施污土壤与污泥中Cu、Pb、Cd、Zn的形态分布

污泥中的重金属元素是限制其大规模农田利用的重要因素。施污土壤和污泥中重金属的形态研究可以用来评价土壤中重金属的生物有效性以及它们在土壤中的移动性。用修正BCR三步连续提取法进行分步提取研究了污水污泥和施污后的西红柿地土壤中Cu、Pb、Cd、Zn的形态分布状况。施用污泥堆肥10t hm-2后的土壤中Cu、Pb、Cd、Zn的全量与各种形态含量无明显增加,Cu、Pb、Zn含量远低于国家土壤环境质量标准。土壤中Cu的各种形态分布关系是:残渣态>可还原态=可氧化态>可交换态和弱酸溶解态,Cu在土壤中的存在是以最稳定的残渣态为主。堆肥污泥与干化污泥相比,残渣态Cu的比例明显增加。土壤中Pb的各种形态分布关系是以残渣态和可还原态为主,但可氧化态的分布比例最小。土壤中Cd的可交换态、可还原态和残渣态各占据相等的含量,但可氧化态Cd的含量几乎为零。Zn在土壤中的各种形态分布关系是:可交换态和弱酸溶解态>可氧化态>可还原态>残渣态,Zn在土壤中的存在是以最易迁移的可交换态和弱酸溶解态为主。这些金属元素在土壤中的相对稳定性顺序为:Cu>Pb>Cd>Zn。Zn在土壤中的移动性要远高于Cu。     

Behavior of heavy metals from sewage sludge in a Chernozem of the dry belt in Saxony‐Anhalt/Germany

In a small‐plot trial different doses of sewage sludge (equivalent 82‐330 tons of dry matter per hectare) were incorporated in 0—25 cm depth (1982—1985). The aim of the investigations was to study the fate of the heavy metals Zn, Cd, Cu, Ni, Pb, and Cr, to determine their concentration in different soil fractions using a sequential extraction method and to ascertain their uptake by Zea mays L. plants. Eleven years after the last application the metals supplied with the sludge had moved as far as 50 cm in depth. The concentrations of Zn, Cd, Cu, Ni, and Cr in the saturation extract of the sampled soil layers were closely correlated with the concentrations of dissolved organic carbon (DOC). This result suggests that the heavy metal displacement was partly connected with the DOC movement in the soil. Considerable amounts of Zn and Cd coming from sewage sludge were found in the mobile fractions of the soil. Cu, Ni, and Pb were located especially in organic particles, and Cr was obviously bound by Fe‐oxides. Nine years after the last application the binding species of heavy metals were still different compared with those in the untreated soil. The whole withdrawal of heavy metals by plants yielded <1 % of the applied amounts. In the case of Zn the uptake from the sludge amended soil decreased during the experimental period. No similar tendency was observed for the other elements. In any case their annual variations of uptake exceeded the effect of sludge application.     

蚯蚓活动对城市生活污泥重金属的影响

采用塑料温棚内垄式堆积污泥培养蚯蚓方式,研究了蚯蚓处理对污泥重金属的影响。结果表明,污泥经蚯蚓处理后,理化性质发生了显著的变化,污泥的pH值、有机质、总氮和总磷都有不同程度的降低;蚯蚓能吸收富集污泥中的重金属,其中对重金属Cd有较强的富集能力;蚯蚓处理使污泥中重金属含量均出现不同程度的下降,重金属Cr、Zn、Pb、Cd、Cu、Ni分别减少27.98%、31.46%、32.81%、13.85%、23.86%和22.92%。利用盆栽试验,研究了污泥施用于土壤后生菜体内重金属积累的情况,结果表明,生菜体内重金属Zn、Cu、Pb和Ni的含量为污泥处理高于蚓粪处理;Cr和Cd则分别为差异不显著和略有降低。     

Effect of solid-phase speciation on metal mobility and phytoavailability in sludge-amended soil

Sequential extraction was utilized for partitioning Cd, Cr, Ni, and Zn, in soil and sludge samples into five operationally-defined fractions: exchangeable, bound to carbonates, bound to Fe-Mn oxides, bound to organic matter and residual. The highest amounts of Cd, Ni, and Zn, expressed as per cent of the total, were found in the Fe-Mn oxide fraction of the sewage sludge. Chromium was significantly associated with the organic fraction of the sludge. The residue was the most abundant fraction for all metals studied in the untreated soil, and for Cd and Ni in the sludge-treated soil. The concentration of exchangeable Cd and Cr was relatively low in the untreated soil and did not change much after sludge application, whereas the concentrations of exchangeable Zn increased about 50 times and the concentrations of exchangeable Ni doubled in the sludge-treated soil. The lysimetric experiment revealed an increase in Zn and Ni uptake by ryegrass and in the percentage of metals leached from the soil profile after massive sludge application. In contrast only negligible changes were observed for Cd and Cr. The assumption that mobility and biological availability are related to metal speciation was confirmed by the agreement between the distribution pattern of Cd, Cr, Ni and Zn in the soils, the uptake of the metals by plants and their capacity for leaching out from the 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.     

The transfer of heavy metals to barley plants from soils amended with sewage sludge with different heavy metal burdens

Purpose

Our main aim objective was to evaluate the transfer of Cd, Cr, Cu, Ni, Pb and Zn to barley (Hordeum vulgare) grown in various soils previously amended with two sewage sludges containing different concentrations of heavy metals. This allowed us to examine the transfer of heavv metals to barley roots and shoots and the occurrence of restriction mechanisms as function of soil type and for different heavy metal concentration scenarios.

Material and methods

A greenhouse experiment was performed to evaluate the transfer of heavy metals to barley grown in 36 agricultural soils from different parts of Spain previously amended with a single dose (equivalent to 50 t dry weight ha^?1) of two sewage sludges with contrasting levels of heavy metals (common and spiked sludge: CS and SS).

Results and discussion

In soils amended with CS, heavy metals were transferred to roots in the order (mean values of the bio-concentration ratio in roots, BCF_Roots, in brackets): Cu (2.4)?~?Ni (2.3)?>?Cd (2.1)?>?Zn (1.8)?>?Cr (0.7)?~?Pb (0.6); similar values were found for the soils amended with SS. The mean values of the soil-to-shoot ratio were: Cd (0.44)?~?Zn (0.39)?~?Cu (0.39)?>?Cr (0.20)?>?Ni (0.09)?>?Pb (0.01) for CS-amended soils; Zn (0.24)?>?Cu (0.15)?~?Cd (0.14)?>?Ni (0.05)?~?Cr (0.03)?>?Pb (0.006) for SS-amended soils. Heavy metals were transferred from roots to shoots in the following order (mean values of the ratio concentration of heavy metals in shoots to roots in brackets): Cr (0.33)?>?Zn (0.24)?~?Cd (0.22)?>?Cu (0.19)?>?Ni (0.04)?>?Pb (0.02) for CS-amended soils; Zn (0.14)?>?Cd (0.09)?~?Cu (0.08)?>?Cr (0.05)?>?Ni (0.02)?~?Pb (0.010) for SS-amended soils.

Conclusions

Soils weakly restricted the mobility of heavy metals to roots, plant physiology restricted the transfer of heavy metals from roots to shoots, observing further restriction at high heavy metal loadings, and the transfer of Cd, Cu and Zn from soils to shoots was greater than for Cr, Ni and Pb. Stepwise multiple linear regressions revealed that soils with high sand content allowed greater soil-plant transfer of Cr, Cu, Pb and Zn. For Cd and Ni, soils with low pH and soil organic C, respectively, posed the highest risk.     

Schwermetalle im Boden eines Klärschlamm-Versuchsfeldes

Heavy metals in soil of a sewage sludge experimental field The total amounts of Zn, Cd, Pb, Cu, Cr and Ni were determined in different depths of soils which have obtained sewage sludges in amounts between 180 and 1620 dt dry matter/ha. The elements Zn, Cd. Pb and Cu have been most enriched in the first twenty cm of the soils. The contents of Zn, Cd and Pb in the depth of 40–60 cm also showed a significant increase. The treshold values for Zn and Cd in soils were almost attained respectivly slightly exceeded in the first twenty cm of the soil which has obtained 1440 dt dry matter sewage sludge per ha.     

Concentrations and forms of heavy metals in Slovak soils

The risk assessment of heavy‐metal contamination in soils requires knowledge of the controls of metal concentrations and speciation. We tested the relationship between soil properties (pH, CEC, C_org, oxide concentrations, texture) and land use (forest, grassland, arable) and the partitioning of Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn among the seven fractions of a sequential extraction procedure in 146 A horizons from Slovakia. Using a cluster analysis, we identified 92 soils as representing background metal concentrations while the remaining 54 soils showed anthropogenic contamination. Among the background soils, forest soils had the lowest heavy‐metal concentrations except for Pb (highest), because of the shielding effect of the organic layer. Arable soils had the highest Cr, Cu, and Ni concentrations suggesting metal input with agrochemicals. Grassland soils had the highest Cd and Zn concentrations probably for geogenic reasons. Besides the parent material (highest metal concentrations in soils from carbonatic rock, lowest in quartz‐rich soils with sandy texture), pedogenic eluviation processes controlled metal concentrations with podzols showing depletion of most metals in E horizons. Partitioning among the seven fractions of the sequential extraction procedure was element‐specific. The pH was the overwhelming control of the contributions of the bioavailable fractions (fractions 1–4) of all metals and even influenced the contributions of Fe oxide‐associated metals (fractions 5 and 6) to total metal concentrations. For fractions 5 and 6, Fe concentrations in oxides were the most important control of contributions to total metal concentrations. After statistically separating the pH from land use, we found that the contributions of Cu in fractions 1–4 and of NH₄NO₃‐extractable Al, Cd, Pb, and Zn to total metal concentrations were significantly higher under forest than under grassland and in some cases arable use. Our results confirm that metal speciation in soils is mainly controlled by the pH. Furthermore, land use has a significant effect.     

Chemical extractability of heavy metals during and after long-term applications of sewage sludge to soil

Sequential extractions were used on soils from a long-term experiment treated with either metal-contaminated sewage sludge or inorganic fertilizers between 1942 and 1961. The four extracts employed were CaCl₂, NaOH, EDTA and aqua regia. These showed that large increases in the proportions of Pb, Cu, Zn, Ni and Cd in at least one of the first three fractions occurred during the first 10 years of sewage sludge additions. Cr always remained predominantly in the aqua regia-soluble fraction. For 30 years after this, including a period of more than 20 years after application of sludges to the field had ceased, there was very little change in the percentage of each metal extracted by each reagent. Although the ‘residual’ (aqua regia-soluble) and EDTA fractions usually contained the largest amounts of metals in either sludge- or fertilizer-treated soils, there were clear differences between the metals: Pb represented the largest fraction of any metal extracted by EDTA, Cu of any metal extracted by NaOH and Cd of any metal extracted by CaCl₂. The same extractions were made of the sewage sludges that were applied to the field, and the distributions of the metals differed from those found in the treated soils. It was particularly apparent that more Pb and Cu was present as the ‘residual’ (aqua regia) fraction in sludges than in the soils.     

Heavy‐Metal Contamination of Soil and Vegetables in Wastewater‐Irrigated Agricultural Soil in a Suburban Area of Hanoi,Vietnam

The To Lich and Kim Nguu Rivers, laden with untreated waste from industrial sources, serve as sources of water for irrigating vegetable farms. The purposes of this study were to identify the impact of wastewater irrigation on the level of heavy metals in the soils and vegetables and to predict their potential mobility and bioavailability. Soil samples were collected from different distances from the canal. The average concentrations of the heavy metals in the soil were in the order zinc (Zn; 204 mg kg^?1) > copper (Cu; 196 mg kg^?1) > chromium (Cr; 175 mg kg^?1) > lead (Pb; 131 mg kg^?1) > nickel (Ni; 60 mg kg^?1) > cadmium (Cd; 4 mg kg^?1). The concentrations of all heavy metals in the study site were much greater than the background level in that area and exceeded the permissible levels of the Vietnamese standards for Cd, Cu, and Pb. The concentrations of Zn, Ni, and Pb in the surface soil decreased with distance from the canal. The results of selective sequential extraction indicated that dominant fractions were oxide, organic, and residual for Ni, Pb, and Zn; organic and oxide for Cr; oxide for Cd; and organic for Cu. Leaching tests for water and acid indicated that the ratio of leached metal concentration to total metal concentration in the soil decreased in the order of Cd > Ni > Cr > Pb > Cu > Zn and in the order of Cd > Ni > Cr > Zn > Cu > Pb for the ethylenediaminetetraaceitc acid (EDTA) treatment. The EDTA treatment gave greater leachability than other treatments for most metal types. By leaching with water and acid, all heavy metals were fully released from the exchangeable fraction, and some heavy metals were fully released from carbonate and oxide fractions. The concentrations of Cd, Cr, Cu, Ni, Pb, and Zn in the vegetables exceeded the Vietnamese standards. The transfer coefficients for the metals were in the order of Zn > Ni > Cu > Cd = Cr > Pb.     

Simultaneous Sorption of Cd,Cu, Ni,Zn, Pb,and Cr on Soils Treated with Sewage Sludge Supernatant

Disposal of sewage sludge creates the potential for heavy metal accumulation in theenvironment. This study assessed nine soils currently used as Dedicated Land Disposal units(DLDs) for treatment and disposal of municipal sewage sludge in the vicinity of Sacramento,California. Adsorption characteristics of these soils for Cd, Cu, Ni, Zn, Pb, and Cr were studiedby simultaneously mixing these elements in the range of 0-50 µmol L-1 with sludgesupernatant and reacting with the soil using a soil:supernatant ratio of 1:30, pH = 4.5 or 6.5, andconstant ionic strength (0.01 M Na-acetate). The concentration of metals in the supernatant wasdetermined after a 24 hr equilibration period. Adsorption isotherms showed that metal sorptionwas linearly related to its concentration in the supernatant solution. The distribution coefficientKd (Kd = concentration on solid phase/concentration in solution phase) was computed as theslope of the sorption isotherm. The distribution coefficients were significantly correlated to soilorganic matter content for Ni, Cu, Cd, and Pb at pH 4.5 and for Ni, Cu, Zn, and Cd at pH 6.5.There was also a correlation between Kd and soil specific surface area but no relationship to othersoil properties such as CEC, clay content, and noncrystalline Fe and Al materials. Therefore, soilorganic carbon and surface area appear to be the most important soil properties influencing metaladsorption through formation of organo-metal complexes. The Kd values for all elements werehigher at pH 6.5 than at 4.5. Selectivity between metals resulted in the following metal affinitiesbased on their Kd values: Pb>Cu>Zn>Ni>Cd≈Cr at pH 4.5 andPb>Cu≈Zn>Cd>Ni>Cr at pH 6.5.     

Removal of Heavy Metals from Soil Components and Soils by Natural Chelating Agents. Part II. Soil Extraction by Sugar Acids

Aqueous solutions of the natural chelatingagents D-gluconic acid and D-glucaric acid (D[+]-saccharic acid) were tested for their ability to remove heavy metals (Cd, Cr, Cu,Ni, Pb, Zn) from a soil polluted by long-term application of sewage sludge. Batch equilibrium experiments were performed undervariation of fundamental process parameters, i.e. pH value, sugaracid concentration, batch solution volume, solid:liquid ratioand number of treatment cycles.The extractability of heavy metals was low under near-neutral andslightly basic pH conditions. It increased drastically between pH12.0 and 13.0. Pb and Cu were preferentially extracted metals.Compared with the extraction efficiency of pH adequate puresodium hydroxide solutions, the sugar acids enhanced thesolubilisation of Pb and Cr especially. The metal depletion fromsoil was the highest when applying 20 or 50 g L^-1 solutionsof the chelating agents. Under strongly basic conditions solid:liquid ratios of 1:10 or 1:20 were proofed to be advantageous.Except Ni, multi-step extraction improved the metal removalstrongly. This effect was the greatest for Cr extraction. Underoptimised conditions the following metal extraction degrees wereachieved with strongly alkaline D-gluconic acid solutions: Ni 43%%, Cr 60%%, Cd 63%%,Zn 70%%, Pb 80%%, and Cu 84%%.     

新乡市大棚菜田土壤重金属积累特征及污染评价

采用微波消解-ICP-AES技术,测定不同种植年限大棚菜田土壤样品中As、Pb、Zn、Cd、Cr、Mn、Ni、Cu等重金属的含量,研究不同种植年限与大棚菜田土壤重金属累积的相关性以及大棚菜田土壤重金属累积特征,并利用地积累指数法进行污染评价。结果表明:大棚菜田土壤重金属Zn、Pb、Ni、Mn和Cu的含量与种植年限具有极显著相关性;大棚菜田土壤中重金属Cd和Cr的含量与种植年限不相关。重金属元素间相关性分析表明,Zn与Pb、Cd、Ni、Mn、Cr、Cu,Pb与Cd、Ni、Mn、Cr、Cu,Cd与Ni、Mn、Cr,Ni与Mn、Cr、Cu,Mn与Cr、Cu具有污染同源性,Cu与Cd、Cr不具有污染同源性。地积累指数法污染评价结果显示Cd的污染等级达到了6级,已构成了极严重污染;Zn和Cu的污染等级达到2级,已构成了中度污染;Pb、Mn的污染等级达到1级,已经构成了轻~中度污染;As、Ni、Cr均未构成污染。     

Prediction of available heavy metals by six chemical extractants in a sewage sludge‐amended soil

Abstract

In a field experiment conducted during three years in a sandy‐loam, calcareous soil, one aerobically digested sewage sludge (ASL) and another anaerobically digested sewage sludge (ANSL) were applied at rates of 400, 800, and 1,200 kg N/ha/year, and compared with mineral nitrogen fertilizer at rates of 0, 200, 400, and 600 kg N/ha/year in a cropping sequence of potato‐corn, potato‐lettuce, and potato, the first, second, and third year, respectively. Results showed that the highest values of soil extractable metals were obtained with aqua regia, whereas the lowest levels with DTPA. All metal (Zn, Cu, Cd, Ni, Pb, and Cr) gave significant correlations between metal extracted with the different extractants and metal loading applied with the sludges. The metal extractable ion increased over the control for Zn, Cu, Cd, Ni, Pb, and Cr extracted with DTPA, EDTA (pH 8.6) and 0.1 N HC1, for Zn, Cd, Ni, Pb, and Cr extracted with EDTA (pH 4.65) and AB‐DTPA, and for Zn, Cd, Ni, and Cr extracted with aqua regia. The level of metal‐DTPA extractable resulted highly correlated with that obtained by the other methods, except the Ni‐aqua regia extractable. The soil extractable elements which showed significant correlations with metals in plant were: Zn, Cu, Cd, and Ni in potato leaves, Cd, Ni, and Pb in corn grain, and Zn and Cd for lettuce wrapper leaves. In general, all the chelate based extractants (DTPA, EDTA pH 4.6, EDTA pH 8.6, AB‐DTPA) were equally useful as indicator of plant available metals in the soil amended with sludge.     

The feasibility of using an industrial sewage sludge produce in Pakistan as agricultural fertilizer used for cultivation of Sorghum bicolor L

Abstract

In the present study we evaluate the feasibility of using untreated industrial sewage sludge by liming before use as a fertilizer, produced in Pakistan. In a pots experiment, limed industrial sewage sludge (LSW) and non-limed sewage sludge (NLSW), were amended with soil separately and grown sorghum. After maturity, the sorghum grains were analysed for total contents of potentially toxic metals (TPTM), As, Cd, Cr, Cu, Ni, Pb and Zn. The proportion of different mobility fractions of each element in LWS and NLSW, a modified BCR sequential extraction procedure (Community Bureau of Reference) and single extractions with mild extractants (deionized water and CaCl₂) were used. In LSW, the availability of most of the elements under study was reduced, probably due to the increased pH of soil, while this was the reverse in the cases of Cd and Cu, their mobility was slightly increased by lime-treated sludge. The sorghum grains grown in LSW have low level As, Cr, Ni, Pb and Zn as compared to grains grown in NLSW, except Cu and Cd, which, however, never exceeded legal limits. Thus the research showed that liming, by augmenting soil alkalinity, allows a safe agricultural use even of industrial sludge, which is environmentally hazardous for its great content of heavy metals.     

Long-term changes in soil and plant metal concentrations in an acidic dredge disposal site receiving sewage sludge

A long-term experiment was conducted to determine the distribution of sludge-borne metals applied to a revegetated acidic dredge spoil disposal site. The initial soil was infertile and highly acidic (pH 2.4). Sewage sludge and lime were applied in 1974 at the rates of 100 and 23 mt ha^?1, respectively, and tilled into the soil to a depth of 20 cm. In 1974 an adjacent site was also revegetated with topsoil and lime but without sludge. Soil and plants were sampled 2, 4 and 16 yr following seeding. After 16 yr the total and DTPA-extractable Cu, Zn, Cr, Pb, Ni and Cd decreased in soils to nearly the levels of the control soils. Concentrations of metals in plants also decreased. Decreases in tissue concentrations ranged from 40 to 70% for Cu, Cr, Pb, Ni and Cd and up to 90% for Zn. The results showed that a single 100 mt ha^?1 application of sewage sludge containing high concentrations of metals was a cost-effective method for improving plant growing conditions on highly acidic soils.

     

Changes of Al and Heavy Metal Concentrations in Slovak Soils During the Last 25 Years

The objective of this study was to investigate changes of total concentrations and various extract-defined Al and heavy metal fractions in Slovak agricultural soils during the last 25 years. We compared 7 stored soil samples collected between 1966 and 1970 with samples collected in 1994 at the same sites. Seven fractions of Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn were determined with a sequential extraction procedure in all samples. Total concentrations of Cd, Zn, Mn, Ni, and Cu were lower in the 1994 samples; those of Al, Fe, Pb, and Cr were higher. Based on the initial concentrations, the average total concentration changes were: Cd(-10,3%)<Zn(-7,2%)<Mn(-4,8%)<Ni(-2,3%)<Cu(-1,4%)<Al(+2,1%)<Fe(+2,9%)<Cr(+7,4%)<Pb(+8,3%). This row is consistent with the decrease in metal mobility. The differences in salt-extractable metals showed the same pattern; however, changes were more pronounced than for total concentrations. The results suggest that decreases during the last 25 years are caused by higher leaching than deposition rates and increases vice versa. The highest increase in Cr and Pb concentrations is observed in the EDTA-extractable fraction, which mainly characterizes organically bound metals.     

Comparison of routine soil tests and EPA method 3050 as extractants for heavy metals in Delaware soils

Abstract

Agricultural use of sewage sludges can be limited by heavy metal accumulations in soils and crops. Information on background levels of total heavy metals in soils and changes in soil metal content due to sludge application are; therefore, critical aspects of long‐term sludge monitoring programs. As soil testing laboratories routinely, and rapidly, determine, in a wide variety of agricultural soils, the levels of some heavy metals and soil properties related to plant availability of these metals (e.g. Cu, Fe, Mn, Zn, pH, organic matter, texture), these labs could participate actively in the development and monitoring of environmentally sound sludge application programs. Consequently, the objective of this study was to compare three soil tests (Mehlich 1, Mehlich 3, and DTP A) and an USEPA approved method for measuring heavy metals in soils (EPA Method 3050), as extractants for Cd, Cu, Ni, Pb and Zn in representative agricultural soils of Delaware and in soils from five sites involved in a state‐monitored sludge application program.

Soil tests extracted less than 30% of total (EPA 3050) metals from most soils, with average percentages of total metal extracted (across all soils and metals) of 15%, 32%, and 11% for the Mehlich 1, Mehlich 3, and DTPA, respectively. Statistically significant correlations between total and soil test extractable metal content were obtained with all extractants for Cu, Pb, and Zn, but not Cd and Ni. The Mehlich 1 soil test was best correlated with total Cu and Zn (r=0.78***, 0.60***, respectively), while the chelate‐based extractants (DTPA and Mehlich 3) were better correlated with total Pb (r=0.85***, 0.63***). Multiple regression equations for the prediction of total Cu, Ni, Pb, and Zn, from soil test extractable metal in combination with easily measured soil properties (pH, organic matter by loss on ignition, soil volume weight) had R² values ranging from 0.41*** to 0.85***, suggesting that it may be possible to monitor, with reasonable success, heavy metal accumulations in soils using the results of a routine soil test.     

Chemical extractability and availability of heavy metals after seven years application of organic wastes to a citrus soil

Abstract. The chemical extractability of heavy metals introduced into the soil during 7 years application of sewage sludge, composted municipal solid waste and sheep manure, and their availability to citrus plants were studied. The total content of metals in the soil (0-20 cm)was increased by the use of sludges and compost, but only the Ni content in the saturation extracts of soil was significantly increased. Total Cd, Cr, Cu, Ni, Pb, and Zn were sequentially fractionated into water-soluble plus exchangeable, organically bound, carbonate-associated, and residual fractions. Most of the heavy metals were present in carbonate and residual fractions, although substantial amounts of water-soluble plus exchangeable Cd, and organically bound Cu and Ni were found. No significant increases in the metal contents in leaves and orange fruits were observed, with the exception of Pb in leaves. Several statistically significant correlations between metal content in plants, metal content in soil fractions, and chemical characteristics of soil were also found.     

Distribution of Trace Elements in Soils from the Sudbury Smelting Area (Ontario,Canada)

The sequential extraction procedure proposed by the European Commission Measurement and Testing Programme, combined with Scanning Electron Microscopy and Energy Dispersive X-ray Analysis(SEM/EDS), was applied to identify and quantify the chemical andmineralogical forms of Cu, Ni, Fe, Mn, Zn, Pb, Cr and Cd presentin the topsoil from a mining and smelting area near Sudbury (Ontario, Canada). The possible mobility of the chemical forms was also assessed. The metal fractions: (1) soluble and exchangeable, (2) occluded in manganese oxides and in easily reducible iron oxides, (3) organically bound and in form of sulphides, (4) residual mainly present in the mineral lattice structures were separated. Cu and Ni were the major metallic contaminants, occurring in soils in broad ranges of concentrations: Cu 11–1890 and Ni 23–2150 mg kg^-1. Cu was uniformly distributed among allthe extracted fractions. Ni was found associated mainly withthe residual forms, accounting for 17–92%, with an averageof 64%, of the total Ni present in the soils. Fe, Mn, Zn,Pb, Cr and Cd, while occurring in most analysed samples innormal soil concentrations, were primarily held in theresidual mineral fraction (on average >50%). The solubleand exchangeable forms made a small contribution (≤8.1%)to the total content of metals extracted. At least 14% ofthe total Cd, Mn and Pb was mobilised from the reducibleforms. The oxidizable fraction assumed mean values higher than10% only for Pb and Zn. Statistical treatment of the experimental data showed significant correlations between totalmetal content of the soils, some soil properties such as pH value, clay and organic matter content, and metal concentrationsin the various fractions. SEM/EDS analysis showed Fe in form ofoxides and sulphides in soils and Cu, Ni, Mn, Zn and Cr in association with iron oxides. Numerous black carbonaceous particles and precipitates of aluminium fluoride salts, observedin the solid residue left after `total’ digestion, were found tocontain Fe, Ni and Cr.