RESUMO
Nitrite (NO2-)-sensitized photolysis plays an important role in the attenuation of effluent-derived trace organic contaminants (e.g., anilines, phenolic compounds, etc.) in surface waters. However, the kinetics, mechanisms, and influencing factors of photolysis of many emerging contaminants sensitized by NO2- still remain largely unknown. Herein, we report that NO2--sensitized photolysis of the antimicrobial agents parachlormetaxylenol (PCMX) and chlorophene (CP) in aqueous solution under ultraviolet 365 nm (UV365) radiation. A nonlinear increase in photolysis rate constants of PCMX and CP was observed with increasing NO2- concentration. Radical quenching studies and kinetic modeling revealed that hydroxyl radical (HOâ¢) and nitrogen dioxide radicals (NO2â¢) contributed dominantly to the removal of PCMX and CP. Solid phase extraction (SPE) combined with high resolution-mass spectrometry (HR-MS) analysis identified a series of intermediate products including hydroxylated, nitrated, nitrosated, and dimerized derivatives. Experiments with isotopically labelled nitrite (15NO2-) showed that the nitro- and nitroso-substituents of intermediate products were derived from the nitrite nitrogen. Based on the identified products and theoretical computations, the mechanisms and pathways of NO2--sensitized photolysis of PCMX and CP are elucidated. Deoxygenation partially inhibited the formation of 4-chloro-3,5-dimethyl-2-nitrophenol (nitro-PCMX) while the presence of HO⢠scavenger such as isopropanol (i-PrOH) suppressed the further transformation of nitro-PCMX. The presence of Mississippi River natural organic matter (MRNOM) inhibited the removal of PCMX and CP, likely due to light screening and radical quenching. However, appreciable degradation of PCMX and CP was still observed in wastewater and wetland water matrices. Results of this study shed some light on the transformation and fate of PCMX and CP in NO2--rich wastewater effluents or effluent-impacted surface waters under solar radiation.
Assuntos
Anti-Infecciosos , Poluentes Químicos da Água , Diclorofeno/análogos & derivados , Mississippi , Nitritos , Fotólise , Água , Poluentes Químicos da Água/análiseRESUMO
Chlorophene is an important antimicrobial agent present in disinfectant products which has been related to health and environmental effects, and its detection has been limited to chromatographic techniques. Thus, there is a lack of research that attempts to develop new analytical tools, such as biosensors, that address the detection of this emerging pollutant. Therefore, a new biosensor for the direct detection of chlorophene in real water is presented, based on surface plasmon resonance (SPR) and using a laccase enzyme as a recognition element. The biosensor chip was obtained by covalent immobilization of the laccase on a gold-coated surface through carbodiimide esters. The analytical parameters accomplished resulted in a limit of detection and quantification of 0.33 mg/L and 1.10 mg/L, respectively, fulfilling the concentrations that have already been detected in environmental samples. During the natural river's measurements, no significant matrix effects were observed, obtaining a recovery percentage of 109.21% ± 7.08, which suggested that the method was suitable for the fast and straightforward analysis of this contaminant. Finally, the SPR measurements were validated with an HPLC method, which demonstrated no significant difference in terms of precision and accuracy, leading to the conclusion that the biosensor reflects its potential as an alternative analytical tool for the monitoring of chlorophene in aquatic environments.
Assuntos
Técnicas Biossensoriais , Diclorofeno/análogos & derivados , Anti-Infecciosos , Carbodi-Imidas/análise , Diclorofeno/análise , Ouro , Limite de Detecção , Ressonância de Plasmônio de SuperfícieRESUMO
Mineral-humic complexes, known as mineral-associated organic matter (MAOM), are ubiquitous in natural waters. However, the interaction between organic pollutants and MAOM remains elusive, which may affect their degradation process. In this study, photochemical transformation of chlorophene (CP) in the presence of MAOM, prepared by coating aluminum hydroxide with humic acid (HA-HAO), was investigated. Our results showed that the degradation of CP was significantly enhanced in the presence of HA-HAO, and the degradation rate constant was ~5 times as that with HA only. It was because the adsorption of CP to HA-HAO particles was greatly enhanced, and concentration of reactive oxygen species (ROS) was increased on HA-HAO surfaces, which further promoted the reactions between CP and ROS. The quenching experiments combined with EPR technology confirmed that superoxide anion (O2·-) was the primary reactive radical on CP photodegradation. More importantly, the degradation of CP with HA-HAO followed a hydroxylation process, rather than the oligomerization reaction with HA only. Spectroscopic analysis provided direct evidence for the formation of hydrogen bonding between CP phenolic hydroxyl group and surface oxygen of HAO, which would suppress the reactivity of phenolic hydroxyl group, consequently the ortho- and meta-positions of CP became more facile for the hydroxylation reaction. This study shows the importance of MAOM in altering the photochemical behavior and transformation pathway of organic contaminants.
Assuntos
Diclorofeno , Poluentes Químicos da Água , Hidróxido de Alumínio , Diclorofeno/análogos & derivados , Substâncias Húmicas/análise , Fotólise , Poluentes Químicos da Água/análiseRESUMO
BACKGROUND: Endocrine-disrupting chemicals can interfere with hormonal homeostasis and have adverse effects for both humans and the environment. Their identification is increasingly difficult due to lack of adequate toxicological tests. This difficulty is particularly problematic for cosmetic ingredients, because in vivo testing is now banned completely in the European Union. OBJECTIVES: The aim was to identify candidate preservatives as endocrine disruptors by in silico methods and to confirm endocrine receptors' activities through nuclear receptors in vitro. METHODS: We screened preservatives listed in Annex V in the European Union Regulation on cosmetic products to predict their binding to nuclear receptors using the Endocrine Disruptome and VirtualToxLab™ version 5.8 in silico tools. Five candidate preservatives were further evaluated for androgen receptor (AR), estrogen receptor (ERα), glucocorticoid receptor (GR), and thyroid receptor (TR) agonist and antagonist activities in cell-based luciferase reporter assays in vitro in AR-EcoScreen, hERα-HeLa-9903, MDA-kb2, and GH3.TRE-Luc cell lines. Additionally, assays to test for false positives were used (nonspecific luciferase gene induction and luciferase inhibition). RESULTS: Triclocarban had agonist activity on AR and ERα at 1µM and antagonist activity on GR at 5µM and TR at 1µM. Triclosan showed antagonist effects on AR, ERα, GR at 10µM and TR at 5µM, and bromochlorophene at 1µM (AR and TR) and at 10µM (ERα and GR). AR antagonist activity of chlorophene was observed [inhibitory concentration at 50% (IC50) IC50=2.4µM], as for its substantial ERα agonist at >5µM and TR antagonist activity at 10µM. Climbazole showed AR antagonist (IC50=13.6µM), ERα agonist at >10µM, and TR antagonist activity at 10µM. DISCUSSION: These data support the concerns of regulatory authorities about the endocrine-disrupting potential of preservatives. These data also define the need to further determine their effects on the endocrine system and the need to reassess the risks they pose to human health and the environment. https://doi.org/10.1289/EHP6596.
Assuntos
Disruptores Endócrinos/toxicidade , Receptores Androgênicos/efeitos dos fármacos , Receptores de Estrogênio/efeitos dos fármacos , Receptores de Glucocorticoides/efeitos dos fármacos , Antagonistas de Receptores de Andrógenos , Carbanilidas/toxicidade , Linhagem Celular , Simulação por Computador , Diclorofeno/análogos & derivados , Diclorofeno/toxicidade , Genes Reporter , Humanos , Imidazóis/toxicidade , Triclosan/toxicidadeRESUMO
Increasing attention has been attracted in developing new technologies to remove chlorofene (CF) and dichlorofene (DCF), which were active agents in antimicrobials for general cleaning and disinfecting. This study investigated the significant influences of bicarbonate (HCO3-) on the degradation of CF and DCF in the Cu(II)-mediated Fenton-like system Cu2+/H2O2. Our results indicate that HCO3- may play a dual role to act 1) as a ligand to stabilize Cu(II), forming soluble [CuII(HCO3-)(S)]+ species to catalyze H2O2 producing hydroxyl radical (OH) and superoxide ion (O2-) and 2) as a OH scavenger. Furthermore, the reaction kinetics, mechanisms, and intermediates of CF and DCF were assessed. The apparent rate constants of CF and DCF were enhanced by a factor of 8.5 and 5.5, respectively, in the presence of HCO3- at the optimized concentration of 4â¯mM. Based on the intermediate identification and frontier electron densities (FEDs) calculations, the associated reaction pathways were tentatively proposed, including C-C scission, single or multiple hydroxylation, and coupling reaction. In addition, significant reduction in the aquatic toxicity of CF and DCF was observed after treatment with Cu2+/H2O2-HCO3- system, evaluated by Ecological Structure Activity Relationships (ECOSAR) program. These findings provide new insights into Cu(II)-mediated reactions to better understand the environmental fate of organic contaminants in carbonate-rich waters.
Assuntos
Antibacterianos/química , Bicarbonatos/química , Clorofenóis/química , Cobre/química , Diclorofeno/análogos & derivados , Desinfetantes/química , Recuperação e Remediação Ambiental/métodos , Hidrocarbonetos Halogenados/química , Fenol/química , Carbonatos/química , Diclorofeno/química , Peróxido de Hidrogênio/química , Radical Hidroxila/química , Ferro/química , Cinética , OxirreduçãoRESUMO
Potassium ferrate [Fe(VI)] is a promising oxidant widely used in water treatment for the elimination of organic pollutants. In this work, the reaction kinetics, products, and mechanisms of the antimicrobial agent chlorophene (CP) undergoing Fe(VI) oxidation in aqueous solutions were investigated. CP is very readily degraded by Fe(VI), with the apparent second-order rate constant, k, being 423.2 M-1 s-1 at pH 8.0. A total of 22 oxidation products were identified using liquid chromatography-quadrupole time-of-flight-mass spectrometry , and their structures were further elucidated using tandem mass spectrometry. According to the extracted peak areas in mass spectra, the main reaction products were the coupling products (dimers, trimers, and tetramers) that formed via single-electron coupling. Theoretical calculations demonstrated that hydrogen abstraction should easily occur at the hydroxyl group to produce reactive CP· radicals for subsequent polymerization. Cleavage of the C-C bridge bond, electrophilic substitution, hydroxylation, ring opening, and decarboxylation were also observed during the Fe(VI) oxidation process. In addition, the degradation of CP by Fe(VI) was also effective in real waters, which provides a basis for potential applications.
Assuntos
Diclorofeno , Poluentes Químicos da Água , Purificação da Água , Diclorofeno/análogos & derivados , Elétrons , Ferro , Cinética , OxirreduçãoRESUMO
Reaction with soluble Mn(II) has been considered as a main decay pathway for superoxide in natural waters, accompanied by an important Mn redox cycling. In this study, the interaction of Mn(II) and humic acid (HA) was investigated in visible light irradiated water. Our results indicate that HA may play a dual role to act as a photosensitizer to produce superoxide anions (O2-) and as a strong ligand to stabilize the Mn(III), forming soluble Mn(III)L species for substrate transformation. Furthermore, the reaction kinetics, products, and mechanisms of chlorophene (CP) and estradiol (E2) mixture in the Mn(II)/HA/visible light reaction systems were assessed. The removal of CP and E2 was enhanced by 24.3% and 13.2%, respectively, in mixture solution at initial concentration of 1.0 µM for each target contaminant, as compared to the case of single-compound degradation. Product identification and density functional theory calculations indicated that cross-coupling reaction of CP and E2 radicals was more likely to occur than the self-coupling reaction in mixture solution. In addition, estrogenic activities of initial reaction solution were also effectively decreased during the transformation process. These findings provide new insights into Mn(III)-mediated reactions to better understand the environmental fate of organic contaminant mixture in waters.
Assuntos
Substâncias Húmicas , Poluentes Químicos da Água , Diclorofeno/análogos & derivados , Estradiol , Cinética , OxirreduçãoRESUMO
This paper evaluates the oxidation of an antibacterial agent, chlorophene (4-chloro-2-(phenylmethyl)phenol, CP), by permanganate (Mn(VII)) in water. Second-order rate constant (k) for the reaction between Mn(VII) and CP was measured as (2.05⯱â¯0.05)â¯×â¯101â¯M-1â¯s-1 at pH 7.0 for an initial CP concentration of 20.0⯵M and Mn(VII) concentration of 60.0⯵M. The value of k decreased with increasing pH in the pH range of 5.0-7.0, and then increased with an increase in solution pH from 7.0 to 10.0. The presence of MnO2 and Fe3+ in water generally enhanced the removal of CP, while the effect of humic acid was not obvious. Fourteen oxidation products of CP were identified by an electrospray time-of-flight mass spectrometer, and direct oxidation, ring-opening, and decarboxylation were mainly observed in the reaction process. The initial reaction sites of CP by Mn(VII) oxidation were rationalized by density functional theory calculations. Toxicity changes of the reaction solutions were assessed by the luminescent bacteria P. phosphoreum, and the intermediate products posed a relatively low ecological risk during the degradation process. The efficient removal of CP in secondary clarifier effluent and river water demonstrated the potential application of this Mn(VII) oxidation method in water treatment.
Assuntos
Antibacterianos/química , Diclorofeno/análogos & derivados , Compostos de Manganês/química , Óxidos/química , Poluentes Químicos da Água/química , Antibacterianos/toxicidade , Diclorofeno/química , Diclorofeno/toxicidade , Cinética , Espectrometria de Massas , Oxirredução , Photobacterium/efeitos dos fármacos , Rios , Poluentes Químicos da Água/toxicidade , Purificação da Água/métodosRESUMO
An analytical method for determining the presence and levels of residual active ingredients found in neutralized suspensions of phenolic and quaternary ammonium salt-based antimicrobial products was developed using solid-phase extraction in combination with LC-tandem MS. A single-laboratory validation of the method was performed at three concentration levels for the quaternary ammonium compounds (also referred to as benzalkonium chlorides or BACs) and the phenols in the presence of letheen broth neutralizer at 2.5 and 2.75 µg/mL, respectively, as well as at dilutions of 1:10 and 1:100 in those concentrations. The method's lowest LODs were 0.005 µg/g for BACs and 0.006 µg/g for phenols. The average recovery of the fortified samples for both active ingredients ranged between 80 and 124%, and RSDs were generally <20%. In a related study, the effectiveness of letheen broth with and without sodium thiosulfate was evaluated as a neutralizer for sodium hypochlorite. The results showed that letheen broth without sodium thiosulfate neutralizes chlorine concentrations up to 60 ppm, and that 200 µg sodium thiosulfate are required to neutralize a 72 ppm concentrated chlorine solution in letheen broth.
Assuntos
Anti-Infecciosos/análise , Compostos de Benzalcônio/análise , Compostos de Bifenilo/análise , Diclorofeno/análogos & derivados , Cromatografia por Troca Iônica/métodos , Meios de Cultura/química , Diclorofeno/análise , Lipídeos/química , Fenóis/química , Hipoclorito de Sódio/química , Espectrometria de Massas em Tandem/métodos , Tiossulfatos/químicaRESUMO
As active agents in cleaning and disinfecting products, antimicrobials have been widely spread in the environment and have drawn extensive attention as potential threats to the ecological system and human health. In this study, the laccase-catalyzed removal of two emerging antimicrobials, chlorophene (CP) and dichlorophen (DCP), was investigated under simulated environmental conditions. Intrinsic reaction kinetics showed that the removal of CP and DCP followed second-order reaction kinetics, first-order with respect to both the enzyme and the substrate concentration. It was also found that fulvic acid could suppress the transformation of CP and DCP by reversing the oxidation reactions through its action as a scavenger of the free radical intermediates produced from reactions between laccase and the substrates. Several reaction products were identified by a quadrupole time-of-flight mass spectrometer, and detailed reaction pathways were proposed. For both CP and DCP, direct polymerization was the principal pathway, and the coupling patterns were further corroborated based on molecular modeling. The nucleophilic substitution of chlorine by the hydroxyl group was observed, and further oxidation products capable of coupling with each other were also found. Additionally, toxicity evaluation tests using Scenedesmus obliquus confirmed that the toxicity of CP and DCP was effectively eliminated during the reaction processes.
Assuntos
Anti-Infecciosos/análise , Diclorofeno/análogos & derivados , Lacase/química , Scenedesmus/efeitos dos fármacos , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Anti-Infecciosos/toxicidade , Catálise , Diclorofeno/análise , Diclorofeno/toxicidade , Cinética , Poluentes Químicos da Água/toxicidadeRESUMO
Summer Gut Syndrome (SGS) is caused by various Vibrio bacterial species and can have negative effects on aquaculture farms worldwide. In New Zealand, SGS is caused by Vibrio harveyii infecting King Salmon (Oncorhynchus tshawytscha). To find leads for the prevention of SGS, we screened the inhibitory effects of 16 strains of Shewanella upon V. harveyii growth in competitive solid phase cultures. The detailed investigation of Shewanella halifaxensis IRL548 revealed 2-benzyl-4-chlorophenol (1), a known, commercially available antibacterial agent, as the major bioactive component. Synthesis of a small library of congeners to confirm the natural product identity and to provide a structure-activity relationship for the observed activity was also completed. Compound 1 exhibits moderate activity against two pathogenic microorganisms.
Assuntos
Antibacterianos/farmacologia , Diclorofeno/análogos & derivados , Shewanella/química , Bibliotecas de Moléculas Pequenas/farmacologia , Vibrionaceae/efeitos dos fármacos , Antibacterianos/síntese química , Antibacterianos/química , Diclorofeno/química , Diclorofeno/metabolismo , Diclorofeno/farmacologia , Relação Dose-Resposta a Droga , Testes de Sensibilidade Microbiana , Estrutura Molecular , Shewanella/metabolismo , Bibliotecas de Moléculas Pequenas/química , Bibliotecas de Moléculas Pequenas/metabolismo , Relação Estrutura-Atividade , Vibrioses/tratamento farmacológicoRESUMO
Chlorophene-loaded nanospheres with various formulation parameters were evaluated. The optimal formulation was found at 0.1% w/v of poloxamer 407, 15 mL of ethyl acetate and 20% initial chlorophene loading that provided the suitable size (179 nm), the highest loading content (19.2%), encapsulation efficiency (88.0%) and yield (91.6%). Moreover, encapsulation of chlorophene in nanospheres was able to prolong and sustain drug release over one month. Chlorophene-loaded nanospheres were effective against Staphylococcus aureus (S. aureus) and Candida albicans (C. albicans), the main cause of hospital-acquired infections. Chlorophene-loaded nanospheres were effective against S. aureus (>46 µg/mL) and C. albicans (>184 µg/mL). These nanospheres appeared to have profound effect on the time-dependent hemolytic activity due to gradual release of chlorophene. At the concentration of 46 µg/mL, nearly no HRBC hemolysis in 24 h compared to 80% of hemolysis from free drug. In conclusion, polymeric nanospheres were successfully fabricated to encapsulate chlorophene which can eliminate inherent toxicity of drugs and have potential uses in prolonged release of antimicrobial.
Assuntos
Anti-Infecciosos/síntese química , Diclorofeno/análogos & derivados , Sistemas de Liberação de Medicamentos/métodos , Nanosferas/química , Anti-Infecciosos/administração & dosagem , Candida albicans/efeitos dos fármacos , Candida albicans/fisiologia , Química Farmacêutica , Preparações de Ação Retardada , Diclorofeno/administração & dosagem , Diclorofeno/síntese química , Relação Dose-Resposta a Droga , Humanos , Testes de Sensibilidade Microbiana/métodos , Nanosferas/administração & dosagem , Staphylococcus aureus/efeitos dos fármacos , Staphylococcus aureus/fisiologiaRESUMO
An innovative strategy integrating the use of biosurfactant (BS) and persulphate activated by chelated iron for the decontamination of soil from an emerging pollutant chlorophene was studied in laboratory down-flow columns along with other persulphate activation aids including combined application of persulphate and hydrogen peroxide, and persulphate activation with sodium hydroxide. Although BS addition improved chlorophene removal by the persulphate treatment, the addition of chelated iron did not have a significant influence. Combined application of persulphate with hydrogen peroxide resulted in a significant (p≤.05) overall improvement of chlorophene removal compared with treatment with persulphate only. The highest removal rate (71%) of chlorophene was achieved with the base-activated persulphate, but only in the upper part (of 0.0-3.5â cm in depth) of the column. The chemicals at the applied dosages did not substantially influence the Daphnia magna toxicity of the effluent. Dehydrogenase activity (DHA) measurements indicated no substantial changes in the microbial activity during the persulphate treatment. The highest oxygen consumption and a slight increase in DHA were observed with the BS addition. The combined application of persulphate and BS at natural soil pH is a promising method for chlorophene-contaminated soil remediation. Hydroquinone was identified among the by-products of chlorophene degradation.
Assuntos
Diclorofeno/análogos & derivados , Recuperação e Remediação Ambiental/métodos , Poluentes do Solo/isolamento & purificação , Solo/química , Sulfatos/química , Tensoativos/química , Diclorofeno/química , Diclorofeno/isolamento & purificação , Peróxido de Hidrogênio/química , Poluentes do Solo/químicaRESUMO
The photolysis of five frequent emerging contaminants (Benzotriazole, Chlorophene, N,N-diethyl-m-toluamide or DEET, Methylindole, and Nortriptyline HCl) was investigated in ultrapure water under monochromatic ultraviolet radiation at 254 nm and by a combination of UV and hydrogen peroxide. The results revealed that the photolysis rates followed first-order kinetics, with rate constant values depending on the nature of the specific compound, the pH, and the presence or absence of the scavenger tert-butanol. Quantum yields were also determined and values in the range of 53.8 × 10⻳ - 9.4 × 10⻳ mol E⻹ for Benzotriazole, 525 × 10⻳ - 469 × 10⻳ mol E⻹ for Chlorophene, 2.8 × 10⻳ - 0.9 × 10⻳ mol E⻹ for DEET, 108 × 10⻳ - 165 × 10⻳ mol E⻹ for Methylindole, and 13.8 × 10⻳ - 15.0 × 10⻳ mol E⻹ for Nortriptyline were obtained. The study also found that the UV/H2O2 process enhanced the oxidation rate in comparison to direct photolysis. High-performance liquid chromatography coupled to electrospray ionization quadrupole time-of-flight mass spectrometry (HPLC-ESI-QTOF-MS) technique was applied to the concentrations evaluation and further identification of the parent compounds and their by-products, which allowed the proposal of the degradation pathways for each compound. Finally, in order to assess the aquatic toxicity in the photodegradation of these compounds, the Vibrio fischeri acute toxicity test was used, and the results indicated an initial increase of this parameter in all cases, followed by a decrease in the specific case of Benzotriazole, DEET, Methylindole, and Chlorophene.
Assuntos
Modelos Químicos , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Água/química , Aliivibrio fischeri/efeitos dos fármacos , Aliivibrio fischeri/crescimento & desenvolvimento , Anti-Infecciosos Locais/análise , Anti-Infecciosos Locais/química , Anti-Infecciosos Locais/toxicidade , Antidepressivos Tricíclicos/análise , Antidepressivos Tricíclicos/química , Antidepressivos Tricíclicos/toxicidade , DEET/análise , DEET/química , Diclorofeno/análogos & derivados , Diclorofeno/análise , Sequestradores de Radicais Livres/química , Peróxido de Hidrogênio/química , Concentração de Íons de Hidrogênio , Repelentes de Insetos/análise , Repelentes de Insetos/química , Repelentes de Insetos/toxicidade , Cinética , Nortriptilina/análise , Nortriptilina/química , Nortriptilina/toxicidade , Oxidantes/química , Oxirredução , Fotólise , Escatol/toxicidade , Triazóis/análise , Triazóis/toxicidade , Raios Ultravioleta , Poluentes Químicos da Água/química , Poluentes Químicos da Água/toxicidade , terc-Butil Álcool/químicaRESUMO
INTRODUCTION: Endocrine disrupting chemicals (EDCs) are present in the environment and can have serious effects on humans and wildlife. For the establishment of environmental quality guidelines and regulation of EDCs, a better understanding and knowledge of the occurrence and the behavior of environmental EDCs is necessary. The aim of the present study was to comprehensively identify substances that are responsible for the estrogenic effect of an environmental sediment sample taken from the river Elbe/Germany. DISCUSSION: The estrogenic effect of the organic sediment extract was determined using the yeast-estrogen-screen (YES). The sample was fractionated by liquid chromatography (LC) for effect directed analysis. The composition of estrogen-active fractions was further investigated by gas chromatography-mass spectrometry and high-resolution LC-MS analysis. The composition of the environmental sample was rebuilt with pure compounds in order to assess the partition of estrogenic activity caused by the identified compounds. The organic sediment extract showed an estrogenic potential of 1.9 ± 0.4 ng/g ethinylestradiol equivalents in the sediment. The most prominent contaminants with an estrogenic potential were 17ß-estradiol, estrone, and 4-iso-nonylphenols, but other xenoestrogens like bisphenol A and stigmasterol could be found as well. A rebuild of the sample was measured in the YES in order to investigate mixture effects. About 67 % of the observed estrogenic effect in the sediment extract could be explained by a mixture which contained all identified compounds. Chlorophene (o-benzyl-p-chlorophenol)-a widely used antiseptic that was also identified in the sediment extract-has xenoestrogenic properties in the YES that are in the range of other xenoestrogens like 4-n-nonylphenol. This is the first report on chlorophene acting as a xenoestrogen.
Assuntos
Estrogênios/análise , Cromatografia Gasosa-Espectrometria de Massas , Sedimentos Geológicos/química , Rios/química , Bioensaio/métodos , Diclorofeno/análogos & derivados , Diclorofeno/análise , Disruptores Endócrinos/análise , Monitoramento Ambiental/métodos , Estrogênios/farmacologia , Alemanha , Fenóis/análise , Poluentes Químicos da Água/análise , Leveduras/efeitos dos fármacosRESUMO
Manganese oxides typically exist as mixtures with other metal oxides in soil-water environments; however, information is only available on their redox activity as single oxides. To bridge this gap, we examined three binary oxide mixtures containing MnO(2) and a secondary metal oxide (Al(2)O(3), SiO(2) or TiO(2)). The goal was to understand how these secondary oxides affect the oxidative reactivity of MnO(2). SEM images suggest significant heteroaggregation between Al(2)O(3) and MnO(2) and to a lesser extent between SiO(2)/TiO(2) and MnO(2). Using triclosan and chlorophene as probe compounds, pseudofirst-order kinetic results showed that Al(2)O(3) had the strongest inhibitory effect on MnO(2) reactivity, followed by SiO(2) and then TiO(2). Al(3+) ion or soluble SiO(2) had comparable inhibitory effects as Al(2)O(3) or SiO(2), indicating the dominant inhibitory mechanism was surface complexation/precipitation of Al/Si species on MnO(2) surfaces. TiO(2) inhibited MnO(2) reactivity only when a limited amount of triclosan was present. Due to strong adsorption and slow desorption of triclosan by TiO(2), precursor-complex formation between triclosan and MnO(2) was much slower and likely became the new rate-limiting step (as opposed to electron transfer in all other cases). These mechanisms can also explain the observed adsorption behavior of triclosan by the binary oxide mixtures and single oxides.
Assuntos
Compostos de Manganês/química , Metais/química , Óxidos/química , Adsorção , Alumínio/química , Diclorofeno/análogos & derivados , Diclorofeno/química , Meio Ambiente , Concentração de Íons de Hidrogênio , Íons , Cinética , Microscopia Eletrônica de Varredura , Oxirredução , Solubilidade , Suspensões , Triclosan/químicaRESUMO
Ozonation combined with UV irradiation (UV/O(3)) is an advanced oxidation technique that is very promising for the destruction of organic compounds in aqueous solution. In this study, chlorophene was chosen as a model substrate to investigate the effects of pH, initial substrate concentration, ozone dose, and UV light intensity in degradation experiments. The pseudo-first-order rate constant for total organic carbon (TOC) removal was 2.4 × 10(-2), 9.8 × 10(-4), and 6.4 × 10(-2) min(-1) for O(3), UV, and UV/O(3) treatment, respectively. Clearly, UV-enhanced ozonation leads to a synergetic increase in the overall degradation efficiency. Comparative experiments were performed to investigate the effect of the matrix (distilled water or sewage) on chlorophene removal. The organic compounds in sewage retarded the rate of chlorophene removal by 38%, probably by competitively reacting with the oxidizing agent and screening light. The compound 2-benzoylbenzo-1,4-quinone, benzo-1,4-quinone, hydroquinone and maleic acid were identified as primary intermediates by gas chromatography-mass spectrometry. The concentrations of acetic, formic and oxalic anions were detected by ion chromatography. A possible degradation pathway is proposed on the basis of the reaction products identified.
Assuntos
Diclorofeno/análogos & derivados , Ozônio/química , Raios Ultravioleta , Diclorofeno/química , Diclorofeno/efeitos da radiaçãoRESUMO
Targeted multidimensional liquid chromatography (MDLC), commonly referred to as 'coupled-column' or 'heartcutting', has been used extensively since the 1970s for analysis of low concentration constituents in complex biological and environmental samples. A primary benefit of adding additional dimensions of separation to conventional HPLC separations is that the additional resolving power provided by the added dimensions can greatly simplify method development for complex samples. Despite the long history of targeted MDLC, nearly all published reports involve two-dimensional methods, and very few have explored the benefits of adding a third dimension of separation. In this work we capitalize on recent advances in reversed-phase HPLC to construct a three-dimensional HPLC system for targeted analysis built on three very different reversed-phase columns. Using statistical peak overlap theory and one of the most recent models of reversed-phase selectivity we use simulations to show the potential benefit of adding a third dimension to a MDLC system. We then demonstrate this advantage experimentally by developing targeted methods for the analysis of a variety of broadly relevant molecules in different sample matrices including urban wastewater treatment effluent, human urine, and river water. We find in each case that excellent separations of the target compounds from the sample matrix are obtained using one set of very similar separation conditions for all of the target compound/sample matrix combinations, thereby significantly reducing the normally tedious method development process. A rigorous quantitative comparison of this approach to conventional 1DLC-MS/MS also shows that targeted 3DLC with UV detection is quantitatively accurate for the target compounds studied, with method detection limits in the low parts-per-trillion range of concentrations. We believe this work represents a first step toward the development of a targeted 3D analysis system that will be more effective than previous 2D separations as a tool for the rapid development of robust methods for quantitation of low concentration constituents in complex mixtures.
Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Modelos Químicos , Espectrometria de Massas em Tandem/métodos , Poluentes Químicos da Água/isolamento & purificação , Fracionamento Químico , Diclorofeno/análogos & derivados , Diclorofeno/análise , Diclorofeno/isolamento & purificação , Humanos , Hidrocortisona/urina , Masculino , Fenitoína/análise , Fenitoína/isolamento & purificação , Piridinas/análise , Piridinas/isolamento & purificação , Esgotos/química , Compostos de Sulfonilureia/análise , Compostos de Sulfonilureia/isolamento & purificação , Água/química , Poluentes Químicos da Água/análiseRESUMO
A single-laboratory validation study was conducted for an LC method using UV detection for the simultaneous determination of the active ingredients o-phenylphenol (OPP), p-tert-amylphenol (PTAP), and o-benzyl-p-chlorophenol (OBPCP) in disinfectant formulations. Samples were extracted, the extracts diluted with acidified methanol, and the active ingredients separated by LC with a gradient mobile phase and quantified by using UV detection at 285 nm. For each active ingredient, the RSD was < or = 3.7%, and the intermediate reproducibility was < or = 3.4%. The active ingredient content of the spiked samples analyzed in this study ranged from 0.075 to 10.1% for the individual phenol active ingredients. The average recovery ranges were 86.7-104.9, 82.8-115.6, and 91.6-114.7% for the active ingredients OPP, PTAP, and OBPCP, respectively, for the concentration range of 0.075-10.1%. This method, with a relatively short chromatographic run time (about 15 min), proved to be reliable and convenient for analyses of products or samples containing all or a combination of these phenol active ingredients.
Assuntos
Compostos de Bifenilo/análise , Cromatografia Líquida/métodos , Diclorofeno/análogos & derivados , Desinfetantes/análise , Fenóis/análise , Espectrofotometria Ultravioleta/métodos , Diclorofeno/análiseRESUMO
The exposure to and effects of estrogenic compounds in male breams from Dutch freshwater locations were investigated. Ovotestis was observed infrequently (maximum frequency 16%). However, plasma vitellogenin (VTG) concentration was elevated highly at some locations. Estrogenic activities in male bream plasma, liver, and in gastrointestinal content were measured in the estrogen-responsive chemical-activated luciferase gene expression (ER-CALUX) assay. Plasma concentrations of vitellogenin correlated very well with the estrogenic activities in gastrointestinal content. The ER-CALUX activity in gastrointestinal content thus could provide a biomarker for recent exposure to estrogenic compounds, and the gastrointestinal content was chosen as investigative matrix for the toxicity identification and evaluation ([TIE]; bioassay-directed fractionation) of estrogenic compounds in bream. The approach consisted of a reversed-phase high-performance liquid chromatography fractionation of gastrointestinal content extract, directed by ER-CALUX and followed by gas chromatography analysis. The estrogenic hormones 17beta-estradiol and its metabolite estrone were identified as major contributors to the activity at all locations (except the reference location), independent of the presence or absence of a known source of estrogenic activity, such as a sewage treatment plant. Chemical screening showed the presence of other pollutants, such as a lower chlorinated dioxin and the disinfectants clorophene and triclosan. However, these compounds did not have high estrogenic potencies and their concentrations were not high enough to contribute significantly to the observed estrogenic activity.