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Assessment of Energetic Compounds, Semi-volatile Organic Compounds, and Trace Elements in Streambed Sediment and Stream Water from Streams Draining Munitions Firing Points and Impact Areas, Fort Riley, Kansas, 2007-08

An assessment of energetic compounds (explosive and propellant residues) and associated semi-volatile organic compounds (SVOCs) and trace elements in streambed sediment and stream water from streams draining munitions firing points and impact areas at Fort Riley, northeast Kansas, was performed during 2007-08 by the U.S. Geological Survey (USGS) in cooperation with the U.S. Army. Streambed sediment from 16 sampling sites and stream-water samples from 5 sites were collected at or near Fort Riley and analyzed for as many as 17 energetic compounds, 65 SVOCs, and 27 trace elements. None of the energetic compounds or SVOCs were detected in streambed sediment collected from sites within the Fort Riley Military Reservation. This may indicate that these compounds either are not transported from dispersal areas or that analytical methods are not sensitive enough to detect the small concentrations that may be transported. Concentrations of munitions-associated trace elements did not exceed sediment-quality guidelines recommended by the U.S. Environmental Protection Agency (USEPA) and are not indicative of contamination of streambed sediment at selected streambed sampling sites, at least in regards to movement from dispersal areas. Analytical results of stream-water samples provided little evidence of contamination by energetic compounds, SVOCs, or associated trace elements. Perchlorate was detected in 19 of 20 stream-water samples at concentrations ranging from an estimated 0.057 to an estimated 0.236 ug/L (micrograms per liter) with a median concentration of an estimated 0.114 ug/L, substantially less than the USEPA Interim Health Advisory criterion (15 ug/L), and is in the range of documented background concentrations. Because of these small concentrations and possible natural sources (precipitation and groundwater), it is likely that the occurrence of perchlorate in stream water is naturally occurring, although a definitive identification of the source of perchlorate in stream water at Fort Riley is difficult. The only SVOCs detected in stream-water samples were bis(2-ethylhexyl) phthalate and di-n-butyl phthalate but at concentrations substantially less than the most stringent aquatic-life criteria established by the Kansas Department of Health and Environment. All trace element concentrations in stream-water samples were less than the most stringent aquatic-life criteria. The implication of these stream-water results is that contamination arising from firing-range activities, if it exists, is so small as to be nondetectable with current analytical methods or is not distinguishable from background concentrations for constituents that also are naturally occurring. Overall, the munitions-related constituents analyzed in streambed sediment and stream water, when detected, were at concentrations that were less than regulatory criteria

Scientific Investigations Report↗

U.S. Geological Survey laboratory method for methyl tert-butyl ether and other fuel oxygenates

Methyl tert-butyl ether (MTBE) was found in shallow ground-water samples in a study of 8 urban and 20 agricultural areas throughout the United States in 1993 and 1994 (Squillace and others, 1995, p. 1). The compound is added to gasoline either seasonally or year round in many parts of the United States to increase the octane level and to reduce carbon monoxide and ozone levels in the air. The U.S. Geological Survey (USGS) National Water Quality Laboratory (NWQL), near Denver, uses state-of-the-art technology to analyze samples for MTBE as part of the USGS water-quality studies. In addition, the NWQL offers custom analyses to determine two other fuel oxygenates--ethyl tert-butyl ether (ETBE) and tert-amyl methyl ether (TAME). The NWQL was not able to obtain a reference standard for tert-amyl ethyl ether (TAEE), another possible fuel oxygenate (Shelley and Fouhy, 1994, p. 63). The shallow ground-water samples were collected as part of the USGS National Water-Quality Assessment Program. These samples were collected from 211 urban wells or springs and 562 agricultural wells sampled by the USGS in 1993 and 1994. The wells were keyed to specific land-use areas to assess the effects of different uses on ground-water quality (Squillace and others, 1995, p. 2). Ground-water samples were preserved on site to pH less than or equal to 2 with a solution of 1:1 hydrochloric acid. All samples were analyzed at the NWQL within 2 weeks after collection. The purpose of this fact sheet is to explain briefly the analytical method implemented by the USGS for determining MTBE and other fuel oxygenates. The scope is necessarily limited to an overview of the analytical method (instrumentation, sample preparation, calibration and quantitation, identification, and preservation of samples) and method performance (reagent blanks, accuracy, and precision).

Fact Sheet↗

Water- and air-quality monitoring of Sweetwater Reservoir watershed, San Diego County, California — Phase one results continued, 2001-2003

In 1998, the U.S. Geological Survey, in cooperation with the Sweetwater Authority, began a study to monitor water, air, and sediment at the Sweetwater and Loveland Reservoirs in San Diego County, California. The study includes regular sampling of water and air at Sweetwater Reservoir for chemical constituents, including volatile organic compounds (VOC), polynuclear aromatic hydrocarbons (PAH), pesticides, and major and trace elements. The purpose of this study is to monitor changes in contaminant composition and concentration during the construction and operation of State Route 125. To accomplish this, the study was divided into two phases. Phase One sampling (water years 1998–2004) determined baseline conditions for the detection frequency and the concentrations of target compounds in air and water. Phase Two sampling (starting water year 2005) continues at selected monitoring sites during and after construction of State Route 125 to assess the chemical impact this roadway alignment may have on water quality in the reservoir. Water samples were collected for VOCs and pesticides at Loveland Reservoir during Phase One and will be collected during Phase Two for comparison purposes. Air samples collected to monitor changes in VOCs, PAHs, and pesticides were analyzed by adapting methods used to analyze water samples. Bed-sediment samples have been and will be collected three times during the study; at the beginning of Phase One, at the start of Phase Two, and near the end of the study. In addition to the ongoing data collection, several special studies were initiated to assess the occurrence of specific chemicals of concern, such as trace metals, anthropogenic indicator compounds, and pharmaceuticals. This report describes the study design, and the sampling and analytical methods, and presents data from water and air samples collected during the fourth and fifth years of Phase One of the study (October 2001 to September 2003). Data collected during the first three years has been previously published. Three types of quality-control samples were used in this study: blanks, spikes, and replicates. Blanks and spikes are used to estimate result bias, and replicates are used to estimate result variability. Additionally, surrogate compounds were added at the laboratory to samples of VOCs, PAHs, pesticides, anthropogenic indicator compounds, and pharmaceuticals to monitor sample-specific performance of the analytical method.

California↗

Volatile organic compound matrix spike recoveries for ground- and surface-water samples, 1997-2001

The U.S. Geological Survey's National Water-Quality Assessment (NAWQA) Program used field matrix spikes (FMSs), field matrix spike replicates (FMSRs), laboratory matrix spikes (LMSs), and laboratory reagent spikes (LRSs), in part, to assess the quality of volatile organic compound (VOC) data from water samples collected and analyzed in more than 50 of the Nation's largest river basins and aquifers (Study Units). The data-quality objectives of the NAWQA Program include estimating the extent to which variability, degradation, and matrix effects, if any, may affect the interpretation of chemical analyses of ground- and surface-water samples. In order to help meet these objectives, a known mass of VOCs was added (spiked) to water samples collected in 25 Study Units. Data within this report include recoveries from 276 ground- and surface-water samples spiked with a 25-microliter syringe with a spike solution containing 85 VOCs to achieve a concentration of 0.5 microgram per liter. Combined recoveries for 85 VOCs from spiked ground- and surface-water samples and reagent water were used to broadly characterize the overall recovery of VOCs. Median recoveries for 149 FMSs, 107 FMSRs, 20 LMSs, and 152 LRSs were 79.9, 83.3, 113.1, and 103.5 percent, respectively. Spike recoveries for 85 VOCs also were calculated individually. With the exception of a few VOCs, the median percent recoveries determined from each spike type for individual VOCs followed the same pattern as for all VOC recoveries combined, that is, listed from least to greatest recovery-FMSs, FMSRs, LRSs, and LMSs. The median recoveries for individual VOCs ranged from 63.7 percent to 101.5 percent in FMSs; 63.1 percent to 101.4 percent in FMSRs; 101.7 percent to 135.0 percent in LMSs; and 91.0 percent to 118.7 percent in LRSs. Additionally, individual VOC recoveries were compared among paired spike types, and these recoveries were used to evaluate potential bias in the method. Variability associated with field spiking, field handling, transport, and analysis was assessed by comparing recoveries between 107 pairs of FMR and FMSR samples. For most VOCs, FMSR recoveries were greater than the paired FMS recoveries. This may result from routinely processing the FMS sample first, allowing a more fluid and efficient technique when processing the FMSR. Degradation was examined by comparing VOC recoveries between 20 pairs of FMS and LMS samples. For all VOCs, the LMS recoveries were greater than FMS recoveries. However, data presented in a previously published VOC stability study were interpreted, and recoveries indicated that VOC degradation should not affect the recovery for most VOCs monitored by the NAWQA Program. Matrix effects were examined by comparing VOC recoveries from 20 pairs of LMS and LRS samples. With the exception of two VOCs, individual recoveries were not significantly different between LMSs and LRSs, indicating that most VOC recoveries are not affected by matrix effects. Additionally, matrix effects should be negligible due to the analytical technique (purge and trap capillary column gas chromatography/mass spectrometry) used for VOC analysis at the U.S. Geological Survey National Water Quality Laboratory (NWQL). The reason for the lower VOC recoveries from FMSs and FMSRs than from LMSs and LRSs may be associated with differences in spiking technique and experience, and to varying environmental conditions at the time of spiking. However, for all spike types, 87 percent of the individual VOC recoveries were within the range of 60 to 140 percent, a range that is considered acceptable by the U.S. Environmental Protection Agency's established analytical method. Additionally, the median recovery for each spike type was within the range of 60 to 140 percent. The excellent VOC recoveries from LMSs and LRSs demonstrate that low VOC concentrations can routinely and accurately be measured by the analytical methods used by the NWQL.

Scientific Investigations Report↗

New-generation pesticides are prevalent in California's Central Coast streams

Pesticides are widely recognized as important biological stressors in streams, especially in heavily developed urban and agricultural areas like the Central California Coast region. We assessed occurrence and potential toxicity of pesticides in small streams in the region using two analytical methods: a broad-spectrum (223 compounds) method in use since 2012 and a newly developed method for 30 additional new-generation fungicides and insecticides. At least one pesticide compound was identified in 83 of the 85 streams sampled. About one-half (48%) of the 253 pesticides measured were detected at least once and 27 were detected in 10% or more of samples. Three of the top 4, and 6 of the top 10 most frequently detected compounds (chlorantraniliprole, dinotefuran, boscalid, thiamethoxam, clothianidin and the fluopicolide degradate 2,6-dichlorobenzamide) were analyzed by the new method. Pesticide mixtures were common, with two or more pesticide compounds detected in 81% of samples and 10 or more in 32% of samples. The pesticide count at a site was relatively consistent over the 6-week study. Four sites with mixed land-use in the lower basin (<5 km from the sampling site) tended to have the highest pesticide counts and the highest concentrations. Potential toxicity (assessed by comparison to benchmarks) to invertebrates was much more common than potential toxicity to fish or plants and was associated with a wide array of insecticides. The common occurrence of new-generation pesticides highlights the need to continuously update analytical methods to keep pace with changing pesticide use for a fuller assessment of pesticide occurrence and effects on the environment.

California↗

Water- and air-quality and surficial bed-sediment monitoring of the Sweetwater Reservoir watershed, San Diego County, California, 2003-09

In 1998, the U.S. Geological Survey, in cooperation with the Sweetwater Authority, began a study to assess the overall health of the Sweetwater watershed in San Diego County, California. This study was designed to provide a data set that could be used to evaluate potential effects from the construction and operation of State Route 125 within the broader context of the water quality and air quality in the watershed. The study included regular sampling of water, air, and surficial bed sediment at Sweetwater Reservoir (SWR) for chemical constituents, including volatile organic compounds (VOCs), base-neutral and acid- extractable organic compounds (BNAs) that include polycyclic aromatic hydrocarbons (PAHs), pesticides, and metals. Additionally, water samples were collected for anthropogenic organic indicator compounds in and around SWR. Background water samples were collected at Loveland Reservoir for VOCs, BNAs, pesticides, and metals. Surficial bed-sediment samples were collected for PAHs, organochlorine pesticides, and metals at Sweetwater and Loveland Reservoirs. To monitor changes in contaminant concentration in water and air at SWR during the construction and operation of State Route 125, this study was divided into three phases. Phase One sampling (September 1998 to September 2004) was designed to establish baseline conditions for target compounds in terms of detection frequency and concentration in air and water. Phase Two (October 2004 to September 2007) continued sampling at selected monitoring sites during construction of State Route 125 to assess any effect from the construction process and the use of heavy equipment to build the roadway. Phase Three (October 2007 to August 2009) continued sampling for 2 years after the opening of State Route 125 to assess the potential changes in water quality related to vehicle emissions from the roadway alignment. Surficial bed-sediment samples were collected three times during the study&mdash;at the beginning of the study, at the start of Phase Two, and at the end of the study. This report describes the study design and the sampling and analytical methods and presents data from water, air, and surficial bed-sediment samples collected from the sixth to eleventh years of the study (October 2003&ndash;August 2009), spanning the last year of Phase one and all of Phases Two and Three. Data collected during the first 5 years of sampling have been previously published. Three types of quality-control samples were used in this study&mdash;matrix spikes, blanks, and replicates. Matrix-spike data are considered to be adequate if the recovery concentration is within 30 percent of the matrix concentration. Replicate data are considered to be adequate if the replicate sample concentration is within 30 percent of the environmental sample concentration. Additionally, surrogate compounds were added to most samples to monitor sample-specific performance of the analytical method. Most VOC matrix-spike recovery data associated with water samples are within acceptable criteria, but three VOCs had recoveries below the acceptable criteria; these compounds may not have been detected in water samples if they were present at low concentrations. Data for blanks associated with water samples for VOCs and metals showed no detections above their laboratory reporting levels. Most replicate data are within acceptable criteria. Quality-control data for VOC air samples resulted in flagging several reported concentrations for acetone, benzene, ethenylbenzene, and naphthalene because they may be biased high. Acetone, benzene, and toluene were detected at low concentrations in almost every VOC air blank. Some PAH and pesticide concentrations in air samples were designated as estimated because of method performance limitations. PAHs in surficial bed sediment had 83 percent of surrogates below the acceptable criteria. No matrix-spike data for metals in surficial bed sediment were outside the acceptable criteria; only beryllium had a replicate comparison outside the acceptable criteria. Sampling results show concentrations of the gasoline oxygenate methyl tert -butyl ether in water and air samples declined after it was phased out by the State of California in January 2004. The largest concentrations of gasoline hydrocarbons benzene and toluene in water were detected at or near the surface of the SWR. Isophorone and phenol were the two most frequently detected BNA compounds in water. Diuron, prometon, and simazine were the most frequently detected pesticide compounds in water. Concentrations of benzene and toluene in air samples were highest during the cooler months and had a consistent seasonal pattern over time. Ten PAH compounds were detected frequently in air samples. Twelve pesticide compounds were also detected in air samples. Surficial bed-sediment samples were analyzed for 53 PAHs; 22 of the compounds had one or more detections. Surficial bed-sediment samples were analyzed for 22 organic compounds; only 6 compounds had one or more detections. Surficial bed-sediment samples were analyzed for 37 metals.

California↗

Selenium stable isotope ratios as indicators of sources and cycling of selenium: Results from the northern reach of San Francisco Bay

Selenium stable isotope ratios can serve as indicators of Se sources and reduction of Se oxyanions, much as sulfur and nitrogen isotope ratios do in sulfur and nitrogen biogeochemical studies. A new analytical method, which allows precise Se isotope ratio measurements on 500 ng of Se, greatly enhances analysis of environmental samples. This paper presents the first environmental study to use Se stable isotopes. 80Se/76Se ratios, relative to a provisional standard, were measured in water, oil refinery wastewater, total sediment digest, and sediment extracts from the Carquinez area in the San Francisco Bay Estuary, Se isotope ratios in total sediment Se and in extracts designed to recover Se0 are slightly (about 2???) enriched in the lighter isotope relative to local bay water Se. This difference is smaller than the isotopic fractionations expected upon reduction of Se(VI) or Se(IV) to Se(0) and suggests that reduction of soluble selenium from the overlying waters is not the dominant process by which Se is incorporated into the sediments. Consistent isotopic differences between riverine and refinery inputs were not observed, and thus tracing of refinery inputs with Se isotopes is not possible in this system.Selenium stable isotope ratios can serve as indicators of Se sources and reduction of Se oxyanions, much as sulfur and nitrogen isotope ratios do in sulfur and nitrogen biogeochemical studies. A new analytical method, which allows precise Se isotope ratio measurements on 500 ng of Se, greatly enhances analysis of environmental samples. This paper presents the first environmental study to use Se stable isotopes. 80Se/76Se ratios, relative to a provisional standard, were measured in water, oil refinery wastewater, total sediment digests, and sediment extracts from the Carquinez area in the San Francisco Bay Estuary. Se isotope ratios in total sediment Se and in extracts designed to recover Se0 are slightly (about 2 per mil) enriched in the lighter isotope relative to local bay water Se. This difference is smaller than the isotopic fractionations expected upon reduction of Se(VI) or Se(IV) to Se(0) and suggests that reduction of soluble selenium from the overlying waters is not the dominant process by which Se is incorporated into the sediments. Consistent isotopic differences between riverine and refinery inputs were not observed, and thus tracing of refinery inputs with Se isotopes is not possible in this system.

Environmental Science & Technology↗

Nutrient loadings to streams of the continental United States from municipal and industrial effluent?

Data from the United States Environmental Protection Agency Permit Compliance System national database were used to calculate annual total nitrogen (TN) and total phosphorus (TP) loads to surface waters from municipal and industrial facilities in six major regions of the United States for 1992, 1997, and 2002. Concentration and effluent flow data were examined for approximately 118,250 facilities in 45 states and the District of Columbia. Inconsistent and incomplete discharge locations, effluent flows, and effluent nutrient concentrations limited the use of these data for calculating nutrient loads. More concentrations were reported for major facilities, those discharging more than 1 million gallons per day, than for minor facilities, and more concentrations were reported for TP than for TN. Analytical methods to check and improve the quality of the Permit Compliance System data were used. Annual loads were calculated using "typical pollutant concentrations" to supplement missing concentrations based on the type and size of facilities. Annual nutrient loads for over 26,600 facilities were calculated for at least one of the three years. Sewage systems represented 74% of all TN loads and 58% of all TP loads. This work represents an initial set of data to develop a comprehensive and consistent national database of point-source nutrient loads. These loads can be used to inform a wide range of water-quality management, watershed modeling, and research efforts at multiple scales.

Journal of the American Water Resources Associatio↗

Methods for the determination of organic substances in water and fluvial sediments, USGS TWRI, Book 5, Laboratory analysis, Chapter A3

This manual contains analytical methods used by the U.S. Geological Survey for the determination of organic substances in water, water-suspended sediment mixtures, and bottom material. Some of the analytical procedures yield determinations for specific compounds, whereas others provide a measure of the quantity of groups of compounds present in the sample. Examples of the first category are procedures for the organochlorine and organophosphate insecticides, chlorophenoxy acid and triazine herbicides and specific substituted phenols. Examples of the second category are the various organic carbon analyses and the polychlorinated biphenyl methods. Each analytical method is presented in a standardized format which includes conditions for application of the method, a summary of the method, interferences, required apparatus and reagents, analytical procedures, calculations, reporting of results, and estimation of precision.

Open-File Report↗

Occurrence of organic wastewater compounds in selected surface-water supplies, Triangle area of North Carolina, 2002-2005

Selected organic wastewater compounds, such as household, industrial, and agricultural-use compounds, sterols, pharmaceuticals, and antibiotics, were measured at eight sites classified as drinking-water supplies in the Triangle Area of North Carolina. From October 2002 through July 2005, seven of the sites were sampled twice, and one site was sampled 28 times, for a total of 42 sets of environmental samples. Samples were analyzed for as many as 126 compounds using three laboratory analytical methods. These methods were developed by the U.S. Geological Survey to detect low levels (generally less than or equal to 1.0 microgram per liter) of the target compounds in filtered water. Because analyses were conducted on filtered samples, the results presented in this report may not reflect the total concentration of organic wastewater compounds in the waters that were sampled. Various quality-control samples were used to quality assure the results in terms of method performance and possible laboratory or field contamination. Of the 108 organic wastewater compounds that met method performance criteria, 24 were detected in at least one sample during the study. These 24 compounds included 3 pharmaceutical compounds, 6 fire retardants and plasticizers, 3 antibiotics, 3 pesticides, 6 fragrances and flavorants, 1 disinfectant, and 2 miscellaneous-use compounds, all of which likely originated from a variety of domestic, industrial, and agricultural sources. The 10 most frequently detected compounds included acetyl-hexamethyl tetrahydronaphthalene and hexahydro-hexamethyl cyclopentabenzopyran (synthetic musks that are widely used in personal-care products and are known endocrine disruptors); tri(2-chloroethyl) phosphate, tri(dichloroisopropyl) phosphate, and tributyl phosphate (fire retardants); metolachlor (herbicide); caffeine (nonprescription stimulant); cotinine (metabolite of nicotine); acetaminophen (nonprescription analgesic); and sulfamethoxazole (prescription antibiotic). The occurrence and distribution of organic wastewater compounds varied considerably among sampling sites, but at least one compound was detected at every location. The most organic wastewater compounds (19) were detected at the Neuse River above U.S. 70 at Smithfield, where two-thirds of the total number of samples were collected. The fewest organic wastewater compounds (1) were detected at the Eno River at Hillsborough. The detection of multiple organic wastewater compounds was common, with a median of 3.5 and as many as 12 compounds observed in individual samples. Some compounds, including acetaminophen, cotinine, tri(2-chloroethyl) phosphate, and metolachlor, were detected at numerous sites and in numerous samples, indicating that they are widely distributed in the environment. Other organic wastewater compounds, including acetyl-hexamethyl tetrahydronaphthalene and hexahydro-hexamethyl cyclopentabenzopyran, were detected in numerous samples but at only one location, indicating that sources of these compounds are more site specific. Results indicate that municipal wastewater may be a source of antibiotics and synthetic musks; however, the three sites in this study that are located downstream from wastewater discharges also receive runoff from agricultural, urban, and rural residential lands. Source identification was not an objective of this study. Concentrations of individual compounds generally were less than 0.5 microgram per liter. No concentrations exceeded Federal drinking-water standards or health advisories, nor water-quality criteria established by the State of North Carolina; however, such criteria are available for only a few of the compounds that were studied. Compared with other surface waters that have been sampled across the United States, the Triangle Area water-supply sites had fewer detections of organic wastewater compounds; however, differences in study design and analytical methods used among studies must be considered when mak

North Carolina↗

Statistical analysis of major ion and trace element geochemistry of water, 1986-2006, at seven wells transecting the freshwater/saline-water interface of the Edwards aquifer, San Antonio, Texas

This report by the U.S. Geological Survey, in cooperation with the San Antonio Water System, describes the results of a statistical analysis of major ion and trace element geochemistry of water at seven wells transecting the freshwater/saline-water interface of the Edwards aquifer in San Antonio, Texas, either over time or in response to variations in hydrologic conditions. The data used in this report were collected during 1986&ndash;2006. The seven monitoring wells are screened at different depths in the aquifer at three sites that form a generally north-to-south transect. The three wells of the southern site and the deeper of the two middle-site wells are open to the freshwater/saline-water transition zone, which contains saline water. The shallower well of the middle site and the two wells of the northern site are open to the freshwater zone. Mean specific conductance (SC) values were greater at transition-zone wells than at freshwater-zone wells, but SC did not vary systematically with depth. Concentrations of all major ions except bicarbonate were greater at transition-zone wells than at freshwater-zone wells, but concentrations tended to be more variable at freshwater-zone wells. Mean molar ratios of magnesium:calcium, sulfate:chloride, and sodium:chloride were similar at transition-zone wells and freshwater-zone wells. Concentrations of trace elements for many water samples at the seven transect wells were below the laboratory analytical reporting level. Detections of trace elements were more frequent at transition-zone wells, and mean concentrations of cadmium, chromium, copper, lead, and silver were elevated at transition-zone wells relative to freshwater-zone wells. All strong correlations between SC and major ions were positive, and in general there were more and stronger correlations between SC and major ions in the water from the freshwater-zone wells than from the transition-zone wells. Except for the shallowest transition-zone well, the transition-zone wells had relatively few strong correlations overall. The lack of a strong correlation indicates that much of the variability in the major ion concentrations at these wells might be a result of analytical variability caused by the multiple laboratory analytical methods used. In most cases, strong correlations between concentrations of trace elements were positive, and transition-zone wells and freshwater-zone wells had water with a similar number of significant correlations. Principal components analysis indicates dilution of ground water by low-ionic-strength meteoric water at the three freshwater-zone wells and at the shallowest transition-zone well. At the two deeper transition-zone wells at the southern site, principal components analysis indicates that there is no systematic variation in major ion concentrations. At three transition-zone wells, there was a general trend toward less salinity over the 21-year period of sampling. Trends in SC at the freshwater-zone wells were less consistent. There is no systematic change in the direction of trend in SC by water type (saline or fresh), between sites, or with depth. In general, trends in major ion concentrations corresponded to those in SC. For each trace element over the 21-year sampling period, there was either no trend or a downward trend. Relations between SC, major ions, and major ion molar ratios and hydrologic indicators (concurrent or prior time-averaged measures of water level and effective rainfall) were investigated. Correlations between geochemical variables and measures of water level in the freshwater-zone wells were much more frequent than correlations between geochemical variables and measures of water level in the transition-zone wells. There were correlations between SC and all measures of water level at the two freshwater-zone wells at the northern site, but there were no correlations between SC and any measures of water level at any transition-zone wells. SC was correlated with effective rainfall at all freshwater-zone wells and at one transition-zone well. The statistical analyses taken together indicate that the geochemistry at the freshwater-zone wells is more variable than that at the transition-zone wells. The geochemical variability at the freshwater-zone wells might result from dilution of ground water by meteoric water. This is indicated by relatively constant major ion molar ratios; a preponderance of positive correlations between SC, major ions, and trace elements; and a principal components analysis in which the major ions are strongly loaded on the first principal component. Much of the variability at three of the four transition-zone wells might result from the use of different laboratory analytical methods or reporting procedures during the period of sampling. This is reflected by a lack of correlation between SC and major ion concentrations at the transition-zone wells and by a principal components analysis in which the variability is fairly evenly distributed across several principal components. The statistical analyses further indicate that, although the transition-zone wells are less well connected to surficial hydrologic conditions than the freshwater-zone wells, there is some connection but the response time is longer.

Texas↗

Comparison of seven DNA metabarcoding sampling methods to assess diet in a large avian predator

DNA metabarcoding is a rapidly advancing tool for diet assessment in wildlife ecology. Studies have used a variety of field collection methods to evaluate diet; however, there is a pressing need to understand the differences among sampling methods and the downstream inferential consequences they may have on our ability to document diet accurately and efficiently. We evaluated seven DNA metabarcoding sampling methods to assess the diet of a large avian predator: Buteo lagopus (rough-legged hawk). We collected beak swabs, talon swabs, cheek (buccal) swabs, cloacal swabs, and cloacal loops from captured birds, and collected fecal samples from both captured and uncaptured birds. We described and compared variation in prey recovery within and among the seven sampling methods and identified appropriate analytical methods to compare diet among individuals sampled via different methods. Beak and talon swabs produced the highest prey detection rates, yielded the greatest prey richness per sample, and contributed the most to an individual's total prey richness per sampling occasion compared to other sampling methods. Within individuals sampled using five methods during a single capture occasion, cloacal swabs and cheek swabs positively predicted prey richness and average prey mass, respectively, from fecal samples. While all methods identified similar dominant prey taxa that were consistent with prior diet studies, beak and talon swabs detected greater prey richness at both the individual and population levels. We propose a food residue duration hypothesis whereby methods which sample areas containing food DNA consumed from longer and more continuous pre-sampling time intervals explain variation among sampling methods in observed prey richness. Choice of sampling method can influence predator diet characterization and is particularly important if researchers wish to quantify uncommon diet items or compare diet metrics using samples collected via different methods.

Environmental DNA↗

Linking geology and health sciences to assess childhood lead poisoning from artisanal gold mining in Nigeria

Background: In 2010, Médecins Sans Frontières discovered a lead poisoning outbreak linked to artisanal gold processing in northwestern Nigeria. The outbreak has killed approximately 400 young children and affected thousands more. Objectives: Our aim was to undertake an interdisciplinary geological- and health-science assessment to clarify lead sources and exposure pathways, identify additional toxicants of concern and populations at risk, and examine potential for similar lead poisoning globally. Methods: We applied diverse analytical methods to ore samples, soil and sweep samples from villages and family compounds, and plant foodstuff samples. Results: Natural weathering of lead-rich gold ores before mining formed abundant, highly gastric-bioaccessible lead carbonates. The same fingerprint of lead minerals found in all sample types confirms that ore processing caused extreme contamination, with up to 185,000 ppm lead in soils/sweep samples and up to 145 ppm lead in plant foodstuffs. Incidental ingestion of soils via hand-to-mouth transmission and of dusts cleared from the respiratory tract is the dominant exposure pathway. Consumption of water and foodstuffs contaminated by the processing is likely lesser, but these are still significant exposure pathways. Although young children suffered the most immediate and severe consequences, results indicate that older children, adult workers, pregnant women, and breastfed infants are also at risk for lead poisoning. Mercury, arsenic, manganese, antimony, and crystalline silica exposures pose additional health threats. Conclusions: Results inform ongoing efforts in Nigeria to assess lead contamination and poisoning, treat victims, mitigate exposures, and remediate contamination. Ore deposit geology, pre-mining weathering, and burgeoning artisanal mining may combine to cause similar lead poisoning disasters elsewhere globally.

Environmental Health Perspectives↗

Using an analytical geometry method to improve tiltmeter data presentation

The tiltmeter is a useful tool for geologic and geotechnical applications. To obtain full benefit from the tiltmeter, easy and accurate data presentations should be used. Unfortunately, the most commonly used method for tilt data reduction now may yield inaccurate and low-resolution results. This article describes a simple, accurate, and high-resolution approach developed at the Illinois State Geological Survey for data reduction and presentation. The orientation of tiltplates is determined first by using a trigonometric relationship, followed by a matrix transformation, to obtain the true amount of rotation change of the tiltplate at any given time. The mathematical derivations used for the determination and transformation are then coded into an integrated PC application by adapting the capabilities of commercial spreadsheet, database, and graphics software. Examples of data presentation from tiltmeter applications in studies of landfill covers, characterizations of mine subsidence, and investigations of slope stability are also discussed.

Environmental & Engineering Geoscience↗

Assessment of the geoavailability of trace elements from selected zinc minerals

This assessment focused on five zinc-bearing minerals. The minerals were subjected to a number of analyses including quantitative X-ray diffraction, optical microscopy, leaching tests, and bioaccessibility and toxicity studies. Like a previous comprehensive assessment of five copper-bearing minerals, the purpose of this assessment was to obtain structural and chemical information and to characterize the reactivity of each mineral to various simulated environmental and biological conditions. As in the copper minerals study, analyses were conducted consistent with widely accepted methods. Unless otherwise noted, analytical methods used for this study were identical to those described in the investigation of copper-bearing minerals. Two sphalerite specimens were included in the zinc-minerals set. One sphalerite was recovered from a mine in Balmat, New York; the second came from a mine in Creede, Colorado. The location and conditions of origin are significant because, as analyses confirmed, the two sphalerite specimens are quite different. For example, data acquired from a simulated gastric fluid (SGF) study indicate that the hydrothermally formed Creede sphalerite contains orders of magnitude higher arsenic, cadmium, manganese, and lead than the much older metamorphic Balmat sphalerite. The SGF and other experimental results contained in this report suggest that crystallizing conditions such as temperature, pressure, fluidization, or alteration processes significantly affect mineral properties—properties that, in turn, influence reactivity, solubility, and toxicity. The three remaining minerals analyzed for this report—smithsonite, hemimorphite, and hydrozincite—are all secondary minerals or alteration products of zinc-ore deposits. In addition, all share physical characteristics such as tenacity, density, streak, and cleavage. Similarities end there. The chemical composition, unit-cell parameters, acid-neutralizing potential, and other observable and quantifiable properties indicate very different minerals. Only one of each of these minerals was studied. Had this assessment included multiples of these minerals, geochemical and mineralogical distinctions would have emerged, similar to the results for the two sphalerite specimens.

Arizona;Chihuahua;Colorado;New York↗

Corn leaf nitrate reductase - A nontoxic alternative to cadmium for photometric nitrate determinations in water samples by air-segmented continuous-flow analysis

Development, characterization, and operational details of an enzymatic, air-segmented continuous-flow analytical method for colorimetric determination of nitrate + nitrite in natural-water samples is described. This method is similar to U.S. Environmental Protection Agency method 353.2 and U.S. Geological Survey method 1-2545-90 except that nitrate is reduced to nitrite by soluble nitrate reductase (NaR, EC 1.6.6.1) purified from corn leaves rather than a packed-bed cadmium reactor. A three-channel, air-segmented continuous-flow analyzer-configured for simultaneous determination of nitrite (0.020-1.000 mg-N/L) and nitrate + nitrite (0.05-5.00 mg-N/L) by the nitrate reductase and cadmium reduction methods-was used to characterize analytical performance of the enzymatic reduction method. At a sampling rate of 90 h-1, sample interaction was less than 1% for all three methods. Method detection limits were 0.001 mg of NO2- -N/L for nitrite, 0.003 mg of NO3-+ NO2- -N/L for nitrate + nitrite by the cadmium-reduction method, and 0.006 mg of NO3- + NO2- -N/L for nitrate + nitrite by the enzymatic-reduction method. Reduction of nitrate to nitrite by both methods was greater than 95% complete over the entire calibration range. The difference between the means of nitrate + nitrite concentrations in 124 natural-water samples determined simultaneously by the two methods was not significantly different from zero at the p = 0.05 level.

Environmental Science & Technology↗

A modeling approach to compare ΣPCB concentrations between congener-specific analyses

Changes in analytical methods over time pose problems for assessing long-term trends in environmental contamination by polychlorinated biphenyls (PCBs). Congener-specific analyses vary widely in the number and identity of the 209 distinct PCB chemical configurations (congeners) that are quantified, leading to inconsistencies among summed PCB concentrations (&Sigma;PCB) reported by different studies. Here we present a modeling approach using linear regression to compare &Sigma;PCB concentrations derived from different congener-specific analyses measuring different co-eluting groups. The approach can be used to develop a specific conversion model between any two sets of congener-specific analytical data from similar samples (similar matrix and geographic origin). We demonstrate the method by developing a conversion model for an example data set that includes data from two different analytical methods, a low resolution method quantifying 119 congeners and a high resolution method quantifying all 209 congeners. We used the model to show that the 119-congener set captured most (93%) of the total PCB concentration (i.e., &Sigma; 209 PCB) in sediment and biological samples. &Sigma;PCB concentrations estimated using the model closely matched measured values (mean relative percent difference&thinsp;=&thinsp;9.6). General applications of the modeling approach include (a) generating comparable &Sigma;PCB concentrations for samples that were analyzed for different congener sets; and (b) estimating the proportional contribution of different congener sets to &Sigma;PCB. This approach may be especially valuable for enabling comparison of long-term remediation monitoring results even as analytical methods change over time.

Integrated Environmental Assessment and Management↗