农业废弃物中重金属含量特征及农用风险评估

为了解江西省主要农业废弃物中重金属污染状况和评估其再利用产物农用的安全性,在江西省内采集了水稻秸秆、蔬菜废弃物、猪粪和牛粪等样品,对样品中铬、镍、铜、锌、砷、镉、汞和铅重金属含量进行了测定与风险评估。结果表明,动物性废弃物中重金属含量和超标率明显高于植物性废弃物,其中猪粪属于重度污染,牛粪为轻度污染,植物性废弃物尚处于安全水平。若以江西省农业废弃物为原料制成有机肥,并长期施用于设施菜地,猪粪有机肥施用8.4、15.3和23.9 a后土壤中Cu、Cd和Zn将陆续超标,牛粪有机肥施用23.3 a后土壤中Cu将超标,水稻秸秆、蔬菜废弃物有机肥施用约29a后土壤中Cd将超标,故农业废弃物有机肥须严格控制原料中重金属含量,其农用的长期安全性有待加强监测。     

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.     

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.     

不同有机肥中Cu、 Zn在农田土壤中的有效性与形态归趋

【目的】畜禽粪便有机肥的施用是造成我国农田土壤重金属污染的重要原因之一。本文选用两种典型规模化养殖场畜禽粪便有机肥,研究其在石灰性土壤和酸性土壤上施用1年后Cu、 Zn的有效性和形态归趋,为客观评价畜禽粪便有机肥中重金属进入土壤后的环境行为和生态风险提供理论依据。【方法】采用温室土壤培养试验,在石灰性土壤和酸性土壤上分别设对照(CK)、 施2%鸡粪(CM2%)、 施5%鸡粪(CM5%)、 施与CM2%、 CM5%含等量Cu、 Zn的重金属无机盐溶液(CS2%、 CS5%)、 施2%猪粪(PM2%)、 施5%猪粪(PM5%)、 施与PM2%、 PM5%含等量Cu、 Zn的重金属无机盐溶液(PS2%、 PS5%)9个处理,每个处理设3次重复,在温室条件下培养1年。测定土壤pH值, EDTA提取有效态Cu、 Zn以及采用改进Tessier连续提取法提取的各形态Cu、 Zn的含量,分析鸡粪、 猪粪及等量无机盐溶液中Cu、 Zn进入土壤后的有效性和形态归趋。【结果】施用鸡粪和猪粪1年后,石灰性土壤的pH值降低,酸性土壤的pH值升高,施用5%猪粪时石灰性土壤pH值降低了0.23个单位,酸性土壤pH值升高了0.87个单位。施入鸡粪、 猪粪1年后,石灰性土壤中有效态Zn和酸性土壤中有效态Cu、 Zn含量显著增加,施用5%猪粪时酸性土壤中有效态Cu含量增加了1.95倍,施用5%鸡粪时2种土壤中有效态Cu的含量均显著低于等量无机盐。施用鸡粪和等量无机盐后,2种土壤中交换态和有机结合态Cu的含量显著增加,交换态、 碳酸盐结合态、 有机结合态和铁锰氧化物结合态Zn的含量显著增加; 施用猪粪和等量无机盐后,2种土壤中交换态、 铁锰氧化物结合态和有机结合态Cu的含量显著增加,碳酸盐结合态和铁锰氧化物结合态Zn的含量显著增加。【结论】施用鸡粪、 猪粪提高了石灰性土壤中Zn和酸性土壤中Cu、 Zn的有效性,高用量条件下鸡粪中Cu的有效性低于等量无机盐。1年后, 通过畜禽粪便有机肥带入2种土壤中的Cu 主要以交换态和有机结合态的形式存在,Zn则主要以碳酸盐结合态、 铁锰氧化物结合态和有机结合态的形式存在。2种土壤上有机肥带入的Cu、 Zn转化为铁锰氧化物结合态的比例低于等量无机盐,2种有机肥带入2种土壤中的Cu转化为交换态和有机结合态的比例高于等量无机盐。鸡粪带入的Zn转化为交换态的比例在酸性土壤中低于等量无机盐,但在石灰性土壤中则高于等量无机盐。     

华北地区饲料和畜禽粪便中重金属质量分数调查分析

为加强重金属的源头控制,进一步形成农产品产地有机肥源重金属阻控体系,该文对华北地区畜禽饲料和粪便中重金属质量分数进行采样调查分析,结果表明,华北地区畜禽粪便超标以Cu、Zn为主,Pb、Cr和As次之,Cd、Ni和Hg不超标。各种畜禽粪便以猪粪和肉鸡粪的超标情况最为严重,肉牛粪、蛋鸡粪次之,奶牛粪不超标。猪粪的Cu、Zn超标率分别高达100%、91.67%,肉鸡粪主要以Cr、Cu、Zn污染为主,超标率分别为50%、66.67%和50%,而蛋鸡粪仅有Cu超标,超标率为11.11%。不同畜禽饲料中重金属的超标情况以猪饲料和肉牛饲料最为严重,肉鸡饲料及奶牛饲料次之。按照农业部1224公告对Cu、Zn的标准,猪饲料中Cu、Zn超标率为66.67%、80.00%,肉鸡饲料中Zn超标62.50%;按照饲料卫生标准对Cr、Pb的标准,肉牛中Cr、Pb超标83.33%、66.67%,奶牛饲料中Cr超标60.00%,蛋鸡饲料中Pb超标53.85%,不同畜禽饲料中Cd的质量分数均不超标。畜禽粪便中重金属Cd、Cr、Cu、Zn的质量分数与饲料中重金属质量分数呈极显著正相关(P0.01),Pb、As与饲料中重金属呈显著相关性(P0.05)。该调查研究有助于掌握华北地区重金属饲料-畜禽粪便污染现状,揭示了对于畜禽粪便或有机肥的重金属超标问题应从源头控制。     

Modelling the effects of ageing on Cd,Zn, Ni and Cu solubility in soils using an assemblage model

Ageing reactions can reduce trace metal solubility and can explain natural attenuation of contaminated soils. We modelled ageing reactions in soil with an assemblage model that considers slow reactions in Fe‐oxyhydroxides and reversible sorption on organic matter and clay minerals. Metal adsorption kinetics on Fe‐oxyhydroxides was obtained from data with synthetic oxyhydroxides. Metal solubility and isotopic exchangeability data were obtained from 28 soils amended with Ni, Zn, Cu and Cd metal salts and monitored for 850 days. The assemblage model was constructed in WHAM 6.0 and used soil properties and dissolved organic matter as input data. The model was first validated to predict dissolved metal concentrations, based on the concentration of isotopic exchangeable metals. The model overestimated metal solubility without parameter adjustment by mean factors of 4–7, and successful fits were obtained by increasing the specific surface area of Fe‐oxyhydroxides from measured values of synthetic systems to a value of 600 m² g^?1 recommended by other authors. The effect of ageing on the isotopic exchangeable metal fraction was subsequently modelled starting from the predicted fraction of metals present on Fe‐oxyhydroxides immediately after soil spiking. The observed isotopic exchangeable metal fractions of Ni, Zn and Cd agreed reasonably well with predicted values. The model predicts that ageing reactions are more pronounced at higher pH because metal sorption is increasingly directed to oxyhydroxide surfaces with increasing soil pH. Modelling fixation of Cu requires more information on fixation of that metal in organic matter.     

浙江省商品有机肥中重金属含量变化趋势及风险管控对策

  【目的】  有机肥是农业生产的重要肥源，了解有机肥质量安全现状，可为有机肥合理施用和管控提供参考。  【方法】  于2017年采集浙江省96家有机肥生产企业共99个商品有机肥样品，研究分析其Hg、As、Cd、Pb、Cr、Cu、Zn和Ni 8种重金属含量、分布特征、污染成因及施用风险。并与2013年文献进行比较，分析重金属含量的变化。  【结果】  1) 商品有机肥中Hg、As、Cd、Pb、Cr、Cu、Zn、Ni的平均含量分别为0.17、5.5、0.63、17.3、33.2、213.8、660.5、17.7 mg/kg，变异系数为54.9%～151.3%，含量差异较大。相比2013年，Cd、Pb、Cr、Hg和As含量在2017年均有所降低，降幅为23.0%～72.7%，其中Hg和As含量大体呈逐年下降趋势，2017年较2009年平均含量分别下降74.2%和51.8%，Cr和Pb平均含量较2010年分别下降74.9%和54.4%，Cd平均含量在近4年降幅明显，2017年较2013年下降72.7%。但商品有机肥中As仍有8.1%超标，Cu、Zn含量偏高，Ni含量有增加趋势。Cu、Zn、Ni是浙江省商品有机肥主要风险因子。2) 主成分和相关性分析表明，Cu-Zn、Cr-Ni-Hg、Cd-Pb重金属污染来源具有同源性。Cu、Zn、As以饲料添加来源为主，Cr、Hg、Ni主要来源于饲料原料本身，Cd、Pb则以饲料原料本身、生产粘结剂或生产环境来源为主。3) 商品有机肥成分配方复杂，猪粪原料占比较大，其次为鸡粪和牛粪。根据NY 525—2012有机肥重金属限量标准，以猪粪为主要原料的有机肥As超标率9.6%，以鸡粪、羊粪为主要原料的有机肥未出现重金属超标，根据德国腐熟堆肥重金属限量标准，以猪粪和鸡粪为主要原料的有机肥Cu、Zn超标样品较多，Ni只在以猪粪和鸡粪为主要原料的有机肥中出现超标。4) 长期施用含重金属商品有机肥，存在土壤重金属积累风险。按有机肥年施肥量30 t/hm2推算，Cu、Zn和Cd风险相对较大，安全使用年限分别为14、18、34 年。  【结论】  浙江省商品有机肥总体质量安全程度较高，有机肥中Cr、Pb、Hg、As、Cd含量近年来得到较好的控制，但Cu、Zn、Ni含量偏高，部分As含量超标，长期施用条件下存在土壤重金属累积风险，因此需加强对有机肥中重金属的管控，制定商品有机肥中Cu、Zn、Ni限量标准，以保障土壤长期可持续利用。     

新乡市寺庄顶污灌区土壤中重金属的形态分布及生物有效性研究

对长期电池废水灌溉的新乡市寺庄顶污灌区和对照区土壤重金属进行取样分析,结果表明,对照区土壤中Cd,Ni,Zn,Cu和Cr含量都能达标,污灌区土壤中Cr含量能达标,Cd,Ni,Zn和Cu的含量超标,其平均含量分别为65.31,1 196.64,2 799.25,145.78 mg/kg,是国家土壤环境质量二级标准的108.85,19.94,9.33和1.46倍。形态分析结果表明,污灌区污染最严重的Cd主要以铁-锰氧化物结合态存在,所占比例平均为56.84%;Ni主要以铁-锰氧化物结合态和残余态存在,所占比例平均为37.44%和39.55%;Zn主要以残余态存在,所占比例平均为78.24%;Cu主要以有机结合态存在,所占比例平均为57.70%;Cr主要以有机结合态和残余态存在,所占比例平均为45.55%和34.18%。与对照相比,污灌降低了Cd,Ni,Zn,Cu和Cr残余态所占比例,提高了重金属迁移能力和生物有效性。在4种超标重金属中Cd可交换态所占比例最高,平均为24.54%,由于其生物有效性最高,Cd迁移能力和植物毒性最值得关注。     

施用有机物料对土壤镉形态的影响

采用室内培养试验,研究作物新鲜秸秆和腐熟猪粪对模拟镉（Cd）污染的土壤中Cd形态转化的动态影响。结果表明,各处理土壤交换态Cd含量随培养时间均逐渐降低。碳酸盐结合态和铁锰氧化物结合态Cd含量先增加后降低, 而有机质结合态和残渣态Cd含量则逐渐增加。添加秸秆可增加土壤交换态Cd含量,但随时间延长,增幅逐渐降低, 猪粪则可降低土壤交换态Cd含量。添加有机物后土壤交换态Cd含量的变化主要是由有机质结合态或残渣态Cd含量的变化而引起。秸秆和猪粪对土壤Cd形态的转化与土壤胡敏酸（HA）和富里酸（FA）的变化有关。秸秆对能活化土壤Cd的FA增加幅度大于对能钝化土壤Cd的HA增加幅度,降低HA/FA比,但降幅随时间逐渐减少; 猪粪在整个培养阶段对HA增加幅度均大于FA的增加幅度,增加HA/FA比。秸秆和猪粪均可降低潮土pH而提高红壤pH,但只有猪粪可通过提高红壤pH降低Cd向交换态转化。添加秸秆和猪粪后,Cd由低活性态向交换态转化与HA/FA呈显著负相关。     

Long-Term Transformation and Redistribution of Potentially Toxic Heavy Metals in Arid-Zone Soils: II. Incubation at the Field Capacity Moisture Content

Solid-phase transformation of added Cd, Cu, Cr, Ni, Pb and Zn, in two arid-zone soils incubated in the field capacity moisture regime for one year, were studied. The heavy metals were fractionated into six empirically defined fractions using a selective sequential dissolution (SSD) protocol optimized for arid-zone soils. Each of these fractions was named based on the major soil component targeted for dissolution during the specific SSD step, but it is not assumed that they are mineralogically and chemically totally specific. The transformations of the metals in the two soils incubated at the field capacity regime were compared with those at the moisture saturation regime (Han and Banin, 1997). An initial fast stage of transformation of the soluble metals from the exchangeable (EXC) fraction to the less labile fractions (the carbonate (CARB) fraction for Cd, Pb, Zn, Ni and Cu, and the organic matter (OM) fraction for Cr, and to some extent Cu and Ni) occurred during the fractionation and within one hour after addition. This was followed by a second stage, involving long-term transformation processes of all metals: added Cd was transferred from the EXC into the CARB fraction; added Cr was transferred from the CARB to the OM fraction and Pb was transferred very slowly to the easily reducible oxide (ERO) fraction. Added Cu, Ni and Zn were transferred from the EXC and CARB fractions into the ERO fraction and to some extent OM and RO fractions. In Part I of this series, we reported that during incubation in the saturated moisture regime, Zn and Ni were transferred mainly into the RO and OM fractions. Cadmium, Cr and Pb underwent the same transformation pathways during the slow long-term process, with slightly different rates, in both water regimes. At low levels of addition, the incubated soils moved over one year towards a distribution similar to that of the native soil. At higher levels, the soils still remained removed from the quasi-equilibrium which characterized the native soil, even at the end of one year of incubation.     

泉州走马埭典型土壤重金属的赋存形态分析

采用改进的Tessier连续萃取方法研究了泉州走马埭国家农田示范保护区典型土壤中重金属(Cr、Ni、Cu、Zn、Cd、Pb)的化学形态分布,通过土壤重金属的赋存形态分析比较了6种重金属的生物可利用性。研究结果表明,土壤中不同重金属元素化学形态分布具有不同的特点:Cr和Ni主要以残渣态存在,其余形态所占的比例很小;Cu以残渣态含量最高,碳酸盐结合态含量最低;Zn以残渣态为主,可交换态含量最低;Cd以可交换态和碳酸盐结合态为主,水溶态含量最低;Pb以残渣态和铁锰氧化物结合态为主,水溶态含量最低。土壤中除Cd外,Zn、Cu、Cr、Pb、Ni在正常自然条件下相对比较稳定。     

污染水稻土中重金属的形态分布及其影响因素

通过BCR3步提取法研究了江西省贵溪铜冶炼厂污染区水稻土中重金属的形态分布。研究表明,废渣场渗滤液污染区域(渣场区)的污染较污水灌溉污染区(污灌区)严重,渣场区土壤中Cu、Pb、Cd的含量高于污灌区,而污灌区土壤Ni含量较高。在表层(0～20cm)水稻土中,Cu以可氧化态为主,Pb以可还原态和可氧化态为主,Cd以酸溶态为主,Ni以残渣态为主,不同重金属元素的有效态所占总量百分比大小顺序是Cd>Cu>Pb>Ni。土壤重金属不同形态之间也呈现一定的相关性,说明Cu与Pb、Cd、Ni之间具有同源性。土壤pH主要影响了污灌区中Cu的形态分布,以及渣场区土壤酸溶态Ni的分布。土壤有机质含量对各重金属形态分布的影响不明显。     

Trace metal composition and speciation in street sediment: Sault Ste. Marie,Canada

Street sediment collected in Sault Ste. Marie, Ontario was examined for trace element composition (As, Cd, Cr, Cu, Fe, Pb, Hg, Ni and Zn) and the metal partitioning to various sediment properties was determined by sequential extraction. Total Ni, Cu, Zn and Pb concentrations exceeded the lowest effect levels specified in the Ontario Provincial Sediment Quality Guidelines for Metals (Environment Ontario, 1992) and derived from bioassay studies. According to these Guidelines, the disposal of such sediment has to be guided by environmental considerations. A significant fraction of these metals was extractable in 0.5 N HCl over a 12-hour period and considered as potentially bioavailable. The major accumulative phases of toxic metals in this sediment are exchangeable, carbonate, Fe/Mn oxides and organic matter but the relative importance of each phase varied for individual metals. Approximately 20% of the total extractable Cd is found in each of these four fractions. Pb, Zn and Mn are predominantly bound to carbonates, Fe/Mn oxides and organic matter. Cu shows a high affinity for organic matter and to a lesser extent for carbonates. Elevated levels of Cd, Pb, Cu, Zn, Mn and Cr in the exchangeable and/or soluble phase suggest that sediment associated metals, mobilised from streets in Sault Ste. Marie during runoff and snowmelt, would adversely impact water quality in the receiving waters. However, large fractions of the total metal load are associated with coarser particles which are unlikely to be transported through the drainage system into receiving waters.     

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。     

Soil Zinc Transformations as Affected by Applied Zinc and Organic Materials

Information on soil zinc (Zn) distribution is essential for understanding its chemical reactions and bioavailability. An experiment was conducted to evaluate the effect of wheat straw, cow manure, and vermicompost applied with Zn rates on Zn distribution in a calcareous soil. A sequential extraction scheme was used to fractionate Zn into soluble and exchangeable, bound to carbonate, organically bound, bound to manganese (Mn) oxide, bound to amorphous iron (Fe) oxide, bound to crystalline Fe oxide, and residual forms. In untreated soil, Zn was mainly in the residual fraction. Increasing rates of applied Zn increased all forms of Zn. Carbonate and residual forms showed the greatest increase. Organic materials application increased all fractions, except Mn-oxide form, and this increase was more pronounced for the organically bound form. Concentration of soluble, exchangeable, and organically bound forms was greatest in cow manure–amended samples as compared to other organic materials, suggesting that cow manure contained more bioavailable Zn than other organic materials.     

Inter-relationships between soil properties and the uptake of cadmium,copper, lead and zinc from contaminated soils by radish (Raphanus sativus L.)

Radish was grown in 46 garden plots in England and Wales. Some of the gardens had been contaminated by heavy metals from lead mining. The soils were analysed for pH, organic content and cation exchange capacity; also for Cd, Cu, Pb, and Zn (total, organic bound, exchangeable and specifically sorbed). Acetic acid-soluble P and exchangeable K, Mg and Zn were also determined. Radish bulbs and leaves were analysed for heavy metals. The results were interpreted using linear and multiple linear correlation and regression analysis. Acetic acid satisfactorily predicted Cd uptake and Pb uptake was best predicted by total soil Pb. These regressions were not improved by including other soil properties. Zinc uptake was best modeled using exchangeable Zn and the predictive power of the regression was improved by including pH. However, the pH term was positive suggesting that raising soil pH would increase uptake. A poor relationship between total and exchangeable Zn was changed to a highly significant relationship by including cation exchange capacity and pH. The latter term was strongly negative. Uptake of Cu was not satisfactorily predicted.     

Leaching of metals from the A-horizon of a spruce forest soil

The study quantifies the amount of metals (Na, K, Mg, Ca, Al, Fe, Mn, Ni, Cr, V, Cu, Zn, Cd, Pb) leached from the A-horizon of a podzolic spruce forest soil in southern Sweden during 2.5 yr, and offers statistical evidence of environmental conditions of importance to metal release. Considerable losses of Pb, Cr, Ni and V may occur from the A-horizon of forest soils under conditions favoring leaching of organic matter, Fe, and Al, i.e. during periods of comparably high soil temperature and moisture. Metals with a larger fraction present in exchangeable form (Na, Mg, Ca, Zn, Cd) are more susceptible to minor pH changes. An accelerated deposition or internal production of acidic matter therefore will reduce the retention times of these elements particularly.     

Effect of low‐temperature biochar derived from pig manure and poultry litter on mobile and organic matter‐bound forms of Cu,Cd, Pb and Zn in sandy soil

Numerous studies conducted so far have shown that biochar has a significant effect on physical, chemical and biological properties of soils. Biochar can be used to alleviate the effects of soil contamination with organic and inorganic compounds, for instance, to reduce the mobility of heavy metals. The aim of the research was to evaluate the effect of pig manure and poultry litter, as well as biochars produced from these materials at a temperature of 300 °C on Cu, Cd, Pb and Zn contents in mobile and organic matter‐bound forms in soil. The research was conducted under laboratory conditions. The materials were introduced into sandy acid soil in doses of 0.5, 1.0 and 2.0% w/w. The application of pig manure‐derived biochar (BPM) and poultry litter‐derived biochar (BPL), depending on the amount added, reduced the mobility of copper from 28 to 69%, from 77 to 100% in the case of cadmium, from 94 to 99% in the case of lead, and from 15 to 97% in the case of zinc. The 2% amendment of pig manure (PM) and poultry litter (PL) caused an increase in the content of Cu extracted with NH₄NO₃ in comparison with the control treatment. A similar situation was observed in the case of zinc after the application of 0.5 and 1% amendments of pig manure (PM). Cu, Cd, Pb and Zn contents extracted with 0.025 mol C₁₀H₂₂N₄O₈ were higher than contents of these elements extracted with 1 m NH₄NO₃, mainly due to different extraction force of the extractants. The obtained results indicate that, compared with the content determined in soil from the control treatment, 1 and 2% amendments of both unconverted and thermally converted materials to the soil had a greater effect on contents of Cu, Pb and Zn in the organic matter‐bound fraction than the 0.5% amendment. The organic materials applied did not affect the content of cadmium in organic matter‐bound fraction.     

REACTIONS BETWEEN METALS AND HUMIFIED ORGANIC MATTER

We studied the properties of the soluble and dispersed compounds of Cu, Mn, Co, Ni, Pb, Zn, and Cd formed by the action of aerobically decomposing plant matter on the respective metal oxides. The metals were mobilized partly in association with colloidal humified organic matter, and partly in true solution as complexes that seemed to be anionic. In the presence of a clay soil there was no net mobilization of colloidally bound Cu, but the dialysable Cu complex was not appreciably sorbed by the mineral colloids and was leached from the reaction mixture. The metals were not precipitated under alkaline conditions from the dialysable complex forms. Material with similar complexing properties was found in the dialysable fractions of a soil organic matter extract, of water squeezed from a raw peat, and of laboratory lysimeter solutions from a podzol under Calluna. Below about pH 6 the exchange of Cu on a soil clay was not affected by the presence of colloidal decomposition products of lucerne. With Co, Ni, and Zn the corresponding pH value was about 4, and the critical value for Cu in the presence of colloidal soil organic matter was also about 4. Below these values the metal and organic matter sorption curves were diametrically opposed so that under these conditions Cu is apparently not strongly bonded to colloidal organic matter.     

Chemical and Mineralogical Properties of Norwegian Alum Shale Soils,with Special Emphasis on Heavy Metal Content and Availability

Abstract

Alum shale and till soils overlying alum shale bedrock were analysed for aqua regia and NH₄OAc/EDTA extractable Pb, Cu, Zn, Ni, Mn and Cd. The means of these determinations were compared with those of Norwegian, Finnish and Swedish non-alum shale soils. Alum shale soils seemed to contain higher amounts of both total and easily extractable Cu, Zn, Ni and Cd. Total Pb content also seemed to be higher in the alum shale soils. The relative availability of Cd, Ni and Mn, expressed as the ratio of NH₄OAc/EDTA to aqua regia extractable, was found to be greater than that of Pb, Cu and Zn in the alum shale and till soils.