Use of N-Methylmorpholine N-oxide (NMMO) pretreatment to enhance the bioconversion of lignocellulosic residues to methane.

Lignocellulosic residues (LRs) are one of the most abundant wastes produced worldwide. Nevertheless, unlocking the full energy potential from LRs for biofuel production is limited by their complex structure. This study investigated the effect of N-methylmorpholine N-oxide (NMMO) pretreatment on almond shell (AS), spent coffee grounds (SCG), and hazelnut skin (HS) to improve their bioconversion to methane. The pretreatment was performed using a 73% NMMO solution heated at 120 °C for 1, 3, and 5 h. The baseline methane productions achieved from raw AS, SCG, and HS were 54.7 (± 5.3), 337.4 (± 16.5), and 265.4 (± 10.4) mL CH4/g VS, respectively. The NMMO pretreatment enhanced the methane potential of AS up to 58%, although no changes in chemical composition and external surface were observed after pretreatment. Opposite to this, pretreated SCG showed increased porosity (up to 63%) and a higher sugar percentage (up to 27%) after pretreatment despite failing to increase methane production. All pretreatment conditions were effective on HS, achieving the highest methane production of 400.4 (± 9.5) mL CH4/g VS after 5 h pretreatment. The enhanced methane production was due to the increased sugar percentage (up to 112%), lignin removal (up to 29%), and loss of inhibitory compounds during the pretreatment. An energy assessment revealed that the NMMO pretreatment is an attractive technology to be implemented on an industrial scale for energy recovery from HS residues. Supplementary Information: The online version contains supplementary material available at 10.1007/s13399-022-03173-x.

Ultrasounds application for nut and coffee wastes valorisation via biomolecules solubilisation and methane production.

Lignocellulosic materials (LMs) are abundant feedstocks with excellent potential for biofuels and biocommodities production. In particular, nut and coffee wastes are rich in biomolecules, e.g. sugars and polyphenols, the valorisation of which still has to be fully disclosed. This study investigated the effectiveness of ultrasounds coupled with hydrothermal (i.e. ambient temperature vs 80 °C) and methanol (MeOH)-based pretreatments for polyphenols and sugar solubilisation from hazelnut skin (HS), almond shell (AS), and spent coffee grounds (SCG). The liquid fraction obtained from the pretreated HS was the most promising in terms of biomolecules solubilisation. The highest polyphenols, i.e. 123.9 (±2.3) mg/g TS, and sugar, i.e. 146.0 (±3.4) mg/g TS, solubilisation was obtained using the MeOH-based medium. However, the MeOH-based media were not suitable for direct anaerobic digestion (AD) due to the MeOH inhibition during AD. The water-based liquors obtained from pretreated AS and SCG exhibited a higher methane potential, i.e. 434.2 (±25.1) and 685.5 (±39.5) mL CH4/g glucosein, respectively, than the HS liquors despite having a lower sugar concentration. The solid residues recovered after ultrasounds pretreatment were used as substrates for AD as well. Regardless the pretreatment condition, the methane potential of the ultrasounds pretreated HS, AS, and SCG was not improved, achieving maximally 255.4 (±7.4), 42.8 (±3.3), and 366.2 (±4.2) mL CH4/g VS, respectively. Hence, the solid and liquid fractions obtained from HS, AS, and SCG showed great potential either as substrates for AD or, in perspective, for biomolecules recovery in a biorefinery context.

Fed-batch anaerobic digestion of raw and pretreated hazelnut skin over long-term operation.

This study provided important insights on the anaerobic digestion (AD) of hazelnut skin (HS) by operating a fed-batch AD reactor over 240 days and focusing on several factors impacting the process in the long term. An efficient reactor configuration was proposed to increase the substrate load while reducing the solid retention time during the fed-batch AD of HS. Raw HS produced maximally 19.29 mL CH4/g VSadd/d. Polyphenols accumulated in the reactor and the use of NaOH to adjust the pH likely inhibited AD. Maceration and methanol-organosolv pretreatments were, thus, used to remove polyphenols from HS (i.e. 82 and 97%, respectively) and improve HS biodegradation. Additionally, organosolv pretreatment removed 9% of the lignin. The organosolv-pretreated HS showed an increment in methane potential of 21%, while macerated HS produced less methane than the raw substrate, probably due to the loss of non-structural sugars during maceration.

Removal of polycyclic aromatic hydrocarbons during anaerobic biostimulation of marine sediments.

This study proposes the supplementation of digestate, fresh organic fraction of municipal solid waste (OFMSW) and a nutrient solution during the anaerobic biostimulation of marine sediments contaminated by polycyclic aromatic hydrocarbons (PAHs). The experimental activity was conducted with four PAHs (i.e. phenanthrene, anthracene, fluoranthene and pyrene) under controlled mesophilic conditions (37 ± 1 °C) in 100 mL serum bottles maintained at 130 rpm. After 120 days of incubation, the highest total PAH degradation of 53 and 55% was observed in the experiments with digestate + nutrients and OFMSW + nutrients, respectively. Phenanthrene was the most degraded PAH and the highest removal of 69% was achieved with OFMSW + nutrients. The anaerobic PAH degradation proceeded through the accumulation of volatile fatty acids and the production of hydrogen and methane as biogas constituents. The highest cumulative biohydrogen production of 80 mL H2·g VS-1 was obtained when OFMSW was used as the sole amendment, whereas the highest biomethane yield of 140 mL CH4·g VS-1 was obtained with OFMSW + nutrients. The evolution of PAH removal during anaerobic digestion revealed a higher impact of the methanogenic phase rather than acidogenic phase on PAH degradation.

Sensitivity analysis for an elemental sulfur-based two-step denitrification model.

A local sensitivity analysis was performed for a chemically synthesized elemental sulfur (S0)-based two-step denitrification model, accounting for nitrite (NO2 -) accumulation, biomass growth and S0 hydrolysis. The sensitivity analysis was aimed at verifying the model stability, understanding the model structure and individuating the model parameters to be further optimized. The mass specific area of the sulfur particles (a*) and hydrolysis kinetic constant (k1) were identified as the dominant parameters on the model outputs, i.e. nitrate (NO3 -), NO2 - and sulfate (SO4 2-) concentrations, confirming that the microbially catalyzed S0 hydrolysis is the rate-limiting step during S0-driven denitrification. Additionally, the maximum growth rates of the denitrifying biomass on NO3 - and NO2 - were detected as the most sensitive kinetic parameters.

Fluidized-bed denitrification of mining water tolerates high nickel concentrations.

This study revealed that fluidized-bed denitrifying cultures tolerated soluble Ni concentrations up to 500 mg/L at 7-8 and 22°C. From 10 to 40 mg/L of feed Ni, denitrification resulted in complete nitrate and nitrite removal. The concomitant reduction of 30 mg/L of sulfate produced 10 mg/L of sulfide that precipitated nickel, resulting in soluble effluent Ni below 22 mg/L. At this stage, Dechloromonas species were the dominant denitrifying bacteria. From 60 to 500 mg/L of feed Ni, nickel remained in solution due to the inhibition of sulfate reduction. At soluble 60 mg/L of Ni, denitrification was partially inhibited prior to recover after 34 days of enrichment by other Ni-tolerant species (including Delftia, Zoogloea and Azospira) that supported Dechloromonas. Subsequently, the FBR cultures completely removed nitrate even at 500 mg/L of Ni. Visual Minteq speciation model predicted the formation of NiS, NiCO3 and Ni3(PO4)2, whilst only Ni3(PO4)2 was detected by XRD.

Effect of arsenic on nitrification of simulated mining water.

Mining and mineral processing of gold-bearing ores often release arsenic to the environment. Ammonium is released when N-based explosives or cyanide are used. Nitrification of simulated As-rich mining waters was investigated in batch bioassays using nitrifying cultures enriched in a fluidized-bed reactor (FBR). Nitrification was maintained at 100mg AsTOT/L. In batch assays, ammonium was totally oxidized by the FBR enrichment in 48 h. As(III) oxidation to As(V) occurred during the first 3h attenuating arsenic toxicity to nitrification. At 150 and 200mg AsTOT/L, nitrification was inhibited by 25%. Candidatus Nitrospira defluvii and other nitrifying species mainly colonized the FBR. In conclusion, the FBR enriched cultures of municipal activated sludge origins tolerated high As concentrations making nitrification a potent process for mining water treatment.

Fluidized-bed denitrification for mine waters. Part II: effects of Ni and Co.

The dispersion of nitrogenous compounds and heavy metals into the environment is frequent during mining activities. The effects of nickel (Ni) and cobalt (Co) on denitrification of simulated mine waters were investigated in batch bioassays and fluidized-bed reactors (FBRs). At pH 7, batch tests revealed that Co did not exhibit inhibition on denitrification even at 86.6 mg/L. Ni showed to be inhibitory at 50 and 100 mg/L by decreasing nitrate removal efficiencies of 18 and 65 %, respectively. In two FBRs, operated at 7-8 and 22 °C, 5.5 mg/L Ni did not affect nitrate and nitrite removals because of FBR potential of diluting soluble Ni feed concentration. On the contrary, the effluent pH clearly decreased in both FBR1 and FBR2 because of nickel sulfide precipitation and Ni inhibition of the last two steps of denitrification. When Ni injection was stopped, the process recovered more slowly at 22 than 7-8 °C. This is the first study reporting the effect of Ni on denitrification in biological FBRs.

Fluidized-bed denitrification for mine waters. Part I: low pH and temperature operation.

Mining often leads to nitrate and metal contamination of groundwater and water bodies. Denitrification of acidic water was investigated in two up-flow fluidized-bed reactors (FBR) and using batch assays. Bacterial communities were enriched on ethanol plus nitrate in the FBRs. Initially, the effects of temperature, low-pH and ethanol/nitrate on denitrification were revealed. Batch assays showed that pH 4.8 was inhibitory to denitrification, whereas FBR characteristics permitted denitrification even at feed pH of 2.5 and at 7-8 °C. Nitrate and ethanol were removed and the feed pH was neutralized, provided that ethanol was supplied in excess to nitrate. Subsequently, Fe(II) and Cu impact on denitrification was investigated within batch tests at pH 7. Iron supplementation up to 100 mg/L resulted in iron oxidation and soluble concentrations ranging from 0.4 to 1.6 mg/L that stimulated denitrification. On the contrary, 0.7 mg/L of soluble Cu significantly slowed denitrification down resulting in about 45 % of inhibition in the first 8 h. Polymerase chain reaction-denaturant gradient gel electrophoresis demonstrated the co-existence of different denitrifying microbial consortia in FBRs. Dechloromonas denitrificans and Hydrogenophaga caeni were present in both FBRs and mainly responsible for nitrate reduction.

Biological inverse fluidized-bed reactors for the treatment of low pH- and sulphate-containing wastewaters under different COD/SO4(2-) conditions.

The feasibility of removing sulphate using low-density polypropylene pellets as carrier material in two lactate-fed sulphidogenic inverse fluidized-bed reactors was investigated. Two different COD/sulphate ratios and two different feed-sulphate concentrations were used for the operation of the reactors. During the 242 days of operation, the robustness of the system was studied by suddenly decreasing the feed pH to 3.00. A 10% fluidization degree was used since the carrier material adopted showed not to be adequate to attain a satisfactory immobilization of the biomass with higher fluidization degrees. This resulted in a failure of the process when the feed pH was intentionally decreased to 3.00 in reactor 2, operated with a COD/sulphate ratio of 4.00. On the contrary, when a slightly acidic feed solution was fed to reactor 2, a 97% sulphate reduction efficiency was obtained. In reactor 1, operated with a COD/sulphate ratio of 0.67 throughout the experiment, COD removal and sulphate reduction efficiencies reached the highest values of 75% and 35%, respectively. Higher efficiencies were not achieved also due to the accumulation of acetate and the most likely presence of microbial competition between sulphate reducers and other microorganisms.

Influence of sulfide concentration and macronutrients on the characteristics of metal precipitates relevant to metal recovery in bioreactors.

Purity and settling properties determine metal sulfide recovery from bioreactors. The influence of macronutrients commonly present in mineral media and wastewaters on Cu, Pb, Cd and Zn depletion kinetics and characteristics was evaluated in batch experiments with chemically produced sulfide at different concentrations. The metal depletion kinetics showed that metals with slower depletion rates (Zn and Cd) are susceptible to other removal mechanisms such as biosorption onto the sulfate reducing biofilm and precipitation with macronutrients when sulfide is below the stoichiometric metal to sulfide ratio. For Zn, the main mechanism of removal is its sorption onto apatite (Ca(5)(PO(4)))(3)(+)(OH(-)), a compound formed due to the presence of CaCl(2)·2H(2)O and KH(2)PO(4) in the mineral medium. All precipitates were 8.1-10.0µm regardless the sulfide concentration demonstrating that this parameter is less relevant for particle growth and settling, compared to the agglomeration of the precipitates.

Effect of sulfide concentration on the location of the metal precipitates in inversed fluidized bed reactors.

The effect of the sulfide concentration on the location of the metal precipitates within sulfate-reducing inversed fluidized bed (IFB) reactors was evaluated. Two mesophilic IFB reactors were operated for over 100 days at the same operational conditions, but with different chemical oxygen demand (COD) to SO(4)(2-) ratio (5 and 1, respectively). After a start up phase, 10mg/L of Cu, Pb, Cd and Zn each were added to the influent. The sulfide concentration in one IFB reactor reached 648 mg/L, while it reached only 59 mg/L in the other one. In the high sulfide IFB reactor, the precipitated metals were mainly located in the bulk liquid (as fines), whereas in the low sulfide IFB reactor the metal preciptiates were mainly present in the biofilm. The latter can be explained by local supersaturation due to sulfide production in the biofilm. This paper demonstrates that the sulfide concentration needs to be controlled in sulfate reducing IFB reactors to steer the location of the metal precipitates for recovery.