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.

Methanotrophic denitrification in wastewater treatment: microbial aspects and engineering strategies.

Anaerobic technologies are consolidated for sewage treatment and are the core processes for mining marketable products from waste streams. However, anaerobic effluents are supersaturated with methane, which represents a liability regarding greenhouse gas emissions. Meanwhile, anaerobic technologies are not capable of nitrogen removal, which is required to ensure environmental protection. Methane oxidation and denitrification processes can be combined to address both issues concurrently. Aerobic methane oxidizers can release intermediate organic compounds that can be used by conventional denitrifiers as electron donors. Alternatively, anoxic methanotrophic species combine methane oxidation with either nitrate or nitrite reduction in the same metabolism. Engineered systems need to overcome the long doubling times and low NOx consumption rates of anoxic methanotrophic microorganisms. Another commonly reported bottleneck of methanotrophic denitrification relates to gas-liquid mass transfer limitations. Although anaerobic effluents are supersaturated with methane, experimental setups usually rely on methane supply in a gaseous mode. Hence, possibilities for the application of methane-oxidation coupled to denitrification in full scale might be overlooked. Moreover, syntrophic relationships among methane oxidizers, denitrifiers, nitrifiers, and other microorganisms (such as anammox) are not well understood. Integrating mixed populations with various metabolic abilities could allow for more robust methane-driven wastewater denitrification systems. This review presents an overview of the metabolic capabilities of methane oxidation and denitrification and discusses technological aspects that allow for the application of methanotrophic denitrification at larger scales.

Enrichment of Autotrophic Denitrifiers From Anaerobic Sludge Using Sulfurous Electron Donors.

This study compared the rates and microbial community development in batch bioassays on autotrophic denitrification using elemental sulfur (S0), pyrite (FeS2), thiosulfate (S2O3 2-), and sulfide (S2-) as electron donor. The performance of two inocula was compared: digested sludge (DS) from a wastewater treatment plant of a dairy industry and anaerobic granular sludge (GS) from a UASB reactor treating dairy wastewater. All electron donors supported the development of a microbial community with predominance of autotrophic denitrifiers during the enrichments, except for sulfide. For the first time, pyrite revealed to be a suitable substrate for the growth of autotrophic denitrifiers developing a microbial community with predominance of the genera Thiobacillus, Thioprofundum, and Ignavibacterium. Thiosulfate gave the highest denitrification rates removing 10.94 mM NO3 - day-1 and 8.98 mM NO3 - day-1 by DS and GS, respectively. This was 1.5 and 6 times faster than elemental sulfur and pyrite, respectively. Despite the highest denitrification rates observed in thiosulfate-fed enrichments, an evaluation of the most relevant parameters for a technological application revealed elemental sulfur as the best electron donor for autotrophic denitrification with a total cost of 0.38 € per m3 of wastewater treated.

Cathodic selenium recovery in bioelectrochemical system: Regulatory influence on anodic electrogenic activity.

Metal(loid)s are used in various industrial activities and widely spread across the environmental settings in various forms and concentrations. Extended releases of metal(loid)s above the regulatory levels cause environmental and health hazards disturbing the ecological balance. Innovative processes for treating the metal(loid)-contaminated sites and recovery of metal(loid)s from disposed waste streams employing biotechnological routes provide a sustainable way forward. Conventional metal recovery technologies demand high energy and/or resource inputs, which are either uneconomic or unsustainable. Microbial electrochemical systems are promising for removal and recovery of metal(loid)s from metal(loid)-laden wastewaters. In this communication, a bioelectrochemical system (BES) was designed and operated with selenium (Se) oxyanion at varied concentrations as terminal electron acceptor (TEA) for reduction of selenite (Se4+) to elemental selenium (Se0) in the abiotic cathode chamber. The influence of varied concentrations of Se4+ towards Se0 recovery at the cathode was also evaluated for its regulatory role on the electrometabolism of anode-respiring bacteria. This study observed 26.4% Se0 recovery (cathode; selenite removal efficiency: 73.6%) along with organic substrate degradation of 74% (anode). With increase in the initial selenite concentration, there was a proportional increase in the dehydrogenase activity. Bioelectrochemical characterization depicted increased anodic electrogenic performance with the influence of varied Se4+ concentrations as TEA and resulted in a maximum power density of 0.034 W/m2. The selenite reduction (cathode) was evaluated through spectroscopic, compositional and structural analysis. X-ray diffraction and Raman spectroscopy showed the amorphous nature, while Energy Dispersive X-ray spectroscopy confirmed precipitates of the deposited Se0 recovered from the cathode chamber. Scanning electron microscopic images clearly depicted the Se0 depositions (spherical shaped; sized approximately 200 nm in diameter) on the electrode and cathode chamber. This study showed the potential of BES in converting soluble Se4+ to insoluble Se0 at the abiotic cathode for metal recovery.

Physiology and Distribution of Archaeal Methanotrophs That Couple Anaerobic Oxidation of Methane with Sulfate Reduction.

In marine anaerobic environments, methane is oxidized where sulfate-rich seawater meets biogenic or thermogenic methane. In those niches, a few phylogenetically distinct microbial types, i.e., anaerobic methanotrophs (ANME), are able to grow through anaerobic oxidation of methane (AOM). Due to the relevance of methane in the global carbon cycle, ANME have drawn the attention of a broad scientific community for 4 decades. This review presents and discusses the microbiology and physiology of ANME up to the recent discoveries, revealing novel physiological types of anaerobic methane oxidizers which challenge the view of obligate syntrophy for AOM. An overview of the drivers shaping the distribution of ANME in different marine habitats, from cold seep sediments to hydrothermal vents, is given. Multivariate analyses of the abundance of ANME in various habitats identify a distribution of distinct ANME types driven by the mode of methane transport. Intriguingly, ANME have not yet been cultivated in pure culture, despite intense attempts. Further advances in understanding this microbial process are hampered by insufficient amounts of enriched cultures. This review discusses the advantages, limitations, and potential improvements for ANME laboratory-based cultivation systems.

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.

Performance evaluation of duplex constructed wetlands for the treatment of diesel contaminated wastewater.

A duplex constructed wetland (duplex-CW) is a hybrid system that combines a vertical flow (VF) CW as a first stage with a horizontal flow filter (HFF) as a second stage for a more efficient wastewater treatment as compared to traditional constructed wetlands. This study evaluated the potential of the hybrid CW system to treat influent wastewater containing diesel range organic compounds varying from C7 - C40 using a series of 12-week practical and numerical experiments under controlled conditions in a greenhouse (pH was kept at 7.0 ±â€¯0.2, temperature between 20 and 23° C and light intensity between 85 and 100-µmol photons m-2 sec-1 for 16 h d-1). The VF CWs were planted with Phragmites australis and were spiked with different concentrations of NH4+-N (10, 30 and 60 mg/L) and PO43--P (3, 6 and 12 mg/L) to analyse their effects on the degradation of the supplied petroleum hydrocarbons. The removal rate of the diesel range organics considering the different NH4+-N and PO43--P concentrations were simulated using Monod degradation kinetics. The simulated results compared well with the observed database. The results showed that the model can effectively be used to predict biochemical transformation and degradation of diesel range organic compounds along with nutrient amendment in duplex constructed wetlands.

Selenite reduction and ammoniacal nitrogen removal in an aerobic granular sludge sequencing batch reactor.

Simultaneous removal of selenite and ammonium by aerobic granular sludge was investigated to develop an improved biological treatment process for selenium rich wastewaters. Aerobic granules not previously exposed to selenite were able to remove selenite by converting it to elemental selenium (Se(0)) and simultaneously remove ammonium under different conditions in batch experiments. To achieve sustainable selenite and ammonium removal, an aerobic granular sludge reactor was operated in fill-and-draw mode with a cycle of anaerobic (8 h) and aeration (15 h) phases. Almost complete removal of different initial concentrations of selenite up to 100 µM was achieved in the anaerobic phase. Ammonium removal was severely inhibited when the granules were initially exposed to 1.27 mg L-1 selenite, but ammonium and total nitrogen removal efficiencies gradually improved to 100 and 98%, respectively, under selenite-reducing conditions. Selenite loading shifted ammonium removal occurring mainly during the anaerobic phase to both the anaerobic and aeration phases. Selenite was removed from the aqueous phase by converting it to nanoparticulate Se(0), which was entrapped in the granular sludge. Scanning electron microscop-energy dispersive X-ray spectroscopy and X-ray diffraction analysis confirmed the formation of Se(0) nanospheres and their retention in the granular sludge. The effluent Se ranged from 0.02 to 0.25 mg Se L-1, while treating up to 12.7 mg L-1 selenite, which is lower as compared to previous studies on selenite removal using activated sludge or anaerobic granular sludge. This study shows that aerobic granular sludge reactors are not only capable of removing toxic selenite, but offer improved treatment of Se-rich wastewaters.

Fate of heavy metals in vertical subsurface flow constructed wetlands treating secondary treated petroleum refinery wastewater in Kaduna, Nigeria.

This study examined the performance of pilot-scale vertical subsurface flow constructed wetlands (VSF-CWs) planted with three indigenous plants, i.e. Typha latifolia, Cyperus alternifolius, and Cynodon dactylon, in removing heavy metals from secondary treated refinery wastewater under tropical conditions. The T. latifolia-planted VSF-CW had the best heavy metal removal performance, followed by the Cyperus alternifolius-planted VSF-CW and then the Cynodon dactylon-planted VSF-CW. The data indicated that Cu, Cr, Zn, Pb, Cd, and Fe were accumulated in the plants at all the three VSF-CWs. However, the accumulation of the heavy metals in the plants accounted for only a rather small fraction (0.09-16%) of the overall heavy metal removal by the wetlands. The plant roots accumulated the highest amount of heavy metals, followed by the leaves, and then the stem. Cr and Fe were mainly retained in the roots of T. latifolia, Cyperus alternifolius, and Cynodon dactylon (TF < 1), meaning that Cr and Fe were only partially transported to the leaves of these plants. This study showed that VSF-CWs planted with T. latifolia, Cyperus Alternifolius, and Cynodon dactylon can be used for the large-scale removal of heavy metals from secondary refinery wastewater.

Nitrification by microalgal-bacterial consortia for ammonium removal in flat panel sequencing batch photo-bioreactors.

Ammonium removal from artificial wastewater by microalgal-bacterial consortia in a flat-panel reactor (FPR1) was compared with a microalgae-only flat-panel reactor (FPR2). The microalgal-bacterial consortia removed ammonium at higher rates (100±18mgNH4+-NL-1d-1) than the microalgae (44±16mgNH4+-NL-1d-1), after the system achieved a stable performance at a 2days hydraulic retention time. Nitrifiers present in the microalgae-bacteria consortia increased the ammonium removal: the ammonium removal rate by nitrifiers and by algae in FPR1 was, respectively, 50(±18) and 49(±22)mgNH4+-NL-1d-1. Apparently ammonium removal by algae was not significantly different between FPR1 and FPR2. The activity of the nitrifiers did not negatively affect the nitrogen uptake by algae, but improved the total ammonium removal rate of FPR1.

Lactic acid fermentation of human urine to improve its fertilizing value and reduce odour emissions.

During storage of urine, urea is biologically decomposed to ammonia, which can be lost through volatilization and in turn causes significant unpleasant smell. In response, lactic acid fermentation of urine is a cost-effective technique to decrease nitrogen volatilization and reduce odour emissions. Fresh urine (pH = 5.2-5.3 and NH4+-N = 1.2-1.3 g L-1) was lacto-fermented for 36 days in closed glass jars with a lactic acid bacterial inoculum from sauerkraut juice and compared to untreated, stored urine. In the lacto-fermented urine, the pH was reduced to 3.8-4.7 and the ammonium content by 22-30%, while the pH of the untreated urine rose to 6.1 and its ammonium content increased by 32% due to urea hydrolysis. The concentration of lactic acid bacteria in lacto-fermented urine was 7.3 CFU ml-1, suggesting that urine is a suitable growth medium for lactic acid bacteria. The odour of the stored urine was subjectively perceived by four people to be twice as strong as that of lacto-fermented samples. Lacto-fermented urine induced increased radish germination compared to stored urine (74-86% versus 2-31%). Adding a lactic acid bacterial inoculum to one week old urine in the storage tanks in a urine-diverting dry toilet reduced the pH from 8.9 to 7.7 after one month, while the ammonium content increased by 35%, probably due to the high initial pH of the urine. Given that the hydrolyzed stale urine has a high buffering capacity, the lactic acid bacterial inoculum should be added to the urine storage tank of a UDDT before urine starts to accumulate there to increase the efficiency of the lactic acid fermentation.

Biological removal of selenate and ammonium by activated sludge in a sequencing batch reactor.

Wastewaters contaminated by both selenium and ammonium need to be treated prior to discharge into natural water bodies, but there are no studies on the simultaneous removal of selenium and ammonium. A sequencing batch reactor (SBR) was inoculated with activated sludge and operated for 90days. The highest ammonium removal efficiency achieved was 98%, while the total nitrogen removal was 75%. Nearly a complete chemical oxygen demand removal efficiency was attained after 16days of operation, whereas complete selenate removal was achieved only after 66days. The highest total Se removal efficiency was 97%. Batch experiments showed that the total Se in the aqueous phase decreased by 21% with increasing initial ammonium concentration from 50 to 100mgL-1. This study showed that SBR can remove both selenate and ammonium via, respectively, bioreduction and partial nitrification-denitrification and thus offer possibilities for treating selenium and ammonium contaminated effluents.

Simultaneous removal of rotavirus and adenovirus from artificial ground water using hydrochar derived from swine feces.

Hydrothermal carbonization technology can convert fecal waste into a valuable carbonaceous product referred to as hydrochar. We investigated the potential of fecal waste-derived hydrochar as an adsorbent for virus removal in water treatment. Swine feces was hydrothermally treated under two conditions: at 180 °C for 2 h and 230 °C for 7 h. The resulting solid products (hydrochar) were evaluated as virus adsorbents in water treatment. Simultaneous removal of pathogenic rotavirus (RV) and human adenovirus (HAdV) was investigated using a sand column set-up of 10 cm bed height with and without hydrochar supplement (1.5%, w/w). The removal efficiency of both viruses in a hydrochar-amended column was >3 log (complete removal). The amount of virus released in deionized water when flushed into the virus-retaining columns indicated that the secondary energy minimum played a more important role in RV retention than that of HAdV. Zeta-potential and hydrophobicity measurements on hydrochar materials indicated that the improved virus removal performance of hydrochar-amended columns was induced by the provision of extra hydrophobic surfaces. This study provides evidence that fecal waste-derived hydrochar can be used as a competent virus adsorbent.

Recent advances in nutrient removal and recovery in biological and bioelectrochemical systems.

Nitrogen and phosphorous are key pollutants in wastewater to be removed and recovered for sustainable development. Traditionally, nitrogen removal is practiced through energy intensive biological nitrification and denitrification entailing a major cost in wastewater treatment. Recent innovations in nitrogen removal aim at reducing energy requirements and recovering ammonium nitrogen. Bioelectrochemical systems (BES) are promising for recovering ammonium nitrogen from nitrogen rich waste streams (urine, digester liquor, swine liquor, and landfill leachate) profitably. Phosphorus is removed from the wastewater in the form of polyphosphate granules by polyphosphate accumulating organisms. Alternatively, phosphorous is removed/recovered as Fe-P or struvite through chemical precipitation (iron or magnesium dosing). In this article, recent advances in nutrients removal from wastewater coupled to recovery are presented by applying a waste biorefinery concept. Potential capabilities of BES in recovering nitrogen and phosphorous are reviewed to spur future investigations towards development of nutrient recovery biotechnologies.

Effect of heavy metal co-contaminants on selenite bioreduction by anaerobic granular sludge.

This study investigated bioreduction of selenite by anaerobic granular sludge in the presence of heavy metals and analyzed the fate of the bioreduced selenium and the heavy metals. Selenite bioreduction was not significantly inhibited in the presence of Pb(II) and Zn(II). More than 92% of 79 mg/L selenite was removed by bioreduction even in the presence of 150 mg/L of Pb(II) or 400mg/L of Zn(II). In contrast, only 65-48% selenite was bioreduced in the presence of 150-400 mg/L Cd(II). Formation of elemental selenium or selenide varied with heavy metal type and concentration. Notably, the majority of the bioreduced selenium (70-90% in the presence of Pb and Zn, 50-70% in the presence of Cd) and heavy metals (80-90% of Pb and Zn, 60-80% of Cd) were associated with the granular sludge. The results have implications in the treatment of selenium wastewaters and biogenesis of metal selenides.

Recovery of molybdenum, nickel and cobalt by precipitation from the acidic leachate of a mineral sludge.

The objective of this study was to investigate the recovery potential of molybdenum (Mo), nickel (Ni) and cobalt (Co) from synthetic and real acidic leachate of a mineral sludge from a metal recycling plant by sulfide precipitation. The operational parameters (metal sulfide (M/S) ratio 0.1-1, agitation speed 0-100 rpm, contact time 15-120 min and pH 1-5) were optimized in batch conditions on synthetic metal leachate (0.5 M HNO3, Mo = 101.6 mg L(-1), Ni = 70.8 mg L(-1), Co = 27.1 mg L(-1)) with a 0.1 M Na2S solution. Additionally, recovery of the target metals was theoretically simulated with a chemical equilibrium model (Visual MINTEQ 3.0). The optimized Na2S precipitation of metals from the synthetic leachate resulted in the potential selective recovery of Mo at pH 1 (98% by modeling, 95% experimental), after simultaneous precipitation of Ni and Co as sulfide at pH 4 (100% by modeling, 98% experimental). Metal precipitation from the real leachate (18 M H2SO4, Mo = 10,160 mg L(-1), Ni = 7,080 mg L(-1), Co = 2,710 mg L(-1)) was performed with 1 M Na2S, and resulted in a maximal Mo recovery at pH 2 (50%), while maximal recoveries of Ni and Co were observed at pH 4 (56% and 60%, respectively). Real leachate gave a lower metals recovery efficiency compared with synthetic leachate, which can be attributed to changes in the pH, nature of leachant, co-precipitation of Zn and competition for S(2-) ions.

The effect of aeration and recirculation on a sand-based hybrid constructed wetland treating low-strength domestic wastewater.

The Duplex-constructed wetland (CW) is a hybrid system composed of a vertical flow (VF) CW on top of a horizontal flow filter (HFF). Each compartment is designed to play a different role: aerobic treatment in the VF CW due to intermittent feeding and anoxic treatment in the HFF due to saturated conditions. Three Duplex-CWs were used in this study: Control, Aerated and Recirculating. The role of each compartment was tested for pollutant removal and micro-invertebrate abundance. In all systems, the VF CW removed mainly organic matter, solids and NH4(+)-N. Pathogens were removed in both compartments. Likewise, total nitrogen removal occurred in both compartments, only the Recirculating HFF was not able to denitrify the nitrogen due to the slightly more oxic conditions as compared to the other systems. All systems met discharge guidelines for organic matter, but only the Control and Aerated systems met those for total nitrogen. At the applied loading rates, the pollutant removal was not significantly enhanced by the use of aeration and recirculation. Therefore, operation as in the Control system, without aeration or recirculation, is recommended for the tested Duplex-CWs. If artificial aeration will be used in CWs, the support material should be carefully selected to allow a proper air distribution.