First principal observation documenting the three-dimensional uptake of cadmium and spatial distribution of cadmium hydroxyapatite mineral in bone char.

The 3-D matrix scale ion-exchange mechanism was explored for high-capacity cadmium (Cd) removal using bone chars (BC) chunks (1-2 mm) made at 500 °C (500BC) and 700 °C (700BC) in aqueous solutions. The Cd incorporation into the carbonated hydroxyapatite (CHAp) mineral of BC was examined using a set of synchrotron-based techniques. The Cd removal from solution and incorporation into mineral lattice were higher in 500BC than 700BC, and the diffusion depth was modulated by the initial Cd concentration and charring temperature. A higher carbonate level of BC, more pre-leached Ca sites, and external phosphorus input enhanced Cd removal. The 500BC showed a higher CO32-/PO43- ratio and specific surface area (SSA) than the 700BC, providing more vacant sites by dissolution of Ca2+. In situ observations revealed the refilling of sub-micron pore space in the mineral matrix because of Cd incorporation.The X-ray nanodiffraction (XND) analyses revealed that Cd was mainly removed from water by incorporation into the mineral lattice of 500BC via ion exchange, rather than surface sorption and precipitation, and the mineral phase was transformed from hydroxyapatite (HAp) to cadmium hydroxyapatite (Cd-HAp). The Rietveld's refinement of X-ray diffraction (XRD) data resolved up to 91% of the crystal displacement of Ca2+ by Cd2+. The specific phase and stoichiometry of the new Cd-HAp mineral was dependent on the level of ion exchange. This mechanistic study confirmed that 3-D ion exchange was the most important path for heavy metal removal from aqueous solution and immobilization in BC mineral matrix, and put forward a novel and sustainable remediation strategy for Cd removal in wastewater and soil clean-up.

Spent coffee ground torrefaction for waste remediation and valorization.

Spent coffee grounds (SCGs) are a noticeable waste that may cause environmental pollution problems if not treated appropriately. Torrefaction is a promising low-temperature carbonization technique to achieve waste remediation, recovery, and circular bioeconomy efficiently. This study aims to maximize lipids retained in thermally degraded SCGs, thereby upgrading their fuel quality to implement resource sustainability and availability. This work also analyzes the lipid contribution to biochar's calorific value under various carbonization temperatures and times. Torrefaction can retain 11-15 wt% lipids from SCG, but the lipid content decreases when the pyrolysis temperature is higher than 300 °C. Extracted lipid content consisting of fatty acids echoed the results of diesel adsorption capacity. The lipid content in the biochar from SCG torrefied at 300 °C for 30 min is 11.00 wt%, and its HHV is 28.16 MJ kg-1. In this biochar, lipids contribute about 14.84% of the calorific value, and the other carbonized solid contributes 85.16%. On account of the higher lipid content in the biochar, it has the highest diesel adsorption amount per unit mass, with a value of 1.66 g g-1. This value accounts for a 22.1% improvement compared to its untorrefied SCG. Accordingly, torrefaction can sufficiently remediate SCG-derived environmental pollution. The produced biochar can become a spilled oil adsorbent. Furthermore, oil-adsorbed biochar (oilchar) is a potential solid fuel. In summary, SCG torrefaction can simultaneously achieve pollution remediation, waste valorization, resource sustainability, and circular bioeconomy.

Multi-objective operation optimization of spent coffee ground torrefaction for carbon-neutral biochar production.

Many energy-intensive processes are employed to enhance biomass fuel properties to overcome the difficulties in utilizing biomass as fuel. Therefore, energy conservation during these processes is crucial for realizing a circular bioeconomy. This study develops a newly devised method to evaluate SCG biochars' higher heating value (HHV) and predict moisture content from power consumption. It is found that the increasing rates of HHV immediately follow decreases in power consumption, which could be used to determine the pretreatment time for energy conservation. The non-dominated sorting genetic algorithm II (NSGA-II) maximizes SCG biochar's HHV while minimizing energy consumption. The results show that producing SCG biochar with 23.98 MJ∙kg-1 HHV requires 20.042 MJ∙kg-1, using a torrefaction temperature of 244 °C and torrefaction time of 27 min and 43 sec. Every kilogram of biochar with an energy yield of 85.93 % is estimated to cost NT$ 12.21.

Optimization via response surface methodology of palm kernel shell biochar for supplementary cementitious replacement.

The use of sustainable materials in the construction industry has been on the rise recently. Studies have proven that the use of conventional concrete and its raw materials has a negative impact on the environment. Research on incorporating biochar as a supplementary cementitious material has been recently evolving and has shown that the attributes of biochar are highly affected by the pyrolysis parameters. These attributes have enhanced the properties of biochar concrete and mortar composite. This paper identifies the different physiochemical properties exhibited by palm kernel shell biochar through optimization by response surface methodology. Focusing on some of the properties of biochar that have proven beneficial when used as a cement replacement. Very limited research has used optimization tools for the production of biochar with the intention of using it as a cement substitute. Pyrolysis was conducted by a tubular furnace at different temperature ranges from 200 °C to 800 °C. The biomass and biochar have been analyzed with TGA and FESEM-EDX. The targeted biochar properties and selected responses are the yield, carbon, oxygen, silica, and potassium content. The optimized parameters obtained are 409 °C, 15 °C/min, 120 min with responses of 38.2% yield, 73.37% carbon, 25.48% oxygen, 0.39% potassium and 0.44% silica. Thermal properties of the palm kernel shell biochar affected by the pyrolysis factors such as temperature, heating rate and residence time have also been discussed. In conclusion, this study supports and encourages the use of palm waste, which is abundant in Malaysia, as a supplementary cementitious material to promote sustainable growth in construction.

Dual pretreatment of mixing H2O2 followed by torrefaction to upgrade spent coffee grounds for fuel production and upgrade level identification of H2O2 pretreatment.

Biochar is a carbon-neutral solid fuel and has emerged as a potential candidate to replace coal. Meanwhile, spent coffee grounds (SCGs) are an abundant and promising biomass waste that could be used for biochar production. This study develops a biochar valorization strategy by mixing SCGs with hydrogen peroxide (H2O2) at a weight ratio of 1:0.75 to upgrade SCG biochar. In this dual pretreatment method, the H2O2 oxidative ability at a pretreatment temperature of 105 °C contributes to an increase in the higher heating value (HHV) and carbon content of the SCG biochars. The HHV and carbon content of biochar increase by about 6.5% and 7.8%, respectively, when compared to the unpretreated one under the same conditions. Maximized biochar's HHV derived via the Taguchi method is 30.33 MJkg-1, a 46.9% increase compared to the raw SCG, and a 6.5% increase compared to the unpretreated SCG biochar. The H2O2 concentration is 18% for the maximized HHV. A quantitative identification index of intensity of difference (IOD) is adopted to evaluate the contributive level of H2O2 pretreatment in terms of the HHV and carbon content. IOD increases with increasing H2O2 pretreatment temperature. Before torrefaction, SCGs' IOD pretreated at 50 °C is 1.94%, while that pretreated at 105 °C is 8.06%. This is because, before torrefaction, H2O2 pretreatment sufficiently weakens SCGs' molecular structure, resulting in a higher IOD value. The IOD value of torrefied SCGs (TSCG) pretreated at 105 °C is 10.71%, accounting for a 4.59% increase compared to that pretreated at 50 °C. This implies that TSCG pretreated by H2O2 at 105 °C has better thermal stability. For every 1% increase in IOD of TSCG, the carbon content of the biochar increases 0.726%, and the HHV increases 0.529%. Overall, it is demonstrated that H2O2 is a green and promising pretreatment additive for upgrading SCG biochar's calorific value, and torrefied SCGs can be used as a potential solid fuel to approach carbon neutrality.

Co-pyrolysis of microalgae and other biomass wastes for the production of high-quality bio-oil: Progress and prospective.

Microalgae are the most prospective raw materials for the production of biofuels, pyrolysis is an effective method to convert biomass into bioenergy. However, biofuels derived from the pyrolysis of microalgae exhibit poor fuel properties due to high content of moisture and protein. Co-pyrolysis is a simple and efficient method to produce high-quality bio-oil from two or more materials. Tires, plastics, and bamboo waste are the optimal co-feedstocks based on the improvement of yield and quality of bio-oil. Moreover, adding catalysts, especially CaO and Cu/HZSM-5, can enhance the quality of bio-oil by increasing aromatics content and decreasing oxygenated and nitrogenous compounds. Consequently, this paper provides a critical review of the production of bio-oil from co-pyrolysis of microalgae with other biomass wastes. Meanwhile, the underlying mechanism of synergistic effects and the catalytic effect on co-pyrolysis are discussed. Finally, the economic viability and prospects of microalgae co-pyrolysis are summarized.

Green additive to upgrade biochar from spent coffee grounds by torrefaction for pollution mitigation.

A green approach using hydrogen peroxide (H2O2) to intensify the fuel properties of spent coffee grounds (SCGs) through torrefaction is developed in this study to minimize environmental pollution. Meanwhile, a neural network (NN) is used to minimize bulk density at different combinations of operating conditions to show the accurate and reliable model of NN (R2 = 0.9994). The biochar produced from SCGs torrefied at temperatures of 200-300 °C, duration of 30-60 min, and H2O2 concentrations of 0-100 wt% is examined. The results reveal that the higher heating value (HHV) of biochar increases with rising temperature, duration, or H2O2 concentration, whereas the bulk density has an opposite trend. The HHV, ignition temperature, and bulk density of biochar from torrefaction at 230 °C for 30 min with a 100 wt% H2O2 solution (230-100%-TSCG) are 27.00 MJ∙kg-1, 292 °C, and 120 kg∙m-3, respectively. This HHV accounts for a 29% improvement compared to that of untorrefied SCG. The contact angle (126°), water activity (0.51 aw), and moisture content (7.69%) of the optimized biochar indicate that it has higher resistance against biodegradation, and thereby can be stored longer. Overall, H2O2 is a green treatment additive for SCGs solid fuel. This study has successfully produced biochar with greater HHV and low bulk density at low temperatures. The green additive development can effectively reduce environmental pollutants and upgrade wastes into resources, and achieve "3E", namely, environmental (non-polluting green additives), energy (biofuel), and circular economy (waste upgrade). In addition, the produced biochar has great potential in the fields of bioadsorbents and soil amendments.

Pore volume upgrade of biochar from spent coffee grounds by sodium bicarbonate during torrefaction.

A novel approach for upgrading the pore volume of biochar at low temperatures using a green additive of sodium bicarbonate (NaHCO3) is developed in this study. The biochar was produced from spent coffee grounds (SCGs) torrefied at different temperatures (200-300 °C) with different residence times (30-60 min) and NaHCO3 concentrations (0-8.3 wt%). The results reveal that the total pore volume of biochar increases with rising temperature, residence time, or NaHCO3 aqueous solution concentration, whereas the bulk density has an opposite trend. The specific surface area and total pore volume of pore-forming SCG from 300 °C torrefaction for 60 min with an 8.3 wt% NaHCO3 solution (300-TP-SCG) are 42.050 m2 g-1 and 0.1389 cm3·g-1, accounting for the improvements of 141% and 76%, respectively, compared to the parent SCG. The contact angle (126°) and water activity (0.48 aw) of 300-TP-SCG reveal that it has long storage time. The CO2 uptake capacity of 300-TP-SCG is 0.32 mmol g-1, rendering a 39% improvement relative to 300-TSCG, namely, SCG torrefied at 300 °C for 60 min. 300-TP-SCG has higher HHV (28.31 MJ·kg-1) and lower ignition temperature (252 °C). Overall, it indicates 300-TP-SCG is a potential fuel substitute for coal. This study has successfully produced mesoporous biochar at low temperatures to fulfill "3E", namely, energy (biofuel), environment (biowaste reuse solid waste), and circular economy (bioadsorbent).

Synthesis of renewable heterogeneous acid catalyst from oil palm empty fruit bunch for glycerol-free biodiesel production.

Interest in biodiesel research has escalated over the years due to dwindling fossil fuel reserves. The implementation of a carbon-based solid acid catalyst in biodiesel production eradicates the separation problems associated with homogeneous catalysis. However, its application in the glycerol-free interesterification process for biodiesel production is still rarely being studied in the literature. In this study, novel environmentally benign catalysts were prepared from oil palm empty fruit bunch (OPEFB) derived activated carbon (AC) which is sustainable and low cost via direct sulfonation using concentrated sulfuric acid. The effects of synthesizing variables such as carbonization and sulfonation temperatures with different holding times towards the fatty acid methyl ester (FAME) yield in interesterification reaction with oleic acid and methyl acetate were investigated in detail. It was found that the optimum carbonization temperature and duration together with sulfonation temperature and duration were 600 °C, 3 h, 100 °C and 6 h, respectively. The catalyst possessed an amorphous structure with a high total acid density of 9.0 mmol NaOH g-1 due to the well-developed porous framework structure of the carbon support. Under these optimum conditions, the OPEFB derived solid acid catalyst recorded an excellent catalytic activity of 50.5% methyl oleate yield at 100 °C after 8 h with 50:1 methyl acetate to oleic acid molar ratio and 10 wt% catalyst dosage. The heterogeneous acid catalyst derived from OPEFB had shown promising properties that made them highly suitable for cost-effective and environmental-friendly glycerol-free biodiesel production.

Effect of torrefaction pretreatment on the pyrolysis of rubber wood sawdust analyzed by Py-GC/MS.

The aim of this study was to investigate the effect of torrefaction on the pyrolysis of rubber wood sawdust (RWS) using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Three typical torrefaction temperatures (200, 250, and 300 °C) and pyrolysis temperatures (450, 500, and 550 °C) were considered. The results suggested that only diethyl phthalate, belonging to esters, was detected at the torrefaction temperatures of 200 and 250 °C, revealing hemicellulose degradation. With the torrefaction temperature of 300 °C, esters, aldehydes, and phenols were detected, suggesting the predominant decomposition of hemicellulose and lignin. The double-shot pyrolysis indicated that the contents of oxy-compounds such as acids and aldehydes in pyrolysis bio-oil decreased with rising torrefaction temperature, implying that increasing torrefaction severity abated oxygen content in the bio-oil. With the torrefaction temperature of 300 °C, relatively more cellulose was retained in the biomass because the carbohydrate content in the pyrolysis bio-oil increased significantly.

Pyrolysis characteristics and kinetics of microalgae via thermogravimetric analysis (TGA): A state-of-the-art review.

Pyrolysis is a promising route for biofuels production from microalgae at moderate temperatures (400-600°C) in an inert atmosphere. Depending on the operating conditions, pyrolysis can produce biochar and/or bio-oil. In practice, knowledge for thermal decomposition characteristics and kinetics of microalgae during pyrolysis is essential for pyrolyzer design and pyrolysis optimization. Recently, the pyrolysis kinetics of microalgae has become a crucial topic and received increasing interest from researchers. Thermogravimetric analysis (TGA) has been employed as a proven technique for studying microalgae pyrolysis in a kinetic control regime. In addition, a number of kinetic models have been applied to process the TGA data for kinetic evaluation and parameters estimation. This paper aims to provide a state-of-the art review on recent research activities in pyrolysis characteristics and kinetics of various microalgae. Common kinetic models predicting the thermal degradation of microalgae are examined and their pros and cons are illustrated.

Abundant expression and functional participation of TRPV1 at Zusanli acupoint (ST36) in mice: mechanosensitive TRPV1 as an "acupuncture-responding channel".

BACKGROUND: Acupuncture is a therapy that involves applying mechanical stimulation to acupoints using needles. Although acupuncture is believed to trigger neural regulation by opioids or adenosine, still little is known about how physical stimulation is turned into neurological signaling. The transient receptor potential vanilloid receptors 1 and 4 (TRPV1 and TRPV4) and the acid-sensing ion channel 3 (ASIC3) are regarded as mechanosensitive channels. This study aimed to clarify their role at the Zusanli acupoint (ST36) and propose possible sensing pathways linking channel activation to neurological signaling. METHODS: First, tissues from different anatomical layers of ST36 and the sham point were sampled, and channel expressions between the two points were compared using western blotting. Second, immunofluorescence was performed at ST36 to reveal distribution pattern of the channels. Third, agonist of the channels were injected into ST36 and tested in a mouse inflammatory pain model to seek if agonist injection could replicate acupuncture-like analgesic effect. Last, the components of proposed downstream sensing pathway were tested with western blotting to determine if they were expressed in tissues with positive mechanosensitive channel expression. RESULTS: The results from western blotting demonstrated an abundance of TRPV1, TRPV4, and ASIC3 in anatomical layers of ST36. Furthermore, immunofluorescence showed these channels were expressed in both neural and non-neural cells at ST36. However, only capsaicin, a TRPV1 agonist, replicated the analgesic effect of acupuncture when injected into ST36. Components of calcium wave propagation (CWP, the proposed downstream sensing pathway) were also expressed in tissues with abundant TRPV1 expression, the muscle and epimysium layers. CONCLUSIONS: The results demonstrated mechanosensitive channel TRPV1 is highly expressed at ST36 and possibly participated in acupuncture related analgesia. Since CWP was reported by other to occur during acupuncture and its components were shown here to express in tissues with positive TRPV1 expression. These findings suggest TRPV1 might act as acupuncture-responding channel by sensing physical stimulation from acupuncture and conducting the signaling via CWP to nerve terminals. This study provided a better understanding between physical stimulation from acupuncture to neurological signaling.

Biomass torrefaction characteristics in inert and oxidative atmospheres at various superficial velocities.

The reaction characteristics of four biomass materials (i.e. oil palm fiber, coconut fiber, eucalyptus, and Cryptomeria japonica) with non-oxidative and oxidative torrefaction at various superficial velocities are investigated where nitrogen and air are used as carrier gases. Three torrefaction temperatures of 250, 300, and 350 °C are considered. At a given temperature, the solid yield of biomass is not affected by N2 superficial velocity, revealing that the thermal degradation is controlled by heat and mass transfer in biomass. Increasing air superficial velocity decreases the solid yield, especially in oil palm fiber and coconut fiber, implying that the torrefaction reaction of biomass is dominated by surface oxidation. There exists an upper limit of air superficial velocity in the decrement of solid yield, suggesting that beyond this limit the thermal degradation of biomass is no longer governed by surface oxidation, but rather is controlled by internal mass transport.

Electroacupuncture Reduces Carrageenan- and CFA-Induced Inflammatory Pain Accompanied by Changing the Expression of Nav1.7 and Nav1.8, rather than Nav1.9, in Mice Dorsal Root Ganglia.

Several voltage-gated sodium channels (Navs) from nociceptive nerve fibers have been identified as important effectors in pain signaling. The objective of this study is to investigate the electroacupuncture (EA) analgesia mechanism by changing the expression of Navs in mice dorsal root ganglia (DRG). We injected carrageenan and complete Freund's adjuvant (CFA) into the mice plantar surface of the hind paw to induce inflammation and examined the antinociception effect of EA at the Zusanli (ST36) acupoint at 2 Hz low frequency. Mechanical hyperalgesia was evaluated by using electronic von Frey filaments, and thermal hyperalgesia was assessed using Hargreaves' test. Furthermore, we observed the expression and quality of Navs in DRG neurons. Our results showed that EA reduced mechanical and thermal pain in inflammatory animal model. The expression of Nav1.7 and Nav1.8 was increased after 4 days of carrageenan- and CFA-elicited inflammatory pain and further attenuated by 2 Hz EA stimulation. The attenuation cannot be observed in Nav1.9 sodium channels. We demonstrated that EA at Zusanli (ST36) acupoint at 2 Hz low-frequency stimulation attenuated inflammatory pain accompanied by decreasing the expression of Nav1.7 and 1.8, rather than Nav1.9, sodium channels in peripheral DRG neurons.

Attenuation of TRPV1 and TRPV4 Expression and Function in Mouse Inflammatory Pain Models Using Electroacupuncture.

Although pain is a major human affliction, our understanding of pain mechanisms is limited. TRPV1 (transient receptor potential vanilloid subtype 1) and TRPV4 are two crucial receptors involved in inflammatory pain, but their roles in EA- (electroacupuncture-) mediated analgesia are unknown. We injected mice with carrageenan (carra) or a complete Freund's adjuvant (CFA) to model inflammatory pain and investigated the analgesic effect of EA using animal behavior tests, immunostaining, Western blotting, and a whole-cell recording technique. The inflammatory pain model mice developed both mechanical and thermal hyperalgesia. Notably, EA at the ST36 acupoint reversed these phenomena, indicating its curative effect in inflammatory pain. The protein levels of TRPV1 and TRPV4 in DRG (dorsal root ganglion) neurons were both increased at day 4 after the initiation of inflammatory pain and were attenuated by EA, as demonstrated by immunostaining and Western blot analysis. We verified DRG electrophysiological properties to confirm that EA ameliorated peripheral nerve hyperexcitation. Our results indicated that the AP (action potential) threshold, rise time, and fall time, and the percentage and amplitude of TRPV1 and TRPV4 were altered by EA, indicating that EA has an antinociceptive role in inflammatory pain. Our results demonstrate a novel role for EA in regulating TRPV1 and TRPV4 protein expression and nerve excitation in mouse inflammatory pain models.

Torrefaction and low temperature carbonization of oil palm fiber and Eucalyptus in nitrogen and air atmospheres.

Torrefaction is a pretreatment method for upgrading biomass as solid fuels. To provide flexible operations for effectively upgrading biomass at lower costs, the aim of this study was to investigate the properties of oil palm fiber and eucalyptus pretreated in nitrogen and air atmospheres at temperatures of 250-350°C for 1h. Based on energy and solid yield and introducing an energy-mass co-benefit index (EMCI), oil palm fiber pretreatment under nitrogen at 300°C provided the solid fuel with higher energy density and less volume compared to other temperatures. Pretreatment of oil palm fiber in air resulted in the fuel with low solid and energy yields and is therefore not recommended. For eucalyptus, nitrogen and air can be employed to upgrade the biomass, and the suggested temperatures are 325 and 275°C, respectively.

Acid-sensing ion channel 3 mediates peripheral anti-hyperalgesia effects of acupuncture in mice inflammatory pain.

BACKGROUND: Peripheral tissue inflammation initiates hyperalgesia accompanied by tissue acidosis, nociceptor activation, and inflammation mediators. Recent studies have suggested a significantly increased expression of acid-sensing ion channel 3 (ASIC3) in both carrageenan- and complete Freund's adjuvant (CFA)-induced inflammation. This study tested the hypothesis that acupuncture is curative for mechanical hyperalgesia induced by peripheral inflammation. METHODS: Here we used mechanical stimuli to assess behavioral responses in paw and muscle inflammation induced by carrageenan or CFA. We also used immunohistochemistry staining and western blot methodology to evaluate the expression of ASIC3 in dorsal root ganglion (DRG) neurons. RESULTS: In comparison with the control, the inflammation group showed significant mechanical hyperalgesia with both intraplantar carrageenan and CFA-induced inflammation. Interestingly, both carrageenan- and CFA-induced hyperalgesia were accompanied by ASIC3 up-regulation in DRG neurons. Furthermore, electroacupuncture (EA) at the ST36 rescued mechanical hyperalgesia through down-regulation of ASIC3 overexpression in both carrageenan- and CFA-induced inflammation. CONCLUSIONS: In addition, electrical stimulation at the ST36 acupoint can relieve mechanical hyperalgesia by attenuating ASIC3 overexpression.