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1.
The growing use of pharmaceutical drug is mainly due to several diseases in human and in animal husbandry. As these drugs are discharged into waterways via wastewater, they cause a major impact on the environment. Many of these drugs are hormones; in which even at low concentrations can alter metabolic and physiological functions in many organisms. Hormones were found in surface water, groundwater, soil, and sediment at concentrations from nanograms to milligrams per liter of volume—quantities known to cause changes in the endocrine system of aquatic organisms. This study aimed to develop a methodology for hormone detection (estriol, estrone, 17β-estradiol, 17α-ethinylestradiol, progesterone, and testosterone) on surface and treated water samples. Sample toxicity was assessed by ecotoxicology tests using Daphnia magna. A liquid chromatograph coupled to a mass spectrometer with an electrospray ionization source (LC-ESI-MS/MS) was used for the analysis. The results showed that samples were contaminated by the hormones estriol, estrone, progesterone, 17β-estradiol, and 17α-ethinylestradiol during the sampling period, and the highest concentrations measured were 90, 28, 26, 137, and 194 ng·L?1, respectively. This indicates the inflow of sewage containing these hormones at some points in the Piracicaba River in the State of Sao Paulo—Brazil. Results indicated little toxicity of the hormone estriol in D. magna, indicating that chronic studies with this microcrustacean are necessary.  相似文献   

2.
Hospital effluent and connected waste water treatment plant (WWTP) influent and effluent were sampled daily to determine the levels and inter-day variations of three naturally occurring steroid estrogens: estrone, 17β-estradiol, estriol, and synthetic 17α-ethinylestradiol. After solid phase extraction, interferences were removed with a silica gel clean-up step and the samples analysed using gas chromatography with mass selective detection (GC-MSD). The determined inter-day concentrations in hospital effluent were between 8.6 to 31.3 ng L(-1) for estrone, 相似文献   

3.
Endocrine disrupting compounds (EDCs), represented by steroid hormones, organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and bisphenol A have been determined in four sediment cores from the Gulf of Mexico, from New Orleans surface water (Lake Pontchartrain and Mississippi River), and from the influent and effluent of a New Orleans municipal sewage treatment plant. During the five-month monitoring of selected EDCs in the Mississippi River (MR) and Lake Pontchartrain (LP) in 2008, 21 of 29 OCPs in MR and 17 of 29 OCPs in LP were detected; bisphenol A was detected in all of the samples. Steroid hormones (estrone, 17β-estradiol and 17α-ethinylestradiol) were detected occasionally. Total EDC (OCPs + PCBs + steroid hormones + bisphenol A) concentrations in the two surface water samples were found to vary from 148 to 1112 ng L(-1). Strong correlation of the distribution of total OCPs, total PCBs and total EDCs between solid and water phases was found in LP, while moderate or no correlation existed in MR. OCPs, PCBs, steroid hormones, and bisphenol A were all detected in the ocean sediments, and total EDCs were measured in the range of 77 to 1796 ng g(-1) dry sediment weight. The EDCs were also found in untreated and treated municipal sewage samples with a removal efficiency of 83% for OCPs but no removal efficiency for 17α-ethinylestradiol.  相似文献   

4.
The presence of natural estrogen hormones as trace concentrations in the environment has been reported by many researchers and is of growing concern due to its possible adverse effects on the ecosystem. In this study, municipal biosolids, poultry manure (PM) and cow manure (CM), and spent mushroom compost (SMC) were analyzed for the presence of seven estrogen hormones. 17α-estradiol, 17β-estradiol, 17α-dihydroequilin, and estrone were detected in the sampled biosolids and manures at concentrations ranging from 6 to 462 ng/g of dry solids. 17α-estradiol, 17β-estradiol, and estrone were also detected in SMC at concentrations ranging from 4 to 28 ng/g of dry solids. Desorption experiments were simulated in the laboratory using deionized water (milli-Q), and the aqueous phase was examined for the presence of estrogen hormones to determine their desorption potential. Very low desorption of 0.4% and 0.2% estrogen hormones was observed from municipal biosolids and SMC, respectively. An estimate of total estrogen contribution from different solid waste sources is reported. Animal manures (PM and CM) contribute to a significant load of estrogen hormones in the natural environment.  相似文献   

5.
Steroid estrogens such as estrone (E1), 17β-estradiol (E2), estriol (E3), and 17α-ethynylestradiol (EE2) have been suspected to be the main contaminants, which can affect the endocrine system of animals. Many authors have investigated these chemicals in the domestic wastewater treatment plants (WTP). However, wastewater from industries producing steroid contraceptives has not got ample attention. From the environmental point of view, the four steroids are very significant because even very low concentrations (ng/L) can cause reproductive disturbances in human, livestock and wildlife. The main purpose of the present investigation was to develop an analytical method for the determination of the four steroid estrogens present in WTP of a pharmacy factory, mainly producing contraceptive medicine in Beijing, China. Analysis was performed by solid-phase extraction (SPE) system and liquid chromatography combined with tandem mass spectrometry (LC/MS/MS). The average recoveries from effluent samples ranged from 88% to 103% and the precision of the method ranged from 9% to 4%. Based on 0.5-L wastewater samples, the limit of quantification (LOQ) was determined at 0.7 ng/L for E1, 0.8 for E2, 0.9 ng/L for E3, and 0.5 ng/L for EE2 in influent, and 1.0 ng/L for E2 and EE2, and 2.0 ng/L for E1 and E3 in effluent. In the influent samples, average concentrations of 80, 85, 73 and 155 ng/L were determined for E1, E2, E3 and EE2, respectively, showing that they were removed in this WTP to the extent of 79, 73, 85 and 67%, respectively.  相似文献   

6.
The utility of HPLC with a size exclusion chromatography (SEC) column for the fractionation of environmental samples was examined to expand the applicability of recombinant yeast assays (RYAs) for the measurement of estrogenic activity in environmental samples. The elution of steroidal hormone standards through SEC was tested, and river water and sediment samples were subjected to SEC fractionation. The retention times of all estrogen standards were longer than those of the major components with absorbance at 230 nm of the environmental sample matrix. The estrogenic activity of SEC fractions of environmental samples from highly polluted sites was measured using RYA and revealed the existence of estrogenic compounds that could not be detected or quantified in extracted samples before fractionation. The fractions from environmental samples that corresponded to the retention time of estrone, 17[small beta]-estradiol, and estriol were analyzed with LC/MS/MS. These three estrogens were separated into three different fractions, and the concentration of estrone coincided with the estrogenic activity of the fraction in which it was detected. The profile of estrogenic activity of SEC fractions indicated the molecular size of the estrogenic compounds and the yeast growth inhibitors in samples.  相似文献   

7.
Concern over steroid estrogens has increased rapidly in recent years due to their adverse health effects. Effluent discharge from wastewater treatment plants (WWTPs) is the main pollutant source for environmental water. To understand the pollutant level and fate of steroid estrogens in WWTPs, the occurrence of estrone (E1), 17-β-estradiol (E2), estriol (E3), and 17-β-ethinylestradiol (EE2) was investigated in the Gaobeidian WWTP in Beijing, China. Water samples from influent as well as effluent from second sedimentation tanks and advanced treatment processes were taken monthly during 2006 to 2007. In influent, steroid estrogen concentrations varied from 11.6 to 1.1?×?10(2)?ng/l, 3.7 to 1.4?×?10(2)?ng/l, no detection (nd) to 7.6×10(2)?ng/l and nd to 3.3?×?10(2)?ng/l for E1, E2, E3, and EE2, respectively. Compared with documented values, the higher steroid estrogen concentrations in the WWTP influent may be due to higher population density, higher birthrate, less dilution, and different sampling time. Results revealed that a municipal WWTP with an activated sludge system incorporating anaerobic, anoxic, and aerobic processes could eliminate natural and synthetic estrogens effectively. The mean elimination efficiencies were 83.2%, 96.4%, 98.8%, and 93.0% for E1, E2, E3, and EE2, respectively. The major removal mechanism for natural estrogens and synthetic estrogen EE2 were biodegradation and sorption on the basis of mass balance in water, suspension particles, and sludge. In the WWTP effluent, however, the highest concentrations of E1, E2, E3, and EE2 attained were 74.2, 3.9, 5.1, and 4.6?ng/l, respectively. This is concerning as residual steroid estrogens in WWTP effluent could lead to pollution of the receiving water. Advanced flocculation treatment was applied in the WWTP and transformed the residual estrogen conjugates to free species, which were reduced further by filtration with removal shifting from 32% to 57% for natural estrogen, although no EE2 was removed.  相似文献   

8.
Environmental occurrence of CECs poses a great threat to both aquatic life and human health. The aim of this study was to optimize and validate SPE/LC-(ESI)MS-MS method for simultaneous quantitative monitoring of two sub-classes of CECs (pharmaceuticals and hormones) and to estimate the concentrations of select CECs in environmental water samples. For all the tested analytes, recoveries in laboratory reagent water were greater than 81%. Average percent (relative standard deviation) RSD of the analytes in recovery, repeatability, and reproducibility experiments were ≤?10%. Determination coefficients (r2) of primidone, diclofenac, testosterone, and progesterone were estimated to be 0.9979, 0.9972, 0.9968, and 0.9962, respectively. Limits of detection (LOD) for primidone, diclofenac, testosterone, and progesterone were 4.63 ng/L, 5.36 ng/L, 0.55 ng/L, and 0.88 ng/L, respectively. Limits of quantification (LOQ) for primidone, diclofenac, testosterone, and progesterone were 14.72 ng/L, 17.06 ng/L, 1.766 ng/L, and 2.813 ng/L, respectively. Average recoveries in environmental water and wastewater samples were greater than 74% and RSD were ≤?7%. Trace levels (68.33–125.70 ng/L) of primidone were detected in four environmental water samples, whereas diclofenac was not detected in any of the tested sample. Trace levels of progesterone were observed in two environmental samples (16.64 –203.73 ng/L), whereas testosterone was detected in STP inlet sample (178.16 ng/L).  相似文献   

9.
10.
Concentrated animal feeding operations have been recognized as one of the most important contributors of natural estrogens which show significant endocrine-disrupting properties in aquatic environments. In this study, the concentrations of 17α-estradiol (17α-E2), 17β-estradiol (17β-E2), estrone (E1), and estriol (E3) in several matrices, including soils (surface and deep), sediments (surface and deep), and groundwaters, around a typical dairy farm were surveyed using gas chromatography/mass spectrometry. Of the two farmlands, surface and subsurface sediments in waste lagoon and along effluent drainage drench, the concentrations of 17α-E2, 17β-E2, and E1 ranged from below detection limit to the highest level of 6.60 μg/kg, except that E3 was not detectable. Three estrogens of 17α-E2, 17β-E2, and E1 with the concentrations of 3.18-31.61 ng/L were observed in two groundwater samples. The results clearly demonstrated the vertical migration and horizontal transport of estrogens in the investigated area. Within 750-m distance, it was observed the attenuation of 17α-E2, 17β-E2, and E1 along the effluent route and the horizontal migration of estrogens was less than 1,350 m in this survey.  相似文献   

11.
A passive sampler (the polar organic chemical integrative sampler; POCIS) was assessed for its ability to sample natural estrogens (17β-estradiol, E2; estrone, E1 and estriol, E3) and the synthetic estrogen (17α-ethynylestradiol, EE2) in the outlet of a sewage treatment works over several weeks. The performance of the POCIS was investigated and optimised in the laboratory before field deployment with high recoveries (66-99%) were achieved for all estrogens. Moreover, it was shown that POCIS does not exhibit any preferential selectivity towards any of the target compounds. The sampling rates of E1, E2 and E3 were 0.018 ± 0.009, 0.025 ± 0.014 and 0.033 ± 0.019 L d(-1), respectively. Following field deployments of 28 days in the discharge of a sewage works, POCIS was shown to enhance the sensitivity of estrogen detection, especially for E3, and provide time-weighted average (TWA) concentrations of E1, E2 and E3, ranging from undetectable to 12 ng L(-1) upstream of the outflow of a sewage treatment works, 13 to 91 ng L(-1) at the outflow and 8 to 39 ng L(-1) downstream of the outflow. This revealed that E1, E2 and E3 are not completely removed during sewage treatment, with concentrations most likely being maintained by contributions from conjugated estrogen analogues. Grab water samples showed considerable variation in the concentrations of estrogens over a longer period (6 months). The results confirm that POCIS is an effective and non-discriminatory method for the detection of low concentrations of estrogens in the aquatic environment.  相似文献   

12.
The development of a high-throughput method for the analysis of 14 endocrine-disrupting substances in environmental solid matrices has been investigated. Selected compounds were: hormones (estrogens and progestogens), parabens and triclocarban. The ultrafast method (15 s per sample) is based on the laser diode thermal desorption-atmospheric pressure chemical ionization (LDTD-APCI) coupled to tandem mass spectrometry (MS/MS). This novel approach was tested and validated in three different solid matrices (municipal sludge cakes, aquatic sediments and agricultural soils) and its performance was evaluated by estimation of extraction recovery, linearity, precision, and detection limits. In contrast to other methods based on LC-MS/MS, a cleanup step is not necessary or minimal for the municipal sludge cake matrix. Extraction recoveries ranged from 80 to 109% for all compounds in all matrix types except for estriol which was 60-75%. The intra- and inter-day precisions, as indicated by % RSD, were ≤ 14% and ≤ 16%, respectively. The method detection limits ranged from 0.7 to 4.0 ng g?1 in sediments and soil matrices and 2.8 to 16.8 ng g?1 for municipal sludge cake samples. The results for real environmental samples collected in different areas of Quebec (Canada) are illustrated.  相似文献   

13.
The partitioning of steroid estrogens in wastewater treatment and receiving waters is likely to influence their discharge to, and persistence in, the environment. This study investigated the partitioning behaviour of steroid estrogens in both laboratory and field studies. Partitioning onto activated sludge from laboratory-scale Husmann units was rapid with equilibrium achieved after 1 h. Sorption isotherms and Kd values decreased in the order 17??-ethinyl estradiol > 17??-estradiol > estrone > estriol without a sorption limit being achieved (1/n?>1). Samples from a wastewater treatment works indicated no accumulation of steroid estrogens in solids from primary or secondary biological treatment, however, a range of steroid estrogens were identified in sediment samples from the River Thames. This would indicate that partitioning in the environment may play a role in the long-term fate of estrogens, with an indication that they will be recalcitrant in anaerobic conditions.  相似文献   

14.
In this study, a method for the simultaneous determination of two steroid hormones, 17β-estradiol (E2) and estriol (E3), and a hormone mimicking polycarbonate, bisphenol-A (BPA), was developed and validated. This was thereafter used for the determination of the levels of the hormones in surface water collected around some livestock farms. The sensitivity of the method allowed the LODs and LOQs of the hormones and mimic hormone in the range 1.14–2.510 and 3.42–7.53 μg/L, respectively. The results revealed wide variability in the concentrations of E2 and E3, while BPA was not detected at any of the sampling stations. The concentration of E3 ranged between <1.14 and 45.5 μg/L (N = 120) in station 2 water. The highest concentration of E2 (15.7 μg/L, N = 80) was observed in water from station 1. The varied concentrations may be connected with the nature and sources of release, inconsistencies in analyte distribution due to dynamics of water flow pattern and the physical/chemical properties of the receiving water bodies.  相似文献   

15.
The occurrence of twenty pharmaceutical compounds was quantitatively determined in effluents from two major Oslo city hospitals, Rikshospitalet and Ullev?l, along with influent, sludge and final effluent from the city's VEAS wastewater treatment works (WTW). Composite hospital effluents were collected over a twelve week period and were showed to contain paracetamol, metoprolol, diclofenac, ibuprofen, 17beta-Estradiol, estriol, estrone, oxytetracycline, tetracycline, doxycycline, chlorotetracycline, demeclocycline, trimethoprim, ciprofloxacin, sulfamethoxazole, cyclophosphamide and ifosfamide. Three pharmaceuticals were not detected above the limit of detection; cefuroxime, 17alpha-ethinylestradiol and meclocycline. Composite influent, sludge and effluent samples were collected from VEAS WTW over a seven week period. The influent into VEAS WTW contained all of the same selected substances detected in the hospital effluents, except for oxytetracycline, chlorotetracycline, demeclocycline, cyclophosphamide and ifosfamide. The percentage of pharmaceuticals entering the works from the hospitals was <10% for all of the selected compounds. VEAS sludge samples contained a different profile of substances reflecting their physico-chemical properties. Hydrophobic antibiotics, such as oxytetracycline, tetracycline and ciprofloxacin, were detected in all of the collected sludge samples. Their absence in the collected influent samples suggests that they enter the works bound to effluent particles, with the dissolved fraction observed in the hospital effluents partitioning onto particulate matter within the sewerage network. The final effluent from VEAS WTW contained reduced concentrations of many pharmaceuticals, including paracetamol, ibuprofen and sulfamethoxazole. For other compounds, such as metoprolol, diclofenac and trimethoprim, there were often higher concentrations in the effluent than the influent. These effluent concentrations represent median inputs varying from low g day(-1) (e.g. paracetamol and ibuprofen) to nearly 200 g day(-1) (e.g. metoprolol and trimethoprim) into Oslofjord. A simple risk assessment showed that the antibiotic ciprofloxacin may at times pose an acute risk to the Oslofjord aquatic environment.  相似文献   

16.
Occurrence and fate of eight kinds of selected endocrine-disrupting compounds (EDCs) in three sewage treatment plants (STPs) of Beijing, China was investigated. These EDCs, composed of 4-octylphenol (4-OP), 4-n-nonylphenol (4-n-NP), bisphenol A (BPA), estrone (E1), 17α-estradiol (17α-E2), 17β-estradiol (E2), estriol (E3) and 17α-ethinylestradiol (EE2), in every step of STPs, were simultaneously analysed by gas chromatography/mass spectrometry after derivatisation. All the EDCs were detected in the influents of three STPs, and BPA was the most abundant compound. The concentrations of EDCs ranged from 36.6 ng/l of 17α-E2 (STP C) to 1342.3 ng/l of BPA (STP B) in the influent sewages and from below limits of detection of E2 and E3 (STP C) to 142.5 ng/l of E1 (STP B) in the effluent sewages. The STPs could not remove alkylphenols effectively from the aqueous phase with less than 40% reduction. BPA decreased over 90%, and steroid estrogens achieved considerable reductions from 64.8% of E2 to 94.9% of E3. Generally, biological treatment was more effective in removing alkylphenols, BPA and natural estrogens from the aqueous phase than primary treatment. However, the synthetic estrogen, EE2, was mostly removed by the primary treatment with about 63.5% reduction. It is the first time that the concentration of 17α-E2 in the sewage of China was reported in this paper. The compound might have a bearing with the waste effluents of dairy farms around urban area of Beijing.  相似文献   

17.
Concentration levels of six natural and anthropogenic origin steroid estrogens, namely, diethylstilbestrol (DES), estrone (E1), estradiol (E2), estriol (E3), ethinylestradiol (EE2), and estradiol-17-valerate (Ev), from different effluents in Beijing were assessed. Sampling sites include two wastewater treatment plants (WWTPs), a chemical plant, a hospital, a pharmaceutical factory, a hennery, and a fish pool. In general, concentrations of estrogens in the effluents varied from no detection (nd) to 11.1 ng/l, 0.7 to 1.2 × 103 ng/l, nd to 67.4 ng/l, nd to 4.1 × 103 ng/l, nd to 1.2 × 103 ng/l, and nd to 11.2 ng/l for DES, E1, E2, EE2, E3, and Ev, respectively. The concentration levels of steroid estrogens from different effluents decreased in the order of pharmaceutical factory and WWTP inlets > hospital > hennery > chemical factory > fish pool. This study indicated that natural estrogens E1, E2, and E3 and synthetic estrogen EE2 are the dominant steroid estrogens found in the different Beijing effluents. For source identification, an indicator (hE = E3/(E1 + E2 + E3)) was used to trace human estrogen excretion. Accordingly, hE in effluents from the hospital and WWTP inlets exceeded 0.4, while much smaller values were obtained for the other effluents. Human excretions were the major contributor of natural estrogens in municipal wastewater. Estimation results demonstrated that direct discharge was the major contributor of steroid estrogen pollution in receiving waters.  相似文献   

18.
山东省主要河流中抗生素污染组成及空间分布特征   总被引:1,自引:0,他引:1  
采用固相萃取-液相色谱/串联质谱法研究了山东省境内四大流域主要河流中抗生素污染组成及空间分布特征,涉及我国用量最大的6类共20种抗生素。结果表明:20种抗生素均有检出,且大环内酯类、喹诺酮类和四环素类抗生素整体检出浓度较高。就流域而言,半岛诸河流域抗生素污染较小,平均总质量浓度61.4 ng/L;海河流域、小清河流域和淮河流域相对较为严重,平均总质量浓度分别为232、175、118 ng/L。抗生素空间分布呈现一定的规律,检出浓度较高的点位主要集中在人口密集区下游,抗生素污染与周边生活污水、养殖企业废水和城市污水处理厂排水密切相关,而且抗生素组成可从一定程度上反映出污染来源。  相似文献   

19.
Concentrations of six endocrine-disrupting compounds (EDCs), bisphenol A (BPA), estrone (E(1)), 17β-estradiol (E(2)), estriol (E(3)), 17α-ethynylestradiol (EE(2)) and diethylstilbestrol (DES), were assessed in influents, effluents and excess sludge in ten municipal wastewater treatment plants (WWTPs) in the Three Gorges Reservoir (TGR) area, Chongqing, China. Three types of activated sludge treatment processes, oxidation ditch (OD), reversed anaerobic-anoxic-oxic (rA(2)/O) technology and sequential batch reactor (SBR), were used in the surveyed WWTPs. These WWTPs were all combined landfill leachate-sewage treatment plants. All analytes were extracted by solid-phase extraction (SPE) in the dissolved phase and by accelerated solvent-based extraction (ASE) in sludge. Gas chromatography-mass spectrometry (GC-MS) was employed for the analysis of EDCs. Among these EDCs, BPA was the most frequently detected and abundant compound (100.0-10566.7 ng L(-1), 15.5-1210.7 ng L(-1) and 85.0-2470.4 ng g(-1) with respect to the influents, effluents and excess sludge samples). The greatest levels of steroidal estrogens in municipal influents were observed in E(3) which were all >100 ng L(-1), followed by E(1) (42.2-110.7 ng L(-1)) and E(2) (7.4-32.7 ng L(-1)), and in the effluents and sludge were E(1) > E(3) > E(2) which were all <31 ng L(-1) and 105 ng g(-1), respectively. Regarding synthetic estrogens, EE(2) was frequently detected in the influents, occurring below 50 ng L(-1), while DES was not detected at all. A high correlation coefficient was observed between the leachate-sludge ratio and concentrations of influent EDCs, and it was statistically significant (i.e., R > 0.65, P < 0.05), but removal efficiency of the EDCs did not show significant differences with OD, rA(2)/O and SBR processes. Furthermore, modification of treatment technology as well as operational parameters, such as hydraulic retention time (HRT), sludge retention time (SRT) and disinfection process (DP), were recommended to further eliminate the residual EDCs.  相似文献   

20.
长江南京段新兴污染物污染特征及风险评估   总被引:1,自引:0,他引:1  
在长江南京段上游至下游依次布设6个采样点采集水样,使用固相萃取和LC-MS/MS相结合的方法对5种选定药物的质量浓度进行测定,并采用风险熵模型评估其生态风险。结果表明,6个采样点均检测到药物存在。其中,四环素、红霉素、罗红霉素和氯霉素的检出率为100%,最高检出值为10.29 ng/L(氯霉素)。与国内外其他地表水相比,长江南京段水中的药物质量浓度较低。生态风险评估结果表明,长江南京段水中5种药物的风险熵值均低于1,对水生生物不存在高风险。  相似文献   

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