Lake basins can behave as accumulators of microplastics released in wastewaters as such or resulting from degradation of larger items before and/or during their journey toward the marine environment as a final sink. A novel multianalytical approach was adopted for the detection and quantification of microplastics with size < 2 mm in the sediments of the volcanic lake of Bracciano, Italy. Simple analytical techniques such as solvent extraction/fractionation (for polyolefins and polystyrene) or depolymerization (for polyethylene terephthalate, PET), along with chromatographic detection (SEC and HPLC), allowed quantitative and qualitative determination of the main synthetic polymer contaminants. In particular, PET microplastic concentrations of 0.8–36 ppm were found, with variability related to the sampling site (exposure to incoming winds and wave action). Proton Nuclear Magnetic Resonance (1H-NMR) and Attenuated Total Reflectance Fourier Transformed InfraRed (ATR-FTIR spectroscopic investigations supported the identification and chemical characterization of plastic fragments and polymer extracts. The average molecular weight of solvent extractable polymers was evaluated from 2D 1H-NMR diffusion ordered spectroscopy (DOSY) experiments. The proposed, easily accessible multianalytical approach can be considered as a useful tool for improving our knowledge on the nature and the concentration of microplastics in sediments, giving insights on the impact of human activities on the health status of aquatic ecosystems.
The structure of two biochars and of their activated carbons was investigated by Electron Paramagnetic Resonance, Solid State Nuclear Magnetic Resonance, and Fourier Transform Infrared spectroscopies, together with X-ray diffraction and nitrogen adsorption/desorption isotherm measurements. The biochars were obtained from wood and Posidonia Oceanica by slow pyrolysis up to 600 °C, whereas the activated carbons were prepared from the biochars by impregnation with KOH, heating up to 800 °C. Two different KOH:biochar mass ratios were tested in the case of Posidonia, namely 4:1 and 2:1, while only the 4:1 ratio was used for wood. When the larger ratio was used, activation significantly increased the microporosity of the starting biochar, also creating bottle-neck pores not accessible to water molecules, and induced the formation of larger condensed aromatic networks arranged in interconnected conducting domains. In the case of Posidonia, activation using the 2:1 ratio mainly created mesopores and induced an increase in organic radical content by almost four orders of magnitude. This huge increase was related to the presence of minerals in the starting biochar.
The elastic response of chromium-tanned leather was successfully improved by treatment with XSBR, a carboxylated styrene-butadiene copolymer. The carboxylic groups pending from a styrene-butadiene rubber (SBR) backbone were found to promote penetration of the aqueous polymer dispersion into the fibrous tanned leather and participated in pH-reversible physical crosslinking by H-bonding. The different penetrations of XSBR or SBR were investigated using a micro-FTIR cross-sectional analysis from the grain (outer) to the flesh (inner) side of 18 wt% elastomer-treated samples, based on the shaved leather weight. In particular, the profile of the diagnostic out-of-plane =C-H bending of butadiene and styrene units was consistent with a more effective penetration of XSBR. The leather with XSBR showed a comparatively lower elastic modulus of 10–15% and roughly a 10% increase in elongation at the break, indicating better flexibility and shape recovery. Also, the leather was characterized by a 15% higher burst strength. These results suggest the better swelling of the ionomeric XSBR in the initial stage of retanning performed at a pH higher than the isoelectric point of the leather when both the tanned leather and the XSBR ionomer had a negative surface charge. The high pH favored the penetration of XSBR due to a poor attractive interaction with the tanned fibrous leather network. Subsequent processing in an acid bath caused further physical crosslinking through hydrogen bonding between XSBR and the leather.