Rayleigh Distillation Research Articles

Oxygen isotope analysis of bacterial and fungal manganese oxidation.

The ability of micro-organisms to oxidize manganese (Mn) from Mn(II) to Mn(III/IV) oxides transcends boundaries of biological clade or domain. Many bacteria and fungi oxidize Mn(II) to Mn(III/IV) oxides directly through enzymatic activity or indirectly through the production of reactive oxygen species. Here, we determine the oxygen isotope fractionation factors associated with Mn(II) oxidation via various biotic (bacteria and fungi) and abiotic Mn(II) reaction pathways. As oxygen in Mn(III/IV) oxides may be derived from precursor water and molecular oxygen, we use a twofold approach to determine the isotope fractionation with respect to each oxygen source. Using both 18 O-labeled water and closed-system Rayleigh distillation approaches, we constrain the kinetic isotope fractionation factors associated with O atom incorporation during Mn(II) oxidation to -17.3‰ to -25.9‰ for O2 and -1.9‰ to +1.8‰ for water. Results demonstrate that stable oxygen isotopes of Mn(III/IV) oxides have potential to distinguish between two main classes of biotic Mn(II) oxidation: direct enzymatic oxidation in which O2 is the oxidant and indirect enzymatic oxidation in which superoxide is the oxidant. The fraction of Mn(III/IV) oxide-associated oxygen derived from water varies significantly (38%-62%) among these bio-oxides with only weak relationship to Mn oxidation state, suggesting Mn(III) disproportionation may account for differences in the fraction of mineral-bound oxygen from water and O2 . Additionally, direct incorporation of molecular O2 suggests that Mn(III/IV) oxides contain a yet untapped proxy of δ18OO2 of environmental O2 , a parameter reflecting the integrated influence of global respiration, photorespiration, and several other biogeochemical reactions of global significance.

Salt precipitation and dissolution in the late Quaternary Dead Sea: Evidence from chemical and δ37Cl composition of pore fluids and halites

The chemical composition and δ37Cl of pore fluids from the ICDP core drilled in the deepest floor of the terminal and hypersaline Dead Sea, and halites from the adjacent Mount Sedom salt diapir, are used to establish the dynamics of halite precipitation and dissolution during the last interglacial and glacial periods. Between ∼132 and 116 thousand years ago (ka) halites precipitated in the lake resulting in the expulsion of Na+ and Cl− from the residual solution. Over 50% of the Cl− reservoir was removed, resulting in a decrease in the Na/Cl ratio from 0.57 to 0.19. This process was accompanied by a decrease in δ37Cl values in the precipitating halites and the associated residual Cl− in the lake. The observed decrease fits a Rayleigh distillation curve with a fractionation factor of Δ(NaCl–Dead Sea solution) = +0.32‰ (±0.12) determined in the present study. This behavior implies negligible contribution of external sources of Cl− to the lake during the main peak of the last interglacial, MIS5e. Subsequently, during the last glacial (ca. 117 to 17 ka) dissolution of halite took place, the Na+ and Cl− inventory were replenished, accompanied by an increase in Na/Cl from 0.21 to 0.55 and in the δ37Cl values from −0.46‰ to −0.12‰. While the lake underwent significant dilution during that time, the decrease in salinity was somewhat suppressed by the dissolution of the halite which was mostly derived from Mount Sedom salt diapir.

Sulfur isotope's signal of nanopyrites enclosed in 2.7 Ga stromatolitic organic remains reveal microbial sulfate reduction.

Microbial sulfate reduction (MSR) is thought to have operated very early on Earth and is often invoked to explain the occurrence of sedimentary sulfides in the rock record. Sedimentary sulfides can also form from sulfides produced abiotically during late diagenesis or metamorphism. As both biotic and abiotic processes contribute to the bulk of sedimentary sulfides, tracing back the original microbial signature from the earliest Earth record is challenging. We present in situ sulfur isotope data from nanopyrites occurring in carbonaceous remains lining the domical shape of stromatolite knobs of the 2.7-Gyr-old Tumbiana Formation (Western Australia). The analyzed nanopyrites show a large range of δ34 S values of about 84‰ (from -33.7‰ to +50.4‰). The recognition that a large δ34 S range of 80‰ is found in individual carbonaceous-rich layers support the interpretation that the nanopyrites were formed in microbial mats through MSR by a Rayleigh distillation process during early diagenesis. An active microbial cycling of sulfur during formation of the stromatolite may have facilitated the mixing of different sulfur pools (atmospheric and hydrothermal) and explain the weak mass independent signature (MIF-S) recorded in the Tumbiana Formation. These results confirm that MSR participated actively to the biogeochemical cycling of sulfur during the Neoarchean and support previous models suggesting anaerobic oxidation of methane using sulfate in the Tumbiana environment.

The Fe-Zn Isotopic Characteristics and Fractionation Models: Implications for the Genesis of the Zhaxikang Sb-Pb-Zn-Ag Deposit in Southern Tibet

The genesis of the Zhaxikang Sb-Pb-Zn-Ag deposit remains controversial. Three different geological environments have been proposed to model mineralization: a hot spring, a magmatic-hydrothermal fluid, and a sedimentary exhalative (SEDEX) overprinted by a hot spring. Here, we present the electron probe microanalysis (EPMA) and Fe-Zn isotopic data (microsampled) of four samples from the first pulse of mineralization that show annular textures to constrain ore genesis. The Zn/Cd ratios from the EPMA data of sphalerite range from 296 to 399 and overlap the range of exhalative systems. The δ56Fe values of Mn-Fe carbonate and δ66Zn values of sphalerite gradually decrease from early to late stages in three samples. A combination of the EPMA and isotopic data shows the Fe-Zn contents also have different correlations with δ66Zn values in sphalerite from these samples. Rayleigh distillation models this isotope and concentration data with the cause of fractionation related to vapour-liquid partitioning and mineral precipitation. In order to verify this Rayleigh distillation model, we combine our Fe-Zn isotopic data with those from previous studies to establish 12 Fe-Zn isotopic fractionation models. These fractionation models indicate the δ56Fei and δ66Zni values (initial Fe-Zn isotopic compositions) of the ore-forming system are in the range of -0.5‰​​ ~−1‰ and -0.28‰​ ~0‰, respectively. To conclude, the EPMA data, Fe-Zn isotopic characteristics, and fractionation models support the SEDEX model for the first pulse of mineralization.

Chromium isotope fractionation during Cr(VI) reduction in a methane-based hollow-fiber membrane biofilm reactor

Chromium (Cr) isotope fractionation analysis is a promising tool for monitoring Cr(VI) reduction in natural aqueous systems. In addition, large amounts of CH4 in natural aqueous sediments are oxidized to CO2 through methanotrophs, thereby mitigating emissions to the atmosphere. However, the investigations on the Cr(VI) reduction process with methanotrophs, and the associated Cr isotope fractionation patterns are scarce. In this study, we have shown that Cr(VI) reduction can occur in the presence of CH4 as the sole electron donor in a hollow-fiber membrane reactor (HfMBR) after direct bacteria enrichment from sediment samples. Products of the methane oxidation by the methanotrophs are used by microbes to reduce Cr(VI) as shown by the progressive increase in δ53Cr with time in the CH4 feed reactor. The isotope fractionation factor (ε) of −2.62 ± 0.20‰ was obtained from the application of the Rayleigh distillation model. The results of Cr isotope fractionation analysis also explained the decrease of Cr(VI) concentration in the N2 feed reactor, where the δ53Cr values remained steady in the first two weeks but significantly increased in the last two weeks, indicating that physical adsorption and subsequent Cr(VI) reduction occurred. This study extended the application of Cr isotope fractionation, showing the suitability of this method for clarifying different Cr(VI) removal processes.

A stable isotope record of late Cenozoic surface uplift of southern Alaska

Although the timing of an acceleration in late-Cenozoic exhumation of southern Alaska is reasonably well constrained as beginning ∼5–∼6 Ma, the surface uplift history of this region remains poorly understood. To assess the extent of surface uplift relative to rapid exhumation, we developed a stable isotope record using the hydrogen isotope composition (δD) of paleo-meteoric water over the last ∼7 Ma from interior basins of Alaska and Yukon Territory. Our record, which is derived from authigenic clays (δDclay) in silicic tephras, documents a ∼50–60‰ increase in δD values from the late Miocene (∼6–∼7 Ma) through the Plio-Pleistocene transition (∼2–∼3 Ma), followed by near-constant values over at least the last ∼2 Ma. Although this enrichment trend is opposite that of a Rayleigh distillation model typically associated with surface uplift, we suggest that it is consistent with indirect effects of surface uplift on interior Alaska, including changes in aridity, moisture source, and seasonality of moisture. We conclude that the δDclay record documents the creation of a topographic barrier and the associated changes to the climate of interior Alaska and Yukon Territory.

Tracing the role of endogenous carbon in denitrification using wine industry by-product as an external electron donor: Coupling isotopic tools with mathematical modeling

Nitrate removal through enhanced biological denitrification (EBD), consisting of the inoculation of an external electron donor, is a feasible solution for the recovery of groundwater quality. In this context, liquid waste from wine industries (wine industry by-products, WIB) may be feasible for use as a reactant to enhance heterotrophic denitrification. To address the feasibility of WIB as electron donor to promote denitrification, as well as to evaluate the role of biomass as a secondary organic C source, a flow-through experiment was carried out. Chemical and isotopic characterization was performed and coupled with mathematical modeling. Complete nitrate attenuation with no nitrite accumulation was successfully achieved after 10 days. Four different C/N molar ratios (7.0, 2.0, 1.0 and 0) were tested. Progressive decrease of the C/N ratio reduced the remaining C in the outflow and favored biomass migration, producing significant changes in dispersivity in the reactor, which favored efficient nitrate degradation. The applied mathematical model described the general trends for nitrate, ethanol, dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) concentrations. This model shows how the biomass present in the system is degraded to dissolved organic C (DOCen) and becomes the main source of DOC for a C/N ratio between 1.0 and 0. The isotopic model developed for organic and inorganic carbon also describes the general trends of δ13C of ethanol, DOC and DIC in the outflow water. The study of the evolution of the isotopic fractionation of organic C using a Rayleigh distillation model shows the shift in the organic carbon source from the WIB to the biomass and is in agreement with the isotopic fractionation values used to calibrate the model. Isotopic fractionations (ε) of C-ethanol and C-DOCen were −1‰ and −5‰ (model) and −3.3‰ and −4.8‰ (Rayleigh), respectively. In addition, an inverse isotopic fractionation of +10‰ was observed for biomass degradation to DOCen. Overall, WIB can efficiently promote nitrate reduction in EBD treatments. The conceptual model of the organic C cycle and the developed mathematical model accurately described the chemical and isotopic transformations that occur during this induced denitrification.

The effect of changing seawater Ca and Mg concentrations upon the distribution coefficients of Mg and Sr in the skeletons of the scleractinian coral Pocillopora damicornis

The skeletal composition of calcifying organisms, in particular Mg/Ca and Sr/Ca ratios, have been widely used to understand fluctuations in seawater chemistry throughout the Phanerozoic. While the success of applying these data to the geologic record depends on a knowledge of the distribution coefficients for these elements (DMg and DSr), there are scarcely any studies which have described how these values vary as a result of changing seawater Mg/Ca ratios. To address this, we have cultured the scleractinian coral, Pocillopora damicornis, in seawater with ranges of Mg and Ca concentrations. Here, we demonstrate that Mg/Ca and Sr/Ca ratios of coral skeletons correlate with total seawater Mg/Ca and Sr/Ca molar ratios, but that apparent DMg and DSr values do not remain constant across the range of experimental seawater treatments, with DMg values significantly increasing with seawater Mg/Ca ratios and DSr values significantly increasing with seawater Ca concentrations. These trends are not rate dependent and may be best explained by a Rayleigh distillation model, in which the calcifying space is semi-isolated from seawater during skeletogenesis (i.e. leaky). As there is a slight increase in DMg and decrease in DSr values between our “Jurassic” and “Modern” seawater treatments, the application of a constant distribution coefficient to estimate changes in ancient seawater chemistry may underestimate seawater Mg/Ca ratios and overestimate Sr/Ca throughout the Mesozoic and Cenozoic. We suggest that interpretations of seawater chemistry from fossil corals may be improved by using the relationships derived for skeletal and seawater Mg/Ca and Sr/Ca ratios established by our experiments, as they incorporate the effect of seawater Mg/Ca ratios on skeletal Mg/Ca and Sr/Ca ratios.

Chromium isotope fractionation in ferruginous sediments

Ferrous Fe is a potent reductant of Cr(VI), and while a number of laboratory studies have characterized Cr isotope fractionation associated with Cr(VI) reduction by ferrous iron, the expression of this fractionation in real-world ferrous Fe-rich environments remains unconstrained. Here we determine the isotope fractionation associated with Cr(VI) reduction in modern ferrous Fe-rich sediments obtained from the previously well studied Lake Matano, Indonesia. Whole core incubations demonstrate that reduction of Cr(VI) within ferruginous sediments provides a sink for Cr(VI) leading to Cr(VI) concentration gradients and diffusive Cr(VI) fluxes across the sediment water interface. As reduction proceeded, Cr(VI) remaining in the overlying lake water became progressively enriched in the heavy isotope (53Cr), increasing δ53Cr by 2.0 ± 0.1‰ at the end of the incubation. Rayleigh distillation modelling of the evolution of Cr isotope ratios and Cr(VI) concentrations in the overlying water yields an effective isotope fractionation of εeff = 1.1 ± 0.2‰ (53Cr/52Cr), whereas more detailed diagenetic modelling implies an intrinsic isotope fractionation of εint = 1.80 ± 0.04‰. Parallel slurry experiments performed using anoxic ferruginous sediment yield an intrinsic isotope fractionation of εint = 2.2 ± 0.1‰. These modelled isotope fractionations are corroborated by direct measurement of the δ53Cr composition on the upper 0.5 cm of Lake Matano sediment, revealing an isotopic offset from the lake water of Δ53Cr=0.21–1.81‰. The data and models reveal that effective isotope fractionations depend on the depth at which Cr(VI) reduction takes place below the sediment water interface—the deeper the oxic non-reactive zone, the smaller the effective fractionation relative to the intrinsic fractionation. Based on the geochemistry of the sediment we suggest the electron donors responsible for reduction are a combination of dissolved Fe(II) and 0.5 M HCl extractable (solid phase) Fe(II). Our results are in line with the range of intrinsic fractionation factors observed for such phases in previous laboratory studies. We suggest that intrinsic isotope fractionations of around 1.8‰, may be broadly characteristic of ferruginous environments, but we note that the partitioning of ferrous Fe between dissolved and solid phases may modulate this value. These results indicate that seawater δ53Cr is only captured with high-fidelity by ferruginous sediments when oxygen penetration, and therefore the upper boundary of the zone of Cr(VI) reduction, extends to more than 10 cm below the sediment-water-interface, as can be the case in sediments deposited below oligotrophic waters. In more productive regions, with thinner oxic zones, ferruginous sediments would record δ53Cr as much as 1.8‰ lower than seawater δ53Cr. This implies that a range of sediment δ53Cr compositions, that include that of the igneous silicate earth (ISE), are possible even when seawater is isotopically heavier than the ISE.

Strontium isotope fractionation during strontianite (SrCO3) dissolution, precipitation and at equilibrium

In this study we examine the behavior of stable Sr isotopes between strontianite [SrCO3] and reactive fluid during mineral dissolution, precipitation, and at chemical equilibrium. Experiments were performed in batch reactors at 25°C in 0.01M NaCl solutions wherein the pH was adjusted by bubbling of a water saturated gas phase of pure CO2 or atmospheric air. The equilibrium Sr isotope fractionation between strontianite and fluid after dissolution of the solid under 1atm CO2 atmosphere was estimated as Δ88/86SrSrCO3-fluid = δ88/86Sr SrCO3−δ88/86Srfluid=−0.05±0.01‰. On the other hand, during strontianite precipitation, an enrichment of the fluid phase in 88Sr, the heavy isotopomer, was observed. The evolution of the δ88/86Srfluid during strontianite precipitation can be modeled using a Rayleigh distillation approach and the estimated, kinetically driven, fractionation factor αSrCO3-fluid between solid and fluid is calculated to be 0.99985±0.00003 corresponding to Δ88/86SrSrCO3-fluid = −0.15‰. The obtained results further support that under chemical equilibrium conditions between solid and fluid a continuous exchange of isotopes occurs until the system approaches isotopic equilibrium. This isotopic exchange is not limited to the outer surface layer of the strontianite crystal, but extends to ∼7–8 unit cells below the crystal surface. The behavior of Sr isotopes in this study is in excellent agreement with the concept of dynamic equilibrium and it suggests that the time needed for achievement of chemical equilibrium is generally shorter compared to that for isotopic equilibrium. Thus it is suggested that in natural Sr-bearing carbonates an isotopic change may still occur close to thermodynamic equilibrium, despite no observable change in aqueous elemental concentrations. As such, a secondary and ongoing change of Sr isotope signals in carbonate minerals caused by isotopic re-equilibration with fluids has to be considered in order to use Sr isotopes as environmental proxies in aquatic environments.

Effect of waterlogging on carbon isotope discrimination during photosynthesis in Larix gmelinii

ABSTRACTSoil moisture is a major factor controlling carbon isotope discrimination (Δ13C), which has been demonstrated to decrease under dry conditions in many studies; however, few studies on Δ13C under waterlogging condition have been conducted. In this study, a pot experiment was conducted with Larix gmelinii, a major larch species in the east Siberian Taiga, to investigate the effect of waterlogging on Δ13C during photosynthesis. Assimilation rate and Δ13CRD (instantaneous Δ13C calculated with Rayleigh distillation equation) decreased drastically soon after waterlogging, followed by recovery in their values, which was caused by a change in stomatal conductance. Thereafter, assimilation rate decreased gradually, whereas Δ13CRD decreased more gently. These results were thought to be caused by the decrease in both stomatal conductance and carboxylation. Our results indicate that extreme wet events may cause a decrease in Δ13C, which is important information for detecting flooding events in the past using tree-ring isotope analyses and for studying impacts of flooding on plants in areas where waterlogging might occur.

Younger-Dryas cooling and sea-ice feedbacks were prominent features of the Pleistocene-Holocene transition in Arctic Alaska

Declining sea-ice extent is currently amplifying climate warming in the Arctic. Instrumental records at high latitudes are too short-term to provide sufficient historical context for these trends, so paleoclimate archives are needed to better understand the functioning of the sea ice-albedo feedback. Here we use the oxygen isotope values of wood cellulose in living and sub-fossil willow shrubs (δ18Owc) (Salix spp.) that have been radiocarbon-dated (14C) to produce a multi-millennial record of climatic change on Alaska's North Slope during the Pleistocene-Holocene transition (13,500–7500 calibrated 14C years before present; 13.5–7.5 ka). We first analyzed the spatial and temporal patterns of δ18Owc in living willows growing at upland sites and found that over the last 30 years δ18Owc values in individual growth rings correlate with local summer temperature and inter-annual variations in summer sea-ice extent. Deglacial δ18Owc values from 145 samples of subfossil willows clearly record the Allerød warm period (∼13.2 ka), the Younger Dryas cold period (12.9–11.7 ka), and the Holocene Thermal Maximum (11.7–9.0 ka). The magnitudes of isotopic changes over these rapid climate oscillations were ∼4.5‰, which is about 60% of the differences in δ18Owc between those willows growing during the last glacial period and today. Modeling of isotope-precipitation relationships based on Rayleigh distillation processes suggests that during the Younger Dryas these large shifts in δ18Owc values were caused by interactions between local temperature and changes in evaporative moisture sources, the latter controlled by sea ice extent in the Arctic Ocean and Bering Sea. Based on these results and on the effects that sea-ice have on climate today, we infer that ocean-derived feedbacks amplified temperature changes and enhanced precipitation in coastal regions of Arctic Alaska during warm times in the past. Today, isotope values in willows on the North Slope of Alaska are similar to those growing during the warmest times of the Pleistocene-Holocene transition, which were times of widespread permafrost thaw and striking ecological changes.

Fe isotope fractionation during Fe(II) oxidation by the marine photoferrotroph Rhodovulum iodosum in the presence of Si – Implications for Precambrian iron formation deposition

The iron (Fe) isotopic composition of Precambrian iron formations (IFs), besides providing geological context through its mineralogical properties, was suggested to function as a biosignature that can be used to infer a potential microbial role in the formation of the deposited Fe minerals. Anoxygenic phototrophic Fe(II)-oxidizing bacteria (photoferrotrophs), capable of oxidizing Fe(II) anoxically using light energy, were potentially involved in Fe(II) oxidation in anoxic or suboxic Precambrian oceans. The effect of Si on Fe isotopic fractionation between aqueous Fe(II) and Fe–Si-co-precipitates has been investigated before. However, it is currently unknown how stable Fe isotopes are fractionated during enzymatic Fe(II) oxidation under marine hydrogeochemical conditions, and particularly how the presence of Si affects the Fe isotope composition and the isotopic exchange among different Fe phases. We therefore studied Fe isotope fractionation during Fe(II) oxidation by the marine photoferrotroph Rhodovulum iodosum in simulated Precambrian seawater amended with 1mM dissolved Si. Our results show that the change in the Fe isotope compositions over time for both the initial aqueous Fe(II) (Feaq) and the Fe(III) precipitates (Feppt) follow a Rayleigh distillation model. Moreover, the fractionation (ε56Feppt-aq) determined independently from either δ56Feaq or δ56Feppt data resulted in a value of 2.3±0.3 (2SD, N=6). This value differs from the fractionation factor determined previously for Fe(II) oxidation by R. iodosum in the absence of Si, where the fractionation calculated from δ56Feaq (i.e. 0.96–1.18) was different from that calculated from δ56Feppt (1.96–1.98). This difference was attributed to isotopic exchange processes with soluble and sorbed Fe species. The present study suggests that Si present in Precambrian oceans retards Fe isotopic exchange, likely through combined effects of complexation of dissolved Fe species by Si and sorption of Si to Fe(III) minerals, thus lowering sorption of Fe(II) to the Fe(III) minerals, which is necessary for isotopic exchange. In summary our data suggests that Si in ancient oceans played a key role for the Fe isotope composition of Fe(III) minerals that were deposited by photoferrotrophic iron oxidation in Precambrian oceans by minimizing subsequent isotope exchange and recrystallization processes with aqueous Fe(II).

Volatile earliest Triassic sulfur cycle: A consequence of persistent low seawater sulfate concentrations and a high sulfur cycle turnover rate?

Marine biodiversity decreases and ecosystem destruction during the end-Permian mass extinction (EPME) have been linked to widespread marine euxinic conditions. Changes in the biogeochemical sulfur cycle, microbial sulfate reduction (MSR), and marine dissolved sulfate concentrations during the Permian-Triassic transition can provide insights into the role of ocean chemistry change in the largest mass extinction in Earth history. In this study, we constrain marine dissolved sulfate concentrations using the MSR-trend method of Algeo et al. [Algeo, T.J., Luo, G.M., Song, H.Y., Lyons, T.W., Canfield, D.E., 2015. Reconstruction of secular variation in seawater sulfate concentrations. Biogeosciences 12, 2131–2151] on sulfur (S) isotope records from Iran (the Kuh-e-Ali Bashi and Zal sections) and Hungary (the Bálvány North and Bálvány East sections). This empirically derived transfer function is based on the S isotope fractionation between sulfate and sulfide associated with MSR in natural aquatic environments. This fractionation is proxied by the difference in S isotope compositions between chromium-reducible sulfur (CRS) and carbonate-associated sulfate (CAS), i.e., Δ34SCAS-CRS. We show that, despite region-specific redox conditions, Δ34SCAS-CRS exhibits a nearly invariant value of 15–16‰ in both study sections. By comparing our record with a Δ34Ssulfate-sulfide density distribution for modern marine sediments, we deduce that porewater Rayleigh distillation, carbonate diagenesis, and other effects are unlikely to have appreciably altered the S isotope offset between CRS and CAS in the study sections. In addition, differences in sedimentary regimes and organic carbon (OC) fluxes between the Iranian and Hungarian sections exclude major influence of the electron donor on MSR-S isotope fractionation and point to a more universal control, i.e., contemporaneous seawater sulfate concentration.The MSR-trend transfer function yielded estimates of seawater sulfate of 0.6–2.8mM for the latest Permian to earliest Triassic, suggesting a balanced oceanic S-cycle with equal S inputs and outputs and no major changes in sulfate concentrations during this interval. However, a secular trend toward heavier δ34SCAS (by >5‰) in the earliest Triassic can be explained only by increasing the turnover rate of the S-cycle (by ca. one order of magnitude) and a concomitant change in terrestrial S sources in a box model experiment. Exposure of evaporite deposits having a high δ34S may account for the source change, with a possible role for the Siberian Traps volcanism by magmatic remobilization of Cambrian rock salt. A high sulfur cycle turnover rate would have left the ocean system vulnerable to development of widespread euxinic conditions, posing a sustained threat to marine life during the Early Triassic.

Isotope evidence for quantifying river evaporation and recharge processes in the lower reaches of the Yellow River

Evaporation and recharge are important hydrological processes in the water cycle. However, accurately quantifying these two processes of river remains to be difficult due to their spatial heterogeneity and the limitations of traditional methods. In this study, a more reliable method of stable isotopes of δ 18O and δ 2H based on the Rayleigh distillation equation and mass conservation was used to estimate the evaporation and recharge of the rivers in the lower reaches of the Yellow River, North China Plain. Comprehensive sampling campaigns including 30 surface water samples from 10 rivers, 33 groundwater samples from domestic and observation wells, and two Yellow River water samples were conducted. The results showed that the evaporation proportion of the rivers based on δ 18O and δ 2H both averaged 14.4%. The evaporation proportions in each river did not completely follow a linear increasing trend along the flow path. This phenomenon could be mainly explained by the different proportions of recharge from groundwater and Yellow River water. With closer to the Yellow river, evaporation of the rivers decreased while the recharge by the Yellow River increased. Regression equations based on δ 18O, δ 2H, and their average revealed that the evaporation proportion respectively increased by 1.02, 0.79, and 0.90% with the increase in the distance to the Yellow River per 10 km. On the contrary, the recharge proportion decreased by 7.68, 5.51, and 6.59%, respectively. In addition, using δ 18O rather than δ 2H was more reliable in studying the spatial influence of the Yellow River on evaporation and recharge. Sensitivity analysis showed that the evaporation model was most sensitive to isotopic composition, rather than to air temperature or relative humidity. The results of this study provide insights into the determination of river hydrological processes and the management of water resources.

Isotopic spatial variations and isotopic effects of two heavy summer precipitation events across Beijing

Stable isotopes of precipitation samples collected during two heavy rainfall events on July 29 and September 1, 2014 at 11 stations from Beijing Network of Isotopes in Precipitation, are analyzed to discuss eventful isotopic effects. No significant correlations between precipitation δ18O and temperature/elevation are found. After correction with the Rayleigh distillation model for the rainfall on July 29, a significant correlation between isotopes and latitude was obtained for both rainfall events. This implies both rainfalls are formed by southern moisture sources, which were also confirmed by water vapor budget and HYSPLIT model.

Soil n-alkane δD and glycerol dialkyl glycerol tetraether (GDGT) distributions along an altitudinal transect from southwest China: Evaluating organic molecular proxies for paleoclimate and paleoelevation

Organic molecular proxies provide a record of the hydrogen isotopic composition of ambient precipitation and paleoenvironmental temperature. In terrestrial settings, two classes of organic biomarkers are commonly utilized to reconstruct these past environmental conditions: straight-chained normal alkanes (n-alkanes) and branched glycerol dialkyl glycerol tetraethers (brGDGTs). We measured the δDn-alkane and the ratio of cyclisation and methylation indexes of branched tetraethers (CBT/MBT) from surface soils along a ∼1000km transect along the southeast margin of the Tibetan Plateau to assess how these proxies record changes in climate parameters that are related to elevation, despite variations in ecosystem. Abundance-weighted δDnC27-31 data record the δD of precipitation across the orogen and indicate minimal change in apparent fractionation (εn-alkane/water=−133‰) with elevation. n-Alkane δD mirrors the pattern of Rayleigh distillation of an air mass undergoing rainout as moisture moves from the Bay of Bengal into the SE margin of the Tibetan plateau. Soil tetraether temperatures provide a reliable measure of modern temperature with an MBT/CBT calculated temperature lapse rate (5.8°C/km) close to the moist adiabat. These data reflect “ground-level” conditions that are independent of the shape of the orogen or the source of moisture. In combination with a Rayleigh distillation model that incorporates temperature and precipitation isotope data, paired tetraether temperature and leaf wax isotope data produce a reliable record of changes in environmental conditions associated with modern elevation change across the largest orogen. However, some tetraether calibrations may impart systematic temperature bias, most notably in cold or dry climates. These calibration uncertainties can result in underestimates of paleoelevations by up to 1.5–2km. Paired isotopic and temperature paleoelevation reconstructions can minimize errors associated with an individual proxy method, however we recommend that application of tetraether temperature paleoelevation reconstruction take potential calibration biases into account in paleoelevation estimates.

Sulphur cycling in a Neoarchaean microbial mat.

Multiple sulphur (S) isotope ratios are powerful proxies to understand the complexity of S biogeochemical cycling through Deep Time. The disappearance of a sulphur mass‐independent fractionation (S‐MIF) signal in rocks <~2.4 Ga has been used to date a dramatic rise in atmospheric oxygen levels. However, intricacies of the S‐cycle before the Great Oxidation Event remain poorly understood. For example, the isotope composition of coeval atmospherically derived sulphur species is still debated. Furthermore, variation in Archaean pyrite δ34S values has been widely attributed to microbial sulphate reduction (MSR). While petrographic evidence for Archaean early‐diagenetic pyrite formation is common, textural evidence for the presence and distribution of MSR remains enigmatic. We combined detailed petrographic and in situ, high‐resolution multiple S‐isotope studies (δ34S and Δ33S) using secondary ion mass spectrometry (SIMS) to document the S‐isotope signatures of exceptionally well‐preserved, pyritised microbialites in shales from the ~2.65‐Ga Lokammona Formation, Ghaap Group, South Africa. The presence of MSR in this Neoarchaean microbial mat is supported by typical biogenic textures including wavy crinkled laminae, and early‐diagenetic pyrite containing <26‰ μm‐scale variations in δ34S and Δ33S = −0.21 ± 0.65‰ (±1σ). These large variations in δ34S values suggest Rayleigh distillation of a limited sulphate pool during high rates of MSR. Furthermore, we identified a second, morphologically distinct pyrite phase that precipitated after lithification, with δ34S = 8.36 ± 1.16‰ and Δ33S = 5.54 ± 1.53‰ (±1σ). We propose that the S‐MIF signature of this secondary pyrite does not reflect contemporaneous atmospheric processes at the time of deposition; instead, it formed by the influx of later‐stage sulphur‐bearing fluids containing an inherited atmospheric S‐MIF signal and/or from magnetic isotope effects during thermochemical sulphate reduction. These insights highlight the complementary nature of petrography and SIMS studies to resolve multigenerational pyrite formation pathways in the geological record.

Volatility of Benzaldehyde in Water/Wort

The brewing process defines the final taste of beer, and therefore it is important to minimize unwanted flavor components in the brewing process. The best tool is the boiling process, in which unwanted components are vaporized. Vaporization requires energy, and it is the scope of every new development in the brewhouse to reduce energy and to save money. For reducing and optimizing the vaporization of unwanted flavor components, it is important to understand the thermodynamic behavior of flavors in wort. Each component has its own thermodynamic behavior. This article is about the unwanted flavor benzaldehyde (BENZ). Therefore, its volatility in water/wort at infinite dilution over a broad temperature range (30, 40, 50, 60, 70, 80, and 90°C) is determined. The volatility describes the thermodynamic behavior of a component i soluted in a component j, and as the volatility becomes higher less energy is needed for vaporization. To calculate the needed vaporization energy to reduce the content of BENZ the volatility has to be measured. Therefore, four different and independent measurement methods (recirculating still, Rayleigh distillation, Dohnal method, and flash distillation) were used. The central result of the measurements is that BENZ in water at infinite dilution has a maximum volatility (KBENZ,60° = 42 ± 3) at a temperature of 60°C. Thus, vaporization at this temperature is the most efficient tool to reduce this special flavor component.

Spatial distribution and controlling factors of stable isotopes in meteoric waters on the Tibetan Plateau: Implications for paleoelevation reconstruction

Debates persist about the interpretations of stable isotope based proxies for the surface uplift of the central–northern Tibetan Plateau. These disputes arise from the uncertain relationship between elevation and the δ18O values of meteoric waters, based on modern patterns of isotopes in precipitation and surface waters. We present a large river water data set (1,340 samples) covering most parts of the Tibetan Plateau to characterize the spatial variability and controlling factors of their isotopic compositions. Compared with the amount-weighted mean annual oxygen isotopic values of precipitation, we conclude that river water is a good substitute for isotopic studies of precipitation in the high flat (e.g., elevation >3,300 m) interior of the Tibetan Plateau in the mean annual timescale. We construct, for the first time based on field data, contour maps of isotopic variations of meteoric waters (δ18O, δD and d-excess) on the Tibetan Plateau. In the marginal mountainous regions of the Plateau, especially the southern through eastern margins, the δ18O and δD values of river waters decrease with increasing mean catchment elevation, which can be modeled as a Rayleigh distillation process. However, in the interior of the Plateau, northward increasing trends in δ18O and δD values are pronounced and present robust linear relations; d-excess values are lower than the marginal regions and exhibit distinct contrasts between the eastern (8‰–12‰) and western (<8‰) Plateau. We suggest that these isotopic features of river waters in the interior of the Tibetan Plateau result from the combined effects of: 1) mixing of different moisture sources transported by the South Asian monsoon and Westerly winds; 2) contribution of moisture from recycled surface water; and 3) sub-cloud evaporation. We further provide a sub-cloud evaporation modified Rayleigh distillation and mixing model to simulate the isotopic variations in the western Plateau. Results of this work suggest that stable isotope-based paleoaltimetry studies are reliable in the southern through eastern Plateau margins; towards the central–northern Plateau, this method cannot be applied without additional constraints and/or large uncertainties.