Contribution of modified P-enriched biochar on pH buffering capacity of acidic soil.

Biochar can directly hold cations in soil because of the negative charge that exists on its surfaces. Besides, improving soil cation exchange capacity, the negative charges on biochar surfaces can buffer acid soil by protonation and deprotonation mechanisms. Moreover, biochar ameliorates soil acidity due to the presence of oxides, carbonates, and hydroxides of its basic cations (Ca, Na, K, and Mg). Both biochar surface functional group and basic cation concentrations can be altered by modification with chemical agents which can affect its soil pH buffering capacity. However, the impact of modified biochar application on soil pH buffering capacity is still scanty. This study investigated the pH buffering capacity of acidic soil amended with three P-enriched modified Douglas fir biochars and compared this buffering capacity to amendment with untreated Douglas fir biochar. These three P-enriched biochars, were prepared by treating Douglas fir biochar (DFB), respectively, with: 1) anhydrous calcium chloride (CaCl2) and potassium phosphate monobasic (KH2PO4), 2) calcium carbonate (CaCO3) and diammonium phosphate {(NH4)2HPO4} and 3) an aqueous solution of magnesium sulfate (MgSO4), potassium hydroxide (KOH) and potassium phosphate monobasic (KH2PO4). The three P-enriched biochars were designated as CCPP, CAPP and MSPP, respectively. The soil pH buffering abilities were largely dependent on the added biochar's alkalinity and ash contents. The residual soil CEC was highly correlated (r ≥ 0.9), with the soil buffering capacity. Both alkalinity and pH buffering capacity improved following the order CCAP > CCPP > MSPP > DFB, while residual soil CEC followed the order CAPP > MSPP > CCPP > DFB. The pH buffering capacity of the soil after amendments with 10% CAPP, CCPP MSPP and BFB rose by 84.8, 58.3, 3.0 and 2.5%, respectively. Whereas MSPP had higher concentrations of K+ and Mg2+, greater concentrations of Ca2+ were present in CCAP and CCPP than MSPP. So, Ca2+ concentrations in biochar exerts a greater influence on alkalinity and buffering capacity than Mg2+ and K+ because of 1) its smaller effective hydration radius and larger charge density. 2) calcium hydroxide has a greater water solubility than magnesium hydroxide providing more available base. Since pH buffering capacity depends on cation exchange sites, soil additives containing Ca2+ are prone to create greater impacts than Mg2+ and K+ additives.

Lead immobilization in simulated polluted soil by Douglas fir biochar-supported phosphate.

This study compared the lead (Pb2+) immobilization efficacy of biochar-supported phosphate to conventional in-situ heavy metal immobilization methods (with lime, neat biochar and phosphate). The biochar-supported phosphate was obtained by treating Douglas fir biochar (BC) with anhydrous calcium chloride and potassium dihydrogen phosphate. The amount of Pb2+ immobilized was determined by comparing the concentration of ammonium nitrate extractable Pb2+ lead from lead-spiked soil (without amendment) to that of a 30 d incubation with (a) lead-spiked soil plus 5% (wt./wt.) biochar supported-phosphate, (b) lead-spiked soil plus 5% (wt./wt.) untreated Douglas fir biochar, (c) lead-spiked soil plus 5% (w/w) lime and (d) lead-spiked soil plus 5% (wt./wt.) potassium dihydrogen phosphate. The control (lead-spiked soil without amendment) produced the largest quantity (96.08 ± 9.22 mg L-1) of NH4NO3-extractable Pb2+, while lead-spiked soil treated with 5% (wt./wt.) biochar-supported phosphate resulted in the lowest quantity of NH4NO3 extractable Pb2+ (0.3 ± 0.2 mg L-1). The mechanism for immobilization of Pb2+ by BP occurs at pH < 7 through dissolution of hydroxyapatite embedded in BP during modification, followed by precipitation of insoluble Pb10(PO4)6(OH)2. The residual lead fraction in the lead-spiked soil increased by 20.9% following amendment with BP. These results indicate that biochar-supported phosphate is a candidate to reduce lead mobility (bioavailability) in polluted soil. This amendment may lower Pb2+ uptake into plants while minimizing the potential for water contamination due to Pb2+mobility.