膨润土调质对污泥堆肥的脱毒及重金属钝化和雌酮消除作用

利用干基添加比例为0~10%钙基膨润土对污泥进行了调质,通过52 d的好氧堆肥研究了调质对堆体温度、pH、水溶性盐分(EC)、有机碳、总氮、铵态氮(NH_4~+-N)、硝态氮(NO_3~--N)的影响,并进一步分析了其对污泥脱毒(种子萌发)和重金属(Zn、Cu、Pb、Cd)钝化及雌酮(E1)消除的影响.结果表明,污泥经外加膨润土调质后,可以促进堆肥物料的热灭活无害化,能使有机碳矿化率达到15.27%~19.71%;堆肥过程中各处理堆肥pH先降低后升高,最终稳定在6.76~7.05之间,但膨润土调质堆肥pH的波动变缓;添加膨润土的堆肥EC显著低于对照处理(1 132μS·cm~(-1)),整个堆肥过程EC值随着膨润土添加比例的增加而稍有降低.堆肥过程中的总氮含量逐渐增加,但对照处理在堆肥初期存在一定的氮素损失,而污泥经过调质可减少堆肥初期氮素损失;整个堆肥中NH_4~+-N含量先增加后降低,各处理NO_3~--N均呈现出逐渐增加的趋势,表明污泥调质促进NO_3~--N的转化.虽然调质对种子发芽产生一定的抑制作用,但均不影响堆肥的腐熟,且能显著促进重金属的钝化,同时添加膨润土处理显著降低堆料E1含量,添加比例5%处理使E1含量由90.48μg·kg~(-1)降低至28.27μg·kg~(-1).研究表明,膨润土不高于5%的添加比例是适合的污泥调质措施,在污泥堆肥物料的安全化、脱毒及重金属钝化和雌酮消除方面具有较好的应用潜力.     

Risk assessment of xenoestrogens in a typical domestic sewage-holding lake in China

Release of domestic sewage leads to accumulation of xenoestrogens in holding waters, especially in closed or semi-enclosed waters such as lakes. In the study, the occurrence, distribution, estrogenic activity and risk of eight xenoestreogens were evaluated in Lake Donghu, China. Nonylphenol (NP), octylphenol (OP), and bisphenol A (BPA) were identified as the main xenoestrogens ranging from tens of ng L⁻¹ (in the surface water) or ng g⁻¹ dw (in the suspended particles and sediment) to tens of μg L⁻¹ or μg g⁻¹ dw. The sum of 17β-estradiol equivalents (∑EEQs) ranged from 0.32 to 45.02 ng L⁻¹ in the surface water, 0.53 to 71.86 ng g⁻¹ dw in the suspended particles, and 0.09 to 24.73 ng g⁻¹ dw in the sediment. Diethylstilbestrol (DES) was determined as the main contributor to ∑EEQs followed by NP. The risk assessment showed a higher risk in the surface water than in the suspended particles and sediment in such domestic sewage-holding lake.     

雌酮的氯化产物及其内分泌干扰作用活性

利用固相萃取-LC/ESI-MS分析测定雌酮及其在氯气消毒过程中产生的副产物,结果表明,雌酮容易和次氯酸发生反应,并检出了包括一氯雌酮、二氯雌酮在内的4种副产物．用酵母双杂交方法对副产物的内分泌干扰活性进行了测试,发现副产物也具有内分泌干扰作用．     

Microbial degradation of 17β -estradiol and 17α -ethinylestradiol followed by a validated HPLC-DAD method

This work aimed at studying the biodegradation of two estrogens, 17α -estradiol (E2) and 17β -ethinylestradiol (EE2), and their potential metabolism to estrone (E1) by microbial consortia. The biodegradation studies were followed by High Performance Liquid Chromatography–Diode Array Detector (HPLC–DAD) using a specifically developed and validated method. Biodegradation studies of the estrogens (E2 and EE2) were carried out with activated sludge (consortium A, CA) obtained from a Wastewater Treatment Plant (WWTP) and with a microbial consortium able to degrade recalcitrant compounds, namely fluorobenzene (consortium B, CB). E2 was more extensively degraded than EE2 by CA whereas CB was only able to degrade E2. The addition of acetate as a supplementary carbon source led to a faster biodegradation of E2 and EE2. E1 was detected as a metabolite only during the degradation of E2. The 16S rRNA gene sequence analyses of strains recovered from the degrading cultures revealed the presence of the genera Pseudomonas, Chryseobacterium and Alcaligenes. The genera Pseudomonas and Chryseobacterium were retrieved from cultures supplied with E2 and EE2, while the genus Alcaligenes was found in the presence of E2, suggesting that they might be involved in the degradation of these compounds.     

The effects of soil and Trifolium repens (white clover) on the fate of estrogen

In this study, we investigated the behavior of estrogens in the rhizosphere of white clover (Trifolium repens, clover hereafter) with two different pot tests, using soil and agar as growth media. In a pot test using agar spiked with estrogen, the estrogen concentration in the agar with clover decreased to non-detectable levels within one month, while in the agar without clover, 60% of initially added estrogen remained after one month. The half-lives of estrone (E1) and 17β -estradiol (E2) in the agar with clover were 2.4–3.8 and 13.2 d, respectively. The dissipation of E1 followed first-order rate law, while that of E2 fitted a zero-order reaction, indicating that they had different mechanisms of dissipation from agar. In the soil pot test, the behavior of E1 and E2 was not influenced by clover. An initial rapid decrease in the amount of estrogen extracted by methanol/acetic acid was followed by persistence for 1–3 months, regardless of presence of clover. Moreover, in three weeks E1 and E2 were only partly degraded by microbes extracted from the soil used in the pot test. In this study, abiotic degradation of estrogens and sorption of estrogen to soil, rather than the effects of soil microbes and clover, contributed to the initial rapid dissipation of estrogens in the soil. However, the results of the agar pot test suggested that vegetation such as clover may significantly contribute to removal of estrogens when estrogens in aqueous phase are discharged with surface runoff and preferential flow after heavy rain in agricultural fields, or when present in soils with low estrogen sorptivity.     

高碑店湖表层水中雌激素的分布及其光降解影响因素

雌激素等内分泌干扰物在水体中普遍存在,其在再生水中的存在以及在水体中的迁移转化会产生潜在的健康和生态风险。光降解是水体中雌激素消除的主要途径之一,水体中共存的无机离子及有机质等对雌激素的光解存在不同的影响。对高碑店湖再生水体中雌激素的污染状况进行了调查,结果显示表层水中天然雌激素雌酮(E1)和人工合成雌激素17α-乙炔基雌二醇(EE2)的浓度最高。在模拟太阳光照射条件下对E1在水溶液中的降解规律及影响因素进行了研究,发现在模拟1 SUN的光密度条件下,15 min时E1降解率可达85%(C0=5μg·L-1),而氨氮对E1的光降解存在一定的抑制作用,并且抑制作用随着氨氮的升高而变大。与纯水系统相比,高碑店湖表层水基质中E1的光降解速率较低,说明整体上氨氮、HCO-3、浊度等因素对E1光降解产生的抑制作用占主导。对雌酮及其降解产物进行了红外光谱分析,结果显示1 720 cm-1对应的C=O键特征峰在光照时间为0、10和20 min样品中的强度逐渐减弱,而2 854 cm-1和2 925 cm-1对应的脂肪碳的C-H键特征峰先增强后减弱,可能是因为E1结构中的C-C=O发生了反应生成了C=C-OH,而随着反应的继续,C=C也被进一步氧化,但降解产物的结构需要进一步研究推断。随着E1的光降解,E1水溶液的内分泌干扰活性逐渐下降,氨氮虽然对E1的光降解有一定的抑制作用,但随着降解反应的进行E1水溶液的内分泌干扰活性依然呈下降趋势。     

Environmental transport of endogenous dairy manure estrogens

Although estrogens originating from dairy manure applied to agricultural soils as a fertilizer can potentially contaminate surface water and groundwater, the variables that control transport are poorly understood. Our objective was to assess the potential for off-site movement of endogenous dairy cattle estrogens when manure is applied on fields at agronomically relevant fertilization rates. Estrone (E1), 17α-estradiol (α-E2), and 17β-estradiol (β-E2) were used in laboratory sorption, desorption, and transformation incubations with both manure and an agriculturally relevant soil. Sorption on manure containing 44% organic carbon exceeded sorption on soil containing 0.8% organic carbon by 20 to 150 times, following the pattern of β-E2 > α-E2 > E1. Approximately 20% of E1 and 17% of α-E2 were desorbed from manure, whereas only about 4% of β-E2 was desorbed. Thirty to seventy percent of α-E2 and β-E2 were converted to E1 in soil and manure, making it imperative that transformation reactions be considered when predicting transport and potential biological effects in the environment. Overall results indicate that high organic carbon concentrations and relatively low amounts of desorption inhibit the potential for off-site transport of endogenous dairy manure estrogens.     

MBR中活性污泥对雌酮E1的吸附性能研究

研究了MBR中灭活污泥对雌酮(El)的吸附行为,考察了污泥浓度、污泥粒径和El初始浓度对E1吸附效果的影响,并探讨了不同污泥组分(悬浮颗粒、胶体和溶解物)对E1的吸附作用贡献.结果表明,在E1初始浓度为l～500μg·L-1,4h左右达到吸附平衡;E1的吸附符合Freundlich吸附模型,呈线性吸附;E1初始浓度越大,吸附速率越小.随着污泥浓度升高,单位污泥对E1的吸附量显著下降,出现了固体浓度效应;而吸附去除率却随着污泥浓度的升高而显著增加,且两者之间呈显著正相关(p＜0.05).活性污泥对E1的单位吸附容量随着污泥粒径增大而减小.污泥中悬浮颗粒、胶体和溶解物的含量分别为87.8％、9.6％和2.6％,吸附平衡时,E1在3种组分中的浓度分别为13.9 μg·g-1、24.1 g·g-1和12.5 μg· g-1,胶体吸附效果最好.不同组分对E1的吸附贡献与其含量正相关,吸附贡献为:悬浮颗粒＞胶体＞溶解物.     

水体类固醇雌激素污染现状研究进展

类固醇雌激素被认为具有极强的内分泌干扰性和生物活性,在极低浓度下就能引起人体或动物生殖障碍、行为异常和幼体变异等.由于水体中的类固醇雌激素的生态环境效应最为直接,因此,本文综述了近年来关于水环境中几种常见的类固醇雌激素的基本特征、污染现状、来源及迁移过程的研究,以期为类固醇雌激素的水处理技术研究提供基础信息.     

不同硝化负荷MBR去除类固醇雌激素的研究

以雌酮(E1)和17α-乙炔基雌二醇(EE2)2种典型类固醇雌激素为研究对象,考察了不同硝化负荷好氧MBR对其的去除特性.结果表明,硝化负荷为6.19,0.35,10.58mg/(gMLSS·d)的MBR对E1平均去除率分别为72.33%、64.06%和71.77%,去除负荷分别为29.98,23.06,27.66mg/(gMLSS·d);对EE2平均去除率分别为55.40%、42.87%和58.90%,去除负荷分别为22.39,16.54,23.58mg/(gMLSS·d).E1去除效果均优于EE2.MBR硝化负荷与氨氧化细菌之间有较好的线性关系;而SEs去除负荷与氨氧化细菌及硝化负荷之间不满足线性关系.硝化负荷为0.35mg/(gMLSS·d)时,SEs去除负荷较低,硝化负荷达到6.19mg/(gMLSS·d)时,SEs的去除负荷显著提高,而当硝化负荷增加到10.58mg/(gMLSS·d)时,SEs去除负荷不再有效提高.