Chlorine isotopic composition in seafloor serpentinites and high-pressure metaperidotites. Insights into oceanic serpentinization and subduction processes

Bulk-rock chlorine content and isotopic composition (δ³⁷Cl) were determined in oceanic serpentinites, high-pressure metaperidotites and metasediments in order to gain constraints on the global chlorine cycle associated with hydrothermal alteration and subduction of oceanic lithosphere. The distribution of insoluble chlorine in oceanic serpentinites was also investigated by electron microprobe. The hydrothermally-altered ultramafic samples were dredged along the South West Indian Ridge and the Mid-Atlantic Ridge. The high-pressure metamorphic samples were collected in the Western Alps: metaperidotites in the Erro-Tobbio unit and metasediments in the Schistes Lustrés nappe.Oceanic serpentinites show relatively large variations of bulk-rock Cl contents and δ³⁷Cl values with mean values of 1105 ± 596 ppm and −0.7 ± 0.4‰, respectively (n = 8; 1σ). Serpentines formed after olivine (meshes) show lower Cl content than those formed after orthopyroxene (bastites). In bastites of two different samples, Cl is positively correlated with Al₂O₃ and negatively correlated with SiO₂. These relationships are interpreted as reflecting preferential Cl-incorporation into the bastite structure distorted by Al (substituted for Si) rather than different alteration conditions between olivine and orthopyroxene minerals. High-pressure metaperidotites display relatively homogeneous Cl contents and δ³⁷Cl values with mean values of 467 ± 88 ppm and −1.4 ± 0.1‰, respectively (n = 7; 1σ). A macroscopic high-pressure olivine-bearing vein, formed from partial devolatilization of serpentinites at ∼2.5 GPa and 500-600 °C, shows a Cl content and a δ³⁷Cl value of 603 ppm and −1.6‰, respectively. Metasediments (n = 2) show low whole-rock Cl contents (<15 ppm Cl) that did not allow Cl isotope analyses to be obtained.The range of negative δ³⁷Cl values observed in oceanic serpentinites is likely to result from water-rock interaction with fluids that have negative δ³⁷Cl values. The homogeneity of δ³⁷Cl values from the high-pressure olivine-bearing vein and the metaperidotite samples implies that progressive loss of Cl inherited from oceanic alteration throughout subduction did not significantly fractionate Cl isotopes. Chlorine recycled in subduction zones via metaperidotites should thus show a range of δ³⁷Cl values similar to the range found in oceanic serpentinized peridotites.     

Chlorine stable isotope studies of old groundwater,southwestern Great Artesian Basin,Australia

Stable Cl isotope ratios (³⁷Cl/³⁵Cl) were measured in groundwater samples from the southwestern flow system of the Great Artesian Basin, Australia to gain a better understanding of the Cl⁻ sources and transport mechanisms. δ³⁷Cl values range from 0‰ to −2.5‰ (SMOC), and are inversely correlated with Cl⁻ concentration along the inferred flow direction. The Cl isotopic compositions, in conjunction with other geochemical parameters, suggest that Cl⁻ in groundwaters is not derived from salt dissolution. Mixing of the recharge water with saline groundwater cannot explain the relationship between δ³⁷Cl and Cl⁻ concentration measured. Marine aerosols deposited via rainfall and subsequent evapotranspiration appear to be responsible for the Cl⁻ concentrations observed in wells that are close to the recharge area, and in groundwaters sampled along the southern transect. δ³⁷Cl values measured in the leachate of the Bulldog shale suggest that the aquitard is the subsurface source of Cl⁻ for the majority of groundwater samples studied. Diffusion is likely the mechanism through which Cl⁻ is transported from the pore water of the Bulldog shale to the aquifer. However, a more detailed study of the aquitard rocks is required to verify this hypothesis.     

Stable chlorine isotopes in Phanerozoic evaporites

Modern seawater has a uniform δ³⁷Cl value (0.0‰), with an exception in the upper current of the Bosphorus (0.4‰). Marine halite ranging in age from Cambrian to Miocene has δ³⁷Cl values of 0.0 ± 0.9‰, with most of the data in the range 0.0 ± 0.5‰. Mean δ³⁷Cl values differ measurably between basins, with no evident relationship to basin size or to age. Smaller evaporite bodies have the largest δ³⁷Cl ranges. Potash facies halite has mean δ³⁷Cl values lower than those of halite facies salt in the East Siberia and Zechstein basins. The bulk δ³⁷Cl of bedded halite preserving sedimentary textures cannot be shifted measurably after deposition under plausible natural conditions. During the Phanerozoic, a detectable change in the δ³⁷Cl values of the oceans is unlikely as a result of Cl fluxes to and from the mantle and evaporites. In halite, the values of δ³⁷Cl that cannot be explained by fractionation occurring on crystallization are best explained by the addition of non-marine Cl with δ³⁷Cl ≠ 0.0‰ to evaporite brine.     

The stable isotopic composition (Cl/Cl) of dissolved chloride in rainwater

The stable isotopic composition of dissolved Cl^-${\text{Cl}}^{-}$ in rainwater was measured from a coastal and an interior location in eastern Canada. At the interior Bonner Lake, Ontario, site the δ³⁷Cl values of dissolved Cl^-${\text{Cl}}^{-}$ in precipitation ranged from −3.5‰ to −1.2‰ (SMOC) with an amount-weighted annual average of −2.3‰. At the coastal site, Bay D’Espoir, Newfoundland, δ³⁷Cl values of dissolved Cl^-${\text{Cl}}^{-}$ values ranged from −3.1‰ to 0.0‰ with an amount-weighted annual average of −1.3‰. These negative δ³⁷Cl values provide evidence that atmospheric HCl is ³⁷Cl depleted, presumably from acidification of sea-salt aerosols. Accordingly, dissolved Cl^-${\text{Cl}}^{-}$ in the headwaters of two montane rivers in Western Canada had similarly depleted δ³⁷Cl values. These results have implications to the interpretation of the isotopic compositions of dissolved Cl^-${\text{Cl}}^{-}$ in surface waters, formation fluids, and groundwaters.     

Low temperature volatile production at the Lost City Hydrothermal Field, evidence from a hydrogen stable isotope geothermometer

Although commonly utilized in continental geothermal work, the water-hydrogen and methane-hydrogen isotope geothermometers have been neglected in hydrothermal studies. Here we report δD-CH₄ and δD-H₂ values from high-temperature, black smoker-type hydrothermal vents and low-temperature carbonate-hosted samples from the recently discovered Lost City Hydrothermal Field. Methane deuterium content is uniform across the dataset at − 120 ± 12‰. Hydrogen δD values vary from − 420‰ to − 330‰ at high-temperature vents to − 700‰ to − 600‰ at Lost City. The application of several geothermometer equations to a suite of hydrothermal vent volatile samples reveals that predicted temperatures are similar to measured vent temperatures at high-temperature vents, and 20-60 °C higher than those measured at the Lost City vents. We conclude that the overestimation of temperature at Lost City reflects 1) that methane and hydrogen are produced by serpentinization at > 110 °C, and 2) that isotopic equilibrium at temperatures < 70 °C is mediated by microbial sulfate reduction. The successful application of hydrogen isotope geothermometers to low-temperature Lost City hydrothermal samples encourages its employment with low-temperature diffuse hydrothermal fluids.     

Effect of precipitation regime on δD values of soil n-alkanes from elevation gradients - Implications for the study of paleo-elevation

We measured δD values of long chain n-alkanes isolated from 30 surface soil samples along two elevation transects on the Tibetan Plateau differing in precipitation regime and water source. The East Asian Monsoon precipitation dominates the wetter regime on the eastern slope (from 1230 to 4300 m) of Gongga Shan on the eastern Tibetan Plateau. Precipitation from the Polar Westerlies dominates the drier region on the slope from 1900 to 5000 m in the West Kunlun Shan on the northwestern Tibetan Plateau. The decrease in δD value with elevation in the wetter region greatly exceeded that in drier region by, −1.9 ± 0.1‰/100 m and −1.4 ± 1.0‰/100 m respectively. The apparent fractionation between leaf wax and precipitation ε_wax-p values in the wetter region (ca. −164‰) were more negative than those in drier region (ca. −125‰ above 3200 m).We also measured δD values in leaves of six common living trees (values from −287‰ to −193‰) from Gongga Shan, ranging from about 2900-4200 m. The abundance-weighted average values of the n-alkanes (δD_wax) show a strong reverse correlation with sample source elevation (R² 0.78 for soils from Gongga Shan; R² 0.85 for soils from West Kunlun Shan above 3200 m), suggesting that n-alkane δD_wax faithfully records the precipitation δD and that the isotopic altitude effect of precipitation controls δD_wax altitudinal gradients in the mountains. The data show a fairly strong monotonic dependency of n-alkane δD values on elevation for the eastern Plateau, but a complex relationship between n-alkane δD values and elevation for the northwestern Plateau. The δD_wax values at sites below 3200 m from the Kunlun Shan area exhibit an unexpected positive correlation with elevation. The study confirms the potential for using sediment δD_wax values to reconstruct paleo-elevation in wetter regions, but suggests caution in applying the approach to dry regions. Our results also show it is essential to consider the intricacy of the pattern of atmospheric circulation and water sources and their influence on the lapse rate of δD values with elevation.     

Tissue N content and N natural abundance in epilithic mosses for indicating atmospheric N deposition in the Guiyang area,SW China

Tissue N contents and δ¹⁵N signatures in 175 epilithic mosses were investigated from urban to rural sites in Guiyang (SW China) to determine atmospheric N deposition. Moss N contents (0.85–2.97%) showed a significant decrease from the urban area (mean = 2.24 ± 0.32%, 0–5 km) to the rural area (mean = 1.27 ± 0.13%, 20–25 km), indicating that the level of N deposition decreased away from the urban environment, while slightly higher N contents re-occurred at sites beyond 30 km, suggesting higher N deposition in more remote rural areas. Moss δ¹⁵N ranged from −12.50‰ to −1.39‰ and showed a clear bimodal distribution (−12‰ to −6‰ and −5‰ to −2‰), suggesting that there are two main sources for N deposition in the Guiyang area. More negative δ¹⁵N (mean = −8.87 ± 1.65‰) of urban mosses mainly indicated NH₃ released from excretory wastes and sewage, while the less negative δ¹⁵N (from −3.83 ± 0.82‰ to −2.48 ± 0.95‰) of rural mosses were mainly influenced by agricultural NH₃. With more negative values in the urban area than in the rural area, the pattern of moss δ¹⁵N variation in Guiyang was found to be opposite to cities where N deposition is dominated by NO_x–N. Therefore, NH_x–N is the dominant N form deposited in the Guiyang area, which is supported by higher NH_x–N than NO_x–N in local atmospheric deposition. From the data showing that moss is responding to NH_x–N/NO_x–N in deposition it can be further demonstrated that the variation of moss δ¹⁵N from the Guiyang urban to rural area was more likely controlled by the ratio of urban-NH_x/agriculture-NH_x than the ratio of NH_x–N/NO_x–N. The results of this study have extended knowledge of atmospheric N sources in city areas, showing that urban sewage discharge could be important in cities co-generic to Guiyang.     

Chlorine isotope evidence for the anthropogenic origin of tris-(4-chlorophenyl)methane

Compound-specific Cl-isotope analysis was performed on the persistent and bioaccumulating compound tris-(4-chlorophenyl)methane (4,4′,4″-TCPMe, referred to as TCPMe in this study) to elucidate whether its main source is natural or anthropogenic. Blubber from the Baltic grey seal (Halichoerus grypus) was extracted by continuous acetonitrile partitioning, and the TCPMe was isolated from the extract by preparative-capillary gas chromatography. Chlorine isotope analysis was subsequently performed by sealed-tube combustion in conjunction with thermal-ionization mass spectrometry (TIMS). The δ³⁷Cl of TCPMe was −3.5 ± 0.5‰, similar to the previously reported δ³⁷Cl of technical grade p,p′-DDT (referred to as DDT in this study). The data is not consistent with a putative marine natural source of TCPMe, as enzymatic (biotic) production is reported to give values of δ³⁷Cl < −10‰. The δ³⁷Cl–TCPMe data thus supports the hypothesis that TCPMe is produced as a byproduct during DDT synthesis and is released to the environment through the same pathways as DDT. It is also consistent with tris-(4-chlorophenyl)methanol as the primary biotransformation product of TCPMe.     

Note on the isotopic geochemistry of fossil-lacustrine tufas in carbonate plateau—A study from Dungul region (SW Egypt)

Lithological, chemical, and stable isotope data are used to characterize lacustrine tufas dating back to pre-late Miocene and later unknown times, capping different surfaces of a Tertiary carbonate (Sinn el-Kedab) plateau in Dungul region in the currently hyperarid south-western Egypt. These deposits are composed mostly of calcium carbonate, some magnesium carbonate and clastic particles plus minor amounts of organic matter. They have a wide range of (Mg/Ca)_molar ratios, from 0.03 to 0.3. The bulk-tufa carbonate has characteristic isotope compositions: (δ¹³C_mean = −2.49 ± 0.99‰; δ¹⁸O_mean = −9.43 ± 1.40‰). The δ¹³C values are consistent with a small input from C4 vegetation or thinner soils in the recharge area of the tufa-depositing systems. The δ¹⁸O values are typical of fresh water carbonates. Covariation between δ¹³C and δ¹⁸O values probably is a reflection of climatic conditions such as aridity. The tufas studied are isotopically similar to the underlying diagenetic marine chalks, marls and limestones (δ¹³C_mean = −2.06 ± 0.84‰; δ¹⁸O_mean = −10.06 ± 1.39‰). The similarity has been attributed to common meteoric water signatures. This raises large uncertainties in using tufas (Mg/Ca)_molar, δ¹³C and δ¹⁸O records as proxies of paleoclimatic change and suggests that intrinsic compositional differences in material sources within the plateau may mask climatic changes in the records.     

An experimental determination of chlorine isotope fractionation in acid systems and applications to volcanic fumaroles

The δ³⁷Cl values of volcanic fumarole gases and bubbling springs were measured from the Central American and the Kurile arcs. Low temperature gas samples from the Central American arc have δ³⁷Cl values generally between −2 and 2‰, whereas high-temperature fumaroles (>100 °C) range from 4 to 12‰, with several outliers. This is in contrast to the high-temperature fumaroles from the Kurile island Kudryavy which have slightly positive δ³⁷Cl values, averaging 0.8‰ (±0.6, 1σ), and from our previous work on Izu and Mariana arc samples in which the δ³⁷Cl values of fumarole and ash samples are similar to each other and negative. Assuming that the source for the high-T Central American fumaroles has typical subduction δ³⁷Cl values (−2.5 to 1‰), then there must be a large Cl isotope fractionation in the near-surface fumarolic system. The most likely fractionation mechanism for the high δ³⁷Cl values is between Cl⁻_aq − HCl(g), but published theoretical fractionation for this pair is only ∼1.5‰, insufficient to explain the large range of values observed in the fumaroles. Three experiments were undertaken in order to identify a process that could cause the wide range of δ³⁷Cl values observed in the high-temperature fumaroles. Results are the following: (1) A sub-boiling equilibration experiment between aqueous chloride and HCl gas had , in agreement with the theoretical calculations. (2) Evaporation of HCl(g) from hydrochloric acid at room temperature had fractionation in the opposite sense, with a . (3) A ‘synthetic fumarole’ gave large positive fractionations up to 9‰, with ³⁷Cl strongly partitioned into the vapor phase. The ‘fumarole’ experiments were made by bubbling dry air through boiling hydrochloric acid in an Erlenmeyer flask, and collecting the evolved HCl(g) in a second ‘downstream’ flask filled with distilled water. This extreme enrichment is likely due to a distillation process in which ³⁷Cl-enriched HCl(g) is stripped from the hydrochloric acid followed by a significant fraction of the light HCl(g) redissolving into the constantly condensing water vapor on the walls of the first flask. This distillation experiment creates a Cl isotope fractionation that is the same order of magnitude as observed in the high-temperature fumaroles in Central America. These results suggest that there must be a H₂O liquid-vapor region in the sub-surface fumarole conduit where light Cl is stripped from the HCl gas as it passes through the fumarole. Similar ³⁷Cl enrichments are expected in fossil epithermal boiling systems.     

The origins and behaviour of carbon in a major semi-arid river,the Murray River,Australia, as constrained by carbon isotopes and hydrochemistry

δ¹³C values of dissolved inorganic C (DIC), dissolved organic C (DOC), and particulate organic C (POC) together with δ¹⁸O and δ²H values of water, δ³⁴S values of dissolved SO₄, and major ion concentrations were measured in the Murray River and its tributaries between November 2005 and April 2007 to constrain the origins and behaviour of riverine C. δ¹³C_DIC values in the Murray River vary between −9.5 and −4.7‰ with a range of <3‰ within any sampling round. δ¹³C_DIC values of the tributaries are −11.0‰ to −5.1‰. DIC concentrations of the Murray River increase from ∼25 mg/L in the middle and upper reaches of the river to 45–55 mg/L in the lower reaches. However, the mass ratio of DIC as a proportion of the total dissolved solids (TDS) decreases from ∼0.6–0.7 in the headwaters to ∼0.2–0.3 in the lower reaches of the river, with similar downstream changes in DIC/Cl ratios. This precludes simple evaporative concentration of DIC and is interpreted as the river evading CO₂; this interpretation is consistent with pCO₂ values that are in the range 550–11,200 ppm volume (ppmv), which are far higher than those in equilibrium with the atmosphere (∼360 ppmv). The δ¹³C_DIC values are similar to those that would be produced by the weathering of marine limestone (δ¹³C ∼ 0‰). However, the lack of marine limestones cropping out in the Murray–Darling Basin and the relatively uniform δ¹³C_DIC values of the Murray River (even in upland reaches where the dominant rock types are metamorphosed silicates and granites) make this unlikely. Rather the high pCO₂ values and δ¹³C_DIC values are best explained by a combination of mineralisation of low δ¹³C organic C and evasion to the atmosphere. The rate of these two processes may attain near steady state and control both DIC concentrations and δ¹³C values.     

Sulfur and carbon isotope records from 1700 to 800 Ma carbonates of the Jixian section, northern China: Implications for secular isotope variations in Proterozoic seawater and relationships to global supercontinental events

This study is a comprehensive, stable isotope survey of the marine carbonate-dominated, upper Paleo- to lower Neoproterozoic stratigraphy of Jixian County, China. Carbonate-associated sulfate (CAS) was extracted and measured for δ³⁴S_CAS using the same samples analyzed for δ¹³C_carbonate. This integrated proxy approach is a step towards a more comprehensive picture of secular variation in the composition of Proterozoic seawater. We specifically sampled marine carbonate intervals from the lower section of the Chuanlinggou Formation, Changcheng Group (ca. 1700 Ma) to the top of the Jingeryu Formation, Qingbaikou Group (ca. 800 Ma). δ¹³C_carbonate values are mostly negative in the upper Paleoproterozoic Changcheng Group, with an ascending trend from −3‰ to 0‰. We observed variation of approximately 0 ± 1‰ in the Mesoproterozoic Jixian Group, and positive values of +2 ± 2‰ characterize the lower Neoproterozoic Qingbaikou Group. Stratigraphic variations in δ³⁴S_CAS are more remarkable in their ranges and magnitudes, including conspicuously high values exceeding +30‰ in the three intervals at ca. 1700 Ma, 1300-1100 Ma, and 1000-900 Ma. In the Changcheng Group, δ³⁴S_CAS values are typically higher than +25‰, with only a few values of less than +15‰. In contrast, most of the data spanning from the Mesoproterozoic Tieling Formation of the Jixian Group to the lower Neoproterozoic Jingeryu Formation of the Qingbaikou Group are highly variable between +10‰ and +25‰, with some values exceeding +25‰.In the late Paleoproterozoic (1700-1600 Ma), a >10‰ decrease in δ³⁴S_CAS and ∼3‰ increase in δ¹³C_carbonate are coincident with, and likely related to, the breakup of Columbia, a supercontinent that predated Rodinia. Carbon and sulfur isotope data from the Mesoproterozoic, when global tectonic activity was comparatively weaker, fall mostly in the ranges of +15 ± 10‰ and 0 ± 1‰, respectively, but fluctuations of >20‰ for δ³⁴S_CAS and >3‰ for the δ¹³C_carbonate at ca. 1450-1400 Ma may reflect subduction and large-scale magmatic activity in island arcs marking the end of Columbia breakup. From the late Mesoproterozoic (ca. 1300-1100 Ma) to the early Neoproterozoic (ca. 800 Ma), the δ¹³C and δ³⁴S of seawater increased gradually with increasing variability. Most impressive areδ³⁴S_CAS values that exceed +30‰ in two intervals at ca. 1300-1100 Ma and ca. 1000-900 Ma, which may reflect the assembly and early breakup of Rodinia. Although gaps in the record remain, and studies of even higher resolution are warranted, our results suggest that changes in paleoceanographic conditions linked to global tectonics strongly influenced the biogeochemical cycles of C and S. Furthermore, periods of the Proterozoic previously noted for their isotopic invariability show clear isotopic expressions of this tectonic activity.     

Abundance of mass 47 CO2 in urban air, car exhaust, and human breath

Atmospheric carbon dioxide is widely studied using records of CO₂ mixing ratio, δ¹³C and δ¹⁸O. However, the number and variability of sources and sinks prevents these alone from uniquely defining the budget. Carbon dioxide having a mass of 47 u (principally ¹³C¹⁸O¹⁶O) provides an additional constraint. In particular, the mass 47 anomaly (Δ₄₇) can distinguish between CO₂ produced by high temperature combustion processes vs. low temperature respiratory processes. Δ₄₇ is defined as the abundance of mass 47 isotopologues in excess of that expected for a random distribution of isotopes, where random distribution means that the abundance of an isotopologue is the product of abundances of the isotopes it is composed of and is calculated based on the measured ¹³C and ¹⁸O values. In this study, we estimate the δ¹³C (vs. VPDB), δ¹⁸O (vs. VSMOW), δ47, and Δ₄₇ values of CO₂ from car exhaust and from human breath, by constructing ‘Keeling plots’ using samples that are mixtures of ambient air and CO₂ from these sources. δ47 is defined as , where is the R⁴⁷ value for a hypothetical CO₂ whose δ¹³C_VPDB = 0, δ¹⁸O_VSMOW = 0, and Δ₄₇ = 0. Ambient air in Pasadena, CA, where this study was conducted, varied in [CO₂] from 383 to 404 μmol mol⁻¹, in δ¹³C and δ¹⁸O from −9.2 to −10.2‰ and from 40.6 to 41.9‰, respectively, in δ47 from 32.5 to 33.9‰, and in Δ₄₇ from 0.73 to 0.96‰. Air sampled at varying distances from a car exhaust pipe was enriched in a combustion source having a composition, as determined by a ‘Keeling plot’ intercept, of −24.4 ± 0.2‰ for δ¹³C (similar to the δ¹³C of local gasoline), δ¹⁸O of 29.9 ± 0.4‰, δ47 of 6.6 ± 0.6‰, and Δ₄₇ of 0.41 ± 0.03‰. Both δ¹⁸O and Δ₄₇ values of the car exhaust end-member are consistent with that expected for thermodynamic equilibrium at∼200 °C between CO₂ and water generated by combustion of gasoline-air mixtures. Samples of CO₂ from human breath were found to have δ¹³C and δ¹⁸O values broadly similar to those of car exhaust-air mixtures, −22.3 ± 0.2 and 34.3 ± 0.3‰, respectively, and δ47 of 13.4 ± 0.4‰. Δ₄₇ in human breath was 0.76  ± 0.03‰, similar to that of ambient Pasadena air and higher than that of the car exhaust signature.     

Br/Cl ratios and O, H, C, and B isotopic constraints on the origin of saline waters from eastern Canada

Saline groundwaters were recovered from undisturbed (Restigouche deposit) and active (Brunswick #12 mine) Zn-Pb volcanogenic massive sulfide deposits in the Bathurst Mining Camp (BMC), northern New Brunswick, Canada. These groundwaters, along with fresh to brackish meteoric ground and surface waters from the BMC, have been analyzed to determine their major, trace element and stable isotopic (O, H, C, and B) compositions. Saline groundwaters (total dissolved solids = 22-45 g/L) are characterized by relatively high Na/Ca ratios compared to brines from the Canadian Shield and low Na/Cl_molar and δ¹¹B isotopic compositions (−2.5‰ to 11.1‰) compared to seawater. Although saline waters from the Canadian Shield commonly have oxygen and hydrogen isotopic compositions that plot to the left of the global meteoric water line, those from the BMC fall close to the water line. Fracture and vein carbonate minerals at the Restigouche deposit have restricted carbon isotopic compositions of around −5‰ to −6‰. The carbon isotopic compositions of the saline waters at the Restigouche deposit (+12‰ δ¹³C_DIC) are the result of fractionation of dissolved inorganic carbon by methanogenesis. We suggest that, unlike previous models for shield brines, the composition of saline waters in the BMC is best explained by prolonged water-rock reaction, with no requirement of precursor seawater. We suggest that elevated Br/Cl ratios of saline waters compared to seawater may be explained by differential uptake of Br and Cl during groundwater evolution through water-rock reaction.     

Indoor and outdoor urban atmospheric CO2: Stable carbon isotope constraints on mixing and mass balance

From July to November 2009, concentrations of CO₂ in 78 samples of ambient air collected in 18 different interior spaces on a university campus in Dallas, Texas (USA) ranged from 386 to 1980 ppm. Corresponding δ¹³C values varied from −8.9‰ to −19.4‰. The CO₂ from 22 samples of outdoor air (also collected on campus) had a more limited range of concentrations from 385 to 447 ppm (avg. = 408 ppm), while δ¹³C values varied from −10.1‰ to −8.4‰ (avg.=-9.0‰). In contrast to ambient indoor and outdoor air, the concentrations of CO₂ exhaled by 38 different individuals ranged from 38,300 to 76,200 ppm (avg. = 55,100 ppm), while δ¹³C values ranged from −24.8‰ to −17.7‰ (avg. = −21.8‰). The residence times of the total air in the interior spaces of this study appear to have been on the order of 10 min with relatively rapid approaches (∼30 min) to steady-state concentrations of ambient CO₂ gas. Collectively, the δ¹³C values of the indoor CO₂ samples were linearly correlated with the reciprocal of CO₂ concentration, exhibiting an intercept of −21.8‰, with r² = 0.99 and p < 0.001 (n = 78). This high degree of linearity for CO₂ data representing 18 interior spaces (with varying numbers of occupants), and the coincidence of the intercept (−21.8‰) with the average δ¹³C value for human-exhaled CO₂ demonstrates simple mixing between two inputs: (1) outdoor CO₂ introduced to the interior spaces by ventilation systems, and (2) CO₂ exhaled by human occupants of those spaces. If such simple binary mixing is a common feature of interior spaces, it suggests that the intercept of a mixing line defined by two data points (CO₂ input from the local ventilation system and CO₂ in the ambient air of the room) could be a reasonable estimate of the average δ¹³C value of the CO₂ exhaled by the human occupants. Thus, such indoor spaces appear to constitute effective “sample vessels” for collection of CO₂ that can be used to determine the average proportions of C₃ and C₄-derived C in the diets of the occupants. For the various groups occupying the rooms sampled in this study, C₄-derived C appears to have constituted ∼40% of the average diet.     

The oxygen-isotope composition of chondrules and isolated forsterite and olivine grains from the Tagish Lake carbonaceous chondrite

The oxygen-isotope compositions (obtained by laser fluorination) of hand-picked separates of isolated forsterite, isolated olivine and chondrules from the Tagish Lake carbonaceous chondrite describe a line (δ¹⁷O = 0.95 * δ¹⁸O − 3.24; R² = 0.99) similar to the trend known for chondrules from other carbonaceous chondrites. The isolated forsterite grains (Fo_99.6-99.8; δ¹⁸O = −7.2‰ to −5.5‰; δ¹⁷O = −9.6‰ to −8.2‰) are more ¹⁶O-rich than the isolated olivine grains (Fo_39.6-86.8; δ¹⁸O = 3.1‰ to 5.1‰; δ¹⁷O = −0.3‰ to 2.2‰), and have chemical and isotopic characteristics typical of refractory forsterite. Chondrules contain olivine (Fo_97.2-99.8) with oxygen-isotope compositions (δ¹⁸O = −5.2‰ to 5.9‰; δ¹⁷O = −8.1‰ to 1.2‰) that overlap those of isolated forsterite and isolated olivine. An inverse relationship exists between the Δ¹⁷O values and Fo contents of Tagish Lake isolated forsterite and chondrules; the chondrules likely underwent greater exchange with ¹⁶O-poor nebular gases than the forsterite. The oxygen-isotope compositions of the isolated olivine grains describe a trend with a steeper slope (1.1 ± 0.1, R² = 0.94) than the carbonaceous chondrite anhydrous mineral line (CCAM_slope = 0.95). The isolated olivine may have crystallized from an evolving melt that exchanged with ¹⁶O-poor gases of somewhat different composition than those which affected the chondrules and isolated forsterite. The primordial components of the Tagish Lake meteorite formed under conditions similar to other carbonaceous chondrite meteorite groups, especially CMs. Its alteration history has its closest affinities to CI carbonaceous chondrites.     

Copper isotope fractionation in acid mine drainage

We measured the Cu isotopic composition of primary minerals and stream water affected by acid mine drainage in a mineralized watershed (Colorado, USA). The δ⁶⁵Cu values (based on ⁶⁵Cu/⁶³Cu) of enargite (δ⁶⁵Cu = −0.01 ± 0.10‰; 2σ) and chalcopyrite (δ⁶⁵Cu = 0.16 ± 0.10‰) are within the range of reported values for terrestrial primary Cu sulfides (−1‰ < δ⁶⁵Cu < 1‰). These mineral samples show lower δ⁶⁵Cu values than stream waters (1.38‰ ? δ⁶⁵Cu ? 1.69‰). The average isotopic fractionation (Δ_aq-min = δ⁶⁵Cu_aq − δ⁶⁵Cu_min, where the latter is measured on mineral samples from the field system), equals 1.43 ± 0.14‰ and 1.60 ± 0.14‰ for chalcopyrite and enargite, respectively. To interpret this field survey, we leached chalcopyrite and enargite in batch experiments and found that, as in the field, the leachate is enriched in ⁶⁵Cu relative to chalcopyrite (1.37 ± 0.14‰) and enargite (0.98 ± 0.14‰) when microorganisms are absent. Leaching of minerals in the presence of Acidithiobacillus ferrooxidans results in smaller average fractionation in the opposite direction for chalcopyrite (Δ_aq-min^o=-0.57±0.14‰, where min^o refers to the starting mineral) and no apparent fractionation for enargite (Δ_aq-min^o=0.14±0.14‰). Abiotic fractionation is attributed to preferential oxidation of ⁶⁵Cu⁺ at the interface of the isotopically homogeneous mineral and the surface oxidized layer, followed by solubilization. When microorganisms are present, the abiotic fractionation is most likely not seen due to preferential association of ⁶⁵Cu_aq with A. ferrooxidans cells and related precipitates. In the biotic experiments, Cu was observed under TEM to occur in precipitates around bacteria and in intracellular polyphosphate granules. Thus, the values of δ⁶⁵Cu in the field and laboratory systems are presumably determined by the balance of Cu released abiotically and Cu that interacts with cells and related precipitates. Such isotopic signatures resulting from Cu sulfide dissolution should be useful for acid mine drainage remediation and ore prospecting purposes.     

Isotopic constraints on ice age fluids in active geothermal systems: Reykjanes, Iceland

The Reykjanes geothermal system is located on the landward extension of the Mid-Atlantic Ridge in southwest Iceland, and provides an on-land proxy to high-temperature hydrothermal systems of oceanic spreading centers. Previous studies of elemental composition and salinity have shown that Reykjanes geothermal fluids are likely hydrothermally modified seawater. However, δD values of these fluids are as low as −23‰, which is indicative of a meteoric water component. Here we constrain the origin of Reykjanes hydrothermal solutions by analysis of hydrogen and oxygen isotope compositions of hydrothermal epidote from geothermal drillholes at depths between 1 and 3 km. δD_EPIDOTE values from wells RN-8, -9, -10 and -17 collectively range from −60 to −78‰, and δ¹⁸O_EPIDOTE in these wells are between −3.0 and 2.3‰. The δD values of epidote generally increase along a NE trend through the geothermal field, whereas δ¹⁸O values generally decrease, suggesting a southwest to northeast migration of the geothermal upflow zone with time that is consistent with present-day temperatures and observed hydrothermal mineral zones. For comparative analysis, the meteoric-water dominated Nesjavellir and Krafla geothermal systems, which have a δD_FLUID of ∼ −79‰ and −89‰, respectively, show δD_EPIDOTE values of −115‰ and −125‰. In contrast, δD_EPIDOTE from the mixed meteoric-seawater Svartsengi geothermal system is −68‰; comparable to δD_EPIDOTE from well RN-10 at Reykjanes.Stable isotope compositions of geothermal fluids in isotopic equilibrium with the epidotes at Reykjanes are computed using published temperature dependent hydrogen and oxygen isotope fractionation curves for epidote-water, measured isotope composition of the epidotes and temperatures approximated from the boiling point curve with depth. Calculated δD and δ¹⁸O of geothermal fluids are less than 0‰, suggesting that fluids of meteoric or glacial origin are a significant component of the geothermal solutions. Additionally, δD_FLUID values in equilibrium with geothermal epidote are lower than those of modern-day fluids, whereas calculated δ¹⁸O_FLUID values are within range of the observed fluid isotope composition. We propose that modern δD_EPIDOTE and δD_FLUID values are the result of diffusional exchange between hydrous alteration minerals that precipitated from glacially-derived fluids early in the evolution of the Reykjanes system and modern seawater-derived geothermal fluids. A simplified model of isotope exchange in the Reykjanes geothermal system, in which the average starting δD_ROCK value is −125‰ and the water to rock mass ratio is 0.25, predicts a δD_FLUID composition within 1‰ of average measured values. This model resolves the discrepancy between fluid salinity and isotope composition of Reykjanes geothermal fluids, explains the observed disequilibrium between modern fluids and hydrothermal epidote, and suggests that rock-fluid interaction is the dominant control over the evolution of fluid isotope composition in the hydrothermal system.     

The elemental and isotopic composition of sulfur and nitrogen in Chinese coals

Coal combustion is an important atmospheric pollution source in most Chinese cities, so systematic studies on sulfur and nitrogen in Chinese coals are needed. The sulfur contents in Chinese coals average 0.9 ± 1.0%, indicating that most Chinese coals are low in sulfur. A nearly constant mean δ³⁴S value is observed in low sulfur (TS < 1) Chinese coals of different ages (D, P₁, T₃ and J₃). High sulfur Chinese coals (OS > 0.8%), often found at late Carboniferous (C₃) and late Permian (P₂) in southern China, had two main sulfur sources (original plant sulfur and secondary sulfur). The wide variety of δ³⁴S values of Chinese coals (−15‰ to +50‰) is a result of a complex sulfur origin. The δ¹⁵N values of Chinese coals ranged from −6‰ to +4‰, showing a lack of correlation with coal ages, whereas nitrogen contents are higher in Paleozoic coals than in Mesozoic coals. This may be related to their original precursor plant species: high nitrogen pteridophytes for the Paleozoic coals and low nitrogen gymnosperms for the Mesozoic coals. Different to δ³⁴S values, Chinese coals showed higher δ¹⁵N values in marine environments than in freshwater environments.