Assessing main process mechanism and rates of sulfate reduction by granular biomass fed with glycerol under sulfidogenic conditions.

Sulfate-reducing bioreactors for sulfide production are the initial stage of processes targeting elemental sulfur recovery from sulfate-rich effluents. In this work, the principal reactions involved in glycerol fermentation and sulfate reduction using glycerol and its fermentation products as electron donors were assessed together with their specific consumption/production rates. A battery of batch activity tests with and without sulfate were performed with glycerol and with each fermentation product using a non-methanogenic but sulfidogenic granular sludge from an up-flow anaerobic sludge blanket (UASB) reactor operated under long-term while fed with crude glycerol. As a result, a mechanistic approach based on the experimental observations is proposed in this work. Glycerol was mainly fermented to 1,3-propanediol, ethanol, formate, propionate and acetate by fermentative bacteria. All organic intermediates were found to be further used by sulfate reducing bacteria (SRB) for sulfate reduction except for acetate. The most abundant genus detected under sulfidogenic conditions were Propionispora (15.2%), Dysgonomonas (13.2%), Desulfobulbus (11.6%) and Desulfovibrio (10.8%). The last two SRB genera accounted for 22.4% of the total amount of retrieved sequences, which were probably performing an incomplete oxidation of the carbon source in the sulfidogenic UASB reactor. As single substrates, specific sulfate reduction rates (SRRs) using low molecular weight (MW) carbon sources (formate and ethanol) were 39% higher than those using high-MW ones (propionate, 1,3-propanediol and butanol). However, SRRs in glycerol-fed tests showed that 1,3-propanediol played a major role in sulfate reduction in addition to formate and ethanol.

Microbial Diversity Dynamics in a Methanogenic-Sulfidogenic UASB Reactor.

In this study, the long-term performance and microbial dynamics of an Upflow Anaerobic Sludge Blanket (UASB) reactor targeting sulfate reduction in a SOx emissions treatment system were assessed using crude glycerol as organic carbon source and electron donor under constant S and C loading rates. The reactor was inoculated with granular sludge obtained from a pulp and paper industry and fed at a constant inlet sulfate concentration of 250 mg S-SO42-L-1 and a constant C/S ratio of 1.5 ± 0.3 g Cg-1 S for over 500 days. Apart from the regular analysis of chemical species, Illumina analyses of the 16S rRNA gene were used to study the dynamics of the bacterial community along with the whole operation. The reactor was sampled along the operation to monitor its diversity and the changes in targeted species to gain insight into the performance of the sulfidogenic UASB. Moreover, studies on the stratification of the sludge bed were performed by sampling at different reactor heights. Shifts in the UASB performance correlated well with the main shifts in microbial communities of interest. A progressive loss of the methanogenic capacity towards a fully sulfidogenic UASB was explained by a progressive wash-out of methanogenic Archaea, which were outcompeted by sulfate-reducing bacteria. Desulfovibrio was found as the main sulfate-reducing genus in the reactor along time. A progressive reduction in the sulfidogenic capacity of the UASB was found in the long run due to the accumulation of a slime-like substance in the UASB.

Feasibility of S-rich streams valorization through a two-step biosulfur production process.

A bioscrubbing process named SONOVA has been developed, tested and assessed herein to valorize flue gases containing SOx. The process consists in a first scrubbing stage, to absorb and oxidize SO2 to sulfate, followed by a two-step biological stage. It consists of (1) an up-flow anaerobic sludge (UASB) reactor to reduce sulfate to sulfide with crude glycerol and (2) a continuous stirred tank reactor (CSTR) to partially oxidize sulfide to elemental sulfur (S0). SONOVA integrates the reutilization of resources, using the effluent of the biological stage as a sorbent agent and the residual heat of flue gases to dry the product. S0 is then obtained as a value-added product, which nowadays is produced from fossil fuels. In this research, SO2 concentrations up to 4000 ppmv were absorbed in 2 s of gas contact time in the spray-scrubber with removal efficiencies above 80%. The UASB reduced up to 9.3 kg S-Sulfate m-3 d-1 with sulfide productivities of 6 kg S m-3 d-1 at an hydraulic retention time (HRT) as low as 2 h. Finally, CSTR was fed with the UASB effluent and operated at HRT ranging from 12 h to 4 h without biomass wash-out. Sulfide was fully oxidized to S0 with a productivity of 2.3 kg S m-3 d-1 at the lowest HRT tested. Overall, this research has explored not only maximum capabilities of each SONOVA stage but has also assessed the interactions between the different units, which opens up the possibility of recovering S0 from harmful SOx emissions, optimizing resources utilization and costs.

Exploring the performance limits of a sulfidogenic UASB during the long-term use of crude glycerol as electron donor.

SOx contained in flue gases and S-rich liquid effluents can be valorized to recover elemental sulfur in a two-stage bioscrubbing process. The reduction of sulfate to sulfide is the most crucial stage to be optimized. In this study, the long-term performance of an up-flow anaerobic sludge blanket (UASB) reactor using crude glycerol as electron donor was assessed. The UASB was operated for 400 days with different sulfate and organic loading rates (SLR and OLR, respectively) and a COD/S-SO42- ratio ranging from 3.8 g O2 g-1 S to 5.4 g O2 g-1 S. After inoculation with methanogenic, granular biomass, the competition between sulfate-reducing and methanogenic microorganisms determined to what extent dissolved sulfide and methane were produced. After the complete washout of methanogens, which was revealed by next-generation sequencing analysis, the highest S-EC was reached in the system. The highest average sulfate elimination capacity (S-EC = 4.3 kg S m-3d-1) was obtained at a COD/S-SO42- ratio of 5.4 g O2 g-1 S and an OLR of 24.4 kg O2 m-3d-1 with a sulfate removal efficiency of 94%. The conversion of influent COD to methane decreased from 12% to 2.5% as the SLR increased while a large fraction of acetate (35% of the initial COD) was accumulated. Our data indicate that crude glycerol can promote sulfidogenesis. However, the disappearance of methanogens in the long-term due to the out competition by sulfate reducing bacteria, lead to such large accumulation of acetate.

Evolution of physical-chemical parameters, microbial diversity and VOC emissions of olive oil mill waste exposed to ambient conditions in open reservoirs.

In the olive oil extraction process, 20% olive oil is obtained. About 80% corresponds to waste, mainly alperujo and orujo. When these residues are stored in open reservoirs for later stabilization or potential reuse, odorous Volatile Organic Compounds (VOCs) are generated as products of waste decomposition. In this work, these emissions were studied by means of TD-GC/MS in relation to the changes in the physical-chemical (ashes, moisture, total phenols, pH, proteins, fibers, oils, fats) and biological parameters (bacterial and fungal diversity in Illumina platform) of waste for 6 months. The dynamics of these parameters were statistically related to the evolution of environmental variables (temperature, relative humidity, precipitation) and their effects on the most relevant physical-chemical parameters in order to evaluate their incidence in odorant VOCs emissions over time. The results showed a progressive increase in the diversity of both fungi and bacteria that were related, mainly, to a progressive decrease in the concentration of fatty acid methyl esters and the concentration of alkenes in the emissions; and to an increase of odorous compounds, mainly aldehydes, ketones and carboxylic acids, which were responsible for the unpleasant odors of waste. No significant differences were observed between the evolution of orujo characteristics compared to those of alperujo.