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USGS2009

Depleted uranium analysis in blood by inductively coupled plasma mass spectrometry

In this study we report depleted uranium (DU) analysis in whole blood samples. Internal exposure to DU causes increased uranium levels as well as change in the uranium isotopic composition in blood specimen. For identification of DU exposure we used the 235U/238U ratio in blood samples, which ranges from 0.00725 for natural uranium to 0.002 for depleted uranium. Uranium quantification and isotopic composition analysis were performed by inductively coupled plasma mass spectrometry. For method validation we used eight spiked blood samples with known uranium concentrations and isotopic composition. The detection limit for quantification was determined to be 4 ng L-1 uranium in whole blood. The data reproduced within 1-5% RSD and an accuracy of 1-4%. In order to achieve a 235U/238U ratio range of 0.00698-0.00752% with 99.7% confidence limit a minimum whole blood uranium concentration of 60 ng L??1 was required. An additional 10 samples from a cohort of veterans exposed to DU in Gulf War I were analyzed with no knowledge of their medical history. The measured 235U/ 238U ratios in the blood samples were used to identify the presence or absence of DU exposure within this patient group. ?? 2009 The Royal Society of Chemistry.

Journal of Analytical Atomic Spectrometry↗

USGS2014

Groundwater-quality data in the North San Francisco Bay Shallow Aquifer study unit, 2012: results from the California GAMA Program

Groundwater quality in the 1,850-square-mile North San Francisco Bay Shallow Aquifer (NSF-SA) study unit was investigated by the U.S. Geological Survey (USGS) from April to August 2012, as part of the California State Water Resources Control Board (SWRCB) Groundwater Ambient Monitoring and Assessment (GAMA) Program’s Priority Basin Project (PBP). The GAMA-PBP was developed in response to the California Groundwater Quality Monitoring Act of 2001 and is being conducted in collaboration with the SWRCB and Lawrence Livermore National Laboratory (LLNL). The NSF-SA study unit was the first study unit to be sampled as part of the second phase of the GAMA-PBP, which focuses on the shallow aquifer system. The GAMA NSF-SA study was designed to provide a spatially unbiased assessment of untreated-groundwater quality in the shallow aquifer systems and to facilitate statistically consistent comparisons of untreated-groundwater quality throughout California. The shallow aquifer system in the NSF-SA study unit was defined as the part of the aquifer system that is used by many private domestic wells and is shallower than the primary aquifer system used by many public-supply wells. In the NSF-SA study unit located in Marin, Mendocino, Napa, Solano, and Sonoma Counties, groundwater samples were collected from 71 wells. Seventy of the wells were selected by using a spatially distributed, randomized grid-based method to provide statistical representation of the study unit (grid wells), and one well was selected to aid in evaluation of water-quality issues (understanding well). The groundwater samples were analyzed for organic constituents (volatile organic compounds [VOCs], pesticides, and pesticide degradates); constituents of special interest (perchlorate and 1,2,3-trichloropropane [1,2,3-TCP]); naturally occurring inorganic constituents (trace elements, nutrients, major and minor ions, silica, and total dissolved solids [TDS]); and radioactive constituents (radon-222 and gross alpha and gross beta radioactivity). Naturally occurring isotopes (stable isotopes of hydrogen, oxygen, boron, strontium, and inorganic carbon in water, tritium activities, and carbon-14 abundances) were measured to help identify the sources and ages of the sampled groundwater. In total, 207 constituents and water-quality indicators were measured. Three types of quality-control samples (blanks, replicates, and matrix spikes) were collected at up to 13 percent of the wells in the NSF-SA study unit, and the results for these samples were used to evaluate the quality of the data for the groundwater samples. Blanks rarely contained detectable concentrations of any constituent, suggesting that contamination from sample-collection procedures was not a significant source of bias in the data for the groundwater samples. Replicate samples generally were within the limits of acceptable analytical reproducibility. Matrix-spike recoveries were within the acceptable range (70 to 130 percent) for approximately 91 percent of the compounds. Most of the wells sampled for this study were private domestic wells. Private domestic wells are not regulated in California, and groundwater from these wells is rarely analyzed for water-quality constituents. Although regulatory benchmarks for drinking-water quality do not apply to private domestic wells, to provide some context for the results, concentrations of constituents measured in the untreated groundwater were compared with regulatory and non-regulatory health-based benchmarks established by the U.S. Environmental Protection Agency (USEPA) and California Department of Public Health (CDPH), to non-regulatory health-based benchmarks established by the USGS in cooperation with the USEPA, and to non-regulatory benchmarks established for aesthetic concerns by the CDPH. Comparisons between data collected for this study and benchmarks for drinking water are for illustrative purposes only and are not indicative of compliance or non-compliance with those benchmarks. Most of the organic and inorganic constituents that were detected in groundwater samples from the 70 grid wells in the NSF-SA study unit were detected at concentrations less than drinking-water benchmarks. Of the 149 organic and special-interest constituents analyzed for in groundwater samples, 31 were detected; concentrations of most detected constituents were less than regulatory and non-regulatory health-based benchmarks. One VOC, benzene, and one insecticide, dieldrin, were detected at concentrations above their respective health-based benchmarks. In total, VOCs were detected in 40 percent of the grid wells sampled, pesticides and pesticide degradates were detected in 13 percent, and perchlorate was detected in 27 percent of the 70 grid wells sampled. Groundwater samples from 70 grid wells were analyzed for trace elements, major and minor ions, nutrients, and radioactive constituents; most detected concentrations were less than health-based benchmarks. Exceptions are 12 detections of manganese greater than the USGS Health-Based Screening Level (HBSL), 7 detections of arsenic greater than the USEPA maximum contaminant level (MCL-US) of 10 micrograms per liter (μg/L), 2 detections of boron greater than the HBSL of 6,000 μg/L, 2 detections of fluoride greater than the CDPH maximum contaminant level (MCL-CA) of 2 milligrams per liter (mg/L), 2 detections of nitrate greater than the MCL-US of 10 mg/L, and two detections of radon-222 greater than the proposed MCL-US of 4,000 picocuries per liter. Results for constituents with non-regulatory benchmarks set for aesthetic concerns from the grid wells showed that iron concentrations greater than the CDPH secondary maximum contaminant level (SMCL-CA) of 300 μg/L were detected in 13 grid wells. Chloride was detected at a concentration greater than the SMCL-CA recommended benchmark of 250 mg/L in two grid wells. Sulfate concentrations greater than the SMCL-CA recommended benchmark of 250 mg/L were measured in two grid wells, and the concentration in one of these wells was also greater than the SMCL-CA upper benchmark of 500 mg/L. TDS concentrations greater than the SMCL-CA recommended benchmark of 500 mg/L were measured in 15 grid wells, and concentrations in 4 of these wells were also greater than the SMCL-CA upper benchmark of 1,000 mg/L.

California↗

USGS2006

Use of field-applied quality control samples to monitor performance of a Goulden large-sample extractor/GC-MS method for pesticides in water

Since 1985, the Goulden large-sample extractor (GLSE) has been used to isolate a broad array of trace-organic contaminants from large volumes of water. In this study, field-applied quality control measures, including matrix and surrogate spikes and blanks, were used to monitor method performance from GLSE extraction through GC-MS analysis. The method was applied to the determination of multiple classes of pesticides isolated from 4- to 112-L filtered surface-water samples. Average recoveries of six surrogate compounds ranged from 84 ?? 18% for [2H10]diazinon to 15 ?? 13% for 4,4'-[2H8]DDT, the low recoveries for which were largely a result of unmonitored breakdown of this surrogate by the GC injection system. Field-matrix-spike samples were prepared by fortifying 10-L, 35-L, and 110-L filtered surface-water samples with 68 pesticides to amended concentrations of 11- to 50-ng/L each. Recoveries ranged from not detected to greater than 100%. Variability in pesticide recoveries from triplicate 10-L water samples collected at one site averaged 5.7% relative standard deviation and did not exceed 19%.Since 1985, the Goulden large-sample extractor (GLSE) has been used to isolate a broad array of trace-organic contaminants from large volumes of water. In this study, field-applied quality control measures, including matrix and surrogate spikes and blanks, were used to monitor method performance from GLSE extraction through GC-MS analysis. The method was applied to the determination of multiple classes of pesticides isolated from 4- to 112-L filtered surface-water samples. Average recoveries of six surrogate compounds ranged from 84 ?? 18% for [2H10]diazinon to 15 ?? 13% for 4,4???-[2H8]DDT, the low recoveries for which were largely a result of unmonitored breakdown of this surrogate by the GC injection system. Field-matrix-spike samples were prepared by fortifying 10-L, 35-L, and 110-L filtered surface-water samples with 68 pesticides to amended concentrations of 11- to 50-ng/L each. Recoveries ranged from not detected to greater than 100%. Variability in pesticide recoveries from triplicate 10-L water samples collected at one site averaged 5.7% relative standard deviation and did not exceed 19%.

International Journal of Environmental Analytical ↗

USGS2012

User guide for MODPATH version 6—A particle-tracking model for MODFLOW

MODPATH is a particle-tracking post-processing model that computes three-dimensional flow paths using output from groundwater flow simulations based on MODFLOW, the U.S. Geological Survey (USGS) finite-difference groundwater flow model. This report documents MODPATH version 6. Previous versions were documented in USGS Open-File Reports 89-381 and 94-464. The program uses a semianalytical particle-tracking scheme that allows an analytical expression of a particle's flow path to be obtained within each finite-difference grid cell. A particle's path is computed by tracking the particle from one cell to the next until it reaches a boundary, an internal sink/source, or satisfies another termination criterion. Data input to MODPATH consists of a combination of MODFLOW input data files, MODFLOW head and flow output files, and other input files specific to MODPATH. Output from MODPATH consists of several output files, including a number of particle coordinate output files intended to serve as input data for other programs that process, analyze, and display the results in various ways. MODPATH is written in FORTRAN and can be compiled by any FORTRAN compiler that fully supports FORTRAN-2003 or by most commercially available FORTRAN-95 compilers that support the major FORTRAN-2003 language extensions.

Techniques and Methods↗

USGS2002

Comparison of δ18O measurements in nitrate by different combustion techniques

Three different KNO 3 salts with δ 18 O values ranging from about −31 to +54‰ relative to VSMOW were used to compare three off-line, sealed glass tube combustion methods (widely used for isotope studies) with a more recently developed on-line carbon combustion technique. All methods yielded roughly similar isotope ratios for KNO 3 samples with δ 18 O values in the midpoint of the δ 18 O scale near that of the nitrate reference material IAEA-NO-3 (around +21 to +25‰). This reference material has been used previously for one-point interlaboratory and intertechnique calibrations. However, the isotope ratio scale factors by all of the off-line combustion techniques are compressed such that they are between 0.3 and 0.7 times that of the on-line combustion technique. The contraction of the δ 18 O scale in the off-line preparations apparently is caused by O isotope exchange between the sample and the glass combustion tubes. These results reinforce the need for nitrate reference materials with δ 18 O values far from that of atmospheric O 2 , to improve interlaboratory comparability.

Analytical Chemistry↗

USGS2009

Groundwater-quality data in the South Coast Interior Basins study unit, 2008: Results from the California GAMA Program

Groundwater quality in the approximately 653-square-mile South Coast Interior Basins (SCI) study unit was investigated from August to December 2008, as part of the Priority Basins Project of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA Priority Basins Project was developed in response to Legislative mandates (Supplemental Report of the 1999 Budget Act 1999-00 Fiscal Year; and, the Groundwater-Quality Monitoring Act of 2001 [Sections 10780-10782.3 of the California Water Code, Assembly Bill 599]) to assess and monitor the quality of groundwater used as public supply for municipalities in California, and is being conducted by the U.S. Geological Survey (USGS) in cooperation with the California State Water Resources Control Board (SWRCB). SCI was the 27th study unit to be sampled as part of the GAMA Priority Basins Project. This study was designed to provide a spatially unbiased assessment of the quality of untreated groundwater used for public water supplies within SCI, and to facilitate statistically consistent comparisons of groundwater quality throughout California. Samples were collected from 54 wells within the three study areas [Livermore, Gilroy, and Cuyama] of SCI in Alameda, Santa Clara, San Benito, Santa Barbara, Ventura, and Kern Counties. Thirty-five of the wells were selected using a spatially distributed, randomized grid-based method to provide statistical representation of the study unit (grid wells), and 19 were selected to aid in evaluation of specific water-quality issues (understanding wells). The groundwater samples were analyzed for organic constituents [volatile organic compounds (VOCs), pesticides and pesticide degradates, polar pesticides and metabolites, and pharmaceutical compounds], constituents of special interest [perchlorate and N-nitrosodimethylamine (NDMA)], naturally occurring inorganic constituents [trace elements, nutrients, major and minor ions, silica, total dissolved solids (TDS), and alkalinity], and radioactive constituents [gross alpha and gross beta radioactivity and radon-222]. Naturally occurring isotopes [stable isotopes of hydrogen, oxygen, and carbon, and activities of tritium and carbon-14] and dissolved noble gases also were measured to help identify the sources and ages of the sampled groundwater. In total, 288 constituents and water-quality indicators (field parameters) were investigated. Three types of quality-control samples (blanks, replicates, and matrix spikes) each were collected at approximately 4–11 percent of the wells, and the results for these samples were used to evaluate the quality of the data for the groundwater samples. Field blanks rarely contained detectable concentrations of any constituent, suggesting that contamination was not a significant source of bias in the data obtained from the groundwater samples. Differences between replicate samples generally were less than 10 percent relative standard deviation, indicating acceptable analytical reproducibility. Matrix spike recoveries were within the acceptable range (70 to 130 percent) for most compounds. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, untreated groundwater typically is treated, disinfected, and/or blended with other waters to maintain water quality. Regulatory thresholds apply to water that is served to the consumer, not to untreated groundwater. However, to provide some context for the results, concentrations of constituents measured in the untreated groundwater were compared with regulatory and nonregulatory health-based thresholds established by the U.S. Environmental Protection Agency (USEPA) and California Department of Public Health (CDPH), and to nonregulatory thresholds established for aesthetic and technical concerns by CDPH. Comparisons between data collected for this study and thresholds for drinking water are for illustrative purposes only, and are not indicative of compliance or noncompliance with those thresholds. Most inorganic constituents that were detected in groundwater samples from the 35 grid wells in the SCI study unit were found at concentrations below drinking-water thresholds; additionally, all detections of organic constituents in SCI grid well samples were below health-based thresholds.

California↗

USGS1985

Retention behavior of long chain quaternary ammonium homologues and related nitroso-alkymethylamines

Several chromatographic methods have been utilized to study the retentionbehavior of a homologous series of n -alkylbenzyldimethylammonium chlorides (ABDAC) and the corresponding nitroso- n -alkylmethylamines (NAMA). Linear correlation of the logarithmic capacity factor ( k ') with the number of carbons in the alkyl chain provides useful information on both gas chromatographic (GC) and high-performance liquid chromatographich (HPLC) retention parameters of unknown components. Under all conditions empolyed, GC methodology has proved effective in achieving complete resolution of the homologous mixture of NMA despite its obvious inadequacy in the separation of E-Z configurational isomers. Conversely, normal-phase HPLC on silica demonstrates that the selectivity (a) value for an E-Z pair is much higher than that for an adjacent homologous pair. In the reversed-phase HPLC study, three different silica-based column systems were examined under various mobile phase conditions. The extent of variation in k ' was found to be a function of the organic modifier, counter-ion concentration, eluent pH, nature of counter-ion, and the polarity and type of stationary phase. The k '—[NaClO 4 ] profiles showed similar trends between the ABDAC and the NAMA series, supporting the dipolar electronic structures of the latter compounds. Mobile phase and stationary phase effects on component separation are described. The methodology presented establishes the utility of HPLC separation techniques as versatile analytical tools for practical application.

Journal of Chromatography↗

USGS2010

Comparison of XAD with other dissolved lignin isolation techniques and a compilation of analytical improvements for the analysis of lignin in aquatic settings

This manuscript highlights numerous incremental improvements in dissolved lignin measurements over the nearly three decades since CuO oxidation of lignin phenols was first adapted for environmental samples. Intercomparison of the recovery efficiency of three common lignin phenol concentration and isolation techniques, namely XAD, C 18 with both CH 3 OH (C 18 M) and CH 3 CN (C 18 A) used independently for priming and elution steps, and tangential flow filtration (TFF) for a range of aquatic samples including fresh, estuarine and marine waters, was undertaken. With freshwater samples XAD8-1, C 18 M and TFF were all observed to recover ca. 80–90% of the lignin phenols and showed no fractionation effects with respect to diagnostic lignin parameters. With estuarine and marine samples more lignin phenols were recovered with C 18 M and XAD8-1 than TFF because of the increased prevalence of low molecular weight lignin phenols in marine influenced samples. For marine systems, differences were also observed between diagnostic lignin parameters isolated via TFF vs. C 18 M and XAD8-1 as a result of the high molecular weight lignin phenols being less degraded than the bulk. Therefore, it is recommended for future studies of marine systems that only one technique is utilized for ease of intercomparison within studies. It is suggested that for studies solely aimed at recovering bulk dissolved lignin in marine environments that C 18 M and XAD8-1 appear to be more suitable than TFF as they recover more lignin. Our results highlight that, for freshwater samples, all three common lignin phenol concentration and isolation techniques are comparable to whole water concentrated by rotary evaporation (i.e. not isolated) but, that for marine systems, the choice of concentration and isolation techniques needs to be taken into consideration with respect to both lignin concentration and diagnostic parameters. Finally, as the study highlights XAD8-1 to be a suitable method for the isolation of dissolved lignin phenols from aquatic systems (statistically indistinguishable from C 18 M, P < 0.1), lignin data representative of whole waters can be produced for IHSS reference materials or other XAD sample archives.

Organic Geochemistry↗

USGS2013

Spatially explicit models for inference about density in unmarked or partially marked populations

Recently developed spatial capture–recapture (SCR) models represent a major advance over traditional capture–recapture (CR) models because they yield explicit estimates of animal density instead of population size within an unknown area. Furthermore, unlike nonspatial CR methods, SCR models account for heterogeneity in capture probability arising from the juxtaposition of animal activity centers and sample locations. Although the utility of SCR methods is gaining recognition, the requirement that all individuals can be uniquely identified excludes their use in many contexts. In this paper, we develop models for situations in which individual recognition is not possible, thereby allowing SCR concepts to be applied in studies of unmarked or partially marked populations. The data required for our model are spatially referenced counts made on one or more sample occasions at a collection of closely spaced sample units such that individuals can be encountered at multiple locations. Our approach includes a spatial point process for the animal activity centers and uses the spatial correlation in counts as information about the number and location of the activity centers. Camera-traps, hair snares, track plates, sound recordings, and even point counts can yield spatially correlated count data, and thus our model is widely applicable. A simulation study demonstrated that while the posterior mean exhibits frequentist bias on the order of 5–10% in small samples, the posterior mode is an accurate point estimator as long as adequate spatial correlation is present. Marking a subset of the population substantially increases posterior precision and is recommended whenever possible. We applied our model to avian point count data collected on an unmarked population of the northern parula (Parula americana) and obtained a density estimate (posterior mode) of 0.38 (95% CI: 0.19–1.64) birds/ha. Our paper challenges sampling and analytical conventions in ecology by demonstrating that neither spatial independence nor individual recognition is needed to estimate population density—rather, spatial dependence can be informative about individual distribution and density.

Annals of Applied Statistics↗

USGS2009

Groundwater quality data in the Mojave study unit, 2008: Results from the California GAMA Program

Groundwater quality in the approximately 1,500 square-mile Mojave (MOJO) study unit was investigated from February to April 2008, as part of the Priority Basin Project of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA Priority Basin Project was developed in response to the Groundwater Quality Monitoring Act of 2001 and is being conducted by the U.S. Geological Survey (USGS) in cooperation with the California State Water Resources Control Board (SWRCB). MOJO was the 23rd of 37 study units to be sampled as part of the GAMA Priority Basin Project. The MOJO study was designed to provide a spatially unbiased assessment of the quality of untreated ground water used for public water supplies within MOJO, and to facilitate statistically consistent comparisons of groundwater quality throughout California. Samples were collected from 59 wells in San Bernardino and Los Angeles Counties. Fifty-two of the wells were selected using a spatially distributed, randomized grid-based method to provide statistical representation of the study area (grid wells), and seven were selected to aid in evaluation of specific water-quality issues (understanding wells). The groundwater samples were analyzed for a large number of organic constituents [volatile organic compounds (VOCs), pesticides and pesticide degradates, and pharmaceutical compounds], constituents of special interest (perchlorate and N-nitrosodimethylamine [NDMA]) naturally occurring inorganic constituents (nutrients, dissolved organic carbon [DOC], major and minor ions, silica, total dissolved solids [TDS], and trace elements), and radioactive constituents (gross alpha and gross beta radioactivity, radium isotopes, and radon-222). Naturally occurring isotopes (stable isotopes of hydrogen, oxygen, and carbon, stable isotopes of nitrogen and oxygen in nitrate, and activities of tritium and carbon-14), and dissolved noble gases also were measured to help identify the sources and ages of the sampled ground water. In total, over 230 constituents and water-quality indicators (field parameters) were investigated. Three types of quality-control samples (blanks, replicates, and matrix spikes) each were collected at approximately 5–8 percent of the wells, and the results for these samples were used to evaluate the quality of the data for the groundwater samples. Field blanks rarely contained detectable concentrations of any constituent, suggesting that contamination was not a significant source of bias in the data for the groundwater samples. Differences between replicate samples generally were within acceptable ranges, indicating acceptable analytical reproducibility. Matrix spike recoveries were within acceptable ranges for most compounds. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, untreated groundwater typically is treated, disinfected, or blended with other waters to maintain water quality. Regulatory thresholds apply to water that is served to the consumer, not to untreated ground water. However, to provide some context for the results, concentrations of constituents measured in the untreated ground water were compared with regulatory and non-regulatory health-based thresholds established by the U.S. Environmental Protection Agency (USEPA) and California Department of Public Health (CDPH) and thresholds established for aesthetic and technical concerns by CDPH. Comparisons between data collected for this study and thresholds for drinking-water are for illustrative purposes only, and are not indicative of compliance or non-compliance with those thresholds. Most constituents that were detected in groundwater samples in the 59 wells in MOJO were found at concentrations below drinking-water thresholds. In MOJO’s 52 grid wells, volatile organic compounds (VOCs) were detected in 40 percent of the wells, and pesticides and pesticide degradates were detected in 23 percent of the grid wells. Results for health-based thresholds in MOJO grid wells showed that all of the detections of organic compounds in samples from MOJO grid wells were below health-based thresholds, with the exception of a single detection of NDMA above the California Department of Public Health notification level (NL-CA). Trace elements and radioactive constituents were sampled for at 19 MOJO grid wells and most detections were below health-based thresholds. Exceptions include: six detections of arsenic above the USEPA maximum contaminant level (MCL-US), two detections of boron and one detection of vanadium above the NL-CA, one detection each of molybdenum and strontium that were above the USEPA lifetime health advisory level (HAL-US), and one detection of fluoride just above the MCL-CA of 2 µg/L. Most detections of radioactive constituents in the MOJO grid wells were below health-based thresholds, with the exception of one detection of gross alpha radioactivity (72-hour count and 30-day count) above the MCL-CA, and 17 grid wells (of 19 sampled) that had activities of radon-222 above the proposed MCL-US of 300 pCi/L, but all were below the proposed alternative MCL-US of 4,000 pCi/L. All of the samples collected from the 19 MOJO grid wells for trace elements, and most of the samples for major ions and total dissolved solids (TDS), had measured concentrations below the non-enforceable thresholds set for aesthetic concerns. Four grid wells had TDS concentrations above the California Department of Public Health secondary maximum contaminant level (SMCL-CA) recommended threshold of 500 mg/L, and three of these wells were also above the SMCL-CA upper threshold of 1,000 mg/L. Four grid wells (of 19 sampled) had sulfate measured at concentrations above the recommended SMCL-CA threshold of 250 mg/L, and one of these detections was also above the upper SMCL-CA threshold of 500 mg/L. One grid well had chloride levels at a concentration above the upper SMCL-CA threshold of 500 mg/L. Eleven grid wells (of 52 sampled) had pH values outside of the SMCL-US range for pH.

California↗

USGS2008

Inverse modeling of surface-water discharge to achieve restoration salinity performance measures in Florida Bay, Florida

The use of numerical modeling to evaluate regional water-management practices involves the simulation of various alternative water-delivery scenarios, which typically are designed intuitively rather than analytically. These scenario simulations are used to analyze how specific water-management practices affect factors such as water levels, flows, and salinities. In lieu of testing a variety of scenario simulations in a trial-and-error manner, an optimization technique may be used to more precisely and directly define good water-management alternatives. A numerical model application in the coastal regions of Florida Bay and Everglades National Park (ENP), representing the surface- and ground-water hydrology for the region, is a good example of a tool used to evaluate restoration scenarios. The Southern Inland and Coastal System (SICS) model simulates this area with a two-dimensional hydrodynamic surface-water model and a three-dimensional ground-water model, linked to represent the interaction of the two systems with salinity transport. This coastal wetland environment is of great interest in restoration efforts, and the SICS model is used to analyze the effects of alternative water-management scenarios. The SICS model is run within an inverse modeling program called UCODE. In this application, UCODE adjusts the regulated inflows to ENP while SICS is run iteratively. UCODE creates parameters that define inflow within an allowable range for the SICS model based on SICS model output statistics, with the objective of matching user-defined target salinities that meet ecosystem restoration criteria. Preliminary results obtained using two different parameterization methods illustrate the ability of the model to achieve the goals of adjusting the range and reducing the variance of salinity values in the target area. The salinity variance in the primary zone of interest was reduced from an original value of 0.509 psu2 to values 0.418 psu2 and 0.342 psu2 using different methods. Simulations with one, two, and three target areas indicate that optimization is limited near model boundaries and the target location nearest the tidal boundary may not be improved. These experiments indicate that this method can be useful for designing water-delivery schemes to achieve certain water-quality objectives. Additionally, this approach avoids much of the intuitive type of experimentation with different flow schemes that has often been used to develop restoration scenarios. ?? 2007 Elsevier B.V. All rights reserved.

Journal of Hydrology↗

USGS2009

Ground-Water Quality Data in the Santa Clara River Valley Study Unit, 2007: Results from the California GAMA Program

Ground-water quality in the approximately 460-square-mile Santa Clara River Valley study unit (SCRV) was investigated from April to June 2007 as part of the statewide Priority Basin project of the Ground-Water Ambient Monitoring and Assessment (GAMA) Program. The GAMA Priority Basin project was developed in response to the Groundwater Quality Monitoring Act of 2001 and is being conducted by the U.S. Geological Survey (USGS) in cooperation with the California State Water Resources Control Board (SWRCB). The study was designed to provide a spatially unbiased assessment of the quality of raw ground water used for public water supplies within SCRV, and to facilitate a statistically consistent basis for comparing water quality throughout California. Fifty-seven ground-water samples were collected from 53 wells in Ventura and Los Angeles Counties. Forty-two wells were selected using a randomized grid-based method to provide statistical representation of the study area (grid wells). Eleven wells (understanding wells) were selected to further evaluate water chemistry in particular parts of the study area, and four depth-dependent ground-water samples were collected from one of the eleven understanding wells to help understand the relation between water chemistry and depth. The ground-water samples were analyzed for a large number of synthetic organic constituents (volatile organic compounds [VOC], pesticides and pesticide degradates, potential wastewater-indicator compounds, and pharmaceutical compounds), a constituent of special interest (perchlorate), naturally occurring inorganic constituents (nutrients, major and minor ions, and trace elements), radioactive constituents, and microbial constituents. Naturally occurring isotopes (tritium, carbon-13, carbon-14 [abundance], stable isotopes of hydrogen and oxygen in water, stable isotopes of nitrogen and oxygen in nitrate, chlorine-37, and bromine-81), and dissolved noble gases also were measured to help identify the source and age of the sampled ground water. Quality-control samples (blanks or replicates, or samples for matrix spikes) were collected from approximately 26 percent of the wells, and the analyses of these samples were used to evaluate the quality of the data for the ground-water samples. Assessment of the quality-control results showed that the quality of the environmental data was good, with low bias and low variability, and as a result, less than 0.1 percent of the analytes detected in ground-water samples were censored. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, water typically is treated, disinfected, and (or) blended with other waters to maintain acceptable water quality. Regulatory thresholds apply to treated water that is delivered (or, supplied) to the consumer, not to raw ground water. However, to provide some context for the results, concentrations of constituents measured in the raw ground water were compared with regulatory and non-regulatory thresholds established by the U.S. Environmental Protection Agency (USEPA) and the California Department of Public Health (CDPH) and thresholds established for aesthetic concerns (secondary maximum contaminant levels, SMCL-CA) by CDPH. Most constituents that were detected in ground-water samples were reported at concentrations below their established health-based thresholds. VOCs, pesticides and pesticide degradates, and potential wastewater-indicator compounds were detected in about 33 percent or less of the 42 SCRV grid wells. Concentrations of all detected organic constituents were below established health-based thresholds. Perchlorate was detected in approximately 12 percent of the SCRV grid wells; all concentrations reported were below the NL-CA threshold. Additional constituents, including major ions, trace elements, and nutrients were collected at 26 wells (16 grid wells and 10 understanding wells) of the 53 wells sampled f

Data Series↗

USGS2012

Groundwater-quality data in the Borrego Valley, Central Desert, and Low-Use Basins of the Mojave and Sonoran Deserts study unit, 2008-2010--Results from the California GAMA Program

Groundwater quality in the 12,103-square-mile Borrego Valley, Central Desert, and Low-Use Basins of the Mojave and Sonoran Deserts (CLUB) study unit was investigated by the U.S. Geological Survey (USGS) from December 2008 to March 2010, as part of the California State Water Resources Control Board (SWRCB) Groundwater Ambient Monitoring and Assessment (GAMA) Program's Priority Basin Project (PBP). The GAMA-PBP was developed in response to the California Groundwater Quality Monitoring Act of 2001 and is being conducted in collaboration with the SWRCB and Lawrence Livermore National Laboratory (LLNL). The CLUB study unit was the twenty-eighth study unit to be sampled as part of the GAMA-PBP. The GAMA CLUB study was designed to provide a spatially unbiased assessment of untreated-groundwater quality in the primary aquifer systems, and to facilitate statistically consistent comparisons of untreated-groundwater quality throughout California. The primary aquifer systems (hereinafter referred to as primary aquifers) are defined as parts of aquifers corresponding to the perforation intervals of wells listed in the California Department of Public Health (CDPH) database for the CLUB study unit. The quality of groundwater in shallow or deep water-bearing zones may differ from the quality of groundwater in the primary aquifers; shallow groundwater may be more vulnerable to surficial contamination. In the CLUB study unit, groundwater samples were collected from 52 wells in 3 study areas (Borrego Valley, Central Desert, and Low-Use Basins of the Mojave and Sonoran Deserts) in San Bernardino, Riverside, Kern, San Diego, and Imperial Counties. Forty-nine of the wells were selected by using a spatially distributed, randomized grid-based method to provide statistical representation of the study unit (grid wells), and three wells were selected to aid in evaluation of water-quality issues (understanding wells). The groundwater samples were analyzed for organic constituents (volatile organic compounds [VOCs], pesticides and pesticide degradates, and pharmaceutical compounds), constituents of special interest (perchlorate and N -nitrosodimethylamine [NDMA]), naturally-occurring inorganic constituents (trace elements, nutrients, major and minor ions, silica, total dissolved solids [TDS], alkalinity, and species of inorganic chromium), and radioactive constituents (radon-222, radium isotopes, and gross alpha and gross beta radioactivity). Naturally-occurring isotopes (stable isotopes of hydrogen, oxygen, boron, and strontium in water, stable isotopes of carbon in dissolved inorganic carbon, activities of tritium, and carbon-14 abundance) and dissolved noble gases also were measured to help identify the sources and ages of sampled groundwater. In total, 223 constituents and 12 water-quality indicators were investigated. Three types of quality-control samples (blanks, replicates, and matrix spikes) were collected at up to 10 percent of the wells in the CLUB study unit, and the results for these samples were used to evaluate the quality of the data for the groundwater samples. Field blanks rarely contained detectable concentrations of any constituent, suggesting that contamination from sample collection procedures was not a significant source of bias in the data for the groundwater samples. Replicate samples generally were within the limits of acceptable analytical reproducibility. Median matrix-spike recoveries were within the acceptable range (70 to 130 percent) for approximately 85 percent of the compounds. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, untreated groundwater typically is treated, disinfected, and (or) blended with other waters to maintain water quality. Regulatory benchmarks apply to water that is delivered to the consumer, not to untreated groundwater. However, to provide some context for the results, concentrations of constituents measured in the untreated groundwater were compared with regulatory and non-regulatory health-based benchmarks established by the U.S. Environmental Protection Agency (USEPA) and CDPH, and to non-regulatory benchmarks established for aesthetic concerns by CDPH. Comparisons between data collected for this study and benchmarks for drinking water are for illustrative purposes only and are not indicative of compliance or non-compliance with those benchmarks. Most inorganic constituents detected in groundwater samples from the 49 grid wells were detected at concentrations less than drinking-water benchmarks. In addition, all detections of organic constituents from the CLUB study-unit grid-well samples were less than health-based benchmarks. In total, VOCs were detected in 17 of the 49 grid wells sampled (approximately 35 percent), pesticides and pesticide degradates were detected in 5 of the 47 grid wells sampled (approximately 11 percent), and perchlorate was detected in 41 of 49 grid wells sampled (approximately 84 percent). Trace elements, major and minor ions, and nutrients were sampled for at 39 grid wells, and radioactive constituents were sampled for at 23 grid wells; most detected concentrations were less than health-based benchmarks. Exceptions in the grid-well samples include seven detections of arsenic greater than the USEPA maximum contaminant level (MCL-US) of 10 micrograms per liter (μg/L); four detections of boron greater than the CDPH notification level (NL-CA) of 1,000 μg/L; six detections of molybdenum greater than the USEPA lifetime health advisory level (HAL-US) of 40 μg/L; two detections of uranium greater than the MCL-US of 30 μg/L; nine detections of fluoride greater than the CDPH maximum contaminant level (MCL-CA) of 2 milligrams per liter (mg/L); one detection of nitrite plus nitrate (NO 2- +NO 3- ), as nitrogen, greater than the MCL-US of 10 mg/L; and four detections of gross alpha radioactivity (72-hour count), and one detection of gross alpha radioactivity (30-day count), greater than the MCL-US of 15 picocuries per liter. Results for constituents with non-regulatory benchmarks set for aesthetic concerns showed that a manganese concentration greater than the CDPH secondary maximum contaminant level (SMCL-CA) of 50 μg/L was detected in one grid well. Chloride concentrations greater than the recommended SMCL-CA benchmark of 250 mg/L were detected in three grid wells, and one of these wells also had a concentration that was greater than the upper SMCL-CA benchmark of 500 mg/L. Sulfate concentrations greater than the recommended SMCL-CA benchmark of 250 mg/L were measured in six grid wells. TDS concentrations greater than the SMCL-CA recommended benchmark of 500 mg/L were measured in 20 grid wells, and concentrations in 2 of these wells also were greater than the SMCL-CA upper benchmark of 1,000 mg/L.

California↗

USGS2008

Field determination of the three-dimensional hydraulic conductivity tensor of anisotropic media: 2. Methodology and application to fractured rocks

The analytical solutions developed in the first paper can be used to interpret the results of cross-hole tests conducted in anisotropic porous or fractured media. In the particular case where the injection and monitoring intervals are short relative to the distance between them, the test results can be analyzed graphically. From the transient variation of hydraulic head in a given monitoring interval, one can determine the directional hydraulic diffusivity, K d ( e )/ S s , and the quantity D / S s , by curve matching. (Here K d ( e ) is directional hydraulic conductivity parallel to the unit vector, e , pointing from the injection to the monitoring interval, S s is specific storage, and D is the determinant of the hydraulic conductivity tensor, K .) The principal values and directions of K , together with S s , can then be evaluated by fitting an ellipsoid to the square roots of the directional diffusivities. Ideally, six directional measurements are required. In practice, a larger number of measurements is often necessary to enable fitting an ellipsoid to the data by least squares. If the computed [ K d ( e )/ s s ] ½ values fluctuate so severely that a meaningful least squares fit is not possible, one has a direct indication that the subsurface does not behave as a uniform anisotropic medium on the scale of the test. Test results from a granitic rock near Oracle in southern Arizona are presented to illustrate how the method works for fractured rocks. At the site, the Oracle granite is shown to respond as a near-uniform, anisotropic medium, the hydraulic conductivity of which is strongly controlled by the orientations of major fracture sets. The cross-hole test results are shown to be consistent with the results of more than 100 single-hole packer tests conducted at the site.

Water Resources Research↗

USGS2013

Groundwater-quality data in the Santa Barbara study unit, 2011: Results from the California GAMA Program

Groundwater quality in the 48-square-mile Santa Barbara study unit was investigated by the U.S. Geological Survey (USGS) from January to February 2011, as part of the California State Water Resources Control Board (SWRCB) Groundwater Ambient Monitoring and Assessment (GAMA) Program’s Priority Basin Project (PBP). The GAMA-PBP was developed in response to the California Groundwater Quality Monitoring Act of 2001 and is being conducted in collaboration with the SWRCB and Lawrence Livermore National Laboratory (LLNL). The Santa Barbara study unit was the thirty-fourth study unit to be sampled as part of the GAMA-PBP. The GAMA Santa Barbara study was designed to provide a spatially unbiased assessment of untreated-groundwater quality in the primary aquifer system, and to facilitate statistically consistent comparisons of untreated-groundwater quality throughout California. The primary aquifer system is defined as those parts of the aquifers corresponding to the perforation intervals of wells listed in the California Department of Public Health (CDPH) database for the Santa Barbara study unit. Groundwater quality in the primary aquifer system may differ from the quality in the shallower or deeper water-bearing zones; shallow groundwater may be more vulnerable to surficial contamination. In the Santa Barbara study unit located in Santa Barbara and Ventura Counties, groundwater samples were collected from 24 wells. Eighteen of the wells were selected by using a spatially distributed, randomized grid-based method to provide statistical representation of the study unit (grid wells), and six wells were selected to aid in evaluation of water-quality issues (understanding wells). The groundwater samples were analyzed for organic constituents (volatile organic compounds [VOCs], pesticides and pesticide degradates, and pharmaceutical compounds); constituents of special interest (perchlorate and N-nitrosodimethylamine [NDMA]); naturally occurring inorganic constituents (trace elements, nutrients, major and minor ions, silica, total dissolved solids [TDS], alkalinity, and arsenic, chromium, and iron species); and radioactive constituents (radon-222 and gross alpha and gross beta radioactivity). Naturally occurring isotopes (stable isotopes of hydrogen and oxygen in water, stables isotopes of inorganic carbon and boron dissolved in water, isotope ratios of dissolved strontium, tritium activities, and carbon-14 abundances) and dissolved noble gases also were measured to help identify the sources and ages of the sampled groundwater. In total, 281 constituents and water-quality indicators were measured. Three types of quality-control samples (blanks, replicates, and matrix spikes) were collected at up to 12 percent of the wells in the Santa Barbara study unit, and the results for these samples were used to evaluate the quality of the data for the groundwater samples. Blanks rarely contained detectable concentrations of any constituent, suggesting that contamination from sample collection procedures was not a significant source of bias in the data for the groundwater samples. Replicate samples generally were within the limits of acceptable analytical reproducibility. Matrix-spike recoveries were within the acceptable range (70 to 130 percent) for approximately 82 percent of the compounds. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, untreated groundwater typically is treated, disinfected, and (or) blended with other waters to maintain water quality. Regulatory benchmarks apply to water that is served to the consumer, not to untreated groundwater. However, to provide some context for the results, concentrations of constituents measured in the untreated groundwater were compared with regulatory and non-regulatory health-based benchmarks established by the U.S. Environmental Protection Agency (USEPA) and CDPH and to non-regulatory benchmarks established for aesthetic concerns by CDPH. Comparisons between data collected for this study and benchmarks for drinking water are for illustrative purposes only and are not indicative of compliance or non-compliance with those benchmarks. All organic constituents and most inorganic constituents that were detected in groundwater samples from the 18 grid wells in the Santa Barbara study unit were detected at concentrations less than drinking-water benchmarks. Of the 220 organic and special-interest constituents sampled for at the 18 grid wells, 13 were detected in groundwater samples; concentrations of all detected constituents were less than regulatory and non-regulatory health-based benchmarks. In total, VOCs were detected in 61 percent of the 18 grid wells sampled, pesticides and pesticide degradates were detected in 11 percent, and perchlorate was detected in 67 percent. Polar pesticides and their degradates, pharmaceutical compounds, and NDMA were not detected in any of the grid wells sampled in the Santa Barbara study unit. Eighteen grid wells were sampled for trace elements, major and minor ions, nutrients, and radioactive constituents; most detected concentrations were less than health-based benchmarks. Exceptions are one detection of boron greater than the CDPH notification level (NL-CA) of 1,000 micrograms per liter (μg/L) and one detection of fluoride greater than the CDPH maximum contaminant level (MCL-CA) of 2 milligrams per liter (mg/L). Results for constituents with non-regulatory benchmarks set for aesthetic concerns from the grid wells showed that iron concentrations greater than the CDPH secondary maximum contaminant level (SMCL-CA) of 300 μg/L were detected in three grid wells. Manganese concentrations greater than the SMCL-CA of 50 μg/L were detected in seven grid wells. Chloride was detected at a concentration greater than the SMCL-CA recommended benchmark of 250 mg/L in four grid wells. Sulfate concentrations greater than the SMCL-CA recommended benchmark of 250 mg/L were measured in eight grid wells, and the concentration in one of these wells was also greater than the SMCL-CA upper benchmark of 500 mg/L. TDS concentrations greater than the SMCL-CA recommended benchmark of 500 mg/L were measured in 17 grid wells, and concentrations in six of these wells were also greater than the SMCL-CA upper benchmark of 1,000 mg/L.

California↗

USGS2020

Methylmercury exposure in wildlife: A review of the ecological and physiological processes affecting contaminant concentrations and their interpretation

Exposure to methylmercury (MeHg) can result in detrimental health effects in wildlife. With advances in ecological indicators and analytical techniques for measurement of MeHg in a variety of tissues, numerous processes have been identified that can influence MeHg concentrations in wildlife. This review presents a synthesis of theoretical principals and applied information for measuring MeHg exposure and interpreting MeHg concentrations in wildlife. Mercury concentrations in wildlife are the net result of ecological processes influencing dietary exposure combined with physiological processes that regulate assimilation, transformation, and elimination. Therefore, consideration of both physiological and ecological processes should be integrated when formulating biomonitoring strategies. Ecological indicators, particularly stable isotopes of carbon, nitrogen, and sulfur, compound-specific stable isotopes, and fatty acids, can be effective tools to evaluate dietary MeHg exposure. Animal species differ in their physiological capacity for MeHg elimination, and animal tissues can be inert or physiologically active, act as sites of storage, transformation, or excretion of MeHg, and vary in the timing of MeHg exposure they represent. Biological influences such as age, sex, maternal transfer, and growth or fasting are also relevant for interpretation of tissue MeHg concentrations. Wildlife tissues that represent current or near-term bioaccumulation and in which MeHg is the predominant mercury species (such as blood and eggs) are most effective for biomonitoring ecosystems and understanding landscape drivers of MeHg exposure. Further research is suggested to critically evaluate the use of keratinized external tissues to measure MeHg bioaccumulation, particularly for less-well studied wildlife such as reptiles and terrestrial mammals. Suggested methods are provided to effectively use wildlife for quantifying patterns and drivers of MeHg bioaccumulation over time and space, as well as for assessing the potential risk and toxicological effects of MeHg on wildlife.

Science of the Total Environment↗

USGS2020

Approaches to highly parameterized inversion: PEST++ Version 5, a software suite for parameter estimation, uncertainty analysis, management optimization and sensitivity analysis

PEST++ Version 5 extends and enhances the functionality of the PEST++ Version 3 software suite, providing environmental modeling practitioners access to updated Version 3 tools as well as new tools to support decision making with environmental models. Version 5 of PEST++ includes tools for global sensitivity analysis (PESTPP-SEN); least-squares parameter estimation with integrated first-order, second-moment parameter and forecast uncertainty estimation (PESTPP-GLM); an iterative, localized ensemble smoother (PESTPP-IES); and a tool for management optimization under uncertainty (PESTPP-OPT). Additionally, all PEST++ Version 5 tools have a built-in fault-tolerant, multithreaded parallel run manager and are model independent, using the same protocol as the widely used PEST software suite. PEST++ Version 5 is consistent with PEST++ Version 3 conventions and design philosophy. The software’s emphasis continues to target efficient and optimized algorithms that have proven beneficial in decision-support settings and can accommodate large, highly parameterized problems. Expanded and new capabilities are now available to express uncertainty using Monte Carlo and analytical uncertainty approaches and allow evaluation of thousands to millions of parameters. New management optimization capabilities in Version 5 also allow environmental models to be used to answer management questions using multiple societal constraints in a risk-based framework. The PEST++ Version 5 software suite can be compiled for Microsoft Windows® and Unix-based operating systems such as Apple and Linux®; the source code is available with a Microsoft Visual Studio® 2019 solution; and CMake support for all three operating system is also provided. PEST++ Version 5 continues to build a foundation for an open-source framework capable of producing model-independent, robust, and efficient decision-support tools for large environmental models. The functionality of each of the PEST++ tools are demonstrated on a simple example problem. Implications of decisions used when using the PEST++ suite tools are also discussed.

Techniques and Methods↗

USGS2002

Field determination of microgram quantities of niobium in rocks

A rapid, simple, and moderately accurate method was needed for the determination of traces of niobium in rocks. The method developed is based on the reaction of niobium(V) with thiocyanate ion in a 4 M hydrochloric acid and 0.5 M tartaric acid medium, after which the complex is extracted with ethyl ether. The proposed procedure is applicable to rocks containing from 50 to 2000 p.p.m. of niobium, and, with modifications, can be used on rocks containing larger amounts. Five determinations on two rocks containing 100 p.p.m. or less of niobium agree within 5 p.p.m. of the mean, and the confidence limits at the 95% level are, respectively, ± 6 and ± 4 p.p.m. The addition of acetone to the ether extract of the niobium thiocyanate inhibits the polymerization of the thiocyanate ion and stabilizes the solution for at least 20 hours. The proposed procedure permits the determination of 20 γ of niobium in the presence of 1000 γ of iron, titanium, or uranium; 500 γ of vanadium; or 100 γ of tungsten or molybdenum or both.

Analytical Chemistry↗