Recent studies suggested that under low to moderate wind conditions without bubble entraining wave breaking, the air-water gas transfer velocity k 1 can be mechanistically parameterized by the nearsurface turbulence, following the small eddy model (SEM). Field measurements have supported this model in a variety of environmental forcing systems. Alternatively, surface divergence model (SDM) has also been shown to predict the gas transfer velocity across the air-water interface in laboratory settings. However, the empirically determined model coefficients (a in SEM and c 1 in SDM) scattered over a wide range. Here we present the first field measurement of the near-surface turbulence with a novel floating PIV system on Lake Michigan, which allows us to evaluate the SEM and SDM in situ in the natural environment. k 1 was derived from the CO 2 flux that was measured simultaneously with a floating gas chamber. Measured results indicate that a and c 1 are not universal constants. Regression analysis showed that a $ logðeÞ while the near-surface turbulence dissipation rate e is approximately greater than 10 26 m 2 s 23 according to data measured for this study as well as from other published results measured in similar environments or in laboratory settings. It also showed that a scales linearly with the turbulent Reynolds number. Similarly, coefficient c 1 in the SDM was found to linearly scale with the Reynolds number. These findings suggest that larger eddies are also important parameters, and the dissipation rate in the SEM or the surface divergence b 0 in the SDM alone may not be adequate to determine k 1 completely.

Abstract. Air quality forecast models typically predict large summertime ozone abundances over water relative to land in the Great Lakes region. While each state bordering Lake Michigan has dedicated monitoring systems, offshore measurements have been sparse, mainly executed through specific short-term campaigns. This study examines ozone abundances over Lake Michigan as measured on the Lake Express ferry, by shoreline differential optical absorption spectroscopy (DOAS) observations in southeastern Wisconsin and as predicted by the Community Multiscale Air Quality (CMAQ) model. From 2008 to 2009 measurements of O 3 , SO 2 , NO 2 and formaldehyde were made in the summertime by DOAS at a shoreline site in Kenosha, WI. From 2008 to 2010 measurements of ambient ozone were conducted on the Lake Express, a high-speed ferry that travels between Milwaukee, WI, and Muskegon, MI, up to six times daily from spring to fall. Ferry ozone observations over Lake Michigan were an average of 3.8 ppb higher than those measured at shoreline in Kenosha, with little dependence on position of the ferry or temperature and with greatest differences during evening and night. Concurrent 1-48 h forecasts from the CMAQ model in the upper Midwestern region surrounding Lake Michigan were compared to ferry ozone measurements, shoreline DOAS measurements and Environmental Protection Agency (EPA) station measurements. The bias of the model O 3 forecast was computed and evaluated with respect to ferry-based measurements. Trends in the bias with respect to location and time of day were explored showing nonuniformity in model bias over the lake. Model ozone bias was consistently high over the lake in comparison to landbased measurements, with highest biases for 25-48 h after initialization.

Abstract. Air quality forecast models typically predict large ozone abundances over water relative to land in the Great Lakes region. While each state bordering Lake Michigan has dedicated monitoring systems, offshore measurements have been sparse, mainly executed through specific short-term campaigns. This study examines ozone abundances over Lake Michigan as measured on the Lake Express ferry, by shoreline Differential Optical Absorption Spectroscopy (DOAS) observations in southeastern Wisconsin, and as predicted by the National Air Quality Forecast System. From 2008–2009 measurements of O3, SO2, NO2 and formaldehyde were made in the summertime by DOAS at a shoreline site in Kenosha, WI. From 2008–2010 measurements of ambient ozone conducted on the Lake Express, a high-speed ferry that travels between Milwaukee, WI and Muskegon, MI up to 6 times daily from spring to fall. Ferry ozone observations over Lake Michigan were an average of 3.8 ppb higher than those measured at shoreline in Kenosha with little dependence on position of the ferry or temperature but with highest differences during evening and night. Concurrent ozone forecast images from National Weather System's National Air Quality Forecast System in the upper Midwestern region surrounding Lake Michigan were saved over the ferry ozone sampling period in 2009. The bias of the model O3 forecast was computed and evaluated with respect to ferry-based measurements. The model 1 and 8 h ozone mean biases were both 12 ppb higher than observed ozone, and maximum daily 1 h ozone mean bias was 10 ppb, indicating substantial ozone over-prediction over water. Trends in the bias with respect to location and time of day or month were also explored showing non-uniformity in model bias. Extreme ozone events were predicted by the model but not observed by ferry measurements.