Automatic on-line monitoring of atmospheric volatile organic compounds: gas chromatography-mass spectrometry and gas chromatography-flame ionization detection as complementary systems

Traditionally air quality networks have been carrying out the continuous, on-line measurement of volatile organic compounds (VOC) in ambient air with GC-FID. In this paper some identification and coelution problems observed while using this technique in long-term measurement campaigns are described. In order to solve these problems a GC-MS was set up and operated simultaneously with a GC-FID for C₂-C₁₁ VOCs measurement.There are few on-line, unattended, long term measurements of atmospheric VOCs performed with GC-MS. In this work such a system has been optimized for that purpose, achieving good repeatability, linearity, and detection limits of the order of the GC-FID ones, even smaller in some cases. VOC quantification has been made by using response factors, which is not frequent in on-line GC-MS. That way, the identification and coelution problems detected in the GC-FID, which may led to reporting erroneous data, could be corrected.The combination of GC-FID and GC-MS as complementary techniques for the measurement of speciated VOCs in ambient air at sub-ppbv levels is proposed. Some results of the measurements are presented, including concentration values for some compounds not found until now on public ambient air VOC databases, which were identified and quantified combining both techniques. Results may also help to correct previously published VOC data with wrongly identified compounds by reprocessing raw chromatographic data.     

Screening of organic matter in leachates from sanitary landfills using gas chromatography combined with mass spectrometry

Sanitary landfills are potential groundwater pollution sources, normally producing leachate with very high content of organic matter. Leachates from five Danish sanitary landfills were sampled in order to investigate the composition of the organic matter. The samples were extracted using dichloromethane followed by sodium hydroxide solution, in this way dividing the sample into one phase containing the basic and neutral compounds and one containing the acidic compounds. One of the leachates was extracted using pentane, for analysis of volatile compounds. The three extracts were analysed using gas chromatography combined with mass spectrometry. Several compounds were identified, including chlorinated pesticides (2 of the 5 leachates), aromatic carboxylic acids and alkylbenzenes. Benzene, toluene and trichloroethylene were found in the leachate analysed for volatile compounds. Some of the compounds identified in this work have been reported in the literature to give rise to severe groundwater problems.     

Predicting the importance of oxidative aging on indoor organic aerosol concentrations using the two‐dimensional volatility basis set (2D‐VBS)

Organic aerosol (OA) is chemically dynamic, continuously evolving by oxidative chemistry, for instance, via hydroxyl radical (OH) reactions. Studies have explored this evolution (so‐called OA aging) in the atmosphere, but none have investigated it indoors. Aging organic molecules in both particle and gas‐phases undergo changes in oxygen content and volatility, which may ultimately either enhance or reduce the condensed‐phase OA concentration (C_OA). This work models OH‐induced aging using the two‐dimensional volatility basis set (2D‐VBS) within an indoor model and explores its significance on C_OA relative to prior modeling methodologies which neglect aging transformations. Lagrangian, time‐averaged, and transient indoor simulations were conducted. The time‐averaged simulations included a Monte Carlo procedure and sensitivity analysis, using input distributions typical of U.S. residences. Results demonstrate that indoors, aging generally leads to C_OA augmentation. The extent to which this is significant is conditional upon several factors, most notably temperature, OH exposure, and OA mass loading. Time‐averaged C_OA was affected minimally in typical residences (<5% increase). However, some plausible cases may cause stronger C_OA enhancements, such as in a sunlit room where photolysis facilitates significant OH production (~20% increase), or during a transient OH‐producing cleaning event (~35% peak increase).     

Source apportionment of human personal exposure to volatile organic compounds in homes, offices and outdoors by chemical mass balance and genetic algorithm receptor models

A number of past studies have shown the prevalence of a considerable amount of volatile organic compounds (VOCs) in workplace, home and outdoor microenvironments. The quantification of an individual's personal exposure to VOCs in each of these microenvironments is an essential task to recognize the health risks. In this paper, such a study of source apportionment of the human exposure to VOCs in homes, offices, and outdoors has been presented. Air samples, analysed for 25 organic compounds and sampled during one week in homes, offices, outdoors and close to persons, at seven locations in the city of Leipzig, have been utilized to recognize the concentration pattern of VOCs using the chemical mass balance (CMB) receptor model. In result, the largest contribution of VOCs to the personal exposure is from homes in the range of 42 to 73%, followed by outdoors, 18 to 34%, and the offices, 2 to 38% with the corresponding concentration ranges of 35 to 80 microg m(- 3), 10 to 45 microg m(- 3) and 1 to 30 microg m(- 3) respectively. The species such as benzene, dodecane, decane, methyl-cyclopentane, triethyltoluene and trichloroethylene dominate outdoors; methyl-cyclohexane, triethyltoluene, nonane, octane, tetraethyltoluene, undecane are highest in the offices; while, from the terpenoid group like 3-carane, limonene, a-pinene, b-pinene and the aromatics toluene and styrene most influence the homes. A genetic algorithm (GA) model has also been applied to carry out the source apportionment. Its results are comparable with that of CMB.     

Daily concentrations of trace metals in aerosols in Beijing, China, determined by using inductively coupled plasma mass spectrometry equipped with laser ablation analysis, and source identification of aerosols

This paper describes the daily concentrations of trace metals and ionic constituents in the aerosol of Beijing, China from March 2001 to August 2003. Daily PM10 concentrations were also measured from September 2001 to August 2003. The daily average PM10 concentration at Beijing, China from September 2001 to August 2003 was 171+/-117 microg m(-3) (n = 673), which is 5-fold higher than at Yokohama, Japan. Trace metal concentrations were analyzed by using inductively coupled plasma mass spectrometry equipped with a laser ablation sample introduction (LA/ICP-MS), which is a rapid and simultaneous method for multi-element analysis. The daily average metal concentrations in TSP in Beijing from March 2001 to August 2003 were: Al: 3.5+/-2.4 (n = 727), Ti: 0.47+/-0.35 (n = 720), V: 0.013+/-0.010 (n = 716), Cr: 0.019+/-0.015 (n = 618), Mn: 0.24+/-0.16 (n = 730), Fe: 5.5+/-3.9 (n = 728), Co: 0.0046+/-0.0055 (n = 629), Ni: 0.022+/-0.024 (n = 680), Cu: 0.11+/-0.11 (n = 660), Zn: 0.77+/-0.60 (n = 726), As: 0.048+/-0.047 (n = 731), Se: 0.010+/-0.010 (n = 550), Cd: 0.0068+/-0.0082 (n = 709), Sb: 0.033+/-0.036 (n = 687), and Pb: 0.43+/-0.50 (n = 728) (unit, microg m(-3)). All the metal concentrations in TSP in Beijing, China were 1.7-21.8 times higher than those in TSP in the center of Tokyo, Japan. Notably, As concentrations in TSP in Beijing were 20-fold higher than those in Tokyo. Source identification of aerosols in Beijing was carried out by using the chemical mass balance (CMB) receptor model, with the daily concentration of metals in the aerosol. The major primary sources of the aerosol of Beijing were considered to be soil dust and coal combustion. Vehicle exhaust contribution tended to increase.