Restructuring Co-CoOx Interface with Titration Rate in Co/Nb-CeO2 Catalysts for Higher Water-Gas Shift Performance.

H2 production via water-gas shift reaction (WGS) is an important process and applied widely. Cobalt-modified CeO2 are promising catalysts for WGS reaction. Herein, a series of Co/Nb-CeO2 catalysts were prepared by varying the rate of precipitant addition during the coprecipitation method and examined for hydrogen generation through WGS reaction. The rates of precipitant addition were 1, 5, 15, and 25 mL/min. We obtained ceria supported cobalt catalysts with different sizes and morphology such as 3, 8 nm nanoclusters, 30 nm cubic nanoparticles, and 50 nm hexagonal nanoparticles. The well dispersed small cobalt particles in Co/Nb-CeO2 that was prepared at 5 mL/min titration rate exhibit strong interaction between cobalt oxide and CeO2 that retards the reduction of CoOx producing Co-CoOx pairs. In contrast, 1-Co/Nb-CeO2 and 25-Co/Nb-CeO2 result in bigger and aggregated Co particles, resulting in fewer interfaces with CeO2. The Co0, Coδ+, Ce3+, and Ov species are responsible for improved reducibility in Co/Nb-CeO2 catalysts and were quantitively measured using XPS, XAS, and Raman spectroscopy. The Co-CoOx interface assists dissociation of the H2O molecule; CO oxidation requires low activation energy and realizes a high turnover frequency of 9.8 s-1. The 5-Co/Nb-CeO2 catalyst achieved thermodynamic equilibrium equivalent CO conversion with efficient H2 production during WGS reaction at a gas hourly space velocity of 315,282 h-1. Successively, the 5-Co/Nb-CeO2 catalyst exhibited stable performance for straight 168 h attributed to stable CO-Coδ+ intermediate formation, achieving efficient inhibition of typical CO chemistry over the Co metal, suitable for hydrogen generation from waste derived synthesis gas.

In-situ physical and chemical remediation of Cd and Pb contaminated mine soils cultivated with Chinese cabbage: A three-year field study.

Soils pollution with heavy metals (HMs) is a serious concern due to their toxic effects on crop yield, crop quality, soil environment, and human health. In the current study, four stabilizers of calcium carbonate (CC), dolomite (DL), zeolite (ZL), and steel slag (SS) were applied to cadmium (Cd) and lead (Pb)-contaminated soils as in-situ chemical remediation techniques along with in-situ physical remediation techniques i.e. soil covering (SC) and soil dilution (SD) under real field conditions. For three years, Chinese cabbage (Brassica rapa L.) was grown on the amended fields to examine how the amendments impacted Cd and Pb uptake in plants. The stabilization efficiency of SS, CC, and SC were 75.7 %, 66.0 %, and 71.1 %, respectively, for Cd, and 55.6 %, 55.6 %, and 70.0 %, respectively, for Pb. Results indicated that stabilizer soil amendments significantly decreased the exchangeable (F1) and carbonates bound (F2) fractions of both Cd and Pb. For instance, F1 fraction of Cd decreased from 10.2 (control) to 1.8-2.9 % (with stabilizers). The stabilizers increased Chinese cabbage dry weight by 11.4-22.5 % and decreased Cd and Pb uptake by 67.4 % and 24 %, respectively. The results demonstrated that in-situ chemical remediation technique showed promising results and maintained its efficiency for more than 130 weeks. Current study indicated that chemical remediation of Cd and Pb contaminated soil is more effective and last longer than physical remediation.

Advances in physicochemical pretreatment strategies for lignocellulose biomass and their effectiveness in bioconversion for biofuel production.

The inherent recalcitrance of lignocellulosic biomass is a significant barrier to efficient lignocellulosic biorefinery owing to its complex structure and the presence of inhibitory components, primarily lignin. Efficient biomass pretreatment strategies are crucial for fragmentation of lignocellulosic biocomponents, increasing the surface area and solubility of cellulose fibers, and removing or extracting lignin. Conventional pretreatment methods have several disadvantages, such as high operational costs, equipment corrosion, and the generation of toxic byproducts and effluents. In recent years, many emerging single-step, multi-step, and/or combined physicochemical pretreatment regimes have been developed, which are simpler in operation, more economical, and environmentally friendly. Furthermore, many of these combined physicochemical methods improve biomass bioaccessibility and effectively fractionate ∼96 % of lignocellulosic biocomponents into cellulose, hemicellulose, and lignin, thereby allowing for highly efficient lignocellulose bioconversion. This review critically discusses the emerging physicochemical pretreatment methods for efficient lignocellulose bioconversion for biofuel production to address the global energy crisis.

Highly Exposed NH2 Edge on Fragmented g-C3 N4 Framework with Integrated Molybdenum Atoms for Catalytic CO2 Cycloaddition: DFT and Techno-Economic Assessment.

This study focuses on the applicability of single-atom Mo-doped graphitic carbon nitride (GCN) nanosheets which are specifically engineered with high surface area (exfoliated GCN), NH2 rich edges, and maximum utilization of isolated atomic Mo for propylene carbonate (PC) production through CO2 cycloaddition of propylene oxide (PO). Various operational parameters are optimized, for example, temperature (130 °C), pressure (20 bar), catalyst (Mo2 GCN), and catalyst mass (0.1 g). Under optimal conditions, 2% Mo-doped GCN (Mo2 GCN) has the highest catalytic performance, especially the turnover frequency (TOF) obtained, 36.4 h-1 is higher than most reported studies. DFT simulations prove the catalytic performance of Mo2 GCN significantly decreases the activation energy barrier for PO ring-opening from 50-60 to 4.903 kcal mol-1 . Coexistence of Lewis acid/base group improves the CO2 cycloaddition performance by the formation of coordination bond between electron-deficient Mo atom with O atom of PO, while NH2 surface group disrupts the stability of CO2 bond by donating electrons into its low-level empty orbital. Steady-state process simulation of the industrial-scale consumes 4.4 ton h-1 of CO2 with PC production of 10.2 ton h-1 . Techno-economic assessment profit from Mo2 GCN is estimated to be 60.39 million USD year-1 at a catalyst loss rate of 0.01 wt% h-1 .

Integrative chemical and omics analyses reveal copper biosorption and tolerance mechanisms of Bacillus cereus strain T6.

A comprehensive understanding of the cellular response of microbes to metal stress is necessary for the rational development of microbe-based biosorbents for metal removal. The present study investigated the copper (Cu) sorption and resistance mechanism of Bacillus cereus strain T6, a newly isolated Cu-resistant bacterium, by integrative analyses of physiochemistry, genomics, transcriptomics, and metabolomics. The growth inhibition assay and biosorption determination showed that this bacterium exhibited high tolerance to Cu, with a minimum inhibitory concentration of 4.0 mM, and accumulated Cu by both extracellular adsorption and intracellular binding. SEM microscopic images and FTIR spectra showed significant cellular surface changes at the high Cu level but not at low, and the involvement of surface functional groups in the biosorption of Cu, respectively. Transcriptomic and untargeted metabolomic analyses detected 362 differentially expressed genes and 60 significantly altered metabolites, respectively. Integrative omics analyses revealed that Cu exposure dramatically induced a broad spectrum of genes involved in Cu transport and iron homeostasis, and suppressed the denitrification pathway, leading to significant accumulation of metabolites for metal transporter synthesis, membrane remolding, and antioxidant activities. The results presented here provide a new perspective on the intricate regulatory network of Cu homeostasis in bacteria.

Syntrophic metabolism facilitates Methanosarcina-led methanation in the anaerobic digestion of lipidic slaughterhouse waste.

Different inoculum to slaughterhouse waste (SHW) ratios (Ino/SHW) influences the digester performance, substrate utilization, and methane yield through microbial shift and their metabolic syntrophy. Acetoclastic Methanosarcina (68-87%) was dominant in the exponential phase, overpowering the initial abundance of Methanosaeta (86% of methanogens) in the SHW digesters. Positive interactions among acetogenic and acetate-oxidizing species of Clostridium (11%) with Methanosarcina (84% of methanogens) improved the methanogenic activity (292 mL g-1 VSinitial d-1) and final VS utilization (90%) at the highest Ino/SHW loading. In contrast, significant improvement of methane yield (152% higher than the control) at the lowest Ino/SHW loading was attributed to strong syntrophy among Methanosaeta (24% of methanogens) and its exoelectrogenic partners, Bythopirellula (0.52%) and Mariniphaga (0.08%) and the acetogenic Cloacimonas (0.16%) and Longilinea (0.32%). These syntrophic interactions among the core microbiota induced major metabolic activities, including butanoate, glycine, serine and threonine, methane, propanoate, and pyruvate metabolism, and quorum sensing.

Energy-efficient pretreatments for the enhanced conversion of microalgal biomass to biofuels.

The physiological properties, including biochemical composition and cell wall thickness, of microalgal species have a remarkable effect on the pretreatment of biomass and its further conversion to biofuels. In the present study, multiple biofuels (bioethanol, higher alcohols (C3-C5), and biodiesel) were produced using energy-efficient microwave pretreatment, successive carbohydrate/protein fermentation, and lipid transesterification from three microalgal strains (Pseudochlorella sp., Chlamydomonas mexicana, and Chlamydomonas pitschmannii). The microwave pretreatment method required the lowest specific energy (5 MJ/kg) compared to ultrasound pretreatment. The proposed integrated approach achieved high conversion efficiency (46%) and maximum biomass utilization (93%) of C. mexicana with improved yields of bioethanol (0.46 g-ethanol/g-carbohydrates), higher alcohols (0.44 g-higher alcohols/g-proteins), and biodiesel (0.74 g-biodiesel/g-lipids). This study suggests that the application of an appropriate pretreatment method for microalgal strains having different physiological properties is essential for improving the extraction efficiency and conversion of biomass to biofuels with less waste production.

Biocomponent-based microalgal transformations into biofuels during the pretreatment and fermentation process.

Microalgal cell wall integrity and composition have a significant impact on the fermentation process and biofuel recovery. In this study, various biofuels (bioethanol, higher alcohols (C3-C5), and biodiesel) were produced by the fermentation of carbohydrates and proteins, and transesterification of lipids from three different microalgal strains (Pseudochlorella sp., Chlamydomonas mexicana, and Chlamydomonas pitschmannii), each possessing different proportions of bioconstituents (carbohydrates, proteins, and lipids). Changes in the cell wall structure and thickness were observed before and after fermentation using transmission electron microscopy. Pseudochlorella sp. showed the highest yields of bioethanol (0.45 g-ethanol/g-carbohydrates), higher alcohols (0.44 g-higher alcohols/g-proteins), and biodiesel (0.55 g-biodiesel/g-lipids), which consequently revealed a maximum energy recovery (42%) from whole constituents. This study suggests that different physiological properties, including cell wall thickness and the proportion of bioconstituents in microalgae, could have a significant impact on the pretreatment and fermentation efficiencies for biofuels production.

Microbial community acclimatization for enhancement in the methane productivity of anaerobic co-digestion of fats, oil, and grease.

The methane productivity and long chain fatty acids (LCFAs) degradation capability of unacclimatized seed sludge (USS) and acclimatized seed sludge (ASS) at different substrate ratios of fats oil and grease (FOG) and mixed sewage sludge were investigated in this study. Biogas produced in ASS in initial phase of anaerobic digestion had higher methane content (65-76%) than that in USS (26-73%). The degradation of major LCFAs in the ASS was 22-80%, 33-191%, and 7-64% higher for the substrate ratios of 100:10, 100:20, and 100:30, respectively, as compared to the LCFAs' degradation in USS. Microbial acclimatization increased the population of Firmicutes (40%), Bacteroidetes (32%), Synergistetes (10%), and Euryarchaeota (8%) in ASS, which supported the faster rate of LCFAs degradation for its later conversion to methane. The significant abundance of Syntrophomonas and Methanosarcina genera in ASS supported faster generation rate of methane in an obligatory syntrophic relationship.

Interspecies microbial nexus facilitated methanation of polysaccharidic wastes.

Compositional variations in organic wastes influence microbial abundancy and syntrophy during anaerobic digestion (AD), impacting the normal performance of digesters for methanation. Investigation of the microbial dynamics during AD following augmentation with polysaccharidic wastes (PW) revealed the association of effective digester performance and methane yields with the microbial nexus. Dominance of the acidogenic saccharolytic genera, Prevotella, Eubacterium, and Lachnoclostridium, enhanced the utilization of carbohydrates (54%) in PW-augmented digesters. Spearman's rs correlation showed dynamic interspecies interactions among acetogenic syntrophs, and that of iron oxidizers/reducers with acetoclastic and hydrogenotrophic methanogens. Propionate oxidizers in Chloroflexi (i.e., Bellilinea, Levilinea, and Longilinea) exhibited positive associations with acetoclastic methanogens. Increase in the population of acetoclastic methanogens (Methanosaeta, 77% and Methanosarcina, 9%) accelerated the methanogenic activity of PW-augmented digesters by 7 times during the exponential phase, increasing the methane yield (75%) compared to the control. Thus, microbial syntrophy facilitated the effective methanation of PW during AD process.

Algae as a green technology for heavy metals removal from various wastewater.

Urbanization, industrialization, and natural earth processes have potentially increased the contamination of heavy metals (HMs) in water bodies. These HMs can accumulate in human beings through the consumption of contaminated water and food chains. Various clean-up technologies have been applied to sequester HMs, especially conventional methods including electrolytic technologies, ion exchange, precipitation, chemical extraction, hydrolysis, polymer micro-encapsulation, and leaching. However, most of these approaches are expensive for large-scale projects and require tedious control and constant monitoring, along with low efficiency for effective HMs removal. Algae offer an alternative, sustainable, and environmentally friendly HMs remediation approach. This review presents a state-of-the-art technology for potential use of algae as a low-cost biosorbent for the removal of HMs from wastewater. The mechanisms of HMs removal, including biosorption and bioaccumulation along with physical and chemical characterization of the algae are highlighted. The influence of abiotic factors on HMs removal and changes in algal biocomponents (including, carbohydrate, lipid, and protein) are discussed. Recent progresses made in the development of HMs-tolerant algal strains and the direction of future research toward the development of sustainable technology for advanced wastewater treatment and biomass production are covered.

Can Omics Approaches Improve Microalgal Biofuels under Abiotic Stress?

Microalgae hold the promise of an inexpensive and sustainable source of biofuels. The existing microalgal cultivation technologies need significant improvement to outcompete other biofuel sources such as terrestrial plants. Application of 'algomics' approaches under different abiotic stress conditions could be an effective strategy for optimization of microalgal growth and production of high-quality biofuels. In this review, we discuss the roles of omics in understanding genome structure and biocomponents metabolism in various microalgal species to optimize sustainable biofuel production. Application of individual and integrated omics revealed that genes and metabolic pathways of microalgae have been altered under multiple stress conditions, resulting in an increase in biocomponents, providing a research platform for expansion of genetic engineering studies in microalgal strains.

Uptake and biodegradation of emerging contaminant sulfamethoxazole from aqueous phase using Ipomoea aquatica.

Plants serve as appropriate markers of worldwide pollution because they are present in almost every corner of the globe and bioaccumulate xenobiotic chemicals from their environment. The potential of a semi-aquatic plant, Ipomoea aquatica, to uptake and metabolize sulfamethoxazole (SMX) was investigated in this study. I. aquatica exhibited 100% removal of 0.05 mg L-1 SMX from synthetic media within 30 h. The I. aquatica achieved 93, 77 and 72% removal of SMX at 0.2, 0.5 and 1 mg L-1, respectively, after 48 h. This indicated that removal efficiency of I. aquatica was deteriorating at high concentrations of SMX. The chlorophyll and carotenoid content of I. aquatica was insignificantly influenced by SMX irrespective of its high concentration. Similarly, scanning electron microscopy (SEM) showed that exposure to SMX had an insignificant impact on morphology of the plant organelles. The mechanisms of removal by I. aquatica were explored by evaluating contributions of bioadsorption, bioaccumulation and biodegradation. There was negligible adsorption of SMX to plant roots. Accumulation of SMX within plant roots and stems was not observed; however, I. aquatica accumulated 17% of SMX in leaves. Thus, the major mechanism of elimination of SMX was biodegradation, which accounted for 82% removal of SMX. Gas chromatography-mass spectrometry (GC-MS) confirmed that I. aquatica biodegraded SMX into simpler compounds, and generated 4-aminophenol as its final product. A laboratory scale phytoreactor was used to investigate the application of I. aquatica in a simulated system, where it achieved 49% removal of SMX (0.2 mg L-1) in 10 d.

Combined effects of sulfamethazine and sulfamethoxazole on a freshwater microalga, Scenedesmus obliquus: toxicity, biodegradation, and metabolic fate.

This study investigated the environmental effects of two common emerging contaminants, sulfamethazine (SMZ) and sulfamethoxazole (SMX), and their mixture using a green microalga, Scenedesmus obliquus. The calculated EC50 values of SMZ, SMX, and their mixture (11:1 wt/wt) after 96 h were 1.23, 0.12, and 0.89 mg L-1, respectively. The toxicity of the mixture could be better predicted using a concentration addition model than an independent action model. The risk quotients of SMZ, SMX, and their mixture were >1 during the experiment, indicating their high potential risks on aquatic microorganisms. Despite their toxicity, S. obliquus exhibited 17.3% and 29.3% removal of 0.1 mg L-1 and 0.2 mg L-1 after 11 days of cultivation. The changes of SMZ and SMX removal were observed when combined, which showed a significantly improved removal of SMZ (up to 3.4 folds) with addition of SMX (0.2 mg L-1). The metabolic pathways of SMZ and SMX were proposed according to mass spectroscopic analysis, which showed six metabolites of SMX and seven intermediates of SMZ, formed as a result of ring cleavage, hydroxylation, methylation, nitrosation, and deamination.

Toxicity of sulfamethazine and sulfamethoxazole and their removal by a green microalga, Scenedesmus obliquus.

A comprehensive ecotoxicological evaluation of a sulfamethazine (SMZ) and sulfamethoxazole (SMX) mixture was conducted using an indicator microalga, Scenedesmus obliquus. The toxicological effects of this mixture were studied using microalgal growth patterns, biochemical characteristics (total chlorophyll, carotenoid, carbohydrate, fatty acid methyl ester), and elemental and Fourier-transform infrared spectroscopy analyses. The 96-h half maximal effective concentration (EC50) of the SMZ and SMX mixture was calculated to be 0.15 mg L-1 according to the dose-response curves obtained. The chlorophyll content decreased with elevated SMZ and SMX concentrations, while the carotenoid content initially increased and then decreased as concentration raised. The unsaturated fatty acid methyl esters (FAMEs) content was enhanced with higher SMZ and SMX concentrations, while that of saturated FAMEs simultaneously decreased due to SMZ and SMX stress. Elemental analyses showed an improved percentage of nitrogen and sulfur in the microalgal biomass as SMZ and SMX concentrations increased. The microalga S. obliquus was shown to biodegrade the chemicals tested and removed 31.4-62.3% of the 0.025-0.25 mg SMZ L-1 and 27.7-46.8% of the 0.025-0.25 mg SMX L-1 in the mixture after 12 days of cultivation. The greater biodegradation observed at higher SMZ and SMX concentrations indicates that microalgal degradation of SMZ and SMX could act as an efficient adaptive mechanism to antibiotics.

Ciprofloxacin toxicity and its co-metabolic removal by a freshwater microalga Chlamydomonas mexicana.

This study evaluated the toxicity and cellular stresses of ciprofloxacin (CIP) and its co-metabolic removal in a freshwater microalga Chlamydomonas mexicana. The toxicological effects of CIP on C. mexicana were assessed by studying the growth and biochemical characteristics of the microalga including total chlorophyll, carotenoid content, malondialdehyde (MDA) and superoxide dismutase (SOD) activity. The calculated effective concentration (EC50) of CIP on C. mexicana was 65±4mgL-1 at 96h. The growth of C. mexicana was significantly inhibited at increased concentrations of CIP, showing 36±1, 75±3. and 88±3% inhibition at 40, 60 and 100mgL-1 CIP, respectively, compared to the control after 11days of cultivation. The total chlorophyll, carotenoid, MDA and SOD activity were significantly increased as a result of relatively high concentrations of CIP stress. C. mexicana showed 13±1% removal of CIP (2mgL-1) after 11days of cultivation; however, the addition of an electron donor (sodium acetate, 4gL-1) highly enhanced the removal of CIP (2mgL-1) by>3-fold after 11days. Kinetic studies showed that removal of CIP followed a first-order model (R2 0.94-0.97) with the apparent rate constants (k) ranging from 0.0121 to 0.079 d-1.

Bio-Diesel Production from Deoxygenation Reaction Over Ce0.6Zr0.4O2 Supported Transition Metal (Ni, Cu, Co, and Mo) Catalysts.

Ce0.6Zr0.4O2 supported transition metal (Me = Ni, Cu, Co, and Mo) catalysts have been investigated to screen for the catalytic activity and selectivity for deoxygenation reaction of oleic acid. Me-Ce0.6Zr0.4O2 catalysts were prepared by a co-precipitation method. Ni-Ce0.6Zr0.4O2 catalyst exhibited much higher oleic acid conversion, selectivity for C9 to C17 compounds, and oxygen removal efficiency than the others. This is mainly ascribed to the presence of free Ni species, synergy effects between Ni and Ce0.6Zr0.4O2, and the highest BET surface area.

Highly Active and Stable Pt-Loaded Ce0.75Zr0.25O2 Yolk-Shell Catalyst for Water-Gas Shift Reaction.

Multishelled, Pt-loaded Ce0.75Zr0.25O2 yolk-shell microspheres were prepared by a simple spray pyrolysis process for use in the water-gas shift (WGS) reaction. The Pt-loading was optimized, obtaining highly active Pt/Ce0.75Zr0.25O2 yolk-shell nanostructures for the WGS. Of the prepared catalysts, a 2% Pt loading of the Ce0.75Zr0.25O2 yolk-shell microspheres showed the highest CO conversion. The high catalytic activity of the 2% Pt/Ce0.75Zr0.2O2 catalyst was mainly due to its easier reducibility and the maintenance of active catalytic Pt species. The Pt-loaded Ce0.75Zr0.25O2 catalyst microspheres were highly resistant to Pt sintering because of their unique yolk-shell structure. Spray pyrolysis was found to be highly efficient for the production of precious-metal-loaded, multicomponent metal oxide yolk-shell microspheres for catalytic applications.

The effects of salinity on the growth and biochemical properties of Chlamydomonas mexicana GU732420 cultivated in municipal wastewater.

A freshwater microalga Chlamydomonas mexicana was grown on municipal wastewater with different levels of salinity up to 400 mmol/L NaCl, and the biochemical properties were characterized after 10 days of cultivation. C. mexicana showed the higher specific growth rates for 100 and 200mmol/L NaCl. Nitrogen was completely removed within 10 days as a result of algal growth promoted by the addition of 200-400 mmol/L NaCl. Phosphorus removal increased from 77-84% as the concentration of NaCI increased from 100 to 400 mmol/L. The highest removal of total inorganic carbon (66%) was obtained with the addition of 200 mmol/L NaCl. The lipid content increased from 17% to 38% as the concentration of NaCl increased from 0 to 400mmol/L. The total fatty acid content and glycerol yield of C. mexicana increased 1.8- and 4-fold in wastewater amended with NaCl, respectively. Fatty acids accumulated in the algal biomass were mainly composed of palmitic (27-29%), y-linolenic (27-30%), and linolelaidic acids (16-18%). The optimal condition for fatty acids production in C. mexicana was observed when the municipal wastewater was amended with 100-200 mmol/L NaCl with a simultaneous removal of nutrients.

Effect of mine wastewater on nutrient removal and lipid production by a green microalga Micratinium reisseri from concentrated municipal wastewater.

Effect of mine wastewater on the nutrient removal efficiency of a green microalga Micratinium reisseri from concentrated municipal wastewater (CMW) with simultaneous lipid production was investigated. Different dilution ratios (1-10%) of CMW either with mine wastewater (MWF) or mine wastewater without Fe (MWOF) were used. M. reisseri showed the highest growth (0.8gL(-1)) and nutrient uptake (35.9mgTNL(-1) and 5.4mgTPL(-1)) at 3% MWF ([Fe]tot=6.7mgL(-1)), and the highest lipid productivity (10.4mgL(-1)day(-1)) at 5% MWF ([Fe]tot=11.2mgL(-1)) after 15days. CMW supported the algal autoflocculation due to formation of phosphate, calcium and magnesium precipitates at a high suspension pH. Fatty acid methyl ester analysis revealed that the microalgal lipids possessed 79-82% of C16/C18 fatty acids. Application of mine wastewater improved the nutrient removal efficiency, growth and lipid productivity of M. reisseri cultivated in CMW.