固相萃取-超高效液相色谱/三重四极杆质谱法同时测定地表水中8种亚硝胺类化合物

建立了固相萃取（SPE）-超高效液相色谱/三重四极杆串联质谱（UPLC-MS/MS）同时测定地表水中8种亚硝胺类化合物的方法。水样中目标物经椰壳活性炭固相萃取小柱吸附富集,小柱经氮气吹干后采用二氯甲烷洗脱。待测样品采用Atlantis T₃柱,以水-甲醇作为流动相进行梯度洗脱,大气压力化学电离源（APCI）正离子模式多反应监测方式（MRM）进行检测,内标法定量分析。8种目标物在相关线性范围内线性良好(r≥0.9950),地表水加标回收率为55.4%~90.4%,相对标准偏差为3.1%~14.3%,方法检出限为1.1 ~1.8 ng/L。本方法准确度和灵敏度高,适用于快速测定地表水中8种亚硝胺类化合物含量。     

Determination of Steroid Estrogens in Wastewater Treatment Plant of A Controceptives Producing Factory

Steroid estrogens such as estrone (E1), 17β-estradiol (E2), estriol (E3), and 17α-ethynylestradiol (EE2) have been suspected to be the main contaminants, which can affect the endocrine system of animals. Many authors have investigated these chemicals in the domestic wastewater treatment plants (WTP). However, wastewater from industries producing steroid contraceptives has not got ample attention. From the environmental point of view, the four steroids are very significant because even very low concentrations (ng/L) can cause reproductive disturbances in human, livestock and wildlife. The main purpose of the present investigation was to develop an analytical method for the determination of the four steroid estrogens present in WTP of a pharmacy factory, mainly producing contraceptive medicine in Beijing, China. Analysis was performed by solid-phase extraction (SPE) system and liquid chromatography combined with tandem mass spectrometry (LC/MS/MS). The average recoveries from effluent samples ranged from 88% to 103% and the precision of the method ranged from 9% to 4%. Based on 0.5-L wastewater samples, the limit of quantification (LOQ) was determined at 0.7 ng/L for E1, 0.8 for E2, 0.9 ng/L for E3, and 0.5 ng/L for EE2 in influent, and 1.0 ng/L for E2 and EE2, and 2.0 ng/L for E1 and E3 in effluent. In the influent samples, average concentrations of 80, 85, 73 and 155 ng/L were determined for E1, E2, E3 and EE2, respectively, showing that they were removed in this WTP to the extent of 79, 73, 85 and 67%, respectively.     

土地利用/覆盖变化对长江上游非点源污染影响研究

在国内外相关研究的基础上,利用输出系数模型,结合RS和GIS技术,对长江上游的非点源污染负荷进行了空间模拟和负荷估算.模拟结果表明,在不考虑流域损失的前提下,由于土地利用造成的非点源污染负荷TN总量从20世纪70年代的123万t下降至2000年的116万t,基本呈逐年减少的趋势,由土地利用造成的TP的变化趋势与TN基本相同,从70年代的3.7万t下降到2000年的3.5万t左右.就省份、土地利用类型和水系而言,四川省、种植用地和草地以及金沙江水系和嘉陵江水系对长江上游的非点源污染贡献较大.在非点源污染负荷强度上,重庆市和嘉陵江水系单位面积负荷最高,是今后应重点治理的地区.结果表明,该模型可以对长江上游这样的超大尺度空间的非点源污染进行较好的空间模拟.     

光电催化降解壬基酚影响因素研究

采用sol-gel法制备TiO2薄膜光电极,以该电极为工作电极,铂丝作对电极,饱和甘汞电极为参比电极,对壬基酚的光电催化降解进行了研究。结果表明:该电极具有n型半导体的特征行为。在外加偏压为+0.8V、pH=5、、30mg/L的H2O2中对初始浓度为20mg/L的壬基酚溶液光照180min降解率达62.22%。讨论了氧的存在、外加偏压、pH等因素对光电催化反应的影响。     

层状氢氧化镁铝对偶氮染料酸性黑10B的脱色性能研究

分别用层状氢氧化镁铝(LDH)和焙烧层状氢氧化镁铝(CLDH)作为吸附剂吸附脱除水溶液中偶氮染料酸性黑10B.考察了脱色时间、pH值、吸附剂的投加量、温度、染料初始浓度和焙烧温度等因素对脱色率的影响.结果表明,LDH及CLDH对酸性黑10B染料具有良好的脱除效果,室温下,10g/L LDH和1g/L的CLDH对浓度为100mg/L的染料的脱色率分别达95.93%和99.97%.pH值是影响吸附能力的关键因素,吸附剂对溶液pH值有一定缓冲作用.LDH及CLDH对酸性黑10B吸附结果符合Langmuir吸附等温式.饱和吸附后的LDH及CLDH用高温热解法再生,吸附性能良好,随再生次数增多,脱色率下降.     

改良倒置A2/O工艺设计

在目前广泛采用的AO、A2O、倒置A2O等工艺的基础上,为提高脱氮除磷效率,提出改良倒置A2O工艺。并对其工艺的特点、设计和脱氮除磷效率进行了详细的研究和分析。     

偏电压对Ti/TiO2光电催化氧化富里酸的影响

采用光电催化反应器对水中天然有机物富里酸(FA)进行降解试验,考察了外加阳极偏电压对光电催化反应器降解富里酸的影响.结果表明,当外加电压为1.2V时,具有最佳的UV254和有机碳TOC去除率,当反应时间为2h时,富里酸的UV254和总有机碳TOC的去除率分别为77.4%和45.4%.另外,在反应初期(前1h内)富里酸光电催化反应动力学常数主要受外加偏电压的影响.     

生活垃圾与危险废物焚烧二噁英类排放特征研究

对某省52家焚烧企业(21家生活垃圾和31家危险废物)排放烟气数据进行了分析,结果表明,两类焚烧企业二噁英类17种单体分布有所不同,生活垃圾焚烧烟气中浓度较高的是O8CDD和O8CDF;危险废物焚烧烟气中较大的是2,3,4,7,8-P5CDF、2,3,7,8-T4CDD和1,2,3,7,8-P5CDD;两类焚烧企业二噁英类单体对I-TEQ贡献最高的都是2,3,4,7,8-P5CDF,贡献率分别为0. 7%～45%和10%～67%;两者的17种二噁英类与I-TEQ的相关性分析表明,1,2,3,7,8-P5CDF在2类焚烧炉中与I-TEQ均存在较高的相关性,其相关系数分别0. 932和0. 927,可以作为潜在的测定指示物。     

Ozone facilitated degradation of caffeine using Ce-TiO2 catalyst

The ozone initiated oxidation of 1,3,7-trimethylxanthine (caffeine), commonly found in wastewaters as model compound is reported using cerium (Ce)/titanium dioxide (TiO₂) as catalyst. The effect of pH and loading of ceria on titania were investigated. Effect of reaction conditions on degradation of caffeine based on their pseudo first-order rate constants were compared. The combination of catalyst Ce-TiO₂ and ozone aeration significantly enhanced the degradation of caffeine compared to uncatalysed ozonation. The oxidation of caffeine ensued via the free radical mechanism, through enhanced ozone decomposition into OH radicals. Ce/TiO₂(0.5?wt%) showed good activity in degradation of caffeine at pH 6, in both natural stream and river water samples showing about 60% total organic carbon removal in 2?h ozonation period. Using liquid chromatography-mass spectroscopy, degradation products were analysed. A reaction intermediate and one final product were positively identified. Nano-catalysts with different loadings of Ce on TiO₂ synthesized by sol-gel route were characterized by scanning electron microscope, transmission electron microscopy, BET and powder X-ray diffraction spectrum techniques. The results showed that the material retained a highly ordered mesoporous structure and possessed large surface area.     

Dissipation,residues, and risk assessment of imidacloprid in Zizania latifolia and purple sweet potato under field conditions using LC-MS/MS

A shortened version of Quick, Easy, Cheap, Effective, Rugged, and Safe method (QuEChERS) for determining the dissipation and residue of imidacloprid present in Zizania latifolia and purple sweet potato was established by using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The average recoveries of imidacloprid in the two crops ranged from 82.12 to 113.79%, with relative standard deviation (RSD) of <7.32%. The dissipation dynamics of imidacloprid in Z. latifolia plants and purple sweet potato plants followed first-order kinetics, with half-lives of 3.2–5.5?days in each of sampling locations. The terminal imidacloprid residues in Z. latifolia and purple sweet potato at each of location were <0.005–0.120?mg kg^?1. According to the risk assessment results, both the acute dietary risk quotient and chronic dietary risk quotient values were <1, indicating that imidacloprid is unlikely to pose health risks to humans with normal recommended use. The present study may serve as a valuable reference for the safe and reasonable use of imidacloprid in Z. latifolia and purple sweet potato fields.