Improving Estimates of Dissolved Organic Carbon (DOC) Concentration from In Situ Fluorescence Measurements across Estuaries and Coastal Wetlands.

The use of optical proxies is essential to the sustained monitoring of dissolved organic carbon (DOC) in estuaries and coastal wetlands, where dynamics occur on subhour time scales. In situ dissolved organic matter (DOM) fluorescence, or FDOM, is now routinely measured along with ancillary water-quality indicators by commercial sondes. However, its reliability as an optical proxy of DOC concentration is often limited by uncertainties caused by in situ interferences and by variability in DOM composition and water matrix (ionic strength, pH) that are typical at the land-ocean interface. Although corrections for in situ interferences already exist, validated strategies to account for changes in the DOM composition and water matrix in these systems are still lacking. The transferability of methods across systems is also poorly known. Here, we used a comprehensive data set of laboratory-based excitation-emission matrix fluorescence and DOC concentration matched to in situ sonde measurements to develop and compare approaches that leverage ancillary water-quality indicators to improve estimates of DOC concentration from FDOM. Our analyses demonstrated the validity of in situ interference correction schemes, the importance of ancillary water-quality indicators to account for DOM composition and water matrix change, and the good transferability of the proposed methods.

The apparent quantum yield matrix (AQY-M) of CDOM photobleaching in estuarine, coastal, and oceanic surface waters.

The photochemical degradation of chromophoric dissolved organic matter (CDOM) upon solar exposure, known as photobleaching, can significantly alter the optical properties of the surface ocean. By leading to the breakdown of UV- and visible-radiation-absorbing moieties within dissolved organic matter, photobleaching regulates solar heating, the vertical distribution of photochemical processes, and UV exposure and light availability to the biota in surface waters. Despite its biogeochemical and ecological relevance, this sink of CDOM remains poorly quantified. Efforts to quantify photobleaching globally have long been hampered by the inherent challenge of determining representative apparent quantum yields (AQYs) for this process, and by the resulting lack of understanding of their variability in natural waters. Measuring photobleaching AQY is made challenging by the need to determine AQY matrices (AQY-M) that capture the dual spectral dependency of this process (i.e., magnitude varies with both excitation wavelength and response wavelength). A new experimental approach now greatly facilitates the quantification of AQY-M for natural waters, and can help address this problem. Here, we conducted controlled photochemical experiments and applied this new approach to determine the AQY-M of 27 contrasting water samples collected globally along the land-ocean aquatic continuum (i.e., rivers, estuaries, coastal ocean, and open ocean). The experiments and analyses revealed considerable variability in the magnitude and spectral characteristics of the AQY-M among samples, with strong dependencies on CDOM composition/origin (as indicated by the CDOM 275-295-nm spectral slope coefficient, S275-295), solar exposure duration, and water temperature. The experimental data facilitated the development and validation of a statistical model capable of accurately predicting the AQY-M from three simple predictor variables: 1) S275-295, 2) water temperature, and 3) a standardized measure of solar exposure. The model will help constrain the variability of the AQY-M when modeling photobleaching rates on regional and global scales.

Modeling benthic solar exposure (UV and visible) in dynamic coastal systems to better inform seagrass habitat suitability.

Seagrass meadows worldwide provide valuable ecosystem services but have experienced sharp declines in recent decades. This rapid loss has prompted numerous restoration efforts with variable levels of success, often depending on the suitability of the restoration sites. The selection of sites can be guided by simple habitat suitability models driven with environmental variables deemed critical to the successful growth of new transplants. Habitat suitability models typically consider the influence of bathymetry, sediment type, salinity, wave exposure, and water quality. However, they typically do not explicitly include benthic exposure to ultraviolet (UV) and commonly use depth as a coarse proxy for photosynthetically active radiation (PAR). Benthic exposure to UV and PAR are both key parameters for habitat suitability but can be challenging to determine, especially in coastal environments influenced by rivers and tides where they are extremely variable. Here, we demonstrate the development of a simple but effective model of spectrally-resolved benthic solar irradiance for a dynamic marsh-influenced mesotidal estuary in Massachusetts. In-situ measurements were used to develop and validate an empirical model predicting the UV-visible vertical diffuse attenuation coefficient spectra of downwelling irradiance, Kd(λ), from simple physical parameters about tides, river discharge and location. Spectral benthic solar irradiances (280-700 nm) were calculated hourly for 3 years (2017-2019) using modeled and validated cloud-corrected surface downwelling irradiances, estimates of water depth, and the modeled Kd(λ) spectra. The mapped irradiances were used to provide improved seagrass habitat suitability maps that will guide future restoration efforts in the estuary. We expect the approach presented here can be adapted to other dynamic coastal environments influenced by tides and rivers and/or applied to other light-dependent organisms and biogeochemical processes.