Determination of gaseous semi- and low-volatile organic halogen compounds by barrier-discharge atomic emission spectrometry

A group parameter approach using "total organic halogen" is effective for monitoring gaseous organic halogen compounds, including fluorine, chlorine, and bromine compounds, generated from combustion. We described the use of barrier-discharge radiofrequency- helium-plasma/atomic emission spectrometry, for the detection of semi- and low-volatile organic halogen compounds (SLVOXs), which can be collected by Carbotrap TM adsorbents and analyzed using thermal desorption. The optimal carrier gas flow rates at the injection and desorption lines were established to be 100 mL/min. The detection range for SLVOXs in the gaseous samples was from 10 ng to tens of micrograms. Measuring F was more difficult than measuring Cl or Br, because the wavelength of F is close to that of air. The barrier- discharge radiofrequency-helium-plasma/atomic emission spectrometry measured from 85% to 103% of the SLVOXs in the gas sample. It has been found that Carbotrap B is appropriate for high-boiling-point compounds, and Carbotrap C is suitable for the determination of organic halogen compounds with lower boiling points, in the range 200-230°C. Under optimal analysis conditions, a chlorine- containing plastic was destroyed using different oxygen concentrations. Lower oxygen concentrations resulted in the production of lower amounts of organic halogen compounds.     

热脱附气相色谱质谱法测定空气中萜烯有机物

采用自动热脱附(ATD)和气相色谱质谱(GC/MS)联用技术,研究并建立了空气中11种萜烯有机物的测试方法。采用吸附剂Tenax TA进行吸附捕集时,α-蒎烯、莰烯、β-蒎烯极易发生穿透现象,三者的穿透率超过60%;与Tenax TA相比,吸附剂Carbopack B/CarbosieveTMS-Ⅲ可有效抑制萜烯有机物的穿透行为。ATD优化的操作参数为:一级脱附温度和时间分别选择为260℃和10 min,冷肼温度为-20℃,二级热脱附温度和时间分别为280℃和5 min。该方法测试结果准确,重现性和稳定性较好,方法的加标回收率为89%¹12%,相对标准偏差(RSD)小于11%。将该法用于室内空气中萜烯类有机物的测试,发现不同空气样品中均含有多种萜烯有机物,其总量约占总挥发性有机物(TVOC)的15%112%,相对标准偏差(RSD)小于11%。将该法用于室内空气中萜烯类有机物的测试,发现不同空气样品中均含有多种萜烯有机物,其总量约占总挥发性有机物(TVOC)的15%⁶5%,出现几率较大的有α-蒎烯、β-蒎烯、香叶烯、蒈烯、柠檬烯和柏木烯,松油醇较少出现。     

广州大气挥发性有机物的臭氧生成潜势及来源研究

2008年秋季在广州城区及其下风向沿海乡村地区采用活性炭吸附管采集大气挥发性有机化合物(VOC),应用二次热解吸-GC/MS联用技术测量56种VOC的大气浓度,研究在典型海陆风条件下VOC的组成特征和日变化规律,并采用臭氧最大增量及OH自由基反应活性两种方法估算了该地区各VOC的臭氧生成潜力,探讨了VOC优先控制物种及...     

城市污水处理厂挥发性卤代有机物的排放特征及影响因素研究

建立液氮浓缩采样/热解析脱附/GC/MS联用分析方法,测量了广州猎德污水处理厂6个不同处理单元及2个周边环境点中挥发性卤代有机物的组分及含量水平,研究了其排放特征及影响因素.结果表明,8个采样点共检测出19种挥发性卤代有机物,包括11种卤代烷烃、3种卤代烯烃及3种卤代芳香烃、2种卤代酸酯等,平均检出浓度范围为n.d.～33.39μg·m-3,总浓度均值范围为34.91～127.74μg·m-3·CH2Cl2、CHCl3、CFC-12、C2H4Cl2、CFC-11、C2HCl3、C2Cl4是污水处理厂主要的挥发性卤代有机物,它们主要由污水中相应物质挥发而来.脱水机房挥发性卤代有机物浓度最高,提升泵房次之,污泥浓缩池最低;研究还发现,提升泵房、曝气池及生化池的挥发性卤代有机物排放过程中受温度、湿度因素影响明显.     

被动式采样器在大区域大气VOC监测中的应用

应用VOC被动式采样器监测了地中海东部塞浦路斯岛大气中挥发性有机化合物(volatile organic compounds,VOC)的浓度。通过岛上设置的80个VOC采样点对苯,甲苯,对、邻、间二甲苯(Benzene、Toluene、o-xylene、m,p-xylene,BTX)数次采样及分析结果表明,其被动采样器中BTX回收率>95%,BTX平行实验的相对标准偏差<6.28%,采样和分析方法准确。得到的污染物分布图较准确地反映了塞浦路斯岛实际污染情况。     

In-vehicle VOCs composition of unconditioned, newly produced cars

The in-vehicle volatile organic compounds （VOCs） concentrations gains the attention of both car producers and users. In the present study, an attempt was made to determine if analysis of air samples collected from an unconditioned car cabin can be used as a quality control measure. The VOCs composition of in-vehicle air was analyzed by means of active sampling on Carbograph 1TD and Tenax TA sorbents, followed by thermal desorption and simultaneous analysis on flame ionization and mass detector （TD-GC/FID-MS）. Nine newly produced cars of the same brand and model were chosen for this study. Within these, four of the vehicles were equipped with identical interior materials and five others differed in terms of upholstery and the presence of a sunroof; one car was convertible. The sampling event took place outside of the car assembly plant and the cars tested left the assembly line no later than 24 hr before the sampling took place. More than 250 compounds were present in the samples collected; the identification of more than 160 was confirmed by comparative mass spectra analysis and 80 were confirmed by both comparison with single/multiple compounds standards and mass spectra analysis. In general, aliphatic hydrocarbons represented more than 60% of the total VOCs （TVOC） determined. Depending on the vehicle, the concentration of aromatic hydrocarbons varied from 12% to 27% of total VOCs. The very short period between car production and sampling of the in-vehicle air permits the assumption that the entire TVOC originates from off-gassing of interior materials. The results of this study expand the knowledge of in-vehicle pollution by presenting information about car cabin air quality immediately after car production.     

中国涂料应用过程挥发性有机物的排放计算及未来发展趋势预测

基于各行业的涂料当前消费量和未来消费预测,以及各行业使用涂料的挥发性有机物(VOC)含量,建立了分省、分行业、分化学组分的排放清单模型,获得2005~2020年中国涂料应用过程的VOC排放清单.结果表明,2005年,我国涂料应用共排放VOC约1 883 kt,以苯系物、醇、酯、醚、酮5类化合物为主,平均增量反应活性指标(以O3/VOC计)约为3.6 g/kg,其中31%的VOC为有毒物质.如不加强控制,到2020年该部门VOC排放量将激增至5 673 kt;因此,国家应及时开展其排放控制行动.排放控制情景分析表明,通过提高涂料产品品质达到发达国家上世纪末水平,且要求新建规模企业安装有机废气末端处理设施,2020年该部门VOC排放量可控制在3 519 kt;通过进一步将建筑涂料和木器涂料改进到当前欧美发达国家先进水平,且规模企业均安装有机废气末端处理设施,2020年该部门VOC排放量有可能控制在2 243 kt.2种控制情景下所排放VOC的化学毒性和大气氧化活性均得到了有效改善.     

基于树种蓄积量的中国森林VOC排放估算

以中国森林优势树种为对象,应用《全国森林资源统计》提供的林分优势树种蓄积量资料和Guenther提出的光温影响模型,估算各优势树种的VOC排放量,建立了中国森林生态系统的VOC排放清单,并探讨了森林源VOC在不同时空和不同龄级林分中的分配规律.结果表明,中国森林VOC总排放量为8 565.76 Gg,其中异戊二烯5 689.38 Gg(66.42%),单萜烯1 343.95 Gg(15.69%),其他VOC 1 532.43 Gg(17.89%);不同树种的VOC排放量差异较大,栎类、云杉、马尾松等为主要贡献树种,贡献率分别为45.22%、6.34%和5.22%;西南和东北地区为中国森林VOC主要排放区域,云南、四川、黑龙江、吉林、陕西5省排放最多,分别占全国总量的15.09%、12.58%、10.35%、7.49%和7.37%;森林VOC排放存在非常强的季节性变化,夏季排放量最大,占全年的56.66%;不同龄级林分对VOC排放的贡献有所不同,中龄林贡献最多,占森林排放总量的38.84%.     

Determining indoor air quality and identifying the origin of odour episodes in indoor environments

A methodology for identifying volatile organic compounds (VOC) and determining air quality of indoor air has been developed. The air samples are collected using pump samplers by the inhabitants when they perceive odorous and/or discomfort episodes. Glass multi-sorbent tubes are connected to the pump samplers for the retention of VOC. The analysis is performed by automatic thermal desorption (ATD) coupled with gas chromatography-mass spectrometry (GC/MS). This methodology can be applied in cases of sick building syndrome (SBS) evaluation, in which building occupants experience a series of varied symptoms that appear to be linked to time spent in the building. Chemical pollutants concentrations (e.g., VOC) have been described to contribute to SBS. To exemplify the methodology, a qualitative determination and an evaluation of VOC present were performed in a dwelling where the occupants experienced the SBS symptoms. Higher total VOC (TVOC) value was detected in episodes in indoor air (1.33 ( 1.53 mg/m3) compared to outdoor air (0.71 ( 0.46 mg/m3). The concentrations of individual VOCs, such as ethanol, acetone, isopropanol, 1-butanol, acetic acid, acetonitrile and 1-metoxy-2-propanol, were also higher than the expected for a standard dwelling. The external source of VOC was found to be a not declared activity of storage and manipulation of solvents located at the bottom of a contiguous building.     

Adsorption of benzene, cyclohexane and hexane on ordered mesoporous carbon

Ordered mesoporous carbon(OMC) with high specific surface area and large pore volume was synthesized and tested for use as an adsorbent for volatile organic compound(VOC)disposal. Benzene, cyclohexane and hexane were selected as typical adsorbates due to their different molecular sizes and extensive utilization in industrial processes. In spite of their structural differences, high adsorption amounts were achieved for all three adsorbates, as the pore size of OMC is large enough for the access of these VOCs. In addition, the unusual bimodal-like pore size distribution gives the adsorbates a higher diffusion rate compared with conventional adsorbents such as activated carbon and carbon molecular sieve. Kinetic analysis suggests that the adsorption barriers mainly originated from the difficulty of VOC vapor molecules entering the pore channels of adsorbents. Therefore, its superior adsorption ability toward VOCs, together with a high diffusion rate, makes the ordered mesoporous carbon a promising potential adsorbent for VOC disposal.     

Adsorption of benzene,cyclohexane and hexane on ordered mesoporous carbon

Ordered mesoporous carbon (OMC) with high specific surface area and large pore volume was synthesized and tested for use as an adsorbent for volatile organic compound (VOC) disposal. Benzene, cyclohexane and hexane were selected as typical adsorbates due to their different molecular sizes and extensive utilization in industrial processes. In spite of their structural differences, high adsorption amounts were achieved for all three adsorbates, as the pore size of OMC is large enough for the access of these VOCs. In addition, the unusual bimodal-like pore size distribution gives the adsorbates a higher diffusion rate compared with conventional adsorbents such as activated carbon and carbon molecular sieve. Kinetic analysis suggests that the adsorption barriers mainly originated from the difficulty of VOC vapor molecules entering the pore channels of adsorbents. Therefore, its superior adsorption ability toward VOCs, together with a high diffusion rate, makes the ordered mesoporous carbon a promising potential adsorbent for VOC disposal.     

大气中挥发性有机物在线监测系统

一种新型的监测大气中挥发性有机物（包括含氧挥发性有机物）的在线监测系统被研制,即将超低温冷阱捕集-热解析装置与气相色谱-质谱仪联用.其分析方法是大气样品经除水、除O3后以60 mL·min-1的流速通过温度为-150℃的超低温冷阱捕集5min,然后样品在110℃下解析后进入GC-FID/MS系统进行分析,时间分辨率为1h.系统使用混和标气进行标定.目标化合物定量曲线的R2值为0.9137~0.9998,相对标准偏差(RSD)均小于10%.将系统与相关商业化的VOC在线监测仪器进行比对,对于相同目标化合物进行分析,其相关系数r在0.7412~0.9620之间.     

室内空气中芳香烃的测定与污染源模拟

采用Ｔｅｎａｘ树脂吸附－热解吸／氢火焰气相色谱法定量测定室内空气中芳香烃类有机的。现场采样测定了某办公楼装修前后室内空气环境中芳香烃浓度。     

北京市安定生活垃圾填埋场VOCs恶臭物质及其臭气强度

挥发性有机物(VOCs)是填埋场重要的恶臭源之一.为了深入了解造成填埋场恶臭的VOCs及其臭气强度情况,在2014年7—8月采用固相微萃取(SPME)-气相色谱(GC)-质谱(MS)联用法测定了北京市安定生活垃圾卫生填埋场内各代表性地点的VOCs.共确认了48种化合物,包括烷烃、烯烃、芳香烃、环烷烃、萜类、酯类、醛酮类、卤代烃、醇类及含硫化合物和含氮化合物.烷烃的种类最多,达到13种,其次是芳香烃,为9种.以内标法和外标法相结合测定了其中35种物质的含量,发现浓度在0.05~40 mg·m~(-3)之间.在厂区入口和作业面浓度最高的VOC是2,2,4,6,6-五甲基庚烷,在沼气干管是甲苯.从实际经验和臭气强度出发,建立了一种恶臭物质筛选方法,即首先以检出频次和各地点浓度比值筛选出可能的恶臭物质,然后由臭气强度确定最终的恶臭物质.筛选结果表明,填埋场内的恶臭VOCs是对伞花烃、对二甲苯、乙苯、甲苯和邻二甲苯,其中对伞花烃和对二甲苯对恶臭贡献尤为显著.这些恶臭VOCs浓度之间呈现出显著的相关关系,表明这些物质均来源于填埋场内生活垃圾的降解过程.     

河南省某典型垃圾焚烧发电厂的VOCs排放特征

为评估河南省生活垃圾焚烧发电厂排放的挥发性有机物(VOCs)对臭氧生成的贡献,选取某典型企业进行调研. 采用气袋、苏玛罐和吸附管进行采样,通过气质联用(GC/MS)和高效液质(HPLC/MS)联用分析方法对117种VOCs物种排放水平进行监测,并计算本地化VOCs排放因子. 采用最大增量反应活性(MIR)法计算臭氧生成潜势(OFP),并识别OFP贡献率较大的物种. 结果表明:①主排放口实测的VOCs总浓度为4.28 mg/m3,VOCs排放量为3.5 t/a,计算的VOCs排放因子为0.016 g/kg (以垃圾计,下同). ②MIR系数法计算的有组织OFP总排放量为9.3 t/a,对应的MIR系数平均值为2.67. ③排放量占比较大的VOCs组分依次为芳香烃(38.37%)、卤代烃(28.79%)、含氧化合物(14.32%)和烷烃(12.75%). 对OFP贡献率较大的VOCs组分为芳香烃(53.91%)和含氧化合物(28.16%),OFP贡献率排名前5位的VOCs物种分别为乙醛(20.5%)、间/对-二甲苯(20.2%)、正丁烯(6.2%)、1,2,4-三甲苯(5.4%)和正丁醛(4.9%). ④固废间、锅炉房、锅炉房外、渗滤液泵房及房顶采样点测得的VOCs无组织排放总浓度分别为83.6、6.19、1.24、5.71、1.79 mg/m3. 研究显示,该垃圾焚烧发电厂固废间VOCs浓度较高,需要进一步提高车间内VOCs收集率,以减少无组织VOCs排放,同时可在主排放口安装合适的VOCs去除装置以进一步削减VOCs有组织排放量.      

Surface microlayer enrichment of volatile organic compounds and semi-volatile organic compounds in drinking water source

Enrichment of volatile organic compounds(VOC) and semi-volatility organic compounds(SVOC) in surface microlayer(SM) of three ddnking water sources were studied. The enrichment factor(EFs) were 0.67 to 13.37 and 0.16 to 136, respectively. The results showed some VOC and most SVOC could enrich in SM. Some EFs of SVOC was quite high. Suspension and temperature could affect EFs of SVOC, slim wind and water movement do not destroy enrichment of organic in SM.     

挥发性有机物泄漏检测与修复技术经验研究

近年来挥发性有机物的泄漏检测及有效修复越来越受环保重视,介绍了挥发性有机物泄漏检测与修复技术,详细分析了检测过程中的实施经验,结合实际经验对现存现场检测中排放源遗漏、挂牌、检测及复测、泄漏检测介质的选择、人员、泄漏量统计及控制标准等问题进行了探讨.提出了对该项技术今后的展望,化工类企业可通过泄漏和逸散排放的检测以及相关管理体制的建立有效查找泄漏并及时修复.     

粤港澳地区大气中有机污染物初步研究

用Ｔｅｋｍａｒ多填层吸附管连接ＴＭＰ－１５００空气采样采集ＶＯＣｓ样,然后在Ｔｅｋｍａｒ６０３２／３０００吹扫捕集系统与ＧＣ／ＭＳＤ联用仪上分析,用ＴＨ－１０００Ｌ型大量采样器收集ＴＳＰ气溶胶样,ＴＳＰ滤膜经抽提分离后,烷径和芳烃进行ＧＣ／ＭＳＤ分析,了广州,香港和澳门地区大气 有机物和气溶胶可溶有机物的与成因。     

Spatially resolved monitoring for volatile organic compounds using remote sector sampling

Sector sampling for volatile organic compounds (VOCs) is conducted within an integrated sampling scheme and relies on a wind direction sensor. The wind sensor directs whole air, sampled at a constant rate, into either an “IN” sector canister or an “OUT” sector canister; when the wind comes from the suspected emissions area, sample is routed into the IN sector canister; otherwise, sample is collected in the OUT sector canister. This method is analogous to “upwind/downwind” sampling but does not require two distinct sites or manual sampler control. For this set of experiments, the IN and OUT sectors were 90 and 270°, respectively, and the IN sector was centered on the VOC source. Two sampling sites were used. The first was about 2 miles north-northeast of a group of industrial facilities, and the second was located about 1 mile south-southeast of the same sources. Sites were operated concurrently with one sampler each; a third sampler was rotated between the sites to obtain duplicate samples. The air samples were analysed by gas chromatography for VOCs. The resultant data comparisons between IN and OUT duplicate samples show good correlation with expected VOC emissions, which were determined by grab samples within the target area. A t-test method for interpreting the sometimes subtle differences between IN and OUT sample data is presented.     

Characterization of odorous charge and photochemical reactivity of VOC emissions from a full-scale food waste treatment plant in China

Food waste treatment plants (FWTPs) are usually associated with odorous nuisance and health risks, which are partially caused by volatile organic compound (VOC) emissions. This study investigated the VOC emissions from a selected full-scale FWTP in China. The feedstock used in this plant was mainly collected from local restaurants. For a year, the FWTP was closely monitored on specific days in each season. Four major indoor treatment units of the plant, including the storage room, sorting/crushing room, hydrothermal hydrolysis unit, and aerobic fermentation unit, were chosen as the monitoring locations. The highest mean concentration of total VOC emissions was observed in the aerobic fermentation unit at 21,748.2–31,283.3 μg/m³, followed by the hydrothermal hydrolysis unit at 10,798.1–23,144.4 μg/m³. The detected VOC families included biogenic compounds (oxygenated compounds, hydrocarbons, terpenes, and organosulfur compounds) and abiogenic compounds (aromatic hydrocarbons and halocarbons). Oxygenated compounds, particularly alcohols, were the most abundant compounds in all samples. With the use of odor index analysis and principal components analysis, the hydrothermal hydrolysis and aerobic fermentation units were clearly distinguished from the pre-treatment units, as characterized by their higher contributions to odorous nuisance. Methanthiol was the dominant odorant in the hydrothermal hydrolysis unit, whereas aldehyde was the dominant odorant in the aerobic fermentation unit. Terpenes, specifically limonene, had the highest level of propylene equivalent concentration during the monitoring periods. This concentration can contribute to the increase in the atmospheric reactivity and ozone formation potential in the surrounding air.