畜禽养殖雌激素排放特征及生物炭对典型雌激素运移控制研究

CHARACTERISTICS OF ESTROGENIC EMISSIONS FROM LIVESTOCK AND POULTRY BREEDING AND BIOCHAR CONTROL OF TYPICAL ESTROGENIC TRANSPORT

陶寰宇

11649134

硕士

环境科学与工程

史江红

2018-05-29

2018-07-09

哈尔滨工业大学

深圳

雌激素包括天然雌激素雌酮（E1）、17β-雌二醇（17β-E2）、雌三醇（E3）以及人工合成雌激素 17α-乙炔基雌二醇（EE2），双酚 A（BPA）是环境中类雌激素的典型代表物质。雌激素在 ng/L 浓度水平下可导致雄性鱼的雌性化、生殖异常和性别比例失调，因此雌激素的污染防控对水环境生态安全和人群健康至关重要。集约化养殖场是雌激素排放的主要来源之一，由于南北地域等畜禽养殖类型、畜禽生长特性和养殖方式均有不同，因此针对性的掌握各地区畜禽养殖场雌激素的排放特征并合理的控制污染排放，方可有效解决畜禽养殖场带来的雌激素环境风险。本研究选取深圳市新陂头奶牛养殖场，采样分析对比研究了奶牛不同生长阶段其尿液中雌激素的污染排放特征；以深圳市特有的荔枝产业废弃物荔枝树枝为原料制备生物炭，并通过官能团修饰改性生物炭，探讨了生物炭对水溶液中雌激素的吸附去除特性，以及添加生物炭的土壤中雌激素的运移特征。在实验室建立了奶牛尿液雌激素的分析方法，在此基础上分析了养殖场奶牛尿液中雌激素的浓度水平。尿液样品采用 HLB/NH2 固相萃取柱和 Florisil 固相萃取柱进行净化，净化后样品利用 LC/MS/QE 分析。E1、E2、E3、EE2 和 BPA 的方法回收率分别为 63±8.4%、52±3.2%、44±2.4%、44.3±2.7%和 63±7.9%。分析表明怀孕期奶牛尿液雌激素浓度最高，E1 为 581-653 ng/L，17β-E2 为 529-579 ng/L，BPA 为 239-305 ng/L；E3 和 EE2 未检出。产奶期奶牛尿液仅检测到 E1 和 BPA，浓度分别为 72-79 ng/L 和 194-200 ng/L。育成牛尿液亦仅检测到 E1（45-49 ng/L） 和 BPA（189-289 ng/L）。生物炭以及改性生物炭作为较为廉价的吸附剂，对于水体和土壤中雌激素的去除有潜在的应用前景。研究制备了荔枝树枝生物炭（BC），通过钙负载修饰制备了钙改性生物炭（Ca-BC），通过铁和锰负载修饰制备了铁锰改性生物炭（FeMn-BC）。BET 比表面积分析结果表明，改性后的钙生物炭和铁锰生物炭的表面积分别为 214 m2/g 和 424 m2/g，分别是原生物炭比表面积的二倍和四倍，且同时具备微孔结构和介孔结构。XRD 结果表明，钙生物炭在 2θ =29.4 的特征峰特别尖锐，表明有 CaCO3 的晶体的产生，说明钙改性生物炭成功负载碳酸钙晶体，与FTIR 的结果一致。XPS 的窄谱结果表明，铁锰生物炭在 711 ev 和 724 ev 出现 Fe2O3的吸收峰，在 642 ev 和 653 ev 出现 MnO2 的吸收峰，表明生物炭成功负载铁锰氧化物。研究探讨了三种生物炭 BC、Ca-BC 和 Fe-Mn-BC 对养殖场排放的 E1 污染调控特征。通过静态吸附试验表明，BC、Ca-BC 和 Fe-Mn-BC 的吸附率分别是 59.9%、72.9%和 92.3%，且三种生物炭吸附均为快吸附，60min 达到吸附平衡。BC、Ca-BC和 Fe-Mn-BC 对 E1 的吸附过程均符合伪二级动力学方程。BC 的吸附等温线符合Freundlich 模型，Ca-BC 吸附等温线在低温条件 288K 时符合 Langmuir 模型，而Fe-Mn-BC 的吸附等温线在考察范围内呈非线性。雌激素的土壤淋溶实验表明，没有添加生物炭的土壤在淋溶液 200mL 时，检测到淋出液中 E1 浓度为 43.3 μg/L，穿透曲线 E1 最高浓度为 163 μg/L；分别添加BC 和 Fe-Mn-BC 的土壤淋溶实验表明，在其滤出液中并未检测到 E1。但是在添加Ca-BC 的土壤淋溶实验结果表明，Ca-BC 对土壤中雌激素的淋出具有促进作用。此外，E1 在不同土壤和添加生物炭土壤中穿透曲线均呈现非对称性，即迅速上升后缓慢下降，且拖尾现象明显。

Estrogens include natural estrogen estrone (E1), 17β-estradiol (17β-E2), estriol (E3) and synthetic estrogen 17α-ethynyl estradiol (EE2), bisphenol A (BPA) is a typical representative of estrogens in the environment. Estrogens could cause feminization, abnormal reproductive and gender imbalance in male fish at ng/L concentrations. Therefore, the prevention and control of estrogen pollution is very significant for the ecological safety of water environment and population health. Concentrated animal feeding operation(CAFO) are one of the major sources of estrogen emissions. Due to differences in the type of livestock and poultry, the growth characteristics and the farming methods in the north and south regions, it is necessary for us to understand the estrogen emission characteristics of livestock and poultry farms in different regions. And reasonable control of pollution emissions can effectively solve the estrogen environmental risks brought by livestock and poultry farms. In this study, the xin pi tou dairy farm in Shenzhen City was selected to compare the characteristics of estrogen emissions in urine during different stages of growth of cows. The biochar was prepared from the litchi twigs of Shenzhen's unique litchi industrial waste. The modified biochar was modified by functional groups to investigate the characteristics of biochar adsorption and removal of estrogen in aqueous solution, and the migration characteristics of estrogen in soil with biochar added.In our laboratory, an analytical method for urinary estrogens in dairy cows was established. On this basis, the concentration of estrogen in the urine of dairycows was analyzed. The urine samples were purified using HLB/NH2 solid phase extraction columns and Florisil solid phase extraction columns. The purified samples were analyzed by LC/MS/QE. The method recoveries rate of E1, E2, E3, EE2, and BPA were 63±8.4%, 52±3.2%, 44±2.4%, 44.3±2.7%, and 63±7.9% respectively. The analysis showed that the urine estrogen concentration was highest in dairy cows during pregnancy, E1 was 581-653 ng/L, 17β-E2 was 529-579 ng/L, and BPA was 239-305 ng/L; E3 and EE2 were not detected. The urine of dairy cows only detected E1 and BPA at a concentration of 72-79 ng/L and 194-200 ng/L, respectively. The urine of bred cows also detected only E1 (45-49 ng/L) and BPA (189-289 ng/L).As a cheaper adsorbent, biochar and modified biochar have potential application prospects for the removal of estrogens in water and soil. Litchi twig biochar (BC) was prepared, calcium modified biochar (Ca-BC) was prepared by calcium loading modification, and iron-manganese modified biochar (Fe-Mn-BC) was prepared by loading modification with iron and manganese. The BET specific surface area analysis results showed that the specific surface areas of the modified calcium biochar and ironmanganese biochar were 214 m2/g and 424 m2/g, respectively, which were twice and four times larger than the specific surface area of the raw biochar, with microporous structure and mesoporous structure. XRD results showed that the characteristic peak of Ca-BC at 2θ = 29.4 was particularly sharp, indicating the presence of CaCO3 crystals, indicating that the calcium modified biochar was successfully loaded with calcium carbonate crystals, which is consistent with the FTIR results. The narrow-spectrum results of XPS indicate that the Fe-Mn biochar exhibited an absorption peak of Fe2O3 at 711 ev and 724 ev, and an absorption peak of MnO2 at 642 ev and 653 ev, indicating that the biochar was successfully loaded with iron-manganese oxide.In order to investigate the adsorption, migration and transformation process of estrogen in the soil of the orchard, and the adsorption effect of biochar, E1 was used as the targeted chemical, and the modified soil and the raw soil of biochars and were respectively subjected to leaching experiments.The leaching results of E1 soil column showed that the estrogen concentration in the leach solution was 43.27 μg/L when the unmodified soil was in 200ml of leach solution, and the highest concentration in the breakthrough curve was 163.17 μg/L. The BC-modified soil and Fe-Mn-modified soil did not detect estrogen concentration in the filtrate, while the Ca-BC-modified biochar promoted estrogenic leakage. E1 showed asymmetry in the penetration curves of different soils and modified soils, they rose rapidly and then slowly declined, and the tailing phenomenon was obvious.

雌激素 奶牛尿液 改性生物炭 吸附 土壤淋溶

Estrogen Cow urine Modified biochar Adsorption Leaching of soil

中文

联合培养

哈尔滨工业大学

陶寰宇. 畜禽养殖雌激素排放特征及生物炭对典型雌激素运移控制研究[D]. 深圳. 哈尔滨工业大学,2018.