万山汞矿区土壤重金属污染特征及来源解析

以万山汞矿区土壤为研究对象,采用电感耦合等离子体质谱仪和原子荧光光谱仪测定土壤中的重金属含量,分别运用内梅罗综合污染指数（NPI）法和潜在生态风险指数（RI）法评价土壤重金属污染和潜在生态风险,并应用相关性分析、主成分分析和聚类分析对土壤重金属来源进行分析。结果表明：土壤Hg、Cd、As、Pb、Cu、Ni和Zn出现不同程度累积,分别达贵州省背景值的263.61、2.31、1.28、2.11、1.70、1.01和3.52倍;土壤重金属平均NPI为188.00,属于严重污染水平,Hg是主要污染因子;土壤重金属平均RI为10 655.70,属于极强潜在生态风险水平,Hg是主要潜在生态风险因子;土壤中Cu、Ni、Cr主要源于自然活动,As、Pb、Zn主要源于燃煤和交通运输污染,Cd主要源于农业污染,Hg主要源于汞冶炼污染。     

Fractionation of heavy metals in sludge from anaerobic wastewater stabilization ponds in southern Spain

The analysis of heavy metals is a very important task to assess the potential environmental and health risk associated with the sludge coming from wastewater treatment plants (WWTPs). However, it is necessary to apply sequential extraction techniques to obtain suitable information about their bioavailability or toxicity. In this paper, a sequential extraction scheme according to the Standard, Measurements and Testing Programme of the European Commission was applied to sludge samples collected from ten anaerobic wastewater stabilization ponds (WSPs) located in southern Spain. Al, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Ti and Zn were determined in the sludge extracts by inductively coupled plasma atomic emission spectrometry. In relation to current international legislation for the use of sludge for agricultural purposes, none of the metal concentrations exceeded maximum permitted levels. Overall, heavy metals were mainly associated with the two less-available fractions (34% oxidizable metal and 55% residual metal). Only Mn and Zn showed the highest share of the available (exchangeable and reducible) fractions (25-48%).     

Survey of mercury,cadmium and lead content of household batteries

The objective of this work was to provide updated information on the development of the potential impact of heavy metal containing batteries on municipal waste and battery recycling processes following transposition of the new EU Batteries Directive 2006/66/EC. A representative sample of 146 different types of commercially available dry and button cells as well as lithium-ion accumulators for mobile phones were analysed for their mercury (Hg)-, cadmium (Cd)- and lead (Pb)-contents. The methods used for preparing the cells and analysing the heavy metals Hg, Cd, and Pb were either developed during a former study or newly developed. Several batteries contained higher mass fractions of mercury or cadmium than the EU limits. Only half of the batteries with mercury and/or lead fractions above the marking thresholds were labelled. Alkaline–manganese mono-cells and Li-ion accumulators, on average, contained the lowest heavy metal concentrations, while zinc–carbon batteries, on average, contained the highest levels.     

Assessment of benefits and risks of landfill materials for agriculture in Eritrea

In Eritrea, farmers have applied landfill materials as fertiliser to their fields for several decades. A sampling scheme in the landfill site of Asmara and selected farmers' fields was carried out to investigate the benefits and risks of using landfill materials for agriculture. Soil samples were collected from farmers' fields (7 samples) and from the Asmara landfill site (12 samples). The samples were analysed for major plant nutrients, heavy metals (Cd, Cr, Cu, Pb, Ni, Hg and Zn), and some physical properties. Nearly 65% (by weight) of the total landfill material mined from the landfill site constituted waste fractions of various substances. The remaining 35% was composed of soil-like materials, which are apparently used to fertilize agricultural soils. The average organic matter, total nitrogen, and available phosphorus contents of soils with landfill material measured 2.4%, 0.13%, and 45 mg kg(-1), respectively. However, soils without landfill material consisted of 1.1 % organic matter, 0.04% total N, and <40 mg kg(-1) of available P. Except for Hg, all the other heavy metals in the landfill site showed values above the permissible limits. In particular, the average concentrations of Cu (913 mg kg(-1)) and Pb (598 mg kg(-1)) in the landfill site were nine-fold and four-fold greater than the allowable limits, respectively. It is, therefore, suggested that composting fresh organic wastes should be considered and tested as an alternative material for fertilising agricultural soils and to maintain the quality of the environment.     

Investigation on the heavy metal content of zinc-carbon and alkaline manganese dry cells

The objective of this work was to test the compliance of commercially available batteries with the German Battery Ordinance, a project of the German government that was initiated by the Federal Environment Agency. Different types of commercially available dry cells were analysed for their cadmium, lead and mercury contents. The dry cells underwent mechanical pre-treatment, separation of the different components and microwave-assisted digestion before determination of the heavy metals. Mercury is sometimes added to prevent the generation of gaseous hydrogen from the electrochemical process. Lead could be present since it is sometimes used as an alloying element of zinc. Cadmium has no technical importance and is an undesirable impurity. None of the batteries contained higher heavy metal mass fractions than the permissible limits.     

Enrichment of elements in industrial waste incineration bottom ashes obtained from three different types of incinerators,as studied by ICP-AES and ICP-MS

The elemental composition of the industrial waste incineration bottom ash (IWIBA) samples collected from three different types of incinerator with different kinds of wastes were compared. The major-to-ultratrace elements in the IWIBA samples were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). As a result, ca. 40 elements in the concentration range from milligrams per gram to submicrograms per gram could be determined with relative standard deviations of less than 5%. The IWIBA sample from petrochemical wastes contained lower concentrations of the elements, because fewer mineral constituents were contained in the input waste materials. On the contrary, the elemental concentrations in the IWIBA sample from industrial solid wastes provided the highest values for most elements, while the elemental compositions of the IWIBA sample from food wastes were similar to those of municipal solid waste incineration bottom ash. In addition, it was found from the analytical results that the levels of various heavy metals such as Cr, Mn, Fe, Ni, Cu, As, Zr, Mo, Sb, Ba, and Pb were higher in the IWIBA samples than in municipal solid waste incineration bottom ash. The enrichment factors of the elements in the IWIBA samples were estimated from the analytical results to compare the elemental distributions in incineration bottom ashes in relation to their mining influence factors, which are the indices for human use of the elements.     

Qualitative and quantitative determination of heavy metals in waste cellular phones

Twenty four waste cellular phones, manufactured between 2002 and 2011, were selected in order to determine the total heavy metal content in each of their parts (printed circuit boards (PCBs), plastic housing (PH) and liquid crystal display monitors (LCDs)) and compare the results with the permissible limits set by the 2003 Directive on Restriction of Hazardous Substances (RoHS). All the selected samples were pulverized and digested with strong acids. Inductively coupled plasma-mass spectrometry was used to measure the heavy metal content in each sample. The results revealed that concentration levels of the examined heavy metals were higher in PCBs, followed by PH and LCD in that particular order (PCB > PH > LCD). With the exception of Pb and Cr present in PCBs of mobile phones released before the year 2006, all the other metal concentrations were according to the Directive. Concentration levels of Cd, Hg were lower than the permissible limits set by the EU, either before or after the validity of the 2003 RoHS Directive. Considering their significant heavy metal content, coupled with their large quantities produced worldwide in an annual rate, waste cellular phones need to be treated under an environmentally sound management scheme, prioritizing recycling and at the same time eliminating the possibility of any harm.     

电感耦合等离子体发射光谱法测定石化废水中的重金属

建立了硝酸加热消解后采用电感耦合等离子体发射光谱(ICP-OES)测定石化废水中重金属(As,Cd,Cr,Cu,Zn,Pb,Mn)的方法,优化了仪器工作参数,得到了线性回归方程,并对该方法进行了评价。优化后的仪器工作参数为射频功率1 150 W、雾化器流量0.70 L/min、辅助气流量0.50 L/min。各重金属元素回归方程的相关系数均在0.999 9以上,检出限为0.000 18~0.007 00 mg/L,相对标准偏差为0.1%~2.0%,加标回收率为96.3%~102.2%。该方法具有线性关系好、检出限低、精密度和准确度高、分析速度快等优点。     

Metal leachability, heavy metals, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in fly and bottom ashes of a medical waste incineration facility

Medical waste from hospitals and other healthcare institutions has become an imperative environmental and public safety problem. Medical waste in Greece has become one of the most urgent environmental problems, because there are 14,000 tons produced annually, of which only a small proportion is incinerated. In the prefecture of Attica there is only one modern municipal medical waste incinerator (started 2004) burning selected infectious hospital waste (5-6 tons day(-1)). Fly and bottom residues (ashes) are collected and stored temporarily in barrels. High values of metal leachability prohibit the landfilling of these ashes, as imposed by EU directives. In the present study we determined quantitatively the heavy metals and other elements in the fly and bottom ashes of the medical waste incinerator, by inductively coupled plasma emission spectrometry (ICP) and by energy dispersive X-ray analysis (EDAX). Heavy metals, which are very toxic, such as Pb, Cd, Ni, Cr, Cu and Zn were found in high concentrations in both fly and bottom ashes. Metal leachability of fly and bottom ashes by water and kerosene was measured by ICP and the results showed that toxic metals in both ashes, such as Pb, Cr, Cd, Cu and Zn, have high leaching values. These values indicate that metals can become soluble and mobile if ash is deposited in landfills, thus restricting their burial according to EU regulations. Analysis of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in fly and bottom ashes showed that their concentrations were very low. This is the first known study in Greece and the results showed that incineration of medical waste can be very effective in minimizing the most hazardous and infectious health-care waste. The presence of toxic metals with high leachability values remains an important draw back of incineration of medical waste and various methods of treating these residues to diminish leaching are been considered at present to overcome this serious technical problem.     

Mercury speciation in fluorescent lamps by thermal release analysis

In this work, mercury speciation in phosphorus powder matrices and soda lime glass waste from new and spent fluorescent lamp wastes has been studied by thermo-desorption/atomic absorption spectrometry (TDAAS), X-ray diffraction (XRD), cold vapor-atomic absorption (CV-AAS) and atomic emission spectrometry/inductively coupled plasma (ICP/AES). TDAAS results show the presence of oxidized forms of mercury, i.e., Hg(1+) and Hg(2+), especially in wastes with high mercury concentration. Such forms are mobile, and therefore represent a potential hazard waste material. Glass TD profiles of spent fluorescent lamps suggested the presence of mercury strongly linked to the matrix, which desorbs only at high temperatures.     

Characteristics of ashes from different locations at the MSW incinerator equipped with various air pollution control devices

The characteristics of ashes from different locations at a municipal solid waste incinerator (MSWI) equipped with a water spray tower (WST) as a cooling system, and a spray dryer adsorber (SDA), a bag filter (BF) and a selective catalytic reactor (SCR) as air pollution control devices (APCD) was investigated to provide the basic data for further treatment of ashes. A commercial MSWI with a capacity of 100 tons per day was selected. Ash was sampled from different locations during the normal operation of the MSWI and was analyzed to obtain chemical composition, basicity, metal contents and leaching behavior of heavy metals. Basicity and pH of ash showed a broad range between 0.08-9.07 and 3.5-12.3, respectively. Some major inorganics in ash were identified and could affect the basicity. This could be one of the factors to determine further treatment means. Partitioning of hazardous heavy metals such as Pb, Cu, Cr, Hg and Cd was investigated. Large portions of Hg and Cd were emitted from the furnace while over 90% of Pb, Cu and Cr remained in bottom ash. However 54% of Hg was captured by WST and 41% by SDA/BF and 3.6% was emitted through the stack, while 81.5% of Cd was captured by SDA/BF. From the analysis data of various metal contents in ash and leach analysis, such capturing of metal was confirmed and some heavy metals found to be easily released from ash. Based on the overall characteristics of ash in different locations at the MSWI during the investigation, some considerations and suggestions for determining the appropriate treatment methods of ash were made as conclusions.     

Accumulation and fate of selected heavy metals in a biological wastewater treatment system

The aim of this research was to study the accumulation and removal of heavy metals (Cd, Cu, Pb, Zn) by a biological wastewater treatment system. Heavy metal contents in the influent and effluent wastewater were compared. Also, the heavy metal contents in the sludge before and after anaerobic digestion were compared. The results showed: (1) more pronounced variations in the contents of Cu and Zn than that of Cd and Pb, which showed that at 0.02 for Cd and 0.05 mg/l for Pb, the reduction in their contents was insignificant; (2) that removal of heavy metals was directly proportional to their initial contents in the influent wastewater. Corresponding to the influent contents, in increasing order, the reduction in heavy metal contents was: Cd相似文献   

Toxicity of char residues produced in the co-pyrolysis of different wastes

Char residues produced in the co-pyrolysis of different wastes (plastics, pine biomass and used tyres) were characterized using chemical and toxicity assays. One part of the solid chars was submitted to extraction with dichloromethane (DCM) in order to reduce the toxicity of the char residues by removing organic contaminants. The different volatility fractions present in the extracted char (Char A) and in the raw char (Char B) were determined by progressive weight loss combustion. A selected group of heavy metals (Cd, Pb, Zn, Cu, Hg and As) was determined in both chars.The chars were subjected to the leaching test ISO/TS 21268 – 2, 2007 and the resulting eluates were further characterized by determining a group of inorganic parameters (pH, conductivity, Cd, Pb, Zn, Cu, Hg and As contents) and the concentrations of several organic contaminants (volatile aromatic hydrocarbons and alkyl phenols). An ecotoxicological characterization was also performed by using the bio-indicator Vibrio fischeri.The chemical and ecotoxicological results were analyzed according to the Council Decision 2003/33/CE and the criteria on the evaluation methods of waste ecotoxicity (CEMWE).The results obtained in this work indicated that the extraction with DCM is an effective method for the removal of organic contaminants of high to medium volatility from pyrolysis solid residues, thus decreasing their toxicity potential. Zn can be leached from the chars even after the DCM extraction treatment and can contribute to the ecotoxicity of the eluates obtained from chars.Both chars (treated and non treated with DCM) were classified as hazardous and ecotoxic wastes.     

Laboratory study on the leaching potential of spent alkaline batteries

Four different leaching tests were carried out with spent alkaline batteries as an attempt to quantify the environmental potential burdens associated with landfilling. The tests were performed in columns filled up with batteries either entire or cross-cut, using either deionized water or nitric acid solution as leachant. In a first set of tests, the NEN 7343 standard procedure was followed, with leachant circulating in open circuit from bottom to top through columns. These tests were extended to another leaching step where leachant percolated the columns in a closed loop process.Leachate solutions were periodically sampled and pH, conductivity, density, redox potential, sulphates, chlorides and heavy metals (As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl and Zn) were determined in the samples.The results showed that the total amount of substances leached in tests with cross-cut batteries was higher than with entire ones; zinc and sulphates were the substances found the most in the leachate solutions. In general, the amount of substances dissolved in open circuit is higher than in closed loop due to the effect of solution saturation and the absence of fresh solution addition.Results were compared with metal contents in the batteries and with legal limits for acceptance in landfill (Decision 2003/33/CE and Decree-Law 152/2002). None of the metals were meaningfully dissolved comparatively to its content in the batteries, except Hg. Despite the differences in the experiment procedure used and the one stated in the legislation (mixing, contact time and granulometry), the comparison of results obtained with cross-cut batteries using deionized water with legal limits showed that batteries studied could be considered hazardous waste.     

喀斯特山区燃煤电厂土壤重金属污染评价

选取地处贵州省喀斯特山区的金沙电厂为研究对象,对电厂周围的表层土壤、蔬菜(莲花白)试样的重金属含量进行了测定,采用模糊数学法对土壤重金属污染进行了评价,采用富集系数法分析了莲花白对重金属的富集能力。实验结果表明:电厂周围表层土壤中Hg,As,Cd,Pb,Cu的平均含量分别达0.70,26.40,0.61,44.83,35.51 mg/kg,其中,Hg和Cd的平均含量分别为GB 15618—1995《土壤环境质量标准》中二级标准的1.40和2.03倍;电厂周围土壤受到较为严重的Hg,As,Cd污染,各个方向的重金属污染程度大小顺序为西北西东南西南东北东,总体趋势为西向大于东向;莲花白对土壤中Cd的富集作用较强,对其他重金属的富集作用较弱。     

Solubility and Potential Mobility of Heavy Metals in Two Contaminated Urban Soils from Stockholm,Sweden

The solubility and potential mobility of heavy metals (Cd, Cu,Hg, Pb and Zn) in two urban soils were studied by sequential andleaching extractions (rainwater). Compared to rural (arable) soils on similar parent material, the urban soils were highlycontaminated with Hg and Pb and to a lesser extent also with Cd,Cu and Zn. Metal concentrations in rainwater leachates were related to sequential extractions and metal levels reported fromStockholm groundwater. Cadmium and Zn in the soils were mainly recovered in easily extractable fractions, whereas Cu and Pb were complex bound. Concentrations of Pb in the residual fractionwere between two- and eightfold those in arable soils, indicatingthat the sequential extraction scheme did not reflect the solidphases affected by anthropogenic inputs. Cadmium and Zn conc. inthe rainwater leachates were within the range detected in Stockholm groundwater, while Cu and Pb conc. were higher, whichsuggests that Cu and Pb released from the surface soil were immobilised in deeper soil layers. In a soil highly contaminatedwith Hg, the Hg conc. in the leachate was above the median concentration, but still 50 times lower than the max concentration found in groundwater, indicating the possibilityof other sources. In conclusion, it proved difficult to quantitatively predict the mobility of metals in soils by sequential extractions.     

Atmospheric Metal Pollutants-Archives, Methods, and History

Pollution of the atmosphere with cadmium (Cd), mercury (Hg), and lead (Pb) is a consequence of human activities. Natural archives are necessary to reconstruct the long-term history of metal deposition because accurate measurement of atmospheric deposition is a recent accomplishment. Reconstructions require: (1) accurate determination of concentrations of elements and isotopes, (2) accurate chronology of archives, and (3) archives that faithfully record atmosphere deposition. The most useful long-term archives are accumulations of ice and snow, peat, and lake sediment. Quantification of Cd deposition is uncommon because of its low concentration and substantial chemical mobility. Nonetheless, trends in peat and lake sediment are similar to those of Hg and Pb since ca. 1800 a.d. Both Hg and Pb are relatively chemically immobile and thus the peat and lake archives are believed to record historic trends of atmospheric deposition. Isotopic and concentration studies of Pb indicate a history of northern hemisphere atmospheric pollution extending back prior to 0 a.d. Although measurements of Hg concentration are now routine, isotopic measurements are in their infancy. Some Hg pollution sources have unique isotopic ratios, thereby contributing unique signals to the total Hg. Maximum accumulation rates of Hg and Pb occur up to 10 years later than for Cd (1970s versus 1960s in eastern North America, perhaps slightly later in Europe). By 2004, deposition of Cd, Hg, and Pb had declined from peak values in eastern North America more than 75, 75, and 90%, respectively.     

Trace elements in the leachate of automobile-scrap shredder waste

Leachate from composite samples of automobile-scrap shredder waste was analyzed for trace elements by inductively coupled plasma atomic emission spectrometry, according to the USEPA Toxicity Characteristic Leaching Procedure for solid waste (TCLP). Analytical results confirmed the existence of several environmentally important elements such as barium, cadmium, copper and lead. However, the concentrations of these elements were below the USEPA regulatory limits for the leachate of solid waste. It was also found that representative average values for trace elements, as well as their variability in the leachate of such heterogeneous solid waste, can be arrived at by analyzing composite samples rather than single samples, if a stratified sample selection and composition plan were implemented. Effect of extraction fluids used in the TCLP method was also investigated. The results indicated that the more acidic extraction fluid can leach more of the elements from the shredder waste, regardless of the selection criterion specified in the method.     

Assessment of toxic metals in waste personal computers

Considering the enormous production of waste personal computers nowadays, it is obvious that the study of their composition is necessary in order to regulate their management and prevent any environmental contamination caused by their inappropriate disposal. This study aimed at determining the toxic metals content of motherboards (printed circuit boards), monitor glass and monitor plastic housing of two Cathode Ray Tube (CRT) monitors, three Liquid Crystal Display (LCD) monitors, one LCD touch screen monitor and six motherboards, all of which were discarded. In addition, concentrations of chromium (Cr), cadmium (Cd), lead (Pb) and mercury (Hg) were compared with the respective limits set by the RoHS 2002/95/EC Directive, that was recently renewed by the 2012/19/EU recast, in order to verify manufacturers’ compliance with the regulation. The research included disassembly, pulverization, digestion and chemical analyses of all the aforementioned devices. The toxic metals content of all samples was determined using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). The results demonstrated that concentrations of Pb in motherboards and funnel glass of devices with release dates before 2006, that is when the RoHS Directive came into force, exceeded the permissible limit. In general, except from Pb, higher metal concentrations were detected in motherboards in comparison with plastic housing and glass samples. Finally, the results of this work were encouraging, since concentrations of metals referred in the RoHS Directive were found in lower levels than the legislative limits.     

Urban Metal Flows – A Case Study of Stockholm. Review and Conclusions

Metals have rapidly accumulated in the anthroposphere, especiallyin urban areas, indicating possible environmental and resource problems. Here, Stockholm City was chosen for a case study of urban metal flows, i.e. metal inflow to, metals in the stock of,and metal outflow from the anthroposphere to the biosphere. Themetal stock of Stockholm is large and still growing. The large amounts of metals in the solid waste fraction totally dominatethe outflow from the city. For major parts of the stock, the emissions from goods in use are negligible. There are, however,goods applications corresponding to significant emissions: e.g. the traffic sector (Cu, Zn, Cr, Ni, Pb), the tapwater system (Cu), roofs/fronts or other metal surfaces (Cu, Zn). Today's known metal flows from the anthroposphere of Stockholm to the biosphere and sewage sludge are quantitatively dominated by Zn(34 ton y^-1) and Cu (14 ton y^-1). Historical and present emissions have resulted in high metal concentrations insediments (especially Cd, Hg and Pb, but also Cu and Zn), groundwater (Cu, Hg) and in soils (Hg, Cu, Pb). At present theannual median concentrations are below the Swedish limits for metals in sewage sludge, even if the safety margins aresmall for Cd, Hg and to some extent Cu. The flows of Cu and Zn to Stockholm soils are high with a significant accumulationindicating an environmental impact in a longer time perspective.High levels of metals in surface sediments in the waterenvironments reflects an ongoing input where these metals aretransported from known (Cu, Zn) and or partly unknown (Cd, Hg, Pb) sources. In future urban areas, monitoring of metal flows must be performed both in the anthroposphere and the biospherein order to have a pro active approach to urban environmentalproblems and to get prompt answers to measures taken.