Unsteady diffusional mass transfer at the sediment/water interface: Theory and significance for SOD measurement.

Dissolved oxygen uptake at a sediment/water interface (SOD) is controlled by mass transport and/or biochemical reactions in two adjacent boundary layers: the diffusive boundary layer delta(D) in the water and the penetration depth delta in the sediment. Either one of those boundary layers or both can be controlling. The transition from sediment control to water control is a function of shear velocity at the sediment/water interface (U(*)) and biochemical activity rate (micro(0)) in the sediment. A model was developed for the unsteady response of SOD and DO profiles near the sediment/water interface. Michaelis-Menten kinetics were used initially, but zero order kinetics work just as well when the half saturation coefficient K(O(2)) is small as was suggested by field data. Beginning with zero DO in the sediments the times required to reach steady state DO profiles and SOD was on the order of minutes to hours, faster where biochemical activity is strong. The values of SOD estimated by the model were compared with experimental data to verify the reliability of the model. The model can reproduce observed penetration depths and diffusive boundary layer thickness. Values of SOD estimated by the model were of same magnitude as observed data. The unsteady DO uptake model can be used to provide guidance for field measurements of SOD. Placing a chamber (with a stirrer) into the sediments disturbs the DO equilibrium at the sediment/water interface. A new equilibrium will be reached within a time that can be measured in terms of cumulative DO consumption in the chamber (SOD exerted). Upper bounds for (SOD exerted) are larger when biochemical activity in the sediments is smaller. Values of SOD exerted are less than 0.1gm(-2) when micro(0) is less than 50mgl(-1)d(-1) and U(*)>0.1cm/s. In other words, steady state conditions are easier to reach for high SOD values. Actual times required to reach steady state can be from minutes to hours. If flow conditions in the chamber and at the natural sediment/water interface are much different, measured SOD values have to be adjusted. A procedure for the adjustments, which can be substantial, has been developed.

A model of microbial activity in lake sediments in response to periodic water-column mixing.

Under stagnant conditions, the mass transport of a soluble substrate from a lake's water column to the sediment/water interface is limited by molecular diffusion. Stagnant conditions coupled with a continuing sediment biological demand create a substrate depletion zone above the sediment/water interface. The frequency at which the substrate depletion zone is destroyed by internal seiches and other intermittent flow phenomena influences the time-averaged substrate concentration at the sediment/water interface. A more frequent mixing results in a greater time-averaged interface concentration and consequently affects the amount of microbial biomass that can be supported in the lake sediments and the flux of the substrate into the sediment. A one-dimensional, two-substrate model is used to examine the impact of mixing frequency on the activity of sulfate-reducing bacteria (SRB) in lake sediments. In the model, sulfate is supplied from the water column, while acetate is generated within the sediments. Mass transport to and within the sediments is by molecular diffusion except for instantaneous mixing events. Between mixing events, sulfate concentration gradients form above the sediment/water interface in the diffusive boundary layer. Sulfate depletion zones can be centimeters thick. When typical biological rate and diffusion coefficients for sulfate and acetate are used as inputs, the model indicates that a more frequent water-column mixing results in greater SRB concentrations. For an assumed bulk water-column sulfate concentration of 4.8 mg x l(-1), the sediment SRB concentrations for the modeled hourly, 6-hourly, daily, and weekly mixing frequencies were 175, 136, 91, and 30 mg x m(-2), respectively. The model also predicts higher time-averaged sulfate flux rates at more frequent water-column mixing. The time-averaged sulfate flux rates for the hourly, 6-hourly, daily, and weekly mixing frequencies were 1.26, 1.13, 0.78, and 0.30 mg x m(-2)h(-1), respectively. Thus, mixing frequency can significantly impact microbial activity in lake sediments.