Structural characterization of humic acids, extracted from sewage sludge during composting, by thermochemolysis–gas chromatography–mass spectrometry

Thermochemolysis coupled with gas chromatography and mass spectrometry were applied to determine the structure of humic acids (HA) extracted from a sewage sludge and straw mixture at different steps of composting. The HA extracted from sludge mixture released various compounds, such as mono-, di-, tri-methoxy (alkyl) benzene and (alkyl) benzoic acids, which originated from lignin like derivatives of phydroxyphenyl, guiaicyl and syringyl units. In addition, other aromatic non-lignin derived structures were found along with series of branched C15, linear C16, C18 fatty acid methyl esters. The follow-up of various lignin-derived units during composting shows a decrease in phydroxyphenyl type-compounds (C) after the stabilisation phase. In parallel the more oxidized units, derived from guaiacyl (G) and syringyl (S) units, corresponding mainly to methylated derivatives of cafeic acids, protocatechuic acids, gallic acids and aldehydes, significantly increased in comparison with the other aromatic structures. Various ratios commonly used as parameters to determine the degree of lignin decomposition during humification were followed to monitor the chemical structure changes of the HA extracted from sludge mixture during composting. In the present case, the S/G ratio did not present significant changes during composting. The acid/aldehyde ratio was supervised using the ratio of gallic acids to gallic aldehyde methylated derivatives and showed an increase from 0.73 to 2.13 after the stabilisation phase but a decrease to 0.93 at the end of composting. This evolution may be explained by the increase of acid-containing derivatives following the intense oxidation of lignin side-chains during the stabilisation phase. But, the decrease of the acid/aldehyde ratio during the maturation phase could be attributed to a decrease in acid units by polymerisation of benzoic acid type-compounds through ester/ether linkages. The follow up of six families of compounds of similar chemical structures during composting showed a decrease of lignin-type compounds C6–C3 and that C6–C1 units predominated in the humic acid isolated from end compost sludge. The fatty acid methyl esters showed an increase in the intermediate phase of composting probably originating from the activities and tissues of microorganisms, which are numerous during the process. The final decrease in the amount of fatty acids may be explained by the death of most of the microbial population at the end of composting typified by a low respiratory rate. The index of Shannon-Weaver (Ish) remained constant at about 3 in course of composting indicating the neoformation of HA from subunits of similar chemical nature. A similitude index (Sij, S0 i j) showed a split between 30 and 90 days of composting indicating a change in the rate of neoformation of HA after a stabilisation phase. Afterwards, the rate of HA neoformation varied linearly with the duration of composting

Deciphering the Anti-Aflatoxinogenic Properties of Eugenol Using a Large-Scale q-PCR Approach

Produced by several species of Aspergillus, Aflatoxin B1 (AFB1) is a carcinogenic mycotoxin contaminating many crops worldwide. The utilization of fungicides is currently one of the most common methods; nevertheless, their use is not environmentally or economically sound. Thus, the use of natural compounds able to block aflatoxinogenesis could represent an alternative strategy to limit food and feed contamination. For instance, eugenol, a 4-allyl-2-methoxyphenol present in many essential oils, has been identified as an anti-aflatoxin molecule. However, its precise mechanism of action has yet to be clarified. The production of AFB1 is associated with the expression of a 70 kB cluster, and not less than 21 enzymatic reactions are necessary for its production. Based on former empirical data, a molecular tool composed of 60 genes targeting 27 genes of aflatoxin B1 cluster and 33 genes encoding the main regulatory factors potentially involved in its production, was developed. We showed that AFB1 inhibition in Aspergillus flavus following eugenol addition at 0.5 mM in a Malt Extract Agar (MEA) medium resulted in a complete inhibition of the expression of all but one gene of the AFB1 biosynthesis cluster. This transcriptomic effect followed a down-regulation of the complex composed by the two internal regulatory factors, AflR and AflS. This phenomenon was also influenced by an over-expression of veA and mtfA, two genes that are directly linked to AFB1 cluster regulation

Conclusion

Arrivés au terme de ce tour d’Europe des architectures funéraires monumentales néolithiques, faisons le bilan des multiples apports et pistes de réflexion que nous proposent les diverses contributions de cet ouvrage. Ces dernières ont montré la pertinence de l’espace en tant qu’objet et question archéologique, ainsi que l'intérêt général qu'il suscite, parfois très concrètement de l'archéologie préventive à la fouille programmée pluriannuelle de monuments de grande taille. Car si l'espace et ..

Structural characterization of fulvic acids, extracted from sewage sludge during composting, by thermochemolysis–gas chromatography–mass spectrometry

Thermochemolysis coupled with gas chromatography and mass spectrometry were applied to determine the chemical structure of fulvic acids (FA) extracted from a sewage sludge and straw mixture at different steps of composting. The FA starting structures were composed mainly of mono-, di- and tri-methoxy (alkyl) benzoic acids representing lignin derivatives in an advanced stage of oxidation, as well as of methylated polyphenols and a series of fatty acids saturated C15, C16, C18, unsaturated and branched C18:1. Besides, there are many unidentified structures suspected to be N-containing compounds. During the composting process, the fate of the three structural typical monomer units of lignin was followed. The p-hydroxyphenyl units showed a strong relative decrease especially at the beginning of composting. The guiaicyl units showed a steady increase in course of composting. A relative decrease of syringyl units was noted at the beginning of composting, but they then relatively increased towards the end of composting. These changes support the formation during composting of more oxidized units. All subunits composing the fulvic acid structures have been subdivided into main five groups of similar chemical structure. The lignin-like C6–C3 subunits showed a relative decrease during composting attributed to microbial oxidation, but there was a relative increase during the intermediate step of composting related probably of an enhancing of lignin solubility. The C6–C1 subunits were reduced at the beginning of composting, which mainly attributed to the oxidation of 4-methoxybenzaldehyde to hydroquinones derivatives under the composting conditions. Although, the relative increase of these subunits (C6–C1) at the end of composting originates from oxidation of C6–C3 lignin side-chains or could be partly attributed to microbial neosynthesis. The unidentified N-containing compounds increased strongly during course of composting. The rise in the level of fatty acids at the beginning of composting is attributed to an increase of branched-chain fatty acids such as C18:1 commonly used as bacterial biomarkers. Their amounts were greatly reduced at the end of composting. Both the Shannon–Weaver and similitude indices show a relative increase in structural diversity at the start of composting conditions following the appearance of hydroquinone derivatives and unidentified nitrogen compounds in the FA network. But, the produced FA structure reaches a certain level of homogeneity at the end of composting through self-polycondensation or recombination of C6–C1 subunits and hydroquinones derivatives with N-containing compounds

Internal vein texture and vein evolution of the epithermal Shila-Paula district, southern Peru.

The epithermal Shila-Paula Au–Ag district is characterized by numerous veins hosted in Tertiary volcanic rocks of the Western Cordillera (southern Peru). Field studies of the ore bodies reveal a systematic association of a main E–W vein with secondary N55–60°W veins—two directions that are also reflected by the orientation of fluid-inclusion planes in quartz crystals of the host rock. In areas where this pattern is not recognized, such as the Apacheta sector, vein emplacement seems to have been guided by regional N40°E and N40°W fractures. Two main vein-filling stages are identified. stage 1 is a quartz–adularia–pyrite–galena–sphalerite–chalcopyrite–electrum–Mn silicate–carbonate assemblage that fills the main E–W veins. stage 2, which contains most of the precious-metal mineralization, is divided into pre-bonanza and bonanza substages. The pre-bonanza substage consists of a quartz–adularia–carbonate assemblage that is observed within the secondary N45–60°W veins, in veinlets that cut the stage 1 assemblage, and in final open-space fillings. The two latter structures are finally filled by the bonanza substage characterized by a Fe-poor sphalerite–chalcopyrite–pyrite–galena–tennantite–tetrahedrite–polybasite–pearceite–electrum assemblage. The ore in the main veins is systematically brecciated, whereas the ore in the secondary veins and geodes is characteristic of open-space crystallization. Microthermometric measurements on sphalerite from both stages and on quartz and calcite from stage 2 indicate a salinity range of 0 to 15.5 wt% NaCl equivalent and homogenization temperatures bracketed between 200 and 330°C. Secondary CO2-, N2- and H2S-bearing fluid inclusions are also identified. The age of vein emplacement, based on 40Ar/39Ar ages obtained on adularia of different veins, is estimated at around 11 Ma, with some overlap between adularia of stage 1 (11.4±0.4 Ma) and of stage 2 (10.8±0.3 Ma). A three-phase tectonic model has been constructed to explain the vein formation. Phase 1 corresponds to the assumed development of E–W sinistral shear zones and associated N60°W cleavages under the effects of a NE–SW shortening direction that is recognized at Andean scale. These structures contain the stage 1 ore assemblage that was brecciated during ongoing deformation. Phase 2 is a reactivation of earlier structures under a NW–SE shortening direction that allowed the reopening of the preexisting schistosity and the formation of scarce N50°E-striking S2-cleavage planes filled by the stage 2 pre-bonanza minerals. Phase 3 coincides with the bonanza ore emplacement in the secondary N45–60°W veins and also in open-space in the core of the main E–W veins. Our combined tectonic, textural, mineralogical, fluid-inclusion, and geochronological study presents a complete model of vein formation in which the reactivation of previously formed tectonic structures plays a significant role in ore formation

Influence of the gun barrel straightness on projectile exit conditions

Gun accuracy is influenced by several parameters during the internal ballistics phase. Accuracy is defined by the bias and dispersion of impact points on the target. The aim of this study is to determine the influence of gun barrel straightness on projectile exit conditions, in order to understand how to improve weapon accuracy. A numerical firing analysis was carried out with LS-Dyna software. The model validity is proven by its ability to accurately predict the measured circumferential strains caused by the forcing effect of the projectile, and by the consistency of the contact forces at the projectile-tube interface. To validate the firing simulation, circumferential strains of the tube were measured and compared to LS-Dyna results. Subsequently, the barrel geometry was modified to add a straightness defect to the initial curvature due to gravity. Lastly, a post-treatment was performed to determine the angular and transverse velocities of the projectile during internal ballistics phase. This analysis shown the influence of specific shapes on ammunition balloting and velocity

Analytic curves in algebraic varieties over number fields

We establish algebraicity criteria for formal germs of curves in algebraic varieties over number fields and apply them to derive a rationality criterion for formal germs of functions, which extends the classical rationality theorems of Borel-Dwork and P\'olya-Bertrandias valid over the projective line to arbitrary algebraic curves over a number field. The formulation and the proof of these criteria involve some basic notions in Arakelov geometry, combined with complex and rigid analytic geometry (notably, potential theory over complex and $p$-adic curves). We also discuss geometric analogues, pertaining to the algebraic geometry of projective surfaces, of these arithmetic criteria.Comment: 55 pages. To appear in "Algebra, Arithmetic, and Geometry: In Honor of Y.i. Manin", Y. Tschinkel & Yu. Manin editors, Birkh\"auser, 200