气相色谱负离子化学电离质谱测定环境中土壤与水中硫丹及其代谢物

建立一种气相色谱负离子化学电离质谱(GC-NCI-MS)测定环境中土壤和水中硫丹及其代谢物残留的检测方法,环境中土壤样用丙酮/水浸渍,乙酸乙酯提取,固相萃取小柱净化,水样经乙酸乙酯提取,采用GC-NCI-MS选择离子监测方式进行定性和定量分析,以外标法定量,方法中每种化合物的检出限土壤为0.05 μg/kg,水为0.005 μg/L,在方法的检测限与50 μg/kg(5 μg/L)范围内,线性相关系数大于0.999 5,在所添加三个浓度水平下,方法的回收率70%~95%,相对标准偏差(RSD)1.2%~11.8%。结果表明,该方法简便、快速、灵敏、精密度好,适合对环境中土壤和水样中硫丹及其代谢物进行有效监测。     

半干旱地区典型POPs硫丹环境多介质迁移归趋模拟研究——以兰州河谷盆地为例

以硫丹为研究对象,利用三级多介质逸度模型,对硫丹在半干旱的兰州河谷盆地大气、水体、土壤、沉积物和植物相中的浓度分布进行模拟研究;对硫丹在研究区环境多介质问的迁移通量进行分析,确定其在环境中的主要迁移过程;并结合实际监测数据,对模型的可靠性进行验证;此外,还对除常数之外的20个模型参数进行灵敏度分析,并对较高的模型灵敏度影响因素进行不确定性分析.研究结果表明:土壤、植物和沉积物相是硫丹在兰州河谷盆地环境污染的主要储库;大气平流输入和农药施用是研究区硫丹的主要输入源,沉积物降解和大气平流输出为研究区的主要消耗和输出途径;亨利常数、辛醇-水分配系数等化合物理化性质参数,以及沉积物、土壤有机碳含量等环境参数对模型的灵敏度影响比较显著;模拟浓度与实测浓度相差在一个数量级之内,吻合较好,表明建立的三级多介质逸度模型适用于半干旱的兰州河谷盆地α-硫丹和β-硫丹的环境多介质迁移及归趋行为模拟.     

表面流人工湿地中硫丹的去除规律研究

硫丹是一种环境中广泛存在的有机氯类污染物,本研究探讨了3个不同浓度梯度的硫丹在表面流人工湿地各组成成分中的去除规律.利用索氏提取-气相色谱法分别测定水、植物、非根际基质以及根际基质中硫丹的含量.结果表明,人工湿地在去除硫丹方面具有很大的优势,30 d内硫丹在人工湿地的水、非根际基质、根际基质中的平均去除率分别为87.9%、63.0%、70.9%.在该系统中,α-硫丹比β-硫丹更加容易去除,主要累积的降解产物为硫丹硫酸酯.基质吸附对人工湿地去除硫丹有很大作用,3 d内,水中约80.0%的硫丹被吸附到基质中.植物对硫丹的去除有很大的促进作用,由于植物的影响,根际基质对硫丹的平均去除率比非根际基质高7.9%.     

紫色土对硫丹的吸附与解吸特征

为揭示硫丹在紫色土中的残留过程、保护土壤生态环境,采用静态吸附和解吸实验,研究了紫色土对硫丹的吸附与解吸特征,考察了温度、吸附剂用量和吸附液初始p H等因素对吸附量的影响.结果表明紫色土对硫丹的吸附动力学过程可以用二级动力学方程很好地描述,获得α-,β-硫丹的初始吸附速率常数分别为0.157 mg·(g·min)-1和0.115 mg·(g·min)-1;吸附热力学过程可以用Langmuir等温吸附模型很好地描述,获得α-,β-硫丹的最大吸附量分别为0.257 mg·g-1和0.155mg·g-1,紫色土吸附硫丹是放热的物理化学过程,但以物理吸附为主.在本研究所设条件下,吸附液初始p H对吸附量的影响较大,温度和吸附剂用量的影响相对较小.解吸实验发现,紫色土吸附的α-,β-硫丹分别在6和4 h时达到最大解吸量(0.029mg·g-1和0.017 mg·g-1),分别占最大吸附量的10.5%和16.1%.     

Changes in lipid profiles of liver microsomes of rats following intratracheal administration of DDT or endosulfan

Abstract

The effect of intratracheal administration of DDT (5 mg/100 g body weight) or endosulfan (1 mg/100 g body weight) to rats for three consecutive days, has been studied on liver lipid metabolism. The administration of DDT but not endosulfan significantly increased the liver weight and the microsomal protein contents. Both DDT and endosulfan treatments significantly increased the contents of microsomal phosphatidylcholine (PC), total‐free‐ and esterified cholesterol. The distribution of unsaturated fatty acids of microsomal PC and PE was increased by DDT treatment. The intratracheal administration of DDT caused fatty infiltration of liver which was probably due to increased synthesis of triglycerides (TG). This is supported by the increased incorporation of radioactive palmitate‐l‐¹⁴C into microsomal TG. However, the increased incorporation of palmitate‐l‐¹⁴C into microsomal PC and phosphatidylethanolamine (PE) after the DDT treatment, was due to the increased transacylation reaction supported by the decreased activity of microsomal phospholipase A. The intratracheal adminstration of endosulfan did not has pronounced effect on liver fatty infiltration, or transacylation reaction in microsomal PC and PE. However, the results have shown that the treatments of DDT or endosulfan increased the PC contents and the incorporation of radioactive [methyl‐³H]choline into PC of microsomes, resulting the increased synthesis of PC via CDPcholine pathway. Thus, the intratracheally administered DDT or endosulfan to rats showed that both the insecticides cause manifestations in the biochemistry of microsomal membrane lipids, although the effects of DDT being more pronounced. Therefore, the translocation effects of these insecticides or metabolites from lung to liver is established.     

Induction of cytochrome p‐450 and phosphatidylcholine synthesis by endosulfan in liver of rats : Effect of quality of dietary proteins

Abstract

Administration of endosulfan significantly increased microsomal protein, cytochrome P‐450 content and the activity of aminopyrine N‐demethylase. Effect of endosulfan and actinomycin D either alone or together on microsomal protein, cytochrome P‐450, NADPH cytochrome c reductase, aniline hydroxylase, aminopyrine N‐demethylase, phosphatidylcholine content, incorporation of ³H‐choline and ¹⁴C‐methionine were studied in rats given amino acid deficient and supplemented diets. Administration of endosulfan significantly increased the above parameters in both the dietary groups, whereas administration of actinomycin D did not have any effect in rats fed supplemented diets, however, significant decrease in the PC and the incorporation of choline and methionine into PC of rats fed deficient diet were observed. A positive correlation in the effect of endosulfan on hepatic mixed function oxidase activity and hepatic phosphatidylcholine is observed.     

Surface-enhanced Raman scattering of the adsorption of pesticide endosulfan on gold nanoparticles

The absorption of pesticide endosulfan on the surface of gold nanoparticles results from the formation of micrometric structures (1–10 μm) with irregular shape because of the aggregation of individual particles. Such aggregation of gold nanoparticles after absorption of pesticide shows a surface-enhanced Raman scattering (SERS) spectrum, whose intensity depends on the concentration of endosulfan. In addition, the discoloration of the colloidal solution and a diminishing of the intensity of the surface plasmon resonance absorption from individual particles were observed by UV-visible spectroscopy. At the same time, a second band between 638 and 700 nm confirms the formation of aggregates of gold nanoparticles as the concentration of endosulfan increases. Finally, we used the SERS intensity of the S?O stretching vibration at 1239 cm^?1 from the SO₃ group as a measure of concentration of pesticide endosulfan. This method could be used to estimate the level of pollution in water by endosulfan in a simple and practical form.     

Toxicity persistence in runoff and soil from experimental soybean plots following insecticide applications

Persistence of toxicity in runoff water and soil was investigated in experimental soybean plots subjected to successive runoff events following pesticide application. Runoff events were produced by irrigation using a sprinkler system. The pesticides applied were cypermethrin and endosulfan, which are widely used in soy production in Argentina. Toxicity tests were performed on two abundant components of the regional fauna, the amphipod Hyalella curvispina and the fish Cnesterodon decemmaculatus. Runoffs from two pesticide applications were assayed at different stages of the growing season: an early application when the soil was almost bare and a late one close to harvest, when the ground was covered by vegetation and just before soy leaves fell. Toxicity to H. curvispina in runoff ceased almost one month after the early application of the two pesticides, while it persisted for over three months after the late application. Soil toxicity to H. curvispina and runoff toxicity to C. decemmaculatus followed the same pattern. Higher temperatures and solar radiation are likely to have enhanced insecticide degradation after the early application. Lower temperatures and solar radiation in combination with increased organic matter from litter probably contributed to the longer persistence of toxicity recorded after the late application, as compared with the early application. Cypermethrin caused no mortality to C. decemmaculatus after the early application, while endosulfan toxicity persisted for almost four months after the late one.     

Endosulfan acute toxicity and histomorphological alterations in Jenynsia multidentata (Anablepidae,Cyprinodontiformes)

Toxicity tests using adult specimens of Jenynsia multidentata were carried out during 96 hours in order to determine the lethal concentration (LC50) of endosulfan. Histological alterations were determined in gills and liver. Gill damage was quantified as secondary lamellae thickness. The 96 hr LC50 values were significantly different between males (0.719 μ g.L^{? 1}) and females (1.317 μg.L^{? 1}). The sex difference was attributed to the dimorphism in the lipid content in females (2.16%) and males (1.79%). Histological alterations in gills included hypertrophy and lifting of the epithelium of the secondary lamellae and aneurisms. These alterations caused a significant increase of the secondary lamellae thickness in treatment versus control fish. Finally, reversible histological alterations (such as hydropic degeneration and dilation of sinusoids) were observed in the liver of exposed fish as well as an irreversible change such as necrosis at the highest concentrations.     

灰分对挺水植物生物炭吸附硫丹的影响

将美人蕉、菖蒲和芦苇等挺水植物通过限氧高温热解（500℃）制备生物炭,探究灰分对生物炭吸附硫丹的影响.研究表明：挺水植物生物炭表面孔隙发育成熟,以介孔为主,灰分含量较高（15.86%~27.29%）,主要成分可能为碳酸钙.生物炭对硫丹的非线性吸附常数介于0.63~0.80之间,较去灰生物炭大（0.61~0.72）.去灰后,生物炭对β-硫丹和α-硫丹的吸附能力降低（logK_F在6744~11111mg/kg之间）.但各生物炭比表面积增大（20.55~58.13m²/g）,（O+N）/C值变小,炭表面极性降低,疏水性增强;且表层碳元素与主体碳占比增加,炭表面暴露出更多的有机质,增强对硫丹的疏水作用.加入上清液后,去灰后美人蕉、菖蒲和芦苇生物炭对硫丹的吸附变化显著,其上清液中的溶解性物质增强了去灰生物炭对硫丹的吸附作用.