32 2 Vol 32 No 2 2013 5 Journal of Applied Oceanography May 2013-1 3 1 4 1 2 1 361005 2 361005 3 350002 4 350003 建立了超声波振荡提取 固相萃取 ( SPE) 小柱净化 气相色谱 - 质谱 ( GC-MS) 同时测定缢蛏 ( Sinonovacula Constricta) 中 13 种邻苯二甲酸酯 ( ) 的方法 样品用二氯甲烷超声波振荡提取和 硅胶 - 中性氧化铝 ( 2 1,m m) 固相萃取小柱对待测 净化后, 使用 GC-MS 对 进行定性 定量分析 在优化实验条件下, 方法的相对标准偏差 ( RSD) 9 5 % ( 20 ng /g,n = 5) ; 缢蛏样品中 添加标准的回收率, 除邻苯二甲酸二甲酯 ( DMP,58 6 % ) 邻苯二甲酸二乙酯 ( DEP,62 6 % ) 和 邻苯二甲酸二丙酯 ( DPRP,75 5 % ) 偏低外, 其他组分在 87 9 % ( 邻苯二甲酸丁苄酯,BBP) ~ 111 1 %[ 邻苯二甲酸二 ( 2- 乙基己基 ) 酯,DEHP] 之间 方法的定量检出限范围为 6 3 ng /g( DMP) ~ 32 8 ng /g( 邻苯二甲酸二异丁酯,DiBP), 可满足海洋生物缢蛏中痕量 日常监测的需要 市 售缢蛏样品中共检出 3 种, 分别为 DiBP( 31 2 ~ 55 3 ng /g) 邻苯二甲酸二丁酯 DnBP( 39 7 ~ 51 6 ng /g) 和 DEHP( 22 3 ~ 149 2 ng /g), 与缢蛏生长环境受 污染种类及 理化性质有 关 DEHP 污染的地区差异, 是样品中 DEHP 含量差异的原因之一 海洋化学 ; 邻苯二甲酸酯 ; 缢蛏 ; 固相萃取净化 ; 气相色谱 - 质谱 DOI 10 3969 /J ISSN 2095-4972 2013 02 021 P76 B 2095-4972 2013 02-0288-06 DiNP DiDP 6 0 1% 10 DMP DnBP DnOP 1-4 11 - K ow 5 12-13 Si- nonovacula Constricta 4 6-8 EPA DMP DEP DnBP BBP 2- DEHP 4 DnOP 6 9 DnBP BBP DEHP DnOP 2012-07-08 200705029 1983 ~ E-mail wezhuang@ sina com E-mail zbgong@ xmu edu cn
2-289 GC-MS 10 min - 20 14 95 0 % Dr Ehrenstorfer Gmbh DUP 97 0% -D4 Di-n-butyl phthalate- D4 DnBP-D4 98 0 % Sigma-Aldrich SIM 50 ~ 500 Amu - 20 EM Autotune + 200 V 4 Tedia ± Tedia 75 ~ 150 μm Na 2 SO 4 D4 DEHP-D4 13 Na 2 SO 4 180 8 h 450 4 h DnBP-D4 75 ~ 150 μm DMP DEP DPRP DiBP DnBP 150 μm Supelco 250 5 h 650 6 h HLB 0 5 g 2 cm 3 Waters C18 40 ~ 60 μm YGW 5 0 g 50 cm 3 10 0 cm 3 1 10 min 1 1 2 3 1 0 g Agilent 7890A-5975C - Na 2 SO 4 1 0 cm 3 Agilent Technologies 0 03 g 1 0 g 0 5 g 10 0 cm 3 Supelco 800 20 0 cm 3 - V V 2 8 13 DnBP-D4 DEHP-D4 DMP DEP 0 5 cm 3 GC-MS DPRP Dn- 1 3 - BP DiBP 99 999 % DAP DHXP Agilent DB-35MS 30 m 250 DHPP BBP μm 0 25 μm 300 1 0 DCHP 2- mm 3 250 kpa 1 DEHP DnOP min 1 0 cm 3 /min 97 0 % 2-100 30 /min 220 -D4 Di-2-ethylhexyl phthalate-d4 DEHP-D4 5 /min 250 25 /min 320 5 min EI 70 ev 230 150 280 3 5 min Scan 20% DnBP- DAP DEHP-D4 DHXP BBP DEHP DHPP DCHP DnOP DUP 1 2 1 1 Tab 1 1 Retention times specific ions and relative abundances of and internal standards /min m /z 1 DMP 4 541 163 * 164 194 100 10 6 2 DEP 5 137 149 * 177 222 100 22 1
290 32 1 /min m /z 3 DPRP 6 131 149 * 150 191 100 5 5 4 DiBP 6 392 149 * 223 205 100 5 3 IS 1 DnBP-D4 7 469 153 * 100 5 DnBP 7 488 149 * 205 223 100 4 4 6 DAP 9 255 149 * 237 219 100 5 2 7 DHXP 11 079 149 * 251 334 100 1 1 8 BBP 11 857 149 * 206 238 100 22 4 9 DEHP 12 154 149 * 279 113 100 10 9 IS 2 DEHP-D4 12 166 153 * 171 100 33 10 DHPP 12 297 149 * 265 247 100 9 1 11 DCHP 12 823 149 * 83 249 100 17 5 12 DnOP 13 224 149 * 279 261 100 9 1 13 DUP 16 844 149 * 150 321 100 14 11 * Fig 1 1 13 Total ion chromatography of mixed 13 standards 1 DMP 2 DEP 3 DPRP 4 DiBP 5 DnBP -D4 DnBP-D4 6 DAP 7 DHXP 8 BBP 9 2- DEHP 2- -D4 DEHP-D4 10 DHPP 11 DCHP 12 DnOP 13 DUP 2 2 1 V V - 7 3 V V - 7 3 2-1 1 V V - 7 3 V V - 7 3 V V 30 0 cm 3 1 10 min 30 0 cm 3 1-1 1 20 min 30 0 cm 3 1 30 min 15 0 cm 3 2 15 min / 10 0 cm 3 V V 3 3 10 min / GC-MS 30 0 cm 3 2 30 cm 3 3
2-291 1 30 0 cm 3 3 10 min 2 2-1 0 g - 0 5 - g 1 0 g C18 1 0 g C18 1 0 g - 0 2 g HLB C18 HLB Fig 2 2 Efficiencies of extraction by different solvents for from razor clam samples 2 4 8 2 5 5 2 8 V V 20 cm 3 2 8 V V - 6 5 0 g 13 2 3 0 0 20 0 50 0 100 0 200 0 500 0 ng /g - 4 5 5 0 g 1 2 ~ 1 3-4 PAE 20 ng /g PAE y 1 2 ~ 1 3 PAE x PAE 2 20 ng /g 2 PAE PAE 9 5 % Tab 2 2 13 Recoveries after addictions of 13 standards * /% R RSD /% n = 5 LOD /ng g -1 LOQ /ng g -1 DMP y = 92 15x + 330 4 58 6 0 999 8 4 7 1 9 6 3 DEP y = 174 72x - 1 138 0 62 6 0 996 6 7 1 3 4 11 3 DPRP y = 326 51x - 2 640 7 75 5 0 995 5 4 6 3 3 10 9 DiBP y = 324 54x - 177 3 91 5 0 997 0 9 5 9 8 32 8 DnBP y = 411 45x - 724 3 95 0 0 996 0 9 4 9 3 31 2 DAP y = 435 84x - 2 848 3 90 7 0 997 9 5 0 4 4 14 8 DHXP y = 477 02x - 3 346 3 92 4 0 998 4 5 1 3 6 12 1
292 32 2 * /% R RSD /% n = 5 LOD /ng g -1 LOQ /ng g -1 BBP y = 176 15x - 1 504 1 87 9 0 995 9 2 4 4 6 15 4 DEHP y = 231 72x + 13 227 111 1 0 999 2 8 7 5 2 17 3 DHPP y = 454 74x - 2 502 1 92 9 0 999 2 5 0 2 6 8 7 DCHP y = 296 44x - 1 072 6 92 8 0 998 6 4 2 3 7 12 4 DnOP y = 456 87x - 1 837 9 96 7 0 999 6 5 3 4 7 15 8 DUP y = 380 23x - 2 047 3 97 2 0 999 6 5 2 4 3 14 2 * 0 0 20 0 50 0 100 0 200 0 500 0 ng /g 2 16 13 DMP 58 6 % 3 10 10 DEP 62 6 % DPRP 75 5 % 3 87 9 % BBP ~ 111 1 % DEHP Tab 3 Analytical results of razor calm samples from the market DMP DEP DPRP C DiBP /ng g -1 C DnBP /ng g -1 C DEHP /ng g -1 1 32 9 48 7 35 4 2 31 2 43 0 22 3 3 55 3 51 6 149 2 4 41 4 39 7 106 4 2 5 20 ng /g 3 3 LOD 10 DiBP DnBP LOQ 13 DEHP 4 3 2 13 4 DEHP 1 2 DEHP 1 9 ~ 9 8 ng /g 6 3 ~ 32 8 ng /g 2008 2 6 4 17 DEHP 13 3 DEHP 4 DiBP 31 2 ~ 55 3 3 ng /g DnBP 39 7 ~ 51 6 ng /g DEHP 22 3 ~ - 149 2 ng /g DiBP 4 DnBP DEHP 15 GC-MS 13 1 - - J 2005 33 8 1 063-1 067 2 / J 2005 24 5 35-38 3 Peijnenburg W Struijs J Occurrence of phthalate esters in the environment of the Netherlands J Ecotoxicology and Environmental Safety 2006 63 2 204-215 4 J 2011 28 10 898-902 5 J 2006 25 4
2-293 47-49 6 - / J 2007 25 2 272-275 7 J 2010 33 1 116-118 8 Xu X Li X Sorption behaviour of benzyl butyl phthalate on marine sediments equilibrium assessments effects of organic carbon content temperature and salinity J Marine Chemistry 2009 115 1 /2 66-71 9 Yuan S Huang I Chang B Biodegradation of dibutyl phthalate and di- 2-ethylhexyl phthalate and microbial community changes in mangrove sediment J Journal of Hazardous Materials 2010 184 1 /3 826-831 10 M 2002 11 6 J 2009 28 12 1 419-1 423 12 Staples C Peterson D Parkerton T et al The environmental fate of phthalate esters a literature review J Chemosphere 1997 35 4 667-749 13 - J 2008 25 5 1 011-1 014 14 GB /T17378 6-1998 6 S 1998 15 D 2012 16 J 2003 13 2 9-14 17 J 2008 25 3 202-205 Study on the determination method of phthalate esters in Sinonovacula constricta by gas chromatography-mass spectrometry ZHUANG Wan-e 1 3 LIANG Jing 1 HUANG Dong-ren 4 GONG Zhen-bin 1 2 1 State Key Laboratory of Marine Environmental Science College of Oceanography and Environmental Science Xiamen University Xiamen 361005 China 2 College of the Environment & Ecology Xiamen University Xiamen 361005 China 3 College of Life Sciences Fujian Agriculture and Forestry University Fuzhou 350002 China 4 Monitoring Center of Marine Environment and Fishery Resources of Fujian Province Fuzhou 350003 China Abstract A method for accurate determination of 13 phthalate esters in Sinonovacula constricta by solid phase extraction SPE clean-up and gas chromatography-mass spectrometry GC-MS detection was developed The were first extracted with dichloromethane aided by ultrasonic cleaner and then purified using SPE column packed with 1 0 g silica gel and 0 5 g neuter alumina Finally qualitative and quantitative analyses were achieved by gas chromatography-mass spectrometry The precisions for developed method represented by relative standard deviations RSD were lower than 9 5 % 20 ng /g n = 5 The standard spiked recoveries for 13 were between 87 9% BBP and 111 1 % DEHP with the exception of DMP DEP and DPRP which were 58 6 % 62 6 % and 75 5 % respectively Limits of quantifications LOQ for developed method were 6 3 ng /g DMP ~ 32 8 ng /g DiBP DiBP DnBP and DEHP were detected in the clam samples with the concentration ranges of 31 2 ~ 55 3 ng /g 39 7 ~ 51 6 ng /g and 22 3 ~ 149 2 ng /g That was influenced by the pollutant species in environment and the physicochemical properties of The different concentrations of DEHP in the clam samples may resulted from DEHP contaminated levels in the environment they lived Key words marine chemistry phthalate esters Sinonovacula constricta solid phase extraction SPE gas chromatography-mass spectrometry GC-MS DOI 10 3969 /J ISSN 2095-4972 2013 02 021 ( 责任编辑 : 杜俊民 )