两种苯并咪唑类杀菌剂高效液相色谱分析方法及其环境行为研究
|
摘要
已有调查表明，人类癌症的发病率与农药的使用量呈平行关系。因此，农药的大量使用，已对全世界的环境和人类身体健康造成了重大的危害。近年来杀菌剂的产量逐年上升。苯并咪唑类杀菌剂由于它们的广谱、低毒而得到广泛使用。但它们仍然有一定的毒性，在环境中比较稳定，而且由于它们的内吸性还可以在植物体内残留。因此，对它们在水、土壤中的残留状况进行分析研究有实际意义。
固相萃取技术（SPE）是近些年来发展起来的样品处理方法。它具有操作简单、省时、安全、溶剂用量少、不易乳化以及高富集因子等优点，广泛应用于痕量有机物的分离富集。
本论文简要介绍了固相萃取的基本原理、富集装置及影响萃取效率的因素和在环境分析中的应用及发展趋势，介绍了固相萃取新技术。
获得的主要研究结果如下：
1.对高效液相色谱测定条件进行了优化。通过试验确定：分析柱为ODS柱，检测波长为286nm，流动相为甲醇/水=50:50(v/v)，流速为0.7mL/min，柱温为55oC。
2.选定3M Empore 6mL C18相作为富集水样中苯并咪唑类杀菌剂的固定相。研究了影响方法回收率的诸多因素，优化了固相萃取条件。选定甲醇为洗脱剂；洗脱剂的用量为2mL；向水样中加入1%甲醇作为改性剂可加大苯并咪唑类杀菌剂的回收效果；样品以10mL/min的流速通过萃取柱较为合适；水样的pH值基本上对苯并咪唑类杀菌剂的回收率没有影响；水样中氯化钾的质量浓度为5g/L。并对此作了理论上的探讨。
3.通过研究苯并咪唑类杀菌剂在水体中的降解状况得知，水解速率与温度和pH值有关。在太阳光照下，在纯水中光解速率较快，丙酮
加速光解；而在紫外灯下光解速率很快，只有几十个小时。
4.研究了多菌灵和噻菌灵在长春地区四种典型土壤中的吸附状况。结果表明，影响吸附的主要因素是有机碳含量。从有机碳吸附常数看，多菌灵和噻菌灵均具有“中等移动性”，说明它们在土壤中的迁移性较差。
5.检测了多菌灵和噻菌灵在实际水样中的残留状况。固相萃取有效地消除了杂质的干扰。测定结果的精密度和准确度都很好。
Some research has testified that the incidence of cancer disease has direct ratio to the use of pesticides. With the use of a lot of pesticides, there was harm to human being’s health and the environment in the world. In recent years, the fungicide’s yield increases year after year. Benzimidazolic compounds were used widely because of their broad-spectrum, high- performance and little toxicity. But they still have some toxicity, were steady in the environment, and they could stay in the vegetable because they were systemic fungicide. Therefore, the analysis into their persistence in the water and the soil was of great importance.
Solid phase extraction (SPE), as a sample pretreatment technique was developed in the recent years. It had the advantage of analytical speed, simplicity, low costs, safety, no emulsification, flexibility and high preconcentration factor, and was used to separate and preconcentrate lots of organic analytes.
This article totally described the development, principle, performing procedure, devices and the factors influencing process and recovery of SPE. Its applications in environmental analysis were also well reviewed. Furthermore, the detection methods and its trend were summarized. Finally the new techniques of solid phase extraction were outlined.
The main conclusions were as follows:
1. The best chromatographic conditions were UV detection wavelength of 286nm, mobile phase of methanol/water at 50/50(v/v), mobile phase flow rate of 0.7mL/min, column temperature of 55 oC, the column used was ODS, were used to determine the benzimidazolic compounds in the environment.
2. 3M Empore 6mL C18 was selected as the best solid phase for extracting trace benzimidazolic compounds in water samples. In addition, most of the influencing factors were studied and optimized. The result
showed that methanol was the preferred elution solvents for the absorbed benzimidazolic compounds. When the elution solvent (2mL) was selected, the variation of recoveries as a function of the volume of elution solvent used can be determined. The addition of 1% methanol into the sample prior to spiking could greatly improve the recoveries. The flow rate of sample loading was 10mL/min. The acid of samples had no influence on the recoveries. Meanwhile, the concentration of potassium chloride in the water was 5 g/L. What’s more; these were discussed in the theory.
3. The degradation of the benzimidazolic compounds was investigated in the water. The results showed that hydrolysis of the benzimidazolic compounds depended on both pH and the temperature. The rate of photo degradation in the water under sunlight was very slow, when acetone was added, the rate was fast. However, the rate of photo degradation was much faster than those, when it was under UV lamp, only several ten hours.
4. Research on the adsorption of carbendazim and thiabendazole in four different types of soil in Changchun region showed that the content of
organic carbon was the major factor of adsorption in the soil. From the organic carbon adsorption constant, carbendazim and thiabendazole had middling transference, suggesting that they had worse transference in the soil.
5. In the analysis of real samples such as surface run-off water, Solid phase extraction technique enabled the elimination of matrix interference and the work was possible.
固相萃取技术（SPE）是近些年来发展起来的样品处理方法。它具有操作简单、省时、安全、溶剂用量少、不易乳化以及高富集因子等优点，广泛应用于痕量有机物的分离富集。
本论文简要介绍了固相萃取的基本原理、富集装置及影响萃取效率的因素和在环境分析中的应用及发展趋势，介绍了固相萃取新技术。
获得的主要研究结果如下：
1.对高效液相色谱测定条件进行了优化。通过试验确定：分析柱为ODS柱，检测波长为286nm，流动相为甲醇/水=50:50(v/v)，流速为0.7mL/min，柱温为55oC。
2.选定3M Empore 6mL C18相作为富集水样中苯并咪唑类杀菌剂的固定相。研究了影响方法回收率的诸多因素，优化了固相萃取条件。选定甲醇为洗脱剂；洗脱剂的用量为2mL；向水样中加入1%甲醇作为改性剂可加大苯并咪唑类杀菌剂的回收效果；样品以10mL/min的流速通过萃取柱较为合适；水样的pH值基本上对苯并咪唑类杀菌剂的回收率没有影响；水样中氯化钾的质量浓度为5g/L。并对此作了理论上的探讨。
3.通过研究苯并咪唑类杀菌剂在水体中的降解状况得知，水解速率与温度和pH值有关。在太阳光照下，在纯水中光解速率较快，丙酮
加速光解；而在紫外灯下光解速率很快，只有几十个小时。
4.研究了多菌灵和噻菌灵在长春地区四种典型土壤中的吸附状况。结果表明，影响吸附的主要因素是有机碳含量。从有机碳吸附常数看，多菌灵和噻菌灵均具有“中等移动性”，说明它们在土壤中的迁移性较差。
5.检测了多菌灵和噻菌灵在实际水样中的残留状况。固相萃取有效地消除了杂质的干扰。测定结果的精密度和准确度都很好。
Some research has testified that the incidence of cancer disease has direct ratio to the use of pesticides. With the use of a lot of pesticides, there was harm to human being’s health and the environment in the world. In recent years, the fungicide’s yield increases year after year. Benzimidazolic compounds were used widely because of their broad-spectrum, high- performance and little toxicity. But they still have some toxicity, were steady in the environment, and they could stay in the vegetable because they were systemic fungicide. Therefore, the analysis into their persistence in the water and the soil was of great importance.
Solid phase extraction (SPE), as a sample pretreatment technique was developed in the recent years. It had the advantage of analytical speed, simplicity, low costs, safety, no emulsification, flexibility and high preconcentration factor, and was used to separate and preconcentrate lots of organic analytes.
This article totally described the development, principle, performing procedure, devices and the factors influencing process and recovery of SPE. Its applications in environmental analysis were also well reviewed. Furthermore, the detection methods and its trend were summarized. Finally the new techniques of solid phase extraction were outlined.
The main conclusions were as follows:
1. The best chromatographic conditions were UV detection wavelength of 286nm, mobile phase of methanol/water at 50/50(v/v), mobile phase flow rate of 0.7mL/min, column temperature of 55 oC, the column used was ODS, were used to determine the benzimidazolic compounds in the environment.
2. 3M Empore 6mL C18 was selected as the best solid phase for extracting trace benzimidazolic compounds in water samples. In addition, most of the influencing factors were studied and optimized. The result
showed that methanol was the preferred elution solvents for the absorbed benzimidazolic compounds. When the elution solvent (2mL) was selected, the variation of recoveries as a function of the volume of elution solvent used can be determined. The addition of 1% methanol into the sample prior to spiking could greatly improve the recoveries. The flow rate of sample loading was 10mL/min. The acid of samples had no influence on the recoveries. Meanwhile, the concentration of potassium chloride in the water was 5 g/L. What’s more; these were discussed in the theory.
3. The degradation of the benzimidazolic compounds was investigated in the water. The results showed that hydrolysis of the benzimidazolic compounds depended on both pH and the temperature. The rate of photo degradation in the water under sunlight was very slow, when acetone was added, the rate was fast. However, the rate of photo degradation was much faster than those, when it was under UV lamp, only several ten hours.
4. Research on the adsorption of carbendazim and thiabendazole in four different types of soil in Changchun region showed that the content of
organic carbon was the major factor of adsorption in the soil. From the organic carbon adsorption constant, carbendazim and thiabendazole had middling transference, suggesting that they had worse transference in the soil.
5. In the analysis of real samples such as surface run-off water, Solid phase extraction technique enabled the elimination of matrix interference and the work was possible.
引文
[1] 梁诚. 我国农药工业生产现状及发展趋势. 河南化工,2001年第10期
[2] 张辉, 刘广民等. 农药在土壤环境中迁移转化规律研究的现状与展望. 世界地质, Vol.19 No.2, Jun. 2000
[3] 龙惠珍, 陆贻通. 世界农药急性中毒概况. 农药译丛, 1997, 19 (3): 54-46
[4] 仲维科, 郝戬. 我国食品的农药污染问题. 农药, Vol.39, No.7 (2000)
[5] 王晓光, 王哲光. 国内外农药工业发展态势. 化工技术经济, 2001年第5期
[6] 林玉锁, 龚瑞忠. 农药环境管理与污染控制. 环境导报, 2000年第3期
[7] 顾晓军, 田素芬. 农药的负面效应：过去、现状及展望. 福建农业大学学报. 2001, 30 (1): 80-83
[8] Serge Chiron, Amadeo Fernadez Alba etc. Comparison of on-line solid-phase disk extraction to liquid-liquid extraction for monitoring selected pesticides in environment waters. Environ. Sci. Techno. 1993, 27, 2352-2359
[9] Michelangelo Anastassiades, Wolfgang Schwack. Analysis of carbendazim, benomyl, thiophanate methyl and 2,4-dichloro- phenoxyacetic acid in fruits and vegetables after superc- ritical fluid extraction. Journal of Chromatography A, 825 (1998) 45-54
[10]张海霞, 朱彭龄. 固相萃取, 分析化学,Vol.28 No.9 Sep. 2000
[11]贾瑞宝, 孙韶华, 刘德珍. 用固相萃取技术富集水中多环芳烃. 色谱. 1997,15（6）: 524-526
[12]M. -C Hennion, C.Cau-Dit-Coumes, V. Pichon.Trace analysis of polar organic pollutants in aqueous samples Tools for the rapid prediction and optimization of the solid-phase extraction parameters. Journal of Chromatography A. 823(1998) 147-161
[13]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. Journal of Chromatography A, 885(2000) 41-49
[14]董玉瑛, 孙成等. 固相萃取技术在水体有机物分析中的应
用. 环境污染治理技术与设备.1999,7（4）: 83-90
[15]Ricard Panades, Albert Ibarz, Santiago Esplugas.
Photodecomposition of carbendazim in aoueous solutions.
Wat. Res. Vol. 34, No. 11, pp. 2951-2954, 2000
[16]张莘民，杨凯. 固相萃取技术在我国环境化学分析中的应用. 中国环境监测，Vol.16 No.6 Dec.2000
[17]范毅，冯钰锜，达世禄. 固相微萃取与高效液相色谱联用技术的进展. 色谱Vol.19 No.6,Nov.2001
[18]刘俊亭. 新一代萃取分离技术——固相微萃取. 色谱，Vol.15 No.2,March 1997
[19]马继平，王涵文，关亚风. 色谱，Vol.20 No.1,January 2002
[20]Silvia Suare-Luque, Ines Mato, Jose F. Huidobro, Jesus Simal-Lozano. Solid-phase extraction procedure to remove organic acids from honey. Journal of chromatography B, 2002,770,77-82
[21]Frank J.Schenk, Dan J. Donoghue. Determination of organo-chlorine and organophosphorus pesticide residues in eggs using a solid phase extraction cleanup. J.Agric. Food Chem.2000, 48,6412-6415
[22]R.Dommarco, A.Santilio, L. Fornareli, M.Rubbiani. Simultaneous quantitative determination of thirteen urea pesticides at sub-ppb levels on a Zorbax SB-C18 column. Journal of chromatography A. 1998,825,200-204
[23]戴华, 李拥军, 张莹. 稻谷中吡虫啉农药残留量的固相萃取高效液相色谱测定. 分析测试学报, Vol.21 No.1 Jan. 2002
[24]张博, 李素珍等. 固相萃取结合HPLC法快速测定石油中的微量酚. 石油化工, 2002年第31卷第2期
[25]胡秋芬, 杨光宇等. 固相萃取-高效液相色谱法测定水中酚类物质. 分析化学, 2002, 30 (5): 560-563
[26]张维昊, 徐小清. 固相萃取高效液相色谱法测定水中痕量微囊藻毒素. 分析化学, 2001, 29 (5): 522-525
[27]Wang Shui, Tang Lin mordiside A in Bitter Melon by etal.
Rapid analysis of Mo high performance liquid chromatography following solid phase extraction. Chinese Journal of Chromatography, Vol.19 No.2 March 2001
[28]Gou Y, Eisert R, Pawliszyn J. Automated in-tube SPME-HPLC for carbamate pesticides analysis. J. Chromatography, 2000, A873: 137-147
[29]Jimenez B, Molto J C, Font G, et al. Evaluation of HPLC of polar pesticides in rice fields. J. Bull. Environ Toxicology, 1999, 63: 813-820
[30]Jimenez B, Molto J C, Font G. The effect of surfactant and polycyclic aromatic hydrocarbons interference on SPE and HPLC determination of nitrogen containing pesticides. J. LC-GC, 1996, 14 (11): 970-976.
[31]Juhler K R, Optimized method for the determination of organophosphorous pesticides in meat and fatty matrices. J.Chromatography, 1997, A786 (1-2): 145-153
[32]Molina C, Honing M, Barcelo D, Determination of organophosphorous pesticides in water by SPE followed by LC/high flow pneumatically assisted electrospray MS. J. Anal. Chem., 1994, 66 (24): 4444- 4449
[33]Aguillar C, Ferrer I, Borrull F, et al. On-line and off-line SPE with styrene-divinylbenzene membrane extraction disks for determining pesticides in water by reversed-phase LC-DAD. J. Chromatography, 1996, A754: 77-84
[34]Ruey-an Dong, Lee C Y, Determination of pesticide residues in foods using SPE cleanup cartridges.J. Analyst [London], 1999, 124: 1287-1289
[35]Dejarger L S, Andrews A R, Solvent micro-extraction of chlorinated pesticides. J. Chromatographia. 1999,50, (11-12): 733-738
[36]Horitaka Obana, Kazuhiko Akutsu, Masahiro Okihashi and Shinjiro Hori; Multiresidue analysis of pesticides in vegetables and fruits using two-layered column with graphitized carbon and water adsorbent polymer.J. Analyst.2001 (126): 1529-1534
[37]Imma Ferer, Damia Barcelo and E.M Thurman, Double-Disk Solid-Phase Extraction: Simultaneous Cleanup and Trace
Enrichment of Herbicides and Metabolites from Environmental Samples.J.Anal.Chem 1999(71): 1009-1015
[38]Vandecasteele K, Gaus I, Debreuck W, et al. Identification and quantification of 77 pesticides in ground water using solid-phase coupled to L-L micro-extraction and reversed-phase LC.J. Anal. Chem.2000, 72: 3093-3101
[39]Cappiello A, Famiglini G, Mangani F, Simultaneous determination of acidic and basic-neutral pesticides in water at ppt concentration level by ion-interaction micro-HPLC/MS. J. Environ. Sci. Technol., 1999, 33 (1-2): 3906-3910
[40]Morellicardooso M H W, Mcardozo R T, Mello J L, et al. HRC J. High Resolution Chromatography.1999, 22 (11): 619-622
[41]于世林编著. 高效液相色谱方法及应用. 化学工业出版社
[42]A.COLLINGE,A.NOIRFALISE. Determination of thiabendazole residues in marmalades by high-performance liquid chromatography. Journal of Chromatography. 257 (1983) 416-418
[43]Dilna M, Victor, Rex E. Hall. Jeff D. Shamis, Stuart A.Whitlock. Methods for maleic hydrazide, ethoxyquin and thiabendazole in wastewaters. Journal of Chromatography, 283 (1984) 383-389
[44]Promode C. Bardalaye, Wilis B. Wheeler. Simplified method for the clean-up and reversed-phase high-performance liquid chromatographic determination of benomyl in mangoes. Journal of Chromatography, 330 (1985) 403-407
[45]Rodney J. Bushway, Heather L. Hurst, Jasotha Kugabalasooriar and Lewis B. Perkins. Determination of carbendazim in blueberries by reversed-phase high-performance liquid chromatography. Journal of Chromatography, 587 (1991) 321-324
[46]Jagdev S. Dhoot, Aurora R. del Rosario. Determination and confirmation of benomyl and carbendazim in water using high-performance liquid chromatography and diode array
detection. Journal of Chromatography, 645 (1993) 178-181
[47]Alfonso Di Muccio, Silvana Girolimetti,Danilo Attard Barbini etal. Selective clean-up applicable to aqueous acetone extracts for the determination of carbendazim and thiabendazole in fruits and vegetables by high-performance liquid chromatography with UV detection. Journal of Chromatography A, 833 (1999) 61-65
[48]陈夏娇. 40%苯菌?福美可湿性粉剂的液相色谱分析. 农药科学与管理, 2001, 22 (4)
[49]王以燕,李国屏,孙绮丽. 多菌灵、福美双复配种衣剂高效液相色谱分析. 农药科学与管理, 1997年第1期
[50]王多加,周向阳. 用HPLC法测定五氯硝基苯和多菌灵的复配制剂. 分析测试学报，Vol.18, No.2 (1999)
[51]李桂凤,郝征红等.花生中多菌灵残留量的高效液相色谱分析方法的研究.分析测试学报, Vol.17, No.3 (1998)
[52]段文仲，郝冬升. 高效液相色谱法同时测定水果中多种农药残留量的方法研究. 农药，Vol.37,No.8 （1998）
[53]朱凤霞, 董鹏. 多菌灵原药有效成分含量的高效液相色谱测定. 化工标准化与质量监督, 1999年第8期
[54]吴亚玉,张耀中. 噻菌灵、百菌清烟剂的分析方法. 农药科学与管理,1996年第4期
[55]张友松,徐烽,杜少容.杀菌剂噻菌灵在香菇上残留量测定. 农药,Vol.35 No.5（1996）
[56]徐作珽，李林，张传模，孙培贤，王焕文，朱光华，姜孟雪. 山东农业科学，1994年，第1期
[57]《农药知识》编写组 编. 农药知识. 上海人民出版社
[58][英]R.W.马什 主编. 内吸性杀菌剂. 化学工业出版社
[59][美]W.D.冈吉 等编. 土壤和水中的农药.科学出版社
[60]岳永德, 樊德方, 花日茂. 乙草胺在水中的光化学降解. 农药学学报, 2000, 12 (1): 71-74
[61]花日茂, 李湘琼, 李学德等.丁草胺在不同类型水中的光化学降解.应用生态学报，1999，10(1):57-59
[62]花日茂 岳永德 潘学冬等. 腐殖质对丁草胺在水中的光解 效
应研究.安徽农业大学学报,1999,26(1):63-67
[63]页：70
简明农药词典. 化学工业出版社
[64][苏]H.H.麦尔尼科夫，A.И.沃尔科夫，O.A.科罗特科娃 著. 农药与环境. 化学工业出版社
[65]陈锡岭，樊德方.杀菌剂叶青双在水中的降解特性研究. 农村生态环境. 1999，15（4）：47-51
[66]郑和辉，叶常明. 乙草胺和丁草胺的水解及其动力学. 环境化学. 2001，20（2）：168-171
[67]陈锡岭，石明旺. 新型杀菌剂叶青双光解动态研究. 农业环境保护. 2000，19（4）：239-241
[68]陈锡岭，樊德方. 杀菌剂叶青双水解动态研究. 农业环境保护. 2000，19（3）：164-166
[69]王一茹，刘长武，牛成玉，蔡罗保，李治祥，朱昌寿，贺水济，王琴孙. 丁草胺在水体中的光解和稻田中归趋的研究. 环境科学学报，Vol.16,No.4, Oct.1996
[70]石利利。三十烷醇在水体中的光解与水解特性。农村生态环境，1997，13（4）：55-56
[71]徐宝才，岳永德，胡颍蕙等。多菌灵的光化学降解研究。环境科学学报，2000，20（5）：616-620
[72]李勋光，李小平. 土壤砷吸附及砷的水稻毒性. 土壤，1996年，第2期
[73]丁疆华，温琰茂，舒强. 土壤汞吸附和甲基化探讨. 农业环境与发展，2001年第1期
[74]高健磊，李冰，范顺利，侯杰. 农药废液中氧乐果及其中间体土壤吸附系数和降解速率的测定. 河南科学，Vol.17 No.4,Dec.1998
[75]陈桂秋，胡瑞芝. 南方主要母质发育的水稻土对硅酸盐的吸附与解吸特征的研究. 土壤，2002年第6期
[76]杨杰文，蒋新，徐仁扣，季国亮，赵其国. 离子强度和对土壤吸附Al的影响. 环境化学，Vol.21,No.3,May 2002
[77]沈阿林，崔转铃，姚同山. 几种土壤对付的吸附和解吸. 植物营养与肥料学报.Vol.3 No.1,Mar.1997
[78]郭晓冬，张雪琴，杨玲. 甘肃省主要农业区土壤对磷的吸附与解吸特性. 西北农业学报. 1997，6（2）：7-12
[79]徐仲艳，王晓蓉. 改性土壤对模拟含硝基苯废水的吸附. 环境化学. Vol.21 No.3,May 2002
[80]龙新宪，倪吾钟，杨肖娥. 菜园土壤锌的吸附-解吸特性研究. 土
壤通报. Vol.23 No.1,Feb. 2003
[81]孙建华，李继云. 北京郊区几种典型土壤对硼的吸附性能. 环境科学. 1998年9月
[90]周伟，李继云. 北京地区几种典型土壤吸附Zn的研究. 环境科学. Vol.17 No.6,Dec. 1996
[91]刘立丽，史建君，赵希岳，张永熙. 95Zr在土壤中的淋溶与垂直迁移. 环境科学. Vol.22 No.6,Nov. 2001
[92]毕新慧，储少岗，徐晓白。多氯联苯在土壤中的吸附行为。中国环境科学，2001，21（3）：284-288
[93]花日茂 岳永德 汤锋等. 多菌灵在土壤中的吸附和移动性.安徽农业科学，1995，23（2）：171-173
[94]石利利，朱忠林，单正军，蔡道基.氯唑磷在土壤中的降解性能与移动性研究.环境科学学报，1999，19（4）：456-458
[95]苏允兰， 莫汉宏，安凤春.土壤中苯氧羧酸类除草剂的降解动态.环境科学，2000，21（6）：92-94
[96]曹罡，莫汉宏，安凤春.除草剂2,4-D在胡敏酸上的吸附.环境科学学报，2002，22（1）：120-122
[97]奚南山，刘振声. 多效唑在土壤中的行为研究. 生态科学. 1994年第2期
[98]Bernhard M. Berger. Factors influencing transformation rates and formation of products of phenylurea herbicides in soil. J.Agric. Food Chem.1997.47, 3389-3396
[99]渠锋，莫汉宏，安凤春等。2甲4氯在土壤中吸附常数的测定。环境科学，1999，20（3）：69-71
[100]刘维屏，王琪全，方卓。新农药环境化学行为研究-除草剂绿草定在土壤-水中的吸附和光解。中国环境科学，1995，15（4）：311-315
[101]卢颖，韩朔睽，除草剂苯噻草胺在土壤中的吸附.环境化学，2000，19（6）：513-517
[102]丁言斌，宋卫华，王连生，张正.批量平衡法研究芳香酮类化合物在东北黑土上的吸附.环境化学，2000，19（4）：330-334
[103]单正军，朱忠林，华晓梅. 除草剂拉索对地下水影响研究.环境科学学报.1994，14（1）：72-78
[2] 张辉, 刘广民等. 农药在土壤环境中迁移转化规律研究的现状与展望. 世界地质, Vol.19 No.2, Jun. 2000
[3] 龙惠珍, 陆贻通. 世界农药急性中毒概况. 农药译丛, 1997, 19 (3): 54-46
[4] 仲维科, 郝戬. 我国食品的农药污染问题. 农药, Vol.39, No.7 (2000)
[5] 王晓光, 王哲光. 国内外农药工业发展态势. 化工技术经济, 2001年第5期
[6] 林玉锁, 龚瑞忠. 农药环境管理与污染控制. 环境导报, 2000年第3期
[7] 顾晓军, 田素芬. 农药的负面效应：过去、现状及展望. 福建农业大学学报. 2001, 30 (1): 80-83
[8] Serge Chiron, Amadeo Fernadez Alba etc. Comparison of on-line solid-phase disk extraction to liquid-liquid extraction for monitoring selected pesticides in environment waters. Environ. Sci. Techno. 1993, 27, 2352-2359
[9] Michelangelo Anastassiades, Wolfgang Schwack. Analysis of carbendazim, benomyl, thiophanate methyl and 2,4-dichloro- phenoxyacetic acid in fruits and vegetables after superc- ritical fluid extraction. Journal of Chromatography A, 825 (1998) 45-54
[10]张海霞, 朱彭龄. 固相萃取, 分析化学,Vol.28 No.9 Sep. 2000
[11]贾瑞宝, 孙韶华, 刘德珍. 用固相萃取技术富集水中多环芳烃. 色谱. 1997,15（6）: 524-526
[12]M. -C Hennion, C.Cau-Dit-Coumes, V. Pichon.Trace analysis of polar organic pollutants in aqueous samples Tools for the rapid prediction and optimization of the solid-phase extraction parameters. Journal of Chromatography A. 823(1998) 147-161
[13]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. Journal of Chromatography A, 885(2000) 41-49
[14]董玉瑛, 孙成等. 固相萃取技术在水体有机物分析中的应
用. 环境污染治理技术与设备.1999,7（4）: 83-90
[15]Ricard Panades, Albert Ibarz, Santiago Esplugas.
Photodecomposition of carbendazim in aoueous solutions.
Wat. Res. Vol. 34, No. 11, pp. 2951-2954, 2000
[16]张莘民，杨凯. 固相萃取技术在我国环境化学分析中的应用. 中国环境监测，Vol.16 No.6 Dec.2000
[17]范毅，冯钰锜，达世禄. 固相微萃取与高效液相色谱联用技术的进展. 色谱Vol.19 No.6,Nov.2001
[18]刘俊亭. 新一代萃取分离技术——固相微萃取. 色谱，Vol.15 No.2,March 1997
[19]马继平，王涵文，关亚风. 色谱，Vol.20 No.1,January 2002
[20]Silvia Suare-Luque, Ines Mato, Jose F. Huidobro, Jesus Simal-Lozano. Solid-phase extraction procedure to remove organic acids from honey. Journal of chromatography B, 2002,770,77-82
[21]Frank J.Schenk, Dan J. Donoghue. Determination of organo-chlorine and organophosphorus pesticide residues in eggs using a solid phase extraction cleanup. J.Agric. Food Chem.2000, 48,6412-6415
[22]R.Dommarco, A.Santilio, L. Fornareli, M.Rubbiani. Simultaneous quantitative determination of thirteen urea pesticides at sub-ppb levels on a Zorbax SB-C18 column. Journal of chromatography A. 1998,825,200-204
[23]戴华, 李拥军, 张莹. 稻谷中吡虫啉农药残留量的固相萃取高效液相色谱测定. 分析测试学报, Vol.21 No.1 Jan. 2002
[24]张博, 李素珍等. 固相萃取结合HPLC法快速测定石油中的微量酚. 石油化工, 2002年第31卷第2期
[25]胡秋芬, 杨光宇等. 固相萃取-高效液相色谱法测定水中酚类物质. 分析化学, 2002, 30 (5): 560-563
[26]张维昊, 徐小清. 固相萃取高效液相色谱法测定水中痕量微囊藻毒素. 分析化学, 2001, 29 (5): 522-525
[27]Wang Shui, Tang Lin mordiside A in Bitter Melon by etal.
Rapid analysis of Mo high performance liquid chromatography following solid phase extraction. Chinese Journal of Chromatography, Vol.19 No.2 March 2001
[28]Gou Y, Eisert R, Pawliszyn J. Automated in-tube SPME-HPLC for carbamate pesticides analysis. J. Chromatography, 2000, A873: 137-147
[29]Jimenez B, Molto J C, Font G, et al. Evaluation of HPLC of polar pesticides in rice fields. J. Bull. Environ Toxicology, 1999, 63: 813-820
[30]Jimenez B, Molto J C, Font G. The effect of surfactant and polycyclic aromatic hydrocarbons interference on SPE and HPLC determination of nitrogen containing pesticides. J. LC-GC, 1996, 14 (11): 970-976.
[31]Juhler K R, Optimized method for the determination of organophosphorous pesticides in meat and fatty matrices. J.Chromatography, 1997, A786 (1-2): 145-153
[32]Molina C, Honing M, Barcelo D, Determination of organophosphorous pesticides in water by SPE followed by LC/high flow pneumatically assisted electrospray MS. J. Anal. Chem., 1994, 66 (24): 4444- 4449
[33]Aguillar C, Ferrer I, Borrull F, et al. On-line and off-line SPE with styrene-divinylbenzene membrane extraction disks for determining pesticides in water by reversed-phase LC-DAD. J. Chromatography, 1996, A754: 77-84
[34]Ruey-an Dong, Lee C Y, Determination of pesticide residues in foods using SPE cleanup cartridges.J. Analyst [London], 1999, 124: 1287-1289
[35]Dejarger L S, Andrews A R, Solvent micro-extraction of chlorinated pesticides. J. Chromatographia. 1999,50, (11-12): 733-738
[36]Horitaka Obana, Kazuhiko Akutsu, Masahiro Okihashi and Shinjiro Hori; Multiresidue analysis of pesticides in vegetables and fruits using two-layered column with graphitized carbon and water adsorbent polymer.J. Analyst.2001 (126): 1529-1534
[37]Imma Ferer, Damia Barcelo and E.M Thurman, Double-Disk Solid-Phase Extraction: Simultaneous Cleanup and Trace
Enrichment of Herbicides and Metabolites from Environmental Samples.J.Anal.Chem 1999(71): 1009-1015
[38]Vandecasteele K, Gaus I, Debreuck W, et al. Identification and quantification of 77 pesticides in ground water using solid-phase coupled to L-L micro-extraction and reversed-phase LC.J. Anal. Chem.2000, 72: 3093-3101
[39]Cappiello A, Famiglini G, Mangani F, Simultaneous determination of acidic and basic-neutral pesticides in water at ppt concentration level by ion-interaction micro-HPLC/MS. J. Environ. Sci. Technol., 1999, 33 (1-2): 3906-3910
[40]Morellicardooso M H W, Mcardozo R T, Mello J L, et al. HRC J. High Resolution Chromatography.1999, 22 (11): 619-622
[41]于世林编著. 高效液相色谱方法及应用. 化学工业出版社
[42]A.COLLINGE,A.NOIRFALISE. Determination of thiabendazole residues in marmalades by high-performance liquid chromatography. Journal of Chromatography. 257 (1983) 416-418
[43]Dilna M, Victor, Rex E. Hall. Jeff D. Shamis, Stuart A.Whitlock. Methods for maleic hydrazide, ethoxyquin and thiabendazole in wastewaters. Journal of Chromatography, 283 (1984) 383-389
[44]Promode C. Bardalaye, Wilis B. Wheeler. Simplified method for the clean-up and reversed-phase high-performance liquid chromatographic determination of benomyl in mangoes. Journal of Chromatography, 330 (1985) 403-407
[45]Rodney J. Bushway, Heather L. Hurst, Jasotha Kugabalasooriar and Lewis B. Perkins. Determination of carbendazim in blueberries by reversed-phase high-performance liquid chromatography. Journal of Chromatography, 587 (1991) 321-324
[46]Jagdev S. Dhoot, Aurora R. del Rosario. Determination and confirmation of benomyl and carbendazim in water using high-performance liquid chromatography and diode array
detection. Journal of Chromatography, 645 (1993) 178-181
[47]Alfonso Di Muccio, Silvana Girolimetti,Danilo Attard Barbini etal. Selective clean-up applicable to aqueous acetone extracts for the determination of carbendazim and thiabendazole in fruits and vegetables by high-performance liquid chromatography with UV detection. Journal of Chromatography A, 833 (1999) 61-65
[48]陈夏娇. 40%苯菌?福美可湿性粉剂的液相色谱分析. 农药科学与管理, 2001, 22 (4)
[49]王以燕,李国屏,孙绮丽. 多菌灵、福美双复配种衣剂高效液相色谱分析. 农药科学与管理, 1997年第1期
[50]王多加,周向阳. 用HPLC法测定五氯硝基苯和多菌灵的复配制剂. 分析测试学报，Vol.18, No.2 (1999)
[51]李桂凤,郝征红等.花生中多菌灵残留量的高效液相色谱分析方法的研究.分析测试学报, Vol.17, No.3 (1998)
[52]段文仲，郝冬升. 高效液相色谱法同时测定水果中多种农药残留量的方法研究. 农药，Vol.37,No.8 （1998）
[53]朱凤霞, 董鹏. 多菌灵原药有效成分含量的高效液相色谱测定. 化工标准化与质量监督, 1999年第8期
[54]吴亚玉,张耀中. 噻菌灵、百菌清烟剂的分析方法. 农药科学与管理,1996年第4期
[55]张友松,徐烽,杜少容.杀菌剂噻菌灵在香菇上残留量测定. 农药,Vol.35 No.5（1996）
[56]徐作珽，李林，张传模，孙培贤，王焕文，朱光华，姜孟雪. 山东农业科学，1994年，第1期
[57]《农药知识》编写组 编. 农药知识. 上海人民出版社
[58][英]R.W.马什 主编. 内吸性杀菌剂. 化学工业出版社
[59][美]W.D.冈吉 等编. 土壤和水中的农药.科学出版社
[60]岳永德, 樊德方, 花日茂. 乙草胺在水中的光化学降解. 农药学学报, 2000, 12 (1): 71-74
[61]花日茂, 李湘琼, 李学德等.丁草胺在不同类型水中的光化学降解.应用生态学报，1999，10(1):57-59
[62]花日茂 岳永德 潘学冬等. 腐殖质对丁草胺在水中的光解 效
应研究.安徽农业大学学报,1999,26(1):63-67
[63]页：70
简明农药词典. 化学工业出版社
[64][苏]H.H.麦尔尼科夫，A.И.沃尔科夫，O.A.科罗特科娃 著. 农药与环境. 化学工业出版社
[65]陈锡岭，樊德方.杀菌剂叶青双在水中的降解特性研究. 农村生态环境. 1999，15（4）：47-51
[66]郑和辉，叶常明. 乙草胺和丁草胺的水解及其动力学. 环境化学. 2001，20（2）：168-171
[67]陈锡岭，石明旺. 新型杀菌剂叶青双光解动态研究. 农业环境保护. 2000，19（4）：239-241
[68]陈锡岭，樊德方. 杀菌剂叶青双水解动态研究. 农业环境保护. 2000，19（3）：164-166
[69]王一茹，刘长武，牛成玉，蔡罗保，李治祥，朱昌寿，贺水济，王琴孙. 丁草胺在水体中的光解和稻田中归趋的研究. 环境科学学报，Vol.16,No.4, Oct.1996
[70]石利利。三十烷醇在水体中的光解与水解特性。农村生态环境，1997，13（4）：55-56
[71]徐宝才，岳永德，胡颍蕙等。多菌灵的光化学降解研究。环境科学学报，2000，20（5）：616-620
[72]李勋光，李小平. 土壤砷吸附及砷的水稻毒性. 土壤，1996年，第2期
[73]丁疆华，温琰茂，舒强. 土壤汞吸附和甲基化探讨. 农业环境与发展，2001年第1期
[74]高健磊，李冰，范顺利，侯杰. 农药废液中氧乐果及其中间体土壤吸附系数和降解速率的测定. 河南科学，Vol.17 No.4,Dec.1998
[75]陈桂秋，胡瑞芝. 南方主要母质发育的水稻土对硅酸盐的吸附与解吸特征的研究. 土壤，2002年第6期
[76]杨杰文，蒋新，徐仁扣，季国亮，赵其国. 离子强度和对土壤吸附Al的影响. 环境化学，Vol.21,No.3,May 2002
[77]沈阿林，崔转铃，姚同山. 几种土壤对付的吸附和解吸. 植物营养与肥料学报.Vol.3 No.1,Mar.1997
[78]郭晓冬，张雪琴，杨玲. 甘肃省主要农业区土壤对磷的吸附与解吸特性. 西北农业学报. 1997，6（2）：7-12
[79]徐仲艳，王晓蓉. 改性土壤对模拟含硝基苯废水的吸附. 环境化学. Vol.21 No.3,May 2002
[80]龙新宪，倪吾钟，杨肖娥. 菜园土壤锌的吸附-解吸特性研究. 土
壤通报. Vol.23 No.1,Feb. 2003
[81]孙建华，李继云. 北京郊区几种典型土壤对硼的吸附性能. 环境科学. 1998年9月
[90]周伟，李继云. 北京地区几种典型土壤吸附Zn的研究. 环境科学. Vol.17 No.6,Dec. 1996
[91]刘立丽，史建君，赵希岳，张永熙. 95Zr在土壤中的淋溶与垂直迁移. 环境科学. Vol.22 No.6,Nov. 2001
[92]毕新慧，储少岗，徐晓白。多氯联苯在土壤中的吸附行为。中国环境科学，2001，21（3）：284-288
[93]花日茂 岳永德 汤锋等. 多菌灵在土壤中的吸附和移动性.安徽农业科学，1995，23（2）：171-173
[94]石利利，朱忠林，单正军，蔡道基.氯唑磷在土壤中的降解性能与移动性研究.环境科学学报，1999，19（4）：456-458
[95]苏允兰， 莫汉宏，安凤春.土壤中苯氧羧酸类除草剂的降解动态.环境科学，2000，21（6）：92-94
[96]曹罡，莫汉宏，安凤春.除草剂2,4-D在胡敏酸上的吸附.环境科学学报，2002，22（1）：120-122
[97]奚南山，刘振声. 多效唑在土壤中的行为研究. 生态科学. 1994年第2期
[98]Bernhard M. Berger. Factors influencing transformation rates and formation of products of phenylurea herbicides in soil. J.Agric. Food Chem.1997.47, 3389-3396
[99]渠锋，莫汉宏，安凤春等。2甲4氯在土壤中吸附常数的测定。环境科学，1999，20（3）：69-71
[100]刘维屏，王琪全，方卓。新农药环境化学行为研究-除草剂绿草定在土壤-水中的吸附和光解。中国环境科学，1995，15（4）：311-315
[101]卢颖，韩朔睽，除草剂苯噻草胺在土壤中的吸附.环境化学，2000，19（6）：513-517
[102]丁言斌，宋卫华，王连生，张正.批量平衡法研究芳香酮类化合物在东北黑土上的吸附.环境化学，2000，19（4）：330-334
[103]单正军，朱忠林，华晓梅. 除草剂拉索对地下水影响研究.环境科学学报.1994，14（1）：72-78
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |