Sustainable Valorisation of Sewage Sludge via Carbon Dioxide-Assisted Pyrolysis.

The escalating volume of sewage sludge (SS) generated poses challenges in disposal, given its potential harm to the environment and human health. This study explored sustainable solutions for SS management with a focus on energy recovery. Employing CO2-assisted pyrolysis, we converted SS into flammable gases (H2 and CO; syngas). Single-stage pyrolysis of SS in a CO2 conditions demonstrated that CO2 enhances flammable gas production (especially CO) through gas phase reactions (GPRs) with volatile matter (VM) at temperatures ≥ 520 ˚C. Specifically, the CO2 partially oxidized the VM released from SS and concurrently underwent reduction into CO. To enhance the syngas production at temperatures ≤ 520 ˚C, multi-stage pyrolysis setup with additional heat energy and a Ni/Al2O3 catalyst were utilized. These configurations significantly increased flammable gas production, particularly CO, at temperatures ≤ 520 ˚C. Indeed, the flammable gas yield in the catalytic pyrolysis of SS increased from 200.3 mmol under N2 conditions to 219.2 mmol under CO2 conditions, representing a 4.4-fold increase compared to single-stage pyrolysis under CO2 conditions (50.0 mmol). By integrating a water-gas-shift reaction, the flammable gases produced from CO2-assisted catalytic pyrolysis were expected to have the potential to generate revenue of US$4.04 billion. These findings highlight the effectiveness of employing CO2 in SS pyrolysis as a sustainable and effective approach for treating and valorising SS into valuable energy resources.

Towards Sustainable Production of Polybutylene Adipate Terephthalate: Non-biological Catalytic Syntheses of Biomass-derived Constituents.

Renewable chemicals, which are made from renewable resources such as biomass, have attracted significant interest as substitutes for natural gas- or petroleum-derived chemicals to enhance the sustainability of the chemical and petrochemical industries. Polybutylene adipate terephthalate (PBAT), which is a copolyester of 1,4-butanediol (1,4-BDO), adipic acid (AA), and dimethyl terephthalate (DMT) or terephthalic acid (TPA), has garnered significant interest as a biodegradable polymer. This study assesses the non-biological production of PBAT monomers from biomass feedstocks via heterogeneous catalytic reactions. The biomass-based catalytic routes to each monomer are analyzed and compared to conventional routes. Although no fully commercialized catalytic processes for direct conversion of biomass into 1,4-BDO, AA, DMT, and TPA are available, emerging and promising catalytic routes have been proposed. The proposed biomass-based catalytic pathways toward 1,4-BDO, AA, DMT, and TPA are not yet fully competitive with conventional fossil fuel-based pathways mainly due to high feedstock prices and the existence of other alternatives. However, given continuous technological advances in the renewable production of PBAT monomers, bio-based PBAT should be economically viable in the near future.

Stabilization mechanism and long-term stability of endogenous heavy metals in manure-derived biochar.

Pyrolysis has been proposed to stabilize heavy metals present in livestock manure. However, many studies have not considered the applicability of manure-derived biochar containing endogenous heavy metals as an agricultural fertilizer. This study investigated the mechanisms through which pyrolysis stabilizes endogenous heavy metals in swine manure and the long-term stability of endogenous heavy metals in the biochar. As pyrolysis temperature increased from 300 °C to 700 °C, the potential ecological risk index decreased from 46.3 to 4.8 because the unstable fraction converted to organic-sulfide bonds and residues. Biochar prepared at 600 °C was the most stable and met the World Health Organization's phyto-availability standards (Cu 10 mg/kg, Zn 0.6 mg/kg). Fourier transform infrared spectroscopy and X-ray diffraction analyses indicated that endogenous heavy metals were stabilized by complexation with organic matter and precipitated as metal-phosphate forms. After 40 cycles of wet-dry aging, the leachability of heavy metals (Cu 6.0 mg/kg, Zn 460.6 mg/kg) from biochar was still lower than that of swine manure (Cu 102.5 mg/kg and Zn 704.9 mg/kg), indicating the long-term stability of the heavy metals in the biochar. Pyrolysis dramatically lowered the environmental threat posed by endogenous heavy metals, demonstrating the applicability of swine manure-derived biochar compared to manure.

Functional use of carbon dioxide for the sustainable valorization of orange peel in the pyrolysis process.

Although biomass is carbon-neutral, its use as a primary feedstock faces challenges arising from inconsistent supply chains. Therefore, it becomes crucial to explore alternatives with reliable availability. This study proposes a strategic approach for the thermochemical valorization of food processing waste, which is abundantly generated at single sites within large-scale processing plants. As a model biomass waste from the food industry, orange peel waste was particularly chosen considering its substantial consumption. To impart sustainability to the pyrolysis system, CO2, a key greenhouse gas, was introduced. As such, this study highlights elucidating the functionality of CO2 as a reactive feedstock. Specifically, CO2 has the potential to react with volatile pyrolysates evolved from orange peel waste, leading to CO formation at ≥490 °C. The formation of chemical constituents, encompassing acids, ketones, furans, phenols, and aromatics, simultaneously decreased by 15.1 area% in the presence of CO2. To activate the efficacy of CO2 at the broader temperature spectrum, supplementary measures, such as an additional heating element (700 °C) and a nickel-based catalyst (Ni/Al2O3), were implemented. These configurations promote thermal cracking of the volatiles and their reaction kinetics with CO2, representing an opportunity for enhanced carbon utilization in the form of CO. Finally, the integrated process of CO2-assisted catalytic pyrolysis and water-gas shift reaction was proposed. A potential revenue when maximizing the productivity of H2 was estimated as 2.62 billion USD, equivalent to 1.11 times higher than the results from the inert (N2) environment. Therefore, utilizing CO2 in the pyrolysis system creates a promising approach for enhancing the sustainability of the thermochemical valorization platform while maximizing carbon utilization in the form of CO.

Applications of charcoal, activated charcoal, and biochar in aquaculture - A review.

Environmental pollution and poor feed quality pose potential threats to aquatic organisms and human health, representing challenges for the aquaculture industry. In light of the rising demand for aquatic organisms, there is an urgent need to improve aquacultural production and protect the products from contamination. Char, a carbonaceous material derived through pyrolysis of organic carbon-rich biomass, has proven advantages in soil, air, and water remediation. While char's performance and the associated physicochemical characteristics depend strongly on the pyrolysis temperature, residence time, and feedstock type, char generally shows advantages in pollutant removal from the environment and livestock. This enables it to enhance the health and growth performance of livestock. Given the growing attention to char application in aquaculture in recent years, this review summarises major studies on three applications: aquacultural water treatment, sediment remediation, and char-feed supplement. Most of these studies have demonstrated char's positive effects on pollutant removal from organisms and aquacultural environments. Moreover, adopting char as fish feed can improve fish growth performance and the condition of their intestinal villi. However, due to insufficient literature, further investigation is needed into the mechanistic aspects of pollutants removal in aquatic organisms by char as a feed additive, such as the transportation of char inside aquatic organisms, the positive and negative effects of char on these products, and how char alters the gut microbiota community of these products. This paper presents an overview of the current application of char in aquaculture and highlights the research areas that require further investigation to enrich future studies.

Thermal hydrolysis alleviates polyethylene microplastic-induced stress in anaerobic digestion of waste activated sludge.

Microplastics are known to negatively affect anaerobic digestion (AD) of waste activated sludge. However, whether thermal hydrolysis (TH) pretreatment alters the impact of microplastics on sludge AD remains unknown. Herein, the effect of TH on the impact of polyethylene (PE) microplastics in sludge AD was investigated. The results showed that the inhibition of methane production by PE at 100 particles/g total solids (TS) was reduced by 31.4% from 12.1% to 8.3% after TH at 170 °C for 30 min. Mechanism analysis indicated TH reduced the potential for reactive oxygen species production induced by PE, resulting in a 29.1 ± 5.5% reduction in cell viability loss. In addition, additive leaching increased as a result of rapid aging of PE microplastics by TH. Acetyl tri-n-butyl citrate (ATBC) release from PE with 10 and 100 particles/g TS increased 11.5-fold and 8.6-fold after TH to 68.2 ± 5.5 µg/L and 124.0 ± 5.1 µg/L, respectively. ATBC at 124.0 µg/L increased methane production by 21.4%. The released ATBC enriched SBR1031 and Euryarchaeota, which facilitate the degradation of proteins and promote methane production. This study reveals the overestimated impact of PE microplastics in sludge AD and provides new insights into the PE microplastics-induced impact in practical sludge treatment and anaerobic biological processes.

Thermochemical conversion of silkworm by-product into syngas.

This study explored the valorisation of silkworm by-product, a major by-product of the silk industry (sericulture), which amounts to 16 million tonnes annually. The focus was on transforming waste into energy resources through pyrolysis under CO2 conditions. In one-stage pyrolysis, the evolution of syngas under N2 was found to be comparable to that under CO2. A notable allocation of carbon to biocrude rather than syngas was observed. The two-stage pyrolysis resulted in increased syngas production. However, achieving a homogeneous reaction between CO2 and the volatiles liberated from silkworm byproduct proved challenging. Indeed, the reaction kinetics governing CO2 reactivity was not fast although the temperature windows of the reaction were aligned in the two-stage pyrolysis. To address this issue, pyrolysis was performed using a Ni-based catalyst to expedite the reaction kinetics. Consequently, syngas formation, particularly CO formation, was significantly enhanced under CO2 conditions compared to that under N2 conditions. The syngas yield under CO2 was 36.42 wt% which was 2-fold higher than that of N2. This suggested the potential of CO2 altering the carbon distribution from biocrude to syngas. This strategy would contribute to the establishment of sustainable production of silk by converting sericulture by-product into energy/chemical resources.

Direct conversion of apricot seeds into biodiesel.

Using edible lipids for biodiesel production has been criticized, causing biodiesel production from inedible food resources to be desirable. Lipid extraction must be prioritized to produce biodiesel using an acid/base-catalyzed transesterification process, but this conversion process suffers from technical reliability. Therefore, this study introduced non-catalytic conversion of oil-bearing biomass into biodiesel. Apricot seeds were used as a model compound (oil content 44.3 wt%). The non-catalytic transesterification of apricot seed oil recovered 98.28 wt% biodiesel at 360 °C for 1 min, while alkali-catalysis of apricot seed oil recovered 91.84 wt% at 63 °C for 60 min. The direct conversion of apricot seeds into biodiesel was attempted. The trends in the yields of biodiesel from apricot seeds and seed oil obtained by non-catalytic transesterification as a function of reaction temperature were similar. The yield of biodiesel from apricot seed was 43.06 wt%, suggesting that 97.20 wt% of lipids were converted into biodiesel.

Hepatotoxicity evaluations of different surface charged carbon quantum dots in vivo and in vitro.

Recently, carbon quantum dots (CQDs) have become popular because of their simple synthesis and potential applications. Although CQDs have high biocompatibility, their biotoxicity must be verified to reduce the possible risks associated with large-scale application. In this study, the hepatotoxicity of three CQD types, namely diammonium citrate (AC)-based (CQDs-AC), spermidine trihydrochloride (Spd)-based (CQDs-Spd), and AC- and Spd-based CQDs (CQDs-AC/Spd), were evaluated in vivo and in vitro. It was observed in vivo that CQDs-Spd and CQDs-AC/Spd, but not CQDs-AC, caused histopathological damage, including liver steatosis and mild mixed inflammatory cell infiltration; however, reduced liver function was only observed in CQD-Spd-treated mice. The in vitro results revealed that only CQDs-Spd significantly decreased the number of viable HepG2 cells (NADH depletion) and induced oxidative stress (heme oxygenase-1 activation) after 24 h of exposure, which promoted inflammatory factor secretion (NF-κB activation). Additionally, decreasing zonula occludens-2 and α1-antitrypsin protein expression in HepG2 cells suggested that CQD-Spd exposure increases the risk of liver diseases. Our results revealed that CQDs-Spd had greater hepatotoxic potential than CQDs-AC and CQDs-AC/Spd, which might be attributable to their high positive surface charge. Overall, the risk of CQD-induced hepatotoxic risk must be considered when applying positively charged CQDs.

Species identification, reproductive biology, and nutritional value of marine shellfish (Meretrix lyrata) in the Bay of Bengal.

Meretrix lyrata which is under the family of Veneridae and under the order of Venerida, is a nutritionally and economically important edible mussel in Bangladesh. However, studies on species identification and nutritional value in M. lyrata are scarce. Therefore, a detailed investigation was conducted on (i) species identification of the common edible mussel through DNA-barcoding and morphometrics, (ii) reproductive features, such as size at sexual maturity, spawning, and peak-spawning seasons under different environmental factors, and (iii) nutritional status through proximate analysis of M. lyrata mussel collected from the Bay of Bengal, Bangladesh. The results indicated that the size at sexual maturity for M. lyrata was 4.2 cm and the spawning seasons were significantly affected by the dissolve oxygen and salinity. The study also demonstrated that the spawning of M. lyrata occurred from January to June and December while peak spawning season was May in the Bay of Bengal. The higher protein and moisture contents with lower fat in M. lyrata indicated that are value-added seafood with higher nutritional values for consumers.

Sustainable ethylene production: Recovery from plastic waste via thermochemical processes.

The concept of monomer recovery from plastic waste has recently gained broad interest in industry as a powerful strategy to reduce the environmental impacts of chemical production and plastic waste pollution. Herein, we focus on the ethylene recovery from plastic waste via thermochemical pathways, such as pyrolysis, gasification, and steam cracking of pyrolysis oil derived from plastic waste. Ethylene recovery performance of different thermochemical conversion processes is evaluated and compared with respect to plastic waste types, process types, ethylene recovery yields, and process operating conditions. Based on the analysis of available data in earlier literature, future research is recommended to further enhance the viability of the thermochemical ethylene recovery technologies. This review is expected to offer a meaningful guideline on developing efficient platforms for the value-added monomer recovery from plastic waste through thermochemical conversion routes. It is also hoped that this review serves as a preliminary step to encourage the widespread adoption of thermochemical conversion-based ethylene recovery from plastic waste by industries.

Occurrences, sources, fate and impacts of plastic on aquatic organisms and human health in global perspectives: What Bangladesh can do in future?

Bangladesh is not an exception to the growing global environmental problem of plastic pollution. Plastics have been deemed a blessing for today's world thanks to their inexpensive production costs, low weight, toughness, and flexibility, but poor biodegradability and massive misuse of plastics are to blame for widespread contamination of the environmental components. Plastic as well as microplastic pollution and its adverse consequences have attracted significant investigative attention all over the world. Plastic pollution is a rising concern in Bangladesh, but scientific studies, data, and related information are very scarce in numerous areas of the plastic pollution problem. The current study examined the effects of plastic and microplastic pollution on the environment and human health, and it examined Bangladesh's existing knowledge of plastic pollution in aquatic ecosystems in light of the rapidly expanding international research in this field. We also made an effort to investigate the current shortcomings in Bangladesh's assessment of plastic pollution. This study proposed several management approaches to the persistent plastic pollution problem by analyzing studies from industrialized and emerging countries. Finally, this work pushed investigators to investigate Bangladesh's plastic contamination thoroughly and develop guidelines and policies to address the issue.

Evaluation of the pulmonary toxicity of PSNPs using a Transwell-based normal human bronchial epithelial cell culture system.

To reduce the nanoplastics (NPs) toxicity assessment error, we established a Transwell-based bronchial epithelial cell exposure system to assess the pulmonary toxicity of polystyrene NPs (PSNPs). Transwell exposure system was more sensitive than submerged culture for toxicity detection of PSNPs. PSNPs adhered to the BEAS-2B cell surface, were ingested by the cell, and accumulated in the cytoplasm. PSNPs induced oxidative stress and inhibited cell growth through apoptosis and autophagy. A noncytotoxic dose of PSNPs (1 ng/cm2) increased the expression levels of inflammatory factors (ROCK-1, NF-κB, NLRP3, ICAM-1, etc) in BEAS-2B cells, whereas a cytotoxic dose (1000 ng/cm2) induced apoptosis and autophagy, which might inhibit the activation of ROCK-1 and contribute to reducing inflammation. In addition, the noncytotoxic dose increased the expression levels of zonula occludens-2 (ZO-2) and α1-antitrypsin (α-AT) proteins in BEAS-2B cells. Therefore, in response to PSNP exposure, a compensatory increase in the activities of inflammatory factors, ZO-2, and α-AT may be triggered at low doses as a mechanism to preserve the survival of BEAS-2B cells. In contrast, exposure to a high dose of PSNPs elicits a noncompensatory response in BEAS-2B cells. Overall, these findings suggest that PSNPs may be harmful to human pulmonary health even at an ultralow concentration.

Applications of agricultural residue biochars to removal of toxic gases emitted from chemical plants: A review.

Crop residues are representative agricultural waste materials, massively generated in the world. However, a large fraction of them is currently being wasted, though they have a high potential to be used as a value-added carbon-rich material. Also, the applications of carbon-rich materials from agricultural waste to industries can have economic benefit because waste-derived carbon materials are considered inexpensive waste materials. In this review, valorization methods for crop residues as carbon-rich materials (i.e., biochars) and their applications to industrial toxic gas removals are discussed. Applications of crop residue biochars to toxic gas removal can have significant environmental benefits and economic feasibility. As such, this review discussed the technical advantages of the use of crop residue biochars as adsorbents for hazardous gaseous pollutants and greenhouse gases (GHGs) stemmed from combustion of fossil fuels and the different refinery processes. Also, the practical benefits from the activation methods in line with the biochar properties were comprehensively discussed. The relationships between the physico-chemical properties of biochars and the removal mechanisms of gaseous pollutants (H2S, SO2, Hg0, and CO2) on biochars were also highlighted in this review study. Porosity controls using physical and chemical activations along with the addition of specific functional groups and metals on biochars have significantly contributed to the enhancement of flue gas adsorption. The adsorption capacity of biochar for each toxic chemical was in the range of 46-76 mg g-1 for H2S, 40-182 mg g-1 for SO2, 80-952 µg g-1 for Hg0, and 82-308 mg g-1 CO2, respectively. This helps to find suitable activation methods for adsorption of the target pollutants. In the last part, the benefits from the use of biochars and the research directions were prospectively provided to make crop residue biochars more practical materials in adsorption of pollutant gases.

Templating agent-mediated Cobalt oxide encapsulated in Mesoporous silica as an efficient oxone activator for elimination of toxic anionic azo dye in water: Mechanistic and DFT-assisted investigations.

While Azorubin S (AZRS) is extensively used as a reddish anionic azo dye for textiles and an alimentary colorant in food, AZRS is mutagenic/carcinogenic, and it shall be removed from dye-containing wastewaters. In view of advantages of SO4•--related chemical oxidation technology, oxone (KHSO5) would an ideal source of SO4•- for degrading AZRS, and heterogeneous Co3O4-based catalysts is required and shall be developed for activating oxone. Herein, a facile protocol is proposed for fabricating mesoporous silica (MS)-confined Co3O4 by a templating agent-mediated dry-grinding procedure. As the templating agent retained inside the ordered pores of MS (before calcination) would facilitate insertion and dispersion of Co ions into pores, the resulting Co3O4 nanoparticles (NPs) would be grown and confined within the pores of MS after calcination, affording Co@MS. On the contrary, another analogue, Co/MS, is also prepared using the similar protocol without the templating agent-mediated introduction of Co, but Co3O4 NPs seriously aggregate as clusters on MS. Therefore, Co@MS outperforms Co/MS for activating oxone to eliminate AZRS. Co@MS shows a noticeably lower activation energy of AZRS elimination than the existing catalysts, revealing its advantage over the reported catalysts. Moreover, the mechanistic investigation of AZRS elimination by Co@MS-activated oxone has been also elucidated for identifying the presence of SO4•‒, •OH, and 1O2 in AZRS degradation using scavengers, electron paramagnetic resonance spectroscopy, and semi-quantification. The AZRS decomposition pathway is also investigated and unveiled in details via the DFT calculation. These results validate that Co@MS appears as a superior catalyst of oxone activation for AZRS degradation.

Amine/hydrazone functionalized Cd(II)/Zn(II) metal-organic framework for ultrafast sensitive detection of hazardous 2,4,6-trinitrophenol in water.

Amine/hydrazone functionalized dual ligand Cd(II)/Zn(II) based metal-organic frameworks (MOFs) denoted as CdMOF- and ZnMOF-NH2, respectively were synthesized via a simple conventional high-yield reflux method using low-cost and readily available starting materials, i.e., a Schiff base linker, 4-pyridylcarboxaldehydeisonicotinoylhydrazone (L1) and 2-aminoterephthalic acid (H2ata) linker. Crystallographic and thermogravimetric studies confirmed the formation of MOFs with good crystallinity and thermal stability. Photoluminescence studies point out that both MOFs can be used efficiently for fast sensing of 2,4,6-trinitrophenol (TNP) in water with noticeable turn-off quenching response. Their limits of detection (LODs) for TNP were 7 ppb and 10 ppb, respectively with enhanced selectivity toward TNP (over other nitro explosives) as verified by competitive nitro explosive tests. Density functional theory calculations and spectral overlap were used to assess the sensing mechanism. These MOF-based fluorescent sensing systems for TNP are demonstrated to have easy recoverability and high sensitivity.

Polycarbonate microplastics induce oxidative stress in anaerobic digestion of waste activated sludge by leaching bisphenol A.

Polycarbonate (PC) microplastics are frequently detected in waste activated sludge. However, understanding the potential impact of PC microplastics on biological sludge treatment remains challenging. By tracking the changes in methane production under different concentrations of PC microplastics, a dose-dependent effect of PC microplastics on anaerobic digestion of sludge was observed. PC microplastics at 10-60 particles/g total solids (TS) improved methane production by up to 24.7 ± 0.1 % (at 30 particles/g TS), while 200 particles/g TS PC microplastics reduced methane production by 8.09 ± 0.1 %. Bisphenol A (BPA) leached from 30 particles/g TS PC microplastics (1.26 ± 0.18 mg/L) down-regulated intracellular reactive oxygen species (ROS) production, thereby enhancing enzyme activity, biomass viability, and abundance of methanogenic (Methanobacterium sp. and Methanosarcina sp.), ultimately boosting methane production. Conversely, BPA leached from 200 particles/g TS PC microplastics (4.02 ± 0.15 mg/L) stimulated ROS production, resulting in decreased biomass viability and even apoptosis. Modulation of oxidative stress by leaching monomeric BPA is an underappreciated transformative mechanism for improving the mastery of the potential behavior of microplastics in biological sludge treatment.

Synergic degradation Chloramphenicol in photo-electrocatalytic microbial fuel cell over Ni/MXene photocathode.

The abuse of Chloramphenicol (CAP) has become the increasingly serious environmental problem for its harmfulness and toxicity. A novel strategy was achieved by photocatalysis coupled with microbial fuel cell (Photo-MFC) over Ni/MXene photocathode for enhancing the degradation efficiency of (CAP). It was demonstrated that the best degradation efficiency of CAP can reach 82.62% (original concentration of 30 mg/L) after 36 h under the optimal conditions (pH = 2). Based on density functional theory (DFT) calculations and high-performance liquid chromatography-mass (HPLC-MS) spectrometry, it was speculated that the degradation mechanism of CAP in Photo-MFC over Ni/MXene photoelectrode was achieved by destroying the two asymmetric centers and nitro, including the hydrodechlorination, nitro reduction reaction, hydroxylation reaction, cleavage of CN bond and ring-opening reaction of benzene ring. Finally, the ecotoxicity evaluation of the degradation products showed that the CAP degradation in the Ni/MXene modified photo-MFC system showed a remarkable tendency to the low-toxicity level.

Isotherm models for adsorption of heavy metals from water - A review.

Adsorption is a widely used technology for removing and separating heavy metal from water, attributed to its eco-friendly, cost-effective, and high efficiency. Adsorption isotherm modeling has been used for many years to predict the adsorption equilibrium mechanism, adsorption capacity, and the inherent characteristics of the adsorption process, all of which are substantial in evaluating the performance of adsorbents. This review summarizes the development history, fundamental characteristics, and mathematical derivations of various isotherm models, along with their applicable conditions and application scenarios in heavy metal adsorption. The latest progress in applying isotherm models with a one-parameter, two-parameter, and three-parameter in heavy metal adsorption using carbon-based materials, which has gained much attention in recent years as low-cost adsorbents, is critically reviewed and discussed. Several experimental factors affecting the adsorption equilibrium, such as solution pH, temperature, ionic strength, adsorbent dose, and initial heavy metal concentration, are briefly discussed. The criteria for selecting the optimum isotherm for heavy metal adsorption are proposed by comparing various adsorption models and analyzing mathematical error functions. Finally, the relative performance of different isotherm models for heavy metal adsorption is compared, and the future research gaps are identified.