17 β-estradiol and 17 α-ethinylestradiol mineralization in sewage sludge and biosolids

Natural steroid estrogens (e.g., 17 β-estradiol, E2), synthetic steroid estrogens (e.g., 17 α-ethinylestradiol, EE2) and pharmaceutical antibiotics (e.g., ciprofloxacin) are chemicals detected in biosolids and sewage sludges because they partition into the solids fraction during the wastewater treatment process. This research utilized a three-way factorial design (six media × two estrogens × three antibiotic treatments) to quantify cumulative E2 and EE2 mineralization over 133 d (MAX) in a range of sewage sludge and biosolid samples in the presence (4 and 40 mg kg^?1) and absence of ciprofloxacin. The same three-way factorial design was utilized to quantify the impact of the six media, E2 or EE2, and ciprofloxacin on cumulative soil respiration over 133 d (RESP). Minimal ciprofloxacin mineralization was observed (<0.05% over 133 d), but despite its persistence, ciprofloxacin had no significant effect on MAX of E2 or EE2, and, in general, no significant effect on RESP. MAX ranged from 38.38% to 48.44% for E2 but from only 0.72% to 24.27% for EE2 although RESP was relatively similar, ranging from 101.00 to 866.54 mg CO₂ in the presence of E2 and from 69.55 to 893.95 mg CO₂ in the presence of EE2. The sorption-limited bioavailability of EE2, which is inherently resistant to biodegradation due to chemical structure, as MAX and Freundlich sorption coefficients (K_f) were negatively correlated. As such, the K_f values of EE2 were largest in composted biosolids in which EE2 was particularly resistant to microbial degradation as the MAX of EE2 was <3%. In contrast, the MAX of E2 showed a positive association with the K_f values of E2 because some steps in the E2 transformation process have been found to occur in the sorbed phase. The MAX of E2 was significantly greater in the biosolid and composted biosolid media than in any other media, whereas the MAX of E2 decreased in the following order: secondary sewage sludge > primary sewage sludge > biosolid = composted biosolid. This suggests that sewage sludges in municipal lagoons and pre-treatment holding lagoons are a more favorable media for mineralization of EE2, whereas biosolids in post-treatment storage lagoons are a more favorable media for the mineralization of E2. The presence of ciprofloxacin will have no impact on the potential E2 or EE2 mineralization rates in these cases.     

Microbial transformation of synthetic estrogen 17α-ethinylestradiol

Natural estrogens such as estrone, 17β-estradiol, estriol, and the particularly recalcitrant synthetic estrogen 17α-ethinylestradiol used as oral contraceptive, accumulate in the environment and may give rise to health problems. The processes participating in their removal from soil, wastewater, water-sediments, groundwater-aquifer material, and wastewater or sewage treatment plant effluents may involve the action of bacterial and microbial consortia, and in some cases fungi and algae. This review discusses the different efficiencies of bacterial degradation of 17α-ethinylestradiol under aerobic and anaerobic conditions, the role of sulfate-, nitrate-, and iron-reducing conditions in anaerobic degradation, and the role of sorption. The participation of autotrophic ammonia oxidizing bacteria and heterotrophic bacteria in cometabolic degradation of estrogens, the estrogen-degrading action of ligninolytic fungi and their extracellular enzymes (lignin peroxidase, manganese-dependent peroxidase, versatile peroxidase, laccase), and of algae are discussed in detail.     

17β-Estradiol mineralization under field and laboratory incubations

Mineralization studies of natural steroid hormones (e.g., 17β-estradiol, E2) are performed in environmental incubators, usually under a constant temperature such as 20°C. In this paper, we present a microcosm protocol that quantified the mineralization of E2 in soils under field temperatures. The nine agricultural soils tested had a wide range of soil organic carbon (1.1 to 5.2%) and clay (9 to 57%) contents. The calculated time over which half of the applied E2 was mineralized (E2-½) ranged from 299 to 910 d, and total E2 mineralization at 48 d (E2-TOT48) ranged from 4 to 13%. In subsequent laboratory incubations, the same soils were incubated under a constant temperature of 20°C, as well as under cyclic temperatures of 14.5°C (14 h) and 11.5°C (10h), which was within the temperature extremes observed in the field microcosms. E2-½ ranged from 157 to 686 d at 20°C and from 103 to 608 d at the cyclic temperatures, with the E2-TOT48 ranging from 6 to 21% at 20°C and from 7 to 30% under cyclic temperatures. Despite the overall 6.75°C lower mean temperatures under the cyclic versus constant temperatures, E2 mineralization was stimulated by the temperature cycles in three soils. Regardless of the incubation, the same loamy sand soil always showed larger E2 mineralization than the other eight soils and this loamy sand soil also had the smallest E2 sorption. Current modeling approaches do not take into consideration the effects of temperature fluctuations in the field because the input parameters used to describe degradation are derived from laboratory incubations at a constant temperature. Across the eight soils, E2-½ was on average 1.7 times larger and E2-TOT48 was on average 0.8 times smaller under field temperatures than under a constant 20°C. Hence, we conclude that incubations at 20°C give a reasonable representation of E2 mineralization occurring under field conditions to be expected in a typical Prairie summer season.     

QF-1、OV-17柱老化温度的探讨

一、问题的提出 色谱柱是气相色谱分析的心脏部分,好的柱子使分析得心应手,不好的柱子往往使分析归咎失败。2％QF-1、1.5％OV-17柱是目前公认用来分析有机氯农药残留量的理想柱子,人们大多认真地照此配柱,装柱,但对柱的老化问题考虑得尚少。由于过高的老化温度而造成电子捕     

Abiotic oxidation of 17β-estradiol by soil manganese oxides

The degradation of 17β-estradiol (E2) in sterile soil and Mn-free soil slurries was determined. In 0.075 g ml⁻¹ soil slurry, E2 with an initial concentration of 0.0267 μmol g⁻¹ was rapidly degraded and near equimolar estrone (E1) accumulated. A mass balance involving E2 and E1 existed throughout the reaction. The E2 degradation was thus an oxidation process and E1 was the only product. The concurrent release of Mn(II) during E2 oxidation and a lack of E2 oxidation in Mn-free soil slurry together demonstrated that soil manganese oxides were responsible for E2 oxidation. The degree of E2 oxidation was higher at high pH than at low pH, consistent with the fact that the reaction released protons. This study suggests that manganese oxides may be used as soil amendments to effectively oxidize E2 to less potent E1 in soil.     

高频脉冲介质阻挡放电去除水中17β-雌二醇

实验采用高频脉冲介质阻挡放电工艺处理水体中的17β-雌二醇（E2）。结果表明,该工艺可以有效地降解水中的E2,E2的降解过程符合一级反应动力学模型。当体系脉冲峰-峰电压为24kV,初始浓度为100μg／L的E2在超纯水中的降解一级反应速率常数为0．1314min^-1。E2的降解速率常数随脉冲峰-峰电压的增大而升高,随E2初始浓度和溶液初始pH增加而降低,溶液初始电导率对E2的降解影响不大。     

类-Fenton体系对水中17β-雌二醇的光降解

以250W照明金属卤化物灯为光源研究了水中17β-雌二醇（E2）在类-Fenton体系中的光降解。结果表明，Fe（Ⅲ）／H2O2体系能有效地光降解E2。pH3～6范围内，E2光降解率及反应初始速率随酸度的增大而增大；H2O2初始浓度越大，E2降解率及反应初始速率越大；E2初始浓度越低，E2降解率越高，反应初始速率越低。     

类-Fenton体系对水中17β-雌二醇的光降解

以250W照明金属卤化物灯为光源研究了水中17β雌二醇(E2)在类Fenton体系中的光降解。结果表明,Fe(Ⅲ)/H2O2体系能有效地光降解E2。pH3～6范围内,E2光降解率及反应初始速率随酸度的增大而增大;H2O2初始浓度越大,E2降解率及反应初始速率越大;E2初始浓度越低,E2降解率越高,反应初始速率越低。     

Biotransformation of 17α-methyltestosterone in sediment under different electron acceptor conditions

17α-Methyltestosterone (MT), an anabolic androgenic steroid, is used widely in inducing an all male population in aquaculture farming of fish, such as Nile tilapia (Oreochromis niloticus). Current understanding of the occurrence and fate of MT in the sediments and the surrounding areas of the aquaculture ponds are very limited. Bioassay tests showed that MT was biotransformed under aerobic and sulfate-reducing conditions with a half-life of 3.8 d and 5.3 d, respectively, with complete disappearance of androgenic activity. However, under methanogenic condition, MT was found to biotransform but the androgenic activity continued to persist even after 45 d of incubation. In contrast, MT was found to transform slowly under iron(III)-reducing condition and was hardly transformed under nitrate-reducing condition. A possible reason for the lack of transformation of MT under nitrate-reducing condition is the presence of the methyl group at the C-17 position. The results of this study suggest that MT and its degradation products with androgenic activity may potentially accumulate in the sediments of fish farming ponds under iron(III)-reducing, nitrate-reducing and methanogenic conditions.     

好氧污泥对17β-雌二醇吸附性能的研究

研究了好氧活性污泥与失活好氧污泥对17β-雌二醇的吸附性能.17β-雌二醇初始质量浓度为500～10 000 ng/L,采用失活好氧污泥进行吸附,考察了吸附平衡时间、pH与温度对吸附的影响.研究结果表明,失活好氧污泥对17β-雌二醇的吸附在30 min内达到平衡;pH在6～9时对吸附没有影响,pH为9以上时,随着pH升高吸附量减少;温度升高吸附能力降低;其吸附符合Freundlich吸附,且呈线性吸附.在10、20、30 ℃时,Freundlich吸附常数KF分别为91.81、80.65、61.49 L/kg,分配系数Kd分别为561.80、 435.60、306.70 L/kg.另外研究了20 ℃时好氧活性污泥的KF与Kd,它们分别为91.72、514.90 L/kg,与同温下失活好氧污泥的KF和Kd差别均小于20%.     

水体中17种持久性和可迁移有机污染物的检测

持久性和移动性有机污染物(persistent and mobile organic contaminants,PMOCs)在环境中降解缓慢,并且可以通过水体循环进行迁移。由于缺乏水体中PMOCs的高效富集和准确测定方法,导致关于PMOCs在水体中存在水平的可靠监测数据较少。通过优化固相萃取条件和高效液相色谱-串联质谱参数,建立了同时检测水中17种PMOCs的分析方法。采用HLB固相萃取柱对水样中的PMOCs进行富集,乙腈和含10 mmol·L^-1乙酸铵的水溶液作为流动相进行梯度洗脱,PMOCs检出限为0.04～0.35 ng·L^-1,定量限为0.13～1.16 ng·L^-1,回收率为65.01%～98.65%。在北京潮白河、广东北江和河北滹沱河进行布点采样,并测定其PMOCs的质量浓度。实验结果表明：17种PMOCs在潮白河、北江和滹沱河中均有检出,其∑PMOCs平均质量浓度分别为604.69、740.45和505.11 ng·L^-1。潮白河地表水中安赛蜜、金刚烷胺和己内酰胺的质量浓度相对较高,分...     

Adsorption behavior of 17α-ethynylestradiol onto soils followed by fluorescence spectral deconvolution

In this study, a simple and rapid procedure for monitoring adsorption of 17α-ethynylestradiol (EE2) onto soil samples was developed. The used method is based on a multiwavelength fluorescence spectral deconvolution (FSD) where the emission fluorescence spectrum of a sample is considered as a linear combination of emission spectra, named reference spectra. The combination of the reference spectra allows the restitution of the shape of the emission spectrum of any unknown sample. This approach was applied to follow EE2 adsorption onto four soil samples and is an easy and low cost alternative.Adsorption experimental data showed a good fit with the Hill equation, mathematically equivalent to the Langmuir-Freundlich model assuming that the adsorption is a cooperative process influenced by adsorbate-adsorbate interactions. Molecular modelling studies clearly support the “co-operative adsorption” model, showing that after the adsorption of the first layer of EE2 molecules onto the soil, at least one more layer of EE2 is adsorbed, due to interactions established with the first adsorbed layer. Notwithstanding, packing a third row would imply interactions between two EE2 molecules that differ from the ones verified in the lowest energy structure, which also explains the plateau achieved in the adsorption curve.     

An on-farm survey of spatial and temporal stratifications of 17β-estradiol concentrations

17β-estradiol (E2) is a natural estrogenic hormone found in animal manure and urine, which may cause endocrine disruption in sensitive organisms. 17β-Estradiol has been widely detected in the environment, and animal agriculture may be an important source. The objectives of this study were to investigate the potential sources and/or spatial and temporal characteristics contributing to detections of E2 at the farm-scale. Soil cores, segmented into 0.15 m increments, were taken down to the water table from four locations (three potential E2 sources and one control) at or around a swine (Sus scrofa domesticus) farm on five different dates between 2006 and 2007. Estradiol was quantified in the soil-water extracts using liquid chromatography-with tandem mass spectrometry (LC/MS/MS) analysis. Estradiol detections were widespread and found in 128 out of 345 extractions (37%). Concentrations ranged from 0 to 1910 ng L⁻¹ (porewater equivalents). A location that received field application of manure had significantly lower E2 concentrations compared to other locations. Also, the spring 2007 E2 concentrations were significantly higher than all other sample dates, perhaps related to climatic and hydrological events. Results suggested E2 was not directly related to manure sources, but was widespread in this environment. Where E2 was detected, highest concentrations favored the upper profile, while the greatest frequency of detections was in the lower profile and near the water table. Detections of E2 were associated with high organic mater contents in the upper profile and high sand contents in the lower profile. The study suggests that E2 is widespread in some soil environments, raising questions as to the source and mechanisms that facilitate its transport and mobility.     

天然有机物共存时生物活性炭对17β-雌二醇的去除

以17β-雌二醇（E2）为目标物,研究了在天然有机物共存的情况下,生物活性炭（BAC）小柱和粒状活性炭（GAC）小柱去除E2的效果。结果表明,BAC小柱和GAC小柱都可有效去除E2,运行600d后出水仍未检出E2。从纵向浓度分布来看,BAC小柱对E2的处理效果略好于GAC小柱。BAC小柱去除E2主要是通过活性炭吸附作用和生物降解作用。空床接触时间也会对E2的去除产生影响。在BAC小柱和GAC小柱中,NOM的去除率随时间延长而降低,E2的去除率始终保持在100％,由此可以推断E2和NOM在活性炭的不同位置进行吸附。     

Identification of new ozonation disinfection byproducts of 17β-estradiol and estrone in water

Estrogens are a class of micro-pollutants found in water at low concentrations (in the ng L⁻¹ range), but often sufficient to exert estrogenic effects due to their high estrogenic potency. Disinfection of waters containing estrogens through oxidative processes has been shown to lead to the formation of disinfection byproducts, which may also be estrogenic. The present work investigates the formation of disinfection byproducts of 17β-estradiol (E2) and estrone (E1) in the treatment of water with ozone. Experiments have been carried out at two different concentrations of the estrogens in ground water (100 ng L⁻¹ and 100 μg L⁻¹) and at varying ozone dosages (0-30 mg L⁻¹). Detection of the estrogens and their disinfection byproducts in the water samples has been performed by means of ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) with a triple quadrupole (QqQ) and a quadrupole-time of flight (QqTOF) instrument. Both E2 and E1 have been found to form two main byproducts, with molecular mass (MM) 288 and 278 in the case of E2, and 286 and 276 in the case of E1, following presumably the same reaction pathways. The E2 byproduct with MM 288 has been identified as 10epsilon-17beta-dihydroxy-1,4-estradieno-3-one (DEO), in agreement with previously published results. The molecular structures and the formation pathways of the other three newly identified byproducts have been suggested. These byproducts have been found to be formed at both high and low concentrations of the estrogens and to be persistent even after application of high ozone dosages.     

含17β-雌二醇饮用水氯化消毒前后水质生物毒性的变化

选择饮用水中经常暴露的17β-雌二醇(E2)为研究对象,考察了含有E2饮用水在氯化消毒前后的水质生物毒性变化规律。小球藻急性毒性实验结果表明,不同浓度E2(0、2、4、8、16 mg·L~(-1))单独暴露条件下,其对小球藻的生长抑制率呈现出较为明显的剂量-效应关系,即随着E2暴露浓度的升高,对小球藻的生长抑制率有所增加;在较高氯投量下(E2与氯摩尔浓度比值为1∶2和1∶5),氯化消毒后水样对小球藻的生长抑制率均高于氯化消毒前,而在低氯投量下(E2与氯摩尔浓度比值为4∶1和1∶1),水样对小球藻的生长抑制率均低于氯化消毒前,表明低氯投量可降低E2产生的水质急性毒性风险。小球藻酶活性实验结果表明,无论是SOD活力、CAT活力,还是MDA含量,并没有出现因受E2暴露和氯氧化胁迫而产生显著上升的趋势,表明E2单独暴露或E2经氯化消毒后并不会对小球藻的酶活性产生显著影响。     

盐单胞菌H17降解苯酚的响应面法优化及动力学

为获得盐单胞菌(Halomonas sp.)H17降解苯酚的最优条件,在单因素试验的基础上,通过Box-Behnken设计试验与响应面法,考察温度、pH、葡萄糖浓度对H17降解苯酚的影响,并通过动力学模型探究该菌株的生长和苯酚降解特性。结果表明,H17降解苯酚的最优条件为30℃、pH=8.0、葡萄糖质量浓度0.8g/L,在此条件下,苯酚降解率预测值为74.39%,实际值为73.92%,表明该模型可靠。该菌株降解苯酚动力学模型符合Haldane模型,其最大比降解速率、饱和常数和抑制常数分别为0.35h~(-1)、165.91mg/L和460.13mg/L。响应面法优化得到的生物降解条件准确,可为高盐含酚废水处理提供依据。     

Assessment of the abiotic transformation of 17β-estradiol in the presence of vegetable matter

A study using 17β-¹⁴C₄-estradiol (¹⁴C-E2) was performed to confirm and characterize the catalytic transformation of estrogens in the presence of a model vegetable matter (namely rabbit food) as a surrogate material for vegetable wastes found in sewage. Results corroborated the occurrence of an abiotic transformation. Unknown transformation byproduct(s) accounted, respectively, for 38% and 9% of the initial radioactivity in liquid and extractable solid phases after 72 h; on the other hand, only 15% and 7% of this radioactivity corresponded to ¹⁴C-E2 in those same matrices. Mass balance was closed including the radioactivity irreversibly bounded to the solid phase. Formation of ¹⁴C₄-estrone was monitored by Liquid Chromatography with tandem Mass Spectrometry detection; negative results were found in all sampling events. This process could be harnessed to optimize sustainable technologies for the removal of phenolic microcontaminants from wastewater.     

三种藻类引发水中17α-乙炔基雌二醇的光降解实验研究

研究了普通小球藻、铜绿微囊藻和柱孢鱼腥藻3种藻类引发水中17α-乙炔基雌二醇(EE2)的光降解.结果表明,在250 W高压汞灯(HPML,nm)的照射下,一定藻浓度下,EE2的光降解率可达19%-20%.另外,还研究光强、藻悬浮液浓度和EE2初始浓度等对EE2光降解速率的影响,发现在本实验体系中,光通量大、藻浓度高及EE2初始浓度低有利于提高EE2的光降解速率.