Mineralogical and geochemical characterization of precipitates on stream receiving acid mine water, Korea

Seasonal variations of water chemistry occurred in acid mine drainage receiving mine and leachate water. Sulfate and metal concentrations were low in winter but high in spring and summer. Mine waters were highly acidic (up to pH 3.4) in nature with high concentrations of manganese, copper and zinc but high electrical conductivity and sulfate in leachate. The blue and brownish yellow precipitates were formed under different chemical environments of acid mine drainage. Brownish yellow (Munsell color 7.5YR 8/12), blue (Munsell color 2.5B 9/7) and light blue (Munsell color 2.5B 9/3) precipitates deposited on the stream bottom receiving acid mine water. The brownish yellow precipitates formed in the acid mine water, whereas the blue and light blue precipitates formed in the leachate water. The brownish yellow precipitates consisted mainly of ferrihydrite, whereas the blue and light blue precipitates consisted of glaucocerinite and/or woodwardite.     

Effects on nutrient regime in two recipients of nitrogen-rich mine effluents in northern Sweden

The question of the limiting nutrient(s) for production of phytoplankton and macrophytes was explored in two contrasting freshwater systems receiving N- and P-rich mine effluents from the Boliden and Kiruna mine sites, northern Sweden. For both sites, total N (TN), total P (TP) and TN:TP mass ratios in water, sediment and macrophytes were used to examine (1) spatial variations within the systems, (2) differences between the systems and (3) seasonal variations. The TN concentration from the discharge point at the Kiruna site was about seven times higher than at the Boliden discharge point, while the TP concentration was 10 times lower than in the discharge point at the Boliden site. The majority of the studied lakes showed elevated biomass of phytoplankton, with maximum values found in Lake Bruträsket (Boliden). Mining activities have affected the nutrient regime of the two recipients by contributing to elevated TN and TP concentrations and TN:TP mass ratios as well as elevated production of phytoplankton and macrophytes compared to the reference sites. Depending on the NH₄ concentration in the effluent at the Boliden site, water column TN:TP mass ratios shifted from being >22, indicating P-deficiency, to between 9 and 22, indicating a transition from N- to P-deficiency (co-limitation). However, water column TN:TP mass ratios at the Kiruna site always indicated P-deficiency, while TN:TP mass ratios of macrophytes indicate that both sites may vary from N- to P-limitation. The study suggests that for the design of efficient monitoring programmes and remediation measures, it is important to consider the major N and P species in water, phytoplankton, sediment and macrophytes.     

Geochemical changes during neutralisation of acid mine drainage in a dynamic mountain stream, New Zealand

The Mangatini Stream drains a coal mining area in the mountains of northwestern South Island of New Zealand. Abundant rainfall on pyritic rocks yields acid mine drainage (AMD) to the stream, which flows through a steep gorge at discharges that rapidly increase from <1 to >100 m³/s during frequent rain events. The AMD is treated with finely ground limestone, which is discharged as a slurry at a point in the middle of the gorge. The limestone slurry mixes and reacts with the AMD during flow ∼4 km downstream over ∼12 h. Neutralisation reactions increase stream pH from near 3 (untreated Mangatini Stream water impacted by AMD) to 5–6 in the first 250 m downstream, although mixing is commonly incomplete in this zone. Large stream discharge volumes in rain events dilute the neutralising material input, thus driving the pH back towards 4 downstream of treatment. More complete neutralisation is achieved 4 km downstream, even in major rain events, and pH can rise to >7. Partial neutralisation is sufficient to remove most of the dissolved Fe(III) (typically ∼30 mg/L) from the Mangatini Stream in the first 10 m, and remaining dissolved Fe is essentially all Fe(II), which decreases over time as it oxidises and precipitates. Dissolved Al in the Mangatini Stream (typically ∼50 mg/L) decreases steadily downstream over ∼100 m in the limestone mixing zone. Precipitated Fe and Al form amorphous oxyhydroxides that are transported as suspended solids and deposited on the stream bed with excess limestone in zones of low flow velocity. Dissolved Zn is removed from solution by adsorption to Fe oxyhydroxide when pH reaches ∼5, but dissolved Ni remains in solution despite the neutralisation process. Gypsum precipitation occurs throughout the limestone mixing zone, resulting in at least 30% decrease in dissolved . Minor ettringite forms in the first 100 m, but then probably redissolves. The limestone dosing system is an effective method of neutralising the effects of AMD and removing most dissolved metals in a steep mountain stream with frequent rain events where this dynamic environment places many constraints on treatment options.     

Geochemistry of suspended particles in a mine-affected mountain stream

The particles in a mine drainage and the creek into which it drains were examined using microbeam and filtration methods. The composition of the particles in the drainage and creek were distinctly different, though both carried a chemical signal from the mine. High concentrations of particles made up of Fe and S were seen in the drainage, especially during low flow. The molar Fe:S ratio of these suspended particles was 3.5:1. The influx of the mine drainage into the creek increased the relative number of aggregates and particles with associated Fe. However, few discrete Fe–S particles were seen in the creek, where solid-phase Fe and S were consistently associated with aluminosilicate minerals. Instream precipitation is predicted and appears to be an important additional source of Fe and Al oxyhydroxides to the particles. Some of the Fe and Al associated with particles in the creek was acid-soluble, but most of the acid-soluble Zn, Mn, Cu, Ca, Mg and Si were transported in the <0.45 μm fraction at a site downstream of the mine drainage. One third of the suspended particles had associated P. These suspended particles take part in the complex geochemistry of this system, and represent an important pool as a potential sink and source of metals and other elements.     

Modeling hydrothermal, suspended solids transport and residence time in a deep reservoir

This article presents the modeling of hydrothermal characteristics and suspended solids in a long and large-volume reservoir with a highly fluctuating water level. A laterally averaged two-dimensional hydrothermal and water quality model was configured for the Shihmen Reservoir in northern Taiwan. The model was validated with measured data of water surface elevation, water temperature, and concentration of suspended solids in 2006. The results show that the numerical model was able to reproduce the measured data. The validated model was then used to investigate the effects of water withdrawal schemes at different depths and to estimate the residence time in the reservoir. When water is withdrawn from a great depth, the relatively warm water from the upper layers can replace that in the deep layers, thereby facilitating heat transfer from the surface to the deeper layer. Bottom-water withdrawal results in a lower concentration of suspended solids compared with withdrawal from depths of 20 and 40 m. The simulated results show that the residence time is approximately 154 days in the Shihmen Reservoir.     

Impacts of acid mine drainage on a stream in subtropical China during a major flood event

Field and laboratory work was carded out to investigate the chemistry and ecotoxicity of stream water affected by acid mine drainage in a tributary catchment of the Pearl River in subtropical China during a major flood event that corresponded to a return period of 100 years occurred in the study area. The results indicate that stream water was affected by acid mine drainage from the Dabaoshan Mine at least to a distance of 25 km downstream of the mine water discharge point. It appears that sulfide-H^＋ from the waste rock dumps was readily available for discharging and the amount of H^＋ being transported outwards depended on the volume of out-flowing waters. However, there was a lag time for the discharge of the metals. This may be attributed to the slower release of metals, relative to H^＋, because it might take more time for the dissolution of heavy metal-bearing compounds. Fe, Zn and Al were the major metals of potential toxicity contained in the AMD-affected stream water, followed by Mn, Cu, Pb, As, Cd and Ni. Acute toxicity tests show that the AMD-affected stream water at 3.5 km downstream of the discharge point was highly toxic to the test organisms.     

Pollutant association with suspended solids in stormwater in Tijuana,Mexico

Stormwater runoff from urban areas is a major source of many pollutants to water bodies. Suspended solids are one of the main pollutants because of their association with other pollutants. The objective of this study was to evaluate the relationship between suspended solids and other pollutants in stormwater runoff in the city of Tijuana. Seven sites were sampled during seven rain events during the 2009–2010 season and the different particle size fractions were separated by sieving and filtration. The results have shown that the samples have high concentration of total suspended solids, the values of which ranged from 725 to 4,411.6 mg/L. The samples were analyzed for chemical oxygen demand, total phosphorus, total nitrogen, and turbidity. The results show that most of the particles in suspended solids are in the particle fraction between 10 and 62 μm. A high association between the concentrations of suspended solids was found for chemical oxygen demand, phosphorus, and turbidity but not for total nitrogen.     

Metal contamination and solid phase partitioning of metals in the stream and bottom sediments in a reservoir receiving mine drainage

This study was conducted to assess the anthropogenic impact on metal concentrations in the bottom sediments of the Juam reservoir, Korea, and in stream sediments in its catchment, and to estimate the potential mobility of selected metals (Fe, Mn, Cu, Ni, Pb and Zn) using sequential extraction. A comparison of the metal concentrations in the stream sediments with mean background values in sediments collected from first- or second-order creeks shows that Pb, Cu and Ni are the most affected by anthropogenic inputs. The ²⁰⁶Pb/²⁰⁷Pb ratios of the bottom and core sediments (means: 1.2320 ± 0.0502 and 1.2212 ± 0.0040, respectively) suggest that Pb contamination is mainly due to the waste discharge of abandoned coal and metal mines rather than industrial and airborne sources. Considering the proportion of metals bound to the exchangeable, carbonate and reducible fractions, the comparative mobility of metals is suggested to decrease in the order Mn > Pb > Zn > Ni > Fe ≫ Cu.     

Downstream patterns of bed sediment-borne metals,minerals and organic matter in a stream system receiving acidic mine effluent: A preliminary study

Different downstream variation patterns were observed for a range of bed sediment-borne metals (aqua regia-extractable fraction) in a subtropical stream system receiving acid mine drainage. Mine-originated Fe tended to be deposited in the acidic (mean pH < 4.9) upstream reach in forms of goethite and/or hematite. In contrast, other metals tended to be transported farther downstream and settled in a low-gradient reach with high pH (mean pH > 5.6). The peak of sediment-borne Al, Be, Ca, Cd, Co, Cu, La, Mn, Ni and Zn corresponded very well with the peak of the sediment-borne organic matter, suggesting a close association between the water-borne organic colloids and the inorganic metal oxides/hydroxides during their transport. The marked increase in the sediment-borne Al and Pb started more upstream than the other metals, suggesting that the water-borne Al and Pb were more susceptible to pH rise-induced precipitation, as compared to the other metals. It appeared that the organic colloids played no important role in Pb transport and settlement. The iron precipitates had a limited role to play in affecting the transport and fates of other metals since they were predominantly formed and deposited in the acidic reach, which made them incapable of scavenging cationic metals by co-precipitation or adsorption.     

Distribution of reduced inorganic sulfur compounds in lake sediments receiving acid mine drainage

The sediments of Lake Anna, Virginia, act as a major sink for incoming acid mine drainage (AMD) pollutants (Fe, SO₄²⁻, H⁺) due to bacterial sulfate reduction (SR). Acid-volatile sulfide (AVS), elemental S, and pyrite concentrations in the sediments of the polluted arm of the lake are significantly greater than those in unpolluted sections of the lake. Measurements of SR using ³⁵SSO₄²⁻ showed that AVS and S⁰ are the major short-term (48 h) products of SR in these sediments. Inorganic forms of S(AVS, S⁰, and FeS₂) made up from 60 to 100% of the total sediment S concentration. Pyrite concentrations in the sediment were high but decreased exponentially with distance from the AMD source, suggesting that the pyrite was deposited as stream detritus from the abandoned mines. Iron monosulfide and elemental S concentrations were highest at a station 1 km away from the AMD inflow, indicating formation in situ. There was no evidence for the formation of organic S species. The results suggest that in Fe- and S-rich locations such as those contaminated with acid mine drainage, the distribution of end products of SR may vary substantially from those reported for more moderate environments.     

Seasonal variations of ochreous precipitates in mine effluents in Finland

Ochreous precipitate and water samples were collected from the surroundings of seven closed sulphide mines in Finland. In the Hammaslahti Zn–Cu–Au mine, Otravaara pyrite mine and Paroistenjärvi Cu–W–As mine, the collection was repeated in different seasons to study mineralogical and geochemical variations of precipitates. The sampling was done in 1999–2002 from the ditches and drainage ponds of the tailings and waste rock piles that are susceptible to seasonal changes. Mineralogy of the precipitates was evaluated by X-ray diffraction (XRD) and infrared spectroscopy (IR), and precipitate geochemistry was examined by selective extractions. Schwertmannite (Fe₈O₈(OH)₆SO₄) was the most typical Fe hydroxide mineral found. Goethite was almost as common as schwertmannite, was often poorly ordered, and contained up to 10 wt.% of SO₄. Goethite and schwertmannite were commonly found as mixtures, and they occurred in similar pH and SO₄ concentrations. Ferrihydrite (nominally Fe₅HO₈ · 4H₂O) was typically found in areas not influenced by acid mine drainage, and also in acid mine waters with high organic matter or As content. Jarosite (KFe₃(SO₄)₂(OH)₆) was found only in one site. In addition, some gypsum (CaSO₄ · 2H₂O) and aluminous sulphate precipitates (presumably basaluminite, Al₄(SO₄)(OH)₁₀ · 5H₂O) were identified. Selective extractions showed that acid extracts Fe_tot/S_tot-ratios of schwertmannite and goethite samples were similar, but the ratio of oxalate-extractable to total Fe, Fe_ox/Fe_tot, of goethite samples were lower than those of the schwertmannite samples. Only Al, Si and As were bound to precipitates in substantial amounts, up to several wt.%. In schwertmannites and goethites, Al, Cu, Co, Mn and Zn were mostly structural, substituting for Fe in an Fe oxyhydroxide structure or bound to surface adsorption sites in pores limited by diffusion. In ferrihydrites, heavy metals were also partly bound in adsorbed form dissolving in acid ammonium acetate. Ferrihydrites and goethites were more enriched in Co, Mn and Zn than schwertmannites, but schwertmannites and ferrihydrites were more enriched in As than goethites. Mineralogical and geochemical evidence showed that in the spring, after the snowmelt, the acid mine drainage precipitates were predominantly schwertmannite, and were partly transformed during warm summer months to goethite. The phase transformation of precipitates was followed by a decrease in pH values and increase in SO₄ concentrations of waters. Adsorbed As retarded the phase transformation.     

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.     

The concentration control of soluble copper in a mine tailings stream

Comparison of decreasing total copper content and increasing pH of an abandoned copper mine drainage stream to the stability fields of malachite, tenorite, and cupric hydroxide indicates that soluble copper is not lost by precipitation but by sorption on the stream sediments.     

Influence of acid mine drainage on microbial communities in stream and groundwater samples at Guryong Mine,South Korea

The effects of acid mine drainage (AMD) in a stream and groundwater near an abandoned copper mine were characterized by physicochemical properties, bacterial community structure using denaturing gel gradient electrophoresis (DGGE), and microbial activity/diversity using Ecoplate technique. Based on DGGE fingerprints, the eubacterial community structures grouped into the stream water (GRS1, GRS2 and GRS3) and groundwater samples (GW1 and GW2), apparently based on differences in water temperature and the concentrations of dissolved oxygen, nitrate and sulfate. The most highly AMD-contaminated sample (GRS1) had additional α-Proteobacteria whereas the groundwater samples included additional β-Proteobacteria, suggesting the development of populations resistant to AMD toxicity under aerobic and anaerobic conditions, respectively. Community level physiological activities on the 31 Ecoplate substrates suggested that the activities decreased with increasing concentrations of sulfate and heavy metals derived from AMD. The Shannon index showed that microbial diversity was greatest in GRS2, and lowest in GRS1, and was probably related to the level of AMD.     

Effects of colloids on metal transport in a river receiving acid mine drainage,upper Arkansas River,Colorado, U.S.A.

Inflows of metal-rich, acidic water that drain from mine dumps and tailings piles in the Leadville, Colorado, area enter the non-acidic water in the upper Arkansas River. Hydrous iron oxides precipitate as colloids and move downstream in suspension, particularly downstream from California Gulch, which has been the major source of metal loads. The colloids influence the concentrations of metals dissolved in the water and the concentrations in bed sediments. To determine the role of colloids, samples of water, colloids, and fine-grained bed sediment were obtained at stream-gaging sites on the upper Arkansas River and at the mouths of major tributaries over a 250-km reach. Dissolved and colloidal metal concentrations in the water column were operationally defined using tangential-flow filtration through 0.001-pm membranes to separate the water and the colloids. Surface-extractable and total bed sediment metal concentrations were obtained on the <60-μm fraction of the bed sediment. The highest concentrations of metals in water, colloids, and bed sediments occurred just downstream from California Gulch. Iron dominated the colloid composition, but substantial concentrations of As, Cd, Cu, Mn, Pb, and Zn also occurred in the colloidal solids. The colloidal load decreased by one half in the first 50 km downstream from the mining inflows due to sedimentation of aggregated colloids to the streambed. Nevertheless, a substantial load of colloids was transported through the entire study reach to Pueblo Reservoir. Dissolved metals were dominated by Mn and Zn, and their concentrations remained relatively high throughout the 250-km reach. The composition of extractable and total metals in bed sediment for several kilometers downstream from California Gulch is similar to the composition of the colloids that settle to the bed. Substantial concentrations of Mn and Zn were extractable, which is consistent with sediment-water chemical reaction. Concentrations of Cd, Pb, and Zn in bed sediment clearly result from the influence of mining near Leadville. Concentrations of Fe and Cu in bed sediments are nearly equal to concentrations in colloids for about 10 km downstream from California Gulch. Farther downstream, concentrations of Fe and Cu in tributary sediments mask the signal of mining inflows. These results indicate that colloids indeed influence the occurrence and transport of metals in rivers affected by mining.     

Seasonal variations in the composition of mine drainage-contaminated groundwater in Dalarna, Sweden

Groundwater down-gradient from a mine rock dump in Dalarna, Sweden was sampled from the onset of snowmelt runoff (April) until October in order to investigate seasonal variations in groundwater composition. The results demonstrate that considerable variation in solute concentration (Al, Cu, Fe, SO₄²⁻, Zn) and acidity occurs in groundwater; the greatest change in solute concentrations occurs during the melting of the snow cover, when sulfide oxidation products are flushed from the rock dump. During this period, groundwater flow is concentrated near the soil surface with an estimated velocity of 1 m/day. Groundwater acidity varied by a factor of four closest to the rock dump during the sampling period, but these variations were attenuated with distance from the rock dump. Over a distance of 145 m, groundwater pH increases from 2.5 to 4.0 and acidity decreases from 3–13 to 0.8–1.1 meq/L, which is the combined effect of ferric iron precipitation and aluminosilicate weathering. As a result of flushing from the upper soil horizons, peaks in total organic carbon and ammonium concentrations in groundwater are observed at the end of snowmelt. In soils impacted by acidic surface runoff, the sequential extraction of C horizon soils indicates the accumulation of Cu in well-crystallized iron oxyhydroxides in the upper C horizon, while Cu, Fe, Ni and Zn accumulate in a well-crystallized iron oxyhydroxide hardpan that has formed 2.5m below the ground surface. Surface complexation modeling demonstrates that SO₄²⁻ and Cu adsorb to the abundant iron oxyhydroxides at pH < 4, while Zn adsorption in this pH range is minimal.     

Secondary copper enrichment in tailings at the Laver mine, northern Sweden

 Field and laboratory studies of the sulphide-bearing tailings at Laver, northern Sweden, show that the present release of metals from the tailings is low, especially with regard to Cu. A large part of the Cu released by sulphide oxidation is enriched in a distinct zone just below the oxidation front. The enrichment zone occurs almost all over the tailings area except in areas with a shallow groundwater table. The Cu enrichment is caused by formation of covellite and adsorption onto mineral surfaces. The transport of Zn, Co, Cd, Ni and S seems to be controlled mainly by adsorption. No secondary zone or secondary minerals containing these metals have been found. Just below the groundwater table, metals are released into solution when the enrichment zone reaches the groundwater due to the low pH. An increased release of metals, especially Cu, can be expected in the future, since the enrichment zone is moving towards the groundwater table. Received: 4 December 1997 · Accepted: 17 December 1998     

Impact of discharge wastewater effluents on the physico-chemical qualities of a receiving watershed in a typical rural community

The qualities of the treated final effluents of a wastewater treatment plant located in a rural community of the Eastern Cape Province of South Africa were assessed over the duration of 12 months. Parameters measured include pH, temperature, electrical conductivity, salinity, turbidity, total dissolved solid, dissolved oxygen, chemical oxygen demand, nitrate, nitrite and orthophosphate levels and these were simultaneously monitored in the treated final effluents and the receiving watersheds using standard methods. Unacceptably, high levels of the assayed parameters were observed in many cases for chemical oxygen demand (7.5–248.5 mg/L), nitrate (1.82–13.14 mg/L), nitrite (0.09–1.3 mg/L), orthophosphate (0.07–4.81 mg/L), dissolved oxygen (4.15–11.22 mg/L) and turbidity (3.68–159.06 NTU) during the study period and are severally outside the compliance levels of the South African Guidelines and World Health Organization tolerance limits for effluents intended for discharge through public sewers into receiving watersheds. The study has revealed that there was an adverse impact on the physico-chemical characteristics of the receiving watershed as a result of the discharge of inadequately treated effluents from the wastewater treatment facility. This poses a health risk to several rural communities which rely on the receiving water bodies primarily as their sources of domestic water. There is need for the intervention of appropriate regulatory agencies to ensure production of high quality treated final effluents by wastewater treatment facilities in rural communities of South Africa.