Retention of Ni,Zn and Cd by Si-associated goethite

Synthetic goethite used to study the effects of reaction time and temperature on the pH-dependent sorption of Ni, Zn and Cd was associated with amorphous silica. Ni interacted with dissolved Si and formed a Ni/Si precipitate on the goethite surface. Individual metals added at a concentration of 0.5 μmol g^?1 and sorbed during a reaction period of 504 hours (21 days) at 35°C were extracted by 0.7 M HNO₃ for 14 days. At the end of this period 11,28 and 40 percent of Ni, Cd and Zn, respectively, were not extracted whereas 20 percent of the total Fe content of the goethite and 39 percent of the associated Si were dissolved. During the sorption process metals became immobilized in the goethite particles. This effect can be related to a diffusion of metal ions into micropores. A total mobilization of sorbed metals can only be achieved by a complete dissolution of the goethite. The strong fixation of Ni, Zn and Cd by goethite suggests that additions of this Fe oxide could be used to ameliorate highly contaminated sludges or soils.     

Influence of different temperatures on metal tolerance measurements and growth response in bacterial communities from unpolluted and polluted soils

The effects of temperature on the growth rate and metal toxicity in soil bacterial communities extracted from unpolluted and polluted soils were investigated using the thymidine and leucine incorporation techniques. An agricultural soil, which was contaminated in the laboratory with Cu, Cd, Zn, Ni or Pb, and an uncontaminated forest soil were used. Measurements were made at 0°C and 20°C. Leucine incorporation was found to be as sensitive to heavy metals as thymidine incorporation in the short-term trial used to indicate heavy metal tolerance. Similar IC₅₀ values (the log of the metal concentration that reduced incorporation to 50%) were also obtained at 0 and 20°C, independently of the technique used. Metal tolerance could thus be measured using both techniques at any temperature in the range 0–20°C. In the long-term experiment different temperature-growth relationships were obtained on the basis of the rate of thymidine or leucine incorporation into bacterial assemblages from unpolluted and polluted soils, as judged from the minimum temperature values. This could not be attributed to the metal addition alone since different patterns were observed when different metals were added to the soil. Thus, the minimum temperature for thymidine incorporation was similar in Cu-polluted and unpolluted soil, while in soils polluted with Cd and Zn the minimum temperature increased by 2°C, and Ni and Pb additions increased the minimum temperature by 4°C compared to the unpolluted soil. This suggested that heavy metal pollution led to bacterial communities showing different temperature characteristics to those in the corresponding unpolluted soil. Similar observations were deduced from the minimum temperatures required for leucine incorporation. Three groups of bacterial communities were distinguished according to the growth response to temperature in polluted soils, one group in Cu-polluted soil, a second group in soil polluted with Zn and Cd, and a third group in soils polluted with Ni and Pb.     

Additive effects of copper and zinc on cadmium toxicity on phosphatase activities and ATP content of soil as estimated by the ecological dose (ED50)

The ecological dose (ED₅₀) of Cd on alkaline and acid phosphatase activity and the ATP content of three contrasting forest soils was measured with or without Cu and Zn to assess the additive toxic effects of these two metals. Soils polluted with Cu and/or Zn were treated with increasing Cd concentrations to give the following metal combinations: Cd, Cd+Cu, Cd+Zn and Cd+Cu+Zn. Alkaline and acid phosphatase activities and ATP content of the three soils were analysed 4 h, 7 and 28 days after the metal additions. The ED₅₀ values were obtained by interpolating the enzyme activities or ATP data with a kinetic model and the goodness of fit was satisfactory.Generally, the ED₅₀ values of both acid and alkaline phosphatase activities for Cd were lower (higher toxicity) with than without Cu and Zn and the effect of Cu and Zn was particularly adverse when these two metals were both added to soils. The alkaline phosphatase was more sensitive in the acid and neutral soil whereas the acid phosphatase was more sensitive in the alkaline soil. Both phosphatase activities and the ATP content were more sensitive in the sandy than in the finer textured soils. The ATP content was less sensitive to the additive effects. Increasing toxicity was observed during the incubation.Analysis of 1 M NH₄NO₃-extractable Cd, Cu and Zn revealed that Cd competed with Zn for the adsorption sites but not with Cu. However, the lower ED₅₀ values for Cd of the two phosphatase activities and of the ATP content in the presence of heavy metal combinations could be not explained by the heavy metal solubility data. It is concluded that the ED₅₀ may be a sensitive tool for assessing additve toxic effects to soil biochemical parameters.     

The effect of EDTA on the extractability of Zinc (Zn), Cadmium (Cd) and Nickel (Ni) in Vertisol and Alluvial soils

Ethylendiamintetraacetic acid (EDTA) is persistent in the environment. The presence of EDTA in soil may alter the mobility and transport of Zn, Cd and Ni in soils because of the formation of water soluble chelates, thus increasing the potential for metal pollution of natural waters. Mobility of metals is related to their extractability. To investigate metal extractability affected by EDTA, Zn, Cd and Ni were added to Vertisol and Alluvial soil at rates of 50, 2 and 5 mg kg^-1, respectively. Both natural and metal amended soils were treated with Na₂EDTA at rates of 0; 0.2 and 0.5 mg kg^-1. After five months of incubation soil samples were extracted with 0.1 N HCl, 0.005 M DTPA + 0.01 M CaCl₂ + 0.1 M TEA (0.005 M Diethylenetriaminepentaacetic acid + 0.01 M Calcium cloride + 0.1 M Triethanolamine) and 1 M Mg(NO₃)₂, the latter of which extracts the exchangeable from of metald (Zn, Cd and Ni).

According to experiment results, Zn, Cd and Ni in all extraction increased with increasing rates of EDTA in the natural and metal amended soils.     

Role of soil constituents in fixation of soluble Zn, Cu, Ni and Cd added to soils

Slow immobilization of trace metals in soil, termed ‘fixation’, affects their natural attenuation but it is still unclear which reactions occur. Twenty‐eight soils were selected to assess the role of Fe oxides and carbonates on fixation of Cu, Cd, Zn and Ni. Soils included samples from 2 toposequences (Vietnam, Spain) and 13 European topsoils with different soil characteristics (pH 3.4–7.7). Samples were amended with 250 mg Zn kg⁻¹, 100 mg Cu kg⁻¹, 80 mg Ni kg⁻¹ and 2.5 mg Cd kg⁻¹ as metal salts and incubated for 850 days. Fixation was measured as the increase of the fraction of added metals that were not isotopically exchangeable. Fixation increased with time and was, averaged over all the soils, 43% (Cu), 41% (Zn), 41% (Ni) and 28% (Cd) after 850 days. Metal fixation within samples from each toposequence was generally positively related to total Fe oxide concentration (Fe_d) for Zn, Ni and Cd. However, the fixation of Cd, Zn and Ni was mainly explained by pH and not by Fe_d when considering all soils. Fixation of Zn and Cd in soils with pH >7.0 increased with increasing concentrations of carbonates at initial ageing times. Fixed fractions of Zn, Ni and Cd were significantly released when experimentally removing 50% of carbonates by acidification. Fixation of Cu was most poorly related to soil properties. Our data suggest that fixation of Cd, Zn and Ni is related to a pH‐dependent diffusion into oxides and that of Cd and Zn also to diffusion and/or coprecipitation in carbonates. Fixation of Ni at neutral pH may also be related to stabilization of precipitates that form readily in soil.     

酸雨地区蔬菜对重金属的吸收及重金属健康风险基准的估算

通过盆栽实验,以小白菜(上海青)、大白菜和萝卜为指示作物,研究了酸雨作用下Cu,Zn,Pb,Cd,Cr和Ni复合污染物在土壤-作物系统中的吸收与富集情况。结果表明,酸雨-重金属复合污染处理使Cu,Pb,Cr和Ni在蔬菜中积累量明显高于对照处理;Zn和Cd一般只有在复合污染处理中外源Zn或Cd含量较高时才明显高于对照处理。与对照相比,酸雨-重金属复合污染处理使Pb和Ni的富集系数增大,Cu的富集系数多数情况下增大,Cd的富集系数多数情况下减小,Zn和Cr富集系数的变化在不同蔬菜之间存在较明显的差异;重金属在不同蔬菜中的富集系数一般表现为萝卜>上海青>大白菜,蔬菜中不同重金属富集系数一般表现为Zn>Cd>Ni>Cu>Pb>Cr。酸雨-重金属复合污染条件下蔬菜中重金属积累量与其在土壤中总量之间的相关性均达到显著或极显著水平。以大宗蔬菜上海青、大白菜和萝卜为指示作物对酸雨地区蔬菜地中重金属的健康风险基准进行了估算,这对开展酸雨地区土壤重金属环境容量评价、重金属污染修复目标及地方性土壤环境质量标准的制订提供了参考依据。     

Chemical pools of cadmium, nickel and zinc in polluted soils and some preliminary indications of their availability to plants

This study was conducted to determine the chemical distribution and plant availability of Cd, Zn and Ni in eight metal-polluted soils in southern Ontario, Canada. There were altogether 30 different soil samples because two of the soils had received various sewage sludge treatments. The soils were sequentially extracted with 1 m ammonium acetate to remove soluble plus exchangeable metals, with 0.125 m Cu(II) acetate to remove complexed metals, and with 1 m HNO₃ to dissolve chemisorbed or occluded metals and precipitates such as oxides and carbonates. Expressed as a percentage of the metal so extracted, exchangeable Cd and Zn and Ni; complexed Cd and Zn>Ni and Ni>Zn>Cd in the acid-soluble pool. With a few exceptions (soils with high organic matter content or low pH) at least 50 per cent of the extracted metal was in the acid-soluble pool. The percentage of metal complexed was significantly correlated with organic matter content. The percentage of metal in the acid-soluble fraction was significantly correlated with soil pH. Preliminary findings based on the results with two soils suggested that for Cd and Zn plant availability was correlated with the concentrations of exchangeable, complexed or acid-soluble pools of Cd and Zn.     

长期化肥配施不同有机肥对土壤和玉米中重金属累积的影响

  【目的】  明确长期化肥配施有机肥对重金属元素在土壤和农作物籽粒、秸秆中积累的影响及其环境效应,为安全高效施肥提供科学依据。  【方法】  在北京市农林科学院新型肥料长期定位试验站进行了为期10年的田间试验,其种植模式为冬小麦–夏玉米轮作,试验处理为不施肥 (CK)、单施化肥 (NPK)、氮磷钾 + 鸡粪堆肥的有机肥料 (NPKJF)、氮磷钾 + 污泥堆肥的有机肥料 (NPKWN)、氮磷钾 + 垃圾堆肥的有机肥料 (NPKLJ) 和氮磷钾 + 秸秆粉碎还田 (NPKJG) 共6个处理,施肥处理依据等氮量施肥原则,每季作物施 N 180 kg/hm2、P₂O₅ 90.0 kg/hm2、K₂O 90.0 kg/hm2。在玉米收获后测定了玉米秸秆、籽粒和0—20 cm耕层土壤中重金属全量。  【结果】  添加污泥处理显著提高了土壤中Cd、Hg、As、Cu、Zn的含量,单因子污染指数分别比对照提高了45.10%、150.00%、104.00%、44.60%、65.80%。不同施肥处理对土壤中全量Cd、Cr、Hg、Cu、Zn存在一定的富集效果。各处理重金属单项污染指数在0.02～0.46,远小于1,综合污染指数为0.23～0.36,均小于0.7,试验区土壤重金属均为无污染等级。施用有机废弃物堆肥的处理玉米籽粒Cd、Cu、Zn含量比对照显著增加,各处理间Hg、As、Cr、Pb、Ni含量差异不显著,连续10年定位施肥后试验站土壤以及玉米籽粒中重金属含量均未超标。同一作物不同部位对重金属的富集能力不同,玉米秸秆对重金属的富集能力大于籽粒。玉米籽粒中Pb、Cu、Zn含量与土壤Pb、Cu、Zn含量存在正相关性,玉米秸秆中Cd、Hg、Cr、Ni含量与土壤中Cd、Hg、Cr、Ni含量呈正相关或者显著负相关。  【结论】  在施氮总量不变的前提下,连续施用供试有机堆肥10年后,土壤重金属含量均未超标,土壤重金属单项污染指数在0.02～0.46,综合污染指数为0.23～0.36,无污染风险。只有污泥堆肥需要加强土壤Cd的监测。玉米秸秆对重金属的富集能力大于籽粒。玉米籽粒中Pb、Cu、Zn含量与土壤相应重金属含量存在正相关性,秸秆中Cd、Pb、Hg、Zn与Cr、Ni含量与土壤中相应重金属含量呈正相关,而秸秆中Cr、Ni含量与土壤中相应重金属含量呈负相关。     

The Influence of Heavy Metals on Carbon Dioxide Evolution from a Typic Xerochrept Soil

In a laboratory study the effects on soil respiration of trace metals (Ni, Cd, Cu, Mn, Pb, Zn)added at loading rates ranging from 0 to 1000 µg g-1 were determined. Differences intoxicity with respect to the type of metal salt added were also evaluated. The inhibitory effect onsoil respiration differed considerably among the heavy metals and increased with the increasingloading rate. No linear relationships were found between the degree of inhibition and the levels oftotal and available metals. Toxicity evaluation at 20 and 50% inhibition of soil respiration showedCu as the most toxic and Mn as the most tolerable metal. A ‘metal equivalent’ was calculated asthe sum of the amounts of the available metals weighted to their relative toxicity with respect tothe least toxic one: Mn equivalent = Mn + 1.9Pb + 2.1Ni + 2.5Zn + 6.7Cd + 6.7Cu. The ionicpotential of the heavy metals was found to be positively related to the percent inhibition of soilrespiration. Chlorides and sulphates appeared to depress soil respiration more than nitrates, thelatter counter-balancing the toxic effect of the heavy metals.     

Soil microbial biomass estimates in soils contaminated with metals

The validity of the chloroform fumigation-incubation procedure for measuring soil microbial biomass in field soils contaminated with metals (e.g. Cu, Ni, Zn, Cd) was assessed. The metal contamination was the result of past sewage sludge additions and the contaminated field soils now contain metals at about current maximum U.K. recommended levels. The decomposition of native soil biomass or microbial material added after fumigation was little affected by the presence of metals and it was concluded that fumigation-incubation is a reliable procedure for measuring biomass in soils contaminated with moderate amounts of metals. This conclusion was confirmed by direct microscopy: similar soil biomass estimates were obtained by both methods.     

Extractability and plant uptake of heavy metals in alum shale soils

Abstract

Fifty soil samples (0–20 cm) with corresponding numbers of grain, potatoes, cabbage, and cauliflower crops were collected from soils developed on alum shale materials in Southeastern Norway to investigate the availability of [cadmium (Cd), copper (Cu), zinc (Zn), lead (Pb), nickel (Ni), and manganese (Mn)] in the soil and the uptake of the metals by these crops. Both total (aqua regia soluble) and extractable [ammonium nitrate (NH₄NO₃) and DTPA] concentrations of metals in the soils were studied. The total concentration of all the heavy metals in the soils were higher compared to other soils found in this region. Forty‐four percent of the soil samples had higher Cd concentration than the limit for application of sewage sludge, whereas the corresponding values for Ni, Cu, and Zn were 60%, 38%, and 16%, respectively. About 70% the soil samples had a too high concentration of one or more of the heavy metals in relation to the limit for application of sewage sludge. Cadmium was the most soluble of the heavy metals, implying that it is more bioavailable than the other non‐essential metals, Pb and Ni. The total (aqua regia soluble) concentrations of Cd, Cu, Zn, and Ni and the concentrations of DTPA‐extractable Cd and Ni were significantly higher in the loam soils than in the sandy loam soils. The amount of NH₄NCyextractable metals did not differ between the texture classes. The concentrations of DTPA‐extractable metals were positively and significantly correlated with the total concentrations of the same metals. Ammonium nitrate‐extractable metals, on the other hand, were not related to their total concentrations, but they were negatively and significantly correlated to soil pH. The average concentration of Cd (0.1 mg kg^‐1 d.w.) in the plants was relatively high compared to the concentration previously found in plants grown on the other soils. The concentrations of the other heavy metals Cu, Zn, Mn, Ni, and Pb in the plants were considered to be within the normal range, except for some samples with relatively high concentrations of Ni and Mn (0–11.1 and 3.5 to 167 mg kg‘¹ d.w., respectively). The concentrations of Cd, Cu, Zn, Ni, and Mn in grain were positively correlated to the concentrations of these respective metals in the soil extracted by NH₄NO₃. The plant concentrations were negatively correlated to pH. The DTPA‐extractable levels were not correlated with plant concentration and hence DTPA would not be a good extractant for determining plant availability in these soils.     

LONG-TERM TRANSFORMATIONS AND REDISTRIBUTION OF POTENTIALLY TOXIC HEAVY METALS IN ARID-ZONE SOILS INCUBATED: I. UNDER SATURATED CONDITIONS

Solid-phase transformations of Cd, Cu, Cr, Ni and Zn, added as soluble salts at several levels to two arid-zone soils, were studied over a period of one year. The soils were maintained under a saturated-paste regime and sampled periodically. A selective sequential dissolution procedure was employed to determine the changes in metal distribution among six operationally defined solid-phase fractions. A function,U _ts was introduced to measure the fractional attainment of equilibrium of the soils following a perturbation. The direction and rate of redistribution of the added metals in the soils were affected by the nature of the metal, the soil properties and the metal loading level. Cd added to the soils was transferred from the exchangeable (EXC) into the carbonate (GARB) fraction. When soluble Cu, Cr, Ni and Zn were added at low loading levels, metals were transferred from the reducible oxides(RO) bound and easily reducible oxides (ERO) bound fractions and the EXC fraction, into the CARB fraction. However, at the higher loading level, metals were transferred from the EXC and CARB fractions into the organic matter bound (OM), ERO and RO fractions. TheU _ts function approached lower values as incubation continued but remained removed from 1. The overall flux of metals among fractions was the combined result of the readjustment of the metals in the native soil to changing conditions due to saturation, and the transfer of added soluble metals to the less labile fractions.     

After effects of metals derived from a highly metal-polluted sludge on maize (Zea mays L.)

High Cd and Ni concentrations in sandy soils were built up in a field experiment, receiving an unusually metal-polluted sewage sludge between 1976 and 1980, at Bordeaux, France. The study evaluates the availability of metals and their after effects on maize at one point in time, the 8th year following termination of sludge application (1988). Plant parts (leaves, stalks, roots, grains) and soil samples were collected from plots which received 0 (Control), 50 (S1) and 300 Mg sludge DW ha^?1 (S2) as cumulative inputs. Dry-matter yield, plant metal concentrations, total, and extractable metals in soils were determined. Metal inputs resulted in a marked increase in total and extractable metals in soils, except for extractable Mn and Cu with either 0.1 N Ca(NO₃)₂ or 0.1 N CaCl₂. Total metal contents in the metal-loaded topsoils (0–20 cm depth) were very often lower, especially for Cd, Zn, and Ni, than the expected values. Explanation was partly given by the increases of metal contents below the plow layer, particularly for Cd at the low metal loading rate, and for Cd, Ni, and Cu at the high one (Gomez et al., 1992). In a control plot beside a highly metal- polluted plot, Cd, Zn, and Ni concentration in soil increased whereas the concentration of other metals was unchanged; lateral movement, especially with soil water, is plausible. Yield of leaves for plants from the S2 plot was reduced by 27%, but no toxicity symptoms developed on shoots. Yields of stalks for plants in both sludge-treated plots numerically were less than the controls but the decrease was not statistically significant. Cd and Ni concentrations increased in all plant parts with metal loading rate while Mn concentrations decreased. Leaf Cd concentration in plants from sludge-treated plots (i.e. 44 and 69 mg Cd kg^?1 DM for S1 and S2) was above its upper critical level (i.e. dry matter yield reduced by 10%: 25μg Cd g^?1 DM in corn leaves, Macnicol and Beckett, 1985). Yield reduction at the high metal-loading rate was probably due to 3 main factors: Mn deficiency in leaves, the accumulation of Ni especially in roots, and the increase of Cd in leaves. The amount of metal taken up by plants from the control plot ranked in the following order (mole ha^?1): Fe(22)? Mn(7)>Zn (5.6)?Cu (0.7), Ni (0.6), Cd (0.4). For sludge-treated plots, the order was (values for S1 and S2 in mole ha ^?1): Fe (16, 15)>Zn (7.9, 7.7)>Ni (4.3, 4.7)>Cd (1.9, 2.1)>Cu (1.0,1.2), Mn (1.5, 1.1). Zn and Cd had the greatest offtake percent from the soil to the above ground plant parts. Cd or Ni uptake by maize were correlated with extractable metals by unbuffered salts (i.e. 0.1 N Ca(NO₃)₂ and 0.1 N CaCl₂). It is concluded that part of the sludge-borne Cd and Ni can remain bioavailable in this sandy soil for a long period of time (e.g. 8 yr) after the termination of metal-polluted sludge application.     

包头市铜厂周边土壤中重金属垂直分布特征与形态分析

为了解包头市铜厂周边地区土壤剖面中重金属污染状况,采用火焰原子吸收分光光度法和Tessier连续提取法,对土壤中6种重金属（Cu,Zn,Mn,Ni,Pb和Cd）的垂直分布特征、形态及潜在生物可利用性进行了分析。结果表明:研究区土壤剖面各层土壤中6种重金属含量均超过内蒙古土壤背景值,Cu,Pb和Cd为主要污染物。随采样深度的增加,Cu,Zn,Pb和Mn的含量呈现下降趋势,且由相关性系数可知重金属Cu,Zn和Pb可能有相同人为或自然污染源;土壤剖面中6种重金属均主要以残渣态存在,含量均在50%以上,对生物危害较小;潜在生物可利用性分析结果为:Cu（32.61%） > Mn（31.85%） > Ni（24.90%） > Zn（16.60%） > Cd（15.23%） > Pb（14.87%）,Cu和Mn的潜在生物可利用性较大,其次为Ni,Zn,Cd和Pb潜在生物可利用性较小。     

Applications of fertilizer cations affect cadmium and zinc concentrations in soil solutions and uptake by plants

A pot experiment was conducted to study changes over time of Cd and Zn in soil solution and in plants. Radish was grown in a soil which had been contaminated with heavy metals prior to 1961. Constant amounts of a fertilizer solution (NH₄NO₃, KNO₃) were added daily. Soil solution was obtained at intervals by displacement with water. The cumulative additions of small amounts of fertilizers were made equal to the plants' requirements at the final harvest but were found to exceed them during most of the experiment. Excess fertilizers caused substantial increases of major (K, Ca, Mg) and heavy-metal (Cd, Zn) ions in soil solutions and a decrease in soil pH, probably due to ion-exchange mechanisms and the dissolution of carbonates. Uptake of Cd and Zn into leaves was correlated with the mass flow of Cd (adjusted r²= 0.798) and Zn (adjusted r²= 0.859). Uptake of K, Ca and Mg by the plants was independent of their concentrations in solution. It is concluded that, in order to study effects of plants on heavy-metal availability and obtain soil solution that has not been altered by fertilizer ions, nutrients must be added according to the needs and growth of the plants. This could be achieved by linking fertilizer additions to the rate of transpiration, as nutrient uptake and transpiration were closely correlated in this experiment.     

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.     

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.     

重金属复合处理对小麦锌铜镍镉积累和分布的影响

为增加粮食可食用部分有益元素的浓度,同时减少有毒重金属元素的含量,需要更好地了解元素在植株和籽粒内的运输和分布。在温室盆栽条件下,以春小麦为供试材料,设置对照（不添加重金属）和重金属复合处理（同时添加铜、锌、镍、镉,以不影响小麦生长为前提）,研究锌（Zn）、铜（Cu）、镍（Ni）、镉（Cd）在成熟植株和籽粒不同部位的分布特点。结果表明,重金属复合处理对小麦成熟期籽粒和秸秆产量、收获指数以及粒重均无显著影响,但使小麦各器官重金属浓度均显著增加,增幅因不同器官和不同元素而异,籽粒中Zn、Cu、Ni和Cd浓度分别增加1.8、0.5、48.1倍和45.3倍。重金属复合处理还显著改变了Zn和Ni在地上部各器官中的分配模式：对照小麦吸收的Zn更易向生殖器官中转运,处理植株则更多地滞留在营养器官中,而Ni呈相反的趋势。激光剥蚀电感耦合等离子体质谱仪（LA-ICP-MS）对籽粒糊粉层和胚乳的定量分析表明,重金属复合处理使糊粉层Zn和Cu浓度仅增加了78%和86%,而糊粉层Ni和Cd浓度分别增加了30倍和121倍。重金属复合处理使胚乳Zn和Cu浓度分别增加了49%和48%,使Ni和Cd浓度均超出小麦标准中Ni和Cd的最大允许浓度（对照籽粒胚乳中没有检验到Ni和Cd）。以上结果表明,在小麦生物强化实践中,在增加有益营养元素（如Cu和Zn）的同时亦存在有毒重金属（如Ni和Cd）超标的巨大风险。     

Kinetics of Desorption of Heavy Metals from Polluted Soils: Influence of Soil Type and Metal Source

Kinetics of desorption of heavy metal ions (Cd, Cu, Ni and Zn) from the surface (0–15 cm) samples of an acidic soil (Inceptisol) and a neutral soil (Mollisol) spiked with inorganic salts of these metals or through an acidic sludge were studied by the column method. The rate of desorption of soil applied heavy metals was initially rapid and gradually declined with time. In general, the release of heavy metals from soils polluted by inorganic or sludge sources conformed to a multi-site model of first order kinetics; however, the release of Cd and Ni applied through inorganic sources to the neutral soil could be adequately accounted for by single-site model. The double-site model could adequately explain the release of Cd from sludge amended acidic soil and the release of Zn applied though inorganic salt or sludge to the neutral soil. In acidic soil, the apparent desorption rate coefficients of heavy metals applied through inorganic sources were higher than those for the sludge source. In neutral soil, however, the apparent desorption rate coefficients of heavy metals added through sludge were higher than for inorganic sources. Among the heavy metals, the higher apparent desorption coefficient value and percent desorption of Cd indicated a higher potential of this metal for leaching and ground water contamination. The results also suggested that the acidic soil pH might reduce the ability of the soil to naturally sequester heavy metal cations and lead to their leaching.     

Effects of addition of 12 metals on carbon dioxide release during incubation of an acid sandy soil

Samples of a sandy soil (pH 4.9) were mixed with 10 and 100 p.p.m. of 12 metals (as sulphates) and incubated (30°C) aerobically for 2 and 8 weeks. Depression of CO₂ release with 100 p.p.m. metal levels over 8 weeks increased in the order Bi, Cd, Co, Cu, Pb, Ni, Tl, Sb, Sn, Zn, Hg, Ag. Toxicity order differed somewhat with 10 p.p.m. metal levels and with incubation period.