Dehydrochlorination of PCDDs on SWCN-Supported Ni10 and Ni13 Clusters, a DFT Study.

Polychlorinated dibenzo-p-dioxins (PCDDs) are known to be a group of compounds of high toxicity for animals and, particularly, for humans. Given that the most common method to destroy these compounds is by high-temperature combustion, finding other routes to render them less toxic is of paramount importance. Taking advantage of the physisorption properties of nanotubes, we studied the reactions of atomic hydrogen on physisorbed PCDDs using DFT; likewise, we investigated the reaction of molecular hydrogen on PCDDs aided by Ni10 and Ni13 clusters adsorbed on single-wall carbon nanotubes. Because dihydrogen is an easily accessible reactant, we found these reactions to be quite relevant as dehydrohalogenation methods to address PCDD toxicity.

Applying the Global Monitoring Plan and analysis of POPs results in atmospheric air in Mexico (2017-2018).

Air is one of the target matrices of the Global Monitoring Plan (GMP) of the Stockholm Convention to determine concentrations and transport of Persistent Organic Pollutants (POPs). Mexico participates in the GMP for POPs in ambient air through the AIR-Global Environment Facility (GEF) program. The objective of this study was to analyze the results of POPs monitoring of air samples collected in Los Mochis, Sinaloa, Mexico, between 2017 and 2018. Passive samplers were used for the determination of chlorinated basic POPs, indicator polychlorinated biphenyls (Ind. PCBs), polybrominated biphenyl ethers (PBDEs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dl-PCBs). A principal component analysis was applied to determine relationships between pollutants and groups present in the ambient air of the rural study area. Of the total POPs analyzed, 85.56% were detected in ambient air samples from Mexico. Organochlorine compounds, as DDT derivatives, were identified mainly, as well as PBDEs, PCDDs, and PCDFs. The prevalence of compounds differed according to the seasonality of sampling, with no change in average concentration between monitoring years.

Levels of Polychlorinated Dibenzo-p-Dioxins/Furans (PCDD/Fs) and Dioxin-Like Polychlorinated Biphenyls (DL-PCBs) in Human Breast Milk in Chile: A Pilot Study.

Persistent organic pollutants (POPs) are organic compounds that resist biochemical degradation, moving long distances across the atmosphere before deposition occurs. Our goal was to provide up-to-date data on the levels of polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in breast milk from Chilean women and to estimate the exposure of infants due to breast milk consumption. In Chile, we conducted a cross-sectional study based on methodologies proposed by the WHO, with a sample of 30 women recruited from three defined areas: 10 from the Arica Region (urban; Arica and Parinacota Region), 10 from Coltauco (rural; O'Higgins Region), and 10 from Molina (40% rural; Maule Region). High-resolution gas chromatography coupled with high-resolution mass spectrometry (HRGC/HRMS) was performed on pooled samples from each area. We calculated equivalent toxic concentrations (WHO-TEQ) based on the current WHO Toxic Equivalency Factors (TEF). The minimum and maximum values of ∑ PCDDs/Fs + DL-PCBs-TEQ were 4.317 pg TEQ/g fat in Coltauco and 6.31 pg TEQ/g fat in Arica. Molina had a total TEQ of 5.50 pg TEQ/g fat. The contribution of PCDD/Fs was approximately five-fold higher than that of DL-PCBs. The Estimated Daily Intake (EDI) of ∑ PCDDs/Fs + DL-PCBs based on the three pooled samples ranged between 6.71 and 26.28 pg TEQ/kg body weight (bw)/day, with a mean intake of 16.11 (±6.71) pg TEQ/kg bw/day in breastfed children from 0 to 24 months old. These levels were lower than those reported in international studies. Despite the fact that the observed levels were low compared to those in most industrialized countries, the detection of a variety of POPs in breast milk from Chilean women indicates the need for follow-up studies to determine whether such exposures during childhood could represent a health risk in adulthood.

High levels of dioxins and PCBs in meat, fat and livers of free ranging pigs, goats, sheep and cows from the island of Curaçao.

Samples of adipose tissue, meat and livers from pigs, cows, sheep and goats from Curaçao were analysed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and dioxin-like (dl-) and non-dioxin-like (ndl-) PCBs (polychlorinated biphenyls). Levels in many samples of adipose tissue were higher than the EU maximum levels (MLs) for PCDD/Fs and the sum of PCDD/Fs and dl-PCBs (sum-TEQ), indicating unusually high levels. Median sum-TEQ (Toxic Equivalents) levels for pigs, cows, sheep and goats were 0.9 (range 0.3-35), 3.0 (0.5-14), 5.7 (0.3-28) and 6.5 (0.5-134) pg TEQ g-1 fat. For most samples, the congener pattern pointed to the burning of waste as the major source, in line with the fact that most animals forage outside. MLs for ndl-PCBs were also exceeded in some of the samples, indicating that some areas are additionally contaminated with PCBs. Meat levels showed similar lipid based levels as adipose tissue, contrary to liver levels, which were much higher in most animals. Pigs showed liver sequestration at lower levels in adipose tissue than the ruminants. The relatively high levels observed in this study are likely to result in high exposure of consumers and measures were taken to reduce the contamination of areas where animals forage.

Reduction of Management Costs and Avoidance of Air Release of Carcinogens Through a Waste Segregation Program in a Brazilian Medical Institution.

Hospital waste management is a current sustainability challenge. Although not always performed, the most applied approach in current protocols is the proper segregation of waste. The incineration of hospital waste is an significant source of emission of specific toxic particles and gases. We highlighted dioxins, whose representatives have been considered carcinogenic agents since 1994. Several experimental and epidemiologic studies have shown greater cancer morbidity and mortality associated with dioxin exposure. In the present study, we presented the impact of a hospital waste management program implemented in an oncology institution based on proper segregation and consequent reduction of incinerated mass. Data were collected for 8 years and the waste was separated into five categories: infectious (A4), chemical (B), recyclable (DR), non-recyclable (DNR), and sharps (E). The classes addressed to incineration were A4, B, and E. A team education starting from the admission process and with a continued education program was essential for a successfully implemented program. We achieved a 66% saving of waste from incineration, equivalent to 76 tons, of which 71.9 tons corresponded to recyclable waste. If the waste separation protocol was not implemented, the biohazardous and chemical material would contaminate the rest of the residues, making incineration as a final destination mandatory for all the waste. This scenario would result in significantly more dioxins release and a 64% higher cost of waste management. This low-cost implementation measure was effective in the cost reduction of waste management and minimization of air release of human carcinogens.

Metabolic and Hematological Responses to Endotoxin-Induced Inflammation in Chicks Experiencing Embryonic 2,3,7,8-Tetrachlorodibenzodioxin Exposure.

Dioxin exposure during bird embryonic development disrupts immunity as well as mechanisms involved in energy metabolism, potentially affecting negatively acute-phase responses to pathogens. Thus, we hypothesized that embryonic exposure to 2,3,7,8-tetrachlorodibenzodioxin (TCDD) changes the metabolism and blood physiology of domestic chicks, affecting their physiological competence for responding to immune challenges. To test this hypothesis, we injected doses of 0, 1.5, and 3 ng TCDD/egg (based on survival experiments) on embryonic day 4 and then measured O2 consumption and CO2 production for metabolic rate, ventilation, and body temperature (TB ) in 5-d-old chicks. Then, chicks were injected with lipopolysaccharide (LPS, endotoxin) or saline prior to repeating the physiological measurements. A second chick group exposed to identical TCDD and LPS treatments had blood partial pressure of oxygen, partial pressure of carbon dioxide, pH, bicarbonate concentration, lactate concentration, osmolality, hemoglobin concentration, red blood cell concentration, and hematocrit, as well as TB , analyzed at 1 and 5 h after LPS injection. Metabolism in chicks embryonically exposed to 1.5 and 3 ng TCDD/egg was up to 37% higher, whereas body mass of chicks exposed to 3 ng TCDD/egg was approximately 6% lower. Chicks embryonically exposed to 3 ng TCDD/egg challenged with LPS showed a relative persistent hypometabolism accompanied by elimination of the normal hematological and osmotic responses to LPS. We conclude that embryonic exposure to TCDD affects posthatching metabolism as well as impairs metabolic, hematological, and osmotic responses to LPS. Environ Toxicol Chem 2020;39:2208-2220. © 2020 SETAC.

Polychlorinated biphenyls are still alarming persistent organic pollutants in marine-origin animal feed (fishmeal).

The presence of polychlorinated biphenyls (PCBs) in feed materials has caused great public concern because PCBs can accumulate in farmed animals, be transferred farm-to-fork and, ultimately, have a detrimental impact on human health. Recently, the occurrence of PCBs in marine environments has garnered scientific attention due to their high levels and potential reproductive threats to marine apex predators. Fishmeal is marine-origin feed material and is susceptible to PCB contamination from the aquatic trophic chain. The present study collected 102 fishmeal samples during 2012-2017 from major global fishmeal production areas (United States, Europe, China, South America and Southeast Asia). The levels of PCBs (26 congeners) were between 0.4 and 19.9 ng g-1 dw (mean: 1.94 ng g-1 dw), with a 75.3% contribution from indicator PCBs on a weight basis. Together with PCDD/Fs, 4.9% of fishmeal exceeded the maximum levels set by the European Commission for dioxin-like compounds (4.0 pg WHO-TEQ/g). The highest PCB levels were found in fishmeal from the U.S. (6.85 ng g-1 dw), which was nearly five times higher than the other four sampling areas. No clear time trends were found for PCBs in fishmeal during the sampling period. Predicted PCB concentrations in farmed fish via fishmeal consumption were between 1.24 and 2.76 ng g-1 dw, which was comparable to PCBs in market fish. When compared to other emerging POPs in the same batches of fishmeal, PCBs were still found to be an alarming class of POPs. Some PCB and PBDE congeners might have similar sources and environmental behaviors.

The History of the Dioxin issue in Brazil: From citrus pulp crisis to food monitoring (REVIEW).

Dioxins and furans are ubiquitous, anthropogenic environmental contaminants which can be found even in isolated places. Exposition to these chemicals poses several risks to humans such as thyroid dysfunction, cardiovascular diseases, and even cancer. In this review, the dioxin issue is analyzed in the light of the events that brought the World's attention to these pollutants, and the evolution of Brazilian scientific data on this matter since the citrus pulp crisis in 1998. Soil and air have been the main environmental matrices studied in Brazil. However, most of the research focuses on contaminated areas, with few or no data available on background levels. With the ratification of the Stockholm Convention in 2010, Brazil started to implement some measures to monitor the release of dioxins to the environment, such as the national inventory of sources. Still, the country lacks specific legislation stating acceptable limits for some industrial processes known to be source of dioxins emissions. Likewise, food monitoring has grown in recent years with the expansion of food groups monitored in the National Control Plan for Residues and Contaminants, but the available data do not allow affirming whether Brazilian residents are safe, as regard to exposure via food consumption. The implementation of a systemic survey such as a Total Diet Study would be a good strategy for a long-term monitoring not only for dioxins but also for other contaminants. Unfortunately, progressive cuts in science funds are holding back the scientific production in Brazil, whereas worldwide new emerging contaminants are being monitored and included in National Monitoring Plans both on food and environment matrices.

Aryl hydrocarbon receptor-based bioassays for dioxin detection: Thinking outside the box.

Despite intensive media coverage and international regulations, man-made persistent organic pollutants such as dioxins represent a serious environmental and health threat. Their detection by sophisticated chromatography technologies is highly complex, impeding the constant monitoring of food or environmental samples. This limitation has fostered the development of generations of bioassays exploiting the molecular function of the aryl hydrocarbon receptor (AhR), which binds toxic compounds and directly activates the transcription of target genes. Here, we review the rich panel of available AhR-dependent bioassays and propose a novel classification based on the source of AhR, which can either be endogenously produced by cell types or tissues naturally responsive to dioxins, or exogenously introduced into a wide range of cellular contexts. In both cases, in vitro and in vivo strategies have been engineered to monitor the formation of molecular complexes, and the activation of direct downstream targets or reporter genes. We evaluate and compare bioassays based on exogenous and endogenous AhR proteins and discuss their specific challenges, strengths and opportunities for futures applications. Undoubtedly, the dynamic field of AhR-dependent bioassays will keep providing new and original strategies to help protect human health and ecosystems from persistent organic pollutants.

Environmental Exposure to Dioxins, Dibenzofurans, Bisphenol A, and Phthalates in Children with and without Autism Spectrum Disorder Living near the Gulf of Mexico.

Environmental exposure to organic endocrine disrupting chemicals, including dioxins, dibenzofurans, bisphenol A (BPA), and phthalates has been associated with neurodevelopmental disorders, including autism spectrum disorder (ASD). We conducted a pilot monitoring study of 30 ASD cases and 10 typically developing (TD) controls ages 2-8 years from communities along the Gulf of Mexico near Alabama, which houses 14 Superfund sites, to assess the concentrations of dioxins and dibenzofurans in serum, and BPA and phthalate ester metabolites in urine. Based on General Linear Models, the lipid- or creatinine-adjusted geometric mean concentrations of the aforementioned chemicals did not differ between the ASD case and TD control groups (all p ≥ 0.27). We compared our findings to the adjusted means as reported by the National Health and Nutrition Examination Survey, survey years 2011-2012, and found that TD controls in our study had lower BPA (59%) and MEHHP (26%) concentrations, higher MBP (50%) concentration, and comparable (<20% difference) MEP, MBZP, MEOHP, and MCPP concentrations. We also conducted a preliminary investigation of dietary exposures and found that the consumption of certain types of fish may be associated with higher OCDD concentrations, and the consumption of soft drinks and juices may be associated with lower BPA and MEOHP concentrations, respectively.

Aryl hydrocarbon receptor overexpression in miniaturized follicles in female pattern hair loss

Abstract The etiopathogenesis of female pattern hair loss is still poorly understood. In addition to genetic and hormonal elements, environmental factors could be involved. The aryl hydrocarbon receptor is expressed in keratinocytes and can be activated by environmental pollutants leading to alterations in the cell cycle, inflammation, and apoptosis. Here we demonstrate the overexpression of nuclear aryl hydrocarbon receptors in miniaturized hair follicles in female pattern hair loss.

Fast extraction of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran in sewage sludge and soil samples.

The current environmental legislations recommend monitoring chemical contaminants such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans before the use of sewage sludge on the agricultural land. In this study, a solid-liquid extraction with low-temperature purification (SLE-LTP) was optimized and validated to determine 2,3,7,8-tetrachlorodibenzo-p-dioxin and 2,3,7,8-tetrachlorodibenzofuran in sewage sludge and soil samples. The analyses were performed by gas chromatography-mass spectrometry operating in the selective ion mode (GC-MS-SIM). Acetonitrile:ethyl acetate 6.5:1.5 (v/v) was the best extraction phase, and the recoveries percentages were close to 100%. The linearity was demonstrated in the range of 1.25-25 µg L-1 of 1.25-20 µg L-1 for sewage sludge and soil, respectively. Matrix effect was proved for the two compounds and in the two matrices studied. Extraction percentages were between 78 and 109% and relative standard deviations ≤ 19%. The proposed method is faster than methods described in the literature because showed a few steps. The quantification limits (LOQ) in sewage sludge were 6.4 and 32 ng TEQ kg-1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. In soil, LOQs were 0.8 and 8.0 ng TEQ kg-1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. These values are lower than the maximum residue limits established by European Legislation. The method was applied to 22 agricultural soil samples from different Brazilian cities and 2,3,7,8-TCDF was detected in one of these samples.

Determination of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in Brazilian cow milk.

The determination of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in raw cow milks have never been reported in Brazil. Since the consumption of food of animal origin, including milk and dairy products, is the major source of human exposure to these compounds, this study aimed to establish the levels and profile of seven PCDDs and ten PCDFs in raw cow milk samples collected in eight Brazilian states which among the major milk producer states. Raw milk samples were collected in 34 different dairy cattle farms during the summer of 2013. All PCDD/Fs congeners were found at least in some of the 34 samples studied. The octa-chlorinated congeners (OCDD and OCDF) were ubiquitous and also present in high concentrations. The mean values of WHO-TEQ1998;2005 were respectively 1.66 and 1.36pgTEQg-1 fat and samples taken in São Paulo showed the highest WHO-TEQ values (2.46 TEQ1998g-1 fat and 2.10pgTEQ2005g-1 fat). Although all samples showed some contamination level, all values were below the limit established by European Union for total PCDD/Fs in cow milk (3pgWHO-TEQ1998g-1 fat). Principal Component Analysis (PCA) showed that OCDD and OCDF were responsible for 73% and 20% of the total data variance, respectively and they presented an independent behavior, probably as a result of distinct origins. The use of TEQ as weights in the PCA, revealed the importance of the penta-chloro congeners and it was possible to identify sample distribution patterns probably associated with the main PeCDD and PeCDF. The importance of local sources to PCDD/Fs concentrations is still to be evaluated and determined.

Impact of forest fires on the concentrations of polychlorinated dibenzo-p-dioxin and dibenzofurans in coastal waters of central Chile.

The relationship between the occurrence of forest fires in central Chile and the total concentration of dioxins and furans (PCDD/F) in nearby coastal waters was analyzed. The data for this analysis was obtained from a long-term environmental monitoring program (PROMNA) in the Bio-Bio Region. Quantification of PCDD/F was performed using HRGC/HRMS at the MSS laboratory in England. Between 2006 and 2014, peaks were observed in February 2007 and 2012. These concentration maxima coincided with major forest fires in the Bio-Bio Region and particularly with those in the Itata River Basin. The January 2012 fires generated an intense short-term response that was associated with atmospheric transport which increases medium toxicity furan-type congeners concentrations (TCDF, PCDF and HxCDF) and six months later a concentration increase of low toxicity dioxin-type congeners was observed (OCDD, HpCDD and HxCDD) coinciding with maximum winter river flow. These results suggest that forest fires near the coastal zone are responsible for increases in PCDD/F concentration observed in the study area.

Polychlorinated dibenzo-p-dioxins, dibenzofurans and dioxin-like PCBs in commercialized food products from Colombia.

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) are commonly known as dioxins and are the most toxic members of persistent organic pollutants (POPs) because present a variety of health effects especially as promoting agent of growing and transformation of cancer cells. They are bio-accumulate in humans primarily via the diet, specifically by ingestion of foods that have high lipid content which are generally associated with foods of animal origin such as oils and fats and with fishery and dairy products. In Colombia the Ministry of Health and Social Protection which is the entity responsible for surveillance food conditions, has established maximum levels for dioxins and dl-PCBs in oils from animal and vegetable origins. Oils of vegetable and animal origin represent an appreciable intake in the country thus the presence of dioxins and dl-PCBs in these materials is a matter of concern because they can bioaccumulate in fat. In this contribution the levels of PCDD/Fs and dl-PCBs in olive, soybean, fish oil, butter and shrimp consumed in Colombia were determined using HRGC-HRMS and were compared with the maximum levels permitted in oil samples according to both the Colombian and European regulations. WHO-TEQ concentrations for PCDD/Fs and dioxin like PCBs ranged from 0.24 to 1.710pgWHO-TEQ PCDD/Fg(-1) of fat and from 0.050 to 3.000pgWHO-TEQ PCBg(-1) of fat, respectively. As expected, fish oils and shrimp present the highest WHO-TEQ PCDD/Fs and dl-PCBs values followed by butter and soybean oil sample, while the olive oil shows the lowest levels. In general, the vegetable oils show levels below the limits established by both the Colombian and European regulations. The levels from soybean oil found in this study were slightly higher than the threshold established both by the Commission Regulation European Union (EU) and the Colombian legislation, while fish oils showed concentrations above the European regulations. Furthermore, shrimp exhibited values below the maximum concentration levels established by the EU and Colombian regulation.

Occurrence, variability and human exposure to Polychlorinated Dibenzo-p-dioxins (PCDDs), Polychlorinated Dibenzofurans (PCDFs) and Dioxin-Like Polychlorinated Biphenyls (DL-PCBs) in dairy products from Chile during the 2011-2013 survey.

Levels, congener profiles of PCDD/Fs, DL-PCBs and human exposure for these xenobiotics never have been reported in Chile. For that purpose 102 raw cow milk samples were collected from seven different regions of Chile during 2011 until 2013. The highest mean level for PCDD/Fs, corresponds to 0.32 pg WHO-TEQ2005 g(-1) fat (2012) and for DL-PCBs 0.17 pg WHO-TEQ2005 g(-1) fat (2011), using the upper bound approach. Penta and tetra chlorinated congeners dominated PCDD/Fs profiles in a WHO-TEQ2005 basis during the survey. In the case of DL-PCBs, PCB 126 dominated the profiles with 89%. Statistical analysis showed significant difference among years only in DL-PCBs residues. Also dietary intake was estimated, and the highest level for total sum of PCDD/Fs and DL-PCBs for adult was 0.16 pg WHO-TEQ kg(-1) b.w d(-1) (2011) and for children correspond to 0.65 pg WHO-TEQ kg(-1) b.wd(-1) (2011). Concentrations and dietary intake for the studied compounds in milk and butter samples were below international and national regulations.

Biodegradation of 1,2,3,4-tetrachlorodibenzo-p-dioxin in liquid broth by brown-rot fungi.

Dioxins are a class of extremely hazardous molecules that might pose a threat to the environment. This work evaluated the microbial degradation of 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD), in liquid broth using three brown-rot fungi and one white-rot fungi as control. A fast and reliable extraction method with recoveries of over 98% together with a validated GC-MS method was developed, and applied to quantify 1,2,3,4-TCDD in liquid broth, mycelia and reaction flask, with detection limits of 10 ppb. Among the four strains tested, brown-rot fungus Aspergillus aculeatus showed best results, removing up to 21% of dioxin after 30-day incubation. The results open both a path for biotechnological interest in bioremediation purposes and environmental behavior studies by using brown-rot fungus.

Dioxins and polychlorinated biphenyls concentrations in Larus dominicanus. Case study: Marambaia island, Sepetiba bay, Rio de Janeiro State, Brazil / Concentrações de dioxinas e bifenilas policloradas em Larus dominicanus. Estudo de caso: ilha da Marambaia, baía de Sepetiba, Estado do Rio de Janeiro, Brasil

Seabirds play a significant role as bioindicators: they are conspicuous, relatively easy to observe, well-established studied group of organisms, and in the focus of public interest due to pollution in aquatic ecosystem. Systematically, a significant number of man-made chemicals have been introduced in the marine environment and represent the major problem arising in the development worldwide. Many of these chemical contaminants are persistent, known to bioaccumulate and biomagnify through the aquatic food web, affecting species associated with aquatic systems. Dioxins [polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF)] and polychlorinated biphenyls (PCB) concentrations were measured in Kelp gull Larus dominicanus collected from 2006 to 2011 on Marambaia Island, Sepetiba Bay, Rio de Janeiro State, Brazil. Detectable liver concentrations of PCDD Fs-1 and PCBs were found in all samples analyzed. These represent some of the first measurements of PCDD Fs-1 and PCBs in seabirds from this area. Although levels of these contaminants in the tested species currently appear to fall below critical values, a continuous and systematic monitoring on these compounds becomes essential and desirable to not express toxic values in the future.(AU)

Aves marinhas desempenham uma função significativa como bioindicadores: elas são conspícuas, relativamente fáceis de observar, grupos de organismos de estudo bem estabelecidos e no foco de interesse público devido à poluição no ecossistema aquático. Sistematicamente, um número significativo de produtos químicos sintéticos vêm sendo introduzidos no ambiente marinho, representando um dos principais problemas que se coloca no desenvolvimento em todo o mundo. Muitos desses contaminantes químicos são persistentes, conhecidos por bioacumular e biomagnificar através de suas movimentações na cadeia alimentar, afetando espécies associadas aos sistemas aquáticos. Concentrações de dioxinas [dibenzo-p-dioxinas policloradas (PCDD), dibenzofuranos (PCDF)] e bifenilas policloradas (PCB) foram medidas em gaivotões Larus dominicanus coletadas de 2006 a 2011 na Ilha da Marambaia, Baía de Sepetiba, Rio de Janeiro, Brasil. Estes dados representam algumas das primeiras medições de PCDD Fs-1 e PCBs em aves marinhas nesta área estudada. Embora os níveis destes contaminantes na espécie testada apresentarem níveis abaixo dos valores críticos, o monitoramento contínuo, sistemático, torna-se imprescindível e desejável para que estes compostos não expressem no futuro valores tóxicos.(AU)

High accumulation of PCDD, PCDF, and PCB congeners in marine mammals from Brazil: a serious PCB problem.

Blubber samples from three delphinid species (false killer whale, Guiana and rough-toothed dolphin), as well as liver samples from franciscana dolphins were analyzed for dioxins and related compounds (DRCs). Samples were collected from 35 cetaceans stranded or incidentally captured in a highly industrialized and urbanized area (Southeast and Southern Brazilian regions). Dioxin-like PCBs accounted for over 83% of the total TEQ for all cetaceans. Non-ortho coplanar PCBs, for franciscanas (82%), and mono-ortho PCBs (up to 80%), for delphinids, constituted the groups of highest contribution to total TEQ. Regarding franciscana dolphins, significant negative correlations were found between total length (TL) and three variables, ΣTEQ-DRCs, ΣTEQ-PCDF and ΣTEQ non-ortho PCB. An increasing efficiency of the detoxifying activity with the growth of the animal may be a plausible explanation for these findings. This hypothesis is reinforced by the significant negative correlation found between TL and PCB126/PCB169 concentration ratio. DRC concentrations (ng/g lipids) varied from 36 to 3006, for franciscana dolphins, as well as from 356 to 30,776, for delphinids. The sum of dioxin-like and indicator PCBs varied from 34,662 to 279,407 ng/g lipids, for Guiana dolphins from Rio de Janeiro state, which are among the highest PCB concentrations ever reported for cetaceans. The high concentrations found in our study raise concern not only on the conservation of Brazilian coastal cetaceans, but also on the possibility of human health problem due to consumption of fish from Brazilian estuaries.

Dioxins and polychlorinated biphenyls concentrations in Larus dominicanus. Case study: Marambaia island, Sepetiba bay, Rio de Janeiro State, Brazil / Concentrações de dioxinas e bifenilas policloradas em Larus dominicanus. Estudo de caso: ilha da Marambaia, baía de Sepetiba, Estado do Rio de Janeiro, Brasil

Seabirds play a significant role as bioindicators: they are conspicuous, relatively easy to observe, well-established studied group of organisms, and in the focus of public interest due to pollution in aquatic ecosystem. Systematically, a significant number of man-made chemicals have been introduced in the marine environment and represent the major problem arising in the development worldwide. Many of these chemical contaminants are persistent, known to bioaccumulate and biomagnify through the aquatic food web, affecting species associated with aquatic systems. Dioxins [polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF)] and polychlorinated biphenyls (PCB) concentrations were measured in Kelp gull Larus dominicanus collected from 2006 to 2011 on Marambaia Island, Sepetiba Bay, Rio de Janeiro State, Brazil. Detectable liver concentrations of PCDD Fs-1 and PCBs were found in all samples analyzed. These represent some of the first measurements of PCDD Fs-1 and PCBs in seabirds from this area. Although levels of these contaminants in the tested species currently appear to fall below critical values, a continuous and systematic monitoring on these compounds becomes essential and desirable to not express toxic values in the future.

Aves marinhas desempenham uma função significativa como bioindicadores: elas são conspícuas, relativamente fáceis de observar, grupos de organismos de estudo bem estabelecidos e no foco de interesse público devido à poluição no ecossistema aquático. Sistematicamente, um número significativo de produtos químicos sintéticos vêm sendo introduzidos no ambiente marinho, representando um dos principais problemas que se coloca no desenvolvimento em todo o mundo. Muitos desses contaminantes químicos são persistentes, conhecidos por bioacumular e biomagnificar através de suas movimentações na cadeia alimentar, afetando espécies associadas aos sistemas aquáticos. Concentrações de dioxinas [dibenzo-p-dioxinas policloradas (PCDD), dibenzofuranos (PCDF)] e bifenilas policloradas (PCB) foram medidas em gaivotões Larus dominicanus coletadas de 2006 a 2011 na Ilha da Marambaia, Baía de Sepetiba, Rio de Janeiro, Brasil. Estes dados representam algumas das primeiras medições de PCDD Fs-1 e PCBs em aves marinhas nesta área estudada. Embora os níveis destes contaminantes na espécie testada apresentarem níveis abaixo dos valores críticos, o monitoramento contínuo, sistemático, torna-se imprescindível e desejável para que estes compostos não expressem no futuro valores tóxicos.