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.     

Metal Concentrations in Pore Water of the Lusatian Lignite Mining Sediments and Internal Metal Distribution in Juncus bulbosus

The aim of this study was to determine a suite of four metals (Fe, Mn, Zn, Cu) in the sediment, porewater and a pioneer plant (Juncus bulbosus) of Lusatian lignite mining lakes in eastern Germany. An attempt was made to understand the factors which affect element concentrations in the above- and below-ground biomass of Juncus bulbosus in an extreme environment. Water samples, sediments, porewater and plant material collected from two different mining lakes dominated by Juncus bulbosus species were analyzed for their elemental content. Additionally, scanning electron microscopy (SEM) and an energy-dispersive X-ray (EDX) detector were used to follow the internal metal distribution in the roots of Juncus plant. Results showed that sediment and porewater element concentrations in the lakes decreased in the order Fe > Mn > Zn and Cu. All the four elements were higher in the roots than in above-ground tissues, suggesting that iron plaque induced on roots under anaerobic conditions served as a metal reservoir, but not as an ultimate mechanism to control metal concentrations in the above-ground tissues. SEM and EDX analyses revealed that the rhizodermis, exodermis and endodermis cells regulate the traffic of transition metals and therefore avoid excess levels that are toxic to the plant in acidic mining-impacted lake sediments.     

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.     

Study concerning the recovery of zinc and manganese from spent batteries by hydrometallurgical processes

Used batteries contain numerous metals in high concentrations and if not disposed of with proper care, they can negatively affect our environment. These metals represent 83% of all spent batteries and therefore it is important to recover metals such as Zn and Mn, and reuse them for the production of new batteries. The recovery of Zn and Mn from used batteries, in particular from Zn–C and alkaline ones has been researched using hydrometallurgical methods. After comminution and classification of elemental components, the electrode paste resulting from these processes was treated by chemical leaching. Prior to the leaching process the electrode paste has been subjected to two washing steps, in order to remove the potassium, which is an inconvenient element in this type of processes. To simultaneously extract Zn and Mn from this paste, the leaching method in alkaline medium (NaOH solution) and acid medium (sulphuric acid solution) was used. Also, to determine the efficiency of extraction of Zn and Mn from used batteries, the following variables were studied: reagents concentration, S/L ratio, temperature, time. The best results for extraction yield of Zn and Mn were obtained under acid leaching conditions (2 M H₂SO₄, 1 h, 80 °C).     

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.     

Effect of the addition of sugarcane bagasse composts on micronutrient assimilability in ryegrass

An experiment was conducted under greenhouse conditions to determine the effect of different applied sugarcane bagasse composts on micronutrient assimilability. Five treatments were prepared: soil alone (C), soil+mineral complements of N, P and K (NPK) and three treatments, containing soil+different sugarcane bagasse composts at 100 t ha⁻¹. A ryegrass culture (Lolium perenne L. c.v. Varna) was grown in pots from which five harvests of plant material were obtained. Soil samples of each treatment were collected before sowing and after the third and fifth harvests. The addition of sugarcane bagasse composts to soil increased DTPA-extractable Fe, Mn, Cu and Zn throughout the entire experiment in comparison with C and NPK. These organic materials also led to an increase in Fe, Cu and Zn uptake by plants after the second harvest.     

Sludge earthworm composting technology by Eisenia fetida

Prior to vermicompost application to the soils, there is a need to determine the heavy metal concentrations in the final vermicomposts. Acute toxicity on Eisenia fetida for copper (Cu) and cadmium (Cd) were conducted by artificial soils tests. The dosage of interest is typically the median lethal concentration (LC₅₀) that will kill 50 % of the population of organisms within the test period. The dry artificial soil is pre-moistened 1 or 2 days before the test by adding deionized water to obtain approximately half of the required final water content of 40–60 % of the maximum water holding capacity. The 14-day LC₅₀ values (95 % confidence interval) for Cu and Cd were 530 (450–624) and 1118 (988–1265) mg kg^?1, respectively. The vermicomposting was designed to evaluate the effects of earthworm activity on heavy metals in sewage sludge. Compared with the sludge before vermicomposting by Eisenia fetida, the results are as follows: (1) water content, the pH value and organic matter content decreased, (2) total nitrogen content increased, total phosphorus content and total potassium content decreased, (3) available nitrogen concentration, available phosphorus content increased, and (4) the total content of five metals (Cu, Ni, Cd, Pb and Zn) decreased, and the bioaccumulation factor shows that vermicomposting can efficiently remove heavy metals. Therefore, it can be concluded that the soil use of sludge of the Wastewater Treatment Plant in Huaibei is feasible.     

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.     

Variations of metal distribution in sewage sludge composting

In the study, the variations of heavy metal distributions (of Cu, Mn, Pb, and Zn) during the sewage sludge composting process were investigated by sequential extraction procedures. The total content of Cu and Zn in the composted mixture increased after the composting process. Mn and Zn were mainly found in mobile fractions (exchangeable fraction (F1), carbonate fraction (F2), and Fe/Mn oxide fraction (F3)). Cu and Pb were strongly associated with the stable fractions (organic matter/sulfides fraction (F4) and residual fraction (F5)). These five metal fractions were used to calculate the metal mobility (bioavailability) in the sewage sludge and composted mixture. The mobility (bioavailability) of Mn, Pb, and Zn (but not Cu) increased during the composting process. The metal mobility in the composted mixture ranked in the following order: Mn>Zn>Pb>Cu.     

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.     

Distribution of Cd,Ck, Pb and Zn in Soil and Vegetation Compartments in Stands of Five Boreal Tree Species in N.E. Sweden

Concentrations and total quantity of cadmium (Cd), cupper (Cu),lead (Pb) and zink (Zn) were determined in biomass and soil compartments in a replicated tree species experiment with 27-yr-old stands growing on former farmland in N.E. Sweden. Sequentialextractions of soil samples were performed in order to estimate the exchangeable and an organically bound fraction of each element. The tree species included were Picea abies (L.)H. Karst., Pinus sylvestris L., Pinus contorta Dougl., Larix sibirica Ledeb., and Betula pendula Roth.Tree species influenced the rate of removal of Cu, Pb and Zn incase of stemwood harvesting, and of Cd, Cu and Zn in the case ofwhole-tree harvesting. B. pendula and P. abies had higher quantities and average concentrations of Zn in the biomass. For all species, >50% of the Zn in the stems was found in the bark. P. abies and L. sibirica had higher quantities of Cu in the biomass than the other species.P. abies and P. contorta had high quantities of Cd inthe biomass in relation to the other species. Branches and stembark contained high concentrations of Cd and Pb in relation to foliage and stemwood. Dead branches had especially high concentrations of Pb. The high accumulation rate of Zn in thebiomass of B. pendula was related to a low exchangeable amount of Zn in the A horizon. In the superficial centimeters ofthe A horizon, a depletion similar to that found for Zn was detected for Cu, whereas for Cd and Pb, no correlations were found between quantities of elements in the trees and element pools in the soil.     

Landfill leachate as irrigation water for tree and vegetable crops

The effects of landfill leachate (from Gin Drinker's Bay landfill, Hong Kong) on the growth of tree and vegetable crops were studied in a greenhouse. Higher yields were obtained for Brassica chinensis (Chinese White Cabbage) and B. parachinensis (Flowering Chinese Cabbage) with 5, 10, 20 and 40% leachate dilutions than in the non-leachate control. Yield was reduced for Acacia confusa (Acacia) under all concentrations of leachate treatments. Inhibition of root growth was also observed in the three species with 40% leachate treatment.Leachate-treated soil had elevated levels of electrical conductivity, total-, ammonia) and nitrate-N, exchangeable Na and P. For all heavy metals analysed, only Mn significantly (p < 0.05) accumulated in soil after leachate irrigation.Uptake of N, Na, Fe and Mn was evident for all test species after leachate irrigation. The degree of uptake was positively correlated (p < 0.05) with the leachate concentrations used for irrigation.     

Filter-based treatment of leachate from an industrial landfill containing shredder residues of end-of-life vehicles and white goods

A pilot plant was set up to treat leachate from an industrial landfill containing shredder residues of end-of-life vehicles and white goods. The treatment plant consisted of aeration and sedimentation steps for pre-treatment, and a filter. The plant was designed to simultaneously remove various types of pollutants. The efficiencies of pre-treatment and of the main treatment step were investigated over a period of 3 years at the landfill site. By continuous aeration of the leachate the concentrations of Fe and Mn were reduced by 55% and 49%, respectively. By prolonged sedimentation suspended solid content was noticeably reduced (72%). In the filter, consisting of a mixture of peat and carbon-containing ash as a treatment medium, very high reduction of polar organic compounds, e.g. phenol (74%), o-and p-cresol (91%), and 2,4-dimethylphenol (73%), high average reduction of metals, e.g. Pb (78%), Fe (74%), Cu (73%), Mn (56%), Sn (55%), and Zn (47%), and good average reduction of DOC (26%), Tot-N (23%) and NH₄-N (46%) were achieved. Sixty non-polar compounds in the leachate, identified by GC–MS screening, occurred at trace level. Most of them were considerably reduced in the filter.     

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.     

Disposal of agro-industrial by-products by organic cultivation of the culinary and medicinal mushroom Hypsizygus marmoreus

Organic mushroom cultivation is one of the fastest growing segments of agriculture. At the core of the organic philosophy lies a ban on the use of synthetic fertilizers, pesticides and herbicides, in addition to such tenets as animal welfare, energy efficiency, and social justice. Hypsizygus marmoreus (HM) is a highly praised cultivated culinary and medicinal mushroom. The objective of this paper was to assess the suitability of different spawn media and then the potential of various cultivation substrates to support HM mushroom production compatible with organic standards. This objective was met through the setup of a low-cost cultivation infrastructure. First, seven types of spawn media were tested; then we tested 24 substrates made from organic by-products for their biological efficiency (BE) with strain HM 830, using the liquid inoculation method. The best substrate in terms of BE was corn cob with bran and olive press cake, with a BE of 85.6%. The BE of the same composition but without olive press cake was only 67.5%. The next best substrates were cotton straw combinations with a BE of 31.5–53%. The spent mushroom substrate provides a good method for the disposal of solid waste. The guidance provided in this research complies with organic mushroom cultivation standards and can be used to produce certified organic mushrooms. In addition, it allows responsible and beneficial disposal of a large amount of solid agro-industrial waste.     

Phytostabilisation—A Sustainable Remediation Technique for Zinc in Soils

Two studies were conducted to determine a feasible and practical phytoremediation strategy for Zn-contaminated soils. The aim of the first study was to identify promising plant species capable of Zn remediation for the soils and climatic conditions of British Columbia. The purpose of the second study was to assess the effects of soil amendments in modifying the soil properties and providing the right conditions for the plants to immobilise Zn. Promising plants for phytostabilisation in the first study (Lolium perenne, Festuca rubra and Poa pratensis) were tested in the presence of soil amendments (lime, phosphate and compost, both individually and in combination) in the second study. The efficiency of treatments to stabilise Zn was based on Zn fractionation in the soil and on absorption and partitioning of Zn in plants. Maximum Zn immobilisation was achieved in the soil by a combination of lime, phosphate and compost, in conjunction with growth of P. pratensis.     

Effect of composting on the Cd,Zn and Mn content and fractionation in feedstock mixtures with wood chips from a short-rotation coppice and bark

Micronutrient content and availability in composts may be affected by the addition of wood chips or tree bark as a bulking agent in the compost feedstock. In the first part of this study, micronutrient levels were assessed in bark and wood of poplar and willow clones in a short-rotation coppice. Large differences between species were observed in bark concentrations for Cd, Zn and Mn. In the second part of the study, we aimed to determine the effect of feedstock composition and composting on Cd, Zn and Mn concentrations and availability. By means of three composting experiments we examined the effect of (a) bark of different tree species, (b) the amount of bark, and (c) the use of bark versus wood chips. In general, compost characteristics such as pH, organic matter and nutrient content varied due to differences in feedstock mixture and composting process. During the composting process, the availability of Cd, Zn and Mn decreased, although the use of willow and poplar bark or wood chips resulted in elevated total Cd, Zn or Mn concentrations in the compost. Cd concentrations in some composts even exceeded legal criteria. Cd and Zn were mainly bound in the reducible fraction extracted with 0.5 M NH₂OH?HCl. A higher acid-extractable fraction for Mn than for Cd and Zn was found. Higher Cd concentrations in the compost due to the use of bark or wood chips did not result in higher risk of Cd leaching. The results of the pH-stat experiment with gradual acidification of composts illustrated that only a strong pH decline in the compost results in higher availability of Cd, Zn and Mn.     

Laboratory study on the leaching potential of spent alkaline batteries using a MSW landfill leachate

Two leaching tests were carried out, one with whole batteries and another with cross-cut batteries. In both cases, NEN 7343 (a Nederland’s Standard) procedure was followed using a municipal solid waste (MSW) landfill leachate as extraction solution. Seven fractions were collected corresponding to cumulative liquid/solid (L/S) ratio from 0.1 to 10.0. Those fractions were separately characterized in terms of pH, conductivity, redox potential, density, sulphate, chloride, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl and Zn. Results showed that the influence of the alkaline batteries in the landfill leachate composition varies with their physical integrity and with the L/S ratio, and several variations were observed throughout the tests. The leachate pH and redox potential increased as result of the contact with batteries, particularly pH in the test with the cross-cut batteries. The leachate density and conductivity did not change significantly with the whole batteries, in contrast with the test with cross-cut batteries.     

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.     

Concentrations of heavy metals in fly ash from a coal-fired power plant with respect to the new Finnish limit values

In Finland, the new limit values for heavy metals in fertilizers used in agriculture and in forestry came into force in March 2007, and for materials used as earth construction agents, in June 2006. From the utilization point of view, it was notable that the total heavy metal concentrations (Cd, Cu, Pb, Cr, Mo, Zn, As, Ni, Ba, and Hg) in fly ash from a coal-fired power plant were lower than those limit values. The concentrations of the easily soluble elements Ca, Mg, Na, P, and Zn in the fly ash were between 3.5 and 35 times higher than those found in the coarse mineral soils of Finland. Fly ash is a potential agent for soil remediation and for improving soil fertility. If inorganic materials and by-products are utilized in earthworks, the content of harmful compounds must be low and the harmful components must be tightly bound to the matrix. Therefore, a five-stage sequential extraction procedure was used to evaluate the extractability of different elements in fly ash into the following fractions: (1) the water-soluble fraction, (2) the exchangeable fraction (CH₃COOH), (3) the easily reduced fraction (NH₂OH-HCl), (4) the oxidizable fraction (H₂O₂ + CH₃COONH₄), and (5) the residual fraction (HF + HNO₃ + HCl).