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.

Efficient aqueous molybdenum removal using commercial Douglas fir biochar and its iron oxide hybrids.

Molybdenum (Mo) is a naturally-occurring trace element in drinking water. Most commonly, molybdate anions (MoO42-) are in well water and breast milk. In addition, it is used in medical image testing. Recently, the EPA classified Mo as a potential contaminant, as exposure can lead to health effects such as gout, hyperuricemia, and even lung cancer. We have assessed the sorptive removal of aqueous molybdate using Douglas fir biochar (DFBC) and a hybrid DFBC/Fe3O4 composite containing chemically-coprecipitated iron oxide (Fe3O4). Adsorption was studied at various: pH values, equilibrium times (5 min-24 h), initial Mo concentrations (2.5-1000 mg/L), and temperatures (5, 25, and 40 °C) using batch sorption and fixed-bed column equilibrium methods. Langmuir capacities for DFBC and DFBC/Fe3O4 (at pH 3, 2 hrs equilibrium) were within 459.3-487.9 mg/g and 288-572 mg/g, respectively. These adsorbents and their Mo-laden counterparts were characterized by elemental analysis, BET, PZC, SEM, TEM, EDS, XRD, and XPS. MoO42- adsorption on DFBC is thought to be governed primarily via electrostatic attraction. Adsorption by DFBC/Fe3O4 is primarily governed by chemisorption onto magnetite surface hydroxyl groups, while electrostatics prevail in the DFBC-exposed phase. Stoichiometric precipitation of iron molybdates triggered by iron dissolution was also considered. The data suggest that DFBC and DFBC/Fe3O4 are promising candidates for molybdate sorption.