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Water availability for human and ecological uses depends on both water quantity and water quality. The U.S. Geological Survey (USGS) is developing strategies for prioritizing regional-scale and watershed basin-scale studies of water availability across the nation. Previous USGS ranking processes for basin-scale studies incorporated primarily water quantity factors but are now considering additional water quality factors. This study presents a ranking based on the potential impacts of geogenic constituents on water quality and consideration of societal factors related to water quality. High-concentration geogenic constituents, including trace elements and radionuclides, are among the most prevalent contaminants limiting water availability in the USA and globally. Geogenic constituents commonly occur in groundwater because of subsurface water-rock interactions, and their distributions are controlled by complex geochemical processes. Geogenic constituent mobility can also be affected by human activities (e.g., mining, energy production, irrigation, and pumping). Societal factors and relations to drinking water sources and water quality information are often overlooked when evaluating research priorities. Sociodemographic characteristics, data gaps resulting from historical data-collection disparities, and infrastructure condition/age are examples of factors to consider regarding environmental justice. This paper presents approaches for ranking and prioritizing potential basin-scale study areas across the contiguous USA by considering a suite of conventional physical and geochemical variables related to geogenic constituents, with and without considering variables related to societal factors. Simultaneous consideration of societal and conventional factors could provide decision makers with more diverse, interdisciplinary tools to increase equity and reduce bias in prioritizing focused research areas and future water availability studies., (© 2024. This is a U.S. Government work and not under copyright protection in the US; foreign copyright protection may apply.)

Increases in fluxes of nitrogen (N) and phosphorus (P) in the environment have led to negative impacts affecting drinking water, eutrophication, harmful algal blooms, climate change, and biodiversity loss. Because of the importance, scale, and complexity of these issues, it may be useful to consider methods for prioritizing nutrient research in representative drainage basins within a regional or national context. Two systematic, quantitative approaches were developed to (1) identify basins that geospatial data suggest are most impacted by nutrients and (2) identify basins that have the most variability in factors affecting nutrient sources and transport in order to prioritize basins for studies that seek to understand the key drivers of nutrient impacts. The "impact" approach relied on geospatial variables representing surface-water and groundwater nutrient concentrations, sources of N and P, and potential impacts on receptors (i.e., ecosystems and human health). The "variability" approach relied on geospatial variables representing surface-water nutrient concentrations, factors affecting sources and transport of nutrients, model accuracy, and potential receptor impacts. One hundred and sixty-three drainage basins throughout the contiguous United States were ranked nationally and within 18 hydrologic regions. Nationally, the top-ranked basins from the impact approach were concentrated in the Midwest, while those from the variability approach were dispersed across the nation. Regionally, the top-ranked basin selected by the two approaches differed in 15 of the 18 regions, with top-ranked basins selected by the variability approach having lower minimum concentrations and larger ranges in concentrations than top-ranked basins selected by the impact approach. The highest ranked basins identified using the variability approach may have advantages for exploring how landscape factors affect surface-water quality and how surface-water quality may affect ecosystems. In contrast, the impact approach prioritized basins in terms of human development and nutrient concentrations in both surface water and groundwater, thereby targeting areas where actions to reduce nutrient concentrations could have the largest effect on improving water availability and reducing ecosystem impacts., (© 2024. This is a U.S. Government work and not under copyright protection in the US; foreign copyright protection may apply.)

Widely used isotope ratio mass spectrometers have limited capabilities to measure metabolites, drugs, or small polyatomic ions without the loss of structural isotopic information. A new approach has recently been introduced that uses electrospray ionization Orbitrap to measure multidimensional isotope signatures of intact polar compounds. Using nitrate as a model compound, this study aims to establish performance metrics for comparisons with conventional IRMS at the natural abundance level. We present a framework on how to convert isotopolog intensities to δ values that are commonly used in the isotope geochemistry community. The quantification of seven nitrate isotopologs provides multiple pathways for obtaining the primary N and O δ values including non-mass-dependent O isotope variations, as well as opportunities to explore nonrandom isotopic distributions (i.e., clumping effects) within molecular nitrate. Using automation and the adaptation of measurement principles that are specific to isotope ratio analysis, nitrate δ 15 N AIR , δ 18 O VSMOW , and δ 17 O VSMOW were measured with a long-term precision of 0.4‰ or better for isotopic reference materials and purified nitrate from environmental samples. In addition, we demonstrate promising results for unpurified environmental samples in liquid form. With these new developments, this study connects the two largely disparate mass spectrometry fields of bioanalytical MS and isotope ratio MS, thus providing a route to measure new isotopic signatures in diverse organic and inorganic solutes.

Natural chlorate (ClO 3 - ) is widely distributed in terrestrial and extraterrestrial environments. To improve understanding of the origins and distribution of ClO 3 - , we developed and tested methods to determine the multi-dimensional isotopic compositions (δ 18 O, Δ 17 O, δ 37 Cl, 36 Cl/Cl) of ClO 3 - and then applied the methods to samples of natural nitrate-rich caliche-type salt deposits in the Atacama Desert, Chile, and Death Valley, USA. Tests with reagents and artificial mixed samples indicate stable-isotope ratios were minimally affected by the purification processes. Chlorate extracted from Atacama samples had δ 18 O = +7.0 to +11.1‰, Δ 17 O = +5.7 to +6.4‰, δ 37 Cl = -1.4 to +1.3‰, and 36 Cl/Cl = 48 × 10 -15 to 104 × 10 -15 . Chlorate from Death Valley samples had δ 18 O = -6.9 to +1.6‰, Δ 17 O = +0.4 to +2.6‰, δ 37 Cl = +0.8 to +1.0‰, and 36 Cl/Cl = 14 × 10 -15 to 44 × 10 -15 . Positive Δ 17 O values of natural ClO 3 - indicate that its production involved reaction with O 3 , while its Cl isotopic composition is consistent with a tropospheric or near-surface source of Cl. The Δ 17 O and δ 18 O values of natural ClO 3 - are positively correlated, as are those of ClO 4 - and NO 3 - from the same localities, possibly indicating variation in the relative contributions of O 3 as a source of O in the formation of the oxyanions. Additional isotopic analyses of ClO 3 - could provide stronger constraints on its production mechanisms and/or post-formational alterations, with applications for environmental forensics, global biogeochemical cycling of Cl, and the origins of oxyanions detected on Mars., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Hundreds of explosive-contaminated marine sites exist globally, many of which contain the common munitions constituent hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Quantitative information about RDX transformation in coastal ecosystems is essential for management of many of these sites. Isotopically labelled RDX containing 15 N in all 3 nitro groups was used to track the fate of RDX in three coastal ecosystem types. Flow-through mesocosms representing subtidal vegetated (silt/eel grass), subtidal non-vegetated (sand) and intertidal marsh ecosystems were continuously loaded with isotopically labelled RDX for 16-17 days. Sediment, pore-water and overlying surface water were analyzed to determine the distribution of RDX, nitroso-triazine transformation products (NXs) and nitrogen containing complete mineralization products, including ammonium, nitrate+nitrite, nitrous oxide and nitrogen gas. The marsh, silt, and sand ecotypes transformed 94%, 90% and 76% of supplied RDX, respectively. Total dissolved NXs accounted for 2%-4% of the transformed 15 N-RDX. The majority of RDX transformation in the water column was by mineralization to inorganic N (dissolved and evaded; 64%-78% of transformed 15 N-RDX). RDX was mineralized primarily to N 2 O (62-74% of transformed 15 N-RDX) and secondarily to N 2 (1-2% of transformed 15 N-RDX) which exchanged with the atmosphere. Transformation of RDX was favored in carbon-rich lower redox potential sediments of the silt and marsh mesocosms where anaerobic processes of iron and sulfate reduction were most prevalent. RDX was most persistent in the carbon-poor sand mesocosm. Partitioning of 15 N derived from RDX onto sediment and suspended particulates was negligible in the overall mass balance of RDX transformation (2%-3% of transformed 15 N-RDX). The fraction of 15 N derived from RDX that was sorbed or assimilated in sediment was largest in the marsh mesocosm (most organic carbon), and smallest in the sand mesocosm (largest grain size and least organic carbon). Sediment redox conditions and available organic carbon stores affect the fate of RDX in different coastal marine habitats., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Rationale: The isotope ratios of nitrogen ( 15 N/ 14 N) and oxygen ( 18 O/ 16 O) in nitrite (NO 2 - ) can be measured by conversion of the nitrite into nitrous oxide (N 2 O) with azide, followed by mass spectrometric analysis of N 2 O by gas chromatography isotope ratio mass spectrometry (GC/IRMS). While applying this method to brackish samples, we noticed that the N and O isotope ratio measurements of NO 2 - are highly sensitive to sample salinity and to the pH at which samples are preserved., Methods: We investigated the influence of sample salinity and sample preservation pH on the N and O isotope ratios of the N 2 O produced from the reaction of NO 2 - with azide. The N 2 O isotope ratios were measured by GC/IRMS., Results: Under the experimental reaction conditions, the conversion of NO 2 - into N 2 O was less complete in lower salinity solutions, resulting in respective N and O isotopic offsets of +2.5‰ and -14.0‰ compared with seawater solutions. Differences in salinity were also associated with differences in the fraction of O atoms exchanged between NO 2 - and water during the reaction. Similarly, aqueous NO 2 - samples preserved at elevated pH values resulted in the incomplete conversion of NO 2 - into N 2 O by azide, and consequent pH-dependent isotopic offsets, as well as differences in the fraction of O atoms exchanged with water. The addition of sodium chloride to the reaction matrix of samples and standards largely mitigated salinity-dependent isotopic offsets in the N 2 O product, and nearly homogenized the fraction of O atom exchange among samples of different salinity. A test of the hypobromite-azide method to measure N isotope ratios of ammonium by conversion into NO 2 - then N 2 O revealed no influence of sample salinity on the N isotope ratios of the N 2 O product., Conclusions: We outline recommendations to mitigate potential matrix effects among samples and standards, to improve the accuracy of N and O isotope ratios in NO 2 - measured with the azide method., (© 2019 John Wiley & Sons, Ltd.)

Concentrations and emissions of greenhouse gases CO 2 , CH 4 , and N 2 O commonly are examined individually in aquatic environments in which each is expected to be relatively important; however, their co-occurrence and dynamic interactions in fluvial settings could provide important information about their controlling biogeochemical processes and potential contributions to global climate change. Spatial and temporal variability of CH 4 , N 2 O, and CO 2 concentrations were measured from June 1999 to September 2003 in two nitrate-rich (40-1200 μM) streams draining agricultural land in the midwestern USA that differed ~13-fold in flow. Seasonal (biweekly), diel (hourly), and transport-oriented (reach-scale) sampling approaches were compared. Dissolved gas concentrations exceeded atmospheric equilibrium values up to 700- and 16-fold, for CH 4 and N 2 O, respectively. Mean concentrations were higher in the larger stream than in the smaller stream. In both streams, CH 4 emissions were generally higher in summer-fall and negatively correlated with flow and NO 3 - concentration while N 2 O emissions were generally higher in winter/spring and positively correlated with flow and NO 3 - . In the small stream, diel variations in the concentrations, emissions, and isotopic compositions of CH 4 , N 2 O, and NO 2 - resulted from diel variations in sources, sinks, and air-water gas exchange velocities. Seasonal mean total (CH 4  + N 2 O) area-normalized emission rates, expressed as CO 2 warming potential equivalents, were similar for the two streams, but the total reach-scale emission rate for the larger stream, including CO 2 , was about 2.9 times that of the smaller stream (131.6 vs 46.0 kg CO 2 equivalents km -1  day -1 , respectively). The CH 4 contribution to this flux was 9-28%, despite the relatively high NO 3 - and O 2 concentrations in the streams, indicating contributions from upwelling groundwater or reactions in streambed sediment., (Published by Elsevier B.V.)

Measurements of the stable isotope ratios of nitrogen ( 15 N/ 14 N) and oxygen ( 18 O/ 16 O) in nitrate (NO 3 - ) enable identification of sources, dispersal, and fate of natural and contaminant NO 3 - in aquatic environments. The 18 O/ 16 O of NO 3 - produced by nitrification is often assumed to reflect the proportional contribution of oxygen atom sources, water, and molecular oxygen, in a 2:1 ratio. Culture and seawater incubations, however, indicate oxygen isotopic equilibration between nitrite (NO 2 - ) and water, and kinetic isotope effects for oxygen atom incorporation, which modulate the NO 3 - 18 O/ 16 O produced during nitrification. To investigate the influence of kinetic and equilibrium effects on the isotopic composition of NO 3 - produced from the nitrification of ammonia (NH 3 ), we incubated streamwater supplemented with ammonium (NH 4 + ) and increments of 18 O-enriched water. Resulting NO 3 - 18 O/ 16 O ratios showed (1) a disproportionate sensitivity to the 18 O/ 16 O ratio of water, mediated by isotopic equilibration between water and NO 2 - , as well as (2) kinetic isotope discrimination during O atom incorporation from molecular oxygen and water. Empirically, the NO 3 - 18 O/ 16 O ratios thus produced fortuitously converge near the 18 O/ 16 O ratio of water. More elevated NO 3 - 18 O/ 16 O values commonly reported in soils and oxic groundwater may thus derive from processes additional to nitrification, including NO 3 - reduction.

Coastal marine habitats become contaminated with the munitions constituent, Hexahydro-1,3,5-trinitro-1,3,5-trazine (RDX), via military training, weapon testing and leakage of unexploded ordnance. This study used 15 N labeled RDX in simulated aquarium-scale coastal marine habitat containing seawater, sediment, and biota to track removal pathways from surface water including sorption onto particulates, degradation to nitroso-triazines and mineralization to dissolved inorganic nitrogen (DIN). The two aquaria received continuous RDX inputs to maintain a steady state concentration (0.4 mg L -1 ) over 21 days. Time series RDX and nitroso-triazine concentrations in dissolved (surface and porewater) and sorbed phases (sediment and suspended particulates) were analyzed. Distributions of DIN species (ammonium, nitrate + nitrite and dissolved N 2 ) in sediments and overlying water were also measured along with geochemical variables in the aquaria. Partitioning of RDX and RDX-derived breakdown products onto surface sediment represented 13% of the total added 15 N as RDX ( 15 N-[RDX]) equivalents after 21 days. Measured nitroso-triazines in the aquaria accounted for 6-13% of total added 15 N-[RDX]. 15 N-labeled DIN was found both in the oxic surface water and hypoxic porewaters, showing that RDX mineralization accounted for 34% of the 15 N-[RDX] added to the aquaria over 21 days. Labeled ammonium ( 15 NH 4 + , found in sediment and overlying water) and nitrate + nitrite ( 15 NO X , found in overlying water only) together represented 10% of the total added 15 N-[RDX]. The production of 15 N labeled N 2 ( 15 N 2 ), accounted for the largest individual sink during the transformation of the total added 15 N-[RDX] (25%). Hypoxic sediment was the most favorable zone for production of N 2 , most of which diffused through porous sediments into the water column and escaped to the atmosphere., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This paper uses chemical and physical data from a large 2017 U.S. Geological Survey groundwater dataset with wells in the U.S. and three smaller international groundwater datasets with wells primarily in Australia and Spain to carry out a comprehensive investigation of brackish groundwater composition in relation to minimum desalination energy costs. First, we compute the site-specific least work required for groundwater desalination. Least work of separation represents a baseline for specific energy consumption of desalination systems. We develop simplified equations based on the U.S. data for least work as a function of water recovery ratio and a proxy variable for composition, either total dissolved solids, specific conductance, molality or ionic strength. We show that the U.S. correlations for total dissolved solids and molality may be applied to the international datasets. We find that total molality can be used to calculate the least work of dilute solutions with very high accuracy. Then, we examine the effects of groundwater solute composition on minimum energy requirements, showing that separation requirements increase from calcium to sodium for cations and from sulfate to bicarbonate to chloride for anions, for any given TDS concentration. We study the geographic distribution of least work, total dissolved solids, and major ions concentration across the U.S. We determine areas with both low least work and high water stress in order to highlight regions holding potential for desalination to decrease the disparity between high water demand and low water supply. Finally, we discuss the implications of the USGS results on water resource planning, by comparing least work to the specific energy consumption of brackish water reverse osmosis plants and showing the scaling propensity of major electrolytes and silica in the U.S. groundwater samples., (Copyright © 2018. Published by Elsevier Ltd.)

Natural perchlorate (ClO 4 - ) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ 37 Cl, δ 18 O, and Δ 17 O), indicating that ClO 4 - may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO 4 - , but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO 4 - in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO 4 - was transported from solutions into plants similarly to NO 3 - but preferentially to Cl - (4-fold). The ClO 4 - isotopic compositions of initial ClO 4 - reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO 4 - uptake or accumulation. The ClO 4 - isotopic composition of field-grown snap beans was also consistent with that of ClO 4 - in varying proportions from irrigation water and precipitation. NO 3 - uptake had little or no effect on NO 3 - isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε ( 15 N/ 18 O) ratio of 1.05 was observed between NO 3 - in hydroponic solutions and leaf extracts, consistent with partial NO 3 - reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO 4 - in commercial produce, as illustrated by spinach, for which the ClO 4 - isotopic composition was similar to that of indigenous natural ClO 4 - . Our results indicate that some types of plants can accumulate and (presumably) release ClO 4 - to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO 4 - and NO 3 - in plants may be useful for determining sources of fertilizers and sources of ClO 4 - in their growth environments and consequently in food supplies., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Subsurface brines with high nitrate (NO 3 - ) concentration are common in desert environments as atmospheric nitrogen is concentrated by the evaporation of precipitation and little nitrogen uptake. However, in addition to having an elevated mean concentration of ∼525 mg/L (as N), NO 3 - in the coastal sabkhas of Abu Dhabi is enriched in 15 N (mean δ 15 N ∼17‰), which is an enigma. A NO 3 - solute mass balance analysis of the sabkha aquifer system suggests that more than 90% of the nitrogen is from local atmospheric deposition and the remainder from ascending brine. In contrast, isotopic mass balances based on Δ 17 O, δ 15 N, and δ 18 O data suggest approximately 80 to 90% of the NO 3 - could be from ascending brine. As the sabkha has essentially no soil, no vegetation, and no anthropogenic land or water use, we propose to resolve this apparent contradiction with a density-driven free-convection transport model. In this conceptual model, the density of rain is increased by solution of surface salts, transporting near-surface oxygenated NO 3 - bearing water downward where it encounters reducing conditions and mixes with oxygen-free ascending geologic brines. In this environment, NO 3 - is partially reduced to nitrogen gas (N 2 ), thus enriching the remaining NO 3 - in heavy isotopes. The isotopically fractionated NO 3 - and nitrogen gas return to the near-surface oxidizing environment on the upward displacement leg of the free-convection cycle, where the nitrogen gas is released to the atmosphere and new NO 3 - is added to the system from atmospheric deposition. This recharge/recycling process has operated over many cycles in the 8000-year history of the shallow aquifer, progressively concentrating and isotopically fractionating the NO 3 - ., (© 2016, National Ground Water Association.)

Rationale: Perchlorate (ClO 4 - ) is a common trace constituent of water, soils, and plants; it has both natural and synthetic sources and is subject to biodegradation. The stable isotope ratios of Cl and O provide three independent quantities for ClO 4 - source attribution and natural attenuation studies: δ 37 Cl, δ 18 O, and δ 17 O (or Δ 17 O or 17 Δ) values. Documented reference materials, calibration schemes, methods, and interferences will improve the reliability of such studies., Methods: Three large batches of KClO 4 with contrasting isotopic compositions were synthesized and analyzed against VSMOW-SLAP, atmospheric O 2 , and international nitrate and chloride reference materials. Three analytical methods were tested for O isotopes: conversion of ClO 4 - to CO for continuous-flow IRMS (CO-CFIRMS), decomposition to O 2 for dual-inlet IRMS (O2-DIIRMS), and decomposition to O 2 with molecular-sieve trap (O2-DIIRMS+T). For Cl isotopes, KCl produced by thermal decomposition of KClO 4 was reprecipitated as AgCl and converted into CH 3 Cl for DIIRMS., Results: KClO 4 isotopic reference materials (USGS37, USGS38, USGS39) represent a wide range of Cl and O isotopic compositions, including non-mass-dependent O isotopic variation. Isotopic fractionation and exchange can affect O isotope analyses of ClO 4 - depending on the decomposition method. Routine analyses can be adjusted for such effects by normalization, using reference materials prepared and analyzed as samples. Analytical errors caused by SO 4 2 - , NO 3 - , ReO 4 2 - , and C-bearing contaminants include isotope mixing and fractionation effects on CO and O 2 , plus direct interference from CO 2 in the mass spectrometer. The results highlight the importance of effective purification of ClO 4 - from environmental samples., Conclusions: KClO 4 reference materials are available for testing methods and calibrating isotopic data for ClO 4 - and other substances with widely varying Cl or O isotopic compositions. Current ClO 4 - extraction, purification, and analysis techniques provide relative isotope-ratio measurements with uncertainties much smaller than the range of values in environmental ClO 4 - , permitting isotopic evaluation of environmental ClO 4 - sources and natural attenuation. Copyright © 2016 John Wiley & Sons, Ltd., (Copyright © 2016 John Wiley & Sons, Ltd.)

Brackish groundwater (BGW) is increasingly used for water supplies where fresh water is scarce, but the distribution and availability of such resources have not been characterized at the national scale in the United States since the 1960s. Apart from its distribution and accessibility, BGW usability is a function of the chemical requirements of the intended use, chemical characteristics of the resource, and treatment options to make the resource compatible with the use. Here, we discuss relations between these three chemical factors using national-scale examples and local case studies. In a preliminary compilation of BGW data in the United States, five water types accounted for the major-ion composition of 70% of samples. PHREEQC calculations indicate that 57-77% of samples were oversaturated with respect to barite, calcite, or chalcedony. In the study, 5-14% of samples had concentrations of arsenic, fluoride, nitrate, or uranium that exceeded drinking-water standards. In case studies of the potential use of BGW for drinking water, irrigation, and hydraulic fracturing, PHREEQC simulations of a hypothetical treatment process resembling reverse osmosis (RO) showed that BGW had the potential to form various assemblages of mineral deposits (scale) during treatment that could adversely affect RO membranes. Speciation calculations showed that most boron in the irrigation example occurred as boric acid, which has relatively low removal efficiency by RO. Results of this preliminary study indicate that effective national or regional assessments of BGW resources should include geochemical characterizations that are guided in part by specific use and treatment requirements., (Published 2015. This article is a U.S. Government work and is in the public domain in the USA.)

Unlabelled: Kinetic isotopic fractionation of carbon and nitrogen during RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) biodegradation was investigated with pure bacterial cultures under aerobic and anaerobic conditions. Relatively large bulk enrichments in (15)N were observed during biodegradation of RDX via anaerobic ring cleavage (ε(15)N = -12.7‰ ± 0.8‰) and anaerobic nitro reduction (ε(15)N = -9.9‰ ± 0.7‰), in comparison to smaller effects during biodegradation via aerobic denitration (ε(15)N = -2.4‰ ± 0.2‰). (13)C enrichment was negligible during aerobic RDX biodegradation (ε(13)C = -0.8‰ ± 0.5‰) but larger during anaerobic degradation (ε(13)C = -4.0‰ ± 0.8‰), with modest variability among genera. Dual-isotope ε(13)C/ε(15)N analyses indicated that the three biodegradation pathways could be distinguished isotopically from each other and from abiotic degradation mechanisms. Compared to the initial RDX bulk δ(15)N value of +9‰, δ(15)N values of the NO2 (-) released from RDX ranged from -7‰ to +2‰ during aerobic biodegradation and from -42‰ to -24‰ during anaerobic biodegradation. Numerical reaction models indicated that N isotope effects of NO2 (-) production were much larger than, but systematically related to, the bulk RDX N isotope effects with different bacteria. Apparent intrinsic ε(15)N-NO2 (-) values were consistent with an initial denitration pathway in the aerobic experiments and more complex processes of NO2 (-) formation associated with anaerobic ring cleavage. These results indicate the potential for isotopic analysis of residual RDX for the differentiation of degradation pathways and indicate that further efforts to examine the isotopic composition of potential RDX degradation products (e.g., NOx) in the environment are warranted., Importance: This work provides the first systematic evaluation of the isotopic fractionation of carbon and nitrogen in the organic explosive RDX during degradation by different pathways. It also provides data on the isotopic effects observed in the nitrite produced during RDX biodegradation. Both of these results could lead to better understanding of the fate of RDX in the environment and help improve monitoring and remediation technologies., (Copyright © 2016, American Society for Microbiology. All Rights Reserved.)

Explosives used in construction have been implicated as sources of NO3(-) contamination in groundwater, but direct forensic evidence is limited. Identification of blasting-related NO3(-) can be complicated by other NO3(-) sources, including agriculture and wastewater disposal, and by hydrogeologic factors affecting NO3(-) transport and stability. Here we describe a study that used hydrogeology, chemistry, stable isotopes, and mass balance calculations to evaluate groundwater NO3(-) sources and transport in areas surrounding a highway construction site with documented blasting in New Hampshire. Results indicate various groundwater responses to contamination: (1) rapid breakthrough and flushing of synthetic NO3(-) (low δ(15)N, high δ(18)O) from dissolution of unexploded NH4NO3 blasting agents in oxic groundwater; (2) delayed and reduced breakthrough of synthetic NO3(-) subjected to partial denitrification (high δ(15)N, high δ(18)O); (3) relatively persistent concentrations of blasting-related biogenic NO3(-) derived from nitrification of NH4(+) (low δ(15)N, low δ(18)O); and (4) stable but spatially variable biogenic NO3(-) concentrations, consistent with recharge from septic systems (high δ(15)N, low δ(18)O), variably affected by denitrification. Source characteristics of denitrified samples were reconstructed from dissolved-gas data (Ar, N2) and isotopic fractionation trends associated with denitrification (Δδ(15)N/Δδ(18)O ≈ 1.31). Methods and data from this study are expected to be applicable in studies of other aquifers affected by explosives used in construction.

2,4,6-Trinitrotoluene (TNT) has been used as a military explosive for over a hundred years. Contamination concerns have arisen as a result of manufacturing and use on a large scale; however, despite decades of work addressing TNT contamination in the environment, its fate in marine ecosystems is not fully resolved. Here we examine the cycling and fate of TNT in the coastal marine systems by spiking a marine mesocosm containing seawater, sediments, and macrobiota with isotopically labeled TNT ((15)N-[TNT]), simultaneously monitoring removal, transformation, mineralization, sorption, and biological uptake over a period of 16 days. TNT degradation was rapid, and we observed accumulation of reduced transformation products dissolved in the water column and in pore waters, sorbed to sediments and suspended particulate matter (SPM), and in the tissues of macrobiota. Bulk δ(15)N analysis of sediments, SPM, and tissues revealed large quantities of (15)N beyond that accounted for in identifiable derivatives. TNT-derived N was also found in the dissolved inorganic N (DIN) pool. Using multivariate statistical analysis and a (15)N mass balance approach, we identify the major transformation pathways of TNT, including the deamination of reduced TNT derivatives, potentially promoted by sorption to SPM and oxic surface sediments.

Anaerobic ammonium oxidation (anammox) couples the oxidation of ammonium with the reduction of nitrite, producing N2. The presence and activity of anammox bacteria in groundwater were investigated at multiple locations in an aquifer variably affected by a large, wastewater-derived contaminant plume. Anammox bacteria were detected at all locations tested using 16S rRNA gene sequencing and quantification of hydrazine oxidoreductase (hzo) gene transcripts. Anammox and denitrification activities were quantified by in situ (15)NO2(-) tracer tests along anoxic flow paths in areas of varying ammonium, nitrate, and organic carbon abundances. Rates of denitrification and anammox were determined by quantifying changes in (28)N2, (29)N2, (30)N2, (15)NO3(-), (15)NO2(-), and (15)NH4(+) with groundwater travel time. Anammox was present and active in all areas tested, including where ammonium and dissolved organic carbon concentrations were low, but decreased in proportion to denitrification when acetate was added to increase available electron supply. Anammox contributed 39-90% of potential N2 production in this aquifer, with rates on the order of 10 nmol N2-N L(-1) day(-1). Although rates of both anammox and denitrification during the tracer tests were low, they were sufficient to reduce inorganic nitrogen concentrations substantially during the overall groundwater residence times in the aquifer. These results demonstrate that anammox activity in groundwater can rival that of denitrification and may need to be considered when assessing nitrogen mass transport and permanent loss of fixed nitrogen in aquifers.

Perchlorate (ClO) is a contaminant that occurs naturally throughout the world, but little is known about its distribution and interactions in terrestrial ecosystems. The objectives of this Amargosa Desert, Nevada study were to determine (i) the local-scale distribution of shallow-soil (0-30 cm) ClO with respect to shrub proximity (far and near) in three geomorphic settings (shoulder slope, footslope, and valley floor); (ii) the importance of soil, plant, and terrain variables on the hillslope-distribution of shallow-soil and creosote bush [ (Sessé & Moc. ex DC.) Coville] ClO; and (iii) atmospheric (wet plus dry, including dust) deposition of ClO in relation to soil and plant reservoirs and cycling. Soil ClO ranged from 0.3 to 5.0 μg kg. Within settings, valley floor ClO was 17× less near shrubs due in part to enhanced leaching, whereas shoulder and footslope values were ∼2× greater near shrubs. Hillslope regression models (soil, = 0.42; leaf, = 0.74) identified topographic and soil effects on ClO deposition, transport, and cycling. Selective plant uptake, bioaccumulation, and soil enrichment were evidenced by leaf ClO concentrations and Cl/ClO molar ratios that were ∼8000× greater and 40× less, respectively, than soil values. Atmospheric deposition ClO flux was 343 mg ha yr, ∼10× that for published southwestern wet-deposition fluxes. Creosote bush canopy ClO (1310 mg ha) was identified as a previously unrecognized but important and active reservoir. Nitrate δO analyses of atmospheric deposition and soil supported the leaf-cycled-ClO input hypothesis. This study provides basic data on ClO distribution and cycling that are pertinent to the assessment of environmental impacts in desert ecosystems and broadly transferable to anthropogenically contaminated systems., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

Leachate from municipal landfills can create groundwater contaminant plumes that may last for decades to centuries. The fate of reactive contaminants in leachate-affected aquifers depends on the sustainability of biogeochemical processes affecting contaminant transport. Temporal variations in the configuration of redox zones downgradient from the Norman Landfill were studied for more than a decade. The leachate plume contained elevated concentrations of nonvolatile dissolved organic carbon (NVDOC) (up to 300 mg/L), methane (16 mg/L), ammonium (650 mg/L as N), iron (23 mg/L), chloride (1030 mg/L), and bicarbonate (4270 mg/L). Chemical and isotopic investigations along a 2D plume transect revealed consumption of solid and aqueous electron acceptors in the aquifer, depleting the natural attenuation capacity. Despite the relative recalcitrance of NVDOC to biodegradation, the center of the plume was depleted in sulfate, which reduces the long-term oxidation capacity of the leachate-affected aquifer. Ammonium and methane were attenuated in the aquifer relative to chloride by different processes: ammonium transport was retarded mainly by physical interaction with aquifer solids, whereas the methane plume was truncated largely by oxidation. Studies near plume boundaries revealed temporal variability in constituent concentrations related in part to hydrologic changes at various time scales. The upper boundary of the plume was a particularly active location where redox reactions responded to recharge events and seasonal water-table fluctuations. Accurately describing the biogeochemical processes that affect the transport of contaminants in this landfill-leachate-affected aquifer required understanding the aquifer's geologic and hydrodynamic framework., (Ground Water © 2011, National Ground Water Association. No claim to original US government works.)

A new ion chromatography electrospray tandem mass spectrometry (IC-ESI/MS/MS) method has been developed for quantification and confirmation of chlorate (ClO₃⁻) in environmental samples. The method involves the electrochemical generation of isotopically labeled chlorate internal standard (Cl¹⁸O₃⁻) using ¹⁸O water (H₂¹⁸O) he standard was added to all samples prior to analysis thereby minimizing the matrix effects that are associated with common ions without the need for expensive sample pretreatments. The method detection limit (MDL) for ClO₃⁻ was 2 ng L⁻¹ for a 1 mL volume sample injection. The proposed method was successfully applied to analyze ClO₃⁻ in difficult environmental samples including soil and plant leachates. The IC-ESI/MS/MS method described here was also compared to established EPA method 317.0 for ClO₃⁻ analysis. Samples collected from a variety of environments previously shown to contain natural perchlorate (ClO₄⁻) occurrence were analyzed using the proposed method and ClO₃⁻ was found to co-occur with ClO₄⁻ at concentrations ranging from < 2 ng L⁻¹ in precipitation from Texas and Puerto Rico to >500 mg kg⁻¹ in caliche salt deposits from the Atacama Desert in Chile. Relatively low concentrations of ClO₃⁻ in some natural groundwater samples (0.1 µg L⁻¹) analyzed in this work may indicate lower stability when compared to ClO₄⁻ in the subsurface. The high concentrations ClO₃⁻ in caliches and soils (3-6 orders of magnitude greater) as compared to precipitation samples indicate that ClO₃⁻, like ClO₄⁻, may be atmospherically produced and deposited, then concentrated in dry soils, and is possibly a minor component in the biogeochemical cycle of chlorine.

Perchlorate (ClO(4)(-)) has been detected widely in groundwater and soils of the southwestern United States. Much of this ClO(4)(-) appears to be natural, and it may have accumulated largely through wet and dry atmospheric deposition. This study evaluates the isotopic composition of natural ClO(4)(-) indigenous to the southwestern U.S. Stable isotope ratios were measured in ClO(4)(-) (delta(18)O, Delta(17)O, delta(37)Cl) and associated NO(3)(-) (delta(18)O, Delta(17)O, delta(15)N) in groundwater from the southern High Plains (SHP) of Texas and New Mexico and the Middle Rio Grande Basin (MRGB) in New Mexico, from unsaturated subsoil in the SHP, and from NO(3)(-)-rich surface caliche deposits near Death Valley, California. The data indicate natural ClO(4)(-) in the southwestern U.S. has a wide range of isotopic compositions that are distinct from those reported previously for natural ClO(4)(-) from the Atacama Desert of Chile as well as all known synthetic ClO(4)(-). ClO(4)(-) in Death Valley caliche has a range of high Delta(17)O values (+8.6 to +18.4 per thousand), overlapping and extending the Atacama range, indicating at least partial atmospheric formation via reaction with ozone (O(3)). However, the Death Valley delta(37)Cl values (-3.1 to -0.8 per thousand) and delta(18)O values (+2.9 to +26.1 per thousand) are higher than those of Atacama ClO(4)(-). In contrast, ClO(4)(-) from western Texas and New Mexico has much lower Delta(17)O (+0.3 to +1.3 per thousand), with relatively high delta(37)Cl (+3.4 to +5.1 per thousand) and delta(18)O (+0.5 to +4.8 per thousand), indicating either that this material was not primarily generated with O(3) as a reactant or that the ClO(4)(-) was affected by postdepositional O isotope exchange. High Delta(17)O values in ClO(4)(-) (Atacama and Death Valley) are associated with high Delta(17)O values in NO(3)(-), indicating that both compounds preserve characteristics of O(3)-related atmospheric production in hyper-arid settings, whereas both compounds have low Delta(17)O values in less arid settings. Although Delta(17)O variations in terrestrial NO(3)(-) can be attributed to mixing of atmospheric (high Delta(17)O) and biogenic (low Delta(17)O) NO(3)(-), variations in Delta(17)O of terrestrial ClO(4)(-) are not readily explained in the same way. This study provides important new constraints for identifying natural sources of ClO(4)(-) in different environments by multicomponent isotopic characteristics, while presenting the possibilities of divergent ClO(4)(-) formation mechanisms and(or) ClO(4)(-) isotopic exchange in biologically active environments.

Perchlorate (ClO4(-)) is ubiquitous in the environment. It is produced naturally by atmospheric photochemical reactions, and also is synthesized in large quantities for military, aerospace, and industrial applications. Nitrate-enriched salt deposits of the Atacama Desert (Chile) contain high concentrations of natural ClO4(-), and have been exported worldwide since the mid-1800s for use in agriculture. The widespread introduction of synthetic and agricultural ClO4(-) into the environment has contaminated numerous municipal water supplies. Stable isotope ratio measurements of Cl and O have been applied for discrimination of different ClO4(-) sources in the environment. This study explores the potential of 36Cl measurements for further improving the discrimination of ClO4(-) sources. Groundwater and desert soil samples from the southwestern United States (U.S.) contain ClO4(-) having high 36Cl abundances (36Cl/Cl = 3100 x 10(-15) to 28,800 x 10(-15)), compared with those from the Atacama Desert (36Cl/Cl = 0.9 x 10(-15) to 590 x 10(-15)) and synthetic ClO4(-) reagents and products (36Cl/Cl = 0.0 x 10(-15) to 40 x 10(-15)). In conjunction with stable Cl and O isotope ratios, 36Cl data provide a clear distinction among three principal ClO4(-) source types in the environment of the southwestern U.S.

Perchlorate (ClO4-) is a common groundwater constituent with both synthetic and natural sources. A potentially important source of ClO4- is past agricultural application of ClO4(-)-bearing natural NO3- fertilizer imported from the Atacama Desert, Chile, but evidence for this has been largely circumstantial. Here we report ClO4- stable isotope data (delta37Cl, delta18O, and delta17O), along with other supporting chemical and isotopic environmental tracer data, to document groundwater ClO4 contamination sources and history in parts of Long Island, New York. Sampled groundwaters were oxic and ClO4- apparently was not affected by biodegradation within the aquifers. Synthetic ClO4- was indicated by the isotopic method in groundwater near a fireworks disposal site at a former missile base. Atacama ClO4- was indicated in agricultural and urbanizing areas in groundwaters with apparent ages > 20 years. In an agricultural area, ClO4- concentrations and ClO4-/NO3- ratios increased with groundwater age, possibly because of decreasing application rates of Atacama NO3- fertilizers and/or decreasing ClO4- concentrations in Atacama NO3- fertilizers in recent years. Because ClO4-/NO3- ratios of Atacama NO3- fertilizers imported in the past (approximately 2 x 10(-3) mol mol(-1)) were much higher than the CO4-/NO3- ratio of recommended drinking-water limits (7 x 10(-5) mol mol(-1) in New York), ClO4- could exceed drinking-water limits even where NO3- does not, and where Atacama NO3- was only a minor source of N. Groundwater ClO4- with distinctive isotopic composition was a sensitive indicator of past Atacama NO3- fertilizer use on Long Island and may be common in other areas that received NO3- fertilizers from the late 19th century through the 20th century.

Watershed mass balances for solutes of atmospheric origin may be complicated by the residence times of water and solutes at various time scales. In two small forested headwater catchments in the Appalachian Mountains of Virginia, USA, mean annual export rates of SO(4)(=) differ by a factor of 2, and seasonal variations in SO(4)(=) concentrations in atmospheric deposition and stream water are out of phase. These features were investigated by comparing (3)H, (35)S, delta(34)S, delta(2)H, delta(18)O, delta(3)He, CFC-12, SF(6), and chemical analyses of open deposition, throughfall, stream water, and spring water. The concentrations of SO(4)(=) and radioactive (35)S were about twice as high in throughfall as in open deposition, but the weighted composite values of (35)S/S (11.1 and 12.1x10(-15)) and delta(34)S (+3.8 and +4.1 per thousand) were similar. In both streams (Shelter Run, Mill Run), (3)H concentrations and delta(34)S values during high flow were similar to those of modern deposition, delta(2)H and delta(18)O values exhibited damped seasonal variations, and (35)S/S ratios (0-3x10(-15)) were low throughout the year, indicating inter-seasonal to inter-annual storage and release of atmospheric SO(4)(=) in both watersheds. In the Mill Run watershed, (3)H concentrations in stream base flow (10-13 TU) were consistent with relatively young groundwater discharge, most delta(34)S values were approximately the same as the modern atmospheric deposition values, and the annual export rate of SO(4)(=) was equal to or slightly greater than the modern deposition rate. In the Shelter Run watershed, (3)H concentrations in stream base flow (1-3 TU) indicate that much of the discharging ground water had been deposited prior to the onset of atmospheric nuclear bomb testing in the 1950s, base flow delta(34)S values (+1.6 per thousand) were significantly lower than the modern deposition values, and the annual export rate of SO(4)(=) was less than the modern deposition rate. Concentrations of (3)H and (35)S in Shelter Run base flow, and of (3)H, (3)He, CFC-12, SF(6), and (35)S in a spring discharging to Shelter Run, all were consistent with a bimodal distribution of discharging ground-water ages with approximately 5-20% less than a few years old and 75-95% more than 40 years old. These results provide evidence for 3 important time-scales of SO(4)(=) transport through the watersheds: (1) short-term (weekly to monthly) storage and release of dry deposition in the forest canopy between precipitation events; (2) mid-term (seasonal to interannual) cycles in net storage in the near-surface environment, and (3) long-term (decadal to centennial) storage in deep ground water that appears to be related to relatively low SO(4)(=) concentrations in spring discharge that dominates Shelter Run base flow. It is possible that the relatively low concentrations and low delta(34)S values of SO(4)(=) in spring discharge and Shelter Run base flow may reflect those of atmospheric deposition before the middle of the 20th century. In addition to storage in soils and biota, variations in ground-water residence times at a wide range of time scales may have important effects on monitoring, modeling, and predicting watershed responses to changing atmospheric deposition in small watersheds.

Internationally distributed organic and inorganic oxygen isotopic reference materials have been calibrated by six laboratories carrying out more than 5300 measurements using a variety of high-temperature conversion techniques (HTC)a in an evaluation sponsored by the International Union of Pure and Applied Chemistry (IUPAC). To aid in the calibration of these reference materials, which span more than 125 per thousand, an artificially enriched reference water (delta(18)O of +78.91 per thousand) and two barium sulfates (one depleted and one enriched in (18)O) were prepared and calibrated relative to VSMOW2b and SLAP reference waters. These materials were used to calibrate the other isotopic reference materials in this study, which yielded: Reference material delta(18)O and estimated combined uncertainty IAEA-602 benzoic acid+71.28 +/- 0.36 per thousand USGS 35 sodium nitrate+56.81 +/- 0.31 per thousand IAEA-NO-3 potassium nitrate+25.32 +/- 0.29 per thousand IAEA-601 benzoic acid+23.14 +/- 0.19 per thousand IAEA-SO-5 barium sulfate+12.13 +/- 0.33 per thousand NBS 127 barium sulfate+8.59 +/- 0.26 per thousand VSMOW2 water 0 per thousand IAEA-600 caffeine-3.48 +/- 0.53 per thousand IAEA-SO-6 barium sulfate-11.35 +/- 0.31 per thousand USGS 34 potassium nitrate-27.78 +/- 0.37 per thousand SLAP water-55.5 per thousand The seemingly large estimated combined uncertainties arise from differences in instrumentation and methodology and difficulty in accounting for all measurement bias. They are composed of the 3-fold standard errors directly calculated from the measurements and provision for systematic errors discussed in this paper. A primary conclusion of this study is that nitrate samples analyzed for delta(18)O should be analyzed with internationally distributed isotopic nitrates, and likewise for sulfates and organics. Authors reporting relative differences of oxygen-isotope ratios (delta(18)O) of nitrates, sulfates, or organic material should explicitly state in their reports the delta(18)O values of two or more internationally distributed nitrates (USGS 34, IAEA-NO-3, and USGS 35), sulfates (IAEA-SO-5, IAEA-SO-6, and NBS 127), or organic material (IAEA-601 benzoic acid, IAEA-602 benzoic acid, and IAEA-600 caffeine), as appropriate to the material being analyzed, had these reference materials been analyzed with unknowns. This procedure ensures that readers will be able to normalize the delta(18)O values at a later time should it become necessary.The high-temperature reduction technique for analyzing delta(18)O and delta(2)H is not as widely applicable as the well-established combustion technique for carbon and nitrogen stable isotope determination. To obtain the most reliable stable isotope data, materials should be treated in an identical fashion; within the same sequence of analyses, samples should be compared with working reference materials that are as similar in nature and in isotopic composition as feasible., (Copyright (c) 2009 John Wiley & Sons, Ltd.)

The biogeochemistry at the interface between sediments in a seasonally ponded wetland (slough) and an alluvial aquifer contaminated with landfill leachate was investigated to evaluate factors that can effect natural attenuation of landfill leachate contaminants in areas of groundwater/surface-water interaction. The biogeochemistry at the wetland-alluvial aquifer interface differed greatly between dry and wet conditions. During dry conditions (low water table), vertically upward discharge was focused at the center of the slough from the fringe of a landfill-derived ammonium plume in the underlying aquifer, resulting in transport of relatively low concentrations of ammonium to the slough sediments with dilution and dispersion as the primary attenuation mechanism. In contrast, during wet conditions (high water table), leachate-contaminated groundwater discharged upward near the upgradient slough bank, where ammonium concentrations in the aquifer where high. Relatively high concentrations of ammonium and other leachate constituents also were transported laterally through the slough porewater to the downgradient bank in wet conditions. Concentrations of the leachate-associated constituents chloride, ammonium, non-volatile dissolved organic carbon, alkalinity, and ferrous iron more than doubled in the slough porewater on the upgradient bank during wet conditions. Chloride, non-volatile dissolved organic carbon (DOC), and bicarbonate acted conservatively during lateral transport in the aquifer and slough porewater, whereas ammonium and potassium were strongly attenuated. Nitrogen isotope variations in ammonium and the distribution of ammonium compared to other cations indicated that sorption was the primary attenuation mechanism for ammonium during lateral transport in the aquifer and the slough porewater. Ammonium attenuation was less efficient, however, in the slough porewater than in the aquifer and possibly occurred by a different sorption mechanism. A stoichiometrically balanced increase in magnesium concentration with decreasing ammonium and potassium concentrations indicated that cation exchange was the sorption mechanism in the slough porewater. Only a partial mass balance could be determined for cations exchanged for ammonium and potassium in the aquifer, indicating that some irreversible sorption may be occurring. Although wetlands commonly are expected to decrease fluxes of contaminants in riparian environments, enhanced attenuation of the leachate contaminants in the slough sediment porewater compared to the aquifer was not observed in this study. The lack of enhanced attenuation can be attributed to the fact that the anoxic plume, comprised largely of recalcitrant DOC and reduced inorganic constituents, interacted with anoxic slough sediments and porewaters, rather than encountering a change in redox conditions that could cause transformation reactions. Nevertheless, the attenuation processes in the narrow zone of groundwater/surface-water interaction were effective in reducing ammonium concentrations by a factor of about 3 during lateral transport across the slough and by a factor of 2 to 10 before release to the surface water. Slough porewater geochemistry also indicated that the slough could be a source of sulfate in dry conditions, potentially providing a terminal electron acceptor for natural attenuation of organic compounds in the leachate plume.

Septic tank systems are an important source of NO3(-) to many aquifers, yet characterization of N mass balance and isotope systematics following septic tank effluent discharge into unsaturated sediments has received limited attention. In this study, samples of septic tank effluent before and after transport through single-pass packed-bed filters (sand filters) were evaluated to elucidate mass balance and isotope effects associated with septic tank effluent discharge to unsaturated sediments. Chemical and isotopic data from five newly installed pairs and ten established pairs of septic tanks and packed-bed filters serving single homes in Oregon indicate that aqueous solute concentrations are affected by variations in recharge (precipitation, evapotranspiration), NH4+ sorption (primarily in immature systems), nitrification, and gaseous N loss via NH3 volatilization and(or) N2 or N2O release during nitrification/denitrification. Substantial NH4+ sorption capacity was also observed in laboratory columns with synthetic effluent. Septic tank effluent delta15N-NH4+ values were almost constant and averaged +4.9 per thousand+/-0.4 per thousand (1 sigma). In contrast, delta15N values of NO3(-) leaving mature packed-bed filters were variable (+0.8 to +14.4 per thousand) and averaged +7.2 per thousand+/-2.6 per thousand. Net N loss in the two networks of packed-bed filters was indicated by average 10-30% decreases in Cl(-)-normalized N concentrations and 2-3 per thousand increases in delta15N, consistent with fractionation accompanying gaseous N losses and corroborating established links between septic tank effluent and NO3(-) in a local, shallow aquifer. Values of delta18O-NO3(-) leaving mature packed-bed filters ranged from -10.2 to -2.3 per thousand (mean -6.4 per thousand+/-1.8 per thousand), and were intermediate between a 2/3 H2O-O+1/3 O2-O conceptualization and a 100% H2O-O conceptualization of delta18O-NO3(-) generation during nitrification.

BaSO(4) precipitated from mixed salt solutions by common techniques for SO(4) (2-) isotopic analysis may contain quantities of H(2)O and NO(3) (-) that introduce errors in O isotope measurements. Experiments with synthetic solutions indicate that delta(18)O values of CO produced by decomposition of precipitated BaSO(4) in a carbon reactor may be either too low or too high, depending on the relative concentrations of SO(4) (2-) and NO(3) (-) and the delta(18)O values of the H(2)O, NO(3) (-), and SO(4) (2-). Typical delta(18)O errors are of the order of 0.5 to 1 per thousand in many sample types, and can be larger in samples containing atmospheric NO(3) (-), which can cause similar errors in delta(17)O and Delta(17)O. These errors can be reduced by (1) ion chromatographic separation of SO(4) (2-) from NO(3) (-), (2) increasing the salinity of the solutions before precipitating BaSO(4) to minimize incorporation of H(2)O, (3) heating BaSO(4) under vacuum to remove H(2)O, (4) preparing isotopic reference materials as aqueous samples to mimic the conditions of the samples, and (5) adjusting measured delta(18)O values based on amounts and isotopic compositions of coexisting H(2)O and NO(3) (-). These procedures are demonstrated for SO(4) (2-) isotopic reference materials, synthetic solutions with isotopically known reagents, atmospheric deposition from Shenandoah National Park, Virginia, USA, and sulfate salt deposits from the Atacama Desert, Chile, and Mojave Desert, California, USA. These results have implications for the calibration and use of O isotope data in studies of SO(4) (2-) sources and reaction mechanisms., (Copyright 2008 John Wiley & Sons, Ltd.)

Aerobic conditions in desert aquifers commonly allow high nitrate (NO3-) concentrations in recharge to persist for long periods of time, an important consideration for N-cycling and water quality. In this study, stable isotopes of NO3- (delta15N(NO3) and delta18O(NO3)) were used to trace NO3- cycling processes which affect concentrations in groundwater and unsaturated zone moisture in the arid Badain Jaran Desert in northwestern China. Most groundwater NO3- appears to be depleted relative to Cl- in rainfall concentrated by evapotranspiration, indicating net N losses. Unsaturated zone NO3- is generally higher than groundwater NO3- in terms of both concentration (up to 15 476 microM, corresponding to 3.6 mg NO3(-)-N per kg sediment) and ratios with Cl-. Isotopic data indicate that the NO3- derives primarily from nitrification, with a minor direct contribution of atmospheric NO3- inferred for some samples, particularly in the unsaturated zone. Localized denitrification in the saturated zone is suggested by isotopic and geochemical indicators in some areas. Anthropogenic inputs appear to be minimal, and variability is attributed to environmental factors. In comparison to other arid regions, the sparseness of vegetation in the study area appears to play an important role in moderating unsaturated zone NO3- accumulation by allowing solute flushing and deterring extensive N2 fixation.

The ability of natural attenuation to mitigate agricultural nitrate contamination in recharging aquifers was investigated in four important agricultural settings in the United States. The study used laboratory analyses, field measurements, and flow and transport modeling for monitoring well transects (0.5 to 2.5 km in length) in the San Joaquin watershed, California, the Elkhorn watershed, Nebraska, the Yakima watershed, Washington, and the Chester watershed, Maryland. Ground water analyses included major ion chemistry, dissolved gases, nitrogen and oxygen stable isotopes, and estimates of recharge date. Sediment analyses included potential electron donors and stable nitrogen and carbon isotopes. Within each site and among aquifer-based medians, dissolved oxygen decreases with ground water age, and excess N(2) from denitrification increases with age. Stable isotopes and excess N(2) imply minimal denitrifying activity at the Maryland and Washington sites, partial denitrification at the California site, and total denitrification across portions of the Nebraska site. At all sites, recharging electron donor concentrations are not sufficient to account for the losses of dissolved oxygen and nitrate, implying that relict, solid phase electron donors drive redox reactions. Zero-order rates of denitrification range from 0 to 0.14 micromol N L(-1)d(-1), comparable to observations of other studies using the same methods. Many values reported in the literature are, however, orders of magnitude higher, which is attributed to a combination of method limitations and bias for selection of sites with rapid denitrification. In the shallow aquifers below these agricultural fields, denitrification is limited in extent and will require residence times of decades or longer to mitigate modern nitrate contamination.

Nitrite is an important intermediate species in the biogeochemical cycling of nitrogen, but its role in natural aquatic systems is poorly understood. Isotopic data can be used to study the sources and transformations of NO2- in the environment, but methods for independent isotopic analyses of NO2- in the presence of other N species are still new and evolving. This study demonstrates that isotopic analyses of N and O in NO2- can be done by treating whole freshwater or saltwater samples with the denitrifying bacterium Stenotrophomonas nitritireducens, which selectively reduces NO2- to N2O for isotope ratio mass spectrometry. When calibrated with solutions containing NO2- with known isotopic compositions determined independently, reproducible delta15N and delta18O values were obtained at both natural-abundance levels (+/-0.2-0.5 per thousand for delta15N and +/-0.4-1.0 per thousand for delta18O) and moderately enriched 15N tracer levels (+/-20-50 per thousand for delta15N near 5000 per thousand) for 5-20 nmol of NO2- (1-20 micromol/L in 1-5 mL aliquots). This method is highly selective for NO2- and was used for mixed samples containing both NO2- and NO3- with little or no measurable cross-contamination. In addition, mixed samples that were analyzed with S. nitritireducens were treated subsequently with Pseudomonas aureofaciens to reduce the NO3- in the absence of NO2-, providing isotopic analyses of NO2- and NO3- separately in the same aliquot. Sequential bacterial reduction methods like this one should be useful for a variety of isotopic studies aimed at understanding nitrogen cycling in aquatic environments. A test of these methods in an agricultural watershed in Indiana provides isotopic evidence for both nitrification and denitrification as sources of NO2- in a small stream.

Perchlorate is a widespread environmental contaminant having both anthropogenic and natural sources. Stable isotope ratios of O and Cl in a given sample of perchlorate may be used to distinguish its source(s). Isotopic ratios may also be useful for identifying the extent of biodegradation of perchlorate, which is critical for assessing natural attenuation of this contaminant in groundwater. For this approach to be useful, however, the kinetic isotopic fractionations of O and Cl during perchlorate biodegradation must first be determined as a function of environmental variables such as temperature and bacterial species. A laboratory study was performed in which the O and Cl isotope ratios of perchlorate were monitored as a function of degradation by two separate bacterial strains (Azospira suillum JPLRND and Dechlorospirillum sp. FBR2) at both 10 degrees C and 22 degrees C with acetate as the electron donor. Perchlorate was completely reduced by both strains within 280 h at 22 degrees C and 615 h at 10 degrees C. Measured values of isotopic fractionation factors were epsilon(18)O = -36.6 to -29.0% per hundred and epsilon(37)Cl = -14.5 to -11.5% per hundred, and these showed no apparent systematic variation with either temperature or bacterial strain. An experiment using (18)O-enriched water (delta(18)O = +198% per hundred) gave results indistinguishable from those observed in the isotopically normal water (delta(18)O = -8.1% per hundred) used in the other experiments, indicating negligible isotope exchange between perchlorate and water during biodegradation. The fractionation factor ratio epsilon(18)O/epsilon(37)Cl was nearly invariant in all experiments at 2.50 +/- 0.04. These data indicate that isotope ratio analysis will be useful for documenting perchlorate biodegradation in soils and groundwater. The establishment of a microbial fractionation factor ratio (epsilon(18)O/ epsilon(37)Cl) also has significant implications for forensic studies.

Ground water processes affecting seasonal variations of surface water nitrate concentrations were investigated in an incised first-order stream in an agricultural watershed with a riparian forest in the coastal plain of Maryland. Aquifer characteristics including sediment stratigraphy, geochemistry, and hydraulic properties were examined in combination with chemical and isotopic analyses of ground water, macropore discharge, and stream water. The ground water flow system exhibits vertical stratification of hydraulic properties and redox conditions, with sub-horizontal boundaries that extend beneath the field and adjacent riparian forest. Below the minimum water table position, ground water age gradients indicate low recharge rates (2-5 cm yr(-1)) and long residence times (years to decades), whereas the transient ground water wedge between the maximum and minimum water table positions has a relatively short residence time (months to years), partly because of an upward increase in hydraulic conductivity. Oxygen reduction and denitrification in recharging ground waters are coupled with pyrite oxidation near the minimum water table elevation in a mottled weathering zone in Tertiary marine glauconitic sediments. The incised stream had high nitrate concentrations during high flow conditions when much of the ground water was transmitted rapidly across the riparian zone in a shallow oxic aquifer wedge with abundant outflow macropores, and low nitrate concentrations during low flow conditions when the oxic wedge was smaller and stream discharge was dominated by upwelling from the deeper denitrified parts of the aquifer. Results from this and similar studies illustrate the importance of near-stream geomorphology and subsurface geology as controls of riparian zone function and delivery of nitrate to streams in agricultural watersheds.

Nitrite is a central intermediate in the nitrogen cycle and can persist in significant concentrations in ocean waters, sediment pore waters, and terrestrial groundwaters. To fully interpret the effect of microbial processes on nitrate (NO3-), nitrite (NO2-), and nitrous oxide (N2O) cycling in these systems, the nitrite pool must be accessible to isotopic analysis. Furthermore, because nitrite interferes with most methods of nitrate isotopic analysis, accurate isotopic analysis of nitrite is essential for correct measurement of nitrate isotopes in a sample that contains nitrite. In this study, nitrite salts with varying oxygen isotopic compositions were prepared and calibrated and then used to test the denitrifier method for nitrite oxygen isotopic analysis. The oxygen isotopic fractionation during nitrite reduction to N2O by Pseudomonas aureofaciens was lower than for nitrate conversion to N2O, while oxygen isotopic exchange between nitrite and water during the reaction was similar. These results enable the extension of the denitrifier method to oxygen isotopic analysis of nitrite (in the absence of nitrate) and correction of nitrate isotopes for the presence of nitrite in "mixed" samples. We tested storage conditions for seawater and freshwater samples that contain nitrite and provide recommendations for accurate oxygen isotopic analysis of nitrite by any method. Finally, we report preliminary results on the equilibrium isotope effect between nitrite and water, which can play an important role in determining the oxygen isotopic value of nitrite where equilibration with water is significant.

Rates of benthic denitrification were measured using two techniques, membrane inlet mass spectrometry (MIMS) and isotope ratio mass spectrometry (IRMS), applied to sediment cores from two NO3(-)-rich streams draining agricultural land in the upper Mississippi River Basin. Denitrification was estimated simultaneously from measurements of N2:Ar (MIMS) and 15N[N2] (IRMS) after the addition of low-level 15NO3- tracer (15N:N = 0.03-0.08) in stream water overlying intact sediment cores. Denitrification rates ranged from about 0 to 4400 micromol N x m(-2) x h(-1) in Sugar Creek and from 0 to 1300 micromol N x m(-2) x h(-1) in Iroquois River, the latter of which possesses greater streamflow discharge and a more homogeneous streambed and water column. Within the uncertainties of the two techniques, there is good agreement between the MIMS and IRMS results, which indicates that the production of N2 by the coupled process of nitrification/denitrification was relatively unimportant and surface-water NO3- was the dominant source of NO3- for benthic denitrification in these streams. Variation in stream NO3- concentration (from about 20 micromol/L during low discharge to 1000 micromol/L during high discharge) was a significant control of benthic denitrification rates, judging from the more abundant MIMS data. The interpretation that NO3- concentration directly affects denitrification rate was corroborated by increased rates of denitrification in cores amended with NO3-. Denitrification in Sugar Creek removed < or = 11% per day of the instream NO3- in late spring and removed roughly 15-20% in late summer. The fraction of NO3- removed in Iroquois River was less than that of Sugar Creek. Although benthic denitrification rates were relatively high during periods of high stream flow, when NO3 concentrations were also high, the increase in benthic denitrification could not compensate for the much larger increase in stream NO3- fluxes during high flow. Consequently, fractional NO3- losses were relatively low during high flow.

Denitrification, the reduction of the nitrogen (N) oxides, nitrate (NO3-) and nitrite (NO2-), to the gases nitric oxide (NO), nitrous oxide (N2O), and dinitrogen (N2), is important to primary production, water quality, and the chemistry and physics of the atmosphere at ecosystem, landscape, regional, and global scales. Unfortunately, this process is very difficult to measure, and existing methods are problematic for different reasons in different places at different times. In this paper, we review the major approaches that have been taken to measure denitrification in terrestrial and aquatic environments and discuss the strengths, weaknesses, and future prospects for the different methods. Methodological approaches covered include (1) acetylene-based methods, (2) 15N tracers, (3) direct N2 quantification, (4) N2:Ar ratio quantification, (5) mass balance approaches, (6) stoichiometric approaches, (7) methods based on stable isotopes, (8) in situ gradients with atmospheric environmental tracers, and (9) molecular approaches. Our review makes it clear that the prospects for improved quantification of denitrification vary greatly in different environments and at different scales. While current methodology allows for the production of accurate estimates of denitrification at scales relevant to water and air quality and ecosystem fertility questions in some systems (e.g., aquatic sediments, well-defined aquifers), methodology for other systems, especially upland terrestrial areas, still needs development. Comparison of mass balance and stoichiometric approaches that constrain estimates of denitrification at large scales with point measurements (made using multiple methods), in multiple systems, is likely to propel more improvement in denitrification methods over the next few years.

Denitrification is a critical process regulating the removal of bioavailable nitrogen (N) from natural and human-altered systems. While it has been extensively studied in terrestrial, freshwater, and marine systems, there has been limited communication among denitrification scientists working in these individual systems. Here, we compare rates of denitrification and controlling factors across a range of ecosystem types. We suggest that terrestrial, freshwater, and marine systems in which denitrification occurs can be organized along a continuum ranging from (1) those in which nitrification and denitrification are tightly coupled in space and time to (2) those in which nitrate production and denitrification are relatively decoupled. In aquatic ecosystems, N inputs influence denitrification rates whereas hydrology and geomorphology influence the proportion of N inputs that are denitrified. Relationships between denitrification and water residence time and N load are remarkably similar across lakes, river reaches, estuaries, and continental shelves. Spatially distributed global models of denitrification suggest that continental shelf sediments account for the largest portion (44%) of total global denitrification, followed by terrestrial soils (22%) and oceanic oxygen minimum zones (OMZs; 14%). Freshwater systems (groundwater, lakes, rivers) account for about 20% and estuaries 1% of total global denitrification. Denitrification of land-based N sources is distributed somewhat differently. Within watersheds, the amount of land-based N denitrified is generally highest in terrestrial soils, with progressively smaller amounts denitrified in groundwater, rivers, lakes and reservoirs, and estuaries. A number of regional exceptions to this general trend of decreasing denitrification in a downstream direction exist, including significant denitrification in continental shelves of N from terrestrial sources. Though terrestrial soils and groundwater are responsible for much denitrification at the watershed scale, per-area denitrification rates in soils and groundwater (kg N x km(-2) x yr(-1)) are, on average, approximately one-tenth the per-area rates of denitrification in lakes, rivers, estuaries, continental shelves, or OMZs. A number of potential approaches to increase denitrification on the landscape, and thus decrease N export to sensitive coastal systems exist. However, these have not generally been widely tested for their effectiveness at scales required to significantly reduce N export at the whole watershed scale.

Mobilization of natural nitrate (NO3-) deposits in the subsoil by irrigation water in arid and semiarid regions has the potential to produce large groundwater NO3-concentrations. The use of isotopes to distinguish between natural and anthropogenic NO3- sources in these settings could be complicated by the wide range in delta15N values of natural NO3-. An approximately 10 000 year record of paleorecharge from the regionally extensive High Plains aquifer indicates that delta15N values for NO3- derived from natural sources ranged from 1.3 to 12.3 per thousand and increased systematically from the northern to the southern High Plains. This collective range in delta15N values spans the range that might be interpreted as evidence for fertilizer and animal-waste sources of NO3-; however, the delta15N values for NO3- in modern recharge (< 50 years) under irrigated fields were, for the most part, distinctly different from those of paleorecharge when viewed in the overall regional context. An inverse relation was observed between the delta15N[NO3-] values and the NO3-/Cl- ratios in paleorecharge that is qualitatively consistent with fractionating losses of N increasing from north to south in the High Plains. N and O isotope data for NO3- are consistent with both NH3 volatilization and denitrification, having contributed to fractionating losses of N prior to recharge. The relative importance of different isotope fractionating processes may be influenced by regional climate patterns as well as by local variation in soils, vegetation, topography, and moisture conditions.

Groundwater from remote parts of the Middle Rio Grande Basin in north-central New Mexico has perchlorate (ClO4-) concentrations of 0.12-1.8 micro/L. Because the water samples are mostly preanthropogenic in age (0-28000 years) and there are no industrial sources in the study area, a natural source of the ClO4- is likely. Most of the samples have Br-, Cl-, and SO4(2-) concentrations that are similar to those of modern bulk atmospheric deposition with evapotranspiration (ET) factors of about 7-40. Most of the ET values for Pleistocene recharge were nearly twice that for Holocene recharge. The N03-/Cl- and CIO-/Cl-ratios are more variable than those of Br-/Cl- or S04(2-)/Cl-. Samples thought to have recharged under the most arid conditions in the Holocene have relatively high N03-/Cl- ratios and low delta 15N values (+1 per mil (% per thousand)) similar to those of modern bulk atmospheric N deposition. The delta 18O values of the N03- (-4 to 0% per thousand) indicate that atmospheric N03- was not transmitted directly to the groundwater but may have been cycled in the soils before infiltrating. Samples with nearly atmospheric N03-/CI- ratios have relatively high Cl04- concentrations (1.0-1.8 ug/L) with a nearly constant Cl04-/CI- mole ratio of (1.4 +/- 0.1) x 10(-4), which would be consistent with an average Cl04-concentration of 0.093 0.005 ,ug/L in bulk atmospheric deposition during the late Holocene in north-central NM. Samples thought to have recharged under wetter conditions have higher delta 15N values (+3 to +8 % per thousando), lower NO3-/Cl- ratios, and lower ClO4-/Cl- ratios than the ones most likely to preserve an atmospheric signal. Processes in the soils that may have depleted atmospherically derived NO3-also may have depleted ClO4- to varying degrees prior to recharge. If these interpretations are correct, then ClO4- concentrations of atmospheric origin as high as 4 microg/L are possible in preanthropogenic groundwater in parts of the Southwest where ET approaches a factor of 40. Higher Cl04- concentrations in uncontaminated groundwater could occur in recharge beneath arid areas where ET is greater than 40, where long-term accumulations of atmospheric salts are leached suddenly from dry soils, or where other (nonatmospheric) natural sources of ClO4- exist.

Nitrification was measured within a sand and gravel aquifer on Cape Cod, MA, using a series of single-well injection tests. The aquifer contained a wastewater-derived contaminant plume, the core of which was anoxic and contained ammonium. The study was conducted near the downgradient end of the ammonium zone, which was characterized by inversely trending vertical gradients of oxygen (270 to 0 microM) and ammonium (19 to 625 microM) and appeared to be a potentially active zone for nitrification. The tests were conducted by injecting a tracer solution (ambient ground water + added constituents) into selected locations within the gradients using multilevel samplers. After injection, the tracers moved by natural ground water flow and were sampled with time from the injection port. Rates of nitrification were determined from changes in nitrate and nitrite concentration relative to bromide. Initial tests were conducted with (15)N-enriched ammonium; subsequent tests examined the effect of adding ammonium, nitrite, or oxygen above background concentrations and of adding difluoromethane, a nitrification inhibitor. In situ net nitrate production exceeded net nitrite production by 3- to 6- fold and production rates of both decreased in the presence of difluoromethane. Nitrification rates were 0.02-0.28 mumol (L aquifer)(-1) h(-1) with in situ oxygen concentrations and up to 0.81 mumol (L aquifer)(-1) h(-1) with non-limiting substrate concentrations. Geochemical considerations indicate that the rates derived from single-well injection tests yielded overestimates of in situ rates, possibly because the injections promoted small-scale mixing within a transport-limited reaction zone. Nonetheless, these tests were useful for characterizing ground water nitrification in situ and for comparing potential rates of activity when the tracer cloud included non-limiting ammonium and oxygen concentrations.

Perchlorate has been detected recently in a variety of soils, waters, plants, and food products at levels that may be detrimental to human health. These discoveries have generated considerable interest in perchlorate source identification. In this study, comprehensive stable isotope analyses (37Cl/35Cl and 18O/17O/16O) of perchlorate from known synthetic and natural sources reveal systematic differences in isotopic characteristics that are related to the formation mechanisms. In addition, isotopic analyses of perchlorate extracted from groundwater and surface water demonstrate the feasibility of identifying perchlorate sources in contaminated environments on the basis of this technique. Both natural and synthetic sources of perchlorate have been identified in water samples from some perchlorate occurrences in the United States by the isotopic method.

The bacterial denitrification method for isotopic analysis of nitrate using N(2)O generated from Pseudomonas aureofaciens may overestimate delta(15)N values by as much as 1-2 per thousand for samples containing atmospheric nitrate because of mass-independent (17)O variations in such samples. By analyzing such samples for delta(15)N and delta(18)O using the denitrifier Pseudomonas chlororaphis, one obtains nearly correct delta(15)N values because oxygen in N(2)O generated by P. chlororaphis is primarily derived from H(2)O. The difference between the apparent delta(15)N value determined with P. aureofaciens and that determined with P. chlororaphis, assuming mass-dependent oxygen isotopic fractionation, reflects the amount of mass-independent (17)O in a nitrate sample. By interspersing nitrate isotopic reference materials having substantially different delta(18)O values with samples, one can normalize oxygen isotope ratios and determine the fractions of oxygen in N(2)O derived from the nitrate and from water with each denitrifier. This information can be used to improve delta(15)N values of nitrates having excess (17)O. The same analyses also yield estimates of the magnitude of (17)O excess in the nitrate (expressed as Delta(17)O) that may be useful in some environmental studies. The 1-sigma uncertainties of delta(15)N, delta(18)O and Delta(17)O measurements are +/-0.2, +/-0.3 and +/-5 per thousand, respectively., (Copyright 2004 John Wiley & Sons, Ltd.)

Analytical grade L-glutamic acid is chemically stable and has a C/N mole ratio of 5, which is close to that of many of natural biological materials, such as blood and animal tissue. Two L-glutamic acid reference materials with substantially different 13C and 15N abundances have been prepared for use as organic reference materials for C and N isotopic measurements. USGS40 is analytical grade L-glutamic acid and has a delta13C value of -26.24 per thousand relative to VPDB and a delta15N value of -4.52 per thousand relative to N2 in air. USGS41 was prepared by dissolving analytical grade L-glutamic acid with L-glutamic acid enriched in 13C and 15N. USGS41 has a delta13C value of +37.76 per thousand and a delta15N value of +47.57 per thousand. The delta13C and delta15N values of both materials were measured against the international reference materials NBS 19 calcium carbonate (delta13C=+1.95 per thousand ), L-SVEC lithium carbonate (delta13C=-46.48 per thousand ), IAEA-N-1 ammonium sulfate (delta15N=0.43 per thousand ), and USGS32 potassium nitrate (delta15N=180 per thousand ) by on-line combustion continuous-flow and off-line dual-inlet isotope-ratio mass spectrometry. Both USGS40 and USGS41 are isotopically homogeneous; reproducibility of delta13C is better than 0.13 per thousand, and that of delta15N is better than 0.13 per thousand in 100-microg amounts. These two isotopic reference materials can be used for (i) calibrating local laboratory reference materials, and (ii) quantifying drift with time, mass-dependent fractionations, and isotope-ratio-scale contraction in the isotopic analysis of various biological materials. Isotopic results presented in this paper yield a delta13C value for NBS 22 oil of -29.91 per thousand, in contrast to the commonly accepted value of -29.78 per thousand for which off-line blank corrections probably have not been quantified satisfactorily., (Published in 2003 by John Wiley & Sons, Ltd.)

Despite a rapidly growing literature on analytical methods and field applications of O isotope-ratio measurements of NO(3)(-) in environmental studies, there is evidence that the reported data may not be comparable because reference materials with widely varying delta(18)O values have not been readily available. To address this problem, we prepared large quantities of two nitrate salts with contrasting O isotopic compositions for distribution as reference materials for O isotope-ratio measurements: USGS34 (KNO(3)) with low delta(18)O and USGS35 (NaNO(3)) with high delta(18)O and 'mass-independent' delta(17)O. The procedure used to produce USGS34 involved equilibration of HNO(3) with (18)O-depleted meteoric water. Nitric acid equilibration is proposed as a simple method for producing laboratory NO(3)(-) reference materials with a range of delta(18)O values and normal (mass-dependent) (18)O:(17)O:(16)O variation. Preliminary data indicate that the equilibrium O isotope-fractionation factor (alpha) between [NO(3)(-)] and H(2)O decreases with increasing temperature from 1.0215 at 22 degrees C to 1.0131 at 100 degrees C. USGS35 was purified from the nitrate ore deposits of the Atacama Desert in Chile and has a high (17)O:(18)O ratio owing to its atmospheric origin. These new reference materials, combined with previously distributed NO(3) (-) isotopic reference materials IAEA-N3 (=IAEA-NO-3) and USGS32, can be used to calibrate local laboratory reference materials for determining offset values, scale factors, and mass-independent effects on N and O isotope-ratio measurements in a wide variety of environmental NO(3)(-) samples. Preliminary analyses yield the following results (normalized with respect to VSMOW and SLAP, with reproducibilities of +/-0.2-0.3 per thousand, 1sigma): IAEA-N3 has delta(18)O = +25.6 per thousand and delta(17)O = +13.2 per thousand; USGS32 has delta(18)O = +25.7 per thousand; USGS34 has delta(18)O = -27.9 per thousand and delta(17)O = -14.8 per thousand; and USGS35 has delta(18)O = +57.5 per thousand and delta(17)O = +51.5 per thousand.

Three different KNO3 salts with delta18O values ranging from about -31 to +54 per thousand relative to VSMOW were used to compare three off-line, sealed glass tube combustion methods (widely used for isotope studies) with a more recently developed on-line carbon combustion technique. All methods yielded roughly similar isotope ratios for KNO3 samples with delta18O values in the midpoint of the delta18O scale near that of the nitrate reference material IAEA-NO-3 (around +21 to +25 per thousand). This reference material has been used previously for one-point interlaboratory and intertechnique calibrations. However, the isotope ratio scale factors by all of the off-line combustion techniques are compressed such that they are between 0.3 and 0.7 times that of the on-line combustion technique. The contraction of the 6180 scale in the off-line preparations apparently is caused by O isotope exchange between the sample and the glass combustion tubes. These results reinforce the need for nitrate reference materials with delta18O values far from that of atmospheric O2, to improve interlaboratory comparability.

A thermal decomposition method was developed and tested for the simultaneous determination of delta 18O and delta 17O in nitrate. The thermal decomposition of AgNO3 allows for the rapid and accurate determination of 18O/ 16O and 17O/16O isotopic ratios with a precision of +/- 1.5 per thousand for delta 18O and +/- 0.11 per thousand for delta 17O (delta 17O = delta 17O - 0.52 x delta 18O). The international nitrate isotope reference material IAEA-NO3 yielded a delta 18O value of +23.6 per thousand and delta 17O of -0.2 per thousand, consistent with normal terrestrial mass-dependent isotopic ratios. In contrast, a large sample of NaNO3 from the Atacama Desert, Chile, was found to have delta 17O = 21.56 +/- 0.11 per thousand and delta 18O = 54.9 +/- 1.5 per thousand, demonstrating a substantial mass-independent isotopic composition consistent with the proposed atmospheric origin of the desert nitrate. It is suggested that this sample (designated USGS-35) can be used to generate other gases (CO2, CO, N2O, O2) with the same delta 17O to serve as measurement references for a variety of applications involving mass-independent isotopic compositions in environmental studies.