Studies on removal of metal ions and sulphate reduction using rice husk and Desulfotomaculum nigrificans with reference to remediation of acid mine drainage

The utility of rice husk as an adsorbent for metal ions such as iron, zinc and copper from acid mine water was assessed. The adsorption isotherms exhibited Langmuirian behavior and were endothermic in nature. The free energy values for adsorption of the chosen metal ions onto rice husk were found to be highly negative attesting to favorable interaction. Over 99% Fe(3+), 98% of Fe(2+) and Zn(2+) and 95% Cu(2+) uptake was achieved from acid mine water, with a concomitant increase in the pH value by two units using rice husk. The remediation studies carried out on acid mine water and simulated acid mine water pretreated with rice husk indicated successful growth of Desulfotomaculum nigrificans (D. nigrificans). The amount of sulphate bioreduction in acid mine water at an initial pH of 5.3 was enhanced by D. nigrificans from 21% to 40% in the presence of rice husk filtrate supplemented with carbon and nitrogen. In simulated acid mine water with fortified husk filtrate, the sulphate reduction was even more extensive, with an enhancement to 73%. Concurrently, almost 90% Fe(2+), 89% Zn(2+) and 75% Cu(2+) bioremoval was attained from simulated acid mine water. Metal adsorption by rice husk was confirmed in desorption experiments in which almost complete removal of metal ions from the rice husk was achieved after two elutions using 1M HCl. The possible mechanisms of metal ion adsorption onto rice husk and sulphate reduction using D. nigrificans are discussed.     

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.     

Natural organic matter (NOM) in roof runoff and its impact on the Fe0 treatment system of dissolved metals

The present work investigates the impacts and mechanisms associated with natural organic matter (NOM) in the Fe0 treatment system of Cu2+ and Zn2+ under roof runoff conditions. The NOM in runoff waters was characterized using XAD-4/8 adsorption resins, copper complexation, acidic capacity and liquid chromatography with online carbon detection. Batch kinetic experiments and flow-through configurations were performed and the results of metal removal were elucidated taking into account the characteristics of NOM. Based on the findings, it is shown that NOM influences the removal of metals through several complex pathways. At an un-favored condition for adsorption of metals, i.e., on iron corrosion products, at pH相似文献   

High-level arsenite removal from groundwater by zero-valent iron

The objectives of this study were to conduct batch and column studies to (i) assess the effectiveness of zero-valent iron for arsenic remediation in groundwater, (ii) determine removal mechanisms of arsenic, and (iii) evaluate implications of these processes with regard to the stability of arsenic and long-term remedial performance of the permeable reactive barrier (PRB) technology. A high concentration arsenic solution (50 mg l(-1)) was prepared by using sodium arsenite (arsenic (III)) to simulate groundwater at a heavily contaminated Superfund site in the USA. Batch studies indicate that the removal of arsenic is a two-step reaction with fast initial disappearance of arsenite followed by a slow subsequent removal process. Flow-through columns were conducted at a flow rate of 17 ml h(-1) under reducing conditions for 6.6 mo. Kinetic analysis suggested that arsenic removal behaves as a zero-order reaction at high arsenic concentrations. Arsenic removal rate constants decreased with time and arsenic breakthrough was observed in the column study. Arsenic removal capacity of zero-valent iron was determined to be approximately 7.5 mg As/g Fe. Carbonate green rust was identified from the analysis of surface precipitates; arsenite uptake by green rust may be a major mechanism responsible for arsenic remediation by zero-valent iron. Analysis of HCl-extractable arsenic from iron samples indicated that approximately 28% of arsenic was in the form of arsenate suggesting that a surface oxidation process was involved in the arsenic removal with zero-valent iron.     

Amendment of hydroxyapatite in reduction of tetrachloroethylene by zero-valent zinc: its rate enhancing effect and removal of Zn(II)

The effects of hydroxyapatite (HAP) on dechlorination of tetrachloroethylene (PCE) by zero-valent zinc (ZVZ) were examined in batch systems. PCE was primarily transformed to trichloroethylene by ZVZ, with 1,2-trans-dichloroethylene representing a minor product. Dechlorination of PCE was accelerated by the presence of HAP, and the pseudo-first order rate constants increased with increasing amount of HAP. Zn(II), mostly generated from oxidative dissolution of ZVZ by PCE, was effectively removed from the solution by HAP. Ion substitution, coprecipitation, and adsorption are proposed as the possible mechanisms for Zn(II) removal. These reactions appeared to occur simultaneously and the contribution of each reaction to overall removal of Zn(II) was primarily dependent on HAP loading at constant ZVZ loading. The results indicate that the use of HAP in combination with conventional zero-valent metals is promising in that it can achieve both degradation of organic contaminants and stabilization of inorganic contaminants.     

The addition of organic carbon and nitrate affects reactive transport of heavy metals in sandy aquifers

Organic carbon introduction in the soil to initiate remedial measures, nitrate infiltration due to agricultural practices or sulphate intrusion owing to industrial usage can influence the redox conditions and pH, thus affecting the mobility of heavy metals in soil and groundwater. This study reports the fate of Zn and Cd in sandy aquifers under a variety of plausible in-situ redox conditions that were induced by introduction of carbon and various electron acceptors in column experiments. Up to 100% Zn and Cd removal (from the liquid phase) was observed in all the four columns, however the mechanisms were different. Metal removal in column K1 (containing sulphate), was attributed to biological sulphate reduction and subsequent metal precipitation (as sulphides). In the presence of both nitrate and sulphate (K2), the former dominated the process, precipitating the heavy metals as hydroxides and/or carbonates. In the presence of sulphate, nitrate and supplemental iron (Fe(OH)(3)) (K3), metal removal was also due to precipitation as hydroxides and/or carbonates. In abiotic column, K4, (with supplemental iron (Fe(OH)(3)), but no nitrate), cation exchange with soil led to metal removal. The results obtained were modeled using the reactive transport model PHREEQC-2 to elucidate governing processes and to evaluate scenarios of organic carbon, sulphate and nitrate inputs.     

Arsenic accumulation in duckweed (Spirodela polyrhiza L.): a good option for phytoremediation

Some unavoidable drawbacks of traditional technologies have made phytoremediation a promising alternative for removal of arsenic from contaminated soil and water. In the present study, the potential of an aquatic macrophyte Spirodela polyrhiza L. for phytofiltration of arsenic, and the mechanism of the arsenic uptake were investigated. The S. polyrhiza L. were grown in three test concentrations of arsenate and dimethylarsinic acid (DMAA) (i.e. 1.0, 2.0 and 4.0microM) with 0 (control), 100 or 500microM of phosphate. One control treatment was also set for each test concentrations of arsenic. The PO(4)(3-) concentration in control treatment was 0.02microM. When S. polyrhiza L. was cultivated hydroponically for 6d in culture solution containing 0.02microM phosphate and 4.0microM arsenate or DMAA, the arsenic uptake was 0.353+/-0.003micromolg(-1) and 7.65+/-0.27nmolg(-1), respectively. Arsenic uptake into S. polyrhiza L. was negatively (p<0.05) correlated with phosphate uptake when arsenate was applied to the culture solutions owing to similar in the sorption mechanism between AsO(4)(3-) and PO(4)(3-), and positively (p<0.05) correlated with iron uptake due to adsorption of AsO(4)(3-) onto iron oxides. Thus, the S. polyrhiza L. accumulates arsenic by physico-chemical adsorption and via the phosphate uptake pathway when arsenate was added to the solutions. These results indicate that S. polyrhiza L. would be a good arsenic phytofiltrator. In contrast, DMAA accumulation into S. polyrhiza L. was neither affected by the phosphate concentration in the culture nor correlated (p>0.05) with iron accumulation in plant tissues, which indicates that S. polyrhiza L. uses different mechanisms for DMAA uptake.     

Zero-valent iron and iron oxide-coated sand as a combination for removal of co-present chromate and arsenate from groundwater with humic acid

The combination of zero-valent iron (Fe⁰) and iron oxide-coated sand (IOCS) was used to remove Cr(VI) and As(V) from groundwater in this study. The efficiency and the removal mechanism of Cr(VI) and As(V) by using this combination, with the influence of humic acid (HA), were investigated using batch experiments. Results showed that, compared to using Fe⁰ or IOCS alone, the Fe⁰-IOCS can perform better on the removal of both Cr(VI) and As(V). Metal extraction studies showed that As(V) was mainly removed by IOCS and iron corrosion products while Cr(VI) was mainly removed by Fe⁰ and its corrosion products. Competition was found between Cr(VI) and As(V) for the adsorption sites on the iron corrosion products. HA had shown insignificant effects on Cr(VI) removal but some effects on As(V) removal kinetics. As(V) was adsorbed on IOCS at the earlier stage, but adsorbed/coprecipitated with the iron corrosion products at the later stage.     

Metal accumulation in wild plants surrounding mining wastes

Four sites were selected for collection of plants growing on polluted soil developed on tailings from Ag, Au, and Zn mines at the Zacatecas state in Mexico. Trace element concentrations varied between sites, the most polluted area was at El Bote mine near to Zacatecas city. The ranges of total concentration in soil were as follows: Cd 11-47, Ni 19-26, Pb 232-695, Mn 1132-2400, Cu 134-186 and Zn 116-827 mg kg(-1) air-dried soil weight. All soil samples had concentrations above typical values for non-polluted soils from the same soil types (Cd 0.6+/-0.3, Ni 52+/-4, Pb 41+/-3mg kg(-1)). However, for the majority of samples the DTPA-extractable element concentrations were less than 10% of the total. Some of the wild plants are potentially metal tolerant, because they were able to grow in highly polluted substrates. Plant metal analysis revealed that most species did not translocate metals to their aerial parts, therefore they behave as excluder plants. Polygonum aviculare accumulated Zn (9236 mg kg(-1)) at concentrations near to the criteria for hyperaccumulator plants. Jatropha dioica also accumulated high Zn (6249 mg kg(-1)) concentrations.     

Effects of various ions on the dechlorination kinetics of hexachlorobenzene by nanoscale zero-valent iron

The effect of several anions and cations normally co-present in soil and groundwater contamination sites on the degradation kinetics and removal efficiency of hexachlorobenzene (HCB) by nanoscale zero-valent iron (NZVI) particles was examined. The degradation kinetics was not influenced by the HCO(3)(-), Mg(2+), and Na(+) ions. It was enhanced in the presence of the Cl(-) and SO(4)(2-) ions due to their corrosion promotion. The NO(3)(-) competes with HCB so it inhibits the degradation reaction. The Fe(2+) ions would inhibit the degradation reaction due to passivation layer formed, while it was enhanced in the presence of Cu(2+) ions resulted from the reduced form of copper on NZVI surfaces. These observations lead to a better understanding of HCB dechlorination with NZVI particles and can facilitate the remediation design and prediction of treatment efficiency of HCB at remediation sites.     

Modification of trace metal accumulation in the green mussel Perna viridis by exposure to Ag, Cu, and Zn

To examine the Cd, Hg, Ag, and Zn accumulation in the green mussel Perna viridis affected by previous exposure to Cu, Ag, or Zn, the dietary metal assimilation efficiency (AE) and the uptake rate from the dissolved phase were quantified. The mussel's filtration rate, metallothionein (MT) concentration, and metal tissue burden as well as the metal subcellular partitioning were also determined to illustrate the potential mechanisms underlying the influences caused by one metal pre-exposure on the bioaccumulation of the other metals. The green mussels were pre-exposed to Cu, Ag, or Zn for different periods (1-5 weeks) and the bioaccumulation of Cd, Hg, Ag, and Zn were concurrently determined. Pre-exposure to the three metals did not result in any significant increase in MT concentration in the green mussels. Ag concentration in the insoluble fraction increased with increasing Ag exposure period and Ag ambient concentration. Our data indicated that Cd assimilation were not influenced by the mussel's pre-exposure to the three metals (Cu, Ag, and Zn), but its dissolved uptake was depressed by Ag and Zn exposure. Although Hg assimilation from food was not affected by the metal pre-exposure, its influx rate from solution was generally inhibited by the exposure to Cu, Ag, and Zn. Ag bioaccumulation was affected the most obviously, in which its AE increased with increasing Ag tissue concentration, and its dissolved uptake decreased with increasing tissue concentrations of Ag and Cu. As an essential metal, Zn bioaccumulation remained relatively stable following the metal pre-exposure, suggesting the regulatory ability of Zn uptake in the mussels. Zn AE was not affected by metal pre-exposure, but its dissolved uptake was depressed by Ag and Zn pre-exposure. All these results indicated that the influences of one metal pre-exposure on the bioaccumulation of other metals were metal-specific due to the differential binding and toxicity of metals to the mussels. Such factors should be considered in using metal concentrations in mussel's soft tissues to evaluate the metal pollution in coastal waters.     

Removal of chromium from synthetic plating waste by zero-valent iron and sulfate-reducing bacteria.

Experiments were conducted to evaluate the potential of zero-valent iron and sulfate-reducing bacteria (SRB) for reduction and removal of chromium from synthetic electroplating waste. The zero-valent iron shows promising results as a reductant of hexavalent chromium (Cr+6) to trivalent chromium (Cr+3), capable of 100% reduction. The required iron concentration was a function of chromium concentration in the waste stream. Removal of Cr+3 by adsorption or precipitation on iron leads to complete removal of chromium from the waste and was a slower process than the reduction of Cr+6. Presence SRB in a completely mixed batch reactor inhibited the reduction of Cr+6. In a fixed-bed column reactor, SRB enhanced chromium removal and showed promising results for the treatment of wastes with low chromium concentrations. It is proposed that, for waste with high chromium concentration, zero-valent iron is an efficient reductant and can be used for reduction of Cr+6. For low chromium concentrations, a SRB augmented zero-valent iron and sand column is capable of removing chromium completely.     

Use of waste iron metal for removal of Cr(VI) from water

Cr(VI) removal from water was evaluated using waste iron particles in batch experimental mode. The reaction rates were inversely proportional to the initial Cr(VI) concentrations, and the reaction rates of Cr(VI) removal with the waste iron metal were faster than those with Peerless iron, a commercial zero-valent iron. The loss in iron reactivity due to the oxidation, from Fe(0) to Fe(II), ultimately to Fe(III), could be recovered by adding iron-reducing consortium (IRC) to the oxidized iron. Bacterial reduction of Cr(VI) also helped to decrease the aqueous concentration of Cr(VI), but the reduction of oxidized iron by IRC and the consequent reduction of Cr(VI) to Cr(III) by the reduced iron was more significant. Thus, reusing waste iron metal for Cr(VI) removal can reduce the cost of reactive media. Furthermore, the addition of IRC to the waste iron metal can accelerate the removal rate of Cr(VI), and can recover the reactivity of irons which were oxidized by Cr(VI).     

Impact of selected solution factors on arsenate and arsenite removal by nanoiron particles

Introduction  

The nano-scale zero-valent iron (NZVI) was used for the removal of arsenite (As(III)) and arsenate (As(V)) in aqueous solution. Batch experiments were conducted to investigate the effects of initial pH, initial arsenic concentration, dissolved oxygen (DO), and ratio of As(III)/As(V) on arsenic removal.     

Octanol-solubility of dissolved and particulate trace metals in contaminated rivers: implications for metal reactivity and availability

The lipid-like, amphiphilic solvent, n-octanol, has been used to determine a hydrophobic fraction of dissolved and particulate trace metals (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) in contaminated rivers. In a sample from the River Clyde, southwest Scotland, octanol-solubility was detected for all dissolved metals except Co, with conditional octanol-water partition coefficients, D(ow), ranging from about 0.2 (Al and Cu) to 1.25 (Pb). In a sample taken from the River Mersey, northwest England, octanol-solubility was detected for dissolved Al and Pb, but only after sample aliquots had been spiked with individual ionic metal standards and equilibrated. Spiking of the River Clyde sample revealed competition among different metals for hydrophobic ligands. Metal displacement from hydrophobic complexes was generally most significant following the addition of ionic Al or Pb, although the addition of either of these metals had little effect on the octanol-solubility of the other. In both river water samples hydrophobic metals were detected on the suspended particles retained by filtration following their extraction in n-octanol. In general, particulate Cu and Zn (up to 40%) were most available, and Al, Co and Pb most resistant (<1%) to octanol extraction. Distribution coefficients defining the concentration ratio of octanol-soluble particle-bound metal to octanol-soluble dissolved metal were in the range 10(3.3)-10(5.3)mlg(-1). The presence of hydrophobic dissolved and particulate metal species has implications for our understanding of the biogeochemical behaviour of metals in aquatic environments. Specifically, such species are predicted to exhibit characteristics of non-polar organic contaminants, including the potential to penetrate the lipid bilayer. Current strategies for assessing the bioavailability and toxicity of dissolved and particulate trace metals in natural waters may, therefore, require revision.     

某矿区土壤和地下水重金属污染调查与评价

为了解湘南某矿区土壤和地下水重金属污染状况，对该矿区东河流域附近重金属污染源进行了调查，同时，对地下水和土壤样品进行了采样分析，结果表明：（1）该矿区东河流域附近的主要污染源有18个，其中有色金属选厂、尾矿库、采矿场和冶炼厂是排放重金属较多的污染源；（2）20个采样点中土壤重金属Pb、Cd、Zn、As和Hg大部分超过国家土壤环境质量标准（GB15618-1995），综合污染指数P综〉1，该矿区主要的重金属污染元素为Cd、As和Hg，且土壤中Cd、Zn和As的含量两两之间存在着极显著的正线性相关关系；（3）重金属元素在土壤中的纵向迁移不明显，该矿区附近20个采样点的地下水并未受到污染，综合污染指数P综〈1。20个采样点地下水Pb、Cd、Zn、As、Hg浓度均能达到地下水质量标准（GB／T14848．9）中的Ⅲ类标准。     

Evaluation of boron removal from water by hydrotalcite-like compounds

Layered double hydroxides (LDHs) or hydrotalcite (HT)-like compounds with different kinds of metal ions (Mg-Al and Mg-Fe) in the brucite-like sheets were prepared and their adsorption properties were studied in the boron removal from aqueous solution under laboratory conditions. The hydrotalcites were synthesized by the coprecipitation method and were characterized by chemical analyses, X-ray diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR) and specific surface area measurements (BET). The affinity of these materials with a mixture of B(OH)(3) and B(OH)(4)(-) was studied as a function of contact time, initial pH of the solutions, HT quantity and B concentration (adsorption isotherms). It was found that 120 min is enough time for the equilibrium state to be reached in boron adsorption. Boron removal was independent of the initial pH of the solutions because of the high buffering capacity of the LDHs. On the other hand, the adsorption capacity increases with increasing the adsorbent quantity. The adsorption isotherms, described by the Langmuir model, are of L-type, suggesting that B(OH)(4)(-) is adsorbed preferentially on HT-like materials. Besides, Mg-Al hydrotalcites showed higher adsorption capacity than Mg-Fe. We proposed that in Mg-Al hydrotalcites, the boron removal occurs by both adsorption on external surface and ion exchange, whereas for Mg-Fe it occurs only by surface adsorption. After treatment of a solution containing 5.2 mgBl(-1) with Mg-Al hydrotalcites the final boron concentration reached the recommended limit by WHO for drinking water (0.5 mgl(-1)).     

Enhanced dehalogenation of halogenated methanes by bimetallic Cu/Al

A low-cost and high effective copper/aluminum (Cu/Al) bimetal has been developed for treatments of halogenated methanes, including dichloromethane, in near neutral and high pH aqueous systems. Bimetallic Cu/Al was prepared by a simple two-step synthetic method where Cu was deposited onto the Al surface. The presence of Cu on Al significantly enhanced rates of degradation of halogenated methanes and reduced toxic halogenated intermediates. The stability of Cu/Al was preliminarily studied by a multi-spiking batch experiment where complete degradation of carbon tetrachloride was achieved for seven times although the Cu/Al aging was found. Roles of Cu may involve protecting Al against an undesirable oxidation with water, enhancing reaction rates through the galvanic corrosion, and increasing the selectivity to a benign compound (i.e., methane). Kinetic analyses indicated that the activity of bimetallic Cu/Al was comparable to that of iron-based bimetals (e.g., palladized iron) and zero-valent metals. Bimetallic Cu/Al could be a promising reactive reagent for remediation of halogenated solvents-contaminated groundwater associated with high pH problems.     

Speciation of heavy metals in marine sediments vs their bioaccumulation by mussels.

Total contents and speciation of selected heavy metals, including Al, Fe, Co, Ni, Pb, Zn, Cu, Cr, were measured in sediment samples and mussels Mya arenaria and Astarte borealis collected in the Horsund Fjord off Spitsbergen (Norwegian Sea) and the Bay of Gdansk (Baltic Sea). The investigation aimed at revealing differences in the accumulation pattern of heavy metals in mussels inhabiting sediments characterized by varying metal bioavailability. The contents of metals adsorbed to sediments and associated with iron and manganese hydroxides, which were obtained by sequential extraction, were utilized as a measure of metal bioavailability. The contents of Cd, Pb, Zn, Cu and Cr in mussels collected off Spitsbergen were generally lower than those in mussels from the Baltic Sea. In sediments collected off Spitsbergen the bioavailable fraction represented a small proportion (0-3.7% adsorbed metals and 0-11% associated with metals hydroxides) of total heavy metal contents. In sediments from the Baltic Sea the percentages of metals adsorbed and bound to hydroxides were 1-46% and 1-13%, respectively. The differences in bioavailable metal contents measured in sediments were utilized to explain the different contents of metals in mussels collected in the corresponding sites.