Simultaneous determination of estrogenic odorant alkylphenols,chlorophenols, and their derivatives in water using online headspace solid phase microextraction coupled with gas chromatography-mass spectrometry

A simple online headspace solid-phase microextraction (HS-SPME) coupled with the gas chromatography-mass spectrometry (GC-MS) method was developed for simultaneous determination of trace amounts of nine estrogenic odorant alkylphenols and chlorophenols and their derivatives in water samples. The extraction conditions of HS-SPME were optimized including fiber selection, extraction temperature, extraction time, and salt concentration. Results showed that divinylbenzene/Carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was the most appropriate one among the three selected commercial fibers, and the optimal extraction temperature, time, and salt concentration were 70 °C, 30 min, and 0.25 g/mL, respectively. The developed method was validated and showed good linearity (R ²?>?0.989), low limit of detection (LOD, 0.002–0.5 μg/L), and excellent recoveries (76–126 %) with low relative standard deviation (RSD, 0.7–12.9 %). The developed method was finally applied to two surface water samples and some of these target compounds were detected. All these detected compounds were below their odor thresholds, except for 2,4,6-TCAS and 2,4,6-TBAS wherein their concentrations were near their odor thresholds. However, in the two surface water samples, these detected compounds contributed to a certain amount of estrogenicity, which seemed to suggest that more attention should be paid to the issue of estrogenicity rather than to the odor problem.     

Research and application of method of oxygen isotope of inorganic phosphate in Beijing agricultural soils

Phosphorus (P) in agricultural ecosystems is an essential and limited element for plants and microorganisms. However, environmental problems caused by P accumulation as well as by P loss have become more and more serious. Oxygen isotopes of phosphate can trace the sources, migration, and transformation of P in agricultural soils. In order to use the isotopes of phosphate oxygen, appropriate extraction and purification methods for inorganic phosphate from soils are necessary. Here, we combined two different methods to analyze the oxygen isotopic composition of inorganic phosphate (δ¹⁸O_P) from chemical fertilizers and different fractions (Milli-Q water, 0.5 mol L^?1 NaHCO₃ (pH = 8.5), 0.1 mol L^?1 NaOH and 1 mol L^?1 HCl) of agricultural soils from the Beijing area. The δ¹⁸O_P results of the water extracts and NaHCO₃ extracts in most samples were close to the calculated equilibrium value. These phenomena can be explained by rapid P cycling in soils and the influence of chemical fertilizers. The δ¹⁸O_P value of the water extracts and NaHCO₃ extracts in some soil samples below the equilibrium value may be caused by the hydrolysis of organic P fractions mediated by extracellular enzymes. The δ¹⁸O_P values of the NaOH extracts were above the calculated equilibrium value reflecting the balance state between microbial uptake of phosphate and the release of intracellular phosphate back to the soil. The HCl extracts with the lowest δ¹⁸O_P values and highest phosphate concentrations indicated that the HCl fraction was affected by microbial activity. Hence, these δ¹⁸O_p values likely reflected the oxygen isotopic values of the parent materials. The results suggested that phosphate oxygen isotope analyses could be an effective tool in order to trace phosphate sources, transformation processes, and its utilization by microorganisms in agricultural soils.     

基于多元统计分析的渭河西咸段水质评价

基于2012年旱季和雨季的水质监测数据,采用主成分分析(PCA)和绝对主成分多元线性回归分析(APCS-MLR)方法对渭河西咸段水体的污染特征进行了综合评价。结果表明,2012年渭河西咸段水体主要以有机污染和富营养化污染为主,同时存在一定的As污染。总体上,研究水体旱季比雨季污染严重,旱季和雨季提取的主成分及大部分断面综合排名不同,说明降雨对水质产生一定的影响。渭河西咸段水体在皂河入渭之前的上游污染相对较轻,污染贡献以干流排污为主;对应的下游水质较差,皂河是其最大的污染源。     

臭氧活性炭-后置砂滤工艺对水中农药的控制效能

选择我国饮用水水质标准中有相关规定,以及部分用量较大或虽被禁用但仍有残留的农药共25种,对黄浦江水源水以及采用臭氧活性炭-后置砂滤工艺的某水厂工艺段出水中的浓度分布进行了调查,评估了砂滤后置工艺条件下相应农药的实际处理效果。结果表明:原水中有包括莠去津、乐果、六氯苯、敌敌畏、乙草胺、丁草胺、仲丁威和p,p'-DDT的8种农药检出,且总浓度较高达到760 ng/L,其中莠去津和乙草胺含量较高,最高浓度分别达到531 ng/L和277 ng/L;从季节性分布来看,春季总农药浓度最高达760 ng/L,秋季最低为175 ng/L。从工艺去除效果来看,臭氧活性炭砂滤后置工艺对农药的总体去除率为62%~78%,与冬春季相比,夏秋季节的农药的去除率提高约10%左右,这可能与高温期微生物活性较高有关。值得关注的是,砂滤后置工艺与同期常规臭氧活性炭工艺相比农药的总去除率要低10%左右,应结合总体出水水质情况对其进一步评估。     

紫外-Fenton法处理高盐有机废水

以某电镀厂水回用系统产生的高盐有机废水为对象,对比研究了Fenton、UV-Fenton等工艺去除COD性能,考察了初始pH、H2O2投加量、Fe2+与H2O2摩尔比、反应时间等参数对处理效果的影响。结果表明:UV-Fenton工艺的最佳条件为初始pH=3.0,H2O2的投加量3 mmol/L,RFe2+:H2O2=1:1,反应时间30 min;在此条件下,COD去除率可达到60%以上,分别较Fenton和UV-H2O2工艺提高23.0%和39.3%。UV-Fenton工艺中,Fenton与UV表现出良好的协同效果,其处理效果较单独Fenton和单独UV处理效果之和高14.7%。UV的引入促进Fe(II)/Fe(Ⅲ)循环,可以提高·OH生成量以及Fe2+与H2O2利用率。UV-Fenton是处理高盐有机废水的可行工艺之一。     

Fenton-like/TiO2催化介质阻挡放电体系对活性艳蓝的降解

为了提高等离子放电对染料的降解效率,研究了Fenton-like/TiO2耦合催化介质阻挡放电体系对活性艳蓝(X-BR)的脱色效果及降解机理。结果表明,投加Fe2+ 或Fe3+与TiO2组成的耦合催化体系可以显著提高X-BR的脱色率。反应10 min后,紫外可见扫描光谱和阴离子(Cl-、NO3-、SO42-)产量分析表明,介质阻挡放电体系可以有效破环蒽醌发色基团,耦合催化体系不仅强化了蒽醌结构的破坏,同时更加有效地破坏了苯环和萘环结构从而提高了TOC降解率。最后,比较研究了投加Mn2+ 和Cu2+对X-BR的脱色效果,在投加浓度均为0.5 mmol/L条件下,两者对X-BR的脱色起到抑制作用,因此,两者不适合作为耦合催化介质阻挡放电体系的添加离子。     

热活化过硫酸钾降解呋虫胺

以新烟碱类杀虫剂呋虫胺为目标污染物,以过硫酸钾为氧化剂,研究不同热活化条件下过硫酸钾对呋虫胺降解率的影响。实验结果表明:呋虫胺的降解率与溶液中过硫酸钾的浓度成正比;随着温度的升高,呋虫胺的降解率也逐渐升高;虽然中性时呋虫胺的降解率稍高于酸性和碱性时的降解率,但pH的变化对呋虫胺的降解率影响不大;Cl-和HCO3-对反应的影响比较复杂,当溶液中的Cl-和HCO3-的浓度低于5 mmol/L时,均促进呋虫胺的降解,而浓度升高时则抑制呋虫胺的降解;通过添加自由基捕获剂发现,该反应体系中同时存在·SO4-和·OH,但起主要作用的是·SO4-。     

电絮凝-超滤除氟工艺参数优化研究

电絮凝-超滤(electrocoagulation-ultrafiltration,EC-UF)工艺在饮用水除氟方面具有良好的应用前景。研究了EC-UF除氟效果和膜污染过程,考察了电流密度、水力停留时间、初始pH、初始氟浓度对除氟效果和膜污染的影响。结果表明,在连续流下EC-UF工艺除氟效果良好,在电流密度30 A/m2、水力停留时间20 min、初始pH在6.0~7.0的最佳工艺条件下,氟的去除率达到80%以上。膜污染主要是由电解过程产生的铝絮凝剂与氟离子形成的颗粒物质导致。上述结果为EC-UF除氟工艺改进提供了参考和依据。     

一株铅镉抗性菌株的分离鉴定及其生物学特性

鉴定了从黑龙江扎龙湿地土壤中筛选出的一株抗铅镉的菌株,研究了其生物学特性和部分生理生化指标。利用16SrDNA序列分析鉴定其菌属,并且研究Pb2+、Cd2+、Pb2+/Cd2+、温度、pH、盐以及抗生素对菌株生长的影响。经鉴定,该菌株为阴沟肠杆菌属(Enterobacter cloacae)。该菌株对Pb2+的去除率和吸附率分别达到了70.34%和44.39%,对Cd2+的去除率和吸附率分别达到了40.54%和25.14%。该菌株最适生长温度为25℃,最适生长pH为7.0左右。此菌株对抗生素亚胺培南最敏感。随着盐、Pb2+、Cd2+、Pb2+/Cd2+混合浓度的升高,该菌株生长受到抑制。     

同步进出水SBR设备最佳进水方式流态模拟

借助流体计算软件Fluent对某同步进出水SBR设备4种不同进水位置以及3种进水孔排布分别进行流态模拟,根据模拟结果得到最佳的进水方式;同时在该进水方式下对进水流量为0.5、0.7、1.0、1.3和1.5 m3/h时反应器内的流态分布情况进行了数值模拟,最后通过示踪剂实验与模拟结果对比验证。对于实验用SBR(长×宽×高为2 m×2 m×1.2 m),进水流量1.0 m3/h是最佳进水流量,此时反应器内流态稳定,进水区域主要分布于反应器中下部以及远离堰口的池壁附近,死水区面积较小,冲击负荷适中,进水对出水水质影响较小;当进水流量小于1.0 m3/h时,进水主要分布于反应器池底,对角线方向以及远离进水端池壁附近3个区域且彼此相对独立,池内死水区面积较大;当进水流量大于1.0 m3/h时,进水冲击负荷过大,迅速形成短流,影响出水水质。