Contaminant vulnerability in the critical zones like groundwater (GW)-seawater (SW) continuum along the entire Gujarat coast was investigated for the first time through an extensive water monitoring survey. The prime focus of the study was to evaluate whether or not: i) seawater intrusion induced metal load translates to toxicity; ii) in the coastal groundwater, metal distribution follows the pattern of other geogenic and anthropogenic contaminants like NO₃- and F-; and iii) what future lies ahead pertaining to metal fate in association with saturation conditions of the coastal aquifers. The spatial distribution of contaminants depicts that the Gulf of Khambhat area is highly contaminated. Ecological risk assessment (ERA) indicates that the Gujarat coast is experiencing a high ecological risk compared to the southeast coast of India. Investigation results revealed that metals, pH, NO₃, and CO₃ are more vulnerable at the SW-GW mixing interface. An increase in pH is reflected in fewer ionic species of metals in the GW. Salinity ingress due to seawater intrusion (SWI) reduces the toxicities of all trace metals except Cu, attributed to the increase of Ca in GW, leading to dissociation of CuCO₃. Reactive species are dominant for Zn and Cd; and M-CO₃ ligands are dominant for Cu and Pb owing to the undersaturation of dolomite and calcite in the aquifer system. SWI tends to increase the metal load but the toxicity of metals varies with the density of industries, anthropogenic activities, changes in the mixing-induced saturation conditions, and intensive salt production across the coast. Multivariate analysis confirmed that the hydrogeochemical processes change due to GW-SW mixing and dictates over natural weathering. The ecological risk index (ERI) for the Arabian sea is experiencing moderate (300 ≥ ERI>150) to high ecological risk (ERI >600). Children population is likely to encounter a high health risk through ingestion and dermal exposure than adults. Overall, the study emphasizes the complexity of toxicity-related health impacts on coastal communities and suggests the dire need for frequent water monitoring along the coastal areas for quick realization of sustainable development goals.

In acidic medium, hazardous heavy metals of lead-zinc tailing (LZT) are easily leachable and mobilizable. Thus, the hazard, amount, form, and complexity of the leached heavy metals under acidic precipitation become a major environmental concern. This work investigates the gangue minerals, toxicity, speciation, leaching characteristics of heavy metals in LZT under simulated acid rain, as well as immobilization effects and mechanisms using a sustainable binder. In LZT, dolomite, quartz, calcite, and muscovite are the main gangue minerals, tiny hazardous metallic minerals were absorbed in the surface. The results revealed that Pb, Zn, Cr, and Cd were the predominant harmful elements, particularly Pb and Zn. Zn is leached completely and is the concerned hazardous element under simulated acid rain. In the acid rain neutralization ability test, the amount of leachable Pb, Cr, Ca, and Si maintained in equilibrium, leached Zn, Cd, Al, and Mg depended on the addition of acid. Pb and Ca were sedimented in residues. Immobilization of Pb, Zn, Cr, and Cd depended on the stability of Ca(OH)₂/C–S–H of hydrates, and 70% LZTHP after curing 7 days can be used for some practical engineering projects. This work opens up deeply understandings for the leached heavy metals under acidic precipitation and improves the sustainable and safe in the field of immobilization of heavy metals.

Mine waste classification preceding mining constitutes a proactive solution to classify and segregate mine waste into geo-environmental domains based upon the magnitude of their environmental risks. However, upstream classification requires multi-disciplinary and integrated approaches. This study integrates geological modeling and kinetic modeling to inform upstream mine waste classification based on the pH generated from the main acid-generating and acid-neutralizing reactions once the mine solid waste is stored in oxidizing conditions. Geological models were used to depict the ante-mining spatial distribution of the main reactive minerals: pyrite, albite and calcite. Subsequently, the corresponding block models were created. The dimension of the elementary voxels for each block model was set at 40х40х40 m for this study. The kinetic modeling approach was performed using PHREEQC and VS2DRTI to consider unsaturated conditions. The kinetic modeling simulated a 1D column for each voxel. The column simulates the excavated state of the hosting rock involving kinetic reactions and unsaturated flow under highly oxidizing conditions. Subsequently, the resulting pH for different intervals of time was assigned to its respective voxel. The outcome consists of a spatio-temporal visualization of the pH defining ante-mining geo-environmental domains, thereby providing the opportunity for formulating proactive management measures regarding the hazardous geo-environmental domains.

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.

Wastewater containg proteinaceous ossein effluents are problematic to be treated. We studied the possibility to treat ossein effluents with the marine cyanobacterium strain Cylindrospermum stagnale. After optimizing the culture conditions of the bacterium, three different types of ossein effluents were tested: dicalcium phosphate (DCP), high total dissolved solids (HTDS) and low total dissolved (LTDS). The effluents were diluted with sea water at the following ratios 1:1, 2:1 and 3:2. The optimum operating conditions were at 3000 lux light intensity and 37 °C temperature. The highest degradation of ossein effluens by C. stagnale was attained for a dilution ratio of 1:1. However, less diluted ossein effluents reduced the growth of C. stagnale drastically. The degradation was shown by measuring the chlorophyll a content and the dry weight of bacterial cells during a seven-day incubation period degradation. Fourier Transform Infrared Spectroscopy (FT-IR) analysis verified the degradation showing the presence of the degradation products of ossein (i.e. calcium carbonate and calcite) in the culture medium. Lipid composition in fatty acids appeared to be suitable for biofuel production. The results showed that the marine cyanobacterium C. stagnale can be used to treat ossein effluents, and at the same time, to produce biofuel in a sustainable way.

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.

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.

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.

A chronological sequence of urban soils 3–92 years old was studied to determine the effects of time on morphogenesis, artifact weathering, and the geochemical partitioning of Pb. Key chronofunctions determined are an increase in ˆA horizon Development Index (defined herein based on soil color) and water-soluble Pb, and a decrease in pH and C/N, with increasing soil age. Key artifact weathering reactions are: 1) portlandite in mortar altered to calcite, 2) ferrite in wrought-iron altered to ferrihydrite and goethite, and 3) carbonaceous materials altered to water-soluble organic substances. Mortar and wrought-iron were found to be Pb-bearing, but weather to produce immobilizing agents. Hence, they are both a source and a sink for Pb. The origin and mobilization of water-soluble Pb is complex and probably includes microbial extracellular polymeric substances, biodegraded soil organic matter, and solubilized organic substances derived from carbonaceous anthropogenic microparticles (soot, char and coal-related wastes).

Biochar modification by metals and metal oxides is considered a practical approach for enhancing the adsorption capacity of anionic compounds such as phosphate (P). This study obtained paper mill sludge (PMS) biochar (PMSB) via a one-step process by pyrolyzing PMS waste containing ferric salt to remove anionic P from water. The ferric salt in the sludge was transformed into ferric oxide and zero-valent-iron (Fe⁰) in N₂ atmosphere at pyrolysis temperatures ranging from 300 to 800 °C. The maximum adsorption (Qₘ) of the PMSBs for P ranged from 9.75 to 25.19 mg P/g. Adsorption is a spontaneous and endothermic process, which implies chemisorption. PMSB obtained at 800 °C (PMSB800) exhibited the best performance for P removal. Fe⁰ in PMSB800 plays a vital role in P removal via adsorption and coprecipitation, such as forming the ≡Fe–O–P ternary complex. Furthermore, the possible chemical precipitation of P by CaO decomposed from calcite (CaCO₃; an additive of paper production that remains in PMS) may also contribute to the removal of P by PMSB800. Moreover, PMSBs can be easily separated magnetically from water after application and adsorption. This study achieved a waste-to-wealth strategy by turning waste PMS into a metal/metal oxide-embedded biochar with excellent P removal capability and simple magnetic separation properties via a one-step pyrolysis process.