32 12 2011 12 ENVIRONMENTAL SCIENCE Vol 32 No 12 Dec 2011 1 2 3 2 2* 2 2 4 1 1 200234 2 314006 3 314000 4 100084 PID GC GC 1 RAE-SEP 80% ~ 97% 90% 2 GC 1 012 R 2 > 0 99 3 GC R 2 > 0 99 n = 47 X833 A 0250-3301 2011 12-3641-06 Applicability of an Electronic Nose for Detection of Volatile Chlorinated Hydrocarbons in Soil BU Fan-yang 1 2 WEN Xiao-gang 3 WAN Mei 2 LIU Rui 2 CAI Qiang 2 CHEN Lü-jun 2 4 ZHANG Yong-ming 1 1 College of Life and Environmental Science Shanghai Normal University Shanghai 200234 China 2 Department of Environmental Technology and Ecology Yangtze Delta Region Institute of Tsinghua University Jiaxing 314006 China 3 Mechanical and Electrical Engineering College Jiaxing University Jiaxing 314000 China 4 School of Environment Tsinghua University Beijing 100084 China Abstract An electronic nose principally composed of a photo ionization detector PID was developed for rapid detection of volatile chlorinated hydrocarbons VCHs in contaminated soil Removal of interference gas such as benzene homologues with a pre-filtration tube was analyzed with gas chromatography GC A standard gas generator was applied to generate different concentrations of perchloroethylene PCE and trichloroethylene TCE gas with which the determine precision and reproducibility of the electronic nose were evaluated by comparison with GC Finally simulated contamination soil with three typical paddy soils in Yangtze river delta region were used for ventilation purification experiments the change of VCHs concentrations in the ventilation gas was monitored based on which the applicability of the electronic nose was evaluated for on-line detection of the on-going of the ventilation purification process Results showed that a halogenated hydrocarbon RAE-SEP tube was effective to remove interference gas with 80% -97% of benzene homologues such as benzene and ethyl benzene being removed while more than 90% of VCHs passed through With PCE or TCE gas a linear dependence was derived between the data determined with the electronic nose and GC the linear slope being 1 012 and R 2 > 0 99 The electronic nose showed data consistent with GC R 2 > 0 99 n = 47 when applied for monitoring the remediation progress in a soil ventilation process The electronic nose is therefore possibly applicable for rapid determination of soil pollution by VCHs improving the efficiency of pollution diagnosis and remediation Key words electronic nose trichloroethylene TCE perchloroethylene PCE soil contamination soil remediation 4 ~ 6 trichloroethylene TCE perchloroethylene PCE 1 ~ 3 soil vapor extraction SVE 2011-05-11 2011-07-24 2008DFA91300 10K11ESPCT 1986 ~ E-mail bufanyang1986@ 163 com * E-mail liuruitsinghuazj@ gmail com
3642 32 ethyl benzene chlorobenzene 7 ~ 9 dimethylbenzene xylene SVE gas chromatography GC 10 15 1 2 1 2 1 PC RAE RAE-SEP PID 11 ~ 14 H 2 S SO 2 CO NO 2 H 2 CH 4 C 2 H 2 PCE TCE CT GC PID 1 2 2 TCE PCE 40 0 2 0 4 0 6 0 8 1 0 1 6 2 0 L min - 1 GC 3 1 2 3 1 1 1 3 SHIMADZU GC- 2014 ECD FID isa-m2 GASTEC PD-1B DHG- 9240 AL204-IC Mettler-Toledo trichloroethylene TCE PTFE perchloroethylene PCE carbon tetrachloride CT methylbenzene 3 2 mm 3 PCE 3 5 g 5 cm 1 1 Fig 1 Photo of soil ventilation desorption device
12 3643 0 1 L min - 1 1 min GC 30 h 3 1 98% 1 2 4 200 μl 1 200 250 40 10 min - 1 100 ECD 200 μl 1 20 180 220 40 10 min - 1 100 FID 2 Fig 2 Photo of electronic nose system and sensor array 0 2 0 4 0 6 0 8 1 0 1 6 2 0 L min - 1 1 000 μl 200 μl 6 PC 4 2 min 3 5 min 10 min Matlab 7 0 2 V max - V 0 2 1 Origin 2 2 2 1 11 0 ev volatile chlorinated olefins benzene series 1 10 6 10 6 ev 10 6 ev PID ev PID 3 16 Figaro 17 RAE-SEP PID PCE TCE 3 VCHs
3644 32 3 CCl 4 C 2 HCl 3 C 2 Cl 4 1 90% 2 GC Table 2 Detection results of standard gas using GC and electronic nose 97% GC / mg m - 3 / mg m - 3 80% / L min - 1 PCE TCE PCE TCE 90% 0 2 412 9 ± 3 21 126 7 ± 3 7 420 5 ± 3 87 122 3 ± 3 16 0 4 204 9 ± 5 91 65 1 ± 1 99 198 8 ± 4 29 64 2 ± 1 86 PCE TCE CCl 4 10 6 ev PID 2 0 44 3 ± 1 91 14 3 ± 0 72 43 4 ± 2 25 13 5 ± 0 71 PCE 1 y = 1 012x - 0 131 R 2 = 0 99 1 2 4 Table 1 Ionization potential of VOCs / ev 4 3-1 2- CHCl = CHCl 9 65 CCl 2 = CHCl 9 45 CCl 2 = CCl 2 9 32 C 6 H 6 9 24 C 6 H 5 CH 3 8 82 C 6 H 5 C 2 H 5 8 76 CCl 3 11 37 CCl 4 11 47 Fig 3 3 Separation effect of RAE-SEP TUBES 0 6 139 4 ± 5 89 43 2 ± 2 21 137 5 ± 5 2 43 1 ± 1 93 1 0 84 7 ± 4 65 25 9 ± 2 06 82 7 ± 3 79 24 5 ± 1 67 GC 200 min mg m - 3 mg m - 3 500 min dense non-aqueous phase liquids DNAPL PCE PCE PCE PCE 18 ~ 20 SVE t 0 VOCs VOCs c c = A t - t 0 - n 2 3 21 ~ 23 GC TCE PCE 2 GC 2 1 012 R 2 > 0 99 1% ~ 8%
12 3645 Fig 5 5 GC n = 47 Linear fitting of data with GC and electronic nose n = 47 4 PCE Fig 4 Real-time detection of the PCE concentrations in the process of desorption for Huangban soil Qingzi soil Fenni soil 2 3 24 25 R 2 > 0 99 n = 47 99% 1 Kobayashi T Shimizu Y Urano K Estimation of adsorbed amounts of volatile chlorinated organic compounds to wet soil 2 5 GC 4 GC n = 47 5 2 3 1 97% 80% 90% PCE TCE 90% CCl 4 PID PCE 2 GC TCE PCE 1 012 R 2 > 0 99 1% ~ 8% 3 GC 3 based on the properties of the compounds and soils J Science of the Total Environment 2003 301 1-3 215-223 2 Jendrzejewski N Eggenkamp H G M Coleman M L Characterisation of chlorinated hydrocarbons from chlorine and carbon isotopic compositions scope of application to R 2 > 0 99 99% environmental problems J Applied Geochemistry 2001 16
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