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Estimates of tracer-based piston-flow ages of groundwater from selected sites: National Water-Quality Assessment Program, 1992–2005

This report documents selected age data interpreted from measured concentrations of environmental tracers in groundwater from 1,399 National Water-Quality Assessment (NAWQA) Program groundwater sites across the United States. The tracers of interest were chlorofluorocarbons (CFCs), sulfur hexafluoride (SF 6 ), and tritium/helium-3 ( 3 H/ 3 He). Tracer data compiled for this analysis primarily were from wells representing two types of NAWQA groundwater studies—Land-Use Studies (shallow wells, usually monitoring wells, in recharge areas under dominant land-use settings) and Major-Aquifer Studies (wells, usually domestic supply wells, in principal aquifers and representing the shallow, used resource). Reference wells (wells representing groundwater minimally impacted by anthropogenic activities) associated with Land-Use Studies also were included. Tracer samples were collected between 1992 and 2005, although two networks sampled from 2006 to 2007 were included because of network-specific needs. Tracer data from other NAWQA Program components (Flow System Studies, which are assessments of processes and trends along groundwater flow paths, and various topical studies) were not compiled herein. Tracer data from NAWQA Land-Use Studies and Major-Aquifer Studies that previously had been interpreted and published are compiled herein (as piston-flow ages), but have not been reinterpreted. Tracer data that previously had not been interpreted and published are evaluated using documented methods and compiled with aqueous concentrations, equivalent atmospheric concentrations (for CFCs and SF 6 ), estimates of tracer-based piston-flow ages, and selected ancillary data, such as redox indicators, well construction, and major dissolved gases (N 2 , O 2 , Ar, CH 4 , and CO 2 ). Tracer-based piston-flow ages documented in this report are simplistic representations of the tracer data. Tracer-based piston-flow ages are a convenient means of conceptualizing groundwater age. However, the piston-flow model is based on the potentially limiting assumptions that tracer transport is advective and that no mixing occurs. Additional uncertainties can arise from tracer degradation, sorption, contamination, or fractionation; terrigenic (natural) sources of tracers; spatially variable atmospheric tracer concentrations; and incomplete understanding of mechanisms of recharge or of the conditions under which atmospheric tracers were partitioned to recharge. The effects of some of these uncertainties are considered herein. For example, degradation, contamination, or fractionation often can be identified or inferred. However, detailed analysis of the effects of such uncertainties on the tracer-based piston-flow ages is constrained by sparse data and an absence of complementary lines of evidence, such as detailed solute transport simulations. Thus, the tracer-based piston-flow ages compiled in this report represent only an initial interpretation of the tracer data.

Scientific Investigations Report↗

Analysis of groundwater response to tidal fluctuations, Operable Unit 2, Area 8, Naval Base Kitsap, Keyport, Washington

Operable Unit 2, Area 8, at Naval Base Kitsap, Keyport is the site of a former chrome-plating facility that released metals (primarily chromium and cadmium), chlorinated volatile organic compounds, and petroleum compounds into the local environment. To ensure long-term protectiveness, as stipulated in the Fourth Five-Year Review for the site, Naval Facilities Engineering Command Northwest collaborated with the U.S. Environmental Protection Agency, the Washington State Department of Ecology, and the Suquamish Tribe, to collect data to monitor the contamination left in place and to ensure the site does not pose a risk to human health or the environment. To support these efforts, refined information was needed on the interaction of fresh groundwater with seawater in response to the up-to 13-ft tidal fluctuations at this nearshore site adjacent to Port Orchard Bay. The information was analyzed to meet the primary objective of this investigation, which was to determine the optimal time during the semi-diurnal and the neap-spring tidal cycles to sample groundwater for freshwater contaminants in Area 8 monitoring wells. Groundwater levels and specific conductance in five monitoring wells, along with marine water-levels (tidal levels) in Port Orchard Bay, were monitored every 15 minutes during a 3-week duration to determine how nearshore groundwater responds to tidal forcing. Time series data were collected from October 24, 2017, to November 16, 2017, a period that included neap and spring tides. Vertical profiles of specific conductance were also measured once in the screened interval of each well prior to instrument deployment to determine if a freshwater/saltwater interface was present in the well during that particular time. The vertical profiles of specific conductance were measured only one time during an ebbing tide at approximately the top, middle, and bottom of the saturated thickness within the screened interval of each well. The landward-most well, MW8-8, was completely freshwater, while one of the most seaward wells, MW8-9, was completely saline. A distinct saltwater interface was measured in the three other shallow wells (MW8-11, MW8-12, and MW8-14), with the topmost groundwater occurring fresh underlain by higher conductivity water. Lag times between minimum spring-tide level and minimum groundwater levels in wells ranged from about 2 to 4.5 hours in the less-than 20-ft deep wells screened across the water table, and was about 7 hours for the single 48-ft deep well screened below the water table. Those lag times were surprisingly long considering the wells are all located within 200-ft of the shoreline and the local geology is largely coarse-grained glacial outwash deposits. Various manmade subsurface features, such as slurry walls and backfilled excavations, likely influence and confuse the connectivity between seawater and groundwater. The specific-conductance time-series data showed clear evidence of substantial saltwater intrusion into the screened intervals of most shallow wells. Unexpectedly, the intrusion was associated with the neap part of the tidal cycle around November 13–16, when relatively low barometric pressure and high southerly winds led to the highest high and low tides measured during the monitoring period. The data consistently indicated that the groundwater had the lowest specific conductance (was least mixed with seawater) during the prior neap tides around October 30, the same period when the shallow groundwater levels were lowest. Although the specific conductance response is somewhat different between wells, the data do suggest that it is the heights of the actual high-high and low-low tides, regardless of whether or not they occur during the neap or spring part of the cycle, that allows seawater intrusion into the nearshore aquifer at Area 8. With all the data taken into consideration, the optimal time for sampling the shallow monitoring wells at Area 8 would be centered on a 2–5-hour period following the predicted low-low tide during neap tide, with due consideration of local atmospheric pressure and wind conditions that have the potential to generate tides that can be substantially higher than those predicted from lunar-solar tidal forces. The optimal time for sampling the deeper monitoring wells at Area 8 would be during the 6–8-hour period following a predicted low-low tide, also during the neap tide part of the tidal cycle. The specific time window to sample each well following a low tide can be found in table 5. Those periods are when groundwater in the wells is most fresh and least diluted by seawater intrusion. In addition to timing, consideration should be given to collecting undisturbed samples from the top of the screened interval (or top of the water table if below the top of the interval) to best characterize contaminant concentrations in freshwater. A downhole conductivity probe could be used to identify the saltwater interface, above which would be the ideal depth for sampling.

Washington↗

Organic contaminants, trace and major elements, and nutrients in water and sediment sampled in response to the Deepwater Horizon oil spill

Beach water and sediment samples were collected along the Gulf of Mexico coast to assess differences in contaminant concentrations before and after landfall of Macondo-1 well oil released into the Gulf of Mexico from the sinking of the British Petroleum Corporation's Deepwater Horizon drilling platform. Samples were collected at 70 coastal sites on the Gulf of Mexico between May 7 and July 7, 2010, to document baseline, "pre-landfall" conditions. A subset of these sites was resampled during October 4 to 14, 2010, after oil had made landfall on the Gulf of Mexico coast ("post-landfall") to determine if actionable concentrations of oil were present along shorelines. Few organic contaminants were detected in water; their detection frequencies were generally low and similar in pre-landfall and post-landfall samples. Only one organic contaminant, toluene, had significantly higher concentrations in post-landfall than pre-landfall water samples. No samples exceeded any human-health benchmarks, and only one sample exceeded an aquatic-life benchmark-the toxic-unit benchmark for polycyclic aromatic hydrocarbons (PAH) mixtures was exceeded in one post-landfall water sample from Louisiana. No exceedance was observed in the corresponding pre-landfall water sample at this site. In sediment, several PAHs were detected at over 20 percent of sites. Concentrations of 3 parent PAHs and 17 alkylated PAH groups were significantly higher in post-landfall samples than pre-landfall samples. One pre-landfall sample from Texas exceeded the sediment toxic-unit benchmark for PAH mixtures; this site was not sampled during the post-landfall period, so no comparison between sampling periods could be made. Twenty-seven percent of sediment samples exceeded empirical sediment-quality benchmarks (upper screening values) for PAHs, indicating these samples are in the probable-effect range. A higher percentage of post-landfall samples exceeded upper screening-value benchmarks (37 percent) than did pre-landfall samples (22 percent), but there was no significant difference in the proportion of samples exceeding one or more benchmarks between paired pre-landfall and post-landfall samples. Seven sites had the largest concentration differences between post-landfall and pre-landfall samples for fifteen alkylated PAHs. Five of these seven sites (1 site in Louisiana, 1 in Mississippi, and 3 in Alabama) were identified on the basis of diagnostic geochemical biomarkers as containing Macondo-1 oil in post-landfall sediments and tarballs, as described in a companion report by Rosenbauer and others (2010). For trace and major elements in water, analytical reporting levels for several elements were highly variable; after censoring to a common reporting threshold, concentrations were significantly different between pre-landfall and post-landfall samples for a few elements, all of which are elements in seawater. No human-health benchmarks were exceeded, although these were available for only two elements. Aquatic-life benchmarks for trace elements were exceeded in almost 50 percent of water samples. Post-landfall samples exceeded one or more acute benchmarks in 21 percent, and chronic benchmarks in 93 percent of samples, compared to 1 percent (acute) and 39 percent (chronic) for pre-landfall samples. The elements responsible for the most exceedances in post-landfall samples were boron (48 samples), copper (22), and manganese (12). Nickel and vanadium, which U.S. Environmental Protection Agency specifically identified as relevant to the oil spill, were responsible for exceedances in only one of the fifty-two post-landfall samples with exceedances. These results represent the minimum number of exceedances for several trace elements because a substantial number of samples could not be compared with benchmarks because the element was determined during only one sampling period (boron and vanadium) or the reporting level for the sample was higher than the applicable benchmark value (for example, cobalt, copper, lead, and nickel). The high and variable reporting levels for trace elements in water also precluded the statistical comparison between sampling periods of the proportion of samples exceeding benchmarks. For trace elements in whole (unsieved) sediment, 47 percent of samples exceeded empirical upper screening-value benchmarks, indicating these samples are in the probable-effect range. However, there was no significant difference in the proportion of samples exceeding one or more benchmarks between paired pre-landfall post-landfall samples. Benchmark exceedance frequencies could be conservatively high, because they are based on measurements of total trace-element concentrations, including the sediment matrix. In fine sediment (the less than 63-micrometer sediment fraction), one or more trace or major elements were anthropogenically enriched relative to national baseline values for U.S. streams for almost all sediment samples (123 of 124). Sixteen percent of sediment samples exceeded upper screening-value benchmarks for, and were enriched in, one or more of the element(s) barium (in 14 samples), vanadium (5), aluminum (3), manganese (3), arsenic (2), chromium (2), and cobalt (1). These samples, collected from Louisiana and Texas, were evenly divided between the pre-landfall (9 samples) and post-landfall (10 samples) periods. Considering all the information evaluated in this report, there were significant differences between pre-landfall and post-landfall samples for PAH concentrations in sediment. Pre-landfall and post-landfall samples did not differ significantly in concentrations or benchmark exceedances for most organics in water or trace elements in sediment. For trace elements in water, aquatic-life benchmarks were exceeded in almost 50 percent of samples, but the high and variable analytical reporting levels precluded statistical comparison of benchmark exceedances between sampling periods. Concentrations of several PAH compounds in sediment were significantly higher in post-landfall samples than pre-landfall samples, and five of seven sites with the largest differences in PAH concentrations also had diagnostic geochemical evidence of Deepwater Horizon Macondo-1 oil from Rosenbauer and others (2010).

Open-File Report↗

Statewide analysis of the drainage-area ratio method for 34 streamflow percentile ranges in Texas

The drainage-area ratio method commonly is used to estimate streamflow for sites where no streamflow data are available using data from one or more nearby streamflow-gaging stations. The method is intuitive and straightforward to implement and is in widespread use by analysts and managers of surface-water resources. The method equates the ratio of streamflow at two stream locations to the ratio of the respective drainage areas. In practice, unity often is assumed as the exponent on the drainage-area ratio, and unity also is assumed as a multiplicative bias correction. These two assumptions are evaluated in this investigation through statewide analysis of daily mean streamflow in Texas. The investigation was made by the U.S. Geological Survey in cooperation with the Texas Commission on Environmental Quality. More than 7.8 million values of daily mean streamflow for 712 U.S. Geological Survey streamflow-gaging stations in Texas were analyzed. To account for the influence of streamflow probability on the drainage-area ratio method, 34 percentile ranges were considered. The 34 ranges are the 4 quartiles (0-25, 25-50, 50-75, and 75-100 percent), the 5 intervals of the lower tail of the streamflow distribution (0-1, 1-2, 2-3, 3-4, and 4-5 percent), the 20 quintiles of the 4 quartiles (0-5, 5-10, 10-15, 15-20, 20-25, 25-30, 30-35, 35-40, 40-45, 45-50, 50-55, 55-60, 60-65, 65-70, 70-75, 75-80, 80-85, 85-90, 90-95, and 95-100 percent), and the 5 intervals of the upper tail of the streamflow distribution (95-96, 96-97, 97-98, 98-99 and 99-100 percent). For each of the 253,116 (712X711/2) unique pairings of stations and for each of the 34 percentile ranges, the concurrent daily mean streamflow values available for the two stations provided for station-pair application of the drainage-area ratio method. For each station pair, specific statistical summarization (median, mean, and standard deviation) of both the exponent and bias-correction components of the drainage-area ratio method were computed. Statewide statistics (median, mean, and standard deviation) of the station-pair specific statistics subsequently were computed and are tabulated herein. A separate analysis considered conditioning station pairs to those stations within 100 miles of each other and with the absolute value of the logarithm (base-10) of the ratio of the drainage areas greater than or equal to 0.25. Statewide statistics of the conditional station-pair specific statistics were computed and are tabulated. The conditional analysis is preferable because of the anticipation that small separation distances reflect similar hydrologic conditions and the observation of large variation in exponent estimates for similar-sized drainage areas. The conditional analysis determined that the exponent is about 0.89 for streamflow percentiles from 0 to about 50 percent, is about 0.92 for percentiles from about 50 to about 65 percent, and is about 0.93 for percentiles from about 65 to about 85 percent. The exponent decreases rapidly to about 0.70 for percentiles nearing 100 percent. The computation of the bias-correction factor is sensitive to the range analysis interval (range of streamflow percentile); however, evidence suggests that in practice the drainage-area method can be considered unbiased. Finally, for general application, suggested values of the exponent are tabulated for 54 percentiles of daily mean streamflow in Texas; when these values are used, the bias correction is unity.

Scientific Investigations Report↗

Hydrogeologic framework, ground-water geochemistry, and assessment of nitrogen yield from base flow in two agricultural watersheds, Kent County, Maryland

Hydrostratigraphic and geochemical data collected in two adjacent watersheds on the Delmarva Peninsula, in Kent County, Maryland, indicate that shallow subsurface stratigraphy is an important factor that affects the concentrations of nitrogen in ground water discharging as stream base flow. The flux of nitrogen from shallow aquifers can contribute substantially to the eutrophication of streams and estuaries, degrading water quality and aquatic habitats. The information presented in this report includes a hydrostratigraphic framework for the Locust Grove study area, analyses and interpretation of ground-water chemistry, and an analysis of nutrient yields from stream base flow. An understanding of the processes by which ground-water nitrogen discharges to streams is important for optimal management of nutrients in watersheds in which ground-water discharge is an appreciable percentage of total streamflow. The U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency (USEPA), collected and analyzed hydrostratigraphic and geochemical data in support of ground-water flow modeling by the USEPA. The adjacent watersheds of Morgan Creek and Chesterville Branch have similar topography and land use; however, reported nitrogen concentrations are generally 6 to 10 milligrams per liter in Chesterville Branch but only 2 to 4 milligrams per liter in Morgan Creek. Ground water in the surficial aquifer in the recharge areas of both streams has high concentrations of nitrate (greater than 10 milligrams per liter as N) and dissolved oxygen. One component of the ground water discharging to Morgan Creek typically is anoxic and contains virtually no dissolved nitrate; most of the ground water discharging to Chesterville Branch is oxygenated and contains moderately high concentrations of nitrate. The surficial aquifer in the study area is composed of the deeply weathered sands and gravels of the Pensauken Formation (the Columbia aquifer) and the underlying glauconitic sands of the upper Aquia Formation (the Aquia aquifer). The lower 6 to 9 meters of the Aquia Formation is a low-permeability silt-clay with abundant glauconite. The Aquia confining layer underlies the Columbia-Aquia surficial aquifer throughout the study area. The sediment redox transition, identified in cores, that occurs in the upper 0.5 to 1 meter of the Aquia confining layer is thought to be a site for subsurface denitrification of ground water. The first confined aquifer is composed of the glauconitic sands in the upper 9 to 11 meters of the Hornerstown Formation. The Hornerstown aquifer is underlain by 10 to 15 meters of glauconitic silt-clay at the base of the Hornerstown Formation (the Hornerstown confining layer), and 5 meters of low-permeability clay in the underlying Severn Formation. The Aquia and Hornerstown Formations dip and thicken to the southeast, and the Aquia confining layer subcrops shallowly (within 5 meters of the land surface) in a band that strikes southwest to northeast across the northern edge of the study area. The surficial aquifer is very thin (generally less than 5 meters) north of Morgan Creek, and the alluvial valley of Morgan Creek has incised into the top of the Aquia confining layer. In contrast, the Aquia confining layer lies 22 meters below Chesterville Branch, and the surficial aquifer approaches 30 meters in thickness (away from the creek). Chemically reduced iron sulfides and glauconite in the Aquia confining layer are likely substrates for denitrification of nitrate in ground water. Evidence from the dissolved concentrations of nitrate, sulfate, iron, argon, and nitrogen gas, and stable nitrogen isotopes support the interpretation that ground water flowing near the top of the Aquia confining layer, or through the confined Hornerstown aquifer, has undergone denitrification. This process appears to have the greatest effect on ground-water chemistry north of Morgan Creek, where the surficial aquifer is thin and a greater percentage of the ground water contacts the Aquia confining layer. The base-flow discharges of total nitrogen from the two watersheds are of similar magnitude, although Chesterville Branch has somewhat higher loads (29,000 kilograms of nitrogen per year) than Morgan Creek (20,000 kilograms of nitrogen per year), although Morgan Creek has a larger drainage area and a greater discharge of water. The base-flow yield of nitrogen (load per unit area) in Chesterville Branch (median of 0.058 grams per second per square kilometer at the outlet) is more than twice that of Morgan Creek (median of 0.022 grams per second per square kilometer at the outlet), reflecting the higher concentration of nitrate in ground water discharging to Chesterville Branch. Total nitrogen concentrations tend to decrease downstream in Chesterville Branch and increase downstream in Morgan Creek. The downstream trend in Chesterville Branch may be affected by instream nitrogen uptake and denitrification, and an increasing proportion of older, denitrified ground water in downstream discharge. The downstream trends in Morgan Creek may be affected by inflow from tributaries, downstream changes in the source of discharge water, and downstream changes in the riparian zone, which could affect the processes and degree of denitrification. Although these two watersheds appear to have landscape features (such as topography, land use, and soils) that would produce similar nitrogen discharges, a more detailed examination of landscape features indicates that Chesterville Branch has soils that are slightly better drained, tributary stream outlets at higher altitudes, and a slightly higher percentage of agricultural land. All of these factors have been related to higher nitrogen yields. Nonetheless, most of the data support the interpretation that hydrostratigraphy has the greatest effect in producing the difference in nitrogen yields between the two watersheds.

Maryland↗

Composition and distribution of fish environmental DNA in an Adirondack watershed

Background Environmental DNA (eDNA) surveys are appealing options for monitoring aquatic biodiversity. While factors affecting eDNA persistence, capture and amplification have been heavily studied, watershed-scale surveys of fish communities and our confidence in such need further exploration. Methods We characterized fish eDNA compositions using rapid, low-volume filtering with replicate and control samples scaled for a single Illumina MiSeq flow cell, using the mitochondrial 12S ribosomal RNA locus for taxonomic profiling. Our goals were to determine: (1) spatiotemporal variation in eDNA abundance, (2) the filtrate needed to achieve strong sequencing libraries, (3) the taxonomic resolution of 12S ribosomal sequences in the study environment, (4) the portion of the expected fish community detectable by 12S sequencing, (5) biases in species recovery, (6) correlations between eDNA compositions and catch per unit effort (CPUE) and (7) the extent that eDNA profiles reflect major watershed features. Our bioinformatic approach included (1) estimation of sequencing error from unambiguous mappings and simulation of taxonomic assignment error under various mapping criteria; (2) binning of species based on inferred assignment error rather than by taxonomic rank; and (3) visualization of mismatch distributions to facilitate discovery of distinct haplotypes attributed to the same reference. Our approach was implemented within the St. Regis River, NY, USA, which supports tribal and recreational fisheries and has been a target of restoration activities. We used a large record of St. Regis-specific observations to validate our assignments. Results We found that 300 mL drawn through 25-mm cellulose nitrate filters yielded greater than 5 ng/µL DNA at most sites in summer, which was an approximate threshold for generating strong sequencing libraries in our hands. Using inferred sequence error rates, we binned 12S references for 110 species on a state checklist into 85 single-species bins and seven multispecies bins. Of 48 bins observed by capture survey in the St. Regis, we detected eDNA consistent with 40, with an additional four detections flagged as potential contaminants. Sixteen unobserved species detected by eDNA ranged from plausible to implausible based on distributional data, whereas six observed species had no 12S reference sequence. Summed log-ratio compositions of eDNA-detected taxa correlated with log(CPUE) (Pearson’s R = 0.655, P < 0.001). Shifts in eDNA composition of several taxa and a genotypic shift in channel catfish ( Ictalurus punctatus ) coincided with the Hogansburg Dam, NY, USA. In summary, a simple filtering apparatus operated by field crews without prior expertise gave useful summaries of eDNA composition with minimal evidence of field contamination. 12S sequencing achieved useful taxonomic resolution despite the short marker length, and data exploration with standard bioinformatic tools clarified taxonomic uncertainty and sources of error.

New York↗

Reconnaissance of mixed organic and inorganic chemicals in private and public supply tapwaters at selected residential and workplace sites in the United States

Safe drinking water at the point-of-use (tapwater, TW) is a United States public health priority. Multiple lines of evidence were used to evaluate potential human health concerns of 482 organics and 19 inorganics in TW from 13 (7 public supply, 6 private well self-supply) home and 12 (public supply) workplace locations in 11 states. Only uranium (61.9 μg L –1 , private well) exceeded a National Primary Drinking Water Regulation maximum contaminant level (MCL: 30 μg L –1 ). Lead was detected in 23 samples (MCL goal: zero). Seventy-five organics were detected at least once, with median detections of 5 and 17 compounds in self-supply and public supply samples, respectively (corresponding maxima: 12 and 29). Disinfection byproducts predominated in public supply samples, comprising 21% of all detected and 6 of the 10 most frequently detected. Chemicals designed to be bioactive (26 pesticides, 10 pharmaceuticals) comprised 48% of detected organics. Site-specific cumulative exposure–activity ratios (∑ EAR ) were calculated for the 36 detected organics with ToxCast data. Because these detections are fractional indicators of a largely uncharacterized contaminant space, ∑ EAR in excess of 0.001 and 0.01 in 74 and 26% of public supply samples, respectively, provide an argument for prioritized assessment of cumulative effects to vulnerable populations from trace-level TW exposures.

Environmental Science & Technology↗

Dieback of Acacia koa in Hawaii: Ecological and pathological characteristics of affected stands

Koa (Acacia koa) is an endemic Hawaiian tree that serves as a keystone species in the upper elevation forests of all the main islands. In the Mauna Loa Strip area of Hawaii Volcanoes National Park, mature koa stands are suffering from an unexplained dieback that has increased in severity since it was first noticed approximately 25 years ago. The dieback is often evident in patches, and generally spreads within stands in a radial fashion from a localized infection center. Entire crowns of affected trees become wilted, with foliage gradually progressing from an apparent healthy to a completely chlorotic condition. Although most trees die soon after the onset of symptoms, some trees are able to survive crown death by producing epicormic shoots on the lower portions of the trunk. Previously published studies reported that a vascular wilt fungus (Fusarium oxysporum f. sp. koae) was associated with koa seeds and the rhizosphere of healthy and dieback-affected koa stands. The purpose of this study was to characterize the stand structure, soil conditions, and physiological condition of dieback-affected trees, and to assess the possible role of F. oxysporum f. sp. koae in the current dieback stands. This fungus was isolated from branches of symptomatic koa in dieback-affected stands and roots from healthy and dieback-affected stands. Possible differences in the pathogenicity and virulence of F. oxysporum f. sp. koae isolates obtained from the roots of healthy koa in unaffected stands and those from branches of dieback-affected koa were determined by greenhouse inoculations of koa seedlings. Healthy koa saplings in stands unaffected by dieback were also inoculated to determine if disease symptoms could be induced by inoculation of injured roots in the field. Both branch and root isolates were pathogenic; with the percent mortality of inoculated seedlings ranging from 30 to 60% for all isolates. Disease severity between branch and root isolates was not significantly different. Wilt symptoms were not observed in field inoculations of koa saplings after 8 months. Investigation of the dieback stand structure determined that the larger size classes (i.e., DBH > 3 cm) were all affected equally, with the smallest size class (i.e., 0-3 cm DBH) having the lowest percentage of dieback at each site. Soil from dieback stands had higher water content and was more acidic than that from neighboring unaffected stands. Phyllodes on epicormic shoots of dieback trees had a reduced area, mass, and mass to area ratio. Phyllodes on dieback trees also had reduced stomatal conductance and higher (less negative) leaf water potential. Results from the greenhouse inoculations demonstrated that F. oxysporum f. sp. koae is pathogenic to koa, but the pathogen's activity in the field may be influenced by predisposing factors such as temperature fluctuations, water availability, soil type, and interactions with other soil organisms. F. oxysporum f. sp. koae appears to play an important role in regulating koa stand dynamics, growth, and physiology under environmental and edaphic conditions favorable for disease development. ?? 2002 Elsevier Science B.V. All rights reserved.

Forest Ecology and Management↗

Bioaccumulation and toxicity of selenium during a life-cycle exposure with desert pupfish (Cyprinodon macularius)

Populations of desert pupfish ( Cyprinodon macularius ; pupfish), a federally-listed endangered species, inhabit irrigation drains in the Imperial Valley agricultural area of southern California. These drains have varying degrees of selenium (Se) contamination of water, sediment, and aquatic biota. Published Se toxicity studies suggest that these levels of Se contamination may pose risk of chronic toxicity to Se-sensitive fish, but until recently there have been no studies of the chronic toxicity of Se to desert pupfish. A life-cycle Se exposure with pupfish was conducted to estimate dietary and tissue thresholds for toxic effects of Se on all life stages. The dietary exposure was based on live oligochaete worms ( Lumbriculus variegatus ) dosed with Se by a laboratory food chain based on selenized yeast. Oligochaetes readily accumulated Se from mixtures of selenized and control yeasts. The protocol for dosing oligochaetes for pupfish feeding studies included long-term (at least 28 days) feeding of a low-ration of yeast mixtures to large batches of oligochaetes. Oligochaetes were dosed at five Se levels in a 50-percent dilution series. Pupfish were simultaneously fed Se-dosed oligochaetes and exposed to a series of Se concentrations in water (consisting of 85 percent selenate and 15 percent selenite) to produce exposures that were consistent with Se concentrations and speciation in pupfish habitats. The nutritional characteristics of oligochaete diets were consistent across the range of oligochaete Se concentrations tested. The life-cycle exposure started with laboratory-cultured juvenile pupfish that were exposed to Se through sexual maturation and reproduction (150 days; F0 exposure). The Se exposure continued with eggs, larvae, and juveniles produced by Se-exposed parents (79 days; F1 exposure). Selenium exposure (water and diets), Se bioaccumulation (whole-body and eggs), and toxicity endpoints (juvenile and adult survival and growth; egg production and hatching success, larval survival and deformities) were documented throughout the life-cycle study. Selenium concentrations in water (as much as 52 micrograms per liter [μg/L]) and diets (as much as 53 micrograms per gram [μg/g], on a dry weight basis) bracketed concentrations reported in pupfish habitats. Juvenile F0 pupfish rapidly accumulated Se and bioaccumulation models indicated that pupfish had reached more than 97 percent of maximum whole-body Se concentrations by the time they reached reproductive maturity. Adult pupfish accumulated whole-body Se concentrations that averaged about 40 percent of those in the oligochaete diets. Selenium concentrations in eggs and F1 juveniles were similar to or slightly greater than Se concentrations in F0 adults. Juvenile F0 pupfish contained selenomethionine fractions (62–71 percent of whole-body Se) greater than the average reported for wild pupfish from the Imperial Valley (53 percent). Selenium exposure had minimal effects on survival or growth of juvenile and adult pupfish. There was evidence of toxic effects on pupfish in the highest Se treatment (Se–5), including reduced growth of F0 and F1 juvenile pupfish (17–21 percent less than controls) on some sampling dates. These growth reductions did not persist to subsequent sampling dates, but reduced growth of F1 pupfish in the Se–5 treatment was associated with reduced survival (12 percent less than controls). Egg production was greatest in the controls and decreased with increasing Se exposure, reaching a minimum (51 percent less than controls) in the Se–4 treatment, but egg production was reduced by only 24 percent in the Se–5 treatment, a lesser reduction than in other Se treatments except Se–1. There was no statistically significant overall effect of Se treatment on mean pupfish egg production, reflecting large variation among replicates and among sampling dates. However, comparisons of daily mean egg production for 23 sampling dates indicated that egg production in each of 5 Se treatments was significantly less than controls on multiple (3–7) sampling dates, but no mean for any Se treatment was significantly greater than controls on any date. Significant reductions in daily egg production occurred mainly during the middle of the study and egg production increased in several Se treatments during the final 2 weeks of the study. These results suggest that pupfish egg production, although a highly variable endpoint, was adversely affected by elevated Se exposure. Neither egg hatching success nor survival of F1 larvae indicated clear evidence of Se toxicity. Egg hatching success did not differ significantly among treatments, with means ranging from 84–91 percent. The frequency of morphological deformities (primarily spinal deformities) was greater in larvae 10 days post-fertilization (dpf) from a preliminary reproduction study than in older larvae (14 dpf) from the main reproduction study. The frequency of larval deformities was generally greater in Se treatments than controls, but mean frequencies did not differ significantly among treatments. Survival of F1 larvae to 21 dpf was not reduced significantly by parental Se exposure, but the Se–5 treatment had the lowest larval survival (84 percent), and lowest combined egg hatching and larval survival (76 percent). Results of the Se treatments indicate that pupfish were insensitive to Se toxicity through most of their life cycle. Consistent toxic effects on survival and growth of juvenile and adult pupfish (defined as at least 10 percent reduction compared to controls) occurred only in treatment Se–5, which had a mean dietary Se concentration of 52 μg/g and a mean pupfish whole-body Se concentration of 27 μg/g. These apparent toxicity thresholds for growth and survival rank among the least sensitive chronic Se toxicity values reported for nonreproductive endpoints in freshwater fish. Comparisons of these thresholds to surveys of Se concentrations in the Imperial Valley suggest that risks of Se toxicity are low in pupfish habitats. The dietary threshold was about twice as high as the greatest mean Se concentrations reported in midge larvae from seven sites in the Imperial Valley. Whole-body thresholds were greater than mean whole-body Se concentrations reported for field-collected pupfish from three sites and for the sailfin molly (Poecilia latipinna), a potential bioaccumulation surrogate for pupfish, from seven sites. Reduced egg production, although highly variable, was the most sensitive response of pupfish to Se exposure. Toxic effects on egg production (reductions of 24–51 percent relative to controls) occurred in the four highest Se treatments, corresponding to reproductive toxicity thresholds of 7.3 μg/g for Se in diet, 3.4 μg/g in pupfish (whole body), and 4.4 μg/g in pupfish eggs. These thresholds are substantially lower than published Se toxicity values for reproductive effects in other freshwater fish (for example, 17–24 μg/g in eggs). Reduced egg production has not been reported as a sensitive endpoint in Se toxicity studies, although abnormal ovarian development has been reported in Se-exposed fish, and reduced egg production has been reported as a sensitive response of other Cyprinodon pupfish to other environmental stressors. Selenium concentrations in tissues of pupfish, mollies, and diet items from Imperial Valley sites frequently exceeded concentrations associated with reduced pupfish egg production in the laboratory study. Reduced egg production may limit the ability of pupfish populations to persist and recover in Se-contaminated habitats in the Imperial Valley and elsewhere in their limited range. However, these apparent risks of Se toxicity are not supported by recent surveys of desert pupfish populations in the Imperial Valley. These surveys indicated that desert pupfish made up a small, but variable, component of fish communities in Imperial Valley habitats, including sites with increased levels of Se exposure, and that pupfish distribution and population density indicated no clear relationships with Se concentrations in diets or fish tissues. Additional studies could determine the role of egg production in the maintenance and recovery of desert pupfish populations in Se-contaminated habitats.

Scientific Investigations Report↗

Equations for estimating bankfull channel geometry and discharge for streams in Massachusetts

Regression equations were developed for estimating bankfull geometry—width, mean depth, cross-sectional area—and discharge for streams in Massachusetts. The equations provide water-resource and conservation managers with methods for estimating bankfull characteristics at specific stream sites in Massachusetts. This information can be used for the adminstration of the Commonwealth of Massachusetts Rivers Protection Act of 1996, which establishes a protected riverfront area extending from the mean annual high-water line corresponding to the elevation of bankfull discharge along each side of a perennial stream. Additionally, information on bankfull channel geometry and discharge are important to Federal, State, and local government agencies and private organizations involved in stream assessment and restoration projects. Regression equations are based on data from stream surveys at 33 sites (32 streamgages and 1 crest-stage gage operated by the U.S. Geological Survey) in and near Massachusetts. Drainage areas of the 33 sites ranged from 0.60 to 329 square miles (mi2). At 27 of the 33 sites, field data were collected and analyses were done to determine bankfull channel geometry and discharge as part of the present study. For 6 of the 33 sites, data on bankfull channel geometry and discharge were compiled from other studies done by the U.S. Geological Survey, Natural Resources Conservation Service of the U.S. Department of Agriculture, and the Vermont Department of Environmental Conservation. Similar techniques were used for field data collection and analysis for bankfull channel geometry and discharge at all 33 sites. Recurrence intervals of the bankfull discharge, which represent the frequency with which a stream fills its channel, averaged 1.53 years (median value 1.34 years) at the 33 sites. Simple regression equations were developed for bankfull width, mean depth, cross-sectional area, and discharge using drainage area, which is the most significant explanatory variable in estimating these bankfull characteristics. The use of drainage area as an explanatory variable is also the most commonly published method for estimating these bankfull characteristics. Regional curves (graphic plots) of bankfull channel geometry and discharge by drainage area are presented. The regional curves are based on the simple regression equations and can be used to estimate bankfull characteristics from drainage area. Multiple regression analysis, which includes basin characteristics in addition to drainage area, also was used to develop equations. Variability in bankfull width, mean depth, cross-sectional area, and discharge was more fully explained by the multiple regression equations that include mean-basin slope and drainage area than was explained by equations based on drainage area alone. The Massachusetts regional curves and equations developed in this study are similar, in terms of values of slopes and intercepts, to those developed for other parts of the northeastern United States. Limitations associated with site selection and development of the equations resulted in some constraints for the application of equations and regional curves presented in this report. The curves and equations are applicable to stream sites that have (1) less than about 25 percent of their drainage basin area occupied by urban land use (commercial, industrial, transportation, and high-density residential), (2) little to no streamflow regulation, especially from flood-control structures, (3) drainage basin areas greater than 0.60 mi2 and less than 329 mi2, and (4) a mean basin slope greater than 2.2 percent and less than 23.9 percent. The equations may not be applicable where streams flow through extensive wetlands. The equations also may not apply in areas of Cape Cod and the Islands and the area of southeastern Massachusetts close to Cape Cod with extensive areas of coarse-grained glacial deposits where none of the study sites are located. Regardless of the setting, the regression equations are not intended for use as the sole method of estimating bankfull characteristics; however, they may supplement field identification of the bankfull channel when used in conjunction with field verified bankfull indicators, flood-frequency analysis, or other supporting evidence.

Massachusetts↗

A preliminary survey of marine contamination from mining-related activities on Marinduque Island, Philippines: porewater toxicity and chemistry results from a field trip, October 14-19, 2000

As a follow-up of an initial overview of environmental problems caused by mining activities on Marinduque Island, Philippines, USGS and TAMU-CC scientists went to Marinduque in October 2000 to do a preliminary assessment of potential impacts of mining-related activities on the marine environment. Like the previous visit in May 2000, the marine assessment was conducted at the invitation of Philippine Congressman Edmund O. Reyes. In this report we present the results of sediment porewater toxicity tests and chemical analyses. Toxicity tests consist of laboratory analyses for the assessment of adverse effects caused by environmental contaminants to animals or plants. Sediments (sand or mud) are known to accumulate contaminants (e.g., copper and other heavy metals). Therefore, it is common to perform toxicity tests using different phases of the sedimentary environment in order to analyze adverse effects of contaminants accumulated in the sediment. Sediment pore water (or interstitial water, i.e., the water distributed among the sediment grains) is a sedimentary phase which controls the bioavailability of contaminants to bottom dwelling aquatic organisms (both plants and animals). There are several different kinds of organisms with which toxicity tests can be performed. Among those, tests with sea urchin early life stages (gametes and embryos) are very common due to their high sensitivity to contaminants, ease of maintenance under laboratory conditions, and ecological importance, particularly in coral reefs. The basis of these tests is the exposure of gametes or embryos to the pore water to be analyzed for toxicity. If the pore water contains contaminants in levels that can adversely affect a number of marine species, fertilization and/or embryological development of sea urchins is inhibited. Chemical analyses provide additional information and aid in the interpretation of the toxicity test results. For the current study, chemical analyses were performed for the measurement of porewater concentrations of several heavy metals associated with copper mining activities. Pore waters for toxicological and chemical analyses were collected at several stations on the coast of Marinduque, near the mouths of the Boac and Mogpog rivers, and near the causeways formed by mine tailings disposal. Porewater samples were also collected at the Tres Reyes Marine Reserve, so that these non-contaminated samples could serve as a reference for test performance. Sea urchin embryological development and fertilization were only significantly impaired by two porewater samples, suggesting the presence of contaminants in toxic amounts at those stations. The toxic samples were collected near the up current side of the Calancan (Marcopper) mine tailings causeway (stations 2 and 3 – see figure 10). The pore water from station 2 also had the highest levels of heavy metals, particularly cadmium, cobalt, copper, nickel, lead and zinc (Table 5). The concentrations of cobalt, nickel and zinc were also elevated 2 at station 3. Copper concentrations were also elevated at the two river mouth stations (8 and 9) and near the CMI tailings causeway (station 7). Visual observations also indicated biological degradation due to heavy siltation and smothered coral at a gradient off the Calancan causeway, suggesting that siltation might also be causing a physical impact. This preliminary survey suggests that effects related to past mining activities are still evident and warrant a more comprehensive study to assess their severity and areal extent.

Open-File Report↗

Cancer risk and estimated lithium exposure in drinking groundwater in the US

Importance Lithium is a naturally occurring element in drinking water and is commonly used as a mood-stabilizing medication. Although clinical studies have reported associations between receiving lithium treatment and reduced cancer risk among patients with bipolar disorder, to our knowledge, the association between environmental lithium exposure and cancer risk has never been studied in the general population. Objectives To evaluate the association between exposure to lithium in drinking groundwater and cancer risk in the general population. Design, Setting, and Participants This cohort study included participants with electronic health record and residential address information but without cancer history at baseline from the All of Us Research Program between May 31, 2017, and June 30, 2022. Participants were followed up until February 15, 2023. Statistical analysis was performed from September 2023 through October 2024. Exposure Lithium concentration in groundwater, based on kriging interpolation of publicly available US Geological Survey data on lithium concentration for 4700 wells across the contiguous US between May 12, 1999, and November 6, 2018. Main Outcome and Measures The main outcome was cancer diagnosis or condition, obtained from electronic health records. Stratified Cox proportional hazards regression models were used to estimate the hazard ratios (HRs) and 95% CIs for risk of cancer overall and individual cancer types for increasing quintiles of the estimated lithium exposure in drinking groundwater, adjusting for socioeconomic, behavioral, and neighborhood-level variables. The analysis was further conducted in the western and eastern halves of the US and restricted to long-term residents living at their current address for at least 3 years. Results A total of 252 178 participants were included (median age, 52 years [IQR, 36-64 years]; 60.1% female). The median follow-up time was 3.6 years (IQR, 3.0-4.3 years), and 7573 incident cancer cases were identified. Higher estimated lithium exposure was consistently associated with reduced cancer risk. Compared with the first (lowest) quintile of lithium exposure, the HR for all cancers was 0.49 (95% CI, 0.31-0.78) for the fourth quintile and 0.29 (95% CI, 0.15-0.55) for the fifth quintile. These associations were found for all cancer types investigated in both females and males, among long-term residents, and in both western and eastern states. For example, for the fifth vs first quintile of lithium exposure for all cancers, the HR was 0.17 (95% CI, 0.07-0.42) in females and 0.13 (95% CI, 0.04-0.38) in males; for long-term residents, the HR was 0.32 (95% CI, 0.15-0.66) in females and 0.24 (95% CI, 0.11-0.52) in males; and the HR was 0.01 (95% CI, 0.00-0.09) in western states and 0.34 (95% CI, 0.21-0.57) in eastern states. Conclusions and Relevance In this cohort study of 252 178 participants, estimated lithium exposure in drinking groundwater was associated with reduced cancer risk. Given the sparse evidence and unknown mechanisms of this association, follow-up investigation is warranted.

contiguous United States↗

Using semi-permeable membrane devices and stable nitrogen isotopes to detect anthropogenic influences on the Truckee River, USA

Stable nitrogen isotopes (??15N) and semipermeable membrane devices (SPMDs) were used together to provide evidence of potential anthropogenic connections to aquatic organisms in the Truckee River, which flows through the Reno/Sparks metropolitan area in Nevada. Crayfish, snail, and periphyton ??15N values, and SPMD toxicity data collected during high and low flow periods at seven primary sites on the river were used with water quality and flow data for the assessment. All biota showed an increase of ??15N on both dates at sites downstream of inflows of a water-quality impaired tributary and urban drain relative to upstream. In addition, most of the lowest ??15N values on each date occurred at the most downstream site on the river. SPMDs sample lipophilic organic contaminants and can be used to assess organic contaminant toxicity to aquatic organisms because they use a membrane that mimics organic contaminant uptake by fish. In this study, results from a fluoroscan test [pyrene index (PI)] of SPMD extracts that responds to higher molecular weight polycyclic aromatic hydrocarbons (PAHs) showed patterns similar to stable isotope data, although observed peaks in PI values occurred in the urban area upstream of where peak ??15N values occurred. The CYP1A biomarker test, which responds to PAHs, certain polychlorinated biphenyls (PCBs), and organochlorines, showed peak toxic equivalents (TEQ) values farther downstream of the urban area. Thus, it is likely that PAHs were contributing to toxicity in the urban area, whereas other nonurban sources of organic carbon may have been present farther downstream. The combined use of stable isotope measurements and SPMDs provided a means of simultaneously examining whether aquatic biota are incorporating constituents from potential food sources (via stable isotopes) or exposure through water (via SPMDs). ?? Mary Ann Liebert, Inc. 2008.

Environmental Engineering Science↗

Occurrence of cyanobacteria, microcystin, and taste-and-odor compounds in Cheney Reservoir, Kansas, 2001-16

Cheney Reservoir, located in south-central Kansas, is one of the primary drinking-water supplies for the city of Wichita and an important recreational resource. Since 1990, cyanobacterial blooms have been present occasionally in Cheney Reservoir, resulting in increased treatment costs and decreased recreational use. Cyanobacteria, the cyanotoxin microcystin, and the taste-and-odor compounds geosmin and 2-methylisoborneol have been measured in Cheney Reservoir by the U.S. Geological Survey, in cooperation with the city of Wichita, for about 16 years. The purpose of this report is to describe the occurrence of cyanobacteria, microcystin, and taste-and-odor compounds in Cheney Reservoir during May 2001 through June 2016 and to update previously published logistic regression models that used continuous water-quality data to estimate the probability of microcystin and geosmin occurrence above relevant thresholds. Cyanobacteria, microcystin, and geosmin were detected in about 84, 52, and 31 percent of samples collected in Cheney Reservoir during May 2001 through June 2016, respectively. 2-methylisoborneol was less common, detected in only 3 percent of samples. Microcystin and geosmin concentrations exceeded advisory values of concern more frequently than cyanobacterial abundance; therefore, cyanobacteria are not a good indicator of the presence of these taste-and-odor compounds in Cheney Reservoir. Broad seasonal patterns in cyanobacteria and microcystin were evident, though abundance and concentration varied by orders of magnitude across years. Cyanobacterial abundances generally peaked in late summer or early fall (August through October), and smaller peaks were observed in winter (January through February). In a typical year, microcystin was first detected in June or July, increased to its seasonal maxima in the summer (July through September), and then decreased. Seasonal patterns in geosmin were less consistent than cyanobacteria and microcystin, but geosmin typically had a small peak during winter (January through March) during most years and a large peak during summer (July through September) during some years. Though the relation between cyanobacterial abundance and microcystin and geosmin concentrations was positive, overall correlations were weak, likely because production is strain-specific and cyanobacterial strain composition may vary substantially over time. Microcystin often was present without taste-and-odor compounds. By comparison, where taste-and-odor compounds were present, microcystin frequently was detected. Taste-and-odor compounds, therefore, may be used as indicators that microcystin may be present; however, microcystin was present without taste-and-odor compounds, so taste or odor alone does not provide sufficient warning to ensure human-health protection. Logistic regression models that estimate the probability of microcystin occurrence at concentrations greater than or equal to 0.1 micrograms per liter and geosmin occurrence at concentrations greater than or equal to 5 nanograms per liter were developed. Models were developed using the complete dataset (January 2003 through June 2016 for microcystin [14-year dataset]; May 2001 through June 2016 for geosmin [16-year dataset]) and an abbreviated 4-year dataset (January 2013 through June 2016 for microcystin and geosmin). Performance of the newly developed models was compared with previously published models that were developed using data collected during May 2001 through December 2009. A seasonal component and chlorophyll fluorescence (a surrogate for algal biomass) were the explanatory variables for microcystin occurrence at concentrations greater than or equal to 0.1 micrograms per liter in all models. All models were relatively robust, though the previously published and 14-year models performed better over time; however, as a tool to estimate microcystin occurrence at concentrations greater than or equal to 0.1 micrograms per liter in a real-time notification system near the Cheney Dam, the 4-year model is most representative of recent (2013 through 2016) conditions. All models for geosmin occurrence at concentrations greater than or equal to 5 nanograms per liter had different explanatory variables and model forms. The previously published and 16-year models were not robust over time, likely because of changing environmental conditions and seasonal patterns in geosmin occurrence. By comparison, the abbreviated 4-year model may be a useful tool to estimate geosmin occurrence at concentrations greater than or equal to 5 nanograms per liter in a real-time notification system near the Cheney Dam. The better performance of the abbreviated 4-year geosmin model during 2013 through 2016 relative to the previously published and 16-year models demonstrates the need for continuous reevaluation of models estimating the probability of occurrence.

Kansas↗

Quality characteristics of ground water in the Ozark aquifer of northwestern Arkansas, southeastern Kansas, southwestern Missouri and northeastern Oklahoma, 2006-07

Because of water quantity and quality concerns within the Ozark aquifer, the State of Kansas in 2004 issued a moratorium on most new appropriations from the aquifer until results were made available from a cooperative study between the U.S. Geological Survey and the Kansas Water Office. The purposes of the study were to develop a regional ground-water flow model and a water-quality assessment of the Ozark aquifer in northwestern Arkansas, southeastern Kansas, southwestern Missouri, and northeastern Oklahoma (study area). In 2006 and 2007, water-quality samples were collected from 40 water-supply wells completed in the Ozark aquifer and spatially distributed throughout the study area. Samples were analyzed for physical properties, dissolved solids and major ions, nutrients, trace elements, and selected isotopes. This report presents the results of the water-quality assessment part of the cooperative study. Water-quality characteristics were evaluated relative to U.S. Environmental Protection Agency drinking-water standards. Secondary Drinking-Water Regulations were exceeded for dissolved solids (11 wells), sulfate and chloride (2 wells each), fluoride (3 wells), iron (4 wells), and manganese (2 wells). Maximum Contaminant Levels were exceeded for turbidity (3 wells) and fluoride (1 well). The Maximum Contaminant Level Goal for lead (0 milligrams per liter) was exceeded in water from 12 wells. Analyses of isotopes in water from wells along two 60-mile long ground-water flow paths indicated that water in the Ozark aquifer was at least 60 years old but the upper age limit is uncertain. The source of recharge water for the wells along the flow paths appeared to be of meteoric origin because of isotopic similarity to the established Global Meteoric Water Line and a global precipitation relation. Additionally, analysis of hydrogen-3 (3H) and carbon-14 (14C) indicated that there was possible leakage of younger ground water into the lower part of the Ozark aquifer. This may be caused by cracks or fissures in the confining unit that separates the upper and lower parts of the aquifer, poorly constructed or abandoned wells, or historic mining activities. Analyses of major ions in water from wells along the flow paths indicated a transition from freshwater in the east to saline water in the west. Generally, ground water along flow paths evolved from a calcium magnesium bicarbonate type to a sodium calcium bicarbonate or a sodium calcium chloride bicarbonate type as water moved from recharge areas in Missouri into Kansas. Much of this evolution occurred within the last 20 to 25 miles of the flow paths along a water-quality transition zone near the Kansas-Missouri State line and west. The water quality of the Kansas part of the Ozark aquifer is degraded compared to the Missouri part. Geophysical and well-bore flow information and depth-dependent water-quality samples were collected from a large-capacity (1,900-2,300 gallons per minute) municipal-supply well to evaluate vertical ground-water flow accretion and variability in water-quality characteristics at different levels. Although the 1,050-foot deep supply well had 500 feet of borehole open to the Ozark aquifer, 77 percent of ground-water flow entering the borehole came from two 20-foot thick rock layers above the 1,000-foot level. For the most part, water-quality characteristics changed little from the deepest sample to the well-head sample, and upwelling of saline water from deeper geologic formations below the well was not evident. However, more saline water may be present below the bottom of the well.

Arkansas, Kansas, Missouri, Oklahoma↗

Subsurface occurrence and potential source areas of chlorinated ethenes identified using concentrations and concentration ratios, Air Force Plant 4 and Naval Air Station-Joint Reserve Base Carswell Field, Fort Worth, Texas

The U.S. Geological Survey, in cooperation with the U.S. Air Force Aeronautical Systems Center, Environmental Management Directorate, conducted a study during 2003-05 to characterize the subsurface occurrence and identify potential source areas of the volatile organic compounds classified as chlorinated ethenes at U.S. Air Force Plant 4 (AFP4) and adjacent Naval Air Station-Joint Reserve Base Carswell Field (NAS-JRB) at Fort Worth, Texas. The solubilized chlorinated ethenes detected in the alluvial aquifer originated as either released solvents (tetrachloroethene [PCE], trichloroethene [TCE], and trans -1,2-dichloroethene [ trans -DCE]) or degradation products of the released solvents (TCE, cis -1,2-dichloroethene [ cis -DCE], and trans -DCE). The combined influences of topographic- and bedrock-surface configurations result in a water table that generally slopes away from a ground-water divide approximately coincident with bedrock highs and the 1-mile-long aircraft assembly building at AFP4. Highest TCE concentrations (10,000 to 920,000 micrograms per liter) occur near Building 181, west of Building 12, and at landfill 3. Highest PCE concentrations (500 to 920 micrograms per liter) occur near Buildings 4 and 5. Highest cis -DCE concentrations (5,000 to 710,000 micrograms per liter) occur at landfill 3. Highest trans -DCE concentrations (1,000 to 1,700 micrograms per liter) occur just south of Building 181 and at landfill 3. Ratios of parent-compound to daughter-product concentrations that increase in relatively short distances (tens to 100s of feet) along downgradient ground-water flow paths can indicate a contributing source in the vicinity of the increase. Largest increases in ratio of PCE to TCE concentrations are three orders of magnitude from 0.01 to 2.7 and 7.1 between nearby wells in the northeastern part of NAS-JRB. In the northern part of NAS-JRB, the largest increases in TCE to total DCE concentration ratios relative to ratios at upgradient wells are from 17 to 240 or from 17 to 260. In the southern part of NAS-JRB, the largest ratio increases with respect to those at upgradient wells are from 22 and 24 to 130, and from 0 and 7.2 to 71. Numerous maximum historical ratios of trans -DCE to cis -DCE are greater than 1, which can indicate that trans -DCE likely was released as a solvent and does not occur only as a result of degradation of TCE. High concentrations of TCE, PCE, cis -DCE, and trans -DCE, abrupt increases in ratios of PCE to TCE and TCE to total DCE, and ratios of trans -DCE to cis -DCE greater than 1 were used to identify 16 potential source areas of chlorinated ethenes at NAS-JRB. The evidence for some of the potential source areas is stronger than for others, but each area reflects one or more of the conditions indicative of chlorinated ethenes entering the aquifer. Potential source areas supported by the strongest evidence are Building 181, between buildings 4 and 5, just west of Building 12, and landfills 1 and 3. The highest historical TCE concentration in the study area, 920,000 micrograms per liter, is near Building 181. The potential source area between Buildings 4 and 5 primarily is identified by notably high PCE concentrations (to 920 micrograms per liter). Primary evidence for the potential source are just west of Building 12 is the notably high TCE concentrations (for example, 160,000 micrograms per liter) that appear to originate in the area. Primary evidence for the potential source area at landfills 1 and (primarily) 3 is the magnitudes of TCE concentrations (for example, two in the 100,000-to-920,000-microgram-per-liter range), cis -DCE concentrations (several in the 5,000-to-710,000-microgram-per-liter range), and trans -DCE concentrations (several in the 500-to-1,700-microgram-per-liter range). The ratio of trans -DCE to cis -DCE at one well in landfill 3 (6.7) is appreciably above the threshold that can indicate likely solvent release as opposed to TCE degradation alone.

Texas↗

Geochemical and isotopic variations in shallow groundwater in areas of the Fayetteville Shale development, north-central Arkansas

Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH 4 gas content and its C isotopes (&delta; 13 C CH4 ), and select isotope tracers (&delta; 11 B, 87 Sr/ 86 Sr, &delta; 2 H, &delta; 18 O, &delta; 13 C DIC ) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH 4 was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5 mg CH 4 /L. The &delta; 13 C CH4 of dissolved CH 4 ranged from &minus;42.3&permil; to &minus;74.7&permil;, with the most negative values characteristic of a biogenic source also associated with the highest observed CH 4 concentrations, with a possible minor contribution of trace amounts of thermogenic CH 4 . The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (&delta; 13 C CH4 = &minus;35.4&permil; to &minus;41.9&permil;). Based on major element chemistry, four shallow groundwater types were identified: (1) low (<100 mg/L) total dissolved solids (TDS), (2) TDS > 100 mg/L and Ca&ndash;HCO 3 dominated, (3) TDS > 100 mg/L and Na&ndash;HCO 3 dominated, and (4) slightly saline groundwater with TDS > 100 mg/L and Cl > 20 mg/L with elevated Br/Cl ratios (>0.001). The Sr ( 87 Sr/ 86 Sr = 0.7097&ndash;0.7166), C (&delta; 13 C DIC = &minus;21.3&permil; to &minus;4.7&permil;), and B (&delta; 11 B = 3.9&ndash;32.9&permil;) isotopes clearly reflect water&ndash;rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca&ndash;HCO 3 , and higher-mineralized Na&ndash;HCO 3 composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na&ndash;Cl type Fayetteville flowback/produced waters (TDS &sim;10,000&ndash;20,000 mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH 4 and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale.

Applied Geochemistry↗

Final report: Baseline selenium monitoring of agricultural drains operated by the Imperial Irrigation District in the Salton Sea Basin

This report summarizes comprehensive findings from a 4-year-long field investigation to document baseline environmental conditions in 29 agricultural drains and ponds operated by the Imperial Irrigation District along the southern border of the Salton Sea. Routine water-quality collections and fish community assessments were conducted on as many as 16 sampling dates at roughly quarterly intervals from July 2005 to April 2009. The water-quality measurements included total suspended solids and total (particulate plus dissolved) selenium. With one exception, fish were surveyed with baited minnow traps at quarterly intervals during the same time period. However, in July 2007, fish surveys were not conducted because we lacked permission from the California Department of Fish and Game for incidental take of desert pupfish ( Cyprinodon macularius ), an endangered species. During April and October 2006–08, water samples also were collected from seven intensively monitored drains (which were selected from the 29 total drains) for measurement of particulate and dissolved selenium, including inorganic and organic fractions. In addition, sediment, aquatic food chain matrices [particulate organic detritus, filamentous algae, net plankton, and midge (chironomid) larvae], and two fish species (western mosquitofish, Gambusia affinis ; and sailfin molly, Poecilia latipinna ) were sampled from the seven drains for measurement of total selenium concentrations. The mosquitofish and mollies were intended to serve as surrogates for pupfish, which we were not permitted to sacrifice for selenium determinations. Water quality (temperature, dissolved oxygen, pH, specific conductance, and turbidity) values were typical of surface waters in a hot, arid climate. A few drains exhibited brackish, near-anoxic conditions, especially during summer and fall when water temperatures occasionally exceeded 30 degrees Celsius. Total selenium concentrations in water were directly correlated with salinity and inversely correlated with total suspended-solids concentrations. Although pupfish were found in several drains, sometimes in relatively high numbers, the fish faunas of most drains and ponds were dominated by nonnative species, especially mosquitofish, mollies, and red shiner ( Cyprinella lutrensis ). Dissolved selenium in water samples from the seven intensively monitored drains ranged from 0.700 to 32.8 micrograms per liter (?g/L), with selenate as the major constituent. Selenium concentrations in other matrices varied widely among drains and ponds, with one drain (Trifolium 18) exhibiting especially high concentrations in food chain matrices [particulate organic detritus, 5.98–58.0 micrograms of selenium per gram (?g Se/g); midge larvae, 12.7–50.6 ?g Se/g] and in fish (mosquitofish, 13.2–20.2 ?g Se/g; sailfin mollies, 12.8–30.4 ?g Se/g; all concentrations are based on dry weights). Although selenium was accumulated by all trophic levels, biomagnification (defined as a progressive increase in selenium concentration from one trophic level to the next higher level) in midge larvae and fish occurred only at lower exposure concentrations. Judging mostly from circumstantial evidence, the health and wellbeing of poeciliids and pupfish are not believed to be threatened by ambient exposure to selenium in the drains and ponds.

California↗