超声波提取-气相色谱氢火焰测定土壤中六溴环十二烷
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摘要
HBCD (六溴环十二烷,hexabromocyclododecane)是一种常用的溴代阻燃剂,其对环境和生物体造成的影响已被定性为持久性有机污染物.为了建立超声波提取、气相色谱检测土壤中w(HBCD)的方法,分别对超声波提取HBCD条件及气相色谱检测HBCD参数进行优化,并对超声波提取法与索氏提取法进行了比较.结果表明:①最佳超声波提取土壤中HBCD条件为以体积比为1∶1的正己烷:丙酮溶液为提取溶剂,60℃水浴振荡,超声波提取50 min.②气相色谱优化后提取HBCD的最佳分离条件为进样口温度240℃;初始温度90℃,保留1 min;升温程序为90℃时以15℃/min升温至160℃,保留2 min,再以10℃/min升至220℃,保留2 min,最后以5℃/min升至280℃,保留3 min;分流模式为不分流;以氮气为载气;进样量为1μL; FID检测器温度为300℃.③HBCD在土壤中的平均回收率可达97. 1%,相对标准偏差为3. 5%,方法精密度高.④与索氏提取方法相比,超声波提取法提取时间短、样品用量少、灵敏度高,并且方法重现性和精密度较好,能更有效地分析土壤中w(HBCD).研究显示,场地土壤中w(HBCD)平均值为0. 757 mg/kg,相对标准偏差为4. 22%(小于5%),超声波提取及气相色谱检测土壤中HBCD的方法准确度高、重现性好,对分析土壤中HBCD更加简便快捷.
Hexabromocyclododecane( HBCD),a commonly used brominated flame retardant,has been identified as a persistent organic pollutant( POP) due to its effects on the environment and organisms. In order to establish a method for the determination of HBCD in soils by ultrasonic extraction and gas chromatography( GC),the conditions of ultrasonic extraction and gas chromatography analysis were optimized. The ultrasonic extraction was compared with soxhlet extraction. The experimental results indicated that:( 1) The optimum extraction conditions were 25 m L of mixed solvents of hexane and acetone( 1 ∶ 1 V/V),60 ℃,and 50 min extraction time.( 2) The optimum inlet temperature for the gas chromatography was 240 ℃. The initial temperature of the column was kept at 90 ℃ for 1 min,increased to 160 ℃ at 15 ℃ /min for 2 min,and then raised to 220 ℃ at 10 ℃ /min for 2 min. Finally,the temperature was raised to 280℃ at 5 ℃ /min for 3 min. The sample volume was 1 μL and the temperature of FID( flame ionization detector) was 300 ℃.( 3) The average extraction efficiency of HBCD with the optimal parameters could be as high as 97. 1% and the relative standard deviation( RSD)was 3. 5%. The precision of the method was high.( 4) In comparison with soxhlet extraction,ultrasonic extraction had many advantages,such as short time,low sample consumption,high sensitivity,good reproducibility and precision,and more effective for analysis of HBCD in the soil. Finally,the established analytical methods were successfully used to detect HBCD in real soils. The results showed that the concentration of w( HBCD) in the soil was 0. 757 mg/kg,and the RSD was 4. 22%( less than 5%). This method had high accuracy and good reproducibility,and it was more convenient and faster to analyze HBCD in soils.
Hexabromocyclododecane( HBCD),a commonly used brominated flame retardant,has been identified as a persistent organic pollutant( POP) due to its effects on the environment and organisms. In order to establish a method for the determination of HBCD in soils by ultrasonic extraction and gas chromatography( GC),the conditions of ultrasonic extraction and gas chromatography analysis were optimized. The ultrasonic extraction was compared with soxhlet extraction. The experimental results indicated that:( 1) The optimum extraction conditions were 25 m L of mixed solvents of hexane and acetone( 1 ∶ 1 V/V),60 ℃,and 50 min extraction time.( 2) The optimum inlet temperature for the gas chromatography was 240 ℃. The initial temperature of the column was kept at 90 ℃ for 1 min,increased to 160 ℃ at 15 ℃ /min for 2 min,and then raised to 220 ℃ at 10 ℃ /min for 2 min. Finally,the temperature was raised to 280℃ at 5 ℃ /min for 3 min. The sample volume was 1 μL and the temperature of FID( flame ionization detector) was 300 ℃.( 3) The average extraction efficiency of HBCD with the optimal parameters could be as high as 97. 1% and the relative standard deviation( RSD)was 3. 5%. The precision of the method was high.( 4) In comparison with soxhlet extraction,ultrasonic extraction had many advantages,such as short time,low sample consumption,high sensitivity,good reproducibility and precision,and more effective for analysis of HBCD in the soil. Finally,the established analytical methods were successfully used to detect HBCD in real soils. The results showed that the concentration of w( HBCD) in the soil was 0. 757 mg/kg,and the RSD was 4. 22%( less than 5%). This method had high accuracy and good reproducibility,and it was more convenient and faster to analyze HBCD in soils.
引文
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[8]ZHU H,ZHANG K,SUN H,et al.Spatial and temporal distributions of hexabromocyclododecanes in the vicinity of an expanded polystyrene material manufacturing plant in Tianjin,China[J].Environmental Pollution,2017,222:338-347.
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[11]ZHANG Y Q,LU Y L,WANG P,et al.Transport of Hexabromocyclododecane(HBCD)into the soil,water and sediment from a large producer in China[J].Science of the Total Environment,2018,610:94-100.
[12]CHEN X M.Colorimetric sensing of non-ionic and cationic surfactants using a versatile anionic poly(3,4-propylenedioxythiophene)derivative[J].Analytical Methods,2015,7:2800-2805.
[13]COVACI A,GERECKE A C,LAW R J,et al.Hexabromocyclododecanes(HBCDs)in the environment and humans:a review[J].Environmental Science&Technology,2006,40:3679-3688.
[14]PETROVA S,REZEK J,SOUDEK P,VANEK T.Preliminary study of phytoremediation of brownfield soil contaminated by PAHs[J].Science of the Total Environment,2017,599:572-580.
[15]潘荷芳,惠阳,王静,等.土壤中痕量六溴环十二烷的超高效液相色谱/质谱联用分析[J].分析科学学报,2008,24(4):414-416.PAN Hefang,HUI Yang,WANG Jing,et al.Analysis of trace HBCDs in soil by vitra performance liquid chromatography-mass spectrometry[J].Journal of Analystical Science,2008,24(4):414-416.
[16]JIN J,YANG C Q,WANG Y,et al.Determination of hexabromocyclododecane diastereomers in soil by ultra performance liquid chromatography:electrospray ion source/tandem mass spectrometry[J].Chinese Journal of Analytical Chemistry,2009,37:585-588.
[17]POMA G,BINELLI A,VOLTA P,et al.Evaluation of spatial distribution and accumulation of novel brominated flame retardants,HBCD and PBDEs in an Italian subalpine lake using zebra mussel(dreissena polymorpha)[J].Environmental Science and Pollution Research,2014,21:9655-9664.
[18]ZHANG X L,LUO X J,CHEN S J,et al.Analysis of free and bound residues of polybrominated diphenyl ethers and Tetrabromobisphenol A in sediment[J].Chinese Journal of Analytical Chemistry,2009,37:1577-1582.
[19]TANG L,SHAO H Y,ZHU J Y,et al.Hexabromocyclododecane diastereoisomers in surface sediments from river drainage basins of Shanghai,China:occurrence,distribution,and mass inventory[J].Environmental Science and Pollution Research,2015,22:11993-12000.
[20]SODRE F F,PESCARA I C,MONTAGNER C C,et al.Assessing selected estrogens and xenoestrogens in brazilian surface waters by liquid chromatography-tandem mass spectrometry[J].Microchemical Journal,2010,96:92-98.
[21]JUNG D,LEE J,KIM B W.Optimum empty bed retention time for toluene degradation in a biofilter packed with ceramic beads[J].Korean Journal of Chemical Engineering,2011,28:1873-1885.
[22]KIM D W,PARK W S,PARK J T.The optimum fin width in p-MuGFETs with the consideration of NBTI and hot carrier degradation[J].Microelectronics Reliability,2010,50:1316-1329.
[23]LEE D H,LEE S M,YU C G,et al.Guideline for the optimum fin width considering hot-carrier and NBTI degradation in MuGFETs[J].Ieee Electron Device Letters,2011,32:1176-1188.
[24]HAN C,CHEN X,XIE W,et al.Determination of hexabromocyclododecane diastereoisomers in sargassum fusiforme and comparison of the extraction efficiency of ultrasonication,microwave-assisted extraction,soxhlet extraction and pressurised liquid extraction[J].Journal of Separation Science,2010,33:3319-3325.
[25]TEN-DAM G,PARDO O,TRAAG W,et al.Simultaneous extraction and determination of HBCD isomers and TBBPA by ASE and LC-MSMS in fish[J].Journal of chromatography B,2012,898:101-110.
[26]ZHONG Y,LI D,ZHU X,et al.Solvent effects on quantitative analysis of brominated flame retardants with soxhlet extraction[J].Environmental Geochemistry&Health,2017(11):1-10.
[27]OLUKUNLE O I,OKONKWO O J.Concentration of novel brominated flame retardants and HBCD in leachates and sediments from selected municipal solid waste landfill sites in Gauteng Province,South Africa[J].Waste Management,2015,43:300-306.
[28]SCHULZE T,SEILER T B,STRECK G,et al.Comparison of different exhaustive and biomimetic extraction techniques for chemical and biological analysis of polycyclic aromatic compounds in river sediments[J].Journal of Soils and Sediments,2012,12:1419-1434.
[29]WU H,DAI X,ZHOU S L,et al.Ultrasound-assisted alkaline pretreatment for enhancing the enzymatic hydrolysis of rice straw by using the heat energy dissipated from ultrasonication[J].Bioresour Technology,2017,241:70-74.
[30]LEE S Y,SHOW P L,LING T C,et al.Single-step disruption and protein recovery from chlorella vulgaris using ultrasonication and ionic liquid buffer aqueous solutions as extractive solvents[J].Biochemical Engineering Journal,2017,124:26-35.
[31]ANSARI J A,ISMAIL M,FARID M.Investigation of the use of ultrasonication followed by heat for spore inactivation[J].Food and Bioproducts Processing,2017,104:32-39.
[32]VILAPLANA F,KARLSSON P,RIBES-GREUS A,et al.Analysis of brominated flame retardants in styrenic polymers:comparison of the extraction efficiency of ultrasonication,microwave-assisted extraction and pressurised liquid extraction[J].Journal of Chromatography A,2008,1196(1):139-146.
[33]CHEMAT S,AISSA A,BOUMECHHOUR A,et al.Extraction mechanism of ultrasound assisted extraction and its effect on higher yielding and purity of artemisinin crystals from Artemisia annua L.leaves[J].Ultrason Sonochem,2017,34:310-316.
[34]李岩,王龙星,朱秀华,等.高效液相色谱-电喷雾质谱法测定环境大气中的六溴环十二烷[J].色谱,2017,35(10):1080-1085.
[35]HUANG H,WANG D,WAN W,et al.Hexabromocyclododecanes in soils and plants from a plastic waste treatment area in North China:occurrence,diastereomer-and enantiomer-specific profiles,and metabolization[J].Environmental Science&Pollution Research,2017,24(27):1-11.
[36]XU W,WANG X,CAI Z.Analytical chemistry of the persistent organic pollutants identified in the stockholm convention:a review[J].Analytica Chimica Acta,2013,790:1-13.
[37]ANIM A K,DRAGE D S,GOONETILLEKE A,et al.Distribution of PBDEs,HBCDs and PCBs in the Brisbane River estuary sediment[J].Marine Pollution Bulletin,2017,120:165-173.
[38]ROZE E,MEIJER L,BAKKER A,et al.Prenatal exposure to organohalogens,including brominated flame retardants,influences motor,cognitive,and behavioral performance at school age[J].Environmental Health Perspectives,2009,117:1953-1958.
[39]SHAW S D,BLUM A,WEBER R,et al.Halogenated flame retardants:do the fire safety benefits justify the risks?[J].Reviews on Environmental Health,2010,25(4):261-306.
[40]张永芳,王润梅,刘文英,等.超声波辅助提取黑木耳多糖及其果冻的制作[J].农业与技术,2018,38(15):30-33.
[41]叶威,何祥,柳龙,等.超声波降解溴系阻燃剂六溴环十二烷[J].化学与生物工程,2014,31(4):60-63.YE Wei,HE Xiang,LIU Long,et al.Study on ultrasonic degradation of brominated flame retardant hexabromocyclododecane[J].Chemical and Biological Engineering,2014,31(4):60-63.
[2]ERIKSSON P,FISCHER C,WALLIN M,et al.Impaired behaviour,learning and memory,in adult mice neonatally exposed to hexabromocyclododecane(HBCD)[J].Environmental Toxicology and Pharmacology,2006,21:317-322.
[3]GERECKE A C,GIGER W,HARTMANN P C,et al.Anaerobic degradation of brominated flame retardants in sewage sludge[J].Chemosphere,2006,64:311-317.
[4]ALAEE M,ARIAS P,SJODIN A,et al.An overview of commercially used brominated flame retardants,their applications,their use patterns in different countries/regions and possible modes of release[J].Environment International,2003,29:683-689.
[5]YI S,LIU J G,JIN J,et al.Assessment of the occupational and environmental risks of hexabromocyclododecane(HBCD)in China[J].Chemosphere,2016,150:431-437.
[6]WANG Y,CAI Y,JIANG G.Research processes of persistent organic pollutants(POPs)newly listed and candidate POPs in Stockholm Convention[J].Scientia Sinica Chimica,2010,40:99-123.
[7]ZACS D,RJABOVA J,PUGAJEVA I,et al.Ultra high performance liquid chromatography-time-of-flight high resolution mass spectrometry in the analysis of hexabromocyclododecane diastereomers:method development and comparative evaluation versus ultra high performance liquid chromatography coupled to Orbitrap high resolution mass spectrometry and triple quadrupole tandem mass spectrometry[J].Journal of Chromatography A,2014,1366:73-83.
[8]ZHU H,ZHANG K,SUN H,et al.Spatial and temporal distributions of hexabromocyclododecanes in the vicinity of an expanded polystyrene material manufacturing plant in Tianjin,China[J].Environmental Pollution,2017,222:338-347.
[9]YUAN J P,SUN Y M,LIU J H,et al.Determination of hexabromocyclododecane enantiomers in chicken whole blood by a modified quick,easy,cheap,effective,rugged,and safe method with liquid chromatography and tandem mass spectrometry[J].Journal of Separation Science,2016,39:2846-2852.
[10]GARCIA-VALCARCEL A I,TADEO J L.Determination of hexabromocyclododecane isomers in sewage sludge by LC-MS/MS[J].Journal of Separation Science,2009,32:3890-3897.
[11]ZHANG Y Q,LU Y L,WANG P,et al.Transport of Hexabromocyclododecane(HBCD)into the soil,water and sediment from a large producer in China[J].Science of the Total Environment,2018,610:94-100.
[12]CHEN X M.Colorimetric sensing of non-ionic and cationic surfactants using a versatile anionic poly(3,4-propylenedioxythiophene)derivative[J].Analytical Methods,2015,7:2800-2805.
[13]COVACI A,GERECKE A C,LAW R J,et al.Hexabromocyclododecanes(HBCDs)in the environment and humans:a review[J].Environmental Science&Technology,2006,40:3679-3688.
[14]PETROVA S,REZEK J,SOUDEK P,VANEK T.Preliminary study of phytoremediation of brownfield soil contaminated by PAHs[J].Science of the Total Environment,2017,599:572-580.
[15]潘荷芳,惠阳,王静,等.土壤中痕量六溴环十二烷的超高效液相色谱/质谱联用分析[J].分析科学学报,2008,24(4):414-416.PAN Hefang,HUI Yang,WANG Jing,et al.Analysis of trace HBCDs in soil by vitra performance liquid chromatography-mass spectrometry[J].Journal of Analystical Science,2008,24(4):414-416.
[16]JIN J,YANG C Q,WANG Y,et al.Determination of hexabromocyclododecane diastereomers in soil by ultra performance liquid chromatography:electrospray ion source/tandem mass spectrometry[J].Chinese Journal of Analytical Chemistry,2009,37:585-588.
[17]POMA G,BINELLI A,VOLTA P,et al.Evaluation of spatial distribution and accumulation of novel brominated flame retardants,HBCD and PBDEs in an Italian subalpine lake using zebra mussel(dreissena polymorpha)[J].Environmental Science and Pollution Research,2014,21:9655-9664.
[18]ZHANG X L,LUO X J,CHEN S J,et al.Analysis of free and bound residues of polybrominated diphenyl ethers and Tetrabromobisphenol A in sediment[J].Chinese Journal of Analytical Chemistry,2009,37:1577-1582.
[19]TANG L,SHAO H Y,ZHU J Y,et al.Hexabromocyclododecane diastereoisomers in surface sediments from river drainage basins of Shanghai,China:occurrence,distribution,and mass inventory[J].Environmental Science and Pollution Research,2015,22:11993-12000.
[20]SODRE F F,PESCARA I C,MONTAGNER C C,et al.Assessing selected estrogens and xenoestrogens in brazilian surface waters by liquid chromatography-tandem mass spectrometry[J].Microchemical Journal,2010,96:92-98.
[21]JUNG D,LEE J,KIM B W.Optimum empty bed retention time for toluene degradation in a biofilter packed with ceramic beads[J].Korean Journal of Chemical Engineering,2011,28:1873-1885.
[22]KIM D W,PARK W S,PARK J T.The optimum fin width in p-MuGFETs with the consideration of NBTI and hot carrier degradation[J].Microelectronics Reliability,2010,50:1316-1329.
[23]LEE D H,LEE S M,YU C G,et al.Guideline for the optimum fin width considering hot-carrier and NBTI degradation in MuGFETs[J].Ieee Electron Device Letters,2011,32:1176-1188.
[24]HAN C,CHEN X,XIE W,et al.Determination of hexabromocyclododecane diastereoisomers in sargassum fusiforme and comparison of the extraction efficiency of ultrasonication,microwave-assisted extraction,soxhlet extraction and pressurised liquid extraction[J].Journal of Separation Science,2010,33:3319-3325.
[25]TEN-DAM G,PARDO O,TRAAG W,et al.Simultaneous extraction and determination of HBCD isomers and TBBPA by ASE and LC-MSMS in fish[J].Journal of chromatography B,2012,898:101-110.
[26]ZHONG Y,LI D,ZHU X,et al.Solvent effects on quantitative analysis of brominated flame retardants with soxhlet extraction[J].Environmental Geochemistry&Health,2017(11):1-10.
[27]OLUKUNLE O I,OKONKWO O J.Concentration of novel brominated flame retardants and HBCD in leachates and sediments from selected municipal solid waste landfill sites in Gauteng Province,South Africa[J].Waste Management,2015,43:300-306.
[28]SCHULZE T,SEILER T B,STRECK G,et al.Comparison of different exhaustive and biomimetic extraction techniques for chemical and biological analysis of polycyclic aromatic compounds in river sediments[J].Journal of Soils and Sediments,2012,12:1419-1434.
[29]WU H,DAI X,ZHOU S L,et al.Ultrasound-assisted alkaline pretreatment for enhancing the enzymatic hydrolysis of rice straw by using the heat energy dissipated from ultrasonication[J].Bioresour Technology,2017,241:70-74.
[30]LEE S Y,SHOW P L,LING T C,et al.Single-step disruption and protein recovery from chlorella vulgaris using ultrasonication and ionic liquid buffer aqueous solutions as extractive solvents[J].Biochemical Engineering Journal,2017,124:26-35.
[31]ANSARI J A,ISMAIL M,FARID M.Investigation of the use of ultrasonication followed by heat for spore inactivation[J].Food and Bioproducts Processing,2017,104:32-39.
[32]VILAPLANA F,KARLSSON P,RIBES-GREUS A,et al.Analysis of brominated flame retardants in styrenic polymers:comparison of the extraction efficiency of ultrasonication,microwave-assisted extraction and pressurised liquid extraction[J].Journal of Chromatography A,2008,1196(1):139-146.
[33]CHEMAT S,AISSA A,BOUMECHHOUR A,et al.Extraction mechanism of ultrasound assisted extraction and its effect on higher yielding and purity of artemisinin crystals from Artemisia annua L.leaves[J].Ultrason Sonochem,2017,34:310-316.
[34]李岩,王龙星,朱秀华,等.高效液相色谱-电喷雾质谱法测定环境大气中的六溴环十二烷[J].色谱,2017,35(10):1080-1085.
[35]HUANG H,WANG D,WAN W,et al.Hexabromocyclododecanes in soils and plants from a plastic waste treatment area in North China:occurrence,diastereomer-and enantiomer-specific profiles,and metabolization[J].Environmental Science&Pollution Research,2017,24(27):1-11.
[36]XU W,WANG X,CAI Z.Analytical chemistry of the persistent organic pollutants identified in the stockholm convention:a review[J].Analytica Chimica Acta,2013,790:1-13.
[37]ANIM A K,DRAGE D S,GOONETILLEKE A,et al.Distribution of PBDEs,HBCDs and PCBs in the Brisbane River estuary sediment[J].Marine Pollution Bulletin,2017,120:165-173.
[38]ROZE E,MEIJER L,BAKKER A,et al.Prenatal exposure to organohalogens,including brominated flame retardants,influences motor,cognitive,and behavioral performance at school age[J].Environmental Health Perspectives,2009,117:1953-1958.
[39]SHAW S D,BLUM A,WEBER R,et al.Halogenated flame retardants:do the fire safety benefits justify the risks?[J].Reviews on Environmental Health,2010,25(4):261-306.
[40]张永芳,王润梅,刘文英,等.超声波辅助提取黑木耳多糖及其果冻的制作[J].农业与技术,2018,38(15):30-33.
[41]叶威,何祥,柳龙,等.超声波降解溴系阻燃剂六溴环十二烷[J].化学与生物工程,2014,31(4):60-63.YE Wei,HE Xiang,LIU Long,et al.Study on ultrasonic degradation of brominated flame retardant hexabromocyclododecane[J].Chemical and Biological Engineering,2014,31(4):60-63.