高温高压下H2O-CH4体系PVTx性质的分子动力学模拟研究

Geological fluids are important components in the earth system. To study thephysical chemistry properties and the evolution of fluid system turns out to be one of the most challenging issues in geosciences. Besides the conventional experimental approaches and theoretical or semi-theoretical modeling, molecular level computer simulation(MLCS) emerges as an alternative tool to quantificationally study the physico-chemical properties of fluid under extreme conditions in order to find out the characteristics and interaction of geological fluids in and around earth. Based on our previous study of the intermolecular potential for pure H2O and thestrict evaluation of the competitive potential models for pure CH4 and the ab initio fitting potential surface across H2O-CH4 molecules in this study, we carried out more than two thousand molecular dynamics simulations for the PVTx properties of pure CH4 and the H2O-CH4 mixtures. Comparison of 1941 simulations with experimental PVT data for pure CH4 shows an average deviation of 0.96% and a maximum deviation of 2.82%. The comparison of the results of 519 simulations of the mixtures with the experimental measurements reveals that the PVTx properties of the H2O-CH4 mixtures generally agree with the extensive experimental data with an average deviation of 0.83% and 4% in maximum, which is equivalent to the experimental uncertainty. Moreover, the maximum deviation between the experimental data and the simulation results decreases to about 2% as temperature and pressure increase,indicating that the high accuracy of the simulation is well retained in the high temperature and pressure region. After the validation of the simulation method and the intermolecular potential models, we systematically simulated the PVTx properties of this binary system from 673 K and 0.05 GPa to 2573 K and 10 GPa. In order to integrate all the simulation results and the experimental data for the calculation of thermodynamic properties, an equation of state (EOS) is developed for the H2O-CH4 system covering 673 to 2573 K and 0.01 to 10 GPa. Isochores for compositions < 4 mol% CH4 up to 773 K and 600 MPa are also determined in this thesis.

海南土壤中Zn、Pb、Cu、Cd四种重金属含量及其生物有效性的研究

对海南63 个土壤样品中的Zn、Pb、Cu、Cd 四种重金属的总量和生物有效态含量以及45 个植物样(根、茎、叶) 中的重金属含量分别进行了测定,采样点基本上覆盖了海南全省,测定结果表明,土壤中Zn 总量低于全国平均值,而Pb、Cu、Cd 高于全国平均值,土壤中重金属生物有效态含量一般低于其总量的10 % ,其中Pb 最高为7. 71 % ,而Cu 仅为1. 13 % ,具有较大的变异性;植物中重金属含量与土壤中重金属总量呈现负相关性,但与土壤中有效态重金属含量一般呈现正相关性,叶中的重金属含量与土壤中有效态重金属含量之间的相关性更为显著,叶中的重金属含量与土壤中有效态重金属含量之间的相关系数分别为: Zn (01726) ,Cu (01626) , Pb(01774) ,Cd(01512) 。这说明土壤中重金属总量并不能全面的评价土壤的环境效应和重金属的生物有效性,应该把重金属总量和生物有效态含量结合起来加以研究,并应将土壤中重金属的含量与植物中该元素含量之间作相关分析,根据其相关系数的大小来判断其生物有效性的程度。