采用光谱学技术分析邻苯二甲酸酯与DNA互作机制

邻苯二甲酸酯(PAEs)作为增塑剂被广泛使用,易渗透到环境中产生环境毒性,多种PAEs已被美国环境保护署和中国环境监测中心列为优先控制污染物,其生态毒理学机制被广泛关注。本试验以小牛胸腺DNA(ct DNA)为供试材料,旨在通过光谱学技术探究PAEs与DNA的相互作用机制。在紫外可见光谱试验中,随着PAEs浓度的增加,DNA紫外光谱出现增色效应,证明DNA的部分碱基对被PAEs破坏,且PAEs与DNA通过嵌插作用结合。荧光光谱试验中,随着PAEs浓度的增加,EBct DNA体系荧光强度逐渐降低,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)的最大荧光抑制率分别为55%、50%和36%;KI荧光猝灭试验中,在加入DNA之后KI对DMP、DEP和DBP的荧光猝灭常数Ksv分别从7.992(R2=0.9970)、10.270(R2=0.9960)和13.52(R2=0.9806)降低到6.721(R2=0.9963)、7.047(R2=0.9599)和11.03(R2=0.9803),荧光猝灭常数均降低,实验结果证明PAEs与DNA通过嵌插作用结合。盐离子试验中,随着Na Cl浓度的增加,PAEsct DNA的荧光强度没有发生变化。试验结果排除了PAEs与DNA分子之间沟槽作用的可能,确定了其结合方式为嵌插作用,随着PAEs侧链的逐渐增长,嵌插作用逐渐减弱。     

巢湖水中邻苯二甲酸酯安全性评价

本文测定了5种PAEs在巢湖水中的质量浓度,邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯和邻苯二甲酸二异辛酯在所有采样点位均有检出,邻苯二甲酸二甲酯的最高质量浓度为3．15μg／L、邻苯二甲酸二乙酯的最高质量浓度为1．82μg／L、邻苯二甲酸二丁酯的最高质量浓度为12．95μg／L,邻苯二甲酸二异辛酯最高为7．21μg／L,未检出邻苯二甲酸二正辛酯。运用数学模型对PAEs在水中的环境行为进行了安全性评价,结果显示巢湖水受到邻苯二酸酯不同程度的污染。     

固相萃取-气相色谱法测定水环境中邻苯二甲酸酯

采用固相萃取法对水样进行提取富集,气相色谱法测定水中6种邻苯二甲酸酯类有机污染物,并对方法进行了探索、优化和验证。对水体pH在固相萃取过程中对邻苯二甲酸酯萃取回收率的影响进行了研究,解决了邻苯二甲酸2-乙基己基酯和邻苯二甲酸二正辛酯回收率不高的问题。在空白水加标实验中,邻苯二甲酸酯的回收率能达到93.2%~116.3%。除此之外,还对工业废水和地表水进行了加标回收实验,获得了较高的回收率及测定精度。     

液液萃取-气相色谱-质谱法同时测定饮用水中的酞酸酯、百菌清和联苯胺

建立了液液萃取-气相色谱-质谱（LLE -GC/MS）同时测定饮用水中的6种酞酸酯类化合物、百菌清和联苯胺的方法。选用3种有机溶剂进行萃取,筛选出回收率高、操作简单的前处理方法,萃取后经气相色谱-质谱分析。方法表明：8种物质线性良好,相关系数为0．9978～0．9995,用二氯甲烷萃取回收率最佳,回收率在90．1％～118％之间,相对标准偏差在0．24％～7．21％之间。     

加速溶剂萃取-液相色谱测定土壤中酞酸酯类化合物

建立了加速溶剂萃取-液相色谱法测定土壤中14种酞酸酯类化合物的方法。结果表明,该方法对14种酞酸酯分离度较好,加标回收率为67.1%~128%,精密度RSD(n=6)为5.2%~15.0%,方法检出限为0.021~0.034 mg/kg。该方法操作简便、准确,具有较好的实用性。     

CTMAB／SDS改性沸石对水中痕量邻苯二甲酸酯吸附机制

以季铵盐阳离子表面活性剂CTMAB及阴离子表面活性剂SDS对粉末状天然沸石进行复合改性,制备得到了CTMAB／SDS改性沸石。对改性沸石及天然沸石进行红外吸收光谱及XRD衍射表征,并研究了PAEs在天然沸石和CT-MAB／SDS改性沸石上的吸附机制。结果表明,阴阳离子表面活性剂没有对层状结构的键型造成较大的影响;PAEs在天然沸石和CTMAB／SDS改性沸石上的吸附更符合表面吸附一分配作用复合模型;PAEs的表面吸附和分配作用对吸附作用的贡献主要受吸附剂中有机质含量及吸附物质大小、极性及溶解度的影响。     

东莞地下水邻苯二甲酸酯分布特征及来源探讨

在广东东莞地区采集了59组地下水水样和9组地表水水样,采用气相色谱-质谱联用技术进行测定,结果表明,地下水中邻苯二甲酸酯(PAEs)的检出率为39.0％,6种PAEs的质量浓度在未检出～6.70 μg/L.其中,邻苯二甲酸双(2-乙基己基)酯(DEHP)检出率最高,为22.O％,最大值为6.20 μg/L;邻苯二甲酸二...     

Biodegradation of mono-alkyl phthalate esters in natural sediments

Mono-alkyl phthalate esters (MPEs) are primary metabolites of di-alkyl phthalate esters (DPEs), a family of industrial chemicals widely used in the production of soft polyvinyl chloride and a large range of other products. To better understand the long term fate of DPEs in the environment, we measured the biodegradation kinetics of eight MPEs (-ethyl, -n-butyl, -benzyl, -i-hexyl, -2-ethyl-hexyl, -n-octyl, -i-nonyl, and -i-decyl monoesters) in marine and freshwater sediments collected from three locations in the Greater Vancouver area. After a lag period in which no apparent biodegradation occurred, all MPEs tested showed degradation rates in both marine and freshwater sediments at 22 °C with half-lives ranging between 16 and 39 h. Half-lives increased approximately 8-fold in incubations performed at 5 °C. Biodegradation rates did not differ between marine and freshwater sediments. Half-lives did not show a relationship with increasing alkyl chain length. We conclude that MPEs can be quickly degraded in natural sediments and that the similarity in MPE degradation kinetics among sediment types suggests a wide occurrence of nonspecific esterases in microorganisms from various locations, as has been reported previously.     

环境内分泌干扰物--邻苯二甲酸酯的研究

介绍了环境内分泌干扰物的生殖毒性，综述了不同环境样品中邻苯二甲酸酯类内分泌干扰物的前处理技术和分析测试技术，并指出环境中邻苯二甲酸酯的污染状况。     

Performance studies of a low heat rejection engine operated on non-volatile vegetable oils with exhaust gas recirculation

During recent decades, considerable effort has been expended world-wide to reduce dependency on petroleum fuels for power generation and transportation through the search for suitable alternative fuels that are environmentally friendly. In this respect, vegetable oils are a promising alternative to diesel fuel. However, the high viscosity, poor volatility and cold flow characteristics of vegetable oils can cause some problems such as injector coking, severe engine deposits, filter gumming and piston ring sticking and thickening of lubrication from long-term use in diesel engines. These problems can be eliminated or minimised by transesterification of the vegetable oils to form monoesters. Although transesterification improves the fuel properties of vegetable oil, the viscosity and volatility of biodiesel are still worse than those of petroleum diesel fuel. The performance of a diesel engine with such biodiesel operation can be improved further with the concept of the low heat rejection (LHR) engine. In the LHR engine, combustion surfaces on the pistons, cylinder walls and valves can be coated with ceramic materials. The objective of this study was to apply the LHR engine concept for improving engine performance when either honge biodiesel, known as honge oil methyl ester (HOME), or neem biodiesel, known as neem oil methyl ester (NOME) oils was used as an alternative fuel. For this purpose, experiments were conducted on a single cylinder, four-stroke, direct injection, water-cooled compression ignition engine using diesel, HOME and NOME oils at different injection timings of 19, 23 and 27° before top dead centre (BTDC) with and without the induction of exhaust gas recirculation (EGR). The percentage of EGR was varied from 5 to 20% in steps of 5%. The results showed that specific fuel consumption and brake thermal efficiency were improved for both of the biodiesel fuels in the LHR engine. An EGR of 10% resulted in better performance with trade-off between oxides of nitrogen and hydrocarbons/carbon monoxide emissions and hence 10% EGR is taken as the best of the range from 5 to 20%. However, readings with other EGR ratios are not reported.