41 2013 2 FENXI HUAXUE Chinese Journal of Analytical Chemistry 2 268 ~ 272 檵檵 研究简报 檵檵檵檵檵檵檵檵檵檵檵檵檵檵檵檵 DOI: 10. 3724 / SP. J. 1096. 2013. 20769 - * 361005 Chlorofluorocarbons CFCs CFCs #60 8 min 20 ml /min 1. 5 min 130 CFC-11 CFC-12 CFC-113 CCl 4 Carbon tetrachloride 0. 004 0. 008 0. 001 0. 006 pmol /L 99. 92% ± 1. 77% 98. 77% ± 1. 50% 98. 95% ± 3. 92% 97. 13% ± 1. 78% 0. 99 27 1 Chlorofluorocabons CFCs CFC-11 CCl 3 F CFC-12 CCl 2 F 2 CFC-113 CCl 2 FCClF 2 CCl 4 1 CFCs / CFCs Transient tracers 2 3 CO 2 4 5 6 CFCs ng /L 7 CFCs Gammon 8 CFCs Bullister Weiss CFC-11 CFC-12 9 CFC-113 10 CCl 11 4 CFCs 12 ~ 15 - CFC-11 CFC-12 CFC-113 CCl 4 CFCs 2 2. 1 Electric Capture Detector ECD Varian3800 Varian CP-Select 624 CB 75 m 0. 53 mm I. D. d f = 3!m Varian Tekmar- Dohramann 3100 Tekmar 2 mm I. D. 20 cm 0. 18 ~ 0. 25 mm Porapak 2012-07-22 2012-10-29 No. 41076133 * E-mail mgcai@ xmu. edu. cn
2-269 T 99. 999% 60 ~ 80 CFCs CFC-11 CFC-12 CCl 4 0. 45 mg /m 3 CFC- 113 0. 045 mg /m 3 25 ml SGE VICI 5 10 20 50 100!L VICI 100 ml CNW 2. 2 1 1 Fig. 1 2. 3 Diagram of purge and trap system 25 ml 20 ml /min 8 min #60 130 1. 5 min #150 180 0. 069 MPa 35 3 min 10 /min 100 2. 5 min 300 2. 4 1 h 5 10 20 50 100!L CFCs - CFCs 5!L 10 3 CFCs 20!L A 1 A 2 A 0 R % R = A 1 - A 0 /A 2 100% 3 3. 1 3. 1. 1 CFCs Porapak Q 14 Porasil C 8 Unibeads 2S 12 Porapak T 13 #30 Porapak T
270 41 / #60 130 3. 1. 2 CFCs 100!L CFC-12 CFC-11 2 3 min 1. 5 min 1. 5 min 3. 1. 3 CFCs 100!L 20 ml /min 3. 1. 4 CFCs 100!L 4 6 8 10 12 min 4 ~ 12 min 2 CFCs Fig. 2 Relationship between desorb time and peak area 1. Chlorofluorocarbon-12 CFC-12 2. Chlorofluorocarbon-11 CFC-11 3. Chlorofluorocarbon-113 CFC-113 4. Carbontetrachloride CCl 4. 3 CFCs A 1 A 2 A 3 PE % = A 1 / A 1 + A 2 + A 3 100 3 6 min CFC-12 CFC-113 99% CFC-11 CCl 4 8 min 99% 95% 8 min 3. 2 2. 4 CFCs 20!L 7 CFC-11 CFC-12 CFC-113 CCl 4 RSD 1. 5% 4. 7% 1. 3% 4. 5% CFCs CFC-12 98. 8% ± 1. 5% CFC-11 99. 9% ± 1. 8% CFC-113 98. 9% ± 3. 9% CCl 4 97. 1% ± 1. 8% ECD CFCs 3 Fig. 3 Relationship between purge time and purge efficiency 13 1 1 Table 1 Calibration curves and detection limit Analyte * Regression equation Correlation coefficient R 2 Detection limit pmol /L CFC-11 y = #1. 41920 10 #15 x 2 + 8. 36036 10 #8 x - 6. 45326 10 #5 0. 9987 0. 004 CFC-12 y = 6. 88038 10 #13 x 2 + 7. 67122 10 #7 x - 3. 78105 10 #3 0. 9992 0. 008 CFC-113 y = 3. 1781 10 #12 x 2 + 1. 59715 10 #7 x + 1. 8897 10 #3 0. 9948 0. 001 CCl 4 y = #2. 68551 10 #15 x 2 + 1. 04097 10 #7 x - 4. 66336 10 #3 0. 9991 0. 006 * x y pmol x is CFCs peak area y is the moles of standard gas pmol.
2-271 3. 3 CFCs 2. 4 4 27 CFC-12 0. 145 ~ 2. 80 pmol /kg CFC-11 1. 75 ~ 7. 71 pmol /kg CFC-113 0. 074 ~ 0. 446 pmol /kg CCl 4 2. 22 ~ 7. 91 pmol /kg 15 4 Fig. 4 Chromatograms of Chlorofluorocarbons seawater sample standard and blank a. Blank b. Standard c. Seawater sampel References 1 Bullister J L. Oceanography 1989 2 2 12-17 2 Fine R A Smethie W M Bullister J L Rhein M Min D H Warner M J Poisson A Weiss R F. Deep-Sea Research Part I-Oceanographic Research Papers 2008 55 1 20-37 3 Hartin C A Fine R A Sloyan B M Talley L D Chereskin T K Happell J. Deep-Sea Research Part I-Oceanographic Research Papers 2011 58 5 524-534 4 Sonnerup R E Bullister J L Warner M J. Journal of Geophysical Research-Oceans 2008 113 C12 C12007 5 Dutay J C Bullister J L Doney S C Orr J C Najjar R Caldeira K Campin J M Drange H Follows M Gao Y Gruber N Hecht M W Ishida A Joos F Lindsay K Madec G Maier-Reimer E Marshall J C Matear R J Monfray P Mouchet A Plattner G K Sarmiento J Schlitzer R Slater R Totterdell I J Weirig M F Yamanaka Y Yool A. Ocean Modelling 2002 4 2 89-120 6 Smethie W M Jacobs S S. Deep-Sea Research Part I-Oceanographic Research Papers 2005 52 6 959-978 7 CHEN Yong YUAN Dong-Xing LI Quan-Long. Chinese J. Anal. Chem. 2007 35 6 897-900. 分析化学,2007 35 6 897-900 8 Gammon R H Cline J Wisegarver D. Journal of Geophysical Research-Oceans and Atmospheres 1982 87 NC12 9441-9454 9 Bullister J L Weiss R F. Deep-Sea Research Part a-oceanographic Research Papers 1988 35 5 839-853 10 Wisegarver D P Gammon R H. Geophysical Research Letters 1988 15 2 188-191 11 Krysell M Wallace D W R. Science 1988 242 4879 746-749 12 Bulsiewicz K Rose H Klatt O Putzka A Roether W. Journal of Geophysical Research-Oceans 1998 103 C8 15959-15970 13 Vollmer M K Weiss R F. Marine Chemistry 2002 78 2-3 137-148 14 Bullister J L Wisegarver D P. Deep Sea Research Part I Oceanographic Research Papers 2008 55 8 1063-1074 15 Massolo S Rivaro P Frache R. Talanta 2009 80 2 959-966
272 41 A Purge and Trap-Gas Chromatographic Method for Determination of Chlorofluorocarbons in Seawater CAI Ming-Gang * HUANG Peng ZHANG Mi-Ming LI Wen-Quan College of Ocean and Earth Sciences Xiamen University Xiamen 361005 China Abstract A purge and trap system was developed for the determination of chlorofluorocarbons CFCs in seawater. The optimum conditions were as follows trap temperature of #60 purge time of 8 min purge flow rate of 20 ml /min desorption time of 1. 5 min desorption temperature of about 130. The method is simple and sensitive the detection limit of CFC-11 CFC-12 CFC-113 and CCl 4 were 0. 004 0. 008 0. 001 and 0. 006 pmol /L and the recoveries of them were 99. 92% ± 1. 77% 98. 77% ± 1. 50% 98. 95% ± 3. 92% and 97. 13% ± 1. 78% respectively. The R 2 values of all the calibration curves were greater than 0. 99. This method was successfully used in the analysis of the samples collected in Prydz Bay in 27th Chinese Antarcitc Research Expedition. Keywords Purge and trap Gas chromatography Chlorofluorocarbons Seawater Received 22 July 2012 accepted 29 October 2012 櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫櫫 18 9787122126603 89. 0 16 2012 2