Anthropogenic And Environmental Drivers Of The Input And Uptake Of Dissolved Organic Matter In Temperate Streams PDF Download

Dissolved organic matter (DOM) in the atmosphere affects air quality and climate. Unlike inorganic constituents that typically consist of single compounds, DOM is a mixture of multiple organic compounds having varying molecular weights, reactivity and solubility. Dissolved organic carbon (DOC) is typically used as a measure of the total DOM present in solution. In the atmosphere, DOC originates from emissions of various biogenic and anthropogenic sources, such as vegetation, incomplete combustion of fossil fuels, biomass burning, and sea-spray. The ultimate fate of atmospheric DOC is to be oxidized to inorganic forms of carbon dioxide and carbon monoxide, or to be removed from the atmosphere and transferred to the landscape through deposition. Deposition can occur as wet deposition via precipitation and as dry deposition via surface settling of particles and gases. The concentration, or quantity, of DOC in precipitation plays an important role in the carbon cycle and in other elemental cycles; while the chemical composition, or quality, of DOC in precipitation largely determines its fate in the environment. Rain and snow deposited to the landscape are a source of nutrient enrichment to ecosystems and water bodies, and are especially important as an input of carbon in coastal regions. Since DOC in precipitation is highly chemically reactive and bioavailable it influences rates of productivity in aquatic ecosystems. Despite the significance of DOC to many ecosystem processes, knowledge about its contributions to landscapes in precipitation remains limited. With anthropogenic influences on the carbon cycle now widely recognized, the need for synthesis of existing datasets on atmospheric deposition of DOC and further determining its rates and drivers is great. My dissertation is focused on wet deposition of DOC and assesses the magnitude and patterns of variation of organic matter in precipitation over space and time. The dissertation is organized into four manuscripts. Chapter 1 is a literature review where I provide a new data synthesis from 83 contemporary, peer-reviewed studies where organic carbon (OC) in precipitation was measured at sites around the world. Data regarding the concentrations of OC in precipitation and rates of atmospheric deposition were compiled in a common set of units and presented along with the summary statistics. These data give insights into the magnitude and regional variability of OC in precipitation. Organic carbon was ubiquitous in precipitation in rural and urban locations; with DOC in precipitation spanning several orders of magnitude between locations. This synthesis brings attention to atmospheric deposition as an under-sampled piece of the global carbon cycle; highlights gaps in data availability and challenges for data inter-comparison; and provides a unique data set that can be used for toward exploring future changes in the carbon cycle. Chapter 2 aims to understand how DOC concentration and composition in precipitation change temporally from storm to storm. Precipitation samples were collected at the Susquehanna Shale Hills Critical Zone Observatory watershed (Pennsylvania, USA) during 90 storm events. Observational data revealed temporal variability associated with seasonality and meteorological conditions. Using a mixed modeling statistical approach, I showed that there are multiple processes that work in synergy to influence the quantity and quality of DOC in precipitation. Factors related to storm properties, emission sources, and to the chemical composition of the atmosphere could explain more than 60% of the storm to storm variability in DOC concentrations. This study provided observations on changes in DOC that can be useful in modeling of atmospheric chemistry and in considering temporal changes in ecosystem nutrient balances and microbial activity.Chapter 3 explores how DOC concentration and composition vary throughout the course of storm events. I measured DOC in sequential samples during 13 storms at the Shale Hills watershed. The observational data generated hypotheses about potential factors that influence variability of DOC within storms. While previous studies have observed that concentrations of other elements in precipitation typically decrease over the course of individual storms, results from this study showed that DOC concentrations are highly variable. During most storms concentrations decreased towards the end of the event; however increasing concentrations in the later stages of some storms highlight that DOC removal with precipitation is not merely an exponential decay process. The variability of DOC during events is related to the balance between the cloud microphysics, atmospheric chemical transformations, and synoptic scale gradients in the abundance of organic compounds in the boundary layer. This work advances understanding of physicochemical processes occurring during storms that are relevant to studies of atmospheric chemistry, carbon cycling, and ecosystem responses.Chapter 4 quantifies spatial gradients in wet atmospheric DOC deposition across the state of Pennsylvania (USA). DOC concentrations were measured in selected precipitation samples collected for six years at a network of atmospheric deposition monitoring sites. A simple modeling approach was used to estimate the first statewide, annual estimates of wet atmospheric DOC deposition. Results showed that DOC inputs with wet deposition in Pennsylvania represented about one-third as much as literature reported values for DOC exported by rivers from watersheds in the region. The rates of DOC wet deposition showed a pronounced seasonality and spatial distribution, with highest deposition rates observed in the summer, especially at the sites located in western Pennsylvania.