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 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.

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.

Excessive enrichment of fluoride threatens ecological stability and human health. The high-fluoride groundwater in the Chagan Lake area has existed for a long time. With the land consolidation and irrigation area construction, the distribution and migration process of fluoride have changed. It is urgent to explore the evolution of fluoride under the dual effects of nature and human. Based on 107 groundwater samples collected in different land use periods, hydrogeochemistry and isotope methods were combined to explore the evolution characteristics and hydrogeochemical processes of fluoride in typical high-fluoride background area and elucidate the impact of anthropogenic activities on fluoride migration. The results indicate that large areas of paddy fields are developed from saline-alkali land, and its area has increased by nearly 30%. The proportion of high-fluoride groundwater (>2 mg/L) has increased by nearly 10%, mainly distributed in the new irrigation area. Hydrogeochemical processes such as dissolution of fluorine-containing minerals, precipitation of carbonate minerals and exchange of Na⁺, Ca²⁺ on the water-soil interface control the enrichment of fluoride. The groundwater d-excess has no obvious change with the increase of TDS, and human activities are one of the reasons for the increase of fluoride. The concentration of fluoride is diluted due to years of diversion irrigation in old irrigation area, whereas the enrichment of δ²H, δ¹⁸O and Cl⁻ in new irrigation area indicates that the vertical infiltration of washing alkali and irrigation water brought fluoride and other salts to groundwater. Fertilizer and wastewater discharges also contribute to the accumulation of fluoride, manifesting as co-increasing nitrate and chloride salts. The results of this study provide a new insight into fluoride migration under anthropogenic disturbance in high-fluoride background areas.

We report for the first time the Os isotopic composition of tree bark samples from a steel town. Osmium concentrations and ¹⁸⁷Os/¹⁸⁸Os isotopic ratios of ashed bark samples range from 1.40 to 24 ppt and 0.70 to 1.54, respectively, with the lowest ¹⁸⁷Os/¹⁸⁸Os recorded in samples close to the steel plant. Compositional variations in the bark samples can be explained by mixing between at least two sources with different Os isotopic signatures: a radiogenic source consistent with crust-derived materials and a relatively less radiogenic source consistent with mantle-derived chromite. The exact origin of the radiogenic Os component cannot be constrained, as background signatures and crustal materials used in the steel industry (e.g., coal and iron ore) likely have overlapping radiogenic signatures. Cr shows a similar distribution pattern to Os, indicating that both metals have a common origin, which provides further evidence that the Os budget in the bark samples is controlled primarily by the chromite used in the steel manufacturing. This study shows that Os isotopes are an effective tool for tracing steel production-related emissions.

The installation rate of denitrification devices is accelerating in Chinese urban boilers. Previous studies on pulverized coal-fired boilers without denitrification devices showed that combustion products containing mainly oxidized mercury (Hg) preferably enriched lighter Hg isotopes than feed coals. However, the magnitude of this enrichment becomes less pronounced if denitrification devices are installed. The underlying Hg isotope fractionation mechanisms are still unclear. In this study, three types of urban boilers (two pulverized coal-fired boilers, one circulating fluidized bed boiler and one municipal waste incinerator boiler) all installed with denitrification devices were measured for Hg isotope compositions of their feed fuels and corresponding combustion products. We observed little mass independent fractionation but very significant mass dependent fractionation (MDF) between feed fuels and combustion products. The fly ash and desulfurization products both enriched heavier Hg isotopes than feed coals in three coal-fired boilers, and the enrichment of heavy Hg isotopes increased with sequential removal of combustion products in all boilers. Different from previously suggested kinetic MDF for gaseous Hg⁰(g)→Hgᴵᴵ(g) and gaseous Hgᴵᴵ(g)→particulate Hgᴵᴵ(p) in coal combustion flue gases, we propose an equilibrium MDF for Hg⁰(g)↔Hgᴵᴵ(g) followed by a kinetic MDF for Hgᴵᴵ(g)→Hgᴵᴵ(p). This equilibrium MDF most likely occurs during Hg⁰(g) oxidation in denitrification devices, which enriches heavy Hg isotopes in oxidized products (Hgᴵᴵ(g) and Hgᴵᴵ(p)) that are then sequestrated in fly ash and desulfurization products. The paradigm shift of MDF in boilers with denitrification devices was further verified by parallel Hg isotope measurement in urban atmosphere particulates. Our study clearly demonstrates that modern coal-fired boilers with denitrification devices have a quite different MDF compared to traditional boilers without denitrification devices. This has important implications for estimating isotope signatures of urban boiler Hg emissions, and for isotope tracing of anthropogenic Hg emissions.

Biochar may variably impact nitrogen (N) transformation and N-cycle-related microbial activities. Yet the mechanism of biochar amendment on nitrous oxide (N₂O) emissions from agricultural ecosystems remains unclear. Based on a 6-year long-term biochar amendment experiment, we applied a dual isotope (¹⁵N–¹⁸O) labeling technique with tracing transcriptional genes to differentiate the contribution of nitrifier nitrification (NN), nitrifier denitrification (ND), nitrification-coupled denitrification (NCD) and heterotrophic denitrification (HD) pathway to N₂O production. Then the field experiment provided quantitative data on dynamic N₂O emissions, soil mineral N and key functional marker gene abundances during the wheat growing season. By using ¹⁵N–¹⁸O isotope, biochar decreased N₂O emission derived from ND (by 45–94%), HD (by 35–46%) and NCD (by 30–64%) compared to the values under N application. Biochar increased the relative contribution of NN to total N₂O production as evidenced by the increase in ammonia-oxidizing bacteria, but did not influence the cumulative NN-derived N₂O. The field experiment found that the majority of the N₂O emissions peaked following fertilization, in parallel with soil NH₄⁺ and nitrite dynamics. Soil N₂O emissions during the wheat growing stage were effectively decreased (by 38–48%) by biochar amendment. Based on the correlation analyses and random forest analysis in both microcosm and field experiments, the decrease in nitrite concentration (by 62–65%) and increase in N₂O consumption were mainly responsible for net N₂O mitigation, as evidenced by the decrease in the ratios of nitrite reductase genes/transcripts (nirS, nirK and fungal nirK) and N₂O reductase gene/transcripts (nosZI and nosZII). Based on the extrapolation from microcosm to field, biochar significantly mitigated N₂O emissions by weakening the ND processes, since NCD and HD contributed little during the N₂O emission “peaks” following urea fertilization. Therefore, emphasis should be put on the ND process and nitrite accumulation during N₂O emission peaks and extrapolated to all agroecosystems.

The present study aims to explore the bioaccumulation and biotic transformations of inorganic (iHg) and monomethyl mercury (MMHg) by natural pico-nanoplankton community from eutrophic lake Soppen, Switzerland. Pico-nanoplankton encompass mainly bacterioplankton, mycoplankton and phytoplankton groups with size between 0.2 and 20 μm. Species-specific enriched isotope mixture of ¹⁹⁹iHg and ²⁰¹MMHg was used to explore the accumulation, the subcellular distribution and transformations occurring in natural pico-nanoplankton sampled at 2 different depths (6.6 m and 8.3 m). Cyanobacteria, diatoms, cryptophyta, green algae and heterotrophic microorganisms were identified as the major groups of pico-nanoplankton with diatoms prevailing at deeper samples. Results showed that pico-nanoplankton accumulated both iHg and MMHg preferentially in the cell membrane/organelles, despite observed losses. The ratios between the iHg and MMHg concentrations measured in the membrane/organelles and cytosol were comparable for iHg and MMHg. Pico-nanoplankton demethylate added ²⁰¹MMHg (~4 and 12% per day depending on cellular compartment), although the involved pathways are to further explore. Comparison of the concentrations of ²⁰¹iHg formed from ²⁰¹MMHg demethylation in whole system, medium and whole cells showed that 82% of the demethylation was biologically mediated by pico-nanoplankton. No significant methylation of iHg by pico-nanoplankton was observed. The accumulation of iHg and MMHg and the percentage of demethylated MMHg correlated positively with the relative abundance of diatoms and heterotrophic microorganisms in the pico-nanoplankton, the concentrations of TN, Mg²⁺, NO₃⁻, NO₂⁻, NH₄⁺ and negatively with the concentrations of DOC, K⁺, Na⁺, Ca²⁺, SO₄²⁻. Taken together the results of the present field study confirm the role of pico-nanoplankton in Hg bioaccumulation and demethylation, however further research is needed to better understand the underlying mechanisms and interconnection between heterotrophic and autotrophic microorganisms.