电解锰行业硒及重金属污染物的环境风险研究
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摘要
随着国际世界市场对锰需求的持续增加,电解锰行业不断发展,尤其是在中国的发展更为突出,然而也导致了诸多生态环境问题,主要表现为“三废”的潜在危害及对周边环境的污染和硒及重金属的环境风险。
本文以10家典型电解锰企业为研究对象,采集锰矿石、锰渣和厂区周边土壤、植物及水等样品,以微波消解土壤样品,电解板消解植物样品,ICP-MS(电感耦合等离子体)分析其中的Se及Cr、Mn、Co、Ni、Cu、Zn、As、Cd、Pb等10种有毒有害重金属元素的相对含量,土壤中元素的分析结果与全国土壤背景值比较,水体分类检测,并于生活饮用水及地下水卫生标准比较,分析了电解锰企业对土壤和水体的环境风险,根据植物各部位对土质中监测元素的富集程度分析了植物受电解企业的污染情况；以SES法提取锰渣中10种监测元素的六种形态,并结合HPLC-ICP-MS(高效液相色谱-电感耦合等离子体)分析结果探索锰渣中监测元素的迁移转化特性,通过同步辐射XANES进一步研究锰渣中Se的毒理学特性。
结果表明：电解锰企业的原料-锰矿石品位普遍偏低、伴生元素多、伴生情况复杂、硒及重金属元素相对含量高,潜在环境风险较大。企业“三废”对周边土壤、植物和水体的污染严重,主要为Se、Cd的污染,并已经威胁到了企业周边人的健康,存在极大的环境隐患和风险。
陆地土壤受污染程度较水稻田土壤重,主要为Se和Cd污染,监测元素含量随采样点离渣库距离的增大呈现递减趋势。植物各部位对监测元素的富集能力普遍较强,Se尤为突出,Cd其次,植物根附带土壤中监测元素超标程度与该元素在植物体内的富集程度成正比；农产品受该行业的污染较为严重。锰渣库周边河水中Mn含量超地下水质Ⅲ类标准高达143.49倍；农田水中受污染程度低于河水；企业附近居民集聚区的地下水中Mn和Se的含量均已超出了国家规定的生活饮用水卫生标准中关于这两种元素的安全值上限；水体也因此存在着很大的环境风险。
锰渣是环境污染的最大源头,10种监测元素的含量相对较高。在自然条件下,锰渣中Se及重金属元素主要以水溶态、交换态和酸溶态这3种形式迁移到外环境,且随着周围环境pH值的减小,从锰渣中迁移和转化到外环境中的量就越大；通过同步辐射定性分析可知,锰渣中Se主要以Se032-形式存在,且毒性最大,与工艺过程中添加Se02有密切关系,除了产品锰片中夹带着少量的含硒物之外,其余大部份的含硒物质均随着滤渣进入到渣库,在长期的雨水浸泡和冲刷作用,大量有毒害的含硒物流入外环境,污染河流、地下水源,使得农作物体内富集更多的有毒有害元素。
图[21]表[29]参考文献[80]
With the increase of foreign and domestic market demand for manganese, the development in industry of electrolysis manganese was rapid in the world. And above all in our country, this development was also improved by leaps and bounds. However, it also leads to many ecological environment problems. Three wastes existed potential risks to environment. Se and heavy metals pollution also damaged environment nearby in industry of electrolysis manganese.
Manganese ore stone, manganese residues and surrounding soil, plants and water which comes from10typical electrolysis manganese industries was used in this paper. This paper used microwave and electrolytic plate digestion for pretreat samples and quantitative analyzed10types of elements by ICP-MS technology, including Se, Cr, Mn, Co, Ni, Cu, Zn, As, Cd, Pb. It further comprehensive analyzed pollution which came from electrolysis manganese industry affected on neighboring soil, plant and water. Testing results of soil samples based on the national background average value. And the results of water sample based on standard of drinking water and groundwater. Enrichment extent of monitored elements in accessory soil with plants was researched in this paper. Six kind species of10types of elements were extracted in manganese residues by SES technology. The characteristics about migration and transformation of monitored elements in manganese residues were studied by combining analysis results of HPLC-ICP-MS. Finally, it further studied toxicologic characteristics of Se was studied furtherly by synchrotron radiation XANES technology.
Results showed that raw materials about the industry of electrolysis manganese had potential risk. Many associated elements existed in manganese ore stone and its grade was generally low. However, the situation of association was very complex. Relative content of Se and heavy metal elements was higher. Soil, plants and water near by electrolysis manganese industry suffered serious pollution by three wastes which from industry. This pollution of Se and Cr was mainly showed. It had affected human health and safety living in surrounding in industry of electrolysis manganese and also was a great environmental risk and potential troubles.
By the extent of the pollution about land soil was more serious than rice paddies. It mainly showed Se and Cr pollution. But the content of monitored elements was gradually decreased with the increase of distance between sample point and manganese residues library. Capacity of the enrichment was generally stronger to monitored elements each part of plant. This capacity of Se was strongest and secondly was Cr. The extent of exceeding standard on monitored elements in accessory soil with plants proportional to it's enrichment in plant. This extent to the edible part of crops was more serious. Content of Mn in the river water surrounding manganese residues library was143.49times than that in the groundwater III type of standard. Generally, the exceeding multiple of farmland water was lower than river water. The content of Mn and Se in resident drinking water was beyond national sanitary standard for living and drinking water. Therefore, there was a huge water environmental risk.
The biggest source of environmental pollution was manganese residues. But the content of monitored elements was relatively bigger. In the natural conditions, Se and some heavy metal elements, including water dissolves species, exchangeable species and sour dissolves species, could migrate and transform to external environment. With acidity increase in environment, the capacity of migration and transformation was increased gradually. Qualitative analysis by synchrotron radiation technology was showed that the species of Se in manganese residues was mainly SeO32-, but the toxicity of this species was largest. It closely related to add SeO2to the process of technology. Only a small amount of Se was contained in products but most of rest accessed to manganese residues library along with filter residues. A large number of materials containing Se were sent to the environment under the long-term soaked and scoured action of rain. It not only polluted groundwater and crops even threaten human life.
Figure [21] table [29] reference [80]
本文以10家典型电解锰企业为研究对象,采集锰矿石、锰渣和厂区周边土壤、植物及水等样品,以微波消解土壤样品,电解板消解植物样品,ICP-MS(电感耦合等离子体)分析其中的Se及Cr、Mn、Co、Ni、Cu、Zn、As、Cd、Pb等10种有毒有害重金属元素的相对含量,土壤中元素的分析结果与全国土壤背景值比较,水体分类检测,并于生活饮用水及地下水卫生标准比较,分析了电解锰企业对土壤和水体的环境风险,根据植物各部位对土质中监测元素的富集程度分析了植物受电解企业的污染情况；以SES法提取锰渣中10种监测元素的六种形态,并结合HPLC-ICP-MS(高效液相色谱-电感耦合等离子体)分析结果探索锰渣中监测元素的迁移转化特性,通过同步辐射XANES进一步研究锰渣中Se的毒理学特性。
结果表明：电解锰企业的原料-锰矿石品位普遍偏低、伴生元素多、伴生情况复杂、硒及重金属元素相对含量高,潜在环境风险较大。企业“三废”对周边土壤、植物和水体的污染严重,主要为Se、Cd的污染,并已经威胁到了企业周边人的健康,存在极大的环境隐患和风险。
陆地土壤受污染程度较水稻田土壤重,主要为Se和Cd污染,监测元素含量随采样点离渣库距离的增大呈现递减趋势。植物各部位对监测元素的富集能力普遍较强,Se尤为突出,Cd其次,植物根附带土壤中监测元素超标程度与该元素在植物体内的富集程度成正比；农产品受该行业的污染较为严重。锰渣库周边河水中Mn含量超地下水质Ⅲ类标准高达143.49倍；农田水中受污染程度低于河水；企业附近居民集聚区的地下水中Mn和Se的含量均已超出了国家规定的生活饮用水卫生标准中关于这两种元素的安全值上限；水体也因此存在着很大的环境风险。
锰渣是环境污染的最大源头,10种监测元素的含量相对较高。在自然条件下,锰渣中Se及重金属元素主要以水溶态、交换态和酸溶态这3种形式迁移到外环境,且随着周围环境pH值的减小,从锰渣中迁移和转化到外环境中的量就越大；通过同步辐射定性分析可知,锰渣中Se主要以Se032-形式存在,且毒性最大,与工艺过程中添加Se02有密切关系,除了产品锰片中夹带着少量的含硒物之外,其余大部份的含硒物质均随着滤渣进入到渣库,在长期的雨水浸泡和冲刷作用,大量有毒害的含硒物流入外环境,污染河流、地下水源,使得农作物体内富集更多的有毒有害元素。
图[21]表[29]参考文献[80]
With the increase of foreign and domestic market demand for manganese, the development in industry of electrolysis manganese was rapid in the world. And above all in our country, this development was also improved by leaps and bounds. However, it also leads to many ecological environment problems. Three wastes existed potential risks to environment. Se and heavy metals pollution also damaged environment nearby in industry of electrolysis manganese.
Manganese ore stone, manganese residues and surrounding soil, plants and water which comes from10typical electrolysis manganese industries was used in this paper. This paper used microwave and electrolytic plate digestion for pretreat samples and quantitative analyzed10types of elements by ICP-MS technology, including Se, Cr, Mn, Co, Ni, Cu, Zn, As, Cd, Pb. It further comprehensive analyzed pollution which came from electrolysis manganese industry affected on neighboring soil, plant and water. Testing results of soil samples based on the national background average value. And the results of water sample based on standard of drinking water and groundwater. Enrichment extent of monitored elements in accessory soil with plants was researched in this paper. Six kind species of10types of elements were extracted in manganese residues by SES technology. The characteristics about migration and transformation of monitored elements in manganese residues were studied by combining analysis results of HPLC-ICP-MS. Finally, it further studied toxicologic characteristics of Se was studied furtherly by synchrotron radiation XANES technology.
Results showed that raw materials about the industry of electrolysis manganese had potential risk. Many associated elements existed in manganese ore stone and its grade was generally low. However, the situation of association was very complex. Relative content of Se and heavy metal elements was higher. Soil, plants and water near by electrolysis manganese industry suffered serious pollution by three wastes which from industry. This pollution of Se and Cr was mainly showed. It had affected human health and safety living in surrounding in industry of electrolysis manganese and also was a great environmental risk and potential troubles.
By the extent of the pollution about land soil was more serious than rice paddies. It mainly showed Se and Cr pollution. But the content of monitored elements was gradually decreased with the increase of distance between sample point and manganese residues library. Capacity of the enrichment was generally stronger to monitored elements each part of plant. This capacity of Se was strongest and secondly was Cr. The extent of exceeding standard on monitored elements in accessory soil with plants proportional to it's enrichment in plant. This extent to the edible part of crops was more serious. Content of Mn in the river water surrounding manganese residues library was143.49times than that in the groundwater III type of standard. Generally, the exceeding multiple of farmland water was lower than river water. The content of Mn and Se in resident drinking water was beyond national sanitary standard for living and drinking water. Therefore, there was a huge water environmental risk.
The biggest source of environmental pollution was manganese residues. But the content of monitored elements was relatively bigger. In the natural conditions, Se and some heavy metal elements, including water dissolves species, exchangeable species and sour dissolves species, could migrate and transform to external environment. With acidity increase in environment, the capacity of migration and transformation was increased gradually. Qualitative analysis by synchrotron radiation technology was showed that the species of Se in manganese residues was mainly SeO32-, but the toxicity of this species was largest. It closely related to add SeO2to the process of technology. Only a small amount of Se was contained in products but most of rest accessed to manganese residues library along with filter residues. A large number of materials containing Se were sent to the environment under the long-term soaked and scoured action of rain. It not only polluted groundwater and crops even threaten human life.
Figure [21] table [29] reference [80]
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