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.     

Heavy metals speciation in soakaways sediment and evaluation of metal retention properties of surrounding soil.

Heavy metals speciation analysis was carried out on sediment samples accumulated within soakaways in an old stormwater infiltration facility in Tokyo, Japan and on a soil core sample collected near the facility. Heavy metals content in soakaways sediments were much elevated compared to nearby surface soil with the content for Zn, Pb and Cd reaching about 5 to 10 times the content in surface soil. Speciation results revealed that significant amount of the accumulated heavy metals were present in potential mobile fractions, posing threat of release to underlying soil with changing environmental conditions. Detail analyses of soil characteristics indicated significant heterogeneity with depth, especially between the surface soil and underlying soil at site. Decrease in potential adsorption sites with depth was observed in case of underlying soil. Reduced adsorption capacity for heavy metals was evidenced for underlying soil when compared with surface soil. Furthermore, less capability of the soil organic matter to bind heavy metals was evidenced through speciation analyses, which raises concern over the long-term pollution retention potential of the underlying soil receiving infiltrated runoff.     

A new installation for treatment of road runoff: up-flow filtration by porous polypropylene media.

We installed a new device on a paved road to treat runoff from a roadway surface. All the stormwater runoff was transferred into the device and the runoff equivalent to 10 mm/hr or less was treated. The treatment method consists of sedimentation and up-flow filtration with porous polypropylene (PPL) processes. The treated runoff was discharged into the existing storm drainage pipe. The average removal efficiency of the initial runoff at the beginning of rainfall which has high pollution intensity was about 90% for SS, about 70% for COD, about 40% for total phosphorus (T-P), about 80% for Pb and Cd, about 70% for Zn, Cu, Mn and Cr, and about 60% for polycyclic aromatic hydrocarbons (PAHs). The overall removal efficiencies of the experiment that ran for four months remained > 60% of SS, > 40% of COD, > 60% of heavy metals, and > 40% of PAHs. The PPL is excellent for removing smaller size particulates of suspended solids, which originate basically from diesel exhaust, as well as larger size particulates from automobile tires, asphalt roads, and other accumulated source(s) of clay and sand, etc.     

Influence of compost characteristics on heavy metal sorption from synthetic stormwater.

This paper has the aim to assess the ability of garden derived compost to remove dissolved heavy metal contaminants typically found in stormwater. Compost was found to have excellent chemical and physical properties for the sorption of dissolved metal ions (Cu2+, Pb2+ and Zn2+). Batch sorption data were used to determine the sorption efficiency of Cu (93%), Zn (88%) and Pb (97%) by compost. The relative sorption affinity of these metals by compost is found to be in the order of Pb2+ > Cu2+ Zn2+. The effect of different particle size fractions of compost upon the sorption of Cu was also investigated. Sorption conformed to the linear form of the Freundlich isotherm and can be considered favourable because the sorption intensity values obtained in this study are between 0.1 and 1. Compost with a smaller particle size fraction has larger surface areas and greater sorption than the larger particle size fraction. Compost derived from garden waste is efficient for removal of heavy metals from wastewater or treating water for industries.     

Adsorption of Zn(II) and Cd(II) ions in batch system by using the Eichhornia crassipes

In this work, the displacement effects on the sorption capacities of zinc and cadmium ions of the Eichornia crassipes-type biosorbent in batch binary system has been studied. Preliminary single metal sorption experiments were carried out. An improvement on the Zn(II) and Cd(II) ions removal was achieved by working at 30 °C temperature and with non-uniform biosorbent grain sizes. A 60 min equilibrium time was achieved for both Zn(II) and Cd(II) ions. Furthermore, it was found that the overall kinetic data were best described by the pseudo second-order kinetic model. Classical multi-component adsorption isotherms have been tested as well as a modified extended Langmuir isotherm model, showing good agreement with the equilibrium binary data. Around 0.65 mequiv./g maximum metal uptake associated with the E. crassipes biosorbent was attained and the E. crassipes biosorbent has shown higher adsorption affinity for the zinc ions than for the cadmium ones in the binary system.     

Hydrocarbons and heavy metals fixed to the lift station sediment of the Paris combined sewer network.

This work aims to characterise the pollutant loads fixed to the Lift Station (LS) sediments. Firstly, levels of n-alkanes, PAH and heavy metals (Fe, Zn, Cu, Pb and Cd) of LS sediments were assessed, and were found of the same order of magnitude as those reported for street runoff. In addition, investigations on LS sediment reveal that n-alkane distributions reflect the combination of biologic and petrogenic inputs, while PAH distributions indicate a major pyrolytic origin with traces of petrogenic contaminations. The metallic fingerprints also attest to the important contribution of road traffic emissions. Secondly, a comparison between LS sediment and the Gross Bed Sediment (GBS) pollutant contamination was established in order to optimize the in-sewer deposits management. For hydrocarbons, a similar contamination between both sediments is found. For the heavy metals, this comparison indicates a similar Fe and Zn content, while Pb, Cu and Cd contents differ. Indeed, LS sediment shows a higher Cu content, linked to the occurrence of intensive brake lining abrasion, compared with GBS, which reflects a higher Pb and Cd content, owing to the contribution of roof runoff. This result reveals the impact of specific inputs such as road traffic or roof runoff on the in-sewer sediments contamination, and provides a complete overview of the LS sediment contamination. This database could be used by the municipality to optimize their contaminated in-sewer sediment management.     

Evaluation of heavy metal inhibition of activated sludge by TTC and INT-electron transport system activity tests.

TTC and INT-electron transport system activity tests were compared for assessing heavy metal inhibition of activated sludge. The median inhibitory concentrations (IC50s) of Cu2+, Zn2+, Cd2+, Hg2+, Ni2+, Pb2+ and Ag+ measured via TTC test were lower than those measured via INT test, which indicates that the INT-electron transport system activity test was less sensitive to heavy metal toxicity than the TTC test. Tested heavy metals brought about similar decrease in TTC-electron transport system activity and COD removal rate, but less decrease in INT-electron transport system activity than COD removal rate, which suggests that the TTC-electron transport system activity is a better parameter for reflecting heavy metal inhibition of activated sludge than INT-electron transport system activity. The ranking of tested heavy metals in order of decreasing toxicity based on TTC test was Hg2+, Cd2+, Cu2+, Ag+, Zn2+, Ni2+ and Pb2+, and the ranking based on INT test was Hg2+, Ag+, Cu2+, Cd2+, Zn2+, Ni2+ and Pb2+.     

松花江流域鱼体内重金属含量的监测与污染评价

为研究松花江流域鱼体重金属的污染现状,采用微波消解-电感耦合等离子体质谱法测定松花江流域鱼类体内的Cu、Zn、Cr、Cd、Pb、Hg、As等7种重金属的残留量,使用综合污染指数法对污染情况进行了评价。结果表明,松花江鱼体中7种重金属的基准值由高到低依次为Zn、Cu、Cr、As、Pb、Hg和Cd,且除Hg以外,其他6种重金属的来源具有一定的相似性;第二松花江流域中鱼体内重金属残留量高于嫩江和松花江干流两条流域中鱼体内重金属残留量;参照《无公害食品水产品中有毒有害物质的限量标准》(NK 5073-2006)和《食品中锌限量卫生标准》(GB13106-1991),鱼体内Pb、As、Cr和Zn的超标率很高,特别是Pb和As的污染比较严重。     

Zinc, lead and cadmium speciation in Dnieper water-bodies

Data on the concentrations and movements of Zn, Pb and Cd in Dnieper reservoirs and the Dnieper‐Bug estuary are considered. There is a clear trend of increasing concentrations, often two‐ to fourfold, of these materials from the 1960s to the end of the 1980s. Large increases may be explained as the result of increased human impact on the water‐bodies and also because of reduced water discharge in the Dnieper River (discharge has been reduced by nearly 10 km³ in recent years). At present, the average concentrations of Zn, Pb and Cd in Dnieper water‐bodies are 35.0–50.0, 15.0–18.0 and 0.5–1.8 μg L^–1, respectively. Anodic stripping voltammetry, membrane filtration, ion‐exchange and gel permeation chromatography on neutral sephadexes were methods used for analysis. The influence of adsorption and complexation processes on the mobility of Zn, Pb and Cd, and the ratio of their forms were compared. Ratios of free metal ions to ions bound in complexes with natural organic ligands were studied. The binding of metals in complexes with dissolved organic matter (DOM), or their adsorption onto suspended particles, were major processes reducing the concentration of free ions in their most toxic form. The percentage of Zn, Pb, and Cd free ions in the total balance of dissolved forms was no more than 3.6–4.8, 0.2–0.6 and 7.2–9.5%, respectively. The molecular‐weight distribution of organic metal complexes and their chemical nature, as well as the potential for complexing of DOM were investigated. Most Zn, Pb and Cd was found as complex compounds with DOM of different chemical natures and molecular weights. Humic substances, particularly fulvic acids, played a major role in the migration of the metals. These ligands bind from 40 to 80% of metals in the composition of organic complexes. Metal complex compounds of relatively low molecular weight (< 5000 Da) predominated in organic complexes of Zn (38–50%), Pb (38–52%) and Cd (22–47%). The role of inorganic ligands in complexation in surface waters was less important.     

The sorption of lead, cadmium, copper and zinc ions from aqueous solutions on a raw diatomite from Algeria

The adsorption of Cu(2+), Zn(2+), Cd(2+) and Pb(2+) ions from aqueous solution by Algerian raw diatomite was studied. The influences of different sorption parameters such as contact pH solution, contact time and initial metal ions concentration were studied to optimize the reaction conditions. The metals ions adsorption was strictly pH dependent. The maximum adsorption capacities towards Cu(2+), Zn(2+), Cd(2+) and Pb(2+) were 0.319, 0.311, 0.18 and 0.096 mmol g(-1), respectively. The kinetic data were modelled using the pseudo-first-order and pseudo-second-order kinetic equations. Among the kinetic models studied, the pseudo-second-order equation was the best applicable model to describe the sorption process. Equilibrium isotherm data were analysed using the Langmuir and the Freundlich isotherms; the results showed that the adsorption equilibrium was well described by both model isotherms. The negative value of free energy change ΔG indicates feasible and spontaneous adsorption of four metal ions on raw diatomite. According to these results, the high exchange capacities of different metal ions at high and low concentration levels, and given the low cost of the investigated adsorbent in this work, Algerian diatomite was considered to be an excellent adsorbent.     

黄土高原北洛河沉积物生态风险解析

以黄土高原的典型工业污染河流北洛河为研究对象,测定其干支流 17 个采样点沉积物中的 8 种重金属（Hg、 As、Cd、Cr、Cu、Pb、Ni、Zn）质量分数,结合描述性统计结果对重金属的空间分布特征进行分析。进一步利用地 累积指数法、内梅罗综合污染指数法和潜在生态风险指数法分析重金属的污染程度与生态风险,利用 PMF 模型 和相关性分析进行来源解析。结果表明：北洛河上游沉积物中重金属的平均质量分数高于中下游,As、Cd 和 Zn 的均值分别为背景值的 1.26、1.28 和 1.41 倍,Zn、Hg、Cd、Pb、As 和 Cu 的变异系数大于 30%,为高度变异水平。 地累积指数法与内梅罗综合污染指数法显示,北洛河上游 B1处和下游 B13处沉积物中重金属污染处于中高水平; 潜在生态风险指数法显示,单一元素污染危害程度依次为 Cd?>?Hg?>?As?>?Cu?>?Ni?>?Pb?>?Zn?>?Cr,整体来看,Cd 和 Hg 的潜在生态危害较大,中游 B10和下游 B13存在中等生态风险,其余点位均为轻微生态风险。来源解析表明,北 洛河沉积物中重金属的 3 个来源分别为交通污染源（30.74%）、煤炭石油类工业污染源（35.51%）及农业活动和自 然母质的混合来源（33.75%）。研究成果可为北洛河沉积物重金属污染的科学治理及流域生态管理提供理论 参考。     

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.     

东湖沉积物中重金属垂向分布特征及污染评价

为了掌握武汉东湖的水环境状况,以沉积物为研究对象,使用电感耦合等离子体质谱仪(ICP-MS)测定了不同湖域沉积物柱状样中9种重金属(Cd、Zn、As、Cu、Co、Pb、Mn、Cr、Ni)含量,对重金属元素的垂向分布特征进行了研究,并采用地累积指数法对重金属的污染程度进行评价。结果表明:沉积物中9种重金属元素含量排序为MnCrPbZnNiCuCoAsCd;垂向分布特征为Cr、Ni的含量随沉积物深度增加而增加,Cu、As、Cd的含量随沉积物深度增加而减少。地累积指数评价表明,郭郑湖西岸污染最为严重,汤菱湖最轻,累积较为严重的是Cr、Mn、Cd和Pb,其中Cd和Pb达到中度污染程度。     

Geochemical Availability of Some Trace and Major Elements in Surficial Sediments of the Detroit River and Western Lake Erie

Surficial bottom sediment from twenty locations in the Detroit River and western Lake Erie has been analyzed for potentially available Ba, Be, Cd, Cr, Co, Cu, Pb, Mn, Mo, Ni, P, V, and Zn. The highest concentrations of all but one of these elements were found at a station at the river-lake interface very close to a dumping ground. The environmental mobility of Cd, Zn, Co, Pb, Cr, Ni, and P is controlled by hydrous iron oxides, whereas V and Mo is controlled by aluminosilicates. The iron oxide phase exhibits a very high sorption capacity for phosphorus (molar adsorption coefficient = .361) which is attributed to the high loadings of Fe and P at the confluence of the Rouge and Detroit rivers as well as continuous inputs along the length of the Detroit River. It is suggested that phosphorus controls instituted in the 1970s will probably result in the iron oxide phase having greater sorption capacity for toxic metals because of the decreasing competition from phosphorus for binding sites.     

大燕河沉积物重金属污染特征及生态风险分析

为了解大燕河表层沉积物重金属污染特征及潜在生态风险,对大燕河干流和支流沉积物重金属污染物进行了分析,并采用Hakanson生态危害指数法进行评价。结果表明,大燕河干流沉积物重金属含量明显高于支流,重金属含量高于广东省土壤背景值,Cu、Cd、Zn、Pb、Hg超出了土壤环境质量Ⅰ级标准。沉积物中重金属Cu、Cd的富集系数明显高于其他重金属,不同采样点重金属超出背景值的程度具有明显的差异性,呈现干流高于支流,下游高于上游的特征。沉积物中重金属具有极强的生态危害,各种重金属造成的平均生态危害程度由大到小依次为:CdHgCuAsPbZnNiCr,其潜在生态风险应引起足够的重视。     

长江中下游底泥重金属污染特征、潜在生态风险评价及来源分析

为探究长江中下游底泥重金属污染状况,对长江中下游主干河流及湖泊的27个断面的底泥进行采集并测定镉、铅、铬、铜、锌、砷和汞的浓度。运用潜在生态风险指数法对重金属污染进行评价,并采用相关分析和主成分分析对重金属的污染来源进行分析。结果表明:Hg、Cd、Pb、Cr、Cu、Zn和As的含量分别为0.010～0.55 mg/kg、0.016～0.17 mg/kg、13.04～110.03 mg/kg、42.03～121.03 mg/kg、21.70～75.10 mg/kg、48.01～750.01 mg/kg和6.03～82.95 mg/kg。重金属浓度较高的地方位于较为发达的城市(武汉和南京)、采矿业发达的地区(安庆、大通和芜湖)、港口城市(城陵矶)以及湖泊(鄱阳湖和东洞庭湖)。由潜在生态风险评价可知,7种重金属污染程度的大小顺序为:HgAs PbCdCuCrZn。相关分析和主成分分析结果表明Pb、Cd、Zn、Cu、Hg和Cr主要来源于煤炭燃烧、农业活动及生活污水,As主要来源于采矿业和航运业。长江中下游及湖泊底泥所有点位的Pb、Cu、Cr、Zn和Cd均处于轻微潜在生态风险状态,As和Hg在部分点位具有较高潜在生态风险。结合所有重金属元素来说,长江中下游以及湖泊底泥的潜在生态风险水平较低。     

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.     

海河流域中部表层沉积物中重金属分布特征及污染评价

为了解海河流域中部表层沉积物中重金属分布特征和污染现状,分别测定了17个采样点表层沉积物中Cr、Ni、Cu、Zn、As、Cd、Hg、Pb共8种重金属元素质量比,并采用相关性分析法、富集系数法、地累积指数法分析其同源性、污染来源及污染程度。结果表明：海河流域中部表层沉积物中重金属质量比整体上较历史水平有所下降,8种重金属元素的污染系数从高到低依次为Cd（1-98）、Hg（1-80）、Cu（1-37）、Zn（1-18）、Pb（1-12）、Ni（1-07）、Cr（1-02）、As（0-77）,Cd污染相对严重;Cd和Hg的富集系数平均值均高于1-5,污染来源以人为输入为主,其余6种重金属元素则主要以自然来源为主;海河流域中部重金属总体上污染较轻,个别点位污染等级达到中度污染。     

Enhanced heavy metals removal without phosphorus loss from anaerobically digested sewage sludge

Heavy metals removal without phosphorus loss from anaerobically digested sewage sludge was investigated by conducting batch experiments using hydrogen peroxide and/or iron sulphate under acidified conditions at pH 3. The addition of hydrogen peroxide to the sludge improved the elution efficiencies of As, Cd, Cu and Zn with phosphorus loss from the sludge. The optimum initial concentrations of hydrogen peroxide were. Respectively. 0.1% for As, Cd, Mn and Zn and 0.5% for Cu and Ni. The combined process of 0.1% hydrogen peroxide and 1 g Fe/L ferric sulphate enhanced the initial elution rate of Cu and Cr compared to the addition of either ferric sulphate or hydrogen peroxide, indicating that oxidants stronger than hydrogen peroxide were produced in the sludge. Furthermore, the combined process immobilised phosphorus in the sludge due to co-precipitation with ferric hydroxide or precipitation as ferric phosphate. It was concluded that there is a possibility that the combined process could remove heavy metals effectively without phosphorus loss from anaerobically digested sewage sludge.     

生态雨水设施的污染物积累效应及风险研究进展

对植被浅沟、雨水花园及雨水塘3种具有代表性的生态雨水设施应用于径流中有机质、颗粒物、重金属等污染物控制时,污染物在设施内的积累特性进行了归纳总结,分析了设施长期运行时面临的污染风险,提出了这3种生态雨水设施运行管理与维护的建议:植被浅沟运行寿命应结合我国道路雨水径流水质综合确定,超期运行的植被浅沟应对表层5cm种植土进行更换;雨水花园表层介质重金属含量较高时,可更换0~10 cm深度范围内的种植土,为减少表层磷溶出量,可在表层覆盖树皮以加强对磷的吸附;雨水塘中沉积物的清理周期应按功能区分类确定,对于沉积物中多环芳烃含量较高的干塘应酌情增加清理次数。