the value given in the right- hand column of Appendix A is greater than zero, and for two uses at the HBMN station Bear Den Creek near Mandaree, North Dakota (06332515). It is to be clearly understood, however, that the actual number of usages authorized between schedules 176 and 177 is four, not eight, for NASQAN, and two, not four, for HBMN. The District Water-Quality Specialist has 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. 7. The barometric pressure in millimeters of mercury (mm Hg, WATSTORE code 00025) is to continue to be measured in the field at the time of measurement of dissolved-oxygen concentration, and entered into WATSTORE. Be sure that the true atmospheric pressure existing at the time and elevation of measurement of dissolved-oxygen concentration is entered into WATSTORE; no correction to sea level should be made. This measurement was added so that the percent dissolved- oxygen saturation can be computed upon retrieval from WATSTORE. Trend analysis of percent saturation of dissolved oxygen is preferred to dissolved-oxygen concentration because it eliminates the variable effects of temperature, barometric pressure, and dissolved solids when comparing values over time or among stations. The barometric pressure must be measured with a barometer. Use of Thommen model 2000 pocket barometer is recommended, although an equivalent instrument is permitted. The Thommen model 2000 barometer is available from the Hydrologic Instrumentation Facility (HIF) in Bay St. Louis, Mississippi, at a cost of $160.00. The accuracy of all field barometers should be checked at least two times per year, and whenever the barometer has been accidently dropped, etc. This should be done at a weather station or airport. To enable comparison among locations, the barometric pressure readings reported by airports and weather stations are adjusted to sea level, and must therefore be adjusted back to the elevation of the weather station or airport to ensure proper comparison with the true barometric pressure reading of the field barometer. The following table is given as an aid in computing the values to subtract from barometric readings which are reported to sea level in mm Hg, and thus determine the actual barometric pressure at the elevation of the weather station or airport. Elevation, NGVD of Value to subtract, 1929, in feet mm Hg 0 0 1,000 27 2,000 53 3,000 79 4,000 104 5,000 128 6,000 151 The left-hand column represents the elevation of the weather station or airport, and the right-hand column represents the values to subtract from the reported barometric pressure readings, and thereby obtain the true barometric pressure with which to compare with the field barometer. Atmospheric pressure does not decrease at a linear rate for increases in elevation. However, because the table is subdivided into classes of elevation, linear interpolation is acceptable within the ranges of given elevation (reference: Smithsonian Miscellaneous Collections, vol. 114, Smithsonian Meterological Tables, prepared by Robert J. Sist, published by the Smithsonian Institution, 1951). The following example is given to clarify the procedure to be used. You are at an airport and the existing barometric pressure is reported to be 744 mm Hg. The pocket barometer you use for field work reads 672 mm Hg. The elevation of the airport is 2,750 feet above sea level. The value to subtract from 744 mm Hg is computed as: correction = 53 + (2750-2000)/(3000-2000) * (79-53) = 72 Alternately, the values given in the table can be plotted and the necessary values to subtract can be read directly from the graph. The actual barometric pressure at the airport is thus 744 mm Hg minus 72 mm Hg, or 672 mm Hg. Because the pocket barometer reading is also 672 mm Hg, no correction is necessary for the pocket barometer. 8. 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. 9. Districts are encouraged, but not required, to coordinate sampling trips with other District activities, especially stream gaging trips, to minimize field costs. A fixed- sampling time within each time period should, however, be the goal where feasible so that the original concept of a fixed- station, fixed-sampling interval monitoring network is maintained, and to the degree possible, random samples are collected. Exceptions to this rule can be made when conditions permit samples to be collected at high- or low- flow conditions at stations where the number of samples at extreme streamflows is limited. 10. Although the unique number, date, and time are all that are required on the Analytical Services Request Form used with the Water-Quality File in WATSTORE, other information such as station name, special sampling conditions, National-Networks program (NASQAN, Bench-Mark), etc., are also helpful both to 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. 11. Districts are reminded of the importance to ensure that all NASQAN and HBMN stations be sampled for the same measurements as specified later in this memorandum. In particular, all field measurements specified should be done for each sample; exceptions to this rule are to be justified in writing to the National Water-Quality Networks Coordinator. 12. Samples will be analyzed by the Central Laboratories for the same properties and constituents in FY 1985 as in FY 1984. No changes have been made, therefore, in the Central Laboratories analytical schedules used by NASQAN and HBMN. For the convenience of District personnel, all Central Laboratories' analytical schedules for NASQAN and HBMN are given in Appendix B. NASQAN NASQAN stations to be operated during the period October 1, 1984 through September 30, 1985, are listed in Appendix A. No stations have been added, relocated, or discontinued from FY 1984. Because the Tennessee-Tombigbee Waterway will open in December 1984, and may affect the water quality at the NASQAN station Tombigbee River at Gainesville, Alabama (02449000), the site sampling frequency for that station has been increased to monthly, effective October 1, 1984. The following Hydrologic Accounting Units (with the respective state abbreviation) are not represented in the NASQAN program: MI-WI MO AZ AZ CA HI HI 040602 103002 150501 150803 180902 200300 200900 LA TX AZ UT CA HI PR 080701 121102 150503 160203 181001 200400 210200 LA WY AZ NV AK HI 080903 140402 150802 160600 190200 200800 If a District feels that any of these Hydrologic Accounting Units should be included in the NASQAN program, it should submit a detailed memorandum describing the proposed sampling site, basin characteristics, etc., to the National Water-Quality Networks Coordinator (with a copy to the Regional Hydrologist's office) justifying its recommendation. NASQAN Sampling Schedule for FY 1985 There will be one station sampled monthly, 231 NASQAN stations sampled quarterly, and 269 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 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) Alkalinity (WATSTORE Code 00410) 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 (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 umho/cm) or lab schedule 177 (specific conductance > 2,000 umho/cm) Cross-section surveys of temperature, pH, specific conductance, dissolved oxygen, and suspended sediment as needed. 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 umho/cm) or lab schedule 177 (specific conductance > 2,000 umho/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 of temperature, pH, specific conductance, dissolved oxygen, and suspended sediment as needed. 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, common and trace dissolved inorganic constituents: lab schedule 176 2 per year - Physical properties and common dissolved inorganic constituents: lab schedule 1904 (not used when schedule 176 is used) Cross-section surveys of temperature, pH, specific conductance, dissolved oxygen, and suspended sediment as needed. NASQAN RADIOCHEMICAL SUBNETWORK NASQAN Radiochemical Subnetwork stations for FY 1985 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 collected at low-flow as before. 2 per year - Radiochemicals, lab schedule 1703 HYDROLOGIC BENCH-MARK NETWORK Hydrologic Bench-Mark Network stations with water-quality sampling in FY 1985 are listed in Appendix A. One station has been added to the network: water-quality sampling is being initiated on a quarterly basis at the HBMN station Blackwater River near Bradley, Alabama (02369800). This station was previously funded for daily surface-water discharge only. McDonalds Branch in Lebanon State Forest, New Jersey (01466500), and Upper Twin Creek at McGaw, Ohio (03237280), are to be sampled on a monthly basis in association with interpretive investigations in both HBMN drainage basins. Of the remaining 50 stations to be sampled for water quality during FY 1985, forty-two (42) HBMN stations will be sampled quarterly and 8 HBMN stations will be sampled bimonthly. 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. The specific conductance is likely to exceed 2,000 umho/cm at only one HBMN station-Bear Den Creek at Mandaree, ND (06332515). Therefore, this station may require schedule 177 for analysis of semiannual 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) Alkalinity (WATSTORE Code 00440) 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 (WATSTORE Code 70331) 4 per year - Nutrients, lab schedule 86 2 per year - Physical properties, common and trace dissolved inorganic constituents: lab schedule 176 2 per year - Physical properties and common dissolved inorganic constituents: lab schedule 1904 (not used when schedule 176 is used) 1 per year - Radiochemicals, lab schedule 1703 Cross-section surveys of temperature, pH, specific conductance, dissolved oxygen, and suspended sediment as needed. Hydrologic Bench-Mark Network Sampling Schedule (Bimonthly Stations) 6 per year - Field measurements (same as quarterly stations) 6 per year - Suspended sediment (same as quarterly stations) 6 per year - Nutrients, lab schedule 86 2 per year - Physical properties, common and trace dissolved inorganic constituents: lab schedule 176 (specific conductance < 2,000 umho/cm) or lab schedule 177 (specific conductance > 2,000 umho/cm) 4 per year - Physical properties and common dissolved inorganic constituents: lab schedule 1904 (not used when schedule 176 or 177 is used) 1 per year - Radiochemicals, lab schedule 1703 Cross-section surveys of temperature, pH, specific conductance, dissolved oxygen, and suspended sediment as needed. Hydrologic Bench-Mark Network Sampling Schedule (Monthly Stations) 12 per year - Field measurements (same as quarterly stations) 12 per year - Suspended sediment (same as quarterly stations) 12 per year - Nutrients, lab schedule 86 4 per year - Physical properties, 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) 1 per year - Radiochemicals, lab schedule 1703 Cross-section surveys of temperature, pH, specific conductance, dissolved oxygen, and suspended sediment as needed. PROGRAM ACTIVITIES AND PRODUCTS In addition to the ongoing data-collection program, the following diverse groups of activities are being supported by the National Networks Program: (1) interpretation of National Networks data by Headquarters staff, and Water Resources Division (WRD) District personnel; (2) collection of background information for planning new program initiatives, such as the National Organic Substances Monitoring Program and the Radiochemical Program; (3) development of new or improved analytical procedures; (4) development of new data-analysis procedures; and (5) development and distribution of information products related to the National Networks data base. 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. DATA INTERPRETATION PROJECTS o Data collected for the 1983 reconnaissance of organic substances in bottom sediment at selected NASQAN stations are presently being interpreted. The reconnaissance had two objectives. The first objective was to evaluate the gas chromatograph/flame ionization detector (GC/FID) procedure as a low cost and quick scanning technique for preselecting those samples that should be further analyzed by gas chromatograph mass spectrometer detector (GC/MS) for semiquantitative and possible qualitative identification of specific compounds. The second objective was to use these techniques to document the occurrence and distribution of organic substances in bottom materials of major rivers throughout the United States. The reconnaissance was based upon recommendations of the Organic Substances Task Group as an initial effort in the overall design of a National Organic Substances Monitoring Program (NOSMP), following the discontinuation of the former cooperative USGS/EPA Pesticide Subnetwork operated within NASQAN. The sampling program, which was planned and executed in a short period of time, was very successful. The cooperation of the WRD Districts and field personnel responsible for collecting the samples played a prime role in the overall effort. Based upon questionnaires completed by the Districts regarding bottom-sediment characteristics at all active NASQAN stations, samples from 303 stations were to be collected. Out of these 303 stations, samples from 273 stations were extracted by the Central Laboratories. Three projects are underway to assess the analytical data and methodology, and quality-assurance data for the reconnaissance. First, results of the samples analyzed are being interpreted by Al Harr of the Wisconsin District. The distribution and occurrence of the compounds identified and their associated concentrations will be studied. Second, Rolle Grabbe of the Denver Central Laboratory assessed quality-assurance aspects of analytical methodology used by both Central Laboratories to analyze reconnaissance samples. Third, Dennis Helsel of the Systems Analysis Group is assessing analytical results of quality-assurance samples to determine, by statistical procedures, the analytical variability, both within each Central Laboratory and between the Central Laboratories, for quality-assurance samples split between both Central Laboratories. An administrative report for each project will be submitted to the Chief of the Quality of Water Branch. Analytical results of reconnaissance samples will be forwarded to the Districts in October 1984. As stated before, the analytical results are not to be stored in WATSTORE. o Bob Gilliom, Richard Alexander, and Richard Smith interpreted all historical data from the former cooperative USGS/EPA Pesticide Subnetwork of NASQAN. A water-supply paper will be available in FY 1985. o Two interpretive reports by the Wisconsin District which deal with HBMN data will be available soon. The objectives of the first project are to: (1) summarize all water-quality data collected at each HBMN station through the 1979 water year; (2) determine, to the extent possible, whether water quality at these stations is representative of natural conditions; (3) estimate the magnitude of anthropogenic effects on the quality of the nation's rivers; (4) demonstrate methods for increasing the visibility of the HBMN program and for presenting and disseminating information from this program to water-data users; and (5) recommend procedures for improving the HBMN water-quality data collection program. The Wisconsin District is also preparing 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. The publication covers all available streamflow data collected through the 1981 water year. o The Pennsylvania District initiated a project in March 1983 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. A final report will be available at the beginning of FY 1985. o The North Dakota District is evaluating 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 regional atmospheric emissions, annual snow accumulation, and the magnitude of trace constituent enrichments observed, if any. A report will be available during FY 1985. o Streamflow data from HBMN stations in the Pacific Northwest and California regions will be studied by the Oregon 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 1985. o Streamflow and water-quality data for the HBMN station Falling Creek near Juliett, Georgia will be interpreted by the Georgia District to: (1) determine the presence or absence and magnitude of statistically significant temporal trends in water-quality parameters; (2) based upon the results of objective 1, determine which waterr-quality parameters are suitable for use as baseline trend indicators; (3) identify and characterize temporal trends at nearby studies representing basins undergoing development and those which are relatively static; and (4) analyze observed differences in trend slopes for selected water-quality parameters as they relate to differences in basin characteristics and to changes in land cover, land use, and water use. A final report will be available during FY 1985. o Interpretive reports will be available in FY 1985 for eight projects initiated by the NASQAN 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 have 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: Region River Basin and State Northeastern Region West Branch Susquehanna River, Pennsylvania Northeastern Region Upper Mississippi River, Minnesota Northeastern Region St. Croix River, Wisconsin Southeastern Region Peace River, Florida Southeastern Region Green River, Kentucky Southeastern Region Tennessee River, Tennessee Central Region Trinity River, Texas Central Region San Juan River, New Mexico Western Region Umpqua River, Oregon o An interpretive report by the New Mexico District will be available in FY 1985 which assesses the purpose, goals, methods, and results of the various WRD radiochemical data- collection programs. The report will also assess and identify new program needs and suggest alternatives. o Trend analysis of NASQAN and HBMN data is, and will continue to be, an important component of the research component of the National Water-Quality Networks program. The Seasonal Kendall 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 and are being compared with available soil information in an attempt to provide a geochemical interpretation for chemical changes at each station. Also, historical changes in atmospheric sulfur emissions are being 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 from the National Academy of Sciences due to be published in March 1985. 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 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 investigatin to develop and test prototype multivariate statistical procedures that can be used in regional and national assessments that predict abundances of solected 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 particularly interested in using the Seasonal Kendall tau trend analysis results by Richard Smith and Richard Alexander of the Quality of Water Branch. 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 of the Use and Health of United States Coastal Waters. NEW PROGRAM INITIATIVES o A project will be initiated in FY 1985 by John Turk and Don Campbell of the Colorado District to evaluate the hypothesis that observed trends in surface quality of HBMN stations are caused by atmospheric emissions and deposition. Approximately twenty HBMN stations will be chosen for detailed analysis. Selection criteria will include a significant trend in acidification representative of the region in which the station is located, and watershed characteristics representative of a large number of streams in the region. 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 chemistry, 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 plausible, the watershed will be examined to verify assumptions of no change in land use. Available 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. ANALYTICAL METHODS DEVELOPMENT o Two methods for the direct determination of total metals in bottom and suspended sediments have been developed and approved for use in the Central Laboratories 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 milligrams. Additional work is underway to permit total quantification of mercury, arsenic, antimony and selenium in sediment. A method(s) for the concentration of suspended sediment, after sampling, is also being developed and the final procedure should be available by the end of October 1984. This will permit the direct analysis of suspended sediment for total trace metal concentrations. Additional work is in progress and/or is planned for developing particle-sizing techniques for subsequent chemical analysis, and for determining sediment- chemical partitioning (how and/or where metals are held by sediments). NEW DATA-ANALYSIS PROCEDURES 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 1985. o A one-year project was initiated in May 1983 by Chuck Robinove to determine if land cover changes can be mapped from digital Landsat images and high altitude aerial photographs in sufficient detail and precision to determine if the water regime remains constant. The approach is to digitize land cover changes from Landsat images taken between 1972 and 1983 and to evaluate how well the changes are mapped and described. The mapping will be evaluated to determine if the method can and should be used in all HBMN drainage basins. Results of the project will be included in the January/June 1984 issue of the WRD Bulletin. INFORMATION PRODUCTS 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 WRD Operations Prime minicomputer (QVARSB). 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. 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) format currently being designed by a special task force of WRD personnel. o In addition to the raw data files, the Headquarters staff is implementing 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. Once completed, the file, in conjunction with the file management capabilities of the INFO software, will provide a flexible and powerful tool for generating information (reports on the operation of National Networks stations. The DATAGRAF software system discussed below will 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 questionaires forwarded to them in 1982 will be requested by memorandum to provide selected information for entry into the file. o As an aid in making use of 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 statistidal, graphical and geographical 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 Quality of Water Branch. DATAGRAF is currently only available for use on the Operations Prime. Potential users should contact Gail Kalen at FTS 928-7955 to become a registered user on QVARSB. If sufficient interest is shown in the system, arrangements can be made to purchase additional copies. Potential users should also consult the upcoming issue of DISCUSSIONS for more information on DATAGRAF and its available procedures. o The open Prime continuum "nasqn" is to be dropped because it is felt that the exchange of ideas and information concerning operation of NASQAN and HBMN can be handled just as easily by the use of the four Regional water-quality specialist's continuums. 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. For the purpose of distribution of this memorandum, District and Subdistrict offices will receive only that portion of Appendix A that pertains to their respective District. All others on the distribution list will receive a complete copy of Appendix A. District and Subdistrict Chiefs are requested to ensure that all personnel in their various offices (especially field offices) responsible for collecting 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 Jim Schornick or Mike Yurewicz of my staff (FTS 928-6834). R. J. Pickering Attachments WRD Distribution: A, S, FO, PO Key Words: Water quality, networks, project activities, sampling, NASQAN, Bench-Mark, FY 1985. This memorandum does not supersede any previous memorandum.