Distribution and speciation of metals,phosphorus, sulfate and organic material in brackish estuary water affected by acid sulfate soils

Dissolved (<1 kDa) and colloidal (1 kDa-0.45 μm) size fractions of sulfate, organic carbon (OC), phosphate and 17 metals/metalloids were investigated in the acidic Vörå River and its estuary in Western Finland. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these waters. The sampling was carried out during high-water flow in autumn and in spring when the abundantly occurring acid sulfate (AS) soils in the catchment area are extensively flushed. Based on the high concentrations of sulfate, acidity and several metals, it is clear that the Vörå River and its estuary is strongly affected by AS soils. The high dissolved form of metals limits also the existence of fish and other organisms in this estuary, and certainly also in other similar shallow brackish estuaries elsewhere in the Gulf of Bothnia. However, generally already <20% saline sea water reduces the concentration for OC and several elements (Al, Cu, Cr, Fe, Pb, PO₄ and U) by half and c. 20–30% saline sea water is needed to halve concentrations of Cd, Co, Mn, Ni and Zn. Consequently, these elements as well as organic matters were rapidly precipitated in the estuary, even after mixing with fairly small amounts of the alkaline brackish sea water. Aluminium, Cu, Fe and U most likely precipitate together with organic matter closest to the river mouth. Manganese is relatively persistent in solution and, thus, precipitates further down the estuary as Mn oxides, which concomitantly capture Ba, Cd, Co, Cu, Ni and Zn. In the inner estuary, the high contents of Al is as important than Fe in removing PO₄ and, thus, also reducing the risk of algae blooms in near coastal areas influenced by AS soils in the Gulf of Bothnia. Moreover, the dispersion of metals far out in the estuary is dependent on hydrological conditions, i.e. with high flows the plume of metal-rich water will spread further out in the estuary. Furthermore, the extensive drainage of the catchment and subsequent artificial enlargement of the river channel during recent decades has not only enabled oxidation of sulfidic sediments, but strongly increased flow peaks that reach further out in the estuary.     

Effectiveness of various dispersed alkaline substrates for the pre-treatment of ferriferous acid mine drainage

Dispersed alkaline substrates (DAS) have been successfully used in passive treatment of highly contaminated acid mine drainage (AMD) to limit coating and clogging issues. However, further optimization of DAS systems is still needed, especially for their long-term efficiency during the treatment of ferriferous AMD. In the present study, three types of DAS comprised of natural alkaline materials (wood ash, calcite, dolomite), in different proportions (20%v/v, 50%v/v, 80%v/v), and a substrate with high surface area (wood chips) were tested in 9 batch reactors. The testing was carried out, in duplicate, for a period of 91 days, to evaluate the comparative performance of the mixtures for iron pre-treatment in ferriferous AMD (2500 mg/L Fe, at pH 4). Results showed increasing of pH (between 4.15 and 7.12), regardless of the proportion of alkaline materials in the DAS mixtures. Among the tested mixtures, wood ash type DAS were more effective for Fe removal (99.9%) than calcite or dolomite type DAS (up to 66%). All tested DAS had limited efficiency for sulfate removal and an additional treatment unit, such as a sulfate-reducing biochemical reactor, is needed. Moreover, due to the similar performances of the calcite and dolomite DAS, they could be potentially substituted and rather be used in a polishing treatment unit. Based on these findings, the most promising mixture was the 50% wood ash type DAS (WA50-DAS).     

Mineralogical and geochemical characterization of the Old Tailings Dam,Australia: Evaluating the effectiveness of a water cover for long-term AMD control

Establishing a shallow water cover over tailings deposited in a designated storage facility is one option to limit oxygen diffusion and retard oxidation of sulfides which have the potential to form acid mine drainage (AMD). The Old Tailings Dam (OTD) located at the Savage River mine, western Tasmania contains 38 million tonnes of pyritic tailings deposited from 1967 to 1982, and is actively generating AMD. The OTD was constructed on a natural gradient, resulting in sub-aerial exposure of the southern area, with the northern area under a natural water cover. This physical contrast allowed for the examination of tailings mineralogy and geochemistry as a function of water cover depth across the OTD. Tailings samples (n = 144, depth: ≤ 1.5 m) were collected and subjected to a range of geochemical and mineralogical evaluations. Tailings from the southern and northern extents of the OTD showed similar AMD potential based on geochemical (NAG pH range: 2.1 to 4.2) and bulk mineralogical parameters, particularly at depth. However, sulfide alteration index (SAI) assessments highlighted the microscale contrast in oxidation. In the sub-aerial zone pyrite grains are moderately oxidized to a depth of 0.3 m (maximum SAI of 6/10), under both gravel fill and oxidized covers, with secondary minerals (e.g., ferrihydrite and goethite) developed along rims and fractures. Beneath this, mildly oxidized pyrite is seen in fresh tailings (SAI = 2.9/10 to 5.8/10). In the sub-aqueous zone, the degree of pyrite oxidation demonstrates a direct relationship with cover depth, with unoxidized, potentially reactive tailings identified from 2.5 m, directly beneath an organic-rich sediment layer (SAI = 0 to 1/10). These findings are broadly similar to other tailings storage facilities e.g., Fox Lake, Sherritt-Gordon ZnCu mine, Canada and Stekenjokk mine, Sweden where water covers up to 2 m have successfully reduced AMD. Whilst geotechnical properties of the OTD restrict the extension of the water cover, pyrite is enriched in cobalt (up to 2.6 wt%) indicating reprocessing of tailings as an alternative management option. Through adoption of an integrated mineralogical and geochemical characterization approach for tailings assessment robust management strategies after mine closure can be developed.     

Iron isotopes in acid mine waters and iron-rich solids from the Tinto–Odiel Basin (Iberian Pyrite Belt, Southwest Spain)

The isotopic composition of Fe was determined in water, Fe-oxides and sulfides from the Tinto and Odiel Basins (South West Spain). As a consequence of sulfide oxidation in mine tailings both rivers are acidic (1.45 < pH < 3.85) and display high concentrations of dissolved Fe (up to 420 mmol l^− 1) and sulphates (up to 1190 mmol l^− 1).The δ⁵⁶Fe of pyrite-rich samples from the Rio Tinto and from the Tharsis mine ranged from − 0.56 ± 0.08‰ to + 0.25 ± 0.1‰. δ⁵⁶Fe values for Fe-oxides precipitates that currently form in the riverbed varied from − 1.98 ± 0.10‰ to 1.57 ± 0.08‰. Comparatively narrower ranges of values (− 0.18 ± 0.08‰ and + 0.21 ± 0.14‰) were observed in their fossil analogues from the Pliocene–Pleistocene and in samples from the Gossan (the oxidized layer that formed through exposure to oxygen of the massive sulfide deposits) (− 0.36 ± 0.12‰ to 0.82 ± 0.07‰). In water, δ⁵⁶Fe values ranged from − 1.76 ± 0.10‰ to + 0.43 ± 0.05‰.At the source of the Tinto River, fractionation between aqueous Fe(III) and pyrite from the tailings was less than would be expected from a simple pyrite oxidation process. Similarly, the isotopic composition of Gossan oxides and that of pyrite was different from what would be expected from pyrite oxidation. In rivers, the precipitation of Fe-oxides (mainly jarosite and schwertmannite and lesser amounts of goethite) from water containing mainly (more than 99%) Fe(III) with concentrations up to 372 mmol l^− 1 causes variable fractionation between the solid and the aqueous phase (− 0.98‰ < Δ⁵⁶Fe_{solid–water} < 2.25‰). The significant magnitude of the positive fractionation factor observed in several Fe(III) dominated water may be related to the precipitation of Fe(III) sulphates containing phases.     

Remediation of a major acid mine drainage point source discharge restores headwater connectivity for a diadromous native fish

Rivers receiving acid mine drainage (AMD) are frequently depauperate in fish and impacts may extend long distances downstream. AMD inputs may form chemical barriers for migratory species and isolate fish in unimpacted headwaters. We investigated the response of a diadromous fish, kōaro (Galaxias brevipinnis), to remediation of an AMD tributary in a 5th order river in New Zealand. A 2005 survey indicated limited recruitment of kōaro in the river likely due to the chemical barrier of AMD. By 2010, water treatment in the contaminated tributary had raised pH from a median value of 4.3 to 6 and reduced metals in the lower river, notably aluminium from a median of 2.48 to 0.41?mg/L. In 2012, kōaro density had increased by an order of magnitude relative to 2005. Furthermore, a greater proportion of juvenile fish were present. These results indicate that large-scale remediation of discharges can reverse the impacts of AMD on fish migration.     

湖南土壤生态系统对酸沉降的相对敏感性区划

以成土母质、土壤酸碱度、土壤类型、植被类型和湿度类型等5个生境因子为基础,建立湖南土壤生态系统对酸沉降的相对敏感性评价指标体系;利用地理信息系统(GIS)工具进行湖南土壤生态系统对酸沉降的相对敏感性区划,结果表明,湖南省可以划分为极敏感区、敏感区、中等敏感区、不敏感区和极不敏感区等5个酸相对敏感性分区,分别占湖南省总面积的2.15%、30.02%、55.01%、10.56%和2.26%.     

Precambrian Acid Volcanism in Central India - Geochemistry and Origin

The Early Proterozoic Bijli rhyolites (2180 ± 25 Ma) constitute an important part of the Nandgaon group in the Central Indian craton, a tectonically active block sandwiched between the Dharwar craton in the south and the Bundelkhand craton in the north. The rhyolites are chemically heterogeneous. They have high SiO₂ (74.4%), K₂O (4.41%), Ba (834 ppm), and low MgO (0.22%), CaO (1.0%), iron (2.8%) V, Cr and Ni (5, 6 and 1 ppm respectively). They contain moderate Sr (88 ppm), Rb (140 ppm), Th (27 ppm) and U (6 ppm). Total REE ranges from 223 ppm to 453 ppm with high LREE (ΣLREE = 307) and all the rhyolites have low to high negative europium anomalies (Eu/Eu* 0.03 to 0.77). The overall chemical signatures support a crustal anatectic origin for the rhyolites from a source of intermediate composition. Basalt pooling below the crust and associated rifting most likely initiated anatexis.     

A review of the Study of Hydrogen Peroxide in Seawater

Hydrogen peroxide can oxidize or reduce a number of biological important trance metals in seawater. Therefore, it can indirectly affect the marine ecosystem by causing the changes in the speciation of these metals. The results of researches about hydrogen peroxide in seawater in the last more than thirty years were reviewed and the direction of study in the further was proposed in this paper. Hydrogen peroxide can be found rather ubiquitously in the upper water at concentration of 0~102 nmol/L. In water column the maximum of the concentrations of hydrogen peroxide presents in surface water and the concentrations decrease with the increase of depth. In general, the concentrations in costal seawater are higher than these in the oligotrophic ocean. Diel variation of hydrogen peroxide occurs in seawater: the concentrations increase since sunup until the mixmum of afternoon and decrease until the minimum at drawn. The sources of hydrogen peroxide in marine environment include photochemical production, atmospheric deposition and biological production, and the photochemical production is primary among them. The sinks of hydrogen peroxide in the ocean consist of biological and chemical and photochemical decomposition and the main one is biological decomposition. The biogeochemistry of hydrogen peroxide in the continental shelf influenced by river water and factors affecting photochemical production and detail of decomposition should be studied in the future.     

云南兰坪高含泥低品位氧化铜矿选矿试验

原矿为高含泥高氧化率低品位铜矿。根据矿石的工艺矿物学特性,开展“直接浮选”、“预先脱泥＋浮选”和“酸浸”三种工艺流程试验。试验结果表明,“酸浸”是最佳的提铜工艺流程。在较佳的酸浸工艺条件下,可获得铜浸出率92．09％,硫酸耗量54kg／T的技术经济指标。     

Interaction of acid mine drainage with waters and sediments at the Corona stream, Lousal mine (Iberian Pyrite Belt, Southern Portugal)

This study investigates the geochemical characteristics of the acid mine drainage discharged from the abandoned mine adits and tailing piles in the vicinity of the Lousal mine and evaluates the extent of pollution on water and on the stream sediments of the Corona stream. Atmospheric precipitation interacting with sulphide minerals in exposed tailings produces runoff water with pH values as low as 1.9–2.9 and high concentrations of (9,249–20,700 mg l⁻¹), Fe (959–4,830 mg l⁻¹) and Al (136–624 mg l⁻¹). The acidic effluents and mixed stream water carry elevated Cu, Pb, Zn, Cd and As concentrations that exceed the water quality standards. However, the severity of contamination generally decreases 4 km downstream of the source due to mixing with fresh waters, which causes the dilution of dissolved toxic metals and neutralization of acidity. Some natural attenuation of the contaminants also occurs due to the general reduced solubility of most trace metals, which may be removed from solution, by either co-precipitation or adsorption to the iron and aluminium precipitates.