Effect of ammonia on methane production pathways and reaction rates in acetate-fed biogas processes.

In order to understand the correlation between ammonia and methanogenesis metabolism, methane production pathways and their specific rates were studied at total ammonium nitrogen (TAN) concentrations of 0.14-9 g/L in three methanogenic sludges fed with acetate, at both mesophilic and thermophilic conditions. Results showed that high levels of TAN had significant inhibition on methanogenesis; this could, however, be recovered via syntrophic acetate oxidation (SAO) coupled with Hydrogenotrophic Methanogenesis (HM) performed by acetate oxidizing syntrophs or through Acetoclastic Methanogenesis (AM) catalyzed by Methanosarcinaceae, after a long lag phase >50 d. Free ammonia (NH3) was the active component for this inhibition, of which 200 mg/L is suggested as the threshold for the pathway shift from AM to SAO-HM. Methane production rate via SAO-HM at TAN of 7-9 g/L was about 5-9-fold lower than that of AM at TAN of 0.14 g/L, which was also lower than the rate of AM pathway recovered at TAN of 7 g/L in the incubations with a French mesophilic inoculum. Thermophilic condition favored the establishment of the SAO-catalyzing microbial community, as indicated by the higher reaction rate and shorter lag phase. The operational strategy is thus suggested to be adjusted when NH3 exceeds 200 mg/L.

Similar evolution in delta 13CH4 and model-predicted relative rate of aceticlastic methanogenesis during mesophilic methanization of municipal solid wastes.

Similar evolution was obtained for the stable carbon isotope signatures delta (13)CH(4) and the model-predicted relative rate of aceticlastic methanogenesis during mesophilic methanization of municipal solid wastes. In batch incubations, the importance of aceticlastic and hydrogenotrophic methanogenesis changes in time. Initially, hydrogenotrophic methanogenesis dominated, but increasing population of Methanosarcina sp. enhances aceticlastic methanogenesis. Later, hydrogenotrophic methanogenesis intensified again. A mathematical model was developed to evaluate the relative contribution of hydrogenotrophic and aceticlastic pathways of methane generation during mesophilic batch anaerobic biodegradation of the French and the Chinese Municipal Solid Wastes (FMSW and CMSW). Taking into account molecular biology analysis reported earlier three groups of methanogens including strictly hydrogenotrophic methanogens, strictly aceticlastic methanogens (Methanosaeta sp.) and Methanosarcina sp., consuming both acetate and H(2)/H(2)CO(3) were considered in the model. The total organic and inorganic carbon concentrations, methane production volume, methane and carbon dioxide partial pressures values were used for the model calibration and validation. Methane isotopic composition (delta (13)CH(4)) evolution during the incubations was used to independently validate the model results. The model demonstrated that only the putrescible solid waste was totally converted to methane.

Anaerobic biodegradation of cellulosic material: batch experiments and modelling based on isotopic data and focusing on aceticlastic and non-aceticlastic methanogenesis.

Utilizing stable carbon isotope data to account for aceticlastic and non-aceticlastic pathways of methane generation, a model was created to describe laboratory batch anaerobic decomposition of cellulosic materials (office paper and cardboard). The total organic and inorganic carbon concentrations, methane production volume, and methane and CO(2) partial pressure values were used for the model calibration and validation. According to the fluorescent in situ hybridization observations, three groups of methanogens including strictly hydrogenotrophic methanogens, strictly aceticlastic methanogens (Methanosaeta sp.) and Methanosarcina sp., consuming both acetate and H(2)/H(2)CO(3) as well as acetate-oxidizing syntrophs, were considered. It was shown that temporary inhibition of aceticlastic methanogens by non-ionized volatile fatty acids or acidic pH was responsible for two-step methane production from office paper at 35 degrees C where during the first and second steps methane was generated mostly from H(2)/H(2)CO(3) and acetate, respectively. Water saturated and unsaturated cases were tested. According to the model, at the intermediate moisture (150%), much lower methane production occurred because of full-time inhibition of aceticlastic methanogens. At the lowest moisture, methane production was very low because most likely hydrolysis was seriously inhibited. Simulations showed that during cardboard and office paper biodegradation at 55 degrees C, non-aceticlastic syntrophic oxidation by acetate-oxidizing syntrophs and hydrogenotrophic methanogens were the dominant methanogenic pathways.

Evaluation of analytical strategies for the determination of metal concentrations to assess landfill leachate contamination.

Due to the complex nature of landfill leachates, metal and metalloid analyses prove to be tricky and suffer from a lack of standard protocols. A complete approach has been adopted to investigate the influence of the different steps during the sample processing of French landfill leachates. The validation of the entire protocol has been achieved using a laboratory reference material. This material, which is a real landfill leachate, is representative of real samples. Its evaluation has allowed a quality control for metal and metalloid analyses in landfill leachates. Precautions concerning storage temperature, aeration and filtration are proposed to perform accurate metal analyses in these complex matrices. The sample processing has been applied to the seasonal monitoring of a French landfill. The assessment of major leachate metallic contaminants such as As, Cr, Sb, Sn, has been performed by evaluating the relative enrichment of metals and metalloids in comparison with rain water and groundwater. In addition, hydrological data are useful and complementary information for pointing out the main factors affecting metal concentrations and thus their potential remobilisation pathways.

Leachate pre-treatment strategies before recirculation in landfill bioreactors.

Nitrified leachate recirculation represents a promising strategy for a more sustainable landfill management. Our objective was to determine the reactions involved in nitrate reduction in municipal solid waste batch biodegradation tests. Anaerobic digestion of waste in the three control reactors showed a good reproducibility. In two test reactors, nitrate was added at various moments of the waste degradation process. We observed that: (1) H2S concentration controlled the nitrate reduction pathway: above a certain threshold of H2S, dissimilatory nitrate reduction to ammonium (DNRA) replaced denitrification. (2) N2O/N2 ratio varied with the organic carbon concentration: the lower the easily biodegradable carbon concentration, the higher the N2O/N2 ratio. (3) N2 was consumed after denitrification. The possibility of a nitrogen fixation reaction in the presence of NH4 is discussed. Nitrified leachate recirculation during acidogenesis should be avoided because of higher H2S production which could induce DNRA.

Molecular and stable carbon isotopic source identification of oil residues and oiled bird feathers sampled along the Atlantic Coast of France after the Erika oil spill.

The Erika tanker broke in two close to the Atlantic coast of France on December 12, 1999. On December 25th, some heavy fuel oil released by the tanker came ashore along the French Atlantic Coast. Some oil residues and oiled bird feathers were collected all along the Atlantic Shoreline of France after the wreck of the Erika tanker. The aim of this study was to differentiate oil residues and oiled bird feathers related to the Erika oil spill from the ones resulting from the numerous tar ball incidents which had occurred after the Erika oil spill. Alkane and PAH quantification of oil residues allowed differentiation of the samples collected on the north part of the Atlantic Coast from those collected on the south part of the Atlantic shoreline. All oiled birds appear to have been contaminated by the Erika oil. Samples collected on the south part of the Atlantic Coast contain a different molecular fingerprint compared to the Erika oil indicating that they are not related to the Erika oil spill. Bulk and molecular 13C/12C ratio measurements were performed in order to check the discriminative feature and the stability of the isotopic approach. Bulk stable carbon isotopic composition has been shown to be a valuable screening correlation tool as it confirms the link of samples collected in the north part of the Atlantic Coast with the Erika oil spill. All the samples collected along the south part of the Atlantic Shoreline exhibit 13C-enriched bulk isotopic compositions compared to Erika oil. Molecular isotopic composition of saturated hydrocarbons and of phenanthrene compounds also allows unambiguous differentiation of samples related to the Erika oil spill from those due to tar ball incidents. Over the long-term, when molecular distribution will have been modified by the different processes affecting oil in the marine environment, molecular isotopic composition should then be of particular help for Erika oil residues identification.

Polycyclic aromatic hydrocarbon 13C/12C ratio measurement in petroleum and marine sediments application to standard reference materials and a sediment suspected of contamination from the Erika oil spill.

This paper describes a simple and rapid sample preparation procedure allowing to measure the stable carbon isotopic composition of polycyclic aromatic hydrocarbons (PAHs) in petroleum and in sediments. The aromatic fraction is first purified and isolated on alumina and silica micro-columns. A high-performance liquid chromatography fractionation allows one then to isolate each aromatic family in order to limit coelutions between PAHs. Moreover, this purification step reduces the importance of the unresolved complex mixture which otherwise contribute to the GC-isotope ratio MS background signal. The application of this analytical procedure has allowed one to determined PAH isotopic composition in a reference material crude oil (SRM 1582) and a marine sediment (SRM 1944) with good reproducibility as uncertainties between three independent assays performed were lower than 0.5 per thousand. This analytical procedure has then been successfully applied to confirm the contamination of a sediment by the petroleum product spilled by the Erika tanker after its wreck on 12 December 1999 close to the Atlantic Coast of France.