Effects of technosols based on organic amendments addition for the recovery of the functionality of degraded quarry soils under semiarid Mediterranean climate: A field study.

This study aims to evaluate the effects of technosols made with different organic amendments to restore degraded soils in a semiarid limestone quarry. The effects on soil quality, functionality and organic matter dynamics of the technosols amended with waste of gardening, greenhouse horticultural, stabilized sewage sludge and two mixtures of sludge with both vegetable composts were assessed. Several physical and chemical properties, humus fractions, soil respiration and molecular composition was performed after 6 and 18 months. Un-amended soils, and nearby natural undegraded soils served as reference. Amended technosols increased water retention capacity, electrical conductivity, total organic carbon and nitrogen, respect to not amended and natural soils. Humus fraction composition was not altered over time. Un-amended soils, very poor in organic matter, did not show any pyrolyzable compounds or labile soil organic matter by thermogravimetry. In contrast, the pyrochromatograms of natural soils showed lignocellulosic materials, polypeptides and a noticeable presence of alkylic compounds. In technosols with both types vegetable compost, the organic matter structure was more complex, showing compounds from lignin-derived and long-chain alkyl, polysaccharides, chlorophyll isoprenoids and nitrogen. In sludge technosol, a set of sterols was outstanding. The mixtures showed a molecular fingerprint of materials derived from the decomposition of the organic amendments that formed them. These signs of the contribution of different organic matter forms derived from the amendments were also reported by the series exothermic peaks found in the calorimetry. This short-term study indicates a clear effect of the amendments on the recovery of soil organic matter and presumably of its functionality. After the amendments application, microbial activity and soil respiration rates increased rapidly but ceased 18 months later. The molecular composition of the organic matter of the soils amended with plant compost was very similar to that of natural, non-degraded soils in nearby areas.

Ultra-high resolution mass spectrometry of physical speciation patterns of organic matter in fire-affected soils.

Fire is one of the most important modulating factors of the environment and the forest inducing chemical and biological changes on the most reactive soil component, the soil organic matter (SOM). Assuming the complex composition of the SOM, we used an ultra-high resolution mass spectrometry analysis technique to assess the chemical composition and fire-induced alterations in soil particle size fractions (coarse and fine) from a sandy soil in a Mediterranean oak forest at Doñana National Park (Southwest Spain). Electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) showed that the coarse fraction of soils not affected by fires consisted mainly of polyphenolic compounds consistent with little-transformed SOM and fresh biomass, whereas the fine fraction was enriched in protein and lipid like homologues suggesting microbially reworked SOM. In fire-affected SOM, the coarse fraction contained a high proportion of aromatic compounds, consistent with inputs of charred litter or in situ chemical transformation of the SOM. Analysis of the fine fraction revealed two differentiated chemical families pointing to the existence of two carbon pools; a native microbial-derived moiety composed of lipids and polypeptide compounds, and a secondary, pyrogenic or thermally-altered moiety rich in aromatic compounds. This work represents the first application of ultra-high resolution mass spectrometry to study the chemical composition of SOM in different particle size fractions.

Assessing the effects of UVA photocatalysis on soot-coated TiO2-containing mortars.

The deposition of soot on building surfaces darkens their colour and leads to undesirable black crusts, which are one of the most serious problems on the conservation of built cultural heritage. As a preventive strategy, self-cleaning systems based on the use of titanium dioxide (TiO2) coatings have been employed on building materials for degrading organic compounds deposited on building surfaces, improving their durability and performance. In this study, the self-cleaning effect of TiO2-containing mortars coated with diesel soot has been appraised under laboratory conditions. The mortar samples were manufactured using lime putty and two different doses of TiO2 (2.5% and 5%). The lime mortars were then coated with diesel engine soot and irradiated with ultraviolet A (UVA) illumination for 30days. The photocatalytic efficiency was evaluated by visual inspection, field emission scanning electron microscopy (FESEM) and colour spectrophotometry. Changes in the chemical composition of the soot particles (including persistent organic pollutants) were assessed by analytical pyrolysis (Py-GC/MS) and solid state 13C NMR spectroscopy. The FESEM and colour spectrophotometry revealed that the soot-coated TiO2-containing mortars promoted a self-cleaning effect after UVA irradiation. The combination of analytical pyrolysis and 13C solid state NMR showed that the UVA irradiation caused the cracking of polycyclic aromatic structures and n-alkyl compounds of the diesel soot and its transformation into methyl polymers. Our findings also revealed that the inclusion of TiO2 in the lime mortar formulations catalysed these transformations promoting the self-cleaning of the soot-stained mortars. The combined action of TiO2 and UVA irradiation is a promising proxy to clean lime mortars affected by soot deposition.

Genotoxicity evaluation of carvacrol in rats using a combined micronucleus and comet assay.

Genotoxic data of substances which could be incorporated into food packaging are required by the European Food Safety Authority. Due to its antioxidant and antibacterial properties carvacrol is one of these compounds. This work aims to study for the first time the in vivo genotoxic effects produced in rats orally exposed to 81, 256 or 810 mg cavacrol/kg body weight (bw) at 0, 24 and 45 h. A combination of the micronucleus assay (OECD 474) in bone marrow and the standard (OECD 489) and enzyme-modified comet assay was used to determine the genotoxicity on cells isolated from stomach and liver of exposed animals. In addition, a histopathological study was performed on the assayed tissues, and also in the lungs due to the volatility of carvacrol. Direct analytical pyrolysis was used to search for carvacrol in viscera and to ensure that the compound reaches stomach and liver cells. Results from MN-comet assay revealed that carvacrol (81-810 mg/kg bw) did not induce in vivo genotoxicity or oxidative DNA damage in any of the tissues investigated. Moreover, no histopathological changes were observed. Altogether, these results suggest lack of genotoxicity of carvacrol and therefore its good profile for its potential application as food preservative.

Molecular characterisation of a bio-based active packaging containing Origanum vulgare L. essential oil using pyrolysis gas chromatography-mass spectrometry.

BACKGROUND: Environmental, economic and safety challenges motivate shift towards safer materials for food packaging. New bioactive packaging techniques, i.e. addition of essential plant oils (EOs), are gaining attention by creating barriers to protect products from spoilage. Analytical pyrolysis gas chromatography-mass spectrometry (Py-GC-MS) was used to fingerprint a bioactive polylactic acid (PLA) with polybutylene succinate (PBS) (950 g kg(-1) :50 g kg(-1) ) film extruded with variable quantities (0, 20, 50 and 100 g kg(-1) ) of Origanum vulgare EO. RESULTS: Main PLA:PBS pyrolysis products were lactide enantiomers and monomer units from the major PLA fraction and succinic acid anhydride from the PBS fraction. Oregano EO pyrolysis released cymene, terpinene and thymol/carvacrol peaks as diagnostic peaks for EO. In fact, linear correlation coefficients better than 0.950R(2) value (P < 0.001) were found between the chromatographic area of the diagnostic peaks and the amount of oregano EO in the bioplastic. CONCLUSION: The pyrolytic behaviour of a bio-based active package polymer including EO is studied in detail. Identified diagnostic compounds provide a tool to monitor the quantity of EO incorporated into the PLA:PBS polymeric matrix. Analytical pyrolysis is proposed as a rapid technique for the identification and quantification of additives within bio-based plastic matrices. © 2015 Society of Chemical Industry.