Isotopic Composition Of Water Research Articles

Tracing nitrate contamination sources and dynamics in an unconfined alluvial aquifer system (Velika Gorica well field, Croatia).

Nitrate ions (NO3-) are one of the most common contaminants in the groundwater of the Zagreb alluvial aquifer, which hosts strategic groundwater reserves of the Republic of Croatia and supplies drinking water to one million inhabitants of the capital city. To better understand the origin and the dynamics of NO3- in the unsaturated and saturated zones, the stable isotopes of nitrogen (δ15N) and oxygen (δ18O) in dissolved nitrate, combined with physico-chemical, hydrogeochemical and water stable isotope data, were used in the current work, together with statistical tools and mixing models. The study involved monthly sampling of groundwater, surface water, precipitation and soil water samples. Additionally, the isotopic composition of total nitrogen (δ15Nbulk) was determined in solid samples representing the local nitrate sources. The combination of a nitrous oxide isotopic analyzer and the titanium(III) reduction method provides reliable measurements of δ15NNO3 and δ18ONO3, with optimal stability achieved under specific conditions. Nitrate in the study area predominantly originates from organic sources, with nitrification as the main biogeochemical process, while denitrification was identified at sampling sites under specific anaerobic conditions. Although statistical analysis can be a valuable tool, it should be applied with caution if NO3- originates from multiple sources. The isotopic composition of water showed that groundwater is predominantly recharged by the Sava River but its contribution varied spatially. The results also show the existence of a different recharge source in the southern part of the aquifer. Our findings highlighted the importance of employing a diverse range of analytical methods to obtain reliable and comprehensive understanding of nitrate contamination. By integrating multi-method approaches, stakeholders can better understand the complexities of groundwater contamination and implement more targeted measures to safeguard the water supplies for future generations.

The formation conditions of subglacial Lake Vostok’s accreted ice based on its stable water isotope composition

In this paper, we present a new dataset on the stable water isotopic composition (δD and δ18O) in a sequence of subglacial Lake Vostok’s accreted ice (3538–3769 m) measured along three parallel ice cores. The high precision of the new data has allowed us to characterize the formation conditions of different sections of the ice. The whole lake ice interval may be divided into 3 zones: 1) “zone 0”, 3538.8–3549.8 m, is under the strong influence of the local water formed from melted meteoric ice likely entering from under the glacier on the lake’s west coast; 2) “zone 1” (accreted ice 1), 3549.8–3607.4 m, is experiencing significant variability due to the slightly different effective fractionation coefficient in the course of “water inclusions” in the ice matrix during the freezing process; 3) “zone 2” (accreted ice 2), 3607.4–3768.8 m, is under the influence of glacial melt water from the northern part of the lake and the hydrothermal flux from the lake’s bottom. We defined the exact boundary between the accreted ice 1 and ice 2, which corresponds to a sharp isotopic excursion at a depth of 3607.4 m. In this work, we present for the first time data on the “17O-excess” parameter in the lake ice and water, which allowed us to make a direct calculation of the equilibrium fractionation coefficient for oxygen 17 during water freezing.

Spatiotemporal characterization of the isotopic composition of meteoric waters in Cuba

The stable isotope composition of meteoric water has been widely used to understand hydrological processes worldwide. We present a unique dataset, with the isotopic composition (δ18O and δ2H) of meteoric waters, derived from a nationwide study in Cuba. It includes monthly composite and event-based precipitations, from January 2017 to December 2021 (N = 526 and N = 111 respectively). Monthly data showed minor seasonal trends (dry vs. rainy), with a notable influence of tropical cyclones. Event-based data demonstrated that precipitation associated with tropical cyclones exhibited lower isotopic compositions. The analysis of potential factors influencing the isotopic composition of precipitation showed a minor influence of the rainfall amount, but negligible influence of factors such are relative humidity, elevation, and air temperature. This data set can be used as a tool not only to understand hydrological processes at the country scale, but also to further improve and develop isotope-enabled modelling for assessing water balances and fluxes, understanding the impact of extreme events, and paleoreconstruction in the Intra-Americas Sea.

Measuring the Stable Isotope Composition of Water in Brine from Halite Fluid Inclusions and Borehole Brine Seeps Using Cavity Ring-Down Spectroscopy

Measuring the Stable Isotope Composition of Water in Brine from Halite Fluid Inclusions and Borehole Brine Seeps Using Cavity Ring-Down Spectroscopy

Triple oxygen isotopes of lunar water unveil indigenous and cometary heritage

The origin of water in the Earth-Moon system is a pivotal question in planetary science, particularly with the need for water resources in the race to establish lunar bases. The candidate origins of lunar water are an indigenous lunar component, solar wind water production, and the delivery of meteoritic and cometary material. Characterizing the oxygen isotopic composition of water provides information on lunar oxygen sources. The scarcity of lunar water required the development of a high-precision analytical technique for small samples. This method employs stepwise heating, fluorination, and oxygen isotopic measurements using a dual inlet isotope ratio mass spectrometer. The three heating steps were selected based on other extraterrestrial material studies to release loosely bound water that may have been terrestrially contaminated (50 °C), loosely bound water (150 °C), and tightly bound water (as OH) (1,000 °C). This method was applied to a suite of 9 Apollo samples (basalts, breccias, and a regolith), along with terrestrial and meteoritic controls. We present here measurements of the triple oxygen isotopic composition of this water. Our data predominantly show high Δ'17O values (≥ 0‰) for lunar water. These values are consistent with enstatite, ordinary, and CI chondrite-like signatures, although coupling Δ'17O with δ18O forms mixing trends that dominantly overlap enstatite signatures. The other end of the mixing line is in the positive Δ'17O space with cometary δ18O values, providing constraints for cometary Δ'17O between 0.75 to 1.75‰.

Triple oxygen and hydrogen stable isotope composition of water in Murchison carbonaceous chondrite accessed by thermogravimetry-enabled laser spectroscopy

Triple oxygen and hydrogen stable isotope composition of water in Murchison carbonaceous chondrite accessed by thermogravimetry-enabled laser spectroscopy

Physicochemical and isotopic similarity between well water and intruding surface water is not synonymous with similarity in prokaryotic diversity and community composition

Intruding surface water can impact the physicochemical and microbiological quality of groundwater. Understanding these impacts is important because groundwater provides much of the world's potable water, and reduced quality is a potential public health risk. In this study, we monitored six shallow groundwater wells and three surface water bodies in the North Ostrobothnia region of Finland twice monthly for 12 months (October 2021–October 2022) via (i) on-site and off-site measurements of physicochemical water quality parameters, (ii) determination of stable water isotope compositions, and (iii) analysis of microbial communities (via amplicon sequencing of the V3–V4 16S rRNA gene sub-regions). Water from one well showed clear overall physicochemical and isotopic similarity with a nearby pond, as well as temporal fluctuations in water temperature and isotopes that mirrored those of the pond. Isotope mixing analyses suggested that about 80–95 % of the well water comes from the pond. Such large-scale intrusion might be expected to reduce prokaryotic diversity and composition in the aquifer, either by strong influx of surface water taxa or changes to aquifer physicochemistry. Compared to the pond, however, prokaryotic communities from the well showed significantly higher alpha diversity and a composition more similar to a nearby well unaffected by intrusion. The finding that physicochemical and isotopic similarity between well water and intruding surface water is not synonymous with similarity in prokaryotic diversity and community composition makes clear the need for a multi-method approach when studying the impact of surface water intrusion on shallow wells.

Synthesis of a hydrological, water chemistry, and contaminants research program in the Peace-Athabasca Delta (Canada) to inform long-term monitoring of shallow lakes

In a multistressor world, evidence-based stewardship of aquatic ecosystems requires long-term monitoring data to understand the timing and magnitude of environmental change and potential causes. At the Peace-Athabasca Delta (PAD; northeastern Alberta, Canada), concern for aquatic ecosystem degradation has triggered renewed and urgent calls by Indigenous, national, and international governance bodies for implementation of a long-term lake monitoring program capable of tracking changes in hydrological conditions and contaminant deposition attributable to major energy projects located upstream, climate change, and other unnatural and natural processes. Challenges imposed by the delta's size, hydrological complexity, inaccessibility of lakes, and other factors, however, have long impeded implementation of a delta-wide lake monitoring program. To address this pressing need, here we review and synthesize results obtained during 7 years (2015–2021) of intensive, multifaceted research at 60 shallow lakes spanning the delta's broad hydroecological gradients to inform an integrated hydrology, water chemistry, and contaminants monitoring program. The research involved systematic, repeated measurements of water isotope composition, water depth variation, water chemistry and turbidity, and metal(loid) concentrations in lake surface sediment and periphytic biofilm. Results reveal marked spatial and temporal variation of hydrological processes and their affects on lake water balance and depth, strong association between hydrological processes and lake water chemistry, and that concentrations of nickel and vanadium (key oil sands indicators) remain within the range of natural variation. Correspondence of generalized additive model trendlines for isotope-derived lake evaporation-to-inflow ratios and water chemistry with climate indices (Pacific Decadal Oscillation, Oceanic Niño Index) demonstrates the sensitivity, and predictability, of lake ecosystem processes in the delta to large-scale climatic patterns. We provide recommendations for field sampling, sample analysis, data display, and integration of information for ongoing monitoring at the PAD. These approaches are readily transferable to other complex landscapes with abundant shallow waterbodies threatened by multiple stressors that may alter hydrological regimes and contaminant delivery.

Carbonate precipitation-derived CO2 outgassing offsets the mineral weathering sink in the orogenic regime of southwestern Taiwan: Insights from triple Sr isotopes

Secondary carbonate precipitation plays a crucial role in determining the CO2 outgassing from carbonate-saturated rivers and influences the short-term terrestrial carbon cycle. The fractionation of stable isotopes has been extensively employed to quantify post-weathering reactions in rivers and assess the quantities of metals removed by secondary carbonates. However, a major challenge is that water isotopic compositions usually reflect both lithological mixing and biogeochemical fractionation, which complicates distinguishing between these signals. In this study, we applied triple Sr isotopes (87Sr/86Sr and δ88/86Sr) to determine the “unfractionated” δ88/86Sr of water. This method allowed us to precisely quantify the precipitation-derived fractionation. Our results show that a median of 48 % of Sr was incorporated into carbonates in southwestern (SW) Taiwan, corresponding to the removal of 69 % of the originally weathered Ca. This process is closely related to a significant increase in HCO3− concentration in the water. In SW Taiwan, high river discharge during wet periods typically enhances carbonate dissolution, leading to increased carbonate precipitation along with CO2 outgassing. Thus, hydrology and river discharge constraints significantly influence CaCO3 precipitation and CO2 outgassing processes and their associated CO2 budget. Using a machine learning model, we estimated that the precipitation-derived CO2 outgassing from rivers is +7.9 × 108 mol per year. This flux is nearly twice the long-term (~10 kyr) emission flux of +4.2 ± 1.4 × 108 mol per year in this region. This indicates that precipitation-driven CO2 emissions from rivers constitute a significant carbon source within the terrestrial carbon cycle of orogenic regions.

Discriminative characteristics of hydrochemical components and sedimentary organic matter in Korean coastal aquaculture systems during summer

Understanding the spatial distribution and sources of sedimentary organic matter (OM) in coastal environments is crucial for effective water quality management and the preservation of ecosystem health. Although extensive research has been conducted on OM dynamics, there remains a gap in understanding the ongoing biogeochemical processes in Korean coastal aquaculture zones, particularly during the summer season. To address this gap, we investigated the spatial variation of water chemical properties and isotopic composition of sedimentary OM to trace the composition, source, and reactivity of mixed OM in aquaculture systems along the Korean coast during the summer season. The isotopic approach was applied to surface sediments from five sections: western (W)-1, W-2, southern (S)-1, S-2, and eastern (E)-1. With respect to increased nutrients (mainly nitrate; 1.2 ± 0.6 mg/L) by dam-water discharge near W sections, our isotopic signatures revealed that a substantial fraction of sedimentary OM might dominantly originated from autochthonous OM source (algae; 36.5%) related to the increase of terrestrial nutrients. Simultaneously, the deposition of allochthonous OM (aquacultural feces; 44%) was predominant in the S-2 sections. The 34S-depleted patterns (approximately -7.2‰) in the S-2 section was indicative of active sulfate reduction occurring at the sedimentary boundary. Therefore, together with the precise determination of ongoing OM, our isotopic results provide valuable insights for effectively managing water-sedimentary qualities under the increase of anthropogenic contamination.

Different continuous freshwater contributions to submarine groundwater discharge at a coastal peatland, southern Baltic Sea

ABSTRACT The impact of freshwater sources like surface river runoff and submarine groundwater discharge (SGD) on coastal waters is currently in focus of intense debate and investigation. One of the ongoing challenges in SGD research is the characterization and quantification of the freshwater endmember contributions to the subsurface mixing zone and their influences on element balance and biogeochemical transformations. Long-term investigations of the sediment porewater composition provide characterization and understanding of the physical, hydrological and biogeochemical processes controlling the substance exchanges. In this study, we focus on the hydrochemical and stable isotope (δ 2H, δ 18O) compositions of sediment porewaters along the coastline of a southern Baltic Sea peatland. Coastal surface water and groundwater dynamics were monitored at two coastal sites using 5-m-long stationary lances over a 5-year period. The vertical compositional gradients were used to extrapolate to zero-salinity (ZS) components applying a binary mixing model on the salinity and water isotope composition. The results characterize a subterranean estuary (STE) with three potential mixing endmembers: two fresh groundwaters and the brackish Baltic Sea. Tritium–helium (3H–3He) porewater dating gave ages of more than about 20 years for the freshwater components. The ZS components were compared with other SGD sites along the southern Baltic Sea and North Sea and highlight the importance of local SGD studies for a proper groundwater endmember characterization as basis to understand hydrological and biogeochemical developments at the land–ocean continuum in times of current climate change.

Isotopic composition of natural waters of Kuzbass in coalbed methane production areas

Relevance. In Kuzbass, a coalbed methane production project is being implemented for the first time in Russia. Formation water extracted together with coalbed methane plays an important role, since it has been in contact with the coal-bearing rocks for a long time, therefore it contains rich geochemical information. Over the period 2002–2022, new isotopic data were accumulated both on the waters of the region coal deposits and on overlying waters, including surface waters. Aim. Based on the material accumulated on the isotopic composition (δD, δ18O, δ13C, 34S, 3H, 14C) of natural waters in coal-bearing areas, create an evolutionary scheme for the formation of waters within the framework of the developed hypothesis on the interaction of water-rock-coal-methane. Objects. River, underground waters of the zone of active water exchange, upper and lower parts of the zone of slow water exchange (extracted together with coalbed methane). Methods. Studies of the isotopic composition of waters were carried out in several laboratories: in the Multielement and Isotope Research Center of the SB RAS, the Technical Branch of the Federal State Unitary Enterprise “SNIIGGIMS”, in the radiocarbon AMS laboratory based on the Center for Collective Use “Cenozoic Geochronology” and in the Pacific Oceanological Institute Far Eastern Branch Russian Academy of Sciences (POI) FEB RAS. Results and conclusions. The paper introduces the data on δD, δ18О, δ13С и δ34S for surface and groundwater in Kuzbass in coalbed methane production areas. It is shown that all the waters under consideration are infiltration based on their isotopic composition (δD and δ18О). The waters of the lower part of the slow water exchange, produced together with coalbed methane, are characterized by a positive oxygen shift and very light hydrogen. A diagram of the evolution of the isotopic composition of water-dissolved carbon in the region has been compiled according to the data obtained. It is noted that the atmospheric source of CO2 is characteristic only of river waters, and only biogenic carbon dioxide is present in groundwater. The wide range of δ13СDIC values of the latter is explained by the varying degrees of participation of light soil carbon dioxide and heavy biochemical carbon dioxide formed during methane formation in the coal seam. The heaviest values are typical for waters produced together with coalbed methane, which is associated with long-term interaction with coal and methane. The time of such interaction was determined using the radiocarbon method: 17–30 thousand years. In areas where coalbed methane is produced, an increase in δ13СDIC values for all natural waters is observed, which requires further study.

Fast dehydration reduces bundle sheath conductance in C4 maize and sorghum.

In the face of anthropogenic warming, drought poses an escalating threat to food production. C4 plants offer promise in addressing this threat. C4 leaves operate a biochemical CO2 concentrating mechanism that exchanges metabolites between two partially isolated compartments (mesophyll and bundle sheath), which confers high-productivity potential in hot climates boosting water use efficiency. However, when C4 leaves experience dehydration, photosynthesis plummets. This paper explores the physiological mechanisms behind this decline. In a fast dehydration experiment, we measured the fluxes and isotopic composition of water and CO2 in the gas exchanged by leaves, and we interpreted results using a novel biochemical model and analysis of elasticity. Our findings show that, while CO2 supply to the mesophyll and to the bundle sheath persisted during dehydration, there was a decrease in CO2 conductance at the bundle sheath-mesophyll interface. We interpret this as causing a slowdown of intercellular metabolite exchange - an essential feature of C4 photosynthesis. This would impede the supply of reducing power to the bundle sheath, leading to phosphoglycerate accumulation and feedback inhibition of Rubisco carboxylation. The interplay between this rapid sensitivity and the effectiveness of coping strategies that C4 plants deploy may be an overlooked driver of their competitive performance.

Produced water geochemistry from hydraulically stimulated Niobrara Formation petroleum wells: Origin of salinity and temporal perspectives on treatment and reuse

Produced water (i.e., a mixture of returned injection fluids and geologic formation brines) represents the largest volumetric waste stream associated with petroleum production in the United States. As such, produced water has been the focus of intense study with emphasis on understanding the geologic origin of the fluids, environmental impacts of unintended or intentional release, disposal concerns, and their commodity (e.g., lithium) potential. However, produced water geochemistry from many active petroleum plays remain poorly understood leading to knowledge gaps associated with the origin of brine salinity and parameters (e.g., radium levels) that can impact treatment, disposal, and possible reuse. Here we evaluate the major ion geochemistry, radium concentrations, and stable water isotope composition of ~120 produced water samples collected from 17 producing unconventional petroleum wells in Weld County, Colorado from the Late Cretaceous Niobrara Formation. This sample set encompasses eight produced water time series from four new wells across production days 0 to ~365 and from four established wells across production days ~1000 to ~1700. Additionally, produced water from nine other established Niobrara Formation wells were sampled at discrete time points ranging from day 458 to day 2256, as well as hydraulic fracturing input fluids. These results expand the available Niobrara Formation produced water geochemical data, previously limited to a few wells sampled within the first year of production, allowing for the heterogeneity of major ions and radium to be evaluated. Specific highlights include: (i) observations that boron and bromide concentrations are higher in produced waters from new wells compared to older, established wells, suggesting the role of input fluids contributing to fluid geochemistry; and (ii) barium and radium concentrations vary between the producing benches of the Niobrara Formation with implications for treating radiological hazards in produced waters from this formation. Furthermore, we explore the geochemical relationships between major ion ratios and stable water isotope composition to understand the origin of salinity in Niobrara Formation brines from the Denver-Julesburg Basin. These findings are discussed with perspective toward potential treatment and reuse of Niobrara produced water prior to disposal.

Soil moisture and water redistribution patterns in white oak (Quercus alba) saplings and trees in fragmented urban woodlands

In the midwestern United States, models predict extended summer heatwaves and increasingly frequent and prolonged drought conditions. In the Chicago region, the potential for large-scale mortality of white oak trees (Quercus alba) coupled with the ongoing decline of white oak sapling recruitment are major concerns for researchers and practitioners. In this study, we determined the sources of water used by mature white oak trees and saplings in three qualitatively different sites within a remnant oak forest in Chicago during the 2021 drought. We investigated soil moisture dynamics (volumetric water content, VWC) and water isotope composition of leaf tissues (δD, δ18O), rainwater, and groundwater. These data were linked to sapling height (proxy for biomass) and ectomycorrhizal (ECM) functional types. We predicted that: (i) mature oak trees use deeper water sources and conducted hydraulic redistribution (HR), and (ii) mature trees shared water with saplings during dry periods via long-distance ECM functional types. Soil moisture decreased progressively from June to October (spring to fall), with August and September having the lowest moisture (<20 % VWC). Following rainfall recharge, temporal patterns of soil moisture showed gravity drainage and then ongoing stair-stepwise drawdown consistent with plant evapotranspiration. Leaf δD and δ18O values in mature trees and saplings were consistent with water uptake from rainfall and subsequent enrichment via evapotranspiration. In two sites, mature trees and saplings demonstrated distinct δD: δ18O slopes, with mature trees more enriched than saplings. In the third site, mature trees and saplings δD: δ18O slopes overlapped but here, the ECM community was dominated by contact-type ECM and sapling height increased with distance from the mature oak. Our findings indicate that HR was not a component of site ecohydrology, and future climate conditions may present increasing challenges for white oak recruitment as both mature trees and saplings compete for limited rainfall-derived soil moisture.

Isotopic steady state or non-steady state transpiration? Insights from whole-tree chambers.

Unravelling the complexities of transpiration can be assisted by understanding the oxygen isotope composition of transpired water vapour (δE). It is often assumed that δE is at steady state, thereby mirroring the oxygen isotope composition of source water (δsource), but this assumption has never been tested at the whole-tree scale. This study utilized the unique infrastructure of 12 whole-tree chambers enclosing Eucalyptus parramattensis E.C.Hall trees to measure δE along with concurrent temperature and gas exchange data. Six chambers tracked ambient air temperature and six were exposed to an ambient +3°C warming treatment. Day time means for δE were within 1.2‰ of δsource (-3.3‰) but varied considerably throughout the day. Our observations show that E. parramattensis trees are seldom transpiring at isotopic steady state over a diel period, but transpiration approaches source water isotopic composition over longer time periods.

Effects of Short‐Term Climate Variations on Young Water Fraction in a Small Pre‐Alpine Catchment

AbstractContinuous and extended observations of hydrometeorological parameters, alongside the analysis of the isotopic composition across diverse waters within catchments, can significantly enhance our understanding of the potential ramifications of climate change on the hydrological response. In this study, a comprehensive analysis of hydrometeorological and isotopic data was conducted over 10 hydrological years (October 2012–September 2022) within a small, forested catchment in the Italian pre‐Alps, aiming to investigate the impacts of short‐term climatic changes on the isotopic composition of waters and the young water fraction (Fyw). The results showed that the catchment experienced climate conditions with rapid warming and drying trends. Significant isotopic enrichments were observed in all sampled water sources, driven primarily by air temperature. Fyw was estimated to be 0.64 ± 0.06, 0.45 ± 0.07, and 0.16 ± 0.03 for stream water, soil water, and shallow groundwater based on the whole‐period sinusoidal fittings, respectively. Comparative analyses comprising different approaches for the estimation of Fyw showed that time‐windows scenarios and detrending corrections yielded smaller Fyw than approaches based on the whole‐period fitting and discharge‐sensitivity modeling. Such differences can be attributed to an uneven temporal distribution of stream water isotopic data, the difficulties in capturing high flows in a humid catchment characterized by a fast runoff response during rainfall‐runoff events, and the presence of isotopic trends. Our findings underscore the imperative of integrating interannual isotopic trends and adopting appropriate sampling strategy and methodological approaches to ensure a robust Fyw estimation.

ИЗУЧЕНИЕ ФИЗИКО-ХИМИЧЕСКИХ СВОЙСТВ «ЛЕГКОЙ» ВОДЫ И ЕГО ВЛИЯНИЕ НА РОСТ И РАЗВИТИЕ РАСТЕНИЙ

The article is devoted to the study of the physico-chemical properties of light water and its effect on plant growth and development. The author focuses on the fact that water does not occur in nature in its pure form, since it always contains various chemical elements. The types of water are considered: chemically and physically bound, as well as free water. Special attention is paid to the isotopic composition of water, including heavy water, and its physical characteristics such as density, boiling point and melting point. An experiment on the effect of light water depleted with deuterium on the growth of indoor roses is described. The study showed that plants watered with light water develop better compared to control groups watered with ordinary water. The author provides data on the results of plant growth for 12 weeks, which confirms the unique properties of light water, which helps to improve the condition of plants. In addition, an analysis of the chemical composition of drinking water and a phytochemical analysis of the content of flavonoids in plants watered with various types of water is provided. In conclusion, it is emphasized that light water has significant advantages over conventional water, which makes it promising for use in agriculture.

The Inca child of the Quehuar volcano: Stable isotopes clue to geographic origin and seasonal diet, with putative seaweed consumption

The Incas occupied the west coast of South America between 1438 and 1532 CE. Among the many rites they practised was the Capacocha, which involved the offering of children. Here we studied the mummy of a child found on the Quehuar volcano, Salta, Argentina. In order to determine the geographical origin of the child and to understand the living habits prior to its presentation as an offering, we incrementally measured the δ13C, δ15N, δ34S and δ2H values of keratin from a hair strand and the δ18O value of apatite phosphate from a rib bone. Although the origin of the child remains uncertain, the oxygen isotope composition of the drinking water deduced from the rib composition argues for an origin between 2,500 and 3,000 m.a.s.l. bordering the Andes. Furthermore, the sinusoidal δ2H signal measured in hair is compatible with the recording of local seasonal precipitation variations. The results indicate that the child did not move or moved only briefly prior to death. This offering may have occurred at the onset of the wet season (summer), as suggested by the hair δ2H values. By combining δ13C, δ15N and δ34S measurements in hair, we also proposed as the most parsimonious hypothesis that seaweed constituted a proportion (16.2 ± 12.9 %) of the diet, with a peak of consumption during the wet season (summer).

Coupled sulfur and nitrogen cycling at a catchment scale: insights from isotopic and molecular techniques

The biogeochemical cycles of nitrogen (N) and sulfur (S) play important roles in sustaining the Earth's ecosystem. However, their potential coupling process and underlying mechanisms in the nature remain unclear. Through joint applications of river water's isotopic compositions, isotope-pairing experiments, and molecular techniques, this study revealed the coupled N-S cycling processes at a catchment scale from both geochemical and biological perspectives. The river water's natural abundance isotopic compositions indicated that sulfide oxidation was an important source (67.0 ± 5.5 % in summer and 72.0 ± 5.5 % in winter) of riverine sulfate (SO42−). In addition, sulfide oxidation and NOx reduction (especially denitrification) were tightly coupled in summer but less significantly so in winter. However, the coupling of sulfide oxidation and dissimilatory nitrate reduction to ammonium (DNRA) could not be overlooked in winter. The 15N pairing experiments quantitatively showed that the high sulfide oxidation rates in summer (4.7 ± 2.3 mol/km2/h) were significantly associated with the denitrification. Metagenomics and qPCR analyses of the soils supported the isotopic interpretations, substantiating the metabolic potential and coexistence of bacterial denitrification, DNRA, and sulfide oxidation, which was more prevalent in summer. This study reveals comprehensive evidence that sulfide oxidation and NOx reduction are tightly coupled at the catchment scale, which provides a new perspective towards a better understanding of N-S cycling.