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.

We investigate the use of hydrated lime and calcite waste marble powder as remediation treatments of contaminated jarosite-rich sediments from Portman Bay (SE, Spain), one of the most contaminated points in the Mediterranean coast by mining-metallurgical activities. We tested two commercial hydrated limes with different Ca(OH)₂ percentages (28 and 60% for Lime-1 and Lime-2 respectively) and two different waste marble powder, WMP, from the marble industry (60 and 96% of calcite for WMP-1 and WMP-2 respectively). Mixture and column experiments and modelling of geochemical reactions using PHREEQC were performed. Lime caused the precipitation of hematite, gypsum and calcite, whereas WMP treatments formed iron carbonates and hematite. The fraction of amorphous phases was mainly composed of iron oxides, hydroxides and oxyhydroxides that was notably higher in the lime treatment in comparison to the WMP treatment. The reactive surface area showed a positive trend with the amorphous phase concentration. Results highlighted the effectiveness of lime treatments, where Lime-2 showed a complete elimination of jarosite. Column experiments revealed a clear reduction of heavy metal concentration in the lixiviate for the treated sediments compared to the original sediments. Particularly, Lime-2 showed the highest reduction in the peak concentration of Fe, Mn, Zn and Cd. The studied treatments limited the stabilisation of Cr and Ni, whereas contrarily As increases in the treated sediment. PHREEQC calculations showed that the most concentrated heavy metals (Zn and Mn) are stabilized mainly by precipitation whereas Cu, Pb and Cd by a combination of precipitation and sorption processes. This chemical environment leads to the precipitation of stable iron phases, which sorb and co-precipitate considerable amounts of potentially toxic elements. Lime is significantly more effective than WMP, although it is recommended that the pH value of the mixture should remain below 9 due to the amphoteric behaviour of heavy metals.

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.

Rapid economic expansion poses serious problems for groundwater resources in arid areas, which typically have high rates of groundwater depletion. In this study, integration of hydrochemical investigations involving chemical and statistical analyses are conducted to assess the factors controlling hydrochemistry and potential pollution in an arid region. Fifty-four groundwater samples were collected from the Dhurma aquifer in Saudi Arabia, and twenty-one physicochemical variables were examined for each sample. Spatial patterns of salinity and nitrate were mapped using fitted variograms. The nitrate spatial distribution shows that nitrate pollution is a persistent problem affecting a wide area of the aquifer. The hydrochemical investigations and cluster analysis reveal four significant clusters of groundwater zones. Five main factors were extracted, which explain >77% of the total data variance. These factors indicated that the chemical characteristics of the groundwater were influenced by rock–water interactions and anthropogenic factors. The identified clusters and factors were validated with hydrochemical investigations. The geogenic factors include the dissolution of various minerals (calcite, aragonite, gypsum, anhydrite, halite and fluorite) and ion exchange processes. The anthropogenic factors include the impact of irrigation return flows and the application of potassium, nitrate, and phosphate fertilizers. Over time, these anthropogenic factors will most likely contribute to further declines in groundwater quality.

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).

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.

Microplastics are extremely widespread aquatic pollutants that severely detriment marine life. In this study, the influence of microplastics on biomineralization was investigated. For the first time, multiple forms and types of microplastics were detected and isolated from the shells and pearls of Pinctada fucata. According to the present study, the abundance of microplastics in shells and pearls was estimated at 1.95 ± 1.43 items/g and 0.53 ± 0.37 items/g respectively. Interestingly, microplastics were less abundant in high-quality round pearls. Microplastics may hinder the growth of calcite and aragonite crystals, which are crucial components required for shell formation. During the process of biomineralization microplastics became embedded in shells, suggesting the existence of a novel pathway by which microplastics accumulate in bivalves. After a 96-h exposure to microplastics, the expression level of typical biomineralization-related genes increased, including amorphous calcium carbonate binding protein (ACCBP) gene which experienced a significant increase. ACCBP promotes the formation of amorphous calcium carbonate (ACC), which is the pivotal precursor of shell formation-related biominerals. ACCBP is highly expressed during the developmental stage of juvenile oysters and the shell-damage repair process. The increased expression of ACCBP suggests biomineralization is enhanced as a result of microplastics exposure. These results provide important evidence that microplastics exposure may impact the appearance of biominerals and the expression of biomineralization-related genes, posing a new potential threat to aquatic organisms.