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Organic Pollutants (organic + pollutant)
Kinds of Organic Pollutants Selected AbstractsThe European Union in international environmental negotiations: an analysis of the Stockholm Convention negotiationsENVIRONMENTAL POLICY AND GOVERNANCE, Issue 1 2009Tom Delreux Abstract This article focuses on the way the European Union acted as a negotiating party during the international negotiations leading to the Stockholm Convention on Persistent Organic Pollutants (1998,2000). Starting from a principal,agent model, the article discusses how the EU participated in these negotiations and how the internal decision-making process developed. It argues that the EU was able to negotiate in a unified and influential way by defending a common position, which was expressed by a flexible negotiation arrangement, at the international level. Three features of the EU decision-making process engendered such a strong EU negotiation arrangement: homogeneous preferences among the actors in the EU, symmetrically distributed information among them and a cooperative and institutionally dense decision-making context. Copyright © 2009 John Wiley & Sons, Ltd and ERP Environment. [source] Impact of Kerogen Heterogeneity on Sorption of Organic Pollutants.ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 8 2009Abstract The overall goal of the present study was to establish correlations between organic pollutant sorption and physicochemical properties of kerogen materials. Three coal samples, each representing a typical kerogen type, were used as the starting materials. A thermal technique was employed to treat the kerogen materials under seven different temperatures ranging from 200 to 500C to simulate different diagenetic history. These samples were systematically characterized for their chemical compositions, functionalities, physical rigidity, and optical properties. The results showed that the chemical, spectroscopic, and optical microscopic properties of each kerogen series changed consistently as a function of treatment temperature or kerogen maturation. The oxygen-to-carbon atomic ratio decreased from 0.29, 0.12, and 0.07 for the original lignite (XF0), fusinite (HZ0), and lopinite (LP0) samples, respectively, to 0.07, 0.06, and 0.04 for XF7, HZ7, and LP7, respectively, that underwent the highest temperature treatment. The hydrogen-to-carbon atomic ratio exhibited similar reducing trend, which is consistent with the aromaticity increasing from 45 to 58% of the original samples to 76 to 81% of highly mature samples. Under the fluorescence microscope, the organic matrix changed from yellow (original lignite sample) and red-brown (original lopinite sample) to colorless for the samples of higher maturation. The measured reflecting index increased from the original samples to the highly mature samples. Moreover, the original and the slightly matured samples exhibited very different chemical compositions and structural units among the three types due to the difference in their source materials. As the kerogen maturation increased, such differences decreased, indicating highly mature kerogen became homogenized regardless of the source material. [source] Persistent Organic Pollutants in Fish Oil Supplements on the Canadian Market: Polychlorinated Biphenyls and Organochlorine InsecticidesJOURNAL OF FOOD SCIENCE, Issue 1 2009Dorothea F.K. Rawn ABSTRACT:, Fish and seal oil dietary supplements, marketed to be rich in omega-3 fatty acids, are frequently consumed by Canadians. Samples of these supplements (n,= 30) were collected in Vancouver, Canada, between 2005 and 2007. All oil supplements were analyzed for polychlorinated biphenyls (PCBs) and organochlorine insecticides (OCs) and each sample was found to contain detectable residues. The highest ,PCB and ,DDT (1,1,1-trichloro-di-(4-chlorophenyl)ethane) concentrations (10400 ng/g and 3310 ng/g, respectively) were found in a shark oil sample while lowest levels were found in supplements prepared using mixed fish oils (anchovy, mackerel, and sardine) (0.711 ng ,PCB/g and 0.189 ng ,DDT/g). Mean ,PCB concentrations in oil supplements were 34.5, 24.2, 25.1, 95.3, 12.0, 5260, 321, and 519 ng/g in unidentified fish, mixed fish containing no salmon, mixed fish with salmon, salmon, vegetable with mixed fish, shark, menhaden (n,= 1), and seal (n,= 1), respectively. Maximum concentrations of the other OCs were generally observed in the seal oil. The hexachlorinated PCB congeners were the dominant contributors to ,PCB levels, while ,DDT was the greatest contributor to organochlorine levels. Intake estimates were made using maximum dosages on manufacturers' labels and results varied widely due to the large difference in residue concentrations obtained. Average ,PCB and ,DDT intakes were calculated to be 736 ± 2840 ng/d and 304 ± 948 ng/d, respectively. [source] Dietary accumulation of hexabromocyclododecane diastereoisomers in juvenile rainbow trout (Oncorhynchus mykiss) I: Bioaccumulation parameters and evidence of bioisomerizationENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 7 2006Kerri Law Abstract Juvenile rainbow trout (Oncorhynchus mykiss) were exposed to three diastereoisomers (,, ,, ,) of hexabromocyclododecane (C12H18Br6) via their diet for 56 d followed by 112 d of untreated food to examine bioaccumulation parameters and test the hypothesis of in vivo bioisomerization. Four groups of 70 fish were used in the study. Three groups were exposed to food fortified with known concentrations of an individual diastereoisomer, while a fourth group were fed unfortified food. Bioaccumulation of the ,-diastereoisomer was linear during the uptake phase, while the ,- and ,-diastereoisomers were found to increase exponentially with respective doubling times of 8.2 and 17.1 d. Both the ,- and the ,-diastereoisomers followed a first-order depuration kinetics with calculated half-lives of 157 ± 71 and 144 ± 60 d (±1 × standard error), respectively. The biomagnification factor (BMF) for the ,-diastereoisomer (BMF = 9.2) was two times greater than the ,-diastereoisomer (BMF = 4.3); the large BMF for the ,-diastereoisomer is consistent with this diastereoisomer dominating higher-trophic-level organisms. Although the BMF of the ,-diastereoisomer suggests that it will biomagnify, it is rarely detected in environmental samples because it is present in small quantities in commercial mixtures. Results from these studies also provide evidence of bioisomerization of the ,- and ,-diastereoisomers. Most importantly, the ,-diastereoisomer that was recalcitrant to bioisomerization by juvenile rainbow trout in this study and known to be the dominant diastereosiomer in fish was bioformed from both the ,- and the ,-diastereoisomers. To our knowledge, this is the first report of bioisomerization of a halogenated organic pollutant in biota. [source] Multifunctional Au-Coated TiO2 Nanotube Arrays as Recyclable SERS Substrates for Multifold Organic Pollutants DetectionADVANCED FUNCTIONAL MATERIALS, Issue 17 2010Xuanhua Li Abstract A multifunctional Au-coated TiO2 nanotube array is made via synthesis of a TiO2 nanotube array through a ZnO template, followed by deposition of Au particles onto the TiO2 surface using photocatalytic deposition and a hydrothermal method, respectively. Such arrays exhibit superior detection sensitivity with high reproducibility and stability. In addition, due to possessing stable catalytic properties, the arrays can clean themselves by photocatalytic degradation of target molecules adsorbed to the substrate under irradiation with UV light into inorganic small molecules using surface-enhanced Raman spectroscopy (SERS) detection, so that recycling can be achieved. Finally, by detection of Rhodamine 6G (R6G) dye, herbicide 4-chlorophenol (4-CP), persistent organic pollutant (POP) dichlorophenoxyacetic acid (2,4-D), and organophosphate pesticide methyl-parathion (MP), the unique recyclable properties indicate a new route in eliminating the single-use problem of traditional SERS substrates and show promising applications for detecting other organic pollutants. [source] Inorganic Macroporous Films from Preformed Nanoparticles and Membrane Templates: Synthesis and Investigation of Photocatalytic and Photoelectrochemical Properties,ADVANCED FUNCTIONAL MATERIALS, Issue 10 2003D.G. Shchukin Abstract Colloidal dispersions of titania, zirconia, tin oxide, indium oxide, and ceria have been successfully used to impregnate membrane templates and form the respective metal oxide (MO) porous films. The use of alumina and iron oxide sols in the same procedure, however, resulted in compact structures. By mixing different nanoparticle solutions before impregnation, final inorganic films containing two metal oxides, of variable metal oxide ratios, were obtained. The porous inorganic materials were analyzed in terms of surface area, pore size, film thickness, and crystallinity. The mechanism of nanoparticle infiltration and particle adsorption to the template walls is proposed based on the stability of the inorganic film and a study of the influence of either the sol concentration or washing times on the amount of inorganic substance incorporated in the hybrid material. The photocatalytic decomposition of an organic pollutant, 2-chlorophenol, was demonstrated for the porous titania material along with the structures containing mixtures of titania with zirconia, indium oxide, and tin oxide. A ratio of 9:1 TiO2/MO gave the highest photocatalytic activity, which was higher than the activity of Degussa P25 for the TiO2/In2O3 and TiO2/SnO2 systems under the same conditions. The titania films have also been attached to substrates,glass or indium tin oxide (ITO) surfaces,and the photoelectrochemical properties of the porous film attained. A comparison with a spin-coated titania film (prepared from the same colloidal dispersion) showed that the structured porous inorganic film has two times the photoelectrochemical efficiency as the spin-coated film. [source] Evaluation of Bioaccumulation Using In Vivo Laboratory and Field Studies,INTEGRATED ENVIRONMENTAL ASSESSMENT AND MANAGEMENT, Issue 4 2009Annie V Weisbrod Abstract A primary consideration in the evaluation of chemicals is the potential for substances to be absorbed and retained in an organism's tissues (i.e., bioaccumulated) at concentrations sufficient to pose health concerns. Substances that exhibit properties that enable biomagnification in the food chain (i.e., amplification of tissue concentrations at successive trophic levels) are of particular concern due to the elevated long-term exposures these substances pose to higher trophic organisms, including humans. Historically, biomarkers of in vivo chemical exposure (e.g., eggshell thinning, bill deformities) retrospectively led to the identification of such compounds, which were later categorized as persistent organic pollutants. Today, multiple bioaccumulation metrics are available to quantitatively assess the bioaccumulation potential of new and existing chemicals and identify substances that, upon or before environmental release, may be characterized as persistent organic pollutants. This paper reviews the various in vivo measurement approaches that can be used to assess the bioaccumulation of chemicals in aquatic or terrestrial species using laboratory-exposed, field-deployed, or collected organisms. Important issues associated with laboratory measurements of bioaccumulation include appropriate test species selection, test chemical dosing methods, exposure duration, and chemical and statistical analyses. Measuring bioaccumulation at a particular field site requires consideration of which test species to use and whether to examine natural populations or to use field-deployed populations. Both laboratory and field methods also require reliable determination of chemical concentrations in exposure media of interest (i.e., water, sediment, food or prey, etc.), accumulated body residues, or both. The advantages and disadvantages of various laboratory and field bioaccumulation metrics for assessing biomagnification potential in aquatic or terrestrial food chains are discussed. Guidance is provided on how to consider the uncertainty in these metrics and develop a weight-of-evidence evaluation that supports technically sound and consistent persistent organic pollutant and persistent, bioaccumulative, and toxic chemical identification. Based on the bioaccumulation information shared in 8 draft risk profiles submitted for review under the United Nations Stockholm Convention, recommendations are given for the information that is most critical to aid transparency and consistency in decision making. [source] Isolation and characterization of a biphenyl-utilizing psychrotrophic bacterium, Hydrogenophaga taeniospiralis IA3-A, that cometabolize dichlorobiphenyls and polychlorinated biphenyl congeners in Aroclor 1221JOURNAL OF BASIC MICROBIOLOGY, Issue 2 2006Adewale J. Lambo A psychrotrophic bacterium isolated from polychlorinated biphenyls (PCBs)-contaminated soil grew on biphenyl as sole carbon and energy source, and actively cometabolized PCBs at low temperature. Analysis of cellular fatty acids indicate that the bacterium is most closely related to Hydrogenophaga taeniospiralis . Resting cells incubated with 10 ppm of Aroclor 1221 at 5 or 30 °C for 48 h removed all mono-, most di-, and several trichlorobiphenyls. At 5 °C, removal of MCBs (monochlorobiphenyls) was between 63 to 89%, DCBs (dichlorobiphenyls) was between 30 to 78%, and TCBs (trichlorobiphenyls) was between 30 to 75%. At 30 °C, removal of MCBs was 100%, DCBs was between 30 to 100%, and TCBs was between 27 to 59%. Congeners with two or more ortho chlorine were generally resistant to degradation. However, removal of di- ortho plus para -substituted congeners at 30 °C and not at 5 °C, suggest that the presence of a para -chlorine enhanced the cometabolism of these congeners at 30 °C. Furthermore, after 72 h, resting cells removed 68 and 83% of 500 ,m of 2,4,-dichlorobiphenyl (2,4,-DCB) and, 35 and 44% of 500 ,m of 2,3-dichlorobiphenyl (2,3-DCB) at 5 and 30 °C, respectively. Analysis of metabolites by GC-MS indicates that the cometabolized 2,3-DCB was completely recovered as 2,3-chlorobenzoic acid (2,3-CBA), while the cometabolized 2,4,-DCB was not completely recovered as chlorobenzoic acid. To our knowledge, it is the first strain of Hydrogenophaga taeniospiralis found to degrade an organic pollutant, and also the first psychrotrophic strain of a member of the genus Hydrogenophaga to grow on biphenyl or cometabolize PCBs at low temperature. Results suggest that the bacterium has potential use in the bioremediation of PCB-contaminated sites in cold regions. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Dead-End Liposomal Electro-Filtration: Phenol Removal by Dioctadecyl Dimethyl Ammonium Chloride as a Case StudyCHEMICAL ENGINEERING & TECHNOLOGY (CET), Issue 8 2010M. Hakimhashem Abstract Among the important efforts that have been made for the removal of trace organic molecules, sorption by micelles and subsequent membrane filtration is a promising method which, however, still suffers from a number of disadvantages such as low efficiency and high energy consumption. In this article, we present the results of the sorption of phenol (as an important trace organic pollutant in industrial wastewater) to dioctadecyl dimethyl ammonium chloride (DODAC) liposomes, as well as the filtration properties of the resulting dispersion. Whereas the sorption of phenol by a 0.5,wt,% DODAC dispersion at neutral pH and ambient temperature was only 26,35,%, it increased to above 95,% at pH,11. Applying an electric field during the filtration process considerably improved both the filtrate flow rate and the retention. An electric field of 5,V/cm increased the filtrate flow rate at 200,kPa 30-fold. [source] Fate of Pesticides in the Environment and its BioremediationENGINEERING IN LIFE SCIENCES (ELECTRONIC), Issue 6 2005M. Gavrilescu Abstract The present paper is an overview of the presence and fate of pesticides as persistent organic pollutants in the environment as well as of the potential for their detoxification, also combined with chemical and physical treatment. It contains information gathered from a range of currently available sources. The fate of pesticides in the environment is analyzed considering the processes that determine their persistence and mobility, grouped into transport, transfer and transformation processes. Few pesticide characteristics such as persistence, mobility and biodegradability are emphasized. The fate of a pesticide and the potential for its persistence and mobility from the site of application are considered to be affected by the chemical and physical properties of the pesticide, site characteristics such as soil and groundwater individuality, climate and local weather conditions, biological population, and the handling practices of the pesticide user. Bioremediation, as one of the most environmentally-sound and cost-effective methods for the decontamination and detoxification of a pesticide-contaminated environment is discussed especially considering the factors affecting the biodegradability of pesticides such as biological factors and the characteristics of the chemical compounds. In situ and ex situ bioremediation as possible types of bioremediation activities are weighted up. Also, the paper includes some considerations for developing strategies regarding the choice of bioremediation technology, as well as advantages and disadvantages of the bioremediation of environmental components polluted with pesticides. [source] Tissue-specific distribution and whole-body burden estimates of persistent organic pollutants in the bottlenose dolphin (Tursiops truncatus)ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 6 2010Jennifer E. Yordy Abstract Most exposure assessments for free-ranging cetaceans focus on contaminant concentrations measured in blubber, and few data are available for other tissues or the factors governing contaminant distribution among tissues. The goal of this study was to provide a detailed description of the distribution of persistent organic pollutants (POPs) within the common bottlenose dolphin (Tursiops truncatus) body and assess the role of lipid dynamics in mediating contaminant distribution. Thirteen tissues (brain, blubber, heart, liver, lung, kidney, mammary gland, melon, skeletal muscle, spleen, thyroid, thymus, and testis/uterus) were sampled during necropsy from bottlenose dolphins (n,=,4) and analyzed for lipid and 85 POPs, including polychlorinated biphenyls, organochlorine pesticides, and polybrominated diphenyl ethers. Significant correlations between tissue POP concentrations and lipid suggest that distribution of POPs is generally related to tissue lipid content. However, blubber:tissue partition coefficients ranged widely from 0.753 to 6.25, suggesting that contaminant distribution is not entirely lipid-dependent. Tissue-specific and whole-body contaminant burdens confirmed that blubber, the primary site of metabolic lipid storage, is also the primary site for POP accumulation, contributing >90% to the whole-body burdens. Observations also suggest that as lipid mobilizes from blubber, contaminants may redistribute, leading to elevated tissue concentrations. These results suggest that individuals with reduced blubber lipid may be at increased risk for exposure-related health effects. However, this study also provides evidence that the melon, a metabolically inert lipid-rich structure, may serve as an alternate depot for POPs, thus preventing the bulk of blubber contaminants from being directly available to other tissues. This unique physiological adaptation should be taken into consideration when assessing contaminant-related health effects in wild cetacean populations. Environ. Toxicol. Chem. 2010;29:1263,1273. © 2010 SETAC [source] Polybrominated diphenyl ethers, toxaphenes, and other halogenated organic pollutants in great blue heron eggsENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 2 2010Louise Champoux Abstract The great blue heron (Ardea herodias) has been used as a bioindicator of the state of the St. Lawrence River (Québec, Canada) since 1996. At 5-year intervals, selected breeding colonies along the River and its estuary are visited to estimate reproductive success and determine levels of contamination. Brominated flame retardants are found in many ecosystems and are increasing in concentration in the Great Lakes, which is the source of much of the water for the St. Lawrence River. In 2001 and 2002, in addition to polychlorinated biphenyls (PCBs) and chlorinated pesticides, the levels of polybrominated diphenyl ethers (PBDEs), polychlorinated bornanes (toxaphene) congeners and non- ortho -substituted PCBs were measured for the first time in pools of great blue heron eggs. The PBDE levels in great blue heron eggs (70,1,377,ng/g wet wt) were comparable to those measured in herring gull (Larus argentatus) eggs from the Great Lakes. Toxaphene was detected in great blue heron eggs at levels comparable to those of other major chlorinated pesticides. Major toxaphene congeners were octachlorobornane P44 and the nonachlorobornane P50. Environ. Toxicol. Chem. 2010;29:243,249. © 2009 SETAC [source] Long-range transport of organic chemicals in the environmentENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 4 2009Martin Scheringer Abstract The long-range transport (LRT) of organic chemicals in the environment is reviewed, with particular focus on the role of environmental fate and transport models and the relationship between model results and field data. Results from generic multimedia box models, spatially resolved multimedia box models, and atmospheric transport models are highlighted, including conceptual investigations of cold-trap effect and global fractionation as well as results for particular chemicals, such as hexachlorocyclohexanes, DDT, polychlorinated biphenyls, perfluoroocctanoic acid, and polybrominated diphenyl ethers. Comparison of model results to field data shows that in many cases environmental fate models provide a good description of the distribution dynamics observed in the field, with deviations between measured and modeled concentrations around a factor of five. Sorption to atmospheric aerosols as a key process influencing the LRT of semivolatile organic chemicals (SOCs) is discussed, and the need for more measurements of the aerosol,air partitioning of SOCs and of the reactivity of particle-bound chemicals is pointed out. Key findings from field campaigns measuring legacy persistent organic pollutants (POPs) as well as new POPs are summarized. Finally, the relationship between science and politics in the field of POPs is addressed. Research into the LRT of organic chemicals has always occurred in interaction with political activities aiming to reduce the emissions of POPs. Since the late 1990s, the Stockholm Convention and the Aarhus Protocol on POPs have formed an important political context for research concerning POPs; the implementation of these international treaties creates a demand for ongoing research into the LRT of organic chemicals. [source] Anthropogenic persistent organic pollutants , lessons to learn from halogenated natural productsENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 11 2007Walter Vetter First page of article [source] Accumulation of polycyclic aromatic hydrocarbons in rural soils based on mass balances at the catchment scaleENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 4 2007Tilman Gocht Abstract Polycyclic aromatic hydrocarbons (PAHs) are hydrophobic organic pollutants that are ubiquitously distributed in the environment at relatively high concentrations. In our study we investigated the long-term fate of atmospheric PAHs in soils of rural areas, resulting from diffuse pollution based on mass balances at the catchment scale. By determining PAHs in several environmental compartments, estimates of soil storages and water fluxes were made and compared with atmospheric deposition. The results indicate that more than 90% of the incoming PAHs remain in the catchments and accumulate in the topsoils. Furthermore, revolatilization of PAHs from soils and degradation in the soils is very limited, resulting in ongoing accumulation in topsoils, in particular for low-volatile PAHs. Combustion-derived carbonaceous particles were detected in atmospheric deposition as well as in the soil samples. Since these particles are very strong adsorbents, they are suspected to play a key role in the environmental fate of the diffuse distributed PAHs. [source] Effects of brominated flame retardants and brominated dioxins on steroidogenesis in H295R human adrenocortical carcinoma cell lineENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 4 2007Ling Ding Abstract Brominated flame retardants (BFRs) and brominated dioxins are emerging persistent organic pollutants that are ubiquitous in the environment and can be accumulated by wildlife and humans. These chemicals can disturb endocrine function. Recent studies have demonstrated that one of the mechanisms of endocrine disruption by chemicals is modulation of steroidogenic gene expression or enzyme activities. In this study, an in vitro assay based on the H295R human adrenocortical carcinoma cell line, which possesses most key genes or enzymes involved in steroidogenesis, was used to examine the effects of five bromophenols, two polybrominated biphenyls (PBBs 77 and 169), 2,3,7,8-tetrabromodibenzo- p -dioxin, and 2,3,7,8-tetrabromodibenzofuran on the expression of 10 key steroidogenic genes. The H295R cells were exposed to various BFR concentrations for 48 h, and the expression of specific genes,cytochrome P450 (CYP11A, CYP11B2, CYP17, CYP19, and CYP21), 3,-hydroxysteroid dehydrogenase (3,HSD2), 17,-hydroxysteroid dehydrogenase (17,HSD1 and 17,HSD4), steroidogenic acute regulatory protein (StAR), and 3-hydroxy-3-methylglutaryl coenzyme A reductase (HMGR),was quantitatively measured using real-time polymerase chain reaction. Cell viability was not affected at the doses tested. Most of the genes were either up- or down-regulated, to some extent, by BFR exposure. Among the genes tested, 3,HSD2 was the most markedly up-regulated, with a range of magnitude from 1.6- to 20-fold. The results demonstrate that bromophenol, bromobiphenyls, and bromodibenzo- p -dioxin/furan are able to modulate steroidogenic gene expression, which may lead to endocrine disruption. [source] Bioconcentration of persistent organic pollutants in four species of marine phytoplanktonENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 11 2005Antje Gerofke Abstract The uptake of polychlorinated biphenyls (PCBs) was studied in four species of marine algae. A novel experimental system to establish and maintain constant dissolved concentrations of PCBs was employed. Headspace sampling was used to verify that the freely dissolved concentrations remained constant with time. The headspace analysis also allowed sorption to dissolved organic carbon (DOC) to be quantified for all but the most lipophilic PCB congeners. Equilibration with the dissolved phase was rapid for three of the four algae species (<1 d for the majority of congeners). Organic carbon,normalized algae/water partition coefficients (KAlgW) were similar for three of the four species, but were lower by a factor of 10 to 20 for Phaeodactylum tricornutum. The KAlgW values of the first three species were similar to the octanol/water partition coefficient (KOW) for those PCB congeners for which DOC sorption could be quantified. These KAlgW values also agreed well with organic carbon,normalized bioconcentration factors for PCBs in suspended particulate matter (BCFSPM) sampled in Baltic Sea surface water during the summer. [source] Interactions between metabolism of trace metals and xenobiotic agonists of the aryl hydrocarbon receptor in the antarctic fish Trematomus bernacchii: Environmental perspectivesENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 6 2005Francesco Regoli Abstract Although Antarctica is a pristine environment, organisms are challenged with contaminants either released locally or transported from industrialized regions through atmospheric circulation and marine food webs. Organisms from Terra Nova Bay also are exposed to a natural enrichment of cadmium, but to our knowledge, whether such environmental conditions influence biological responses to anthropogenic pollutants has never been considered. In the present study, the Antarctic rock cod (Trematomus bernacchii) was exposed to model chemicals, including polycyclic aromatic hydrocarbons (benzo[a]pyrene), persistent organic pollutants (2,3,7,8-tetrachlorodibenzo- p -dioxin [TCDD]), cadmium, and a combination of cadmium and TCDD. Analyzed parameters included chemical bioaccumulation, activity, and levels of biotransformation enzymes (cytochrome P4501A); metallothioneins and the efficiency of the antioxidant system measured as individual defenses (catalase, glutathione, glutathione reductase, glutathione S -transferases, and glutathione peroxidases); and total scavenging capacity toward peroxyl and hydroxyl radicals. Reciprocal interactions between metabolism of inorganic and organic pollutants were demonstrated. Dioxin enhanced the accumulation of cadmium, probably stored within proliferating endoplasmic reticulum, and cadmium suppressed the inducibility of cytochrome P4501A, allowing us to hypothesize a posttranscriptional mechanism as the depletion of heme group availability. Clear evidence of oxidative perturbation was provided by the inhibition of antioxidants and enhanced sensitivity to oxyradical toxicity in fish exposed to organic chemicals. Exposure to cadmium revealed counteracting responses of glutathione metabolism; however, these responses did not prevent a certain loss of antioxidant capacity toward peroxyl radicals. The pattern of antioxidant responses exhibited by fish coexposed to cadmium and TCDD was more similar to that observed for cadmium than to that observed for TCDD. The overall results suggest that elevated natural levels of cadmium in Antarctic organisms from Terra Nova Bay can limit biotransformation capability of polycyclic (halogenated) hydrocarbons, thus influencing the bioaccumulation and biological effects of these chemicals in key sentinel species. [source] Association between lymphocyte proliferation and polychlorinated biphenyls in free-ranging harbor seal (Phoca vitulina) pups from British Columbia, CanadaENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 5 2005Milton Levin Abstract Recent pinniped die-offs have led to the speculation that persistent organic pollutants (POPs) are immunomodulatory, making individuals more susceptible to viral infections. Eighteen healthy harbor seal (Phoca vitulina) pups (aged 3,4 weeks) were live-captured from southern British Columbia, Canada, and maintained temporarily in captivity for an immunotoxicological assessment. The relationships between mitogen-induced peripheral blood lymphocyte proliferation and blubber concentrations of three major immunotoxic POP classes (the polychlorinated biphenyls [PCBs], polychlorinated dibenzo- p -dioxins [PCDDs], and the polychlorinated dibenzofurans [PCDFs]) were evaluated. A significant body weight-independent positive correlation was observed between both T-cell mitogen (phytohemagglutinin [PHA])- and B-cell mitogen (lipopolysaccharide [LPS])-induced lymphocyte proliferation and the blubber concentrations of total PCB. Best subset regression analysis revealed that total PCBs, and not total PCDD or total PCDF, explained 24 and 29% of the changes in both T-cell mitogen-and B-cell mitogen-induced lymphocyte proliferation, respectively. Further regression analysis performed on the PCB classes measured in this study showed that di - ortho PCBs accounted for 25 and 30% of the changes in both T-cell and B-cell lymphocyte proliferation, respectively. Results suggest that POPs, and PCBs in particular, are associated with changes in lymphocyte proliferation, something that could result in increased susceptibility to infections in harbor seal pups. Further research is needed to evaluate the relative roles of natural and contaminant-related influences on the immune system of marine mammals. [source] Role of black carbon in the partitioning and bioavailability of organic pollutantsENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 11 2004Robert M. Burgess No abstract is available for this article. [source] Kinetics of toluene sorption and desorption in Ca- and Cu-montmorillonites investigated with Fourier transform infrared spectroscopy under two different levels of humidityENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 9 2004Yang-Hsin Shih Abstract Clays in soils or groundwater aquifer materials play roles in the sorption of organic pollutants. The intrinsic sorption kinetics of toluene in dry and humid clay films was investigated by tracking the change of infrared absorbance. Under the humid condition, similar toluene-sorbed intensities were found in Ca- and Cu-montmorillonites. However, a higher intensity of sorbed toluene was found in the Cu-form than in the Ca-form under the dry condition, which indicates a stronger interaction occurring in dry Cu-montmorillonite. The general time scale of sorption of toluene on clays is around 100 s. In both forms of montmorillonite, some portion of toluene was desorbed at an extremely slow rate under the dry condition. Some newly identified peaks were persistent against desorption from montmorillonites, suggesting the existence of irreversibly sorbed species and the possibility of toluene transformation occurring in clay systems. [source] Ecological risk assessment of persistent toxic substances for the clam Tapes philipinarum in the lagoon of venice, italyENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 6 2004Christian Micheletti Abstract Because of contamination of sediments of the Lagoon of Venice, Italy, by inorganic pollutants (e.g., arsenic, cadmium, chromium, copper, lead, mercury, nickel, and zinc) and organic pollutants (e.g., polychlorobiphenyls), as well as the ecological and economical relevance of the edible clam Tapes philipinarum, an ecological risk assessment was undertaken to ascertain the extent of bioaccumulation that would pose a significant risk. Risk was estimated by means of toxic units and hazard quotient approaches, by comparing the exposure concentration with the effect concentration. Clam exposure was estimated by applying previous results based on bioaccumulation spatial regression models. In addition, a comparison was made between sum of dioxin-like polychlorinated biphenyl (PCB) congeners and total PCB bioaccumulation provided by spatial regression models and by a partitioning model. The effect concentrations were calculated as tissue screening concentrations, as the product of pollutant sediment quality criteria and the bioaccumulation factor. Finally, the cumulative risk posed by selected inorganic pollutants and total PCBs was estimated and a map of risk was drawn. The resulting chemicals of potential ecological concern were mercury, cadmium, arsenic, and nickel, as well as, to a lesser extent, total PCBs. [source] Persistent organic pollutants in air and vegetation from the canadian rocky mountainsENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 3 2004Deborah A. Davidson Abstract The exchange of chlorinated organic pollutants between air and vegetation in cold, mountain environments was investigated through the extraction of coniferous vegetation and high-volume air samples collected from the Canadian Rocky Mountains during the summers of 1999 and 2000. Concentrations of several compounds in vegetation increased as temperatures decreased, whereas atmospheric concentrations were not related to temperature. Daily cycling of these compounds between air and vegetation as a result of diurnal temperature changes was not observed. Compared with concentrations in vegetation from the Canadian Rocky Mountains, plant samples from the western valley in British Columbia (Canada) showed higher pollutant levels. Chemical partitioning between vegetation and air was not correlated with temperature, indicating that air contamination is governed by long-range transport and not by local revolatilization events. Based on these observations, we show that both deposition at higher altitudes and long-range atmospheric transport influence chemical accumulation in vegetation from the Canadian Rocky Mountains. [source] Metalloporphyrin solubility: A trigger for catalyzing reductive dechlorination of tetrachloroethyleneENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 2 2004Ishai Dror Abstract Metalloporphyrins are well known for their electron-transfer roles in many natural redox systems. In addition, several metalloporphyrins and related tetrapyrrole macrocycles complexed with various core metals have been shown to catalyze the reductive dechlorination of certain organic compounds, thus demonstrating the potential for using naturally occurring metalloporphyrins to attenuate toxic and persistent chlorinated organic pollutants in the environment. However, despite the great interest in reductive dechlorination reactions and the wide variety of natural and synthetic porphyrins currently available, only soluble porphyrins, which comprise a small fraction of this particular family of organic macrocycles, have been used as electron-transfer shuttles in these reactions. Results from the present study clearly demonstrate that metalloporphyrin solubility is a key factor in their ability to catalyze the reductive dechlorination of tetrachloroethylene and its daughter compounds. Additionally, we show that certain insoluble and nonreactive metalloporphyrins can be activated as catalysts merely by changing solution conditions to bring about their dissolution. Furthermore, once a metalloporphyrin is fully dissolved and activated, tetrachloroethylene transformation proceeds rapidly, giving nonchlorinated and less toxic alkenes as the major reaction products. Results from the present study suggest that if the right environmental conditions exist or can be created, specific metalloporphyrins may provide a solution for cleaning up sites that are contaminated with chlorinated organic pollutants. [source] Harbor seals (Phoca vitulina) in British Columbia, Canada, and Washington State, USA, reveal a combination of local and global polychlorinated biphenyl, dioxin, and furan signalsENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 1 2004Peter S. Ross Abstract The harbor seal (Phoca vitulina) can serve as a useful indicator of food web contamination by persistent organic pollutants (POPs) because of its high trophic level, wide distribution in temperate coastal waters of the Northern Hemisphere, and relative ease of capture. In 1996 through 1997, we live-captured 60 harbor seal pups from three regions, spanning remote (Queen Charlotte Strait, BC, Canada), moderately industrialized (Strait of Georgia, BC, Canada), and heavily industrialized (Puget Sound, WA, USA) marine basins straddling the Canada-United States border. Biopsy samples of blubber were taken and analyzed for congener-specific polychlorinated biphenyls (PCBs), polychlorinated dibenzo- p -dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) by using high-resolution gas chromatography-high-resolution mass spectrometry. Harbor seals in Puget Sound were heavily contaminated with PCBs, whereas seals from the Strait of Georgia had relatively high concentrations of PCDDs and PCDFs. Pattern evaluation and principal components analysis suggested that proximity to sources influenced the mixture to which seals were exposed, with those inhabiting more remote areas being exposed to lighter PCB congeners (those with lower Henry's law constant and KOW) that disperse more readily through atmospheric and other processes. Total toxic equivalents to 2,3,7,8-tetrachlorodibenzo- p -dioxin for the PCBs, PCDDs, and PCDFs suggest that Puget Sound seals are at greatest risk for adverse health effects, and that PCBs represent the class of dioxinlike contaminants of greatest concern at all sites. [source] Prediction of uptake dynamics of persistent organic pollutants by bacteria and phytoplanktonENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 10 2002Sabino Del Vento Abstract Phytoplankton and bacteria play an important role on the biogeochemical cycles of persistent organic pollutants (POPs). However, experimental data and quantitative knowledge of the kinetics of uptake and depuration of most POPs by bacteria and phytoplankton are scarce. In the present paper, a procedure to predict the sorption kinetics to bacteria and phytoplankton is developed. The prediction method is the combination of a mechanistic model for sorption and quantitative structure,activity relationships relating bioconcentration factors and membrane permeability to the chemical physical-chemical properties. The model consists of two compartments where the first compartment is the cellular surface and the second compartment is the cell biomass or matrix. Equations for estimating uptake and depuration rate constants into the matrix and adsorption and desorption rate constants onto the surface are obtained. These expressions depend on the physical-chemical properties of the chemical, the environmental temperature, the microorganism size, and species-specific quality of organic matter. While microorganism shape has a secondary influence on uptake dynamics, microorganism size and chemical hydrophobicity arise as the key factors controlling the kinetics of POP incorporation into bacteria and plankton. Uptake, depuration, adsorption, and desorption rate constants are reported for POPs such as polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated dioxins and furans (PCDD/Fs), and POPs of emerging concern, such as polybrominated diphenyl ethers (PBDEs). Finally, implications of uptake and depuration dynamics on the biogeochemical cycling of POPs are discussed. [source] Optimization of activated carbon-based decontamination of fish oil by response surface methodologyEUROPEAN JOURNAL OF LIPID SCIENCE AND TECHNOLOGY, Issue 7 2007Åge Oterhals Abstract The effect of activated carbon (AC) adsorption on the reduction of persistent organic pollutants (POP) in fish oil was studied based on response surface methodology at a 5-g/kg AC inclusion level. Pretreatment of the oil by alkali refining and bleaching increased the POP levels. The tested process variables (contact time and temperature) affected the AC adsorption rate and significant first- and second-order response models could be established. Polychlorinated dibenzo- p -dioxins and dibenzofurans (PCDD/F) showed a very rapid adsorption behavior and the concentration and toxic equivalent (TEQ) level could be reduced by 99%. Adsorption of dioxin-like polychlorinated biphenyls (DL-PCB) was less effective and depended on ortho substitution, i.e. non- ortho PCB were adsorbed more effectively than mono- ortho PCB with a maximum of 87 and 21% reduction, respectively, corresponding to a DL-PCB-TEQ reduction of 73%. A common optimum for both PCDD/F and DL-PCB adsorption could not be identified. AC treatment had no effect on the level of polybrominated diphenyl ether flame retardants. The differences in adsorption patterns may be explained based on molecular conformation. No change in oil quality could be observed based on oxidation parameters. Compliance with present PCDD/F and DL-PCB legislation levels in fish oil can be achieved based on AC adsorption. [source] Thermodynamic Study of ,H Complexes in Nucleophilic Aromatic Substitution Reactions: Relative Stabilities of Electrochemically Generated RadicalsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 14 2008Iluminada Gallardo Abstract The mechanism for the electrochemical oxidation of ,H complexes, such as 1-hydro-1-alkoxy/sulfoxy or -fluoro-2,4-dinitro/2,4,6-trinitrocyclohexadienyl anions, has been widely studied by means of cyclic voltammetry and controlled-potential electrolysis. Previous studies have shown that the electrochemical oxidation of ,H complexes, formed by the addition of carbon or nitrogen nucleophiles followed by a two electron mechanism, corresponding to the formal elimination of the hydride anion (nucleophilic aromatic substitution of hydrogen mechanism, the NASH mechanism). For these ,H complexes (Nu, = OH,, ,OR, ,SR, ,F), the electrochemical reaction takes place by a one-electron mechanism and is followed by the radical elimination of the leaving group with the consequent recovery of the starting material. This mechanism is similar to that proposed for the electrochemical oxidation of ,X complexes (nucleophilic aromatic substitution of a heteroatom, the NASX mechanism). The operating mechanism in each case, the NASH or NASX, can be rationalized in terms of thermodynamics. The standard potentials of the , complex and/or the leaving group as well as the bond dissociation energies (BDEs) are determinant factors. This study has not led to a significant improvement in the electrochemical preparation of aromatic-substituted compounds, but does help to understand and predict the usefulness or uselessness of using the nucleophilic aromatic substitution route to obtain a desired product. Finally, the current approach extends the electrochemical methodology to different chemical fields, for example, to general nondestructive methods for the detection, identification, and quantification of either organic pollutants or explosives in different solvents. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Multifunctional Au-Coated TiO2 Nanotube Arrays as Recyclable SERS Substrates for Multifold Organic Pollutants DetectionADVANCED FUNCTIONAL MATERIALS, Issue 17 2010Xuanhua Li Abstract A multifunctional Au-coated TiO2 nanotube array is made via synthesis of a TiO2 nanotube array through a ZnO template, followed by deposition of Au particles onto the TiO2 surface using photocatalytic deposition and a hydrothermal method, respectively. Such arrays exhibit superior detection sensitivity with high reproducibility and stability. In addition, due to possessing stable catalytic properties, the arrays can clean themselves by photocatalytic degradation of target molecules adsorbed to the substrate under irradiation with UV light into inorganic small molecules using surface-enhanced Raman spectroscopy (SERS) detection, so that recycling can be achieved. Finally, by detection of Rhodamine 6G (R6G) dye, herbicide 4-chlorophenol (4-CP), persistent organic pollutant (POP) dichlorophenoxyacetic acid (2,4-D), and organophosphate pesticide methyl-parathion (MP), the unique recyclable properties indicate a new route in eliminating the single-use problem of traditional SERS substrates and show promising applications for detecting other organic pollutants. [source] Enhanced Photocatalytic Activity using Layer-by-Layer Electrospun Constructs for Water RemediationADVANCED FUNCTIONAL MATERIALS, Issue 15 2010Jung Ah Lee Abstract Endocrine disruptors such as bisphenol A (BPA) are environmental pollutants that interfere with the body's endocrine system because of their structural similarity to natural and synthetic hormones. Due to their strong oxidizing potential to decompose such organic pollutants, colloidal metal oxide photocatalysts have attracted increasing attention for water detoxification. However, achieving both long-term physical stability and high efficiency simultaneously with such photocatalytic systems poses many challenges. Here a layer-by-layer (LbL) deposition approach is reported for immobilizing TiO2 nanoparticles (NPs) on a porous support while maintaining a high catalytic efficiency for photochemical decomposition of BPA. Anatase TiO2 NPs ,7,nm in diameter self-assemble in consecutive layers with positively charged polyhedral oligomeric silsesquioxanes on a high surface area, porous electrospun polymer fiber mesh. The TiO2 LbL nanofibers decompose approximately 2.2,mg BPA per mg of TiO2 in 40,h of illumination (AM 1.5G illumination), maintaining first-order kinetics with a rate constant (k) of 0.15,h,1 for over 40,h. Although the colloidal TiO2 NPs initially show significantly higher photocatalytic activity (k,,,0.84,h,1), the rate constant drops to k,,,0.07,h,1 after 4,h of operation, seemingly due to particle agglomeration. In the BPA solution treated with the multilayered TiO2 nanofibers for 40,h, the estrogenic activity, based on human breast cancer cell proliferation, is significantly lower than that in the BPA solution treated with colloidal TiO2 NPs under the same conditions. This study demonstrates that water-based, electrostatic LbL deposition effectively immobilizes and stabilizes TiO2 NPs on electrospun polymer nanofibers for efficient extended photochemical water remediation. [source] |