Isotopically Enriched Geogenic δ81 Br and δ37 Cl: Primary Evidence for the Ascending Brine Model.

Mass balance calculations and hydrodynamics of groundwater flow suggest that the solutes in brines of the coastal sabkha aquifer from the Emirate of Abu Dhabi are derived largely from ascending geologic brines into the sabkha from the underlying formations. Solute interpretation for the ascending brine model (ABM) was based on two independent but secondary lines of evidence (solute ratios and solute fluxes). In the current study, direct primary evidence for this ABM was provided through analyses of δ81 Br, δ37 Cl, and 87 Sr/86 Sr. Different solute histories of geologic brine and sea water provide an "isotopic fingerprint" that can uniquely distinguish between the two possible sources. Samples from the coastal sabkha aquifer of Abu Dhabi were determined to have a mean δ81 Br of 1.17‰ that is statistically equal, at the 95% confidence level, to the mean of 1.11‰ observed in the underlying geologic brine and statistically different than sea water. Similarly, the δ37 Cl in sabkha brine has a mean of 0.25‰ and is statistically equal to a mean of 0.21‰ in the underlying geologic brines at the 95% confidence level and statistically different from sea water. Also, dissolved strontium isotope data are consistent with the ABM and even with the complex set of processes in the sabkha, the variance in strontium isotope results is similar to the geologic brine. These observations provide primary direct evidence consistent that the major source of these solutes (and presumably others in the aquifer) is from discharging geologic brines, not from adjacent sea water.

Comparison of δ81Br and δ37Cl composition of volatiles, salt precipitates, and associated water in terrestrial evaporative saline lake systems.

This study provides the first characterization of the variability of bromine and chlorine stable isotopic composition in evaporites, associated residual brines, and shoreline gases in terrestrial evaporative saline lakes. The lakes investigated here are groundwater discharge locations, and include both potash-rich alkaline lakes and sodic-dominated neutral pH lakes at a variety of salinities and evaporative stages. The chlorine and bromine isotope systems behave consistently different during evaporative salt precipitation, with 37Cl more enriched in the salt than in the fluid, but 81Br more enriched in the fluid compared with the precipitated salt. The 81Br concentration of shore off-gassing was even smaller than mineral precipitate compositions. The trends observed for bromine isotopes are surprising compared with published laboratory studies, indicating that a process besides inorganic mineral precipitation is affecting δ81Br. Additional processes explored include diffusion, salt deflation, microbial and photolytic conversion to the gas phase, and oxidative bromination of organic matter. Dedicated to Professor Peter Fritz on the occasion of his 80th birthday.

Compound-Specific Isotope Analyses to Assess TCE Biodegradation in a Fractured Dolomitic Aquifer.

The potential for trichloroethene (TCE) biodegradation in a fractured dolomite aquifer at a former chemical disposal site in Smithville, Ontario, Canada, is assessed using chemical analysis and TCE and cis-DCE compound-specific isotope analysis of carbon and chlorine collected over a 16-month period. Groundwater redox conditions change from suboxic to much more reducing environments within and around the plume, indicating that oxidation of organic contaminants and degradation products is occurring at the study site. TCE and cis-DCE were observed in 13 of 14 wells sampled. VC, ethene, and/or ethane were also observed in ten wells, indicating that partial/full dechlorination has occurred. Chlorine isotopic values (δ37 Cl) range between 1.39 to 4.69‰ SMOC for TCE, and 3.57 to 13.86‰ SMOC for cis-DCE. Carbon isotopic values range between -28.9 and -20.7‰ VPDB for TCE, and -26.5 and -11.8‰ VPDB for cis-DCE. In most wells, isotopic values remained steady over the 15-month study. Isotopic enrichment from TCE to cis-DCE varied between 0 and 13‰ for carbon and 1 and 4‰ for chlorine. Calculated chlorine-carbon isotopic enrichment ratios (ϵCl /ϵC ) were 0.18 for TCE and 0.69 for cis-DCE. Combined, isotopic and chemical data indicate very little dechlorination is occurring near the source zone, but suggest bacterially mediated degradation is occurring closer to the edges of the plume.

Sediment color tool for targeting arsenic-safe aquifers for the installation of shallow drinking water tubewells.

In rural Bangladesh, drinking water supply mostly comes from shallow hand tubewells installed manually by the local drillers, the main driving force in tubewell installation. This study was aimed at developing a sediment color tool on the basis of local driller's perception of sediment color, arsenic (As) concentration of tubewell waters and respective color of aquifer sediments. Laboratory analysis of 521 groundwater samples collected from 144 wells during 2009 to 2011 indicate that As concentrations in groundwater were generally higher in the black colored sediments with an average of 239 µg/L. All 39 wells producing water from red sediments provide safe water following the Bangladesh drinking water standard for As (50 µg/L) where mean and median values were less than the WHO guideline value of 10 µg/L. Observations for off-white sediments were also quite similar. White sediments were rare and seemed to be less important for well installations at shallow depths. A total of 2240 sediment samples were collected at intervals of 1.5m down to depths of 100 m at 15 locations spread over a 410 km(2) area in Matlab, Bangladesh and compared with the Munsell Color Chart with the purpose of direct comparison of sediment color in a consistent manner. All samples were assigned with Munsell Color and Munsell Code, which eventually led to identify 60 color shade varieties which were narrowed to four colors (black, white, off-white and red) as perceived and used by the local drillers. During the process of color grouping, participatory approach was considered taking the opinions of local drillers, technicians, and geologists into account. This simplified sediment color tool can be used conveniently during shallow tubewell installation and thus shows the potential for educating local drillers to target safe aquifers on the basis of the color characteristics of the sediments.

Hydrogeology, chemical and microbial activity measurement through deep permafrost.

Little is known about hydrogeochemical conditions beneath thick permafrost, particularly in fractured crystalline rock, due to difficulty in accessing this environment. The purpose of this investigation was to develop methods to obtain physical, chemical, and microbial information about the subpermafrost environment from a surface-drilled borehole. Using a U-tube, gas and water samples were collected, along with temperature, pressure, and hydraulic conductivity measurements, 420 m below ground surface, within a 535 m long, angled borehole at High Lake, Nunavut, Canada, in an area with 460-m-thick permafrost. Piezometric head was well above the base of the permafrost, near land surface. Initial water samples were contaminated with drill fluid, with later samples <40% drill fluid. The salinity of the non-drill fluid component was <20,000 mg/L, had a Ca/Na ratio above 1, with δ(18) O values ∼5‰ lower than the local surface water. The fluid isotopic composition was affected by the permafrost-formation process. Nonbacteriogenic CH(4) was present and the sample location was within methane hydrate stability field. Sampling lines froze before uncontaminated samples from the subpermafrost environment could be obtained, yet the available time to obtain water samples was extended compared to previous studies. Temperature measurements collected from a distributed temperature sensor indicated that this issue can be overcome easily in the future. The lack of methanogenic CH(4) is consistent with the high sulfate concentrations observed in cores. The combined surface-drilled borehole/U-tube approach can provide a large amount of physical, chemical, and microbial data from the subpermafrost environment with few, controllable, sources of contamination.

Microbial communities in subpermafrost saline fracture water at the Lupin Au mine, Nunavut, Canada.

We report the first investigation of a deep subpermafrost microbial ecosystem, a terrestrial analog for the Martian subsurface. Our multidisciplinary team analyzed fracture water collected at 890 and 1,130 m depths beneath a 540-m-thick permafrost layer at the Lupin Au mine (Nunavut, Canada). 14C, 3H, and noble gas isotope analyses suggest that the Na-Ca-Cl, suboxic, fracture water represents a mixture of geologically ancient brine, approximately25-kyr-old, meteoric water and a minor modern talik-water component. Microbial planktonic concentrations were approximately10(3) cells mL(-1). Analysis of the 16S rRNA gene from extracted DNA and enrichment cultures revealed 42 unique operational taxonomic units in 11 genera with Desulfosporosinus, Halothiobacillus, and Pseudomonas representing the most prominent phylotypes and failed to detect Archaea. The abundance of terminally branched and midchain-branched saturated fatty acids (5 to 15 mol%) was consistent with the abundance of Gram-positive bacteria in the clone libraries. Geochemical data, the ubiquinone (UQ) abundance (3 to 11 mol%), and the presence of both aerobic and anaerobic bacteria indicated that the environment was suboxic, not anoxic. Stable sulfur isotope analyses of the fracture water detected the presence of microbial sulfate reduction, and analyses of the vein-filling pyrite indicated that it was in isotopic equilibrium with the dissolved sulfide. Free energy calculations revealed that sulfate reduction and sulfide oxidation via denitrification and not methanogenesis were the most thermodynamically viable consistent with the principal metabolisms inferred from the 16S rRNA community composition and with CH4 isotopic compositions. The sulfate-reducing bacteria most likely colonized the subsurface during the Pleistocene or earlier, whereas aerobic bacteria may have entered the fracture water networks either during deglaciation prior to permafrost formation 9,000 years ago or from the nearby talik through the hydrologic gradient created during mine dewatering. Although the absence of methanogens from this subsurface ecosystem is somewhat surprising, it may be attributable to an energy bottleneck that restricts their migration from surface permafrost deposits where they are frequently reported. These results have implications for the biological origin of CH4 on Mars.

Determination of bromine stable isotopes using continuous-flow isotope ratio mass spectrometry.

A new methodology for bromine stable isotope determination by continuous-flow isotope ratio mass spectrometry (CF-IRMS) was developed. The technique was tested on inorganic samples. Inorganic bromide was precipitated in the form of silver bromide by using silver nitrate in a standard methodology. Bromine stable isotope analysis was carried out on methyl bromide (CH3Br) after converting silver bromide to methyl bromide by reacting it with methyl iodide (CH3I). The system used in this study is an IsoPrime IRMS, with analytical capabilities of both dual-inlet and continuous-flow modes coupled with an Agilent 6890 GC equipped with a CTC Analytics CombiPAL autosampler. This new technique measures samples as small as 0.2 mg of AgBr (1 micromol of Br-). The bromine stable isotope analysis using continuous flow technology showed excellent precision and accuracy. The internal precision using pure methyl bromide gas is better than +/-0.03 per thousand (+/-SD); the external precision using seawater standard is better than +/-0.06 per thousand (+/-SD) for n = 12. Moreover, the sample analysis time is 16 min, as compared to 75 min needed in previous techniques. This allows for 50 samples to be analyzed in 1 day, as compared to 8 samples using the conventional techniques. A series of natural saline formation waters and brines from sedimentary and crystalline rock environments was measured by this new methodology to test the potential natural range of delta81Br. The bromine isotopic composition of the samples ranged from 0.00 to +1.80 per thousand relative to standard mean ocean bromide (SMOB). Initial trends and distinctive isotopic difference were noticed between crystalline shield brines and sedimentary formation brines.

Determination of inorganic chlorine stable isotopes by continuous flow isotope ratio mass spectrometry.

Chlorine stable isotope analyses of inorganic samples were conducted using continuous flow isotope ratio mass spectrometry (CF-IRMS) coupled with gas chromatography (GC). Inorganic chloride was precipitated in the form of silver chloride (AgCl) by using silver nitrate in a standard methodology. Chlorine stable isotope analysis was carried out on methyl chloride (CH3Cl) after converting AgCl into CH3Cl by reacting it with methyl iodide (CH3I). The reaction between AgCl and CH3I took place in 20 mL size vials. Addition of CH3I was performed in a glove bag under helium flow. An Agilent 6890 gas chromatograph equipped with a CTC Analytics CombiPAL autosampler and a DB-5MS 60 m column was used to separate CH3Cl from CH3I. This new technique uses samples as small as 0.2 mg of AgCl (1.4 micromol of Cl-). The chlorine stable isotope analysis using continuous flow technology showed excellent precision and accuracy. The internal precision using pure CH3Cl gas is better than +/-0.04 per thousand (+/-STDV). The external precision using seawater standard is better than +/-0.07 per thousand (+/-STDV) for n=12. Moreover, the sample analysis time is much shorter and many more samples can be analyzed in one day than by using the conventional off-line techniques.

Stable hydrogen, carbon and chlorine isotope measurements of selected chlorinated organic solvents.

Stable hydrogen isotopes of two chlorinated solvents, trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA), provided by five different manufacturers, were determined and compared to their carbon and chlorine isotopic signatures. The isotope ratio for delta2H of different TCEs ranged between +466.9 per thousand and +681.9 per thousand, for delta13C between -31.57 per thousand and -27.37 per thousand, and for delta37Cl between -3.19 per thousand and +3.90 per thousand. In the case of the TCAs, the isotope ratio for delta2H ranged between -23.1 per thousand and +15.1 per thousand, for delta13C between -27.39 per thousand and -25.84 per thousand, and for delta37Cl between -3.54 per thousand and +1.39 per thousand. As well, a column experiment was carried out to dechlorinate tetrachloroethylene (PCE) to TCE using iron. The dechlorination products have completely different hydrogen isotope ratios than the manufactured TCEs. Compared to the positive values of delta2H in manufactured TCEs (between +466.9 per thousand and +681.9 per thousand), the dechlorinated products had a very depleted delta2H (less than -300 per thousand). This finding has strong implications for distinguishing dechlorination products (PCE to TCE) from manufactured TCE. In addition, the results of this study show the potential of combining 2H/1H analyses with 13C/12C and 37Cl/35Cl for isotopic fingerprinting applications in organic contaminant hydrogeology.