Impacts of Chemical-Assisted Thermal Pretreatments on Methane Production from Fruit and Vegetable Harvesting Wastes: Process Optimization.

The increasing population creates excess pressure on the plantation and production of fruits and vegetables across the world. Consumption demand during the whole year has made production compulsory in the covered production system (greenhouse). Production, harvesting, processing, transporting, and distribution chains of fruit and vegetables have resulted in a huge amount of wastes as an alternative source to produce biofuels. In this study, optimization of two pretreatment processes (NaOH and HCl assisted thermal) was investigated to enhance methane production from fruit and vegetable harvesting wastes (FVHW) that originate from greenhouses. NaOH concentration (0-6.5%), HCl concentration (0-5%), reaction temperature (60-100 °C), solid content (1-5%), time of reaction (1-5 h), and mixing speed (0-500 rpm) were chosen in a wide range of levels to optimize the process in a broad design boundary and to evaluate the positive and negative impacts of independent variables along with their ranges. Increasing NaOH and HCl concentrations resulted in higher COD solubilization but decreased the concentration of soluble sugars that can be converted directly into methane. Thus, the increasing concentrations of NaOH and HCl in the pretreatments have resulted in low methane production. The most important independent variables impacting COD and sugar solubilization were found to be chemical concentration (as NaOH and HCl), solid content and reaction temperature for the optimization of pretreatment processes. The high amount of methane productions in the range of 222-365 mL CH4 gVS-1 was obtained by the simple thermal application without using chemical agents as NaOH or HCl. Maximum enhancement of methane production was 47-68% compared to raw FVHW when 5% solid content, 1-hour reaction time and 60-100 °C reaction temperature were applied in pretreatments.

Enhancement of corn stover conversion to carboxylates by extrusion and biotic triggers in solid-state fermentation.

Solid-state fermentation is a potential technology for developing lignocellulosic biomass-based biorefineries. This work dealt with solid-state fermentation for carboxylates production from corn stover, as building blocks for a lignocellulosic feedstock-based biorefinery. The effect of extrusion pretreatment, together with the action of a microbial consortia and hydrolytic enzymes as biotic triggers, was investigated on corn stover conversion, microbial metabolic pathways, and populations. The extrusion caused changes in the physical and morphological characteristics, without altering the biochemical composition of the corn stover. Extrusion also led to remarkable differences in the composition of the indigenous microbial population of the substrate. Consequently, it affected the structure of community developed after fermentation and the substrate conversion yield, which increased by 118% (from 23 ± 4 gCOD/kgVSi obtained with raw substrate to 51 ± 1 gCOD/kgVSi with extruded corn stover) with regard to self-fermentation experiments. The use of activated sludge as inoculum further increased the total substrate conversion into carboxylates, up to 60 ± 2 gCOD/kgVSi, and shaped the microbial communities (mainly composed of bacteria from the Clostridia and Bacteroidia classes) with subsequent homogenization of the fermentation pathways. The addition of hydrolytic enzymes into the reactors further increased the corn stover conversion, leading to a maximum yield of 142 ± 1 gCOD/kgVSi. Thus, extrusion pretreatment combined with the use of an inoculum and enzyme addition increased by 506% corn stover conversion into carboxylates. Beside biomass pretreatment, the results of this study indicated that biotic factor greatly impacted solid-state fermentation by shaping the microbial communities and related metabolic pathways.

Electrical Initialization of Electron and Nuclear Spins in a Single Quantum Dot at Zero Magnetic Field.

The emission of circularly polarized light from a single quantum dot relies on the injection of carriers with well-defined spin polarization. Here we demonstrate single dot electroluminescence (EL) with a circular polarization degree up to 35% at zero applied magnetic field. The injection of spin-polarized electrons is achieved by combining ultrathin CoFeB electrodes on top of a spin-LED device with p-type InGaAs quantum dots in the active region. We measure an Overhauser shift of several microelectronvolts at zero magnetic field for the positively charged exciton (trion X+) EL emission, which changes sign as we reverse the injected electron spin orientation. This is a signature of dynamic polarization of the nuclear spins in the quantum dot induced by the hyperfine interaction with the electrically injected electron spin. This study paves the way for electrical control of nuclear spin polarization in a single quantum dot without any external magnetic field.

Soft Microwave Pretreatment to Extract P-Hydroxycinnamic Acids from Grass Stalks.

The aim of this article is to provide an analysis of microwave effects on ferulic and coumaric acids (FA and CA, respectively) extraction from grass biomass (corn stalks and miscanthus). Microwave pretreatment using various solvents was first compared to conventional heating on corn stalks. Then, microwave operational conditions were extended in terms of incident power and treatment duration. Optimal conditions were chosen to increase p-hydroxycinnamic acids release. Finally, these optimal conditions determined on corn stalks were tested on miscanthus stalks to underlie the substrate incidence on p-hydroxycinnamic acids release yields. The optimal conditions-a treatment duration of 405 s under 1000 W-allowed extracting 1.38% FA and 1.97% CA in corn stalks and 0.58% FA and 3.89% CA in miscanthus stalks. The different bioaccessibility of these two molecules can explain the higher or lower yields between corn and miscanthus stalks.

Lime Pretreatment of Miscanthus: Impact on BMP and Batch Dry Co-Digestion with Cattle Manure.

In Europe, the agricultural biogas sector is currently undergoing fast developments, and cattle manure constitutes an important feedstock. Batch dry digester processes with leachate recirculation prove to be particularly interesting for small-scale plants. However, their startup being relatively slow, the process could be facilitated by co-digestion with energy crops. In this study, Miscanthus xgiganteus was chosen for its high biomass yields and low input requirements. The carbohydrate accessibility of this lignocellulosic biomass is limited but may be improved with alkali pretreatment. The efficiency of lime (CaO) pretreatment with low water addition on the biochemical methane potential (BMP) of miscanthus was investigated through two experimental designs (CaO concentrations ranged between 2.5 and 17.5% and pretreatment lasted 1, 3, or 5 days). The pretreated miscanthus was then co-digested with cattle manure in dry leach bed reactors. CaO pretreatments led to a 14⁻37% improvement of miscanthus BMP, and a 67⁻227% increase in the first-order kinetics constant; a high contact time was shown to favor methane production. According to these results and to industrial requirements, miscanthus was pretreated with 5 and 10% CaO for 5 days, then co-digested with manure in dry leach bed reactors. Nevertheless, the promising results of the BMP tests were not validated. This could be related to the high water absorption capacity of miscanthus.

Combination of Dry Milling and Separation Processes with Anaerobic Digestion of Olive Mill Solid Waste: Methane Production and Energy Efficiency.

This experimental work aims at investigating the effects of milling; sieving; and electrostatic separation on the biochemical methane potential of two olive pomaces from traditional olive oil extraction (M) and from a three-phase system (T). Sieving proved to be efficient for increasing the soluble chemical oxygen demand in the smallest fractions of the sieve of both M (62%) and T (78%) samples. The positive fraction following electrostatic separation also enhanced chemical oxygen demand (COD) solubilisation by 94%, in comparison to sample T milled at 4 mm. Sieve fractions with a size greater than 0.9 mm contained 33% and 47% less lipids for the M and T biomasses; respectively. Dry fractionation modified sample properties as well as lipid and fiber distribution. Concomitantly; milling increased the accessibility and facilitated the release of organic matter. The energy balance was positive after knife milling and sieving; while ball milling and ultrafine milling proved to be inefficient.

Two-stage alkaline-enzymatic pretreatments to enhance biohydrogen production from sunflower stalks.

Because of their rich composition in carbohydrates, lignocellulosic residues represent an interesting source of biomass to produce biohydrogen by dark fermentation. Nevertheless, pretreatments should be applied to enhance the solubilization of holocelluloses and increase their further conversion into biohydrogen. The aim of this study was to investigate the effect of thermo-alkaline pretreatment alone and combined with enzymatic hydrolysis to enhance biohydrogen production from sunflower stalks. A low increase of hydrogen potentials from 2.3 ± 0.9 to 4.4 ± 2.6 and 20.6 ± 5.6 mL of H2 g(-1) of volatile solids (VS) was observed with raw sunflower stalks and after thermo-alkaline pretreatment at 55 °C, 24 h, and 4% NaOH and 170 °C, 1 h, and 4% NaOH, respectively. Enzymatic pretreatment alone showed an enhancement of the biohydrogen yields to 30.4 mL of H2 g(-1) of initial VS, whereas it led to 49 and 59.5 mL of H2 g(-1) of initial VS when combined with alkaline pretreatment at 55 and 170 °C, respectively. Interestingly, a diauxic effect was observed with sequential consumption of sugars by the mixed cultures during dark fermentation. Glucose was first consumed, and once glucose was completely exhausted, xylose was used by the microorganisms, mainly related to Clostridium species.

Application of optimized alkaline pretreatment for enhancing the anaerobic digestion of different sunflower stalks varieties.

The use of lignocellulosic residues such as sunflower stalks (SS) for the production of bioenergy such as methane is a promising alternative to fossil fuels. However, their recalcitrant structure justifies the use of pretreatment to enhance the accessibility of holocelluloses and their further conversion into methane. First, different conditions of alkaline pretreatment (i.e. duration and NaOH concentration (g/100 g TS) at a fixed temperature of 55 degrees C) were tested to enhance the methane potential of the stalks of the Serin sunflower (193 mL of methane per gram of volatile solids (VS)). The greatest improvement to the methane potential (262 mL CH4 g(-1) VS) was observed at 55 degrees C, 24 h, 4 g NaOH/100 g TS. Fourier Transform Infrared spectra highlighted an accumulation of lignin in the digestate and the degradation of holocelluloses during the anaerobic process, both for pretreated and untreated SS. In a second stage, this optimum condition for alkaline pretreatment (55 degrees C, 24 h, 4 g NaOH/100 g TS) was applied to the stalks of three other varieties of sunflower. Alkaline pretreatment was effective in the delignification of the stalks of the different sunflower varieties, with lignin reduction varying from 23.3% to 36.3% VS. This reduction of lignin was concomitant with the enhancement of methane potential as compared to that of raw SS, with an increase ranging from 29% to 44% for the different SS.

Use of additives to improve collective biogas plant performances: A comprehensive review.

Nowadays, anaerobic digestion (AD) is being increasingly encouraged to increase the production of biogas and thus of biomethane. Due to the high diversity among feedstocks used, the variability of operating parameters and the size of collective biogas plants, different incidents and limitations may occur (e.g., inhibitions, foaming, complex rheology). To improve performance and overcome these limitations, several additives can be used. This literature review aims to summarize the effects of the addition of various additives in co-digestion continuous or semi-continuous reactors to fit as much as possible with collective biogas plant challenges. The addition of (i) microbial strains or consortia, (ii) enzymes and (iii) inorganic additives (trace elements, carbon-based materials) in digester is analyzed and discussed. Several challenges associated with the use of additives for AD process at collective biogas plant scale requiring further research work are highlighted: elucidation of mechanisms, dosage and combination of additives, environmental assessment, economic feasibility, etc.

Lactic acid fermentation of food waste as storage method prior to biohydrogen production: Effect of storage temperature on biohydrogen potential and microbial communities.

This study aims to investigate the impact of utilizing lactic acid fermentation (LAF) as storage method of food waste (FW) prior to dark fermentation (DF). LAF of FW was carried out in batches at six temperatures (4 °C, 10 °C, 23 °C, 35 °C, 45 °C, and 55 °C) for 15 days followed by biological hydrogen potential (BHP) tests. Different storage temperatures resulted in different metabolites distribution, with either lactate or ethanol being dominant (159.2 ± 20.6 mM and 234.4 ± 38.2 mM respectively), but no negative impact on BHP (averaging at 94.6 ± 25.1 mL/gVS). Maximum hydrogen production rate for stored FW improved by at least 57%. Microbial analysis showed dominance of lactic acid bacteria (LAB) namely Lactobacillus sp., Lactococcus sp., Weisella sp., Streptococcus sp. and Bacillus sp. after LAF. Clostridium sp. emerged after DF, co-existing with LAB. Coupling LAF as a storage method was demonstrated as a novel strategy of FW management for DF, for a wide range of temperatures.

Predictive models of biohydrogen and biomethane production based on the compositional and structural features of lignocellulosic materials.

In an integrated biorefinery concept, biological hydrogen and methane production from lignocellulosic substrates appears to be one of the most promising alternatives to produce energy from renewable sources. However, lignocellulosic substrates present compositional and structural features that can limit their conversion into biohydrogen and methane. In this study, biohydrogen and methane potentials of 20 lignocellulosic residues were evaluated. Compositional (lignin, cellulose, hemicelluloses, total uronic acids, proteins, and soluble sugars) as well as structural features (crystallinity) were determined for each substrate. Two predictive partial least square (PLS) models were built to determine which compositional and structural parameters affected biohydrogen or methane production from lignocellulosic substrates, among proteins, total uronic acids, soluble sugars, crystalline cellulose, amorphous holocelluloses, and lignin. Only soluble sugars had a significant positive effect on biohydrogen production. Besides, methane potentials correlated negatively to the lignin contents and, to a lower extent, crystalline cellulose showed also a negative impact, whereas soluble sugars, proteins, and amorphous hemicelluloses showed a positive impact. These findings will help to develop further pretreatment strategies for enhancing both biohydrogen and methane production.

Screening and Application of Ligninolytic Microbial Consortia to Enhance Aerobic Degradation of Solid Digestate.

Recirculation of solid digestate through digesters has been demonstrated to be a potential simple strategy to increase continuous stirred-tank reactor biogas plant efficiency. This study extended this earlier work and investigated solid digestate post-treatment using liquid isolated ligninolytic aerobic consortia in order to increase methane recovery during the recirculation. Based on sampling in several natural environments, an enrichment and selection method was implemented using a Lab-scale Automated and Multiplexed (an)Aerobic Chemostat system to generate ligninolytic aerobic consortia. Then, obtained consortia were further cultivated under liquid form in bottles. Chitinophagia bacteria and Sordariomycetes fungi were the two dominant classes of microorganisms enriched through these steps. Finally, these consortia where mixed with the solid digestate before a short-term aerobic post-treatment. However, consortia addition did not increase the efficiency of aerobic post-treatment of solid digestate and lower methane yields were obtained in comparison to the untreated control. The main reason identified is the respiration of easily degradable fractions (e.g., sugars, proteins, amorphous cellulose) by the selected consortia. Thus, this paper highlights the difficulties of constraining microbial consortia to sole ligninolytic activities on complex feedstock, such as solid digestate, that does not only contain lignocellulosic structures.

Kinetics and reversibility of micropollutant sorption in sludge.

The fate of micropollutants throughout wastewater treatment systems is highly dependent on their sorption interactions with sludge matter. In this study, both the sorption and desorption kinetics of polycyclic aromatic hydrocarbons (PAHs) in activated sludge were shown to be very rapid in comparison to biodegradation kinetics. It was concluded that PAH transfer does not limit their biodegradation and that their fate is governed by the sorption/desorption equilibrium state. The effect of contact time between sludge and PAHs was also investigated. It was shown that aging did not influence the sorption/desorption equilibrium although PAH losses during aging suggest that sequestration phenomena had occurred. This implies that for PAH sorption assessment within treatment processes there is no need to include a contact time dimension. As a consequence, thanks to an innovative approach taking into account sorption equilibria and sequestration, this work has demonstrated that studies in the literature which, in main, deal with micropollutant sorption in sewage sludge with only a short contact time can be extrapolated to real systems in which sorption, desorption and aging occur.

Effect of coupling alkaline pretreatment and sewage sludge co-digestion on methane production and fertilizer potential of digestate.

This study aims at investigating how organic waste co-digestion coupled with alkaline pretreatment can impact the methane production and agronomic value of produced digestates. For this purpose, sludge alone and mixed with olive pomace or macroalgal residues were subjected to anaerobic digestion with and without alkaline pretreatment. In addition, co-digestion of pretreated sludge with raw substrates was also carried out and compared to the whole mixture pretreatment. KOH pretreatment enhanced methane production by 39%, 15% and 49% from sludge, sludge mixed with olive pomace and sludge mixed with macroalgal residues, respectively. The digestates were characterised according to their physico-chemical and agronomic properties. They were then applied as biofertilizers for tomato growth during the first vegetative stage (28 days of culture). Concentrations in chlorophyll a and carotenoids in tomato plants, following sludge digestate addition, rose by 46% and 41% respectively. Sludge digestate enhanced tomato plant dry weight by 87%, while its nitrogen content increased by 90%. The impact of nitrogen and phosphorus contents in the digestate was strongest on tomato plant dry weight, thus explaining the efficiency of sludge digestate relative to other types of digestate. However, when methane production is considered, the combination of pre-treatment with co-digestion of macroalgal residues and sludge appears most beneficial for maximizing energy recovery and for biofertilizer generation.

Evaluation of agronomic properties of digestate from macroalgal residues anaerobic digestion: Impact of pretreatment and co-digestion with waste activated sludge.

The aim of this paper is to investigate the impact of pretreating macroalgal residue (MAR) from agar-agar extraction and its co-digestion with sewage sludge on methane production and the agronomic quality of the digestates produced. First, different pretreatments were assessed on BMP tests. Among milling technologies used, knife milling with a 4 mm-screen improved methane production by 25%. The MAR was then knife milled before alkaline, acid and thermal pretreatment. KOH pretreatment (5% TS basis, 25 °C for 2 days) led to the highest methane improvement. It was applied to semi-continuous anaerobic digestion and methane production achieved 237 Nml/gVS which was 20% higher than the control (198 Nml/gVS). In comparison to MAR mono-digestion, co-digestion with thickened activated sludge produced less methane (184 Nml/gVS) but reduced H2S emission by 91%. None of the digestates was toxic for the germination or growth of wheat and tomato plants. Particularly, co-digestion had the highest impact on tomato plant dry weight (+94% compared to soil alone) mainly due to the phosphorous brought by sludge. However, the impact of alkaline pretreatment on plant growth was not significant.

Mild microwaves, ultrasonic and alkaline pretreatments for improving methane production: Impact on biochemical and structural properties of olive pomace.

This study aims to investigate the effects of microwaves, ultrasonic and alkaline pretreatments on olive pomace properties and its biomethane potential. Alkaline pretreatment was found to reduce lipid and fiber contents (especially lignin) and to increase soluble matter. The alkali pretreatment at a dose of 8% (w/w TS) under 25 °C and for 1 day removed 96% of initial lipids from the solid olive pomace. Unlike NaOH addition, mild microwaves and ultrasonic pretreatments had no impact on lignin. However, in the case of long microwaves pretreatment (450 W-10 min), cellulose and lignin contents were reduced by 50% and 26% respectively. Similarly, the combination of ultrasonic and alkali reagent showed a positive effect on fiber degradation and lipid solubilization as well as a positive impact on methane production. Statistical analysis highlighted the correlation between NaOH dose, solubilization and methane production. The alkaline pretreatment at ambient temperature appeared the most energetically efficient.

Dataset of organic sample near infrared spectra acquired on different spectrometers.

This dataset presents 127 raw near infrared spectra of different organic samples acquired on three different spectrometers in three different labs. An example of data processing is shown to create six spectra transfer models between the three spectrometers (two by two). In order to build and validate these transfer models, the dataset was split into two sets of spectra: a first set was used to compute six spectra transfer models thanks to the Piecewise Direct standardisation function (PDS). A second set of spectra, independent of the first one was used to validate transfer models. Spectrum treatments and models were created on ChemFlow (https://vm-chemflow-francegrille.eu/), a free online chemometric software that includes all the necessary functions.

Removal of polycyclic aromatic hydrocarbons (PAH) during anaerobic digestion with recirculation of ozonated digested sludge.

PAH are particularly monitored because of their carcinogenic properties and their ubiquity in the environment. Their presence in municipal sewage sludge is a major problem due to the environmental risks associated with the sludge spreading on agricultural soils. The objective of this work was to asses the removal of PAH naturally present in sludge by continuous anaerobic digestion with recirculation of ozonated sludge. Recirculation of ozonated digested sludge allowed to enhance PAH removals, the highest efficiency was obtained with the highest ozone dose (0.11gO(3)/g(TS)). In order to study the effect of recirculation, a reactor was operated without recirculation but was fed with a mixture of raw and ozonated digested sludge. This process led to the best performances in terms of PAH and solid removals. This pointed out some accumulation of nonbiodegradable or recalcitrant compounds during recirculation assay. Smallest and most soluble compounds presented the highest biodegradation efficiencies.

Solid-state anaerobic digestion of wheat straw: Impact of S/I ratio and pilot-scale fungal pretreatment.

Solid State Anaerobic Digestion (SSAD) of fungal pretreated wheat straw was evaluated in a leach bed reactor. During a first experiment, the effect of Substrate/Inoculum (S/I) ratios on the start-up phase was investigated. High S/I increased methane productivity but also raised the risk of reactor failure due to Volatile Fatty Acid (VFA) accumulation. With S/I ratios between 1.2 and 3.6 (Volatile Solid (VS) basis), the SSAD start-up using wheat straw was successful. Moreover, reactors were able to recover from acidification when the Total VFA/alkalinity ratio was lower than 2 gHAc_eq/gCaCO3, with VFA concentrations lower than 10 g/L and a pH close to 5.5. The conventional threshold of 0.6 gHAc_eq/gCaCO3 for stable wet AD is therefore not adapted to SSAD. During a second experiment, after the wheat straw was submitted to a fungal pretreatment in a non-sterile pilot-scale reactor, it was digested with an S/I ratio of 2.8-2.9. Under batch SSAD conditions, the biodegradability of pretreated wheat straw was slightly improved in comparison to the control (254 versus 215 NmL/g VS, respectively). Considering mass losses occurring during the pretreatment step, suboptimal pretreatment conditions caused a slightly lower methane production (161 versus 171 NmL/gTSinitial after 60-days anaerobic digestion). Nevertheless, pretreatment improved the start-up phase with lower acidification relative to controls. It would be particularly beneficial to improve the methane production in reactors with short reaction times.

Assessment of cross-flow filtration as microalgae harvesting technique prior to anaerobic digestion: Evaluation of biomass integrity and energy demand.

In the present study, the effect of cross-flow filtration (CFF) on the overall valorization of Chlorella spp. microalgae as biogas was assessed. The effect of CFF on microalgae cell integrity was quantified in terms of viability which was correlated with the anaerobic biodegradability. The viability dropped as the biomass concentration increased, whereas anaerobic biodegradability increased linearly with the viability reduction. It was hypothesized that a stress-induced release and further accumulation of organic polymers during CFF increased the flux resistance which promoted harsher shear-stress conditions. Furthermore, the volume reduction as the concentration increased entailed an increase in the specific energy supply to the biomass. The energy demand was positive in the whole range of concentrations studied, yielding an overall energy efficiency as high as 22.9% for the highest concentration studied. Specifically, heat requirements were lower than electricity requirements only when the biomass concentrations exceeded 10 g COD·L-1.