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1.
Aquat Toxicol ; 257: 106458, 2023 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-36863155

RESUMO

Silver nanoparticles (AgNPs) are antimicrobial additives in many consumer products with high potential for release into aquatic ecosystems. Though AgNPs have been shown to have negative impacts on fish in laboratory experiments, these effects are rarely observed at ecologically relevant concentrations or in situ in field settings. To evaluate ecosystem-level effects of this contaminant, AgNPs were added to a lake at the IISD Experimental Lakes Area (IISD-ELA) during 2014 and 2015. Mean total silver (TAg) concentrations in the water column were 4 µg L-1 during additions. The growth of Northern Pike (Esox lucius) declined, and their primary prey, Yellow Perch (Perca flavescens) became less abundant after AgNP exposure. Here, we used a combined contaminant-bioenergetics modeling approach to show that individual activity and both individual and population-level consumption of Northern Pike declined significantly in the lake dosed with AgNPs, which, combined with other evidence, suggests that observed declines in body size were likely a result of indirect effects (i.e., reduced prey availability). Further, we found the contaminant-bioenergetics approach was sensitive to modelled elimination rates of mercury, overestimating consumption and activity by 43% and 55%, respectively, when using the mercury elimination rate commonly used in these models versus field-derived estimates for this species. This study contributes to the growing evidence of potentially long-term negative impacts on fish from chronic exposure to environmentally relevant concentrations of AgNPs in a natural setting.


Assuntos
Mercúrio , Nanopartículas Metálicas , Percas , Poluentes Químicos da Água , Animais , Lagos , Esocidae , Prata/toxicidade , Ecossistema , Nanopartículas Metálicas/toxicidade , Poluentes Químicos da Água/toxicidade
2.
Environ Res ; 207: 112658, 2022 05 01.
Artigo em Inglês | MEDLINE | ID: mdl-34990614

RESUMO

Many classes of compounds are known or suspected to disrupt the endocrine system of vertebrate and invertebrate organisms. This review of the sources and fate of selected endocrine disrupting chemicals (EDCs) in the environment includes classes of compounds that are "legacy" contaminants, as well as contaminants of emerging concern. EDCs included for discussion are organochlorine compounds, halogenated aromatic hydrocarbons, brominated flame retardants, per- and polyfluoroalkyl substances, alkylphenols, phthalates, bisphenol A and analogues, pharmaceuticals, drugs of abuse and steroid hormones, personal care products, and organotins. An exhaustive survey of the fate of these contaminants in all environmental media (e.g., air, water, soil, biota, foods and beverages) is beyond the scope of this review, so the priority is to highlight the fate of EDCs in environmental media for which there is a clear link between exposure and endocrine effects in humans or in biota from other taxa. Where appropriate, linkages are also made between the fate of EDCs and regulatory limits such as environmental quality guidelines for water and sediments and total daily intake values for humans.


Assuntos
Disruptores Endócrinos , Retardadores de Chama , Hidrocarbonetos Clorados , Poluentes Químicos da Água , Disruptores Endócrinos/análise , Humanos , Poluentes Químicos da Água/análise
3.
Environ Res ; 208: 112584, 2022 05 15.
Artigo em Inglês | MEDLINE | ID: mdl-34951986

RESUMO

Endocrine disrupting chemicals (EDCs) are ubiquitous in aquatic and terrestrial environments. The main objective of this review was to summarize the current knowledge of the impacts of EDCs on reproductive success in wildlife and humans. The examples selected often include a retrospective assessment of the knowledge of reproductive impacts over time to discern how the effects of EDCs have changed over the last several decades. Collectively, the evidence summarized here within reinforce the concept that reproduction in wildlife and humans is negatively impacted by anthropogenic chemicals, with several altering endocrine system function. These observations of chemicals interfering with different aspects of the reproductive endocrine axis are particularly pronounced for aquatic species and are often corroborated by laboratory-based experiments (i.e. fish, amphibians, birds). Noteworthy, many of these same indicators are also observed in epidemiological studies in mammalian wildlife and humans. Given the vast array of reproductive strategies used by animals, it is perhaps not surprising that no single disrupted target is predictive of reproductive effects. Nevertheless, there are some general features of the endocrine control of reproduction, and in particular, the critical role that steroid hormones play in these processes that confer a high degree of susceptibility to environmental chemicals. New research is needed on the implications of chemical exposures during development and the potential for long-term reproductive effects. Future emphasis on field-based observations that can form the basis of more deliberate, extensive, and long-term population level studies to monitor contaminant effects, including adverse effects on the endocrine system, are key to addressing these knowledge gaps.


Assuntos
Disruptores Endócrinos , Animais , Animais Selvagens , Disruptores Endócrinos/toxicidade , Sistema Endócrino , Humanos , Mamíferos , Reprodução , Estudos Retrospectivos
4.
Environ Res ; 206: 112616, 2022 04 15.
Artigo em Inglês | MEDLINE | ID: mdl-34953884

RESUMO

Endocrine disrupting chemicals (EDCs) are heterogenous in structure, chemical and physical properties, and their capacity to partition into various environmental matrixes. In many cases, these chemicals can disrupt the endocrine systems of vertebrate and invertebrate organisms when present at very low concentrations. Therefore, sensitive and varied analytical methods are required to detect these compounds in the environment. This review summarizes the analytical methods and instruments that are most used to monitor for EDCs in selected environmental matrixes. Only those matrixes for which there is a clear link between exposures and endocrine effects are included in this review. Also discussed are emerging methods for sample preparation and advanced analytical instruments that provide greater selectivity and sensitivity.


Assuntos
Disruptores Endócrinos , Poluentes Químicos da Água , Disruptores Endócrinos/análise , Disruptores Endócrinos/toxicidade , Sistema Endócrino , Poluentes Químicos da Água/análise
5.
Sci Total Environ ; 408(24): 6158-64, 2010 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-20889190

RESUMO

Synthetic musks have been detected in sewage effluents, surface waters, and fish tissues where the polycyclic musk compound, HHCB (Galaxolide®) is the dominant compound in those matrices. In the present study, the Galaxolide® formulation was tested in the yeast estrogenicity screening (YES) assay, and also tested in in vitro and in vivo teleost systems to determine whether it interacts with the estrogen receptor as either an agonist or antagonist. In those tests, Galaxolide® did not act as an estrogen agonist, however there was strong evidence of antagonistic activity as Galaxolide® inhibited the estrogenic activity of 17ß-estradiol (E2). In the YES assay based on a recombinant strain of yeast containing the human estrogen receptor (i.e. hERα), Galaxolide® inhibited the effects of E2 in a dose-dependent manner (IC50=1.63×10(-5)M). In a luciferase reporter gene assay based on the rainbow trout estrogen receptor (i.e. rtER) transfected into a rainbow trout gonadal (RTG-2) cell line, the IC50 for the antagonistic effect of Galaxolide® was 2.79×10(-9)M. In an in vivo assay based on modulation of vitellogenin in rainbow trout, Galaxolide® i.p. injected into trout at a dose of 3.64mg/kg caused inhibition of E2-induced vitellogenin production. That dose is within the range of concentrations of Galaxolide® that have been detected in tissues of fish from contaminated locations.


Assuntos
Benzopiranos/toxicidade , Receptor alfa de Estrogênio/sangue , Estrogênios/toxicidade , Oncorhynchus mykiss/sangue , Perfumes/toxicidade , Animais , Bioensaio , Feminino , Humanos , Vitelogeninas/sangue , Poluentes Químicos da Água/toxicidade
6.
Sci Total Environ ; 407(14): 4220-30, 2009 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-19394680

RESUMO

Land application of municipal biosolids can be a source of environmental contamination by pharmaceutical and personal care products (PPCPs). This study examined PPCP concentrations/temporally discrete mass loads in agricultural tile drainage systems where two applications of biosolids had previously taken place. The field plots received liquid municipal biosolids (LMB) in the fall of 2005 at an application rate of approximately 93,500 L ha (-1), and a second land application was conducted using dewatered municipal biosolids (DMB) applied at a rate of approximately 8Mg dw ha (-1) in the summer of 2006 [corrected].The DMB land application treatments consisted of direct injection (DI) of the DMB beneath the soil surface at a nominal depth of approximately 0.11 m, and surface spreading (SS) plus subsequent tillage incorporation of DMB in the topsoil (approximately 0.10 m depth). The PPCPs examined included eight pharmaceuticals (acetaminophen, fluoxetine, ibuprofen, gemfibrozil, naproxen, carbamazepine, atenolol, sulfamethoxazole), the nicotine metabolite cotinine, and two antibacterial personal care products triclosan and triclocarban. Residues of naproxen, cotinine, atenolol and triclosan originating from the fall 2005 LMB application were detected in tile water nearly nine months after application (triclocarban was not measured in 2005). There were no significant differences (p>0.05) in PPCP mass loads among the two DMB land application treatments (i.e., SS vs. DI); although, average PPCP mass loads late in the study season (>100 days after application) were consistently higher for the DI treatment relative to the SS treatment. While the concentration of triclosan (approximately 14,000 ng g(-1) dw) in DMB was about twice that of triclocarban (approximately 8000 ng g(-1) dw), the average tile water concentrations for triclosan were much higher (43+/-5 ng L(-1)) than they were for triclocarban (0.73+/-0.14 ng L(-1)). Triclosan concentrations (maximum observed in 2006 approximately 235 ng L(-1)) in tile water resulting from land applications may warrant attention from a toxicological perspective.


Assuntos
Agricultura , Cosméticos/análise , Preparações Farmacêuticas/análise , Esgotos , Poluentes Químicos da Água/análise
7.
Sci Total Environ ; 399(1-3): 50-65, 2008 Jul 25.
Artigo em Inglês | MEDLINE | ID: mdl-18455753

RESUMO

Land application of municipal biosolids (sewage) is a common farming practice in many parts of the world. There is potential for transport of pharmaceuticals and personal care products (PPCPs) from agricultural fields to adjacent surface waters via tile drainage systems. In this study, liquid municipal biosolids (LMB) (total solids=11,933 mg L(-1)), supplemented with selected PPCPs and the fluorescent dye tracer rhodamine WT (RWT), were applied to tile drained fields using two land application approaches. Objectives included evaluating the relative benefits of land application practices with respect to reducing PPCP loadings to tile drains, evaluating PPCP persistence in tile water, and determining whether rhodamine WT can be used to estimate PPCP mass loads in tile. The PPCPs examined included an antibacterial agent used in personal care products (triclosan), a metabolite of nicotine (cotinine), and a variety of drugs including two sulfonamide antimicrobials (sulfapyridine, sulfamethoxazole), a beta-blocker (atenolol), an anti-epileptic (carbamazepine), an antidepressant (fluoxetine), analgesic/anti-inflammatories (acetaminophen, naproxen, ibuprofen), and a lipid-regulator (gemfibrozil). Maximum observed PPCP concentrations in the spiked LMB were about 10(3) ng g(-1) dry weight. PPCPs were shown to move rapidly via soil macropores to tile drains within minutes of the land application. Maximum observed PPCP concentrations in tile effluent associated with the LMB application-induced tile flow event were approximately 10(1) to 10(3) ng L(-1). PPCP mass loads, for the application-induced tile-hydrograph event, were significantly (p<0.1) higher for surface spreading over non-tilled soil (incorporation tillage occurring 20 h post-application), relative to aerating soil immediately prior to surface spreading using an AerWay slurry deposition system. PPCP concentrations that were detected above the limit of quantitation (LOQ) in tile water during several precipitation-induced tile flow events that occurred post-application, included: triclosan (max. approximately 1.5 x 10(2) ng L(-1)), carbamazepine (max. approximately 7 x 10(1) ng L(-1)), atenolol (max approximately 4 x 10(1) ng L(-1)), and cotinine (max approximately 2 x 10(1) ng L(-1)). In spite of their presence in biosolids, the other PPCPs were not observed above LOQ concentrations during these events. PPCP concentrations were predicted from RWT concentrations over a 40 day study period. Tile mass loads as a percent of PPCP mass applied to soil ranged from 4.2%+/-SD of 9.2% to 7.1%+/-10.9% for the AerWay system and surface spreading plus incorporation treatments, respectively.


Assuntos
Monitoramento Ambiental , Produtos Domésticos/análise , Preparações Farmacêuticas/análise , Esgotos/análise , Poluentes do Solo/análise , Eliminação de Resíduos Líquidos , Cidades , Cromatografia Gasosa-Espectrometria de Massas , Humanos , Rodaminas/análise , Medição de Risco , Esgotos/química
8.
Chemosphere ; 71(10): 1957-62, 2008 May.
Artigo em Inglês | MEDLINE | ID: mdl-18294675

RESUMO

Quintozene is a fungicide containing the active ingredient, pentachloronitrobenzene (PCNB) that is used to control "snow mold" on golf courses in temperate regions of North America. In this study, quintozene and a formulation of quintozene widely used on golf courses, FFII were tested for toxicity to early life stages of the Japanese medaka, Oryzias latipes. For medaka exposed in static non-renewal assays to quintozene for 17d from the fertilized egg stage to yolk resorption at the fry stage, the LC(50) for mortality was a nominal concentration of 707 microgl(-1) and the effective concentration for 50% hatch (i.e. EC(50)) was a nominal concentration of 71 microgl(-1). Eggs and fry showed developmental abnormalities, including ocular malformations and retarded development of the brain, notochord, organs and body segmentation, which were interpreted as teratogenic responses to exposure to PCNB. For medaka exposed to quintozene, the LOECs for abnormalities of the eye and all other developmental abnormalities were 750 and 100 microgl(-1), respectively. In medaka exposed to the FFII formulation, similar patterns of mortalities, reduced hatching success and developmental abnormalities were observed, but at higher test concentrations that were consistent with the proportion of quintozene in the formulation. For medaka exposed to the formulation, the LOECs for abnormalities of the eye and all other developmental abnormalities were 10,000 and 1,000microgl(-1), respectively. Overall, these data indicate that studies should be conducted to assess the risk of exposure of early life stages of fish to quintozene in watersheds impacted by golf courses.


Assuntos
Fungicidas Industriais/toxicidade , Nitrobenzenos/toxicidade , Oryzias/anormalidades , Teratogênicos/toxicidade , Compostos de Anilina/toxicidade , Animais , Embrião não Mamífero/anormalidades , Embrião não Mamífero/efeitos dos fármacos , Anormalidades do Olho/induzido quimicamente , Hexaclorobenzeno/toxicidade , Dose Letal Mediana , Reprodução/efeitos dos fármacos , Zigoto/efeitos dos fármacos , Zigoto/crescimento & desenvolvimento
9.
Aquat Toxicol ; 73(1): 44-54, 2005 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-15892991

RESUMO

Human and veterinarian pharmaceuticals have been detected in the aquatic environment for a number of years, but the potential for biological effects in exposed aquatic organism is only now being reported. The lipid regulator, gemfibrozil (GEM) is detected at microg/L concentrations in domestic wastewater and ng/L concentrations in surface waters. We investigated the uptake of GEM in goldfish (Carassius auratus) over a 96 h time period by measuring GEM in blood plasma using LC-MS/MS. Results indicated that GEM can be taken up from water through the gills. In goldfish exposed to GEM by a single intraperitoneal injection, concentrations of GEM in the blood plasma declined rapidly over 96 h post-injection, with a half-life estimated at approximately 19 h. Exposure of goldfish to waterborne GEM at an environmentally relevant concentration over 14 days resulted in a plasma bioconcentration factor of 113. In goldfish exposed to aqueous concentrations of GEM for 96 h or 14 days, plasma testosterone (T) was reduced by over 50% in fish from all treatments. As a possible mechanistic explanation for the observed reduction in T, levels of steroid acute regulatory (StAR) protein transcript in goldfish testes were assessed by RT-PCR. StAR protein is involved in the transport of cholesterol from the outer to the inner mitochondrial membrane for transformation by the first enzyme in steroidogenesis. After exposure to GEM for 96 h, a 50% decrease in StAR mRNA levels was observed in goldfish. Gonadal StAR mRNA levels were not affected in the 14 days exposure, indicating that the observed decreases in plasma testosterone were not solely due to impaired delivery of cholesterol to the inner mitochondrial membrane. Our results demonstrate that exposure to environmental levels of GEM leads to bioconcentration of the drug in plasma and the potential for endocrine disruption in fish.


Assuntos
Genfibrozila/farmacocinética , Genfibrozila/toxicidade , Carpa Dourada/metabolismo , Fosfoproteínas/metabolismo , Testosterona/sangue , Análise de Variância , Animais , Sequência de Bases , Cromatografia Líquida , Clonagem Molecular , Primers do DNA , Glândulas Endócrinas/efeitos dos fármacos , Genfibrozila/sangue , Brânquias/metabolismo , Masculino , Espectrometria de Massas , Dados de Sequência Molecular , Fosfoproteínas/genética , Reação em Cadeia da Polimerase Via Transcriptase Reversa , Análise de Sequência de DNA , Fatores de Tempo
10.
Environ Toxicol Chem ; 20(9): 1968-78, 2001 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-11521823

RESUMO

The sheepshead minnow (Cyprinodon variegatus Lacépède), an estuarine fish species, was exposed to 17alpha-ethynylestradiol (EE2) at nominal test concentrations of 0.2, 2, 20, 200, 400, 800, 1,600, and 3,200 ng/L. Fish were exposed for up to 59 d, from subadult stages to sexual maturity, under flow-through conditions. The exposure period was followed by an evaluation of reproductive success and survival of progeny. The reproductive success of exposed sheepshead minnows, as determined from data on egg production from two subsequent spawning trials, was reduced in fish exposed to 200 ng/L EE2 and, in one spawning trial, in the 20-ng/L treatment. Hatching success was reduced in the progeny of fish exposed to 200 ng/L EE2, but survival was good among fry that successfully hatched. Histological examination indicated generalized edema, damage to gill epithelia, hepatic toxicity, fibrosis of the testis, and evidence of sex reversal, including testes-ova and spermatagonia-like cells in ovaries. The maximum acceptable toxicant concentration (MATC) for gonadal development in males was within the normal range of EE2 concentrations in sewage treatment plant effluents. The exposure regimen and choice of test organism, combined with histological examination, allowed independent evaluation of ecologically significant acute, reproductive and estrogenic endpoints. Estrogen receptor-mediated effects occurred at concentrations where reproductive effects were measurable under standard reproduction assays. The sheepshead minnow appears to be a sensitive in vivo model for partial life-cycle testing of compounds that have the potential to disrupt the endocrine system as well as reproduction in estuarine and coastal marine fish species.


Assuntos
Cyprinidae , Congêneres do Estradiol/efeitos adversos , Etinilestradiol/efeitos adversos , Receptores de Estrogênio/efeitos dos fármacos , Reprodução/efeitos dos fármacos , Poluentes Químicos da Água/efeitos adversos , Animais , Bioensaio , Biomarcadores/análise , Relação Dose-Resposta a Droga , Monitoramento Ambiental/métodos , Feminino , Brânquias/patologia , Gônadas/crescimento & desenvolvimento , Gônadas/patologia , Fígado/patologia , Masculino , Receptores de Estrogênio/fisiologia , Análise de Sobrevida
11.
Arch Environ Contam Toxicol ; 40(3): 355-62, 2001 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-11443366

RESUMO

There recently have been increasing interest in South America on organic pollutants from the coastal marine environment. This study intended to seek out the occurrence and distribution of persistent organochlorine compounds in the Mar Chiquita coastal lagoon watershed. The levels were measured in sediments and associated crabs. Though a significant number of PCBs (mainly penta- and hexachlorinated congeners) were detected, the concentrations were very low (in the order of ppbs), indicative of an estuarine environment with little industrial development. On the other hand, pesticide residues were higher than PCBs in one or two orders of magnitude, as a result of the important agricultural activities in the area. Heptachlor epoxide, DDT and its metabolites, and gamma-HCH were the predominant OC pesticides in sediments as well as in crabs. Significant differences among geographical areas: Channel 5 and Vivoratá Creek (northern and southern sampling sites, respectively) contained detectable pesticide concentrations (heptachlor epoxide, DDE, DDD, and mirex).


Assuntos
Braquiúros/fisiologia , Poluentes Ambientais/análise , Inseticidas/análise , Bifenilos Policlorados/análise , Poluentes Químicos da Água/análise , Animais , Argentina , Monitoramento Ambiental , Sedimentos Geológicos/química
12.
Environ Toxicol Chem ; 20(2): 297-308, 2001 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-11351429

RESUMO

Gonadal intersex and high prevalences of the female phenotype have been observed in fish populations in urbanized areas. Environmental estrogens discharged in sewage treatment plant effluents may be responsible for feminization of fish but many compounds with the potential to induce these responses occur in effluents, including natural and synthetic estrogen hormones, degradation products of alkylphenol ethoxylate surfactants, and plasticizers. In this study, the estrogen hormones 17 alpha-ethinylestradiol, 17 beta-estradiol, estrone, and estriol induced intersex (i.e., testis-ova) and altered sex in Japanese medaka (Oryzias latipes) when these fish were exposed to nanogram per liter concentrations of test compounds from hatch to approximately 100 d after hatch. A mix of nonylphenol mono- and diethoxylate induced a weak response and a mix of nonylphenol mono- and diethoxycarboxylate did not give a response in this assay at microgram per liter concentrations, indicating that these degradation products of nonylphenol ethoxylates have little or no estrogenic activity in fish. Bisphenol A induced testis-ova in medaka exposed to a concentration of 10 micrograms/L, but diethylhexyl phthalate did not induce a response. Results with the medaka assay were consistent with estrogenic responses in the yeast estrogen screening assay. Analyses of monitoring data reported in the literature indicate that concentrations of estrogen hormones detected in the final effluents of sewage treatment plants are generally greater than the lowest-observed-effect levels for alterations to gonadal development in medaka.


Assuntos
Estrogênios não Esteroides/farmacologia , Resíduos Industriais , Esgotos , Razão de Masculinidade , Poluentes Químicos da Água/farmacologia , Animais , Feminino , Masculino , Nível de Efeito Adverso não Observado , Oryzias , Ovário/efeitos dos fármacos , Ovário/patologia , Saccharomyces cerevisiae/efeitos dos fármacos , Testículo/efeitos dos fármacos , Testículo/patologia
13.
Rapid Commun Mass Spectrom ; 14(23): 2154-7, 2000.
Artigo em Inglês | MEDLINE | ID: mdl-11114024

RESUMO

While developing a liquid chromatography/tandem mass spectrometry method for the analysis of the flavonoid quercitin, it was observed that quercetin (3,3',4',5,7-pentahydroxyflavone) exhibited clustering in both the positive and negative ion mode. Two series of positive ion clusters were observed; the first series corresponds to singly charged [2M + Na](+) at m/z 627.2 to [13M + Na](+) at m/z 3947.5, while the second series corresponds to doubly charged [7M + 2Na](2+) at m/z 1080.4 to [25M + 2Na](2+) at m/z 3798.5. In the negative ion mode, the behavior of quercetin parallels that of apigenin (4',5,7-trihydroxyflavone) in that [M + NO(3)](-), [2M + NO(3)](-), and [3M + NO(3)](-) were observed at m/z 364.1, 666.0, and 968.9, respectively; in addition, quercitin clusters with chloride ions ([2M + Cl](-) at m/z 638.9 and [3M + Cl](-) at m/z 940. 9) were observed. The results of tandem mass spectrometric examination of several cluster ions are reported.


Assuntos
Substâncias Macromoleculares , Quercetina/química , Sódio/química , Gases , Íons , Espectrometria de Massas/métodos , Quercetina/análise
14.
J Mass Spectrom ; 35(7): 818-30, 2000 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-10934435

RESUMO

A mass spectrometric study was carried out on two nonylphenoxycarboxylic acids, NP1EC and NP2EC (where 1 and 2 indicate the number of ethoxylate units attached to the nonylphenoxy moiety), that are persistent metabolites of widely used nonionic surfactant nonylphenol ethoxylates. In a gas chromatographic/mass spectrometric (GC/MS) study of the methyl esters of NP1EC and NP2EC, two series of fragment ions were observed in electron ionization (EI) mass spectra; m/z (179 + 14n, n = 0-7) and m/z (105 + 14n, n = 0-4) for NP1ECMe and m/z (223 + 14n, n = 0-7) and m/z (107 + 14n, n = 0-5) for NP2ECMe. Similarity indices were used to compare quantitatively the mass spectra of isomers. The mass spectra of two isomers were found to be similar whereas those of the remaining isomers were readily distinguishable from each other. The abundant fragment ions of the two NPECMes were investigated further by GC/MS/MS; product ions resulting from cleavage in the alkyl moiety, cleavage in the ECMe moiety and cleavage in both moieties were detected. Possible structures of the nonyl groups in the two esters were inferred. GC/chemical ionization (CI) mass spectra of the NPECMes with isobutane as reagent gas showed characteristic hydride ion-abstracted fragment ions shifted by 1 Da from those in the corresponding EI mass spectra. The sensitivity of a selected ion monitoring quantitation method for the NPECMes is enhanced under CI conditions compared with that under EI conditions. With electrospray ionization MS/MS, [M - H](-) ions of NP1EC (m/z 277) and NP2EC (m/z 321) were observed and, upon collision-induced dissociation of [M - H](-) of each of the two acids, fragment ions of m/z 219 corresponding to deprotonated nonylphenol, were observed in each case. Based on this observation, a rapid, simple and reliable selected product ion quantitation method is proposed for NP1EC and NP2EC.


Assuntos
Etilenoglicóis/química , Tensoativos/química , Cromatografia Líquida de Alta Pressão/métodos , Detergentes/química , Etilenoglicóis/farmacocinética , Cromatografia Gasosa-Espectrometria de Massas/métodos , Espectrometria de Massas/métodos , Tensoativos/farmacocinética
15.
Rapid Commun Mass Spectrom ; 14(13): 1087-93, 2000.
Artigo em Inglês | MEDLINE | ID: mdl-10867682

RESUMO

Environmental analytical chemistry has recently changed focus from analysis of non-polar, persistent contaminants (e.g. polychlorinated biphenyls and dioxins) to more polar and labile compounds that interfere with biological processes. For example, natural and synthetic estrogens and their metabolites have been detected in sewage treatment plant effluents at nanogram/liter concentrations that are similar to those at which both total sex reversal and intersex (containing both testes and ova) is induced in fish exposed to these compounds in laboratory experiments. The development of techniques for the analysis of natural and synthetic estrogens in biological fluids (i.e. serum and urine) has been a priority in the biomedical field. However, the recent recognition that estrogen hormones are contaminants in the environment that may contribute to endocrine disruption has focused attention on the need for highly sensitive and specific techniques that are applicable for trace analysis in complex environmental matrices. Three optimized mass spectrometric protocols have been developed for the determination and quantitation of steroid hormones in environmental matrices using gas chromatography/tandem mass spectrometry (GC/MS/MS), liquid chromatography/mass spectrometry selected ion monitoring, (LC/MS - SIM) and liquid chromatography/tandem mass spectrometry (LC/MS/MS). The advantages and disadvantages of each method are presented.


Assuntos
Estrogênios/análise , Cromatografia Líquida , Poluentes Ambientais/análise , Congêneres do Estradiol/análise , Cromatografia Gasosa-Espectrometria de Massas , Espectrometria de Massas
16.
Arch Environ Contam Toxicol ; 38(2): 202-8, 2000 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-10629283

RESUMO

A freshwater fish species, silverside (Odontesthes bonariensis) from Mar Chiquita coastal lagoon, Argentina, was analyzed for concentrations of several organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs) in liver, gonads, mesenteric fat and muscle, and the contents of the digestive tract over several stages of sexual maturation. PCBs and OCs were detected at ng/g concentrations (wet weight) in pooled samples, with levels generally in the order of fat > liver > gonad > muscle, reflecting the differences in tissue lipid content. Lipid-normalized concentrations of the analytes were relatively consistent among tissues, except for significantly higher concentrations of PCBs (e.g., 447.7 ng/g lipid wt) in the ovaries of female silverside. DDT and its metabolites, gamma-HCH, and several insecticides from the cyclodiene class, including endosulfan and endosulfan sulfate, were the predominant OCs in fish tissues and the contents of the digestive tract, reflecting recent and past pesticide use in this region. The ratio of OCs to PCBs in all tissues was >1; consistent with contamination of the region with OC pesticides. However, PCBs were dominated by penta- and hexachlorobiphenyls, which is consistent with direct (i.e. , nonatmospheric) inputs. Biomagnification of penta- and hexachlorobiphenyl PCB congeners was noted in fish tissues relative to the contents of the digestive tract. Total OC and PCB concentrations in the ovaries and muscle of silverside were below concentrations associated with reproductive impairment in fish or the limits for human consumption, respectively.


Assuntos
Peixes/metabolismo , Hidrocarbonetos Clorados/análise , Bifenilos Policlorados/análise , Tecido Adiposo/química , Animais , Argentina , Feminino , Alimentos/normas , Gônadas/química , Fígado/química , Masculino , Músculos/química , Reprodução
17.
Sci Total Environ ; 201(3): 245-72, 1997 Aug 18.
Artigo em Inglês | MEDLINE | ID: mdl-9241874

RESUMO

The distribution of polychlorinated biphenyls (PCBs) in the food-web of Lake Ontario was studied to determine the parameters that control the trophodynamics of PCB congeners; including toxic non-ortho and mono-ortho PCBs. 'Biomagnification' of PCBs was evident in the food-web as total PCBs increased through trophic levels when concentrations were calculated on both a wet wt. and lipid weight basis; although there was no evidence of biomagnification between forage fish and piscivorous fish. Biomagnification was greatest for congeners with log octanol-water partition (log Kow) coefficients between 6 and 7.5. Non-ortho congeners 77 and 126, and congener 151 were not biomagnified to the extent of other congeners with similar Kow, which was attributed to high rates of metabolic clearance of these compounds. The Toxic Equivalent Quantities (TEQs) associated with non-ortho and mono-ortho PCBs increased throughout the Lake Ontario food-web. The high TEQ observed in herring gull eggs was primarily the result of very high concentrations of congener 126 in this component of the food web.


Assuntos
Ração Animal/análise , Ecossistema , Bifenilos Policlorados/análise , Poluentes Químicos da Água/análise , Animais , Aves , Cromatografia Gasosa , Feminino , Peixes , Água Doce/química , Sedimentos Geológicos/química , Great Lakes Region , Masculino
18.
Mutat Res ; 343(2-3): 121-35, 1995 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-7791806

RESUMO

Micronucleus assays with fish have been shown to be useful in vivo techniques for genotoxicity testing, and show potential for in situ monitoring of water quality. In this paper, we review the literature on the clastogenic effects of chemical and physical agents on fish cells, with emphasis on the induction of micronuclei in teleosts. Included in the review is a description of the mechanisms for formation of micronuclei in cells, and a summary of the various techniques that have been used for micronucleus analysis in fish. This review is directed to assisting laboratories in the development of fish genotoxicity assays for water quality monitoring.


Assuntos
Peixes/genética , Testes para Micronúcleos , Poluentes da Água/toxicidade , Animais , Eritrócitos/efeitos dos fármacos , Sensibilidade e Especificidade
20.
Sci Total Environ ; 94(1-2): 125-41, 1990 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-2163105

RESUMO

In order to investigate the putative association between chemical contamination in western Lake Ontario and high prevalences of fish tumors, sediments from Hamilton Harbour and Oakville Creek in Lake Ontario and reference sites in non-polluted areas of Ontario, Canada were collected and extracted for organic contaminants. Sediment extracts from Hamilton Harbour had the highest concentrations of polychlorinated biphenyls and organochlorine insecticides (ppb) and contained very high concentrations of polynuclear aromatic hydrocarbons (ppm); although the levels of these compounds varied widely with sampling location in the harbor. A sediment extract from Hamilton Harbour was mutagenic in the Ames bacterial assay, both with and without microsomal activation. High levels of aromatic DNA adducts were induced in cultured mouse C3H1OT1/2 cells after in vitro exposure to Hamilton Harbour sediment extract. In two separate carcinogenicity experiments involving a sac fry microinjection assay with rainbow trout (Oncorhynchus mykiss), Hamilton Harbour sediment extract induced hepatocellular carcinomas in fish. No hepatic neoplasms were observed in fish that had been treated with sediment extract from Oakville Creek, or with extract from a reference sediment. The significance of these results is discussed in relation to the distribution of neoplasms in feral fish within western Lake Ontario.


Assuntos
Carcinógenos/análise , Carcinoma Hepatocelular/veterinária , Doenças dos Peixes/induzido quimicamente , Neoplasias Hepáticas/veterinária , Mutagênicos/análise , Neoplasias/veterinária , Poluentes Químicos da Água/análise , Poluentes da Água/análise , Animais , Testes de Carcinogenicidade , Carcinoma Hepatocelular/induzido quimicamente , Carcinoma Hepatocelular/patologia , Células Cultivadas , DNA/metabolismo , Doenças dos Peixes/patologia , Peixes , Água Doce , Neoplasias Hepáticas/induzido quimicamente , Neoplasias Hepáticas/patologia , Testes de Mutagenicidade , Mutagênicos/farmacologia , Neoplasias/induzido quimicamente , Neoplasias/patologia , Ontário , Salmonella typhimurium/efeitos dos fármacos , Truta
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