ALBERT

Description: Author Posting. © Association for the Sciences of Limnology and Oceanography, 2012. This article is posted here by permission of Association for the Sciences of Limnology and Oceanography for personal use, not for redistribution. The definitive version was published in Limnology and Oceanography 57 (2012): 97-112, doi:10.4319/lo.2012.57.1.0097.

Description: We investigated the influences of organic content and mineralogical composition on light absorption by mostly mineral suspended particles in aquatic and coastal marine systems. Mass-specific absorption spectra of suspended particles and surface sediments from coastal Louisiana and the lower Mississippi and Atchafalaya rivers were measured with a centered sample-mount integrating sphere and analyzed in conjunction with organic carbon (OC), hydrochloric acid– (HCl-) extractable iron, and dithionite-extractable iron contents. Compositions and absorption properties were comparable to published values for similar particles. Dithionite-extractable iron was strongly correlated with absorption at ultraviolet (UV) and blue wavelengths, while OC and HCl-extractable iron were weakly but positively correlated. Oxidative removal of OC from sediments caused small and variable changes in absorption, while dithionite extraction of iron oxides strongly reduced absorption. Shoulders in the absorption spectra corresponded to absorption bands of iron oxide minerals, and their intensities were well correlated to dithionite-extractable iron contents of the samples. These findings support a primary role for iron oxide and hydroxide minerals in the mass-specific absorption of mostly inorganic particles from the terrestrially influenced coast of Louisiana. Riverine particles had higher dithionite-extractable iron contents and iron oxide–specific absorption features than did marine particles, consistent with current knowledge regarding differential transport of particulate iron oxides and hydroxides through estuarine salinity gradients and reductive alteration of these oxide phases on the Louisiana shelf. The quantifiable dependence of UV absorption features on iron oxide content suggests that, under certain conditions, in situ hyperspectral absorption measurements could be designed to monitor water-column iron mineral transport and transformation.

Description: We would like to acknowledge funding support from the National Science Foundation Chemical Oceanography program (L.M. and M.L.E.), a National Aeronautics and Space Administration Earth Systems Science Graduate Fellowship (M.L.E.), and the Office of Naval Research Environmental Optics program (E.B. and C.R.).

Description: Author Posting. © American Society of Limnology and Oceanography, 2011. This article is posted here by permission of American Society of Limnology and Oceanography for personal use, not for redistribution. The definitive version was published in Limnology and Oceanography 56 (2011): 1355-1371, doi:10.4319/lo.2011.56.4.1355.

Description: We assessed monomethylmercury (MeHg) dynamics in a tidal wetland over three seasons using a novel method that employs a combination of in situ optical measurements as concentration proxies. MeHg concentrations measured over a single spring tide were extended to a concentration time series using in situ optical measurements. Tidal fluxes were calculated using modeled concentrations and bi-directional velocities obtained acoustically. The magnitude of the flux was the result of complex interactions of tides, geomorphic features, particle sorption, and random episodic events such as wind storms and precipitation. Correlation of dissolved organic matter quality measurements with timing of MeHg release suggests that MeHg is produced in areas of fluctuating redox and not limited by buildup of sulfide. The wetland was a net source of MeHg to the estuary in all seasons, with particulate flux being much higher than dissolved flux, even though dissolved concentrations were commonly higher. Estimated total MeHg yields out of the wetland were approximately 2.5 µg m−2 yr−1—4–40 times previously published yields—representing a potential loading to the estuary of 80 g yr−1, equivalent to 3% of the river loading. Thus, export from tidal wetlands should be included in mass balance estimates for MeHg loading to estuaries. Also, adequate estimation of loads and the interactions between physical and biogeochemical processes in tidal wetlands might not be possible without long-term, high-frequency in situ measurements.

Description: This work was supported by funding from the California Bay Delta Authority Ecosystem Restoration and Drinking Water Programs (grant ERP-00-G01) and matching funds from the U.S. Geological Survey Cooperative Research Program.

Description: Author Posting. © Association for the Sciences of Limnology and Oceanography, 2012. This article is posted here by permission of Association for the Sciences of Limnology and Oceanography for personal use, not for redistribution. The definitive version was published in Limnology and Oceanography 57 (2012): 1743-1756, doi:10.4319/lo.2012.57.6.1743.

Description: We quantified rates of photochemical dissolution (photodissolution) of organic carbon in coastal Louisiana suspended sediments, conducting experiments under well-defined conditions of irradiance and temperature. Optical properties of the suspended sediments were characterized and used in a radiative transfer model to compute irradiances within turbid suspensions. Photodissolution rate increased with temperature (T), with activation energy of 32 ± 7 kJ mol−1, which implicates indirect (non-photochemical) steps in the net reaction. In most samples, dissolved organic carbon (DOC) concentration increased approximately linearly with time over the first 4 h of irradiation under broadband simulated sunlight, after higher rates in the initial hour of irradiation. Four-hour rates ranged from 2.3 µmol DOC m−3 s−1 to 3.2 µmol DOC m−3 s−1, but showed no relation to sample origin within the study area, organic carbon or reducible iron content, or mass-specific absorption coefficient. First-hour rates were higher—from 3.5 µmol DOC m−3 s−1 to 7.8 µmol DOC m−3 s−1—and correlated well with sediment reducible iron (itself often associated with organic matter). The spectral apparent quantum yield (AQY) for photodissolution was computed by fitting DOC photoproduction rates under different spectral irradiance distributions to corresponding rates of light absorption by particles. The photodissolution AQY magnitude is similar to most published dissolved-phase AQY spectra for dissolved inorganic carbon photoproduction, which suggests that in turbid coastal waters where particles dominate light absorption, DOC photoproduction from particles exceeds photooxidation of DOC.

Description: We would like to acknowledge funding support from the National Science Foundation Chemical Oceanography program (L.M. and M.L.E.), a National Aeronautics and Space Administration Earth Systems Science Graduate Fellowship (M.L.E.), and the Office of Naval Research Environmental Optics program (E.B.).