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Heavy metal contents in water, sediment and fish in a karst aquatic ecosystem of the Plitvice Lakes National Park (Croatia)
2014
Vukosav, Petra | Mlakar, Marina | Cukrov, Neven | Kwokal, Željko | Pižeta, Ivanka | Pavlus, Natalija | Špoljarić, Ivanka | Vurnek, Maja | Brozinčević, Andrijana | Omanović, Dario
An evaluation of the quality status of the pristine karst, tufa depositing aquatic environment of the Plitvice Lakes National Park based on the analysis of heavy (ecotoxic) metals was examined for the first time. Analyses of trace metals in water, sediment and fish (Salmo trutta, Oncorhynchus mykiss, Squalius cephalus) samples were conducted either by stripping voltammetry (Zn, Cd, Pb and Cu) or cold vapour atomic absorption spectrometry (Hg). The concentration of dissolved trace metals in water was very low revealing a pristine aquatic environment (averages were, in ng/L: 258 (Zn), 10.9 (Cd), 11.7 (Pb), 115 (Cu) and 1.22 (Hg)). Slightly enhanced concentrations of Cd (up to 50 ng/L) and Zn (up to 900 ng/L) were found in two main water springs and are considered as of natural origin. Observed downstream decrease in concentration of Cd, Zn and Cu in both water and sediments is a consequence of the self-purification process governed by the formation and settling of authigenic calcite. Anthropogenic pressure was spotted only in the Kozjak Lake: Hg concentrations in sediments were found to be up to four times higher than the baseline value, while at two locations, Pb concentrations exceeded even a probable effect concentration. The increase of Hg and Pb was not reflected on their levels in the fish tissues; however, significant correlations were found between Cd level in fish tissues (liver and muscle) and in the water/sediment compartments, while only partial correlations were estimated for Zn and Cu. A high discrepancy between values of potentially bioavailable metal fraction estimated by different modelling programs/models raised the question about the usefulness of these data as a parameter in understanding/relating the metal uptake and their levels in aquatic organism. The aquatic environment of the Plitvice Lakes National Park is characterized, in general, as a clean ecosystem.
Show more [+] Less [-]Fourteenth National Congress of the Environmental and Cultural Heritage Chemistry Division, “Chemistry in a Sustainable Society,” held in Rimini (Italy) in June 2013
2014
Bernardi, Elena | Passarini, Fabrizio | Morselli, Luciano
This report briefly presents the aims and the fields of interest of the Environmental and Cultural Heritage Division (Italian Chemical Society) and the issues addressed during its national congress, held in Rimini in June 2013. The broad range of topics raised by different speakers, the variety of affiliations and institutions participating at the conference, the scientific organisations and private companies co-sponsoring the different sessions give a clear picture of the interdisciplinarity which is a hallmark of this division.
Show more [+] Less [-]Decolourisation of Acid Orange 7 recalcitrant auto-oxidation coloured by-products using an acclimatised mixed bacterial culture
2014
Bay, Hui Han | Lim, Chi Kim | Kee, Thuan Chien | Ware, Ismail | Chan, Giek Far | Shahir, Shafinaz | Ibrahim, Zaharah
This study focuses on the biodegradation of recalcitrant, coloured compounds resulting from auto-oxidation of Acid Orange 7 (AO7) in a sequential facultative anaerobic–aerobic treatment system. A novel mixed bacterial culture, BAC-ZS, consisting of Brevibacillus panacihumi strain ZB1, Lysinibacillus fusiformis strain ZB2, and Enterococcus faecalis strain ZL bacteria were isolated from environmental samples. The acclimatisation of the mixed culture was carried out in an AO7 decolourised solution. The acclimatised mixed culture showed 98 % decolourisation within 2 h of facultative anaerobic treatment using yeast extract and glucose as co-substrate. Subsequent aerobic post treatment caused auto-oxidation reaction forming dark coloured compounds that reduced the percentage decolourisation to 73 %. Interestingly, further agitations of the mixed culture in the solution over a period of 48 h significantly decolourise the coloured compounds and increased the decolourisation percentage to 90 %. Analyses of the degradation compounds using UV–visible spectrophotometer, Fourier transform infrared spectroscopy (FTIR) and high performance liquid chromatography (HPLC) showed complete degradation of recalcitrant AO7 by the novel BAC-ZS. Phytotoxicity tests using Cucumis sativus confirmed the dye solution after post aerobic treatment were less toxic compared to the parent dye. The quantitative real-time PCR revealed that E. faecalis strain ZL was the dominant strain in the acclimatised mix culture.
Show more [+] Less [-]Post-acquisition data processing for the screening of transformation products of different organic contaminants. Two-year monitoring of river water using LC-ESI-QTOF-MS and GCxGC-EI-TOF-MS
2014
López, S Herrera | Ulaszewska, M. M. | Hernando, M. D. | Bueno, M. J Martínez | Gómez, M. J. | Fernández-Alba, A. R.
This study describes a comprehensive strategy for detecting and elucidating the chemical structures of expected and unexpected transformation products (TPs) from chemicals found in river water and effluent wastewater samples, using liquid chromatography coupled to electrospray ionization quadrupole-time-of-flight mass spectrometer (LC-ESI-QTOF-MS), with post-acquisition data processing and an automated search using an in-house database. The efficacy of the mass defect filtering (MDF) approach to screen metabolites from common biotransformation pathways was tested, and it was shown to be sufficiently sensitive and applicable for detecting metabolites in environmental samples. Four omeprazole metabolites and two venlafaxine metabolites were identified in river water samples. This paper reports the analytical results obtained during 2 years of monitoring, carried out at eight sampling points along the Henares River (Spain). Multiresidue monitoring, for targeted analysis, includes a group of 122 chemicals, amongst which are pharmaceuticals, personal care products, pesticides and PAHs. For this purpose, two analytical methods were used based on direct injection with a LC-ESI-QTOF-MS system and stir bar sorptive extraction (SBSE) with bi-dimensional gas chromatography coupled with a time-of-flight spectrometer (GCxGC-EI-TOF-MS).
Show more [+] Less [-]Heavy metal pollution in vegetables grown in the vicinity of a multi-metal mining area in Gejiu, China: total concentrations, speciation analysis, and health risk
2014
Li, Yanyan | Wang, Hongbin | Wang, Haijuan | Yin, Fei | Yang, Xiaoyan | Hu, Yongjun
A field survey was conducted to investigate the present situation and health risk of arsenic (As), lead (Pb), cadmium (Cd), copper (Cu), and zinc (Zn) in soils and vegetables in a multi-metal mining area, Gejiu, China. Furthermore, three vegetables (water spinach, potato, and summer squash) containing high metal concentrations were selected to further analyze metal speciation. The results showed that the average concentrations of five metals in soil exceeded the limiting values, and their bioavailable concentrations were significantly positively correlated to the total ones. Heavy metals in the edible parts of vegetables also exceeded the corresponding standards. The leaves of pakchoi, peppermint, and coriander had a strong metal-accumulative ability and they were not suitable for planting. Except the residue forms, the main forms of metals in the edible parts of three selected vegetables were ethanol-, NaCl-, and HAc-extractable fractions for As, Pb, and Cd, respectively; however, Cu was mainly presented as NaCl-extractable and Zn as HAc-extractable fractions. A high proportion of ethanol-extractable As showed that As bioactivity and toxic effects were the highest. Although the total and bioavailable Cd were high in soil, its speciation in vegetables was mainly presented as HAc-extractable fraction, which has a relatively low bioactivity. Lead and arsenic were imposing a serious threat on the local residents via vegetable consumption.
Show more [+] Less [-]Coupling digestion in a pilot-scale UASB reactor and electrochemical oxidation over BDD anode to treat diluted cheese whey
2014
Katsoni, Αthanasia | Mantzavinos, Dionissios | Diamadopoulos, Evan
The efficiency of the anaerobic treatment of cheese whey (CW) at mesophilic conditions was investigated. In addition, the applicability of electrochemical oxidation as an advanced post-treatment for the complete removal of chemical oxygen demand (COD) from the anaerobically treated cheese whey was evaluated. The diluted cheese whey, having a pH of 6.5 and a total COD of 6 g/L, was first treated in a 600-L, pilot-scale up-flow anaerobic sludge blanket (UASB) reactor. The UASB process, which was operated for 87 days at mesophilic conditions (32 ± 2 °C) at a hydraulic retention time (HRT) of 3 days, led to a COD removal efficiency between 66 and 97 %, while the particulate matter of the wastewater was effectively removed by entrapment in the sludge blanket of the reactor. When the anaerobic reactor effluent was post-treated over a boron-doped diamond (BDD) anode at 9 and 18 A and in the presence of NaCl as the supporting electrolyte, complete removal of COD was attained after 3–4 h of reaction. During electrochemical experiments, three groups of organochlorinated compounds, namely trihalomethanes (THMs), haloacetonitriles (HANs), and haloketons (HKs), as well as 1,2-dichloroethane (DCA) and chloropicrin were identified as by-products of the process; these, alongside free chlorine, are thought to increase the matrix ecotoxicity to Artemia salina.
Show more [+] Less [-]Study of the SRF-derived ashes melting behavior and the effects generated by the optimization of their composition on the furnaces energy efficiency in the incineration plants
2014
Mercurio, Vittorio | Venturelli, Chiara | Paganelli, Daniele
As regards the incineration process of the urban solid waste, the composition correct management allows not only the valorization of precise civil and industrial groups of waste as alternative fuels but also a considerable increase of the furnace work temperature leading to a remarkable improvement of the related energy efficiency. In this sense, the study of the melting behavior of ashes deriving from several kinds of fuels that have to be processed to heat treatment is really important. This approach, indeed, ensures to know in depth the features defining the melting behavior of these analyzed samples, and as a consequence, gives us the necessary data in order to identify the best mixture of components to be incinerated as a function of the specific working temperatures of the power plant. Firstly, this study aims to find a way to establish the softening and melting temperatures of the ashes because they are those parameters that strongly influence the use of fuels. For this reason, in this work, the fusibility of waste-derived ashes with different composition has been investigated by means of the heating microscope. This instrument is fundamental to prove the strict dependence of the ashes fusion temperature on the heating rate that the samples experienced during the thermal cycle. In addition, in this work, another technological feature of the instrument has been used allowing to set an instantaneous heating directly on the sample in order to accurately reproduce the industrial conditions which characterize the incineration plants. The comparison between the final results shows that, in effect, the achievement of the best performances of the furnace is due to the a priori study of the melting behavior of the single available components.
Show more [+] Less [-]Bioaccumulation of butyltins and liver damage in the demersal fish Cathorops spixii (Siluriformes, Ariidae)
2014
dos Santos, Dayana Moscardi | Santos, Gustavo Souza | Cestari, Marta Margarete | de Oliveira Ribeiro, Ciro Alberto | de Assis, Helena Cristina Silva | Yamamoto, Flavia | Guiloski, Izonete Cristina | de Marchi, Mary Rosa Rodrigues | Montone, Rosalinda Carmela
The toxicity of butyltin compounds (BTs), mainly tributyltin (TBT), has been reported in different organisms. However, such an analysis in fish after field exposure with reference to the related biomarkers has not been commonly observed in the literature. This study presents the uptake of BTs in the liver of a neotropical marine catfish Cathorops spixii in Paranagua Bay, an important estuarine system located in southern Brazil. Two different areas, close to and distant from the harbor, were used for chemical analysis evaluation of hepatotoxicity through genetic, enzymatic, and histopathological biomarkers. The presence of polycyclic aromatic hydrocarbons in bile was also considered as a biomarker. The results showed a significant relationship between TBT levels and the inhibition of biotransformation enzymes and high occurrence of melanomacrophages in fish collected close to the harbor site. These effects were linked to the absence of TBT metabolites in the liver. In the second site, the presence of DBT was associated with an increase in EROD and GST activity. The larger amount of DNA damage as well as the highest oxidative stress was noted in fish from the less TBT-polluted area, where DBT and bile PAHs occurred. These findings showed different impact levels due to or increased by the chronic exposure of biota to BTs.
Show more [+] Less [-]Organotin compounds in surface sediments of the Southern Baltic coastal zone: a study on the main factors for their accumulation and degradation
2014
Filipkowska, Anna | Kowalewska, Grażyna | Pavoni, Bruno
Sediment samples were collected in the Gulf of Gdańsk, and the Vistula and Szczecin Lagoons—all located in the coastal zone of the Southern Baltic Sea—just after the total ban on using harmful organotins in antifouling paints on ships came into force, to assess their butyltin and phenyltin contamination extent. Altogether, 26 sampling stations were chosen to account for different potential exposure to organotin pollution and environmental conditions: from shallow and well-oxygenated waters, shipping routes and river mouths, to deep and anoxic sites. Additionally, the organic carbon content, pigment content, and grain size of all the sediment samples were determined, and some parameters of the near-bottom water (oxygen content, salinity, temperature) were measured as well. Total concentrations of butyltin compounds ranged between 2 and 182 ng Sn g⁻¹d.w., whereas phenyltins were below the detection limit. Sediments from the Gulf of Gdańsk and Vistula Lagoon were found moderately contaminated with tributyltin, whereas those from the Szczecin Lagoon were ranked as highly contaminated. Butyltin degradation indices prove a recent tributyltin input into the sediments adjacent to sites used for dumping for dredged harbor materials and for anchorage in the Gulf of Gdańsk (where two big international ports are located), and into those collected in the Szczecin Lagoon. Essential factors affecting the degradation and distribution of organotins, based on significant correlations between butyltins and environmental variables, were found in the study area.
Show more [+] Less [-]Mercury contamination in alligators (Melanosuchus niger) from Mamirauá Reservoir (Brazilian Amazon) and human health risk assessment
2014
Correia, Jozélia | Cesar, Ricardo | Marsico, Eliane | Diniz, George Tadeu Nunes | Camargo, Mauricio (Camargo-Zorro) | Castilhos, Zuleica
Mercury (Hg) concentrations in muscles of wild alligators (Melanosuchus niger) from the Mamirauá Reservoir (a reference area in the Brazilian Amazon) and the human health risks associated with its consumption were assessed. The mean Hg concentration in alligator muscles was 0.407 ± 0.114 μg/g (N = 61). Close to 5 % of the muscle samples showed Hg levels above the World Health Organization guideline for fish consumption (0.5 μg/g). A positive and significant relationship was observed between Hg concentrations in muscle and the age of the specimens. The dose-response approach suggests that close to 27.4 years is required for half of the exposed specimens to attain 0.5 μg/g. The hazard quotient (HQ) is a risk indicator which defines the ratio of exposure level and a toxicological reference dose. HQ resulted above the unity for all the specimens when the ingestion rate for riverine communities (200 g of muscle per day) is considered, indicating the existence of hazard. When the ingestion rate for market consumers (28.57 g/day) is considered, the risks are much lower (mean HQ = 0.55), suggesting that such group is not at risk. The establishment of local and regional ingestion rates for riverine populations and market consumers is extremely recommended.
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