Deep learning insights into spatial patterns of stable isotopes in Iran's precipitation: a novel approach to climatological mapping.

Stable isotope techniques are precise methods for studying various aspects of hydrology, such as precipitation characteristics. However, understanding the variations in the stable isotope content in precipitation is challenging in Iran due to numerous climatic and geographic factors. To address this, forty-two precipitation sampling stations were selected across Iran to assess the fractional importance of these climatic and geographic parameters influencing stable isotopes. Additionally, deep learning models were employed to simulate the stable isotope content, with missing data initially addressed using the predictive mean matching (PMM) method. Subsequently, the recursive feature elimination (RFE) technique was applied to identify influential parameters impacting Iran's precipitation stable isotope content. Following this, long short-term memory (LSTM) and deep neural network (DNN) models were utilized to predict stable isotope values in precipitation. Interpolated maps of these values across Iran were developed using inverse distance weighting (IDW), while an interpolated reconstruction error (RE) map was generated to quantify deviations between observed and predicted values at study stations, offering insights into model precision. Validation using evaluation metrics demonstrated that the model based on DNN exhibited higher accuracy. Furthermore, RE maps confirmed acceptable accuracy in simulating the stable isotope content, albeit with minor weaknesses observed in simulation maps. The methodology outlined in this study holds promise for application in regions worldwide characterized by diverse climatic conditions.

Isotopic and trace element record of changing metal source contributions to tropical freshwater Lake Naivasha (Kenya).

Lake Naivasha, Kenya's second-largest freshwater body is a wetland of international ecological importance and currently subjected to unprecedented anthropogenic influence. The study aims to chronologically reconstruct the main human activities and background weathering reactions that govern metal mobilizations into the lake and their potentially adverse effects on its ecological status. We combine extensive geochemical analyses (major, trace elements, Zn-Pb isotope ratios) in a dated lake sediment record and catchment rocks with remote sensing techniques. Downcore geochemical variations reflect natural ecosystem destabilizations occurring as early as the first half of the 20th century. These coincide with changes towards less radiogenic Pb-isotope values which persist towards the top of the core (206Pb/207Pb = 1.243 at core base ∼1843, to 206Pb/207Pb = 1.225 at ∼1978). We interpret the land-clearance for agricultural purposes on the Aberdare Range and documented early aviation activities as possible vectors of this early Pb-isotope excursion. The overlapping Pb-isotope signatures between sediment sources and anthropogenic contributions challenges a straightforward deconvolution of the two. Our conservative model calculations suggest, nevertheless, that an addition of up to ∼1.8 % Pb-gasoline influx to the total Pb flux, peaking in the 1980s is able to explain the Pb distribution trend. Homogeneous Zn-isotope compositions in sediments deposited until ∼1970s (δ66/64Zn = 0.216-0.225 ‰) do not follow major hydro-climatic events or anthropogenic forcing but likely reflect lake-specific natural cycling. Subsequent higher variations to both heavier (up to δ66/64Zn = 0.242 ± 0.005 ‰) and lighter (down to δ66/64Zn = 0.184 ± 0.003 ‰) Zn-isotope values are contemporaneous with intensification of large-scale horticultural industry in the catchment. Together with supporting indicators, the lighter Zn-isotope compositions in youngest analysed sediments (21st century) are attributable to increased biological productivity (algal blooms) and ongoing lake eutrophication. Our study demonstrates the applicability of the heavy metal isotope tool to reconstruct human influences on lake environments with complex geological settings such as the East African Rift System.

Traceability and dispersion of highly toxic soluble phases from historical mine tailings: insights from Pb isotope systematics.

Dispersion of potentially toxic elements associated with efflorescent crusts and mine tailings materials from historical mine sites threaten the environment and human health. Limited research has been done on traceability from historical mining sites in arid and semi-arid regions. Pb isotope systematics was applied to decipher the importance of identifying the mixing of lead sources involved in forming efflorescent salts and the repercussions on traceability. This research assessed mine waste (sulfide-rich and oxide-rich tailings material and efflorescent salts) and street dust from surrounding settlements at a historical mining site in northwestern Mexico, focusing on Pb isotope composition. The isotope data of tailings materials defined a trending line (R2 = 0.9); the sulfide-rich tailings materials and respective efflorescent salts yielded less radiogenic Pb composition, whereas the oxide-rich tailings and respective efflorescent salts yielded relatively more radiogenic compositions, similar to the geogenic component. The isotope composition of street dust suggests the dispersion of tailings materials into the surroundings. This investigation found that the variability of Pb isotope composition in tailings materials because of the geochemical heterogeneity, ranging from less radiogenic to more radiogenic, can add complexity during environmental assessments because the composition of oxidized materials and efflorescent salts can mask the geogenic component, potentially underestimating the influence on the environmental media.

Neutron activation of stable isotopes in soil and groundwater from a radionuclide production facility, South Africa.

The neutron activation of stable isotopes in environmental matrices, such as soil and groundwater, is a critical aspect of assessing the impact of radionuclide production facilities on the surrounding ecosystem. The envisioned Low-Energy Radioactive Ion Beams (LERIB) facility at the iThemba LABS, South Africa is anticipated to generate significant sources of ionising radiation. The study investigated the possible repercussions of neutron irradiation stemming from the facility, focusing on the activation of stable isotopic compositions in the environment. The investigation employed a combination of experimental and analytical techniques to characterize the neutron activation products in soil and groundwater samples collected from the vicinity. Samples were collected from designated areas for background radiological measurements and were irradiated with neutrons for a period of 1 h. The induced radioactivity measured by the High Purity Germanium detector included 24Na, 22Na, 54Mn, 52Mn, and 46Sc. The application of Darcy's law for groundwater velocity suggests that radionuclides in groundwater will migrate at an average flow velocity of 0.8 m/day. The isotopes with longer half-lives have count rates at background concentrations; therefore, environmental impacts on the site and surrounding communities might be minimal.

Assessment of groundwater hydrogeological processes, isotopic composition, and associated health risks of the Banaz (Usak) Basin, Turkey.

The study area covers the Banaz (Usak) basin located in the Aegean Region in the western part of Turkey. Metamorphic, sedimentary, ultramafic, and volcanic rocks are dominant in the basin. The groundwaters in the study area are used for domestic, irrigational, and industrial purposes. Hence, the groundwater chemistry and major geochemical processes in the region were determined. The dominance of major elements was of the order of Ca2+ > Mg2+ > Na+ > K+ and HCO3- > CO3- > Cl- > SO42-. Piper, Durov, Chadha, and Radial plots identified generally Ca2+-Mg2+-HCO3- type waters as the dominant types of water in this area. In terms of physical parameters in the basin, the waters are suitable for drinking. However, arsenic content in Yesilyurt and Corum settlements exceeds the limit values of drinking water standards. In addition, the ammonium value is high in the water sample in the Corum region. Isotope contents in water samples from 2008 to 2023 were evaluated in the study area. The waters in the basin are of meteoric origin according to their stable isotope content. Tritium content in the plain waters indicates recent recharge. Additionally, for children, As and U elements were identified as risky with oral intake and As with dermal contact.

Novel stable isotope concepts to track antibiotics in wetland systems.

Antibiotics, their transformation products, and the translocation of antibiotic-resistant genes in the environment pose significant health risks to humans, animals, and ecosystems, aligning with the One Health concept. Constructed wetlands hold substantial yet underutilized potential for treating wastewater from agricultural, domestic sewage, or contaminated effluents from wastewater treatment plants, with the goal of eliminating antibiotics. However, the comprehensive understanding of the distribution, persistence, and dissipation processes of antibiotics within constructed wetlands remains largely unexplored. In this context, we provide an overview of the current application of stable isotope analysis at natural abundance to antibiotics. We explore the opportunities of an advanced multiple stable isotope approach, where isotope concepts could be effectively applied to examine the fate of antibiotics in wetlands. The development of a conceptual framework to study antibiotics in wetlands using multi-element stable isotopes introduces a new paradigm, offering enhanced insights into the identification and quantification of natural attenuation of antibiotics within wetland systems. This perspective has the potential to inspire the general public, governmental bodies, and the broader research community, fostering an emphasis on the utilization of stable isotope analysis for studying antibiotics and other emerging micropollutants in wetland systems.

FREE: Enhanced Feature Representation for Isotopic Envelope Evaluation in Top-Down Mass Spectra Deconvolution.

The aim of deconvolution of top-down mass spectra is to recognize monoisotopic peaks from the experimental envelopes in raw mass spectra. So accurate assessment of similarity between theoretical and experimental envelopes is a critical step in mass spectra data deconvolution. Existing evaluation methods primarily rely on intensity differences and m/z similarity, potentially lacking a comprehensive assessment. To overcome this constraint and facilitate a comprehensive and refined assessment of the similarity between theoretical and experimental envelopes, there exists an imperative to systematically explore and identify increasingly efficacious features for assessing this correspondence. We present enhanced feature representation for isotopic envelope evaluation (FREE) that derives diverse feature representations, encapsulating fundamental physical attributes of envelopes, including peak intensity and envelope shape. We trained FREE and evaluated its performance on both the ovarian tumor (OT) (human OT cells) data set and zebrafish (ZF) (brain in mature female ZF) data set. Specifically, comparing the state-of-art method, FREE demonstrates higher performance in multiple evaluation metrics across both the OT and ZF data sets, with a particular emphasis on precision, and it demonstrates accurate predictions of a greater number of positive envelopes among the top-ranked envelopes based on their scores. Moreover, within a cross-species data set of ZF, FREE identified a higher number of proteoform-spectrum matches (PrSMs), increasing the count from 50,795 to 52,927 compared to EnvCNN, the amalgamation of FREE with TopFD also exhibits a commendable capacity to discern 117,883 fragment ions, thus surpassing the 97,554 fragment ions identified through the application of EnvCNN in conjunction with TopFD. To further validate the performance of FREE, we have tested 10 a cross-species top-down proteomes containing 36 subdata set from ProteomeXchange. The results reveal that, after deconvolution with TopFD + FREE, TopPIC identifies more PrSMs across these 10 data sets in both the first and second rounds of experiments. These findings underscore the robustness and generalization capabilities of the FREE approach in diverse proteomes.

Compost amendment in urban gardens: elemental and isotopic analysis of soils and vegetable tissues.

Urban horticulture poses a sustainable form of food production, fosters community engagement and mitigates the impacts of climate change on cities. Yet, it can also be tied to health challenges related to soil contamination. This work builds on a previous study conducted on eleven urban gardens in the city of Vienna, Austria. Following the findings of elevated Pb levels in some soil and plant samples within that project, the present study investigates the elemental composition of soil and plants from two affected gardens 1 year after compost amendment. Inductively coupled plasma mass spectrometry (ICP-MS) analysis of skin, pulp and seeds of tomato fruits revealed minor variations in elemental composition which are unlikely to have an impact on food safety. In turn, a tendency of contaminant accumulation in root tips and leaves of radishes was found. Washing of lettuce led to a significant reduction in the contents of potentially toxic elements such as Be, Al, V, Ni, Ga and Tl, underscoring the significance of washing garden products before consumption. Furthermore, compost amendments led to promising results, with reduced Zn, Cd and Pb levels in radish bulbs. Pb isotope ratios in soil and spinach leaf samples taken in the previous study were assessed by multi-collector (MC-) ICP-MS to trace Pb uptake from soils into food. A direct linkage between the Pb isotopic signatures in soil and those in spinach leaves was observed, underscoring their effectiveness as tracers of Pb sources in the environment.

How strongly does diet variation explain variation in isotope values of animal consumers?

Analysis of stable isotopes in consumers is used commonly to study their ecological and/or environmental niche. There is, however, considerable debate regarding how isotopic values relate to diet and how other sources of variation confound this link, which can undermine the utility. From the analysis of a simple, but general, model of isotopic incorporation in consumer organisms, we examine the relationship between isotopic variance among individuals, and diet variability within a consumer population. We show that variance in consumer isotope values is directly proportional to variation in diet (through Simpson indices), to the number of isotopically distinct food sources in the diet, and to the baseline variation within and among the isotope values of the food sources. Additionally, when considering temporal diet variation within a consumer we identify the interplay between diet turnover rates and tissue turnover rates that controls the sensitivity of stable isotopes to detect diet variation. Our work demonstrates that variation in the stable isotope values of consumers reflect variation in their diet. This relationship, however, can be confounded with other factors to the extent that they may mask the signal coming from diet. We show how simple quantitative corrections can recover a direct 1:1 correlation in some situations, and in others we can adjust our interpretation in light of the new understanding arising from our models. Our framework provides guidance for the design and analysis of empirical studies where the goal is to infer niche width from stable isotope data.

Introducing Isotòpia: A stable isotope database for Classical Antiquity.

We present Isotòpia, an open-access database compiling over 36,000 stable isotope measurements (δ13C, δ15N, δ18O, δ34S, 87Sr/86Sr, 206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb, 207Pb/206Pb, and 208Pb/206Pb) on human, animal, and plant bioarchaeological remains dating to Classical Antiquity (approximately 800 BCE - 500 CE). These were recovered from different European regions, particularly from the Mediterranean. Isotòpia provides a comprehensive characterisation of the isotopic data, encompassing various historical, archaeological, biological, and environmental variables. Isotòpia is a resource for meta-analytical research of past human activities and paleoenvironments. The database highlights data gaps in isotopic classical archaeology, such as the limited number of isotopic measurements available for plants and animals, limited number of studies on spatial mobility, and spatial heterogeneity of isotopic research. As such, we emphasise the necessity to address and fill these gaps in order to unlock the reuse potential of this database.

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Precipitation in the plum rain period accounts for 40%-50% of annual precipitation in the monsoon region. To clarify the temporal variability of the isotopic composition of precipitation during the plum rain period from event to interannual time scale and identify the influencing factors, we analyzed the isotopic composition of precipitation and its influencing factors in Nanjing from 2015 to 2022. By using the Hybrid Single-particle Lagran-gian Integrated Trajectory (HYSPLIT) model with specific humidity analysis, we investigated the water vapor source and influencing factors. The results showed that 1) the isotopic abundance of atmospheric precipitation was depleted in the summer and enriched in winter. dx was lower in summer and higher in winter. The isotopic abundance of precipitation from the plum rain was depleted compared to mean value of the whole-year. 2) There was no significant correlation between δ2H and δ18O of the plum rain (precipitation) with local meteorological factors. However, dx was lower in light rain, reflecting the effect of sub-cloud evaporation. The average dx was higher during plum rain period in years with more total plum rain precipitation. 3) The low-latitude South China Sea and the western Pacific Ocean source area provided water vapor for the plum rain. The shift of moisture source region led to abrupt changes in precipitation isotopes. Our results could provide data support for studies on precipitation isotopes in the monsoon region, as well as a reference point for further understanding the precipitation mechanism of the plum rain and stu-dying the seasonal variability of atmospheric circulation in the East Asian monsoon region.

Determination of contamination sources and geochemical reactions in groundwater of a mine area using Cu, Zn, and S-O isotopes.

To determine contamination sources and pathways, the use of multiple isotopes, including metal isotopes, can increase the reliability of environmental forensic techniques. This study differentiated contamination sources in groundwater of a mine area and elucidated geochemical processes using Cu, Zn, S-O, and O-H isotopes. Sulfate reduction and sulfide precipitation were elucidated using concentrations of dissolved sulfides, δ34SSO4, δ18OSO4, and δ66Zn. The overlying contaminated soil was possibly responsible for the contamination of groundwater at <5 mbgl, which was suggested by low δ65Cu values (0.419-1.120‰) reflecting those of soil (0.279-1.115‰). The existence of dissolved Cu as Cu(I) may prevent the increase in δ65Cu during leaching of contaminated soil in the sulfate-reducing environment. In contrast, the groundwater at >5 mbgl seemed to be highly affected by the contamination plume from the adit water, which was suggested by high SO42- concentrations (407-447 mg L-1) and δ65Cu (0.252-2.275‰) and δ66Zn (-0.105‰-0.362‰) values at a multilevel sampler approaching those of the adit seepages. Additionally, the O-H isotopic ratios were distinguished between <5 mbgl and >5 mbgl. Using δ65Cu and δ66Zn to support the determination of groundwater contamination sources may be encouraged, particularly where the isotopic signatures are distinct for each source.

Elevated lead mobility in sediments of a eutrophic drinking water reservoir during spring and summer seasons: Insights from isotopic signatures.

Lead (Pb) pollution in sediments remains a major concern for ecosystem quality due to the robust interaction at the sediment/water interface, particularly in shallow lakes. However, understanding the mechanism behind seasonal fluctuations in Pb mobility in these sediments is lacking. Here, the seasonal variability of Pb concentration and isotopic ratio were investigated in the uppermost sediments of a shallow eutrophic drinking lake located in southeast China. Results reveal a sharp increase in labile Pb concentration during autumn-winter period, reaching ∼ 3-fold higher levels than during the spring-summer seasons. Despite these fluctuations, there was a notable overlap in the Pb isotopic signatures within the labile fraction across four seasons, suggesting that anthropogenic sources are not responsible for the elevated labile Pb concentration in autumn-winter seasons. Instead, the abnormally elevated labile Pb concentration during autumn-winter was probably related to reduction dissolution of Fe/Mn oxides, while declined labile Pb concentration during spring-summer may be attributed to adsorption/precipitation of Fe/Mn oxides. These large seasonal changes imply the importance of considering seasonal effects when conducting sediment sampling. We further propose a solution that using Pb isotopic signatures within the labile fraction instead of the bulk sediment can better reflect the information of anthropogenic Pb sources.

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Nitrate pollution in groundwater has become a global concern. One of the most important issues in controlling the nitrate pollution of groundwater is to identify the pollution source quickly and accurately. In this review, we firstly summarized the isotopic background values of potential sources of nitrate pollution in groundwater in 17 provinces (cities, autonomous regions) and 29 study areas in China, which could provide the fundamental database for subsequent research. Secondly, we reviewed the research progress of nitrate isotopes combined with multiple tracers for tracing nitrate in groundwater, and discussed their applicable conditions, advantages, and disadvantages. We found that halides and microorganisms combined with nitrate isotopes could accurately trace the pollution sources of domestic sewage, excrement and agricultural activities. The combination of Δ17O and nitrate isotopes could effectively distinguish the source of atmospheric deposition of nitrate in groundwater. The combination of groundwater age and nitrate isotopes could further determine the time scale of nitrate pollution. In addition, we summarized the application cases and compared the characteristics of mass balance mixing model, IsoSource model, Bayesian isotope mixing model, and EMMTE model for quantitative identification of nitrate pollution in groundwater. For the complexity and concealment of groundwater pollution sources, the coupling of nitrate isotopes with other chemical and biological tracing methods, as well as the application of nitrate isotope quantitative models, are effective tools for reliably identifying groundwater nitrate sources and transformation processes.

Towards the compatibility of stable isotope data: review of related concepts, recent progress with reference materials and current challenges.

Comparing and combining stable isotope datasets from different laboratories and different years is essential for many research areas, such as isotope hydrology, greenhouse gas observations, food studies, isotope forensics, palaeo-reconstructions, etc. Data compatibility (i.e. the ability to combine data) is related to the data quality. The prerequisite for data comparability is data normalization to a common stable isotope scale (often referred to as calibration) based on reliable reference materials (RMs) with accurately assigned values and uncertainties. Still, that does not guarantee the data compatibility (mutual agreement). Albeit metrological concepts related to data compatibility and measurement uncertainty have been developed and applied to analytical chemistry in general, these concepts have not yet been fully applied to stable isotope research. This can affect daily calibrations, analytical data and, therefore, data compatibility. In addition, IRMS users often prepare different laboratory standards themselves. Thereafter, users should then understand the contemporary concepts used for assigning RM value and uncertainty, as well as the limitations and potential problems associated with RMs. The history of RMs, preparation reports and also some problems in the past provide lessons to be learned. These include the δ13C drift of LSVEC (the second anchor on the δ13C scale before 2017), revisions to the value assignment principles, the introduction of replacements for LSVEC, related disputes and the potential underestimation of uncertainties for secondary RMs. The review describes metrological concepts related to isotopic scales, RMs and calibration hierarchies and data compatibility. The main RMs and their uncertainties are reviewed through the lens of metrology concepts. Additional focus is given to the VPDB scale for δ13C and issues of scale discontinuity, which can significantly reduce data compatibility in δ13C. The given examples of value and uncertainty assignment for RMs should be viewed as an example of value and uncertainty calculation in daily practice.

Characterization of the inhalable fraction (< 10 µm) of soil from highly urbanized and industrial environments: magnetic measurements, bioaccessibility, Pb isotopes and health risk assessment.

Soil in urban and industrial areas is one of the main sinks of pollutants. It is well known that there is a strong link between metal(loid)s bioaccessibility by inhalation pathway and human health. The critical size fraction is < 10 µm (inhalable fraction) since these particles can approach to the tracheobronchial region. Here, soil samples (< 10 µm) from a highly urbanized area and an industrialized city were characterized by combining magnetic measurements, bioaccessibility of metal(loids) and Pb isotope analyses. Thermomagnetic analysis indicated that the main magnetic mineral is impure magnetite. In vitro inhalation analysis showed that Cd, Mn, Pb and Zn were the elements with the highest bioaccessibility rates (%) for both settings. Anthropogenic sources that are responsible for Pb accumulation in < 10 µm fraction are traffic emissions for the highly urbanized environment, and Pb related to steel emissions and coal combustion in cement plant for the industrial setting. We did not establish differences in the Pb isotope composition between pseudo-total and bioaccessible Pb. The health risk assessment via the inhalation pathway showed limited non-carcinogenic risks for adults and children. The calculated risks based on pseudo-total and lung bioaccessible concentrations were identical for the two areas of contrasting anthropogenic pressures. Carcinogenic risks were under the threshold levels (CR < 10-4), with Ni being the dominant contributor to risk. This research contributes valuable insights into the lung bioaccessibility of metal(loids) in urban and industrial soils, incorporating advanced analytical techniques and health risk assessments for a comprehensive understanding.

Using stable isotopes to inform water resource management in forested and agricultural ecosystems.

Present and future climatic trends are expected to markedly alter water fluxes and stores in the hydrologic cycle. In addition, water demand continues to grow due to increased human use and a growing population. Sustainably managing water resources requires a thorough understanding of water storage and flow in natural, agricultural, and urban ecosystems. Measurements of stable isotopes of water (hydrogen and oxygen) in the water cycle (atmosphere, soils, plants, surface water, and groundwater) can provide information on the transport pathways, sourcing, dynamics, ages, and storage pools of water that is difficult to obtain with other techniques. However, the potential of these techniques for practical questions has not been fully exploited yet. Here, we outline the benefits and limitations of potential applications of stable isotope methods useful to water managers, farmers, and other stakeholders. We also describe several case studies demonstrating how stable isotopes of water can support water management decision-making. Finally, we propose a workflow that guides users through a sequence of decisions required to apply stable isotope methods to examples of water management issues. We call for ongoing dialogue and a stronger connection between water management stakeholders and water stable isotope practitioners to identify the most pressing issues and develop best-practice guidelines to apply these techniques.

Disaster victim identification: Stable isotope analysis and the identification of unknown decedents.

Within the complex world of disaster victim identification, or DVI, forensic science practitioners use a variety of investigative techniques to work toward a common goal: identification of the decedents, bringing closure to the affected communities. Identification is a complex undertaking; the event (disaster) also can be extraordinarily complex, as it may be an acute event, or one that spans months or years. Compounding this time issue, remains may be heavily fragmented, dispersed, commingled, or otherwise disrupted by either the perpetrators or the disaster itself. To help solve these complexities, we explore the use of stable isotope analysis (SIA) in DVI events. SIA can be used with a variety of body tissues (hair, nail, bone, and teeth), and each represents different time depths in a decedent's life. Bone collagen and tooth enamel carbonate are useful to reconstruct an individual's diet and source water intakes, respectively, leading to likely population or geographic origin determinations. Additionally, the carbon and nitrogen isotopic signatures of bone collagen have calculated intraperson ranges. These facts allow investigators to determine likely origin of remains using isotopic data and can be used to link skeletal elements (to an individual), or perhaps more importantly, show that remains are not linked. Application of SIA can thus speed remains identification by eliminating individuals from short lists for identification, linking or decoupling remains, and reducing the need for some DNA testing. These strategies and hypothesis tests should commence early in the DVI process to achieve maximum effectiveness.

Thallium in Technosols from Allchar (North Macedonia): Isotopic and speciation insights.

Allchar (North Macedonia) mining area is known for anomalous background Tl concentrations. In this study, we combine accurate detection of Tl stable isotope ratios with data on mineralogy/speciation and chemical extraction of Tl in Tl-contaminated Technosol profiles. We demonstrate that Tl in the studied soils varies significantly in both concentration (500 mg/kg-18 g/kg) and isotopic composition (-1.6 and +3.2 of ε205Tl, a ∼0.5‰ spread), which is due to changes in the phase chemistry and/or mineralogy of Tl. Moreover, the observed 205Tl/203Tl ratios do not reflect the extent to which individual soils undergo Tl isotopic fractionation during mineral weathering and soil formation. Clearly, they reflect the initial isotopic signal(s) of the primary ore or ore minerals, and thus, the general history or type of their genesis. As the Tl carriers, various types of Tl-Me-arsenates, mixtures of jarosite and dorallcharite and minor Mn-oxides predominated. We revealed intense adsorption of Tl by the identified Mn-oxides (≤6.7 at.%). It is hypothesized that these phases are of key importance in the fractionation of Tl isotopes, meaning at this type of secondary oxide-soil solution interface. However, model studies involving primary/secondary components (sulfides, sulfates, oxides and arsenates) are required to understand the mechanisms that may lead to post-depositional Tl isotopic redistribution in soils, as well as Tl isotope systematics in mining wastes in general.

Spatiotemporal and multi-isotope assessment of metal sedimentation in the Great Lakes.

This study investigates spatiotemporal dynamics in metal sedimentation in the North American Great Lakes and their underlying biogeochemical controls. Bulk geochemical and isotope analyses of n = 72 surface and core sediment samples show that metal (Cu, Zn, Pb) concentrations and their isotopic compositions vary spatially across oligotrophic to mesotrophic settings, with intra-lake heterogeneity being similar or higher than inter-lake (basin-scale) variability. Concentrations of Cu, Zn, and Pb in sediments from Lake Huron and Lake Erie vary from 5 to 73 mg/kg, 18-580 mg/kg, and 5-168 mg/kg, respectively, but metal enrichment factors were small (<2) across the surface- and core sediments. The isotopic signatures of surface sediment Cu (δ65Cu between -1.19‰ and +0.96‰), Zn (δ66Zn between -0.09‰ and +0.41‰) and Pb (206/207Pb from 1.200 to 1.263) indicate predominantly lithogenic metal sourcing. In addition, temporal trends in sediment cores from Lake Huron and Lake Erie show uniform metal concentrations, minor enrichment, and Zn and Pb isotopic signatures suggestive of negligible in-lake biogeochemical fractionation. In contrast, Cu isotopic signatures and correlation to chlorophyll and macronutrient levels suggest more differentiation from source variability and/or redox-dependent fractionation, likely related to biological scavenging. Our results are used to derive baseline metal sedimentation fluxes and will help optimize water quality management and strategies for reducing metal loads and enrichment in the Great Lakes and beyond.