ABSTRACT
Species sensitivity distribution (SSD) is commonly used in prospective risk assessment to derive predicted no-effect concentrations, toxicity exposure ratios, and environmental quality standards for individual chemicals such as pesticides. The application of SSD in the retrospective risk assessment of chemical mixtures at the river basin scale (i.e., the estimation of "multiple substance potentially affected fractions" [msPAFs]) has been suggested, but detailed critical assessment of such an application is missing. The present study investigated the impact of different data validation approaches in a retrospective model case study focused on seven herbicides monitored at the Scheldt river basin (Belgium) between 1998 and 2009. The study demonstrated the successful application of the SSD approach. Relatively high impacts of herbicides on aquatic primary producers were predicted. Often, up to 40 % of the primary producer communities were affected, as predicted by chronic msPAF, and in some cases, the predicted impacts were even more pronounced. The risks posed by the studied herbicides decreased during the 1998-2009 period, along with decreasing concentrations of highly toxic pesticides such as simazine or isoproturon. Various data validation approaches (the removal of duplicate values and outliers, the testing of different exposure durations and purities of studied herbicides, etc.) substantially affected SSD at the level of individual studied compounds. However, the time-consuming validation procedures had only a minor impact on the outcomes of the retrospective risk assessment of herbicide mixtures at the river basin scale. Selection of the appropriate taxonomic group for SSD calculation and selection of the species-specific endpoint (i.e., the most sensitive or average value per species) were the most critical steps affecting the final risk values predicted. The present validation study provides a methodological basis for the practical use of SSD in the retrospective risk assessment of chemical mixtures.
Subject(s)
Herbicides/adverse effects , Herbicides/chemistry , Models, Biological , Rivers/chemistry , Water Pollutants, Chemical/chemistry , Animals , Belgium , Ecosystem , Environmental Monitoring/methods , Reproducibility of Results , Risk Assessment , Risk Factors , Water MovementsABSTRACT
Electrospun polymeric nanofiber materials doped with 5,10,15,20-tetraphenylporphyrin (TPP) photosensitizer were prepared from four different polymers and were characterized with microscopic methods, steady-state, and time-resolved fluorescence and absorption spectroscopy. The polymers used included polyurethane Larithane™ (PUR), polystyrene (PS), polycaprolactone (PCL), and polyamide 6 (PA6). The antibacterial activity of all nanofiber materials against E. coli was activated by visible light and it was dependent on oxygen permeability/diffusion coefficients and the diameter of the polymeric nanofibers. This activity is based on oxidation ability of singlet oxygen O2(¹Δ(g)) that is generated upon irradiation. All tested nanofiber materials exhibited prolonged antibacterial properties, even in the dark after long-duration irradiation. The post-irradiation effect was explained by the photogeneration of H2O2, which provided the material with long-lasting antibacterial properties.
Subject(s)
Anti-Bacterial Agents/chemistry , Light , Nanofibers/chemistry , Photosensitizing Agents/chemistry , Porphyrins/chemistry , Anti-Bacterial Agents/pharmacology , Caprolactam/analogs & derivatives , Caprolactam/chemistry , Escherichia coli/drug effects , Hydrogen Peroxide/chemistry , Materials Testing , Oxidants/chemistry , Polyesters/chemistry , Polymers/chemistry , Polystyrenes/chemistry , Polyurethanes/chemistry , Singlet Oxygen/chemistryABSTRACT
Polyurethane (PUR) nanofabrics based on nanofibers of average diameters in the range of 250-110 nm with different meso-tetraphenylporphyrin (TPP) loading (0.01-5 wt %) were prepared by an electrospinning process. The oxygen quenching of excited states and singlet oxygen-sensitized delayed fluorescence (SODF) of TPP were studied at different oxygen pressures. We found that TPP in PUR matrix is present in monomeric state, and it is easily accessed by oxygen. Analysis of the kinetics of the TPP triplet, singlet oxygen, and SODF indicates that repopulation of TPP fluorescent state includes reaction of singlet oxygen with TPP triplets. The integrated SODF achieved more than 20% of the prompt fluorescence for nanofabric loaded with 5 wt % TPP. The dependence of SODF intensity on the TPP concentration in nanofibers is nearly quadratic.
