Correlation of the absorption coefficient with a reduction in mean mass for dissolved organic matter in southwest Florida river plumes

Results are presented from an investigation of the relationship between molecular mass distribution and optical properties for colored dissolved organic matter (CDOM); a complex assembly of organic macromolecules of marine and freshwater origin found throughout the surface ocean. Unique data are derived from the application of a new technique, a combination of a hydrophilic-lipophilic copolymer-based solid phase extraction (SPE) with electrospray ionization (ESI) continuous flowing ion trap mass spectrometry (cf-MS), for the direct determination of CDOM mass distribution. An evaluation of this copolymer-based extraction technique for the analysis of Suwannee River Natural Organic Matter (SRNOM) reference material revealed that the current method compares favorably with C-18 modified silica or XAD resin-based extraction methods reported in the literature when considering extraction efficiency or low extraction bias for CDOM. The mass distribution of CDOM in several freshwater to marine transition zones along coastal southwestern Florida has been determined with this technique. All rivers in the study region had a bimodal distribution of masses. A case study of the Caloosahatchee River outflow CDOM mass distribution data are presented as an example of the modification in mass distributions. The lower mass mode of the bimodal distribution was observed to have a relatively stable mean throughout the study region at 406 +/- 9 Da, while decreasing in concentration in a non-conservative manner with salinity. In contrast, the upper mass mode of the bimodal distribution was observed to have a variable mean, reaching 1408 Da in the least saline waters and decreasing by 174 Da through the transect toward higher salinity coastal waters. Coinciding with this reduction in mean mass for the upper distribution is a non-conservative reduction in concentration when compared with salinity. We define apparent organic carbon (AOC) as a function of the cf-MS determined total integrated area and use this value to determine concentration of the total extracted CDOM. Unique correlations between the CDOM fluorescence (350-nm excitation/450-nm emission) and the AOC for these coastal samples have been observed for each of three rivers in the study region. The steepest slope and highest correlation between optical and mass spectral properties are observed in rivers with strongly absorbing waters originating in the Florida Everglades and lowest in rivers draining clearer waters from widely variable and anthropogenic influenced regions. The trends in molecular mass distribution and corresponding optical properties support the theory that CDOM in coastal zones is environmentally processed material from terrestrial sources. Probable cause of the reduction in mean mass and suggestions for further investigation of sources and transformations of CDOM are discussed. (C) 2004 Elsevier B.V. All rights reserved.