The most prominent source of Cu contamination in soils is metal mining and processing, partly since the Middle Age. However, coal mining and combustion can also cause (some) Cu contamination. We studied the distribution of Cu concentrations and isotope ratios in soils of the Huaibei coal mining area. The contribution of the coal mining and combustion to total Cu concentrations in soil was determined with a two-end-member mixing model based on the distinct δ⁶⁵Cu values of the Cu emitted from coal mining and combustion and in native soil. The mean Cu concentration of 75 mg kg⁻¹ exceeded the local soil background value (round to 22.13 mg kg⁻¹). The similar δ⁶⁵Cu value of grass near the coal mining and combustion operation as in gangue and flying ash indicated a superficial Cu contamination. Mining input was the dominant source of Cu in the contaminated soils, contributing up to 95% and on average 72% of the total Cu in the topsoils. The mining-derived Cu was leached to a depth of 65 cm, where still 29% of the Cu could be attributed to the mining emissions. Grasses showed lower δ⁶⁵Cu values than the topsoils, because of the preferential uptake of light Cu isotopes. However, the Δ⁶⁵Cugᵣₐₛₛ₋ₛₒᵢₗ was lower in the contaminated than the uncontaminated area because of superficial adsorption of isotopically heavy Cu from the mining emissions. Overall, in this study the distinct δ⁶⁵Cu values of the mining-derived Cu emissions and the native soil allowed for the quantification of the mining-derived Cu and had already reached the subsoil and contaminated the grass by superficial adsorption in only 60 years of mining operation.

The Nanfei River was one of dominant inflowing rivers of the fifth largest freshwater Chaohu Lake in China, which had been subjected to increasing nutrients and contaminants from population expansion, rapid industrialization and agricultural intensification in recent decades. In present study, surface sediment from the Nanfei River was collected to investigate the anthropogenic impact on distribution and bioavailability of heavy metals. Possible Cd sources along the river were constrained by using Cd isotope signatures and labile concentrations of heavy metals in sediment were determined through the DGT technique for risk assessment. Results showed that Cd in river sediment showed greatest enrichment (EF 0.8–9.4), indicating massive pollution from anthropogenic activities. Among the various possible Cd source materials, urban road dust, industrial soil and chicken manure, displayed higher Cd abundance and enrichment that might contribute to Cd accumulation in river sediment. Cadmium isotopic composition in river sediment was ranged from −0.21 ± 0.01‰ to 0.13 ± 0.03‰, whereas yielded relative variation from −0.31 ± 0.02‰ to 0.23 ± 0.01‰ in source materials. Accordingly, Cd sources along the river were constrained, i.e. traffic and industrial activities in the upper and middle reaches whereas agricultural activities in the lower reaches. Furthermore, the evaluation on ecological risk of heavy metals in sediment on basis of SQGs and DGT-labile concentrations demonstrated that Pb and Zn might pose higher risk on aquatic species. The present study confirmed that Cd isotopes were promising source tracer in environmental studies.

The North Sea and its coastal zones are heavily impacted by anthropogenic activities, which has resulted in significant chemical pollution ever since the beginning of the industrialization in Europe during the 19th century. In order to assess the chemical Anthropocene, natural archives, such as sediment cores, can serve as a valuable data source to reconstruct historical emission trends and to verify the effectiveness of changing environmental legislation. In this study, we investigated 90 contaminants covering inorganic and organic pollutant groups analyzed in a set of sediment cores taken in the North Seas' main sedimentation area (Skagerrak). We thereby develop a chemical pollution fingerprint that records the constant input of pollutants over time and illustrates their continued great relevance for the present. Additionally, samples were radiometrically dated and PAH and PCB levels in porewater were determined using equilibrium passive sampling. Furthermore, we elucidated the origin of lead (Pb) contamination utilizing non-traditional stable isotopic analysis. Our results reveal three main findings: 1. for all organic contaminant groups covered (PAHs, OCPs, PCBs, PBDEs and PFASs) as well as the elements lead (Pb) and titanium (Ti), determined concentrations decreased towards more recent deposited sediment. These decreasing trends could be linked to the time of introductions of restrictions and bans and therefor our results confirm, amongst possible other factors, the effectiveness of environmental legislation by revealing a successive change in contamination levels over the decades. 2. concentration trends for ΣPAH and ΣPCB measured in porewater correspond well with the ones found in sediment which suggests that this method can be a useful expansion to traditional bulk sediment analysis to determine the biologically available pollutant fraction. 3. Arsenic (As) concentrations were higher in younger sediment layers, potentially caused by emissions of corroded warfare material disposed in the study area after WW II.

Black carbon (BC) aerosol negatively affects air quality and contributes to climate warming globally. However, little is known about the relative contributions of different source control measures to BC reduction owing to the lack of powerful source-diagnostic tools. We combine the fingerprints of dual-carbon isotope using an optimized Bayesian Markov chain Monte Carlo (MCMC) scheme and for the first time to study the key sources of BC in megacity Guangzhou of the Pearl River Delta (PRD) region, China in 2018 autumn season. The MCMC model-derived source apportionment of BC shows that the dominant contributor is petroleum combustion (39%), followed by coal combustion (34%) and biomass burning (27%). It should be noted that the BC source pattern is highly sensitive to the variations of air masses transported with an enhanced contribution of fossil source from the eastern area, suggesting the important impact of regional atmospheric transportation on the BC source profile in the PRD region. Also, we further found that fossil fuel combustion BC contributed 84% to the total BC reduction during 2013–2018. The response of PM₂.₅ concentration to the ¹⁴C-derived BC source apportionment is successfully fitted (r = 0.90) and the results predicted that it would take ∼6 years to reach the WHO PM₂.₅ guideline value (10 μg m⁻³) for the PRD region if the emission control measures keep same as they are at present. Taken together, our findings suggest that dual-carbon isotope is a powerful tool in constraining the source apportionment of BC for the evaluations of air pollution control and carbon emission measures.

To provide insight into how climate-driven diet shifts may impact contaminant exposures of Arctic species, we compared feeding ecology and contaminant concentrations in ringed seals (Pusa hispida) from two Canadian sub-Arctic (Nain at 56.5°N, Arviat at 61.1°N) and two Arctic sites (Sachs Harbour at 72.0 °N, Resolute Bay at 74.7 °N). In the sub-Arctic, empirical evidence of changing prey fish communities has been documented, while less community change has been reported in the Arctic to date, suggesting current sub-Arctic conditions may be a harbinger of future Arctic conditions. Here, Indigenous partners collected tissues from subsistence-harvested ringed seals in 2018. Blubber fatty acids (FAs) and muscle stable isotopes (δ¹⁵N, δ¹³C) indicated dietary patterns, while measured contaminants included heavy metals (e.g., total mercury (THg)), legacy persistent organic pollutants (e.g., dichlorodiphenyltrichloroethanes (DDTs)), polybrominated diphenyl ethers (PBDEs), and per-/polyfluoroalkyl substances (PFASs). FA signatures are distinct between sub-Arctic and Resolute Bay seals, likely related to higher consumption of southern prey species including capelin (Mallotus villosus) in the sub-Arctic but on-going feeding on Arctic species in Resolute Bay. Sachs Harbour ringed seals show FA overlap with all locations, possibly consuming both southern and endemic Arctic species. Negative δ¹³C estimates for PFAS models suggest that more pelagic, sub-Arctic type prey (e.g., capelin) increases PFAS concentrations, whereas the reverse occurs for, e.g., THg, ΣPBDE, and ΣDDT. Inconsistent directionality of δ¹⁵N estimates in the models likely reflects baseline isotopic variation not trophic position differences. Adjusting for the influence of diet suggests that if Arctic ringed seal diets become more like sub-Arctic seals due to climate change, diet-driven increases may occur for newer contaminants like PFASs, but not for more legacy contaminants. Nonetheless, temporal trends studies are still needed, as are investigations into the potential confounding influence of baseline isotope variation in spatial studies of contaminants in Arctic biota.

Pyrite oxidation and sedimentary sulfate dissolution are the primary components of riverine sulfate (SO₄²⁻) and are predominant in global SO₄²⁻ flux into the ocean. However, the proportions of anthropogenic SO₄²⁻ inputs have been unclear, and their tempo-spatial variations due to human activities have been unknown. Thus, field work was conducted in a spatially heterogeneous human-affected area of the Yihe River Basin (YRB) during a wet year (2010) and drought years (2017/2018). Dual sulfate isotopes (δ³⁴S–SO₄²⁻ and δ¹⁸O–SO₄²⁻) and Bayesian isotope mixing models were used to calculate the variable anthropogenic SO₄²⁻ inputs and elucidate their temporal impacts on riverine SO₄²⁻ flux. The results of the mixing models indicated acid mine drainage (AMD) contributions increased from 56.1% to 83.1% of upstream sulfate and slightly decreased from 46.3% to 44.0% of midstream sulfate in 2010 and 2017/2018, respectively, in the Yihe River Basin. The higher upstream contribution was due to extensive metal-sulfide-bearing mine drainage. Sewage-derived SO₄²⁻ and fertilizer-derived SO₄²⁻ inputs in the lower reaches had dramatically altered SO₄²⁻ concentrations and δ³⁴S–SO₄²⁻ and δ¹⁸O–SO₄²⁻ values. Due to climate change, the water flow discharge decreased by about 70% between 2010 and 2017/2018, but the riverine sulfate flux was reduced by only about 58%. The non-proportional increases in anthropogenic sulfate inputs led to decreases in the flow-weighted average values of δ³⁴S–SO₄²⁻ and δ¹⁸O–SO₄²⁻ from 10.3‰ to 9.9‰ and from 6.1‰ to 4.4‰, respectively. These outcomes confirm that anthropogenic SO₄²⁻ inputs from acid mine drainage (AMD) have increased, but sewage effluents SO₄²⁻ inputs have decreased.

In arid inland irrigated areas, the role of human activities on fluoride enrichment in groundwater is not fully understood. There is an extremely arid climate, high-intensity irrigation, and severe soil salinization in the Hotan Oasis within the Tarim Basin, Northwestern China. In this study, hydrogeochemistry and environmental isotope methods were combined to explore the distribution characteristics and controlling processes of fluoride enrichment in groundwater. The F⁻ concentration in groundwater had a range of 1.12–9.4 mg/L. F⁻ concentrations of all the groundwater samples were higher than 1.0 mg/L (Chinese Standards for Drinking Water Quality), and about 89% were higher than 1.5 mg/L (WHO Guidelines for Drinking Water Quality). High fluoride groundwater was mainly distributed downstream of the river and in the middle of the interfluvial zone. Vertically, the fluoride concentration was higher when the sampling depth was less than 15 m. There was a significant positive correlation between F⁻ concentration and salinity in groundwater. F⁻ in groundwater was mainly derived from river water fluoride, which could be imported to groundwater with infiltration of rivers and irrigation canals as well as irrigation return flow. Anthropogenic inputs may be partly responsible for fluoride enrichment in groundwater. Fluoride accumulated in the vadose zone by strong evapotranspiration and then leached into groundwater with irrigation return flow was the main mechanism of F⁻ enrichment in groundwater in the study area. This work is a clear example of how human activities together with natural processes can affect the chemical quality of groundwater, which is essential to safeguard the sustainable management of water and soil resources inland arid oasis areas.

Nitrate pollution in oxygenated karst aquifers is common due to nitrification and anthropogenic inputs. However, the shift of nitrogen sources influenced by enhanced rural tourism activities and land use changes are not well understood. In this study, hydrochemistry and dual nitrate isotopes of water samples from a rural karst basin in Chongqing, southwestern China were employed to investigate the nitrate fate and its decadal change during the periods from 2007–2008 and 2017–2019. The results showed that δ¹⁵N–NO₃ and δ¹⁸O–NO₃ values at the groundwater basin resurgence averaged 9 ± 3.4‰ and 2.5 ± 3.4‰, respectively, with a mean NO₃⁻ concentration of 19.7 ± 5.4 mg/L in 2017–2019, clearly exceeding natural background levels. The dual isotope results suggested that nitrification occurred at the sampled sites. From 2007–2008 to 2017–2019, the mean δ¹⁵N–NO₃ values from the primary sink point and the resurgence of the underground river water samples increased from −0.2 ± 2.1 to 11.2 ± 4.8‰, 4.2 ± 0.9 to 9.0 ± 3.4‰, respectively. A Bayesian mixing model in R (MixSIAR) based on the isotopes revealed that soil organic nitrogen, and manure and sewage proportions for the groundwater increased by 34% and 23%, respectively, while chemical fertilizer and atmospheric precipitation proportions decreased by 32% and 25%, respectively. These decadal changes resulted from reforestation practices and enhanced rural tourism activities in the basin, which were evidenced by the change of land use patterns. The elevated nitrogen load from the rapid development of rural tourism is likely to increase this contamination in the near future if the infrastructure cannot meet the demands. The results from this study could contribute to minimizing environmental health risks in drinking water when rural tourism activities are increasing.

The contamination status of heavy metals in urban environment changes frequently with the industrial structure adjustment, energy conservation and emission reduction and thus requires timely investigation. Based on enrichment factor, multivariate statistical analysis and isotope fingerprinting, we assessed comprehensively the inputs and sources of heavy metals in different samples from an urban area that was less impacted by leaded gasoline exhaust. The road dust contained relatively high levels of Cr, Pb and Zn (with enrichment factor >2) that originated from both exhaust and non-exhaust traffic emissions, while the moss plants could accumulate high levels of Pb and Zn from the deposition of traffic exhaust emission. This suggest that the traffic emission is still an important source of metals in the urban area although gasoline is currently lead free. On the contrary, the occurrences of metals in the urban soils were controlled by natural sources and non-traffic anthropogenic emission. These findings revealed that different samples would receive different inputs of metals from different sources in the urban area, and the responsiveness and sensitiveness of these urban samples to metal inputs can be ranked as moss ≥ dust > soil. Taken together, our results suggested that in order to avoid generalizing and get detail source information, multi-samples and multi-measures must be adopted in the assessment of integrated urban environmental quality.

Iron (Fe) is an essential nutrient for living organisms and Fe deficiency is a worldwide problem for the health of both rice and humans. Zinc (Zn) contamination in agricultural soils is frequently observed. Here, we studied Fe isotope compositions and transcript levels of Fe transporter genes in rice growing in nutrient solutions having a range of Zn concentrations. Our results show Zn stress reduces Fe uptake by rice and drives its δ⁵⁶Fe value to that of the nutrient solution. These observations can be explained by the weakened Fe(II) uptake through Strategy I but enhanced Fe(III) uptake through Strategy II due to the competition between Zn and Fe(II) combining with OsIRT1 (Fe(II) transporter) in root, which is supported by the downregulated expression of OsIRT1 and upregulated expression of OsYSL15 (Fe(III) transporter). Using a mass balance box model, we also show excess Zn reduces Fe(II) translocation in phloem and its remobilization from senescent leaf, indicating a competition of binding sites on nicotianamine between Zn and Fe(II). This study provides direct evidence that how Zn regulates Fe uptake and translocation in rice and is of practical significance to design strategies to treat Fe deficiency in rice grown in Zn-contaminated soils.