Development,validation and application of a method to analyze phenols in water samples by solid phase micro extraction-gas chromatography-flame ionization detector

In this work the development, validation and application of method using Solid Phase Microexctration (SPME) for the analyses of five pollutants (phenol, 2-nitrophenol, 2,4-dimethylphenol, 2,4-dichlorophenol and 4-chloro, 3-methyl phenol) in supplying water, using gas chromatography (GC) with flame ionization detector (FID) is described. The optimal conditions obtained for SPME were: fiber type: Poliacrylate (PA); extraction time: 40 minutes; extraction temperature: 70°C; amount of salt added to sample (NaCl): 15%; desorption temperature: 8 minutes. The parameters studied in the method validation were: limit of detection (0.3 and 3.5 μ g.L^{? 1}); precision, measured by the variation coefficient (between 2.1 and 8.8%); calibration curve and linearity, by using the external standardization method (between 1 and 50 50 μ g.L^{? 1}). After the methodology development, samples of water collected in Atibaia River (São Paulo - Brazil) were analyzed, using the optimized methodology. Three water samples collected in the rain season showed a peak with retention time close to 4-chloro, 3 methyl phenol further analyzed by Gas Chromatography-Mass Spectrometry for the identity confirmation. In spite of the fact that none target compounds were found in the river water samples analyzed, the presence of two phenols different from those investigated (p-terc butyl phenol; butylated hydroxytoluene) were detected. These results together with the results of the limit of detection (that showed to be lower than the maximum concentration of phenols demanded by different environment control agencies), and the results of the validation, indicate the applicability of this method for the analysis of selected phenols in river water samples.     

Gas chromatographic and mass spectrometric characterization of terbufos sulfoxide and its hydration product

Abstract

Terbufos sulfoxide is a primary metabolite of the organophosphorus insecticide terbufos. The identification of terbufos sulfoxide was determined by combined gas chromatography/mass spectrometry and the direct probe. Mass spectral data are presented and discussed. The data indicate that thermal degradation occurred in the heated GC column. A hydration product of terbufos sulfoxide was detected and its mass spectral data are discussed.     

生物悬浮填料对微孔曝气氧传质影响的中试研究

生物填料在污水处理中常用来增加生物量以提高污水的净化效率,同时生物填料的加入会影响曝气氧转移效率.考察了典型的SPR-1生物悬浮填料在清水中对微孔曝气氧传质过程的影响.结果表明,在水深为6.00 m时,SPR-1生物悬浮填料有助于促进微孔曝气的氧传质,当填料填充率为40％,单位体积通气量为0.755 m3/h时,氧总转移系数(KL a20)和标准氧转移效率(SOTE)提高程度最大,分别为19.32％和5.78％;当水深为2.33 m时,SPR-1生物悬浮填料对微孔曝气氧传质有阻碍作用.在实际污水处理过程中,可以根据水深,调节填料填充率来使填料最大限度地促进氧传质.     

杂质对白泥-石膏法烟气脱硫传质反应的影响

白泥中含有大量的杂质,如钠、镁、氯及黑色胶状物,在脱硫过程中可能会对二氧化硫的吸收传质过程存在影响。为明确各杂质在脱硫过程中作用,详细考察了上述物质对二氧化硫的吸收传质过程的影响。结果表明,硫酸钠、高浓度硫酸镁均对传质反应具有增强作用;而氯离子、黑色胶状物、低浓度硫酸镁却对传质反应起阻碍作用。实验同时研究了杂质浓度对传质反应的影响,在硫酸镁低浓度范围内K/β-c符合高斯函数形式。     

Monitoring and modelling of siloxanes in a sewage treatment plant in the UK

Monitoring of cyclic volatile methylsiloxanes (cVMS) carried out at Anglian Water’s Broadholme sewage treatment plant (STP) is described. The method deployed used headspace gas chromatography/mass spectrometry (HS-GC/MS) and the addition of isotopically labelled cVMS to correct for partitioning in samples containing high levels of particulate and dissolved organic carbon. The method was capable of measuring cVMS in raw sewage samples, with recoveries of 80%, 85% and 71% respectively, for D₄, D₅ and D₆. The limit of quantification was 0.2 μg L⁻¹ for all three substances. Recoveries close to 100% were observed for all cVMS spiked into treated effluent (LOQ = 0.01 μg L⁻¹). Despite the volatile nature of cVMS and its ubiquitous presence in the ambient atmosphere, the methods deployed showed excellent recoveries, reproducibility and quantification limits. A distinct diurnal variation in cVMS concentration, probably linked with the use of personal care products was observed for raw sewage but not in treated sewage effluent. The estimated per capita consumption of D₅ (∼2.7 mg cap⁻¹ d⁻¹) derived for the population served by this plant was significantly lower than that derived in the Environment Agency (UK) risk assessment (11.6 mg cap⁻¹ d⁻¹). The cVMS were highly removed during sewage treatment with efficiencies greater than 98%. The methods and findings of this pilot study can be used as the basis for future studies on the fate of cVMS substances in STPs.     

Predictors of urinary bisphenol A and phthalate metabolite concentrations in Mexican children

Exposure to endocrine disrupting chemicals such as bisphenol A (BPA) and phthalates is prevalent among children and adolescents, but little is known regarding important sources of exposure at these sensitive life stages. In this study, we measured urinary concentrations of BPA and nine phthalate metabolites in 108 Mexican children aged 8–13 years. Associations of age, time of day, and questionnaire items on external environment, water use, and food container use with specific gravity-corrected urinary concentrations were assessed, as were questionnaire items concerning the use of 17 personal care products in the past 48-h. As a secondary aim, third trimester urinary concentrations were measured in 99 mothers of these children, and the relationship between specific gravity-corrected urinary concentrations at these two time points was explored. After adjusting for potential confounding by other personal care product use in the past 48-h, there were statistically significant (p < 0.05) positive associations in boys for cologne/perfume use and monoethyl phthalate (MEP), mono(3-carboxypropyl) phthalate (MCPP), mono(2-ethyl-5-hydroxyhexyl) phthalate (MEHHP), and mono(2-ethyl-5-oxohexyl) phthalate (MEOHP), and in girls for colored cosmetics use and mono-n-butyl phthalate (MBP), mono(2-ethylhexyl) phthalate (MEHP), MEHHP, MEOHP, and mono(2-ethyl-5-carboxypentyl) phthalate (MECPP), conditioner use and MEP, deodorant use and MEP, and other hair products use and MBP. There was a statistically significant positive trend for the number of personal care products used in the past 48-h and log-MEP in girls. However, there were no statistically significant associations between the analytes and the other questionnaire items and there were no strong correlations between the analytes measured during the third trimester and at 8–13 years of age. We demonstrated that personal care product use is associated with exposure to multiple phthalates in children. Due to rapid development, children may be susceptible to impacts from exposure to endocrine disrupting chemicals; thus, reduced or delayed use of certain personal care products among children may be warranted.     

喷淋塔传质特性的实验与模型研究

从液滴受力分析入手,分析了喷淋塔内液滴的运动特性,采用类比定律推导了气相传质系数计算式,建立了喷淋塔脱氨传质模型,并进行了实验验证,分别在不同的喷淋密度和空塔气速的条件下,对传质系数、比表面积及容积吸收率沿塔高的分布进行了模拟.结果表明,沿着液滴的下落方向,比表面积逐渐减小,传质系数缓慢增大,二者在塔顶附近变化显著;传质速率受比表面积和传质推动力的影响较大,增大喷淋密度可显著增加比表面积,提高空塔气速可增大平均传质系数;喷淋塔下半段比表面积小,增大比表面积是强化传质的有效手段.     

Rapid and Sensitive LC/MS/MS Direct Injection Method for the Determination of Trace Level Corexit EC9500A Oil Dispersant in Seawater

A rapid and sensitive liquid chromatography tandem mass spectrometry (LC/MS/MS) method for the determination of trace dioctyl sulfosuccinate (DOSS) concentrations in seawater samples has been established. The method is well suited to aquatic environment impact monitoring following application of the dispersant Corexit EC9500A. Linearity of the method was demonstrated down to 0.05 ng/mL^?1 (0.05 µgL^?1) DOSS in seawater, with a 2.4% relative standard deviation precision for preparation replicates. A US EPA method limit of detection of <0.02 ng/mL^?1 (<0.02 µgL^?1) was calculated and specificity was confirmed by monitoring of two qualifier ions at 291.1 m/z and 227.1 m/z. These transitions were confirmed by QToF analysis to be associated with the DOSS precursor ion at 421.2 m/z. For application to seawater samples and samples containing oil particulates, a practical and repeatable calibration range of 0.5 ng/mL^?1 (0.5 µgL^?1) to 25.0 ng/mL^?1 (25.0 µgL^?1) DOSS is reported. The method was shown to have excellent precision and accuracy, with a consistent ≤1.6% relative standard deviation for system suitability standards at 0.5 ng/mL^?1 (0.5 µgL^?1) and linear weighted (1/x) regression coefficients of determination ≥0.995. The surfactant nature of the analyte is discussed in relation to detection limit and loss of analyte. Speculation of a relationship between DOSS in association or aggregation with divalent cations, such as Ca²⁺ present in salt water and hard water, is suggested. The consequent effects on cell ionic balance and membrane function are discussed.     

用于普通小球藻固碳的气升式内环流平板光生物反应器设计参数优化

为构建适宜普通小球藻快速生长及生物固碳的内环流气升式平板光生物反应器,通过正交实验方法考察了表观气速(SGV)、高径比(H/D)、降流区与升流区的面积比(Ad/Ar)等设计参数对传递特性变量(气含率、液相循环流速、体积传质系数)和微藻固碳速率的影响。结果表明,SGV对微藻固碳速率影响最为显著,Ad/Ar次之,H/D最小。最适设计参数为SGV=0.3 vvm,Ad/Ar=3∶1,H/D=6∶1。SGV主要通过提高了藻液的气含率而对微藻固碳起到积极作用;微藻生长受多重因素影响,仅仅考察体积传质系数对反应器性能的提升并不全面,气含率的提高对微藻高效固碳更为有利。     

绍兴平原二种典型农田系统中重金属流及其平衡分析

以浙江省绍兴平原为例,选择水稻（Orgza sativa L.）和蔬菜[大白菜（Brassica campestris L.ssp.pekinensis）]等2种典型农田系统,进行为期1年的观察分析,研究了农田系统中主要重金属元素流及平衡状况。结果表明,研究区农田系统中重金属来源物和农产品及排水中重金属含量有较大的空间变异性。有机肥和生活垃圾中重金属含量明显高于化肥,不同化肥品种中重金属含量：磷肥、复合肥钾肥氮肥。农田系统中重金属的输入量：有机肥施用（60.40%～99.36%）大气沉降（0.46%～39.26%）化肥施用（0.17%～1.45%）灌溉水（0.0016%～1.62%）。农田系统中Pb、Cd、Zn和Hg的输出量：农产品地表排水;重金属总积累量和输入强度：ZnCuPbCdHg。总体上,蔬菜生产系统中重金属的输入和累积量水稻生产系统。