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Selenium in irrigated agricultural areas of the western United States

Selenium was recognized as an important aquatic contaminant following the identification of widespread deformities in waterfowl at the agricultural drainage evaporation ponds of the Kesterson Reservoir (California) in 1983. Since then, California has been the focal point for global research and management of Se contamination. We analyzed the history and current developments in science, policy, and management of irrigation-induced Se contamination in California. In terms of management, we evaluated the effects of improvements in the design of local attenuation methods (drainage reuse and evaporation ponds) in conjunction with the development of programs for Se load reductions at the regional scale (namely the Grassland Bypass Project). In terms of policy, the USEPA is currently working on site-specific water quality criteria for the San Francisco Bay Delta that may be a landmark for future legislation on Se in natural water bodies. We provide a critical analysis of this approach and discuss challenges and opportunities in expanding it to other locations such as the Salton Sea. Management lessons learned in California and the novel policy approach may help prevent future events of Se contamination.

Journal of Environmental Quality↗

Volatilization of benzene and eight alkyl-substituted benzene compounds from water

Predicting the fate of organic compounds in streams and rivers often requires knowledge of the volatilization characteristics of the compounds. The reference-substance concept, involving laboratory-determined ratios of the liquid-film coefficients for volatilization of the organic compounds to the liquid-film coefficient for oxygen absorption, is used to predict liquid-film coefficients for streams and rivers. In the absence of experimental data, two procedures have been used for estimating these liquid-film coefficient ratios. These procedures, based on the molecular-diffusion coefficient and on the molecular weight, have been widely used but never extensively evaluated. Liquid-film coefficients for the volatilization of benzene and eight alkyl-substituted benzene compounds (toluene through n-octylbenzene) from water were measured in a constant-temperature, stirred water bath. Liquid-film coefficients for oxygen absorption were measured simultaneously. A range of water mixing conditions was used with a water temperature of 298.2 K. The ratios of the liquid-film coefficients for volatilization to the liquid-film coefficient for oxygen absorption for all of the organic compounds were independent of mixing conditions in the water. Experimental ratios ranged from 0.606 for benzene to 0.357 for n-octylbenzene. The molecular-diffusion-coefficient procedure accurately predicted the ratios for ethylbenzene through n-pentylbenzene with a power dependence of 0.566 on the molecular-diffusion coefficient, in agreement with published values. Predicted ratios for benzene and toluene were slightly larger than the experimental ratios. These differences were attributed to possible interactions between the molecules of these compounds and the water molecules and to benzene-benzene interactions that form dimers. Because these interactions also are likely to occur in natural waters, it was concluded that the experimental ratios are more correct than the predicted ratios for application purposes in the reference-substance concept. Predicted ratios for n-hexylbenzene, n-heptylbenzene, and n-octylbenzene were larger than the experimental ratios. These differences were attributed to a sorption-desorption process between these compounds and the surfaces of the constant-temperature water bath. Other experimental problems associated with preparing water solutions of these slightly soluble compounds also may have contributed to the differences. Because these processes are not part of the true volatilization process, it was concluded that the predicted ratios for these three compounds are probably more correct than the experimental ratios for application purposes in the reference-substance concept. Any model of the fate of these compounds in streams and rivers would have to include terms accounting for sorption processes, however. The molecular-weight procedure accurately predicted the ratios for ethylbenzene through n-pentylbenzene, but only if the power dependence on the molecular weight was decreased from the commonly used -0.500 to -0.427. Deviations for the low- and high-molecular-weight compounds were similar to those observed for the molecular-diffusion-coefficient procedure.

Water Supply Paper↗

One-Water Hydrologic Flow Model: A MODFLOW based conjunctive-use simulation software

The U.S. Geological Survey’s (USGS) Modular Ground-Water Flow Model (MODFLOW-2005) is a computer program that simulates groundwater flow by using finite differences. The MODFLOW-2005 framework uses a modular design that allows for the easy development and incorporation of new features called processes and packages that work with or modify inputs to the groundwater-flow equation. A process solves a flow equation or set of equations. For example, the central part of MODFLOW is the groundwater-flow process that solves the groundwater-flow equation; the surface-water routing process is an additional process that solves the surface-water flow equation. Packages are code related to the groundwater-flow process. For example, the subsidence package modifies the groundwater-flow process by including aquifer compaction effects on flow. With the development of new packages and processes, the MODFLOW-2005 base framework diverged into multiple independent versions designed for specific simulation needs. This divergence limited each independent MODFLOW release to its specific purpose, so that there was no longer a single, comprehensive, general-purpose hydraulic-simulation framework. The MODFLOW One-Water Hydrologic Flow Model (MF-OWHM, also informally known as OneWater) is an integrated hydrologic flow model that combines multiple MODFLOW-2005 variants in one cohesive simulation software; changes were made to enable multiple capabilities in one code. This fusion of the MODFLOW-2005 versions resulted in a simulation software that can be used to address and analyze a wide class of conjunctive-use, water-management, water-food-security, and climate-crop-water scenarios. As a second core version of MODFLOW-2005, MF-OWHM maintains backward compatibility with existing MODFLOW-2005 versions, with features that include the following: Process-based simulation. Saturated groundwater flow (three-dimensional). Surface-water flow (one- and two-dimensional). Stream and river flow. Lake and reservoir storage. Landscape simulation and irrigated agriculture. Land-use and crop simulation. Root uptake of groundwater. Actual evapotranspiration. Estimated irrigation demand. Reservoir operations. Aquifer compaction and subsidence by vertical model-grid deformation. Seawater intrusion by a sharp-interface assumption. Karst-aquifer and fractured-bedrock flow. Turbulent and laminar-pipe network flow. Unsaturated groundwater flow (one-dimensional). Internal linkages among the processes that couple hydraulic head, flow, and deformation. Redesigned code for faster simulation, increased user-input options, easier model updates, and more robust error reporting than in previous models. MF-OWHM is a MODFLOW-2005 based integrated hydrologic model that can simulate and analyze varying environmental conditions to allow for the evaluation of management options from many components of human and natural water movement through a physically based, supply and demand framework. The term “integrated,” in the context of this report, refers to the tight coupling of groundwater flow, surface-water flow, landscape processes, aquifer compaction and subsidence, reservoir operations, and conduit (karst) flow. Another benefit of this integrated hydrologic model is that models developed to run by MODFLOW-2005, MODFLOW-NWT, MODFLOW-CFP, or MODFLOW-FMP can also be simulated with MF-OWHM. At the time of this report’s publication, MF-OWHM version 2 (MF-OWHM2) does not include a direct internal simulation of snowmelt, advanced mountainous watershed rainfall-runoff simulation, detailed shallow soil-moisture accounting, or atmospheric moisture content. Atmospheric moisture may be accounted for indirectly by, optionally, specifying a pan-evaporation rate, reference evapotranspiration, and precipitation. These features are not included to ensure that simulation runtime remains short enough to enable the use of automated methods of calibrating model parameters to field observations, which typically require many simulation model runs. The MF-OWHM approach is to include as much detail as possible to simulate hydrological processes, providing the simulation runtimes remain reasonable enough to allow for robust parameter estimation and model calibration. To represent both natural and human-influenced flow, MF-OWHM integrates physically based flow processes derived from MODFLOW-2005 in a supply and demand framework. From this integration, the physically based movement of groundwater, surface water, imported water, and precipitation serve as supply to meet consumptive demands associated with irrigated and non-irrigated agriculture, natural vegetation, and urban water uses. Water consumption is determined by balancing the available water supply with water demand, leading to the concept of a demand-driven, supply-constrained simulation. The MF-OWHM Supply-and-Demand Framework is especially useful for the analysis of agricultural water use, where there are often few data available to describe changes in land-use through time, such as crop type and distribution, and the associated changes in groundwater pumpage. This framework attempts to satisfy each land-use water demand with available water supplies—that is, groundwater uptake, precipitation, and irrigation. An option provided in MF-OWHM2 is to automatically increase groundwater pumping for irrigation, which often is unknown, by the calculated residual between demand and the other available sources of supply. From large- to small-scale applications, the physically based supply and demand framework provides key capabilities for simulating and analyzing historical, current, and future conjunctive-use of surface water and groundwater. To achieve the physically based supply and demand framework, the MODFLOW-2005 standard of no inter-package and -process communication was relaxed for MF-OWHM2. Traditional MODFLOW simulation models required that all packages and processes interact through the groundwater-flow equation or by removing the water flow from the simulation domain. For example, the MODFLOW-2005 representation of a groundwater well extracts water from the groundwater-flow equation (by subtraction) and removes it from the simulation domain. This feature is available in the MF-OWHM framework, but options have been added to allow the specification of a use or destination of pumped groundwater within the model domain, for example, it can be used for irrigation, managed aquifer recharge, or return-flow to streams.

Techniques and Methods↗

Methods of analysis by the U.S. Geological Survey Organic Geochemistry Research Group: Determination of triazine and phenylurea herbicides and their degradation products in water using solid-phase extraction and liquid chromatography/mass spectrometry

An analytical method for the determination of 7 triazine and phenylurea herbicides and 12 of their degradation products in natural water samples using solid-phase extraction and liquid chromatography/mass spectrometry is presented in this report. Special consideration was given during the development of the method to prevent the formation of degradation products during the analysis. Filtered water samples were analyzed using 0.5 gram graphitized carbon as the solid-phase extraction media followed by liquid chromatography/mass spectrometry. Three different water-sample matrices ground-water, surface-water, and reagent-water samples?spiked at 0.2 and 2.0 micrograms per liter were analyzed. Method detection limits ranged from 0.013 to 0.168 microgram per liter for the parent triazine herbicides and the triazine degradation products. Method detection limits ranged from 0.042 to 0.141 microgram per liter for the parent phenylurea herbicides and their degradation products. Mean recoveries for the triazine compounds in the ground- and surface-water samples generally ranged from 72.6 to 117.5 percent, but deethyl-cyanazine amide was recovered at 140.5 percent. Mean recoveries from the ground- and surface-water samples for the phenylurea compounds spiked at the 2.0-micrograms-per-liter level ranged from 82.1 to 114.4 percent. The mean recoveries for the phenylureas spiked at 0.2-microgram per liter were less consistent, ranging from 87.0 to 136.0 percent. Mean recoveries from reagent-water samples ranged from 87.0 to 109.5 percent for all compounds. The triazine compounds and their degradation products are reported in concentrations ranging from 0.05 to 2.0 micrograms per liter, with the exception of deethylcyanazine and deethylcyanazine amide which are reported at 0.20 to 2.0 micrograms per liter. The phenylurea compounds and their degradation products are reported in concentrations ranging from 0.20 to 2.0 micrograms per liter. The upper concentration limit was 2.0 micrograms per liter for all compounds without dilution.

Open-File Report↗

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory - Determination of moderate-use pesticides and selected degradates in water by C-18 solid-phase extraction and gas chromatography/mass spectrometry

A method for the isolation and analysis of 21 parent pesticides and 20 pesticide degradates in natural-water samples is described. Water samples are filtered to remove suspended particulate matter and then are pumped through disposable solid-phase-extraction columns that contain octadecyl-bonded porous silica to extract the analytes. The columns are dried by using nitrogen gas, and adsorbed analytes are eluted with ethyl acetate. Extracted analytes are determined by capillary-column gas chromatography/mass spectrometry with selected-ion monitoring of three characteristic ions. The upper concentration limit is 2 micrograms per liter (µg/L) for most analytes. Single-operator method detection limits in reagent-water samples range from 0.00 1 to 0.057 µg/L. Validation data also are presented for 14 parent pesticides and 20 degradates that were determined to have greater bias or variability, or shorter holding times than the other compounds. The estimated maximum holding time for analytes in pesticide-grade water before extraction was 4 days. The estimated maximum holding time for analytes after extraction on the dry solid-phase-extraction columns was 7 days. An optional on-site extraction procedure allows for samples to be collected and processed at remote sites where it is difficult to ship samples to the laboratory within the recommended pre-extraction holding time. The method complements existing U.S. Geological Survey Method O-1126-95 (NWQL Schedules 2001 and 2010) by using identical sample preparation and comparable instrument analytical conditions so that sample extracts can be analyzed by either method to expand the range of analytes determined from one water sample.

Water-Resources Investigations Report↗

Methods of analysis by the U.S. Geological Survey Organic Geochemistry Research Group: Determination of selected herbicides and their degradation products in water using solid-phase extraction and gas chromatography/mass spectrometry

A method for the extraction and analysis of eight herbicides and five degradation products using solid-phase extraction from natural water samples followed by gas chromatography/mass spectrometry is presented in this report. This method was developed for dimethenamid; flufenacet; fluometuron and its degradation products, demethylfluometuron (DMFM), 3-(trifluromethyl) phenylurea (TFMPU), 3-(trifluromethyl)-aniline (TFMA); molinate; norflurazon and its degradation product, demethylnorflurazon; pendamethalin; the degradation product of prometryn, deisopropylprometryn; propanil; and trifluralin. The eight herbicides are used primarily in the southern United States where cotton, rice, and soybeans are produced. The exceptions are dimethenamid and flufenacet, which are used on corn in the Midwest. Water samples received by the U.S. Geological Survey's Organic Geochemistry Research Group in Lawrence, Kansas, are filtered to remove suspended particulate matter and then passed through disposable solid-phase extraction columns containing octadecyl-bonded porous silica (C-18) to extract the compounds. The herbicides and their degradation products are removed from the column by ethyl acetate elution. The eluate is evaporated under nitrogen, and components then are separated, identified, and quantified by injecting an aliquot of the concentrated extract into a high-resolution, fused-silica capillary column of a gas chromatograph/mass spectrometer under selected-ion mode. Method detection limits ranged from 0.02 to 0.05 μg/L for all compounds with the exception of TFMPU, which has a method detection limit of 0.32 μg/L. The mean absolute recovery is 107 percent. This method for the determination of herbicides and their degradation products is valuable for acquiring information about water quality and compound fate and transport in water.

Open-File Report↗

Water-mineral relations of Quaternary deposits in the Lower Platte River drainage area in eastern Nebraska

The partial pressure of carbon dioxide (PCO2), the degree of saturation with respect to calcite (IAP/K calcite), the pH, and the concentrations of selected constituents in solution were determined for water from 52 wells and the Platte River. Compared to the PCO2 in the atmosphere, the average PCO2 in the ground water was many times greater and that in .the river water was about twice as great. The high PCO2 in the ground water probably results from the absorption, by infiltrating precipitation, of carbon dioxide produced in the soil by respiration of plant roots ,and microorganisms. The values for IAP/K calcite for the ground water ranged from 0.141 to 1.29 and for the river water the average was 9.6. Water from each of the 10 sampled wells on the terrace plain in southeastern Saunders County was unsaturated with respect to calcite, whereas water from seven of the 42 wells on the Platte River flood plain was nearly saturated or supersaturated. Of the ,seven, two were in the Lincoln city well field where hydrologic relations indicate that a large fraction of the water yielded by the wells is induced seepage from the .river. That more of the city wells did not yield supersaturated water is surprising in view of the high IAP/K calcite values for the river water. Supersaturation of water from five of nine sampled wells downvalley from the well field probably is due to the presence of numerous limestone fragments in the Quaternary deposits in that part of the area. also surprising was the finding that the average pH of the water from the city wells was 1 unit lower than that of the river water. The presence of both dissolved iron and dissolved oxygen in the water from several of the city wells probably reflects derivation of the water from two distinct sources : ground water naturally in the aquifer and induced seepage from the river.

Water Supply Paper↗

Tolerance of developing salmonid eggs and fry to nitrate exposure

This paper reports on tests which show significant effects on early salmonid life stages of nitrates at levels commonly found in groundwaters in geographical areas that are influenced by fertilizer application. It has long been known, from fish cultural experience, that in certain site specific locations, chronic problems can be expected with salmonid egg development and early fry mortality. However, fingerlings which survive usually grow normally. A complete explanation is lacking although several environmental factors have been proposed to account for this phenomenon. One, which has so far received little attention, is that nitrate levels in the ground and surface waters of many areas have been increasing significantly over historical background levels. Ammonia, urea, and other potential sources of nitrate can enter natural waters from a variety of sources, such as domestic or industrial sewage, animal feedlots, or seepage and return flows from agricultural lands. The latter may be the largest contributor, since billions of tons of nitrate fertilizers are applied to agricultural crops on a worldwide basis each year. In addition, intensive forest management techniques include the aerial application of nitrate fertilizer to increase the yield of wood products, while range management practices call for use of nitrates to increase forage production. The nitrate that is not taken up by plants ultimately appears in ground or surface waters.

Bulletin of Environmental Contamination and Toxico↗

Fractionation of Cu and Zn isotopes during adsorption onto amorphous Fe(III) oxyhydroxide: Experimental mixing of acid rock drainage and ambient river water

Fractionation of Cu and Zn isotopes during adsorption onto amorphous ferric oxyhydroxide is examined in experimental mixtures of metal-rich acid rock drainage and relatively pure river water and during batch adsorption experiments using synthetic ferrihydrite. A diverse set of Cu- and Zn-bearing solutions was examined, including natural waters, complex synthetic acid rock drainage, and simple NaNO 3 electrolyte. Metal adsorption data are combined with isotopic measurements of dissolved Cu ( 65 Cu/ 63 Cu) and Zn ( 66 Zn/ 64 Zn) in each of the experiments. Fractionation of Cu and Zn isotopes occurs during adsorption of the metal onto amorphous ferric oxyhydroxide. The adsorption data are modeled successfully using the diffuse double layer model in PHREEQC. The isotopic data are best described by a closed system, equilibrium exchange model. The fractionation factors ( α soln–solid ) are 0.99927 ± 0.00008 for Cu and 0.99948 ± 0.00004 for Zn or, alternately, the separation factors ( Δ soln–solid ) are −0.73 ± 0.08‰ for Cu and −0.52 ± 0.04‰ for Zn. These factors indicate that the heavier isotope preferentially adsorbs onto the oxyhydroxide surface, which is consistent with shorter metal–oxygen bonds and lower coordination number for the metal at the surface relative to the aqueous ion. Fractionation of Cu isotopes also is greater than that for Zn isotopes. Limited isotopic data for adsorption of Cu, Fe(II), and Zn onto amorphous ferric oxyhydroxide suggest that isotopic fractionation is related to the intrinsic equilibrium constants that define aqueous metal interactions with oxyhydroxide surface sites. Greater isotopic fractionation occurs with stronger metal binding by the oxyhydroxide with Cu > Zn > Fe(II).

Geochimica et Cosmochimica Acta↗

“Iron Water” from wells: Causes and prevention

Chemical analyses of ground‐ water samples taken from differing depths in a four‐county area in east Texas showed a general stratification with respect to dissolved iron , pH and hardness. On the basis of this stratification the waters of the ground‐ water reservoir were divided into a shallow zone of oxidation, A; a deep zone of reduction, C; and an intermediate and unstable zone, B, in which waters from above and below are mixed. Ground water from zones A and C generally is almost free of iron , whereas water from zone B generally contains objectionable amounts. This zoning is explained by recent laboratory work and theoretical data on iron in natural waters. Wells constructed to draw only from zones A or C should yield water relatively free of iron .

Groundwater↗

Toxicity of TFM (lampricide) to six early stages of rainbow trout (Salmo gairdneri)

The lampricide TFM (3-trifluoromethyl-4-nitrophenol) was tested against the following life stages of rainbow trout ( Salmo gairdneri ): green eggs, eyed eggs, sac fry, swim-up fry, fry, and fingerlings in four water hardnesses (12, 44, 170, and 320 mg/liter as CaCO 3 ). The eyed-egg stage was one of the most resistant stages tested, and the sac-fry stage was one of the least resistant. Increased water hardness decreases toxicity to all stages. The LC50’s range from 0.532 mg/liter to 40.0 mg/liter depending upon life stage, water hardness, and duration of exposure. The margin of safety for coexisting species exposed to TFM ranges from 3.2 to 4.1 in natural waters. The margin of safety for early life stages of rainbow trout and larval lamprey under controlled laboratory conditions ranges from 4.2 to 12.2. Therefore, all six early life stages of rainbow trout are safe in minimum lampricidal concentrations of TFM.

Journal of the Fisheries Research Board of Canada↗

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory-A method supplement for the determination of Fipronil and degradates in water by gas chromatography/mass spectrometry

A method for the isolation and detemrination of fipronil and four of its degradates has been developed. This method adapts an analytical method created by the U.S. Geological Survey National Water Quality Laboratory in 1995 for the determination of a broad range of high-use pesticides typically found in filtered natural-water samples. In 2000, fipronil and four of its degradates were extracted, analyzed, and validated using this method. The recoveries for these five compounds in reagent-water samples fortified at 1 microgram per liter (ug/L) avereraged 98 percent. Initial method detection limits averaged 0.0029 ug/L. The performance of these five new compounds is consistent with the performance of the compounds in the initial method, making it possible to include them in addition to the other 41 pesticides and pesticide degradates in the original method.

Open-File Report↗

Water quality and hydrology of the Silver River Watershed, Baraga County, Michigan, 2005-08

The Silver River Watershed comprises about 69 square miles and drains part of northeastern Baraga County, Michigan. For generations, tribal members of the Keweenaw Bay Indian Community have hunted and fished in the watershed. Tribal government and members of Keweenaw Bay Indian Community are concerned about the effect of any development within the watershed, which is rural, isolated, and lightly populated. For decades, the area has been explored for various minerals. Since 2004, several mineral-exploration firms have been actively investigating areas within the watershed; property acquisition, road construction, and subsurface drilling have taken place close to tributary streams of the Silver River. The U.S. Geological Survey, in cooperation with Keweenaw Bay Indian Community, conducted a multi-year water-resources investigation of the Silver River Watershed during 2005-08. Methods of investigation included analyses of streamflow, water-quality sampling, and ecology at eight discrete sites located throughout the watershed. In addition, three continuous-record streamgages located within the watershed provided stage, discharge, specific conductance, and water-temperature data on an hourly basis. Water quality of the Silver River Watershed is typical of many streams in undeveloped areas of Upper Michigan. Concentrations of most analytes typically were low, although several exceeded applicable surface-water-quality standards. Seven samples had concentrations of copper that exceeded the Michigan Department of Environmental Quality standards for wildlife, and one sample had concentrations of cyanide that exceeded the same standards. Concentrations of total mercury at all eight sampling sites exceeded the Great Lakes Basin water-quality standard, but the ratio of methylmercury to total mercury was similar to the 5 to 10 percent found in most natural waters. Concentrations of arsenic and chromium in bed sediments were near the threshold-effect concentration. A qualitative ecological assessment of fishes and macroinvertebrates showed that intolerant salmonids were present at most sampled sites, and macroinvertebrate communities were indicative of near-excellent or excellent conditions at all eight sites. This baseline information will aid in an ongoing monitoring effort designed to protect the water resources of the

Scientific Investigations Report↗

Field application methods for recovery of the selective lampricide, 3-trifluoromethyl-4-nitrophenol

Colorimetric methods are described for the detection of residues of the selective lampricide, 3-trifluoromethyl-4-nitrophenol (TFM), in natural waters and fish tissues. Solvent extraction and anion exchange were used to separate and concentrate the lampricide, and to reduce high background colors which often interfere with the determinations. Data from the Pentwater and Muskegon Rivers (Michigan) showed an exponential rate of disappearance of TFM from the water immediately after treatments to eradicate larvae of the sea lamprey ( Petromyzon marinus ). No TFM was recovered from fish exposed in their natural environment to low levels of the lampricide during treatment; residues were recovered, however, from fish exposed to high concentrations in the laboratory.

Conference Paper↗

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory-Determination of pesticides in water by C-18 solid-phase extraction and capillary-column gas chromatography/mass spectrometry with selected-ion monitoring

A method for the isolation of 41 pesticides and pesticide metabolites in natural-water samples using C-18 solid-phase extraction and determination by capillary-column gas chromatography/mass spectrometry with selected-ion monitoring is described. Water samples are filtered to remove suspended particulate matter and then are pumped through disposable solid-phase extraction columns containing octadecyl-bonded porous silica to extract the pesticides. The columns are dried using carbon dioxide or nitrogen gas, and adsorbed pesticides are removed from the columns by elution with 3.0 milliliters of hexane-isopropanol (3:1). Extracted pesticides are determined by capillary- column gas chromatography/mass spectrometry with selected-ion monitoring of three characteristic ions. The upper concentration limit is 4 micrograms per liter (g/L) for most pesticides, with the exception of widely used corn herbicides--atrazine, alachlor, cyanazine, and metolachlor--which have upper concentration limits of 20 g/L. Single- operator method detection limits in reagent-water samples range from 0.001 to 0.018 g/L. Average short-term single-operator precision in reagent- water samples is 7 percent at the 0.1- and 1.0-g/L levels and 8 percent at the 0.01-g/L level. Mean recoveries in reagent-water samples are 73 percent at the 0.1- and 1.0-g/L levels and 83 percent at the 0.01-g/L level. The estimated holding time for pesticides after extraction on the solid-phase extraction columns was 7 days. An optional on-site extraction procedure allows for samples to be collected and processed at remote sites where it is difficult to ship samples to the laboratory within the recommended pre-extraction holding time.

Open-File Report↗

Assessment of the water resources of the Grand Ronde area, Oregon

Stream hydrographs show that throughout the Grand Ronde area most precipitation follows surface or shallow subsurface pathways to streams, resulting in rapid runoff and little natural water storage within the basin. Limited storage and low aquifer permeability restrict base flow to streams, and streamflows therefore decline rapidly once precipitation ceases. Shallow ground water and springs occur throughout the area, but because of the low permeability of aquifer materials, nearly all wells and springs have low yields. Water quality in streams, wells, and springs is generally good, but saline ground water has been reported on a number of drillers' logs for the study area and in several previous investigations of nearby areas. Further development of water resources in the Grand Ronde area is likely to be constrained by existing downstream water rights, the low permeability of geologic materials throughout the area, and possibly the intrusion of saline water. However, construction of facilities to store available water and thus compensate for low yields could provide a reliable, sustainable water supply for the Grand Ronde area.

Oregon↗

Stabilized liquid membrane device (SLMD) for the passive, integrative sampling of labile metals in water

A stabilized liquid membrane device (SLMD) is described for potential use as an in situ, passive, integrative sampler for cadmium (Cd), cobalt (Co), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) in natural waters. The SLMD (patent pending) consists of a 2.5-cm-wide by 15-cm-long strip of low-density polyethylene (LDPE) layflat tubing containing 1 mL of an equal mixture (v/v) of oleic acid (cis-9-octadecenoic acid) and EMO-8Q (7-[4-ethyl-1-methyloctyl]-8-quinolinol). The reagent mixture continuously diffuses to the exterior surface of the LDPE membrane, and provides for sequestration of several divalent metals for up to several weeks. Depending on sampler configuration, concentration factors of several thousand can be realized for these metal ions after just a few days. In addition to in situ deployment, the SLMD may be useful for laboratory determination of labile metal species in grab samples. Methods for minimizing the effects of water flow on the sampling rate are currently under investigation.

Water, Air, & Soil Pollution↗

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory-Determination of organophosphate pesticides in whole water by continuous liquid-liquid extraction and capillary-column gas chromatography with flame photometric detection

A method for the isolation of 20 parent organophosphate pesticides and 5 organophosphate pesticide degradates from natural-water samples is described. Compounds are extracted from water samples with methylene chloride using a continuous liquid-liquid extractor for 6 hours. The solvent is evaporated using heat and a flow of nitrogen to a volume of 1 milliliter and solvent exchanged to ethyl acetate. Extracted compounds are determined by capillary-column gas chromatography with flame photometric detection. Single-operator derived method detection limits in three water-matrix samples ranged from 0.003 to 0.009 microgram per liter. Method performance was validated by spiking all compounds in three different matrices at three different concentrations. Eight replicates were analyzed at each concentration in each matrix. Mean recoveries of most method compounds spiked in surface-water samples ranged from 54 to 137 percent and those in ground-water samples ranged from 40 to 109 percent for all pesticides. Recoveries in reagent-water samples ranged from 42 to 104 percent for all pesticides. The only exception was O-ethyl-O-methyl-S-propylphosphorothioate, which had variable recovery in all three matrices ranging from 27 to 79 percent. As a result, the detected concentration of O-ethyl-O-methyl-S-propylphosphorothioate in samples is reported in this method with an estimated remark code. Based on the performance issue, two more compounds, disulfoton and ethion monoxon, also will be reported in this method with an estimated remark code. Estimated-value compounds, which are ?E-coded? in the data base, do not meet the performance criteria for unqualified quantification, but are retained in the method because the compounds are important owing to high use or potential environmental effects and because analytical performance has been consistent and reproducible.

Water-Resources Investigations Report↗