Biochar alters hydraulic conductivity and impacts nutrient leaching in two agricultural soils

Biochar is purported to provide agricultural benefits when added to the soil, through changes in saturated hydraulic conductivity (Ksat) and increased nutrient retention through chemical or physical means. Despite increased interest and investigation, there remains uncertainty regarding the ability of biochar to deliver these agronomic benefits due to differences in biochar feedstock, production method, production temperature, and soil texture. In this project, a suite of experiments was carried out using biochars of diverse feedstocks and production temperatures, in order to determine the biochar parameters which may optimize agricultural benefits. Sorption experiments were performed with seven distinct biochars to determine sorption efficiencies for ammonium and nitrate. Only one biochar effectively retained nitrate, while all biochars bound ammonium. The three biochars with the highest binding capacities (produced from almond shell at 500 and 800 ∘C (AS500 and AS800) and softwood at 500 ∘C (SW500)) were chosen for column experiments. Biochars were amended to a sandy loam and a silt loam at 0 % and 2 % (w/w), and Ksat was measured. Biochars reduced Ksat in both soils by 64 %–80 %, with the exception of AS800, which increased Ksat by 98 % in the silt loam. Breakthrough curves for nitrate and ammonium, as well as leachate nutrient concentration, were also measured in the sandy loam columns. All biochars significantly decreased the quantity of ammonium in the leachate, by 22 % to 78 %, and slowed its movement through the soil profile. Ammonium retention was linked to high cation exchange capacity and a high oxygen-to-carbon ratio, indicating that the primary control of ammonium retention in biochar-amended soils is the chemical affinity between biochar surfaces and ammonium. Biochars had little to no effect on the timing of nitrate release, and only SW500 decreased total quantity, by 27 % to 36 %. The ability of biochar to retain nitrate may be linked to high micropore specific surface area, suggesting a physical entrapment rather than a chemical binding. Together, this work sheds new light on the combined chemical and physical means by which biochar may alter soils to impact nutrient leaching and hydraulic conductivity for agricultural production.

Adsorption of Cr(VI) onto cross-linked chitosan-almond shell biochars: equilibrium, kinetic, and thermodynamic studies

In this study, to remove Cr(VI) from the solution environment by adsorption, the almond shell was pyrolyzed at 400 and 500 °C and turned into biochar (ASC400 and ASC500) and composite adsorbents were obtained by coating these biochars with chitosan (Ch-ASC400 and Ch-ASC500). The resulting biochars and composite adsorbents were characterized using Fourier transform infrared (FTIR) spectroscopy; Brunauer, Emmett, and Teller (BET) surface area; scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX); and the point of zero charge pH (pHpzc) analyses. The parameters affecting the adsorption were examined with batch adsorption experiments and the optimum parameters for the efficient adsorption of Cr(VI) in 55 mg L−1 solution were determined as follows; adsorbent dosages: 5 g L−1 for biochars, 1.5 g L−1 for composite adsorbents, contact time: 120 min, pH: 1.5. It was seen that the temperature did not affect the adsorption much. Under optimum conditions, Cr(VI) adsorption capacities of ASC400, ASC500, Ch-ASC400, and Ch-ASC500 adsorbents are 11.33, 11.58, 37.48, and 36.65 mg g−1, respectively, and their adsorption percentages are 95.2%, 97.5%, 94.3%, and 94.0%, respectively. Adsorption data were applied to Langmuir, Freundlich, Scatchard, Dubinin-Radushkevic, and Temkin isotherms and pseudo-first-order kinetic model, pseudo-second-order kinetic model, intra-particle diffusion model, and film diffusion model. The adsorption data fitted well to the Langmuir isotherm and pseudo-second-order kinetic models. From these results, it was determined that chemical adsorption is the dominant mechanism. Also, both intra-particle diffusion and film diffusion is effective in the adsorption rate. For all adsorbents, the Langmuir isotherm proved to be the most appropriate model for adsorption. The maximum monolayer adsorption capacities calculated from this model are 24.15 mg g−1, 27.38 mg g−1, 54.95 mg g−1, and 87.86 mg g−1 for ASC400, ASC500, Ch-ASC400, and Ch-ASC500, respectively. The enthalpy change, entropy change, and free energy changes during the adsorption process were calculated and the adsorption was also examined thermodynamically. As a result, adsorption occurs spontaneously for all adsorbents.

Organic Dyes Adsorption on the Almond Shell (Prunus dulcis) as Agricultural Solid Waste from Aqueous Solution in Single and Binary Mixture Systems

Almond shell (AS) is a low-cost adsorbent used in this study for the removal of methylene blue (MB), crystal violet (CV), and Congo red (CR) from an aqueous solution in single and mixture binary systems. The low-cost adsorbent was characterized by FTIR and SEM analysis. The effects of AS dose, contact time, initial dye concentration, pH, and temperature on MB, CV, and CR adsorption were studied in a single system. In a binary system, the MB, CV, and CR were removed from the mixture of MB+CR, CV+MB, and CV+CR with a percentage in volume ranging from 0 to 100 % in MB and CV, and CR. Kinetic studies showed rapid sorption following a second-order kinetic model with of contact time of 10 min. The modulation of adsorption isotherms showed that retention follows the Langmuir model. The thermodynamic parameters proved that the MB, CV, and CR adsorption process was feasible, spontaneous, and exothermic. The synergy adsorption between dyes in a binary mixture of MB+CR and CV+CR, while the competition adsorption between dyes in a binary mixture of MB+ CV.

Extraction and Characterization of Cellulose and Cellulose Nanowhiskers from Almond Shell Biomass, Metal Removal and Toxicity Analysis

Almond shell is a major agro-industry waste. Cellulose is the major crystalline component of naturally porous almond shell biomass. In this study, cellulose (ASC) was isolated from almond shell (AS) by the dewaxing-alkali treatment-bleaching method, and nanocrystalline cellulose (ASN) was obtained by sulphuric acid hydrolysis of the obtained ASC. Separation efficiency was confirmed by X-ray diffraction and IR absorption studies. ASC exhibited predominantly microporous monolithic structures under a scanning electron microscope. Its porosity resulted in significant absorption of Cu(II) and Pb(II) ions when applied as an absorbent in their solutions. Transmission electron microscopy and atomic force microscopy revealed the formation of ASN nanowhiskers with an average length and diameter of 170 nm and 20 nm, respectively. Zeta potential of -32.4 mV suggested good colloidal dispersibility of the nanowhiskers. No hemolytic toxicity to erythrocyte cells was recorded, which suggested the potential applicability of the obtained nanomaterial in foods and pharmaceuticals. Remarkably high crystallinity and thermal resistance observed from calorimetry and thermogravimetry studies indicated enhanced density of the crystalline moiety during synthesis. ASC and ASN can be developed as effective metal absorption substrates and reinforcement agents in heat-resistant composite materials.