Direct numerical simulations (DNS) of an initially quiescent coupled air-water interface driven by an air flow with free stream speed of 5 m/s have been conducted. The DNS solves a scalar advection-diffusion equation for dissolved gas (or scalar) concentration in order to determine the impact of the water-side turbulence on scalar (mass) transfer from the air side to the water side and subsequent vertical transport in the water column. Two simulations are compared: one with a freely deforming interface and a second one with a flat interface. In the first simulation, the deforming interface evolves in the form of gravity-capillary waves generating aqueous Langmuir turbulence characterized by small-scale (centimeter-scale) Langmuir cells (LCs). The second simulation is characterized by pure shear-driven turbulence in the absence of LCs as the interface is intentionally held flat. It is concluded that the Langmuir turbulence serves to enhance vertical transport of the scalar in the water side and in the process increases scalar transfer efficiency relative to the shear-dominated turbulence in the flat interface case. Furthermore, transition to Langmuir turbulence was observed to be accompanied by a spike in scalar flux via molecular diffusion across the interface characterized by an order of magnitude increase. Such episodic flux increases, if linked to gusts and overall unsteadiness in the wind field, are expected to be an important contributor in determining the long-term average of the air-sea gas fluxes. The effectiveness of popular transfer velocity models, namely the small eddy model and the surface divergence model, in predicting this spike is evaluated via the DNS. In addition to LCs, DNS reveals that the water side turbulence is characterized by smaller, shear-driven turbulent eddies at the surface embedded within the LCs. LES with momentum equation augmented with the well-known Craik-Leibovich (C-L) vortex force is used to understand the roles of the wave and shear-driven LCs (i.e. the Langmuir turbulence) and the smaller shear-driven eddies (i.e. the shear turbulence) in determining molecular diffusive scalar flux from the air side to the water side and vertical scalar transport beneath. The C-L force consists of the cross product between the Stokes drift velocity (induced by the interfacial waves) and the flow vorticity. It is observed that Stokes drift shear intensifies the smaller eddies (with respect to purely wind-driven flow, i.e. without wave effects) leading to enhanced diffusive scalar flux at the air-water interface. LC leads to increased vertical scalar transport at depths below the interface and thus greater scalar transfer efficiency.