Hydroliquefaction of green wastes to produce fuels.

The direct liquefaction of a biomass composed of a mixture of wastes (straw, wood and grass) was studied using Nickel Raney as catalyst and tetralin as a solvent. Tetralin allows to solubilize green waste from 330°C at relatively low hydrogen pressure, and avoids the recondensation of the intermediate products. The green waste deoxygenation results mainly from a decarboxylation reaction. The addition of Raney Ni in the feed, increases the gas yield due to methane formation, without diminishing the yield in solvolysis oil. The catalyst hydrogenolyses the small molecules present in the light fraction. Moreover, it improves the quality of the oil by increasing the hydrogen transfer between the solvent and the solvolysis oil. As a consequence, the oxygen content decreases and the yield of oil soluble in hexane strongly increases. The catalyst allows to obtain straight long chain alkanes (C(13)-C(26)), which result from the hydrogenation of the extractives compounds of the green waste.

Stability and maturity of a green waste and biowaste compost assessed on the basis of a molecular study using spectroscopy, thermal analysis, thermodesorption and thermochemolysis.

The organic matter (OM) of a green waste and bio waste compost was characterised over 8months and the observed evolution was correlated with physico-chemical parameters (temperature, pH, carbon content, C/N ratio). Thermochemolysis and thermodesorption were used to monitor bacterial activity (stability) whereas diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) and thermodifferential analysis (TDA) permitted to determine the degree of OM humification (maturity). DRIFT spectroscopy and TDA provide two indicators of maturity since, with these two techniques, the signals associated with the biodegradable organic matter decrease relatively to the signals associated with refractory organic matter. This increase in R(TG) and R(IR) ratios between aromatic to aliphatic signals constitutes a proof for OM complexification. It correlates with humic acids/fulvic acids ratio known to be a maturity index. Pyrolysates are mainly constituted of lignin moieties, terpenoids, nitrogen containing compounds, carbohydrates (furanosic moiety), mono- and diacids (as methyl esters), and methoxyesters. The R(branched/linear) ratio between branched to linear acids traduces the evolution of the bacterial activity during composting. Moreover the R(di/mono) ratio between aliphatic mono to diacids correlates with the latter showing that diacids can occur from the biological oxidation of monoacids. These two ratios determined by thermochemolysis are useful to monitor the stability of compost. VOC, observed by thermodesorption are mainly constituted of terpenes, light acids, aldehydes and ketone. An unexpected result was obtained since the amount of phytol increases relatively to the isoprenoid ketone considered to originate from the latter.

Mobility of trace metals in retention pond sediments.

This paper presents the results of a study on trace metal mobility in the sediments of several road and urban infiltration/decantation ponds in France; the trace metal concentrations are indeed high. The potential mobility of trace metals (cadmium, nickel, chromium, copper, lead and zinc) was evaluated by application of the sequential extraction BCR protocol. Results have been compared with those from the IHSS protocol, which allows for the extraction of various forms of organic matter. Cadmium is the most easily exchangeable element in the case of variations in physical-chemical conditions (50% to 60% of Cd is exchangeable and 70% to 80% of Cd remains within the fulvic acid fraction) and is thus easily releasable within an acidic medium. Zinc is also potentially mobile and stays mainly concentrated in fulvic acids, except in the case of the Ronchin sediment (more than 50% in humin). In contrast, nickel and chromium are primarily present in the residual fraction and do not exhibit high mobility. Copper and lead are concentrated in both the humic acid fraction (IHSS protocol) and the organic phase (BCR scheme); consequently, their mobility is limited.

Characterization of the organic matter of sludge: determination of lipids, hydrocarbons and PAHs from road retention/infiltration ponds in France.

This paper presents the results of the organic matter characterization of sludge from two ponds (retention and infiltration) located in France. Special focus was placed on studying hydrocarbons and PAHs. This investigation is part of a global project on road and urban sludge with the aim of identifying a better means for managing these materials. Gas chromatographic and GC/MS analyses indicate that the main component of the organic fraction stems from petroleum-derived products like diesel fuel and motor oil. This finding was confirmed by the presence of biomarkers from the hopane series, as well as by pyrolytic and alkylated PAHs. Results from this study clearly show that the contaminants are mainly generated from anthropogenic petroleum sources. Due to their levels of hydrocarbon contamination, these sludge deposits must be considered as waste and cannot therefore be disposed anywhere, especially within the current context of sustainable development.

Changes in lipids and sterols during composting.

Pyrolysis-gas (Py-GC) chromatography was used to characterize organic [(diethyl ether (DEE) and chloroform (CHCl3)] extracts of raw and composted duck excreta enriched wood shavings from two finishing cycles (C1 and C2). Materials were collected on days 0, 8 and 23. C1 contained 1.7 % total N while C2 contained 0.9 % total N. Py-GC-MS (mass spectrometry) showed that the extracts contained n-alkanes (C12 to C32), alkenes (C12:1 to C33:1), n-fatty acids (C12 to C28), unsaturated fatty acids (C18:1 and C18:2), and sterols (cholestene, cholestadiene, stigmastene, stigmastadiene, stigmastatriene, cholesterol, stigmastanol, stigmastanone, stigmastadienone, 17-methyl dialkylsulfanyl decahydro-1H-cyclopenta [a] phenanthrene, 17-methyl dialkylsulfanyl dodecahydro-1H-cyclopenta [a] phenanthrene, and 17-methyl-17-dialkylsulfanyl decahydro-1H-cyclopenta [a] phenanthrene). Other components identified were prystene, squalene (precursor of cholesterol), phthalic acid, diphenylpropane, diphenylbut-2-ene and 1,3,6 triphenyl hex-4-ene. Our data showed significant changes in the lipid composition of duck excreta enriched wood shavings during composting, which appeared to be related to the total N content of the system.

Hydrocarbon infiltration and biodegradation in a landfarming experiment.

The infiltration and biodegradation of medium molecular weight hydrocarbons were studied in field and lysimeter experiments. An initial loading rate of 4 kg m(-2) of a gas-oil cut (nC12-nC21) was applied and the weathering of hydrocarbons was monitored by gravimetry and capillary gas-chromatography. The composition and vertical distribution of biogenic hydrocarbons were studied in control plots. After 3.5 years, 94% of the fossil hydrocarbons were removed from the field and 83% from the lysimeter. Microbial degradation was active in the 30 cm upper layer of the soil. The undegraded residue was composed of cyclic alkanes and aromatics. Hydrocarbons were shown to penetrate down to 60 cm in the field and 80 cm in the lysimeter. A preferential infiltration of light hydrocarbons was noted in the lysimeter, and a selective adsorption of the heaviest compounds on the organo-mineral matrix was demonstrated in the superficial layer of the soil. The potential for leaching of unmodified hydrocarbons towards the groundwater was slight, whereas the input of total organic carbon resulting from microbial activity could account for more than 1% of the initial carbon load.