Department of Soil Science Erosion and Land Protection, Institute of Soil Science and Plant Cultivation-State Research Institute, Czartoryskich 8, 24-100 Puławy, Poland.
Molecules. 2020 Jan 29;25(3):587. doi: 10.3390/molecules25030587.
Pesticides belong to a group of xenobiotics harmful to humans and wildlife, whose fate and activity depends on their susceptibility to degradation. Therefore, the monitoring of their residue level in agricultural soils is very important because it provides very valuable information on the actual level of soil contamination and environmental risk resulting from their application. The aim of this study was to evaluate contemporary concentrations of organochlorine (OCPs) and non-chlorinated pesticides (NCPs) in arable soils of Poland as an example of Central and Eastern European countries. The results were assessed in relation to Polish regulations, which are more restrictive compared to those of other European countries. The sampling area covered the territory of arable lands in Poland (216 sampling points). The distribution of sampling points aimed to reflect different geographical districts, conditions of agricultural production, and various soil properties. The collected soil samples were extracted with organic solvents in an accelerated solvent extractor (ASE 2000). The OCPs, including α-HCH, β-HCH, γ-HCH, and p,pDDT, p,pDDE, and p,pDDD, were extracted with a hexane/acetone mixture (70:30 /) and determined by gas chromatography with an electron capture detector (GC-μECD). NCPs included atrazine, carbaryl, and carbofuran were extracted with a dichloromethane/acetone mixture (50:50 /), while maneb was extracted by intensive shaking the sample with acetone (1:1 /) and ethylenediamine-tertraacetic acid. The NCPs were identified by a dual mass- spectrometry (GC-MS/MS). The total content of individual OCPs ranged from 0.61 to 1031.64 µg kg, while the NCP concentrations were significantly lower, from 0.01 to 43.92 µg kg. DDTs were detected in all soils samples (p,p'DDD (23.60 µg kg) > p,p'DDT (18.23 µg kg) > p,p'DDE (4.06 µg kg), while HCHs were only in 4% of the analyzed samples (β-HCH (339.55 µg kg) > α-HCH (96.96 µg kg) > γ-HCH (3.04 µg kg)), but in higher values than DDTs. Among NCPs, higher concentration was observed for carbaryl (<0.01-28.07 µg kg) and atrazine (<0.01-15.85 µg kg), while the lower for carbofuran (<0.01-0.54 µg kg). Maneb was not detected in analyzed soils. Assessment of the level of soil pollution based on Polish regulations indicated that several percentages of the samples exceeded the criterion for OCPs, such as ∑3DDTs (14 samples; 6.5% of soils) and HCH congeners (α-HCH in one sample; 0.5% of soils), while NCP concentration, such as for atrazine, carbaryl and carbofuran were below the permissible levels or were not detected in the analyzed soils, e.g. maneb. The obtained results indicated that residues of the analyzed pesticides originate from historical agricultural deposition and potentially do not pose a direct threat to human and animal health. The behavior and persistence of pesticides in the soils depend on their properties. Significantly lower NCP concentration in the soils resulted from their lower hydrophobicity and higher susceptibility to leaching into the soil profile. OCPs are characterized by a high half-life time, which affect their significantly higher persistence in soils resulting from affinity to the soil organic phase.
农药属于对人类和野生动物有害的一类外来化合物,其命运和活性取决于它们对降解的敏感性。因此,监测其在农业土壤中的残留水平非常重要,因为它提供了有关土壤污染实际水平和应用农药带来的环境风险的非常有价值的信息。本研究的目的是评估波兰耕地土壤中有机氯农药(OCPs)和非氯农药(NCPs)的当代浓度,波兰作为中东欧国家的一个例子。研究结果与波兰法规进行了评估,这些法规比其他欧洲国家更为严格。采样区域覆盖了波兰耕地的领土(216 个采样点)。采样点的分布旨在反映不同的地理区域、农业生产条件和各种土壤特性。采集的土壤样品用加速溶剂萃取器(ASE 2000)中的有机溶剂提取。OCPs 包括α-HCH、β-HCH、γ-HCH 和 p,pDDT、p,pDDE 和 p,pDDD,用正己烷/丙酮混合物(70:30 /)提取,并通过带有电子捕获检测器的气相色谱(GC-μECD)进行测定。NCPs 包括莠去津、西维因和克百威,用二氯甲烷/丙酮混合物(50:50 /)提取,而代森锰锌则通过剧烈摇动样品与丙酮(1:1 /)和乙二胺四乙酸混合提取。NCPs 通过双质量谱(GC-MS/MS)进行鉴定。个别 OCPs 的总含量范围从 0.61 到 1031.64 µg kg,而 NCP 浓度则明显较低,从 0.01 到 43.92 µg kg。所有土壤样品中均检测到滴滴涕(p,p'DDD(23.60 µg kg)> p,p'DDT(18.23 µg kg)> p,p'DDE(4.06 µg kg),而 HCHs 仅在 4%的分析样品中(β-HCH(339.55 µg kg)> α-HCH(96.96 µg kg)> γ-HCH(3.04 µg kg)),但其值高于滴滴涕。在 NCPs 中,西维因(<0.01-28.07 µg kg)和莠去津(<0.01-15.85 µg kg)的浓度较高,而克百威(<0.01-0.54 µg kg)的浓度较低。在分析的土壤中未检测到代森锰锌。根据波兰法规评估土壤污染程度表明,有几个百分比的样品超过了 OCPs 的标准,例如∑3DDTs(14 个样品;土壤的 6.5%)和 HCH 同系物(一个样品中的α-HCH;土壤的 0.5%),而莠去津、西维因和克百威等 NCP 浓度低于允许水平或未在分析土壤中检出,例如代森锰锌。所得结果表明,分析农药的残留来源于历史农业沉积,并且不会对人类和动物健康构成直接威胁。农药在土壤中的行为和持久性取决于它们的性质。土壤中 NCP 浓度显著较低,是由于其疏水性较低,更容易淋滤到土壤剖面中。OCPs 的半衰期较长,这影响了它们在土壤中显著较高的持久性,因为它们与土壤有机相有亲和力。