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Global genetic diversity status and trends: Towards a suite of Essential Biodiversity Variables (EBVs) for genetic composition

Biodiversity underlies ecosystem resilience, ecosystem function, sustainable economies, and human well-being. Understanding how biodiversity sustains ecosystems under anthropogenic stressors and global environmental change will require new ways of deriving and applying biodiversity data. A major challenge is that biodiversity data and knowledge are scattered, biased, collected with numerous methods, and stored in inconsistent ways. The Group on Earth Observations Biodiversity Observation Network (GEO BON) has developed the Essential Biodiversity Variables (EBVs) as fundamental metrics to help aggregate, harmonize, and interpret biodiversity observation data from diverse sources. Mapping and analyzing EBVs can help to evaluate how aspects of biodiversity are distributed geographically and how they change over time. EBVs are also intended to serve as inputs and validation to forecast the status and trends of biodiversity, and to support policy and decision making. Here, we assess the feasibility of implementing Genetic Composition EBVs (Genetic EBVs), which are metrics of within-species genetic variation. We review and bring together numerous areas of the field of genetics and evaluate how each contributes to global and regional genetic biodiversity monitoring with respect to theory, sampling logistics, metadata, archiving, data aggregation, modeling, and technological advances. We propose four Genetic EBVs: ( i ) Genetic Diversity; ( ii ) Genetic Differentiation; ( iii ) Inbreeding; and ( iv ) Effective Population Size ( N e ). We rank Genetic EBVs according to their relevance, sensitivity to change, generalizability, scalability, feasibility and data availability. We outline the workflow for generating genetic data underlying the Genetic EBVs, and review advances and needs in archiving genetic composition data and metadata. We discuss how Genetic EBVs can be operationalized by visualizing EBVs in space and time across species and by forecasting Genetic EBVs beyond current observations using various modeling approaches. Our review then explores challenges of aggregation, standardization, and costs of operationalizing the Genetic EBVs, as well as future directions and opportunities to maximize their uptake globally in research and policy. The collection, annotation, and availability of genetic data has made major advances in the past decade, each of which contributes to the practical and standardized framework for large-scale genetic observation reporting. Rapid advances in DNA sequencing technology present new opportunities, but also challenges for operationalizing Genetic EBVs for biodiversity monitoring regionally and globally. With these advances, genetic composition monitoring is starting to be integrated into global conservation policy, which can help support the foundation of all biodiversity and species' long-term persistence in the face of environmental change. We conclude with a summary of concrete steps for researchers and policy makers for advancing operationalization of Genetic EBVs. The technical and analytical foundations of Genetic EBVs are well developed, and conservation practitioners should anticipate their increasing application as efforts emerge to scale up genetic biodiversity monitoring regionally and globally.

Biological Reviews↗

Radiochemical sampling and analysis of shallow ground water and sediment at the BOMARC Missile Facility, east-central New Jersey, 1999-2000

A field sampling experiment was designed using low-flow purging with a portable pump and sample-collection equipment for the collection of water and sediment samples from observation wells screened in the Kirkwood-Cohansey aquifer system to determine radionuclide or trace-element concentrations for various size fractions. Selected chemical and physical characteristics were determined for water samples from observation wells that had not been purged for years. The sampling was designed to define any particulate, colloidal, and solution-phase associations of radionuclides or trace elements in ground water by means of filtration and ultrafiltration techniques. Turbidity was monitored and allowed to stabilize before samples were collected by means of the low-flow purging technique rather than by the traditional method of purging a fixed volume of water at high-flow rates from the observation well. A minimum of four water samples was collected from each observation well. The samples of water from each well were collected in the following sequence. (1) A raw unfiltered sample was collected within the first minutes of pumping. (2) A raw unfiltered sample was collected after at least three casing volumes of water were removed and turbidity stabilized. (3) A sample was collected after the water was filtered with a 0.45-micron filter. (4) A sample was collected after the water passed through a 0.45-micron filter and a 0.003-micron tangential-flow ultrafilter in sequence. In some cases, a fifth sample was collected after the water passed through a 0.45-micron filter and a 0.05-micron filter in sequence to test for colloids of 0.003 microns to 0.05 microns in size. The samples were analyzed for the concentration of manmade radionuclides plutonium-238 and -239 plus -240, and americium-241. The samples also were analyzed for concentrations of uranium-234, -235, and -238 to determine whether uranium-234 isotope enrichment (resulting from industrial processing) is present. A subset of samples was analyzed for concentrations of thorium-232, -230, and -228 to determine if thorium-228 isotope enrichment, also likely to result from industrial processing, is present. Concentrations of plutonium isotopes and americium-241 in the water samples were less than 0.1 picocurie per liter, the laboratory reporting level for these manmade radionuclides, with the exception of one americium-241 concentration from a filtered sample. A sequential split sample from the same well did not contain a detectable concentration of americium-241, however. Other filtered and unfiltered samples of water from the same well did not contain quantities of americium-241 nearly as high as 0.1 pCi/L. Therefore, the presence of americium-241 in a quantifiable concentration in water samples from this well could not be confirmed. Neither plutonium nor americium was detected in samples of settled sediment collected from the bottom of the wells. Concentrations of uranium isotopes (maximum of 0.05 and 0.08 picocuries per liter of uranium-238 and uranium-234, respectively) were measurable in unfiltered samples of turbid water from one well and in the settled bottom sediment from 6 wells (maximum concentrations of 0.25 and 0.20 picocuries per gram of uranium-238 and uranium-234, respectively). The uranium-234/uranium-238 isotopic ratio was near 1:1, which indicates natural uranium. The analytical results, therefore, indicate that no manmade radionuclide contamination is present in any of the well-bottom sediments, or unfiltered or filtered water samples from any of the sampled wells. No evidence of manmade radionuclide contamination was observed in the aquifer as settled or suspended particulates, colloids, or in the dissolved phase.

New Jersey↗

Resolving global versus local/regional Pu sources in the environment using sector ICP-MS

Sector inductively coupled plasma mass spectrometry is a versatile method for the determination of plutonium activities and isotopic compositions in samples containing this element at fallout levels. Typical detection limits for 239+240Pu are 0.1, 0.02 and 0.002 Bq kg -1Pu for samples sizes of 0.5 g, 3 g, and 50 g of soil, respectively. The application of sector ICP-MS-based Pu determinations is demonstrated in studies in sediment chronology, soil Pu inventory and depth distribution, and the provenance of global fallout versus local or regional Pu sources. A sediment core collected from Sloans Lake (Denver, Colorado, USA) exhibits very similar 137Cs and 239+240Pu activity profiles; 240Pu/239Pu atom ratios indicate possible small influences from the Nevada Test Site and/or the Rocky Flats Environmental Technology Site. An undisturbed soil profile from Lockett Meadow (Flagstaff, Arizona, USA) exhibits an exponential decrease in 239+240Pu activity versus depth; 240Pu/239Pu in the top 3 cm is slightly lower than the global fallout range of 0.180 ?? 0.014 due to possible regional influence of Nevada Test Site fallout. The 239??240Pu inventory at Lockett Meadow is 56 ?? 4 Bq m-2, consistent with Northern Hemisphere mid-latitude fallout. Archived NdF3 sources, prepared from Polish soils, demonstrate that substantial 239+240Pu from the 1986 Chernobyl disaster has been deposited in north eastern regions of Poland; compared to global fallout, Chernobyl Pu exhibits higher abundances of 240Pu and 241Pu. The ratios 240Pu/239pu and 241Pu/239Pu co-vary and range from 0.186-0.348 and 0.0029-0.0412, respectively, in forest soils (241Pu/239Pu = 0.2407??[240Pu/239Pu] - 0.0413; r2 = 0.9924). ?? The Royal Society of Chemistry 2004.

Journal of Analytical Atomic Spectrometry↗

Toward a transport-based analysis of nutrient spiraling and uptake in streams

Nutrient addition experiments are designed to study the cycling of nutrients in stream ecosystems where hydrologic and nonhydrologic processes determine nutrient fate. Because of the importance of hydrologic processes in stream ecosystems, a conceptual model known as nutrient spiraling is frequently employed. A central part of the nutrient spiraling approach is the determination of uptake length ( S w ), the average distance traveled by dissolved nutrients in the water column before uptake. Although the nutrient spiraling concept has been an invaluable tool in stream ecology, the current practice of estimating uptake length from steady‐state nutrient data using linear regression (called here the “ S w approach”) presents a number of limitations. These limitations are identified by comparing the exponential S w equation with analytical solutions of a stream solute transport model. This comparison indicates that (1) S w is an aggregate measure of uptake that does not distinguish between main channel and storage zone processes, (2) S w is an integrated measure of numerous hydrologic and nonhydrologic processes—this process integration may lead to difficulties in interpretation when comparing estimates of S w , and (3) estimates of uptake velocity and areal uptake rate ( v f and U ) based on S w are not independent of system hydrology. Given these findings, a transport‐based approach to nutrient spiraling is presented for steady‐state and time‐series data sets. The transport‐based approach for time‐series data sets is suggested for future research on nutrient uptake as it provides a number of benefits, including the ability to (1) separately quantify main channel and storage zone uptake, (2) quantify specific hydrologic and nonhydrologic processes using various model parameters (process separation), (3) estimate uptake velocities and areal uptake rates that are independent of hydrologic effects, and (4) use shortterm, non‐plateau nutrient additions such that the effects of regeneration and mineralization are minimized. In summary, the transport‐based, time‐series approach provides a means of estimating traditional measures of nutrient uptake ( S w , v f , U ) while providing additional information on the location and magnitude of uptake (main channel versus storage zone). Application of the transport‐based approach to time‐series data from Green Creek, Antarctica, indicates that the bulk of nitrate uptake (~74% to 100%) occurred within the main channel where benthic uptake by algal mats is a likely process. Substantial uptake (~26%) also occurred in the storage zone of one reach, where uptake is attributed to the microbial community.

Limnology and Oceanography: Methods↗

Reconnaissance of arsenic concentrations in ground water from bedrock and unconsolidated aquifers in eight northern-tier counties of Pennsylvania

Samples of ground water for analysis of total-arsenic concentrations were collected in eight counties--Potter, Tioga, Bradford, Susquehanna, Wayne, Pike, Sullivan, and Wyoming--and from eight bedrock formations (bedrock aquifers) and overlying glacial aquifers in the north-central and northeastern parts of Pennsylvania in July 2005 and from March through June 2006. The samples were collected from a total of 143 domestic wells, 2 stock wells, 4 non-community wells, 2 community water-system wells, and 3 domestic springs by well or spring owners using sampling kits provided by the U.S. Geological Survey (USGS). An additional 15 domestic wells were sampled by the USGS for analysis of total arsenic. These 15 samples were collected using the same methods and sampling kits provided to the homeowners. Samples were analyzed for total arsenic by the Pennsylvania Department of Environmental Protection Laboratory using a minimum reporting level of 4.0 µg/L (micrograms per liter). Arsenic was detected in water from 18 domestic wells in four counties--Bradford (3 wells), Sullivan (1 well), Tioga (13 wells), and Wayne (1 well). The median concentration of total arsenic was less than 4.0 µg/L, and the maximum concentration was 188 µg/L. Water from 10 wells had concentrations of total arsenic greater than the U.S. Environmental Protection Agency Maximum Contaminant Level of 10 µg/L. Detectable concentrations of total arsenic were measured in water from wells that ranged in depth from 29 to 400 feet, and that were completed in three aquifers--Lock Haven Formation, Catskill Formation, and unconsolidated glacial sediments; no springs had detectable concentrations of total arsenic. Water samples representing the Lock Haven Formation were collected from 60 wells; water from 12 of these wells had detectable concentrations of total arsenic. Water samples representing the Catskill Formation were collected from 57 wells; water from 4 wells had detectable concentrations of total arsenic. Water samples representing the unconsolidated glacial sediments were collected from 17 wells; 2 wells had water with detectable concentrations of total arsenic. Contingency tables tested for significant differences in total arsenic between aquifers, topographic settings, and well depths. Concentrations of total arsenic were significantly greater (95-percent confidence level) in the Lock Haven Formation than in the other bedrock units. Concentrations of total arsenic also varied significantly by topographic setting. Wells completed in the Lock Haven Formation and located in valleys had significantly greater concentrations of total arsenic than similar wells located on hilltops or slopes. Concentrations of total arsenic did not vary significantly by topographic setting in the Catskill Formation. Concentrations of total arsenic did not vary significantly by well depth for any aquifer. Iron staining, hydrogen-sulfide odor, or both were common complaints of well owners. Iron staining was a complaint of 44 well owners. Hydrogen-sulfide odor was a complaint of 35 well owners. Fourteen well owners complained of both iron staining and hydrogen sulfide. No correlation to the presence of arsenic in the wells sampled was found with iron staining, hydrogen-sulfide odor, or both. Water from 8 of the 10 wells that contained concentrations of total arsenic greater than 10 µg/L were sampled by USGS personnel for the determination of concentrations of dissolved arsenic (minimum reporting level 0.3 µg/L) and arsenic species {arsenite [As (III)], arsenate [As (V)], monomethylarsonate (MMA), and dimethylarsinate (DMA)} at the USGS National Water Quality Laboratory. Analytical results from these samples showed a median concentration of 38.7 µg/L dissolved arsenic in water and a maximum of 178 µg/L. As (III) was the most common arsenic species present in the water for seven of the eight wells and was found in water characteristic of reducing environments [pH 8.2 to 9.1, dissolved oxygen 0.06 to 0.29 milligrams per liter (mg/L), and oxidation reduction potential -63 to -203 millivolts (mv)]. As (V) was the dominant arsenic species in water characteristic of an oxidizing environment (pH 4.8, dissolved oxygen 2.15 mg/L, oxidation reduction potential 265 mv). The arsenic species MMA and DMA were detected in the water from two wells. The arsenic species MMA was detected at an estimated concentration of 0.9 µg/L in water from one well; the concentration was less than 1.2 µg/L in water from seven wells. The arsenic species DMA was detected at concentrations of 1.0 and 1.5 µg/L in water from two wells; the concentration was less than 0.6 µg/L in water from six wells. Both wells that contained detectable concentrations of MMA and DMA produced water that was characteristic of reducing environments.

Pennsylvania↗

Determination of the δ 15 N of nitrate in water; RSIL lab code 2899

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 2899 is to determine the δ 15 N of nitrate (NO 3 - ) in water. The δ 15 N of the dissolved NO 3 - is analyzed by conversion of the NO 3 - to nitrous oxide (N 2 O), which serves as the analyte for mass spectrometry. A culture of denitrifying bacteria is used in the enzymatic conversion of the NO 3 - to N 2 O, which follows the pathway shown in equation 1: NO 3 - → NO 2 - → NO → 1/2 N 2 O (1) Because the bacteria Pseudomonas aureofaciens lack N 2 O reductive activity, the reaction stops at N 2 O, unlike the typical denitrification reaction that goes to N 2 . After several hours, the conversion is complete, and the N 2 O is extracted from the vial, separated from volatile organic vapor and water vapor by an automated -65 °C isopropanol-slush trap, a Nafion drier, a CO 2 and water removal unit (Costech #021020 carbon dioxide absorbent with Mg(ClO 4 ) 2 ), and trapped in a small-volume trap immersed in liquid nitrogen with a modified Finnigan MAT (now Thermo Scientific) GasBench 2 introduction system. After the N 2 O is released, it is further purified by gas chromatography before introduction to the isotope-ratio mass spectrometer (IRMS). The IRMS is a Thermo Scientific Delta V Plus continuous flow IRMS (CF-IRMS). It has a universal triple collector, consisting of two wide cups with a narrow cup in the middle; it is capable of simultaneously measuring mass/charge ( m/z ) of the N 2 O molecule 44, 45, and 46. The ion beams from these m/z values are as follows: m/z = 44 = N 2 O = 14 N 14 N 16 O; m/z = 45 = N 2 O = 14 N 15 N 16 O or 14 N 14 N 17 O; m/z = 46 = N 2 O = 14 N 14 N 18 O. The 17 O contributions to the m/z 44 and m/z 45 ion beams are accounted for before δ 15 N values are reported.

Techniques and Methods↗

Determination of the δ 15 N and δ 18 O of nitrate in water; RSIL lab code 2900

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 2900 is to determine the δ 15 N and δ 18 O of nitrate (NO 3 - ) in water. The δ 15 N and δ 18 O of the dissolved NO 3 - are analyzed by converting the NO 3 - to nitrous oxide (N 2 O), which serves as the analyte for mass spectrometry. A culture of denitrifying bacteria is used in the enzymatic conversion of the NO 3 - to N 2 O, which follows the pathway shown in equation 1: NO 3 - → NO 2 - → NO → 1/2 N 2 O (1) Because the bacteria Pseudomonas aureofaciens lack N 2 O reductive activity, the reaction stops at N 2 O, unlike the typical denitrification reaction that goes to N 2 . After several hours, the conversion is complete, and the N 2 O is extracted from the vial, separated from volatile organic vapor and water vapor by an automated -65 °C isopropanol-slush trap, a Nafion drier, a CO 2 and water removal unit (Costech #021020 carbon dioxide absorbent with Mg(ClO 4 ) 2 ), and trapped in a small-volume trap immersed in liquid nitrogen with a modified Finnigan MAT (now Thermo Scientific) GasBench 2 introduction system. After the N 2 O is released, it is further purified by gas chromatography before introduction to the isotope-ratio mass spectrometer (IRMS). The IRMS is a Thermo Scientific Delta V Plus continuous flow IRMS (CF-IRMS). It has a universal triple collector, consisting of two wide cups with a narrow cup in the middle; it is capable of simultaneously measuring mass/charge ( m/z ) of the N 2 O molecule 44, 45, and 46. The ion beams from these m/z values are as follows: m/z = 44 = N 2 O = 14 N 14 N 16 O; m/z = 45 = N 2 O = 14 N 15 N 16 O or 14 N 14 N 17 O; m/z = 46 = N 2 O = 14 N 14 N 18 O. The 17 O contributions to the m/z 44 and m/z 45 ion beams are accounted for before δ 15 N values are reported.

Techniques and Methods↗

Hexavalent and total chromium at low reporting concentrations in source-water aquifers and surface waters used for public supply in Illinois, 2013

On the basis of their recent review of the human health effects of hexavalent chromium [Cr(VI)] in public drinking water, the U.S. Environmental Protection Agency is considering the need for Federal regulation of Cr(VI). Presently, only total chromium is regulated, at a Maximum Contaminant Level (MCL) of 100 micrograms per liter (µg/L). The occurrence of Cr(VI) in groundwater and surface waters generally is attributed to industrial sources, but can be of natural origin. California’s recently established MCL for Cr(VI) of 10 µg/L illustrates the drinking-water concerns associated with Cr(VI). To improve understanding of the possible impact of a Cr(VI)-specific standard that approximates the California level on the management of Illinois’ public drinking water, the U.S. Geological Survey, in cooperation with the Illinois Environmental Protection Agency, assessed the occurrence and distribution of Cr(VI) in the State’s public-water supplies. During 2013, untreated water samples were collected to be analyzed for Cr(VI) and total chromium [Cr(T)] at 119 water-supply wells and 32 surface-water intakes; also, 32 treated surface-water samples were collected near the point of treatment and 32 near the furthest point of distribution. Public-supply sample sites were selected by a stratified random method. Samples typically were analyzed within 24 hours of collection at reporting limits of 0.02 µg/L for Cr(VI) and 0.1 µg/L for Cr(T). The occurrence of Cr(VI) was compared with selected geophysical, physical, and sampling factors that might more fully explain its distribution and magnitude of concentrations. The maximum concentration of Cr(VI) in groundwater was 2.1 µg/L. Maximum concentrations in untreated and treated surface water were 0.29 µg/L and 2.4 µg/L, respectively. All sample concentrations were below the California MCL; only 35 percent were below that State’s non-enforceable public health goal of 0.02 of µg/L. Cr(VI) was undetected in 43 percent of untreated groundwater samples, with a median of 0.06 µg/L when detected. All but two (94 percent) of untreated surface-water samples had detections. In untreated surface water, the median concentration was 0.09 µg/L, whereas in treated (tap and distributed) water the median was 0.20 µg/L. Surface waters treated with lime for softening typically had the greatest Cr(VI) concentrations (maximum, 2.4 µg/L; median, 1.2 µg/L). The maximum concentration of Cr(T) in groundwater was 1.8 µg/L. Maximum concentrations in untreated and treated surface water were 1.8 µg/L and 2.5 µg/L, respectively. All sample concentrations were below the Federal MCL. Total chromium was detected in 65 percent of untreated groundwater samples, with a median of 0.40 µg/L, when detected. All but one (97 percent) of untreated surface-water samples had detections. In untreated surface water, the median concentration was 0.40 µg/L, whereas in treated (tap and distributed) water the median was 0.30 µg/L. As with Cr(VI), surface waters treated with lime typically had the greatest Cr(T) concentrations. Examination of factors that might account for or be associated with the occurrence of Cr(VI) in public-supply source waters found few clearly evident factors. Associations in frequencies of occurrence and range of concentrations indicate that surface waters and groundwaters of shallow, unconsolidated, unconfined aquifers, particularly alluvial aquifers, are possibly most commonly affected by anthropogenic sources of Cr(VI). Groundwaters of deep (greater than 500 feet) bedrock aquifers, particularly the Cambrian-Ordovician aquifer system, are possibly most commonly affected by geologic sources of Cr(VI). Additional study, with supporting geologic and geochemical data that were not collected in this study, would be necessary to verify these associations. There was a weak positive relation (ρ = 0.23) between concentrations of Cr(VI) and Cr(T) in untreated water samples, with a much stronger positive relation (ρ = 0.86 and ρ = 0.90, respectively) in samples collected soon after treatment and near the endpoint of distribution. The stronger relation and greater similarity between Cr(VI) and Cr(T) concentrations in treated water samples indicate that Cr(VI) represents a greater proportion of the measured concentrations of Cr(T) in treated waters than in untreated waters. The analysis of spikes and other quality-assurance samples indicate uncertainties associated with obtaining or confirming consistently accurate analytical results for Cr(VI) at near the applied reporting limit of 0.02 µg/L.

Illinois↗

Groundwater quality data in 15 GAMA study units: results from the 2006–10 Initial sampling and the 2009–13 resampling of wells, California GAMA Priority Basin Project

The Priority Basin Project (PBP) of the Groundwater Ambient Monitoring and Assessment (GAMA) program was developed in response to the Groundwater Quality Monitoring Act of 2001 and is being conducted by the U.S. Geological Survey (USGS) in cooperation with the California State Water Resources Control Board (SWRCB). From May 2004 to March 2012, the GAMA-PBP collected samples from more than 2,300 wells in 35 study units across the State. Selected wells in each study unit were sampled again approximately 3 years after initial sampling as part of an assessment of temporal trends in water quality by the GAMA-PBP. This triennial (every 3 years) trend sampling of GAMA-PBP study units concluded in December 2013. Fifteen of the study units, initially sampled between January 2006 and June 2010 and sampled a second time between April 2009 and April 2013 to assess temporal trends, are the subject of this report. The initial sampling was designed to provide a spatially unbiased assessment of the quality of untreated groundwater used for public water supplies in the 15 study units. In these study units, 730 wells were selected by using a spatially distributed, randomized grid-based method to provide statistical representation of the areas assessed (grid wells, also called “status wells”). Approximately 3 years after the initial sampling, 93 of the previously sampled status wells (approximately 10 percent in each study unit) were randomly selected for trend sampling (“trend wells”). The 15 study units sampled for trends were distributed among 4 hydrogeologic provinces: Central Valley, Basin and Range, Desert, and Transverse and selected Peninsular Ranges. The total number of status wells sampled, along with those sampled again for trends, varied by study unit. In the Central Valley hydrogeologic province, the numbers of status wells and trend wells in each study unit were as follows: Kern County subbasin study unit—47 status wells, 5 trend wells Central Eastside San Joaquin Basin study unit—58 status wells, 6 trend wells Middle Sacramento Valley study unit—71 status wells, 8 trend wells Northern Sacramento Valley study unit—43 status wells, 4 trend wells Madera–Chowchilla study unit—30 status wells, 4 trend wells Western San Joaquin Valley study unit—39 status wells, 4 trend wells. The Basin and Range hydrogeologic province had only one study unit: Owens and Indian Wells Valleys study unit—53 status wells, 6 trend wells. In the Desert hydrogeologic province, the numbers of wells were as follows: Coachella Valley study unit—19 status wells 4 trend wells Colorado River study unit—20 status wells, 3 trend wells Antelope Valley study unit—56 status wells, 6 trend wells Mojave study unit—52 status wells, 7 trend wells Borrego Valley, Central Desert and Low-Use Basins of the Mojave and Sonoran Deserts study unit—49 status wells, 6 trend wells. In the Transverse and Selected Peninsular Ranges hydrogeologic province, the numbers of wells were as follows: Coastal Los Angeles Basin study unit—61 status wells, 8 trend wells Upper Santa Ana Watershed study unit—90 status wells, 16 trend wells Santa Clara River Valley study unit—42 status wells, 6 trend wells. The groundwater samples were analyzed for a number of synthetic organic constituents (volatile organic compounds, pesticides, and pesticide degradates), constituents of special interest (perchlorate, N -nitrosodimethylamine [NDMA], and 1,2,3-trichloropropane [1,2,3-TCP]), and naturally occurring inorganic constituents (nutrients, major and minor ions, and trace elements). Naturally occurring isotopes (tritium, carbon-14, and stable isotopes of hydrogen and oxygen in water) also were measured to help identify processes affecting groundwater quality and the sources and ages of the sampled groundwater. More than 200 constituents and water-quality indicators were investigated. Quality-control samples (blanks, replicates, or samples for matrix spikes) were collected at 34 percent of the trend wells, and the results for these samples were used to evaluate the quality of the data for the groundwater samples. On the basis of detections in laboratory and field blanks in samples from GAMA-PBP study units, including the study units presented here, some groundwater results were adjusted in this report. Differences between replicate samples were mostly within acceptable ranges, indicating acceptably low variability in analytical results. Median matrix-spike recoveries were within the acceptable range (70 to 130 percent) for 189 of the 224 compounds for which matrix spikes were analyzed (84 percent). This study did not attempt to evaluate the quality of water delivered to consumers. After withdrawal, groundwater used for drinking water typically is treated, disinfected, and blended with other waters to attain acceptable water quality. The benchmarks used in this report apply to treated water that is served to the consumer, not to untreated groundwater. To provide some context for the results, however, concentrations of constituents measured in these groundwater samples were compared with benchmarks established by the U.S. Environmental Protection Agency and California Department of Public Health. Comparisons between data collected for this study and benchmarks for drinking-water quality are for illustrative purposes only and are not indicative of compliance or non-compliance with those benchmarks. Most constituents that were detected in groundwater samples from the trend wells were found at concentrations less than drinking-water benchmarks. Two volatile organic compounds (VOCs)—tetrachloroethene and trichloroethene—were detected in samples from one or more wells at concentrations greater than their health-based benchmarks, and three VOCs—chloroform, tetrachloroethene, and trichloroethene—were detected in at least 10 percent of the trend-well samples from the initial sampling period and the later trend sampling period. No pesticides were detected at concentrations near or greater than their health-based benchmarks. Three pesticide constituents—atrazine, deethylatrazine, and simazine—were detected in more than 10 percent of the trend-well samples in both sampling periods. Perchlorate, a constituent of special interest, was detected at a concentration greater than its health-based benchmark in samples from one trend well in the initial sampling and trend sampling periods, and in an additional trend well sample only in the trend sampling period. Most detections of nutrients, major and minor ions, and trace elements in samples from trend wells were less than health-based benchmarks in both sampling periods. Exceptions included nitrate, fluoride, arsenic, boron, molybdenum, strontium, and uranium; these were all detected at concentrations greater than their health-based benchmarks in at least one well sample in both sampling periods. Lead and vanadium were detected above their health-based benchmarks in one sample each collected in the initial sampling period only. The isotopic ratios of oxygen and hydrogen in water and the activities of tritium and carbon-14 generally changed little between sampling periods.

California↗

Insights and strategic opportunities from the USGS 2024 Per- and Polyfluoroalkyl Substances (PFAS) Interagency Workshop

Introduction In 2021, the U.S. Geological Survey (USGS) published Circular 1490 titled, “Integrated Science for the Study of Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) in the Environment: A Strategic Science Vision for the U.S. Geological Survey” (Tokranov and others, 2021). Circular 1490 was created to be a resource for USGS scientists prioritizing and planning research related to per- and polyfluoroalkyl substances (PFAS) and to be a guide for developing partnerships with other scientists, State and Federal agencies, and stakeholders engaged in PFAS research and management and mitigation of the environmental and human-health effects of PFAS. This USGS PFAS Strategic Science Vision document was intended to be the foundation for a “living strategic vision,” periodically providing updates on the state of USGS PFAS research, emerging PFAS data gaps and needs, and progress on interagency and stakeholder PFAS partnerships and priorities. To meet this objective, the USGS planned to host an Interagency and Stakeholder PFAS Workshop every 2–3 years. During September 10–12, 2024, the USGS hosted the first Interagency and Stakeholder PFAS Workshop in Reston, Virginia. The Workshop brought together experts from other Federal agencies (U.S. Environmental Protection Agency, National Institute of Environmental Health Sciences, Food and Drug Administration, Department of Defense [Air Force, Army]), State agencies (Washington Fish and Wildlife, Virginia Department of Transportation), and academia (Harvard University, University of Maryland) to address key challenges relating to the measurement and modeling of PFAS and the implications for environmental health. Participants engaged in in-depth discussions centered around six pivotal topics related to PFAS: (1) sampling protocols, methods and interpretation; (2) environmental sources, source apportionment, and occurrence; (3) environmental fate and transport; (4) human and wildlife exposure routes and risk; (5) bioconcentration, bioaccumulation, and biomagnification; and (6) ecotoxicology and effects. Each topic had three breakout sessions. A recurrent theme of workshop discussions was how data on a nationwide scale for PFAS occurrence in various environmental matrices, including air, water, food crops, biota, soil, and streambed sediment could help to advance scientific understanding. Participants noted significant geospatial data gaps, particularly in the midwestern and southern United States and the Pacific Northwest. PFAS data collection tends to be more robust along the eastern seaboard and in California. Participants stressed how enhancing the integration of large and small datasets across various agencies could help to support national scale understanding of PFAS. To address these gaps, attendees suggested leveraging datasets from Federal entities like the USGS and the U.S. Department of Defense, State agencies, and municipal utility services to develop predictive contaminant detection and transport models. Improved coordination between water quality programs and USGS research could help to facilitate access to valuable data, leading to comprehensive databases that inform PFAS point (wastewater treatment plants and landfills) and nonpoint (runoff from land, atmospheric deposition, food packaging) sources, environmental transport mechanisms, environmental detection and concentrations, potential exposure routes, and health effects on different biota, including humans. A specific request was made to develop a map demarking the depth of modern (1953 or later) groundwater, which is susceptible to surface-derived anthropogenic (that is, human-made) contamination, based on tritium-age dating. Emphasis was placed on incorporation of hydrology, groundwater flow paths, groundwater–surface water interactions, and landscape factors in predictive statistical models as a step to improve contaminant source identification and tracking. Molecular fingerprinting approaches garnered attention as techniques to link specific PFAS mixtures detected in a sample to environmental sources and levels in biota (Dávila-Santiago and others, 2022). Integrating data from abiotic (that is, water, soil, and air) and biotic (that is, living organisms) systems identified as a research opportunity. For example, understanding the composition of soils and sediments, which include a mixture of mineral, plant, and animal components, could advance understanding of exposure pathways. The discussions highlighted opportunities to explore and understand the potential redistribution and biotic exposures of PFAS from biosolid and wastewater treatment plant effluent land application practices, in addition to atmospheric releases and discharges from landfill and wastewater treatment plants. Participants identified research gaps surrounding how these sources may contribute to contamination and may affect surrounding ecosystems, including a better definition of anthropogenic background concentrations. Moving forward, the collection of co-occurrence data was noted as a means to improve understanding of complex mixtures and to leverage companion modeling efforts focused on areas with high and low contamination levels to identify areas of concern and unaffected resources. Participants emphasized how centralized USGS databases and the establishment of sample-metadata archives can help to ensure that samples are preserved and accessible for future research. In conclusion, the workshop participants identified opportunities to bridge data gaps and improve measurement techniques, modeling frameworks, databases, and communication, to enhance the understanding of PFAS and their effects on environmental and human health. Upon completion of the workshop, participants indicated an interest in developing strategic data collection, modeling, and analytical approaches to address these challenges.

Open-File Report↗

Sources and characteristics of dissolved organic carbon in the McKenzie River, Oregon, related to the formation of disinfection by-products in treated drinking water

Executive Summary This study characterized the concentration and quality of dissolved organic carbon (DOC) in the McKenzie River, a relatively undeveloped watershed in western Oregon, and its link to forming disinfection by-products (DBPs) in treated drinking water. The study aimed to identify the primary source(s) of DOC in source water for the Eugene Water & Electric Board’s (EWEB) conventional treatment plant on the McKenzie River near river mile 11, upstream of Hayden Bridge. The two classes of regulated compounds examined—trihalomethanes (THMs) and haloacetic acids (HAAs)—form when organic carbon in raw source water reacts with chlorine and (or) bromine during water treatment. The objectives of the study were to: characterize the amount and quality of DOC in the McKenzie River and select tributaries during storms; identify the most common types of carbon using UV-vis spectroscopy and other methods; evaluate optical properties for predicting DBP precursors in surface water; and identify land cover classes or vegetation types that may be important sources of organic carbon and DBP precursors in EWEB’s source water. Eleven storms were sampled synoptically in upstream-to-downstream fashion to provide a “snapshot” of water quality conditions at four sites on the McKenzie River from Frissell Bridge (6 miles downstream from Trail Bridge Reservoir) to the EWEB water treatment plant at Hayden Bridge and nine contributing tributaries. Storms included late summer and early autumn “first flush” events and late autumn, winter, and spring storms spanning a range in streamflows from 3,000 to 26,000 cubic feet per second as measured in the main stem McKenzie River at the EWEB water intake. Water samples were analyzed for DOC concentrations and optical properties (fluorescence and ultraviolet absorbance [UVA]) across a range of wavelengths to characterize the quantity and quality of dissolved organic matter (DOM) in the McKenzie River at the drinking water intake and upstream locations. Paired sets of source and finished water samples were collected at the EWEB treatment plant to identify DOC quality parameters in raw source water that might predict DBP concentrations in finished drinking water. DOC concentrations were relatively low in the McKenzie River (0.4–3 milligrams per liter [mg/L]; average 1.5 mg/L) but much higher in the tributaries. The highest DOC concentrations occurred during “first flush” storms in October 2012 and September 2013; the highest value (16 mg/L) was measured at the 52nd Street stormwater outfall. The average DOC concentration in the lower basin-tributaries was 3.8 mg/L; three middle basin tributaries—Quartz, Gate, and Haagen Creeks, which drain private forestland with less coniferous forest compared with other higher elevation tributaries— had slightly lower average DOC concentrations (2.8 mg/L). These middle-basin watersheds may be important sources of DOC and DBP precursors to the McKenzie River, even more so than the lower basin tributaries, depending on their flows (and loads). This is particularly true after the September 2020 Holiday Farm fire, which burned much of this area. DOC concentrations increased 68 percent in the McKenzie River between the uppermost reference site at Frissell Bridge and Vida; this includes drainage from Quartz Creek, Blue River Lake and Cougar Reservoir, which all contributed DOC to the main stem. In contrast, the lowermost tributaries draining most of the agricultural and urban land did not have a large effect on DOC in the McKenzie River despite their higher DOC concentrations because of their presumed relatively low streamflows and, consequently, DOC loads. Apart from the continuous flow monitors in the McKenzie River and some tributaries (Blue River and South Fork McKenzie River, and streamflow at Hayden Bridge and Vida, Camp Creek and some other locations), streamflow was not assessed during sample collection for this study. This lack of streamflow data precludes a detailed analysis of loads, which is discussed in the future studies section. All DBP concentrations in finished drinking water were less than EPA maximum contaminant levels (MCLs) of 0.080 mg/L for the four trihalomethanes (THM4) and 0.060 mg/L for five haloacetic acids (HAA5). During the 11 storm sampling events the maximum summed concentrations were about 0.040 mg/L for both THM4 and HAA5. Compliance monitoring samples, collected separately by EWEB, yielded some higher concentrations—0.046 mg/L THM4 and 0.047 HAA5—during the December 2012 storm. The corresponding benchmark quotient (BQ) values, which indicate how close a measured DBP concentration is to the MCL, were 0.58 and 0.78, respectively, for THM4 and HAA5. Compared with a similar 2007–08 McKenzie River study that did not target storm events, concentrations of THM4 and HAA5 in finished water were 68 percent and 33 percent higher, respectively, during the current study. Due to the high dilution rates in the McKenzie River main stem, many of the individual fluorescence excitation-emission measurements were low (<0.1 Raman units) and approached analytical detection limits. Parallel factor analysis (PARAFAC) resulted in a five-component model (C1–C5) that represents five unique organic fluorophores. Components C1, C2, and C3 represent DOM associated with soil-derived, humic-like, more degraded organic matter. In contrast, components C4 and C5 represent “fresher” DOM, derived from terrestrial and aquatic plants, including algae and cyanobacteria that are common in the McKenzie River and its tributaries and reservoirs. The fluorescence data and PARAFAC modeling suggest that most of the DOC in the McKenzie River originated from terrestrial sources (primarily components C1 and C2). The largest increases in DOC in the main stem occurred in the reach upstream of Vida, from inflows by Quartz Creek, Blue River, South Fork McKenzie River, and other tributaries. Concentrations of DBPs in EWEB’s finished drinking water were positively correlated with DOC concentrations in raw source water (THM4, p <0.05; HAA5, p <0.01) for paired samples collected 12−24 hours apart. DOC concentrations were significantly positively correlated ( p <0.001) with laboratory-based fluorescent dissolved organic matter (fDOM) measurements, suggesting fDOM as a useful parameter for monitoring and predicting DOC concentration in surface water and DBP concentrations in finished water. Of all the PARAFAC components in surface water, C5 had the highest correlations with DBPs in finished water (rho = 0.77–0.84, p <0.01), followed by components C1 and C2 (rho = 0.75 and 0.71, respectively, p <0.01). This C5 carbon is associated with recently produced DOM, possibly from decomposed terrestrial and aquatic vegetation. Model loadings of these three components were considerably higher in the sampled tributaries relative to the main stem McKenzie River, with most of the observed increases in the main stem apparent at Vida. This points to Quartz Creek or other tributaries in the reach between Frissell Bridge and the sampling site near Vida (South Fork McKenzie and Blue Rivers) as potentially key contributors of DOM source material that leads to the production of DBPs in treated drinking water. A limited load analysis showed that the reservoirs contributed 8–37 percent of the instantaneous DOC loads observed at Vida at the time of sampling, which suggests other sources such as Quartz Creek and other streams in the reach between Frissell Bridge and Vida are more important. Random forest analyses identified PARAFAC components C1 and C5 and fluorescence peaks A, C, M, T and N as the best predictors for HAA5 concentrations in finished drinking water, explaining 62.5 percent of the variation. The best predictors for THM4 were C1, C4 + C5, and peaks T, A, and N, which explained 33 percent of the variation. Several land cover and vegetation classes were correlated with DOC concentration and other optical measurements. The percentage of evergreen forest in each of the subwatersheds sampled was negatively correlated ( p <0.001) with DOC concentration and many optical indicators of DOM quantity: UVA 254 , fDOM, and all of the fluorescence peaks. In contrast, mixed (deciduous) forest was positively correlated ( p <0.001) with DOC, fDOM, UVA 254 , and several fluorescence peaks, demonstrating the importance of deciduous leaf fall in generating DOC and DBP precursors. The high level of human activities in the middle and lower portion of the basin—including timber harvesting and road construction on private forestland, agricultural, rural, industrial, and urban development—have resulted in the greatest loss in native coniferous and mixed deciduous forests in the basin. DOC loading from these tributaries and reservoir releases, which contain DOC from terrestrial and aquatic productivity, both enrich the McKenzie River. Concentrations of DOC increased an average of 71 percent (range 30–120 percent) in the McKenzie River between Frissell Bridge, the upstream reference site, and Vida. PARAFAC components C1, C2, and C5—which were correlated with DBPs in finished water—increased, on average, 109–136 percent (range 20–250 percent) in this same Frissell-to-Vida reach. These increases occur from input of tributaries in the middle basin such as Quartz Creek and others, as noted above. Future monitoring, field, and lab studies can improve our understanding of seasonal and spatial sources of organic carbon contributing DBP precursors to the McKenzie River and allow detection of long-term trends resulting from the recent Holiday Farm Fire, which burned 173,393 acres of forestland, including riparian areas along the main stem, and numerous structures, homes, and outbuildings in September 2020. Future studies could examine DOC fluxes and flushing of carbon from the watershed, investigate the role of precipitation amount and intensity in mobilizing carbon and sediment, and evaluate impacts to aquatic communities and human health as part of a post-fire assessment. Other areas ripe for study include evaluating the impacts of potential temperature increases on carbon sequestration and decomposition in the burned and unburned forests and identifying practices that foster sequestration of carbon in forest soils. The use of fluorescence sensors such as fDOM to monitor the concentration and composition of raw water supplies may be improved for detection of specific DBP precursors, to provide continuous and real-time information to treatment plant operators. Future studies that monitor DOM amount and quality, and DBP Formation Potential (FP), particularly during storm events, paired with streamflow measurements, as suggested above, could help identify areas that contribute high DOC loads and thus help managers identify the key areas to focus restoration activities. Other studies could examine treatment options for currently regulated DBPs and potentially unregulated compounds, including advanced biological treatments for their removal. This study was a collaboration between the U.S. Geological Survey (USGS) and EWEB in Eugene, Oregon, with additional funding provided from USGS Cooperative Matching Funds Program.

Oregon↗

Quality of pesticide data for groundwater analyzed for the National Water-Quality Assessment Project, 2013–18

The National Water-Quality Assessment (NAWQA) Project of the U.S. Geological Survey (USGS) submitted nearly 1,900 samples collected from groundwater sites across the United States in 2013–18 for analysis of 225 pesticide compounds (pesticides and pesticide degradates, hereafter referred to as “pesticides”) by USGS National Water Quality Laboratory schedule 2437 (S2437). For the associated NAWQA study of pesticide occurrence and concentration in groundwater, and for other studies using pesticide results determined by S2437, it is necessary to assess the ability of reported results to meet data-quality requirements that will allow study objectives to be achieved. This assessment of the quality of S2437 results reported in 2013–18 examined data from field and laboratory quality-control samples, along with third-party performance assessment samples, to estimate bias and variability and to identify their potential sources, with an emphasis on implications for the interpretation of pesticide data for groundwater. Results indicate that measurements produced by the S2437 method for most pesticides have bias and variability that would be considered acceptable for many interpretative studies, which could therefore use the results without qualification or censoring. However, the reported data for a subset of pesticides have the potential for unacceptable contamination bias, high or low recovery bias, or high variability as a consequence of method performance and (or) nonlaboratory factors that could preclude their use for certain common objectives or could necessitate adjustment or qualification to meet those objectives. Based on data for laboratory blanks, censoring of some detections for a subset of pesticides reported by the laboratory in environmental samples might be necessary or desirable to avoid an unacceptably high likelihood of a false-positive result caused by laboratory contamination. The 90-percent upper confidence limit for the 95th percentile of laboratory blank concentration equals or exceeds the minimum reported groundwater concentration in at least 1 water year for 28 pesticides. During at least 1 water year, this upper confidence limit exceeds the maximum laboratory detection limit for 17 pesticides and exceeds the maximum laboratory reporting limit for 3 pesticides (ametryn, atrazine, and diazinon). The level of contamination indicated by this upper confidence limit should not substantially affect the suitability of reported environmental concentrations for any compound for comparison with corresponding human-health benchmarks. Despite being subjected to the same laboratory processes as laboratory blanks, field blanks indicated little evidence of contamination bias. This observation could largely be the consequence of data-reporting practices, which utilize detections in laboratory blanks to censor results in associated field samples (including blanks and environmental samples) when relative concentrations indicate that a result could have a substantial contribution from laboratory contamination. Laboratory censoring appears likely to reduce the risk of false-positive results in environmental samples below the level that laboratory blank results alone would imply. Whereas data available for third-party blind blank samples analyzed in 2018 indicate that only propoxur had any false-positive results, data for pesticides that were not spiked into blind spike samples analyzed in 2013–18 indicate that the false-positive rates for 31 pesticides exceeded 1 percent when considering only detections reported at concentrations greater than the maximum detection limit. Although about half of these pesticides lack substantial supporting evidence of contamination bias based on laboratory blank or field blank detections, indicating that spiking issues or degradation of parent compounds within the spiked samples might be a contributing factor to some false-positive results, these results indicate the need to closely examine detections reported for some pesticides in environmental samples analyzed during a similar period for possible contributions from contamination bias. Data for blind spike samples that were spiked at concentrations above the maximum reporting limit indicate that false-negative rates for eight pesticides exceed 10 percent; substantial low bias could affect results reported for these pesticides in environmental samples analyzed during a similar period. Data for laboratory reagent spikes, which measure recovery of pesticides in blank water, show little evidence for unacceptable recovery bias for S2437 pesticides. However, field matrix spikes, which measure recovery of pesticides in environmental matrices, indicate that degradation and (or) matrix effects could result in moderate to substantial low bias for groundwater results for several pesticides. Low bias could cause some reported concentrations to be categorized as being below a benchmark when the actual concentration in groundwater is greater than the benchmark. Occurrence and concentrations in groundwater could be substantially underrepresented for six pesticides with benchmarks (1H-1,2,4-triazole, asulam, bifenthrin, cis-permethrin, fenbutatin oxide, and naled) that have median recoveries between zero and 50 percent in field matrix spikes. Two compounds (didealkylatrazine and 2-hydroxy-6-ethylamino-4-amino-s-triazine) have median recoveries near or greater than 150 percent in field matrix spikes, indicating a substantial high bias. Plots of data for all spike types show clear changes in the typical recovery with time for some pesticides, which would require further examination for evaluation of temporal trends in environmental concentrations. Data for laboratory reagent spikes indicate that nearly all S2437 pesticides have acceptable variability resulting from random measurement error. Only two compounds (fenbutatin oxide and naled) have F-pseudosigma values greater than 30 percent for recovery, which implies the potential for relatively high variability in reported concentrations and could affect comparison of concentrations to benchmarks and determination of whether concentrations for samples collected at separate locations or times are truly different with a specified level of confidence. Data for third-party blind spike samples show relatively high variability for a greater number of pesticides, although these results likely reflect the influence of degradation and (or) differences in the magnitude and variability of concentrations used for blind spikes relative to laboratory reagent spikes. Detailed analysis of variability using field replicate data is possible for only 12 pesticides on S2437; low variability in analyte detection and concentration is indicated for most of these pesticides in groundwater.

Scientific Investigations Report↗

Geophysics- and geochemistry-based assessment of the geochemical characteristics and groundwater-flow system of the U.S. part of the Mesilla Basin/Conejos-Médanos aquifer system in Doña Ana County, New Mexico, and El Paso County, Texas, 2010–12

One of the largest rechargeable groundwater systems by total available volume in the Rio Grande/Río Bravo Basin (hereinafter referred to as the “Rio Grande”) region of the United States and Mexico, the Mesilla Basin/Conejos-Médanos aquifer system, supplies water for irrigation as well as for cities of El Paso, Texas; Las Cruces, New Mexico; and Ciudad Juárez, Chihuahua, Mexico. The U.S. Geological Survey in cooperation with the Bureau of Reclamation assessed the groundwater resources in the Mesilla Basin and surrounding areas in Doña Ana County, N. Mex., and El Paso County, Tex., by using a combination of geophysical and geochemical methods. The study area consists of approximately 1,400 square miles in Doña Ana County, N. Mex., and 100 square miles in El Paso County, Tex. The Mesilla Basin composes most of the study area and can be divided into three parts: the Mesilla Valley, the West Mesa, and the East Bench. The Mesilla Valley is the part of the Mesilla Basin that was incised by the Rio Grande between Selden Canyon to the north and by a narrow valley (about 4 miles wide) to the southeast near El Paso, Tex., named the Paso del Norte, which is sometimes referred to in the literature as the “El Paso Narrows.” Previously published geophysical data for the study area were compiled and these data were augmented by collecting additional geophysical and geochemical data. Geophysical resistivity measurements from previously published helicopter frequency domain electromagnetic data, previously published direct-current resistivity soundings, and newly collected (2012) time-domain electromagnetic soundings were used in the study to detect spatial changes in the electrical properties of the subsurface, which reflect changes that occur within the hydrogeology. The geochemistry of the groundwater system was evaluated by analyzing groundwater samples collected in November 2010 for physicochemical properties, major ions, trace elements, nutrients, pesticides (reported but not used in the assessment), and environmental tracers. The data obtained from these samples (with the exception of the pesticide data) were used to gain insights into processes controlling the groundwater movement through the groundwater system in the study area. Results from the geophysical and geochemical assessments facilitated the interpretation of the geochemical characteristics of the groundwater sources and geochemical groups within the groundwater system. The groundwater-flow system in the study area consists primarily of the Mesilla Basin aquifer system, which can be divided into four hydrogeologic units by using an informal classification scheme based on basin-fill stratigraphy and sedimentology with an emphasis on aquifer characteristics. The four hydrogeologic units are (1) the Rio Grande alluvium, which is the shallow aquifer of the Mesilla Basin within the confines of the Mesilla Valley, and the three hydrogeologic units that compose the Santa Fe Group: (2) the lower part of the Santa Fe Group, which is the least productive zone, (3) the middle part of the Santa Fe Group, which is the primary water-bearing hydrogeologic unit in the basin and is generally saturated, and (4) the upper part of the Santa Fe Group, which is the most productive water-bearing unit within the Santa Fe Group but is only partially saturated in the north and largely unsaturated in the south and western parts of the Mesilla Basin. The helicopter frequency domain electromagnetic survey results indicated that approximately half of the resistivity values were less than 10 ohm-meters at depths of 50 and 100 feet with a transition where the resistivity values changed from relatively high values (greater than 20 ohm-meters) to relatively low resistivity values (less than 10 ohm-meters) near Vado, New Mexico. Slightly more than 25 percent of the gridded resistivity values from the three-dimensional grid of the combined inverse modeling results of the direct-current resistivity and time-domain electromagnetic soundings were equal to or less than 10 ohm-meters with large regions of low resistivity becoming apparent in the southernmost part of the study area near the Paso Del Norte where these low resistivity features are spatially the widest at or below the top of the bedrock. These low resistivity values might represent clayey deposits, sediments composed largely of sand and gravel saturated with saline water, or both. Historical dissolved-solids-concentration data within the surface geophysical subset area of the study area were compiled and compared to the inverse modeling results of the combined direct-current resistivity and time-domain soundings; this comparison was done to strengthen the interpretation made from the combined inverse modeling results that the low resistivity features were representative of sand and gravel deposits saturated with saline water and not clayey deposits. Water-level altitudes within the Rio Grande alluvium generally decreased from north to south, with a west to east decrease in water-level altitudes near Las Cruces, New Mexico, as a result of groundwater pumping. Groundwater flow within the Santa Fe Group is more complex than the groundwater flow within the Rio Grande alluvium because of the larger lateral and vertical extent of the Santa Fe Group compared to the Rio Grande alluvium. Groundwater from the Organ Mountains flows directly south towards the Paso del Norte. Groundwater from the Robledo Mountains, the Rough and Ready Hills, and the Sleeping Lady Hills generally flows to the southeast. Groundwater flowing near the north end of the midbasin uplift generally continues east towards the Rio Grande and then flows south on the east side of the midbasin uplift. Groundwater flowing near the west side of the midbasin uplift generally continues south parallel to the faults that make up the midbasin uplift and then flows east towards the Paso del Norte when it reaches the south end of the midbasin uplift. Groundwater from the Aden Hills and the East and West Potrillo Mountains flows to the south end of the midbasin uplift and then continues east towards the Paso del Norte. Throughout most of the Mesilla Valley, the vertical hydraulic gradient was downward because the water-level altitude in the Rio Grande alluvium was higher than it was in the Santa Fe Group, but in some areas (typically in the middle and southern parts of the Mesilla Valley), the vertical hydraulic gradient was substantially reduced or even reversed to an upward hydraulic gradient. The geochemistry data indicate that there was a complex system of multiple geochemical endmembers and mixing between these endmembers with recharge to the Rio Grande alluvium and Santa Fe Group composed mostly of seepage from the Rio Grande, inflows from deeper or neighboring water systems, and mountain-front recharge. Five distinct geochemical groups were identified in the Mesilla Basin study area: (1) ancestral Rio Grande (pre-Pleistocene) geochemical group, (2) modern Rio Grande (Pleistocene to present) geochemical group, (3) mountain-front geochemical group, (4) deep groundwater upwelling geochemical group, and (5) unknown freshwater geochemical group. The ancestral Rio Grande groundwater was water that recharged into the system as seepage losses from the ancestral Rio Grande; this groundwater generally flows from north to south-southeast towards the Paso del Norte. Groundwater on the west side of the midbasin uplift generally flows south until it reaches the southern part of the study area; from the southern part of the study area, the groundwater flows east towards the Paso del Norte. Groundwater on the east side of the midbasin uplift flows south-southeast towards the Paso del Norte where it mixes with groundwater from the modern Rio Grande, uplifted areas in the west, and the deep saline source. The water type of the modern Rio Grande geochemical group ranged from calcium-sulfate water type in the northern part of the study area to sodium-chloride-sulfate water type in the southern part of the study area; from north to south there was a substantial increase in specific conductance, strontium-87/strontium-86 ratio, potassium, and the trace metals of iron and lithium, changing the water chemistry such that it became similar to the water chemistry of the deep groundwater upwelling geochemical group. From age-dating results, water in the modern Rio Grande geochemical group was recharged to the Rio Grande alluvium within the past 10 years. The mountain-front geochemical group was generally old water (apparent age was greater than 10,000 carbon-14 years before present) that was somewhat mineralized and has relatively high concentrations of fluoride and silica, which might indicate longer exposure to volcanic and siliciclastic rocks or aluminosilicate minerals. There were five different locations of recharge determined from the groundwater geochemistry within the mountain-front geochemical group, all having a slightly different geochemical signature: (1) the Rough and Ready Hills, Robledo Mountains, and the Sleeping Lady Hills, (2) the Doña Ana Mountains, (3) the Aden Hills and West Potrillo Mountains, (4) the East Potrillo Mountains, and (5) the Sierra Juárez in Mexico. The groundwater from the Rough and Ready Hills, Robledo Mountains, the Sleeping Lady Hills, and the Doña Ana Mountains generally flows toward the Rio Grande and eventually mixes together and with the modern Rio Grande groundwater. The groundwater originating from the Aden Hills and East and West Potrillo Mountains generally flows east to southeast at a slow rate and eventually mixes and continues east, where it mixes with groundwater from the ancestral Rio Grande geochemical group and with the groundwater from the Sierra Juárez. The groundwater from the Sierra Juárez flows north and then east towards the Paso del Norte where it mixes with groundwater from the uplifted areas in the west, ancestral and modern Rio Grande groundwater, and the upwelling groundwater from a deep saline source. The deep groundwater upwelling geochemical group had the highest concentrations of bicarbonate, potassium, silica, aluminum, iron, and lithium within the study area, indicating that it had been in contact with carbonate and siliciclastic rocks for a much longer period of time and at higher temperatures compared to the other geochemical groups, and was most likely ancient marine groundwater originating from the Paleozoic and Cretaceous carbonate rocks which was upwelling into the Mesilla Basin aquifer system in the southeastern part of the study area through the extensive fault systems. Direct-current resistivity and time-domain electromagnetic soundings support the interpretation of ancient marine groundwater upwelling into the Mesilla Basin aquifer system, as do the analytical results from wells, and the helicopter frequency domain electromagnetic data collected along the Rio Grande. The hydrogen-2/hydrogen-1 ratio and oxygen-18/oxygen-16 ratio isotopic results for samples in the unknown freshwater geochemical group did not plot on the Rio Grande evaporation line, indicating this group did not have a Rio Grande signature (that is, there was no isotopic evidence of a component of Rio Grande water) and it also had the lowest mineralized content of any geochemical group in the study area.

New Mexico, Texas↗