Long hydraulic retention time mediates stable volatile fatty acids production against slight pH oscillations

•Long hydraulic retention time ensured stable carboxylate production.•Microbial robustness mediated stable performance against pH oscillations.•20 d of retention time was identified as an upper threshold of process efficiency.•Metabolic redundancy is key for a robust microbiome development. The effect of operational conditions on the stability of acidogenic fermentation (AF) devoted to volatile fatty acids (VFAs) production still presents numerous gaps to achieve high yields and fully understand the responses of open microbiomes associated to this technology. To cope with that, this investigation was designed to assess the stability of VFAs production via AF of agro-food wastes at high hydraulic retention times (HRTs) (20 and 30 d) and pH oscillations (5.8–6.2). Similar bioconversion efficiencies (∼50 %) were reached regardless of the HRT, revealing that HRT of 20 d can be considered as a threshold from which, no further improvement was achieved. The combination of long HRTs, 25 °C and acid pHs promoted a robust microbiome that resulted in a stable outcome against pH variations, being Clostridiales order identified as key player of AF stability. These conditions mediated a high selectivity in the VFAs production profile, with acetic and butyric acids, prevailing in the VFAs pool (∼80 % of total VFAs) at HRT 20 d. The selection of appropriated conditions was shown to be critical to maximize the hydrolysis and acidogenesis of the substrate and attain a stable effluent against pH oscillations.