Browsing by Subject "Dissolved organic matter"
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Item Dissolved organic matter in major rivers across the Pan-Arctic from remote sensing(2016-05) Griffin, Claire Genevieve; McClelland, James W.; Frey, Karen E; Gardner, Wayne S; Liu, Zhanfei; Shank, Gerald CClimate-driven changes in Arctic hydrology and biogeochemistry are impacting transport of water and water-borne material from land to ocean. This includes massive amounts of organic matter that are mobilized and exported from the pan-Arctic watershed via rivers each year. Dissolved organic matter (DOM), an important part of the Arctic carbon cycle, has received growing attention in recent years, yet long-term studies of riverine biogeochemistry remain rare in these remote and logistically challenging regions. Remote sensing of chromophoric dissolved organic matter (CDOM, the portion of the DOM pool that absorbs light), provides a unique opportunity to investigate variations in DOM in major Arctic rivers over multiple decades. CDOM is a useful proxy for dissolved organic carbon (DOC) and is essential to photochemical processes in surface waters. This dissertation presents the development and application of remote sensing regression models across six major Arctic rivers: the Kolyma, Lena, Mackenzie, Ob’, Yenisey and Yukon. Frozen, archival samples of CDOM were used to develop calibration data for remote sensing regressions. Remote sensing methods estimated CDOM with R2 of 85% across all rivers, although individual rivers varied in their predictability in association with sediment loading and hydrology. As with previous studies of Arctic systems, concentrations and export of CDOM and DOC were highest during spring freshet in most of these rivers. Interannual variability in DOM export may be linked to the Arctic Oscillation. Within the Mackenzie, Ob’, and Yenisey rivers, observations of DOM concentration and export were extended back to the 1980s, the first known empirical records of this length for Arctic rivers that span both continents. Although no pan-Arctic trends in CDOM export were detected, there is some evidence of long-term changes in riverine DOM. For example, discharge-specific CDOM concentrations decreased in the Yenisey River and increased in the Ob’ River. Additionally, CDOM concentrations increased over the past ~30 years within the Mackenzie River. This dissertation also includes results from experiments used to quantify the effects of cryopreservation on CDOM analyses, and potential approaches for ameliorating freezing effects. These experiments showed that freezing for preservation introduces some error into CDOM measurements, although these effects vary between river systems. Sonication may improve CDOM measurements in some river systems, but the effects of both cryopreservation and sonication should be quantified on a case-by-case basis. Overall, this dissertation work demonstrates that 1) remote sensing of CDOM is a viable tool for tracking fluvial DOM in the major Arctic rivers, 2) only the Mackenzie River showed significant increases in CDOM concentration from the 1980s to present and 3) long-term changes in discharge-specific CDOM concentrations have occurred in the Yenisey and Ob’ rivers. These long-term trends cannot be definitively linked to climate change, but may be related to effects of warming on permafrost, hydrology, and biogeochemistry within in Arctic watersheds with consequences for carbon cycling on both regional and global scales.Item Seasonal dynamics of organic matter and inorganic nitrogen in surface waters of Alaskan Arctic streams and rivers(2015-12) Khosh, Matthew Solomon; McClelland, James W.; Dunton, Kenneth H; Liu, Zhanfei; Shank, Gerald C; Townsend-Small, AmyClimate-linked changes in hydrology and biogeochemical processes within Arctic watersheds are likely already affecting fluvial export of waterborne materials, including organic matter (OM) and dissolved inorganic nitrogen (DIN). Our understanding of Arctic watershed OM and DIN export response to climate change is hampered by a lack of contemporary baselines, as well as a dearth of seasonally comprehensive studies. This work focuses on characterizing OM and DIN concentrations and sources in six streams/rivers on the North Slope of Alaska during the entirety of the hydrologic year (May through October) in 2009 and 2010. The highest OM concentrations occurred during spring snowmelt, with results indicating that terrestrial vegetation leachates are the major source of dissolved OM, while particulate OM originates from a degraded soil source. Over the hydrologic year, soils became a progressively increasing source of dissolved OM, while autochthonous production made up a sizeable proportion of particulate OM during base flow conditions. DIN concentrations were low throughout the spring and summer and increased markedly during the late summer and fall. Our findings suggest that penetration of water into thawed mineral soils, and a reduction in nitrogen assimilation relative to remineralization, may increase DIN export from Arctic watersheds during the late summer and fall. Although recent studies of Arctic rivers have emphasized the importance of the spring thaw period on OM export, our understanding of the mechanisms that control water chemistry observations during this time are still lacking. Experimental leaching results, from experiments conducted in 2014, suggest that aboveground plant biomass is a major source of dissolved OM in Arctic catchments during the spring, and that the timing of freezing and drying conditions during the fall may impact dissolved OM leaching dynamics on that same material the following snowmelt. Improved knowledge of OM and DIN temporal trends and the mechanisms that control seasonal concentrations is essential for understanding export dynamics of these water constituents in Arctic river systems. Perhaps more importantly, increased understanding of the seasonal controls on OM and DIN export in Arctic rivers is critical for predicting how these systems will respond under future climate change scenarios.Item Solar radiation-enhanced dissolution (photodissolution) of particulate organic matter in Texas estuaries(2013-05) Liu, Qiyuan, active 2013; Shank, Gerald ChristopherDissolved organic matter (DOM) is crucial to carbon and nutrient biogeochemical cycling in the marine environment because it helps fuel heterotrophic microbial activity by providing substrates for degradation and remineralization. This study shows that substantial production of DOM in Texas estuaries can result from the solar radiation-enhanced dissolution (photodissolution) of particulate organic matter (POM). Experimental results showed that 0.4-6.6 mg C L⁻¹gsed⁻¹ of dissolved organic carbon (DOC) and 0.03-0.93 mg N L⁻¹gsed⁻¹ of total dissolved nitrogen (TDN) can be produced from irradiated sediment suspensions within 24 hours, and further that photodissolution may augment DOC and TDN loads in Texas estuarine waters by as much as 3-85% and 4-75%, respectively. Photodissolution can also enhance the optical thickness of the water column via the release of chromophoric dissolved organic matter (CDOM), which may subsequently further enhance photochemical processes in surrounding waters. Photoproduced CDOM appears to be of relatively high molecular weight and dominantly exhibits humic-like fluorescence, suggesting that photodissolution primarily occurs for humic moieties. Photodissolution was also observed for sterilized sediment suspensions, indicating that photochemical degradation of POM is the primary pathway of DOM production during photodissolution, as opposed to microbial mediated degradation or stimulation of benthic primary production by benthic phytoplankton or algae. Environmental and mechanistic factors controlling the extent of photodissolution in Texas estuaries may include sediment desiccation, water organic content, and sediment characteristics (organic content and lability of POM). Desiccated-rewetted sediments suspended in artificial seawater under solar irradiation produced ~40% more DOC and TDN than wet sediments, indicating the sediment dry-wet cycle may alter the 3-D structure of sediment grain matrices and thus might be a major controlling factor of photodissolution in salt marsh systems. The organic content of water used in sediment suspensions did not significantly influence DOC or TDN photoproduction by itself, but the combined influence of water organic content and sediment dry-rewet event played a substantial role in controlling the extent of photodissolution. In contrast to the results in artificial seawater, wet sediments produced slightly more DOC ([Delta]DOC=0.10 mg C gsed⁻¹) and substantially more TDN ([Delta]TDN=0.14 mg N gsed⁻¹) than dry-rewetted sediments in organic-rich Nueces Marsh water during 24 hours of photoincubation. Photodissolution dominantly produced humic-like DOM even though biologically labile organic matter was available in sediments, indicating that photochemical reactions preferentially occur with humic-like rather than protein-like organic matter. DOC and TDN production during photodissolution was strongly proportional to the amount of POC in sediment suspensions. On average, 69.2 ± 11.0 mg C of DOC and 9 ± 3.1 mg N of TDN was produced from 1 g of organic carbon in sediment suspensions after 24 hours of photodissolution.