Column experiments for microbiological treatment of acid mine drainage: low-temperature, low-pH and matrix investigations

The lifetime of traditional sulfate-reducing bacteria (SRB) bioreactors that utilize a source of reducing equivalents contained within the matrix (e.g. manure) is limited by the amount of readily available reducing equivalents within that matrix. In order to extend bioreactor lifetime indefinitely, the addition of known concentrations of alternative reducing equivalents (methanol and ethanol) to a depleted matrix was tested at low pH and low temperatures. Following acclimation, up to 100% efficiencies of reducing equivalents were directed toward sulfate reduction. Alcohol was added in stoichiometric concentrations to remove 50% of the added sulfate (900 mg/L), producing sufficient sulfide to precipitate all of the iron from solution. An average of 42% of the sulfate was removed following acclimation, reflecting 84% efficiency. An average of 93% of the iron was removed (93 mg/L). Bacteria acclimated to ethanol more rapidly than methanol, although both alcohols were effective as carbon sources. Efficient treatment was observed at the lowest temperatures (6 degrees C) and lowest pHs (pH=2.5) tested. The use of ethanol-fed, highly permeable bioreactor matrices of wood chip, pulverized plastic and rock was also examined to determine which of these porous matrices could be implemented in a field bioreactor. Results indicated that >95% of the 100mg/L iron added was removed by all matrices. Sufficient reducing equivalents were added to remove 450 mg/L of sulfate, wood and rock matrices removed approximately 350 mg/L plastic removed approximately 225 mg/L. A study comparing rock size indicated that small rocks removed iron and sulfate more efficiently than medium- and large-size rocks. The results suggest that wood and rock in conjunction with ethanol are viable alternatives to traditional bioreactor matrices. These findings have direct application to semi-passive sustained operation of SRB bioreactors for treatment of acidic drainage at remote sites.     

Performance of a passive treatment system for net-acidic coal mine drainage over five years of operation

A full-scale passive treatment system (PTS) was commissioned in 2003 to treat two net-acidic coal mine water discharges in the Durham coalfield, UK. The principal aim of the PTS was to decrease concentrations of iron (< 177 mg L⁻¹) and aluminium (< 85 mg L⁻¹) and to increase pH (> 3.2) and alkalinity (≥ 0 mg L⁻¹ CaCO₃ eq). Secondary objectives were to decrease zinc (< 2.8 mg L⁻¹), manganese (< 20.5 mg L⁻¹) and sulfate (< 2120 mg L⁻¹). Upon treatment, water qualities were improved by 84% in the case of Fe, 87% Al, 83% acidity, 51% Zn, 23% Mn and 29% SO₄²⁻. Alkalinity (74%) and pH (95% as H⁺) were increased. Area adjusted removal rates (Fe = 1.49 ± 0.66 g d⁻¹ m⁻²; acidity = 6.7 ± 4.9 g d⁻¹ m⁻²) were low compared to design criteria, mainly due to load limitation. Disregarding seasonality effects, acidity removal and effluent pH were stable over time. A substantial temporal decrease in calcium and alkalinity generation suggests that limestone is increasingly armoured. Once pH is no longer buffered by the carbonate system, metals could be remobilized, putting treatment efficiency at risk.     

Methods for estimation of long-term non-carbonate neutralisation of acid rock drainage

In the long-term phase of an acid rock drainage (ARD) evolution profile, after any short-term neutralisation capacity provided by carbonate minerals is exhausted, the net acid release is a product of a declining acid generation rate (AGR) and a slower, long-term acid neutralisation rate mainly provided by gangue silicate minerals. At some point, the AGR and the non-carbonate acid neutralisation rate (ANRnc) will be similar. Matching of the AGR and ANRnc near 10 mg H₂SO₄/kg/week is demonstrated in data from 10-year columns. This long-term neutralisation is not measured at present in any accepted assessment tests. Methods to estimate ANRnc, based on silicate mineralogy and solution assays from long-term column leach tests, are compared. Good agreement is demonstrated between rates measured from the solution assay data and those calculated from mineralogy using kinetic databases. More rigorous analysis of the leachate chemistry of selected long-term leach tests also suggests possible cover design criteria based on the maximum AGR that will maintain a pH > 4 in leachate from ARD materials. The data show a distinct break at an AGR of 3 mg H₂SO₄/kg/week, below which no leachate pH is less than 4. The results indicate that an AGR of 10 t H₂SO₄/ha/year is conservative and a suitable cover design target for ARD control that would be matched by ANRnc.     

In situ calcite formation in limestone-saturated water leaching of acid rock waste

The result of leaching of a 75% acid rock/25% limestone column with limestone-saturated solution has shown that the pH of the effluent recovered from 2.5, after apparent loss of acid neutralizing capacity after 4 years with water leaching, to pH 7 in less than 3 years. Bulk assay results, XRD and SEM/EDS analyses of samples from the column at 384 weeks (pH 3.6) and 522 weeks (pH 6.9) during this recovery have suggested that this is due to formation in situ of fine calcite. Calcite, initially blended to the column material at 25 wt.% was not found in the XRD of the 384 week sample but is clearly found in the 522 week XRD. This increased calcite content appears to be derived from the limestone-saturated water as finely divided solid precipitated in the drying cycles in the column. This result is confirmed by assessment of the 522 week sample as non-acid forming. Loss of some reactive aluminosilicate minerals, formation of secondary, precipitated, surface-attached gypsum and loss of fine secondary jarosite occurs across this pH range but fine, surface-attached jarosite is still found in the 522 week sample implying relatively slow dissolution kinetics. In comparison with the 384 week sample, armouring of highly reacted pyrite particles by surface layers of iron oxyhydroxides and aluminosilicates has become more extensive at 522 weeks after return of the pH to neutral values. This is consistent with results from Freeport field samples from limestone blended test pads where pyrite armouring was also substantially increased at higher pH. The results suggest that it may be possible to effectively maintain neutral pH and passivate pyrite, reducing oxidation rates by more than an order of magnitude, using limestone-saturated solution dump feed rather than bulk limestone blending or covers.     

The potential role of geosynthetic clay liners in mine water treatment systems

Combined passive treatment technologies have been used to treat acidic rock drainage (ARD), the well-known acute and costly environmental problem facing the mining industry. It is shown that geosynthetic clay liners (GCLs) were able to attenuate metals from lime treated ARD water, and maintain a neutral pH and low hydraulic conductivity (less than 4.0 × 10⁻11 m/s) after 16 pore volumes of permeation; this implies their usefulness as a potentially significant component in combined passive treatment systems. Presented are laboratory breakthrough data for Cu, Cd, Ni, Mn, and Zn from the permeation of GCLs with 16 pore volumes of ARD, treated ARD (TARD), and a landfill leachate. Metal retention occurred in all solutions, but was greatest for the TARD, producing removal efficiencies of greater than 80%.     

A simplified method for estimation of jarosite and acid-forming sulfates in acid mine wastes

In acid base accounting (ABA) estimates of acid mine wastes, the acid potential (AP) estimate can be improved by using the net carbonate value (NCV) reactive sulfide S method rather than total S assay methods but this does not give recovery of potentially acid producing ferrous and ferric sulfates present in many wastes. For more accurate estimation of AP, an effective, site-specific method to quantify acid sulfate salts, such as jarosite and melanterite, in waste rocks has been developed and tested on synthetic and real wastes. The SPOCAS (acid sulfate soils) methods have been modified to an effective, rapid method to speciate sulfate forms in different synthetic waste samples. A three-step sequential extraction procedure has been established. These steps are: (1) argon-purged water extraction (3 min) to extract soluble Fe(II) salts (particularly melanterite), epsomite and gypsum (<10 wt.%), (2) roasting at 550 degrees C (1 h) to remove sulfur from pyrite and other reactive sulfides, (3) HCl extraction (4 M, 30 min) for determination of jarosites. Products (solid and aqueous) have been characterized at each step including the jarosite decomposition process in Step 2 where temperature control is critical to avoid S loss. The sequential extraction procedure was used to quantitatively determine melanterite, epsomite, gypsum, pyrite and jarosite concentrations in a synthetic waste sample containing these mineral phases at 5 wt.% in quartz, and also tested using a tailings waste sample to quantitatively determine epsomite, gypsum and jarosite contents. The method is applicable to most waste samples including those with non-pyrite sulfides but for samples containing significant amounts of sulfur (>1 wt.% S) as copper sulfides, the second step of roasting needs to be excluded from the procedure with an increased time of 4 M HCl extraction to 16 h for jarosite determination.     

The Use of an Objective Index for the Assessment of the Contamination of Surface Water and Groundwater by Acid Mine Drainage

Temporal and spatial comparisons of acid mine-drainage contaminated waters are difficult because of the complex physico-chemical nature of the pollutant, and an objective index has been developed and evaluated for the assessment of such waters. The acid mine-drainage index is calculated using a modified arithmetic weighted index utilizing seven parameters which are most indicative of acid mine-drainage contamination, i.e. pH value, sulphate, iron, zinc, aluminium, copper and cadmium. Weighting is used to express the relative indicator value of each parameter. pH and sulphate are considered to be of greatest indicator value as they are unaffected by sorption processes, while sulphate is also unaffected by natural neutralization processes. The acid mine-drainage index, as proposed, is designed to detect and quantify contamination from acid mine drainage, and to help categorize samples, quantify impact and to monitor the recovery of receiving waters.     

浅析山地城市湿地公园的规划途径——以重庆市北部新区九曲河湿地公园规划设计为例

本文以重庆市北部新区九曲河湿地公园规划设计为例,介绍了湿地公园建设对城市的重要性以及山地城市湿地公园的特点和规划途径,以期为山地城市的生态保护和湿地公园规划设计提供参考。     

Tannery effluent as a carbon source for biological sulphate reduction

Tannery effluent was assessed as a carbon source for biological sulphate reduction in a pilot-scale upflow anaerobic sludge blanket (UASB), stirred tank reactor (STR) and trench reactor (TR). Sulphate removals of between 60-80% were obtained in all three reactors at total sulphate feed levels of up to 1800 mg l(-1). Sulphate removal in the TR (400-500 mg SO4 l(-1) day(-1)) and UASB (up to 600 mg SO4 l(-1) day(-1)) were higher than those obtained in the STR (250 mg SO4 l(1) day(-1)). A change in operation mode from a UASB to a STR had a large impact on chemical oxygen demand (COD) removal efficiencies. COD removal rates decreased by 25% from 600-700 mg COD l(-1) day(-1) to 200-600 mg COD l(-1) day(-1). The TR had an average COD removal rate of 500 mg COD l(-1) day(-1). Large quantities of sulphide were produced in the reactors (up to 1500 mg l(-1)). However due to the elevated pH in the reactor, only a small amount was in the form of H2S and thus the odour problem normally associated with biological sulphate reduction was not present.     

气提升交替环流符合滤料滤池污水处理工艺的应用

介绍了气提升交替循环流复合滤料滤池的基本结构、工作原理及工艺特点,并将其应用于马鞍山市中心医院污水处理.运行结果表明,污水经该工艺处理后,CODcr、BOD5、SS及氨氮的平均去除率分别达到82.80％,88.64％,67.84％和93.72％,粪大肠菌群的灭活率在99.99％以上,且耐冲击负荷能力强,运行稳定,是一种...     

Post-reclamation water quality trend in a Mid-Appalachian watershed of abandoned mine lands

Abandoned mine land (AML) is one of the legacies of historic mining activities, causing a wide range of environmental problems worldwide. A stream monitoring study was conducted for a period of 7 years to evaluate the water quality trend in a Mid-Appalachian watershed, which was heavily impacted by past coal mining and subsequently reclaimed by reforestation and revegetation. GIS tools and multivariate statistical analyses were applied to characterize land cover, to assess temporal trends of the stream conditions, and to examine the linkages between water quality and land cover. In the entire watershed, 15.8% of the land was designated as AML reclaimed by reforestation (4.9%) and revegetation (10.8%). Statistic analysis revealed sub-watersheds with similar land cover (i.e. percentage of reclaimed AML) had similar water quality and all tested water quality variables were significantly related to land cover. Based on the assessment of water quality, acid mine drainage was still the dominant factor leading to the overall poor water quality (low pH, high sulfate and metals) in the watershed after reclamation was completed more than 20 years ago. Nevertheless, statistically significant improvement trends were observed for the mine drainage-related water quality variables (except pH) in the reclaimed AML watershed. The lack of pH improvement in the watershed might be related to metal precipitation and poor buffering capacity of the impacted streams. Furthermore, water quality improvement was more evident in the sub-watersheds which were heavily impacted by past mining activities and reclaimed by reforestation, indicating good reclamation practice had positive impact on water quality over time.     

Metal sulphides from wastewater: assessing the impact of supersaturation control strategies

Metal sulphide precipitation forms an important component of acid mine drainage remediation systems based on bacterial sulphate reduction. However, the precipitation reaction is inherently driven by very high levels of supersaturation with the generation of small particles with poor solid-liquid separation characteristics. In this study, the effect of strategies used to manage supersaturation was investigated during copper and zinc sulphide precipitation reactions. Initial batch studies showed the origin of sulphide (biological or chemical) had no significant effect on the efficiency of zinc sulphide precipitation. For copper, low metal removal efficiency was obtained at metal to sulphide molar ratios below 1.6 in the synthetic sulphide system. This was improved in the biogenic sulphide system, due to the presence of residual volatile fatty acids, but the presence or absence of particulate organic matter had no effect on recovery. Subsequent studies, conducted using synthetic sulphide solutions in a seeded fluidised bed reactor with multiple reagent feed points (2FP and 6FP) and different recirculation flow rates (300 and 120 mL min⁻¹) showed efficient zinc sulphide precipitation, but limited (<10%) deposition on the seeds. Increasing the number of sulphide feed points (2-6) reduced precipitate loss as fines by approximately 10%. Zinc sulphide fines could be effectively recovered from suspension by settling under quiescent conditions. In the copper system, metal recovery was low (ca 40%) due to the formation of very small copper sulphide particles (mean particle size of ca 0.01 μm). Increasing the number of reagent feed points did not affect supersaturation to the extent of altering particle characteristics. The copper sulphide fines could not be recovered by settling, remaining in a stable colloidal suspension due to their highly charged surfaces (zeta potential −50 mV). The change in recirculation flow rate had a limited effect (ca 5% improvement) on process efficiency. The results show that the extremely high supersaturation prevalent during metal sulphide precipitation is difficult to control using conventional approaches and suggest that the seeded fluidised bed reactor is not suitable for this application.     

Bench-scale study of active mine water treatment using cement kiln dust (CKD) as a neutralization agent

The overall objective of this study was to investigate the potential impact on settled water quality of using cement kiln dust (CKD), a waste by-product, to replace quicklime in the active treatment of acidic mine water. Bench-scale experiments were conducted to evaluate the treatment performance of calcium hydroxide (Ca(OH)₂) slurries generated using four different CKD samples compared to a control treatment with quicklime (CaO) in terms of reducing acidity and metals concentrations in acid mine drainage (AMD) samples taken from the effluent of a lead/zinc mine in Atlantic Canada. Results of the study showed that all of the CKD samples evaluated were capable of achieving greater than 97% removal of total zinc and iron. The amount of solid alkaline material required to achieve pH targets required for neutralization of the AMD was found to be higher for treatment with the CKD slurries compared to the quicklime slurry control experiments, and varied linearly with the free lime content of the CKD. The results of this study also showed that a potential benefit of treating mine water with CKD could be reduced settled sludge volumes generated in the active treatment process, and further research into the characteristics of the sludge generated from the use of CKD-generated calcium hydroxide slurries is recommended.     

The use of micro-algal biomass as a carbon source for biological sulphate reducing systems

An upflow anaerobic digestor was fed dried algal biomass as a carbon source to establish the feasibility of using micro-algal biomass as the sole carbon source for biological sulphate reduction. The effect of the COD:SO4 ratio on substrate consumption and sulphate removal efficiencies were assessed by varying the organic carbon content of the media. Similar COD removal efficiencies were obtained irrespective of the influent COD:SO4 ratios, which were 8.1, 11.2 and 15.0. However, the rates of COD removal did differ with influent COD:SO4 ratios. The percentage sulphate removed decreased as the ratio of COD:SO4 increased. Not all of the COD was used for sulphate reduction, with only 31% being accounted for.     

A Method to Simulate the Impact of Acid Mine Drainage on River Systems

Abandoned mines create pollution problems in rivers as minewater levels rise and discharges of metal-rich acidic waters occur. Mines adjacent to rivers can cause serious pollution problems, reducing fish stocks and preventing restocking. A computer model has been used to simulate the impact of these discharges and to devise an optimal treatment strategy to meet river quality objectives. The use of this model, through application to two case studies, is described.     

Effect of pH, ionic strength, dissolved organic carbon, time, and particle size on metals release from mine drainage impacted streambed sediments

Acid-mine drainage (AMD) input to a stream typically results in the stream having a reduced pH, increased concentrations of metals and salts, and decreased biological productivity. Removal and/or treatment of these AMD sources is desired to return the impacted stream(s) to initial conditions, or at least to conditions suitable for restoration of the aquatic ecosystem. Some expected changes in the water chemistry of the stream following removal of AMD input include an increase in pH, a decrease in ionic strength, and an increase in dissolved organic carbon (DOC) concentrations from increased biological activity in the absence of toxic metals concentrations. These changes in water chemistry may cause the existing contaminated bed sediments to become a source of metals to the stream water. Streambed sediments, collected from North Fork Clear Creek (NFCC), Colorado, currently impacted by AMD, were assessed for the effects of pH, ionic strength, DOC concentration, time, and particle size on metals release using a factorial design. The design included two levels for each chemical parameter (ionic strength = 40 and 80% lower than ambient; pH = 6 and 8; and DOC = 1 and 3 mg/l higher than ambient), ten sampling times (from zero to 48 h), and two size fractions of sediments (63 μm ≤ x < 2 mm and <63 μm). Greater concentrations of metals were released from the smaller sized sediments compared with the larger, with the exception of Cu. A mild acid digestion (0.6 M HCl) evaluated the amount of each metal that could be removed easily from each of the sediment size fractions. Release of all metals over all time points, treatments, and from both sediment sizes was less than 1% of the extractable concentrations, with the exception of Mn, which ranged from 4 to 7% from the smaller sized sediment. Greater percentages of the 0.6 M HCl-extractable concentrations of Cu, Fe, and Zn were released from the larger sized sediment, while this was true for release of Cd and Mn from the smaller sized sediment. Thus, at least for Cd and Mn, the observed higher concentrations released from the smaller sized sediment with each treatment solution is not simply a function of these particles having higher concentrations available for release, but that these metals also are more readily released from the smaller sediment particles versus the larger. DOC concentration strongly influenced the release of Cu; ionic strength strongly influenced the release of Cd, Mn, and Zn; and interaction effects were observed with the release of Cu, Mn, and Zn from the larger size fraction and with the release of Zn from the smaller size fraction. Overall, results suggest that the expected changes in water chemistry following removal/treatment of the AMD sources would result in a release of metals from the existing sediments, with a greater effect on the release of Cu and Fe, than on the release of Cd, Mn, and Zn.     

Substrate characterisation for a subsurface reactive barrier to treat colliery spoil leachate

Subsurface permeable reactive barriers (PRB) have been used to successfully treat acidic mine drainage in Canada and offer great potential for doing the same in the United Kingdom. A PRB for the treatment of colliery spoil leachate from a site near Newcastle upon Tyne, UK, has been designed. The selection of the reactive media to be used is of paramount importance, with particular reference to permeability and reactivity. A number of reactive media mixtures containing varying proportions of cattle slurry screenings, green waste compost, calcite limestone chips and pea gravel were prepared and their respective permeabilities and reactivities were investigated. Media mixtures containing 50% 10 mm grade calcite limestone chips showed better alkalinity addition and metals removal than a blank containing 50% pea gravel. A media mixture containing 50% limestone chips and 50% green waste compost showed a 24 h period to achieve maximum addition of alkalinity and maximum removal of acidity and metals. Mixtures containing 25% green waste compost and 25% slurry screenings achieved maximum addition/removal in 4 h. The likely presence of iron sulphide in samples drawn from test vessels during both test runs indicates that bacterial sulphate reduction is occurring in this composite.     

Removal of phosphorus from agricultural wastewaters using adsorption media prepared from acid mine drainage sludge

Excess phosphorus in wastewaters promotes eutrophication in receiving waterways. A cost-effective method for the removal of phosphorus from water would significantly reduce the impact of such wastewaters on the environment. Acid mine drainage sludge is a waste product produced by the neutralization of acid mine drainage, and consists mainly of the same metal hydroxides used in traditional wastewater treatment for the removal of phosphorus. In this paper, we describe a method for the drying and pelletization of acid mine drainage sludge that results in a particulate media, which we have termed Ferroxysorb, for the removal of phosphorus from wastewater in an efficient packed bed contactor. Adsorption capacities are high, and kinetics rapid, such that a contact time of less than 5 min is sufficient for removal of 60-90% of the phosphorus, depending on the feed concentration and time in service. In addition, the adsorption capacity of the Ferroxysorb media was increased dramatically by using two columns in an alternating sequence so that each sludge bed receives alternating rest and adsorption cycles. A stripping procedure based on treatment with dilute sodium hydroxide was also developed that allows for recovery of the P from the media, with the possibility of generating a marketable fertilizer product. These results indicate that acid mine drainage sludges - hitherto thought of as undesirable wastes - can be used to remove phosphorus from wastewater, thus offsetting a portion of acid mine drainage treatment costs while at the same time improving water quality in sensitive watersheds.