Trace level determination of selected organophosphorus pesticides and their degradation products in environmental air samples by liquid chromatography-positive ion electrospray tandem mass spectrometry

This paper describes a new analytical method for determination of organophosphorus pesticides (OPs) along with their degradation products involving liquid chromatography (LC) positive ion electrospray (ESI+) tandem mass spectrometry (MS-MS) with selective reaction monitoring (SRM). Chromatography was performed on a Gemini C6-Phenyl (150 mmx2.0 mm, 3 microm) with a gradient elution using water-methanol with 0.1% formic acid, 2 mM ammonium acetate mobile phase at a flow rate of 0.2 mL min(-1). The LC separation and MS/MS operating conditions were optimized with a total analysis time less than 40 minutes. Method detection limits of 0.1-5 microg L(-1) for selected organophosphorus pesticides (OP), OP oxon degradation products, and other degradation products: 3,5,6-trichloro-2-pyridinol (TCP); 2-isopropyl-6-methyl-4-pyrimidol (IMP); and diethyl phosphate (DEP). Some OPs such as fenchlorphos are less sensitive (MDL 30 microg L(-1)). Calibration curves were linear with coefficients of correlation better than 0.995. A three-point identification approach was adopted with area from first selective reaction monitoring (SRM) transition used for quantitative analysis, while a second SRM transition along with the ratio of areas obtained from the first to second transition are used for confirmation with sample tolerance established by the relative standard deviation of the ratio obtained from standards. This new method permitted the first known detection of OP oxon degradation products including chlorpyrifos oxon at Bratt's Lake, SK and diazinon oxon and malathion oxon at Abbotsford, BC in atmospheric samples. Atmospheric detection limits typically ranged from 0.2-10 pg m(-3).     

Characterization of controlled-release KMnO4 (CRP) barrier system for groundwater remediation: a pilot-scale flow-tank study

Release and spreading of permanganate (MnO(4)(-)) in the well-based controlled-release potassium permanganate (KMnO(4)) barrier system (CRP system) was investigated by conducting column release tests, model simulations, soil oxidant demand (SOD) analyses, and pilot-scale flow-tank experiments. A large flow tank (L x W x D=8m x 4m x 3m) was constructed. Pilot-scale CRP pellets (OD x L=0.05 m x1.5m; n=110) were manufactured by mixing approximately 198 kg of KMnO(4) powders with paraffin wax and silica sands in cylindrical moulds. The CRP system (L x W x D=3m x 4m x 1.5m) comprising 110 delivery wells in three discrete barriers was constructed in the flow tank. Natural sands (organic carbon content=0.18%; SOD=3.7-11 g MnO(4)(-)kg(-1)) were used as porous media. Column release tests and model simulations indicated that the CRP system could continuously release MnO(4)(-) over several years, with slowly decreasing release rates of 2.5 kg d(-1) (day one), 109 g d(-1) (day 100), 58 g d(-1) (year one), 22 g d(-1) (year five), and 12 g d(-1) (year 10). Mean MnO(4)(-) concentrations within the CRP system ranged from 0.5 to 6 mg l(-1) during the 42 days of testing period. The continuously releasing MnO(4)(-) was gradually removed by SOD limiting the length of MnO(4)(-) zone in the porous media. These data suggested that the CRP system could create persistent and confined oxidation zone in the subsurface. Through development of advanced tools for describing agent transport and facilitating lateral agent spreading, the CRP system could provide new approach for long-term in situ treatment of contaminant plumes in groundwater.     

Inorganic arsenic levels in baby rice are of concern

Inorganic arsenic is a chronic exposure carcinogen. Analysis of UK baby rice revealed a median inorganic arsenic content (n = 17) of 0.11 mg/kg. By plotting inorganic arsenic against total arsenic, it was found that inorganic concentrations increased linearly up to 0.25 mg/kg total arsenic, then plateaued at 0.16 mg/kg at higher total arsenic concentrations. Inorganic arsenic intake by babies (4-12 months) was considered with respect to current dietary ingestion regulations. It was found that 35% of the baby rice samples analysed would be illegal for sale in China which has regulatory limit of 0.15 mg/kg inorganic arsenic. EU and US food regulations on arsenic are non-existent. When baby inorganic arsenic intake from rice was considered, median consumption (expressed as μg/kg/d) was higher than drinking water maximum exposures predicted for adults in these regions when water intake was expressed on a bodyweight basis.     

Titanium dioxide mediated photocatalytic degradation of 17beta-estradiol in aqueous solution

Photocatalytic degradation of 17beta-estradiol (E2) in aqueous medium mediated with titanium dioxide (TiO(2)) was studied. Moreover, effect of TiO(2) dosage on the degradation efficiency was investigated. Particular attention was paid to the identification of intermediates and analysis of photocatalytic degradation mechanism of E2 under neutral and alkaline conditions. The degradation efficiency of E2 increased with increasing concentration of TiO(2) but decreased due to light scattering as TiO(2) concentration was greater than 0.5mgml(-1). Several intermediates were formed during photocatalytic degradation of E2. However, only a few of the compounds could be identified and confirmed by LC-MS and LC-MS/MS. Six intermediates were observed by photocatalytic oxidation under alkaline conditions, namely 2-hydroxyestradiol, 10epsilon-17beta-dihydroxy-1,4-estradien-3-one (DEO), 10epsilon-hydroperoxide-17beta-hydroxy-1,4-estradien-3-one and three kinds of dicarboxylic acids formed by the opening of aromatic ring. In addition to the six intermediates mentioned above, 17beta-hydroxy-1,4-estradien-3-one (EO) was observed under neutral conditions and in the presence of methanol. Based on these intermediates, which were hardly degraded even after E2 was fully degraded, the mechanism of E2 degradation by TiO(2) photocatalysis was elucidated.     

沉淀剂对稀土Gd掺杂SnO2/Ti涂层阳极性能的影响

实验采用共沉淀法,以无机盐SnCl4·5H2O、Sb2O3、Gd(NO3)3为前驱体,制备稀土Gd掺杂SnO2/Ti多组分涂层阳极。研究了用不同沉淀剂制备的电极以苯酚为目标有机物的电化学降解特性,以考察沉淀剂对稀土Gd掺杂SnO2/Ti阳极性能的影响;并对所制备的涂层阳极进行了SEM、XRD、XPS等表征及阳极极化曲线、循环伏安曲线测试,分析并讨论了沉淀剂对稀土Gd掺杂SnO2/Ti阳极性能的影响机理。结果表明,沉淀剂对稀土Gd掺杂SnO2/Ti电极性能有较大的影响,在本实验条件,以氨水为沉淀剂所制备的电极电催化性能较好,稳定性能较高。     

生物质燃气高温过滤材料的研究

日趋严格的环保要求和某些工艺过程的特殊需要,对生物质燃气中灰尘的数量和粒度提出了更高的要求,即对生物质气化系统中的过滤工艺有了新的要求。针对生物质气化工艺的特点及其灰尘的特性,重点研究了针刺过滤毡和金属多孔材料两类高温过滤材料。通过研究比较,两种材料各有优缺点,针刺过滤毡过滤精度高,运行工况比较稳定,但是过滤气速小,适用温度低,设备比较庞大;金属多孔材料过滤精度相对较低,但是过滤气速和使用温度高,设备相对紧凑。     

自组装单层材料对水中除草剂西玛津的吸附研究

以SiO2微粉为基底制备了终端接有SO3H基的自组装单层材料(SO3H/SiO2),研究了其吸附水中弱碱性除草剂西玛津的性能及机制.结果表明,SO3H/SiO2能有效清除水中西玛津,如0.12 g SO3H/SiO2对20 mL 1.4 mg/L西玛津吸附3 h,其吸附率达91%.吸附等温实验数据用Langmuir吸附等温式拟合效果优于Freundlich吸附等温式.吸附机制为静电相互作用,西玛津分子大部分以分子形式到达自组单层的表面,SO3H基电离的H 使西玛津质子化而带正电,从而与-SO3-通过静电作用而保留在SO3H/SiO2的表面.     

Simultaneous measurements of arsenic and sulfide using diffusive gradients in thin films technique (DGT)

Diffusive gradients in thin films technique (DGT) is a dynamically passive sampling technique which has been applied increasingly to the environmental monitoring field. In the preliminary period, the DGT with zirconium hydroxide-silver iodide as the binding phase (ZrO-AgI DGT) has been developed for the determination of sulfide (S(II)). On this basis, this paper developed its determination method for inorganic arsenite (As(III)) to further realize the simultaneous and high-resolution measurements of labile inorganic As and S(II) in sediments. ZrO-AgI binding gel had a strong ability in adsorbing and fixing As(III), showing a linear increase in the initial 12.5 min. After saturation of S(II) on ZrO-AgI binding gel, the adsorption rate and adsorption capacity of As(III) reduced by 8 and 14%, respectively. A stable elution rate (89.1 ± 2.2%) was obtained by extraction of As(III) on the binding gel using a mixture solution of 1.0 M NaOH and 1.0 M H₂O₂ (1:1). The DGT capacity of As(III) determined by the ZrO-AgI DGT was 23.6 μg cm^?2. DGT uptakes of As(III) were independent of pH (4.0–9.0) and ionic strength (0.01–100 mM), and they did not interfere with each other during the uptake process. Simultaneous measurements of labile As and S(II) in four sediment cores of Taihu Lake (China) with ZrO-AgI DGT showed that they had similarly vertical distributions in the top 16-mm layer in one core and in the whole profile up to the 35 mm depth in two cores. It likely reflected a simultaneous release of As and S(II) in sediments by synchronous reduction of As-hosted oxidized iron and sulfate, respectively. The simultaneous decreases of labile As and S(II) from their co-precipitation (e.g., As₂S₃) were not obvious in deeper sediment layer through the measurement with ZrO-AgI DGT.     

Broadening of appropriate demulsifier dosage range for latex-containing wastewater by sulfate addition

Investigation of demulsification of polybutadiene latex (PBL) wastewater by polyaluminum chloride (PAC) indicated that there was an appropriate dosage range for latex removal. The demulsification mechanism of PAC was adsorption-charge neutralization and its appropriate dosage range was controlled by zeta potential. When the zeta potential of the mixture was between -15 and 15 mV after adding PAC, the demulsification effect was good. Decreasing the latex concentration in chemical oxygen demand (COD) from 8.0 g/L to 0.2 g/L made the appropriate PAC dosage range narrower and caused the maximum latex removal efficiency to decrease from 95% to 37%. Therefore, more accurate PAC dosage control is required. Moreover, adding 50 mg/L sulfate broadened the appropriate PAC dosage range, resulting in an increase in maximum latex removal efficiency from 37% to 91% for wastewater of 0.2 g COD/L. The addition of sulfate will favor more flexible PAC dosage control in demulsification of PBL wastewater.

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