Chlorine Isotope Research Articles

Technical note: Optimizing the in situ cosmogenic 36Cl extraction and measurement workflow for geologic applications

Abstract. In situ cosmogenic 36Cl analysis by accelerator mass spectrometry (AMS) is routinely employed to date Quaternary surfaces and assess rates of landscape evolution. However, standard laboratory preparation procedures for 36Cl dating require the addition of large amounts of isotopically enriched chlorine spike solution; these solutions are expensive and increasingly difficult to acquire from commercial sources. In addition, the typical workflow for 36Cl dating involves measuring both 35Cl/37Cl and 36Cl/Cl concurrently on the high-energy (post-accelerator) end of the AMS system, but 35Cl/37Cl determinations using this technique can be complicated by isotope fractionation and system memory during measurement. The traditional workflow also does not provide 36Cl extraction laboratories with the data needed to calculate native Cl concentrations in advance of 36Cl/Cl measurements. In light of these concerns, we present an improved workflow for extracting and measuring chlorine in geologic materials. Our initial step is to characterize 35Cl/37Cl on sample aliquots of up to ∼1 g prepared in Ag(Cl, Br) matrices, which greatly reduces the amount of isotopically enriched spike solution required to measure native Cl content in each sample. To avoid potential issues with isotope fractionation through the accelerator, 35Cl/37Cl is measured on the low-energy, pre-accelerator end of the AMS line. Then, for 36Cl/Cl measurements, we extract Cl as AgCl or Ag(Cl, Br) in analytical batches with a consistent total Cl load across all samples; this step is intended to minimize source memory effects during 36Cl/Cl measurements and allows the preparation of AMS standards that are customized to match known Cl contents in the samples. To assess the efficacy of this extraction and measurement workflow, we compare chlorine isotope ratio measurements on seven geologic samples prepared using standard procedures and the updated workflow. Measurements of 35Cl/37Cl and 36Cl/Cl are consistent between the two workflows, and 35Cl/37Cl values measured using our methods have considerably higher precision than those measured following standard protocols. The chemical preparation and measurement workflow presented here (1) reduces the amount of isotopically enriched chlorine spike used per rock sample by up to 95 %; (2) identifies rocks with high native Cl concentrations, which may be lower priority for 36Cl surface exposure dating, at an early stage of analysis; and (3) allows laboratory users to maintain control over the total chlorine content within and across analytical batches. These methods can be incorporated into existing laboratory and AMS protocols for 36Cl analyses and will increase the accessibility of 36Cl dating for geologic applications.

Vitamin B12 as a source of variability in isotope effects for chloroform biotransformation by Dehalobacter.

Carbon and chlorine isotope effects for biotransformation of chloroform by different microbes show significant variability. Reductive dehalogenases (RDase) enzymes contain different cobamides, affecting substrate preferences, growth yields, and dechlorination rates and extent. We investigate the role of cobamide type on carbon and chlorine isotopic signals observed during reductive dechlorination of chloroform by the RDase CfrA. Microcosm experiments with two subcultures of a Dehalobacter-containing culture expressing CfrA-one with exogenous cobamide (Vitamin B12, B12+) and one without (to drive native cobamide production)-resulted in a markedly smaller carbon isotope enrichment factor (εC, bulk) for B12- (-22.1 ± 1.9‰) compared to B12+ (-26.8 ± 3.2‰). Both cultures exhibited significant chlorine isotope fractionation, and although a lower εCl, bulk was observed for B12- (-6.17 ± 0.72‰) compared to B12+ (-6.86 ± 0.77‰) cultures, these values are not statistically different. Importantly, dual-isotope plots produced identical slopes of ΛCl/C (ΛCl/C, B12+ = 3.41 ± 0.15, ΛCl/C, B12- = 3.39 ± 0.15), suggesting the same reaction mechanism is involved in both experiments, independent of the lower cobamide bases. A nonisotopically fractionating masking effect may explain the smaller fractionations observed for the B12- containing culture.

New chloromethane preparation line for the stable chlorine isotope composition analysis*

ABSTRACT Stable isotopes of chlorine have great application potential due to the widespread occurrence of the chlorine anion in water, minerals, living organisms and the environment. In most studies, the chloride ion from the samples is converted to chloromethane, which is then analysed isotopically using a mass spectrometer. In the present study, a new design for a chloromethane preparation line is proposed. In particular, the new chloromethane preparation line uses a new system for injecting iodomethane into the preparation system, as well as ampoules with Teflon valves and the u-shaped freezers. These improvements reduced the preparation time to about 1 h, and also achieved a decent measurement uncertainty of 0.05 permil.

Cycling of fluid-mobile elements through the forearc: Insights from the Cl, B, and Li isotope composition of Costa Rican spring fluids

Loss of slab-derived volatile and fluid-mobile elements (FME) through the forearc may represent a large, unaccounted for flux out of convergent margins. To address volatile recycling through the forearc and potential changes in fluid source from the progressively dehydrating subducting slab, we collected water samples from 44 different cold and thermal (>40 °C) springs on a transect across the outer forearc (∼20–40 km to the subducting slab), forearc (∼40–80 km to the slab), and arc (∼80–120 km to the slab) in Costa Rica. We focused on the heavy halogens (Cl, Br, I), as well as B and Li, given their high fluid mobility and thus limited potential for modification by subsequent fluid-rock interaction. Chlorine, boron, and lithium stable isotope ratios show dramatic ranges from −1.7 to +1.0 ‰ (n = 43), −12.0 to +30.9 ‰ (n = 35), and −2.4 to + 27.5 ‰ (n = 38), respectively, with distinct changes across the transect consistent with a sedimentary pore fluid component in the outer forearc, fluids sourced from dehydration of the slab (sediment and altered oceanic crust) in the forearc, and minimal slab input near the arc. Variations in elemental ratios (Br/Cl, I/Cl, B/Cl, Li/B) across the transect are also largely consistent with evolving FME sources during subduction. Boron isotope ratios in some higher-temperature fluids are modified due to phase separation, whereas, lithium and chlorine isotope ratios are minimally modified. Springs located in the outer forearc along a major fault (Falla Morote) deviate from the consistent across-arc trend and record almost the full range of observed isotopic values. This extreme range in values along the fault likely represents a combination of adsorption/desorption effects, weathering, and mixing with crustal fluids. Mass balance calculations show that up to ∼ 70 % of Cl, ∼50 % of Br, ∼30 % of B, ∼15 % of I, and minimal Li may be recycled through the outer forearc and forearc springs of the Costa Rican margin, therefore fluid emission via springs in global forearc regions are a potentially significant output for FME at convergent margins.

Isotopic evidence of long-lived volcanism on Io.

Jupiter's moon Io hosts extensive volcanism, driven by tidal heating. The isotopic composition of Io's inventory of volatile chemical elements, including sulfur and chlorine, reflects its outgassing and mass loss history, and thus records information about its evolution. We used millimeter observations of Io's atmosphere to measure sulfur isotopes in gaseous SO2 and SO, and chlorine isotopes in gaseous NaCl and KCl. We find 34S/32S = 0.0595 ± 0.0038 (equivalent to δ34S = +347 ± 86‰), which is highly enriched compared to average Solar System values and indicates that Io has lost 94 to 99% of its available sulfur. Our measurement of 37Cl/35Cl = 0.403 ± 0.028 (δ37Cl = +263 ± 88‰) shows that chlorine is similarly enriched. These results indicate that Io has been volcanically active for most (or all) of its history, with potentially higher outgassing and mass-loss rates at earlier times.

Dual C–Cl isotope fractionation offers potential to assess biodegradation of 1,2-dichloropropane and 1,2,3-trichloropropane by Dehalogenimonas cultures

1,2-dichloropropane (1,2-DCP) and 1,2,3-trichloropropane (1,2,3-TCP) are hazardous chemicals frequently detected in groundwater near agricultural zones due to their historical use in chlorinated fumigant formulations. In this study, we show that the organohalide-respiring bacterium Dehalogenimonas alkenigignens strain BRE15 M can grow during the dihaloelimination of 1,2-DCP and 1,2,3-TCP to propene and allyl chloride, respectively. Our work also provides the first application of dual isotope approach to investigate the anaerobic reductive dechlorination of 1,2-DCP and 1,2,3-TCP. Stable carbon and chlorine isotope fractionation values for 1,2-DCP (ƐC = −13.6 ± 1.4 ‰ and ƐCl = −27.4 ± 5.2 ‰) and 1,2,3-TCP (ƐC = −3.8 ± 0.6 ‰ and ƐCl = −0.8 ± 0.5 ‰) were obtained resulting in distinct dual isotope slopes (Λ12DCP = 0.5 ± 0.1, Λ123TCP = 4 ± 2). However direct comparison of ΛC-Cl among different substrates is not possible and investigation of the C and Cl apparent kinetic isotope effects lead to the hypothesis that concerted dichloroelimination mechanism is more likely for both compounds. In fact, whole cell activity assays using cells suspensions of the Dehalogenimonas-containing culture grown with 1,2-DCP and methyl viologen as electron donor suggest that the same set of reductive dehalogenases was involved in the transformation of 1,2-DCP and 1,2,3-TCP. This study opens the door to the application of isotope techniques for evaluating biodegradation of 1,2-DCP and 1,2,3-TCP, which often co-occur in groundwaters near agricultural fields.

Comprehensive exploration of the anaerobic biotransformation of polychlorinated biphenyls in Dehalococcoides mccartyi CG1: Kinetics, enantioselectivity, and isotope fractionation

Anaerobic microbial transformation is a key pathway in the natural attenuation of polychlorinated biphenyls (PCBs). Much less is known about the transformation behaviors induced by pure organohalide-respiring bacteria, especially kinetic isotope effects. Therefore, the kinetics, pathways, enantioselectivity, and carbon and chlorine isotope fractionation of PCBs transformation by Dehalococcoides mccartyi CG1 were comprehensively explored. The results indicated that the PCBs were mainly dechlorinated via removing their double-flanked meta-chlorine, with their first-order kinetic constants following the order of PCB132 > PCB174 > PCB85 > PCB183 > PCB138. However, PCBs occurred great loss of stoichiometric mass balance during microbial transformation, suggesting the generation of other non-dehalogenation products and/or stable intermediates. The preferential transformation of (−)-atropisomers and generation of (+)-atropisomers were observed during PCB132 and PCB174 biotransformation with the enantiomeric enrichment factors of −0.8609 ± 0.1077 and −0.4503 ± 0.1334 (first half incubation times)/−0.1888 ± 0.1354 (second half incubation times), respectively, whereas no enantioselectivity occurred during PCB183 biotransformation. More importantly, although there was no carbon and chlorine isotope fractionation occurring for studied substrates, the δ13C values of dechlorination products, including PCB47 (−28.15 ± 0.35‰ ∼ −27.77 ± 0.20‰), PCB91 (−36.36 ± 0.09‰ ∼ −34.71 ± 0.49‰), and PCB149 (−28.08 ± 0.26‰ ∼ −26.83 ± 0.10‰), were all significantly different from those of their corresponding substrates (PCB85: −30.81 ± 0.02‰ ∼ −30.22 ± 0.21‰, PCB132: −33.57 ± 0.15‰ ∼ −33.13 ± 0.14‰, and PCB174: −26.30 ± 0.09‰ ∼ −26.01 ± 0.07‰), which further supported the generation of other non-dehalogenation products and/or stable intermediates with enrichment or depletion of 13C. These findings provide deeper insights into the anaerobic microbial transformation behaviors of PCBs.

Estimates of chlorine isotope fractionation factors using density functional theory: Applications to ore-forming systems

Chloride is the most important anion in ore-forming hydrothermal fluids, and chlorine isotopes are therefore potentially sensitive tracers of the origin and evolution of ore-forming fluids. However, they remain a relatively under-utilized tool in ore deposit geochemistry due to the lack of knowledge of chlorine isotope fractionation during ore-forming processes. Using first-principles density functional theory, this study estimates chlorine isotope fractionation factors for various ore-forming processes. All metal-Cl complexes in hydrothermal fluids are enriched in 37Cl compared to chloride ions, but the change in δ37Cl of the fluid trapped in ore minerals is small after the destabilization of metal-chloride complexes during ore mineral deposition. In the precipitation of evaporite minerals from brine, the sequence of enrichment of the heavy Cl isotope (37Cl) is halite > carnallite > aqueous chloride > kainite > sylvite > bischofite. The results of this study agree with the experimental observations that progressive precipitation of halite from brine lowers the δ37Cl value of the residual fluid until the formation of K-Mg chlorides. In low-temperature deposits, δ37Cl values for fluid inclusions and minerals reflect those of the hydrothermal fluid provenance and the mixing of this fluids with saltwater or basinal brines. In high-temperature magmatic-hydrothermal ore deposits that undergo liquid–vapour phase separation, chlorine isotopes fractionate among phases of silicate melt, vapour and chloride-rich liquid. The considerable range in δ37Cl in fluid inclusions may also reflect fluid mixing and hydrothermal alteration. At ambient temperature, the δ37Cl values may reflect evaporative processes and, in the case of chemical weathering of metallic mineral deposits, may record the supergene enrichment of the metals. This study highlights the use of chlorine isotopes as a new tool for interpreting ore-forming processes.

Chlorine isotope evidence for Farallon-derived metasomatism of the North American lithospheric mantle

Metasomatism of the sub-continental lithospheric mantle (SCLM) can result in enrichment in volatile elements introduced via subduction of seawater-altered oceanic lithosphere. Subduction-related metasomatism can introduce chlorine isotope heterogeneity to the SCLM inherited from the subducted source, which can be used to characterize the source of metasomatism. This study presents Cl isotope compositions (δ37Cl) of variably metasomatized continental lithospheric mantle xenoliths from the Colorado Plateau and southern Rio Grande Rift (southwestern United States). Fertile mantle xenoliths that represent asthenosphere that has recently been emplaced at the base of the North American lithosphere have δ37Cl values of 0.0 ‰ to +0.1 ‰, suggesting that the convecting mantle has an average δ37Cl value similar to seawater and chondrites. In contrast, metasomatized xenoliths span a range of δ37Cl values from +0.1 ‰ to +1.9 ‰, extending above the average convecting mantle value. The range in δ37Cl values can be explained by mixing between a subduction-related fluid with δ37Cl values between +1.0 ‰ and +1.9 ‰ and a shallow crustal fluid with a δ37Cl value less than +0.3 ‰. The most likely source of the high δ37Cl subduction-related signature is the lower crust in the subducted Farallon plate. Lower crustal Cl likely entered the SCLM either through direct dehydration of lawsonite ± phengite in the deeply subducted Farallon plate or from a mixed serpentinite-oceanic crust source in the subducted Farallon. Regardless of the mechanism, this study provides evidence for subduction of crustal Cl into the mantle, which can introduce isotopic heterogeneity into the SCLM and has implications for the volatile cycling in the HIMU mantle and SCLM.

A Novel Multi-ion Evaluation Scheme to Determine Stable Chlorine Isotope Ratios (37Cl/35Cl) of Chlordecone by LC-QTOF.

Organochlorinated pesticides are highly persistent organic pollutants having important adverse effects in the environment. To study their fate, compound-specific isotope analysis (CSIA) may be used to investigate their degradation pathways and mechanisms but is currently limited to 13C isotope ratios. The assessment of 37Cl isotope ratios from mass spectra is complicated by the large number of isotopologues of polychlorinated compounds. For method development, chlordecone (C10Cl10O2H2; hydrate form), an organochlorine insecticide that led to severe contamination of soils and aquatic ecosystems of the French West Indies, was taken as a model analyte. Chlorine isotope analysis of chlordecone hydrate was evaluated using high-resolution liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS), enabling smooth ionization to detect the molecular ion. First, a new evaluation scheme is presented to correct for multiple isotope presence in polychlorinated compounds. The scheme is based on probability calculations of the most frequent isotopologues, distributions by binomial probability functions, and corrections for the presence of nonchlorine heavy isotopes. Second, mobile-phase modifiers, ionization energy (sampling cone tension) and scan time were optimized for accurate chlorine isotope ratios. Chlordecone standard samples were measured up to 10-fold and bracketed with a second chlordecone external standard. δ37Cl values were obtained after conversion to the SMOC scale by a two-point calibration. The robustness of the analysis method and evaluation scheme were tested and gave satisfactory results with standard errors (σm) of ±0.34‰ for precision and ±0.89‰ for long-term accuracy of chlorine isotope ratios of chlordecone hydrate. This work opens perspectives for applications of the C-Cl CSIA approach to investigate the fate of highly toxic and low reactive polychlorinated compounds in the environment.

Unraveling the Complexities of Groundwater Salinization in Coastal Environments: Insights from Laizhou Bay’s Eastern Coast, China

Coastal areas have made substantial contributions to global economic development but are plagued by challenges such as groundwater salinization. Groundwater serves as the primary source for drinking, industrial, and domestic purposes in these coastal areas. Therefore, understanding the causes and processes of groundwater salinization holds paramount significance for effective groundwater management. The coastal area of Laizhou Bay in northern China serves as a quintessential example of such a scenario. With substantial groundwater extraction and severe groundwater salinization issues, it exacerbates the disparity between water-resource supply and demand. Currently, our understanding of the processes and influencing factors related to groundwater salinization in this region remains limited. In this study, employing hydrochemical and stable chlorine isotope analyses on 35 groundwater and seawater samples, an in-depth investigation into the complex mechanisms underlying groundwater salinization in the Quaternary aquifers of the eastern coastal plain of Laizhou Bay was conducted. The test results of the samples indicate that brine and saline groundwater are primarily of the Na-Cl type, exhibiting a hydrochemical composition similar to that of seawater. Brackish groundwater exhibits a diverse hydrochemical composition. The hydrogen and oxygen isotope characteristics of brackish and fresh groundwater resemble atmospheric precipitation, while brine, seawater, and saline groundwater show hydrogen and oxygen isotope depletion. Compared to seawater, brine exhibits significant δ37Cl depletion. The analysis of the test results reveals that the formation of brine aquifers results from a complex interplay of climate change, tectonic movements, and sea–land evolution, involving lagoon development during seawater regression, salt concentration through evaporation, and subsequent water–rock interactions. The genesis of saline groundwater involves a complex interplay of brine–seawater mixing, significant evaporation, and potential input of fresh groundwater from atmospheric precipitation and river sources. The formation of brackish groundwater is predominantly influenced by atmospheric precipitation, and agricultural activities, with significant variations in NO3− concentrations attributed to varying intensities of fertilizer application in the northern plain area. These insights contribute to a deeper understanding of the origins of groundwater and can inform the development of policies for groundwater protection in this area.

Chloride exchanges between oceanic sediments and seawater: Constraints from chlorine isotopes

We investigate the chlorine isotope disequilibrium between chlorides in pore fluids and chlorides in seawater and infer its consequences for chlorine isotope exchange between ocean sediment pore fluids and seawater. We illustrate our methodology with pore fluids from two IODP drilled to depths of ≈1000 m (U1456 and U1457) in the Indus River fan dominated by clay-detritus sediments of the western Himalayas. At these two sites, the concentrations of chloride and sodium ions do not show significant changes with depth and remain very close to those of seawater. As a function of depth, however, chlorides show a progressive decrease in 37Cl (downto −2.5 and −1.4 ‰ respectively), while Ca2+ increases and Mg2+ decreases, as commonly observed in clay-rich oceanic sediments. The rate of the δ37Cl decrease is correlated to the lithology and sedimentation rate. Examining the chlorine budget on these two sites, we conclude that: (1) Most of the chlorine (≥96% of the total Cl) is contained in the pore fluids as chlorides, while the chlorine stored in the other sinks (minerals or organochlorine) is generally very minor (representing <4% of the total Cl). (2) These other sinks are too small to sequester the lost 37Cl-enriched chlorine, which could compensate for the decreased δ37Cl of the chlorides observed in the pore fluids (assuming that the pore fluids originally had chlorides with the chlorine isotopic composition of seawater, δ37Cl = 0 ‰). (3) This lost 37Cl-enriched chlorine has been released from the sediment into the overlying seawater, with fluxes of about 20 mol of chloride per square metre per kiloyear.In order to evaluate the consequence of this unbalanced on a global scale, we extend this chlorine budget analysis to 22 other oceanic sites drilled by IODP in a variety of tectonic environments. It is estimated that worldwide oceanic sediment pore fluids contain 1 × 1020 mol of chloride with mean δ37Cl at −2.3 ± 0.1 ‰ and mean chlorinity at 0.290 ± 0.055 mol Cl- per kg of sediment. Most of the calculated values of the lost 37Cl-enriched chlorine flux are between 3.5 and 45.6 mol of chloride per square metre per kiloyear (mean value of 18.3 mol Cl.m−2.kyr−1), corresponding to a typical chloride exchange time between sediments and seawater of between 5.5 and 71 Myr with a mean value of 14 Myr. Importantly, in oceanic sediments, a relationship between the δ37Cl of the chlorides in their pore fluids and the nature of the detrital minerals (smectite, illite, kaolinite, carbonate, quartz, …) may exists. This relationship should be modulated by the detrital input from the continents to the oceanic sediments and should therefore be a consequence of the climatic conditions on the continents (mainly rain, temperature). The δ37Cl of the seawater should vary according to these detrital inputs. The expected range of variation would be between −0.3 and +0.3 ‰. This is consistent with the range of δ37Cl in seawater predicted by the study of evaporites deposited since 2 Ga (Eggenkamp et al., 2019).

Decay Characteristics of Neutron Excess Chlorine Nuclei

In neutron star mergers, neutron excess nuclei and the r-process are important factors governing the production of heavier nuclear systems. A single-particle model evaluation of chlorine nuclei suggests that the heaviest Z = 17 nucleus will have mass 62 with filling of the 1g9/2 neutron shell. A = 48 – 62 chlorine isotopes have limited experimental half-life data, but the model predicts beta decay half-lives in the range of 0.535 – 51.9 ms. Based on previous calculations for Z = 9 - 16, 20, 26, and 30 systems and comparisons to the 48Cl - 53Cl, and 55Cl calculations, summarized in the Japanese Nuclear Data Compilation, the single-particle model results likely overestimate the half-lives of A = 48 – 62 neutron excess chlorine nuclei.

Partial proton ordering during phase transition in Friedel's salt

Friedel's salt, also known as Cl-Hydrocalumite, (Ca2[Al(OH)6]· Cl·2H2O), is one of the calcium aluminates phases (AFm phases). It can accommodate radioactive chlorine isotopes, serving as a potential material in radioactive waste applications. Earlier X-Ray diffraction and nuclear magnetic resonance (NMR) experiments demonstrated the existence of the first-order phase transition between 303 K and 313 K. The phase transition involves an orientational ordering of water molecules while lowering the temperature. However, such behavior was not properly reproduced in computer simulations using classical molecular dynamics. Here we apply density functional theory and ab initio molecular dynamics to study structural properties and rotational dynamics of water molecules in the interlayer space of Cl-AFm. The transition is characterized by the partial proton ordering in the low-temperature phase, which was not previously observed in experiments and computer simulations.

Profiling and annotation of carbonyl compounds in Baijiu Daqu by chlorine isotope labeling-assisted ultrahigh-performance liquid chromatography-high resolution mass spectrometry

Carbonyl compounds are among the most important flavor substances that affect the taste of Baijiu. However, high coverage analysis of carbonyl compounds is obstructed due to the poor ionization efficiency of these compounds. Here we report a chlorine isotope labeling-assisted ultrahigh-performance liquid chromatography-high resolution mass spectrometry-based method (CIL-UHPLCHRMS) for profiling and annotation of carbonyl compounds in sauce flavored-Baijiu Daqu. 4-Chloro-2-hydrazinylpyridine was demonstrated to be a good labeling reagent that could achieve highly sensitive profiling and high-coverage screening of carbonyl compounds in the absence of heavy isotope labeling reagents. In the analysis of eight carbonyl standards representing different carbonyl categories, l-(-)-fucose, 2-carboxybenzaldehyde, 2-hydroxyacetophenone and heptan-2-one could be ionized only after labeling and MS signals were significantly increased for other 4 standards with an enhancement factor ranging from 181-fold for 3-methoxysalicylaldehyde to 3141-fold for tridecan-2-one. The annotation was achieved based on multidimensional information including MS1, predicted tR, in silico MS/MS and manually annotated fragments. In total, 487 carbonyl compounds were detected in Baijiu Daqu, among which, 314 (64.5%) of them were positively or putatively identified. The outcome of the linearity (with a linear range of 2, 3 orders of magnitude), precision (less than 10%), and limit of detection (varied from 0.07 to 0.10 nM) indicated that the method was adequate for profiling carbonyl compounds in complex biological samples. The established method was successfully applied to study carbonyl compounds in Baijiu Daqu with different colors and different seasons. Taken collectively, the present work provides an effective, simple and economic strategy for comprehensive analysis of carbonyl compounds in complex matrix samples.

Study of S, Cl and Ar isotopes with $$N \ge Z$$ using microscopic effective sd-shell interactions

In the present work, newly developed microscopic effective $sd$-valence shell interactions such as chiral next-to-next-to-next-to-leading order (N3LO), $J$-matrix inverse scattering potential (JISP16), Daejeon16 (DJ16), and monopole-modified DJ16 (DJ16A) are employed to study the nuclear structural properties of sulphur, chlorine, and argon isotopes with $N \geq Z$. These interactions are derived using the \textit{ab initio} no-core shell-model and the OLS unitary transformation method. We calculate energy spectra and electromagnetic properties to test the predictive strength of the effective interactions for these heavier $sd$-shell nuclei. For a complete systematic study, we compare the microscopic results with the phenomenological USDB results and experimental data. By looking at the excitation energies of these nuclei, the DJ16A interaction is found to be {the} most suitable for these $sd$-shell nuclei among all microscopic interactions. The electric quadrupole transition strength and excitation energy of the first $2^+$ state data of even-even sulphur isotopes indicate the presence of the $N=20$ shell closure. Quadrupole moment predictions are also made using these interactions where experimental data are unknown. Magnetic moments are in excellent agreement with the experimental values. The root-mean-square deviations are also calculated to provide an idea of how accurate the interactions are.

Isotopic evidence (δ13C, δ37Cl, δ2H) for distinct transformation mechanisms of chloroform: Catalyzed H2-water system vs. zero-valent iron (ZVI)

Catalytic hydrodechlorination is an efficient technology for degrading organochlorinated compounds, such as chloroform (CF), into harmless products. Compound-specific stable isotope analysis (CSIA) of multiple elements is widely used for the investigation of degradation mechanisms. Yet, its application in the study of catalytic hydrodechlorination is still limited. We have applied CSIA to derive chlorine, carbon, and hydrogen isotope enrichment factors (ε) during the degradation of CF over Pd/Al2O3 and over Rh/Al2O3. In addition, the enrichment factors for the same isotopes were derived for the reaction of CF with zero-valent iron (ZVI) for comparison. For the reactions of CF over Pd/Al2O3 and Rh/Al2O3, εC values (−21.9 ± 0.25 ‰ and −23.4 ± 2.3 ‰) and εCl values (−12.1 ± 1.7 ‰ and −10.3 ± 0.6 ‰) were determined, respectively. The corresponding εC and εCl values, for the dechlorination of CF with ZVI were −22.2 ± 2.8 ‰ and −4.7 ± 0.45 ‰, respectively. The apparent kinetic isotope effects (AKIE) of Cl suggest that the transformation mechanism in the catalyzed hydrogen-water system is a non-concerted reaction, unlike the known reductive dechlorination of CF with ZVI. Moreover, dual-isotope slopes (ΛC/Cl) for both catalyzed reactions (ΛPd = 1.8 ± 0.13 and ΛRh = 2.1 ± 0.14) are markedly different than for the ZVI (ΛZVI = 5.8 ± 0.41), reflecting that the reactions proceed in different mechanisms. For hydrogen isotopes, while there was no clear trend for the catalyzed reactions, an inverse secondary hydrogen isotope effect was observed for the reaction of CF with ZVI.

An approach combining chlorine isotopes and hydrochemistry for identification of magmatic fluid-affected hydrothermal systems

Identification of hydrothermal systems affected by magmatic fluid input is relevant for geothermal energy development. Thus, an approach for identifying such systems based on chlorine isotope composition and auxiliary hydrochemical indices was proposed. The approach enabled us to distinguish Rehai, a magmatic hydrothermal area in the Tengchong volcanic region of China, from several other typical non-magmatic hydrothermal areas in Tengchong: Menglian, Shiqiang, and Jietou. The hot springs in the non-Rehai areas featured high δ37Cl values, reflecting an exclusive contribution of chlorine from hostrock leaching. By contrast, some hot springs with much lower δ37Cl values occurred in Rehai, all of which were nearly fully equilibrated waters with respect to reservoir hostrocks, rich in chloride and bromide. These springs should have the closest relationship with the fluids released from the underlying magma chamber. Notably, the potential reservoir processes that geothermal waters may undergo after receiving an input of magmatic fluids can further alter their chlorine isotope compositions to various degrees. Therefore, a deep understanding of these processes would help improve the use of the proposed approach based primarily on chlorine isotopes. Regarding Rehai, all the neutral to alkaline hot springs with δ37Cl values ranging from −0.44 ‰ to 0.31 ‰ evolved from a parent geothermal fluid that received an input of magmatic fluids—via adiabatic cooling, conductive cooling, mixing with low-temperature shallow groundwaters, or a combination of some of these processes. By contrast, the acidic Rehai hot springs with the highest δ37Cl values (up to 1.12 ‰) were essentially locally perched groundwaters heated by geothermal steam separated from underlying geothermal fluids upon their adiabatic cooling; thus, they were much less to do with the parent geothermal fluid than the neutral to alkaline springs were. Hence, only the neutral to alkaline Rehai hot springs not strongly affected by the mixing of shallow groundwaters and adiabatic cooling can reflect the chlorine isotope characteristics of intrusive magmatic fluids. Overall, chlorine isotope composition in combination with hydrochemistry has proven to be a robust tool for identifying a magmatic fluid-affected hydrothermal system.

Diffusive‐Dispersive Isotope Fractionation of Chlorinated Ethenes in Groundwater: The Key Role of Incomplete Mixing and Its Multi‐Scale Effects

AbstractDiffusive‐dispersive processes are ubiquitous in porous media with important implications for solute transport in many natural and engineered systems; however, their effects on isotope fractionation of organic contaminants in subsurface flow‐through systems is not well understood. In this study, we investigate the propagation of isotope shifts in groundwater systems, induced by lateral diffusive‐dispersive isotope fractionation, on carbon and chlorine isotope signatures of chlorinated ethene plumes at steady state. We consider three distinct spatial scales (i.e., pore, laboratory, and field scales) and explore isotope fractionation with high‐resolution pore‐scale simulations, flow‐through experiments, and field‐scale numerical modeling. The experimental lab‐scale investigation was carried out using cis‐dichloroethene (cis‐DCE) as model contaminant, whereas cis‐DCE and trichloroethene (TCE) were considered in the multi‐scale numerical simulations. The pore‐scale analysis of transverse displacement demonstrates significant isotope fractionation over a wide range of seepage velocities (0.1–10 m/day). The pore‐scale simulations illuminate the key role of incomplete mixing, which sustains isotopologue‐specific gradients in the pore channels and results in the strongest isotope fractionation (−6‰ for carbon; −10‰ for chlorine) at the fastest flow velocity. The outcomes of the flow‐through experiments support the key role of isotopologue‐specific aqueous diffusion also at the laboratory scale, where significant diffusive‐dispersive isotopic shifts were observed at the outlet of the setup. Finally, the detailed field‐scale numerical simulations, performed in a cross‐section of a heterogeneous aquifer, illustrate that the microscopic diffusion‐induced isotope fraction propagates at macroscopic scales.

Oxygen and chlorine isotope fractionation during microbial perchlorate reduction in static and flow through systems

Perchlorate (ClO4−) is an oxyanion with both anthropogenic and natural sources that is widespread on earth and throughout the solar system. Stable isotope ratio measurements are a powerful tool to assess the origin and predict the fate of perchlorate in the environment. The aim of this study was to perform an experimental survey of parameters that influence microbial O and Cl isotope fractionation during microbial perchlorate reduction, covering microbiological (genetic background and community context) and environmental (temperature, salinity, electron donor type and limitation) factors. A new method for the purification of perchlorate for isotope ratio mass spectrometry (IRMS) was developed to allow for more efficient sample preparation and suitable for samples containing small amounts of perchlorate (0.4–2 mg). Although most experiments, regardless of treatment, yielded a consistent isotope enrichment factor ratio (Λ = ε18O/ε37Cl ∼ 2.5), a greater variability was observed of individual isotope enrichment factors (ε18O and ε37Cl). Although most experiments yielded isotope enrichment factors (epsilon) in the larger negative range of previously published values, smaller negative values of ε18O and ε37Cl were observed for a halophilic isolate, Haloarcula marismortui, (ε18O = −15 to −22‰ and ε37Cl = −5 to −7‰), and in sediment column experiments (ε18O = −4 to −15‰ and ε37Cl = −1 to −6‰). Given the complexity of isolating individual parameters from our proposed model, we view our dataset as a survey that points to future opportunities where a particular parameter could be isolated to better understand controls on O and Cl isotope fractionation during microbial perchlorate reduction.