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At least 253 records · Page 14Linked to original sources

Updated polychlorinated biphenyl mass budget for Lake Michigan

This study revisits and updates the Lake Michigan Mass Balance Project (LMMBP) for polychlorinated biphenyls (PCBs) that was conducted in 1994–1995. This work uses recent concentrations of PCBs in tributary and open lake water, air, and sediment to calculate an updated mass budget. Five of the 11 LMMBP tributaries were revisited in 2015. In these five tributaries, the geometric mean concentrations of ∑PCBs (sum of 85 congeners) ranged from 1.52 to 22.4 ng L –1 . The highest concentrations of PCBs were generally found in the Lower Fox River and in the Indiana Harbor and Ship Canal. The input flows of ∑PCBs from wet deposition, dry deposition, tributary loading, and air to water exchange, and the output flows due to sediment burial, volatilization from water to air, and transport to Lake Huron and through the Chicago Diversion were calculated, as well as flows related to the internal processes of settling, resuspension, and sediment–water diffusion. The net transfer of ∑PCBs is 1240 ± 531 kg yr –1 out of the lake. This net transfer is 46% lower than that estimated in 1994–1995. PCB concentrations in most matrices in the lake are decreasing, which drove the decline of all the individual input and output flows. Atmospheric deposition has become negligible, while volatilization from the water surface is still a major route of loss, releasing PCBs from the lake into the air. Large masses of PCBs remain in the water column and surface sediments and are likely to contribute to the future efflux of PCBs from the lake to the air.

Lake Michigan

Method for determination of methyl tert-butyl ether and its degradation products in water

An analytical method is described that can detect the major alkyl ether compounds that are used as gasoline oxygenates (methyl tert-butyl ether, MTBE; ethyl tert-butyl ether, ETBE; and tert-amyl methyl ether, TAME) and their most characteristic degradation products (tert-butyl alcohol, TBA; tert-butyl formate, TBF; and tert-amyl alcohol, TAA) in water at sub-ppb concentrations. The new method involves gas chromatography (GC) with direct aqueous injection (DAI) onto a polar column via a splitless injector, coupled with detection by mass spectrometry (MS). DAI-GC/MS gives excellent agreement with conventional purge-and-trap methods for MTBE over a wide range of environmentally relevant concentrations. The new method can also give simultaneous identification of polar compounds that might occur as degradation products of gasoline oxygenates, such as TBA, TBF, TAA, methyl acetate, and acetone. When the method was applied to effluent from a column microcosm prepared with core material from an urban site in New Jersey, conversion of MTBE to TBA was observed after a lag period of 35 days. However, to date, analyses of water samples from six field sites using the DAI-GC/MS method have not produced evidence for the expected products of in situ degradation of MTBE.An analytical method is described that can detect the major alkyl ether compounds that are used as gasoline oxygenates (methyl tert-butyl ether, MTBE; ethyl tert-butyl ether, ETBE; and tert-amyl methyl ether, TAME) and their most characteristic degradation products (tert-butyl alcohol, TBA; tert-butyl formate, TBF; and tert-amyl alcohol, TAA) in water at sub-ppb concentrations. The new method involves gas chromatography (GC) with direct aqueous injection (DAI) onto a polar column via a splitless injector, coupled with detection by mass spectrometry (MS). DAI-GC/MS gives excellent agreement with conventional purge-and-trap methods for MTBE over a wide range of environmentally relevant concentrations. The new method can also give simultaneous identification of polar compounds that might occur as degradation products of gasoline oxygenates, such as TBA, TBF, TAA, methyl acetate, and acetone. When the method was applied to effluent from a column microcosm prepared with core material from an urban site in New Jersey, conversion of MTBE to TBA was observed after a lag period of 35 days. However, to date, analyses of water samples from six field sites using the DAI-GC/MS method have not produced evidence for the expected products of in situ degradation of MTBE.

Environmental Science & Technology

Health risks due to radon in drinking water

Following more than a decade of scientific debate about the setting of a standard for 222Rn in drinking water, Congress established a timetable for the promulgation of a standard in the 1996 Amendments to the Safe Drinking Water Act. As a result of those Amendments, the EPA contracted with the National Academy of Sciences to undertake a risk assessment for exposure to radon in drinking water. In addition, the resulting committee was asked to address several other scientific issues including the national average ambient 222Rn concentration and the increment of 222Rn to the indoor- air concentration arising from the use of drinking water in a home. A new dosimetric analysis of the cancer risk to the stomach from ingestion was performed. The recently reported risk estimates developed by the BEIR VI Committee for inhalation of radon decay products were adopted. Because the 1996 Amendments permit states to develop programs in which mitigation of air- producing health-risk reductions equivalent to that which would be achieved by treating the drinking water, the scientific issues involved in such 'multimedia mitigation programs' were explored.

Environmental Science & Technology

Transport, behavior, and fate of volatile organic compounds in streams

Volatile organic compounds (VOCs) are compounds with chemical and physical properties that allow the compounds to move freely between the water and air phases of the environment. VOCs are widespread in the environment because of this mobility. Many VOCs have properties that make them suspected or known hazards to the health of humans and aquatic organisms. Consequently, understanding the processes affecting the concentration and distribution of VOCs in the environment is necessary. The transport, behavior, and fate of VOCs in streams are determined by combinations of chemical, physical, and biological processes. These processes are volatilization, absorption, wet and dry deposition, microbial degradation, sorption, hydrolysis, aquatic photolysis, oxidation, chemical reaction, biocon-centration, advection, and dispersion. The relative importance of each of these processes depends on the characteristics of the VOC and the stream. The U.S. Geological Survey National Water-Quality Assessment Program selected 55 VOCs for study. This article reviews the characteristics of the various processes that could affect the transport, behavior, and fate of these VOCs in streams.

Critical Reviews in Environmental Science and Tech

Uptake of per- and polyfluoroalkyl substances by fish, mussel, and passive samplers in mobile laboratory exposures using groundwater from a contamination plume at a historical fire training area, Cape Cod, Massachusetts

Aqueous film-forming foams historically were used during fire training activities on Joint Base Cape Cod, Massachusetts, and created an extensive per- and polyfluoroalkyl substances (PFAS) groundwater contamination plume. The potential for PFAS bioconcentration from exposure to the contaminated groundwater, which discharges to surface water bodies, was assessed with mobile-laboratory experiments using groundwater from the contamination plume and a nearby reference location. The on-site continuous-flow 21-day exposures used male and female fathead minnows, freshwater mussels, polar organic chemical integrative samplers (POCIS), and polyethylene tube samplers (PETS) to evaluate biotic and abiotic uptake. The composition of the PFAS-contaminated groundwater was complex and 9 PFAS were detected in the reference groundwater and 17 PFAS were detected in the contaminated groundwater. The summed PFAS concentrations ranged from 120 to 140 ng L –1 in reference groundwater and 6100 to 15,000 ng L –1 in contaminated groundwater. Biotic concentration factors (CF b ) for individual PFAS were species, sex, source, and compound-specific and ranged from 2.9 to 1000 L kg –1 in whole-body male fish exposed to contaminated groundwater for 21 days. The fish and mussel CF b generally increased with increasing fluorocarbon chain length and were greater for sulfonates than for carboxylates. The exception was perfluorohexane sulfonate, which deviated from the linear trend and had a 10-fold difference in CF b between sites, possibly because of biotransformation of precursors such as perfluorohexane sulfonamide. Uptake for most PFAS in male fish was linear over time, whereas female fish had bilinear uptake indicated by an initial increase in tissue concentrations followed by a decrease. Uptake of PFAS was less for mussels (maximum CF b = 200) than for fish, and mussel uptake of most PFAS also was bilinear. Although abiotic concentration factors were greater than CF b , and values for POCIS were greater than for PETS, passive samplers were useful for assessing PFAS that potentially bioconcentrate in fish but are present at concentrations below method quantitation limits in water. Passive samplers also accumulate short-chain PFAS that are not bioconcentrated.

Massachusetts

Identification of Marbon in the Indiana Harbor and Ship Canal

Marbon is isomeric with Dechlorane Plus (DP). Both are produced by the Diels− Alder condensation of hexachlorocyclopentadiene with cyclic dienes, and both have elemental compositions of C18H12Cl12. Dechlorane Plus is commonly found in the environment throughout the world, but Marbon has, so far, only been detected at low levels in one sediment core collected near the mouth of the Niagara River in Lake Ontario. Here we report on the concentrations of Marbon and anti-DP in 59 water samples from five Lake Michigan tributaries [the Grand, Kalamazoo, St. Joseph, and Lower Fox Rivers, and the Indiana Harbor and Ship Canal (IHSC)], 10 surface sediment samples from the IHSC, and 2 surface sediment samples from the Chicago Sanitary and Ship Canal. Three Marbon diastereomers were detected in the water and sediment samples from the IHSC, which is far from the location of its previous detection in Lake Ontario. The sum of the concentrations of the three Marbons was greater in the water from the IHSC (N = 11, median =150 pg/L) compared to those in water from the other four tributaries (N = 11−13, medians =0.9−2.0 pg/L). Marbon concentrations in sediment samples from the IHSC were up to 450 ng/g dry weight. Anti-DP was also measured for comparison. Its concentrations were not significantly different among the water samples, but its sediment concentrations in the IHSC were significantly correlated with those of Marbon. The source of Marbon contamination in the IHSC is not clear.

Indiana

Current-use flame retardants in the water of Lake Michigan tributaries

In this study, we measured the concentrations of 65 flame retardants in water samples from five Lake Michigan tributaries. These flame retardants included organophosphate esters (OPEs), brominated flame retardants (BFRs), and Dechlorane-related compounds. A total of 59 samples, including both the particulate and the dissolved phases, were collected from the Grand, Kalamazoo, Saint Joseph, and Lower Fox rivers and from the Indiana Harbor and Ship Canal (IHSC) in 2015. OPEs were the most abundant among the targeted compounds with geometric mean concentrations ranging from 20 to 54 ng/L; OPE concentrations were comparable among the five tributaries. BFR concentrations were about 1 ng/L, and the most-abundant compounds were bis (2-ethylhexyl) tetrabromophthalate, 2-ethylhexyl 2,3,4,5-tetrabromobenzoate, and decabromodiphenyl ether. The highest BFR concentrations were measured in either the IHSC or the Saint Joseph River. The dechlorane-related compounds were detected at low concentrations (<1 pg/L). The fraction of target compounds in the particulate phase relative to the dissolved phase varied by chemical and tended to increase with their octanol–water partition coefficient. The chemical loading from all the five tributaries into Lake Michigan were <10 kg/year for the BFRs and about 500 kg/year for the OPEs.

Lake Michigan

Using carbon, nitrogen, and mercury isotope values to distinguish mercury sources to Alaskan lake trout

Lake trout ( Salvelinus namaycush ), collected from 13 remote lakes located in southwestern Alaska, were analyzed for carbon, nitrogen, and mercury (Hg) stable isotope values to assess the importance of migrating oceanic salmon, volcanic activity, and atmospheric deposition to fish Hg burden. Methylmercury (MeHg) bioaccumulation in phytoplankton (5.0–6.9 kg L –1 ) was also measured to quantify the basal uptake of MeHg to these aquatic food webs. Hg isotope values in lake trout revealed that while the extent of precipitation-delivered Hg was similar across the entire study area, volcanic Hg is likely an important additional source to lake trout in proximate lakes. In contrast, migratory salmon ( Oncorhynchus nerka ) deliver little MeHg to lake trout directly, although indirect delivery processes via decay could exist. A high level of variability in carbon, nitrogen, and Hg isotope values indicates niche partitioning in lake trout populations within each lake and that a complex suite of ecological interactions is occurring, complicating the conceptually linear assessment of the contaminant source to the receiving organism. Without connecting energy and contaminant isotope axes, we would not have understood why lake trout from these pristine lakes have highly variable Hg burdens despite consistently low water Hg and comparable age-length dynamics.

Alaska

Biogeochemical controls on diel cycling of stable isotopes of dissolved 02 and dissolved inorganic carbon in the Big Hole River, Montana

Rivers with high biological productivity typically show substantial increases in pH and dissolved oxygen (DO) concentration during the day and decreases at night, in response to changes in the relative rates of aquatic photosynthesis and respiration. These changes, coupled with temperature variations, may impart diel (24-h) fluctuations in the concentration of trace metals, nutrients, and other chemical species. A better understanding of diel processes in rivers is needed and will lead to improved methods of data collection for both monitoring and research purposes. Previous studies have used stable isotopes of dissolved oxygen (DO) and dissolved inorganic carbon (DIC) as tracers of geochemical and biological processes in streams, lakes, and marine systems. Although seasonal variation in δ 18 O of DO in rivers and lakes has been documented, no study has investigated diel changes in this parameter. Here, we demonstrate large (up to 13‰) cycles in δ 18 O-DO for two late summer sampling periods in the Big Hole River of southwest Montana and illustrate that these changes are correlated to variations in the DO concentration, the C-isotopic composition of DIC, and the primary productivity of the system. The magnitude of the diel cycle in δ 18 O-DO was greater in August versus September because of the longer photoperiod and warmer water temperatures. This study provides another biogeochemical tool for investigating the O 2 and C budgets in rivers and may also be applicable to lake and groundwater systems.

Montana

Enhanced biological processes associated with alopecia in polar bears ( Ursus maritimus )

Populations of wildlife species worldwide experience incidents of mass morbidity and mortality. Primary or secondary drivers of these events may escape classical detection methods for identifying microbial insults, toxin exposure, or additional stressors. In 2012, 28% of polar bears sampled in a study in the southern Beaufort Sea region of Alaska had varying degrees of alopecia that was concomitant with reduced body condition. Concurrently, elevated numbers of sick or dead ringed seals were detected in the southern Beaufort, Chukchi, and Bering seas in 2012, resulting in the declaration of an unusual mortality event (UME) by the National Oceanic and Atmospheric Administration (NOAA). The primary and possible ancillary causative stressors of these events are unknown, and related physiological changes within individual animals have been undetectable using classical diagnostic methods. Here we present an emerging technology as a potentially guiding investigative approach aimed at elucidating the circumstances responsible for the susceptibility of certain polar bears to observed conditions. Using transcriptomic analysis we identified enhanced biological processes including immune response, viral defense, and response to stress in polar bears with alopecia. Our results support an alternative mechanism of investigation into the causative agents that, when used proactively, could serve as an early indicator for populations and species at risk. We suggest that current or classical methods for investigation into events of unusual morbidity and mortality can be costly, sometimes unfocused, and often inconclusive. Advances in technology allow for implementation of a holistic system of surveillance and investigation that could provide early warning of health concerns in wildlife species important to humans.

Science of the Total Environment

Food, beverage, and feedstock processing facility wastewater: A unique and underappreciated source of contaminants to U.S. streams

Process wastewaters from food, beverage, and feedstock facilities, although regulated, are an under-investigated environmental contaminant source. Food process wastewaters (FPWWs) from 23 facilities in 17 U.S. states were sampled and documented for a plethora of chemical and microbial contaminants. Of the 576 analyzed organics, 184 (32%) were detected at least once, with concentrations as large as 143 μg L –1 (6:2 fluorotelomer sulfonic acid), and as many as 47 were detected in a single FPWW sample. Cumulative per/polyfluoroalkyl substance concentrations up to 185 μg L –1 and large pesticide transformation product concentrations (e.g., methomyl oxime, 40 μg L –1 ; clothianidin TMG, 2.02 μg L –1 ) were observed. Despite 48% of FPWW undergoing disinfection treatment prior to discharge, bacteria resistant to third-generation antibiotics were found in each facility type, and multiple bacterial groups were detected in all samples, including total coliforms. The exposure–activity ratios and toxicity quotients exceeded 1.0 in 13 and 22% of samples, respectively, indicating potential biological effects and toxicity to vertebrates and invertebrates associated with the discharge of FPWW. Organic contaminant profiles of FPWW differed from previously reported contaminant profiles of municipal effluents and urban storm water, indicating that FPWW is another important source of chemical and microbial contaminant mixtures discharged into receiving surface waters.

Alabama, Arkansas, California, Idaho, Illinois, Io

Municipal and industrial wastewater treatment plant effluent contributions to per- and polyfluoroalkyl substances in the Potomac River: A basin-scale measuring and modeling approach

Managing per- and polyfluoroalkyl substances (PFAS) in water resources requires a basin-scale approach. Predicted environmental concentrations (PEC) and stream-vulnerability scores for PFAS were determined for the Potomac River watershed in the eastern United States. Approximately 15% of stream reaches contained municipal and/or industrial wastewater treatment plant (WWTP) discharges that are presumptive PFAS sources, comprising from <1 to >90% of streamflow. Mean annual PEC, based on the summed concentrations of eight PFAS detected in WWTP effluents (ΣPFAS PEC ), for all stream reaches in the watershed was 3.8 ng L –1 , and stream reaches impacted by WWTP had perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) PEC of 0.39 and 0.14 ng L –1 . For locations where measured-environmental concentrations (MEC) were determined, municipal and industrial WWTP contributed 7.8% (0 to 65%) of the total annual streamflow and MEC were greater than PEC in 99% of the samples, indicating additional potential PFAS sources. The mean ΣPFAS PEC was 9.1 ng L –1 compared to a mean sum of PFAS MEC of 34 ng L –1 . Under mean-August low-flow, 17% and 9.4% of the water-supply intakes had maximum PFOA and PFOS PEC exceeding drinking water maximum contaminant levels.

Maryland, Pennsylvania, Virginia, West Virginia

Fort Collins Science Center: science accomplishments for fiscal years 2012 and 2013

The Fort Collins Science Center (FORT) is a multi-disciplinary research and development center of the U.S. Geological Survey (USGS) located in Fort Collins, Colorado. Organizationally, FORT is within the USGS Southwest Region, although our work extends across the Nation and into several other countries. FORT research focuses on needs of the land- and water-management bureaus within the U.S. Department of the Interior (DOI), other Federal agencies, and those of State and non-government organizations. As a Science Center, we emphasize a multi-disciplinary science approach to provide information for resource-management decisionmaking. FORT’s vision is to maintain and continuously improve the integrated, collaborative, world-class research needed to inform effective, science-based land and resource management. Our science and technological development activities and unique capabilities support all USGS scientific Mission Areas and contribute to successful, collaborative science efforts across the USGS and DOI. We organized our report into an Executive Summary, a cross-reference table, and an appendix. The executive summary provides brief highlights of some key FORT accomplishments for each Mission Area. The table cross-references all major FY2012 and FY2013 science accomplishments with the various Mission Areas that each supports. The one-page accomplishment descriptions in the appendix are organized by USGS Mission Area and describe the many and diverse ways in which our science is applied to resource issues. As in prior years, lists of all FY2012 and FY2013 publications and other product types also are appended.

Open-File Report

The Mars Orbiter for Resources, Ices, and Environments (MORIE) science goals and instrument trades in radar, imaging, and spectroscopy

The Mars Orbiter for Resources, Ices, and Environments (MORIE) was selected as one of NASA's 2019 Planetary Mission Concept Studies. The mission builds upon recent discoveries and current knowledge gaps linked to two primary scientific questions: (1) when did elements of the cryosphere form and how are ice deposits linked to current, recent, and ancient climate, and (2) how does the crust record the evolution of surface environments and their transition through time? Addressing these questions has emerged in numerous recent reports as a high priority in investigating the evolution of Mars as a habitable world. A subsidiary goal of the mission concept is to provide information relevant to the eventual human exploration of Mars, specifically helping to locate and quantify near-surface water ice and hydrated mineral resources. The proposed instrument suite includes polarimetric synthetic aperture radar imaging, radar sounding, high-resolution visible and infrared imaging, both short-wave and thermal-infrared spectroscopy, and multichannel wide-angle imaging. MORIE would provide novel measurements of Mars expected to lead to significant new discoveries by the first radar imaging from orbit, radar sounding directly over the poles, and mineral mapping at spatial scales that will unravel geologic sequence stratigraphy through time. The final report of the mission concept provides details on the spacecraft, orbital design, technological maturity, results from systems-level integration studies, and costs. This article is intended to expand upon the science motivation for the mission, the measurement goals and objectives, and the instrument trade space that was examined in detail during the concept study.

The Planetary Science Journal

XANES evidence for rapid arsenic(III) oxidation at magnetite and ferrihydrite surfaces by dissolved O2 via Fe2+-mediated reactions

To reduce the adverse effects of arsenic on humans, various technologies are used to remove arsenic from groundwater, most relying on As adsorption on Fe-(oxyhydr)oxides and concomitant oxidation of As(III) by dissolved O 2 . This reaction can be catalyzed by microbial activity or by strongly oxidizing radical species known to form upon oxidation of Fe(II) by dissolved O 2 . Such catalyzed oxidation reactions have been invoked to explain the enhanced kinetics of As(III) oxidation in aerated water, in the presence of zerovalent iron or dissolved Fe(II). In the present study, we used arsenic K-edge X-ray absorption near edge structure (XANES) spectroscopy to investigate the role of Fe(II) in the oxidation of As(III) at the surface of magnetite and ferrihydrite under oxygenated conditions. Our results show rapid oxidation of As(III) to As(V) upon sorption onto magnetite under oxic conditions at neutral pH. Moreover, under similar oxic conditions, As(III) oxidized upon sorption onto ferrihydrite only after addition of Fe(II) aq within the investigated time frame of 24 h. These results confirm that Fe(II) is able to catalyze As(III) oxidation in the presence of dissolved O 2 and suggest that oxidation of As(III) upon sorption on magnetite under oxic conditions can be explained by an Fe 2+ -mediated Fenton-like reactions. Thus, the present study shows that magnetite might be an efficient alternative to the current use of oxidants and Fe(II) to remove As from aerated water. In addition, this study emphasizes that special care is needed to preserve arsenic oxidation state during laboratory sorption experiments as well as in collecting As-bearing samples from natural environments.

Environmental Science and Technology

Cyanobacterial harmful algal blooms and U.S. Geological Survey science capabilities

Cyanobacterial harmful algal blooms (CyanoHABs) are increasingly a global concern because CyanoHABs pose a threat to human and aquatic ecosystem health and cause economic damages. Despite advances in scientific understanding of cyanobacteria and associated compounds, many unanswered questions remain about occurrence, environmental triggers for toxicity, and the ability to predict the timing, duration, and toxicity of CyanoHABs. U.S. Geological Survey (USGS) scientists are leading a diverse range of studies to address CyanoHAB issues in water bodies throughout the United States, using a combination of traditional methods and emerging technologies, and in collaboration with numerous partners. By providing practical applications of cutting edge CyanoHAB research, USGS studies have advanced scientific understanding, enabling the development of approaches to help protect ecological and human health.

Open-File Report

Water stress from high-volume hydraulic fracturing potentially threatens aquatic biodiversity and ecosystem services in Arkansas, United States

Demand for high-volume, short duration water withdrawals could create water stress to aquatic organisms in Fayetteville Shale streams sourced for hydraulic fracturing fluids. We estimated potential water stress using permitted water withdrawal volumes and actual water withdrawals compared to monthly median, low, and high streamflows. Risk for biological stress was considered at 20% of long-term median and 10% of high- and low-flow thresholds. Future well build-out projections estimated potential for continued stress. Most water was permitted from small, free-flowing streams and “frack” ponds (dammed streams). Permitted 12-h pumping volumes exceeded median streamflow at 50% of withdrawal sites in June, when flows were low. Daily water usage, from operator disclosures, compared to median streamflow showed possible water stress in 7–51% of catchments from June–November, respectively. If 100% of produced water was recycled, per-well water use declined by 25%, reducing threshold exceedance by 10%. Future water stress was predicted to occur in fewer catchments important for drinking water and species of conservation concern due to the decline in new well installations and increased use of recycled water. Accessible and precise withdrawal and streamflow data are critical moving forward to assess and mitigate water stress in streams that experience high-volume withdrawals.

Arkansas

Constraining the oxygen isotopic composition of nitrate produced by nitrification

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.

Environmental Science & Technology