Geology topics

J.K. Bohlke

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

At least 37 records · Page 2Linked to original sources

USGS2019

Seasonality of nitrate sources and isotopic composition in the Upper Illinois River

To improve understanding of spatial, seasonal, and inter-annual variations in nitrate sources and in-stream processes in the Illinois River system, nitrate concentrations and isotopic compositions were measured in 445 water samples collected over a four-year period (2004–2008) from the Upper Illinois River Basin (UIRB). Samples included surface water in the river and major tributaries, effluent samples from Chicago’s largest wastewater treatment plant (WTP), and representative groundwater from shallow wells in agricultural land. Two principal nitrate endmember sources within the UIRB had distinctive isotopic compositions: WTP effluent with δ 15 N = 8.6 ± 1.7‰ and δ 18 O = 0.8 ± 1.4‰ and agricultural groundwater with δ 15 N-NO 3 = 3.4 ± 0.6‰ and δ 18 O = 3.7 ± 0.5‰ (when minimally affected by nitrate reduction). Isotopic data indicated that the large pulse of nitrate exported from the river basin during the spring was mostly derived from agricultural land drainage, while nitrate from large WTP effluent point sources was predominant in the upper reaches of the river near Chicago. During low base-flow conditions in late-summer and fall, the agricultural nitrate source was greatly diminished and the headwater WTP source was predominant in the river basin export. Our results indicated biogeochemical nitrate reduction and isotopic fractionation occurred within the river network, affecting both agricultural and urban sources during surface-water transport. In addition, diminished agricultural nitrate export was attributable to preferential discharge of biogeochemically reduced groundwater during low base flow. Isotopic indicators of spatial and seasonal variations in the relative importance of different nitrate sources, and their relative susceptibility to natural attenuation, might be useful for guiding monitoring and management practices to reduce nitrate export from complex watersheds with mixed land uses.

Upper Illinois River↗

USGS2019

Tracing the cycling and fate of the munition, Hexahydro-1,3,5-trinitro-1,3,5-triazine in a simulated sandy coastal marine habitat with a stable isotopic tracer, 15N-[RDX]

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.

Science of the Total Environment↗

USGS2019

Methane and nitrous oxide temporal and spatial variability in two midwestern USA streams containing high nitrate concentrations

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.

Illinois, Indiana↗

USGS2019

Reactive transport modeling to understand attenuation of arsenic concentrations in anoxic groundwater during Fe(II) oxidation by nitrate

A previously published field-experimental investigation showed that injection of nitrate in anoxic groundwater that contained aqueous and sediment-bound Fe(II) diminished concentrations of As(V) and As(III) to below drinking-water limits. In the current study, reactive transport modeling confirmed that the observed attenuation was consistent with oxidation of Fe(II) by nitrate, leading to precipitation of hydrous ferric oxide, which, in turn, sorbed both As(V) and As(III). After calibration with site-specific observations, reactive transport modeling could aid in designing effective treatment to remove arsenic using injection of nitrate to oxidize Fe(II).

Book chapter↗

USGS2018

IUPAC Periodic Table of the Elements and Isotopes (IPTEI) for the education community (IUPAC Technical Report)

The IUPAC (International Union of Pure and Applied Chemistry) Periodic Table of the Elements and Isotopes (IPTEI) was created to familiarize students, teachers, and non-professionals with the existence and importance of isotopes of the chemical elements. The IPTEI is modeled on the familiar Periodic Table of the Chemical Elements. The IPTEI is intended to hang on the walls of chemistry laboratories and classrooms. Each cell of the IPTEI provides the chemical name, symbol, atomic number, and standard atomic weight of an element. Color-coded pie charts in each element cell display the stable isotopes and the relatively long lived radioactive isotopes having characteristic terrestrial isotopic compositions that determine the standard atomic weight of each element. The background color scheme of cells categorizes the 118 elements into four groups: (1) white indicates the element has no standard atomic weight, (2) blue indicates the element has only one isotope that is used to determine its standard atomic weight, which is given as a single value with an uncertainty, (3) yellow indicates the element has two or more isotopes that are used to determine its standard atomic weight, which is given as a single value with an uncertainty, and (4) pink indicates the element has a well-documented variation in its atomic weight, and the standard atomic weight is expressed as an interval. An element-by-element review accompanies the IPTEI and includes a chart of all known stable and radioactive isotopes for each element. Practical applications of isotopic measurements and technologies are included for the following fields: forensic science, geochronology, Earth-system sciences, environmental science, and human health sciences, including medical diagnosis and treatment.

Pure and Applied Chemistry↗

USGS2018

Geochemical conditions and nitrogen transport in nearshore groundwater and the subterranean estuary at a Cape Cod embayment, East Falmouth, Massachusetts, 2013–14

Nitrogen transport and transformation were studied during 2013 to 2014 by the U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency, in a subterranean estuary beneath onshore locations on the Seacoast Shores peninsula, a residential area in Falmouth, Massachusetts, served by septic systems and cesspools, and adjacent offshore locations in the Eel River, a saltwater embayment connected to the ocean. The field investigation included installation and sampling of clusters of wells and temporary sampling points near a transect extending from about 35 meters (m) onshore to 18 m offshore. The fresh groundwater at the study site formed a lens about 11 m thick at the shoreline that was underlain by saline groundwater. Groundwater flow in the water-table aquifer was oriented northwestward toward the embayment. Nitrate concentrations in the fresh groundwater at a site about 35 m onshore increased in the downward direction from less than 500 micromoles per liter near the water table to about 1,700 micromoles per liter just above the freshwater/saltwater transition zone. Dissolved oxygen was largely absent in the onshore fresh groundwater. Distributions of salinity, dissolved oxygen, and nitrate at the shoreline and offshore generally were similar to those onshore; at some locations, however, shallow saline water was present above the freshwater, and there were scattered occurrences of elevated dissolved oxygen concentrations. Geochemical indicators of nitrate reduction, including concentrations of the reaction product nitrogen gas, stable isotope ratios of nitrate and nitrogen gas, and changes in alkalinity, provided evidence for nitrate reduction in two zones separated vertically by a zone 7–8 m thick with no evidence of nitrate reduction. The shallow nitrate-reduction zone was near the water table in fresh groundwater onshore, where nitrate reduction may be related to particular recharge conditions at nearby sources. The shallow nitrate-reduction zone also may be related to an interval of fine-grained sediments at about the same altitude (−1 to −6 m relative to the National Geodetic Vertical Datum of 1929), where flow is slower and reactive electron donors such as solid organic carbon, iron, or sulfide phases may be present to drive the reduction. The deep nitrate-reduction zone was near the freshwater/saltwater transition zone, where nitrate reduction may be related to mixing of freshwater containing nitrate and saltwater containing dissolved organic carbon and ammonium, or to fine-grained sediments near the transition zone. The maximum amount of nitrate converted to nitrogen gas was estimated to be less than or equal to 300 micromoles per liter in both nitrate-reduction zones. The presence of nitrate and low dissolved oxygen concentrations in the 7–8-meter-thick zone between the shallow and deep nitrate-reduction zones are conditions that could permit nitrate reduction. The absence of evidence of nitrate reduction in the high-nitrate zone may have resulted from the lack of reactive electron donors in that depth interval. The high-nitrate zone dissipated somewhat in the offshore direction, but the current study did not extend far enough to encompass the fresh groundwater discharge area or determine how much of the nitrate was removed prior to discharge. A shallow intertidal saltwater cell was formed during a spring tide by saltwater infiltration during tidal run-up on the beach. Nitrate reduction might have occurred if nitrate-containing fresh groundwater discharging to the estuary mixed with the saltwater containing dissolved organic carbon in this zone, but samples collected from the intertidal saltwater cell during this study were not analyzed for indicators of nitrate reduction. Elevated dissolved oxygen concentrations in fresh groundwater 9 m offshore may indicate that groundwater flow was partly oblique to the sampling transect or that groundwater from a regional flow system was converging under the river near the study area. Flow directions also may have been affected by aquifer heterogeneity such as the shallow fine-grained sediments onshore and at the bottom of the Eel River. Improved understanding of the fate of nitrate in this type of complex setting might be gained by including additional characterization of aquifer heterogeneity and groundwater flow and extending investigations of nitrate reduction to the shallow sediments in the intertidal saltwater cell and adjacent subtidal zone and to locations farther offshore beneath the estuary.

Massachusetts↗

USGS2018

Preliminary assessment of stable nitrogen and oxygen isotopic composition of USGS51 and USGS52 nitrous oxide reference gases and perspectives on calibration needs

Rationale Despite a long history and growing interest in isotopic analyses of N 2 O, there is a lack of isotopically characterized N 2 O isotopic reference materials (standards) to enable normalization and reporting of isotope‐delta values. Here we report the isotopic characterization of two pure N 2 O gas reference materials, USGS51 and USGS52, which are now available for laboratory calibration ( https://isotopes.usgs.gov/lab/referencematerials.html ). Methods A total of 400 sealed borosilicate glass tubes of each N 2 O reference gas were prepared from a single gas filling of a high vacuum line. We demonstrated isotopic homogeneity via dual‐inlet isotope‐ratio mass spectrometry. Isotopic analyses of these reference materials were obtained from eight laboratories to evaluate interlaboratory variation and provide preliminary isotopic characterization of their δ 15 N, δ 18 O, δ 15 N α , δ 15 N β and site preference ( S P ) values. Results The isotopic homogeneity of both USGS51 and USGS52 was demonstrated by one‐sigma standard deviations associated with the determinations of their δ 15 N, δ 18 O, δ 15 N α , δ 15 N β and S P values of 0.12 mUr or better. The one‐sigma standard deviations of S P measurements of USGS51 and USGS52 reported by eight laboratories participating in the interlaboratory comparison were 1.27 and 1.78 mUr, respectively. Conclusions The agreement of isotope‐delta values obtained in the interlaboratory comparison was not sufficient to provide reliable accurate isotope measurement values for USGS51 and USGS52. We propose that provisional values for the isotopic composition of USGS51 and USGS52 determined at the Tokyo Institute of Technology can be adopted for normalizing and reporting sample data until further refinements are achieved through additional calibration efforts.

Rapid Communications in Mass Spectrometry↗

USGS2018

Clarification of the term “normal material” used for standard atomic weights (IUPAC Technical Report)

The standard atomic weights of the elements apply to normal materials. Since 1984, the Commission on Isotopic Abundances and Atomic Weights (Commission) has defined a normal material as: “The material is a reasonably possible source for this element or its compounds in commerce, for industry or science; the material is not itself studied for some extraordinary anomaly and its isotopic composition has not been modified significantly in a geologically brief period.” The term “a geologically brief period” in this definition is confusing, and confusion can be reduced by revising this definition to the following, which was accepted by the Commission on Isotopic Abundances and Atomic Weights at its meeting in Groningen, Netherlands in September 2017: “ Normal materials include all substances, except (1) those subjected to substantial deliberate, undisclosed, or inadvertent artificial isotopic modification, (2) extraterrestrial materials, and (3) isotopically anomalous specimens, such as natural nuclear reactor products from Oklo (Gabon) or other unique occurrences.”

Pure and Applied Chemistry↗

USGS2018

Four-dimensional isotopic approach to identify perchlorate sources in groundwater: Application to the Rialto-Colton and Chino subbasins, southern California (USA)

Perchlorate (ClO 4 − ) in groundwater can be from synthetic or natural sources. Natural sources include ClO 4 − associated with historical application of imported natural nitrate fertilizer from the Atacama Desert of Chile, and indigenous ClO 4 − that accumulates locally in arid regions from atmospheric deposition. The Rialto-Colton groundwater subbasin, 80 km east of Los Angeles, California, includes two mapped ClO 4 − plumes from known military/industrial sources. Larger areas downgradient from those plumes, and in the Chino subbasin to the southwest, also contain ClO 4 − . Perchlorate from wells was analyzed for chlorine and oxygen stable isotope ratios (δ 37 Cl, δ 18 O, Δ 17 O) and radioactive chlorine-36( 36 Cl) isotopic abundance, along with other geochemical, isotopic, and hydrogeologic data. Isotopic data show that synthetic ClO 4 − was the dominant source within the mapped plumes. Downgradient from the mapped plumes, and in the Chino subbasin, the dominant source of ClO 4 − was related to past agricultural use of Chilean (Atacama) nitrate fertilizer. The 36 Cl and δ 18 O data indicate that wells having predominantly synthetic or Atacama ClO 4 − also contained small fractions of indigenous ClO 4 − . Little or no differences were observed in isotopic composition or ClO 4 − source with depth in depth-dependent data from selected wells. Indigenous ClO 4 − was most evident in upgradient wells having ClO 4 − concentrations <1 μg/L, consistent with its occurrence as a background constituent throughout the region. Stable isotope ratios of chlorine and oxygen and 36 Cl isotopic abundance data provided relatively unambiguous discrimination of synthetic and Atacama sources in most wells having ClO 4 − concentrations greater than 1 μg/L.

California↗

USGS2018

Minimum energy requirements for desalination of brackish groundwater in the United States with comparison to international datasets

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.

Water Research↗

USGS2018

Validation of stable isotope ratio analysis to document the biodegradation and natural attenuation of RDX, ESTCP Project ER-201208

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a common soil contaminant at current and former military facilities, including many training and testing ranges. Because RDX is readily transported through soils to the subsurface, this nitramine explosive now also impacts groundwater and drinking water at numerous locations across the country. A significant issue with RDX contamination on ranges and at other military installations is that it often occurs over expansive areas, where in situ or ex situ treatment technologies are difficult to implement. One potential alternative for military ranges and other facilities is monitored natural attenuation (MNA), in which contaminant degradation by natural processes, including biodegradation, are evaluated. However, one limitation of this approach for RDX is the inability to accurately evaluate whether the nitramine is biodegrading under field conditions, as rates may be relatively slow. One potential technique to overcome this limitation is the use of compound-specific stable isotope analysis (CSIA), where biological contaminant destruction can be documented as changes in the ratio of stable isotopes of specific elements in a molecule; for RDX, ratios of 15 N/ 14 N and 13 C/ 12 C are relevant. The objective of this project is to validate a CSIA method to confirm and constrain rates of aerobic and anaerobic biodegradation of RDX at field sites. This technique can be utilized by DoD to provide critical data to support MNA as a remedy for treating this energetic in groundwater, and confirm the effectiveness of in situ enhanced bioremediation remedies. The stable isotopic composition of NO 3 - and NO 2 - was also measured when these anions co-occurred with RDX to evaluate whether these potential degradation products from RDX could be used to further demonstrate MNA in the field.

Report↗

USGS2017

Response of deep groundwater to land use change in desert basins of the Trans-Pecos region, Texas, USA: Effects on infiltration, recharge, and nitrogen fluxes

Quantifying the effects of anthropogenic processes on groundwater in arid regions can be complicated by thick unsaturated zones with long transit times. Human activities can alter water and nutrient fluxes, but their impact on groundwater is not always clear. This study of basins in the Trans-Pecos region of Texas links anthropogenic land use and vegetation change with alterations to unsaturated zone fluxes and regional increases in basin groundwater NO 3 − concentrations. Median increases in groundwater NO 3 − (by 0.7–0.9 mg-N/l over periods ranging from 10 to 50+ years) occurred despite low precipitation (220–360 mm/year), high potential evapotranspiration (~1570 mm/year), and thick unsaturated zones (10–150+ m). Recent model simulations indicate net infiltration and groundwater recharge can occur beneath Trans-Pecos basin floors, and may have increased due to irrigation and vegetation change. These processes were investigated further with chemical and isotopic data from groundwater and unsaturated zone cores. Some unsaturated zone solute profiles indicate flushing of natural salt accumulations has occurred. Results are consistent with human-influenced flushing of naturally accumulated unsaturated zone nitrogen as an important source of NO 3 − to the groundwater. Regional mass balance calculations indicate the mass of natural unsaturated zone NO 3 − (122–910 kg-N/ha) was sufficient to cause the observed groundwater NO 3 − increases, especially if augmented locally with the addition of fertilizer N. Groundwater NO 3 − trends can be explained by small volumes of high NO 3 − modern recharge mixed with larger volumes of older groundwater in wells. This study illustrates the importance of combining long-term monitoring and targeted process studies to improve understanding of human impacts on recharge and nutrient cycling in arid regions, which are vulnerable to the effects of climate change and increasing human reliance on dryland ecosystems.

Texas↗

USGS2017

Tracking the fate of nitrate through pulse-flow wetlands: A mesocosm scale 15N enrichment tracer study

Quantitative information about the fate of applied nitrate (NO 3 -N) in pulse-flow constructed wetlands is essential for designing wetland treatment systems and assessing their nitrogen removal services for agricultural and stormwater applications. Although many studies have documented NO 3 -N losses in wetlands, controlled experiments indicating the relative importance of different processes and N sinks are scarce. In the current study, 15 NO 3 -N isotope enrichment tracer experiments were conducted in wetland mesocosms of two different wetland soil types at two realistic agricultural NO 3 -N source loads. The 15 N label was traced from the source NO 3 -N into plant biomass, soil (including organic matter and ammonium), and N-gas constituents over 7–10 day study periods. All sinks responded positively to higher NO 3 -N loading. Plant uptake exceeded denitrification 2–3 fold in the low NO 3 -N loading experiments, while both fates were nearly equivalent in the high loading experiments. One to two years later, soils largely retained the assimilated tracer N, whereas plants had lost much of it. Results demonstrated that plant and microbial assimilation in the soil (temporary N sinks) can exceed denitrification (permanent N loss) in pulse-flow environments and must be considered by wetland designers and managers for optimizing nitrogen removal potential.

Ecological Engineering↗

USGS2017

Stable isotopic composition of perchlorate and nitrate accumulated in plants: Hydroponic experiments and field data

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.

Science of the Total Environment↗

USGS2016

Stable isotope analyses of oxygen (18O:17O:16O) and chlorine (37Cl:35Cl) in perchlorate: reference materials, calibrations, methods, and interferences

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.

Rapid Communications in Mass Spectrometry↗

USGS2016

Density-driven free-convection model for isotopically fractionated geogenic nitrate in sabkha brine

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 − .

Groundwater↗

USGS2016

Corrigendum to “Widespread occurrence of (per)chlorate in the Solar System” [Earth Planet. Sci. Lett. 430 (2015) 470–476]

The authors regret that two sets of data (Atacama (Rao et al., 2010) and Mars Meteorite Range (Kounaves et al., 2014)) in Fig. 2 of our article were plotted in the wrong units. The correction does not change the relationship between ClO 3 − "> ClO3− and ClO 4 − "> ClO4− ; it only shifts the magnitude of the concentrations. The conclusions of the article are not affected. The corrected Fig. 2 appears below.

Earth and Planetary Science Letters↗

USGS2016

Relating carbon and nitrogen isotope effects to reaction mechanisms during aerobic or anaerobic degradation of RDX (Hexahydro-1,3,5-Trinitro-1,3,5-Triazine) by pure bacterial cultures

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 NO 2 − 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 NO 2 − production were much larger than, but systematically related to, the bulk RDX N isotope effects with different bacteria. Apparent intrinsic ε 15 N-NO 2 − values were consistent with an initial denitration pathway in the aerobic experiments and more complex processes of NO 2 − 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., NO x ) in the environment are warranted.

Applied and Environmental Microbiology↗