Matrix effects in analysis of dialkyl phosphate metabolites of organophosphate pesticides in urine by gas chromatography/tandem mass spectrometer

Urinary dialkyl phosphate metabolites (DAPs) are used as biomarkers to evaluate human exposure to organophosphate pesticides. The objective was to evaluate potential artifacts in urinary DAPs analysis during sample preparation and method calibration. Diluted urine pools were commonly used to prepare calibration standards to minimize the effects due to the complexity of urine matrix. Matrix effects on measurements of DAPs were evaluated by spiking known amount of standards into distilled water, synthetic urine and diluted urine pool. Different matrices resulted in similar concentrations detected for all target compounds, except dimethylphosphate (DMP) with the deviation of measurement as large as eight times the spiked amount. In this study, we also found that urinary particles, which usually appeared after thawing frozen human urine samples, could affect the measurements of DAPs, especially DMP and diethylthiophosphate (DETP). Results of DAPs measurements in three types of sample matrices, i.e. urine without particles, urine with particles and particles only were compared. DETP could be subject to large error during this preparation step. The use of deuterated and ¹³C₁₂-labeled DAPs as internal standards is also evaluated. Overall, these issues can cause misidentification and inaccuracies, which may significantly affect the data quality.     

Carbonyl Emissions from Commercial Cooking Sources in Hong Kong

Abstract

Cooking fumes are an important carbonyl emission source, especially in a highly urbanized city, such as Hong Kong. Cooking exhaust from 15 commercial kitchens of a variety of cooking styles was sampled and analyzed for a suite of 13 carbonyl compounds. Carbonyl compositions were varied among the different cooking styles. Formal dehyde was generally the most abundant carbonyl, and its contribution to the total carbonyl amount on a molar basis ranged from 12 to 60%. Acrolein was also found to be an abundant carbonyl in the cooking exhaust. The highest contribution by acrolein to the total carbonyls was found to be 30% in the exhaust of a western-style steak restaurant. Long-chain saturated carbonyls, that is, heptanal, octanal, and nonanal, accounted for a signifi-cant fraction (>40%) of the total carbonyls in kitchens that always used heated cooking oils. Two dicarbonyls, glyoxal and methylglyoxal, had a various presence in the cooking emissions, ranging from negligible to 10%. The presence of benzaldehyde and tolualdehyde was mostly negligible in the sampled kitchen exhaust. Annual emission rates of both individual carbonyls and total carbon-yls were estimated for various types of commercial kitchens. Local-style fast-food shops contributed the highest total carbonyl emissions per year mainly because of the large number of this kind of restaurant in Hong Kong. The citywide annual emission rates of the three most toxic carbonyls, formaldehyde, acetaldehyde, and acrolein, were estimated assuming that the limited number of sampled restaurants were representative of the average restaurants. Such estimates of carbonyl emission rates were comparable to the estimated carbonyl emissions from vehicular sources, suggesting the importance of commercial cooking as a source for carbonyls in Hong Kong.     

Two-stage biofilter for effective NH3 removal from waste gases containing high concentrations of H2S

A high H2S concentration inhibits nitrification when H2S and NH3 are simultaneously treated in a single biofilter. To improve NH3 removal from waste gases containing concentrated H2S, a two-stage biofilter was designed to solve the problem. In this study, the first biofilter, inoculated with Thiobacillus thioparus, was intended mainly to remove H2S and to reduce the effect of H2S concentration on nitrification in the second biofilter, and the second biofilter, inoculated with Nitrosomonas europaea, was to remove NH3. Extensive studies, which took into account the characteristics of gas removal, the engineering properties of the two biofilters, and biological parameters, were conducted in a 210-day operation. The results showed that an average 98% removal efficiency for H2S and a 100% removal efficiency for NH3 (empty bed retention time = 23-180 sec) were achieved after 70 days. The maximum degradation rate for NH3 was measured as 2.35 g N day(-1) kg of dry granular activated carbon(-1). Inhibition of nitrification was not found in the biofilter. This two-stage biofilter also exhibited good adaptability to shock loading and shutdown periods. Analysis of metabolic product and observation of the bacterial community revealed no obvious acidification or alkalinity phenomena. In addition, a lower moisture content (approximately 40%) for microbial survival and low pressure drop (average 24.39 mm H2O m(-1)) for system operation demonstrated that the two-stage biofilter was energy saving and economic. Thus, the two-stage biofilter is a feasible system to enhance NH3 removal in the concentrated coexistence of H2S.     

Advances in integrated and continuous measurements for particle mass and chemical composition

Recent improvements in integrated and continuous PM2.5 mass and chemical measurements from the Supersite program and related studies in the past decade are summarized. Analytical capabilities of the measurement methods, including accuracy, precision, interferences, minimum detectable levels, comparability, and data completeness are documented. Upstream denuders followed by filter packs in integrated samplers allow an estimation of sampling artifacts. Efforts are needed to: (1) address positive and negative artifacts for organic carbon (OC), and (2) develop carbon standards to better separate organic versus elemental carbon (EC) under different temperature settings and analysis atmospheres. Advances in thermal desorption followed by gas chromatography/ mass spectrometry (GC/MS) provide organic speciation of approximately 130 nonpolar compounds (e.g., n-alkanes, alkenes, hopanes, steranes, and polycyclic aromatic hydrocarbons [PAHs]) using small portions of filters from existing integrated samples. Speciation of water-soluble OC (WSOC) using ion chromatography (IC)-based instruments can replace labor-intensive solvent extraction for many compounds used as source markers. Thermal gas-based continuous nitrate and sulfate measurements underestimate filter ions by 10-50% and require calibration against on-site filter-based measurements. IC-based instruments provide multiple ions and report comparable (+/-10%) results to filter-based measurements. Maintaining a greater than 80% data capture rate in continuous instruments is labor intensive and requires experienced operators. Several instruments quantify black carbon (BC) by optical or photoacoustic methods, or EC by thermal methods. A few instruments provide real-time OC, EC, and organic speciation. BC and EC concentrations from continuous instruments are highly correlated but the concentrations differ by a factor of two or more. Site- and season-specific mass absorption efficiencies are needed to convert light absorption to BC. Particle mass spectrometers, although semiquantitative, provide much information on particle size and composition related to formation, growth, and characteristics over short averaging times. Efforts are made to quantify mass by collocating with other particle sizing instruments. Common parameters should be identified and consistent approaches are needed to establish comparability among measurements.     

Biodegradation of crystal violet by a Shewanella sp. NTOU1

A bacterial isolate, strain NTOU1, originally isolated from the cooling system in an oil refinery could decolorize and detoxify crystal violet under anaerobic conditions. The strain was characterized and identified as a member of Shewanella decolorationis based on Gram staining, morphology characters, biochemical tests, the 16S rRNA gene and the gyrase subunit beta gene (gyrB). The optimum pH value and temperature for decolorization of crystal violet by this strain under anaerobic conditions were pH 8-9 and 30-40 degrees C, respectively. Formate (20 mM) was the best electron donor. Addition of ferric citrate did not inhibit decolorization of crystal violet, the addition of thiosulfate, ferric oxide, or manganese oxide slightly decreased decolorization, while addition of nitrite (20 mM) inhibited the decolorization of crystal violet. By supplementing the medium with formate and ferric citrate and cultivating it under optimum pH and temperature, this strain could remove crystal violet, at a concentration of 1500 mg l(-1), at the rate of 298 mg l(-1) h(-1) (during decolorization the OD(600) of the cell culture increased from approximately 0.6 to approximately 1.2). GC/MS analysis of the degradation products of crystal violet detected the presence of N,N'-bis(dimethylamino) benzophenone (Michler's Ketone), [N,N-dimethylaminophenyl] [N-methylaminophenyl] benzophenone, N,N-dimethylaminobenzaldehyde, N,N-dimethylaminophenol, and 4-methylaminophenol. These results suggest that crystal violet was biotransformed into N,N-dimethylaminophenol and Michler's Ketone prior to further degradation of these intermediates. This paper proposes a probable pathway for the degradation of crystal violet by this Shewanella sp. Cytotoxicity and antimicrobial tests showed that the process of decolorization also detoxify crystal violet.     

环保标识与区域性可持续发展评估

从“商品环境影响评估”的角度,探讨环境标识与可持续发展的因果关系。世界各地现已因应环境保法例及商品的市场需求,循“品质圈”的模式革新产品。虽然生命周期评价（ＬＣＡ）是环保标识的重要支柱,可惜迄今对估并需强化它在环境安全与健康资源运用、公众咨询、环境管理和审核（ＥＭ＆Ａ）、环境补偿和生态修复等重要领域的工作,确立它在区域性可持续发展中的战略作用。文章以香港为例案,探讨推动环境标识所面对的困难和解决方     

整全,互动和可持续的EIA：香港上水屠宰场的例案研究

以香港上水屠宰场的ＥＩＡ为例,阐述了ＥＩＡ过程须结合“清洁工艺”、“环境管理系统”、“持续生的本底监测”和“开放的公众咨询”四个重要单元,互动灵活,以增强环保效益、省时及经济。传统的ＥＩＡ较为被动,如果项目“倡议人”缺乏环保意识,就会妨碍了它的实质功能。通行的末期性公众咨询,很容易激发冲突,与西方冗长的公众参与同样妨碍进度。文章探讨互动式ＥＩＡ的优点,论证它对改善环评工序和可持续发展的重要性。     

UASB和EGSB反应器中厌氧颗粒污泥生物学特性的比较

测定了实验室规模的２Ｌ ＥＧＳＢ和ＵＡＳＢ反应器中培养的厌氧颗粒污泥在不同基质中的比产甲烷活性、辅酶Ｆ４２０含量和胞外多聚酶物含量,结果表明,ＥＧＳＢ反应器颗粒污泥在葡萄糖上的比产甲烷活性、利用乙酸的甲烷菌和产氢产乙酸菌的活怀和胞外多聚物／含量高于ＵＡＳＢ反应器颗粒污泥,而ＵＡＳＢ反应器颗粒污泥中利用甲酸和氢的甲烷菌的活性以及辅酶Ｆ４２０的含量较ＥＧＳＢ反应器颗粒污泥更高,辅酶Ｆ４２０可以指示同种     

Biofiltration of trimethylamine, dimethylamine, and methylamine by immobilized Paracoccus sp. CP2 and Arthrobacter sp. CP1

A biofilter using granular activated carbon with immobilized Paracoccus sp. CP2 was applied to the elimination of 10–250 ppm of trimethylamine (TMA), dimethylamine (DMA), and methylamine (MA). The results indicated that the system effectively treated MA (>93%), DMA (>90%), and TMA (>85%) under high loading conditions, and the maximum degradation rates were 1.4, 1.2, and 0.9 g-N kg⁻¹ GAC d⁻¹. Among the three different amines treated, TMA was the most difficult to degrade and resulted in ammonia accumulation. Further study on TMA removal showed that the optimal pH was near neutral (6.0–8.0). The supply of high glucose (>0.1%) inhibited TMA removal, maybe due to substrate competition. However, complete TMA degradation was achieved under the co-immobilization of Paracoccus sp. CP2 and Arthrobacter sp. CP1 (96%). Metabolite analysis results demonstrated that the metabolite concentrations decreased by a relatively small 27% while the metabolite apparently increased by heterotrophic nitrification of Arthrobacter sp. CP1 in the co-immobilization biofilter.