Geochemical Transactions最新文献

Acid generation and metal(loid) release are growing considerations for oil sands mine closure in northern Alberta, Canada. Oxidative weathering of pyrite-bearing froth treatment tailings (FTT) has potential to promote acid generation and metal(loid) release. However, the acid-neutralization reactions and their influence on pore-water pH and metal(loid) mobility have not yet been reported. Laboratory column experiments examined acid-neutralization reactions and metal(loid) release for variably weathered (i.e., non-weathered, partially weathered, highly weathered) FTT samples collected from a commercial-scale beach deposit. Solvent-washed and non-solvent-washed splits of each sample were included to assess the influence of residual hydrocarbons. Acidic influent (i.e., 0.05 M H₂SO₄; pH ~ 1.5) was continuously pumped through each column, and effluent samples were collected for geochemical analysis over time. Effluent pH decreased from ~ 7.0 to 5.5 over the first 5 pore volumes for the non-weathered and partially weathered columns, while gradual pH decreases to ~ 4.5 were observed over the following 30 to 70 pore volumes. Subsequent decreases in effluent pH from ~ 4.5 to < 3.0 occurred over the next 2 to 5 pore volumes for these columns. In contrast, effluent pH consistently remained below 2.0 for the highly weathered columns. We attribute these effluent pH trends to the dissolution of Ca- and Mg-bearing carbonates (pH ~ 6.5 to 6), Fe-bearing carbonates (pH ~ 5.6 to 4.5), Al (oxy)hydroxides (pH ~ 4.5 to 4.0), and silicates (pH < ~ 2). Corresponding increases in effluent concentrations of Fe (< 1 to > 500 mg L^− 1), Al (< 0.1 to > 10 mg L^− 1), Si (< 0.1 to > 10 mg L^− 1), and additional metal(loid)s (e.g., Ni, Zn, V, As) were observed with decreasing pH. Cumulative mass releases (e.g., Ca, Mg, Fe) were greatest for the non-weathered samples and solvent-washed splits. These results offer new insights into relationships between acid neutralization reactions and metal(loid) release that can inform FTT management and reclamation.

Perfluorooctane sulfonate (PFOS) is an emerging contaminant frequently detected in subsurface environments, raising significant concern due to its environmental persistence, mobility, and potential human health impacts. This study examines PFOS adsorption onto a range of solid substrates, including pure minerals, mineral assemblages, and natural soils. Specifically, the adsorption behavior of 2-line ferrihydrite, ferrihydrite-coated sand, and soil collected from a PFOS-impacted site in Killingworth, Connecticut was investigated to evaluate their capacity to retain PFOS under varying geochemical conditions. By integrating batch adsorption experiments with surface complexation modeling (SCM) and applying the component additivity approach, this study elucidates the reactive transport mechanisms governing PFOS behavior under a range of geochemical conditions. Our findings demonstrate that PFOS adsorption occurs significantly on both ferrihydrite and quartz surfaces, with the ferrihydrite-coated sand and soil exhibiting retention behavior attributable to contributions from both mineral phases. At lower pH values, sorption is predominantly governed by outer-sphere complexation driven by the surface charge characteristics of ferrihydrite. Specifically, under acidic conditions (pH < 5.5 for ferrihydrite-coated sand and pH < 6.0 for soil), PFOS retention is primarily facilitated through an outer-sphere hydrogen-bonded complex at ferrihydrite’s surface, while a secondary outer-sphere complex involving Na⁺ co-adsorption contributes to a lesser extent. At elevated pH levels, however, electrostatic interactions become less favorable, and non-electrostatic hydrophobic interactions with quartz surfaces become increasingly dominant, highlighting the transition in sorption mechanisms from charge-driven to hydrophobic partitioning under neutral to alkaline conditions. A comparison with traditional partitioning coefficients (K_d) revealed that their variability closely corresponds with changes in dominant surface complexes across different pH conditions. Given the critical role of solid-phase partitioning in governing PFAS transport in the subsurface, enhanced predictive capabilities are essential for advancing site-specific risk assessments and informing management strategies aimed at protecting both public and private water resources.

Graphical abstract

Bitumen extraction from mined oil sands ore generates a large volume of fluid fines tailings (FFT) that must be incorporated into either aquatic or terrestrial reclamation landforms. Mine operators are developing various tailings technologies to accelerate FFT dewatering, including the addition of chemical coagulants and flocculants. However, the impacts of these coagulants and flocculants on biogeochemical processes in treated FFT are not fully understood. We conducted anaerobic batch experiments to examine the influence of different doses (i.e., 0, 500, 1000, and 1500 ppm) of sulfate-based coagulants, including aluminum sulfate (alum) [Al₂(SO₄)₃∙nH₂O], ferric sulfate (ferric) [Fe₂(SO₄)₃∙nH₂O], and calcium sulfate (gypsum) [CaSO₄∙2H₂O], on biogenic gas production and microbial communities in treated FFT. Our results show that sulfate addition stimulated microbial sulfate reduction, which inhibited methanogenesis in coagulated FFT relative to experimental controls. Sulfate depletion preceded increased methane production in the 500 ppm gypsum experiment, while larger ferric and alum doses produced higher sulfate concentrations and larger pH decreases. 16 S rRNA sequencing revealed that Comamonadaceae, Anaerolineaceae, and Desulfocapsaceae were the major bacterial families, while Methanoregulaceae and Methanosaetaceae dominated the archaeal families in all treatments. Precipitation of iron(II) sulfides limited dissolved hydrogen sulfide concentrations in experiments where Fe availability was not limited. Our results indicate that addition of sulfate-based coagulants can stimulate microbial sulfate reduction and suppress methanogenesis. However, resumption of methane production following sulfate depletion reveals complex interactions among biogeochemical reaction pathways. Overall, this study demonstrates that biogeochemical cycling of carbon, sulfur, and iron are important considerations for the development and implementation of tailings treatment technologies.

The present research work aims to understand the geochemistry of groundwater resources of the Yamuna—Hindon interfluve region of Bagpat district, Western Uttar Pradesh, India. The region is a part of Indo-Gangetic belt, one of the world's most fertile and intensely farmed areas. To investigate the geochemical processes governing groundwater quality, a total of 105 groundwater samples were collected during pre-monsoon season and analyzed for various physico-chemical parameters, namely, pH, electrical conductivity (EC), total dissolved solid (TDS), total hardness (TH), turbidity, major anions (HCO₃⁻, SO₄²⁻, F⁻, Cl⁻, NO₃⁻)_, cations (Ca²⁺, Mg²⁺, Na⁺, K⁺) following the methods outlined in the American Public Health Association (APHA). The dissolved heavy metals (Fe, Mn, Zn, Pb, Cu, Cr, Ni, As, Se, Co, Cd and Al) in groundwater were analyzed by ICP-MS following the instrument manual. The analysis results revealed that the groundwater is pre-dominantly neutral to mildly alkaline in nature. The major cation chemistry majorly followed the occurrence pattern of Na⁺ > Mg²⁺ > Ca²⁺ > K⁺, while for anions it was HCO₃⁻ > Cl⁻ > SO₄²⁻ > NO₃⁻ > F⁻. The data plotted on Piper triangular diagram indicated that Ca²⁺-Mg²⁺-HCO₃⁻ and Na⁺-K⁺-HCO₃⁻-Cl⁻ were major hydrogeochemical facies. Weathering of rock-forming minerals mainly governed the groundwater geochemistry in this region, although part of the cations associated with Cl⁻, F⁻ and NO₃⁻ may originate from anthropogenic sources. TDS, TH, turbidity and F⁻ were identified as the major parameters that violated the prescribed limits for drinking water. Most of the heavy metals were found within the drinking water prescribed limits except for Fe, Mn, Al and Se. Elevated salinity, %Na, and magnesium hazard (MH) at certain sites limit its suitability for agricultural use. The assessment of selected organochlorine and organophosphorus pesticides in five samples indicated presence of lindane, β-endosulfan and DDT isomers in few samples. However, a detailed investigation of possible pesticide contamination in this intensive agriculture area is required before drawing any final conclusions.

This study presents the first kinetic model to predict the solid and pore solution composition of Na-bentonite clay reacting with slaked lime over a period of 720 days. The model successfully accounts for most experimental data using a single kinetic rate constant. The following sequence of reactions was predicted by the model: initial rapid dissolution of portlandite within the first 7 days, leading to a decrease in pH and dissolved calcium, and concurrent formation of calcium silicate hydrates (C-S-H: jennite), calcium aluminate hydrate (C-A-H: C₄AH₁₃), calcium aluminosilicate hydrates (stratlingite) and hydrotalcite. After 7 days, jennite and stratlingite are predicted to transform into tobermorite-II, contributing to strength development up to 28 days. From 28 to 90 days, continued montmorillonite dissolution is predicted, along with minor formation of ettringite, partial tobermorite-II dissolution, and precipitation of secondary phases such as albite and talc. Experimentally, portlandite dissolution was confirmed by TGA and XRD and found to be complete within 7 days, in agreement with model predictions. However, other predicted solid-phase transformations (e.g., tobermorite-II formation and dissolution, ettringite, albite, and talc formation) could not be conclusively verified through experimental techniques. Aqueous phase measurements confirmed that the pH and Ca trends in solution, and that equilibrium was reached by 90 days.

Groundwater resources in mica mining areas of Jharkhand are vital for local communities, agriculture, and domestic utilization. The study investigates the major ion chemistry of groundwater in the mica mining regions, focusing on key physicochemical parameters such as pH, electrical conductivity (EC), total dissolved solids (TDS), and concentrations of major cations (Ca²⁺, Mg²⁺, Na⁺, K⁺) and anions (HCO₃⁻, Cl⁻, SO₄²⁻, NO₃⁻, F⁻). Groundwater samples from the study area were collected before the monsoon season, during the monsoon season, and after the monsoon season. The hydro-chemical analysis reveals that groundwater in the mica mining zones exhibits elevated levels of dissolved ions, with NO₃⁻, F⁻, Ca²⁺, Mg²⁺ and total hardness exceeding permissible limits set by Bureau of Indian Standards (BIS) for drinking purposes at some locations. Water Quality Index (WQI) assessments suggest that a significant proportion of groundwater samples fall into the “good” to “very good” category for drinking and about 29% of the samples fall under the “poor” category. The groundwater was generally suitable for irrigational use with exception of a few due to high salinity. The principal component analysis revealed rock weathering as a dominant source of ions along with anthropogenic sources like mining and agriculture contributing minorly to the ionic load. The predominant hydro-chemical facies identified were Ca-Mg-HCO₃ and Ca-Mg-Cl-SO₄ types. Both carbonate and silicate weathering play an important role in the geochemical signature of the groundwater in the area. The study implicates the potential health impacts of using the groundwater as drinking water without treatment at a few locations owing to high fluoride, nitrate and dissolved solids. The study also highlights the need for sustainable water management practices and regular monitoring of groundwater quality to mitigate the anthropogenic impacts on groundwater resources.

This study investigates the trace element concentrations in the surface waters of four north-joining Himalayan tributaries of the Ganga river (Ramganga, Ghaghara, Gandak, and Kosi), highlighting the combined effects of geogenic processes and anthropogenic activities on trace element chemistry and water quality. A knowledge gap exists in understanding the sources of trace elements in these tributaries and the contribution of trace elements from these tributaries to the Gangariver. The novelty of the study lies in its assessment of sources, human health risks, and ecological impacts. The investigation was conducted by assessing trace element concentrations and comparing them with national and international standards. Various human health and ecological risk indicators, including the Heavy Metal Pollution Index (HPI), Hazard Quotient (HQ), Health Index (HI), Chronic Daily Intake (CDI), and the Potential Ecological Risk Index (PERI), were applied. The results reveal high concentrations of copper (Cu), zinc (Zn) and lead (Pb) in the Ramganga, indicating contamination from industrial activities in the catchment. Although most trace element concentrations are within safe limits, Pb concentration in the Ramganga exceeds the limit prescribed by WHO. The Ramganga shows the highest health risks, with a HI_total of 1.876 for adults and 1.616 for children. In contrast, the Ghaghara, Gandak, and Kosi exhibit lower but moderate contamination levels. HPI values for these rivers- 93.74 for the Ghaghara, 83.95 for the Kosi, 83.13 for the Gandak, and 80.43 for the Ramganga—indicate that although contamination is below critical thresholds, targeted mitigation strategies are needed. The findings provide valuable insights into trace metal sources and their implications for human health and ecological risks, and emphasize the need for frequent monitoring and pollution control measures for maintaining sustainable water quality in these tributaries.

The quality of water can significantly affect the regional water resources due to scarcity of potable water in industrial area. The purpose of this study was to explore potentially toxic trace elements (PTEs) contamination and their seasonal variations in different water sources within the coal mining area of the Mahan River command area, Central India. To achieve this, 96 water samples were collected across two distinct seasons and analysed for PTEs. The results indicate that during the pre-monsoon season, the concentrations of Mn (18%), Cu (4%), Pb (8%), Ni (18%), Cd (2%), Al (4%), Cr (2%), and Fe (30%) exceeded permissible limits. In the post-monsoon season, Mn (15%), Pb (6%), Ni (15%), Cd (2%), Al (15%), Fe (46%) and Ba (4%) surpassed the standards. The multiple groundwater pollution indexical methods further revealed that 14% [Heavy metal pollution index (HPI)], 14% [Heavy metal evaluation index (HEI)], 18% [Contamination index (CI)], 14% [the entropy-weight based HM contamination index (EHCI)] and 20% [Heavy metal index (HMI)] of the samples exceeded permissible thresholds during the pre-monsoon season. Similarly, during the post-monsoon period, 10% (HPI), 10% (HEI), 15% (CI), 15% (EHCI) and 17% (HMI) of the samples were above acceptable limits. The relationship between the pH of water and the total load of dissolved metals is established using Caboi plot, confirming that mine water from mine water from Bhatgaon Underground (UG), Mahamaya UG, and Mahan Opencast (OC) [PR40, PR41, PR42, PR43, PR47, and PR48], surrounding rivers, and groundwater sources, exhibited an “Acid-High Metal” characteristic. This suggests significant contamination from acid mine drainage and mineral dissolution. Apart from the anthropogenic inputs, geogenic and environmental processes are responsible for the current distribution of PTEs and their seasonal variations.

In anoxic subsurface environments, low Fe(III) bioaccessibility greatly limits in situ biodegradation of petroleum hydrocarbons (PHCs). Ferric ammonium citrate is a soluble compound that has the potential to increase the bioaccessibility of Fe(III). However, in neutral to alkaline environments, Fe(III) hydrolysis can produce Fe(III) (oxyhydr)oxides that may subsequently transform or recrystallize to relatively stable and less bioaccessible phases. Accordingly, the objective of this study was to elucidate the transformation and fate of Fe(III) contributed by ferric ammonium citrate in a gasoline-contaminated subsurface environment that was undergoing in situ bioremediation. Ferric ammonium citrate, together with sodium tripolyphosphate, magnesium sulphate, and nitric acid, was continuously injected into the contaminated groundwater for about 22 weeks. Colloids in the groundwater (solid particles retained on a 0.45 (upmu)m filter) and soil cores were collected from the site. Fe speciation in these samples was characterized using X-ray absorption near edge structure (XANES) and Fourier transform infrared (FTIR) spectroscopy. The groundwater colloids (GWCs) contained mostly octahedrally coordinated Fe(III), but the subsoils contained both octahedrally coordinated Fe(III) and Fe(II). The fraction of Fe(II) in the subsoils generally increased after about 22 weeks of continuous amendment injection. Ferric ammonium citrate did not persist in the PHC-contaminated subsurface: the Fe(III) it contained was transformed to solid phases. Fe(III)-organic-matter (Fe(III)-OM) complex/coprecipitate and sulfate green rust were the major phases present in the GWCs; akaganeite, chloride green rust, vivianite, ferrihydrite, Fe(III)-silicate, and magnetite were present as minor phases. The subsoils contained three major phases: Fe(III)-OM complex/coprecipitate, magnetite, and calcium ferric silicate. The presence of major Fe(II) phases in the subsoils strongly indicate that secondary Fe(III) phases (especially Fe(III)-OM complex/coprecipitate) served as terminal electron acceptors during the microbial degradation of PHCs in the contaminated subsurface.