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1.
J Environ Qual ; 49(5): 1322-1333, 2020 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-33016441

RESUMO

Antibiotics and estrogens are recognized as emerging contaminants in the water environment because of their potentially adverse effects on aquatic ecosystems. The concentrations of four steroid estrogens (17α-estradiol, 17ß-estradiol, estrone, and estriol) and eight antibiotics (norfloxacin, levofloxacin, ciprofloxacin, enrofloxacin, metronidazole, sulfapyridine, doxycycline, and sulfamethoxazole) in the Chaohu Lake basin in Anhui province, China, were analyzed along with adjacent wastewater. The levels of the target antibiotics and estrogens were below detection limits (not detected [nd])-89.86 and nd-118.09 ng L-1 , respectively, in the lake water. All of the target antibiotics and estrogens were detected in sediment, and the concentrations ranged widely (nd-35,544 and nd-16,344 ng kg-1 , respectively). Antibiotics and estrogens varied spatially in the study area and mostly came from untreated wastewater. Antibiotics and estrogens were associated with water parameters such as pH and total nitrogen. A significant positive correlation was observed between estriol and levofloxacin concentrations (r = .65; p < .01), indicating that levofloxacin from the same source might have inhibited the microbiological degradation of estriol in the surface water. Overall, the estrogens pose a more severe risk than antibiotics to the Chaohu Lake system. However, co-occurrence of antibiotics may affect the fate of estrogens in the same lake media. More attention should be given to estrogens than to antibiotics in wastewater-affected lake systems.


Assuntos
Águas Residuárias , Poluentes Químicos da Água/análise , Antibacterianos/análise , China , Ecossistema , Monitoramento Ambiental , Estrogênios/análise , Lagos/análise
2.
J Chromatogr A ; 1627: 461400, 2020 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-32823105

RESUMO

In this work, a single cross-linking functional monomer, 2,5-divinylterephthalaldehyde, was designed and synthesized to simplify the preparation of molecularly imprinted polymers (MIPs). In the presence of estradiol as a template, MIPs were successfully prepared using 2,5-divinylterephthalaldehyde along with a solvent and initiator. This method reduced most of the complex variables encountered in the traditional synthesis. Characterization of the morphology and structure of the MIPs was performed by scanning electron microscopy, Fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller analysis. Compared with non-imprinted polymers, the MIPs had higher adsorption capacities for five estrogens with imprinting factors above 2.9. The MIPs had high extraction efficiencies, good functional properties, long lifetimes, and good reproducibility, which made them suitable for solid-phase microextraction (SPME). Coupled with ultra-high performance liquid chromatography tandem mass spectrometry, the MIP-based fibers were applied to SPME for the analysis of five estrogens in milk samples. Under the best conditions, the established method had a wide linear range (0.5-10000 ng kg-1), low limits of detection (0.08-0.26 ng kg-1) and quantification (0.26-0.87 ng kg-1), good precision (3.2-8.1%, n = 6), and fiber-to-fiber reproducibility (4.3%-8.8%, n = 3). The MIPs-based fibers can be reused at least 60 times without apparent loss of extraction efficiency. Finally, this method was applied to the determination of target estrogens in milk samples with satisfactory relative recoveries (84.3%-105%, relative standard deviation ≤ 7.8%).


Assuntos
Estrogênios/isolamento & purificação , Leite/química , Impressão Molecular , Polímeros/química , Microextração em Fase Sólida/métodos , Adsorção , Animais , Cromatografia Líquida de Alta Pressão , Estradiol/análise , Estrogênios/análise , Limite de Detecção , Reprodutibilidade dos Testes , Solventes/química , Espectrometria de Massas em Tandem
3.
Water Res ; 182: 115976, 2020 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-32622129

RESUMO

As endocrine disruptors, natural estrogens including estrone (E1), 17ß-estradiol (E2), and estriol (E3) in wastewaters of municipal wastewater treatment plant (WWTP) as well as other environmental matrix have been widely studied. However, the far-less studied natural estrogens such as 2-hydroxyestrone (2OHE1), 16α-hydroxyestrone (16α-OHE1), 4-hydroxyestrone (4OHE1), etc., found in human urine have been almost ignored. Therefore, it is important to investigate the occurrence of these far-less studied natural estrogens in municipal WWTP and other environment. In this study, a GC-MS analytical method was firstly established and validated for trace determination of eleven natural estrogens in waste and surface waters, including E1, E2, E3, 2OHE1, 16α-OHE1, 4OHE1, 2-hydroxyestradiol (2OHE2), 4-hydroxyestradiol (4OHE2), 17-epiestriol (17epiE3), 16-epiestriol (16epiE3), and 16keto-estradiol (16ketoE2). All the eleven natural estrogens were detected in the influent of one municipal WWTP, which ranged from 7.9 to 62.9 ng/L. The top five natural estrogens in the influent were E1, E3, 16α-OHE1, 16ketoE2, and 2OHE1 with respective concentrations of 62.9, 62.6, 46.9, 32.7, and 28.8 ng/L. Most of them were detected in both the effluent and river water, in which their detected concentrations were n.d-14.7 and n.d-51.7 ng/L, respectively. This work is the first to indicate that the so far less commonly studied natural estrogens in the environment likely pose adverse health effect on humans and wildlife due to their relative strong estrogenic potencies and high levels in wastewater and river water. More work should be done to understand their removals in municipal WWTPs and their occurrence in surface waters.


Assuntos
Águas Residuárias , Poluentes Químicos da Água/análise , Monitoramento Ambiental , Estradiol/análise , Estrogênios/análise , Estrona/análise , Humanos , Rios
4.
J Chromatogr A ; 1624: 461242, 2020 Aug 02.
Artigo em Inglês | MEDLINE | ID: mdl-32540080

RESUMO

Natural estrogens (estrone: E1, 17ß-estradiol: E2, estriol: E3) and the synthetic estrogen (17α-ethinylestradiol: EE2) are endocrine disruptors harmful to aquatic wildlife. The European Commission included these molecules in the surface water Watch Lists issued in 2015 and 2018 under the Water Framework Directive regarding emerging aquatic pollutants, proposing maximum detection limits (LOD) of 0.035 ng/L for EE2 and 0.4 ng/L for E1 and E2. Attaining these limits represents a challenge even with the most up-to-date analytical tools, in particular in surface water. A two-step sample preparation, involving a preliminary extraction of a whole water sample on a solid-phase extraction (SPE) disk and further purification on a Florisil SPE cartridge, was optimized. The purified extract was derivatized subsequently and quantified by LC-MS/MS. The main goal was to maximize the recoveries to achieve the very low LODs required by the European Watch Lists. The method was fully validated in seven surface water. The LODs calculated were below the maximum acceptable limits required by the European Commission.


Assuntos
Estrogênios/análise , Poluentes Químicos da Água/análise , Calibragem , Cromatografia Líquida , Disruptores Endócrinos/análise , Monitoramento Ambiental/métodos , União Europeia , Água Subterrânea/química , Limite de Detecção , Silicatos de Magnésio/isolamento & purificação , Minerais/química , Reprodutibilidade dos Testes , Extração em Fase Sólida , Espectrometria de Massas em Tandem
5.
Environ Monit Assess ; 192(7): 426, 2020 Jun 13.
Artigo em Inglês | MEDLINE | ID: mdl-32533378

RESUMO

Estrogen in streams threatens aquatic animals, especially where wastewater treatment plant (WWTP) effluent contributes to baseflow. We investigated total estrogen (E1+E2+E3) as estradiol equivalent (E2) and ethynylestradiol (EE2) concentration in Cibolo Creek (Cibolo), a groundwater-fed stream near San Antonio, TX, receiving effluent via two WWTP. We collected water samples bi-monthly from late spring to early fall 2018 in Cibolo and WWTP effluent, and used ELISA analysis and discharge measurements to determine concentrations and loads of estrogens. We measured several environmental variables to investigate what factors influenced estrogen concentrations in Cibolo downstream from WWTP inputs. Mean concentrations of WWTP effluent (E2, 41.43 ± 15.48; EE2, 11.40 ± 2.07 ng L-1) were higher compared with concentrations in Cibolo, both downstream (E2, 30.09 ± 25.85; EE2, 6.33 ± 1.92 ng L-1) and upstream (E2, 12.91 ± 11.12; EE2, 4.5 ± 1.38 ng L-1) of WWTP inputs. Both E2 and EE2 concentrations decreased downstream from WWTP inputs, a section of stream without large quantities of fine sediments for sorption, indicating potential dilution or chemical and biological degradation. Effluent into Cibolo via the first, and older, WWTP contributed the most estrogen load in Cibolo. Median concentrations of E2 and EE2 were 19 and 5 ng L-1, respectively, downstream of WWTP inputs, concentrations known to affect reproductive processes of aquatic biota and impair human health. Results suggest estrogens may pose a risk to aquatic ecosystems wherever WWTP effluent comprises a majority of baseflow, though further studies are required in this stream to verify biological impacts.


Assuntos
Águas Residuárias , Poluentes Químicos da Água/análise , Animais , Ecossistema , Monitoramento Ambiental , Estradiol/análise , Estrogênios/análise , Humanos , Eliminação de Resíduos Líquidos
6.
Chemosphere ; 256: 127122, 2020 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-32470735

RESUMO

The occurrence of hormones and hormone-like compounds in water has been regarded as an emerging environmental concern. These water contaminants are known to cause endocrine disruption that may affect aquatic organisms. In this study, hormones and phenolic xenoestrogens were investigated and measured in the surface waters of Laguna Lake, Philippines. Laguna Lake is the largest lake in the country that has many uses including fish cultivation and source for potable water production. The hormones estrone, 17-beta-estradiol, 17-alpha-ethynylestradiol, progesterone and testosterone as well as the plasticizer bisphenol A in the lake water were determined by solid phase extraction and LC-MS/MS. The extraction method exhibited good recoveries (75-90% in spiked lake water) while the instrumental method of analysis has low detection limits (0.01-0.24 µg/L) and good linear response (>99% in the 0-50 µg/L concentration range). In the nine sampling sites across the lake, estrone was found in concentrations between 0.03 and 0.30 ng/L. 17-Beta-estradiol, testosterone and progesterone were detected in some of the sites in concentrations up to 0.36, 0.22, and 2.05 ng/L, respectively. Bisphenol A was detected in all sites in higher concentrations of 0.71-47.40 ng/L. Although there are no local guidelines yet, the determination and monitoring of these emerging water contaminants are important because of their potential environmental impacts. Further to this initial study, investigations on point sources spanning the tributary rivers, long-term determination of locational and temporal variations, and assessment of ecotoxicological risks are needed. These are crucial in the regulation and mitigation of discharges into the lake.


Assuntos
Compostos Benzidrílicos/análise , Disruptores Endócrinos/análise , Monitoramento Ambiental/métodos , Hormônios/análise , Lagos/química , Fenóis/análise , Rios/química , Poluentes Químicos da Água/análise , Cromatografia Líquida/métodos , Estradiol/análise , Estrogênios/análise , Estrona/análise , Etinilestradiol/análise , Filipinas , Espectrometria de Massas em Tandem
7.
Ecotoxicol Environ Saf ; 200: 110718, 2020 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-32464437

RESUMO

Bisphenol A (BPA) has been frequently found in surface waters worldwide, and its estrogenic effects in humans are well documented. Nevertheless, less is known about other bisphenol analogues (BPs), such as bisphenol S (BPS) and bisphenol F (BPF) which are alternative to BPA. There have been few environmental investigations on BPs in developing countries, especially India. In the present study, eight BPs were analyzed, among which BPA, BPS, and BPF were found prevalent in surface water and wastewater from drains collected from 12 states and Delhi-National Capital Territory in India. The detection frequencies of BPA, BPS, and BPF were 67.6%, 41.9%, and 29.7%, respectively in all samples (n = 74). BPA was the predominant species among the three analogues. The highest BPA concentration was observed in the Yamuna River (14,800 ng/L), followed by the Cooum River (1,420 ng/L). The highest concentrations of BPS and BPF were 438 ng/L and 333 ng/L, respectively, both found in wastewater samples. The occurrence of BPS and BPF in nationwide surface water and wastewater samples from India for the first time suggests that new BPs as BPA replacements are being used and released in India. Ecological risk assessment of BPA, BPS and BPF exposure was performed using hazard quotient (HQ) for three aquatic taxonomic groups: algae, crustaceans, and fish, with the last group exhibiting the highest HQs (0.89-148) for BPA exposure. The human exposure risk of BPA through drinking river water was observed negligible in the present study. Our findings indicate the urgent need for, (1) regulations on the use and release of BPs in India, (2) effective processes to remove BPs in wastewater treatment plants, (3) more investigations on the distribution and toxicity of BPs in India, in particular BPA, BPS and BPF, as these analogues were detected at substantial concentration in Indian waters.


Assuntos
Compostos Benzidrílicos/análise , Estrogênios/análise , Fenóis/análise , Sulfonas/análise , Poluentes Químicos da Água/análise , Animais , Crustáceos , Peixes , Humanos , Índia , Medição de Risco , Rios/química , Águas Residuárias/química
8.
J Chromatogr A ; 1622: 461137, 2020 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-32414518

RESUMO

In this study, conventional Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method was modified by magnetic solid-phase extraction (MSPE) for purification/pre-concentration of eleven estrogens and estrogen mimics from the extracts of pork and chicken muscles, prior to dansyl chloride (DNS-Cl) derivatization coupled with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) assay. Dual octadecyl- and 2-aminoethyl-3-aminopropyl- groups functionalized mesoporous silica core-shell magnetic nanoparticles (C18/NH2-Fe3O4@mSiO2 MNPs) were synthesized and employed as MSPE sorbent with remarkable aqueous compatibility in comparison with conventional C18 functionalized sorbent. The proposed MSPE is easier to handle than the traditional SPE purification process in QuEChERS method. The lab-prepared MNPs were characterized by transmission electron microscope (TEM), brunner-emmet-teller (BET), dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FT-IR), thermo-gravimetric analysis (TGA) and vibrating sample magnetometer (VSM). Pre-column derivatization was conducted to significantly enhance the sensitivity of the analytes in MS/MS via analyzing their derivatives in positive ion mode instead of analyzing their original forms in negative ion mode. Under the optimal sample pretreatment and instrumental analysis conditions, the approach showed low limits of detection (LODs, 0.02‒3.00 µg kg-1), appropriate recoveries (81.1‒115.4%) and acceptable precisions (0.48‒15.1%, n = 6), with good feasibility and future prospect of trace compounds analysis in complex food samples.


Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Estrogênios/análise , Magnetismo , Carne Vermelha/análise , Extração em Fase Sólida/economia , Extração em Fase Sólida/métodos , Espectrometria de Massas em Tandem/métodos , Adsorção , Animais , Galinhas , Concentração de Íons de Hidrogênio , Limite de Detecção , Nanopartículas de Magnetita/ultraestrutura , Concentração Osmolar , Dióxido de Silício/química , Solventes , Espectroscopia de Infravermelho com Transformada de Fourier , Suínos , Fatores de Tempo
9.
Environ Pollut ; 262: 114344, 2020 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-32443213

RESUMO

The present study is the first comprehensive monitoring of 13 selected endocrine disrupting compounds (EDCs) in untreated urban and industrial wastewater in Serbia to assess their impact on the Danube River basin and associated freshwaters used as sources for drinking water production in the area. Results showed that natural and synthetic estrogens were present in surface and wastewater at concentrations ranging from 0.1 to 64.8 ng L-1. Nevertheless, they were not detected in drinking water. For alkylphenols concentrations ranged from 1.1 to 78.3 ng L-1 in wastewater and from 0.1 to 37.2 ng L-1 in surface water, while in drinking water concentrations varied from 0.4 to 7.9 ng L-1. Bisphenol A (BPA) was the most abundant compound in all water types, with frequencies of detection ranging from 57% in drinking water, to 70% in surface and 84% in wastewater. Potential environmental risks were characterized by calculating the risk quotients (RQs) and the estrogenic activity of EDCs in waste, surface and drinking water samples, as an indicator of their potential detrimental effects. RQ values of estrone (E1) and estradiol (E2) were the highest, exceeding the threshold value of 1 in 60% of wastewater samples, while in surface water E1 displayed potential risks in only two samples. Total estrogenic activity (EEQt) surpassed the threshold of 1 ng E2 L-1 in about 67% of wastewater samples, and in 3 surface water samples. In drinking water, EEQt was below 1 ng L-1 in all samples.


Assuntos
Disruptores Endócrinos/análise , Poluentes Químicos da Água/análise , Monitoramento Ambiental , Estrogênios/análise , Rios , Sérvia , Águas Residuárias
10.
Environ Pollut ; 263(Pt A): 114424, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32247920

RESUMO

Natural and synthetic steroid hormones and many persistent organic pollutants are of concern for their endocrine-disrupting activities observed in receiving surface waters. Apart from the demonstrated presence of estrogen- and estrogen-mimicking compounds in surface waters, antagonistic (anti-estrogenic) responses originating from wastewater effluent have been reported but are less known. Estrogenicity and anti-estrogenicity were assessed using recombinant yeast estrogen receptor binding assays (YES/YAES) at ten South African wastewater treatment works (WWTWs) and receiving rivers in two separate sampling campaigns during the summer- and winter periods in the area. Four WWTWs were then further investigated to show daily variation in estrogenic endocrine-disrupting activities during the treatment process. Although estrogenicity was notably reduced at most of the WWTWs, some treated effluent and river water samples were shown to be above effect-based trigger values posing an endocrine-disrupting risk for aquatic life and potential health risks for humans. Furthermore, estrogenicity recorded in samples collected upstream from some WWTW discharge points also exceeded some calculated risk trigger values, which highlights the impact of alternative pollution sources contributing towards endocrine disrupting contaminants (EDCs) in the environment. The YAES further showed variable anti-estrogenic activities in treated wastewater. The current study highlights a variety of factors that may affect bioassay outcomes and conclusions drawn from the results for risk decision-making. For example, mismatches were found between estrogenic and anti-estrogenic activity, which suggests a potential masking effect in WWTW effluents and highlights the complexity of environmental samples containing chemical mixtures having variable endocrine-disrupting modes of action. Although the recombinant yeast assay is not without its limitations to show endocrine-disrupting modulation in test water systems, it serves as a cost-effective tier-1 scoping assay for further risk characterisation and intervention.


Assuntos
Disruptores Endócrinos/análise , Poluentes Químicos da Água/análise , Bioensaio , Monitoramento Ambiental , Estrogênios/análise , Humanos , Rios , Águas Residuárias
11.
Chemosphere ; 250: 126323, 2020 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-32126332

RESUMO

This study investigated occurrence, source, and risks of endocrine disrupting chemicals (EDCs) in coastal groundwater and adjacent seawater influenced by reclaimed water irrigation in a typical coastal region of China. All target EDCs were detected in coastal groundwater and reclaimed water while only estrone, bisphenol A (BPA), and nonylphenol were detected in seawater. Concentrations of BPA that was the predominant EDC in coastal groundwater ranged from 35.9 to 52.9 ng/L and estradiol was easy to accumulate in groundwater under reclaimed water irrigation. Concentrations of all target EDCs in seawater ranged from 18.9 to 30.9 ng/L, much lower than those in groundwater. Ecological risks posed by EDCs in groundwater and seawater were very high. Estrone contributed to 51.3%-62.9% of total acute risk quotients for seawater while detected 17-α-ethynylestradiol contributed to 41.1%-56.2% of total acute risk quotients for groundwater. Estradiol equivalent concentrations of target EDCs in groundwater/seawater were in the range of (3.5-7.6)/(1.4-2.3) ng/L while non-cancer risks posed by EDCs in groundwater/seawater were acceptable. Dual-isotope analysis illustrated that reclaimed water was the main source of EDCs in coastal groundwater. About 82% of EDCs was discharged into the Laizhou Bay through the submarine groundwater discharge based on the flux analysis. The pollution of the coastal groundwater through reclaimed water irrigation subsequently led to EDCs pollution of the adjacent seawater through the submarine groundwater discharge. Therefore, effective control of EDCs in reclaimed water for irrigation will be beneficial to control EDCs in groundwater and seawater of the coastal regions.


Assuntos
Disruptores Endócrinos/análise , Monitoramento Ambiental , Poluentes Químicos da Água/análise , Compostos Benzidrílicos/análise , Estradiol/análise , Estrogênios/análise , Estrona/análise , Etinilestradiol/análise , Água Subterrânea/química , Fenóis/análise , Água do Mar/química , Águas Residuárias/análise , Águas Residuárias/química , Água/análise
12.
J Chromatogr A ; 1621: 461035, 2020 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-32188564

RESUMO

The present work described two triacontyl-bonded silica adsorbents containing different polar embedded groups (i.e. amide- and carbamate-type) for high performance liquid chromatography, which were prepared by covalent surface modification of silica gel with respective pre-synthesized polar-embedded triacontyl (C30) silane. The acylimidazole-mediated method was used for the first time for the synthesis of amide-type alkyl silane, while the carbamate-type silane was obtained via an improved solvent-free procedure. A conventional C30 stationary phase was also developed on the same silica substrate in the similar manner, which was used as a reference column for comparison of the unique mechanisms facilitated and/or furnished by the polar groups. The successful immobilization of the designed C30 species was confirmed by infrared spectroscopy and elemental analysis. In further comparison with an amide-embedded octadecyl (C18) two other conventional C18 stationary phases of different surface chemistry, detailed chromatographic characterization of the C30 series stationary phases was performed in terms of surface density, hydrophobicity, aromatic selectivity, shape selectivity and water tolerance using a diversified range of analytes, including homologous alkylbenzenes, isomeric polycyclic aromatic hydrocarbons, carotenes, congeners of polychlorobiphenyls, aromatic amines, phenolic compounds, estrogens and nucleosides. A high resemblance between the chromatographic behaviors of the two polar-modified C30 stationary phases was observed, meanwhile they demonstrated noticeable differences from non-polar C30 stationary phase. The polar-embedded C30 phases showed satisfactory performance towards the solutes of interest in the studied conditions. The beneficial synergy of the polar groups and the triacontyl chains enabled these polar-enhanced C30 stationary phases to address challenging separation tasks with high selectivity.


Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Dióxido de Silício/química , Amidas/química , Aminas/análise , Derivados de Benzeno/análise , Carbamatos/química , Carotenoides/análise , Estrogênios/análise , Interações Hidrofóbicas e Hidrofílicas , Nucleosídeos/análise , Fenóis/análise , Bifenilos Policlorados/análise , Hidrocarbonetos Policíclicos Aromáticos/análise , Silanos/química , Sílica Gel/química
13.
PLoS One ; 15(2): e0225354, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32040477

RESUMO

The North American cheetah population serves as a reservoir for the species, and acts as a research population to help understand the unique biology of the species. Little is known about the intrauterine physiology of the cheetah, including embryo differentiation, implantation, and the development of the placenta. After mating, cheetah females frequently experience (30-65% of matings) a non-pregnant luteal phase where progestogen metabolite levels match those found in pregnant females for the first ~55 days of gestation, but parturition does not occur. Immunoglobulin J chain (IgJ) is a molecule that is involved in the activation of the secretory immune response and has been found to be indicative of pregnancy in the cheetah using fecal monitoring. In this study, western blotting was employed to track IgJ abundance in pooled weekly fecal samples following natural breeding or exogenous stimulation to ovulate, and IgJ levels were compared between individuals undergoing a pregnant (n = 12) and non-pregnant (n = 19) luteal phase. It was revealed that IgJ abundance was increased in pregnant females compared to non-pregnant females at week 4 and week 8 post-breeding, indicating the potential modulation of maternal immunity in response to sensitive events such as implantation and the increased secretory activity of the placenta. IgJ levels also tended to be higher early after breeding in females that were bred naturally with intact males compared to exogenously stimulated females with no exposure to seminal plasma, potentially indicating a response to the act of intromission or the stress of breeding, or possibly demonstrating an immune response resulting in the promotion of maternal tolerance to seminal antigens present upon embryonic implantation. Monitoring fecal IgJ may be a potential method to determine gestational status in the cheetah and will aid future conservation efforts of the species.


Assuntos
Acinonyx/fisiologia , Cadeias J de Imunoglobulina/análise , Gravidez/imunologia , Reprodução/imunologia , Animais , Animais de Zoológico , Biomarcadores/análise , Biomarcadores/metabolismo , Estrogênios/análise , Fezes/química , Feminino , Cadeias J de Imunoglobulina/metabolismo , Fase Luteal/imunologia , Masculino , Indução da Ovulação , Progestinas/análise , Sêmen , Comportamento Sexual Animal , Estados Unidos
14.
Chemosphere ; 247: 125907, 2020 May.
Artigo em Inglês | MEDLINE | ID: mdl-31978658

RESUMO

Coastal waters are the critical ecologically fragile regions under the influence of the fastest economic developing pace and the extensive anthropogenic activities in coastal zone. Little information on the seasonal distribution, risks, and sources of endocrine disrupting chemicals (EDCs) which are emerging contaminants to pose potential risks at very low concentrations in coastal waters at continental-scale is available. This study investigated the coastline-based distribution, risks, and sources of target EDCs in coastal water of China. EDCs in coastal waters of China showed significant spatio-temporal variation with phenolic compounds serving as predominant EDCs. Bisphenol A (BPA) was detected in all water samples with average concentration of 449.2/186.3 ng/L in winter/summer while estrone was the main steroidal estrogen with the average concentration of 87.2/2.7 ng/L in winter/summer. EDCs in coastal waters of South China Sea Area showed higher concentrations. EDCs in coastal waters exerted high ecological risks and estrone/BPA averagely accounted for over 61%/71% of total risk quotient in winter/summer. Average estradiol equivalent concentration of all target EDCs reached 68.87/1.76 ng/L in winter/summer. EDCs in coastal waters did not pose potential non-cancer health risks for humans. The positive matrix factorization (PMF) model was firstly used to identify and quantify possible sources of EDCs. The PMF analysis showed that wastewater and sewage might be the main source for EDCs in coastal waters. EDCs in coastal waters showed high estradiol equivalent concentration and ecological risks at continental-scale, highlighting that EDCs contamination has become a crucial stress affecting the sustainable development of coastal regions.


Assuntos
Disruptores Endócrinos/análise , Monitoramento Ambiental , Poluentes Químicos da Água/análise , Compostos Benzidrílicos , China , Estradiol/análise , Estrogênios/análise , Estrona/análise , Humanos , Fenóis , Medição de Risco , Estações do Ano , Esgotos/química , Águas Residuárias/análise , Poluição Química da Água/estatística & dados numéricos
15.
Environ Monit Assess ; 192(2): 114, 2020 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-31940101

RESUMO

17ß-Estradiol (E2) is a natural estrogen produced by the feminine endocrine system. It is excreted mainly through urine and feces. Exposure to E2 may affect the reproductive system of both animals and humans, especially since the removal of E2 in conventional processes and technologies present in the wastewater treatment plants is not sufficient. Chlorine is one of the most studied and used oxidant worldwide. Although there are studies that demonstrate the endocrine disrupting compounds removal like E2, its reaction with organic matter can originate by-products, namely, trihalomethanes, which are known to have high toxic potential. The main aim of the present study was to evaluate the removal of E2 (50 µg E2 L-1-maximum concentration) using peracetic acid (PAA), a seeming cleaner and innocuous alternative to chlorine. To this end, a series of jar tests were performed, using different peracetic acid concentrations (1, 5, 10, and 15 mg L-1) and contact times (10, 15, and 20 min). The results obtained showed that a peracetic acid concentration of 15 mg L-1 with a contact time of 20 min had a removal efficacy of approximately 100%. The second main goal of this study was to evaluate the ecotoxicological potential of the tested treatments on the zebrafish Danio rerio. Several oxidative stress biomarkers were evaluated, namely glutathione S-transferase, lipid peroxidation, and catalase, besides vitellogenin. Both peracetic acid and E2 caused significant increases in the oxidative stress biomarkers, although this did not lead to increased lipid peroxidation levels. In addition, peracetic acid significantly decreased the estrogenic activity of E2, as indicated by decreased vitellogenin levels. Peracetic acid demonstrated to have great potential as an alternative disinfectant for chlorine treatments, and indications for future research are discussed.


Assuntos
Monitoramento Ambiental , Estrogênios/análise , Ácido Peracético/química , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/análise , Animais , Cloro , Desinfetantes , Disruptores Endócrinos/análise , Estradiol/análise , Estrona , Humanos , Trialometanos , Vitelogeninas , Águas Residuárias
16.
Talanta ; 209: 120542, 2020 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-31891994

RESUMO

Several magnetic ionic liquids (MILs), [P6,6,6,14+][FeCl4-], [P6,6,6,14+]2[MnCl42-], [P6,6,6,14+]2[CoCl42-] and [P6,6,6,14+]2[NiCl42-] were synthesized and applied for the extraction of six estrogens (estrone, estradiol, 17-α-hydroxyprogesterone, chloromadinone 17-acetate, megestrol 17-acetate and medroxyprogesterone 17-acetate) in dispersive liquid-liquid microextraction (DLLME). The [CoCl42-]-based MIL was selected as extraction solvent for the separation and concentration of estrogens from milk and cosmetics due to its visual recognition, no sign of hydrolysis, solution acquisition easier and the highest extraction capacity. In addition, the [CoCl42-]-based MIL with low UV absorbance allows direct analysis of the extraction solvent by HPLC-UV. The influence of the mass of MIL, extraction time, salt concentration, and the pH of the sample solution was investigated to obtain optimized extraction efficiency. Besides, extraction conditions including salt concentration, mass of MIL and extraction time were further optimized by the Box-Behnken design through the response surface method. Under optimized conditions, the limits of detection (LODs) of all estrogens were ranged from 5 ng mL-1 to 15 ng mL-1. The recoveries ranging from 98.5% to 109.3% in milk and from 96.3% to 111.4% in cosmetics were also studied, respectively. Furthermore, the proposed method were statistically compared with the reported conventional IL-DLLME method and the National standard methods of food safety and cosmetics. The experimental results showed that the functionalized MIL could successfully applied for extraction, separation and pretreatment of estrogens in milk and cosmetics.


Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Cosméticos/análise , Estrogênios/análise , Líquidos Iônicos/química , Leite/química , Animais , Cromatografia Líquida de Alta Pressão/economia , Limite de Detecção , Imãs/química , Fatores de Tempo
17.
Arch Pathol Lab Med ; 144(5): 545-563, 2020 05.
Artigo em Inglês | MEDLINE | ID: mdl-31928354

RESUMO

PURPOSE.­: To update key recommendations of the American Society of Clinical Oncology/College of American Pathologists estrogen receptor (ER) and progesterone receptor (PgR) testing in breast cancer guideline. METHODS.­: A multidisciplinary international Expert Panel was convened to update the clinical practice guideline recommendations informed by a systematic review of the medical literature. RECOMMENDATIONS.­: The Expert Panel continues to recommend ER testing of invasive breast cancers by validated immunohistochemistry as the standard for predicting which patients may benefit from endocrine therapy, and no other assays are recommended for this purpose. Breast cancer samples with 1% to 100% of tumor nuclei positive should be interpreted as ER positive. However, the Expert Panel acknowledges that there are limited data on endocrine therapy benefit for cancers with 1% to 10% of cells staining ER positive. Samples with these results should be reported using a new reporting category, ER Low Positive, with a recommended comment. A sample is considered ER negative if < 1% or 0% of tumor cell nuclei are immunoreactive. Additional strategies recommended to promote optimal performance, interpretation, and reporting of cases with an initial low to no ER staining result include establishing a laboratory-specific standard operating procedure describing additional steps used by the laboratory to confirm/adjudicate results. The status of controls should be reported for cases with 0% to 10% staining. Similar principles apply to PgR testing, which is used primarily for prognostic purposes in the setting of an ER-positive cancer. Testing of ductal carcinoma in situ (DCIS) for ER is recommended to determine potential benefit of endocrine therapies to reduce risk of future breast cancer, while testing DCIS for PgR is considered optional. Additional information can be found at www.asco.org/breast-cancer-guidelines .


Assuntos
Neoplasias da Mama/patologia , Carcinoma Intraductal não Infiltrante/patologia , Estrogênios/análise , Receptores de Progesterona/análise , American Medical Association , Neoplasias da Mama/diagnóstico , Carcinoma Intraductal não Infiltrante/diagnóstico , Feminino , Humanos , Imuno-Histoquímica , Oncologia , Patologistas , Patologia Clínica , Prognóstico , Estados Unidos
18.
Sci Total Environ ; 704: 135277, 2020 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-31831230

RESUMO

The occurrence of endocrine disrupting chemicals (EDCs) in swimming pool waters has been scarcely investigated. In this study, the concentrations of 20 EDCs (4 phenols, 6 estrogens, 4 progestogens, 5 androgens, and 1 pharmaceutical) in 40 outdoor and indoor swimming pools in Changsha, China were investigated. Out of them, two phenols (bisphenol A and 4-tert-octylphenol), three estrogens (17ß-estradiol, 17ɑ-ethinlestradiol (EE2), and hexestrol), one pharmaceutical (caffeine), and two progestogens (progesterone and levonorgestrel) were detected in the collected samples. The androgens were not detected. Bisphenol A and caffeine were the dominant EDCs at concentrations of ND-23.22 ng/L and ND-39.08 ng/L, respectively. The levels of caffeine were significantly higher in indoor swimming pools (11.15 ng/L in average) than those in outdoor pools (1.90 ng/L in average) (p < 0.05), owing to the less sun's UV radiation and less use of sunscreens containing caffeine. The progestogens (progesterone and levonorgestrel) and estrogens (17ß-estradiol and hexestrol) were only detected in outdoor swimming pools. The detection frequencies and concentrations of bisphenol A and caffeine in downtown pools were significantly higher than those in outskirt pools. Besides, the correlations between the concentrations of EDCs and water quality parameters evaluated by the Spearman correlation analysis implied that residual chlorine had strong oxidant capable to bisphenol A and suggested that caffeine could be a potential indicator of organic contamination in swimming pool water. Finally, a quantitative risk assessment revealed that non-athletic child and athletic adult female were vulnerable subpopulations. The EDItotal of EE2 for athletic child, non-athletic female, non-athletic male, and non-athletic child were higher than ADIEE2 adopted by Australia and the EDItotal of EE2 for athletic female and athletic male were higher than ADIEE2 adopted by the United States.


Assuntos
Disruptores Endócrinos/análise , Monitoramento Ambiental , Piscinas , Poluentes Químicos da Água/análise , Compostos Benzidrílicos , China , Estradiol/análise , Estrogênios/análise , Estrona/análise , Fenóis , Progestinas/análise , Medição de Risco
19.
Environ Pollut ; 257: 113636, 2020 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-31780365

RESUMO

Little is known about sediment-bound exposure of fish to endocrine disrupting chemicals (EDC) under field conditions. This study aimed to investigate potential routes of EDC exposure to fish and whether sediment-bound contaminants contribute towards exposure in fish. Tench (Tinca tinca) and roach (Rutilus rutilus) as a benthic and pelagic living fish species, respectively, were sampled at the Luppe River, previously described as a "hotspot" for accumulation of EDC in sediment. A field reference site, the Laucha River, additionally to fish from a commercial fish farm as reference were studied. Blackworms, Lumbriculus variegatus, which are a source of prey for fish, were exposed to sediment of the Luppe River and estrogenic activity of worm tissue was investigated using in vitro bioassays. A 153-fold greater estrogenic activity was measured using in vitro bioassays in sediment of the Luppe River compared the Laucha River. Nonylphenol (NP; 22 mg/kg) was previously identified as one of the main drivers of estrogenic activity in Luppe sediment. Estrogenic activity of Luppe exposed worm tissue (14 ng 17ß-estradiol equivalents/mg) indicated that food might act as secondary source to EDCs. While there were no differences in concentrations of NP in plasma of tench from the Luppe and Laucha, vitellogenin, a biomarker for exposure to EDCs, was induced in male tench and roach from the Luppe River compared to both the Laucha and cultured fish by a factor of 264 and 90, respectively. However, no histological alterations in testis of these fish were observed. Our findings suggest that sediments substantially contribute to the overall EDC exposure of both benthic and pelagic fish but that the exposure did not impact gonad status of the fish.


Assuntos
Disruptores Endócrinos , Estrogênios , Peixes , Sedimentos Geológicos , Poluentes Químicos da Água , Animais , Disruptores Endócrinos/análise , Estrogênios/análise , Estrogênios/toxicidade , Água Doce/química , Sedimentos Geológicos/química , Masculino , Rios
20.
Environ Pollut ; 256: 113384, 2020 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-31677876

RESUMO

Although livestock manure, such as from swine (Sus scrofa domestica), have high capacity to introduce endocrine-disrupting free estrogens into the environment, the frequency of estrogen detections from reconnaissance studies suggest that these compounds are ubiquitous in the environment, perhaps resulting from historic manure inputs (e.g. cattle grazing residues, undocumented historic manure applications) or uncontrolled natural sources. Compared to free estrogens, conjugates of estrogens are innocuous but have greater mobility in the environment. Estrogen conjugates can also hydrolyze to re-form the potent free estrogens. The objective of this study was to identify the transport of free and conjugated estrogens to subsurface tile drains and groundwater beneath fields treated with swine manure slurry. Three field treatments were established, two receiving swine lagoon manure slurry and one with none. Manure slurry was injected into soils at a shallow depth (∼8 cm) and water samples from tile drains and shallow wells were sampled periodically for three years. Glucuronide and sulfate conjugates of 17ß-estradiol (E2) and estrone (E1) were the only estrogen compounds detected in the tile drains (total detects = 31; 5% detection frequency; conc. range = 3.9-23.1 ng L-1), indicating the important role conjugates played in the mobility of estrogens. Free estrogens and estrogen conjugates were more frequently detected in the wells compared to the tile drains (total detects = 70; 11% detection frequency; conc. range = 4.0-1.6 × 103 ng L-1). No correlations were found between estrogen compound detections and dissolved or colloidal organic carbon (OC) fractions or other water quality parameters. Estrogenic compounds were detected beneath both manure treated and non-treated plots; furthermore, the total potential estrogenic equivalents (i.e. estrogenicity of hydrolyzed conjugates + free estrogens) were similar between treated and non-treated plots.


Assuntos
Disruptores Endócrinos/análise , Estrogênios Conjugados (USP)/análise , Estrogênios/análise , Água Subterrânea/química , Esterco/análise , Águas Residuárias/química , Animais , Bioensaio , Bovinos , Estradiol/análise , Estrona/análise , Gado , Solo/química , Suínos
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