Significant Isotope Fractionation Research Articles

Stable isotopic evidence of cadmium enrichment in soils of black shale distribution areas

Black shale-derived soils exhibit significant heavy metal enrichment, notably cadmium (Cd) enrichment. This study pioneered the reporting of δ114/110Cd isotopic values within a black shale-soil system, offering novel insights into the geochemical behaviors and enrichment mechanisms of Cd during soil formation processes influenced by weathering. Systematic rock‒soil sampling was conducted on the lower Cambrian Hetang Formation in western Zhejiang, China, which is characterized by Cd-rich black shale. Employing analytical methods, including principal component analysis and multiple linear regression, we investigated the factors influencing heavy metal content in soil, such as element dissolution during weathering, soil pH, and the presence of iron-manganese oxides, sulfides, organic matter, and clay minerals. Our findings revealed a compositional range of δ114/110Cd in black shale (1.93‰–3.31‰) contrasting with that in adjacent soils (0.31‰–1.82‰), illustrating significant Cd isotopic fractionation during weathering, where heavier Cd isotopes are preferentially leached, and lighter isotopes are enriched in the soil in association with iron-manganese oxides. This research not only deepens the understanding of Cd enrichment mechanisms within the rock‒soil system against a black shale geological background but also elucidates the formation processes of soil Cd pollution in areas with a high geochemical background.

Impact sculpting of the early martian atmosphere.

Intense bombardment of solar system planets in the immediate aftermath of protoplanetary disk dissipation has played a key role in their atmospheric evolution. During this epoch, energetic collisions will have removed substantial masses of gas from rocky planet atmospheres. Noble gases are powerful tracers of this early atmospheric history, xenon in particular, which on Mars and Earth shows significant depletions and isotopic fractionations relative to the lighter noble gasses. To evaluate the effect of impacts on the loss and fractionation of xenon, we measure its ionization and recombination efficiency by laser shock and apply these constraints to model impact-driven atmospheric escape on Mars. We demonstrate that impact bombardment within the first 200 to 300 million years of solar system history generates the observed Xe depletion and isotope fractionation of the modern martian atmosphere. This process may also explain the Xe depletion recorded in Earth's deep mantle and provides a latest date for the timing of giant planet instability.

Revisiting magnesium isotope constraints on the petrogenesis of the Fe-Ti oxide-bearing mafic–ultramafic intrusions

Stable isotopes of metals, such as magnesium (Mg) and iron (Fe), typically undergo minimal fractionation at magmatic temperatures. However, in Fe-Ti oxide-bearing intrusions, significant Mg isotope fractionation (Δ26Mg values of up to 23 ‰) has been observed between silicates and Fe-Ti oxides. The mechanism responsible for this substantial fractionation remains unclear. This study presents Mg isotopic compositions for bulk rocks and mineral separates—including olivine, clinopyroxene, titanomagnetite, ilmenite—from sixteen Fe-Ti oxide ores in both the lower and the upper zones of the Baima layered mafic–ultramafic intrusion, as well as bulk rocks from three high-Ti basalts of the Emeishan large igneous province, SW China. Oxide ores from the lower zone and the lower section of the upper zone of the Baima intrusion are characterized by a low abundance of volatile-bearing minerals, such as apatite and hornblende. These ores exhibit δ26Mg values ranging from −0.30 to −0.14 ‰ for olivine, −0.26 to −0.06 ‰ for clinopyroxene, 0.16 to 0.60 ‰ for titanomagnetite and −0.33 to −0.21 ‰ for ilmenite, indicative of near-equilibrium fractionation. In contrast, oxide ores from the upper section of the upper zone exhibit a high abundance of volatile-bearing minerals and significantly different δ26Mg values, ranging from −0.19 to −0.05 ‰ for olivine, −0.25 to −0.10 ‰ for clinopyroxene, 0.57 to 0.60 ‰ for titanomagnetite and 0.86 to 2.34 ‰ for ilmenite, indicative of disequilibrium fractionation. A negative correlation between Fo content and δ26Mg value in olivine suggests that Mg isotopes fractionate as olivine undergoes fractional crystallization. Trapped liquid fractions, calculated based on Ce contents in apatite, suggest that rocks with high volatile-bearing mineral content have undergone re-equilibration with trapped liquids during cooling. The large disequilibrium Mg isotopic fractionation between silicates and Fe-Ti oxides is likely due to sub-solidus re-equilibration between minerals and trapped liquids. We propose that the extent of sub-solidus, diffusion-driven kinetic Mg isotopic fractionation in Fe-Ti oxide-bearing intrusions likely correlates with the volume of trapped liquids, which may serve as a significant medium accelerating ion exchange between silicates and Fe-Ti oxides. Moreover, mass balance calculations indicate that data of Mg isotopes on their own are insufficient to determine the petrogenesis of Fe-Ti oxides in layered intrusions. This insufficiency is primarily due to the low MgO content in titanomagnetite and ilmenite, where their separation causes minimal Mg isotopic fractionation of the melts.

Variation and fractionation of δ2H, δ18O, and δ17O stable isotopes from irrigation water to soil, grapes, and wine for the traceability of geographical origins

To investigate the variation and fractionation of stable isotopes from irrigation water to soil, grapes, and wine, δ2H, δ18O, and δ17O in different samples from 10 regions in China were determined using a water isotope analyser. The values were significantly different among regions according to the chemometric analysis. All isotopes were significantly and positively correlated with irrigation water–soil and grape–wine. A significant water isotopic fractionation effect was observed from the irrigation water to the soil, grapes, and wine. Stable isotope distribution characteristics correlated with longitude, latitude, altitude, temperature, precipitation, station pressure and wind speed. The linear discriminant analysis (LDA), random forest (RF), support vector machine (SVM), and feed-forward neural network (FNN) models 58.33–100 %, 80–100 %, 53.33–100 %, and 73.33–100 % accurate for distinguishing the geographical origins of all samples from training and test data, respectively. These findings provide a theoretical basis for authenticating the geographic origin of Chinese wines using stable isotope analysis.

Dynamic fractionation of methane carbon isotope during mass transport in coal with bidisperse pore structures: Experiments, numerical modeling, and applications

Gas-in-place (GIP) content and the in-situ free/adsorbed gas ratio are crucial factors for evaluating resource potential and optimizing production strategies of deep coalbed methane (CBM). While the prevailing notion that adsorbed gas predominates is widely accepted in shallow CBM, this idea has been contested in deep CBM. Various numerical models for calculating GIP content based on gas volume data from canister degassing experiments commonly suffer from low accuracy, strong multiplicity, and inability to evaluate critical parameters of free/adsorbed gas ratio. Isotope fractionation is an important tool for studying the occurrence state and transport mechanism of natural gas, and numerical modeling that considers both cumulative degassing content and carbon isotope data has proven effective in determining the GIP content and adsorbed gas ratio in shale. However, the applicability of the existing isotope fractionation models in deep CBM has yet to be demonstrated experimentally and theoretically. In this study, four coal samples from the Shanxi and Taiyuan formations in Ordos Basin were subjected to canister degassing, gas metering, and methane isotopic composition testing. The results revealed significant multi-stage carbon isotope fractionation characteristics throughout deep CBM degassing, reflecting the strong heterogeneous pore structure characteristics within the coal. Existing carbon isotope fractionation (CIF) models are unable to effectively characterize this complex phenomenon. Based on these findings, we innovatively developed a CIF model that considers bidisperse pore structures and multiple transport mechanisms. The model can better characterize the complex isotope fractionation behavior and reveal the mechanisms of carbon isotope transport in series structures of multi-scale pores. Using the model, we calculated the GIP content of four experimental samples from the Shanxi and Taiyuan formations on the southeastern edge of the Ordos Basin, ranging from 27.78 m3/t to 39.13 m3/t, with an average of 31.68 m3/t, and the in-suit free gas ratio ranges from 13.30 % to 32.89 %, with an average of 19.45 %. These research findings provided new insights for assessing the resource potential of deep CBM, screening sweet spots, and predicting gas well performance.

Vitamin B12 as a source of variability in isotope effects for chloroform biotransformation by Dehalobacter.

Carbon and chlorine isotope effects for biotransformation of chloroform by different microbes show significant variability. Reductive dehalogenases (RDase) enzymes contain different cobamides, affecting substrate preferences, growth yields, and dechlorination rates and extent. We investigate the role of cobamide type on carbon and chlorine isotopic signals observed during reductive dechlorination of chloroform by the RDase CfrA. Microcosm experiments with two subcultures of a Dehalobacter-containing culture expressing CfrA-one with exogenous cobamide (Vitamin B12, B12+) and one without (to drive native cobamide production)-resulted in a markedly smaller carbon isotope enrichment factor (εC, bulk) for B12- (-22.1 ± 1.9‰) compared to B12+ (-26.8 ± 3.2‰). Both cultures exhibited significant chlorine isotope fractionation, and although a lower εCl, bulk was observed for B12- (-6.17 ± 0.72‰) compared to B12+ (-6.86 ± 0.77‰) cultures, these values are not statistically different. Importantly, dual-isotope plots produced identical slopes of ΛCl/C (ΛCl/C, B12+ = 3.41 ± 0.15, ΛCl/C, B12- = 3.39 ± 0.15), suggesting the same reaction mechanism is involved in both experiments, independent of the lower cobamide bases. A nonisotopically fractionating masking effect may explain the smaller fractionations observed for the B12- containing culture.

Compound-Specific Carbon, Nitrogen, and Hydrogen Isotope Analysis to Characterize Aerobic Biodegradation of 2,3-Dichloroaniline by a Mixed Enrichment Culture.

Compound-specific isotope analysis (CSIA) is an established tool to track the in situ transformation of organic chemicals at contaminated sites. In this work, we evaluated the potential of multi-element CSIA to assess biodegradation of 2,3-dichloroaniline (2,3-DCA), which is a major industrial feedstock. Using controlled laboratory experiments, we determined, for the first time, negligible carbon (<0.5‰) and hydrogen (<10‰) isotope fractionation and a significant inverse nitrogen isotope fractionation (>10‰) during aerobic 2,3-DCA biodegradation by a mixed enrichment culture. The tentative identification of a glutamate conjugate of 2,3-DCA as a reaction intermediate indicates that the initial multistep enzymatic reaction may be rate-limiting. The formation of the glutamate adduct would increase the bond energy at the N atom, thus likely explaining the observed inverse N isotope fractionation. The corresponding nitrogen enrichment factor was +6.8 ± 0.6‰. This value was applied to investigate the in situ 2,3-DCA biodegradation at a contaminated site where the carbon and nitrogen isotope signatures from field samples suggested similar aerobic processes by native microorganisms. Under the assumption of the applicability of the Rayleigh model in a pilot wetland treating contaminated groundwater, the extent of biodegradation was estimated to be up to 80-90%. This study proposes multi-element CSIA as a novel application to study 2,3-DCA fate in groundwater and surface water and provides insights into biodegradation pathways.

Role of natural isotopic fractionation in isotope geo- and cosmo-chronology: A theoretical investigation

We introduce a new isotope chronological model in which the natural mass-dependent isotopic fractionation effects of the radioactive (“parent”) and radiogenic (“daughter”) elements are systematically and rigorously considered. Using this model, we show that internally-normalized radiogenic isotopic ratios, commonly determined for daughter elements such as Sr, Nd, Cr, Ni, Hf, W, and Os, are dependent on the extent of natural isotopic fractionation of the daughter and parent elements at the time of system closure. This dependence indicates that (1) in two samples derived from the same isotopically homogeneous source at the same time and with identical radiogenic ingrowth over time, the present-day internally-normalized radiogenic isotope ratios would be different if they were initially fractionated to different degrees, and (2) if different internally-normalized radiogenic isotopic ratios are observed for two co-genetic objects, the difference between them would include contributions from both radiogenic ingrowth and natural isotopic fractionation. Consequently, the isochron dating equations employed in traditional chronological studies will yield inaccurate results when significant natural isotopic fractionation is present among the studied samples. Modified isochron equations that can be used to retrieve correct chronological information from isotopically-fractionated samples are presented. These theoretical considerations are applied to the 87Rb–87Sr, 147Sm–143Nd, and 146Sm–142Nd isotope systems of calcium–aluminium-rich inclusions (CAIs), a set of samples that have undergone significant natural Sr, Nd, and Sm isotope fractionation during their formation. The large natural Sr isotope fractionation (up to ca. 5.3 ‰ for 88Sr/86Sr) in fine-grained CAIs can generate analytically well-resolvable biases (>120 ppm) in the internally-normalized 87Sr/86Sr ratios and lead to significant scatters of their 87Rb–87Sr isochron (in conjunction with scatters induced by open-system disturbances). The 87Rb–87Sr systems of coarse-grained CAIs, on the contrary, are essentially not affected by natural Sr isotopic fractionation due to their much subdued fractionation degrees, resulting in a more robust isochron. Similarly, the large natural Nd (up to ca. 4.0 ‰ for 146Nd/144Nd) and Sm (up to ca. 7.1 ‰ for 152Sm/148Sm) isotopic fractionation in fine-grained CAIs can induce significant scatters of the 147Sm–143Nd isochron if the natural fractionation followed the kinetic or power law, and 146Sm–142Nd isochron if the natural fractionation followed the equilibrium, Rayleigh, or power law. This implies that when studying radioactive isotope systems in objects whose daughter and parent elements can undergo significant isotope fractionation in nature, accompanying stable isotope analyses are necessary for accurate chronological interpretations.

Calcium isotope fractionation during weathering of argillaceous carbonates in a humid climate

The continental weathering is a key process that controls calcium (Ca) transportation from the continental crust to the waters. To elucidate the behavior of Ca isotopes during carbonate weathering, the concentrations and δ44/40Ca (relative to NIST SRM 915a) of bulk saprolites, exchangeable, acid-leachable and residual phases of a weathering profile developed on the marine carbonates, Guangdong province, South China, were investigated. Upwards the profile, δ44/40Ca values of the bulk saprolites systematically decrease from 0.77 ± 0.12 ‰ to −0.44 ± 0.12 ‰, suggesting that significant Ca isotope fractionation occurred during chemical weathering. The exchangeable fractions have δ44/40Ca values higher than those of the bulk saprolites with Δ44/40Caexchangeable-saprolite varying from −0.01 ‰ to 0.73 ‰, suggesting that heavy isotopes are preferentially adsorbed onto the clays. The acid-leachable phases display a relatively narrow δ44/40Ca range from 0.52 ‰ to 0.74 ‰ with Ca fractions varying from 7.4 % to 100.3 %, potentially indicating that limited Ca isotopic fractionation occurs during the dissolution of primary carbonates. The residual Ca pool is strongly fractionated with δ44/40Ca ranging from 0.64 ± 0.08 ‰ to −0.98 ± 0.02 ‰, systematically lower than their bulk saprolites, perhaps indicating light Ca isotopes are preferentially incorporated into the clay lattices. Altogether, it seems that the Ca isotopic fractionation directions are opposite between clay structural incorporation and adsorption. Our study provides important insight of Ca behavior and Ca isotopic fractionation during chemical weathering, which is critical to shape Ca isotopic compositions of the upper continental crust and trace the global biogeochemical cycle of Ca.

Tl, Mo and U isotopes in U-ore deposits record Earth's fundamental redox processes

Understanding changes in redox conditions in the Earth's geological record is fundamental to unravelling some of the major events of our planet's history, such as the Great Oxidation Event (G.O.E.), biological changes through time related to mass extinctions, or the formation of ore deposits for primordial metal resources. Rocks from uranium deposits are ideal candidates to examine the coupled isotopic fractionation of Tl, Mo and U, as they are fundamentally caused by redox processes, occur in a wide variety of geological settings throughout much of geological history (from about 3 Ga), and result from the interplay between fluids and rocks of variable redox states. Herein we measure δ97Mo (−10.2 to +6.1 ‰), ε205Tl (−9.5 to +5.0 ε-units), and δ238U (−0.72 to 0.30 ‰) for 34 samples from granite-related, intrusive, metamorphic, and Proterozoic unconformity related U deposits. Collectively, these results suggest: 1) in metamorphic and unconformity-related contexts, samples with decreasing ε205Tl values also have decreasing δ238U values, indicative of change in redox conditions, 2) ε205Tl values in the sulfide-rich samples likely reflect the affinity of 205Tl for these minerals, 3) Tl undergoes significant isotopic fractionation during the reduction of U-bearing fluids to precipitate uraninite, and 4) Tl isotopes do not fractionate during secondary remobilization of elements within these systems, and thus retain a record of the conditions of formation, whereas Mo isotopes are heavily fractionated by secondary remobilization. We suggest that the study of U, Mo, and Tl isotopes in U-ore deposits conveys new information related to building blocks of life on Earth and shows great potential for the study of past oxygenation events, thus potentially allowing us to reconstruct the geological and chemical history of our planet.

Nitrogen isotopes of marine oils in the Tarim Basin, China: Implications for the origin of organic matters and the paleoenvironment

Nitrogen isotope compositions (δ15N) of sedimentary rocks are usually used to reconstruct the paleoenvironment and nitrogen (N) biogeochemical cycle. The δ15N values of crude oils inherit the characteristics of relevant source rocks and can well reflect the information of hydrocarbon-forming organisms and environment in ancient water column. However, studies on the δ15N of crude oils are limited due to the low N content. In this study, a new efficient method is applied to the marine oils from the Bashituo (BST) and Halahatang (HLHT) areas of the Tarim Basin to obtain the nitrogenous components (i.e., nonhydrocarbons and asphaltenes) for the achievement of N concentration. The carbon and nitrogen isotopes of these components and the biomarkers of oils were measured. The δ15N values in asphaltenes (δ15NAsp) are significantly heavier than those in nonhydrocarbons (δ15NNSOs) in these oils, which are attributed to the potential directional N transfer and kinetic isotope fractionation during the thermal evolution of organic matters (OM). The δ15NAsp values have significant correlations with OM origin associated parameters and weak correlations with environmental parameters, suggesting that the difference in δ15NAsp values is mainly resulted from biological source rather than redox conditions. The δ15NNSOs values have a closer relationship with the redox condition than biological characteristics, indicating that they have a good response to paleoenvironmental variation in the water column, which is not completely overprinted by the difference of OM origin. Different redox conditions give rise to distinct nitrogen cycles, resulting in various δ15N values. Anammox occurs in the water column of the Early Cambrian dominated by physically stratified conditions with significant isotope fractionation, resulting in relatively heavier δ15N of OM in the BST area. In the Middle–Late Ordovician period, the limited suboxic zone leads to an insignificant positive bias of δ15N caused by partial denitrification in the HLHT oils. The evaluation of δ15N in nitrogenous fractions enables a more comprehensive reconstruction of N cycle for ancient oceans.

Sulfide mineralization in orogenic eclogites of the North Muya block (northeastern Transbaikalia): genesis and the first data on the isotopic composition of sulfur

Subduction processes are accompanied by the sites of hydrothermal activity including large deposits of gold and transitional metals of island-arc or back-arc origin, whereas volcanic arcs host most part of the worldwide resources of metallic minerals. However, the role of suprasubduction metal transfer and the associated role of redox processes in their formation are still ambiguous and require direct studies of sulfide mineralization in high-pressure rocks, as well as their formation stages and sulfide preservation during progressive and peak metamorphism. In order to describe the behavior of chalcophile elements in the paleozones of continental subduction we performed preliminary mineralogical (SEM-EDX) and isotope (S) studies of sulfides in the North Muya block eclogites (northeastern Transbaikalia). Sulfide mineralization of pyrite-chalcopyrite-pyrrhotite composition has a metasomatic origin associated with the retrograde fluid transformation of initially “dry” eclogite assemblages during exhumation to lower- or mid-crust levels after or synchronously to the decompression and formation of plagioclase-diopside±amphibole symplectites (below 10-12 kbar). Extremely heterogeneous isotopic composition of pyrite sulfur (δ34SVCDT) was caused by various sources of fluids of presumably metasedimentary origin (from -8.2 to -6 %) in the paragneiss segments of the North Muya block. But they also could be predominantly buffered by hydrothermally altered metabasites (from +0.7 to +7.1 %). An alternative mechanism could be the participation of a single predominantly oxidized (sulfate-containing) fluid with the significant isotopic fractionation (up to ~15–20 %).

The First Spatially Resolved Detection of 13CN in a Protoplanetary Disk and Evidence for Complex Carbon Isotope Fractionation

Recent measurements of carbon isotope ratios in both protoplanetary disks and exoplanet atmospheres have suggested a possible transfer of significant carbon isotope fractionation from disks to planets. For a clearer understanding of the isotopic link between disks and planets, it is important to measure the carbon isotope ratios in various species. In this paper, we present a detection of the 13CN N = 2 − 1 hyperfine lines in the TW Hya disk with the Atacama Large Millimeter/submillimeter Array. This is the first spatially resolved detection of 13CN in disks, which enables us to measure the spatially resolved 12CN/13CN ratio for the first time. We conducted nonlocal thermal equilibrium modeling of the 13CN lines in conjunction with previously observed 12CN lines to derive the kinetic temperature, H2 volume density, and column densities of 12CN and 13CN. The H2 volume density is found to range between (4 − 10) × 107 cm−3, suggesting that CN molecules mainly reside in the disk's upper layer. The 12CN/13CN ratio is measured to be 70−6+9 at 30 < r < 80 au from the central star, which is similar to the 12C/13C ratio in the interstellar medium. However, this value differs from the previously reported values found for other carbon-bearing molecules (CO and HCN) in the TW Hya disk. This could be self-consistently explained by different emission layer heights for different molecules combined with preferential sequestration of 12C into the solid phase toward the disk midplane. This study reveals the complexity of the carbon isotope fractionation operating in disks.

Fractionation Mechanism and Flux Estimation of Strontium Isotopes During Basalt Weathering

AbstractThe fluxes of metal cations and isotopes released by weathering of silicate rocks are crucial and a prerequisite for constraining geochemical fluxes to rivers and oceans. This study presents mineral and elemental compositions along with 87Sr/86Sr and δ88Sr data from a basaltic weathering regolith on Hainan Island, South China to elucidate Sr isotope fractionation and weathering fluxes. The 87Sr/86Sr ratios vary from 0.703936 to 0.706338 as a result of differential weathering of the minerals. δ88Sr values in the weathering regolith range from −0.29 to 0.37‰, with the majority of the weathering regolith having lower δ88Sr values than the parent rock. Sr is leached into the soil solution during plagioclase decomposition, while 86Sr is preferentially adsorbed on the surface of secondary minerals. As weathering progresses, smectite decomposes and kaolinite desorbs under weakly acidic conditions, releasing the previously adsorbed 86Sr into the soil solution. The differential weathering of kaolinite and smectite controls the δ88Sr values of the weathering regolith, with pH being an important determinant of isotope fractionation. Furthermore, Sr elemental fluxes (SrFlux) and Sr isotopic fluxes (δ88SrFlux) of this weathering regolith were calculated using a mass balance model, yielding mean values of 0.20 (mg cm−3 Myr−1) and 0.052 (‰ (mg cm−3 Myr−1)), respectively. The δ88SrFlux exhibits a nonlinear positive correlation with the Chemical Index of Alteration (CIA), indicating that enhanced weathering leads to significant stable Sr isotope fractionation at CIA values below 95%. Our research promotes the understanding of Sr recycling and the fractionation behavior of stable Sr isotopes during consecutive weathering.

Refining the roles of productivity, redox, and remineralization on the cadmium isotope composition of marine sediments

Cadmium (Cd) has a nutrient-like distribution in the ocean, similar to the macronutrient phosphate. Significant isotope fractionation induced by the biological cycling of Cd makes it a potential tracer for nutrients and productivity. However, the Cd flux and Cd isotope composition of marine sediments may also be influenced by local redox conditions and partial remineralization of organically hosted Cd. These confounding factors are under-constrained and render it challenging to use Cd as a reliable paleoproxy. To understand the relative importance of each of these processes, we examined the Cd isotope systematics of 69 modern sediments deposited across a wide range of environments. We complement these data with four profiles of particulate Cd isotope compositions from the Southern Ocean. We report three main results. First, we show that the sedimentary flux of Cd is tightly coupled to that of organic matter. Second, most Cd burial occurs in regions with some bottom-water oxygen, and the flux of CdS to anoxic regions is, globally, minor. Finally, we find that remineralization can substantially modify sedimentary Cd isotope compositions, though it is challenging to relate pelagic and sedimentary processes. For example, we find that the relationship between sedimentary Cd isotope compositions and surface seawater [Cd] is the reverse of that predicted by isotope reactor models. Likewise, sedimentary Cd isotope compositions are anti-correlated with bottom-water oxygen. While this pattern is consistent with preferential remineralization of isotopically heavy Cd, profiles of marine particulate matter reveal the reverse, whereby the Cd isotope composition of large particles, which are most likely to reach the seafloor, becomes increasingly ‘heavy’ with depth. These results highlight how productivity, redox, and remineralization all influence the flux and isotope composition of Cd to marine sediments. While our study suggests that there is no simple way to relate sedimentary Cd isotopes to surface nutrient utilization, our data point toward several potential controls that could form the basis of novel proxies for local redox conditions and remineralization.

Experimental simulation of thermal evolution of nitrogen content and isotopes in source rocks: Implications for nitrogen cycling characterization and oil-source correlation

Sedimentary nitrogen isotopes have been widely used to reconstruct the nitrogen cycling and redox characteristics of ancient oceans, but they also have important value in the study of oil genesis, such as oil classification. However, the thermal evolution of nitrogen isotopes in the source rock and associated oil is currently unclear. In this study, the thermal evolution (from the oil generation to the dry gas stage) of three types of low-maturity source rock was simulated. And the content and isotope composition of total organic carbon (TOC) and total nitrogen (TN) of the pyrolyzed source rock, expelled oil and retained oil were measured. In combination with weight-quantitative analyses, the following conclusions can be drawn: (1) During the main oil and gas generation stage, the pyrolyzed source rocks lost 15.1–28.3% of TN, which is much lower than the loss of TOC (26.2–46.1%). This difference may be related to the fact that the TOC content of the generated oil and gas is two orders of magnitude higher than the TN. In addition, TOC loss occurred mainly within the oil generation-expulsion stage, whereas TN loss occurred mainly in the dry gas stage and higher maturity stage. (2) The nitrogen isotope compositions of three types of source rocks and associated kerogens became heavier by 0.5–1.5‰ as thermal maturity increased, which is similar to the change of organic carbon isotope compositions. The δ15N values of pyrolyzed source rocks generally have poor relationships with either the amount of expelled oil and gas or the TN loss, which is different from the δ13Corg values. The δ15N fluctuations may be attributed to three processes: oil generation-expulsion, N2 gas generation-expulsion, and inorganic N (like NH4+) expulsion. The bulk nitrogen isotope composition of source rocks is only slightly affected by thermal maturity and can be used to indicate the nitrogen biogeochemical cycle and water redox conditions during the deposition. (3) Similar to δ13Corg values, δ15N values of both expelled oil and retained oil increased gradually with enhanced thermal maturity, implying a control of kinetic isotope effect. Among the three types of source rock, two of them having relatively light nitrogen isotope compositions (δ15N value of ∼2.5‰) generated and expelled oils with similar nitrogen isotope compositions, while the third type, which has heavy nitrogen isotope composition (δ15N value of ∼13.0‰), generated and expelled oils with much lighter nitrogen isotope compositions (by 3–6‰). This finding shows that there may be significant nitrogen isotope fractionation during the generation and primary migration of oil from source rocks. The nitrogen isotopes should be used in oil-source correlation with caution, even though related mechanisms need to be further studied. Nevertheless, using a combination of organic carbon and nitrogen isotopes, the oil generated and expelled by the three types of source rocks could be distinguished. Therefore, the use of nitrogen isotopes for oil-source correlation under geological conditions should be combined with other isotope and molecular indicators.

Isotope fractionation of alkaline and alkaline-earth elements (Li, K, Rb, Mg, Ca, Sr, Ba) during diffusion in aqueous solutions

In this study, we used an improved “diffusion cell” method to precisely determine the diffusion-driven kinetic isotope fractionation factors of the Li, K, Rb, Mg, Ca, Sr, and Ba cations in aqueous solutions under room temperature. The obtained isotope fractionation factors (±2σ errors) are, α7/6Li = 0.996139 ± 0.000140, α41/39K = 0.998572 ± 0.000072, α87/85Rb = 0.999333 ± 0.000020, α26/24Mg = 0.999877 ± 0.000010, α44/42Ca = 0.999704 ± 0.000010, α88/86Sr = 0.999781 ± 0.000014, α138/135Ba = 0.999716 ± 0.000018. The results show that the charge of the cation and the ion-water bond length for the aquo ions are the two predominant factors affecting the mass dependence of isotope fractionation (β factor) during cation diffusion in aqueous solutions. Cations with higher charge numbers and shorter ion-water bond lengths exhibit less kinetic isotope fractionation during diffusion. Therefore, the isotope separation effect during diffusion (or β factor) in fluids is fundamentally controlled by the intensity of ion-water interaction. Weaker ion-water interaction (e.g., lower charge number, longer ion-water bond length) leads to less prominent hydrodynamic behavior for diffusing ions at the molecular level, thus more significant isotope fractionation in bulk solutions, and vice versa. Ions of larger radius would show stronger mass dependence of isotope fractionation (β factor), which can cancel the effect of decreasing relative isotope mass difference for heavier elements, thus kinetic isotope fractionation during diffusion in aqueous solutions remains prominent even for heavy elements such as Rb, Sr, and Ba. The diffusion-driven kinetic isotope fractionation factors measured in this study could provide a useful basis for interpreting specific natural isotopic variability of alkaline and alkaline-earth elements in supergene environments where chemical diffusion takes place.

Stable isotope composition of pesticides in commercial formulations: The ISOTOPEST database

By assessing the changes in stable isotope compositions within individual pesticide molecules, Compound Specific Isotope Analysis (CSIA) holds the potential to identify and differentiate sources and quantify pesticide degradation in the environment. However, the environmental application of pesticide CSIA is limited by the general lack of knowledge regarding the initial isotopic composition of active substances in commercially available formulations used by farmers. To address this limitation, we established a database aimed at cataloguing and disseminating isotopic signatures in commercial formulations to expand the use of pesticide CSIA. Our study involved the collection of 25 analytical standards and 120 commercial pesticide formulations from 23 manufacturers. Subsequently, 59 commercial formulations and 25 standards were extracted, and each of their active substance was analyzed for both δ13C (n = 84) and δ15N CSIA (n = 43). The extraction of pesticides did not cause significant isotope fractionation (Δ13C and Δ15N < 1‰). Incorporating existing literature data, stable carbon and nitrogen isotope signatures varied in a relatively narrow range among pesticide formulations for different pesticides (Δ13C and Δ15N < 10‰) and within different formulations for a single substance (Δ13C and Δ15N < 2‰). Overall, this suggests that pesticide CSIA is more suited for identifying pesticide transformation processes rather than differentiating pesticide sources. Moreover, an inter-laboratory comparison showed similar δ13C (Δ13C ≤ 1.2 ‰) for the targeted substances albeit varying GC-IRMS instruments. Insignificant carbon isotopic fractionation (Δ13C < 0.5‰) was observed after 4 years of storing the same pesticide formulations, confirming their viability for long-term storage at 4 °C and future inter-laboratory comparison exercises. Altogether, the ISOTOPEST database, in open access for public use and additional contributions, marks a significant advancement in establishing an environmentally relevant pesticide CSIA approach.

Significant carbon isotopic fractionation during early formation of biological soil crusts with indications for dryland carbon cycling

Clarifying the accumulation and decomposition of soil organic carbon (SOC) is crucial for comprehending carbon cycling in terrestrial ecosystems. SOC enrichment and decomposition lead to the fractionation of stable carbon isotopes, a complex process influenced by various factors, including microbes. However, this fractionation process during early soil formation and the role of microorganisms remain poorly explored. This study investigated the relative composition of stable carbon isotopes (δ13C) of recently formed biological soil crusts (BSCs) on stabilized sand dunes in the Tengger Desert, Northern China. A notable increase in δ13C was observed during early BSC development, likely driven by cyanobacteria's direct fixation of CO2. Yet, δ13C values of BSCs gradually declined, approaching those of soils under native vegetation, probably linked to microbial succession within the BSCs. This finding highlights the potential microbial influence on early soil carbon turnover and underscores the effectiveness of isotope tracers for studying this process.

Gallium isotope fractionation during precipitation of α-GaOOH from aqueous solution

Gallium (Ga) has two naturally-occurring stable isotopes: 69Ga (60.1%) and 71Ga (39.9%). Their isotopic ratios were employed as a potential proxy to trace the geochemical behavior of Ga and its analogue Al. Ga is also an important component of many semiconductors. When exposed to aqueous solutions, it may be dissolved and then precipitate as Ga-bearing crystals (e.g., GaOOH). Thus, the exploration of Ga isotope fractionation during α-GaOOH precipitation could be helpful for understanding geochemical behaviors of Ga and other metals (including Al and Fe) during oxyhydroxide precipitation. In this study, three series of precipitation experiments with variable initial aqueous Ga concentrations (about 9.2, 2.0, and 1.8 ppm) were carried out to determine Ga isotope fractionation factor during α-GaOOH precipitation at ∼20 °C and neutral pH as a function of time. The experimental results could be modeled using a Rayleigh precipitation process, in which fractionation factors between crystals and solution (Δ71Gasolid-solution) are between −0.28 and − 0.37‰, depending on the initial Ga concentration and type of matrix anion (Cl− vs. NO3−). This isotope fractionation is significantly smaller in magnitude than the values reported for Ga adsorption on goethite (−0.89‰) and calcite (−1.27‰). The isotope fractionation is mainly caused by the increase in GaO bond length from ∼1.84 Å in aqueous GaOH4— to ∼1.991 Å in α-GaOOH solid, with a simultaneous change of Ga coordination number from 4 to 6, although kinetic isotope fractionation may play an important role. Our study provides the first experimental evidence of significant Ga isotope fractionation during kinetic oxyhydroxide precipitation, and suggests that the measurable Ga isotope fractionation occurred at water-solid interface and during precipitations can be potentially used for tracing global geochemical cycling of Ga and its analogue Al and Fe.