Nitrogen Oxides in the North Atlantic Troposphere: Impacts of Boreal Wildfire and Anthropogenic Emissions

Nitrogen oxides play a crucial role in the budget of tropospheric ozone (O sub(3)) and the formation of the hydroxyl radical. Anthropogenic activities and boreal wildfires are large sources of emissions in the atmosphere. However, the influence of the transport of these emissions on nitrogen oxides and O sub(3) levels at hemispheric scales is not well understood, in particular due to a lack of nitrogen oxides measurements in remote regions. In order to address these deficiencies, measurements of NO, NO sub(2) and NO sub(y) (total reactive nitrogen oxides) were made in the lower free troposphere (FT) over the central North Atlantic region (Pico Mountain station, 38 degree N 28 degree W, 2.3 km asl) from July 2002 to August 2005. These measurements reveal a well-defined seasonal cycle of nitrogen oxides (NO sub(x) = NO+NO sub(2) and NO sub(y)) in the background central North Atlantic lower FT, with higher mixing ratios during the summertime. Observed NO sub(x) and NO sub(y) levels are consistent with long-range transport of emissions, but with significant removal en-route to the measurement site. Reactive nitrogen largely exists in the form of PAN and HNO sub(3) ( similar to 80-90% of NO sub(y)) all year round. A shift in the composition of NO sub(y) from dominance of PAN to dominance of HNO sub(3) occurs from winter-spring to summer-fall, as a result of changes in temperature and photochemistry over the region. Analysis of the long-range transport of boreal wildfire emissions on nitrogen oxides provides evidence of the very large-scale impacts of boreal wildfires on the tropospheric NO sub(x) and O sub(3) budgets. Boreal wildfire emissions are responsible for significant shifts in the nitrogen oxides distributions toward higher levels during the summer, with medians of NO sub(y) (117-175 pptv) and NO sub(x) (9-30 pptv) greater in the presence of boreal wildfire emissions. Extreme levels of NO sub(x) (up to 150 pptv) and NO sub(y) (up to 1100 pptv) observed in boreal wildfire plumes suggest that decomposition of PAN to NO sub(x) is a significant source of NO sub(x), and imply that O sub(3) formation occurs during transport. Ozone levels are also significantly enhanced in boreal wildfire plumes. However, a complex behavior of O sub(3) is observed in the plumes, which varies from significant to lower O sub(3) production to O sub(3) destruction. Long-range transport of anthropogenic emissions from North America also has a significant influence on the regional NO sub(x) and O sub(3) budgets. Transport of pollution from North America causes significant enhancements on nitrogen oxides year-round. Enhancements of CO, NO sub(y) and NO sub(x) indicate that, consistent with previous studies, more than 95% of the NO sub(x) emitted over the U.S. is removed before and during export out of the U.S. boundary layer. However, about 30% of the NO sub(x) emissions exported out of the U.S. boundary layer remain in the airmasses. Since the lifetime of NO sub(x) is shorter than the transport timescale, PAN decomposition and potentially photolysis of HNO sub(3) provide a supply of NO sub(x) over the central North Atlantic lower FT. Observed Delta O sub(3)/ Delta NO sub(y) and large NO sub(y) levels remaining in the North American plumes suggest potential O sub(3) formation well downwind from North America. Finally, a comparison of the nitrogen oxides measurements with results from the global chemical transport (GCT) model GEOS-Chem identifies differences between the observations and the model. GEOS-Chem reproduces the seasonal variation of nitrogen oxides over the central North Atlantic lower FT, but does not capture the magnitude of the cycles. Improvements in our understanding of nitrogen oxides chemistry in the remote FT and emission sources are necessary for the current GCT models to adequately estimate the impacts of emissions on tropospheric NO sub(x) and the resulting impacts on the O sub(3) budget.

VERIFYING SUCCESS OF ARTIFICIAL REEFS IN THE HURON-ERIE CORRIDOR FOR LAKE STURGEON

Lake sturgeon (Acipenser fulvescens) were historically abundant in the Huron-Erie Corridor (HEC), a 160 km river/channel network composed of the St. Clair River, Lake St. Clair, and the Detroit River that connects Lake Huron to Lake Erie. In the HEC, most natural lake sturgeon spawning substrates have been eliminated or degraded as a result of channelization and dredging. To address significant habitat loss in HEC, multi-agency restoration efforts are underway to restore spawning substrate by constructing artificial spawning reefs. The main objective of this study was to conduct post-construction monitoring of lake sturgeon egg deposition and larval emergence near two of these artificial reef projects; Fighting Island Reef in the Detroit River, and Middle Channel Spawning Reef in the lower St. Clair River. We also investigated seasonal and nightly timing of larval emergence, growth, and vertical distribution in the water column at these sites, and an additional site in the St. Clair River where lake sturgeon are known to spawn on a bed of ~100 year old coal clinkers. From 2010-12, we collected viable eggs and larvae at all three sites indicating that these artificial reefs are creating conditions suitable for egg deposition, fertilization, incubation, and larval emergence. The construction methods and materials, and physical site conditions present in HEC artificial reef projects can be used to inform future spawning habitat restoration or enhancement efforts. The results from this study have also identified the likelihood of additional uncharacterized natural spawning sites in the St. Clair River. In addition to the field study, we conducted a laboratory experiment involving actual substrate materials that have been used in artificial reef construction in this system. Although coal clinkers are chemically inert, some trace elements can be reincorporated with the clinker material during the combustion process. Since lake sturgeon eggs and larvae are developing in close proximity to this material, it is important to measure the concentration of potentially toxic trace elements. This study focused on arsenic, which occurs naturally in coal and can be toxic to fishes. Total arsenic concentration was measured in samples taken from four substrate treatments submerged in distilled water; limestone cobble, rinsed limestone cobble, coal clinker, and rinsed coal clinker. Samples were taken at three time intervals: 24 hours, 11 days, and 21 days. ICP-MS analysis showed that concentrations of total arsenic were below the EPA drinking water standard (10 ppb) for all samples. However, at the 24 hour sampling interval, a two way repeated measures ANOVA with a Holm-Sidak post hoc analysis (α= 0.05) showed that the mean arsenic concentration was significantly higher in the coal clinker substrate treatment then in the rinsed coal clinker treatment (p=0.006), the limestone cobble treatment (p

Modeling and classifying variable width riparian zones utilizing digital elevation models, flood height data, digital soil data and national wetlands inventory : a new approach for riparian zone delineation

Riparian zones are dynamic, transitional ecosystems between aquatic and terrestrial ecosystems with well defined vegetation and soil characteristics. Development of an all-encompassing definition for riparian ecotones, because of their high variability, is challenging. However, there are two primary factors that all riparian ecotones are dependent on: the watercourse and its associated floodplain. Previous approaches to riparian boundary delineation have utilized fixed width buffers, but this methodology has proven to be inadequate as it only takes the watercourse into consideration and ignores critical geomorphology, associated vegetation and soil characteristics. Our approach offers advantages over other previously used methods by utilizing: the geospatial modeling capabilities of ArcMap GIS; a better sampling technique along the water course that can distinguish the 50-year flood plain, which is the optimal hydrologic descriptor of riparian ecotones; the Soil Survey Database (SSURGO) and National Wetland Inventory (NWI) databases to distinguish contiguous areas beyond the 50-year plain; and land use/cover characteristics associated with the delineated riparian zones. The model utilizes spatial data readily available from Federal and State agencies and geospatial clearinghouses. An accuracy assessment was performed to assess the impact of varying the 50-year flood height, changing the DEM spatial resolution (1, 3, 5 and 10m), and positional inaccuracies with the National Hydrography Dataset (NHD) streams layer on the boundary placement of the delineated variable width riparian ecotones area. The result of this study is a robust and automated GIS based model attached to ESRI ArcMap software to delineate and classify variable-width riparian ecotones.