BCR Speciation Analysis of Mercury in Smelting Slag at Yunnan Arsenic Mining Area
水体中汞及其形态检测方法的研究进展
Advances in Environmental Protection 环境保护前沿, 2021, 11(2), 243-251Published Online April 2021 in Hans. /journal/aephttps:///10.12677/aep.2021.112025水体中汞及其形态检测方法的研究进展赵健，张林楠*，宋青岳，姜杰沈阳工业大学环境与化学工程学院，辽宁沈阳收稿日期：2021年3月8日；录用日期：2021年4月9日；发布日期：2021年4月16日摘要汞是一种对人类、动物、植物和自然环境均存在危害的金属，对动物和人类的心血管系统、血液系统、肺系统、肾脏系统、免疫系统、神经系统、内分泌系统、生殖系统和胚胎系统均存在毒性影响，因此对水体中的汞及其形态及时地测定是非常必要的。
本文综述了几种测定汞的前处理方法，列举了其原理和应用，并介绍了汞测定中的检测方法，总结了其检测原理及优缺点等，为测定水体中的汞及其形态的科研人员提供了理论参考。
关键词汞，前处理方法，检测方法Research Progress on the Detection Method of Mercury and Its Species in WaterJian Zhao, Linnan Zhang*, Qingyue Song, Jie JiangSchool of Environmental Chemistry and Engineering, Shenyang University of Technology, Shenyang LiaoningReceived: Mar. 8th, 2021; accepted: Apr. 9th, 2021; published: Apr. 16th, 2021AbstractMercury is a kind of metal which is harmful to human beings, animals, plants and natural envi-ronment, and it has toxic effects on cardiovascular system, blood system, lung, kidney system, immune system, nervous system, endocrine system, reproductive system and embryos system of animal and human; therefore, it is very necessary to determine the mercury and species in water timely. In this paper, several pretreatment methods for the determination of mercury are re-*通讯作者。
氢化物发生-原子荧光法测田螺中硒、汞
第49卷第1期 当 代 化 工 Vol.49，No.1 2020年1月 Contemporary Chemical Industry January，2020收稿日期：2019-03-20氢化物发生-原子荧光法测田螺中硒、汞余文丽1，王振生1，王小强2（1. 河南有色金属地质矿产局第七地质大队，河南 郑州 450018； 2. 河南省有色金属地质勘查总院 ，河南 郑州 450052）摘 要： 为了提高分析测试工作效率，探索了双道氢化物发生-原子荧光法同时测定田螺中硒、汞的分析方法，该实验采用硝酸-高氯酸消解样品，以盐酸为预还原剂，KBH 4为还原剂，确定了最佳反应条件和仪器工作条件，并对试剂进行了选择和优化，同时针对硒和汞之间的相互干扰进行了分析。
结果表明，荧光强度与硒、汞浓度在0~8 ng/mL 范围呈良好线性关系，硒和汞的检出限分别为0.043 9、0.004 2 ng/mL，回收率分别为92.5%~101%，78%~87%，并且硒和汞之间的干扰可忽略不计。
该方法操作简便，灵敏度高，结果稳定可靠，具有较好的精密度及准确度，并且实现了硒、汞同时测定，降低了分析成本，提高了工作效率。
关 键 词：氢化物发生-原子荧光法；田螺；硒；汞中图分类号：O655.1 文献标识码： A 文章编号： 1671-0460（2020）01-0204-04Determination of Selenium and Mercury in River Snail by Hydride Generation -Atomic Fluorescence SpectrometryYU Wen-li 1, WANG Zhen-sheng 1, WANG Xiao-qiang 2（1. Henan Provincial Nonferrous Metals Geological and Mineral Resources Bureau No. 7 Geological Team,Henan Zhengzhou 450018, China;2. General Institute for Nonferrous Metals and Geological Exploration of Henan Province, Henan Zhengzhou 450052, China ）Abstract : A method of simultaneously determining Hg and Se in river snail was developed for improving the analytic efficiency by hydride generation-double channel atomic fluorescence spectrometry,using nitric acid-perchloric acid to digest samples, using hydrochloric acid as pre-reducing agent, KBH4 as reducing agent. The best reaction conditions and the instrument working conditions were determined. The reagents were selected and optimized, and the interference between selenium and mercury was analyzed. The results showed that its linear range was 0~8 ng/mL for Se and Hg, the detection limit and recovery were 0.043 9 ng/mL and 92.5%~101% for Se, 0.004 2 ng/mL and 78%~87% for Hg, and the interference between selenium and mercury was negligible. The method is simple, stability and highly accurate, the simultaneous determination of selenium and mercury can be realized,which reduces the cost of analysis and improves the work efficiency.Key words : Hydride generation-atomic fluorescence spectrometry ；River snail ；Selenium ；Mercury硒是人体必需的微量元素之一，人体缺硒或摄入量过多均会导致相关疾病或不良反应[1]。
液相色谱-原子荧光联用仪测定生活饮用水中的甲基汞
液相色谱-原子荧光联用仪测定生活饮用水中的甲基汞摘要：通过液相色谱-原子荧光法联用技术,确定生活饮用水中的甲基汞分析方法。
实验中采用水相滤膜过滤后，再进行固相的提取富集、净化，并采用液相色谱-原子荧光光谱联用法测定，即先保留时间定性，后再采用外标法峰面积定性。
试验结果：线性范围为0-10.0μg/L左右，相关系数分析结果为0.9999，检出限为0.0198μg/L，相对标准偏差RSD%为4.9，用生活饮用水进行甲基汞加标回收实验，加标回收率在87.5%-92.0%%之间。
该方法简便、可靠，为测定生活饮用水中甲基汞的风险监测中提供了重要的技术手段。
关键词：液相色谱-原子荧光联用仪；甲基汞；形态分析；生活饮用水Determination of methyl mercury in domestic drinking water by liquid chromatography-atomic fluorescence combination analyzerZhang Renli, He Kangli, Yang Hongjuan(Ningxia Shuirun Testing Technology Co., LTD., Yinchuan City, Ningxia Hui Autonomous Region 750000)Abstract: Abstract: The analysis method of methyl mercury in drinking water is determined by using liquid chromatography and atomic fluorescence method. In the experiment, the water phase filter membrane was filtered, and then the solid phase was extracted and purified, and the liquid chromatography-atomic fluorescence spectroscopy was used, that is, the retention time was determined first, and then the peak area was determined by the external standard method. Test results: the linear range was about 0-10.0 μg/L, the correlation coefficient analysis result was 0.9999, the detectionlimit was 0.0198 μg/L, and the relative standard deviation RSD% was4.9. Methmercury spike recovery experiment was conducted with domestic drinking water, and the spike recovery rate was between 87.5% and92.0%. This method is simple and reliable, and provides an important technical means for determining the risk monitoring of MeHg indomestic drinking water.Key words: liquid chromatography-atomic fluorescence instrument; methyl mercury; morphological analysis; drinking water汞是具有毒性的一种重金属元素，它的毒性与存在的形式有关，有机汞毒性远高于无机汞。
赣江中下游城市断面表层沉积物中重金属形态分析
赣江中下游城市断面表层沉积物中重金属形态分析摘要：利用欧洲共同体参考物机构（European Community Bureau of Reference，BCR）逐步提取法对赣江中下游10个断面表层沉积物样品中重金属Cu、Zn、Pb、Cd、Cr 和As的形态进行调查研究，评估了沉积物中重金属的生物有效性，探讨了沉积物中总有机碳（TOC）与重金属不同形态之间的关系。
结果表明，表层沉积物中可提取态重金属的空间分布特征明显，表现为中游>下游>中下游>小城镇断面；可交换态、氧化态与残渣态是赣江中下游城市断面表层沉积物中6种重金属的主要赋存形态，6种重金属的可提取态比例均大于50%，具有较高的二次释放潜力。
可提取态重金属Cu和Cr与TOC呈显著正相关性。
关键词：赣江；沉积物；重金属；形态Analysis of Heavy Metals in Surface Sediments at City Sections of Middle and Lower Reaches of Ganjiang RiverAbstract：BCR three stage sequential extraction procedure was applied to examine the speciation and concentrations of heavy metals （Cu，Zn，Pb，Cd，Cr and As）in sediments of middle and lower reaches of Ganjiang River to determine the bioavailability of these heavy metals. The relationship between TOC and speciation of heavy metals in the sediments was explored. Results showed that total content of extractable heavy metals in surface sediment was as follows：midstream>downstream>lower-middle stream>section of small towns. The major speciation of six heavy metals were exchangeable fraction，oxidizable fraction and residual fraction. The percentage of extractable fraction in total content was higher than 50%. The six heavy metals had a high potential for secondary release. TOC was similar to the extractable fractions of Cu and Cr in sediment and there were significantly positive correlations between the extractable fractions of Cu and Cr.Key words：Ganjiang River；sediment；heavy metals；speciation进入水体的重金属大部分通过水体中悬浮物的吸附作用发生迁移和沉降，蓄积在沉积物中[1]。
水中污染物形态分析-
14
氢氧化物
溶度积Ksp
开始沉淀时的pH 假定[M]=0.01mol/L
沉淀完全时的pH 假定[M]=10-5mol/L
Fe(OH)3 Al(OH)3 Zn(OH)2 Fe(OH)2 Mn(OH)2 Mg(OH)2
3.5×10-38 2×10-32 1.2×10-17 1×10-15 4.5×10-13 1.8×10-11
22
水中痕量金属的物理形态可以按照其粒径大小分类。 为区分水中金属不同粒径的形态，常常应用不同孔径 的膜（0.45μm，0.20μm，截留分子量为1000的膜） 将水样过滤。先用0.45μm膜将颗粒物除去，然后再 用0.20μm膜过滤粒径较大的胶体结合部分，接着再 用截留分子量为1000的膜过滤掉粒径较小的胶体部分 ，而能通过截留分子量为1000道尔顿的膜的部分可视 为游离金属离子与真正可溶部分。 当然这种胶体分级是不严格的。
6
computer modeling
通过实验操作进行形态分析受到很多问题的阻碍。 因为自然环境样品的复杂性，样品中可能有非常多的 元素存在，其中大部分的浓度可能都低于仪器的检出 限。但尽管这些元素的浓度可能非常低，但它们可以 被生物利用从而产生毒性。因此，这些形态能否被准 确的测定，是非常重要的。 另外还有一个问题是实验操作对系统平衡的破坏。自 然界中的系统应该是一个接近热力学平衡的系统。对 任何系统问题的分析都可能破坏这种不稳定的平衡。 为了避开曾经在对形态分析进行的实验测定中所遇到 的这些问题，电脑模型被引入到形态分析中。
9
10
Species
Ca2+(aq) CaCO3(aq) CaOH+ Species CO32H2C6 100 0 0
重金属在土壤中的赋存形态
（土壤中重金属存在形态的研究方法）
一 土壤重金属污染现状
目前，全世界平均每年排放Hg约1.5万吨， Cu 340万吨，Pb 500万吨，Mn 1500万吨，Ni 100万吨。我国受镉、砷、铬、铅等重金属污 染的耕地面积近2000万hm2,约占总耕地面积 的1/5。
二 来源
•Cancès采用土柱-DMT技术结合NICA-Donnan、CDMUSIC 模型对土壤中金属离子形态进行分析，认为土 壤溶液中Cd、Zn主要为易迁移的自由水合离子，Cu、 Pb形态则主要由溶解有机质(DOM)控制，土壤固相中Cd、 Zn、Pb形态则由有机质、铁锰氧化物、富锌矿物控制。
四 结语
具有预见性的模式计算方法与实验分离和测 定方法的结合是形态分析手段的趋势。
1.3表面分析技术
2、重金属的形态分离
2.1固相(土壤/沉积物)重金属的形态分离：Tessier法， BCR法，其它提取法（超临界流体提取(SFE)、微波辅助 提取(MAE)、加速溶剂提取(ASE)、超声提取(USE)）
2.2液相重金属的形态分离：高效液相色谱(HPLC)，气 相色谱(GC)，毛细管电泳(CE)，联用技术，其它分离方 法（道南膜技术(Donnan Membrane Technique，DMT)）
fertilizer bin. Environmental pollution, 2001, 113: 35-40.
[10] S. Sauvé, W.A. Norvell, M. Mcbride, et al. Speciation and complexation of cadmium in
extracted soil solutions. Environ. Sci. Technol., 2000, 34: 291-296. [11] 王学军，陈静生.土壤、沉积物中微量重金属形态分配预测初步研究.环境化学, 1993, 12(4): 245-250. [12] 黄圣彪，王子健.水环境中重金属的生物毒性预测模型.上海环境科学，2002, 21(1): 20-23.
硒(Ⅳ)预处理下根表铁膜对水稻幼苗吸收和转运汞的影响
硒(Ⅳ)预处理下根表铁膜对水稻幼苗吸收和转运汞的影响高阿祥;周鑫斌;张城铭【摘要】[Objective] Iron plaque on root adsorbs heavy metal elements in the soil,thus reducing the content of heavy metals in the environment the plant grows in,while selenium is antagonistic to heavy metal elements in plant roots,thus inhibiting the transfer of Cd,As,Mn and some other heavy metals in the roots of rice seedlings as was found in the researches.In the presence of a proper amount of iron plaque,selenium reacts withCd,As,Mn,and so on to form insoluble compounds that accumulate in the iron plaque,thus reducing toxicity of these heavy metals to the plants.In this study,a hydroponic experiment was conducted to explore effects of the iron plaque on the surface of the roots of rice seedlings on absorption and transport of mercury by the plants treated with selenium.[Method] Having been disinfected and washed clean,rice seeds were sown in Hoagland culture medium for germination.Out of the seedlings,24 consistent in growth were selected and transplanted into two groups of vessels with Hogland culture medium,one treated without selenium (Se0) and the other with selenium (Se0.5,0.5 mg L-1 in the form of Na2SeO3),for cultivation for 2 weeks.Then the rice plants were moved into Fe2+ (FeSO4) solutions (pH=5.5),0,25,50 and 100 mg L-1 in concentration,or Treatment Fe0,Fe25,Fe50 and Fe100,separately,for 24 h,to let iron plaque form on root surface.And then the rice plants were then transferred into HgCl2 solution,0.3 mg L-1 in concentration for 72 h of cultivation.Each treatmenthad three replicates.[Result] No significant effect of the iron plaque was found on growth of the rice seedlings,but selenium was to be able to increase the plants in biomass.With rising Fe concentration in the solution,iron contents in the shoots and roots of the plants and in the dithionite-citrate-bicarbonate (DCB) solution all increased.The iron content in the DCB solution (extraction of root surface iron plaque) reached57.3％～ 96.2％,significantly higher than that (1.1％～ 17.5％) in the shoot and (2.7％～ 25.9％) in the root of the rice seedlings,Most of the iron in the seedling plants were accumulated in the iron plaque or DCB extract.With the rising amount of iron plaque on the root surface,the content of mercury in the roots and shoots of the plants decreased significantly.The addition of selenium did not affect much the content of mercury in the shoots and roots of the plants in Treatments Fe0 andFe25,but it did reduce the content of mercury significantly in Treatments FeS0 and Fel00.With the formation of iron plaque on the root surface,the content of mercury in the shoots and roots reduced because the iron plaque adsorbed much mercury and the addition of Se (Ⅳ) enabled the iron plaque to adsorb more mercury,thus increasing the proportion of mercury in the iron plaque and consequently reducing that in the shoots of the plans.Quite obviously,Se significantly enhances Hg fixation capacity of the iron plaque on the root surface of rice seedlings.[Conclusion] Under hydroponic conditions,iron deposits on the root surface to form iron plaque,which inhibits Hg adsorption by rice roots and upward transfer of Hg in the plant.With the forming of more iron plaque,Hg fixation capacityof the coating increases significantly,too,thus markedly reducing Hg accumulati on in the rice seedling.Se (Ⅳ) can alleviate the effect of mercury stress on rice,inhibit Hg transfer from roots to shoots and reduce Hg accumulation in the shoots,thus playing a role in protecting rice from mercury toxication.This study has certain practical significance in improving the quality of rice in mercury contaminated area and eusuring food safety.%采用水培试验的方法研究硒(Se,Ⅳ)预处理下,根表铁膜对水稻幼苗吸收和转运汞(Hg)的影响.将水稻幼苗置于Se0和Se0.5 (mg L-1)培养液中培养2周,再用4种不同浓度的Fe2+溶液(0、25、50和100 mg L-1即Fe0、Fe25、Fe50、Fe100)诱导水稻根表形成不同数量的铁膜,随后置于0.3 mg L-1的HgCl2培养液中继续培养72 h.结果表明,根表铁膜对水稻幼苗生长无显著影响,但硒可以增加其生物量.碳酸氢钠—柠檬酸三钠—连二亚硫酸钠(DCB)提取液(即根表铁膜)中含铁比例(57.3％～96.2％)显著高于水稻幼苗地上部(1.1％～17.5％)和根部(2.7％～25.9％),水稻幼苗的大部分铁被积累至DCB提取液中.随着根表铁膜数量的增加,根和地上部汞含量均显著降低.在Fe50和Fe100处理中,硒的加入显著减少了地上部和根部的汞含量,也显著降低了汞的分配系数,Se(Ⅳ)预处理能明显提高铁膜固持汞的量.综上所述,Se(Ⅳ)预处理和根表铁膜均能阻碍水稻幼苗对汞的吸收和向地上部的转运,减轻水稻汞胁迫,从而起到保护水稻避免汞毒害的作用.本研究对于提高汞污染区稻米质量和保证粮食安全具有一定的现实意义.【期刊名称】《土壤学报》【年(卷),期】2017(054)004【总页数】10页(P989-998)【关键词】铁膜;水稻幼苗;硒;汞【作者】高阿祥;周鑫斌;张城铭【作者单位】西南大学资源环境学院,重庆400716;西南大学资源环境学院,重庆400716;西南大学资源环境学院,重庆400716【正文语种】中文【中图分类】S143.7+1汞是一种毒性很强的污染物，并通过食物链在人和动物体内富集，因其在环境中具有持久性、生物累积性和强毒性被国际组织列为优先控制污染物［1］。
油气田含汞污泥处理技术现状与展望
671 前言汞是常温下唯一一种液态金属，且会发生蒸发，含汞化合物多有剧毒，自然界中汞主要以无机汞、有机汞及其化合物存在[1]。
近年来，随着《水俣公约》对我国正式生效，国内逐渐加强了对汞检测、汞防护及汞污染治理方面的研究。
工业发展进程中遗留下来的含汞产地及废物（矿渣、土壤、沉积物等）和工业上（石油、冶金、化工等）正在产生的含汞固体废弃物，严重威胁着人类的健康，迫切需要安全性强且经济可靠的技术来治理[2]。
含汞油气田正常生产作业及污水处理过程中均会产生大量含汞污泥和失效的脱汞剂。
其中主要来源于2方面：一是含汞油气田勘探开发产生的作业污泥、清罐污泥、落地污泥以及气田水净化处理产生的絮凝沉淀污泥；二是隔油池的底泥、浮选池的浮渣以及活性污泥等。
国内部分含汞油气田汞含量如表1所示，含汞污泥具有组成复杂、含水率高、体积大、流动性强和污泥中汞高毒性、存在形态多变、易迁移转化等特点[3]。
表1 国内含汞气田汞含量[4]油气田名称汞含量（ng/m 3）范围值平均值文留气田1110～5110026105苏桥气田199000～204000201500深县西气田180000～254000217000辽河坳陷东部14400～6900036578辽河坳陷西部41200～1930000736400中原油田文25-33井140000140000华北盆地马24井142000142000长庆油田胜利井93～64800024468玉泉气田5200～1815011675崖13-1气田430000～450000440000目前，国内外关于含汞污泥的成熟处理技术，相对较少。
国内气田污泥处理技术多集中偏向于含油污泥处理技术方面[5]。
国外气田含汞污泥处理主要采用热处理工艺，极少采用深井回注工艺[3]。
本文通过对国内外可兼顾处理含汞污泥的含油污泥处理技术的概述，并对含汞污泥处理技术进行展望，旨在为含汞污泥减量化、无害化处理处置提供可靠的技术思路。
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BCR Speciation Analysis of Mercury in Smelting Slag at Yunnan ArsenicMining AreaBin Li1,2, a, Ping Ning1,b, Yuntao Gao2,c , Hongbin Wang2, d1Faculty of Environmental Science and Engineering,Kunming University of Science and Technology,Kunming 650093,China2Key Laboratory of Chemistry in Ethnic Medicinal Resources, State Ethnic Affairs Commission & Ministry of Education, Yunnan University of Nationalities, Kunming, Yunnan 650093, Chinaa break.li@,b ningping58@ ,c yuntaogao@ ,d wanghb2152@ Keywords: Atomic Fluorescence Spectrometry; Mercury; BCR Speciation; Arsenic Mining. Abstract: BCR three-step extraction method was used to evaluate the speciation of mercury in mining area soil. The results showed that the major existent form of mercury in NO.1 and NO.3 area were acid-soluble speciation, the major existent form of mercury in NO.2 and NO.4 area were nitric acid-soluble speciation, and the total content of mercury in entrance area, shade area, sunny area and low-lying area were 419.977 mg/kg, 182.945 mg/kg, 290.313 mg/kg and 798.718 mg/kg, respectively. The bioavailability of mercury in mining area soil was evaluated based on BCR speciation. Acid-soluble speciation, nitric acid-soluble speciation and oxidation speciation were considered to be potential bioavailability.1. IntroductionThe study of heavy metals speciation plays an essential role in the evaluation of ecotoxicological risk and mobility in soils [1]. Sequential extraction procedures such as Tessier et al [2], Maiz [3], and McGrath [4] are often used in soil studies to determine the speciation or phases of elements[5]. The EC standard substances Bureau (European Communities Bureau of Reference) proposed a three-step extraction method [6-8] (referred to as the BCR Act). This method appears to be more operationally effective than others proposed previously, like simple, high accuracy, and high stability.Yunnan Mining Industry has become a leading industry group with the rapid development of economic [9]. Mercury pollution is one of the most serious environmental problems in Yunnan. It is essential to study the speciation of mercury due to understand clearly the environmental behaviors and pollution characteristics of mercury in arsenic mining area. The speciation of mercury in arsenic mining area has rarely been reported. In this study, BCR three-step extraction method is used to analyze the speciation of mercury in arsenic mining area.2. EXPERIMENTALMaterials: Ascorbic acid, Thiourea, Nitric acid, Perchloric acid, Hydrogen fluoride, Hydroxylamine hydrochloride, Sulfuric acid, Hydrochloric acid, Potassium permanganate, Hydroxylamine hydrochloride and Potassium borohydride were were obtained from Alfa Company and used as received with no further purify (analytical reagent). Hg standard stock solution 1000 μg/ml were purchased from national steel materials testing center system, china.Milli-Q water (18MΩ.cm) was used for all solution preparations. All glassware used in the following procedures was cleaned in a bath of a piranha solution (H2SO4/30% H2O2 = 7: 3 v/v) and boiling for 30 min.Experimental methods: Four soil samples were collected on the surface layer (0 to 20 cm in depth) at four different area(entrance area, shade area, sunny area and low-lying area) of the arsenic mine in Yunnan province, in December, 2011. And the samples were signed as 1#, 2#, 3#, 4#samples, respectively. The soil samples were air-dried for 3 d, and passed through a 100-mesh sieve. BCR three-step extraction method is used to analyze the speciation of mercury. BCR was divided into four tractions: acid-soluble, nitric acid-soluble, oxidation and residual. The sequential extraction procedure was carried out step-by-step as described in the literature [4].Atomic fluorescence spectrometry was used to determine the content of mercury in all the samples. The soil sample was treated by HClO3-HNO3-HF digestion method. In a typical procedure, 5.0 g soil sample, 4.5 ml perchloric acid, 4.5 ml nitric acid and 1.5 ml hydrogen fluoride were mixed uniformly in a PTFE digestion tank. Then the samples were digested for 3 h at180 ℃. After that, the samples were taken out and cooling down to room temperature. Finally, the acid in samples was drove, and 0.3 g ascorbic acid and thiourea were added to the samples, and the sample was diluted to a final volume of 50 ml.3. RESULTS AND DISCUSSIONThe determination of mercury in soil sample: According to the Water and wastewater analysis method, the content and speciation of mercury in the samples were determined by atomic fluorescence spectrometry [10]. The results of linear regression analysis are shown in Table 1.Table 1 Quantitative method of linear regression analysisDetermination Standard curveequationLinearrange/(mg·L-1)R2Standard curve 1 Total determination Y=297.62X-31.328 0~10 0.9989Standard curve 2SpeciationdeterminationY=422.25X+41.187 0~10 0.9980The BCR speciation analysis of mercury: Table 2 shows the BCR speciation analysis of mercury in mining area soil. The result shows that the major existent form of mercury in 1# area is acid-soluble speciation. The percentage of acid-soluble speciation, nitric acid-soluble speciation, oxidation speciation and residual speciation are 65.7%, 28.2%, 4.3% and 1.7% respectively, ranked in descending order: acid-soluble speciation＞nitric acid-soluble speciation＞oxidation speciation＞residual speciation. The major existent form of mercury in 2# area is nitric acid-soluble speciation. The percentage of nitric acid-soluble speciation, acid-soluble speciation, oxidation speciation and residual speciation are 76.8%, 10.6%,7.3% and 5.3% respectively, ranked in descending order: nitric acid-soluble speciation＞acid-soluble speciation＞oxidation speciation＞residual speciation. The major existent form of mercury in 3# area is acid-soluble speciation. The percentage of acid-soluble speciation, nitric acid-soluble speciation, oxidation speciation and residual speciation are 48.5%,44.0%, 5.7% and 1.8% respectively, ranked in descending order: acid-soluble speciation＞nitric acid-soluble speciation＞oxidation speciation＞residual speciation. The major existent form of mercury in 4# area is nitric acid-soluble speciation. The percentage of nitric acid-soluble speciation, acid-soluble speciation, oxidation speciation and residual speciation are 77.4%, 21.1%, 1.3% and 0.2%, respectively.The total content of mercury in entrance area, shade area, sunny area and the low-lying area are 419.977mg/kg, 182.945mg/kg, 290.313mg/kg, and 798.718mg/kg, respectively. The total content of mercury in four sampling points ranked in descending order: 4#>1#>3#>2#.Table 2 Determination of mercury content and speciation Sampling points SpeciationAcid-soluble speciationNitricacid-solublespeciationOxidationspeciationResidualspeciationTotalcontent1# Content /(mg/kg) 276.039 118.639 18.230 7.069 419.977 Percentage/(%) 65.7 28.2 4.3 1.7 RSD/(%) 6.33 7.22 4.64 10.69 5.59 The recovery/(%) 84.4 85.1 108.9 97.2 91.42# Content /(mg/kg) 19.454 140.465 13.345 9.681 182.945Percentage /(%) 10.6 76.8 7.3 5.3RSD/(%) 6.36 6.43 5.57 10.66 10.80 The recovery/(%)104.3 73.2 79.0 74.1 90.63# Content /(mg/kg) 140.894 127.857 16.465 5.097 290.313RSD/(%) 8.84 7.47 10.85 4.96 5.18Percentage /(%) 48.5 44.0 5.7 1.8The recovery/(%)123.4 120.3 108.2 73.7 84.64# Content /(mg/kg) 168.335 618.140 10.335 1.908 798.718Percentage /(%) 21.1 77.4 1.3 0.2RSD/(%) 8.22 6.44 9.49 8.69 6.35 The recovery/(%)78.5 89.1 97.8 90.1 107.2Bioavailability analysis: As shown in Fig.1, the content of mercury in the four sampling points is higher than the standard content. For three BCR speciation, like acid-soluble speciation, nitric acid-soluble speciation and oxidation speciation, it can be considered to be potential bioavailability. While residual speciation of heavy metals can keep long-term stability in soil due to it is uneasy to release and to be absorbed by plants under normal conditions.Figure 1 Distribution of mercury speciation4. ConclusionsBCR speciation analysis of mercury speciation of mining area soil in Yunnan province showed that the total content of mercury in entrance area, shade area, sunny area and low-lying area of the arsenic mine were 419.977 mg/kg, 182.945 mg/kg, 290.313 mg/kg and 798.718 mg/kg respectively, ranked in descending order: 4#>1#>3#>2#. The result showed that the highest content of mercury could reach 798.718mg/kg. However, the mercury content varied with the different area for the mercury content in sunny area was lower than shade area. The bioavailability of mercury in mining area soil was evaluated based on BCR speciation. Acid-soluble speciation, nitric acid-soluble speciation and oxidation speciation were considered to be potential bioavailability.AcknowledgementThis work was supported by the National Natural Science Fundation of China (51062018), the Natural Science Foundation of Yunnan (2010FXW004), Program for Innovative Research Team (in Science and Technology) in University of Yunnan Province (2010UY08, 2011UYN09), and Program for Yunnan Provincial Innovation Team (2011HC008).References[1] L. YI, Y. T. Hong, D. J. Wang and Y.X. Zhu, Geochemical Journal, 41, 235 (2007).[2] A. Tessier, P. G. C. Campbell, M. Bisson, Analytical Chenistry, 7 (51), 844 (1979).[3] I. Maiz, I. Arambarri, R. Garcia, etc,Environmental Pollution, 110, 3 (2000).[4] D. Mcgrath, The Science of the Total Environment, 178, 37 (1996).[5] R. Pardo, M. Vega, L. Debán, etc,Anal Chim Acta, 606, 26 (2008).[6] A. M. Ure, P.H. Quevauvillier, H. Muntau, etc, EUR Report, 14763(1992).[7] E. F. Liu, J. Shen, Y. X. Zhu,Research of Environmental Science, 18(2), 57 (2005).[8] T.D. Cuong, J.P. Obbard,Applied Geochemistry, 21, 1335(2006).[9] Youbin Lin, Lei Zhao, Bulletin of Mineralogy Petrology and Geochemistry, 21(2),7(2002).[10]Water and wastewater analysis method[M]. China Environment science press,364.。