Towards quantifying the glacial runoff signal in the freshwater input to Tyrolerfjord–Young Sound,NE Greenland

Terrestrial freshwater runoff strongly influences physical and biogeochemical processes at the fjord scale and can have global impacts when considered at the Greenland scale. We investigate the performance of the HIRHAM5 regional climate model over the catchments delivering freshwater to Tyrolerfjord and Young Sound by comparing to the unique Greenland Ecological Monitoring database of in situ observations from this region. Based on these findings, we estimate and discuss the fraction of runoff originating from glacierized and non-glacierized land delivered at the daily scale between 1996 and 2008. We find that glaciers contributed on average 50–80% of annual terrestrial runoff when considering different sections of Tyrolerfjord–Young Sound, but snowpack depletion on land and consequently runoff happens about one month earlier in the model than observed in the field. The temporal shift in the model is a likely explanation why summer surface salinity in the inner fjord did not correlate to modelled runoff.     

The adaptive response of lichens to mercury exposure involves changes in the photosynthetic machinery

Lichens are an excellent model to study the bioaccumulation of heavy metals but limited information is available on the molecular mechanisms occurring during bioaccumulation. We investigated the changes of the lichen proteome during exposure to constant concentrations of mercury. We found that most of changes involves proteins of the photosynthetic pathway, such as the chloroplastic photosystem I reaction center subunit II, the oxygen-evolving protein and the chloroplastic ATP synthase β-subunit. This suggests that photosynthesis is a target of the toxic effects of mercury. These findings are also supported by changes in the content of photosynthetic pigments (chlorophyll a and b, and β-carotene). Alterations to the photosynthetic machinery also reflect on the structure of thylakoid membranes of algal cells. Response of lichens to mercury also involves stress-related proteins (such as Hsp70) but not cytoskeletal proteins. Results suggest that lichens adapt to mercury exposure by changing the metabolic production of energy.     

Matrine and oxymatrine in corroborant plant extracts and fertilizers: HPLC/MS-MS method development and single-laboratory validation

A reversed phase high-performance liquid chromatographic method (HPLC/MS-MS) has been developed and validated for detection of alkaloids matrine and oxymatrine in fertilizer with labeled enhancer plant defense activities. The analytical method was validated statistically. The results show a strong matrix effect, requiring quantification by standard addition method. The regression lines showed r² > 0.994. Recoveries ranging from 97 to 104% were obtained for the fortification level of 0.01% wt wt^?1 and the relative standard deviations ranged from 3 to 4% (n = 10). The limits of detection were below 0.0001% wt wt^?1, while the limits of quantification did not exceed 0.0004% wt wt^?1. The method is currently applied in ICQRF Laboratory of Catania on fertilized and corroborant plant extract collected in the Italian market in the frame of MIPAAF institutional quality control activity, with the aim to dectect these unpermitted active substances.     

Photo-Stabilisation and UV Blocking Efficacy of Coated Macro and Nano-Rutile Titanium Dioxide Particles in Paints and Coatings

Surface treated macro and nanoparticle TiO₂ samples have been prepared, characterised and their efficiency as UV blockers evaluated in clear coatings and paints. The particle size of the ‘base’ TiO₂ has been optimised to block UV radiation and the surface treatment developed to deactivate the photocatalytic activity of the surface of the TiO₂ particles. The resultant UV blockers have been evaluated in both solvent and water-based clear coatings. Nanoparticle TiO₂ has been prepared from ‘seed’ and the particle size was controlled by calcination. It was found that the choice of particle size is a compromise between UVA absorption, UVB absorption, visible transmission and photoactivity. It has been demonstrated that TiO₂ with a crystallite size of 25 nm yields a product with the optimum properties. A range of dispersants was successfully used to disperse and mill the TiO₂. Both organic and inorganic dispersants were used; 2-amino-2-methyl-1-propanol and 1-amino-2-propanol (MIPA) and P₂O₅ and Na₂SiO₃ respectively. The surface of the nano-TiO₂ was coated with mixed oxides of silicon, aluminium, zirconium and phosphorous. Addition of the resultant coated nano-rutiles to an Isocyanate Acrylic clear coating prolonged the lifetime of that coating compared to the blank. Generally, a surface treatment based on SiO₂, Al₂O₃ and P₂O₅ was more successful than one based on ZrO₂, Al₂O₃ and P₂O₅. Higher addition levels of the surface treatment were beneficial for protecting the polymeric coating. The UV blocker products were also evaluated in a water-based acrylic, first a water-based dispersion of the UV blocker was prepared before addition to the acrylic. The dispersions and resultant acrylic thin films were evaluated using UV/Vis spectroscopy and durability assessed. The ratio of absorbance at 300:500 nm for the water-based dispersion was shown to be a good predictor of both the transparency of the resultant acrylic thin film and the durability of that film, in terms of weight loss. Macro grade titanium dioxide pigments were also prepared and coated with treatments of silica, alumina and siloxane and their photo-stabilising activity in alkyd paint film assessed and found to be directly related to the electron–hole pair mobility and trapping as determined by micro-wave spectroscopy.     

Monitoring of marine mucilage formation in Italian seas investigated by infrared spectroscopy and independent component analysis

The aim of this study is to present and to discuss some characteristics of recalcitrant organic matter mechanism and formation. These aggregates called mucilages that are produced by the degradation reactions of several algae, have been investigated by infrared (FTIR) spectroscopy. FTIR spectra of macroaggregates produced by different algal samples have been daily collected in order to investigate the steps of aggregation. Afterwards, they have been elaborated by means of Independent Component Analysis (ICA). ICA investigation of FTIR spectra showed that the global aggregation process of marine mucilage always consisted of two different phases or independent components (ICs). One IC is related to the first degradation step of algal cells leading to the production of mono and oligosaccharides with aminoacids and oligopeptides. The second IC is related to the polymerization of oligosaccharides with aminoacids and oligopeptides and to their interaction with less polar compounds such as lipids thus producing supramolecular structures. The emerging mechanisms of anomalous size aggregates of organic matter match those of natural organic matter aggregation. The approach we suggest is to use synthetic mucilages which allows to monitor the macroaggregates formation because it can hardly be performed by means of natural marine macroaggregates.     

Fate and degradation of triasulfuron in soil and water under laboratory conditions

The behavior and fate of triasulfuron (TRS) in water and soil systems were examined in laboratory studies. The degradation of TRS in both buffer solution and soil was highly pH-sensitive. The rate of degradation could be described with a pseudo first-order kinetic and was much faster at pH 4 than at pH 7 and 9. Aqueous hydrolysis occurred by cleavage of the sulfonylurea bridge to form 2-(2-chloroethoxy) benzenesulfonamide (CBSA) and [(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino] (AMMT). AMMT was unstable in aqueous solutions in any pH condition but it degraded more quickly at pH 4 and 9. CBSA did not degrade in aqueous solutions or in enriched cultures but it underwent a quick degradation in the soil. The rates of TRS degradation in sterile and non-sterile soils were similar, suggesting that microorganisms played a minimal role in the breakdown process. This hypothesis is supported by the results of studies on the degradation of TRS by enriched cultures during which the molecule underwent a prevalently chemical degradation.