Fractionation of heavy metals and assessment of contamination of the sediments of Lake Titicaca

Chemical weathering is one of the major geochemical processes that control the mobilization of heavy metals. The present study provides the first report on heavy metal fractionation in sediments (8–156 m) of Lake Titicaca (3,820 m a.s.l.), which is shared by the Republic of Peru and the Plurinational State of Bolivia. Both contents of total Cu, Fe, Ni, Co, Mn, Cd, Pb, and Zn and also the fractionation of these heavy metals associated with four different fractions have been determined following the BCR scheme. The principal component analysis suggests that Co, Ni, and Cd can be attributed to natural sources related to the mineralized geological formations. Moreover, the sources of Cu, Fe, and Mn are effluents and wastes generated from mining activities, while Pb and Zn also suggest that their common source is associated to mining activities. According to the Risk Assessment Code, there is a moderate to high risk related to Zn, Pb, Cd, Mn, Co, and Ni mobilization and/or remobilization from the bottom sediment to the water column. Furthermore, the Geoaccumulation Index and the Enrichment Factor reveal that Zn, Pb, and Cd are enriched in the sediments. The results suggest that the effluents from various traditional mining waste sites in both countries are the main source of heavy metal contamination in the sediments of Lake Titicaca.     

Geochemical characterization of acid mine drainage from a waste rock pile, Mine Doyon, Québec, Canada

Water quality in the unsaturated and saturated zones of a waste rock pile containing sulphides was investigated. The main objectives of the project were (1) the evaluation of geochemical trends including the acid mine drainage (AMD)-buffering mechanism and the role of secondary minerals, and (2) the investigation of the use of stable isotopes for the interpretation of physical and geochemical processes in waste rock. Pore water in unsaturated zone was sampled from suction lysimeters and with piezometers in underlying saturated rocks. The investigation revealed strong temporal (dry period vs. recharge period), and spatial (slope vs. central region of pile) variability in the formation of acid mine drainage. The main secondary minerals observed were gypsum and jarosite. There was a higher concentration of gypsum in solid phase at Site TBT than at Site 6, suggesting that part of the gypsum formed at Site 6 in the early stage of AMD has been already dissolved. Formation of secondary minerals contributed to the formation of AMD by opening of foliation planes in waste rock, thus increasing the access of oxidants like O2 and Fe3+ to previously encapsulated pyrite. The behavior of several dissolved species such as Mg, Al, and Fe2+ can be considered as conservative in the leachate. Stable isotopes, deuterium and 18O, indicated internal evaporation within the pile, and were used to trace recharge pulses from snowmelt. Isotope trends for 34S and 18O(SO4) indicated a lack of sulfate reduction and zones of active oxidation of pyrite, respectively. Results of numerical modeling of pyrite oxidation and gas and water transport were consistent with geochemical and isotopic trends and confirmed zones of high evaporation rate within the rock pile close to the slope. The results indicate that physical and chemical processes within the pile are strongly coupled and cannot be considered separately when oxidation rates are high and influence gas transport as a result of heat generation.     

Geochemistry and pH control of seepage from Ni-Cu rich mine tailings at Selebi Phikwe,Botswana

Acid mine drainage from mine tailings at Selebi Phikwe, eastern Botswana, has been investigated using a combination of total decomposition, sequential extraction, X-ray diffraction, Mössbauer spectroscopy, and SEM analyses of solid phase samples, water analyses, isotopic analyses, and geochemical modeling. The principal ferric phases in the seepage stream sediments are jarosite and goethite, which incorporate Ni and Cu. The Mössbauer spectroscopy (MS) indicated exclusively 3+ oxidation state of iron with typical features of ferric hydroxides/sulfates. A fraction of dissolved sulfate is also sequestered in gypsum which precipitates further downstream. Significant portions of Fe, Ni, and Cu are transported in suspension. Values of pH decreased downstream due to H⁺ generated by the precipitation of jarosite. Values of δ²H and δ¹⁸O indicate evaporation of pore water in the mine tailings before seepage. Values of δ³⁴S(SO₄) are consistent with the oxidation of sulfides, but sample from the seepage face is affected by dissolution of gypsum. No minerals of Ni and Cu were detected and the principal attenuation processes seem to be adsorption and co-precipitation with jarosite. Higher contents of Cu are sequestered in solid phases compared to Ni, in spite of much higher dissolved Ni concentrations. Based on the speciation calculations, seepage water is undersaturated with respect to all Ni and Cu phases and adsorption and co-precipitation with jarosite seems to be the principal attenuation processes. Direct geochemical modeling was able to reproduce downstream pH trends, thus confirming the precipitation of jarosite as the principal pH-controlling process.     

Hydrogeochemical comparison and effects of overlapping redox zones on groundwater arsenic near the Western (Bhagirathi sub-basin, India) and Eastern (Meghna sub-basin, Bangladesh) margins of the Bengal Basin

Although arsenic (As) contamination of groundwater in the Bengal Basin has received wide attention over the past decade, comparative studies of hydrogeochemistry in geologically different sub-basins within the basin have been lacking. Groundwater samples were collected from sub-basins in the western margin (River Bhagirathi sub-basin, Nadia, India; 90 samples) and eastern margin (River Meghna sub-basin; Brahmanbaria, Bangladesh; 35 samples) of the Bengal Basin. Groundwater in the western site (Nadia) has mostly Ca-HCO(3) water while that in the eastern site (Brahmanbaria) is much more variable consisting of at least six different facies. The two sites show differences in major and minor solute trends indicating varying pathways of hydrogeochemical evolution However, both sites have similar reducing, postoxic environments (p(e): +5 to -2) with high concentrations of dissolved organic carbon, indicating dominantly metal-reducing processes and similarity in As mobilization mechanism. The trends of various redox-sensitive solutes (e.g. As, CH(4), Fe, Mn, NO(3)(-), NH(4)(+), SO(4)(2-)) indicate overlapping redox zones, leading to partial redox equilibrium conditions where As, once liberated from source minerals, would tend to remain in solution because of the complex interplay among the electron acceptors.     

Modelling of iron cycling and its impact on the electron balance at a petroleum hydrocarbon contaminated site in Hnevice, Czech Republic

Over a period of several decades multiple leaks of large volumes from storage facilities located near Hnevice (Czech Republic) have caused the underlying Quaternary aquifer to be severely contaminated with nonaqueous phase liquid (NAPL) petroleum hydrocarbons. Beginning in the late 1980's the NAPL plume started to shrink as a consequence of NAPL dissolution exceeding replenishment and due to active remediation. The subsurface was classified geochemically into four different zones, (i) a contaminant-free zone never occupied by NAPL or dissolved contaminants, (ii) a re-oxidation zone formerly occupied by NAPL, (iii) a zone currently occupied by NAPL, and (iv) a lower fringe zone between the overlying NAPL and the deeper underlying contaminant-free zone. The study investigated the spatial and temporal variability of the redox zonation at the Hnevice site and quantified the influence of iron-cycling on the overall electron balance. As a first step inverse geochemical modelling was carried out to identify possible reaction models and mass transfer processes. In a subsequent step, two-dimensional (forward) multi-component reactive transport modelling was performed to evaluate and quantify the major processes that control the geochemical evolution at the site. The study explains the observed enrichment of the lower fringe zone with ferrihydrite as a result of the re-oxidation of ferrous iron. It suggests that once the NAPL zone started to shrink the dissolution of previously formed siderite and FeS by oxygen and nitrate consumed a significant part of the oxidation capacity for a considerable time period and therefore limited the penetration of electron acceptors into the NAPL contaminated zone.     

Geochemistry of mine tailings and behavior of arsenic at Kombat,northeastern Namibia

The mine tailings at Kombat, in semiarid northeastern Namibia, were investigated by the combination of solid-phase analyses, mineralogical methods, leaching tests, and speciation modeling. Dissolution of the most abundant primary sulfides, chalcopyrite and galena, released copper and lead which were adsorbed onto ferric oxyhydroxides or precipitated in the form of malachite, Cu₂CO₃(OH)₂, and cerussite, PbCO₃, respectively. Arsenic released from arsenopyrite was incorporated into ferric oxyhydroxides. Based on sequential extraction and ⁵⁷Fe Mössbauer spectroscopy, a large amount of ferric iron is present as low solubility hematite and goethite formed rapidly (<10 years) under warm semiarid climatic conditions, and arsenic in these phases is relatively tightly bound. It seems that Cu and especially Pb in carbonate minerals represent a more serious environmental risk. Immobilization of As in hematite has implications for other mining sites in regions with similar climatic conditions because this process results in long-term immobilization of As.     

Evaluation of the impacts of mine drainage from a coal waste pile on the surrounding environment at Smolnica, southern Poland

Mine drainage impacts from a coal waste pile at Smolnica, Poland have been monitored. Groundwater in an unconfined aquifer downgradient from the pile has near-neutral pH, but high concentrations of sulfate (up to 3,827 mg/l), chloride (up to 903 mg/l), and sodium (up to 2,606 mg/l). Concentrations of iron and manganese are elevated only locally, and concentrations of other metals are low. The behavior of sulfate seems to be conservative in the downgradient aquifer, and gypsum may only be precipitating locally. Concentrations of iron and manganese seem to be controlled by the precipitation of ferric oxide and hydroxides and rhodochrosite, respectively. Complete neutralization of mine drainage by carbonates is consistent with high concentrations of calcium (up to 470 mg/l) and magnesium (up to 563 mg/l) and also with high strontium concentrations of up to 3.08 mg/l, observed in groundwater downgradient from the pile. Hydraulic head profiles at two sites within the river bottom sediments indicate upward flow toward the river with large local differences in groundwater recharge. Water chemistry profiles in the river bottom sediments and geochemical modeling suggest conservative behavior of Na, Cl, and SO₄ and precipitation of Fe and Mn at the groundwater/river water interface. Mine drainage enters the Bierawka River and causes increasing sulfate concentrations. In contrast, concentrations of sodium and chloride in the Bierawka River decrease downgradient from the pile because water in the river upgradient from the pile is already highly contaminated by these species from the discharge of mining waters. Concentrations of Fe and Mn in the river water are low, as a consequence of the precipitation of Fe and Mn oxide and hydroxides. Direct geochemical modeling was able to reproduce measured concentrations of conservative species (e.g., Na, Cl, and SO₄), but errors for metals and Ba were relatively large. In addition, calculated P_CO2 values in the river water are very high, suggesting that equilibrium with atmospheric P_CO2 and P_O2 has not been reached, and at least some reactions should be modeled as kinetic processes. High concentrations of Na, Cl, and SO₄ contribute to the contamination of the Odra River, which is joined by the Bierawka River farther downgradient, thus limiting the use of river water for recreation and other purposes.     

Attenuation of dissolved metals in neutral mine drainage in the Zambian Copperbelt

Behaviour of metals like Cu and Co was studied in nearly neutral (pH ?? 6.4) mine drainage seepage in a stream downgradient of a tailing dam at Chambishi site in the Copperbelt of Zambia. They are attenuated by precipitation of ferruginous ochres that incorporate significant quantities of metals. Using chemical analysis, X-ray powder diffraction and M?ssbauer spectroscopy, we show that the ochres are composed mostly of amorphous ferric hydroxide. Close to the seepage face, the total Fe content of ochres increases due to precipitation of amorphous ferric hydroxide, but total Fe in sediment decreases further downstream. The stream then flows through wetland (dambo) where the remaining fraction of metals is removed. During rainy periods, increased flow rate may result in re-suspension of ochres, increasing thus the mobility of metals. Major ions like sulphate are conservative at the start of the dry period (May), but gypsum may probably precipitate later at the end of the dry period. Sequential extractions of bulk sediments indicate that Mn behaves differently to Fe, with a trend of increasing Mn with distance from the tailing dam. There is much more Fe than Mn in residual (Aqua Regia) fraction, indicating that amorphous ferric hydroxides are transformed to more crystalline phases deeper in sediment. Environmental impact of mine drainage is relatively limited due to its neutral character.