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.     

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.     

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.     

Cadmium,Lead, Copper,Zinc, and Nickel in Lettuce and Dry Beans as Related to Mehlich-3 Extraction in Three Brazilian Latossols

Lettuce (Lactuca sativa L.) and dry beans (Phaseolus vulgaris L.) were grown in three Brazilian Red-Yellow Latossols (Oxisols) in greenhouse conditions with cadmium (Cd), lead (Pb), copper (Cu), zinc (Zn), and nickel (Ni) applied to soils in treatments arranged as a randomized complete block design. Plant metals were analyzed in lettuce shoots and dry beans roots, stems, leaves, and seeds. After plant growth, soil samples from the pots were extracted with Mehlich-3 (M-3) for metal availability evaluation. The release of Ni in the M-3 extraction was dependent on the soil exchangeable aluminum (Al^{3 +}). Mehlich-3 was efficient for determination of availability of Cd, Pb, Cu, Zn, and Ni for dry beans and availability of Cd and Ni for lettuce. The dry bean leaves Cd, Pb, Cu, Zn, and Ni were highly correlated with their recovering from soils with M-3. The same was observed for Cd and Ni in lettuce shoots and the M-3 recovered metals from soils.     

在法国前铅和锌冶炼厂附近的城市土壤重金属的污染、分离和利用

smelters in Northern France were studied by analysing the chemical forms of these metals and evaluating their phytoavailability. These metals were determined using flame or electrothermal absorption atomic spectrometry （FAAS or ETAAS）, depending on their concentration levels. After optimisation of the ETAAS method, characteristic mass of In in water and aqua regia were 9.9 and 18 pg, respectively, showing the high sensitivity of the analytical Soil contamination by metals from anthropogenic activities （e.g., mining and smelting） is a major concern for the environment and human health. Environmental availability of cadmium （Cd）, lead （Pb）, zinc （Zn）, copper （Cu）, and indium （In） in 27 urban soils located around two former Pb and Zn smelters in Northern France were studied by analysing the chemical forms of these metals and evaluating their phytoavailability. These metals were determined using flame or electrothermal absorption atomic spectrometry （FAAS or ETAAS）, depending on their concentration levels. After optimisation of the ETAAS method, characteristic mass of In in water and aqua regia were 9.9 and 18 pg, respectively, showing the high sensitivity of the analytical procedure. Metal partitioning was conducted using a four-step sequential extraction procedure. The results showed that Cd and Zn were mainly in the acid-extractable and reducible forms in the urban soils studied. In contrast, Pb and In were largely in the reducible fraction. However, in some samples, the amount of In extracted in the residual or exchangeable fraction was higher than that in the reducible fraction. Copper was mainly found in the reducible and residual fractions. A pot experiment was conducted in a glasshouse with seven soils （six contaminated and one uncontaminated） and two plant species, ryegrass and lettuce. The results showed transfer of metals from the contaminated soils to the shoots of ryegrass and the edible part of lettuce. The metal bioconcentration factor was in the order of Cd Cu > In > Zn Pb for lettuce leaves, whereas for ryegrass shoots, three orders were found, Cd > Zn > Cu In > Pb, Cd ≥ In > Zn > Cu Pb, and Zn > Cd > Cu > In > Pb, depending on the physico-chemical properties of the soils, such as pH, cation exchange capacity, carbonates, and organic matter. It was established that the metal toxicity was related to the contamination levels and the physico-chemical properties, including pH, organic matter, and in a lesser extent, Ca, Mg, and phosphorus contents, of the soils. However, it was shown that lettuce could grow on soils having high Cd and CaCO₃ contents. Cadmium was one of the most available metals while Pb was always the least available in the soils studied.     

共培养对土壤重金属污染植物修复的调控作用

A co-culture of two plant materials, Astragalus sinicus L., a leguminous plant with concomitant nodules, and Elsholtzia splendens Naki-a Cu accumulator, along with treatments of a chelating agent (EDTA), root excretions (citric acid), and a control with E. splendens only were used to compare the mobility of heavy metals in chelating agents with a co-culture and to determine the potential for co-culture phytoremediation in heavy metal contaminated soils. The root uptake for Cu, Zn, and Pb in all treatments was significantly greater (P < 0.05) than that of the control treatment. However with translocation in the shoots, only Cu, Zn, and Pb in plants grown with the EDTA treatment and Zn in plants co-cropped with the A. sinicus treatment increased significantly (P < 0.05). In addition, when a co-culture in soils with heavy and moderate contamination was compared, for roots in moderately contaminated soils only Zn concentration was significantly less (P < 0.05) than that of heavily contaminated soils, however, Cu, Zn, and Pb concentrations of shoots were all significantly lower (P < 0.05). Overall, this "co-culture engineering" could be as effective as or even more effective than chelating agents, thereby preventing plant metal toxicity and metal leaching in soils as was usually observed in chelate-enhanced phytoremediation.     

The role of earthworms (<Emphasis Type="Italic">Eisenia fetida</Emphasis>) in influencing bioavailability of heavy metals in soils

The effects of earthworm (Eisenia fetida) activity on soil pH, dissolved organic carbon (DOC), microbial populations, fraction distribution and bioavailability of heavy metals (Zn, Cu, Cr, Cd, Co, Ni, and Pb) in five Chinese soils were investigated using pot experiments. A three-step extraction procedure recommended by the European Community Bureau of Reference (BCR; now Standards, Measurements and Testing Programme of the European Community) was used to fractionate the metals in soils into water soluble, exchangeable and carbonate bound (B1), Fe-oxides and Mn-oxides bound (B2) and organic matter and sulfide bound (B3). After the soils were treated with earthworms, the soil pH, water-soluble metal fraction and DOC increased. A significant correlation was obtained between the increased DOC and the increased metals in the water-soluble fraction. The heavy metals in fraction B1 increased after earthworm treatments, while those in fraction B3 decreased. No significant differences were observed for heavy metals in fraction B2. The microbial populations in soil were enumerated with the dilution plate method using several media in the presence of earthworms. The microbial populations increased due to earthworm activity. The biomass of wheat shoots and roots, and the heavy metal concentrations in wheat roots and shoots, were also increased due to the earthworm activity. The present results demonstrated that earthworm activity increases the mobility and bioavailability of heavy metals in soils.     

盐分胁迫下番茄盐分离子和重金属的分布特征

采用盆栽试验方法研究了不同盐分含量处理下番茄不同器官盐分离子（Na＋、K＋、Ca2＋）和重金属离子（Cd2＋、Pb2＋、Cr2＋、Zn2＋、Cu2＋、Ni2＋）的分布特征,探讨盐分离子对番茄不同器官吸收重金属离子的影响机制,为重金属污染盐渍土壤的农业可利用性评价提供科学依据。结果表明,番茄根、茎、叶和果实Na＋含量均随盐分含量增加而增加;番茄根K＋含量随盐分含量增加小幅上升,茎K＋含量则显著下降,叶K＋含量无显著变化;番茄各器官Ca2＋含量随盐分含量增加无明显变化。番茄根Cd、Pb、Cr、Zn和Cu含量以及番茄茎、叶Cd含量均随盐分含量增加而增加;番茄根Ni含量、番茄茎叶Pb、Cr、Ni、Zn和Cu含量以及番茄果实各重金属含量受盐分含量变化影响不大。因此,土壤盐分含量的增加对番茄根部吸收重金属（Ni除外）有促进作用。     

Zeitschrift für Pflanzenernährung und Bodenkunde: Schwermetallgehalt von Wurzel und Sproßorganen der Rebe (Vitis vinifera L.) nach Düngung mit Müll-Klärschlammkompost

Heavy metal content of roots and shoots of vines (Vitis vinifera L.) after fertilization with garbage-sewage-sludge-compost The enrichment of Zn, Cu, Pb, Cd, Co, Ni and Cr from garbage-sewage-sludge-compost in vineyard soils, vines and must was studied in field-and pot-experiments. The following results were obtained: 1. In a field experiment, in which garbage-sewage-sludge-compost was applied, a marked soil enrichment of Zn, Cu, Pb, Cd and Cr was found. It was most evident at the 0–20 cm depth but also obvious at the 40–60 cm depth thus indicating downward migration. The soil was not enriched with Co and Ni. The heavy metal content of leaves, berries and must of riesling vines did not increase on the plots treated with garbage-sewage-sludge-compost. 2. In a pot trial, using an acid and an alkaline soil each mixed with garbage-sewage-sludge-compost, it was observed that only the uptake of Zn and Cu increased into the leaves, tendrils and wood of the riesling cuttings. In relation to the content of the substrate, the heavy metals were detected in the roots percentually in the following order: Cu, Cd > Zn > > Pb, Co, Ni, Cr The root contents were mostly substantially higher than those of the shoot. The migration from root to shoot decreased in the following percentual order: Zn > Cu > Cd, Pb 3. The heavy metal content decreased considerably from the roots to the upper plant organs. This was reflected in low concentrations of heavy metals in the vine must.     

Distribution of different fractions of cadmium,zinc, lead,and copper in unpolluted and polluted soils

McLaren and Crawford's method for fractionating soil Cu was modified, and used to fractionate soil Cd, Zn, Pb, and Cu in 38 soil samples from 11 soil profiles from industrially polluted and nearby unpolluted areas. Pollutant metals, especially Cd and Zn, were more soluble than the native soil metals. On average, approximately 45% of Cd was present in the CaCl₂ soluble (CA) fraction, whereas corresponding values for the other metals were below 10%. The percentages of each metal in the CA fraction followed the order Cd > Zn > Pb > Cu. The same order was observed for the acetic acid soluble (AAC) fraction. Approximately 30% of total Pb and Cu were present in the pyrophosphate soluble (PYR) fraction, and only 10% of total Cd and Zn. Approximately 20% of total Zn or Pb and 10% of Cd or Cu were present in the free oxide (OX) fraction. Only 20% of Cd and between 40–50% of the other 3 metals were present in the residual (RES) fraction. The results show that Cd is more labile than the other 3 metals.     

养殖废水灌溉下施用生物质炭和果胶对土壤养分和重金属迁移的影响

【目的】 养殖废水中含有丰富的养分,但也含有一定的重金属。本文研究了生物质炭和果胶对养殖废水灌溉下的土壤–植物系统养分和重金属迁移规律的影响,以利用养殖废水中的养分,并对其重金属进行调控。 【方法】 选取新乡市郊区农田土壤为供试土壤,采用根箱试验方法种植玉米。设置根箱土壤中添加1%的生物质炭和果胶,分别灌溉蒸馏水和养殖废水发酵产生的沼液。测定了土壤中养分和重金属的含量,探讨了其在土壤–植物系统的迁移规律。 【结果】 沼液灌溉的植株地上部生长与蒸馏水灌溉无显著差异。果胶相比于生物质炭可以促进植株生长。沼液灌溉时,果胶处理的根系和地上部生物量分别比对照增加了25.38%和31.21%。沼液灌溉普遍降低了根际和非根际土壤的pH,生物质炭处理和果胶处理与对照根际和非根际土壤的pH均无显著差异。沼液灌溉增加了非根际土壤的电导,生物质炭相比于果胶增加了土壤的电导。沼液灌溉增加了土壤全氮、有效磷、速效钾和有机质含量。果胶根际土壤的全磷、碱解氮、有效磷、有效Fe、有效Mn均高于生物质炭处理,生物质炭处理根际和非根际土壤的全钾和速效钾含量均高于果胶处理。沼液灌溉相比于蒸馏水灌溉,增加了植株根、茎中N含量和Ca含量。生物质炭处理植株根茎叶N含量、根茎P含量、茎K含量、根茎叶Ca含量、根茎Mg含量高于果胶处理,但果胶处理养分的转运系数较高。养殖废水灌溉增加了根际和非根际土壤中有效Cu和Zn尤其是Zn的含量。与对照相比,生物质炭降低了根际土壤Cu、Pb、Ni的含量,而果胶增加了它们的含量。沼液灌溉增加了植株根茎叶中Cu、Zn、Pb含量,果胶处理植株根系Cu、Zn、Pb、Cd、Ni含量最高,但向地上部转运较少。 【结论】 在北方碱性土壤灌溉养殖废水发酵产生的沼液时,施用生物质炭和果胶可以提高土壤肥力和植株养分含量,生物质炭通过减少土壤中有效态重金属含量以减少重金属在植物体内累积,果胶虽然增加土壤有效态重金属含量,但可以降低其向地上部的转运,避免了重金属在植物体内的累积。      

复合污染土壤中水稻根际元素特性及效应研究

【目的】以广东大宝山重金属复合污染农田为生长介质,通过研究水稻不同部位生长量、 金属含量、 对金属的富集系数,及其与根际、 非根际土金属含量、 形态变化的相关关系,探讨根际效应可能对水稻体内金属积累转运以及生物量的影响。【方法】选取了广东大宝山稻田重金属复合污染(As、 Pb、 Fe、 Cu、 Zn)土壤及当地常见的20个水稻品种进行根际袋试验,即将根际袋内的土视为根际土,根际袋外的土视为非根际土,将供试水稻品种种植于根际袋土壤中60天后收获,测定水稻各部位的生长量、 不同金属的含量,根际土和非根际土中各金属有效态的含量。【结果】Fe、 Cu、 Pb、 Zn、 As在根部的富集系数均大于其在茎叶的富集系数,各金属在茎叶和根部的富集能力排序分别为Zn Cu As ≈ Pb ≈ Fe和Fe Zn As Cu Pb。根际土和非根际土中各种金属有效态含量均为Fe Cu Pb Zn As。研究还发现,有效态Fe、 Cu和Zn浓度对整株干重的影响显著,作用强弱顺序为Cu Zn Fe,对水稻生长影响作用显著的三种有效态金属Fe、 Cu和Zn均为植物生长所必需的元素。供试土壤中有效态Cu浓度对水稻的生长所起的作用最强。根际土有效态Fe浓度对根系Fe的积累作用效果显著,有效态As浓度显著抑制了根系Fe的积累,且有效态As浓度的作用强于有效态Fe。【结论】根际土中有效态Fe对株高、 根干重、 茎叶干重和整株干重均起着抑制作用,有效态Cu对水稻生长起到了促进作用。根际土有效态As和非根际土有效态Zn对根部Fe的积累起到了抑制作用,根际土有效态Fe和非根际土有效态Cu则起到了促进作用。非根际土有效态Fe和有效态Zn对水稻根长的增加均起到了促进作用。     

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.     

Fractionation and Prediction of Copper,Lead, and Zinc Uptake by Two Leaf Vegetables from Their Geochemical Fractions in Urban Garden Fields in Northern Nigeria

The bioavailability and mobility of heavy metals in soil are strongly influenced by the chemical or geochemical species of the metals in soils. We determined the geochemical fractions of copper (Cu), lead (Pb), and zinc (Zn) in garden soils, using the seven-step Zeien and Bruemmer fractionation scheme in relation to metal uptake by two leaf vegetables (lettuce, Latuca sativa, and amaranthus, Amaranthus caudatus). Our objective was to develop predictive models for assessing the lability of these metals from the soil metal fractions. The sums of fractions of Cu, Pb, and Zn did not differ by more than 10% from the “pseudo” total concentrations of the metals determined independently by aqua regia digestion. The general distribution of Cu and Pb among the soil fractions was in the order organic-matter-bound > Fe_o and Fe_c > Mn_ox > exchangeable > residual > mobile, except for Cu, where residual and the exchangeable were reversed. Zinc was fairly evenly distributed among organic matter (20%), Fe_o (22%), Fe_c (20%), and residual (21%). Averaged across sites, Cu, Pb, and Zn concentrations in the lettuce were almost twice as great as the concentrations in amaranthus even though they were raised in the same fields. The variance in Cu, Pb, and Zn uptake by amaranthus was predicted up to 51–99% from soluble, exchangeable, organic matter, and Fe_o-bound fractions; the variance in metal uptake by lettuce was best predicted from Fe_c- and Fe_o-bound fractions up to 76–90%. Our results indicated differential accessibility to metal fractions by lettuce and amaranthus grown in the same field.     

水稻子实对不同形态重金属的累积差异及其影响因素分析

在分析成都平原核心区土壤重金属(Cd、Cr、Pb、Cu、Zn)全量、各形态含量及相应点位种植的水稻子实重金属含量的基础上,通过统计分析、空间插值及线性回归方程的模拟,研究了土壤Cd、Cr、Pb、Cu、Zn全量的空间分布状况、各形态重金属含量统计特征,以及水稻子实对重金属各形态的累积差异及其影响因素。结果表明,成都平原水稻土重金属污染较轻,除Cd外,均低于国家土壤环境质量二级标准。土壤中重金属的可交换态含量均较低,Cd主要以铁锰氧化态存在,Cr、Cu、Zn、Pb主要以残渣态存在。水稻子实对5种重金属的累积效应顺序为:Cd>Zn>Cu>Pb>Cr。与水稻重金属累积关系密切的重金属活性形态(可交换态、碳酸盐结合态、铁锰氧化物结合态和有机物结合态)主要有:Cd的碳酸盐结合态、Cr的可交换态、Pb的有机物结合态和Cu的碳酸盐结合态含量;Zn各活性形态对水稻子实含量的影响不明显。土壤理化性质对不同活性形态重金属元素的影响效应各不相同。活性态Cd主要受有机质、pH和容重的影响;活性态Cr与pH、有机质、CEC和容重密切相关;活性态Pb与有机质、容重、中细粉粒、砂粒等均有密切的关系;Cu的活性主要受粘粒、有机质含量的影响;Zn的有效性主要受pH、有机质、砂粒、容重的影响。总的看来,对土壤Cd、Cr、Pb、Cu、Zn各活性形态含量影响效应较强的是有机质、pH、容重,而与土壤吸附性能密切相关的颗粒组成、CEC的影响不甚明显。     

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。     

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.     

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.     

Metal Extractability in Binary and Multi-metals Spiked Calcareous Soils

In the present study, a laboratory experiment was designed to compare the 0.01 M calcium chloride (CaCl₂) and diethylenetriaminepentaacetic acid (DTPA) extraction methods for their ability to predict cadmium (Cd), copper (Cu), iron (Fe), Manganese (Mn), nickel (Ni), and zinc (Zn) availability and mobility in five calcareous soils. The soils were spiked with different amounts of metals (0, 50, 100, 200, and 400 mg kg^?1) both in binary (Cu and Zn; Ni and Cd; Fe and Mn) and in multi-systems (Cd, Cu, Fe, Mn, Ni, and Zn) and incubated for 1 months at field capacity. In metal-spiked soils, both extraction methods showed a linear relationship of extractable to total metals for all soils. The fraction of total metals extracted by DTPA was much higher than the fraction extracted by CaCl₂, which was attributed to the formation of soluble metal-complexes in the complexing extracts calculated by the Visual Minteq program. DTPA extraction method showed higher selectivity for Cu over other metals both in binary and in multi-systems. Different order of metals extractability was found in binary and multi-systems for both extraction methods. Solid/solution distribution coefficient (K_d) was calculated by the ratio of the solid phase to soil solution concentration of metals extracted by CaCl₂ or DTPA extraction methods. Both in binary and in multi-systems, the average K_d (l kg^?1) of metals by soils were in the order of Mn (5398) > Fe (4413) > Zn (3376) > Cu (2520) > Ni (969) > Cd (350) in the CaCl₂-extractable metals and Fe (35) ≥ Ni (34) > Zn (18) > Mn (11.2) > Cu (6.3) > Cd (4) in the DTPA-extractable metals. Results showed that among the six studied metals, Cd had the lowest K_d, implying a relative higher mobility in these calcareous soils. The Visual Minteq indicated that in the CaCl₂-extraction method and in both binary and multi-systems the dominant species for Cu, Mn, Ni, and Zn were Cu²⁺, Mn²⁺, Ni²⁺ and Zn²⁺, respectively, while for Cd and Fe, the dominant species were CdCl⁺ and Fe(OH)²⁺, respectively.     

Sequential fractionation and plant availability of heavy metals as affected by sewage sludge applications to soil

Abstract

The effect of sewage sludge applications on extractability and uptake by chard and lettuce of soil cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni), leaf (Pb), and zinc (Zn) was investigated. Ten different treatments (0, 150, 300, and 500 kg N ha^‐1) as mineral fertilizer, and 400, 800, and 1,200 kg N ha^‐1 of aerobically and anaerobically‐digested sewage sludges were applied annually to a sandy‐loam soil since 1984. Seven years after the start of the treatments, higher levels of heavy metals were detected in the soil, depending on the type of metal, depth of sampling, type of sludge used, and, especially, rate of application. Following a sequential extraction procedure incorporating 0.1M CaCl₂, 0.5M NaOH, and 0.05M Na₂EDTA, most of the heavy metals in soil were detected in the Na₂EDTA solution and the residual fractions. Large amounts of Cd appeared to be extracted by CaCl₂, whereas substantial amounts of Cu and Ni were isolated by NaOH. The effect of treatments on the percentages of the metals found in each fraction depended on the type of metal, sampling depth, sludge used, and application rate. No significant increases were found in the heavy metal contents of chard and lettuce leaves, but some of the treatments resulted in a significant decrease of Cd and Cr levels in lettuce leaves.