Fluoro‐mobilization of metals in a Slovak forest soil affected by the emissions of an aluminum smelter

Depositions originating from a central Slovak Al smelter may increase metal solubility in adjacent soils because they contain F (mainly HF). The reason for fluoro‐mobilization of metals may be the formation of soluble fluoro‐metal complexes or the mobilization of organic matter and subsequent formation of organo‐metal complexes. The objectives of our work were (1) to assess the extent of metal mobilization by fluoride in a Slovak Lithic Eutrochrept affected by the emissions of an Al smelter and (2) to model the dissolved metal species with the help of a chemical equilibrium model (MINEQL+). The O (Moder), A, and B horizons were equilibrated with solutions at F concentrations of 0, 0.9, 2.7, and 9.0 mmol l^—1. In the extracts, the concentrations of Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Ni, Pb, Zn, dissolved organic carbon (DOC), free and complexed F, and the pH and electrical conductivity (EC) were determined. The heavy metal concentrations in the O horizon (Cd: 0.99, Cr: 18.0, Cu: 44, Ni: 26, Pb: 110, and Zn: 84 mg kg^—1) were 2.5 to 9 times larger than those in the A and B horizons. The concentrations of H₂O‐soluble F decreased from the O (261 mg kg^—1) to the A (103 mg kg^—1) and B horizon (92 mg kg^—1). In batch experiments increasing addition of F increased the equilibrium concentrations of Al, Cr, Cu, Fe, Ni, Pb, and DOC in all samples, of Cd in the A, and of K in the B horizon. At the same time the concentrations of complexed F and pH increased whereas EC decreased. Chemical equilibrium modelling indicated that the mobilizing effect of F resulted from the formation of fluoro‐Al complexes and organo‐complexes of all other metals.     

某冶炼厂周边农田土壤重金属复合污染研究

通过实地采样调查和室内样品分析,研究了蓝田冶炼厂周边农田土壤重金属含量空间分布特征.并运甩地积累指数法对该区土壤重金属污染水平进行了评价.结果表明:该区农田土壤已受到了不同程度的重金属污染,水平方向上,距冶炼厂100m处的表层土壤污染最重,Pb、Zn、Cu、Cd含量均严重超标,分别为国家土壤环境质量二级标准的3.833、0.630、2.510、36.349倍.随着距离的增大,重金属含量大体都呈现出先上升、后下降最后趋于稳定的分布状况;剖面土壤中,重金属含量从表层到深层递减,0-35cm范围各层含量变化幅度较大,35cm以下基本上趋于稳定.从地积累指数来看,表层土壤和剖面土壤各样点的主要污染因子为Pb和Cd,Pb为中-强度污染,Zn和Cu为中等程度的污染,Cd已达到强-极严重污染程度.     

蓝田冶炼厂周边农田土壤重金属复合污染分析评价

为了解粗铅冶炼活动对周边土壤的污染情况,防止重金属再污染和修复改良已污染土壤,对蓝田冶炼厂周边农田土壤中重金属含量的空间分布规律进行初步分析,并运用单项污染指数法和内梅罗综合污染指数法对该区重金属污染水平进行评价.结果表明:水平方向上,距冶炼厂100 m处的表层土壤中Pb、Zn、Cu、Cd四种重金属的含量最高,分别达1 341.693、188.877、251.015、21.810 mg/kg,依次为国家土壤环境质量二级标准的3.833、0.630、2.510、36.349倍.随着距离的增大,重金属含量大体都呈现出先上升、后下降最后趋于稳定的分布状况;剖面土壤中,重金属含量从表层到深层递减,0～35 cm范围各层含量变化幅度较大,35 cm以下基本上趋于稳定.从综合污染指数来看,表层土壤和剖面土壤各样点的综合污染指数均远大于3,说明该区农田土壤已处于重度复合污染状态.     

丘陵区水稻土Cu污染空间变异的协同克里格分析

针对丘陵红壤区铜冶炼厂周围水稻土污染区(1.40 km2),在景观尺度上,采用协同克里格方法,研究了影响表层土壤Cu含量空间分布预测的辅助因子.基于空间自相关性、间距、长轴方位角以及各种预测误差,评价了辅助变量(包括秸秆全Cu含量StrawCu、籽粒全Cu含量GrainCu、土壤全Cd含量Cd、土壤pH、土壤有机质OM、高程H)对表层土壤Cu含量分布预测精度的影响.结果表明,单辅助变量的协同克里格预测值与实测值相关系数的大小顺序为Cu/Cd＞Cu/H＞Cu/StrawCu＞Cu/GrainCu＞Cu/OM、Cu/pH,而多辅助变量协同克里格预测的相关系数大小顺序为Cu/(Cd,StrawCu)＞Cu/(Cd,StrawCu,H)＞Cu/(Cd,StrawCu,GrainCu)＞Cu/(StrawCu,GrainCu)＞Cu/(Cd,H).与土壤全Cu含量的普通克里格插值精度相比,利用表层土壤全Cd含量、水稻秸秆全Cu含量、高程作为辅助变量与水稻土表层全Cu含量进行协同克里格插值可以显著提高预测精度;但水稻籽粒全Cu含量作为辅助变量对预测精度影响不显著;而土壤有机质含量和土壤pH作为辅助变量反而降低了预测精度.在对表层土壤全Cu含量分布的多辅助变量协同克里格预测中,表层土壤全Cd含量和水稻秸秆全Cu含量的影响最大,其次是高程,水稻籽粒全Cu含量不能提高对表层土壤全Cu含量分布的预测精度.     

苏南某冶炼厂周边农田土壤重金属分布及风险评价

选择江苏南部冶炼厂周边污染的水稻田,采集耕层0～15cm的土壤,分析土壤中重金属Cd、Pb、Hg、As、Zn、Cu的污染程度及其空间变异特征。结果表明,土壤Cd、Pb、Cu、Zn、Hg的全量随着距污染源距离的增加而减少,呈现由东北向西南扩散的趋势,As则是由西北向东南扩散。6种重金属中Cd、Hg的污染范围相对较大,Zn的污染范围最小。DTPA浸提的6种重金属有效态含量都是距污染源距离越远而越少。采用内梅罗综合污染指数法对土壤中的重金属进行风险评价,土壤重金属的综合污染指数为39.27,污染程度已超过5级,为重度污染,其中Cd、Hg污染最为严重,含量范围分别为3.98～44.58mg·kg-1、0.36～2.01mg·kg-1,As为中度污染,Pb、Cu、Zn则为轻度污染,说明研究区域农产品安全生产存在很大的风险。     

Long-term irrigation with zinc smelter effluent affects important soil properties and heavy metal content in food crops and soil in Rajasthan,India

Use of wastewater for irrigating agricultural crops is on the rise, particularly in the developing countries. The present study was undertaken to assess the long-term effect of irrigation with zinc smelter effluent on important soil properties including heavy metal status. Metal concentration in the edible parts of the crops grown on smelter effluent-irrigated soils was also measured. For this purpose, the agricultural lands which have been receiving the zinc smelter effluent irrigation for about five decades at Debari, Udaipur, India were selected. The adjacent tubewell water-irrigated fields were selected as reference. Long-term irrigation with smelter effluent resulted into significant buildup of ethylenediaminetetraacetic acid extractable Zn (57.7 fold), Cu (4.51 fold), Fe (3.35 fold), Mn (1.77 fold), Ni (1.20 fold), Pb (45.1 fold), and Cd (79.2 fold) in soils over tubewell water-irrigated fields. Total Zn, Cu, Mn, Ni, Pb, and Cd content in effluent-irrigated soils was also increased by 27.0, 1.60, 1.40, 1.30, 26.2, and 167 fold, respectively. Risk assessment indicated a very high to moderate potential ecological risk due to Cd, Pb, and Zn in soils close to the immediate vicinity of the smelter plant. Cadmium and Pb concentrations in edible parts of almost all the crops grown on effluent-irrigated soils were above the safe limit of CODEX commission. On an average, soil pH dropped by 0.31 units due to smelter effluent irrigation. Smelter effluent irrigation resulted into significant increase in soil organic carbon, electrical conductivity, and CaCO₃ content. On an average, there was decrease in available N (21.0%) and P (20.8%) content in effluent-irrigated soils over the tubewell water-irrigated ones. An increase in available K (102%) and S (26.0 fold) was recorded in effluent-irrigated soils. Long-term irrigation with zinc smelter effluent resulted into reduced microbial activities in soil as evidenced from the level of microbial biomass carbon and dehydrogenase activity. In view of the buildup of heavy metals and subsequent imbalance in essential plant nutrients in smelter effluent-irrigated soils, appropriate remediation-cum-fertilization strategy needs to be adopted for better soil health and plant nutrition.     

丘陵区水稻土Cu污染空间变异的协同克里格分析

针对丘陵红壤区铜冶炼厂周围水稻土污染区（1.40km^2）,在景观尺度上,采用协同克里格方法,研究了影响表层土壤Cu含量空间分布预测的辅助因子。基于空间自相关性、间距、长轴方位角以及各种预测误差,评价了辅助变量（包括秸秆全Cu含量StrawCu、籽粒全Cu含量GrainCu、土壤全Cd含量Cd、土壤pH、土壤有机质OM、高程H）对表层土壤Cu含量分布预测精度的影响。结果表明,单辅助变量的协同克里格预测值与实测值相关系数的大小顺序为Cu/Cd〉Cu/H〉Cu/StrawCu〉Cu/GrainCu〉Cu/OM、Cu/pH,而多辅助变量协同克里格预测的相关系数大小顺序为Cu（/Cd,StrawCu）〉Cu（/Cd,StrawCu,H）〉Cu（/Cd,StrawCu,GrainCu）〉Cu/（StrawCu,GrainCu）〉Cu（/Cd,H）。与土壤全Cu含量的普通克里格插值精度相比,利用表层土壤全Cd含量、水稻秸秆全Cu含量、高程作为辅助变量与水稻土表层全Cu含量进行协同克里格插值可以显著提高预测精度;但水稻籽粒全Cu含量作为辅助变量对预测精度影响不显著;而土壤有机质含量和土壤pH作为辅助变量反而降低了预测精度。在对表层土壤全Cu含量分布的多辅助变量协同克里格预测中,表层土壤全Cd含量和水稻秸秆全Cu含量的影响最大,其次是高程,水稻籽粒全Cu含量不能提高对表层土壤全Cu含量分布的预测精度。     

陕西某铅锌冶炼区土壤重金属污染特征与形态分析

为了探讨铅锌冶炼对土壤环境质量的影响,对陕西某铅锌冶炼区土壤中重金属的含量和形态进行了分析,并运用单因子污染指数法和内梅罗综合污染指数法对土壤重金属污染程度进行评价。结果表明,Pb、Cd、Cu、Zn含量的平均值分别是陕西省土壤背景值的19.27、135.32、2.76、8.02倍。单因子污染指数评价结果显示,Cd(19.53)达到重度污染,Zn(1.78)和Pb(1.09)达到轻度污染,Cu(0.56)无污染。内梅罗综合污染指数评价结果表明,冶炼厂东、西10 km范围内土壤均处于重度污染程度,且东部高于西部。重金属形态分析结果显示,Pb、Cd、Cu、Zn各形态在全量中所占的比例都以残渣态(34.45%～45.98%)最大,其次为可氧化态(27.45%～30.57%),再次为可还原态(17.63%～23.61%),最后为可交换态(6.80%～14.41%)。重金属形态比例和土壤理化性质的相关性分析表明,pH值与Cd、Cu的可交换态比例呈显著负相关,与Zn的残渣态比例呈显著正相关。土壤有机质与Cd的可交换态比例、可还原态比例呈显著负相关,与Cd的残渣态比例呈显著正相关。铅锌冶炼厂周围土壤受到以Cd污染为主的多种重金属的复合污染,冶炼厂大气沉降、采矿场扬尘是主要污染源。土壤重金属污染防治中应当加强冶炼厂烟尘点源控制,防止土壤酸化。     

苏南某冶炼厂周边农田土壤重金属分布及风险评价

选择江苏南部冶炼厂周边污染的水稻田,采集耕层0～15cm的土壤,分析土壤中重金属Cd、Pb、Hg、As、Zn、Cu的污染程度及其空间变异特征。结果表明,土壤Cd、Pb、Cu、Zn、Hg的全量随着距污染源距离的增加而减少,呈现由东北向西南扩散的趋势,As则是由西北向东南扩散。6种重金属中Cd、Hg的污染范围相对较大,Zn的污染范围最小。DTPA浸提的6种重金属有效态含量都是距污染源距离越远而越少。采用内梅罗综合污染指数法对土壤中的重金属进行风险评价,土壤重金属的综合污染指数为39.27,污染程度已超过5级,为重度污染,其中Cd、Hg污染最为严重,含量范围分别为3.98～44.58mg·kg-1、0.36～2.01mg·kg-1,As为中度污染,Pb、Cu、Zn则为轻度污染,说明研究区域农产品安全生产存在很大的风险。     

Heavy Metal Concentrations,Partitioning, and Storage in Slovak Forest and Arable Soils Along a Deposition Gradient

Along a heavy metal deposition gradient, caused by a Cu smelter, heavy metal concentrations, partitioning, and storage in forest and arable soils were examined. We sampled organic and mineral soil horizons (0—50 cm) at ten pairs of forest and arable sites derived from the same parent material. A-horizons were extracted with a seven-step sequence; O- and subsoil horizons were digested with strong acids (HNO₃/HClO₄). We found high concentrations of Cd (up to 17.38 mg kg^—1 in the O horizons/up to 2.44 mg kg^—1 in the A horizons), Cu (8437/415), Pb (3343/126), and Zn (1482/637) which decreased exponentially with distance from the smelter and with soil depth. The metal concentrations in the organic layers indicate that the average transport distance decreases in the order Cd > Zn > Pb > Cu. With regard to metal partitioning, NH₄NO₃- + NH₄OAc-extractable forms in the A horizons were most affected by the deposition being more pronounced under forest. In the uppermost 50 cm of the four soils nearest to the smelter two to four times higher Cd, Cu, Pb, and Zn storages were found in forest than in arable soils. At greater distance, the higher deposition onto forest soils due to the scavenging effect of the canopy obviously was compensated by stronger leaching.