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Behaviour and variability of local and regional oxidant levels (OX = O₃ + NO ₂) measured in a polluted area in central-southern of Iberian Peninsula
2013
Notario, Alberto | Bravo, Iván | Adame, José Antonio | Díaz-de-Mera, Yolanda | Aranda, Alfonso | Rodríguez, Ana | Rodriguez, Diana
The purpose of this work is to contribute to the understanding of the photochemical air pollution in central-southern of the Iberian Peninsula, analysing the behaviour and variability of oxidant levels (OX = O₃ + NO₂), measured in a polluted area with the highest concentration of heavy industry in central Spain. A detailed air pollution database was observed from two monitoring stations. The data period used was 2008 and 2009, around 210,000 data, selected for its pollution and meteorological statistics, which are very representative of the region. Data were collected every 15 min, however hourly values were used to analyse the seasonal and daily ozone, NO, NO₂ and OX cycles. The variation of OX concentrations with NO ₓ is investigated, for the first time, in the centre of the Iberian Peninsula. The concentration of OX was calculated using the sum of a NO ₓ -independent ‘regional’ contribution (i.e. the O₃ background), and a linearly NO ₓ -dependent ‘local’ contribution. Monthly dependence of regional and local OX concentration was observed to determine when the maximum values may be expected. The variation of OX concentrations with levels of NO ₓ was also measured, in order to pinpoint the atmospheric sources of OX in the polluted areas. The ratios [NO₂]/[OX] and [NO₂]/[NO ₓ ] vs. [NO ₓ ] were analysed to find the fraction of OX in the form of NO₂, and the possible source of the local NO ₓ -dependent contribution, respectively. The progressive increase of the ratio [NO₂]/[OX] with [NO ₓ ] observed shows a greater proportion of OX in the form of NO₂ as the level of NO ₓ increases. The higher measured values in the ratio [NO₂]/[NO ₓ ] should not be attributed to NO ₓ emissions by vehicles; they could be explained by industrial emission, termolecular reactions or formaldehyde and HONO directly emitted by vehicles exhausts. We also estimate the rate of NO₂ photolysis, J NO₂ = 0.18–0.64 min⁻¹, a key atmospheric reaction that influence O₃ production and then the regional air quality. The first surface plot study of annual variation of the daily mean oxidant levels, obtained for this polluted area may be used to improve the atmospheric photochemical dynamic in this region of the Iberian Peninsula where there are undeniable air quality problems.
Mostrar más [+] Menos [-]Kinetics of Remazol Black B adsorption onto carbon prepared from sugar beet pulp
2013
Dursun, Arzu Y. | Tepe, Ozlem | Uslu, Gülşad | Dursun, Gülbeyi | Saatci, Yusuf
Dried sugar beet pulp, an agricultural solid waste, was used for the production of carbon. Carbonised beet pulp was tested in the adsorption of Remazol Black B dye, and adsorption studies with real textile wastewater were also performed. Batch kinetic studies showed that an equilibrium time of 180 min was needed for the adsorption. The maximum dye adsorption capacity was obtained as 80.0 mg g⁻¹ at the temperature of 25 °C at pH = 1.0. The Langmuir and Freundlich adsorption models were used for the mathematical description of the adsorption equilibrium, and it was reported that experimental data fitted very well to the Langmuir model. Mass transfer and kinetic models were applied to the experimental data to examine the mechanisms of adsorption and potential rate-controlling steps. It was found that both external mass transfer and intraparticle diffusion played an important role in the adsorption mechanisms of dye, and adsorption kinetics followed the pseudo-second-order type kinetic model. The thermodynamic analysis indicated that the sorption process was exothermic and spontaneous in nature.
Mostrar más [+] Menos [-]Quantification and in situ localisation of abcb1 and abcc9genes in toxicant-exposed sea urchin embryos
2013
Bošnjak, Ivana | Lepen Pleić, Ivana | Borra, Marco | Mladineo, Ivona
A multixenobiotic resistance (MXR) mechanism mediated by ABC binding cassette (ABC) transport proteins is an efficient chemical defence mechanism in sea urchin embryos. The aim of our work was to evidence whether exposure to sub-lethal doses of specific contaminants (oxybenzone (OXI), mercuric chloride (HgCl₂) and trybutiltin (TBT)) would induce MXR transporter activity during embryonic development (from zygote to blastula stage) in purple sea urchin (Paracentrotus lividus) embryos. Further, we present data on molecular identification, transport function, expression levels and gene localisation of two ABC efflux transporters—P-glycoprotein (ABCB1/P-gp) and sulfonylurea-receptor-like protein (ABCC9/SUR-like). Partial cDNA sequences of abcb1 and abcc9 were identified and quantitative PCR (qPCR) evidenced an increase in mRNA transcript levels of both ABC transporters during the two-cell, as well as an overall decrease during the blastulae stage. Calcein-AM efflux activity assay indicated the activation of multidrug resistance-associated protein/ABCC-like transport in the presence of HgCl₂ and TBT in exposed blastulae. The in situ hybridisation of the two-cell and blastula stages showed ubiquitous localisation of both transcripts within cells, supporting qPCR data. In conclusion, ABCB1 and ABCC9 are constitutive, as are HgCl₂, TBT and OXI-inducible ABC membrane transporters, coexpressed in the zygote, two-cell and blastula stages of the P. lividus. Their ubiquitous cell localisation further fortifies their protective role in early embryonic development.
Mostrar más [+] Menos [-]Glutathione and its dependent enzymes’ modulatory responses to toxic metals and metalloids in fish—a review
2013
Toxic metals and metalloid are being rapidly added from multiple pathways to aquatic ecosystem and causing severe threats to inhabiting fauna including fish. Being common in all the type of aquatic ecosystems such as freshwater, marine and brackish water fish are the first to get prone to toxic metals and metalloids. In addition to a number of physiological/biochemical alterations, toxic metals and metalloids cause enhanced generation of varied reactive oxygen species (ROS) ultimately leading to a situation called oxidative stress. However, as an important component of antioxidant defence system in fish, the tripeptide glutathione (GSH) directly or indirectly regulates the scavenging of ROS and their reaction products. Additionally, several other GSH-associated enzymes such as GSH reductase (GR, EC 1.6.4.2), GSH peroxidase (EC 1.11.1.9), and GSH sulfotransferase (glutathione-S-transferase (GST), EC 2.5.1.18) cumulatively protect fish against ROS and their reaction products accrued anomalies under toxic metals and metalloids stress conditions. The current review highlights recent research findings on the modulation of GSH, its redox couple (reduced glutathione/oxidised glutathione), and other GSH-related enzymes (GR, glutathione peroxidase, GST) involved in the detoxification of harmful ROS and their reaction products in toxic metals and metalloids-exposed fish.
Mostrar más [+] Menos [-]The function of digestive enzymes on Cu, Zn, and Pb release from soil in in vitro digestion tests
2013
The bioaccessibility of soil heavy metals is the solubility of soil heavy metals in synthetic human digestive juice, which is usually determined using in vitro digestion test. To reveal the effects of digestive enzymes on soil heavy metals bioaccessibility, three representative in vitro digestion tests, Simple Bioaccessibility Extraction Test (SBET), Physiologically Based Extraction Test (PBET), and Simple Gastrointestinal Extraction Test (SGET), were chosen. The bioaccessibility of soil Cu, Zn, and Pb in each method were respectively evaluated with and without digestive enzymes, and the differences were compared. The results showed that the effects of digestive enzymes varied with different methods and elements. Because of digestive enzymes addition, the environmental change from acid gastric phase to neutral intestinal phase of PBET did not result in apparently decrease of the bioaccessibility of soil Cu. However, the solubility of soil Zn and Pb were pH-dependent. For SGET, when digestive enzymes were added, its results reflected more variations resulting from soil and element types. The impacts of digestive enzymes on heavy metal dissolution are mostly seen in the intestinal phase. Therefore, digestive enzyme addition is indispensable to the gastrointestinal digestion methods (PBET and SGET), while the pepsin addition is not important for the methods only comprised of gastric digestion (SBET).
Mostrar más [+] Menos [-]Spatial distribution of mercury in topsoil from five regions of China
2013
Shi, Jian-bo | Meng, Mei | Shao, Jun-juan | Zhang, Ke-gang | Zhang, Qing-hua | Jiang, Gui-bin
The concentrations and distributions of mercury (Hg) in topsoil from four provinces and one municipality in China were investigated. A total of 1,254 samples were collected and analyzed. The average concentrations of Hg were 0.064 mg kg⁻¹ for Liaoning Province, 0.100 mg kg⁻¹ for Jiangsu Province, 0.110 mg kg⁻¹ for Zhejiang Province, 0.154 mg kg⁻¹ for Sichuan Province, and 0.098 mg kg⁻¹ for Chongqing Municipality. Although differences were found among the ranges of Hg concentrations, the average values for each region were similar with other published data. The concentrations of Hg in topsoil varied largely upon the sampling locations. More than 80 % of the soil samples from Liaoning Province, Jiangsu Province, Zhejiang Province, and Chongqing Municipality, were ranked Grade I by the China Environmental Quality Standard for Soils, which can be considered as not contaminated by Hg. The concentrations of Hg in 0.3–0.4 % of soils collected from Jiangsu Province, Zhejiang Province and Chongqing Municipality exceeded the limitation for Grade III, indicating the contamination of Hg in these sites. The sources and potential risks of Hg in these sites should be brought to attention and further investigated.
Mostrar más [+] Menos [-]Fenton-like degradation of nalidixic acid with Fe³⁺/H ₂O ₂
2013
Fan, Xiangqun | Hao, Hongyuan | Wang, Yongchuan | Chen, Feng | Zhang, Jinlong
The Fenton-like degradation of nalidixic acid was studied in this work. The effects of Fe³⁺ concentration and initial H₂O₂ concentration were investigated. Increasing the initial H₂O₂ concentration enhances the degradation and mineralization efficiency for nalidixic acid, while Fe³⁺ shows an optimal concentration of 0.25 mM. A complete removal of nalidixic acid and a TOC removal of 28 % were achieved in 60 min under a reaction condition of [Fe³⁺] = 0.25 mM, [H₂O₂] = 10 mM, T = 35 °C, and pH = 3. LC–MS analysis technique was used to analyze the possible degradation intermediates. The degradation pathways of nalidixic acid were proposed according to the identified intermediates and the electron density distribution of nalidixic acid. The Fenton-like degradation reaction of nalidixic acid mainly begins with the electrophilic attack of hydroxyl radical towards the C₃ position which results in the ring-opening reaction; meanwhile, hydroxyl radical attacking to the branched alkyl groups of nalidixic acid leads to the oxidation at the branched alkyl groups.
Mostrar más [+] Menos [-]Perfluoroalkyl substances (PFASs) in food and water from Faroe Islands
2013
Diet and drinking water are suggested to be major exposure pathways for perfluoroalkyl substances (PFASs). In this study, food items and water from Faroe Islands sampled in 2011/2012 were analyzed for 11 perfluoroalkyl carboxylic acids (PFCAs) and 4 perfluoroalkane sulfonic acids (PFSAs). The food samples included milk, yoghurt, crème fraiche, potatoes, fish, and fish feed, and the water samples included surface water and purified drinking water. In total, nine PFCAs and four PFSAs were detected. Generally, the levels of PFAS were in the lower picogram per gram range. Perfluorobutanoic acid was a major contributor to the total PFASs concentration in water samples and had a mean concentration of 750 pg/L. Perfluoroundecanoic acid (PFUnDA) was predominating in milk and wild fish with mean concentrations of 170 pg/g. Perfluorooctane sulfonic acid (PFOS) was most frequently detected in food items followed by PFUnDA, perfluorononanoic acid, and perfluorooctanoic acid (PFOA). Levels of PFUnDA and PFOA exceeded those of PFOS in milk and fish samples. Prevalence of long-chain PFCAs in Faroese food items and water is confirming earlier observations of their increase in Arctic biota. Predominance of short-chain and long-chain homologues indicates exposure from PFOS and PFOA replacement compounds.
Mostrar más [+] Menos [-]Distribution and accumulation of elements (As, Cu, Fe, Hg, Mn, and Zn) in tissues of fish species from different trophic levels in the Danube River at the confluence with the Sava River (Serbia)
2013
Subotić, S. | Višnjić Jeftić, Ž | Spasić, S. | Hegediš, A. | Krpo-Ćetković, J. | Lenhardt, M.
Pikeperch (Sander lucioperca), European catfish (Silurus glanis), common carp (Cyprinus carpio), and gobies (Neogobius gymnotrachelus, Neogobius melanostomus) were collected from the Danube River (Belgrade section), and samples of liver, muscle, or whole-body composites (in the case of gobies) were analyzed for As, Cu, Fe, Hg, Mn, and Zn with inductively coupled plasma optical spectrometry to find out if there was a correlation between accumulation of these elements in predatory and prey species, as well as in pairs of species with overlapping diets. Concentrations of all analyzed elements were either higher (Cu, Fe, Mn, Zn) in liver than in muscle, or equal (As, Hg), except for Hg in carp, which was higher in muscle. Mercury concentration in liver and muscle of predators (catfish, pikeperch) was significantly (<10⁻⁴) higher than in prey fishes (carp and gobies). The results indicate that Hg concentration was biomagnified through the food chain. Concentrations of As, Fe, and Hg in carp liver and gobies whole-body composite were similar, but carp had significantly (<10⁻⁴) higher values of Zn and Cu in liver. The regression analysis and trendline equations indicate that the concentrations of all tested elements, except for As in liver, and Mn and Fe in muscle, were similar in predatory fish (pikeperch and catfish), on one hand, and in prey fish (carp and gobies), on the other hand. Distinctly high Zn concentration in carp is very common in this species due to its physiology. Concentrations of Hg and Zn were higher than the maximum acceptable concentration due to the high pollution level in this section of the Danube River, accordingly posing a risk for the human consumption of these fish species.
Mostrar más [+] Menos [-]Applicability of MIEX®DOC process for organics removal from NOM laden water
2013
Karpinska, Anna M. | Boaventura, Rui A. R. | Vilar, Vítor J. P. | Bilyk, Andrzej | Molczan, Marek
The aim of this study was to evaluate applicability of ion exchange process for organics removal from Douro River surface water at the intake of Lever water treatment plant using magnetized ion exchange resin MIEX®. Qualitative analysis of the natural organic matter present in the surface water and prediction of its amenability to removal in conventional coagulation process were assessed. Results obtained in MIEX®DOC process kinetic batch experiments allowed determination of ion exchange efficiency in dissolved organic carbon (DOC), UV absorbing organics, and true color removal. The data were compared with the efficiencies of the conventional unit processes for organics removal at Lever WTP. MIEX®DOC process revealed to be more efficient in DOC removal than conventional treatment achieving the efficiencies in the range of 61–91 %, lowering disinfection by-products formation potential of the water. DOC removal efficiency at Lever WTP depends largely on the raw water quality and ranges from 28 % for water of moderated quality to 89 % of significantly deteriorated quality. In this work, MIEX®DOC process was also used as a reference method for the determination of contribution of anionic fraction to dissolved organic matter and selectivity of the unit processes at Lever WTP for its removal.
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