Metal Removal from Water Discharges by a Constructed Treatment Wetland

A full‐scale constructed wetland treatment system consisting of four pairs of wetland cells (3.2 ha total area) with water flowing through a pair of cells in series prior to discharge was investigated. A retention basin provided stable water flow to the system. Water retention time in the wetland system was approximately 48 hours, and the wetland cells operated at circumneutral pH. Vegetation development within the cells has been excellent. Copper removal efficiency was greater than 75 % from the start‐up of the system, while mercury efficiency improved with maturation of the treatment cells. Sampling of the water course through the wetlands conducted during the fourth year of operation validated continued performance, and assessed the fate of a larger suite of metals present in the water. Copper and mercury removal efficiencies were still very high, both in excess of 80 % removal from the water after passage through the wetland system. Mercury removal continued along the entire water course through the system, while copper was removed almost immediately upon entering the wetland cells. Lead removal from the water by the system was 83 %, zinc removal was 60 %, and nickel was generally unaffected. Organic carbon in the water was also increased by the system and reduced the bioavailability of some metals. Operation and maintenance of the system continued to be minimal, and mainly consisted of checking for growth of the vegetation and free flow of the water through the system. The system was entirely passive, relying on gravity as the power source of water flow. No reportable permit exceedances have been experienced since the wetland began treating an outfall discharge.     

Bioleaching of Heavy Metal Polluted Sediment: Influence of Temperature and Oxygen (Part 1)

A remediation process for heavy metal polluted sediment has previously been developed in which the heavy metals are removed from the sediment by solid‐bed bioleaching using elemental sulfur (S⁰): the added S⁰ is oxidized by the indigenous microbes to sulfuric acid that dissolves the heavy metals which are finally extracted by percolating water. In this process, the temperature is a factor crucially affecting the rate of S⁰ oxidation and metal solubilization. Here, the effect of temperature on the kinetics of S⁰ oxidation has been studied: oxidized Weiße Elster River sediment (dredged near Leipzig, Germany) was mixed with 2 % S⁰, suspended in water and then leached at various temperatures. The higher the temperature was, the faster the S⁰ oxidized, and the more rapid the pH decreased. But temperatures above 35 °C slowed down S⁰ oxidation, and temperatures above 45 °C let the process – after a short period of acidification to pH 4.5 – stagnate. The latter may be explained by the presence of both neutrophilic to less acidophilic thermotolerant bacteria and acidophilic thermosensitive bacteria. Within 42 days, nearly complete S⁰ oxidation and maximum heavy metal solubilization only occurred at 30 to 45 °C. The measured pH(t) courses were used to model the rate of S⁰ oxidation depending on the temperature using an extended Arrhenius equation. Since molecular oxygen is another factor highly influencing the activity of S⁰‐oxidizing bacteria, the effect of dissolved O₂ (controlled by the O₂ content in the gas supplied) on S⁰ oxidation was studied in suspension: the indigenous S⁰‐oxidizing bacteria reacted quite tolerant to low O₂ concentrations; the rate of S⁰ oxidation – measured as the specific O₂ consumption – was not affected until the O₂ content of the suspension was below 0.05 mg/L, i.e., the S⁰‐oxidizing bacteria showed a high affinity to O₂ with a half‐saturation constant of about 0.01 mg/L. Stoichiometric coefficients describing the relationship between the mass of S⁰, O₂ and CO₂ consumed are scarcely available. The growth of S⁰‐oxidizing, obligate aerobic, autotrophic bacteria was, therefore, stoichiometrically balanced (by using a yield coefficient of Y_X/S = 0.146 g cells/g S⁰, calculated with data from the literature): 24.14 S⁰ + 29.21 O₂ + 27.14 H₂O + 5 CO₂ + NO₃^–→ C₅H₇O₂N + 24.14 SO₄^2– + 47.28 H⁺, which resulted in Y = 1.21 g O₂/g S⁰ and Y = 0.28 g CO₂/g S⁰.     

Bioleaching of Heavy Metal Polluted Sediment: Influence of Sediment Properties (Part 2)

A remediation process for heavy metal polluted sediment has previously been developed, in which the heavy metals are removed from the sediment by solid‐bed bioleaching using sulfuric acid as a leaching agent arising from added elemental sulfur (S⁰). This process has been engineered with Weiße Elster River sediment (dredged near Leipzig, Germany), as an example. Here, six heavy metal polluted sediments originating from various bodies of water in Germany were subjected to bioleaching to evaluate the applicability of the developed process on sediment of different nature: each sediment was mixed with 2 % S⁰, suspended in water and then leached under identical conditions. The buffer characteristics of each sediment were mainly governed by its carbonate and Ca content, i.e., by its geological background, the redox potential and oxidation state depended on its pre‐treatment (e.g., on land disposal), while the pH value was influenced by both. The added S⁰ was quickly oxidized by the indigenous microbes even in slightly alkaline sediment. The microbially generated H₂SO₄ accumulated in the aqueous phase and was in part precipitated as gypsum. Significant acidification and heavy metal solubilization only occurred with sediment poor in buffer substances. With the exception of one sediment, the behavior in bioleaching correlated well with the behavior in titration with H₂SO₄. Since the content in carbonate seemed to be the most important factor deciding on the leachability of a sediment, oxic Weiße Elster River sediment was mixed with 2 % S⁰ and 0 to 100 g/kg of ground limestone to simulate various buffer capacities, suspended in water and then leached. The lime did not inhibit microbial S⁰ oxidation but generated a delay in acidification due to neutralization of formed H₂SO₄, where the pH only started to decrease when the lime was completely consumed. The more lime the sediment contained, the longer this lag period lasted, and the higher the pH and the lower the fraction of the solubilized heavy metals finally was. Since Cu requires stronger acidic conditions for its solubilization, it responded more sensitively to lime addition than Zn, Ni, and Cd. Heavy metal polluted sediment containing large amounts of carbonate may, in principle, also be remediated by bioleaching, but metal solubilization requires excessive amounts of the leaching agent and is thus uneconomical.     

Removal of Heavy Metals from the Environment by Biosorption

The pollution of the environment with toxic metals is a result of many human activities, such as mining and metallurgy, and the effects of these metals on the ecosystems are of large economic and public‐healthsignificance. This paper presents the features and advantages of the unconventional removal method of heavy metals – biosorption – as a part of bioremediation. Bioremediation consists of a group of applications, which involvethe detoxification of hazardous substances instead of transferring them from one medium to another, by means of microbes and plants. This process is characterized as less disruptive and can be often carried out on site, eliminating the need to transport the toxic materials to treatment sites. The biosorption (sorption of metallic ions from solutions by live or dried biomass) offers an alternative to the remediation of industrial effluents as well as the recovery of metals contained in other media. Biosorbents are prepared from naturally abundant and/or waste biomass. Due to the high uptake capacity and very cost‐effective source of the raw material, biosorption is a progression towards a perspective method. The mechanism by which microorganisms take up metals is relatively unclear, but it has been demonstrated that both living and non‐living biomass may be utilized in biosorptive processes, as they often exhibit a marked tolerance towards metals and other adverse conditions. One of their major advantages is the treatment of large volumes of effluents with low concentrations of pollutants. Models developed were presented to determine both the number of adsorption sites required to bind each metal ion and the rate of adsorption, using a batch reactor mass balance and the Langmuir theory of adsorption to surfaces or continuous dynamic systems. Two main categories of bioreactors used in bioremediation – suspended growth and fixed film bioreactors – are discussed. Reactors with varying configurations to meet the different requirements for biosorption are analyzed considering two major groups of reactors – batch reactors and continuous reactors. Biosorption is treated as an emerging technology effective in removing even very low levels of heavy metal.     

Comparison of the Adsorption Capabilities of Myriophyllum spicatum and Ceratophyllum demersum for Zinc,Copper and Lead

Industrial wastewaters contain various heavy metal components and therefore threaten aquatic bodies. Heavy metals can be adsorbed by living or non‐living biomass. Submerged aquatic plants can be used for the removal of heavy metals. This paper exhibits the comparison of the adsorption properties of two aquatic plants Myriophyllum spicatum and Ceratophyllum demersum for lead, zinc, and copper. The data obtained from batch studies conformed well to the Langmuir Model. Maximum adsorption capacities (q_max) were obtained for both plant species and each metal. The maximum adsorption capacities (q_max) achieved with M. spicatum were 10.37 mg/g for Cu²⁺, and 15.59 mg/g for Zn²⁺ as well as 46.49 mg/g for Pb²⁺ and with C. demersum they were 6.17 mg/g for Cu²⁺, 13.98 mg/g for Zn²⁺ and 44.8 mg/g for Pb²⁺. It was found that M. spicatum has a better adsorption capacity than C. demersum for each metal tested. Gibbs free energy and the specific surface area based on the q_max values were also determined for each metal.     

Specific Treatment Technologies for Removing Arsenic from Water

Arsenic (As) is a highly toxic metalloid found in ground and surface water. Arsenic contamination in drinking water leads to harmful effects on human health. To eliminate arsenic from drinking water, several technologies such as coagulation, adsorption, ion exchange, filtration, membrane processes, etc., have been used. In this study, three technologies were evaluated for arsenic removal. Results from batch kinetic experiments showed that iron coated sand (IOCS‐2) can remove more than 90 % of As from synthetic water. Experiments were conducted with three different pH values (6, 7, and 8) and an initial As concentration of 260 μg/L. A new material, developed in this study, namely iron coated sponge (IOCSp), was found to have a high capacity in removing both As (V) and As (III). Each gram of IOCSp adsorbed about 160 μg of As within a 9‐hour contact period of IOCSp with As solution. Low pressure nanofiltration removed more than 94 % of As from an influent containing 440 μg/L As. The applied pressure was varied from 85 to 500 kPa.     

Assessment of Contaminant Retention in Constructed Wetland Sediments

The A‐01 wetland treatment system (WTS) was designed to remove metals from an industrial effluent at the Savannah River Site, Aiken, SC. Sequential extraction data were used to evaluate remobilization and retention of Cu, Pb, Zn, Mn, and Fe in the wetland sediment. Remobilization of metals was determined by the Potentially Mobile Fraction (PMF) and metal retention by the Recalcitrant Factor (RF). The PMF, which includes water soluble, exchangeable, and amorphous oxides fractions, is the contaminant fraction that has the potential to enter into the mobile aqueous phase under fluctuating environmental conditions. PMF values were low for Cu, Zn, and Pb (13–27 %) and high for Fe and Mn (62–70 %). The RF, which includes crystalline oxides, sulfides or silicates and aluminosilicates, is the ratio of strongly bound fractions to the total concentration of elements in sediment. RF values ranged from 73–87 % for Cu, Zn, and Pb, indicating high retention in the sediment and from 30–38 % for Fe and Mn, indicating low retention. Contaminant retention, which is determined by solid phase metal speciation, determines the potential mobility and bioavailability of captured metals in wetland sediments; hence, their likelihood of being released if chemical, physical, or biological conditions within the wetland change.     

白腐菌的研究进展及其在重金属修复中的展望

白腐菌是一类特殊的丝状真菌,能降解多种污染物质,具有广谱、彻底、高效、无专一性的 特点,在生物修复中有广阔的应用前景。综述了白腐菌的分类、酶系、降解机理以及应用于有机 物污染的研究现状,特别介绍了白腐菌在重金属污染的生物修复的应用进展情况,包括白腐菌吸 附重金属的原理、在重金属污染的废水中的研究应用现状及在修复重金属污染土壤中需考虑的 因素。同时展望了白腐菌在重金属污染及复合污染的生物修复中的应用前景。     

Uptake of lead by bacteria isolated from industrial effluents and their potential use in bioremediation of wastewater

Due to rising populations and human activities, heavy metals (HM) toxicity has become a serious problem for all life forms. The present study deals with isolating and identifying lead-resistant bacteria from contaminated wastewater of tanneries effluents. Two isolated strains were identified as Bacillus cereus (ID1), and Bacillus sp. (ID3), and both strains resisted a 25 mM concentration of Lead nitrate (Pb (NO₃)₂). After four days of treatment, Bacillus cereus (ID1) showed 80% lead uptake, and Bacillus sp. (ID3) showed 88%. Lead uptake was confirmed by Energy dispersive X-Ray (EDX) analysis. Fourier transform infrared spectroscopy (FTIR) showed that structural alterations had occurred in functional groups of the treated samples compared to the controls. Our research indicates that these Bacillus strains may be useful in bioremediating heavy metals from polluted environments. Further investigation into the processes involved in the uptake and homeostasis of heavy metals by these strains is required, as is the identification of the genes and enzymes responsible for Pb-bioremediation.     

The Light Quanta Modulated Physiological Response of Brassica Juncea Seedlings Subjected to Ni(II) Stress

This work is a study of the inter‐relationship between parameters that principally affect the metal up‐take in the plant. The relationships between the concentration of metal in the growth medium, C_s, the concentration of metal absorbed by the plant, C_p, and the total biomass achieved, M, all of which are factors relevant to the efficiency of phytoremediation of the plant, have been investigated via the macro‐physiological response of Brassica juncea seedlings to Ni(II) stress. The factorial growth experiments treated the Ni(II) concentration in the agar gel and the diurnal light quanta (DLQ) as independently variable parameters. Observations included the evidence of light enhancement of Ni toxicity at the root as well as at the whole plant level, the shoot mass index as a possible indicator of shoot metal sequestration in B. juncea, the logarithmic variation of C_p with C_s and the power‐law dependence of M on C_p. The sum total of these observations indicates that for the metal accumulator B. juncea with regard to its capacity to accumulate Ni, the overall metabolic nature of the plant is important – neither rapid biomass increase nor a high metal concentration capability favor the removal of high metal mass from the medium, but rather the plant with the moderate photosynthetically driven biomass growth and moderate metal concentrations demonstrated the ability to remove the maximum mass of metal from the medium. The implications of these observations in the context of the perceived need in phytoremediation engineering to maximize C_p and M simultaneously in the same plant, are discussed.     

Effectiveness of Various Small‐Scale Constructed Wetland Designs for the Removal of Iron and Zinc from Acid Mine Drainage under Field Conditions

A system of planted and unplanted small‐scale subsurface flow (SSF) and surface flow (SF) constructed wetlands together with hydroponic systems (HP) were installed to compare the removal efficiencies of Fe and Zn from acid mine drainage (AMD) under long‐term field conditions. Maximum removal of 94–97 % (116–142 mg/m² d) for Fe and 69–77 % (6.2–7.9 mg/m² d) for Zn was calculated for the planted soil systems. The planted SSF was most sensitive to heavy rain fall. Short‐term increases of the metal concentration in the outflows, short‐term breakdowns of the Fe removal and continual long‐term breakdowns of the Zn removal were observed. In contrast to Zn removal, all wetland types are applicable for Fe removal with maximum removal in the range of 60–98 %. Most of the removed Fe and Zn was transformed and deposited inside the soil bed. The amount absorbed by the plants (0.03 to 0.3 %) and gravel‐associated soil beds (0.03 to 1.7 %) of the total input were low for both metals. The response of the planted SSF to rainfall suggests a remobilization of metals accumulated inside the rhizosphere and the importance of buffering effects of the surface water layers of SF systems. The importance of plants for metal removal was shown.     

Nickel Removal from Aqueous Solutions Using Sheep Manure Wastes

This paper reports a study on the potential use of sheep manure waste (SMW) for the removal of nickel ions from aqueous solutions. The adsorption of nickel ions from aqueous solutions on SMW has been studied as functions of contact time, initial pH, amount of sorbent, sorbent particle size, initial concentration of nickel ions, salt, and chelating agents. The experimental results showed that the SMW has a high affinity for nickel binding, where 79 % removal of 100 ppm initial nickel ions concentration was obtained using 8.0 mg SMW/mL, at pH 6.5 in 4 minutes equilibrium time. The equilibrium adsorption data were analyzed using four different isotherms: the Langmuir, Freundlich, Redlich‐Peterson, and Sips isotherm equations. The results of the kinetic studies showed that the adsorption of nickel ions on SMW is a pseudo‐first order with respect to the nickel ions solution concentration.     

A Laboratory Assessment of Potentials and Limitations of Using EDTA,Rhamnolipids, and Compost-derived Humic Substances (HS) in Enhanced Phytoextraction of Copper and Zinc Polluted Calcareous Soils

Phytoextraction is an economically and environmentally attractive in-situ method for cleaning heavy metal polluted soil. Phytoextraction is a rather slow process, but it can be enhanced by the application of chelating agents such as the synthetic ethylenediaminetetraacetic acid (EDTA). However, EDTA is persistent, toxic, and can promote heavy metal leaching. Replacement of EDTA by natural, non-toxic compounds such as humic substances (HS) or rhamnolipids (bacterial-produced biosurfactants) might be environmentally attractive but before recommending such alternatives, their suitability must be assessed. Therefore, compost-derived HS and rhamnolipids were compared with EDTA as natural non-toxic alternatives in a multi-step batch extraction test. The test included 10 steps carried out on two Cu and Zn polluted calcareous soils using a solution:soil ratio of 10 (L/kg). In each step, soil was extracted with an extractant containing EDTA, HS, or rhamnolipids corresponding to 250 mmol DOC/kg of soil (3 g C/kg). By HS extraction, each step resulted in the release of ～0.29 mg Cu/L and ～0.19 mg Zn/L, which is considered to enhance plant uptake without leading to unacceptable leaching and toxification of the plants (and the environment), suggesting HS can enhance phytoextraction. In contrast, the EDTA and the rhamnolipid treatments were found to be unsuitable because the EDTA released Cu and Zn in concentrations that may be toxic to plants and can lead to leaching, whereas the rhamnolipids showed insufficient capacity to mobilize Cu (and Zn). However, future investigations in the field are needed to confirm these laboratory results.     

Elimination of Heavy Metals from Leachates by Membrane Electrolysis

The elimination of heavy metals from bioleaching process waters (leachates) by electrolysis was studied in the anode and cathode region of a membrane electrolysis cell at current densities of 5–20 mA/cm² using various electrode materials. The leaching waters containing a wide range of dissolved heavy metals, were high in sulfate, and had pH values of approx. 3. In preliminary tests using a rotating disc electrode the current density‐potential curve (CPK) was recorded at a rotation velocity of 0, 1000 and 2000 rpm and a scan rate of 10 mV/s in order to collect information on the influence of transport processes on the electrochemical processes taking place at the electrodes. The electrochemical deposition‐dissolution processes at the cathode are strongly dependent on the hydrodynamics. Detailed examination of the anodic oxidation of dissolved Mn(II) indicated that the manganese dioxide which formed adhered well to the electrode surface but in the cathodic return run it was again reduced. Electrode pairs of high‐grade steel, lead and coal as well as material combinations were used to investigate heavy metal elimination in a membrane electrolysis cell. Using high‐grade steel, lead and carbon electrode pairs, the reduction and deposition of Cu, Zn, Cr, Ni and some Cd in metallic or hydroxide form were observed in an order of 10–40 % in the cathode chamber. The dominant process in the anode chamber was the precipitation of manganese dioxide owing to the oxidation of dissolved Mn(II). Large amounts of heavy metals were co‐precipitated by adsorption onto the insoluble MnO₂. High‐grade steel and to some extent lead anodes were dissolved and hence were proven unsuitable as an anode material. These findings were largely confirmed by experiments using combination electrodes of coal and platinized titanium as an anode material and steel as a cathode material. With both electrode combinations and current densities of 5 or 10 mA/cm², in the cathode region low depositions of 10–20 % Cd, 2–10% Mn, 5–20 % Zn, 1–20 % Co and 5–15 % Ni were measured. By contrast, the elimination of other metals was substantially larger: Fe 40 –60 %, Cu 20–40 %, and Cr 40–60 %. In the anode region the removal of heavy metals was in the order of 30–50%, with Mn being as high as 80 %. The anode materials exhibit good resistance at the current densities tested. The precipitates deposited in both electrode regions contained as main components Al with 10–20 %, Mg with approximately 10 %, and SO₄ with 5–20 %. The solid material in the cathode chamber consisted of relatively high proportions of Zn and Mn. Calcium in the solids indicated the co‐precipitation of calcium sulfate. The main components in the solids of the anode chamber were Mn in the form of pyrolusite, Al as basic sulfate, and Mg. The results indicate that electrochemical metal separation in the membrane electrolysis cell can represent a practical alternative to the metal separation by alkalization. Regarding the main heavy metals Zn, Mn and Ni in the process water, combination electrodes using steel as a cathode material and coal or platinized titanium as an anode material proved to be suitable for eliminating the heavy metals from the aqueous phase. However, for practical application, further work is necessary to improve the efficiency, applicability and costs of the process.     

Physicochemical Conditioning of Dredged Heavy Metal‐Polluted Sediment in Suspension

The remediation of heavy metal‐polluted aquatic sediment by solid‐bed bioleaching requires a material well permeable to air and water. Freshly dredged sediment is nearly impermeable and needs previous conditioning to make it suitable for solid‐bed leaching. This conditioning – in practice carried out by planting sediment packages with helophytes – comprises water removal by evapotranspiration, abiotic and microbial oxidation of sediment‐borne reduced compounds, acidification, as well as structural changes improving the sediment permeability. The rate of this process seems to be limited by the transport of oxygen into the sediment bed. For a better understanding of the physicochemical processes occurring during conditioning, sediment oxidation was studied in a stirred suspension to minimize transport limitations. Freshly dredged, silty, anoxic, heavy metal‐polluted sediment from the Weisse Elster River (Germany) was suspended in water and then continuously stirred and aerated at 20 °C. Aerobic conditions appeared within a few hours. The redox potential increased from – 400 to + 220 mV, at first very quickly and later more slowly. Sediment‐borne inorganic sulfur compounds were oxidized to sulfate (S⁰ mainly within two days and sulfide within ten days), which reduced the pH from 7.2 to 5.9. A successive oxidation of FeS to Fe(II) sulfate, the oxidation of Fe(II) to Fe(III) followed by Fe(III) oxyhydrate formation caused the dissolved Fe to sharply increase and thereafter rapidly decrease. Ammonium was completely oxidized in a nitrification process to form nitrate, further decreasing the pH to 5.5. The acidification increased the solubility of Mn, Zn, Mg, Ca, and K. The increase in dissolved Mn rules out any oxidation of Mn(II) to Mn(IV) since Mn(IV) would have been insoluble under the prevailing pH and redox conditions. Sediment oxidation did not proceed in a well‐defined, redox‐potential‐directed order, but individual (partly microbially) oxidation processes superimposed each other. Physicochemical conditioning of suspended sediment was completed after 20 days while conditioning in a solid bed would require months or even years. These different rates result from transport limitations in the solid bed. Sediment conditioning in a solid bed could therefore possibly be accelerated by prior sediment aeration.     

Kinetics of Mercury Reduction by Serratia marcescens Mercuric Reductase Expressed by Pseudomonas putida Strains

Mercury (Hg) resistance is widespread among microorganisms and is based on the intracellular transformation of Hg(II) to less toxic elemental Hg(0). The use of microbial consortia to demercurize polluted wastewater streams and environments has been demonstrated. To develop efficient and versatile microbial cleanup strategies requires detailed knowledge of transport and reaction rates. This study focuses on the kinetics of the key enzyme of the microbial transformation, e.g., the mercuric reductase (MerA) under conditions closely resembling the cell interior. To this end, previously constructed and characterized Pseudomonas putida strains expressing MerA from Serratia marcescens were applied. Of the P. putida strains considered in this study P. putida KT2442::mer73 constitutively expressing broad spectrum mercury resistance (merTPAB) yielded the highest mercuric reductase (MerA) activity directly after cell disruption. MerA in the raw extract was further purified (about 100 fold). Reduction rates were measured for various substrates (HgCl₂, Hg₂SO₄, Hg(NO₃)₂ and phenyl mercury acetate) up to high concentrations dependent on the purification grade. In all cases, a pronounced substrate inhibition was found. The kinetic constants determined for the cell raw extract are in agreement with those measured for intact cells. However, the rate data exhibit reduced affinity and inhibition with rising purification grade (specific activity). Therefore, the findings seemingly point to reactions preceding the catalytic reduction. Based on simplified assumptions, a kinetic model is suggested which reasonably describes the experimental findings and can advantageously be applied to the bioreactor design.     

Biotechnological strategies applied to the decontamination of soils polluted with heavy metals

Soils have been submitted to several contaminants that vary in concentration and composition. Heavy metals can be widely spread and accumulated in those environments due to some inappropriate actions. In this present review some remediation techniques to remediate soils are presented, focusing on the use of plants that are capable of surviving in soils with heavy metals along with the function of some microorganisms in the restoration process.     

Treatment of Process Water Containing Heavy Metals with a Two‐Stage Electrolysis Procedure in a Membrane Electrolysis Cell

The capability of a two‐stage electrochemical treatment for the regeneration of acidic heavy‐metal containing process water was examined. The process water came from sediment bioleaching and was characterized by a wide spectrum of dissolved metals, a high sulfate content, and a pH of about 3. In the modular laboratory model cell used, the anode chamber and the cathode chamber were separated by a central chamber fitted with an ion exchanger membrane on either side. The experiments were carried out applying a platinum anode and a graphite cathode at a current density of 0.1 A/cm². The circulation flow of the process water in the batch process amounted to 35 L/h, the electrolysis duration was 5.5 h at maximum and the total electrolysis current was about 1 A. In the first stage, the acidic process water containing metals passed through the cathode chamber. In the second stage, the cathodically pretreated process water was electrolyzed anodically. In the cathode chamber the main load of dissolved Cu, Zn, Cr and Pb was eliminated. The sulfuric acid surplus of 3–4 g/L decreased to about 1 g/L, the pH rose from initially 3.0 to 4–5, but the desired pH of 9–10 was not achieved. Precipitation in the proximity to the cathode evidently takes place at a higher pH than farther away. The dominant process in the anode chamber was the precipitation of amorphous MnO₂ owing to the oxidation of dissolved Mn(II). The further depletion of the remaining heavy metals in the cathodically pretreated process water by subsequent anodic treatment was nearly exhaustive, more than 99 % of Cd, Cr, Cu, Mn, Ni, Pb, and Zn were removed from the leachate. The high depletion of heavy metals might be due to both the sorption on MnO₂ precipitates and/or basic ferrous sulfate formed anodically, and the migration of metal ions through the cation exchanger membrane via the middle chamber into the cathode chamber. In the anode chamber, the sulfuric acid content increased to 6–7 g/L and the pH sank to 1.7. All heavy metals contained, with the exception of Zn, were removed to levels below the German limits for discharging industrial wastewaters into the receiving water. Moreover, the metal‐depleted and acid‐enriched process waters could be returned to the leaching process, hence reducing the output of wastewater. The results indicated that heavy metals could be removed from acidic process waters by two‐stage electrochemical treatment to a large extent. However, to improve the efficiency of metal removal and to establish the electrochemical treatment in practice, further work is necessary to optimize the operation of the process with respect to current density, energy consumption, discharging of metal precipitates deposited in the electrode chambers and preventing membrane clogging.     

土壤重金属污染生态过程、效应及修复

本文探讨了重金属在土壤中的行为特性及其生态化学过程作用的特点,不同的重金属元素在土壤胶体颗粒表面的吸附特性及不同元素间的交互作用类型有所不同,自然对重金属迁移积累的影响有所不同。土壤重金属污染影响了种子萌发、幼苗生长、作物产量及体内重金属含量,探讨了污染土壤的酶学评价方法。阐述了重金属污染土壤生物修复的特点,展望了重金属污染生态过程研究的未来发展趋势。