Geology topics

Linnea J. Heraty

Publications and source records attributed to Linnea J. Heraty.

4 recordsLinked to original sources

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

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↗

USGS2011

Applications of selective ion exchange for perchlorate removal, recovery, and environmental forensics

Perchlorate (ClO4-) is a widespread contaminant found in drinking water and groundwater that has caused far-reaching ramifications ranging from public health issues to potential liabilities arising from environmental clean-up requirements. The chapter summarizes recent developments in highly selective and regenerable ion exchange technologies for removing ClO4- from contaminated water. The technologies rely on a unique, highly specific resin to trap ClO4-. The resin is then regenerated and ClO4- is either destroyed or recovered—leading to significant cost reduction and waste minimization. The ability to recover trace quantities of pure ClO4- from contaminated media also allows unambiguous identification of the sources of its contamination through stable isotope ratio analysis of chlorine and oxygen atoms. We provide detailed descriptions of the techniques for extracting, purifying, and crystallizing trade amounts of ClO4- and characterizing its isotopic composition for fingerprinting in the environment.

Book chapter↗

USGS2007

Oxygen and chlorine isotopic fractionation during perchlorate biodegradation: Laboratory results and implications for forensics and natural attenuation studies

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

Environmental Science & Technology↗