Application of ionic liquids for the removal of heavy metals from wastewater and activated sludge

This paper presents the results of adsorption studies on the removal of heavy metals (Cr, Cu, Cd, Ni, Pb and Zn) from standard solutions, real wastewater samples and activated sewage sludge using a new technique of liquid-liquid extraction using quaternary ammonium and phosphonium ionic liquids (ILs). Batch sorption experiments were conducted using the ILs [PR4][TS], [PR4][MTBA], [A336][TS] and [A336][MTBA]. Removal of these heavy metals from standard solutions were not effective, however removal of heavy metals from the industrial effluents/wastewater treatment plants were satisfactory, indicating that the removal depends mainly on the composition of the wastewater and cannot be predicted with standard solutions. Removal of heavy metals from activated sludge proved to be more successful than conventional methods such as incineration, acid extraction, thermal treatment, etc. For the heavy metals Cu, Ni and Zn, ≥90% removal was achieved.     

Influent concentrations and removal performances of metals through municipal wastewater treatment processes

This extensive study aimed at quantifying the concentrations and removal efficiency of 23 metals and metalloids in domestic wastewater passing through full-scale plants. Nine facilities were equipped with secondary biological treatment and three facilities were equipped with a tertiary treatment stage. The metals investigated were Li, B, Al, Ti, V, Cr, Fe, Ni, Co, Cu, Zn, As, Se, Rb, Mo, Ag, Cd, Sn, Sb, Ba, TI, Pb and U. Particulate and dissolved metals were measured using 24 h composite samples at each treatment stage. In influents, total concentrations of Cd, Sb, Co, Se, U, Ag, V were below a few microg/L, whereas at the other extremity Zn, B, Fe, Ti, Al were in the range of 0.1 to > 1 mg/L. It was demonstrated that secondary treatment stage (activated sludge, biodisc and membrane bioreactor) were efficient to remove most metals (removal rate > 70%), with the exception of B, Li, Rb, Mo, Co, As, Sb and V due to their low adsorption capacities. With the tested tertiary stages (polishing pond, rapid chemical settler, ozonation), a removal efficiency was obtained for Ti, Cr, Cd, Cu, Zn, Sn, Pb, Fe, Ag and Al, whereas a little removal (< 30%) was obtained for other metals.     

Occurrence and fate of heavy metals in large wastewater treatment plants treating municipal and industrial wastewaters.

This paper deals with a detailed study on the occurrence and fate of heavy metals (plus As, Fe and Al) in five Italian large wastewater treatment plants treating municipal and industrial wastewaters. The study showed that some of the compounds (As, Hg and Cd) were present at trace levels, while others were dispersed in a broad range of concentrations and were sometimes under the detection limit. The occurrence followed the order Hg = As < Hg < Pb < Ni < Cu < Cr < Fe < Zn < Al. Metals were mainly present bound to particulate organic matter in municipal wastewaters while they were often present in soluble phase in industrial wastewaters. Some heavy metals, like Hg and Pb, showed clear correlations with Al and Fe, therefore the last could be used as control parameters. Metals were removed with good efficiency in the treatment works, with the order As < Cd = Cr = Zn < Pb < Hg < Ni = Al < Cu < Fe. Metals then concentrated in waste activated sludge and accumulated after sludge stabilisation because of volatile solids degradation, therefore some problems may arise with limit for agricultural application, in particular for Hg, Cd and Ni.     

On-site evaluation of the removal of 100 micro-pollutants through advanced wastewater treatment processes for reuse applications

The next challenge of wastewater treatment is to reliably remove micro-pollutants at the microgram per litre range in order to meet reuse applications and contribute to reach the good status of the water bodies. A hundred priority and relevant emerging substances were measured to evaluate at full-scale the removal efficiencies of seven advanced treatment lines (one membrane bioreactor process and six tertiary treatment lines) that were designed for reuse applications. To reliably compare the processes, specific procedures for micro-pollutants were applied for sampling, analysis and calculation of removal efficiencies. The membrane bioreactor process allowed to upgrade the removal efficiencies of about 20% of the substances measured, especially those that were partially degraded during conventional processes. Conventional tertiary processes like high rate clarification, sand filtration and polishing pond achieved significant removal for some micro-pollutants, especially for adsorbable substances. Advanced tertiary processes, like ozonation, activated carbon and reverse osmosis were all very efficient to complete the removal of polar pesticides and pharmaceuticals; metals and less polar substances were better retained by reverse osmosis.     

Modification of submerged membrane bioreactors (MBRS) by inserting baffles: pilot scale study.

Submerged membrane bioreactors (MBRs) have been gaining in popularity in various types of wastewater treatment. One drawback of submerged MBRs is difficulty in removing nitrogen as they are accompanied with intensive aeration inside the reactor and therefore principally operated under aerobic conditions. In order to address this problem, a simple modification for submerged MBRs, insertion of baffles to create alternative aerobic/anoxic conditions, was proposed. In this study, the performance of the proposed baffled membrane bioreactor (BMBR) was investigated based on a pilot-scale experiment using a real municipal wastewater. With appropriate operating conditions, the BMBR could remove more than 70% of total nitrogen contained in the feed water without any external carbon source. The BMBR demonstrated a good treatment performance in terms of TOC and phosphorus removal as well. Increase of trans-membrane pressure difference was subtle, which might be attributed to the alternative creation of aerobic/anoxic conditions.     

Membrane bioreactor aeration: investigation of the velocity flow pattern.

Results of investigations concerning membrane bioreactor aeration are presented which were carried out at the Institute of Environmental Engineering of RWTH Aachen University (ISA) in cooperation with the Department of Chemical Engineering of the Technische Universit?t Berlin. In the field of industrial and municipal wastewater treatment the use of membrane bioreactors (MBR) is of increasing interest especially due to the high requirements on effluent quality nowadays. The design of aeration systems is a very important aspect of MBR development because it influences both cost of operation and filtration flux. The ISA has carried out tests concerning the velocity flow pattern in flat sheet membrane modules (developed by the A3 Water Solutions GmbH) to identify the effects of different aeration systems, aeration intensities and module constructions. The Department of Chemical Engineering is currently using the results obtained from the ADV to calibrate a numerical model which simulates two phase water and gas flow within an aerated membrane module. Optical investigations concerning the bubble distribution give a better understanding of the flow conditions in MBR. Developing a numerical tool for membrane module optimization concerning the hydrodynamics is the aim of the investigation of membrane bioreactor aeration.     

Optimal sludge retention time for a bench scale MBR treating municipal sewage.

Membrane bioreactors allow for higher sludge concentrations and improved degradation efficiencies with respect to conventional activated sludge. However, in the current practice these systems are often operated under sub-optimal conditions, since so far no precise indications have yet been issued on the optimal operating conditions of MBR for municipal wastewater treatment. This paper reports some results of four years of operation of a bench scale membrane bioreactor where steady state conditions were investigated under different sludge retention times. The whole experimental campaign was oriented towards the investigation of optimal process conditions in terms of COD removal and nitrification, biomass activity and growth, and sludge characteristics. The membrane bioreactor treated real municipal sewage, and four different sludge ages were tested (20, 40, 60, and 80 days) and compared with previous data on complete sludge retention. The results showed that the the biology of the system, as assessed by the oxygen uptake rate, is less affected than the sludge physical parameters. In particular, although the growth yield was observed to dramatically drop for SRT higher than 80 days, the biological activity was maintained under all the tested conditions. These considerations suggest that high SRT are convenient in terms of limited excess sludge production without losses of the treatment capacity. Physical characteristics such as the viscosity and the filterability appear to be negatively affected by prolonged sludge retention times, but their values remain within the ranges normally reported for conventional activated sludge.     

Evaluation of a hybrid vertical membrane bioreactor (HVMBR) for wastewater treatment

A new hybrid membrane bioreactor (HMBR) has been developed to obtain a compact module, with a small footprint and low requirement for aeration. The aim of this research was to assess its performance. The system consists of a single vertical reactor with a filtration membrane unit and, above this, a sponge fixed bed as support medium. The aeration system is located under the membrane unit, allowing for membrane cleaning, oxygenation, biofilm thickness control and bulk liquid mixing. Operated under continuous aeration, a bench-scale reactor (70 L) was fed with pre-treated, raw (unsettled) municipal wastewater. BOD(5) and suspended solids removal efficiencies (96 and 99% respectively) were comparable to those obtained with other membrane bioreactors (MBRs). Total nitrogen removal efficiencies of 80% were achieved, which is better than those obtained in other HMBRs and similar to the values reached using more complex MBRs with extra anoxic tanks, intermittent aeration or internal deflectors.     

Distribution and removal efficiency of heavy metals in two constructed wetlands treating landfill leachate

The results of heavy metals (Fe, Mn, Zn, Ni, Cu, Cr, Pb, Cd) removal and partitioning between aqueous and solid phases at two treatment wetlands (TWs) treating municipal landfill leachates are presented. One of the TWs is a surface flow facility consisting of 10 ponds. The other TW is a newly constructed pilot-scale facility consisting of three beds with alternately vertical and horizontal subsurface flow. The metals concentrations were analysed in leachate (both TWs) and bottom sediments (surface flow TW). Very high (90.9-99.9%) removal rates of metals were observed in a mature surface flow TW. The effectiveness of metals removal in a newly constructed pilot-scale sub-surface flow wetland were considerably lower (range 0-73%). This is attributed to young age of the TW, different hydraulic conditions (sub-surface flow system with much shorter retention time, unoxic conditions) and presence of metallic complexes with refractory organic matter.     

Application of sequencing batch membrane bioreactors (SB-MBR) for the treatment of municipal wastewater

Sequencing batch membrane bioreactors can be a good option in up-grading small municipal plant and for industrial applications, maintaining some of the advantages of both original technologies (effluent quality improvement, flexibility and simplicity of realization, operation and control). In this study, the effects of volumetric exchange ratio (VER) and aeration/filtration strategy have been evaluated. Moreover, with the adoption of cycles shorter than 8 h, the opportunity of further simplification of the membrane operation has been tested by choosing a continuous filtration mode instead of the usual short cycle of permeation/relaxation. Two lab-scales MBR equipped with Zenon hollow fiber modules were fed on real primary effluent. For all tests, hydraulic retention time of 10 h and sludge retention time of 60 days have been adopted. Different cycles have been investigated, lasting between 1 and 8 h and all comprising an anoxic phase to allow for denitrification. Operation at low VER resulted in better effluent quality with no limitations to the denitrification phase. For VER >33% a pre-aeration step was required before effluent withdrawal for optimal ammonium removal. Moreover, VER appeared to have limited negative effect on sludge concentration and yield, while the membrane cleaning frequency slightly increased for increasing VER.     

Continuous and sequencing membrane bioreactors applied to food industry effluent treatment.

This work focuses on the performances of two immersed membrane bioreactors used for the treatment of easily biodegradable organic matter present in food industry effluents, for the purpose of water reuse. Two reactor functioning modes (continuous and sequencing) were compared in terms of organic carbon removal and of membrane permeability. For each working mode, pollutant removal was very high, treated water quality presented a low COD concentration (< 125 mg x L(-1)), no solids in suspension and low turbidity (< 0.5 NTU). The quality of the treated water (including germ removal) enabled its reuse on site. Moreover, by developing high biomass concentrations in the reactor, excess sludge production remained very low (< 0.1 gVSS x gCOD(-1)). The performances appeared slightly better for the continuous system (lower COD concentration in the effluent, < 50 mg x L(-1), and lower sludge production). In terms of filtration, a distinct difference was observed between continuous and sequencing systems; transmembrane pressure showed a small and constant evolution rate in continuous membrane bioreactor (CMBR) although it appeared more difficult to control in sequencing membrane bioreactor (SMBR) probably due to punctually higher permeate flow rate and modified suspension properties. The rapid evolution of membrane permeability observed in SMBR was such that more frequent chemical cleaning of the membrane system was required.     

Landfill leachate treatment by an experimental subsurface flow constructed wetland in tropical climate countries.

Municipal leachate was treated in an experimental unit of constructed wetlands of subsurface flow type. The parameters studied were organics (BOD and COD), solids and heavy metals (Zn, Ni, Cu, Cr and Pb). Using two types of emergent plants of Scirpus globulosus and Eriocaulon sexangulare, more than 80% removal was achieved for all the parameters. E. sexangulare removed organics and heavy metals better than Scirpus globulosus. A higher concentration of heavy metals in the influent did not change the removal efficiency.     

吉林市排污河底泥的污染状况及其生态风险评价

以吉林市排污河中底泥为主要研究对象,布置12个监测断面35个代表性采样点,采集并分析了河道内底泥样品中8种重金属及16种USEPA优先控制的多环芳烃的含量,并分别采用地质累积指数法(I_(geo))、潜在生态风险评价法(PERI)、沉积物质量基准法(SQGs)对排污河底泥中污染物进行了生态风险评价。结果表明,该排污河底泥中重金属及多环芳烃均不同程度超过松花江水系沉积物背景值,其中Hg、Pb、Cu、As、NAP、ANT超标倍数分别为87.5、10.2、6.18、5.90、115.6和228.5;I_(geo)显示Hg的生态风险最大,I_(geo)达到了5.82,而Cd和Ni的风险较小,这与PERI中Hg风险最大的结果一致;SQGs评价结果表明由重金属及多环芳烃引起的污染会产生生物毒性,且不利生物毒性将频繁发生;(3)以上结果说明,该排污河呈现以Hg为主要风险因子的重金属与多环芳烃复合污染现象,在今后应加强底泥监测和定期清淤,从而推动区域生态环境的治理与恢复。     

Biological treatment of heavy metals in acid mine drainage using sulfate reducing bioreactors.

The uncontrolled release of acid mine drainage (AMD) from abandoned mines and tailing piles threatens water resources in many sites worldwide. AMD introduces elevated concentrations of sulfate ions and dissolved heavy metals as well as high acidity levels to groundwater and receiving surface water. Anaerobic biological processes relying on the activity of sulfate reducing bacteria are being considered for the treatment of AMD and other heavy metal containing effluents. Biogenic sulfides form insoluble complexes with heavy metals resulting in their precipitation. The objective of this study was to investigate the remediation of AMD in sulfate reducing bioreactors inoculated with anaerobic granular sludge and fed with an influent containing ethanol. Biological treatment of an acidic (pH 4.0) synthetic AMD containing high concentrations of heavy metals (100 mg Cu(2+)l(-1); 10 mg Ni(2+)l(-1), 10 mg Zn(2+)l(-1)) increased the effluent pH level to 7.0-7.2 and resulted in metal removal efficiencies exceeding 99.2%. The highest metal precipitation rates attained for Cu, Ni and Zn averaged 92.5, 14.6 and 15.8 mg metal l(-1) of reactor d(-1). The results of this work demonstrate that an ethanol-fed sulfidogenic reactor was highly effective to remove heavy metal contamination and neutralized the acidity of the synthetic wastewater.     

浸提时间对城市污泥重金属浸出特性的影响

在研究含工业废水污泥中Zn、Cu、Pb、Cr、Mn、Ni含量的基础上,应用固体废物浸出毒性方法,以不同浸出时间对污泥中重金属的浸出特性进行了实验研究.结果表明:污泥中Mn和Zn含量较高,其次为Cu和Ni,而毒性较大的Pb和Cr含量较低.浸提时间对污泥中重金属的浸出具有重要影响,污泥中的Zn、Cu、Ni最大浸出浓度在8h时,而Fe和Mn随着浸提时间增加而增加;浸提时间对污泥中重金属浸出量的影响因该重金属的化学性质不同而存在较明显的差别,这可能与浸提过程中的吸附-解吸过程、络合-解离过程和溶解-沉淀/共沉淀等因素有关.     

Removal of endocrine disrupting compounds with membrane processes in wastewater treatment and reuse.

Endocrine disrupting compounds can affect the hormone system in organisms and are the subject of environmental and human health concerns. The effluents of wastewater treatment plants contribute to the emission of estrogenically active substances into the environment. Membrane technology, which is an advanced wastewater treatment option, is the subject of this research. The removal techniques under investigation are membrane bioreactors, reverse osmosis, and nanofiltration. Eleven different nanofiltration membranes were tested in the laboratory set-up. The observed retention of NP and BPA ranged between 70% and 100%. The contact angle is an indicator for the hydrophobicity of a membrane, whose influence on the permeability and retention of NP was evident. Regarding the retention of BPA no dependency on the contact angle was observed. Results of the investigation of a full-scale landfill leachate treatment plant indicate a bisphenol A (BPA) removal of more than 98% with membrane bioreactors and reverse osmosis. The mass balance indicates that biological degradation is the most important removal process in the membrane bioreactor configuration.     

MBR工艺处理城镇污水处理厂污泥水中试研究

将平板膜组件与传统脱氮除磷工艺相结合,构建了膜生物反应器强化生物脱氮除磷中试系统,并用于处理城镇污水处理厂的污泥系统废水。结果表明,出水CODCr、BOD5、NH3—N、TN和TP的平均浓度分别为70.8 mg/L、8.7 mg/L、15.1 mg/L、29.7 mg/L和0.38 mg/L,达到或接近了《城镇污水处理厂污染物排放标准》(GB 18918—2002)的一级标准。     

长寿湖水库沉积物中重金属来源及生态风险评价

水库作为生活饮用水水源地,受人类活动影响较大,且污染物种类多、来源广、危害大。目前,关于水库沉积物中重金属污染状况分析的研究较少。以三峡库区长寿湖水库沉积物为研究对象,利用地累积指数(I_(geo))和潜在生态风险指数法,结合沉积年代学序列,对沉积物中重金属Co,Cd,Cr,Cu,Ni,Pb和Zn的垂直变化特征、重金属来源及生态风险评价进行了分析。地累积指数分析表明:表层沉积物中重金属累积顺序为CdCoZnNiPbCuCr,其中Cd和Zn累积较明显,属于轻度污染。潜在生态风险系数评价结果表明:沉积物中重金属潜在生态风险指数RI值大多数低于150,说明潜在生态风险整体较轻,但自1889年以来,RI值一直大于150,应当引起重视。应用主成分析法分析长寿湖水库沉积物中重金属来源,结果表明:水库沉积物中重金属主要来源于流域土壤的自然风化和土壤侵蚀,同时也受到龙溪河流域城市化、工业化发展导致的工业废水和生活污水排放的影响。     

Sustainability assessment of advanced wastewater treatment technologies

As a consequence of the EU Water Framework Directive more focus is now on discharges of hazardous substances from wastewater treatment plants and sewers. Thus, many municipalities in Denmark may have to adopt to future advanced treatment technologies. This paper describes a holistic assessment, which includes technical, economical and environmental aspects. The technical and economical assessment is performed on 5 advanced treatment technologies: sand filtration, ozone treatment, UV exclusively for disinfection of pathogenic microorganisms, membrane bioreactor (MBR) and UV in combination with advanced oxidation. The technical assessment is based on 12 hazardous substances comprising heavy metals, organic pollutants, endocrine disruptors as well as pathogenic microorganisms. The environmental assessment is performed by life cycle assessment (LCA) comprising 9 of the specific hazardous substances and three advanced treatment methods; sand filtration, ozone treatment and MBR. The technical and economic assessment showed that UV solely for disinfection purposes or ozone treatment is the most advantageous advanced treatment methods if the demands are restricted to pathogenic microorganisms. In terms of sustainability, sand filtration is the most advantageous method based on the technical and environmental assessment due to the low energy consumption and high efficiency with regards to removal of heavy metals.     

Use of citric acid for heavy metals extraction from contaminated sewage sludge for land application.

Recent studies revealed that organic acids such as citric and oxalic acids seemed to be more promising as chemical extracting agents for removal of heavy metals from contaminated sludge, since they are biodegradable and can attain a higher metal extraction efficiency at mildly acidic pH compared to other extracting agents. Results of a lab-scale study on the efficiency of citric acid in the extraction of chromium (Cr), copper (Cu), lead (Pb), nickel (Ni) and zinc (Zn) from anaerobically digested sludge, revealed that citric acid seemed to be highly effective in extracting Cr (at 100%), Cu (at 88%), Ni (at 98%) and Zn (at 100%) at pH 2.33, mostly at 5 days leaching time except for Cu and Zn, which are at 1 day and 2 h contact times respectively. Lead removal at the same pH was also high at 95% but at a longer leaching time of 11 days. At pH 3, citric acid seemed to be highly effective in extracting Pb (at 100%) at 1 day leaching time, although higher removals were also attained for Ni (70%) and Zn (80%) at only 2 h leaching time. Chemical speciation studies showed that Cr, Cu and Ni in the sludge sample seem to predominate in residual fractions, while Pb and Zn were found mostly bound to organic and inorganic matter forms, hence the potential of the sludge for land application.