GYIG OpenIR  > 研究生
贵州万山矿区稻田重金属污染风险评价
其他题名Risk assessment of heavy metals contamination in rice paddies in Wanshan mining area, Guizhou, Southwest China
ADLANE BAYOU
学位类型博士
导师仇广乐
2019
学位授予单位中国科学院大学
学位授予地点中国科学院地球化学研究所
关键词重金属 万山矿区 土壤污染 人体暴露
摘要

五十多年来,污染一直是我们当今世界所面临的最严重问题之一,其主要由工业化快速发展、技术进步和人口显著增加所导致。污染是指在环境中通常为人造的大量的危险化学品,其有害影响可能在全球各地长期进行。污染会影响水、空气、土壤和沉积物,它可能以明显的形式存在(漂浮在海面上的石油),也可能肉眼观察不到(田间广泛使用的农药或土壤中广泛存在的重金属,沉积物或溶解在水生系统中)。重金属被定义为相对原子量和密度至少比水高5倍的金属元素。在化学背景下,重金属通常基于它们的物理化学性质来定义。在土壤科学中,人们认为“金属微量元素”指存在的矿物质化合物浓度很低。近年来,与这些金属微量元素的环境污染相关的生态和全球公共卫生问题日益增加。此外,由于其在若干工业,农业,家庭和技术应用中的使用呈指数增长,人类暴露也急剧增加。据报道,环境中的重金属来源包括地质,工业,农业,制药,生活污水和大气来源。环境污染在采矿和冶炼厂以及其他金属工业作业等点源地区非常突出。重金属通过地质过程和生物循环在环境中自然重新分布。然而,工业和技术活动减少了金属在岩石中的停留时间,它们形成了新的金属化合物,通过化石产品的燃烧引入大气中。我们将其区分由人类来源(人为)和自然部分(天然)造成污染的部分。陆地地壳中天然存在重金属有助于火山岩,变质岩和沉积岩的矿物组成,重金属通过自然过程在环境中发生,包括火山活动,风化森林火灾和气溶胶形成,火山活动具有大量贡献,由于爆炸活动或低容量连续排放造成的排放,特别是地热活动和岩浆脱气。 相比于天然金属通常以相对惰性的形式固定,来自人为输入的金属往往以相当活泼的化学形式存在,因此其比天然存在的金属具有更高的风险。其中,人为因素包括:石油化工;化石燃料(燃煤发电厂、工业锅炉、水泥窑等);运输(公路和非公路车辆和发动机、船舶);废物焚烧;工业产品(电子开关、牙科用汞合金、荧光灯);城市垃圾(污水、污水污泥、家庭垃圾);农药。吸入空气污染物,污染水的消耗以及接触受工业废物污染的土壤会使人类暴露在外。金属可以以无机形式或有机形式吸收。对于某些元素,如砷和铜,无机形式是毒性最大的。对于其他人,如汞和铅,有机形式是最有毒的。人们吸收的金属量直接影响健康。它可能具有剧毒性(空气或水中的高峰污染),或由于累积效应(通过持续暴露于污染环境或因为人类处于食物链的末端)而产生毒性。重金属在生物体内积累,破坏平衡和生物机制,造成毒害作用。它们可以影响神经系统,肾脏,肝脏,血液成分,呼吸系统等。众所周知,在中国,采矿和农业活动一直是人为金属的主要来源。长期以来,不同种类(金,朱砂等)的大规模采矿活动进行,1000年来农业用地也被人们所利用,尽管在过去30年中,中国经济发展迅速,与不同领域的大规模工业相关,需要开发更多的资源,中国经济的这一显着变化引领中国经济发展。作为世界上最大的经济体之一,随着任何发展,对中国不同地区的环境影响已经发生,影响土壤,水,空气和农作物质量,并使公众面临不同的健康风险,成为当今中国面临的最大变化之一,在中国环境中开展了许多科学研究,使公众面临不同的健康风险。据报道,工业区的污染较高,其中30%具有潜在的致癌风险,且致癌风险处于相当高的程度。中国是最大的汞生产国,汞作为一种高毒性元素已被证明会影响到中国不同地区和环境,现大约已有402吨的汞被释放到大气中。其中,煤炭燃烧包括燃煤电厂是中国大气中汞排放的主要人为来源,占总排放量的36%。据报道,中国土地受重金属影响较大,其中天津市和湖南省土地面积为40,01至71.04%,污染最为严重,其次是贵州、广西和广东省。受影响的粮食产量所占比例为30%至40%,其中各省受影响的粮食产量占中国粮食总产量的比例与耕地产量相似。本论文的主要目的是研究中国西南贵州万山矿区不同重金属(Hg,Sb,As,Cu,Mn,Zn,Cr,Cr,Ni和Pb)的现状,并评估土壤污染风险及对有毒元素的人类暴露。具体的科学目标如下:定位稻田土壤中不同重金属的热点,确定污染源;使用不同的环境因素评估土壤污染及其生态风险;确定从土壤到水稻的转移因子,并通过确定万山矿区污染物的致癌和非致癌潜力来评估人类暴露。贵州省万山汞矿区是中国最大的汞产区。在万山矿区,大约估计了2.2万吨金属汞和6千吨朱砂,以及大量的矿山废弃物。在万山Hg矿区,周围的生态系统释放了大约1.258亿吨煅烧物和202亿立方米含汞有毒气体。1949年至1990年初。由于这种大规模的采矿生产,万山的各个地区都发生了严重的汞污染,包括不同的环境区,河流,沉积物,土壤,植被和大气。朱砂矿石通常与其他有毒元素有关,如锑(Sb)、砷(As)、铜(Cu)、锰(Mn)、锌(Zn)和铅(Pb),它们也可以释放到附近的环境中在矿石加工和干馏过程中。除采矿业外,农业活动也是微量金属的另一个来源,土地的长期使用伴随着农用化学品的频繁使用,导致各种微量金属如铜(Cu),锌(锌),镍的积累土壤中的(Ni)和镉(Cd)。迄今为止,关于除汞以外的有毒元素的系统研究很少,特别是关于万山汞矿区的稻田土壤。考虑到土壤吸收和向可食用部分的运输,作为全球主要作物的水稻被认为是人类饮食中汞的重要来源。它构成了汞污染区域的潜在风险,例如汞污染的采矿最重要的甲基汞(MeHg)暴露源不是鱼类,而是大米。这是贵州省(中国)汞矿区的情况。考虑到来自该地区的水稻中的汞浓度可达到500 ng g-1 以及该主食谷物的每日食用量,估计膳食摄入量约为400 g。通过大米摄入的甲基汞摄入量反映在这些地区居民头发中的甲基汞水平。以往的研究表明,万山地区不同村庄的人发中总汞和甲基汞浓度较高,分别为3.3±1.4μg/ g至5.5±2.7μg/ g,T为1.2±0.5μg1.9±0.9μg/ g -Hg和Me-Hg Hg,这表明该地区人口的汞暴露。从万山地区的138个地点采集了稻米和土壤样本。从每个地点收集2个米粒子样品和相对土壤。收集所有样品并储存在密封的聚乙烯袋中以避免交叉污染,然后运送到实验室,在那里将所有样品风干,在陶瓷盘磨机中研磨并筛分至150目。使用Lumex机器RA-915 +(Lumex Ltd.,Russia)测定Hg。在HNO3-HF的混合酸中消化约0.1-0.3g固体土壤和固体稻米样品,并通过消化物中的Cd,Sb,Cr,Ni,Cu,Zn,Pb,Mn,As和Ti浓度测定。电感耦合等离子体质谱(ICP-MS,Element,Finnegan MAT Co)。万山地区土壤重金属含量测定结果表明,万山地区大部分土壤样品中Hg和Sb均有明显富集,浓度分别为0.14~21 mg / kg和0.01~78 mg / kg。这两种元素的浓度高于背景水平和国家标准水平。 As,Pb,Zn,Cd,Cu和Mn的浓度范围为0.41-92 mg / kg,10-103 mg / kg,0.25-508 mg / kg,01-3.6 mg / kg,0.05-56 mg / kg和2.2-760毫克/千克。这些微量元素在某些点上显示出明显富集,但是在大多数样品中浓度低于背景水平。没有观察到明显的Ni和Cr富集,分别在0.12-52mg / kg和0.11-109.39mg / kg之间。本文计算污染负荷指数(PLI)、地质累积指数(I-Geo)和富集因子(EF),以评估万山矿区稻田土壤重金属的潜在风险。表3.3中列出的PLI结果显示出Hg和Sb的严重污染。还观察到Pb和As的明显污染,而Cr,Cd,Zn,Cu,Ni和Mn没有发生污染。I-Geo和EF的结果显示出极高的Hg值和极高的Sb富集值,暗示Hg、Sb严重污染。砷,铅,锌,镉,铜,锰,镍和铬的EF结果显示亏损至中度富集,考虑到这些元素的PLI结果,说明万山地区稻田的土壤被砷,铅和镉污染,Zn、Cd和Cu未被污染至中度污染,而Ni和Mn没有污染。万山矿区稻田土壤重金属和类金属的生态影响,其中 RI达到了很高的水平,表明研究区域存在严重的重金属污染。每种重金属元素的相对贡献,以Ei与RI相比的百分比计算为Hg为93.78%作为研究区域的主要污染物,Sb为2.41%作为第二主要污染物,则As和Cd贡献率为1.33% Cr,Pb,Zn,Cu,Ni和Mn的相对贡献率非常低,<0.5%。 RI的高水平和Hg的高相对贡献表明,历史上大规模的Hg矿采矿业和万山地区的人工采矿是土壤中污染物的主要来源。另外,汞不是从朱砂干馏中释放的唯一有毒元素,其他元素如Sb,Cd,Pb和As可能也与采矿业有关。万山地区的重金属评估显示出高生态风险,主要归因于大规模汞矿开采以及人工干馏产生的高水平汞的存在。此外,这种采矿活动还导致其他重金属如Sb,As,Pb,Cr,Cd的释放,但是万山地区的其他人为来源可能释放出重金属。显示,Zn、Mn、Cu、Ni和Cr的含量高达8.08至21.42 mg / kg,3,17至29,89 mg / kg,0.32至20.34 mg / kg,0.07至4,56和0.32至20.33 mg / kg,而Hg、Sb、As、Pb、Cd和Ni含量较低,为0.001至0.45 mg / kg,0.003至0.18 mg / kg,分别为0.02至0.18mg / kg,0.001至0.31mg / kg,0.004至0.25mg / kg。万山矿区每种重金属的转移因子(TF)如图4.2所示。 Hg、Sb、As、Pb、Zn、Cd、Cu、Mn、Ni和Cr的TF平均值按Cu> Zn> Cr> Cd> Mn> Sb> Hg> Ni> As> Pb的顺序降低(图4.2)。 Cu、Zn、Cr和Cd分别具有30%,17.16%,10.22和8.85的高TF,其中Mn、Sb、Hg分别为4.24%,2.11%和1.45%,而Ni,As和Pb低于1。我们对这两个变量进行了一系列线性回归分析,以研究水稻从土壤中吸收重金属的能力(转移因子TF)与以下因素之间的相互作用:1-土壤重金属浓度,2-土壤pH值,3-总含量土壤中的碳。结果表明: Hg、Sb、As、Pb、Zn、Cd、Cu、Mn、Ni和Cr的转移因子与相应的重金属浓度呈下降关系。这一显著特征表明,土壤中重金属浓度较高,水稻从土壤中吸收重金属的潜力较低。转移因子和pH之间的关系是在除了Hg之外的所有元素的负回归之后,其似乎随pH增加,土壤中转移因子与土壤总含量之间的关系依次为负回归,提示高碳浓缩区转移因子减少。然而,这一结果还不足以解释水稻对重金属的吸收机制,许多以前的生物地球化学研究表明水稻从土壤中吸收重金属的能力不仅仅取决于土壤中元素的浓度,地球化学土壤中的土壤,细菌和微生物活动的特征以及不同部位水稻(根,茎,叶和谷粒)的生理特征无疑是了解土壤中重金属垂直运动机制的关键。人类风险暴露本文采用每日估计摄入EDI,危险系数(HQ)和致癌风险CR的方法,通过大米消耗评估万山矿区重金属的健康状况 。Zn的EDI估计最高,值为42.5μg/ kg / d,EDI Mn,Cu和Cr含量高,分别为26.08,20.65和13.12μg/ kg / d,其次是Ni和EDI 4,15μg/ kg / d,然后是As,Pb,Sb,Cd和Hg,EDI分别为0.26,0.17,0.12,0.11和0.06μg/ kg / d。 Hg,Sb,As,Pb,Zn,Cd,Cu,Mn,Ni,Cr的危险商数分别估计为0.4,0.03,0.09,0.05,0.14,0.14,0.11,0.56,0.19,0.21和0.01。对于所有测量的重金属,Hazard Quotient HQ估计的非致癌风险小于1,这表明没有物质对健康安全造成风险。然而,危险指数是所有元素的危险商数的总和高于1,其值为1.77,这表明存在潜在风险,使当地人口遭受由重金属混合物引起的非致癌疾病大米摄入。 As的致癌风险CR低于1,表示安全性为0.38,而对于Zn,Ni和Cr,致癌风险高于1,估计值分别为1.69,3.78和6.56,表明当地人群中可能发生癌症,这是由上述因素通过大米摄入引起的。总癌症风险CRt估计超过1,CRt为12,41表明可能由多种致癌元素引起的癌症。本论文根据研究结果,得出以下结论:1-万山矿区特别是矿区附近Hg和Sb的高积累,As、Pb、Zn、Cd、Cu和Mn的中高程度富集,Ni和Cr没有明显的富集。2-空间分布格局和统计分析表明,Hg、Sb和Cd之间存在显着的相似性,在周围地区以高浓度呈现,手工干馏使矿山成为万山地区Hg和Sb的主要来源。 Ni、Cu与Pb之间存在显着的相关性,这些元素的一种可能来源可能是朱砂干馏,但程度小于Hg、Sb和Cd。第三组相似性元素包括Cr,As,Zn和Mn,它们也可能与朱砂干馏有关。因此,这些元素的主要来源是汞开采,而As的另一个来源是煤炭燃烧,被万山地区的当地人口高度使用,并且Mn也可以从万山地区的锰工厂释放到环境土壤中。3-评估万山地区土壤重金属污染,三个环境因素:污染负荷指数,地质累积指数I-geo和富集因子EF;PLI结果表明Hg,Sb,As和Pb存在污染,而Zn,Cd,Cu,Mn,Ni和Cr不存在污染。从I-geo和EF获得的结果表明,Hg严重污染,Sb严重污染,As,Pb和Zn中度污染,Zn,Cd,Cu,Mn,Ni和Cr轻度污染。对万山矿区稻田土壤重金属和类金属生态影响的评价表明,风险指数水平较高(RI = 126013.03),表明万山地区土壤重金属污染严重。 Hg是主要污染物,对RI的贡献率为93.78%,其次是Sb为2.41%,As和Cd分别贡献率为1.33%和1.32%,以及Cr,Pb,Zn,Cu,Ni和Mn的相对贡献非常低(小于<0.5%)。 RI的高水平和Hg的高相对贡献表明,历史上大规模的Hg采矿业和万山地区的手工采矿是土壤中污染物的主要来源。由于汞不是从朱砂干馏中释放的唯一有毒元素,因此其他元素如Sb,Cd,Pb和As可能与采矿业有关。4-万山矿区水稻重金属检测结果显示,锌,锰铜,镍,铬含量较高,为8.08~21.42 mg / kg,3,17~29,89 mg / kg,0.32分别为20.34 mg / kg,0.07至4,56和0.32至20.33 mg / kg,而Hg,Sb,As,Pb,Cd和Ni含量较低,范围为0.001至0.45 mg / kg,0.003至0.18 mg / kg,0.02至0.18mg / kg,0.001至0.31mg / kg,0.004至0.25mg / kg。十种重金属的迁移系数依次为Cu> Zn> Cr> Cd> Mn> Sb> Hg> Ni> As> Pb。 TF与土壤中重金属浓度的关系越来越明显,这表明其他参数对土壤中重金属浓度的影响,水稻吸收土壤中重金属的能力也取决于地球化学特征,如pH值和有机质土壤中的细菌和微生物活动以及不同部位水稻(根,茎,叶和谷粒)的生理特征。5-通过大米消费评估非致癌风险表明,十种重金属中皆不存在非致癌性慢性病的潜在风险,所有HQ均小于1,但所有金属的风险指数HI均达到1.77,其中表明在当地人口中发生慢性病的潜在风险。对风险指数HI的主要贡献是Cu,因为每日较高摄入量(EDI =26.65μg/ kg / d)和Hg,及其高毒性(RfD = 1.6 * 10-4)。万山地区水稻的致癌风险分别为Cd,Ni和Cr,CR分别为CR = 1.69,3.78和6.56,而As的CR小于1,表明安全性较高,未来有必要对镍和铬开展研究,以了解更多关于这两种元素在万山地区的致癌作用。考虑到得出的结论,建议对万山地区的所有重金属进行连续监测,不仅要关注汞,还要关注重金属运输机理,更多地研究人为来源,特别是手工干馏,必要时采取调节措施。

其他摘要

In the last few decades, environmental issues related to heavy metal contamination have became a major concern worldwide as a result of rapid economic development, associated by massive increase of mining, industrialization, the use of agrochemicals , mining and advanced technology application, large quantities of heavy metals have been released into the different part of the ecosystem (air, water, soil, sediments) conducting to serious case of pollution in many areas around the world Pollution means the presence in the environment of large quantities of dangerous chemicals, fairly from man-made sources. This pollution can affect the water, the air, the soil and sediments. It also can harm the human health through the food chain. Heavy metals are naturally redistributed in the environment through geological processes and biological cycles. However, Industrial and technological activities reduce the residence time of metals in rocks, Metals from anthropogenic inputs are present in fairly reactive chemical forms and, as a result, carry much higher risks than naturally occurring metals, which are most often immobilized in relatively inert forms.Heavy metal contamination can occur in deferent parts of the ecosystem, soil, water and air conducting to possible effect on the food chain, so the public health, humans is exposed by inhalation of air pollutants, consumption of contaminated water, and exposure to soils contaminated with industrial waste. The metals can be absorbed in the inorganic form or in the organic form. For some elements, such as arsenic and copper, the inorganic form is the most toxic. For others, like mercury and lead, organic forms are the most toxic. Heavy metals accumulate in living organisms and disrupt equilibrium and biological mechanisms, causing toxic effects. They can affect the nervous system, kidney, liver, blood composition, respiratory system...etcIn China, Mining and agriculture have been the main anthropogenic sources of metals for long time. But, In the last 30 years, China has known a rapid economic development, lead the country to the top as one of the biggest economies in worldwide, however, as a result, the environment was affected in many regions in china, heavy metal pollution is actually one big challenge in china now, The pollution has been documented to be higher in industrial areas, in which 30% pose potential non-carcinogenic risk, and the As carcinogenic risk is at some unacceptable levels. China is also the largest producer of mercury in the world, mercury pollution has been reported in various areas in China, and about 402 Tone metric of mercury have been released into the atmosphere 1995. Coal combustion including coal fired power plant and domestic uses are the main anthropogenic sources of mercury emission into the atmosphere in china contributing with 36% of the total emission.In this research project, Wanshan abandoned mining area in Guizhou province was selected to assess the heavy metal in soil and rice.The main objective of this study was to investigate the current status of different heavy metals (Hg, Sb , As , Cu , Mn , Zn , Cr, Cr, Ni, and Pb) in Wanshan mining Area, Guizhou, southwest China, in order to evaluate the soil contamination risk and the human exposure to these toxic elements. The specific scientific objectives were as follows:ü Localize the hot spots of different heavy metals in rice paddy soil and identify the pollution sourceü Asses the soil contamination and its ecological risk, using different environmental factorü Determine the transfer factor from soil to the rice and evaluate the human exposure by determining carcinogenic and non-carcinogenic potential of pollutants in Wanshan mining area.The Wanshan region located in the east part of in Guizhou Province was for long time known by its large scale Hg mining, it wa actually the largest mercury mine in China. An approximate estimation of 22 thousand tons of metal Hg and 6 thousand tons of cinnabar, plus large quantities of mine wastes were produced at Wanshan mining area. 125.8 million tons of calcines and 20.2 billion m3 of Hg-containing toxic gas have been estimated to be introduced in the surrounding ecosystems, in the Wanshan Hg mining region between 1949 and early 1990. Due to this massive mining production, Wanshan region have been suffering severe Hg contamination that occurred in various areas in all parts of the ecosystem; rivers, sediments, soil, vegetation and atmosphere. . To date, few studies on those toxic elements except for Hg have been systematically conducted, particularly in regarding to paddy soils in Wanshan Hg mining region. Rice, the dominant crop in the world, is recognized to be an important source of Hg in human diet considering the soil uptake and transport to the edible part. It constitutes a potential risk in Hg polluted areas, such Hg-contaminated mining regions, where the most important Methylmercury (MeHg) exposure source is not fish, but rice consumption. This is the case of Hg mining areas in Guizhou province (China). Considering that Hg concentration in rice from this region can reach values up to 500 ng g-1, MeHg intake through rice ingestion has been reflected on the levels of MeHg in hair of inhabitants of such areas.Rice and Soil samples were collected from 138 sites in Wanshan area. 2 sub samples of rice grains and relative soil were collected from each site. All samples were collected and stored in sealed polyethylene bags to avoid cross contamination, then transported to the laboratory, where all were air dried, grinded in a ceramic disc mill and sieved to150 meshes. Hg was determined using Lumex machine RA-915+ (Lumex Ltd., Russia). Approximately 0.1-0.3 g of solid soil and solid rice samples were digested in the mixed acid of HNO3–HF, and Cd, Sb, Cr, Ni, Cu, Zn, Pb, Mn, As and Ti concentrations in the digests were determined by Inductively Coupled Plasma Mass Spectroscopy (ICP-MS, Element, Finnegan MAT Co)The results of heavy metal concentration in soil from Wanshan area have shown Significant accumulation of Hg and Sb was observed in most of the soil samples from Wanshan area, with concentrations ranging from 0.14 to 21 mg/kg and 0.01 to 78 mg/kg, respectively. The concentration of these two elements was higher than the background level and the national limit levels. Concentrations of As, Pb, Zn, Cd, Cu, and Mn ranged between 0.41-92 mg/kg, 10-103 mg/kg, 0.25-508 mg/kg, 0.01-3.6 mg/kg, 0.05-56 mg/kg and 2.2-760 mg/kg, respectively. Those trace elements showed a significant accumulation in some points, but the concentration was lower than the background level in the majority of the samples. No significant accumulation of Ni and Cr was observed, ranging between 0.12-52 mg/kg and 0.11-109.39 mg/kg respectively. The pollution Load Index (PLI), the Geo-accumulation Index (I-Geo), and the Enrichment Factor (EF) were calculated to assess the potential risk of heavy metals in soil in rice paddies in Wanshan mining area. The results of the PLI presented in Table 3.3 have shown extreme pollution by Hg and Sb. Significant pollution by Pb and As was also observed, while no pollution occurred by Cr, Cd, Zn, Cu, Ni and Mn. The results of the I-Geo and the EF have shown very to extremely high values for Hg and significant to very high enrichment values of Sb, conducting to an extreme pollution according to the I-Geo results. The EF results for As, Pb, Zn, Cd, Cu, Mn, Ni, and Cr have shown a depletion to mineral enrichment to moderate enrichment, considering with the PLI results for these elements indicate that soil from rice paddies in Wanshan area were moderately polluted by As, Pb, and Cd, from unpolluted to moderately polluted by Zn, Cd and Cu, while there was no pollution by Ni and Mn occurred.The ecological impacts of heavy metals and metalloids in soil from rice paddies in Wanshanmining area. The RI reached a very high level, which indicates severe heavy metal pollution in the study area. The relative contribution from each element, as calculated as the percentage of Ei compared to RI as Hg of 93.78% as the major pollutant. The results of trace elements in rice samples has shown high levels on Zn, Mn Cu, Ni and Cr ranging from 8.08 to 21.42 mg/kg, 3,17 to 29,89 mg/kg, 0.32 to 20.34 mg/kg, 0.07 to 4,56 and 0.32 to 20.33 mg/kg respectively, while Hg, Sb, As, Pb, Cd and Ni are presented in low levels, ranging from 0.001 to 0.45 mg/kg, 0.003 to 0.18 mg/kg, 0.02 to 0.18 mg/kg, 0.001 to 0.31 mg/kg, 0.004 to 0.25 mg/kg respectively.The transfer factor (TF) for each heavy metal in Wanshan mining area is shown in Figure 4.2. The average values of TF for Hg, Sb, As, Pb, Zn, Cd, Cu, Mn, Ni and Cr decreased in the order of Cu > Zn > Cr > Cd > Mn > Sb > Hg>Ni>As>Pb (Figure 4.2). Cu, Zn, Cr and Cd had the high TF with 30%, 17.16%,10.22 and 8.85 respectively, followed Mn, Sb, Hg with TF of 4.24%, 2.11% and 1.45% respectively, whereas the TF for Ni, As and Pb was lower than 1 a series of regression analyses for the two variables was conducted to investigate the interaction between capabilities that rice uptakes heavy metal from soil (the transfer factor TF) and: 1- soil’s heavy-metal concentrations and 2-soil pH, 3- Total content of Carbon in soil. The results have shown that:- The transfer factors of Hg, Sb, As, Pb, Zn, Cd, Cu, Mn, Ni and Cr have decreasing relationships with the corresponding heavy-metal concentrations. This remarkable phenomenon indicates the higher heavy metal concentration in soil, the lower potential of rice plant to uptake heavy metals from soil.- The relationship between the transfer factor and the pH was following negative regression fol all element except for Hg which seems to increase with pH- The relationship between the transfer factor and the Total content of carbon in soil was following negative regression for all element , suggestion that the transfer factor decrease in high carbon contemning areas.However, this results are not enough explain the mechanism of heavy metal uptake by rice, many previous bio-geochemical studies have shown that the capability of rice to absorb heavy metals from soil does not depend only on the concentration of an element in soil, geochemical characteristic of soil, bacterial and microbial activities in soil and the physiological characteristic of the different parts rice plant (roots, stems, leaves and grains) are without doubt the keys to understand the mechanism of the vertical movement of heavy metals from soil to rice plant.The methods of Daily Estimated Intake EDI, the Hazard Quotient (HQ) and Carcinogenic Risk CR were used to assess the health exposure to heavy metals in Wanshan mining area through rice consumption; EDI of Zn was estimated to be the highest, with values of 42.5 μg/kg/d., EDI Mn, Cu and Cr high levels with values of 26.08, 20.65, and 13.12 μg/kg/d respectively, followed by Ni with EDI of 4,15μg/kg/d, then As, Pb, Sb, Cd and Hg, with EDI of 0.26, 0.17, 0.12, 0.11 and 0.06 μg/kg/d respectively. The Hazard Quotient for Hg, Sb, As, Pb, Zn, Cd, Cu, Mn, Ni, Cr was estimated to be 0.4, 0.03, 0.09, 0.05, 0.14, 0.14, 0.11, 0.56, 0.19, 0.21 and 0.01 respectively. The non-carcinogenic risk estimated by the Hazard Quotient HQ was less than 1 for all the measured heavy metals, which indicate no risk to the health safety from any of the substance. However the Hazard Index which is the sum of the Hazard Quotient of all elements was higher than 1whith a value of 1.77, which indicates the existence of potential risk, exposing the local population to suffer non-carcinogenic diseases caused by the mixture of heavy metals through rice consumption. The Carcinogenic Risk CR was lower than 1 one for As with a value of 0,38 indicating safety, whereas for Zn, Ni and Cr, the Carcinogenic Risk was higher than 1, with estimated values of 1.69, 3.78 and 6.56 respectively, indicating that cancer may occur among the local population, caused by the above elements through rice consumption. The total Cancer Risk CRt was estimated to exceed 1, CRt was 12, 41 which indicate that cancer may occur, caused by multiple carcinogenic elements The examination of heavy metal in soil and rice from Wanshan mining area has conducted to the following conclusion:1-High accumulation of Hg and Sb in Wanshan mining area, moderate to high accumulation of As, Pb Zn, Cd, Cu and Mn and no significant accumulation of Ni and Cr. high level of mercury occur in the mine surrounding are and near artisanal retorting in Gouxi. 2- The main source of those elements is Hg mining, but another source of As is coal combustion, highly used by the local population of Wanshan area, and Mn can also be released into the environmental soil from manganese factories in Wanshan area. 3- The evaluation of ecological impacts of heavy metals and metalloids in soil from rice paddies in Wanshan mining has shown very high level of risk index (which indicates severe heavy metal pollution in Wanshan area. The very high level of RI (93%) and the high relative contribution of Hg indicate that the historically large scale Hg mining industry and artisanal mining in Wanshan area are the major source of pollutants in soil. Since Hg is not the only toxic element that is being released from cinnabar retorting, other elements such as Sb, Cd, Pb, and As could be associated to the mining industry.4- The examination of heavy metals in rice from Wanshan mining area has shown high has shown high levels on Zn, Mn Cu, Ni and Cr ranging from 8.08 to 21.42 mg/kg, 3,17 to 29,89 mg/kg, 0.32 to 20.34 mg/kg, 0.07 to 4,56 and 0.32 to 20.33 mg/kg respectively, while Hg, Sb, As, Pb, Cd and Ni are presented in low levels, ranging from 0.001 to 0.45 mg/kg, 0.003 to 0.18 mg/kg, 0.02 to 0.18 mg/kg, 0.001 to 0.31 mg/kg, 0.004 to 0.25 mg/kg respectively. the transfer factor of the ten heavy metals was following the order Cu > Zn > Cr > Cd > Mn > Sb > Hg>Ni>As>Pb. The TF is Showing increasing relationship with the heavy metal concentration in soil, which indicate the implication of other parameter than heavy metal concentration in soil, the capability of rice to absorb heavy metals from soil does also depend on geochemical characteristic such us pH and organic matter, bacterial and microbial activities in soil and the physiological characteristic of the different parts rice plant (roots, stems, leaves and grains).5- The assessment non-carcinogenic risk through rice consumption have shown that none of the ten heavy metal present potential risk of non-carcinogenic chronics, all HQ were less than 1, but the Risk Index HI of all the metal together reached 1.77, which indicates potential risk of occurring of chronics among the local population. The main contribution to the risk index HI were Cu because of its high estimated daily intake (EDI=26.65 μg/kg/d) and Hg because of its high toxicity (RfD =1.6*10-4). The carcinogenic risk occurred in rice from Wanshan area is presented by Cd, Ni and Cr which has CR= 1.69, 3.78 and 6.56 respectively, whereas As has CR less than 1although indicating safety. Although the study of Ni and Cr would be necessary to understand more about the carcinogenic effect of these two elements in Wanshan area.Considering the conclusions obtained, it is recommended to have continuous monitoring of all heavy metals in Wanshan area, not only mercury, and focus on the mechanism of heavy metal transport, to investigate more the anthropogenic source, especially artisanal retorting and to take regulation action if necessary.

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ADLANE BAYOU. 贵州万山矿区稻田重金属污染风险评价[D]. 中国科学院地球化学研究所. 中国科学院大学,2019.
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