Highly removal of anionic dye from aqueous medium using a promising biochar derived from date palm petioles: Characterization,adsorption properties and reuse studies

The present work investigates the preparation of promising biochar derived from date palm petioles powder (DPB) via a thermal treatment. DPB was characterized through various techniques to analyze the chemical (FTIR), morphological (SEM) and point of zero charges to investigate changes incorporated through the pyrolysis process.The adsorption of methyl orange (MO) onto the biochar was investigated using batch experiments according to different parameters which influence the adsorption process such as: initial dye concentration, equilibrium time, pH, and temperature. Isothermal and reuse studies of MO adsorption onto DPB were also investigated.Results of MO removal on DPB have demonstrated that the adsorption process was initial dye concentration-dependent, and equilibrium time was occurred in 60 min. The biochar presented high stability of MO adsorption capacity in a large domain of pH. Thermodynamic analysis of this process revealed that methyl orange adsorption was exothermic and spontaneous in nature.The experimental data were analyzed by pseudo-first-order, pseudo-second-order model, and the intraparticle-diffusion for kinetics and Langmuir, Freundlich, and Temkin models for isotherms.Kinetic adsorption followed the pseudo-second-order model and the intraparticle-diffusion within pores controlled the adsorption rate. The experimental data yielded good fits with in the following isotherms order: Langmuir > Temkin > Freundlich, The maximum adsorption capacity of MO on DPB was found 461 mg.g^?1. The reusability study reveals the possibility of the reuse of DPB for three (03) cycles of adsorption–desorption, a slight decrease in the ability of methyl orange adsorption has noticed with the increase of the number of adsorption–desorption cycles : 81.03 %, 67.84 %, and 51.72 %, respectively. The found results of the present study show that the biochar derived from date palm petioles have the potential to be used as a promising adsorbent for the treatment of MO dye.     

Kinetics and thermodynamics of bromophenol blue adsorption by a mesoporous hybrid gel derived from tetraethoxysilane and bis(trimethoxysilyl)hexane

A mesoporous hybrid gel is prepared with tetraethoxysilane (TEOS) and bis(trimethoxysilyl)hexane (TSH) as precursors without using any templating agent. Nitrogen sorption, TG-DTA, FTIR, and point of zero charge (PZC) measurement are used to characterize the gel. The gel has a specific surface area of 695 m(2) g(-1) with a pore size of 3.5 nm, a pore volume of 0.564 cm(3) g(-1), and a point of zero charge (PZC) of 6.2. The kinetics and thermodynamics of bromophenol blue (BPB) adsorption by the gel in aqueous solution are investigated comprehensively. The effects of initial BPB concentration, pH, ionic strength, and temperature on the adsorption are investigated. Kinetic studies show that the kinetic data are well described by the pseudo-second-order kinetic model. Initial adsorption rate increases with the increase in initial BPB concentration and temperature. Adsorption activation energy is found to be 62.5-67.5 kJ mol(-1) depending on the initial BPB concentration. Internal diffusion appears to be the rate-limiting step for the adsorption process. The equilibrium adsorption amount increases with the increase in the initial BPB concentration, solution acidity, and ionic strength, but decreases with the increase in temperature. The thermodynamic analysis indicates that the adsorption is spontaneous and exothermic. The adsorption isotherms can be well described with Freundlich equation indicating the heterogeneity of the hybrid gel surface. Electrostatic and hydrophobic interactions are suggested to be the dominant mechanism for adsorption.     

Characterization and Artificial Neural Networks Modelling of methylene blue adsorption of biochar derived from agricultural residues: Effect of biomass type,pyrolysis temperature,particle size

Biochar has been explored as a sorbent for contaminants, soil amendment and climate change mitigation tool through carbon sequestration. Through the optimization of the pyrolysis process, biochar can be designed with qualities to suit the intended uses. Biochar samples were prepared from four particle sizes (100–2000 µm) of three different feedstocks (oak acorn shells, jift and deseeded carob pods) at different pyrolysis temperatures (300–600 °C). The effect of these combinations on the properties of the produced biochar was studied. Biochar yield decreased with increasing pyrolysis temperature for all particle sizes of the three feedstocks. Ash content, fixed carbon, thermal stability, pH, electrical conductivity (EC), specific surface area (SSA) of biochar increased with increasing pyrolysis temperature. Volatile matter and pH value at the point of zero charge (pH_pzc) of biochar decreased with increasing pyrolysis temperature. Fourier-transform infrared spectroscopy (FTIR) analysis indicated that the surface of the biochar was rich with hydroxyl, phenolic, carbonyl and aliphatic groups. Methylene blue (MB) adsorption capacity was used as an indicator of the quality of the biochar. Artificial neural networks (ANN) model was developed to predict the quality of the biochar based on operational conditions of biochar production (parent biomass type, particle size, pyrolysis temperature). The model successfully predicted the MB adsorption capacity of the biochar. The model is a very useful tool to predict the performance of biochar for water treatment purposes or assessing the general quality of a design biochar for specific application.     

Differentiation of various traditional Chinese medicines derived from animal bile and gallstone: simultaneous determination of bile acids by liquid chromatography coupled with triple quadrupole mass spectrometry

Animal biles and gallstones are popularly used in traditional Chinese medicines, and bile acids are their major bioactive constituents. Some of these medicines, like cow-bezoar, are very expensive, and may be adulterated or even replaced by less expensive but similar species. Due to poor ultraviolet absorbance and structural similarity of bile acids, effective technology for species differentiation and quality control of bile-based Chinese medicines is still lacking. In this study, a rapid and reliable method was established for the simultaneous qualitative and quantitative analysis of 18 bile acids, including 6 free steroids (cholic acid, chenodeoxycholic acid, deoxycholic acid, lithocholic acid, hyodeoxycholic acid, and ursodeoxycholic acid) and their corresponding glycine conjugates and taurine conjugates, by using liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS). This method was used to analyze six bile-based Chinese medicines: bear bile, cattle bile, pig bile, snake bile, cow-bezoar, and artificial cow-bezoar. Samples were separated on an Atlantis dC₁₈ column and were eluted with methanol–acetonitrile–water containing ammonium acetate. The mass spectrometer was monitored in the negative electrospray ionization mode. Total ion currents of the samples were compared for species differentiation, and the contents of bile acids were determined by monitoring specific ion pairs in a selected reaction monitoring program. All 18 bile acids showed good linearity (r² > 0.993) in a wide dynamic range of up to 2000-fold, using dehydrocholic acid as the internal standard. Different animal biles could be explicitly distinguished by their major characteristic bile acids: tauroursodeoxycholic acid and taurochenodeoxycholic acid for bear bile, glycocholic acid, cholic acid and taurocholic acid for cattle bile, glycohyodeoxycholic acid and glycochenodeoxycholic acid for pig bile, and taurocholic acid for snake bile. Furthermore, cattle bile, cow-bezoar, and artificial cow-bezoar could be differentiated by the existence of hyodeoxycholic acid and the ratio of cholic acid to deoxycholic acid. This study provided bile acid profiles of bile-based Chinese medicines for the first time, which could be used for their quality control.     

Ultra‐performance liquid chromatography coupled with electrospray ionization/quadrupole time‐of‐flight mass spectrometry for the rapid analysis of constituents in the traditional Chinese medical formula Danggui San

In this work, ultra‐performance LC with ESI quadrupole TOF‐MS (UPLC–ESI‐Q‐TOF‐MS) and automated MetaboLynx analysis was used to rapidly separate and identify the chemical constituents of Danggui San, a traditional Chinese medical formula. The analysis was performed on a Waters UPLC BEH C₁₈ column using a gradient elution system. A hyphenated ESI and Q‐TOF analyzer was used for the determination of the accurate mass of the protonated or deprotonated molecule and fragment ions in both positive and negative modes. Based on retention times, accurate mass, and the mass spectrometric fragmentation characteristics, a total of 47 compounds distributed over the chemical groups of phthalides, flavonoids, monoterpene glycosides, sesquiterpenoids, phenolics, and alkaloids, were simultaneously separated within 18 min and identified or tentatively elucidated in Danggui San for the first time. UPLC–ESI‐Q‐TOF‐MS analysis revealed the complexity of the chemical composition of this formula. The method developed is rapid, accurate, reliable, and highly sensitive to characterize the chemical constituents of Danggui San.