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.     

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.     

Residues characterisation from the fluidised bed combustion of East London’s solid recovered fuel

Waste thermal treatment in Europe is moving towards the utilisation of the combustible output of mechanical, biological treatment (MBT) plants. The standardisation of solid recovered fuels (SRF) is expected to support this trend and increase the amount of the generated combustion residues. In this work, the residues and especially the fly ashes from the fluidised bed combustion (FBC) of East London’s NCV 3, Cl 2, and Hg 1 class SRF, are characterised. The following toxicity indicators have been studied: leachable chlorine, organochlorides expressed as pentachlorobenzene and hexachlorobenzene, and the heavy metals Cu, Cr, Cd, Zn, Ni, and Pb. Furthermore the mineralogical pattern of the ashes has been studied by means of XRD and SEM–EDS. The results suggest that these SRF derived ashes have significantly lower quantities of Cu, Cd, Pb, Zn, leachable Cl, and organochlorides when compared to other literature values from traditional waste thermal treatment applications. This fact highlights the importance of modern separation technologies employed in MBT plants for the removal of components rich in metals and chlorine from the combustible output fraction of SRF resulting to less hazardous residues.     

Improved understanding of key elements governing the toxicity of energy ash eluates

Ash from incinerated waste consists mainly of a complex mixture of metals and other inorganic elements and should be classified based on its inherent hazardous effects according to EUs Waste Framework Directive. In a previous study, we classified eight eluates from ash materials from Swedish incineration plants, both chemically and ecotoxicologically (using bacteria, algae, crustacean and fish). Based on measured concentrations in the eluates together with literature acute toxicity data on the crustacean Nitocra spinipes we identified six elements (i.e. Zn, Cu, Pb, Al, K and Ca) potentially responsible for the observed ecotoxicity. However, comparing the used test methods with N. spinipes, the acute test was relatively insensitive to the eluates, whereas the (sub)chronic test (i.e. a partial life cycle test, investigating larval development ratio) was very sensitive. The overall aim of this follow-up study was to verify if the pinpointed elements could be responsible for the observed (sub)chronic toxicity of the eluates. Individual effect levels (i.e. NOEC values) for these six elements were therefore generated using the (sub)chronic test. Our results show that for six of the eight eluates, the observed ecotoxicity can be explained by individual elements not classified as ecotoxic (Al, K and Ca) according to chemical legislation. These elements will not be considered using summation models on elements classified as ecotoxic in solid material for the classification of H-14, but will have significant implications using ecotoxicological test methods for this purpose.     

Characterization of char derived from various types of solid wastes from the standpoint of fuel recovery and pretreatment before landfilling

Carbonization is a kind of pyrolysis process to produce char from organic materials under an inert atmosphere. In this work, chars derived from various solid wastes were characterized from the standpoint of fuel recovery and pretreatment of waste before landfilling. Sixteen kinds of municipal and industrial solid wastes such as residential combustible wastes, non-combustible wastes, bulky wastes, construction and demolition wastes, auto shredder residue, and sludges were carbonized at 500 degrees C for 1h under nitrogen atmosphere. In order to evaluate the quality of char as fuel, proximate analysis and heating value were examined. The composition of raw waste had a significant influence on the quality of produced char. The higher the ratio of woody biomass in waste, the higher heating value of char produced. Moreover, an equation to estimate heating value of char was developed by using the weight fraction of fixed carbon and volatile matter in char. De-ashing and chlorine removal were performed to improve the quality of char. The pulverization and sieving method seems to be effective for separation of incombustibles such as metal rather than ash. Most char met a 0.5 wt% chlorine criterion for utilization as fuel in a shaft blast furnace after it was subjected to repeated water-washing. Carbonization could remove a considerable amount of organic matter from raw waste. In addition, the leaching of heavy metals such as chrome, cadmium, and lead appears to be significantly suppressed by carbonization regardless of the type of raw waste. From these results, carbonization could be considered as a pretreatment method for waste before landfilling, as well as for fuel recovery.     

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.     

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。     

Chemical properties of heavy metals in typical hospital waste incinerator ashes in China

Incineration has become the main mechanism for hospital waste (HW) disposal in China after the outbreak of Severe Acute Respiratory Syndrome (SARS) in 2003. However, little information is available on the chemical properties of the resulting ashes. In the present study, 22HW ash samples, including 14 samples of bottom ash and eight samples of fly ash, were collected from four typical HW incineration plants located across China. Chemical analysis indicated that the HW ashes contained large amounts of metal salts of Al, Ca, Fe, K, Mg, Na with a concentration range of 1.8-315gkg(-1). Furthermore, the ashes contained high concentrations of heavy metals such as Ag, As, Ba, Bi, Cd, Cr, Cu, Mn, Ni, Pb, Ti, Sb, Sn, Sr, Zn with a vast range of 1.1-121,411mgkg(-1), with higher concentrations found in the fly ash samples. Sequential extraction results showed that Ba, Cr, Ni and Sn are present in the residual fraction, while Cd existed in the exchangeable and carbonate fractions. As, Mn, Zn existed in the Fe-Mn oxide fraction, Pb was present in the Fe-Mn oxide and residual fractions, and Cu was present in the organic matter fraction. Furthermore, toxicity characteristic leaching procedure (TCLP) results indicated that leached amounts of Cd, Cu and Pb from almost all fly ash samples exceeded the USEPA regulated levels. A comparison between the HW ashes and municipal solid waste (MSW) ash showed that both HW bottom ash and fly ash contained higher concentrations of Ag, As, Bi, Cd, Cr, Cu, Pb, Ti, and Zn. This research provides critical information for appropriate HW incineration ash management plans.     

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%).     

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.     

Metal distribution in incineration residues of municipal solid waste (MSW) in Japan

This study aimed to identify distribution of metals and the influential factors on metal concentrations in incineration residues. Bottom ash and fly ash were sampled from 19 stoker and seven fluidized bed incinerators, which were selected to have a variety of furnace capacity, furnace temperature, and input waste. In the results, shredded bulky waste in input waste increased the concentration of some metals, such as Cd and Pb, and the effect was confirmed by analysis of shredded bulky waste. During MSW incineration, lithophilic metals such as Fe, Cu, Cr, and Al remained mainly in the bottom ash while Cd volatilized from the furnace and condensed to the fly ash. About two thirds of Pb and Zn was found in the bottom ash despite their high volatility. Finally, based on the results obtained in this study, the amount of metal in incineration residues of MSW was calculated and the loss of metal was estimated in terms of mass and money. A considerable amount of metal was found to be lost as waste material by landfilling of incineration residues.     

Potential emissions from two mechanically-biologically pretreated (MBT) wastes

The interaction of parameters determining the potential emissions of two different mechanically-biologically pretreated municipal solid wastes (MBT wastes) is elucidated in this work. The origins of the wastes are Germany and Sweden. By means of lab-scale experiments, increased stabilisation through composting is preferably determined by a decrease in respiration activity. Concurrently, the stabilisation is verified for the leachates by a decrease in COD, DOC, and BOD(5). Total organic carbon content reflects stabilisation less accurately. FT-IR and thermal analytical methods add valuable information about the state of degradation, especially when several distinct thermal parameters are taken into account. Mobility of Cr, Ni, Pb, and Zn produced by a batch leaching test with deionized water is reduced by the pretreatment of both materials. Mobility of copper unambiguously increased. A principle component analysis (PCA) of membrane fractionated leachates indicates an affinity of Cu to mobile humic acids or dissolved organic carbon. High Cr, Zn, and Ni contents in the solid co-occur with high contents of solid humic acids. To a lesser extent, this is also true for solid Cd, Cu, and Pb contents. Due to differences in required landfilling conditions, actual emissions and after-care phase length will depend on whether each waste is landfilled in Germany or Sweden.     

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.     

A simple and convenient empirical survey method with a soil electrical conductivity meter for incineration residue-derived soil contamination

To facilitate field surveys for identifying areas of incineration residue-derived soil contamination, a simple and convenient method with a soil electrical conductivity meter was examined. First, the leaching test specified by Notification No. 13 of the Ministry of the Environment, 1973, was conducted on 506 samples of 11 types of wastes and compost, and the relationship between the concentrations of toxic elements [total Hg (T-Hg), Cd, Pb, Cr⁶⁺, and As] and values of electrical conductivity (EC) was examined. The results showed that bottom ash and fly ash were wastes with high EC values and that these wastes indicated higher levels of toxic elements. Second, an estimation method for the soil EC value of contaminated soil (ECc) was proposed based on the EC values of noncontaminated soil, and its usefulness was examined. The results of field surveys conducted at sites whose soils were suspected of contamination by dioxins and other pollutants derived from incineration residues showed that the contaminated spots and areas were identified by using ECc values. Moreover, comparison of the elemental contents of soils in terms of Cr, Ni, Zn, Na, K, Ca, Fe, Mn, and others, in addition to the above-mentioned toxic elements (excluding Cr⁶⁺), with those of the potential sources of pollution was verified to be effective for identifying the source of soil contamination.     

Effect of composting process on phytotoxicity and speciation of copper, zinc and lead in sewage sludge and swine manure

The concentration and bioavailability of heavy metals in composted organic wastes have negative environmental impacts following land application. Aerobic composting procedures were conducted to investigate the influences of selected parameters on heavy metal speciation and phytotoxicity. Results showed that both of sewage sludge (SSC) and swine manure (SMC) composting systems decreased the pH, the content of organic matter (OM) and dissolved organic carbon (DOC), and total amounts of Cu, Zn and Pb. Sequential extraction showed that readily extractible fractions of exchangeable and carbonate in Cu and Zn increased during SSC composting but decreased during SMC composting, thus their bioavailability factors (BF) enhanced in SSC but declined in SMC. The fraction of reducible iron and manganese (FeMnOX) of Cu and Zn in SSC and FeMnOX-Cu in SMC decreased, but FeMnOX-Zn in SMC gradually increased in the process of compost. In contrast, the changes of Pb distributions were similar in two organic wastes. Pb was preferentially bound to the residual fraction and its BF decreased. The evolution of heavy metal distributions and BF depended on not only total metal concentrations but also the other properties, such as pH, decomposition of OM and decline of DOC. The germination rate (RSG), root growth (RRG) and germination index (GI) of pakchoi (Brassica Chinensis L.) increased during the composting process. Linear regression analysis demonstrated that GI, which could represent phytotoxic behavior to the plants, could be poorly predicted by BF or total amount of metals, i.e., BF-Zn, T-Cu. However, the inclusion of other physicochemical parameters (pH, OM and DOC) could enhance the linear regression significances (R).     

Phytoremediation: The uptake of metals and metalloids by rhodes grass grown on metal‐contaminated soil

An experiment was performed to examine the phytoremediation potential of Rhodes grass (Chloris gayana Kunth cv. ‘Pioneer’). The study sought to determine substrate tolerance, biomass production, and plant uptake of antimony (Sb), arsenic (As), cadmium (Cd), lead (Pb), silver (Ag), and zinc (Zn). The plants were grown on weight percent mixtures (5 percent, 15 percent, 25 percent, 35 percent, 50 percent) of a vertisol soil and base‐metal mine tailings (7–2,040 μg/g As, ≥ 30 μg/g Cd, 30–12,000 μg/g Pb, and 72–4,120 μg/g Zn). The 5 percent and 15 percent amendment of mine tailings increased the biomass production of Rhodes grass (from 0.1 g/plant to ≈ 3.5 g/plant) without appreciably elevating plant concentrations of the elements. Plant growth decreased by greater than 50 percent for the substrate containing greater than 25 percent tailings (3,023 μg/g Pb and 1,084 μg/g Zn). Reduced biomass production coincided with maximal Zn uptake by Rhodes grass (249.8 μg/g), indicating tailings induced phytotoxicity. The total concentrations of metals and metalloids tolerated by Rhodes grass in the plant‐growth medium indicated hypertolerance to elevated As, Pb, and Zn concentrations. Partial extraction of the plant‐growth medium determined that plant‐available Pb was ten times higher than Ag, As, Cd, and Zn availability. However, Rhodes grass accumulated low levels of Pb, in addition to As and Cd, over the experimental range, indicating low fodder toxicity risk to browsing livestock. This study concludes that if there are no invasive species issues associated with conservation land uses, Rhodes grass is well suited to metalliferous mined land revegetation and would therefore be highly effective for such programs in subtropical and tropical Australia. © 2005 Wiley Periodicals, Inc.     

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.     

An overview of metals recovery from thermal power plant solid wastes

Thermal power plants (TPPs) that burn fossil fuels emit several pollutants linked to the environmental problems of acid rain, urban ozone, and the possibility of global climate change. As coal is burned in a power plant, its noncombustible mineral content is partitioned into bottom ash, which remains in the furnace, and fly ash, which rises with flue gases. Two other by-products of coal combustion air-pollution control technologies are flue gas desulfurization (FGD) wastes and fluidized-bed combustion (FBC) wastes. This paper analyzed and summarized the generation, characteristics and application of TPP solid wastes and discussed the potential effects of such solid wastes on the environment. On this basis, a review of a number of methods for recovery of metals from TPP solid wastes was made. They usually contain a quantity of valuable metals and they are actually a secondary resource of metals. By applying mineral processing technologies and hydrometallurgical and biohydrometallurgical processes, it is possible to recover metals such as Al, Ga, Ge, Ca, Cd, Fe, Hg, Mg, Na, Ni, Pb, Ra, Th, V, Zn, etc., from TPP solid wastes. Recovery of metals from such wastes and its utilization are important not only for saving metal resources, but also for protecting the environment.     

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.     

Predicting the mobility of Zn, Fe, Cu, Pb, Cd from roasted sulfide (pyrite) residues—A case study of wastes from the sulfuric acid industry in Sweden

Leachates from roasted sulfide residues, which are the wastes from the production of sulfuric acid at Falun, Sweden, have low pH and high concentrations of Zn, Fe, and SO₄. The minerals are mainly hematite and maghemite and, because the various sulfides in the feed behave differently during the roasting process, the residual sulfides minerals are pyrrhotite and sphalerite. Oxidation of the residual sulfides contributes acidity, Zn, Fe, Cu, Cd, and sulfate to the effluents from the waste deposits. The dissolution of sphalerite is most likely accelerated in acid solution rich in Fe (III). The formation of Pb-sulfate coatings on galena may provides an armoring effect which slows the oxidation of the galena. Residual sulfides are source phases controlling long-term contaminant release. Other source minerals for Zn, Fe, Pb, Cu, Cd and SO₄ in the effluents are iron oxides which retained percentage quantities of SO₄, roast-derived alteration rims of Zn oxides on sphalerite, alterated silicates formed during the roasting process, and secondary minerals (e.g. Zn, Fe, Cu sulfates, iron hydroxides) that were precipitated by in-site oxidation in the waste dumps. The Zn, Fe, and Cu sulfates most likely control short-term changes in the chemistry of the leachate, while Pb concentration in the leachates may be controlled predominantly by Pb-release from the altered silicates. The mineralogical and geochemical data provide fundamental information essential for the remedial management of this type of industial waste.