Isotopic Model Research Articles

Applying 224Ra and 223Ra to Trace Lateral Groundwater Discharge into Lake Qinghai, China

AbstractQuantifying lacustrine groundwater discharge (LGD) is important for understanding the dynamics of lake ecosystems and their expansion. This study focuses on Lake Qinghai, employing radium isotope models to evaluate the contributions of both shallow and deep groundwater. The data indicate that the activity of 223Ra and 224Ra demonstrates a pronounced gradient, decreasing from the shoreline to the center of Lake Qinghai. Additionally, vertical stratification characteristics were observed. The spatial distribution of radium isotope activity suggests that there is discharge of both shallow and deep groundwater into the lake. Deep groundwater migrates slowly and its apparent age reflects the time elapsed since the water became enriched in Ra and was isolated from the source, in the study system this age is estimated to be 10.1 d. In contrast, shallow groundwater displayed varied apparent ages in different regions: 7.9 d in the north, 13.1 d in the south, and 7.4 d in the southeastern area of the lake. The LGDs of shallow groundwater discharge in the north, south, and southeast areas of Lake Qinghai were estimated by 224Ra as 1.89 × 106 to 2.69 × 106 m3/d, 3.25 × 106 to 3.99 × 106 m3/d, and 4.51 × 106 to 6.33 × 106 m3/d, respectively. For deep groundwater, the LGD was 0.16 × 106 to 0.29 × 106 m3/d. Annually, the total LGD fluxes of shallow and deep groundwater are 27.86 × 108 to 37.59 × 108 m3/year and 0.58 × 108 to 1.06 × 108 m3/year, respectively. This study is the first to evaluate shallow and deep groundwater discharge around the lake. Understanding these discharge dynamics is essential for developing effective management strategies to preserve lake environments.

Characterizing and sourcing metal air contamination coupling concentrations and lead isotopes from moss biomonitoring in urban cemeteries

Populations are constantly exposed to airborne metals, in particular in urban areas. Despite their proven links to health issues, their origin and fate are still subject to debate. Bioindicators, by taking up and cumulating atmospheric metals over time, have been widely used to proxy environmental quality over large areas, at various time scales. Using the example of the Paris region, we investigated the potential for the Grimmia pulvinata moss species to both characterize air metal contamination and to identify its main sources. To this end, we coupled metal/metalloid (Al, As, Cd, Cr, Cu, Fe, Ni, Pb, Sb, Sr, V and Zn) concentrations and Pb isotope ratios from samples collected in cemeteries in the city and its suburbs. Metal enrichment factors ranged between 2 and 10 for As, Cr, Fe, Ni, Sr, V, between 50 and 100 for Cu, Pb and Zn and > 100 for Cd and Sb, indicating a dominant anthropogenic origin. Principal component analysis showed that 3 principal components explained 89% of the metal variations: (i) European atmospheric background, (ii) regional urban sources, and (iii) resuspension of regional soils. This was corroborated by Pb isotope ratios, whose variations were modelled by a ternary mixing that considered the same 3 emission sources. Using a MixSIAR isotope model, we reveal that the European atmospheric background contributes slightly (< ~ 5%) and that within 20 km of the city center bioindicators are mostly impacted by urban sources (contributions: 50–80%). Samples collected > 20 km show almost equal contributions of the endmembers representing urban activities and agricultural soil resuspension.

Assessing the Hydrological Impact of Gravity‐Fed Irrigation on Groundwater Recharge Using Long‐Term Isotope Monitoring and Modelling

ABSTRACTThis study investigates the hydrological processes driving groundwater recharge in the Avignon Plain (south‐eastern France) through a detailed analysis of the interactions between irrigation, rainfall and soil water using long‐term isotopic monitoring and lumped parameter modelling. More than 15 years of monthly isotopic data from rainwater, surface water, soil water and groundwater were analysed to quantify the contributions of gravity‐fed irrigation and natural rainfall to aquifer recharge. Our results show that gravity‐fed irrigation contributes about 85% of the recharge, highlighting the significant role of traditional agricultural practices in maintaining groundwater levels. Through isotopic tracing and modelling, we observed variations in transit times, with faster infiltration pathways associated with irrigation flows compared to more prolonged recharge from rainfall. This study not only demonstrates the effectiveness of isotopic techniques for assessing water sources in complex recharge scenarios but also provides insights into how irrigation practices affect groundwater sustainability. These results contribute to current thinking on sustainable water management and highlight the need for integrated approaches that reconcile agricultural water use efficiency and groundwater conservation.

Dissolved Nitrogen Cycling in the Eastern Canadian Arctic Archipelago and Baffin Bay From Stable Isotopic Data.

Climate change is expected to alter the input of nitrogen (N) sources in the Eastern Canadian Arctic Archipelago and Baffin Bay due to increased discharge from glacial meltwater and permafrost thaw. Since dissolved inorganic N is generally depleted in surface waters, dissolved organic N (DON) could represent a significant N source fueling phytoplankton activity in Arctic ecosystems. Yet, few DON data for this region exist. We measured concentrations and stable isotope ratios of DON (δ15N) and nitrate (NO3 -; δ15N and δ18O) to investigate the sources and cycling of dissolved nitrogen in regional rivers and marine samples collected in the Eastern Canadian Arctic Archipelago and Baffin Bay during the summer of 2019. The isotopic signatures of NO3 - in rivers could be reproduced in a steady state isotopic model by invoking mixing between atmospheric NO3 - and nitrified ammonium as well as NO3 - assimilation by phytoplankton. DON concentrations were low in most rivers (≤4.9μmolNL-1), whereas the concentrations (0.54-12μmolNL-1) and δ15N of DON (-0.71-9.6‰) at the sea surface were variable among stations, suggesting dynamic cycling and/or distinctive sources. In two regions with high chlorophyll-a, DON concentrations were inversely correlated with chlorophyll-a and the δ15N of DON, suggesting net DON consumption in localized phytoplankton blooms. We derived an isotope effect of 6.9‰ for DON consumption. Our data helps establish a baseline to assess future changes in the nutrient regime for this climate-sensitive region.

Integrating isotope mixing and hydrologic models towards a more accurate riverine nitrate source apportionment

Nitrate (NO3–) is the major form of bioavailable nitrogen in most rivers, and its dramatic increase may lead to a number of serious environmental issues, such as eutrophication and biodiversity decline. Quantification of NO3– sources and fluxes in rivers is essential for effective management of NO3– pollution. Isotope mixing and hydrological models are proven practical tools for quantifying the sources of NO3– in rivers, yet both methods have severe limitations. To improve the accuracy and reliability of riverine NO3– source apportionment, this study proposed a protocol that integrates the strengths of both tools, capable of solving issues such as the calculation bias caused by isotope endmember overprinting in isotope mixing model and the lack of validation data for hydrological models. We applied the framework to a typical agricultural river, the Qihe River, and illustrated the effectiveness of the method in quantifying riverine NO3– sources. The proportional contribution of sewage simulated by the SWAT model approximated that estimated by the isotopic mixing model, yet the SWAT-based contributions of soil organic nitrogen and chemical fertilizer were 16.3 % lower and 14.0 % higher, respectively than the MCMC-based results. After integrating both models, we adopted the proportions of NO3– sources in the river from chemical fertilizer, sewage, and soil organic nitrogen as 45.1 %, 30.9 %, and 23.9 %, respectively. This study showed that coupling isotopic and hydrological models provided a new dimension for the accurate quantification of N sources in rivers.

Isotopic evidence of diet breadth hunter-gatherers changes during the Holocene in the Central Pampean Dunefields (Argentina, South America).

Based on the analysis of stable carbon and nitrogen isotopes of bone collagen, stable carbon isotopes of bone apatite and an extensive AMS dating series (~10,000-299 years cal BP), the human paleodiets of 34 individuals from the Central Pampean Dunefields (Argentina, South America) are evaluated. These data are interpreted from the isotopic ecology of animals with archaeofaunal evidence of consumption and isotopic models of human diet. Multivariate carbon and nitrogen stable isotope model and Bayesian stable isotope ellipses were used to interpret human diets. Analysis of isotopic values indicates intake of enriched lipids and/or carbohydrates in relation to the proteins consumed throughout the Holocene. The isotopic values of Middle Holocene humans in relation to the values of exploited resources point out that individuals obtained protein mainly from guanaco. Subsequently, there was an increase in the human breadth diet during the Late Holocene, with a greater relevance of small prey of high trophic levels and vegetables. This contrasts with zooarchaeological information indicating generalist human diets during the Middle Holocene and specialized human diets in guanaco during the Late Holocene. It is proposed that during the Middle Holocene arid period, the combination of low human population density and high residential mobility in wide foraging ranges allowed the guanaco to be the main source of protein. During the Late Holocene humid period, there was an increase in human population density and a decrease in residential mobility, which caused greater pressure on foraging territories and increased dietary breadth.

Nanoscale Characteristics of Carlin-Type Auriferous Pyrite from the Nadaleen Trend, Yukon

Abstract Gold deposits of the Nadaleen trend in central Yukon host over 1.7 million ounces (Moz) of Au and share many characteristics in common with Nevada’s Carlin-type deposits, including similar host rock types, structural setting, alteration, and geochemistry, as well as the occurrence of gold in hydrothermal arsenian pyrite. We examined the textures, minor and trace element geochemistry, and δ34S signatures of precursor pyrite and hydrothermal pyrite overgrowths in samples grading over 35 g/t Au from the Sunrise and Conrad deposits. In the Osiris limestone at Sunrise, hydrothermal pyrite occurs as rims ranging from &amp;lt;1 to 5 µm overgrowing subhedral to euhedral sedimentary pyrite grains that are 20 to 100 µm in diameter; as rims (&amp;lt;1 to 3 µm thick) of hydrothermal pyrite that cement together the individual aggregates (measuring &amp;lt;1 to 5 µm) in framboidal pyrite; and as disseminated hydrothermal pyrite grains (&amp;lt;1 µm) that may be single stage. The hydrothermal pyrite in our Sunrise samples contains up to 45 ppm Au, 29 ppm Cu, 1,053 ppm As, and 15 ppm Ag, with δ34S compositions that are 1 to 8‰ higher than the sedimentary pyrite. The hydrothermal pyrite is zoned at the nanoscale, with the highest Au concentrations typically in the outermost portion of the rims. In the Conrad gabbroic dike, hydrothermal pyrite occurs as rims ranging from &amp;lt;1 to 5 µm overgrowing earlier pyrite grains that are 5 to 100 µm in diameter. The inner rims of the hydrothermal pyrite contain up to about 20 ppm Au, 900 ppm As, 60 ppm Ag, and 50 ppm Cu, whereas the outer margins of the hydrothermal pyrite contain up to about 670 ppm Au, 23,400 ppm As, 385 ppm Ag, and 115 ppm Cu. Relatively coarse hydrothermal rims (up to 5-µm) occur on the coarsest grains of precursor pyrite, suggesting that the substrate partially controls the texture of the hydrothermal pyrite, potentially due to the availability of Fe during sulfidation. The δ34S plateau values of the hydrothermal rims range from 1.2 to 11.0‰. Bayesian stable isotope modeling shows that the δ34S compositions of the hydrothermal pyrite can be generated by mixing the locally present sedimentary rocks with locally present magmatic sulfur. The modeling indicates that additional sources are not required, although they cannot be ruled out. At high Au concentrations, the modeling shows that most of the sulfur in the hydrothermal pyrite comes from a magmatic source, potentially from buried plutons visible as aeromagmetic anomalies. The modeling does not differentiate between whether (1) these magmatic rocks contributed sulfur and metals during passive leaching by an amagmatic hydrothermal fluid or (2) cooling magmas exsolved a sulfur- and metal-bearing fluid that led to magmatic-hydrothermal mineralization. We favor the latter interpretation, since the available geochronological evidence suggests that mineralization on the Nadaleen trend occurred during or shortly after Late Cretaceous emplacement of volumetrically limited, mantle-derived gabbroic dikes. Collectively, the evidence supports a Carlin-type origin for the gold deposits on the Nadaleen trend. Continued study is needed to link site-specific characteristics and processes to the regional metallogenic setting.

Utilizing fluorescence indicators to apportion organic sources in estuarine/coastal sediments: A comparison with a stable isotopic model

Coastal sediments accumulate organic matter (OM) from diverse sources, including local anthropogenic pollution. Effective source tracking of sediment OM is crucial for pollution source management. This study compares fluorescence proxies and stable isotopic ratios as tracers for sediment OM in Gangu Port, Korea. An optimized extraction method using distilled water for 0.5 h yielded distinct fluorescence signatures. The humification index (HIX) and protein-like component (C3%) showed ideal mixing behavior with two end-members (fishery market sediment and algae). A Bayesian end-member mixing analysis model revealed that agricultural soil is the prevalent contributor to sediments, aligning with land use patterns. The fluorescence-based model showed higher sensitivity to anthropogenic influences compared to traditional stable isotope ratios. The results strongly agreed with isotope ratio-based predictions, exhibiting a positive correlation (p < 0.05) at 8 out of 14 sites. This study highlights the potential of fluorescence-based tracking to complement or replace conventional stable isotope methods.

Effects of different surface water flow frequencies on water use characteristics of Tamarix ramosissima in the hinterland of the Taklamakan Desert

Tamarix ramosissima is a dominant species in desert ecosystems and an ecological barrier species in arid areas, playing a crucial role in stabilizing dunes and preventing desertification. In this study, river water, groundwater, soil water, and T. ramosissima individual samples were collected from three sites in July and October 2023 at the Daliyaboyi Oasis located at the tail of the Kriya River in the hinterland of the Taklamakan Desert. The three sites are referred to as the center (SE), west (SW), and north (SN) sites within the Daliyaboyi Oasis, and each experienced different flood frequencies. The SE site experienced flooding in July and October, the SW site experienced flooding only in July, and the SN site experienced no flooding in July or October. The spatial and temporal variation in hydrogen and oxygen stable isotopes and line-conditional excess (lc-excess) in water and plant samples were analyzed, and the potential changes in water use of T. ramosissima were analyzed by the hydrogen and oxygen stable isotope and MixSIAR model. The findings indicated that the slope of SWL at the SE, SW, and SN sites was higher in July (6.77, 6.42, and 3.05, respectively) than in October (7.37, 3.30, and 2.14, respectively). The lc-excess value of the SE site did not exhibit seasonal changes; only the lc-excess values of soil water in SW and SN sites showed seasonal changes. MixSIAR results indicated frequent flood events at the SE site, with relatively constant proportions of water source utilization by T. ramosissima in July and October. In addition, shallow soil water (0–60 cm) and deeper soil water (60–80 cm) were the main water sources of T. ramosissima at SE. The SN site was slightly influenced by surface water, resulting in statistically non-significant changes in the water source utilization by T. ramosissima. Indeed, deep soil water (60–200 cm) and groundwater were the sources of water for T. ramosissima at this site. In contrast with October, the SW site experienced flood events in July, resulting in the utilization of water by T. ramosissima from the shallow soil (0–60 cm) and deep soil (60–280 cm) in July and October, respectively. Different surface water flow patterns led to different water use characteristics of T. ramosissima, which further demonstrated that T. ramosissima has high resilience and ecological plasticity. This work provides a useful reference for the implementation of effective ecological water transport measures in the Daliyaboyi Oasis and similar arid habitats.

Testing tree-ring cellulose δ18O with water isotopes for Holocene lake δ18O interpretations in the central Rocky Mountains USA

Stable isotopes of water preserved in geologic archives, primarily as oxygen (δ18O), have proven critical for documenting Earth’s climatic and hydrologic systems past and present. However, timescale differences of water isotope inputs to proxy systems and the signal embedded in long paleorecords often confound translation to observed hydroclimatic metrics. Here, a unique 20-year dataset of meteorology, hydrology, and the isotopic composition of weekly meteoric and surface water samples (δ18O, δ2H) are combined with paleoclimate δ18O data from tree-ring cellulose and lake carbonate to better understand proxy signals of Upper Colorado river basin drought. Annual tree-ring cellulose δ18O from Picea engelmannii growing within a glacier-fed creek and a spring discharge area were used to derive annual source water δ18O using a cellulose source-water isotope model. Comparisons with the monitoring record indicates that tree-ring cellulose δ18O tracks variations in wet and dry hydroclimatic extremes. Source water isotopes are shown to reflect the hydroclimate of the current year and some number of previous years as an effective moisture-discharge proxy rather than a precipitation isotope proxy. Results contextualize Holocene lake carbonate δ18O data. The contemporary-to-paleo comparison identifies changes in seasonal precipitation extremes during recent millennia and several earlier arid and monsoon-dominated Holocene periods that exceed the arid maximum of the calibration period.

Hydrological controls of a riparian wetland based on stable isotope data and model simulations.

Isotopic evidence of groundwater and stream water is frequently used to investigate water exchanges with groundwater. Monthly sampling of rain, stream water, and groundwater was conducted at Tims Branch watershed in South Carolina for the oxygen and hydrogen stable isotope (δ2H and δ18O) measurement, as well as pH and oxidation-reduction potential (ORP). Together with a mass balance perspective, it was determined that it takes a few weeks to one month for groundwater in the hyporheic zone to fully exchange with stream water. From hydrodynamic modelling, we show that substantial (up to 70 %) groundwater exchange occurs at gaining and losing sites. Groundwater exfiltration, i.e. inflow into stream water, contributes up to 4 % to stream water, with the remainder from upstream exfiltration. A 2-4 % per day renewal rate of adjacent groundwater would indirectly indicate a groundwater residence time in the order of half a month to a full month (assuming either a well-mixed case or large dispersion rate in pulse flow case), in agreement with a greatly reduced variability of δ2H and δ18O of groundwater compared to stream water and rain. This reduced variability of stable isotope signal from groundwater confirms our hypothesis that riparian groundwater mixing at Tims Branch is more of a mixed type rather than a pulse flow type. A monthly time scale is sufficient for groundwater to become anoxic at exit points into stream water resulting in the episodic production of natural organic matter- and iron-rich flocs upon oxidation.

Deciphering the impact of cascade reservoirs on nitrogen transport and nitrate transformation: Insights from multiple isotope analysis and machine learning

Construction of cascade reservoirs has altered nutrient dynamics and biogeochemical cycles, thereby influencing the composition and productivity of river ecosystems. The Lancang River (LCR), characterized by its cascade reservoir system, presents uncertainties in nitrogen transport and nitrate transformation mechanisms. Herein, we conducted monthly monitoring of hydrochemistry and multiple stable isotopes (δ15N-NO3-, δ18O-NO3-, δ18O-H2O, δD-H2O) throughout 2019 in both the natural river reach (NRR) and cascade reservoirs reach (CRR) of the LCR. Through the monthly detection of nitrogen forms and runoff in the import (M2) and export (M9) section, the average annual retention ratios for Total nitrogen (TN), Nitrate nitrogen (NO3--N), Particulate Nitrogen (PN) and Ammonium Nitrogen (NH4+-N) were about -35%, -53%, 48% and -65%, respectively. The retention rates were positively correlated with hydraulic retention time and negatively correlated with reservoir age, especially in the flood season. Compared to the NRR, the reservoir had significantly affected the nitrogen transport characteristics, especially for the large reservoirs (like Xiaowan and Nuozhadu), which enhanced phytoplankton uptake of NO3--N to form PN capabilities in the lentic environment and subsequently to precipitate or intercept it at the reservoir. This led to the overall decreasing trend of TN and PN concentrations along the CRR. The Bayesian stable isotope model quantified NO3--N sources from the NRR to the CRR. During this transition, soil nitrogen (SN) ratios decreased from 69.3% to 61.8%, while Manure & sewage (M&S) increased from 24.0% to 31.3%. Anthropogenic and natural factors, including urban sewage discharge, population density, and precipitation, were selected as key predictor variables. The eXtreme Gradient Boosting (XGBoost) model exhibited superior predictive performance for NO3--N concentrations, achieving an R2 of 0.70. These findings deepen our understanding of the impact of reservoirs on river ecology.

The δ2H and δ18O isotopic evidence for hydraulic redistribution by Alnus acuminata in an agricultural landscape

Understanding of the process of hydraulic redistribution in agricultural landscapes is important for informing agroforestry design and agricultural management. The measurement of hydraulic lift and redistribution in the field is still a challenge. Due to the robustness of stable isotope analysis, we hypothesized that the measurement and analysis of the natural abundance of stable isotopes δ2H and δ1⁸O, in the twigs of agroforestry trees, stems of wheat intercrop, rain, and soil water coupled to an isotopic mixing modeling by IsoSource supplemented with other physiological crop parameters, would estimate the extent of hydraulic redistribution in intercropping, and inform the design of an agroforestry system. There are still many plant species that have not been investigated for their potential hydraulic redistribution yet, and Alnus acuminata is among them, therefore this study aimed to contribute to filling that gap. The field experiment was conducted in an Andic soil of the northern Rwanda highlands to address the extent of water efflux redistribution from tree roots of Alnus acuminata to the wheat intercrop across bench terraces. The study involved the measurement of the natural abundance of stable isotopes δ2H, and δ1⁸O of the tree twigs, soil and wheat stems at distances of 1, 3, 5, and 7 m from the tree lines of Alnus acuminata, and of rainwater. The isotopic mixing modeling was supplemented by measuring both specific leaf area (SLA) and carbon discrimination (Δ13C) in the wheat leaf. We noted a significant (p < 0.01) gradient in the depletion of wheat xylem water δ2H and δ18O signatures moving further away from the tree lines. Based on the wheat value of δ2H, the isoSource indicated that the trees may have contributed the wheat water up to 64.3 ± 2.6% at 5 m from the trees, and the values of both the SLA (cm2 g–1) and ∆13C (‰) of wheat leaf indicated the water use efficiency of wheat significantly improved around the trees up to 3 m away from the trees with 140.10 ± 3.74 cm2 g–1, 149.56 ± 3.43 cm2 g–1 and 20.6 ± 0.1‰, 20.8 ± 0.1‰ at 1 m and 3 m for SLA and ∆13C respectively. We concluded that Alnus acuminata exhibits significant hydraulic redistribution in the field.

Differences in Nitrogen Sources and Contributions in Shallow Groundwater in Plateau Lake Area with Different Climate Types

Clarifying the concentration, major sources, and contribution differences of nitrogen in shallow groundwater in plateau lake areas with different climate types can provide a novel direction for the control of nitrate （NO3-） pollution in regional groundwater. Taking the shallow groundwater around Erhai Lake in the subtropical monsoon climate zone and Chenghai Lake in the dry-hot valley area of the Jinsha River as the research objects, using hydrochemical indexes and multi-isotope techniques （δ15N-NO3-, δ18O-NO3-, δ18O-H2O, and δ2H-H2O） combined with the stable isotope （SIAR） model； the differences in nitrogen concentration in shallow groundwater around Erhai Lake and Chenghai Lake were analyzed, the sources of NO3- were identified, and the contribution rates of each pollution source were calculated. The results showed that water quality of more than 33% and 5% of shallow groundwater sampling points around Erhai Lake and Chenghai Lake was worse than the groundwater Class Ⅲ quality requirements （GB/T 14848） of 20 mg·L-1 for nitrate nitrogen （NO3--N）, respectively. The δ18O-H2O and δ2H-H2O in shallow groundwater around Erhai Lake and Chenghai Lake were parallel to the global and Chinese atmospheric precipitation lines, and a large intercept was present, indicating that atmospheric precipitation was not the major recharge source of groundwater in the two regions. The contribution rate of different NO3- sources in shallow groundwater around Erhai Lake was the highest for soil organic nitrogen （53.77%）, followed by nitrogen fertilizer （21.75%） and manure and sewage （21.55%）, and atmospheric deposition nitrogen （2.93%） was the lowest. Denitrification occurred in the transformation process of nitrogen in groundwater. The contribution rate of different NO3- sources in shallow groundwater around Chenghai Lake was manure and sewage （44.88%） &gt; soil organic nitrogen （37.03%） &gt; nitrogen fertilizer （16.17%） &gt; atmospheric deposition nitrogen （1.92%）, and nitrification occurred in the transformation process of nitrogen in groundwater. The climate type significantly affected the shallow groundwater level, altering the migration and transformation process of nitrogen, thereby affecting the nitrogen concentration in groundwater and the contribution of NO3- as the chief source. However, the major source of NO3- was not affected by the climate type； however was more affected by land use, agricultural activities, and manure treatment methods.

Isotope Evidence for Rice Accumulation of Newly Deposited and Soil Legacy Cadmium: A Three-Year Field Study.

Biogeochemical processes of atmospherically deposited cadmium (Cd) in soils and accumulation in rice were investigated through a three-year fully factorial atmospheric exposure experiment using Cd stable isotopes and diffusive gradients in thin films (DGT). Our results showed that approximately 37-79% of Cd in rice grains was contributed by atmospheric deposition through root and foliar uptake during the rice growing season, while the deposited Cd accounted for a small proportion of the soil pools. The highly bioavailable metals in atmospheric deposition significantly increased the soil DGT-measured bioavailable fraction; yet, this fraction rapidly aged following a first-order exponential decay model, leading to similar percentages of the bioavailable fraction in soils exposed for 1-3 years. The enrichment of light Cd isotopes in the atmospheric deposition resulted in a significant shift toward lighter Cd isotopes in rice plants. Using a modified isotopic mass balance model, foliar and root uptake of deposited Cd accounted for 47-51% and 28-36% in leaves, 41-45% and 22-30% in stems, and 45-49% and 26-30% in grains, respectively. The implications of this study are that new atmospheric deposition disproportionately contributes to the uptake of Cd in rice, and managing emissions thus becomes very important versus remediation of impacted soils.

Geochronology and Origin of Quaternary Dacites from the Daliuchong Volcano in the Tengchong Volcanic Field (TVF), SE Tibetan Plateau

Quaternary volcanoes from the southeastern Tibetan Plateau occur at the Tengchong volcanic field (TVF). The Daliuchong volcano is the largest volcano in the TVF, which has the most felsic compositions with explosive eruptions. The eruption history and origin of the Daliuchong volcano are a matter of debate. In the present paper, we report the groundmass K-Ar ages, whole-rock Sr-Nd-Pb-Hf isotopes, zircon U-Pb ages, and Hf-O isotopic compositions for the Daliuchong volcano to constrain its eruption history and petrogenesis. The groundmass K-Ar ages and zircon U-Pb ages indicate mid-Pleistocene (0.6 Ma to 0.3 Ma) eruptions. The presence of zircon phenocrysts with enriched mantle-like O-Hf isotopes (δ18O &lt; 6‰, and εHf about −2) suggests the involvement of mantle-derived basaltic magmas. The whole-rock Pb isotope compositions and Sr-Nd isotope modeling reveal the involvement of magma from the lower crust. The zircon xenocrysts reveal previously unrecognized 20-Ma magmatic activity at the TVF and contamination of late Cretaceous (66–80 Ma) S-type granites during the formation of the Daliuchong dacites. The dacite magma at Daliuchong was formed by mixing of the mantle-derived magma and lower-crust-derived magma and subsequently contaminated by upper crustal materials, including late Cretaceous S-type granitic rocks.

Isotopic trophic discrimination factors (Δ13C, Δ15N) and their determinants in a subtropical macroinvertebrate food chain

The accurate estimation of trophic discrimination factors (TDFs) for stable carbon and nitrogen isotopes (Δ13C and Δ15N) requires studies for each particular species or taxonomic group, because the use of general TDFs values for all animals obtained from the literature represents an important bias in isotopic modelling. Values for Δ13C and Δ15N were estimated in an aquatic food chain (periphyton-Chironomini-Perithemis sp.), in a subtropical region of South America, under experimental conditions using two approaches: i) Traditional arithmetic equation and ii) Bayesian inference from mixing models. The effect of diet quality on TDF variability was also evaluated. We report values for Δ13C and Δ15N for Chironomini when feeding on periphyton (1.12 ± 1.31‰ and 0.92 ± 1.94‰ for C and N, respectively using the arithmetic equation) and for Perithemis sp. when feeding on Chironomini (0.65 ± 1.52‰ and 0.90 ± 1.08‰ for C and N, respectively, according to the arithmetic equation). We obtained similar results when using Bayesian inference. We did not find effects of diet quality on Δ13C and Δ15N values; although we highlighted that, unexpectedly, the taxonomic composition of periphyton strongly affected the isotopic values of C and N. These reported values improve the accuracy of isotopic modeling for subtropical aquatic macroinvertebrates in future food web research.

Control of magmatic halogen composition and redox state on the zonation of metal mineralization across active continental margins: Perspectives from the world-class South China metallogenic province

Active continental margins are the major sites of continental magmatism and associated hydrothermal ore deposits with a broad metal spectrum. Mineralization across active continental margins typically displays spatial zonation, with porphyry copper-(molybdenum‑gold) deposits in volcanic arcs and tin- and tungsten-dominated mineralization occurring further inland in a back-arc setting. Particularly, tin and tungsten commonly form separate deposits in back-arc regions, even though both metals exhibit similar lithophile behavior. The key factors governing this metallogenic zonation remain unclear. The world-class South China metallogenic province hosts over 50 % of the global tungsten resources, along with a significant amount of tin and copper resources distributed in different mineralization belts, making it an ideal location in which to study regional metal zonation. Here, we comprehensively integrate a very large dataset of the halogen volatile composition (F, Cl) and oxygen fugacity of granites related to tin, tungsten, and copper mineralization in the South China continental margin. Our compilation, derived from a substantial collection of zircon, apatite, mica, and whole-rock geochemistry data, suggests that lateral variations in granite magmatism (away from the trench), transitioning from chlorine-rich and oxic to fluorine-rich and reduced conditions, exert the primary control on copper versus tin‑tungsten mineralization in the arc and back-arc regions, respectively. Differences in oxygen fugacity have a minor impact on the decoupling of tin and tungsten mineralization despite tin granites being universally reduced (ΔFMQ = −1.8 to −0.1, where FMQ is the fayalite-magnetite-quartz redox buffer) and tungsten granites having a broader redox range (ΔFMQ = −1.5 to +1.2). Instead, the disparity in fluorine content plays a more crucial role in controlling the spatial separation of tin and tungsten mineralization observed in the back-arc setting. Nd-Hf and He-Ar isotopic modeling calculations suggest that magmas linked to tin mineralization have a more pronounced involvement of F-rich mantle components compared to those associated with tungsten. Elevated fluorine (ca. 650–8000 ppm) in tin-associated magmas allowed an extreme degree of magmatic differentiation and delayed fluid exsolution due to high H2O solubility in F-rich silicate melts, ensuring Sn enrichment in highly evolved melts. In contrast, early fluid exsolution under less F-rich conditions (ca. 100–700 ppm) led to early tin loss from the melts, ultimately resulting in tungsten-dominant mineralization. This work emphasizes the combined influence of halogen composition and redox state on the regional mineralization zonation in world-class metallogenic provinces, providing vectors for global metal exploration in both past and currently active continental margins.

Tracing nitrogen and phosphorus pollution in urban runoff: Insights from isotopic tracers and SWMM modeling

Water contamination in certain rivers during rainfall necessitates the evaluation of pollutant levels within pipelines and the identification of their sources to ensure effective pollution control. In this study, we assess pollutant concentrations during runoff from surfaces, pipelines, and channels, identify pollutant sources within pipelines, and analyze sewage leakage contributions to channel pollution in residential areas in Wuxi City, China. The results showed that the event mean concentrations of total nitrogen (TN), total phosphorus (TP), ammonium (NH4+-N), and nitrate (NO3−-N) in the drainage outlet runoff were 3.4, 1.1, 8.8, and 14.9 times higher than in impervious surface runoff. The predominant forms of nitrogen and phosphorus in runoff shift from organic to inorganic as they move from the surface to pipelines. The pipeline load and contribution were further estimated by combining water quantity calculations from the calibrated and verified Storm Water Management Model (SWMM) with measured nitrogen and phosphorus concentrations in the runoff. TN, NH4+-N, NO3−-N, and PO43--P within the pipelines accounted for 59%, 83%, 90%, and 77% of the discharge loads, respectively. The application of the Stable Isotope Analysis in R (SIAR) package (MixSIAR) revealed that the domestic sewage and soil organic N were the predominant sources of pollutants within drainage pipelines, contributing 23.7% and 32.6% of NO3−-N, respectively. Additionally, the sewage leakage accounted for 33.7% and 66.9% of NO3−-N in drainage runoff and channels, respectively. Unlike existing methods, this study quantitatively highlights the significant impact of pipeline pollutants and sewage leakage on urban river water quality, providing essential insights for developing effective strategies to mitigate non-point source water pollution.

End-Member Mixing Model for Methane Carbon Isotope Fractionation During Shale Gas Desorption and Its Application.

Unlike conventional natural gas reservoirs, shale gas development involves systematic changes in methane carbon isotopes that cannot be effectively described by existing isotope fractionation models and mechanisms. Therefore, based on fundamental theories such as Rayleigh fractionation, mass transfer flow, and mass conservation, this study established isotopic fractionation equations for methane in adsorbed and free gas. By considering adsorbed and free gases as two end-members and using an isotope mixing model, a fractionation model for methane carbon isotopes during shale gas desorption was constructed. This model quantifies the isotopic fractionation effects during shale gas desorption and elucidates the mechanism of methane carbon isotope fractionation. Using on-site desorbed gas content and isotope data, parameter fitting and model calculations were conducted to characterize methane carbon isotope variations throughout the process of shale core field desorption. The results show a pattern of "initially negative and then turning positive," consistent with those of physical simulation experiments. It was clarified that differences in mixing the two end-members and isotopic fractionation play key roles in the variation of methane carbon isotopic composition in shale gas. By applying the methane carbon isotope fractionation model, the contribution of adsorbed gas during shale gas production was explored. It was found that in the early stage of development, the adsorbed gas in Well JY 1 was negligible. After nearly seven years of development, the contribution of adsorbed gas in the later stage has only reached nearly 15%, indicating that the production contribution of adsorbed gas is still less than 0.3 million cubic feet per day. The open flow of Well JY 6-2 is more conducive to the production of adsorbed gas, but the production capacity is still mainly contributed by free gas, indicating that the shale gas production capacity in the later stage in the Jiaoshiba gas field is still primarily dominated by free gas.