饲料添加剂喹乙醇在猪粪中的残留检测及吸附特征研究
摘要
喹乙醇作为饲料添加剂长期用于动物疾病的预防和促进生长,但由于不能完全被动物机体吸收,以原形或代谢物形式经由畜禽粪尿排入环境,通过不同途径对土壤和水体造成污染。有关喹乙醇在环境中的分布、迁移和稳定性等的研究资料很少。本论文旨在研究喹乙醇残留检测方法及吸附特征,为评估药物饲料添加剂在环境中的分布、转归及对人和环境影响的进一步研究,提供科学依据。
实验一研究建立了猪粪中喹乙醇残留的高效液相色谱检测方法.外源添加喹乙醇的猪粪经蒸馏水提取震荡后,加入硼砂和硫酸锌等净化剂净化样品,离心,过0.22μm滤膜,HPLC检测,用ZORBAX SB-C18色谱柱为固定相,12%甲醇水溶液为流动相,在检测器波长382nm状态下进行检测,喹乙醇浓度在0.05-10.0μg.mL-1之间,其标准曲线线性相关,相关系数r2=0.9999,在0.6mg.kg-1-3.0mg.kg-1添加浓度范围内,回收率在70.07%-83.44%之间,日内变异系数1.20%-4.38%,日间变异系数4.64%-9.62%,样品的检出限0.4μg.kg-1。
实验二通过振荡平衡吸附试验研究了兽药喹乙醇在猪粪上的吸附特征并对其吸附机制和影响因素进行探讨。结果表明,喹乙醇能被猪粪吸附,吸附过程属于快速吸附,吸附等温线呈非线性,能用Freundlich模型很好地描述,被粪便吸附的喹乙醇易被雨水解吸,进入自然环境。粪便对喹乙醇的吸附受溶液pH值和离子强度的影响,随pH值增加粪便对喹乙醇的吸附增加,但碱性条件下有下降趋势。背景溶液离子强度增加,粪便对喹乙醇的吸附量下降。同等浓度的二价Ca2+离子背景下,粪便吸收的喹乙醇能力要比一价Na+离子体系要弱。猪粪对喹乙醇的吸附存在多种吸附机制,物理吸附整个吸附贡献较大。
实验三研究了含喹乙醇猪粪养鱼对鱼塘水质变化和鱼体残留。在猪粪中混入90mg/kg和180mg/kg喹乙醇,对鲤进行了30d的慢性毒性试验。检测每日水中喹乙醇浓度,每10天抽检鱼体内的喹乙醇残留。实验发现,水体中喹乙醇含量逐渐上升,各组在第10、20和30天的采样所测得的鱼体喹乙醇的残留分别是1.87mg/kg、5.25 mg/kg、3.83mg/kg；2.96mg/kg、4.33mg/kg、4.23 mg/kg。通过实验试验模拟施肥养鱼的过程表明,含喹乙醇的动物粪便养鱼,与直接肌肉注射喹乙醇及用含喹乙醇的饲料饲喂鲤鱼对鱼体和生态环境造成的危害相近。
Antibiotics are commonly used at sub-therapeutic levels to livestock to prevent diseases and promote growth. As results of incomplete metabolism and absorption up to 85 % of antibiotics with the parent compound and their metabolites may be excreted into the enviornment via animal manure and human waste, and then be discharged to the soil and water system through different exposure routes. Recent studies had indicated the presence of antibiotics in municipal wastewater effluent and surface water. Despite the detection of antibiotics, little is known about their distribution, mobility and persistence in natural and engineered systems. Presence of antibiotics in environment could perturb ecosystem including bacteria, water and soil microorganism and plants, increase the proliferation of antibiotics-resistant pathogens, and could pose threats to human health.
To assess the magnitude of the potential impacts of antibiotics released into environment, a review was conducted on the occurrence, fate and environmental ecotoxicology of antibiotics in enviornment, and the possible future study was also discussed.
The experiment I:A HPLC method was developed for determination of olaquindox residues in pig manure in this study to establish the analytical method for antibiotics residues in environment and offer reference for the environmental risk assessment. The pig manure were extracted with distilled water, added depurant, and centrifuged then filtrated to detect. ZORBAX SB-C18 was used for stationary phase, whereas the mobile phase comprised 88.0% distilled water and 12% methanol. Olaquindox residues in pig manure were detected by VWD at wavelength of 382nm. The calibration curves for olaquindox standard solution was linear in a concentration range of 0.05-10.0μg.mL-1 (r2=0.9999). The recoveries at levels of 0.6,1.5, and 3.0mg.kg-1 fortified samples ranged from 70.07%-83.44% with coefficient of variation of intra-and inter-assay were 1.20%-4.38% and 4.64%-9.62% respectively. The limit of detection was 0.4μg.kg-1.
The experimentⅡ:The experiment was conducted to study the olaquindox on pig manure sorption characteristics and investigated sorption mechanism and affected factors. The results showed that olaquindox was rapidly adsorbed to manures and Freundlich model could describe preferably the olaquindox nonlinear sorption isotherms. The adsorbed olaquindox was easy to be desorbed by rain with desorption. The sorption of olaquindox on manure were affected by solution pH and ionic strength, the amount of adsorbed olaquindox on manure increased with an increase of pH value and decreased with an increase of ionic strength, and greater sorption effect in the Na systems than the Ca systems was observed. These results suggest that physical adsorption was the mainly contribution to the sorption of olaquindox on pig manure.
The experimentⅢ:The water quality change and tissue concentration of the chronic olaquindox poisoning in common carp were studied. The test was conducted for 30days, under fertilization with 90mg/kg and 180mg/kg olaquindox for fishfarming. Experimental results showed that the concentration of olaquindox in water increased gradually. Olaquindox residue in fish tissue of each group were 1.87mg/kg,5.25 mg/kg,3.83 mg/kg and 2.96 mg/kg,4.33 mg/kg,4.23 mg/kg at the 10th,20th and 30th. It revealed that the harm were similar between fertilization for fishfarming and injection or feeding with olaquindox.
实验一研究建立了猪粪中喹乙醇残留的高效液相色谱检测方法.外源添加喹乙醇的猪粪经蒸馏水提取震荡后,加入硼砂和硫酸锌等净化剂净化样品,离心,过0.22μm滤膜,HPLC检测,用ZORBAX SB-C18色谱柱为固定相,12%甲醇水溶液为流动相,在检测器波长382nm状态下进行检测,喹乙醇浓度在0.05-10.0μg.mL-1之间,其标准曲线线性相关,相关系数r2=0.9999,在0.6mg.kg-1-3.0mg.kg-1添加浓度范围内,回收率在70.07%-83.44%之间,日内变异系数1.20%-4.38%,日间变异系数4.64%-9.62%,样品的检出限0.4μg.kg-1。
实验二通过振荡平衡吸附试验研究了兽药喹乙醇在猪粪上的吸附特征并对其吸附机制和影响因素进行探讨。结果表明,喹乙醇能被猪粪吸附,吸附过程属于快速吸附,吸附等温线呈非线性,能用Freundlich模型很好地描述,被粪便吸附的喹乙醇易被雨水解吸,进入自然环境。粪便对喹乙醇的吸附受溶液pH值和离子强度的影响,随pH值增加粪便对喹乙醇的吸附增加,但碱性条件下有下降趋势。背景溶液离子强度增加,粪便对喹乙醇的吸附量下降。同等浓度的二价Ca2+离子背景下,粪便吸收的喹乙醇能力要比一价Na+离子体系要弱。猪粪对喹乙醇的吸附存在多种吸附机制,物理吸附整个吸附贡献较大。
实验三研究了含喹乙醇猪粪养鱼对鱼塘水质变化和鱼体残留。在猪粪中混入90mg/kg和180mg/kg喹乙醇,对鲤进行了30d的慢性毒性试验。检测每日水中喹乙醇浓度,每10天抽检鱼体内的喹乙醇残留。实验发现,水体中喹乙醇含量逐渐上升,各组在第10、20和30天的采样所测得的鱼体喹乙醇的残留分别是1.87mg/kg、5.25 mg/kg、3.83mg/kg；2.96mg/kg、4.33mg/kg、4.23 mg/kg。通过实验试验模拟施肥养鱼的过程表明,含喹乙醇的动物粪便养鱼,与直接肌肉注射喹乙醇及用含喹乙醇的饲料饲喂鲤鱼对鱼体和生态环境造成的危害相近。
Antibiotics are commonly used at sub-therapeutic levels to livestock to prevent diseases and promote growth. As results of incomplete metabolism and absorption up to 85 % of antibiotics with the parent compound and their metabolites may be excreted into the enviornment via animal manure and human waste, and then be discharged to the soil and water system through different exposure routes. Recent studies had indicated the presence of antibiotics in municipal wastewater effluent and surface water. Despite the detection of antibiotics, little is known about their distribution, mobility and persistence in natural and engineered systems. Presence of antibiotics in environment could perturb ecosystem including bacteria, water and soil microorganism and plants, increase the proliferation of antibiotics-resistant pathogens, and could pose threats to human health.
To assess the magnitude of the potential impacts of antibiotics released into environment, a review was conducted on the occurrence, fate and environmental ecotoxicology of antibiotics in enviornment, and the possible future study was also discussed.
The experiment I:A HPLC method was developed for determination of olaquindox residues in pig manure in this study to establish the analytical method for antibiotics residues in environment and offer reference for the environmental risk assessment. The pig manure were extracted with distilled water, added depurant, and centrifuged then filtrated to detect. ZORBAX SB-C18 was used for stationary phase, whereas the mobile phase comprised 88.0% distilled water and 12% methanol. Olaquindox residues in pig manure were detected by VWD at wavelength of 382nm. The calibration curves for olaquindox standard solution was linear in a concentration range of 0.05-10.0μg.mL-1 (r2=0.9999). The recoveries at levels of 0.6,1.5, and 3.0mg.kg-1 fortified samples ranged from 70.07%-83.44% with coefficient of variation of intra-and inter-assay were 1.20%-4.38% and 4.64%-9.62% respectively. The limit of detection was 0.4μg.kg-1.
The experimentⅡ:The experiment was conducted to study the olaquindox on pig manure sorption characteristics and investigated sorption mechanism and affected factors. The results showed that olaquindox was rapidly adsorbed to manures and Freundlich model could describe preferably the olaquindox nonlinear sorption isotherms. The adsorbed olaquindox was easy to be desorbed by rain with desorption. The sorption of olaquindox on manure were affected by solution pH and ionic strength, the amount of adsorbed olaquindox on manure increased with an increase of pH value and decreased with an increase of ionic strength, and greater sorption effect in the Na systems than the Ca systems was observed. These results suggest that physical adsorption was the mainly contribution to the sorption of olaquindox on pig manure.
The experimentⅢ:The water quality change and tissue concentration of the chronic olaquindox poisoning in common carp were studied. The test was conducted for 30days, under fertilization with 90mg/kg and 180mg/kg olaquindox for fishfarming. Experimental results showed that the concentration of olaquindox in water increased gradually. Olaquindox residue in fish tissue of each group were 1.87mg/kg,5.25 mg/kg,3.83 mg/kg and 2.96 mg/kg,4.33 mg/kg,4.23 mg/kg at the 10th,20th and 30th. It revealed that the harm were similar between fertilization for fishfarming and injection or feeding with olaquindox.
引文
[1]王丽平,顾国平,章明奎.抗生素残留对农产品安全与生态环境的影响[J].安徽农学通报,2007,13(2)：74-76
[2]李凯年,抗生素饲料添加剂酌作用与发展趋势[J]饲料广角,2005,13：28-32
[3]赵红梅,金升藻.滥用抗生素对人畜的危害及对策研究[J].国外医药抗生素分册,2003,24(4)：164-167
[4]Diaz-Cruz, M.S., Lopez de Alda, M.J., Barcelo, D.Environ-mental behavior and analysis of veterinary and human drugs in soils.sediments and sludge[J].Trends in AnalyticalChemistry,2003,22(6): 340-350
[5]俞道进,曾振灵,陈杖榴.四环素类抗生素残留对水生态环境影响的研究进展[J].中国兽医学报,2004,9(5)：515-517
[6]Heilig S, Lee P, Breslow L. Curtailing antibiotic use in agriculture [J]. Western Journal of Medicine, 2002.176:9-11
[7]Tolls J. Sorption of veterinary pharmaceuticals in soils:Areview[J]. Environmental Science and Technology,2001,35(17):3397-3406
[8]Halling-Sφrensen B, Nors Nielsen S, Lanzky P F, Ingerslev F,Holten Lutzhφft H C, Jφrgensen S E. Occurrence, fate and effects of pharmaceutical substances in the environment a review [J]. Chemosphere, 1998,36(2):357-393
[9]WoHenberger L, Hailing-Sφrensen B, Kusk K O. Acute and chronic toxicity of veterinary antibiotics to Daphnia magna[J]. Chemosphere,2000,40:723-730
[10]Hirsch R, Terlles T, Haberer K. Occurrence of antibiotics in the aquatics environment[J]. Science of the Total Environment,1999,36:3573-3593
[11]Animal Health Institute.1997. Market research report[R].Alexandria VA:U.S. Animal Health Product Industry,59
[12]Benbrook C M. Antibiotic drug use in U.S. aquaculture[OL].Institute for Agriculture and Trade Policy Report.2002-02. http:www.iatp.org/library/antibiotics
[13]Boxall A B A, Kolpin D W, Halling-Sorensen B, Tolls J. Are veterinary medicines causing environmental risks?[J]. Environmental Science and Technology,2003.37:286A-294 A
[14]梁红杏,张名涛.饲用抗生素在绿色畜牧业中的应用前景[J].畜牧业,2002,12：50-52
[15]Rooklidge, S.J.Environmental antimicrobial contamination from ter-raccumulation and diffuse pollution pathways[J] Science of the Total Environment,2004,325:1-13
[16]EMEA-The European Agency for the Evaluation of Medician Products.Antibiotic resistance in the European Union associated with the therapeutic use of veterinarymedicines[M].EMEA/CVMP/342 /99-final.1999
[17]顾君华,王欣.完善养殖模式抵制滥用抗生素[J].饲料广角,2003,20：3-6
[18]候放亮.饲料添加剂应用大全[M].北京：中国农业出版社.2003.
[19]Koplin D W. Pharmaceuticals, hormones and other organic wastewater contaminates in U.S. streams,1999-2000[J].A National econaissance. Environmental Science and Technology,2002,36(6): 1202-1211
[20]曹卫东,王旭,刘传平.当前部分有机肥料中的持久性有机污染问题[J].土壤肥料,2006(2)：8-11
[21]王冉,刘铁铮,耿志明.兽药磺胺二甲嘧啶在土壤中的生态行为[J].土壤学报,2007,3(2)：307-311
[22]王冉,刘铁铮,魏瑞成.猪粪便中兽药盐霉素残留的降解动态研究[J].农业环境科学学报,2007,26(增刊)：219-223
[23]DijckPV,vande VoordeH.Sensitivity of environmental microorganism to antimicrobial agents[J]. Applied and Environmental Microbiology,1976,31:332-336.
[24]WollenbergerL,Halling-SφrensenB,KuskKO.Acute and chronic toxicity of veterinary antibiotics to Daphniamagna[J].Chemospere,2000,40:723-730.
[25]MiglioreL, BrambillaG, CasoriaP, etal. Effects of sulphadime-thoxine on barley in Laboratory terrestrialmodels[J].Agriculture Ecosystems Environment,1996,60:121-128.
[26]Rooklidge,S.J.Environmental antimicrobial contamination from ter-raccumulation and diffuse pollution pathways[J].Science of the Total Environment,2004,325:1-13.
[27]Ingerslev, R, Holten, Lutzhoft, H.C., Halling-Sφrensen, B.Humant anvendte lagemidlers vej tilmiljoet er gennem rensningsanagget[J].DanskKem,1999,80:222-225
[28]Jemba, P.K.The potential impactofveterinary and human therapeutic agents in manure and biosolids on plants grown on arable land:areview[J]. Agriculture, Ecosystems and Environment,2002,93: 267-278
[29]Kolpin D W, Furlong E T, Meyer E M, Zaugg S D, Barber LB, Buxton H T. Pharmaceuticals, hormones, and other organic wastewater contaminants in US streams,1999-2000:Anational reconnais-sance[J]. Environmental Science and Technology,2002,36(6):1202-1211
[30]Hoper H, Kues J, Nau H, Hanscher G Eintrag and Verbleib von Tierarzneimittelwirkstoffen in B6den[J]. Bodenschutz,2002,4:141-148
[31]Hamscher G, Sczesny S, Hoper H, Nau H. Determination of persistent tetracycline residues in soil fertilized with liquidmanure by high-performance liquid chromatography with electrosprayionization tandem mass spectrometry[J]. Analytical Chemistry,2002,74(7):1509-1518
[32]Sengelφv G, Agerso Y, Halling-Sφrensen B, Baloda S B, Andersen J S, Jensen L B.Bacterial antibiotic resistance levels in Danish farmland as a result of treatment with pig manure slurry [J].Environmental International,2003.28(7):587-595
[33]王丽平,顾国平,章明奎.抗生素残留对农产品安全与生态环境的影响[J].安徽农学通报,2007,13(2)：74-76
[34]Halling-Sφrensen B, Nors Nielsen S, Lanzky P F, Ingerslev F, Holten Lutzhφft H C, Jφrgensen S E. Occurrence, fate and effects of pharmaceutical substances in the environment a review[J].Chemosphere, 1998,36(2):357-393
[35]Animal Health Institute. Market research report[R].Alexandria VA:U.S. Animal Health Product Industry,1997,59
[36]Spaepen K R I, Van Leemput L J J, Wislocki P G, WerschuernC. A uniform procedure to estimate the predicted environmental concentration of the residues of veterinary medicines in soil[J].Environ mental Toxicology and Chemistry,1997.16:1977-1982
[37]Montforts M H M M, Kalf D F, Van Vlaardingen P L A,Linders J B H J. The exposure assessment for veterinarymedicinal products [J]. Science of the Total Environment,1999,225:119-133
[38]Meyer M T, Bumgarner J E, Varns J L, Thurman E M,Hostetler K A. Use of radioimmunoassay as a screen for antibiotics in confined animal feeding operations and confirmation by liquid chromatogra-phymass spectrometry[J]. Science of the Total Environment,2000,248(2-3):181-187
[39]HamscherG, SczesnyS, AbuQareA, HoperH, NauH. Sub-stances with pharmacological effects including hormonally active substances in the environment:identification of tetracyclines in soil fertilized with animal slurry[J].Dtsch Tierarztl Wochenschr,2000,107(8):332-334.
[40]Jemba,P.K.The potential impact of veterinary and humantherapeutic agents in manure and biosolids on plants grown on arable land:a review[J].Agriculture,Ecosystems and Environment,2002,93:267-278.
[41]Thiele-Bruhn,S. Pharmaceutical antibiotic compounds in soils a review[J]. Journal of Plant Nutrition and Soil Science,2003,166:145-167.
[42]Campagnolo E R, Johnson K R, Karpati A, Rubin C S, Kolpin D W, Meyer M T, Esteban J E, Currier R W, Smith K, Thu K M, McGeehin M. Antimicrobial residues in animal waste and water resources proximal to large scale swine and poultry feeding operations[J]. Science of the Total Environment,2002,299:89-95
[43]Hamscher G, Sczesny S, Hoper H, Nau H. Determination of persistent tetracycline residues in soil fertilized with liquid manure by high performance liquid chromatography with electrospray ionization tandem mass spectrometry[J]. Analytical Chemistry,2002,74(7):1509-1518
[44]Golet E M, Strehler A, Alder A C, Giger W. Determination of fluoroquinolone antibacterial agents in sewage sludge and sludge treated soil using accelerated solvent extraction followed by solid phase extraction[J]. Analytical Chemistry,2002,74:5455-5462
[45]Morales-Muoz S, Luque-Garcia J L, Luque de Castro M D. Continuous microwave assisted extraction coupled with derivatization and fluorimetric monitoring for the determination of fluoroqu-inolone antibacterial agents from soil samples[J]. Journal of Chromatography A,2004,1059(1-2):25-31
[46]Haller M Y, Muller S R, McArdell C S, Alder A C, Suter M J F. Quantification of veterinary antibiotics(sulfonamides and trimethoprim) in animal manure by liquid chromatography mass spectrometry[J]. Journal of Chromatography A,2002,952:111-120
[47]De Liguoro M, Cibin V, Capolongo F, Halling-Sφrensen B,Montesissa C. Use of oxytetracycline and tylosin in intensive calf farming:evaluation of transfer to manure and soil[J]. Chemosphere,2003,52: 203-212
[48]Aga D S, O'Connor S, Enslev S O, Payero J, Snow D, Tarkalson D. Determination of the persistence of tetracycline antibiotics and their degradates in manure-amended soil using enzyme-linked immunosorbent assay and liquid chromatography mass spectrometry[J]. Journal of Agriculture Food Chemosphere,2006,53:7165-7171
[49]Hailing-Sφrensen B. Inhibition of aerobic growth and nitrification of bacteria in sewage sludge by antibacterial agents[J].Archives of Environmental Contamination and Toxicology,2001,40:451-460
[50]Pearson M,Inglis V J F DA sensitive mi crobioassay for the detection of antibacterial agents in the-aquatic environment[J].Journal of Fish Diseases,1993.16:255-260
[51]Hirsch R,Ternes T,Haberer K,Kratz K LOccurrence of antibiotics in the aquatic environment [J].Science of the Total Environment,1999,225:109-118
[52]Ternes T A,Joss A,Siegrist H.Scrutinizing pharmaceutical and personal care products in wastewater treatment[J].Environmental Science and Technology,2004,38:392A-399A
[53]Kolpin D W, Furlong E T, Meyer M T, ThllI-E M, Zaugg S D, Barber L B, Buxton H T. Pharmaceuticals, horm ones and other waste water contaminants in US streams 1999-2000.A national [J].Environmental Science and Technology,2002.36:1202-1211
[54]Batt A L, Bruce I B, Aga D S.Evaluating the vulnerability of surface watem to antibiotic contamination from varying wastewater treatment plant discharges[J].Environmental Pollution, 2006,142(2):295-302
[55]Zuccato E,Calamari D,Natangelo M,Fanelli R.Presence of therapeutic drugs in the environment [J].The Lancet,2000,355 (9217):1789-1790
[56]Kim S D,Cho J,Kim I S,Vandefford B J,Snyder S A.Occurrence and removal of pharmac-euticals and endocrine disruptors in South Korean surface, drinking, and waste water[J].Water Research,2007,41 (5):1013-1021
[57]Capo ne D G, Weston D P,Miller V, Shoemaker C. Antibacterial residues in Illarine sediments an d invertebrates following chemotherapy in aquaculture[J].Aquaculture,1996,145:55-75
[58]Holm J V, Rugge K, Sjerg P L, Christensen T H.Occurrence and distribution of pharmaceutical organic compoundsin the groundwater downgradient of a landfill Frinsted,Denmark[J].Environmental Science and Technology,1995,36:1-6
[59]Sarmah A K, Meyer M T, Boxall A B A. A global perspective on the use, sales, exposure pathways, occurrence, fate and effects of veterinary antibiotics (VAs) in the environment[J]. Chemosphere,2006,65(5):725-759
[60]Yang W, Carlson K.Evolution of antibiotic occurrence in a fiver through pristine, urban, and agricultural landscapes[J].Water Research,2003,37:4645-4656
[61]Mellon M, Benbrook C, Benbrook K L. Hogging It. Estimates of Antimicrobial Abuse in Livestock[J].Union of Concerned Scientists Publications, Washington DC,2001:7-9
[62]Loke ML, SonjaJespersen, Vreeken R, Hailing-Sφrensen B, Tjornelund J.Determ ination of oxytetracycline and its degradation products by high perform ance liquid chroma tographytandem mass spectrometry in manure-containing anaerobic test system[J].Journal of Chromatography B,2003,783 (1):11-23
[63]Hailing-Sφrensen B, Lykkeberg A, Ingerslev F'Blackwell TjCrnelund J.Characterisation of the abiotic degradation pathways of Oxytetracyclines in soil interstitial water using LC-MS-MS[J]. Chemosphere,2003,50(10):1331-1342
[64]Thiele-Brn hn S, Peters D, Hailing-Sφrensen B, Leinwebe P.Photodegradate on and ageing of antibiotic pharmaceutical on soil.Lyon:Presentation of project results on Envirpharma Europe an conference[J].2003:14-16
[64]W arman PR.The effect of Amprolium and Aureomycin antibiotic on the nitrification of poultry manure amended soil.Joumal of the soil Science Society of America[J].1980,44(6):1333-1334
[65]Pursell L, Samuelsen OB, Smith P.Reduction in the in-vitro activity of flumequine against Aeromonas salmonicida in the presence of the concentration of Mg and Ca ions in found in sea water.Aquaculture[J].1995,135(4):245-255
[66]Backhaus Grimme LH.The toxicity of antibiotic agents to the lumi nescent bacterium Vibrio fischeri[J].Chemosphere,1999,38(14):3291-3301
[67]Hamscher QSczesny S,Hoper H, Nau H.Determ ination of persistent tetracycline residues in soil fertilized with liquid manure by high-perform ance liquid chromatography with electrospray ionization tandem mass spectrometry[J]. Analytical Chemistry,2002,74(7):1509-1518
[68]Boleas S, Alonso C, Pro J, Fernandez A, Carbonell G, TarazonaJ V.2005. Toxicity of the antimicrobial oxytetracycline to soil organisms in a multi-species-soil system and influence of manure coaddition[J]. Journal of Hazardous Materials,2005,122:233-241
[69]Kong W D, Zhu Y G, Fu B J, Marschner P, He J Z. The veterinary antibiotic oxytetracycline and Cu influence functional diversity of the soil microbial community[J]. Environmental Pollution,2006,143: 129-137
[70]Batchelder AR.Chlortetracycline and oxytetracycljne effects on plant growth and development in liquid cultures[J].Journal of Environment Quality,1981,10(4):515-518
[71]Batchelder AR.Chlonetracycljne and Oxytetracycline effects on plant growth and development in soil systems[J].Joumal of Environment Quality,1982,11(4):675-678
[72]Migliore L,Civitareale C,Brambilla G Cozzolino S,Casoria Gaudio L.Effects of sulphadimethoxine on cosmopolitan weeds maranthus retroflexus L. Plantago major L and Rumex acetoseUa L[J]. Agriculture,Ecosystems & Environment,1997,65(2):163-68
[73]Lanzky PF, Hailing-SrφnsenB.he toxic effect of the antibiotic metronidazole on aquatic organ-isms[J].Chemosphere,1997,5(11):2553-2561
[74]Patten D K, Wolf D C, Kunkle W E, Douglass L W. Effects of antibiotics in beef cattle feces on notrogen and carbon mineralization in soil and on plant growth and conposition[J].Journal of Environmental Qualty,1980:167-172
[75]Migliore L, Civitareale C, Cozzolino S, Fiori M. Phytotoxicity to and uptake of enrofloxacin in crop plants[J].Chemosphere,2003,52:1233-1244
[76]Batchelder A R. Chlortetracycline and oxytetracycline effects on plant growth and development in soil systems[J]. Journal of Environmental Qualty,1982,11:675-678
[77]Jjemba P K. The effect of chloroquine, quinacrine, and metronidazole on both soybean plants and soil microbiota[J].Chemosphere,2002,46:1019-1025
[78]Migliore L, Civitareale C, Cozzolino S, Fiori M. Phytotoxicity to and uptake of enrofloxacin in crop plants [J].Chemosphere,2003,52:1233-1244
[79]Boxall A B A, Kolpin D W, Halling-Sφrensen B, Tolls J. Are veterinary medicines causing environmental risks?[J].Environmental Science and Technology,2003,7:286A-294A
[80]Migliore L, Civitareale C, Cozzolino S, Casoria P, Brambilla, G, Gaudio L. Laboratory models to evaluate phytotoxicity of sulphadimethoxine on terrestrial plants[J].Chemosphere,1998,7(14-15): 2957-2961
[81]Bradel B G, Preil W, Jeske H.2000. Remission of the freebranching pattern of Euphorbia pulcherrima by tetracyclinetreatment[J]. Journal of Phytopathology,148:587-590
[82]Wollenberger L,Hailing-Sφrensen B,Kusk KO.Acute and chronic toxicity of veterinary antibiotics to Daphnia magna[J].Chemosepere,2000,40;23-730.
[83]俞道进,曾振灵,陈杖榴.四环素类抗生素残留对水生态环境影响的研究进展[J].中国兽医学报,2004,9(5)：515-517
[84]Hoekstra JA.van Ewijk PH.Altematives for the No-bserved-effect level[J]. Environmental Toxicol-ogy and Chemistry,1993,12(1):187-194
[85]Baguer AJ,Jensen J,Krogh PH.Effects of the antibiotics oxytetracycline and tylosin on soil fauna[J]. Chemosphere,2000,40(7):751-757
[86]Hamscher G, Sczesny S, Hoper H, Nau H.Determ ination of persistent tetracycline residues in soil fertilized with liquid manure by high performance liquid chromatography with electrospray ionization tandem mass spectrometry[J]. Analytical Chemistry,2002,74(7):1509-1518
[87]Loke ML, Ingerslev Hailing-Sφrensen B, TjCrnelund J Stability of Tylosin A in manure containing test systems determined by high performance liquid chromatography[J].Chemosphere,2000,40 (7):759-765
[88]Boleas S, Alonso C, Pro J, Fernandez A, Carbonell G, Tarazona J V.2005. Toxicity of the antimicrobial oxytetracycline to soil organisms in a multi-species-soil system(MS) and influence ofmanure coaddition [J]. Journal of Hazardous Materials,122:233-241
[89]Kong W D, Zhu Y G, Fu B J, Marschner P, He J Z. The veterinary antibiotic oxytetracycline and Cu influence functional diversity of the soil microbial community [J].Environmental Pollution,2006,43: 129-137
[90]Westergaard K, Muller A K, Bloem J, Sφrensen S J. Effects of tylosin as a disturbance on the soil microbial community[J].Soil Biology and Biochemistry,2001,2(15):2061-2071
[91]Thiele SPharmaceutical antibiotic compound in soils a review[J]. Journal of Plant Nutrition and Soil Science,2003,66:145-167
[92]Bailey V L, Smith J L, Jr Bolton H.2002. Fungal-to-bacterial ratios in soils investigated for enhanced C sequestration [J]. Soil Biol Biochem,34(7):997-1007
[93]Bailey V M, Smith J L, Bolton H. Novel antibiotics as inhibitors for the selective respiratory inhibition method of measuring fungal:bacterial ratios in soil[J]. Biol Fertil Soils,2003,8:154-160
[94]王冰,孙成,胡冠九.环境中抗生素残留潜在风险及其研究进展[J].环境科学与技术,2007,3(3)：108-111
[95]Diaz-Cruz,M.S.,LopezdeAlda,M.J.,Barcelo,D.Environ-mental behavior and analysis of veterinary and human drugs in soils,sediments and sludge[J].Trends in Analytical Chemistry,2003,22(6):340-350.
[96]Ying GG, Kookana RS, Ru YJ.Occurrence and fate of horm one steroids in the environment[J]. ironment International,2002,28(6):545-551
[97]Rabolle M, Spliid NH. Sorption and mobility of metronidazole, olaquindox, oxytetracycline and tylosin in soil[J]. Chemosphere,2000,40(7):715-722
[98]Lunestad B Goksoyr J.eduction in the antibacterial effect of Oxytetracycline in sea water by complex formation with magnesium and alcium[J]. Diseases of Aquatic Organisms,1990,9:67-72
[99]Boxall ABA,Blackwell Cavallo R.Kay E The sorption and transport of a sulphonamide antibiotic in soil systems[J].Toxicology Letters,2002,131(1-2):19-28
[100]Bakal RS,Stoskopf M K.In vitro studies of the fate of sulfadimethoxine and ormetoprim in the aquatic environment[J].Aquaculture,2001,195(1-2):95-102
[101]Capone DG Weston DP, Miller V' Shoemaker C.Antibacterial residues in marine sediments and invertebrates following chemotherapy in aquaculture.Aquaculture,1996,145(14):55-75
[102]Aboul-Kassim. Simoneit BR The handbook of environmental chemistry Vol.5 Part E, Pollutant solid phase i nteractions:M echanism, chemistry and modeling[J].BerlinHeidelberg:Springer Verlag, 2001,141-159
[103]卞永荣,蒋新,王代长.五氯酚在酸性土壤表面的吸附-解吸特征研究[J].土壤,2004,36(2)：181-186
[104]梁重山,党志,刘丛强.菲在土壤／沉积物上的吸附-解吸过程及滞后现象的研究[J].土壤学报,2004,41(3)：329-335
[105]罗雪梅,杨志峰,何孟常.土壤／沉积物中天然有机质对疏水性有机污染物的吸附作用[J].土壤,2005,37(1)：25-31
[106]Jia LQ, Ou ZQ,Ouyang ZY.Ecological behavior of linear alkylbenzene sulfonate(LAS) in soil plant system[J].Pedosphere,2005,15(2):216-224
[107]Jacobsen P, Berglind L. Persistence of oxytetracycline in sediments from fish farms[J]. Aquaculture,1988,70(4):365-370
[108]Richardson ML,Bowron JM.The fate of pharmaceutica chemicals in the aquatic environment[J]. Pharmacy and Pharmacology,1985,37(l):1-12
[109]Ingerslev F.Hailing-Sφerensen B.Biodegradabilit properties of sulfonamides in activated sludge [J].Environment Toxicology and Chemistry,2000,19(10):2467-2473
[110]Campos JL,Garrido JM,M fndez R,Lema JM.Effect of two broad spectrum antibiotics on activity and stability of continuous nitrifying system.Applied Biochemistry and Bjotechnology PartA[J],Enzyme Engineering and Biotechnology,2001,95(1):1-10
[111]W arman PR,Thom as RL.Chlortetracycline in soil amended with poultry manure[J].Canadian Jo-umal of Soil Science,1981,61(1):161-163
[112]曹卫东,王旭,刘传平.当前部分有机肥料中的持久性有机污染问题[J].土壤肥料,2006(2)：8-11
[113]周启星,罗义,王美娥.抗生素的环境残留生态毒性及抗性基因污染[J].生态毒理学报,2007,9(3)：243-251
[1]Benbrook C M. Antibiotic Drug Use in U.S. Aquaculture.Institute for Agriculture and Trade Policy Report, February 2002. www.iatp.org/library/antibiotics.
[2]Halling-Sφrensen, B., Nors Nielsen, S., Lanzky, P. F., Ingerslev, F., Holten Lutzheft, H. C., and Jφrgensen, S. E. Occurrence, fate and effects of pharmaceutical substances in the Environment--A review. Chemosphere [J].1998,36,357-393.
[3]Hartmann A, Alder A C, Koller T, et al. Identification of fluoroquinolone antibiotics as the main source of human genotoxicity in native hospital wastewater[J]. Environmental Toxicology and Chemistry,1998,17:377-382
[4]B.Halling-Sφrensen, Algal toxicity of antibacterial agents used in intensive farming[J]. Chemosphere, 2000,40,731-739
[5]王冉,刘铁铮,王恬.抗生素在环境中的转归及其生态毒性[J].生态学报,2006,1,(1)：265-270
[6]Bertschinger, H.U.,Die chemotherapeutiche Wirksamkeit von Olaquindox bei Ferkeln mit experimenteller Colidiarrhoe und Colinenterotoxamie. Schweitz.Arch[J].Tierheilkd.1976,118,397-407.
[7]Holmgren, N., Profylaktiska effekter av zinkoxid eller olaquindox mot awa njningsdiarre hos svin(Prophylactic effects of zinc oxide or olaquindox against weaning diarrhoea in pigs)[J]. Svensk Veterinartidn,1994,46,217-222 (in Swedish, with English abstract).
[8]Holmgren, N., Lundeheim, M., Djurhalsomassiga behovet av fodermedelsantibiotika i sma grisproducerandebesa'ttningar (The medicated feed requirement of piglet-producing herds)[J]. Svensk Veterinartidn,1994.46,57-65 (in Swedish, with English abstract).
[9]Fellstrom, C., Pettersson, B., Johansson, K.E., Lundeheim, N., Gunnarsson, A., Prevalence of Serpulina speciesin relation to diarrhoea and feed medication in pig rearing herds in Sweden[J]. American Journal of Veteriary Research.1996,57,807-811.
[10]李俊锁,钱传范.残留分析中的检测限和测定限[J].农药译丛,1997,19(1)：56-60
[11]Tunney, H., Molloy, S., Variations between farms in N,P, K, Mg and dry matter composition of cattle, pig and poultry manures[J]. Ireland Journal of Agricultural Research.1975,14,71-79.
[12]Japenga, J., Harmsen, K., Determination of mass balance and ionic balances in animal manure[J]. Netherlands Journal of Agricultural Science,1990,38,353-367.
[13]Choudhary, M., Bailey, L.D., Grant, C.A., Review of the use of swine manure in crop production: effects on yield and composition and on soil and water quality[J]. Waste Management & Research.1996, 14,581-595.
[14]Da la Torre, A.I., Jim_enez, J.A., Carballo, M., Fernandez, J.R.,Mu～noz, M.J., Ecotoxicological evaluation of pig slurry[J]. Chemosphere,2000,41,1629-1635.
[15]G F Bories. High-performance liquid chromatography determination of Olaquindox in feeds[J]. Journal of Chromatography,1979,172:505-508.
[16]杨文军,张丽英,李德发.反相高效液相色谱法测定饲料中喹乙醇的含量[J].中国兽药杂志,2003,37(2)：20-23
[17]艾晓辉,刘长征,文华.鱼组织中喹乙醇残留量高效液相色谱检测方法研究[J].湖北农学院学报,2003,8(4)：266-270
[1]Kolpin D W, Furlong E T, et al. Pharmaceuticals, hormones, and other organic wastewater contaminantsin U.S.streams,1999-2000:anationalreconnaissance[J]. Environmental science & technol-ogy,2002,36,1202-1211
[2]Halling-Sφrensen,B.,Nors Nielsen,S., Lanzky, P. R, et al. Occurrence, fate and effects of pharma-ceutical substances in the Environment--A review. Chemosphere[J].1998,36,357-393.
[3]Hartmann A, Alder A C, Koller T, et al. Identification of fluoroquinolone antibiotics as the main source of human genotoxicity in native hospital wastewater[J]. Environmental Toxicology and Chemistry,1998,17,377-382
[4]B.Halling-Sφrensen. Algal toxicity of antibacterial agents used in intensive farming[J]. Chemosphere, 2000,40,731-739
[5]王冉,刘铁铮,王恬.抗生素在环境中的转归及其生态毒性[J].生态学报,2006,1,(1)：265-270
[6]Mette Rabulle, Niels Henrik Spliid. Sorption and mobility of metronidazole, olaquindox, oxytetracycline and tylosin in soil[J]. Chemosphere,2000,40,715-722
[7]Flemming Ingerslev, Bent Halling-Sφrensen. Biodegradability of Metronidazole, Olaquindox, and Tylosin and Formation of Tylosin Degradation Products in Aerobic SoilIManure Slurries[J]. Ecotoxic-ology and Environmental Safety,2001,48,311-320
[8]Allare S.E, Castillo J D, and Juneau V, Sorption kinetics of chlortetracycline and tylosin on sandy loam and heavy clay soils[J]. Journal of Environmental Quality,2006,135,969-972.
[9]Gu C, Karthikeyan K G,Interaction of tetracycline with aluminum and iron hydrous oxides[J]. Environmental science & technology,2005,39,2660-2667.
[10]Pouliquen H, Bris H L, Sorption of oxolinic acid and oxytetracycline to marine sediments[J]. Chemosphere,1996,33,801-815.
[11]Sithole B B, Guy R D, Models for tetracycline in aquatic environments. I. Interaction with bentonite clay sytems [J]. Water, Air, Soil Pollution.1987,32,303-314.
[12]OECD Adsorption/desorption using a batch equilibrium method. OECD guidelines for testing of chemicals, test guideline 106. Organization for Economic Cooperation and Development:Paris, France, 2000.
[13]Van Dijk J, Keukens H J. In Residues of Veterinary Drugs in Food:Proceedings of the Euroresidue IV Conference; Van Ginkel,L.A.,Ruiter,A.,Eds.Veldhoven,The Netherlands,2000.178-182
[14]Rabφlle M, Spliid N H, Sorption and mobility of metronidazole, olaquindox, oxytetracycline, and tylosin in soil[J], Chemosphere,2000,40,715-722.
[15]Marie-Louise Loke, Jette Tjφrnelund, Bent Halling-Sφrensen. Determination of the distribution coefficient (logKd) of oxytetracycline, tylosin A, olaquindox and metronidazole in manure[J]. Chemosphere,2002,48,351-361
[1]Halling-Sorensen, B., Nors Nielsen, S., Lanzky, P. F., Ingerslev, F., Holten Lutzhφft, H. C., and Jφrgensen, S. E. Occurrence, fate and effects of pharmaceutical substances in the Environment--A review. Chemosphere [J].1998,36,357-393.
[2]Hartmann A, Alder A C, Koller T, et al. Identification of fluoroquinolone antibiotics as the main source of human genotoxicity in native hospital wastewater[J].Environmental Toxicology and Chemistry, 1998,17:377-382
[3]B.Halling-Sφrensen, Algal toxicity of antibacterial agents used in intensive farming[J].Chemosphere, 2000,40,731-739
[4]王冉,刘铁铮,王恬.抗生素在环境中的转归及其生态毒性[J].生态学报,2006,1,(1)：265-270
[5]郭庆,任泽林,曾虹.喹乙醇在水产养殖中的应用[J].中国饲料,1997,(5)：27-28
[6]Zeng H. Nutrient requirements of fish [M]. Beijing:China Agricultural Press,1993:70-71.
[7]Cheng J R. Water chemistry[M]. Beijing:China Agricultural Press,1998:260-261.
[8]于慧娟,毕士川,黄冬梅高效液相色谱法测定水产品中喹乙醇的残留量[J].分析科学学报,2004,6：281-283
[9]艾晓辉,陈正望,张春光,喹乙醇在鲤体内的药物代谢动力学及组织浓度[J].水生生物学报,2003,27,(3)：273-276
[10]杨先乐,胡鲲,邱军强,喹乙醇在鱼体内蓄积及其对鱼类的影响[J].水生生物学报,2005,29(1)：13-18
[2]李凯年,抗生素饲料添加剂酌作用与发展趋势[J]饲料广角,2005,13：28-32
[3]赵红梅,金升藻.滥用抗生素对人畜的危害及对策研究[J].国外医药抗生素分册,2003,24(4)：164-167
[4]Diaz-Cruz, M.S., Lopez de Alda, M.J., Barcelo, D.Environ-mental behavior and analysis of veterinary and human drugs in soils.sediments and sludge[J].Trends in AnalyticalChemistry,2003,22(6): 340-350
[5]俞道进,曾振灵,陈杖榴.四环素类抗生素残留对水生态环境影响的研究进展[J].中国兽医学报,2004,9(5)：515-517
[6]Heilig S, Lee P, Breslow L. Curtailing antibiotic use in agriculture [J]. Western Journal of Medicine, 2002.176:9-11
[7]Tolls J. Sorption of veterinary pharmaceuticals in soils:Areview[J]. Environmental Science and Technology,2001,35(17):3397-3406
[8]Halling-Sφrensen B, Nors Nielsen S, Lanzky P F, Ingerslev F,Holten Lutzhφft H C, Jφrgensen S E. Occurrence, fate and effects of pharmaceutical substances in the environment a review [J]. Chemosphere, 1998,36(2):357-393
[9]WoHenberger L, Hailing-Sφrensen B, Kusk K O. Acute and chronic toxicity of veterinary antibiotics to Daphnia magna[J]. Chemosphere,2000,40:723-730
[10]Hirsch R, Terlles T, Haberer K. Occurrence of antibiotics in the aquatics environment[J]. Science of the Total Environment,1999,36:3573-3593
[11]Animal Health Institute.1997. Market research report[R].Alexandria VA:U.S. Animal Health Product Industry,59
[12]Benbrook C M. Antibiotic drug use in U.S. aquaculture[OL].Institute for Agriculture and Trade Policy Report.2002-02. http:www.iatp.org/library/antibiotics
[13]Boxall A B A, Kolpin D W, Halling-Sorensen B, Tolls J. Are veterinary medicines causing environmental risks?[J]. Environmental Science and Technology,2003.37:286A-294 A
[14]梁红杏,张名涛.饲用抗生素在绿色畜牧业中的应用前景[J].畜牧业,2002,12：50-52
[15]Rooklidge, S.J.Environmental antimicrobial contamination from ter-raccumulation and diffuse pollution pathways[J] Science of the Total Environment,2004,325:1-13
[16]EMEA-The European Agency for the Evaluation of Medician Products.Antibiotic resistance in the European Union associated with the therapeutic use of veterinarymedicines[M].EMEA/CVMP/342 /99-final.1999
[17]顾君华,王欣.完善养殖模式抵制滥用抗生素[J].饲料广角,2003,20：3-6
[18]候放亮.饲料添加剂应用大全[M].北京：中国农业出版社.2003.
[19]Koplin D W. Pharmaceuticals, hormones and other organic wastewater contaminates in U.S. streams,1999-2000[J].A National econaissance. Environmental Science and Technology,2002,36(6): 1202-1211
[20]曹卫东,王旭,刘传平.当前部分有机肥料中的持久性有机污染问题[J].土壤肥料,2006(2)：8-11
[21]王冉,刘铁铮,耿志明.兽药磺胺二甲嘧啶在土壤中的生态行为[J].土壤学报,2007,3(2)：307-311
[22]王冉,刘铁铮,魏瑞成.猪粪便中兽药盐霉素残留的降解动态研究[J].农业环境科学学报,2007,26(增刊)：219-223
[23]DijckPV,vande VoordeH.Sensitivity of environmental microorganism to antimicrobial agents[J]. Applied and Environmental Microbiology,1976,31:332-336.
[24]WollenbergerL,Halling-SφrensenB,KuskKO.Acute and chronic toxicity of veterinary antibiotics to Daphniamagna[J].Chemospere,2000,40:723-730.
[25]MiglioreL, BrambillaG, CasoriaP, etal. Effects of sulphadime-thoxine on barley in Laboratory terrestrialmodels[J].Agriculture Ecosystems Environment,1996,60:121-128.
[26]Rooklidge,S.J.Environmental antimicrobial contamination from ter-raccumulation and diffuse pollution pathways[J].Science of the Total Environment,2004,325:1-13.
[27]Ingerslev, R, Holten, Lutzhoft, H.C., Halling-Sφrensen, B.Humant anvendte lagemidlers vej tilmiljoet er gennem rensningsanagget[J].DanskKem,1999,80:222-225
[28]Jemba, P.K.The potential impactofveterinary and human therapeutic agents in manure and biosolids on plants grown on arable land:areview[J]. Agriculture, Ecosystems and Environment,2002,93: 267-278
[29]Kolpin D W, Furlong E T, Meyer E M, Zaugg S D, Barber LB, Buxton H T. Pharmaceuticals, hormones, and other organic wastewater contaminants in US streams,1999-2000:Anational reconnais-sance[J]. Environmental Science and Technology,2002,36(6):1202-1211
[30]Hoper H, Kues J, Nau H, Hanscher G Eintrag and Verbleib von Tierarzneimittelwirkstoffen in B6den[J]. Bodenschutz,2002,4:141-148
[31]Hamscher G, Sczesny S, Hoper H, Nau H. Determination of persistent tetracycline residues in soil fertilized with liquidmanure by high-performance liquid chromatography with electrosprayionization tandem mass spectrometry[J]. Analytical Chemistry,2002,74(7):1509-1518
[32]Sengelφv G, Agerso Y, Halling-Sφrensen B, Baloda S B, Andersen J S, Jensen L B.Bacterial antibiotic resistance levels in Danish farmland as a result of treatment with pig manure slurry [J].Environmental International,2003.28(7):587-595
[33]王丽平,顾国平,章明奎.抗生素残留对农产品安全与生态环境的影响[J].安徽农学通报,2007,13(2)：74-76
[34]Halling-Sφrensen B, Nors Nielsen S, Lanzky P F, Ingerslev F, Holten Lutzhφft H C, Jφrgensen S E. Occurrence, fate and effects of pharmaceutical substances in the environment a review[J].Chemosphere, 1998,36(2):357-393
[35]Animal Health Institute. Market research report[R].Alexandria VA:U.S. Animal Health Product Industry,1997,59
[36]Spaepen K R I, Van Leemput L J J, Wislocki P G, WerschuernC. A uniform procedure to estimate the predicted environmental concentration of the residues of veterinary medicines in soil[J].Environ mental Toxicology and Chemistry,1997.16:1977-1982
[37]Montforts M H M M, Kalf D F, Van Vlaardingen P L A,Linders J B H J. The exposure assessment for veterinarymedicinal products [J]. Science of the Total Environment,1999,225:119-133
[38]Meyer M T, Bumgarner J E, Varns J L, Thurman E M,Hostetler K A. Use of radioimmunoassay as a screen for antibiotics in confined animal feeding operations and confirmation by liquid chromatogra-phymass spectrometry[J]. Science of the Total Environment,2000,248(2-3):181-187
[39]HamscherG, SczesnyS, AbuQareA, HoperH, NauH. Sub-stances with pharmacological effects including hormonally active substances in the environment:identification of tetracyclines in soil fertilized with animal slurry[J].Dtsch Tierarztl Wochenschr,2000,107(8):332-334.
[40]Jemba,P.K.The potential impact of veterinary and humantherapeutic agents in manure and biosolids on plants grown on arable land:a review[J].Agriculture,Ecosystems and Environment,2002,93:267-278.
[41]Thiele-Bruhn,S. Pharmaceutical antibiotic compounds in soils a review[J]. Journal of Plant Nutrition and Soil Science,2003,166:145-167.
[42]Campagnolo E R, Johnson K R, Karpati A, Rubin C S, Kolpin D W, Meyer M T, Esteban J E, Currier R W, Smith K, Thu K M, McGeehin M. Antimicrobial residues in animal waste and water resources proximal to large scale swine and poultry feeding operations[J]. Science of the Total Environment,2002,299:89-95
[43]Hamscher G, Sczesny S, Hoper H, Nau H. Determination of persistent tetracycline residues in soil fertilized with liquid manure by high performance liquid chromatography with electrospray ionization tandem mass spectrometry[J]. Analytical Chemistry,2002,74(7):1509-1518
[44]Golet E M, Strehler A, Alder A C, Giger W. Determination of fluoroquinolone antibacterial agents in sewage sludge and sludge treated soil using accelerated solvent extraction followed by solid phase extraction[J]. Analytical Chemistry,2002,74:5455-5462
[45]Morales-Muoz S, Luque-Garcia J L, Luque de Castro M D. Continuous microwave assisted extraction coupled with derivatization and fluorimetric monitoring for the determination of fluoroqu-inolone antibacterial agents from soil samples[J]. Journal of Chromatography A,2004,1059(1-2):25-31
[46]Haller M Y, Muller S R, McArdell C S, Alder A C, Suter M J F. Quantification of veterinary antibiotics(sulfonamides and trimethoprim) in animal manure by liquid chromatography mass spectrometry[J]. Journal of Chromatography A,2002,952:111-120
[47]De Liguoro M, Cibin V, Capolongo F, Halling-Sφrensen B,Montesissa C. Use of oxytetracycline and tylosin in intensive calf farming:evaluation of transfer to manure and soil[J]. Chemosphere,2003,52: 203-212
[48]Aga D S, O'Connor S, Enslev S O, Payero J, Snow D, Tarkalson D. Determination of the persistence of tetracycline antibiotics and their degradates in manure-amended soil using enzyme-linked immunosorbent assay and liquid chromatography mass spectrometry[J]. Journal of Agriculture Food Chemosphere,2006,53:7165-7171
[49]Hailing-Sφrensen B. Inhibition of aerobic growth and nitrification of bacteria in sewage sludge by antibacterial agents[J].Archives of Environmental Contamination and Toxicology,2001,40:451-460
[50]Pearson M,Inglis V J F DA sensitive mi crobioassay for the detection of antibacterial agents in the-aquatic environment[J].Journal of Fish Diseases,1993.16:255-260
[51]Hirsch R,Ternes T,Haberer K,Kratz K LOccurrence of antibiotics in the aquatic environment [J].Science of the Total Environment,1999,225:109-118
[52]Ternes T A,Joss A,Siegrist H.Scrutinizing pharmaceutical and personal care products in wastewater treatment[J].Environmental Science and Technology,2004,38:392A-399A
[53]Kolpin D W, Furlong E T, Meyer M T, ThllI-E M, Zaugg S D, Barber L B, Buxton H T. Pharmaceuticals, horm ones and other waste water contaminants in US streams 1999-2000.A national [J].Environmental Science and Technology,2002.36:1202-1211
[54]Batt A L, Bruce I B, Aga D S.Evaluating the vulnerability of surface watem to antibiotic contamination from varying wastewater treatment plant discharges[J].Environmental Pollution, 2006,142(2):295-302
[55]Zuccato E,Calamari D,Natangelo M,Fanelli R.Presence of therapeutic drugs in the environment [J].The Lancet,2000,355 (9217):1789-1790
[56]Kim S D,Cho J,Kim I S,Vandefford B J,Snyder S A.Occurrence and removal of pharmac-euticals and endocrine disruptors in South Korean surface, drinking, and waste water[J].Water Research,2007,41 (5):1013-1021
[57]Capo ne D G, Weston D P,Miller V, Shoemaker C. Antibacterial residues in Illarine sediments an d invertebrates following chemotherapy in aquaculture[J].Aquaculture,1996,145:55-75
[58]Holm J V, Rugge K, Sjerg P L, Christensen T H.Occurrence and distribution of pharmaceutical organic compoundsin the groundwater downgradient of a landfill Frinsted,Denmark[J].Environmental Science and Technology,1995,36:1-6
[59]Sarmah A K, Meyer M T, Boxall A B A. A global perspective on the use, sales, exposure pathways, occurrence, fate and effects of veterinary antibiotics (VAs) in the environment[J]. Chemosphere,2006,65(5):725-759
[60]Yang W, Carlson K.Evolution of antibiotic occurrence in a fiver through pristine, urban, and agricultural landscapes[J].Water Research,2003,37:4645-4656
[61]Mellon M, Benbrook C, Benbrook K L. Hogging It. Estimates of Antimicrobial Abuse in Livestock[J].Union of Concerned Scientists Publications, Washington DC,2001:7-9
[62]Loke ML, SonjaJespersen, Vreeken R, Hailing-Sφrensen B, Tjornelund J.Determ ination of oxytetracycline and its degradation products by high perform ance liquid chroma tographytandem mass spectrometry in manure-containing anaerobic test system[J].Journal of Chromatography B,2003,783 (1):11-23
[63]Hailing-Sφrensen B, Lykkeberg A, Ingerslev F'Blackwell TjCrnelund J.Characterisation of the abiotic degradation pathways of Oxytetracyclines in soil interstitial water using LC-MS-MS[J]. Chemosphere,2003,50(10):1331-1342
[64]Thiele-Brn hn S, Peters D, Hailing-Sφrensen B, Leinwebe P.Photodegradate on and ageing of antibiotic pharmaceutical on soil.Lyon:Presentation of project results on Envirpharma Europe an conference[J].2003:14-16
[64]W arman PR.The effect of Amprolium and Aureomycin antibiotic on the nitrification of poultry manure amended soil.Joumal of the soil Science Society of America[J].1980,44(6):1333-1334
[65]Pursell L, Samuelsen OB, Smith P.Reduction in the in-vitro activity of flumequine against Aeromonas salmonicida in the presence of the concentration of Mg and Ca ions in found in sea water.Aquaculture[J].1995,135(4):245-255
[66]Backhaus Grimme LH.The toxicity of antibiotic agents to the lumi nescent bacterium Vibrio fischeri[J].Chemosphere,1999,38(14):3291-3301
[67]Hamscher QSczesny S,Hoper H, Nau H.Determ ination of persistent tetracycline residues in soil fertilized with liquid manure by high-perform ance liquid chromatography with electrospray ionization tandem mass spectrometry[J]. Analytical Chemistry,2002,74(7):1509-1518
[68]Boleas S, Alonso C, Pro J, Fernandez A, Carbonell G, TarazonaJ V.2005. Toxicity of the antimicrobial oxytetracycline to soil organisms in a multi-species-soil system and influence of manure coaddition[J]. Journal of Hazardous Materials,2005,122:233-241
[69]Kong W D, Zhu Y G, Fu B J, Marschner P, He J Z. The veterinary antibiotic oxytetracycline and Cu influence functional diversity of the soil microbial community[J]. Environmental Pollution,2006,143: 129-137
[70]Batchelder AR.Chlortetracycline and oxytetracycljne effects on plant growth and development in liquid cultures[J].Journal of Environment Quality,1981,10(4):515-518
[71]Batchelder AR.Chlonetracycljne and Oxytetracycline effects on plant growth and development in soil systems[J].Joumal of Environment Quality,1982,11(4):675-678
[72]Migliore L,Civitareale C,Brambilla G Cozzolino S,Casoria Gaudio L.Effects of sulphadimethoxine on cosmopolitan weeds maranthus retroflexus L. Plantago major L and Rumex acetoseUa L[J]. Agriculture,Ecosystems & Environment,1997,65(2):163-68
[73]Lanzky PF, Hailing-SrφnsenB.he toxic effect of the antibiotic metronidazole on aquatic organ-isms[J].Chemosphere,1997,5(11):2553-2561
[74]Patten D K, Wolf D C, Kunkle W E, Douglass L W. Effects of antibiotics in beef cattle feces on notrogen and carbon mineralization in soil and on plant growth and conposition[J].Journal of Environmental Qualty,1980:167-172
[75]Migliore L, Civitareale C, Cozzolino S, Fiori M. Phytotoxicity to and uptake of enrofloxacin in crop plants[J].Chemosphere,2003,52:1233-1244
[76]Batchelder A R. Chlortetracycline and oxytetracycline effects on plant growth and development in soil systems[J]. Journal of Environmental Qualty,1982,11:675-678
[77]Jjemba P K. The effect of chloroquine, quinacrine, and metronidazole on both soybean plants and soil microbiota[J].Chemosphere,2002,46:1019-1025
[78]Migliore L, Civitareale C, Cozzolino S, Fiori M. Phytotoxicity to and uptake of enrofloxacin in crop plants [J].Chemosphere,2003,52:1233-1244
[79]Boxall A B A, Kolpin D W, Halling-Sφrensen B, Tolls J. Are veterinary medicines causing environmental risks?[J].Environmental Science and Technology,2003,7:286A-294A
[80]Migliore L, Civitareale C, Cozzolino S, Casoria P, Brambilla, G, Gaudio L. Laboratory models to evaluate phytotoxicity of sulphadimethoxine on terrestrial plants[J].Chemosphere,1998,7(14-15): 2957-2961
[81]Bradel B G, Preil W, Jeske H.2000. Remission of the freebranching pattern of Euphorbia pulcherrima by tetracyclinetreatment[J]. Journal of Phytopathology,148:587-590
[82]Wollenberger L,Hailing-Sφrensen B,Kusk KO.Acute and chronic toxicity of veterinary antibiotics to Daphnia magna[J].Chemosepere,2000,40;23-730.
[83]俞道进,曾振灵,陈杖榴.四环素类抗生素残留对水生态环境影响的研究进展[J].中国兽医学报,2004,9(5)：515-517
[84]Hoekstra JA.van Ewijk PH.Altematives for the No-bserved-effect level[J]. Environmental Toxicol-ogy and Chemistry,1993,12(1):187-194
[85]Baguer AJ,Jensen J,Krogh PH.Effects of the antibiotics oxytetracycline and tylosin on soil fauna[J]. Chemosphere,2000,40(7):751-757
[86]Hamscher G, Sczesny S, Hoper H, Nau H.Determ ination of persistent tetracycline residues in soil fertilized with liquid manure by high performance liquid chromatography with electrospray ionization tandem mass spectrometry[J]. Analytical Chemistry,2002,74(7):1509-1518
[87]Loke ML, Ingerslev Hailing-Sφrensen B, TjCrnelund J Stability of Tylosin A in manure containing test systems determined by high performance liquid chromatography[J].Chemosphere,2000,40 (7):759-765
[88]Boleas S, Alonso C, Pro J, Fernandez A, Carbonell G, Tarazona J V.2005. Toxicity of the antimicrobial oxytetracycline to soil organisms in a multi-species-soil system(MS) and influence ofmanure coaddition [J]. Journal of Hazardous Materials,122:233-241
[89]Kong W D, Zhu Y G, Fu B J, Marschner P, He J Z. The veterinary antibiotic oxytetracycline and Cu influence functional diversity of the soil microbial community [J].Environmental Pollution,2006,43: 129-137
[90]Westergaard K, Muller A K, Bloem J, Sφrensen S J. Effects of tylosin as a disturbance on the soil microbial community[J].Soil Biology and Biochemistry,2001,2(15):2061-2071
[91]Thiele SPharmaceutical antibiotic compound in soils a review[J]. Journal of Plant Nutrition and Soil Science,2003,66:145-167
[92]Bailey V L, Smith J L, Jr Bolton H.2002. Fungal-to-bacterial ratios in soils investigated for enhanced C sequestration [J]. Soil Biol Biochem,34(7):997-1007
[93]Bailey V M, Smith J L, Bolton H. Novel antibiotics as inhibitors for the selective respiratory inhibition method of measuring fungal:bacterial ratios in soil[J]. Biol Fertil Soils,2003,8:154-160
[94]王冰,孙成,胡冠九.环境中抗生素残留潜在风险及其研究进展[J].环境科学与技术,2007,3(3)：108-111
[95]Diaz-Cruz,M.S.,LopezdeAlda,M.J.,Barcelo,D.Environ-mental behavior and analysis of veterinary and human drugs in soils,sediments and sludge[J].Trends in Analytical Chemistry,2003,22(6):340-350.
[96]Ying GG, Kookana RS, Ru YJ.Occurrence and fate of horm one steroids in the environment[J]. ironment International,2002,28(6):545-551
[97]Rabolle M, Spliid NH. Sorption and mobility of metronidazole, olaquindox, oxytetracycline and tylosin in soil[J]. Chemosphere,2000,40(7):715-722
[98]Lunestad B Goksoyr J.eduction in the antibacterial effect of Oxytetracycline in sea water by complex formation with magnesium and alcium[J]. Diseases of Aquatic Organisms,1990,9:67-72
[99]Boxall ABA,Blackwell Cavallo R.Kay E The sorption and transport of a sulphonamide antibiotic in soil systems[J].Toxicology Letters,2002,131(1-2):19-28
[100]Bakal RS,Stoskopf M K.In vitro studies of the fate of sulfadimethoxine and ormetoprim in the aquatic environment[J].Aquaculture,2001,195(1-2):95-102
[101]Capone DG Weston DP, Miller V' Shoemaker C.Antibacterial residues in marine sediments and invertebrates following chemotherapy in aquaculture.Aquaculture,1996,145(14):55-75
[102]Aboul-Kassim. Simoneit BR The handbook of environmental chemistry Vol.5 Part E, Pollutant solid phase i nteractions:M echanism, chemistry and modeling[J].BerlinHeidelberg:Springer Verlag, 2001,141-159
[103]卞永荣,蒋新,王代长.五氯酚在酸性土壤表面的吸附-解吸特征研究[J].土壤,2004,36(2)：181-186
[104]梁重山,党志,刘丛强.菲在土壤／沉积物上的吸附-解吸过程及滞后现象的研究[J].土壤学报,2004,41(3)：329-335
[105]罗雪梅,杨志峰,何孟常.土壤／沉积物中天然有机质对疏水性有机污染物的吸附作用[J].土壤,2005,37(1)：25-31
[106]Jia LQ, Ou ZQ,Ouyang ZY.Ecological behavior of linear alkylbenzene sulfonate(LAS) in soil plant system[J].Pedosphere,2005,15(2):216-224
[107]Jacobsen P, Berglind L. Persistence of oxytetracycline in sediments from fish farms[J]. Aquaculture,1988,70(4):365-370
[108]Richardson ML,Bowron JM.The fate of pharmaceutica chemicals in the aquatic environment[J]. Pharmacy and Pharmacology,1985,37(l):1-12
[109]Ingerslev F.Hailing-Sφerensen B.Biodegradabilit properties of sulfonamides in activated sludge [J].Environment Toxicology and Chemistry,2000,19(10):2467-2473
[110]Campos JL,Garrido JM,M fndez R,Lema JM.Effect of two broad spectrum antibiotics on activity and stability of continuous nitrifying system.Applied Biochemistry and Bjotechnology PartA[J],Enzyme Engineering and Biotechnology,2001,95(1):1-10
[111]W arman PR,Thom as RL.Chlortetracycline in soil amended with poultry manure[J].Canadian Jo-umal of Soil Science,1981,61(1):161-163
[112]曹卫东,王旭,刘传平.当前部分有机肥料中的持久性有机污染问题[J].土壤肥料,2006(2)：8-11
[113]周启星,罗义,王美娥.抗生素的环境残留生态毒性及抗性基因污染[J].生态毒理学报,2007,9(3)：243-251
[1]Benbrook C M. Antibiotic Drug Use in U.S. Aquaculture.Institute for Agriculture and Trade Policy Report, February 2002. www.iatp.org/library/antibiotics.
[2]Halling-Sφrensen, B., Nors Nielsen, S., Lanzky, P. F., Ingerslev, F., Holten Lutzheft, H. C., and Jφrgensen, S. E. Occurrence, fate and effects of pharmaceutical substances in the Environment--A review. Chemosphere [J].1998,36,357-393.
[3]Hartmann A, Alder A C, Koller T, et al. Identification of fluoroquinolone antibiotics as the main source of human genotoxicity in native hospital wastewater[J]. Environmental Toxicology and Chemistry,1998,17:377-382
[4]B.Halling-Sφrensen, Algal toxicity of antibacterial agents used in intensive farming[J]. Chemosphere, 2000,40,731-739
[5]王冉,刘铁铮,王恬.抗生素在环境中的转归及其生态毒性[J].生态学报,2006,1,(1)：265-270
[6]Bertschinger, H.U.,Die chemotherapeutiche Wirksamkeit von Olaquindox bei Ferkeln mit experimenteller Colidiarrhoe und Colinenterotoxamie. Schweitz.Arch[J].Tierheilkd.1976,118,397-407.
[7]Holmgren, N., Profylaktiska effekter av zinkoxid eller olaquindox mot awa njningsdiarre hos svin(Prophylactic effects of zinc oxide or olaquindox against weaning diarrhoea in pigs)[J]. Svensk Veterinartidn,1994,46,217-222 (in Swedish, with English abstract).
[8]Holmgren, N., Lundeheim, M., Djurhalsomassiga behovet av fodermedelsantibiotika i sma grisproducerandebesa'ttningar (The medicated feed requirement of piglet-producing herds)[J]. Svensk Veterinartidn,1994.46,57-65 (in Swedish, with English abstract).
[9]Fellstrom, C., Pettersson, B., Johansson, K.E., Lundeheim, N., Gunnarsson, A., Prevalence of Serpulina speciesin relation to diarrhoea and feed medication in pig rearing herds in Sweden[J]. American Journal of Veteriary Research.1996,57,807-811.
[10]李俊锁,钱传范.残留分析中的检测限和测定限[J].农药译丛,1997,19(1)：56-60
[11]Tunney, H., Molloy, S., Variations between farms in N,P, K, Mg and dry matter composition of cattle, pig and poultry manures[J]. Ireland Journal of Agricultural Research.1975,14,71-79.
[12]Japenga, J., Harmsen, K., Determination of mass balance and ionic balances in animal manure[J]. Netherlands Journal of Agricultural Science,1990,38,353-367.
[13]Choudhary, M., Bailey, L.D., Grant, C.A., Review of the use of swine manure in crop production: effects on yield and composition and on soil and water quality[J]. Waste Management & Research.1996, 14,581-595.
[14]Da la Torre, A.I., Jim_enez, J.A., Carballo, M., Fernandez, J.R.,Mu～noz, M.J., Ecotoxicological evaluation of pig slurry[J]. Chemosphere,2000,41,1629-1635.
[15]G F Bories. High-performance liquid chromatography determination of Olaquindox in feeds[J]. Journal of Chromatography,1979,172:505-508.
[16]杨文军,张丽英,李德发.反相高效液相色谱法测定饲料中喹乙醇的含量[J].中国兽药杂志,2003,37(2)：20-23
[17]艾晓辉,刘长征,文华.鱼组织中喹乙醇残留量高效液相色谱检测方法研究[J].湖北农学院学报,2003,8(4)：266-270
[1]Kolpin D W, Furlong E T, et al. Pharmaceuticals, hormones, and other organic wastewater contaminantsin U.S.streams,1999-2000:anationalreconnaissance[J]. Environmental science & technol-ogy,2002,36,1202-1211
[2]Halling-Sφrensen,B.,Nors Nielsen,S., Lanzky, P. R, et al. Occurrence, fate and effects of pharma-ceutical substances in the Environment--A review. Chemosphere[J].1998,36,357-393.
[3]Hartmann A, Alder A C, Koller T, et al. Identification of fluoroquinolone antibiotics as the main source of human genotoxicity in native hospital wastewater[J]. Environmental Toxicology and Chemistry,1998,17,377-382
[4]B.Halling-Sφrensen. Algal toxicity of antibacterial agents used in intensive farming[J]. Chemosphere, 2000,40,731-739
[5]王冉,刘铁铮,王恬.抗生素在环境中的转归及其生态毒性[J].生态学报,2006,1,(1)：265-270
[6]Mette Rabulle, Niels Henrik Spliid. Sorption and mobility of metronidazole, olaquindox, oxytetracycline and tylosin in soil[J]. Chemosphere,2000,40,715-722
[7]Flemming Ingerslev, Bent Halling-Sφrensen. Biodegradability of Metronidazole, Olaquindox, and Tylosin and Formation of Tylosin Degradation Products in Aerobic SoilIManure Slurries[J]. Ecotoxic-ology and Environmental Safety,2001,48,311-320
[8]Allare S.E, Castillo J D, and Juneau V, Sorption kinetics of chlortetracycline and tylosin on sandy loam and heavy clay soils[J]. Journal of Environmental Quality,2006,135,969-972.
[9]Gu C, Karthikeyan K G,Interaction of tetracycline with aluminum and iron hydrous oxides[J]. Environmental science & technology,2005,39,2660-2667.
[10]Pouliquen H, Bris H L, Sorption of oxolinic acid and oxytetracycline to marine sediments[J]. Chemosphere,1996,33,801-815.
[11]Sithole B B, Guy R D, Models for tetracycline in aquatic environments. I. Interaction with bentonite clay sytems [J]. Water, Air, Soil Pollution.1987,32,303-314.
[12]OECD Adsorption/desorption using a batch equilibrium method. OECD guidelines for testing of chemicals, test guideline 106. Organization for Economic Cooperation and Development:Paris, France, 2000.
[13]Van Dijk J, Keukens H J. In Residues of Veterinary Drugs in Food:Proceedings of the Euroresidue IV Conference; Van Ginkel,L.A.,Ruiter,A.,Eds.Veldhoven,The Netherlands,2000.178-182
[14]Rabφlle M, Spliid N H, Sorption and mobility of metronidazole, olaquindox, oxytetracycline, and tylosin in soil[J], Chemosphere,2000,40,715-722.
[15]Marie-Louise Loke, Jette Tjφrnelund, Bent Halling-Sφrensen. Determination of the distribution coefficient (logKd) of oxytetracycline, tylosin A, olaquindox and metronidazole in manure[J]. Chemosphere,2002,48,351-361
[1]Halling-Sorensen, B., Nors Nielsen, S., Lanzky, P. F., Ingerslev, F., Holten Lutzhφft, H. C., and Jφrgensen, S. E. Occurrence, fate and effects of pharmaceutical substances in the Environment--A review. Chemosphere [J].1998,36,357-393.
[2]Hartmann A, Alder A C, Koller T, et al. Identification of fluoroquinolone antibiotics as the main source of human genotoxicity in native hospital wastewater[J].Environmental Toxicology and Chemistry, 1998,17:377-382
[3]B.Halling-Sφrensen, Algal toxicity of antibacterial agents used in intensive farming[J].Chemosphere, 2000,40,731-739
[4]王冉,刘铁铮,王恬.抗生素在环境中的转归及其生态毒性[J].生态学报,2006,1,(1)：265-270
[5]郭庆,任泽林,曾虹.喹乙醇在水产养殖中的应用[J].中国饲料,1997,(5)：27-28
[6]Zeng H. Nutrient requirements of fish [M]. Beijing:China Agricultural Press,1993:70-71.
[7]Cheng J R. Water chemistry[M]. Beijing:China Agricultural Press,1998:260-261.
[8]于慧娟,毕士川,黄冬梅高效液相色谱法测定水产品中喹乙醇的残留量[J].分析科学学报,2004,6：281-283
[9]艾晓辉,陈正望,张春光,喹乙醇在鲤体内的药物代谢动力学及组织浓度[J].水生生物学报,2003,27,(3)：273-276
[10]杨先乐,胡鲲,邱军强,喹乙醇在鱼体内蓄积及其对鱼类的影响[J].水生生物学报,2005,29(1)：13-18