Rayleigh Distillation Model Research Articles

Isotopic Fractionation during Sublimation of Low Porosity Ice

The magnitude of isotopic fractionation during sublimation of ice remains poorly constrained. Field and laboratory studies that span decades have persistently shown conflicting results. A better understanding of fractionation during sublimation is needed to improve interpretation of alpine hydrology, glaciology, paleoclimate and planetary histories that rely on stable isotopic records stored in icy reservoirs. At the core of the problem is the question of whether sublimation occurs as a layer-by-layer process with no fractionation or whether diffusion within the ice and vapor-ice exchange generate fractionation. We present results from an experiment where we suspended ice spheres in temperatures ranging from −25 to -10 °C in an unsaturated atmosphere and used a Rayleigh distillation model to estimate fractionation of the spheres. A small, yet statistically significant and repeatable, isotope fractionation (103lnα18O of ~ −0.6 ‰ and 103lnα2H between −3 and − 4 ‰ or α = 0.999, α = 0.994 to 0.997, respectively) was found during the sublimation of ice. The results definitively indicate the presence of fractionation yet the values are an order of magnitude smaller than would be predicted for equilibrium fractionation at this temperature and humidity. By assuming a porosity for the ice of 0.0005 % - which is typical for ice frozen under these conditions - we estimate a sufficient increase in diffusivity relative to solid ice to explain the observed fractionation values. The results help to reconcile how fractionation estimates during sublimation could vary between experimental and observational studies where porosity is not controlled for and can vary substantially across a continuum from porous firn layers to low porosity ice deep in glaciers.

Controls on the distribution of dissolved Cr in the upper water column of the Atlantic Basin

Over the last decades, the chromium (Cr) stable isotope system (referred to as δ53Cr) has emerged as a proxy to reconstruct past oxygenation changes in Earth’s atmosphere and oceans. Although Cr is a promising paleoproxy, uncertainties remain as to the modern marine Cr cycle, and limited data are yet available in large swaths of the ocean, including the Atlantic Ocean. Here we present dissolved seawater Cr concentrations ([Cr]) and δ53Cr along a meridional transect from the North to the South Atlantic (AMT 29). Chromium concentrations range from of 2.51 to 3.96 nmol kg−1 (n = 68) and δ53Cr values range from +0.86 ± 0.04 ‰ (2SEM) to +1.20 ± 0.02 ‰ (2SEM) (n = 68). In contrast to data from other ocean basins [Cr] and δ53Cr show only a weak correlation (δ53Cr vs. Ln([Cr]) R2 = 0.17), inconsistent with a closed-system Rayleigh distillation model. These results can mainly be explained by horizontal advection and water mass mixing, which our data demonstrate are the dominant processes controlling [Cr] and δ53Cr distributions throughout much of the Atlantic, while the impact of in situ biogeochemical cycling is comparatively minor. There is, indeed no clear impact of biological productivity nor of dysoxic environments in the (sub)tropical Atlantic on the cycling of Cr along the transect. This is likely explained by insufficiently depleted oxygen concentrations and relatively low biological productivity, resulting in these processes being of secondary importance relative to water mass mixing in shaping the distribution of Cr in the low- to mid-latitude Atlantic Ocean.

Dissolved Cu isotope compositions in hydrothermal plumes over back-arc volcanoes in the Northeast Lau Basin, Southwest Pacific Ocean

Seafloor hydrothermal venting may be an important source of marine Cu and affect the biogeochemical cycling of Cu in the oceans. The distribution of Cu and its isotope compositions (δ65Cu) can provide insight into seafloor hydrothermal processes and their role in the mass balance of global Cu. To date, there are no published Cu isotope data for hydrothermal plumes and very few reports on Cu concentration distributions. This study presents both Cu concentrations and dissolved Cu isotope (δ65Cu) in hydrothermal plumes from back-arc volcanoes in the Northeast Lau Basin. The dissolved Cu (dCu) concentrations range from 2.14 to 5.66 nM most of which are higher than the deep seawater concentrations. However, the concentrations for some plume samples were lower than the deep seawater dCu concentrations due to adsorption onto particles in the plumes. The δ65Cu of hydrothermal plumes vary from 0.25 to 1.05 ‰. As plumes dispersed, the Cu isotopes from high-temperature Mata Fitu and Mata Ua vents shifted towards light values. In contrast, the δ65Cu in plumes from low-temperature East Mata and West Mata vents show increasingly higher values with plume dispersal. Rayleigh distillation models are built based on the adsorption of dCu onto Fe particles and complexation with organic ligands to describe the dCu isotope evolution in hydrothermal plumes. The results suggest that the adsorption and organic complexation may be the likely explanations for the observed dCu isotope compositions in plumes from high- and low-temperature venting, separately, besides the mixing with background seawater. Our measured δ65Cu in three fluid samples (0.08, 0.09 and 0.20 ‰) are lower than that of the characterized sinks (∼0.3 ‰) in the oceans, indicating that hydrothermal fluids might be a source of light Cu isotopes. However, the δ65Cu (0.53 ‰ on average) in plume samples are higher than 0.3 ‰ and these seafloor hydrothermal plumes do not seem to be a source of light Cu isotope of dCu, at least near the venting sites. Our study first reveals the Cu isotope compositions and evolution in hydrothermal plumes and provides new hints about the impact of seafloor hydrothermal venting on the modern oceanic Cu isotope budget.

Nitrogen behavior during fluid-rock interaction in a continental subduction zone: Results from the UHP Dora-Maira Massif whiteschists and Eastern Alps leucophyllites

Deep-Earth cycling of nitrogen (N) along the subduction pathway, remains relatively poorly understood, particularly that related to deep subduction of continental crust. The ultrahigh-pressure (UHP) Dora-Maira Massif whiteschists in the Western Alps and their lower-P-T equivalent leucophyllites in the Eastern Alps show a decrease in N concentration and an increase in δ15N relative to their presumed country rock protoliths. On average, the whiteschists contain 20.7 ± 10.5 ppm N (mean ± 1σ) with δ15Nair = +2.7 ± 2.5‰ (mean ± 1σ) and the leucophyllites contain 59.8 ± 12.3 ppm N with δ15Nair = +4.3 ± 2.0‰, whereas the metagranitic country rocks from Dora-Maira contain 41.3 ± 12.5 ppm N with δ15Nair = −1.9 ± 3.2‰ and the country rocks from the Eastern Alps contain 91.1 ± 42.5 ppm N with δ15Nair = +1.7 ± 2.1‰. The loss of N and isotope shift in the whiteschists and leucophyllites from these two localities was accompanied by loss of LILE (Rb, Ba), Sr, CaO, Na2O, and FeOtotal. The other stable isotope systems applied to study both suites (Mg, Fe, O, Li and Ba) show no obvious correlation with variations in δ15N. Infiltration by and interaction with a serpentinite-derived fluid depleted in N and LILE could have led to leaching of N from the country rock protoliths and production of the +4.6‰ (Dora-Maira Massif) and +2.6‰ (Eastern Alps) isotope shifts adequately explained using a Rayleigh distillation model. The N exchange and leaching process is best explained as involving N2-NH4 or NH3-NH4 at about 550–600 °C, the latter the approximate temperatures at which the fluid infiltration is thought to have occurred. These results provide new insights regarding N behavior and isotopic fractionation during fluid-rock interactions occurring in UHP rocks and point to the importance of H2O-rich fluids from serpentinite dehydration as agents of metasomatism along deep subduction interfaces. Furthermore, the data for the metagranites indicate the potential of this lithology to retain significant amounts of N to at least 100 km and beyond sub-arc depths.

Mercury Isotope Fractionation during Dark Abiotic Reduction of Hg(II) by Dissolved, Surface-Bound, and Structural Fe(II).

Stable mercury (Hg) isotope ratios are an emerging tracer for biogeochemical transformations in environmental systems, but their application requires knowledge of isotopic enrichment factors for individual processes. We investigated Hg isotope fractionation during dark, abiotic reduction of Hg(II) by dissolved iron(Fe)(II), magnetite, and Fe(II) sorbed to boehmite or goethite by analyzing both the reactants and products of laboratory experiments. For homogeneous reduction of Hg(II) by dissolved Fe(II) in continuously purged reactors, the results followed a Rayleigh distillation model with enrichment factors of -2.20 ± 0.16‰ (ε202Hg) and 0.21 ± 0.02‰ (E199Hg). In closed system experiments, allowing reequilibration, the initial kinetic fractionation was overprinted by isotope exchange and followed a linear equilibrium model with -2.44 ± 0.17‰ (ε202Hg) and 0.34 ± 0.02‰ (E199Hg). Heterogeneous Hg(II) reduction by magnetite caused a smaller isotopic fractionation (-1.38 ± 0.07 and 0.13 ± 0.01‰), whereas the extent of isotopic fractionation of the sorbed Fe(II) experiments was similar to the kinetic homogeneous case. Small mass-independent fractionation of even-mass Hg isotopes with 0.02 ± 0.003‰ (E200Hg) and ≈ -0.02 ± 0.01‰ (E204Hg) was consistent with theoretical predictions for the nuclear volume effect. This study contributes significantly to the database of Hg isotope enrichment factors for specific processes. Our findings show that Hg(II) reduction by dissolved Fe(II) in open systems results in a kinetic MDF with a larger ε compared to other abiotic reduction pathways, and combining MDF with the observed MIF allows the distinction from photochemical or microbial Hg(II) reduction pathways.

Temporal variability in seawater Sr/Ca ratios within a coral atoll as an indicator of marine calcifier community diversity

Coral reefs are marine environments where calcium carbonate production and dissolution along with photosynthesis and respiration can have a large impact on the daily biogeochemical cycles of seawater dissolved inorganic carbon (DIC), total alkalinity (TA), oxygen (O2), and major nutrients. Using seawater samples from Tetiaroa Atoll, French Polynesia, we apply isotope dilution thermal ionization mass spectrometry (ID-TIMS) to show that these daily cycles of variability extend to the dissolved seawater Sr/Ca ratio (Sr/Casw). Hourly measurements over a 27+ hour period indicate that Sr/Casw covaries with DIC and TA and exhibits up to a 2% relative difference compared to the regional Pacific Ocean source water Sr/Casw value of 8.53 mmol/mol. We hypothesize that the primary mechanism of hourly variability in Sr/Casw is carbonate precipitation/dissolution by corals and other marine calcifiers on the Tetiaroa reef, while sedimentary redox processes may significantly contribute to an apparent decoupling between net calcification rates estimated from TA compared to dissolved calcium [Ca]sw concentrations. Using a simple Rayleigh distillation model and a two-member mixing equation, we estimate the net partition coefficient of Sr (KD-Sr) for each hourly sample as a mixture of coral (aragonite; KD-Sr ∼ 1.06) and crustose coralline algae (high Mg-calcite; KD-Sr ∼ 0.39) contributions to the measured variability of [Ca]sw and Sr/Casw. As the high Mg-calcites of crustose coralline algae are (1) integral components to the structure and stability of the reef framework and (2) more soluble than aragonite under more acidic conditions, we propose that continued analyses of Sr/Casw within coral reef environments could be a useful tool for monitoring the ecological distribution and contributions of marine calcifiers on reefs as ocean warming and acidification intensify in response to anthropogenic climate change. Additionally, seasonal, interannual, and/or centennial-scale offsets between the Sr/Casw of open ocean source seawater and ambient reef seawater may have significant implications for interpreting past changes in sea surface temperatures derived from the coral Sr/Ca paleothermometer.

Stable chromium isotope compositions of hydrogenetic ferromanganese crusts potentially linked to primary productivity

Stable chromium isotope composition (δ53Cr) is a widely used paleo-redox proxy. However, modern seawater δ53Cr values do not correlate with dissolved O2 concentrations, suggesting that non-O2 factors may influence marine Cr cycling. We present new δ53Cr data for two hydrogenetic ferromanganese (FeMn) crusts deposited in the western- and central-north Pacific Ocean since the late Eocene, a period when the ocean remained largely oxic. Simple isotope mass balance and Rayleigh distillation models suggest that trivalent Cr is likely the major Cr species incorporated from seawater into the Fe phases of hydrogenetic FeMn crusts. The δ53Cr values of FeMn crusts decrease from −0.35‰ in the late Eocene to −0.74‰ in the middle Miocene, followed by increasing to modern values ranging from −0.33 to −0.47‰. The temporal trend of δ53Cr follows that of the regional pelagic sedimentation rate, suggesting that primary productivity may have played a role in shaping the δ53Cr signals recorded in the hydrogenetic FeMn crusts. Our data show that non-O2 factors may influence δ53Cr values recorded in Fe-rich sedimentary archives deposited in a largely oxic ocean, thus adding more complexities to the Cr isotope paleoproxy.

Uniquely low stable iron isotopic signatures in deep marine sediments caused by Rayleigh distillation

Dissimilatory iron reduction (DIR) is suggested to be one of the earliest forms of microbial respiration. It plays an important role in the biogeochemical cycling of iron in modern and ancient sediments. Since microbial iron cycling is typically accompanied by iron isotope fractionation, stable iron isotopes are used as tracer for biological activity. Here we present iron isotope data for dissolved and sequentially extracted sedimentary iron pools from deep and hot subseafloor sediments retrieved in the Nankai Trough off Japan. Dissolved iron (Fe(II)aq) is isotopically light throughout the ferruginous sediment interval but some samples have exceptionally light isotope values. Such light values have never been reported in natural marine environments and cannot be solely attributed to DIR. We show that the light isotope values are best explained by a Rayleigh distillation model where Fe(II)aq is continuously removed from the pore water by adsorption onto iron (oxyhydr)oxide surfaces. While the microbially mediated Fe(II)aq release has ceased due to an increase in temperature beyond the threshold of mesophilic microorganisms, the abiotic adsorptive Fe(II)aq removal continued, leading to uniquely light isotope values. These findings have important implications for the interpretation of dissolved iron isotope data especially in deep subseafloor sediments.

Middle Eastern cloud distillation throughout the Holocene - Quantified using oxygen isotopes from speleothems and deep-sea cores

The Middle East is considered a climate change “hot spot”, where rainfall is expected to decline in the upcoming decades due to Global Warming. Reconstructing the long-term natural climate variability of this region is critical for understanding and contextualizing the current hydroclimate change and enables evaluating potential mechanisms that govern it. Oxygen isotopes (δ18O) from cave deposits are a high-resolution paleohydrological proxy, which previously has been interpreted as direct measures of rainfall amount. However, cave δ18O is controlled by a series of processes (e.g., evaporation, condensation and rainout history), and therefore, any paleohydrological interpretation using cave δ18O requires a thorough understanding and quantification of the full hydrological cycle. In this paper, we use a simple Rayleigh distillation model to assess the various processes that govern the isotopic composition of precipitation and quantify changes in cloud distillation during the Holocene throughout the Middle East. The results show that a west-east isotopic distillation gradient persisted throughout the Holocene in the Middle East. The early Holocene, coeval with Sapropel 1, was characterized by high distillation and a large west-east distillation gradient. At the end of sapropel 1, distillation dropped and the west-east gradient declined. The middle to late Holocene was characterized by a gradual increase in distillation, however the west-east distillation gradient continued declining. Similarity between the late Holocene distillation reconstruction and the Dead Sea lake-levels, strengthens the reliability of cloud distillation as a suitable hydroclimate proxy. These results show that periods of high distillation in the Levant occurred during both high and low summer insolation (early and late Holocene, respectively), and thus, were most likely the result of two different climatic mechanisms. Our distillation and distillation gradient records provide a new way to characterize the long-term natural climate variability in the Middle East and thus help resolve the climatic mechanisms governing this variability.

Molybdenum and titanium isotopic signatures of arc-derived cumulates

Fluid migration and/or differentiation of magmas in arc settings are important drivers of stable-isotope fractionation of elements like molybdenum and titanium, respectively. For both isotope systems, evolved magmas are heavier than average arc-basalts, which requires an isotopically light reservoir counterbalancing the heavy felsic lithologies.In an attempt to better define this isotopically light reservoir, we investigate Mo and Ti isotopic signatures of upper crustal magmatic cumulates comprising hornblendites and gabbros from the Alpine orogen, the Sierra Nevada batholith, the Sanandaj-Sirjan zone and the Kos volcano-plutonic system. The cumulates and mafic enclaves exhibit Ti isotopic compositions ranging from that of arc-basalts/andesites to significantly lighter values (δ49Ti between −0.15 and + 0.08‰), which is in agreement with a Rayleigh distillation model. The δ49Ti correlates negatively with the abundance of FeTi oxides, suggesting that in samples which have δ49Ti signatures similar to those of arc-basalts, most of the Ti is hosted in pyroxene and amphibole. This indicates that the degree to which Ti isotopes are fractionated in a melt is controlled by the fraction of Ti incorporated into silicate phases versus that incorporated into FeTi oxides.In contrast, the corresponding Mo isotopic compositions of the upper crustal magmatic cumulates and mafic enclaves are more dispersed (δ98MoNIST = −0.02 ± 0.22‰, 2 s.d.) and similar to average arc-basalts. However, Mo concentrations throughout several cumulate and mafic enclave bulk rocks measured are too enriched to be explained by pure fractional crystallization as they do not match modelled melt-cumulate fractionation trends. We distinguish between purely magmatic and predominantly fluid mediated processes leading to Mo enrichment in cumulates, and show that both can play an important role in the generation of high Mo cumulates.

The stable chromium isotope composition of different mantle reservoirs

The stable chromium isotope composition of Earth’s mantle has been suggested to be heterogeneous, with mantle-derived chromitites slightly enriched in heavier Cr isotopes than mantle-derived silicate rocks. To better understand such heterogeneity and to search for a potentially complementary light Cr isotope reservoir in the mantle, we analyzed the stable Cr isotope compositions (δ53Cr expressed as deviation of sample 53Cr/52Cr from NIST SRM 979) of whole-rock pyroxenite and peridotite xenoliths from the North China Craton using a double spike technique. The δ53Cr values of the peridotites vary from −0.21‰ to −0.07‰ with an average value of −0.14 ± 0.10‰ (2SD, N = 5), which overlaps with the range of the Bulk Silicate Earth (−0.12 ± 0.10‰). In contrast, pyroxenites in this study yield lower δ53Cr values (−0.30‰ to −0.14‰ with an average value of −0.21 ± 0.08‰, 2SD, N = 20). The variation in the δ53Cr values of the pyroxenites can be explained by a Rayleigh distillation model during partial melting of the primitive mantle. The model provides minimum Cr isotope fractionation factors during partial melting ranging from 0.01‰ to 0.12‰, with light isotopes enriched in the melt. Combined with literature data, our results suggest that both peridotites and basalts are indistinguishable from the Bulk Silicate Earth in terms of δ53Cr. However, pyroxenites and chromitites are isotopically lighter and heavier than the Bulk Silicate Earth, respectively. Future work is needed to investigate the petrogenetic relationship between chromitites and pyroxenites in order to understand why they seem to complement each other in δ53Cr.

Thermodynamic behaviour of an e-cigarette: Investigation of nicotine delivery consistency using nicotine yield

In 2014, the Tobacco Product Directive imposed a regulatory framework to protect the users of vaping products. One of the items requires that vaping devices shall deliver nicotine doses at consistent levels. However, this item is not evident to grasp and results from a lack of understanding of the physical behaviour of a vaping device. This publication aims to provide a physical explanation of ”nicotine doses at a consistent levels”. Numerical and an experimental approaches are developed in parallel. The first is based on the Rayleigh distillation model to describe the vaporisation of a volume initially in liquid phase under vapour–liquid equilibrium conditions. The second generates emissions using in-lab or commercial e-liquids under standardised conditions (AFNOR XP-D90-300-3) and the Cubis atomiser with a 1Ω coil. The comparison is focused on the nicotine delivery efficiency obtained with these two approaches. Emissions are collected using a cold trap. The results show a mean nicotine recovery that is around 93% with a standard deviation of 12% over more 1000 tested e-liquids. A comparison of these results with simulation, allow assuming a complete vaporisation rather than a partial one. Therefore, the nicotine’s consistency postponed the problem of the consistency of the mass of e-the vaporised liquid. This consistency is verified under laboratory conditions (with a controlled and regulated power supply). In real life, the power units that are used in vaping products are discharging devices, and therefore the consistency will depend on the number of puffs expected, the power set-up and the battery’s characteristics.

Iron ligands and isotopes in hydrothermal plumes over backarc volcanoes in the Northeast Lau Basin, Southwest Pacific Ocean

Deep-sea hydrothermal venting is an important source of dissolved iron (dFe) to the oceans. Fe isotopes can be used as a potential tool to trace the dispersal of hydrothermal plumes. However, Fe isotope fractionation and its relation with Fe speciation as hydrothermal plumes disperse is still poorly constrained. In this study, we determined the Fe speciation and total and dissolved Fe isotope composition (δ56tFe, δ56dFe) for several hydrothermal plumes from backarc volcanoes in the Northeast Lau Basin. This combined approach provides important insights into the evolution of Fe isotopes in hydrothermal plumes. The results suggest δ56tFe variation in plumes is related to the loss of particulate Fe-sulfides or Fe-oxyhydroxides (FeOOH), both of which are dependant on the H2S concentrations and Fe/H2S in the source hydrothermal fluids. δ56dFe compositions in the hydrothermal plumes increase during plume dispersal/dilution and can be as high as 0.85 ‰, demonstrating that hydrothermal plumes can export dissolved Fe with a significantly heavier δ56dFe than hydrothermal fluids. The reasons may be ascribed to the organic Fe complexes (FeL) and colloidal FeOOH in the dissolved phase. Another interpretation might be associated with the low pH in volcanic arc hydrothermal systems rich in magmatic CO2 and SO2, which decreases the Fe(II) oxidation rate. Further, we demonstrate for the first time that the δ56dFe is positively correlated with the conditional stability constants of FeL (logKʹFeL). A Rayleigh distillation model is presented based on the mass balance of the determined FeL, and colloidal FeOOH in hydrothermal plumes, which can explain the observed Fe isotope compositions in hydrothermal plumes. Our data show how Fe isotopes are transformed within a hydrothermal plume above arc volcanoes and how these may differ from that of the original vent fluids. It adds to our understanding of the processes that have an impact on the Fe speciation and isotope composition in deep-sea hydrothermal plumes.

Variations of Stable Isotopes in Daily Precipitation in a Monsoon Region

The stable isotopes of hydrogen and oxygen in precipitation provide a useful reference for the study of hydrological processes, but concerns have been raised regarding the established patterns in their variations in a monsoon climate zone. In this study, stable isotopes (δ18O and δ2H) of 539 daily precipitation samples from seven hydrometeorological stations in the Beijing area were used to investigate short-term isotopic variations and the controlling factors at a region with a monsoon climate. The δ18O in the precipitation increases from the northwest to the south, which is controlled by the monsoon from the south and continental moisture from the northwest. Consistently, both the high δ18O values and low deuterium excess values from May to September reveal the impact of the monsoon. The amount effect is significant during the monsoon season. In contrast, the T effect is significant, with a gradient of 0.4‰ per °C during the non-monsoon season. A Rayleigh distillation model indicates that the moisture source and residual vapor fraction are the two most important factors in controlling the δ18O patterns in precipitation in a monsoon region, independent of temperature. The result of this study is helpful for the understanding of the regional atmospheric water cycle.

Impact of estuaries on fluvial Cr input into the ocean: Perspectives from the Mobile Bay Estuary, Northern Gulf of Mexico

The chromium (Cr) stable isotope system has been recently developed as a promising redox proxy to study Earth’s oxygenation history. However, an incomplete understanding of the global marine Cr isotope mass balance hinders its quantitative application. Specifically, whether estuary environments can alter fluvial Cr flux into the global ocean, together with its isotopic composition, is still debated. Here, we report the first systematic redox-dependent stable Cr isotope data for an oxic estuary (the Mobile Bay Estuary in the northern Gulf of Mexico). Our data suggest that the Cr(VI) supplied by the Mobile River is completely reduced to Cr(III) before salinity reaches 5. A Rayleigh distillation model calculates an isotope fractionation factor of −0.1‰ to −0.3‰ (isotopically light Cr(VI) preferentially reduced). Approximately 15–30% of fluvial Cr(III) is removed from solution in the mixing zone, and this process likely preferentially removes isotopically heavy Cr(III). Therefore, if the face values of the Cr concentration and δ53Cr of the Mobile River were used as input terms for the Gulf of Mexico, Cr flux would have been overestimated by a factor of 5–7 and its δ53Cr overestimated by 0.3–0.7‰. A literature survey suggests that seasonally variable fluvial Cr flux is lost from solution in the majority of estuaries studied thus far. Estuary loss of Cr and annual variation combined add an order of magnitude uncertainty to the global fluvial Cr flux estimated previously. How fluvial δ53Cr is affected in an estuary environment is difficult to generalize because of the competition between partial Cr(VI) reduction that removes light isotopes and Cr(III) scavenging that likely removes heavy isotopes, and such competition likely varies among estuaries.

Enhanced Oxidation of SO2 by H2O2 During Haze Events: Constraints From Sulfur Isotopes

AbstractSulfate aerosols play a critical role in atmospheric chemistry and climate change. However, the mechanism of sulfate formation during haze events remains highly uncertain. In this study, sulfur isotopic compositions of SO2 and sulfate in PM2.5 samples collected in Tianjin, China as well as a Rayleigh distillation model are used to constrain SO2 oxidation pathways. The sulfur isotopic fractionation (ε) between SO2 and sulfate displays a seasonal change with low values in summer (−0.1 ± 1.0‰, n = 16) and high values in winter (2.1 ± 1.2‰, n = 16). Although an influence of temperature effect to this seasonal trend cannot be ignored, the relation between ε values and SO2 oxidation ratios indicates that the seasonality is mainly attributed to the changes in relative contributions of oxidation pathways. In addition, an elevated ε value has been observed during the first stage of haze event, suggesting that the relative contribution of H2O2 pathway to sulfate formation is higher in haze days than that in normal days. Our results highlight the important role of SO2 oxidation by H2O2 in the first stage of haze event.

Temporal Variations of Stable Isotopes in Precipitation from Yungui Plateau: Insights from Moisture Source and Rainout Effect

Abstract Long-term continuous monitoring of precipitation isotopes has great potential to advance our understanding of hydrometeorological processes that determine stable isotope variability in the monsoon regions. This study presents 4-yr daily precipitation isotopes from Yungui Plateau in southwestern China that are influenced by Indian summer monsoon and East Asian monsoon. The local meteoric water line (LMWL; δ2H = 8.12δ18O + 11.2) was first established at the Tengchong (TC) site, which was close to the global meteoric water line (GMWL; δ2H = 8δ18O + 10), indicating little secondary subcloud evaporation in the falling rain. Precipitation δ18O values exhibited significant inverse relationships with precipitation amount (r = −0.42), air temperature (r = −0.43), and relative humidity (r = −0.41) with lower correlation coefficients throughout the entire period, which indicated that precipitation isotopic variability in TC could not be well explained by the local meteorological factors but influenced by other combined factors of regional precipitation amount and upstream rainout. Precipitation δ18O values showed a clear V-shaped trend throughout the observation period, characterized by higher δ18O values during the premonsoon period whereas lower values during the postmonsoon period. This seasonal variation of precipitation δ18O values was associated with the seasonal movement of the intertropical convergence zone and seasonal changes in moisture transport. Combined with backward trajectory analysis, precipitation δ18O values were estimated by a Rayleigh distillation model showing that upstream rainout processes from the Bay of Bengal (BoB) toward land (Myanmar) and recycling moisture over land were key factors affecting the isotopic compositions of the TC precipitation. These findings could enhance our understanding of atmospheric dynamics and moisture source in the monsoon regions and will potentially facilitate the interpretation of numerous isotopic proxy records from this region. SIGNIFICANCE STATEMENT The variability of the summer monsoon and its onset, duration, and failure directly determine the strong rainfall and drought in a given region and have great impacts on regional societies and agriculture. To better understand this variability, this study presented a 4-yr daily dataset of precipitation isotopes on the Yungui Plateau of southwestern China to explore atmospheric processes and moisture sources that drive isotopic variability in this region. Precipitation δ18O exhibited remarkably seasonal variability, with higher values in premonsoon period and lower values in the postmonsoon period. During the Indian summer monsoon period, moisture sources primarily originated from the BoB toward the TC site, experiencing rainout processes and local moisture recycling over land using a Rayleigh fractionation model. These findings shed new light on the temporal variations of precipitation stable isotopes and facilitate our understanding of hydrological cycle in the monsoon regions.

Isotope hydrogeochemical models for assessing the hydrological processes in a part of the largest continental flood basalts province of India

Continental Flood Basalts (CFB) occupy one fourth of the world’s land area. Hence, it is important to discern the hydrological processes in this complex hydrogeological setup for the sustainable water resources development. A model assisted isotope, geochemical, geospatial and geophysical study was conducted to understand the monsoonal characteristics, recharge processes, renewability and geochemical evolution in one of the largest continental flood basalt provinces of India. HYSPLIT modelling and stable isotopes were used to assess the monsoonal characteristics. Rayleigh distillation model were used to understand the climatic conditions at the time of groundwater recharge. Lumped parameter models (LPM) were employed to quantify the mean transit time (MTT) of groundwater. Statistical and geochemical models were adopted to understand the geochemical evolution along the groundwater flow path. A geophysical model was used to understand the geometry of the aquifer. The back trajectory analysis confirms the isotopic finding that precipitation in this region is caused by orographic uplifting of air masses originating from the Arabian Sea. Stable isotopic data of groundwater showed its meteoric origin and two recharge processes were discerned; (i) quick and direct recharge by precipitation through fractured and weathered basalt, (ii) low infiltration through the clayey black cotton soil and subjected to evaporation prior to the recharge. Tritium data showed that the groundwater is a renewable source and have shorter transit times (from present day to <30 years). The hydrogeochemical study indicated multiple sources/processes such as: the minerals dissolution, silicate weathering, ion exchange, anthropogenic influences etc. control the chemistry of the groundwater. Based on the geo-electrical resistivity survey, the potential zones (weathered and fractured) were delineated for the groundwater development. Thus, the study highlights the usefulness of model assisted isotopic hydrogeochemical techniques for understanding the recharge and geochemical processes in a basaltic aquifer system.

Redox-controlled antimony isotope fractionation in the epithermal system: New insights from a multiple metal stable isotopic combination study of the Zhaxikang Sb–Pb–Zn–Ag deposit in Southern Tibet

Redox reactions, biological processes, evaporation and precipitation processes, adsorption, and Rayleigh distillation mechanisms have been proposed to account for the fractionation of antimony (Sb) isotopes in natural materials. However, only one paper was published to support and characterize the Rayleigh distillation induced Sb isotopic fractionation in a hydrothermal system. Therefore, the Sb isotopic fractionation mechanism research in the epithermal system is still negligible, which severely restricts future application. The Zhaxikang Sb–Pb–Zn–Ag deposit is the only super-large deposit within the North Himalayan Metallogenic Belt (NHMB), which comprises two episodes of mineralization (First episode: Pb–Zn mineralization, Stages 1 and 2; Second episode: Sb mineralization, Stages 3 to 6). Herein, we measured the δ123SbNIST 3102A values of stage 4 sulfosalt minerals and stage 5 stibnite from the Zhaxikang Sb–Pb–Zn–Ag deposit, to resolve the fractionation direction and relative magnitude of Sb isotopes caused by these aforesaid geologically prominent mechanisms in the epithermal systems with an auxiliary investigation of Fe–Cu isotopes. The second episode of Sb-containing hydrothermal fluid has leached metals (e.g., Pb, Ag, Fe, Cu) from pre-existing Pb–Zn orebodies, to initiate the formation of stage 4 sulfosalt minerals. According to XPS (X-ray Photoelectron Spectroscopy) analyses, the Cu isotopic variation of stage 4 bournonite (0.08‰ – 0.89‰) must be controlled primarily by the reduction reaction (Cu2+ + e− → Cu+) during leaching and precipitation. Keeping in mind a good linear correlation between δ123Sb and δ65Cu values (R2 = 0.99) for bournonite, the same mechanism was used to decipher the variation in δ123Sb values (0.10‰ – 0.48‰) of bournonite (Sb5+ + 2e− → Sb3+). Abundant native sulfur within the orefield allowed for the overall reaction equation of CuFeS2 + FeS2 + PbS + Sb5+(aq) = CuPbSbS3 + Fe2+(aq) + 2S to describe the bournonite formation. Accordingly, the Sb isotopic variations (−0.27‰ to 0.48‰) of Sb-bearing minerals (boulangerite, bournonite and stibnite) were empirically attributed to redox reactions. The Rayleigh distillation model indicated that the observed fractionation was most likely induced by redox reactions, while the related theoretical calculations revealed a great antimony exploration potential in deeper parts of the orefield. Overall, the Sb isotopes could be used to identify redox changes in the epithermal system, and exhibit great potential in tracing metal sources, monitoring fluid evolution and ore formation, and providing insights into mineral exploration.

High-resolution stable isotope signature of a land-falling atmospheric river in southern Norway

Abstract. Heavy precipitation at the west coast of Norway is often connected to elongated meridional structures of high integrated water vapour transport known as atmospheric rivers (ARs). Here we present high-resolution measurements of stable isotopes in near-surface water vapour and precipitation during a land-falling AR in southwestern Norway on 7 December 2016. In our analysis, we aim to identify the influences of moisture source conditions, weather system characteristics, and post-condensation processes on the isotope signal in near-surface water vapour and precipitation. A total of 71 precipitation samples were collected during the 24 h sampling period, mostly taken at sampling intervals of 10–20 min. The isotope composition of near-surface vapour was continuously monitored in situ with a cavity ring-down spectrometer. Local meteorological conditions were in addition observed from a vertical pointing rain radar, a laser disdrometer, and automatic weather stations. We observe a stretched, “W”-shaped evolution of isotope composition during the event. Combining paired precipitation and vapour isotopes with meteorological observations, we define four different stages of the event. The two most depleted periods in the isotope δ values are associated with frontal transitions, namely a combination of two warm fronts that follow each other within a few hours and an upper-level cold front. The d-excess shows a single maximum and a step-wise decline in precipitation and a gradual decrease in near-surface vapour. Thereby, the isotopic evolution of the near-surface vapour closely follows that of the precipitation with a time delay of about 30 min, except for the first stage of the event. Analysis using an isotopic below-cloud exchange framework shows that the initial period of low and even negative d-excess in precipitation was caused by evaporation below cloud base. The isotope signal from the cloud level became apparent at ground level after a transition period that lasted up to several hours. Moisture source diagnostics for the periods when the cloud signal dominates show that the moisture source conditions are then partly reflected in surface precipitation and water vapour isotopes. In our study, the isotope signal in surface precipitation during the AR event reflects the combined influence of atmospheric dynamics, moisture sources, and atmospheric distillation, as well as cloud microphysics and below-cloud processes. Based on this finding, we recommend careful interpretation of results obtained from Rayleigh distillation models in such events, in particular for the interpretation of surface vapour and precipitation from stratiform clouds.