Isotopic Model Research Articles

Fate and Transport of Mercury through Waterflows in a Tropical Rainforest.

Knowledge gaps of mercury (Hg) biogeochemical processes in the tropical rainforest limit our understanding of the global Hg mass budget. In this study, we applied Hg stable isotope tracing techniques to quantitatively understand the Hg fate and transport during the waterflows in a tropical rainforest including open-field precipitation, throughfall, and runoff. Hg concentrations in throughfall are 1.5-2 times of the levels in open-field rainfall. However, Hg deposition contributed by throughfall and open-field rainfall is comparable due to the water interception by vegetative biomasses. Runoff from the forest shows nearly one order of magnitude lower Hg concentration than those in throughfall. In contrast to the positive Δ199Hg and Δ200Hg signatures in open-field rainfall, throughfall water exhibits nearly zero signals of Δ199Hg and Δ200Hg, while runoff shows negative Δ199Hg and Δ200Hg signals. Using a binary mixing model, Hg in throughfall and runoff is primarily derived from atmospheric Hg0 inputs, with average contributions of 65 ± 18 and 91 ± 6%, respectively. The combination of flux and isotopic modeling suggests that two-thirds of atmospheric Hg2+ input is intercepted by vegetative biomass, with the remaining atmospheric Hg2+ input captured by the forest floor. Overall, these findings shed light on simulation of Hg cycle in tropical forests.

Regional vs. Local Isotopic Gradient: Insights andModeling from Mid-Mountain Areas inCentral Italy.

Mountainous zones are often characterized by complex orography and contacts between different aquifers that usually complicate the use of isotope hydrology techniques. The Apennine chain (Italy) and 10 mountain and mid-mountain areas belonging to it are the objective of this study. An original isotopic data treatment, able to identify the most probable recharge area for several springs/springs' groups/wells, has been developed. The method consists of a two-step approach: (1) the determination of the spring/wells computed isotope recharge elevation; (2) an advanced δ18O precipitation distribution model over the study area supported by statistical and GIS-based procedures implemented by two processes: first, the clipping of precipitation δ18O values (depicted from the δ18O-elevation relationships obtained for each study area) over a most probable recharge area for each analyzed spring or well and, second, the calculation of the overlapping distribution between the spring/well mean δ18O values ± σ and the precipitation δ18O content for each outcropping aquifer. A new regional δ18O gradient covering 150 km latitudinal length of central Italy has been defined. Seven LMWL and δ18O-elevation relationships able to represent the local precipitation isotopic composition have been obtained. The mean elevation of the springs and wells recharge areas have been assessed by a comparison between the obtained gradient with nine δ18O gradients available in the literature and those obtained at a local scale. The new isotopic modeling approach can stress whether the mere isotope modeling based on the stable isotope of oxygen agrees with the hydrogeological setting of the study areas.

Lithium isotope fractionation in highly evolved granites and associated magmatic-hydrothermal process: the case of the Xintianling granites in the Nanling Range, South China

ABSTRACT The highly evolved granites are closely associated with rare-metal mineralization. It is still debated whether the enrichment of rare metals is mainly controlled by magmatic or hydrothermal processes. Lithium is a fluid-mobile element that preferentially partitions to the fluid phase when the melt reaches H2O saturation, making the Li isotope system a powerful geochemical tool to record the potential melt-fluid interaction during magma evolution. This study addresses the issue of Li isotope fractionation in highly evolved fine syenogranites (FSGs) from the Xintianling pluton in the Nanling Range, South China. The Xintianling pluton consists of the coarse biotite monzogranites (CBMGs) and evolved FSGs. The identical Nd isotope data of the CBMGs (εNd(t) = -8.2–-8.8) and FSGs (εNd(t) = -7.9–-8.9) suggest that they were derived from the same crustal magma. The FSGs were derived from the highly evolved melts extracted from CBMGs through the fractionation of major rock-forming minerals. This is supported by the compositional shifts and validated by Rb, Sr, and Ba trace element modelling. Li isotopic analysis shows that highly evolved FSGs have heavier Li isotope compositions (δ7Li = 2.6–7.9 ‰) than the CBMGs (δ7Li = 0.1–1.9 ‰). Isotopic modelling, coupled with variations in Li concentrations in FSGs, suggests that diffusive kinetic fractionation by disequilibrium fluid exsolution during the late stage of the granitic magma evolution controls the Li isotope fractionation of the Xintianling granites. Rapid fluid exsolution not only modified the Li isotope composition of the FSGs but also transported the rare metals (e.g. W) and fluxing components (Li, F, and Cl), which resulted in the formation of the large Xintianling W deposits.

Implication of self-organizing map, stable isotopes combined with MixSIAR model for accurate nitrogen control in a well-protected reservoir

Nitrogen pollution and eutrophication in reservoirs is a global environmental geochemical concern. Occasional algal blooms still exist in reservoirs that have undergone pollution treatment. The lack of quantitative evidence of nitrogen sources and fate limits long-term stable ecological safety management. This work applied an approach integrated zonal mapping, stable isotopes (δ18OH2O, δ15Nnitrate, δ18Onitrate, and δ13C-DIC) and a Bayesian isotope model to analyze regional and seasonal differences in the contribution and sources of nitrogen to a well-protected reservoir. The values of δ18Onitrate and the positive relationship between NO3− and δ13C-DIC suggested that nitrification was the primary NO3− production in the rivers. While Denitrification was present at only a few sites. Results of the MixSIAR model coupled the NO3−/Cl− indicator revealed that the domestic sewage contributed high riverine NO3− loading (68.6 ± 10.6 %) in the dry season. In the wet season, the main nitrate sources of upper watershed were ammonia and carbamide fertilizers (47.5 % and 40.3 %). While the domestic sewage was still the major contributor of downstream region (a dense residential area), indicating possible problems with rainwater and sewage drainage networks. The results implied that the colleting and treatment of sewages were the priority in downstream region, and non-point source pollution control and wastewater treatment plant upgrading were essential to control nitrate pollution in the two upstream regions. These findings provide new insights into precise nitrogen pollution traceability and identification of treatment priorities in the sub-region, and promote the management other well-protected watershed in similar need of further nitrogen contamination control.

Mariculture may intensify eutrophication but lower N/P ratios: a case study based on nutrients and dual nitrate isotope measurements in Sansha Bay, southeastern China

The mariculture industry has grown rapidly worldwide over the past few decades. The industry helps meet growing food demands and may provide an effective means of carbon sequestration; however, it may harm the marine ecological environment, and the extent of its impact depends on the type of mariculture. Here we focus on the impact of mariculture on the nutrient status and eutrophication in Sansha Bay, which is a typical aquaculture harbor in southeastern China that employs a combination of shellfish and seaweed farming. Nutrient concentrations and dual nitrate isotopes were measured in Sansha Bay during the winter of 2021. The average concentrations of nitrate and phosphate were 31.3 ± 10.5 and 2.26 ± 0.84 µM, respectively, indicating that the water was in a eutrophic state. However, the N/P ratios were relatively low (14.3 ± 2.2). Nitrate isotope measurements were 8.8‰–11.9‰ for δ15N-NO3− and 2.2‰–6.0‰ for δ18O-NO3−. Source analysis based on the nitrate isotope measurements indicates that nitrate in Sansha Bay is derived mainly from the excretion of organisms and sewage discharge from mariculture. The isotopic fractionation model of nitrate assimilation by organisms indicates that surface waters in Sansha Bay experience strong biological uptake of nitrate, which is likely related to seaweed farming in winter. The low N/P ratios may be attributed to excessive nitrogen uptake (relative to phosphorus) during shellfish and seaweed farming, as well as nitrogen removal through sediment denitrification, which is fueled by the sinking of particulate organic matter from mariculture. Overall, our study shows that mariculture activities dominated by shellfish and seaweed cultivation in Sansha Bay may exacerbate eutrophication but reduce N/P ratios in the water column in aquaculture areas.

A nitrogen isoscape of phytoplankton in the western North Pacific created with a marine nitrogen isotope model

The nitrogen isotopic composition (δ15N) of phytoplankton varies substantially in the ocean reflecting biogeochemical processes such as N2 fixation, denitrification, and nitrate assimilation by phytoplankton. The δ15N values of zooplankton or fish inherit the values of the phytoplankton on which they feed. Combining δ15N values of marine organisms with a map of δ15N values (i.e., a nitrogen isoscape) of phytoplankton can reveal the habitat of marine organisms. Remarkable progress has been made in reconstructing time-series of δ15N values of migratory fish from various tissues, such as otoliths, fish scales, vertebrae, and eye lenses. However, there are no accurate nitrogen isoscapes of phytoplankton due to observational heterogeneity, preventing improvement in the accuracy of estimating migratory routes using the fish δ15N values. Here we present a nitrogen isoscape of phytoplankton in the western North Pacific created with a nitrogen isotope model. The simulated phytoplankton is relatively depleted in 15N at the subtropical site (annual average δ15N value of phytoplankton of 0.6‰), where N2 fixation occurs, and at the subarctic site (2.1‰), where nitrate assimilation by phytoplankton is low due to iron limitation. The simulated phytoplankton is enriched in 15N at the Kuroshio–Oyashio transition site (3.9‰), where nitrate utilization is high, and in the region around the Bering Strait site (6.7‰), where partial nitrification and benthic denitrification occur. The simulated δ15N distributions of nitrate, phytoplankton, and particulate organic nitrogen are consistent with δ15N observations in the western North Pacific. The seamless nitrogen isoscapes created in this study can be used to improve our understanding of the habitat of marine organisms or fish migration in the western North Pacific.

Isotopic and geochemical modeling approach to evaluate abiotic nitrite reduction by ferrous iron

Nitrite reduction has often been treated as a biotic process in water treatment systems, but it also occurs abiotically, and it is difficult to distinguish both reactions as they can co-occur at field-scale. The potential reduction of NO2− was tested in 3 anaerobic experimental scenarios using a NO2− bearing solution amended with: i) siderite (FeCO3) (Sid experiment); ii) Fe(II) solution from FeCl2.4H2O(s) (DFe experiment); and iii) siderite mixed with Fe(II) solution (Sid+DFe experiment). Non-sterilized batch experiments were carried out in anaerobic conditions with an initial ratio of nitrogen to dissolved iron of 5 in DFe and Sid+DFe (Sid had no initially dissolved Fe(II)) and 1000 mg L−1 of siderite in Sid and Sid+DFe experiments. At the end of the experiments, the NO2− removed was 3% for Sid, 54% for DFe and 84% for Sid+DFe. The NO2− concentration decrease over time was characterized by an enrichment in the δ15NNO2 of the unreacted NO2−, increasing from −26.9 ‰ to −26.4 ‰ (Sid), −18.0 ‰ (DFe) and −15.9 ‰ (Sid+DFe). The calculated ε15NNO2 for Sid was −11.8 ‰, whereas for DFe was −12.0 ‰ and Sid+DFe was −13.0 ‰, suggesting a common NO2− degradation mechanism in all experiments. The Rayleigh distillation equation showed that the generated N2O was the final product of the abiotic nitrite reduction reaction, and the calculated N2O site preference (SP) was 22.5 ± 0.7 ‰ for DFe and 23.5 ± 0.5 ‰ for Sid+DFe. The continuous N2O measurement showed that only 25.3 ± 5.1% in DFe and 31.0 ± 6.3% in Sid+DFe of the generated N2O in water was recovered in the headspace vials, suggesting that a large portion of the produced N2O(aq) in solution did not diffuse from water. The coupled NO2− reduction and Fe(II) oxidation followed a second-order kinetic reaction with a rate equal to (9.39 ± 0.36)·10−4·[NO2−]·[Fe(II)] (mol L−1 s−1) in all experiments. The experimental conditions supported by the Rayleigh distillation equation using the experimentally calculated ε15N values, coupled with NO2− isotopic data and N2O SP values, showed that biological denitrification had a negligible influence on nitrite reduction and that chemodenitrification was the main NO2− attenuation pathway. A geochemical model coupling the kinetic chemodenitrification, isotope fractionation, aqueous speciation in equilibrium and precipitation and dissolution of calcite has been implemented and reproduced the experimental results. The geochemical model developed in our study can be applied to similar experimental studies and to field-scale studies to predict the efficiency of abiotic nitrite reduction treatments using Fe(II).

Thermotopes-COH—A software for carbon isotope modeling and speciation of COH fluids

Carbon-bearing fluids and condensed carbon are common on and inside planetary bodies. Understanding the mechanisms capable of transferring carbon from fluids into solids and vice-versa is central in many fundamental and applied research targets within the Earth and Planetary Sciences. A broad range of applications can benefit from the thermodynamic properties of carbon-oxygen-hydrogen (COH) systems. As an example, the precipitation of natural graphite or diamond can be modeled within the COH thermodynamic systems. Because the evolution of COH fluids implies isotopic fractionation among different species, carbon stable isotopes can be used in conjunction with thermodynamic calculations to reconstruct graphite or diamond formation mechanisms, or the evolution of fluid species such as carbon dioxide or methane.Thermotopes-COH is a Python-based graphical user interface (GUI) software for computation of thermodynamic and carbon isotopic modeling in the C–O–H system within the 0.1–5 GPa and 300–900 °C range. The software allows generic and process-oriented thermodynamic and carbon stable isotope calculations including fluid mixing, fluid-graphite/diamond interactions with changing pressure or temperature, and fluid desiccation. This versatile numerical tool is designed to model processes of dissolution/precipitation of graphite or diamond. Along with a description of the software functions, this contribution also provides practical examples.

Control priority based on source-specific DALYs of PM2.5-bound heavy metals by PMF-PSCF-IsoSource model in urban and suburban Beijing

To determine the priority control sources, an approach was proposed to evaluate the source-specific contribution to health risks from inhaling PM2.5-bound heavy metals (PBHMs). A total of 482 daily PM2.5 samples were collected from urban and suburban areas of Beijing, China, between 2018 and 2019. In addition to the PMF-PSCF model, a Pb isotopic IsoSource model was built for more reliable source apportionment. By using the comprehensive indicator of disability-adjusted life years (DALYs), carcinogenic and noncarcinogenic health risks could be compared on a unified scale. The study found that the annual average concentrations of the total PBHMs were significantly higher in suburban areas than in urban areas, with significantly higher concentrations during the heating season than during the nonheating season. Comprehensive dust accounted for the largest contribution to the concentration of PBHMs, while coal combustion contributed the most to the DALYs associated with PBHMs. These results suggest that prioritizing the control of coal combustion could effectively reduce the disease burden associated with PBHMs, leading to notable public health benefits.

Denitrification regulates spatiotemporal pattern of N2O emission in an interconnected urban river-lake network

Urban rivers are hotspots of N2O production and emission. Interconnected river-lake networks are constructed to improve the water quality and hydrodynamic conditions of urban rivers in many cities of China. However, the impact of the river-lake connectivity project on N2O production and emission remains unclear. This study investigated dissolved N2O and emission of the river-lake network in Wuhan City, China from March 2021 to December 2021. The results showed that river-lake connection greatly decreased riverine Nitrogen (N) concentration and increased dissolved oxygen (DO) concentration compare to traditional urban rivers. N2O emissions from the urban river interconnected with lakes (LUR: 67.3 ± 92.6 μmol/m2/d) were much lower than those from the traditional urban rivers (UR: 467.3 ± 1075.7 μmol/m2/d) and agricultural rivers (AR: 20.4 ± 15.3μmol/m2/d). Regression tree analysis suggested that the N2O concentrations were extremely high when hypoxia exists (DO < 1.6 mg/L), and TDN was the primary factor regulating N2O concentrations when hypoxia does not occur. Thus, we ascribe the low N2O emission in the LUR and AR to the lower N contents and higher DO concentrations. The microbial process of N2O production and consumption were quantitatively estimated by isotopic models. The mean proportion of denitrification derived N2O (fbD) was 63.5 %, 55.6 %, 42.3 % and 42.7 % in the UR, LUR, lakes and AR, suggested denitrification dominated N2O production in the urban rivers, but nitrification dominated N2O production in the lakes and AR. The positive correlation between logN2O and fbD suggested that denitrification is the key process to regulate the N2O production and emission. The abundance of denitrification genes (nirS and nirK) was much higher than that of nitrification genes (amoA and amoB), also evidenced that denitrification was the main N2O source. Therefore, river-lake interconnected projects changed the nutrients level and hypoxic condition, leading to the inhibition of denitrification and nitrification, and ultimately resulting in a decrease of N2O production and emission. These results advance the knowledge on the microbial processes that regulate N2O emissions in inland waters and illustrate the integrated management of water quality and N2O emission.

Petrogenesis of early Paleozoic peraluminous A-type granites from southern China

ABSTRACT Early Paleozoic A-type granites in South China are rare, and their petrogenesis is still highly debated. This study focuses on the controversial Epo pluton in the Wuyi-Yunkai Orogen and conducts petrological and petrogeochemical research to discuss its origin. The Epo granites were emplaced at approximately 414 Ma and exhibit petrological and geochemical features of A-type granites. They contain only one ferromagnesian mineral, ferrum biotite. The granites mostly have high alkalis contents (Na2O + K2O = 6.48–8.85 wt.%), high field strength element (HFSE) contents (Zr + Nb + Ce + Y = 353–461 ppm), and high Ga/Al (104×Ga/Al = 2.50–3.72) and FeOT/(FeOT + MgO) (0.74–0.85) ratios. Besides, they formed under high-temperature (>850°C) and low-pressure (≤5 kbar) conditions. Their high A/CNK (average 1.20) and Eu/Eu* (average 0.46) values as well as Sr (average 128 ppm) and Ba (average 628 ppm) contents but relatively low Zr contents (approximately 200 ppm) further suggest a strongly peraluminous A-type affinity, a distinctive subtype of A-type granites. The Epo granites display enriched Sr-Nd-Hf isotope compositions with a whole-rock87Sr/86Sri average ratio of 0.712, whole-rock εNd(t) values ranging from − 8.9 to − 7.6, and zircon εHf(t) values clustering at − 8. Their two-stage Nd and Hf isotope model ages are 1.7 Ga to 2.0 Ga, suggesting ancient crustal sources. Furthermore, Nb/U (average 7.46), Ce/Pb (average 4.06) and other trace element ratios indicate negligible contributions from juvenile mantle materials. Our data on the Epo pluton, coupled with other contemporary A-type granites in South China, suggest that the high-temperature melting of metasedimentary basements generated strongly peraluminous A-type granites, while the involvement of metaigneous rocks or mantle-derived magmas resulted in metaluminous to weakly peraluminous A-type granites. Source diversity leads to different aluminium saturations. The heat required to produce high-temperature A-type magmas was supplied by upwelling mantle-derived magma in a postcollisional extensional setting.

Identifying recycled oceanic components and volatiles in the Lizhuang carbonatite-associated REE deposit in southwest China: New constrain from in situ Hf–O isotopes

Carbonatite-associated rare earth element (REE) deposits (CARD) are mainly found at the edges of cratons in the rift or post-collisional settings, but only a minority carbonatite can form large to giant REE deposit. Fluids rich in volatiles (such as F, Cl, S) are critical for the extraordinary enrichment of REE, but the manner in which volatiles and REE concentrate in the mantle source of CARD remains unclear. This study focuses on the Lizhuang syenite from the Mianning–Dechang REE belt, southwest China, to investigate its petrogenesis, source characteristics, and volatiles evolution, through in situ Hf–O isotope analysis, coupled with mineral chemistry, bulk-rock geochemistry, and geochronology. The Lizhuang syenite was generated in a post-collisional setting at about 27 Ma, resulting from partial melting of an enriched lithospheric mantle, followed by fractional crystallization and immiscibility. When contrasted with barren carbonatite-syenite complexes worldwide, the syenite in REE deposit has a relatively higher content of F and S, with no significant difference in Cl content, and there is no clear correlation between magma oxygen fugacity and REE mineralization. The Hf–O isotopic signatures of zircon and apatite, along with bulk-rock Sr–Nd isotopic modeling, reveal that the mantle source of the Mianning–Dechang CARD experienced metasomatic processes related to the melts/fluids derived from both marine sediments and altered oceanic crust during subduction. The cratonic root, enriched in volatiles and REE, is reactivated during the upwelling of asthenosphere, and the released volatiles are able to participate in the formation of CARD.

Assessment of nursery areas for the scalloped hammerhead shark (Sphyrna lewini) across the Eastern Tropical Pacific using a stable isotopes approach

The scalloped hammerhead shark (Sphyrna lewini) is one of the most iconic marine species across the Eastern Tropical Pacific (ETP), yet little is still known about its reproductive biology and the origin of their nursery areas, despite a continuous global decline in their populations. Understanding the origin of shark nurseries is a complex task; however, it is known that the obtention of resources in the first stages of life of placental sharks occurs through maternal reminiscence, thus it is possible to infer the origin of the energy that neonates accumulate during their gestation. In this study we assessed the ecological connectivity and nursery ground use by undertaking a stable isotope analysis of carbon (δ13C) and nitrogen (δ15N) in skin samples of neonates S. lewini across much of their distribution in the ETP, including the Galapagos Marine Reserve (GMR). Our isotopic mixing models revealed that the S. lewini neonates found in the GMR, have isotopic information similar to adult females inhabit in the Galapagos archipelago, suggesting that they are direct descendants of the females that inhabit the GMR. While neonates found off the continental coasts of Ecuador and Panama have isotopic signatures like those of adult females inhabiting several locations across the ETP. This work provides insight into the origin of nursery areas used by adult S. lewini that aggregate in large numbers across oceanic islands of the ETP, highlighting the value of isotopic models to generate useful information for the conservation of sharks.

Applications of First-Order Ordinary Differential Equations to Real-Life Systems

This article discussed applications of first-order ordinary differential equations to real-life systems, various types of differential equations with examples are presented. When a dead body is discovered somewhere, Police and detective security agencies are eager to identify the time of death and what caused the death. In this article, Newton’s Law of Cooling is used to estimate the time of death of a dead body discovered at midnight with the aid of information about the body’s surrounding temperature. It was discovered in this study that Newton’s law of cooling only works when the temperature of the body’s surroundings is kept constant. The study also considered other applications of first-order differential equations such as the population growth model and radioactive decay of radioactive isotopes and illustrative examples are given in each case.

The world-class carbonate-hosted Fankou Zn-Pb deposit in China. Part II. Alterations: C-O isotopic halos footprint the nature and transfer pathway of ore-fluids, and quantitative water-rock interaction process

The giant Fankou Zn-Pb deposit (more than 10 Mt Zn + Pb metals, grading at 15 %), situated in northern margin of the Quren Basin, is one of the largest Zn-Pb deposits in China. The stratiform orebodies are jointly bounded by both the strata (in the specific layers of Middle to Upper Devonian Donggangling and Tianziling carbonate sequences) and the fault system (a three-order thrusting fault system). Ore textures of carbonate dissolution, replacement-infilling and cementation are widespread in Fankou, analogous to a MVT (Mississippi Valley-type) deposit. Owing to the poorly developed fluid inclusions, the nature of the Fankou ore fluids remains indeterminate. To address this problem, we herein utilize micro-petrography, carbon-oxygen (C-O) isotopes and quantitative isotopic exchange modelling to trace the ore-fluids and water-rock interaction process. A total of ninety-three (93) carbonate samples, covering the majorities of stratigraphic horizons, planar locations, and various alteration intensities, were systematically collected. Micro-petrography reveals the primitively sedimentary bioclastic limestone suffer from heterogeneous dolomitization and carbonatization followed by massive Zn-Pb precipitation. These carbonate samples display a widely-ranged, δ18O- and δ13C-depleted isotope signature (δ18O = 12.57 to 23.82 ‰, δ13C = −7.79 to −0.46 ‰), relative to normal marine carbonates (δ18O = 25 ‰, δ13C = 0 ‰). Further modelling of isotopic exchange indicates a low-temperature (100 to 250 °C), δ18O-depleted (−3 to 7 ‰) and δ13C-depleted (−10 to −7‰) ore fluid equilibrated with the host rock by a relatively low water-rock ratio (W/R = 1 to 10). In terms of space, we identified a relatively decreasing trend of δ18O and δ13C isotopic compositions of carbonates, from southeast to northwest, and from bottom to up. Based upon the previous structural analysis, we interpret that the δ18O and δ13C isotopic distribution patterns are caused by a northwestwards transfer pathway of ore-fluids along the thrusting fault system, and the metalliferous, δ18O- and δ13C-depleted fluids are sourced from the interior of the Quren Basin. Collectively, we clarify the deep southeastern part of the Fankou Zn-Pb deposit and the interiors of the Quren Basin is the favorable exploration target in future.

From atmospheric water isotopes measurement to firn core interpretation in Adélie Land: a case study for isotope-enabled atmospheric models in Antarctica

Abstract. In a context of global warming and sea level rise acceleration, it is key to estimate the evolution of the atmospheric hydrological cycle and temperature in polar regions, which directly influence the surface mass balance of the Arctic and Antarctic ice sheets. Direct observations are available from satellite data for the last 40 years and a few weather data since the 1950s in Antarctica. One of the best ways to access longer records is to use climate proxies in firn or ice cores. The water isotopic composition in these cores is widely used to reconstruct past temperature variations. We need to progress in our understanding of the influence of the atmospheric hydrological cycle on the water isotopic composition of ice cores. First, we present a 2-year-long time series of vapor and precipitation isotopic composition measurement at Dumont d’Urville Station, in Adélie Land. We characterize diurnal variations of meteorological parameters (temperature, atmospheric water mixing ratio (hereafter humidity) and δ18O) for the different seasons and determine the evolution of key relationships (δ18O versus temperature or humidity) throughout the year: we find that the temperature vs. δ18O relationship is dependent on synoptic events dynamics in winter contrary to summer. Then, this data set is used to evaluate the atmospheric general circulation model ECHAM6-wiso (model version with embedded water stable isotopes) in a coastal region of Adélie Land where local conditions are controlled by strong katabatic winds which directly impact the isotopic signal. We show that a combination of continental (79 %) and oceanic (21 %) grid cells leads model outputs (temperature, humidity and δ18O) to nicely fit the observations, at different timescales (i.e., seasonal to synoptic). Therefore we demonstrate the added value of long-term water vapor isotopic composition records for model evaluation. Then, as a clear link is found between the isotopic composition of water vapor and precipitation, we assess how isotopic models can help interpret short firn cores. In fact, a virtual firn core built from ECHAM-wiso outputs explains much more of the variability observed in S1C1 isotopic record than a virtual firn core built from temperature only. Yet, deposition and post-deposition effects strongly affect the firn isotopic signal and probably account for most of the remaining misfits between archived firn signal and virtual firn core based on atmospheric modeling.

Isotopic evolutionary track of water due to interaction with rocks and its use for tracing water cycle through the lithosphere

Hydrogen and oxygen isotopic compositions of natural spa waters from hot and/or mineral-rich springs (including flowing/pumping wells) potentially provide important clues about water cycle in Earth's interior, because some of the waters are deep-seated and non-meteoric. However, the isotopic compositions of these waters are typically altered by contamination with meteoric water and are thus poorly known. To reconstruct their original (i.e., before these waters mix with meteoric water) isotope compositions, here we develop an isotopic evolution model of the lithosphere-enclosed waters and derive the “ocean-origin lithospheric water curve” (OLWC; δ2H = 60 / (δ18O – 11)) as a typical evolutionary track starting from ocean water. Then we apply them to spa waters from central Japan, a globally unique geotectonic region where double subduction of slabs occurs. The OLWC explains well observed isotope data of subseafloor pore waters, submarine mud volcano pore waters, coastal oil-field brines, and subduction zone volcanic steam. Mixing analysis indicates that lithospheric water accounts for 19–95 % of each spa water we investigated. The nonlinear relationships of the reconstructed water δ18O and Cl or Li concentrations justify our hypothesis that the lithospheric waters are undergoing evolution from ocean water to magmatic water by rock-water isotopic exchange and that they are not simply mixtures of the two. A comparison of the reconstruction results with model predictions under slab subduction settings suggests that most spa waters in the southern to central part of the study region contain progressively evolving lithospheric waters released from the subducting Philippine Sea slab, and that a few at western edge of the region contain waters released from the Pacific slab. The others in the northern and eastern part of the region contain waters at the early-to-mid evolutionary stage, which are discharged from Tertiary marine sedimentary rocks (including tuffs). All these waters were enclosed in the lithosphere for more than 1–5 Ma. Our approach provides useful tools for tracing sources of non-meteoric water and highlights water cycle through lithosphere for more than one million years.

Climate change-informed dietary modeling in Pacific cod: Experimentally-derived effects of temperature and dietary quality on carbon and nitrogen stable isotope trophic discrimination factors

Stable isotope analysis is a powerful tool for dietary modeling and trophic ecology research. A crucial piece of information for isotopic dietary modeling is the accurate estimation of trophic discrimination factors (TDFs), or the isotopic offset between a consumer’s tissue and its diet. In order to parameterize stable isotope dietary models for future climate scenarios, we investigated the effect of water temperature and dietary protein and lipid content on TDFs in juvenile Pacific cod (Gadus macrocephalus). Pacific cod are a commercially and ecologically important species, with stock numbers in the northeast Pacific recently having dropped by more than 70%. We tested four water temperatures (6, 8, 10, and 12°C) and two dietary regimens (low and high lipid content), representing a range of potential ocean temperature and prey quality scenarios, in order to determine carbon and nitrogen TDFs in juvenile Pacific cod. Additionally, we assessed dietary intake and proximate composition of the experimental fish in order to estimate consumption, assimilation, and retention of dietary nutrients. The results of this study suggest that dietary protein catabolism is a primary driver of nitrogen TDF variability in juvenile Pacific cod. Across all temperature treatments from 6 to 12°C, fish reared on the lower quality, lower lipid content diet had higher nitrogen TDFs. The mean TDFs for fish raised on the higher lipid, lower protein diet were +3.40 ‰ for nitrogen (Δ15N) and +0.36 ‰ for lipid-corrected carbon (Δ LC 13C). The mean TDFs for fish raised on the lower lipid, higher protein diet were +4.09 ‰ for nitrogen (Δ15N) and 0.00 ‰ for lipid-corrected carbon (Δ LC 13C). Lipid-corrected carbon isotope data showed that, regardless of temperature, fish consuming the lower lipid diet had essentially no trophic discrimination between diet and bulk tissues. We found no ecologically meaningful differences in TDFs due to water temperature across the 6°experimental range. The results of this experiment demonstrate that dietary quality, and more specifically the use of dietary protein for energetic needs, is a primary driver of trophic discrimination factors. The TDFs determined in this study can be applied to understanding trophic ecology in Pacific cod and closely related species under rapidly changing prey availability and ocean temperature conditions.

Prebiotic synthesis on meteorite parent bodies: Insights from hydrogen and carbon isotope models

Several mechanisms could produce the biorelevant organic compounds contained in carbonaceous meteorites. The ratio of heavy-to-light stable isotopes can constrain a compound's formation history because substrates, mechanisms, and physiochemical conditions impact isotope ratios of a reaction's products. Prior stable isotope studies of meteoritic organic compounds have interpreted data via qualitative or semi-quantitative models. Here we create quantitative models (i.e., explicitly fit to measurements) for hydrogen and carbon isotope compositions of organic compounds in primitive carbonaceous meteorite and use these models to reach broader conclusions regarding the environments, substrates, and chemical processes that contributed to their synthesis.The hydrogen isotope model gathers previous molecular-average δD measurements, sorts them into compounds classes (e.g., amines, carboxylic acids), and fits the measurements in each class as linear combinations of the non-exchangeable hydrogen moieties, which are determined by their chemical environment (e.g., R-CH3, R-CH(NH2)(COOH)). In the chondrites studied, methyl hydrogens are the most deuterium-enriched moiety (up to 5000 ‰) and hydrogens attached to α‑carbons are the least. Deuterium enrichment is inversely related to a moiety's acidity and a meteorite sample's degree of aqueous alteration and terrestrial weathering, which suggests that ISM-sourced compounds reacted to form deuterium-enriched organic molecules before parent body accretion or during parent body evolution and that those D enrichments were variably attenuated through exchange with water during aqueous alteration on the parent body and subsequent terrestrial processing.The carbon isotope model tests five potential chemical reaction networks by taking δ13C of reactants for each network and applying isotope effects to determine a range of product δ13C from minimal to complete reactant conversion. The model that fits compounds in the Murchison meteorite most accurately (70% of previous measurements fall within the values predicted by model ±5‰) with the lowest average residuals (6‰) uses an integrated aldehyde network (oxidation, reductive amination, and Strecker synthesis acting on an initial pool of aldehydes and ketones) to produce straight-chain compounds, which then react with aldehydes to create branched-chain compounds. The addition of aldehydes provides a parsimonious fit the carbon isotope contents of compounds that span over 100‰ in δ13C, making it an attractive working hypothesis.

Origin of Archean Pb isotope variability through open-system Paleoarchean crustal anatexis

Abstract Lead isotopic data imply that thorium and uranium were fractionated from one another in Earth’s early history; however, the origin of this fractionation is poorly understood. We report new in situ Pb isotope data from orthoclase in 144 granites sampled across the Archean Yilgarn craton (Western Australia) to characterize its Pb isotope variability and evolution. Granite Pb isotope compositions reveal three Pb sources, a mantle-derived Pb reservoir and two crustal Pb reservoirs, distinguished by their implied source 232Th/238U (κPb). High-κPb granites reflect sources with high 232Th/238U (~4.7) and are largely co-located with Eoarchean–Paleoarchean crust. The Pb isotope compositions of most granites, and those of volcanic-hosted massive sulfide (VHMS) and gold ores, define a mixing array between a mantle Pb source and a Th-rich Eoarchean–Paleoarchean source. Pb isotope modeling indicates that the high-κPb source rocks experienced Th/U fractionation at ca. 3.3 Ga. As Th/U fractionation in the Yilgarn craton must have occurred before Earth’s atmosphere was oxygenated, subaerial weathering cannot explain the apparent differences in their geochemical behavior. Instead, the high Th/U source reflects Eoarchean–Paleoarchean rocks that experienced prior high-temperature metamorphism, partial melting, and melt loss in the presence of a Th-sequestering mineral like monazite. Archean Pb isotope variability thus has its origins in open-system high-temperature metamorphic processes responsible for the differentiation and stabilization of Earth’s continental crust.