Sorption and release process of polybrominated diphenyl ethers (PBDEs) from different composition microplastics in aqueous medium: Solubility parameter approach.

Microplastics represent a growing environmental concern in the aquatic environment due to its size resemblance to microplankton in addition to its ability to act as concentrators of persistent organic pollutants (POPs). Among them, polybrominated diphenyl ethers (PBDEs) stand out as POPs with dangerous levels in the aquatic environment. In this paper we have developed a methodology for studying the sorption and extraction process of twelve congeners of PBDE from four microplastics: polyethylene terephthalate (PET), polypropylene (PP), low density polyethylene (LDPE) and polystyrene (PS). We have proved that there is a dependence between the polymer composition and the solvent used for the extraction of the analytes. The extraction is function of the ability of the solvent to partially or totally dissolve the plastic that will allow the analyte to have a greater capacity to be released from the polymer structure. The solution of the polymer is achieved by making the free energy (ΔG, or Gibbs potential) of the system negative making the process occurs spontaneously, this will depend on the solubility parameter (∂), specific of both, solvent and polymer. Therefore, this study helps to determine which methodology to be applied for the extraction of pollutants before the start of the analysis. This approach has been applied to microplastic samples collected in different locations in the four oceans and collected from the Barcelona World Race (BWR) 2014-2015 sailing race.

Analytical methodology for sampling and analysing eight siloxanes and trimethylsilanol in biogas from different wastewater treatment plants in Europe.

Siloxanes and trimethylsilanol belong to a family of organic silicone compounds that are currently used extensively in industry. Those that are prone to volatilisation become minor compounds in biogas adversely affecting energetic applications. However, non-standard analytical methodologies are available to analyse biogas-based gaseous matrixes. To this end, different sampling techniques (adsorbent tubes, impingers and tedlar bags) were compared using two different configurations: sampling directly from the biogas source or from a 200 L tedlar bag filled with biogas and homogenised. No significant differences were apparent between the two sampling configurations. The adsorbent tubes performed better than the tedlar bags and impingers, particularly for quantifying low concentrations. A method for the speciation of silicon compounds in biogas was developed using gas chromatography coupled with mass spectrometry working in dual scan/single ion monitoring mode. The optimised conditions could separate and quantify eight siloxane compounds (L2, L3, L4, L5, D3, D4, D5 and D6) and trimethylsilanol within fourteen minutes. Biogas from five waste water treatment plants located in Spain, France and England was sampled and analysed using the developed methodology. The siloxane concentrations in the biogas samples were influenced by the anaerobic digestion temperature, as well as the nature and composition of the sewage inlet. Siloxanes D4 and D5 were the most abundant, ranging in concentration from 1.5 to 10.1 and 10.8 to 124.0 mg Nm(-3), respectively, and exceeding the tolerance limit of most energy conversion systems.

Di-(2-ethylhexyl)phthalate in sewage sludge and post-treated sludge: quantitative determination by HRGC-MS and mass spectral characterization.

DEHP was quantified into sewage sludge, thermally dried sludge and compost samples from different areas of Catalonia (North East Spain) using high-resolution gas chromatography (HRGC) coupled to a mass spectrometry (MS). The aim of the work was to determine the evolution of this ubiquitous environmental contaminant along some post-treatment sludge processes, such as composting and thermally drying. DEHP concentration detected in some sludges are above the maximum limit suggested by the EC (100 ppm d.m.) for agricultural use. However, the composting and thermally drying reduce the amount of DEHP in sewage sludge to acceptable level for safe land application. The study was completed with the characterization and long-term observation of DEHP in sewage sludge, composted sludge and thermally dried sludge mixed with two types of soils. In all cases, the percentage of DEHP degraded was higher than 50% after 9 months of incubation.

Application of the new C18 speedisks to the analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans in water and effluent samples.

A recently introduced disk for solid-phase extraction of pollutants from water (C18 Speedisk) has been tested for the analysis of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF). The complete procedure of analysis has been validated with spiked deionized water. The accuracy, expressed as recovery for the sum of 2,3,7,8-substituted congeners. is 92% and the precision, expressed as the RSD of reproducibility, is 5.8%. The limit of detection (LOD), using 2 l of water, is 4.2 pg/l (0.6 pg ITEQ/l) for the sum of 2,3,7,8-substituted congeners. Actually, the C18 Speedisks have substituted the use of other C18 membrane disks in our laboratory because they allow the fast and efficient analysis of samples with high content of suspended material and reduce the time of elution of free-particulate samples. These disks have been successfully applied to the analysis of water from different sources and with very different physical and chemical characteristics: seawater, rain water, an industrial effluent, a landfill leachate and the inlet and chlorinated and non-chlorinated outlet water from a wastewater treatment plant.

Analysis of dioxin-like compounds in vegetation and soil samples burned in Catalan forest fires. Comparison with the corresponding unburned material.

Only a few data are reported about the formation of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) in forest fires. However, the inventories of sources undertaken by several European and American countries consider natural fires as a possible source of PCDD/F and, in some cases, as one of the most important. In our work we have analysed vegetation and soil samples burned in four forest fires which happened in Catalonia in the summer of 1998. The concentration of dioxin-like compounds (PCDD/F, non-ortho polychlorinated bi-phenyls (PCB) and mono-ortho PCB) has been compared to the concentration present in the corresponding unburned material collected in places near the fires but not affected. The results of this preliminary study show very low concentrations in all the samples, both burned and unburned. Although a change in the profile (proportional increase of tetrachlorinated congeners in PCDD/F) is observed in burned samples compared to unburned ones, the absolute values of concentration decrease in most samples. Therefore, natural fires seem not to be an important source of dioxin-like compounds. These results will be confirmed with air emissions measurements in future studies.

Separation of non-ortho polychlorinated biphenyl congeners on pre-packed carbon tubes. Application to analysis in sewage sludge and soil samples.

The analysis of planar (non-ortho) polychlorinated biphenyls (PCB) by HRGC-ECD or HRGC-HRMS requires a fractionation step to avoid the interferences of the bulk of PCB, usually in much higher concentration than the planar ones. In this paper, a new method, based on the fractionation of PCB on SPE commercial tubes pre-packed with Carbopack B, has been developed. After the extract has been applied on the stationary phase, the bulk of PCD are eluted with 15 ml of hexane (fraction I), mono-ortho PCB with 20 ml of hexane/toluene 99:1 (fraction II) and planar PCB with 20 ml of toluene (fraction III) in a station under vacuum. The method has been validated: accuracy (expressed as recovery in %) is >70% and precision (expressed as % RSD) is <20% considering changes of day, analyst and batch of tubes. The method is linear in the range studied. Other advantages are that the method is simple, rapid and it can be easily automated. The application of this separation to the determination of planar PCB in fly-ash extracts from an intercalibration exercise and to sewage sludge, sediment and soil samples has been successful. In addition, this method removes hydrocarbons from the planar PCB fraction and allows its concentration to very small volumes.

Study of evolution of PCDD/F in sewage sludge-amended soils for land restoration purposes.

The evolution of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in sewage sludge-amended soils used in the restoration of degraded lands, like quarries, has been studied. Two experiments were performed: one in the lab, under controlled conditions, and another in a quarry. Two different doses of sewage sludge were applied in both experiments (with two types of application in the quarry experiment) and the evolution of the amended soils were compared with that of the respective control soils (without addition of sewage sludge). The samples were analyzed with a previously validated method by HRGC HRMS after the extraction and the necessary clean-up steps. The results reveal that polluted sewage sludge increases PCDD/F concentration in soils and that these compounds are persistent in the matrix after long periods of time.