Effectiveness of sulfate-reducing passive bioreactors for treating highly contaminated acid mine drainage: II. Metal removal mechanisms and potential mobility

Column bioreactors were used for studying mechanisms of metal removal, assessment of long-term stability of spent reactive mixtures, as well as potential metal mobility after treating highly contaminated acid mine drainage (AMD; pH 2.9–5.7). Several physicochemical, microbiological, and mineralogical analyses were performed on spent reactive mixtures collected from 4 bioreactors, which were tested in duplicate for two hydraulic retention times (7.3d and 10d), with downward flow over an 11-month period. Consistent with the high metal concentrations in the AMD feed, and with low metal concentrations measured in the treated effluent, the physicochemical analyses indicated very high concentrations of metals (Fe, Mn, Cd, Ni, and Zn) in the top and bottom layers of the reactive mixtures from all columns. Moreover, the concentrations of Fe (50.8–57.8 g/kg) and Mn (0.53–0.70 g/kg) were up to twice as high in the bottom layers, whereas the concentrations of Cd (6.77–13.3 g/kg), Ni (1.80–5.19 g/kg) and Zn (2.53–13.2 g/kg) were up to 50-times higher in the top layers. Chemical extractions and elemental analysis gave consistent results, which indicated a low fraction of metals removed as sulfides (up to 15% of total metals recovered in spent reactive mixtures). Moreover, Fe and Mn were found in a more stable chemical form (residual fraction was 42–74% for Mn and 30–77% for Fe) relative to Cd, Ni or Zn, which seemed more weakly bound (oxidisable/reducible fractions) and showed higher potential mobility. Besides identifying (oxy)hydroxide and carbonate minerals, the mineralogical analyses identified metal sulfides containing Fe, Cd, Ni and Zn. Metal removal mechanisms were, therefore, mainly adsorption and other binding mechanisms with organic matter (for Cd, Ni and Zn), and the precipitation as (oxy)hydroxide minerals (for Fe and Mn). After 15 months, however, the column bioreactors did not lose their capacity for removing metals from the AMD. Although the metals were immobile during the bioreactor treatment, their mobility could increase from spent reactive mixtures, if stored inappropriately. Metal recovery by acidic leaching of spent substrates at the end of bioreactor operation could be an alternative.     

Laboratory and field evaluation of a flushable oxic limestone drain for treatment of net-acidic drainage from a flooded anthracite mine, Pennsylvania, USA

This paper demonstrates the use of dissolution-rate data obtained in the laboratory to indicate the potential quality of effluent from a field-scale oxic limestone drain (OLD) treatment system for neutralization of dilute acidic mine drainage (AMD). Effluent from the Reevesdale Mine South Dip Tunnel, a large source of AMD and base flow to the Wabash Creek and Little Schuylkill River in the Southern Anthracite Coalfield of east-central Pennsylvania, is representative of AMD with low concentrations but high loadings of dissolved Fe, Al and other metals because of a high flow rate. In January 2003, rapid neutralization of the AMD from the Reevesdale Mine was achieved in laboratory tests of its reaction rate with crushed limestone in closed, collapsible containers (Cubitainers). The tests showed that net-alkaline effluent could be achieved with retention times greater than 3 h and that effluent alkalinities and associated dissolution rates were equivalent for Fe(OH)₃-coated and uncoated limestone. On the basis of the laboratory results, a flushable OLD containing 1450 metric tons of high-purity calcitic limestone followed by two 0.7-m deep wetlands were constructed at the Reevesdale Mine. During the first year of operation, monthly data at the inflow, outflow and intermediate points within the treatment system were collected (April 2006–2007). The inflow to the treatment system ranged from 6.8 to 27.4 L/s, with median pH of 4.7, net acidity of 9.1 mg/L CaCO₃, and concentrations of dissolved Al, Fe and Mn of 1.0, 1.9 and 0.89 mg/L, respectively. The corresponding effluent from the OLD had computed void-volume retention times of 4.5–18 h, with median pH of 6.6, net acidity of −93.2 mg/L CaCO₃, and concentrations of dissolved Al, Fe and Mn of <0.1, 0.08 and 0.52 mg/L, respectively. The wetlands below the OLD were effective for retaining metal-rich solids flushed at monthly or more frequent intervals from the OLD, but otherwise had little effect on the effluent quality. During the first year of operation, approximately 43 metric tons of limestone were dissolved and 2 metric tons of Al, Fe and Mn were precipitated within the OLD. However, because of the accumulation of these metals within the OLD and possibly other debris from the mine, the effectiveness of the treatment system declined. Despite the installation of a flush-pipe network at the base of the OLD to remove precipitated solids, the limestone bed clogged near the inflow. Consequently, a large fraction of the AMD bypassed the treatment system. To promote flow through the OLD, the flush pipes were open continuously during the last 4 months of the study; however, this effluent was only partially treated because short-circuiting through the pipes decreased contact between the effluent and limestone. A reconfiguration of the flow path through the limestone bed from horizontal to vertical upward could increase the limestone surface area exposed to the metal-laden influent, increase the cross-sectional area perpendicular to flow, decrease the flow path for solids removal, and, consequently, decrease potential for clogging.     

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).     

Sulfate reducing bioreactor dependence on organic substrates for remediation of coal-generated acid mine drainage: Field experiments

Field experiments were conducted over a 460-day period to assess the efficiency of different mixtures of organic substrates to remediate coalmine-generated acid mine drainage (AMD). Five pilot-scale, flow-through bioreactors containing mixtures of herbaceous and woody organic substrates along with one control reactor containing only limestone were constructed at the Tab-Simco site and exposed to AMD in situ. Tab-Simco is an abandoned coal mine near Carbondale, Illinois that produces AMD with pH ∼2.5 and notably high average concentrations of SO₄ (5050 mg/L), Fe (950 mg/L), Al (200 mg/L), and Mn (44 mg/L). Results showed that the sequestration of SO₄ and metals was achieved in all reactors; however, the presence and type of organic carbon matrix impacted the overall system dynamics and the AMD remediation efficiency. All organic substrate-based reactors established communities of sulfate reducing microorganisms that contributed to enhanced removal of SO₄, Fe, and trace metals (i.e., Cu, Cd, Zn, Ni) via microbially-mediated reduction followed by precipitation of insoluble sulfides. Additional mechanisms of contaminant removal were active in all reactors and included Al- and Fe-rich phase precipitation and contaminant surface sorption on available organic and inorganic substrates. The organic substrate-based reactors removed more SO₄, Fe, and Al than the limestone-only control reactor, which achieved an average removal of ∼19 mol% SO₄, ∼49 mol% Fe, 36 mol% Al, and 2 mol% Mn. In the organic substrate-based reactors, increasing herbaceous content correlated with increased removal efficiency of SO₄ (26–35 mol%), Fe (36–62 mol%), Al (78–83 mol%), Mn (2–6 mol%), Ni (64–81 mol%), Zn (88–95 mol%), Cu (72–85 mol%), and Cd (90–92 mol%), while the diversity of the intrinsic microbial community remained relatively unchanged. The extrapolation of these results to the full-scale Tab-Simco treatment system indicated that, over the course of a 460-day period, the predominantly herbaceous bioreactors could remove up to 92,500 kg SO₄, 30,000 kg Fe, 8,950 kg Al, and 167 kg Mn, which represents a 18.3 wt%, 36.8 wt%, 4.1 wt% and 82.3 wt% increase in SO₄, Fe, Al, and Mn, respectively, removal efficiency compared to the predominantly ligneous bioreactors.The results imply that anaerobic organic substrate bioreactors are promising technologies for remediation of coal-generated AMD and that increasing herbaceous content in the organic substrate matrix can enhance contaminant sequestration. However, in order to improve the remediation capacity, future designs must optimize not only the organic carbon substrate but also include a pretreatment phase in which the bulk of dissolved Fe/Al-species are removed from the influent AMD prior to entering the bioreactor because of 1) seasonal variations in temperature and redox gradients could induce dissolution of the previously formed redox sensitive compounds, and 2) microbially-mediated sulfate reduction activity may be inhibited by the excessive precipitation of Al- and Fe-rich phases.     

Fuzzy modelling of acid mine drainage environments using geochemical,ecological and mineralogical indicators

Fuzzy logic was applied to model acid mine drainage (AMD) and to obtain a classification index of the environmental impact in a contaminated riverine system. The data set used to develop this fuzzy model (a fuzzy classifier) concerns an abandoned mine in Northern Portugal—Valdarcas mining site. Here, distinctive drainage environments (spatial patterns) can be observed based on the AMD formed in the sulphide-rich waste-dumps. Such environments were established, as the effluent flows through the mining area, using several kinds of indicators. These are physical–chemical, ecological and mineralogical parameters, being expressed in a quantitative or qualitative basis. The fuzzy classifier proposed in this paper is a min–max fuzzy inference system, representing the spatial behaviour of those indicators, using the AMD environments as patterns. As they represent different levels (classes) of contamination, the fuzzy classifier can be used as a tool, allowing a more reasonable approach, compared with classical models, to characterize the environmental impact caused by AMD. In a general way it can be applied to other sites where sulphide-rich waste-dumps are promoting the pollution of superficial water through the generation of AMD. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Understanding of the biochemical events in a chemo-bioreactor during continuous acid mine drainage treatment

Spent mushroom compost (SMC) is widely used as reactor matrix in passive bioreactor involving sulfate reducing bacteria (SRB) for acid mine drainage (AMD) treatment. Follow-up our previous report, recent work has been established the extent of activity, sustained organic carbon availability, and the biochemical events of successive alkalinity producing system-based chemo-bioreactor for continuous performance using SMC. Removal of iron and sulfate from influent was over 77 and 90%, respectively, for first 13 weeks, while sulfate removal efficiency suddenly dropped down to 31% thereafter. Ahead of 13th week, process failure was beginning to be noticed when available dissolved organic carbon (DOC) value dropped down to 50 mg/L. SRB population was mostly affected with DOC drought at this stage. Sulfur was one of the major elements found with other tested metals in blackish green effluent precipitate. Sulfide compounds of the tested metals were formed on both exhausted chemo-bioreactor bed and precipitate. FTIR analysis indicated that SMC was responsible for metal binding and available nutrients supply. The present study revealed the feasibility of SMC as a host for treating AMD by this chemo-bioreactor that will assist in designing the continuous treatment practice.     

Treatment of septic tank effluent using moving-bed biological reactor: kinetic and biofilm morphology

Septic tanks are very commonly used wastewater collection systems throughout the world, and especially in rural areas. In this study, the use of moving-bed biological reactors (MBBR) for the treatment of septic tank effluent (STE) was examined. The study was conducted in two phases. In Phase I, the performance of septic tanks from four projects working under different operational conditions and with different service lives was followed to determine the parameters that required further treatment. In Phase II, four specially designed continuous flow pilot-plant MBBRs and one laboratory-scale batch reactor were tested for their efficiency in treating STE. Experiments were carried out at various temperatures (8–25 °C) and with different hydraulic retention times (HRTs). MBBR effectively reduced STE’s nutrients and chemical oxygen demand by 90 and 85 %, respectively, over 180 days of operation. The average ammonia removal rate at 25 °C increased from 0.279 to 0.540 kg N/m³ when the reactor HRT changed from 5.7 to 13.3 h. Under these conditions, the ammonia removal kinetics were successfully correlated with a theta model with an average θ value of 1.054. The biofilm morphology showed a stable and global biomass coverage (>70 %) and a high percentage of live cells. A thinner biofilm was observed when the MBBR operated at high temperatures. The results of this study showed that MBBR is a promising technology for post-treatment of septic tank effluent.     

Solid phase characterization and metal deportment in a mussel shell bioreactor for the treatment of AMD,Stockton Coal Mine,New Zealand

The Stockton Coal Mine, located on the West Coast of New Zealand, is evaluating the use of a mussel shell bioreactor (MSB) to treat acidic metalliferous runoff from acid forming overburden. This novel approach is similar in concept to vertical flow wetlands (VFWs) and successive alkalinity producing systems (SAPS). The MSB system is a trapezoidal pit 2 m deep, 35 m long, 3–10 m wide with 60° angle sides. During operation it contained 160 tonnes (240 m³) of mussel shell material and was saturated with a 100–200 mm water cap. Influent flowed through the reactor at a mean rate of 0.3 L s⁻¹ resulting in a hydraulic retention time (HRT) of ≈6 days. The prototype MSB was in operation for a total of 1027 days, from June 2009 through March 2012, and effectively sequestered 99.7% of Al, 99.3% of Fe, 98.8% of Ni, 98.4% Tl and 99.3% of Zn, as determined from a previous evaluation of MSB performance. The MSB also effectively neutralized acidity, which resulted in an increase in influent pH from 2.8 to 6.9 in the effluent. Based on an examination of several excavated pits, five distinct reaction zones developed within the MSB. The reaction zones consisted of an allochthonous sediment layer (0–330 mm), an oxidized iron-rich ocherous layer (at 330–350 mm depth), an aluminum layer (at 350–600 mm depth) with geochemical variations throughout (350–500 mm and 500–600 mm); and a chemically reduced bottom shell layer (at 600–1100 mm). Representative samples were collected from each layer and analyzed using a combination of geochemical and physical methods to assess the stability of the secondary minerals and trace metal deportment within the MSB. Major elements Fe, Al, Ni, Tl, and Zn where preferentially associated with particular layers within the MSB. Elevated concentrations of Fe (110,000 mg kg⁻¹) were observed in the allochthonous sediment and ocherous precipitate layers, while Al (27,816 mg kg⁻¹), Ni (55 mg kg⁻¹), and Zn (655 mg kg⁻¹) were elevated within the aluminum and lower reduced depths within the MSB. Trace Tl (21 mg kg⁻¹) showed varying concentrations throughout the MSB, but was strongly correlated to lower layers of the system. Microbial biofilms were observed within the reduced portions of the shell layers often proximal to bacterial shaped sulfides. The geochemical assessment of the MSB presented in this study is the first of its kind for a MSB, and supports the argument that this system is another viable option for passive treatment of AMD.     

Acid mine drainage at Cerro Rico de Potosí II: severe degradation of the Upper Rio Pilcomayo watershed

Ag, Pb, Sn and Zn ores have been intensively mined and processed at Cerro Rico de Potosí, Bolivia since 1545. Acid mine drainage (AMD) and mineral processing plant effluent are prime sources of water contamination in the headwaters of the Upper Rio Pilcomayo watershed. Streams receiving AMD drainage from the slopes of Cerro Rico and surrounding landscapes were sampled during the dry (July–August 2006) and wet (March 2007) seasons of one water-year. In-stream waters contained total metal concentrations of up to 16 mg/L As, 4.9 mg/L Cd, 0.97 mg/L Co, 1,100 mg/L Fe, 110 mg/L Mn, 4.1 mg/L Pb, and 1,500 mg/L Zn with pH ranging from 2.8 to 9.5. AMD-impacted streams contained elevated concentrations of the same major ecotoxic constituents present in AMD discharges at concentrations orders of magnitude greater than in those streams unimpacted by AMD. Many of the AMD impacted water bodies are more degraded than class “D” of the Bolivian receiving water body criteria, rendering them unfit for domestic or agricultural use. Natural attenuation is insufficient to render waters safe for use, however, some of these waters are currently being utilized for irrigation and livestock watering. The data indicate that historic and current mining activities have transformed these key natural resources into potential human and environmental health hazards.     

Assessment of heavy metal accumulation in macrophyte, agricultural soil, and crop plants adjacent to discharge zone of sponge iron factory

The present study deals with the characterization of effluent released from sponge iron industries and distribution of heavy metals in soil and macrophytes near to effluent discharge channel. Apart from this, accumulation of heavy metals in nearby soil and vegetation system irrigated with effluent-contaminated water is also the subject of this study. Physico-chemical analysis of effluent reveals that the concentration of total suspended solids (TSS), total hardness (TH), iron (Fe²⁺), and oil and grease are greater than the IS (1981) norms for discharge of water into inland water body. The soil along the sides of the effluent channel also shows higher concentration of heavy metals than the background soil. The enrichment of the heavy metals are in the order of Chromium (Cr) > Iron (Fe) > Manganese (Mn) > Zinc (Zn) > Copper (Cu) > Cadmium (Cd). Macrophytes growing along the sides of the effluent channel also show significant accumulation of heavy metals almost in the same order as accumulated in soil. Higher uptake of heavy metals by these varieties reveals that these species can be used for future phytoremediation. The effluent as well as contaminated water is extensively used for irrigation for growing vegetables like tomato (Lycopersicon esculatum) in the surrounding areas. Heavy metal accumulation in this agricultural soil are in the sequence of Cr > Fe > Mn > Zn > Cu > Cd. More or less similar type of accumulation pattern are also found in tomato plants except Fe and Zn exceeding Cr and Mn. Transfer Factor of heavy metals from soil to tomato plants (TF_S) shows average value of <1, suggesting less uptake of heavy metals from soil. Among the plant parts studied, fruit shows least accumulation. Although tomato plants show some phenotypic changes, the survival of tomato plants as well as least accumulation of metals in fruit reveals their tolerance to heavy metals. Therefore it may be suggested that this plant can be grown successfully in the heavy metal contaminated soil. Further research work on in situ toxicity test will be necessary in order to identify the most resistive variety on this particular type of contaminated site.     

In situ biotreatment of acidic mine drainage using straw as sole substrate

Feasibility of using straw as sole substrate for in situ bioremediation of acidic mine drainage (AMD) was studied. The result showed that straw was more suitable than woodchips, which had been successfully used for bioremediating AMD at the source, for establishing bioremediation layer. The sulfate removal rate of rice straw treatment was almost two times higher than that of the woodchips treatment when the initial pH of the synthetic AMD was set to 3.0. Straw treatment may be more efficient at reducing sulfate than woodchips treatment under stressful conditions. The sulfate removal rate of the rice straw treatment increased from 8.67 to 21.77 mg L⁻¹ day⁻¹ when initial pH increased from 1 to 7 while the removal rate of woodchips treatment increased from 3.80 to 11.95 mg L⁻¹ day⁻¹. The sulfate removal rate of the rice straw treatment decreased from 13.93 to 9.91 mg L⁻¹ day⁻¹ when temperature decreased from 25 to 5°C while the removal rate of woodchips treatment decreased from 7.43 to 4.98 mg L⁻¹ day⁻¹. Differences in soluble organic carbon release between rice straw and woodchips led to the differences in bioremediation efficiency. Concentrations of Cu²⁺ maintained at low level in the column effluent during the whole bioremediation period. Cu²⁺ was removed by forming sulfide precipitates. Microbial community analysis showed that sulfate reducing bacteria in the bioremediation layer together with microorganisms capable of degrading rice straw caused the bioremediation of AMD. These findings have significant environmental implications in terms of in situ bioremediation of AMD using straw as sole substrate.     

Treatment of Acid Mine Drainage (AMD) in South Brazil: Comparative active processes and water reuse

This work describes AMD techniques of neutralization, with lime, flocculation of the precipitates and comparative flocs/liquid separation by flotation with microbubbles or by lamellar settling (LS). The AMD treated water was characterized by its quality for recycling in terms of inorganic or organic elements, suspended or dissolved solids, among others. Two types of flocs were formed, “aerated” or not, in a special flocculation reactor, patented by this research group (RGF^®). Aerated flocs formed (within seconds) entered into contact with microbubbles under high shearing and raised-up at rates > 120 mh^− 1 allowing a rapid solid–liquid separation by flotation (HR-high rate), at about 13–15 m³m^− 2 h^− 1 loading capacity. Conversely, the non-aerated flocs settled at about 5–6 m h^− 1 in a lamella settler. Both AMD treatment techniques showed similar efficiencies (removal of ions > 90%) but the separation by lamella settling presented advantages, namely less reagents (no flotation collector required), lower power requirements and easier to operate. The operating costs (approximate values) of the AMD treatment by LS at pH 9 reaches about 0.3 US$ m^− 3 against 0.6 US$ m^− 3 for the HR-flotation process. Results found were proved to be similar to those found in recent ADM treatment installations in South Brazil. The quality of the treated water is fairly good, nearly free of heavy metals ion, low BOD (biological oxygen demand) and TOC (total organic content), low solids content and may be readily reused for irrigation, industrial processes and as wash water (among others, streets, vehicles, dust control). However, there is a need to extend the use of this treated water resource, but this, at least in Brazil, has not been legislated properly. It is concluded that this research will contribute in the discussion of this old and complex problem in acid mining effluents worldwide.     

Interactions Between Soils and Laboratory Simulated Electrolyte Solution

To study the impact of salt water intrusion on two types of soils from west coast region of India were investigated in the laboratory. The key characteristics evaluated included Atterberg limits, compaction characteristics, hydraulic conductivity and chemical characteristics of selected soils. The sea at this coast receives effluent from different points and hence the characteristics change with time and locality. Therefore, to maintain uniform composition, 0.5 N sodium chloride solution (NaCl) was prepared in the laboratory and batch tests were used to determine the immediate effect on soils. Soil specimens were prepared by mixing the soils with 0.5 N NaCl in the increments of 0, 5, 10 and 20% by weight to vary the degree of contamination. Experimental results of soils mixed with 0.5 N NaCl showed that the maximum dry density increases and the optimum moisture content (OMC) decreases with increasing sodium chloride concentration. The study also revealed that the hydraulic conductivity of the soils tested increases with increase in sodium chloride concentration. The Atterberg limits of contaminated specimens show a remarkable change when compared with uncontaminated specimens.     

Investigation of the hydro-mechanical behaviour of GMZ bentonite pellet mixtures

Bentonite pellet mixtures are considered as one of the candidate sealing materials for deep geological disposals of radioactive waste. One of the particularities of this material is the initial heterogeneous distribution of pellets and porosity within the mixture, leading to complex hydro-mechanical behaviour. In this paper, the hydro-mechanical properties of GMZ bentonite pellet mixtures were investigated in the laboratory by carrying out water retention tests on pellet mixtures under constant-volume condition and single pellets under free swelling condition, as well as a infiltration test on a column specimen of pellet mixture. In the infiltration test, the relative humidity and radial swelling pressure were monitored at five heights, the axial swelling pressure was also recorded. The instantaneous profile method was applied to determine the unsaturated hydraulic conductivities. Results show that, in high suction range (>?10 MPa) the water retention curve of pellet mixture under constant-volume condition was comparable to that of a single pellet under free swelling condition, while in low suction range (<?10 MPa) the latter exhibits a much higher water retention capacity. Due to clogging of large pores, the unsaturated hydraulic conductivity decreases as suction decreases to around 25 MPa. However, with further suction decrease, the hydraulic conductivity increases continuously until the value at saturated state, as in the case of most unsaturated soils. The radial swelling pressure at different heights develops with local sudden increase and decrease, which was attributed to local rearrangement of pellets upon wetting. By contrast, as the axial swelling pressure was measured on the global surface of the specimen, it develops in a more regular fashion.

     

Electrokinetic retention, migration and remediation of nitrates in silty loam soil under hydraulic gradients

Contamination of groundwater by nitrates leaching from intensive agricultural and livestock operations have become a major concern for surrounding communities that use groundwater as their water supply. High levels of nitrate in drinking water poses a significant risk to human health, i.e., methaemoglobinaemia (“blue baby” syndrome).

The traditional pump-and-treat method is ineffective in medium to fine-textured agricultural soils due to the low hydraulic conductivity. This paper presents the results of a laboratory experiment investigating the feasibility of using electrokinetic treatment in retaining, accumulating, moving and remediating nitrates in a silty loam soil under hydraulic gradients.

A hydraulic gradient of 1.25 was applied to the horizontal soil columns to simulate a groundwater movement system. The study was performed in two stages. During the first stage of the experiment, the anode located at the inflow end of the columns was able to retard the movement of nitrates even under a hydraulic gradient of 1.25. After 15 days of flow, the effluent nitrate concentration in the control column rose to 90 mg l⁻¹ while no nitrates were detected in the effluent from columns subjected to the electrokinetic treatment.

After 15 days, the polarity of the electrodes was switched and this second stage lasted another 20 days. The cathode near the inflow end promoted the conversion of nitrates entering the column to other forms. The anode near the outflow end promoted the migration and accumulation of negatively charged nitrate ions towards the outflow end. By the 12th day, the nitrate concentrations in the electrokinetically treated columns were brought down to <5 mg NO₃-N l⁻¹. Electrokinetic treatment retarded nitrate movement against a hydraulic gradient of 1.25 and effectively restored a medium-textured soil contaminated with NO₃-N.

The NO₂-N level remained below 1 mg l⁻¹ throughout the experiment. The hydraulic conductivity varied between 1.0E–7 and 3.6E–7 m s⁻¹. The current requirement varied between 3 and 6 mA.     

Investigating remote sensing indices to monitor drought impacts on a local scale (case study: Fars province,Iran)

As drought occurs in different climates, assessment of drought impacts on parameters such as vegetation cover is of utmost importance. Satellite remote sensing images with various spectral and spatial resolutions represent information about different land covers such as vegetation cover. Hence, the purpose of this study was to investigate the performance of satellite vegetation indices to monitor the agricultural drought on a local scale. In this regard, satellite images including Moderate Resolution Imaging Spectroradiometer (MODIS) and Advanced Very High Resolution Radiometer (AVHRR) data were used to evaluate vegetation cover and their gradual changes effects on agricultural drought. Fars province in Iran with relatively low precipitation values was selected as the study area. Modified Perpendicular Drought Index (MPDI), MPDI1, Vegetation Condition Index (VCI), Normalized Difference Vegetation Index Anomalies (NDVIA), and Standardized Vegetation Index (SVI), were evaluated to select the remote sensing based index with the best performance in drought monitoring. The performance of such indices were investigated during 13 years (2000–2013) for MODIS and 29 years (1985–2013) for AVHRR. To assess the efficiency of the satellite indices in drought investigation, Standardized Precipitation Index (SPI) data of five selected stations were used for 3, 6, and 9 month periods on August. The results showed that NDVI-based vegetation indices had the highest correlation with SPI in cold climate and long-term timescale (6 and 9 month). The highest correlation values between remote sensing based indices and SPI were acquired, respectively, in 9-month and 6-month time-scales, with the values of 43.5% and 40%. Moreover, VCI showed the highest capability for agricultural drought investigating in different climate regions of the study area. Overall, the results proved that NDVI-based indices can be used for drought monitoring and assessment in a long-term timescale on a local time-scale.

     

Reactive transport modelling of the long-term interactions of corrosion products and compacted bentonite in a HLW repository in granite: Uncertainties and relevance for performance assessment

Here we present a long-term nonisothermal reactive transport model for the interactions of the corrosion products of a carbon-steel canister and the compacted bentonite of the engineered barrier of a high-level radioactive waste repository in granite. Canister corrosion causes an increase in the pH and the concentration of dissolved Fe²⁺ of the bentonite porewater. Iron precipitates as magnetite and siderite and sorbs via cation exchange and surface complexation on weak sites. Magnetite precipitation reduces significantly the porosity of the bentonite near the canister. The thickness of the zone of reduced porosity is 7 cm at t = 1 Ma. This thickness increases significantly when the dependence of the corrosion rate on the chemical conditions is considered and decreases 3 cm when smectite dissolution and analcime precipitation are taken into account. Model results are not significantly sensitive to the thermal transient and the effect of temperature on the corrosion rate. The conclusions of our simulations are consistent for the most part with those reported by others for engineered barrier systems at similar chemical conditions.     

Mercury distribution and transport in a contaminated river system in Kazakhstan and associated impacts on aquatic biota

The River Nura in Central Kazakhstan has been heavily polluted by Hg originating from an acetaldehyde plant. A number of studies were undertaken to investigate the transport, fate and bioavailability of Hg in this river system. The sediments within a 20 km section of the river downstream of the effluent outfall canal are highly polluted and are acting as a strong source of surface water contamination. Mercury transport in the river is dominated by the remobilization of contaminated bed sediments and river bank erosion during the annual spring flood. Peak Hg concentrations in unfiltered surface water samples during a larger than usual flood event in 2004 were in the order of 1600–4300 ng L⁻¹. The majority of the particulate-bound Hg appears to be sedimented in the shallow Intumak reservoir 75 km downstream of the source of the pollution, leading to a drop in aqueous Hg concentrations by an order of magnitude. Nevertheless, background concentrations of Hg in surface water are not reached until at least 200 km downstream, and during the flood period Hg is also detected in the terminal wetlands of the river.Mercury concentrations in sediment cores taken from the river bed in the most contaminated section of the Nura ranged from 9.95 to 306 mg kg⁻¹. Methylmercury (MeHg) levels in shallow sediment cores were highest in surface sediments and ranged between 4.9 and 39 μg kg⁻¹, but were generally less than 0.1% of total Hg (THg). A significant inverse relationship was found between THg concentrations and the percentage of MeHg formed in the sediments, irrespective of the sampling depth. The observed relationship was confirmed by comparison with results from a different river system, indicating that it may be true also for other highly contaminated aquatic systems. It is hypothesized that at high THg levels in severely contaminated sediments, the accumulation of MeHg may be limited by increasingly efficient demethylation processes, and that this underlying trend in sediments is the reason why MeHg levels in surface water are often found to be higher at less contaminated sites compared to upstream sites.Mercury concentrations in biota in the most contaminated section of the river were 15–20 times higher than background levels. Fish were found to be impacted for more than 125 km downstream from the source, indicating significant transport of dissolved MeHg to downstream areas and/or in-situ MeHg production in less contaminated downstream reaches. There were also indications that impoundments may increase the bioavailability of Hg.     

Zero-valent iron and organic carbon mixtures for remediation of acid mine drainage: Batch experiments

A series of laboratory batch experiments was conducted to evaluate the potential for treatment of acid mine drainage (AMD) using organic C (OC) mixtures amended by zero-valent Fe (Fe⁰). Modest increases in SO₄ reduction rates (SRRs) of up to 15% were achieved by augmenting OC materials with 5 and 10 dry wt% Fe⁰. However, OC was essential for supporting SO₄ reducing bacteria (SRB) and therefore SO₄ reduction. This observation suggests a general absence of autotrophic SRB which can utilize H₂ as an electron donor. Sulfate reduction rates (SRRs), calculated using a mass-based approach, ranged from −12.9 to −14.9 nmol L⁻¹ d⁻¹  g⁻¹ OC. Elevated populations of SRB, iron reducing bacteria (IRB), and acid producing (fermentative) bacteria (APB) were present in all mixtures containing OC. Effective removal of Fe (91.6–97.6%), Zn (>99.9%), Cd (>99.9%), Ni (>99.9%), Co (>99.9%), and Pb (>95%) was observed in all reactive mixtures containing OC. Abiotic metal removal was achieved with Fe⁰ only, however Fe, Co and Mn removal was less effective in the absence of OC. Secondary disordered mackinawite [Fe_1+xS] was observed in field-emission scanning electron microscopy (FE-SEM) backscatter electron micrographs of mixtures that generated SO₄ reduction. Energy dispersive X-ray (EDX) spectroscopy revealed that Fe–S precipitates were Fe-rich for mixtures containing OC and Fe⁰, and S-rich in the absence of Fe⁰ amendment. Sulfur K-edges determined by synchrotron-radiation based bulk X-ray absorption near-edge structure (XANES) spectroscopy indicate solid-phase S was in a reduced form in all mixtures containing OC. Pre-edge peaks on XANES spectra suggest tetragonal S coordination, which is consistent with the presence of an Fe–S phase such as mackinawite. The addition of Fe⁰ enhanced AMD remediation over the duration of these experiments, however long-term evaluation is required to identify optimal Fe⁰ and OC mixtures.     

新型组合工艺(CSTR-UASBAF-NMBR)处理有机废水实验及数学建模

采用一套新型生物组合工艺(CSTR产酸发酵反应罐-UASBAF复合厌氧反应池-NMBR新型多级环流膜生物反应器)处理玉米深加工企业生产废水。研究结果表明:经过50d的启动期后系统进入稳定运行阶段,在稳定运行的155d内,组合工艺对COD和BOD的去除率高达99.4%和99.8%。基于厌氧消化数学模型(ADM1)和活性污泥数学模型(ASM1)对本组合工艺进行数学模拟研究,结果表明,该模型对每个工艺的出水COD预测平均误差均在15%以内,表明该模型对这套新型工艺具有很好的预测效果。