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Simulation of soluble waste transport and buildup in surface waters using tracers

Soluble tracers can be used to simulate the transport and dispersion of soluble wastes that might have been introduced or are planned for introduction into surface waters. Measured tracer-response curves produced from the injection of a known quantity of soluble tracer can be used in conjunction with the superposition principle to simulate potential waste buildup in streams, lakes, and estuaries. Such information is particularly valuable to environmental and water-resource planners in determining the effects of proposed waste discharges. The theory, techniques, analysis, and presentation of results of tracer-waste simulation tests in rivers, lakes, and estuaries are described. This manual builds on other manuals on dye tracing with emphasis on the expanded use of time-of-travel type data.

Open-File Report↗

Simulation of soluble waste transport and buildup in surface waters using tracers

Soluble tracers can be used to simulate the transport and dispersion of soluble wastes that might have been introduced or are planned for introduction into surface waters. Measured tracer-response curves produced from the injection of a known quantity of soluble tracer can be used in conjunction with the superposition principle to simulate potential waste buildup in streams, lakes, and estuaries. Such information is particularly valuable to environmental and water-resource planners in determining the effects of proposed waste discharges. The theory, techniques, analysis, and presentation of results of tracer-waste simulation tests in rivers, lakes, and estuaries are described. This manual builds on other manuals dealing with dye tracing by emphasizing the expanded use of data from time-of-travel studies.

Techniques of Water-Resources Investigations↗

Percentage change in saturated thickness of the High Plains Aquifer, west-central Kansas, 1950 to average 1984-86

Continuing studies are being made in west-central Kansas to provide up-to-date information that will aid in the management of groundwater for irrigation. The results are presented of the sixth in a series of studies that used a statistical technique called kriging, to produce hydrologic maps. The kriging technique interpolates water level altitudes at the center of each 1 sq mi section in the study area on the basis of water level measurements from 169 observation wells. For this study, measurements made at each site during the winter months of 1984, 1985, and 1986 were averaged. These interpolated altitudes (1 ,859 in all), along with bedrock-surface and base yr water level altitudes, were used to prepare a hydrologic map that illustrates percentage change in saturated thickness. Saturated thickness, as used in this report, is the thickness of the High Plains aquifer between the groundwater surface, as indicated by water level altitudes, and the bedrock surface. Because irrigation development in west-central Kansas was minimal prior to 1950, the saturated thickness during 1950 represented a nearly static condition in the aquifer. Thus, the decrease in saturated thickness of the aquifer since 1950 is related to the effects of irrigation withdrawals on the volume of water in storage.

Kansas↗

Geology and ground-water resources of the Lawrenceville area, Georgia

The population of the Atlanta Metropolitan area continues to grow at a rapid pace and the demand for water supplies steadily increases. Exploration for ground-water resources, as a supplement to surface-water supplies, is being undertaken by many city and county governments. The application of effective investigative methods to characterization of the complex igneous and metamorphic fractured bedrock aquifers of the Piedmont physiographic province is essential to the success of these ground-water exploration programs. The U.S. Geological Survey, in cooperation with the City of Lawrenceville, Ga., began a study in December 1994 to apply various investigative techniques for field characterization of fractured crystalline-bedrock aquifers near Lawrenceville. Five major lithologic units were mapped in the Lawrenceville, Ga., area as part of an ongoing study of ground-water resources-amphibolite, biotite gneiss, button schist, granite gneiss, and quartzite/aluminous schist. These units generally are thin in outcrop width, have low angles of dip (nearly 0 to 20 degrees, dip reversals occur over short distances), and exhibit some shearing characteristics. The most productive unit for ground-water resources, on the basis of subsurface data collected through 1997, is the amphibolite. Historically, two wells drilled into this unit are recognized as having possibly the highest yields in the Piedmont region of northern Georgia. The City of Lawrenceville refurbished one well at the Rhodes Jordan Wellfield in 1990, and has pumped this well at an average rate of about 230 gallons per minute since 1995. In general, the composition of water collected from the bedrock wells, regolith wells, and City Lake is similar; calcium and bicarbonate are the dominant cation and anion, respectively. Water from the regolith wells and the lake have lower concentrations of major ions than does water from the bedrock wells. Many of the ground-water samples collected from the Rhodes Jordan Wellfield during October-November 1995, and from the wellfield and three additional observation well sites during August 1996, contain volatile organic compounds. Volatile organic compounds were detected in ground-water samples collected from several bedrock and regolith wells located in urban areas. Trace concentrations of tetrachloroethylene, trichloroethylene, 1,1-dichloroethane, trichlorofluoromethane, 1,1,1-trichloroethane, and cis-1,2-dichloroethene were detected. Methyl-tert-butyl ether (MTBE)-a compound used to increase the octane level in gasoline-was detected at concentrations above expected urban background levels in bedrock wells in the Rhodes Jordan Wellfield. Concentrations of MTBE ranged from 0.6 to 12 micrograms per liter in October-November 1995, and from 0.6 to 26 micrograms per liter in August 1996. Continuous ground-water-level data suggest that the fractured crystalline-bedrock aquifer (amphibolite unit) at the Rhodes Jordan Wellfield, generally is dewatered to a depth near a productive fracture during the regular pumping cycle of 18 hours per day, 5 days on and 2 days off per week. However, when the stress on the aquifer is increased by extending the pumping period up to as much as 18 days, or by pumping longer that 18 hours per day, the aquifer exhibits an unusual condition of recovery. Areal effects of pumping have been observed at distances of as much as one mile, extending across surface-water drainage divides.

Georgia↗

Guide to the Revised Ground-Water Flow and Heat Transport Simulator: HYDROTHERM - Version 3

The HYDROTHERM computer program simulates multi-phase ground-water flow and associated thermal energy transport in three dimensions. It can handle high fluid pressures, up to 1 ? 109 pascals (104 atmospheres), and high temperatures, up to 1,200 degrees Celsius. This report documents the release of Version 3, which includes various additions, modifications, and corrections that have been made to the original simulator. Primary changes to the simulator include: (1) the ability to simulate unconfined ground-water flow, (2) a precipitation-recharge boundary condition, (3) a seepage-surface boundary condition at the land surface, (4) the removal of the limitation that a specified-pressure boundary also have a specified temperature, (5) a new iterative solver for the linear equations based on a generalized minimum-residual method, (6) the ability to use time- or depth-dependent functions for permeability, (7) the conversion of the program code to Fortran 90 to employ dynamic allocation of arrays, and (8) the incorporation of a graphical user interface (GUI) for input and output. The graphical user interface has been developed for defining a simulation, running the HYDROTHERM simulator interactively, and displaying the results. The combination of the graphical user interface and the HYDROTHERM simulator forms the HYDROTHERM INTERACTIVE (HTI) program. HTI can be used for two-dimensional simulations only. New features in Version 3 of the HYDROTHERM simulator have been verified using four test problems. Three problems come from the published literature and one problem was simulated by another partially saturated flow and thermal transport simulator. The test problems include: transient partially saturated vertical infiltration, transient one-dimensional horizontal infiltration, two-dimensional steady-state drainage with a seepage surface, and two-dimensional drainage with coupled heat transport. An example application to a hypothetical stratovolcano system with unconfined ground-water flow is presented in detail. It illustrates the use of HTI with the combination precipitation-recharge and seepage-surface boundary condition, and functions as a tutorial example problem for the new user.

Techniques and Methods↗

Differentiating sediment sources using sediment fingerprinting techniques, in the Sprague River Basin, South-Central Oregon

Identifying sources of sediment to streams in the Sprague River Basin, in south-central Oregon, is important for restoration efforts that are focused on reducing sediment erosion and transport. Reducing sediment loads in these streams also contributes to compliance with the total maximum daily load reduction requirements for total phosphorus in this basin. In the Sprague River Basin, phosphorus occurs in surface waters in both dissolved phase and particulate phase, and particulate phosphorus is readily transported in streams on fine-grained suspended sediments, which eventually deposit in Upper Klamath Lake. The lake has seasonal blooms of cyanobacteria that require phosphorus for growth and degrade water-quality conditions, violating State water-quality standards and creating conditions that are stressful to two endangered suckers that reside in the lake. Identifying sources of sediment to the Sprague River could help inform restoration actions by determining the principal locations in the basin contributing fine sediment to the river. The U.S. Geological Survey, in cooperation with the U.S. Fish and Wildlife Service, conducted a proof-of-concept study to determine if sediment fingerprinting can differentiate sources of bank erosion by source material, basin, river reach, and soil horizon. The sediment fingerprinting approach uses properties of streambank and streambed sediment to differentiate between multiple sediment sources by determining a composite signature, or fingerprint. The composite fingerprint is established by combining fingerprint properties from laboratory results of elemental analysis, stable isotopes, and total carbon and nitrogen. The methods for differentiating sediment samples for this study include grouping bank and bed samples by basin, river reach, and soil horizon, and using non-parametric statistics to determine which fingerprint properties could be used to differentiate the sample groups. Results indicate that fingerprint properties differentiated source material, river reach, and basin, and were more successful at differentiating samples grouped by geographic location (basin and reach) compared to source material. Source material (banks, bed, levees) were differentiated with three fingerprint properties—Antimony (Sb), copper (Cu), and manganese (Mn). The basin category (South Fork and main-stem Sprague River) differentiated the South Fork and main stem with stable nitrogen isotopes (δ 15 N), aluminum (Al), silicon (Si), and vanadium (V). Specific river reaches within the study area were differentiated with 11 different fingerprint properties. These results can be used for apportionment studies using suspended sediment samples and mixing models to determine sediment source contributions within the basin.

Oregon↗

Influence of size-fractioning techniques on concentrations of selected trace metals in bottom materials from two streams in northeastern Ohio

Identical stream-bottom material samples, when fractioned to the same size by different techniques, may contain significantly different trace-metal concentrations. Precision of techniques also may differ, which could affect the ability to discriminate between size-fractioned bottom-material samples having different metal concentrations. Bottom-material samples fractioned to less than 0.020 millimeters by means of three common techniques (air elutriation, sieving, and settling) were analyzed for six trace metals to determine whether the technique used to obtain the desired particle-size fraction affects the ability to discriminate between bottom materials having different trace-metal concentrations. In addition, this study attempts to assess whether median trace-metal concentrations in size-fractioned bottom materials of identical origin differ depending on the size-fractioning technique used. Finally, this study evaluates the efficiency of the three size-fractioning techniques in terms of time, expense, and effort involved. Bottom-material samples were collected at two sites in northeastern Ohio: One is located in an undeveloped forested basin, and the other is located in a basin having a mixture of industrial and surface-mining land uses. The sites were selected for their close physical proximity, similar contributing drainage areas, and the likelihood that trace-metal concentrations in the bottom materials would be significantly different. Statistically significant differences in the concentrations of trace metals were detected between bottom-material samples collected at the two sites when the samples had been size-fractioned by means of air elutriation or sieving. Statistical analyses of samples that had been size fractioned by settling in native water were not measurably different in any of the six trace metals analyzed. Results of multiple comparison tests suggest that differences related to size-fractioning technique were evident in median copper, lead, and iron concentrations. Technique-related differences in copper concentrations most likely resulted from contamination of air-elutriated samples by a feed tip on the elutriator apparatus. No technique-related differences were observed in chromium, manganese, or zinc concentrations. Although air elutriation was the most expensive sizefractioning technique investigated, samples fractioned by this technique appeared to provide a superior level of discrimination between metal concentrations present in the bottom materials of the two sites. Sieving was an adequate lower-cost but more laborintensive alternative.

Ohio↗

Quantifying background nitrate removal mechanisms in an agricultural watershed with contrasting subcatchment baseflow concentrations

Numerous studies have documented the linkages between agricultural nitrogen loads and surface water degradation. In contrast, potential water quality improvements due to agricultural best management practices are difficult to detect because of the confounding effect of background nitrate removal rates, as well as the groundwater-driven delay between land surface action and stream response. To characterize background controls on nitrate removal in two agricultural catchments, we calibrated groundwater travel time distributions with subsurface environmental tracer data to quantify the lag time between historic agricultural inputs and measured baseflow nitrate. We then estimated spatially distributed loading to the water table from nitrate measurements at monitoring wells, using machine learning techniques to extrapolate the loading to unmonitored portions of the catchment to subsequently estimate catchment removal controls. Multiple models agree that in-stream processes remove as much as 75% of incoming loads for one subcatchment while removing <20% of incoming loads for the other. The use of a spatially variable loading field did not result in meaningfully different optimized parameter estimates or model performance when compared with spatially constant loading derived directly from a county-scale agricultural nitrogen budget. Although previous studies using individual well measurements have shown that subsurface denitrification due to contact with a reducing argillaceous confining unit plays an important role in nitrate removal, the catchment-scale contribution of this process is difficult to quantify given the available data. Nonetheless, the study provides a baseline characterization of nitrate transport timescales and removal mechanisms that will support future efforts to detect water quality benefits from ongoing best management practice implementation.

Maryland↗

Caution on the use of NBS 30 biotite for hydrogen-isotope measurements with on-line high-temperature conversion systems

RATIONALE The supply of NBS 30 biotite is nearly exhausted. During measurements of NBS 30 and potential replacements, reproducible δ 2 H VSMOW-SLAP values could not be obtained by three laboratories using high-temperature conversion (HTC) systems. The cause of this issue has been investigated using the silver-tube technique for hydrogen-isotope measurements of water. METHODS The δ 2 H VSMOW-SLAP values of NBS 30 biotite, other biotites, muscovites, and kaolinite with different particle sizes, along with IAEA-CH-7 polyethylene, and reference waters and NBS 22 oil that were sealed in silver-tube segments, were measured. The effect of absorbed water on mineral surfaces was investigated with waters both enriched and depleted in 2 H. The quantitative conversion of hydrogen from biotite into gaseous hydrogen as a function of mass and particle size was also investigated. RESULTS The δ 2 H VSMOW-SLAP values of NBS 30 obtained by three laboratories were as much as 21 ‰ too high compared with the accepted value of −65.7 ‰, determined by conventional off-line measurements. The experiments showed a strong correlation between grain size and the δ 2 H VSMOW-SLAP value of NBS 30 biotite, but not of biotites with lower iron content. The δ 2 H VSMOW-SLAP values of NBS 30 as a function of particle size show a clear trend toward −65.7 ‰ with finer grain size. CONCLUSIONS Determination of the δ 2 H VSMOW-SLAP values of hydrous minerals and of NBS 30 biotite by on-line HTC systems coupled to isotope-ratio mass spectrometers may be unreliable because hydrogen in this biotite may not be converted quantitatively into molecular hydrogen. Extreme caution in the use and interpretation of δ 2 H VSMOW-SLAP on-line measurements of hydrous minerals is recommended.

Rapid Communications in Mass Spectrometry↗

Modeling hyporheic zone processes

Stream biogeochemistry is influenced by the physical and chemical processes that occur in the surrounding watershed. These processes include the mass loading of solutes from terrestrial and atmospheric sources, the physical transport of solutes within the watershed, and the transformation of solutes due to biogeochemical reactions. Research over the last two decades has identified the hyporheic zone as an important part of the stream system in which these processes occur. The hyporheic zone may be loosely defined as the porous areas of the stream bed and stream bank in which stream water mixes with shallow groundwater. Exchange of water and solutes between the stream proper and the hyporheic zone has many biogeochemical implications, due to differences in the chemical composition of surface and groundwater. For example, surface waters are typically oxidized environments with relatively high dissolved oxygen concentrations. In contrast, reducing conditions are often present in groundwater systems leading to low dissolved oxygen concentrations. Further, microbial oxidation of organic materials in groundwater leads to supersaturated concentrations of dissolved carbon dioxide relative to the atmosphere. Differences in surface and groundwater pH and temperature are also common. The hyporheic zone is therefore a mixing zone in which there are gradients in the concentrations of dissolved gasses, the concentrations of oxidized and reduced species, pH, and temperature. These gradients lead to biogeochemical reactions that ultimately affect stream water quality. Due to the complexity of these natural systems, modeling techniques are frequently employed to quantify process dynamics.

Advances in Water Resources↗

Adsorption and desorption of atrazine and deethylatrazine by low organic carbon geologic materials

The adsorption and desorption of atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) and a primary metabolite, deethylatrazine (2-amino-4-chloro-6-isopropylamino-s-triazine; DEA), by low organic C (≤ 3.3 g kg −1 ) materials were measured by batch-equilibrium techniques. The adsorbents were samples of glacial outwash sand, till, and stream sediments. The adsorption of both atrazine and DEA conformed to linear isotherms. The adsorption of atrazine by most of the adsorbents yielded apparent K oc values that were in excess of those based on surface agricultural soils. Adsorption correlated with only the pH of the sand-water suspensions. The desorption of atrazine was hysteretic under the conditions of the measurement. DEA had a lower affinity for the same adsorbents; the mean ratio of K d values of DEA to those of atrazine was 0.37 ± 0.20. DEA adsorption did not correlate with organic C, surface area, clay content of the adsorbents, or with the pH of the suspensions. DEA adsorption, unlike atrazine, tended to be reversible. There was a linear relationship between the adsorption constants of atrazine and those of DEA.

Journal of Environmental Quality↗

Numerical simulation of groundwater flow in the Columbia Plateau Regional Aquifer System, Idaho, Oregon, and Washington

A three-dimensional numerical model of groundwater flow was constructed for the Columbia Plateau Regional Aquifer System (CPRAS), Idaho, Oregon, and Washington, to evaluate and test the conceptual model of the system and to evaluate groundwater availability. The model described in this report can be used as a tool by water-resource managers and other stakeholders to quantitatively evaluate proposed alternative management strategies and assess the long‑term availability of groundwater. The numerical simulation of groundwater flow in the CPRAS was completed with support from the Groundwater Resources Program of the U.S. Geological Survey Office of Groundwater. The model was constructed using the U.S. Geological Survey modular three-dimensional finite-difference groundwater-flow model, MODFLOW-NWT. The model uses 3-kilometer (9,842.5 feet) grid cells that subdivide the model domain by 126 rows and 131 columns. Vertically, the model domain was subdivided into six geologic model units. From youngest to oldest, the units are the Overburden, the Saddle Mountains Basalt, the Mabton Interbed, the Wanapum Basalt, the Vantage Interbed, and the Grande Ronde Basalt. Natural recharge was estimated using gridded historical estimates of annual precipitation for the period 1895&ndash;2007. Pre-development recharge was estimated to be the average natural recharge for this period. Irrigation recharge and irrigation pumping were estimated using a remote-sensing based soil-water balance model for the period 1985&ndash;2007. Pre-1985 irrigation recharge and pumping were estimated using previously published compilation maps and the history of large-scale irrigation projects. Pumping estimates for municipal, industrial, rural, residential, and all other uses were estimated using reported values and census data. Pumping was assumed to be negligible prior to 1920. Two models were constructed to simulate groundwater flow in the CPRAS: a steady-state predevelopment model representing conditions before large-scale pumping and irrigation altered the system, and a transient model representing the period 1900&ndash;2007. Automated parameter-estimation techniques (steady-state predevelopment model) and traditional trial-and-error (transient model) methods were used for calibration. To calibrate the steady-state and transient models, 10,525 and 46,460 water level measurements, respectively, and 50 base-flow estimates were used. The steady-state model simulated the shape, slope, and trends of a potentiometric surface that was generally consistent with mapped water levels. For the transient model, the mean and median difference between simulated and measured hydraulic heads is -10 and 4 ft, respectively, with a standard deviation of 164 ft over a 5,648 ft range of measured heads. The residuals for the simulation period show that 52 percent of the simulated heads exceeded measured heads with a median residual value of 43 ft, and 48 percent were less than measured heads with a median residual value of -76 ft. The CPRAS model was constructed to derive components of the groundwater budget and help understand the interactions of stresses, such as recharge, groundwater pumping, and commingling wells on the groundwater and surface-water system. Through these applications, the model can be used to identify trends in groundwater storage and use, and quantify groundwater availability. The annual groundwater budgets showed several patterns of change over the simulation period. Groundwater pumping was negligible until the 1950s and began to increase significantly during the 1970s and 1980s. Recharge was highly variable due to the interannual variability of precipitation, but began to increase in the late 1940s due to the increase in surface-water irrigation projects. Groundwater contributions to streamflow (base flow) followed recharge closely. However, in areas of significant groundwater-level decline, base flow is reduced. Groundwater pumping had the greatest effect on water levels, followed by irrigation enhanced recharge. Commingling was a larger factor in structurally complex upland areas where hydraulic-head gradients are naturally high. Groundwater pumping has increased substantially over the past 40&ndash;50 years; this increase resulted in declining water levels at depth and decreased base flows over much of the study area. The effects of pumping are mitigated somewhat by the increase of surface-water irrigation, especially in the shallow Overburden unit, and commingling wells in some areas. During dry to average years, groundwater pumping causes a net loss of groundwater in storage and current condition (2000&ndash;2007) groundwater pumping exceeds recharge in all but the wettest of years.

Idaho, Oregon, Washington↗

A comparison of analog and digital modeling techniques for simulating three-dimensional ground-water flow on Long Island, New York

A three-dimensional electric-analog model of the Long Island, NY , groundwater system constructed by the U.S. Geological Survey in the early 1970 's was used as the basis for developing a digital, three-dimensional finite-difference model. The digital model was needed to provide faster modifications and more rapid solutions to water-management questions. Results generated by the two models are depicted as potentiometric-surface maps of the upper glacial and Magothy aquifers. Results compare favorably for all parts of Long Island except the northwestern part, where hydrologic discontinuities are most prevalent and which the two models represent somewhat differently. The mathematical and hydrologic principles used in development of ground-water models, and the procedures for calibration and acceptance, are presented in nontechnical terms. (USGS)

Water-Resources Investigations Report↗

Complex resistivity signatures of ethanol in sand-clay mixtures

We performed complex resistivity (CR) measurements on laboratory columns to investigate changes in electrical properties as a result of varying ethanol (EtOH) concentration (0% to 30% v/v) in a sand–clay (bentonite) matrix. We applied Debye decomposition, a phenomenological model commonly used to fit CR data, to determine model parameters (time constant: τ, chargeability: m, and normalized chargeability: m n ). The CR data showed a significant (P ≤ 0.001) time-dependent variation in the clay driven polarization response (~ 12 mrad) for 0% EtOH concentration. This temporal variation probably results from the clay–water reaction kinetics trending towards equilibrium in the sand–clay–water system. The clay polarization is significantly suppressed (P ≤ 0.001) for both measured phase (ϕ) and imaginary conductivity (σ″) with increasing EtOH concentration. Normalized chargeability consistently decreases (by up to a factor of ~ 2) as EtOH concentration increases from 0% to 10% and 10 to 20%, respectively. We propose that such suppression effects are associated with alterations in the electrical double layer (EDL) at the clay–fluid interface due to (a) strong EtOH adsorption on clay, and (b) complex intermolecular EtOH–water interactions and subsequent changes in ionic mobility on the surface in the EDL. Changes in the CR data following a change of the saturating fluid from EtOH 20% to plain water indicate strong hysteresis effects in the electrical response, which we attribute to persistent EtOH adsorption on clay. Our results demonstrate high sensitivity of CR measurements to clay–EtOH interactions in porous media, indicating the potential application of this technique for characterization and monitoring of ethanol contamination in sediments containing clays.

Journal of Contaminant Hydrology↗

The interaction of natural organic matter with iron in a wetland (Tennessee Park, Colorado) receiving acid mine drainage

Pore water from a wetland receiving acid mine drainage was studied for its iron and natural organic matter (NOM) geochemistry on three different sampling dates during summer 1994. Samples were obtained using a new sampling technique that is based on screened pipes of varying length (several centimeters), into which dialysis vessels can be placed and that can be screwed together to allow for vertical pore-water sampling. The iron concentration increased with time (through the summer) and had distinct peaks in the subsurface. Iron was mainly in the ferrous form; however, close to the surface, significant amounts of ferric iron (up to 40% of 2 mmol L-1 total iron concentration) were observed. In all samples studied, iron was strongly associated with NOM. Results from laboratory experiments indicate that the NOM stabilizes the ferric iron as small iron oxide colloids (able to pass a 0.45μm dialysis membrane). We hypothesize that, in the pore water of the wetland, the high NOM concentrations (>100 mg C L-1) allow formation of such colloids at the redoxcline close to the surface and at the contact zone to the adjacent oxic aquifer. Therefore, particle transport along flow paths and resultant export of ferric iron from the wetland into ground water might be possible.

Aquatic Geochemistry↗

Changes in Rice Pesticide Use and Surface Water Concentrations in the Sacramento River Watershed, California

Pesticides applied to rice fields in California are transported into the Sacramento River watershed by the release of rice field water. Despite monitoring and mitigation programs, concentrations of two rice pesticides, molinate and thiobencarb, continue to exceed the surface-water concentration performance goals established by the Central Valley Regional Water Quality Control Board. There have been major changes in pesticide use over the past decade, and the total amount of pesticides applied remains high. Molinate use has declined by nearly half, while thiobencarb use has more than doubled; carbofuran has been eliminated and partially replaced by the pyrethroid pesticide lambda-cyhalothrin. A study was conducted in 2002 and 2003 by the U.S. Geological Survey to determine if the changes in pesticide use on rice resulted in corresponding changes in pesticide concentrations in surface waters. During the rice growing season (May-July), water samples, collected weekly at three sites in 2002 and two sites in 2003, were analyzed for pesticides using both solid-phase and liquid-liquid extraction in combination with gas chromatography/mass spectrometry. Analytes included lambda-cyhalothrin, molinate, thiobencarb, and two degradation products of molinate: 2-keto-molinate and 4-keto-molinate. Molinate, thiobencarb, and 4-keto-molinate were detected in all samples, 2-keto-molinate was detected in less than half of the samples, and lambda-cyhalothrin was not detected in any samples. At two of the sites sampled in 2002 (Colusa Basin Drain 1 and Sacramento Slough), concentrations of molinate were similar, but thiobencarb concentrations differed by a factor of five. Although concentrations cannot be estimated directly from application amounts in different watersheds, the ratio of molinate to thiobencarb concentrations can be compared with the ratio of molinate to thiobencarb use in the basins. The higher concentration ratio in the Sacramento Slough Basin, compared with the ratio in the basin area feeding the Colusa Basin Drain 1, is consistent with the higher use ratio, suggesting that differences in application amounts can explain the observed concentration differences. The samples from the downstream site (Tower) sampled in 2002 had the lowest concentrations of pesticides. Performance goals were exceeded for either molinate or thiobencarb in six samples from the upstream sites, but not in any samples from the downstream Tower site. In 2003, concentrations at upstream sites were much lower than the previous year with only one sample containing thiobencarb at a concentration above the performance goal. Lower concentrations could be partially due to delays in rice planting and pesticide application owing to spring rainstorms. Historical data is available on peak concentrations of molinate and thiobencarb measured at Colusa Basin Drain 5 (one of our sites in 2003) since 1981. Implementing holding times for pesticide-treated rice field water in the early 1980s succeeded in decreasing concentrations in surface waters. Detailed pesticide use data is available since 1991 and changing use patterns for molinate and thiobencarb can explain some, but not all, of the trends in peak pesticide concentrations. A stronger relationship is seen between the lengths of time that performance goals were exceeded and the amount of a pesticide applied within a basin. Different extraction and analytical techniques were used to improve the recovery and lower the method detection limit for lambda-cyhalothrin. Recoveries of lambda-cyhalothrin from solid-phase extraction cartridges typically vary, so subsamples were processed by liquid-liquid extraction. The advantage of using a larger sample volume (3 L instead of 1 L) to lower detection limits was offset by poor recovery during the cleanup step using an activated carbon column. Results suggest that as the concentrations of dissolved organic carbon in the sample increase, the recovery g

Scientific Investigations Report↗

Estimated use of water in the Delaware River Basin in Delaware, New Jersey, New York, and Pennsylvania, 2010

The Delaware River Basin (DRB) was selected as a Focus Area Study in 2011 by the U.S. Geological Survey (USGS) as part of the USGS National Water Census. The National Water Census is a USGS research program that focuses on national water availability and use and then develops new water accounting tools and assesses water availability at both the regional and national scales. One of the water management needs that the DRB study addressed, and that was identified by stakeholder groups from the DRB, was to improve the integration of state water use and water-supply data and to provide the compiled water use information to basin users. This water use information was also used in the hydrologic modeling and ecological components of the study. Instream and offstream water use was calculated for 2010 for the DRB based on information received from Delaware, New Jersey, New York, and Pennsylvania. Water withdrawal, interbasin transfers, return flow, and hydroelectric power generation release data were compiled for 11 categories by hydrologic subregion, basin, subbasin, and subwatershed. Data availability varied by state. Site-specific data were used whenever possible to calculate public supply, irrigation (golf courses, nurseries, sod farms, and crops), aquaculture, self-supplied industrial, commercial, mining, thermoelectric, and hydroelectric power withdrawals. Where site-specific data were not available, primarily for crop irrigation, livestock, and domestic use, various techniques were used to estimate water withdrawals. Total water withdrawals in the Delaware River Basin were calculated to be about 7,130 million gallons per day (Mgal/d) in 2010. Calculations of withdrawals by source indicate that freshwater withdrawals were about 4,130 Mgal/d (58 percent of the total) and the remaining 3,000 Mgal/d (42 percent) were from saline water. Total surface-water withdrawals were calculated to be 6,590 Mgal/d, or 92 percent of the total; about 54 percent (3,590 Mgal/d) of surface water withdrawn was freshwater. Total groundwater withdrawals were calculated to be 545 Mgal/d (8 percent of the total), all of which was freshwater. During 2010, calculated withdrawals by category, in decreasing order, were: thermoelectric power, 4,910 Mgal/d; public supply, 1,490 Mgal/d; self-supplied industrial, 350 Mgal/d; irrigation, 175 Mgal/d; self-supplied domestic, 117 Mgal/d; mining, 41.3 Mgal/d; aquaculture, 19.3 Mgal/d; livestock, 6.72 Mgal/d, and commercial, 5.89 Mgal/d. The amount of instream use for hydroelectric power generation purposes in 2010 was reported to be 273 Mgal/d for the Wallenpaupack Plant and 127 Mgal/d for the Mongaup River system. Total return flows in the DRB were 2,960 Mgal/d in 2010. Although municipal wastewater-treatment plants accounted for 539 (97 percent) of the return-flow sites, they accounted for about 70 percent of the total return flows in the DRB. There was limited information on return flows from thermoelectric power.

Delaware, New Jersey, New York, Pennsylvania↗

Percentage change in saturated thickness of the High Plains aquifer, west-central Kansas, 1950 to average 1985-87

Continuing studies are being made in west-central Kansas to provide up-to-date information that will aid in the management of groundwater for irrigation. This report, prepared by the U.S> Geological Survey in cooperation with the Western Kansas Groundwater Management District No. 1, presents the results of the seventh in a series of studies that uses a statistical technique, called kriging, to produce hydrologic maps. The kriging technique interpolates water-level altitudes at the center of each 1-square-mile section in the study area on the basis of water-level measurements from 164 observation wells. For this study, measurements made at each site during the winter months of 1985, 1986, and 1987 were averaged. These interpolated altitudes (1859 in all), along with bedrock-surface and base-year water-level altitudes were used to prepare a hydrologic map that illustrates percentage change in saturated thickness. Saturated thickness, as used in this report, is the thickness of the High Plains Aquifer between the groundwater surface, as indicated by water-level altitudes, and the bedrock surface. Because irrigation development in west-central Kansas was minimal prior to 1950, the saturated thickness during 1950 represented a nearly static condition in the aquifer. Thus, the decrease in saturated thickness of the aquifer since 1950 is related to the effects of irrigation withdrawals on the volume of water in storage.

Kansas↗