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“老化”作用对有机污染物与土壤相互作用的影响
安显金
导师肖保华
2013
学位授予单位中国科学院研究生院
学位授予地点北京
学位名称硕士
学位专业环境工程
关键词土壤有机质 胡敏素 吸附/解吸 老化 矿物质
摘要土壤是自然环境的重要组成要素。土壤有机质是土壤的重要组成部分和功能单元,它主要包括胡敏酸(HA)、富里酸(FA)和胡敏素(HM)三种组分。土壤有机质一直是土壤学和环境学领域的研究热点。土壤有机质是土壤中吸附有机污染物的主要组分,它对有机污染物在自然环境中的分布和迁移有着重要影响。所处自然环境的物理化学特性不同,土壤有机质所表现出来的对有机污染物的吸附/解吸性质存在不同;不同演化阶段的土壤有机质,其吸附/解吸有机污染物的行为也存在差异。有机污染物的观测浓度和实验室中模拟试验所获取的吸附/解吸等温线等数据是有机污染风险评估的主要依据。但是,实验室模拟试验的时间尺度相对短暂,自然环境中有机污染物(特别是,持久性有机污染物)和土壤的相互作用则可能延续很长的时间,在这样的时间尺度下,有机污染物分子可能深入到模拟试验无法到达的土壤内部的一些微孔结构,从而造成不可逆的吸附,或者,土壤组分和土壤孔隙结构的动态变化导致进入其中的有机污染物难以被重新释放,由此有机污染物在土壤等环境介质上吸附/解吸的行为与模拟试验的结果存在一定的差异。研究人员提出 “老化效应”这个概念来解释这种差异。“老化效应”对正确评估自然环境中有机污染物的环境风险和生物可利用性至关重要。前任的“老化”研究主要集中于稳定体系中长时间尺度的土壤与有机污染物的吸附/解吸行为。我们认为有机污染物在土壤等环境介质中产生“老化”的机制不仅仅是相互作用时间尺度的增加。自然环境中,土壤等环境介质不断受到表生地球化学作用(例如,干湿交替、冰冻融化、溶解沉淀等等)的影响,在吸附/解吸有机污染物的同时,它们本事的理化性质和物理结构也在发生变化,可以预见它们对有机污染物的吸附/解吸也会与模拟试验的结果存在不同,表现出类似“老化”的效果,在一些特定的环境条件下,这种“老化效应”甚至可以在很短的时间内出现,从而影响污染物的环境风险和生物可利用性。迄今,有关表生地球化学过程如何影响有机污染物在土壤等环境介质中“老化”的研究报道还很少。本文的主要目的是通过在实验室中模拟自然界的表生地球化学过程,比如,土壤矿物质在土壤有机质颗粒表面的溶解与沉淀,揭示表生地球化学过程也是造成有机污染物在自然土壤中“老化”的重要机制。为此,我选取了用2种具有代表性的疏水性有机污染物(菲和芘),定量研究了它们在不同土壤上的吸附/解吸特性;选取了2种常见的土壤矿物质(CaCO3和Fe(OH)3)在实验室中模拟了表生地球化学过程(溶解与沉淀)对两种自然土壤的有机质进行“老化”处理,即,土壤有机质的颗粒表面被矿物质沉淀所覆盖包裹;对比研究了老化过程对有机污染物的吸附/解吸的影响。论文的主要结论如下:1. 菲和芘在两同全土壤样品(黄壤和石灰土)及其有机质组分(胡敏素,HM)上的吸附/解吸等温线均可用Freundlich 方程来拟合。同时对解吸的研究发现,解吸滞后系数HI都大于0,说明所有吸附剂都存在解吸滞后现象,进一步说明土壤有机质的结构复杂、具有高度异质性。2. 土壤组分HM对有机污染物的吸附能力比原始土壤的吸附能力要高很多。就污染物菲而言,黄壤土HM组分的Kf和n分别为9597.2 (ug?kg-1)/(ug?L-1)n,0.78;而石灰土HM组分Kf和n分别为52599 (ug?kg-1)/(ug?L-1)n,0.70。黄壤土和石灰土对污染物菲的吸附参数Kf和n分别为1280.8 (ug?kg-1)/(ug?L-1)n,0.66和1712.6 (ug?kg-1)/(ug?L-1)n,0.66。对污染物芘的吸附发现,黄壤土HM组分的Kf和n分别为28004 (ug?kg-1)/(ug?L-1)n,0.80;而石灰土HM组分Kf和n分别为94528 (ug?kg-1)/(ug?L-1)n和0.85。黄壤土和石灰土对污染物芘的吸附参数Kf和n分别为3304.2 (ug?kg-1)/(ug?L-1)n,0.73和4396.2(ug?kg-1)/(ug?L-1)n,0.71。从上面可以看出,无论是菲还是芘,原始土壤HRT,SHT的n值都要比相应土壤HM组分的n值要低。从标准有机碳分配系数Koc(Ce= 0.5 Cw),我们可以发现黄壤土对菲和芘的吸附有机碳标化系数分别为67613.6和117823.7,而其HM组分29368.5和100907.1,而石灰土对菲和芘的吸附有机碳标化系数分别为63272.7和152594.2,其HM组分分别为115130.7和34141.9。3. 实验有效的验证了表生地球化学过程(土壤矿物质的溶解沉淀)是导致土壤中毒害有机污染物“老化”的重要机制之一。CaCO3和Fe(OH)3胶体包裹以后的HM组分,其Kf显著降低,说明钙和铁等矿物质可能覆盖有机质的有效表面、阻塞土壤有机质结构中的微孔,从而导致吸附能力下降。从研究结果,我们可以明显的看出,解吸滞后系数HI值(Ce=1 ug?L-1),两种无机矿物包裹老化后的黄壤土HM的HI值分别为菲:11.2,9.1;芘:6.7,16.0,而对石灰土HM的HI值对应为菲:4.3,4.5;芘: 3.6,2.6,都要比未包裹黄壤土和石灰土HM的HI值,菲:4.5和2.0;芘:3.3和1.92要高。说明“老化”后解吸滞后性有一定的增加,同时也可以说明矿物质包裹能降低有机污染物生物可利用性,能有效的减少对生物体的危害。
其他摘要Soil is an important component of the natural environment. Soil organic matter (SOM), which may be subdivided into three components of humic acids (HAs), fulvic acids (FAs) and humin (HM), is an important component and functional unit of natural soil. The research on the soil organic matters has become a focus in the field of soil and environmental sciences. SOM is a major component for adsorbing organic pollutants in the soil and plays an important role in distribution and migration of pollutants in the natural environment. According to the different physicochemical characteristics of the ambient environment, sorption/desorption properties of SOM are different coordinately; sorption/desorption behaviors of SOM are also different during its different evolution stages. The principles underlie the environmental risk assessment of organic pollutants are on the basis of the isotherms of organic pollutants on the selected media, which were measured mainly in the artificial environments. However,the time scales of processes in the natural environment may be much longer than those of in the laboratory. Given enough time, either organic pollutants can penetrate deeply into the matrix of soil and enter into micropores or physicochemical properties of soil can be changed to cause irreversible sorption, even sequestration, of organic pollutants in soil. Therefore, remarkable errors are often found between the results of field observation and laboratory modeling of risk assessments. A concept of “aging effect” was proposed to interpret and to complement the errors. The “aging effect” is very important for accurately evaluating environmental risks and bioavailability of organic pollutants. The prior studies of “aging effect” mainly focused on the effects of long time scales to interactions of organic pollutants and soils in stable systems, hardly any attention was paid to the evolutions of the environment and the soil itself. This study advised that some naturally occurred processes to the soil are also the reasons of “aging effect”. Actually, in the natural environment, many surficial geochemical processes, such as, wetting and drying, freezing and melting, dissolving and precipitating, etc., are never stopped themselves on the soil to keep changing the properties and the structures of the soil during or after organic pollutants sorption. It is not difficult to tell that these surficial geochemical processes will change the sorption/desorption behaviors of the soil to cause the “aging effect”, and, in certain circumstance, the “aging effect” will be done in a short time. Unfortunately, the studies of the role of surficial geochemical processes in the “aging effect” are scarce. The goal of this study is to demonstrate that the surficial geochemical processes are important mechanisms of “aging effect” by simulating these processes in the laboratory. To achieve this goal, I selected two natural soils and their humin fractions as the experiment samples and two polycyclic aromatic hydrocarbons (PAHs), phenanthrene and pyrene, as the target chemicals, two common soil minerals, Fe(OH)3 and CaCO3, were chosen to “age” the samples by simulating their precipitating on the surface or soils and soil fractions. This study systematically studied the sorption/desorption behaviors of the chemicals on the treated and the untreated soil samples to reveal how the surficial geochemical processes affect the bioavailability of the chemicals. The major findings of this study are as following: 1. The sorption/desorption isotherms of phenanthrene and pyrene on the soils and soil humin fractions are well fit by the Freundlich Equation. All the sorption/desorption hysteresis indices (HI) are greater than zero, indicating that all sorbent samples are highly heterogeneous and show remarkable desorption hysteresis2. The soil humin fractions (HM) show much higher sorption capacity of organic chemicals than the soils do. In the case of phenanthrene,sorption coefficients Kf and n of HM component of yellow soil (HRT) are 9597.2 (ug?kg-1)/(ug?L-1
学科领域环境地球化学
语种中文
文献类型学位论文
条目标识符http://ir.gyig.ac.cn/handle/352002/5870
专题研究生_研究生_学位论文
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安显金. “老化”作用对有机污染物与土壤相互作用的影响[D]. 北京. 中国科学院研究生院,2013.
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