Plutonium Speciation and Oxidation State Distributions in the Presence of Citrate.

We explored the speciation and kinetics of the Pu(VI)-citrate and Pu(III)-citrate systems (pHm = 2.5-11.0, I = 0.1 M NaCl, T = 23 °C, O2(g) < 2 ppm) using ultraviolet-visible-near-infrared (UV-vis-NIR) spectrophotometry, solvent extraction, and PHREEQC modeling. Formation constants were determined for PuO2(HcitH)(aq) (log K°1,1 = 1.09 ± 0.05) and PuO2(HcitH)(citH)3- (log K°1,2 = -0.20 ± 0.07), and evidence for (PuO2)m(citH-k)n(OH)x2m(3+k)n-x was identified under alkaline conditions. Pu(VI) species were found to be less stable in the presence of citrate than in the absence of citrate (t ≤ 168 days); the rate of reduction increased with increasing pH. The direct reduction of Pu(VI) to Pu(IV) was required to fit experimental data in the presence of citrate but did not improve the fit for Pu in the absence of citrate. We also observed increased Pu(III) stability in the presence of citrate (t ≤ 293 days), with higher concentrations of Pu(III) favored at lower pH. Finally, we provide evidence of a radiolysis-driven mechanism for the citrate-mediated reduction of plutonium that involves electron transfer from the oxidative breakdown of citrate. Our work highlights the need to investigate the redox effect of organic ligands on plutonium oxidation states under repository-relevant conditions.

Modeling the geochemical evolution of mine waters during mixing.

This study focuses on assessing the hydrogeochemical processes influencing the mobility of dissolved metal and metalloid species during mine effluent mixing. Field samples were collected to characterize effluents at an active gold mine located in the Abitibi Greenstone belt in western Québec, Canada. Controlled laboratory mixing experiments were further performed with real effluents. In situ physicochemical parameters, concentrations of major dissolved ions and trace elements were analyzed. Mineralogical analyses were also performed on precipitates from the laboratory mixtures. The data were used for statistical analyses and for modeling the geochemical evolution of effluents using PHREEQC with the wateq4f.dat database (with modifications). The results suggest that the formation of secondary minerals such as schwertmannite, Fe(OH)3, and jarosite could significantly affect the concentrations of trace elements in effluents. The precipitation of secondary minerals immobilized trace elements through coprecipitation and sorption processes. The main limitations of the modeling approach used here include the evaluation of the ion balance for low pH samples with high Fe and Al concentrations and the omission of biological processes. The approach provides insights into the geochemical evolution of mine effluents and could be adapted to several mining sites as a tool for improving water management.

Simulation of hexavalent chromium removal by electrocoagulation using iron anode in flow-through reactor.

An electrocoagulation (EC) model is developed for hexavalent chromium reduction and precipitation, using iron electrodes. Parallel removal mechanisms such as adsorption of chromium on ferrihydrite and direct reduction at the cathode is assumed negligible due to low concentration of Cr(VI). The reaction model presented for batch system represents species complexation, precipitation/dissolution, acid/base, and oxidation-reduction reactions. Batch reactor simulation is verified using experimental data obtained by Sarahney et al. (2012), where the effect of initial chromium concentration, pH, volumetric current density, and ionic strength is considered (Sarahney et al., 2012). The model couples multicomponent ionic transport in MATLAB with chemical reaction model in PHREEQC, as a widely used computational programming tool and a geochemical reaction simulator with comprehensive geochemistry databases. The suggested current density is 0.05-0.3mA/cm2 and the surface to volume ratio in batch reactor is considered 0.017 1/cm. Design parameters are presented for operation of a flow-through hexavalent chromium removal using electrocoagulation by iron electrode to treat Cr(VI) in range of 10-50 mg/L. The operational parameters for a flow-through EC reactor for Cr(VI) removal is suggested to follow [Formula: see text] .

Reactivity and bioconcentration of stable cesium in a hyperturbid fluvial-estuarine continuum: A combination of field observations and geochemical modeling.

Effective, post-accidental management needs an accurate understanding of the biogeochemical behavior of radionuclides in surface environments at a regional scale. Studies on stable isotopes (element homologs) can improve this knowledge. This work focuses on the biogeochemical behavior of stable cesium (Cs) along a major European fluvial-estuarine system, the Gironde Estuary (SW France). We present results obtained from (i) a long-term monitoring (2014-2017) of dissolved (Csd) and particulate (Csp) Cs concentrations at five sites along the freshwater continuum of the Garonne watershed, (ii) Csd and Csp concentrations during four oceanographic campaigns at contrasting hydrological conditions along longitudinal profiles of the estuarine system, (iii) a 24 h cycle of Csp at the estuary mouth, and (iv) a historical trend of Cs bioconcentration in wild oysters at the estuary mouth (RNO/ROCCH, 1984-2017). In addition, we model the partitioning of Cs within the estuarine environment for clay mineral interactions via PhreeqC. At fluvial sites, we observe a geogenic dependence of the Csp and a seasonal variability of Csd, with a downstream increase of the solid-liquid partitioning (log10 Kd values from 3.64 to 6.75 L kg-1) for suspended particulate matter (SPM) < 200 mg L-1. Along the estuarine salinity gradients, Cs shows a non-conservative behavior where fresh SPM (defined as Cs-depleted particles recently put in contact with Csd) act as a Cs sink during both flood and low discharge (drought) conditions. This sorption behavior was explained by the geochemical model, highlighting the relevance of ionic strength, water and SPM residence times. However, at high salinities, the overall log10 Kd value decreases from 6.02 to 5.20 for SPM ∼300-350 mg L-1 due to the Csd oceanic endmember. Despite wild oysters showing low bioconcentration factors (∼1220 L kg-1) at the estuary mouth, they are sensitive organisms to Cs fluxes.

Effect of temperature on the dissolution of the lead (II) carbonate hydrocerussite for varying pH and dissolved inorganic carbon conditions.

The effect of temperature on the solubility of lead-bearing solid phases in water distribution systems for different water chemistry conditions remains unclear although lead concentrations are known to vary seasonally. The study objective is to explore the effect of temperature on the solubility of the lead(II) carbonate hydrocerussite under varying pH and DIC conditions. This is achieved through batch dissolution experiments conducted at multiple pHs (6-10) and DIC concentrations (20-200 mg CL-1) at temperatures ranging from 5 to 40 °C. A thermodynamic model was also applied to evaluate the model's ability to predict temperature effects on lead(II) carbonate solubility including solid phase transformations. In general, increasing temperature increased total dissolved lead at high pHs and the effect of temperature was greater for high DIC conditions, particularly for pH > 8. Temperature also influenced the pH at which the dominant lead(II) solid phase switched from hydrocerussite to cerussite (occurred between pH 7.25 to 10). Finally, the model was able to capture the overall trends observed despite thermodynamic data limitations. While this study focuses on a simple lead solid-aqueous system, findings provide important insights regarding the way in which temperature and water chemistry interact to affect lead concentrations.

Vertical migration behavior simulation and prediction of Pb and Cd in co-contaminated soil around Pb-Zn smelting slag site.

Heavy metal migration in soil poses a serious threat to the soil and groundwater. Understanding the migration pattern of heavy metals (HMs) under different factors could provide a more reasonable position for pollution evaluation and targetoriented treatment of soil heavy metal. In this study, the migration behavior of Pb and Cd in co-contaminated soil under different pH and ionic strength (NaCl concentration) was simulated using convective dispersion equation (CDE). We predicted the migration trends of Pb and Cd in soils after 5, 10, and 20 years via PHREEQC. The results showed that the migration time of Cd in the soil column experiment was about 60 days faster than that of Pb, and the migration trend was much steeper. The CDE was proved to describe the migration behavior of Pb and Cd (R2 > 0.75) in soil. The predicted results showed that Cd migrated to 15-20 cm of soil within 7 years and Pb stayed mainly in the top 0-6 cm of soil within 5 years as the duration of irrigation increased. Overall, our study is expected to provide new insight into the migration of heavy metal in soil ecosystems and guidance for reducing risk of heavy metal in the environment.

Study on inverse geochemical modeling of hydrochemical characteristics and genesis of groundwater system in coal mine area - a case study of Longwanggou Coal Mine in Ordos Basin.

The exploitation of coal resources has disturbed the equilibrium of the original groundwater system, resulting in a perturbation of the deep groundwater dynamic conditions and hydrochemical properties. Exploring the formation of mine water chemistry under the conditions of deep coal seam mining in the Ordos Basin provides a theoretical basis for the identification of sources of mine water intrusion and the development and utilization of water resources. This paper takes Longwanggou Coal Mine as the research area, collects a total of 106 groups of water samples from the main water-filled aquifers, comprehensively uses Piper trilinear diagram, Gibbs diagram, ion correlation, ion ratio coefficient and mineral saturation index analysis, and carries out inverse geochemical modeling with PHREEQC software, so as to analyze the hydrochemical characteristics and causes of the main water-filled aquifers in deep-buried coal seams in the research area. The results show that the main hydrochemical processes in the study area are leaching and cation exchange, and the groundwater is affected by carbonate (calcite, dolomite), silicate (gypsum) and evaporite. Calculations of mineral saturation indices and PHREEQC simulations have led to the conclusion that the dissolution of rock salt and gypsum in groundwater accounts for most of the ionic action. Na+, Cl- and SO42- are mainly derived from the dissolution of rock salt and gypsum minerals, while Ca2+ and Mg2+ are mostly derived from the dissolution of dolomite and calcite. The results of the inverse geochemical modeling are consistent with the theoretical analysis.

Identifying sources of acid mine drainage and major hydrogeochemical processes in abandoned mine adits (Southeast Shaanxi, China).

Acid mine drainage (AMD) has resulted in significant risks to both human health and the environment of the Han River watershed. In this study, water and sediment samples from typical mine adits were selected to investigate the hydrogeochemical characteristics and assess the environmental impacts of AMD. The interactions between coexisting chemical factors, geochemical processes in the mine adit, and the causes of AMD formation are discussed based on statistical analysis, mineralogical analysis, and geochemical modeling. The results showed that the hydrochemical types of AMD consisted of SO4-Ca-Mg, SO4-Ca, and SO4-Mg, with low pH and extremely high concentrations of Fe and SO42-. The release behaviors of most heavy metals are controlled by the oxidation of sulfide minerals (mainly pyrite) and the dissolution/precipitation of secondary minerals. Along the AMD pathway in the adit, the species of Fe-hydroxy secondary minerals tend to initially increase and later decrease. The inverse model results indicated that (1) oxidative dissolution of sulfide minerals, (2) interconversion of Fe-hydroxy secondary minerals, (3) precipitation of gypsum, and (4) neutralization by calcite are the main geochemical reactions in the adit, and chlorite might be the major neutralizing mineral of AMD with calcite. Furthermore, there were two sources of AMD in abandoned mine adits: oxidation of pyrite within the adits and infiltration of AMD from the overlying waste rock dumps. The findings can provide deeper insight into hydrogeochemical processes and the formation of AMD contamination produced in abandoned mine adits under similar mining and hydrogeological conditions.

Identification of Playa Lakes and tracking their evolution pathways using geochemical models in the Great Indian Thar desert.

Playa Lakes of the great Indian Thar desert are unique and intricate systems with pronounced scientific and ecological significance. In this study, the combined use of geospatial and field data assisted in depicting and understanding the changes within these natural systems. The purpose of this study is to provide a comprehensive dataset of Playa Lakes, which can help with an overall understanding of playas from a geochemical, ecological, and economic perspective. The 1163 surface depressions were accounted for as possible playas considering the threshold area of >5 km2. A total of 42 representative surface water samples were collected from the selected playas (Sambhar, Didwana, Pachpadra, and Pokhran) and hydrochemical analysis was carried out to identify the geochemical evolution of these playas. The major water types were Na-Cl and Na-Cl-SO4 type. Hardie and Eugster's model was used to explain the possible sequence of evolutionary pathways and brine shifts in the selected playas. Simulated evaporation modeling suggests precipitation of major evaporites (chlorides, carbonates, and sulphates) during progressive evaporation. Surface sediment analysis (X-ray diffraction) confirmed the presence of calcite, halite, and dolomite minerals in the playa sediments. The greatest economic value of these playas may be mineral production and providing food and habitat for migratory birds, though conservation and policy intervention is required for their sustainable utilization.

Geochemical modeling of systems affected by irrigation: The case of Lerma basin (Spain, 2004-2020).

Geologically "saline" zones with scarce pluviometry, which are already susceptible to the salinization of natural drainage, can experience the acceleration of the salinization of the receiving water systems with the implementation of irrigation. The main objective of this paper is to analyze the geochemical processes that control the variations of the hydrosaline balance due to the implementation of irrigation of the Lerma basin (Spain) from the beginning of its transformation into irrigation land (2004) until the consolidation of irrigation (2020). The results of this study evidence the dissolution of some mineral phases, such as halite, gypsum, and dolomite, and the precipitation of others, such as calcite. Additionally, the final composition of the irrigation return flows cannot be explained without consideration of the NaCa exchange. Part of the dissolved Ca2+ is deposited in the soil, which, in turn, contributes with Na+ to the solution. These natural processes are accelerated with irrigation but progressively slow down as the soil salts are washed with time. Although less evident, there is an additional negative agroenvironmental effect associated with the precipitation of calcite and the possible formation of petrocalcic horizons in the soil. The results obtained herein indicate that studies focusing on the salinity of irrigated zones should go a step further and include the geochemical processes in quantifying the global mass of exported salts.

A novel hydrogeochemical approach to delineate the origin of potentially toxic elements in groundwater: Sophisticated molar ratios as environmental tracers.

The occurrence, mobilization, and origin of Potentially Toxic Eelements (PTEs) in the environment is always a difficult research question that has not been fully addressed to date; solving this problem would be a major achievement for environmental science and pollution research, a significant scientific breakthrough, and an important contribution to environmental analysis and monitoring. The lack of a holistic methodology that uses chemical analysis to determine the origin of each PTE in the environment is the main motivation for this project. Therefore, the hypothesis tested here is to develop a scientific approach applied to each PTE to determine whether its origin is geogenic (i.e., water-rock interaction with dominance of silicate or carbonate mineral phases) or anthropogenic (i.e., agricultural practices, wastewater, industrial activities). A total of 47 groundwater samples from the Psachna Basin in central Euboea, Greece, were used and plotted on geochemical mole ratio diagrams (i.e., Si/NO3 vs. Cl/HCO3) and used to perform a robust geochemical modeling analysis. The proposed method showed that elevated groundwater concentrations of various PTEs in groundwater were mainly related to intensive fertilization (e.g., Cr, U), water-rock interaction (e.g., Ni), and saltwater intrusion. (i.e., As, Se). This work highlights that a comprehensive framework with sophisticated molar ratios combined with modern statistical methods, multi-isotope signatures, and geochemical modeling could provide answers to unresolved scientific questions about the origin of PTEs in water resources and improve environmental resilience.

Reactive transport model of uranium by CO2 + O2 in situ leaching.

Uranium is an important strategic resource, and its safe and efficient development and utilization are of great significance to ensuring a nation's energy supply and strategic security. Sandstone-type uranium ore is commonly mined by CO2 + O2 in situ leaching, for which understanding the coupling mechanism between the hydrodynamic and chemical fields is key to predicting uranium leaching. This study focused on a coal-uranium ore deposit in China. A convection and dispersion model of the solute transport by in situ leaching was constructed in COMSOL, and a thermodynamic model of CO2 + O2 in situ leaching in sandstone-type uranium ore was constructed in PHREEQC. The two models were coupled to simulate the reactive transport and dynamic leaching processes of uranium by CO2 + O2 in situ leaching. A sensitivity analysis was performed to quantitatively analyze the effects of different model parameters on the uranium leaching efficiency and uranium contamination remediation. The results showed that the coupled model could simulate and predict the reaction and transport of uranium. The sensitivity analysis indicated that the production rate and the injected CO2 and O2 concentrations are the key parameters that control the uranium leaching efficiency, followed by the formation permeability and injection rate. The uranium leaching efficiency does not increase monotonically with the formation permeability and production rate. The results also indicated that natural dilution is insufficient for remediating uranium-contaminated groundwater, but the remediation efficiency can be improved by increasing solution extraction. The results of this study can be used to develop guidelines for the safe and efficient development and utilization of uranium ore while protecting the ecological environment.

Hydrogeochemical characterization and geochemical modeling for the evaluation of groundwater quality and health risk assessment in the Varuna River basin, India.

This study focuses on determining significant controlling factors of chemical consequences, inverse geochemical modeling, water quality, and human health risk in the Varuna River basin of India. The study interprets that according to pH, total dissolved solids, and total hardness, the maximum number of groundwater samples are alkaline, fresh, and have substantial hardness. The abundance of major ions follows a pattern: Na > Ca > Mg > K, and HCO3 > Cl > SO4 > NO3 > F. Piper diagram shows that Ca-Mg-HCO3 facies are predominant during both seasons. Na-normalized molar ratios of HCO3/Na, Mg/Na, and Ca/Na are 0.62, 0.95, and 1.82 (pre-monsoon) and 0.69, 0.91, and 1.71 (post-monsoon), respectively, elucidating the coupled silicate and carbonate weathering (dolomite dissolution) sources. The Na/Cl molar ratio is 5.3 (pre-monsoon) and 3.2 (post-monsoon), indicating silicate alteration as the primary process rather than halite dissolution. The chloro-alkaline indices confirm the presence of reverse ion- exchange. Geochemical modeling using PHREEQC identifies the formation of secondary kaolinite minerals. The inverse geochemical modeling categorizes the groundwaters along the flow path from recharge area waters (Group I: Na-HCO3-Cl), transitional area waters (Group II: Na-Ca-HCO3), and discharge area waters (Group III: Na-Mg-HCO3). The model demonstrates the prepotency of water-rock interactions in pre-monsoon justified by the precipitation of Chalcedony and Ca-montmorillonite. The mixing analysis shows that in the alluvial plains, groundwater mixing is a significant hydrogeochemical process that affects groundwater quality. The Entropy Water Quality Index ranks 45% (pre-monsoon) and 50% (post-monsoon) of samples as an excellent category. However, the non-carcinogenic health risk assessment shows that children are more susceptible to fluoride and nitrate contamination.

Ferrocyanide enhanced evaporative flux to remediate soils contaminated with produced water brine.

Accidental releases of highly saline produced water (PW) to land can impact soil quality. The release of associated salts can clog soil pores, disperse soil clays, and inhibit plants and other soil biota. This study explores a novel remediation technique using ferrocyanide to enhance the evaporative flux of soil porewater to transport dissolved salts to the soil surface, where crystallization then occurs. The addition of ferrocyanide modifies crystal growth that enhances salt transport, allowing salt efflorescence on the soil surface and physical removal. Release sites were simulated through beaker sand column experiments using two PWs collected from the Permian Basin. PW composition altered efflorescence, with up to ten times as much ferrocyanide required in PWs than comparable concentrations of pure NaCl solutions. The addition of EDTA reduced dissolved cation competition for the ferrocyanide ion, improving PW salt recovery at the soil surface. The speciation model, PHREEQC, was used to predict the onset of salt precipitation as a function of evaporative water loss and model the effect of aqueous ferrocyanide and EDTA speciation on efflorescence. The results highlight the utility of predictive modeling for optimizing additive dosages for a given release of PW.

Hydrogeochemical assessment and health-related risks due to toxic element ingestion and dermal contact within the Nnewi-Awka urban areas, Nigeria.

Awka and Nnewi metropolises are known for intensive socioeconomic activities that could predispose the available groundwater to pollution. In this paper, an integrated investigation of the drinking water quality and associated human health risks of contaminated groundwater was carried out using geochemical models, numerical water quality models, and the HHRISK code. Physicochemical analysis revealed that the groundwater pH is acidic. Predicted results from PHREEQC model showed that most of the major chemical and trace elements occurred as free mobile ions while a few were bounded to their various hydrated, oxides and carbonate phases. This may have limited their concentration in the groundwater; implying that apart from anthropogenic influx, the metals and their species also occur in the groundwater as a result of geogenic processes. The PHREEQC-based insights were also supported by joint multivariate statistical analyses. Groundwater quality index, pollution index of groundwater, heavy metal toxicity load, and heavy metal evaluation index revealed that 60-70% of the groundwater samples within the two metropolises are unsuitable for drinking as a result of anthropogenic influx, with Pb and Cd identified as the priority elements influencing the water quality. The HHRISK code evaluated the ingestion and dermal exposure pathway of the consumption of contaminated water for children and adult. Results revealed that groundwater from both areas poses a very high chronic and carcinogenic risk from ingestion than dermal contact with the children population showing greater vulnerability. Aggregated and cumulative HHRISK coefficients identified Cd, Pb, and Cu, to have the highest health impact on the groundwater quality of both areas; with residents around Awka appearing to be at greater risks. There is, therefore, an urgent need for the adoption of a state-of-the-art waste management and water treatment strategies to ensure safe drinking water for the public.

Hydrochemical evolution characteristics and genesis of groundwater under long-term infiltration (2007-2018) of reclaimed water in Chaobai River, Beijing.

The reuse of reclaimed water (RW) for river ecological restoration in global water-shortage regions has inevitably brought some potential risks for groundwater. However, little is known about the effects of reclaimed water on the hydrochemical evolution of groundwater especially under long-term infiltration conditions. Herein, 11-years monitoring data (2007-2018) of reclaimed water and groundwater were adopted to analyze the characteristics and genesis of groundwater hydrochemical evolution under long-term infiltration of reclaimed water from Jian River to Chaobai River in Beijing. The results showed that the hydrochemical components in groundwater totally performed a significant increase in Na+, Cl-, and K+and decrease in Ca2+, Mg2+, and HCO3- concentration after long-term infiltration of reclaimed water. Meanwhile, a significant hydrochemical evolution difference between the groundwater of Jian River and Chaobai River was observed. In Jian River, the hydrochemical type in groundwater shifted gradually from HCO3-Ca·Mg to the type of HCO3·Cl-Na·Ca approaching reclaimed water. In contrast, the hydrochemical evolution in the Chaobai River shows an obvious opposite trend from HCO3-Ca·Mg to HCO3·Cl-Na·Mg and finally deviating reclaimed water type of Cl·HCO3·SO4-Na. PHREEQC simulation indicated that the differences in hydrochemical evolution were mediated synergically by sediment thickness and geochemical processes (e.g. mixing and sulfate reduction). In such mediators, thinner sediment and strong mixing in the Jian River were confirmed to be the genesis of groundwater hydrochemical evolution progressively approaching reclaimed water. Different from the Jian River, multiple regression analyses revealed that the genesis of groundwater hydrochemical evolution in the Chaobai River was divided into two stages according to the increase of sediment thickness. Reclaimed water quality and infiltration amount are the leading proposed cause in the initial stage (2007-2008) due to thinner sediment formation, contributing 53.5% and 29.8% within the 95% confidence interval, respectively. Subsequently, the rise in sediment thickness is proved to play a crucial role in groundwater hydrochemical evolution trend away from reclaimed water (2009-2018), with a contribution of 41.6% within the 95% confidence interval. It is mainly attributed to the reduced reclaimed water infiltration rate and favorable sulfate reduction conditions. These findings advance our understanding on groundwater hydrochemical evolution under long-term infiltration of reclaimed water and also guide future prediction of evolution trends.

Insights into mechanisms governing the passive removal of inorganic contaminants from acid mine drainage using permeable reactive barrier.

The permeable reactive barrier has been deemed as the most prudent and pragmatic way to passively manage and remediate acid mine drainage (AMD). Herein, insights into mechanisms governing the removal of inorganic contaminants from AMD using a permeable reactive barrier (PRB), i.e. pervious concrete, were reported. In particular, the effects of varying dosages, i.e., 6, 10, 30, and 60 g, of cementitious materials comprising CEM I 52.5R with or without fly ash, hydrated lime, and gypsum were evaluated whilst the fate of chemical species was underpinned using the state-of-the-art analytical techniques, along with PHREEQC geochemical modelling. The role of gypsum, a product formed from the interaction of PRB with AMD in heavy metals attenuation was also elucidated. Findings revealed cementitious materials to play an indispensable role in the removal of inorganic contaminants from AMD. Furthermore, alkalinity from used materials increases the pH (i.e. pH ≥ 12.5) of AMD leading to the precipitation of chemical species. Specifically, the efficacy registered the following sequence: Lime ≥ CEM I ≥ 30%FA ≥ Gypsum with ≥99 for Al and Fe except for Gypsum which attained ≥98 while the performance for Zn removal registered the following sequence, 97 ≥ 98 ≥ 88.8 ≥ 45% for CEM I ≥ Lime ≥30%FA ≥ Gypsum, respectively. Chemical species exist as divalent, trivalent, oxyanions, and other complexes in solution as predicted by PHREEQC. Moreover, they were removed as metal hydroxides, oxyhydrosulphates, and gypsum hence corroborating findings from XRD, SEM-EDS, and FTIR results. Mechanisms which were responsible for the removal of chemical species were precipitation, adsorption, co-adsorption, co-precipitation, ion exchange, and complexation. Henceforth, this study explicitly demonstrated mechanisms that underpin the removal of inorganic contaminants from AMD using PRB and findings from this study will be used to develop effective PRB for the management of acid mine drainage and the receiving environment.

Mining minerals and critical raw materials from bittern: Understanding metal ions fate in saltwork ponds.

Seawater represents a potential resource for raw materials extraction. Although NaCl is the most representative mineral extracted other valuable compounds such as Mg, Li, Sr, Rb and B and elements at trace level (Cs, Co, In, Sc, Ga and Ge) are also contained in this "liquid mine". Most of them are considered as Critical Raw Materials by the European Union. Solar saltworks, providing concentration factors of up-to 20 to 40, offer a perfect platform for the development of minerals and metal recovery schemes taking benefit of the concentration and purification achieved along the evaporation saltwork ponds. However, the geochemistry of these elements in this environment has not been yet thoroughly evaluated. Their knowledge could enable the deployment of technologies capable to achieve the recovery of valuable minerals. The high ionic strengths expected (0.5-7 mol/kg) and the chemical complexity of the solutions imply that only numerical geochemical codes, as PHREEQC, and the use of Pitzer model to estimate the activity coefficients of the different species in solution can be adopted to provide valuable description of the systems. In the present work, for the first time, PHREEQC Pitzer code database was extended to include the target minor and trace elements using Trapani saltworks (Sicily, Italy) as a case study system. The model was able to predict: i) the purity in halite and the major impurities contained, mainly Ca, Mg and sulphate species; ii) the fate of minor components as B, Sr, Cs, Co, Ge and Ga along the evaporation ponds. The results obtained pose a fundamental step in critical raw materials mining from seawater brine, for process intensification and combination with desalination.

Hydrocalumite as well as the Formation of Scheelite Induced by Its Dissolution, Removing Aqueous Tungsten with Varying Concentrations.

As a toxic element, tungsten (W) in elevated concentrations, originating from human activities or geological sources, poses a severe threat to the environment. However, there has been a lack of robust remediation techniques focusing on aqueous tungsten contamination with varying initial concentrations, because only recently have the toxicity and the environmental threat of tungsten been fully realized. In this study, the removal of tungsten from an aqueous solution by hydrocalumite was investigated for the first time. Systematic removal experiments were carried out at designated contact time, temperature, and initial tungsten concentration. The results showed that hydrocalumite is capable of effectively removing tungsten under various conditions, especially at high initial tungsten concentrations, with the maximum uptake capacity being up to 1120.5 mg (tungsten)/g (hydrocalumite). The mechanisms of tungsten removal were studied based on the measured chemical compositions of the solution samples and their PHREEQC simulations as well as the solid sample characterization by XRD, SEM-EDX, and XPS. At low initial tungsten concentrations (below 1 mmol/L), anion exchange between the tungsten in solution and the Cl in the hydrocalumite interlayers played a critical role in tungsten removal. At high initial tungsten concentrations (higher than 5 mmol/L), the removal of W from the solution was solely caused by the precipitation of scheelite (CaWO4), facilitated by the substantial release of Ca2+ from hydrocalumite dissolution. At moderate tungsten concentrations (1-5 mmol/L), however, both mechanisms were responsible for the uptake of tungsten, with scheelite precipitation being more important. Hydrocalumite is promising for wide use in the treatment of high-tungsten natural waters or wastewaters.

Delineating the origins and processes of groundwater salinization and quality degradation in a coastal irrigated plain, Korba (Northeastern Tunisia).

From 2006 to 2020, groundwater investigations were conducted in the Korba coastal aquifer in northern Tunisia along two flow paths (transects S1 and S2), perpendicular to the shoreline. Groundwater sampling, hydrodynamic monitoring, and electrical tomography imaging were performed in situ. Geochemical analysis (Ionic ratios, ionic deltas, conventional diagrams, and stable isotopes) and modelling using PHREEQC, and multivariate statistical analysis were applied. The objective was to identify the potential origin of groundwater salinization (i.e., high TDS and NO3) and to study associated processes. The groundwater flow inversion was corroborated by the piezometric survey in transect S1, where a piezometric depression of 5 m was detected at 4000 m from the seashore. Seawater intrusion and agricultural contamination, mainly through N-fertilizers, both contribute to groundwater mineralization and consequently salinization, according to PCA analysis. The impacted geochemical area of seawater intrusion was estimated to be 4000 and 1500 m, respectively, along transect S1 and transect S2. Inversely, agricultural contamination acts in internal areas beginning at 2000 m and 1500 m from the shoreline for S1 and S2, respectively. Results of different scenarios of inverse geochemical modelling along flow paths indicated that mixing, ion exchange, dissolution of gypsum, and precipitation of dolomite and calcite are the main processes controlling the groundwater composition in the coastal study area.