Analysis Of Isotopic Composition Research Articles

Subduction-collision and rapid uplift of the NW Yangtze Block during the Ediacaran-Cambrian transition: new evidence from the shoshonite series

ABSTRACT The NW Yangtze Block has long been regarded as a passive continental margin during Ediacaran and Cambrian. However, with the deepening of the regional geological survey and deep oil and gas exploration, the depositional sequence and palaeogeographic patterns of Ediacaran and Cambrian in the Sichuan basin are not consistent with the general sedimentary evolution process of passive margin more and more. To fully understand the tectonic property and palaeogeography of the NW Yangtze Block, a comprehensive study of the whole rock geochemistry, zircon U-Pb chronology and Hf isotopic composition analysis were carried out on the Weimen volcanic rocks, which mainly consist of trachyte, trachy-andesite, andesite, dacite, and rhyodacite in Maoxian area. They have high light rare earth element (LREE) and large ion lithophile element (LILE) concentrations, but are depleted in high field strength elements (HFSE). They are characterized by having high K2O+Na2O (5.60–9.48%), MgO (1.47–4.58%), Ce/Yb (11.67–25.79), and normalized hypersthene (Hy = 2.14–14.17), indicate an unambiguous feature of the shoshonite series. LA-ICP-MS zircon U-Pb dating results show that the volcanic rocks have crystallization ages ranging from 528 Ma to 523 Ma, with positive zircon εHf (t) ranging from + 1.31 to + 5.26. In combination with previous studies, the early Cambrian shoshonite series in Maoxian area are interpreted to be formed in a continental collision setting. Therefore, the discovery of the shoshonite series suggests that the NW Yangtze Block has experienced an important process of continental subduction and collisional orogeny in response to the Gondwana assembly, and consequently provided a large amount of terrigenous sources to rapidly fill into the early Cambrian foreland basin.

Evolution of continental inputs and watermass during cretaceous oceanic anoxic event 2 in the Neo-Tethyan region: Evidence from Nd-isotopes in southern Tibet

During the mid-Cretaceous extreme greenhouse (∼ 90 to 125 Ma), changes in continental inputs and water-mass circulation influenced nutrient distribution and set the stage for ocean anoxia. Investigation of these changes is critical for an understanding of contemporaneous global-ocean evolution. Previous studies on δ66Zn, δ15N, δ13C and 187Os/188Os isotopes in the Neo-Tethyan Ocean inferred both of these changes might be responsible for the continuous nutrient supply required to cause expansion of carbon burial during Oceanic Anoxic Event 2 (OAE2). Here, we applied the hydroxylamine hydrochloride (HH) extraction procedure to the analysis of Nd isotopic compositions of sediments collected from the mid-Cretaceous Dongshan and Lengqingre formations in southern Tibet. Our Nd isotope [εNd(t)] records exhibit a large negative excursion (from −9.8 to −6.1) during the Cenomanian-Turonian period, but little variation (−6.5 to −5.2) during the Aptian period. Major and trace elements as well as εNd(t) of residues indicate that the HH-extracted Nd in this study is mainly sourced from authigenic FeMn oxides. To evaluate the robustness of our εNd(t) records, we examined the potential influences of the detrital fraction. Our ɛNd(t) records reflect a mixing signal of surface currents from the Central Pacific and continental weathering inputs, and the corresponding negative excursion is triggered by the changes of continental weathering inputs in the Neo-Tethyan region, which was synchronous with the change of riverine systems during the drift of the Greater Indian Plate in the mid-Cretaceous greenhouse. Further, the enhanced continental weathering inputs, which supplied continuous nutrients to the Neo-Tethyan ocean, have likely caused OAE2 and extended the duration of OAE2. Our εNd(t) records shed new lights on our understanding of OAE2 during the mid-Cretaceous.

Paired X‐Ray Micro CT Scanning and Individual Foraminifera Isotopic Analysis Reveal (De)coupled Changes in Carbonate Preservation and Temperature

AbstractThe composition and preservation state of biogenic carbonate archives, such as foraminiferal tests, record ocean chemistry during the lifetime of the organism and post‐depositional changes in ambient conditions via carbonate compensation. Depending upon the specific paleoclimate proxy, post‐depositional processes, including dissolution, may alter original paleoenvironmental signals captured by the foraminifer's test composition. Accordingly, quantifying dissolution independent of geochemical measurements can improve proxy interpretation. Developing independent tools may also be useful for investigating whether changes in paleoclimatic conditions are associated with changes in seawater carbonate chemistry. Such approaches can be improved further if they are applied to individual foraminiferal tests, as specimen‐to‐specimen differences can record higher‐frequency environmental changes compared to conventional bulk‐scale analyses. Here, we combine individual foraminiferal carbon and oxygen isotopic analyses (IFA) with X‐ray MicroCT Scanning to generate paired analyses of test density (a proxy for the extent of post‐depositional dissolution) and isotopic composition. As a proof‐of‐concept application of this approach, we analyze Globigerina bulloides tests from both coretop and latest Miocene/earliest Pliocene‐aged sediment from Ocean Drilling Project (ODP) Site 1088 (Agulhas Ridge). Our measurements and mixing model calculations show that within‐population differences in carbon and oxygen isotopic ratios are largely independent of dissolution extent. By comparing population averages from coretop and downcore sediments, we find that lower oxygen isotopic ratios (likely driven by higher calcification temperatures) are associated with greater extents of dissolution at ODP Site 1088. We interpret this finding to reflect coupled changes in carbonate chemistry and climatic conditions over million‐year timescales.

Decoding organic compounds in lava tube sulfates to understand potential biomarkers in the Martian subsurface

Exploring molecular biomarkers in lava tube speleothems offers insights into environmental dynamics, biogeochemical processes, and subsurface life, with implications for astrobiology, particularly in Martian analog environments. Despite extensive biomarker research in marine and terrestrial settings, lava tube studies are limited. This study employed molecular, isotope and mineralogical characterization to analyze sulfate speleothems from six lava tubes of Lanzarote (Canary Islands), considered analog for the Moon and Mars. The combination of mass spectrometry, thermogravimetry, and mineralogical techniques, revealed geological processes, biomarkers and their biological sources. The identified minerals were primarily calcium and sodium sulfates. Sulfur isotope analyses indicated volcanic and oceanic origins, while carbon isotope composition and pyrolysis analyses suggested influences from vegetation and microbial activity. Lipidic profiles highlighted branched and n-alkanes, as well as palmitic and stearic acid methyl esters, suggesting microbial origins. These findings contribute to understanding geological and environmental dynamics in lava tubes and recognizing potential biosignatures on Earth and other planets.

Results of the CO2 diffuse degassing survey from the 2017 IAVCEI CCVG 13th volcanic gas workshop: Pululahua Dome Complex, Ecuador

Pululahua is a potentially active andesite and dacite lava dome complex. This paper presents the results of a survey focused on carbon dioxide (CO2) diffuse degassing at Pululahua, which was conducted during the 2017 International Association of Volcanology and Chemistry of the Earth's Interior (IAVCEI) Commission of the Chemistry of Volcanic Gases (CCVG) 13th Gas Workshop. Our objective was to conduct a comprehensive investigation of CO2 diffuse degassing by employing standard methods for measuring CO2 flux and temperature, and data processing. These methods were applied to map the spatial distribution of the measured parameters, investigate the origin of CO2, and quantify the volcanic CO2 output within the surveyed area of Pululahua. We carried out a total of 350 soil CO2 flux and 329 soil temperature measurements and collected 12 gas samples for carbon isotopic composition analysis, surrounding the three youngest domes in the complex. In addition, seventeen CO2 flux measurements over a thermal water pool were performed. Our findings indicate that the diffuse emission at Pululahua's crater floor is fed by both biogenic and volcanic CO2. Fluxes from each source are similar in magnitude, with approximately 90% of the measurements falling into an intermediate flux range. The occurrence of volcanic CO2 emissions is supported by the carbon isotopic composition. Diffuse degassing distribution highlights a CO2 anomaly surrounding the younger domes within the crater. We estimated the CO2 diffuse emission using both statistical and geostatistical approaches over area of 3.36 km2, resulting in values of 154.2 t d−1 and 126.2 t d−1 respectively. Based on the geostatistical quantification of the total CO2 emission from soil degassing, Pululahua's crater volcanic CO2 contribution is estimated between 59 and 97 t d−1. Finally, the potential hazards associated with the release of cold CO2 at Pululahua's crater are also discussed.

New chloromethane preparation line for the stable chlorine isotope composition analysis*

ABSTRACT Stable isotopes of chlorine have great application potential due to the widespread occurrence of the chlorine anion in water, minerals, living organisms and the environment. In most studies, the chloride ion from the samples is converted to chloromethane, which is then analysed isotopically using a mass spectrometer. In the present study, a new design for a chloromethane preparation line is proposed. In particular, the new chloromethane preparation line uses a new system for injecting iodomethane into the preparation system, as well as ampoules with Teflon valves and the u-shaped freezers. These improvements reduced the preparation time to about 1 h, and also achieved a decent measurement uncertainty of 0.05 permil.

Deep sea cold seeps are a sink for mercury and source for methylmercury

The effect of seafloor cold seeps on the biogeochemical cycling of mercury (Hg) remains enigmatic. Here we demonstrate substantial enrichments of mercury and methylmercury, along with the presence of microbes capable of metabolizing mercury in sediments of the Haima cold seep, South China Sea, by analyzing mercury and methylmercury concentrations, mercury isotopic composition analyses and metagenomic analyses of sediment cores. Compared to the reference area, the sediments in the upper sediment column of the active-seep area were 2.4 times enriched in Hg and 10.5 times in methylmercury. The slope of the capital delta ratio of mercury 199 to mercury 201 (Δ199Hg/Δ201Hg) with 1.23 ± 0.10 in the active-seep area indicate the occurrence of dark redox reactions. Genes related to mercury methylation (hgcA), demethylation (merB) and reduction (merA) were phylogenetically associated with several bacterial and archaeal linages. We roughly estimated an additional 2,835 Mg mercury and 9 Mg methylmercury are stored in cold seep globally. In summary, we propose that cold seeps globally function as a previously unrecognized sink for mercury and source for methylmercury in the deep ocean.

Characteristics, Sources, and Mechanisms of Soil Respiration under Simulated Rainfall in a Native Karst Forest in Southwestern China

Rainfall significantly affects soil respiration rates by altering microbial activity and organic matter decomposition. In karst regions, it also impacts carbonate dissolution and precipitation, further influencing soil CO2 flux. Investigating the mechanism of rainfall’s impact on soil respiration is essential for accurately evaluating and predicting changes in terrestrial ecosystems. However, our understanding of the interaction between rainfall and soil respiration in the extensive karst ecosystems of southwestern China remains limited. This study conducted field-based simulated rainfall experiments to examine variations in soil respiration rates and elucidate the associated control mechanisms through stable carbon isotope composition analysis. Simulated rainfall significantly increased the CO2 release via soil respiration. We observed significant differences in the δ13C value of soil-respired CO2 before and after simulated rainfall. Following the rain, the δ13C of soil-respired CO2 was enriched compared to that before the rain. Through isotope data analysis, we found that the increased soil CO2 emissions were primarily driven by heterotrophic respiration, likely stimulated via changes in soil moisture, affecting microbial growth conditions. Furthermore, the variation in soil moisture affected carbonate dissolution and precipitation, potentially increasing the soil CO2 release after rainfall. In conclusion, these findings expand our understanding of rainfall’s effects on soil respiration in the native karst forests of southwestern China, contributing to the prediction of carbon cycling processes in such ecosystems. The data from this study have significant implications for addressing the release of greenhouse gases in efforts to combat climate change.

Using isotope-geochemical criteria for Olympiadinskoye gold deposit gas system genesis diagnosis

The authors studied modern gas manifestations spatially associated with the ore deposits in the Kaitbinskaya lithological-facies zone of the Yenisei Ridge. The purpose of the research is to obtain scientifically based data on the genesis of gaseous and vaporous fluids in various sampling environments of the Vostochny open-pit mine of the Olympiadinskoye gold deposit: rocks, natural waters, free-flowing gases from blastholes and air of the surface atmosphere. It has been conducted a complex of field and analytical works including degassing, gas chromatography, pyrolysis of the organic substance of lithified and metamorphosed deposits, analysis of carbon isotopic composition in carbon dioxide and methane in fluidal systems. In order to study normal gas-geochemical field (natural background) of the work area an atmospheric geochemical survey was carried out at the reference site – an “environmentally friendly” site with the minimal influence of technogenic factors. It has been determined that the surface atmosphere of the site had been formed due to the landscape and geomorphological conditions of the Kaitbinskaya lithological-facies zone as well as fluidal systems of deep horizons. The latter, due to the presence of an extensive network of disruptive disturbances and diffusion-filtration processes of mass transfer reached the zone of exploratory geochemical sounding. The conducted pyrolytic studies of rocks have proved that within the open section of the Vostochny open-pit mine the organic substance of the Kordinskaya series of the lower Riphean deposits has implemented its oil and gas generation potential and cannot serve the formation source of abnormal gas fields of the Olympiadinskoye gold deposit. The studied gas systems are polygenic in nature and, being allochthonous to the host sediments, are formed without the participation of gases from the upper generating (bio) zone. According to isotope-geochemical criteria, these are mainly endogenous and naphthidogenic fluids identical to the gas condensate accumulations of the Yurubcheno-Tokhomskaya oil and gas accumulation zone.

Sediment resuspension as a driving force for organic carbon transference and rebalance in marginal seas

The transfer of particulate organic carbon (POC) to dissolved organic carbon (DOC; OC transferP-D) is crucial for the marine carbon cycle. Sediment resuspension driven by hydrodynamic forcing can affect the burial of sedimentary POC and benthic biological processes in marginal sea. However, the role of sediment grain size fraction on OC transferP-D and the subsequent impact on OC cycling remain unknown. Here, we conduct sediment resuspension simulations by resuspending grain-size fractionated sediments (< 20, 20–63, and > 63 μm) into filtered seawater, combined with analyses of OC content, optical characteristics, 13C and 14C isotope compositions, and molecular dynamics simulations to investigate OC transferP-D and its regulations on OC bioavailability under sediment resuspension. Our results show that the relative intensities of terrestrial humic-like OC (refractory DOC) increase in resuspension experiments of < 20, 20–63, and > 63 μm sediments by 0.14, 0.01, and 0.03, respectively, likely suggesting that sediment resuspension drives refractory DOC transfer into seawater. The variations in the relative intensities of microbial protein-like DOC are linked to the change of terrestrial humic-like OC, accompanied by higher DOC content and reactivity in seawater, particularly in finer sediments resuspension experiments. This implies that transferred DOC likely fuels microbial growth, contributing to the subsequent enhancement of DOC bioavailability in seawater. Our results also show that the POC contents increase by 0.35 %, 0.66 %, and 0.93 % in < 20, 20–63, and > 63 μm resuspension experiments at the end of incubation, respectively. This suggests that the re-absorption of OC on particles may be a significant process, but previously unrecognized during sediment resuspension. Overall, our findings suggest that sediment resuspension promotes the OC transferP-D, and the magnitudes of OC transferP-D further influence the DOC and POC properties by inducing microbial production and respiration. These processes significantly affect the dynamics and recycling of biological carbon pump in shallow marginal seas.

Multistage evolution of gold mineralization in the Kibali gold district: Insights from pyrite analyses

The Kibali gold district, located on the Congo Craton, comprises a Neoarchean gold resource exceeding 28.7 Moz. The district is located within a westerly-verging stacked fold-and-thrust belt associated with a compressional tectonic regime active from ca. 2.64–2.60 Ga. Deposits are hosted by a major fault zone that consists of a complex series of smaller thrust faults, shear zones, and folds, which extend over 60 km. Gold deposits are primarily hosted in BIF and clastic sedimentary rocks. The gold and associated sulfides are in veins and disseminated in NE-to NNE-trending ore shoots within the deformed and metamorphosed volcanosedimentary rocks. Pyrite is the dominant sulfide mineral and hosts both solid solution gold and free gold. Because of its strong association with the gold mineralization, our study focusses on unravelling the metallogeny of the area by considering pyrite textural analyses, in situ trace element analyses using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS), and S isotopic composition (δ34S) analyses using Secondary Ion Mass Spectrometry (SIMS).Eight distinct pyrite types were identified, including microcrystalline sooty (py-0a), small grains (<40 μm) (py-0b), aggregate recrystallized (py-1), core-rich inclusion (py-2), vein-like (py-3), non-zoned (py-4a), oscillatory As-bands zoned (py-4b), and cubic euhedral (py-5) pyrite. The ore-forming processes occurred over a polyphase evolution. Syn-diagenetic pyrite py-0a in volcaniclastic layers of older basin sediments served as the primary repository of Au (15.6 ppm median) with a near-zero δ34S value. Late diagenetic or early metamorphic pyrite (py-0b) was found in younger basin sediments. Py-1 resulted from solid-state recrystallization of py-0a and py-0b. During the early ore stage, porous py-2 with high Au concentrations (3.1 ppm) and various trace element enrichments precipitated due to fluid-rock interaction. Metal precipitation occurred through sulfidation and carbonation of wall rock with a relatively reduced fluid undergoing 34S-depletion. However, py-3 displayed notable trace element depletion and a complex mineral association. In a second ore stage, py-4a and zoned py-4b deposition occurred, dominated by an over-pressured fluid fracturing brittle rock. Py-4b, rich in Au (5.5 ppm) concentrated in oscillatory zoned As-rich bands, resulted from interactions during pulsed fluid flow. This process involved fluid phase separation, non-equilibrium conditions, 32S-depletion, and precipitation of py-4b with a high δ34S value (6.4 ‰ mean). Subsequently, pyrite (0–4) generations underwent deformation during a later ductile deformation event, leading to the remobilization and concentration of invisible gold into adjacent gold grains within the high-grade shoot plunging NE. This process involved shearing, boudinaging, and folding ore minerals in tightly folded structures. Late-stage py-5 formed under gold-poor fluid conditions or inefficient gold depositional conditions. Brittle fracturing of these grains later provided local sites for remobilized gold. The study contributes insights into the origin and evolution of gold mineralization in the Kibali gold district, supporting a multistage ore-forming fluid system.

Facies and geochemical characteristics of the Middle-Lower Ordovician Yingshan Formation in the Tarim Basin, NW China: Implications for the high-frequency sequence stratigraphy in shallow-water carbonate platform

Shallow-water carbonates from the Yingshan Formation are important target of hydrocarbon exploration in Tarim Basin. Detailed descriptions of outcrop, core, and thin sections, isotopic composition analysis, and trace element analysis were conducted. Seven lithofacies which consists of two facies belt groups were identified and used to interpret deposition environments of Yingshan Formation: (1) peritidal carbonate, with relatively lower δ13C values from −4.2% to −1.9%, mainly represented by intertidal to supratidal facies and restricted subtidal facies and (2) open-marine subtidal carbonate, with higher δ13C values (−1.5% to −0.3%), mainly consists of shoal facies and interbank sea facies. On the basis of the lithology sets, four types of meter-scale cycle model (types A–D) were grouped into peritidal sequences and subtidal sequences. On the basis of vertical lithofacies, cycle stacking patterns, and accommodation variations in Fischer plots, two third-order depositional sequences (SQ1–SQ2) were recognized. The sequence boundary between SQ1 and SQ2 is not only a surface of a positive shift of δ13C values, but also the transitional zone of cycle stacking patterns. The sequences can be further divided into four fourth-order sequence sets: Sq1–Sq4. The lower sequences (Sq1–Sq2) are dominated by peritidal facies and characterized by a progressive decreasing in accommodation space probably indicates a longer-term fall in sea level. The upper sequences (Sq3–Sq4) are mainly dominated by subtidal facies and characterized by the accommodation space with a progressive increasement, likely indicates a rising sea level with a longer term. The facies-controlled reservoirs are mainly present in the Sq3, related to the sequence boundary between SQ1 and SQ2.

Tracking the transformation of persistent organic pollutants in food webs using multi element isotope and enantiomer fractionation

In order to track the transformation of persistent organic pollutants (POPs) in food webs, field experiments were conducted at two sites using stable isotope and enantiomer fractionation concepts. The enantiomers of α-hexachlorocyclohexane (α-HCH) were selected as representative compounds for POPs. Isotope and enantiomer fractionation allowed the characterization of α-HCH enantiomer biotransformation processes along trophic levels of the food web - from soil and plants to animal livers, fat tissues and milk. The enrichment of heavy isotopes in soils, plants and sediments as well as the changes of enantiomer fractionation indicate that the biotransformation of α-HCH occurred in these compartments. Moreover, the increase of carbon and chlorine isotopic compositions as well as the changes of enantiomer fractionation of liver, fat tissues and milk demonstrated that the overall HCH exposure was much higher than estimates based on concentration levels, while the isotope and enantiomer fractionation revealed the enantiomer specific enantiomer uptake across the blood-brain barriers. Dual element isotope analysis suggested that complex transformation processes have occurred along the potential food web from the HCH sources over different environmental compartments to animal livers, fat tissues and milk. The results imply that the analyses of stable isotope compositions and concentrations has potential to reconstruct the exposure of higher organisms to POPs.

Genesis of the Beizhan Iron Deposit in Western Tianshan, China: Insights from Trace Element and Fe-O Isotope Compositions of Magnetite

The Beizhan iron deposit (468 Mt at an average grade of 41% Fe) is the largest iron deposit in the Awulale iron metallogenic belt of Western Tianshan, northwest China. The high-grade magnetite ores are hosted in the Carboniferous volcanic rocks with extensive development of skarn alteration assemblages. While considerable progress has been made in understanding the characteristics of Beizhan and its genetic association with volcanic rocks, the genetic models for ore formation are poorly constrained and remain controversial. This study combines detailed petrographic investigations with in situ LA-ICP-MS analyses of trace elements and Fe-O isotope compositions of magnetite to elucidate the origin of magnetite and the conditions of ore formation. The trace element concentrations in magnetite unveil intricate origins for various ore types, implying the precipitation of magnetite from both magmatic and hydrothermal fluids. The application of the Mg-in magnetite thermometer (TMg-mag) reveals a notable temperature divergence across different magnetite varieties, spanning from relatively higher temperatures in magmatic brecciated magnetite (averaging ~641 and 612 °C) to comparatively lower temperatures in hydrothermal platy magnetite (averaging ~552 °C). The iron isotopic composition in massive and brecciated magnetite grains, characterized by lighter δ56Fe values (ranging from −0.078 to +0.005‰ and −0.178 to −0.015‰, respectively), suggest a magmatic or high-temperature hydrothermal origin. Conversely, the heavier δ56Fe values observed in platy magnetite (+0.177 to +0.200‰) are attributed to the influence of pyrrhotite, signifying late precipitation from low-temperature hydrothermal fluids. Additionally, the δ18O values of magnetite, ranging from +0.6 to +4.6‰, provide additional evidence supporting a magmatic–hydrothermal origin for the Beizhan iron deposit. Overall, the identified genetic associations among the three magnetite types at Beizhan provide valuable insights into the evolution of ore-forming conditions and the genesis of the deposit. These findings strongly support the conclusion that the Beizhan iron deposit underwent a process of magmatic–hydrothermal mineralization.

Controlling effects of terrestrial organic matter on metal contamination and toxicity risks in port sediments

The contents of metals, total carbon, total nitrogen (TN), total organic carbon (TOC), and stable isotope composition (δ13Corg and δ15N) of sediment organic matter (SOM) were investigated to explore the sources and spatial distribution of metals and SOM in the surface sediments (Kaohsiung Port, Taiwan). Results showed that TOC and metals in estuarine sediments are high, gradually decreasing toward the port entrances. The δ13Corg, δ15N, and TOC/TN ratios indicate that SOM comes mainly from terrestrial sources. This study proposes a befitting model between metal pollution and toxicity risk index and SOM sources in port sediments by combining stable isotope composition, correlation matrix, and multiple linear regression analysis. The model indicates that the degree of metal pollution and toxicity risk in sediments are mainly affected by TOCterr content and SOM source. The results help to understand the influence of organic matter sources in port sediments on metal concentration distribution.

Toward a common methodological framework for the sampling, extraction, and isotopic analysis of water in the Critical Zone to study vegetation water use

AbstractThe analysis of the stable isotopic composition of hydrogen and oxygen in water samples from soils and plants can help to identify sources of vegetation water uptake. This approach requires that the heterogeneous nature of plant and soil matrices is carefully accounted for during experimental design, sample collection, water extraction and analyses. The comparability and shortcomings of the different methods for extracting water and analyzing isotopic composition have been discussed in specialized literature. Yet, despite insightful comparisons of extraction methods and benchmarking methodologies of laboratories worldwide, the community still lacks a roadmap to guide sample collection, extraction, and isotopic analyses, and many practical issues for potential users remain unresolved: for example, which (soil or plant) water pool(s) does the extracted water represent? These constitute a hurdle for the implementation of the approach by newcomers. Here, we summarize discussions led in the framework of the COST Action WATSON (“WATer isotopeS in the critical zONe: from groundwater recharge to plant transpiration”—CA19120). We provide guidelines for (1) sampling soil and plant material for isotopic analysis, (2) methods for laboratory or in situ water extraction, and (3) measurements of isotopic composition. We highlight the importance of considering the process chain as a whole, from experimental design to isotopic analysis to minimize biased estimates of the relative contribution of different water sources to plant water uptake. We conclude by acknowledging some of the limitations of this methodology and advice on the collection of key environmental parameters prior to sample collection for isotopic analyses.This article is categorized under: Science of Water &gt; Hydrological Processes Science of Water &gt; Water and Environmental Change Science of Water &gt; Water Extremes

High-precision analysis of carbon isotopic composition for individual CO2 inclusions via Raman spectroscopy: Addressing issues arising from the laser-heating effects

The carbon isotopic composition of carbon dioxide fluid inclusions trapped within minerals reflects the origin and evolution of the CO2-bearing fluids and melts. Recently, we developed a highly accurate method using Raman spectroscopy to determine the carbon isotopic composition of CO2 fluid inclusions, by simultaneously collecting 13CO2 and hot bands at a controlled temperature, and using the peak height ratio of 13CO2 and one of hot bands near 1410 cm−1 (HR) to determine δ13C value. This microanalytical technique enables precise measurements of the δ13C values of different CO2 fluid inclusions within zoned mineral crystals to reveal the multiple-stages evolution of CO2-bearing fluids and melts. However, when studying fluid inclusions hosted within high laser heating coefficient minerals such as olivine and pyroxene in mantle xenoliths, local temperature near the inclusions will be higher than the temperature controlled by heating-cooling stage. To address this issue, we examined the effects of laser heating on CO2 isotopic standard samples sealed in the silica capillary, and developed a novel procedure to determine the δ13C values of natural fluid inclusions by using two CO2 standard samples with known carbon isotopic compositions. The proposed workflow successfully determines the δ13C values of natural CO2 inclusions, with an average deviation of 0.58 ‰ between the measurements and the model.

Comparative Analysis of Water Isotopic Compositions: Evaluating Isotope Analyzer for Soil and Extraction Method for Stem Water

Stable isotopes of water (δ2H and δ18O) are reliable tracers for the investigation of plant–soil–water interactions in forest ecosystems. However, variations in isotopic compositions may arise due to differences in analytical instruments and water extraction methods. In this study, we conducted three different experiments to identify isotopic differences caused by analytical and methodological variations. First, we analyzed soil water by using the two most commonly applied methods: isotope ratio mass spectrometry (IRMS) and cavity ring-down spectroscopy (CRDS). Second, we compared the isotopes in xylem water extracted from the stems of nine tree species using cryogenic vacuum distillation (CVD) with different heating times. Third, we compared the compositions in xylem water extracted with three different methods: mechanical squeezing using a pressure chamber (PC), an induction module (IM), and CVD. The differences in isotopic composition between IRMS and CRDS were significant but minimal. Soil properties were not significant factors contributing to differences between the two instruments. For the xylem water extraction with CVD, each of the nine tree species required heating for more than three hours. Significant differences were observed in δ2H among the three extraction methods for xylem water. Xylem water extracted by CVD showed more depleted values compared to those obtained by PC and IM. Our results highlight the importance of considering analytical and methodological variations in stable isotope analysis.

Stable Isotope Analyses Reveal Impact of Fe and Zn on Cd Uptake and Translocation by Theobroma cacao.

High concentrations of toxic cadmium (Cd) in soils are problematic as the element accumulates in food crops such as rice and cacao. A mitigation strategy to minimise Cd accumulation is to enhance the competitive uptake of plant-essential metals. Theobroma cacao seedlings were grown hydroponically with added Cd. Eight different treatments were used, which included/excluded hydroponic or foliar zinc (Zn) and/or iron (Fe) for the final growth period. Analyses of Cd concentrations and natural stable isotope compositions by multiple collector ICP-MS were conducted. Cadmium uptake and translocation decreased when Fe was removed from the hydroponic solutions, while the application of foliar Zn-EDTA may enhance Cd translocation. No significant differences in isotope fractionation during uptake were found between treatments. Data from all treatments fit a single Cd isotope fractionation model associated with sequestration (seq) of isotopically light Cd in roots and unidirectional mobilisation (mob) of isotopically heavier Cd to the leaves (ε114Cdseq-mob = -0.13‱). This result is in excellent agreement with data from an investigation of 19 genetically diverse cacao clones. The different Cd dynamics exhibited by the clones and seen in response to different Fe availability may be linked to similar physiological processes, such as the regulation of specific transporter proteins.

Spatial distribution, environmental behavior, and health risk assessment of PAHs in soils at prototype coking plants in Shanxi, China: Stable carbon isotope and molecular composition analyses

To investigate the environmental behavior of and carcinogenic risk posed by 16 priority-controlled polycyclic aromatic hydrocarbons (PAHs), soil samples and air samples from the coke oven top were collected in two prototype coking plants (named PF and JD). The PF soils contained more PAHs than the JD soils because the PF plant employed the side-charging technique and had a lower coke oven height. The soils from both plants contained enough PAHs to pose a carcinogenic risk, and this risk was higher in the PF plant. Data were collected on the source characteristic spectrum of stable carbon isotopic composition (δ13C) of PAHs emitted from the coke oven top (δ13C values of −36.02‰ to −32.05‰ for gaseous PAHs and −34.09‰ to −25.28‰ for particulate PAHs), and these data fill a research gap and may be referenced for isotopic-technology-based source apportionment. Diagnostic ratios and isotopic technology revealed that the coking plant soils were mainly influenced by the coking process, followed by vehicle exhaust; the soils near the boundary of each plant were slightly affected by C3 plant burning. For most PAHs [excluding fluoranthene, benzo(k)fluoranthene, indeno(1,2,3-c,d)pyrene, and dibenzo(a,h)anthracene], the dominant migration process was the net volatilization of PAHs from soil to air. In the PF plant, 13C was depleted in gaseous PAHs during volatilization.