Chlorine Stable Isotope Research Articles

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.

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.

Chlorine geochemistry of various geothermal waters in China: Implications for geothermal system geneses

Understanding the geneses of geothermal systems is critical for their efficient and sustainable exploitation. Chlorine is one of the most conservative elements in geothermal waters and capable of providing valuable information related to the formation and evolution of geothermal systems, thereby being a promising indicator for identifying geothermal system geneses. In this study, representative hydrothermal systems located in various tectonic regions in China, including Daggyai, Semi, and Gudui in plate margin as well as Xinzhou and Xiong’an in inland Basins, were selected for investigating the chloride sources of the geothermal waters and possible mechanisms of chlorine isotope fractionation occurring in the relevant geochemical processes. The chloride of geothermal waters in Tibet originated predominantly from magmatic fluids input, whereas water–rock interaction was the primary chloride source for the Xinzhou geothermal waters. As for the chloride in Xiong’an, it was primary derived from the dissolution of halite in carbonate rocks. In addition, the major processes resulting in the chlorine isotope fractionation were supposed to be magma degassing in the Tibetan geothermal systems and ion filtration in the Xiong’an geothermal system. Based on the discovered chloride sources and possible processes inducing non-negligible chlorine isotope fractionation, the geneses of various geothermal systems investigated in this study were proposed. This study suggests that stable chlorine isotopes, coupled with other geochemical parameters, have the potential for discriminating geothermal systems with different geneses.

Development towards stable chlorine isotope measurements of astromaterials using the modified Middleton source of an accelerator mass spectrometer

The volatile element Cl can be lost during the formation and evolution of planetary bodies, leading to fractionation of its two stable isotopes 35Cl and 37Cl. Chlorine isotope variations (reported as δ37Cl in parts per thousand (‰) relative to Standard Mean Ocean Chloride, SMOC) are documented to exceed 80‰ between different lunar rock samples and have been variably interpreted as the fingerprint of degassing during accretion, magma ocean, or volcanic portions of lunar history. The large intersample and intrasample variations observed by both bulk isotope ratio mass spectrometry (IRMS) and in-situ secondary ion mass spectrometry (SIMS) methods are difficult to interpret in part because of a paucity of bulk Cl isotope measurements. This lack of high-precision bulk data is due to the relative rarity of IRMS laboratories capable of making these high precision measurements on small samples of precious planetary materials such as those returned by human or robotic exploration. Here we present a new method for performing high precision δ37Cl measurements using the modified Middleton ion source of an existing accelerator mass spectrometer. For samples with as little as 1 μg Cl–the equivalent of 2–4 mm3 of a typical lunar rock sample–the average cathode accuracy is ∼1‰. Cathode reproducibility is typically ∼1‰ (2σ) for samples with at least 10 μg of Cl, increasing to ∼3–6‰ for aliquots with ∼1–2 μg Cl, similar to published SIMS results and sufficient to study astromaterials from the Moon, Mars, or 4 Vesta, which have tens of ‰ observed variations.

Determination of Stable Chlorine Isotopes by Isotopic Preparative Chromatography (IPC) with Positive–Thermal Ionization Mass Spectrometry (P-TIMS)

A novel approach to chlorine isotope analysis is presented to overcome many drawbacks of existing methods. Contemporary methods often require several laborious off-line procedures prior to instrumental determination; interfering ions (SO4 2- and NO3 -) in real samples are difficult to completely remove, especially when the concentrations of those ions are equal to that of the Cl- ion. This study was aimed to develop an automatic sample preparation method with chromatographic purity for determination of chlorine isotopes using isotopic preparative chromatography (IPC), which was a modified ion chromatograph and a fraction collector. An AS19 chromatographic column was employed to separate chlorine from interference ions using an eluent, flow rate, and suppressor current of 30 mM NaOH, 1 mL/min, and 70 mA, respectively. After the original solutions introduced into the IPC, eluted pure chlorine in the form of HCl was collected in an automated procedure from the outlet of the detector for 6 to 10 mins. The recoveries of chlorine were more than 95% with the relative standard deviation (RSD) of the separation less than 1.8%. After transforming the HCl into CsCl with a resin and concentration in a super-clean laboratory, the samples were sent to the thermal ionization mass spectrometer. The present method was validated by certified reference materials and real samples. The precision of 37Cl/35Cl ratio value was generally below 0.20 ‰. This method provides a potential approach for the analysis of samples with low chlorine concentrations.

Isotopic Tracing of Perchlorate Sources in the Environment

Perchlorate (ClO4−) is an emerging persistent pollutant that is ubiquitous in the environment at trace concentrations. Perchlorate ingestion poses a risk to human health because it interferes with thyroidal hormone production. The identification of perchlorate sources in groundwater is a primary concern. Chlorine and multi-oxygen isotopic tracing of perchlorate (δ37Cl, 36Cl/Cl, δ18O, and Δ17O) can provide a unique tool for identifying the origin and transport of perchlorate in groundwater. Along with the kinetic fractionation of chlorine and oxygen isotopes, the Δ17O value, 36Cl/Cl ratio, and ε18O/ε37Cl (the fractionation coefficient of oxygen and chlorine isotopes) are constant, potentially indicating the biodegradation of perchlorate, without disguising its source information. Therefore, comprehensive characterization of stable chlorine and poly-oxygen isotopes is expected to provide direct evidence for identifying the source of perchlorate in groundwater. However, further studies are needed to increase the amount of isotopic data of different perchlorate sources, to make the end-member model available to broader regions. It is critically important to understand the range of values and differences of isotopes among natural perchlorate sources and the perchlorate formation mechanisms.

Chlorine-bearing species and the 37Cl/35Cl isotope ratio in the coma of comet 67P/Churyumov–Gerasimenko

ABSTRACT A full-mission analysis has been conducted of Cl-bearing species in the coma of comet 67P/Churyumov–Gerasimenko as detected by the Double Focusing Mass Spectrometer (DFMS) of Rosetta's ROSINA instrument. The isotope ratio of the two stable chlorine isotopes 37Cl/35Cl is found to be 0.336 ± 0.017, to be compared with the standard mean ocean chloride value of 0.320. The isotope ratio does not change appreciably throughout the mission. The Cl-bearing species fingerprint in DFMS indicates that there is at least one additional chlorine-bearing species in the coma next to HCl, CH3Cl, and NH4Cl. The identity of this volatile or semivolatile species is unknown at this time.

Stable chlorine isotope analysis of triclosan using GC-qMS: Method development and applications

Occurrence of triclosan (TCS) in water environment caused a serious concern due to TCS toxic properties as well as yield of toxic byproducts during natural attenuation. Here we developed an online approach for chlorine compound specific isotope analysis (CSIA) of TCS based on gas chromatography quadrupole mass spectrometry (GC-qMS). Specifically, the instrumental parameters including dwell time, ionization energy and split ratio values were tested and optimized. Moreover, the calculation scheme considering all the TCS molecular ions presented better precision compared with the method using the most abundant neighboring ion pairs. The optimized method was validated by applying it to differentiate various TCS manufacturers, and was used to resolve chlorine isotope fractionation occurring during TCS photodegradation induced by simulated solar radiation. Chlorine isotopic enrichment factor (εCl) of −2.61 ± 0.37‰ and −0.72 ± 1.95‰ were obtained at pH values of 8.3 and 4.5, respectively. This indicates that preferential cleavage of C-Cl bonds occurred at a higher pH value. Thus, this study provides a robust and sensitive approach for chlorine CSIA of TCS, and could be readily applied to monitor chlorine isotope effects during TCS environmental transformations.

Origin and Evolution of Eocene Rock Salts in Pakistan and Implications for Paleoclimate Studies: Insights From Chemistry and Cl Stable Isotopes

The Kohat Basin (KB) lies on the Himalayan Foothills and is of scientific importance as it directly recorded the closure of the Tethys Sea and the Himalayan collision between India, Asia, and a number of other small plates. During the Eocene, after the collision between the Indian and Eurasian plates terminated the Tethys Sea, thick-bedded marine evaporite sequences developed in the KB. In this study, we combined mineralogy, geochemistry, fluid inclusion and chlorine stable isotope compositions to discuss the origin and evolution of the KB Eocene halite deposits with the ultimate objective of defining the paleoclimate that was prevailing in Asia during the Eocene. Our results showed that halite samples were SO42− rich (225–370.103 ppm) and Br− poor (<3 ppm). Cl−, B+, Mg2+, K+, SO42− and very low Br concentrations as well as the (Br/Cl) ratios indicated that halite resulted of a mixture of solutions with variable compositions and that dissolution, recrystallization and a progressive decrease in dolomitization were the mechanisms leading to the formation of these evaporites. A Br/Cl vs Cl plot revealed that the end members involved were: seawater (sw), saline waters and/or freshwaters. The recrystallization process prevented identifying the primary structures and primary fluid-inclusions. Most of Cl isotope compositions (−0.54‰<δ37Cl < 0.83‰) were within the usual range (0 ± 0.5‰) associated to seawater as the initial source for the halite. The higher isotope compositions (δ37Cl ≥ 0.83‰) comforted the hypothesis of the genesis by mixing of solutions of different origins as well as the involvement of recrystallization. Based on our results, we are proposing the following to explain the regional paleoclimate sequence: 1) shallow water conditions; 2) halite precipitation induced by evaporation, 3) unstable paleoclimatic conditions that resulted in the morphing from an evaporite basin into a terrestrial foreland basin. All these events were controlled by regional tectonic and linked to both the overall uplift times of the NW Indian Craton and the Eocene thermal maximum one during the Eocene-Oligocene period.

Compound-Specific Chlorine Isotope Analysis of Organochlorine Pesticides by Gas Chromatography-Negative Chemical Ionization Mass Spectrometry.

Compound-specific stable chlorine isotope analysis (CSIA-Cl) is an important method for identifying sources of organochlorine contaminants and helping assess their quantification of transformation processes. However, the present CSIA-Cl is challenged by either redundant conversion pretreatment or complicated mathematical correction. To overcome the mentioned problems, a novel method has been developed for the CSIA-Cl of eight organochlorine pesticides using gas chromatography-negative chemical ionization mass spectrometry (GC-NCI-qMS) in this study. The instrument parameters, acquisition mode, and required injection amounts were optimized in terms of the precision of GC-NCI-qMS. An ionization energy of 90 eV and emission current of 90 μA were selected, and the precisions for eight organochlorine pesticides were in the range of 0.37‰–2.15‰ in single ion monitoring (SIM) mode when the injected amount was 0.50 mg L−1 (viz. 0.5 ng on column). Furthermore, when standards from Supelco and O2si were calibrated using standards from AccuStandard regarded as external isotope standard, chlorine isotope composition of α-hexachlorocyclohexane (α-HCH) and 2, 2-dichloro−1, 1-bis (4-chlorophenyl) ethylene (p, p′-DDE) in Supelco and O2si was confidently differentiated. The provenance identification method was validated by three organochlorine contaminated groundwater samples and showed a prospect in identifying the source of organochlorine pesticides.

Simultaneous determination of stable chlorine and bromine isotopic ratios for bromochlorinated trihalomethanes using GC-qMS

Bromochlorinated compounds are organic contaminants originating from different natural and anthropic sources and increasingly found in different environmental compartments. This work presents an online approach for compound specific stable isotope analysis of chlorine and bromine isotope ratios for bromochlorinated trihalomethanes using gas chromatography coupled to quadrupole mass spectrometry (GC-qMS). An evaluation scheme was developed to simultaneously determine stable chlorine and bromine isotope ratios based on the mass spectral data of two target compounds: dibromochloromethane and dichlorobromomethane. The analytical technique was optimized by assessing the impact of different instrumental parameters, including dwell time, split ratios, and ionization energy. Successively, static headspace samples containing the two target compounds at aqueous concentrations ranging from 0.1 mg/L to 5 mg/L were analyzed in order to test the precision and reproducibility of the proposed approach. The results showed a good precision under the optimized instrumental conditions, with relative standard deviations ranging between 0.05% and 0.5% for chlorine and bromine isotope analysis. Finally, the method was tested in a source identification problem in which the simultaneous determination of chlorine and bromine stable isotope ratios allowed the clear distinction of dibromochloromethane from three different manufacturers.

Optimization of compound-specific chlorine stable isotope analysis of chloroform using the Taguchi design of experiments.

Chloroform, a probable human carcinogen, is commonly detected in various concentration levels in many surface water and groundwater sources. Compound-specific chlorine stable isotope analysis (Cl-CSIA) is significant in investigating the fate of chlorinated contaminants in the environment. Analytical conditions should, however, be thoroughly examined for any isotopic fractionation. In this study, we simultaneously optimize three analytical parameters for a robust online Cl-CSIA of chloroform using the Taguchi design of experiments. For Cl-CSIA, a purge-and-trap autosampler coupled to a gas chromatograph in tandem with a quadrupole mass spectrometer, with electron ionization in selected ion monitoring (SIM) mode, was used. Using the Taguchi method, the dominant parameter affecting the results of Cl-CSIA for chloroform was identified through concurrent investigation of the signal-to-noise ratios (S/N) of three parameters, each at three levels: purging time (5, 10, 15 min), transfer time (80, 120, 160 s), and dwell time (20, 60, 100 ms). Moreover, the optimum combination of the levels was identified. The purging time, with a maximum S/N, resulted in the highest influence on the isotope ratios determined. It was further refined through additional experiments to sufficiently extract chloroform from the aqueous phase. Accordingly, 8 min of purging time, 120 s transfer time and 100 ms dwell time were the optimum conditions for Cl-CSIA of chloroform. Post-optimization, a precision of ±0.28 ‰ was achieved for 8.4 nmol of chloroform (equivalent to 0.89 μg or approx. 25 nmol Cl-mass on column). A simple online method for Cl-CSIA of chloroform was optimized with the Taguchi design of experiments. The Taguchi method was very useful for the optimization of the analytical conditions. However, the purging conditions should be fine-tuned and selected so that sufficient extraction of a target compound is confirmed to acquire a stable and higher precision of the method.

Structural Controls on Crustal Fluid Circulation and Hot Spring Geochemistry Above a Flat‐Slab Subduction Zone, Peru

AbstractHot spring geochemistry from the Cordillera Blanca and Cordillera Huayhuash, Peru, reveal the influence of crustal‐scale structures on geothermal fluid circulation in an amagmatic region located above a flat‐slab subduction zone. To test the influence of contrasting modes of faulting in these regions, springs were targeted along the Cordillera Blanca detachment fault, within its hanging wall, in the footwall of the detachment, and in the Cordillera Huayhuash. Hot springs along the Cordillera Blanca detachment fault zone are associated with recent extension and normal faulting, and those in its footwall and the Cordillera Huayhuash are located in the Marañon fold and thrust belt where compressional structures dominate. Springs along and in the hanging wall of the Cordillera Blanca detachment fault yield brackish‐saline, alkaline‐chloride waters, with oxygen, hydrogen, carbon, and chlorine stable isotope values that suggest mixing between meteoric groundwater and saline brine affected by high water‐rock interaction. Geothermometry reservoir temperature estimates (RTEs) of 91–226°C indicate maximum flow path depths of 8.7 or 11 km, depending on geothermal gradient, associated with the Cordillera Blanca detachment fault. In contrast, springs in the footwall and in the Cordillera Huayhuash exhibit a wide range of water types with an isotopic affinity to meteoric water, suggesting a greater influence from shallow groundwater and less water‐rock interaction. For these springs, RTEs of 40–98°C correspond to much shallower circulation (1.6–4 km). Results indicate that the Cordillera Blanca detachment system accommodates significantly deeper circulation of crustal fluids compared to other regional compressional structures.

The origin and chemical composition of Carpathians chloride CO2-rich waters in the light of stable chlorine isotope studies (37Cl and 35Cl)

Investigations into chloride CO 2 -rich water occurring in the Polish and Slovakian Carpathians were carried out to gain a better understanding of the Cl – sources. The primary Cl – concentration in sea water, processes accompanying diagenesis, together with water-rock-gas interactions, have undoubtedly influenced the present content of chlorides. The Cl – - concentrations in the waters analysed vary from 35.5 to 4148.3 mg/l, lower than in sea water, with a mean ~19000 mg/l. The measured δ 37 Cl values range from –1.15 to –0.26‰, below the typical sea water value of 0‰. It might be concluded that the chemical and isotopic composition of these waters are the result of reactions during diagenesis (e.g., ion exchange or diffusion through low-permeability clay layers) as well as meteoric water influx.

Chlorine Isotope Fractionation of the Major Chloromethane Degradation Processes in the Environment.

Chloromethane (CH3Cl) is an important source of chlorine in the stratosphere, but detailed knowledge of the magnitude of its sources and sinks is missing. Here, we measured the stable chlorine isotope fractionation (εCl) associated with the major abiotic and biotic CH3Cl sinks in the environment, namely, CH3Cl degradation by hydroxyl (·OH) and chlorine (·Cl) radicals in the troposphere and by reference bacteria Methylorubrum extorquens CM4 and Leisingera methylohalidivorans MB2 from terrestrial and marine environments, respectively. No chlorine isotope fractionation was detected for reaction of CH3Cl with ·OH and ·Cl radicals, whereas a large chlorine isotope fractionation (εCl) of -10.9 ± 0.7‰ (n = 3) and -9.4 ± 0.9 (n = 3) was found for CH3Cl degradation by M. extorquens CM4 and L. methylohalidivorans MB2, respectively. The large difference in chlorine isotope fractionation observed between tropospheric and bacterial degradation of CH3Cl provides an effective isotopic tool to characterize and distinguish between major abiotic and biotic processes contributing to the CH3Cl sink in the environment. Our findings demonstrate the potential of emerging triple-element isotopic approaches including chlorine to carbon and hydrogen analysis for the assessment of global cycling of organochlorines.

Stable chlorine isotopes in saline springs from the Nangqen basin, Qinghai–Tibet Plateau: Brine genesis and evolution

Chlorine isotopes can be used to study the evolution of different fluids, sources and the causes of various related deposits. In this study, Cl concentrations and chlorine isotope (δ37Cl, IAEA ISL-354 NaCl standard) values were determined for brine samples from Nangqen basin, located on the southern boundary of the Qinghai–Tibet plateau to study the source and the processes of these saline springs. The results demonstrated that the saline springs are distributed around a fault or fault zone, with a high average salinity of 228.30 g/l and flow rates ranging from 1.7 to 0.01 l/s. Na+ and Cl− are the predominant cations and anions, respectively, accounting for more than 90% of the total. The δ37Cl values range from −1.55‰ to +0.97‰, and the Cl/Br ratios are from 1739 to 175,260. Coupled with the previous H, O and B isotope compositions (δD, VSMOW2 standard, ranges from −100.91‰ to −132.98‰, δ18O, VSMOW2 standard, from −12.88‰ to −16.05‰ and δ11B, NIST 951 standard, from +3.55‰ to +29.59‰), it can be interpreted that the saline springs are mainly the result of the dissolution of halite hosted in mudstone and volcanic country rocks.

Temperature-dependent variations in mineralogy, major element chemistry and the stable isotopes of boron, lithium and chlorine resulting from hydration of rhyolite: Constraints from hydrothermal experiments at 150 to 350 °C and 25 MPa

Rhyolite-hosted hydrothermal systems in the continental crust contain valuable energy and mineral resources that make them of special interest across several scientific disciplines. Despite extensive research on these systems, the temperature-dependence of chemical reactions between host rocks and aqueous-rich fluids and the mineralogical transformations resulting from these reactions are not well quantified. To expand our understanding of the controlling processes operating in these systems, we carried out seven laboratory experiments in which rhyolite was reacted with deionized water at 150 °C to 350 °C and 25 MPa. An additional experiment at 200 °C was carried out to examine the effect of dissolved CO 2 on the reactions. The overarching goal of this experimental study was to provide new insights on the temperature-dependence of water-rock interaction in continental hydrothermal systems. We applied a wide range of chemical, isotopic and mineralogical methods to analyze the reacted rhyolite and waters, and the major observations are: (1) the rhyolite progressively hydrates with increasing temperature between 150 °C to a maximum of 8.2 wt% H 2 O at 275 °C; hydration then decreases until 350 °C in conjunction with the destruction of the rhyolite glass and crystallization of secondary mineral phases; (2) the ratio of molecular water (H 2 O m ) to hydroxyl (OH − ) of the water that is dissolved in the reacted rhyolite decreases from ∼7 at 150 °C to ∼4 at 250 °C; (3) the main secondary minerals formed are the zeolite ferrierite (T ≥ 275 °C); biotite, albite and cristobalite mainly form at higher experimental temperatures (T ≥ 300 °C); (4) the reacted waters are nearly saturated with respect to amorphous silica; (5) at temperatures ≥ 275 °C nearly all the chlorine is leached into solution; (6) fluorine leaching from the rhyolite gradually increases between 150 °C and 250 °C, but then gradually decreases at higher temperatures and is incorporated into a secondary mineral phase; (7) dissolved CO 2 in the water enhances alkali metal cation leaching from the rhyolite; and (8) calculated Na-K and silica geothermometer temperatures differ from the experimental temperatures by varying amounts. In addition, apart from some small lithium isotope fractionation at temperatures ≤ 250 °C, the stable isotopes of boron, lithium and chlorine do not fractionate during rhyolite-water reactions, and the stable isotope compositions of these species in the reacted water are similar to those in the reactant rhyolite. These results provide new insights for a broad range of applications, including quantifying processes involving rhyolite glass hydration (obsidian hydration dating, perlite formation and discriminating secondary from magmatic water in rhyolitic matrix-glass of volcanic pyroclasts), for geothermal energy and mineral deposit exploration and for monitoring volcanoes.

Chlorine isotope fractionation recorded in atacamite during supergene copper oxidation

In the Atacama Desert of northern Chile, large amounts of the copper hydroxy-chloride mineral atacamite (Cu2Cl(OH)3) are formed in the supergene oxidation zone of Cu deposits. Since atacamite requires saline water to form and is commonly preserved under hyperarid conditions, it has been proposed as a climate-sensitive mineral marker that can also provide relevant geochemical information regarding halogen (in particular chlorine) fluid sources during supergene Cu oxidation. However, chlorine stable isotope data for atacamite in Cu deposits are scarce and no experimental data for chlorine isotope fractionation between atacamite and water are currently available that could provide constraints on the possible mechanisms of fractionation. In this study we report δ37Cl values of atacamite along a thick (~100 m) and well-developed supergene enrichment profile at the Barreal Seco iron oxide-copper-gold (IOCG) deposit in the Atacama Desert. The δ37Cl values of atacamite along this profile range from +2.1‰ to −0.6‰ (mean = +0.4‰ ± 0.7‰; median = +0.3‰), and show a distinct trend with depth, characterized by higher δ37Cl values towards the top of the profile, with lower values at the bottom. In addition, the chlorine isotope compositions of experimentally synthetized atacamite crystals and coexisting CuCl2 solutions were determined at room temperature (23 °C). The per mil fractionation factor (Δ37Clatacamite-Cl) was determined at +0.75‰, showing that the heavy isotope (37Cl) is preferentially incorporated into atacamite. We used numerical models to test two possible scenarios that might explain the observed δ37Cl profile at Barreal Seco. A first scenario involves lowering of the water table with concomitant precipitation of atacamite, which removes Cl from solution following a Rayleigh fractionation process. This model qualitatively fits our observations but does not explain the full magnitude of the observed δ37Cl shift along the supergene profile. In contrast, a model that simulates Cl- diffusion following the upward injection of a deep brine that overlies fresh groundwater reproduces well the observed δ37Cl data, suggesting that seismic pumping of basinal brines, followed by Cl diffusion, is a feasible mechanism to explain the formation of atacamite at Barreal Seco. These data are a first step towards interpreting δ37Cl profiles of atacamite in Cu deposits in the Atacama Desert and exploring the potential use of stable chlorine isotopes to monitor Cu weathering and enrichment in supergene environments.

Climate Change Impact on the Evolution of the Saline Lakes of the Soan-Sakaser Valley (Central Salt Range; Pakistan): Evidences from Hydrochemistry and Water (δD, δ18O) and Chlorine (δ37Cl) Stable Isotopes

The surfaces of saline lakes are shrinking at a threatening rate worldwide. Likewise, the Uchhali complex (formed by three saltwater lakes located in the Salt Range, Pakistan) that serves as a major regional source of water for humans and as a habitat for water birds must be monitored. With this objective in mind, we conducted a study coupling hydrochemistry and stable isotope compositions (δ37Cl, δ18O and δD) in order to characterize its hydrochemical properties and the main processes controlling them. Results showed that the Uchhali complex salinity has dramatically increased compared to other similar lakes in the world. While the Uchhali (UL) and Khabbeki (KL) lakes present a sodium-chloride hydrofacies, the Jahlar (JL) is of a sodium-bicarbonate type. Hydrochemistry parameters indicate that the weathering of surrounding rocks is the major vector for the increase of total dissolved solids in the water. On the other hand, the observed enrichment in heavy isotopes of the water stable isotope compositions implies that the different lakes are undergoing a long history of intense evaporation. The study of the corresponding δ37Cl isotope compositions supports the conclusion that evaporation, along with weathering, are the main driving processes. Besides climate effects that result in the decrease of annual precipitation and the increase of evaporation, water consumption for domestic purposes (household and agriculture) aggravates the rise of the lakes’ salinity.