Partition Constants and Adsorption/Desorption Hysteresis for Volatile Organic Compounds on Soil from a Louisiana Superfund Site

The adsorption of four volatile organic compounds (1,4-dichloro-benzene, 1,2-dichloroethane, 1,2,2-trichloroethane and 1,1,2,2,-tetrachloroethane) on three soil types from a Superfund site (Petroprocessors Inc) in Baton Rouge, LA was studied with the purpose of obtaining an overall correlation for inclusion in a groundwater transport model being developed for site remediation. The soil-water partition constant, K_d was determined using a standard ASTM procedure (E–1195–87). Using the data for different soil types (fraction organic carbon between 0.11% and 1.13%) and different mineral surface areas (7 to 45 m²/g), the organic carbon contribution (K_oc) and the mineral matter contribution (K_min) to the partition constant were determined. The soils obtained were either from the Pleistocene period or recent shallow deposits at the site. Both log K_oc and log K_min were linearly correlated to log K_ow, the octanol-water partition constant. This data provided the basis for obtaining a general correlation for K_d on different soil types at the site. The predicted values were in agreement with that for a composite soil from the same site. The desorption of compounds from the high clay soil after the 24 hour adsorption period was observed to show a biphasic behavior, namely, an easily desorbed fraction and a desorption resistant fraction. The easily desorbed fraction was found to be satisfactorily predicted using the conventional K_d as obtained from the adsorption experiment. The slowly desorbing fraction had a time constant of several weeks. The concentration in the desorption resistant compartment was found to be dependant on the initial amount of contaminant available for adsorption. The aqueous phase concentration in equilibrium with the desorption resistant fraction was found to be 8 g/L for dichlorobenzene and 12 g/L for dichloroethane.     

Rate-Limited Desorption of Volatile Organic Compounds from Soils and Implications for the Remediation of a Louisiana Superfund Site

The rates of desorption of trichloroethylene (TCE) and 1,3-dichlorobenzene (DCB) from a silty soil at a Superfund site and a silty-clayey soil from an uncontaminated bottomland hardwoodswamp in Baton Rouge, Louisiana were studied in laboratory batchsystems. The effect of the age of soil contamination was studiedusing a laboratory-spiked soil incubated for 3 days, 3 months and5 months. An empirical non-linear model was used to describe thebi-phasic nature of desorption with one fraction (labile) beingreleased in relatively short periods of time (typically 24–100 hr) and a second fraction (non-labile or irreversible) beingresistant to desorption. The non-linear model parameters, viz.,the fraction of the chemical released rapidly (F), and the firstorder desorption rate coefficients, k ₁ and k ₂respectively for the labile and slowly released fractions weredetermined by fitting the experimental data to the model. Thedata fit the model well as indicated by the high r ² values.The estimate of k ₁ was good. However, the values of k ₂are known with less precision due to the limited duration of theexperiment and number of samples taken at long times. In addition, desorption kinetics of 3 and 5-month old contaminatedsoils showed that progressively less amount of contaminant was available for facile desorption (lower F) compared to freshly contaminated soil. The labile fraction had desorption rate constants of the order of 10^-1 h^-1, whereas the slowlyreleased fraction had rate constants of the order of 10^-4 h^-1 in accord with literature reported values for a varietyof other compounds and soils. Possible mechanisms describing these rates and implications for the site clean up are discussed.     

常州某农药生产场地土壤中挥发性有机物污染状况调查

对常州某农药生产场地土壤中挥发性有机物污染状况进行了调查。数据表明,该场地土壤中挥发性有机物污染以苯系物和卤代烃为主。苯系物浓度为0～56.7mg/kg,卤代烃浓度为0～1.14mg/kg,有潜在风险。     

土壤中挥发性有机物的快速测定方法

本文建立了用便携式气相色谱-质谱仪快速测定土壤中VOCs的方法。该方法能够快速对土壤样品中VOCs进行定性分析和定量测定。当采样量达到5 g时,方法检出限0.02~2.11μg/L,相对标准偏差2.0%~13.5%;加标20μg/L时,回收率63%~123%。采用该方法测定北京地区5个土壤样品,总体质量浓度为0~873μg/kg。     

水质中多种挥发性有机物的同时测定

在采用双柱双检测器的基础上,对水中24种挥发性有机物进行了同时测定。当进样体积为5ml时,最低检测限为0．5俐L,线性范围及测定范围为0．5～50倒L,1μg/L和20μg/L浓度水平的加标回收率在80．0％-110％之间,变异系数为0．6％～9．2％,实验结果令人满意。     

城市大气中挥发性有机化合物监测技术进展

挥发性有机物(VOCs)是臭氧及二次有机颗粒物(SOA)的主要前体物。近年来,我国逐步将VOCs纳入大气污染物控制体系。准确可靠的监测技术是大气VOCs研究及控制的重要前提保障。按照采样方法、分析方法 2个方面介绍并讨论了城市大气中VOCs的现有监测方法,较为详细地介绍了几类广泛采用的离线及在线监测技术,简要讨论了目前VOCs监测中存在的一些问题,展望了今后的发展趋势。     

Distribution Of Volatile Organic Compounds In Ambient Air Of Kaohsiung, Taiwan

Automobile emissions have created a major hydrocarbon pollution problem in the ambient air of Taiwan. The aim of this study was to determine the volatile organic compounds (VOCs) in the ambient air of Kaohsiung, Taiwan. The spatial distribution, temporal variation, and correlations of VOCs at three study sites, selected based on traffic densities and distances from a freeway, were discussed. Sixty-four hydrocarbons were identified in the ambient air. Among all of the VOC species, acetone, aromatic and aliphatic compounds constituted the major constituents. Higher concentrations of VOCs existed further away from major arteries as compared to those found near the freeway. Therefore, the distance from the freeway may not be a sufficient index for reflecting actual air quality in the study area. Weather conditions, wind speed and direction did not affect the distribution of VOC concentrations in the three study sites. Other factors, such as the height and density of buildings, traffic conditions or commercial activities, might affect the distribution of VOCs.     

成都市人为源挥发性有机物排放清单及特征

基于成都市实地调查和环境统计等活动水平数据,采用排放因子法和计算模型等,编制了2014年成都市人为源VOCs排放清单,并完成了空间分配和不确定性分析。成都市人为源VOCs排放量为15.8×10~4t,其中化石燃料固定燃烧源、工艺过程源、溶剂使用源、移动源、储存运输源、其他源排放量分别为0.5×10~4、3.8×10~4、6.0×10~4、4.9×10~4、0.4×10~4、2.2×10~4t,溶剂使用源为最大人为排放源,其次是移动源和工艺过程源。木材加工业为最大工业贡献源,然后依次是医药制造业、非金属矿物制品业、化学原料、化学制品制造业、汽车制造业等。成都市人为源82%的VOCs排放量分布于二、三圈层的工业园区,而中心城区主要为移动源和建筑施工所贡献,其排放分布已随建成区联片发展而形成整体。排放清单活动水平数据可靠性较高,而排放因子存在一定不确定性。     

垃圾填埋场不同区域挥发性有机污染物季节变化特点

通过对北京某垃圾填埋场大气中不同区域挥发性有机污染物(VOCs)的定性和定量分析,研究了其中部分VOCs的季节性特点和浓度分布规律。结果表明,夏、冬2季分别检测出98种和86种化合物,有12种美国环保署(USEPA)优先控制污染物在夏、冬季样品中均有检出。夏季样品中VOCs的浓度大多比冬季高,有的甚至高1个数量级以上。采用不同卫生填埋技术的各代表性区域的臭气浓度也呈现出规律性变化。为加强科学管理,减少扩散,降低风险提供参考。     

空气中挥发性有机物污染状况及健康风险评价

为了了解南京某县空气中挥发性有机污染物(VOCs)的污染状况,采用苏码罐采样-气相色谱-质谱法分析了该县不同功能区空气中的VOCs,探讨了其可能来源并采用国际公认的评价模型,对空气中的VOCs进行了健康风险评价。     

遂宁市夏季大气挥发性有机物污染特征及来源解析

2019年7-8月在四川省遂宁市实验学校、遂宁中学、金鱼小学、石溪浩4个点位同步开展为期20d的挥发性有机物(VOCs)离线观测,分析了遂宁市VOCs浓度时空分布特征、臭氧生成潜势(OFP)和VOCs主要来源。遂宁市TVOC体积浓度为39.4×10^-9,占比较高的组分为OVOCs和烷烃,体积浓度分别为15.6×10^-9和13.3×10^-9,占比分别为39.5%和33.6%。遂宁中学、金鱼小学、石溪浩24 h平均体积浓度分别为29.8 ×10^-9、58.4 ×10^-9、30.0×10^-9;加密点实验学校的小时平均浓度为22.9×10^-9。遂宁市总OFP为166.7 μg/m³,占比最大的为烯烃(33.1%)。实验学校、遂宁中学、金鱼小学、石溪浩OFP浓度分别为101.2、134.4、243.6、122.1 μg/m³。金鱼小学采样点位于工业园区下风向,受工业园区企业排放源影响,VOCs浓度和OFP值均明显高于其他点位。PMF模型源解析结果表明:遂宁市VOCs来源占比最大的为工业排放源,达32%;其次为机动车尾气源、燃烧源,占比均达17%;油气挥发源、天然源、溶剂使用源分别占13%、11%、10%。工业源、机动车尾气来源占比最高的均是金鱼小学,分别为39%、30%;天然源占比较高的是实验学校(13%)和石溪浩(10%)。     

欧洲大气挥发性有机物大尺度监测进展及启示

开展大气臭氧前体物挥发性有机物(VOCs)的大尺度监测对于臭氧污染的联防联控有重要意义。欧洲早在20世纪90年代初就开展VOCs大尺度监测,而中国自2018年才开始建设全国性的VOCs监测网络,目前处于起步发展阶段。通过总结欧洲VOCs大尺度监测的发展历程、监测指标、质量保证及监测结果等,对中国VOCs监测提出建议:开展VOCs监测的顶层设计,对全国VOCs监测进行统一科学规划,保持VOCs监测的稳定性和持续性;通过科学方法筛选优化VOCs监测指标体系,构建统一的监测技术体系和质量管理体系,优先确保监测结果的准确性和可比性;将VOCs监测与现有的大气常规六参数常规监测网、颗粒物组分监测网等其他大气监测网有机融合,形成一个综合而丰富的大气环境监测网络,同时满足业务和科研需求。     

南京市环境空气挥发性有机物监测方法比对研究

2018年9月20—29日,开展了南京市环境空气非甲烷烃(PAMS)原清单中57种挥发性有机物的手工和在线比对监测,监测项目主要包括碳氢化合物、卤代烃和含氧挥发性有机物。通过对VOCs 3 h均值、日均值和主要污染物指标等进行比对,分析在线监测数据与手工监测数据的相关性。测试结果表明,两种方法得到的3 h均值的差异度(1.43)和相关系数(0.897),日均值的差异度(2.16)和相关系数(0.946),呈现出差异度不显著、高度线性相关的特征。同时,进一步分析了监测数据产生偏离的原因,建议加强环境空气手工监测的质控管理,强化在线监测设备的运维管理,推进环境空气挥发性有机物监测的合理、有序发展。     

江苏某县乡镇饮用水中挥发性有机物的检测及其风险评价

在江苏某癌症高发县5个乡镇10个村进行布点取样,采集深层地下水与浅层地下水共计20个水样。采用吹扫捕集与气相色谱-质谱联用方法测定水样中14种挥发性有机物(VOCs),检出二氯甲烷、1,3-二氯丙烷、三氯甲烷、苯和四氯化碳5种VOCs,其质量浓度分别为0.14～1.71、ND～50.98、0.29～90.02、0.09～2.35、0.18～3.45μg/L。2个水样中的三氯甲烷和6个水样中四氯化碳超过《生活饮用水卫生标准》(GB 5749—2006)规定的限值。采用优化的美国环保局风险评价模型进行人体健康风险评价,其非致癌风险指数为0.000 7～0.072,致癌风险水平1.70×10-7～2.03×10-5,70%水样的致癌风险水平超过10-6水质监控值,2个浅层地下水的致癌风险水平较高。四氯化碳和三氯甲烷对非致癌风险指数和致癌风险水平贡献较大。     

基于城市大气挥发性有机物特征分析的数据质量评估方法及案例

城市大气挥发性有机物(VOCs)监测是空气质量监测网的重要组成部分,而数据质量控制和质量保证是VOCs监测的基础。基于8次中国城市大气VOCs外场监测,通过挖掘VOCs浓度、组成和化学活性的内在规律,对VOCs监测数据质量进行评估并总结方法。分析结果显示:城市大气乙烷和苯等长寿命组分具有明显的背景浓度,且区域背景值较为接近,可以用来诊断长寿命VOCs组分浓度异常偏低或偏高现象。而示踪组分的季节(日)变化规律可以用来识别VOCs组分定性问题(如夏季大气异戊二烯和烷基硝酸酯浓度日变化规律应反映植被排放和光化学反应特征)。另外,在气团混合均匀的情况下,VOCs浓度波动与其活性之间存在负相关,这一规律可以用来核查数据准确性或局地源影响。     

便携式气相色谱质谱测定水中挥发性有机物再现性和准确度研究

建立了便携式顶空-气相色谱-质谱（HS-GC-MS）测定水中挥发性有机物的方法。以水中苯系物、卤代烃和氯代苯等VOCs为研究对象,在同一实验室内,使用3台便携式HS-GC-MS模拟现场应急监测环境开展检测活动,研究测定结果的再现性和准确度。实验结果表明,检测结果的相对标准偏差为0.7%~13%;绝大多数目标化合物测定结果的回收率为80%~120%。综合来看,方法的精密度和准确度基本满意,能够满足应急监测工作的需要。     

宁波市环境空气中VOCs污染状况及变化趋势分析

基于近7年来的连续监测数据,对宁波市环境空气中挥发性有机物(VOCs)的污染状况及变化趋势进行了初步分析。研究表明:在宁波市环境空气中检测出94种VOCs,其主要成分是饱和烷烃、芳烃、烯烃、卤代烃、卤代芳烃、含氧有机物等,有37种属有毒有害物质,其中苯系物含量最高;宁波市环境空气中苯系物的污染程度与国内外城市基本处于同一水平,近年来的污染状况变化不大,没有明显恶化;空间分布特征显示一类保护区VOCs的排放以天然源为主,二类各功能区VOCs的排放由天然源和局部人为污染源共同形成,三类区以工业污染源排放为主;时间变化趋势显示VOCs在冬季和春季的平均浓度比其他季节高,VOCs的日变化基本呈现2个主浓度峰值特征,跟城市交通流量变化具有很好相关性。     

油田周边环境典型敏感区大气挥发性有机物特征

采用苏玛罐采样-超低温预浓缩气相色谱质谱联用方法,开展油田特征VOCs成分的分析工作.通过对某油田生产开发区及周边环境敏感区环境空气的持续监测,发现油田特征VOCs的整体扩散规律,低温、温度骤降以及高湿度环境极不利于VOCs扩散,对特征VOCs成分解析并核算其光化学反应特征,明确了臭氧生成潜势,研究表明烷烃及苯系物对臭...     

预冷浓缩系统与气相色谱——质谱法测定室内空气中挥发性有机物

针对室内空气挥发性有机物测定方法的不足,本文采用预冷浓缩系统和气相色谱,质谱联用。建立了测定室内空气中39种挥发性有机物的分析方法,该方法采用苏码罐采样,经液氮预冷冻浓缩后,用心城由检测。该方法灵敏度高,操作简便、重现性好、准确度高,适用于室内空气中挥发性有机物的测定。     

Soil Gas Volatile Organic Compound Concentration Contours for Locating Vadose Zone Nonaqueous Phase Liquid Contamination

Diffusion of VOC from cylindrical vadose zone domains contaminatedwith distributed nonaqueous phase liquid is examined in the steadystate approximation. The effects of first-order biodegradation and ofan extended underlying pool of LNAPL floating on the water table belowthe cylindrical domain are explored by means of an orthogonal functionsapproach. The distribution of VOC in the vadose zone above a floatingcircular LNAPL pool of finite size is explored by a numerical method.The results provide information useful in estimating the spacing anddepth at which soil gas samples should be taken in order to detect thepresence of such source areas. Comparison of model results with soilgas VOC measurements at various depths also provides insight into theextent to which natural biodegradation of the VOCs is taking place.