污染土壤中汞的形态特征及其释放的初步研究
摘要
本文以原沈阳冶炼厂废旧厂区自然污染土壤和模拟汞污染土壤(均为草甸土)为研究对象，采用连续浸提形态分析法对土壤中汞的赋存形态进行了分析，共分为水溶态汞，交换态汞，碳酸盐、铁锰氧化物及部分有机态汞，腐殖酸结合或络合态汞，易氧化降解有机质结合态汞，难氧化降解有机质及某些硫化物结合态汞和残渣态或晶格态汞等七种形态，并采用一次平衡法对其潜在毒性进行了研究，分析研究得出以下主要结论：
1．供试土壤中汞的形态分布存在很大差异。其中水溶态汞含量均很低，最高为模拟污染土壤中占到总量的0．50％，明显高于自然污染土壤；交换态汞以模拟污染土壤和pH较低的制酸车间土壤中最高，分别占总量的25．63％和19．99％；碳酸盐、铁锰氧化物及部分有机态汞以制酸车间土壤中最高，占到总量的20．33％；腐殖酸结合或络合态汞以模拟污染土壤和制酸车间土壤中最高，均超过总量的10%；而易氧化降解有机质结合态汞则以废水排污口土壤中最高，占总量的43．06％，其次是模拟污染土壤，占总量的35．47％；难氧化降解有机质及某些硫化物结合态汞以试验田土壤(对照)中所占比例最高为14．81％；残渣态或晶格态汞以原料库区土壤和生产车间土壤中所占比例最高，占总量的87．04％和87．66％，而以模拟污染土壤中最低，只占总量的18．28％。
2．在10～2000 mmol·L~(-1)浓度范围内SO_4~(2-)、Cl~-、Na~+和Ca~(2+)对污染土壤汞的释放量均随离子浓度的增大而增大；CO_3~(2-)、OH~-则没有表现出这一规律。同一离子对不同土壤汞的释放量并不与汞全量成正相关关系。同一无机离子在相同浓度条件下，对模拟污染土壤的释放量要明显高于自然污染土壤。
3．从不同离子的释放特征曲线来看，供试无机离子对污染土壤汞的释放能力(即潜在毒性)大致表现为：Cl~->OH~->CO_3~(2-)>SO_4~(2-);Ca~(2+)>Na~+。
4．酸度是影响土壤汞潜在毒性的重要因素之一。随H~+浓度的增大，对污染土壤汞的释放率也随之增大。
5．在所有的释放实验中，以残渣态或晶格态汞为主的原料库区土壤和生产车间土壤均表现出相一致的释放特征。
6．除OH~-和CO_3~(2-)外，实验所选用的无机离子SO_4~(2-)、Cl~-、Na~+、Ca~(2+)及盐酸浓度(mol·L~(-1))与污染土壤汞的释放量(mg·kg~(-1))之间的关系能很好地用多项式方程：y=ax~3+bx~2+cx+d加以描述，相关系数r均达到显著水平(p<0．05)。
This article focuses on the natural contaminated soil samples from a deposed smelt factory's region in Shenyang and the simulative contaminated soil which are all meadow soil as the tested soils, the soils' mercury species are analyzed by sequential extraction species method can be divided the following kinds: water soluble species, exchangeable species, species combined with carbonate and Fe and Mn oxides, species combined with humic acid, species combined with easily oxidized and degraded organic matter, species combined with hardly oxidized and degraded organic matter and residual species existing in mineral lattice et al. seven groups. And investigated their underlying toxicity used the means of the first balance. The results show the following main conclusions:
1.The mercury species distribution in the tested soil exist greatly differences. In these soil, mercury existed in water soluble species are all very low, the highest is in simulative contaminated soil which is 0.50 percent of total, but distinctly higher than the natural contaminated soil; mercury existed in exchangeable species is the highest in simulative contaminated soil and lower pH of made acid plant soil, which are 25.63 and 19.99 percent of total; mercury existed in species combined with carbonate and Fe and Mn oxides is the highest in made acid plant soil, which is 20.33% of total; mercury existed in species combined with humic acid is higher in contaminated soil and lower pH of made acid plant soil, which are all higher than 10%; mercury existed in species combined with easily oxidized and degraded organic matter is the highest in drained waste water region soil of 43.06%, the second is contaminated soil which percent is 35.47%; mercury existed in species combined with hardly oxidized and degraded organic matter is the highest in testing farmland soil which is antitheses, is 14.81%; mercury existed in residual species existing in mineral lattice is the highest in raw material storeroom section soil and produced workshop soil, which are 87.04 and 87.66 percent of total, but the lowest is in simulative contaminated soil which is only 18.28%.
2.In 10-2000 mmol·L~(-1) concentration range, the mercury releasing amount enhanced with the increment of SO_4~(2-)、Cl~-、Na~+ and Ca~(2+), but CO_3~(2-)and OH~-can't put up this uniform disciplinarian. The mercury releasing amount can't take on positive correlativity with the total mercury in tested soil. In the same abio-ion under the uniform concentration, the mercury releasing amount in the simulative contaminated soil are distinct fatter than the natural contaminated soil.
3.From the characteristic curves of Hg released by different ions for the contaminated soil, the mercury releasing ability (namely: underlying toxicity) in the tasted soil approximately behaves: Cl~->OH~->CO_3~(2-)>SO_4~(2-);Ca~(2+)>Na~+.
4.Acidity is one of the importance factors which affects the underlying toxicity of mercury in contaminated soil. The mercury releasing rate increases with the increment of hydrochloric acid concentration.
5.In all released experiments, mercury existed in residual species existing in mineral lattice is primary in raw material storeroom section soil and produced workshop soil which put up accordant released character.
6.In the tasted all abio-ions, with the exception of OH~- and CO_3~(2-), the connection with concentration (mol·L~(-1)) and the mercury releasing amount (mg·kg~(-1)) in contaminated soil can primly be described by multinomial equation: y=ax~3+bx~2+cx+d. All correlative relations reach prominent level (p<0.05).
1．供试土壤中汞的形态分布存在很大差异。其中水溶态汞含量均很低，最高为模拟污染土壤中占到总量的0．50％，明显高于自然污染土壤；交换态汞以模拟污染土壤和pH较低的制酸车间土壤中最高，分别占总量的25．63％和19．99％；碳酸盐、铁锰氧化物及部分有机态汞以制酸车间土壤中最高，占到总量的20．33％；腐殖酸结合或络合态汞以模拟污染土壤和制酸车间土壤中最高，均超过总量的10%；而易氧化降解有机质结合态汞则以废水排污口土壤中最高，占总量的43．06％，其次是模拟污染土壤，占总量的35．47％；难氧化降解有机质及某些硫化物结合态汞以试验田土壤(对照)中所占比例最高为14．81％；残渣态或晶格态汞以原料库区土壤和生产车间土壤中所占比例最高，占总量的87．04％和87．66％，而以模拟污染土壤中最低，只占总量的18．28％。
2．在10～2000 mmol·L~(-1)浓度范围内SO_4~(2-)、Cl~-、Na~+和Ca~(2+)对污染土壤汞的释放量均随离子浓度的增大而增大；CO_3~(2-)、OH~-则没有表现出这一规律。同一离子对不同土壤汞的释放量并不与汞全量成正相关关系。同一无机离子在相同浓度条件下，对模拟污染土壤的释放量要明显高于自然污染土壤。
3．从不同离子的释放特征曲线来看，供试无机离子对污染土壤汞的释放能力(即潜在毒性)大致表现为：Cl~->OH~->CO_3~(2-)>SO_4~(2-);Ca~(2+)>Na~+。
4．酸度是影响土壤汞潜在毒性的重要因素之一。随H~+浓度的增大，对污染土壤汞的释放率也随之增大。
5．在所有的释放实验中，以残渣态或晶格态汞为主的原料库区土壤和生产车间土壤均表现出相一致的释放特征。
6．除OH~-和CO_3~(2-)外，实验所选用的无机离子SO_4~(2-)、Cl~-、Na~+、Ca~(2+)及盐酸浓度(mol·L~(-1))与污染土壤汞的释放量(mg·kg~(-1))之间的关系能很好地用多项式方程：y=ax~3+bx~2+cx+d加以描述，相关系数r均达到显著水平(p<0．05)。
This article focuses on the natural contaminated soil samples from a deposed smelt factory's region in Shenyang and the simulative contaminated soil which are all meadow soil as the tested soils, the soils' mercury species are analyzed by sequential extraction species method can be divided the following kinds: water soluble species, exchangeable species, species combined with carbonate and Fe and Mn oxides, species combined with humic acid, species combined with easily oxidized and degraded organic matter, species combined with hardly oxidized and degraded organic matter and residual species existing in mineral lattice et al. seven groups. And investigated their underlying toxicity used the means of the first balance. The results show the following main conclusions:
1.The mercury species distribution in the tested soil exist greatly differences. In these soil, mercury existed in water soluble species are all very low, the highest is in simulative contaminated soil which is 0.50 percent of total, but distinctly higher than the natural contaminated soil; mercury existed in exchangeable species is the highest in simulative contaminated soil and lower pH of made acid plant soil, which are 25.63 and 19.99 percent of total; mercury existed in species combined with carbonate and Fe and Mn oxides is the highest in made acid plant soil, which is 20.33% of total; mercury existed in species combined with humic acid is higher in contaminated soil and lower pH of made acid plant soil, which are all higher than 10%; mercury existed in species combined with easily oxidized and degraded organic matter is the highest in drained waste water region soil of 43.06%, the second is contaminated soil which percent is 35.47%; mercury existed in species combined with hardly oxidized and degraded organic matter is the highest in testing farmland soil which is antitheses, is 14.81%; mercury existed in residual species existing in mineral lattice is the highest in raw material storeroom section soil and produced workshop soil, which are 87.04 and 87.66 percent of total, but the lowest is in simulative contaminated soil which is only 18.28%.
2.In 10-2000 mmol·L~(-1) concentration range, the mercury releasing amount enhanced with the increment of SO_4~(2-)、Cl~-、Na~+ and Ca~(2+), but CO_3~(2-)and OH~-can't put up this uniform disciplinarian. The mercury releasing amount can't take on positive correlativity with the total mercury in tested soil. In the same abio-ion under the uniform concentration, the mercury releasing amount in the simulative contaminated soil are distinct fatter than the natural contaminated soil.
3.From the characteristic curves of Hg released by different ions for the contaminated soil, the mercury releasing ability (namely: underlying toxicity) in the tasted soil approximately behaves: Cl~->OH~->CO_3~(2-)>SO_4~(2-);Ca~(2+)>Na~+.
4.Acidity is one of the importance factors which affects the underlying toxicity of mercury in contaminated soil. The mercury releasing rate increases with the increment of hydrochloric acid concentration.
5.In all released experiments, mercury existed in residual species existing in mineral lattice is primary in raw material storeroom section soil and produced workshop soil which put up accordant released character.
6.In the tasted all abio-ions, with the exception of OH~- and CO_3~(2-), the connection with concentration (mol·L~(-1)) and the mercury releasing amount (mg·kg~(-1)) in contaminated soil can primly be described by multinomial equation: y=ax~3+bx~2+cx+d. All correlative relations reach prominent level (p<0.05).
引文
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65. Coquery M, Cossa D, Sanjuan. Speciation and sorption of mercury in two macro-tidal estuaries [J]. Marine Chemistry, 1997, 58(2):213-227.
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72. Lindberg S. E., Dong Weijin, Jeff Chanton. A mechanism for bimodal emission of gaseous mercury from aquatic macrophytes. Atmospheric Environment.2005, 39:1289-1301.
73. Lindberg S E, Turner P R, Meyers T P, et al. Atmospheric concentrations and deposition of mercury to a deciduous forest at Walker branch watershed, Tennessee, USA [J]. Water Air and Soil Pollution, 1991, 56:577-594.
74. Lindberg,S,E, et al. Micrometeorological gradient approach for quantifying air/surface exchange of mercury vapor tests over contamination soils[J].Environ.Sci.Technol., 1995,29:126-135.
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78. Paul J Lechler, Jerry R Miller, Liang-Chishu, et al. Mercury mobility at the Carson River Superfund??Site, west-central Nevada, USA: interpretation of mercury speciation data in mill tailings, soils and sediments [J].Journal of Geochemical Exploration, 1997, 58: 259-267.
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80. Revis, E, Distribution of mercury species in soil from a mercury contaminated [J]. Water Air and Soil Poll., 1989,45:105-113.
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82. Schroeder W.H. and Munthe J. Atmospheric mercury-An overview. Atmospheric Environment [J]. 1998,32(5):809-822.
83. Sun B, Zhao F J, Lombi E, et al. Leaching of heavy metals from contaminated soils using EDTA [J]. Environmental Pollution.2001, 113:111-120.
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85. Xiao, Z. F., Munthe, J., Schroeder, W.H., Lindqvist, O.Vertical fluxes of volatile mercury over forest soil and lake surfaces in Sweden [J]. Technol, 43B:267-279.
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61. Anthony, C, et al. Sunlight-mediated emission of elemental mercury from soil amended with municipal sewage sludge [J]. Environ Qual., 1997,31(3):2085-2091.
62. AzzariaL M and Aftabt A. Stepwise thermal analysis technique for estimating mercury phases in soils and sediments [J]. Water, Air and Soil Pollution, 1991, 56:203-217.
63. Biester H, Christian S. Determination of mercury binding forms in contaminated soils: mercury pyrolysis versus sequential extraction [J]. Environ. Sci. Technol., 1997,31:233-239.
64. Biester, Muller G, Scholer H L. Binding and mobility of mercury in soils contaminated by emissions from chlor-alkali plants [J].The Science of the Total Environment, 2002,284:191-203.
65. Coquery M, Cossa D, Sanjuan. Speciation and sorption of mercury in two macro-tidal estuaries [J]. Marine Chemistry, 1997, 58(2):213-227.
66. Fitzgerald W F, Is mercury increasing in the atmosphere? The need for an atom-sphere mercury network (AMNET) [J]. Water Air and Soil Pollution, 1995, 80:245-254.
67. Gambrell. Chemical availability of mercury, lead and zinc in mobile bay sediment suspensions as affected by ph and Eh conditions [J].Environ. Sci. Tech., 1980, 14(4):31-36.
68. Garcfa-Sanchez A, Alastuey A, Querol X. Heavy metal adsorption by different minerals: Application to the remediation if pollution soils [J]. The Science of the Total Environment, 1999, 242:179-188.
69. Haidouti C. Soil mercury pollution in area surrounding the state of oil refinery of Aspropirgos Greece [J].Catena, 1991,18:1-10.
70. Higueras P, Oyarzun R, Biester H. A first insight into mercury distribution and speciation in soils from the Almandine mining district, Spain [J].Journal of GeochemicalExploration, 2003, 80:95-100.
71. Lee. Y, H, et al. Fluxes and turnover of methylmercury: mercury pods in forest soil [A].In: Watras. X, J(eds). Mercury Pollution: Integrations and Syntheses [J]. Florida: CRC Press Inc, 1994, 329-342.
72. Lindberg S. E., Dong Weijin, Jeff Chanton. A mechanism for bimodal emission of gaseous mercury from aquatic macrophytes. Atmospheric Environment.2005, 39:1289-1301.
73. Lindberg S E, Turner P R, Meyers T P, et al. Atmospheric concentrations and deposition of mercury to a deciduous forest at Walker branch watershed, Tennessee, USA [J]. Water Air and Soil Pollution, 1991, 56:577-594.
74. Lindberg,S,E, et al. Micrometeorological gradient approach for quantifying air/surface exchange of mercury vapor tests over contamination soils[J].Environ.Sci.Technol., 1995,29:126-135.
75. Lindpvist, et al. Atmospheric mercury in the Swedish environment [J]. Water Air and Soil Poll., 1995, 55:254-261.
76. Mason R P, Sullivan K A. The distribution and speciation of mercury in the South and equatorial Atlantic[J].Deep-Sea Research II, 1999, (46): 937-956.
77. Mason RP, Lawson N M, Sullivan K A, The concentration, speciation and sources of mercuryin Chesapeake Bay precipitation [J].Atmospheric Environment, 1997, 31(21):3541-3550.
78. Paul J Lechler, Jerry R Miller, Liang-Chishu, et al. Mercury mobility at the Carson River Superfund??Site, west-central Nevada, USA: interpretation of mercury speciation data in mill tailings, soils and sediments [J].Journal of Geochemical Exploration, 1997, 58: 259-267.
79. Pirrone N, Keeler G J and Nriagu J O ,Regional differences in worldwide emissions of mercury to theammosphere[J]. Atmospheric Environment, 1996, 30(17):1069-1077.
80. Revis, E, Distribution of mercury species in soil from a mercury contaminated [J]. Water Air and Soil Poll., 1989,45:105-113.
81. Rogers R D and Mcfarlane J C. Impact factors of mercury volatile from soils. Journal of Environmental Quality, 1979, 8:255-260.
82. Schroeder W.H. and Munthe J. Atmospheric mercury-An overview. Atmospheric Environment [J]. 1998,32(5):809-822.
83. Sun B, Zhao F J, Lombi E, et al. Leaching of heavy metals from contaminated soils using EDTA [J]. Environmental Pollution.2001, 113:111-120.
84. Tessier A. Cambell P G C, Bisson M. Sequential Extraction Procedure for the Speciation of Particulate Trace Metal [J]. Analytical Chemistry, 1979, 51 (7)844-850.
85. Xiao, Z. F., Munthe, J., Schroeder, W.H., Lindqvist, O.Vertical fluxes of volatile mercury over forest soil and lake surfaces in Sweden [J]. Technol, 43B:267-279.
86. Ying G, Sebasten S, William H. Epuilibrium speciation of Cd, Cu and Pb in soil solutions. In: Evans L, et al. Eds.Proc.6th International Conference on the Biogeochemistry of Trace Elements. Guelph, Canada, 2001, 459-465.