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.     

Heavy metals in source-separated compost and digestates

The production of compost and digestate from source-separated organic residues is well established in Europe. However, these products may be a source of pollutants when applied to soils. In order to assess this issue, composts, solid and liquid digestates from Switzerland were analyzed for heavy metals (Cd, Co, Cr, Cu, Ni, Pb and Zn) addressing factors which may influence the concentration levels: the treatment process, the composition, origin, particle size and impurity content of input materials, the season of input materials collection or the degree of organic matter degradation.Composts (n = 81) showed mean contents being at 60% or less of the legal threshold values. Solid digestates (n = 20) had 20–50% lower values for Cd, Co, Pb and Zn but similar values for Cr, Cu and Ni. Liquid digestates (n = 5) exhibited mean concentrations which were approximately twice the values measured in compost for most elements. Statistical analyses did not reveal clear relationships between influencing factors and heavy metal contents. This suggests that the contamination was rather driven by factors not addressed in the present study.According to mass balance calculations related to Switzerland, the annual loads to agricultural soils resulting from the application of compost and digestates ranged between 2% (Cd) and 22% (Pb) of total heavy metal loads. At regional scale, composts and digestates are therefore minor sources of pollution compared to manure (Co, Cu, Ni, Zn), mineral fertilizer (Cd, Cr) and aerial deposition (Pb). However, for individual fields, fertilization with compost or digestates results in higher heavy metal loads than application of equivalent nutrient inputs through manure or mineral fertilizer.     

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.     

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.     

Fixation and partitioning of heavy metals in slag after incineration of sewage sludge

Fixation of heavy metals in the slag produced during incineration of sewage sludge will reduce emission of the metals to the atmosphere and make the incineration process more environmentally friendly. The effects of incineration conditions (incineration temperature 500-1100°C, furnace residence time 0-60min, mass fraction of water in the sludge 0-75%) on the fixation rates and species partitioning of Cd, Pb, Cr, Cu, Zn, Mn and Ni in slag were investigated. When the incineration temperature was increased from 500 to 1100°C, the fixation rate of Cd decreased from 87% to 49%, while the fixation rates of Cu and Mn were stable. The maximum fixation rates for Pb and Zn and for Ni and Cr were reached at 900 and 1100°C, respectively. The fixation rates of Cu, Ni, Cd, Cr and Zn decreased as the residence time increased. With a 20min residence time, the fixation rates of Pb and Mn were low. The maximum fixation rates of Ni, Mn, Zn, Cu and Cr were achieved when the mass fraction of water in the sludge was 55%. The fixation rate of Cd decreased as the water mass fraction increased, while the fixation rate of Pb increased. Partitioning analysis of the metals contained in the slag showed that increasing the incineration temperature and residence time promoted complete oxidation of the metals. This reduced the non-residual fractions of the metals, which would lower the bioavailability of the metals. The mass fraction of water in the sludge had little effect on the partitioning of the metals. Correlation analysis indicated that the fixation rates of heavy metals in the sludge and the forms of heavy metals in the incinerator slag could be controlled by optimization of the incineration conditions. These results show how the bioavailability of the metals can be reduced for environmentally friendly disposal of the incinerator slag.     

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。     

赤泥中重金属元素的浸出性与结合形态

采用等离子体质谱仪分析了拜耳法赤泥(BRM)和烧结法赤泥(SRM)中Cr,Ni,Cu,Zn,As,Cd,Cs,Pb等8种重金属元素的含量。采用逐级提取的方法分析了BRM和SRM中8种重金属元素的浸出情况和形态分布差异。实验结果表明:SRM中水溶态As的质量浓度达到17.3μg/L,BRM和SRM中可交换态Cr的质量浓度均在2 300μg/L以上,对水环境可能存在潜在危害;两种赤泥中不同形态重金属的浸出率有较大差异,SRM中Ni和BRM中Zn的总浸出率分别在60%和50%以上。     

Century Perspective of Heavy Metal Use in Urban Areas. A Case Study in Stockholm

The inflow and stock (amount in use) of heavy metals (cadmium(Cd), chromium (Cr), copper (Cu), lead (Pb), mercury (Hg), nickel (Ni) and zinc (Zn)) in goods in 1995 have been quantifiedin the anthroposphere of Stockholm, Sweden. Statistics on national, regional and local level were used. Contacts were established with representatives from production and constructionin the industrial sector and with authorities. The results show that the stock of Cd is 0,2 kg per capita. For the other heavymetals the corresponding result per capita is: Cr 8, Cu 170, Hg 0,01, Ni 4, Pb 73 and Zn 40 kg. The inflow varies between2–8%of the stock indicating the importance of the stock. The lowestlevels are for Cu and Pb. Heavy metal levels in solid waste are high, between 15–45% of the amount in the inflow (Hg excluded), the lowest values were for Cu and Pb. Thus, recyclingis incomplete. Long life expectancy goods form the majority of the stock but there is a tendency that short life expectancy goods increase their importance in the inflow. Concealedgoods are also more frequent in inflow than in the stock.     

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.     

An investigation on the potential of metal recovery from the municipal waste incinerator in Taiwan

This study aimed to identify distribution of metals and to estimate the amount of these metals that can be potentially recovered from incineration residues. First, the partitioning behavior of Cr, Cu, Fe, Cd, Al, Zn, and Pb in bottom ash and fly ash was investigated in one large municipal waste incinerator in Taiwan. In addition, the material flow analysis (MFA) method was used to estimate the material flux of metals within incinerator plant, and to calculate the amount of metal recovery. According to the findings of this study, six metals (Fe, Al, Cu, Zn, Cr, and Pb) concentrated in bottom ash mostly, while Cd existed primarily in fly ash. The weight percentages of Fe (4.49%), Al (5.24%), Cu (1.29%), Zn (2.21%), and Pb (0.58%) in incinerator ash are high, and even higher than the compositions of natural minerals. Finally, the amount of Cr, Cu, Fe, Cd, Al, Zn and Pb that can be potentially recovered from incineration residues will reach 2.69 x 10(2), 1.46 x 10(4), 4.91 x 10(4), 6.92 x 10(1), 5.10 x 10(4), 1.85 x 10(4) and 4.66 x 10(3) ton/yr, respectively.     

Use of dewatered municipal sludge on Canna growth in pot experiments with a barren clay soil

The present study evaluated the possibility of using the dewatered municipal sludge for non-agricultural purposes. The sludge was amended with soil and was applied at 0, 165, 330, 495 and 660 t/ha to promote the growth of Canna. The results showed that the Canna growth pattern exhibited a pronounced positive growth response in the range of 165–495 t/ha, and the Canna could not survive at an amendment rate of 660 t/ha. The analysis of chlorophyll fluorescence parameters showed that sludge did no harm to Canna, while under the conditions of barren soil alone, the plants were put into nutrients stress conditions. Due to the application of sludge, the concentration of heavy metals (Cu, Zn, Cr, Cd, Pb and Ni) in soil increased. However, by planting of Canna, contents of Cd, Ni and Zn showed trends of decline; Cd and Ni have shown a significant decline in concentration, while Zn had only limit response. As a result, dewatered sludge might be used to amend the barren soil and Canna could be used for phytoremediation of sludge.     

添加CaO对燃煤重金属元素富集效果的影响

选取CaO作为吸附剂,探究了不同燃烧温度下添加CaO对重金属元素在燃煤灰渣中富集效果的影响规律。实验结果表明:添加CaO对重金属元素Cr未起到富集作用,而对Mn,Ni,Cu,Zn,As,Cd,Pb 7种重金属元素的富集效果显著;随燃烧温度的升高,CaO对各赋存形态的Mn,Ni,Cu,Zn,As的富集效果先变好而后变差,对各赋存形态的Cd和Pb的富集效果越来越好;CaO添加比(预处理后的CaO颗粒与预处理后的原煤的质量比)越大,CaO对Mn,Ni,Cu,Zn,As,Cd,Pb的富集效果越好,燃烧温度为850℃时的最佳CaO添加比为4%。     

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.     

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.     

Heavy metal content of combustible municipal solid waste in Denmark.

Data on the heavy metal composition of outlets from Danish incinerators was used to estimate the concentration of Zn, Cu, Pb, Cr, Ni, Cd, As and Hg in combustible waste (wet as received) at 14 Danish incinerators, representing about 80% of the waste incinerated in Denmark. Zn (1020 mg kg(-1)), Cu (620 mg kg(-1)) and Pb (370 mg kg(-1)) showed the highest concentration, whereas Hg (0.6 mg kg(-1)) showed the lowest concentration. The variation among the incinerators was in most cases within a factor of two to three, except for Cr that in two cases showed unexplained high concentrations. The fact that the data represent many incinerators and, in several cases, observations from a period of 4 to 5 years provides a good statistical basis for evaluating the content of heavy metals in combustible Danish waste. Such data may be used for identifying incinerators receiving waste with high concentrations of heavy metals suggesting the introduction of source control, or, if repeated in time, the data must also be used for monitoring the impacts of national regulation controlling heavy metals. It is recommended that future investigations consider the use of sample digestion methods that ensure complete digestion in order to use the data for determining the total heavy metal content of waste.     

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.     

Potential use of lateritic and marine clay soils as landfill liners to retain heavy metals

The potential of a lateritic soil and a marine clay, typical of those found in hot and humid climatic regions, was assessed for use as a landfill liner material. A series of tests were conducted - physical and chemical, batch adsorption, column, hydraulic conductivity, etc., - to evaluate the heavy metal sorption capacity, chemical compatibility of hydraulic conductivity, and transport parameters of the soils. Experimental results showed that the marine clay had better adsorption capacity than that of the lateritic soil and that its hydraulic conductivity was an order of magnitude lower. In addition, the hydraulic conductivities of both soils when permeated with low concentration heavy metal solutions were below 1x10(-7)cm/s. When permeated with Cr, Pb, Cd, Zn, and Ni solutions, the retardation factors of the lateritic soil and the marine clay ranged from 10 to 98 and 37 to 165, respectively, while the diffusion coefficients ranged from 1.0x10(-5) to 7.5x10(-6) and 3.0 to 9.14x10(-7)cm2/s, respectively. For both soils, Cr and Pb were retained relatively well, while Cd, Zn, and Ni were more mobile. The marine clay had higher retardation factors and lower diffusion coefficients, and its hydraulic conductivity was more compatible with Cr solution, than that of the lateritic soil. In general, the properties of the marine clay indicate that it has significant advantages over the lateritic soil as landfill liner material.     

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.     

Nutrients and heavy metals distribution in thermally treated pig manure.

Ash from pig manure treated by combustion and thermal gasification was characterized and compared in terms of nutrient, i.e., potassium (K), phosphorus (P) and heavy metal, i.e., cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni) and zinc (Zn) contents. Total nutrient and metal concentrations were measured using energy dispersive X-ray fluorescence analysis. Acid (HNO3, H2SO4) and water-extractable concentrations were also measured both in non-classified ash and in selected ash particle size fractions using flame atomic absorption spectrometry and colorimetric spectrometry. Results indicate that ash from gasified manure contained more water-extractable K in comparison with combusted manure whereas the opposite was the case with respect to P. Heavy metals Ni, Cr and Cd were present in higher concentrations in the fine particle size fractions (< 30 microm of particle diameter), whereas K, P, Zn and Cu exhibited higher concentrations in the coarser particle size fractions (> 30 microm).