湘西北黑色泥灰岩风化剖面重金属富集的地球化学机制

通过对湘西北地区黑色泥灰岩风化剖面（DM剖面）中Cr、Ni、Cu、Zn、Cd、Pb、Th、U 8种重金属元素地球化学特征的研究,并与区域上发育于黑色页岩的2条风化剖面的对比分析,初步揭示了黑色泥灰岩风化剖面中重金属富集的地球化学机制。结果表明：（1）与黑色页岩相比,黑色泥灰岩风化成土过程中重金属元素普遍呈现出低背景、高富集的地球化学特征。（2）黑色泥灰岩风化剖面的形成,是在基岩中碳酸盐快速溶蚀的基础上（基岩的酸溶相含量为78.57%）,由酸不溶相进一步演化的结果。在此过程中,对于无明显外源输入的元素Cr、Ni、Cu、Zn、Pb、Th、U,一方面,赋存在酸溶相的部分随碳酸盐的淋失而亏损甚至强烈亏损（其中Th相对惰性）;另一方面,残余在酸不溶相的部分因基岩中大量碳酸盐的淋失而显著富集,且随风化剖面的演化未显示出进一步的亏损。因此,这些元素在风化剖面中的富集是绝对（强烈）亏损和显著相对富集的综合结果。对于Cd,存在明显的外源输入,可能主要以水溶态形式带入并大量淀积在剖面下部。（3）在黑色泥灰岩风化剖面,有机质（OM）不是重金属元素的主要赋存介质,其对重金属元素地球化学行为的影响有限。（4）黑色泥灰岩发育的土壤中,Cu和Cd的平均含量分别为54.58 mg/kg和0.58 mg/kg,高于农用地土壤污染风险筛选值,特别是Cd,对土壤生态环境可能形成不利影响,应引起关注。     

Decomposition of silicate minerals by Bacillus mucilaginosus in liquid culture

The extraction of K⁺ and SiO₂ from silicate minerals by Bacillus mucilaginosus in liquid culture was studied in incubation experiments. B. mucilaginosus was found to dissolve soil minerals and mica and simultaneously release K⁺ and SiO₂ from the crystal lattices. In contrast, the bacterium did not dissolve feldspar. B. mucilaginosus also produced organic acids and polysaccharides during growth. The polysaccharides strongly adsorbed the organic acids and attached to the surface of the mineral, resulting in an area of high concentration of organic acids near the mineral. The polysaccharides also adsorbed SiO₂ and this affected the equilibrium between the mineral and fluid phases and led to the reaction toward SiO₂ and K⁺ solubilization. These two processes led to the decomposition of silicate minerals by the bacterium.     

燃煤型氟中毒区石煤氟的环境地球化学行为研究

通过对比典型剖面上的石煤及其风化发育的土壤的氟含量、流经石煤层的水与不经过石煤层的水的氟含量,研究石煤风化、淋溶时氟对土壤、地表水和农作物的影响。采集居民家中石煤、石煤燃后底灰、室内降尘、玉米、辣椒、水缸水和开水,分析其含氟量,研究石煤燃烧时氟的迁移富集机制。结果表明石煤的风化、淋溶虽导致土壤含氟量大幅升高但对地表水和新鲜粮食的含氟量无显著影响;石煤燃烧后释放出的氟污染室内玉米、辣椒和饮水,导致氟中毒流行。     

土壤中氧化铁的有机还原溶解动力学

研究了土壤中的氧化铁被两种酚化合物还原而溶解的动力学，结果表明，在ｐＨ恒定和有机还原剂过量的情况下，氧化铁的还原溶解符合一级反应动力学方程，还原溶解速率大小与土壤中氧化铁的结晶形态有关．氧化锰的存在影响着氧化铁的还原溶解，在存在足够的还原剂的条件下，两者可同时还原．实验中求得黄壤和赤红壤中氧化铁的还原溶解反应对［Ｈ＋］的反应级数分别为０．１２６和０．１７４。土壤中氧化铁的还原溶解是一个受表面反应控制的过程，反应的速率控制步骤是表面的电子转移反应，磷酸根在土壤中的吸附占据了氧化铁表面的反应位，因而明显抑制还原溶解反应．     

Acidification of groundwater in water-filled gravel pits -- a new environmental and geomedical threat

Swimmers and users of motor boats frequenting old, water-filled gravel pits in Kiiminki, Northern Finland, found in August 1993 that they were suffering from painful irritation of the eyes and that their boats had developed a finely polished surface on their aluminium hulls, evidently due to the corrosive action of the water. Subsequent measurements carried out by the water authority showed that the pH of the water in some of the pits was extremely low, reaching a value of 3.4 at its lowest. To find out the causes of the abnormally low pH values, the present authors began systematic measurements of the pH and determination of the chemical composition (Si, Al, Ca, Mg, K, Na, Fe, Mn, Cu, Pb, Ni, Cd, Cl^-, NO₃ ^-, SO₄ ^2-) of the water in 23 gravel pits. In addition, a series of laboratory experiments was carried out to examine the interaction of water with samples of the soil and bedrock of the area to evaluate the role of this process as a possible cause of the acidification. The results show that the reaction of water with the moderately to intensively weathered sulphide and jarosite-bearing black schists, typical of the bedrock of the area, can bring about aqueous solutions similar in pH and sulphate--nitrate ratios to those found naturally in the gravel pits. The contribution of other possible mechanisms, e.g. acidic precipitation as such or combined with enhanced evaporation, the possible use of the pits as dumping sites for acidic waste or the flow or seepage of acidic peat-bog waters into the pits from the surrounding wetlands, cannot be ruled out entirely, but their contribution seems to be of minor importance. Since the concentrations of several heavy metals (notably Pb, Cd, Ni, Fe and Mn) and of sulphate and aluminium has increased in the pit water as a result of the acidification process and exceed the norms laid down in the EU Drinking Water Directive, acidification of water in gravel pits due to the oxidation of sulphides must be regarded as a new, serious environmental and geomedical threat which has so far remained poorly known or unrecognised.     

Mass balance modeling of arsenic processes in cropland soils

This study delineated the mathematical forms for the reactions involved in the mass balance of As in cropland soils. Even mathematically simplified, many model parameters are required to define the reactive processes involved. Example simulations were conducted based on the range of parameter values and initial conditions derived from published literature. The outcomes showed that the As inputs due to fertilizers and irrigation water caused total As content of the root zone to gradually increase over time. The plant uptake and leaching were equally important as pathways for removal of the added As. In turn, the dissolution kinetics of the mineral phase and the distribution coefficient of the adsorbed phase affected the availability of the As for plant uptake and leaching. Parameters based on laboratory-derived data on the dissolution of As mineral phase, mineralization and oxidation of As(III), and the As plant uptake however appeared to overestimate the As transformations in soils. While the development of mathematical model was a straightforward process, its application to realistic situations was hindered by difficulties of defining model parameter values with confidence. Current knowledge on the processes and reactions of As transformation in the soil–plant system is inadequate to calibrate or validate the model. Studies are needed to understand the kinetics of soil As mineral dissolution and precipitation and the dynamics of root growth and As uptake by plant in soils.     

赣南小流域的水文地球化学特征和主要风化过程

对赣南花岗岩小流域进行采样、测试及分析,发现其河水含有较低的矿化度,水化学组成以Na ,Ca2 ,Cl-1和HCO-3为主,溶解性Si的含量明显较高,代表了典型硅酸盐地区河流的相应化学组成.通过Gibbs图分析,赣南流域大部分地区受大气降水的影响比较显著,"蒸发-浓缩"类型的小流域也较多.根据主成分分析和因子分析的结果,定量地估算了大气中CO2和三类岩石对河水中各种离子的贡献比例.与黄河相比,赣南流域受硅酸盐岩风化作用强烈,但主要影响因素仍是碳酸盐和蒸发盐岩,二者对赣南流域溶解质的贡献率分别为42.8%和29.2%,大气中CO2对河水溶解质的贡献率为21.4%,低于世界平均水平.主要风化反应以岩盐和方解石的溶解为主,Si/(Na* K)比值较低,说明风化反应在表生环境中进行,其产物是富含阳离子的次生矿物.     

汽车内饰材料的人工老化试验

讨论了光的能量和辐射强度、环境温度和湿度对汽车内饰材料老化的作用,介绍了国外广泛使用于汽车内饰材料老化的试验方法和试验设备,认为以氙灯和金属卤素灯为光源的试验设备配置适当的滤波器可进行模拟性最好的人工老化试验,建议加强汽车用材料的老化试验技术和评价方法的研究,尽快制定我国的汽车内饰材料老化试验方法的标准.     

土壤风化速率的实验测定

利用模拟淋溶实验测定了中国几种土壤（砖红壤，赤红壤，红壤，黄棕壤和紫色土）的风化速率，并研究了土壤pH值和降水量对土壤风化速度的影响，结果表明，土壤的风化速度在pH≥4时随pH值的下降而显著增加，但是当pH值低于4时，风化速率却急剧下降，造成这种现象的原因可能是在低pH值时盐基阳离子和铝离子大量溶出，过高的产物浓度限制了风化反应的进行。土壤的风化速度与淋溶速率之间近似成线性关系。用淋溶液pH值和淋溶液量两个因素对实验结果进行了校正。     

Intercomparison of reactive transport models applied to UO2 oxidative dissolution and uranium migration

Oxidative dissolution of uranium dioxide (UO₂) and the subsequent migration of uranium in a subsurface environment and an underground waste disposal have been simulated with reactive transport models. In these systems, hydrogeological and chemical processes are closely entangled and their interdependency has been analyzed in detail, notably with respect to redox reactions, kinetics of mineralogical evolution and hydrodynamic migration of species of interest.Different codes, where among CASTEM, CHEMTRAP and HYTEC, have been used as an intercomparison and verification exercise. Although the agreement between codes is satisfactory, it is shown that the discretization method of the transport equation (i.e. finite elements (FE) versus mixed-hybrid FE and finite differences) and the sequential coupling scheme may lead to systematic discrepancies.