Multiresidue determination of carbamate,organochlorine, organophosphorus,and dicarboximide pesticides in lettuce by GC/MS

An extraction method based on matrix solid-phase dispersion was developed to determine pirimicarb, methyl parathion, malathion, procymidone, α -endosulfan and β -endosulfan in lettuce using gas chromatography-mass spectrometry. The best results were obtained using 4.0 g of lettuce, 2.0 g of silica as dispersant sorbent, 0.1 g of activated carbon as clean up sorbent and acetonitrile as eluting solvent. The method was validated using lettuce samples fortified with pesticides at six different concentration levels (0.1 to 2.0 mg/kg). Average recoveries (7 replicates) ranged from 50 to 120 %, with relative standard deviations between 0.6 and 8.0 %. Detection and quantification limits for lettuce ranged from 0.01 to 0.02 mg/kg and 0.04 to 0.10 mg/kg, respectively.     

Evaluation and validation of two different chromatographic methods (HPLC and LC-MS/MS) for the determination and confirmation of ochratoxin A in pig tissues

This study was undertaken to compare two different analytical methods for the determination and confirmation of ochratoxin A (OTA) in blood serum, kidney and liver of pigs. Sample clean-up was based on liquid-liquid phase extraction. The detection of OTA was accomplished with high-performance liquid chromatography (HPLC) combined either with fluorescence detection (FL) or electro spray ionization (ESI+) tandem mass spectrometry (MS–MS). Comparative method evaluation was based on the investigation of 90 samples of blood serum, kidney and liver per animal originating from different regions of Serbia. The analytical results are discussed in view of the respective method validation data and the corresponding experimental protocols. In general, analytical data obtained with (LC–MS–MS) liquid chromatography electro spray tandem mass spectro metry detection offered comparable good results at the sub-ppb concentration level. The results indicate that the liquid chromatography electro spray tandem mass spectrometric (LC-MS/MS) method was more specific and sensitive for the analysis and confirmation of ochratoxin A in pig tissues then high pressure liquid chromatography (HPLC) method after methylation of OTA.     

Lindane removal by pure and mixed cultures of immobilized actinobacteria

Stereoselective dissipation of epoxiconazole had been studied in grape and soil during plant growing under field conditions in this paper. A sensitive and rapid chiral method was developed and validated for the determination of epoxiconazole stereoisomers in grape and soil based on liquid chromatography coupled with triple quadrupole mass spectrometry (LC-MS/MS). Phenomenex Lux Cellulose-1 column was used for enantioseparation with a mixture of acetonitrile/water (90/10, v/v) as mobile phase at flow rate of 0.3 mL min⁻¹. Fortified recoveries in grape and soil samples ranged from 76.0% to 91.9% and relative standard deviations were less than 11.4% with fortified levels of 0.025-1.0 mg kg⁻¹. The limits of detection and quantification were 0.005 mg kg⁻¹ and 0.025 mg kg⁻¹, respectively, with linear calibration curves extending up to 5.0 mg kg⁻¹. The field experimental results showed that dissipations of epoxiconazole stereoisomers in grape followed first-order kinetics (R² > 0.92) and stereoselectivity occurred in 2 h after spraying. The (−)-stereoisomer with half-life of 9.3 d degraded faster than (+)-stereoisomer with that of 13.2 d, and resulted in relative enrichment of (+)-stereoisomer. However, the stereoisomeric dissipations in soil were triphasic (“increase-decrease-steady”) with lower dissipation rates, and also occurred with preferential degradation of (−)-stereoisomer under field condition. The results for stereoselective dissipations can be applied for food and environmental assessments of chiral pesticides.     

The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products

For several decades, perfluorooctane sulfonate (PFOS) has widely been used as a fluorinated surfactant in aqueous film forming foams used as hydrocarbon fuel fire extinguishers. Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company. The major component of Forafac®1157 is a 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), and a link between the trade name and the exact chemical structure is presented here to the scientific community for the first time. In the present work, the structure of the 6:2 FTAB was elucidated by ¹H, ¹³C and ¹⁹F nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Moreover, its major metabolites from blue mussel (Mytilus edulis) and turbot (Scophthalmus maximus) and its photolytic transformation products were identified. Contrary to what has earlier been observed for PFOS, the 6:2 FTAB was extensively metabolized by blue mussel and turbot exposed to Forafac®1157. The major metabolite was a deacetylated betaine species, from which mono- and di-demethylated metabolites also were formed. Another abundant metabolite was the 6:2 fluorotelomer sulfonamide. In another experiment, Forafac®1157 was subjected to UV-light induced photolysis. The experimental conditions aimed to simulate Arctic conditions and the deacetylated species was again the primary transformation product of 6:2 FTAB. A 6:2 fluorotelomer sulfonamide was also formed along with a non-identified transformation product. The environmental presence of most of the metabolites and transformation products was qualitatively demonstrated by analysis of soil samples taken in close proximity to an airport fire training facility.     

混凝-生物接触氧化处理合成橡胶碱洗废水

对化学合成橡胶碱洗废水进行了有机组分和可生化性分析,废水主要含有氯甲烷、六甲苯、异丁醇、甲醇等污染物质,生化降解实验中废水TOC可在6d内从60．9mg／L下降至0．0mg／L,可生化降解性好,适于生化处理。选择混凝．生物接触氧化组合工艺对废水进行处理,采用优化条件（pH=8、PAC=40mg／L、PAM=8mg／L）进行混凝,碱洗废水COD去除率为9．95％～72．94％（平均31．51％）;混凝后的碱洗废水与冲洗废水1：5混合进行接触氧化处理,在HRT为36h的情况下,COD去除率为65．6％-72．6％（平均70．4％）,出水COD为134～331mg／L,满足企业废水排放市政管网的要求;同时,实验发现COD去除率与COD容积负荷存在指数函数变化关系。     

Determination of antibiotics in sewage from hospitals, nursery and slaughter house, wastewater treatment plant and source water in Chongqing region of Three Gorge Reservoir in China

Sewage samples from 4 hospitals, 1 nursery, 1 slaughter house, 1 wastewater treatment plant and 5 source water samples of Chongqing region of Three Gorge Reservoir were analyzed for macrolide, lincosamide, trimethoprim, fluorouinolone, sulfonamide and tetracycline antibiotics by online solid-phase extraction and liquid chromatography-tandem mass spectrometry. Results showed that the concentration of ofloxacin (OFX) in hospital was the highest among all water environments ranged from 1.660 μg/L to 4.240 μg/L and norfloxacin (NOR, 0.136-1.620 μg/L), ciproflaxacin (CIP, ranged from 0.011 μg/L to 0.136 μg/L), trimethoprim (TMP, 0.061-0.174 μg/L) were commonly detected. Removal range of antibiotics in the wastewater treatment plant was 18-100% and the removal ratio of tylosin, oxytetracycline and tetracycline were 100%. Relatively higher removal efficiencies were observed for tylosin (TYL), oxytetracycline (OXY) and tetracycline (TET)(100%), while lower removal efficiencies were observed for Trimethoprim (TMP, 1%), Epi-iso-chlorotetracycline (EICIC, 18%) and Erythromycin-H₂O (ERY-H₂O, 24%). Antibiotics were removed more efficiently in primary treatment compared with those in secondary treatment.     

Perfluorochemicals in wastewater treatment plants and sediments in Hong Kong

The study reported in this paper examined the concentrations of nineteen perfluorochemicals (PFCs), including perfluoroalkyl sulfonates, carboxylates, and sulfonamides in samples collected from Hong Kong wastewater treatment plants (WWTPs) and sediments. The study was the first to use an external isolator column to assist in the quantification of PFCs in environmental samples without having to make internal modifications to a liquid chromatography system. Perfluorooctanesulfonate was found to be the dominant PFC pollutant in Hong Kong, and the WWTP sludge was the major sink of PFCs discharged from the urban areas. Compared to discharge influenced by industrial activities, much less perfluorooctanoate was found in waste streams. The significantly lower level of perfluorodecanesulfonate in WWTP sludge reflects the important influence of consumer products on PFC distribution. The dominance of even-chain length perfluoroalkyl carboxylates in all of the WWTP sludge samples investigated further suggests the strong aerobic degradation of fluorotelomer alcohols in WWTPs.     

Identification of microcystins from three collection strains of Microcystis aeruginosa

Microcystins (MCs) are toxic cyclic heptapeptides produced by various cyanobacteria genera, especially Microcystis. We identified 10 out of 12 MCs produced by three Microcystis aeruginosa strains from cyanobacteria collections, UTEX 2666, UTEX 2670 and UAM 1303, by using two analytical methods: Matrix-assisted Laser Desorption Ionization Time of Flight Mass Spectrometry (MALDI-TOF/MS) and HPLC Photodiode Array Detector coupled to a hybrid Quadrupole Time of Flight Mass Spectrometry (HPLC-PDA-QTOF/MS). MALDI-TOF/MS failed to detect non-polar MCs, such as MC-LY and MC-LW. HPLC-QTOF/MS permitted the accurate identification of most MCs present in methanolic extracts. Besides, three new MCs, namely: [D-Glu(OCH₃)⁶, D-Asp³] MC-LAba, MC-YL and MC-YM were detected by HPLC-QTOF/MS.     

Analysis of Herbicide Krovar I™ by Liquid Chromatography with Atmospheric Pressure Chemical Ionization Mass Spectrometry

Abstract

A simple, very efficient method is presented for routine analysis of herbicide Krovar I? (active components bromacil and diuron) in water and soil samples. Water samples were extracted by liquid–liquid extraction with dichloromethane (DCM) as extraction solvent. For soil samples two different extraction techniques were compared: microwave-assisted solvent extraction and a shaking technique using a platform shaker. Extracts were analyzed by high performance liquid chromatography using a water:methanol gradient. Liquid chromatography was coupled with atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) for quantification of bromacil and diuron. Optimization of the APCI-MS was done by using standards in the flow injection analysis mode (FIA). Method detection limit for liquid samples for bromacil is 0.04 µg L^?1 and for diuron 0.03 µg L^?1. Method detection limit for soil samples is 0.01 µg g^?1 dry weight for both compounds. Results of analysis of field samples of water and soil are also presented.     

Parental phenols exposure and spontaneous abortion in Chinese population residing in the middle and lower reaches of the Yangtze River

Widespread use of phenols has led to ubiquitous exposure to phenols. In experimental animals, phenols increased resorptions, reduced live litter size and fetal body weights. However, there are limited epidemiological evidences of the relationships between exposure to phenols and pregnancy outcomes. We evaluated the associations between parental urinary levels of various phenols and spontaneous abortion in a Chinese population residing in the middle and lower reaches of the Yangtze River. A case-control study was conducted that included 70 case couples with medically unexplained spontaneous abortion and 180 control couples who did not have a history of spontaneous abortion and had at least one living child. Both parental urinary phenols were measured by ultra-high performance liquid chromatography-tandem mass spectrometry including bisphenol A (BPA), benzophenone-3 (BP-3), 2,3,4-trichlorophenol (2,3,4-TCP), pentachlorophenol (PCP), 4-n-octylphenol (4-n-OP) and 4-n-nonylphenol (4-n-NP). Compared with the low exposure group, there was an increased risk of spontaneous abortion with high paternal urinary PCP concentration [odds ratio (OR) = 2.09, 95% Confidence Interval (CI), 1.05–4.14], and maternal exposure to 4-n-OP and alkylphenol(s) also significantly increased the risk of spontaneous abortion (OR = 2.21, 95% CI, 1.02–4.80; OR = 2.81, 95% CI, 1.39–5.65, respectively). Our study firstly provides the evidence that paternal PCP exposure, maternal 4-n-OP and alkylphenol(s) exposure are associated with spontaneous abortion in humans.