Application of fluorescence and PARAFAC to assess vertical distribution of subsurface hydrocarbons and dispersant during the Deepwater Horizon oil spill.

We evaluated the use of excitation and emission matrix (EEM) fluorescence and parallel factorial analysis (PARAFAC) modeling techniques for monitoring crude oil components in the water column. Four of the seven derived PARAFAC loadings were associated with the Macondo crude oil components. The other three components were associated with the dispersant, an unresolved component and colored dissolved organic matter (CDOM). The fluorescence of the associated benzene and naphthalene-like components of crude oil exhibited a maximum at ∼1200 m. The maximum fluorescence of the component associated with the dispersant (i.e., Corexit EC9500A) was observed at the same depth. The plume observed at this depth was attributed to the dispersed crude oil from the Deepwater Horizon oil spill. Results demonstrate the application of EEM and PARAFAC to simultaneously monitor selected PAH, dispersant-containing and humic-like fluorescence components in the oil spill region in the Gulf of Mexico.

Resolving DOM fluorescence fractions during a Karenia brevis bloom patch on the Southwest Florida Shelf.

Organic matter can be supplied naturally from land through rivers or produced in-situ in the marine environment. Current methods of examining natural bulk dissolved organic matter (DOM) are not able to discriminate multiple sources of DOM. A diagnostic tool to identify DOM sources is critical to determine possible sources of organic nutrients that influence K. brevis harmful algal bloom (HAB) development. This study applied multi-wavelength fluorescence coupled with a supervised pattern recognition technique (e.g., parallel factorial analysis (PARAFAC) using samples collected from river, estuary and shelf waters where the toxic dinoflagellate Karenia brevis off of Sanibel Island, Florida was observed. The PARAFAC model distinguished four different fractions of DOM components containing humic-like and protein-like components. The derived terrestrial humic-like material was indicative of land-based sources while the tryptophan-like component was likely produced from in-situ biological production. The study developed and tested the hypothesis that the direct relationship of the protein-like DOM fluorescence with K. brevis cell density indicated that the bloom patch was most likely supported by organic nutrients produced in-situ. The results demonstrated that multi-wavelength fluorescence analysis coupled with PARAFAC modeling technique simultaneously resolved DOM fluorescence fractions and their possible sources-information that are critical in explaining harmful algal bloom formation.

Sunlight-induced photochemical decay of oxidants in natural waters: implications in ballast water treatment.

The transport and discharge of ship ballast water has been recognized as a major vector for the introduction of invasive species. Chemical oxidants, long used in drinking water and wastewater treatment, are alternative treatment methods for the control of invasive species currently being tested for use on ships. One concern when a ballasted vessel arrives in port is the adverse effects of residual oxidant in the treated water. The most common oxidants include chlorine (HOCl/OCl-), bromine (HOBr/OBr-), ozone (03), hydrogen peroxide (H2O2), chlorine dioxide (ClO2), and monochloramine (NH2Cl). The present study was undertaken to evaluate the sunlight-mediated photochemical decomposition of these oxidants. Sunlight photodecomposition was measured at various pH using either distilled water or oligotrophic Gulf Stream water for specific oxidants. For selected oxidants, quantum yields at specific wavelengths were obtained. An environmental photochemical model, GCSOLAR, also provided predictions of the fate (sunlight photolysis half-lives) of HOCI/OCl-, HOBr/OBr-, ClO2, and NH2Cl for two different seasons at latitude 40 degrees and in water with two different concentrations of chromophoric dissolved organic matter. These data are useful in assessing the environmental fate of ballast water treatment oxidants if they were to be discharged in port.

Comparison of the molecular mass and optical properties of colored dissolved organic material in two rivers and coastal waters by flow field-flow fractionation.

Colored dissolved organic material (CDOM) is an important sunlight absorbing substance affecting the optical properties of natural waters. However, little is known about its structural and optical properties mainly due to its complex matrix and the limitation of the techniques available. A comparison of two southwestern Florida rivers [the Caloosahatchee River (CR) and the Shark River (SR)] was done in terms of molecular mass (MM) and diffusion coefficients (D). The novel technique Frit inlet/frit outlet-flow field-flow fractionation (FIFO-FIFFF) with absorbance and fluorescence detectors was used to determine these properties. The SR receives organic material from the Everglades. By contrast, the CR arises from Lake Okeechobee in central Florida, receiving anthropogenic inputs, farming runoff, and natural organics. Both rivers discharge to the Gulf of Mexico. Fluorescence identified, for both rivers, two different MM distributions in low salinity water samples: the first was centered at approximately 1.7 kDa (CR) and approximately 2 kDa (SR); the second centered at approximately 13 kDa for both rivers, which disappeared gradually in the river plumes to below detection limit in coastal waters. Absorbance detected only one MM distribution centered at approximately 2 kDa (CR) and 2.2-2.4 kDa (SR). Fluorescence in general peaked at a lower MM than absorbance, suggesting a different size distribution for fluorophores vs chromophores. A photochemical study showed that, after sunlight, irradiated freshwater samples have similar characteristics to more marine waters, including a shift in MM distribution of chromophores. The differences observed between the rivers in the optical characteristics, MM distributions, and D values suggest that the CDOM sources, physical, and photochemical degradation processes are different for these two rivers.