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An innovative approach based on the combination of analytical pyrolysis coupled with gas chromatography-mass spectrometry (Py-GC/MS) with compound-specific isotope analysis (Py-CSIA) is used to study the composting process of maize biomass. This multidisciplinary approach aims to elucidate the decomposition rate of the main biogenic materials (lignin, cellulose, proteins, lipids, and waxes) responses to the composting process. According to Py-GC/MS data/structural composition, a noticeable and significant decrease during the first stage of the composting process of carbohydrates and aromatic compounds is found, followed by a gradual increase of all compounds till the end of the experiment. This trend, along with an increase of fatty acids methyl-ester at the first composting stage, sustains the microbial activity and its stabilization over time. Py-CSIA data showed a significant enrichment in 13C in all identified compounds over time, supporting the semi-quantitative results and the decomposition of initial biomass throughout the composting process. This trend is also perceptible in lignin moieties, long-chain aliphatic structures, and isoprenoids, as highly recalcitrant compounds, presumably due to depolymerization and carbon translocation of side-chain molecules during the composting process. Compound-specific isotope values showed a good correlation with the bulk isotope data, and this served as validation of the technique. However, bulk values showed higher heterogeneity because those represent an average of all organic compounds in the sample. By combining isotopic and structural information using Py-GC/MS and Py-CSIA, we are able to provide further information and a more detailed approach to the study of the decomposition process of biomass by considering the diverse dynamics of the main biogenic compounds. [ABSTRACT FROM AUTHOR]

Sedimentary organic matter (OM) origin and molecular composition provide useful information to understand carbon cycling in coastal wetlands. Core sediments from threors' Contributionse transects along Ria Formosa lagoon intertidal zone were analysed using analytical pyrolysis (Py-GC/MS) to determine composition, distribution and origin of sedimentary OM. The distribution of alkyl compounds (alkanes, alkanoic acids and alkan-2-ones), polycyclic aromatic hydrocarbons (PAHs), lignin-derived methoxyphenols, linear alkylbenzenes (LABs), steranes and hopanes indicated OM inputs to the intertidal environment from natural—autochthonous and allochthonous—as well as anthropogenic. Several n-alkane geochemical indices used to assess the distribution of main OM sources (terrestrial and marine) in the sediments indicate that algal and aquatic macrophyte derived OM inputs dominated over terrigenous plant sources. The lignin-derived methoxyphenol assemblage, dominated by vinylguaiacol and vinylsyringol derivatives in all sediments, points to large OM contribution from higher plants. The spatial distributions of PAHs (polyaromatic hydrocarbons) showed that most pollution sources were mixed sources including both pyrogenic and petrogenic. Low carbon preference indexes (CPI > 1) for n-alkanes, the presence of UCM (unresolved complex mixture) and the distribution of hopanes (C29–C36) and steranes (C27–C29) suggested localized petroleum-derived hydrocarbon inputs to the core sediments. Series of LABs were found in most sediment samples also pointing to domestic sewage anthropogenic contributions to the sediment OM. [ABSTRACT FROM AUTHOR]

Purpose: Data management strategies of pyrolysis results and NMR acquisition modes were examined in humic acids (HAs) from control soils and fire-affected soils. The information supplied by dipolar dephasing (DD) 13C NMR spectroscopy and Curie-point pyrolysis were used to assess chemical structures hardly recognizable and measurable, or of unclear interpretation, when using 13C NMR under standard acquisition pulses (cross-polarization/magic angle spinning, CPMAS).Materials and methods: The HAs were isolated from two forest soils under Pinus halepensis and Pinus sylvestris in control and burned sites affected by medium or severe-intensity wildfires. For NMR analyses, during DD acquisition conditions, a 180° 13C pulse was inserted to minimize phase shifts. Curie-Point pyrolysis was carried out at 510 °C for 5 s, and the pyrolysis fragments were analyzed by GC/MS. The total abundances of the major pyrolysis products were compared by an update of the classical Van Krevelen’s graphical-statistical approach, i.e., as surface density values in the space defined by the compound-specific H/C and O/C atomic ratios.Results and discussion: The DD 13C NMR experiments displayed significant differences in the HA spectral profiles as regards to the standard CPMAS 13C NMR acquisition conditions, mainly in the chemical shift region of alkyl structures as well as for tannin- or carbohydrate-like O-alkyl structures. In fact, the comparison between DD and CPMAS solid-state NMR suggested shortening of alkyl chains and generation of carbohydrate-derived, unsaturated structures—viz. furans—which adds to the aromatic domain. Pyrolytic results showed fire-induced specific changes in HAs chemical structure and its molecular diversity. The changes were evident in the location and sizes of the different clusters of pyrolysis compounds defined by their atomic ratios.Conclusions: The DD 13C NMR provided specific information on the fate of aliphatic structures and the origin of unsaturated HA structures, which could be helpful in differentiating “inherited” from “pyrogenic” aromatic structures. This is further confirmed by the analysis of the molecular assemblages of pyrolytic products, which showed accumulation of condensed polyaromatic domains in the HAs after the high-intensity fire, accompanied by a recalcitrant alkyl hydrocarbon domain. Medium-intensity fire led to aromaticity increase due to a selective accumulation of lignin-derived phenols concomitant to the depletion of aliphatic hydrocarbon constituents. [ABSTRACT FROM AUTHOR]

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 0.950 R2 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 [ABSTRACT FROM AUTHOR]

The relationship between soil organic matter (SOM) content and organic molecular assemblages ( n-alkane/alkenes pairs and n-fatty acids) with soil water repellency (WR) in different sieve fractions (1-2, 0·25-1, 0·05-0·5 and <0·05 mm) was studied in sandy soils from the Doñana National Park (SW Spain) under four vegetation species: Quercus suber (QS), Pteridium aquilinum (PA), Pinus pinea (PP) and Halimium halimifolium (HH). The severity of soil WR [assessed according to the water drop penetration time (WDPT) test] was ordered according to the sequence QS > PA > PP > HH. A positive correlation was found between soil WR from each sieve fraction and SOM content. Most severe soil WR was detected in QS for all sieve fractions, followed by the finer fractions (<0·05 mm) from PA, PP and HH samples. The finer fraction had the highest SOM content, ranging between 20·9% (PP) and 46·9% (QS). Coarser PA, PP and HH soil fractions (1-2 mm) showed the highest long-chain-even C numbered fatty acids in the order PP > PA > HH. A significant correlation was observed between SOM content and the severity of soil WR in QS samples and finer fractions of soil under other vegetation (PA, PP and HH). Coarser fractions (1-2 mm) from PP, PA and HH 1-2 mm sieve fractions showed high severity of WR and relatively low SOM contents that could be explained by a low degree of evolution of the organic residues as seen by analytical pyrolysis, that is, higher alkane/alkene carbon preference index values and the presence of a higher diversity of fatty acid structures. Copyright © 2014 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

BACKGROUND Pyrolysis-compound specific isotopic analysis (Py- CSIA: Py- GC-( FID)-C- IRMS) is a relatively novel technique that allows on-line quantification of stable isotope proportions in chromatographically separated products released by pyrolysis. Validation of the Py- CSIA technique is compulsory for molecular traceability in basic and applied research. In this work, commercial sucrose from C4 (sugarcane) and C3 (sugarbeet) photosystem plants and admixtures were studied using analytical pyrolysis (Py- GC/ MS), bulk δ 13C IRMS and δ 13C Py- CSIA. RESULTS Major pyrolysis compounds were furfural (F), furfural-5-hydroxymethyl ( HMF) and levoglucosan ( LV). Bulk and main pyrolysis compound δ 13C (‰) values were dependent on plant origin: C3 (F, −24.65 ± 0.89; HMF, −22.07 ± 0.41‰; LV, −21.74 ± 0.17‰) and C4 (F, −14.35 ± 0.89‰; HMF, −11.22 ± 0.54‰; LV, −11.44 ± 1.26‰). Significant regressions were obtained for δ 13C of bulk and pyrolysis compounds in C3 and C4 admixtures. Furfural (F) was found 13C depleted with respect to bulk and HMF and LV, indicating the incorporation of the light carbon atom in position 6 of carbohydrates in the furan ring after pyrolysis. CONCLUSION This is the first detailed report on the δ 13C signature of major pyrolytically generated carbohydrate-derived molecules. The information provided by Py- CSIA is valuable for identifying source marker compounds of use in food science/fraud detection or in environmental research. © 2015 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

Soil health refers to the biological, chemical, and physical features of soil that are essential to long-term, sustainable agricultural productivity with minimal environmental impact. Thus, soil health provides an overall picture of soil functionality. Although it cannot be measured directly, soil health can be inferred by measuring specific soil properties (e.g. organic matter content) and by observing soil status (e.g. fertility). There is also increased interest in studying soil microorganisms in their particular environments, as microbial diversity is intimately related to soil structure and function. One of the key objectives in determining soil health is to acquire indicators that can be used to evaluate the soil's current status and hence to develop sustainable agricultural systems. In this regard, significant progress has been made over the last few years in the development of specific biomarkers and macromolecular probes, enabling rapid and reliable measurements of soil microbial communities. In addition, modern molecular biological techniques, such as fluorescence in situ hybridization (FISH), reverse transcriptase polymerase chain reaction (RT-PCR), denaturing gradient gel electrophoresis (DGGE), and terminal restriction fragment length polymorphism (T-RFLP), have facilitated the analysis of microbial biodiversity and activity, whereas the application of modern analytical techniques, such as nuclear magnetic resonance (NMR) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS), have provided data on soil chemistry. The combination of these two approaches offers promise in determining soil health status. [Int Microbiol 2005; 8(1):13-21] [ABSTRACT FROM AUTHOR]