Humic-like Fluorescent Dissolved Organic Matter Research Articles

Photochemical reactivity of dissolved organic carbon in subarctic lakes along a color gradient

ABSTRACT Lake–atmosphere carbon exchanges can be significantly affected by photochemical dissolved organic matter (DOM) mineralization. However, our understanding of how increasing allochthonous organic carbon input affects the photoreactivity of DOM per unit of absorbed incoming light is incomplete. Here, we measured the absorption of ultraviolet (UV) light and subsequent photochemical DOM decay in 148 lakes within the subarctic region of Abisko, Sweden. These lakes range from brown-water lakes with allochthonous input from mires to tundra clear-water lakes with relatively more autochthonous input. We used fluorescence excitation–emission matrix analysis to assess the DOM chemical composition to determine how increasing colored DOM (CDOM) affects photomineralization. We found that the photo decay rates in absolute values were positively correlated to CDOM. However, the photo decay per unit of absorbed light energy did not increase with increasing CDOM; rather, it showed a weak decreasing trend. Fluorescence analyses helped explain these patterns; humic-like fluorescent DOM, presumably of terrestrial origin, was associated with high absolute photo decay rates, but not generally with higher photoreactivity per unit of absorbed light energy than other types of DOM. The results suggest that even though increasing inputs of terrestrial substances lead to a higher abundance of photodegradable materials, CO2 emissions do not necessarily increase in lakes where browning limits the ability of light to penetrate deeper water.

Estimation of net accumulation and removal of fluorescent dissolved organic matter in different Baltic Sea water masses

This study aimed to detect non-conservative processes that affect the distribution of fluorescent dissolved organic matter (FDOM) in the Baltic Sea. An extensive data set comprised of 408 FDOM data, optical and physical profiles, and the development of a water masses balance model allowed us to ascertain the sources of mixing anomalies. These were seen as second-order deviations in the FDOM distribution as a function of salinity in three layers: surface water, Baltic Sea Winter Water, and deep water. The difference between modeled and measured FDOM values at three different excitation/emission wavelengths allowed to show the strength of non-conservative processes, such as photochemical and microbial decomposition (negative residual values) or extracellular release of dissolved organic matter from phytoplankton, heterotrophic uptake and release from anoxic sediments (positive residual values). Humic-like FDOM fractions displayed positive residuals in all seasons for intermediate and deep layers and negative residuals in surface waters. Largest accumulation rates of humic-like fractions were reached in the Gulf of Gdańsk during summer in intermediate and deep layers, while the greatest removal in surface waters was observed during spring in the Bornholm and Gotland Basins and during summer in the Gulf of Gdańsk, probably due to photodegradation. Positive residuals of the protein-like fraction were observed at the surface in summer and autumn in the Gulf of Gdańsk, probably linked to the abundance of phytoplankton and also due to the low molecular weight by-products of photodegradation of humic-like components. Spatial transects revealed an increase in humic-like residuals with depth and a strong correlation with apparent oxygen utilization, increasing with higher fluorescence and exhibiting an asymptotic trend. A relationship was found between the protein-like fractions and phytoplankton biomass proxies. A generalized concept for FDOM cycling in the Baltic Sea was proposed, highlighting photobleaching as the dominant non-linear process determining the efficiency of humic-like FDOM removal. The protein-like component was found to be more efficiently taken up by aerobic prokaryotes at the surface. Microbial utilization and reworking of organic matter, release from sediments, and a decade-long stagnation of bottom water masses, all contribute to the observed accumulation of FDOM in mesohaline deep waters below the permanent pycnocline in the Baltic Sea.

Distribution, characteristics and fate of fluorescent dissolved organic matter (FDOM) in the Bay of Bengal

The Bay of Bengal (BoB) is the largest sink to retain discharges from major rivers and the Sundarbans Mangrove Forest in Bangladesh and upholds significant ecological and resource diversity. This study aims to characterize, and identify sources, spatial dynamics, and the fate of the principal ecological web driver that is fluorescent dissolved organic matter (FDOM) in the BoB using advanced techniques of excitation-emission matrix (EEM) fluorescence spectroscopy and multivariate parallel factor (PARAFAC) analyses. The identified four protein-, two humic- and one detergent-like FDOM components mostly showed higher abundance in the shallow water than deep unlike a protein-like component. Such exceptional protein-like component was identified to form colloidal structure under elevated salinity in deep water. Autochthonous humic-like FDOM originated from primary production and water temperature counteracted microbial polymerization in shallow and deep water, respectively. The annual mass deposition indicated the influx of anthropogenic pollutants from both terrestrial and internal marine systems.

Distributions of humic substances in an estuarine region (Otsuchi Bay, Japan) determined using electrochemical and optical methods

Humic substances are major components of the dissolved organic carbon pool in aquatic environments that can bind to trace metals like copper and iron as organic ligands. The unique chromophoric and fluorescence properties of humic substances enabled measurements using conventional optical methods but recently a new electrochemical method using cathodic stripping voltammetry has emerged. In this study, we employed both methods to measure humic substances and elucidate their distribution patterns in Otsuchi Bay in Japan. The electroactive humic substances (eHS) detected using the electrochemical method were higher in the rivers (range 0.24 to 4.3 mg L−1) than in the coastal bay (range 0.08 to 0.69 mg L−1). Both methods revealed significantly higher humic concentrations in the surrounding rivers than in Otsuchi Bay, indicating that riverine sources are an important source of humic substances to Otsuchi Bay, consistent with previous observations in riverine systems globally. eHS correlated well with optical indices of dissolved organic matter (DOM) including humic and marine humic-like fluorescent DOM and chromophoric DOM. Furthermore, comparison with data from the literature suggests that about 20% of the weaker Cu-binding organic ligand pool in Otsuchi Bay may consist of eHS. As Cu-binding organic ligands, eHS may be important in buffering temporal or seasonal increases in Cu fluxes in estuarine regions, with possible implications for nutrient bioavailability and toxicity for primary producers.

Land use impact on the levels of fluorescent dissolved organic matter, phytoplankton and zooplankton in urban lakes

Urban lakes are vulnerable ecosystems, sensitive to environmental challenges, such as pollution, land use transformation and climate change. Closed and open lakes play relatively different roles in the accumulation, transport and transformation of pollutants and organic matter. Land use can influence the concentration of dissolved organic matter and the abundance of phytoplankton. Little is known about the relationship between fluorescent dissolved organic matter (FDOM), phytoplankton and zooplankton in open and closed lakes, relative to the impact of land use. This study aims to determine the connection between various types of land use and FDOM characteristics, as well as phytoplankton and zooplankton abundances in urban lakes. For the closed lakes samples, results showed positive associations between Bacillariophyceae and Testacea, and the protein-like fraction, while for open lakes, positive associations were found between these groups and the microbial humic-like fraction. Also, copepods and rotifers were associated with the humic-like fraction, in closed lakes, but in open lakes copepods correlated with the biological index, and rotifers with the humification index and fluorescence T/C ratio. Results suggested that discontinuous urban fabric, dump sites and abandoned lands decreased the abundance of protein-like fraction and phytoplankton. However, lakes with the highest quantity of protein-like FDOM also had the highest coverage of continuous urban fabric around the lake. Green urban areas decreased the quantity of humic-like FDOM. No impact by land use type was observed on zooplankton groups, suggesting that zooplankton may be less vulnerable to land use. Our findings will contribute to an improved urban water management and to an effective control of FDOM and phytoplankton abundances in urban lakes.

Quantification of groundwater versus fish-farm sources of nutrients in the coastal water off Jeju Island, Korea, using fluorescent dissolved organic matter as a tracer

The concentrations of nutrients and dissolved organic matter (DOM) in the coastal waters off Jeju Island, Korea, are known to be influenced mainly by submarine groundwater discharge (SGD) and fish-farm effluents, in addition to the background open-ocean seawater from the Tsushima Current. However, the differentiation of the effect of fish-farm effluents from SGD is very challenging since most of the farms in this island utilize groundwater as a rearing water. Thus, in this study, we measured the concentrations of nutrients and fluorescent DOM (FDOM) in seawater, fresh groundwater (FGW), and farm water in two coastal areas off Jeju Island, in May and August 2021, in order to determine the effect of SGD versus fish-farm effluents. The results showed that humic-like FDOM (FDOMH) and NH4+ concentrations were greatly enriched owing to organic matter decomposition in the farm waters. We used FDOMH, as a tracer for the farm effluent. The end-member mixing model for FDOMH and salinity showed that FGW contributed about 73% of NO3− (avg. 17 ± 20 μM), whereas the farm effluent contributed about 95% of NH4+ (avg. 5.6 ± 4.1 μM) and 71% of FDOMH (avg. 0.86 ± 0.49 R.U.) in the coastal waters. Thus, our result shows that fish-farm effluents can be an important source of anthropogenic DOM and nutrients in coastal waters, where farms are being operated intensively.

Hypolimnetic deoxygenation enhanced production and export of recalcitrant dissolved organic matter in a large stratified reservoir

Global impoundment of river systems represents a major anthropogenic forcing to carbon cycling in reservoirs with seasonal thermal stratification. Currently, a quantitative and mechanistic understanding of how hypolimnetic deoxygenation in stratified reservoirs alters dissolved organic matter (DOM) cycling and lateral transport along the river continuum remains unresolved. Herein, we used optical and high-resolution mass spectrometric analyses to track seasonal and spatial compositional changes of DOM from a large, subtropical impounded river in southeast China. Aliphatic compounds were contributed by algal blooms to epilimnetic DOM during the spring/summer and by baseflow to the overall DOM pool during low-discharge periods. Deoxygenation-driven hypolimnetic mineralization enhanced in situ production of bio-refractory molecules and humic-like fluorescent DOM (FDOMH) by utilizing bio-labile DOM and settling biogenic particles during periods of stratification. Production efficiency of hypolimnetic FDOMH was 159–444% higher than that of the global dark ocean, and was strongly regulated by temperature and possibly substrate supply. The in situ production rate of hypolimnetic FDOMH was four to five orders-of-magnitude higher than the dark ocean, with much faster turnover rates in dark inland waters versus the dark ocean. Collectively, these findings indicate that the hypolimnion is a hotspot for microbial carbon transformations, and hence an important source and pool of refractory DOM in aquatic systems. The lateral FDOMH flux increased 10.8–32.1% due to hypolimnetic reservoir release during periods of stratification, highlighting the importance of incorporating hypolimnetic carbon transformations into models for carbon cycling of inland waters and the land-sea interface.

Does Nitrate Enrichment Accelerate Organic Matter Turnover in Subterranean Estuaries?

Due to the widespread pollution of coastal groundwaters with fertilizers, submarine groundwater discharge (SGD) is often thought to be a large dissolved inorganic nitrogen (DIN) source to the ocean. Whether this N is autochthonous or allochthonous to the subterranean estuary (STE), the availability of large quantities of DIN can nevertheless interact with the cycling of other elements, such as carbon (C). In previous studies, we documented the discharge of large quantities of freshwater and NO3– from the mouth of an STE into the Ria Formosa lagoon (SW Iberian Peninsula). For the period covered in this study (2009–2011), the same STE site was dominated by recirculating seawater due to a prolonged fall in piezometric head in the coupled coastal aquifers. Total SGD rates remained similarly high, peaking at 144 cm day–1 at the lower intertidal during fall. We observed a progressive increase of NO3– availability within the STE associated with the recovery of piezometric head inland. Interestingly, during this period, the highest SGD-derived dissolved organic C and DIN fluxes (112 ± 53 and 10 ± 3 mmol m–2 day–1, respectively) originated in the lower intertidal. NO3– enrichment in the STE influences the benthic reactivity of fluorescent dissolved organic matter (FDOM): when seawater recirculation drives STE dynamics, only small changes in the benthic distribution of recalcitrant humic-like FDOM are observed (from −2.57 ± 1.14 to 1.24 ± 0.19 10–3 R.U. “bulk” sediment h–1) in the absence of DIN. However, when DIN is available, these recalcitrant fractions of FDOM are actively generated (from 1.32 ± 0.15 to 11.56 ± 3.39 10–3 R.U. “bulk” sediment h–1), accompanied by the production of labile protein-like FDOM. The results agree with previous studies conducted with flow-through reactor experiments at the same site and suggest that DIN enrichment in the STE enhances the metabolic turnover of sedimentary organic matter up to the point of discharge to surface waters. DIN pollution of coastal aquifers may therefore promote a contraction of the residence time of particulate organic C within the STE, driving carbon from continental storage into the sea.

Fluorescent Dissolved Organic Matter (FDOM) in the East Sea (Japan Sea): Distributions, Sources, and Sinks

We measured the north–south transactional distributions of nutrients, dissolved organic carbon (DOC), and fluorescent dissolved organic matter (FDOM) in the East Sea (Japan Sea) in November 2019. The humic-like (C peak and M peak) and protein-like (T peak) components were identified using the parallel factor analysis model. The concentrations of C peak, M peak, and nutrients increased with depth, while T peak and DOC concentrations decreased with depth. However, unusually higher DOC concentrations were observed in the deep layer of some stations near the Ulleung Basin, relative to those in the other stations, perhaps by internal oceanic waves driven by a combination of the anti-cyclonic eddy and the unique bottom topography. The humic-like FDOM in the deep layer was found to be produced mainly by aerobic degradation of sinking organic matter in the water column and additionally by anaerobic processes in the sediments, based on its plot against apparent oxygen utilization. Although the concentrations of M peak were almost constant in the entire depth, C peak decreased gradually from 1000 m to the surface, suggesting relatively ineffective production of M peak in the deep ocean and/or more effective UV degradation of C peak in the surface layer. The labile portion of FDOM, T peak, was observed only in the euphotic layer, indicating its rapid removal before reaching the deep ocean. Our results observed in the East Sea, a miniature of the global ocean, provide new insights into the production and removal mechanisms regarding the FDOM distributions in the ocean.

Characterizing the origins of dissolved organic carbon in coastal seawater using stable carbon isotope and light absorption characteristics

Abstract. In order to determine the origins of dissolved organic matter (DOM) occurring in the seawater of Sihwa Lake, we measured the stable carbon isotope ratios of dissolved organic carbon (DOC-δ13C) and the optical properties (absorbance and fluorescence) of DOM in two different seasons (March 2017 and September 2018). Sihwa Lake is enclosed by a dike along the western coast of South Korea, and the water is exchanged with the Yellow Sea twice a day through the sluice gates. The DOC concentrations were generally higher in lower-salinity waters in both periods, and excess of DOC was also observed in 2017 in high-salinity waters. Here, the excess DOC represents any DOC concentrations higher than those in the incoming open-ocean seawater. The excess DOC occurring in the lower-salinity waters originated mainly from marine sediments of tidal flats, based on the DOC-δ13C values (-20.7±1.2 ‰) and good correlations among the DOC, humic-like fluorescent DOM (FDOMH), and NH4+ concentrations. However, the origins of the excess DOC observed in 2017 appear to be from two different sources: one mainly from marine sources such as biological production based on the DOC-δ13C values (−19.1 ‰ to −20.5 ‰) and the other mainly from terrestrial sources by land–seawater interactions based on its depleted DOC-δ13C values (−21.5 ‰ to −27.8 ‰). This terrestrial DOM source observed in 2017 was likely associated with DOM on the reclaimed land, which experienced extended exposure to light and bacterial degradation as indicated by the higher spectral slope ratio (SR) of light absorbance and no concurrent increases in the FDOMH and NH4+ concentrations. Our study demonstrates that the combination of these biogeochemical tools can be a powerful tracer of DOM sources and characteristics in coastal environments.

Widespread distribution of allochthonous fluorescent dissolved organic matter in the intermediate water of the North Pacific

Visible wavelength fluorescent dissolved organic matter (FDOM), usually defined as humic-like FDOM, plays important roles in marine carbon and iron cycles as biorefractory dissolved organic matter and organic ligands, respectively. The major fractions of FDOM in the open ocean have been considered to be of marine origin (autochthonous) according to linear relationships between FDOM and apparent oxygen utilization (AOU) in the mesopelagic (200–1000 m) and bathypelagic (>1000 m) layers. Recently, Yamashita et al. (2020) quantified allochthonous FDOM from the positive deviation of the general FDOM–AOU relationship in the bathypelagic layer and found that allochthonous FDOM derived from the Sea of Okhotsk was conservatively transported to the western North Pacific through the circulation of intermediate water, including North Pacific Intermediate Water (NPIW). However, the contribution of allochthonous FDOM from the Bering Sea, the other source region of NPIW, has not been evaluated. Here, we determined the distributions of allochthonous FDOM in the entire North Pacific, including the Sea of Okhotsk and the Bering Sea, and the spatial distribution of allochthonous FDOM in the density range of NPIW for the entire North Pacific. We found that the major source region of allochthonous FDOM in NPIW was the Sea of Okhotsk but not the Bering Sea, although the water mass contributing to the lower part of NPIW is known to be mainly derived from the Bering Sea. Such different contributions of allochthonous FDOM from the marginal seas are likely due to a lack of expansion of the dense shelf water, which forms at coastal polynya and interacts with shelf sediments with a strong tidal current, to the basin region of the Bering Sea. We also demonstrated that allochthonous FDOM derived from the shelf sediments of the Sea of Okhotsk was conservatively distributed to the wide area of the North Pacific through the circulation of intermediate water, particularly the upper part of NPIW. Furthermore, the negative deviations of the FDOM-AOU relationship in the bathypelagic layer were evident for other water masses, such as Antarctic Intermediate Water (AAIW), suggesting that FDOM can help determine the spatiotemporal distribution of NPIW and its mixing with other water masses, such as AAIW.

Experimental Analysis of Diurnal Variations in Humic-Like Fluorescent Dissolved Organic Matter in Surface Seawater

Humic-like fluorescent dissolved organic matter (FDOM) have been widely used as tracers for bio-refractory dissolved organic matter to understand its dynamics in the oceans. Vertical distributions of humic-like FDOM are controlled by microbial production in the ocean interiors and photobleaching in surface layers. Although humic-like FDOM is expected to be actively produced in surface layers with high bacterial activity, its production in surface seawater is not well understood. To examine the diurnal variations in humic-like FDOM due to microbial production and photobleaching in surface seawater, we conducted seven experiments from night to day using surface seawater in the subtropical Pacific and coastal regions. Parallel factor analysis determined that FDOM in the incubated seawater was composed of three components: two types of humic-like FDOM and a protein-like FDOM. The fluorescence intensity of humic-like FDOM increased to 104.0 ± 2.5% of the initial intensity during the night and decreased to 101.2 ± 2.5% under sunlight exposure during the day. Conversely, its intensity significantly increased to 114.0 ± 2.7% under dark conditions during the day. The turnover rates of humic-like FDOM by the increase and decrease in its intensity were estimated to be 0.14 and 0.11 d–1, respectively. These comparable turnover rates indicated that the production and photobleaching of humic-like FDOM were almost in equilibrium in the surface layer, with a low level of humic-like FDOM. Linear correlations between the intensity of humic-like FDOM and concentrations of dissolved oxygen in all experiments under dark conditions indicated that humic-like FDOM were produced as the by-products of microbial respiration processes in the surface seawater. Using global bacterial respiration rates, the net production rate of humic-like FDOM in the global photic layer was estimated as 4.2–5.5 x 1017 R.U. yr–1, contributing to 75% of its production in the entire ocean.

Evaluation of the Production of Dissolved Organic Matter by Three Marine Bacterial Strains.

A large part of marine dissolved organic matter (DOM) is considered to be recalcitrant DOM (RDOM) produced by marine bacteria. However, it is still unclear whether differences in bacterial species and/or physiology control the efficiency of RDOM production. Here, batch culture experiments with glucose as the sole carbon source were carried out using three model marine bacterial strains, namely, Alteromonas macleodii (Alt), Vibrio splendidus (Vib), and Phaeobacter gallaeciensis (Pha). Dissolved organic carbon (DOC) concentrations drastically decreased during the exponential growth phases of these bacteria due to the consumption of glucose. The efficiency of bacterial DOC production at the end of incubation was largely different among the strains and was higher for Vib (20%) than for the other two strains (Alt, 4%; Pha, 6%). All strains produced fluorescent DOM (FDOM), including humic-like FDOM which is considered as recalcitrant component in the ocean, even though the composition of bacterial FDOM was also different among the strains. The efficiency of humic-like FDOM production during the exponential growth phase was different among the bacterial strains; that is, Pha produced humic-like FDOM efficiently compared with the other two species. The efficiency of humic-like FDOM production with mineralization of organic matter was lower during the exponential growth phase than during the stationary phase of Alt and Pha. Four processes for the production of bacterially derived recalcitrant humic-like FDOM are suggested from this study: (1) production during active growing (in all strains), (2) production with the reutilization of bacterial DOM (Alt), (3) production with the consumption of cellular materials (Pha), and (4) release from lysis (Vib). Our results suggest that bacterial species and physiology can regulate RDOM production and accumulation in the ocean.

Climatic, land cover, and anthropogenic controls on dissolved organic matter quantity and quality from major alpine rivers across the Himalayan-Tibetan Plateau

Alpine rivers in mountainous regions are crucial not only for land-ocean transfer of chemical species and sediments, but also for water, food, and energy security. Here, we examined dissolved organic matter (DOM) from the major alpine waters on the Tibetan Plateau. Our results revealed a decreasing trend of DOM quantity juxtaposed to an increasing trend of aromaticity from the northern to southern plateau. This is potentially caused by a general decreasing gradient of dust load combined with an increasing gradient of precipitation and vegetation from the NW to SE plateau. Furthermore, most proglacial streams and smaller tributaries were found to be relatively dominated by tyrosine-like fluorescent DOM from glaciers. In contrast, most main stems of rivers and tributaries within larger catchment basins were more controlled by humic-like fluorescent DOM from terrestrial origins. Condensed aromatics accounts for 14–21% of molecular formulas for riverine DOM, much higher than the world's average of ~11%, which indicated anthropogenic black soot pollution. In addition, there is a higher level of DOM amount in the monsoon season than in winter, and DOM characteristics varied more widely (dissolved organic carbon concentration: 0.2-37 mg-C L−1, Fluorescence Index: 1.2-1.8) on the Tibetan Plateau in comparison to other global alpine watersheds. This suggests heterogeneous land cover, anthropogenic, and climatic factors at play, which is reflected in DOM quantity and quality, over the highest plateau on Earth.

Biogeochemical alteration and fluxes of dissolved organic matter and nutrients in coastal bays

We measured dissolved organic carbon (DOC), δ13C-DOC, fluorescent dissolved organic matter (FDOM), dissolved inorganic and organic nitrogen (DIN; DON), dissolved inorganic phosphate (DIP), and radium isotopes (223Ra, 224Ra, and 226Ra) in three different bays: Gwangyang Bay (GB), Suyoung Bay (SB), and Ulsan Bay (UB), Korea. The water residence times based on Ra isotopes were approximately 15 (±7) for GB and 1–3 days for SB and UB. UB and SB showed clear two (terrestrial and marine) endmember mixing trends for DOC, DIN, and DIP. In addition, significant “excess” DOC (10–50% of outer bay) was observed for SB under depleted nutrient conditions. GB, which had the longest water-residence time, showed depleted DIN and DIP, with large “excess” DOC (40–60% of the outer bay) and DON (10–40% of the outer bay) concentrations. The excess DOC observed in SB and GB was found to be marine in origin, although there was a slight influence of terrestrial DOC in the low-salinity waters of SB based on δ13C-DOC values. Terrestrial humic-like FDOM was conservatively mixed in the three bays. The net fluxes of these components, estimated using the water residence times, suggest that GB is a significant source of DOM (DOC, DON, and humic FDOM) but a sink of DIN and DIP. SB and UB are the sources of inorganic nutrients as well as DOM to the open ocean. Therefore, our study reveals that the residence time of coastal embayment play an important role in the biogeochemical production and alteration of nutrients and DOM.

Factors controlling the distributions of dissolved organic matter in the East China Sea during summer

To determine the distribution of dissolved organic matter (DOM) in the East China Sea (ECS) during the summer, we measured the dissolved organic carbon (DOC) and nitrogen (DON), fluorescent dissolved organic matter (FDOM), and chlorophyll a (Chl. a) in the upper 100-m layer of this region during July and September 2015. The DOC (r2 = 0.72 and 0.78 in July and September, respectively) and DON (r2 = 0.43 and 0.33) were significantly correlated with salinity, suggesting that the river is the primary origin of DOM. However, we found that at a DOC “pulse” under a salinity ranging from 24 to 35, the extrapolating DOC values (304 ± 11 μM) were twice higher than those with a salinity of close to 0, as found in a previous study. The excess DOC concentration seemed to be attributed to the microbial metabolism during transport from the estuary based on the good relationships between DOC and marine humic-like FDOM (r2 = 0.42 and 0.47), as well as the fluorescence, humification, and biological indexes, but showed no correlation with Chl. a. Thus, the results of our study indicate that microbial activities can be a significant factor controlling the distribution of DOM in the ECS during summer.

Conditions of nutrients and dissolved organic matter for the outbreaks of Paralytic Shellfish Poisoning (PSP) in Jinhae Bay, Korea

We measured the concentrations of nutrients, fluorescent dissolved organic matter (FDOM), and photosynthetic pigments in seawater during the springs of 2018 and 2019 in Jinhae Bay, Korea. The samplings were carried out during the severe and weak outbreaks of paralytic shellfish poisoning (PSP) in April 2018 and March 2019, respectively. The additional sampling campaigns were carried out before and after the PSP outbreak for the comparison. During the severe PSP outbreak, lower salinities, higher organic and total nutrients, and higher humic-like FDOM were observed. Although the environmental condition of April 2018 is favorable for the growth of dinoflagellates, the lowest peridinin (dinoflagellate index) and highest fucoxanthin (diatom index) concentrations were observed amongst all sampling periods. Thus, our results suggest that PSP could be more effectively produced by dinoflagellates in the course of the ecological shift by interspecific competition under the environmental condition favorable for dinoflagellates.

Coupling Between Carbon and Nitrogen Metabolic Processes Mediated by Coastal Microbes in Synechococcus-Derived Organic Matter Addition Incubations.

Phytoplankton are major contributors to labile organic matter in the upper ocean. Diverse heterotrophic bacteria successively metabolize these labile compounds and drive elemental biogeochemical cycling. We investigated the bioavailability of Synechococcus-derived organic matter (SOM) by estuarine and coastal microbes during 180-day dark incubations. Variations in organic carbon, inorganic nutrients, fluorescent dissolved organic matter (FDOM), and total/active microbial communities were monitored. The entire incubations could be partitioned into three phases (labeled I, II, and III) based on the total organic carbon (TOC) consumption rates of 6.38–7.01, 0.53–0.64, and 0.10–0.13 μmol C L–1 day–1, respectively. This corresponded with accumulation processes of NH4+, NO2–, and NO3–, respectively. One tryptophan-like (C1) and three humic-like (C2, C3, and C4) FDOM components were identified. The intensity variation of C1 followed bacterial growth activities, and C2, C3, and C4 displayed labile, semi-labile, and refractory DOM characteristics, respectively. Alphaproteobacteria, Gammaproteobacteria, Bacteroidetes, and Actinobacteria dominated the quickly consumed process of SOM (phase I) coupled with a substantial amount of NH4+ generation. Thaumarchaeota became an abundant population with the highest activities in phase II, especially in the free-living size-fraction, and these organisms could perform chemoautotroph processes through the ammonia oxidation. Microbial populations frequently found in the dark ocean, even the deep sea, became abundant during phase III, in which Nitrospinae/Nitrospirae obtained energy through nitrite oxidation. Our results shed light on the transformation of different biological availability of organic carbon by coastal microorganisms which coupled with the regeneration of different form of inorganic nitrogen.

Evaluation of carbon mineralization and structural alterations of organic carbon in high-moor peat soils during incubation

The quantity and quality of soil organic matter (SOM) in the wetlands and peatlands are important for evaluating of the effects of environmental changes. This study’s aim was to evaluate the change in the chemical properties of SOM and dissolved organic matter (DOM) during a constant temperature incubation of high-moor peat soil under two types of vegetation. Incubation of high-moor peat soils collected from marsh vegetation and dwarf bamboo was conducted for 108 days at each temperature of 25 °C and 35 °C. The chemical properties of alkaline extract and DOM in soil samples during incubation were analyzed by tetramethylammonium hydroxide thermochemolysis-gas chromatography-mass spectrometry (TMAH-GC/MS) and fluorescence analysis. The cumulative CO2 emission from peat under dwarf bamboo was higher than that of peat under marsh vegetation. During incubation at 35 °C, plant and microbial residues in DOM extracted from dwarf bamboo soil were increased significantly at the early stages of culture. On the other hand, the components of DOM in the marsh vegetation soil sample did not significantly change between incubation at each temperature. The fluorescence spectra showed that protein-like fluorescent DOM contained in dwarf bamboo soil is consumed by microorganisms, which promotes leaching of humic-like fluorescent DOM and carbon mineralization during the incubation period at a higher temperature. Compared with marsh vegetation soil, the DOM in dwarf bamboo soil is susceptible to temperature rises and can be a larger source of CO2 emissions. This study shows that evaluation of DOM properties in soil could be useful to assess the effect of climate change on soil environment.

Contrasting bacterial and archaeal distributions reflecting different geochemical processes in a sediment core from the Pearl River Estuary

Microbial community structure and metabolic activities have profound impacts on biogeochemical processes in marine sediments. Functional bacteria such as nitrate- and sulfate-reducing bacteria respond to redox gradients by coupling specific reactions amenable to relevant energy metabolisms. However, similar functional patterns have not been observed for sedimentary archaea (except for anaerobic methanotrophs and methanogens). We coupled taxonomic composition with comprehensive geochemical species to investigate the participation of distinct bacteria and archaea in sedimentary geochemical cycles in a sediment core (300 cm) from Pearl River Estuary (PRE). Geochemical properties (NO3−, dissolved Mn and Fe, SO42+, NH4+; dissolved inorganic carbon (DIC), δ13CDIC, dissolved organic carbon (DOC), total organic carbon (TOC), δ13CTOC, and fluorescent dissolved organic matter (FDOM)) exhibited strong depth variability of different trends. Bacterial 16S rRNA- and dsrB gene abundance decreased sharply with depth while archaeal and bathyarchaeotal 16S rRNA gene copies were relatively constant. This resulted in an increase in relative abundance of archaea from surface (11.6%) to bottom (42.8%). Network analysis showed that bacterial groups of Desulfobacterales, Syntrophobacterales and Gammaproteobacteria were significantly (P < 0.0001) associated with SO42− and dissolved Mn while archaeal groups of Bathyarchaeota, Group C3 and Marine Benthic Group D (MBGD) showed close positive correlations (P < 0.0001) with NH4+, δ13CTOC values and humic-like FDOM. Our study suggested that these bacterial groups dominated in redox processes relevant to sulfate or metal oxides, while the archaeal groups are more like to degrade recalcitrant organic compounds in anaerobic sediments.