土壤和水体中毒杀芬残留检测方法研究
|
摘要
毒杀芬具有高毒、高残留、难降解、容易被生物富集及远距离迁移等特性,是一种持久性有机污染物,目前已成为环境监测的重点目标。毒杀芬组成复杂,在土壤和水体等环境样品中的准确定量分析一直是有机污染物分析中的难点。本文对土壤和水体中毒杀芬的提取、净化、检测技术进行了系统研究,分别建立了加速溶剂萃取-负化学电离质谱法测定土壤中的毒杀芬;圆盘固相萃取-负化学电离质谱法测定水体中的毒杀芬,建立的检测方法方便、快捷、环保、准确、灵敏度高、精密度好,满足现代绿色分析技术的要求。
文中采用现在国内应用较少的气相色谱-负化学电离质谱联用技术(GC-NCI/MS)与气相色谱-电子轰击电离质谱联用技术(GC-EI/MS)、气相色谱-电子捕获检测技术(GC-ECD)对毒杀芬的检测方法进行了对比研究。结果表明,GC-NCI/MS、GC-EI/MS、GC-ECD三种方法的仪器检出限分别为0.1ng/mL、5ng/mL、0.4ng/mL。GC-EI/MS具有很好的定性能力,但是检出限比较高,无法实现样品中痕量及微量毒杀芬的检测;GC-ECD虽具有和GC-NCI/MS相当的检出限,但无法实现对毒杀芬的准确定性和定量;GC-NCI/MS不仅具有很低的检出限,而且具有很强的定性、定量功能,在三种方法中最适合基质复杂、痕量或微量样品中毒杀芬的检测。
单一净化技术对复杂基质样品无法达到较好的净化效果,本文比较研究了磺化法、弗罗里硅土、硅胶、氧化铝、Cleanert PestiCarb活性碳黑等对毒杀芬的净化效果,选定Cleanert PestiCarb活性碳黑与弗罗里硅土组成的复合层析柱净化样品,毒杀芬回收率为87.5%～97.9%,精密度(n=7)为5.05%～12.25%。
加速溶剂萃取与微波辅助萃取是新型的固体样品前处理技术,本文将其用于土壤样品中毒杀芬的前处理方法研究。加速溶剂萃取方法中优化了萃取溶剂、萃取压力、萃取温度、萃取时间、循环次数等参数;微波辅助萃取实验中优化了提取溶剂、微波功率、萃取温度、萃取时间等参数;优化后的两种方法的平均回收率分别为102.5%、95.2%,明显高于经典索氏提取方法的回收率79.6%。两种方法均可以用于土壤样品中毒杀芬的提取,微波辅助提取虽一批次可以处理24个样品,但相对加速溶剂萃取具有操作步骤较多、溶剂用量大、安全系数小等劣势。在优化的加速溶剂萃取实验条件下,重复七次实验,得到的方法平均回收率为92.2%～105.6%,方法检出限为0.1-3.0ng/g,精密度为2.97%-12.35%。实验表明,加速溶剂萃取具有操作简单、高效、环保等优点,是一种方便、有效的提取方法。
GDX-502树脂是国产的一种比较好的吸附剂,目前主要用于酚类化合物的富集提取。本文将GDX-502树脂用于装填固相萃取小柱,选用Empore~(TM)-C18 DISK作为固相萃取膜,优化了两种前处理方法中的样品pH值、水样流速、洗脱溶剂等条件。结果表明,圆盘固相萃取的回收率为90.5%～103.1%,稍高于固相小柱萃取的回收率78.4%～95.3%,并且分析效率是后者的3倍,但前两种方法的回收效果明显高于液-液萃取的66.7%～86.7%。采用优化后的圆盘固相萃取方法处理七个重复水样,方法检出限达0.5-30ng/L,精密度为3.64%-10.16%。
本文利用上述建立的土壤和水体中毒杀芬残留检测方法对实际样品进行检测,结果表明方法实用,检测数据可靠。
As one of the most important group of Persistent Organic Pollutants (POPs), Toxaphene, with intense toxicity, high residuary, hardness of being metabolized, easier to be enriched by biology and with long-range transportability, so that ,it have stirred interest in the study of Environment Science. Up to now, Toxaphene has become main object in environment investigation. The complexity of the toxaphene mixture has intrigued and challenged analytical chemists for decades, and it is still difficult to quantitative analysis. The present thesis studied systematism the process of detection toxaphene, and covered toxaphene extraction, cleanup and detection technique. Moreover, the method of toxaphene analysis in soil by ASE - NCI/ MS, and analysis the object in water by solid-phase disk extraction (SPE) - NCI/MS were developed. These methods are convenient, fast, environmental protection, high sensitivity, accuracy, good relative standard deviation and content with Green Analytical Chemistry's requirement.
Comparative study of using GC-NCI/MS, GC-EI/MS, GC-ECD to detecting toxaphene was conducted, the GC-NCI/MS technique has few applications in china. The equipment detection limit was 0.1ng/mL,5ng/mL,0.4ng/mL. The accurate qualitative and quantitative of tocxaphene can't be achieved by GC-ECD,the GC-EI/MS can't detect trace samples, but GC-NCI/MS method not only has a very low detection limit, but also have a very strong qualitative capacity, which is showed to be the best detection method.
The co-cleanup techniques of solid phase extraction with florisil column, silica gel column, alunima column and Cleanert PestiCarb which were used to eliminate the recoveries of toxaphene. The average recoveries of the co-cleanup technique by Cleanert PestiCarb and Florisil column was the best, the recoveries of toxaphene was ranged from 87.5% to 97.9%, the relative standard deviation was in range of 5.05% to 12.25%.
The ASE and MAE were modern pre-treatment technology of solid sample. The power, solvent, pressure, temperature, and times were optimized. The average recoveries of two optimized mothods were 102.5% and 95.2%, they were significantly higher than 79.6% of the SE method. Two methods can be used in soil sample's extraction, MAE can deal with twenty-four samples at the same time, but it need more solvent, more steps and not safe than ASE. In the optimized conditions of ASE, the average recovery was 92.2%- 105.6%, the MRL were 0.1-3.0ng/g,the precision is 2.97%-12.35% (n=7),so it was suitable to be used in laboratory.
Three methods of liquid - liquid extraction (LLE), solid-phase column extraction (SPE column) and solid-phase disk extraction (SPE disk) were used in pre-treatment of water samples. In SPE methods we selected Empore~(TM)-C18 DISK membrane and GDX-502 resin which made in china was used to the enrichment of phenolic compound. Some factors influencing the extraction efficiency of SPE method, such as pH value of water sample, extraction pressure and elution solution were studied. The result indicated that the average recovery of the LLE, the column SPE and the disk SPE were 66.7%-86.7%,78.4%-95.3% and 90.5%-103.1%, respectively, but the efficiency of the disk SPE was three times than the column SPE. The MRL of the SPE disk was 0.5-30ng/L, the precision is 3.64%-10.16% (n=7). This SPE disk method has fast flow, high, absorbability, lower counter pressure, so it has been used more widely in domestic and abroad these years.
Finally, the established pretreatment and detection method were applied successfully to soil and water samples obtained from different regions for the determination of toxaphene residue. The results showed that most of samples had been polluted in different levels. The method has been proved to be credible.
文中采用现在国内应用较少的气相色谱-负化学电离质谱联用技术(GC-NCI/MS)与气相色谱-电子轰击电离质谱联用技术(GC-EI/MS)、气相色谱-电子捕获检测技术(GC-ECD)对毒杀芬的检测方法进行了对比研究。结果表明,GC-NCI/MS、GC-EI/MS、GC-ECD三种方法的仪器检出限分别为0.1ng/mL、5ng/mL、0.4ng/mL。GC-EI/MS具有很好的定性能力,但是检出限比较高,无法实现样品中痕量及微量毒杀芬的检测;GC-ECD虽具有和GC-NCI/MS相当的检出限,但无法实现对毒杀芬的准确定性和定量;GC-NCI/MS不仅具有很低的检出限,而且具有很强的定性、定量功能,在三种方法中最适合基质复杂、痕量或微量样品中毒杀芬的检测。
单一净化技术对复杂基质样品无法达到较好的净化效果,本文比较研究了磺化法、弗罗里硅土、硅胶、氧化铝、Cleanert PestiCarb活性碳黑等对毒杀芬的净化效果,选定Cleanert PestiCarb活性碳黑与弗罗里硅土组成的复合层析柱净化样品,毒杀芬回收率为87.5%～97.9%,精密度(n=7)为5.05%～12.25%。
加速溶剂萃取与微波辅助萃取是新型的固体样品前处理技术,本文将其用于土壤样品中毒杀芬的前处理方法研究。加速溶剂萃取方法中优化了萃取溶剂、萃取压力、萃取温度、萃取时间、循环次数等参数;微波辅助萃取实验中优化了提取溶剂、微波功率、萃取温度、萃取时间等参数;优化后的两种方法的平均回收率分别为102.5%、95.2%,明显高于经典索氏提取方法的回收率79.6%。两种方法均可以用于土壤样品中毒杀芬的提取,微波辅助提取虽一批次可以处理24个样品,但相对加速溶剂萃取具有操作步骤较多、溶剂用量大、安全系数小等劣势。在优化的加速溶剂萃取实验条件下,重复七次实验,得到的方法平均回收率为92.2%～105.6%,方法检出限为0.1-3.0ng/g,精密度为2.97%-12.35%。实验表明,加速溶剂萃取具有操作简单、高效、环保等优点,是一种方便、有效的提取方法。
GDX-502树脂是国产的一种比较好的吸附剂,目前主要用于酚类化合物的富集提取。本文将GDX-502树脂用于装填固相萃取小柱,选用Empore~(TM)-C18 DISK作为固相萃取膜,优化了两种前处理方法中的样品pH值、水样流速、洗脱溶剂等条件。结果表明,圆盘固相萃取的回收率为90.5%～103.1%,稍高于固相小柱萃取的回收率78.4%～95.3%,并且分析效率是后者的3倍,但前两种方法的回收效果明显高于液-液萃取的66.7%～86.7%。采用优化后的圆盘固相萃取方法处理七个重复水样,方法检出限达0.5-30ng/L,精密度为3.64%-10.16%。
本文利用上述建立的土壤和水体中毒杀芬残留检测方法对实际样品进行检测,结果表明方法实用,检测数据可靠。
As one of the most important group of Persistent Organic Pollutants (POPs), Toxaphene, with intense toxicity, high residuary, hardness of being metabolized, easier to be enriched by biology and with long-range transportability, so that ,it have stirred interest in the study of Environment Science. Up to now, Toxaphene has become main object in environment investigation. The complexity of the toxaphene mixture has intrigued and challenged analytical chemists for decades, and it is still difficult to quantitative analysis. The present thesis studied systematism the process of detection toxaphene, and covered toxaphene extraction, cleanup and detection technique. Moreover, the method of toxaphene analysis in soil by ASE - NCI/ MS, and analysis the object in water by solid-phase disk extraction (SPE) - NCI/MS were developed. These methods are convenient, fast, environmental protection, high sensitivity, accuracy, good relative standard deviation and content with Green Analytical Chemistry's requirement.
Comparative study of using GC-NCI/MS, GC-EI/MS, GC-ECD to detecting toxaphene was conducted, the GC-NCI/MS technique has few applications in china. The equipment detection limit was 0.1ng/mL,5ng/mL,0.4ng/mL. The accurate qualitative and quantitative of tocxaphene can't be achieved by GC-ECD,the GC-EI/MS can't detect trace samples, but GC-NCI/MS method not only has a very low detection limit, but also have a very strong qualitative capacity, which is showed to be the best detection method.
The co-cleanup techniques of solid phase extraction with florisil column, silica gel column, alunima column and Cleanert PestiCarb which were used to eliminate the recoveries of toxaphene. The average recoveries of the co-cleanup technique by Cleanert PestiCarb and Florisil column was the best, the recoveries of toxaphene was ranged from 87.5% to 97.9%, the relative standard deviation was in range of 5.05% to 12.25%.
The ASE and MAE were modern pre-treatment technology of solid sample. The power, solvent, pressure, temperature, and times were optimized. The average recoveries of two optimized mothods were 102.5% and 95.2%, they were significantly higher than 79.6% of the SE method. Two methods can be used in soil sample's extraction, MAE can deal with twenty-four samples at the same time, but it need more solvent, more steps and not safe than ASE. In the optimized conditions of ASE, the average recovery was 92.2%- 105.6%, the MRL were 0.1-3.0ng/g,the precision is 2.97%-12.35% (n=7),so it was suitable to be used in laboratory.
Three methods of liquid - liquid extraction (LLE), solid-phase column extraction (SPE column) and solid-phase disk extraction (SPE disk) were used in pre-treatment of water samples. In SPE methods we selected Empore~(TM)-C18 DISK membrane and GDX-502 resin which made in china was used to the enrichment of phenolic compound. Some factors influencing the extraction efficiency of SPE method, such as pH value of water sample, extraction pressure and elution solution were studied. The result indicated that the average recovery of the LLE, the column SPE and the disk SPE were 66.7%-86.7%,78.4%-95.3% and 90.5%-103.1%, respectively, but the efficiency of the disk SPE was three times than the column SPE. The MRL of the SPE disk was 0.5-30ng/L, the precision is 3.64%-10.16% (n=7). This SPE disk method has fast flow, high, absorbability, lower counter pressure, so it has been used more widely in domestic and abroad these years.
Finally, the established pretreatment and detection method were applied successfully to soil and water samples obtained from different regions for the determination of toxaphene residue. The results showed that most of samples had been polluted in different levels. The method has been proved to be credible.
引文
1.曹群立,陈凤鳞.毒杀芬诱变作用的研究[J].中国劳动卫生职业病杂志,1985,3(1):17-19.
2.戴晖.微波萃取-毛细管气相色谱法快速分析土壤中有机氯农药[J].分析仪器,2004,2:31-34.
3.范元中,张莘民.半渗透膜采样技术在有机污染监测中的应用[J].环境监测管理技术,2003,15(2):14-16.
4.郭丽青,朱雪梅,崔艳红等.污染水稻土有机氯农药残留分析的样品净化[J].环境化学,2002,21(2):177-182.
5.江泉观,纪云晶,常元勋.环境化学毒物防治手册[M].北京:化学工业出版社,2004:987-988.
6.郎印海,蒋新,赵振华等.土壤中13种有机氯农药超声波提取方法研究[J].环境科学学报,2004,24(2):291-296.
7.李樱,储晓刚,仲维科等.凝胶渗透色谱-气相色谱同时测定糙米中拟除虫菊酯、有机氯农药和多氯联苯的残留量[J].色谱,2002,22(5):551-554.
8.刘伟,张明祥,杨海鹏.美国EPA新方法-微波快速溶剂萃取技术[J].现代科学仪器,2005,(1):52-55.
9.邱月明,温可可,白桦.超临界流体萃取-气相色谱法测定粮谷和茶叶中的有机氯农药残留量[J].分析化学,1997,25(12):1391-1394.
10.王明泰,刘志研,李爱军.纺织品的毒杀芬残留量测定,印染,2006,60:55-59.
11.吴欣江.三种POPs物质与环境致突变物苯并[a]芘的联合遗传毒性研究[J].华中科技大学学报,2002,267(5):134-142.
12.熊国华,邹世春,张展霞.环境分析试样预处理的新方法-微波萃取法[J].环境科学进展,1997,5(5):58-62.
13.熊国华,邹世春,张展霞.微波萃取土壤中PAHs的研究[J].高等学校化学学报,1998,19(10):1560-1565.
14.许行义,刘劲松,庞晓露.土壤中有机氯农药残留分析前处理方法研究[J].浙江科技学院学报,2003,15增刊:36-38.
15.杨春,陈彬,陈敏.毒杀芬对孤儿受体雌激素相关受体1(ERRα—1)的拮抗作用[J].第三军医大学学报,2001,23(10):1183-1185.
16.叶明立,朱岩.ASE加速溶剂萃取技术在食品、农残方面的应用[J].现代科学仪器,2003,1:35-37.
17.易军,李云春,弓振斌.食品中农药残留分析的样品前处理技术进展[J].化学进展,2002,16:119-124.
18.岳永德.农药残留分析.北京:中国农业出版社.2004.
19.张道宁,周志平,汤友志等.固相微萃取与色谱联用方法分析水中12种有机氯农药[J].分析化学,1999,27(7):768-772.
20.张海霞,朱彭龄.固相萃取.分析化学,2000,28:1172-1180.
21.张静,寇登民.农药残留现代仪器分析方法[J].现代仪器,2005,1:8-10.
22.张俊增,王秀凤,王兆文.气相色谱法测定黄河底泥中多氯联苯及有机氯农药[J].上海环境科学,2001,21(6):299-306.
23.张玲金,谢文明.多壁纳米碳管固相萃取测定水中的有机氯农药[J].分析测试学报.2004,23(5)增刊:258-261.
24.朱雪梅,崔艳红,郭丽青等.用加速溶剂提取仪提取污染土壤中的有机氯农药[J].环境科学,2002,23(5):113-116.
25.Adou K,Bontoyan W R,Sweeney P J.Multiresidue method for the analysis of pesticide residues in fruits and vegetables by accelerated solvent extraction and capillary gas chromatography[J].Agri Food Chem,2005,53:9374-9382.
26.Annika Smeds,Pekka Saukko.Identification of polychlorinated biphenyls and some endocrine disrupting pesticides in human adipose tissue from Finland[J].Chemosphere,2001.44(6):1463-1471.
27.Attard Barbini D,Stefanelli P,GIrolimetti S,Muccio Di,Dommarco R.Determination of Toxaphene Residues in Fish Foodstuff by GC-MS[J].Environment ComtanentToxicolity,2007,79:226-230.
28.Beltran J,Lopez F J,Hernandez E Solid-phase microextraction in pesticide residue analysis[J].Chromatography A,2000,885:389-404.
29.BuntinGA.Insecticidal Compositions Comprising Chlorinated Camphene[P].U.S.:2,565,471,Aug.28,1951.
30.Can Quan.Supercritical fluid extraction and clean-up of organochlorine pesticides in ginseng[J].The Journal of Supercritical Fluids,2004,31(2):149-157.
31.Caroline E Green,Michael H Abraham.Investigation into the effects of temperature and stirring rate on the solid-phase extraction of diuron from water using a C18 extraction disk[J].Journal of Chromatography A.2000.885(12):41-49.
32. Chen J, Pawliszyn J, Solid phase microextraction coupled tohigh-perfonnance liquid chromatography [J].Anal Chem, 1995,67:2630-2533.
33. Conka K, drobna B, kocan A, Petrik J. Simple solid-phase extraction mothod for determination of polychlorinated biphenyls and selected organochlorine pesticides in human serum[J].Journal of Chromatography A, 2005.1084(12):33-38.
34. Covaci A, Gheorghe A, Voorspoels S, et al. Polychlorinated biphenyls and organochlorine pesticides in sediment cores from the Western Scheldt River (Belgium):analytical aspects and depth profiles[J]. Environment International.2005,31(3): 367-375.
35. DeGeus H,De Boer J,Brinkman J. Multidimensional gas chromatography analysis of toxaphene[J]. Environment Science Technology,1997,767:137-151.
36. Fatoki O S, Awofolu R O. Methods for selective determination of persistent organochlorine pesticide residues in water and sediments by capillary gas chromatography and electron capture detection[J]. Journal of Chromatography A,2003,983 (12): 225-236.
37. Gan J, Papiemik S K, Koskinen W C, et al. Evaluation of accelerated solvent extraction(ASE) for analysis of pesticide residues in soil[J]. Environ Sci Technol,1999,33:3249-3253.
38. Ganzler K, Salgo A, Valko K. Micromave Extravtion: A novel sample preparation method for chromatography[J]. Chromatogr, 1986,371(1):299-306.
39. Goncalves C, Alpendurada M F. Solid phase microextraction-gas chromatography (tandem) mass spectrometry as a tool for pesticide residue analysis in water samples at high sensitivity and selectivity with confirmation capabilities[J]. Chromatography A,2004,1026:239-250.
40. Goncalves C, Alpendurada, M.F. Assessment of pesticide contamination in soil samples from an intensive horticulture area , using ultrasonic extraction and gas chromatography-mass spectrometry[J].Talana.2005,65(5): 1179-1189.
41. Hooper K, Ames N, Saleh A. Toxaphene, a complex mixture polychloroterpenes and a major insecticide[J]. Science,1979,4406:591-593.
42. Husers N, Kleibohmer W, Camman C, Schulz I, Schw. Erdt P, Stoffers H. Procssdings of 13~(th) Intern. Symp. Dioxins and Related Compounds, Organohalogen Compounds[C]. Helsinki:Finish Institute of Occupational Health,publicationsoffice,1993.
43. Jinno K, Taniguchi M, Hayashida M. Solid phase micro extraction coupled with semi-microcolumn high performance liquid chromatography for the analysis of benzodiazepines in human urine[J]. Pharmaceutical and Biomedical.1998,17:1081-1091.
44. John Andrew, Mahugija Marco, Michael A, kishimba. Cancentrations of pesticide residues in grasses and sedges due to point source contimation and the indications for public health risks, Vikuge, Tanzania[J]. Chemosphere,2005.61(9):1293-1398.
45. John RAdrian RWoolfitt,Vincent L,Maggio,Donald G,Patteason J. Measurement of Toxaphene Congeners in Pooled Human Serum Collected in Three US Cities Using High-Resolution Mass Spectrometry [J]. Arch Environment Contament Toxicolity,2004,46:551-556.
46. John R, Paul A Helm. Advances in the environmental analysis of olychlorinated naphthalenes and toxaphene[J]. Anal Bioanal Chemistry, 2006 386(4):819-836.
47. Karina S B, Miglioranza, Julia E. Aizpum de Moreno, et al. Evaluation of canventionally and organically produced vegetables for high lipophilic organochlorine pesticide(OCP) residues[J]. Food and Chemical Toxicology,2005.43(2):261-269.
48. Koichi Saito, Andreas Sjodin, Courtney D, Sandau, et al. Development of a accelerated solvent extraction and gel permeation chromatography analytical method for measuring persistent organohalogen compounds in adipose and organ tissue analysis[J]. Chemosphere, 2005,57(5);373-381.
49. Korytor P,Van Stee, Leonards P, De Boer J, Brinkman C. A ttempt to unravel the composition of toxaphene by comprehensive two-dimensional gas chromatography with selective detectionf J]. Journal of Chromatography, 2003,994: 179-189.
50. Min-Woo Jung, Kyu-Hong Ahn, Yonghum Lee, et al. Evalution on the adsorption capabilities of new chemically modified polymeric adsorbents with protoporphyrinfJ]. Journal of Chromatography A. 2001.917(12):87-93.
51. Nam K S, Kapila S, Puri R K, Yanders A F, Larsen BT. Proc. Of 12~(th) Intern. Symp. On Dioxins and Related Compounds, Organohalogen Compounds[C]. Helsinki: Finish Institute of Occupational Health, publicationsoffice, 1992.15.
52. Nerin C, Batlle R, Sartaguda M, et al. Supercritical fluid extraction of organochlorine pesticides and some metabolities in frogs from National Park of Ordesa and Monte Perdido [J]. Analytical ChimicaActa, 2002,464(2):303-312.
53. Niessen K H, Helbich H M, Teufel M,Witt K I, Bonn W, Muler J. Altbekannte Schadstoffe und neuentdeckte Toxaphene in Fettgewe bevon Kindern[J]. Environmental Pollution, 1998, 146(5):235-240.
54. Obana H,Okihashi M,Akutsu K,et al. CPPU(N-(2-chloro-4-pyridy)-N'-phenylurea) on fruit growth, maturity, and storage quatity of kiwifruit.N.ZJ.Crop Hort.Sci.2003,21:253-261.
55. Phillips J B, Xu J. Hexachlorocyclohexane isomers as markers in the water flow of the Atlantic Ocean[J]. Organohalogen Compounds, 2000,31:199-201.
56. Pichon V.Solid-phase extraction for multiresidue analysis of organic contaminants in water. Chromatogr A,2000,885:195-215.
57. Pihlstrom T, Osterdahl B G. Analysis of pesticide residues in fruit and vegetables after cleanup with solid-phase extraction using ENV+(Polystyrene-Divinylbenzene) cartridges. Agric Food Chem, 1999,47:2549-2552.
58. Polder A, Odland J O, Tkachev A. Geographic variation of chlorinated pesticides, toxaphenes and PCBs in human milk from sub- arctic and arctic locations in Russia[J] . Science of the Total Environment, 2003 , 306:179-195.
59. Sakamoto M, Tsutsumi T. Applicability of headspace solid-phase microextraction to the determination of multi-class pesticides in waters[J]. Chromatography A,2004,10:63-74.
60. Schenck F J, Donoghue D J. Determination of organochlorine and organophosphorus pesticide residue eggs using a solid phase extraction cleanup. Agric Food Chem, 2000,48:6412-6415.
61. Takazawa Y, Yoshikane M, Shibata Y. Toxaphene and Other Organochlorine Compounds in Pintails (Anas acuta) from Saitama Kamoba in Japan during Oct 2000-Feb 2002[J]. Bull Environment Contament Toxicolity,2007, 79:87-90
62. U.S.EPA, Soil Screening for Toxaphene by Immunoassay, Method 4040[D]. 1996,125-197.
63. Vania Gomes Zuin, Alexandre Leite Lopes, Janete Harumi Yariwake, et al. Application of a novel sol-gel polydimethylsiloxane (vinyl alcohol) solid-phase microextraction fiber for gas chromatographic determination of pesticide residues in herbal infusions[J]. Journal of Chromatography A,2004,1056 (12): 21-26.
64. Vetter W, Luckas B. Enantioselective determination of persistent and partly degradable toxaphene congeners in high trophic level biota[J]. Chemosphere, 2000 ,41:499- 506.
65. Vetter W, Krock B, Lucks B.Congener Specific Determination of Compounds of Technical Toxaphene(CTTs) in Different Antarctic Seal Species[J].Chromatographia,1997,44:65-73
66. Vetter W, Oehme M. Toxaphene analysis and environmental fate of congeners[J]. New Types of Persistent Halogenated Compounds,2000, (3):237- 239.
67.Vetter W,Oehme M.Toxaphene analysis and the environmental fate of congeners[A].In:Paasivirta J(Ed).New Types of Persistent Halogenated Compounds[C].Springer,Berlin,2003,(3):237-287.
68.Viorica Lopez-Avila,Janet Benedicto.Microwave assisted extration combined with gas chromatography and enzyme-linked immunosorbent assay[J].TrAC Trends in Analytical Chemistry.1996,15(8):334-341.
69.Wester P G,Geus H J,Boer J.From Chemosphere to biosphere[J].World Journal of Microbiology and Biotechnology,2001,17(6):651-655.
70.Witte J,Buthe A,Ternes W.Congener-specific analysis of toxaphene in eggs of seabirds from Germany by HRGC- NCI-MS using a carborane-siloxane copolymer phase[J].Chemosphere,2000,41:529-539.
71.Xu J,Stem G A.Selective accumulation of polychlorochampenes in aquatic biota from the Canadian Artic[J].Environment Toxicolity Chemistry,1998,12:701-709.
72.Zinmmerma L R.Detection of persistent organic pollutants in the Mississippi Delta using semipermeable membrane devices[J].The Science of the Total Environment,2000,248(23):169-179.
2.戴晖.微波萃取-毛细管气相色谱法快速分析土壤中有机氯农药[J].分析仪器,2004,2:31-34.
3.范元中,张莘民.半渗透膜采样技术在有机污染监测中的应用[J].环境监测管理技术,2003,15(2):14-16.
4.郭丽青,朱雪梅,崔艳红等.污染水稻土有机氯农药残留分析的样品净化[J].环境化学,2002,21(2):177-182.
5.江泉观,纪云晶,常元勋.环境化学毒物防治手册[M].北京:化学工业出版社,2004:987-988.
6.郎印海,蒋新,赵振华等.土壤中13种有机氯农药超声波提取方法研究[J].环境科学学报,2004,24(2):291-296.
7.李樱,储晓刚,仲维科等.凝胶渗透色谱-气相色谱同时测定糙米中拟除虫菊酯、有机氯农药和多氯联苯的残留量[J].色谱,2002,22(5):551-554.
8.刘伟,张明祥,杨海鹏.美国EPA新方法-微波快速溶剂萃取技术[J].现代科学仪器,2005,(1):52-55.
9.邱月明,温可可,白桦.超临界流体萃取-气相色谱法测定粮谷和茶叶中的有机氯农药残留量[J].分析化学,1997,25(12):1391-1394.
10.王明泰,刘志研,李爱军.纺织品的毒杀芬残留量测定,印染,2006,60:55-59.
11.吴欣江.三种POPs物质与环境致突变物苯并[a]芘的联合遗传毒性研究[J].华中科技大学学报,2002,267(5):134-142.
12.熊国华,邹世春,张展霞.环境分析试样预处理的新方法-微波萃取法[J].环境科学进展,1997,5(5):58-62.
13.熊国华,邹世春,张展霞.微波萃取土壤中PAHs的研究[J].高等学校化学学报,1998,19(10):1560-1565.
14.许行义,刘劲松,庞晓露.土壤中有机氯农药残留分析前处理方法研究[J].浙江科技学院学报,2003,15增刊:36-38.
15.杨春,陈彬,陈敏.毒杀芬对孤儿受体雌激素相关受体1(ERRα—1)的拮抗作用[J].第三军医大学学报,2001,23(10):1183-1185.
16.叶明立,朱岩.ASE加速溶剂萃取技术在食品、农残方面的应用[J].现代科学仪器,2003,1:35-37.
17.易军,李云春,弓振斌.食品中农药残留分析的样品前处理技术进展[J].化学进展,2002,16:119-124.
18.岳永德.农药残留分析.北京:中国农业出版社.2004.
19.张道宁,周志平,汤友志等.固相微萃取与色谱联用方法分析水中12种有机氯农药[J].分析化学,1999,27(7):768-772.
20.张海霞,朱彭龄.固相萃取.分析化学,2000,28:1172-1180.
21.张静,寇登民.农药残留现代仪器分析方法[J].现代仪器,2005,1:8-10.
22.张俊增,王秀凤,王兆文.气相色谱法测定黄河底泥中多氯联苯及有机氯农药[J].上海环境科学,2001,21(6):299-306.
23.张玲金,谢文明.多壁纳米碳管固相萃取测定水中的有机氯农药[J].分析测试学报.2004,23(5)增刊:258-261.
24.朱雪梅,崔艳红,郭丽青等.用加速溶剂提取仪提取污染土壤中的有机氯农药[J].环境科学,2002,23(5):113-116.
25.Adou K,Bontoyan W R,Sweeney P J.Multiresidue method for the analysis of pesticide residues in fruits and vegetables by accelerated solvent extraction and capillary gas chromatography[J].Agri Food Chem,2005,53:9374-9382.
26.Annika Smeds,Pekka Saukko.Identification of polychlorinated biphenyls and some endocrine disrupting pesticides in human adipose tissue from Finland[J].Chemosphere,2001.44(6):1463-1471.
27.Attard Barbini D,Stefanelli P,GIrolimetti S,Muccio Di,Dommarco R.Determination of Toxaphene Residues in Fish Foodstuff by GC-MS[J].Environment ComtanentToxicolity,2007,79:226-230.
28.Beltran J,Lopez F J,Hernandez E Solid-phase microextraction in pesticide residue analysis[J].Chromatography A,2000,885:389-404.
29.BuntinGA.Insecticidal Compositions Comprising Chlorinated Camphene[P].U.S.:2,565,471,Aug.28,1951.
30.Can Quan.Supercritical fluid extraction and clean-up of organochlorine pesticides in ginseng[J].The Journal of Supercritical Fluids,2004,31(2):149-157.
31.Caroline E Green,Michael H Abraham.Investigation into the effects of temperature and stirring rate on the solid-phase extraction of diuron from water using a C18 extraction disk[J].Journal of Chromatography A.2000.885(12):41-49.
32. Chen J, Pawliszyn J, Solid phase microextraction coupled tohigh-perfonnance liquid chromatography [J].Anal Chem, 1995,67:2630-2533.
33. Conka K, drobna B, kocan A, Petrik J. Simple solid-phase extraction mothod for determination of polychlorinated biphenyls and selected organochlorine pesticides in human serum[J].Journal of Chromatography A, 2005.1084(12):33-38.
34. Covaci A, Gheorghe A, Voorspoels S, et al. Polychlorinated biphenyls and organochlorine pesticides in sediment cores from the Western Scheldt River (Belgium):analytical aspects and depth profiles[J]. Environment International.2005,31(3): 367-375.
35. DeGeus H,De Boer J,Brinkman J. Multidimensional gas chromatography analysis of toxaphene[J]. Environment Science Technology,1997,767:137-151.
36. Fatoki O S, Awofolu R O. Methods for selective determination of persistent organochlorine pesticide residues in water and sediments by capillary gas chromatography and electron capture detection[J]. Journal of Chromatography A,2003,983 (12): 225-236.
37. Gan J, Papiemik S K, Koskinen W C, et al. Evaluation of accelerated solvent extraction(ASE) for analysis of pesticide residues in soil[J]. Environ Sci Technol,1999,33:3249-3253.
38. Ganzler K, Salgo A, Valko K. Micromave Extravtion: A novel sample preparation method for chromatography[J]. Chromatogr, 1986,371(1):299-306.
39. Goncalves C, Alpendurada M F. Solid phase microextraction-gas chromatography (tandem) mass spectrometry as a tool for pesticide residue analysis in water samples at high sensitivity and selectivity with confirmation capabilities[J]. Chromatography A,2004,1026:239-250.
40. Goncalves C, Alpendurada, M.F. Assessment of pesticide contamination in soil samples from an intensive horticulture area , using ultrasonic extraction and gas chromatography-mass spectrometry[J].Talana.2005,65(5): 1179-1189.
41. Hooper K, Ames N, Saleh A. Toxaphene, a complex mixture polychloroterpenes and a major insecticide[J]. Science,1979,4406:591-593.
42. Husers N, Kleibohmer W, Camman C, Schulz I, Schw. Erdt P, Stoffers H. Procssdings of 13~(th) Intern. Symp. Dioxins and Related Compounds, Organohalogen Compounds[C]. Helsinki:Finish Institute of Occupational Health,publicationsoffice,1993.
43. Jinno K, Taniguchi M, Hayashida M. Solid phase micro extraction coupled with semi-microcolumn high performance liquid chromatography for the analysis of benzodiazepines in human urine[J]. Pharmaceutical and Biomedical.1998,17:1081-1091.
44. John Andrew, Mahugija Marco, Michael A, kishimba. Cancentrations of pesticide residues in grasses and sedges due to point source contimation and the indications for public health risks, Vikuge, Tanzania[J]. Chemosphere,2005.61(9):1293-1398.
45. John RAdrian RWoolfitt,Vincent L,Maggio,Donald G,Patteason J. Measurement of Toxaphene Congeners in Pooled Human Serum Collected in Three US Cities Using High-Resolution Mass Spectrometry [J]. Arch Environment Contament Toxicolity,2004,46:551-556.
46. John R, Paul A Helm. Advances in the environmental analysis of olychlorinated naphthalenes and toxaphene[J]. Anal Bioanal Chemistry, 2006 386(4):819-836.
47. Karina S B, Miglioranza, Julia E. Aizpum de Moreno, et al. Evaluation of canventionally and organically produced vegetables for high lipophilic organochlorine pesticide(OCP) residues[J]. Food and Chemical Toxicology,2005.43(2):261-269.
48. Koichi Saito, Andreas Sjodin, Courtney D, Sandau, et al. Development of a accelerated solvent extraction and gel permeation chromatography analytical method for measuring persistent organohalogen compounds in adipose and organ tissue analysis[J]. Chemosphere, 2005,57(5);373-381.
49. Korytor P,Van Stee, Leonards P, De Boer J, Brinkman C. A ttempt to unravel the composition of toxaphene by comprehensive two-dimensional gas chromatography with selective detectionf J]. Journal of Chromatography, 2003,994: 179-189.
50. Min-Woo Jung, Kyu-Hong Ahn, Yonghum Lee, et al. Evalution on the adsorption capabilities of new chemically modified polymeric adsorbents with protoporphyrinfJ]. Journal of Chromatography A. 2001.917(12):87-93.
51. Nam K S, Kapila S, Puri R K, Yanders A F, Larsen BT. Proc. Of 12~(th) Intern. Symp. On Dioxins and Related Compounds, Organohalogen Compounds[C]. Helsinki: Finish Institute of Occupational Health, publicationsoffice, 1992.15.
52. Nerin C, Batlle R, Sartaguda M, et al. Supercritical fluid extraction of organochlorine pesticides and some metabolities in frogs from National Park of Ordesa and Monte Perdido [J]. Analytical ChimicaActa, 2002,464(2):303-312.
53. Niessen K H, Helbich H M, Teufel M,Witt K I, Bonn W, Muler J. Altbekannte Schadstoffe und neuentdeckte Toxaphene in Fettgewe bevon Kindern[J]. Environmental Pollution, 1998, 146(5):235-240.
54. Obana H,Okihashi M,Akutsu K,et al. CPPU(N-(2-chloro-4-pyridy)-N'-phenylurea) on fruit growth, maturity, and storage quatity of kiwifruit.N.ZJ.Crop Hort.Sci.2003,21:253-261.
55. Phillips J B, Xu J. Hexachlorocyclohexane isomers as markers in the water flow of the Atlantic Ocean[J]. Organohalogen Compounds, 2000,31:199-201.
56. Pichon V.Solid-phase extraction for multiresidue analysis of organic contaminants in water. Chromatogr A,2000,885:195-215.
57. Pihlstrom T, Osterdahl B G. Analysis of pesticide residues in fruit and vegetables after cleanup with solid-phase extraction using ENV+(Polystyrene-Divinylbenzene) cartridges. Agric Food Chem, 1999,47:2549-2552.
58. Polder A, Odland J O, Tkachev A. Geographic variation of chlorinated pesticides, toxaphenes and PCBs in human milk from sub- arctic and arctic locations in Russia[J] . Science of the Total Environment, 2003 , 306:179-195.
59. Sakamoto M, Tsutsumi T. Applicability of headspace solid-phase microextraction to the determination of multi-class pesticides in waters[J]. Chromatography A,2004,10:63-74.
60. Schenck F J, Donoghue D J. Determination of organochlorine and organophosphorus pesticide residue eggs using a solid phase extraction cleanup. Agric Food Chem, 2000,48:6412-6415.
61. Takazawa Y, Yoshikane M, Shibata Y. Toxaphene and Other Organochlorine Compounds in Pintails (Anas acuta) from Saitama Kamoba in Japan during Oct 2000-Feb 2002[J]. Bull Environment Contament Toxicolity,2007, 79:87-90
62. U.S.EPA, Soil Screening for Toxaphene by Immunoassay, Method 4040[D]. 1996,125-197.
63. Vania Gomes Zuin, Alexandre Leite Lopes, Janete Harumi Yariwake, et al. Application of a novel sol-gel polydimethylsiloxane (vinyl alcohol) solid-phase microextraction fiber for gas chromatographic determination of pesticide residues in herbal infusions[J]. Journal of Chromatography A,2004,1056 (12): 21-26.
64. Vetter W, Luckas B. Enantioselective determination of persistent and partly degradable toxaphene congeners in high trophic level biota[J]. Chemosphere, 2000 ,41:499- 506.
65. Vetter W, Krock B, Lucks B.Congener Specific Determination of Compounds of Technical Toxaphene(CTTs) in Different Antarctic Seal Species[J].Chromatographia,1997,44:65-73
66. Vetter W, Oehme M. Toxaphene analysis and environmental fate of congeners[J]. New Types of Persistent Halogenated Compounds,2000, (3):237- 239.
67.Vetter W,Oehme M.Toxaphene analysis and the environmental fate of congeners[A].In:Paasivirta J(Ed).New Types of Persistent Halogenated Compounds[C].Springer,Berlin,2003,(3):237-287.
68.Viorica Lopez-Avila,Janet Benedicto.Microwave assisted extration combined with gas chromatography and enzyme-linked immunosorbent assay[J].TrAC Trends in Analytical Chemistry.1996,15(8):334-341.
69.Wester P G,Geus H J,Boer J.From Chemosphere to biosphere[J].World Journal of Microbiology and Biotechnology,2001,17(6):651-655.
70.Witte J,Buthe A,Ternes W.Congener-specific analysis of toxaphene in eggs of seabirds from Germany by HRGC- NCI-MS using a carborane-siloxane copolymer phase[J].Chemosphere,2000,41:529-539.
71.Xu J,Stem G A.Selective accumulation of polychlorochampenes in aquatic biota from the Canadian Artic[J].Environment Toxicolity Chemistry,1998,12:701-709.
72.Zinmmerma L R.Detection of persistent organic pollutants in the Mississippi Delta using semipermeable membrane devices[J].The Science of the Total Environment,2000,248(23):169-179.