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Anaerobic digestion of agricultural waste can contribute to the European renewable energy needs. The 71% of the 20,000 anaerobic digestion plants in operation already uses these agro-waste as feedstock; part of these plants can be converted into two stage processes to produce hydrogen and methane in the same plant. Biomethane enriched in hydrogen can replace natural gas in grids while contributing to the sector decarbonisation. Straw is the most abundant agricultural residue (156 Mt/y) and its conventional final fate is uncontrolled soil disposal, landfilling, incineration or, in the best cases, composting. The present research work focuses on the fermentation of spent mushroom bed, an agricultural lignocellulosic byproduct, composed mainly from wheat straw. The substrate has been characterized and semi-continuous tests were performed evaluating the effect of the hydraulic retention time on hydrogen and volatile fatty acids production. It was found that all the tests confirmed the feasibility of the process even on this lignocellulosic substrate, and also, it was identified HRT 4.0 d as the best option to optimize the productivity of volatile fatty acids (17.09 gCODVFAs/(KgVS*d)), and HRT 6.0 d for hydrogen (7.98 LH 2 /(KgVS*d)). The fermentation effluent was used in biomethanation potential tests to evaluate how this process affects a subsequent digestion phase, reporting an increase in the energetical feedstock exploitation up to 30%., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Federico Battista reports financial support was provided by National Institute for Insurance against Accidents at Work. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

The performance parameters of volatile fatty acids (VFAs) measurements were assessed for the first time by a multi-laboratory validation study among 13 laboratories. Two chromatographic techniques (GC and HPLC) and two quantification methods such as external and internal standard (ESTD/ISTD) were combined in three different methodologies GC/ESTD, HPLC/ESTD and GC/ISTD. Linearity evaluation of the calibration functions in a wide concentration range (10-1000mg/L) was carried out using different statistical parameters for the goodness of fit. Both chromatographic techniques were considered similarly accurate. The use of GC/ISTD, despite showing similar analytical performance to the other methodologies, can be considered useful for the harmonization of VFAs analytical methodology taking into account the normalization of slope values used for the calculation of VFAs concentrations. Acceptance criteria for VFAs performance parameters of the multi-laboratory validation study should be established as follows: (1) instrument precision (RSDINST≤1.5%); (2) linearity (R(2)≥0.998; RSDSENSITIVITY≤4%; REMAX≤8%; REAVER≤ 3%); (3) precision (RSD≤1.5%); (4) trueness (recovery of 97-103%); (5) LOD (≤3mg/L); and (6) LOQ (10mg/L)., (Copyright © 2015 Elsevier B.V. All rights reserved.)