Algal Dissolved Organic Matter Research Articles

Unveiling the effects of dissolved organic matter (DOM) extracted from coastal algae and river on the photooxidation of arsenite

The coastal environment is an important ecosystem connecting land and sea, and arsenite (As(III)) in coastal seawater can seriously affect human health through the food chain. However, the effects of dissolved organic matter (DOM) extracted from coastal algae and rivers on As(III) photooxidation remain unclear. Results show that coastal algal DOM (CA-DOM) is significantly more effective than Suwannee River natural organic matter (SRNOM) in photooxidation of As(III), with a rate 8.3 times higher after correcting for light screening effects. CA-DOM accelerates As(III) photooxidation mainly through the 3DOM⁎ pathway, contributing 78.7 % to the process, whereas 3NOM⁎ contributes only 37.2 % for SRNOM. CA-DOM consists primarily of low-excited tyrosine and tryptophan-like protein substances, whereas SRNOM consists of humic and fulvic acid-like substances. Thus, CA-DOM exhibits a higher steady-state concentration of 3DOM⁎, and the 3DOM⁎ reacts much faster with As(III) than the 3NOM⁎. The increase in CA-DOM concentration can significantly accelerate the photooxidation of As(III), whereas the effect of SRNOM concentration is negligible. Increased salinity can accelerate As(III) photooxidation for all types of DOM. Our results provide new insights into the role of DOM from different sources in the photooxidation of As(III) in the natural environment or engineering applications.

Photochemical processes transform dissolved organic matter differently depending on its initial composition

Dissolved organic matter (DOM) is one of the most important fluxes in the global carbon cycle but its response to light exposure remains unclear at a molecular-level. The chemical response of DOM to light should vary with its molecular composition and environmental conditions while some basic hypotheses are still unclear, such as the balance between photobleaching and photo-humification and the question of oxidative properties. Here we exposed aquatic DOM from diverse freshwaters impacted by different levels of anthropogenic activity and algal exudates to environmentally-realistic light conditions. We found that photobleaching occurred in DOM with relatively high initial humic content producing low H/C molecules, whereas DOM with low initial humic content was humified. DOM pools with relatively high initial saturation and low aromaticity were prone to transform towards more unsaturated molecular formulae and high H/C molecules with a distinct decrease of bioavailability. Photo-transformation was mainly influenced by reactive intermediates, with reactive oxygen species (ROS) playing a dominant role in humification when the initial humus content of DOM was high. In contrast, for algal DOM with high protein content, it was likely that the autoxidation of excited state DOM was more important than indirect oxidation involving ROS. Our results reveal how photo-transformation patterns depend on the initial composition of DOM and provide new insights into the role of photochemical processes in biogeochemical cycling of DOM.

Characterizing photochemical production carboxyl content of dissolved organic matters using absorbance spectroscopy combined with FT-ICR MS

Irradiation can significantly impact the structure, reactivity and environmental behavior of dissolved organic matter (DOM). The extent of these processes remains to be ascertained in more detail but the heterogeneity and site-specificity of DOM, and the lack of methods to characterize DOM at its environmentally-relevant concentrations make it a challenge. In this study, the differences of DOM response to photodegradation in four typical origins (i.e., surface water, sediment and intracellular and extracellular algal DOM) were tracked on the molecular-level using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS). Changes of the carboxyl and phenolic DOM moieties induced by irradiation were quantified by spectroscopic titrations, and the mechanism of functional groups affecting the changes of specific molecular composition was qualitatively proposed. The results demonstrated that intracellular algal organic matter (I-DOM) was most susceptible to photodegradation (ca. 63% DOM loss), then came extracellular algal organic matter (E-DOM) and surface water DOM (W-DOM) (ca. 15% DOM loss). Sediment DOM (S-DOM) was most resistant to irradiation, with a very small level of its mineralization. Lipids, lignin-like compounds and tannin-like compounds in I-DOM and E-DOM were relatively photo-labile. The photodegradation of lipids was related to the decarboxylation of carboxyl functional groups, while the photodegradation of tannin-like compounds was related to the rupture of phenolic functional groups. In comparison, the molecular composition of W-DOM and S-DOM was less affected by irradiation, which was also reflected in the fact that the carboxyl and phenolic functional groups were highly photo-resistant. This study showed that the photoactivity of DOM in surface water was closely related to the abundance of algae, so controlling the excessive reproduction of algae may have a positive effect on stability of quality and quantity of organic matter in surface water.

Impact of light-aged microplastic on microalgal production of dissolved organic matter

Microplastics (MPs) can affect phytoplankton and its photosynthetic performance in many but often in negative ways. Phytoplankton is an important source of dissolved organic matter (DOM) in aquatic ecosystems, but the impact of MPs on the algal production of DOM is poorly known. We investigated the impacts of polyvinyl chloride MPs on the growth and DOM production by Chlamydomonas reinhardtii microalgae in a 28-day-long experiment. During the exponential growth phase of C. reinhardtii, MPs slightly affected algal growth and DOM production. At the end of experiment, MPs decreased the biomass of C. reinhardtii by 43 % in the treatment with MPs exposed to simulated solar radiation prior the experiment (light-aged) and more than in the treatment with virgin MPs. The light-aged MPs decreased algal DOM production by 38 % and modified the chemical composition of DOM. According to spectroscopic analyses, the light-aged MPs increased aromaticity, average molecular weight and fluorescence of DOM produced by C. reinhardtii. The elevated fluorescence was associated with humic-like components identified by a 5-component parallel factor analysis (PARAFAC) from the excitation-emission matrices. We conclude that although MPs can leach DOM to aquatic ecosystems, they potentially modify the aquatic DOM more by interfering with the algal production of DOM and changing the composition of produced DOM.

Transformation of algal-dissolved organic matter via sunlight-induced photochemical and microbial processes: interactions between two processes.

Algal-dissolved organic matter (ADOM) is an important fraction of dissolved organic carbon (DOC) in eutrophic water. Although ADOM is known to be readily transformed by microbes, the role of sunlight-induced photochemical process and the interactions between two processes on ADOM transformation remains unclear. In this study, three types of treatments for ADOM, including photochemical process under natural solar light (L treatment), microbial process (M treatment), and the simultaneous photochemical plus microbial process (L&M), were performed for 18days. Our results showed that M treatment was more effective for the loss of DOC, chromophoric DOM (CDOM) at short wavelengths (a254 and a280), than L treatment, while L treatment was more effective for the transformation of a350 and the fluorescent components of the ubiquitous humic-like component and the tryptophan-like component. Comparison in the decay kinetics of DOC and CDOM in the three treatments showed that the simultaneous photochemical and biological processes exhibited an inhibitory effect on DOC decay rate but not the percentage of labile DOC fraction. Higher relative abundance of protein-like substances was found after L&M treatment, while the relative abundance of humic-like substance and aromaticity increased after M treatment, and the low molecular-weight compounds were produced after L treatment. Our results emphasized the importance of photochemistry in processing ADOM to mediate the chemodiversity in natural water.

A study of peatland-derived dissolved organic matter from headstream to sea using multiple analytical tools.

The River Thurso, North Scotland, receives substantial terrestrial deliveries of dissolved organic matter (DOM) leached from Europe's most extensive blanket bogs. The relatively short distance between peatlands and coastal ocean offers potential for research to investigate source-to-sea processing of terrigenous dissolved organic carbon (DOC). Here, we determined DOC concentrations in the bulk (< 0.4μm), truly dissolved (< 5kDa), and colloidal fraction (5kDa - 0.4μm) as well as DOM absorbance and fluorescence spectra during two river catchment surveys and two corresponding coastal plume surveys, in early spring (1st sampling period) and late spring (2nd sampling period). DOC concentrations ranged from 79 to 3799μM in early spring and from 115 to 5126μM in late spring. DOM exhibited conservative mixing across the plume in both surveys, but the plume extended further offshore in the second survey due to a pulse of freshwater caused by recent rainfall. Fluorescence excitation-emission matrices (EEMs) and fluorescence indices revealed that the flushed DOM was humic-like, recently synthesized DOM. Coupled with C/N ratio analyses and molecular weight fractionation, the fluorescence indices also provided evidence for the gradual altering of DOM characteristics along the bog - headstream - loch - river continuum. The same analytical tools revealed that seasonal variations occurred within the DOM pool of marine origin, i.e., greater abundance of low-molecular weight bacterial or algal DOM in the late spring survey. The time scale of such variations relative to the flushing time of water through the aquatic continuum should be taken into account when interpreting the DOM property-salinity distributions of major river plumes.

Effect of UV and Visible Radiation on Optical Properties of Chromophoric Dissolved Organic Matter Released by Emiliania huxleyi

Photodegradation is a natural process that strongly affects the chromophoric fraction of dissolved organic matter (DOM), especially in surface water of the oceans. In the euphotic zone, the concentration and quality of DOM are mostly dependent on primary production by phytoplankton. The effect of photodegradation on algal DOM has not been investigated as much as on terrestrial DOM. In this study, we explored the effect of different spectral regions (i.e., full sun spectrum, visible light, 295–800 nm, 305–800 nm, and 320–800 nm) on algal exudates by Emiliania huxleyi, a ubiquitous coccolithophore. The optical properties (absorption and fluorescence) of algal DOM were investigated before and after irradiation with the different spectral regions. The absorption and fluorescence spectra were compared before and after irradiation. The results showed an increase in the effect of photobleaching with increasing irradiation energy for all of the absorbance indices. Similarly, the protein-like fluorescence decreased at increasing irradiation energy. The humic-like fluorescence, which was the most affected, did not show a linear trend between photobleaching and irradiation energy, which suggested that irradiation mainly determined a change in these molecules’ quantum yield.

Characterization and Dynamic Analysis of Dissolved Proteins in Lake Biwa Using Two-Dimensional Electrophoresis.

Concentrated protein-like fluorophores of dissolved organic matter (DOM) in Lake Biwa were analyzed using sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and two-dimensional electrophoresis (2-DE). As a result, it was found that the protein-like fluorophores in Lake Biwa are likely to be dissolved proteins released from phytoplankton. SDS-PAGE analysis revealed that protein-like fluorophores from Lake Biwa usually consist of proteins with molecular weights of 33 - 35, 42 - 45, 56 - 59 and 62 - 66 kDa. The molecular weights (MWs) and isoelectric points (pIs) of dissolved proteins in Lake Biwa were firstly clarified using 2-DE. The 2-DE patterns of proteins in Lake Biwa were compared with those for algal DOM released from four kinds of lake phytoplankton, Microcystis aeruginosa, Staurastrum dorsidentiferum, Cryptomonas ovata, and Fragilaria capucina. Some of the protein spots in 2-DE of Lake Biwa were similar to those of algal DOM released during cultivation. The relations between monthly changes in the electrophoretic gel images of lake water samples and those in the community structure of phytoplankton in Lake Biwa were observed. These results suggest that some of the dissolved proteins in Lake Biwa are likely derived from phytoplankton.

Aerobic and Anaerobic Bacterial Mercury Uptake is Driven by Algal Organic Matter Composition and Molecular Weight.

The biological mobilization of mercury (Hg) into microbes capable of Hg methylation is one of the limiting steps in the formation of the neurotoxin methylmercury (MeHg). Although algal dissolved organic matter (DOM) has been associated with increased MeHg production, the relationship between bacterial Hg uptake and algal DOM remains unexplored. In this study, we aimed to address how the quantity and quality of DOM, freshly harvested from several algae, affected the bacterial uptake of Hg with the use of a biosensor capable of functioning both aerobically and anaerobically. We combined biosensor measurements with high-resolution mass spectrometry and field-flow fractionation to elucidate how DOM composition and molecular weight influenced microbial Hg uptake. We showed that freshly harvested DOM from Chlorophyte and Euglena mutabilis strongly inhibited aerobic and anaerobic Hg uptake, whereas DOM harvested from Euglena gracilis did not exhibit this same pronounced effect. Once fractionated, we found that amino acids and polyamines, most abundant in Euglena gracilis DOM, were positively correlated to increase Hg uptake, suggesting that these molecules are potentially underappreciated ligands affecting Hg bioavailability. As water quality is affected by eutrophication, algal community assemblages will change, leading to variations in the nature of autochthonous DOM released in aquatic systems. Our results highlight that variations in the emergent properties of DOM originating from varying algal species can have a profound effect on bacterial Hg uptake and thus methylation.

Influence of parasitic chytrids on the quantity and quality of algal dissolved organic matter (AOM)

Algae-derived dissolved organic matter (AOM) is an important nutrient source for heterotrophic bacteria, while AOM such as humic substances pose significant challenges during water treatment processing. We hypothesized that the parasitic infection of algae could change the composition and concentration of AOM. This study investigated the quality and quantity of DOM and bacterial abundance in diatom (Synedra) cultures, with and without parasitic fungi (chytrids). The quality of DOM was analyzed using three-dimensional excitation-emission matrix combined with parallel factor analysis (EEM-PARAFAC) and was compared to changes in algal and bacterial cell numbers. Bacterial abundance was higher and dissolved organic carbon concentrations were lower in the diatom cultures infected with parasitic fungi. Among the DOM compounds, the concentrations of tryptophan-like material derived from algae were significantly lower and the concentrations of humic substance-like material were higher in the infected treatment. The parasitic fungi may have consumed tryptophan-like material and stimulated the release of humic substances. These results provide the first evidence that fungal infection may modulate algal–bacterial interactions, which are associated with changes in the nature of AOM.

Unique characteristics of algal dissolved organic matter and their association with membrane fouling behavior: a review.

Over the last several decades, the frequent occurrence of algal bloom in drinking water supplies, driven by increasing anthropogenic input and climate change, has posed serious problems for membrane filtration processes, resulting in reduced membrane permeability and increased energy consumption. It is essential to comprehensively understand the characteristics of algal dissolved organic matter (DOM) and the subsequent effects on the filtration processes for better insight into membrane fouling mitigation. Many studies have revealed that algal DOM has displayed unique characteristics distinguished from other sources of DOM with respect to the chemical composition, the structures, and the molecular weight distributions. Algal DOM is considered to be a major obstacle in understanding membrane fouling due to its complicated interactions among dissimilar algal DOM constituents as well as between algal DOM and membrane material matrices. The present review article summarizes (1) recent characterizing methods for algal DOM, (2) environmental factors affecting the characteristics of algal DOM, (3) the discrepancies between algal DOM and other sources of aquatic DOM, particularly terrestrial sources, and (4) potential fouling effects of algal DOM on membrane filtration processes and their associations with algal DOM characteristics. A broad understanding of algal DOM-driven membrane fouling can lead to breakthroughs in efficient membrane filtration processes to treat algal bloom water sources.

Impact of seasonality and anthropogenic impoundments on dissolved organic matter dynamics in the Klamath River (Oregon/California, USA)

AbstractRivers play a major role in the transport and processing of dissolved organic matter (DOM). Disturbances that impact DOM dynamics, such as river impoundments and flow regulation, have consequences for biogeochemical cycling and aquatic ecosystems. In this study we examined how river impoundments and hydrologic regulation impact DOM quantity and quality by tracking spatial and seasonal patterns of DOM in a large, regulated river (Klamath River, USA). Dissolved organic carbon (DOC) concentrations decreased downstream and longitudinal patterns in DOC load varied by season. Export of DOM (as DOC) was largely driven by river flow, while DOM composition was strongly influenced by impoundments. Seasonal algal blooms in upstream lentic reaches provided a steady source of algal DOM that was processed in downstream reaches. DOM at upstream sites had an average spectral slope ratio (SR) &gt; 1, indicating algal‐derived material, but decreased downstream to an average SR &lt; 1, more indicative of terrestrial‐derived material. The increasingly terrestrial nature of DOM exported from reservoirs likely reflects degraded algal material that becomes increasingly more recalcitrant with distance from upstream source and additional processing. As a result, DOM delivered to free‐flowing river reaches below impoundments was less variable in composition. Downstream of impoundments, tributary influences resulted in increasing contributions of terrestrial DOM from the surrounding watershed. Removal of the four lower dams on the Klamath River is scheduled to proceed in the next decade. These results suggest that management should consider the role of impoundments on altering DOM dynamics, particularly in the context of dam removal.

Molecular-level changes of dissolved organic matter along the Amazon River-to-ocean continuum

Coastal oceans link terrestrial and marine carbon cycles. Yet, carbon sources and sinks in these biomes remain poorly understood. Here, we explore the dynamics of dissolved organic matter (DOM) along the Amazon River-to-ocean continuum from the lower mainstem at Óbidos to the open ocean of the western tropical North Atlantic. We molecularly characterized DOM via ultrahigh-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), determined DOM stable carbon isotopes, and interpreted the data in the context of bacterial abundance and production, phytoplankton biomass and composition. Multivariate analysis revealed that the DOM molecular variability in the plume was mainly influenced by the input of terrigenous DOM. Incubation experiments with water from close to the river mouth showed that photo- and bio-degradation preferentially removed 13C-depleted and 13C-enriched terrigenous DOM, respectively. However, there was no significant quantitative change in the total amount of dissolved organic carbon (DOC) over five days. This result suggests that most of the reactive DOM had already been bio-degraded upstream within the river and that photo-degradation was diminished in the turbid plume close to the river mouth. Terrigenous DOM therefore appeared to be relatively non-reactive nearshore. In the less turbid offshore plume, enhanced light penetration stimulated growth of phytoplankton and increased bacterial production. Although marine DOM compounds became relatively enriched, bulk DOC concentrations were 9 to 30% below levels expected from conservative mixing of river and ocean endmembers suggesting that quantitative removal of terrigenous DOM was not compensated by marine DOM production. We propose that removal of terrigenous DOM in the outer plume may be enhanced by (i) bio-degradation primed by reactive algal DOM, (ii) photo-degradation, which may further break down DOM into more bio-available forms, and possibly (iii) sorption of DOM to sinking particles.

Critical evaluation of spectroscopic indices for organic matter source tracing via end member mixing analysis based on two contrasting sources

Despite the wide use of absorption and fluorescence spectroscopy for tracking the sources of dissolved organic matter (DOM), there are limited studies on evaluating their source discrimination capabilities at variable solution chemistry (pH, NaCl, Ca2+, and DOM concentration). For this study, we compared the applicability of several well-known spectroscopic indices via end member mixing analysis based on two contrasting DOM sources (Suwannee River fulvic acid and an algal DOM). The absorption coefficients and the intensities of fluorescent components from parallel factor analysis (PARAFAC) showed linear relationships with increasing algal carbon fraction in the mixture of the two DOMs. In contrast, although they still behaved conservatively, spectral ratio indices such as spectral slopes, ratios of PARAFAC components, humification index, and fluorescence index changed in nonlinear patterns with the mixing ratios. The indices based on PARAFAC results exhibited strong discrimination capabilities, as indicated by high susceptibility to the changes in DOM sources relative to the analytical precision. While variable NaCl concentrations had limited effects, most fluorescence indices were considerably affected by other solution chemistry such as pH, Ca2+, and DOM level. Our study demonstrated that the applicability of the source discrimination indices should be critically examined especially in the environments with notable changes in the solution chemistry. The solution chemistry effects could be minimized by adjusting samples to a constant condition prior to the measurements or otherwise the effects should be fully taken into account in interpreting the field observations.

Limnology of the Green Lakes Valley: phytoplankton ecology and dissolved organic matter biogeochemistry at a long-term ecological research site

ABSTRACTBackground: Surface waters are the lowest points in the landscape, and therefore serve as excellent integrators and indicators of changes taking place in the surrounding terrestrial and atmospheric environment.Aims: Here we synthesise the findings of limnological studies conducted during the past 15 years in streams and lakes in the Green Lakes Valley, which is part of the Niwot Ridge Long Term Ecological Research (LTER) Site.Methods: The importance of these studies is discussed in the context of aquatic ecosystems as indicators, integrators, and regulators of environmental change. Specifically, investigations into climatic, hydrologic, and nutrient controls on present-day phytoplankton, and historical diatom, community composition in the alpine lake, Green Lake 4, are reviewed. In addition, studies of spatial and temporal patterns in dissolved organic matter (DOM) biogeochemistry and reactive transport modelling that have taken place in the Green Lakes Valley are highlighted.Results and conclusions: The findings of these studies identify specific shifts in algal community composition and DOM biogeochemistry that are indicative of changing environmental conditions and provide a framework for detecting future environmental change in the Green Lakes Valley and in other alpine watersheds. Moreover, the studies summarised here demonstrate the importance of long-term monitoring programmes such as the LTER programme.

Biodegradation of Dissolved Organic Matter (DOM) Released from Phytoplankton in Lake Biwa

The biodegradation study of algal dissolved organic matter (DOM) released from Microcystis aeruginosa, Staurastrum dorsidentiferum and Cryptomonas ovata was carried out. The algal DOM released from Microcystis aeruginosa and Staurastrum dorsidentiferum is relatively stable, while a part of the algal DOM released from Cryptomonas ovata may be easily decomposed. Before biodegradation, two fulvic-like fluorescence peaks (A and B) and a protein-like fluorescence peak (C) and another peak with E(x)/E(m) values of 320 - 330/390 nm (peak D) were observed in the algal DOM released from three kinds of phytoplankton. The fulvic-like fluorophores may be refractory regardless of the kinds of phytoplankton, while protein-like fluorophores released from Microcystis aeruginosa and Staurastrum dorsidentiferum may be relatively refractory and those from Cryptomonas ovata may be unstable. Peak D in the surface water of Lake Biwa may be attributed to low-molecular-weight substances produced during cultivation and/or biodegradation of several kinds of phytoplankton. The ratios of the fluorescence intensities (RFI/DOC) of peak A to peak B in algal DOM (< 1.0) were lower than those in soil Dando FA (1.8). On the other hand, no relationships between peak A and peak C were observed for three kinds of phytoplankton.

Characterization of binding site heterogeneity for copper within dissolved organic matter fractions using two-dimensional correlation fluorescence spectroscopy

The heterogeneity of copper binding characteristics for dissolved organic matter (DOM) fractions was investigated based on the fluorescence quenching of the synchronous fluorescence spectra upon the addition of copper and two-dimensional correlation spectroscopy (2D-COS). Hydrophobic acid (HoA) and hydrophilic (Hi) fractions of two different DOM (algal and leaf litter DOM) were used for this study. For both DOM, fluorescence quenching occurred at a wider range of wavelengths for the HoA fractions compared to the Hi fractions. The combined information of the synchronous and asynchronous maps derived from 2D-COS provided a clear picture of the heterogeneous distribution of the copper binding sites within each DOM fraction, which was not readily recognized by a simple comparison of the changes in the synchronous fluorescence spectra upon the addition of copper. For the algal DOM, higher stability constants were exhibited for the HoA versus the Hi fractions. The logarithms of the stability constants ranged from 4.8 to 6.1 and from 4.5 to 5.0 for the HoA and the Hi fractions of the algal DOM, respectively, depending on the associated wavelength and the fitted models. In contrast, no distinctive difference in the binding characteristics was found between the two fractions of the leaf litter DOM. This suggests that influences of the structural and chemical properties of DOM on copper binding may differ for DOM from different sources. The relative difference of the calculated stability constants within the DOM fractions were consistent with the sequential orders interpreted from the asynchronous 2D-COS. It is expected that 2D-COS will be widely applied to other DOM studies requiring detailed information on the heterogeneous nature and subsequent effects under a range of environmental conditions.

Characterization of Fluorophores Released from Three Kinds of Lake Phytoplankton Using Gel Chromatography and Fluorescence Spectrophotometry

Three kinds of phytoplankton were cultivated, and the contribution of dissolved organic matter (DOM) released from the phytoplankton was examined to clarify the cause of organic pollution of Lake Biwa. Microcystis aeruginosa, Staurastrum dorcidentiferum, and Cryptomonas ovata were evaluated with regard to cultivation. A significant peak (M(w): <3000 Da) was mainly detected in the algal DOM released from plankton during cultivation by gel chromatography with a fluorescence detector (E(x) = 340 nm, E(m) = 435 nm). Since this peak corresponds to a peak with lower molecular weight in three peaks detected in the surface water of Lake Biwa, it can be concluded that the algal DOM released from the plankton during cultivation makes a considerable contribution to the refractory organic matter in Lake Biwa. Three fluorescence maxima were observed in the cultivation of three kinds of phytoplankton: two fulvic-like fluorescence peaks (A and B) and a protein-like fluorescence peak (C). These peaks became larger as their cell counts of plankton increased. As for the fractionations of algal DOM using DAX-8, the ratio of hydrophilic DOM is fairly high in DOM produced by three kinds of phytoplankton. The order of the amount of algal DOM per cell volume during cultivation was Cryptomonas ovata > Microcystis aeruginosa > Staurastrum dorcidentiferum. These results suggest that the increase of the refractory organic matter in Lake Biwa may be attributed to a change of the predominant phytoplankton.

Characterization of Dissolved Organic Matter Released from Microcystis aeruginosa

The contribution of dissolved organic matter (DOM) released from phytoplankton (Microcystis aeruginosa) during cultivation and biodegradation was examined to clarify the causes of the organic pollution of Lake Biwa. Two peaks, peak 2 (retention time (RT) = 32 min) and peak 3 (RT = 35 min), were detected in the algal DOM released from Microcystis aeruginosa during cultivation and biodegradation by gel chromatography with a fluorescence detector (Ex = 340 nm, Em = 435 nm). As these peaks correspond with the peaks detected in the surface water of Lake Biwa, one can conclude that the algal DOM released from Microcystis aeruginosa during cultivation and biodegradation makes a considerable contribution to the refractory organic matter in Lake Biwa. Three fluorescence maxima were observed in the cultivation of Microcystis aeruginosa: a fulvic-like fluorescence peak (peak A) with Ex/Em values of 320/430 nm, a protein-like fluorescence peak (peak C) with Ex/Em values of 280/360 nm, and another peak with Ex/Em values of 240/370 nm. The fluorescence material of peak C has a larger MW than that of peak A. The algal-derived DOM from Microcystis aeruginosa has similar fluorescence to fulvic acid of soil origin but exhibits mainly hydrophilic characteristics. In the biodegradation of Microcystis aeruginosa, a fulvic-like fluorescence peak (peak B) with Ex/Em values of 250/440 nm and a peak with Ex/Em values of 320/380 nm were observed.

ＨＰＬＣ‐ＰＡＤ法を用いた糖類の高感度分析法への応用と湖水及び藻類由来溶存有機物の糖類組成

We determined the monosaccharide composition of dissolved organic matter (DOM) to evaluate the origin of DOM in Lake Kasumigaura. We applied high-performance liquid chromatography coupled with pulsed amperometric detection (HPLC-PAD) for the analysis of monosaccharides. We collected water samples from Lake Kasumigaura in 2004 and prepared samples from culture medium used for growing blue-green algae that are typically found in Lake Kasumigaura. The dissolved total saccharides (DTS) content of the lake water ranged from 1.8 to 3.0 μM. The DTS content of the DOM from lake water ranged from 3 to 6%. The monosaccharide composition in the lake water was uniform all year round. The main monosaccharides were fucose, rhamnose, arabinose, galactose, glucose, mannose, xylose and ribose. The algae released a large amount of DTS during the stationary phase. The concentration and composition of the released DTS differed substantially among the algal species. The released DTS was 43.2 to 126 μM. Glucose was the most predominant among the monosaccharides of the DTS. The DTS content of the algal DOM ranged from 11 to 33% depending on the type of algae. The monosaccharide composition was very different between the lake-water-derived and algal-derived DOMs.