养殖场沼液中雌激素排放特征及去除效果研究

为探究典型奶牛养殖场沼液中类固醇雌激素的排放特征，采用固相萃取-高效液相色谱串联质谱（SPE-HPLC-MS/MS）分析方法，对重庆市某奶牛养殖场厌氧池和好氧池出水中类固醇雌激素进行夏、秋、冬3季连续监测.结果表明：类固醇雌激素（含雌酮；17α-雌二醇；17β-雌二醇；雌三醇；硫酸雌酮）在厌氧池和好氧池出水中总浓度分别在347.28~2117.65ng/L和10.75~1070.00ng/L之间，其中厌氧池出水以雌酮（E1）、17α-雌二醇（17α-E2）和17β-雌二醇（17β-E2）为主，好氧池出水以E1和17β-E2为主.研究显示：好氧处理对E1、17β-E2、17α-E2的平均去除率达85.70%、56.82%、57.32%，厌氧处理可有效去除硫酸雌酮（E1-3S）.在微生物作用下，厌氧和好氧处理均存在E1、17α-E2和17β-E2的相互转化，但雌三醇（E3）的低检出率则显示体系中雌激素转化为E3的比例较低.对雌激素活性（EEQ_95th）的评估显示厌氧-好氧处理后雌激素活性平均降低70.34%，但沼液的雌激素生态环境风险仍不可忽视，需持续观察及研究.

Study of emission characteristics and removal efficiency of estrogens in biogas slurry at farm

To explore the emission characteristics of steroid estrogens in biogas slurry, the anaerobic and aerobic tank effluent samples were continuously monitored in summer, autumn, and winter by solid phase extraction-high performance liquid chromatography-tandem mass spectrometry (SPE-HPLC-MS/MS) analysis method from a typical dairy farm in Chongqing city, China. The results showed that the total amounts of five steroid estrogens (estrone; 17α-estradiol; 17β-estradiol; estriol; estrone-3-sulfate) were ranged at 347.28~2117.65ng/L and 10.75~1070.00ng/L in anaerobic and aerobic tank effluent, respectively. The anaerobic tank effluent was dominated by E1, 17α-E2, and 17β-E2, and the aerobic tank effluent was dominated by E1 and 17β-E2.The average removal efficiency of E1, 17β-E2, and 17α-E2by aerobic treatment reached 85.70%, 56.82%, and 57.32%, respectively. Moreover, E1-3S was effectively removed under anaerobic treatment. Under the effect of microorganisms, the interconversion amongE1, 17α-E2, and 17β-E2 was found both in anaerobic and aerobic treatment. However, the low detection frequency of E3 indicated that the ratio of estrogen to E3 was lower in the system. The assessment of simulated estrogen activity (EEQ_95th) was reduced by an average of 70.34% after anaerobic-aerobic treatment, but the estrogens ecological risk of biogas slurry could not be ignored and required continuous monitoring.