Photo-dissolution of flocculent, detrital material in aquatic environments: Contributions to the dissolved organic matter pool

This study shows that light exposure of flocculent material (floc) from the Florida Coastal Everglades (FCE) results in significant dissolved organic matter (DOM) generation through photo-dissolution processes. Floc was collected at two sites along the Shark River Slough (SRS) and irradiated with artificial sunlight. The DOM generated was characterized using elemental analysis and excitation emission matrix fluorescence coupled with parallel factor analysis. To investigate the seasonal variations of DOM photo-generation from floc, this experiment was performed in typical dry (April) and wet (October) seasons for the FCE. Our results show that the dissolved organic carbon (DOC) for samples incubated under dark conditions displayed a relatively small increase, suggesting that microbial processes and/or leaching might be minor processes in comparison to photo-dissolution for the generation of DOM from floc. On the other hand, DOC increased substantially (as much as 259 mgC gC−1) for samples exposed to artificial sunlight, indicating the release of DOM through photo-induced alterations of floc. The fluorescence intensity of both humic-like and protein-like components also increased with light exposure. Terrestrial humic-like components were found to be the main contributors (up to 70%) to the chromophoric DOM (CDOM) pool, while protein-like components comprised a relatively small percentage (up to 16%) of the total CDOM. Simultaneously to the generation of DOC, both total dissolved nitrogen and soluble reactive phosphorus also increased substantially during the photo-incubation period. Thus, the photo-dissolution of floc can be an important source of DOM to the FCE environment, with the potential to influence nutrient dynamics in this system.

Solar radiation–enhanced dissolution of particulate organic matter from coastal marine sediments

We investigated the influence of solar radiation on the transfer of organic matter from the particulate to dissolved phase during resuspension of coastal sediments collected from seven sites across Florida Bay (organic carbon values ranged from 2% to 9% by weight). Sediments were resuspended in oligotrophic seawater for 48 h in 1-liter quartz flasks in the dark and under simulated solar radiation (SunTest XLS+) at wet weight concentrations of 100 mg L21 and 1 g L21 (dry weights ranged from 27 to 630 mg L21). There were little to no dissolved organic carbon (DOC) increases in dark resuspensions, but substantial DOC increases occurred in irradiated resuspensions. DOC levels increased 4 mg C L21 in an irradiated 1 g L21 suspension (dry weight 400 mg L21) of an organic-rich (7% organic carbon) sediment. At a particle load commonly found in coastal waters (dry weight 40 mg L21), an irradiated suspension of the same organic-rich sediment produced 1 mg C L21. DOC increases in irradiated resuspensions were well-correlated with particulate organic carbon (POC) added. Photodissolution of POC ranged from 6% to 15% at high sediment levels and 10% to 33% at low sediment levels. Parallel factor analysis modeling of excitation-emission matrix fluorescence data (EEM PARAFAC) suggested the dissolved organic matter (DOM) produced during photodissolution included primarily humic-like components and a less important input of protein-like components. Principal component analysis (PCA) of EEM data revealed a marked similarity in the humic character of photodissolved DOM from organic-rich sediments and the humic character of Florida Bay waters.

Effect of pH and temperature on the carbonate promoted dissolution of sodium meta-autunite

Release of uranium from Na-autunite, an artificial mineral created as a result of polyphosphate injection in the subsurface at the DOE Hanford Site, takes place during slow dissolution of the mineral structure. Stability information of the uranyl-phosphate phases is limited to conditions involving pH, temperature, and a few aqueous organic materials. The carbonate ion, which creates very strong complexes with uranium, is the predominant ion in the groundwater composition. The polyphosphate technology with the formation of autunite was identified as the most feasible remediation strategy to sequester uranium in contaminated groundwater and soil in situ. The objectives of the experimental work were (i) to quantify the effect of bicarbonate on the stability of synthetic sodium meta-autunite created as a result of uranium stabilization through polyphosphate injection, (ii) calculate the kinetic rate law parameters of the uranium release from Na-autunite during dissolution, and (iii) to compare the process parameters with those obtained for natural calcium meta-autunite. Experiments were conducted using SPTF apparatus, which consists of syringe pumps for controlling flow rate, Teflon reactors and a heating/cooling system. 0.25 grams of synthetic Na-autunite was placed in the reactor and buffer solutions with varying bicarbonate concentrations (0.0005 to 0.003 M) at different pH (6 - 11) were pumped through the reactors. Experiments were conducted at four different temperatures in the range of 5 - 60oC. It was concluded that the rate of release of uranium from synthetic Na-autunite is directly correlated to the bicarbonate concentration. The rate of release of uranium increased from 1.90 x 10-12 at pH 6 to 2.64 x 10-10 (mol m-2 s-1) at pH 11 at 23oC over the bicarbonate concentration range tested. The activation energy values were invariant with the change in the bicarbonate concentration; however, pH is shown to influence the activation energy values. Uranyl hydroxides and uranyl carbonates complexes helped accelerate the dissolution of autunite mineral.