集约化养殖场产生的类固醇雌激素(SEs)对沼灌区水土环境和动植物生长具有较大危害.为评估沼灌区SEs渗入土壤并进入周边水体的污染风险,试验选取3种自由态和1种结合态SEs,通过土柱模拟沼灌试验,估算沼灌区土壤不同纵深SEs迁移转化的17β-雌二醇当量(EEQ)以评估污染风险.结果表明:土壤渗滤液中E2与E1-3S的总17β-雌二醇当量(ΣEEQ)最大,E2的总17β-雌二醇当量中位数(ΣEEQm)与总17β-雌二醇当量第95个百分位(ΣEEQ95th)高达 14.16～38.99 μg eeq/L 和 21.11～47.42 μg eeq/L,E1-3S 的ΣEEQm与 ΣEEQ95th分别为 20.70～32.11 μg eeq/L 和30.35～37.97 μg eeq/L;而 17β-E2 的 ΣEEQ 均值整体较低.E1随土层越深而ΣEEQ降低,17α-E2的ΣEEQ均值由大到小为底层、表层、中层、中下层;17β-E2的ΣEEQ均值随土壤纵深增加而减小,E2的ΣEEQ均值由大到小为中层、表层、底层、中下层,E1-3S的ΣEEQ均值随纵深增加而逐渐升高.估算EEQ的评估结果显示,沼灌区周边水体中高浓度E2与E1-3S存在较大污染风险,17β-E2污染风险相对较小.

Steroid estrogens have received worldwide attention and given rise to great challenges of aquatic ecosystems security, posing potential adverse effects on aquatic organisms and human health even at low levels (ng/L). The present study focused on understanding the mobility and abiotic transformation of estrone (E1) and estrone-3-sulfate (E1-3S) over spatial and time scales during soil transport. Column transport experiments showed that the migration capacity of E1-3S was far stronger than E1 in soil. The calculated groundwater ubiquity score and leachability index values also indicated the high leaching mobility of E1-3S. The hydrolysis of E1-3S and abiotic transformation into estradiol and estriol was observed in the sterilized soil. Furthermore, possible transformation products (e.g., SE239, E2378, E1 dimer538, E1-E2 dimer541) of E1 and E1-3S in soil were analyzed and identified after the column transport experiments. The estrogenic activity was estimated by 17β-estradiol equivalency values during the transport process in aqueous and soil phases. Additionally, the potential leaching transport to groundwater of E1-3S requires further critical concern.

Animal husbandry is the second largest source of steroid estrogen (SE) pollutants in the environment, and it is significant to investigate the occurrence and fate of SEs discharged from concentrated animal feeding operations. In this research, with a Chinese typical concentrated dairy farm as the object, the concentrations of SEs (E1, 17α-E2, 17β-E2, E3, and E1-S3) in slurry, lagoon water, and slurry-irrigated soil samples in summer, autumn, and winter were determined. The total concentrations of SEs (mainly E1, 17α-E2, and 17β-E2) in slurry were very high in the range of 263.1-2475.08 ng·L-1. In the lagoon water, the removal efficiencies of the aerobic tank could reach up to 89.53%, with significant fluctuation in different seasons. In the slurry-irrigated soil, the maximum concentrations of SEs in the topsoil and subsoil were 21.54 ng·g-1 to 6.82 g·g-1, respectively. Most of the SEs tended to transport downward and accumulate in the soil accompanied with the complex mutual conversion. Correlations and hierarchical clustering analysis showed a variety of intertransformation among SEs, and the concentrations of SEs were correlated with various physicochemical indexes, such as TN and NO3--N of the slurry, chemical oxygen demand of the lagoon water, and the heavy metals of soil. In addition, 17β-estradiol equivalency assessment and risk quotients indicated that the slurry irrigation and discharge of the lagoon water would cause potential estrogenic risks to the environment. Consequently, reasonable slurry irrigation and lagoon water discharge are essential to efficiently control SE pollution in the environment.

The environmental behaviors of steroid estrogens (SEs) associated with land irrigation and application are of critical concern worldwide. Understanding the spatio-temporal distribution and transformation process of these estrogenic compounds in soil is greatly significant. In this study, laboratory soil column experiments were conducted to investigate and explore the migration and abiotic transformation of 17α-estradiol (17α-E2) and 17β-estradiol (17β-E2) over spatial and time scales. Results indicated that the migration tendency of 17α-E2 and 17β-E2 was similar. Discrepancies in transport for different SEs groups might be due to the competitive sorption and isomeric transformation in the binary-solute system. 17α-E2 and 17β-E2 can also undergo the abiotic transformation during soil column transport. The soil with naturally abundant mineral substances (e.g., iron and manganese oxides) indicated that E2 isomers tended to mineral-promoted racemization, oxidation, reduction, and radical coupling reactions. Some possible transformation products (e.g., SE239, E2378, and SE dimer476) were identified and proposed in soil samples. Compared to the single compound tests, the estimated 17β-estradiol equivalency (EEQ) values of E2 mixture were higher during SEs migration process.

为探究纳米零价铁(nZVI)对水中17β-雌二醇(17β-E2)的降解机制和降解路径,本研究采用降解动力学拟合分析不同初始pH(3、5和7)对17β-E2降解过程的影响.结果表明,酸性条件下17β-E2可被nZVI高效降解,而中性条件下其降解受到极大限制.随着pH进一步降低,nZVI的降解17β-E2的能力仅从降解速率上提升而非降解效率.?OH和?O-2在降解过程中占据主导地位,且随着pH上升?OH的主导地位逐渐被?O-2取代.nZVI自身腐蚀下Fe2+产量和产生速率与17β-E2的降解率和降解速率呈正相关.对降解产物的分析表明,17β-E2可在nZVI作用下转化为E1并在酸性条件下被进一步降解;17β-E2的降解路径可归纳为芳香环基团的替换、断裂和开环;降解产物二聚体和三聚体的证实了仿漆酶反应对17β-E2降解的贡献.实验结果为雌激素污染水体的修复以及nZVI的定向优化提供了理论支撑.

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氯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(EEQ95th)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.

Natural steroid estrogens (NSEs), including free estrogens (FEs) and conjugated estrogens (CEs), are of emerging concern globally among public and scientific community due to their recognized adverse effects on human and wildlife endocrine systems in recent years. In this review, the properties, occurrence, sorption process, and transformation pathways of NSEs are clarified in the environment. The work comprehensively summarizes the occurrence of both free and conjugated estrogens in different natural and built environments (e.g., river, WWTPs, CAFOs, soil, and sediment). The sorption process of NSEs can be impacted by organic compounds, colloids, composition of clay minerals, specific surface area (SSA), cation exchange capacity (CEC), and pH value. The degradation and transformation of free and conjugated estrogens in the environment primarily involves oxidation, reduction, deconjugation, and esterification reactions. Elaboration about the major, subordinate, and minor transformation pathways of both biotic and abiotic processes among NSEs is highlighted. The moiety types and binding sites also would affect deconjugation degree and preferential transformation pathways of CEs. Notably, some intermediate products of NSEs still remain estrogenic potency during transformation process; the elimination of total estrogenic activity needs to be addressed in further studies. The in-depth researches regarding the behavior of both free and conjugated estrogens are further required to tackle their contamination problem in the ecosystem. Graphical abstract ᅟ

为集约化奶牛养殖场沼液在紫色土上的安全合理施用提供参考,采用集约化奶牛养殖场厌氧发酵15d产生的沼液施用于紫色土,定量考察不同施用量(40 m3/hm2、20 m3/hm2、10 m3/hm2、7 m3/hm2)和施用周期(20 m3/hm2,周期为2d、4d、6d、8d、10 d)后5个月(8-12月)对紫色土土壤脲酶、转化酶、过氧化氢酶和磷酸酶活性的影响.结果表明:施用沼液后土壤脲酶、转化酶、磷酸酶活性变化明显,土壤过氧化氢酶活性变化不大,其中低施用量和长施用周期的土壤酶活性相对较高.施用量20 m3/hm2,施用周期为10 d时9月的土壤脲酶活性最高,为61.7 μg NH4+-N/g;施用周期为8d时9月的土壤转化酶活性最高,为0.362 mL(0.1 mol/L)Na2S2O3/g;施用周期为4d时11月的土壤磷酸酶活性较高,为60.1 μg Phenol/g;在整个试验阶段不同施用负荷和使用周期条件下,土壤过氧化氢酶活性均较高,分别为4.94～6.25 mL(0.1 mol/L)KMnO4/g和4.34～5.71 mL(0.1 mol/L)KMnO4/g.

采用实验室内模拟配制沼液方法研究了在382.2(T1)、191.1(T2)、127.4 (T3) m3·hm-2·d-1沼灌负荷下模拟灌溉土柱,从时间尺度与纵深尺度上考察氨氮(NH4+-N)和总磷(TP)在土壤中的迁移吸附行为.结果表明,土壤消纳氮磷能力受沼灌负荷影响较显著,紫色土对沼液中的NH4+-N和TP吸附量随时间变化,均呈现出3个不同阶段,吸附能力由强到陡降,再到短时相对稳定期.在沼灌负荷为382.2 m3·hm-2·d-1时,紫色土存在NH4+-N纵向迁移的较大风险,从降低污染的角度应将沼灌负荷控制在不高于191 m3·hm-2·d-1.

模拟沼液浓度对紫色土进行灌溉,研究沼灌负荷对土壤酶活性及氮、磷迁移的影响,以期有效控制沼灌负荷、降低面源污染.结果表明:逐步提高沼灌负荷在一定程度上能改善土壤脲酶、磷酸酶与转化酶活性,然而过高的沼灌负荷则会抑制表层土壤磷酸酶活性.沼灌可成倍提高土壤中氮、磷含量,在沼灌负荷为382.2 m3/(hm2·d)时,铵态氮和有效磷含量总体均最大,0 cm处分别为680.48 mg/kg和81.68 mg/kg;土壤铵态氮在土层纵深上的分布表现为0 cm＞-15 cm＞-45 cm,具有一定的向下迁移趋势,但有效磷无向深层土壤迁移趋势.X射线衍射图谱定性分析表明,不同沼灌负荷对紫色土土壤成分影响不明显.综合考虑,沼灌负荷以191.1 m3/(hm2·d)较好.

结合贵安新区海绵城市总体规划内容,充分发挥月亮湖景观公园开敞空间大、自然山体植被多、新建绿地广等优势,对雨水起到吸纳、蓄渗和缓释的作用,对月亮湖景观公园给水排水、道路及驳岸工程、水环境等进行了设计.通过建设雨水收集池、植草沟、雨水花园、超标雨水排放系统以及下凹式绿地,有效控制了雨水径流,形成了自然积存、自然渗透、自然净化的景观公园海绵城市系统.

Soil enzyme plays an important role in converting soil nutrient, improving soil fertility and enhancing agricultural products quality. In this paper, the effect of purple soil enzyme activities was investigated by different biogas slurry (BS) recirculation load and period at large-scale farm in southwest China. The results indicated that the value of soil enzyme activities all increased by different BS recirculation load and period comparing to control check group. Its value was at high level by low BS recirculation load and long BS recirculation period. Soil urease and invertase activity reached highest value by T4 (7 m3·hm-2) and T8d (8 d), respectively. The value of soil catalase activity was highest by T1 (40 m3·hm-2) and T10d (10 d). In addition, soil phosphatase activity got peak value by T4 (7 m3·hm-2) and T4d (4 d). The effect of purple soil enzyme activities by BS recirculation at large-scale farms was explored to provide the theoretical basis for utilizing biogas slurry rationally.

The multistage A/O + suspended carrier combined process was applied to treat low carbon source domestic sewage,and the effect of hydraulic retention time (HRT) on chemistry oxygen demand (COD),ammonia nitrogen (NH3-N),total nitrogen (TN) and total phosphorus (TP) removal efficiency was investigated.The experimental results showed that the effluent concentrations of COD,NH3-N and TN could steadily achieve the first class A criteria specified in Discharge Standard of Pollutants for Municipal Wastewater Treatment Plant (GB 18918-2002).However,the removal efficiency of TP was relatively poor with removal rate of less than 75 ％.Anoxic microenvironment condition formed by biofilm on suspended carrier was in favor of simultaneous nitrification and denitrification (SND),so the nitrogen removal efficiency was better than traditional activated sludge system.This provides a theoretical basis for selecting suitable HRT for low-carbon source sewage treatment.