密云水库沉积物中腐殖酸特征及其与重金属吸附作用研究
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摘要
饮用水水源地的环境安全是关系民生的重大问题,重金属污染已经严重影响着居民生活用水安全。腐殖酸广泛的分布于地球的生态环境中,沉积物中腐殖酸可以有效吸附水环境中无机和有机污染物,这种结合能力取决于腐殖酸的化学结构和组成。而腐殖酸与重金属离子的结合强度不同,使得腐殖酸成为水环境中重金属离子的“汇”和“源”。因此,开展沉积物中腐殖酸的结构特征、腐殖酸结合态重金属的特征、腐殖酸吸附重金属离子的研究,对于水源地环境保护具有重要的现实价值。
本论文以北京市唯一的地表水水源地密云水库为研究对象,通过国际腐殖质协会推荐的方法提取水库表层沉积物中的腐殖酸,利用固态核磁共振技术分析腐殖酸的结构组成；通过表层沉积物腐殖酸与对应沉积物中重金属分布,研究密云水库重金属的来源、重金属在腐殖酸中的结合能力以及腐殖酸结合重金属的环境效应；选取腐殖酸吸附量大的Cu元素、工矿业活动来源的Cd和Pb元素作为研究元素,探讨水库潮河区域和白河区域的两个腐殖酸对这三种重金属元素的吸附作用及影响因素。其主要的研究结果如下：
1.密云水库表层沉积物中总有机碳的平均含量为16.40mg/g,腐殖酸平均含量为0.71mg/g。总有机碳的空间分布表现为中间区域>白河区域>潮河区域,表层沉积物中有机碳主要来源是白河和潮河径流,水库北岸的大量农田对水库中间区域的表层沉积物有机碳有重要的影响。腐殖酸的含量与有机碳含量没有出现一致性的关系,腐殖酸在水库的白河区域的含量相对较高。
2.密云水库表层沉积物中腐殖酸具有相似的结构,主要结构为非极性脂肪链、羧基结构、芳香结构、甲氧基和碳水化合物。部分腐殖酸上存在烷基取代的芳香碳结构、异构的O-C-O和羰基,而羰基主要出现在水库潮河和中间区域,白河区域腐殖酸结构中则没有这一官能团。腐殖酸中的非极性脂肪链含量最高,平均值为42.79%,其次为羧基20.38%,含氧官能团(甲氧基和碳水化合物)19.03%,芳香官能团14.11%,其它结构含量都较小。水库不同区域的腐殖酸结构存在差异,潮河区域腐殖酸中的羧基含量高于其它区域。腐殖酸的脂化度较高,芳香度和氧化度较低。在白河和潮河入库口附近,腐殖酸主要来为陆源的生物来源,而在受水流作用较弱的其它区域则也有部分来源于水库内的水生生物。
3.密云水库表层沉积物重金属含量与页岩平均值相比没有出现明显的富集,地累积指数表明表层沉积物重金属没有受到污染。水库表层沉积物重金属主要由潮、白河及其支流的径流携带进入水库沉积,水库中白河和潮河区域的地理环境不同,使得两河携带的重金属在水库中的空间分布规律不同。潮河区域大部分金属的含量在入库口附近和潮河大坝附近的含量较高,水流方向的中间区域较低；而白河区域在入库口附近和白河大坝处含量较低,水流方向的中间区域含量较高；密云水库中间区域的金属含量总体较低,但在牤牛河汇入水库附近区域的金属含量有明显的增大。表层沉积物重金属的主成分和相关性分析结果表明,重金属来源主要有两个来源,第一主成分包括Ni、Cr、Cu、V、Zn、Mn以及部分的Pb,代表流域的风化和土壤侵蚀来源,第二主成分包括Cd和Pb,以及部分的Cr、Cu、V、Zn、Mn,代表工矿业来源。牤牛河上游堆放的金矿尾砂已经对密云水库重金属污染构成了一种潜在的威胁。
4.水库表层沉积物腐殖酸中重金属结合容量的大小顺序为Zn(143.21-2858.13μg/g)>Cu(236.07-4887.07μg/g)>Cr(18.17-2137.81μg/g)>>Ni(13.56-1757.581μg/g)>>V(0.55-46.97μ.g/g)>Pb(0.71-29.04μ.g/g)>Cd(0-2.59μg/g)。在研究的金属元素中,腐殖酸中Cu和Zn含量显著高于对应表层沉积物中的含量,Cu和Zn在腐殖酸上比沉积物中有更强的结合能力,并形成更加稳定的络合物,因此腐殖酸可以有效的去除水环境中Cu和Zn离子,并降低其生物有效性。由于表层沉积物中腐殖酸含量较低,腐殖酸中的Cu和Zn分别占沉积物中总量的0.31%-4.16%和0.11%-1.91%,其它金属元素在腐殖酸中的含量占沉积物总量比例都小于1%。其它的金属元素更容易与沉积物中的其它组分结合,但由于腐殖酸的结构和环境条件(如氧化还原条件等)不同,在一些区域腐殖酸也与Cr和Ni有较强的结合能力。地累积指数结果表明腐殖酸中的Cu和Zn具有中强度的污染,腐殖酸中的其它重金属含量则没有明显的污染。腐殖酸中重金属含量可以反映水环境重金属污染和来源,对于水源地的水环境安全评价有重要的指示作用。
5.研究了不同区域腐殖酸(潮河区域腐殖酸CHHA和白河区域BHA)对Cu2+、Cd2+和Pb2+吸附作用。其结果表明：在重金属离子的不同起始浓度下,随着重金属离子的浓度增加,腐殖酸对Cu2+、Cd2+和Pb2+吸附量逐渐增大并最终趋于平衡,吸附率反而逐渐减小；在不同的pH值下,腐殖酸对Cu2+和Cd2+吸附量随着pH值增加而增大并逐渐稳定,Cu2+吸附的临界点为pH=6.0,Cd2+临界点为pH=5.0,而Pb2+的吸附量受pH值变化的影响较小；在不同温度下,随着温度的降低,腐殖酸对Cu2+、Cd2+和Pb2+吸附量都相应的增加；在相同的条件下,不同腐殖酸对Cu2+、Cd2+和Pb2+吸附量表现为CHHA>BHA,主要是因为CHHA中的羧基和酚羟基官能团含量高于BHA,表明Cu2+、Cd2+和Pb2+在腐殖酸上的吸附作用主要是发生在羧基和酚羟基官能团上。
6.腐殖酸对Cu2+、Cd2+和Pb2+的等温吸附符合Freundlich方程,Langmuir方程和Temkin方程,其中Langmuir方程达到极显著水平。在相同条件下,腐殖酸对三种重金属离子的饱和吸附量大小为Pb2+>Cu2+>Cd2+。在25℃,pH6.0时,CHHA对Cu2+、Cd2+和Pb2+的饱和吸附量分别为23.65mg/g,4.64mg/g和44.64mg/g,BHA饱和吸附量分别为17.29mg/g,3.23mg/g和38.09mg/g；在15℃,pH6.0时,CHHA对Cu2+、Cd2+和Pb2+的饱和吸附量分别为25.49mg/g,5.79mg/g,69.45mg/g；BHA的饱和吸附量为18.30mg/g,4.85mg/g,41.65mg/g。
综上所述,不同区域中腐殖酸结构、腐殖酸结合金属含量和腐殖酸吸附金属饱和容量都存在着一定的差异。腐殖酸对金属离子吸附量远大于腐殖酸本身结合态的金属离子含量,腐殖酸与重金属离子的作用既包括表面吸附也有内部结合。因此,腐殖酸能够有效去除水环境中的重金属,降低重金属的生物有效性,同时,当水体环境条件发生变化时,一部分腐殖酸吸附结合的重金属会释放到环境中形成重金属的“二次污染”。因此,对腐殖酸与重金属的研究不仅对其吸附机理有重要的作用,同时也为水源地的环境保护提供了重要的科学依据。
Water quality of the drinking water source is strong and direct link between people's health and improvement of communities. The pollution by heavy metal has been a serious impact on the safety of drinking water. Humic acid, the most widely distributed in natural environment, can effectively react on inorganic and organic pollutants, and is very important in the formation of a variety of complexes. In general, heavy metals can be substracted from water environment by humic acid. However, the ability of binding capacity and affinity depends on the chemical structure and composition of humic acid. The different complexion strength can determine to the "sink" and "source" for heavy metals in the water environment. Therefore, the metal binding capacities of Humic acid are important to practical signification for the the environmental protection of drinking water source.
Miyun Reservoir has been used as unique surface drinking water storage for Beijing. The sediments of Miyun Reservoir are an important repository for nutrient substances and heavy metals from rivers and surrounding environment. The water quality of Miyun Reservoir directly affects health and safety of residents in Beijing. The sediments of Miyun Reservoir were studied as the research object. Humic acid extracted from surface sediment followed by a method from the International Humic Substance Society (IHSS). The structural characterization of humic acid was investigated by solid state NMR, and the content and distribution of humic acid and TOC were determined to the nutrient levels. The concentration and distribution of metal binding humic acid and corresponding sediments were analyzed for the sources of heavy metals, the capacities of metal binding by humic acid and the environmental effects. Cu, Cd and Pb were chosen for adsorption on sedimentary humic acid at different location of Miyun Reserovior, the characterization of the adsorption and the impact factors were discussiong. The main results are following:
1. The average content of total organic carbon in the surface sediments was about16.40mg/g, and the average concentration of humic acid was0.71mg/g. The spatial distribution of total organic carbon was the order of the middle region> the flow area of Bai River> the flow area of Chao River. The main source of organic carbon in the surface sediments were the runoff by Bai River and Chao River. However, a large of farmland in north of middle reservoir had become an important source of organic carbon. The content of humic acid and organic carbon appeared an unconsistent relationship, and the concentration of humic acid was relatively higher in the flow area of Bai River.
2. The sedimentary humic acids in Miyun Reservor were found to be quiet similar, the main structure of sedimentary humic acid was comprised of non-polar aliphatic chain, carboxyl groups, aromatic group, methoxy group and carbohydrates. Partial of humic acid also included aromatic C-O, O-C-O anomerics and carbonyl. However, carbonyl occurred mainly at the middle region and the flow area of Chao River in Miyun Reservior, and this group was not found at in the flow area of Bai River. Among all the groups, the content of non-polar aliphatic chain was the highest and the average value reached to42.79%, the following was carboxyl groups (about20.38%), oxygen-containing groups (including methoxy group and carbohydrates, about19.03%), aromatic group (about14.11%), and other groups were smaller. Howerver, the structure of humic acids were diversity at different regions, such as the carboxyl group was higher at the flow area of Chao River than other regions. Aliphaticity of humic acid was higher, and armoaa' city and degree of oxidation were lower. At the near of infall to Chao River and Bai River, humic acid mainly came from land-based biological origin, and the other regions suffered from weak water flow were derived from aquatic organisms within the reservoir.
3. The contents of heavy metals in surface sediments were at a low level comparing with the average shale values. Index of geoaccumluation showed heavy metals were uncontamination. Heavy metals in surface sediments were mainly carried by the river into the reservoir and deposition, The spatial distribution of heavy metals at Miyun Reservior was different due to the geographical environment of the two rivers. At the flow area of Chao River, the higher contents of metals were found near the input of reservoir and Chao Dam, and the lower was at the middle of the flow direction. However, at the flow area of Bai River, the lower concentrations of metals were found near the the input of reservoir and Bai Dam, and the hiher was at at the middle of the flow direction. At the middle of Miyun Reservoir, the contents of most metals were lower, but there were a significant increase near the import of the Mangniu River. The results of principal component and correlation analysis showed there were two main sources for metals in surface sediments. The first principal component, including Ni, Cr, Cu, V, Zn, Mn, and part of Pb, represented the source of rock wreathing and soil erosion. The second principal component, consisting of Cd and Pb, and partial concentration of Cr, Cu, V, Zn and Mn, represented the source of industrial mining. The gold mine tailings stacked at the upstream of Mangniu River were potential threat to heavy metals pollution for drinking water source.
4. The order of the heavy metals binding to humic acid in surface sediments was as follows:Zn (143.21-2858.13μg/g)> Cu (236.07-4887.07μg/g)> Cr (18.17-2137.81μg/g)> Ni (13.56-1757.58μg/g)> V (0.55-46.97μg/g)> Pb (0.71-29.04μg/g)>Cd (0-2.59μg/g). Of the studied metals, the concentrations of Cu and Zn in humic acid were significantly higher than the corresponding sediments, and Cu and Zn showed a greater affinity for humic acid than sediment, suggesting the possible formation of more stable complexes with humic acid, and it could reduce the bioavailability of these contaminats. With lower content of humic aicd, respectively0.31%-4.16%and0.11%-1.91%of the total Cu and Zn in surface sediments were recovered into humic acid, and other metals were lower than1%. Other metals seemed to prefer sediment, even though Cr and Ni were found a general increase in its content in humic acid in some areas, probably because of the structure of humic acid and environmental conditions (such as oxic to anoxic conditions). The results of index of geoaccumluation showed Cu and Zn had a stronger enrichment in humic acid, but the contents of other metals showed no obvious enrichment in humic acid. The contents of heavy metals in humic acid reflected the source and pollution of heavy metals in water environment, and provided valuable information on drinking water source for environmental safe assessment.
5. The adsorption of Cu2+、Cd2+and Pb2+on the different surface sedimentary humic acids (CHHA and BHA) were investigated under different conditions. Under the different initial concentrations of heavy metals, the adsorptive capacity of Cu2+、 Cd2+and Pb2+was increased gradually and eventually equilibrium with the ions of three heavy metals increased, but the adsorption rate was gradually decreased. The pH value could impact on the adsorption of Cu2+and Cd2+, the adsorptive capacity of Cu2+and Cd2+was increased and eventually up to a certain scope no longer to increase as the pH value increased, and the bound of pH value for Cu2+on humic acid with experimental range was6.0, and Cd2+was5.0, but the pH values palyed a smaller effect on adsorptive capacity of Pb2+. Temperature also affected the adsorptive capacity of Cu2+, Cd2+and Pb2+, and the adsorptive capacities of these three ions were increased as the temperature decreased. Under the same conditions, the size of the amount of adsorption for Cu2+, Cd2+and Pb2+on different humic acid was CHHA> BHA, this was mainly due to the content of the carboxyl and phenolic hydroxyl functional groups in CHHA was higher than BHA.
6. The results showed that the adsorption isotherm of Cu2+> Cd2+and Pb2+on humic acids complied with the Freundlich equation, the Langmuir equation and the Temkin equation, and the Langmuir equation showed a significant level. In the same conditions, the order of the highest capacity to metal ions on humic acid was Pb2+> Cu2+>Cd2+. In the conditions of25癈and pH6.0, the highest capacities to Cu2+> Cd2+and Pb2+on CHHA were respectively23.65mg/g,4.64mg/g and44.64mg/g, while on the BHA were respectively17.29mg/g,3.23mg/g and38.09mg/g. However, in15"C and pH6.0, the highest capacities to Cu2+> Cd2+and Pb2+on CHHA were respectively25.49mg/g,5.79mg/g and69.45mg/g, but on BHA were respectively18.30mg/g,4.85mg/g and41.65mg/g.
In summary, the structure of humic acid, metal binding by humic acid, and the saturated adsorption capacities of humic acid were differences in different regions. The amount of adsorption capacity was much larger than the content of metal binding to the humic acid, and the reaction of heavy metals on humic acid included both surface adsorption and internal combination. Heavy metals in water environment were effectively removed by humic acid, and bioavailability of heavy metals was reduced. However, when the water environmental conditions were changed, a part of surface adsorptive content on humic acid would be release to water and form a "secondary pollution" for heavy metals. Therefor, the study on the reaction of humic acid and heavy metals can provide an important scientific basis for the environmental protection of water sources.
本论文以北京市唯一的地表水水源地密云水库为研究对象,通过国际腐殖质协会推荐的方法提取水库表层沉积物中的腐殖酸,利用固态核磁共振技术分析腐殖酸的结构组成；通过表层沉积物腐殖酸与对应沉积物中重金属分布,研究密云水库重金属的来源、重金属在腐殖酸中的结合能力以及腐殖酸结合重金属的环境效应；选取腐殖酸吸附量大的Cu元素、工矿业活动来源的Cd和Pb元素作为研究元素,探讨水库潮河区域和白河区域的两个腐殖酸对这三种重金属元素的吸附作用及影响因素。其主要的研究结果如下：
1.密云水库表层沉积物中总有机碳的平均含量为16.40mg/g,腐殖酸平均含量为0.71mg/g。总有机碳的空间分布表现为中间区域>白河区域>潮河区域,表层沉积物中有机碳主要来源是白河和潮河径流,水库北岸的大量农田对水库中间区域的表层沉积物有机碳有重要的影响。腐殖酸的含量与有机碳含量没有出现一致性的关系,腐殖酸在水库的白河区域的含量相对较高。
2.密云水库表层沉积物中腐殖酸具有相似的结构,主要结构为非极性脂肪链、羧基结构、芳香结构、甲氧基和碳水化合物。部分腐殖酸上存在烷基取代的芳香碳结构、异构的O-C-O和羰基,而羰基主要出现在水库潮河和中间区域,白河区域腐殖酸结构中则没有这一官能团。腐殖酸中的非极性脂肪链含量最高,平均值为42.79%,其次为羧基20.38%,含氧官能团(甲氧基和碳水化合物)19.03%,芳香官能团14.11%,其它结构含量都较小。水库不同区域的腐殖酸结构存在差异,潮河区域腐殖酸中的羧基含量高于其它区域。腐殖酸的脂化度较高,芳香度和氧化度较低。在白河和潮河入库口附近,腐殖酸主要来为陆源的生物来源,而在受水流作用较弱的其它区域则也有部分来源于水库内的水生生物。
3.密云水库表层沉积物重金属含量与页岩平均值相比没有出现明显的富集,地累积指数表明表层沉积物重金属没有受到污染。水库表层沉积物重金属主要由潮、白河及其支流的径流携带进入水库沉积,水库中白河和潮河区域的地理环境不同,使得两河携带的重金属在水库中的空间分布规律不同。潮河区域大部分金属的含量在入库口附近和潮河大坝附近的含量较高,水流方向的中间区域较低；而白河区域在入库口附近和白河大坝处含量较低,水流方向的中间区域含量较高；密云水库中间区域的金属含量总体较低,但在牤牛河汇入水库附近区域的金属含量有明显的增大。表层沉积物重金属的主成分和相关性分析结果表明,重金属来源主要有两个来源,第一主成分包括Ni、Cr、Cu、V、Zn、Mn以及部分的Pb,代表流域的风化和土壤侵蚀来源,第二主成分包括Cd和Pb,以及部分的Cr、Cu、V、Zn、Mn,代表工矿业来源。牤牛河上游堆放的金矿尾砂已经对密云水库重金属污染构成了一种潜在的威胁。
4.水库表层沉积物腐殖酸中重金属结合容量的大小顺序为Zn(143.21-2858.13μg/g)>Cu(236.07-4887.07μg/g)>Cr(18.17-2137.81μg/g)>>Ni(13.56-1757.581μg/g)>>V(0.55-46.97μ.g/g)>Pb(0.71-29.04μ.g/g)>Cd(0-2.59μg/g)。在研究的金属元素中,腐殖酸中Cu和Zn含量显著高于对应表层沉积物中的含量,Cu和Zn在腐殖酸上比沉积物中有更强的结合能力,并形成更加稳定的络合物,因此腐殖酸可以有效的去除水环境中Cu和Zn离子,并降低其生物有效性。由于表层沉积物中腐殖酸含量较低,腐殖酸中的Cu和Zn分别占沉积物中总量的0.31%-4.16%和0.11%-1.91%,其它金属元素在腐殖酸中的含量占沉积物总量比例都小于1%。其它的金属元素更容易与沉积物中的其它组分结合,但由于腐殖酸的结构和环境条件(如氧化还原条件等)不同,在一些区域腐殖酸也与Cr和Ni有较强的结合能力。地累积指数结果表明腐殖酸中的Cu和Zn具有中强度的污染,腐殖酸中的其它重金属含量则没有明显的污染。腐殖酸中重金属含量可以反映水环境重金属污染和来源,对于水源地的水环境安全评价有重要的指示作用。
5.研究了不同区域腐殖酸(潮河区域腐殖酸CHHA和白河区域BHA)对Cu2+、Cd2+和Pb2+吸附作用。其结果表明：在重金属离子的不同起始浓度下,随着重金属离子的浓度增加,腐殖酸对Cu2+、Cd2+和Pb2+吸附量逐渐增大并最终趋于平衡,吸附率反而逐渐减小；在不同的pH值下,腐殖酸对Cu2+和Cd2+吸附量随着pH值增加而增大并逐渐稳定,Cu2+吸附的临界点为pH=6.0,Cd2+临界点为pH=5.0,而Pb2+的吸附量受pH值变化的影响较小；在不同温度下,随着温度的降低,腐殖酸对Cu2+、Cd2+和Pb2+吸附量都相应的增加；在相同的条件下,不同腐殖酸对Cu2+、Cd2+和Pb2+吸附量表现为CHHA>BHA,主要是因为CHHA中的羧基和酚羟基官能团含量高于BHA,表明Cu2+、Cd2+和Pb2+在腐殖酸上的吸附作用主要是发生在羧基和酚羟基官能团上。
6.腐殖酸对Cu2+、Cd2+和Pb2+的等温吸附符合Freundlich方程,Langmuir方程和Temkin方程,其中Langmuir方程达到极显著水平。在相同条件下,腐殖酸对三种重金属离子的饱和吸附量大小为Pb2+>Cu2+>Cd2+。在25℃,pH6.0时,CHHA对Cu2+、Cd2+和Pb2+的饱和吸附量分别为23.65mg/g,4.64mg/g和44.64mg/g,BHA饱和吸附量分别为17.29mg/g,3.23mg/g和38.09mg/g；在15℃,pH6.0时,CHHA对Cu2+、Cd2+和Pb2+的饱和吸附量分别为25.49mg/g,5.79mg/g,69.45mg/g；BHA的饱和吸附量为18.30mg/g,4.85mg/g,41.65mg/g。
综上所述,不同区域中腐殖酸结构、腐殖酸结合金属含量和腐殖酸吸附金属饱和容量都存在着一定的差异。腐殖酸对金属离子吸附量远大于腐殖酸本身结合态的金属离子含量,腐殖酸与重金属离子的作用既包括表面吸附也有内部结合。因此,腐殖酸能够有效去除水环境中的重金属,降低重金属的生物有效性,同时,当水体环境条件发生变化时,一部分腐殖酸吸附结合的重金属会释放到环境中形成重金属的“二次污染”。因此,对腐殖酸与重金属的研究不仅对其吸附机理有重要的作用,同时也为水源地的环境保护提供了重要的科学依据。
Water quality of the drinking water source is strong and direct link between people's health and improvement of communities. The pollution by heavy metal has been a serious impact on the safety of drinking water. Humic acid, the most widely distributed in natural environment, can effectively react on inorganic and organic pollutants, and is very important in the formation of a variety of complexes. In general, heavy metals can be substracted from water environment by humic acid. However, the ability of binding capacity and affinity depends on the chemical structure and composition of humic acid. The different complexion strength can determine to the "sink" and "source" for heavy metals in the water environment. Therefore, the metal binding capacities of Humic acid are important to practical signification for the the environmental protection of drinking water source.
Miyun Reservoir has been used as unique surface drinking water storage for Beijing. The sediments of Miyun Reservoir are an important repository for nutrient substances and heavy metals from rivers and surrounding environment. The water quality of Miyun Reservoir directly affects health and safety of residents in Beijing. The sediments of Miyun Reservoir were studied as the research object. Humic acid extracted from surface sediment followed by a method from the International Humic Substance Society (IHSS). The structural characterization of humic acid was investigated by solid state NMR, and the content and distribution of humic acid and TOC were determined to the nutrient levels. The concentration and distribution of metal binding humic acid and corresponding sediments were analyzed for the sources of heavy metals, the capacities of metal binding by humic acid and the environmental effects. Cu, Cd and Pb were chosen for adsorption on sedimentary humic acid at different location of Miyun Reserovior, the characterization of the adsorption and the impact factors were discussiong. The main results are following:
1. The average content of total organic carbon in the surface sediments was about16.40mg/g, and the average concentration of humic acid was0.71mg/g. The spatial distribution of total organic carbon was the order of the middle region> the flow area of Bai River> the flow area of Chao River. The main source of organic carbon in the surface sediments were the runoff by Bai River and Chao River. However, a large of farmland in north of middle reservoir had become an important source of organic carbon. The content of humic acid and organic carbon appeared an unconsistent relationship, and the concentration of humic acid was relatively higher in the flow area of Bai River.
2. The sedimentary humic acids in Miyun Reservor were found to be quiet similar, the main structure of sedimentary humic acid was comprised of non-polar aliphatic chain, carboxyl groups, aromatic group, methoxy group and carbohydrates. Partial of humic acid also included aromatic C-O, O-C-O anomerics and carbonyl. However, carbonyl occurred mainly at the middle region and the flow area of Chao River in Miyun Reservior, and this group was not found at in the flow area of Bai River. Among all the groups, the content of non-polar aliphatic chain was the highest and the average value reached to42.79%, the following was carboxyl groups (about20.38%), oxygen-containing groups (including methoxy group and carbohydrates, about19.03%), aromatic group (about14.11%), and other groups were smaller. Howerver, the structure of humic acids were diversity at different regions, such as the carboxyl group was higher at the flow area of Chao River than other regions. Aliphaticity of humic acid was higher, and armoaa' city and degree of oxidation were lower. At the near of infall to Chao River and Bai River, humic acid mainly came from land-based biological origin, and the other regions suffered from weak water flow were derived from aquatic organisms within the reservoir.
3. The contents of heavy metals in surface sediments were at a low level comparing with the average shale values. Index of geoaccumluation showed heavy metals were uncontamination. Heavy metals in surface sediments were mainly carried by the river into the reservoir and deposition, The spatial distribution of heavy metals at Miyun Reservior was different due to the geographical environment of the two rivers. At the flow area of Chao River, the higher contents of metals were found near the input of reservoir and Chao Dam, and the lower was at the middle of the flow direction. However, at the flow area of Bai River, the lower concentrations of metals were found near the the input of reservoir and Bai Dam, and the hiher was at at the middle of the flow direction. At the middle of Miyun Reservoir, the contents of most metals were lower, but there were a significant increase near the import of the Mangniu River. The results of principal component and correlation analysis showed there were two main sources for metals in surface sediments. The first principal component, including Ni, Cr, Cu, V, Zn, Mn, and part of Pb, represented the source of rock wreathing and soil erosion. The second principal component, consisting of Cd and Pb, and partial concentration of Cr, Cu, V, Zn and Mn, represented the source of industrial mining. The gold mine tailings stacked at the upstream of Mangniu River were potential threat to heavy metals pollution for drinking water source.
4. The order of the heavy metals binding to humic acid in surface sediments was as follows:Zn (143.21-2858.13μg/g)> Cu (236.07-4887.07μg/g)> Cr (18.17-2137.81μg/g)> Ni (13.56-1757.58μg/g)> V (0.55-46.97μg/g)> Pb (0.71-29.04μg/g)>Cd (0-2.59μg/g). Of the studied metals, the concentrations of Cu and Zn in humic acid were significantly higher than the corresponding sediments, and Cu and Zn showed a greater affinity for humic acid than sediment, suggesting the possible formation of more stable complexes with humic acid, and it could reduce the bioavailability of these contaminats. With lower content of humic aicd, respectively0.31%-4.16%and0.11%-1.91%of the total Cu and Zn in surface sediments were recovered into humic acid, and other metals were lower than1%. Other metals seemed to prefer sediment, even though Cr and Ni were found a general increase in its content in humic acid in some areas, probably because of the structure of humic acid and environmental conditions (such as oxic to anoxic conditions). The results of index of geoaccumluation showed Cu and Zn had a stronger enrichment in humic acid, but the contents of other metals showed no obvious enrichment in humic acid. The contents of heavy metals in humic acid reflected the source and pollution of heavy metals in water environment, and provided valuable information on drinking water source for environmental safe assessment.
5. The adsorption of Cu2+、Cd2+and Pb2+on the different surface sedimentary humic acids (CHHA and BHA) were investigated under different conditions. Under the different initial concentrations of heavy metals, the adsorptive capacity of Cu2+、 Cd2+and Pb2+was increased gradually and eventually equilibrium with the ions of three heavy metals increased, but the adsorption rate was gradually decreased. The pH value could impact on the adsorption of Cu2+and Cd2+, the adsorptive capacity of Cu2+and Cd2+was increased and eventually up to a certain scope no longer to increase as the pH value increased, and the bound of pH value for Cu2+on humic acid with experimental range was6.0, and Cd2+was5.0, but the pH values palyed a smaller effect on adsorptive capacity of Pb2+. Temperature also affected the adsorptive capacity of Cu2+, Cd2+and Pb2+, and the adsorptive capacities of these three ions were increased as the temperature decreased. Under the same conditions, the size of the amount of adsorption for Cu2+, Cd2+and Pb2+on different humic acid was CHHA> BHA, this was mainly due to the content of the carboxyl and phenolic hydroxyl functional groups in CHHA was higher than BHA.
6. The results showed that the adsorption isotherm of Cu2+> Cd2+and Pb2+on humic acids complied with the Freundlich equation, the Langmuir equation and the Temkin equation, and the Langmuir equation showed a significant level. In the same conditions, the order of the highest capacity to metal ions on humic acid was Pb2+> Cu2+>Cd2+. In the conditions of25癈and pH6.0, the highest capacities to Cu2+> Cd2+and Pb2+on CHHA were respectively23.65mg/g,4.64mg/g and44.64mg/g, while on the BHA were respectively17.29mg/g,3.23mg/g and38.09mg/g. However, in15"C and pH6.0, the highest capacities to Cu2+> Cd2+and Pb2+on CHHA were respectively25.49mg/g,5.79mg/g and69.45mg/g, but on BHA were respectively18.30mg/g,4.85mg/g and41.65mg/g.
In summary, the structure of humic acid, metal binding by humic acid, and the saturated adsorption capacities of humic acid were differences in different regions. The amount of adsorption capacity was much larger than the content of metal binding to the humic acid, and the reaction of heavy metals on humic acid included both surface adsorption and internal combination. Heavy metals in water environment were effectively removed by humic acid, and bioavailability of heavy metals was reduced. However, when the water environmental conditions were changed, a part of surface adsorptive content on humic acid would be release to water and form a "secondary pollution" for heavy metals. Therefor, the study on the reaction of humic acid and heavy metals can provide an important scientific basis for the environmental protection of water sources.
引文
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