Many xenobiotics, including several pharmaceuticals and pesticides, are poorly treated in domestic wastewater treatment plants. Adsorption processes, such as with activated carbons, could be a solution to curb their discharge into the aquatic environment. As adsorbent-like activated carbon is known to be expensive, identifying promising alternative adsorbent materials is a key challenge for efficient yet affordable xenobiotic removal from wastewaters. As part of the effort to address this challenge, we surveyed the literature on pharmaceutical and pesticide xenobiotics and built a database compiling data from 38 scientific publications covering 65 xenobiotics and 58 materials. Special focus was given to the relevance and comparability of the data to the characteristics of the adsorbent materials used and to the operating conditions of the batch tests inventoried. This paper gives an in-depth overview of the adsorption capacities of various adsorbents. The little data on alternative adsorbent materials, especially for the adsorption of pharmaceuticals, makes it difficult to single out any one activated carbon alternative capable of adsorbing pesticides and pharmaceuticals at the tertiary stage of treatment. There is a pressing need for further lab-scale experiments to investigate the tertiary treatment of discharged effluents. We conclude with recommendations on how future data should best be used and interpreted.

[Departement_IRSTEA]Ecotechnologies [TR1_IRSTEA]TED [Axe_IRSTEA]TED-SOWASTE [Axe_IRSTEA]TED-EPURE | Many xenobiotics, including several pharmaceuticals and pesticides, are poorly treated in domestic wastewater treatment plants. Adsorption processes, such as with activated carbons, could be a solution to curb their discharge into the aquatic environment. As adsorbent-like activated carbon is known to be expensive, identifying promising alternative adsorbent materials is a key challenge for efficient yet affordable xenobiotic removal from wastewaters. As part of the effort to address this challenge, we surveyed the literature on pharmaceutical and pesticide xenobiotics and built a database compiling data from 38 scientific publications covering 65 xenobiotics and 58 materials. Special focus was given to the relevance and comparability of the data to the characteristics of the adsorbent materials used and to the operating conditions of the batch tests inventoried. This paper gives an in-depth overview of the adsorption capacities of various adsorbents. The little data on alternative adsorbent materials, especially for the adsorption of pharmaceuticals, makes it difficult to single out any one activated carbon alternative capable of adsorbing pesticides and pharmaceuticals at the tertiary stage of treatment. There is a pressing need for further lab-scale experiments to investigate the tertiary treatment of discharged effluents. We conclude with recommendations on how future data should best be used and interpreted.

The purpose of this study was to explore the effects of soil contamination by selected metals (cadmium, copper, nickel, lead or zinc) on the antioxidant response of Vicia faba plants. The levels of the antioxidants: glutathione, proline, non-protein thiols, as well as guaiacol peroxidase and catalase activities were measured in the upperparts of plants. Additionally, the potential bioavailability of metals in the soil and their concentrations in V. faba plants were compared. Treatment with metal caused the problem of an elevation in its bioavailability in soil and its concentration in leaves and stems. The most serious problems seemed to be metal elevations in soil, especially Zn and Ni as well as in the aerial parts of V. faba plants. The antioxidant responses appeared to be metal specific. The elevation of guaiacol peroxidase activity in leaves and stems as well as the proline in leaves was the only more general reaction to metal exposure. Upon analysis of the effects of soil metal contamination on V. faba plants, we recommend the use of some measurements such as guaiacol peroxidase activity and proline level as useful tools in biological monitoring.

The purpose of this study was to explore the effects of soil contamination by selected metals (cadmium, copper, nickel, lead or zinc) on the antioxidant response of Vicia faba plants. The levels of the antioxidants: glutathione, proline, non-protein thiols, as well as guaiacol peroxidase and catalase activities were measured in the upperparts of plants. Additionally, the potential bioavailability of metals in the soil and their concentrations in V. faba plants were compared. Treatment with metal caused the problem of an elevation in its bioavailability in soil and its concentration in leaves and stems. The most serious problems seemed to be metal elevations in soil, especially Zn and Ni as well as in the aerial parts of V. faba plants. The antioxidant responses appeared to be metal specific. The elevation of guaiacol peroxidase activity in leaves and stems as well as the proline in leaves was the only more general reaction to metal exposure. Upon analysis of the effects of soil metal contamination on V. faba plants, we recommend the use of some measurements such as guaiacol peroxidase activity and proline level as useful tools in biological monitoring. | Antioxidant response, Metal contamination, Vicia faba | 30 | 1124-1134 | 2

Rainwater contains a complex mixture of organic compounds which may influence climate, terrestrial and maritime ecosystems and thus human health. In this work, the characteristics of DOM of bulk deposition at a coastal town on the southwest of Europe were assessed by UV–visible and three-dimensional excitation–emission matrix fluorescence spectroscopies and by dissolved organic carbon (DOC) content. The seasonal and air mass trajectory effects on dissolved organic matter (DOM) of bulk deposition were evaluated. The absorbance at 250 nm (UV₂₅₀ₙₘ) and integrated fluorescence showed to be positively correlated with each other, and they were also positively correlated to the DOC in bulk deposition, which suggest that a constant fraction of DOM is likely to fluoresce. There was more chromophoric dissolved organic matter (CDOM) present in summer and autumn seasons than in winter and spring. Bulk deposition associated with terrestrial air masses contained a higher CDOM content than bulk deposition related to marine air masses, thus highlighting the contribution of terrestrial/anthropogenic sources.

Rainwater contains a complex mixture of organic compounds which may influence climate, terrestrial and maritime ecosystems and thus human health. In this work, the characteristics of DOM of bulk deposition at a coastal town on the southwest of Europe were assessed by UV-visible and three-dimensional excitation-emission matrix fluorescence spectroscopies and by dissolved organic carbon (DOC) content. The seasonal and air mass trajectory effects on dissolved organic matter (DOM) of bulk deposition were evaluated. The absorbance at 250 nm (UV(250 nm)) and integrated fluorescence showed to be positively correlated with each other, and they were also positively correlated to the DOC in bulk deposition, which suggest that a constant fraction of DOM is likely to fluoresce. There was more chromophoric dissolved organic matter (CDOM) present in summer and autumn seasons than in winter and spring. Bulk deposition associated with terrestrial air masses contained a higher CDOM content than bulk deposition related to marine air masses, thus highlighting the contribution of terrestrial/anthropogenic sources. | Authors acknowledge funding from the Portuguese FCT (Foundation for Science and Technology) to CESAM (Centre for Environmental and Marine Studies). The FCT fellowship given to P.S.M. Santos (Ref. SFRH/BPD/75350/2010) is also acknowledged. Authors would like to gratefully thank the Group of Organic Chemistry of University of Aveiro for making available to us the use of their Fluoromax 3 equipment of molecular fluorescence spectrophotometer. TOC analyses were carried out at the “Administração Regional de Saúde” (Aveiro) and authors wish to here express their gratitude to this Centre and especially to Dra. Ana Maria Félix and Dra. Rosário Figueiredo. The authors also wish to thank Professor Maria Dolores Orgaz from the Department of Physics at the University of Aveiro for meteorological information support. | published

A set of periurban calcareous agricultural Mediterranean soils was spiked with a mixture of Cd, Cu, Pb and Zn at two levels within the limit values proposed by current European legislation, incubated for up to 12 months, and subjected to various one-step extraction procedures to estimate mobile (neutral salts) and potentially mobile metal fractions (complexing and acidic extraction methods). The results obtained were used to study metal extractability patterns according to the soil characteristics. The analytical data were coupled with mineralogical investigations and speciation modelling using the Visual Minteq model. The formation of soluble metal-complexes in the complexing extracts (predicted by the Visual Minteq calculations) led to the highest extraction efficiency with complexing extractants. Metal extractability patterns were related to both content and composition of carbonate, organic matter, Fe oxide and clay fractions. Potentially mobile metal fractions were mainly affected by the finest soil fractions (recalcitrant organic matter, active lime and clay minerals). In the case of Pb, scarce correlations between extractable Pb and soil constituents were obtained which was attributed to high Pb retention due to the formation of 4PbCO3·3PbO (corroborated by X-ray diffraction). In summary, the high metal proportion extracted with complexing agents highlighted the high but finite capacity to store potentially mobilizable metals and the possible vulnerability of these soils against environmental impact from metal accumulation.

A set of periurban calcareous agricultural Mediterranean soils was spiked with a mixture of Cd, Cu, Pb and Zn at two levels within the limit values proposed by current European legislation, incubated for up to 12 months, and subjected to various one-step extraction procedures to estimate mobile (neutral salts) and potentially mobile metal fractions (complexing and acidic extraction methods). The results obtained were used to study metal extractability patterns according to the soil characteristics. The analytical data were coupled with mineralogical investigations and speciation modelling using the Visual Minteq model. The formation of soluble metal-complexes in the complexing extracts (predicted by the Visual Minteq calculations) led to the highest extraction efficiency with complexing extractants. Metal extractability patterns were related to both content and composition of carbonate, organic matter, Fe oxide and clay fractions. Potentially mobile metal fractions were mainly affected by the finest soil fractions (recalcitrant organic matter, active lime and clay minerals). In the case of Pb, scarce correlations between extractable Pb and soil constituents were obtained which was attributed to high Pb retention due to the formation of 4PbCO3·3PbO (corroborated by X-ray diffraction). In summary, the high metal proportion extracted with complexing agents highlighted the high but finite capacity to store potentially mobilizable metals and the possible vulnerability of these soils against environmental impact from metal accumulation. © 2013 Springer-Verlag Berlin Heidelberg.

In summer, high levels of ozone (O₃) are frequently measured at both Galicia and Northern Portugal air quality monitoring stations, even exceeding the limit values imposed by legislation. This work aims to investigate the origin of these high O₃ concentrations by the application of a chemical transport modelling system over the northwestern area of the Iberian Peninsula. The WRF–CHIMERE modelling system was applied with high resolution to simulate the selected air pollution episodes that occurred simultaneously in Galicia and North Portugal and in order to study both the contribution of local emission sources and the influence of transboundary pollution. Emission inputs have been prepared based on the development of the Portuguese and Galician emission inventories. The obtained results for O₃ have been evaluated and validated against observations. Modelling results show possible contribution of the transboundary transport over the border of two neighbour regions/countries, indicating that the O₃ episode starts over the urban and industrialised area of North coast of Portugal, reaching the maximum peaks over this region; at the same time, O₃ levels increased over Galicia region, where lower concentrations, but still high, were observed. These results pointed out that air quality management should not be driven by political boundaries and highlight the importance of joining efforts between neighbouring countries.

Insummer,highlevelsofozone(O3)arefrequently measured at both Galicia and Northern Portugal air quality monitoring stations, even exceeding the limit values imposed by legislation. This work aims to investigate the origin of these high O3 concentrations by the application of a chemical transport modelling system over the northwestern area of the Iberian Peninsula. The WRF–CHIMERE modelling system was applied with high resolution to simulate the selected air pollutionepisodesthatoccurredsimultaneouslyinGaliciaand North Portugal and in order to study both the contribution of local emission sources and the influence of transboundary pollution. Emission inputs have been prepared based on the development of the Portuguese and Galician emission inventories. The obtained results for O3 have been evaluated and validated against observations. Modelling results show possiblecontributionofthetransboundarytransportovertheborder of two neighbour regions/countries, indicating that the O3 episode starts over the urban and industrialised area of North coast of Portugal, reaching the maximum peaks over this region; at the same time, O3 levels increased over Galicia region, where lower concentrations, but still high, were observed. These results pointed out that air quality management should not be driven by political boundaries and high light the importance of joining efforts between neigh bouring countries. | TheauthorsacknowledgethePortugueseEnvironmental Protection Agency, MeteoGalicia, Laboratorio de Medio Ambiente de Galicia (Xunta de Galicia) and As Pontes Power Plant (Endesa) for the observational dataset support. The authors gratefully acknowledge the NOAA Air Resources Laboratory (ARL) for the provision of the HYSPLIT transport and dispersion model and/or READY website (http://www.arl. noaa.gov/ready.php) used in this publication. Thanks are extended to the Portuguese Ministério da Ciência, da Tecnologia e do Ensino Superior for the post-doctoral grants of A. Monteiro (SFRH/BPD/63796/2009) and J. Ferreira (SFRH/BPD/40620/2007). PhD grants of A. Rodríguez and M. Dios (‘María Barbeito’ Programme) and the research stay abroad grant of M.Dios(09.02.561B.444.0) at the University of Aveiro were supported by Xunta de Galicia regional government. This work was developed as part of the project ‘XIMERE/FUXIMERE’ (10MDS009E), also with support of Endesa Generación, S.A. (‘Characterization of ozone episodes’) and Troposfera S.C. (‘Collaboration in air quality modeling over Galicia’). | published

In recent decades, many toxicological tests based on in vivo or in vitro models, mainly from mammalian (rat–mouse) and fish species, were used to assess the risks raised by contact or ingestion of molecules of pharmaceutical, agricultural, or natural origin. But no, or few, in vitro tests using other non-mammalian models such as bird have been explored despite their advantages: the embryonic gonads of birds have a high plasticity of development sensitive to estrogen, and sperm production is nearly two times faster than in rodents. Hence, we have established an in vitro culture of germ cells and somatic cells from chicken post-natal testis, and we have evaluated the sensitivity against the endocrine disruptor compound mono-(2-ethylhexyl) phthalate (MEHP) in comparison to previous studies using rodent and human models. After 96 h of exposure in presence of 10 μM MEHP, chicken seminiferous tubules cultures present a structural alteration, a reduction in cell proliferation and in germ cells population. Apoptosis of germ and somatic cells increases in presence of 1 μM MEHP. Furthermore, MEHP does not affect inhibin B and lactate production by Sertoli cells. These results are in accordance with previous studies using rat, mice, or human culture of testicular cells and in similar range of exposures or even better sensitivity for some “end-points” (biological parameters). In conclusion, the establishment of this postnatal testicular cells culture could be considered as an alternative method to in vivo experiments frequently used for evaluating the impact on the terrestrial wildlife species. This method could be also complementary to mammal model due to the limiting number of animals used and its elevated sensitivity.

In recent decades, many toxicological tests based on in vivo or in vitro models, mainly from mammalian (rat-mouse) and fish species, were used to assess the risks raised by contact or ingestion of molecules of pharmaceutical, agricultural, or natural origin. But no, or few, in vitro tests using other non-mammalian models such as bird have been explored despite their advantages: the embryonic gonads of birds have a high plasticity of development sensitive to estrogen, and sperm production is nearly two times faster than in rodents. Hence, we have established an in vitro culture of germ cells and somatic cells from chicken post-natal testis, and we have evaluated the sensitivity against the endocrine disruptor compound mono-(2-ethylhexyl) phthalate (MEHP) in comparison to previous studies using rodent and human models. After 96 h of exposure in presence of 10 μM MEHP, chicken seminiferous tubules cultures present a structural alteration, a reduction in cell proliferation and in germ cells population. Apoptosis of germ and somatic cells increases in presence of 1 μM MEHP. Furthermore, MEHP does not affect inhibin B and lactate production by Sertoli cells. These results are in accordance with previous studies using rat, mice, or human culture of testicular cells and in similar range of exposures or even better sensitivity for some "end-points" (biological parameters). In conclusion, the establishment of this postnatal testicular cells culture could be considered as an alternative method to in vivo experiments frequently used for evaluating the impact on the terrestrial wildlife species. This method could be also complementary to mammal model due to the limiting number of animals used and its elevated sensitivity.