Adsorption Characteristics of Three Precedence-Controlled Phthalate Esters on Purple Soil

Wei ZENG; Chu ZHANG; Qiang WANG; Fa WANG

doi:10.13718/j.cnki.xdzk.2017.08.003

2017 Volume 39 Issue 8

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Wei ZENG, Chu ZHANG, Qiang WANG, et al. Adsorption Characteristics of Three Precedence-Controlled Phthalate Esters on Purple Soil[J]. Journal of Southwest University Natural Science Edition, 2017, 39(8): 17-25. doi: 10.13718/j.cnki.xdzk.2017.08.003

Citation:

Wei ZENG, Chu ZHANG, Qiang WANG, et al. Adsorption Characteristics of Three Precedence-Controlled Phthalate Esters on Purple Soil[J]. Journal of Southwest University Natural Science Edition, 2017, 39(8): 17-25. doi: 10.13718/j.cnki.xdzk.2017.08.003

Adsorption Characteristics of Three Precedence-Controlled Phthalate Esters on Purple Soil

1.
Key Laboratory of Eco-Environment in Three Gorges Reservoir Region of Ministry of Education, School of Resources and Environment, Southwest University, Chongqing 400716, China
2.
Key Laboratory of Agricultural Resources and Environment of Chongqing, Chongqing 400716, China
3.
Chongqing Environment & Sanitation Holding (Group) Corporation Limited, Chongqing 400020, China

More Information

Corresponding author: Qiang WANG ;
Received Date: 14/12/2015
Available Online: 20/08/2017
MSC: S151.9

Abstract

The characteristics of adsorption kinetics and adsorption thermodynamics of three kinds of precedence-controlled organic pollutants [DMP (dimethyl phthalate), DEP (diethyl phthalate) and DBP (dibutyl phthalate)] on purple soil the typical soil in the Three Gorges Reservoir Area and the influencing factors in the process were studied with the solid phase extraction-HPLC method. The results showed that the adsorption kinetics of DMP, DEP and DBP by purple soil could be divided into two stages: the initial surface fast adsorption and the slow diffusion of soil particles, which could be well explained by the pseudo-second-order kinetic equation, and the adsorption rate constants could be arranged in the order of DMP > DEP > DBP. The isothermal adsorption characteristics of the three kinds of phthalate esters (PAEs) could be well fitted by the Langmuir equation, and the equilibrium adsorption capacity could be arranged in the order of DBP > DEP > DMP. Competitive adsorption of the three kinds of mixed PAEs on the purple soil was detected, and the order of competitive ability was DBP > DEP > DMP. Thermodynamic experiments showed that temperature had a significant effect on the adsorption of the three PAEs on purple soil. The adsorption capacity of PAEs decreased gradually with increasing temperature. The thermodynamic parameters of ΔG, ΔH and ΔS suggested that the adsorption reaction was a spontaneous and exothermic process. In the reaction system, pH and ionic strength made a difference in adsorption. The adsorption capacity decreased with increasing pH and increased with increasing ionic strength.
- purple soil,
- (phthalate esters) PAEs,
- adsorption kinetics,
- thermodynamics,
- competitive adsorption

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邻苯二甲酸酯类化合物(PAEs)是化工制造业中重要的有机化合物之一，作为可塑剂与聚氯乙烯、聚氨酯聚合物等化合物共同应用于建筑行业、家装行业、运输行业、服装行业、食品包装行业和药品生产中^[1].由于容易被皮肤吸附，因此PAEs能轻易进入人体从而造成婴儿出生缺陷、器官损伤、内分泌失调，甚至影响人类生育能力导致不孕和癌症^[2].其中主要的酯类物质，邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)和邻苯二甲酸二丁酯(DBP)等3种污染物已被美国环境保护机构列为环境优先控制污染物^[3].近些年来，国内已经有很多学者对广东、天津、重庆等地农业土壤和水环境中PAEs的分布情况做了研究，结果发现在我国大部分江河、湖泊、土壤等环境中PAEs污染分布广泛而且在部分流域已具有一定的环境风险^[4-8]，同时在部分饮用水和蔬菜等作物中也检测到了PAEs.研究结果表明，邻苯二甲酸酯类具有致畸性、致突变、致癌性和较强的雌激素效应，一旦进入体内，对动物和人类具有严重的危害，因而进一步研究PAEs的环境行为是环境科学家的紧要任务之一^[9-16].目前我国在对于环境中PAEs的研究上已经取得了一定的成果，建立了适用于大气、土壤、水和植物等实际样品测定的分析检测方法^[17-21]，同时，对PAEs生物降解、光解、水解方面进行了大量研究，但大部分研究成果仍局限于理论研究阶段，对于实际环境中PAEs的去除仍需开展大量的研究，PAEs在环境介质中的迁移转化依然需进行深入研究.水-土界面是有机污染物相互作用较频繁的环境介质，是影响污染物质迁移转化和归趋的重要场所，研究污染物在土-水界面的迁移转化及其机理具有重要的意义，虽然目前也有较多的研究成果，然而对于PAEs在三峡库区典型土壤与水体界面的迁移转化机理还少见报道.课题组前期研究了PAEs在三峡库区土-水界面的静态/动态迁移及其影响因素，获得了较为新颖的研究结果，显示DBP在土-水界面的迁移释放呈现出一定规律并受周围环境因子的影响^[22].进一步研究PAEs与三峡库区典型土壤相互作用机制及其影响因素，对于全面阐明PAEs在三峡库区土-水界面的迁移转化特征具有重要的作用.紫色土是由紫色母岩发育而成的幼年土，主要分布在重庆、四川、云南、湖南、贵州等地，总面积达16万km²，是长江上游极为重要的耕地资源，且集中分布在四川省与重庆市(三峡库区)，具有易受侵蚀、持水性较差等特点，与有机碳具有较为特殊的相互作用.因而本研究以三峡库区典型土壤紫色土为供试土壤，采用固相萃取-高效液相色谱法对比研究了DMP，DEP和DBP 3种优先控制有机污染物在紫色土上的吸附动力学和热力学及其影响因子，研究结果对于土壤及水环境PAEs污染风险及其控制具有重要指导意义.

1. 材料与方法

1.1. 主要仪器设备及试剂

高效液相色谱系统(岛津，日本)，可见紫外检测器(岛津，Spd-20A)，自动进样器(岛津，Sil-20A)，色谱柱(intersil ODS-SP，4.6×250 mm)(GL Sciences Inc，日本)，固相萃取柱(3CC/60 mg，Waters Corporation Milford，Massachusetts USA)，菲恰尔TDL-5C台式离心机.

甲醇，色谱纯(HPLC)级，美国Tedia公司；邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DMP)、邻苯二甲酸二丁酯(DBP)，分析纯，国营重庆无机化学试剂厂，理化性质见表 1.

1.2. 实验土样

供试土壤为三峡库区典型土壤—紫色土，采自重庆市北碚区西南大学国家紫色土研究基地表层土壤(0~20 cm)，样品具有代表性.去除其中的石块、树枝、落叶等杂物，经过风干、磨碎后，过2 mm筛备用，基本理化性质见表 2.

1.3. 试验方法

1.3.1. 紫色土对PAEs吸附动力学特征

称取紫色土1.000±0.002 g放入系列100 mL离心管中，分别加入250 mg/L的DMP，DEP和DBP甲醇溶液2 mL，再加入1.0 mol/L的CaCl₂溶液5 mL作为离子强度调节剂，最后加去离子水将溶液体积定容至50 mL，滴入2滴NaN₃抑制微生物活性，盖上塞，并将土壤摇散，用黑色薄膜包裹避光.此时反应体系离子强度为0.10 mol/L，pH为其自然状态下的pH.将离心管放入恒温振荡箱(298K，180 r/min)分别振荡0，1，2，4，8，16和24 h后取出，3 000 r/min离心5 min，取上清液抽滤后检测其中剩余的DMP，DEP和DBP质量浓度.

1.3.2. 紫色土对单一DMP，DEP和DBP等温吸附特性

采用经典的等温吸附方法，在系列离心管中分别加入不同质量浓度的DMP，DEP和DBP溶液，再加入1 mol/L的CaCl₂溶液5 mL，加纯水定容至50 mL，振荡24 h后离心，检测上清液中剩余的DMP，DEP和DBP质量浓度，探讨等温吸附特征.

1.3.3. 环境条件对等温吸附的影响

1) 温度对紫色土等温吸附PAEs特征的影响初始PAEs分别为10 mg/L，将温度分别设置为15 ℃，25 ℃，35 ℃ 3个梯度，参照1.3.2等温吸附方法探讨温度对等温吸附的影响.

2) pH对紫色土等温吸附PAEs特征的影响初始PAEs分别为10 mg/L，用HCl和NaOH调整反应体系pH分别为4，5，6，7，8，9，10，参照1.3.2等温吸附方法探讨pH对等温吸附的影响.

3) 离子强度对紫色土吸附PAEs特征的影响初始PAEs分别为10 mg/L，用CaCl₂溶液调节反应体系离子强度分别为0，0.05，0.10，0.15，0.20和0.25 mol/L.参照1.3.2等温吸附方法探讨离子强度对等温吸附的影响.

1.3.4. 紫色土对多种PAEs竞争吸附特性

称取紫色土1.000±0.002 g放入100 mL离心管中，加入含有DMP，DEP和DBP的混合溶液，使定容后三者初始质量浓度均为10.0 mg/L，参照1.3.2等温吸附方法探讨紫色土对DMP，DEP和DBP机制吸附特性.

所有试验平行3次，取均值加以计算.

1.3.5. DMP，DEP和DBP的测定方法

采用固相萃取-高效液相色谱法测定DMP，DEP和DBP质量浓度.用2 mL甲醇活化固相萃取柱，用5 mL去离子水冲洗干净.取上清液(20~50 mL)以2 mL/min的速度流过萃取柱，流出液不再使用，用10 mL甲醇溶液洗脱萃取柱，将洗脱液用甲醇定容至25 mL，最后用高效液相色谱法检测萃取的DMP，DEP和DBP质量浓度. DMP，DEP和DBP 3种物质的萃取回收率分别为85.1%~104.5%，81.4%~105.6%和88.7%~109.2%.

高效液相色谱法：流动相甲醇，流速1 mL/min，检测波长224 nm，样品进样量15 μL，运行时间为6 min. DMP，DEP和DBP保留时间分别为1.8，2.2，3.4 min，3种物质出峰完整且较清晰，主峰明显，干扰峰少. DMP，DEP和DBP 3种物质的检出限分别为0.020，0.025，0.038 μg/mL.

3. 结论

1) 紫色土对DMP，DEP和DBP的吸附动力学过程可分为最初的表面快速吸附与有机污染物向土壤颗粒内部慢速扩散的两个阶段，假二级动力学方程可以很好地描述紫色土对DMP，DEP和DBP的吸附动力学特征，紫色土对3种PAEs的吸附速率常数由大到小顺序为DMP，DEP，DBP.

2) Langmuir方程可以较好地拟合紫色土对3种邻苯二甲酸酯(PAEs)的等温吸附量特征，平衡吸附量由大到小顺序为DBP，DEP，DMP.

3) 3种混合的PAEs在紫色土上存在明显的竞争吸附，竞争力由大到小顺序为DBP，DEP，DMP.

4) 热力学试验表明温度对紫色土对吸附3种PAEs有明显影响，随着温度的升高，紫色土对PAEs的吸附量逐渐减少.热力学参数ΔG，ΔH和ΔS表明紫色土对3种邻苯二甲酸酯的吸附反应是自发、放热的过程，由表面物理吸附和化学吸附共同控制.

5) 反应体系pH对紫色土吸附3种邻苯二甲酸酯的影响较大，随着pH值的增加而减少；紫色土对DMP，DEP和DBP的吸附量随离子强度的增大而增大.

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Adsorption Characteristics of Three Precedence-Controlled Phthalate Esters on Purple Soil