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Diets of nesting laughing gulls (Larus atricilla) at the Virginia Coast Reserve: observations from stable isotope analysis

Food web studies often ignore details of temporal, spatial, and intrapopulation dietary variation in top-level consumers. In this study, intrapopulation dietary variation of a dominant carnivore, the Laughing Gull ( Larus atricilla ), was examined using carbon, nitrogen, and sulfur isotope analysis of gull tissues as well as their prey (fish, invertebrates, and insects) from the Virginia Coast Reserve estuarine system. As earlier traditional diet studies found evidence of individual dietary specialization within gull populations, this study used stable isotope analysis to assess specialization in a coastal Laughing Gull population. Specifically, blood, muscle, and feather isotope values indicated significant intrapopulation dietary specialization. Some gulls relied more heavily on estuarine prey (mean blood δ 13 C = -17.5, δ 15 N = 12.6, and δ 34 S = 9.3), whereas others appeared to consume more foods of marine origin (mean blood δ 13 C = -19.4, δ 15 N = 14.8, and δ 34 S = 10.4). It is important to account for such dietary variability when assessing trophic linkages in dynamic estuarine systems.

Isotopes in Environmental and Health Studies

Online induction heating for determination of isotope composition of woody stem water with laser spectrometry: A methods assessment

Application of stable isotopes of water to studies of plant–soil interactions often requires a substantial preparatory step of extracting water from samples without fractionating isotopes. Online heating is an emerging approach for this need, but is relatively untested and major questions of how to best deliver standards and assess interference by organics have not been evaluated. We examined these issues in our application of measuring woody stem xylem of sagebrush using a Picarro laser spectrometer with online induction heating. We determined (1) effects of cryogenic compared to induction-heating extraction, (2) effects of delivery of standards on filter media compared to on woody stem sections, and (3) spectral interference from organic compounds for these approaches (and developed a technique to do so). Our results suggest that matching sample and standard media improves accuracy, but that isotopic values differ with the extraction method in ways that are not due to spectral interference from organics.

Isotopes in Environmental and Health Studies

Stable isotope deltas: Tiny, yet robust signatures in nature

Although most of them are relatively small, stable isotope deltas of naturally occurring substances are robust and enable workers in anthropology, atmospheric sciences, biology, chemistry, environmental sciences, food and drug authentication, forensic science, geochemistry, geology, oceanography, and paleoclimatology to study a variety of topics. Two fundamental processes explain the stable isotope deltas measured in most terrestrial systems: isotopic fractionation and isotope mixing. Isotopic fractionation is the result of equilibrium or kinetic physicochemical processes that fractionate isotopes because of small differences in physical or chemical properties of molecular species having different isotopes. It is shown that the mixing of radioactive and stable isotope end members can be modelled to provide information on many natural processes, including 14C abundances in the modern atmosphere and the stable hydrogen and oxygen isotopic compositions of the oceans during glacial and interglacial times. The calculation of mixing fractions using isotope balance equations with isotope deltas can be substantially in error when substances with high concentrations of heavy isotopes (e.g. 13C, 2H, and 18O ) are mixed. In such cases, calculations using mole fractions are preferred as they produce accurate mixing fractions. Isotope deltas are dimensionless quantities. In the International System of Units (SI), these quantities have the unit 1 and the usual list of prefixes is not applicable. To overcome traditional limitations with expressing orders of magnitude differences in isotope deltas, we propose the term urey (symbol Ur), after Harold C. Urey, for the unit 1. In such a manner, an isotope delta value expressed traditionally as−25 per mil can be written as−25 mUr (or−2.5 cUr or−0.25 dUr; the use of any SI prefix is possible). Likewise, very small isotopic differences often expressed in per meg ‘units’ are easily included (e.g. either+0.015 ‰ or+15 per meg can be written as+15 μUr.

Isotopes in Environmental and Health Studies

Quality assurance and quality control in light stable isotope laboratories: A case study of Rio Grande, Texas, water samples

New isotope laboratories can achieve the goal of reporting the same isotopic composition within analytical uncertainty for the same material analysed decades apart by (1) writing their own acceptance testing procedures and putting them into their mass spectrometric or laser-based isotope-ratio equipment procurement contract, (2) requiring a manufacturer to demonstrate acceptable performance using all sample ports provided with the instrumentation, (3) for each medium to be analysed, prepare two local reference materials substantially different in isotopic composition to encompass the range in isotopic composition expected in the laboratory and calibrated them with isotopic reference materials available from the International Atomic Energy Agency (IAEA) or the US National Institute of Standards and Technology (NIST), (4) using the optimum storage containers (for water samples, sealing in glass ampoules that are sterilised after sealing is satisfactory), (5) interspersing among sample unknowns local laboratory isotopic reference materials daily (internationally distributed isotopic reference materials can be ordered at three-year intervals, and can be used for elemental analyser analyses and other analyses that consume less than 1 mg of material) – this process applies to H, C, N, O, and S isotope ratios, (6) calculating isotopic compositions of unknowns by normalising isotopic data to that of local reference materials, which have been calibrated to internationally distributed isotopic reference materials, (7) reporting results on scales normalised to internationally distributed isotopic reference materials (where they are available) and providing to sample submitters the isotopic compositions of internationally distributed isotopic reference materials of the same substance had they been analysed with unknowns, (8) providing an audit trail in the laboratory for analytical results – this trail commonly will be in electronic format and might include a laboratory information management system, (9) making at regular intervals a complete backup of laboratory analytical data (both of samples logged into the laboratory and of mass spectrometric analyses), being sure to store one copy of this backup offsite, and (10) participating in interlaboratory comparison exercises sponsored by the IAEA and other agencies at regular intervals.

Isotopes in Environmental and Health Studies

On the conversion of tritium units to mass fractions for hydrologic applications

We develop a general equation for converting laboratory-reported tritium levels, expressed either as concentrations (tritium isotope number fractions) or mass-based specific activities, to mass fractions in aqueous systems. Assuming that all tritium is in the form of monotritiated water simplifies the derivation and is shown to be reasonable for most environmental settings encountered in practice. The general equation is nonlinear. For tritium concentrations c less than 4.5×10 12 tritium units (TU) - i.e. specific tritium activities<5.3×10 11 Bq kg -1 - the mass fraction w of tritiated water is approximated to within 1 part per million by w ≈ c×2.22293×10 -18 , i.e. the conversion is linear for all practical purposes. Terrestrial abundances serve as a proxy for non-tritium isotopes in the absence of sample-specific data. Variation in the relative abundances of non-tritium isotopes in the terrestrial hydrosphere produces a minimum range for the mantissa of the conversion factor of [2.22287; 2.22300].

Isotopes in Environmental and Health Studies

USGS48 Puerto Rico precipitation - A new isotopic reference material for δ 2 H and δ 18 O measurements of water

A new secondary isotopic reference material has been prepared from Puerto Rico precipitation, which was filtered, homogenised, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity, and calibrated by dual-inlet isotope-ratio mass spectrometry. This isotopic reference material, designated as USGS48, is intended to be one of two isotopic reference waters for daily normalisation of stable hydrogen (δ 2 H) and stable oxygen (δ 18 O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The δ 2 H and δ 18 O values of this reference water are−2.0±0.4 and−2.224±0.012 ‰, respectively, relative to Vienna Standard Mean Ocean Water on scales normalised such that the δ 2 H and δ 18 O values of Standard Light Antarctic Precipitation reference water are−428 and−55.5 ‰, respectively. Each uncertainty is an estimated expanded uncertainty ( U =2 u c ) about the reference value that provides an interval that has about a 95 % probability of encompassing the true value. This isotopic reference water is available by the case of 144 glass ampoules containing 5 mL of water in each ampoule.

Puerto Rico

Carbon isotope analysis of dissolved organic carbon in fresh and saline (NaCl) water via continuous flow cavity ring-down spectroscopy following wet chemical oxidation

This work examines the performance and limitations of a wet chemical oxidation carbon analyser interfaced with a cavity ring-down spectrometer (WCO-CRDS) in a continuous flow (CF) configuration for measuring &delta; 13 C of dissolved organic carbon ( &delta; 13 C-DOC) in natural water samples. Low-chloride matrix (<5 g Cl/L) DOC solutions were analysed with as little as 2.5 mg C/L in a 9 mL aliquot with a precision of 0.5 &permil;. In high-chloride matrix (10&ndash;100 g Cl/L) DOC solutions, bias towards lighter &delta; 13 C-DOC was observed because of incomplete oxidation despite using high-concentration oxidant, extended reaction time, or post-wet chemical oxidation gas-phase combustion. However, through a combination of dilution, chloride removal, and increasing the oxidant:sample ratio, high-salinity samples with sufficient DOC (>22.5 &micro;g C/aliquot) may be analysed. The WCO-CRDS approach requires more total carbon (&micro;g C/aliquot) than conventional CF-isotope ratio mass spectrometer, but is nonetheless applicable to a wide range of DOC concentration and water types, including brackish water, produced water, and basinal brines.

Isotopes in Environmental and Health Studies

Occurrence and hydrogeochemistry of radiochemical constituents in groundwater of Jefferson County and surrounding areas, southwestern Montana, 2007 through 2010

The U.S. Geological Survey, in cooperation with Jefferson County and the Jefferson Valley Conservation District, sampled groundwater in southwestern Montana to evaluate the occurrence and concentration of naturally-occurring radioactive constituents and to identify geologic settings and environmental conditions in which elevated concentrations occur. A total of 168 samples were collected from 128 wells within Broadwater, Deer Lodge, Jefferson, Lewis and Clark, Madison, Powell, and Silver Bow Counties from 2007 through 2010. Most wells were used for domestic purposes and were primary sources of drinking water for individual households. Water-quality samples were collected from wells completed within six generalized geologic units, and analyzed for constituents including uranium, radon, gross alpha-particle activity, and gross beta-particle activity. Thirty-eight wells with elevated concentrations or activities were sampled a second time to examine variability in water quality throughout time. These water-quality samples were analyzed for an expanded list of radioactive constituents including the following: three isotopes of uranium (uranium-234, uranium-235, and uranium-238), three isotopes of radium (radium-224, radium-226, and radium-228), and polonium-210. Existing U.S. Geological Survey and Montana Bureau of Mines and Geology uranium and radon water-quality data collected as part of other investigations through 2011 from wells within the study area were compiled as part of this investigation. Water-quality data from this study were compared to data collected nationwide by the U.S. Geological Survey through 2011. Radionuclide samples for this study typically were analyzed within a few days after collection, and therefore data for this study may closely represent the concentrations and activities of water being consumed locally from domestic wells. Radioactive constituents were detected in water from every well sampled during this study regardless of location or geologic unit. Nearly 41 percent of sampled wells had at least one radioactive constituent concentration that exceeded U.S. Environmental Protection Agency drinking-water standards or screening levels. Uranium concentrations were higher than the U.S. Environmental Protection Agency maximum contaminant level (MCL) of 30 micrograms per liter in samples from 14 percent of the wells. Radon concentrations exceeded a proposed MCL of 4,000 picocuries per liter in 27 percent of the wells. Combined radium (radium-226 and radium-228) exceeded the MCL of 5 picocuries per liter in samples from 10 of 47 wells. About 40 percent (42 of 104 wells) of the wells had gross alpha-particle activities (72-hour count) at or greater than a screening level of 15 pCi/L. Gross beta-particle activity exceeded the U.S. Environmental Protection Agency 50 picocuries per liter screening level in samples from 5 of 104 wells. Maximum radium-224 and polonium-210 activities in study wells were 16.1 and 3.08 picocuries per liter, respectively; these isotopes are constituents of human-health concern, but the U.S. Environmental Protection Agency has not established MCLs for them. Radioactive constituent concentrations or activities exceeded at least one established drinking-water standard, proposed drinking-water standard, or screening level in groundwater samples from five of six generalized geologic units assessed during this study. Radioactive constituent concentrations or activities were variable not only within each geologic unit, but also among wells that were completed in the same geologic unit and in close proximity to one another. Established or proposed drinking-water standards were exceeded most frequently in water from wells completed in the generalized geologic unit that includes rocks of the Boulder batholith and other Tertiary through Cretaceous igneous intrusive rocks (commonly described as granite). Specifically, of the wells completed in the Boulder batholith and related rocks sampled as part of this study, 24 percent exceeded the MCL of 30 micrograms per liter for uranium, 50 percent exceeded the proposed alternative MCL of 4,000 picocuries per liter for radon, and 27 percent exceeded the MCL of 5 micrograms per liter for combined radium-226 and radium-228. Elevated radioactive constituent values were detected in samples representing a large range of field properties and water types. Correlations between radioactive constituents and pH, dissolved oxygen, and most major ions were not statistically significant (p-value > 0.05) or were weakly correlated with Spearman correlation coefficients (rho) ranging from -0.5 to 0.5. Moderate correlations did exist between gross beta-particle activity and potassium (rho = 0.72 to 0.82), likely because one potassium isotope (potassium-40) is a beta-particle emitter. Total dissolved solids and specific conductance also were moderately correlated (rho = 0.62 to 0.71) with gross alpha-particle and gross beta-particle activity, indicating that higher radioactivity values can be associated with higher total dissolved solids. Correlations were evaluated among radioactive constituents. Moderate to strong correlations occurred between gross alpha-particle and beta-particle activities (rho = 0.77 to 0.96) and radium isotopes (rho = 0.78 to 0.92). Correlations between gross alpha-particle activity (72-hour count) and all analyzed radioactive constituents were statistically significant (p-value < 0.05), and therefore, gross alpha-particle activity likely may be used as a screening tool for determining the presence of radionuclides in area waters. In this study, gross alpha-particle activities of 7 picocuries per liter or greater were associated with all radioactive constituents whose concentrations exceeded drinking-water standards or screening levels. Radiochemical results varied temporally in samples from several of the thirty-eight wells sampled at least twice during the study. The time between successive sampling events ranged from about 1 to 10 months for 29 wells to about 3 years for the other 9 wells. Radiochemical constituents that varied by greater than 30 percent between sampling events included uranium (29 percent of the resampled wells), and radon (11 percent of the resampled wells), gross alpha-particle activity (38 percent of the resampled wells), and gross beta-particle activity (15 percent of the resampled wells). Variability in uranium concentrations from two wells was sufficiently large that concentrations were less than the MCL in the first set of samples and greater than the MCL in the second. Sample holding times affect analytical results in this study. Gross alpha-particle and gross beta-particle activities were measured twice, 72 hours and 30 days after sample collection. Gross alpha-particle activity decreased an average of 37 percent between measurements, indicating the presence of short-lived alpha-emitting radionuclides in these samples. Gross beta-particle activity increased an average of 31 percent between measurements, indicating ingrowth of longer-lived beta-emitting radionuclides.

Montana

A lead isotope distribution study in swine tissue using ICP-MS

In the United States lead is an ubiquitous environmental pollutant that is a serious human health hazard, especially for women of childbearing age, developing fetuses, and young children. Information concerning the uptake and distribution of lead to maternal and fetal tissues during pregnancy is poorly documented. A study was designed using domestic swine and lead isotope enrichment methodology to focus on maternal absorption and distribution of lead into bone and soft tissues, including the fetal compartment, under varying conditions of oral lead exposure and during altered physiological states (pregnant vs unbred). Total lead levels and Pb207/Pb206 ratios in bone (femur and vertebra), blood, and soft tissues (liver, kidney, brain) were determined by ICP-MS. Lead in fetal tissues derived from maternal bone could be differentiated from that derived from exogenous dosing. Unbred swine absorbed much less lead than pregnant females receiving the same dose. The accuracy and precision of ICP-MS at the instrumental level and for the entire method (sample collection, digestion, and analysis) were evaluated for both Pb207/Pb206 ratios and total lead. Several changes were suggested in method design to improve both instrumental and total method precision.

Atomic Spectroscopy

Energetic and health effects of protein overconsumption constrain dietary adaptation in an apex predator

Studies of predator feeding ecology commonly focus on energy intake. However, captive predators have been documented to selectively feed to optimize macronutrient intake. As many apex predators experience environmental changes that affect prey availability, limitations on selective feeding can affect energetics and health. We estimated the protein:fat ratio of diets consumed by wild polar bears using a novel isotope-based approach, measured protein:fat ratios selected by zoo polar bears offered dietary choice and examined potential energetic and health consequences of overconsuming protein. Dietary protein levels selected by wild and zoo polar bears were low and similar to selection observed in omnivorous brown bears, which reduced energy intake requirements by 70% compared with lean meat diets. Higher-protein diets fed to zoo polar bears during normal care were concurrent with high rates of mortality from kidney disease and liver cancer. Our results suggest that polar bears have low protein requirements and that limitations on selective consumption of marine mammal blubber consequent to climate change could meaningfully increase their energetic costs. Although bear protein requirements appear lower than those of other carnivores, the energetic and health consequences of protein overconsumption identified in this study have the potential to affect a wide range of taxa.

Scientific Reports

Overview and methodology for a study to identify fecal contamination sources using microbial source tracking in seven embayments on Long Island, New York

Between June 2018 and July 2019, the U.S. Geological Survey collaborated with the New York State Department of Environmental Conservation to analyze water quality in seven embayments on Long Island, New York, for a study to examine fecal contamination using microbial source tracking. This report documents the approach, methodology, and quality-assurance data used in the study. All samples and field data were collected in accordance with U.S. Geological Survey National Field Manual procedures. Samples were analyzed for host-specific deoxyribonucleic acid (DNA) markers, fecal coliform bacteria, inorganic and total organic nitrogen, and stable isotopes of nitrate and ammonium. Samples for quality control were collected for microbiological analyses at a rate of 1 per 20 environmental samples. A total of 14 blank and 15 replicate samples were collected for DNA markers, 52 sequential field replicates were analyzed by the Public Environmental Health Laboratory of the Suffolk County Department of Health Services and the New York State Department of Conservation Marine Laboratory for fecal coliform, and 7 blank and 7 replicate samples were collected to be analyzed for nutrients. Results from quality-control samples collected throughout the course of the study confirmed that sampling procedures were adequate and did not disqualify any data from analysis.

New York

Mercury biomagnification across food webs with varying non-native fish presence: Implications for native fish conservation in the upper Colorado River Basin

Environmental contaminants and non-native species introductions negatively affect aquatic ecosystem conservation. Mercury (Hg) accumulates within food webs where it can biomagnify to toxic concentrations, which can be affected by altered trophic relationships from non-native species. This study examined Hg concentrations (n samples = 655) and stable carbon and nitrogen isotope ( n = 746) compositions in native ( n = 313) and non-native ( n = 342) species among four river subbasins (Gunnison, Lower Green, Colorado-Dolores, and White-Yampa), in the Upper Colorado River Basin (UCRB) during 2016 and 2017 to inform the potential combined effects of Hg exposure and non-native species interactions on native fishes of conservation concern. We assessed Hg biomagnification at the fish assemblage level, compared concentrations to risk thresholds for fish and human health, and evaluated niche overlap among trophic levels across subbasins. The generalist-invertivores feeding guild had the lowest Hg concentrations (0.001–0.191 μg g −1 wet weight), and no individuals exceeded the U.S. Environmental Protection Agency aquatic life criterion (0.225 μg g −1 ). Piscivores had the highest concentrations (0.008–1.840 μg g −1 ), and 74% of individuals exceeded the criterion. Biomagnification across trophic levels was observed throughout the UCRB, yet varied by subbasin, with higher magnification factors in the Lower Green and White-Yampa subbasins which also had the highest proportion of non-native species. Stable isotope compositions revealed niche overlap among native and non-native species. Additionally, trophic position varied within species among the subbasins. The proliferation of non-native species has likely reshaped food webs and may have intensified the potential threat Hg poses to native fish recovery and conservation. This study documented increased Hg concentrations relative to past assessments, suggesting that continued monitoring could assist in evaluating trends in Hg accumulation. Particularly studies that focus on sources entering the food web, vectors for accumulation, and competitive interactions among native and non-native species.

Colorado, Utah, Wyoming

Drinking water health standards comparison and chemical analysis of groundwater for 72 domestic wells in Bradford County, Pennsylvania, 2016

Pennsylvania has the second highest number of residential wells of any state in the Nation with approximately 2.4 million residents that depend on groundwater for their domestic water supply. Despite the widespread reliance on groundwater in rural areas of the state, publicly available data to characterize the quality of private well water are limited. In Bradford County, more than half of the residents use groundwater from private domestic-supply wells as their primary drinking source. The quality of private well water is influenced by the regional and local setting, including the surrounding soil, geology, land use, household plumbing, and well construction. The groundwater used for domestic water supply in Bradford County is obtained primarily from shallow bedrock and from unconsolidated (glacial) deposits that overlie the bedrock. Historical land use has been predominately forested, agricultural, and residential, but more recently unconventional oil/gas development has been distributed throughout the landscape. Pennsylvania is one of only two states in the Nation without statewide water-well construction standards. To better assess the quality of groundwater used for drinking water supply in Bradford County, data for 72 domestic wells were collected and analyzed for a wide range of constituents that could be evaluated in relation to drinking water health standards, geology, land use, and other environmental factors. Groundwater samples were collected from May through August 2016 and analyzed for physical and chemical properties, including major ions, nutrients, trace elements, volatile organic compounds, ethylene and propylene glycol, alcohols, gross-alpha/beta-particle activity, uranium, radon-222, and dissolved gases. A subset of samples was analyzed for radium isotopes (radium-226 and -228) and for the isotopic composition of methane. This study was conducted by the U.S. Geological Survey in cooperation with the Northern Tier Regional Planning and Development Commission and is part of a regional effort to characterize groundwater in rural areas of Pennsylvania. Results of the 2016 study show that groundwater quality generally met most drinking-water standards. However, a percentage of samples failed to meet maximum contaminant levels (MCLs) for total coliform bacteria (49.3 percent), Escherichia coli (8.5 percent), barium (2.8 percent), and arsenic (2.8 percent); and secondary maximum contaminant levels (SMCL) for sodium (48.6 percent), manganese (30.6 percent), gross alpha and beta activity (16.7 percent), iron (11.1 percent), pH (8.3 percent), total dissolved solids (5.6 percent), chloride (1.4 percent), and aluminum (1.4 percent). Radon-222 activities exceeded the proposed drinking-water standard of 300 picocuries per liter (pCi/L) in 70.4 percent of the samples. There were no exceedances of drinking water health standards for any volatile organic compounds, and the only detections were for three trihalomethanes in one sample. The pH of the groundwater had a large influence on chemical characteristics and ranged from 6.18 to 9.31. Generally, the higher pH samples had higher potential for elevated concentrations of several constituents, including total dissolved solids, sodium, lithium, chloride, fluoride, boron, arsenic, and methane. For the Bradford County well-water samples, calcium/bicarbonate type waters were most abundant, with others classified as sodium/bicarbonate or mixed water types including calcium-sodium/bicarbonate, calcium-sodium/bicarbonate-chloride, sodium/bicarbonate-chloride, sodium/bicarbonate-sulfate, or sodium/chloride types. Six principal components (pH, redox, hardness, chloride-bromide, strontium-barium, and molybdenum-arsenic) explained nearly 78.3 percent of the variance in the groundwater dataset. Groundwater from 12.5 percent of the wells had concentrations of methane greater than the Pennsylvania action level of 7 milligrams per liter (mg/L); detectable methane concentrations ranged from 0.01 to 77 mg/L. In addition, low levels of ethane (as much as 0.13 mg/L) were present in seven samples with the highest methane concentrations. The isotopic composition of methane in five of these groundwater samples was consistent with the isotopic compositions reported for mud-gas logging samples from these geologic units and a thermogenic source. Isotopic composition from a sixth sample suggested the methane in that sample may be of microbial origin. Well-water samples with the higher methane concentrations also had higher pH values and elevated concentrations of sodium, lithium, boron, fluoride, arsenic, and bromide. Relatively elevated concentrations of some other constituents, such as barium and chloride, commonly were present in, but not limited to, those well-water samples with elevated methane. Four of the six groundwater samples with the highest methane concentrations had chloride/bromide ratios that indicate mixing with a small amount of brine (0.02 percent or less) similar in composition to those reported for gas and oil well brines in Pennsylvania. In several other eastern Pennsylvania counties where gas drilling is absent, groundwater with comparable chloride/bromide ratios and chloride concentrations have been reported, implying a potential natural source of brine. Most of Bradford County well-water samples have chloride concentrations less than 20 mg/L, and those with higher chloride concentrations have chloride/bromide ratios that indicate anthropogenic sources (such as road-deicing salt and septic effluent) or brine. Brines that are naturally present may originate from deeper parts of the aquifer system, whereas anthropogenic sources are more likely to affect shallow groundwater because they occur on or near the land surface. The available data for this study indicate that no one physical factor, such as the topographic setting, well depth, or altitude at the bottom of the well, was particularly useful for predicting those well locations with an elevated dissolved concentration of methane. The 2016 assessment of groundwater quality in Bradford County shows groundwater is generally of good quality, but methane and some constituents that occur in high concentration in naturally occurring brine and also in produced waters may be present at low to moderate concentrations in groundwater in various parts of the aquifer.

Pennsylvania

Sanitary quality of surface water during base-flow conditions in the Municipality of Caguas, Puerto Rico, 2014–15: A comparison with results from a similar 1997–99 study

A study was conducted in 2014–15 by the U.S. Geological Survey (USGS), in cooperation with the Municipality of Caguas, to determine if changes in the stream sanitary quality during base-flow conditions have occurred since 1997–99, when a similar study was completed by the USGS. Water samples were collected for the current study during two synoptic surveys in 2014 and 2015. Water samples were analyzed for fecal and total coliform bacteria, nitrate plus nitrite as nitrogen, nitrogen and oxygen isotopes of nitrate, and human health and pharmaceutical products. Water sampling occurred at 39 stream locations used during the 1997–99 study by the USGS and at 11 additional sites. A total of 151 stream miles were classified on the basis of fecal and total coliform bacteria results. The overall spatial pattern of the sanitary quality of surface water during 2014–15 is similar to the pattern observed in 1997–99 in relation to the standards adopted by the Puerto Rico Environmental Quality Board in 1990. Surface water at most of the water-sampling sites exceeded the current standard for fecal coliform of 200 colonies per 100 milliliters adopted by the Puerto Rico Environmental Quality Board in 2010. The poorest sanitary quality was within the urban area of the Municipality of Caguas, particularly in urban stream reaches of Río Caguitas and in rural and suburban reaches bordered by houses in high density that either have inadequate septic tanks or discharge domestic wastewater directly into the stream channels. The best sanitary quality occurred in areas having little or no human development, such as in the wards of San Salvador and Beatriz to the south and southwest of Caguas, respectively. The concentration of nitrate plus nitrite as nitrogen ranged from 0.02 to 9.0 milligrams per liter, and did not exceed the U.S. Environmental Protection Agency drinking-water standard for nitrate as nitrogen of 10 milligrams per liter. The composition of nitrogen and oxygen isotopes of nitrate indicates that the origin of nitrate in the streams is most likely animal and human waste. A baseline was established for the concentrations of selected human health and pharmaceutical products at stations in some of the streams within the Municipality of Caguas. Thirty-eight human health and pharmaceutical products were present at or above the measurement detection level.

Caguas, Puerto Rico

Groundwater quality in relation to drinking water health standards and hydrogeologic and geochemical characteristics for 47 domestic wells in Potter County, Pennsylvania, 2017

As part of a regional effort to characterize groundwater in rural areas of Pennsylvania, water samples from 47 domestic wells in Potter County were collected from May through September 2017. The sampled wells had depths ranging from 33 to 600 feet in sandstone, shale, or siltstone aquifers. Groundwater samples were analyzed for physicochemical properties that could be evaluated in relation to drinking-water health standards, geology, land use, and other environmental factors. Laboratory analyses included concentrations of major ions, nutrients, bacteria, trace elements, volatile organic compounds (VOCs), ethylene and propylene glycol, alcohols, gross-alpha/beta-particle activity, uranium, radon-222, and dissolved gases. A subset of samples was analyzed for radium isotopes (radium-226 and -228) and for the isotopic composition of methane. Results of this 2017 study show that groundwater quality generally met most drinking-water standards that apply to public water supplies. However, a percentage of samples exceeded maximum contaminant levels (MCLs) for total coliform bacteria (69.6 percent), Escherichia coli (30.4 percent), arsenic, and barium; and secondary maximum contaminant levels (SMCLs) for field pH, manganese, sodium, iron, total dissolved solids, aluminum, and chloride. All of the analyzed VOCs were below limits of detection and associated drinking water criteria. Radon-222 activities exceeded the proposed drinking-water standard of 300 picocuries per liter in 80.9 percent of the samples. The field pH of the groundwater ranged from 4.6 to 9.0. Generally, the lower pH samples had greater potential for elevated concentrations of dissolved metals, including beryllium, copper, lead, nickel, and zinc, whereas the higher pH samples had greater potential for elevated concentrations of total dissolved solids, sodium, fluoride, boron, and uranium. Near-neutral samples (pH 6.5 to 7.5) had greater hardness and alkalinity concentrations than other samples with pH values outside this range. Calcium/bicarbonate waters were the predominant hydrochemical type for the sampled aquifers, with mixed water types for many samples, including variable contributions from calcium, magnesium, and sodium combined with bicarbonate, sulfate, chloride, and nitrate. Water from 45 wells had concentrations of methane greater than the 0.0002 milligrams per liter (mg/L) detection limit. One sample had the maximum value of 11 mg/L, which exceeds the Pennsylvania action level of 7 mg/L. Additionally, three other samples had concentrations of methane greater than 4 mg/L. Outgassing of such levels of methane from the water to air within a confined space can result in a potential hazard. The elevated concentrations of methane generally were associated with suboxic groundwater (dissolved oxygen less than 0.5 mg/L) that had near-neutral to alkaline pH with relatively elevated concentrations of iron, manganese, ammonia, lithium, fluoride, and boron. Other constituents, including barium, sodium, chloride, and bromide, commonly were elevated, but not limited to, those well-water samples with elevated methane. Low levels of ethane (as much as 1.2 mg/L) were present in eight samples with the highest methane concentrations. Five samples were analyzed for methane isotopes. The isotopic and hydrocarbon compositions in these five samples suggest the methane may be of microbial origin or a mixture of thermogenic and microbial gas, but differed from the compositions reported for mud-gas logging samples collected during drilling of gas wells. The concentrations of sodium (median 8.2 mg/L), chloride (median 7.64 mg/L), and bromide (median 0.02 mg/L) for the 47 groundwater samples collected for this study ranged widely and were positively correlated with one another and with specific conductance and associated measures of ionic strength. Sixty percent of the Potter County well-water samples had chloride concentrations less than 10 mg/L. Samples with higher chloride concentrations had variable bromide concentrations and corresponding chloride/bromide ratios that are consistent with sources such as road-deicing salt and septic effluent (low bromide) or brine (high bromide). Brines are naturally present in deeper parts of the regional groundwater system and, in some cases, may be mobilized by gas drilling. It is also possible that valley wells were drilled close to or into the brine-freshwater interface, so brine signatures do not necessarily indicate contamination due to drilling. The chloride, bromide, and other constituents in road-deicing salt or brine solutions tend to be diluted by mixing with fresh groundwater in shallow aquifers used for water supply. Although 1 of 8 groundwater samples with the highest methane concentrations (greater than 0.2 mg/L) had concentrations of chloride and bromide with corresponding chloride/bromide ratios that indicated mixing with road-deicing salt, the other 7 of 8 samples with elevated methane had concentrations of chloride and bromide with corresponding chloride/bromide ratios that indicated mixing with a small amount of brine (0.02 percent or less) similar in composition to those reported for gas and oil well brines in Pennsylvania. In several eastern Pennsylvania counties where gas drilling is absent, groundwater with comparable chloride/bromide ratios and chloride concentrations have been reported. Approximately 50 percent of Potter County well-water samples, including two samples with the fourth (72.9 mg/L) and fifth (47.0 mg/L) highest chloride concentrations, have chloride/bromide ratios that indicate predominantly anthropogenic sources of chloride, such as road-deicing salt or septic effluent.

Pennsylvania

Shallow groundwater quality in the Village of Patchogue, Suffolk County, New York

The onsite disposal of wastewater within the Patchogue River Basin-a riverine estuary that discharges into Great South Bay, Suffolk County, Long Island, N.Y. -has adversely affected water quality and aquatic habitats within both the tidal and non-tidal portions of the river. In response to increased development within the approximately 14 square mile basin, the Village of Patchogue has expanded efforts to manage and protect the local groundwater resources, which sustain freshwater base flow and aquatic habitats. Water-quality samples from 10 shallow wells within the Village were collected in March 2009, before the start of seasonal fertilizer application, to document the effects of onsite wastewater disposal on groundwater discharging into the Patchogue River. Each sample was analyzed for physical properties (pH, dissolved oxygen, specific conductance, and temperature), nutrients, organic carbon, major ions, and trace elements. Water samples from eight wells were analyzed for stable isotopes of nitrogen. The nitrate concentration in one well was 40 milligrams per liter (mg/L), which exceeded the U.S. Environmental Protection Agency (USEPA) and New York State Department of Health (NYSDOH) maximum contamination level in drinking water of 10 mg/L. Sodium concentrations at nine wells exceeded the USEPA Drinking Water Advisory Taste Threshold of 60 mg/L. Dissolved iron concentrations at three wells exceeded the NYSDOH and USEPA Secondary Drinking Water Standard of 300 micrograms per liter (?g/L). Nitrogen isotope signatures (d15N) were determined and compared with those reported from previous studies in Nassau and Suffolk Counties to identify possible sources of the nitrate. Local variations in measured ammonia, nitrate, total nitrogen, phosphorus, and organic carbon concentrations and d15N signatures indicate that nitrate enters the surficial aquifer from several sources (fertilizer, septic waste, and animal waste) and reflects biogeochemical processes such as denitrification.

Scientific Investigations Report

Analytical Results for Agricultural Soils Samples from a Monitoring Program Near Deer Trail, Colorado (USA)

Since late 1993, Metro Wastewater Reclamation District of Denver (Metro District, MWRD), a large wastewater treatment plant in Denver, Colorado, has applied Grade I, Class B biosolids to about 52,000 acres of nonirrigated farmland and rangeland near Deer Trail, Colorado, USA. In cooperation with the Metro District in 1993, the U.S. Geological Survey (USGS) began monitoring groundwater at part of this site. In 1999, the USGS began a more comprehensive monitoring study of the entire site to address stakeholder concerns about the potential chemical effects of biosolids applications to water, soil, and vegetation. This more comprehensive monitoring program has recently been extended through 2010. Monitoring components of the more comprehensive study include biosolids collected at the wastewater treatment plant, soil, crops, dust, alluvial and bedrock groundwater, and stream bed sediment. Soils for this study were defined as the plow zone of the dry land agricultural fields - the top twelve inches of the soil column. This report presents analytical results for the soil samples collected at the Metro District farm land near Deer Trail, Colorado, during three separate sampling events during 1999, 2000, and 2002. Soil samples taken in 1999 were to be a representation of the original baseline of the agricultural soils prior to any biosolids application. The soil samples taken in 2000 represent the soils after one application of biosolids to the middle field at each site and those taken in 2002 represent the soils after two applications. There have been no biosolids applied to any of the four control fields. The next soil sampling is scheduled for the spring of 2010. Priority parameters for biosolids identified by the stakeholders and also regulated by Colorado when used as an agricultural soil amendment include the total concentrations of nine trace elements (arsenic, cadmium, copper, lead, mercury, molybdenum, nickel, selenium, and zinc), plutonium isotopes, and gross alpha and beta activity (Colorado Department of Public Health and Environment, Hazardous Materials and Waste Management Division, 1997; Colorado Department of Public Health and Environment,1998; U.S. Environmental Protection Agency, 1993). Since these were the identified priority parameters for the biosolids, the soils have the same set of priority parameters. Although the composite soils' priority analytes have been reported earlier to Metro District, the remaining elemental datasets for both the composite soils samples and selected fields' individual subsamples' data are presented here for the first time. More information about the other monitoring components is presented elsewhere in the literature (http://co.water.usgs.gov/projects/CO406/CO406.html). In general, the objective of each component of the study was to determine whether concentrations of priority parameters (1) were higher than regulatory limits, (2) were increasing with time, and(or) (3) were significantly higher in biosolids-applied areas than in a similar farmed area where biosolids were not applied. The method chosen for sampling the soils proved to be an efficient and reliable representation of the average composition of each field. This was shown by analyzing individual subsamples, averaging the resulting values, and then comparing the values to the composited samples' values. The soil chemistry shows distinct differences between the two sites, most likely due to the different underlying parent material. Biosolids data were used to compile an inorganic-chemical biosolids signature that can be contrasted with the geochemical signature of the agricultural soils for this site. The biosolids signature and an understanding of the geology and hydrology of the site can be used to separate biosolids effects from natural geochemical effects. Elements of particular interest for a biosolids signature after application in the soils include bismuth, copper, silver, mercury, and phosphorus. This signat

Open-File Report

A seasonal and spatial comparison of metals, and stable carbon and nitrogen isotopes, in Chincoteague Bay and the marsh deposits of Assateague Island and the adjacent vicinity, Maryland and Virginia

After Hurricane Sandy, scientists from the U.S. Geological Survey, St. Petersburg Coastal and Marine Science Center conducted a seasonal collection of estuarine, marsh, and sandy overwash surface sediments from Chincoteague Bay, Tom’s Cove, and the surrounding Assateague Island and Delmarva Peninsula in March–April and October 2014. Surplus surface sediment was analyzed for metals, percent carbon and nitrogen, δ 13 C, and δ 15 N as part of a complementary U.S. Geological Survey Coastal and Marine Geology Program Sea-level and Storm Impacts on Estuarine Environments and Shorelines project study. The geochemical subsample analyzed for metals and stable isotopes at each site may be used for comparison with past data sets, to create a modern baseline of the natural distribution of the area, to understand seasonal variability as it relates to the health of the local environment, and to assess marsh-to-bay interactions. The use of metals, stable carbon, and stable nitrogen isotopes allows for a more cohesive snapshot of factors influencing the environment and could aid in tracking environmental change. This report serves as an archive for chemical data derived from the surface sediment. Data are available for a seasonal comparison between the March–April 2014 and October 2014 sampling trips. Downloadable data are available as Microsoft Excel spreadsheets. These additional files include formal Federal Geographic Data Committee metadata ( data downloads ).

Maryland, Virginia