邻苯二甲酸酯在浅层含水层沉积物中的吸附特征研究
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摘要
环境激素是指环境中存在的一类可以改变人类和动物的内分泌系统,导致生殖、发育和行为异常的化学物质。由于环境激素的内分泌干扰效应及对人类的危害,对环境内分泌干扰物的研究已成为国际研究的新热点。
邻苯二甲酸酯是环境激素类物质中一类化合物,它主要用作增塑剂。近年来,随着塑料制品的大量生产和使用,邻苯二甲酸酯类物质不断进入环境,已经成为全球最普遍的一大类污染物。其对生物和人类的侵害主要通过呼吸、饮食和皮肤接触进入人体内,对人体健康造成危害。由于PAEs与塑料基质之间没有形成化学键,而是以氢键和范德华力连接,接触到合适的有机溶剂便会溶解出来,对环境、生物和食品造成污染。国内外有很多报道在大气、土壤、饮用水甚至地下水中检测到邻苯二甲酸酯,国外已称它们为“第二个全球性的PCB污染物”。
地下水是人类赖以生存的水资源的重要组成部分,我国有2/3的人口以地下水为饮用水源,地下水污染及其防治问题已引起了世界各国政府与公众的关注。本论文针对江汉平原地下水及浅层含水层沉积物中邻苯二甲酸酯的分布特征研究,筛选出检出率及含量均较高的五种邻苯二甲酸酯[邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二正丁酯(DBP)、邻苯二甲酸二异丁酯(DIBP)、邻苯二甲酸二乙基己基酯(DEHP)]作为研究对象,对其在浅层含水层沉积物中的吸附行为进行研究。
论文取得了以下成果：
一、主要介绍了环境内分泌干扰物质和邻苯二甲酸酯类化合物的理化性质、危害、污染现状,综述了近年来国内外邻苯二甲酸酯类化合物分析测试方法和邻苯二甲酸酯类物质在各种吸附材料中吸附行为的研究进展。
二、选用江汉平原地区浅层含水层沉积物作为吸附剂,利用反相高效液相色谱技术对筛选出的五种PAEs(DMP、DEP、DBP、DIBP、DEHP)进行吸附动力学研究。结果表明,经四种动力学模型对吸附过程进行拟合,抛物线方程最优,其相关系数(R值)最大,说明吸附过程受到扩散机制的制约。
采用批次吸附实验方法研究了五种PAEs在浅层含水层沉积物上共存的等温吸附行为,在六种浅层含水层沉积物中PAEs的吸附能较好地符合线性吸附规律,在此六种吸附质中PAEs吸附线性拟合的相关性系数均值在0.6744～0.8833之间,且对于同一浅层含水层沉积物中所得参数Kd(沉积物-水分配系数)基本符合：DEP 动态土柱法进行阻滞因子的计算,实验进行100天,只有DMP和DEP穿透,因此只能求出DMP和DEP的阻滞因子。结果表明当地下水迁移10000m时,邻苯二甲酸二甲酯只迁移了65m；当地下水迁移10000m时,邻苯二甲酸二乙酯迁移了55m。
三、分别考察了不同的pH值和不同离子强度条件下五种邻苯二甲酸酯混合溶液在一种浅层含水层沉积物WCD32中的吸附影响。结果显示在溶液中加酸或加碱条件会增加PAEs的吸附量。pH值为3时,DIBP的吸附量明显增加,且DEHP的吸附速率加快,其余PAEs的吸附量所受影响不明显；在碱性条件下,DMP、DEP、DBP、DIBP的吸附量均明显增加,且碱性越强吸附量越大,由于各条件下DEHP均被完全吸附,所以我们无法得知pH对其吸附量的影响,但是其吸附速率随pH增加有所减慢。通过分析吸附后邻苯二甲酸酯在液相色谱测试时的谱图,发现碱性条件下,有新的峰出现,且根据目测新生成的峰面积随pH值增大而增加,这一规律与吸附量的增加规律比较符合。
吸附过程中NaCl的存在使得邻苯二甲酸酯的吸附量增加,但是随着NaCl浓度的变化,吸附量的增加趋势会发生变化：NaCl的存在会增加邻苯二甲酸酯的吸附量,DEHP的吸附量随着其浓度增加而增加,且增加趋势较其他四种邻苯二甲酸酯大；DMP、DIBP、DBP在一定NaCl浓度范围内(浓度为0.0015N、0.003N、0.015N)吸附量随其浓度增加而增加,即在此浓度范围内NaCl会促进其吸附；在NaCl浓度达到0.03这三种PAEs的吸附量反而比0.015N时少,即在在NaCl浓度达到0.015N-0.03N的某一值时对邻苯二甲酸酯吸附的促进作用会减小。
Environmental hormone is a class of chemical compounds in environment. It may affect human and animal on their normal endocrines, leading to reproductive, developmental and behavioral disorder. For Environmental hormone are harmful to human beings and animals, the research of EDCs is worldwide concerned.
Phthalic acid esters (PAEs) are an important group of environment hormones. Their main application is as plasticizers in the manufacture of plastics. In recent years, large amount of plastic acid esters have caused a wide distributions in the world. It can enter human body through breathing, diet and skin. Because there is not chemical bond exist between PAEs and Plastic products. They just joined together with the hydrogen key and vander Waals force. It will be dissolved out in suitable organic solvent and cause pollution to the environment, living beings and food. they have been found in sediments, natural waters, soils, aquatic organism and ground waters, PAEs have become one of the most prevalent contaminants or the second PCBs pollutants.
Groundwater is an important part resource in China for the survival of human, two thirds of the population are living with groundwater for drinking water, groundwater pollution and its prevention have attracted the world's governments' and the public's attention. This thesis aims at the study of characteristics of PAEs in Jianghan plain water and sediment, we studied sorption behavior of five PAEs on Shallow aquifer sediment, including DMP、DEP、DBP、DIBP and DEHP, which have high contents and detection rates.
This thesis about the study of sorption of 5 PAEs on shallow aquifer sediment are as follows:
1. Chapter one introduced the physiological function, existence manner, harm and analytical methods of phthalatic acid esters, summarized the recent advance of analysis method of PAEs in the world and the sorption study on some adsorption materials.
2. Adsorption kinetics and adsorption isotherms of DMP, DEP, DBP, DIBP and DEHP on the shallow aquifer sediment of Jianghan Plain were studied with reverse-phase high performance liquid chromatography. Results showed that parabolic equation has the best correlation coefficient, it means that the adsorption process is restricted by the diffusion mechanism.
The results of the study of batch sorption experiment showed that the adsorption isotherms of five PAEs on shallow aquifer sediment are well fitted linear model.The correlation coefficient of 5 PAEs on 6 shallow aquifer sediment between 0.6744 and 0.8822, Kd (sediment and water distribution coefficient) on the same shallow aquifer sediment are as follows: DEP We used dynamic soil column method to calculate retardation factor, only DMP and DEP can breakthrough. The results showed that when the groundwater transfer 10000m, DMP will move 65m, However, DEP will move 55m.
3. Influence of pH and ionic strength on adsorption behavior was investigated on shallow aquifer sediment WCD32. It can be found that after adding acid or alkali, the adsorption amounts of PAEs increase. pH=3, the adsorption amounts of DIBP increase obviously, the adsorption rate of DEHP quicken, DMP、DEP and DBP don't change a lot. When pH=7 and pH=9, the adsorption amounts of DMP、DEP、DBP、DIBP increase sharply, however, pH=9 have more increased amounts. After the analysis of the spectra tested with liquid chromatographic after adsorption, we found there were some new peaks appeared, when pH=9, the areas of peaks were larger more than pH=7.
The existence of NaCl in solution can increase the adsorption quantity of PAEs. the adsorption quantity of DEHP increased with the concentration of NaCl in solution, increasing amount was much more than others. the adsorption quantity of DMP、DIBP、DBP increased on certain concentration range of NaCl, When the contents of NaCl was 0.0015N、0.003N、0.015N, the adsorption quantity increased with the concentration of NaCl, When the concentration of NaCl was 0.03 N, the adsorption quantity of DMP、DIBP、DBP were less than 0.015N NaCl in solution, It showed that When the contents of NaCl between 0.015N～0.03N, the role of NaCl in promoting of the sorption of PAEs will decrease.
邻苯二甲酸酯是环境激素类物质中一类化合物,它主要用作增塑剂。近年来,随着塑料制品的大量生产和使用,邻苯二甲酸酯类物质不断进入环境,已经成为全球最普遍的一大类污染物。其对生物和人类的侵害主要通过呼吸、饮食和皮肤接触进入人体内,对人体健康造成危害。由于PAEs与塑料基质之间没有形成化学键,而是以氢键和范德华力连接,接触到合适的有机溶剂便会溶解出来,对环境、生物和食品造成污染。国内外有很多报道在大气、土壤、饮用水甚至地下水中检测到邻苯二甲酸酯,国外已称它们为“第二个全球性的PCB污染物”。
地下水是人类赖以生存的水资源的重要组成部分,我国有2/3的人口以地下水为饮用水源,地下水污染及其防治问题已引起了世界各国政府与公众的关注。本论文针对江汉平原地下水及浅层含水层沉积物中邻苯二甲酸酯的分布特征研究,筛选出检出率及含量均较高的五种邻苯二甲酸酯[邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二正丁酯(DBP)、邻苯二甲酸二异丁酯(DIBP)、邻苯二甲酸二乙基己基酯(DEHP)]作为研究对象,对其在浅层含水层沉积物中的吸附行为进行研究。
论文取得了以下成果：
一、主要介绍了环境内分泌干扰物质和邻苯二甲酸酯类化合物的理化性质、危害、污染现状,综述了近年来国内外邻苯二甲酸酯类化合物分析测试方法和邻苯二甲酸酯类物质在各种吸附材料中吸附行为的研究进展。
二、选用江汉平原地区浅层含水层沉积物作为吸附剂,利用反相高效液相色谱技术对筛选出的五种PAEs(DMP、DEP、DBP、DIBP、DEHP)进行吸附动力学研究。结果表明,经四种动力学模型对吸附过程进行拟合,抛物线方程最优,其相关系数(R值)最大,说明吸附过程受到扩散机制的制约。
采用批次吸附实验方法研究了五种PAEs在浅层含水层沉积物上共存的等温吸附行为,在六种浅层含水层沉积物中PAEs的吸附能较好地符合线性吸附规律,在此六种吸附质中PAEs吸附线性拟合的相关性系数均值在0.6744～0.8833之间,且对于同一浅层含水层沉积物中所得参数Kd(沉积物-水分配系数)基本符合：DEP
三、分别考察了不同的pH值和不同离子强度条件下五种邻苯二甲酸酯混合溶液在一种浅层含水层沉积物WCD32中的吸附影响。结果显示在溶液中加酸或加碱条件会增加PAEs的吸附量。pH值为3时,DIBP的吸附量明显增加,且DEHP的吸附速率加快,其余PAEs的吸附量所受影响不明显；在碱性条件下,DMP、DEP、DBP、DIBP的吸附量均明显增加,且碱性越强吸附量越大,由于各条件下DEHP均被完全吸附,所以我们无法得知pH对其吸附量的影响,但是其吸附速率随pH增加有所减慢。通过分析吸附后邻苯二甲酸酯在液相色谱测试时的谱图,发现碱性条件下,有新的峰出现,且根据目测新生成的峰面积随pH值增大而增加,这一规律与吸附量的增加规律比较符合。
吸附过程中NaCl的存在使得邻苯二甲酸酯的吸附量增加,但是随着NaCl浓度的变化,吸附量的增加趋势会发生变化：NaCl的存在会增加邻苯二甲酸酯的吸附量,DEHP的吸附量随着其浓度增加而增加,且增加趋势较其他四种邻苯二甲酸酯大；DMP、DIBP、DBP在一定NaCl浓度范围内(浓度为0.0015N、0.003N、0.015N)吸附量随其浓度增加而增加,即在此浓度范围内NaCl会促进其吸附；在NaCl浓度达到0.03这三种PAEs的吸附量反而比0.015N时少,即在在NaCl浓度达到0.015N-0.03N的某一值时对邻苯二甲酸酯吸附的促进作用会减小。
Environmental hormone is a class of chemical compounds in environment. It may affect human and animal on their normal endocrines, leading to reproductive, developmental and behavioral disorder. For Environmental hormone are harmful to human beings and animals, the research of EDCs is worldwide concerned.
Phthalic acid esters (PAEs) are an important group of environment hormones. Their main application is as plasticizers in the manufacture of plastics. In recent years, large amount of plastic acid esters have caused a wide distributions in the world. It can enter human body through breathing, diet and skin. Because there is not chemical bond exist between PAEs and Plastic products. They just joined together with the hydrogen key and vander Waals force. It will be dissolved out in suitable organic solvent and cause pollution to the environment, living beings and food. they have been found in sediments, natural waters, soils, aquatic organism and ground waters, PAEs have become one of the most prevalent contaminants or the second PCBs pollutants.
Groundwater is an important part resource in China for the survival of human, two thirds of the population are living with groundwater for drinking water, groundwater pollution and its prevention have attracted the world's governments' and the public's attention. This thesis aims at the study of characteristics of PAEs in Jianghan plain water and sediment, we studied sorption behavior of five PAEs on Shallow aquifer sediment, including DMP、DEP、DBP、DIBP and DEHP, which have high contents and detection rates.
This thesis about the study of sorption of 5 PAEs on shallow aquifer sediment are as follows:
1. Chapter one introduced the physiological function, existence manner, harm and analytical methods of phthalatic acid esters, summarized the recent advance of analysis method of PAEs in the world and the sorption study on some adsorption materials.
2. Adsorption kinetics and adsorption isotherms of DMP, DEP, DBP, DIBP and DEHP on the shallow aquifer sediment of Jianghan Plain were studied with reverse-phase high performance liquid chromatography. Results showed that parabolic equation has the best correlation coefficient, it means that the adsorption process is restricted by the diffusion mechanism.
The results of the study of batch sorption experiment showed that the adsorption isotherms of five PAEs on shallow aquifer sediment are well fitted linear model.The correlation coefficient of 5 PAEs on 6 shallow aquifer sediment between 0.6744 and 0.8822, Kd (sediment and water distribution coefficient) on the same shallow aquifer sediment are as follows: DEP
3. Influence of pH and ionic strength on adsorption behavior was investigated on shallow aquifer sediment WCD32. It can be found that after adding acid or alkali, the adsorption amounts of PAEs increase. pH=3, the adsorption amounts of DIBP increase obviously, the adsorption rate of DEHP quicken, DMP、DEP and DBP don't change a lot. When pH=7 and pH=9, the adsorption amounts of DMP、DEP、DBP、DIBP increase sharply, however, pH=9 have more increased amounts. After the analysis of the spectra tested with liquid chromatographic after adsorption, we found there were some new peaks appeared, when pH=9, the areas of peaks were larger more than pH=7.
The existence of NaCl in solution can increase the adsorption quantity of PAEs. the adsorption quantity of DEHP increased with the concentration of NaCl in solution, increasing amount was much more than others. the adsorption quantity of DMP、DIBP、DBP increased on certain concentration range of NaCl, When the contents of NaCl was 0.0015N、0.003N、0.015N, the adsorption quantity increased with the concentration of NaCl, When the concentration of NaCl was 0.03 N, the adsorption quantity of DMP、DIBP、DBP were less than 0.015N NaCl in solution, It showed that When the contents of NaCl between 0.015N～0.03N, the role of NaCl in promoting of the sorption of PAEs will decrease.
引文
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