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Organic aerosols are ubiquitous in the earth's atmosphere. They have been extensively studied in urban, rural and marine environments. However, little is known about the fluorescence properties of water-soluble organic carbon (WSOC) or their transport to and distribution in the polar regions. Here, we present evidence that fluorescent WSOC is a substantial component of High Arctic aerosols. The ratios of fluorescence intensity of protein-like peak to humic-like peak generally increased from dark winter to early summer, indicating an enhanced contribution of protein-like organics from the ocean to Arctic aerosols after the polar sunrise. Such a seasonal pattern is in agreement with an increase of stable carbon isotope ratios of total carbon (delta C-13(TC)) from -26.8 parts per thousand to -22.5 parts per thousand. Our results suggest that Arctic aerosols are derived from a combination of the long-range transport of terrestrial organics and local sea-to-air emission of marine organics, with an estimated contribution from the latter of 8.7-77% (mean 45%)., AuthorCount:11

The location and magnitude of oceanic iron sources remain uncertain owing to a scarcity of data, particularly in the Arctic Ocean. The formation of cold, dense water in the subsurface layer of the western Arctic Ocean is a key process in the lateral transport of iron, macronutrients, and other chemical constituents. Here, we present iron, humic-like fluorescent dissolved organic matter, and nutrient concentration data in waters above the continental slope and shelf and along two transects across the shelf-basin interface in the western Arctic Ocean. We detected high concentrations in shelf bottom waters and in a plume that extended in the subsurface cold dense water of the halocline layer in slope and basin regions. At sigma(theta) = 526.5, dissolved Fe, humic-like fluorescence intensity, and nutrient maxima coincided with N* minima (large negative values of N* indicate significant denitrification within shelf sediments). These results suggest that these constituents are supplied from the shelf sediments and then transported laterally to basin regions. Humic dissolved organic matter probably plays the most important role in the subsurface maxima and lateral transport of dissolved Fe in the halocline layer as natural Fe-binding organic ligand.

Major fraction of marine dissolved organic matter (DOM) is biologically recalcitrant, however, the accumulation mechanism of recalcitrant DOM has not been fully understood. Here, we examine the distributions of humic-like fluorescent DOM, factions of recalcitrant DOM, and the level of apparent oxygen utilization in the Japan Sea. We find linear relationships between these parameters for the deep water (>200 m) of the Japan Sea, suggesting that fluorescent DOM is produced in situ in the Japan Sea. Furthermore, we find that the amount of fluorescent DOM at a given apparent oxygen utilization is greater in the deep water of the Japan Sea than it is in the North Pacific, where the highest level of fluorescent DOM in the open ocean was previously observed. We conclude that the repeated renewal of the deep water contributes to the accumulation of fluorescent DOM in the interior of the Japan Sea.

Chromophoric dissolved organic matter (CDOM) ubiquitously occurs in marine environments and plays a significant role in the marine biogeochemical cycles. Basin scale distributions of CDOM have recently been surveyed in the global ocean and indicate that quantity and quality of oceanic CDOM are mainly controlled by in situ production and photobleaching. However, factors controlling the spectral parameters of CDOM in the UV region, i.e., spectral slope of CDOM determined at 275-295 nm (S275-295) and the ratio of two spectral slope parameters (S-R); the ratio of S275-295 to S350-400, have not been well documented. To evaluate the factor controlling the spectral characteristics of CDOM in the UV region in the open ocean, we determined the quantitative and qualitative characteristics of CDOM in the subarctic and subtropical surface waters (5-300 m) of the western North Pacific. Absorption coefficients at 320 nm in the subarctic region were higher than those in the subtropical region throughout surface waters, suggesting that magnitudes of photobleaching were different between the two regions. The values of S275-295 and SR were also higher in the subtropical region than the subarctic region. The dark microbial incubation showed biodegradation of DOM little affected S275-295, but slightly decreased SR. On the other hand, increases in S275-295 and relative stableness of SR were observed during photo-irradiation incubations respectively. These experimental results indicated that photobleaching of CDOM mainly induced qualitative differences in CDOM at UV region between the subarctic and subtropical surface waters. The results of this study imply that S275-295 can be used as a tracer of photochemical history of CDOM in the open ocean.

The coastal zone of the Florida Keys features the only living coral reef in the continental United States and as such represents a unique regional environmental resource. Anthropogenic pressures combined with climate disturbances such as hurricanes can affect the biogeochemistry of the region and threaten the health of this unique ecosystem. As such, water quality monitoring has historically been implemented in the Florida Keys, and six spatially distinct zones have been identified. In these studies however, dissolved organic matter (DOM) has only been studied as a quantitative parameter, and DOM composition can be a valuable biogeochemical parameter in assessing environmental change in coastal regions. Here we report the first data of its kind on the application of optical properties of DOM, in particular excitation emission matrix fluorescence with parallel factor analysis (EEM-PARAFAC), throughout these six Florida Keys regions in an attempt to assess spatial differences in DOM sources. Our data suggests that while DOM in the Florida Keys can be influenced by distant terrestrial environments such as the Everglades, spatial differences in DOM distribution were also controlled in part by local surface runoff/fringe mangroves, contributions from seasgrass communities, as well as the reefs and waters from the Florida Current. Application of principal component analysis (PCA) of the relative abundance of EEM-PARAFAC components allowed for a clear distinction between the sources of DOM (allochthonous vs. autochthonous), between different autochthonous sources and/or the diagenetic status of DOM, and further clarified contribution of terrestrial DOM in zones where levels of DOM were low in abundance. The combination between EEM-PARAFAC and PCA proved to be ideally suited to discern DOM composition and source differences in coastal zones with complex hydrology and multiple DOM sources.

The coastal zone of the Florida Keys features the only living coral reef in the continental United States and as such represents a unique regional environmental resource. Anthropogenic pressures combined with climate disturbances such as hurricanes can affect the biogeochemistry of the region and threaten the health of this unique ecosystem. As such, water quality monitoring has historically been implemented in the Florida Keys, and six spatially distinct zones have been identified. In these studies however, dissolved organic matter (DOM) has only been studied as a quantitative parameter, and DOM composition can be a valuable biogeochemical parameter in assessing environmental change in coastal regions. Here we report the first data of its kind on the application of optical properties of DOM, in particular excitation emission matrix fluorescence with parallel factor analysis (EEM-PARAFAC), throughout these six Florida Keys regions in an attempt to assess spatial differences in DOM sources. Our data suggests that while DOM in the Florida Keys can be influenced by distant terrestrial environments such as the Everglades, spatial differences in DOM distribution were also controlled in part by local surface runoff/fringe mangroves, contributions from seasgrass communities, as well as the reefs and waters from the Florida Current. Application of principal component analysis (PCA) of the relative abundance of EEM-PARAFAC components allowed for a clear distinction between the sources of DOM (allochthonous vs. autochthonous), between different autochthonous sources and/or the diagenetic status of DOM, and further clarified contribution of terrestrial DOM in zones where levels of DOM were low in abundance. The combination between EEM-PARAFAC and PCA proved to be ideally suited to discern DOM composition and source differences in coastal zones with complex hydrology and multiple DOM sources.

Chromophoric dissolved organic matter (CDOM) ubiquitously occurs in marine environments and plays a significant role in the marine biogeochemical cycles. Basin scale distributions of CDOM have recently been surveyed in the global ocean and indicate that quantity and quality of oceanic CDOM are mainly controlled by in situ production and photobleaching. However, factors controlling the spectral parameters of CDOM in the UV region, i.e., spectral slope of CDOM determined at 275-295 nm (S275-295) and the ratio of two spectral slope parameters (S-R); the ratio of S275-295 to S350-400, have not been well documented. To evaluate the factor controlling the spectral characteristics of CDOM in the UV region in the open ocean, we determined the quantitative and qualitative characteristics of CDOM in the subarctic and subtropical surface waters (5-300 m) of the western North Pacific. Absorption coefficients at 320 nm in the subarctic region were higher than those in the subtropical region throughout surface waters, suggesting that magnitudes of photobleaching were different between the two regions. The values of S275-295 and SR were also higher in the subtropical region than the subarctic region. The dark microbial incubation showed biodegradation of DOM little affected S275-295, but slightly decreased SR. On the other hand, increases in S275-295 and relative stableness of SR were observed during photo-irradiation incubations respectively. These experimental results indicated that photobleaching of CDOM mainly induced qualitative differences in CDOM at UV region between the subarctic and subtropical surface waters. The results of this study imply that S275-295 can be used as a tracer of photochemical history of CDOM in the open ocean.

Fluorescent dissolved organic matter (DOM), a fraction of chromophoric DOM, has been known to be produced in the deep ocean and has been considered to be bio-refractory. However, the factors controlling fluorescence properties of DOM in the deep ocean are still not well understood. In this study, we determined the fluorescence properties of DOM in the deep waters of the Okhotsk Sea and the northwestern North Pacific Ocean using excitation-emission matrix (EEM) fluorescence and parallel factor analysis (PARAFAC). One protein-like, two humic-like components, and one uncertain component, that might be derived from a fluorometer artifact, were identified by EEM-PARAFAC. Fluorescence intensity levels of the protein-like component were highest in the surface waters, decreased with depth, but did not change systematically in the bathypelagic layer (1000 m - bottom). Fluorescence characteristics of the two humic-like components were similar to those traditionally defined as marine and terrestrial humic-like fluorophores, respectively. The fluorescence intensity levels of the two humic-like components were lowest in the surface waters, increased with depth in the mesopelagic layer (200 - 1000 m), and then slightly decreased with depth in the bathypelagic layer. The ratio of the two humic-like components remained in a relatively narrow range in the bathypelagic layer compared to that in the surface layer, suggesting a similar composition of humic-like fluorophores in this layer. In addition, the fluorescence intensities of the two humic-like components were linearly correlated to apparent oxygen utilization (AOU) in the bathypelagic layer, suggesting that both humic-like components are produced in situ as organic matter is oxidized biologically. These findings imply that optical characteristics of humic-like fluorophores once formed might not be altered further biologically or geochemically in the deep ocean. On the other hand, relationships of fluorescence intensities with A

Fluorescent dissolved organic matter (DOM), a fraction of chromophoric DOM, has been known to be produced in the deep ocean and has been considered to be bio-refractory. However, the factors controlling fluorescence properties of DOM in the deep ocean are still not well understood. In this study, we determined the fluorescence properties of DOM in the deep waters of the Okhotsk Sea and the northwestern North Pacific Ocean using excitation-emission matrix (EEM) fluorescence and parallel factor analysis (PARAFAC). One protein-like, two humic-like components, and one uncertain component, that might be derived from a fluorometer artifact, were identified by EEM-PARAFAC. Fluorescence intensity levels of the protein-like component were highest in the surface waters, decreased with depth, but did not change systematically in the bathypelagic layer (1000 m - bottom). Fluorescence characteristics of the two humic-like components were similar to those traditionally defined as marine and terrestrial humic-like fluorophores, respectively. The fluorescence intensity levels of the two humic-like components were lowest in the surface waters, increased with depth in the mesopelagic layer (200 - 1000 m), and then slightly decreased with depth in the bathypelagic layer. The ratio of the two humic-like components remained in a relatively narrow range in the bathypelagic layer compared to that in the surface layer, suggesting a similar composition of humic-like fluorophores in this layer. In addition, the fluorescence intensities of the two humic-like components were linearly correlated to apparent oxygen utilization (AOU) in the bathypelagic layer, suggesting that both humic-like components are produced in situ as organic matter is oxidized biologically. These findings imply that optical characteristics of humic-like fluorophores once formed might not be altered further biologically or geochemically in the deep ocean. On the other hand, relationships of fluorescence intensities with A