Evaluation of Stable Chlorine and Bromine Isotopes in Sedimentary Formation Fluids

Two new analytical methodologies were developed for chlorine and bromine stable isotope analyses of inorganic samples by Continuous-Flow Isotope Ratio Mass Spectrometry (CF-IRMS) coupled with gas chromatography (GC). Inorganic chloride and bromide were precipitated as silver halides (AgCl and AgBr) and then converted to methyl halide (CH3Cl and CH3Br) gases and analyzed. These new techniques require small samples sizes (1.4 µmol of Cl- and 1 µmol of Br-). The internal precision using pure CH3Cl gas is better than ∓0.04 ‰ (∓STDV) while the external precision using seawater standard is better than ∓0.07 ‰ (∓STDV). The internal precision using pure CH3Br gas is better than ∓0.03 ‰ (∓STDV) and the external precision using seawater standard is better than ∓0.06 ‰ (∓STDV). Moreover, the sample analysis time is much shorter than previous techniques. The analyses times for chlorine and bromine stable isotopes are 16 minutes which are 3-5 times shorter than all previous techniques. Formation waters from three sedimentary settings (the Paleozoic sequences in southern Ontario and Michigan, the Williston Basin and the Siberian Platform) were analyzed for 37Cl and 81Br isotopes. The δ37Cl and δ81Br values of the formation waters from these basins are characterized by large variations (between -1.31 ‰ and +1.82 ‰ relative to SMOC and between -1.50 ‰ and +3.35 ‰ relative to SMOB, respectively). A positive trend between δ81Br and δ37Cl values was found in all basins, where an enrichment of δ81Br is coupled by an enrichment of δ37Cl. In the Paleozoic sequences in southern Ontario and Michigan, the δ37Cl and δ81Br signatures of formation water collected from northwest of the Algonquin Arch are distinct from those collected from southeast of the Arch. All of the brines from the northwest of the Algonquin Arch are characterized by depleted isotopic values in comparison with the isotopic values from the brines from southeast of the Arch. The δ81Br signatures of the two brines show total separation with no overlaps. The δ37Cl values show some overlap between the two groups. One of the scenarios that can be put forward is that the Arch forms a water divide, where sediments southeast of the Arch are dominated by Appalachian Basin formation waters, and the sediments located northwest of the Arch are dominated by the Michigan Basin formation waters. The δ81Br and δ37Cl signatures of the Williston Basin brines suggest the existence of several different brines that are isotopically distinct and located in different stratigraphic units, even though they are chemically similar. The relatively wide range of δ37Cl and δ81Br of the formation waters suggests that the ocean isotopic signatures were variable over geologic time. A seawater temporal curve for δ81Br and δ37Cl was proposed with a larger variation of δ81Br in comparison with δ37Cl. The isotopic variations of these two elements agree very well with 87Sr/86Sr seawater variation during the same period. In general, the use of chlorine and bromine stable isotopes can be very useful in assessing the origin and the evolutionary processes involved in evolving formation waters and also in distinguishing different brines (end members). Furthermore, they can be employed to investigate the hydrogeological dynamics of sedimentary basins

Evaluating TCE Abiotic and Biotic Degradation Pathways in a Permeable Reactive Barrier Using Compound Specific Isotope Analysis

A pilot-scale zero valent iron (ZVI) Permeable Reactive Barrier (PRB) was installed using an azimuth-controlled -vertical hydrofracturing at an industrial facility to treat a chlorinated Volatile Organic Compound (VOC) plume. Following ZVI injection, no significant reduction in concentration was observed to occur with the exception of some multilevel monitoring wells, which also showed high levels of total organic carbon (TOC). These patterns suggested that the zero valent iron was not well distributed in the PRB creating leaky conditions. The geochemical data indicated reducing conditions in these areas where VOC reduction was observed, suggesting that biotic processes, associated to the guar used in the injection of the iron, could be a major mechanism of VOC degradation. Compound-Specific Isotope Analysis (CSIA) using both carbon and chlorine stable isotopes were used as a complementary tool for evaluating the contribution of abiotic and biotic processes to VOC trends in the vicinity of the PRB. The isotopic data showed enriched isotope values around the PRB compared to the isotope composition of the VOC source confirming that VOC degradation is occurring along the PRB. A batch experiment using site groundwater collected near the VOC source and the ZVI used in the PRB was performed to evaluate the site-specific abiotic isotopic fractionation patterns. Field isotopic trends, typical of biodegradations were observed at the site and were different from those obtained during the batch abiotic experiment. These differences in isotopic trends combined with changes in VOC concentrations and redox parameters suggested that biotic processes are the predominant pathways involved in the degradation of VOCs in the vicinity of the PRB. Ground Water Monitoring & Remediation. © 2012, National Ground Water Association

Use of dual element isotope analysis and microcosm studies to determine the origin and potential anaerobic biodegradation of dichloromethane in two multi-contaminated aquifers

Many aquifers around the world are impacted by toxic chlorinated methanes derived from industrial processes due to accidental spills. Frequently, these contaminants co-occur with chlorinated ethenes and/or chlorinated benzenes in groundwater, forming complex mixtures that become very difficult to remediate. In this study, a multi-method approach was used to provide lines of evidence of natural attenuation processes and potential setbacks in the implementation of bioremediation strategies in multi-contaminated aquifers. First, this study determined i) the carbon and chlorine isotopic compositions (δ¹³C, δ³⁷Cl) of several commercial pure phase chlorinated compounds, and ii) the chlorine isotopic fractionation (εCl = −5.2 ± 0.6‰) and the dual CCl isotope correlation (ΛC/Cl = 5.9 ± 0.3) during dichloromethane (DCM) degradation by a Dehalobacterium-containing culture. Such data provide valuable information for practitioners to support the interpretation of stable isotope analyses derived from polluted sites. Second, the bioremediation potential of two industrial sites contaminated with a mixture of organic pollutants (mainly DCM, chloroform (CF), trichloroethene (TCE), and mono-chlorobenzene (MCB)) was evaluated. Hydrochemistry, dual (CCl) isotope analyses, laboratory microcosms, and microbiological data were used to investigate the origin, fate and biodegradation potential of chlorinated methanes. At Site 1, δ¹³C and δ³⁷Cl compositions from field samples were consistent with laboratory microcosms, which showed complete degradation of CF, DCM and TCE, while MCB remained. Identification of Dehalobacter sp. in CF-enriched microcosms further supported the biodegradation capability of the aquifer to remediate chlorinated methanes. At Site 2, hydrochemistry and δ¹³C and δ³⁷Cl compositions from field samples suggested little DCM, CF and TCE transformation; however, laboratory microcosms evidenced that their degradation was severely inhibited, probably by co-contamination. A dual CCl isotopic assessment using results from this study and reference values from the literature allowed to determine the extent of degradation and elucidated the origin of chlorinated methanes

Strontium isotopic ratio in brines from the north-east of the Angara-Lenskiy artesian basin

The Sr isotopic composition was measured in a number of samples of highly concentrated oil-field brines from the Angara-Lenskiy artesian basin. The brines are contained in the salt-bearing and subsalt-bearing hydrogeological formations at a depth of 1,500-3,000 m. They have high salinity (385-530 g/L) and high Sr content (2.3-7.0 mg/L). The 87Sr/86Sr ratio ranges from 0.70800 to 0.713062. Most brine samples exhibit an isotopic composition similar to Vendian-Cambrian paleoocean water, however several samples from the Yaraktinskiy horizon are significantly more radiogenic than others. It suggests that a considerable amount of 87Sr is likely to have been carried from terrigenous sediments due to a water-rock interaction

Thermodynamic and hydrochemical controls on CH4 in a coal seam gas and overlying alluvial aquifer: New insights into CH4 origins

Using a comprehensive data set (dissolved CH4, δ13C-CH4, δ2H-CH4, δ13C-DIC, δ37Cl, δ2H-H2O, δ18O-H2O, Na, K, Ca, Mg, HCO3, Cl, Br, SO4, NO3 and DO), in combination with a novel application of isometric log ratios, this study describes hydrochemical and thermodynamic controls on dissolved CH4 from a coal seam gas reservoir and an alluvial aquifer in the Condamine catchment, eastern Surat/north-western Clarence-Moreton basins, Australia. δ13C-CH4 data in the gas reservoir (−58‰ to −49‰) and shallow coal measures underlying the alluvium (−80‰ to −65‰) are distinct. CO2 reduction is the dominant methanogenic pathway in all aquifers, and it is controlled by SO4 concentrations and competition for reactants such as H2. At isolated, brackish sites in the shallow coal measures and alluvium, highly depleted δ2H-CH4 (4 concentrations inhibit CO2 reduction. Evidence of CH4 migration from the deep gas reservoir (200–500 m) to the shallow coal measures (4 at different depth profiles within and between aquifers. Further research, including culturing studies of microbial consortia, will improve our understanding of the occurrence of CH4 within and between aquifers in these basins

Application of Multi-Tracer Methods to Evaluate Nitrate Sources and Transformation in Sabkha Matti (Saudi Arabia)

An unusually high concentration of nitrate (NO3) ranging between 291 and 6790 mg/L (as N) was observed during a review of solute data for brine samples from the inland Sabkha Matti. A multi-tracer approach considering water chemistry, stable nitrate isotopes (δ15N and δ18O), and the radioactive isotope of hydrogen (tritium, 3H) was utilized to evaluate the nitrate sources and transformation in this hydrogeological setting. The results suggested that the source of the high nitrate levels is related to a leakage from a manure/septic system near the proximal eastern edge of the Sabkha. Moreover, the impact of Sabkha’s characteristics on biological denitrifications was evaluated in this study. The results suggest that denitrification was not a major process in Sabkha Matti. Several factors may contribute to the limitation of denitrification on the brine samples including high dissolved oxygen contents, high salinity and chloride

Use of dual carbon-chlorine isotope analysis to identify degradation pathways of 1,1,1-trichloroethane in groundwater

The high susceptibility of chlorinated aliphatic hydrocarbons (CAHs) like 1,1,1-trichloroethane (1,1,1-TCA) to be transformed via different competing pathways (biotic and abiotic) complicates the assessment of their fate in groundwater. This knowledge is necessary to evaluate contaminant degradation and potential formation of toxic intermediates. Identifying pathways is further complicated in sites contaminated by mixed CAHs because some degradation products of 1,1,1-TCA can be formed from different precursors. Here, identification of pathways based solely on substrate-product concentration relationships may lead to ambiguous interpretations. This study investigates, for the first time, dual C−Cl isotope fractionation as a means of identifying and assessing degradation pathways of 1,1,1-TCA in groundwater. Distinctly different dual isotope trends (L = Δδ13C/Δδ37Cl) were observed for 1,1,1-TCA transformation via oxidation with heat-activated persulfate (L = ∞), reduction with zerovalent iron (L = 1.5 ± 0.1), hydrolysis and dehydrohalogenation (HY/DH, L = 0.33 ± 0.04) in laboratory experiments, illustrating the potential of a dual isotope approach. This approach was evaluated in an aerobic aquifer impacted by 1,1,1-TCA and trichloroethylene (TCE) with concentrations of up to 20 mg/L and 3.4 mg/L, respectively. For 1,1,1-TCA, the dual isotope slope determined from field samples (L = 0.6 ± 0.2, r2 = 0.75) was close to the slope observed for HY/DH in the laboratory (L = 0.33 ± 0.04), indicating that HY/DH was the predominant degradation pathway of 1,1,1-TCA in the aquifer. The observed deviation could be explained by a minor contribution of additional degradation processes. This result, along with the little degradation of TCE determined from isotope measurements, confirmed that 1,1,1-TCA was the main source of the 1,1-dichlorethylene (1,1-DCE) detected in the aquifer with concentrations of up to 10 mg/L. This study demonstrates that a dual C-Cl isotope approach can strongly improve the qualitative and quantitative assessment of 1,1,1-TCA degradation processes in the field

Groundwater and Solute Budget (A Case Study from Sabkha Matti, Saudi Arabia)

Sabkha Matti is the largest inland sabkha (2950 km2) in the Arabian Peninsula. The drainage area supporting this sabkha is >250,000 km2 and is the discharge point for part of the ten thousand meter thick regional groundwater systems ranging in age from Precambrian through Miocene in the Rub’ al Khali structural basin. A hydrologic budget was constructed for this sabkha, where water fluxes were calculated on the basis of hydraulic gradient and conductivities measured in both shallow and deep wells. The evaporation rates from the surface of the sabkha were estimated from the published data and indicate that almost all the annual rainfall is lost by surface evaporation. The water flux multiplied by its solute concentration showed that nearly all the solutes in the sabkha were derived by upward leakage from the underlying regional aquifers rather than the weathering of the aquifer framework, from precipitation, or from other sources. Steady-state estimates within a rectilinear control volume of the sabkha indicate that about 1 m3/year of water enters by lateral groundwater flow, 2 m3/year of water exits by lateral groundwater flow, 20 m3/year enters by upward leakage, 780 m3/year enters by recharge from rainfall, and 780 m3/year is lost by evaporation. The proposed conceptual model of the hydrology for sabkha Matti is assumed to apply to the rest of the inland sabkhas of the Arabia Peninsula and to many ancient environments of deposition observed in the geologic record