Assessment of commercially available polymeric materials for sorptive microextraction of priority and emerging nonpolar organic pollutants in environmental water samples

Among the different organic pollutants, persistent organic pollutants and emerging organic contaminants (EOCs) are of particular concern due to their potentially dangerous effects on the ecosystems and on human health. In the framework of the analysis of some of these organic pollutants in water samples, sorptive extraction devices have proven to be adequate for their monitoring. The efficiency of four commercially available and low-cost polymeric materials [polypropylene, poly(ethylene terephthalate), Raffia, and polyethersulfone (PES)] for the simultaneous extraction of 16 organic compounds from five different families from environmental water samples was evaluated in this work. Firstly, the homogeneity of the sorbent materials was confirmed by means of Raman spectroscopy. After the optimization of the parameters affecting the extraction and the liquid desorption steps, it was found that PES showed the largest efficiencies for slightly polar analytes and, to a lesser extent, for nonpolar analytes. Additionally, Raffia rendered good extraction efficiencies for nonpolar compounds. Thus sorptive extraction methods followed by large volume injection-programmable temperature vaporizer-gas chromatography-mass spectrometry were validated using PES and Raffia as sorbent materials. The validation of the method provided good linearity (0.978?r ²?r ²?-1 level). Finally, these materials were applied to the analysis of contaminants in environmental water samples.     

Investigative monitoring within the European Water Framework Directive: a coastal blast furnace slag disposal, as an example

The European Water Framework Directive (WFD) establishes a framework for the protection of estuarine and coastal waters, with the most important objective being to achieve 'good ecological status' for all waters, by 2015. Hence, Member States are establishing programmes for the monitoring of water quality status, through the assessment of ecological and chemical elements. These monitoring programmes can be of three types: surveillance monitoring; operational monitoring (both undertaken on a routine basis); and investigative monitoring (carried out where the reason of any exceedance for ecological and chemical status is unknown). Until now, nothing has been developed in relation to investigative monitoring and no clear guidance exists for this type of monitoring, as it must be tackled on a 'case-by-case' basis. Consequently, the present study uses slag disposal from a blast furnace, into a coastal area, as a case-study in the implementation of investigative monitoring, according to the WFD.In order to investigate the potential threat of such slags, this contribution includes: a geophysical study, to determine the extent of the disposal area; sediment analysis; a chemical metal analysis; and an ecotoxicological study (including a Microtox test and an amphipod bioassay). The results show that metal concentrations are several times above the background concentration. However, only one of the stations showed toxicity after acute toxicological tests, with the benthic communities being in a good status. The approaches used here show that contaminants are not bioavailable and that no management actions are required with the slags.     

Background metal levels determination in bivalves – quality assessment of the European Water Framework Directive

Background levels of metals (Ag, Cd, Cu, Cr, Hg, Ni, Pb and Zn) in biomonitors (Mytilus galloprovincialis mussels and Crassostrea gigas oysters), in estuarine waters within the Basque Country (south-east Bay of Biscay) are estimated using non-parametric statistical tools and data are presented graphically, with the aim of being used in assessing the ecological status, within the European Water Framework Directive (WFD). The basis for this study was the statistical analysis of data compiled from monitoring programmes undertaken along the Basque coast, between 1990 and 2008. For this analysis, a heuristic method was adapted and used. Results showed different metal background ranges throughout the year for both mussels and oysters. Values corresponding to the upper limit of the background range (i.e. value of the upper whisker of the box-plot) are proposed as the ‘high/good’ status boundary, according to the WFD.     

Differences in EDTA-assisted metal phytoextraction between metallicolous and non-metallicolous accessions of Rumex acetosa L.

Two common sorrel (Rumex acetosa) accessions, one from a Zn-Pb contaminated site (CS accession) and the other from an uncontaminated site (UCS accession), were hydroponically exposed to a mixture of heavy metals (Pb²⁺ + Zn²⁺ + Cd²⁺) with and without EDTA at an equimolar rate. The metallicolous CS accession showed a higher tolerance to metal treatment in the absence of the chelating agent, whereas the UCS accession was especially tolerant to EDTA treatment alone. Combination of metal and EDTA treatment resulted in a higher Pb accumulation in shoots of both accessions although plants hardly showed phytotoxic symptoms. Cd and Zn uptake was not augmented by EDTA addition to the polymetallic medium. Chelant-assisted Pb accumulation was 70% higher in the CS accession than in the UCS accession, despite the fact that the former accession evapotranspired less water than the UCS accession. These results support the existence of a non-selective apoplastic transport of metal chelates by R. acetosa roots, not related to transpiration stream.     

Agro-industrial wastes as effective amendments for ecotoxicity reduction and soil health improvement in aided phytostabilization

Aided phytostabilization is a technology that uses metal tolerant plants and organic and/or inorganic amendments to reduce soil metal bioavailability, while improving soil health. Our objective was to determine the effects of the application of amendments [sheep manure (SHEEP), poultry litter (POULTRY), cow slurry (COW), and paper mill sludge mixed with poultry litter (PAPER)], together with the growth of a metallicolous Festuca rubra L. population, on (i) chemical and microbial indicators of soil health and (ii) soil ecotoxicity, during the aided phytostabilization of a Zn/Pb contaminated mine soil. Amendment application led to an increase in soil pH, organic matter content, and inorganic salts, resulting in a decrease in Pb and Zn CaCl₂-extractable concentrations in soil, which, in turn, contributed to lower ecotoxicity and a stimulation of plant growth and soil microbial communities. The factor most affecting the metal extractability was probably soil pH. POULTRY was the best amendment in terms of increasing plant growth, chlorophylls content, and soil microbial biomass and activity, but resulted in higher levels of phytoavailable Pb and Zn. SHEEP and PAPER were more effective at reducing metal CaCl₂-extractability and, consequently, led to lower values of metal accumulation in plant tissues, thereby reducing the risk of metals entering into the food chain. When combined with the application of organic amendments, the metallicolous F. rubra population studied here appears an excellent candidate for aided phytostabilization. Our results indicate that the application of organic amendments is essential for the short-term recovery of highly contaminated metalliferous soils during aided phytostabilization.     

Sources and spatial distribution of polycyclic aromatic hydrocarbons in coastal sediments of the Basque Country (Bay of Biscay)

This contribution characterises the sources and distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments of the Basque coast (Bay of Biscay). Different source characterisation approaches (i.e. GIS assisted-chemometrics, PAH diagnostic ratios and analyses of composition profiles) were used in combination to successfully identify the factors determining the origin and distribution of PAHs. Urban/industrial combustion processes were identified as the main PAH source. However, the analysis of PAH composition patterns and diagnostic ratios identified secondary natural and petrogenic PAH sources on small spatial scales. The median ∑18PAH concentration ranged from 66 μg kg^?1 (d.w.) to 7021 μg kg^?1 (d.w.). The Ibaizabal estuary, which supports most of the anthropogenic pressure in the region (i.e. urban development, industrialisation, commercial and recreational harbours), also showed the highest PAH concentrations. On the shelf, human activities, hydrodynamic conditions and geomorphological features led to spatial differences in the PAH concentrations among sectors: the offshore and west sectors were characterised by higher concentrations, while the lowest values were found in the mid and east sectors. The results enhance the knowledge on PAH-related contamination processes and could be used to support the environmental assessment process required under current European marine legislation.     

Source characterisation and mid-term spatial and temporal distribution of polycyclic aromatic hydrocarbons in molluscs along the Basque coast (northern Spain)

The variability of polycyclic aromatic hydrocarbons (PAH) measured in the soft tissues of Mediterranean mussels (Mytilus galloprovincialis) and Pacific oysters (Crassostrea gigas) are investigated. Samples were collected from estuarine waters within the Basque Country (Bay of Biscay), between 2003 and 2011. PAH bioaccumulation showed some seasonality and significant differences were observed between cold (autumn–winter) and warm (spring–summer) seasons. Sites located within the ports of Bilbao and Pasaia showed the highest PAH concentrations in molluscs, and the highest percentages of samples above the established Environmental Quality Standards and Environmental Assessment Criteria. Probably due to human activities carried out in the area, no clear trends were observed, between 2003 and 2011, for the autumn data. Since the Basque coast is an area with high population density and industrial activity, the congener profiles (which reveal the predominance of tetra-aromatics) and the diagnostic ratios identified urban/industrial combustion processes as the main PAH sources. However, natural and petrogenic sources cannot be disregarded.     

Interactions between plant and rhizosphere microbial communities in a metalliferous soil

In the present work, the relationships between plant consortia, consisting of 1-4 metallicolous pseudometallophytes with different metal-tolerance strategies (Thlaspi caerulescens: hyperaccumulator; Jasione montana: accumulator; Rumex acetosa: indicator; Festuca rubra: excluder), and their rhizosphere microbial communities were studied in a mine soil polluted with high levels of Cd, Pb and Zn. Physiological response and phytoremediation potential of the studied pseudometallophytes were also investigated. The studied metallicolous populations are tolerant to metal pollution and offer potential for the development of phytoextraction and phytostabilization technologies. T. caerulescens appears very tolerant to metal stress and most suitable for metal phytoextraction; the other three species enhance soil functionality. Soil microbial properties had a stronger effect on plant biomass rather than the other way around (35.2% versus 14.9%). An ecological understanding of how contaminants, ecosystem functions and biological communities interact in the long-term is needed for proper management of these fragile metalliferous ecosystems.