Large quantities of lead/zinc (Pb/Zn) mine tailings were deposited at tailings impoundments without proper management, which have posed considerable risks to the local ecosystem and residents in mining areas worldwide. Therefore, the geochemical behaviors of potentially toxic elements (PTEs) in tailings were in–depth investigated in this study by a coupled use of batch kinetic tests, statistical analysis and mineralogical characterization. The results indicated that among these studied PTEs, Cd concentration fluctuated within a wide range of 0.83–6.91 mg/kg, and showed the highest spatial heterogeneity. The mean Cd concentrations generally increased with depth. Cd were mainly partitioned in the exchangeable and carbonate fractions. The release potential of PTEs from tailings was ranged as: Cd > Mn > Zn > Pb > As, Cd > Pb > Zn > Mn > As and Cd > Pb > Mn > Zn > As, respectively, under the assumed environmental scenarios, i.e. acid rain, vegetation restoration, human gastrointestinal digestion. The results from mineralogical characterization indicated that quartz, sericite, calcite and pyrite were typical minerals, cumulatively accounting for over 80% of the tailings. Sulfides (arsenopyrite, galena, and sphalerite), carbonates (calcite, dolomite, cerussite and kutnahorite), oxides (limonite) were identified as the most relevant PTEs–bearing phases, which significantly contributed to PTEs release from tailings. A combined result of statistical, geochemical and mineralogical approaches would be provided valuable information for the alteration characteristics and contaminant release of Pb/Zn mine tailings.

The alkaline mineral amendment is a practical means of alleviating Cd concentration in rice grain (CdR) in the short-term; however, the long-term remediation effect of mineral amendment on the CdR and the eco-environmental controls remains unknown. Here a mineral (Si–Ca–Mg) amendment, calcined primarily from molybdenum tailings and dolomite, was applied biannually over 6 years (12 seasons) to acidic and moderately Cd-contaminated double-rice cropping ecosystems. This study investigated the inter-annual variation of Cd in the rice-soil ecosystem and the eco-environmental controls in subtropical rice ecosystems. CdR was reduced by 50%–86% following mineral amendment. The within-year reduction in CdR was similar between early rice (50%–86%, mean of 68%) and late rice (68%–85%, mean of 74%), leading to CdR in all early rice and in 83% of late rice samples below the upper limit (0.2 mg kg⁻¹) of the China National Food Safety Standards. In contrast, the inter-annual reduction in CdR was moderately variable, showing a greater CdR reduction in the later 3 years (73%–86%) than in the former 3 years (54%–79%). Three years continuous mineral amendment was required to guarantee the safety rice production. The concentrations of DTPA-extractable and exchangeable Cd fractions in soil were reduced, while the concentration of oxides-bound Cd was increased. In addition, the soil pH, concentrations of Olsen-P and exchangeable Ca and Mg were elevated. These imply a lower apparent phytoavailability of Cd in the soil following mineral amendment. An empirical model of the 3-variable using soil DTPA-Cd, soil Olsen-P, and a climatic factor (precipitation) effectively predicted temporal changes in CdR. Our study demonstrates that Cd phytoavailability in soil (indexed by DTPA-extractable Cd) and climatic factors (e.g., temperature and precipitation) may directly/indirectly control the inter-annual reduction in CdR following mineral amendment in slightly and moderately Cd-contaminated paddy ecosystems.

Groundwater chemistry can be affected by and related to earthquakes, thus it is crucial to understand the hydrochemical changes and associated processes caused by earthquakes for post-seismic groundwater utilization. Here we reported the major ion concentrations changes of the Ganze Spring in response to the May 30, 2014 Ms 6.1 Yingjiang earthquake, southwest China based on the daily time series (from 1st January 2012 to 20th July 2014) of Ca²⁺, Mg²⁺ and HCO₃⁻ concentrations, as well as data of bulk strain and Peak Ground Velocity (PGV) recorded at a nearby station. The results showed that the entire hydrochemical response process can be divided into two stages after the earthquake occurred: 1). decline stage which was characterized by an increasingly decline of the three ion concentrations, indicating a gradually significant dilution effect. At first, the relationship of molar concentrations of ions showed no obvious changes; but later as the rate of decrease in ion concentrations increased, the relationship between Ca²⁺ and HCO₃⁻ reversed from Ca²⁺ excess to HCO₃⁻ excess, probably resulting from a relatively decreased Ca²⁺ contribution from dissolution of gypsum and dolomite due to dilution in mixing water. 2). recover stage when the ion concentrations recovered gradually with relatively lower values than that at pre-earthquake, revealing the reduction of dilute water inflow. In combination with the bulk strain and PGV data, the study suggested that major ion concentrations changes are attributed to dilution effect due to new fracture creation or unclogging/clogging of fractures triggered by the earthquake. The results could enhance the understanding of earthquake induced water chemistry changes and could have implications for water resources management and security in tectonically active areas.

Stable isotopes ratios (‰) of Hydrogen (δ2H) and Oxygen (δ1⁸O) were used to trace the groundwater recharge mechanism and geochemistry of arsenic (As) contamination in groundwater from four selected sites (Larkana, Naudero, Ghari Khuda Buksh and Dokri) of Larkana district. The stable isotope values of δ2H and δ1⁸O range from 70.78‰ to −56.01‰ and from −10.92‰ to −7.35‰, relative to Vienna Standard for Mean Ocean Water (VSMOW) respectively, in all groundwater samples, thus indicating the recharge source of groundwater from high-salinity older water. The concentrations of As in all groundwater samples were ranged from 2 μg/L to 318 μg/L, with 67% of samples exhibited As levels exceeding than that of World Health Organization (WHO) permissible limit 10 μg/L and 42% of samples expressed the As level exceeding than that of the National Environmental Quality Standard (NEQS) 50 μg/L. The leaching and vertical mixing with return irrigation water are probably the main processes controlling the enrichment of As in groundwater of Larkana, Naudero, Ghari Khuda Buksh and Dokri. The weathering of minerals mostly controlled the overall groundwater chemistry; rock-water interactions and silicate weathering generated yielded solutions that were saturated in calcite and dolomite in two areas while halite dissolution is prominent with high As area.

The present study aims to investigate the spatial distribution and associated various geochemical mechanisms responsible for fluoride (F⁻) contamination in groundwater of unconfined aquifer system along major rivers in Sindh and Punjab, Pakistan. The concentration of F⁻ in groundwater samples ranged from 0.1 to 3.9 mg/L (mean = 1.0 mg/L) in Sindh and 0.1–10.3 mg/L (mean = 1.0 mg/L) in Punjab, respectively with 28.9% and 26.6% of samples exhibited F⁻ contamination beyond WHO permissible limit value (1.5 mg/L). The geochemical processes regulated F⁻ concentration in unconfined aquifer mainly in Sindh and Punjab were categorized as follows: 1) minerals weathering that observed as the key process to control groundwater chemistry in the study areas, 2) the strong correlation between F⁻ and alkaline pH, which provided favorable environmental conditions to promote F⁻ leaching through desperation or by ion exchange process, 3) the 72.6% of samples from Sindh and Punjab were dominated by Na⁺- Cl⁻ type of water, confirmed that the halite dissolution process was the major contributor for F⁻ enrichment in groundwater, 4) dolomite dissolution was main process frequently observed in Sindh, compared with Punjab, 5) the arid climatic conditions promote evaporation process or dissolution of evaporites or both were contributing to the formation of saline groundwater in the study area, 6) the positive correlation observed between elevated F⁻ and fluorite also suggested that the fluorite dissolution also played significant role for leaching of F⁻ in groundwater from sediments, and 7) calcite controlled Ca2⁺ level and enhanced the dissolution of F-bearing minerals and drive F⁻ concentration in groundwater. In a nut shell, this study revealed the worst scenarios of F⁻ contamination via various possible geochemical mechanisms in groundwater along major rivers in Sindh and Punjab, Pakistan, which need immediate attention of regulatory authorities to avoid future hazardous implications.

Hydrogeochemistry and isotope hydrology were carried out to investigate the spatial distribution of fluoride (F−) and the mechanisms responsible for its enrichment in the western region of the Ordos basin, northwestern China. Sixty-two groundwater samples from the unconfined aquifer and fifty-six from confined aquifer were collected during the pre-monsoon (June 2016). Over 77% of groundwater samples from the unconfined aquifer (F− concentration up to 13.30 mg/L) and approximately 66% from confined aquifer (with a maximum F− concentration of 3.90 mg/L) exhibit F− concentrations higher than the Chinese safe drinking limit (1.0 mg/L). High-F− groundwater presents a distinctive hydrochemical characteristic: a high pH value and HCO3− concentration with Ca-poor and Na-rich. Mineral dissolution (e.g., feldspar, calcite, dolomite, fluorite), cation exchange and evaporation in the aquifers predominate the formation of groundwater chemistry, which are also important for F− enrichment in groundwater. Mixing with unconfined groundwater is a significant mechanism resulting in the occurrence of high-F− groundwater in confined aquifer. These findings indicate that physicochemical processes play crucial roles in driving F− enrichment and that may be useful for studying F− occurrence in groundwater in arid and semi-arid areas.

A massive and dense textured layer (ca. 35–50 cm thick) of hardpan was uncovered at the top layer, which capped the unweathered sulfidic Cu-Pb-Zn tailings in depth and physically supported gravelly soil root zones sustaining native vegetation for more than a decade. For the purpose of understanding functional roles of the hardpan layer in the cover profile, the present study has characterized the microstructures of the hardpan profile at different depth compared with the tailings underneath the hardpans. A suit of microspectroscopic technologies was deployed to examine the hardpan samples, including field emission-scanning electron microscopy coupled with energy dispersive spectroscopy (FE-SEM-EDS), X-ray diffraction (XRD) and synchrotron-based X-ray absorption fine structure spectroscopy (XAFS). The XRD and Fe K-edge XAFS analysis revealed that pyrite in the tailings had been largely oxidised, while goethite and ferrihydrite had extensively accumulated in the hardpan. The percentage of Fe-phyllosilicates (e.g., biotite and illite) decreased within the hardpan profile compared to the unweathered tailings beneath the hardpan. The FE-SEM-EDS analysis showed that the fine-grained Ca-sulfate (possibly gypsum) evaporites appeared as platelet-shaped that deposited around pyrite, dolomite, and crystalline gypsum particles, while Fe-Si gels exhibited a needle-like texture that aggregated minerals together and produced contiguous coating on pyrite surfaces. These microstructural findings suggest that the weathering of pyrite and Fe-phyllosilicates coupled with dolomite dissolution may have contributed to the formation of Ca-sulfate/gypsum evaporites and Fe-Si gels. These findings have among the first to uncover the microstructure of hardpan formed at the top layer of sulfidic Cu-Pb-Zn tailings, which physically capped the unweathered tailings in depth and supported root zones and native vegetation under semi-arid climatic conditions.

High concentration of fluoride (up to 20.9 mg/L) in groundwater with significant variation (p = 5.9E-128) among samples was reported from Birbhum district, an acknowledged fluoride endemic region in India. The groundwater samples (N = 368) were grouped based on their hydrochemical properties and aquifer geology for hydro-geochemical characterization. Friedman’s test showed p < 0.0001 confidence level which indicates that fluoride concentration among geological groups and water groups are independent. Bland-Altman plot was used to study the inter-relationships among the groups through bias value (∂) and limit of agreement (LoA). Among the geological groups, laterites and granite-gneiss groups exhibited statistically significantly difference in fluoride geochemistry; whereas the younger and older alluvium groups displayed similar characteristics. The fluoride concentration was found to be in the order Lateritic > Granite-gneiss > Older alluvium ≥ Younger alluvium. Dissolution of minerals (such as fluorite, biotite) in laterite sheeted basalt, and granite-gneiss is the main source of groundwater fluoride in the region. Fluoride concentration is also influenced by depth of water table. Hydrochemical study indicated that fluoride concentration was higher in Na–HCO₃ than in Ca–SO₄ and Ca–HCO₃ type of groundwater. The fluoride concentration were positively correlated with Na⁺ and pH and negatively correlated with the Ca²⁺ and Mg²⁺ signifying linkage with halite dissolution and calcite, dolomite precipitation. Geostatistical mapping of WQI through empirical bayesian kriging (EBK) with respect to regional optimal guideline value (0.73 mg/L) classified that groundwater in some parts of the district are unfit for drinking purpose. Health survey (N = 1767) based on Dean’s criteria for dental fluorosis indicated presence of slight to moderate dental hazard. Besides, providing baseline data for management of groundwater quality in the study area, the study demonstrated the applicability of Bland-Altman analysis and empirical bayesian kriging (EBK) in delineation and interpolation of fluoride contaminated region.

Nitrous oxide (N2O) is a devastating greenhouse gas mainly released from soils to the atmosphere. Pasture soils, particularly acidic in nature, are large contributors of atmospheric N2O through deposition of urine-N. Devising strategies for reducing N2O emissions in acidic soils are the utmost need of the time. Therefore, the present study was carried out to investigate the possible efficacy of dolomite application to reduce N2O emissions from urine treated acidic soil. Application of urine to soil enlarged the production of NH4+-N, NO3−-N, microbial biomass C (MBC) and dissolved organic C (DOC), resulting in higher N2O emissions as compared to the control (soil only). The highest N2O emission rate (1.35 μg N2O-N kg−1 h−1) and cumulative flux (408 μg N2O-N kg−1) occurred in urine only treated soil. Dolomite addition, especially higher application dose, greatly reduced N2O emissions through improved soil pH. The results suggest that increasing pH of acidic soils is a good applicable approach for reducing N2O emissions from urine-treated soils.

Several studies have been carried out to examine nitrous oxide (N₂O) emissions from agricultural soils in the past. However, the emissions of N₂O particularly during amelioration of acidic soils have been rarely studied. We carried out the present study using a rice-rapeseed rotation soil (pH 5.44) that was amended with dolomite (0, 1 and 2 g kg⁻¹ soil) under 60% water filled pore space (WFPS) and flooding. N₂O emissions and several soil properties (pH, NH₄⁺N, NO₃⁻-N, and nosZ gene transcripts) were measured throughout the study. The increase in soil pH with dolomite application triggered soil N transformation and transcripts of nosZ gene controlling N₂O emissions under both water regimes (60% WFPS and flooding). The 60% WFPS produced higher soil N₂O emissions than that of flooding, and dolomite largely reduced N₂O emissions at higher pH under both water regimes through enhanced transcription of nosZ gene. The results suggest that ameliorating soil acidity with dolomite can substantially mitigate N₂O emissions through promoting nosZ gene transcription.