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Identifying drivers of the molecular composition of dissolved organic matter (DOM) is essential to understand the global carbon cycle, but an unambiguous interpretation of observed patterns is challenging due to the presence of confounding factors that affect the DOM composition. Here, we show, by combining ultrahigh-resolution mass spectrometry and nuclear magnetic resonance spectroscopy, that the DOM molecular composition varies considerably among 43 lakes in East Antarctica that are isolated from terrestrial inputs and human influence. The DOM composition in these lakes is primarily driven by differences in the degree of photodegradation, sulfurization, and pH. Remarkable molecular beta-diversity of DOM was found that rivals the dissimilarity between DOM of rivers and the deep ocean, which was driven by environmental dissimilarity rather than the spatial distance. Our results emphasize that the extensive molecular diversity of DOM can arise even in one of the most pristine and organic matter source-limited environments on Earth, but at the same time the DOM composition is predictable by environmental variables and the lakes’ ecological history.

The stability of black soil carbon in the deep layers of Japanese volcanic ash soil (i.e., buried A horizons) is often explained by its unique chemical (molecular structure) and physical (associate...

The maximum ammonia oxidation potential (AOP) of a topsoil in Langhovde, East Antarctica was 22.1±2.4‍ ‍ng N g-1 dry soil h-1 (2‍ ‍mM ammonium, 10°C, n=3). This topsoil exhibited twin AOP peaks (1 and 2‍ ‍mM ammonium) at 10°C, but not at 20°C. Six and ten operational taxonomic units (OTUs) were identified for ammonia-oxidizing bacteria (AOB) and archaea (AOA) amoA, respectively. AOB were classified into Nitrosospira; the two dominant OTUs corresponded to the Mount Everest cluster. AOA were classified into three clusters; Nitrososphaera and Nitrosocosmicus were the two dominant clusters.

To clarify the effects of crab burrows on variation in sediment CO2 flux in mangrove forest, we measured the traits of crab burrows (density and entrance area size) and the CO2 flux rate from sediment surfaces, in areas with and without burrows, in a subtropical mangrove forest on Ishigaki Island, southwestern Japan. Burrow density and entrance area showed significant differences among seasons (warm, middle, and cool) and mangrove zones (upper-, middle-, and downstream), which may have depended on crab phenology, life cycle, and species composition. The sediment CO2 flux rate was significantly higher at plots with crab burrows (B+) than at those without burrows (B−) in each zone and season. However, standardized sediment CO2 flux rate by burrow surface area at B+ plots did not differ significantly from that at B− plots. In addition, there were no significant differences in sediment temperature and sediment water content between the two types of plots. Moreover, the level of microbial respiration differed significantly between sediments collected from the deep part and those collected from either the ground surface part or burrow walls. These results suggest that crab burrows increase sediment CO2 flux from the mangrove forest floor by increasing the sediment–atmosphere interface area, thereby inducing a change to aerobic conditions in the sediments around burrows. Therefore, the seasonal and spatial effect of crab burrows on the forest floor should be considered when evaluating sediment CO2 flux and examining the role of the mangrove ecosystem as a carbon sink.

The response of soil organic matter (SOM) to global warming is a crucial subject. However, the temperature sensitivity of SOM turnover remains largely uncertain. Changes in the mineralization of na...

Dissolved organic matter (DOM) plays an important role in sustaining ecosystem services of mangrove forests through well-described biogeochemical and ecological functions. This study was conducted in the Fukido River (Ishigaki Island, Japan) to better understand the seasonal and episodic changes in DOM concentration and composition in a subtropical mangrove system. Water samples were collected seasonally along a headwater–mangrove–sea transect on 10 occasions from September 2014 through June 2016. DOM was fractionated based on hydrophobicity into two fractions (hydrophobic and hydrophilic) and also analyzed by excitation-emission matrix spectroscopy combined with parallel factor analysis (PARAFAC). Although seasonal changes in DOM concentration and composition were not observed, both hydrophobic and hydrophilic DOM concentrations and levels of the identified three PARAFAC components clearly increased during a typhoon event. It is suggested that episodic increases in freshwater input due to a typhoon caused enhanced leaching of DOM from mangrove litter and dissolution of mangrove soil organic matter (SOM), which was otherwise retained in the mangrove soil by salinity-induced aggregation. The aggregation–dissolution properties of SOM are crucial in determining the magnitude of DOM outwelling and possibly SOM accumulation rate by enhancing advective DOM exchanges. Future studies are needed to evaluate the size of the carbon pool and outwelling of DOM after classifying mangrove forests based on the hydrological regime that influences biogeochemical conditions in the forests. Regional Index Terms Japan, Okinawa, Ishigaki, Fukido.

Accelerated glacier melt and runoff may lead to inputs of labile dissolved organic matter (DOM) to downstream ecosystems and stimulate the associated biogeochemical processes. However, still little is known about glacial DOM composition and its downstream processing before entering the ocean, although the function of DOM in food webs and ecosystems largely depends on its composition. Here, we employ a set of molecular and optical techniques (UV-vis absorption and fluorescence spectroscopy, 1H NMR, and ultrahigh-resolution mass spectrometry) to elucidate the composition of DOM in Antarctic glacial streams and its downstream change. Glacial DOM consisted largely of a mixture of small microbial-derived biomolecules. 1H NMR analysis of bulk water revealed that these small molecules were processed downstream into more complex, structurally unrecognizable molecules. The extent of processing varied between streams. By applying multivariate statistical (compositional data) analysis of the DOM molecular data, we identified molecular compounds that were tightly associated and moved in parallel in the glacial streams. Lakes in the middle of the flow paths enhanced water residence time and allowed for both more DOM processing and production. In conclusion, downstream processing of glacial DOM is substantial in Antarctica and affects the amounts of biologically labile substrates that enter the ocean.

Despite the recognized organic carbon (OC) sequestration potential of mangrove forests, the ongoing climate change and anthropogenic disturbances pose a great threat to these ecosystems. However, we currently lack the ability to mechanically understand and predict the consequences of such impacts, primarily because mechanisms underlying OC stabilization in these ecosystems remain elusive. Research into OC stabilization has focused on terrestrial soils and marine sediments for decades, overlooking the vegetated coastal ecosystems including mangroves. In terrestrial soils and marine sediments, it is widely accepted that OC stabilization is the integrated consequence of OM’s inherent recalcitrance, physical protection, and interactions with minerals and metals. However, related discussion is rarely done in mangrove soils, and recalcitrance of roots and high net ecosystem production (high primary production and low heterotrophic respiration) have been considered as a primary OC sequestration mechanism in mangrove peat and mineral soils, respectively. This review presents the available information on the mechanisms underlying OC stabilization in mangrove soils and highlights research questions that warrant further investigation. Primary OC stabilization mechanisms differ between mangrove peat and mineral soils. In mangrove mineral soils, physico-chemical stabilization processes are important, yet grossly understudied OC stabilization mechanisms. In mangrove peat, recalcitrance of mangrove roots and the inhibition of phenoloxidase under the anoxic condition may be the primary OC stabilization mechanisms. Salinity-induced OC immobilization likely plays a role in both type of soils. Finally, this review argues that belowground production and allochthonous inputs in mangrove forests are likely underestimated. More studies are needed to constrain C budgets to explain the enigma that mangrove OC keeps accumulating despite much higher decomposition (especially by large lateral exports) than previously considered.

The significance of aquatic lateral carbon (C) export in mangrove ecosystems highlights the extensive contribution of aquatic pathways to the net ecosystem carbon budget. However, few studies have investigated lateral fluxes of dissolved organic carbon (DOC) and inorganic carbon (DIC), partly due to methodological difficulty. Therefore, we evaluated area-based lateral C fluxes in a small mangrove estuary that only had one exit for water exchange to the coast. We sampled water from the mouth of the creek and integrated discharge and consecutive concentration of mangrove-derived C (&Delta, C). Then, we estimated the area-normalized C fluxes based on the inundated mangrove area. DIC and DOC concentrations at the river mouth increased during ebb tide during both summer and winter. We quantified the &Delta, C in the estuary using a two-component conservative mixing model of freshwater and seawater. DIC and DOC proportions of &Delta, C concentrations at the river mouth during ebb tide was between 34% and 56% in the winter and 26% and 42% in the summer, respectively. DIC and DOC fluxes from the estuary were estimated to be 1.36 g C m&minus, 2 d&minus, 1 and 0.20 g C m&minus, 1 in the winter and 3.35 g C m&minus, 1 and 0.86 g C m&minus, 1 in the summer, respectively. Based on our method, daily fluxes are mangrove area-based DIC and DOC lateral exports that can be directly incorporated into the mangrove carbon budget.

The organic-Fe association in Scottish freshwater rivers has received little attention compared with in the estuarine mixing zone. We collected 201 water samples from rivers and lakes in Scotland across different sampling years and seasons. Relationships among the hydrophobic (HPO) fraction of dissolved organic matter (DOM), specific UV absorbance (SUVA254), and dissolved metals (Al and Fe) were examined to better understand their co-transportation in Scottish waters. The average DOM, HPO fraction, Fe, and Al concentrations for all the samples co-varied and were lower during winter than during summer. There was a strong positive correlation between DOM and HPO fraction concentrations (R2 = 0.99, p

The characteristics of humus composition are important for understanding the mechanism of carbon storage in the Qinghai–Tibet Plateau. The aim of this study was to characterize the quality ...

An anion exchange resin, diethylaminoethyl (DEAE) Sepharose®, was utilized for the isolation of dissolved organic matter (DOM) from fresh waters as an alternative to the discontinued DEAE cellulose. We used the following two chemically distinct model DOM samples to determine the optimized adsorption conditions onto DEAE Sepharose: the International Humic Substances Society’s standard samples, Suwannee River Fulvic Acid (FA) and Pony Lake FA. The optimized conditions consisted of the following: a contact time of 1 h (with shaking), a resin dosage of 1 ml mgC−1, and a dissolved organic carbon (DOC) concentration range of 1–100 mgC l−1. In addition, we examined the distribution of the DOM fractions extracted with DEAE Sepharose and DAX-8 from Lake Biwa (Japan) and Scottish river DOM samples. The majority of DOM (70% and 65%) was extracted by both of the resins. As indicated by 1H NMR, the evapo-concentrate (bulk DOM), the DEAE Sepharose fraction and the DAX-8 fraction from the Scottish DOM sample had substantial similarity in their proton distributions, while those of a clear-colored, low DOC sample (Lake Biwa) showed different NMR spectra. These findings highlight a need to pay more attention to the extraction selectivity of resins for experimentally ‘challenging’ samples.

The variation in CO2 flux from the forest floor is important in understanding the role of mangrove forests as a carbon sink. To clarify the effects of soil temperature and tidal conditions on variation in CO2 flux, sediment–atmosphere CO2 fluxes were measured between June 2012 and May 2013. We used the closed chamber method for two plots, with a 0.5 m difference in elevation (B, high elevation; R-B, low elevation), in a mangrove forest in south-western Japan. CO2 fluxes were highest in the warm season and showed a weak positive correlation with soil temperature in both forests. Estimated monthly CO2 flux showed moderate seasonal variation in accordance with the exposure duration of the soil surface under tidal fluctuation. Additionally, measured CO2 flux and soil temperature were slightly higher in the R-B plot than the B plot, although estimated annual CO2 flux was higher in the B plot than the R-B plot due to different exposure durations. These results suggest that variation in the exposure duration of the forest floor, which changes seasonally and microgeographically, is important in evaluating the annual CO2 flux at a local scale and understanding the role of mangrove ecosystems as regulators of atmospheric CO2.

Uptake of six particle-reactive and/or redox-sensitive radionuclides (210Pb, 234Th, 7Be, 59Fe, 237Np and 233Pa) by 14 humic acids (HAs) was investigated in artificial groundwater under mildly acidic conditions (pH~5.5). In HA-groundwater slurry, Pb, Be, Fe and Pa bound strongly to particulate HA (>0.45 µm), supporting their application as tracers of soil erosion. Th bound strongly to the colloidal HA (3 kDa-0.45 µm) and as such, would not be a good candidate as a tracer for monitoring soil erosion. HAs likely reduced the oxidized neptunyl form (Np(V)O4+) to Np(IV) based on its enhanced particle-reactivity and Np uptake by particulate HAs, partially retarding the movement of anthropogenic 237Np in field polluted environments. Particulate/colloidal carbonyl/O-aryl (likely through hydroquinone/quinone) functionalities in the HA correlated to Np and Pa uptake, but only particulate O-aryl functionalities was responsible for Fe uptake. The carboxylate- and carbonyl/O-aryl-containing organic functionalities in the HA correlated strongly with Th uptake. In contrast, no significant correlations between organic parameters and Pb or Be uptake implied their predominance of uniform surface adsorption onto particles. This study provides novel insight into the binding of six radionuclides with different organic functionalities of three size fractions, as well as its possible impact on their application in the soil-tracing research.

Mangroves are increasingly recognized as an important component of regional and global carbon cycles especially for their high carbon storage capacity. Global estimation of mangrove soil organic carbon (SOC) storage requires detailed regional studies, but estimates of SOC data in deep soils are currently missing in many countries. Furthermore, little is explored on the molecular composition of mangrove SOC. Here, we assessed the SOC stock in a Trat mangrove forest (Thailand) by collecting deep soils (3.5 m) and analyzed the SOC composition for better understanding its potential sources and influencing factors. The Trat mangrove forest had four times higher SOC stock than has been considered for Thai mangrove forests, with the per-area SOC stock of nearly 1000 Mg C ha-1 which rivals that of Indo-Pacific mangrove forests. The SOC composition analyzed by C/N ratios and spectroscopic techniques differed by tree species and depth. Compositional data principal component analysis revealed that a biological factor (root abundance) had stronger influences than the soil texture (sand versus clay) on the abundance and composition of mangrove SOC. Although surface soil (~1 m) C density was largely controlled by the recent vegetation, deep soil C density reflected other historical processes. This study contributed to a refined estimate of Thailand mangrove SOC stock and revealed that factors influencing SOC abundance and composition differ by tree species and depth.

In order to assess how environmental factors are affecting the distribution and migration of radioiodine and plutonium that were emitted from the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident, we quantified iodine and (239,240)Pu concentration changes in soil samples with different land uses (urban, paddy, deciduous forest and coniferous forest), as well as iodine speciation in surface water and rainwater. Sampling locations were 53-63 km northwest of the FDNPP within a 75-km radius, in close proximity of each other. A ranking of the land uses by their surface soil (4 cm) stable (127)I concentrations was coniferous forestdeciduous foresturbanpaddy, and (239,240)Pu concentrations ranked as deciduous forestconiferous forestpaddy ≥ urban. Both were quite distinct from that of (134)Cs and (137)Cs: urbanconiferous forestdeciduous forestpaddy, indicating differences in their sources, deposition phases, and biogeochemical behavior in these soil systems. Although stable (127)I might not have fully equilibrated with Fukushima-derived (129)I, it likely still works as a proxy for the long-term fate of (129)I. Surficial soil (127)I content was well correlated to soil organic matter (SOM) content, regardless of land use type, suggesting that SOM might be an important factor affecting iodine biogeochemistry. Other soil chemical properties, such as Eh and pH, had strong correlations to soil (127)I content, but only within a given land use (e.g., within urban soils). Organic carbon (OC) concentrations and Eh were positively, and pH was negatively correlated to (127)I concentrations in surface water and rain samples. It is also noticeable that (127)I in the wet deposition was concentrated in both the deciduous and coniferous forest throughfall and stemfall water, respectively, comparing to the bulk rainwater. Further, both forest throughfall and stemflow water consisted exclusively of organo-iodine, suggesting all inorganic iodine in the original bulk deposition (∼ 28.6% of total iodine) have been completely converted to organo-iodine. Fukushima-derived (239,240)Pu was detectable at a distance ∼ 61 km away, NW of FDNPP. However, it is confined to the litter layer, even three years after the FDNPP accident-derived emissions. Plutonium-239,240 activities were significantly correlated with soil OC and nitrogen contents, indicating Pu may be associated with nitrogen-containing SOM, similar to what has been observed at other locations in the United States. Together, these finding suggest that natural organic matter (NOM) plays a key role in affecting the fate and transport of I and Pu and may warrant greater consideration for predicting long-term stewardship of contaminated areas and evaluating various remediation options in Japan.

A nonionic macroporous resin, Amberlite(®) XAD-8, or its substitute, Supelite™ DAX-8, is used when isolating or quantifying aquatic humic substances (AHS). However, the effect of salinity on the adsorption behavior of AHS onto the resin is yet to be confirmed, rendering the possibility of salinity-induced changes in the values of quantified amounts or characteristics of AHS obtained from a salty system. To verify the results of quantification and isolation of AHS using the resin in different salinity systems, the effect of salinity on such quantitative analyses of AHS has been examined. It has been concluded that the salinity effect is in general trivial and will not hinder comparison of results regardless of sample solution salinity.

Organic matter in marine sediment is mainly categorized into three fractions depending on degradability: labile, semi labile and refractory. The degradability of coastal marine sediments depends on the properties of the organic matter contained in the sediments. The purpose of this study was to quantify labile and refractory organic matter in coastal marine sediments with different characteristics collected from the Seto Inland Sea, and to discover the factors controlling the degradability of organic matter. Refractory organic matter content in sediments ranged from 4.7–21.4 mg g−1, a percent composition equivalent to 72–97% of TOC. In contrast, labile and semi-labile content were 0.1–1.4 mg g−1 and 0.1–2.3 mg g−1, respectively, a percent composition equivalent to 0.5–12.9% and 1.8–17.1% of TOC, respectively. Approximately 93% of refractory organic matter was categorized into humin. Organic matter originated from marine phytoplankton settled on the surface of sediments and changed to humin or a refractory organic matter. This study contributes to a better understanding of the organic matter degradation characteristics of coastal marine sediments and provides important parameters for estimating carbon budget and carbon cycling in coastal sea systems.

We investigated a series of long-term soil samples (1976–2015) collected from a paddy field that underwent a conversion of cropping systems from double cropping to single cropping in 1991, with consistently different fertilization treatments. The fertilization treatments include (i) chemical fertilizer, (ii) chemical fertilizer + rice straw, (iii) chemical fertilizer + cattle manure compost, and (iv) chemical fertilizer + rice straw + fused phosphate + calcium silicate. We extracted dissolved organic matter (DOM) from the soil samples and analyzed it for the concentration of humic substances as well as for optical properties using ultraviolet-visible and excitation-emission matrix (EEM) spectroscopy. Different fertilization treatments did not significantly (P > 0.05) affect DOM and humic substance concentrations, while the soil total carbon (TC) content and DOM concentration consistently increased in the double cropping system and decreased in the single cropping system. The DOM/TC ratio, which is an indicator of the proportion of the labile fraction in TC pool, also showed a similar pattern. These results indicate that cropping systems had a larger effect on DOM concentration than the fertilization treatments. Five fluorescent components identified by parallel factor analysis of EEMs (three humic-like and two protein-like components) showed significant differences in the relative abundances under the different fertilization treatments. The manure compost application resulted in a higher tyrosine-like component relative abundance than the other chemical fertilizer applications. Overall, fertilization affected the DOM composition, while the cropping systems impacted both the concentration and spectroscopic property of paddy soil DOM.

The Ninth Symposium on Polar Science/Ordinary sessions: [OB] Polar biology, Wed. 5 Dec. / 2F Auditorium, National Institute of Polar Research

The Ninth Symposium on Polar Science/Ordinary sessions: [OB] Polar biology, Wed. 5 Dec. / Entrance Hall (1st floor), National Institute of Polar Research

Aquatic humic substances (AHS) have been intensively studied because they have a number of significant biogeochemical functions in water chemistry. In order to evaluate such functions, which are regulated by their quantity and quality, a quantitative understanding of AHS is necessary. This study shows the seasonal and vertical changes in the AHS concentration in Lake Biwa, the largest monomictic lake in Japan, over 4 years. The concentration of dissolved organic matter carbon (DOM-C) and AHS carbon (AHS-C) ranged from 0.85–1.6 mg C/l and 0.32–0.71 mg C/l, respectively. The percentages of AHS-C in the DOM-C ranged from 32% to 65%. At all depths, the DOM-C decreased and the AHS-C slightly increased or remained at nearly the same level, suggesting that the quality of the water may have changed mainly due to changes in the composition of the organic matter. Although the AHS-C to DOM-C ratio fluctuated and had no seasonal tendency, the average AHS-C ratio increased during the 4 year monitoring period. Because AHS can influence the entire food web starting with phytoplankton, unraveling the mechanism by which they accumulate remains an important goal.

Aquatic humic substances (AHSs) are major constituents of dissolved organic matter (DOM) in freshwater bodies. We performed quantitative analyses of AHSs in Japanese lake and wetland waters, focusing mainly on clear waters with low carbon contents, by using a resin isolation technique based on the carbon concentration in the AHSs of each sample. The proportion of AHS to DOM in the clear waters ranged from 38.4 to 64.1 %; these proportions are lower than those widely assumed for freshwater of 20–80 %. Moreover, the proportions of AHSs in DOM were not constant, so regression analysis cannot be used to predict the AHS concentration from the DOM concentration. Thus, AHS and DOM concentrations must be determined separately for each water sample.

To relate the isotopic composition of soil humic acids (HAs) to their source plants and their degree of humification (as indicated by the degree of darkening), as well as to soil type, we determined the stable isotope ratios for carbon (δ13C) and nitrogen (δ15N) of HAs extracted from 26 virgin soil samples (14 Andisols and 12 non-Andisols) and from leaf samples from ten C3 plants and seven C4 plants. The high absorption coefficients (estimated at 600 nm for 1% solutions), low hydrogen and nitrogen contents, low H/C ratios, low alkyl C and O-alkyl C contents, high O/H and C/N ratios, high aryl C contents, and high aromaticity of the Andisol HAs indicated a high degree of humification. The δ13C and δ15N values of the non-Andisol HAs increased along with the progression of humification of C3 plant-derived HAs. A significant correlation was observed between the δ15N and δ13C values of the non-Andisol HAs, but not for the Andisol HAs. Most of the Andisol HA δ13C values were higher than the highest non-Andisol HA δ13C value, and δ13C values were distributed between the δ13C values for the C3 and C4 plants. The contributions of C4 plant-derived carbon to total Andisol HA carbon (CRC4) are usually calculated on the assumption that the δ13C values are not substantially altered during the decomposition of plant materials and the formation of soil organic matter. However, if 13C enrichment occurs during organic matter decomposition, CRC4 will be overestimated. Therefore, we suggest a new method to calculate CRC4 values of Andisol HAs with a correction for isotopic fractionation associated with microbial degradation; the corrected CRC4 values ranged from − 5% to 58% and were approximately 22% lower than the uncorrected values.

Humic substances (HSs) are ubiquitous in various aquatic systems and play important roles in many geochemical processes. There is increasing evidence of the presence of HSs in deep groundwater; nevertheless, their ion binding properties are largely unknown. In this study we investigated the physicochemical and ion-binding properties of humic and fulvic acids extracted from deep sedimentary groundwater. The binding isotherms of protons (H(+)) and copper (Cu(2+)) were measured by potentiometry and fitted to the NICA-Donnan model, and the obtained parameters were compared with the generic parameters of the model, which are the average parameters for HSs from surface environments. The deep groundwater HSs were different from surface HSs, having high aliphaticities, high sulfur contents, and small molecular sizes. Their amounts of acidic functional groups were comparable to or slightly larger than those of surface HSs; however, the magnitude of Cu(2+) binding to the deep groundwater HSs was smaller. The NICA-Donnan model attributed this to the binding of Cu(2+) to chemically homogeneous low affinity sites, which presumably consist of carboxylic groups, via mono-dentate coordination at relatively low pH. The binding mode tended to shift to multi-dentate coordination with carboxylic groups and more heterogeneous alcoholic/phenolic groups at higher pH. X-ray absorption spectroscopy also revealed that Cu(2+) binds to O/N containing functional groups and to a lesser extent S containing functional groups as its divalent from. This study shows the particularity of the deep groundwater HSs in terms of their physicochemical and ion-binding properties, compared with surface HSs.

The Selenga River Basin (Mongolia and Russia) has suffered from heavy metal contamination by placer gold mining and urban activities in recent decades. The objectives of this study were to provide the first distribution data of dissolved organic matter (DOM) and humic substances (HS) in this data-scarce region, and to investigate their association with dissolved and colloidal metals. Two sampling campaigns were conducted in August of 2013 and 2014. A constant proportion of HS (%HS; coefficient of variation of 2%) was observed from the headwater of Tuul River to the end of the delta before Lake Baikal, spanning > 1000 km in distance. The relationships were determined as [HS] = 0.643 × [DOM] (R2 = 0.996, P

In order to examine the influence of the HA molecular composition on the partitioning of Pu, ten different kinds of humic acids (HAs) of contrasting chemical composition, collected and extracted from different soil types around the world were equilibrated with groundwater at low Pu concentrations (10–14 M). Under mildly acidic conditions (pH ∼ 5.5), 29 ± 24% of the HAs were released as colloidal organic matter (>3 kDa to 0.45 μm) and colloidal phases in terms of activity percentage and partitioning coefficient values (logKd). Based on molecular characterization of the HAs by solid state 13C nuclear magnetic resonance (NMR) and elemental analysis, Pu bindin...

The Selenga River contributes to 50% of the total inflow to Lake Baikal. Large tracts of the Selenga River Basin have been developed for industry, urbanization, mining, and agriculture, resulting in the release of suspended solids (SS) that affect downstream water quality and primary productivity. This study addressed SS as the main factor controlling pollutant transport and the primary indicator of land degradation in the Selenga River system. Tributaries with larger areas dedicated to agricultural use had higher SS concentrations, reaching 862 mg L−1, especially during the high runoff and intensive cultivation season. Although the large SS flux was detected in the main river, the small tributaries were distinguished by high SS concentrations. The high SS concentration corresponded to widespread development in the watershed. Watersheds with high potential of SS release are sensitive to intensive land uses. SS in the river system had a constant elemental composition consisting mainly of Fe and Al oxides, indicating that surface soils were major constituents of the tributary SS. Three minor heavy metals (Zn, Cu, and Cr) appeared in high concentrations downstream of urban and mining areas (two- to sixfold increases), indicating that these contaminants are carried by SS. At two tributary junctions, the concentration of contaminants on the SS decreased due to a large influx of SS with low heavy metal contents. Changes in electric conductivity and pH at downstream of tributary junctions enhanced the sedimentation of SS and the removal of contaminants from the water phase after aggregation of the SS. Land use changes in the tributary watersheds are major controlling factors for the fate of contaminants in the river system.

The molecular composition of soil organic matter (SOM) is important in understanding the elemental cycling of mangrove forests. The aim of the study was to investigate the SOM compositional changes with time in a mangrove mineral soil, which is rarely reported in the literature. A 1-m soil core was collected in the subtropical Fukido River mangrove forest (Okinawa, Japan) and separated into 25-cm sections. Humic acids (HA) and fulvic acids (FA) were extracted from the soil, and their relative abundance and chemical characteristics were analyzed by elemental analysis, stable carbon analysis, spectrophotometric measurement, liquid-state 13C nuclear magnetic resonance spectroscopy, and radiocarbon dating. HA exhibited a clear depth trend in the chemical characteristics, with lower H/C and N/C ratios, higher aromaticity, and higher phenolic 13C NMR peaks in the deeper sections. FA did not show such a clear depth trend, and was enriched in O-containing functional groups. A combination of radiocarbon dating and structural analysis of HA indicated that the rapid structural changes in HA (H/C and N/C) occurred during the first years–decades, followed by a gradual change over a time scale of several hundred (~500) years, and these structural changes were best explained by an increase in the relative phenolic C contents. These results show that mangrove SOM is a complex mixture of organic fractions with different biogeochemical reactivities.

The addition of biochar to the forest floor should facilitate efficient carbon sequestration. However, little is known about how biochar addition effects litter decomposition, which is related to carbon and nutrient dynamics in forest ecosystems. This study evaluated the effect of biochar addition on leaf litter decomposition in a forest ecosystem. To examine whether leaf litter decomposition was stimulated above and below biochar, litterbag experiments were carried out for about 3 years in a field site where biochar was added at the rate of 0, 5 and 10 t ha−¹ (C0, C5 and C10 plots) to the forest floor in a temperate oak forest, Japan. Biochar addition at C10 significantly enhanced litter decomposition below biochar for 2 years after treatment and above biochar for 1 year after treatment. Litter water content in biochar plots tended to increase under dry conditions. Biochar addition enhanced litter decomposition because of increased microbial activity with increased moisture content and accelerated the decomposition progress rather than changing the decomposition pattern. However, the carbon emission through changing leaf litter decomposition was small when compared with the carbon addition by biochar, indicating that biochar could be an effective material for carbon sequestration in forest ecosystems.

This study characterized dissolved organic matter (DOM) obtained from 47 lakes and 2 streams on ice-free areas at Lutzow-Holm Bay and Amundsen Bay in East Antarctica (n = 74), where few biogeochemical studies have been historically conducted. Samples were analyzed for basic water chemistry and by resin fractionation, UV–vis spectroscopy, and excitation emission matrix spectroscopy combined with parallel factor analysis (EEM-PARAFAC). Salinity of the samples ranged very broadly from fresh to hypersaline as a result of evaporative concentration. There was a clear positive correlation between log-salinity and the spectral slopes of DOM (S275–295), an indicator of photodegradation. Thus, we interpreted the correlation as a progression of photodegradation by prolonged water retention time. Of the identified seven PARAFAC components, three ubiquitous humic-like components decreased as photodegradation progressed, while a photorefractory UVC humic-like component increased its relative abundance. A non-humic component, traditionally defined as Peak N, did not show a trend depending on photodegradation, and its level was high in nutrient-rich lakes, presumably due to high in-situ production. We found robust correlations between the relative abundance of the ubiquitous humic-like components and that of the Peak N component in the bulk DOM irrespective of water types or ice-free areas. We proposed there were common processes that generated the ubiquitous humic-like components from the Peak N component in the Lutzow-Holm Bay and Amundsen Bay lakes and streams, such as bacterial processing of primary production-derived DOM and photochemical transformation of microbial DOM.

The dynamics of the polyaromatic structures of black humic acids (HAs), which are presumably derived from charred materials, are of significant interest for the global carbon cycle. However, the details of those dynamics are not yet well understood. We investigated differences in the degree of darkness (A600/C values), isotopic ratios (δ13C, δ15N, and Δ14C values), and 13C NMR spectra of size-separated black HAs extracted from Japanese volcanic ash soils in order to estimate the variations in the polyaromatic structures of black HAs during ca. 100 years of natural reforestation of Japanese pampas grassland. For several hundred years, all the study sites were managed similarly as grassland by burning. Subsequently, their management differed: at site G (Miscanthus sinensis: C4 plant), maintenance as of the time of this study was still performed by mowing, while at sites P (Pinus densiflora: C3 plant) and Q (Quercus crispula: C3 plant), maintenance was discontinued ca. 30 and 100 years ago, respectively. Thus, the sites range from grassland (site G) to coniferous forest (site P) to broad-leaved forest (site Q). For all HA size fractions at all sites, we found that δ13C values correlate positively with δ15N values, although the gradients are much lower for fractions of small to medium molecular size than for fractions of medium to large molecular size (denoted as lower-size and higher-size fractions, respectively). Overall, for the lower-size fractions, the contribution ratio of C4-plant-derived carbon shows a significant positive correlation with A600/C values and a negative correlation with Δ14C values, and their aromatic characteristics are greater than those of higher-size fractions within the same black HA. Furthermore, the relative proportion of lower-size fractions decreases with reforestation, especially from site P to Q. The δ13C values for all size fractions are similar for sites G and P, but are relatively low for site Q. The aryl C contents of the lower-size fractions are lower and the O-alkyl C contents and the aliphaticity (alkyl C:O-alkyl ratio) are clearly higher for sites P and Q than for site G. These results strongly suggest that stimulation of HA biodegradation might be achievable by continuous input of new plant litter during reforestation, even for lower-size HA polyaromatic structures, despite the fact that lower-size HAs biodegrade more slowly than higher-size HAs.

Characteristics of dissolved humic and fulvic acids in river waters were studied during 2003–2005 at 4 sites located in the headwaters and in the upper and lower Tokachi River, including a lowland tributary site. Fulvic acids from the headwaters to downstream areas have similar elemental composition and 13C-NMR spectra. Humic acids have similar characteristics in the Tokachi River system. In contrast, δ13C and Δ14C values exhibit a decreasing trend from the upper to the lower and tributary sites, although the headwater site has heavier δ13C and lower Δ14C values than the upper site. Fulvic acids had similar δ13C values from the upper to lower sites, but 123′ higher in Δ14C than those of humic acids on average. The δ13C and Δ14C values exhibited differences in downward variation for humic and fulvic acids. In the Tokachi River system, these results suggest that differences in transport pathways and residence times of humic and fulvic acids reflect differences in the δ13C and Δ14C values in a single river basin.

Although mangrove forests are one of the most well-known soil organic carbon (SOC) sinks, the mechanism underlying SOC accumulation is relatively unknown. High net primary production (NPP) along with the typical bottom-heavy biomass allocation and low soil respiration (SR) have been considered to be responsible for SOC accumulation. However, an emerging paradigm postulates that SR is severely underestimated because of the leakage of dissolved inorganic carbon (DIC) in groundwater. Here we propose a simple yet unique mechanism for SOC accumulation in mangrove soils. We conducted sequential extraction of water extractable organic matter (WEOM) from mangrove soils using ultrapure water and artificial seawater, respectively. A sharp increase in humic substances (HS) concentration was observed only in the case of ultrapure water, along with a decline in salinity. Extracted WEOM was colloidal, and ≤70% of it re-precipitated by the addition of artificial seawater. These results strongly suggest that HS is selectively flocculated and maintained in the mangrove soils because of high salinity. Because sea salts are a characteristic of any mangrove forest, high salinity may be one of mechanisms underlying SOC accumulation in mangrove soils.

Dissolved organic matter (DOM) strongly affects water quality within boreal forest ecosystems. However, how the quality of DOM itself changes spatially is not well understood. In this study, to examine how the diversity of DOM molecules varies in water moving through a boreal forest, the number of DOM molecules in different water samples, i.e., rainwater, throughfall, soil water, groundwater, and stream water was determined using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in Norway spruce and Scots pine stands in eastern Finland during May and June 2010. The number of molecular compounds identified by FT-ICR MS (molecular diversity) ranged from 865 to 2,194, revealing large DOM molecular diversity in the water samples. Additionally, some of the molecular compounds were shared between different water samples. The DOM molecular diversity linearly correlated with the number of low-biodegradable molecules, such as, lignin-like molecules (lignins), but not with dissolved organic carbon concentration. The number of lignins shared between different sampling locations was larger than that of any other biomolecular class. Our results suggest that low-biodegradable molecules, especially lignins, regulate spatial variations in DOM molecular diversity in boreal forests.

The binding of europium to dissolved humic substances (HSs), isolated from deep groundwater in the Horonobe area, Hokkaido, Japan, was evaluated by means of a three-dimensional fluorescence quenching technique. The Ryan and Weber model, extended by the charge neutralization model, was applied to the fluorescence quenching profiles to evaluate the conditional binding constants (K) at pH 5.0 and an ionic strength of 0.1. The K values for fulvic (FA) and humic acids (HA) in the Horonobe groundwater were comparable with each other regardless of the position of the fluorescence peaks. As compared with HSs from Lake Biwa, Aldrich, and Dando soil, the K values of the Horonobe groundwater HSs were the smallest, indicating that the Horonobe groundwater HSs have a lower affinity for the binding of europium compared to the HSs from surface environments. In addition, the results of the Aldrich-based comparison indicate that the Horonobe groundwater HSs have a lower binding affinity for trivalent lanthanides/actinides...

腐植酸（HA）は土壌有機物の主成分であり，植物生育はもとより金属元素や汚染物質の挙動，陸域生態系における炭素循環の要として研究されてきた．しかし，その化学構造は複雑多様であるうえに，生成起源物質や生成環境，生成時間によっても多様に変化する混合高分子物質であるために，十分な理解を得るにはほど遠い．そこで化学構造（分子構造）の決定ではなく，様々な分析手法によって得られた特性値をもとにしてHAを特徴付ける研究が行われてきた．著者らは13C NMR分析法と高速液体サイズ排除クロマトグラフィー（HPSEC）分析法を中心に，土壌HAの官能基炭素種の割合や相対平均分子量の情報を得てきた．本稿では両手法を土壌HAの分析に供するための最適化について触れた上で，様々な土壌HAに両手法を適用して得た化学構造特性の解析結果について解説する．また，両分析法で得られたデータ値を用いて多様な土壌HAを統計的に解析した例についても報告する．

A five-step sequential extraction procedure was developed for the partitioning of soil aluminum (Al) into five fractions: exchangeable, weakly organic bound, strongly organic bound, inorganic non-crystalline and crystalline. The results obtained by the sequential extraction method for Al were compared with those estimated from single extractions using identical operating conditions applied in each individual sequential fraction. The Al content in the extracts was measured by inductively coupled plasma optical emission spectrometry. The results indicated that the first four steps [potassium chloride (KCl), copper chloride (CuCl2), sodium pyrophosphate (Na4P2O7), acid ammonium oxalate ((NH4)2C2O4)] in the sequential procedure could be as effective as single extraction methods at estimating exchangeable Al, weakly organic bound Al, strongly organic bound Al, and non-crystalline Al. However, the crystalline Al content by sequential procedure was not in agreement with single extraction procedures. Further, the...

Seasonal characteristics of surface water fulvic acids (FAs) isolated from Japanese clear-water lakes were investigated. Qualitative changes in Lake Biwa and Lake Tankai FAs were determined and compared. Although the relative molecular weights determined by high-performance size-exclusion chromatography did not change remarkably, the elemental compositions, $$ E_{600}^{1\% } $$ values and 1H- and 13C-NMR spectral properties varied with the season. Both the H/C and N/C ratios for Lake Biwa FAs tended to be higher than those for Lake Tankai FAs, but O/C ratios were lower and decreased from spring to winter. The $$ E_{600}^{1\% } $$ values suggested that Lake Biwa FAs contained lower levels of unsaturated structures than Lake Tankai FAs, and the amounts of these structures increased in winter. The 1H and 13C NMR spectra indicated that Lake Biwa FAs are richer in saturated aliphatic chains, especially in spring. Overall, Lake Biwa FAs exhibited clearer seasonal changes in these characteristics than Lake Tankai FAs, suggesting that the seasonal variation may depend on changes in aquatic microbial activities.

Japanese volcanic ash soils have very thick and dark-colored A horizons with large amounts of black humic acids which are characterized by their extremely high aromatic structure and stabilities such as black carbon. Nevertheless, the disappearance of the melanic epipedon with a decreasing aromatic C and increasing alkyl C proportion of humic acids was observed in ecological succession for only over 20–30 years. To obtain further details regarding the chemical characteristics of this extraordinary changing process quantitatively, humus quantitative analysis, high-performance size exclusion chromatography (HPSEC), and liquid-state 13 C nuclear magnetic resonance ( 13 C NMR) analysis were performed, including those for fulvic acids at the surface of mineral soils (0–20 cm), in the grassland/forest ecotone of volcanic ash soil in Japan. In addition, to obtain information regarding the stability and origin of C which gives the key of changing mechanism of humus along with ecological succession, resistance to hydrogen peroxide oxidation (percent decolorization) and the stable isotope ratio of carbon (δ 13 C) were measured, respectively. The study sites were managed as grassland for several hundred years. Grassland at site 1 was still being maintained by mowing, while the maintenance of sites 2 and 3 was discontinued approximately 30 and more than 100 years ago, respectively. The dominant vegetative cover at site 1 was Miscanthus sinensis , that at site 2 was Pinus densiflora with an understory of Sasa spp., and the vegetation comprised mainly Quercus crispula with an understory of Sasa spp. at site 3.The concentration of humic acids decreased significantly from 60.4 to 47.4 C g kg − 1 in site 2, and then decreased continuously from 47.4 to 30.2 C g kg − 1 in site 3. These trends paralleled those of the total C and N content in soils, and C:N ratio increased along with succession from 11.1 to 17.0 to 19.2, respectively, supporting the hypothesis that changing vegetation from grassland to forest may promote N losses by plant uptake. Simultaneously, the concentration of fulvic acids and humin decreased only slightly throughout the series relative to humic acids. Physicochemical properties appeared to be affected by the succession especially in humic acids. In particular, the apparent content of aryl C moieties in the humic acids of site 2 decreased significantly from 30.0 to 14.9 C g kg − 1 , a level similar to site 3. Percent decolorization of humic acids corresponded to their aromaticity; site 1 had a lower value (55.3%) than those of sites 2 and 3 (65.8% and 66.4%, respectively). The δ 13 C values of humic acids ranged from − 19.6 to − 22.6‰; however, the values for sites 1 and 2 were exactly the same. The findings of this study point to the fact that humic acids, but not other humus fractions, significantly changed with decreasing aryl C moieties and stability over the first 30 years of conversion from managed grassland to forest. Furthermore, the disappearance of the melanic epipedon in the surface volcanic ash soil evidently contributed to the aryl C, but not alkyl C, content of humic acids, and there might be a difference in the major mechanism of chemical change of humic acids before 30 years and more than 100 years. At least for the first 30 years, it is strongly suggested that C losses and changes in chemical properties of humic acids could be due to extraordinary microbial degradation processes through accelerated plant N uptake along with ecological succession from grassland to forest in earlier stages.

Anthraquinones are widely present in plant kingdom, and clinically used as laxatives. Environmental contaminants, dioxins, develop various adverse effects through transformation of a cytosolic aryl hydrocarbon receptor (AhR). We investigated the effects of 18 anthraquinones and 7 of their structurally related compounds on transformation of the AhR estimated by its DNA-binding activity in the cell-free system. 1,4-Dihydroxyanthraquinone (quinizarin), 1,5-dihydroxyanthraquinone (anthrarufin), 1,8-dihydroxyanthraquinone (danthron), and 5-hydroxy-1,4-naphthoquinone (juglone) strongly suppressed DNA-binding activity of the AhR induced by 0.1 nM 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), with their IC(50) values around 1 muM. On the other hand, anthraquinone, 2,6-dihydroxyanthraquinone (anthraflavic acid), and 2-hydroxy-1,4-naphthalendione (lawsone) showed moderate effects. Quantitative structure-activity relationships analysis demonstrated that hydroxyl groups at C1 or C4 but not C3 position of anthraquinone structure are critical for the suppressive effects. In addition, all compounds except lawsone had no agonistic effect. The suppressive effects of anthraquinones in a cultured cell system were also confirmed. In human hepatoma HepG2 cells, chrysophanol, danthron, and rhein also suppressed the DNA-binding activity in a dose-dependent manner, although aloe-emodin showed a moderate effect. The findings of this study may be useful for the design of the novel antagonists of the AhR.

石炭灰の発生量が増加傾向にある現在，その有効利用が一層求められている。石炭灰のうちクリンカアッシュ(以下CA と称す)は，フライアッシュと比較して粒径が粗く飛散のおそれもないため，土壌の代替としての大量利用が期待されるが，利用に際してはホウ素過剰障害の可能性が示唆されている。本研究では，CA を主材料とする緑化基盤で緑化樹木のポット試験を行い，CA の緑化基盤としての有効性を検討した。緑化基盤材料には，CA，真砂土，ピートモス(以下PM と称す)を用い，CA 試験区(CA とPM を混合)をCA 95 ％区，CA 90 ％区，CA 80 ％区の3 区，対照として真砂土にPM を10％ 混合したものを設定し，樹木は，アラカシ，ウバメガシ，シャリンバイ，トベラ，マテバシイの5 種を用いて，約7 ケ月間のポット試験を行った。作製した緑化基盤の化学性，物理性は対照区と比較して有意な差はほとんど無かった。また，国内の法律に照らし合わせると，これらの材料の重金属類濃度は安全であった。緑化樹木の生育に関しては，5 樹種とも，樹高（H），幹直径（D）から表されるD2H の試験期間中の生長率および試験終了時の新鮮重に，試験区間で有意な差はみられなかった。また，CA 試験区の樹木葉中ホウ素含量は，シャリンバイ以外の4 樹種で対照区に対して高い傾向を示したが，生育障害は確認されず，他の金属類に関しても異常な値は認められなかった。これらのことから，本研究に用いたCA を緑化基盤として大量利用することは十分可能であると考えられるが，実際の利用の段階では，CA ごとの性質の違いを検討していく必要がある。

To find a certain relation between the composition of carbon functional groups of humic acids derived from liquid state 13C nuclear magnetic resonance (NMR) spectra acquired with inverse-gated decoupling (IGD), known as a quantitative pulse sequence, and that by solid-state 13C NMR with cross polarization/magic angle spinning (CPMAS) techniques, fifteen soil humic acid samples with a wide range of aromaticity were analyzed. Relationships between the proportions of humic acid carbon as alkyl, O-alkyl, and aromatic carbon assessed by the two methods could be regressed to y = ax (r = 0.932–0.956; P < 0.005), respectively. The contents of alkyl, O-alkyl, and aromatic carbon assessed by CPMAS method were larger than those found by IGD method. However, the differences between the two methods were small and exclusive regression to y = x was also significant (r = 0.775–0.941; P < 0.005). Aromaticity calculated from 13C CPMAS NMR data also did not differ significantly from those computed from 13C NMR spectra with IGD. These observations indicated the comparability of the relative content of carbon functional groups in humic acids except for carboxyl and carbonyl carbon.

To examine the effect of vegetation type and grassland management regimen on the distribution of humus-degrading microorganisms, populations of humic acid-degrading (HAD) bacteria and fungi at three Andosol sites were investigated using the dilution plate method. Each site had three different vegetation types (Eulalia grassland, bamboo grassland, and coniferous plantations). Among the six grassland sites, two were maintained by burning and the others by cutting. HAD microorganisms were found in all soil samples. Low densities and small percentages of HAD bacteria were detected with no significant differences in the number of bacteria found between different vegetation types and grasslands managed in different ways. In contrast, the densities and percentages of HAD fungi differed according to vegetation type and management regimen. Specifically, the percentages of HAD fungi were significantly higher for burned grasslands. At burned sites, the numbers and percentages of HAD bacteria remained at a consistently low level, and no distinct seasonal changes were observed. In contrast, marked seasonal fluctuations in HAD fungi were detected. The percentages of these fungi remained relatively high between April and December. These fluctuations are likely due to the effects of burning on soil microorganisms.

Chemical properties of hydrophobic acid (HoA) fractions in water-soluble organic matter in soil and water are concerned with its interactions with mineral soil surfaces and organic pollutants. In 2004 we examined the seasonal and vertical changes in chemical properties of the HoA fraction in a Cambisol profile and compared these properties with those in the HoA fraction of an adjacent stream (aquatic humic substances) in a temperate forested watershed using high performance size exclusion chromatography (HPSEC) and 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. The HoA fractions from Oi, Oe/Oa, A and B horizon soils in summer had lower O-alkyl C proportions than those recorded in samples in other seasons. The proportions of aromatic C in HoA fractions from A and B horizons were highest in summer. These seasonal variations were less significant than variations with soil depth. O-alkyl C proportions in HoA fractions decreased with increasing soil depth from the Oi to the A horizon. The H...