Environmental screening by capillary gas chromatography combined with mass spectrometry and atomic emission spectroscopy

Capillary gas chromatography (GC) combined with mass spectrometry (MS) and atomic emission spectroscopy (AED) was utilized for a comprehensive investigation of organic micropollutants in a marine sediment. Most compounds were found and identified by GC-MS library search. The elemental information from GC-AED was utilized for confirmation purposes, for analyte characterization in cases where identification by GC-MS was impossible, and for screening on heteroatomic components. In addition, GC-AED was effectively used for the quantitative part, where the total amount of GC amenable material, classes of compounds, and individual components were determined.     

铝箔复合膜集气袋对有机废气的适用性研究

通过在不同的时间段,测定存放于铝箔复合膜集气袋和玻璃注射器的丙酮,醋酸乙酯,苯,异丙醇标准气的浓度,气体浓度与贮存时间的关系,本次试验结果表明,丙酮,醋酸乙酯,苯,异丙醇在铝箔气袋中的稳定性明显优于在玻璃注射器中,应尽可能在８－２４ｈ内测定。     

生物过滤塔处理实验室废气

研究了生物过滤塔处理实验室排放的模拟混合废气,考察了反应器对苯、甲苯、二甲苯、乙醇、丙酮、乙酸乙酯和甲烷等废气的去除效果。运行结果表明,在设备稳定运行期间,进气中总挥发性有机物(TVOCs)的浓度为124～380 mg/m3,而出气浓度在10～40 mg/m3,去除效率保持在85%以上。实验室废气中的多种污染物在生物过滤塔中去除机理不同,亲水性污染物的去除效率高于疏水性污染物。通过系统关停后重启,污染物的去除效果在第2天就能恢复,这为生物过滤塔处理实验室废气过程的停运检修或者系统闲置提供了可行性。     

Application of preparative capillary gas chromatography (pcGC), automated structure generation and mutagenicity prediction to improve effect-directed analysis of genotoxicants in a contaminated groundwater

Background, aim and scope  

The importance of groundwater for human life cannot be overemphasised. Besides fulfilling essential ecological functions, it is a major source of drinking water. However, in the industrial area of Bitterfeld, it is contaminated with a multitude of harmful chemicals, including genotoxicants. Therefore, recently developed methodologies including preparative capillary gas chromatography (pcGC), MOLGEN-MS structure generation and mutagenicity prediction were applied within effect-directed analysis (EDA) to reduce sample complexity and to identify candidate mutagens in the samples. A major focus was put on the added value of these tools compared to conventional EDA combining reversed-phase liquid chromatography (RP-LC) followed by GC/MS analysis and MS library search.     

Validation and application of an analytical method for determining pesticides in the gas phase of ambient air

A method for determining atmospheric concentrations of eight pesticides applied to corn and soybean crops in Mato Grosso state, Brazil is presented. The method involved a XAD-2 resin cartridge coupled to a low volume air pump at 2 L min?1 over 8 hours. Pesticides were recovered from the resin using sonication with n-hexane:ethyl acetate and determined by GC-MS. Good accuracy (76-128%) and precision (CV < 20%) were obtained for atrazine, chlorpyrifos, alpha- and beta-endosulfan, endosulfan sulfate, flutriafol, malathion, metolachlor and permethrin. Method detection ranged from 9.0 to 17.9 ng m?3. This method was applied to 61 gas phase samples collected between December 2008 and June 2009. Atrazine and endosulfan were detected both in urban and rural areas indicating the importance of atmospheric dispersion of pesticides in tropical areas. The simple and efficient extraction method and sampling system employed was considered suitable for identifying pesticides in areas of intense agricultural production.     

Validation and application of an analytical method for determining pesticides in the gas phase of ambient air

A method for determining atmospheric concentrations of eight pesticides applied to corn and soybean crops in Mato Grosso state, Brazil is presented. The method involved a XAD-2 resin cartridge coupled to a low volume air pump at 2 L min^?1 over 8 hours. Pesticides were recovered from the resin using sonication with n-hexane:ethyl acetate and determined by GC-MS. Good accuracy (76–128%) and precision (CV < 20%) were obtained for atrazine, chlorpyrifos, alpha- and beta-endosulfan, endosulfan sulfate, flutriafol, malathion, metolachlor and permethrin. Method detection ranged from 9.0 to 17.9 ng m^?3. This method was applied to 61 gas phase samples collected between December 2008 and June 2009. Atrazine and endosulfan were detected both in urban and rural areas indicating the importance of atmospheric dispersion of pesticides in tropical areas. The simple and efficient extraction method and sampling system employed was considered suitable for identifying pesticides in areas of intense agricultural production.     

An improved algorithm for locating a gas source using inverse methods

We apply an inverse problem approach to locating a known gas source in a desert setting from simultaneous measurements of gas concentration and wind data. We use a random search algorithm with simulated annealing to generate candidate distributions of source strengths and positions. These distributions are then assessed by means of a cost function, which quantifies the degree to which the postulated source distribution accounts for the measured gas concentrations. We present results from using three cost functions with differing regularisation terms. We assess the robustness of these and the differing regularisation terms by the progressive addition of random noise and systematic offsets to the concentration data. We show that for our application, the best reconstructions are obtained by using a multiplicative regularisation parameter defined to minimise the total gas emissions.     

某钢厂烧结烟气脱硫系统滤袋失效原因分析

分析了聚苯硫醚自身特性,从而了解目前烧结烟气脱硫系统袋式除尘器中选择其作为滤料的原因。并就目前某钢厂烧结烟气脱硫系统实际发生的滤袋失效问题,通过扫描电镜、EDS能谱分析及烧失量实验对滤袋进行分析,发现材料中混入的玻璃纤维是造成其失效的主要原因,为今后实际工程中滤袋的选择提供依据,从而尽量减少不必要的损失,确保烟气脱硫项目的正常运行。     

Application of gas diffusion biocathode in microbial electrosynthesis from carbon dioxide

Microbial catalysis of carbon dioxide (CO₂) reduction to multi-carbon compounds at the cathode is a highly attractive application of microbial electrosynthesis (MES). The microbes reduce CO₂ by either taking the electrons or reducing the equivalents produced at the cathode. While using gaseous CO₂ as the carbon source, the biological reduction process depends on the dissolution and mass transfer of CO₂ in the electrolyte. In order to deal with this issue, a gas diffusion electrode (GDE) was investigated by feeding CO₂ through the GDE into the MES reactor for its reduction at the biocathode. A combination of the catalyst layer (porous activated carbon and Teflon binder) and the hydrophobic gas diffusion layer (GDL) creates a three-phase interface at the electrode. So, CO₂ and reducing equivalents will be available to the biocatalyst on the cathode surface. An enriched inoculum consisting of acetogenic bacteria, prepared from an anaerobic sludge, was used as a biocatalyst. The cathode potential was maintained at ?1.1 V vs Ag/AgCl to facilitate direct and/or hydrogen-mediated CO₂ reduction. Bioelectrochemical CO₂ reduction mainly produced acetate but also extended the products to ethanol and butyrate. Average acetate production rates of 32 and 61 mg/L/day, respectively, with 20 and 80 % CO₂ gas mixture feed were achieved with 10 cm² of GDE. The maximum acetate production rate remained 238 mg/L/day for 20 % CO₂ gas mixture. In conclusion, a gas diffusion biocathode supported bioelectrochemical CO₂ reduction with enhanced mass transfer rate at continuous supply of gaseous CO₂.

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Simultaneous determination of organochlorine and pyrethriod pesticide residues in the Chinese patent medicines by gas chromatography-tandem mass spectrometry

A simple, sensitive, reliable method was developed for the simultaneous determination of organochlorine and pyrethriod pesticide residues in Chinese patent medicines Six ingredient rehmannia pills and Xiaoyao pills. These pesticides were extracted by ethyl acetate. The extraction time and volume of ethyl acetate were optimized. Cleanup of extracts was performed with dispersive-solid phase extraction using graphitized carbon black as the sorbent. The determination of pesticides in the final extracts was carried out by gas chromatography–tandem mass spectrometry in multiple reaction monitoring mode (GC-MS/MS, MRM). The linearity of the calibration curves is good in matrix-matched standard and yields the coefficients of determination (R²) ≥0.99 for all of the target analytes. Under optimized conditions, the average recoveries (five replicates) for most pesticides range from 75.5% to 114.6%, and RSDs are less than 10.0%. The LODs of 18 pesticides in Six ingredient rehmannia pill and Xiaoyao pills are in the range of 0.01–8.82 μg kg^?1. The developed method meets the requirements of pesticide residue analysis and could be effectively used for routine analysis of the organochlorine and pyrethriod pesticide residues in Six ingredient rehmannia pills and Xiaoyao pills.     

A laboratory study of sediment and contaminant release during gas ebullition

Significant quantities of gas are generated from labile organic matter in contaminated sediments. The implications for the gas generation and subsequent release of contaminants from sediments are unknown but may include enhanced direct transport such as pore water advection and diffusion. The behavior of gas in sediments and the resulting migration of a polyaromatic hydrocarbon, viz phenanthrene, were investigated in an experimental system with methane injection at the base of a sediment column. Hexane above the overlying water layer was used to trap any phenanthrene migrating out of the sediment layer. The rate of suspension of solid particulate matter from the sediment bed into the overlying water layer was also monitored. The experiments indicated that significant amounts of both solid particulate matter and contaminant can be released from a sediment bed by gas movement with the amount of release related to the volume of gas released. The effective mass transfer coefficient of gas bubble-facilitated contaminant release was estimated under field conditions, being around three orders of magnitude smaller than that of bioturbation. A thin sand-capping layer (2 cm) was found to dramatically reduce the amount of contaminant or particles released with the gas because it could prevent or at least reduce sediment suspension. Based on the experimental observations, gas bubble-facilitated contaminant transport pathways for both uncapped and capped systems were proposed. Sediment cores were sliced to obtain phenanthrene concentration. X-ray computed tomography (CT) was used to investigate the void space distribution in the sediment penetrated by gas bubbles. The results showed that gas bubble migration could redistribute the sediment void spaces and may facilitate pore water circulation in the sediment.     

石灰和石灰石湿法脱硫系统运行控制指标探讨

钙基脱硫剂湿式脱硫系统是目前市场上广泛采用的烟气脱硫系统。文章分析了石灰和石灰石自身不同的物理化学特性对湿法脱硫系统运行控制指标的影响,得出了对于采用石灰和石灰石作为脱硫剂的湿式脱硫系统的最佳pH为8．0和5．8～6．2,脱硫浆液流量与烟气流量之比为10．0和5．6,钙硫比(化学过量比)为1．05～1．15和1．25～1．60。     

垃圾填埋气收集控制的CFD数值模拟应用研究

基于多孔介质渗流理论,给出了填埋气在填埋场内流动控制方程组及其定解条件,但实际填埋场的不规则边界使其很难求得解析解。建立填埋场竖井抽气物理模型,采用计算流体力学数值模拟软件PHONEICS求得控制方程的数值解,并用相关文献的结论进行校验,结果与前人结论相吻合。将该方法应用于实际填埋场抽气系统的设计,通过PHONEICS软件编程接口二次开发计算负压抽气条件下流入抽气系统的外部空气量,由此引入抽气效率做为抽气效果的评价指标,模拟了传统等边三角形布置竖井抽气系统的运行效果,并根据模拟结果对传统竖井抽气系统进行优化。     

固化/稳定化处理污泥填埋气液转化模式

固化/稳定化污泥进行填埋产生填埋气,产气规律是指导填埋气收集处理系统设计的重要依据。通过构建大型填埋柱模拟填埋实验,研究不同固化材料添加量污泥气液转化规律。实验结果表明,原泥和固化污泥产气规律分为2种类型:前期产气速率呈线性增加,达到最大速率后产气速率呈指数降低。低添加量的固化污泥,产气分3个阶段,分别为产气抑制期、增长期和衰减期。高添加量固化污泥,产气只有一个阶段,产气速率随着时间推移逐渐减小,产气量很小。固化污泥降解过程就是有机质含量降低,气体产量、含水率增加相互转化过程,达到固化材料添加量25%时,水分和气体产生量均很小,降解受到很强抑制,产气150 d左右稳定,产气量很小,无需单独设置气体收集系统。     

改进GC/FID法连续观测大气中CO浓度

改进装配有氢火焰离子化检测器(即FID)的气相色谱仪(GC),可连续监测大气中痕量气体CO浓度.本系统采用单阀双柱反吹进样技术,优选前置柱能更有效地剔除杂质,提高了分析柱效率,保持色谱基线平稳,提高分辨率和定量分析的准确率.优化后的气路设计与色谱柱的改进,使GC/FID对CO的最低检出限达到10×10-9、精密度误差小于2%,准确度在±2%之内.将气相色谱与动态气体稀释仪耦合使系统能够自动进行工作曲线校准,系统自动采样、分析和标定,无需人员职守.对北京大气CO连续观测结果表明,北京大气CO浓度变化受气象要素与排放源双重控制.     

湿法烟气脱硫系统的脱汞性能现场实验

分析湿法烟气脱硫系统的脱汞性能,对控制燃煤电厂的汞污染具有重要意义。利用安大略水法和吸附管法分别对某600 MW电厂湿法脱硫系统的进出口的烟气进行了采样,测量了烟气中各形态汞浓度,并分析了该系统对烟气总汞、气态氧化态汞的脱除效果以及对气态单质汞的影响。研究结果表明,安大略水法和吸附管法均能较为准确地测定湿法脱硫系统进出口烟气中的汞含量,测得入口和出口的氧化汞与平均值的相对误差的绝对值分别为3.5%和1.3%;入口和出口的单质汞与平均值相对误差的绝对值分别为16.6%和3.3%。其中吸附管法操作相对简单。通过湿法烟气脱硫系统后,烟气中氧化态汞的浓度可下降87.5%,其中约67.5%的氧化态汞被湿法脱硫系统脱除,约20%的氧化态汞在脱硫浆液的还原作用下被还原为单质汞,导致脱硫系统出口的单质汞浓度高于入口。     

Reduction of dioxin emission by a multi-layer reactor with bead-shaped activated carbon in simulated gas stream and real flue gas of a sinter plant

A laboratory-scale multi-layer system was developed for the adsorption of PCDD/Fs from gas streams at various operating conditions, including gas flow rate, operating temperature and water vapor content. Excellent PCDD/F removal efficiency (>99.99%) was achieved with the multi-layer design with bead-shaped activated carbons (BACs). The PCDD/F removal efficiency achieved with the first layer adsorption bed decreased as the gas flow rate was increased due to the decrease of the gas retention time. The PCDD/F concentrations measured at the outlet of the third layer adsorption bed were all lower than 0.1 ng I-TEQ Nm⁻³. The PCDD/Fs desorbed from BAC were mainly lowly chlorinated congeners and the PCDD/F outlet concentrations increased as the operating temperature was increased. In addition, the results of pilot-scale experiment (real flue gases of an iron ore sintering plant) indicated that as the gas flow rate was controlled at 15 slpm, the removal efficiencies of PCDD/F congeners achieved with the multi-layer reactor with BAC were better than that in higher gas flow rate condition (20 slpm). Overall, the lab-scale and pilot-scale experiments indicated that PCDD/F removal achieved by multi-layer reactor with BAC strongly depended on the flow rate of the gas stream to be treated.     

A new approach for biological online testing of stack gas condensate from municipal waste incinerators

A biological testing system for the monitoring of stack gas condensates of municipal waste incinerators has been developed using Euglena gracilis as a test organism. The motility, velocity and cellular form of the organisms were the endpoints, calculated by an image analysis system. All endpoints showed statistically significant changes in a short time when organisms were exposed to samples collected during combustion situations with increased pollutant concentrations. The velocity of the organisms proved to be the most appropriate endpoint. A semi-continuous system with E. gracilis for monitoring stack gas condensate is proposed, which could result in an online system for testing stack gas condensates in the future.     

Compositions and greenhouse gas emission factors of flared and vented gas in the Western Canadian Sedimentary Basin

A significant obstacle in evaluating mitigation strategies for flaring and venting in the upstream oil and gas industry is the lack of publicly available data on the chemical composition of the gas. This information is required to determine the economic value of the gas, infrastructure and processing requirements, and potential emissions or emissions credits, all of which have significant impact on the economics of such strategies. This paper describes a method for estimating the composition of solution gas being flared and vented at individual facilities, and presents results derived for Alberta, Canada, which sits at the heart of the Western Canadian Sedimentary Basin. Using large amounts of raw data obtained through the Alberta Energy Resources Conservation Board, a relational database was created and specialized queries were developed to link production stream data, raw gas samples, and geography to create production-linked gas composition profiles for approximately half of the currently active facilities. These were used to create composition maps for the entire region, to which the remaining facilities with unknown compositions were geographically linked. The derived data were used to compute a range of solution gas composition profiles and greenhouse gas emission factors, providing new insight into flaring and venting in the region and enabling informed analysis of future management and mitigation strategies.

Implications: Accurate and transparent determination of environmental impacts of flaring and venting of gas associated with oil production, and potential benefits of mitigation, is severely hampered by the lack of publicly available gas composition data. In jurisdictions within the Western Canadian Sedimentary Basin, frameworks exist for regulating and trading carbon offset credits but current potential for mitigation is limited by a lack of standardized methods for calculating CO₂ equivalent emissions. The composition and emission factor data derived in this paper will be useful to industry, regulators, policy researchers, and entrepreneurs seeking statistically significant and openly available data necessary to manage and mitigate upstream flaring and venting activity and estimate greenhouse gas impacts.     

Rapid measurements and mapping of tracer gas concentrations in a large indoor space

Rapid mapping of gas concentrations in air benefits studies of atmospheric phenomena ranging from pollutant dispersion to surface layer meteorology. Here we demonstrate a technique that combines multiple-open-path tunable-diode-laser spectroscopy and computed tomography to map tracer gas concentrations with approximately 0.5 m spatial and 7 s temporal resolution. Releasing CH₄ as a tracer gas in a large (7 m×9 m×11 m high) ventilated chamber, we measured path-integrated CH₄ concentrations over a planar array of 28 “long” (2–10 m) optical paths, recording a complete sequence of measurements every 7 s during the course of hour-long experiments. Maps of CH₄ concentration were reconstructed from the long path data using a computed tomography algorithm that employed simulated annealing to search for a best fit solution. The reconstructed maps were compared with simultaneous measurements from 28 “short” (0.5 m) optical paths located in the same measurement plane. On average, the reconstructed maps capture ∼74% of the variance in the short path measurements. The accuracy of the reconstructed maps is limited, in large part, by the number of optical paths and the time required for the measurement. Straightforward enhancements to the instrumentation will allow rapid mapping of three-dimensional gas concentrations in indoor and outdoor air, with sub-second temporal resolution.