Adsorption of a dye on clay and sand. Use of cyclodextrins as solubility-enhancement agents

Laboratory-scale studies were aimed at elucidating the physico-chemical aspects on the removal process of crystal violet (CV) from waters and solid substrates. The laponite clay (RD) and sand were chosen for the double aim at investigating them as CV adsorbents for water treatment and as substrates which mime the soil components. Sand is very effective in removing CV from waters. The cyclodextrins (CDs) were exploited as solubility-enhancement agents to remove CV from the solid substrates. They are powerful solvent media because they extract the CV from sand forming water-soluble CV/CD inclusion complexes and do not show affinity for sand. Optimum performance was shown by the modified CDs (i.e. hydroxypropyl-β-cyclodextrin and methyl-β-cyclodextrin). A linear correlation between the logarithm of the equilibrium constant for the CV/CD inclusion complexes formation (K_cpx) and the maximum amount of CV extracted from sand in the columns experiments at a flow rate of 1.5 ml min⁻¹ was drawn. This relationship predicts that CDs with K_cpx < 180 M⁻¹ are not suitable for CV removal from sand. CDs failed to displace CV from RD because they generate the formation of RD clusters where CV remains entrapped.     

Significance of urinary arsenic speciation in assessment of seafood ingestion as the main source of organic and inorganic arsenic in a population resident near a coastal area

In order to characterize the different sources of exposure to arsenic (As), urinary excretion of total As, the sum of inorganic As+MMA+DMA determined by the hydride generation-atomic absorption spectrophotometry technique, and the species As(3), As(5), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and arsenobetaine were determined in 49 workers at a steel foundry, with presumed occupational exposure to As, and 50 subjects from the general population, all males. No evidence of occupational exposure to As resulted from environmental monitoring performed in the foundry, although the analysis of minerals used as raw materials showed the presence of As, particularly in fossils and fine ores. The urinary concentrations of As(3), MMA, DMA, the sum of inorganic As+MMA+DMA and total As were not different in the two groups, while arsenobetaine appeared significantly higher in the controls than in the workers. The different species of urinary As were all significantly correlated. Urinary excretion of As(3) was associated with the consumption of mineral water and with residence in an industrial zone, while MMA, DMA, arsenobetaine, the sum of inorganic As+MMA+DMA and total As urinary excretion were associated with the consumption of crustaceans and/or shellfish 3 days or less before urine collection. Multiple regression analysis confirmed these results. In conclusion, in populations with a high consumption of seafood, living in areas characterized by coastal/marine As pollution, only speciation of As can identify a prevalent role of environmental sources, like the consumption of seafood contaminated by As, in determining urinary As excretion, and exclude an occupational origin of the exposure.     

Assessment of noise level and noise propagation generated by light-lift helicopters in mountain natural environments

The use of helicopter rises discussion about environmental noise propagation especially when it operates in proximity of environmentally sensitive areas (ESAs) for an extended period because of its potential implications in wildlife behaviours. In order to support decisions on helicopter logging operation management in proximity of ESAs, this study focused on (i) analysing the noise spectrum of a light-lift helicopter during logging operations and on (ii) assessing the noise propagation in the surrounding environments. This study investigated a helicopter logging operation for wood fuel extraction in the eastern part of the Italian Alps. The potential disturbance area covered for the entire helicopter logging operation was evaluated by a specific GIS application according to hearing sensitivity of the most sensitive wildlife species in the study area (different strigiform species). The noise level at the ground appeared to be affected by the location regardless both the use of equivalent continuous sound pressures level dB(A) (LAeq) and the single-event level (SEL) noise metrics. The lowest values were recorded when the helicopter was flown over the sound meter level located under the forest canopy, while the highest was recorded when the helicopter was unhooking the loads at the landing. The GIS application highlighted the consistent of the exceeded noise area (weighted to strigiform hearing range and sensitivity) for the lower frequency bands (0.016–0.250 kHz). A more restricted exceeded noise area concerned instead the most sensitive frequency bands" for the strigiform (1–2 kHz).

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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.     

Evaluation of groundwater contamination in a coastal area of south-eastern Sicily

This investigation was under taken to evaluate the groundwater resources contamination due to intensive agricultural practices (particularly greenhouses). The study-area is located in the coastal area of the Ragusa province (South-East Sicily), where numerous existing greenhouses may cause the contamination of groundwater systems (unconfined and confined aquifers) beneath the cropped land. The pollution risk is mainly related with the seepage process of macro-elements nitrogen (N), phosphorus (P), potassium (K), held in the irrigation water and the massive use of fertilizers and pesticides, that may pass through the unsaturated zone of the soil profile. Moreover, the area is characterized by the presence of several wells (about 15 wells/km2) for agricultural use that cause the aquifer overexploitation and the consequent risk of seawater intrusion. The agriculture practices adopted in the study area (irrigation volumes, fertilizer concentrations, use of pesticides…) were monitored since February 2009; moreover, the pollution risk of the aquifers was evaluated through the analysis of groundwater water samples collected (monthly) in the monitoring wells; in particular, nitrogen compounds, soluble phosphorous (PO?2?), potassium, as well as the main pesticides commonly used in the study area, were measured.The results show that electrical conductivity and chloride concentration values can cause reduction of production and leaf damage problems, respectively, for most of the monitored farm systems. The high nitrogen compounds concentrations observed in the monitored wells can cause health and environmental problems. Moreover high pesticide contamination of groundwater was found in two of the five monitored wells.     

Concentrations of PCDD/PCDF in soil close to a secondary aluminum smelter

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) were analyzed in samples of the emissions from a secondary aluminum smelter (ALS) and soil samples around the plant. The purpose was to estimate the impact of the emissions on the surrounding environment.PCDD/F soil concentrations were higher in the proximity of the plant, exceeding the limit adopted in Italy in soils for green areas and residential uses and the upper limit of several reference concentrations. The most contaminated sites were less than 500 m from the plant and the dioxin concentration with the distance from the ALS.Principal component analysis (PCA) showed that emissions from the ALS were the source of PCDD/F contamination in the soils closest to the plant. Multivariate data analyses such as PCA are therefore useful to identify sources of emission causing contamination.     

Spatial distribution of soil radon as a tool to recognize active faulting on an active volcano: the example of Mt. Etna (Italy)

This study concerns measurements of radon and thoron emissions from soil carried out in 2004 on the eastern flank of Mt. Etna, in a zone characterized by the presence of numerous seismogenic and aseismic faults. The statistical treatment of the geochemical data allowed recognizing anomaly thresholds for both parameters and producing distribution maps that highlighted a significant spatial correlation between soil gas anomalies and tectonic lineaments. The seismic activity occurring in and around the study area during 2004 was analyzed, producing maps of hypocentral depth and released seismic energy. Both radon and thoron anomalies were located in areas affected by relatively deep (5-10 km depth) seismic activity, while less evident correlation was found between soil gas anomalies and the released seismic energy. This study confirms that mapping the distribution of radon and thoron in soil gas can reveal hidden faults buried by recent soil cover or faults that are not clearly visible at the surface. The correlation between soil gas data and earthquakes depth and intensity can give some hints on the source of gas and/or on fault dynamics.     

Heavy metal distribution and speciation in the Northern Adriatic Sea

In the present study the concentrations of cobalt, copper, iron, manganese, zinc were analysed and the speciation of copper and zinc performed, with a summer and winter sampling, for two areas in the Northern Adriatic Sea and crossing at the farthest zones of the Po river-sea water interface. Results show that when salinity increases the concentrations of all investigated metals (with the exception of cobalt) present some degree of biogeochemical cycling. Copper is the element whose dissolved phase has the highest importance in metal transport across the salinity gradient. Results of speciation analysis demonstrate that the presence of excess amounts (5-8 fold) of unbound ligands confers a buffering capacity for potential inputs of dissolved metals into the Northern Adriatic Sea. The speciation of both copper and zinc in the dissolved phase was dominated by organic complexation.     

Vertical and horizontal distributions of microbial abundances and enzymatic activities in propylene-glycol-affected soils

The natural microbial activity in the unsaturated soil is vital for protecting groundwater in areas where high loads of biodegradable contaminants are supplied to the surface, which usually is the case for airports using aircraft de-icing fluids (ADF) in the cold season. Horizontal and vertical distributions of microbial abundance were assessed along the western runway of Oslo Airport (Gardermoen, Norway) to monitor the effect of ADF dispersion with special reference to the component with the highest chemical oxygen demand (COD), propylene glycol (PG). Microbial abundance was evaluated by several biondicators: colony-forming units (CFU) of some physiological groups (aerobic and anaerobic heterotrophs and microscopic fungi), most probable numbers (MPN) of PG degraders, selected catabolic enzymatic activities (fluorescein diacetate (FDA) hydrolase, dehydrogenase, and β-glucosidase). High correlations were found between the enzymatic activities and microbial counts in vertical soil profiles. All microbial abundance indicators showed a steep drop in the first meter of soil depth. The vertical distribution of microbial abundance can be correlated by a decreasing exponential function of depth. The horizontal trend of microbial abundance (evaluated as total aerobic CFU, MPN of PG-degraders, and FDA hydrolase activity) assessed in the surface soil at an increasing distance from the runway is correlated negatively with the PG and COD loads, suggesting the relevance of other chemicals in the modulation of microbial growth. The possible role of potassium formate, component of runway de-icers, has been tested in the laboratory by using mixed cultures of Pseudomonas spp., obtained by enrichment with a selective PG medium from soil samples taken at the most contaminated area near the runway. The inhibitory effect of formate on the growth of PG degraders is proven by the reduction of biomass yield on PG in the presence of formate.     

Natural resources dynamics: Exhaustible and renewable resources,and the rate of technical substitution

In this paper we study both exhaustible and renewable resources in an endogenous growth model. In particular, we consider the hypotheses in which the rate of technical substitution (RTS) between those two inputs is or is not equal to one. Moreover, we depart from a basic theoretical framework to account for the negative externality constituted by waste accumulation. Finally, a comparative analysis is made between Pigouvian tax and waste recycling, as an environmental policy to correct market failure represented by refuse accumulation.