王佳青(1996—),女,浙江绍兴人,硕士研究生,主要从事环境微塑料污染研究。E-mail:
微塑料影响下土壤中抗生素的解吸行为对抗生素迁移转化和生物有效性具有重要意义,本研究主要探讨不同类型微塑料对土壤抗生素解吸特征的影响。采用酸性水稻土为供试土壤,通过在土壤中添加33.4 mg·kg-1磺胺甲恶唑后老化5 d进行批平衡解吸试验。选择聚乙烯、聚苯乙烯、聚氯乙烯、聚丙烯、聚酯5种不同类型微塑料单一添加到供试土壤中,并调节不同氯化钠和富里酸浓度研究盐度和水溶性有机质探讨对土壤—微塑料混合体系中磺胺甲恶唑解吸行为的影响。结果显示:添加聚乙烯和聚苯乙烯微塑料可使土壤中磺胺甲恶唑的解吸速率降低,使土壤磺胺甲恶唑在10~48 h之间出现明显的慢解吸过程;并且添加聚乙烯和聚氯乙烯微塑料还能显著(
Desorption of antibiotics in soils in the presence of microplastics is key to its migration, transformation, and bioavailability. The objective of this study was to reveal the desorption characteristics of sulfamethoxazole in an artificial antibiotic contaminated soil in the presence of five different microplastics.
Batch equilibrium desorption experiments were carried out using an acid paddy soil that was spiked with 33.4 mg·kg-1 sulfamethoxazole and was aged for 5 days before use. Five polymeric microplastics including polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), polypropylene (PP), and polyethylene terephthalate (PET) (1.67% and 3.33%). The microplastics were added to the soil individually and a soil: solution ratio of 1: 10 was maintained in the experiment. The supernate was sampled for the sulfamethoxazole analysis using high-performance liquid chromatography (HPLC) from 0.25 to 96 h during the desorption kinetic experiment. Also, different concentration of NaCl and fulvic acid were added into the soil-microplastics mixture system to study the effect of salinity and dissolved organic matter (DOC) on sulfamethoxazole desorption, respectively.
The results indicated that the desorption rate of sulfamethoxazole declined significantly and a slow desorption phase was observed from 10 h to 48 h after the addition of polyethylene and polystyrene microplastics. The equilibrium desorbed concentration of sulfamethoxazole declined significantly (
Generally, the desorption of sulfamethoxazole from soils was altered in the presence of microplastics. In soils with a relatively high concentration of DOC, elevated sulfamethoxazole desorption was observed. Therefore, this study highlights the migration and bioavailability of sulfamethoxazole in soils contaminated with microplastics and how different solvents influenced its desorption.
微塑料是指环境中粒径小于5 mm的塑料类污染物,包括碎片、纤维、颗粒、发泡、薄膜等类型,目前正作为一种新兴污染物受到全球关注[
相比纯溶液体系,在土壤介质中,微塑料对抗生素等离子型污染物的吸附—解吸更为复杂。例如,土壤中含有5%的聚丙烯或聚酯微塑料情况下,微塑料可以吸附土壤中的啶虫脒等农药,并且这种吸附行为可能降低土壤自身对农药的滞留能力,导致农药移动性增加[
供试土壤采自杭州临安城区周边的水田(30°18′ 59″ N,119°44′32″E),为红壤母质发育的水稻土,酸性较强,质地为黏壤土,是南方地区一种主要的农田土壤类型。土壤取回后风干过2 mm筛备用,土壤基本性质如
供试土壤基本理化性质
The physico-chemical properties of the soil for experiments
土壤类型 |
pH(H2O) | 土壤有机质 |
可溶性有机碳 |
阳离子交换量 |
2~0.05 mm/% | 0.05~0.002 mm/% | < 0.002 mm/% |
水稻土Paddy soil | 5.02 | 20.2 | 906.8 | 11.6 | 32.6 | 33.2 | 34.2 |
供试微塑料购买自上海冠步机电技术有限公司,包括聚乙烯(PE)、聚苯乙烯(PS)、聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)和聚氯乙烯(PVC)5种聚合物类型,形状均为不规则颗粒。这些微塑料的粒径和表面零点电荷等基本性质如
供试微塑料基本理化性质
The physico-chemical properties of the microplastics for experiments
微塑料类型1) |
聚合物结构式 |
极性特征 |
表面零点电荷 |
平均粒径 |
1)PE,聚乙烯Polyethylene;PS,聚苯乙烯Polystyrene;PP,聚丙烯Polypropylene;PVC,聚氯乙烯Polyvinyl chloride;PET,聚对苯二甲酸乙二醇酯Polyethylene terephthalate. | ||||
PE | |
非极性 | 5.22 | 250 |
PS | 弱极性 | 5.80 | 230 | |
PP | 非极性 | 4.99 | 250 | |
PVC | 强极性 | 5.08 | 300 | |
PET | 极性 | 5.45 | 200 |
取老化后的模拟抗生素污染土壤3.0 g添加至50 mL聚四氟乙烯离心管,分别加入100 mg上述5种聚合物类型的微塑料,再加入0.01 mol·L–1氯化钠电解质溶液30 mL,在避光条件下,25 ℃恒温振荡培养箱以150 r·min–1振荡不同时间(0.25、0.5、1、2、4、8、12、24、36、48、72、96 h)后取上清液,用0.2 μm滤膜过滤后采用高效液相色谱—紫外光法检测上清液中磺胺甲恶唑浓度。试验设计的示意图如
土壤—微塑料混合体系中抗生素解吸试验设计示意图
The schematic diagram of the antibiotics desorption experiment in the soil- microplastics mixture system
微塑料的添加量参照文献[
土壤—溶液—微塑料的混合体系中,将5种微塑料的解吸试验背景溶液设置为不同浓度的氯化钠和氯化钙溶液,其中氯化钠的浓度梯度为0.01 mol·L–1、0.15 mol·L–1、0.6 mol·L–1,氯化钙的浓度为0.2 mol·L–1,与离子强度相同的0.6 mol·L–1氯化钠溶液进行对比试验。每个处理设置3个重复。其他同1.3.1微塑料添加量试验。
土壤—溶液—微塑料的混合体系中,在5种微塑料的解吸试验的0.01 mol·L–1氯化钠背景溶液中添加不同浓度的富里酸,富里酸浓度梯度为:不加富里酸(CK)、10 mg·L–1、20 mg·L–1、50 mg·L–1,每个处理设置3个重复。富里酸(Sigma-Aldrich公司)直接用0.01 mol·L–1氯化钠背景溶液溶解定容。其他同1.3.1微塑料添加量试验。
将磺胺甲恶唑的动力学解吸实验数据采用准一级(式(1))、准二级(式(2))和Elovich模型(式(3))进行解吸动力学拟合,三种模型分别如下所示:
准一级动力学方程:
准二级动力学方程:
Elovich模型:
式中,
采用Origin 2017进行数据制图,SPSS 22软件进行统计分析;不同处理之间的差异显著性分析采用单因素方差分析中的Turkey统计检验法,以0.05水平统计差异的显著性。
微塑料存在下土壤中磺胺甲恶唑的解吸动力学
Desorption kinetic curves of sulfamethoxazole(SMZ)from the soil in the presence of microplastic
微塑料存在下土壤中磺胺甲恶唑解吸的动力学拟合参数
Fitting parameters using different models to the desorption kinetic curves of sulfamethoxazole from the soil in the presence of microplastic
微塑料类型 |
准一级动力学拟合 |
准二级动力学拟合 |
Elovich拟合 |
|||||||
CK | 2.292 | 4.709 | 0.570 | 2.350 | 4.075 | 0.893 | 0.095 | 0.757 | ||
PE | 2.051 | 2.172 | 0.732 | 2.140 | 1.540 | 0.898 | 0.185 | 0.933 | ||
PS | 2.202 | 2.318 | 0.622 | 2.300 | 1.531 | 0.872 | 0.194 | 0.979 | ||
PP | 2.397 | 5.344 | 0.643 | 2.453 | 4.619 | 0.912 | 0.089 | 0.785 | ||
PET | 2.275 | 5.190 | 0.458 | 2.334 | 4.471 | 0.820 | 0.097 | 0.841 | ||
PVC | 2.393 | 4.183 | 0.650 | 2.457 | 3.314 | 0.931 | 0.112 | 0.799 |
微塑料存在下土壤磺胺甲恶唑的平衡解吸量比较
Comparison of the equilibrium desorption concentration of sulfamethoxazole in the presence of microplastic
微塑料类型 |
上清液磺胺甲恶唑浓度Sulfamethoxazole concentration in the supernate/(mg·L–1) | ||
无微塑料添加对照 |
添加50 mg微塑料 |
添加100 mg微塑料 |
|
注:不同小写字母表示不同添加量的处理间存在显著性差异(0.05水平);不同大写之母表示不同类型微塑料之间的处理存在显著性差异(0.05水平)。Note:Different lower case indicate significant difference at 0.05 level between the different treatments of microplastic addition;different upper case indicate significant difference at 0.05 level between the different treatments of microplastic types. | |||
PE | 2.399±0.044a | 2.231±0.041bB | 2.228±0.093bC |
PS | 2.399±0.044a | 2.442±0.040aA | 2.427±0.059aA |
PP | 2.399±0.044a | 2.410±0.032aA | 2.352±0.047bB |
PET | 2.399±0.044a | 2.196±0.085bB | 2.239±0.086bC |
PVC | 2.399±0.044a | 2.246±0.054bB | 2.198±0.062bC |
本研究中,添加微塑料后溶液中磺胺甲恶唑的平衡解吸浓度总体上呈现降低趋势,这与微塑料对磺胺甲恶唑的吸附有关。不同吸附能力的微塑料导致了溶液中平衡解吸浓度的差异。磺胺甲恶唑的解离常数
不同浓度氯化钠溶液条件下土壤中磺胺甲恶唑的解吸情况
Desorption concentration of sulfamethoxazole(SMZ)from the soil in the presence of microplastics under different concentration of NaCl solution
相同离子强度的氯化钠与氯化钙溶液条件下土壤中磺胺甲恶唑的解吸情况
Effects of CaCl2 and NaCl solution with same ionic strength on the sulfamethoxazole desorption in the presence of microplastics
盐度或离子强度对磺胺甲恶唑解吸的影响与吸附作用机制有关,当土壤或微塑料对磺胺甲恶唑的吸附以静电作用主导时,其吸附能力会随着盐度或离子强度的增加而降低[
不同富里酸浓度条件下土壤中磺胺甲恶唑的解吸
Change of sulfamethoxazole(SMZ)desorption from the soil with the increase of fulvic acid concentration in the presence of microplastics
在未添加塑料的情况下,加入的富里酸会首先吸附在土壤上,并可能会进一步通过疏水作用和π-π键与磺胺甲恶唑作用,从而减少土壤中磺胺甲恶唑的解吸[
在土壤—溶液中添加聚乙烯和聚苯乙烯微塑料可使土壤中磺胺甲恶唑的解吸速率变慢,解吸过程与未添加微塑料相比,在10~48 h之间存在明显的缓慢解吸阶段。氯化钠浓度增加降低了供试土壤中磺胺甲恶唑的解吸,而相同离子强度的钙离子却增加了磺胺甲恶唑的解吸;但是,体系中加入微塑料未改变离子类型及其强度对土壤磺胺甲恶唑解吸的影响。添加微塑料总体上可减小富里酸对土壤磺胺甲恶唑解吸的影响,使磺胺甲恶唑解吸量不会随着富里酸浓度的增加而降低。总体而言,在土壤—微塑料混合体系下,微塑料可改变土壤抗生素的解吸,尤其是在富含水溶性有机质土壤中,微塑料的存在能增加抗生素解吸。因此,需要进一步关注微塑料对土壤抗生素迁移性和生物有效性的影响。
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