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Sorption of ammonium and nitrate to biochars is electrostatic and pH-dependent.

ABSTRACT: Biochars are potentially effective sorbents for NH₄⁺ and NO₃^- in water treatment and soil applications. Here we compare NH₄⁺ and NO₃^- sorption rates to acid-washed biochars produced from red oak (Quercus rubra) and corn stover (Zea mays) at three pyrolysis temperatures (400, 500 and 600?°C) and a range of solution pHs (3.5-7.5). Additionally, we examined sorption mechanisms by quantification of NH₄⁺ and NO₃^- sorption, as well as Ca²⁺ and Cl^- displacement for corn stover biochars. Solution pH curves showed that NH₄⁺ sorption was maximized (0.7-0.8?mg?N g^-1) with low pyrolysis temperature (400?°C) biochar at near neutral pH (7.0-7.5), whereas NO₃^- sorption was maximized (1.4-1.5?mg?N g^-1) with high pyrolysis temperatures (600?°C) and low pH (3.5-4). The Langmuir (r²?=?0.90-1.00) and Freundlich (r²?=?0.81-0.97) models were good predictors for both NH₄⁺ (pH 7) and NO₃^- (pH 3.7) sorption isotherms. Lastly, NH₄⁺ and NO₃^- displaced Ca²⁺ and Cl^-, respectively, from previously CaCl₂-saturated corn stover biochars. Results from the pH curves, Langmuir isotherms, and cation displacement curves all support the predominance of ion exchange mechanisms. Our results demonstrate the importance of solution pH and chemical composition in influencing NH₄⁺ and NO₃^- sorption capacities of biochar.

SUBMITTER: Fidel RB

PROVIDER: S-EPMC6279760 | biostudies-literature | 2018 Dec

REPOSITORIES: biostudies-literature

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Sorption of ammonium and nitrate to biochars is electrostatic and pH-dependent.

Fidel Rivka B RB Laird David A DA Spokas Kurt A KA

Scientific reports 20181204 1

Biochars are potentially effective sorbents for NH4+ and NO3- in water treatment and soil applications. Here we compare NH4+ and NO3- sorption rates to acid-washed biochars produced from red oak (Quercus rubra) and corn stover (Zea mays) at three pyrolysis temperatures (400, 500 and 600 °C) and a range of solution pHs (3.5-7.5). Additionally, we examined sorption mechanisms by quantification of NH4 ...[more]

PMID: 30514956

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Project description:The primary purpose of this study is to eliminate Basic Red 46 dye from aqueous solutions utilizing batch experiments by adsorption on biochars prepared from bamboo and rice straw biomass. Biochars prepared from bamboo (B), and rice straw (R) was pyrolyzed at 500°C (B500 and R500). Scanning Electron Microscopy (SEM), Fourier Transform Infrared (FTIR) Spectroscopy, X-ray Diffraction (XRD), and surface area and porosity analyzers were used to characterize the B500 and R500 samples. The characterization results indicated that the biochars possessed an amorphous porous structure with many functional groups consisting primarily of silicates. The adsorption rate of BR46 was evaluated using two kinetic models (pseudo-first-order and pseudo-second-order), and the results indicated that the pseudo-second-order model fitted to the experimental data well (R2>0.99). Nearly 24 h was sufficient to achieve equilibrium with the dye adsorption for the two biochars. R500 had a greater adsorption efficiency than B500. As pH levels increased, the dye's adsorption capability increased as well. The Langmuir and Freundlich isotherm models were used to investigate the equilibrium behavior of BR46 adsorption, and the equilibrium data fitted well with the Langmuir model (R2>0.99) compared to the Freundlich model (R2>0.89). The maximum adsorption capacities of BR46 are 9.06 mg/g for B500 and 22.12 mg/g for R500, respectively. Additionally, adsorption capacity increased as temperature increased, indicating that adsorption is favored at higher temperatures. The electrostatic interaction is shown to be the dominant mechanism of BR46 adsorption, and BR46 acts as an electron-acceptor, contributing to n-π EDA (Electron Donor-Acceptor) interaction. Thermodynamic parameters for the dye-adsorbent system revealed that the adsorption process is spontaneous and feasible. The values of the adsorption coefficient (Kd) were on the order of 102-103. Kd of R500 was greater than that of B500, indicating that R500 had a greater adsorption capacity. The results showed that R500 could be used as a low-cost alternative adsorbent for removing BR46 from effluents.

Project description:The enzyme glycinamide ribonucleotide transformylase (GART) catalyzes the transfer of a formyl group from formyl tetrahydrofolate (fTHF) to glycinamide ribonucleotide (GAR), a process that is pH-dependent with pK(a) of approximately 8. Experimental studies of pH-rate profiles of wild-type and site-directed mutants of GART have led to the proposal that His108, Asp144, and GAR are involved in catalysis, with His108 being an acid catalyst, while forming a salt bridge with Asp144, and GAR being a nucleophile to attack the formyl group of fTHF. This model implied a protonated histidine with pK(a) of 9.7 and a neutral GAR with pK(a) of 6.8. These proposed unusual pK(a)s have led us to investigate the electrostatic environment of the active site of GART. We have used Poisson-Boltzmann-based electrostatic methods to calculate the pK(a)s of all ionizable groups, using the crystallographic structure of a ternary complex of GART involving the pseudosubstrate 5-deaza-5,6,7,8-THF (5dTHF) and substrate GAR. Theoretical mutation and deletion analogs have been constructed to elucidate pairwise electrostatic interactions between key ionizable sites within the catalytic site. Also, a construct of a more realistic catalytic site including a reconstructed pseudocofactor with an attached formyl group, in an environment with optimal local van der Waals interactions (locally minimized) that imitates closely the catalytic reactants, has been used for pK(a) calculations. Strong electrostatic coupling among catalytic residues His108, Asp144, and substrate GAR was observed, which is extremely sensitive to the initial protonation and imidazole ring flip state of His108 and small structural changes. We show that a proton can be exchanged between GAR and His108, depending on their relative geometry and their distance to Asp144, and when the proton is attached on His108, catalysis could be possible. Using the formylated locally minimized construct of GART, a high pK(a) for His108 was calculated, indicating a protonated histidine, and a low pK(a) for GAR(NH(2)) was calculated, indicating that GAR is in neutral form. Our results are in qualitative agreement with the current mechanistic picture of the catalytic process of GART deduced from the experimental data, but they do not reproduce the absolute magnitude of the pK(a)s extracted from fits of k(cat)-pH profiles, possibly because the static time-averaged crystallographic structure does not describe adequately the dynamic nature of the catalytic site during binding and catalysis. In addition, a strong effect on the pK(a) of GAR(NH(2)) is produced by the theoretical mutations of His108Ala and Asp144Ala, which is not in agreement with the observed insensitivity of the pK(a) of GAR(NH(2)) modeled from the experimental data using similar mutations. Finally, we show that important three-way electrostatic interactions between highly conserved His137, with His108 and Asp144, are responsible for stabilizing the electrostatic microenvironment of the catalytic site. In conclusion, our data suggest that further detailed computational and experimental work is necessary.

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Sorption of ammonium and nitrate to biochars is electrostatic and pH-dependent.

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Sorption of ammonium and nitrate to biochars is electrostatic and pH-dependent.

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