A multi-approach monitoring of particulate matter, metals and PAHs in an urban street canyon

For the first time until now, the results from a prediction model (Atmospheric Dispersion Modelling System (ADMS)-Road) of pollutant dispersion in a street canyon were compared to the results obtained from biomonitors. In particular, the instrumental monitoring of particulate matter (PM10) and the biomonitoring of 14 polycyclic aromatic hydrocarbons (PAHs) and 11 metals by Quercus ilex leaves and Hypnum cupressiforme moss bags, acting as long- and short-term accumulators, respectively, were carried out. For both PAHs and metals, similar bioaccumulation trends were observed, with higher concentrations in biomonitors exposed at the leeward canyon side, affected by primary air vortex. The major pollutant accumulation at the leeward side was also predicted by the ADMS-Road model, on the basis of the prevailing wind direction that determines different exposure of the street canyon sides to pollutants emitted by vehicular traffic. A clear vertical (3, 6 and 9 m) distribution gradient of pollutants was not observed, so that both the model and biomonitoring results suggested that local air turbulences in the street canyon could contribute to uniform pollutant distribution at different heights.     

Binding of polycyclic aromatic hydrocarbons by humic acids formed during composting

Binding of two model polycyclic aromatic hydrocarbons (PAHs), phenanthrene and pyrene, by humic acids (HAs) isolated from an organic substrate at different stages of composting and a soil was investigated using a batch fluorescence quenching method and the modified Freundlich model. With respect to soil HA, the organic substrate HA fractions were characterized by larger binding affinities for both phenanthrene and pyrene. Further, isotherm deviation from linearity was larger for soil HA than for organic substrate HAs, indicating a larger heterogeneity of binding sites in the former. The composting process decreased the binding affinity and increased the heterogeneity of binding sites of HAs. The changes undergone by the HA fraction during composting may be expected to contribute to facilitate microbial accessibility to PAHs. The results obtained also suggest that bioremediation of PAH-contaminated soils with matured compost, rather than with fresh organic amendments, may result in faster and more effective cleanup.     

Mobility of heavy metals from polluted sediments of a semi-enclosed basin: in situ benthic chamber experiments in Taranto’s Mar Piccolo (Ionian Sea,Southern Italy)

In situ benthic flux experiments were conducted at two stations in the Mar Piccolo of Taranto (Italy), one of the most industrialised and contaminated coastal areas of the Mediterranean. Sediments of the two stations are notably different in their trace metal content, with a station closer to a Navy harbour showing higher mean concentrations of almost all investigated metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn). Conversely, both stations are characterised by significant Hg contamination, compared to the local baseline. Results of a sequential extraction scheme on surface sediments suggest a relatively scarce mobility of the examined metals (Zn > Ni > Cr > As > Cu > Pb). A Hg-specific extraction procedure showed that most of the element (93.1 %) occurs in a fraction comprising Hg bound to Fe/Mn oxi-hydroxides. Reduction of these oxides may affect Hg remobilisation and redistribution. Porewater profiles of dissolved trace metals were quite similar in the two sites, although significant differences could be observed for Al, Cu, Fe and Hg. The highest diffusive fluxes were observed for As, Fe and Mn. Mobility rates of several trace elements (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn) were directly measured at the sediment–water interface. Results from benthic in situ incubation experiments showed increasing dissolved metal concentrations with time, resulting in higher fluxes for Cu, Fe, Hg, V and Zn in the most contaminated site. Conversely, fluxes of Mn, Ni and Pb were comparable between the two stations. The estimated flux of Hg (97 μg m^?2 day^?1) was the highest observed among similar experiments conducted in other highly contaminated Mediterranean coastal environments. Benthic fluxes could be partially explained by considering rates of organic matter remineralisation, dissolution of Fe/Mn oxy-hydroxides and metal speciation in sediments. Seasonal and spatial variation of biogeochemical parameters can influence metal remobilisation in the Mar Piccolo area. In particular, metals could be promptly remobilised as a consequence of oxygen depletion, posing a serious concern for the widespread fishing and mussel farming activities in the area.     

Removal of heavy metal ions from wastewaters using dendrimer-functionalized multi-walled carbon nanotubes

Dendrimer-functionalized multi-walled carbon nanotubes (MWCNT) for heavy metal ion removal from wastewaters were developed. Triazole dendrimers (TD) were built directly onto the carbon nanotube surface by successive click chemistry reactions affording the zero- and first-generation dendrimer-functionalized MWCNT (MWCNT-TD1 and MWCNT-TD2). The Moedritzer-Irani reaction carried out on the amino groups present on the MWCNT-TD2 sample gave the corresponding α-aminophosphonate nanosystem MWCNT-TD2P. Both MWCNT-TD2 and MWCNT-TD2P nanosystems have been characterized by physical, chemical, and morphological analyses. Their chelating abilities towards the toxic metal ions Pb²⁺, Hg²⁺, and Ni²⁺ and the harmless Ca²⁺ ion have been experimentally evaluated in the two different sets of experiments and at the salt concentrations of 1 mg/mL or 1 μg/mL by inductively coupled plasma mass spectrometry (ICP-MS). The results of these studies pointed out the interesting chelating behavior for the phosphonated nanosystem towards the Hg²⁺ ion. The complexation mode of the best chelating system MWCNT-TD2P with mercury was investigated through density functional theory (DFT) calculations, suggesting a chelation mechanism involving the two oxygen atoms of the phosphate group. The synthesized dendrimers, supported on the multi-walled carbon nanotubes, have shown the potential to be used for the selective toxic metal ion removal and recovery.     

Leaf accumulation of trace elements and polycyclic aromatic hydrocarbons (PAHs) in Quercus ilex L

Quercus ilex L. leaves were collected four times in one year at six urban sites and one remote area in order to determine trace element and PAH accumulation through concomitant analyses of unwashed and water-washed leaves. Both unwashed and washed leaves showed the highest amounts of trace elements and PAHs in the urban area. Unwashed leaves showed greater differences between urban and remote areas and among the urban sites than washed leaves for trace element and PAH concentrations. Water-washing resulted in a significant (P<0.001) decrease in leaf concentrations of Cr, Cu, Fe, Pb, V and Zn. By contrast, Cd and total PAH concentrations showed no differences between unwashed and washed leaves.     

Spatial variability of precipitation in Spain

The spatial variability of annual and seasonal precipitation in the conterminous land of Spain has been evaluated by using correlation decay distance analysis (CDD). The CDD analysis essentially explores how the correlation between neighbouring stations varies according to distance. We analysed CDD independently for the decades 1956–1965, 1966–1975, 1976–1985, 1986–1995, and 1996–2005 using only those stations with no missing values for each decade. To this end, 972, 1,174, 1,242, 773 and 695 complete series were used for each decade, respectively. In particular, for each station and decade, we calculated the threshold distance at which the common variance between target (i) and neighbour series is higher than 50 % (r ²  = 0.5) to evaluate whether current density of the climate data set captures the spatial variability of precipitation within the study area. Results indicate that, at an annual scale, neighbouring stations with 50 % of common variance are restricted on average to about 105 km, but this distance can vary from 28 to 251 km within the study area. The lowest variability is located to the SW and in winter, while the higher spatial variability is found to the north, in the Cantabrian area, and to the east, in the Mediterranean and Pyrenees, during summer. Our results suggest that current density of climate stations (those operating in 2005) is good enough to study precipitation variability at an annual scale for winter, spring and autumn, but not enough for summer.