Stable hydrogen,carbon and chlorine isotope measurements of selected chlorinated organic solvents

Stable hydrogen isotopes of two chlorinated solvents, trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA), provided by five different manufacturers, were determined and compared to their carbon and chlorine isotopic signatures. The isotope ratio for delta2H of different TCEs ranged between +466.9 per thousand and +681.9 per thousand, for delta13C between -31.57 per thousand and -27.37 per thousand, and for delta37Cl between -3.19 per thousand and +3.90 per thousand. In the case of the TCAs, the isotope ratio for delta2H ranged between -23.1 per thousand and +15.1 per thousand, for delta13C between -27.39 per thousand and -25.84 per thousand, and for delta37Cl between -3.54 per thousand and +1.39 per thousand. As well, a column experiment was carried out to dechlorinate tetrachloroethylene (PCE) to TCE using iron. The dechlorination products have completely different hydrogen isotope ratios than the manufactured TCEs. Compared to the positive values of delta2H in manufactured TCEs (between +466.9 per thousand and +681.9 per thousand), the dechlorinated products had a very depleted delta2H (less than -300 per thousand). This finding has strong implications for distinguishing dechlorination products (PCE to TCE) from manufactured TCE. In addition, the results of this study show the potential of combining 2H/1H analyses with 13C/12C and 37Cl/35Cl for isotopic fingerprinting applications in organic contaminant hydrogeology.     

Quantification of potassium permanganate consumption and PCE oxidation in subsurface materials

A series of laboratory scale batch slurry experiments were conducted in order to establish a data set for oxidant demand by sandy and clayey subsurface materials as well as to identify the reaction kinetic rates of permanganate (MnO(4)(-)) consumption and PCE oxidation as a function of the MnO(4)(-) concentration. The laboratory experiments were carried out with 31 sandy and clayey subsurface sediments from 12 Danish sites. The results show that the consumption of MnO(4)(-) by reaction with the sediment, termed the natural oxidant demand (NOD), is the primary reaction with regards to quantification of MnO(4)(-) consumption. Dissolved PCE in concentrations up to 100 mg/l in the sediments investigated is not a significant factor in the total MnO(4)(-) consumption. Consumption of MnO(4)(-) increases with an increasing initial MnO(4)(-) concentration. The sediment type is also important as NOD is (generally) higher in clayey than in sandy sediments for a given MnO(4)(-) concentration. For the different sediment types the typical NOD values are 0.5-2 g MnO(4)(-)/kg dry weight (dw) for glacial meltwater sand, 1-8 g MnO(4)(-)/kg dw for sandy till and 5-20 g MnO(4)(-)/kg dw for clayey till. The long term consumption of MnO(4)(-) and oxidation of PCE can not be described with a single rate constant, as the total MnO(4)(-) reduction is comprised of several different reactions with individual rates. During the initial hours of reaction, first order kinetics can be applied, where the short term first order rate constants for consumption of MnO(4)(-) and oxidation of PCE are 0.05-0.5 h(-1) and 0.5-4.5 h(-1), respectively. The sediment does not act as an instantaneous sink for MnO(4)(-). The consumption of MnO(4)(-) by reaction with the reactive species in the sediment is the result of several parallel reactions, during which the reaction between the contaminant and MnO(4)(-) also takes place. Hence, application of low MnO(4)(-) concentrations can cause partly oxidation of PCE, as the oxidant demand of the sediment does not need to be met fully before PCE is oxidised.     

Non-steady state partitioning of dry cleaning surfactants between tetrachloroethylene (PCE) and water in porous media

Trapped organic solvents, in both the vadose zone and below the water table, are frequent sources of environmental contamination. A common source of organic solvent contamination is spills, leaks, and improper solvent disposal associated with dry cleaning processes. Dry cleaning solvents, such as tetrachloroethylene (PCE), are typically enhanced with the addition of surfactants to improve cleaning performance. The objective of this work was to examine the partitioning behavior of surfactants from PCE in contact with water. The relative rates of surfactants partitioning and PCE dissolution are important for modeling the behavior of waste PCE in the subsurface, in that they influence the interfacial tension of the PCE, and how (or if) interfacial tension changes over time in the subsurface. The work described here uses a flow-through system to examine simultaneous partitioning and PCE dissolution in a porous medium. Results indicate that both nonylphenol ethoxylate nonionic surfactants and a sulfosuccinate anionic surfactant partition out of residual PCE much more rapidly than the PCE dissolves, suggesting that in many cases interfacial tension changes caused by partitioning may influence infiltration and distribution of PCE in the subsurface. Non-steady-state partitioning is found to be well-described by a linear driving force model incorporating measured surfactant partition coefficients.     

Effect of source variability and transport processes on carbon isotope ratios of TCE and PCE in two sandy aquifers

Chlorinated ethenes often migrate over extended distances in aquifers and may originate from different sources. The aim of this study was to determine whether stable carbon isotope ratios remain constant during dissolution and transport of chlorinated ethenes and whether the ratios can be used to link plumes to their sources. Detailed depth-discrete delineation of the carbon isotope ratio in a tetrachloroethene (PCE) plume and in a trichloroethene (TCE) plume was done along cross-sections orthogonal to groundwater flow in two sandy aquifers in the Province of Ontario, Canada. At the TCE site, TCE concentrations up to solubility were measured in one high concentration zone close to the bottom of the aquifer from where dense non-aqueous phase liquid (DNAPL) was collected. A laboratory experiment using the DNAPL indicated that only very small carbon isotope fractionation occurs during dissolution of TCE (0.26 per thousand), which is consistent with field observations. At most sampling points, the delta(13)C of dissolved TCE was similar to that of the DNAPL except for a few sampling points at the bottom of the aquifer close to the underlying aquitard. At these points, a (13)C enrichment of up to 2.4 per thousand was observed, which was likely due to biodegradation and possibly preferential diffusion of TCE with (12)C into the aquitard. In contrast to the TCE site, several distinct zones of high concentration were observed at the PCE site and from zones to zone, the delta(13)C values varied substantially from -24.3 per thousand to -33.6 per thousand. Comparison of the delta(13)C values in the high concentration zones made it possible to divide the plume in the three different domains, each probably representing a different episode and location of DNAPL release. The three different zones could still be distinguished 220 m from the DNAPL sources. This demonstrates that carbon isotope ratios can be used to differentiate between different zones in chlorinated ethene plumes and to link plume zones to their sources. In addition, subtle variations in delta(13)C at plume fringes provided insight into mechanisms of plume spreading in transverse vertical direction. These variations were identified because of the high-resolution provided by the monitoring network.     

Comparison of receptor models for source apportionment of volatile organic compounds in Beijing, China

Identifying the sources of volatile organic compounds (VOCs) is key to reducing ground-level ozone and secondary organic aerosols (SOAs). Several receptor models have been developed to apportion sources, but an intercomparison of these models had not been performed for VOCs in China. In the present study, we compared VOC sources based on chemical mass balance (CMB), UNMIX, and positive matrix factorization (PMF) models. Gasoline-related sources, petrochemical production, and liquefied petroleum gas (LPG) were identified by all three models as the major contributors, with UNMIX and PMF producing quite similar results. The contributions of gasoline-related sources and LPG estimated by the CMB model were higher, and petrochemical emissions were lower than in the UNMIX and PMF results, possibly because the VOC profiles used in the CMB model were for fresh emissions and the profiles extracted from ambient measurements by the two-factor analysis models were "aged".     

Potential of the TCE-degrading endophyte Pseudomonas putida W619-TCE to improve plant growth and reduce TCE phytotoxicity and evapotranspiration in poplar cuttings

The TCE-degrading poplar endophyte Pseudomonas putida W619-TCE was inoculated in poplar cuttings, exposed to 0, 200 and 400 mg l⁻¹ TCE, that were grown in two different experimental setups. During a short-term experiment, plants were grown hydroponically in half strength Hoagland nutrient solution and exposed to TCE for 3 days. Inoculation with P. putida W619-TCE promoted plant growth, reduced TCE phytotoxicity and reduced the amount of TCE present in the leaves. During a mid-term experiment, plants were grown in potting soil and exposed to TCE for 3 weeks. Here, inoculation with P. putida W619-TCE had a less pronounced positive effect on plant growth and TCE phytotoxicity, but resulted in strongly reduced amounts of TCE in leaves and roots of plants exposed to 400 mg l⁻¹ TCE, accompanied by a lowered evapotranspiration of TCE. Dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA), which are known intermediates of TCE degradation, were not detected.     

成都市地铁站及车厢内挥发性有机化合物种类探究及影响因素分析

为探究成都地铁站及车厢内部挥发性有机化合物(VOCs)种类、来源及影响因素,使用恒流气体采样器和TENAX-TA 采样管,对不同路线不同人流量期间地铁车厢内、车厢通风口和站台内部（站厅层和站台层）空气进行采样,利用气相色谱质谱联用仪(GC-MS)对车厢内VOCs进行分析。结果表明：地铁站及车厢内部VOCs主要以烷烯烃类和苯系物为主,分别占污染物种类的42.59%和27.78%;高峰期时段车厢内VOCs整体质量浓度(46.47±3.2) μg·m⁻³略高于非高峰期时段(41.35±3.82) μg·m⁻³;地铁机械通风系统可以有效稀释车厢内VOCs质量浓度;站厅层VOCs质量浓度(44.99±13.84) μg·m⁻³高于站台层的质量浓度(35.05±11.28) μg·m⁻³。由此可以看出,成都地铁内VOCs污染种类受人员密集、大气环境和通风设施等综合因素影响。本研究成果可为西南地区地铁系统VOCs污染的监管和防治提供数据支撑,亦可为相关部门提高地铁内部空气质量、降低乘客健康风险决策的制定提供参考。     

Collection and analysis of organic acids in exhaust gas. Comparison of different methods

This paper reports the development of a specific method to identify organic acids in exhaust gases. The organic acids are collected in two impingers containing liquids (pure water or Na₂CO₃ 1% aqueous solution) and four cartridges containing solids (silica, fluorisil, alumina B and alumina N). Once collected, the acids are eluted of the solids by a hot water stream. These traps performances, in terms of organic acids collection and elution efficiency, are evaluated and compared. Two sources are used to produce the gas flow containing organic acids: one generates a flow whose concentration is known and stable, the other produces organic acids among other combustion products. For eluted solutions analysis, two methods are used: isocratic ionic chromatography/conductivity detection and GC/FID. Their efficiency in separating 10 aliphatic acids are compared. Their characteristics such as detection limits, detection linearity, repeatability and possible interferences with other components found in exhaust gases are determined. The stability of the organic acids solutions is also studied. Lastly, the use of these methods is illustrated by the analysis of the gas-phase organic acids exhausted by a spark ignition and by a diesel engine.     

成都市夏季大气挥发性有机物污染及其对二次有机气溶胶生成的贡献

于2014年7月8日至8月13日在成都市城区和工业区选取两个点位开展挥发性有机物(VOCs)样品采集工作,分析结果显示,成都市夏季城区大气中VOCs质量浓度在34.1~458.8μg/m3,平均值为(137.3±91.8)μg/m3;工业区大气中VOCs质量浓度在26.7~474.9μg/m3,平均值为(135.9±103.5)μg/m3。早高峰时段(7:00~10:00)两个点位VOCs的浓度水平均高于其他时段,说明VOCs浓度受机动车排放的影响较为明显。用·OH消耗速率和臭氧生成潜势评估VOCs大气化学反应活性,结果显示,芳香烃和烯烃是影响大气化学反应活性的关键组分。城区和工业区的二次有机气溶胶(SOA)的生成潜势分别为4.859、4.559μg/m3,芳香烃不仅是臭氧生成潜势的关键活性组分,同时也是SOA的重要前体物。     

典型涂料制造企业VOCs排放量核算与排放特征分析

采集了上海地区8家不同类型的涂料制造企业中不同生产环节有组织排放的废气样本,分析其VOCs组分特征和活性VOCs物种,并应用3种实际排放量核算方法计算企业的VOCs年排放量,分析了其与排污许可排放量的关系。结果表明：1)涂料制造行业排放废气的特征组分为芳香烃、OVOCs、卤代烃,占全部VOCs质量浓度的56.2%~99.1%,乙酸乙酯、乙酸丁酯、4-乙基甲苯、间/对二甲苯、甲苯、甲乙酮是涂料制造行业VOCs排放的典型物种;2)基于MIR值法的计算结果,芳香烃和OVOCs是涂料制造行业排放VOCs的主要活性组分,累计OFP贡献率达36.0%~99.8%,其中,4-乙基甲苯(52.1%)、氯乙烯(48.1%)、乙酸丁酯(47.9%)、乙酸乙酯(42.6%)、间/对二甲苯(41.3%)是各类涂料工艺废气中OFP贡献率最高的物质,除苯系物、乙酸酯类化合物外,氯乙烯、甲乙酮、四氢呋喃也是涂料制造过程中值得关注的活性物质;3)涂料制造企业车间的有组织废气VOCs排放量占全厂VOCs排放量的75.0%以上,其次是实验室废气,VOCs排放量为3.5%~16.8%。在VOCs实际排放量核算中,使用实测法的核算结果与物料衡算法接近,且计算简便,在正常运行时均低于许可排放限值;而产污系数法所核算数值较许可排放限值更高,在现阶段可作为一项惩罚性计算方法。     

我国挥发性有机污染场地修复中存在的问题及对策建议

挥发性有机物 (VOCs) 具有易挥发、易迁移、环境归趋机制复杂、赋存分布异质性高的特点,这导致VOCs污染场地的修复治理难度较大。在进行房地产开发时,未经彻底修复的VOCs污染场地容易出现蒸气入侵等健康风险问题,甚至引发社会群体性事件,故VOCs污染场地修复是环境管理部门监管的重点。经过十几年的发展,我国场地修复工作在科学性和规范性方面取得了长足进步,但仍存在对VOCs特殊性考虑不足的问题。系统总结了我国VOCs污染场地修复管控及效果评估方面存在的5个问题,并揭示了这些问题背后的科学机制,结合国内外的工程实践经验和科学研究成果对这5个问题提出了有针对性的对策建议,以期为我国VOCs类污染场地修复治理和安全利用提供参考。     

Levels and source apportionment of volatile organic compounds in southwestern area of Mexico City

Thirteen volatile organic compounds (VOCs) were quantified at three sites in southwestern Mexico City from July 2000 to February 2001. High concentrations of different VOCs were found at a Gasoline refueling station (GS), a Condominium area (CA), and at the University Center for Atmospheric Sciences (CAS). The most abundant VOCs at CA and CAS were propane, n-butane, toluene, acetylene and pentane. In comparison, at GS the most abundant were toluene, pentane, propane, n-butane, and acetylene. Benzene, a known carcinogenic compound had average levels of 28, 35 and 250 ppbC at CAS, CA, and GS respectively. The main contributing sources of the measured VOCs at CA and CAS were the handling and management of LP (Liquid Propane) gas, vehicle exhaust, asphalt works, and use of solvents. At GS almost all of the VOCs came from vehicle exhaust and fuel evaporation, although components of LP gas were also present. Based on the overall results possible abatement strategies are discussed.     

Levels and composition of volatile organic compounds on commuting routes in Detroit, Michigan

Vehicle emissions can constitute a major share of ambient concentrations of many volatile organic compounds (VOCs) and other air pollutants in urban areas. Especially high concentrations may occur at curbsides, vehicle cabins, and other microenvironments. Such levels are not reflected by monitoring at fixed sites. This study reports on measurements of VOCs made from buses and cars in Detroit, MI. A total of 74 adsorbent tube samples were collected on 40 trips and analyzed by GC-MS for 77 target compounds. Three bus routes, selected to include residential, commercial and heavily industrialized areas, were sampled simultaneously on four sequential weeks during morning and afternoon rush hour periods. Nineteen compounds were regularly detected and quantified, the most prevalent of which included hexane/2-methyl pentane (15.6±5.8 μg m⁻³), toluene (10.2±7.9 μg m⁻³), m,p-xylene (6.8±4.7 μg m⁻³), benzene (4.5±3.0 μg m⁻³), 1,2,4-trimethylbenzene (4.0±2.6 μg m⁻³), o-xylene (2.2±1.6 μg m⁻³), and ethylbenzene (2.1±1.5 μg m⁻³). VOC levels in bus interiors and outdoor levels along the roadway were similar. Despite the presence of large industrial sources, route-to-route variation was small, but temporal variation was large and statistically significant. VOC compositions and trends indicate the dominance of vehicle sources over the many industrial sources in Detroit with the possible exceptions of styrene and several chlorinated VOCs. In-bus levels exceeded concentrations at fixed site monitors by a factor of 2–4. VOC concentrations in Detroit traffic are generally comparable to levels measured elsewhere in the US and Canada, but considerably lower than measured in Asia and Europe.     

Exposure of population and microenvironmental distributions of volatile organic compound concentrations in the EXPOLIS study

Determination of volatile organic compounds (VOCs) formed one part of the EU-EXPOLIS project in which the exposure of European urban populations to particles and gaseous pollutants was studied. The EXPOLIS study concentrated on 30 target VOCs selected on the basis of environmental and health significance and usability of the compounds as markers of pollution sources. In the project, 201 subjects in Helsinki, 50 in Athens, 50 in Basel, 50 in Milan and, 50 in Oxford and 50 in Prague were selected for the final exposure sample. The microenvironmental and personal exposure concentrations of VOCs were the lowest in Helsinki and Basel, while the highest concentrations were measured in Athens and Milan; Oxford and Prague were in between. In all cities, home indoor air was the most significant exposure agent. Workplace indoor air concentrations measured in this study were generally lower than the home indoor concentrations and home outdoor air played a minor role as an exposure agent. When estimating the measured personal exposure concentrations using the measured concentrations and time fractions spent at home indoors, at home outdoors, and at the workplace, it could be concluded that these three microenvironments do not fully explain the personal exposure. Other important sources for personal exposure must be encountered, the most important being traffic/transportation and other indoor environments not measured in this study.     

气相色谱法分离和测定合成革用胶粘剂中的挥发性有机物

对合成革用胶粘剂中的发挥有机成份进行了色谱分离，并测定了胶粘剂中的9种挥发性有机物，方法的加标回收率为89.4%～102.8%，变异系数为1.2%～5.0%。     

我国挥发性有机污染地块调查评估中存在的问题及对策建议

基于多年研究和实践经验,总结了我国挥发性有机污染地块调查评估方面存在的6个问题。从科学机制角度,通过分析实际地块案例,阐述了产生这些问题的原因。最后,针对这6方面的问题分别提出了改进建议,以期为我国VOCs类污染地块调查评估和修复治理提供参考。     

江苏省典型工业源挥发性有机物排污特征与减排潜力分析

VOCs是臭氧和二次有机气溶胶等复合型污染的前驱体。基于原辅料和生产工艺的角度,构建江苏省内人造板、印刷、电子、橡胶和塑料、制药、化工、喷涂为代表的典型工业行业VOCs成分谱。通过最大增量反应活性系数(MIR) 、气溶胶生成系数(FAC),依据原辅料、产品和工艺的区别,分析各行业、企业VOCs 组分区别与臭氧生成潜势和二次颗粒物生成潜势。结果表明：橡胶和塑料行业单位OFP最高,约为4.09 g·g⁻¹;SOA较高的印刷、制药、涂装、橡胶和塑料行业,其值约为1.5 g·g⁻¹;通过MIR 和FAC 系数模型可知,橡胶和塑料行业是O₃污染管控重点,印刷、制药、涂装、橡胶和塑料行业是二次气溶胶的管控重点。基于江苏省典型工业行业VOCs特征,分析我国现行VOCs治理技术指南推荐工艺与现存低效治理工艺的差异,以估算全国典型工业行业VOCs年产污量和污染特性减排潜力,可为VOCs管理相关法规政策制定提供依据。     

有机负荷对酒糟厌氧消化降解及甲烷产率的影响

为了探究有机负荷对酒糟中温厌氧消化运行的稳定性及产气性能的影响,启动了有机负荷分别为1.6、4.8和6.4 kg·（m3·d）-1的厌氧反应器R1、R2和R3,并以半连续方式运行100 d。单因素方差分析（ANOVA）的结果表明,3个反应器在60~90 d的VS降解率无显著性差异（p=0.19>0.05）,分别为（66.9±3.2）%、（68.1±2.7）%和（66.1±1.5）%,但产气率随着有机负荷的提高而升高,分别为（0.48±0.07）、（0.61±0.06）、（0.71±0.06）m3·kg-1,对应的甲烷比例为56.9%、60.9%和59.6%。虽然提高有机负荷促进了有机碳源利用效率,提高了甲烷比例和产量,但其稳定运行存在一定困难,R3在90 d后产气急剧下降,丙酸大量积累,产酸菌和产甲烷菌间的动态平衡受到破坏。因而,适宜的有机负荷是确保酒糟良好的厌氧消化稳定性能和产气性能的关键因素。     

Compound specific carbon and hydrogen stable isotope analyses of volatile organic compounds in various emissions of combustion processes

This study presents carbon (δ¹³C) and hydrogen (δD) isotope values of volatile organic compounds (VOCs) in various emission sources using thermal desorption-gas chromatography-isotope ratio mass spectrometry (TD-GC-irMS). The investigated VOCs ranged from C6 to C10. Samples were taken from (i) car exhaust emissions as well as from plant combustion experiments of (ii) various C3 and (iii) various C4 plants. We found significant differences in δ values of analysed VOCs between these sources, e.g. δ¹³C of benzene ranged between (i) −21.7 ± 0.2‰, (ii) −27.6 ± 1.6‰ and (iii) −16.3 ± 2.2‰, respectively and δD of benzene ranged between (i) −73 ± 13‰, (ii) −111 ± 10‰ and (iii) −70 ± 24‰, respectively. Results of VOCs present in investigated emission sources were compared to values from the literature (aluminium refinery emission). All source groups could be clearly distinguished using the dual approach of δ¹³C and δD analysis. The results of this study indicate that the correlation of compound specific carbon and hydrogen isotope analysis provides the potential for future research to trace the fate and to determine the origin of VOCs in the atmosphere using thermal desorption compound specific isotope analysis.     

吹扫-捕集法在挥发性有机污染物分析中的应用

吹扫 -捕集法为 2 0世纪 70年代中期推出的痕量挥发性有机化合物的富集方法 ,它具有简便、灵敏度高、富集率高、快速、精密、准确、不使用有机溶剂等特点。 2 0多年以来 ,吹扫 -捕集器和GC、GC/MS等仪器联用测定环境中痕量挥发性有机污染物 ,已获得令人满意的结果 ,因而吹扫 -捕集法将在有机污染分析中得到日益广泛的应用