有机氯农药在湖泊水体和沉积物中的污染特征及动力学研究
摘要
有机氯农药是公认的环境优先控制污染物，也是典型的持久性污染物(POPs)。具有难以降解性、半挥发性、生物蓄积性和高毒性，在自然界中可长期存在，并通过食物链富集，对人类健康和环境的危害极大。虽然早在20世纪70年代，西方发达国家就已经开始禁用有机氯农药，而我国也于1983年禁止了它的生产和使用，但由于使用量大，在环境中降解缓慢、滞留时间长，使得有机氯农药仍然是在环境中检出率最高的一类POPs。
有机氯农药可以通过工业废水及生活污水的排放，农业径流、大气的干湿沉降(降尘及降雨)、土壤浸蚀等各种途径进入水体，但是因为它具有疏水亲颗粒的特性，因此很容易被水体中的悬浮颗粒物质(如矿物、生物碎屑和胶体等)所吸附，并最终随着重力沉降等物理化学作用进入沉积物中，在水底的沉积物中富集。因此，沉积物被认为是有机氯农药迁移转化的归宿地与积蓄库。而沉积物中的有机氯农药还可以通过扩散、再悬浮等途径重新进入上覆水体，引起水体的二次污染。因此研究有机氯农药在水体和沉积物中迁移转化规律具有重要的意义，也是国内外关注的热点问题之一。
湖泊具有调节江河径流、灌溉农田、沟通航运以及繁殖水产等一系列生态功能，与人类的生产生活息息相关。近年来，随着经济的发展以及对湖泊资源不合理的开发和利用，湖泊的水质环境已日益恶化，有机氯农药污染就是其中之一。目前，国内外对于有机氯农药污染的研究主要集中于海湾及河口一带，对湖泊的研究较少。洪湖是湖北省最大的湖泊，也是我国重要的淡水水产基地。但是，关于洪湖的有机氯农药污染研究还尚未见到报道。本文以洪湖为例，研究有机氯农药在湖泊水体和沉积物中的污染特征及动力学机制，探讨湖泊水体和沉积物中有机氯农药的来源与归宿，以及沉积物中有机氯农药的重新释放对湖泊水质的影响，对我们深入认识有机氯农药在湖泊水体和沉积物中的迁移转化行为具有十分重要的研究价值，可以为湖泊有机污染的控制与治理提供理论依据。
首先，本文研究了不同季节洪湖表层水体中有机氯农药的含量水平和分布特征。在洪湖共设立了两条采样剖面，并分枯水期和丰水期两次在洪湖采集了表层水样。研究结果表明，在洪湖表层水体中总有机氯农药OCPs在枯水期的浓度范围为1.22-8.02 ng／L，平均值为3.47 ng／L；在丰水期浓度范围为1.15-4.69 ng／L，平均值为2.87 ng／L，枯水期的含量要略高于丰水期。而其中最主要的有机氯农药污染物是六六六和DDTs。两者的含量分别为：HCHs(包括α-HCH、β-HCH、γ-HCH和δ-HCH)，在枯水期和丰水期的浓度范围分别为0.94-7.04 ng／L和0.79-4.0 ng／L，平均值分别为2.97 ng／L和2.36 ng／L；DDTs(包括p，p’-DDT、o，p’-DDT、p，p’-DDD和p，p’-DDE)，在枯水期和丰水期的浓度范围分别为0.06-0.48 ng／L和0.15-0.83 ng／L，平均值分别为0.24 ng／L和0.41 ng／L。与其他地区相比，水体中HCHs和DDTs的浓度普遍低于国内外其他水域。从分布特征来看，洪湖水体中的有机氯农药基本呈现出距河流入湖口及岸边越近，含量越高的趋势，说明其主要来源于地表径流输入及沿岸污染输入。但是，这种分布趋势枯水期不如丰水期明显。据分析，枯水期的有机氯农药主要来源于底泥释放。而丰水期的有机氯农药主要来源于地表径流对土壤的冲刷浸蚀，从而导致土壤中残留的有机氯农药大量溶入或随土壤颗粒物进入水中。另外，在养渔场附近，因为悬浮颗粒物较多，易于吸附有机污染物，水体中有机氯农药的浓度也较高。从组成特征来看，洪湖水体中HCHs的主要成分是γ-HCH和β-HCH，说明洪湖目前还有林丹输入，但工业六六六则主要为以前残留。而DDTs的主要成分是DDE，说明其主要来源于以前的风化土壤残留。另外，硫丹的组成以硫丹2为主，也说明其主要来源于以前的农药残留。
其次，本文研究了洪湖不同深度的水体中有机氯农药的含量分布与组成特征。通过表层水与底层水中有机氯农药的含量对比可以发现，大部分底层水中有机氯农药的浓度要高于表层水，说明底层水中的有机氯农药主要来源于沉积物释放。另外，洪湖间隙水中有机氯农药的含量要远远高于底层水和表层水，反映了有机氯农药在这些环境中经过了长期的沉积和积累，以及间隙水中的胶体对有机氯农药有很强的吸附作用。可能正是因为间隙水与上覆水体之间明显的浓度梯度，才导致有机氯农药从沉积物的孔隙中向湖水中迁移扩散。从组成来看，表、底层水中各有机氯农药的组成基本一致。
第三，本文将洪湖表层沉积物分为上下两层，研究了洪湖表层沉积物中有机氯农药的含量水平和分布特征。从含量上看，含量最高的是DDTs类农药，在上层沉积物和下层沉积物中的含量范围分别为2.39-25.79 ng／g和1.22-27.5 ng／g，平均值分别为9.19 ng／g和8.73ng／g。其次为HCHs类农药，在上层沉积物和下层沉积物中的含量范围分别为2.05-18.95ng／g和0.66-11.25 ng／g，平均值分别为6.91 ng／g和4.73 ng／g。与国内外其他地区相比，洪湖沉积物中HCHs的含量要低于天津海河，但普遍高于其他地区；而DDTs的含量低于罗马尼亚的Merhei湖和天津海河，但高于其他地区。洪湖沉积物中的有机氯农药与水体中的有机氯农药一样，也基本呈现出在河流入湖口及近岸处含量增高的趋势，说明其主要来源于地表径流及近岸输入。另外，在养渔场附近，因为沉积物中有机质含量较多，因此有机氯农药的含量也较高。将上层与下层沉积物中有机氯农药的含量对比，可以发现它们的含量分布趋势相近，而下层沉积物中有机氯农药的含量普遍低于上层沉积物，说明下层沉积物中的有机氯农药可能主要来源于上层沉积物的渗透。从沉积物中各有机氯农药的组成来看，HCHs类农药以γ-HCH和β-HCH为主，说明其主要来源于林丹的使用及以前的工业六六六残留。而DDTs以DDE为主，硫丹以硫丹2和硫丹硫酸盐为主，说明其均主要来源于以前的农药残留。
第四，对沉积物中的有机氯农药向水体中的释放动力学进行了实验研究。通过一系列的模拟实验，对三种状态下，即静止释放状态、紊动悬浮状态及换水清洗状态下沉积物中有机氯农药的释放规律进行了研究。研究发现，沉积物中有机氯农药的释放过程均明显呈现出在初始阶段释放速度快，而后释放速度减慢的规律。沉积物中有机氯农药的释放强度主要受化合物的水溶性控制。一般来说，水溶性高的物质，如α-HCH，在水中的释放浓度较高；而水溶性低的物质，如HCB，在水中的释放浓度较低。另外，温度对有机氯农药的释放也有重要的影响，随着温度的升高，沉积物中有机氯农药的释放明显加强。在静止释放状态下，沉积物中的有机氯农药向水体的释放过程极其缓慢，要相当长一段时间才可达到平衡。并且在此过程中，表层沉积物中的有机氯农药有向下迁移扩散的趋势。而对比静态释放，紊动悬浮状态下沉积物中有机氯农药的释放具有释放速率快，释放强度高的特点，并且在短期内就可达到释放平衡。在换水清洗实验中，在实验初期，随着换水次数的增加，水中有机氯农药的浓度逐渐降低，但达到一定的次数后，水体中有机氯农药的含量就基本不再变化。说明换水清洗对水体中的有机氯农药污染能起到一定的控制作用，但不能根本消除污染沉积物对水质的影响，沉积物的释放仍会使上覆水体中有机氯农药的浓度维持在一定水平上。最后，通过实验数据分析，建立了沉积物中有机氯农药释放的一级动力学模型并确定了模型参数。释放动力学模型的验证结果表明，实测值与模拟值吻合较好，说明该模型能够用来描述沉积物中有机氯农药向水体释放的动力学过程。
第五，对沉积物中的有机氯农药在厌氧条件下的降解动力学进行了实验研究。研究发现，在厌氧条件下，天然沉积物中大部分有机氯农药都可缓慢降解，其中降解较明显的是γ-HCH、p，p’-DDT及o，p’-DDT，降解较慢的是β-HCH和p，p’-DDE。而α-氯丹、α-HCH、HCB及p，p’-DDE的缺氧生物降解均符合准一级反应动力学方程，其厌氧降解速率常数分别为k_1=0.0137d~(-1)，k_2=0.0078d~(-1)，k_3=0.0042d~(-1)，k_4=0.0005d~(-1)。
第六，对沉积物中有机氯农药的向下迁移过程进行了渗滤实验研究。通过渗滤模拟实验，研究了渗滤液及不同深度沉积物中有机氯农药的含量变化趋势。结果表明，随着时间的延长，渗滤液中β-HCH的浓度呈逐渐降低趋势。但是由于沉积物的滞留作用，渗滤液中HCB及p，p’-DDE的浓度峰值出现不同程度的滞后，其中HCB的滞后尤其明显。另外，在渗滤过程中，表层0-5 cm沉积物中的HCHs和DDTs的向下迁移趋势明显，主要为表层0-5cm沉积物中HCHs和DDTs的含量明显降低，而下部5-15 cm沉积物中含量则显著增加，显示了表层沉积物中的HCHs和DDTs向下迁移扩散的趋势，但主要局限于15 cm的深度内，可能主要是由于TOC的吸附作用。而15-20 cm沉积物中的HCHs则还可以继续向深层沉积物迁移，但15 cm以下沉积物中DDTs的继续向下迁移趋势不明显。
第七，对湖泊水质模型进行了研究。根据质量守恒原则，综合考虑各项影响因素，其中包括以前的水质模型未能正确考虑的污染沉积物对水体的释放，将根据模拟实验所建立的静态释放动力学方程引入水质模型中，建立了新的湖泊水质模型。并且以洪湖为例，给出各项参数的选取方法，对所建立的水质模型进行了分析和应用。结果表明，所建立的湖泊水质模型基本反映了水质的污染变化情况。说明建模的思路和方法是可取的，引入的静态释放动力学方程能基本反映沉积物与上覆水之间的物质交换通量。
Organochlorine pesticides (OCPs) are priority pollutants and typical persistent organicpollutants (POPs). Because of their persistence, half-volatility and high toxicity in theenvironment, and biological accumulation through the food web, OCPs have great harm to theenvironment and human health. Because they were used largely and are difficult to degraded,OCPs are still the most widespread POPs in the environment despite their ban or restricted use indeveloped countries in 1970s and in China in 1983.
OCPs are transported into water through different pathways, such as industrial and domesticwastewater, agricultural runoff, atmospheric deposition and soil erosion. Because of theirhydrophobia, OCPs have a strong affinity for suspended particles and subsequently settle downinto sediments under gravity. Therefore, sediments are thought to be one of the major sinks.However, OCPs in sediments can release into water by diffusion and resuspension and lead tothe recontamination of water. The study on transferring and transforming pathways of OCPs inwater and sediments is very important and is a hotspot.
Lakes have important function on adjusting river runoff, irrigating farmland, shipping andaquiculture. In the recent years, with the economical development and irrational exploitation andapplication on lakes, the ecologic environment of many lakes has worsened gradually. OCPscontamination is one of the environmental problems. At present, the studies on OCPs are mainlypaid attention to bays and estuaries, and very few studies on OCPs in lakes. Honghu Lake is thelargest lake in Hubei province, and is an important aquiculture base. However, no data areavailable for OCPs in Honghu Lake. Therefore, Honghu Lake was selected as our case study ofOCPs contamination and kinetics in water and sediments. Through the discussion about theorigin, tendency and release of OCPs, we can know the transferring and transforming pathwaysof OCPs in the water and sediments in Honghu Lake, which may provide theoretical foundationfor controlling and treating organic pollution of lakes.
Firstly, the concentrations and distribution of OCPs in surface water of Honghu Lake in different seasons were studied. The surface water samples were collected from two sectionplanes of Honghu Lake in both low and high water seasons. The results showed that theconcentrations of OCPs in surface water of Honghu Lake in low and high water seasons rangedfrom 1.22 to 8.02 ng/L and 1.15 to 4.69 ng/L, respectively. The average concentrations of OCPsin surface water of Honghu Lake in low and high water seasons were 3.47 ng/L and 2.87 ng/L,respectively, and the average concentration of OCPs in low water season was higher than that inhigh water season. HCHs and DDTs were the most dominant compounds in OCPs in the water.The total HCHs (the sum of a-HCH,β-HCH,γ-HCH andδ-HCH) in low and high waterseasons ranged from 0.94 to 7.04 ng/L and 0.79 to 4.0 ng/L, respectively. The averageconcentrations of HCHs were 2.97 ng/L and 2.36 ng/L, respectively. The total DDTs (the sum ofp,p'-DDT, o,p'-DDT, p,p'-DDD and p,p'-DDE) in low and high water seasons ranged from 0.06to 0.48 ng/L and 0.15 to 0.83 ng/L, respectively. The average concentrations of DDTs were 0.24ng/L and 0.41 ng/L, respectively. Compared with other regions in the world, the concentrationsof HCHs and DDTs in Honghu water were lower than other water areas. The concentrations ofOCPs in Honghu surface water were higher when the sample sites were nearer the mouth ofrivers flowing into the lake and the bank of the lake. It showed that OCPs in Honghu water weremainly derived from the input of surface runoff and pollutants along the bank of the lake. Thisdistribution tendency in high water season was clearer than that in low water season. Accordingto the data analysis, OCPs in low water season were mainly derived from the release of thesediments. And OCPs in high water season were mainly derived from the input of surface runoff,because residual OCPs in soils can transfer to water by rush and erosion of surface runoff. Inaddition, the OCPs concentrations near the fishery were high because there are a lot ofsuspended particles that have a strong affinity to OCPs.γ-HCH andβ-HCH were the mostdominant compounds in HCHs in Honghu surface water, which indicated that there are still newLindane inputs in Honghu Lake, but technical HCHs were old. DDE andβ-endosulfane were themost dominant compounds in respectively DDTs and endosulfane, which indicated that they areboth old residues.
Secondly, the distribution and composition of OCPs in different depth water of HonghuLake were studied. The concentrations of OCPs in bottom water in mostly sample sites werehigher than that in surface water, which indicated that OCPs in bottom water were mainlyderived from the release of the sediments. Moreover, the concentrations of OCPs in porewaterwas much higher than that in surface and bottom water, reflecting possible long-term depositionand accumulation of OCPs in the environment and the strong affinity of OCPs for colloids inporewater. The clear gradient in OCPs concentrations between porewater and overlying watersuggests that OCPs will be transported from sediment porewater to overlying water by processessuch as diffusion. OCPs compositions were almost same between surface and bottom water.
Thirdly, this dissertation divided the surface sediments of Honghu Lake into upper layer anddown layer, and studies the OCPs concentrations and distribution of them. The concentrations of DDTs are highest among OCPs in the sediments. The concentrations in upper and down layersranged from 2.39 to 25.79 ng/g and 1.22 to 27.5 ng/g, and the averages were 9.19 ng/g and 8.73ng/g, respectively. HCHs had higher concentrations in the sediments. The concentrations ofHCHs in upper and down layers ranged from 2.05 to 18.95 ng/g and 0.66 to 11.25 ng/g, and theaverages were 6.91 ng/g and 4.73 ng/g, respectively. The HCHs concentrations in Honghusurface sediments were lower than Haihe River in Tianjin and higher than that in other areas; andthe DDTs concentrations were lower than Merhei Lake in Rumanian and Haihe River in Tianjin,but were higher than other areas. The OCPs concentrations in Honghu surface sediments tendedto increase gradually from the middle of the lake to the bank or the mouth of rivers flowing intothe lake, which was similar with the surface water. Therefore OCPs in the surface sedimentswere mainly derived from the inputs of runoff or the bank. In addition, the OCPs concentrationswere higher near the fishery because of high organic substance. OCPs in upper sediments hadsimilar distribution tendency with the down sediments, but the concentrations of OCPs in upperlayer were higher than down layer. So OCPs in the down sediments might be derived mainlyfrom penetration of the upper sediments.γ-HCH andβ-HCH were the most dominantcompounds in HCHs in the surface sediments, which indicated that HCHs were mainly derivedfrom the application of Lindane and the residues of technical HCHs. DDE was the mostdominant compound in DDTs, andβ-endosulfane and endosulfane-sulfate were the mostdominant compound in endosulfane, which indicated that they were both old.
Fourthly, release kinetics of OCPs in the sediments were studied by experiments. Therelease rules were studied under static, suspended and washing by exchanging water conditions.The results showed that there were faster release speeds at the beginning of the experiment, andthe release speeds slow down gradually with the increasing time. The release intensities of OCPsin the sediments were influenced mainly by the water-solubility of OCPs. Generally, a compoundwith high water-solubility has high release intensity, such asα-HCH; and a compound with lowwater-solubility has low release intensity, such as HCB. Moreover, temperature has importantinfluence to the release of OCPs. With the increase of the temperature in the experiment, thereleases of OCPs in the sediments were enhanced. Under the static condition, the release speedof OCPs in the sediments was very slow, and the balances between desorption and adsorptionmight reach after a long time. In addition, OCPs in the surface sediment had the down tendencyby diffusion. Compared to the static condition, the release speeds of OCPs in the sediments werefaster and the release intensities were stronger under the suspended condition, and it took onlyseveral days to get desorption and adsorption balance. In the experiment exchanging water, theconcentrations of OCPs in the water decreased gradually with the increase of times exchangingwater at begin. However, the concentrations of OCPs in the water kept stabilization after fourtimes exchanging water. Therefore, exchanging water may decrease the OCPs concentrations inwater, but it cannot remove completely OCPs from water. At last the OCPs concentrations in theoverlying water will keep stable levels because of the release from the sediments. A desorption kinetic model of OCPs from aquatic sediments was set up on the basis of these data. The testresult showed that the simulation data by the kinetic model can well fit the measure data, so themodel can be used to describe the release kinetic process of OCPs from the sediments to water.
Fifthly, anaerobic degradation kinetics of OCPs in the sediments were studied. The resultsshowed that most OCPs might degrade slowly in natural sediments under anaerobic condition.The degradation ofγ-HCH, p,p'-DDT and o,p'-DDT was obvious, but the degradation ofβ-HCHand p,p'-DDE was very slow. The anaerobic degradation ofα-chlordane,α-HCH, HCB andp,p'-DDE fitted pesudo-first-order kinetics equation, with kinetic constants ofα-chlordane,α-HCH, HCB and p,p'-DDE were 0.0137d~(-1), 0.0078d~(-1), 0.0042d~(-1), 0.0005d~(-1), respectively.
Sixthly, the processes of moving downwards of OCPs in the sediments were studied.Through the simulation experiment of penetration, the variable tendency of the OCPsconcentrations was studied in filtrate and sediments with different depth. The results showed thatthe concentrations ofβ-HCH in filtrate decreased gradually with the increase of time. However,the highest concentrations of HCB and p,p'-DDE in filtrate had obvious lags. Moreover, inpenetration process, the concentrations of HCHs and DDTs in 0-5cm sediments decreasedobviously, and the concentrations of HCHs and DDTs in the sediments with 5-15 cm depthincreased obviously. It indicated that HCHs and DDTs in surface sediment might movedownwards, but the moving distance was in the 15 cm depth because of sorption of TOC.Besides, HCHs in the sediment with the 15-20 cm depth might move continually down to thedeeper sediment, but the moving tendency of DDTs under 15 cm sediment was not obvious.
Finally, the water quality model about lakes was studied. According to the qualityconservation rule, a new lake water quality model including a variety of influence factors was setup. This model considers correctly the adsorption and desorption of OCPs between sedimentsand water, and the desorption kinetic equation was used in the new model. At last, Honghu Lakewas regarded as a case, and the water quality model was analyzed and used. The results showedthat the model reflected basically the pollution variation of water. Therefore, it indicated that thethought and method of modeling were advisable, and the static release kinetic equation usedcould reflect basically exchanging fluxes of pollutant between sediments and overlying water.
有机氯农药可以通过工业废水及生活污水的排放，农业径流、大气的干湿沉降(降尘及降雨)、土壤浸蚀等各种途径进入水体，但是因为它具有疏水亲颗粒的特性，因此很容易被水体中的悬浮颗粒物质(如矿物、生物碎屑和胶体等)所吸附，并最终随着重力沉降等物理化学作用进入沉积物中，在水底的沉积物中富集。因此，沉积物被认为是有机氯农药迁移转化的归宿地与积蓄库。而沉积物中的有机氯农药还可以通过扩散、再悬浮等途径重新进入上覆水体，引起水体的二次污染。因此研究有机氯农药在水体和沉积物中迁移转化规律具有重要的意义，也是国内外关注的热点问题之一。
湖泊具有调节江河径流、灌溉农田、沟通航运以及繁殖水产等一系列生态功能，与人类的生产生活息息相关。近年来，随着经济的发展以及对湖泊资源不合理的开发和利用，湖泊的水质环境已日益恶化，有机氯农药污染就是其中之一。目前，国内外对于有机氯农药污染的研究主要集中于海湾及河口一带，对湖泊的研究较少。洪湖是湖北省最大的湖泊，也是我国重要的淡水水产基地。但是，关于洪湖的有机氯农药污染研究还尚未见到报道。本文以洪湖为例，研究有机氯农药在湖泊水体和沉积物中的污染特征及动力学机制，探讨湖泊水体和沉积物中有机氯农药的来源与归宿，以及沉积物中有机氯农药的重新释放对湖泊水质的影响，对我们深入认识有机氯农药在湖泊水体和沉积物中的迁移转化行为具有十分重要的研究价值，可以为湖泊有机污染的控制与治理提供理论依据。
首先，本文研究了不同季节洪湖表层水体中有机氯农药的含量水平和分布特征。在洪湖共设立了两条采样剖面，并分枯水期和丰水期两次在洪湖采集了表层水样。研究结果表明，在洪湖表层水体中总有机氯农药OCPs在枯水期的浓度范围为1.22-8.02 ng／L，平均值为3.47 ng／L；在丰水期浓度范围为1.15-4.69 ng／L，平均值为2.87 ng／L，枯水期的含量要略高于丰水期。而其中最主要的有机氯农药污染物是六六六和DDTs。两者的含量分别为：HCHs(包括α-HCH、β-HCH、γ-HCH和δ-HCH)，在枯水期和丰水期的浓度范围分别为0.94-7.04 ng／L和0.79-4.0 ng／L，平均值分别为2.97 ng／L和2.36 ng／L；DDTs(包括p，p’-DDT、o，p’-DDT、p，p’-DDD和p，p’-DDE)，在枯水期和丰水期的浓度范围分别为0.06-0.48 ng／L和0.15-0.83 ng／L，平均值分别为0.24 ng／L和0.41 ng／L。与其他地区相比，水体中HCHs和DDTs的浓度普遍低于国内外其他水域。从分布特征来看，洪湖水体中的有机氯农药基本呈现出距河流入湖口及岸边越近，含量越高的趋势，说明其主要来源于地表径流输入及沿岸污染输入。但是，这种分布趋势枯水期不如丰水期明显。据分析，枯水期的有机氯农药主要来源于底泥释放。而丰水期的有机氯农药主要来源于地表径流对土壤的冲刷浸蚀，从而导致土壤中残留的有机氯农药大量溶入或随土壤颗粒物进入水中。另外，在养渔场附近，因为悬浮颗粒物较多，易于吸附有机污染物，水体中有机氯农药的浓度也较高。从组成特征来看，洪湖水体中HCHs的主要成分是γ-HCH和β-HCH，说明洪湖目前还有林丹输入，但工业六六六则主要为以前残留。而DDTs的主要成分是DDE，说明其主要来源于以前的风化土壤残留。另外，硫丹的组成以硫丹2为主，也说明其主要来源于以前的农药残留。
其次，本文研究了洪湖不同深度的水体中有机氯农药的含量分布与组成特征。通过表层水与底层水中有机氯农药的含量对比可以发现，大部分底层水中有机氯农药的浓度要高于表层水，说明底层水中的有机氯农药主要来源于沉积物释放。另外，洪湖间隙水中有机氯农药的含量要远远高于底层水和表层水，反映了有机氯农药在这些环境中经过了长期的沉积和积累，以及间隙水中的胶体对有机氯农药有很强的吸附作用。可能正是因为间隙水与上覆水体之间明显的浓度梯度，才导致有机氯农药从沉积物的孔隙中向湖水中迁移扩散。从组成来看，表、底层水中各有机氯农药的组成基本一致。
第三，本文将洪湖表层沉积物分为上下两层，研究了洪湖表层沉积物中有机氯农药的含量水平和分布特征。从含量上看，含量最高的是DDTs类农药，在上层沉积物和下层沉积物中的含量范围分别为2.39-25.79 ng／g和1.22-27.5 ng／g，平均值分别为9.19 ng／g和8.73ng／g。其次为HCHs类农药，在上层沉积物和下层沉积物中的含量范围分别为2.05-18.95ng／g和0.66-11.25 ng／g，平均值分别为6.91 ng／g和4.73 ng／g。与国内外其他地区相比，洪湖沉积物中HCHs的含量要低于天津海河，但普遍高于其他地区；而DDTs的含量低于罗马尼亚的Merhei湖和天津海河，但高于其他地区。洪湖沉积物中的有机氯农药与水体中的有机氯农药一样，也基本呈现出在河流入湖口及近岸处含量增高的趋势，说明其主要来源于地表径流及近岸输入。另外，在养渔场附近，因为沉积物中有机质含量较多，因此有机氯农药的含量也较高。将上层与下层沉积物中有机氯农药的含量对比，可以发现它们的含量分布趋势相近，而下层沉积物中有机氯农药的含量普遍低于上层沉积物，说明下层沉积物中的有机氯农药可能主要来源于上层沉积物的渗透。从沉积物中各有机氯农药的组成来看，HCHs类农药以γ-HCH和β-HCH为主，说明其主要来源于林丹的使用及以前的工业六六六残留。而DDTs以DDE为主，硫丹以硫丹2和硫丹硫酸盐为主，说明其均主要来源于以前的农药残留。
第四，对沉积物中的有机氯农药向水体中的释放动力学进行了实验研究。通过一系列的模拟实验，对三种状态下，即静止释放状态、紊动悬浮状态及换水清洗状态下沉积物中有机氯农药的释放规律进行了研究。研究发现，沉积物中有机氯农药的释放过程均明显呈现出在初始阶段释放速度快，而后释放速度减慢的规律。沉积物中有机氯农药的释放强度主要受化合物的水溶性控制。一般来说，水溶性高的物质，如α-HCH，在水中的释放浓度较高；而水溶性低的物质，如HCB，在水中的释放浓度较低。另外，温度对有机氯农药的释放也有重要的影响，随着温度的升高，沉积物中有机氯农药的释放明显加强。在静止释放状态下，沉积物中的有机氯农药向水体的释放过程极其缓慢，要相当长一段时间才可达到平衡。并且在此过程中，表层沉积物中的有机氯农药有向下迁移扩散的趋势。而对比静态释放，紊动悬浮状态下沉积物中有机氯农药的释放具有释放速率快，释放强度高的特点，并且在短期内就可达到释放平衡。在换水清洗实验中，在实验初期，随着换水次数的增加，水中有机氯农药的浓度逐渐降低，但达到一定的次数后，水体中有机氯农药的含量就基本不再变化。说明换水清洗对水体中的有机氯农药污染能起到一定的控制作用，但不能根本消除污染沉积物对水质的影响，沉积物的释放仍会使上覆水体中有机氯农药的浓度维持在一定水平上。最后，通过实验数据分析，建立了沉积物中有机氯农药释放的一级动力学模型并确定了模型参数。释放动力学模型的验证结果表明，实测值与模拟值吻合较好，说明该模型能够用来描述沉积物中有机氯农药向水体释放的动力学过程。
第五，对沉积物中的有机氯农药在厌氧条件下的降解动力学进行了实验研究。研究发现，在厌氧条件下，天然沉积物中大部分有机氯农药都可缓慢降解，其中降解较明显的是γ-HCH、p，p’-DDT及o，p’-DDT，降解较慢的是β-HCH和p，p’-DDE。而α-氯丹、α-HCH、HCB及p，p’-DDE的缺氧生物降解均符合准一级反应动力学方程，其厌氧降解速率常数分别为k_1=0.0137d~(-1)，k_2=0.0078d~(-1)，k_3=0.0042d~(-1)，k_4=0.0005d~(-1)。
第六，对沉积物中有机氯农药的向下迁移过程进行了渗滤实验研究。通过渗滤模拟实验，研究了渗滤液及不同深度沉积物中有机氯农药的含量变化趋势。结果表明，随着时间的延长，渗滤液中β-HCH的浓度呈逐渐降低趋势。但是由于沉积物的滞留作用，渗滤液中HCB及p，p’-DDE的浓度峰值出现不同程度的滞后，其中HCB的滞后尤其明显。另外，在渗滤过程中，表层0-5 cm沉积物中的HCHs和DDTs的向下迁移趋势明显，主要为表层0-5cm沉积物中HCHs和DDTs的含量明显降低，而下部5-15 cm沉积物中含量则显著增加，显示了表层沉积物中的HCHs和DDTs向下迁移扩散的趋势，但主要局限于15 cm的深度内，可能主要是由于TOC的吸附作用。而15-20 cm沉积物中的HCHs则还可以继续向深层沉积物迁移，但15 cm以下沉积物中DDTs的继续向下迁移趋势不明显。
第七，对湖泊水质模型进行了研究。根据质量守恒原则，综合考虑各项影响因素，其中包括以前的水质模型未能正确考虑的污染沉积物对水体的释放，将根据模拟实验所建立的静态释放动力学方程引入水质模型中，建立了新的湖泊水质模型。并且以洪湖为例，给出各项参数的选取方法，对所建立的水质模型进行了分析和应用。结果表明，所建立的湖泊水质模型基本反映了水质的污染变化情况。说明建模的思路和方法是可取的，引入的静态释放动力学方程能基本反映沉积物与上覆水之间的物质交换通量。
Organochlorine pesticides (OCPs) are priority pollutants and typical persistent organicpollutants (POPs). Because of their persistence, half-volatility and high toxicity in theenvironment, and biological accumulation through the food web, OCPs have great harm to theenvironment and human health. Because they were used largely and are difficult to degraded,OCPs are still the most widespread POPs in the environment despite their ban or restricted use indeveloped countries in 1970s and in China in 1983.
OCPs are transported into water through different pathways, such as industrial and domesticwastewater, agricultural runoff, atmospheric deposition and soil erosion. Because of theirhydrophobia, OCPs have a strong affinity for suspended particles and subsequently settle downinto sediments under gravity. Therefore, sediments are thought to be one of the major sinks.However, OCPs in sediments can release into water by diffusion and resuspension and lead tothe recontamination of water. The study on transferring and transforming pathways of OCPs inwater and sediments is very important and is a hotspot.
Lakes have important function on adjusting river runoff, irrigating farmland, shipping andaquiculture. In the recent years, with the economical development and irrational exploitation andapplication on lakes, the ecologic environment of many lakes has worsened gradually. OCPscontamination is one of the environmental problems. At present, the studies on OCPs are mainlypaid attention to bays and estuaries, and very few studies on OCPs in lakes. Honghu Lake is thelargest lake in Hubei province, and is an important aquiculture base. However, no data areavailable for OCPs in Honghu Lake. Therefore, Honghu Lake was selected as our case study ofOCPs contamination and kinetics in water and sediments. Through the discussion about theorigin, tendency and release of OCPs, we can know the transferring and transforming pathwaysof OCPs in the water and sediments in Honghu Lake, which may provide theoretical foundationfor controlling and treating organic pollution of lakes.
Firstly, the concentrations and distribution of OCPs in surface water of Honghu Lake in different seasons were studied. The surface water samples were collected from two sectionplanes of Honghu Lake in both low and high water seasons. The results showed that theconcentrations of OCPs in surface water of Honghu Lake in low and high water seasons rangedfrom 1.22 to 8.02 ng/L and 1.15 to 4.69 ng/L, respectively. The average concentrations of OCPsin surface water of Honghu Lake in low and high water seasons were 3.47 ng/L and 2.87 ng/L,respectively, and the average concentration of OCPs in low water season was higher than that inhigh water season. HCHs and DDTs were the most dominant compounds in OCPs in the water.The total HCHs (the sum of a-HCH,β-HCH,γ-HCH andδ-HCH) in low and high waterseasons ranged from 0.94 to 7.04 ng/L and 0.79 to 4.0 ng/L, respectively. The averageconcentrations of HCHs were 2.97 ng/L and 2.36 ng/L, respectively. The total DDTs (the sum ofp,p'-DDT, o,p'-DDT, p,p'-DDD and p,p'-DDE) in low and high water seasons ranged from 0.06to 0.48 ng/L and 0.15 to 0.83 ng/L, respectively. The average concentrations of DDTs were 0.24ng/L and 0.41 ng/L, respectively. Compared with other regions in the world, the concentrationsof HCHs and DDTs in Honghu water were lower than other water areas. The concentrations ofOCPs in Honghu surface water were higher when the sample sites were nearer the mouth ofrivers flowing into the lake and the bank of the lake. It showed that OCPs in Honghu water weremainly derived from the input of surface runoff and pollutants along the bank of the lake. Thisdistribution tendency in high water season was clearer than that in low water season. Accordingto the data analysis, OCPs in low water season were mainly derived from the release of thesediments. And OCPs in high water season were mainly derived from the input of surface runoff,because residual OCPs in soils can transfer to water by rush and erosion of surface runoff. Inaddition, the OCPs concentrations near the fishery were high because there are a lot ofsuspended particles that have a strong affinity to OCPs.γ-HCH andβ-HCH were the mostdominant compounds in HCHs in Honghu surface water, which indicated that there are still newLindane inputs in Honghu Lake, but technical HCHs were old. DDE andβ-endosulfane were themost dominant compounds in respectively DDTs and endosulfane, which indicated that they areboth old residues.
Secondly, the distribution and composition of OCPs in different depth water of HonghuLake were studied. The concentrations of OCPs in bottom water in mostly sample sites werehigher than that in surface water, which indicated that OCPs in bottom water were mainlyderived from the release of the sediments. Moreover, the concentrations of OCPs in porewaterwas much higher than that in surface and bottom water, reflecting possible long-term depositionand accumulation of OCPs in the environment and the strong affinity of OCPs for colloids inporewater. The clear gradient in OCPs concentrations between porewater and overlying watersuggests that OCPs will be transported from sediment porewater to overlying water by processessuch as diffusion. OCPs compositions were almost same between surface and bottom water.
Thirdly, this dissertation divided the surface sediments of Honghu Lake into upper layer anddown layer, and studies the OCPs concentrations and distribution of them. The concentrations of DDTs are highest among OCPs in the sediments. The concentrations in upper and down layersranged from 2.39 to 25.79 ng/g and 1.22 to 27.5 ng/g, and the averages were 9.19 ng/g and 8.73ng/g, respectively. HCHs had higher concentrations in the sediments. The concentrations ofHCHs in upper and down layers ranged from 2.05 to 18.95 ng/g and 0.66 to 11.25 ng/g, and theaverages were 6.91 ng/g and 4.73 ng/g, respectively. The HCHs concentrations in Honghusurface sediments were lower than Haihe River in Tianjin and higher than that in other areas; andthe DDTs concentrations were lower than Merhei Lake in Rumanian and Haihe River in Tianjin,but were higher than other areas. The OCPs concentrations in Honghu surface sediments tendedto increase gradually from the middle of the lake to the bank or the mouth of rivers flowing intothe lake, which was similar with the surface water. Therefore OCPs in the surface sedimentswere mainly derived from the inputs of runoff or the bank. In addition, the OCPs concentrationswere higher near the fishery because of high organic substance. OCPs in upper sediments hadsimilar distribution tendency with the down sediments, but the concentrations of OCPs in upperlayer were higher than down layer. So OCPs in the down sediments might be derived mainlyfrom penetration of the upper sediments.γ-HCH andβ-HCH were the most dominantcompounds in HCHs in the surface sediments, which indicated that HCHs were mainly derivedfrom the application of Lindane and the residues of technical HCHs. DDE was the mostdominant compound in DDTs, andβ-endosulfane and endosulfane-sulfate were the mostdominant compound in endosulfane, which indicated that they were both old.
Fourthly, release kinetics of OCPs in the sediments were studied by experiments. Therelease rules were studied under static, suspended and washing by exchanging water conditions.The results showed that there were faster release speeds at the beginning of the experiment, andthe release speeds slow down gradually with the increasing time. The release intensities of OCPsin the sediments were influenced mainly by the water-solubility of OCPs. Generally, a compoundwith high water-solubility has high release intensity, such asα-HCH; and a compound with lowwater-solubility has low release intensity, such as HCB. Moreover, temperature has importantinfluence to the release of OCPs. With the increase of the temperature in the experiment, thereleases of OCPs in the sediments were enhanced. Under the static condition, the release speedof OCPs in the sediments was very slow, and the balances between desorption and adsorptionmight reach after a long time. In addition, OCPs in the surface sediment had the down tendencyby diffusion. Compared to the static condition, the release speeds of OCPs in the sediments werefaster and the release intensities were stronger under the suspended condition, and it took onlyseveral days to get desorption and adsorption balance. In the experiment exchanging water, theconcentrations of OCPs in the water decreased gradually with the increase of times exchangingwater at begin. However, the concentrations of OCPs in the water kept stabilization after fourtimes exchanging water. Therefore, exchanging water may decrease the OCPs concentrations inwater, but it cannot remove completely OCPs from water. At last the OCPs concentrations in theoverlying water will keep stable levels because of the release from the sediments. A desorption kinetic model of OCPs from aquatic sediments was set up on the basis of these data. The testresult showed that the simulation data by the kinetic model can well fit the measure data, so themodel can be used to describe the release kinetic process of OCPs from the sediments to water.
Fifthly, anaerobic degradation kinetics of OCPs in the sediments were studied. The resultsshowed that most OCPs might degrade slowly in natural sediments under anaerobic condition.The degradation ofγ-HCH, p,p'-DDT and o,p'-DDT was obvious, but the degradation ofβ-HCHand p,p'-DDE was very slow. The anaerobic degradation ofα-chlordane,α-HCH, HCB andp,p'-DDE fitted pesudo-first-order kinetics equation, with kinetic constants ofα-chlordane,α-HCH, HCB and p,p'-DDE were 0.0137d~(-1), 0.0078d~(-1), 0.0042d~(-1), 0.0005d~(-1), respectively.
Sixthly, the processes of moving downwards of OCPs in the sediments were studied.Through the simulation experiment of penetration, the variable tendency of the OCPsconcentrations was studied in filtrate and sediments with different depth. The results showed thatthe concentrations ofβ-HCH in filtrate decreased gradually with the increase of time. However,the highest concentrations of HCB and p,p'-DDE in filtrate had obvious lags. Moreover, inpenetration process, the concentrations of HCHs and DDTs in 0-5cm sediments decreasedobviously, and the concentrations of HCHs and DDTs in the sediments with 5-15 cm depthincreased obviously. It indicated that HCHs and DDTs in surface sediment might movedownwards, but the moving distance was in the 15 cm depth because of sorption of TOC.Besides, HCHs in the sediment with the 15-20 cm depth might move continually down to thedeeper sediment, but the moving tendency of DDTs under 15 cm sediment was not obvious.
Finally, the water quality model about lakes was studied. According to the qualityconservation rule, a new lake water quality model including a variety of influence factors was setup. This model considers correctly the adsorption and desorption of OCPs between sedimentsand water, and the desorption kinetic equation was used in the new model. At last, Honghu Lakewas regarded as a case, and the water quality model was analyzed and used. The results showedthat the model reflected basically the pollution variation of water. Therefore, it indicated that thethought and method of modeling were advisable, and the static release kinetic equation usedcould reflect basically exchanging fluxes of pollutant between sediments and overlying water.
引文
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