1、80Atomic Mass:200.59 amuMelting Point:-38.87 C(234.28 K)Boiling Point:356.58 C(629.73 K)Number of Protons/Electrons:80 Number of Neutrons:121 Classification:Transition MetalCrystal Structure:Rhombohedral(斜方六 面体)Density 293 K:13.456 g/cm3Color:Silver,Isotope geochemistry of mercury,Mercury and mercur
2、y isotopes,Hg is a chalcophile element,Mercury is a trace element.,Mercury mineral belt,Natural component of earths crust in the form of Cinnabar(HgS)Rytuba 2003,Environ.Geol,1 汞是毒性最强的重金属之一,无机汞毒性弱,甲基 汞的毒性最强高神经毒性心血管毒性生殖毒性免疫系统效应肾脏毒性,无机汞,无机汞,汞污染的危害具有隐Hg2蔽+性MeH和g 突发性,一 旦发生重大污染事件或出现人群病变,将产生灾难性后果。,Chisso公
3、司,1932年日本Chisso公司在水 俣市建厂,1956年出现了震惊世界的水 俣病事件1968年日本政府正式承认水 俣病是当地居民食用甲基汞 污染的海产品引起的2001年3月,日本官方确认 水俣病患者2955人,死亡,1784人,但仍有10072人出,水现俣水俣病病是的世症界状而上未迄得今到为官 止最严重的环境公方 害确认事件,其深刻性和持久性史无前例。,孕妇低剂量长期甲基汞暴露 会严重影响胎儿智力发育,母体发汞含量每增加1 ppm,胎儿智商(IQ)平均下降约 0.18美国每年有316,500-637,200名新生儿受到影响每年给美国带来约87亿美元 的经济损失,2甲基汞有生物富集和生物放大
4、作用,(US EPA,2011),因此环境中少量的汞污染,会造成食物链甲基汞,的显著富集。,3汞是全球性污染物 长距离传输,汞是唯一在大气中主要以气 态单质汞形式存在的重金属大气居留时间可达1年,Hg0,(Munthe et al.,2007;US EPA,2011),北欧,美国不同流域鱼体汞的平均含量,人为活动排放的汞,在大气经长距离 迁移后的沉降梭是造成这类鱼体汞污染 主要原因,人子们认识到汞是一种全球 性污染,这是鱼国际控制汞排放的直接,动因。,政府间谈判委员会系列会议,2013年达成国际汞公约,第一届,2010.6 瑞典斯德哥尔摩,第三届,2011.10 内罗毕,第五届,2013.10
5、 日本水俣 市,旨在控制和削减全球 人为汞排放和含汞产 品的使用汞是国际关注的 全球污染物,全面认识汞的大尺度迁移规律一直是国际 学术界和政府管理部门关注的焦点,2000-2950,300-600,1700-2800,2000-2400,生物质土壤与植人为源排 燃烧被释放放,地质成因 的排放,80-600,沉降 到陆 地与 河流,1500-3200,沉降 到海 洋,3700,河流380,颗粒物 去除,垂直混合,221000,802000,200600腐殖层土壤,矿质层土壤,2900 表层海洋134500,中间层 海洋埋藏,深层 海洋,海洋排放,大气,5000,Hg0,HgII,hv,自由基,汞
6、库单位:吨;通量单位:吨/年,汞排放清单汞在大气中 的迁移转化 规律大气与地表 间汞的相互 作用人为源排放,Selin,2009,Global burden increased from natural background by about a factor 3(air,soils,sediments,fish),Hg has an active redox chemistry,Hg Methylation,Challenge:,Mercury reflects the complexities of one of the most insidiously interesting and s
7、cientifically challenging biogeochemical cycles at the Earths surfaceIsotopes,Concentra ons,Molecular Hg species,MeHg,Research into Hg stable isotope biogeochemistry is offering new insight into the behavior of Hg.,一、汞是国际关注的全球污染物 二、汞同位素测定方法三、汞同位素分馏四、自然体系样品中汞同位素组成 五、应用实例六、展望,报告内容,Element:Mercury,200.
8、59,HgMercury,7 stable isotopes M-196 to M-204,0.15,10.0,16.8,13.2,29.83023.1,6.85,0,10,20,Abundance(%),196,198 199 200 201 202204,Hg isotope,Mass difference of 4%.Active redox chemistry.Hg is a volatile.,Conventions(Madison ICMGP round table),1.Light isotope(198Hg)in the denominator:ex.,199Hg/198Hg,
9、202Hg/198Hg,Delta standard:NIST SRM 3133(10,000 ppm Hg in 10%HNO3)Secondary liquid Hg based reference materials(Hg2+in solution):UM-Almaden:202Hg=-0.54(Joel Blum,Univ.Michigan)CPRG F65A:202Hg=-3.55CRPG RL24H 202Hg=+2.48(Jean Carignan,CRPG),where xxx is 199Hg,200Hg,201Hg,202Hg,204Hg,Conventions(Madis
10、on ICMGP round table),1.Light isotope(198Hg)in the denominator:202Hg=-3.55CRPG RL24H 202Hg=+2.48(Jean Carignan,CRPG),Mass dependent fractionation,XXX:202,201,200,199199Hgmeasured=202Hgmeasured 0.252 200Hgmeasured=202Hgmeasured 0.502 201Hgmeasured=202Hgmeasured 0.752,Conventions(Madison ICMGP round t
11、able),1.Light isotope(198Hg)in the denominator:202Hg=-3.55CRPG RL24H 202Hg=+2.48(Jean Carignan,CRPG),199Hg()=199Hg(0.2520202Hg),200Hg()=200Hg(0.5024202Hg),201Hg()=201Hg(0.7520202Hg),Mass independent fractionation,Hg isotopic measurements a historic perspective,1919 F.W.Aston:discovery of Hg isotopes
12、 1920 Brnsted:fractionation/separation of Hg isotopes by liquid Hg pycnometry1922 Brnsted:pycnometry of different liquid Hg sources,today,1935-1999 Nier,Haeffner(gas source MS).Kumar,Goel,Jovanovich(NAA):anomalous Hg isotopes in meteorites,2009 1st ever ICMGP session on stable Hg isotopes,2000-2001
13、Klaue B,Blum JD Evans RD,Hintelmann H,Jackson T A Q-ICP-MS,single-collector ICP/MS,ICP-TOF-MS.2000 J.D.Blum Hg Cold vapor generation+Multiple Collector ICP-MS 2001 Lauretta et al.,GCA Hg isotopes in Meteorites by CV-MC-ICPMS2003 Hintelmann&Lu Hg isotopic variations in cinnabar(HgS)2006 Mass independ
14、ent Hg isotopes fractionation(MIF)in fish,Multiple Collector Inductively Coupled Plasma Mass Spectrometry,variable multicollector,magnet,ESA,plasma,Ion Transmission Hg2+(aq)2 in 100,000Hg0(g)200 in 100,000,Image by Thermo,Multiple Collector Inductively Coupled Plasma Mass Spectrometry,Nu-instrument,MC-ICP-MS offers the simultaneous detection of multiple isotopes.MC-ICP-MS combines the multi-detectors with very high ionization efficiency of the ICP source,allowing very high precision isotopic analysis for various ele
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