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1.
Mar Pollut Bull ; 142: 576-580, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-31232341

RESUMO

Estrogen levels were assessed in surface sediments from one of the most industrialized and urbanized estuarine systems in Latin America (SSES, Santos and São Vicente estuarine system). Estriol (E3) presented quantifiable levels in all sampled sites, ranging from 20.9 ng g-1 to 694.2 ng g-1. 17ß-estradiol (E2) and 17α-ethinylestradiol (EE2) were also detected in almost all sampled sites. The highest concentration of E2 was 23.9 ng g-1, whereas high levels of EE2 86.3 ng g-1. The occurrence of estrogens in SSES was diffuse and partially related to a domestic sewage outfall. Estrogens were also found in areas with substantial contribution of sanitary effluents from domiciles not covered by sanitation services. Our results reinforce that studies on environmental contamination by estrogens should not be spatially limited to the vicinities of point sources. These results contribute to raise awareness on the need of a formal approach to assess ecological risks of estrogens in the SSES.


Assuntos
Estrogênios/análise , Sedimentos Geológicos/análise , Poluentes Químicos da Água/análise , Brasil , Disruptores Endócrinos/análise , Estradiol/análise , Estriol/análise , Estuários , Etinilestradiol/análise , Esgotos
2.
Environ Pollut ; 246: 914-920, 2019 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-31159141

RESUMO

Pharmaceuticals and analogs of bisphenol A (BPA) are increasingly threatening environmental pollutants. In this study, mixtures of selected pharmaceuticals (diclofenac sodium salt, chloramphenicol, oxytetracycline hydrochloride, fluoxetine hydrochloride, estrone, ketoprofen, progesterone, gemfibrozil and androstenedione) were prepared with BPA and its two analogs (namely, bisphenols F and S) at such ratios to reflect environmentally detectable levels. Then, the mixture solutions were studied with a XenoScreen YES/YAS assay to determine the variations in the initial hormonal response of each pharmaceutical compound due to the presence of a bisphenol analog. The results obtained were modeled with the concentration addition (CA) and independent action (IA) approaches, the trueness of which was studied with model deviation ratios (MDR). The estrogenic agonistic activity of the drugs studied was most strongly affected by the presence of BPA in solution (twenty-one cases of synergy observed for CA models versus twelve cases of antagonism in the case of IA predictions). BPS shows a strong agonistic estrogenic impact on most of the drugs studied at medium and high concentration levels; androgenic agonistic activity was also impaired with elevated concentrations of BPS. Increasing the concentration of BPF in a reaction mixture also increased the number of YES + synergism incidences (for CA modeling). Estrone, progesterone and androstenedione were mostly affected by the highest BPF concentrations studied in the case of androgenic agonistic research performed.


Assuntos
Compostos Benzidrílicos/toxicidade , Disruptores Endócrinos/toxicidade , Poluentes Ambientais/toxicidade , Preparações Farmacêuticas/análise , Fenóis/toxicidade , Saccharomyces cerevisiae/efeitos dos fármacos , Androgênios/análise , Compostos Benzidrílicos/química , Bioensaio , Disruptores Endócrinos/química , Poluentes Ambientais/química , Estrogênios/análise , Fenóis/química , Testes de Toxicidade
3.
Sci Total Environ ; 678: 448-456, 2019 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-31077923

RESUMO

This study reports the performance of a carbon nanotube (CNT) electrochemical filter applied to 17ß-estradiol (E2) and 17α-ethinylestradiol (EE2) degradation and their estrogenic activity removal (calculated in terms of E2 equivalent, EQ-E2). The performance of CNT electrochemical filter was assessed at different applied voltages (0-2.5 V) and aqueous matrices (ultrapure water and urban wastewater), using 37 µM of E2 and EE2, a flow rate of 1.5 mL min-1 and 10 mM of Na2SO4, used as supporting electrolyte. Surface characterization of CNT anodic filters was completed by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV) was used to investigate electron transfer mechanisms. The CNT electrochemical filter was successfully applied to E2 and EE2 degradation and removals higher than 95.3% (oxidative fluxes >2.94 ±â€¯0.05 mmol h-1 m-2) were achieved when 2.5 V was applied for both ultrapure water and urban wastewater. CV results indicate that the oxidation in the CNT electrochemical filter is an irreversible process. SEM and XPS results showed evidence of the polymer formation on the CNT surface after 300 min of reaction, which probably reduced the efficiency of the process under low applied voltages. Estrogenic activity was considerably reduced and minimal EQ-E2 levels were observed when 2.5 V was applied. A residual EQ-E2 was observed, likely due to the presence of estrogens, which suggests the non-formation of estrogenic intermediates. At 2.5 V total cell potential, the energy required to remove estrogenic activity was 0.014 ±â€¯0.001 kWh m-3 for ultrapure water and 0.021 ±â€¯0.001 kWh m-3 for post-secondary wastewater. These results suggest a CNT electrochemical filter may have potential to effectively and efficiently remove estrogenic activity and may be a feasible process for wastewater polishing treatment.


Assuntos
Estradiol/análise , Estrogênios/análise , Etinilestradiol/análise , Nanotubos de Carbono/química , Eliminação de Resíduos Líquidos/instrumentação , Poluentes Químicos da Água/análise , Técnicas Eletroquímicas , Filtração , Eliminação de Resíduos Líquidos/métodos
4.
Environ Pollut ; 248: 1067-1078, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-31091639

RESUMO

Estrogenic endocrine disrupting chemicals (EDCs) are natural hormones, synthetic compounds or industrial chemicals that mimic estrogens due to their structural similarity with estrogen's functional moieties. They typically enter aquatic environments through wastewater treatment plant effluents or runoff from intensive livestock operations. Globally, most natural and synthetic estrogens in receiving aquatic environments are in the low ng/L range, while industrial chemicals (such as bisphenol A, nonylphenol and octylphenol) are present in the µg to low mg/L range. These environmental concentrations often exceed laboratory-based predicted no effect concentrations (PNECs) and have been evidenced to cause negative reproductive impacts on resident aquatic biota. In vertebrates, such as fish, a well-established indicator of estrogen-mediated endocrine disruption is overexpression of the egg yolk protein precursor vitellogenin (Vtg) in males. Although the vertebrate Vtg has high sensitivity and specificity to estrogens, and the molecular basis of its estrogen inducibility has been well studied, there is growing ethical concern over the use of vertebrate animals for contaminant monitoring. The potential utility of the invertebrate Vtg as a biomonitor for environmental estrogens has therefore gained increasing attention. Here we review evidence providing support that the molluscan Vtg holds promise as an invertebrate biomarker for exposure to estrogens. Unlike vertebrates, estrogen signalling in invertebrates remains largely unclarified and the classical genomic pathway only partially explains estrogen-mediated activation of Vtg. In light of this, in the latter part of this review, we summarise recent progress towards understanding the molecular mechanisms underlying the activation of the molluscan Vtg gene by estrogens and present a hypothetical model of the interplay between genomic and non-genomic pathways in the transcriptional regulation of the gene.


Assuntos
Disruptores Endócrinos/análise , Moluscos/metabolismo , Vitelogeninas/análise , Poluentes Químicos da Água/análise , Poluição da Água/análise , Animais , Compostos Benzidrílicos/análise , Biomarcadores/análise , Disruptores Endócrinos/toxicidade , Estrogênios/análise , Estrona/análise , Feminino , Peixes/metabolismo , Masculino , Fenóis/análise , Receptores Estrogênicos/metabolismo , Reprodução , Poluentes Químicos da Água/toxicidade
5.
Environ Pollut ; 250: 1010-1018, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-31085467

RESUMO

There is increasing concern about phenolic environmental estrogens (PEEs) in river systems, especially in economically developed regions, because of their potential to impact ecological systems. We studied the distribution of, ecological risks from, and factors that influenced PEEs in the sediments from the Duliujian River in the Beijing-Tianjin-Hebei Urban Agglomeration and the Pearl River in Guangdong Province in China. The three target PEEs, nonyl phenol (4-NP), octyl phenol (4-t-OP), and bisphenol A (BPA), were detected in the sediments at concentrations ranging from 204.4 to 12604.3, 32.6 to 297.3, and from 12.8 to 298.4 ng g-1 in the Pearl River, and from 153.5 to 3614.9, 90.7 to 990.0, and 83.5-913.3 ng g-1 in the Duliujian River, respectively. The PEE concentrations were significantly and positively correlated with total organic carbon in the river sediments (p < 0.1). Urbanization influenced the distribution of PEEs and applications and discharges of PEEs were associated with large populations and industries. Rainfall and wastewater discharge patterns also influenced how PEEs were distributed in river sediments. The potential ecological risks from 4-NP, 4-t-OP, and BPA in these two rivers were high. Measures should be put in place to control the transport and storage of these compounds in river systems.


Assuntos
Compostos Benzidrílicos/análise , Estrogênios/análise , Sedimentos Geológicos/química , Fenóis/análise , Rios/química , Pequim , China , Ecologia , Monitoramento Ambiental/métodos , Urbanização , Águas Residuárias/química , Poluentes Químicos da Água/análise
6.
Talanta ; 200: 316-323, 2019 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-31036191

RESUMO

In this study, an ASE (Accelerated Solvent extraction)-SPE (Solid Phase Extraction)-GC/MS(SIM) method for the simultaneous determination of five non-steroidal anti-inflammatory drugs (NSAIDs: ibuprofen (IBU), paracetamol (PAR), diclofenac (DIC), naproxen (NAP) and ketoprofen (KET)) and three natural estrogens (estrone (E1), 17ß-estradiol (E2), estriol (E3)) in mussels was proposed, which is simple, cheap and easy for use in environmental laboratories. For the first time, the sorbents: PSA (Primary Secondary Amine) and FLORISIL®, placed directly inside the extraction cells, were used for the improvement of the ASE procedure for the isolation of these pollutants from mussel samples. The application of FLORISIL® especially allowed the purification of the extract to increase recovery, without the loss of analytes, or prolongation of the extraction time. The proposed ASE-SPE-GC/MS(SIM) method was validated (the method detection limit values were in the range of 1 ng/g dry weight (d.w.) for IBU to 7 ng/g d.w. for E1; the measurement intermediate precision was between 0.24% and 7.85%; the mean recovery was in the range of 80-118%) and used for the determination of NSAIDs and estrogenic hormones in whole tissue of the mussels Mytilus edulis trossulus collected from the Gulf of Gdansk (southern Baltic Sea). IBU, NAP, DIC and E1 were determined in these samples; however, the pharmaceuticals were found only in smaller (with a length of 2-3 cm) individuals. The observed differences in the concentrations of CEC in smaller and older mussel organisms were fully discussed. Summarizing, this method could be used for monitoring these CEC in such organisms in order to expand our knowledge of their influence on the water ecosystem, however, in such investigations smaller mussel organisms should be used.


Assuntos
Anti-Inflamatórios não Esteroides/análise , Produtos Biológicos/análise , Estrogênios/análise , Animais , Mytilus edulis , Extração em Fase Sólida
7.
Int J Mol Sci ; 20(7)2019 Apr 08.
Artigo em Inglês | MEDLINE | ID: mdl-30965663

RESUMO

Small fish are an excellent experimental model to screen endocrine-disrupting compounds, but current fish-based assays to detect endocrine disruption have not been standardized yet, meaning that there is not consensus on endpoints and biomarkers to be measured. Moreover, exposure conditions may vary depending on the species used as the experimental model and the endocrine pathway evaluated. At present, a battery of a wide range of assays is usually needed for the complete assessment of endocrine activities. With the aim of providing a simple, robust, and fast assay to assess endocrine-disrupting potencies for the three major endocrine axes, i.e., estrogens, androgens, and thyroid, we propose the use of a panel of eight gene expression biomarkers in zebrafish larvae. This includes brain aromatase (cyp19a1b) and vitellogenin 1 (vtg1) for estrogens, cytosolic sulfotransferase 2 family 2 (sult2st3) and cytochrome P450 2k22 (cyp2k22) for androgens, and thyroid peroxidase (tpo), transthyretin (ttr), thyroid receptor α (trα), and iodothyronine deiodinase 2 (dio2) for thyroid metabolism. All of them were selected according to their responses after exposure to the natural ligands 17ß-estradiol, testosterone, and 3,3',5-triiodo-L-thyronine (T3), respectively, and subsequently validated using compounds reported as endocrine disruptors in previous studies. Cross-talk effects were also evaluated for all compounds.


Assuntos
Bioensaio/métodos , Disruptores Endócrinos/toxicidade , Transcriptoma/genética , Androgênios/análise , Animais , Sistema Endócrino/efeitos dos fármacos , Sistema Endócrino/metabolismo , Estrogênios/análise , Regulação da Expressão Gênica no Desenvolvimento/efeitos dos fármacos , Regulação da Expressão Gênica no Desenvolvimento/genética , Peixe-Zebra
8.
Environ Sci Pollut Res Int ; 26(16): 16800-16813, 2019 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-31001778

RESUMO

An integrated manure treatment system, including a mixed algal-bacterial bioreactor (MABB) and hydrothermal processing of biomass solids, was found to remove 76.4-97.0% of the total estrogenic hormones (estrone (E1), 17ß-estradiol (E2), and estriol (E3)) from the liquid portion of animal manure (LPAM). The mixed biomass was converted into either biocrude oil with a yield up to 40% via hydrothermal liquefaction (HTL) or syngas with a yield up to 54% yield via catalytic hydrothermal gasification (CHG). Adding granular activated carbon (GAC) in the MABB enhanced the removal of estrogenic hormones (+ 7.2%), cytotoxicity (+ 58%), and heavy metals (+ 10.5%). After the integrated system with the MABB, HTL, and CHG processes, the overall percent removal of heavy metals from the LPAM ranged from 27.1 to 40.3%. The concentrations of potentially toxic heavy metals (lead (Pb), copper (Cu), zinc (Zn), cadmium (Cd), nickel (Ni), chromium (Cr)) in the aqueous phase after HTL and CHG tests ranged from 0.01 to 25.3 mg/L.


Assuntos
Biocombustíveis/análise , Reatores Biológicos/microbiologia , Estrogênios/análise , Esterco/análise , Eliminação de Resíduos Líquidos/métodos , Qualidade da Água , Animais , Biomassa , Carvão Vegetal/química , Metais Pesados/análise , Suínos , Águas Residuárias/química , Poluentes Químicos da Água/análise
9.
Chemosphere ; 227: 334-344, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-30999174

RESUMO

Some recent studies showed that in vitro bioassays based on fish or human estrogen receptor (ER) activation may have distinct responses to environmental samples, highlighting the need to better understand bioassay-specific ER response to environmental mixtures. For this purpose, we investigated a 12-compound mixture in two mixture ratios (M1 and M2) on zebrafish (zf) liver cells stably expressing zfERα (ZELHα cells) or zfERß2 (ZELHß2 cells) and on human ER-reporter gene (MELN) cells. The mixture included the well-known ER ligands bisphenol A (BPA) and genistein (GEN), and other compounds representatives of a freshwater background contamination. In this context, the study aimed at assessing the robustness of concentration addition (CA) model and the potential confounding influence of other chemicals by testing subgroups of ER activators, ER inhibitors or ER activators and inhibitors combined. Individual chemical testing showed a higher prevalence of ER inhibitors in zebrafish than human cells (e.g. propiconazole), and some chemicals inhibited zfER but activated hER response (e.g. benzo(a)pyrene, triphenylphosphate). The estrogenic activity of M1 and M2 was well predicted by CA in MELN cells, whereas it was significantly lower than predicted in ZELHß2 cells, contrasting with the additive effects observed for BPA and GEN binary mixtures. When testing the subgroups of ER activators and inhibitors combined, the deviation from additivity in ZELHß2 cells was caused by zebrafish-specific inhibiting chemicals. This study provides novel information on the ability of environmental pollutants to interfere with zfER signalling and shows that non-estrogenic chemicals can influence the response to a mixture of xeno-estrogens in a bioassay-specific manner.


Assuntos
Estrogênios/análise , Receptores Estrogênicos/efeitos dos fármacos , Animais , Compostos Benzidrílicos/farmacologia , Bioensaio/métodos , Linhagem Celular , Estrogênios/química , Feminino , Genisteína/farmacologia , Humanos , Ligantes , Fígado/citologia , Fenóis/farmacologia , Receptores Estrogênicos/antagonistas & inibidores , Peixe-Zebra , Proteínas de Peixe-Zebra/genética
10.
Chemosphere ; 224: 480-486, 2019 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-30831499

RESUMO

Estrogens are of environmental concern because disruptive effect on biological functions at levels as low as ng/L. Wastewater treatment plant effluent is a significant source of estrogens in aquatic environment. Ferric ions (Fe3+)-saturated montmorillonite has been shown to effectively remove 17ß-estradiol (ßE2), a common estrogen, from pure water by catalyzing formation of insoluble ßE2 oligomers on mineral surfaces. We investigated the effects of reaction temperature, dissolved organic matter, pH, and common cations, on Fe3+-saturated montmorillonite-surface catalyzed ßE2 polymerization, and the removal of this estrogen from three different secondary wastewater effluents with more complicated matrixes. Highest ßE2 removal occurred at near neutral pH and it increased with increasing treatment temperatures. Presence of common cations in the water did not affect the reaction efficiency. Dissolved organic matter at 15 mg C/L slightly lowered the ßE2 removal efficiency as compared to that in pure water. Regardless of the source of wastewater effluents, ßE2 removal efficiency of ∼40% was achieved using the dosage of Fe3+-saturated montmorillonite similar to that tested for the aqueous phases with simpler matrix. Doubling this dosage resulted in removal of ∼80% of ßE2 from a tested secondary wastewater effluent within 30 min reaction. For wastewater with complex matrixes at the commonly reported ßE2 levels which are magnitudes lower than the tested concentration in our study, this dosage would provide sufficient available reaction sites for the surface-catalyzed ßE2 polymerization. This study demonstrated that Fe3+-saturated montmorillonite is a promising material for effective removal of phenolic estrogen compounds from domestic wastewater effluents.


Assuntos
Bentonita/química , Estradiol/análise , Estrogênios/análise , Ferro/química , Eliminação de Resíduos Líquidos/métodos , Águas Residuárias/química , Poluentes Químicos da Água/análise , Catálise
11.
Ecotoxicol Environ Saf ; 173: 45-53, 2019 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-30763810

RESUMO

Herein we investigated the multi-phase distribution and estrogenic effects of endocrine disrupting chemicals (EDCs) in suspended particulate matter (SPM), colloids, and soluble phases from the Shaying River to assess the composition of estrogenic compounds and associated estrogenic risk. The yeast two hybrid (YES) method, cross-flow ultrafiltration (CFUF), and LC-MS/MS were employed. Risk quotient (RQ) values ranged from 0.72 to 3.88, revealing that the Shaying River posed high estrogenic risk to aquatic organisms. The contribution ratios of the target EDCs to the EEQYES ranged from 62.7% to 92.5%, indicating that these chemicals were major contributors of estrogenic effects in the Shaying River. Further, 54.0-77.8% of the detected EDCs were distributed in the soluble phase, 15.1-31.7% were bound to colloidal substances, and 3.90-19.4% EDCs were associated with SPM. Significant correlation between total EDC abundance and COD contents was detected, and the concentrations of endogenous estrogens (E1, E2, and E3) were positively correlated with total nitrogen (TN) and total phosphorus (TP). In addition, the in-situ SPM-soluble (Kpoc) and colloid-soluble partition (Kcoc) coefficients were calculated. The log Kpoc values of target compounds varied from 4.10 to 5.19, while log Kcoc values ranged from 4.25 to 5.56. Their Kcoc values were larger than the Kpoc values, indicating that organic colloids were the most important carriers of EDCs in the aquatic environment.


Assuntos
Disruptores Endócrinos/análise , Estrogênios/análise , Rios/química , Poluentes Químicos da Água/análise , Organismos Aquáticos , China , Coloides/química , Disruptores Endócrinos/química , Monitoramento Ambiental , Estrogênios/química , Material Particulado/química , Medição de Risco , Poluentes Químicos da Água/química
12.
Mikrochim Acta ; 186(3): 165, 2019 02 09.
Artigo em Inglês | MEDLINE | ID: mdl-30739225

RESUMO

A seamless two-step extraction procedure integrating ultrasound-assisted emulsification microextraction (USAEME) and vortex-assisted micro-solid-phase extraction (µ-SPE) was developed. A highly porous metal-organic framework of type MIL-101(Cr) is used as the sorbent, and ultra-high-performance liquid chromatography in combination with tandem mass spectrometry is used for detection. The steroid hormones estrone 17ß-estradiol, estriol, and 17α-ethynylestradiol were extracted from water samples by using this method. These steroids are polar and do not pass through the polypropylene membrane that is conventionally used in µ-SPE. In the method presented here, 1-octanol is used in USAEME to extract and pre-concentrate the steroids. This facilitates the transfer to the MIL-101(Cr) phase retained by the membrane in the subsequent µ-SPE step. MIL-101(Cr) was characterized by various methods, and the parameters affecting the overall extraction efficiency were optimized. Under the most favorable conditions, the limits of detection are between 0.95 and 23 ng L-1. Good intra-day and inter-day precisions were obtained, with relative standard deviations of ≤ 9.9%. Enrichment factors are between 34 and 52. The method was applied to genuine environmental water samples in which estrone was detected. Relative recoveries ranged between 85.4% and 120.8%. Graphical abstract Schematic of the emulsification-assisted micro-solid-phase extraction (µ-SPE). By emulsifying 1-octanol in the water sample, polar estrogens dissolved in the solvent can easily pass the hydrophobic polypropylene membrane and then are adsorbed onto the unmodified MIL-101(Cr) held within the µ-SPE device.


Assuntos
Estrogênios/análise , Estruturas Metalorgânicas , Microextração em Fase Sólida/métodos , Poluição Química da Água/análise , Cromatografia Líquida de Alta Pressão , Interações Hidrofóbicas e Hidrofílicas , Limite de Detecção , Reprodutibilidade dos Testes , Espectrometria de Massas em Tandem
13.
Ecotoxicology ; 28(2): 143-153, 2019 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-30612255

RESUMO

Estrogens have been widely detected in water and might pose a potential threat to the aquatic ecosystem. However, little information is available about the occurrence, multi-phase fate and potential risks of estrogens in Hanjiang River (HR). In this work, the concentration, multi-phase distribution and risk assessment of eight estrogens were studied by investigating surface water and sediment samples from HR during two seasons. These samples were analyzed using the solid-phase extraction (SPE) and liquid chromatography-mass spectrometry (LC-MS). The concentrations of eight estrogens were 4.5-111 ng/l in surface water and 1.7-113 ng/g dry weight in sediments. 4-nonylphenol (NP) was the predominant estrogen in both water and sediments. The estrogens showed significantly spatial variability, with the highest average concentration in the lower section of HR (p < 0.01, F > 12.21). Meanwhile, NP, 17α-estradiol (αE2), Bisphenol A (BPA) and 4-tert-octyphenol (OP) in surface water exhibited higher concentrations in summer than in winter (p < 0.05, F > 4.62). The sediment-water partition coefficients of estrogens suggested that these compounds partitioned more to particulate phase. Risk assessment indicated that estriol (E3) was the main contributor to the total estradiol equivalent concentration. Moreover, estrogen mixtures could pose high ecological risks to aquatic organisms in surface water. Overall, estrogens are ubiquitous in HR, and their potential ecological risks should not be neglected.


Assuntos
Monitoramento Ambiental , Estrogênios/toxicidade , Sedimentos Geológicos/química , Rios/química , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/toxicidade , China , Cromatografia Líquida , Estrogênios/análise , Estrogênios/química , Espectrometria de Massas , Medição de Risco , Extração em Fase Sólida , Poluentes Químicos da Água/química
14.
Aquat Toxicol ; 208: 157-167, 2019 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-30677711

RESUMO

Environmental estrogens are a serious concern worldwide due to their ubiquity and adverse ecotoxicological and health effects. Chemical structure of these substances is highly diverse, therefore estrogenicity cannot be predicted on the basis of molecular structure. Furthermore, estimation of estrogenicity of environmental samples based on chemical analytics of suspects is difficult given the complex interaction of chemicals and the impact on estrogenicity. The full estrogenic impact of an environmental sample can thus only be revealed by a series of sensitive in vitro and in vivo ecotoxicological tests. Herein we describe a vitellogenin reporter transgenic zebrafish line (Tg(vtg1:mCherry)) that enables the detection of estrogenicity in the environmentally relevant, low concentration ranges in embryonic tests that are in accordance with 3Rs and relevant animal welfare regulations. The transgene construct used for the development of Tg(vtg1:mCherry) carried a long (3.4 kbp) natural vitellogenin-1 promoter sequence with a high number of ERE sites. A test protocol was developed based on our finding that the endogenous vitellogenin and the reporter show similar spatial expression pattern and both endogenous and vitellogenin reporter is only produced in the left hepatic lobe of 5 dpf zebrafish embryos. Seven generations of Tg(vtg1:mCherry) have been established, and the estrogen responsiveness was tested with different estrogenic substances and wastewater samples. Embryos were exposed from 3 to 5 days post fertilization (dpf). Fluorescence in embryos could be detected upon treatment with 17-ß-estradiol from a concentration of 100 ng/L, 17-α-ethynilestradiol from 1 ng/L, zearalenone from 100 ng/L and bisphenol-A from 1 mg/L. In the adult stage transgene activity appeared to be more sensitive to estrogen treatment, with detectable transgene activity from 5 ng/L 17-ß-estradiol concentration. The transgenic line Tg(vtg1:mCherry) was also suitable for the direct measurement of estrogenicity in wastewater samples without sample extraction. The detection of estrogenic activity using the reporter line was confirmed by the bioluminescent yeast estrogen screen.


Assuntos
Estrogênios/análise , Fígado/metabolismo , Vitelogeninas/metabolismo , Proteínas de Peixe-Zebra/metabolismo , Peixe-Zebra/genética , Animais , Animais Geneticamente Modificados , Biomarcadores/metabolismo , Embrião não Mamífero/metabolismo , Estradiol/metabolismo , Fluorescência , Heterozigoto , Homozigoto , Fígado/efeitos dos fármacos , Masculino , Elementos de Resposta/genética , Transgenes , Águas Residuárias/química , Poluentes Químicos da Água/análise , Peixe-Zebra/embriologia
15.
Talanta ; 195: 290-297, 2019 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-30625545

RESUMO

Herein, a robust and homogeneous porous poly(3,4-ethylenedioxythiophene)/graphene (PEDOT/graphene) thin film surface-assisted laser desorption/ionization (SALDI) functional platform was prepared through a rapid and facile in-situ photopolymerization method. The graphene-embedded PEDOT skeleton well circumvented the aggregation-related problems in the traditional carbon-based SALDI method which combined with time-of-flight mass spectrometer (TOF MS). As a result, the reproducibility and quantitative capacity of the SALDI platform were significantly improved. Furthermore, the highly efficient adsorption performance of the PEDOT/graphene thin film was demonstrated in terms of in vitro and in vivo solid-phase microextraction (SPME) extraction. It showed that porous morphology with abundant graphene doping favored the adsorption and enrichment of target analytes. Owing to the excellent adsorption capability of the PEDOT/graphene thin film and the inherent strong laser absorption ability of graphene, expected SALDI effect (3-13 times higher than the commercial nanomaterial-assisted LDI plate) and quantitative analysis (linear range 0.5-100 µg L-1) of the PEDOT/graphene functional surfaces were achieved. As for the real-world applications, we deployed the PEDOT/graphene thin film SALDI platform for the analysis of five estrogens in biological samples at microliter-volume level, without tedious sample preparation procedures. Satisfactory recoveries ranging from 60.6% to 99.0% were obtained. The present study suggested that the graphene-embedded PEDOT skeleton with porous morphology would be developed as promising coating for the adsorption of analytes of interest. Additionally, the combination of PEDOT with graphene not only expanded the application fields of PEDOT, but also offered an efficient strategy for preparing homogeneous functional surfaces to realize the quantitative analysis in SALDI method.


Assuntos
Compostos Bicíclicos Heterocíclicos com Pontes/química , Estrogênios/análise , Grafite/química , Polímeros/química , Adsorção , Animais , Bovinos , Estrogênios/química , Humanos , Músculos/química , Microextração em Fase Sólida , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz , Tilápia
16.
Sci Total Environ ; 658: 1013-1022, 2019 Mar 25.
Artigo em Inglês | MEDLINE | ID: mdl-30677966

RESUMO

Recently, hydrochar (HC) with existed persistent free radicals (PFRs) has attracted researches' attention for the potential application in heterogeneous Fenton-like reactions, but studies on the interactive effects of H2O2, iron, and HC in removal of organic pollutants are still limited. In this paper, magnetic iron (hydr)oxides immobilized hydrochar composite (Fe/HC) derived from hydrothermal carbon (HTC) of pinewood were synthesized and characterized. The interactive effects of H2O2, iron, and HC in the removal of several estrogens were systematically investigated to understand the removal performance and related mechanism, especially at a pH range close to natural water environment. Batch experiments results showed that estrogens could be efficiently removed over Fe/HC material under a wide pH range of 4-9. Based on the analysis of electron spin resonance, X-ray photoelectron spectroscopy, Mössbauer spectroscopy, and electrochemical impedance spectroscopy, mechanism study indicated that the carbon-centered PFRs on the surface of hydrochar can act as electron donors, and transfer the electrons on adsorbed O2 to generate O2- rapidly, while the addition of H2O2 enhanced the transmission ability of electron to produce OH(ads) on the material surface. The iron and hydrochar components contributed to the desirable removal of estrogens via the synergistic effect between catalysis and adsorption. This study provides a promising application for the use of Fe/HC materials on remediation of pollution with trace estrogens in water environment.


Assuntos
Carvão Vegetal/química , Estrogênios/análise , Peróxido de Hidrogênio/química , Ferro/química , Eliminação de Resíduos Líquidos/métodos , Águas Residuárias/análise , Madeira/química , Radicais Livres/química , Pinus/química
17.
Sci Total Environ ; 657: 1246-1252, 2019 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-30677891

RESUMO

Wastewater treatment plant (WWTP) effluents release complex mixtures of organic and inorganic micropollutants, including endocrine disrupting compounds, into receiving water bodies. These substances may cause adverse effects in aquatic communities as well as in ecosystem functions they provide. The aim of this study was to determine the potential impact of secondary treated wastewater released into a small Swiss stream on leaf litter decomposition based on feeding rates of the amphipod shredder Gammarus fossarum measured in situ. Additionally, endocrine disrupting effects downstream of the WWTP were investigated by measuring vitellogenin (vg) induction in male gammarids exposed in situ, as well as estrogen receptor activation using the Yeast Estrogen Screen (YES) involving passive sampler and grab water sample extracts. Extracts were also analysed for 424 organic micropollutants and selected transformation products. Gammarid feeding rate was significantly reduced 100, 200 and 400 m downstream of the WWTP effluent relative to the upstream site. While YES results showed significantly elevated estrogenicity at downstream sites, vg production in male gammarids was not induced. A laboratory experiment, in which gammarids were exposed to WWTP effluent, supported this observation. These results, hence, suggest that treated wastewater released into aquatic ecosystems impairs the ecosystem function of leaf litter decomposition. Vg levels in male gammarids measured by UPLC-MS/MS did, however, not alter.


Assuntos
Anfípodes/efeitos dos fármacos , Anfípodes/fisiologia , Vitelogeninas/metabolismo , Águas Residuárias/toxicidade , Animais , Ingestão de Alimentos/efeitos dos fármacos , Ecotoxicologia/métodos , Biomarcadores Ambientais , Estrogênios/análise , Suíça , Vitelogeninas/análise , Poluentes Químicos da Água/toxicidade , Qualidade da Água
18.
Talanta ; 194: 852-858, 2019 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-30609615

RESUMO

In this work, we present a method for the clean-up, preconcentration and quantification of the four most widely found estrogens (estrone E1, estradiol E2, estriol E3 and ethynyl estradiol EE2) in seawater samples. A sequential injection analysis-lab on valve system (SIA-LOV) has been developed to perform the microsolid phase extraction (µSPE) of the analytes in a fully automated way. After testing different resins and solvents, C18 resin with acetonitrile (ACN) as eluent have been chosen as they provided the best results. Several parameters affecting the extraction have been studied and optimized. Besides, extraction column lifetime has also been checked as it is indicative of the number of consecutive analysis that the column is able to perform before replacing it. Results showed that the same column can be used up to 50 times. Then, the derivatization of the extracts has been performed unattended by exploiting an in-port derivatization of the analytes with N-methyltrimethylsilyltrifluoroacetamide (BSTFA) prior their quantification using large volume injection with programmable temperature vaporization gas chromatography (LVI-PTV-GC-MS).


Assuntos
Métodos Analíticos de Preparação de Amostras/métodos , Cromatografia Gasosa , Estrogênios/análise , Temperatura Ambiente , Estrogênios/química , Estrogênios/isolamento & purificação , Concentração de Íons de Hidrogênio , Injeções , Análise Multivariada , Resinas Sintéticas/química , Água do Mar/química , Extração em Fase Sólida , Volatilização
19.
Chemosphere ; 221: 99-106, 2019 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-30634153

RESUMO

Paperboard used as packaging, a non-inert material, can transfer chemicals into food. Over the years, endocrine disrupting compounds (EDCs), such as NonylPhenols (NPs), BisPhenol A (BPA) and phthalates have been shown to migrate from packaging materials into food. Due to chronic exposure and mixture effects of these EDCs, they could cause health effects even at very low doses. Many EDCs are still unknown and many more are still unregulated. The ERE-CALUX bioassay was used as a bioanalytical tool to investigate estrogenic activities of paperboard food packaging and its characteristics, including recycling rate and printing ink. A "worst case" scenario with full extraction is compared to a dry food migration experiment. By measuring an overall estrogenic activity, known and unknown estrogenic chemicals and mixture effects are taken into account and the data are compared to molecule specific analysis. Estrogenic activities ranged from 682 ±â€¯66 pg E2 eq./dm2 to 3250 ±â€¯400 pg E2 eq./dm2 for "worst case" extraction and from 347 ±â€¯30 pg E2 eq./dm2 to 1350 ±â€¯70 pg E2 eq./dm2 for migration experiments. A two-factor ANOVA revealed a relationship between estrogenic activity and the recycling rate of the paperboard, but no significant difference with printing ink was observed for these paperboard samples. Bis(2-ethylhexyl)phthalate (DEHP), dibutyl phthalate (DBP), butyl benzyl phthalate (BBP) and 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH) were determined in all extraction and migrations experiment samples. A Spearman rank correlation analysis showed a relationship between the estrogenic activity and the total phthalates as well as with each compound individually.


Assuntos
Bioensaio/métodos , Disruptores Endócrinos/análise , Estrogênios/análise , Embalagem de Alimentos , Dibutilftalato/análise , Exposição Ambiental/efeitos adversos , Humanos , Ácidos Ftálicos/análise , Reciclagem
20.
Chemosphere ; 220: 766-773, 2019 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-30611075

RESUMO

Cypermethrin (CP) is a kind of chiral pesticides that has been defined as endocrine disrupting chemical. The diversity in bioactivity, toxicity, metabolism, bioaccumulation, and degradation behaviors of CP enantiomers as well as the research deficiency had made the risk assessment of CP enantiomers very complicated. Herein, four CP enantiomers were separated as target chemicals to investigate their enantioselective endocrine disrupting effects. Firstly, dual-luciferase reporter gene assays were adopted to investigate their potential endocrine disrupting effects via various receptors. The expression levels of steroid hormones related genes and hormone secretion levels in H295R cell were measured to verify the results. Results from the reporter gene assay showed that 1R-cis-αS-CP (CP11) exhibited glucocorticoid receptor (GR), mineralocorticoid receptor (MR), and thyroid receptor (TR) antagonistic activity with the RIC20 values of 9.22 × 10-7, 3.33 × 10-7, and 4.47 × 10-7 M, respectively; 1R-trans-αS-CP (CP21) also showed androgen receptor (AR) agonist activity and estrogen receptor (ER) antagonistic activity with the REC20 and RIC20 values were 1.07 × 10-4 M and 4.78 × 10-6 M, respectively. Results of qRT-PCR and hormone measurement also showed that CP11 and CP21 could disturb the expression of steroid hormones related genes and hormone secretion accordingly. Results provided here can help to understand the enantioselective ecological and health risks of CP enantiomers comprehensively and provide constructive guidance for the safe use of chiral pesticides and the invention of green pesticides.


Assuntos
Disruptores Endócrinos/farmacologia , Piretrinas/farmacologia , Estereoisomerismo , Androgênios/análise , Linhagem Celular , Estrogênios/análise , Genes Reporter , Humanos , Praguicidas/química , Praguicidas/farmacologia , Piretrinas/química , Receptores de Glucocorticoides/efeitos dos fármacos , Receptores de Mineralocorticoides/efeitos dos fármacos
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