Alkali release was studied in a 10 kWthchemical looping pilot operated with a Linz-Donawitz (LD) slag oxygen carrier (OC) and three biomass fuels. Experiments were performed at three temperatures and in three operation modes: chemical looping combustion (CLC), chemical looping gasification (CLG), and oxygen-carrier-aided combustion (OCAC). Gas-phase alkali release was measured with a surface ionization detector (SID). Fuel reactor (FR) gas-phase alkali emissions increased with the temperature. This occurred as a result of increased evaporation of KCl and enhanced decomposition of alkali salts during char conversion. Air reactor (AR) alkali emissions were lower than in the FR and independent of the operating temperature. In comparison of operating modes, CLC and CLG modes resulted in similar gas-phase alkali emissions due to the similar extent of char conversion. In contrast, operation of the reactor system in OCAC mode resulted in significantly lower levels of gas-phase alkalis. The difference in alkali emission was attributed to the steam-rich atmosphere of CLC. The effect of steam was further investigated in CLC and OCAC tests. Lowering steam concentrations in CLC operation resulted in lower gas-phase alkali emissions, while introducing steam to the FR during OCAC operation resulted in higher alkali emissions. It was concluded that steam likely enhances gas-phase K release through a reaction of K2CO3within the fuel char with steam to produce KOH(g). Solid sampling and analysis for K content was used along with SID measurements to develop a K mass balance for the reactor system. Mass balance results for the straw pellet fuel tests showed that LD slag OC absorbs approximately 15-51% of fuel K, 2.2% of fuel K is released to the gas phase, and up to 3.4% of fuel K is captured in the AR fly ash. The residual 40-80% of fuel K was determined to leave the FR as K-rich fly ash.