畜禽粪便堆肥过程中雌激素降解特征
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摘要
为探究畜禽粪便堆肥过程中雌激素降解特征,测定了南京附近养殖场的鸡粪、猪粪、牛粪中天然雌激素雌三醇(E3)、17β-雌二醇(17β-E2)和人工合成雌激素炔雌醇(EE2)、双酚A(BPA)含量。对三种粪便进行堆肥实验,测定了堆肥0、2、4、8、16 d和32 d时四种雌激素的浓度;并以牛粪为代表,对堆体进行不翻堆、两日一翻堆和一日两翻堆处理,研究了翻堆对堆肥过程中雌激素降解的影响。结果表明,三种畜禽粪便均含有较高浓度的天然雌激素,鸡粪和牛粪还含有人工合成雌激素,而鸡粪、猪粪、牛粪中雌激素的活性当量浓度EEQ值分别为3 595.86、268.84、1 207.12μg·kg-1,存在较大的雌激素污染风险;在堆肥32 d,鸡粪、猪粪、牛粪的EEQ残留率分别为10.1%、10.6%、0,堆肥处理很大程度上降低了雌激素污染风险。当畜禽粪便中多种雌激素共存时,雌激素降解受初始浓度影响显著,浓度高者具有较大的降解速率。雌激素降解速率随堆体内微生物活动发生改变,堆肥中期微生物活动最为活跃,雌激素降解速率高于堆肥前期和后期。对牛粪堆肥进行翻堆处理,增加了堆体内氧气含量,雌激素降解明显加快,翻堆有利于提高堆肥效果。而两日一翻和一日两翻堆肥中雌激素降解无明显差异,增加翻堆次数并不能显著提高堆肥效果。
The aim of this work was to investigate the characteristics of estrogen degradation in livestock manures during composting. Natural estrogens containingestriol(E3)and 17β-estradiol(17β-E2), were detected in chicken, pig, and cow manures from farms in Nanjing.The synthetic estrogen, containing ethinyloestradiol(EE2)and bisphenol A(BPA), were also detected. Experimental composting of three livestock manures was conducted, and the concentrations of four estrogens were detected at 0, 2, 4, 8, 16 days, and 32 days. Cow manure,as a representative of all manures, was composted under different turning frequencies(i.e., never turned, turned once every two days, and turned twice every day)to study the impact of turning frequency on estrogen degradation. The results showed a high concentration of native estrogens detected in all three livestock manures. Chicken and cow manures contained synthetic estrogen. The EEQ values of estrogen in chicken, pig, and cow manures were 3 595.86, 268.84 μg·kg-1, and 1 207.12 μg·kg-1, respectively. A high contamination risk existed in all three livestock manures. The residual rates of EEQ in chicken, pig, and cow manures were 10.1%, 10.6%, and 0 after 32 d of composting,which showed that composting could significantly reduce the risk of estrogen contamination. The initial concentration of estrogen had a significant impact on their degradation when various estrogens were detected in livestock manures. The estrogen with the highest concentration degraded faster than other estrogens. Furthermore, estrogen degradation changed with microbial activity in the manure piles. Microbial activity was most active during the mid-stage of composting, and the degradation rate of estrogens was higher during this period than during the early and later stages. Turning the cow manure pile increased its oxygen content, which significantly accelerated estrogen degradation.Thus, turning the manure pile during composting was effective. However, there was little difference in rate of estrogen degradation between turning once every two days and turning twice per day, and the increase in turning frequency did not significantly influence manure composting.
The aim of this work was to investigate the characteristics of estrogen degradation in livestock manures during composting. Natural estrogens containingestriol(E3)and 17β-estradiol(17β-E2), were detected in chicken, pig, and cow manures from farms in Nanjing.The synthetic estrogen, containing ethinyloestradiol(EE2)and bisphenol A(BPA), were also detected. Experimental composting of three livestock manures was conducted, and the concentrations of four estrogens were detected at 0, 2, 4, 8, 16 days, and 32 days. Cow manure,as a representative of all manures, was composted under different turning frequencies(i.e., never turned, turned once every two days, and turned twice every day)to study the impact of turning frequency on estrogen degradation. The results showed a high concentration of native estrogens detected in all three livestock manures. Chicken and cow manures contained synthetic estrogen. The EEQ values of estrogen in chicken, pig, and cow manures were 3 595.86, 268.84 μg·kg-1, and 1 207.12 μg·kg-1, respectively. A high contamination risk existed in all three livestock manures. The residual rates of EEQ in chicken, pig, and cow manures were 10.1%, 10.6%, and 0 after 32 d of composting,which showed that composting could significantly reduce the risk of estrogen contamination. The initial concentration of estrogen had a significant impact on their degradation when various estrogens were detected in livestock manures. The estrogen with the highest concentration degraded faster than other estrogens. Furthermore, estrogen degradation changed with microbial activity in the manure piles. Microbial activity was most active during the mid-stage of composting, and the degradation rate of estrogens was higher during this period than during the early and later stages. Turning the cow manure pile increased its oxygen content, which significantly accelerated estrogen degradation.Thus, turning the manure pile during composting was effective. However, there was little difference in rate of estrogen degradation between turning once every two days and turning twice per day, and the increase in turning frequency did not significantly influence manure composting.
引文
[1] Tapiero H, Ba G N, Tew K D. Estrogens and environmental estrogens[J]. Biomedicine&Pharmacotherapy, 2002, 56(1):36–44.
[2] Ying G G, Kookana R S, Ru Y J. Occurrence and fate of hormone steroids in the environment[J]. Environment International, 2002, 28(6):545-551.
[3]刘敏,岳波,尹平河,等.畜禽粪便改良土壤中E1和E2自然降解的影响因素[J].环境科学研究, 2011, 24(10):1166–1171.LIU Min, YUE Bo, YIN Ping-he, et al. Factors influencing the natural degradation of E1(Estrone)and E2(17β-Estradiol)in soils amended by animal manure[J]. Research of Environmental Sciences, 2011, 24(10):1166–1171.
[4] Pan B, Lin D, Mashayekhi H, et al. Adsorption and hysteresis of bisphenol A and 17alpha-ethinyl estradiol on carbon nanomaterials[J].Environmental Science&Technology, 2008, 42(15):5480–5485.
[5] Khanal S K, Xie B, Thompson M L, et al. Fate, transport, and biodegradation of natural estrogens in the environment and engineered systems[J]. Environmental Science&Technology, 2006, 40(21):6537-6546.
[6] Zheng W, Yates S R, Bradford S A. Analysis of steroid hormones in a typical dairy waste disposal system[J]. Environmental Science&Technology, 2008, 42(2):530-535.
[7] Xu P C, Zhou X, Xu D F, et al. Contamination and risk assessment of estrogens in livestock manure:A case study in Jiangsu Province, China[J]. International Journal of Environmental Research and Public Health,2018, 15(1):125.
[8] Scherr F F, Sarmah A K, Di H J, et al. Degradation and metabolite formation of 17-estradiol-3-sulphate in New Zealand pasture soils[J]. Environment International, 2009, 35(2):291–297.
[9] Zhang H, Shi J, Liu X, et al. Occurrence of free estrogens, conjugated estrogens, and bisphenol A in fresh livestock excreta and their removal by composting in north China[J]. Environmental Science and Pollution Research, 2014, 21(16):9939–9947.
[10]袁哲军,张洪昌,胡双庆,等.上海典型畜禽场周边河流雌激素污染特征研究[J].农业环境科学学报, 2017, 36(8):1583–1589.YUAN Zhe-jun, ZHANG Hong-chang, HU Shuang-qing, et al. Study on estrogen pollution characteristics of rivers around typical livestock and poultry farms in Shanghai[J]. Journal of Agro-Environment Science, 2017, 36(8):1583-1589.
[11] Hanselman T A, Graetz D A, Wilkie A C. Manure-borne estrogens as potential environmental contaminants:A review[J]. Environmental Science&Technology, 2003, 37(24):5471–5478.
[12]雷平,刘标,尹红梅.过磷酸钙在病死猪堆肥中保氮效果研究[J].农业资源与环境学报, 2017, 34(3):266-271.LEI Ping, LIU Biao, YIN Hong-mei. Effects of calcium superphosphate additive on nitrogen conservation during dead-pig composting[J]. Journal of Agricultural Resources and Environment, 2017, 34(3):266-271.
[13] Derby N, Hakk H, Casey F X, et al. Effects of composting swine manure on nutrients and estrogens[J]. Soil Science, 2011, 176(2):91–98.
[14] Ramaswamy J, Prasher S O, Patel R M, et al. The effect of composting on the degradation of a veterinary pharmaceutical[J]. Bioresource Technology, 2010, 101(7):2294–2299.
[15] Kim K R, Owens G, Ok Y S, et al. Decline of extractable antibiotics in manure-based composts during composting[J]. Waste Management,2011, 32(1):110–116.
[16]王代懿,余洋,张丰松,等.堆肥方式和温度对牛粪堆肥过程中天然类固醇激素降解的影响[J].浙江农业学报, 2017, 29(12):2104-2108.WANG Dai-yi, YU Yang, ZHANG Feng-song, et al. Effects of composting temperature and manner on degradation of natural hormones during cattle manure composting[J]. Acta Agriculturae Zhejiangensis,2017, 29(12):2104-2108.
[17]郑溪.奶牛粪便中甾体雌素污染特征调查及在堆肥过程中的降解行为研究[D].合肥：合肥工业大学, 2013.ZHENG Xi. Occurrence of steriod estrogens in dairy feces and their fate during aerobic composting process[D]. Hefei:Hefei University of Technology, 2013.
[18]刘静娴,刘娟,孙敏霞,等.抗生素对雌二醇降解菌JX-2降解性能的影响[J].农业环境科学学报, 2016, 35(8):1488–1497.LIU Jing-xian, LIU Juan, SUN Min-xia, et al. Effects of antibiotics on the estradiol degradation by strain JX-2[J]. Journal of Agro-Environment Science, 2016, 35(8):1488-1497.
[19] Layton A C, Gregory B W, Seward J R, et al. Mineralization of steroidal hormones by biosolids in wastewater treatment systems in Tennessee USA[J]. Environmental Science&Technology, 2000, 34(18):3925-3931.
[20]曾庆玲.活性污泥法去除城市污水中雌激素E2与EE2的机理研究[D].上海：同济大学, 2007.ZENG Qing-ling. Study on mechanism of removal of estrogen E2 and EE2 from municipal wastewater by activated sludge process[D].Shanghai:Tongji University, 2007.
[21] Ying G G, Kookana R S. Degradation of five selected endocrine-disrupting chemicals in seawater and marine sediment[J]. Environmental Science&Technology, 2003, 37(7):1256–1260.
[22] Lai K M, Johnson K L, And M D S, et al. Binding of waterborne steroid estrogens to solid phases in river and estuarine systems[J]. Environmental Science&Technology, 2000, 34(18):3890–3894.
[23]付银杰,凌婉婷,董长勋,等.应用UE-SPE-HPLC/FLD法检测养殖业畜禽粪便中雌激素[J].应用生态学报, 2013, 24(11):3280–3288.FU Yin-jie, LING Wan-ting, DONG Chang-xun, et al. Estrogens determination of livestock dung based on UE-SPE-HPLC/FLD[J]. Chinese Journal of Applied Ecology, 2013, 24(11):3280–3288.
[24]张梦涛,郑溪,曹飞,等.安徽省奶牛养殖场粪便中甾体雌激素污染特征研究[J].安徽农业科学, 2015(16):263-267.ZHANG Meng-tao, ZHENG Xi, CAO Fei, et al. Pollution characteristics of steroid estrogens in feces from concentrated dairy feeding farms of Anhui Province[J]. Journal of Anhui Agricultural Sciences,2015(16):263-267.
[25] Li J Z, Fu J, Xiang X, et al. Kinetics, equilibrium, and mechanisms of sorption and desorption of 17α-ethynyl estradiol in two natural soils and their organic fractions[J]. Science of the Total Environment, 2013,452/453:404-410.
[26] Li J Z, Fu J, Zhang H L, et al. Spatial and seasonal variations of occurrences and concentrations of endocrine disrupting chemicals in unconfined and confined aquifers recharged by reclaimed water:A field study along the Chaobai River, Beijing[J]. Science of the Total Environment, 2013, 450/451:162-168.
[27]刘敏.畜禽粪便土地利用中典型内固醇雌激素的分析和降解研究[D].广州：暨南大学, 2011.LIU Min. The study on analysis and degradation of typical steroid estrogens in animal waste during land use[D]. Guangzhou:Jinan University, 2011.
[28] Kaiser J. Modelling composting as a microbial ecosystem:A simulation approach[J]. Ecological Modelling, 1996, 91(1/2/3):25-37.
[29] Liu J, Li S Y, Li X, et al. Removal of estrone, 17β-estradiol, and estriol from sewage and cow dung by immobilized Novosphingobium sp.ARI-1[J]. Environmental Technology, 2017, 39(19):2423-2433.
[30]吴飞龙,叶美锋,吴晓梅,等.添加菌糠对猪粪渣堆肥过程及氨排放的影响[J].农业环境科学学报, 2017, 36(3):598-604.WU Fei-long, YE Mei-feng, WU Xiao-mei, et al. Effects of mushroom bran addition on the process and NH3 emissions of swine feces residue composting[J]. Journal of Agro-Environment Science, 2017, 36(3):598-604.
[31]梁东丽,谷洁,高华,等.不同禽畜粪便静态高温堆肥过程中蔗糖酶活性的变化[J].农业环境科学学报, 2009, 28(7):1535-1540.LIANG Dong-li, GU Jie, GAO Hua, et al. Changes of sucrose activities and temperature in static state composting processes of different livestock and fowl excrement[J]. Journal of Agro-Environment Science, 2009, 28(7):1535-1540.
[32]张静,严静娜,郭悦宁,等．阻燃剂四溴双酚A的厌氧-好氧生物降解[J].环境化学, 2016, 35(9):1776-1784.ZHANG Jing, YAN Jing-na, GUO Yue-ning, et al. Anaerobic and aerobic biodegradation of flame retardant tetrabromobisphenol A[J].Environmental Chemistry, 2016, 35(9):1776-1784.
[33] Stanford B D, Weinberg H S. Evaluation of on-site wastewater treatment technology to remove estrogens, nonylphenols, and estrogenic activity from wastewater[J]. Environmental Science&Technology, 2010,44(8):2994-3001.
[34] Rasapoor M, Adl M, Pourazizi B. Comparative evaluation of aeration methods for municipal solid waste composting from the perspective of resource management:A practical case study in Tehran, Iran[J]. Journal of Environmental Management, 2016, 184(5):528-534.
[35]徐鹏翔,王越,杨军香,等.好氧堆肥中通风工艺与参数研究进展[J].农业环境科学学报, 2018, 37(11):2403-2408.XU Peng-xiang, WANG Yue, YANG Jun-xiang, et al. Advances in ventilation systems and parameter choices during aerobic composting[J]. Journal of Agro-Environment Science, 2018, 37(11):2403-2408.
[2] Ying G G, Kookana R S, Ru Y J. Occurrence and fate of hormone steroids in the environment[J]. Environment International, 2002, 28(6):545-551.
[3]刘敏,岳波,尹平河,等.畜禽粪便改良土壤中E1和E2自然降解的影响因素[J].环境科学研究, 2011, 24(10):1166–1171.LIU Min, YUE Bo, YIN Ping-he, et al. Factors influencing the natural degradation of E1(Estrone)and E2(17β-Estradiol)in soils amended by animal manure[J]. Research of Environmental Sciences, 2011, 24(10):1166–1171.
[4] Pan B, Lin D, Mashayekhi H, et al. Adsorption and hysteresis of bisphenol A and 17alpha-ethinyl estradiol on carbon nanomaterials[J].Environmental Science&Technology, 2008, 42(15):5480–5485.
[5] Khanal S K, Xie B, Thompson M L, et al. Fate, transport, and biodegradation of natural estrogens in the environment and engineered systems[J]. Environmental Science&Technology, 2006, 40(21):6537-6546.
[6] Zheng W, Yates S R, Bradford S A. Analysis of steroid hormones in a typical dairy waste disposal system[J]. Environmental Science&Technology, 2008, 42(2):530-535.
[7] Xu P C, Zhou X, Xu D F, et al. Contamination and risk assessment of estrogens in livestock manure:A case study in Jiangsu Province, China[J]. International Journal of Environmental Research and Public Health,2018, 15(1):125.
[8] Scherr F F, Sarmah A K, Di H J, et al. Degradation and metabolite formation of 17-estradiol-3-sulphate in New Zealand pasture soils[J]. Environment International, 2009, 35(2):291–297.
[9] Zhang H, Shi J, Liu X, et al. Occurrence of free estrogens, conjugated estrogens, and bisphenol A in fresh livestock excreta and their removal by composting in north China[J]. Environmental Science and Pollution Research, 2014, 21(16):9939–9947.
[10]袁哲军,张洪昌,胡双庆,等.上海典型畜禽场周边河流雌激素污染特征研究[J].农业环境科学学报, 2017, 36(8):1583–1589.YUAN Zhe-jun, ZHANG Hong-chang, HU Shuang-qing, et al. Study on estrogen pollution characteristics of rivers around typical livestock and poultry farms in Shanghai[J]. Journal of Agro-Environment Science, 2017, 36(8):1583-1589.
[11] Hanselman T A, Graetz D A, Wilkie A C. Manure-borne estrogens as potential environmental contaminants:A review[J]. Environmental Science&Technology, 2003, 37(24):5471–5478.
[12]雷平,刘标,尹红梅.过磷酸钙在病死猪堆肥中保氮效果研究[J].农业资源与环境学报, 2017, 34(3):266-271.LEI Ping, LIU Biao, YIN Hong-mei. Effects of calcium superphosphate additive on nitrogen conservation during dead-pig composting[J]. Journal of Agricultural Resources and Environment, 2017, 34(3):266-271.
[13] Derby N, Hakk H, Casey F X, et al. Effects of composting swine manure on nutrients and estrogens[J]. Soil Science, 2011, 176(2):91–98.
[14] Ramaswamy J, Prasher S O, Patel R M, et al. The effect of composting on the degradation of a veterinary pharmaceutical[J]. Bioresource Technology, 2010, 101(7):2294–2299.
[15] Kim K R, Owens G, Ok Y S, et al. Decline of extractable antibiotics in manure-based composts during composting[J]. Waste Management,2011, 32(1):110–116.
[16]王代懿,余洋,张丰松,等.堆肥方式和温度对牛粪堆肥过程中天然类固醇激素降解的影响[J].浙江农业学报, 2017, 29(12):2104-2108.WANG Dai-yi, YU Yang, ZHANG Feng-song, et al. Effects of composting temperature and manner on degradation of natural hormones during cattle manure composting[J]. Acta Agriculturae Zhejiangensis,2017, 29(12):2104-2108.
[17]郑溪.奶牛粪便中甾体雌素污染特征调查及在堆肥过程中的降解行为研究[D].合肥：合肥工业大学, 2013.ZHENG Xi. Occurrence of steriod estrogens in dairy feces and their fate during aerobic composting process[D]. Hefei:Hefei University of Technology, 2013.
[18]刘静娴,刘娟,孙敏霞,等.抗生素对雌二醇降解菌JX-2降解性能的影响[J].农业环境科学学报, 2016, 35(8):1488–1497.LIU Jing-xian, LIU Juan, SUN Min-xia, et al. Effects of antibiotics on the estradiol degradation by strain JX-2[J]. Journal of Agro-Environment Science, 2016, 35(8):1488-1497.
[19] Layton A C, Gregory B W, Seward J R, et al. Mineralization of steroidal hormones by biosolids in wastewater treatment systems in Tennessee USA[J]. Environmental Science&Technology, 2000, 34(18):3925-3931.
[20]曾庆玲.活性污泥法去除城市污水中雌激素E2与EE2的机理研究[D].上海：同济大学, 2007.ZENG Qing-ling. Study on mechanism of removal of estrogen E2 and EE2 from municipal wastewater by activated sludge process[D].Shanghai:Tongji University, 2007.
[21] Ying G G, Kookana R S. Degradation of five selected endocrine-disrupting chemicals in seawater and marine sediment[J]. Environmental Science&Technology, 2003, 37(7):1256–1260.
[22] Lai K M, Johnson K L, And M D S, et al. Binding of waterborne steroid estrogens to solid phases in river and estuarine systems[J]. Environmental Science&Technology, 2000, 34(18):3890–3894.
[23]付银杰,凌婉婷,董长勋,等.应用UE-SPE-HPLC/FLD法检测养殖业畜禽粪便中雌激素[J].应用生态学报, 2013, 24(11):3280–3288.FU Yin-jie, LING Wan-ting, DONG Chang-xun, et al. Estrogens determination of livestock dung based on UE-SPE-HPLC/FLD[J]. Chinese Journal of Applied Ecology, 2013, 24(11):3280–3288.
[24]张梦涛,郑溪,曹飞,等.安徽省奶牛养殖场粪便中甾体雌激素污染特征研究[J].安徽农业科学, 2015(16):263-267.ZHANG Meng-tao, ZHENG Xi, CAO Fei, et al. Pollution characteristics of steroid estrogens in feces from concentrated dairy feeding farms of Anhui Province[J]. Journal of Anhui Agricultural Sciences,2015(16):263-267.
[25] Li J Z, Fu J, Xiang X, et al. Kinetics, equilibrium, and mechanisms of sorption and desorption of 17α-ethynyl estradiol in two natural soils and their organic fractions[J]. Science of the Total Environment, 2013,452/453:404-410.
[26] Li J Z, Fu J, Zhang H L, et al. Spatial and seasonal variations of occurrences and concentrations of endocrine disrupting chemicals in unconfined and confined aquifers recharged by reclaimed water:A field study along the Chaobai River, Beijing[J]. Science of the Total Environment, 2013, 450/451:162-168.
[27]刘敏.畜禽粪便土地利用中典型内固醇雌激素的分析和降解研究[D].广州：暨南大学, 2011.LIU Min. The study on analysis and degradation of typical steroid estrogens in animal waste during land use[D]. Guangzhou:Jinan University, 2011.
[28] Kaiser J. Modelling composting as a microbial ecosystem:A simulation approach[J]. Ecological Modelling, 1996, 91(1/2/3):25-37.
[29] Liu J, Li S Y, Li X, et al. Removal of estrone, 17β-estradiol, and estriol from sewage and cow dung by immobilized Novosphingobium sp.ARI-1[J]. Environmental Technology, 2017, 39(19):2423-2433.
[30]吴飞龙,叶美锋,吴晓梅,等.添加菌糠对猪粪渣堆肥过程及氨排放的影响[J].农业环境科学学报, 2017, 36(3):598-604.WU Fei-long, YE Mei-feng, WU Xiao-mei, et al. Effects of mushroom bran addition on the process and NH3 emissions of swine feces residue composting[J]. Journal of Agro-Environment Science, 2017, 36(3):598-604.
[31]梁东丽,谷洁,高华,等.不同禽畜粪便静态高温堆肥过程中蔗糖酶活性的变化[J].农业环境科学学报, 2009, 28(7):1535-1540.LIANG Dong-li, GU Jie, GAO Hua, et al. Changes of sucrose activities and temperature in static state composting processes of different livestock and fowl excrement[J]. Journal of Agro-Environment Science, 2009, 28(7):1535-1540.
[32]张静,严静娜,郭悦宁,等．阻燃剂四溴双酚A的厌氧-好氧生物降解[J].环境化学, 2016, 35(9):1776-1784.ZHANG Jing, YAN Jing-na, GUO Yue-ning, et al. Anaerobic and aerobic biodegradation of flame retardant tetrabromobisphenol A[J].Environmental Chemistry, 2016, 35(9):1776-1784.
[33] Stanford B D, Weinberg H S. Evaluation of on-site wastewater treatment technology to remove estrogens, nonylphenols, and estrogenic activity from wastewater[J]. Environmental Science&Technology, 2010,44(8):2994-3001.
[34] Rasapoor M, Adl M, Pourazizi B. Comparative evaluation of aeration methods for municipal solid waste composting from the perspective of resource management:A practical case study in Tehran, Iran[J]. Journal of Environmental Management, 2016, 184(5):528-534.
[35]徐鹏翔,王越,杨军香,等.好氧堆肥中通风工艺与参数研究进展[J].农业环境科学学报, 2018, 37(11):2403-2408.XU Peng-xiang, WANG Yue, YANG Jun-xiang, et al. Advances in ventilation systems and parameter choices during aerobic composting[J]. Journal of Agro-Environment Science, 2018, 37(11):2403-2408.