2，4-D废水的臭氧、臭氧/双氧水处理技术研究
摘要
本文研究了2,4-D废水在O_3和O_3/H_2O_2氧化中的影响因素、去除动力学和降解机理，为臭氧氧化技术处理2,4-D废水的设计、优化和控制提供必要的依据。
对2,4-D废水进行了O_3氧化降解实验研究。在O_3氧化2,4-D的反应中，pH值升高有利于反应；反应温度升高反应速率加快；提高气体流量有利于2,4-D的O_3氧化反应；2,4-D初始浓度增加，2,4-D去除率降低，但绝对降解量增大。通过对实验数据的分析，认为2,4-D的去除过程符合拟一级反应动力学。通过GC-MS、HPLC和IC分析，检测出反应中间产物2,4-二氯苯氧甲醛、2,4-二氯苯酚、草酸、顺丁烯二酸等，并推出O_3氧化降解2,4-D的反应路径。
在单独O_3氧化的基础上，对2,4-D废水进行了O_3/H_2O_2氧化降解研究。在O_3/H_2O_2氧化2,4-D的反应中，pH值升高有利于反应；反应温度升高时，反应速率加快，但是温度越高反应速率的提高的程度也越小；提高气体流量有利于反应；2,4-D初始浓度越大去除率越低，但绝对降解量越大；H_2O_2投加量越大2,4-D的去除速率越快；H_2O_2的投加方式对2,4-D的去除率影响不大。通过对实验数据的分析，认为2,4-D在O_3/H_2O_2体系中的去除过程符合拟一级反应动力学。通过GC-MS、HPLC、IC分析，检测出中间产物2,4-二氯苯酚、乙醇酸、乙醛酸、苯醌、顺丁烯二酸、草酸等，并推出O_3/H_2O_2氧化降解2,4-D的反应途径。
实验发现，O_3/H_2O_2氧化比O_3单独氧化更能有效地降低COD和TOC，COD和TOC去除率分别是O_3单独氧化的191％和325％，弥补了O_3单独氧化的缺陷。而且O_3/H_2O_2氧化比O_3单独氧化不仅更有效而且经济性更加明显。
An investigation of kinetics and reaction mechanisms of 2,4-Dichlorophenoxyacetic acid (2,4-D) degraded by O3 and O3/H2O2 system was performed, and gists for treating with wastewater containing 2,4-D were afforded.
During ozonation of 2,4-D, the remove rate of 2,4-D increased with increasing pH of solution, increasing temperature and enhancing gas flow rate, but the degree of enhancing descended with high temperature. The remove rate of 2,4-D decreased with increasing concentration of 2,4-D. The intermediates were identified by GC-MS, HPLC and IC. The 2,4-D decay followed a pseudo first-order reaction. A possible reaction pathway for 2,4-D degradation by O3 involving all intermediates detected was proposed.
During catalytic ozonation of 2,4-D with H2O2, the remove rate of 2,4-D decreased with increasing pH of solution, increasing temperature, enhancing gas flow rate and increasing dosage of H2O2, but the degree of enhancing descended with high temperature. The remove rate of 2,4-D decreased with increasing concentration of 2,4-D. The methods of adding H2O2 had scarcely any influence on the remove rate of 2,4-D. The intermediates were identified by GC-MS, HPLC and IC. A possible reaction pathway for 2,4-D degradation by H2O2 involving all intermediates detected was proposed.
Comparing with ozonation of 2,4-D, catalytic ozonation of 2,4-D with H2O2 showed higher TOC and COD remove rate owing to the hydroxyl radical produced by catalytic ozonation with H2O2, and was more economical.
对2,4-D废水进行了O_3氧化降解实验研究。在O_3氧化2,4-D的反应中，pH值升高有利于反应；反应温度升高反应速率加快；提高气体流量有利于2,4-D的O_3氧化反应；2,4-D初始浓度增加，2,4-D去除率降低，但绝对降解量增大。通过对实验数据的分析，认为2,4-D的去除过程符合拟一级反应动力学。通过GC-MS、HPLC和IC分析，检测出反应中间产物2,4-二氯苯氧甲醛、2,4-二氯苯酚、草酸、顺丁烯二酸等，并推出O_3氧化降解2,4-D的反应路径。
在单独O_3氧化的基础上，对2,4-D废水进行了O_3/H_2O_2氧化降解研究。在O_3/H_2O_2氧化2,4-D的反应中，pH值升高有利于反应；反应温度升高时，反应速率加快，但是温度越高反应速率的提高的程度也越小；提高气体流量有利于反应；2,4-D初始浓度越大去除率越低，但绝对降解量越大；H_2O_2投加量越大2,4-D的去除速率越快；H_2O_2的投加方式对2,4-D的去除率影响不大。通过对实验数据的分析，认为2,4-D在O_3/H_2O_2体系中的去除过程符合拟一级反应动力学。通过GC-MS、HPLC、IC分析，检测出中间产物2,4-二氯苯酚、乙醇酸、乙醛酸、苯醌、顺丁烯二酸、草酸等，并推出O_3/H_2O_2氧化降解2,4-D的反应途径。
实验发现，O_3/H_2O_2氧化比O_3单独氧化更能有效地降低COD和TOC，COD和TOC去除率分别是O_3单独氧化的191％和325％，弥补了O_3单独氧化的缺陷。而且O_3/H_2O_2氧化比O_3单独氧化不仅更有效而且经济性更加明显。
An investigation of kinetics and reaction mechanisms of 2,4-Dichlorophenoxyacetic acid (2,4-D) degraded by O3 and O3/H2O2 system was performed, and gists for treating with wastewater containing 2,4-D were afforded.
During ozonation of 2,4-D, the remove rate of 2,4-D increased with increasing pH of solution, increasing temperature and enhancing gas flow rate, but the degree of enhancing descended with high temperature. The remove rate of 2,4-D decreased with increasing concentration of 2,4-D. The intermediates were identified by GC-MS, HPLC and IC. The 2,4-D decay followed a pseudo first-order reaction. A possible reaction pathway for 2,4-D degradation by O3 involving all intermediates detected was proposed.
During catalytic ozonation of 2,4-D with H2O2, the remove rate of 2,4-D decreased with increasing pH of solution, increasing temperature, enhancing gas flow rate and increasing dosage of H2O2, but the degree of enhancing descended with high temperature. The remove rate of 2,4-D decreased with increasing concentration of 2,4-D. The methods of adding H2O2 had scarcely any influence on the remove rate of 2,4-D. The intermediates were identified by GC-MS, HPLC and IC. A possible reaction pathway for 2,4-D degradation by H2O2 involving all intermediates detected was proposed.
Comparing with ozonation of 2,4-D, catalytic ozonation of 2,4-D with H2O2 showed higher TOC and COD remove rate owing to the hydroxyl radical produced by catalytic ozonation with H2O2, and was more economical.
引文
[1] Matsumura F, Murti CRK. Biodegradation of pesticide.New York: Plenum Press, 1982, 91-111.
[2] Pichat J, D' Oliveira JC, Maffre JF, Mas D. Destruction of 2,4-D in water by TiO2-UV, H2O2-UV or direct photolysis. Photocatalytic purl. cation and treatment of water and air. Amsterdam, New York: Elsevier Science Publisher, 1993, 683-687.
[3] Foster DM, Rachwal A J, White SL. New treatment processes for pesticides and chlorinated organics control in drinking water. J IWEM 1991,5:466-477.
[4] Rice RG, Cotruvo JA. Ozone/chlorine dioxide, oxidation products of organic materials. Cleveland, OH: Ozone Press International, 1978, 490.
[5] Johnson JD, Jensen JN. THM and TOX formation :routes, rates, and precursors. J Am Water Works Assoc 1986,78:156-162.
[6] Means EG, Krasner SW. D-DBP regulation: issues and rami.cations. J Am Water Works Assoc 1993, 85:68-73.
[7] Miltner RJ, Shukairy HM, Summers RS. Disinfection byproduct formation and control by ozonation and biotreatment. J Am Water Works Assoc 1992, 4:53-62.
[8] Upham BL, Yao JJ, Trosko JE, Masten SJ. Determination of the ef.cacy of ozone treatment systems using a gap junction intercelluar communication bioassay. Environ Sci Technol 1995, 29:2923-2928.
[9] 史惠祥，赵伟荣等，偶氮染料的臭氧氧化机理研究．浙江大学学报(工学版)，2003，37(6)：734—738．
[10] 高蓉菁，夏明芳等，臭氧氧化法处理印染废水，污染防治技术，2003，16(4)：68—70．
[11] 卢宁川，府灵敏等，臭氧处理高浓度有机废水，污染防治技术，2002，15(2)：11—12．
[12] 胥维昌，我国农药废水处理现状及展望．化工进展，2000，(5)：18—23．
[13] 程迪，周跃等．有机磷农药废水生化治理现状及进展，化工环保，1992，12(4)：209—213．
[14] 侯纪蓉等，我国农药工业三废治理方法，化工环保，1998，12(1)：15—21：12(2)：82—87．
[15] 朱伟，农药工业三废处理技术的现状与进展，化工环保，1992，6(6)：336—339
[16] 冀滨弘，臭氧技术及其在水处理中的应用[J]．污染防治技术．1997，10(6)：191-194．
[17] 华小梅等，高效微生物在农药废水治理中的应用，污染防治技术，1999，12(3)：149—153．
[18] 张蔚文，混合菌培养在生物降解中的意义 环境科学与技术．1993，(1)：16—20．
[19] 张本兰．有机磷农药乐果生产废水的生化处理新技术，环境科学进展．1994．2(2)：12—16．
[20] 鲍卫仁，2，4-D酸生成简介，山西化工，1990(4)：58—59．
[21] Eva Piera, Juan C. Calpe, 2,4-Dichlorophenoxyacetic acid degradation by catalyzed ozonation: TiO_2/UVA/O_3 and Fe(Ⅱ)/UVA/O_3 systems, Applied Catalysis B: Environmental 2000 (27):169-177.
[22] Enric Brillas, Juan Carlos Calpe, Degradation of the herbicide 2,4-dichlorophenoxyacetic acid by ozonation catalyzed with Fe~(2+) and UVA light, Applied Catalysis B: Environmental 2003 (46): 381-391.
[23] C.Y. Kwan, W. Chu, Photodegradation of 2,4-dichlorophenoxyacetic acid in various iron- mediated oxidation systems, Water Research 2003(37): 4405-4412.
[24] Yunho Lee, Changha Lee, High temperature dependence of 2,4-dichlorophenoxyacetic acid degradation by Fe~(3+)/H_O_2 system, Chemosphere, 2003(51): 963-971.
[25] Satoshi Horikoshi, Hisao Hidaka, Environmental remediation by an integrated microwave/UV-illumination technique Ⅳ. Non-thermal effects in the microwave- assisted degradation of 2,4-dichlorophenoxyacetic acid in UV-irradiated TiO_2/H_2O_2 dispersions, Journal of Photochemistry and Photobiology A: Chemistry 2003 (159): 289-300.
[26] Robert Zona, Sonja Solar, Oxidation of 2,4-dichlorophenoxyacetic acid by ionizing radiation: degradation, detoxication and mineralization, Radiation Physics and Chemistry 2003 (66): 137-143.
[27] 邱宇平，陈金龙等，超高交联树脂吸附处理2，4-D含酚废水的研究，工业水处理，2003，23(4)：50—52．
[28] M A 谢甫钦柯等著，刘存礼译，臭氧化法水处理工艺学，清华大学出版社，1987．
[29]刘春芳，臭氧高级氧化技术在废水处理中的研究进展，石化技术与应用，2002，20(4)：278—280．
[30] 杨志华，祝万鹏等，H_2O_2-O_3氧化法处理染料中间体H酸和1-氨基葸醌生成废液的研究，环境科学，1994，15(6)：4—8．
[31] 陈英，张浩，钟理等，苯酚的O_3／H_2O_2化学氧化动力学研究，化学反应工程与工艺，2001，17(1)：55—60．
[32] 马军，石枫华，O_3／H_2O_2氧化工艺去除水中硝基苯的研究，环境科学，2002，23(5)：67—71
[33] 马军，高金胜，O_3／H_2O_2系统对水中二苯甲酮的去除效能及其机理探讨，黑龙江大学自然科学
学报，2003，20(1)：86—91．
[34] Criegee,R, Die Ozonolyse, Chemie in unserer Zeit 1975(7): 75-81.
[35] Hoigne J, Bader J, Haag W R, Staehelin J, Rate Constants of Reactions of Ozone with Organic and Inorganic Compounds in Water-Ⅲ, Inorganic Compounds and Radicals Water Research 1985(19): 173-183.
[36] Tomiyasu, H. etal, Kinetics and Mechanisms of Ozone Decompo-sition in Basic Aqueous Solut ion. Inorg. Chem., 1985(24): 2962-2967.
[37] Grasso,D, Ozonation Dynamics in Water Treatment: Autocatalytic Decomposition, Mass Transfer and Impact on Particle Stability.PHD Dissertation,The University of Michigan,Ann Arbor, Mich.
[38] Staehelin J, Hoigne J, Decomposition of Ozone in Water: Rate of Initiation by Hydroxide Ion and Hydrogen Peroxide, Environmental Science & Technology, 1982(16):676-681.
[39] Dore.M, Legube.B, Langlais.B., Mechanism of the reaction of ozone with soluble organic pollutants., Ozone: Sci Eng, 1980(2): 39-54,
[40] Chen.S.M, Kuo.C.H, Kinetic studies of oxidation of toluene by ozone and hydrogen peroxide mixtures, MS Thesis, Miss State Univ, US, 1995.
[41] Bader H, Hoigne J., Determination of ozone in water by the indigo method, Wat. Res., 1981(15): 449-456.
[42] 李金昶，王璐等，固相萃取富集高效液相色谱法测定苯氧乙酸和2，4-二氯苯氧乙酸，分析化学研究简报，2001，29(5)：580-582
[43] 陈耀祖，涂亚平，有机质谱原理及应用，北京：科学出版社，2000．
[44] Hoigne J, Bader H, Rate constants of reactions of ozone with organic and inorganic compounds in water-Ⅱ, dissociating organic compounds, Wat Res, 1983(17): 185-194.
[45] Hornge J., Mechanisms, rates and selectivities of oxidation of organic compounds initiated by ozonation of water, Ozone Technology and its Practical Applications, Ann Arbor Science, Ann Arbor, 1982(1): 341-379.
[46] W. Chu, M.H. Ching, Modeling the ozonation of 2,4-dichlorophenoxyacetic acid through a kinetic approach, Water Research, 2003,37:39-46.
[47] 周明华，吴祖成等，基于均相光化学氧化的光电一体化降解对硝基苯酚的研究，催化学报，2002,23(4)：376-379．
[48] Brunet R, Bourbigot M M, Doté M, Oxidation of Organic Compounds through the Combination
Ozone-Hydrogen Peroxide, Ozone Science & Engineering, 1984, 6: 163-183.
[49] Gottschalk,C, Libra, J A, Saupe,A, Ozonation of Water and Waste Water, WILEY-VCH, New York, 2000: 11-15.
[50] Sklyarov VG, Taran PN, Kerzhner BK. Decomposition of 2,4-dichloroohenoxyacetic acid by ozone in aqueous solutions, Khim Tekhnol Vody, 1986,8(1): 81-83.
[51] Bruno Langlais, David A, Reckhow, Ozone in water treatment: application and engineering, Second Printing, 1991.
[52] 陈云华、周鑫玉、潘玲等．臭氧氧化去除水中芳香族化合物机理初探，化工环保，1998，18(2)：74—29．
[53] 钟理，郭江海，叔丁醇水溶液臭氧氧化的降解过程及反应机理研究，现代化工，1999，(19)：25—27．
[54] 张维佳，王宝贞等，臭氧及深度氧化法去除水中污染物，给水排水，2000，26(5)：11—14．
[55] 童少平，刘维屏等，催化臭氧化降解磺基水杨酸的机理，中国环境科学，2003，23(3)：255—258
[2] Pichat J, D' Oliveira JC, Maffre JF, Mas D. Destruction of 2,4-D in water by TiO2-UV, H2O2-UV or direct photolysis. Photocatalytic purl. cation and treatment of water and air. Amsterdam, New York: Elsevier Science Publisher, 1993, 683-687.
[3] Foster DM, Rachwal A J, White SL. New treatment processes for pesticides and chlorinated organics control in drinking water. J IWEM 1991,5:466-477.
[4] Rice RG, Cotruvo JA. Ozone/chlorine dioxide, oxidation products of organic materials. Cleveland, OH: Ozone Press International, 1978, 490.
[5] Johnson JD, Jensen JN. THM and TOX formation :routes, rates, and precursors. J Am Water Works Assoc 1986,78:156-162.
[6] Means EG, Krasner SW. D-DBP regulation: issues and rami.cations. J Am Water Works Assoc 1993, 85:68-73.
[7] Miltner RJ, Shukairy HM, Summers RS. Disinfection byproduct formation and control by ozonation and biotreatment. J Am Water Works Assoc 1992, 4:53-62.
[8] Upham BL, Yao JJ, Trosko JE, Masten SJ. Determination of the ef.cacy of ozone treatment systems using a gap junction intercelluar communication bioassay. Environ Sci Technol 1995, 29:2923-2928.
[9] 史惠祥，赵伟荣等，偶氮染料的臭氧氧化机理研究．浙江大学学报(工学版)，2003，37(6)：734—738．
[10] 高蓉菁，夏明芳等，臭氧氧化法处理印染废水，污染防治技术，2003，16(4)：68—70．
[11] 卢宁川，府灵敏等，臭氧处理高浓度有机废水，污染防治技术，2002，15(2)：11—12．
[12] 胥维昌，我国农药废水处理现状及展望．化工进展，2000，(5)：18—23．
[13] 程迪，周跃等．有机磷农药废水生化治理现状及进展，化工环保，1992，12(4)：209—213．
[14] 侯纪蓉等，我国农药工业三废治理方法，化工环保，1998，12(1)：15—21：12(2)：82—87．
[15] 朱伟，农药工业三废处理技术的现状与进展，化工环保，1992，6(6)：336—339
[16] 冀滨弘，臭氧技术及其在水处理中的应用[J]．污染防治技术．1997，10(6)：191-194．
[17] 华小梅等，高效微生物在农药废水治理中的应用，污染防治技术，1999，12(3)：149—153．
[18] 张蔚文，混合菌培养在生物降解中的意义 环境科学与技术．1993，(1)：16—20．
[19] 张本兰．有机磷农药乐果生产废水的生化处理新技术，环境科学进展．1994．2(2)：12—16．
[20] 鲍卫仁，2，4-D酸生成简介，山西化工，1990(4)：58—59．
[21] Eva Piera, Juan C. Calpe, 2,4-Dichlorophenoxyacetic acid degradation by catalyzed ozonation: TiO_2/UVA/O_3 and Fe(Ⅱ)/UVA/O_3 systems, Applied Catalysis B: Environmental 2000 (27):169-177.
[22] Enric Brillas, Juan Carlos Calpe, Degradation of the herbicide 2,4-dichlorophenoxyacetic acid by ozonation catalyzed with Fe~(2+) and UVA light, Applied Catalysis B: Environmental 2003 (46): 381-391.
[23] C.Y. Kwan, W. Chu, Photodegradation of 2,4-dichlorophenoxyacetic acid in various iron- mediated oxidation systems, Water Research 2003(37): 4405-4412.
[24] Yunho Lee, Changha Lee, High temperature dependence of 2,4-dichlorophenoxyacetic acid degradation by Fe~(3+)/H_O_2 system, Chemosphere, 2003(51): 963-971.
[25] Satoshi Horikoshi, Hisao Hidaka, Environmental remediation by an integrated microwave/UV-illumination technique Ⅳ. Non-thermal effects in the microwave- assisted degradation of 2,4-dichlorophenoxyacetic acid in UV-irradiated TiO_2/H_2O_2 dispersions, Journal of Photochemistry and Photobiology A: Chemistry 2003 (159): 289-300.
[26] Robert Zona, Sonja Solar, Oxidation of 2,4-dichlorophenoxyacetic acid by ionizing radiation: degradation, detoxication and mineralization, Radiation Physics and Chemistry 2003 (66): 137-143.
[27] 邱宇平，陈金龙等，超高交联树脂吸附处理2，4-D含酚废水的研究，工业水处理，2003，23(4)：50—52．
[28] M A 谢甫钦柯等著，刘存礼译，臭氧化法水处理工艺学，清华大学出版社，1987．
[29]刘春芳，臭氧高级氧化技术在废水处理中的研究进展，石化技术与应用，2002，20(4)：278—280．
[30] 杨志华，祝万鹏等，H_2O_2-O_3氧化法处理染料中间体H酸和1-氨基葸醌生成废液的研究，环境科学，1994，15(6)：4—8．
[31] 陈英，张浩，钟理等，苯酚的O_3／H_2O_2化学氧化动力学研究，化学反应工程与工艺，2001，17(1)：55—60．
[32] 马军，石枫华，O_3／H_2O_2氧化工艺去除水中硝基苯的研究，环境科学，2002，23(5)：67—71
[33] 马军，高金胜，O_3／H_2O_2系统对水中二苯甲酮的去除效能及其机理探讨，黑龙江大学自然科学
学报，2003，20(1)：86—91．
[34] Criegee,R, Die Ozonolyse, Chemie in unserer Zeit 1975(7): 75-81.
[35] Hoigne J, Bader J, Haag W R, Staehelin J, Rate Constants of Reactions of Ozone with Organic and Inorganic Compounds in Water-Ⅲ, Inorganic Compounds and Radicals Water Research 1985(19): 173-183.
[36] Tomiyasu, H. etal, Kinetics and Mechanisms of Ozone Decompo-sition in Basic Aqueous Solut ion. Inorg. Chem., 1985(24): 2962-2967.
[37] Grasso,D, Ozonation Dynamics in Water Treatment: Autocatalytic Decomposition, Mass Transfer and Impact on Particle Stability.PHD Dissertation,The University of Michigan,Ann Arbor, Mich.
[38] Staehelin J, Hoigne J, Decomposition of Ozone in Water: Rate of Initiation by Hydroxide Ion and Hydrogen Peroxide, Environmental Science & Technology, 1982(16):676-681.
[39] Dore.M, Legube.B, Langlais.B., Mechanism of the reaction of ozone with soluble organic pollutants., Ozone: Sci Eng, 1980(2): 39-54,
[40] Chen.S.M, Kuo.C.H, Kinetic studies of oxidation of toluene by ozone and hydrogen peroxide mixtures, MS Thesis, Miss State Univ, US, 1995.
[41] Bader H, Hoigne J., Determination of ozone in water by the indigo method, Wat. Res., 1981(15): 449-456.
[42] 李金昶，王璐等，固相萃取富集高效液相色谱法测定苯氧乙酸和2，4-二氯苯氧乙酸，分析化学研究简报，2001，29(5)：580-582
[43] 陈耀祖，涂亚平，有机质谱原理及应用，北京：科学出版社，2000．
[44] Hoigne J, Bader H, Rate constants of reactions of ozone with organic and inorganic compounds in water-Ⅱ, dissociating organic compounds, Wat Res, 1983(17): 185-194.
[45] Hornge J., Mechanisms, rates and selectivities of oxidation of organic compounds initiated by ozonation of water, Ozone Technology and its Practical Applications, Ann Arbor Science, Ann Arbor, 1982(1): 341-379.
[46] W. Chu, M.H. Ching, Modeling the ozonation of 2,4-dichlorophenoxyacetic acid through a kinetic approach, Water Research, 2003,37:39-46.
[47] 周明华，吴祖成等，基于均相光化学氧化的光电一体化降解对硝基苯酚的研究，催化学报，2002,23(4)：376-379．
[48] Brunet R, Bourbigot M M, Doté M, Oxidation of Organic Compounds through the Combination
Ozone-Hydrogen Peroxide, Ozone Science & Engineering, 1984, 6: 163-183.
[49] Gottschalk,C, Libra, J A, Saupe,A, Ozonation of Water and Waste Water, WILEY-VCH, New York, 2000: 11-15.
[50] Sklyarov VG, Taran PN, Kerzhner BK. Decomposition of 2,4-dichloroohenoxyacetic acid by ozone in aqueous solutions, Khim Tekhnol Vody, 1986,8(1): 81-83.
[51] Bruno Langlais, David A, Reckhow, Ozone in water treatment: application and engineering, Second Printing, 1991.
[52] 陈云华、周鑫玉、潘玲等．臭氧氧化去除水中芳香族化合物机理初探，化工环保，1998，18(2)：74—29．
[53] 钟理，郭江海，叔丁醇水溶液臭氧氧化的降解过程及反应机理研究，现代化工，1999，(19)：25—27．
[54] 张维佳，王宝贞等，臭氧及深度氧化法去除水中污染物，给水排水，2000，26(5)：11—14．
[55] 童少平，刘维屏等，催化臭氧化降解磺基水杨酸的机理，中国环境科学，2003，23(3)：255—258