Anaerobic co-metabolic biodegradation of pharmaceuticals and personal care products driven by glycerol fermentation.

Anaerobic digestion in two sequential phases, acidogenesis and methanogenesis, has been shown to be beneficial for enhancing the biomethane generation from wastewater. In this work, the application of glycerol (GOH) as a fermentation co-substrate during the wastewater treatment was evaluated on the biodegradation of different pharmaceuticals and personal care products (PPCPs). GOH co-digestion during acidogenesis led to a significant increase in the biodegradation of acetaminophen (from 78 to 89%), ciprofloxacin (from 25 to 46%), naproxen (from 73 to 86%), diclofenac (from 36 to 48%), ibuprofen (from 65 to 88%), metoprolol (from 45 to 59%), methylparaben (from 64 to 78%) and propylparaben (from 68 to 74%). The heterotrophic co-metabolism of PPCPs driven by glycerol was confirmed by the biodegradation kinetics, in which kbio (biodegradation kinetics constant) values increased from 0.18 to 2.11 to 0.27-3.60 L g-1-VSS d-1, for the operational phases without and with GOH, respectively. The assessment of metabolic pathways in each phase revealed that the prevalence of aromatic compounds degradation, metabolism of xenobiotics by cytochrome P450, and benzoate degradation routes during acidogenesis are key factors for the enzymatic mechanisms linked to the PPCPs co-metabolism. The phase separation of anaerobic digestion was effective in the PPCPs biodegradation, and the co-fermentation of glycerol provided an increase in the generation potential of biomethane in the system (energetic potential of 5.0 and 6.3 kJ g-1-CODremoved, without and with GOH, respectively). This study showed evidence that glycerol co-fermentation can exert a synergistic effect on the PPCPs removal during anaerobic digestion mediated by heterotrophic co-metabolism.

Two-phase (acidogenic-methanogenic) anaerobic fixed bed biofilm reactor enhances the biological domestic sewage treatment: Perspectives for recovering bioenergy and value-added by-products.

The organic matter bioconversion into methane during anaerobic digestion (AD) comprises different steps, the acidogenic and methanogenic phases being clearly distinct in terms of metabolic activities. In this work, new configurations of anaerobic fixed bed biofilm reactors (AFBBR) were operated under conventional methanogenic conditions (single phase - SP-AFBBR, M1R), and in a sequential two-phase system, acidogenic reactor followed by methanogenic reactor (TP-AFBBR, AcR + M2R), in order to verify the impact of the AD phase separation on the overall system performance in operational, kinetics and microbiological aspects. The results indicated that feeding the methanogenic reactor with the acidogenic effluent stream provided a shorter operating start-up period (11 and 32 days for SP and TP-AFBBR, respectively), a greater alkalinity generation (0.14 and 0.41 g-CaCO3·g-CODremoved-1 for M1R and M2R, respectively), and the optimization of biomethane production (methane yield of 95 and 154 N-mLCH4·g-CODremoved-1 for M1R and M2R, respectively). The COD removal kinetics was also favored in the TP-AFBBR (k1-COD = 1.4 and 2.9 h-1 for M1R and M2R, respectively), since the soluble fermentation products were readily bioavailable to the biomass in the reactor. Hydrogenotrophic methanogenesis was the predominant pathway in the M2R, while the Methanosaeta-driven acetoclastic pathway predominated in the M1R. The greater diversity of Bacteria and Archaea in M2R denotes a better balance between the species that degrade volatile organic acids from AcR (i.e. Syntrophorhabdus, Syntrophus and Syntrophobacter) and the hydrogenotrophic methanogens (Methanoregula, Methanolinea and Methanospirillum) that consume the biodegradation products. The estimated bioenergy generation potential (range of 0.39-0.64 kWh·m-3-sewage considering the COD removed) for full-scale TP-sewage treatment plants evidences the feasibility of energetic recovery in the domestic sewage anaerobic treatment.

Influence of organic loading rate on ciprofloxacin and sulfamethoxazole biodegradation in anaerobic fixed bed biofilm reactors.

Antibiotic compounds, notably sulfamethoxazole (SMX) and ciprofloxacin (CIP), are ubiquitous emerging contaminants (ECs), which are often found in domestic sewage. They are associated with the development of antimicrobial resistance. Operational parameters, e.g. organic loading rate (OLR), hydraulic retention time (HRT) and sludge retention time, may influence EC biodegradation in wastewater treatment plants. This study assessed the impact of the OLR variation on the biodegradation of CIP and SMX, applying two configurations of anaerobic fixed bed reactors: anaerobic packed bed biofilm reactor (APBBR) and anaerobic structured bed biofilm reactor (ASBBR). A significant reduction in the biodegradation of SMX (APBBR: 93-69%; ASBBR: 94-81%) and CIP (APBBR: 85-66%; ASBBR: 85-64%) was observed increasing OLR from 0.6 to 2.0 kgCOD m-3 d-1. The decrease in the HRT from 12 to 4 h resulted in higher liquid-phase mass transfer coefficient (APBBR: ks from 0.01 to 0.05 cm h-1; ASBBR: ks from 0.07 to 0.24 cm h-1), but this was not enough to overcome the decrease in the antibiotic-biomass contact time on biofilm, thus reducing the bioreactors' performance. The ASBBR favored biomethane production (from 7 to 17 mLCH4 g-1VSS L-1 d-1) and biodegradation kinetics (kbio from 1.7 to 4.2 and for SMX and from 2.1 to 4.8 L g-1VSS d-1 for CIP) due to the higher relative abundance of the archaea community in the biofilm and the lower liquid-phase mass transfer resistance in the structured bed. CIP and SMX cometabolic biodegradation was associated to the hydrogenotrophic methanogenesis (mainly Methanobacterium genus) in co-culture with fermentative bacteria (notably the genera Clostridium, Bacillus, Lactivibrio, Syntrophobacter and Syntrophorhabdus). The anaerobic fixed bed biofilm reactors proved to be highly efficient in biodegrading the antibiotics, preventing them from spreading to the environment.

Acidogenesis is a key step in the anaerobic biotransformation of organic micropollutants.

Understanding the role of the different anaerobic digestion stages on the removal of organic micropollutants (OMPs) is essential to mitigate their release from wastewater treatment plants. This study assessed the fate of 21 OMPs during hydrolysis and acidogenesis to elucidate the contribution of these stages to the overall anaerobic removal. Moreover, the removal mechanisms and factors influencing them were investigated. To this purpose, a fermentation reactor was operated and fed with two different substrates: starch (to jointly evaluate hydrolysis and acidogenesis) and glucose (to isolate acidogenesis). Results indicate that sulfamethoxazole was highly biotransformed (>80 %), while galaxolide, celestolide, tonalide, erythromycin, roxithromycin, trimethoprim, octylphenol and nonylphenol achieved a 50-80 % biotransformation. Since no significant differences in the biotransformation efficiencies were found between starch and glucose fermentation, it is stated that the enzymatic activities involved in starch hydrolysis do not significantly contribute to the cometabolic biotransformation of OMPs, while acidogenesis appears as the major player. Moreover, a higher biotransformation (≥15 percentage points and p ≤ 0.05) was found for galaxolide, celestolide, tonalide, erythromycin and roxithromycin during acidogenesis in comparison with the efficiencies reported for the acetogenic/methanogenic step. The biotransformation of some OMPs was explained considering their chemical structure and the enzymatic activities.

Feasibility of anaerobic packed and structured-bed reactors for sulfamethoxazole and ciprofloxacin removal from domestic sewage.

This study assessed the applicability of fixed bed bioreactors in two configurations - anaerobic structured bed reactor (ASBR) and anaerobic packed bed reactor (APBR) - in the removal of Sulfamethoxazole (SMX) and Ciprofloxacin (CIP), two antibiotics frequently detected in sanitary sewage. The problem of these pharmaceuticals as emerging contaminants in conventional sewage treatment systems is mainly because they encourage the development and spread of resistance genes in bacteria. Both reactors had similar performances, and the antibiotics were highly removed - APBR: 85 ±â€¯10% for SMX and 81 ±â€¯16% for CIP; ASBR: 83 ±â€¯12% for SMX and 81 ±â€¯15% for CIP. The ASBR showed to be potentially more feasible in operating and economic terms compared to the APBR, as the former presents a smaller amount of support material in the bed. SMX was completely biotransformed, while the influence of the sorption mechanism was observed for CIP, as its presence was detected sorbed onto biomass throughout the reaction bed of the reactors, with a partition coefficient (log KD) of around 2.8 L·kg-1TSS. The degradation kinetics of the pharmaceuticals were fitted using a first-order kinetic model, whereby the reactors behaved as plug flow ones, indicating the possibility of optimizing the operation for a hydraulic retention time of 6 h. The removal kinetics was more favorable for CIP (higher apparent constant kinetic - kCIPapp > kSMXapp), since its biodegradation is linked to the biomass, which is more concentrated in the bed bottom layer. The experimental results showed the potential of anaerobic fixed bed reactors in removing environmentally relevant concentrations of SMX and CIP found in sewage.