Effect of different types of elemental sulfur on bioleaching of heavy metals from contaminated sediments

The application of two different types of elemental sulfur (S0) was studied to evaluate the efficiency on bioleaching of heavy metals from contaminated sediments. Bioleaching tests were performed in suspension and in the solid-bed with a heavy metal contaminated sediment using commercial sulfur powder (technical sulfur) or a microbially produced sulfur waste (biological sulfur) as substrate for the indigenous sulfur-oxidizing bacteria and thus as acid source. Generally, using biological sulfur during suspension leaching yielded in considerably better results than technical sulfur. The equilibrium in acidification, sulfur oxidation and metal solubilization was reached already after 10-14 d of leaching depending upon the amount of sulfur added. The metal removal after 28 d of leaching was higher when biological sulfur was used. The biological sulfur added was oxidized with high rate, and no residual S0 was detectable in the sediment samples after leaching. The observed effects are attributable to the hydrophilic properties of the biologically produced sulfur particles resulting in an increased bioavailability for the Acidithiobacilli. In column experiments only poor effects on the kinetics of the leaching parameters were observed replacing technical sulfur by biological sulfur, and the overall metal removal was almost the same for both types of S0. Therefore, under the conditions of solid-bed leaching the rate of sulfur oxidation and metal solubilization is more strongly affected by transport phenomena than by microbial conversion processes attributed to different physicochemical properties of the sulfur sources. The results indicate that the application of biological sulfur provides a suitable means for improving the efficiency of suspension leaching treatments by shortening the leaching time. Solid-bed leaching treatments may benefit from the reuse of biological sulfur by reducing the costs for material and operating.     

Remediation of heavy metal polluted sediment by suspension and solid-bed leaching: estimate of metal removal efficiency

Remediation of heavy metal polluted sediment by extracting the metals with sulfuric acid can be performed as follows: abiotic suspension leaching, microbial suspension leaching, abiotic solid-bed leaching, and microbial solid-bed leaching. Abiotic leaching means that the acid is directly added, while microbial leaching means that the acid is generated from sulfur by microbes (bioleaching). These four principles were compared to each other with special emphasis on the effectiveness of metal solubilization and metal removal by subsequent washing. Abiotic suspension leaching was fastest, but suspending the solids exhibits some disadvantages (low solid content, costly reactors, permanent input of energy, high water consumption, special equipment required for solid separation, large amounts of waste water, sediment properties hinder reuse), which prevent suspension leaching in practice. Abiotic solid-bed leaching implies the supply of acid by percolating water which proceeds slowly due to a limited bed permeability. Microbial solid-bed leaching means the generation of acid within the bed and has been proven to be the only principle applicable to practice. Metal removal from leached sediment requires washing with water. Washing of solid beds was much more effective than washing of suspended sediment. The kinetics of metal removal from solid beds 0.3, 0.6 or 1.2m in height were similar; when using a percolation flow of 20lm(-2)h(-1), the removal of 98% of the mobile metals lasted 57-61h and required 8.5, 4.2 or 2.3lkg(-1) water. This means, the higher the solid bed, the lower the sediment-mass-specific demand for time and water.     

Environmental assessment of different advanced oxidation processes applied to a bleaching Kraft mill effluent

Basic research on remediation of polluted sediment by leaching has, to date, been carried out exclusively with suspended material. For economic reasons, only solid-bed leaching is applicable to large-scale processes. Abiotic and microbial solid-bed leaching were comparatively studied in a percolator system using ripened and therefore permeable heavy metal polluted river sediment. In the case of abiotic leaching, sulfuric acid was supplied to the sediment by circulating water; the lower the pH of the percolating water, the higher the percolation flow, and the lower the solid-bed height was, the faster the heavy metals were solubilized. However, the pH and percolation flow are subjected to restrictions: strongly acidic conditions result in dissolution of mineral components, and the percolation flow must not exceed the bed permeability. And a high solid bed is an economic requirement. In the case of bioleaching, elemental sulfur added to the sediment was oxidized to sulfuric acid within the package which, in turn, solubilized the heavy metals. Here, the percolation flow and the solid-bed height did not affect the rate of metal solubilization. Solid-bed leaching on a larger scale will thus be much more efficient applying bioleaching with sulfur as the leaching agent than abiotic leaching with sulfuric acid.     

元素硫颗粒粒径对污泥重金属生物沥滤的影响

以城市污水处理厂剩余污泥作为处理介质,土著嗜酸氧化硫硫杆菌(Acidithiobacillus thiooxidans,A.thiooxi-dans)为主要沥滤微生物,采用序批式生物沥滤装置,就投加150~725μm的不同粒径元素硫对沥滤的酸化效果、硫酸根产率和重金属去除效果的影响进行了研究。结果表明,在元素硫投配量为3 g/L,曝气强度为1.0 L/(min.L)的条件下,元素硫粒径在165~215μm范围减小时能显著改善污泥酸化速度、提高酸化程度和硫酸根产率。底物元素硫的最佳粒径为165μm,此时沥滤体系pH下降速率为0.85个pH单位/d,硫酸根的产率为454.9 mg/(L.d),沥滤6 d后污泥中高浓度重金属Cu、Zn、Cd的去除率达到70.3%、81.2%、87.8%.     

Influence of initial pH on bioleaching of heavy metals from contaminated soil employing indigenous Acidithiobacillus thiooxidans

Bioleaching of heavy metals from contaminated soil was carried out employing indigenous sulfur oxidizing bacterium Acidithiobacillus thiooxidans. Experiments were carried out to assess the influence of initial pH of the system on bioleaching of chromium, zinc, copper, lead and cadmium from metal contaminated soil. pH at the end of four weeks of bioleaching at different initial pH of 3-7 was between 0.9 and 1.3, ORP between 567 and 617mV and sulfate production was in the range of 6090-8418mgl(-1). Chromium, zinc, copper, lead and cadmium solubilization ranged from "59% to 98%" at different initial pH. A. thiooxidans was not affected by the increasing pH of the bioleaching system towards neutral and it was able to utilize elemental sulfur. The results of the present study are encouraging to develop the bioleaching process for decontamination of heavy metal contaminated soil.     

Bioleaching of heavy metals from sediment: significance of pH

Bioleaching process, which causes acidification and solubilization of heavy metals, is one of the promising methods for removing heavy metals from contaminated sediments. The solubilization of heavy metals from contaminated sediments is governed by the sediment pH. In the present study, the significance of pH in bioleaching of heavy metals from contaminated sediment was evaluated at different solid contents of sediments in a bench-scale reactor. Results showed that a temporal change of pH in the bioleaching process was effected by the buffering capacity of the sediment particulates. The variations of pH in this bioleaching process were calculated by a modified logistic model. It was observed that solubilization of heavy metals from sediments is highly pH-dependent. In addition, a non-linear equation for metal solubilization relating pH value in the bioleaching process was established. This allows an easier and faster estimate of metal solubilization by measuring pH in the bioleaching process.     

污泥酸化速率影响因子的探讨

采用城市污水厂污泥作为嗜酸微生物菌株来源,通过添加一定量的单质硫,使其中的嗜酸硫杆菌群大量增殖,并使污泥pH大幅降低.取得的培养物可用于废旧干电池中重金属沥滤等的处理.由于培养物对重金属沥滤效率和污泥的酸化速率密切相关,为此进行了不同的污泥种类、加硫量、污泥浓度和曝气强度对污泥酸化速率影响的实验.实验表明,初沉泥、二沉泥和混合浓缩污泥都能迅速利用硫产酸;加硫量(以100 mL污泥计)在0.5、1.0、2.0、4.0 g时,快速酸化的趋势相同.0.5 g的加硫量显示出略微慢的酸化速率,最后达到的最低pH在1.2左右,其他三个都降至1.0以下.污泥质量分数在0.5%、1.0%、2.0%、3.0%、4.0%时,也具有相同的酸化趋势,0.5%质量分数的污泥下降速率最快,这与较低浓度下污泥对pH的缓冲能力较小有关;曝气强度在0.45 L/min和0.3 L/min差别较小,5 d内能迅速降低pH,0.2 L/min的酸化速率较慢,足够长的时间(12 d)也能将pH降至2.5左右,0.1 L/min的曝气强度的酸化速率最慢,不能达到预期的酸化效果.     

Bioleaching of heavy metals from anaerobically digested sewage sludge using FeS2 as an energy source

The effect of using FeS2 as an energy source, on the bioleaching of heavy metals (Zn, Cr, Cu, Pb and Ni) and nutrients (nitrogen and phosphorus) from anaerobically digested sludge using isolated indigenous iron-oxidizing bacteria was investigated in this paper. Addition of FeS2 in the range of 0.5-4.0 g l(-1) accelerated the acidification of sludge and raised the oxidation-reduction potential of sludge medium with an inoculation of 15% (v/v) of active bacteria, thus resulting in an overall increase in metal dissolution efficiency. After 16 days of bioleaching at 28 degrees C and an initial pH of 3.0, up to 99% of Zn, 65% of Cr, 74% of Cu, 58% of Pb and 84% of Ni can be removed from the sludge. In contrast, only 94% of Zn, 12% of Cr, 21% of Cu, 32% of Pb and 38% of Ni were leached out in the control without inoculation of iron-oxidizing bacteria and the addition of FeS2. Less than 15% of nitrogen and 6% of phosphorous were lost after 16 days of bioleaching when using FeS2 as the energy source. Comparing to 39% and 45% loss respectively for these two nutrients when using FeSO4.7H2O as the energy source, FeS2 appears to be a more suitable energy source for preserving nutrients in sludge while removing heavy metals from sludge.     

超声波及其联用技术降解废水中的氯苯

研究了在降解含氯苯废水的过程中，超声波分别与H2O2、O2、空气联用对氯苯降解效率的影响。结果表明，超声波分别与H2O2、O2、空气联用比单独使用超声波降解效率分别提高40、30、18个百分点。并且随H2O2用量的增加，降解效率明显升高。对于O2、空气，当气体流量小于0．3754mL／s时，降解效率随O2、空气流量的增大而明显升高。     

去除污泥中重金属铬的生物淋滤反应器设计与应用

用微生物方法去除污泥中重金属（生物淋滤法）是近年来发展的新技术，探索工程化的条件有重要的应用价值。设计了一套容积为1m^3的生物淋滤反应器，由生物淋滤池、搅拌器、曝气器和空气压缩机等构成。其中，搅拌叶轮由平叶桨和斜叶桨组合而成。利用制革污泥进行了半连续的生物淋滤试验，结果表明，在反应器中污泥与菌体和营养物质能充分混匀，经过2-5d的处理，污泥pH持续下降到2．0以下，污泥中铬的溶出率达90％-99．5％。     

氧化亚铁硫杆菌对电子垃圾焚烧迹地重金属形态的影响简

采用生物淋滤法处理电子垃圾焚烧迹地重金属严重污染的土壤。所用氧化亚铁硫杆菌是从矿坑废水中通过一系列培养、分离和纯化得到。实验结果表明,生物淋滤法可以有效地去除土壤中重金属Cu、Pb和Zn,去除率的大小顺序为Zn>Cu>Pb;采用五步连续提取法分析处理前后土壤中重金属的存在形态,结果表明,通过氧化亚铁硫杆菌处理受重金属污染的土壤,可以促使易移动的重金属结合态的溶解（可交换态、碳酸盐结合态和Fe-Mn氧化物结合态）,并使难移动的重金属结合态向易移动的重金属结合态转变。     

Cumulative impact of 40 years of industrial sulfur emissions on a forest soil in west-central Alberta (Canada)

The impact of 40 years of sulfur (S) emissions from a sour gas processing plant in Alberta (Canada) on soil development, soil S pools, soil acidification, and stand nutrition at a pine (Pinus contorta x Pinus banksiana) ecosystem was assessed by comparing ecologically analogous areas subjected to different S deposition levels. Sulfur isotope ratios showed that most deposited S was derived from the sour gas processing plant. The soil subjected to the highest S deposition contained 25.9 kmol S ha(-1) (uppermost 60 cm) compared to 12.5 kmol S ha(-1) or less at the analogues receiving low S deposition. The increase in soil S pools was caused by accumulation of organic S in the forest floor and accumulation of inorganic sulfate in the mineral soil. High S inputs resulted in topsoil acidification, depletion of exchangeable soil Ca2+ and Mg2+ pools by 50%, podzolization, and deterioration of N nutrition of the pine trees.     

Major factors influencing bacterial leaching of heavy metals (Cu and Zn) from anaerobic sludge

Anaerobically digested sewage sludges were treated for heavy metal removal through a biological solubilization process called bacterial leaching (bioleaching). The solubilization of copper and zinc from these sludges is described in this study: using continuously stirred tank reactors with and without sludge recycling at different mean hydraulic residence times (1, 2, 3 and 4 days). Significant linear equations were established for the solubilization of zinc and copper according to relevant parameters: oxygen reduction potential (ORP), pH and residence time (t). Zinc solubilization was related to the residence time with a r2 (explained variance) of 0.82. Considering only t=2 and 3 days explained variance of 0.31 and 0.24 were found between zinc solubilization as a function of ORP and pH indicating a minor importance of those two factors for this metal in the range of pH and ORP experimented. Cu solubilization was weakly correlated to mean hydraulic residence time (r2=0.48), while it was highly correlated to ORP (r2=0.80) and pH (r2=0.62) considering only t of 2 and 3 days in the case of pH and ORP. The ORP dependence of Cu solubilization has been clearly demonstrated in this study. In addition to this, the importance of the substrate concentration for Cu solubilization has been confirmed. The hypothesis of a biological solubilization of Cu by the indirect mechanism has been supported. The results permit, under optimum conditions, the drawing of linear equations which will allow prediction of metal solubilization efficiencies from the parameters pH (Cu), ORP (Cu) and residence time (Cu and Zn), during the treatment. The linear regressions will be a useful tool for routine operation of the process.     

Bioleaching of heavy metals from livestock sludge by indigenous sulfur-oxidizing bacteria: effects of sludge solids concentration

A technologically and economically feasible process called bioleaching was used for the removal of heavy metals from livestock sludge with indigenous sulfur-oxidizing bacteria in this study. The effects of sludge solids concentration on the bioleaching process were examined in a batch bioreactor. Due to the buffering capacity of sludge solids, the rates of pH reduction, ORP rise and metal solubilization were reduced with the increase of the solids concentration. No apparent influence of solids concentration on sulfate produced by sulfur-oxidizing bacteria was observed when the solids concentration was less than 4% (w/v). A Michaelis-Menten type of equation was able to well describe the relationship between solids concentration and rate of metal solubilization. Besides, high efficiencies of metal solubilization were achieved after 16 d of bioleaching. Therefore, the bioleaching process used in this study could be applied to remove heavy metals effectively from the livestock sludge.     

Enhanced Cr bioleaching efficiency from tannery sludge with coinoculation of Acidithiobacillus thiooxidans TS6 and Brettanomyces B65 in an air-lift reactor

Bioleaching process has been demonstrated to be an effective technology in removing Cr from tannery sludge, but a large quantity of dissolved organic matter (DOM) present in tannery sludge often exhibits a marked toxicity to chemolithoautotrophic bioleaching bacteria such as Acidithiobacillus thiooxidans. The purpose of the present study was therefore to enhance Cr bioleaching efficiencies through introducing sludge DOM-degrading heterotrophic microorganism into the sulfur-based sludge bioleaching system. An acid-tolerant DOM-degrading yeast strain Brettanomyces B65 was successfully isolated from a local Haining tannery sludge and it could metabolize sludge DOM as a source of energy and carbon for growth. A combined bioleaching experiment (coupling Brettanomyces B65 and A. thiooxidans TS6) performed in an air-lift reactor indicated that the rates of sludge pH reduction and ORP increase were greatly improved, resulting in enhanced Cr solubilization. Compared with the 5 days required for maximum solubilization of Cr for the control (single bioleaching process without inoculation of Brettanomyces B65), the bioleaching period was significantly shorten to 3 days for the combined bioleaching system. Moreover, little nitrogen and phosphorous were lost and the content of Cr was below the permitted levels for land application after 3 days of bioleaching treatment.     

Biological solubilization and mineralization as novel approach for the pretreatment of food waste

The performance of a garbage disposal system to solubilize and mineralize food wastes through biological solubilization was evaluated through the examination of the effects of operational conditions like water supply volume, water supply frequency and aeration on the amount of waste solubilized, mineralized and accumulated in the reactor. The biological solubilization process consisted of a solubilization reactor and a circulation tank. Food waste and fresh water were supplied into the solubilization reactor with support media. Wastewater from the solubilization reactor was discharged to the circulation tank and water in the circulation tank was periodically pumped back to the solubilization reactor. In case of the total food waste loading of 16 kg m(3-1) d(-1), little carbon (0-5.7%) accumulated in the reactor as long as the system was kept under aerobic condition through large volume of water supply (higher than 3.5 lh(-1)) or applying aeration in the circulation tank. However, 42% of the loaded carbon accumulated under anaerobic condition in low water supply (less than 1.8 lh(-1)). The rest of the waste was either solubilized or mineralized. The aeration in the circulation tank, therefore, was effective to provide similar solubilization and mineralization as the large volume of water supply. However, frequency of feeding at the large volume of water supply had no significant effect on the amount of waste solubilization and mineralization.     

Formation of chlorinated phenols, dibenzo-p-dioxins, dibenzofurans, benzenes, benzoquinnones and perchloroethylenes from phenols in oxidative and copper (II) chloride-catalyzed thermal process

Formation of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and chlorinated phenols on CuCl(2) from unsubstituted phenol and three monochlorophenols was studied in a flow reactor over a temperature range of 100-425 degrees C. Heated nitrogen gas streams containing 8.0% oxygen were used as carrier gas. The 0.00024mol of unsubstituted phenol and 0.00039mol of each monochlorophenol were passed through a 1g and 1cm SiO(2) particle containing 0.5% (Cu by mass) CuCl(2). Chlorination preferentially occurred on ortho-(2, 6) and para-(4) positions. Chlorination increased up to 200 degrees C, and thereafter decreased as temperature increased. Chlorination of phenols plays an important role in the formation of the more chlorinated PCDD/Fs. Chlorinated benzenes are formed possibly from both chlorination of benzene and chlorodehydroxylation of phenols. Chlorinated phenols with ortho chlorine formed PCDD products, and major PCDD products were produced via loss of one chlorine. For PCDF formation, at least one unchlorinated ortho carbon was required.     

氧化亚铁硫杆菌对电子垃圾焚烧迹地重金属形态的影响

采用生物淋滤法处理电子垃圾焚烧迹地重金属严重污染的土壤。所用氧化亚铁硫杆菌是从矿坑废水中通过一系列培养、分离和纯化得到。实验结果表明,生物淋滤法可以有效地去除土壤中重金属Cu、Ph和Zn,去除率的大小顺序为Zn〉Cu〉Pb;采用五步连续提取法分析处理前后土壤中重金属的存在形态,结果表明,通过氧化亚铁硫杆菌处理受重金属污染的土壤,可以促使易移动的重金属结合态的溶解（可交换态、碳酸盐结合态和Fe—Mn氧化物结合态）,并使难移动的重金属结合态向易移动的重金属结合态转变。     

Effects of sample preparation on the measurement of organic carbon,hydrogen, nitrogen,sulfur, and oxygen concentrations in marine sediments

The elemental composition of marine sediment provides useful information for the study of environmental processes including biogeochemical cycling and contaminant partitioning. It is common practice to acidify marine sediment samples to remove carbonate before measuring the concentrations of organic carbon (C). To date, however the effects of acidification on the concentrations of hydrogen (H), nitrogen (N), sulfur (S) and oxygen (O) in marine sediments have not been explicitly addressed. Acidification may contaminate or alter the sediment samples and create experimental artifacts affecting the validity of resulting H/C, C/N and O/C ratios. The objective of this study was to quantify how various preparation techniques affect the measured concentrations of C, H, N, S and O in marine sediments. Effects of four different pretreatments: unacidified (whole), acidification by HCl vapor, acidification by direct addition of HCl, and combustion were evaluated using five marine sediments and a standard reference material. The magnitude of carbonate loss between the vapor and direct acidification treatments was evaluated using stable C isotope analysis. Carbonates were most effectively removed by direct addition of HCl; and our results agree with findings of other studies which found direct addition of HCl to be the most accurate method for measuring organic C. However, the acid treatments elevated the apparent concentration of H and O; and in a few cases concentrations of N and S were significantly affected by acidification. In general, combustion significantly reduced all elemental concentrations compared to the whole sample. Based on these results, we recommend analysis of the untreated whole sediment for determining N, H, O, and S.     

Abatement of sulfur hexafluoride emissions from the semiconductor manufacturing process by atmospheric-pressure plasmas

Sulfur hexafluoride (SF6) is an important gas for plasma etching processes in the semiconductor industry. SF6 intensely absorbs infrared radiation and, consequently, aggravates global warming. This study investigates SF6 abatement by nonthermal plasma technologies under atmospheric pressure. Two kinds of nonthermal plasma processes--dielectric barrier discharge (DBD) and combined plasma catalysis (CPC)--were employed and evaluated. Experimental results indicated that as much as 91% of SF6 was removed with DBDs at 20 kV of applied voltage and 150 Hz of discharge frequency for the gas stream containing 300 ppm SF6, 12% oxygen (O2), and 40% argon (Ar), with nitrogen (N2) as the carrier gas. Four additives, including Ar, O2, ethylene (C2H4), and H2O(g), are effective in enhancing SF6 abatement in the range of conditions studied. DBD achieves a higher SF6 removal efficiency than does CPC at the same operation condition. But CPC achieves a higher electrical energy utilization compared with DBD. However, poisoning of catalysts by sulfur (S)-containing species needs further investigation. SF6 is mainly converted to SOF2, SO2F4, sulfur dioxide (SO2), oxygen difluoride (OF2), and fluoride (F2). They do not cause global warming and can be captured by either wet scrubbing or adsorption. This study indicates that DBD and CPC are feasible control technologies for reducing SF6 emissions.