Behavior of nine selected emerging trace organic contaminants in an artificial recharge system supplemented with a reactive barrier

Artificial recharge improves several water quality parameters, but has only minor effects on recalcitrant pollutants. To improve the removal of these pollutants, we added a reactive barrier at the bottom of an infiltration basin. This barrier contained aquifer sand, vegetable compost, and clay and was covered with iron oxide dust. The goal of the compost was to sorb neutral compounds and release dissolved organic carbon. The release of dissolved organic carbon should generate a broad range of redox conditions to promote the transformation of emerging trace organic contaminants (EOCs). Iron oxides and clay increase the range of sorption site types. In the present study, we examined the effectiveness of this barrier by analyzing the fate of nine EOCs. Water quality was monitored before and after constructing the reactive barrier. Installation of the reactive barrier led to nitrate-, iron-, and manganese-reducing conditions in the unsaturated zone below the basin and within the first few meters of the saturated zone. Thus, the behavior of most EOCs changed after installing the reactive barrier. The reactive barrier enhanced the removal of some EOCs, either markedly (sulfamethoxazole, caffeine, benzoylecgonine) or slightly (trimethoprim) and decreased the removal rates of compounds that are easily degradable under aerobic conditions (ibuprofen, paracetamol). The barrier had no remarkable effect on 1H-benzotriazole and tolyltriazole.     

How Should Death Be Taken into Account in Welfare Assessments?

That death is not a welfare issue appears to be a widespread view among animal welfare researchers. This paper demonstrates that this view is based on a mistaken assumption about harm, which is coupled to ‘welfare’ being conceived as ‘welfare at a time’. Assessments of welfare at a time ignore issues of longevity. In order to assess the welfare issue of death, it is necessary to structure welfare assessment as comparisons of possible lives of the animals. The paper also demonstrates that excluding the welfare issues of being deprived of life from the ethical assessment of killing distorts the ethical considerations.     

Monitoring and assessing of landscape heterogeneity at different scales

In numerous studies, spatial and spectral aggregations of pixel information using average values from imaging spectrometer data are suggested to derive spectral indices and the subsequent vegetation parameters that are derived from these. Currently, there are very few empirical studies that use hyperspectral data, to support the hypothesis for deriving land surface variables from different spectral and spatial scales. In the study at hand, for the first time ever, investigations were carried out on fundamental scaling issues using specific experimental test flights with a hyperspectral sensor to investigate how vegetation patterns change as an effect of (1) different spatial resolutions, (2) different spectral resolutions, (3) different spatial and spectral resolutions as well as (4) different spatial and spectral resolutions of originally recorded hyperspectral image data compared to spatial and spectral up- and downscaled image data. For these experiments, the hyperspectral sensor AISA-EAGLE/HAWK (DUAL) was mounted on an aircraft to collect spectral signatures over a very short time sequence of a particular day. In the first experiment, reflectance measurements were collected at three different spatial resolutions ranging from 1 to 3 m over a 2-h period in 1 day. In the second experiment, different spectral image data and different additional spatial data were collected over a 1-h period on a particular day from the same test area. The differently recorded hyperspectral data were then spatially and spectrally rescaled to synthesize different up- and down-rescaled images. The normalised difference vegetation index (NDVI) was determined from all image data. The NDVI heterogeneity of all images was compared based on methods of variography. The results showed that (a) the spatial NDVI patterns of up- and downscaled data do not correspond with the un-scaled image data, (b) only small differences were found between NDVI patterns determined from data recorded and resampled at different spectral resolutions and (c) the overall conclusion from the tests carried out is that the spatial resolution is more important in determining heterogeneity by means of NDVI than the depth of the spectral data. The implications behind these findings are that we need to exercise caution when interpreting and combining spatial structures and spectral indices derived from satellite images with differently recorded geometric resolutions.     

Combining target analysis with sum parameters—a comprehensive approach to determine sediment contamination with PFAS and further fluorinated substances

Recent studies aiming at a fluorine mass balance analysis in sediments combined the determination of extractable organic fluorine (EOF) with target analysis. They reported high fractions of unidentified organic fluorine (UOF) compounds, as the target analysis covers only a limited number of per- and polyfluoroalkyl substances (PFAS). For this reason, in this study, a comprehensive approach was used combining target analysis with an extended PFAS spectrum, the EOF and a modified total oxidisable precursor (TOP) assay, which includes trifluoroacetic acid, to determine the PFAS contamination in sediments (n=41) and suspended solids (n=1) from water bodies in Northern Germany (Lower Saxony). PFAS are ubiquitous in the sediments (detected in 83% of the samples). Perfluorinated carboxylic acids (PFCAs) were found in 64% of the samples; perfluorinated sulfonic acids (PFSAs) were detected less frequently (21%), with the highest concentration observed for perfluorooctanesulfonic acid (PFOS). Levels of precursors and substitutes were lower. Applying the TOP assay resulted in an increase in PFCAs in 43% of the samples analysed. In most cases, target analysis and the TOP assay could not account for the EOF concentrations measured. However, as the fraction of UOF decreased significantly, the application of the TOP assay in fluorine mass balance analysis proved to be an important tool in characterising the PFAS contamination of riverine sediments.

     

Continuous gaseous and total ammonia measurements from the southeastern aerosol research and characterization (SEARCH) study

Continuous ammonia (NH₃) measurements with a temporal resolution of 5 min were implemented at selected SEARCH sites in the southeastern U. S. during 2007. The SEARCH continuous NH₃ instrument uses a citric acid denuder difference technique employing a dual-channel nitric oxide-ozone chemiluminescence analyzer. Data from two SEARCH sites are presented, Jefferson Street, Atlanta (JST) (urban), and Yorkville, Georgia (YRK) (rural), for the period July–December, 2007. Highest NH_x (total ammonia = gaseous NH₃ + PM_2.5 NH₄⁺) values were observed in August and September at both JST and YRK. Highest NH₃ values occurred in August and September at JST, but in August through October at YRK. Lowest NH₃ and NH_x values occurred in December at both sites. YRK is significantly impacted by nearby poultry sources, routinely experiencing hourly average NH₃ mixing ratios above 20 ppbv. Wind sector analysis clearly implicates the nearby poultry operations as the source of the high NH₃ values. Weekday versus weekend differences in composite hourly mean diurnal profiles of NH₃ at JST indicate that mobile sources have a measurable but relatively small impact on NH₃ observed at that site, and little or no impact on NH₃ observed at YRK. A distinctive composite mean hourly diurnal variation was observed at both JST and YRK, exhibiting maxima in the morning and evening with a broad minimum during midday. Analysis of observed NH₃ diurnal variations from the literature suggests a hypothesized mechanism for the observed behavior based on interaction of local emissions and dry deposition with the formation and collapse of the dynamically mixed atmospheric boundary layer during the day and shallow nocturnal layer at night. Simple mixed layer concentration box model simulations confirm the plausibility of the suggested mechanism.     

Heavy metal concentrations in particle size fractions from street dust of Murcia (Spain) as the basis for risk assessment

Street dust has been sampled from six different types of land use of the city of Murcia (Spain). The samples were fractionated into eleven particle size fractions (<2, 2-10, 10-20, 20-50, 50-75, 75-106, 106-150, 150-180, 180-425, 425-850 μm and 850-2000 μm) and analyzed for Pb, Cu, Zn and Cd. The concentrations of these four potentially toxic metals were assessed, as well as the effect of particle size on their distribution. A severe enrichment of all metals was observed for all land-uses (industrial, suburban, urban and highways), with the concentration of all metals affected by the type of land-use. Coarse and fine particles in all cases showed concentrations of metals higher than those found in undisturbed areas. However, the results indicated a preferential partitioning of metals in fine particle size fractions in all cases, following a logarithmic distribution. The accumulation in the fine fractions was higher when the metals had an anthropogenic origin. The strong overrepresentation of metals in particles <10 μm indicates that if the finest fractions are removed by a vacuum-assisted dry sweeper or a regenerative-air sweeper the risk of metal dispersion and its consequent risk for humans will be highly reduced. Therefore, we recommend that risk assessment programs include monitoring of metal concentrations in dust where each land-use is separately evaluated. The finest particle fractions should be examined explicitly in order to apply the most efficient measures for reducing the risk of inhalation and ingestion of dust for humans and risk for the environment.     

Spatial patterns of macroalgal abundance in relation to eutrophication

Based on a large monitoring data set from Danish coastal waters we tested the hypotheses: (1) The vertical pattern of algal abundance is regulated by exposure in shallow water and by light limitation towards deeper water, resulting in a bell-shaped abundance curve, with peak abundance located deeper at more exposed sites, (2) in deeper water, total algal abundance and abundance of perennial algae decrease along a eutrophication gradient while (3) abundance and relative abundance of opportunists increase. The vertical pattern of algal abundance showed a peak at intermediate water depths which was located deeper in more exposed areas and thus confirmed our first hypothesis. For algae growing from depths of peak abundance and deeper, the study demonstrated that total algal abundance and abundance of perennials and opportunists at given depths decreased significantly along a eutrophication gradient and the relationships had high explanatory power (R ² = 0.53–0.73). These results confirmed our second hypothesis. By contrast, the relative abundance of opportunists responded solely to salinity and was largest in the most brackish areas, in contradiction to hypothesis three. The lack of coupling between eutrophication and relative abundance of opportunists arises because both opportunists and the entire algal community were light limited and their ratio therefore relatively insensitive to changing water clarity. The analyses indicated that algal abundance initially responded slowly to increasing eutrophication but showed a more marked response at TN concentrations of 35–40 μM. However, the existence of possible threshold nutrient levels demands further analyses.     

Phytoplankton can bypass nutrient reductions in eutrophic coastal water bodies

The EU-water framework directive aims at nutrient reductions, since anthropogenically induced eutrophication is a major threat for coastal waters. However, phytoplankton biomass in southern Baltic Sea coastal water bodies (CWB) remains high and the underlying mechanisms are not well understood. Therefore, a CWB data set was analysed regarding changes in phytoplankton biomass and nutrient concentration of nitrogen (N) and phosphorus (P) from 2000 to 2014. It was expected to find imbalances between produced phytoplankton biomass and total nutrient concentrations. Inner CWB were cyanobacteria-dominated and showed up to five times higher chlorophyll a-concentrations compared to outer CWB with similar total phosphorus-concentrations. Phytoplankton tended to be P-limited during spring and N-limited during summer. Phytoplankton biomass and nutrient concentrations were even higher during very humid years, which indicated a close coupling of the CWB with their catchment areas. This study suggests that re-mesotrophication efforts need to consider the importance of changed phytoplankton composition and nutrient availabilities.     

Availability of ammonium influences photosynthesis and the accumulation of mycosporine-like amino acids in two<Emphasis Type="Italic"> Porphyra</Emphasis> species (Bangiales,Rhodophyta)

The effect of ammonium concentration on photosynthetic activity estimated as in vivo chlorophyll fluorescence, i.e. maximal quantum yield (F_v/F_m) and electron transport rate (ETR) and on the accumulation of mycosporine-like amino acids (MAAs), chlorophyll a (chl a), biliproteins (BP) and soluble proteins (SP) in the red algae Porphyra leucosticta Thuret in Le Jolis collected from Lagos (Málaga, Spain) and Porphyra umbilicalis (Linnaeus) J. Agardh from Helgoland (Germany) was evaluated. Discs of both species were incubated with three ammonium concentrations (0, 100 and 300 µM) under artificial PAR and UV radiation for 7 days. Photosynthetic activity decreased under the culture conditions due to UV radiation and ammonium availability. The decrease of both F_v/F_m and maximal ETR was related to ammonium supply, i.e. the lowest decrease occurred in algae growing with the highest concentration of ammonium. In both species, after 7 days of culture, the content of chl a, BP and SP was higher under 300 µM than that under 0 and 100 µM ammonium. In both species, the content of MAAs was increased under 300 µM ammonium compared to the initial value, whereas a decrease under 0 and 100 µM ammonium was observed only in P. leucosticta. The content of MAAs in P. umbilicalis did not present significant differences compared to the initial value, probably because of the high initial content of MAAs. In both Porphyra species, four MAAs were identified: shinorine, porphyra-334, palythine and asterina-330. However, P. leucosticta modified its MAA pattern during the incubation time, reaching the same percentages found for P. umbilicalis, which did not show any change during the experimental period. P. leucosticta exhibited a decrease in BP/SP and BP/chl a ratios through the incubation time and an increase in MAAs/BP. The ratio MAAs/chl a did not show any variation with time or treatment, as was also true for all ratios in P. umbilicalis. In summary, ammonium supply diminished the decrease of F_v/F_m, increased the content of photosynthetic pigments (chlorophyll and biliprotein) and soluble protein, and stimulated of the accumulation of MAAs in the red algae P. leucosticta and P. umbilicalis.Communicated by O. Kinne, Oldendorf/Luhe     

Municipal landfills exhale newly formed organotins

For the first time we are able to report the identification and quantification of several unexpected alkylated tin compounds such as dimethyldiethyltin, trimethylethyltin and propyltrimethyltin in European municipal waste deposits, by using GC-ICP-MS. Future studies will reveal whether their origin is from the degradation of butyl-, or octyltin compounds or simply products of de novo synthesis within the landfill environment.