汽油车非常规污染物排放特性研究

选择3种不同排量的典型汽油车,基于国Ⅲ标准的轻型车排放测试循环,用SKC采样泵和2, 4-DNPH、Tenax TA采样管采集尾气中的非常规污染物,利用高效液相色谱仪和热脱附气相色谱质谱联用仪分析汽油车排放中醛酮类化合物和挥发性有机物的组成及含量,同时利用电子低压冲击仪研究了其颗粒物排放的粒径和质量浓度分布特征.结果表明,不同汽油车之间非常规污染物的比排放值有较大差异,3辆汽油车总醛酮比排放量分别为36.44、 16.71、 10.43 mg/km,TVOC分别为155.39、 103.75、 42.29 mg/km.排放的醛酮化合物中甲醛、乙醛、丙烯醛、丙酮和环己酮的检出含量较高,占总醛酮量的77.9%～89.7%,且绝大部分为有毒有害物质;废气中挥发性有机物绝大部分为芳香烃和烷烃,分别占总数的31.6%～39.2%和23.1%～27.9%,其中又以芳香烃类化合物甲苯、二甲苯和苯的检出含量最高,平均占TVOC的16.68%、 16.87%和5.23%;其颗粒物排放以超细颗粒物（<100nm）为主,高速工况下排放的颗粒物明显多于低速和中速工况.     

长白山温带森林挥发性有机物的排放通量

2010年夏季,在长白山温带森林开展了挥发性有机物(VOC)排放通量以及气象参数、PAR的综合测量.VOC排放通量采用松弛涡度积累(RelaxedEddyAccumulation)技术在森林冠层上进行测量.初步发现长白山阔叶林主要排放α-蒎烯、β-蒎烯、莰烯、香桧烯、月桂烯、蒈烯、柠檬烯、罗勒烯、松油烯、繖花烃、萜品油烯、三环烯等.研究表明,长白山阔叶混交林VOC排放有明显的日变化——早晚较低和中午前后较高.2010年夏季,单萜烯总排放通量的平均值为0.242mg·m·h-2-1,其变化范围为0.005～1.668mg·m·h-2-1;各成分排放通量的平均值(和最大值)分别为α-蒎烯0.072(0.234)、莰烯0.028(0.356)、月桂烯0.027(0.433)、蒈烯0.023(0.173)、柠檬烯0.037(0.197)、罗勒烯0.016(0.168)、萜品油烯0.053(0.320)、繖花烃0.067(0.755)mg·m·h-2-1.研究还发现VOC排放通量与气温之间存在一定的联系.     

基于GC-MS对原油装卸VOCs组分的研究

挥发性有机物(VOCs)是二次有机气溶胶(SOA)和光化学烟雾的重要前体物,原油装卸VOCs化学成分随原油种类、伴热温度、搅拌速度等的不同而呈现很大差异。本文以伴热温度和搅拌速度为变量,采用Tenax吸附管采样并利用热脱附-气相色谱-质谱法(GC-MS)对原油在不同伴热和搅拌速度下产生的VOCs进行组分分析。根据谱库检索和图谱解析,利用面积归一化的半定量法分析原油VOCs的具体组分。结果表明:通过热脱附GC-MS法分析检测出54种VOCs,其中,含氧有机物19种,含氮硫化合物13种,碳氢化合物22种;碳氢化合物占VOCs总量的44.75%～50.75%,含氧有机物占VOCs总量的29.47%～37.63%,含氮硫化合物占VOCs总量的15.34%～22.63%。     

超市异味VOCs成分分析及健康风险评估

超市食品容易产生异味,导致顾客产生不愉悦的嗅觉感受,这些异味的主要成分是挥发性有机物(Volatile Organic Compounds,VOCs).为确定超市异味VOCs化学成分及其来源,对超市开展现场采样检测.本研究采用3种不同的VOCs采样检测方法:吸附管采样-热脱附-气相色谱/质谱法(TD-GC/MS)、气袋采样-TD-GC/MS和苏玛罐采样-气相色谱-火焰离子化检测/质谱法(GC-FID/MS),对超市室内空气中的VOCs进行采样检测比较.结果表明,苏玛罐采样法的总挥发性有机物(Total Volatile Organic Compounds,TVOC)体积分数为63.3×10^-9～86.8×10^-9,共检测出26种VOCs,主要包括卤代烃、烷烃和苯系物,但异味贡献较小,未检测出异味较大的VOCs;气袋采样法仅检测出9种VOCs,且φ(TVOC)均小于10.0×10^-9,说明气袋存在显著壁吸附效应,不适用于本次实验;吸附管采样法的检测结果显示,φ(TVOC)为79.5×10^-9～86.1...     

京津冀天然源挥发性有机物排放研究

为探明2017年京津冀地区天然源挥发性有机物(BVOCs)的空间分布,将研究区划分成3 km分辨率的格网,并通过WRF模型提供气象驱动数据,MODIS影像提供植被功能类型和叶面积指数,最终利用MEGAN模型进行模拟研究.结果表明,该模型将BVOCs分成147个细类,其中主要有异戊二烯、单萜烯41类、半萜烯32类、其他VOC73类.2017年京津冀地区BVOCs排放总量为426.26×10~3 t,四大类别的排放比例依次为29.38%、12.32%、6.24%、52.05%.单萜烯中排放较高的类别是α-蒎烯、β-蒎烯、t-β-罗勒烯,而半萜烯中排放较高的是α-法呢烯和β-石竹烯.整个研究区域内BVOCs排放较高的区域位于北部森林与灌丛分布密集的燕山山脉和西南的太行山山脉,其中主要的城市有承德、北京、张家口、保定、石家庄等.排放量较低的地区为廊坊、衡水、天津等地.本研究通过模型模拟得到了京津冀地区2017年高时空分辨率BVOCs排放清单,同时可为以后的大气环境研究提供基础数据.     

一品红挥发性有机物释放日变化规律研究

实验采用静态箱式动态吸附采样,利用热脱附——气质联用分析研究了一品红挥发性有机物(VOCs)的组成及含量的日变化规律。检测到八类共49种挥发性有机物,包括烷烃、酮类、醇类、醛类、烯烃、酯类、芳香烃类和其他物质等在内的。其中三氯乙烯,1,1,2,2-四氯乙烷,苯乙酮,枯烯,甲苯,乙苯,萘和邻苯二甲酸二丁酯等8种挥发性有机物为EPA重点控制空气中有害污染物。实验发现,各种物质的释放具有显著的日变化规律,且不同种类物质释放的日变化规律也不同。同时利用LI-6400XT便携式光合仪测量六项生理生态指标,表明这些挥发性有机物的释放与一品红叶片温度(Tleaf)、光合作用有效辐射(Par)、湿度(%)、光合作用速率(Photo)、气孔导度(Cond)和蒸腾速率(Trmmol)存在一定相关性。不同物质的释放规律与这些环境影响因子的相关性有一定差异。     

北京市某家具城室内空气污染水平与特征

为了解家具城室内空气污染状况,于2009年夏采样测定了北京市某家具城多个展区空气中苯系物(苯、甲苯、二甲苯)、总挥发性有机物(TVOC)、甲醛等羰基化合物的浓度.家具城室内空气中甲醛、苯、甲苯、二甲苯和TVOC的总体浓度(均值±标准差)分别为:(0.37±0.08)、(0.04±0.03)、(0.19±0.16)、(0.47±0.57)和(2.76±2.18)mg/m3;甲醛、二甲苯、TVOC的室内浓度分别为室外浓度的22、46和34倍.甲醛、二甲苯、TVOC的平均浓度均超过《室内空气质量标准》所规定的标准值,甲醛、TVOC最高浓度分别是标准值的5.1倍和14.8倍.家具城内羰基化合物总浓度为(689.3±94.8)μg/m3,超过室外浓度5倍,其中甲醛和乙醛的浓度最高,二者浓度之和占羰基化合物总浓度的75%以上;丙酮、4碳羰基化合物(异丁烯醛、甲乙酮、正丁醛)和己醛的浓度也较高.总之,家具城存在严重的室内空气污染.     

天津某家具城挥发性有机物健康风险评估

为了解家具城室内空气中挥发性有机物的污染状况,对其职工进行慢性暴露健康风险评估,于2011年夏(6月)和2012年秋(10月)对天津某家具城进行了空气采样,通过气相色谱-质谱联用仪(GC-MS)分析污染物浓度.分析得出,家具城室内污染物浓度约高出室外1.9倍,以芳香族化合物和卤代烷烃为主,萜烯也占一定比例,特征VOCs为二氯甲烷、甲苯和α-蒎烯;苯系物浓度明显低于《室内空气质量标准》的限值.苯和二氯甲烷的致癌风险分别为1.24×10-5、2.50×10-5,存在潜在的人群致癌风险;VOCs非致癌危害指数之和小于1,在可接受范围内.健康效应分析表明,工龄和心率及肺通气功能不存在偏相关关系.暴露组和对照组尿中苯巯基尿酸(S-PMA)和8-羟基脱氧鸟苷(8-OHdG)的生物监测及分析表明,在低暴露条件下,吸烟是影响S-PMA浓度的重要因素,但在较高暴露条件下,其影响减弱;S-PMA浓度和8-OHdG正相关,与性别、吸烟与否以及年龄有关,还可能与工龄有关.     

大叶黄杨挥发性有机物日变化规律的实验观测

实验针对北京鹫峰地区的灌木——大叶黄杨(Euonymus japonicus Thunb),测定了其挥发性有机物(VOCs)的种类,并研究其VOCs挥发的变化规律。采样方法是主动吸附套袋采样法,分析方法是热脱附-气相色谱-质谱联动的检测方法。通过实验测定得出,大叶黄杨可挥发的有机物包含烯烃、酯、酮、醛、醇、酸6类。同时对白天三个时段的可挥发有机物进行实验测定后可知:随着时间的变化,各种有机物所占质量分数也不相同。3种有毒物质中,α-蒎烯上午含量最高,然后逐渐减少;2-丁醇比例基本稳定;苯乙酮呈增加趋势。一种有益物质柠檬烯随着时间变化,挥发量逐渐增大,且变化较大。     

杭州市居室空气中挥发性有机物污染研究

用气质联用技术和热解吸方法研究杭州居室空气中挥发性有机物的组成。分析结果表明,杭州居室空气中共存在256种VOCs,其中31种属于EPA划定的有毒化合物,71种污染物的检出率>50%;芳烃、烷烃、环烷烃和卤代烃四种污染物的化合物数量百分比之和达56.1%,是杭州居室空气中种类最多的污染物;芳烃、萜、酮、卤代烃、烷烃5类污染物的总含量为TVOC的86.3%,是杭州居室空气中最主要的VOCs。     

Comparison of Tenax Ta and Carbotrap for sampling and analysis of volatile organic compounds in air

Dynamic recovery data with a simple test system show that many volatile organic compounds (VOC) found in trace amounts in air can be determined quantitatively by adsorption on Tenax TA or Carbotrap and thermal desorption. Tenax TA seems to be inert towards the compounds tested as opposed to Carbotrap, on which α-pinene and aldehydes show some reactivity. Compounds with higher boiling points up to 270°C could be quantitatively desorbed from Tenax TA, but not from Carbotrap. For very volatile organic compounds and various polar VOC, substantial losses, most probably due to breakthrough, were observed on both adsorbents. Therefore, for an overview of all VOC in air, additional adsorbents or methods must be considered.     

Reaction of monoterpenes with ozone,sulphur dioxide and nitrogen dioxide—gas-phase oxidation of SO2 and formation of sulphuric acid

Teflon bag experiments were carried out in the dark in order to study the gas-phase reactions of selected monoterpenes with O₃ in the presence of SO₂ (β-pinene) as well as in the presence of SO₂/NO₂ (α-pinene, β-pinene, limonene). Emphasis was given in identifying the main reaction products and in quantifying the H₂SO₄ aerosol formed. Apart from the H₂SO₄ aerosol no other S containing compounds could be detected.It was found that the reaction of β-pinene with O₃, SO₂ and NO₂ leads mainly to 6,6-dimethyl-bicyclo [3.1.1] heptan-2-one (nopinone), the α-pinene-O₃-SO₂-NO₂-reaction produced 2′,2′-dimethyl-3-acetyl cyclobutyl ethanal (pinonaldehyde). The reaction of limonene with O₃-SO₂-NO₂ leads mainly to an unidentified product with a molecular weight M⁺ 134. In addition to the above-mentioned volatile products, the formation of organic nitrates could be established by means of gas chromatography-mass spectrometry.The yield of H₂SO₄ in the system β-pinene/O₃/SO₂ varies between 0.13 and 0.44 depending on the initial conditions, e.g. humidity. In the system terpene/O₃/SO₂/NO₂ the yield of H₂SO₄ for α-pinene (after 1 h reaction time) was 0.01–0.03, for β-pinene (2 or 4 h reaction time) 0.07–0.13 and for limonene (1 h reaction time) 0.02–0.09.     

Removal characteristics and kinetic analysis of an aerobic vapor-phase bioreactor for hydrophobic alpha-pinene

Biofiltration is considered an effective method to control volatile organic compounds (VOCs) pollution. This study was conducted to evaluate the potential use of a bacterial biofilter packed with wood chips and peat for the removal of hydrophobic α-pinene. When inoculated with two pure degraders and adapted activated sludge, a removal efficiency (RE) of more than 95% was achieved after a start-up period of 11 days. The maximum elimination capacity (EC) of 50 g/(m³. hr) with RE of 94% was obtained at empty bed retention time (EBRT) of 102 sec. When higher α-pinene concentrations and shorter EBRTs were applied, the REs and ECs decreased significantly due to mass-transfer and biological reaction limitations. As deduced from the experimental results, approximately 74% of α-pinene were completely mineralized by the consortiums and the biomass yield was 0.60 g biomass/g α-pinene. Sequence analysis of the selected bands excised from denaturing gradient gel electrophoresis revealed that the inoculated pure cultures could be present during the whole operation, and others were closely related to bacteria being able to degrade hydrocarbons. The kinetic results demonstrated that the whole biofiltration for α-pinene was diffusion-limit controlled owing to its hydrophobic characteristics. These findings indicated that this bacterial biofiltration is a promising technology for the remediation of hydrophobic industrial waste gases containing α-pinene.     

1株α-蒎烯降解菌的分离鉴定及降解特性研究

从处理废气的生物滤塔内筛选到1株能高效降解α-蒎烯的菌株PT.通过菌落形态、生理生化特征、16SrRNA基因序列相似性分析及Biolog鉴定等方法,确定该菌株属于荧光假单胞菌(Pseudomonas fluorescens).菌株PT最佳生长条件为: NaCl浓度0.00%、pH7.13、温度25.5℃,降解速率达到最大值5.22mg/(L×h).降解过程符合Haldane’s抑制生长动力学模型,最大比降解速率为0.0364h-1.菌株PT能不同程度地降解一些分子结构较为简单或与α-蒎烯结构相似的工业有机污染物.代谢产物分析表明,菌株PT在降解α-蒎烯的过程中产生柠檬油精、紫苏酸等结构较为简单的物质,它们最终被完全矿化为CO2或合成细胞自身组成物质.碳平衡分析表明,底物有机碳含量完全矿化和转化为细胞生物量的比例分别为64.83%和30.37%.     

热脱附-气相色谱-质谱法测定环境空气中5种挥发性卤代烃

建立热脱附-气相色谱-质谱联用测定环境空气中三氯甲烷、四氯化碳、三氯乙烯、四氯乙烯、溴仿等5种挥发性卤代烃的分析方法。该方法在一定浓度范围内工作曲线线性良好,相关系数均在0．9990～0．9998之间,加标回收率在94．0％～106．6％之间,RSD为2．18％-7．62％,检出限为0．22μg／m3～0．30μg／m3。该方法具有操作简单、分析快速、准确度高、灵敏高的特点,用热脱附-气相色谱-质谱联用测定环境空气中5种挥发性卤代烃,结果令人满意。     

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.     

Effect of illumination intensity and light application time on secondary organic aerosol formation from the photooxidation of α-pinene

Secondary organic aerosol (SOA) formation from hydroxyl radical (OH.) initiated photooxidation of α-pinene was investigated in a home-made smog chamber. The size distribution of SOA particles was measured using aerodynamic particle sizer spectrometer. The effects of illumination intensity and light application time on SOA formation for α-pinene were evaluated. Experimental results show that the concentration of SOA particles increased significantly with an increasing of illumination intensity, and the light...     

短期干旱胁迫对马尾松排放挥发性有机物的影响

为探究干旱环境对BVOCs排放的影响,应用动态封闭式采样系统和热脱附-气相色谱-飞行质谱仪,对短期干旱胁迫作用下马尾松的BVOCs排放进行了实验室测量,定量分析BVOCs排放速率和排放组成的变化.结果表明,干旱胁迫时异戊二烯的排放受到抑制,排放速率降低约50%;单萜烯和倍半萜烯的排放水平增强,排放速率分别为137.85和0.98μg/（m²·h）,是未受胁迫时的2.9和2.0倍.除反式-α-香柠檬烯外,干旱胁迫促进各单萜烯和倍半萜烯化合物的排放,是未受胁迫时的1.3~42.4倍,其中3-蒈烯排放的响应最敏感,α-葑烯、α-水芹烯和石竹烯的响应最弱.干旱胁迫时单萜烯和倍半萜烯的排放组成有所变化,但主导的化合物种类不变,单萜烯以α-蒎烯、香桧烯和β-蒎烯为主,占比分别为48%、17%和17%;倍半萜烯以石竹烯和长叶烯为主,占比分别为57%和34%.