Utilization of long duration high-volume sampling coupled to SPME-GC-MS/MS for the assessment of airborne pesticides variability in an urban area (Strasbourg,France) during agricultural application

Atmospheric samples have been collected between 14 March and 12 September 2012 on a 2-week basis (15 days of sampling and exchange of traps each 7 days) in Strasbourg (east of France) for the analysis of 43 pesticides. Samples (particle and gas phases) were separately extracted using Accelerated Solvent Extraction (ASE) and pre-concentrated by Solid Phase Micro-Extraction (SPME) before analysis by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Four SPME consecutive injections at distinct temperatures were made in order to increase the sensitivity of detection for the all monitored pesticides. Currently used detected pesticides can be grouped in four classes; those used in maize crops (acetochlor, benoxacor, dicamba, s-metolachlor, pendimethalin, and bromoxynil), in cereal crops (benoxacor, chlorothalonil, fenpropimorph, and propiconazole), in vineyards (tebuconazole), and as herbicides for orchards, meadows of green spaces (2,4-MCPA, trichlopyr). This is in accordance with the diversity of crops found in the Alsace region and trends observed are in accordance with the period of application of these pesticides. Variations observed permit also to demonstrate that the long time sampling duration used in this study is efficient to visualize temporal variations of airborne pesticides concentrations. Then, long time high-volume sampling could be a simple method permitting atmospheric survey of atmospheric contamination without any long analysis time and consequently low cost.     

Human-mediated dispersal of aquatic invertebrates with waterproof footwear

Human-mediated dispersal has rarely been considered in wetland conservation strategies at regional scales, yet high concern exists about this aspect for (inter-)national management considering invasive species in other aquatic systems. In this context, we aim at understanding the role of human-mediated dispersal by footwear in protected wetlands with high conservation value. Zooplankton and zoobenthos were sampled in 13 shallow lakes in central Spain and, at the same time, mud attached to waders was collected and later cultured in deionized water under laboratory conditions for 4 weeks. Two-hundred and four individuals belonging to 19 invertebrate taxa were recovered after hatching; Ostracoda (84 %), Cladocera (53 %), Copepoda (30 %), Anostraca (30 %), and Notostraca (7 %) were the most frequent groups among the hatched crustaceans. NMDS and PERMANOVA analyses showed significant differences between the dispersed (via footwear) and the source active metacommunity, suggesting different dispersal abilities among the species found. Human vectors facilitate dispersal among protected lakes, which could eventuality lead to biotic homogenization and faster spread of non-indigenous species. Preservation strategies and education campaigns associated to target humans in close contact with water bodies should be imperative in conservation management of protected lakes.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-015-0689-x) contains supplementary material, which is available to authorized users.     

The SEAP in the city of Girona,a crossroads between boldness and pragmatism

The Covenant of Mayors has secured the commitments of over 5400 European Cities (as of December 2013) to achieving the European Union 20-20-20 climate change mitigation targets by 2020 through action at the local level. Due to the youth of the initiative, few experiences have been reported in the academic literature. We study the development of the Sustainable Energy Action Plan (SEAP) in the city of Girona (Catalonia, Spain) to analyse the opportunities and challenges this process may present in a small- to medium-sized, compact Mediterranean city. This knowledge can provide information to local authorities in similar municipalities, technical teams and decision-makers at the European level interested in enhancing the performance of such plans in the future. In this article, we explain how the SEAP was developed in Girona, the main results and proposed actions, and discuss the main setbacks. We conclude that an overarching European oversight organism is advisable to coordinate and aid local efforts.     

Open-pit coal-mining effects on rice paddy soil composition and metal bioavailability to Oryza sativa L. plants in Cam Pha, northeastern Vietnam

This study quantified Cd, Pb, and Cu content, and the soil–plant transfer factors of these elements in rice paddies within Cam Pha, Quang Ninh province, northeastern Vietnam. The rice paddies are located at a distance of 2 km from the large Coc Sau open-pit coal mine. Electron microprobe analysis combined with backscattered electron imaging and energy-dispersive spectroscopy revealed a relatively high proportion of carbon particles rimmed by an iron sulfide mineral (probably pyrite) in the quartz–clay matrix of rice paddy soils at 20–30 cm depth. Bulk chemical analysis of these soils revealed the presence of Cd, Cu, and Pb at concentrations of 0.146?±?0.004, 23.3?±?0.1, and 23.5?±?0.1 mg/kg which exceeded calculated background concentrations of 0.006?±?0.004, 1.9?±?0.5, and 2.4?±?1.5 mg/kg respectively at one of the sites. Metals and metalloids in Cam Pha rice paddy soils, including As, Cd, Cr, Cu, Hg, Mn, Ni, Pb, and Zn, were found in concentrations ranging from 0.2?±?0.1 to 140?±?3 mg/kg, which were in close agreement with toxic metal contents in mine tailings and Coc Sau coal samples, suggesting mining operations as a major cause of paddy soil contamination. Native and model Oryza sativa L. rice plants were grown in the laboratory in a growth medium to which up to 1.5 mg/kg of paddy soil from Cam Pha was added to investigate the effects on plant growth. A decrease in growth by up to 60 % with respect to a control sample was found for model plants, whereas a decrease of only 10 % was observed for native (Nep cai hoa vang variety) rice plants. This result suggests an adaptation of native Cam Pha rice plants to toxic metals in the agricultural lands. The Cd, Cu, and Pb contents of the native rice plants from Cam Pha paddies exceeded permitted levels in foods. Cadmium and Pb were highest in the rice plant roots with concentrations of 0.84?±?0.02 and 7.7?±?0.3 mg/kg, suggesting an intake of these metals into the rice plant as shown, for example, by Cd and Pb concentrations of 0.09?±?0.01 and 0.10?±?0.04 mg/kg respectively in the rice grain endosperm. The adaptation of native rice plants, combined with bioaccumulation ratios of 1?±?0.6 to 1.4?±?0.7 calculated for Cd transfer to the rice grain endosperm, and maximum Cd transfer factors of 4.3?±?2.1 to the plant roots, strongly suggest a continuous input of some toxic metals from coal-mining operations to agricultural lands in the region of Cam Pha. In addition, our results imply a sustained absorption of metals by native rice plant varieties, which may lead to metal accumulation (e.g., Cd) in human organs and in turn to severe disease.     

Growth parameters of deep-water decapod crustaceans in the Northwestern Mediterranean Sea: a comparative approach

 Relative and absolute growth were studied in 17 species of deep-water decapod crustaceans, spanning nine families of six different infra-orders, in the Northwestern Mediterranean Sea. The overall maximum abundance of these species lay between 200 m and 750 m (i.e. upper- and mid-slope species). Relative and absolute growth rates were compared by contrasting the slopes of the size–weight relationships for the different species and calculating the von Bertalanffy growth-equation parameters asymptotic length (L _∞ ) and growth rate (k). The size–weight relationships differed significantly as function of the species' life habits. The results revealed a significant decrease in weight relative to size in mesopelagic species (which carry out diel vertical migrations), an almost isometric relationship between size and weight in the less mobile nektobenthic species, and a significant increase in weight relative to size in strictly benthic species. The mean allometric coefficient for each group increased significantly from mesopelagic to benthic species. However, no general trend was observed in the growth-performance index, Φ (an index used to compare absolute growth rates between species, as a function of habit and depth of maximum abundance for all species combined), suggesting that the deep-water decapod crustaceans studied have similar absolute growth rates. Nevertheless, comparison of growth-parameter and growth-performance index values within families did reveal differences. Mesopelagic species of the families Sergestoidae and Pasiphaeidae showed slightly increased growth rates with increasing depth of distribution. Nektobenthic species of the genus Plesionika followed a trend opposite to that shown by mesopelagic species, with a higher growth rate for the shallowest-dwelling species (P. heterocarpus) than the deepest-dwelling species (P. acanthonotus). Taking growth as one of the major components of an organism's energy budget, the growth rates for the decapod crustacean species in this study were significantly lower than those reported in the literature for shallow-water penaeid crustacean species (which are distributed in higher-temperature habitats than deep-water Mediterranean crustaceans) and higher than those reported for mesopelagic myctophid fish species. Hence, the well-defined growth trends shown by deep-water decapod crustacean species in the Northwestern Mediterranean Sea, compared to the less well-defined trends in the other taxa, is discussed in the framework of the overall dynamics of their ecosystem. Received: 25 May 1998 / Accepted: 27 September 1999     

Occurrence of sulfonamide residues along the Ebro River basin: removal in wastewater treatment plants and environmental impact assessment

Sulfonamides (SAs) have become one of the antibiotic families most frequently found in all kind of environmental waters. In the present work, the presence of 16 SAs and one of their acetylated metabolites in different water matrices of the Ebro River basin has been evaluated during two different sampling campaigns carried out in 2007 and 2008. Influent and effluent samples from seven wastewater treatment plants (WWTPs), together with a total of 28 river water samples were analyzed by on-line solid phase extraction-liquid chromathography-tandem mass spectrometry (on-line SPE-LC-MS/MS). Sulfamethoxazole and sulfapyridine were the SAs most frequently detected in WWTPs (96-100%), showing also the highest concentrations, ranging from 27.2 ng L(-1) to 596 ng L(-1) for sulfamethoxazole and from 3.7 ng L(-1) to 227 ng L(-1) for sulfapyridine. Sulfamethoxazole was also the SA most frequently detected in surface waters (85% of the samples) at concentrations between 11 ng L(-1) and 112 ng L(-1). In order to assess the effectiveness of the wastewater treatment in degrading SAs, removal efficiencies in the seven WWTPs were calculated for each individual SA (ranging from 4% to 100%) and correlated to the corresponding hydraulic retention times or residence times of the SAs in the plants. SAs half-lives were also estimated, ranging from to 2.5 hours (sulfadimethoxine) to 128 h (sulfamethazine). The contribution of the WWTPs to the presence of SAs depends on both the load of SAs discharging on the surface water from the WWTP effluent but also on the flow of the receiving waters in the discharge sites and the dilution exerted; WWTP4 exerts the highest pressure on the receiving water course. Finally, the potential environmental risk posed by SAs was evaluated calculating the hazard quotients (HQ) to different non-target organisms in effluent and river water. The degree of susceptibility resulted in algae>daphnia>fish. Sulfamethoxazole was the only SA posing a risk to algae in effluent water, with an HQ>7.     

Environmental distribution of PAHs in pine needles,soils, and sediments

Introduction  

The content of 16 polycyclic aromatic hydrocarbons (PAHs) was determined in 60 samples from three environmental matrices (soils, sediments, and pine needles) in an effort to assess their distribution on a river basin scale.     

Lay perceptions of carbon capture and storage technology

The extent of social acceptance of carbon capture and storage (CCS) is likely to significantly influence the sustainable development of CO₂ storage projects. Acceptance of CCS by the key stakeholders (policy makers, the general public, the media and the local community), linked to specific projects, as well as how the technology is communicated about and perceived by the public, have become matters of interest for the social sciences. This article reports on an investigation of the public perception of CCS technology in Spain. Individuals’ views on CCS are analysed through focus groups with lay citizens using “stimulus materials”. As the analysis shows, lay views of CCS differ significantly from the views of decision-makers and experts. Public concerns and reactions to CCS technology and potential projects, as well as the degree of consensus on its acceptance or rejection are detailed. Implications for the future use of CCS are discussed.     

Mercury levels and liver pathology in feral fish living in the vicinity of a mercury cell chlor-alkali factory

Twenty-three barbels (Barbus graellsii), 30 bleaks (Alburnus alburnus) and 4 sediment samples were collected from four areas of the Cinca River (NE Spain), upstream and downstream of a mercury cell chlor-alkali plant. Mercury concentration in sediments downstream of the plant was about 25 times higher than the concentration upstream. Mercury levels in the muscle and liver of barbels downstream of the chlor-alkali plant were 10 and 30 times higher than those upstream. The average mercury concentration in the muscle and liver of barbels downstream of the factory was 1.48 and 1.78mg/kgw.w., with maximal concentrations of 2.43 and 3.64mg/kgw.w, respectively. Liver/muscle ratio of mercury was significantly higher in barbels sampled downstream of the factory. Bleak showed a similar pattern, with a significantly higher whole-body mercury concentration downstream of the chlor-alkali plant. Nevertheless, a progressive decrease in mercury concentration downstream of the impact area was found in bleak, but not in barbel. Histopathological analysis showed that fish downstream of the factory had significantly higher prevalence of liver pathologies (p<0.05). Although there are no specific histopathological markers of mercury exposure, barbels with the highest Hg levels in the liver also showed the most severe pathologies, and the processes found in these barbels were consistent with the pro-oxidant effect of heavy metals.     

Environmental monitoring by gene expression biomarkers in Barbus graellsii: laboratory and field studies

Barbel (Barbus graellsii) is a freshwater fish used as a sentinel species in environmental monitoring programmes and ecotoxicological studies in northern Spain, particularly in the Ebro River basin, the largest freshwater resource in Spain. We developed specific primers for the quantification of CYP1A and metallothionein (MT)-1 and -2 gene expression by QRT-PCR in barbel in order to assess their suitability in biological effect monitoring of dioxin-like compounds and metals. All three genes responded as expected in laboratory tests, using model inducers. Hepatic CYP1A mRNA levels showed a twofold induction in fish injected intraperitoneally with beta-naphthoflavone, whereas MT-1 and MT-2 gene expression was strongly induced by cadmium (15- and 13-fold, respectively) and mercury (five- and eightfold). Barbel populations from different sites on the Ebro River basin showed a good correlation between the historical records of organochlorine pollution, CYP1A expression levels and EROD activity. Nevertheless, although metallothionein protein levels in the liver of wild fish correlated with hepatic levels of mercury, MT-1 and MT-2 gene expression did not correlate with the mercury content or with the concentration of metals in sediments from the sites inhabited by the fish. These results demonstrate the utility of barbel CYP1A-mRNA expression, but not that of MT-1 or MT-2, as a biomarker in field studies. The tools and protocols developed here are likely to apply to other species of the genus Barbus, with some 700 species distributed throughout most of the Old World.