施用碱稳定固体的酸性土壤的Cu和Zn的形态分布

Fractionation of metals in a granite-derived acid sandy loam soil amended with alkaline-stabilised sewagesIudge biosolids was conducted in order to assess metal bioavailability and environmental mobility soil solution was extracted by a centrifugation and filtration technique. Metal speciation in the soil solution wasdetermined by a cation exchange resin method. Acetic acid and EDTA extracting solutions were used forextraction of metals in soil solid surfaces. Metal distribution in different fractions of soil solid phase was determined using a three-step sequential extraction scheme. The results show that the metals in the soilsolution existed in different fractions with variable lability and metals in the soil solid phase were also presentin various chemical forms with potentially different bioavail ability and environmental mobility Alkaline-stabilised biosolids could elevate solubility of Cu and proportion of Cu in organically complexed fractionsboth in soil liquid and solid phases, and may therefore increase Cu mobility. In contrast, the biosolids lowered the concentrations of water-soluble Zn (labile fraction) and exchangeable Zn and may hence decrease bioavailability and mobility of Zn. However, Fe and Mn oxides bound and organic matter bound fractions are likely to be Zn pools in the sludge-amended soil. These consequences possibly result from the liming effect and metal speciation of the sludge product and the difference in the chemistry between the metals in soil.     

热带土壤上连续9年施入污水污泥后重金属Zn, Cd和Pb的分离研究

A long-term field experiment was carried out in the experiment farm of the Sao Paulo State University, Brazil, to evaluate the phytoavailability of Zn, Cd and Pb in a Typic Eutrorthox soil treated with sewage sludge for nine consecutive years, using the sequential extraction and organic matter fractionation methods. During 2005-2006, maize (Zea mays L.) was used as test plants and the experimental design was in randomized complete blocks with four treatments and five replicates. The treatments consisted of four sewage sludge rates (in a dry basis) : 0.0 (control, with mineral fertilization), 45.0, 90.0 and 127.5 t ha^-1, annually for nine years. Before maize sowing, the sewage sludge was manually applied to the soil and incorporated at 10 cm depth. Soil samples (0-20 cm layer) for Zn, Cd and Pb analysis were collected 60 days after sowing. The successive applications of sewage sludge to the soil did not affect heavy metal (Cd and Pb) fractions in the soil, with exception of Zn fractions. The Zn, Cd and Pb distributions in the soil were strongly associated with humin and residual fractions, which are characterized by stable chemical bonds. Zinc, Cd and Pb in the soil showed low phytoavailability after nine-year successive applications of sewage sludge to the soil.     

污泥加石灰后作为肥料用于玉米生长中施肥研究

The use of sewage sludge on agricultural land provides an alternative for its disposal. Therefore, the aim of the present study was to evaluate the feasibility of using industrial sewage sludge produced in Pakistan, as an agricultural fertilizer. The agricultural soil amended with 250 g kg^-1 sewage sludge with or without lime treatment was used for the growth of the common local grain crop, maize （Zea maize）. The mobility of the trace and toxic metals in the sludge samples was assessed by applying a modified BCR sequential extraction procedure. The single extraction procedure was comprised of the application of a mild extractant （CaCl2） and water, for the estimation of the proportion of easily soluble metal fractions. To check the precision of the analytical results, the concentrations of trace and toxic metals in every step of the sequential extraction procedure were summed up and compared with total metal concentrations. The plant-available metal contents, as indicated by the deionized water and 0.01 mol L^-1 CaCl2 solution extraction fractions and the exchangeable fraction of the sequential extraction, decreased significantly （P 〈 0.05） with lime application because of the reduced metal availability at a higher pH, except in the cases of Cd and Cu, whose mobility was slightly increased. Sludge amendment enhanced the dry weight yield of maize and the increase was more obvious for the soil with lime treatment. Liming the sewage sludge reduced the trace and toxic metal contents in the grain tissues, except Cu and Cd, which were below the permissible limits of these metals. The present experiment demonstrates that liming was an important factor in facilitating the growth of maize in sludge-amended soil.     

苏南地区土壤重金属向蔬菜的迁移研究

Vegetable fields in peri-urban areas receive large amounts of extraneous heavy metals because of rapid urbanization and industrialization in China. The concentrations of Cu, Zn, and Pb in 30 soil samples and 32 vegetable samples, collected from 30 different sites in southern Jiangsu Province of China, were measured and their transfer from soil to vegetable was determined. The results showed that the soil samples had wide ranges of pH (4.25-7.85) and electrical conductivity (EC) (0.24-3.42 dS m^-1). Among the soil samples, there were four soil samples containing higher Cu and two soil samples containing higher Zn concentrations than those specified in the Chinese Soil Environmental Quality Standard II. However, no vegetable sample was found to contain a high level of Cu or Zn. In contrast, one vegetable sample contained 0.243 mg Pb kg^-1 FW, which was above the Chinese Food Hygiene Standard, whereas the corresponding soil Pb concentration was lower than the Chinese Soil Environmental Quality Standard II. The transfer coefficients of Cu of all vegetable samples exceeded the suggested coefficient range, implying that extraneous Cu had high mobility and bioavailability to vegetables. There was no significant correlation between extractable soil heavy metal concentrations with four kinds of extractants and soil pH, EC, heavy metal concentrations in vegetables and soils, except that soil pH correlated well with the extractable soil Cu, Zn, and Pb concentrations with 1.0 mol L^-1 NH₄NO₃. Moreover, diethylenetriamine pentaacetic acid (DTPA) extraction method was a more effcient method of extracting heavy metals from the soils independent of soil pH and EC than other three methods used.     

金属污染土壤中锌铜交互作用对锌吸附和植物有效性的影响

In a previous greenhouse experiment,we showed that there was an interaction between cu and Zn,which affected growth and metal uptake by young barley plants grown on soil to which Cd,Cu,Pb,and Zn had been added.We suggested that the underlying mechanism was the control of the amount of plant-available Zn by competitive adsorption between Cu and Zn,In order to test this hypothesis,the adsorption of Zn alone,and in the presence of added Cd,Cu and Pb,has been measured using the same soil.Following adsorption,the extractability of the Zn in CaCl2 solution was measured .The adsorption isotherms showed that of the added metals only Cu had a large effect on Zn adsorption.The effect of Cu was to reduce Zn adsoption and to increase the amount of CaCl2-extractable(i.e.plant-available) Zn,in agreement with the conclusions from the greenhouse experiment.The magnitude of the effect of Cu on plant-avalilable Zn was similar in both experiments.     

三峡库区坡地表层风化特征研究

Extractability and mobility of Cu and Zn and their relationships with 1） accumulation of Cu and Zn and 2） soil pH were studied in three sandy soils （Wabasso, Ankona, and Winder） from commercial citrus groves in Florida, USA. The soils, with a broad range of Cu and Zn concentrations, were fractionated by a modified procedure of Amacher, while Cu and Zn mobility were evaluated using column leaching. The extractability of Cu and Zn increased with decreasing soil pH. Also with increasing total soil Cu and Zn for extractable Cu in the Wabasso sand a threshold level, where the metal extraction rate increased, was noted at 100 mg kg^-1, whereas for extractable Zn in the Wabasso sand the threshold level was found at 60 mg kg^-1 and in the Ankona sand at 120 mg kg^-1. These results suggested that the release potential of Cu and Zn was greater in the Wabasso sand than in the Ankona sand. The column leaching experiment showed that at total soil Cu or Zn concentrations 〈 100 mg kg^-1 all leachates had low Cu and Zn concentrations. However at total concentrations 〉 200 mg kg^-1 for Cu and 〉 150 mg kg^-1 for Zn with decreasing soil pH, the concentrations of both Cu and Zn in the leachates increased exponentially. Also in these sandy soils soluble Cu and Zn mainly originated from the exchangeable fractions, and pH was a key factor controlling Cu and Zn extractability and mobility.     

华北矿区残留态铜、铅在土壤剖面中的分布与迁移

Residual heavy metals are commonly considered to be immobile in soils, leading to an underestimation of their environmental risk. This study investigated the distribution and transport of residual heavy metals along soil profiles, using the Xiaoqinling gold mining region in North China as a case study. Soil samples were collected at three depths from three locations near the tailing heap. The speciation of copper (Cu) and lead (Pb) (exchangeable, carbonate-bound, Fe-Mn oxide-bound, organic matter-bound, and residual fractions) was determined using a sequential extraction procedure. The residual fraction’s morphology was observed using scanning electron microscopy (SEM). Results showed that metal fraction distributions along the soil profiles were influenced by each fraction’s mobility. Residual fraction with high chemical stability cannot be transformed from or into other fractions. This led to the conclusion that the high concentration of residual metals in soils mainly resulted from residual fraction transport.The SEM analysis showed that fine particles (submicrons) were mainly attached to large particles and were likely released and transported by water flow. The more sorptive fractions (non-residual fractions) were mainly retained in the top soil, and the more mobile fractions (residual fraction) were mainly leached to the deep soil. Cu and Pb concentrations in the residual fraction decreased slightly and those in the non-residual fractions decreased significantly with soil depth. These suggest a relatively higher residual metal mobility along the soil pro?les. Therefore, residual metals can be transported in soils and their environmental risk can not be ignored in assessing soil contamination.     

受土壤类型和金属负荷量影响的重金属形态分布

Two series of soil subsamples, by spiking copper(Cu),lead(Pb),zinc(Zn)and cadmium(Cd)in an orthogonal design,were prepared using red soil and brown soil,respectively.The results indicated that heavy metal fractions in these soil subsamples depended not only on soil types,but also on metal loading quantity as well as on interactions among metals in soil.Lead and Cu in red soil appeared mostly in weakly specifically adsorbed(WSA),Fe and Mn oxides bound(OX),and residual(RES)fractions.Zine cxisted in all fractions except organic bound one,and Cd was major in water soluble plus exchangeable(SE)one.Different from the results of red soil,Pb and Cu was present in brown soil in all fractions except organic one,but over 75% of Zn and 90% of Cd existed only in SE fraction.Meanwhile,SE fraction for any metal in red soil was lower than that in brown soil and WSA and OX fractions were higher.It is in agreernent with low cation exchange capacity and large amounts of metal oxides included in red soil.Metal fractions in soil,especially for water soluble plus exchangeable one ,were obviously influenced by other coexisting metals.The SE fraction of heavy metals increased with increasing loading amounts of metals in red soil but not obviously in brown soil,which suggest that metal availability be easily affected by their total amounts spiked in red soil.In addition,more metals in red soil were extracted with 0.20 mol L^-1 NH4Cl（pH5.40）than that with 1.0 mol L^-1 Mg(NO3)2(pH7.0),but the reverse happened in brown soil,implicating significantly different mechanisms of metal desorption from red soil and brown soil.     

云南滇池沉积物中重金属的形态分布特征

Fractionation of heavy metals in sediments can help in understanding potential hazards of heavy metals. The present study analyzed total concentrations and fractions of selected heavy metals （Cd, Cr, Cu, Pb, and Zn） in surface sediments from Dianchi Lake, Yunnan Province, China, as well as factors that may affect distributions of the various heavy metal fractions. Total concentrations of the heavy metals decreased in the order Zn 〉 Cu 〉 Pb 〉 Cr 〉 Cd. These heavy metals, except Cr, were much higher than their background levels, indicating that Dianchi Lake was polluted by Cd, Zn, Pb, and Cu. Cadmium occurred mainly as the non-residual fraction （sum of the HOAc-soluble, reducible, and oxidizable fractions） （97.6%）, and Zn （55.7%） was also predominantly found in the non-residual fraction. In contrast, most of the Cr （88.5%）, Pb （81.8%）, and Cu （59.2%） occurred in the residual fraction. Correlation analysis showed that total heavy metal concentrations, organic matter and reducible Fe were the main factors affecting the distributions of the various heavy metal fractions. In the Walhai section of Dianchi Lake （comprising 97% of the lake area）, the concentrations of Cd, Zn, Pb, and Cu in the non-residual fraction were significantly lower （P ≤ 0.01 or 0.05） than those of the Caohal section （3% of the lake area）. This indicated that potential heavy metal hazards in the Caohai section were greater than the Waihai section.     

森林土壤重金属的分布和迁移: 一种高密度采样方法的应用

The vertical distribution and migration of Cu, Zn, Pb, and Cd in two forest soil profiles near an industrial emission source were investigated using a high resolution sampling method together with reference element Ti. One-meter soil profile was sectioned horizontally at 2 cm intervals in the first 40 cm, 5 cm intervals in the next 40 cm, and 10 cm intervals in the last 20 cm. The migration distance and rate of heavy metals in the soil profiles were calculated according to their relative concentrations in the profiles, as calibrated by the reference element Ti. The enrichment of heavy metals appeared in the uppermost layer of the forest soil, and the soil heavy metal concentrations decreased down the profile until reaching their background values. The calculated average migration rates of Cd, Cu, Pb, and Zn were 0.70, 0.33, 0.37, and 0.76 cm year^-1, respectively, which were comparable to other methods. A simulation model was proposed, which could well describe the distribution of Cu, Zn, Pb, and Cd in natural forest soils.     

Verhalten von Schwermetallen in Böden 1. Untersuchungen zur Schwermetallmobilität

Behaviour of heavy metals in soils. 1. Heavy metal mobility 158 soil samples with widely varying composition were analysed for their total, EDTA, DTPA and CaCl₂ extractable contents of Cd, Zn, Mn, Cu and Pb. By means of single and multiple regressions the relations between the different heavy metal fractions and the pH, organic carbon and clay content were considered. The correlations between the total, EDTA and DTPA extractable contents are very close, whereas the CaCl₂ extractable contents are not or only weakly correlated with these fractions. According to these statistical results the former fractions are considered to be the total quantity (total content) and the reactive quantity (EDTA and DTPA extractable contents) of the heavy metals, whereas the CaCl₂ extractable fraction represents the mobile fraction of the heavy metals in soils. The multiple regressions show that the mobile content of heavy metals is closely correlated with each of the quantity fractions and with soil pH. In the same way the proportion of the mobile fraction (in %) of the total, EDTA and DTPA extractable heavy metal content of the soil samples is closely related to the soil pH. Hereby the proportion of the mobile content of the various elements increases in the pH range 6,5 - 3 below element-specific threshold pH values (in brackets) in the order Cd (6,5) > Mn (5,7) > Zn (5,3) > Cu (4,5) > Pb (3,5). In the pH range 6,5 - 7,5 mainly Cu and to a lesser degree also Pb show an increasing mobility due to the influence of soluble organic substances.     

Verhalten von Schwermetallen in Böden. 2. Extraktion mobiler Schwermetalle mittels CaCl2 und NH4NO3

Behaviour of heavy metals in soils. 2. Extraction of mobile heavy metals with CaCl₂ and NH₄NO₃ 156 soil samples from arable fields, grassland and forest stands were analysed for the CaCl₂^? and NH₄NO₃^? extractable contents of Cd, Zn, Mn, Cu and Pb. The average amounts of Cd, Zn, Cu and Pb extracted with CaCl₂ are higher compared with NH₄NO₃ whereas the relation for Mn is vice versa. The proportion of the NH₄NO₃^? extractable contents in percent of the CaCl₂^? extractable contents of Cd, Zn and Pb decrease with increasing pH, whereas the contents of Mn and Cu increase. Inspite of a differing extraction behaviour of the two salt solutions the CaCl₂^? and NH₄NO₃^? extractable amounts of Cd, Mn, Zn und Pb are highly correlated and can be converted one into another. The mobile (CaCl₂, NH₄NO₃) proportion of the corresponding total, EDTA and DTPA heavy metal contents is in close relation to the pH of the soils. Using CaCl₂ solution the threshold pH values for an increasing mobility decrease in the order Cd > Mn > Zn > Cu > Pb, using NH₄NO₃ as extractant the order is Mn > Cd > Zn > Cu > Pb. In the case of CaCl₂ as extractant soluble chloro-Cd-complexes will be formed so that the Cd mobility in soils will be overestimated in most cases.     

Investigation of Heavy Metals using Various Extraction Methods in Livestock Manures

The use of animal waste for a soil amendment is a viable option for waste management. For safe and sustainable management of waste, it is important to assess the concentrations of heavy metals (HM). An experiment was conducted to compare metals [copper (Cu), zinc (Zn), and manganese (Mn)] in cow manure (CM), duck litter (DL), poultry litter (PL), and poultry litter ash (PLA) using eight extraction solutions. Extractability of HM was highly dependent upon the type of waste as well as extracting agent. Manures differed for the release of HM in the order of PL > DL > CM. Marked decreases in extractable trace elements were observed after ashing of PL irrespective of extraction method. Except for water, extractions released HM in the order of Mn > Cu > Zn. For Zn and Mn, the amount extracted varied in the order 1 M nitric acid (HNO₃) > 0.1 M HNO₃ > 0.01 M HNO₃ ≈ ethylenediaminetetraacetic acid (EDTA) > ammonium nitrate (NH₄NO₃) > calcium chloride (CaCl₂) > ammonium acetate (NH₄OAc) > H₂O in PL and PLA. Peak concentration of Cu was achieved in 1 M HNO₃ solution and the lowest Cu was found in NH₄OAc solution. On the basis of these results, the low extractability of HM in ash could suggest that the use of burned PL would be less of a water-pollution problem in the fields.     

Use of Single Extraction Methods to Predict Bioavailability of Heavy Metals in Polluted Soils to Rice

Human exposure to toxic heavy metals via dietary intake is of increasing concern. Heavy-metal pollution of a rice production system can pose a threat to human health. Thus, it was necessary to develop a suitable extraction procedure that would represent the content of metal available to rice plants (Oryza sativa L.). The aim of this study was to predict, on the basis of single extraction procedures of soil heavy metals, the accumulation of heavy metals (cadium, lead, copper, and zinc) in rice plants. Six extracting agents [Mehlich 1, Mehlich 3, EDTA (ethylenediaminetetraacetic acid), DTPA–TEA (diethylenetriaminepentaacetic acid–triethanolamine), ammonium acetate (NH₄OAc), and calcium chloride (CaCl₂)] were tested to evaluate the bioavailability of heavy metals from paddy soils contaminated with lead–zinc mine tailings to rice. The extraction capacity of the metals was found to be of the order EDTA > Mehlich 3 > Mehlich 1 > DTPA–TEA > NH₄OAc > CaCl₂. The correlation analysis between metals extracted with different extractants and concentrations of the metals in the grain and stalk of the plant showed positive correlations with all metals. The greatest values of correlation coefficients were determined between the NH₄OAc- and CaCl₂-soluble fractions of soil and contents in plants in all four metals studied. Therefore, NH₄OAc and CaCl₂ were the most suitable extractants for predicting bioavailability of heavy metals in the polluted soils to rice. The results suggested that uptake of heavy metals by rice was mostly from exchangeable and water-soluble fractions of the metals in the soils. Soil-extractable metals were more significantly correlated with metal accumulation in the stalk than in the grain. The pH had more significant influence on availability of heavy metals in the soils than total content of metals and other soil properties. The bioavailability of metals for rice plants would be high in acidic soils.     

Characterization of soil heavy metal pools in paddy fields in Taiwan: chemical extraction and solid-solution partitioning

Background, aim, and scope  Ongoing industrialization has resulted in an accumulation of metals like Cd, Cu, Cr, Ni, Zn, and Pb in paddy fields across Southeast Asia. Risks of metals in soils depend on soil properties and the availability of metals in soil. At present, however, limited information is available on how to measure or predict the directly available fraction of metals in paddy soils. Here, the distribution of Cd, Cu, Cr, Ni, Zn, and Pb in 19 paddy fields among the total, reactive, and directly available pools was measured using recently developed concepts for aerated soils. Solid-solution partitioning models have been derived to predict the directly available metal pool. Such models are proven to be useful for risk assessment and to derive soil quality standards for aerated soils. Material and methods  Soil samples (0–25 cm) were taken from 19 paddy fields from five different communities in Taiwan in 2005 and 2006. Each field was subdivided into 60 to 108 plots resulting in a database of approximately 3,200 individual soil samples. Total (Aqua Regia (AR)), reactive (0.43 M HNO₃, 0.1 M HCl, and 0.05 M EDTA), and directly available metal pools (0.01 M CaCl₂) were determined. Solid-solution partitioning models were derived by multiple linear regressions using an extended Freundlich equation using the reactive metal pool, pH, and the cation exchange capacity (CEC). The influence of Zn on metal partitioning and differences between both sampling events (May/November) were evaluated. Results  Total metals contents range from background levels to levels in excess of current soil quality standards for arable land. Between 3% (Cr) and 30% (Cd) of all samples exceed present soil quality standards based on extraction with AR. Total metal levels decreased with an increasing distance from the irrigation water inlet. The reactive metal pool relative to the total metal content is increased in the order Cr << Ni = Zn < Pb < Cu < Cd and ranged from less than 10% for Cr to more than 70% for Cd. Despite frequent redox cycles, Cd, Pb, and Cu appear to remain rather reactive. The methods to determine the reactive metal pool in soils yield comparable results, although the 0.43 M HNO₃ extraction is slightly stronger than HCl and EDTA. The close correlation between these methods suggests that they release similar fractions from soils, probably those reversibly sorbed to soil organic matter (SOM) and clay. The average directly available pool ranged from less than 1% for Cu, Pb, and Cr to 10% for Ni, Zn, and Cd when compared to the reactive metal pool. For Cd, Ni, Zn, and to a lesser extent for Cu and Pb, solid-solution partitioning models were able to explain up to 93% (Cd) of the observed variation in the directly available metal pool. CaCl₂ extractable Zn increased the directly available pool for Ni, Cd, and Cu but not that of Pb and Cr. In the polluted soils, the directly available pool was higher in November compared to that in May. Differences in temperature, rainfall, and changes in soil properties such as pH are likely to contribute to the differences observed within the year. The solid-solution partitioning model failed to explain the variation in the directly available Cr pool, probably because Cr is present in precipitates rather than being adsorbed onto SOM and clay. Despite obvious differences in parent material, source of pollution, climate, and land use, solid-solution partitioning of Cd in paddy fields studied here was similar to that in soils from Belgium and the Netherlands. Discussion  To assess risks of metals in soils, both analytical procedures as well as models are needed. The three methods tested here to determine the reactive metal pool are highly correlated and either of these can be used. The directly available pool was predicted most accurately by the 0.43 M HNO₃ method. The similarity of metal partitioning in paddy soils compared to well-drained soils suggests that changing redox conditions in paddy fields have a limited effect on the geochemical behavior of metals like Cd, Ni, and Zn. Small but significant differences in the directly available metal pool during the year suggest that redox cycles as well as differences in rainfall and temperature affect the size of the directly available metal pool. The large observed spatial heterogeneity of contaminant levels requires ample attention in the setup of soil monitoring programs. Conclusions  The directly available pool (0.01 M CaCl₂) of Cd, Zn, and Ni in paddy fields can be described well by an extended Freundlich model. For Cu and Pb, more information on dissolved organic carbon is needed to obtain a more accurate estimate of the directly available pool. Recommendations and perspectives  Soil testing protocols and models used in risk assessment consider the availability of pollutants rather than the total metal content. Results from extensive testing indicate that approaches developed for nontropical regions can be applied in paddy fields as well for metals like Cd, Ni, and Zn. This study shows that the chemical behavior under drained conditions in paddy fields is comparable to that observed in soils across the European Union, which allows regions with large scale soil pollution including Taiwan to apply such concepts to derive meaningful experimental protocols and models to assess risks of metals in soils.     

Measuring reactive metal in soil: a comparison of multi‐element isotopic dilution and chemical extraction

The isotopically exchangeable metal pool (E‐value) of zinc (Zn), cadmium (Cd) and lead (Pb) were simultaneously measured, using stable isotope dilution, in soils contaminated by Pb/Zn mining activities and varying in properties likely to affect metal reactivity, including pH, organic matter content, metal concentration and land use. E‐values were compared with single and sequential extraction schemes. Results showed a wide range of metal reactivity (approximately 1–100% of total) depending on the extent of contamination and on the prevailing soil conditions. Across the range of soils, the E‐values showed no consistent correspondence to any single chemical extraction procedure (EDTA, DTPA and HNO₃) although there was reasonable agreement with the extractants 0.05 m EDTA and 0.43 m HNO₃ in acidic organic soils. Extraction with 0.005 m DTPA substantially under‐estimated the isotopically exchangeable metal content. E‐values corresponded reasonably well with the exchangeable metal (fraction 1 (F1) of the sequential extraction procedure) in calcareous soils but relatively poorly and inconsistently with F1–F2, F1–F3 or F1–F4 in acidic‐neutral soils. Operational aspects associated with determination of multi‐element E‐values are discussed.     

Modelling trace metal extractability and solubility in French forest soils by using soil properties

Soil/solution partitioning of trace metals (TM: Cd, Co, Cr, Cu, Ni, Sb, Pb and Zn) has been investigated in six French forest sites that have been subjected to TM atmospheric inputs. Soil profiles have been sampled and analysed for major soil properties, and CaCl₂‐extractable and total metal content. Metal concentrations (expressed on a molar basis) in soil (total), in CaCl₂ extracts and soil solution collected monthly from fresh soil by centrifugation, were in the order: Cr > Zn > Ni > Cu > Pb > Co > Sb > Cd , Zn > Cu > Pb = Ni > Co > Cd > Cr and Zn > Ni > Cu > Pb > Co > Cr > Cd > Sb , respectively. Metal extractability and solubility were predicted by using soil properties. Soil pH was the most significant property in predicting metal partitioning, but TM behaviour differed between acid and non‐acid soils. TM extractability was predicted significantly by soil pH for pH < 6, and by soil pH and Fe content for all soil conditions. Total metal concentration in soil solution was predicted well by soil pH and organic carbon content for Cd, Co, Cr, Ni and Zn, by Fe content for Cu, Cr, Ni, Pb and Sb and total soil metal content for Cu, Cr, Ni, Pb and Sb, with a better prediction for acidic conditions (pH < 6). At more alkaline pH conditions, solute concentrations of Cu, Cr, Sb and Pb were larger than predicted by the pH relationship, as a consequence of association with Fe colloids and complexing with dissolved organic carbon. Metal speciation in soil solutions determined by WHAM‐VI indicated that free metal ion (FMI) concentration was significantly related to soil pH for all pH conditions. The FMI concentrations of Cu and Zn were well predicted by pH alone, Pb by pH and Fe content and Cd, Co and Ni by soil pH and organic carbon content. Differences between soluble total metal and FMI concentrations were particularly large for pH < 6. This should be taken into account for risk and critical load assessment in the case of terrestrial ecosystems.     

Comparison of Four Different Extraction Methods to Assess Plant Availability of Some Metals in Organic Forest Soil

Abstract

The objective was to find an uncomplicated test giving the best correlation between calcium (Ca), magnesium (Mg), manganese (Mn), copper (Cu), zinc (Zn), and lead (Pb) extracted from humic forest soil and the total concentration of the element in some understorey forest plants using well‐known extractants. The elements were selected because Ca, Mg, Mn, Cu, and Zn are essential nutrients to plants and Zn and Pb are potentially harmful heavy metals received over the years in the southern parts of Norway by long‐range atmospheric transport. Extraction of organic podzolic surface soil (Oe and Oa horizon) from 17 different pine forests in central and southern Norway was carried out with four different reagents to evaluate uptake of Ca, Mg, Mn, Cu, Zn, and Pb in the understorey plants Deschampsia flexuosa, Vaccinium myrtillus (leaves and stems), and Vaccinium vitis‐idaea (leaves and stems). The NH₄OAc, NH₄NO₃, HCl, and EDTA solutions used to extract the soil in addition to concentrated HNO₃, demonstrated variability in capacity to extract the different elements from the soil. The extractants yielded significant relations between concentrations of Ca, Mn, and Pb in the Oe or Oa horizon and some of the plants or plant compartments, even though distinct correlation was more dependent on species and plant part than the actual extractant used. In the case of Zn, Cu, and Mg only a few sporadic correlations were observed between the different plant/plant compartments and the element concentrations in the soil extracts. Altogether none of the extractants was shown to be superior to the others in providing the best correlation with the elements concentrations in selected plant/plant compartments. In the case of Ca, Mn, and Pb all the extractants including concentrated HNO₃ provided significant correlations with at least some of the selected plant/plant compartments.     

Schwermetallanreicherungen in Salzmarschen der südlichen Nordseeküste

Heavy metal accumulations in Salic Fluvisols of the southern North Sea coast The total contents of Cd, Pb, Cu and Zn (HNO₃ bomb digestion) and their EDTA extractable fractions in Salic Fluvisols were investigated. The mean total content of Cd was 0,09 mg/kg, of Pb 44,1 mg/kg, of Cu 11,4 mg/kg and of Zn 105,6 mg/kg. Mostly the highly developed soils showed higher contents than poorly developed ones. The EDTA extractable fractions were comparatively small: they were 59% (Cd), 44% (Pb), 15% (Cu) and 10% (Zn) of the total content. The heavy metal contents of the soils in Elisabeth-Außengroden were higher than of those in Jadebusen. The vertical heavy metal distribution showed a different sedimentation pattern over the last hundred years. Compared with the geological background values Cd was 2- to 3-fold enriched, Pb 7-fold, Cu 3- to 4-fold and Zn 3-fold in soils with high sedimentation rates. Even higher values are likely in soils with smaller sedimentation rates.     

Soil extractants used in Estonia and Finland,their extraction power,and suitability for testing Estonian soils

Abstract

The present work was undertaken to obtain information on the effectiveness of extractants used for soil testing in Estonia and in Finland and to evaluate the suitability of the Finnish methods for use with Estonian soils. The sample material involved 86 soils and winter wheat (Triticum aestxvum L.) shoots collected from farmers’ fields in Estonia. The extractants used in Estonia were double lactate (DL) for phosphorus (P) and potassium (K), ammonium lactate (AL) for calcium (Ca) and magnesium (Mg), 1N HCl for copper (Cu), manganese (Mn), and zinc (Zn), ammonium oxalate (AO) for molybdenum (Mo) and 1N HNO₃ for cadmium (Cd) and lead (Pb). In Finland, acid ammonium acetate (AAAc) was used for P, K, Ca, and Mg determination, and acid ammonium acetate‐EDTA (AAAc‐EDTA) for Cu, Mn, Mo, Zn, Cd, and Pb. The order of magnitude of extractable concentrations for these elements was: P_DL > P_AAAc, K_DL < K_AAAc, Ca_AL < Ca_AAAc, Mg_AL> Mg_AAAc, Cu_HCl > Cu_AAAc‐EDTA, Mn_HCl, > Mn_AAc‐EDTA, Zn_HCl < Zn_AAAc‐EDTA, Mo_AO > Mo_AAAc‐EDTA, Cd_HNO3 > Cd_AAAc‐EDTA, and Pb_HNO3 > Pb_AAAc‐EDTA. Correlations between results of respective methods for determining macronutrients were high (r ≥ 0.9). In the case of Cu, Mn, Mo, Zn, Cd, and Pb r values ranged from 0.5 to 0.8 due to difficulties in determining low concentrations. A statistically significant correlation between concentrations of elements in soil and in wheat shoots only existed for few elements. The DL extractable P and K correlated better than those for the AAAc method, and coefficients for the DL method were 0.29 and 0.31, respectively. This indicates that the DL method is better suited to Estonian soils than the AAAc method. In the case of Cu, Mn, Mo, and Zn, no method preference was found.