Surface-enhanced vibrational techniques for the detection of synthetic organic colorants

The research project object of this thesis is focused on the development of an advanced analytical system based on the combination of an improved thin layer chromatography (TLC) plate coupled with infrared (FTIR) and Raman microscopies for the detection of synthetic dyes. Indeed, the characterization of organic colorants, which are commonly present in mixtures with other components and in a very limited amount, still represents a challenging task in scientific analyses of cultural heritage materials. The approach provides selective spectral fingerprints for each compound, foreseeing the complementary information obtained by micro ATR-RAIRS-FTIR and SERS-Raman analyses, which can be performed on the same separated spot. In particular, silver iodide (AgI) applied on a gold coated slide is proposed as an efficient stationary phase for the discrimination of complex analyte mixtures, such as dyes present in samples of art-historical interest. The gold-AgI-TLC plate shows high performances related both to the chromatographic separation of analytes and to the spectroscopic detection of components. The use of a mid-IR transparent inorganic salt as the stationary phase avoids interferences of the background absorption in FTIR investigations. Moreover, by ATR microscopy measurements performed on the gold-AgI surface, a considerable enhancement in the intensity of spectra is observed. Complementary information can be obtained by Raman analyses, foreseeing a SERS activity of the AgI substrate. The method has been tested for the characterization of a mixture of three synthetic organic colorants widely used in dyeing processes: Brilliant Green (BG1), Rhodamine B (BV10) and Methylene Blue (BB9).

Analysis of the relationships between Spartina maritima and nutrient enrichment in North Adriatic salt marshes

Salt marshes are coastal ecosystem in the upper intertidal zone between internal water and sea and are widely spread throughout Italy, from Friuli Venezia Giulia, in the North, to Sicily, in the South. These delicate environments are threatened by eutrophication, habitat conversion (for land reclaiming or agriculture) and climate change impacts such as sea level rise. The objectives of my thesis were to: 1) analyse the distribution and biomass of the perennial native cordgrass Spartina maritima (one of the most relevant foundation species in the low intertidal saltmarsh vegetation in the study region) at 7 sites along the Northern Adriatic coast and relate it to critical environmental parameters and 2) to carry out a nutrient manipulation experiment to detect nutrient enrichment effects on S. maritima biomass and vegetation characteristics. The survey showed significant differences among sites in biological response variables - i.e., live belowground, live aboveground biomass, above:belowground (R:S) biomass ratio, % cover, average height and stem density – which were mainly related to differences in nitrate, nitrite and phosphate contents in surface water. Preliminary results from the experiment (which is still ongoing) showed so far no significant effects of nutrient enrichment on live aboveground and belowground biomass, R:S ratio, leaf %Carbon, average height, stem density and random shoot height; however, a significantly higher (P=0.018) increase in leaf %Nitrogen content in treated plots indicated that nutrient uptake had occurred.