Synthesis of Cobalt-Based Nanoparticles as Catalysts for Methanol Synthesis from CO2 Hydrogenation.

The increasing emission of carbon dioxide into the atmosphere has urged the scientific community to investigate alternatives to alleviate such emissions, being that they are the principal contributor to the greenhouse gas effect. One major alternative is carbon capture and utilization (CCU) toward the production of value-added chemicals using diverse technologies. This work aims at the study of the catalytic potential of different cobalt-derived nanoparticles for methanol synthesis from carbon dioxide hydrogenation. Thanks to its abundance and cost efficacy, cobalt can serve as an economical catalyst compared to noble metal-based catalysts. In this work, we present a systematic comparison among different cobalt and cobalt oxide nanocomposites in terms of their efficiency as catalysts for carbon dioxide hydrogenation to methanol as well as how different supports, zeolites, MnO2, and CeO2, can enhance their catalytic capacity. The oxygen vacancies in the cerium oxide act as carbon dioxide adsorption and activation sites, which facilitates a higher methanol production yield.

Addressing the gaseous and odour emissions gap in decentralised biowaste community composting.

Composting has demonstrated to be an effective and sustainable technology to valorise organic waste in the framework of circular economy, especially for biowaste. Composting can be performed in various technological options, from full-scale plants to community or even individual composters. However, there is scarce scientific information about the potential impact of community composting referred to gaseous emissions. This work examines the emissions of methane and nitrous oxide as main GHG, ammonia, VOC and odours from different active community composting sites placed in Spain, treating kitchen, leftovers and household biowaste. Expectedly, the gaseous emissions have an evident relation with the composting progress, represented mainly by its decrease as temperature or biological activity decreases. GHG and odour emission rates ranged from 5.3 to 815.2 mg CO2eq d-1 kg-1VS and from 69.8 to 1088.5 ou d-1 kg-1VS, respectively, generally being lower than those find in open-air full-scale composting. VOC characterization from the community composting gaseous emissions showed a higher VOC families' distribution in the emissions from initial composting phases, even though terpenes such as limonene, α-pinene and ß-pinene were the most abundant VOC along the composting process occurring in the different sites studied. The results presented in this study can be the basis to evaluate systematically and scientifically the numerous current projects for a worldwide community composting implementation in decentralised biowaste management schemes.

Exploring biorefinery alternatives for biowaste valorization: a techno-economic assessment of enzymatic hydrolysis coupled with anaerobic digestion or solid-state fermentation for high-value bioproducts.

Enzymatic hydrolysis of organic waste is gaining relevance as a complementary technology to conventional biological treatments. Moreover, biorefineries are emerging as a sustainable scenario to integrate waste valorization and high-value bioproducts production. However, their application on municipal solid waste is still limited. This study systematically evaluates the techno-economic feasibility of the conversion of the organic fraction of municipal solid waste (OFMSW) into high-value bioproducts through enzymatic hydrolysis. Two key variables are examined: (a) the source of the enzymes: commercial or on-site produced using OFMSW, and (b) the treatment of the solid hydrolyzate fraction: solid-state fermentation (SSF) for the production of biopesticides or anaerobic digestion for the production of energy. As a result, four different biorefinery scenarios are generated and compared in terms of profitability. Results showed that the most profitable scenario was to produce enzymes on-site and valorize the solid fraction via SSF, with an internal rate of return of 13%. This scenario led to higher profit margins (74%) and a reduced payback time (6 years), in contrast with commercial enzymes that led to an unprofitable biorefinery. Also, the simultaneous production of higher-value bioproducts and energy reduced the economic dependence of OFMSW treatment on policy instruments while remaining energetically self-sufficient. The profitability of the biorefinery scenarios evaluated was heavily dependent on the enzyme price and the efficiency of the anaerobic digestion process, highlighting the importance of cost-efficient enzyme production alternatives and high-quality OFMSW. This paper contributes to understanding the potential role of enzymes in future OFMSW biorefineries and offers economical insights on different configurations.

Techno-economic analysis to assess enzyme origin and solid hydrolysate fate.The viability of enzymatic hydrolysis depends on the cost and origin of enzymes.On-site produced enzymes cut payback time to 6 years, elevating profits by 74%.Anaerobic digestion and solid-state fermentation can be complementary technologies.High-value bioproducts are key to making organic waste biorefineries profitable.

Recent Advances in the Catalytic Conversion of Methane to Methanol: From the Challenges of Traditional Catalysts to the Use of Nanomaterials and Metal-Organic Frameworks.

Methane and carbon dioxide are the main contributors to global warming, with the methane effect being 25 times more powerful than carbon dioxide. Although the sources of methane are diverse, it is a very volatile and explosive gas. One way to store the energy content of methane is through its conversion to methanol. Methanol is a liquid under ambient conditions, easy to transport, and, apart from its use as an energy source, it is a chemical platform that can serve as a starting material for the production of various higher-value products. Accordingly, the transformation of methane to methanol has been extensively studied in the literature, using traditional catalysts as different types of zeolites. However, in the last few years, a new generation of catalysts has emerged to carry out this transformation with higher conversion and selectivity, and more importantly, under mild temperature and pressure conditions. These new catalysts typically involve the use of a highly porous supporting material such as zeolite, or more recently, metal-organic frameworks (MOFs) and graphene, and metallic nanoparticles or a combination of different types of nanoparticles that are the core of the catalytic process. In this review, recent advances in the porous supports for nanoparticles used for methane oxidation to methanol under mild conditions are discussed.

Advances, trends and challenges in the use of biochar as an improvement strategy in the anaerobic digestion of organic waste: a systematic analysis.

A recently strategy applied to anaerobic digestion (AD) is the use of biochar (BC) obtained from the pyrolysis of different organic waste. The PRISMA protocol-based review of the most recent literature data from 2011-2022 was used in this study. The review focuses on research papers from Scopus® and Web of Knowledge®. The review protocol used permits to identify 169 articles. The review indicated a need for further research in the following challenges on the application of BC in AD: i) to increase the use of BC in developing countries, which produce large and diverse amounts of waste that are the source of production of this additive; ii) to determine the effect of BC on the AD of organic waste under psychrophilic conditions; iii) to apply tools of machine learning or robust models that allow the process optimization; iv) to perform studies that include life cycle and technical-economic analysis that allow identifying the potential of applying BC in AD in large-scale systems; v) to study the effects of BC on the agronomic characteristics of the digestate once it is applied to the soil and vi) finally, it is necessary to deepen in the effect of BC on the dynamics of nitrogen and microbial consortia that affect AD, considering the type of BC used. In the future, it is necessary to search for new solutions in terms of the transport phenomena that occurs in AD with the use of BC using robust and precise mathematical models at full-scale conditions.

Filling in the gaps in biowaste biorefineries: The use of the solid residue after enzymatic hydrolysis for the production of biopesticides through solid-state fermentation.

Alternative production processes using waste are necessary to preserve non-renewable resources and prevent scarcity of materials for future generations. Biowaste, the organic fraction of municipal solid waste, is abundant and easily available. It can be fractionated into building blocks for which fermentative processes can be designed. By using solid-state fermentation, this paper proposes a method of valorizing biowaste's residual solid fraction after enzymatic hydrolysis. In a 22 L bioreactor, two digestates from anaerobic digestion processes were evaluated as cosubstrates to modify the acidic pH of the solid residue after enzymatic hydrolysis and promote the growth of the bacterial biopesticide producer Bacillus thuringiensis. Regardless of the cosubstrate used, the final microbial populations were similar indicating microbial specialization. The final product contained 4 × 108 spores per gram of dry matter and also crystal proteins of Bacillus thuringiensis var israelensis, which have insecticidal activity against pests. This method allows for the sustainable use of all materials liberated during the enzymatic hydrolysis of biowaste, including residual solids.

Magnetite-based nanoparticles and nanocomposites for recovery of overloaded anaerobic digesters.

The effect of magnetite nanoparticles and nanocomposites (magnetite nanoparticles impregnated into graphene oxide) supplement on the recovery of overloaded laboratory batch anaerobic reactors was assessed using two types of starting inoculum: anaerobic granular sludge (GS) and flocculent sludge (FS). Both nanomaterials recovered methane production at a dose of 0.27 g/L within 40 days in GS. Four doses of magnetite nanoparticles from 0.075 to 1 g/L recovered the process in FS systems between 30 and 50 days relaying on the dose. The presence of nanomaterials helped to reverse the effect of volatile fatty acids inhibition and enabled microbial communities to recover but also favoured the development of certain microorganisms over others. In GS reactors, the methanogenic population changed from being mostly acetoclastic (Methanothrix soehngenii) to being dominated by hydrogenotrophic species (Methanobacterium beijingense). Nanomaterial amendment may serve as a preventative measure or provide an effective remedial solution for system recovery following overloading.

Microbial biosurfactants: a review of recent environmental applications.

Microbial biosurfactants are low-molecular-weight surface-active compounds of high industrial interest owing to their chemical properties and stability under several environmental conditions. The chemistry of a biosurfactant and its production cost are defined by the selection of the producer microorganism, type of substrate, and purification strategy. Recently, biosurfactants have been applied to solve or contribute to solving some environmental problems, with this being their main field of application. The most referenced studies are based on the bioremediation of contaminated soils with recalcitrant pollutants, such as hydrocarbons or heavy metals. In the case of heavy metals, biosurfactants function as chelating agents owing to their binding capacity. However, the mechanism by which biosurfactants typically act in an environmental field is focused on their ability to reduce the surface tension, thus facilitating the emulsification and solubilization of certain pollutants (in-situ biostimulation and/or bioaugmentation). Moreover, despite the low toxicity of biosurfactants, they can also act as biocidal agents at certain doses, mainly at higher concentrations than their critical micellar concentration. More recently, biosurfactant production using alternative substrates, such as several types of organic waste and solid-state fermentation, has increased its applicability and research interest in a circular economy context. In this review, the most recent research publications on the use of biosurfactants in environmental applications as an alternative to conventional chemical surfactants are summarized and analyzed. Novel strategies using biosurfactants as agricultural and biocidal agents are also presented in this paper.

Multipoint characterization of the emission of odour, volatile organic compounds and greenhouse gases from a full-scale membrane-based municipal WWTP.

Different environmental and social concerns can arise due to the generation of gaseous emissions during the treatment of urban wastewater. However, there is not an extensive knowledge about which are the main potential odour and greenhouse gas (GHG) emission sources in a wastewater treatment plant (WWTP) and their variability. In this study, a multipoint characterization of the gaseous emissions generated in a full-scale municipal WWTP located in Barcelona was conducted, aiming at identifying the main odour and GHG emission sources. The WWTP under study treats an average inlet flow of 33,000 m3 d-1 using a Ludzack-Ettinger system with Membrane BioReactor (MBR) technology, and it has installed a gas caption and treatment system consisting of a biotrickling filter followed by a conventional biofilter to treat part of the off-gases produced during the wastewater treatment. For this work, gaseous emissions characterization campaigns were conducted to assess the proper performance of the gas treatment unit and to estimate the emission factors referred to odorants and GHGs for the different emission sources and to assess the proper performance of the gas treatment system. Besides, a chemical characterization of the different volatile organic compounds (VOC) present in the gaseous emissions was performed through TD-GC/MS. The main potential odour sources were the reception tank, the barscreens building and the primary settler, where odour concentrations were in the range of 1300 and 2600 ou·m-3. Moreover, GHG emissions were found during the primary treatment and in the MBR units, ranging from 2.21 to 68,217.13 mg CO2eq·m-3. Different VOCs such as aromatic hydrocarbons, alkanes and ketones were found in the gaseous emissions with a high variability among all the emission sources. The results obtained are valuable indicators that can be used to develop odour and GHG mitigation strategies in WWTPs and to estimate the environmental impact of these facilities.

Conversion of Carbon Dioxide into Methanol Using Cu-Zn Nanostructured Materials as Catalysts.

Nowadays, there is a growing awareness of the great environmental impact caused by the enormous amounts of carbon dioxide emitted. Several alternatives exist to solve this problem, and one of them is the hydrogenation of carbon dioxide into methanol by using nanomaterials as catalysts. The aim of this alternative is to produce a value-added chemical, such as methanol, which is a cheaply available feedstock. The development of improved materials for this conversion reaction and a deeper study of the existing ones are important for obtaining higher efficiencies in terms of yield, conversion, and methanol selectivity, in addition to allowing milder reaction conditions in terms of pressure and temperature. In this work, the performance of copper, zinc, and zinc oxide nanoparticles in supported and unsupported bimetallic systems is evaluated in order to establish a comparison among the different materials according to their efficiency. For that, a packed bed reactor operating with a continuous gas flow is used. The obtained results indicate that the use of bimetallic systems combined with porous supports, such as zeolite and activated carbon, is beneficial, thus improving the performance of unsupported materials by four times.

Enzymatic hydrolysis of the organic fraction of municipal solid waste: Optimization and valorization of the solid fraction for Bacillus thuringiensis biopesticide production through solid-state fermentation.

To reach a more sustainable society, the implementation of a circular economy perspective in municipal waste management becomes essential. In this work, the enzymatic hydrolysis of source-separated organic fraction of municipal solid waste (OFMSW) has been optimized as a sugar-releasing step. A liquid sugar concentrate, with a maximum reducing sugar concentration of 50.56 g L-1, and a solid hydrolyzed fraction were obtained. The effect of the harshness of the hydrolysis conditions was evaluated on the performance of the resulting solid fraction as a substrate for Bacillus thuringiensis biopesticide production through solid-state fermentation. A production of 3.9 × 108 viable cells g-1 dry matter with a 33% sporulation ratio was achieved for milder hydrolysis conditions, highlighting the potential of the solid fraction of hydrolysis as a substrate of SSF processes. The proposed valorization pathway for the OFMSW results in a sugar concentrate with potential for fermentative processes and a fermented solid containing biopesticides from Bacillus thuringiensis.

Scanning agro-industrial wastes as substrates for fungal biopesticide production: Use of Beauveria bassiana and Trichoderma harzianum in solid-state fermentation.

As a waste valorisation option, agro-industrial residues (rice husk, apple pomace, whisky draff, soy fiber, rice fiber, wheat straw, beer draff, orange peel and potato peel) were tested as feasible substrates for fungal conidia production. Solid-state fermentation tests were conducted at laboratory scale (100 g) with Beauveria bassiana or Trichoderma harzianum which conidia are reported to have biopesticide properties. Conidia concentrations with all substrates were at least two orders of magnitude above inoculum except for both fibers, thus demonstrating the possibilities of the proposed waste recovery option. Highest productions were at least 1 × 109 conidia g-1 dry matter for Beauveria bassiana using rice husk or potato peel and higher than 5 × 109 conidia g-1 dry matter for Trichoderma harzianum using beer draff, potato peel or orange pomace. Principal component analysis has been used to understand which parameters affect the most fungal conidia production for an easier evaluation of other similar wastes, being air-filled porosity and initial pH for Beauveria bassiana and cumulative oxygen consumption, initial moisture and total sugar content for Trichoderma harzianum.

Sustained effect of zero-valent iron nanoparticles under semi-continuous anaerobic digestion of sewage sludge: Evolution of nanoparticles and microbial community dynamics.

The effects of adding zero-valent iron nanoparticles (nZVI) on the physicochemical, biological and biochemical responses of a semi-continuous anaerobic digestion of sewage sludge have been assessed. Two sets of consecutive experiments of 103 and 116 days, respectively, were carried out in triplicate. nZVI were magnetically retained in the reactors, and the effect of punctual doses (from 0.27 to 4.33 g L-1) over time was studied. Among the different parameters monitored, only methane content in the biogas was significantly higher when nZVI was added. However, this effect was progressively lost after the addition, and in 5-7 days, the methane content returned to initial values. The increase in the oxidation state of nanoparticles seems to be related to the loss of effect over time. Higher dose (4.33 g L-1) sustained positive effects for a longer time along with higher methane content, but this fact seems to be related to microbiome acclimation. Changes in microbial community structure could also play a role in the mechanisms involved in methane enhancement. In this sense, the microbial consortium analysis reported a shift in the balance among acetogenic eubacterial communities, and a marked increase in the relative abundance of members assigned to Methanothrix genus, recognized as acetoclastic species showing high affinity for acetate, which explain the rise in methane content in the biogas. This research demonstrates that biogas methane enrichment in semicontinuous anaerobic digesters can be achieved by using nZVI nanoparticles, thus increasing energy production or reducing costs of a later biogas upgrading process.

Valorization of agro-industrial wastes by producing 2-phenylethanol via solid-state fermentation: Influence of substrate selection on the process.

2-phenylethanol (2-PE) is a value-added compound widely used in industry due to its rose-like odor and antibacterial properties that can be bioproduced using wastes as raw materials. This study presents the valorization of nine agro-industrial wastes as potential substrates for 2-PE production using an isolated 2-PE producer Pichia kudriavzevii, and the solid-state fermentation (SSF) technology as an alternative approach. The assessed substrates comprised wastes of varied traits such that each of them provided different characteristics to the fermentation. Thus, by using a principal component analysis (PCA), it was possible to identify the most significant characteristics associated with the substrates affecting the 2-PE production. Results show that L-phenylalanine biotransformation was more efficient than de novo synthesis for producing 2-PE. Besides, from the evaluated set, the maximum 2-PE production was achieved with red apple pomace, reaching 1.7 and 25.2 mg2PE per gram of used waste through de novo and L-phenylalanine biotransformation, respectively. In that scenario, volumetric productivity and precursor yield were 39.6 mg2PE L-1h-1 and 0.69 g2PE per gram of L-phenylalanine added, respectively. From the PCA, it was identified that the reducing sugars content of the substrate, the air-filled porosity of the bed and the L-phenylalanine availability were the most critical parameters (associated with the substrates) influencing the microbial activity and 2-PE production. These results suggest that the desirable traits a solid media needs for promoting 2-PE production via SSF could be reached by using a combination of wastes in a synergistic approach.

Adding value to home compost: Biopesticide properties through Bacillus thuringiensis inoculation.

Home and community composting are considered potential tools for the self-management of organic waste. The production of added value products from biowaste is an encouraging step further to valorise this waste stream. To increase the profits of homemade compost, this paper presents a strategy to produce enriched home compost with biopesticide properties through a simple and low-cost process. Bacillus thuringiensis (Bt) was inoculated in a home composter bin through a solid inoculum previously prepared using the same waste as substrate. The process was monitored and compared with a home composting control process without inoculation. Final composts were analysed and compared in terms of physicochemical and microbiological properties, respiration and germination indices, indicating the suitability of both to be used as organic amendments. Also, a standardized toxicity test proved that Bt-enriched compost can be safely applied to the soil. Microbiological analysis revealed highly diverse communities in both cases, with limited differences at phylum taxonomic level, but dissimilar relative abundances of species within phylum. Bacteroidetes and Proteobacteria were dominant, with the presence of species able to transform organic matter from vegetal origin, but not usually related to compost. Bt-cristal toxin was clearly present in Bt-enriched compost, indicating the coexistence of Bt with the different microbial populations till the end of the composting process. Although Bt has been widely investigated due to its biopesticide properties, the incorporation of this microorganism to home composting level has not been previously reported.

Rice husk as a source for fungal biopesticide production by solid-state fermentation using B. bassiana and T. harzianum.

Solid-state fermentation using rice husk as substrate with either Beauveria bassiana or Trichoderma harzianum was conducted on batch reactors at laboratory scale to establish optimal conditions for spore production. Time course tests were performed to determine maximum spore production time, which was 7.7 days for Beauveria bassiana and 5.7 days for Trichoderma harzianum. The effect of moisture, inoculum concentration, airflow rate, temperature and C/N ratio on spore production was evaluated by two Box-Behnken experimental designs. Final spore concentrations ranged from 2.0 × 108 to 2.0 × 109 spores g-1 dry matter. Main factors influencing spore production were moisture (optimum values of 55-60% for Trichoderma harzianum and 65-70 for Beauveria bassiana) and temperature (25 °C). The effect of mixing enhanced Trichoderma harzianum spore production while influencing negatively in the case of Beauveria bassiana. Robustness of the process has been demonstrated through statistical analysis using box-plots.

Filling in sewage sludge biodrying gaps: Greenhouse gases, volatile organic compounds and odour emissions.

In the present work, a complete study of the sewage sludge (SS) biodrying technology was conducted at bench-scale, aiming at assessing its performance and providing a valuable insight into the different gaseous emission patterns found for greenhouse gases (GHG) and odorant pollutants. As process key parameters, temperature, specific airflow, dynamic respiration index, final moisture content and Lower Calorific Value (LCV) were evaluated. At the end of the biodrying, a product with a 35.9% moisture content and a LCV of 7.1 MJ·kg-1product was obtained. GHGs emission factor was 28.22 kgCO2eq per Mg of initial mass of dry matter in the SS (DM0-SS). During the biodrying process, maximum odour concentration measured was 3043 ou·m-3 and the estimated odour emission factor of the biological treatment was 3.10E + 07 ou per Mg DM0-SS. Finally, VOCs were completely identified and quantified. The most abundant VOCs found in the biodrying gaseous emissions were terpenes, sulphur-compounds and ketones.

The use of magnetic iron oxide based nanoparticles to improve microalgae harvesting in real wastewater.

A novel approach for harvesting Scenedesmus sp. microalgae from real wastewater by using adsorbents of magnetite-based nanoparticles (Fe3O4 NPs) was tested in this study for the first time for this microalgae. Using these NPs, the harvesting efficiency was even higher than 95%. The optimal conditions (0.14 gNPs/L, a short magnetic separation time of only 8 min and 27 min of contact time) were found using the response surface methodology. The best fitting of the adsorption equilibrium results was achieved by the Langmuir isotherm model, and the maximum adsorption capacity for Scenedesmus sp. reached 3.49 g dry cell weight (DCW)/g Fe3O4 NPs. Zeta potential measurements and the Dubinin-Radushkevich isotherm model analysis pointed out that the main adsorption mechanism between Scenedesmus sp. cells and Fe3O4 NPs was electrostatic interaction. Finally, Fe3O4 NPs were six times successfully reused by combining an alkaline treatment with an ultrasonication process, which implies microalgae lysis. The results herein obtained highlight the potential for magnetic separation of microalgae from wastewater, which is capable of reaching a high harvesting efficiency in a very short time.

A systematic study on the VOCs characterization and odour emissions in a full-scale sewage sludge composting plant.

Sewage sludge management is known to cause odour impact over the environment. However, an information gap exists about odour emissions quantification from different treatment strategies. In the present work, odorous emissions generated in a full-scale sewage sludge composting plant were characterized, aiming at providing specific odour emission factors (OEF) and to determine their variability depending on the composting time. Additionally, characterization of VOCs emitted during the process was conducted through TD-GC/MS analyses. Odour emission and VOCs characterization considered both (1) a first stage where a raw sludge and vegetal fraction mixture were actively composted in dynamic windrows and (2) a second curing stage in static piles. After increasing the composting time, a reduction of 40% of the maximum odour concentration referred to the dynamic windrow stage was estimated, whereas a reduction of 89% of the maximum odour concentration was achieved after turning of curing piles. However, global OEF increased from 4.42E + 06 to 5.97E + 06 ou·Mg-1 RS - VF when the composting time increased. Finally, different VOCs such as isovaleraldehyde, indole, skatole, butyric acid, dimethyl sulphide and dimethyl disulphide were identified as main potential odour contributors. Results obtained are a valuable resource for plant management to choose an appropriate sewage sludge composting strategy to mitigate odour emissions.