Os albatrozes e petréis (Procellariiformes) são aves oceânicas e migratórias de grande interesse conservacionista. Neste trabalho foram estudadas duas classes de poluentes bastante conhecidos por afetarem negativamente as aves marinhas: os poluentes orgânicos persistentes e os plásticos. Bifenilos policlorados (PCBs) e pesticidas organoclorados foram detectados no tecido adiposo, fígado e músculo de oito espécies de Procellariiformes. Apesar da grande variabilidade intraespecífica nas concentrações, os perfis de PCBs e pesticidas organoclorados foram semelhantes entre os indíviduos, com predôminância de PCBs penta, hexa e heptaclorados e do p´p-DDE. A condição corporal se mostrou um fator importante na variação e redistribuição dos organoclorados nos tecidos das aves. As análises de isótopos estáveis de carbono e nitrogênio no fígado e músculo das aves mostraram que a dieta não foi suficiente para explicar as concentrações de organoclorados nas espécies estudadas e reforçaram a influência de fatores como idade, distribuição e especifidade da dieta na contaminação por estes compostos em aves marinhas. PCBs e pesticidas organoclorados foram detectados em pellets e fragmentos plásticos encontrados no trato digestório das aves estudadas, com perfis semelhantes aos encontrados nos tecidos dos Procellariiformes. A ocorrência de poluentes orgânicos em plásticos evidencia a capacidade destes de adsorver e transportar estes compostos e reforça o potencial dos plásticos como uma fonte adicional de contaminação para os animais que os ingerem, como as aves marinhas. / Albatrosses and petrels (Procellariiformes) are migratory oceanic birds of considerable conservational interest. The aim of the present study was to evaluate two classes of pollutants that negatively affect seabirds: persistent organic pollutants and plastics. Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were detected in the adipose tissue, liver and muscle of eight species of Procellariiformes. Although organochlorine concentrations exhibited a high degree of intra-species variability, the profiles of PCBs and OCPs were similar among the individuals, with predominance of penta, hexa and heptachlorobiphenyls and p´p-DDE. Body condition was an important factor in the variation and redistribution of organochlorine compounds in the tissues of the birds. Stable isotope analysis of carbon and nitrogen in the liver and muscle revealed that diet alone was insufficient to explain the organochlorine concentrations in the species studied, suggesting the influence of factors such as age, distribution and diet specificity regarding organochlorine contamination in seabirds. PCBs and OCPs were detected in plastic fragments and pellets found in the digestive tract of Procellariiformes, with profiles very similar to those found in the tissues of the birds. The occurrence of organic pollutants in plastics demonstrates their ability to adsorb and transport these compounds and underscores the potential of plastics as an additional source of contamination in organisms that ingest these products, such as seabirds.

Bifenilas policloradas (PCBs) foram produzidas comercialmente entre 1929 e meados da década de 1980 para propósitos industriais. As mesmas propriedades que despertaram o interesse industrial, tais como: inércia química, alta constante dielétrica, resistência à queima; foram responsáveis pelo espalhamento dos PCBs em todos os compartimentos ambientais, de tal forma que são encontrados em amostras de tecidos adiposos de animais e humanos, leite, sedimentos dentre outras matrizes. Enormes quantidades de PCBs continuam em uso ou estão estocadas a espera de uma destinação final. No presente estudo demonstramos o uso da reação de hidrodescloração catalítica como forma de destruição/destoxificação de bifenilas policloradas. Para tanto, a reação foi estudada em amostras reais de PCBs (óleo dielétrico - Ascarel®), amostras comerciais (Aroclor® 1242 e 1254) e amostra sintética (2,4-diclorobifenila). O estudo se baseia no uso de solventes orgânicos como meio reacional e paládio suportado em carvão ativado como catalisador, devido à sua seletividade para a reação desejada, bem como sua baixa capacidade de hidrogenar compostos aromáticos. xii A condição experimental ótima para a hidrodescloração foi determinada a partir da aplicação de planejamento experimental do tipo Doehlert. Esta condição ótima foi aplicada com sucesso a PCBs contidos em outras matrizes. A cinética da reação é apresentada para o 2,4-diclorobifenila como estudo de caso e uma proposta de mecanismo da reação de hidrodescloração de PCBs é apresentada baseada nos resultados experimentais. / Polychlorinated biphenyls (PCBs) were produced between 1929 and the 1980s for industrial applications. The same properties that make it a chemical of interest for industrial applications, such as: chemical inertness, high dielectric constant, fire resistance; were responsible for the widespreading of PCBs over all enviornmental compartments. They can be found in samples of fat tissues of humans and animals, milk, sediments, among other matrices. Enormous quantities of PCBs are still in use or stocked waiting for a final destination. In the present study, we have shown the use of catalytic hydrodechlorination as an alternative for the destruction/detoxification of polychlorinated biphenyls. For this, the reaction was studied in real samples of PCBs (dielectric oil - Ascarel®), commercial samples (Aroclor® 1242 e 1254) and pure chlorinated biphenyls (2,4-dichlorobiphenyl). The study is based in the use of organic solvents as reactional media and palladium supported in activated carbon as catalyst, due to its selectivity for the desired reaction and to its low capacity to hydrogenate aromatic compounds. xiv The optimal hydrodechlorination condition was determined through the application of a Doehlert experimental planning. This optimal condition was applied with success to PCBs contained in other matrices. The reaction kinetics for 2,4-dichlorobiphenyl was presented as a case study and a mechanistic proposal was presented for the hydrodechlorination of PCBs based on these experimental conditions.

No description available.

Due to the risk for human health associated to the presence of polychlorinated biphenyl (PCB) residues in foods, there is an interest in knowing the different factors that could reduce such contamination. Previous research has demonstrated that food processing modifies both qualitative and quantitatively, the organochlorine contamination, specially PCBs, of the raw material. Further, microorganisms of technological interest in food industry could play an important role in the degradation process. The growth of the meat starter Staphylococcus xylosus in liquid media containing PCBs (10, 28, 52, 138, 153 and 180), and its ability to degrade PCBs during 168 h of incubation in liquid media and meat mixture was investigated. PCBs did not affect the growth of the starter microorganism in nutritive (brain heart infusion, BHI) or mineral salt medium (MSM) when compared to control (no PCB). The microorganism was able to degrade some of the PCB congeners tested. PCBs 138 and 153 were degraded both in BHI (78% and 68%, respectively; p<0.05) and in MSM (71% and 66%, respectively; p<0.05), with maximal being observed within 24 hours. Highly significant negative exponential relationships were observed between incubation time and PCB 28 and 180 in BHI, as well as to PCBs 52 and 180 in MSM. In the meat mixture highly significant negative exponential relationships were observed between incubation time and the concentration of PCB 10. These results indicate that fermentation by Staphylococcus xylosus in meat products can reduce some PCB residues and the meat starter can be used to obtain foods with lower toxicological risk. / É de grande importância o conhecimento dos diversos fatores que podem reduzir a contaminação causada por bifenilos policlorados (PCBs) em alimentos, já que resíduos destes compostos podem trazer graves riscos à saúde humana. Diversas investigações têm demonstrado que o processamento dos alimentos modifica, tanto qualitativa quanto quantitativamente, a contaminação organoclorada, especialmente de PCBs, presente na matéria prima. Além disso, os microrganismos de interesse tecnológico na indústria alimentícia poderiam ser de grande importância no processo de degradação. Investigou-se o crescimento do microrganismo starter Staphylococcus xylosus em meio de cultura líquido contendo PCBs (10, 28, 52, 138, 153 e 180), e sua capacidade degradativa em meio liquido e massa cárnea durante 168 horas de incubação. A presença de PCBs não afetou o crescimento do microrganismo em meio de cultura nutritivo (BHI) ou meio de cultura salino (MSM) quando comparados com o controle (sem a presença de PCBs). O microrganismo demonstrou capacidade de degradar alguns dos congêneres de PCBs testados. Os PCBs 138 e 153 foram degradados em meio nutritivo (78% e 68%, respectivamente; p<0,05) e em meio salino (71% e 66%, respectivamente; p<0,05), sendo observada uma máxima degradação nas primeiras 24 horas de incubação. Relação exponencial significativa foi observada entre o período de incubação e os PCBs 28 e 180 em BHI, assim como para os PCBs 52 e 180 em meio salino. Relação exponencial significativa foi observada entre o período de incubação e as concentrações do PCB 10 em massa cárnea. Estes resultados indicam que a fermentação realizada por Staphylococcus xylosus em produtos cárneos pode reduzir resíduos de PCBs e o microrganismo starter pode ser usado na obtenção de alimentos com menor risco toxicológico.

The overall objective of the research presented in this dissertation was to assess exposure to endocrine disrupting chemicals (EDCs), polychlorinated biphenyls (PCBs), phthalates, and bisphenol A (BPA) in the general population and evaluate their associations with adverse reproductive health effects, including cancers, in women. Given the proven contribution of unopposed estrogens to the risk for endometrial neoplasia or breast cancer, renewed health concerns have aroused about estrogen mimicking EDCs found in food, personal care products or as environmental contaminants. Our meta-analysis showed that exposure to estrogen mimicking PCBs increased summary risk of breast cancer and endometriosis. We further evaluated the relationship between endometriosis and breast cancer, and EDCs using a bioinformatics method. Our bioinformatics approach was able to identify genes with the potential to be involved in interaction with PCB, phthalates and BPA that may be important to the development of breast cancer and endometriosis. Therefore, we hypothesized that exposure to EDCs such as PCBs, phthalates, and BPA, results in adverse reproductive health effects in women. Using subject data and biomarkers available from the Center for Disease Controls National Health and Nutrition Examination Survey database we conducted a cross-sectional study of EDCs in relation to self-reported history of endometriosis, uterine leiomyomas, breast cancer, cervical cancer, ovarian cancer, and uterine cancer. Significantly higher body burdens of PCBs were found in women diagnosed with breast cancer, ovarian cancer, and uterine cancer compared to women without cancer. PCB 138 was significantly associated with breast cancer, cervical cancer, and uterine cancer, while PCBs 74 and 118 were significantly associated with ovarian cancer. The sum of dioxin-like PCBs were significantly associated with ovarian cancer (OR of 2.02, 95% CI: 1.06-3.85) and the sum of non-dioxin-like PCBs were significantly associated with uterine cancer (OR of 1.12, 95%CI: 1.03-1.23). Significantly higher body burdens of PCBs were also found in women diagnosed with endometriosis and uterine leiomyomas. Documenting the exposure to EDCs among the general U.S. population, and identifying agents associated with reproductive toxicity have the potential to fill research gaps and facilitate our understanding of the complex role environmental chemicals play in producing toxicity in reproductive organs.

Native and naturalized California plant species were screened for their phytoremediation potential for the cleanup of soil contaminated with petroleum hydrocarbons (PHCs), poly-aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), chlorinated dioxins/furans, and heavy metals. This screening was followed by controlled greenhouse experiments to further evaluate the phytoremediation potential of the best candidates. Field specimens and soils used for this study were collected from the former Energy Technology Engineering Center (ETEC) at the Santa Susana Field Laboratory in Southern California that was operated by the Department of Energy (DOE). Soils at this site contain all of the contaminants of interest (COIs). Nine plant species were screened in the field: Purple Needlegrass (Nassella pulchra), Blue Elderberry (Sambucus nigra), Laurel Sumac (Malosma laurina), Mule Fat (Baccharis salicifolia), Palmer’s Goldenbush (Ericameria palmeri), Summer Mustard (Hirschfeldia incana), Narrowleaf Milkweed (Asclepias fascicularis), Coyote Brush (Baccharis pilularis), and Thickleaf Yerba Santa (Eriodictyon crassifolium). In the field three samples of each species growing in contaminated soil and one of each species growing in uncontaminated soil were selected for harvesting and analysis. The roots, above ground plant tissue, and soil around the roots were sampled separately and analyzed for the COIs: PHCs, PAHs, PCBs, chlorinated dioxins/furans, and metals (which include mercury, silver, cadmium, and lead). All of the plants in the field appeared to generate compounds which result in higher measured PHC concentrations than those measured in the associated soil. The highest concentrations of PAHs in the roots were observed for Blue Elderberry (1740 ug/kg), Purple Needlegrass (703 ug/kg), and Yerba Santa (200 ug/kg). No uptake of PCBs was observed in the roots or foliage of any species. The highest concentrations of total chlorinated dioxins/furans in the roots were observed for Purple Needlegrass (2237 ng/kg), Blue Elderberry (1026 ng/kg), Palmer’s Goldenbush (432 ng/kg), and Yerba Santa (421 ng/kg). The highest concentrations of total chlorinated dioxins/furans in the foliage were observed for Yerba Santa (901 ng/kg), Palmer’s Goldenbush (757 ng/kg), and Purple Needlegrass (694 ng/kg). No uptake of mercury was observed in the roots or foliage of any species. The highest concentration of silver in the roots was observed for Laurel Sumac (7.34 mg/kg). Summer Mustard (SM) was the only species that showed uptake of silver into the foliage (0.405 mg/kg). The highest concentrations of cadmium in the roots and foliage were observed for Mule Fat (1.84 mg/kg and 3.64 mg/kg) and Coyote Brush (1.52 mg/kg and 2.12 mg/kg) and the greatest concentration of lead in the roots and foliage was observed for Purple Needlegrass (8.92 mg/kg and 1.17 mg/kg). Plants with a wide variety of observed contaminant uptake in the field were selected for a second phase of research in which three of the most promising species were grown in greenhouse microcosms to quantify the removal of contaminants from the soil. The three species selected based on preliminary results from the field study were Coyote Brush, Mule Fat, and Purple Needlegrass. Microcosms consisted of 2.17 kg of soil in 4-L glass jars with glass marbles for an underdrain. Plants were watered with deionized water and no leachate was collected. Five replicates of each microcosm type were created and incubated for 211 days with soil sampling at 85 and 211 days. Soil, plant roots/above ground tissue, and volatilization from the plants were analyzed for COIs to determine the mechanisms of phytoremediation. One set of microcosms was used to test the effect of addition of achelating agent (ethylenediaminetetraacetic acid) and another set was used to test the effect of fertilizer addition on phytoremediation potential. Three control treatments were tested: sterilized (gamma irradiation) soil planted with Purple Needlegrass, unplanted soil, and sterilized unplanted soil. None of the plant species demonstrated volatilization of COIs under these conditions. Volatilization of mercury was not tested for. The average PCB concentration (measured as Aroclor 1260) reductions in soils with Purple Needlegrass and chelated Coyote Brush were 49.4% and 51.4% respectively (p < 0.05). However, the sterilized unplanted control also had a decrease of Aroclor 1260 concentrations in the soil of 36.6% (p < 0.05). None of the species phytoextracted PCBs, so the mechanism of PCB remediation appears to be phytostimulation of the rhizosphere. Purple Needlegrass showed the greatest uptake of dioxins/furans into the foliage but did not appear to reduce the dioxin/furan concentrations in the soil. Coyote Brush, fertilized Coyote Brush, and Mule Fat also showed uptake of dioxins/furans into the roots and foliage. Only the Coyote Brush and fertilized Coyote Brush significantly (p = 0.036, p = 0.022) reduced the total dioxin/furan concentration in the soil (17.8% and 19.8% respectively). Coyote Brush may have stimulated microbes in the rhizosphere to better degrade the dioxins/furans. None of the plants were identified as hyper-accumulators of metals, and none of the soil metal concentrations significantly decreased in any of the microcosms. All of the metals (except mercury) were taken into the roots of plants to some degree, with Purple Needlegrass showing the most promise for metal extraction as it showed some of the highest concentrations of metals in roots and was the only species that contained mercury and silver in the foliage. This study suggests that there is some potential for phytoremediation of PCBs and chlorinated dioxins/furans. The results for petroleum hydrocarbons were inconclusive. Metal uptake was not substantial enough to lower metal concentrations in the soils. Thus phytoremediation of COIs at the site is limited and more aggressive forms of remediation may be required to reduce the concentrations of COIs quickly.

Biochar is created during the pyrolysis of organic biomass. Once added into the soil, it can improve its features. Biochars made from sewage sludge have various compositions. It is because of the vast difference between entrance materials. Organic pollutants can be absorbed into its surface during the cooling proces sof pyrolysis. If released into the enviroment, these compounds can cause inhibition of plant growth, get into food chains and adversely affect living organisms. Organic pollutans are determined most often by GC/MS after organic solvent extraction.

Polychlorinated biphenyls (PCBs) are a class of important organic pollutants which undergo very slow degradation and tend to persist for a long time in the environment. PCBs have various negative effects on living organisms, human health and the environment in general. A method for determining PCB levels in aqueous matrices was developed consisting of solid-phase extraction (SPE) and GC/MS determination. The average recoveries of PCB congeners from artificially spiked deionized water were around 85%. The PCB concentration of 3.3±0.1 μg·l-1 (a sum of selected congeners) was detected in contaminated groundwater originated from the area of a former asphalt concrete producing plant. The most abundant PCBs were trichlorinated congeners which together comprised about 80% of the total PCB content. The optimised SPE method was further applied together with accelerated solvent extraction (ASE) to assess the degradation potential of oyster mushroom (Pleurotus ostreatus) which shows high degradation efficiency of various organic pollutants including PCBs. P. ostreatus belongs to ligninolytic (white-rot) fungi, which is a very promising group of microorganisms frequently studied due to their bioremediation potential. P. ostreatus, strain KRYOS was able to remove 41±8% of the initial amount (50 μg) of the...

Polychlorinated Biphenyls (PCB's) are organochlorine molecules which find various industrial and product applications. PCB's are of concern to biologists because they are toxic substances which have become global contaminants. They are also of concern to biologists and analytical chemists because they interfere with the determination of some organochlorine pesticide residues. PCB's were discovered to be environmental contaminants after they showed up as unidentified peaks in pesticide analysis using gas-liquid chromatography with an electron capture detector (GLC-EC). In the present experiment standard GLC-EC techniques were used to assay PCB's in Daphnia experimentally contaminated in the laboratory and in crayfish from the Willamette River. Daphnia were placed in water containing 0.1, 4, 50 or 100 parts per billion (ppb) PCB for 4 to 72 hours. There was no mortality in any of the experiments. The individual PCB compounds were apparently taken up equally, since relative peak heights were similar in the standard and the residues extracted from Daphnia. Final concentrations of PCB's in Daphnis ranged from 1200 times that of the water (at water concentrations of 100 ppb) to 104,000 times that of water (at water concentrations of 0.1 ppb). The lower concentrations used here approximate environmental PCB levels found in some areas of the U.S. and elsewhere. Assuming that chronic exposure to these lower concentrations would not strongly inhibit growth or reproduction of Daphnia,, the high biological magnification found here would suggest that Daphnia and related organisms may play an important role in the accumulation of PCB's in fresh water food webs. Digestive glands of crayfish taken from the Willamette River were analyzed for PCB's. Statistically significant regional differences were found in the concentrations of PCB's in these organisms in the lower Willamette Valley. Crayfish from the center of Portland have the highest residues (7 to 9 parts per million). A similar distribution has been previously reported for other urban areas. In the present investigation, however, the highest residues occurred in crayfish from the river at a point approximately in the center of the city itself, but two miles upstream from the major industrial areas. Thus, in this case, the major source of environmental contamination may have been released from manufactured goods (e.g., automobile tires, paints, etc.) rather than from industrial sewerage. I

No description available.