Determination of the dialdehyde glyoxal in workroom air-development of personal sampling methodology

The dialdehyde glyoxal (ethanedial) is an increasingly used industrial chemical with potential occupational health risks. This study describes the development of a personal sampling methodology for the determination of glyoxal in workroom air. Among the compounds evaluated as derivatizing agents; N-methyl-4-hydrazino-7-nitrobenzofurazan (MNBDH), 1,2-phenylenediamine (OPDA), 1-dimethylaminonaphthalene-5-sulfonylhydrazine (dansylhydrazine, DNSH) and 2,4-dinitrophenylhydrazine (DNPH), DNPH was the only reagent that was suitable. Several different samplers were evaluated for sampling efficiency of glyoxal in workroom air using DNPH as derivatizing agent; in-house DNPH coated silica particles packed in two different types of glass tubes, impingers containing acidified DNPH solution, filter cassettes containing glass fibre filters coated with DNPH, a commercially available solid phase cartridge sampler originally developed for formaldehyde sampling (Waters Sep-Pak DNPH-silica cartridge), and the commercially available SKC UMEx 100 passive sampler originally developed for formaldehyde sampling. Aldehyde atmospheres for sampler evaluation were generated with an in-house made vapour atmosphere generator coupled to a sampling unit, with the possibility of parallel sampling. The resulting glyoxal-DNPH derivative was determined using both LC-UV and LC-APCI-MS with negative ionization. By far, the highest recovery of glyoxal was obtained employing one of the in-house DNPH coated silica samplers (93%, RSD = 3.6%, n = 12).     

Determination of acrylic acid in air by using diffusion denuder tubes combined with HPLC technique

A procedure for the determination of atmospheric acrylic acid in air at the microgram m-3 to mg m-3 level is described. Diffusion-based sampling, designed to discriminate gaseous analytes from their particulate counterparts, has been used. Acrylic acid is collected with an efficiency of > 98% in tubular denuders coated with sodium hydroxide-barium hydroxide-hydroquinone monomethyl ether, and analyzed by high performance liquid chromatography with UV absorbance detection. The detection limit is 2.9 micrograms m-3 at a flow rate of 0.5 L min-1 and 30 min sampling time. A precision (p = 0.95, n = 10) of 7.5% of the overall procedure was achieved at the 100 micrograms m-3 level. Results of laboratory studies concerning the effect of the coating reagent and the relative humidity on the sampling efficiency as well as possible interferences, in particular by ozone, and the elimination of these interferences are discussed. This method was developed to monitor workplace atmospheres as well as ambient air in industrial environments.     

Air exposure assessment and biological monitoring of manganese and other major welding fume components in welders

In a cross-sectional study, 96 welders were compared with 96 control subjects. Also 27 former welders, all diagnosed as having manganism, were examined. Exposure to welding fumes was determined in the 96 welders, while the concentration of elements in whole blood and urine was determined in all subjects. The geometric mean (GM) concentrations of manganese (Mn) and iron in the workroom air were 97 microg m(-3) (range 3-4620 microg m(-3); n=188) and 894 microg m(-3) (range 106-20 300 microg m(-3); n=188), respectively. Thus the Mn concentration in the workroom air was on average 10.6% (GM) of that of the Fe concentration. No substantial difference was observed in the air Mn concentrations when welding mild steel as compared to welding stainless steel. The arithmetic mean (AM) concentration of Mn in whole blood (B-Mn) was about 25% higher in the welders compared to the controls (8.6 vs. 6.9 microg l(-1); p < 0.001), while the difference in the urinary Mn concentrations did not attain statistical significance. A Pearson's correlation coefficient of 0.31 (p < 0.01) was calculated between B-Mn and Mn in the workroom air that was collected the day before blood sampling. Although the exposure to welding fumes in the patients had ceased on average 5.8 years prior to the study (range 4 years-7 years), their AM B-Mn concentration was still higher than in referents of similar age (8.7 microg l(-1) vs. 7.0 microg l(-1)). However, their urinary concentrations of cobolt, iron and Mn were all statistically significantly lower.     

Development of active and diffusive sampling methods for determination of 3-methoxybutyl acetate in workplace air

Monitoring of the workplace concentration of 3-methoxybutyl acetate (MBA), which is used in printer's ink and thinner for screen-printing and as an organic solvent to dissolve various resins, is important for health reasons. An active and a diffusive sampling method, using a gas chromatograph equipped with a flame ionization detector, were developed for the determination of MBA in workplace air. For the active sampling method using an activated charcoal tube, the overall desorption efficiency was 101%, the overall recovery was 104%, and the recovery after 8 days of storage in a refrigerator was more than 90%. For the diffusive sampling method using the 3M 3500 organic vapor monitor, the MBA sampling rate was 19.89 cm(3) min(-1). The linear range was from 0.01 to 96.00 microg ml(-1), with a correlation coefficient of 0.999, and the detection limits of the active and diffusive samplers were 0.04 and 0.07 microg sample(-1), respectively. The geometric mean of stationary sampling and personal sampling in a screen-printing factory were 12.61 and 16.52 ppm, respectively, indicating that both methods can be used to measure MBA in workplace air.     

A diffusive sampling device for the determination of formaldehyde in air using N-methyl-4-hydrazino-7-nitrobenzofurazan (MNBDH) as reagent

A new method utilizing the diffusive sampling of formaldehyde in air has been developed. Formaldehyde is sampled with the use of a glass fiber filter impregnated with N-methyl-4-hydrazino-7-nitrobenzofurazan (MNBDH) and phosphoric acid. The formaldehyde hydrazone formed is desorbed from the filter with acetonitrile and determined by high-performance liquid chromatography (HPLC) with UV/visible detection at 474 nm. The sampling rate was determined to be 24.7 mL min-1 with a relative standard deviation of 7% for 48 experiments. The measured sampling rates were not dependent on the formaldehyde concentration (0.1-1.0 mg m-3), sampling time (15-482 min) or relative humidity (20-85%). The detection limit was 70 micrograms m-3 for a 15 min sampling period and 2 micrograms m-3 for an 8 h sampling period.     

Estimation of required monitoring time for obtaining validation data in enclosed spaces

Methods for estimating airborne contaminant concentrations at specific locations within enclosed spaces, such as mathematical models and computational fluid dynamics (CFD), often are validated against directly measured concentrations. However, concentration variation with time introduces uncertainty into the measured concentration. Failure to determine monitoring time requirements can lead to errors in quantifying representative concentrations, which are likely to be attributed to errors in the method being validated. In the current study, to obtain the representative concentrations at multiple locations with a direct reading instrument, we used the standard deviation ratio (SDR) method to determine the required minimum monitoring time within a specified precision limit. To demonstrate the use of the SDR approach in constructing precision confidence intervals, tracer gas concentrations at nine sampling locations in an experimental room were measured to obtain population parameters. Three flow rates of 0.9, 3.3 and 5.5 m(3) min(-1) were employed and contaminant concentrations were measured using a photoionization analyser. Monitoring time requirements varied substantially with location within the room and were strongly dependent upon the flow rate of air through the room. The proposed method would be very useful for industrial hygienists and indoor air researchers who sometimes need to obtain several hundred measured concentrations for validation purposes or to perform tests under repeatable conditions in enclosed spaces. This study also showed that the proposed method can be used to devise efficient indoor monitoring strategies.     

工业温室气体CO2排放监测技术前期研究

介绍了国内外二氧化碳（ CO2）气体检测方法,选取红外传感器、非分散红外和气相色谱3种方法监测工业燃煤废气中的CO2。试验结果表明,3种方法的精密度和准确度均满足要求;单一燃煤废气中CO2的体积分数范围为6．70％～15．10％,同一排气筒中CO2体积分数5 min的波动范围为0～22．4％;同一排气筒（单一燃煤废气）中CO2和O2的体积分数有一定的关联性,二者之和基本稳定在19％～21％范围;非分散红外法和气相色谱法测定同一样品的相对偏差为0．9％～3．4％;红外传感器适用于有组织排放的现场监测,另2种方法适用于无组织废气和环境空气监测。     

利用SPAMS研究长沙市秋季PM2.5化学组成及来源

2019年10月12日—11月25日,使用单颗粒气溶胶飞行时间质谱仪(SPAMS)在位于长沙市的湖南省生态环境厅点位进行了为期45 d的定点监测。结果表明,监测期间长沙市总体空气质量小时级别优、良天气占比为80.3%。长沙市首要污染物为PM_(2.5),其主要来源为机动车尾气源,二次无机源次之,工业工艺源排在第三位,占比分别为27.4%,21.5%和17.4%。整体来看,监测期间PM_(2.5)质量浓度的升高大多伴随着以上3种污染源颗粒物的同步升高。机动车尾气源具有明显的早高峰,工业工艺源、生物质燃烧源和餐饮源夜间占比增加。在偏东方向气团主导下,工业工艺源和燃煤源贡献最大;在东北方向气团主导下,PM_(2.5)质量浓度最高,且机动车尾气源占比最高。     

重庆市代表性城区冬季和夏季苯系物来源解析

2009—2010年冬季和夏季在重庆市某代表性城区对大气中苯系物进行观测,并应用苯与甲苯特征比值(B/T)和因子分析法对苯系物来源进行了分析。结果表明,2种源分析方法具有较好的一致性,涂料及溶剂的生产与使用以及机动车尾气和油品使用是该研究区域苯系物的主要来源,贡献率分别为59.3%和16.2%。不同功能区、不同季节,苯系物来源构成有所差异。除受汽车尾气影响外,夏季受涂料、溶剂等生产使用的影响也较大,尤其是投诉集中点位、混合区和工业区;冬季,投诉集中点位主要受涂料、溶剂等生产使用等影响,其他点位可能还受到燃烧源的影响。     

可伸缩延长气体采样装置在应急监测中的应用

提出了一种可伸缩延长气体采样装置,并将其与现场气体监测仪器配套使用。初步考察了延长采样装置中Teflon采样管长度对现场监测结果可能产生的影响,并对监测站实验室楼顶废气排出筒气体进行了实际样品监测。结果表明,该装置可有效提高现场应急监测的安全防护保障效果,增加可监测区域范围,使现场应急监测工作能够为突发性环境污染事件的处置提供更多技术支持。     

环境在线监测监控管理与发布系统

阐述了省级环境在线监测监控管理与发布系统的组成及功能特点,介绍了采用GPRS无线数据传输方式,对水、气、污染源等环境在线监测自动化系统进行数据采集、统计与GIS发布的实现方式,指出其具有传输速率高、延时小、实时性强、建设方便、费用低廉等显著优点。     

Seasonal variation, risk assessment and source estimation of PM 10 and PM10-bound PAHs in the ambient air of Chiang Mai and Lamphun, Thailand

Daily PM10 concentrations were measured at four sampling stations located in Chiang Mai and Lamphun provinces, Thailand. The sampling scheme was conducted during June 2005 to June 2006; every 3 days for 24 h in each sampling period. The result revealed that all stations shared the same pattern, in which the PM10 (particulate matters with diameter of less than 10 microm) concentration increased at the beginning of dry season (December) and reached its peak in March before decreasing by the end of April. The maximum PM10 concentration for each sampling station was in the range of 140-182 microg/m(3) which was 1.1-1.5 times higher than the Thai ambient air quality standard of 120 microg/m(3). This distinctly high concentration of PM10 in the dry season (Dec. 05-Mar. 06) was recognized as a unique seasonal pattern for the northern part of Thailand. PM10 concentration had a medium level of negative correlation (r = -0.696 to -0.635) with the visibility data. Comparing the maximum PM10 concentration detected at each sampling station to the permitted PM10 level of the national air quality standard, the warning visibility values for the PM10 pollution-watch system were determined as 10 km for Chiang Mai Province and 5 km for Lamphun Province. From the analysis of PM10 constituents, no component exceeded the national air quality standard. The total concentrations of PM10-bond polycyclic aromatic hydrocarbons (PAHs) are calculated in terms of total toxicity equivalent concentrations (TTECs) using the toxicity equivalent factors (TEFs) method. TTECs in Chiang Mai and Lamphun ambient air was found at a level comparable to those observed in Nagasaki, Bangkok and Rome and at a lower level than those reported at Copenhagen. The annual number of lung cancer cases for Chiang Mai and Lamphun Provinces was estimated at two cases/year which was lower than the number of cases in Bangkok (27 cases/year). The principal component analysis/absolute principal component scores (PCA/APCS) model and multiple regression analysis were applied to the PM10 and its constituents data. The results pointed to the vegetative burning as the largest PM10 contributor in Chiang Mai and Lamphun ambient air. Vegetative burning, natural gas burning & coke ovens, and secondary particle accounted for 46-82%, 12-49%, and 3-19% of the PM10 concentrations, respectively. However, natural gas burning & coke ovens as well as vehicle exhaust also deserved careful attention due to their large contributions to PAHs concentration. In the wet season and transition periods, 42-60% of the total PAHs concentrations originated from vehicle exhaust while 16-37% and 14-38% of them were apportioned to natural gas burning & coke ovens and vegetative burning, respectively. In the dry period, natural gas burning & coke ovens, vehicle exhaust, and vegetative burning accounted for 47-59%, 20-25%, and 19-28% of total PAHs concentrations. The close agreement between the measured and predicted concentrations data (R(2) > 0.8) assured enough capability of PCA/APCS receptor model to be used for the PM10 and PAHs source apportionment.     

上海浦东国际机场飞机尾气排放对机场附近空气质量的影响

统计2012年10月和11月浦东机场飞机机型和航班架次,根据各类飞机起降的污染物排放设计工作参数,估算出2012年浦东机场飞机起降时排放的NO2、SO2、CO和HC的估算值。利用浦东新区13个空气监测子站二氧化氮和二氧化硫数据绘制等值线图。结果显示,机场所在的江镇点位和祝桥点位二氧化氮浓度变化受飞机影响很大,而飞机排放的二氧化硫对两个点位的影响可以忽略不计。建议采用改进飞机滑行路线、探讨征收飞机碳排放税等措施减少飞机尾气排放对空气质量的影响。     

南通市夏季VOCs污染特征与来源研究

运用大气挥发性有机物(VOCs)快速在线连续自动监测系统,于2018年7月对南通市区环境空气中VOCs进行观测,分析VOCs的浓度状况、组成特征、对臭氧生成潜势的贡献及主要来源。结果表明:观测期间共检出100种VOCs,总挥发性有机物(TVOCs)的平均体积分数为(38. 18±23. 63)×10^-9,各物种体积分数从大到小顺序依次为烷烃>含氧有机物>芳香烃>卤代烃>烯、炔烃;芳烃和烯烃是最主要的活性物种,间/对二甲苯、甲苯、邻二甲苯等是VOCs的关键活性组分;利用PMF模型解析得到VOCs的主要污染来源是工业排放与溶剂使用、机动车尾气排放、燃料挥发排放和生物源排放。     

2021年青岛市一次PM_(2.5)和沙尘混合空气污染过程分析

以2021年3月青岛市空气自动站监测数据为依据,借助环境气象激光雷达、气溶胶激光雷达、在线离子色谱仪等技术手段,并利用后向轨迹模式(HYSPLIT)对青岛市一次PM_(2.5)和沙尘混合空气污染过程、气象条件、颗粒物组成以及传输路径等进行了综合分析。结果表明:静小风、湿度大、垂直方向逆温以及高空多次向近地面的污染物输送是第1阶段PM_(2.5)污染的主要原因,NO^(-)_(3)、SO^(2-)_(4)、NH^(+)_(4)浓度分别占水溶性离子浓度总和的51.7%,24.8%,22.4%,三者之和占ρ(PM_(2.5))的52.3%,机动车源、工业源和燃烧源贡献较大,其中尤以机动车源影响最显著;第2阶段各子站颗粒物浓度变化呈现明显的传输特征,PM_(2.5)中Ca^(2+)浓度升至第1阶段的6倍,沙尘源影响显著,污染气团主要来自蒙古国和我国内蒙古,前期由西北地区直接到达青岛,后期是经渤海湾、烟台到达青岛东南海域,最后回流至青岛;冷高压强度较弱导致近地面水平扩散条件不利,ρ(PM_(10))长时间维持在较高水平。     

典型毒害气体的FTIR吸收光谱分析

傅立叶变换红外(FTIR)光谱技术可以对空气、生物气以及各种工业生产过程中的排气、废气进行实时在线监测。但是由于废气的成分复杂,红外吸收光谱互相干扰、重叠,往往难以辨认。本文用FTIR研究工业废气中主要物质的红外吸收光谱特性,确定光谱分析时废气各组分的特征红外频率。分析对象包括水蒸气、一氧化碳、二氧化碳、氨气、氰化氢、氯化氢、氟化氢、一氧化氮、二氧化氮、二氧化硫、甲醛和丙稀醛十二种物质。     

马鞍山市城区主干道近地面空气质量调查

为调查马鞍山市城区主干道近地面空气质量状况,马鞍山市环境监测中心站于1999年1月19日～1月21日对城区3条主干道的5个监测点近地面空气质量进行了监测.结果表明,在城市整体环境空气质量良好的情况下,交通干道近地面空气污染较严重,主要污染源是机动车尾气,NOx、CO、TSP是特征性污染物,其中NOx平均分布浓度与车流量近似成正相关,从时间分布上看,NOx平均分布浓度早上最高,晚上次之,中午最低.指出,为改善城市的环境空气质量,必须加强对机动车尾气的监督管理.     

铵盐气溶胶对烟气排放连续监测系统颗粒物比对监测的影响研究

利用拉曼光谱对采样后的滤筒进行分析,发现废气中的硫酸铵-硫酸氢铵气溶胶是造成成都市部分企业烟气排放连续监测系统(CEMS)颗粒物比对监测结果不合格的主要原因。通过比较分析得出:在对含硫酸铵-硫酸氢铵气溶胶废气进行颗粒物浓度比对监测时,参比方法(重量法)测定的颗粒物浓度是一定标干采样体积下废气中固体微粒和硫酸铵-硫酸氢铵液体微粒结晶后产生的晶体的总质量,基于光散射法的CEMS颗粒物浓度测试系统测定的颗粒物浓度只是一定标干采样体积下废气中固体微粒的质量,由此导致参比方法测出的颗粒物浓度远大于CEMS测出的浓度,造成比对误差远超出允许值范围。     

24 h diffusive sampling of toxic VOCs in air onto Carbopack X solid adsorbent followed by thermal desorption/GC/MS analysis-laboratory studies

Diffusive sampling of a mixture of 42 volatile organic compounds (VOCs) in humidified, purified air onto the solid adsorbent Carbopack X was evaluated under controlled laboratory conditions. The evaluation included variations in sample air temperature, relative humidity and ozone concentration. Linearity of samples with loading was examined both for a constant concentration with time varied up to 24 h and for different concentrations over 24 h. Reverse diffusion and its increase with accumulation of sample were determined for all compounds. Tubes were examined for blank levels, change of blanks with storage time, and variability of blanks. Method detection limits were determined based on seven replicate samples. Based on this evaluation, 27 VOCs were selected for quantitative monitoring in the concentration range from approximately 0.1 to 4 ppbv. Comparison results of active and diffusive samples taken over 24 h and under the same simulated ambient conditions at a constant 2 ppbv were interpreted to estimate the effective diffusive sampling rates (ml min(-1)) and their uncertainties and to calculate the corresponding diffusive uptake rates (ng ppmv(-1) min(-1)).     

典型化工园区大气中挥发性有机物污染调查

对常州市某典型化工园区大气中挥发性有机物(VOCs)污染状况进行了调查。结果表明,该化工园区大气中检出挥发性有机物共有58种,组分有芳香烃、饱和烷烃、卤代烃、烯烃、醛酯类化合物及其他类;苯、甲苯、乙苯、二甲苯为主要挥发性有机污染物,质量浓度为1.0~194μg/m~3;均未超出参考标准的限值。背景点位和园区点位大气中主要ρ总(VOCs)在秋冬季最高,敏感点大气VOCs随季节变化也较为明显;园区T1和T2ρ总(VOCs)年均值高于敏感点位,背景点位年均值最低;园区点位除了汽车尾气排放之外,溶剂的挥发和生产工艺中污染物的排放也增加了大气中苯系物的浓度,同时也对敏感点位和对照点位的大气质量产生了一定的影响。