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J.K. Bohlke

Publications and source records attributed to J.K. Bohlke.

At least 19 recordsLinked to original sources

The nonpoint source challenge: Obstacles and opportunities for meeting nutrient reduction goals in the Chesapeake Bay watershed

This document examines the Chesapeake Bay watershed response to nutrient and sediment reduction efforts under the Clean Water Act's total maximum daily load (TMDL) regulation. As the 2025 Chesapeake Bay TMDL deadline approaches, water quality goals remain unmet, primarily because of nonpoint source pollution, the largest remaining source of nutrients and sediment, and the primary obstacle to meeting the TMDL. We focus on the factors influencing the gap between the expected effect of management to reduce nonpoint source loads reaching the Bay and empirical evidence suggesting that decades of effort have not produced the expected improvement. This gap may be caused by both insufficient scale and type of implemented water quality management practices and by an overestimation of practice effectiveness. Reasons water quality goals remain unmet include legacy nutrients and lag times masking or delaying the effects of management efforts, areas with large nutrient mass imbalances contributing disproportionate loads, and the difficulty of incentivizing behavior change in voluntary nonpoint source programs. Closing the response gap may require fundamental changes to nonpoint source programs. Apart from seeking additional funding, nonpoint source programs could develop policies to more effectively incentivize behavior change, identify and target treatment of high loading areas with appropriate management actions, and address nutrient mass imbalances.

Chesapeake Bay watershed↗

Evidence of nitrate attenuation in intertidal and subtidal groundwater in a subterranean estuary at a Cape Cod embayment, East Falmouth, Massachusetts, 2015–16

Nitrogen dynamics in intertidal and nearshore subtidal groundwater (subterranean estuary) adjacent to the Seacoast Shores peninsula, Falmouth, Massachusetts, were investigated during 2015–16 by the U.S. Geological Survey. The peninsula is a densely populated residential area with septic systems and cesspools that are substantial sources of nitrogen to groundwater. The study area is in the Eel River, an estuarine saltwater embayment connected to the ocean adjacent to the western shore of the peninsula, that was the subject of an earlier study by Colman and others (2018, https://doi.org/10.3133/sir20185095 ) on nitrogen transport and transformations in groundwater between onshore and offshore locations. The previous study documented the distribution of nitrate concentrations and nitrate attenuation reactions in fresh groundwater beneath the peninsula and the estuary. The current study extended those observations with more detailed sampling and analysis of shallow groundwater from wells near discharge sites beneath the estuary. The current field investigation included sampling of existing wells and installation and sampling of clusters of wells and temporary sampling points in the subterranean estuary, including (1) shallow transects 0.3 to 1.2 meters (m) deep extending from 1 to 13.5 m offshore and (2) deeper wells (from 1.83 to 4.88 m deep) extending from 4.3 to 14.3 m offshore. Measurements of hydraulic-head gradients 2–5 m below the sediment/water interface in the intertidal and nearshore subtidal zones indicated that groundwater flow generally was upwards (towards the estuary) under all tide conditions in October 2016. The magnitude of the gradient was greatest during low tide conditions, indicating that groundwater discharge likely decreased during high tides. Measurements of specific conductance in shallow groundwater in the subterranean estuary in three transects perpendicular to shore were consistent with the existence of saltwater flow cells (infiltration of overlying saline water, mixing with fresh groundwater, and discharge to the overlying saline water) in the intertidal and nearshore subtidal regions. The size of these flow cells was variable in space and time and dependent on the elevation of the tide (spring or neap). At this location in the Eel River subterranean estuary, and offshore to at least 13.5 m, offshore flow of fresh groundwater apparently prevented a deeper saltwater wedge from discharging to the surface. Nitrate concentrations in shallow groundwater (30 to 122 centimeters [cm] depth) were variable in space and time, ranging from not detectable to 600 micromoles per liter (μmol/L) (8.4 milligrams per liter as N), and were highest in June 2016 at depths from 61 to 122 cm below the sediment/water interface and from 4 to 9 m offshore. Nitrate generally was not detectable in saline shallow groundwater at 30-cm depth or at any depth from 30 to 122 cm from 10 to 13.5 m offshore. Dissolved oxygen concentrations were suboxic (less than 16 μmol/L) in 60 percent of the sampled subterranean groundwater beneath the intertidal and subtidal zones. In the remaining sites, the range of dissolved oxygen concentrations was from 18 to 272 μmol/L and the median concentration was 43 μmol/L. Evidence for microbial nitrate reduction (denitrification and possibly anammox) was provided by the distribution of the reaction product nitrogen gas (excess N 2 , or N 2MIC ), as determined from analysis of the dissolved nitrogen gas and argon gas (Ar) concentrations in groundwater samples. Excess nitrogen gas provided evidence for nitrate reduction in shallow groundwater below the subtidal and, to a lesser extent, intertidal zones adjacent to the Seacoast Shores peninsula. These zones, where evidence for nitrate reduction was detected, were in fresh and brackish groundwater near subtidal or intertidal saltwater cells where discharging fresh groundwater mixed with infiltrating saline water. Infiltrating seawater may have supplied organic carbon, one of several potential electron donors that are required for denitrification. Other potential electron donors, such as organic carbon, iron, manganese, hydrogen, methane, ammonium, elemental sulfur, or sulfide phases, may have been supplied by the estuarine sediments. Drainage from surface runoff near the shore also may have supplied organic carbon to fresh groundwater near the intertidal saltwater cell. The highest amounts of nitrate converted to excess nitrogen gas were estimated to be in the range of 230 to 430 μmol/L in nearly fresh groundwater near the subtidal saltwater cell at depths of 61 to 122 cm below the sediment/water interface and from 10 to 13.5 m offshore. Evidence of denitrification within 10 m of the shore was sparse (generally limited to less than 50 μmol/L of N 2 -N) despite the presence of high nitrate concentrations. The spatial distribution of estimated nitrate reduction in the intertidal and nearshore subtidal fresh and brackish groundwater may be related to local variability in the distribution of reactive electron donors in those zones. Variations in the amount of nitrate reduction to nitrogen gas were not clearly related to potential aqueous electron donors such as dissolved organic carbon, nor to potential reaction products such as alkalinity, but may have been controlled by combinations of aqueous and solid-phase reactants. The distribution of relatively shallow fresh groundwater containing nitrate could indicate potential nitrate discharge areas in the lower intertidal zone and uncertain locations farther offshore; however, the data did not extend all the way to the sediment/water interface or to the offshore freshwater limit. This study confirmed substantial loss of nitrate from some of the fresh and brackish groundwater in shallow subestuarine sediments prior to discharge but did not quantify how much nitrate eventually discharged to the estuary.

Massachusetts↗

Spatial, seasonal, and diel controls of nitrogen-carbon-oxygen cycling during lake-water infiltration to an aquifer

Many freshwater lakes are groundwater flow-through systems. Although lakes commonly are considered to be sinks for nitrogen inputs, relatively little is known about carbon and nitrogen export from lakes to groundwater. The current study focused on lake-bottom biogeochemical processes accompanying the transport of nitrogen, dissolved oxygen (O 2 ), and dissolved organic carbon (DOC) during lake-water recharge from a groundwater flow-through lake. Lake-water and porewater (15–100 cm below lakebed) samples were collected along transects within the lake downwelling zone. Infiltrating porewater O 2 and DOC concentrations decreased with depth while nitrate (NO 3 − ) concentrations increased, indicating nitrification of organic matter within the profiles. The depth of NO 3 − production and transport was seasonally dependent. In winter, NO 3 − and O 2 were exported beyond 100-cm depth; whereas in summer, shallow nitrification zones were underlain by deeper NO 3 − reduction zones, and diel patterns of O 2 and NO 3 − penetration depths were observed. Microbial community compositions and stable isotope profiles (δ 15 N[NO 3 − ], δ 18 O[NO 3 − ], δ 18 O[O 2 ]) were consistent with apparent C–N–O reaction stoichiometries indicating O 2 reduction and nitrification in shallower porewater, followed by varying NO 3 − reduction at depth. Maximum porewater NO 3 − concentrations (∼10–20 μM) were limited by infiltrating O 2 concentrations and C/N ratios of reacting organic matter. Lake-water level variations caused changes in shoreline position and porewater velocities, while variations in lake-water temperature, DOC, and O 2 contributed to changes in reaction rates and depth of O 2 and NO 3 − penetration into the lakebed. The quality of groundwater recharged by lake water reflected temporally and spatially varying physical and biogeochemical processes in the sediment porewater.

Journal of Geophysical Research: Biogeosciences↗

Prioritizing water availability study settings to address geogenic contaminants and related societal factors

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.

Environmental Monitoring and Assessment↗

Prioritizing river basins for nutrient studies

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.

Environmental Monitoring and Assessment↗

Minimum requirements for publishing hydrogen, carbon, nitrogen, oxygen and sulfur stable-isotope delta results (IUPAC Technical Report)

Stable hydrogen, carbon, nitrogen, oxygen and sulfur (HCNOS) isotope compositions expressed as isotope-delta values are typically reported relative to international standards such as Vienna Standard Mean Ocean Water (VSMOW), Vienna Peedee belemnite (VPDB) or Vienna Cañon Diablo Troilite (VCDT). These international standards are chosen by convention and the calibration methods used to realise them in practice undergo occasional changes. To ensure longevity and reusability of published data, a comprehensive description of (1) analytical procedure, (2) traceability, (3) data processing, and (4) uncertainty evaluation is required. Following earlier International Union of Pure and Applied Chemistry documents on terminology and notations, this paper proposes minimum requirements for publishing HCNOS stable-isotope delta results. Each of the requirements are presented with illustrative examples.

Pure and Applied Chemistry↗

Standard atomic weights of the elements 2021 (IUPAC Technical Report)

Following the reviews of atomic-weight determinations and other cognate data in 2015, 2017, 2019 and 2021, the IUPAC (International Union of Pure and Applied Chemistry) Commission on Isotopic Abundances and Atomic Weights (CIAAW) reports changes of standard atomic weights. The symbol A r °(E) was selected for standard atomic weight of an element to distinguish it from the atomic weight of an element E in a specific substance P, designated A r (E, P). The CIAAW has changed the values of the standard atomic weights of five elements based on recent determinations of terrestrial isotopic abundances: Ar (argon): from 39.948 ± 0.001 to [39.792, 39.963] Hf (hafnium): from 178.49 ± 0.02 to 178.486 ± 0.006 Ir (iridium): from 192.217 ± 0.003 to 192.217 ± 0.002 Pb (lead): from 207.2 ± 0.1 to [206.14, 207.94] Yb (ytterbium): from 173.054 ± 0.005 to 173.045 ± 0.010 The standard atomic weight of argon and lead have changed to an interval to reflect that the natural variation in isotopic composition exceeds the measurement uncertainty of A r (Ar) and A r (Pb) in a specific substance. The standard atomic weights and/or the uncertainties of fourteen elements have been changed based on the Atomic Mass Evaluations 2016 and 2020 accomplished under the auspices of the International Union of Pure and Applied Physics (IUPAP). A r ° of Ho, Tb, Tm and Y were changed in 2017 and again updated in 2021: Al (aluminium), 2017: from 26.981 5385 ± 0.000 0007 to 26.981 5384 ± 0.000 0003 Au (gold), 2017: from 196.966 569 ± 0.000 005 to 196.966 570 ± 0.000 004 Co (cobalt), 2017: from 58.933 194 ± 0.000 004 to 58.933 194 ± 0.000 003 F (fluorine), 2021: from 18.998 403 163 ± 0.000 000 006 to 18.998 403 162 ± 0.000 000 005 (Ho (holmium), 2017: from 164.930 33 ± 0.000 02 to 164.930 328 ± 0.000 007) Ho (holmium), 2021: from 164.930 328 ± 0.000 007 to 164.930 329 ± 0.000 005 Mn (manganese), 2017: from 54.938 044 ± 0.000 003 to 54.938 043 ± 0.000 002 Nb (niobium), 2017: from 92.906 37 ± 0.000 02 to 92.906 37 ± 0.000 01 Pa (protactinium), 2017: from 231.035 88 ± 0.000 02 to 231.035 88 ± 0.000 01 Pr (praseodymium), 2017: from 140.907 66 ± 0.000 02 to 140.907 66 ± 0.000 01 Rh (rhodium), 2017: from 102.905 50 ± 0.000 02 to 102.905 49 ± 0.000 02 Sc (scandium), 2021: from 44.955 908 ± 0.000 005 to 44.955 907 ± 0.000 004 (Tb (terbium), 2017: from 158.925 35 ± 0.000 02 to 158.925 354 ± 0.000 008) Tb (terbium), 2021: from 158.925 354 ± 0.000 008 to 158.925 354 ± 0.000 007 (Tm (thulium), 2017: from 168.934 22 ± 0.000 02 to 168.934 218 ± 0.000 006) Tm (thulium), 2021: from 168.934 218 ± 0.000 006 to 168.934 219 ± 0.000 005 (Y (yttrium), 2017: from 88.905 84 ± 0.000 02 to 88.905 84 ± 0.000 01) Y (yttrium), 2021: from 88.905 84 ± 0.000 01 to 88.905 838 ± 0.000 002

Pure and Applied Chemistry↗

Isotopic discrimination of natural and anthropogenic perchlorate sources in groundwater in a semi-arid region of northeastern Oregon (USA)

Perchlorate (ClO4−) has synthetic and natural sources. Synthetic ClO4− is released to the environment from its use as an oxidant in military and aerospace applications, and from its presence in a variety of common commercial products, such as safety flares, chlorate herbicides, and fireworks. Natural sources of ClO4− in the environment include imported nitrate fertilizers derived from salt deposits in the Atacama Desert of Chile and indigenous natural ClO4− that accumulates in unsaturated soils and groundwaters in other arid and semi-arid environments, largely from atmospheric deposition. The stable isotope ratios of chlorine (37Cl/35Cl) and oxygen (18O/16O, 17O/16O) and the isotopic abundance of radioactive 36Cl in ClO4− can be used to discriminate these different sources. Perchlorate was previously detected at relatively high concentrations (3.8–34.7 μg/L) in groundwater from many wells in the Boardman-Umatilla area near the Columbia River in northeastern Oregon, which is a semi-arid, highly agricultural, heavily irrigated area that includes several past and current military installations. Eight representative groundwater wells were sampled throughout this region and isotopic characteristics of ClO4− collected from each well were measured along with other chemical and isotopic parameters including tritium and other groundwater age indicators. Isotopic data indicate that indigenous natural ClO4− was present in groundwater from all sampled wells and was the predominant source in five of the wells. Synthetic ClO4− was present in the three remaining wells with natural ClO4−, and a minor fraction of Atacama-fertilizer-derived ClO4− was indicated in one of the wells. Data from this study expand the geographic area of the USA in which indigenous natural ClO4− has been detected to include the semi-arid northwest. This study also illustrates the role of irrigation recharge as a mechanism for producing relatively high concentrations of indigenous natural ClO4− in groundwater by flushing accumulated salts from the unsaturated zone.

Oregon↗

Exploring the potential of electrospray-Orbitrap for stable isotope analysis using nitrate as a model

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 δ15NAIR, δ18OVSMOW, and δ17OVSMOW 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.

Analytical Chemistry↗

Determination of vadose zone and saturated zone nitrate lag times using long-term groundwater monitoring data and statistical machine learning

In this study, we explored the use of statistical machine learning and long-term groundwater nitrate monitoring data to estimate vadose zone and saturated zone lag times in an irrigated alluvial agricultural setting. Unlike most previous statistical machine learning studies that sought to predict groundwater nitrate concentrations within aquifers, the focus of this study was to leverage available groundwater nitrate concentrations and other environmental variables to determine mean regional vertical velocities (transport rates) of water and solutes in the vadose zone and saturated zone (3.50 and 3.75 m yr −1 , respectively). The statistical machine learning results are consistent with two primary recharge processes in this western Nebraska aquifer, namely ( 1 ) diffuse recharge from irrigation and precipitation across the landscape and ( 2 ) focused recharge from leaking irrigation conveyance canals. The vadose zone mean velocity yielded a mean recharge rate (0.46 m yr −1 ) consistent with previous estimates from groundwater age dating in shallow wells (0.38 m yr −1 ). The saturated zone mean velocity yielded a recharge rate (1.31 m yr −1 ) that was more consistent with focused recharge from leaky irrigation canals, as indicated by previous results of groundwater age dating in intermediate-depth wells (1.22 m yr −1 ). Collectively, the statistical machine learning model results are consistent with previous observations of relatively high water fluxes and short transit times for water and nitrate in the primarily oxic aquifer. Partial dependence plots from the model indicate a sharp threshold in which high groundwater nitrate concentrations are mostly associated with total travel times of 7 years or less, possibly reflecting some combination of recent management practices and a tendency for nitrate concentrations to be higher in diffuse infiltration recharge than in canal leakage water. Limitations to the machine learning approach include the non-uniqueness of different transport rate combinations when comparing model performance and highlight the need to corroborate statistical model results with a robust conceptual model and complementary information such as groundwater age.

Nebraska↗

Isotopic composition of natural and synthetic chlorate (δ18O, Δ17O, δ37Cl, 36Cl/Cl): Methods and initial results

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.

Chemosphere↗

Origin of the isotopic composition of natural perchlorate: Experimental results for the impact of reaction pathway and initial ClOx reactant

Natural perchlorate (ClO 4 − ) exists in many places on Earth, in lunar regolith, meteorites, and on the surface of Mars. Terrestrial natural ClO 4 − has widely variable Cl and O stable isotopic compositions (δ 37 Cl, δ 18 O, Δ 17 O). The δ 18 O and Δ 17 O values of ClO 4 − from the most hyper-arid locations co-vary. ClO 4 − from less arid areas has relatively little 17 O excess and poor Δ 17 O-δ 18 O correlation. ClO 4 − from the Atacama Desert has unusually low δ 37 Cl (<−10‰) and exhibits a positive correlation between δ 37 Cl and δ 18 O, while the δ 37 Cl of ClO 4 − from all other locations varies between −5 and +7‰ with no δ 37 Cl-δ 18 O covariation. To evaluate the impact of different precursors (ClO x ) and reaction pathways on the isotopic composition of ClO 4 − , we measured the isotopic composition of ClO 4 − produced in the laboratory by UV or O 3 mediated aqueous oxidation of Cl − , OCl − , ClO 2 − , and ClO 2 ° as well as O 3 mediated oxidation of dry NaCl. ClO x oxidation in aqueous or dry systems enriched in O 3 produced ClO 4 − with Δ 17 O values that generally increased with the number of O atoms required and included evidence that the site-specific 17 O anomaly in O 3 was preferentially transferred to ClO 4 − . Based on the inferred number of O atoms sourced from O 3 , and known Cl and O reaction pathways, it appears that ClO 2 ° and ClO 3 * were required intermediates in the production of ClO 4 − in the O 3 experiments. ClO x aqueous oxidation by UV irradiation produced ClO 4 − with a large range of δ 18 O values and little or no 17 O anomaly. ClO 3 − was produced to a much greater extent than ClO 4 − in all experiments except dry oxidation of NaCl by O 3 . The isotopic composition of ClO 3 − was distinct from that of ClO 4 − produced from the same initial reactants. Combined results of O 3 and UV mediated reactions largely bracketed the range of natural ClO 4 − δ 18 O and Δ 17 O values as well as δ 37 Cl values of non-Atacama natural samples, but no conditions produced the low δ 37 Cl values of Atacama ClO 4 − . Our results indicate that variation in production mechanisms, possibly combined with isotopically variable precursors, could be responsible for much of the observed isotopic variation in natural ClO 4 − and ClO 3 − .

Geochimica et Cosmochimica Acta↗

The influence of sample matrix on the accuracy of nitrite N and O isotope ratio analyses with the azide method

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.

Rapid Communications in Mass Spectrometry↗

Degradation of RDX (Hexahydro-1,3,5-trinitro-1,3,5-triazine) in contrasting coastal marine habitats: Subtidal non-vegetated (sand), subtidal vegetated (silt/eel grass), and intertidal marsh

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.

Connecticut, New York↗

Assessing the seasonal dynamics of nitrate and sulfate aerosols at the South Pole utilizing stable isotopes

Atmospheric nitrate (NO 3 − = particulate NO 3 − + gas‐phase nitric acid [HNO 3 ]) and sulfate (SO 4 2− ) are key molecules that play important roles in numerous atmospheric processes. Here, the seasonal cycles of NO 3 − and total suspended particulate sulfate (SO 4 2− (TSP) ) were evaluated at the South Pole from aerosol samples collected weekly for approximately 10 months (26 January to 25 October) in 2002 and analyzed for their concentration and isotopic compositions. Aerosol NO 3 − was largely affected by snowpack emissions in which [NO 3 − ] and δ 15 N(NO 3 − ) were highest (49.3 ± 21.4 ng/m 3 , n = 8) and lowest (−47.0 ± 11.7‰, n = 5), respectively, during periods of sunlight in the interior of Antarctica. The seasonal cycle of Δ 17 O(NO 3 − ) reflected tropospheric chemistry year‐round with lower values observed during sunlight periods and higher values observed during dark periods, reflecting shifts from HO x ‐ to O 3 ‐dominated oxidation chemistry. SO 4 2− (TSP) concentrations were highest during austral summer and fall (86.7 ± 73.7 ng/m 3 , n = 18) and are indicated to be derived from dimethyl sulfide (DMS) emissions, as δ 34 S(SO 4 2− ) (TSP) values (18.5 ± 1.0‰, n = 10) were similar to literature δ 34 S(DMS) values. The seasonal cycle of Δ 17 O(SO 4 2− ) (TSP) exhibited minima during austral summer (0.9 ± 0.1‰, n = 5) and maxima during austral fall (1.3 ± 0.3‰, n = 6) and austral spring (1.6 ± 0.1‰, n = 5), indicating a shift from HO x ‐ to O 3 ‐dominated chemistry in the atmospheric derived SO 4 2− component. Overall, the budgets of NO 3 − and SO 4 2− (TSP) at the South Pole were complex functions of transport, localized chemistry, biological activity, and meteorological conditions, and these results will be important for interpretations of oxyanions in ice core records in the interior of Antarctica.

Journal of Geophysical Research D: Atmospheres↗

Seasonal and spatial variation in the location and reactivity of a nitrate-contaminated groundwater discharge zone in a lakebed

Groundwater discharge delivering anthropogenic N from surrounding watersheds can impact lake nutrient budgets. However, upgradient groundwater processes and changing dynamics in N biogeochemistry at the groundwater-lake interface are complex and difficult to resolve. In this study, hydrograph variations in a groundwater flow-through lake altered discharge patterns of a wastewater-derived, groundwater contaminant plume, thereby affecting biogeochemical processes controlling N transport. Groundwater geochemistry 15 cm under the lakebed along transects perpendicular to shore varied from oxic to anoxic with increasing nitrate concentrations (10-75 M) and corresponding gradients in nitrite and nitrous oxide. Porewater depth profiles of nitrate concentrations and stable isotope compositions largely reflected upgradient groundwater N sources and N-cycle processes, with minor additional nitrate reduction in the shallowest lakebed sediments. Potential denitrification rates determined in laboratory microcosms were 10-100 fold higher in near-surface sediments (0-5 cm) than in deeper sediments (5-30 cm) and were correlated with sediment carbon content and abundance of denitrification genes (nirS, nosZI, and nosZII). Potential anammox-driven N2 production was highest in deeper anoxic sediments. Injection of bromide and nitrite in the lake sediments indicated a vertical porewater velocity of 4-5 cm hr-1, with highest nitrite consumption rates above 10 cm. However, short residence times in the shallow sediments allowed only a small fraction of the contaminant nitrate to be removed before discharging into the lake. Results demonstrate the importance of resolving local versus upgradient biogeochemical processes affecting contaminant distribution in discharge areas, and transient migration of local gradients and processes in response to changing lake levels and groundwater flow paths.

Journal of Geophysical Research: Biogeosciences↗

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↗