Metal fractionation in soil profiles at automobile mechanic waste dumps.

Soil profiles at five automobile mechanic waste dumps in Port-Harcourt, Nigeria were investigated to assess the spatial distribution, chemical speciation, and likely mobility of Cd, Cu, Pb, Zn, Cr and Ni in the soil as a function of the soil properties. A sequential fractionation protocol was used that generated six different fractions into which soil metal could partition. Cadmium was associated with non-residual fractions at surface horizons, but at lower depths it was in the residual fractions. Copper and Cr partitioned into organic and residual fractions, while Pb was associated with an Fe-Mn oxide fraction and the residual fractions. Zinc in surface horizons partitioned into an Fe-Mn oxide fraction and a fraction that captured carbonate-bound species, but in subsurface horizons, it was mainly in the residual fractions. Ni was predominantly found in the residual fractions. Mobility factors were calculated, and their values tended to decrease with increasing profile depth, indicating that these metals are relatively mobile in the surface horizons compared the subsurface except for chromium in the 15-30 cm depths. The mobility factors for the heavy metals follow the order: Cd > Zn > Pb > Cu > Cr > Ni. The results suggest that there is serious contamination hazard with Cd, Pb, and Zn in the soil profiles.     

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.     

Concentrations and Pools of Heavy Metals in Urban Soils in Stockholm,Sweden

The concentrations of heavy metals (Cd, Cr, Cu, Hg, Ni, Pb andZn) and arsenic (As) were surveyed and the metal pools estimatedin soils in Stockholm Municipality. The sampling sites were distributed all over the entire municipality with a higher sampling density in the city centre. Soils were sampled to a maximum depth of 25 to 60 cm. Soil texture, total-C content, electrical conductivity and pH were analysed. Heavy metal concentrations were determined after wet digestion with boiling7 M HNO₃.The results showed a wide range in heavy metal concentrations, as well as in other soil properties. The city centre soils constituted a rather homogeneous group whereas outside this areano geographical zones could be distinguished. These soils were grouped based on present land use, i.e. undisturbed soils, public parks, wasteland (mainly former industrial areas), and roadside soils. The city centre and wasteland soils generally hadenhanced heavy metal concentrations to at least 30 cm depth compared to park soils outside the city centre and rural (arable)soils in the region, which were used to estimate background levels. For example, the mean Hg concentration was 0.9 (max 3.3)mg kg^-1 soil at 0–5 cm and 1.0 (max 2.9) at 30 cm depth in the city centre soils, while the background level was 0,04 mg kg^-1. Corresponding values for Pb were 104 (max 444) and135 (max 339) mg kg^-1, at 0–5 and 30 cm, respectively, while the background level was 17 mg kg^-1.The average soil pools (0–30 cm depth) of Cu, Pb and Zn were 21,38 and 58 g m^-2 respectively, which for Pb was 3–4 timeshigher and for Cu and Zn 1.5–2 times higher than the backgroundlevel. The total amount of accumulated metals (down to 30 cm)in the city centre soils (4.5^*10 ⁶ m² public gardens and green areas) was estimated at 80, 1.1, 120 and 40 t for Cu, Hg, Pb and Zn, respectively. The study showed (1) thatfrom a metal contamination point of view, more homogeneous soilgroups were obtained based on present land use than on geographicdistance to the city centre, (2) the importance of establishing a background level in order to quantify the degree of contamination, and (3) soil samples has to be taken below the surface layer (and deeper than 30 cm) in order to quantify theaccumulated metal pools in urban soils.     

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。     

重金属污染土壤生物毒性的发光菌法测定及评价

向土壤中人为投加重金属污染物,制备了重金属含量不同的一系列污染土壤,对土壤重金属浸提条件进行了探究,并应用明亮发光杆菌T3（Photobacterium phosphoreum T3）对单一Cu、Cd和Pb污染及Cu-Cd和Cu-Pb复合重金属污染土壤的生物毒性进行了测定。实验结果表明,土壤重金属的最佳浸提剂为0.1 mol/L HCl溶液,最佳浸提时间为2.0 h。在单一重金属污染条件下：Cu表现出低浓度促进生长、高浓度抑制生长的双重生物效应,而Cd和Pb则表现出浓度与生物毒性的正相关性;3种重金属污染土壤的毒性强弱顺序为Cd>Pb>Cu。在复合重金属污染条件下,由于重金属之间的相互作用,污染土壤的生物毒性增强。     

Heavy Metal Sediment Load from the City of Stockholm

A transect of upstream lake sitesand downstream coastal sites surrounding the cityof Stockholm, capital of Sweden, wereinvestigated for heavy metals in sediments.Concentrations of Cd, Cu, Hg, Pb and Zn increasedclose to the city. In the most central areas ofStockholm, sediment deposition was increasedabout 5-fold for Cd, Cu, Hg and Pb and 3-fold forZn, as compared to the surrounding areas. Thesediment load from the city was estimated bycorrecting for a background concentration. It canbe concluded that most of the load of Hg and Pbwas trapped in the sediments close to the citywhile Ni, Cu, Cd and Zn to a higher degree weretransported through the archipelago towards theBaltic Sea.     

Investigation of potentially toxic heavy metals in different organic wastes used to fertilize market garden crops

The benefits of using organic waste as fertilizer and soil amendment should be assessed together with the environmental impacts due to the possible presence of heavy metals (HMs). This study involved analysing major element and HM contents in raw and size-fractionated organic wastes (17 sewage sludges and composts) from developed and developing countries. The overall HM concentration pattern showed an asymmetric distribution due to the presence of some wastes with extremely high concentrations. HM concentrations were correlated with the size of cities or farms where the wastes had been produced, and HM were differentiated with respect to their origins (geogenic: Cr–Ni; anthropogenic agricultural and urban: Cu–Zn; anthropogenic urban: Cd–Pb). Size fractionation highlighted Cd, Cu, Zn and Pb accumulation in fine size fractions, while Cr and Ni were accumulated in the coarsest. HM associations with major elements revealed inorganic (Al, Fe, etc.) bearing phases for Cr and Ni, and sulfur or phosphorus species for Cd, Cu Pb and Zn.     

Heavy Metals in Stockholm Groundwater – Concentrations and Fluxes

Sampling of groundwater in theQuaternary deposits was carried out at 70 sitesin Stockholm for, among other things, metalanalyses. The objectives were to get a notion of the metal content and to get a basis for anestimation of the order of magnitude of thegroundwater transported metal contribution to themain surface water bodies in comparison to otherroutes. Thus, in three watershed areaswithin the Stockholm Town, groundwater flow andmetal concentration propagation were simulatedand metal fluxes were calculated. Theconcentrations of heavy metals were in generalfound to be very high in comparison withgroundwater in forested areas. This was mostpronounced for mercury (Hg) and copper (Cu). Themost remarkable result was a Hg concentration of4.57 g L^-1 in the vicinity of a closed downhospital. The annual contribution of heavy metals(kg) by groundwater to the main surface waterbodies was estimated to: As (2.2), Cd (0.20), Co(4.9), Cr (3.1), Cu (34), Hg (0.06), Ni (28), Pb(2.2) Zn (118). These fluxes are much smallerthan those in forest ecosystems, due to lowergroundwater recharge in urban areas, where agreat part of the runoff is diverted bylandsealing, drainage, tunnels etc. The modelingresults emphasize the importance of the sorptionprocesses indicating that the modeled areas arein a non-steady state condition. It also showsthat the sources generating elevatedconcentrations of the high adsorptive metals Pband Hg are likely to be nearby.     

Effects of Acid Rain on Competitive Releases of Cd, Cu, and Zn from Two Natural Soils and Two Contaminated Soils in Hunan, China

Leaching experiments of rebuilt soil columns with two simulated acid rain solutions (pH 4.6–3.8) were conducted for two natural soils and two artificial contaminated soils from Hunan, south-central China, to study effects of acid rain on competitive releases of soil Cd, Cu, and Zn. Distilled water was used in comparison. The results showed that the total releases were Zn>Cu>Cd for the natural soils and Cd>Zn≫Cu for the contaminated soils, which reflected sensitivity of these metals to acid rain. Leached with different acid rain, about 26–76% of external Cd and 11–68% external Zn were released, but more than 99% of external Cu was adsorbed by the soils, and therefore Cu had a different sorption and desorption pattern from Cd and Zn. Metal releases were obviously correlated with releases of TOC in the leachates, which could be described as an exponential equation. Compared with the natural soils, acid rain not only led to changes in total metal contents, but also in metal fraction distributions in the contaminated soils. More acidified soils had a lower sorption capacity to metals, mostly related to soil properties such as pH, organic matter, soil particles, adsorbed SO₄ ²⁻, exchangeable Al³⁺ and H⁺, and contents of Fe₂O₃ and Al₂O₃.     

Goods in the Anthroposphere as a Metal Emission Source A Case Study of Stockholm,Sweden

The aim of this study was to quantify the diffuse emissionsduring use of metal containing goods in the capital of Sweden,Stockholm. The following metals were studied: Cadmium (Cd), Chromium (Cr), Copper (Cu), Lead (Pb), Mercury (Hg), Nickel (Ni) and Zinc (Zn).A major part of the metals are found in a protected environmentwhere degrading processes like corrosion are most limited. However, during the lifetime of some goods the metal release to the environment is significant. The quantitatively most dominant emissions were found for Cu and Zn. The tap water system and roofs/fronts (Cu) represent goods with large exposedareas but with relatively small release rates per unit. In contrast, brake linings, aerial lines and electrical grounding (Cu) and tyres, brake linings and chemicals (Zn) are allgoods with high release rates but mostly limited exposed stocks.High yearly emissions are also found for Pb, ammunition andsinkers dominate the calculated emissions totally. For Cr and Ni, stainless steel represent the major part of the stocks, butcorrosion was estimated to give only a minor contribution to the emissions. Potential emission sources, i.e. stabilisers,pigments and plated goods dominate the exposed Cd stock. Theseemissions were not quantified due to lack of data. Hg is currently phased out, but one major source of emission, i.e. the use of amalgam, will be continuously significant for several decades. The importance of the traffic sector is obvious. The emissionsfrom brake linings (Cu, Zn and Pb), tyres (Zn, Pb, Cr and Ni)and asphalt wear (Cu, Zn, Cr, Ni and Pb) are all of large importance for the total emission from respectively metal.     

Field investigation of the quality of fresh and aged leachates from selected landfills receiving e-waste in an arid climate

The management of electronic waste (e-waste) is a serious problem worldwide and much of it is landfilled. A survey of four selected landfills in an arid region of South Australia was conducted to determine the proportion of e-waste in municipal waste and the properties of each landfill site. Leachate and groundwater samples were collected upgradient and downgradient of the landfills for analysis of polybrominated diphenyl ethers (PBDEs) and 14 metals and metalloids, including Al, As, Ba, Be, Cd, Co, Cr, Cu, Fe, Ni, Pb, Sb, V and Zn. Our data demonstrate that the selected landfills in South Australia continue to receive municipal waste containing in excess of 6%, or 25,000 tonnes per year, of e-waste. The leachates and groundwater collected from the landfills contained significantly elevated concentrations of Pb with the highest concentration in groundwater of 38 μg/l, almost four times higher than the Australian drinking water guideline of 10 μg/l. The presence of PBDEs was detected in both leachate and groundwater samples. Total PBDEs values of 2.13–59.75 ng/l in leachate samples were 10 times higher than in groundwater samples, which recorded a range of 0.41–6.53 ng/l at all sites. Moreover, the concentrations of metals and metalloids in sampled groundwater contained elevated levels of Al, As, Fe, Ni and Pb that exceeded Australian drinking water guideline values. For these reasons potential leaching of these contaminants is of concern and while difficult to attribute elevated contaminant levels to e-waste, we do not recommend continued disposal of e-waste in old landfills that were not originally designed to contain leachates. The survey also revealed temporal variation in the electrical conductivity and concentrations of As, Cd and Pb present in leachates of landfills in arid Mediterranean climates. These results are consistent with the marked variations in rainfall patterns observed for such climates. The solute concentration (EC and other ions including As, Cd and Pb) declines in the leachates during wet winter months (June to September), in contrast to tropical countries where such changes are observed during wet summer months.     

Metals in Sediments from the Stockholm Region: Geographical Pollution Patterns and Time Trends

The city of Stockholm is intersected and surrounded by water.Freshwater flows eastward and mixes with slightly brackish water in central Stockholm to finally reach the Baltic Sea. Inorder to estimate the magnitude and geographical impact of Stockholm as a source of metals to the aquatic environments, sediments from 117 stations in the Stockholm region have beenanalysed for metals (As, Cd, Co, Cr, Cu, Hg, Ni, Pb and Zn).This paper reports on the geographical pollution pattern and onthe time trends in metal pollution in Stockholm during the 20th century. Stockholm is a strong source of Cd, Cu, Hg,Pb and Zn whereas the Cr concentrations are moderately perturbed.In contrast, the concentrations of As, Co, and Ni are in generalclose to preindustrial levels. The concentrations of Cd, Cu, Hg,Pb and Zn are highest in central Stockholm and eastwards (i.e., in the water flow direction). Sediments upstream of Stockholm andin lakes that are not hydrologically connected to central Stockholm show a significantly lower impact. This may be indicative of metals emitted in Stockholm mainly being transported by the water route. Of Cd, Hg, Pb, and Zn, Cd showsthe most pronounced decline in accumulation rates over the lasttwo decades.     

气化炉渣的重金属浸出特性及化学形态分析

分别采用硫酸硝酸法、水平振荡法和醋酸缓冲溶液法制取气化炉渣的浸出液,考察了不同提取方式对浸出液中重金属质量浓度的影响。采用改进BCR连续提取法对气化炉渣中的重金属Cr,Zn,Cu,Pb,Ni,As,Cd的化学形态进行了分析。实验结果表明：煤气化工艺中的气化炉渣属第Ⅰ类一般工业固体废物;在3种提取方式中,醋酸缓冲溶液法的重金属浸出种类最多,且浸出量最大;Cd和Cr对环境具有较高的潜在危害性,Cu次之,Zn,Pb,Ni,As主要以残渣态形式存在,对环境的直接危害性较低。     

Heavy metal mobility and potential availability in animal manure: using a sequential extraction procedure

In this study, dairy cow manure, goat manure, and chicken manure were collected from three farms and analyzed to find out the concentration of Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn. The concentration and potential of mobility and availability of heavy metals were studied in the animal manure samples. BCR Sequential extraction procedure was used to determine the binding forms of the metals. In this study, pseudo total concentrations of Mn and Zn were found out to be predominant in all the types of animal manure samples. According to the results, it was traced that Cr, Cu, and Ni were observed to be at the second highest level while Cd, Co, and Pb were seen at the lowest level in all the manure samples. When extractable amounts of heavy metals are taken into consideration, it is seen that the amount of the mobile fractions of heavy metals except for Cr and Ni are higher in comparison with that of immobile fraction in all the animal manure samples. It was also viewed that Mn, Cd, and Zn are more available in dairy cow manure and chicken manure whereas Cd, Co, and Mn are more available in goat manure.     

典型磷矿区表层土壤重金属空间分布特征研究

以开阳磷矿区为对象,结合地统计学普通克里金插值法以及单因素分析法,研究了矿区表层土壤重金属的空间分布特征,并对其进行了污染评价。结果表明：以矿区当地土壤重金属背景值为标准,Cu,Zn,Pb,Cd,As含量均存在超标情况;5种元素含量的变异程度均为高度变异,Pb,Cd,As的变异系数远大于Cu,Zn的变异系数;土壤重金属空间分布特征为Cd,As含量在东北部的积累程度大于西南部,东北—东南方向Cu,Zn,Pb,Cd,As的富集程度远大于西北—西南方向;不同土地利用类型对重金属的积累没有显著影响,这很可能与其他因素如背景值、风向、人类干扰（如化工产业）等有关。     

Salinity, organic content, micronutrients and heavy metals in pig slurries from South-eastern Spain

The increase in commercial pig production is an opportunity to reuse animal manures in arid and semiarid soils as a source of nutrients and organic matter. However, there are components in pig slurry that are potentially dangerous for the environment. In this study, pig slurries of 36 pig farms in South-eastern Spain were evaluated for salt content (electrical conductivity, chloride and sodium), organic load (BOD5 and COD), micronutrients (Fe, Cu, Mn and Zn), and heavy metals (Cd, Co, Cr, Ni and Pb). Except for electrical conductivity, Cu and Zn, components in pig slurries did not vary considerably between animal production stages, indicating similar management of diverse animal types. Assuming an application rate based on the maximum input of nitrogen from animal manure (210 kg total N/ha/yr), the estimates for soil annual load of Cl and Na, 415 kg/ha, could be a significant salinisation risk. Cu and Zn seemed to be the metals that could be accumulated most in soils where application of pig slurries is common (4 and 15 kg/ha/yr, respectively). The estimated heavy metal (Cd, Co, Cr, Ni and Pb) input to soils would be 260 g/ha/yr, with a relative contribution of Cr>Ni>Pb>Co>Cd.     

Characteristic of heavy metals in biochar derived from sewage sludge

This study investigates the characteristic of heavy metals (Pb, Zn, Cu, Cd, Cr, Ni and As) in biochar derived from sewage sludge at different pyrolysis temperatures (300, 400, 500, 600 and 700 °C). The heavy metal concentrations, chemical speciation distribution, leaching toxicity, and bio-available contents were investigated using ICP-OES after microwave digestion, a sequential extraction procedure recommended by the Community Bureau of Reference (BCR), an improved nitric acid–sulphuric acid method, and diethylenetriamine pentaacetic acid (DTPA) extraction method, respectively. The results showed that a great percentage of the heavy metals remained in biochar, the concentrations of heavy metals in biochar (except Cd in B7) were higher than that in sludge, and the enrichment of the heavy metals in biochar enhanced with the pyrolysis temperature. Although the effect of pyrolysis temperature on the chemical speciation distribution, the leaching toxicity and the bio-available contents of heavy metals in biochar was inconsistent, the potential risk of biochar on soil and groundwater contamination was lower than sewage sludge.     

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。     

无机稳定剂处理重金属污染土壤

以重金属污染土壤为研究对象,比较了铁屑、蒙脱石、碳酸钙和羟基磷灰石4种稳定剂对土壤中Pb,Zn,Cd,Cu 4种重金属的稳定效果。实验结果表明,4种稳定剂稳定效率的大小顺序为：羟基磷灰石﹥碳酸钙﹥蒙脱石﹥铁屑。当稳定剂质量分数为10%时,羟基磷灰石、碳酸钙、蒙脱石和铁屑对Pb,Zn,Cd,Cu 4种重金属的平均稳定效率分别为99.63%,98.53%,97.15%,86.95 %。未加稳定剂时,土壤中的Pb以残渣态为主,Zn以残渣态和可交换态为主,Cd以残渣态为主,Cu以残渣态和可交换态为主;加入稳定剂后,土壤中4种金属可交换态的所占比例（简称占比）均显著降低,还原态的占比明显增大,残渣态的占比略有增大,氧化态的占比基本保持不变。     

Sequential extraction of metals from mixed and digested sludge from aerobic WWTPs sited in the south of Spain

The content of heavy metals is the major limitation to the application of sewage sludge in soil. However, assessment of the pollution by total metal determination does not reveal the true environmental impact. It is necessary to apply sequential extraction techniques to obtain suitable information about their bioavailability or toxicity. In this paper, sequential extraction of metals from sludge before and after aerobic digestion was applied to sludge from five WWTPs in southern Spain to obtain information about the influence of the digestion treatment in the concentration of the metals. The percentage of each metal as residual, oxidizable, reducible and exchangeable form was calculated. For this purpose, sludge samples were collected from two different points of the plants, namely, sludge from the mixture (primary and secondary sludge) tank (mixed sludge, MS) and the digested-dewatered sludge (final sludge, FS). Heavy metals, Al, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Ti and Zn, were extracted following the sequential extraction scheme proposed by the Standards, Measurements and Testing Programme of the European Commission and determined by inductively-coupled plasma atomic emission spectrometry. The total concentration of heavy metals in the measured sludge samples did not exceed the limits set out by European legislation and were mainly associated with the two less-available fractions (27-28% as oxidizable metal and 44-50% as residual metal). However, metals as Co (64% in MS and 52% in FS samples), Mn (82% in MS and 79% in FS), Ni (32% in MS and 26% in FS) and Zn (79% in MS and 62% in FS) were present at important percentages as available forms. In addition, results showed a clear increase of the concentration of metals after sludge treatment in the proportion of two less-available fractions (oxidizable and residual metal).