Sulfidogenic fluidized bed treatment of real acid mine drainage water

The treatment of real acid mine drainage water (pH 2.7-4.3) containing sulfate (1.5-3.34 g/L) and various metals was studied in an ethanol-fed sulfate-reducing fluidized bed reactor at 35 °C. The robustness of the process was tested by increasing stepwise sulfate, ethanol and metal loading rates and decreasing feed pH and hydraulic retention time. Highest sulfate reduction rate (4.6 g/L day) was obtained with feed sulfate concentration of 2.5 g/L, COD/sulfate ratio of 0.85 and HRT of 12 h. The corresponding sulfate and COD removal efficiencies were about 90% and 80%, respectively. The alkalinity produced in sulfidogenic ethanol oxidation neutralized the acidic mine water. Highest metal precipitation efficiencies were observed at HRT of 24 h, the percent metal removal being over 99.9% for Al (initial concentration 55 mg/L), Co (9.0 mg/L), Cu (49 mg/L), Fe (435 mg/L), Ni (3.8 mg/L), Pb (7.5 mg/L) and Zn (6.6 mg/L), and 94% for Mn (7.21 mg/L).     

Treatment of metal-contaminated water using bacterial sulfate reduction: results from pilot-scale reactors

Simple anaerobic reactors were installed to treat metal-contaminated water in an underground coal mine and at a smelting residues dump in Pennsylvania. The reactors consisted of barrels and tanks filled with spent mushroom compost, within which bacterial sulfate reduction became established. Concentrations of Al, Cd, Fe, Mn, Ni, and Zn were typically lowered by over 95% as contaminated water flowed through the reactors. Cadmium, Fe, Ni, and some Zn were retained as insoluble metal sulfides following their reaction with bacterially generated H(2)S. Aluminum, Mn, and some Zn hydrolyzed and were retained as insoluble hydroxides or carbonates. Reactor effluents were typically circumneutral in pH and contained net alkalinity. The principal sources of alkalinity in the reactors were bacterial sulfate reduction and limestone dissolution. This article examines the chemistry of the reactor systems and the opportunities for enhancing their metal-retaining and alkalinity-generating potential. (c) 1992 John Wiley & Sons, Inc.     

Contrasting two methods for determining trace metal partitioning in oxidized lake sediments

A simultaneous (SIM) sediment extraction procedure for low carbonate sediments, which partitions sediment-bound trace metals (Fe, Mn, Zn, Cu, and Cd) into easily reducible (associated with Mn oxides), reducible (associated with Fe oxides) and alkaline extracted (bound to organic) metal is presented. The SIM method was compared to the sequential (SEQ) extraction procedure of Tessier et al. (1979). Both methods showed good agreement for the partitioning of Zn and Cd among the easily reducible, reducible and organic components of sediment. Both methods also showed the same general distribution of Mn, Fe and Cu among the three sediment components, however concentrations of metals recovered by the two methods differed; less Mn and Fe and more Cu was recovered from sediments by the SEQ vs. the SIM procedure. Less recovery of Mn is in part attributed to the loss of this metal in the `in between' reagent rinses required in the SEQ procedure. Greater recovery of Cu by the SEQ vs. the SIM method may be due to the pretreatment of sediment with strong reducing agents prior to the step used for liberating organically bound metals. Advantages of a SIM over the SEQ include rapid sample processing time (i.e. the treatment of 40 samples per day vs. 40 samples in three days), plus minimal sample manipulation. Hence, for partitioning metals into easily reducible, reducible and organic sediment components in sediments low in carbonate, we recommend the use of a SIM extraction over that of a SEQ procedure.     

Size dependent metal concentrations in two marine gastropod species

The effect of size on the accumulation of Cd, Cr, Cu, Mn, Ni, Fe and Zn in the muscle and viscera of the gastropodsMonodonta turbinata andCerithium vulgatum was investigated. The concentration of the essential metals Cr, Mn and Ni and the non-essential metal Cd decreased with increasing size in both of the species and tissues. The concentration of the essential metals Cu, Fe and Zn, showed a less constant relation with size.     

沈阳市住宅区小区与街道灰尘重金属污染评价

城市住宅区是人类活动的重要场所,与居民的日常生活紧密相关。为了解沈阳市住宅区小区与街道灰尘中重金属污染的空间分布,采集了不同住宅区小区与街道的灰尘样品,分析了灰尘中重金属的含量,并使用富集因子和地累积指数评估了其污染程度。结果表明,沈阳市灰尘中重金属Cr、Cd、Cu、Pb和Zn的平均含量均超过辽宁省表层土壤元素背景值。单因素方差分析表明,街道灰尘中重金属Cu、Fe、Mn和Zn的空间分布具有显著性差异,而小区灰尘中重金属Cd、Cr、Fe、Mn和Pb在空间上具有显著性差异。重金属Cd、Zn和Pb的平均污染水平较高,其中小区内Cd和Zn的污染程度高于街道。沈阳市不同方位住宅区灰尘中重金属的污染水平介于轻度污染至中度污染之间。     

山东省部分水岸带土壤重金属含量及污染评价

为了解山东省水岸带土壤重金属的含量特征和污染状况,于2010年9月—10月采集了39个水岸带土壤样品,分析了土壤中Cr、Co、Ni、Cu、Zn、Cd、Pb和Hg的含量以及土壤的pH值、粒度和有机质,采用单因子指数法、综合指数法和潜在生态危害指数法对水岸带土壤重金属污染进行了评价,并利用相关分析和聚类分析对其来源进行了初步的解析。结果表明：水岸带土壤的pH值为5.67—8.66,主要呈碱性;有机质的平均含量为9.39 g/kg,土壤粒度主要以砂粒和粉粒为主,其平均体积百分比分别为50.33%和38.48%,平均粒径为89.69 μm;Cr、Co、Ni、Cu、Zn、Cd、Pb和Hg的平均含量为53.03 mg/kg、10.33 mg/kg、24.96 mg/kg、18.38 mg/kg、56.13 mg/kg、0.142 mg/kg、22.48 mg/kg和0.020 mg/kg。各水岸带土壤重金属的含量均符合《土壤环境质量标准》（GB15618-1995）二级标准。以山东省土壤元素背景值为评价标准,水岸带土壤重金属总体表现为轻度污染和轻微生态风险,其中Cd和Hg是主要的污染因子,其对潜在生态危害指数的平均贡献率分别为46.8% 和33.6%。洙赵新河、廖河、门楼水库和东平湖水岸带土壤重金属污染及潜在生态危害明显高于其他水源地。源解析的结果表明：水岸带土壤重金属的含量受自然源和人为源的双重影响,人为源主要包括地表径流、工业废气、垃圾和交通运输等。     

Spatial distribution of metals in the constructed wetlands

Investigation of the spatial distribution of metals was conducted for two constructed wetlands used as tertiary treatment in Chia Nan University of Pharmacy and Science (CNU) and Metal Processing Industries (MPI) located in Tainan, Taiwan. These two distinguished sites were selected to compare the distribution of metals for constructed wetlands treating different types of wastewater. Along the distance, samples of water, sediment, and macrophytes were analyzed for metals including Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn. Additionally, measurements of water quality including temperature, pH, EC, ORP, DO, TSS, BOD, COD, and turbidity were performed. Results show that, at CNU, wastewater contained higher organic consititute (BOD 29.3 +/- 11.7 mg/, COD 46.7 +/- 33.6 mg/L) with low metals content. Wastewater at MPI contained low level of organic consititute (BOD 7.1 +/- 3.3 mg/L, and COD 66.0 +/- 56.5 mg/L) and higher metals content. Metals distribution of both sites showed similar results where metals in the sediments in the inlet zone have greater concentrations than other areas. The constructed wetlands can remove Cd, Cu, Ni, Pb, and Zn. However, there was no removal of Al, Cr, Fe, and Mn. A distance along the constructed wetlands had no effect on metal concentrations in macrophyte and water.     

Biosorption of nickel and cadmium by metal resistant bacterial isolates from agricultural soil irrigated with industrial wastewater

Agricultural soil irrigated with industrial wastewater (more than two decades) analysed for heavy metals revealed high levels of Fe, Cr, Cu, Zn, Ni and Cd. Out of a total of 40 bacterial isolates obtained from these soils, 17 belonged to the family enterobacteriaceae and 10 were Pseudomonas spp. A maximum MIC of 200 for Cd, 400 for Zn and Cu, 800 for Ni, and 1600 microg/ml for Pb was observed. Biosorption of Ni and Cd studies over a range of metal ion concentrations with Escherichia coli WS11 both in single and bi-metal systems showed that the adsorption of Cd and Ni was dependent on the concentrations and followed the Freundlich adsorption isotherm. The biosorption of Ni increased from 6.96 to 55.31 mg/g of cells, and Cd from 4.96 to 45.37 mg/g of cells at a concentration ranging from 50 to 400 microg/ml after 2h of incubation in a single metal solution. A further increase in incubation time had no significant effect on the biosorption of metals.     

Zn,Cd, S and trace metal bioaccumulation in willow (Salix spp.) cultivars grown hydroponically

Willows (Salix spp.) can be used to phytoremediate soils contaminated by Zn and Cd under certain conditions. In this study, the ability of 14 Salix cultivars to concentrate Cd, Zn and S in leaves was measured in hydroponic culture with 10 and 200 µM Cd and Zn, respectively, in the nutrient medium. The cultivars showed a wide range of biomass yields, tolerance to metals, and foliar concentrations of Zn and Cd, with some cultivars accumulating up to 1000 mg kg^?1 Zn, 70 mg kg^?1 Cd and 10,000 mg kg^?1 S with only mild phytotoxicity symptoms attributable to excess Zn. Cultivars with higher foliar Zn concentrations tended to have higher foliar Cd concentrations as well, and competition between Zn and Cd for uptake was observed. Exposure of Salix cultivars to Cd and Zn did not affect foliar concentrations of secondary metabolites such as polyphenols, but trace metal concentrations in leaves were significantly reduced (Fe and Cu) or increased (Mn) by exposure to excess Zn and Cd. Sulfur-XANES spectroscopy showed foliar S to be predominantly in highly oxidized (sulfate plus sulfonate) and reduced (thiol) forms, with oxidized S more prevalent in willows with the highest total S content.     

Lead removal through biological sulfate reduction process

The feasibility of lead removal through biological sulfate reduction process with ethanol as electron donor was investigated. Sulfide-rich effluent from biological process was used to remove lead as lead sulfide precipitate. The experiments were divided into two stages; Stage I startup and operation of sulfidogenic process in a UASB reactor and Stage II lead sulfide precipitation. In Stage I, the COD:S ratio was gradually reduced from 15:1 to 2:1. At the COD:S ratio of 2:1, sulfidogenic condition was achieved as identified by 80-85% of electron flow by sulfate reducing bacteria (SRB). COD and sulfate removal efficiency were approximately 78% and 50%, respectively. In Stage II, the effluent from UASB reactor containing sulfide in the range of 30-50 mg/L and lead-containing solution of 45-50 mg/L were fed continuously into the precipitation chamber in which the optimum pH for lead sulfide precipitation of 7.5-8.5 was maintained. It was found that lead removal of 85-95% was attained.     

A new approach to the remediation of heavy metal liquid wastes via off-gases produced by Klebsiella pneumoniae M426

When the off-gas from an aerobic culture of Klebsiella pneumoniae M426 grown in the absence of added heavy metals was passed through a solution of Hg(2+), Cd(2+), Pb(2+), or Cu(2+) a yellow-white (Hg), white (Cd, Pb), or blue (Cu) precipitate was formed. Metal removal from solution was >97% within 2 h at initial concentrations of (as metal): Hg, 8.5; Cd, 12.6; Pb, 7.8; Cu, 9.5 mg/mL. Mercury was removed from solution at pH 2 and in up to 1 M NaCl. Energy dispersive X-ray microanalysis (EDX) of the precipitates showed them to comprise metal, sulfur and carbon in the case of Hg, Cd, and Pb, and, in the case of Cd and Pb, also oxygen. The pH of the solution increased by 1-2 units at an initial pH of 7 and by 4-5 units at an initial pH of 2. In the case of cadmium and lead, the presence of crystalline metal carbonates and hydroxides was confirmed by X-ray powder diffraction (XRD) analysis and additional peaks were seen which could not be assigned to known compounds in the diffraction file database. In the case of copper, hydroxides, and a form of copper sulfate, were found. In the case of mercury the XRD patterns could not be assigned to any known compound, except for HgCl in the solution at the acidic initial pH. The absence of sharp peaks in the pattern for the Hg-precipitate was indicative of poorly crystalline, nanocrystalline or amorphous material. The unknown mercury compound, since it contained non-carbonate carbon, was suggested to be derived from a volatile organothiol in the gases evolved from the culture. Analysis of the culture head gas by GC-MS showed the presence of dimethyldisulfide as a likely precipitant. No sulfur compound was found using XRD analysis in the case of cadmium and lead, although EDX analysis suggested this as a major component and the lack of XRD pattern is evidence for a non-crystalline metal-organothiol. The exact chemistry of the new materials remains to be elucidated but metal precipitation via a biogenic organothiol is a potentially effective approach to the remediation of aggressive metal wastes.     

Metal exposures to native populations of the caddisfly Hydropsyche (Trichoptera: Hydropsychidae) determined from cytosolic and whole body metal concentrations

Metal concentrations of the soluble fraction of the cytoplasm (cytosol) and the whole body were determined in the caddisfly Hydropsyche spp. (Trichoptera). Metal accumulation in the cytosol and the whole body were compared in samples collected along 380 kms of a contamination gradient in the Clark Fork river in four consecutive years (1992–1995), and from a contaminated tributary (Flint Creek). Samples from the contaminated sites were compared to an uncontaminated tributary (Blackfoot River). Relations between cytosolic metal concentration and cytosolic protein (used as a general biomarker of protein metabolism) also were examined in 1994 and 1995. Relative to whole body concentrations, cytosolic metal concentrations varied among metals and years. Spatial patterns in whole body and cytosolic Cd, Cu and Pb concentrations were qualitatively similar each year, and these concentrations generally corresponded to contamination levels measured in bed sediments. The proportions of metals recovered in the cytosol of ranged from 12 to 64% for Cd and Cu and from 2 to 38% for Pb. Zinc in the whole body also was consistent with contamination levels, but cytosolic Zn concentrations increased only at the highest whole body Zn concentrations. As a result, the proportion of Zn recovered in the cytosol ranged from 16 to 63% and tended to be inversely related to whole body Zn concentrations. The proportions of cytosolic metals varied significantly among years and, as a result, interannual differences in metal concentrations were greater in the cytosol than in the whole body. The results demonstrated that Hydropsyche in the river were chronically exposed to biologically available metals. Some features of this exposure were not evident from whole body concentrations. In general, protein levels did not correspond to cytosolic metal concentrations. A variety of environmental factors could interact with metal exposures to produce complex responses in protein metabolism. Systematic study will be necessary to differentiate the effects of multiple environmental stressors on organisms living in contaminated ecosystems. This revised version was published online in July 2006 with corrections to the Cover Date.     

Heavy metals extraction from municipal solid waste incineration fly ash using adapted metal tolerant Aspergillus niger

This study focused on the adaptation of Aspergillus niger tolerating high concentration of heavy metals for bioleaching of fly ash. The Plackett-Burman design indicated that Al and Fe inhibited the growth of A. niger (AS 3.879 and AS 3.40) significantly. The single metal (Al and Fe) and multi-metals adapted AS 3.879 strain tolerated up to 3500 mg/L Al, 700 mg/L Fe, and 3208.1mg/L multi-metals, respectively. The order of metal extraction yield in two-step bioleaching of 60 and 70 g/L fly ash using Al adapted, multi-metals adapted and un-adapted AS 3.879 strains was as follows: multi-metals adapted>Al adapted>un-adapted. The multi-metals adapted strain grew with up to 70 g/L fly ash and secreted 256 mmol/L organic acids after 288 h, where 87.4% Cd, 64.8% Mn, 49.4% Zn and 45.9% Pb were dissolved. The extracted metals in TCLP test of the bioleached fly ash by multi-metals adapted strain were under the regulated levels in China.     

Total and speciation analyses of heavy metals in the sand fraction of Nigerian oil sands for human and ecological risk assessment

Total metal analysis and metal speciation of sand fraction of Nigerian oil sands were done to extract and partition heavy metals into six operationally defined fractions in order to assess environmental and health implications of the oil sand development. Soxhlet extraction of bitumen from the oil sand was done using toluene. Traces of water and extracting solvent were removed at 70°C from the sand fraction using oven. Elemental analysis was performed by Atomic Absorption Spectrophotometry. The heavy metals except Cu have low Pollution index values. Negative geo-accumulation index was obtained for the metals except Cu, indicating that the oil sands were uncontaminated with the metals. Strong and significant positive correlations existed between Fe/Pb, Zn/Cu, Cd/Pb, Ni/Cd, Ni/Pb, Cd/Fe, Ni/Fe and Cr/Zn, while strong and significant negative correlations existed between Mn/Pb and As/Mn, indicating common sources or chemical similarities and vice versa. T-test results indicated significant differences between the concentrations of the metals. Cross-plot analysis showed strong positive correlation between the sand fraction and Nigerian bitumen. Speciation analysis indicated highest and lowest indices of metal mobility for Zn and Pb, respectively. This study concluded that the sand fraction may not pose any environmental risks from elemental point of view.     

Performance of sulfidogenic anaerobic baffled reactor (ABR) treating acidic and zinc-containing wastewater

The applicability of anaerobic baffled reactor (ABR) was investigated for the treatment of acidic (pH 4.5–7.0) wastewater containing sulfate (1000–2000 mg/L) and Zn (65–200 mg/L) at 35 °C. The ABR consisted of four equal stages and lactate was supplemented (COD/SO₄²⁻ = 0.67) as carbon and energy source for sulfate reducing bacteria (SRB). The robustness of the system was studied by decreasing pH and increasing Zn, COD, and sulfate loadings. Sulfate-reduction efficiency quickly increased during the startup period and reached 80% within 45 days. Decreasing feed pH, increasing feed sulfate and Zn concentrations did not adversely affect system performance as sulfate reduction and COD removal efficiencies were within 62–90% and 80–95%, respectively. Although feed pH was steadily decreased from 7.0 to 4.5, effluent pH was always within 6.8–7.5. Over 99% Zn removal was attained throughout the study due to formation of Zn-sulfide precipitate.     

Heavy metal contamination in vegetables grown around peri-urban and urban-industrial clusters in Ghaziabad,India

Heavy metal contamination of agricultural soils resulting from rapid industrialization and urbanization is of great concern because of potential health risk due to dietary intake of contaminated vegetables. The present study aims to evaluate the status of heavy metals contamination of agricultural soils and food crops around an urban-industrial region in India. Transfer factor values of Cu, Cr, Pb, Cd, Zn, and Ni from soil to vegetable was estimated. The mean heavy metal concentrations (mg/kg) in agricultural soils (Cu: 17.8, Cr: 27.3, Pb: 29.8, Cd: 0.43, Zn: 87, Mn: 306.6, Fe: 16984, and Ni: 53.8) were within allowable concentrations for Indian agricultural soil. The concentrations of Pb, Cd, Zn, and Ni in crops/vegetables exceeded the World Health Organization/Food and Agriculture Organization safe limits. Relative orders of transfer of metals from soil to edible parts of the crops/vegetables were Cd > Pb > Ni > Zn > Cu > Cr. The enrichment factors of heavy metals in soil indicated minor to moderately severe enrichment for Pb, Cd, and Ni; minor to moderate enrichment for Zn; no enrichment to minor enrichment for Mn; and no enrichment to moderate enrichment for Cu at different sites. Ecological risk index of soil showed considerable contamination in one of the wastewater irrigated sites.     

An internal sedimentation bioreactor for laboratory-scale removal of toxic metals from soil leachates using biogenic sulphide precipitation

An internal-sedimentation bioreactor was employed to provide biomass feedback and process intensification in a laboratory-scale sulphide-bioprecipitation system for toxic metals (Cd, Cr, Cu, Mn, Ni, Zn) present in acid leachates from metal-contaminated soil. Biomass feedback was improved by addition of a cationic polymer flocculant and the activity of the sulphate-reducing bacterial culture was increased by the addition of cornsteep in addition to the ethanol used as carbon/energy substrate. A mass-balance was carried out for carbon and sulphur in the system. Sulphate reduction in the reactor was able to remove acidity at moderate sulphate concentrations up to 50 mM although it was insufficient at the highest levels tested. When presented with a simulated toxic metal-containing leachate, the reactor was able to precipitate metals efficiently under all of the conditions of sulphate concentration and pH tested, producing an effluent with metal concentrations suitable for environmental discharge. Received 29 October 1996/ Accepted in revised form 31 March 1997     

Removal of Contaminating Metals from Soil by Sulfur-Based Bioleaching and Biogenic Sulfide-Based Precipitation

The potential of a hybrid process incorporating sulfur-based bioleaching and sulfide-based precipitation for treatment of metal-contaminated soil was examined in batch-type experiments. The sulfur-based soil bioleaching process with Acidithiobacillus sp. could be initiated at a wide range of initial pH from 4.0 to 6.3. After 15 days, 98% of Zn, 89% of Cu and 79% of Cd was bioleached. The gaseous sulfides recycling from Desulfovibrio sp.-mediated sulfate-reducing reactor via N₂ sparging efficiently treated metal-loaded soil leachate. With a sulfide/metal ratio of 3.0, 88% of Zn, 100% of Cu and 95% of Cd were precipitated, resulting in effluent metal concentrations of 3.5 mg Zn²⁺/L, 0.2 mg Cu²⁺/L and 0.03 mg Cd²⁺/L.

Supplemental materials are available for this article. Go to the publisher's online edition of Geomicrobiology Journal to view the supplemental file.     

The expression of heterologous Fe (III) phytosiderophore transporter HvYS1 in rice increases Fe uptake,translocation and seed loading and excludes heavy metals by selective Fe transport

Many metal transporters in plants are promiscuous, accommodating multiple divalent cations including some which are toxic to humans. Previous attempts to increase the iron (Fe) and zinc (Zn) content of rice endosperm by overexpressing different metal transporters have therefore led unintentionally to the accumulation of copper (Cu), manganese (Mn) and cadmium (Cd). Unlike other metal transporters, barley Yellow Stripe 1 (HvYS1) is specific for Fe. We investigated the mechanistic basis of this preference by constitutively expressing HvYS1 in rice under the control of the maize ubiquitin1 promoter and comparing the mobilization and loading of different metals. Plants expressing HvYS1 showed modest increases in Fe uptake, root‐to‐shoot translocation, seed accumulation and endosperm loading, but without any change in the uptake and root‐to‐shoot translocation of Zn, Mn or Cu, confirming the selective transport of Fe. The concentrations of Zn and Mn in the endosperm did not differ significantly between the wild‐type and HvYS1 lines, but the transgenic endosperm contained significantly lower concentrations of Cu. Furthermore, the transgenic lines showed a significantly reduced Cd uptake, root‐to‐shoot translocation and accumulation in the seeds. The underlying mechanism of metal uptake and translocation reflects the down‐regulation of promiscuous endogenous metal transporters revealing an internal feedback mechanism that limits seed loading with Fe. This promotes the preferential mobilization and loading of Fe, therefore displacing Cu and Cd in the seed.     

Performance of a down-flow fluidized bed reactor under sulfate reduction conditions using volatile fatty acids as electron donors

The use of a down-flow fluidized bed (DFFB) reactor for the treatment of a sulfate-rich synthetic wastewater was investigated to obtain insight into the outcome of sulfate reduction in a biofilm attached to a plastic support under a down-flow regime. Fine low-density polyethylene particles were used as support for developing a biofilm within the reactor. The reactor treated a volatile fatty acids mixture of acetate or lactate, propionate, and butyrate at different chemical oxygen demand (COD) to sulfate ratios ranging from 1.67 to 0.67 (g/g). Organic loading rate changed from 2.5 to 5 g COD/L x day and sulfate loading rate increased from 1.5 to 7.3 g SO(4) (2-)/L x day. At the beginning of continuous operation, methanogenesis was the predominant process; however, after 187 days, sulfate reduction became the main ongoing biological process. After 369 days, a COD removal of 93% and a sulfate removal of 75% were reached. Total sulfide concentrations in the reactor ranged from 105, when the reactor was mainly methanogenic, to around 1,215 mg/L at the end of the experiment. The high sulfide concentrations did not affect the performance of the reactor. Results demonstrated that the configuration of the DFFB reactor was suitable for the anaerobic treatment of sulfate-rich wastewater.