We investigated the behavior of metallic silver nanoparticles (Ag-NP) in a pilot wastewater treatment plant (WWTP) fed with municipal wastewater. The treatment plant consisted of a nonaerated and an aerated tank and a secondary clarifier. The average hydraulic retention time including the secondary clarifier was 1 day and the sludge age was 14 days. Ag-NP were spiked into the nonaerated tank and samples were collected from the aerated tank and from the effluent. Ag concentrations determined by inductively coupled plasma-mass spectrometry (ICP-MS) were in good agreement with predictions based on mass balance considerations. Transmission electron microscopy (TEM) analyses confirmed that nanoscale Ag particles were sorbed to wastewater biosolids, both in the sludge and in the effluent. Freely dispersed nanoscale Ag particles were only observed in the effluent during the initial pulse spike. X-ray absorption spectroscopy (XAS) measurements indicated that most Ag in the sludge and in the effluent was present as Ag(2)S. Results from batch experiments suggested that Ag-NP transformation to Ag(2)S occured in the nonaerated tank within less than 2 h. Physical and chemical transformations of Ag-NP in WWTPs control the fate, the transport and also the toxicity and the bioavailability of Ag-NP and therefore must be considered in future risk assessments.
Despite their common use in animal production the environmental fate of the veterinary sulfonamide antibiotics after excretion is only poorly understood. We performed irrigation experiments to investigate the transport of these substances with surface runoff on grassland. Liquid manure from pigs treated with sulfadimidine was spiked with sulfadiazine, sulfathiazole, the herbicide atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine), and the conservative tracer bromide and spread onto eight plots. Four plots received the same amounts of the spiked substances in aqueous solution (controls). Apart from the application matrix we varied the time between application and irrigation. Manure increased the runoff volume up to six times compared with the controls. It seemed that manure enhanced the runoff by sealing the soil surface. On manured plots the relative antibiotic concentrations in runoff were higher than on the controls, reaching an average of 0.3% (sulfadiazine), 0.8% (sulfathiazole), and 1.4% (sulfadimidine) of the input concentrations after a 1-d contact time. The corresponding values on the controls were 0.16% for sulfadiazine and 0.08% for sulfathiazole. After 3 d, the maximum values on the manured plots were even higher, whereas they had fallen below the limit of quantification on the controls. As a consequence, the sulfonamide losses were 10 to 40 times larger on the manured plots. The relative mobility of the sulfonamides on the control plots followed the trend expected from their chromatographic separation but the opposite was found on the manured plots. Hence it is important to consider explicitly the physical and chemical effects of manure when assessing the environmental fate of sulfonamides.
Biocides are included in organic building façade coatings as protection against biological attack by algae and fungi but have the potential to enter the environment via leaching into runoff from wind driven rain. The following field study correlates wind driven rain to runoff and measured the release of several commonly used organic biocides (terbutryn, Irgarol 1051, diuron, isoproturon, OIT, DCOIT) in organic façade coatings from four coating systems. During one year of exposure of a west oriented model house façade in the Zurich, Switzerland area, an average of 62.7 L/m(2), or 6.3% of annual precipitation came off the four façade panels installed as runoff. The ISO method for calculating wind driven rain loads is adapted to predict runoff and can be used in the calculation of emissions in the field. Biocide concentrations tend to be higher in the early lifetime of the coatings and then reach fairly consistent levels later, generally ranging on the order of mg/L or hundreds of μg/L. On the basis of the amount remaining in the film after exposure, the occurrence of transformation products, and the calculated amounts in the leachate, degradation plays a significant role in the overall mass balance.
This paper was motivated by a recent article in which the levels of electromagnetic energy absorbed in the heads of mobile phone users were compared for children and adults at the frequencies of 835 MHz and 1,900 MHz. Significant differences were found, in particular substantially greater absorption in children's heads at 835 MHz. These findings contradict other studies in which no significant changes had been postulated. The clarification of this issue is crucial to the mobile communications industry since current SAR evaluations as required by the FCC are only performed with phantoms based on the heads of adults. In order to investigate the differences in absorption between adults and children due to their differing anatomies, simulations have been performed using head phantoms based on MRI scans of an adult (voxel size 2 x 2 x 1 mm3) and two children (voxel size 2 x 2 x 1.1 mm3) of the ages of 3 and 7 y. Ten different tissue types were distinguished. The differences in absorption were investigated for the frequencies of 900 MHz and 1,800 MHz using 0.45 lambda dipoles instead of actual mobile phones. These well-defined sources simplified the investigation and facilitated the comparison to previously published data obtained from several numerical and experimental studies on phantoms based on adults. All simulations were performed using a commercial code based on the finite integration technique. The results revealed no significant differences in the absorption of electromagnetic radiation in the near field of sources between adults and children. The same conclusion holds when children are approximated as scaled adults.
Urban water management requires further clarification about pollutants in storm water. Little is known about the release of organic additives used in construction materials and the impact of these compounds to storm water runoff. We investigated sources and pathways of additives used in construction materials, i.e., biocides in facades' render as well as root protection products in bitumen membranes for rooftops. Under wet-weather conditions, the concentrations of diuron, terbutryn, carbendazim, irgarol 1051 (all from facades) and mecoprop in storm water and receiving water exceeded the predicted no-effect concentrations values and the Swiss water quality standard of 0.1 microg/L. Under laboratory conditions maximum concentrations of additives were in the range of a few milligrams and a few hundred micrograms per litre in runoff of facades and bitumen membranes. Runoff from aged materials shows approximately one to two orders of magnitude lower concentrations. Concentrations decreased also during individual runoff events. In storm water and receiving water the occurrence of additives did not follow the typical first flush model. This can be explained by the release lasting over the time of rainfall and the complexity of the drainage network. Beside the amounts used, the impact of construction materials containing hazardous additives on water quality is related clearly to the age of the buildings and the separated sewer network. The development of improved products regarding release of hazardous additives is the most efficient way of reducing the pollutant load from construction materials in storm water runoff.
The European Biocidal Products Directive 98/8/EC requires a risk assessment concerning possible effects of active ingredients on the environment. Biocides can be leached from treated materials exposed to outdoor use. These emissions have to be estimated and evaluated during the authorization procedure. Different immersion and irrigation tests were performed to investigate leaching of biocides from façade coatings. Several marketed formulations of textured coatings and paints spiked with a mixture of commonly used active ingredients (OIT, DCOIT, IPBC, carbendazim, isoproturon, diuron, terbutryn, and Irgarol 1051) were investigated. The emission process can be described by time-dependent functions that depend on the test conditions. The results of all test procedures confirm that leachability is related to water solubility and n-octanol-water partition coefficient of the active ingredients and that leaching of biocides from façade coatings is mainly a diffusion controlled process. Other factors like the composition of the product, availability and transport of water, concentration of active ingredients in the coatings, as well as UV-exposure of the coatings influence biocide emissions.
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