中国沿海三省主要饮用水源有机物监测

采用固相萃取、吹扫捕集和气相色谱-质谱联用仪(GC-MS)对江苏、浙江、山东省的21个主要地表饮用水源、126份水样中的25种VOCs、38种SVOCs进行定量检测。结果有19种VOCs、10种SVOCs至少在一个水源地多次被检出,其中挥发性氯代烃、苯系物、氯代苯类、酚类、硝基苯类、酞酸酯类、农药为中国或美国环境保护局提出的"水中优先控制污染物",最高检出量为27.79μg/L。三省主要地表水受到有机物轻度污染,水体中VOCs、SVOCs含量尚未超过《地表水环境质量标准》(GB 3838-2002)和《生活饮用水卫生标准》(GB 5749-2006)限值,工业废水排放及农田雨水径流是地表水有机物的重要来源。     

Determination of volatile organic compounds pollution sources in malaysian drinking water using multivariate analysis

A field investigation was conducted at all water treatment plants throughout 11 states and Federal Territory in Peninsular Malaysia. The sampling points in this study include treatment plant operation, service reservoir outlet and auxiliary outlet point at the water pipelines. Analysis was performed by solid phase micro-extraction technique with a 100 μm polydimethylsiloxane fibre using gas chromatography with mass spectrometry detection to analyse 54 volatile organic compounds (VOCs) of different chemical families in drinking water. The concentration of VOCs ranged from undetectable to 230.2 μg/l. Among all of the VOCs species, chloroform has the highest concentration and was detected in all drinking water samples. Average concentrations of total trihalomethanes (THMs) were almost similar among all states which were in the range of 28.4--33.0 μg/l. Apart from THMs, other abundant compounds detected were cis and trans-1,2-dichloroethylene, trichloroethylene, 1,2-dibromoethane, benzene, toluene, ethylbenzene, chlorobenzene, 1,4-dichlorobenzene and 1,2-dichloro - benzene. Principal component analysis (PCA) with the aid of varimax rotation, and parallel factor analysis (PARAFAC) method were used to statistically verify the correlation between VOCs and the source of pollution. The multivariate analysis pointed out that the maintenance of auxiliary pipelines in the distribution systems is vital as it can become significant point source pollution to Malaysian drinking water.     

Volatile organic compounds in air at urban and industrial areas in the Tarragona region by thermal desorption and gas chromatography–mass spectrometry

Annual trends of a group of 66 volatile organic compounds (VOCs), containing 20 ozone precursors, were the aim of a sampling campaign carried out for a year in air at urban and industrial areas from Tarragona region. VOCs were determined by active collection on multisorbent tubes, followed by thermal desorption and gas chromatography–mass spectrometry. The analytical method was developed and validated, showing good levels of detection and quantification, recoveries, precision, and linearity for all the compounds in the range being studied. All the industrial and urban samples taken during the sampling campaign were similar in their qualitative composition. The most abundant compound in all urban and industrial sites was i-pentane, with concentrations between 15.2 and 202.1 μg m^???3 in urban sites and between 1.3 and 98.6 μg m^???3 in industrial sites. In urban sites, the following compounds in order of abundance were toluene, n-pentane, m,p-xylene, and o-xylene, with maximum levels of 150.6, 45.8, 42.3, and 31.7 μg m^???3, respectively. In industrial sites, the most abundant compounds depended on the sampled site.     

Characterization of Volatile Organic Compounds (VOCs) and Their Sources in the Air of Izmir, Turkey

Air samples were collected in Izmir, Turkey at two (suburban and urban) sites during three sampling programs in 2002 and 2004 to determine the ambient concentrations of several monoaromatic, chlorinated and oxygenated volatile organic compounds (VOCs). Samples were analyzed for 60 VOCs using gas chromatography/mass spectrometry and 28 compounds were detected in most samples. On the average, urban air VOC concentrations were about four times higher than those measured at the suburban site. Toluene (40.6%) was the most abundant compound in suburban site and was followed by benzene (7.4%), o,m-xylene (6.5%), and 1,2-dichloroethane (5.1%). In urban site, toluene (30.5%), p-xylene (14.9%), o,m-xylene (11.4%), and ethyl benzene (7.2%) were the dominating compounds in summer. In winter, toluene (31.1%), benzene (23.9%), 1,2-dichloroethane (9.5%), and o,m-xylene (8.2%) were the most abundant compounds. Receptor modeling (positive matrix factorization) has been performed to estimate the contribution of specific source types to ambient concentrations. Six source factors (gasoline vehicle exhaust, diesel vehicle exhaust+residential heating, paint production/application, degreasing, dry cleaning, and an undefined source) were extracted from the samples collected in the urban site. Three source factors (gasoline vehicle exhaust, diesel vehicle exhaust, and paint production/application) were identified for the suburban site.     

典型废酸油渣中54种VOCs和16种PAHs的分布特征研究

通过运用GC-MS方法对3家润滑油生产企业废酸油渣中的54种挥发性有机物(VOCs)和16种多环芳烃(PAHs)进行定性及定量分析。结果表明,54种VOCs有12种被检出,检出率为22.2%,其中1,2,4-三甲苯在75个样品中均有检出,检出率为100%。54种VOCs质量分数为ND～12.5 mg/kg,其中质量分数较高的化合物为苯(0.6～11.9 mg/kg)、萘(1.0～12.5 mg/kg)、1,2,4-三甲苯(0.5～10.2 mg/kg)。16种PAHs有12种被检出,检出率为75%,其中萘、菲、芘、苯并[a]蒽和■在58个样品中均有检出,检出率为100%。16种PAHs质量分数为2～2 160 mg/kg,其中质量分数较高的化合物为■(25～2 160 mg/kg)、芘(10～207 mg/kg)、苯并[a]蒽(5～108 mg/kg)。同一个企业不同油样之间的VOCs和PAHs检出种类和质量分数存在明显差异,各目标物质量分数与总量之间并不完全相关,这与油源、生产工艺以及样品的风化程度有关。客观上,大部分样本存在不均匀性,因此桶装废酸油渣样品检测应关注采样环节,应根据样品特点采集足够的样本数,保证测定结果真实可靠。     

Investigation and assessment of volatile organic compounds in water sources in China

456 water samples collected from 152 water sources in 2006 were analyzed for 21 volatile organic compounds (VOCs). Concentrations of 21 VOCs ranged from below method detection limits of the laboratory to 7.65 ??g/L (toluene), but seldom exceeded the concentration limits set in the National Drinking Water Quality Standards (GB5749-2006) or the National Environmental Quality Standards for Surface Water (GB3838-2002) of China. Of the 21 individual VOCs analyzed, 11 VOCs were detected in at least one sample at or above 1.0 ??g/L; 6.6% of the water samples had a detection of at least one VOC at or above 1.0 ??g/L, and 2.6% had a detection of at least two VOCs at or above 1.0 ??g/L. Based on the statistical data of detection frequencies above the method detection limits, 75% of the samples detected at least one VOC, and 65% of the samples detected at least two VOCs. Chloroform, toluene, and 1,2-dichloroethene were the three most frequently detected VOCs, with detection frequencies of 76.97%, 68.42%, and 44.08%, respectively. Volatile halogenated hydrocarbons and gasoline components were the two most frequently detected VOC groups.     

吹扫—捕集／气相色谱法测定水中挥发性有机物

为提高样品分析效率，研究并建立了吹扫-捕集／气相色谱／氢火焰检测器联用同时测定水中1，2-二氯乙烷、苯、甲苯、氯苯、乙苯、对-二甲苯、间-二甲苯、苯乙烯、邻-二甲苯、异丙苯、1，4-二氯苯、1，2-二氯苯、硝基苯、1，3，5-三氯苯、1，2，4-三氯苯、1，2，3-三氯苯、六氯丁二烯17种挥发性有机物的分析方法。结果表明，当进样体积为25．0ml时，最低检出限为0．0034-0．1088μg/L，相对标准偏差为1．8％～6．4％，加标平均回收率为97．6％-105．8％。该方法可快速、简便、准确、高灵敏度的测定水中17种挥发性有机物，并适用于饮用水和地表水中挥发性有机物的测定。     

Analysis of volatile organic compounds released during food decaying processes

A number of volatile organic compounds (VOCs) including acetone, methyl ethyl ketone, toluene, ethylbenzene, m,p-xylene, styrene, and o- xylene released during food decaying processes were measured from three types of decaying food samples (Kimchi (KC), fresh fish (FF), and salted fish (SF)). To begin with, all the food samples were contained in a 100-mL throwaway syringe. These samples were then analyzed sequentially for up to a 14-day period. The patterns of VOC release contrasted sharply between two types of fish (FF and SF) and KC samples. A comparison of data in terms of total VOC showed that the mean values for the two fish types were in the similar magnitude with 280 ± 579 (FF) and 504 ± 1,089 ppmC (SF), while that for KC was much lower with 16.4 ± 7.6 ppmC. There were strong variations in VOC emission patterns during the food decaying processes between fishes and KC that are characterized most sensitively by such component as styrene. The overall results of this study indicate that concentration levels of the VOCs differed significantly between the food types and with the extent of decaying levels through time.     

广州市大气VOCs污染特征及O3生成潜势分析

利用手工及自动监测数据，结合最大增量反应活性(MIR)系数法，对广州市大气挥发性有机物(VOCs)污染特征及臭氧生成潜势(OFP)进行了研究。结果表明：广州市大气VOCs总体积分数为73.85×10^-9,其中，丙烷、甲醛、乙酸乙酯的体积分数最高，分别为5.59×10^-9、4.87×10^-9、4.25×10^-9。组成特征分析结果显示，含氧挥发性有机物(OVOCs)和烷烃为主要污染物种类，分别贡献了总VOCs的34.32%和32.34%。在空间分布上，各站点VOCs体积分数自南向北不断降低，番禺市桥站(南部，76.16×10^-9)>公园前站(中部，75.58×10^-9)>花都梯面站(北部，69.80×10^-9)。广州市大气中甲醛和乙醛的比值为1.22,表明本地排放对广州市醛酮类化合物的贡献较大；乙苯和间/对-二甲苯的比值为0.35,表明广州市气团老化程度低，VOCs主要受本地排放影响；甲苯和苯的比值显示，公园前站苯系物主要受机...     

Long-term measurement of volatile organic compounds in ambient air by canister-based one-week sampling method

A canister-based 1 week sampling method using a mechanical flow controller and a 6 L fused-silica-lined canister was evaluated for the long-term measurement of 47 VOCs in ambient air at pptv (volume/volume) to ppbv levels by use of a three-stage preconcentation method followed by GC-MS analysis. The GC conditions were initially optimized for complete separations of several pptv-level VOCs (e.g. vinyl chloride, 1,3-butadiene, acrylonitrile, 1,2-dichloroethane and chloroform) in ambient air because the selected ions are easily interfered with by coexisting C4-, C5-hydrocarbons and analytes presented at ppbv levels. Thirty-four VOCs determined by the 1 week and 24 h sampling method in December 16-22 (2002) had concentrations of 6.0-15000 pptv per compound. Concentrations of 28 VOCs (including polar VOCs (e.g. methyl isobutyl ketone and butyl acetate)) obtained by the method were approximately equal to the mean values calculated from 24 h sampling (< +/- 10% deviation). Six VOCs that had low concentrations of 6.0-43 pptv showed more than +/- 10% deviation. Thirteen VOCs were not detected during the entire sampling period. The effect of relative humidity or ozone for the specific VOCs (e.g. MIBK, butyl acetate, vinyl chloride, 1,3-butadiene and styrene) was negligible.     

Identification and detection sensitivity of <Emphasis Type="Italic">Microcystis aeruginosa</Emphasis> from mixed and field samples using MALDI-TOF MS

To verify the applicability of identifying Microcystis aeruginosa by matrix-assisted laser desorption-ionization-time-of-flight mass spectrometry (MALDI-TOF MS), mixed and field samples were employed to study the sensitivity and the analysis power, respectively. Series diluted samples and artificially mixed samples by the M. aeruginosa NIES-843 strain were designed to verify the sensitivity. The lowest detection limit was 1.955?×?10⁶ cells in pure samples, while for mixed samples, the lowest detection limit and ratio of NIES-843 strain were 2.88?×?10⁶ cells and 33.7%, respectively. The results provided a reference for the reasonable volume of the water sample in which the M. aeruginosa could be detected. Ribosomal protein biomarkers for identifying M. aeruginosa which were successfully detected from the field samples in Taihu Lake, indicated that the identification of M. aeruginosa by MALDI-TOF MS could be applied in field samples. Furthermore, different genetic types of M. aeruginosa strains were also detected at different locations in Taihu Lake, which revealed the diversity of M. aeruginosa and the detection power of MALDI-TOF MS at the strain level for the field samples. The sensitivity and detection power in the analysis of M. aeruginosa by the MALDI-TOF MS demonstrated the applicability of this method in routine environmental monitoring.     

Ambient Air Quality at the Site of a Former Manufactured Gas Plant

Prior to the 1950's, manufactured gas was commerciallyproduced from the pyrolysis of coal, coke, and oil atfacilities that are termed manufactured gas plants (MGPs). The constituents of residual coal tar present on many MGPsites are an environmental health concern because of theirtoxicity and the possibility for their off-site migration viawater and air. Atmospheric concentrations of five volatileorganic compounds (VOCs, e.g., benzene), sixteen polycyclicaromatic hydrocarbons (PAHs, e.g., naphthalene), and particulate matter less than 10 microns in aerodynamicdiameter (PM₁₀) were measured at the site of a former MGP. Air samples were obtained before, during, and after excavationof subterranean coal tar at the site. The results of thisinvestigation indicate that subterranean coal tar was not aprimary source of VOCs and PAHs in the local atmosphere beforeor after remediation of the site. However, excavation,treatment, blending, and transfer of the coal tar duringremediation generated concentrations of selected aromatic andsemi-volatile organic compounds that were substantiallygreater than typical ambient levels. In addition, these datasuggest that blending and mixing of coal tars could lead toexceedance of the U.S. National Ambient Air Quality Standardfor PM₁₀, although additional research is required to fullyevaluate this possibility. Nuisance odors associated with thesite remediation were likely the result of naphthalene andpossibly isomers of xylene. Air pollutant concentrationsmeasured adjacent to the excavation area and at the siteperimeter during remediation activities were less than therelevant occupational and environmental exposure limits.     

VOCs在线监测系统与SUMMA罐采样-气质联用法的比对分析

将挥发性有机污染物在线监测系统与实验室内SUMMA罐采样气质联用法(GC-MS)的挥发性有机物分析进行了标准气体和实际空气样品的分析比对,并对偏差原因作分析,提出在线监测系统的维护建议。结果表明,挥发性有机物在线监测系统的监测结果与实验室方法有一定的可比性,可用于大气中挥发性有机污染物的在线监测。     

Emission characteristics of VOCs from three fixed-roof p-xylene liquid storage tanks

This study evaluates emission characteristics of volatile organic compounds (VOCs) caused by standing loss (L _S) and working loss (L _W) of three vertical fixed-roof p-xylene (p-X) liquid tanks during 1-year storage and filling operation. The annual net throughput of the tanks reached 70,446 t, resulting in 9,425 kg of p-X vapor emission including 5,046 kg of L _S (53.54 %) and 4,379 kg of L _W (46.46 %). The estimated L _W of AP-42 displayed better agreement with the measured values of a VOC detector than the estimated L _S of AP-42. The L _S was best correlated with the liquid height of the tanks, while the L _W was best correlated with the net throughput of the tanks. As a result, decreasing vapor space volume of the tanks and avoiding high net throughput of the tanks in a high ambient temperature period were considered as effective means to lessen VOC emission from the fixed-roof organic liquid storage tank.     

淮河流域江苏平原区浅层地下水污染分析

以淮河流域江苏平原区浅层地下水为研究对象，通过对当地影响较大的污染源调查采样，分析了该地区所采602组水样的无机和有机污染状况。研究表明，区内浅层地下水无机污染较严重，基本形成面状污染，地下水超标率高达83．4％，超标率最高为碘化物。有机污染物检出率34．2％，主要包括二氯甲烷、萘和1，2-二氯乙烷等，以点状分布为主。在此基础上阐述了大气降水、污水灌溉、农业施肥以及地下水开采等人类活动对浅层地下水的影响和污染状况。     

水体中磺胺、四环素、喹诺酮类抗生素检测方法

建立了固相萃取-高效液相色谱-串联质谱法(SPE-HPLC-MS/MS)同时检测水体中3类15种抗生素的分析方法。水样用Oasis HLB固相萃取小柱净化富集。通过对比水样在不同pH条件下的回收率,优化了环境水样中抗生素固相萃取过程中的前处理条件。采用甲醇和0.1%甲酸溶液作为流动相,经过梯度洗脱进行分离,在HPLC-MS/MS多反应监测模式下进行定性定量分析。结果表明,环境水体中15种抗生素的检出限和定量下限分别为0.12~1.6 ng/L和0.2~3.0 ng/L,自来水加标回收率为34.9%~102.5%(pH=4)。用该方法对海河流域13个地表水水样进行了初步检测,结果表明,部分抗生素普遍存在于地表水体中。其中,磺胺甲基异NFDA1唑检出频率最高,在13个地表水样品中均有检出。     

Development and comparison of methods using MS scan and selective ion monitoring modes for a wide range of airborne VOCs

Adsorbent sampling with analysis by thermal desorption, gas chromatography and mass spectrometry (TD/GC/MS) offers many advantages for volatile organic compounds (VOCs) and thus is increasingly used in many applications. For environmental samples and other complex mixtures, the MS detector typically is operated in the scan mode to aid identification of co-eluting compounds. However, scan mode does not achieve the optimal sensitivity, thus compounds occurring at low concentrations may not be detected. This paper develops and evaluates the application of a more sensitive TD/GC/MS method using selective ion monitoring (SIM) that is applicable to VOC mixtures found in ambient and indoor air. Based on toxicity and prevalence, 94 VOCs (including terpenes, aromatic, halogenated and aliphatic compounds) were selected as target compounds. Two analytical methods were developed: a conventional full scan method for ions from 29 to 270 m/z; and a SIM method using 16 time windows and different ions selected for the compounds in each window. Both methods used the same Tenax GR adsorbent sampling tubes, TD and GC parameters, and target and qualifier ions. Laboratory tests determined calibrations, method detection limits (MDLs), precisions, recoveries and storage stability. Field tests compared scan and SIM mode analyses for duplicate samples of indoor air in 51 houses and outdoor air at 41 sites. Statistical analyses included the development of error/precision models. The laboratory tests showed that most compounds demonstrated excellent precision (<10% for concentrations exceeding approximately 0.5 microg m(-3)), good linearity, near identical calibrations for scan and SIM modes, a wide dynamic range (up to 1500 microg m(-3)), and negligible storage losses after 1 month (7 compounds showed moderate losses). SIM mode MDLs ranged from 0.004 to 0.27 microg m(-3), representing a modest (1.1 to 22-fold) improvement compared to scan mode. However, in field tests the SIM method detected significantly more compounds (e.g., styrene and chloroform). Error models fit most compounds and allow quantification of errors at selected percentiles. Overall, while the new SIM method is somewhat time-consuming to develop, it offers greater sensitivity and maintains the high selectivity of traditional scan methods.     

吹扫捕集-气相色谱质谱法分析土壤和沉积物中挥发性有机物

采用吹扫捕集-气相色谱质谱法对土壤和沉积物中挥发性有机物进行分析,优化了实验条件,所有物质的相对标准偏差小于5.0％,土壤样回收率在78.2％ ～99.8％之间,沉积物样的回收率在55.2％～95.2％之间.     

便携式GC-MS在应急监测中的应用

建立了便携式GC-MS测定空气和水体中挥发性有机物(VOCs)的方法,能快速、有效地对空气中37种和水体中54种挥发性有机物进行现场定性和定量。具有相关性好、检出限低、精密度好、准确度高的特点,适用于空气和水体中挥发性有机物的应急监测工作。     

吹扫捕集-气相色谱联用同时测定水中致嗅挥发性有机硫化物

建立了一种利用吹扫捕集(PT)-气相色谱(GC)/火焰光度检测器(FPD)同时测定水中16种致嗅类有机硫化物的分析方法。研究并优化了捕集阱类型、吹扫温度、吹扫时间,解吸温度以及解吸时间对PT的影响。实验表明:大部分硫醚类和硫醇类化合物分别在1~100 ng/L和3~300 ng/L范围内线性良好,线性相关系数大于0.99;相对标准偏差小于9.47%(n=6);加标回收率为81.68%~115.18%。定量下限(10倍信噪比)范围从0.19 ng/L(二乙基二硫醚)到2.67 ng/L(2-甲基-1-丙硫醇)。采用此方法对北京市3条河流水样进行了检测,除1-丙基二硫醚和2-甲基-2-丙硫醇外,其他14种有机硫化物都有检出,质量浓度为1.95~1 282.35 ng/L。