Youhei Yamashita

Chemical characterization of protein-like fluorophores in DOM in relation to aromatic amino acids

A systematic survey of the protein-like fluorescence intensities was conducted at 11 stations along the 137°E transect from bay to oceanic areas in the northwestern Pacific using three-dimensional excitation emission matrix (3DEEM) spectroscopy and the concentrations of aromatic amino acids obtained by high-performance liquid chromatography (HPLC) in dissolved organic matter (DOM). The 3DEEM patterns of tyrosine-like and tryptophan-like peaks in protein-like fluorophores were variable across different marine environments. The tyrosine-like peak was observed at all stations and depths, while the tryptophan-like peak was only distinguishable as a clear peak in bay and coastal surface waters. These distribution patterns were similar to those of actual concentrations of tyrosine and tryptophan in total hydrolyzable amino acids (THAA) in DOM. Consequently, the tyrosine- and tryptophan-like fluorescence intensities were interpreted to be correlated to the concentrations of tyrosine and tryptophan, respectively, indicating that tyrosine and tryptophan were responsible for the protein-like fluorescence intensities of DOM. The protein-like fluorescence intensities were also correlated to the concentrations of THAA, suggesting that the dynamics of aromatic amino acids were similar to those of THAA. In addition, protein-like fluorescence intensities may be useful indicators as to the dynamics of not only aromatic amino acids but of THAA in bulk DOM as well. Comparison of the tyrosine- and tryptophan-like fluorescence intensities with the concentrations of aromatic amino acids and THAA suggests that the dissolved amino acids were components of relatively small peptides and not protein molecules.

Dissolved Organic Matter Characteristics Across a Subtropical Wetland’s Landscape: Application of Optical Properties in the Assessment of Environmental Dynamics

Wetlands are known to be important sources of dissolved organic matter (DOM) to rivers and coastal environments. However, the environmental dynamics of DOM within wetlands have not been well documented on large spatial scales. To better assess DOM dynamics within large wetlands, we determined high resolution spatial distributions of dissolved organic carbon (DOC) concentrations and DOM quality by excitation–emission matrix spectroscopy combined with parallel factor analysis (EEM–PARAFAC) in a subtropical freshwater wetland, the Everglades, Florida, USA. DOC concentrations decreased from north to south along the general water flow path and were linearly correlated with chloride concentration, a tracer of water derived from the Everglades Agricultural Area (EAA), suggesting that agricultural activities are directly or indirectly a major source of DOM in the Everglades. The optical properties of DOM, however, also changed successively along the water flow path from high molecular weight, peat-soil and highly oxidized agricultural soil-derived DOM to the north, to lower molecular weight, biologically produced DOM to the south. These results suggest that even though DOC concentration seems to be distributed conservatively, DOM sources and diagenetic processing can be dynamic throughout wetland landscapes. As such, EEM–PARAFAC clearly revealed that humic-enriched DOM from the EAA is gradually replaced by microbial- and plant-derived DOM along the general water flow path, while additional humic-like contributions are added from marsh soils. Results presented here indicate that both hydrology and primary productivity are important drivers controlling DOM dynamics in large wetlands. The biogeochemical processes controlling the DOM composition are complex and merit further investigation.

Distribution and alteration of amino acids in bulk DOM along a transect from bay to oceanic waters

Abstract A systematic survey of the concentrations and composition of total hydrolyzable amino acids (THAA) in bulk dissolved organic matter (DOM) was conducted at 11 stations along the 137°E transect from bay to oceanic areas in the northwestern Pacific. Concentrations of THAA and their contributions to dissolved organic carbon were high in the bay and coastal areas, declined toward the oceanic area and decreased with depth in the water columns. From the distribution patterns of the relative abundances of amino acids along the transect, individual amino acids were divided into four groups. One group included tyrosine, valine, isoleucine, phenylalanine, leucine and tryptophan, and was considered to represent easily degradable THAA, while glycine and alanine belonged to a more biorefractory group of THAA. Principal components analysis (PCA) was conducted to quantitatively differentiate patterns of amino acid composition. Amino acid groups based on PCA agreed with the groups classified by distribution patterns, indicating that first principal component scores reflected the degree of degradation of THAA in DOM, and were defined as a degradation index (DI). Two amino acids, glycine and alanine, increased in relative abundance with increasing DI, while valine, isoleucine, phenylalanine and leucine decreased with decreasing DI. The agreement indicated that the degradation process was the key factor controlling the quantity and quality of THAA in bulk DOM.

In situ production of chromophoric dissolved organic matter in coastal environments

[1] The horizontal and vertical distribution of marine humic-like fluorophore, namely, chromophoric dissolved organic matter (CDOM) fluorescence, was surveyed in Ise Bay, Japan. The distribution patterns of salinity and marine humic-like fluorescence intensity suggested that riverine humic-like fluorophore conservatively distributed along with fresh-sea water mixing in surface water at Ise Bay. However, analysis of mixing behavior of riverine CDOM implied that the 25.1 ± 10.6% in average of bulk marine humic-like fluorescence intensity of Ise Bay surface waters was derived not from a terrestrial origin but an in situ production. A degradation experiment using natural plankton demonstrated the rapid production of marine humic-like fluorophore within a day. The results consistently suggested that in situ production of marine humic-like fluorophore plays an important role in the dynamics of CDOM in coastal environments.

Fluorescence characteristics of size-fractionated dissolved organic matter: implications for a molecular assembly based structure?

Surface freshwater samples from Everglades National Park, Florida, were used to investigate the size distributions of natural dissolved organic matter (DOM) and associated fluorescence characteristics along the molecular weight continuum. Samples were fractionated using size exclusion chromatography (SEC) and characterized by spectroscopic means, in particular Excitation-Emission Matrix fluorescence modeled with parallel factor analysis (EEM-PARAFAC). Most of the eight components obtained from PARAFAC modeling were broadly distributed across the DOM molecular weight range, and the optical properties of the eight size fractions for all samples studied were quite consistent among each other. Humic-like components presented a similar distribution in all the samples, with enrichment in the middle molecular weight range. Some variability in the relative distribution of the different humic-like components was observed among the different size fractions and among samples. The protein like fluorescence, although also generally present in all fractions, was more variable but generally enriched in the highest and lowest molecular weight fractions. These observations are in agreement with the hypothesis of a supramolecular structure for DOM, and suggest that DOM fluorescence characteristics may be controlled by molecular assemblies with similar optical properties, distributed along the molecular weight continuum. This study highlights the importance of studying the molecular structure of DOM on a molecular size distribution perspective, which may have important implications in understanding the environmental dynamics such materials.

Dissolved Black Carbon in Grassland Streams: Is There an Effect of Recent Fire History?

While the existence of black carbon as part of dissolved organic matter (DOM) has been confirmed, quantitative determinations of dissolved black carbon (DBC) in freshwater ecosystem and information on factors controlling its concentration are scarce. In this study, stream surface water samples from a series of watersheds subject to different burn frequencies in Konza Prairie (Kansas, USA) were collected in order to determine if recent fire history has a noticeable effect on DBC concentration. The DBC levels detected ranged from 0.04 to 0.11 mg L(-1), accounting for ca. 3.32±0.51% of dissolved organic carbon (DOC). No correlation was found between DBC concentration and neither fire frequency nor time since last burn. We suggest that limited DBC flux is related to high burning efficiency, possibly greater export during periods of high discharge and/or the continuous export of DBC over long time scales. A linear correlation between DOC and DBC concentrations was observed, suggesting the export mechanisms determining DOC and DBC concentrations are likely coupled. The potential influence of fire history was less than the influence of other factors controlling the DOC and DBC dynamics in this ecosystem. Assuming similar conditions and processes apply in grasslands elsewhere, extrapolation to a global scale would suggest a global grasslands flux of DBC on the order of 0.14 Mt carbon year(-1).

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.

Iron(III) hydroxide solubility and humic-type fluorescent organic matter in the deep water column of the Okhotsk Sea and the northwestern North Pacific Ocean

Abstract Vertical distributions of Fe(III) hydroxide solubility were studied in the Okhotsk Sea and the northwestern North Pacific Ocean during May and June 2000. Fe(III) solubility minima (0.35– 0.45 nM ) were present in a narrow depth range (80– 100 m ) below the surface mixed layer at all stations. In general, the Fe(III) solubility levels in intermediate and deep waters are characterized by mid-depth maxima (0.76– 0.86 nM ) at 800– 1250 m depth and, below that, a slight decrease to 0.4– 0.6 nM with depth in association with increase in nutrient, apparent oxygen utilization (AOU) and humic-type fluorescence intensity. The most significant correlation between the Fe(III) solubility and humic-type fluorescence in intermediate and deep waters suggests that the distribution of humic-type fluorescent organic matter may control the distribution of Fe(III) solubility in deep ocean waters. The solubility profiles reveal that dissolved Fe concentrations in deep ocean waters may be controlled primarily by Fe(III) complexation with natural organic ligands, such as marine dissolved humic substances released through the oxidative decomposition and transformation of biogenic organic matter in intermediate and deep waters. In addition, high Fe(III) hydroxide solubility values (1.0– 1.6 nM ) were observed in the surface mixed layer at a station in the northwestern North Pacific Ocean where a phytoplankton bloom was observed. The higher Fe(III) solubility in the surface waters was probably due to a higher concentration or stronger affinity of natural organic Fe(III) chelators, which may be released by dominant phytoplankton and/or bacteria during the spring bloom and probably have a different chemical composition from those found in intermediate and deep waters.

Accumulation of humic-like fluorescent dissolved organic matter in the Japan Sea

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.

Laterally spreading iron, humic-like dissolved organic matter and nutrients in cold, dense subsurface water of the Arctic Ocean

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 σθ = 26.5, 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.