摘要
由于人类和自然的相互作用，城市河流是时刻处于变化中的水动力环境，尤其是接收了来自城市和工业大量人为污染物后，其水体和沉积物来源变得更为复杂。在众多的污染物中，重金属由于其在环境中的持久性、生物地球化学可循环性以及潜在的生态威胁而倍受关注。沉积物既是水环境中重金属的主要汇集场所，又是潜在的次生污染源。研究沉积物中重金属含量、分布特征及赋存形态对于探寻水环境重金属的来源、评价污染现状、预测对生态系统的影响及河流环境保护具有重要的现实意义。
本文以渭河西安段为研究区域，把地表水和沉积物作为一个有机整体，经详细调查、采样和实验，首次系统地研究了渭河西安段地表水的理化特性(pH值、电导率、DO、COD、BOD_5、氟化物)和沉积物的理化性质(pH值、磁学性质、机械组成、烧失量、常量组分)；用X-Ray荧光光谱仪分析了沉积物中重金属元素Cu、Mn、Pb、Zn、Co、Ni、Cr、Fe和As的全量及在不同粒径颗粒中的含量，探讨了重金属的分布特征；采用欧共体修正BCR四步连续提取法及原子吸收分光光度计火焰法分析测定了表层沉积物重金属Cu、Mn、Pb、Zn、Co、Ni、Cr和Fe的赋存形态；通过相关分析和聚类分析讨论了重金属之间的相互关系及影响重金属含量和形态的因素，以期为合理开发利用渭河水资源，制定污染防治措施以及流域治理规划等提供科学依据。
本研究主要结论如下：
(1)渭河西安段地表水属中性水质，各项理化指标的均值分别为：pH值7．129，电导率528μs／cm，DO 0．29mg／L，COD 85．1mg／L，BOD_5 22．6mg／L，氟化物0．4601mg／L。沉积物pH值为8．604，为碱性沉积物；粒径组成平均是黏粒10．050％，粉沙粒50．395％，沙粒39．555％，质地类型主要为粉沙粒：沉积物烧失量平均为3．563％；沉积物低频磁化率(χLF)、高频磁化率(χHF)和频率磁化率(χfd)均值分别为50．7×10~(-8)m~3／kg、46．2×10~(-8)m~3／kg和2．36％；常量元素K_2O、Na_2O、CaO、MgO、Al_2O_3、Fe_2O_3、SiO_2和Ti的平均含量分别为：2．26％、1．86％、6．64％、2．09％、11．20％、3．69％、58．52％和3593．3mg／kg。
(2)渭河西安段表层沉积物中Co、Cr、Fe、Cu和Pb的平均含量高于环境背景值，As、Mn和Ni的平均含量低于环境背景值，Zn平均含量与环境背景值持平。各重金属元素水平呈波折多峰型分布，其中As、Cu、Mn、Pb、Zn、Ni和Fe具有相似的水平分布特征；各断面重金属累积叠加值由高到低依次为：断面4>断面6>断面3>断面2>断面5>断面1，大部分元素高值区均位于河流中下游河段。
(3)筛分实验结果表明：渭河西安段表层沉积物不同粒径颗粒中重金属含量分布具有一定的差异，主要富集于粒径为150-250μm、250-450μm、450-900μm和>900μm的较大颗粒中，其余粒径颗粒中重金属含量相对略小。
(4)渭河西安段柱状沉积物中各重金属元素在垂向上明显地呈波折多峰型分布，其中As、Cu、Mn、zn、Ni和Fe表现出非常相似的垂向变化趋势，表明它们具有同一物质来源或相同的沉积后再迁移行为。Pb、Co和Cr在垂直剖面上变化规律性不强。
(5)渭河西安段地表水中Cu和Zn主要以溶解态存在，Mn、Pb、Co、Ni、Cr和Fe主要以颗粒态存在。表层沉积物中各重金属主要以残余态存在，其中Pb的“非稳态”(易迁移转化部分)含量大于“稳定态”，其余元素“稳定态”占优势。
(6)统计分析表明：地表水中Cu、Mn、Fe的溶解态、颗粒态、全量两两之间均显著相关：Zn的溶解态、颗粒态均与全量显著相关：Co、Ni、Cr的颗粒态与全量显著相关：Pb的全量与DO显著相关，Zn的溶解态与COD、BOD_5、氟化物显著相关，Co的pH值分别与溶解态、全量显著相关。沉积物中大多数重金属的全量和形态与低频磁化率(χLF)、高频磁化率(χHF)、黏粒、粉沙粒含量、烧失量(LOI)及常量组分中的K_2O、Na_2O、MgO、Al_2O_3、Fe_2O_3、SiO_2、Ti之间相关性较好，反映了影响沉积物重金属富集及赋存形态的主要因素。As、Cu、Mn、Pb、Zn、Ni和Fe两两之间均显著相关，Co、Cr与上述元素相关性较弱。Cu的可氧化态、残余态、全量两两之间显著相关；Mn的弱酸提取态、可还原态、残余态、全量两两之间显著相关；Pb的弱酸提取态与残余态、可还原态与全量显著相关；Zn的可还原态与弱酸提取态、全量显著相关;Co和Cr的残余态均与其全量显著相关；Ni的全量分别与弱酸提取态、残余态显著相关；Fe的弱酸提取态、残余态、全量两两之间显著相关，可还原态与可氧化态显著相关。
(7)重金属元素来源分析表明：渭河西安段沉积物中As、Cu、Mn、Pb、Zn、Co、Ni和Fe可能以自然来源为主，Cr可能以人为来源为主，重金属元素在时间跨度内的分布特征反映了其自然来源和人为来源的差异。
Urban river is a complex dynamic system interacted by human and natural environments, especially when receiving large amounts of anthropogenic contaminants from nearby urban areas and industrial sites. Among the various contaminants, heavy metals are of particular concern due to their environmental persistence and biogeochemical recycling and ecological risks. Sediments are not only main places of heavy metals accumulating but also potential pollution sources in water environment. Therefore, it is necessary to research the contents, distribution characteristics and chemical fractionations of heavy metals in sediments. The results would make a great contribution to understand the heavy metal resources, assessing pollution status and the affection to ecosystem, and have a great significance to environmental protection of urban river.
Xi'an section of Wei River is regarded as the research area in this paper. Based on full field survey, collecting samples and experiments, the physio-chemical characteristics of surface water including pH value, conductivity, dissolved oxygen (DO), chemical oxygen demand (COD), biochemical oxygen demand in five days (BOD_5) and fluorides and sediments including pH value, magnetic susceptibility, particle size, loss on ignition and major elements are for the first time studied. The contents with different particle size and total contents of Cu, Mn, Pb, Zn, Ni, Cr, Fe and As are determined by X-ray fluorescence spectrometry (XFS) in sediments and the spatial distributions of all heavy metals are analysed. Chemical fractionations of Cu, Mn, Pb, Zn, Ni, Cr and Fe in surface sediments are studied by BCR sequential extraction method and determined by flame atomic absorption spectrometry (AAS). Factors influencing heavy metal elements concentration and chemical fractionations are discussed through the correlation and cluster analysis. These provided a scientific reference for reasonable development and utilization of water resources of Wei River, constituting the measures of pollution control and the watershed management planning.
The main conclusions in this study are as follows:
(1) The surface water is genera in Xi'an section of Wei River. The averages of pH value, conductivity, dissolved oxygen, chemical oxygen demand, biochemical oxygen demand in five days and fluorides are 7.129, 528μs/cm, 0.29mg/L, 85.1mg/L, 22.6mg/L, 0.4601mg/L, respectively. The average pH value of sediment is 8.604, so it is the alkaline sediment. The sediment texture type is silty sand. The average clay content is 10.050%, and the average silty sand content is 50.395%, and the average sand particle content is 39.555%. The average loss on ignition of sediments is 3.563%. Low-frequency magnetic susceptibility, high-frequency magnetic susceptibility and frequency magnetic susceptibility are 50.7×10~(-8)m~3/kg, 46.2×10~(-8)m~3/kg and 2.36%, respectively. The average contents of K_2O, Na_2O, CaO, MgO, Al_2O_3, Fe_2O,. SiO_2 and Ti are 2.26%, 1.86%, 6.64%, 2.09%, 11.20%, 3.69%, 58.52% and 3593.3mg/kg, respectively.
(2) The average contents of Co, Cr, Fe, Cu and Pb in surface sediments from Xi'an section of Wei River are higher than the environment background, respectively. The average contents of As, Mn and Ni are lower than the environment background, respectively. The average content of Zn is similar to the environment background. The horizontal distribution of all heavy metals in surface sediments is of twists and turns. As, Cu, Mn, Pb, Zn, Ni and Fe in surface sediments have the similar horizontal distribution characters. The cumulative values of sections are in the following order: section 4>section 6>section 3>section 2>section 5>section 1. The higher regions of most heavy metal elements in surface sediment are the middle and lower reaches of Wei River.
(3) The experimental results of sieving indicate that content distributions of heavy metals in surface sediments with different particle size from Xi'an section of Wei River have some differences. The heavy metals mainly accumulate at 150～250μm, 250～450μm, 450～900μm and >900μm.. The rests are fairly little.
(4) The vertical distribution of heavy metals in core sediments from Xi'an section of Wei River is of twists and turns, and do not form a certain feature because of the complex hydrological environment and the different human activity from the coasts. As, Cu, Mn, Zn, Ni and Fe in core sediments have the similar vertical distribution characters, which shows that these heavy metals are of the same material sources or the similar remigration behaviors after depositing. The vertical distribution characters of Pb, Co and Cr are unconspicuous.
(5) In surface water from Xi'an section of Wei River, the main fractionations of Cu and Zn are soluble species, whereas the main fractionations of Mn, Pb, Co, Ni, Cr and Fe are particulate species. In surface sediments from Xi'an section of Wei River, the main fractionation of each heavy metal is residual form. The content of "labile" fractionation for Pb is more than "stable" fractionation. The "stable" fractionations of other heavy metals are in the ascendant.
(6) The statistical data showed that there are significant correlations among soluble fractionations, particulate fractionations, total contents for Cu, Mn and Fe in surface water. Significant correlations also existe between total content and soluble fractionation, particulate fractionation, respectively for Zn in surface water. There are also significant correlations between particulate fractionations and total contents for Co, Ni and Cr in surface water. For Pb in surface water, there is a significant correlation between total content and DO. For Zn in surface water, there are significant correlations between soluble fractionation and COD, BOD_5, fluoride, respectively. For Co in surface water, there are significant correlations between pH value and soluble fractionation, total content, respectively. For most heavy metal elements in sediments, there are significant correlations between fractionations and low-frequency magnetic susceptibility, high-frequency magnetic susceptibility, clay, silty sand, loss on ignition, K_2O, Na_2O, MgO, Al_2O_3, Fe_2O_3, SiO_2, Ti, respectively, so are total contents. The above phenomenon reflects main factors of influencing tomitsumi and fractionations for heavy metals. There are significant correlations among As, Cu, Mn, Pb, Zn, Ni, Fe, but there is not significant correlation between Co and other heavy metal elements in sediments, so is Cr. For Cu in sediments, significant correlations existe among oxidable fractionation, residual fractionation, total content. For Mn in sediments, significant correlations also existe among acid extractable fractionation, reducible fractionation, residual fractionation, total content. For Pb in sediments, there are also significant correlations between acid extractable fractionation and residual fractionation, at the same time between reducible fractionation and total content. For Zn in sediments, significant correlations also existe between reducible fractionation and acid extractable fractionation, total content, respectively. For Co in sediments, there is significant correlation between residual fractionations and total contents, so is Cr. For Ni in sediments, significant correlations also existe between total content and acid extractable fractionation, residual fractionation, respectively. For Fe in sediments, there are also significant correlations among acid extractable fractionation, residual fractionation, total content, at the same time between reducible fractionation and oxidable fractionation.
(7) The source analysis of heavy metal elements shows that As, Cu, Mn, Pb, Zn, Co, Ni and Fe in sediments from Xi'an section of Wei River may be mainly come from natural sources, however, Cr in sediments may be mainly come from pollution due to human activities, which is decided bydistribution characteristics of heavy metals in sediments in the time span.
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