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贵州省典型土法炼汞地区汞的生物地球化学循环和人体汞暴露评价
其他题名Biogeochemical cycle of Mercury and Human Exposure in Typical Artisanal Mercury Mining Areas, Guizhou Province
李平
2008-05-26
学位授予单位中国科学院地球化学研究所
学位授予地点地球化学研究所
学位名称博士
关键词汞矿区 土法炼汞 汞释放量 环境汞污染 人体汞暴露
摘要贵州省是我国最重要的汞工业基地,境内分布着大量的汞矿床,汞金属储量88000 t,占全国总储量近80%。汞矿开采、冶炼历史悠久,大规模的汞矿开采冶炼活动都已经停止。但是,由于汞矿区偏僻的自然地理位置、落后的经济水平和近期金属汞价格的攀升,这些地区仍然存在着较大规模的土法炼汞活动。大面积的土法炼汞活动和长期的大规模汞矿开采冶炼活动,给矿区生态环境造成了严重的汞污染。土法炼汞工艺十分落后,冶炼过程向周围大气释放大量的汞,而土法炼汞工人也必然会遭受严重的汞蒸气暴露。释放到大气的汞在进入周围环境后,在自然条件下通过微生物活动,会转化为毒性、生物有效性更强的甲基汞,并通过食物链富集放大,最终对矿区居民的身体健康构成一定的威胁。 本文选择贵州省务川汞矿区、万山汞矿区和铜仁垢溪、老屋场土法炼汞地区,进行了土法炼汞的汞释放量估算、汞矿地区环境汞污染调查及炼汞工人和矿区居民汞暴露调查和健康风险评价,系统阐述了贵州典型土法炼汞地区汞的生物地球化学循环特征及人体汞暴露评价。 1. 务川和铜仁垢溪地区的土法炼汞活动是当地大气的最主要人为释汞源。务川汞矿区土法炼汞的平均释汞因子为18.2%(6.9-32.1%),土法炼汞活动每年向大气排汞3.7-9.6 t;铜仁垢溪地区土法炼汞的平均释汞因子为9.8%(6.6-14.5%),土法炼汞活动每年向大气排汞1.3-2.7 t。 2. 务川汞矿区大面积的土法炼汞活动和长期大规模的汞矿活动以及垢溪、老屋场地区的土法炼汞活动,给当地的大气、地表水体和土壤造成了严重的汞污染,而汞污染程度受汞矿开采冶炼活动的历史和规模的影响显著。务川汞矿区大气汞浓度空间变化很大(7-40000 ng•m-3),受矿业活动影响的区域,大气汞含量明显升高;重污染区大气汞平均浓度为15000 ng•m-3,轻污染区为120 ng•m-3,对照区为24 ng•m-3。务川矿区地表水体的总汞含量的变化范围为43-2100 ng•L-1,总甲基汞含量变化范围为0.30-1.1 ng•L-1;垢溪、老屋场地区地表水体总汞含量的变化范围为92-2300 ng•L-1,总甲基汞含量变化范围为2.6-7.9 ng•L-1,地表水体显示了极强的甲基化能力。颗粒态汞占地表水体总汞含量的绝大部分比例,是矿区地表水体汞迁移的主要方式;而甲基汞则以溶解态为主。务川汞矿区土壤总汞含量的变化范围为1.3-360 mg•kg-1,垢溪、老屋场地区土壤总汞含量的变化范围为0.18-47.5 mg•kg-1,土壤剖面表层土壤汞的富集表明大气汞的沉降是土壤汞的重要来源,而土壤pH、有机质含量和土地利用类型影响着土壤中汞的迁移和富集。 3. 务川汞矿区土法炼汞工人尿汞含量的平均值高达1060 g•g-1 Cr,铜仁垢溪地区炼汞工人尿汞含量的平均值为347 g•g-1 Cr,铜仁老屋场地区炼汞工人尿汞含量的平均值为917 g•g-1 Cr,土法炼汞工人尿汞平均含量远远超过世界卫生组织规定的职业暴露人群的最大允许值-50 g•g-1 Cr,说明土法炼汞工人遭受严重的汞蒸气暴露。部分土法炼汞工人已经表现出轻度慢性汞中毒的症状,其肾脏已经遭受到一定程度的损伤。铜仁垢溪地区一般居民尿汞的平均值为40.0 g•g-1 Cr,铜仁老屋场地区一般居民尿汞含量的平均值为66.2 g•g-1 Cr,万山汞矿区大水溪居民尿汞含量的平均值为56.9 g•g-1 Cr,说明土法炼汞地区一般居民也遭受一定的汞蒸气暴露。对照区人群尿汞含量的平均值为1.30 g•g-1 Cr,万山下场溪村居民尿汞含量的平均值为2.5 g•g-1 Cr,其尿汞水平与对照组接近。 4. 食用大米是汞矿区居民甲基汞暴露的主要途径。万山汞矿区大水溪、下场溪和报溪3个村庄居民头发总汞含量的几何平均值分别为7.3、1.9和2.3 g•g-1,而头发甲基汞的平均含量分别为2.8、1.3和1.5 g•g-1,说明万山汞矿区居民存在一定程度的汞暴露。3个村庄居民食用大米总汞的平均含量分别为58.5、21.3和33.1 ng•g-1,大米甲基汞的平均含量分别为14.6、5.7和4.0 ng•g-1。居民食用的蔬菜、猪肉和饮水也表现出很高的总汞含量,但是甲基汞含量很低。3个村庄居民食用大米的摄入量占总甲基汞摄入量的平均比例分别为97.5%、94.1%和93.5%,且不同参与者每日通过食用大米的甲基汞摄入量和对应的头发甲基汞含量之间存在显著的相关关系 (r=0.65, p<0.01),这证实了居民头发甲基汞的来源确实是食用大米,食用大米是汞矿区居民甲基汞暴露的主要途径。 5. 铜仁垢溪、老屋场地区炼汞工人头发甲基汞的平均含量分别为5.05 g•g-1(2.35-10.6 g•g-1)和5.63 g•g-1(2.54-9.55 g•g-1),而一般居民头发甲基汞的平均含量分别为3.53 g•g-1(1.87-5.65 g•g-1)和4.01 g•g-1(2.29-9.23 g•g-1)。万山汞矿区大水溪、下场溪和报溪3个村庄居民头发甲基汞的平均含量分别为2.8、1.3和1.5 g•g-1。务川汞矿区土法炼汞工人和居民的头发甲基汞含量的变化范围为0.47-5.69 μg•g-1。对照组头发甲基汞的平均含量为0.65 g•g-1,变化范围为0.26¬-1.38 g•g-1。食用大米甲基汞摄入量的估算表明,铜仁垢溪和老屋场地区部分居民的甲基汞摄入量已经超过世界卫生组织2003年制定的标准-0.23 g•d-1•kg-1,汞矿区大部分人群的甲基汞摄入量超过了美国环保局的推荐值-0.1 g•d-1•kg-1 (USEPA, 1997),而对照区居民的甲基汞摄入量均没有超过这一推荐值,表明铜仁垢溪和老屋场地区居民存在一定的甲基汞暴露风险,而其他汞矿区人群也存在通过食用大米暴露甲基汞的潜在风险。
其他摘要Guizhou province is an important mercury (Hg) production centre in China and it owns many large Hg mineral deposits. The cinnabar deposits in Guizhou amount to about 88000 tons of metal Hg and consist of 80% of the total in whole China. It has a long history of Hg mining activities and large Hg mines had been abandoned recently. However, the illegal artisanal mining activities are extensively existed in Hg mining areas because of its remote position, backward economy and the markup of Hg. The artisanal Hg mining activities together with the long history large scales Hg mining activities have resulted in serious Hg contaminations to local environment in these Hg mining areas. Because the simple mining processes are without any environmental protection measures, a large amount of Hg vapor was released to the ambient air during the mining process and the workers might be seriously exposed to Hg vapor. The Hg that released into the surroundings may, under certain conditions, be converted into Methyl Hg (MeHg), which is an organic form and is more toxic and bio-available than inorganic Hg. This organic Hg is readily accumulated by biota owning to its lipophilic and protein-binding properties and eventually poses a threat to the local residents’ health through the food chains. In order to evaluate the biogeochemistry cycle of Hg in typical artisanal Hg mining areas in Guizhou Province, the Hg emission from the artisanal Hg mining, the Hg pollution investigation, the human exposure and risk assessment were carried out in Wuchuan, Wanshan Hg mining areas and Gouxi, Laowuchang areas in Tongren District. 1. The artisanal Hg mining was the most important anthropogenic Hg emission sources in Wuchuan and Gouxi areas. The average emission factor was 18.2% (ranging from 6.9 to 32.1%) and 9.8% (ranging from 6.6 to 14.5%) for the artisanal Hg mining in Wuchuan and Gouxi area, respectively, and the annual Hg emission was 3.7-9.6 and 1.3-2.7 metric tons in the two areas, respectively. 2. The artisanal Hg mining activities together with the long history large scales Hg mining in Wuchuan Hg mining area and the artisanal Hg mining activities in Gouxi and Laowuchang areas have resulted in serious Hg contaminations to local air, surface water and soil, the extent of Hg contamination depended strongly on the history and the scale of artisanal Hg mining activities. Total gaseous Hg in the ambient air in Wuchuan Hg mining area ranged from 7 to 40000 ng•m-3, the concentration of total gaseous Hg were significantly elevated in the serious affected area by the mining activities; average concentrations of total gaseous Hg in the ambient air were 15000, 120 and 24 ng•m-3 in the high polluted area, the median polluted area and control site, respectively. Hg concentrations in the surface water ranged from 43 to 2100 ng•L-1 for the Total Hg (THg) and from 0.30 to 1.1 ng•L-1 for the total MeHg in Wuchuan area. Hg concentrations in the surface water ranged from 92 to 2300 ng•L-1 for the THg and from 2.6 to 7.9 ng•L-1 for the total MeHg in Gouxi and Laowuchang area, which indicated high methlation abilities in the surface water. The particulate phase was the main route of Hg transportation, but the MeHg was mainly in dissolved phase. THg in the soil ranged from 1.3 to 360 mg•kg-1 and from 0.18 to 47.5 mg•kg-1 for Wuchuan and Gouxi, Laowuchang area, respectively. T-Hg distribution patterns in soil profiles showed that top soil is contaminated with Hg, which was derived from atmospheric deposition. Soil pH, organic matter concentration and the land-using types might play important roles in control of Hg concentrations and transport in the soil. 3. The mean of urinary Hg (UHg) was 1060 g•g-1 Creatinine (g•g-1 Cr), 347 g•g-1 Cr and 917 g•g-1 Cr for the artisanal mining workers in Wuchuan Hg mining area, Gouxi area and Laowuchang area, respectively, which were obviously exceeded the value (50 g•g-1 Cr) for the occupational exposure recommended by WHO. It indicated serious Hg vapor exposure for the artisanal mining workers. Several workers already manifested some clinical symptoms of lightly chronic Hg poisoning and the data showed a serious adverse effect on renal system for the workers. The mean of UHg was 40.0, 66.2 and 56.9 g•g-1 Cr for the residents in Gouxi area, Laowuchang area, and Dashuixi Village, Wanshan Hg mining area, respectively, which also indicated the Hg vapor exposure to the residents. The mean of UHg was2.5 and 1.30 g•g-1 Cr for the residents in Changshun (control site) and Xiachangxi Village, Wanshan Hg mining area, respectively, which indicated a background level. 4. Rice with high Me-Hg levels was the main route of Me-Hg exposure for the local residents in the Hg mining area. The mean of hair THg concentration was 7.3、1.9 and 2.3 g•g-1 for the residents in Dashuixi (DSX), Xiachangxi (XCX) and Baoxi (BX) Village in Wanshan Hg mining area, respectively, and the mean of hair MeHg concentration was 2.8、1.3 and 1.5 g•g-1, correspondingly. The data indicated that the population from Wanshan Hg mining area was exposed to Hg in a certain level. The mean of THg concentration was 58.5、21.3 and 33.1 ng•g-1 for the rice collected from the 3 villages, respectively, and the mean MeHg concentration was 14.6、5.7 and 4.0 ng•g-1, correspondingly. Pork meat, vegetable, and drinking water samples collected in Wanshan Hg mining area also contained highly elevated T-Hg concentrations, but with very low MeHg levels. Rice intake constituted 97.5%, 94.1%, and 93.5% of the total Me-Hg exposure to participants in DSX, XCX, and BX, on average, respectively. The significant relationship between the estimated rice Me-Hg intake and hair Me-Hg levels (r=0.65, p<0.01) confirmed rice with high Me-Hg levels indeed was the main route of Me-Hg exposure for the local residents in the Wanshan Hg mining area. 5. The mean of hair MeHg concentration was 5.05 g•g-1(ranging from 2.35 to 10.6 g•g-1)and 5.63 g•g-1(ranging from 2.54 to 9.55 g•g-1)for artisanal mining workers in GX and LWC area, respectively, and 3.53 g•g-1(ranging from 1.87 to 5.65 g•g-1), 4.01 g•g-1(ranging from 2.29 to 9.23 g•g-1)for the residents. The mean of hair MeHg concentration was 2.8、1.3 and 1.5 g•g-1 for the residents in Dashuixi (DSX), Xiachangxi (XCX) and Baoxi (BX) Village in Wanshan Hg mining area, respectively. The MeHg concentration for the artisanal Hg mining workers and residents in Wuchuan Hg mining area ranged from 0.47 to 5.69 μg•g-1. The mean of hair MeHg concentration was 0.65 g•g-1(ranging from 0.26 ¬to 1.38 g•g-1). The risk assessment indicated the daily MeHg intake through rice consumption for some residents in Gouxi and Laowuchang area were exceeded the WHO recommended value of 0.23 g•d-1•kg-1 and the daily MeHg intake for major residents in Hg mining area were exceeded the USEPA recommended value of 0.10 g•d-1•kg-1. So the residents in Gouxi and Laowuchang area were at a health risk of MeHg exposure and the residents in other Hg mining areas also were at a potential risk of MeHg exposure through rice intake.
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条目标识符http://ir.gyig.ac.cn/handle/352002/3422
专题研究生_研究生_学位论文
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李平. 贵州省典型土法炼汞地区汞的生物地球化学循环和人体汞暴露评价[D]. 地球化学研究所. 中国科学院地球化学研究所,2008.
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