色谱质谱联用技术在一起农药污染事故应急监测中的应用

在一起污染源应急事故中,色谱质谱联用技术在确定污染源类型,并快速做出准确定性定量分析中发挥了重要作用。通过气相色谱-质谱联用技术,首先确定可能污染物类型为三嗪类化合物;之后,通过液相色谱-串连质谱全扫描,推断可能为三嗪类除草剂——甲磺隆。正、负ESI子离子全扫描后图谱与甲磺隆标准物质图谱相对照,完全吻合。最后,通过SRM模式下对380.0→139.0的母、子离子选择反应监测,测定了农田灌溉水源和土壤中甲磺隆的含量。     

Bioanalytical characterisation of multiple endocrine- and dioxin-like activities in sediments from reference and impacted small rivers

A comprehensive evaluation of organic contamination was performed in sediments sampled in two reference and three impacted small streams where endocrine disruptive (ED) effects in fish have been evidenced. The approach combined quantitative chemical analyses of more than 50 ED chemicals (EDCs) and a battery of in vitro bioassays allowing the quantification of receptor-mediated activities, namely estrogen (ER), androgen (AR), dioxin (AhR) and pregnane X (PXR) receptors. At the most impacted sites, chemical analyses showed the presence of natural estrogens, organochlorine pesticides, parabens, polycyclic aromatic hydrocarbons (16 PAHs), bisphenol A and alkylphenols, while synthetic steroids, myco-estrogens and phyto-estrogens were not detected. Determination of toxic-equivalent amounts showed that 28-96% of estrogenic activities in bioassays (0.2-6.3 ng/g 17β-estradiol equivalents) were explained by 17β-estradiol and estrone. PAHs were major contributors (20-60%) to the total dioxin-like activities. Interestingly, high PXR and (anti)AR activities were detected; however, the targeted analysed compounds could not explain the measured biological activities. This study highlighted the presence of multiple organic EDCs in French river sediments subjected to mixed diffuse pollution, and argues for the need to further identify AR and PXR active compounds in the aquatic environment.     

A method for determining the analytical form of a radionuclide depth distribution using multiple gamma spectrometry measurements

When characterizing environmental radioactivity, whether in the soil or within concrete building structures undergoing remediation or decommissioning, it is highly desirable to know the radionuclide depth distribution. This is typically modeled using continuous analytical expressions, whose forms are believed to best represent the true source distributions. In situ gamma ray spectroscopic measurements are combined with these models to fully describe the source. Currently, the choice of analytical expressions is based upon prior experimental core sampling results at similar locations, any known site history, or radionuclide transport models. This paper presents a method, employing multiple in situ measurements at a single site, for determining the analytical form that best represents the true depth distribution present. The measurements can be made using a variety of geometries, each of which has a different sensitivity variation with source spatial distribution. Using non-linear least squares numerical optimization methods, the results can be fit to a collection of analytical models and the parameters of each model determined. The analytical expression that results in the fit with the lowest residual is selected as the most accurate representation. A cursory examination is made of the effects of measurement errors on the method.     

超声波提取-恒波长同步荧光法测定淡水藻中叶绿素a的含量

针对绿藻,采用超声波提取,以荧光激发-发射波长差216nm,建立了同步荧光法测定绿藻叶绿素a含量的新方法,其线性范围为0.02～1.25 mg/L,检出限为1.6ug/L,加标回收率在97.0%～104%之间。与分光光度法测定叶绿素a的对比试验结果表明,两者无显著性差异,但该方法具有快速、灵敏,其他常见色素不干扰测定的优点,能够满足供水中绿藻叶绿素a含量快速检测的需要。     

Determination of o-phthalic acid in snow and its photochemical degradation by capillary gas chromatography coupled with flame ionization and mass spectrometric detection

Phthalic acid and its photochemical degradation has been determined in snow and rainwater samples collected during winters (2003-2010) in the Southeast of Massachusetts using capillary gas chromatography (GC) with flame ionization and mass spectrometric detection. Water samples were dried using a rotary evaporator and derivatized with a 14% BF₃/methanol reagent before GC analysis. The developed method proved simple and accurate. Phthalic acid was found in snow samples collected in a concentration range of 7.22-76.5 nM. The photodegradation of phthalate was carried out under 300 nm UV light. The direct photodecomposition of the acid is slow (5% h⁻¹). However, the addition of dissolved Fe(III) species at 2.0 μM accelerated the light-induced degradation of phthalic acid by 3.5 times in the atmospheric water samples. Photodegradation rates of phthalic acid increases with decreasing pH value of water samples in the range of pH 2.8-4.5.     

Mass flows of perfluorinated compounds (PFCs) in central wastewater treatment plants of industrial zones in Thailand

Perfluorinated compounds (PFCs) are fully fluorinated organic compounds, which have been used in many industrial processes and have been detected in wastewater and sludge from municipal wastewater treatment plants (WWTPs) around the world. This study focused on the occurrences of PFCs and PFCs mass flows in the industrial wastewater treatment plants, which reported to be the important sources of PFCs. Surveys were conducted in central wastewater treatment plant in two industrial zones in Thailand. Samples were collected from influent, aeration tank, secondary clarifier effluent, effluent and sludge. The major purpose of this field study was to identify PFCs occurrences and mass flow during industrial WWTP. Solid-phase extraction (SPE) coupled with HPLC-ESI-MS/MS were used for the analysis. Total 10 PFCs including perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluoropropanoic acid (PFPA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorohexane sulfonate (PFHxS), perfluoronanoic acid (PFNA), perfluordecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA) were measured to identify their occurrences. PFCs were detected in both liquid and solid phase in most samples. The exceptionally high level of PFCs was detected in the treatment plant of IZ1 and IZ2 ranging between 662-847 ng L⁻¹ and 674-1383 ng L⁻¹, respectively, which greater than PFCs found in most domestic wastewater. Due to PFCs non-biodegradable property, both WWTPs were found ineffective in removing PFCs using activated sludge processes. Bio-accumulation in sludge could be the major removal mechanism of PFCs in the process. The increasing amount of PFCs after activated sludge processes were identified which could be due to the degradation of PFCs precursors. PFCs concentration found in the effluent were very high comparing to those in river water of the area. Industrial activity could be the one of major sources of PFCs contamination in the water environment.     

Contamination of nonylphenolic compounds in creek water, wastewater treatment plant effluents, and sediments from Lake Shihwa and vicinity, Korea: comparison with fecal pollution

Nonylphenolic compounds (NPs), coprostanol (COP), and cholestanol, major contaminants in industrial and domestic wastewaters, were analyzed in creek water, wastewater treatment plant (WWTP) effluent, and sediment samples from artificial Lake Shihwa and its vicinity, one of the most industrialized regions in Korea. We also determined mass discharge of NPs and COP, a fecal sterol, into the lake, to understand the linkage between discharge and sediment contamination. Total NP (the sum of nonylphenol, and nonylphenol mono- and di-ethoxylates) were 0.32-875 μg L⁻¹ in creeks, 0.61-87.0 μg L⁻¹ in WWTP effluents, and 29.3-230 μg g⁻¹ TOC in sediments. Concentrations of COP were 0.09-19.0 μg L⁻¹ in creeks, 0.11-44.0 μg L⁻¹ in WWTP effluents, and 2.51-438 μg g⁻¹ TOC in sediments. The spatial distributions of NPs in creeks and sediments from the inshore region were different from those of COP, suggesting that Lake Shihwa contamination patterns from industrial effluents differ from those from domestic effluents. The mass discharge from the combined outfall of the WWTPs, located in the offshore region, was 2.27 kg d⁻¹ for NPs and 1.00 kg d⁻¹ for COP, accounting for 91% and 95% of the total discharge into Lake Shihwa, respectively. The highest concentrations of NPs and COP in sediments were found in samples at sites near the submarine outfall of the WWTPs, indicating that the submarine outfall is an important point source of wastewater pollution in Lake Shihwa.     

Analysis of metabolic changes in Trichoderma asperellum TJ01 at different fermentation time-points by LC-QQQ-MS

Trichoderma spp. are among the most widely recognized biocontrol fungi used to inhibit pathogens and promote plant growth. These functions are related to primary and secondary metabolites. This study investigated the different metabolites in Trichoderma asperellum TJ01 cultured for 24 and 72?h using liquid chromatography with triple-quadrupole mass spectrometry. Compared to the 24?h culture of T. asperellum TJ01, the 72?h culture with amino acid metabolism tended to decrease while sugar and lipid metabolisms tended to increase. Furthermore, the 72?h culture had a higher proportion of upregulated flavonoids, in combination with a higher proportion of downregulated alkaloids, and equal proportions of upregulated and downregulated polyphenols and hormones. This study also identified a few valuable medicinal substances such as trigonelline and 5-hydroxytryptophan in T. asperellum TJ01 fermentation cultures.     

色谱、光谱及联用技术在多农药残留检测中的应用

介绍了国内外多农药残留检测的发展状况,综述了色谱法、光谱法、色谱-质谱联用技术、色谱-光谱联用法、多维气相色谱技术的特点及在多农药残留检测中的应用,指出多农药残留检测在今后的农药残留检测中将占据主导地位.     

电感耦合等离子体发射光谱法测定石化废水中的重金属

建立了硝酸加热消解后采用电感耦合等离子体发射光谱(ICP-OES)测定石化废水中重金属(As,Cd,Cr,Cu,Zn,Pb,Mn)的方法,优化了仪器工作参数,得到了线性回归方程,并对该方法进行了评价。优化后的仪器工作参数为射频功率1 150 W、雾化器流量0.70 L/min、辅助气流量0.50 L/min。各重金属元素回归方程的相关系数均在0.999 9以上,检出限为0.000 18~0.007 00 mg/L,相对标准偏差为0.1%~2.0%,加标回收率为96.3%~102.2%。该方法具有线性关系好、检出限低、精密度和准确度高、分析速度快等优点。