多西环素在鸡粪中吸附-解吸附行为及影响因素研究
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摘要
通过批处理平衡试验,研究了养殖业中广泛使用的典型兽药抗生素多西环素在鸡排泄物中的吸附和解吸附行为及机制,以及pH、离子类型与强度等因素对解吸附的影响。结果表明:多西环素在鸡粪中吸附过程呈现L型吸附,等温线为非线性,吸附和解吸附过程可以用Freundlich方程进行拟合;多西环素在鸡粪中解吸附能力与溶液pH和离子强度相关,在pH<6时,pH越小,鸡粪中多西环素解吸附能力越强,且pH 2和pH 4间解吸附量差异显著(P<0.05),pH≥6时,解吸附能力没有明显变化;在0.01 mol·L~(-1)离子强度下,二价Ca~(2+)离子对鸡粪中多西环素解吸附能力比一价Na~+和K~+有增强趋势,但差异不显著,而在0.1 mol·L~(-1)离子强度下,NO_3~-和Ca~(2+)离子对鸡粪中多西环素解吸附能力与其他离子比较差异极显著(P<0.01)。研究表明:酸雨和化学肥料的施用能促进动物粪便中多西环素的解吸附,对水体和土壤环境存在迁移风险,但在对粪肥处理时,一定的酸性和离子环境有助于残留抗生素的析出与降解。
The adsorption and desorption behaviors of the typical veterinary drug doxycycline in chicken manure under different conditions,i.e., solution pH(2~10)and ion solution(Ca~(2+), Na~+, K~+, Cl~-, and NO_3~-), were studied through batch equilibrium test. The results showed that the doxycycline adsorption process presented a nonlinear shape, and the Freundlich equation fitted the adsorption and desorption behaviors in chicken manure well. The desorption capacity of doxycycline in chicken manure was related to the solution's pH and ionic strength. It was enhanced as the solution pH decreased below pH<6. Significant difference was found for solution pH values of 2 and 4(P<0.05), whereas no significant difference was detected at pH≥6. For the ionic concentration of 0.01 mol·L~(-1), the desorption rate of Ca~(2+)was much higher than those of Na~+and K~+, but the difference was not significant. For the ionic concentration of 0.1 mol·L~(-1), the desorption capacities of NO_3~- and Ca~(2+)were significantly different(P<0.01)in the chicken manure. This research showed that acid rain and chemical fertilizer application in soil could increase the doxycycline desorption capacity in animal manure, leading to the risk of migration to terrestrial and aquatic environments. However, it will be helpful for the precipitation and degradation of residual antibiotics under acidic and ionic environment when dealing with manure.
The adsorption and desorption behaviors of the typical veterinary drug doxycycline in chicken manure under different conditions,i.e., solution pH(2~10)and ion solution(Ca~(2+), Na~+, K~+, Cl~-, and NO_3~-), were studied through batch equilibrium test. The results showed that the doxycycline adsorption process presented a nonlinear shape, and the Freundlich equation fitted the adsorption and desorption behaviors in chicken manure well. The desorption capacity of doxycycline in chicken manure was related to the solution's pH and ionic strength. It was enhanced as the solution pH decreased below pH<6. Significant difference was found for solution pH values of 2 and 4(P<0.05), whereas no significant difference was detected at pH≥6. For the ionic concentration of 0.01 mol·L~(-1), the desorption rate of Ca~(2+)was much higher than those of Na~+and K~+, but the difference was not significant. For the ionic concentration of 0.1 mol·L~(-1), the desorption capacities of NO_3~- and Ca~(2+)were significantly different(P<0.01)in the chicken manure. This research showed that acid rain and chemical fertilizer application in soil could increase the doxycycline desorption capacity in animal manure, leading to the risk of migration to terrestrial and aquatic environments. However, it will be helpful for the precipitation and degradation of residual antibiotics under acidic and ionic environment when dealing with manure.
引文
[1] Zhang Q Q, Ying G G, Pan C G, et al. Comprehensive evaluation of antibiotics emission and fate in the river basins of China:Source analysis,multimedia modeling, and linkage to bacterial resistance[J]. Environmental Science&Technology, 2015, 49(11):6772-6782.
[2] Sarmah A K, Meyer M T, Boxall A B. 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.
[3] Daghrir R, Drogui P. Tetracycline antibiotics in the environment:A review[J]. Environmental Chemistry Letters, 2013, 11(3):209-227.
[4]王瑞,魏源送.畜禽粪便中残留四环素类抗生素和重金属的污染特征及其控制[J].农业环境科学学报, 2013, 32(9):1705-1719.WANG Rui, WEI Yuan-song. Pollution and control of tetracyclines and heavy metals residues in animal manure[J]. Journal of Agro-Environment Science, 2013, 32(9):1705-1719.
[5] Wei R, Ge F, Huang S, et al. Occurrence of veterinary antibiotics in animal wastewater and surface water around farms in Jiangsu Province,China[J]. Chemosphere, 2011, 82(10):1408-1414.
[6] Zhao L, Dong Y H, Wang H. Residues of veterinary antibiotics in manures from feedlot livestock in eight provinces of China[J]. Science of the Total Environment, 2010, 408(5):1069-1075.
[7]孟丽华,史艳伟,时兵,等.四环素类抗生素残留的检测方法及其对渔业环境的影响研究进展[J].中国渔业质量与标准, 2017, 7(1):50-55.MENG Li-hua, SHI Yan-wei, SHI Bing, et al. Research progress of the detection method of tetracyclines antibiotics residues and its influence on fishery environment[J]. Chinese Fishery Quality and Standards,2017, 7(1):50-55.
[8] Hamscher G, Sczesny S, Heinrich H?per A, et al. 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.
[9]李红娜,阿旺次仁,李斌绪,等.兽用抗生素研究的文献计量学分析[J].农业环境科学学报, 2017, 36(11):2297-2306.LI Hong-na, Awangciren, LI Bin-xu, et al. A bibliometric assessment of research into antibiotics in poultry and livestock breeding[J]. Journal of Agro-Environment Science, 2017, 36(11):2297-2306.
[10]王军霞,徐菲,刘瑞民,等.我国畜禽养殖总量空间热点分析及主要污染物核算[J].农业环境科学学报, 2017, 36(7):1316-1322.WANG Jun-xia, XU Fei, LIU Rui-min, et al. Hotspot analysis and estimation of the main pollutants from livestock in China[J]. Journal of Agro-Environment Science, 2017, 36(7):1316-1322.
[11]于子旋.畜禽粪便堆肥理化特征及腐熟度评价研究[D].合肥:安徽农业大学, 2016.YU Zi-xuan. Characterization and identification of maturity of manure composting[D]. Hefei:Anhui Agricultural University, 2016.
[12]张北赢,陈天林,王兵.长期施用化肥对土壤质量的影响[J].中国农学通报, 2010, 26(11):182-187.ZHANG Bei-ying, CHEN Tian-lin, WANG Bing. Effects of long-term uses of chemical fertilizers on soil quality[J]. Chinese Agricultural Science Bulletin, 2010, 26(11):182-187.
[13]刘丹.混合畜禽粪便厌氧发酵特性试验研究[D].哈尔滨:东北农业大学, 2008.LIU Dan. The experimental research on anaerobic fermentation characteristics of mixed livestock manure[D]. Harbin:Northeast Agricultural University, 2008.
[14] Peng P C, Wang Y, Liu L Y, et al. The excretion and environmental effects of amoxicillin, ciprofloxacin, and doxycycline residues in layer chicken manure[J]. Poultry Science, 2016, 95(5):1033-1041.
[15]提清清,高增文,季慧慧,等.抗生素在土壤中的吸附行为研究进展[J].土壤, 2017, 49(3):437-445.TI Qing-qing, GAO Zeng-wen, JI Hui-hui, et al. Adsorption of antibiotics in soils:A review[J]. Soils, 2017, 49(3):437-445.
[16]李鑫,王东升,张婷.土霉素和金霉素在土壤中的吸附-解吸行为[J].地球环境学报, 2015, 6(5):317-322.LI Xin, WANG Dong-sheng, ZHANG Ting. Adsorption-desorption behavior of oxytetracycline(OTC)and chlortetracycline(CTC)[J]. Journal of Earth Environment, 2015, 6(5):317-322.
[17]靳红梅,许彩云,黄红英,等.猪粪中温厌氧消化中磺胺类抗生素的降解和吸附特征[J].农业环境科学学报, 2017, 36(9):1884-1892.JIN Hong-mei, XU Cai-yun, HUANG Hong-ying, et al. The degradation and adsorption of sulfonamides in mesophilic anaerobic digestion of swine manure[J]. Journal of Agro-Environment Science, 2017, 36(9):1884-1892.
[18] Gu C, Karthikeyan K G, Sibley S D, et al. Complexation of the antibiotic tetracycline with humic acid[J]. Chemosphere, 2007, 66(8):1494-1501.
[19] Rab?lle M, Spliid N H, S. E, et al. Sorption and mobility of metronidazole, olaquindox, oxytetracycline and tylosin in soil[J]. Chemosphere,2000, 40(7):715-722.
[20] Mackay A A, Canterbury B. Oxytetracycline sorption to organic matter by metal-bridging[J]. Journal of Environmental Quality, 2005, 34(6):1964-1971.
[21] And S A S, Lee L S. Sorption of three tetracyclines by several soils:Assessing the role of pH and cation exchange[J]. Environmental Science&Technology, 2005, 39(19):7452-7459.
[22] Tang X, Lou C, Wang S, et al. Effects of long-term manure applications on the occurrence of antibiotics and antibiotic resistance genes(ARGs)in paddy soils:Evidence from four field experiments in south of China[J]. Soil Biology&Biochemistry, 2015, 90:179-187.
[23]赵亚平.玉米秸秆生物质炭和硅藻土对外源金霉素的吸附与解吸[D].沈阳:沈阳农业大学, 2013.ZHAO Ya-ping. Adsorption and desorption of exogenous chlortetracycline(CTC)on corn-straw derived biochar and diatomite[D]. Shenyang:Shenyang Agricultural University, 2013.
[24] Figueroa R A, Leonard A, Mackay A A. Modeling tetracycline antibiotic sorption to clays[J]. Environmental Science&Technology, 2004, 38(2):476-483.
[25] Tongaree S, Flanagan D R, Poust R I. The interaction between oxytetracycline and divalent metal ions in aqueous and mixed solvent systems[J]. Pharmaceutical Development&Technology, 1999, 4(4):581-591.
[2] Sarmah A K, Meyer M T, Boxall A B. 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.
[3] Daghrir R, Drogui P. Tetracycline antibiotics in the environment:A review[J]. Environmental Chemistry Letters, 2013, 11(3):209-227.
[4]王瑞,魏源送.畜禽粪便中残留四环素类抗生素和重金属的污染特征及其控制[J].农业环境科学学报, 2013, 32(9):1705-1719.WANG Rui, WEI Yuan-song. Pollution and control of tetracyclines and heavy metals residues in animal manure[J]. Journal of Agro-Environment Science, 2013, 32(9):1705-1719.
[5] Wei R, Ge F, Huang S, et al. Occurrence of veterinary antibiotics in animal wastewater and surface water around farms in Jiangsu Province,China[J]. Chemosphere, 2011, 82(10):1408-1414.
[6] Zhao L, Dong Y H, Wang H. Residues of veterinary antibiotics in manures from feedlot livestock in eight provinces of China[J]. Science of the Total Environment, 2010, 408(5):1069-1075.
[7]孟丽华,史艳伟,时兵,等.四环素类抗生素残留的检测方法及其对渔业环境的影响研究进展[J].中国渔业质量与标准, 2017, 7(1):50-55.MENG Li-hua, SHI Yan-wei, SHI Bing, et al. Research progress of the detection method of tetracyclines antibiotics residues and its influence on fishery environment[J]. Chinese Fishery Quality and Standards,2017, 7(1):50-55.
[8] Hamscher G, Sczesny S, Heinrich H?per A, et al. 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.
[9]李红娜,阿旺次仁,李斌绪,等.兽用抗生素研究的文献计量学分析[J].农业环境科学学报, 2017, 36(11):2297-2306.LI Hong-na, Awangciren, LI Bin-xu, et al. A bibliometric assessment of research into antibiotics in poultry and livestock breeding[J]. Journal of Agro-Environment Science, 2017, 36(11):2297-2306.
[10]王军霞,徐菲,刘瑞民,等.我国畜禽养殖总量空间热点分析及主要污染物核算[J].农业环境科学学报, 2017, 36(7):1316-1322.WANG Jun-xia, XU Fei, LIU Rui-min, et al. Hotspot analysis and estimation of the main pollutants from livestock in China[J]. Journal of Agro-Environment Science, 2017, 36(7):1316-1322.
[11]于子旋.畜禽粪便堆肥理化特征及腐熟度评价研究[D].合肥:安徽农业大学, 2016.YU Zi-xuan. Characterization and identification of maturity of manure composting[D]. Hefei:Anhui Agricultural University, 2016.
[12]张北赢,陈天林,王兵.长期施用化肥对土壤质量的影响[J].中国农学通报, 2010, 26(11):182-187.ZHANG Bei-ying, CHEN Tian-lin, WANG Bing. Effects of long-term uses of chemical fertilizers on soil quality[J]. Chinese Agricultural Science Bulletin, 2010, 26(11):182-187.
[13]刘丹.混合畜禽粪便厌氧发酵特性试验研究[D].哈尔滨:东北农业大学, 2008.LIU Dan. The experimental research on anaerobic fermentation characteristics of mixed livestock manure[D]. Harbin:Northeast Agricultural University, 2008.
[14] Peng P C, Wang Y, Liu L Y, et al. The excretion and environmental effects of amoxicillin, ciprofloxacin, and doxycycline residues in layer chicken manure[J]. Poultry Science, 2016, 95(5):1033-1041.
[15]提清清,高增文,季慧慧,等.抗生素在土壤中的吸附行为研究进展[J].土壤, 2017, 49(3):437-445.TI Qing-qing, GAO Zeng-wen, JI Hui-hui, et al. Adsorption of antibiotics in soils:A review[J]. Soils, 2017, 49(3):437-445.
[16]李鑫,王东升,张婷.土霉素和金霉素在土壤中的吸附-解吸行为[J].地球环境学报, 2015, 6(5):317-322.LI Xin, WANG Dong-sheng, ZHANG Ting. Adsorption-desorption behavior of oxytetracycline(OTC)and chlortetracycline(CTC)[J]. Journal of Earth Environment, 2015, 6(5):317-322.
[17]靳红梅,许彩云,黄红英,等.猪粪中温厌氧消化中磺胺类抗生素的降解和吸附特征[J].农业环境科学学报, 2017, 36(9):1884-1892.JIN Hong-mei, XU Cai-yun, HUANG Hong-ying, et al. The degradation and adsorption of sulfonamides in mesophilic anaerobic digestion of swine manure[J]. Journal of Agro-Environment Science, 2017, 36(9):1884-1892.
[18] Gu C, Karthikeyan K G, Sibley S D, et al. Complexation of the antibiotic tetracycline with humic acid[J]. Chemosphere, 2007, 66(8):1494-1501.
[19] Rab?lle M, Spliid N H, S. E, et al. Sorption and mobility of metronidazole, olaquindox, oxytetracycline and tylosin in soil[J]. Chemosphere,2000, 40(7):715-722.
[20] Mackay A A, Canterbury B. Oxytetracycline sorption to organic matter by metal-bridging[J]. Journal of Environmental Quality, 2005, 34(6):1964-1971.
[21] And S A S, Lee L S. Sorption of three tetracyclines by several soils:Assessing the role of pH and cation exchange[J]. Environmental Science&Technology, 2005, 39(19):7452-7459.
[22] Tang X, Lou C, Wang S, et al. Effects of long-term manure applications on the occurrence of antibiotics and antibiotic resistance genes(ARGs)in paddy soils:Evidence from four field experiments in south of China[J]. Soil Biology&Biochemistry, 2015, 90:179-187.
[23]赵亚平.玉米秸秆生物质炭和硅藻土对外源金霉素的吸附与解吸[D].沈阳:沈阳农业大学, 2013.ZHAO Ya-ping. Adsorption and desorption of exogenous chlortetracycline(CTC)on corn-straw derived biochar and diatomite[D]. Shenyang:Shenyang Agricultural University, 2013.
[24] Figueroa R A, Leonard A, Mackay A A. Modeling tetracycline antibiotic sorption to clays[J]. Environmental Science&Technology, 2004, 38(2):476-483.
[25] Tongaree S, Flanagan D R, Poust R I. The interaction between oxytetracycline and divalent metal ions in aqueous and mixed solvent systems[J]. Pharmaceutical Development&Technology, 1999, 4(4):581-591.