A global model of mass independent mercury stable isotope fractionation

Mass independent fractionation (MIF) of stable isotopes associated with terrestrial geochemical processes was first observed in the 1980s for oxygen and in the 1990s for sulfur isotopes. Recently mercury (Hg) was added to this shortlist when positive odd Hg isotope anomalies were observed in biological tissues. Experimental work identified photoreduction of aquatic inorganic divalent Hg^II and photodegradation of monomethylmercury species as plausible MIF inducing reactions. Observations of continental receptors of atmospheric Hg deposition such as peat, lichens, soils and, indirectly, coal have shown predominantly negative MIF. This has led to the suggestion that atmospheric Hg has negative MIF signatures and that these are the compliment of positive Hg MIF in the aquatic environment. Recent observations on atmospheric vapor phase Hg⁰ and Hg^II in wet precipitation reveal zero and positive Hg MIF respectively and are in contradiction with a simple aquatic Hg^II photoreduction scenario as the origin for global Hg MIF observations.This study presents a synthesis of all terrestrial Hg MIF observations, and these are integrated in a one-dimensional coupled continent-ocean-atmosphere model of the global Hg cycle. The model illustrates how Hg MIF signatures propagate through the various Earth surface reservoirs. The scenario in which marine photoreduction is the main MIF inducing process results in negative atmospheric Δ¹⁹⁹Hg and positive ocean Δ¹⁹⁹Hg of −0.5‰ and +0.25‰, yet does not explain atmospheric Hg⁰ and Hg^II wet precipitation observations. Alternative model scenarios that presume in-cloud aerosol Hg^II photoreduction and continental Hg^II photoreduction at soil, snow and vegetation surfaces to display MIF are necessary to explain the ensemble of natural observations. The model based approach is a first step in understanding Hg MIF at a global scale and the eventual incorporation of Hg stable isotope information in detailed global mercury chemistry and transport models.     

Mass dependent stable isotope fractionation of mercury during mer mediated microbial degradation of monomethylmercury

Controlling bioaccumulation of toxic monomethylmercury (MMHg) in aquatic food chains requires differentiation between biotic and abiotic pathways that lead to its production and degradation. Recent mercury (Hg) stable isotope measurements of natural samples suggest that Hg isotope ratios can be a powerful proxy for tracing dominant Hg transforming pathways in aquatic ecosystems. Specifically, it has been shown that photo-degradation of MMHg causes both mass dependent (MDF) and mass independent fractionation (MIF) of Hg isotopes. Because the extent of MDF and MIF observed in natural samples (e.g., fish, soil and sediments) can potentially be used to determine the relative importance of pathways leading to MMHg accumulation, it is important to determine the potential role of microbial pathways in contributing to the fractionation, especially MIF, observed in these samples. This study reports the extent of fractionation of Hg stable isotopes during degradation of MMHg to volatile elemental Hg and methane via the microbial Hg resistance (mer) pathway in Escherichia coli carrying a mercury resistance (mer) genetic system on a multi-copy plasmid. During experimental microbial degradation of MMHg, MMHg remaining in reactors became progressively heavier (increasing δ²⁰²Hg) with time and underwent mass dependent Rayleigh fractionation with a fractionation factor α_202/198 = 1.0004 ± 0.0002 (2SD). However, MIF was not observed in any of the microbial MMHg degradation experiments indicating that the isotopic signature left by mer mediated MMHg degradation is significantly different from fractionation observed during DOC mediated photo-degradation of MMHg. Additionally, a clear suppression of Hg isotope fractionation, both during reduction of Hg(II) and degradation of MMHg, was observed when the cell densities increased, possibly due to a reduction in substrate bioavailability. We propose a multi-step framework for understanding the extent of fractionation seen in our MMHg degradation experiments and, based on estimates of the rates of the various steps involved in this mer mediated pathway, suggest which steps in the process could contribute towards the observed extent of fractionation. This framework suggests that at lower cell densities catalysis by MerB was the rate limiting step while at higher cell densities transport into the cell, which does not cause fractionation, became the rate limiting step. In addition to presenting evidence for absence of MIF during mer mediated Hg transformations, based on the nature of Hg compounds and microbe-Hg interactions, we suggest that the nuclear spin dependent MIF (i.e., the magnetic isotope effect) is also unlikely to occur during other non mer mediated ‘dark’ microbial Hg transformations (e.g., formation of MMHg and oxidative degradation of MMHg). Because of the important implications of the absence of MIF during biological processes on Hg isotope systematics, we discuss theoretical considerations and experimental strategies that could be used to confirm this suggestion.     

Historical variations in the stable isotope composition of mercury in a sediment core from a riverine lake: Effects of dams,pulp and paper mill wastes,and mercury from a chlor-alkali plant

The Wabigoon River (Ontario, Canada) was affected by dams starting in 1898 and was polluted with pulp and paper mill wastes starting in 1913 and mercury from a chlor-alkali plant from 1962 to 1975. A dated sediment core from a riverine lake was analysed to investigate resultant changes in the biogeochemistry of mercury as revealed by variations in mercury isotope ratios and sediment chemistry. A total mercury maximum formed by the mercury pollution coincided with minimums in the δ-values of the ¹⁹⁸Hg/²⁰²Hg, ¹⁹⁹Hg/²⁰²Hg, ²⁰⁰Hg/²⁰²Hg, and ²⁰¹Hg/²⁰²Hg ratios, and the δ-values decreased in the order δ²⁰¹Hg > δ²⁰⁰Hg > δ¹⁹⁹Hg > δ¹⁹⁸Hg. Thus, mass-dependent fractionation caused depletion in lighter isotopes, implying evaporation of Hg(0) and pollution of the atmosphere as well as the river-lake system. Concurrently, mass-independent fractionation caused ¹⁹⁹Hg enrichment, possibly reflecting an independently documented upsurge in methylmercury production, and ²⁰¹Hg depletion, suggesting removal of methylmercury with anomalously high ²⁰¹Hg/¹⁹⁹Hg ratios by aquatic organisms and accumulation of ²⁰¹Hg-depleted inorganic Hg(II) in sediments. The δ²⁰¹Hg/δ¹⁹⁹Hg ratio rose abruptly when mercury pollution began, reflecting the resultant increase in methylmercury production, and remained high but gradually declined as the pollution abated, paralleling trends shown by methylmercury in aquatic organisms. The δ²⁰¹Hg/δ¹⁹⁹Hg ratio of pre-1962 background mercury increased ca. 1898 and ca. 1913–1929, suggesting accelerated methylmercury production due to stimulation of microbial activities by the damming of the river and the input of pulp and paper mill wastes, respectively. Other variations were linked to economic and technological factors that affected pulp and paper manufacture.     

Mercury isotope fractionation during liquid-vapor evaporation experiments

Liquid-vapor mercury isotope fractionation was investigated under equilibrium and dynamic conditions. Equilibrium evaporation experiments were performed in a closed glass system under atmospheric pressure between 0 and 22 °C, where vapor above the liquid was sampled at chemical equilibrium. Dynamic evaporation experiments were conducted in a closed glass system under 10⁻⁵ bar vacuum conditions varying (1) the fraction of liquid Hg evaporated at 22 °C and (2) the temperature of evaporation (22-100 °C). Both, residual liquid and condensed vapor fractions were analyzed using stannous chloride CV-MC-ICP-MS.Equilibrium evaporation showed a constant liquid-vapor fractionation factor (α_202/198) of 1.00086 ± 0.00022 (2SD, n = 6) within the 0-22 °C range. The 22 °C dynamic evaporations experiments displayed Rayleigh distillation fractionation behavior with liquid-vapor α_202/198 = 1.0067 ± 0.0011 (2SD), calculated from both residual and condensed vapor fractions. Our results confirm historical data (1920s) from Brönsted, Mulliken and coworkers on mercury isotopes separation using evaporation experiments, for which recalculated δ²⁰²Hg′ showed a liquid-vapor α_202/198 of 1.0076 ± 0.0017 (2SD). This liquid-vapor α_202/198 is significantly different from the expected kinetic α_202/198 value ((202/198)^0.5 = 1.0101). A conceptual evaporation model of back condensation fluxes within a thin layer at the liquid-vapor interface was used to explain this discrepancy. The δ²⁰²Hg′ of condensed vapor fractions in the 22-100 °C temperature range experiments showed a negative linear relationship with 10⁶/T², explained by increasing rates of exchange within the layer with the increase in temperature.Evaporation experiments also resulted in non-mass-dependent fractionation (NMF) of odd ¹⁹⁹Hg and ²⁰¹Hg isotopes, expressed as Δ¹⁹⁹Hg′ and Δ²⁰¹Hg′, the deviation in ‰ from the mass fractionation relationship with even isotopes. Liquid-vapor equilibrium yielded Δ¹⁹⁹Hg′/Δ²⁰¹Hg′ relationship of 2.0 ± 0.6 (2SE), which is statistically not different from the one predicted for the nuclear field shift effect (Δ¹⁹⁹Hg/Δ²⁰¹Hg ≈ 2.47). On the other hand, evaporation under dynamic conditions at 22 °C led to negative anomalies in the residual liquid fractions that are balanced by positive anomalies in condensed vapors with lower Δ¹⁹⁹Hg′/Δ²⁰¹Hg′ ratios of 1.2 ± 0.4 (2SD). This suggests that either magnetic isotope effects may have occurred without radical chemistry or an unknown NMF process on odd isotopes operated during liquid mercury evaporation.     

Identification of contamination in a lake sediment core using Hg and Pb isotopic compositions,Lake Ballinger,Washington, USA

Concentrations and isotopic compositions of Hg and Pb were measured in a sediment core collected from Lake Ballinger, near Seattle, Washington, USA. Lake Ballinger has been affected by input of metal contaminants emitted from the Tacoma smelter, which operated from 1887 to 1986 and was located about 53 km south of the lake. Concentrations and loadings of Hg and Pb in Lake Ballinger increased by as much as three orders of magnitude during the period of smelting as compared to the pre-smelting period. Concentrations and loadings of Hg and Pb then decreased by about 55% and 75%, respectively, after smelting ended. Isotopic compositions of Hg changed considerably during the period of smelting (δ²⁰²Hg = −2.29‰ to −0.38‰, mean −1.23‰, n = 9) compared to the pre-smelting period (δ²⁰²Hg = −2.91‰ to −2.50‰, mean −2.75‰, n = 4). Variations were also observed in ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb isotopic compositions during these periods. Data for Δ¹⁹⁹Hg and Δ²⁰¹Hg indicate mass independent fractionation (MIF) of Hg isotopes in Lake Ballinger sediment during the smelting and post-smelting period and suggest MIF in the ore smelted, during the smelting process, or chemical modification at some point in the past. Negative values for Δ¹⁹⁹Hg and Δ²⁰¹Hg for the pre-smelting period are similar to those previously reported for soil, peat, and lichen, likely suggesting some component of atmospheric Hg. Variations in the concentrations and isotopic compositions of Hg and Pb were useful in tracing contaminant sources and the understanding of the depositional history of sedimentation in Lake Ballinger.     

A review of isotopic composition as an indicator of the natural and anthropogenic behavior of mercury

There are seven stable isotopes of Hg that can be fractionated as a result of inorganic and organic interactions. Important inorganic reactions involve speciation changes resulting from variations in environmental redox conditions, and phase changes resulting from variations in temperature and/or atmospheric pressure. Important organic reactions include methylation and demethylation, reactions that are bacterially mediated, and complexing with organic anions in soils. The measurement of Hg isotopes by multi-collector-inductively coupled plasma-mass spectrometry (MC-ICP-MS) is now sufficiently precise and sensitive that it is potentially possible to develop the systematics of Hg isotopic fractionation. This provides an opportunity to evaluate the utility of Hg isotopes in identifying source processes, transport mechanisms, and sinks. New values are provided for, ²⁰¹Hg/¹⁹⁸Hg, ²⁰⁰Hg/¹⁹⁸Hg, ¹⁹⁹Hg/¹⁹⁸Hg for three standard materials (IRMM-AE639, SRM 1641c, SRM 3133) that can be used to make inter-laboratory data comparisons, and these values are tabulated with published isotopic information. Overall, the isotopic data for these standards agree to approximately 0.2‰. The paper reviews Hg isotope studies that deal with hydrothermal ore deposits, sediments, coal and organic complexing.     

煤汞同位素地球化学研究进展

汞是煤中普遍存在的痕量元素,煤炭消耗总量之巨使燃煤成为全球汞污染主要来源之一。汞具有7种稳定同位素, 并且兼具质量分馏和非质量分馏效应,使通过汞同位素对涉煤汞污染源和汞迁移、转化示踪成为理想途径。煤中汞同位素 研究获得长足进展。第一,初步给出了世界11个产煤国煤中汞同位素δ202Hg的特征值及分布范围,为示踪环境介质汞的燃 煤源污染源创造了条件。第二,发现了原煤中汞存在奇数质量汞的非质量分馏效应（Δ199Hg≠0）,有助于配合δ202Hg开展示 踪研究。第三,中国不同产煤地及不同成煤期原煤中汞同位素δ202Hg与Δ199Hg值已被测试,为中国开展煤源汞污染示踪研究 打下一定基础。进一步工作可能有待加强的4个方面：（1） 全球不同地域和时代煤中汞同位素数据库的不断补充、修正和 完善;（2） 煤炭生产遗存物,如残留煤和煤矸石等与气-水环境相互作用中的汞同位素问题;（3） 燃煤派生的且影响人类 健康的环境介质如大气细颗粒物（PM2.5） 的汞同位素问题;（4） 涉及煤火汞的迁移转化是复杂的,部分汞具有二次释放特 性,其中汞同位素问题仍是未知的。总之煤中汞及其关联的汞同位素研究方兴未艾。     

Nuclear field shift effects on stable isotope fractionation: a review

An anomalous isotope effect exists in many heavy element isotope systems (e.g., Sr, Gd, Zn, U). This effect used to be called the “odd–even isotope effect” because the odd mass number isotopes behave differently from the even mass number isotopes. This mass-independent isotope fractionation driving force, which originates from the difference in the ground-state electronic energies caused by differences in nuclear size and shape, is currently denoted as the nuclear field shift effect (NFSE). It is found that the NFSE can drive isotope fractionation of some heavy elements (e.g., Hg, Tl, U) to an astonishing degree, far more than the magnitude caused by the conventional mass-dependent effect (MDE). For light elements, the MDE is the dominant factor in isotope fractionation, while the NFSE is neglectable. Furthermore, the MDE and the NFSE both decrease as temperatures increase, though at different rates. The MDE decreases rapidly with a factor of 1/T², while the NFSE decreases slowly with a factor of 1/T. As a result, even at high temperatures, the NFSE is still significant for many heavy element isotope systems. In this review paper, we begin with an introduction of the basic concept of the NSFE, including its history and recent progress, and follow with the potential implications of the inclusion of the NFSE into the kinetic isotope fractionation effect (KIE) and heavy isotope geochronology.     

Archean Mass-independent Fractionation of Sulfur Isotope:New Evidence of Bedded Sulfide Deposits in the Yanlingguan-Shihezhuang area of Xintai, Shandong Province

Multiple sulfur isotope ratios （^34S/^33S/^32S） of Archean bedded sulfides deposits were measured in the Yanlingguan Formation of the Taishan Group in Xintai, Shandong Province, East of China; 633S = -0.7%o to 3.8‰,δ^34S = 0.1‰-8.8‰, △^33S = -2.3‰ to -0.7‰. The sulfur isotope compositions show obvious mass-independent fractionation （MIF） signatures. The presence of MIF of sulfur isotope in Archean sulfides indicates that the sulfur was from products of photochemical reactions of volcanic SO2 induced by solar UV radiation, implying that the ozone shield was not formed in atmosphere at that time, and the oxygen level was less than 10-5 PAL （the present atmosphere level）. The sulfate produced by photolysis of SO2 with negative △^33S precipitated near the volcanic activity center; and the product of element S with positive △^33S precipitated far away from the volcanic activity center. The lower △^33S values of sulfide （-2.30‰ to --0.25‰） show that Shihezhuang was near the volcanic center, and sulfur was mostly from sulfate produced by photolysis. The higher △^33S values （-0.5‰ to -‰） indicate that Yanlingguan was far away from the volcanic center and that some of sulfur were from sulfate, another from element S produced by photolysis. The data points of sulfur isotope from Yanlingguan are in a line parallel to MFL （mass dependent fractionation line） on the plot of δ^34S--δ^33S, showing that the volcanic sulfur species went through the atmospheric cycle into the ocean, and then mass dependent fractionation occurred during deposition of sulfide. The data points of sulfur isotope from Shihezhuang represent a mix of different sulfur source.     

Mass-independent isotope effects in Archean (2.5 to 3.8 Ga) sedimentary sulfides determined by ion microprobe analysis

We report sulfur isotope anomalies with Δ³³S, the deviation from a mass-dependent fractionation line for the three-isotope system (³⁴S/³²S vs. ³³S/³²S), ranging up to ±2‰ within individual Archean sedimentary sulfides from a variety of localities. Our measurements, which are made in situ by multicollector secondary ion mass spectrometry, unequivocally corroborate prior bulk measurements of mass-independent fractionations (MIF) in sulfur and provide additional evidence for an anoxic atmosphere on the Earth before ∼2 Ga. This technique also offers new opportunities for exploring ancient sulfur metabolisms preserved in the rock record. The presence of MIF sulfur in sulfides from a >3.8-Ga Fe-rich quartzite from Akilia (island), West Greenland, is consistent with a marine sedimentary origin for this rock.     

Mineralogy and Isotope Geochemistry of Active Submarine Hydrothermal Field at Suiyo Seamount, Izu–Bonin Arc, West Pacific Ocean

This report presents mineralogical, geochemical and isotopic data on samples obtained using the Benthic Multi‐coring System (BMS) to drill a submarine hydrothermal deposit developed in a caldera on the summit of the Suiyo Seamount in the Izu–Bonin Island Arc, south of Japan. This deposit is regarded as the first example of Kuroko‐type sulfide mineralization on a volcano at the volcanic front of an island arc. The mineralization and hydrothermal alteration below the 300 × 150‐m area of active venting was investigated to depths of 2–9 m below the sea floor. Drilling beneath the area of active venting recovered a sequence of altered volcanic rocks (dacite lavas, pyroclastic rocks of dacite–rhyolite compositions and pumice) associated with sulfide veining and patches/veins of anhydrite. No massive sulfide was found, however, and the subsea‐floor mineralization to 10 m depth is dominated by anhydrite and clay minerals with some sulfides. Sulfide‐bearing samples contained high Au (up to 42 ppm), Ag (up to 263 ppm), As (up to 1550 ppm), Hg (up to 55 ppm), Sb (up to 772 ppm), and Se (up to 24 ppm). Electron probe microanalyzer indicated that realgar, orpiment, and mimetite were major As‐bearing minerals. The sulfides were also characterized by high Zn (>10%) compared to Cu (<6.3%) and Pb (<0.6%). The δ²⁰²Hg/¹⁹⁸Hg, δ²⁰²Hg/¹⁹⁹Hg and δ²⁰²Hg/²⁰⁰Hg of the sulfide‐bearing dacite samples and a sulfide chimney decreased with increasing Hg/Zn concentration ratio. The variation of the δ²⁰²Hg/¹⁹⁸Hg ranged from ?2.8 to +0.5‰ to relative to S‐HG02027. The large range of these δ²⁰²Hg/¹⁹⁸Hg was greater than might be expected for such a heavy element and may be due to a predominance of kinetic effects. The variation of δ²⁰²Hg/¹⁹⁸Hg of sulfide‐bearing dacite samples suggested that light Hg isotope in the vapor mixed with oxygenated seawater near sea floor during mineralization. Lead isotope ratios of the sulfide were very similar to those of the dacite lava, suggesting that lead is of magmatic origin. The ⁸⁷Sr/⁸⁶Sr ratio (0.70872) of anhydrite was different from that of the dacite lava, and suggests an Sr derivation predominantly from seawater. Hydrothermal alteration of the dacite in the Suiyo hydrothermal field was characterized by Fe‐sulfides, anhydrite, barite, montmorillonite, chlorite/montmorillonite mixed‐layer minerals, mica, and chlorite with little or no feldspar or cristobalite. Hydrothermal clay minerals changed with depth from montmorillonite to chlorite/montmorillonite mixed‐layer minerals to chlorite and mica. Hydrogen isotope ratios of chlorite/montmorillonite and mixed‐layer, mica‐chlorite composites obtained below the active venting sites ranged from ?49 to ?24‰, suggesting seawater as the dominant fluid causing alteration. Oxygen isotope ratios of anhydrite ranged from 9.2 to 10.4‰ and anhydrite formation temperatures were calculated to be 188–207°C. Oxygen isotope ratios ranged from +5.2 to +9.2‰ for montmorillonite, +3.2 to +4.5‰ for chlorite/montmorillonite mixed‐layer minerals, and +2.8 to +3.8‰ in mixtures of chlorite and mica. The formation temperatures of montmorillonite and of the chlorite–mica mixture were 160–250°C and 230–270°C, respectively. The isotope temperatures for clay minerals (220–270°C) and anhydrite (188°C) were significantly lower than the borehole temperature (308.3°C) measured just after the drilling, suggesting that temperature at this site is now higher than when clay minerals and anhydrite were formed.     

Discovery of Mass Independent Oxygen Isotopic Compositions in Superscale Nitrate Mineral Deposits from Turpan‐Hami Basin,Xinjiang, China and Its Significance

<正>The Turpan-Hami Basin in eastern Xinjiang is one of the driest regions on Earth and a premier environment to form and preserve nitrate.A large nitrate ore field in this basin was found recently.It is estimated there are about 2.5 billion tons of resources of nitrate,and the amount is as much as the Atacama Desert super-scale nitrate deposit in Chile.Nitrate is one of a few minerals with mass-independent fractionation(MIF),and the oxygen isotope MIF is an effective method to determine the source of nitrate.Theδ~(17)O,δ~(18)O of nitrate were measured by fluorination and thermal decomposition method.The date indicated that this is the first time that oxygen isotope MIF has been located in inland nitrate minerals.The results obtained by two methods are similar,⊿~(17)=δ~(17)O-0.52×δ~(18)O=12‰-17‰.The experiment and observation data proved that oxygen isotope MIF of nitrate are the result of photochemical reactions in the troposphere and stratosphere.Thus, evidence from MIF oxygen isotopic compositions indicate that long term atmospheric deposition of nitrate aerosol particles produced by photochemical reactions is the source of the deposits.     

Mercury enrichment and Hg isotopes in Cretaceous–Paleogene boundary successions: Links to volcanism and palaeoenvironmental impacts

We investigate the use of Hg as a proxy for volcanism by studying four distal and two proximal sections in relation to the Deccan volcanic center, straddling the Cretaceous–Paleogene (KPg) boundary at (a) Højerup (Denmark), Bottaccione and Padriciano (Italy), (b) Meghalaya and Jhilmili (India), and (c) Bajada del Jagüel (Argentina). Hg sequestration by organic matter results in constant Hg/TOC ratio and linear correlation between Hg content of the sediments and total organic carbon (TOC).Elevated Hg concentrations that deviate from this linear relationship represent most likely true Hg anomalies and these notable Hg/TOC spikes (all TOC <1%) are found in the Meghalaya, Bottaccione and Højerup sections within the CF2 planktic foraminiferal biozone (spike I), at the KPg boundary (spike II), and within the P1a planktic foraminiferal subzone (spike III). Spike III occurs also in the Jhilmili section. No clear correlation between Hg/TOC and Al₂O₃ exists in any of the studied sections. The Hg anomalies probably result from strong volcanic episodes of the Deccan phase-2 (started 250 kyr before the KPg boundary and lasted for 750 kyr) that exhaled sulfuric aerosols, carbon dioxide and other toxic agents which reached a critical threshold, represented in true Hg enrichments in the paleoenvironments. The possibility that Hg enrichments resulted from anoxia scavenging on the seafloor and penetration downward into sediments is not supported in the stratigraphic record of Mo/Al ratios redox proxy.Hg isotopes were analyzed in samples from all KPg boundary sections in this study and from Bidart, France, the latter for comparison. Hg isotopes yielded δ²⁰²Hg values ranging from −1 to −2‰ and Δ²⁰¹Hg signatures from 0 to 0.05‰ (spike II in Højerup, Bottaccione and Meghalaya KPg boundary layers) consistent with volcanic emission of Hg (0 to −2‰). The δ²⁰²Hg in spike I in Meghalaya and Padriciano and spike III in Jhilmili is consistent with volcanic emission of Hg. Two samples from Bajada del Jagüel and four from Bidart, however, display isotope signals compatible with volcanic emission/chondrite Hg. The results of three other samples are characteristic for reworked sediment, soil and/or peat. Most of the data show small positive Δ²⁰¹Hg, in favor of long-term atmospheric transport prior to deposition, supporting a volcanic origin for the Hg. The present study broadens, therefore, the potential use of Hg as stratigraphic marker and, moreover, confirms that in the critical KPg transition, Hg was enriched in paleoenvironments at three distinct stages during the Deccan phase-2.     

An enriched mantle source for potassic basanites: evidence from Karisimbi volcano,Virunga volcanic province,Rwanda

Lavas from Karisimbi, the largest volcano in the Virunga province in the Western Branch of the African rift on the Zaire-Rwandan border, constitute a suite of mafic potassic basanites and more evolved potassic derivatives. All of the lavas are potassic with K₂O/Na₂O1, and enriched in incompatible elements, with chondrite normalised (La/Yb)_n>18 and Nb/Zr>0.25. The ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd ratios reflect these enriched compositions, varying from 0.7052 and 0.51258 respectively in the K-basanites to 0.7132 and 0.51226 in the most evolved K-trachyte, although at MgO abundances >4% there is no systematic variation of isotope ratios with fractionation. At >4% MgO, lava compositions were controlled by assimilation and fractional crystallization in a sub-volcanic magma chamber. Trace-element and isotope variations in the more mafic lavas appear to reflect mixing between a primitive K-basanite (PKB) magma and a Sr-rich end-member, similar to melilite nephelinites from the neighbouring volcano, Nyiragongo. Both endmembers are mantle-derived and isotopically distinct, with the PKB being characterised by ⁸⁷Sr/⁸⁶Sr up to 0.707 and ¹⁴³Nd/¹⁴⁴Nd as low as 0.51236. Alternatively, isotope variations may be the time-integrated response to trace-element fractionations in a variably enriched mantle source. The Pb isotope variations within Karisimbi are complex. In the more evolved lavas all three ratios increase coherently with fractionation, whereas in the mafic varieties ²⁰⁶Pb/²⁰⁴Pb remains roughly constant at 19.2 while ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb vary from 15.67 to 15.78 and 39.49 to 40.80 respectively, defining sub-vertical trends, consistent with PKB-nephelinite magma mixing. The Nd and Sr isotopes indicate trace-element fractionation in the PKB source at 1 Ga, similar to ages derived from the overlying crust and suggesting a lithospheric origin. Elevated ²⁰⁸Pb/²⁰⁴Pb and ²⁰⁸Pb^*/²⁰⁶Pb^* values of the PKB are also consistent with Th/U fractionation at a similar time. However, this 1Ga age contrasts with that derived from the elevated ²⁰⁷Pb/²⁰⁴Pb ratios which indicate U/Pb fractionation during the Archaean. Crustal contamination can be excluded as the major control of Pb isotope variation in the PKB because their high Ce/Pb ratios (27) are similar to those typical of oceanic basalts. Parent/daughter trace-element fractionation and the high Ti, Nb and Ta abundances of the PKB lavas are all consistent with enrichment of a lithospheric source region by small-degree silicate melts at 1Ga. Comparison between measured and time-integrated trace-element ratios suggests that the degree of melting associated with recent magmatism was 5%. These data show that significant Th/U and Rb/Sr fractionation can be produced by intra-mantle melting processes and that high ²⁰⁸Pb/²⁰⁴Pb and ²⁰⁸Pb^*/²⁰⁶Pb^* values can evolve within the upper mantle and do not necessarily require the recycling of crustal material. Comparable isotope features in continental flood basalts and DUPAL ocean island basalts may be explained in a similar way.     

Germanium isotope measurements of high-temperature geothermal fluids using double-spike hydride generation MC-ICP-MS

We present a double-spike isotope dilution MC-ICP-MS technique for the determination of germanium (Ge) isotope fractionation. Using this technique we determined Ge isotope compositions of geothermal spring fluids, a Columbia River Basalt sample, and an in-house diatom standard. Our technique uses a ⁷³Ge/⁷⁰Ge double spike in combination with hydride generation for Ge extraction from the sample matrix. Fractionation is determined on the ⁷⁴Ge/⁷²Ge mass ratio. The double spike allows us to effectively correct analytical isotope fractionation. Our external standard reproducibility is 0.4‰ (2 SD) over the course of several months. The minimum quantity of Ge needed for isotope analysis is approximately 2 ng. Consistent with previous work on geothermal fluids, Ge in the geothermal spring samples presented here is enriched over Si as compared to low temperature weathering signatures. This observation is typically interpreted as Ge exclusion during silicate mineral precipitation (e.g., quartz). Our isotope results indicate that the analyzed high temperature fluids fractionate Ge isotopes with a range in δ⁷⁴Ge between −0.4‰ and −1.4‰ relative to a Columbia River basalt. We cautiously interpret the observed fractionation as preferential removal of heavy Ge isotopes out of solution during cooling of the hydrothermal fluid and subsequent precipitation of quartz.     

High-temperature Si isotope fractionation between iron metal and silicate

The Si stable isotope fractionation between metal and silicate has been investigated experimentally at 1800, 2000, and 2200 °C. We find that there is a significant silicon stable isotope fractionation at high temperature between metal and silicate in agreement with Shahar et al. (2009). Further we find that this fractionation is insensitive to the structure and composition of the silicate as the fractionation between silicate melt and olivine is insignificant within the error of the analyses. The temperature-dependent silicon isotope fractionation is Δ³⁰Si_{silicate-metal} = 7.45 ± 0.41 × 10⁶/T². We also demonstrate the viability of using laser ablation MC-ICPMS as a tool for measuring silicon isotope ratios in high pressure and temperature experiments.     

Non-biological fractionation of stable Ca isotopes in soils of the Atacama Desert, Chile

We measured Ca stable isotope ratios (δ^44/40Ca) in an ancient (2 My), hyperarid soil where the primary source of mobile Ca is atmospheric deposition. Most of the Ca in the upper meter of this soil (3.5 kmol m⁻²) is present as sulfates (2.5 kmol m⁻²), and to a lesser extent carbonates (0.4 kmol m⁻²). In aqueous extracts of variably hydrated calcium sulfate minerals, δ^44/40Ca_E values (vs. bulk Earth) increase with depth (1.4 m) from a minimum of −1.91‰ to a maximum of +0.59‰. The trend in carbonate-δ^44/40Ca in the top six horizons resembles that of sulfate-δ^44/40Ca, but with values 0.1-0.6‰ higher. The range of observed Ca isotope values in this soil is about half that of δ^44/40Ca values observed on Earth. Linear correlation among δ^44/40Ca, δ³⁴S and δ¹⁸O values indicates either (a) a simultaneous change in atmospheric input values for all three elements over time, or (b) isotopic fractionation of all three elements during downward transport. We present evidence that the latter is the primary cause of the isotopic variation that we observe. Sulfate-δ³⁴S values are positively correlated with sulfate-δ¹⁸O values (R² = 0.78) and negatively correlated with sulfate δ^44/40Ca_E values (R² = 0.70). If constant fractionation and conservation of mass with downward transport are assumed, these relationships indicate a δ^44/40Ca fractionation factor of −0.4‰ in CaSO₄. The overall depth trend in Ca isotopes is reproduced by a model of isotopic fractionation during downward Ca transport that considers small and infrequent but regularly recurring rainfall events. Near surface low Ca isotope values are reproduced by a Rayleigh model derived from measured Ca concentrations and the Ca fractionation factor predicted by the relationship with S isotopes. This indicates that the primary mechanism of stable isotope fractionation in CaSO₄ is incremental and effectively irreversible removal of an isotopically enriched dissolved phase by downward transport during small rainfall events.     

Mg isotope constraints on soil pore-fluid chemistry: Evidence from Santa Cruz, California

Mg isotope ratios (²⁶Mg/²⁴Mg) are reported in soil pore-fluids, rain and seawater, grass and smectite from a 90 kyr old soil, developed on an uplifted marine terrace from Santa Cruz, California. Rain water has an invariant ²⁶Mg/²⁴Mg ratio (expressed as δ²⁶Mg) at −0.79 ± 0.05‰, identical to seawater δ²⁶Mg. Detrital smectite (from the base of the soil profile, and therefore unweathered) has a δ²⁶Mg value of 0.11‰, potentially enriched in ²⁶Mg by up to 0.3‰ compared to the bulk silicate Earth Mg isotope composition (although within the range of all terrestrial silicates). The soil pore-waters show a continuous profile with depth for δ²⁶Mg, ranging from −0.99‰ near the surface to −0.43‰ at the base of the profile. Shallow pore-waters (<1 m) have δ²⁶Mg values that are similar to, or slightly lower than the rain waters. This implies that the degree of biological cycling of Mg in the pore-waters is relatively small and is quantified as <32%, calculated using the average Mg isotope enrichment factor between grass and rain (δ²⁶Mg_grass-δ²⁶Mg_rain) of 0.21‰. The deep pore-waters (1-15 m deep) have δ²⁶Mg values that are intermediate between the smectite and rain, ranging from −0.76‰ to −0.43‰, and show a similar trend with depth compared to Sr isotope ratios. The similarity between Sr and Mg isotope ratios confirms that the Mg in the pore-waters can be explained by a mixture between rain and smectite derived Mg, despite the fact that Mg and Sr concentrations may be buffered by the exchangeable reservoir. However, whilst Sr isotope ratios in the pore-waters span almost the complete range between mineral and rain inputs, Mg isotopes compositions are much closer to the rain inputs. If Mg and Sr isotope ratios are controlled uniquely by a mixture, the data can be used to estimate the mineral weathering inputs to the pore-waters, by correcting for the rain inputs. This isotopic correction is compared to the commonly used chloride correction for precipitation inputs. A consistent interpretation is only possible if Mg isotope ratios are fractionated either by the precipitation of a secondary Mg bearing phase, not detected by conventional methods, or selective leaching of ²⁴Mg from smectite. There is therefore dual control on the Mg isotopic composition of the pore-waters, mixing of two inputs with distinct isotopic compositions, modified by fractionation. The data provide (1) further evidence for Mg isotope fractionation at the surface of the Earth and (2) the first field evidence of Mg isotope fractionation during uptake by natural plants. The coherent behaviour of Mg isotope ratios in soil environments is encouraging for the development of Mg isotope ratios as a quantitative tracer of both weathering inputs of Mg to waters, and the physicochemical processes that cycle Mg, a major cation linked to the carbon cycle, during continental weathering.     

天然气甲烷碳同位素动力学模型与地质应用新进展

天然气甲烷碳同位素动力学模拟是在热模拟实验的基础上对甲烷碳同位素值进行数字模拟的一种研究方法。它在石油、天然气地球化学中具有广阔的应用前景：模拟甲烷碳同位素的整个演化趋势，模拟天然气成藏，进行精确的气源对比。分析了国外几个典型的甲烷碳同位素动力学模型，对各模型的特点和优缺点进行了简要的评述，并认识到Cramer 3是目前对实验数据模拟效果最好、适用范围最宽的一个模型。在此基础上，结合一些研究实例，探讨了天然气甲烷碳同位素动力学研究的发展方向。     

Insights into estuarine benthic dissolved organic carbon (DOC) dynamics using δC-DOC values, phospholipid fatty acids and dissolved organic nutrient fluxes

Benthic dissolved organic carbon (DOC) flux rates and changes in DOC isotope ratios, along with nutrient fluxes, phospholipid fatty acids concentration and carbon isotope ratios were measured in productive estuarine sediments over a diel cycle to determine the mechanisms driving benthic-pelagic coupling of DOC. There was uptake of DOC during the dark and efflux during the light at all sites. DOC uptake rates were related to benthic respiration (dark O₂ uptake) and effluxes were coupled to the trophic status (ratio of production to respiration) of the sediments. Highest uptake and efflux rates were observed at two high nutrient concentration sites. The DOC:DON ratio of water column dissolved organic matter (DOM) decreased during the dark and increased during the light indicating preferential uptake and release of carbon rich dissolved organic matter. The calculated carbon isotope ratio of the DOC taken up by the benthos was significantly more depleted than the bulk water column DOC pool, suggesting preferential uptake of selected components of the water column DOC pool. Generally the isotope ratio of the DOC released during the light was more enriched than that taken up during the dark, which suggests that the benthos has the potential to significantly alter the estuarine DOC pool. Uptake and efflux were coupled to respiration and algal grazing/mineralization, therefore increased nutrient loading may shift the composition of the estuarine DOC pool through changes in the magnitude of benthic DOC fluxes. A combination of biological (diel shifts in DOC production and consumption) and abiotic processes (flocculation) appear to be driving the observed benthic DOC dynamics at the study sites. This study was the first to measure carbon isotopic changes in the water column DOC pool due to benthic processes, and shows that the benthos can alter the estuarine DOC pool through diel differences in DOC uptake and efflux.