Solar radiation-enhanced dissolution (photodissolution) of particulate organic matter in Texas estuaries

Dissolved 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.