Effect of copper(II) on natural organic matter removal during drinking water coagulation using aluminum-based coagulants.

Coagulation has been proposed as a best available technology for controlling natural organic matter (NOM) during drinking water treatment. The presence of heavy metals such as copper(II) in source water, which may form copper-NOM complexes and/or interact with a coagulant, may pose a potential challenge on the coagulation of NOM. In this work, the effect of copper(II) on NOM removal by coagulation using alum or PAX-18 (a commercial polymerized aluminum chloride from Kemiron Inc., Bartow, Florida) was examined. The results show that the presence of 1 to 10 mg/L of copper(H) in the simulated waters improved the total organic carbon (TOC) removal by up to 25% for alum coagulation and by up to 22% for PAX-18 coagulation. The increased NOM removal with the presence of copper(II) in the waters can most likely be ascribed to the formation copper-NOM complexes that may be more adsorbable on aluminum precipitates and to the formation of copper(II) co-precipitates that may also adsorb NOM. The presence of 1 to 5 mg/L of copper(I) in the waters containing 3 mg/L NOM as carbon was reduced below the maximum contaminant level goal (1.3 mg/L as copper) using either coagulant. The results suggest that the presence of copper(H) in source water may not adversely affect the NOM removal by coagulation. A good linear correlation was observed between the TOC removal efficiency and the log-total moles of the precipitated metals, which include the metal ion from a coagulant and the divalent metal ion(s) in source water.     

新型混凝剂应用于中水处理的试验研究

围绕着中水回用过程中面临的若干关键问题,通过系统研究筛选高效混凝剂及优化混凝过程来提高污染物去除率,为中水回用提供经济合理的工艺途径.实验结果表明,与FeCl3相比,HPACS系列具有显著优越的除浊与除有机物性能.除磷性能则较为一致,可以达到90%以上的去除率.PFAC系列与FeCl3相比,除浊性能较差,取决于混凝剂中的有效成分的含量,但是具有较为优越的除有机物性能.HPAA系列具有显著优越的除浊和除有机物性能.HPFA与FeCl3系列相比,则具有较高的除磷效果,HPAA的除磷效果则相对较差.不同系列混凝剂具有不同的除浊、除有机物与除磷性能,需要结合分质供水的要求进行优化应用.     

Sub-lethal effects of heavy metals on activated sludge microorganisms

The effects of heavy metals, at sub-lethal concentrations, on activated sludge microbial ecosystem were investigated. Adsorption capacity and rate of copper, chromium, lead and zinc on microbial flocs were much faster than that of organic matters. Metals affected not only the adsorption rate of organic matters but also the COD adsorption capacity of the activated sludge. Effects of heavy metals. on wastewater treatment performance of a sequencing batch reactor were also studied. Metal-laden wastewater at sub-lethal levels affected the performance to different extents, depending on the hydraulic retention time. Metal ions acted as a strong competitor against the organic compounds for active sites on the bioflocs instead of acting as a toxic microbial inhibitor, thus hampering organic adsorption and affecting the COD removal efficiency under shorter HRTs.     

Bacterial leaching of heavy metals from sewage sludge-bioreactors comparison

More than 50% of municipal sewage sludges cannot be used on agricultural land because of their heavy metals content. Therefore, microbial leaching of heavy metal from municipal sludge was studied in a continuously stirred tank reactor without recycling (CSTR) or with sludge recycling (CSTRWR) at residence times of 1, 2, 3 and 4 days. The reactor CSTRWR is supposed to be more efficient for bacterial process due to the recycling of active bacteria from the settling tank to the reactor. The CSTRWR and the CSTR with 1 g litre(-1) FeSO(4).7H(2)O addition were equally efficient because of copper reprecipitation or recomplexation in the settling tank of the CSTRWR. In the CSTR, about 62% of copper and about 77% of zinc were dissolved in 3 days residence time compared to 50% of copper and 64% of zinc in the CSTRWR, if 3 g litre(-1) FeSO(4).7H(2)O was added. Thus with larger amount of substrate, the CSTR was more efficient than the CSTRWR. Residence time and pH were the main factors for zinc solubilization while for copper, the redox potential was also a major factor. The effect of FeSO(4).7H(2)O concentration on bacterial activity to solubilize heavy metals was also studied, increased concentration of FeSO(4).7H(2)O yielded better copper solubilization while it had no effect or a negative effect on zinc. This supports the hypothesis of a direct mechanism for zinc solubilization and of an indirect mechanism for copper solubilization.     

The application of novel coagulant reagent (polyaluminium silicate chloride) for the post-treatment of landfill leachates

Relatively "old" (stabilized) landfill leachates are a special category of wastewaters, which are difficult to treat further, mainly due to their bio-refractory organic content (humic substances). In this study, coagulation-flocculation was examined as post-treatment method for the biologically pre-treated stabilized leachates. The purpose was to examine the coagulation performance of alternative coagulant agents, i.e. the composite coagulant polyaluminium silicate chloride. Composite coagulants with different Al to Si molar ratio and different preparation methods were tested. Their efficiency was evaluated by monitoring from turbidity and phosphate content, other parameters strongly correlated with the presence of organic matter, such as UV absorbance at 254nm, COD and colour. The results suggest that the silica-based coagulants exhibit better coagulation performance, than the relevant conventional coagulant (alum) or simple pre-polymerized coagulants (PACl). Polyaluminium silicate chloride has greater tolerance against pH variation than alum or PACl, whereas this novel coagulant works better at pH values between 7 and 9. Coagulation-flocculation has proved to be an efficient post-treatment method for the biologically pre-treated leachates, promoting the removal of the refractory humic substances, while the treatment efficiency of coagulation can be improved by the application of the new coagulant agent.     

Coagulation and precipitation as post-treatment of anaerobically treated primary municipal wastewater.

The main objective of this study was to investigate the feasibility of coagulation as a post-treatment method of anaerobically treated primary municipal wastewater. Both mesophilic and ambient (20 degrees C) temperature conditions were investigated in a laboratory-scale upflow anaerobic sludge bed (UASB) reactor. In addition, optimization of the coagulant, both in terms of type and dose, was performed. Finally, phosphorus removal by means of aluminum and iron coagulation and phosphorus and ammonia nitrogen removal by means of struvite precipitation were studied. Anaerobic treatment of primary effluent at low hydraulic retention times (less than 15 hours) resulted in mean chemical oxygen demand (COD) removals ranging from 50 to 70%, while, based on the filtered treated effluent, the mean removals increased to 65 to 80%. Alum coagulation of the UASB effluent gave suspended solids removals ranging from approximately 35 to 65%. Turbidity removal reached up to 80%. Remaining COD values after coagulation and settling were below 100 mg/L, while remaining total organic carbon (TOC) levels were below 50 mg/L. Filterable COD levels were generally below 60 mg/L, while filterable TOC levels were below 40 mg/L. All coagulants tested, including prepolymerized aluminum and iron coagulants, demonstrated similar efficiency compared with alum for the removal of suspended solids, COD, and TOC. Regarding struvite precipitation, optimal conditions for phosphorus and nitrogen removal were pH 10 and molar ratio of magnesium: ammonia-nitrogen: phosphate-phosphorus close to the stoichiometric ratio (1:1:1). During struvite precipitation, removal of suspended solids reached 40%, while turbidity removal reached values up to 80%. The removal of COD was approximately 30 to 35%; yet, when removal of organic matter was based on the treated filterable COD, the removal increased to approximately 65%. In addition, nitrogen was removed by approximately 70%, while phosphorus removal ranged between approximately 30 and 45% on the basis of the initial phosphorus concentration. Finally, size fractionation of the organic matter (COD) showed that the various treatment methods were capable of removing different fractions of the organic matter.     

The effect of turbation on zinc relocation in a vertical floodplain soil profile

Turbation is hypothesized to affect the redistribution of heavy metals in polluted floodplain soils by effects on mobility. This hypothesis was tested in microcosms by turbation of zinc-spiked sediment top layers. Manual turbation caused a fast decrease of the zinc content in the upper 15 cm of the soil, even though turbation was only applied to the upper two centimetres. It was especially zinc attached to colloid and organic matter particles that was redistributed from the top layer. Percolation processes resulted in the attached zinc being drained to depths of more than 15 cm. The decrease in zinc content of the topsoil was even stronger in combination with inundation. No indications were found for the redistribution of zinc as a result of an increase of the extractability with 0.01 M CaCl2 or changes in pH. The findings suggest that mechanical turbation and bioturbation may redistribute heavy metals from topsoils in polluted floodplains just after inundation as observed in these turbation experiments.     

Fate and effects of nutrients and heavy metals in experimental salt marsh ecosystems

Fate and effects of the macro nutrients nitrogen and phosphorus, and the heavy metals zinc, copper and cadmium, brought into experimental salt marsh ecosystems via sediment supply, were studied over a three-year period. The supply of sediment from the Marsdiep (at a low and high rate) and from the harbour of Delfzijl (at a high rate) led to an increase of the macro nutrients and heavy metals in the top soil. The growth of the salt marsh plants Aster tripolium, Puccinellia maritima and Spartina anglica and the uptake of the macro nutrients and heavy metals by the plants was only slightly affected by the addition of sediment. A high load of sediment led to an increase in growth or in the concentrations of the macro nutrients or heavy metals in the plants at a number of sampling dates, but only minor differences between treatments were found. From a mass balance constructed over a three-year study period it could be concluded that about 50% of the macro nutrients and heavy metals were retained in the salt marsh sediment. This was equal to the retained amount of organic matter, indicating that retention of the elements was closely related to retention of organic matter. The 50% loss of the macro nutrients and heavy metals probably occurred via ebb tides after resuspension of sediment and organic matter.     

常用城市污水再生处理工艺净化效果比较分析

以城市污水回用为目的,对常规混凝-沉淀-过滤工艺、臭氧生物活性炭和直接超滤等深度处理技术处理城市污水处理厂二级出水的效果进行了试验研究,对各种工艺的去除效果进行了评价。     

Preparation of macromolecular heavy metal coagulant and treatment of wastewater containing copper.

Many treatment technologies for wastewater containing heavy metals have been developed in recent years, but these technologies have some disadvantages, such as poor removing efficiency and complex operation. For this reason, a macromolecular heavy metal coagulant polyethyleneimine-sodium xanthogenate (PEX) was prepared by grafting a xanthogenate group to polyethyleneimine. It was determined that PEX has the function of removing both turbidity and copper ions. It was also determined that copper ions and turbidity have a cooperative removal effect with each other in the process of treating wastewater containing both turbidity and copper ions by PEX. The investigation showed that PEX is an amphoteric polyelectrolyte. At lower pH values, the amino groups of the macromolecule are electrically positive; therefore, turbidity is removed because of electroneutralization coagulation; at higher pH values, both amino groups and xanthogenic radical groups contribute to the removal of heavy metals, as a result of chelation. Compared with traditional chemical precipitation by calcium oxide and coagulation by an ordinary inorganic coagulant, PEX showed obvious advantages, for example, removing both turbidity and copper ions, higher removal efficiency, lower suitable pH value, and higher floc settlement velocity.     

Enhanced removal of heavy metals in primary treatment using coagulation and flocculation.

The goal of this study was to determine the removal efficiencies of chromium, copper, lead, nickel, and zinc from raw wastewater by chemically enhanced primary treatment (CEPT) and to attain a total suspended solids removal goal of 80%. Operating parameters and chemical doses were optimized by bench-scale tests. Locally obtained raw wastewater samples were spiked with heavy metal solutions to obtain representative concentrations of metals in wastewater. Jar tests were conducted to compare the metals removal efficiencies of the chemical treatment options using ferric chloride, alum, and anionic polymer. The results obtained were compared with those from other studies. It was concluded that CEPT using ferric chloride and anionic polymer is more effective than CEPT using alum for metals removal. The CEPT dosing of 40 mg/L ferric chloride and 0.5 mg/L polymer enhanced heavy metals removal efficiencies by over 200% for chromium, copper, zinc, and nickel and 475% for lead, compared with traditional primary treatment. Efficient metals capture during CEPT can result in increased allowable headworks loadings or lower metal levels in the outfall.     

Waste green sands as reactive media for the removal of zinc from water

Waste green sands are industrial byproducts of the gray iron foundry industry. These green sands are composed of fine silica sand, clay binder, organic carbon, and residual iron particles. Because of their potential sorptive and reactive properties, tests were performed to determine the feasibility of using green sands as a low cost reactive medium in permeable reactive barriers (PRBs). Serial batch kinetic tests and conventional batch sorption tests were conducted to determine the removal characteristics for zinc in aqueous solutions. Removal characteristics for zinc in the presence of green sands are comparable to those of Peerless iron, a common reactive medium used in PRBs. High removal capacities for zinc of green sands are attributed to clay, organic carbon, and residual iron particles, which are known sorptive media for heavy metals. Furthermore, high pH values in the presence of clay and residual iron particles enhanced sorption and precipitation of zinc.     

Bioremediation of industrial effluents containing heavy metals using brewing cells of <Emphasis Type="Italic">Saccharomyces cerevisiae</Emphasis> as a green technology: a review

The release of heavy metals into the environment, mainly as a consequence of anthropogenic activities, constitutes a worldwide environmental pollution problem. Unlike organic pollutants, heavy metals are not degraded and remain indefinitely in the ecosystem, which poses a different kind of challenge for remediation. It seems that the “best treatment technologies” available may not be completely effective for metal removal or can be expensive; therefore, new methodologies have been proposed for the detoxification of metal-bearing wastewaters. The present work reviews and discusses the advantages of using brewing yeast cells of Saccharomyces cerevisiae in the detoxification of effluents containing heavy metals. The current knowledge of the mechanisms of metal removal by yeast biomass is presented. The use of live or dead biomass and the influence of biomass inactivation on the metal accumulation characteristics are outlined. The role of chemical speciation for predicting and optimising the efficiency of metal removal is highlighted. The problem of biomass separation, after treatment of the effluents, and the use of flocculent characteristics, as an alternative process of cell–liquid separation, are also discussed. The use of yeast cells in the treatment of real effluents to bridge the gap between fundamental and applied studies is presented and updated. The convenient management of the contaminated biomass and the advantages of the selective recovery of heavy metals in the development of a closed cycle without residues (green technology) are critically reviewed.     

Performance evaluation of intermediate cover soil barrier for removal of heavy metals in landfill leachate

This pilot-scale study evaluated the use of intermediate cover soil barriers for removing heavy metals in leachate generated from test cells for co-disposed fly ash from municipal solid waste incinerators, ash melting plants, and shredder residue. Cover soil barriers were mixtures of Andisol (volcanic ash soil), waste iron powder, (grinder dust waste from iron foundries), and slag fragments. The cover soil barriers were installed in the test cells' bottom layer. Sorption/desorption is an important process in cover soil bottom barrier for removal of heavy metals in landfill leachate. Salt concentrations such as those of Na, K, and Ca in leachate were extremely high (often greater than 30 gL(-1)) because of high salt content in fly ash from ash melting plants. Concentrations of all heavy metals (nickel, manganese, copper, zinc, lead, and cadmium) in test cell leachates with a cover soil barrier were lower than those of the test cell without a cover soil barrier and were mostly below the discharge limit, probably because of dilution caused by the amount of leachate and heavy metal removal by the cover soil barrier. The cover soil barriers' heavy metal removal efficiency was calculated. About 50% of copper, nickel, and manganese were removed. About 20% of the zinc and boron were removed, but lead and cadmium were removed only slightly. Based on results of calculation of the Langelier saturation index and analyses of core samples, the reactivity of the cover soil barrier apparently decreases because of calcium carbonate precipitation on the cover soil barriers' surfaces.     

Selective removal of heavy metals from metal-bearing wastewater in a cascade line reactor

Goal, Scope and Background This paper is a part of the research work on ‘Integrated treatment of industrial wastes towards prevention of regional water resources contamination — INTREAT’ the project. It addresses the environmental pollution problems associated with solid and liquid waste/effluents produced by sulfide ore mining and metallurgical activities in the Copper Mining and Smelting Complex Bor (RTB-BOR), Serbia. However, since the minimum solubility for the different metals usually found in the polluted water occurs at different pH values and the hydroxide precipitates are amphoteric in nature, selective removal of mixed metals could be achieved as the multiple stage precipitation. For this reason, acid mine water had to be treated in multiple stages in a continuous precipitation system-cascade line reactor. Materials and Methods All experiments were performed using synthetic metal-bearing effluent with chemical a composition similar to the effluent from open pit, Copper Mining and Smelting Complex Bor (RTB-BOR). That effluent is characterized by low pH (1.78) due to the content of sulfuric acid and heavy metals, such as Cu, Fe, Ni, Mn, Zn with concentrations of 76.680, 26.130, 0.113, 11.490, 1.020 mg/dm³, respectively. The cascade line reactor is equipped with the following components: for feeding of effluents, for injection of the precipitation agent, for pH measurements and control, and for removal of the process gases. The precipitation agent was 1M NaOH. In each of the three reactors, a changing of pH and temperature was observed. In order to verify efficiency of heavy metals removal, chemical analyses of samples taken at different pH was done using AES-ICP. Results Consumption of NaOH in reactors was 370 cm³, 40 cm³ and 80 cm³, respectively. Total time of the experiment was 4 h including feeding of the first reactor. The time necessary to achieve the defined pH value was 25 min for the first reactor and 13 min for both second and third reactors. Taking into account the complete process in the cascade line reactor, the difference between maximum and minimum temperature was as low as 6°C. The quantity of solid residue in reactors respectively was 0.62 g, 2.05 g and 3.91 g. In the case of copper, minimum achieved concentration was 0.62 mg/dm³ at pH = 10.4. At pH = 4.50 content of iron has rapidly decreased to < 0.1 mg/dm³ and maintained constant at all higher pH values. That means that precipitation has already ended at pH=4.5 and maximum efficiency of iron removal was 99.53%. The concentration of manganese was minimum at pH value of 11.0. Minimum obtained concentration of Zn was 2.18 mg/dm³ at a pH value of 11. If pH value is higher than 11, Zn can be re-dissolved. The maximum efficiency of Ni removal reached 76.30% at a pH value of 10.4. Discussion Obtained results show that efficiency of copper, iron and manganese removal is very satisfactory (higher than 90%). The obtained efficiency of Zn and Ni removal is lower (72.30% and 76.31%, respectively). The treated effluent met discharge water standard according to The Council Directive 76/464/EEC on pollution caused by certain dangerous substances into the aquatic environment of the Community. Maximum changing of temperature during the whole process was 6°C. Conclusion This technology, which was based on inducing chemical precipitation of heavy metals is viable for selective removal of heavy metals from metal-bearing effluents in three reactor systems in a cascade line. Recommendations and Perspectives The worldwide increasing concern for the environment and guidelines regarding effluent discharge make their treatment necessary for safe discharge in water receivers. In the case where the effluents contain valuable metals, there is also an additional economic interest to recover these metals and to recycle them as secondary raw materials in different production routes. ESS-Submission Editor: PhD Hailong Wang, hailong.wang@ensisjv.com     

Effects of heavy metals on sea urchin embryo development. Part 2. Interactive toxic effects of heavy metals in synthetic mine effluents

Interactive toxic effects between heavy metals were investigated using a sea urchin (Anthocidaris crassispina) bioassay. An effluent from an abandoned mine showed significant inhibitory effects on embryo development as well as producing specific malformations. The effects on the embryos were reproduced by synthetic polluted seawater consisting of eight metals (manganese, lead, cadmium, nickel, zinc, chromium, iron, and copper) at the concentrations detected in the mine effluent. This indicated that the heavy metals were responsible for the effects observed. Five heavy metals were ranked in decreasing order of toxicity as follows: Cu>Zn>Pb>Fe>Mn. Among these, zinc and manganese could cause malformation of the embryos. From bioassay results using 27 combinations of heavy metals, 16 combinations including zinc could produce specific malformations, such as radialized, exo-gastrulal, and spaceship Apollo-like gastrulal embryos. Zinc was one of the elements responsible for causing malformations and its effects were intensified by the presence of the other metals, such as manganese, lead, iron, and copper.     

Microbial cellulose decomposition in soils from a rifle range contaminated with heavy metals

The objective of this study was to assess the effects of heavy metals on microbial decomposition of cellulose in heavy metal-contaminated soils using a cotton strip assay. The assay is a measure of the potential of soil microorganisms to decompose the plant polymer, cellulose. Cellulolytic activity in soil was assessed by determining the reduction in tensile strength of the buried cotton strips over a 25- and 45-day period. Soils were obtained from a rifle range that contain high levels of lead, copper and zinc. The site has been used for approximately 50 years, resulting in metal levels of up to 30,000 mg/kg of lead, 4000 mg/kg of copper and 600 mg/kg of zinc in the most contaminated soils. All the metal-contaminated soils had lower degradation rates than the uncontaminated soils tested. Among the contaminated soils, however, the heavy metal concentration was not the major factor in determining the loss in tensile strength of the cotton strips, where cellulose decomposition was governed by other soil physicochemical properties. Soil with a higher cation exchange capacity, readily oxidisable material and volatile solids content had the greatest loss in tensile strength of cotton strips. Microbial adaptation to the presence of high concentrations of soil heavy metals and reduced bioavailability of metals is the likely explanation for this phenomenon.     

Selective recovery of chromium,copper, nickel,and zinc from an acid solution using an environmentally friendly process

Purpose  

Real electroplating effluents contain multiple metals. An important point related with the feasibility of the bioremediation process is linked with the strategy to recover selectively metals. In this work, a multimetal solution, obtained after microwave acid digestion of the ashes resulted from the incineration of Saccharomyces cerevisiae contaminated biomass, was used to recover selectively chromium, copper, nickel, and zinc.     

Plagiochasma appendiculatum as a biotest for water quality assessment

A thalloid pathogen-free liverwort, Plagiochasma appendiculatum, was exposed to different pollution stresses, especially heavy metals, synthesized in the laboratory, to simulate pollutants reported to occur in industrial areas. The plant was found to be sensitive to mercury and copper. Thallus injury and chlorophyll content showed effects with increasing exposure to metals. In contrast, the plant was found to be resistant to lead, zinc and chromium. The plant showed growth in some concentrations of these metals, hence suggesting their accumulation. In this paper, the possible use of Plagiochasma in the assessment of water quality, especially for heavy metals, is discussed, with special reference to thallus deterioration as a simple biomonitoring parameter.     

Measurement of Ozone Levels by Ship Along the Eastern Shore of Lake Michigan

The U.S. Environmental Protection Agency (EPA), in cooperation with the Toronto Harbour Commissioners (THC), conducted a Superfund Innovative Technology Evaluation (SITE) demonstration of the THC Soil Recycle Treatment Train. The treatment train consists of three technologies operated in sequence: a soil wash process, a metals removal process, and a biological treatment process. The THC conducted an extensive demonstration of the treatment train at a 55 tons per day pilot plant in order to evaluate an approach for remediation of industrial/commercial sites that are situated in the Toronto Port Industrial District (PID). Three soils were processed during the THC demonstration. The EPA SITE demonstration project examined, in detail, soil processing from one of the sites being evaluated as part of the overall THC project. Contaminants included organic compounds and heavy metals. It has been estimated by THC that as much as 2,200,000 tons of soil from locations within the PID may require some form of treatment due to heavy metal and/or organic contamination that resulted from various industrial processing operations. The objective of the SITE demonstration was to evaluate the technical effectiveness of the process in relation to THC’s target criteria.

Gravel and sand that met the THC target criteria for medium to fine soil suitable for industrial/commercial sites was produced. The fine soil from the biological treatment process did not meet the target level of 2.4 ppm for benzo(a)pyrene. However, there was a significant reduction in polynuclear aromatic hydrocarbon (PAH) compounds. The metals removal process achieved reductions of greater than seventy percent for copper, lead, nickel, and zinc.