Changes In Isotopic Composition Research Articles

TAG Plume: Revisiting the Hydrothermal Neodymium Contribution to Seawater

We present results on the distribution of eNd and [Nd] from the TAG hydrothermal vent field and adjacent locations collected during the GEOTRACES GA03 cruise in October 2011. Our results show that Nd isotopes directly below and above the plume do not significantly deviate from average NADW (eNd = -12.3±0.2). Within the plume, however, isotope values are shifted slightly towards more radiogenic values up to eNd = -11.4. Interestingly at the same time a significant decrease in [Nd] along with rare earth element (REE) fractionation is observed, indicating enhanced scavenging within the plume despite the change in Nd isotopes. Elemental concentrations of Nd are reduced by 19.6 to 18.5 pmol/kg, coinciding with the maximum increase of mantle derived helium (xs3He) from 0.203 to 0.675 fmol/kg, resulting in an average 1.8 pmol/kg decrease in [Nd] relative to an expected linear increase with depth. The inventory loss of Nd within the plume sums up to 614 nmoles/m2, or 6 %, if a continuous increase of [Nd] with depth is assumed. Compared to BATS and the western adjacent station USGT11-14, the local inventory loss is even higher at 10 %. The tight relationship of xs3He increase and [Nd] decrease allows us to estimate scavenging rates at TAG suggesting 40 mol/yr are removed within the TAG plume. A global estimate using power output along ocean ridges yields an annual Nd removal of 3.44x106 mol/yr, which is about 71% of riverine and dust flux combined or 6 to 8% of the estimated global flux of Nd into the ocean. The change in Nd isotopic composition of up to 0.7 more radiogenic eNd values suggests an exchange process between hydrothermally derived particles and seawater in which during the removal process an estimated 1.1 mol/yr of hydrothermal Nd is contributed to the seawater at the TAG site. This estimate is only 0.1 % of the global Nd signal added to the ocean by boundary exchange processes at ocean margins, limiting the ability of changing the Nd isotopic composition on a global scale in contrast to the more significant estimated sink of elemental Nd in hydrothermal plumes from

Isotopic evolution of the protoplanetary disk and the building blocks of Earth and the Moon.

Nucleosynthetic isotope variability amongst Solar System objects is commonly used to probe the genetic relationship between meteorite groups and rocky planets, which, in turn, may provide insights into the building blocks of the Earth-Moon system1–5. Using this approach, it is inferred that no primitive meteorite matches the terrestrial composition such that the nature of the disk material that accreted to form the Earth and Moon is unconstrained6. This conclusion, however, is based on the assumption that the observed nucleosynthetic variability amongst inner Solar System objects predominantly reflects spatial heterogeneity. Here, we use the isotopic composition of the refractory element calcium to show that the inner Solar System’s nucleosynthetic variability in the mass-independent 48Ca/44Ca ratio (μ48Ca) primarily represents a rapid change in the μ48Ca composition of disk solids associated with early mass accretion to the proto-Sun. In detail, the μ48Ca values of samples originating from the ureilite and angrite parent bodies as well as Vesta, Mars and Earth are positively correlated to the masses of the inferred parent asteroids and planets – a proxy of their accretion timescales – implying a secular evolution of the bulk μ48Ca disk composition in the terrestrial planet-forming region. Individual chondrules from ordinary chondrites formed within 1 Myr of proto-Sun collapse7 record the full range of inner Solar System μ48Ca compositions, indicating a rapid change in the composition of the disk material. We infer that this secular evolution reflects admixing of pristine outer Solar System material to the thermally-processed inner protoplanetary disk associated with the accretion of mass to the proto-Sun. The indistinguishable μ48Ca composition of the Earth (0.2±3.9 ppm) and Moon (3.7±1.9 ppm) reported here is a prediction of our model if the Moon-forming impact involved protoplanets or precursors that completed their accretion near the end of the disk lifetime.

Similar mid-depth Atlantic water mass provenance during the Last Glacial Maximum and Heinrich Stadial 1

The delivery of freshwater to the North Atlantic during Heinrich Stadial 1 (HS1) is thought to have fundamentally altered the operation of Atlantic meridional overturning circulation (AMOC). Although benthic foraminiferal carbon isotope records from the mid-depth Atlantic show a pronounced excursion to lower values during HS1, whether these shifts correspond to changes in water mass proportions, advection, or shifts in the carbon cycle remains unclear. Here we present new deglacial records of authigenic neodymium isotopes – a water mass tracer that is independent of the carbon cycle – from two cores in the mid-depth South Atlantic. We find no change in neodymium isotopic composition, and thus water mass proportions, between the Last Glacial Maximum (LGM) and HS1, despite large decreases in carbon isotope values at the onset of HS1 in the same cores. We suggest that the excursions of carbon isotopes to lower values were likely caused by the accumulation of respired organic matter due to slow overturning circulation, rather than to increased southern-sourced water, as typically assumed. The finding that there was little change in water mass provenance in the mid-depth South Atlantic between the LGM and HS1, despite decreased overturning, suggests that the rate of production of mid-depth southern-sourced water mass decreased in concert with decreased production of northern-sourced intermediate water at the onset of HS1. Consequently, we propose that even drastic changes in the strength of AMOC need not cause a significant change in South Atlantic mid-depth water mass proportions.

Early anthropogenic impact on Western Central African rainforests 2,600 y ago

A potential human footprint on Western Central African rainforests before the Common Era has become the focus of an ongoing controversy. Between 3,000 y ago and 2,000 y ago, regional pollen sequences indicate a replacement of mature rainforests by a forest-savannah mosaic including pioneer trees. Although some studies suggested an anthropogenic influence on this forest fragmentation, current interpretations based on pollen data attribute the ''rainforest crisis'' to climate change toward a drier, more seasonal climate. A rigorous test of this hypothesis, however, requires climate proxies independent of vegetation changes. Here we resolve this controversy through a continuous 10,500-y record of both vegetation and hydrological changes from Lake Barombi in Southwest Cameroon based on changes in carbon and hydrogen isotope compositions of plant waxes. [Formula: see text]13C-inferred vegetation changes confirm a prominent and abrupt appearance of C4 plants in the Lake Barombi catchment, at 2,600 calendar years before AD 1950 (cal y BP), followed by an equally sudden return to rainforest vegetation at 2,020 cal y BP. [Formula: see text]D values from the same plant wax compounds, however, show no simultaneous hydrological change. Based on the combination of these data with a comprehensive regional archaeological database we provide evidence that humans triggered the rainforest fragmentation 2,600 y ago. Our findings suggest that technological developments, including agricultural practices and iron metallurgy, possibly related to the large-scale Bantu expansion, significantly impacted the ecosystems before the Common Era.

Evaporation and abstraction determined from stable isotopes during normal flow on the Gariep River, South Africa

Changes in the stable isotope composition of water can, with the aid of climatic parameters, be used to calculate the quantity of evaporation from a water body. Previous workers have mostly focused on small, research catchments, with abundant data, but of limited scope. This study aimed to expand such work to a regional or sub-continental scale. The first full length isotope survey of the Gariep River quantifies evaporation on the river and the man-made reservoirs for the first time, and proposes a technique to calculate abstraction from the river. The theoretically determined final isotope composition for an evaporating water body in the given climate lies on the empirically determined local evaporation line, validating the assumptions and inputs to the Craig-Gordon evaporation model that was used. Evaporation from the Gariep River amounts to around 20% of flow, or 40 m3/s, of which about half is due to evaporation from the surface of the Gariep and Vanderkloof Reservoirs, showing the wastefulness of large surface water impoundments. This compares well with previous estimates based on evapotranspiration calculations, and equates to around 1300 GL/a of water, or about the annual water consumption of Johannesburg and Pretoria, where over 10 million people reside. Using similar evaporation calculations and applying existing transpiration estimates to a gauged length of river, the remaining quantity can be attributed to abstraction, amounting to 175 L/s/km in the lower middle reaches of the river. Given that high water demand and climate change are global problems, and with the challenges of maintaining water monitoring networks, stable isotopes are shown to be applicable over regional to national scales for modelling hydrological flows. Stable isotopes provide a complementary method to conventional flow gauging for understanding hydrology and management of large water resources, particularly in arid areas subject to significant evaporation.

Faunal and stable isotopic analyses of benthic foraminifera from the Southeast Seep on Kimki Ridge offshore southern California, USA

We investigated the benthic foraminiferal faunal and stable carbon and oxygen isotopic composition of a 15-cm push core (NA075-092b) obtained on a Telepresence-Enabled cruise to the Southeast Seep on Kimki Ridge offshore southern California. The seep core was taken at a depth of 973 m in the vicinity of a Beggiatoa bacterial mat and vesicomyid clams (Calyptogena) and compared to previously published data of living assemblages from ~ 714 m, four reference cores obtained at ~ 1030 m, and another one at 739 m. All of the reference sites are also from the Inner Continental Borderland but with no evidence of methane seepage.No endemic species were found at the seep site and most of the taxa recovered there have been reported previously from other seep or low oxygen environments. Q- and R-mode cluster analyses clearly illustrated differences in the faunal assemblages of the seep and non-seep sites. The living assemblage at Southeast Seep was characterized by abundant Takayanagia delicata, Cassidulina translucens, and Spiroplectammina biformis, whereas the non-seep San Pedro Basin reference assemblage was comprised primarily of Chilostomella oolina and Globobulimina pacifica. Density and species richness were lower at the seep site compared to the non-seep site, reflecting the harsher living conditions there. The dead assemblage at the seep site was dominated by Gyroidina turgida compared to Cassidulina translucens at the ~ 1030 m non-seep site and Cassidulina translucens, Pseudoparrella pacifica, and Takayanagia delicata at the 739 m non-seep site. Density was three times lower at Southeast Seep than at the non-seep sites of comparable water depth but species richness was ~ 30% higher. Stable carbon isotopic values were considerably depleted in the seep samples compared to the non-seep samples, with a progression from lightest to heaviest average δ13C values evident at the seep site reflecting microhabitat preference and vital effect: the deep infaunal species of Globobulimina, the shallow infaunal species Uvigerina peregrina, the epifaunal species Cibicidoides wuellerstorfi, and the shallow infaunal but aragonite-shelled species Hoeglundina elegans. The δ13C values downcore among each benthic species indicates ongoing fluid seepage through at least the last 3800 cal yr B.P. at Southeast Seep. Besides the continual local seepage, evidence from δ13C values of planktic foraminifera in the seep core suggest two pulses of methane (at 3000 and 3700 cal yr B.P.) were released that were large enough to influence much of the water column. Paired benthic and planktic foraminiferal stable oxygen isotope records provide evidence that there were no paleoenvironmental changes such as increased bottom-water temperature or changes in oxygen isotopic composition of bottom and pore waters during this 3800-year record to induce the methane releases. Instead, Southeast Seep appears to be the result of local faulting providing pathways for fluid to flow to the seafloor at a fault stepover or transpressional bend in the regional strike-slip system.

Variations of stable isotope fractionation during bacterial chromium reduction processes and their implications

Abstract Many chemical processes generate subtle but readily measured changes in isotope compositions of elements across the periodic table. The elements involved therefore carry diagnostic information about their chemical histories in complex geochemical or biochemical environments. Distinctive Cr isotope signatures can be used to identify immobilization processes of Cr in the environment, such as microbial Cr(VI) reduction, abiotic Cr(VI) reduction, and adsorption. Here we demonstrate that under well-controlled conditions, Cr isotopes can also be used to distinguish between different biological Cr(VI) reduction pathways. The reduction of Cr(VI) by two facultative anaerobic bacteria, Pseudomonas fluorescens LB 300 and Shewanella oneidensis MR 1, was investigated to determine the conditions under which Cr(VI) is reduced and to quantify the corresponding isotope signatures. The present study considers the effects of a broad range of parameters on Cr isotope fractionation, including bacterial species, electron donors, pH, and respiration pathways (aerobic vs. anaerobic) that must be considered for understanding Cr isotope variations under different experimental and environmental conditions. In the bacterial Cr(VI) reduction experiments, the 53Cr/52Cr isotope ratio of the remaining Cr(VI) increased by up to + 8‰, indicating that lighter isotopes of Cr were preferentially reduced. In aerobic experiments, although Cr reduction rates increased as pH increased from 4 to 8, the fractionation factor did not vary significantly (e = −3.21 ± 0.18‰). Experiments using different electron donors demonstrated that citrate promoted the greatest Cr reduction rate compared with glucose, acetate, and propionate. Under aerobic conditions, although the Cr(VI) reduction rates varied substantially between different experimental settings, the isotope fractionation factors were indistinguishable between all the environmental conditions examined (e = −3.1‰), with the exception of when citrate was the electron donor (e = −4.3‰). Cr reduction rates were generally much faster under anaerobic conditions for both bacteria investigated. The utilisation of different electron donors resulted in the same Cr reduction rates by the bacteria, but fractionated Cr with a broad range of isotope fractionation factors, from − 1.58 ± 0.16‰ to − 4.93 ± 0.36‰. Although it has been proposed in many previous studies that there is an inverse relationship between reduction rates and the fractionation factors, no clear relationship between the reduction rates and fractionation factors was observed in this study. The Cr isotope fractionation factors e were insensitive to pH and electron donor concentration, but dependent on the type of electron donors and redox conditions in the cultures. This indicates that isotope variations may be used to identify when different biological pathways are involved, and so to investigate metabolic processes. The e value from all experimental conditions examined ranged between − 1.58 and − 4.93‰, with a mean value at − 3.3‰. While Cr isotopes might be used to separate the effects of abiotic and microbially mediated reduction in environmental sites, the fractionation factors from reduction by individual bacterial species overlap with those from several individual abiotic reduction processes, suggesting that site-specific data (e.g., fractionation factors associated with indigenous bacterial populations and local groundwater chemistry) are required in order to use Cr isotopes to distinguish between different reduction mechanisms.

Seasonal variations of leaf wax n-alkane molecular composition and δD values in two subtropical deciduous tree species: Results from a three-year monitoring program in central China

We investigated the seasonal variations of the molecular and hydrogen isotopic compositions of leaf cuticular n-alkanes (δDalk) in two subtropical deciduous tree species (Quercus chenii, Liquidambar formosana) over a three-year period. Average chain length values of long chain n-alkanes in both species are lower in young leaves than in mature ones. The δDalk values in both tree species show seasonal fluctuations that can be as large as 78‰ in a single year. The seasonal changes in molecular and isotopic compositions suggest that leaf wax n-alkanes in these subtropical deciduous tree species integrate environmental information over a large portion of the annual growth cycle in response to fluctuations in environmental stresses (e.g. storms, droughts). In addition, the changes reveal that seasonal patterns of δDalk can differ between different deciduous species at the same location and among different years. Spring leaves collected in 2014 had more negative δDalk values than those collected in 2015 and 2016, possibly responding to differences in annual precipitation D/H ratios and associated atmospheric circulation. These preliminary results highlight that extended seasonal monitoring of leaf wax δDalk values can improve their application to reconstructing paleohydrological histories.

Strontium isotopes reveal weathering processes in lateritic covers in southern China with implications for paleogeographic reconstructions.

The isotope ratios of Sr are useful tracers for studying parent material sources, weathering processes, and biogeochemical cycling. Mineralogical and geochemical investigations of two lateritic weathering covers, in an area close to the Tropic of Cancer (Guangxi Province, southern China), were undertaken to study the regional weathering processes and Sr isotopic sources. We found that weathering and decomposition of Rb- and Sr-bearing minerals change the Sr isotopic composition in weathering products (lateritic soils). Weathering of illite lowered the 87Sr/86Sr ratio whereas dissolving and leaching of carbonate minerals increased the 87Sr/86Sr ratio. An Fe nodular horizon is widely developed on the top of the weathering covers in the studied area and it differs from the lateritic soil horizon in mineral composition, construction, and elemental concentration. Furthermore, both Fe2O3 and P2O5 (concentrations) are negatively correlated with the 87Sr/86Sr ratios, suggesting fixation of apatite by Fe oxides is a controlling factor of the Sr isotopic composition in the Fe nodular horizon. The 87Sr/86Sr and Nb/Sr ratios imply the contents and proportions of Fe nodules and clay are critical in controlling the changes of Sr isotopic composition in the Fe nodular horizon. The two stages of the weathering process of carbonate rocks are revealed by the87Sr/86Sr versus Nb/Sr diagram. The 87Sr/86Sr and Rb/Sr ratios suggest that Sr isotopes in the weathering covers within the studied area are derived mainly from parent rock weathering and that the contributions from allothogenic Sr isotopes are limited. A comparison of Sr isotopic composition signatures in the weathering covers of the studied area and Guizhou Province provided insight into the Sr isotopic source and paleogeographic evolution of southern China. From the Permian to the Triassic, the continental fragment sources of the South China sedimentary basin changed significantly. In the Permian, Southern China presented the paleogeographic pattern that the north was higher (in elevation) than the south.

Markers of Soil Organic Matter Transformation in Permafrost Peat Mounds of Northeastern Europe

For the paleoreconstruction of permafrost peat mounds and the identification of plant communities participating in the formation of peat, the contents of n-alkanes (C20–C33) have been determined, and relative changes in the stable isotope compositions of carbon and nitrogen and the C/N ratio have been analysed. Several indices (CPIalkanes, Paq, Pwax) have been calculated to assess the degree of decomposition of the peats studied and the contributions of different plant species to their formation. It has been found that shortand long-chain n-alkanes are concentrated in high-moor peat, while medium-chain alkanes are typical for transitional peat. Integrated analysis of the studied markers has shown that the botanical and material composition of peat, anaerobic conditions of bog formation, and permafrost play an important role in the preservation of organic carbon in permafrost peat mounds. Alternation of plant associations is the main reason for changes in n-alkane concentrations, C/N ratios, and δ13C values.

Origin of carbonatites of the Matcha alkaline pluton from Turkestan-Alai ridge, Kyrgyz Southern Tien Shan

Postorogenic alkaline intrusions in the Turkestan-Alai segment of the Southern Tien Shan coexist with dikes and veins of carbonatites dated at ∼220 Ma. They are primarily composed of calcite and dolomite (60–85 %), as well as sodic amphibole, phlogopite, clinopyroxene, microcline, albite, apatite, and magnetite, with accessory niobate, ilmenite, Nb-rutile, titanite, zircon, baddeleyite, monazite-(Ce), barite, and sulfides. The rocks share mineralogical and geochemical similarity with carbonatites that originated by liquid immiscibility at high temperatures above 500°C. Silicate and salt-carbonate melts are derived from sources with mainly negative bulk εND(t) ∼ from −11 to 0 and high initial 87Sr/86Sr ratios (∼ 0.7061-0.7095) which may be due to mixing of PREMA and EM-type mantle material. Pb isotopic ratios in accessory pyrrhotite (206Pb/204Pb = 18.38; 207Pb/204Pb = 15.64; 208Pb/204Pb = 38.41) exhibit an EM 2 trend. The intrusions bear signatures of significant crustal contamination as a result of magma genesis by syntexis and hybridism. Concordant isotope composition changes of δ13C (−6.5 to −1.9 ‰), δ18O (9.2-23 %„), δD (−58 to −41 %„), and δ34S (12.6-12.8 ‰) in minerals and rocks indicate inputs of crustal material at the stage of melting and effect of hot fluids released during dehydration of metamorphosed oceanic basalts or sediments. The observed HFSE patterns of the oldest alkaline gabbro may be due to interaction of the primary mafic magma with IAB-type material. The isotope similarity of alkaline rocks with spatially proximal basalts of the Tarim large igneous province does not contradict the evolution of the Turkestan-Alai Triassic magmatism as the «last echo» of the Tarim mantle plume.

The Molybdenum Isotope System as a Tracer of Slab Input in Subduction Zones: An Example From Martinique, Lesser Antilles Arc

AbstractMolybdenum isotopes are fractionated by Earth‐surface processes and may provide a tracer for the recycling of crustal material into the mantle. Here, we examined the Mo isotope composition of arc lavas from Martinique in the Lesser Antilles arc, along with Cretaceous and Cenozoic Deep Sea Drilling Project sediments representing potential sedimentary inputs into the subduction zone. Mo stable isotope composition (defined as δ98Mo in ‰ deviation from the NIST 3134 standard) in lavas older than ∼7 million years (Ma) exhibits a narrow range similar to and slightly higher than MORB, whereas those younger than ∼7 Ma show a much greater range and extend to unusually low δ98Mo values. Sediments from DSDP Leg 78A, Site 543 have uniformly low δ98Mo values whereas Leg 14, Site 144 contains both sediments with isotopically light Mo and Mo‐enriched black shales with isotopically heavy Mo. When coupled with published radiogenic isotope data, Mo isotope systematics of the lavas can be explained through binary mixing between a MORB‐like end‐member and different sedimentary compositions identified in the DSDP cores. The lavas older than ∼7 Ma were influenced by incorporation of isotopically heavy black shales into the mantle wedge. The younger lavas are the product of mixing isotopically light sedimentary material into the mantle wedge. The change in Mo isotope composition of the lavas at ∼7 Ma is interpreted to reflect the removal of the Cretaceous black shale component due to the arrival of younger ocean crust where the age‐equivalent Cretaceous sediments were deposited in shallower oxic waters. Isotopic fractionation of Mo during its removal from the slab is not required to explain the observed systematics in this system.

Evidence for major input of riverine organic matter into the ocean

The changes in the structure of XAD-8 isolated dissolved organic matter (DOM) samples along a river (Penobscot River) to estuary (Penobscot Bay) to ocean (across the Gulf of Maine) transect and from the Pacific Ocean were investigated using selective and two dimensional (2D) nuclear magnetic resonance (NMR) spectroscopy coupled with elemental and carbon isotope analysis. The results provide important insights into the nature of relatively stable structures in the river-to-ocean continuum and the enigma of the fate of terrestrial DOM in the marine system. First, lignin and carboxyl-rich alicyclic molecules (CRAMs), which are indistinguishable from mass spectrometry, were clearly differentiated with NMR spectroscopy. NMR unambiguously showed that CRAMs persisted along the river-to-ocean transect and in the Pacific Ocean, while lignin residues dramatically decreased in abundance from the river to the coastal ocean and the Pacific Ocean. The results challenge a previous conclusion that lignin-derived compounds are refractory and can accumulate in the coastal ocean. The loss of terrestrial plant-derived aromatic compounds such as lignin and tannin residues throughout the sequence of riverine, coastal, and open ocean DOM extracts could also partially explain the decreasing organic carbon recovery by XAD-8 isolation and the change in carbon stable isotope composition from riverine DOM (δ13C −27.6‰) to ocean DOM (δ13C −23.0‰) extracts. The observation, from advanced NMR, of similar CRAM molecules in XAD-8 isolated DOM samples from the Penobscot River to the Penobscot Bay and from the ocean refutes a previous conclusion that XAD-isolated DOM samples from seawater and river are distinctly different. The alicyclic structural features of CRAMs and their presence as the major structural units in DOM extracts from the Penobscot River to Gulf of Maine transect, together with the deduced old 14C age of CRAMs in the ocean, imply that terrestrial CRAMs may persist on timescales long enough to be transported into the ocean.

Mineralogy and geochemistry of triassic carbonatites in the Matcha alkaline intrusive complex (Turkestan-Alai Ridge, Kyrgyz Southern Tien Shan), SW Central Asian orogenic belt

Postorogenic intrusions of essexites and alkaline and nepheline syenites in the Turkestan-Alai segment of the Kyrgyz Southern Tien Shan coexist with dikes and veins of carbonatites dated at ∼220 Ma by the Ar–Ar and Rb–Sr age methods. They are mainly composed of calcite and dolomite (60–85%), as well as sodic amphibole, phlogopite, clinopyroxene, microcline, albite, apatite, and magnetite, with accessory niobate, ilmenite, Nb-rutile, titanite, zircon, baddeleyite, monazite-(Ce), barite, and sulfides. The rocks share mineralogical and geochemical similarity with carbonatites that originated by liquid immiscibility at high temperatures above 500 °C. Alkaline silicate and salt-carbonate melts are derived from sources with mainly negative bulk εNd(t) ∼ from −11 to 0 and high initial 87Sr/86Sr ratios (∼0.7061–0.7095) which may be due to mixing of PREMA and EM−type mantle material. Pb isotopic ratios in accessory pyrrhotite (206Pb/204Pb = 18.38; 207Pb/204Pb = 15.64; 208Pb/204Pb = 38.41) exhibit an EM2 trend. The intrusions bear signatures of significant crustal contamination as a result of magma genesis by syntexis and hybridism. Concordant isotope composition changes of δ13C (−6.5 to −1.9‰), δ18O (9.2–23‰), δD (−58 to −41‰), and δ34S (12.6–12.8‰) in minerals and rocks indicate inputs of crustal material at the stage of melting and effect of hot fluids released during dehydration of metamorphosed oceanic basalts or sediments. The observed HFSE patterns of the oldest alkaline gabbro may be due to interaction of the primary mafic magma with IAB-type material. The isotope similarity of alkaline rocks with spatially proximal basalts of the Tarim large igneous province does not contradict the evolution of the Turkestan-Alai Triassic magmatism as the “last echo” of the Tarim mantle plume.

Experimental evaporation of hyperacid brines: Effects on chemical composition and chlorine isotope fractionation

Hyperacid brines from active volcanic lakes are some of the chemically most complex aqueous solutions on Earth. Their compositions provide valuable insights into processes of elemental transfer from a magma body to the surface and interactions with solid rocks and the atmosphere. This paper describes changes in chemical and δ37Cl signatures observed in a 1750 h isothermal evaporation experiment on hyperacid (pH 0.1) sulphate-chloride brine water from the active lake of Kawah Ijen volcano (Indonesia). Although gypsum was the only evaporite mineral identified in the evolving brine, decreasing Si concentrations may ultimately result in amorphous silica precipitation. Geochemical simulations predict the additional formation of elemental sulphur at lower water activities (aH2O ≤ 0.65) that were not reached in the experiment. Absence of other sulphates and halides despite the high load of dissolved elements (initial TDS ca. 100 g/kg) can be attributed to increased solubility of metals, promoted by extensive formation of complexes between the variety of cations and the major anions (HSO4−, Cl−, F−) present. Chlorine deviations from a conservative behaviour point to losses of gaseous hydrogen chloride (HCl(g)) and consequently an increase in Br/Cl ratios.Chlorine isotope fractionation that accompanied the escape of HCl(g) showed a marked change in sign and magnitude in the course of progressive evaporation of the brine. The calculated factor of fractionation between HCl(g) and dissolved Cl for the initial interval (before 500 h) is positive (1000lnαHCl(g)-Cldiss.=+1.55±0.49‰to+3.37±1.11‰), indicating that, at first, the escaping HCl(g) was isotopically heavier than the dissolved Cl remaining in the brine. Conversely, fractionation shifted to the opposite direction in the subsequent interval (1000lnαHCl(g)-Cldiss.=5.67±0.17‰to-5.64±0.08‰), in agreement with values reported in literature. It is proposed that Cl isotopic fractionation in highly acidic brines is controlled by the distribution of dissolved chlorine species, which changes from Cl− to HClo dominance with the progressive pH decline.The Kawah Ijen lake acquired its extreme composition through influx of sulphur and halogen-rich magmatic gas components and extensive rock dissolution. If hyperacid brines with comparable chemical composition existed on Mars, evaporation processes up to the extent reported here (aH2O=0.85), were likely accompanied by losses of gaseous HCl. The resulting changes in Cl isotope compositions, Br/Cl, S/Cl and other ratios in the residual brine might be potentially recorded in assemblages of halogen-bearing secondary evaporation minerals. Also, volcanic-hydrothermal brines as these would extend the stability of liquid water on the Martian surface down to a temperature of −90 °C.

Accounting for seasonal isotopic patterns of forest canopy intercepted precipitation in streamflow modeling

Forest canopy interception alters the isotopic tracer signal of precipitation leading to significant isotopic differences between open precipitation (δOP) and throughfall (δTF). This has important consequences for the tracer-based modeling of streamwater transit times. Some studies have suggested using a simple static correction to δOP by uniformly increasing it because δTF is rarely available for hydrological modeling. Here, we used data from a 38.5 ha spruce forested headwater catchment where three years of δOP and δTF were available to develop a data driven method that accounts for canopy effects on δOP. Changes in isotopic composition, defined as the difference δTF-δOP, varied seasonally with higher values during winter and lower values during summer. We used this pattern to derive a corrected δOP time series and analyzed the impact of using (1) δOP, (2) reference throughfall data (δTFref) and (3) the corrected δOP time series (δOPSine) in estimating the fraction of young water (Fyw), i.e., the percentage of streamflow younger than two to three months. We found that Fyw derived from δOPSine came closer to δTFref in comparison to δOP. Thus, a seasonally-varying correction for δOP can be successfully used to infer δTF where it is not available and is superior to the method of using a fixed correction factor. Seasonal isotopic enrichment patterns should be accounted for when estimating Fyw and more generally in catchment hydrology studies using other tracer methods to reduce uncertainty.

Hinterland drainage closure and lake formation in response to middle Eocene Farallon slab removal, Nevada, U.S.A.

Hinterland basins can accumulate high resolution archives of orogenic processes and continental climate, but are challenging to reconstruct due to tectonic overprinting and the inherent complexity of their lithofacies assemblages. The Cordilleran hinterland of northeast Nevada has been interpreted to have overlain a flattened Farallon slab from the Late Cretaceous to Eocene. Slab removal and advection of asthenospheric mantle beneath Nevada have been invoked to explain a southwestward migrating wave of Eocene to Oligocene volcanism and proposed as a driver for topographic uplift. However, the timing of slab removal and possible subsequent delamination of North American lithospheric mantle can only ambiguously be related to the surface record. Subsequent Neogene extension and basin filling has complicated the correlation and interpretation of strata that record these events. Here we apply single crystal sanidine 40Ar/39Ar geochronology to 26 ash beds in northeast Nevada to reconstruct Paleogene geographic and hydrologic evolution. We use these ages and legacy geochronology to compare lithofacies and isotope proxy records of meteoric waters to regional tectonics and global climate, and assess competing tectonic interpretations for lake basin formation. Lakes formed locally prior to ca. 48.7 Ma in northeast Nevada, coeval with foreland lakes of the Green River Formation. The most expansive phase of lacustrine deposition resulted in onlap onto locally derived fluvial deposits and folded Paleozoic bedrock, and occurred between ca. 43.4 and ca. 40.8 Ma. Elko Formation strata exhibit a basin-wide transition from fluvial-lacustrine to fluctuating profundal lithofacies at ca. 42.7 Ma, suggesting a shift towards regional hydrologic closure. The stromatolitic upper Elko Formation is intercalated with ash fall tuffs and several partially welded to unwelded ignimbrites from increasingly proximal volcanism. Elko Formation deposition ended by ca. 40.4 Ma. 40Ar/39Ar ages for seven ash beds in the Dead Horse Formation at Copper Basin in northern Elko County indicate intermittent ash bed deposition between 45.2 Ma and 38.6 Ma, and an episode of lacustrine deposition between 39.8 Ma and 38.6 Ma that post-dates the main phase of Lake Elko. δD values of volcanic glass sampled from dated ash beds reflect changes in the hydrogen isotope compositions of local Eocene waters, and systematically vary by 80–102‰ according to their depositional environment. The Elko Formation and overlying volcanic strata are overlain regionally by a pronounced unconformity of ∼20 m.y. In the Copper Basin area, deposition continued locally into the Oligocene in the hanging wall of a ductile detachment. The geochronologic and isotopic framework presented here permits reanalysis of the Piñon Range carbonate proxy record that was previously interpreted to record both regional uplift and the middle Eocene climatic optimum. New data suggest instead that isotope values of hydration waters within the Elko Formation were strongly influenced by evaporation, and a change from lacustrine to non-lacustrine conditions can account for the δ18O shift that was interpreted to reflect regional uplift. Moreover, the end of Elko Formation deposition predated the middle Eocene climatic optimum. We interpret the overall record of drainage ponding and paleovalley inundation, progressively more evaporative lacustrine conditions, increasingly proximal volcanism, and subsequent prolonged unconformity to reflect the surface effects of progressive NE to SW removal of the Farallon slab.

Evidence of methane and carbon dioxide migration to the near surface zone in the area of the abandoned coal mines in Wałbrzych District (Lower Silesian Coal Basin, SW Poland) based on periodical changes of molecular and isotopic compositions

The objective of this paper is to determine the reasons, origin and character of periodical changes of methane and carbon dioxide concentrations in the near-surface zone as well as emission of these gases to atmosphere after closing bituminous coal and anthracite mines in the former Wałbrzych Coal District (SW Poland). The measurements were performed during the period including the active impact of “water piston effect” on the migration of a coal-bearing gases as well as the period of stabilization of water table of the Pennsylvanian aquifer. In the years 1997–2005, 20 sampling sessions were completed during which 3210 soil gas samples were collected at a depth of about 1.2m and along 4 measurement lines located in the Gorce and the Sobięcin depressions. Maximum methane and carbon dioxide concentrations measured in soil gas samples reached 32.4 and 15.7vol%, respectively. Isotopic study shows that coal-bed gases, recent microbial methane, and multigenetic carbon dioxide from degassing of ground-waters of the Upper Pennsylvanian aquifer occur within the near-surface zone of the Wałbrzych Coal District. Within the Serpukhovian Wałbrzych and Upper Bashkirian-Moscovian Žacleř coal-bearing formations three genetic types of coal-bed gases occur: Variscan thermogenic (methane, higher gaseous hydrocarbons and carbon dioxide), endogenic (abiogenic) carbon dioxide and “late” (Late Cretaceous) and recent microbial methane and carbon dioxide. Changes of mean concentrations of methane and carbon dioxide in the near-surface zone recorded during years of studies demonstrated the influence of “water piston effect”, which drives migration of coalbed gases towards the earth surface. In both the Gorce and the Sobięcin depressions, gas migrates with various intensity. Generally, the lower methane emission measured in the years 2004–2005, and compared with the period 1999–2000, resulted from the stabilization of groundwater table whereas higher carbon dioxide emission confirms the degassing of shallow groundwaters. Anomalous concentrations of methane and carbon dioxide were related to numerous faults and fracture systems cutting the steeply dipping Upper Mississippian and Pennsylvanian coal-bearing formations, and to the outcrops of these rocks. However, in the near-surface zone, multiproportional mixing of coal-bed gases, recent microbial methane and carbon dioxide is observed. Periodical changes of stable carbon isotope composition of methane and carbon dioxide of near-surface zone in particular sessions are caused by the time-related change of location of water table of Pennsylvanian aquifer in the complicated structure of the Gorce and Sobięcin depressions. Persistently anomalous concentrations of methane and carbon dioxide in the near surface zone, still observed after several-years-long stabilization of groundwater table, seem to indicate a continuous supply of coalbed gases to the near-surface zone through pervious dislocations. Such an interpretation is confirmed by the extreme value of methane emission detected at a particular sampling site after the cessation of the “water piston” effect. It was presumably caused by the secondary intensification of gas flux from deep sources, triggered by neotectonic movements in the study area.

Modeling of biotic and abiotic processes affecting phosphate oxygen isotope ratios in a mineral-water-biota system

Abiotic and biotic reactions operate side by side in the cycling of phosphorus (P) in the environment, but the relative roles of these two reactions vary both spatially and temporally. In biotic reactions, the uptake and release of P are catalyzed by enzymes and thus change phosphate oxygen isotope ratios, while in abiotic reactions, the absence of hydrolysis-condensation reactions results in no apparent changes in isotope composition, except short-term kinetic isotope effect due solely to preferential ion exchange. Therefore, isotope method could be a promising tool to differentiate relative roles of these two reactions in the environment but the relationship of the dynamic concentration and isotope exchange at the biota-water interface is largely unknown. In this study, we aimed to develop a process-based isotope model underpinning the competition of abiotic (sorption, desorption, and ion exchange) and biotic (uptake, metabolism, and release) reactions during uptake and recycling of ferrihydrite-bound P by E. coli. Our model comprises equations describing the partitioning relationship among different P pools and their corresponding oxygen isotope compositions and is based exclusively on oxygen isotope exchange at multiple sites including mineral surface, aqueous phase, and bacterial cells. The process-based model adequately reproduced the measured concentration and isotope compositions over time. Furthermore, parametric and sensitivity analyses using the model indicated that the rate of biological uptake of P was the major factor controlling the changes of phosphate isotope composition. In conclusion, our model provides new insights into a mechanistic aspect of isotope exchange and could be potentially useful for future efforts to understand the interplay of biotic and abiotic factors on phosphorus cycling in natural environments.

Origin of heavy Fe isotope compositions in high-silica igneous rocks: A rhyolite perspective

The origin of heavy Fe isotope compositions in high-silica (>70wt% SiO2) igneous rocks remains a highly controversial topic. Considering that fluid exsolution in eruptive rocks is more straight-forward to constrain than in plutonic rocks, this study addresses the problem of Fe isotope fractionation in high-silica igneous rocks by measuring Fe isotope compositions of representative rhyolitic samples from the Neoproterozoic volcanic-sedimentary basins in southern China and the Triassic Tu Le Basin in northern Vietnam. The samples show remarkably varied δ56FeIRMM014 values ranging from 0.05±0.05‰ to 0.55±0.05‰, which is among the highest values reported from felsic rocks. The extensional tectonic setting and short melt residence time in magma chambers for the studied rhyolites rule out Soret diffusion and thermal migration processes as causes of the high δ56Fe values. Effects of volcanic degassing and fluid exsolution on bulk rock δ56Fe values for the rhyolites are also assessed using bulk rock geochemical indicators and Rayleigh fractionation models, and these processes are found to be insufficient to produce resolvable changes in Fe isotope compositions of the residual melt. The most probable mechanism accounting for heavy Fe isotope compositions in the high-silica rhyolites is narrowed down to fractional crystallization processes in the magma before rhyolite eruption. Removal of isotopically light Fe-bearing minerals (i.e. ulvöspinel-rich titanomagnetite, ilmenite and biotite) is proposed as the main cause of Fe isotope variation in silicic melts during magmatic evolution. This study implies that crystal fractionation is the dominant mechanism that controls Fe isotope fractionation in eruptive rocks and Fe isotopes could be used to study magmatic differentiation of high-silica magmas.