Characterization of water reservoirs affected by acid mine drainage: geochemical,mineralogical, and biological (diatoms) properties of the water

This work presents a combination of geochemical, mineralogical, and biological data obtained in water reservoirs located in one of the most paradigmatic mining regions, suffering from acid mine drainage (AMD) problems: the Iberian Pyrite Belt (IPB). Four water reservoirs located in the Spanish sector of the IBP, storing water for different purposes, were selected to achieve an environmental classification based on the effects of AMD: two mining dams (Gossan and Águas Ácidas), a reservoir for industrial use (Sancho), and one with water used for human supply (Andévalo). The results indicated that the four reservoirs are subject to the effect of metallic loads from polluted rivers, although with different levels: Águas Ácidas > Gossan > Sancho ≥ Andévalo. In accordance, epipsammic diatom communities have differences in the respective composition and dominant taxa. The dominant diatoms in each reservoir indicated acid water: Pinnularia acidophila and Pinnularia aljustrelica were found in the most acidic dams (Gossan and Águas Ácidas, with pH <3), Pinnularia subcapitata in Sancho (pH 2.48–5.82), and Eunotia exigua in Andévalo (pH 2.34–6.15).     

Geochemical behavior of metals and metalloids in an estuary affected by acid mine drainage (AMD)

The Tinto and Odiel rivers in southwest Spain drain the world’s largest sulfide mineral formation: the Iberian Pyrite Belt which has been worked since 2,500 BC. The Tinto and Odiel estuarine zones include both an extensive area of salt marsh and an intensively industrialized urban area. As a consequence of pyrite oxidation, the Tinto and Odiel rivers are strongly acidic (pH?<?3) with unusually high and quite variable metal concentrations. In this study, seasonally varying concentrations of dissolved major and trace elements were determined in the acid mine drainage affected estuary of the Ría de Huelva. During estuarine mixing, ore-derived metal concentrations exhibit excellent correlations with pH as the main controlling parameter. As pH increases, concentrations of dissolved ore-associated elements are attenuated, and this process is enhanced during the summer months. The decrease in Fe and Al concentrations ranged from 80 to 100 % as these elements are converted from dissolved to sediment-associated forms in the estuary. Coprecipitation/adsorption processes also removed between 60 and 90 % of the originally dissolved Co, Cu, Mn, Pb, Zn, and Th; however, Cd and Ni exhibited a greater propensity to remain in solution, with an average removal of approximately 60 %. On the other hand, As and U exhibited a different behavior; it is likely that these elements remain in dissolved forms because of the formation of U carbonates and soluble As species. Concentrations of As remain at elevated levels in the outer estuary (average?=?48 μg L^?1) which exceeds concentrations present in the Tinto River. Nevertheless, the estuary has recently witnessed improvements in water quality, as compared to results of several previous studies reported in the 1990s.     

Distribution of rare earth elements in an alluvial aquifer affected by acid mine drainage: the Guadiamar aquifer (SW Spain)

This work analyses the spatial distribution, the origin, and the shale-normalised fractionation patterns of the rare earth elements (REE) in the alluvial aquifer of the Guadiamar River (south-western Spain). This river received notoriety in April 1998 for a spill that spread a great amount of slurry (mainly pyrites) and acid waters in a narrow strip along the river course. Groundwaters and surface waters were sampled to analyse, among other elements, the REEs. Their spatial distribution shows a peak close to the mining region, in an area with low values of pH and high concentrations of sulphates and other metals such as Zn, Cu, Co, Ni, Pb, and Cd. The patterns of shale-normalised fractionation at the most-contaminated points show an enrichment in the middle rare earth elements (MREE) with respect to the light (LREE) and heavy (HREE) ones, typical of acid waters. The Ce-anomaly becomes more negative as pH increases, due to the preferential fractionation of Ce in oxyhydroxides of Fe.     

Laboratory evaluation of zero-valent iron to treat water impacted by acid mine drainage

This study examines the applicability and limitations of granular zero-valent iron for the treatment of water impacted by mine wastes. Rates of acid-neutralization and of metal (Cu, Cd, Ni, Zn, Hg, Al, and Mn) and metalloid (As) uptake were determined in batch systems using simulated mine drainage (initial pH 2.3-4.5; total dissolved solids 14000-16000 mgl(-1)). Metal removal from solution and acid-neutralization occurred simultaneously and were most rapid during the initial 24 h of reaction. Reaction half-lives ranged from 1.50+/-0.09 h for Al to 8.15+/-0.36 h for Zn. Geochemical model results indicate that metal removal is most effective in solutions that are highly undersaturated with respect to pure-metal hydroxides suggesting that adsorption is the initial and most rapid metal uptake mechanism. Continued adsorption onto or co-precipitation with iron corrosion products are secondary metal uptake processes. Sulfate green rust was identified as the primary iron corrosion product, which is shown to be the result of elevated [SO(4)(2-)]/[HCO(3)(-)] ratios in solution. Reversibility studies indicate that zero-valent iron will retain metals after shifts in redox states are imposed, but that remobilization of metals may occur after the acid-neutralization capacity of the material is exhausted.     

Behavioural and feeding responses of Echinogammarus meridionalis (Crustacea, Amphipoda) to acid mine drainage

As a result of mining activities the exposure of metal sulphides to oxidation takes place with consequent release of acid mine drainage (AMD). Biomonitoring instruments have been proven to have the best deterrent effect upon polluters. A new approach in online biomonitoring, with the Multispecies Freshwater Biomonitortrade mark (MFB), was developed combining behavioural and feeding responses of the Portuguese indigenous benthic shredder, Echinogammarus meridionalis (Pinkster, 1973) (Crustacea, Amphipoda). These endpoints, along with mortality, were measured and analyzed for a gradient of sublethal doses of AMD. Original river water was used as the control and three doses of treatments were attained by adding increasing volumes of AMD to the control. The increase in AMD concentration and concomitant decrease in pH and increase in the concentration of most metals was followed by an overall increase of the mortality, decrease of locomotion/feeding activity and inhibition of the feeding rate. Mortality was observed in the two highest concentrations of AMD. Significant decrease in average locomotion/feeding activity took place in the second treatment. Although an inhibition of feeding was observed along the gradient of AMD concentration only in the highest concentration the feeding rate was significantly reduced.     

Fe0协同生物麦饭石的PRB系统井下原位处理煤矿酸性废水

针对煤矿酸性废水(AMD)具有污染组分多、危害程度严重、地面处理成本高等特点,以固定SRB污泥的生物麦饭石作为PRB活性填料,并添加Fe0构建生物-非生物协同去污的新型PRB井下原位修复系统,对AMD开展了连续动态、变负荷的模拟修复研究。实验结果表明,3个动态柱对pH均具有较强的调节能力,同时仅以麦饭石作为活性填料的PRB-3对Fe2+、Mn2+、NH3-N具有较好的去除效果,最大去除速率分别为45.77、9.23和12.10 mg/(L·d);以Fe0协同生物麦饭石的PRB-2在碳源充足时对SO42-、Fe2+、Mn2+、NH3-N最高去除速率分别为552.29、57.64、14.51和7.05 mg/(L·d),而相同条件下只以生物麦饭石作为活性填料的PRB-1对上述污染物的最高去除速率分别为446.62、57.20、10.87和3.53 mg/(L·d);应用PRB-2系统处理AMD不仅可以实现多种污染物的同步去除,还能实现无外加碳源的井下原位长效修复。     

Macroinvertebrate community response to acid mine drainage in rivers of the High Andes (Bolivia)

Several High Andes Rivers are characterized by inorganic water pollution known as acid mine drainage (AMD). The aim of this study was to assess the relationship between metal concentrations in the sediments and the macroinvertebrate communities in two river basins affected by AMD. In general, the taxon diversity of the macroinvertebrate community at the family level was low. The concentrations of Cd, Cu, Zn, Pb and Ni at mining sites were higher than at unpolluted sites. The pH of the water was alkaline (7.0-8.5) in unpolluted sites, whereas it dropped to very low values (<3) at mining sites. Redundancy Analysis (RDA) showed that pH was the best predictor of macroinvertebrate community richness. The number of macroinvertebrate families decreased gradually with increasing acidity, both in pools and riffles, though it is suggested that riffle communities were more affected because they are in closer contact with the acid water.     

Remediation of acid mine drainage (AMD)-contaminated soil by Phragmites australis and rhizosphere bacteria

Experiments were conducted to assess the impact of citric acid (CA) and rhizosphere bacteria on metal uptake in Phragmites australis cultured in a spiked acid mine drainage (AMD) soil. Rhizosphere iron-oxidizing bacteria (Fe(II)OB) enhanced the formation of Fe plaque on roots, which decreased the uptake of Fe and Mn. CA inhibited the growth of Fe(II)OB, decreased the formation of metal plaque, raised the metal mobility in soil, and increased the accumulation of metals in all tissues of the reeds. The higher the CA dosage, the more metals accumulated into reeds. The total amount of metals in reeds increased from 7.8?±?0.5?×?10^?6 mol plant^?1 (Mn), 1.4?±?0.1?×?10^?3 mol plant^?1 (Fe), and 1.0?±?0.1?×?10^?4 mol plant^?1 (Al) in spiked soil without CA to 22.2?±?0.5?×?10^?6 mol plant^?1 (Mn), 3.5?±?0.06?×?10^?3 mol plant^?1 (Fe), and 5.0?±?0.2?×?10^?4 mol plant^?1 (Al) in soil added with 33.616 g C₆H₈O₇·H₂O for per kilogram soil. CA could be effective at enhancing the phytoremediation of metals from AMD-contaminated soil.     

Characterization of iron-metabolizing communities in soils contaminated by acid mine drainage from an abandoned coal mine in Southwest China

Environmental Science and Pollution Research - Acid mine discharge (AMD) has been demonstrated to have significant impacts on microbial community composition in the surrounding soil environment....     

基于氧化还原-分步沉淀法的酸性矿山废水处理效果

为降低韶关市大宝山酸性矿山废水(AMD)的处理成本,采用氧化还原-分步沉淀法对矿山废水进行处理。结果表明：将石灰石分多次投入经过还原处理的废水中,在反应时间为45 min、转速为250 r·min⁻¹、废水pH为5时,可从AMD中回收高品质石膏;继续用NaOH溶液调节废水pH至5.5,控制曝气量为4 mg·L⁻¹,曝气时间为45 min,通过氧化沉淀法和铁氧体法可分步回收废水中的Fe^2+/3+,再向废水中加入NaOH溶液,调节废水pH至9.5,可沉淀回收废水中的Zn²⁺、Cu²⁺;经过该工艺处理后,废水中各金属离子均低于国家污水综合排放标准(GB 8978-1996);该工艺处理1 t废水,可回收石膏5.4 kg(纯度85.72%),铁渣1.53 kg(w(Fe)=35.4%)、锌铜渣1.4 kg(w(Zn)=10.89%、w(Cu)=0.1%);废水中Fe^2+/3+、Zn²⁺、Cu²⁺回收率分别为84.3%、71.2%、46.2%,废水处理的药剂成本为4.1元·t⁻¹,废水产生可回收资源产品收入为3.8 元·t⁻¹。该工艺可从AMD中回收高品质石膏并分步回收废水中的金属,有效降低废水的处理成本,回收废水中的资源,实现环保与经济效益双赢的目标,并为AMD资源化处理提供理论指导。     

Characterization and reactivity assessment of organic substrates for sulphate-reducing bacteria in acid mine drainage treatment

Acid mine drainage (AMD), which contains high concentrations of sulphate and dissolved metals, is a serious environmental problem. It can be treated in situ by sulphate reducing bacteria (SRB), but effectiveness of the treatment process depends on the organic substrate chosen to supply the bacteria's carbon source. Six natural organic materials were characterized in order to investigate how well these promote sulphate reduction and metal precipitation by SRB. Maple wood chips, sphagnum peat moss, leaf compost, conifer compost, poultry manure and conifer sawdust were investigated in terms of their carbon (TOC, TIC, DOC) and nitrogen (TKN) content, as well as their easily available substances content (EAS). Single substrates, ethanol, a mixture of leaf compost (30% w/w), poultry manure (18% w/w), and maple wood chips (2% w/w), and the same mixture spiked with formaldehyde were then tested in a 70-day batch experiment to evaluate their performance in sulphate reduction and metal removal from synthetic AMD. Metal removal efficiency in batch reactors was as high as 100% for Fe, 99% for Mn, 99% for Cd, 99% for Ni, and 94% for Zn depending on reactive mixtures. Early metal removal (0-12d) was attributed to the precipitation of (oxy)hydroxides and carbonate minerals. The lowest metal and sulphate removal efficiency was found in the reactor containing poultry manure as the single carbon source despite its high DOC and EAS content. The mixture of organic materials was most effective in promoting sulphate reduction, followed by ethanol and maple wood chips, and single natural organic substrates generally showed low reactivity. Formaldehyde (0.015% (w/v)) provided only temporary bacterial inhibition. Although characterization of substrates on an individual basis provided insight on their chemical make-up, it did not give a clear indication of their ability to promote sulphate reduction and metal removal.     

A novel application of H2O2-Fe(II) process for arsenate removal from synthetic acid mine drainage (AMD) water

Batch experiments were carried out to investigate the influences of H₂O₂/Fe(II) molar ratio, pH, sequence of pH adjustment, initial As(V) concentration, and interfering ions on As(V) removal in H₂O₂-Fe(II) process from synthetic acid mine drainage (AMD). The optimum H₂O₂/Fe(II) molar ratio was one for arsenate removal over the pH range of 4-7. Arsenate removal at pH 3 was poor even at high Fe(II) dosage due to the high solubility of Fe(III) formed in situ. With the increase of Fe(II) dosage, arsenate removal increased progressively before a plateau was reached at pH 5 as arsenate concentration varied from 0.05 to 2.0 mg L⁻¹. However, arsenate removal was negligible at Fe/As molar ratio <3 and then experienced a striking increase before a plateau was reached at pH 7 and arsenate concentration ≥1.0 mg L⁻¹. The co-occurring ions exerted no significant effect on arsenate removal at pH 5. The experimental results with synthetic AMD revealed that this method is highly selective for arsenate removal and the co-occurring ions either improved arsenate removal or slightly depressed arsenate removal at pH 5-7. The extended X-ray absorption fine structure (EXAFS) derived As-Fe length, 3.27-3.30 Å, indicated that arsenate was removed by forming bidentate-binuclear complexes with FeO(OH) octahydra. The economic analysis revealed that the cost of the H₂O₂-Fe(II) process was only 17-32% of that of conventional Fe(III) coagulation process to achieve arsenate concentration below 10 μg L⁻¹ in treated solution. The results suggested that the H₂O₂-Fe(II) process is an efficient, economical, selective and practical method for arsenate removal from AMD.     

Macroinvertebrate response to acid mine drainage: community metrics and on-line behavioural toxicity bioassay

The hypothesis is tested that toxicity of acid mine drainage can be detected by a selection of existing macroinvertebrate community and bioindicator metrices supplemented by toxicity tests with the local mosquitofish Gambusia holbrooki Girard and the shrimp Atyaephyra desmaresti Millet. The behavioural responses of A. desmaresti to acid mine drainage were recorded in the Multispecies Freshwater Biomonitor, based on behaviour and survival as parameters. Bioassessment methods were based on community diversity, structure, function, and bioindicators and supplemented by chemical analysis (temperature, pH, metals). The Biological Monitoring Working Party adapted for the Iberian Peninsula, the number of predators (Coleoptera, Hemiptera) and the number of Ephemeroptera and Trichoptera taxa differentiated the sites well. The on-line toxicity test revealed pH-dependent acute toxicity of the acid mine drainage for the shrimp (LC(50)-48 h: pH-AMD=5.8) and a pH- dependent decrease in locomotory activity with the lowest-observed-response-times (LORTs) within 5 h of exposure. Shrimp were more sensitive to acid mine drainage than fish (LC(50)-48 h: pH-AMD=4.9). A new multimetric index combining toxicity testing and bioassessment methods is proposed.     

Metal behaviour in an estuary polluted by acid mine drainage: the role of particulate matter

The concentrations of dissolved and suspended particulate Cd, Cu and Zn have been determined in water samples obtained during two axial transects of the Rio Tinto-Huelva Ria system in south-west Spain, which is severely impacted by acid mine drainage. Although the metal concentrations in both phases were elevated, dissolved metals were dominant and, in the upper estuary, constituted > 99% of total metal in the water column. Dissolved metals behaved non-conservatively on each transect, with maximum concentrations in the low salinity region. There was no evidence of metal adsorption within the turbidity maximum zone, despite the high specific surface areas of resuspending particles. Measurements of electrophoretic mobility showed that the suspended particulate matter (SPM) had a positive surface charge in the salinity range 0-4, where the waters had a pH < 3. Desorption experiments were carried out in which SPM from the turbidity maximum zone was resuspended in coastal seawater. The desorption of the metals was monitored for 24 h, using anodic stripping voltammetry (ASV) to detect the variation in total dissolved Cd, Cu and Zn and the species of Cu and Zn. Total dissolved Cd concentrations doubled during the incubation period, whereas the concentration of total dissolved Cu declined and that of Zn remained rather constant. The ASV-labile fraction of dissolved Cu and Zn showed an initial sharp release followed by a slower uptake. However, desorption was shown to be a minor source of dissolved metals and made little contribution to the non-conservative behaviour in the low salinity zone. The results are used to predict the effects of acid mine drainage on estuarine ecology.     

Depauperate macroinvertebrates in a mine affected stream: clean water may be the key to recovery

Acid mine drainage (AMD) is frequently linked with changes in macroinvertebrate assemblages, but the relative contribution of water and sediment to toxicity is equivocal. We have shown that the macroinvertebrate fauna of Neubecks Ck, a mine impacted stream in New South Wales, Australia, was much poorer than in two reference streams. Multivariate RELATE analyses indicated that the patterns in the biological data were more strongly correlated with the concentrations of common metals in the surface water than the pore water of these streams. From this we hypothesised that the water was more toxic to the biota than the sediment and we tested this hypothesis with a sediment transplant experiment. Sediment from Neubecks Ck that was placed in reference streams retained high concentrations of metals throughout the experiment, yet supported a macroinvertebrate assemblage similar to that in the reference streams. Sediment from the reference streams that was placed in Neubecks Ck supported few, if any, animals. This indicates that water in Neubecks Ck is toxic to biota, but that sediment is able to support aquatic biota in clean water. Therefore, remediation should focus on improving water quality rather than sediment quality.     

Diel cycles of arsenic speciation due to photooxidation in acid mine drainage from the Iberian Pyrite Belt (Sw Spain)

Twenty four hours diel cycles of arsenic speciation in Acid Mine Drainage (AMD) due to photooxidation have been reported for the first time. AMD samples were taken during 48 h (31st March and 1st April, 2005) at 6 h intervals from the effluent of a massive abandoned polymetallic sulphide mine of the Iberian Pyrite Belt (Sw Spain). Samples were preserved in situ using cationic exchange prior to analysis by coupled high performance liquid chromatography, hydride generation and atomic fluorescence spectrometry (HPLC-HG-AFS) for arsenic speciation. The results indicated the presence of inorganic arsenic species with daily means of 262mugl(-1) for As(V) and 107 microg l(-1) for As(III). No marked diel trend was observed for As(V). However, a marked diel trend was observed for As(III) in the two studied days, with maximum concentrations during nighttime (141-143 microg l(-1)) and minimum concentrations at daytime (72-77 microg l(-1)). This difference in concentration during daytime and nighttime is ca. 100%. A similar diel cycle was observed for iron. An explanation for the arsenic diel cycles observed is the light induced photooxidation of As(III) and the elimination of As(V) due to its adsorption onto Fe precipitates during the daytime. Furthermore, the diel changes in arsenic speciation emphasize the importance of designing suitable sampling strategies in AMD systems.     

Kinetic analysis of constructed systems for the recovery of contaminated areas by acid mine drainage

INTRODUCTION: Flowing of the acid mine drainage may contaminate the adjacent water bodies causing substantial changes in the aquatic ecosystem. This aspect is the most relevant problem in the southern of Santa Catarina once the contaminated areas are inserted in the watershed of the Araranguá, Urussanga, and Tubar?o rivers, increasing the need for recovery studies. These areas are between Criciúma, I?ara, Urussanga, Siderópolis, Lauro Müller, Orleans, and Alfredo Wagner towns where a conservation unit exist called the Environmental Preservation Area of Baleia Franca. Aiming to compare the kinetics of the ash derived from burning coal and to neutralize acid mine drainage, different neutralizer, limestone, fly, and bottom ash, was mounted on a pilot scale experiment. DISCUSSION: The transport parameters showed the same order of infiltration and dispersion: fly ash < bottom ash < limestone. The order of measured alkalinity was: limestone < fly ash < bottom ash, with pH values of 9.34, 12.07, and 12.25, respectively. The limestone kinetics of acidic drainage neutralization was first order with reaction rate constant k?=?0.0963 min(-1), bottom ash was 3/4 with k?=?0.0723 mol(1/4) L(-1/4) min(-1), and the fly ash had higher order kinetics, 4/3, with reaction rate constant k?=?27.122 L(1/3) mol(-1/3) min(-1). However, by mathematical modeling, it was found that due to a combination of transport and kinetics, only limestone treatment reached a pH above 6 within 5 years, corresponding to the ideal as planned.     

Improvement of breeding success of the moor frog (Rana arvalis) by liming of acid moorland pools and the consequences of liming for water chemistry and diatoms

Liming experiments with powdered limestone (grain size < 3 mm) were conducted in eight acid shallow moorland pools in the Tongerense Heide heathland area from February 1988 until November 1989. The effects on water chemistry, diatoms and fungal infection of the eggs of the moor frog were studied. After an initial treatment in March 1988, the pH increased from c. 4.0 to c. 5.0 in those pools which dried out in summer and to c. 6.0 in the permanent pools. Alkalinity increased from 0 to 20-200 microeq litre(-1) in temporary pools and from 0 to 300-500 microeq litre(-1) in permanent pools. As drying out of the pools caused reacidification, after refilling the temporary pools were relimed in March 1989. No significant changes were found in concentrations of phosphate and nitrogen compounds. Eunotia paludosa, which is characteristic for ologotrophic, very acid pools and bogs with a fluctuating water table, was the dominant diatom in the untreated pools. It was replaced by eutraphentic and saprophilous taxa, particularly in the permanent pools. Species from extremely soft waters, which are very sensitive to acidification, were found only occasionally in some samples from the treated permanent pools. After liming the proportion of infected moor frog eggs decreased from c. 95% in the untreated to c. 5% in the treated pools.     

Dealing with environmental legacy effects: the economic and social benefits of acid mine drainage remediation

This paper is concerned with developing a practical methodology for prioritising measures to ameliorate the environmental problems associated with the abandonment of mine workings. Although much attention is focused on the pollution associated with on-going industrial production, rather fewer resources are going to develop methodologies for handling the environmental legacy effects of our forefathers. Of the work that has been done, much of it tends to focus on single, incomplete measures or benefits. This paper looks at the particular issues of acid mine drainage (AMD) in the USA, and develops a tractable way of approaching the problem of how allocated resources may be prioritised to maximise net social benefits. In particular, it advocates the use of a combination of established methodologies with rather newer statistical procedures to approach the problem. It offers a number of case studies by way of illustration as to how the methodology can be applied.     

Sulfate-reducing bacterial community shifts in response to acid mine drainage in the sediment of the Hengshi watershed,South China

Environmental Science and Pollution Research - Sulfate-reducing bacteria (SRB) are an attractive option for treating acid mine drainage (AMD) and are considered to be of great significance in the...