Bryan D. Downing

Mississippi River Nitrate Loads from High Frequency Sensor Measurements and Regression-Based Load Estimation

Accurately quantifying nitrate (NO3-) loading from the Mississippi River is important for predicting summer hypoxia in the Gulf of Mexico and targeting nutrient reduction within the basin. Loads have historically been modeled with regression-based techniques, but recent advances with high frequency NO3- sensors allowed us to evaluate model performance relative to measured loads in the lower Mississippi River. Patterns in NO3- concentrations and loads were observed at daily to annual time steps, with considerable variability in concentration-discharge relationships over the two year study. Differences were particularly accentuated during the 2012 drought and 2013 flood, which resulted in anomalously high NO3- concentrations consistent with a large flush of stored NO3- from soil. The comparison between measured loads and modeled loads (LOADEST, Composite Method, WRTDS) showed underestimates of only 3.5% across the entire study period, but much larger differences at shorter time steps. Absolute differences in loads were typically greatest in the spring and early summer critical to Gulf hypoxia formation, with the largest differences (underestimates) for all models during the flood period of 2013. In additional to improving the accuracy and precision of monthly loads, high frequency NO3- measurements offer additional benefits not available with regression-based or other load estimation techniques.

Concurrent photolytic degradation of aqueous methylmercury and dissolved organic matter.

Monomethyl mercury (MeHg) is a potent neurotoxin that threatens ecosystem viability and human health. In aquatic systems, the photolytic degradation of MeHg (photodemethylation) is an important component of the MeHg cycle. Dissolved organic matter (DOM) is also affected by exposure to solar radiation (light exposure) leading to changes in DOM composition that can affect its role in overall mercury (Hg) cycling. This study investigated changes in MeHg concentration, DOM concentration, and the optical signature of DOM caused by light exposure in a controlled field-based experiment using water samples collected from wetlands and rice fields. Filtered water from all sites showed a marked loss in MeHg concentration after light exposure. The rate of photodemethylation was 7.5×10(-3)m(2)mol(-1) (s.d. 3.5×10(-3)) across all sites despite marked differences in DOM concentration and composition. Light exposure also caused changes in the optical signature of the DOM despite there being no change in DOM concentration, indicating specific structures within the DOM were affected by light exposure at different rates. MeHg concentrations were related to optical signatures of labile DOM whereas the percent loss of MeHg was related to optical signatures of less labile, humic DOM. Relationships between the loss of MeHg and specific areas of the DOM optical signature indicated that aromatic and quinoid structures within the DOM were the likely contributors to MeHg degradation, perhaps within the sphere of the Hg-DOM bond. Because MeHg photodegradation rates are relatively constant across freshwater habitats with natural Hg-DOM ratios, physical characteristics such as shading and hydrologic residence time largely determine the relative importance of photolytic processes on the MeHg budget in these mixed vegetated and open-water systems.

Optical techniques for the determination of nitrate in environmental waters: Guidelines for instrument selection, operation, deployment, maintenance, quality assurance, and data reporting

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Assessing contribution of DOC from sediments to a drinking-water reservoir using optical profiling

Abstract Understanding the sources of dissolved organic carbon (DOC) in drinking-water reservoirs is an important management issue because DOC may form disinfection by-products, interfere with disinfection, or increase treatment costs. DOC may be derived from a host of sources—algal production of DOC in the reservoir, marginal production of DOC from mucks and vascular plants at the margins, and sediments in the reservoir. The purpose of this study was to assess if release of DOC from reservoir sediments containing ferric chloride coagulant was a significant source of DOC to the reservoir. We examined the source-specific contributions of DOC using a profiling system to measure the in situ distribution of optical properties of absorption and fluorescence at various locations in the reservoir. Vertical optical profiles were coupled with discrete water samples measured in the laboratory for DOC concentration and optical properties: absorption spectra and excitation emission matrix spectra (EEMs). Modeling the in situ optical data permitted estimation of the bulk DOC profile in the reservoir as well as separation into source-specific contributions. Analysis of the source-specific profiles and their associated optical characteristics indicated that the sedimentary source of DOC to the reservoir is significant and that this DOC is labile in the reservoir. We conclude that optical profiling is a useful technique for understanding complex biogeochemical processes in a reservoir.

High-Resolution Remote Sensing of Water Quality in the San Francisco Bay–Delta Estuary

The San Francisco Bay-Delta Estuary watershed is a major source of freshwater for California and a profoundly human-impacted environment. The water quality monitoring that is critical to the management of this important water resource and ecosystem relies primarily on a system of fixed water-quality monitoring stations, but the limited spatial coverage often hinders understanding. Here, we show how the latest technology in visible/near-infrared imaging spectroscopy can facilitate water quality monitoring in this highly dynamic and heterogeneous system by enabling simultaneous depictions of several water quality indicators at very high spatial resolution. The airborne portable remote imaging spectrometer (PRISM) was used to derive high-spatial-resolution (2.6 × 2.6 m) distributions of turbidity, and dissolved organic carbon (DOC) and chlorophyll-a concentrations in a wetland-influenced region of this estuary. A filter-passing methylmercury vs DOC relationship was also developed using in situ samples and enabled the high-spatial-resolution depiction of surface methylmercury concentrations in this area. The results illustrate how high-resolution imaging spectroscopy can inform management and policy development in important inland and estuarine water bodies by facilitating the detection of point- and nonpoint-source pollution, and by providing data to help assess the complex impacts of wetland restoration and climate change on water quality and ecosystem productivity.