FUJITAKE Nobuhide | ![]() |
Graduate School of Agricultural Science / Department of Agrobioscience | |
Professor | |
Agricultural Chemistry |
May 2020 日本土壌肥料学会, 学会賞, 腐植物質の分析法,特徴付けおよび反応性に関する研究
Nov. 2017 日本腐植物質学会, 日本腐植物質学会第33回講演会優秀ポスター発表賞, 南極湖沼溶存有機物に光を当てる:光学的分析およびフミン物質定量
Japan society
Mar. 2017 日本生態学会, 第64回⽇日本⽣生態学会⼤大会ポスター賞, 亜熱帯マングローブ林林における粗⼤大有機物 の分解速度度と環境要因の関係
Japan society
Sep. 2016 日本土壌肥料学会, ポスター賞, チベット高原祁連(きれん)山脈における標高別土壌の有機物特性
Japan society
Sep. 2016 International Humic Substances Society, The Award for the Best Poster, Determination of aquatic humic substances in lakes and wetlands by the carbon concentration-based DAX-8 batch adsorption technique.
International society
Oct. 2014 独立行政法人 日本学術振興会, 平成26年度「科研費」審査員表彰, 平成26年度「科研費」審査員
有意義な審査意見を付し,公正・公平な審査に大きく貢献したためOthers
Feb. 2014 日本陸水学会近畿支部会, 日本陸水学会近畿支部会第25回研究発表会 優秀発表賞, 国内外の湖沼や河川における腐植物質含量~DAX-8 樹脂吸着法による〜
口頭発表において優秀な成績を収めたJapan society
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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.
{MDPI} {AG}, 11 Sep. 2020, Forests, 11 (9), 981 - 981, English[Refereed]
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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 (ΔC). 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 ΔC in the estuary using a two-component conservative mixing model of freshwater and seawater. DIC and DOC proportions of ΔC 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−2 d−1 and 0.20 g C m−2 d−1 in the winter and 3.35 g C m−2 d−1 and 0.86 g C m−2 d−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.
MDPI AG, Sep. 2020, Forests, 11 (10), 1041 - 1041[Refereed]
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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.
Elsevier BV, Sep. 2020, Marine Chemistry, 225, 103854 - 103854, English[Refereed]
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© 2020, © 2020 Japanese Society of Soil Science and Plant Nutrition. 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 (associated with short-range-order minerals) recalcitrance. However, the stability of black soil C in buried A horizons may be changed by labile C supply for soil microbes. Here, we hypothesized that the mineralization of black soil C in buried A horizons of Japanese volcanic ash soil could be easily accelerated by a supply of labile C (i.e., a priming effect; PE). To test our hypothesis, we investigated the direction and magnitude of the PE with a buried A horizon in Japan using 13C-labeled glucose (2.188 atom %) in a short-term (21 days) incubation study. We also investigated the effect of mineral nitrogen (N), which could contribute to microbial activity in this incubation study. We found that a positive PE occurred by glucose supply with (182%) or without (181%) mineral N input over the 21-day incubation, and its values were very similar to the PE ratios previously reported in other deep soils. The estimated mean residence time (MRT) of black soil C considering PE was clearly accelerated by glucose supply, regardless of mineral N input, compared with the initial soil MRT. These results strongly support our hypothesis that the mineralization rate of black soil C in buried A horizons is easily accelerated by a labile C supply, and it also demonstrates important implications for the effects of global warming on buried A horizons (e.g., increased root exudation, fine root biomass supply, and N deposition) in Japanese volcanic ash soils.
2020, Soil Science and Plant Nutrition[Refereed]
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© 2019, Coastal and Estuarine Research Federation. 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.
Jan. 2020, Estuaries and Coasts, 43 (1), 102 - 110, English[Refereed]
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© 2019 Elsevier Ltd 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.
Elsevier {BV}, Dec. 2019, Estuarine, Coastal and Shelf Science, 231, 106478[Refereed]
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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 (SUVA(254)), 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 (R-2=0.99, p<0.0001). A significant positive correlation was also found between the HPO fraction and Fe and Al concentrations. The regression slope indicating the overall relationships between the HPO fraction and Fe concentrations differed by as much as 12 times depending on both the sampling period and the river. These slope differences were not significantly determined by the chemical structures of DOM, SUVA(254), or Al and Cu concentrations. These results suggest that the Fe transport capacities vary among the Scottish rivers because of other factors such as seasonal effects (temperature and the level of water table) and a suspended solid concentration in the water column.
Springer, Mar. 2019, Limnology, 20 (2), 215 - 224, English[Refereed]
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An anion exchange resin, diethylaminoethyl (DEAE) Sepharose((R)), 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 1h (with shaking), a resin dosage of 1mlmgC(-1), and a dissolved organic carbon (DOC) concentration range of 1-100mgCl(-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 H-1 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.
Springer, Mar. 2019, Limnology, 20 (2), 153 - 162, English[Refereed]
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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.
Nature Publishing Group, 01 Dec. 2018, Scientific Reports, 8 (1), 4795, English[Refereed]
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<p>Sewage sludge is generated 2.26 million Mg annually in Japan, and its dealing is one of the social problems. This study aimed to promote the application of dried sewage sludge in farmlands for recycling purposes. We composted sludge and bamboo chips in the ratios of 5 : 5, 7 : 3, and 9 : 1. Characteristics of hot water extracts during composting were analyzed approximately every week until the end of composting process (41 days) by testing inhibition of germination of Japanese mustard spinach (<i>Brassica rapa</i> var. <i>perviridis</i>) and by chemical analyses such as those using UV-vis spectroscopy and those involving dissolved organic carbon measurement. The concentration of ammonia, which is one of the strongest odor sources, decreased by about 60% in the first 2 weeks of composting. The pH, electrical conductivity, and E2/E3 tended to decrease, whereas specific UV absorbance (SUVA<sub>254</sub>) tended to increase during composting, suggesting the progression of humification and maturation of composts. Although the 7 : 3 and 9 : 1 compost extracts demonstrated considerable germination inhibition in the early stages of composting, the inhibition was alleviated as maturation progressed to 28 days. Inhibition was not observed in the 5 : 5 compost extract, and heavy metals did not exceed the safety standard, so the compost did not exhibit harmful effects on crop growth or safety. We also performed three replicates of a field growth experiment using Tanbaguro black soybean (<i>Glycine max</i>) with and without addition of 50-day-old compost (5 : 5, 7 : 3, and 9 : 1). Results showed that addition of the composts significantly increased the main stem length and the number of pods (p<0.01). Soybean yield was the highest in the 9 : 1 compost addition group, although this difference was not significant. These results suggest that composting of dried sewage sludge and bamboo chips is effective in agricultural production as it recycles local resources, reduces odor, and does not inhibit germination.</p>
Corresponding, Japanese Society of Soil Science and Plant Nutrition, 14 Aug. 2018, Jpn. J. Soil Sci. Plant Nutr., 89 (4), 295 - 301[Refereed]
Humic substances (HS) are the primary constituents of dissolved organic matter (DOM) and play pivotal roles in aquatic systems. Optical indices of DOM, such as specific UV absorbance (SUVA254), the fluorescence index (FI) and biological index (BIX), have gained wide interest because of their ease of use. In this study, we explored the relationship between HS and the indices in the Trat River Basin (eastern Thailand) from headwaters to the river mouth through the distinct dry and rainy seasons to examine whether changes in index values reflect variability in the relative contribution of HS to DOM, or %HS. The results show that %HS and the indices did not exhibit significant linear relationships (FI and BIX, P > 0.05), or the relationships changed seasonally (SUVA254). However, analyzing the indices versus %HS did show clear DOM composition changes by season with more humic-like or terrestrial material in the rainy season. Relationships between DOM and dissolved iron (dFe) concentrations were also explored. Separating the relationships of DOM versus dFe into HS versus dFe and non-HS versus dFe provides us the opportunity to better understand which fraction contributes more to dFe mobilization. The results indicate stronger positive linear relationships between HS and dFe concentrations independent of river tributary. Overall, this study highlights the importance of quantifying HS for the study of DOM dynamics or compositional changes along a river transect as well as for DOM-induced iron mobilization.
Birkhauser Verlag AG, 01 Jul. 2018, Aquatic Sciences, 80 (3), English[Refereed]
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© 2018 Cambridge University Press. 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.
Cambridge University Press, Jun. 2018, Journal of Tropical Ecology, 34 (4), 268 - 275, English[Refereed]
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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 < 0.001), and this value (%HS = 64.3) is recommended as an input parameter for metal speciation modeling based on samples collected from the rivers. The DOM and metal (Al and Fe) concentrations in samples doubled through the Zaamar Goldfield mining area, but the influence was mitigated by mixing with the larger Orkhon River, which has better water quality. Metals were mainly present as colloids and had a strong positive correlation with DOM (Al r = 0.81, P < 0.01 Fe r = 0.61, P < 0.01), suggesting that DOM sustains colloidal Al and Fe in solution and they are co-transported in the Selenga River Basin. Land use changes affect water quality and metal speciation and therefore have major implications for the fate of metals.
Springer Verlag, 01 Apr. 2018, Environmental Science and Pollution Research, 25 (12), 11948 - 11957, English[Refereed]
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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 similar to 5.5), 29 +/- 24% of the HAs were released as colloidal organic matter (>3 kDa to <0.45 mu m), yet this HA fraction accounted for a vast majority of the bound Pu, 76 +/- 13% on average. In comparison, the particulate HA fraction bound only 8 +/- 4% on average of the added Pu. The truly dissolved Pu fraction was typically <1%. Pu binding was strongly and positively correlated with the concentrations of organic nitrogen in both particulate (>0.45 mu m) and colloidal phases in terms of activity percentage and partitioning coefficient values (logK(d)). Based on molecular characterization of the HAs by solid state C-13 nuclear magnetic resonance (NMR) and elemental analysis, Pu binding was correlated to the concentration of carboxylate functionalities and nitrogen groups in the particulate and colloidal phases. The much greater tendency of Pu to bind to colloidal HAs than to particulate HA has implications on whether NOM acts as a Pu source or sink during natural or man-induced episodic flooding.
AMER CHEMICAL SOC, Oct. 2017, ENVIRONMENTAL SCIENCE & TECHNOLOGY, 51 (20), 11742 - 11751, English[Refereed]
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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. (C), 2017 Published by Elsevier Ltd.
PERGAMON-ELSEVIER SCIENCE LTD, Jun. 2017, CHEMOSPHERE, 177, 51 - 55, English[Refereed]
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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 heavymetals (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.
SPRINGER, May 2017, ENVIRONMENTAL EARTH SCIENCES, 76 (9), 346 - 361, English[Refereed]
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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.
NATURE PUBLISHING GROUP, Feb. 2017, SCIENTIFIC REPORTS, 7, 42102, English[Refereed]
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Mangrove forests are tropical forests with carbon-rich soil. Dissolved organic matter (DOM) is important for investigating the mangrove carbon cycle and ecological roles because the forests connect the river tributaries with the coast via rivers running through them. The ecological functions and turnover rate of DOM depend on its composition. Therefore, we characterized the DOM of the Fukido River in a mangrove forest by analyzing the percentage of humic substances (%HS) in DOM. Water sampling from the headwaters to the sea revealed that %HS declined going toward the sea due to mixing with low-%HS seawater and the possible selective precipitation of HS into mangrove soil. The headwaters had a higher %HS than most clear water rivers and may be an important supply of HS for mangrove and coastal areas. The sequential extraction of water-extractable organic matter from mangrove soil (sampling depth: 0–25 cm) using ultrapure water indicated a significant increase in HS concentration along with a decline in salinity. These results suggest that high salinity is responsible for the selective accumulation of HS in mangrove soil, which can be a key to elucidating the mechanism of organic matter accumulation in mangrove soils.
Tohoku University, 2017, Japanese Journal of Ecology, 67 (2), 85 - 93, Japanese[Refereed]
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nonionic macroporous resin, Amberlite (R) XAD-8, or its substitute, Supelite (TM) 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. (C) 2015 Elsevier Ltd. All rights reserved.
PERGAMON-ELSEVIER SCIENCE LTD, Mar. 2016, CHEMOSPHERE, 146, 129 - 132, English[Refereed]
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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 Pu-239,Pu-240 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 I-127 concentrations was coniferous forest > deciduous forest > urban > paddy, and Pu-239,Pu-240 concentrations ranked as deciduous forest > coniferous forest > paddy > urban. Both were quite distinct from that of Cs-134 and Cs-137: urban > coniferous forest > deciduous forest > paddy, indicating differences in their sources, deposition phases, and biogeochemical behavior in these soil systems. Although stable I-127 might not have fully equilibrated with Fukushima-derived I-129, it likely still works as a proxy for the long-term fate of I-129. Surficial soil I-127 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 I-127 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 I-127 concentrations in surface water and rain samples. It is also noticeable that I-127 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 (similar to 28.6% of total iodine) have been completely converted to organo-iodine. Fukushima-derived Pu-239,Pu-240 was detectable at a distance similar to 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. (C) 2016 Elsevier Ltd. All rights reserved.
ELSEVIER SCI LTD, Mar. 2016, JOURNAL OF ENVIRONMENTAL RADIOACTIVITY, 153, 156 - 166, English[Refereed]
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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.
SPRINGER JAPAN KK, Jan. 2016, LIMNOLOGY, 17 (1), 1 - 6, English[Refereed]
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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 (Cu2+) 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 Cu2+ binding to the deep groundwater HSs was smaller. The NICA-Donnan model attributed this to the binding of Cu2+ 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 Cu2+ 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.
ROYAL SOC CHEMISTRY, 2015, ENVIRONMENTAL SCIENCE-PROCESSES & IMPACTS, 17 (8), 1386 - 1395, English[Refereed]
Scientific journal
Research institution
[Refereed]
International conference proceedings
[Refereed]
International conference proceedings
[Refereed][Invited]
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 (A(600)/ C values), isotopic ratios (delta C-13, delta N-15, and Delta C-14 values), and C-13 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 delta C-13 values correlate positively with delta N-15 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 A(600)/C values and a negative correlation with Delta C-14 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 delta C-13 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. (C) 2012 Elsevier Ltd. All rights reserved.
PERGAMON-ELSEVIER SCIENCE LTD, Feb. 2013, SOIL BIOLOGY & BIOCHEMISTRY, 57, 60 - 67, English[Refereed]
Scientific journal
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 C-13-NMR spectra. Humic acids have similar characteristics in the Tokachi River system. In contrast, delta C-13 and Delta C-14 values exhibit a decreasing trend from the upper to the lower and tributary sites, although the headwater site has heavier delta C-13 and lower Delta C-14 values than the upper site. Fulvic acids had similar delta C-13 values from the upper to lower sites, but 123 parts per thousand higher in Delta C-14 than those of humic acids on average. The delta C-13 and Delta C-14 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 delta C-13 and Delta C-14 values in a single river basin.
UNIV ARIZONA DEPT GEOSCIENCES, 2013, RADIOCARBON, 55 (2-3), 1007 - 1016, English[Refereed]
Scientific journal
We analyzed the physicochemical and spectroscopic properties of three charred plant fragments (CPF) that were isolated from three volcanic ash soils in Japan. Values of delta C-13 showed that the CPF originated from C-3 and C-4 plants. The contribution ratio of C-4 plants to the CPF was much higher in Soils 1 and 3 than in Soil 2. Values of delta N-15 of the CPF were higher in Soil 3 isolated from the deeper soil horizons. Light reflectance values suggested that part of the CPF experienced combustion temperatures higher than 400 degrees C in Soil 2 and less than 400 degrees C in the other soils, respectively. Atomic [H]/[C] and [O]/[C] ratios suggested that the CPF were subjected to weathering ( oxidative degradation and hydrolysis) in soil for a long period after burning. The degree of weathering was considered to be larger in Soils 1 and 3. Spectra of C-13-NMR of the CPF, except the area of alkyl-C, were similar. Infrared (IR) spectra of three CPF, except aliphatic C-H stretching, were also similar to each other. The X-ray diffraction patterns of the CPF in Soil 2 clearly revealed the presence of graphite-like structure. From these findings, it was assumed that the physicochemical and spectroscopic characteristics of the CPF were strongly influenced by the type of burnt vegetation.
LIPPINCOTT WILLIAMS & WILKINS, Dec. 2012, SOIL SCIENCE, 177 (12), 695 - 700, English[Refereed]
Scientific journal
[Refereed]
Scientific journal
Aquatic humic substances (AHSs) are major constituents of dissolved organic matter (DOM) in freshwater, where they perform a number of important ecological and geochemical functions, yet no method exists for quantifying all AHSs. We have developed a method for the quantitative analysis of AHSs based on their carbon concentration. Our approach includes: (1) the development of techniques for clear-water samples with low AHS concentrations, which normally complicate quantification; (2) avoiding carbon contamination in the laboratory; and (3) optimizing the AHS adsorption conditions.
JAPAN SOC ANALYTICAL CHEMISTRY, Oct. 2012, ANALYTICAL SCIENCES, 28 (10), 1017 - 1020, English[Refereed]
Scientific journal
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 pH5.0 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 compared with other groundwater HSs obtained from different aquifer. These findings demonstrate that the characteristics and origin of deep groundwater HSs needs to be taken into consideration assessing the effects of HSs on the speciation of radionuclides in deep groundwater in geological disposal systems.
TAYLOR & FRANCIS LTD, Aug. 2012, JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY, 49 (8), 804 - 815, English[Refereed]
Scientific journal
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 H-1- and C-13-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 H-1 and C-13 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.
SPRINGER TOKYO, Apr. 2012, LIMNOLOGY, 13 (1), 45 - 53, English[Refereed]
Scientific journal
Humic acids (HAs), the major components of organic matter in soils, play an important role in global carbon cycling and regulation of the mobility and fate of plant nutrients and organic and inorganic pollutants. Despite intensive research on soil HAs during the past 200 years, the chemical nature of HAs is not fully understood. Studies using a variety of spectroscopic techniques have led to major advances in understanding the chemical nature of HAs, but the macromolecule structure and chemical heterogeneity of HAs is a serious hindrance. Therefore, the characterization and grouping of HAs with various chemical natures has been studied. C-13 NMR analysis and high performance size exclusion chromatography (HPSEC) are the most powerful and popular tools in this study field. We here describe : (i) optimization of the HA measuring condition in both analyses, (ii) characterization of the chemical nature among HAs in various soil origins, and (iii) HA grouping by statistical analysis based on information data obtained by C-13 NMR and HPSEC analyses. Thirty-three of HAs from various soil origins were analyzed and, conclusively, they were classified clearly by their chemical nature.
JAPAN SOC ANALYTICAL CHEMISTRY, Apr. 2012, BUNSEKI KAGAKU, 61 (4), 287 - 298, Japanese[Refereed][Invited]
Scientific journal
Humic like substances (HULISs) extracted from atmospheric aerosols in Osaka city were analyzed by thermochemolysis with tetramethylammonium hydroxide (TMAH) pyrolysis GC/MS. Main components assigned on GC/MS chromatograms were fatty acid methyl esters, dicarboxylic acid dimethyl esters, and phenol derivatives. Compositions of the component of the HULISs were different from that of humic substances in soil and HULIS in standard urban aerosols (SRM 1648a), suggesting differences in origin and formation mechanisms from these substances.
JAPAN ASSOC AEROSOL SCI & TECHNOLOGY, 2012, 29TH SYMPOSIUM ON AEROSOL SCIENCE AND TECHNOLOGY, 2012, 159 - 160, Chinese[Refereed]
International conference proceedings
We investigated the optical absorption properties (A(400)/C and A(600)/C values), elemental composition, weight-averaged molecular weight (Mw), and liquid-state carbon-13 (C-13) nuclear magnetic resonance (NMR) spectroscopy of DAX-8 adsorbed fulvic acid fractions (DAX-8 FAs) in various soils (n = 36) to establish the general trends in their chemical characteristics. We also compared our results with those of humic acids (HAs) obtained from the same soils used in this study and other published data to discuss the differences between them. Our results clearly indicate that DAX-8 FAs with high carboxyl C content have small Mw and low hydrogen to carbon (H/C) ratio. In addition, DAX-8 FAs with high carbonyl C and alkyl C content have high A(400)/C values and H/C ratios, respectively. These results strongly suggest that DAX-8 FAs with high aliphatic chemical properties have low carboxyl C content, large Mw and high H/C ratio. There are significant differences in chemical characteristics among the various soil types in almost all data; e. g., DAX-8 FAs from Podzols showed significantly higher A(400)/C values, larger Mw, higher carbonyl C and O-aryl C content than those obtained from Andosols. However, these two C functional groups are relatively low values in the total C content among all soil types, suggesting that DAX-8 FAs may exhibit only small differences in chemical properties among the various soil types. The comparison with published data regarding soil HAs shows that DAX-8 FAs are characterized by smaller Mw; lower C, H, and nitrogen (N); higher oxygen (O) content; higher O/C; lower O/H ratios; higher carboxyl C content; and lower aryl C content in total C.
TAYLOR & FRANCIS LTD, 2012, SOIL SCIENCE AND PLANT NUTRITION, 58 (4), 404 - 415, English[Refereed]
Scientific journal
[Refereed]
Scientific journal
[Refereed]
Scientific journal
High performance size-exclusion chromatography (HPSEC) is useful for the molecular size separation of soil humic acids (HAs), but there is no method available for various HAs with different chemical properties. In this paper the authors propose a new preparative HPSEC method for various soil HAs. Three soil HAs with different chemical properties were fractionated by a Shodex OHpak SB-2004 HQ column with 10 mM sodium phosphate buffer (pH 7.0)/acetonitrile (3:1, v/v) as an eluent. The HAs eluted within a reasonable column range time (12-25 min) without peak tailing. Preparative HPSEC chromatograms of these HAs indicated that non-size-exclusion effects were suppressed. The separated fractions were analyzed by HPSEC to determine their apparent molecular weights. These decreased sequentially from fraction 1 to fraction 10, suggesting that the HAs had been separated by their molecular size. The size-separated fractions of the soil HA were mixed to compare them with unfractionated HA. The analytical HPSEC chromatogram of the mixed HA was almost identical to that of the unfractionated HA. It appears that the HAs do not adsorb specifically to the column during preparative HPSEC. Our preparative HPSEC method allows for rapid and reproducible separation of various soil HAs by molecular size. (C) 2011 Elsevier B.V. All rights reserved.
ELSEVIER SCIENCE BV, Sep. 2011, JOURNAL OF CHROMATOGRAPHY A, 1218 (37), 6448 - 6453, English[Refereed]
Scientific journal
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 (CuCl(2)), sodium pyrophosphate (Na(4)P(2)O(7)), acid ammonium oxalate ((NH(4))(2)C(2)O(4))] 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 sequential extractions resulted in more consistent estimates of the aluminum/silicon (Al/Si) molar ratio and allophane and crystalline Al contents than single extractions method. Results of X-ray diffraction on the soil samples confirm the presence of appreciable amounts of at least three types of crystalline minerals, including gibbsite, vermiculite or halloysite. Our result implies that the sequential method can be more reliable in estimating the various Al forms in Andisols.
WILEY-BLACKWELL, Aug. 2011, SOIL SCIENCE AND PLANT NUTRITION, 57 (4), 500 - 507, English[Refereed]
Scientific journal
This study reports carbon isotopic ratios (Delta(14)C and delta(13)C) of dissolved humic and fulvic acids in the Tokachi River system, northern Japan. These acids have a refractory feature and they represent the largest fraction of dissolved organic matter in aquatic environments. The acids were isolated using the XAD extraction method from river water samples collected at three sites (on the upper and lower Tokachi River, and from one of its tributaries) in June 2004 and 2005. delta(13)C values were -27.8 to -26.9 parts per thousand for humic and fulvic acids. On the other hand, the Delta(14)C values ranged from -247 to 126 parts per thousand and the average values were -170 +/- 79 parts per thousand for humic acid and -44 +/- 73 parts per thousand for fulvic acid. The difference was attributed to the residence time of fulvic acid in the watershed being shorter than that of humic acid. The large variation suggested that humic substances have a different pathway in each watershed environment.
OXFORD UNIV PRESS, Jul. 2011, RADIATION PROTECTION DOSIMETRY, 146 (1-3), 322 - 325, English[Refereed]
Scientific journal
大規模堆肥化処理方式の違いが牛ふん尿堆肥の腐植化に及ぼす影響を調べるために、堆積方式と撹拌方式により製造された堆肥から抽出された腐植物質の化学的および光学的特性を比較した。いずれの方式についても、堆肥化に伴うC/N比や易分解有機物量の減少、幼植物発芽試験における腐熟化の進行が認められた。一方、処理方式により、堆肥から抽出された腐植酸の光学的特性が著しく異なり、堆積方式では腐植酸の黒色化とカルボキシル基などの官能基構造の発達を伴う腐植化の進行が顕著であったのに対し、撹拌方式では堆肥化後も未熟でリグニン構造が残存した腐植酸であった。植物の生育に影響を及ぼす可能性がある動的な腐食物質を水抽出して比較したところ、堆積方式ではフルボ酸の増加と腐植化に伴う構造変化が認められたが、撹拌方式ではフルボ酸が減少した。処理方式が異なる堆肥の圃場還元においては、腐植化の違いを考慮した使い分けが必要である。
農業施設学会, 25 Jun. 2011, Journal of the Society of Agricultural Structures, Japan, 42 (1), 8 - 17, Japanese[Refereed]
Scientific journal
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 (delta(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 delta(13)C values of humic acids ranged from -19.6 to -22.6 parts per thousand: 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 adds could be due to extraordinary microbial degradation processes through accelerated plant N uptake along with ecological sccession from grassland to forest in earlier stages. (C) 2010 Elsevier B.V. All rights reserved.
ELSEVIER SCIENCE BV, Oct. 2010, GEODERMA, 159 (1-2), 122 - 130, English[Refereed]
Scientific journal
International conference proceedings
[Refereed]
International conference proceedings
[Refereed]
International conference proceedings
[Refereed]
International conference proceedings
Characteristics of aquatic fulvic acids (FAs) from 10 clear waters in Japan (around the temperate zone) were revealed by several analytical techniques high performance size exclusion chromatography (HPSEC), elemental analysis, liquid-state (13)C NMR spectroscopy, isotopic analyses (delta(13)C and delta(15)N), and compared with those of International Humic Substances Society (IHSS) standard samples including FAs from brown waters (Suwannee, Pony, and Nordic FAs). Generally clear-water FAs were different from brown-water FAs in chemical properties. Weight-average molecular weights (Mw) of the clear-water FAs were similar to each other, whereas their elemental compositions and carbon species distribution were different. The clear-water FAs all exhibited a high proportion of alkyl carbons, which may be attributed to microbial activity. delta(13)C and delta(15)N values of the FAs indicated that there would be a huge gap between origin and chemical structure of clear-water FA. Results of the chemical structural analyses described above were not always linked to those of the isotopic analyses (delta(13)C and delta(15)N). Multivariate statistical analysis, i.e. cluster and principal component analysis was applied to reveal differences or similarities in a more objective manner. The FAs were always classified into two clear-water groups and one brown-water group. Aryl-C and O-Alkyl-C contents were important for the grouping. We speculate that the grouping might depend on the differences of aquatic microbial activity caused by the differences of residence time of water. (C) 2010 Elsevier Ltd. All rights reserved.
PERGAMON-ELSEVIER SCIENCE LTD, Jul. 2010, WATER RESEARCH, 44 (13), 3837 - 3846, English[Refereed]
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[Refereed]
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[Refereed]
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Scientific journal
[Refereed][Invited]
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 mu M. 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. (C) 2008, The Society for Biotechnology. Japan. All rights reserved.
SOC BIOSCIENCE BIOENGINEERING JAPAN, Mar. 2009, JOURNAL OF BIOSCIENCE AND BIOENGINEERING, 107 (3), 296 - 300, English[Refereed]
Scientific journal
International conference proceedings
A deficiency of dietary fiber causes digestive tract diseases. In the present study, the effect of β-glucan purified from baker's yeast (BBG) on the rat cecum contents and fecal excretion was examined using cellulose (CE) as a negative control fiber. Rats were fed with AIN-93M-based diet containing BBG or CE at 1%, 3%, or 5%, or a nonfiber diet for 4 weeks. Cecal tissue weight was significantly increased by 5% BBG diet compared with 5% CE diet, whereas the pH of cecal content was significantly decreased. Short-chain fatty acid including acetate, propionate, and n-butyrate in the rat cecum was significantly increased by 5% BBG diet compared with 5% CE diet, indicating that increasing the content of short-chain fatty acids in the cecum decreased the pH of cecal content. In addition, the water content of feces was also significantly increased by 5% BBG diet compared with 5% CE diet. These results suggest that BBG promote cecal fermentation and retain water in the large-intestinal lumen. In conclusion, BBG prevents constipation by modulating intestinal functions and its effectiveness is greater than that of CE.
日本生物工学会, 2009, seibutsu-kogaku kaishi, 87 (4), 170 - 174, Japanese[Refereed]
Scientific journal
A deficiency of dietary fiber causes digestive tract diseases. In the present study, the effect of β-glucan purified from baker's yeast (BBG) on the rat cecum contents and fecal excretion was examined using cellulose (CE) as a negative control fiber. Rats were fed with AIN-93M-based diet containing BBG or CE at 1%, 3%, or 5%, or a nonfiber diet for 4 weeks. Cecal tissue weight was significantly increased by 5% BBG diet compared with 5% CE diet, whereas the pH of cecal content was significantly decreased. Short-chain fatty acid including acetate, propionate, and n-butyrate in the rat cecum was significantly increased by 5% BBG diet compared with 5% CE diet, indicating that increasing the content of short-chain fatty acids in the cecum decreased the pH of cecal content. In addition, the water content of feces was also significantly increased by 5% BBG diet compared with 5% CE diet. These results suggest that BBG promote cecal fermentation and retain water in the large-intestinal lumen. In conclusion, BBG prevents constipation by modulating intestinal functions and its effectiveness is greater than that of CE.
日本生物工学会, 2009, 生物工学会誌, 87 (4), 170 - 174, Japanese[Refereed]
Scientific journal
[Refereed]
Scientific journal
[Refereed]
Scientific journal
[Refereed]
International conference proceedings
[Refereed]
International conference proceedings
[Refereed]
International conference proceedings
To find a certain relation between the composition of carbon functional groups of humic acids derived from liquid state C-13 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 C-13 CPMAS NMR data also did not differ significantly from those computed from C-13 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. (C) 2008 Elsevier B.V. All rights reserved.
ELSEVIER SCIENCE BV, Jun. 2008, ANALYTICA CHIMICA ACTA, 618 (1), 110 - 115, English[Refereed]
Scientific journal
A method of high-performance size-exclusion chromatography (HPSEC) for a wide variety of soil humic acids (HAs) was developed. Two types of soil HAs (Cambisol and Andosol HAs), which have substantially different chemical properties, showed different effects of salt and organic solvent concentrations in the eluent on chromatograms. A Shodex OHpak SB-805 HQ column with 10 mM sodium phosphate buffer (pH 7.0) containing 25% of acetonitrile (v/v) was found to be applicable for different HAs, and showed high reproducibility and recovery (87.0 - 94.5%). The Cambisol HA was fractionated into five fractions using an ultrafiltration with different molecular-weight cut-offs. The order of the molecular weights of the five fractions calculated from the HPSEC analysis corresponded to that defined by ultrafiltration. This supported the reliability of the method.
JAPAN SOC ANALYTICAL CHEMISTRY, May 2008, ANALYTICAL SCIENCES, 24 (5), 607 - 613, English[Refereed]
Scientific journal
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.
JAPANESE SOC MICROBIAL ECOLOGY, DEPT BIORESOURCE SCIENCE, 2008, MICROBES AND ENVIRONMENTS, 23 (1), 44 - 48, English[Refereed]
Scientific journal
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 H-1 and C-13 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 HoA fractions from the B horizon showed a higher alkyl C proportion than samples from other horizons in winter and spring. These changes with soil depth from the Oi to A horizons might result from selective utilization of carbohydrate carbon by microorganisms, whereas those in the B horizon may result from sorption to mineral surfaces. The HoA fractions in the stream were similar in relative molecular weight, distribution of each type of proton and carbon species in HoA fractions from the B horizon, whereas stream HoA fractions collected in summer would be derived from organic horizons. This indicated that vertical changes in the chemical properties of HoA fractions in soil and pathways of water to the stream would largely affect the chemical properties of HoA fractions in the stream.
BLACKWELL PUBLISHING, Oct. 2007, SOIL SCIENCE AND PLANT NUTRITION, 53 (5), 551 - 561, English[Refereed]
Scientific journal
Carbon isotopes (C-13 and C-14) were used to study the characteristics and origin of humic substances in water samples from Lake Biwa in Japan. Humic substances were isolated from surface lake waters in each season by the XAD extraction method and their carbon isotopic ratios were measured by accelerator mass spectrometry. The Delta C-14 values of Biwa humic and fulvic acids indicate that these substances consist mainly of pre-bomb C-14. There is a negative correlation between Delta C-14 and delta C-13 values for the Biwa fulvic acids. The fulvic acid consists of younger organic materials with lower delta C-13 value in January, but older organics with higher delta C-13 in April and October. The major part of fulvic acid may be supplied from soil solution and/or groundwater in the watershed and their contribution varies with season. (c) 2007 Elsevier B.V. All rights reserved.
ELSEVIER SCIENCE BV, Jun. 2007, NUCLEAR INSTRUMENTS & METHODS IN PHYSICS RESEARCH SECTION B-BEAM INTERACTIONS WITH MATERIALS AND ATOMS, 259 (1), 552 - 557, English[Refereed]
Scientific journal
C-14 ages and delta C-13 were examined for sclerotium grains to elucidate the characteristics of these grains distributed in forest soils. The ages of the grains from surface A horizons and buried A horizons were ca 100-200 BP and ca 300-1,200 BP, respectively. In comparison with humic acid extracts, the C-14 ages were in the increasing order: humic acid fraction < humic acid Pg fraction < sclerotium grains. The delta C-13 values for sclerotium grains in surface A horizons and buried A horizons were approximately -31 parts per thousand to -28 parts per thousand, and these values were approximately 2-4 parts per thousand smaller than those of humic acids and soils. The C content of the grains had a tendency to decrease with increasing C-14 ages, while the C content of humic acid was constant with age. The C-14 ages of sclerotium grains indicate the individual age of grain formation, which are more likely to assign closer ages to the beginning of soil forming than the C-14 ages of humic acid. The low delta C-13 values for sclerotium grains have presumably originated from characteristically biological organics, which may be protected from attack in soils because of their structure.
TAYLOR & FRANCIS LTD, Apr. 2007, SOIL SCIENCE AND PLANT NUTRITION, 53 (2), 125 - 131, English[Refereed]
Scientific journal
International conference proceedings
[Refereed]
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[Refereed]
Scientific journal
To clarify the formation condition of Type A humic acids (HAs) from plant residues and to contribute to reducing CO, emission, three plant residues were incubated for 0, 25, 50, 100 and 160 days with fresh volcanic ash and water at 90 degrees C to produce humic acid like substances (HALS). The HALS of all incubation samples showed a decrease in log (A(400)/A(600)) values and an increase in A(600)/C values with increasing incubation time. When HALS were classified, only rice straw HALS of 160 days (RS160) belonged to Type A, whereas broad leaf HALS of 160 days (BL160) and Japanese cedar sawdust HALS of 160 days (JCSD160) belonged to Type B. For elemental and nuclear magnetic resonance (NMR) analysis, the HALS samples were prepared according to the International Humic Substances Society (IHSS) method. Data from the elemental composition of all HALS showed high contents (45.98 to 56.55) of carbon (C), low (3.19 to 5.16) hydrogen (H), and low (0.33 to 2.36) nitrogen (N). Carbon content increased in RS and BL, and increased or fluctuated to some extent in the JCSD, whereas H and N contents decreased in all samples as incubation progressed. The H/C and O/C ratios showed a marked decrease, simultaneously the O/H ratio increased, with increased incubation days. These results suggested that oxidation occurred in the incubation system. Although some HALS samples (RS160 and BL160) appeared in the Type A region in both H/C versus O/C and H/C versus O/H diagrams. HALS plotted in the figures of log (A(400)/A(600)) versus A(600)/C, H/C versus O/C and H/C versus O/H diagrams were generally placed out of the area of natural soil HAs. In the case of 1H NMR, the spectral shape of RS, BL and JCSD differed from that of natural soil HAs. Only the 1H NMR spectrum of RS160 was similar to that of Type A soil HA. Changes in the composition of proton species in HALS showed that percentages of aromatic protons (H-ar) increased with increasing incubation. Spectra obtained using C-13 NMR revealed that RS and BL HALS were different from natural soil HAs, whereas RS160 was similar to Type A HA spectra. In the spectra of RS HALS, the signal intensities of carbohydrate C (approximately 74 and 105 p.p.m.) and methoxyl C (approximately 56 p.p.m.) decreased gradually as incubation time progressed, while carboxylic C (approximately 175 p.p.m.) increased. Simultaneously other distinct signals became broad and overlapped each other. As a result, the changes in RS HALS spectra suggested that progress in the modification of lignin and the oxidative degradation of polysaccharide structure, and the spectrum of RS160 became similar to the spectra of Type A HAs. Although the only signal resulting from phenolic C (approximately 150 p.p.m.) still appeared in RS160, the signal intensity decreased and became broader and weaker from RS0 to RS160 with incubation time. Therefore, it was concluded that RS HALS might form a completely similar spectra to the spectra of natural Type A HAs with longer incubation time.
BLACKWELL PUBLISHING, Jun. 2006, SOIL SCIENCE AND PLANT NUTRITION, 52 (3), 349 - 360, English[Refereed]
Scientific journal
The chemical composition of the hydrophobic acid fraction, which is adsorbed to XAD-8 resin at low pH and desorbed with high pH solution, of water-extractable organic matter in soil probably influences its environmental role and, therefore, it is important to recognize the differences in its chemical composition with season and soil horizon. Hydrophobic acid fractions were collected seasonally in 2004 from Oi, Oe/Oa, A and B horizons of Cambisol and were investigated using elemental analysis, high-performance size exclusion chromatography and H-1 nuclear magnetic resonance (NMR) spectroscopy. Atomic ratios of H/C and O/C decreased with increasing soil depth in winter and summer, suggesting that the hydrophobic acid fraction from lower mineral horizons had lower saturated bond content and carbohydrate content than the fractions from upper organic horizons. Based on high-performance size exclusion chromatography, the molecular weight at peak maximum of the hydrophobic acid fraction decreased significantly with increasing soil depth. The H-1 NMR spectra of the hydrophobic acid fraction showed remarkable changes. The signal intensities of carbohydrate protons (delta 3.0-4.3 p.p.m.) in the hydrophobic acid fraction from organic horizons decreased from winter to summer and increased in autumn, while the signal of aliphatic protons (delta 0-3.0 p.p.m.) increased and decreased. In all seasons of the year, the signal intensities of carbohydrate protons were greater in organic horizons and decreased significantly with depth in mineral soil, but the signal for aliphatic protons increased. Our results demonstrate that season and soil depth influence the chemical composition of the hydrophobic acid fraction of water-extractable organic
BLACKWELL PUBLISHING, Jun. 2006, SOIL SCIENCE AND PLANT NUTRITION, 52 (3), 361 - 370, English[Refereed]
Scientific journal
The effect of three inorganic minerals on the humification of three types of plant residues was determined by employing a model thermal incubation experiment. The plant residues consisiting of rice (Oryza sativa) straw, broadleaf tree (a mixture of oak/beech, Quercus serrata, Q. dentata, Q. acutissima etc.) sawdust and Japanese cedar (Cryptomeria japonica) sawdust were each mixed with Fe, Mn and Al in the form of hydroxides, oxides and sulfates. Humic materials were extracted after incubation and their composition was analyzed using a mixed solution of 0.02 M Na4P2O7 and 0.1 m NaOH. The pH values of the samples after a longer duration of the incubation period were all less than 5.0, with the lowest value of 2.16 for a sample incubated with Al-2(SO4)(3), except for the values of the samples incubated with MnO2, which ranged from 4.75 to 6.0. The Delta logK values decreased with the increase of the duration of the incubation period, whereas the RF values increased, as well as the amount of humus extracted (HE) and percentage of humic acid (PQ). Whereas most of the samples were identified as Type B and Type Rp humic acids, Type A humic acid was formed in all the plant residues incubated with Al-2(SO4)(3), FeO(OH) and MnO2 after <= 180 d of incubation period. Moreover, the degree of humification of the plant residues was observed in the order of broadleaf tree>rice straw>Japanese cedar. It can be concluded that the inorganic compounds Al-2(SO4)(3), FeO(OH) and MnO2 contributed to the acceleration of the humification process of plant residues during the thermal incubation. The effect of Al-2(SO4)(3) may be associated with the increase in the reactivity with other components in the system due to its high solubility, whereas FeO(OH) and MnO2 may be involved in a reduction-oxidation reaction during the incubation. The browning and/or blackening of the plant residues were similar to the production of melanoidin which led us to consider that the mechanism involved in the study was similar to that of the Maillard reaction.
JAPANESE SOC SOIL SCIENCE PLANT NUTRITION, Dec. 2005, SOIL SCIENCE AND PLANT NUTRITION, 51 (7), 925 - 933, English[Refereed]
Scientific journal
Chloroform-extractable green fraction (CEGF) was detected in the supernatant obtained by alkali precipitation from the HCl-dimethylsulfoxide (DMSO) extract of Pg-rich soil. In the alkaline solution, the color of CEGF was green and CEGF showed strong Pg-like absorption bands. Ultraviolet and visible (UV-VIS) spectral analysis and gel chromatography on Sephadex G-50 were performed to compare several properties between CEGF and Pg. CEGF, which was purified by gel chromatography on Bio-Beads SX-1, displayed strong absorption bands at 609, 562, 445 and 280 nm in the alkaline solution. These absorption bands were almost similar to those of Pg. Furthermore, the UV-VIS spectrum of CEGF in the organic solvents showed a similar characteristic pattern of 4,9-dihydroxyperylene-3,10-quinone (DHPQ), which was considered to be a chromophore of Pg. Based on the results of gel chromatography on Sephadex G-50, CEGF mainly consisted of two fractions, corresponding to the G(2) and G(3) fractions of Pg. These results indicated that the method for extracting CEGF from Pg-rich soil in the present study was easy and selective and that CEGF was one of the components of, or a closely related substance to Pg. A colorimetric method for the estimation of the CEGF content in soils was developed. The calibration curve of CEGF was linear over a wide range of contents from 2.75 to 220 mg L-1. The CEGF content in twelve samples of various soils was examined. CEGF was detected in all the soil sampled (5 orders) including three samples (3 orders) where Pg was not detected, and the content ranged from 0.07 to 1.66 g kg(-1) (dry soil). Therefore, the method for estimating the CEGF content in soils developed in the present study was found to be suitable for various soil orders and it was assumed that CEGF occurred in various soil orders.
TAYLOR & FRANCIS LTD, Oct. 2005, SOIL SCIENCE AND PLANT NUTRITION, 51 (6), 779 - 786, English[Refereed]
Scientific journal
Relationships between the distribution of fungal sclerotium grains and soil chemical properties were studied in forest soils of Podsole, Braunfahlerde, and Braunerde-Podsoles in Harz Mts., Germany. Development of sclerotium grains was dominant in surface horizons (Ah, E horizons) within a 10-cm depth and weight density of grains ranged from 0.01 to 4.99 g kg(-1) soil. The SEM-EDX analysis proved that the weight percentage (excluding C and N) of Al2O3 was 39.8-63.9% inside the grains. The content of elgosterol, a biomarker of viable fungal biomass, showed good correlations with weight density of sclerotium grains in grain-detected soils. The sclerotium grains were likely to be formed in soils with high ratios (>0.6) of organic bonding Al (Al-p) to amorphous Al (Al-o), and with high contents of exchangeable Al (Al3+) (>0.54 g kg(-1)). The content and state of active Al were believed to be responsible for the development of sclerotium because sclerotium grains were not detected in acid soils which had lower levels of free colloidal Al (Al-d, Al-o, Al-p). We believed that the intensive clay destruction associated with past lessivage process induced the absence of free colloid Al in such forest soils.
JAPANESE SOC SOIL SCIENCE PLANT NUTRITION, Dec. 2004, SOIL SCIENCE AND PLANT NUTRITION, 50 (6), 863 - 870, English[Refereed]
Scientific journal
The presence of aluminum oxyhydroxide and its micromorphological characteristics in sclerotium. grains were examined by SEM, TEM, and EDX analyses. A spherical fraction with a diameter of 100 nm, which contained C and Al as the predominant elements, was recognized as the unit particle of the matrix of sclerotium grains. The Al polymorphs and the Si spherical structures found in the ignited grains were assumed to correspond to boehmite and opaline silica particles, respectively. SEM analysis revealed the presence of a needle ball structure inside the hollow part of sclerotium grains. The relationship between the inner structure of sclerotium and biochemical processes of the host fungi was discussed.
JAPANESE SOC SOIL SCIENCE PLANT NUTRITION, Dec. 2004, SOIL SCIENCE AND PLANT NUTRITION, 50 (8), 1205 - 1210, EnglishScientific journal
Swollen chips made from trees felled during clear-cutting were composted with various organic and inorganic materials in an aerobic composting reactor for 5 months and then piled for 5 months. The organic materials included chicken feces, urea, nitrogenous lime (calcium cyanamide, manure), and material rapidly composted from food garbage in 24-h bacterial fermentation, while the inorganic materials were coal ash and volcanic ash. In this paper, we first attempt to estimate the quality and degree of maturity of each compost from its chemical properties. Furthermore, we try to calculate the maturity of the fermented wood chip composts from their mixture ratio of the initial materials by multiple linear regression analysis. We measured changes in the ON ratio, nitrate nitrogen (NO3-N) content, percentage of humic acid in the alkali soluble fraction (PQ),-cation exchange capacity, pH, and EC during the composting period. The degrees of maturity of the composts were estimated via a plant growth test using Chinese cabbage. We found that the CN ratio, NO3-N concentration, and PQ were suitable for estimating the degree of maturity of wood chip composts. For maturity, the CN ratio should be less than 14, the PQ more than 66.2, and the NO3-N concentration more than 853 mg kg(-1). We devised an equation to estimate the degree of maturity after 10 months by a multiple linear regression analysis from the mixing ratio of wood chips and the co-composted materials. From the multiple linear regression analysis, the above three indices of compost maturity could be estimated from the mixing ratio of the initial materials. This equation should enable us to determine the degree of compost maturity after 10 months based on the initial mixing ratio. (C) 2004 Elsevier Ltd. All rights reserved.
ELSEVIER SCI LTD, Nov. 2004, BIORESOURCE TECHNOLOGY, 95 (2), 121 - 128, EnglishScientific journal
Radiocarbon (C-14) was used to study the origin and transport of aquatic humic substances in river waters at the Chernobyl area, which received a pulse input of C-14 as a consequence of the nuclear accident. Water samples were collected in April 1999 from the Pripyat and Sakhan Rivers, which flow through the radioactive contaminated area (30 kkm exclusion zone). The Delta(14)C values of humic and fulvic acids ranged from -68parts per thousand to +75parts per thousand and were similar to400parts per thousand lower than those of non-contaminated environments. The aquatic humic substances may be derived mainly from those of bog, peat, and podzolic soil with older C-14 age, and thereby reflect a larger proportion of older groundwater humic substances. Contribution of C-14 by the Chernobyl accident appears to be small because of the long residence time of organic carbon at the surface soil. (C) 2004 Elsevier B.V. All rights reserved.
ELSEVIER SCIENCE BV, Aug. 2004, NUCLEAR INSTRUMENTS & METHODS IN PHYSICS RESEARCH SECTION B-BEAM INTERACTIONS WITH MATERIALS AND ATOMS, 223, 848 - 853, EnglishScientific journal
Sclerotium grain is the resting body of ectomycorrhizal fungi found in forest soils. A melanic-spherical shape in approximately 1-2mm diameter characterizes the external feature of the grain, and a hollow structure with honeycomb transverse wall appears inside the grain. In our previous studies, we reported a high aluminum concentration inside sclerotium grains and suggested the close relationship between the status of active aluminum and the distribution of these grains in Andosols (Watanabe et al., 2001; 2002). Here we examined the chemical properties focused on active aluminum and carbon in several nonallophanic Andosols under forest vegetation for further discussions on the regulating factor of the distribution of the sclerotium grains. In each studied soil profile, the mean weight of sclerotium grain (mg grain^<-1>) had a tendency to increase with the content of exchangeable aluminum, content of total organic carbon and nitrogen, carbon content of humic acid extracted from soils. The ratio of Alp to total organic C(Al_p/T-C) showed a strong negative correlation between the mean weight sclerotium grains regardless of profiles. The bonding ratio of carbon and aluminum in soils was assumed to be one of the factor influencing the development of sclerotium grains.
Japanese Society of Pedology, 2004, ペドロジスト, 48 (1), 24-32 - 32, JapaneseScientific journal
The decolorization of humic acids from five different humic layers of ages from 8, 000 to 30, 000yrs BP by Coriolus consors IFO9078 was studied to understand the factors affecting the stability of humic substances in buried humic layers of the Holocene to late Pleistocene, which developed in weathered tephra beds called loam beds in Japan. After three weeks of incubation, the buried humic acids showed clear decolorization, but the magnitude of decolorization was lower than that of the humic acids from various Holocene surface soils in a previous study. Although the buried humic acids in this study were obtained from layers of different soil ages, the elemental compositions of all humic acids have similar highly dehydrated properties. These results suggest that the high resistance of the buried humic acids against microbial degradation may be due not only to the formation of humic-clay complex and the decline of microbial activity but also to the chemical properties of humic substances.
Japan Association for Quaternary Research, 2004, The Quaternary Research, 43 (5), 367 - 373, JapaneseScientific journal
To obtain fundamental information on the nature and properties of sediments in dammed lakes, we investigated various properties of sediment from dammed Lake Ono using soil scientific methods. Furthermore, the Lake Ono sediment was characterized by comparing its various properties with those of yellow soil. 1) Lake Ono is a eutrophic lake which phosphorus is a limiting factor. 2) The pH, exchangeable base content, and degree of base saturation of the sediment were much higher than those of the soil. 3) The clay content of the sediment was 2 times higher than that of the soil. The texture of the sediment was Heavy clay (HC), while that of the soil was Clay loam (CL). There were no large differences on organic carbon and total nitrogen contents, and the C/N ratio between the sediment and the soil. 5) The "combine"-form humus content of the sediment was higher than that of the soil. The reverse was true for the "free"-form humus content. 6) The X-ray diffraction patterns of the clay fraction of the sediment were almost the same as those of the clay fraction of the soil. 7) The elemental composition and 13C-NMR spectrum of the fulvic acid isolated from the sediment were similar to those of the soil. On the basis of the present findings and previous information on the properties of soil distributed in catchment areas, it was assumed that the Lake Ono sediment is strongly affected by soil particles and Ca in its catchment areas, which flow into the lake.
Japan Society on Water Environment, 2004, 水環境学会誌, 27,9, 597-603 (9), 597 - 603, JapaneseScientific journal
Scientific journal
An attempt to create a soil amendment containing Type A humic acid-like substances was done by means of thermal incubation of a mixture of rice straw (RS) and coal fly ash (CFA). The specific objectives of the study are the following: 1) To make an effective use of CFA, a by-product of coal-fired power stations, and 2) To fix carbon in the soil for a long term period as Type A humic acids which are known to be hard to decompose. Optimal incubation conditions to create Type A humic acid-like substances were examined. Furthermore, the chemical properties of the created samples were analyzed. The results obtained can be summarized as follows: 1) It was found that among the three temperature conditions imposed (60, 75 and 90℃), 90℃ was the most suitable for the progress of humification, and that a water supply was very necessary. 2) Since the humic acid-like substances extracted from the incubated sample showed a high degree of humification at the pH range of 3-4, the increase in the degree of humification of the humic acid-like,substances may be accelerated by maintaining a low pH condition during incubation. 3) The highest RF value was observed in the mixture with a dry weight ratio of 1:1 (CFA:RS) after 180 d incubation at 90℃ with water. The 〓logK and RF values of the humic acid-like substances extracted with the mixed solution (pH 7) of 0.1 mol L^<-1> Na_4P_2O_7 and 0.1 mol L^<-1> H_4P_2O_7 was 0.686 and 94.2 respectively, and these humic acid-like substances corresponded to Type A humic acids. 4) The yields of Type A humic acid-like substances from the incubated mixture of CFA and RS (dry weight ratio of 1:1 and 1:2) were estimated to be at least 13.6% and 14.6% of the carbon contents of the samples at the start of the incubation, respectively. 5) The contents of nutrients, such as nitrogen and phosphorus in the incubated sample were smaller than those reported for other soil amendments such as rice straw compost. Therefore, additional application of nitrogen and phosphate fertilizers would be needed in the actual scene for agronomical application of this soil amendment.
Japanese Society of Soil Science and Plant Nutrition, 2004, 日本土壌肥料学会誌, 75,641-649 (6), 641 - 649, JapaneseScientific journal
International conference proceedings
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Scientific journal
The influence of phosphate addition and low pH condition on humification of three plant residues were determined by performing model thermal incubations of the plant residues rice straw (Oryza sativa), broadleaf sawdust (Kashiwa, Quercus dentate), and coniferous sawdust (Japanese cider, Cryptomeria japonica) with Sakurajima volcanic ash. Four experimental set ups were prepared: (Group 1) plant residues only; (Group 2) plant residues with Sakurajima volcanic ash; (Group 3) plant residues with Sakurajima volcanic ash and Na_2HPO_4; and (Group 4) plant residues with Sakurajima volcanic ash and Na_2HPO_4 with the pH adjusted to 5. Humic acids were extracted using a mixed solution of 0.02 M Na_4P_2O_7 and 0.1 M NaOH. Extractable Fe and Al oxides were determined using three different extraction methods: dithionite-citrate-bicarbonate (DCB), acid-oxalate (TAMM), and Na-pyrophosphate (NaPP). The pH values obtained for Group 1 samples ranged from 2.75 to 6.21; Group 2 samples were from 3.74 to 4.78; Group 3 samples were near neutral or alkaline, ranging from 6.93 to 7.59; and the values for Group 4 samples ranged from 5.38 to 6.28. The ΔlogK values decreased with longer incubation times while the RF values increased. Group 3 samples showed a decrease in RF values compared to Group 2. Type A humic acids were produced only from Group 2 samples derived from rice straw and broad leaf sawdust after about 120 incubation days. The amounts of the Fe and Al from all types of extraction methods decreased in Groups 3 and 4 indicating a possible binding up of these components with phosphate ions. It can be concluded that addition of Na_2HPO_4 increased the pH of the system and at the same time lowers the solubility of Fe and Al present in the Sakurajima volcanic ash. However, adjusting the pH to 5 to maintain lower pH conditions, has slightly increased the solubility of Fe and Al. Therefore, the higher the amount of extractable Fe and Al, the higher the RF values indicating a faster humification process. The relatively small amounts of Fe and Al in higher pH values and their reaction with phosphate rendered these components ineffective in hastening the humification process. Based on the correlation analysis, Al was more effective in hastening the humification process than Fe.
Japanese Society of Pedology, 2004, ペドロジスト, 48 2 72-82 (2), 72 - 82, English[Refereed]
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International conference proceedings
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International conference proceedings
The FT-IR and H-1 NMR spectra of humic acids, which were obtained from four soils of different types (a Fibric Histosol, Dystric Cambisol, Umbric Andosol, and buried Umbric Andosol) by sequential extraction with pyrophosphate solutions at different pH values (i.e. at pH 3, 5, 7, 9, 11, and 13), were measured. The shape of the IR spectra for each humic acid depended on the differences in the soil origin rather than the pH values. The IR spectra of humic acids in the Histosol and Cambisol showed typical absorption associated with lignin. The humic acids in the Andosol and buried Andosol were characterized by the disappearance of the absorption assigned to aliphatic C-H and the prominence of the absorption attributed to aromatic C=C and COOH groups. The humic acids in the Histosol and Cambisol showed aliphatic properties compared with those in the Andosol and buried Andosol. As the pH values of the extractant increased, the absorption strength of the bands attributed to aliphatic and amide groups increased and those to carboxylic groups decreased. The H-1 NMR spectra were broadly divided into five regions, namely aromatic (H-ar), methoxyl (HC-O), and aliphatic protons alpha(H-alpha), beta(H-beta), and gamma(H-gamma) to aromatic rings, while the proportion of each proton species was estimated. The proportion of H., in all the humic acids, except for the humic acids at pH 3 in the Histosol and the Andosol, decreased with the increase of the pH values. The increase of the ratio of H-beta to H-ar with the increase of the pH values, was more conspicuous in the following order: Cambisol > Andosol > Histosol and buried Andosol. Based on the results obtained in this study and the results from repeated analysis of the particle size distribution by gel permeation chromatography conducted in Fujitake et al. (Soil Sci. Plant Nutr., 44: 253-260, 1998), a model representation of the relationship between the proton composition and particle size in taking account of the differences in the properties of humic acids among soil types and extraction pH values, was illustrated.
TAYLOR & FRANCIS LTD, Jun. 2003, SOIL SCIENCE AND PLANT NUTRITION, 49 (3), 347 - 353, EnglishScientific journal
It will be important in future analyses of humic acids (HAs) by various chromatographic and spectrometric methods to obtain high yields of methylated HAs. A derivatization procedure for permethylation of HAs was evaluated in relation to the yield of the chloroform-soluble fraction. The procedure involved a 3 h incubation of HAs (50 mg) with methylsulfinyl carbanion (MSC) obtained by mixing petroleum-purified NaH with anhydrous dimethylsulfoxide (DMSO), followed by incubation with methyl iodide (CH3I). Ten HAs isolated from different Japanese and American soils (three Andisols, four Inceptisols, one Histosol, one Alfisol, and one Ultisol) were used to optimize this procedure. Optimum derivatization was achieved within the first 6 h after the addition of MSC and CH3I; further incubation (up to 24 h) did not result in significant changes in the yield of the chloroform-soluble fraction (60-100%). For most HAs, the maximal yields of chloroform-soluble fractions were obtained at concentrations of 10 mm for MSC and 13 mm for CH3I.
JAPANESE SOC SOIL SCIENCE PLANT NUTRITION, Jun. 2003, SOIL SCIENCE AND PLANT NUTRITION, 49 (3), 453 - 457, EnglishScientific journal
Humic acids (HAs) from 15 different soil samples were added to Czapek-Dox media inoculated with Coriolus consors IFO 9078. After 14 d incubation, decolorization of these culture media at 600 nm absorbance was measured. The aromaticity, the E-600(1%) value, the total acidity, and the elemental composition of the HAs were also determined, and the relationships between the decolorization and the chemical properties of HAs were examined. Percentage of decolorization of these culture media ranged from 8.8 to 39.5%. Andisol HAs showed a lower percentage of decolorization than the Inceptisol HAs. Percentage of decolorization showed highly negative correlations for the aromaticity, the E-600(1%) value, and the 0 H ratio, and highly positive correlations for the hydrogen content and the H / C ratio. In particular, the highest correlation coefficient (r = -0.836**) was obtained between the aromaticity and the decolorization. In addition, the HAs with a lower decolorization were arranged in the direction of dehydration on the H / C versus O / C diagram. These results showed that HAs with a higher aromaticity and a higher humification degree, showed a higher resistance, to microbial decolorization by C. consors.
JAPANESE SOC SOIL SCIENCE PLANT NUTRITION, Apr. 2003, SOIL SCIENCE AND PLANT NUTRITION, 49 (2), 201 - 206, EnglishScientific journal
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[Refereed]
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A small spherical black fungal sclerotium grain from podzolic soils, which was tentatively identified as the resting body of Cenococcum graniforme, was assumed as the source of green polynuclear quinone pigments in P type humic acid (K. Kumada and H.M. Hurst, Nature 214: 631-633, 1967). To examine the presence of bacteria inside sclerotium grains collected from an Andosol profile in Mt. Myoko, central Japan, the grains were repeatedly washed, ultrasonicated and then cultured on diluted nutrient broth. The sum of recovered bacteria as colony-forming units from the wash and ultrasonicate fractions was 1.46×106 (g fresh weight)-1: 88% of the count in the wash fractions (assumably resulting from grain surface and attached soil) and 12% in the ultrasonicate (inside grain). Thirty-one bacterial strains were isolated from the ultrasonicate fraction and their 16S rDNA partial sequences were determined. The predominant group was the Alphaproteobacteria (71%), chiefly the Sphingomonas group (52%). Representative isolates of the Sphingomonas group were examined for their ability to grow on naphthalenesulfonic acids as a model compound of polycyclic aromatic hydrocarbons (PAHs) and also on several phenolic acids. None of the isolates tested utilized the model PAH but many of them used p-hydroxy benzoic, vanillic, p-coumaric and ferulic acids for growth. Based on these results, the relationship between the predominance of Sphingomonas and the chemical character of the sclerotium grain was discussed. © 2003, Japanese Society of Microbial Ecology & The Japanese Society of Soil Microbiology. All rights reserved.
2003, Microbes and Environments, 18 (3), 126 - 132, EnglishScientific journal
The association properties of Am with aquatic humic substances in a 0.01M NaClO4 solution at pH 6-8 were studied on the basis of molecular size distribution. Ten humic substances isolated from river water with different water quality (pH 3.9-8.0 and dissolved organic carbon (DOC) concentration of 2-40 mg/l) were used for comparing their effects on the association of Am. The molecular size distribution of Am in the presence of humic substances from an uncolored river water (DOC 2 mg/l) was different from that of experimental systems using humic substances from brownish and high DOC (14-40 mg/l) river waters.
KLUWER ACADEMIC PUBL, 2003, JOURNAL OF RADIOANALYTICAL AND NUCLEAR CHEMISTRY, 255 (3), 459 - 464, EnglishScientific journal
Scientific journal
The distribution of sclerotium grains, which are considered to be the resting bodies formed by fungi species, was studied in 5 Andosol profiles in central Japan. Sclerotium grains were detected in the surface A and buried A horizons of nonallophanic (Alp / Alo > 0.5) soils but not in allophanic (Alp / Alo < 0.5) soils. The maximum density of the sclerotium grains in each profile was approximately 2.5 g kg(-1). A highly positive relationship was observed between the mean weight of the sclerotium grains and the content of exchangeable aluminum (Al3+) in soils. Aluminum concentration inside of the sclerotium grains was confirmed by energy dispersive X-ray spectrometer (EDS) analysis. The results obtained suggest that the status of active Al3+ in soils is an important factor for sclerotium. development.
TAYLOR & FRANCIS LTD, Aug. 2002, SOIL SCIENCE AND PLANT NUTRITION, 48 (4), 569 - 575, English[Refereed]
Scientific journal
Differences in decolorization of five humic acids, added to Czapek-Dox medium and inoculated with Coriolus consors, Coriolus hirsutus, Lenzites betulina, Streptomyces aureofaciens, or an unidentified actinomycete, were investigated. Percent decolorization after incubation for 21 d at 25 degreesC differed among humic acids and microbial strains. In the case of the three fungi, Cambisol humic acids, characterized as having low aromatic C and high carbohydrate C contents, were decolorized to a greater extent (12-51%) than were Histosol humic acids (3-29%) and Andosol humic acids (0-31%). Among humic acids decolorized by C. consors, those with higher percentage decolorization had high contents of carbohydrate C, low contents of aromatic C and a low degree of aromaticity. In contrast, S. aureofaciens decolorized Andosol humic acid 2 (86.5%) and both Cambisol humic acids (40.4-57.2%) but had little effect on Andosol I and Histosol. These results suggested that the resistance of humic acids to microbial decolorization is related to differences in their chemical structural and is microbial species dependent. (C) 2002 Elsevier Science Ltd. All rights reserved.
PERGAMON-ELSEVIER SCIENCE LTD, May 2002, SOIL BIOLOGY & BIOCHEMISTRY, 34 (5), 729 - 731, English[Refereed]
Scientific journal
Viscosity and molecular weight of particle size fractions obtained from an Andosol humic acid (HA) were determined. Viscosity was determined both in solutions with and without the addition of 0.1 Rr NaCl (Cs 0.1 and Cs 0, respectively) at pH 7.0, Polyelectrolytic character was observed in the particle size fractions based on the changes in the concentration dependence of reduced viscosity with NaCl concentrations. The use of a Cs 0.1 solution was suitable for the determination of the values of intrinsic viscosity ([eta]) of the particle size fractions. The [eta] value increased with increasing weight average molecular weight ((M) over bar (w)) determined by gel permeation chromatography (GPC), and ranged from 4.3 to 12.9 x 10(-3) (L g(-1)) in the Cs 0 solution and from 3.5 to 6.6 x 10-3 (L g(-1)) in the Cs 0.1 solution. A linear relationship between [eta] in the Cs 0.1 solution and (M) over bar (w) on a logarithmic scale, which was similar to the Mark-Houwink equation, was observed. The value of the constant alpha calculated from the relationship, which reflected the polymer morphology, was 0.75 in the Cs 0.1 solution, and it corresponded to a polymer with flexible chains.
TAYLOR & FRANCIS LTD, Jun. 2001, SOIL SCIENCE AND PLANT NUTRITION, 47 (2), 399 - 404, English[Refereed]
Scientific journal
The morphology and chemical composition of fungal sclerotium-like grains collected from the buried humic horizon of volcanic ash soil in Mt, Myoko were examined using a scanning electron microscope (SEM): energy dispersion Xray micro-analyzer (EDX), and electron probe micro-analyzer (EPMA). A high C content, low level of Si and high concentration of Al characterized the grains considered to correspond to the sclerotia of Cenoccocum graniforme. The Al-27 MAS NMR spectrum of the sclerotia showed the existence of 6- and 4-coordinated Al. X-ray diffraction analyses supported the presence of amorphous Al (ex. Al-humus complex) in the sclerotia.
TAYLOR & FRANCIS LTD, Jun. 2001, SOIL SCIENCE AND PLANT NUTRITION, 47 (2), 411 - 418, English[Refereed]
Scientific journal
The metal complexation of the hydroxyanthraquinones, chrysotalunin, chrysophanol and their derivatives, with Al3+, Ni2+ and Zn2+ was studied by electrospray ionization mass spectrometry (ESI-MS). The results showed that chrysophanol and its derivatives form metal complexes with Al3+, Ni2+ and Zn2+ ions, but chrysotalunin does not. Among the metal ions, Al3+ was found to form the complexes most easily.
IM PUBLICATIONS, 2001, EUROPEAN JOURNAL OF MASS SPECTROMETRY, 7 (6), 467 - 471, English[Refereed]
Scientific journal
Elemental composition and solution C-13 NMR spectra for six humic acid fractions with different particle sizes (i.e. 3K, 10K, 30K, 100K, 300K, and 500K) which were prepared from a humic acid in an Umbric Andosol by successive gel permeation chromatography were determined. Elemental composition of the particle size fractions clearly differed from one another. Contents of nitrogen and hydrogen increased with the increase of the particle size. Small and middle particle size fractions (3K to 100K) showed low contents of hydrogen and nitrogen corresponding to those in typical Andosol humic acids, while the contents in the large fractions (300K and 500K) were distributed in the ranges of those in the other humic acids. As the particle size increased, the H/C ratio increased whereas the O/H decreased. In the H/C versus O/C diagram, the large particle size fractions (300K and 500K) were observed in the area around humic acids with a low humification degree. Variation of the chemical structural properties with particle size differences was assumed, based on the analysis of the H/C versus O/H and H/C versus O/C diagrams. The changes of the carbon species with particle size differences were examined based on the C-13 NMR spectra. As the particle size increased, the aliphatic C content increased whereas the carboxylic and aromatic C content decreased and, therefore, the aromaticity decreased. In addition, a negative correlation (r=-0.977) was found to be significant at 0.1% level between the H/C ratios and aromaticity. The peak strength around 30 ppm assigned to chains of methylene group increased remarkably with the increase of the particle size. It was suggested that the changes of the content of the aliphatic carbon with the decrease of the particle size may depend on the changes of the aliphatic chain length. In conclusion, these findings suggest that the Andosol humic acid molecule may be composed of humic acid components with long chains of aliphatic groups for the larger particle size fractions, and of their homologous series through the reduction of the length of the aliphatic long chain for the smaller particle size fractions. These assumptions were compatible with those made in a series of studies previously reported.
JAPANESE SOC SOIL SCIENCE PLANT NUTRITION, Jun. 1999, SOIL SCIENCE AND PLANT NUTRITION, 45 (2), 359 - 366, English[Refereed]
Scientific journal
Humic acids (HAs) obtained from four different soils by sequential extraction with pyrophosphate solutions at different pH values (i.e. at pH 3, 5, 7, 9, 11, and 13), were examined by ultraviolet and visible (UV-VIS) spectroscopy and elemental analysis. UV-VIS spectra from 230 to 700 nm were measured, and absorbance coefficients of 1% humic acid solutions at 600 nm (E-600(1%)) and Delta log K were calculated. The shape of the spectra of humic acids depended on the soil types rather than on the pH values. The E-600(1%) values were higher in the neutral region, and lower in the alkaline region, for each pH value they decreased in the following order: buried Andosol > Andosol > Histosol greater than or equal to Cambisol. The Delta log K values for each pH value were higher in the following order: Histosol > Cambisol > buried Andosol greater than or equal to Andosol. Although the linear correlation was found to be significant between the E-600(1%)) and Delta log K values, the relation between these optical properties and pH values differed among the soil types. However, in the neutral region, the higher E-600(1%) values of humic acids from buried Andosol and Andosol and the lower Delta log K values of humic acids from Cambisol and Histosol suggest that the humification degree was higher in the neutral region. Data of elemental composition and atomic ratios were obtained for each humic acid. The H/C ratios in the four soils increased gradually with increasing pH values from 5 to 13, and those for each pH value were commonly higher in the following order: Cambisol > Histosol > Andosol > buried Andosol. The O/C and O/H ratios decreased with increasing pH values. The results of the H/C versus O/C diagram suggested that decarboxylated humic acids were extracted at the higher pH values. A highly significant correlation coefficient was obtained between the H/C and O/H ratios (r = -0.891***), Results showing that the decrease of the pH values corresponded to the order of the humic acids in the correlation curve in the H/C versus O/H diagram suggest that the humic acids with a higher content of unsaturated bonds and a higher degree of oxidation were extracted at the lower pH values within the range from 5 to,13.
JAPANESE SOC SOIL SCIENCE PLANT NUTRITION, Jun. 1999, SOIL SCIENCE AND PLANT NUTRITION, 45 (2), 349 - 358, English[Refereed]
Scientific journal
Six hydroxyanthraquinones (chrysophanol, chrysotalunin, microcarpin, physcion, 7,7'-biphyscion, and hinakurin) present in the samples of 26 surface soils were quantitatively analyzed, and the contents of HAQs in soil types were compared. The soil samples had been collected from 19 Umbric Andosols and seven Distric Cambisols, and the Andosols were further subdivided into those with allophanic soil materials (exchange acidity (y(1))<5 mL 100 g(-1)) and non-allophanic soil materials (y(1)greater than or equal to 5 mt 100 g(-1)). The following results were obtained. (1) It was determined quantitatively for the first time that chrysotalunin was the major hydroxyanthraquinone in many soils. (2) The amounts of major dimeric hydroxyanthraquinones (chrysotalunin, 7,7'-biphyscion, and microcarpin) in non-allophanic soil materials were significantly larger than those in allophanic soil materials. As the contents of chrysotalunin in Andosols were positively correlated with y(1), which was reported to be positively correlated with aluminum toxicity and exchangeable aluminum in soil, it is suggested that toxic aluminum may be involved in the production of soil hydroxyanthraquinones.
TAYLOR & FRANCIS LTD, Jun. 1999, SOIL SCIENCE AND PLANT NUTRITION, 45 (2), 297 - 306, English[Refereed]
Scientific journal
The vertical distribution of main soil hydroxyanthraquinones (HAQs) in the soil profiles of five Japanese Andosols, one Japanese Gambisol, and one Nepalese Gambisol was analyzed quantitatively, using high performance liquid chromatography and thin Bayer chromatography with a two stage development accompanied by scanning densitormetry. The results were as follows: The vertical distribution patterns of chrysophanol (CIPL) and its dimers in Andosols profiles shewed maximum contents in the middle past of the surface horizon. The vertical distribution of physcion (PYS) and its dimers in soil profiles showed various patterns in each profile. AdditionaBPy, we investigated the vertical distribution of HAQs in AndosoPs under a Miscanthus sinensis grassland, and in an adjacent successional red pine (Pinus densiflora) forest at Sugadaira, Central Japan. En the surface soil (0–15 cm), the contents of the dimers of CPL (microcarpin and chrysotalunin) slightly increased and those of the dimers of PPS (7,7′-biphyscion and Rinakurian) showed a remarkable increase in the succession, whereas the contents of monomeric HAQs (CBL and PYS) slightly decreased suggesting preferential production of dimeric HAQs below a depth of 15 em in the forest Andosol. The dimers of CPL and the dimers sf PPS exhibited diRerent structures, vertical distribution patterns, and changes in the contents in Andosols in the secondary succession. Therefore, it was assumed that dimeric reaction processes of CPL may be different from those of PYS, if dimeric reactions had occurred in soil. © 1999, Taylor & Francis Group, LLC.
1999, Soil Science and Plant Nutrition, 45 (3), 551 - 561, English[Refereed]
Scientific journal
The relationships between surface active properties and humic acid (HA) particle sizes were investigated. Two HAs from an Ando soil and a Brown forest soil were separated into 6 particle size fractions by gel permeation chromatography. Surface-active properties characterized by surface excess value (Gamma mol cm(-2)), cross-sectional surface area per molecule (A nm(2)), critical micelle concentration (CMC g L-1), efficiency and effectiveness of water surface tension reduction were obtained by the measurement of the surface tension of HA solutions from different particle size fractions. For the HA from the Ando soil, except for the smallest particle size fraction, increasing particle size enhanced the efficiency of reduction of the water surface tension and decreased the CMC, while the effectiveness of reduction of the water surface tension was about the same. The surface activity of the HA from the Ando soil increased with increasing particle size. This phenomenon was similar to the surface activity of a homologous series of surfactants, which increased with increasing alkyl chain length. For the HA from the Brown forest soil, the smallest particle size fraction and three large fractions showed a high efficiency, namely a high surface activity. The smallest fraction from the Brown forest soil showed the highest efficiency and the lowest CMC value. In both HAs, the smallest particle size fraction showed exceptional surface-active properties compared with the other fractions and three fractions with large particle size showed a higher surface activity than other smaller fractions.
JAPANESE SOC SOIL SCIENCE PLANT NUTRITION, Dec. 1998, SOIL SCIENCE AND PLANT NUTRITION, 44 (4), 497 - 505, English[Refereed]
Scientific journal
Humic (HAs) and fulvic acids (FAs) were obtained from A horizons of four different soils (a Fibric Histosol, Dystric Cambisol, Umbric Andosol, and buried Umbric Andosol) by the sequential extraction with pyrophosphate solutions at different pHs (i.e. at pH 3, 5, 7, 9, 11, and 13). The yield of the FAs from the four different soils decreased with the increase in pH values from 3 to 7, and then, increased or remained constant with pH values from 9 to 13. The distribution pattern of the yield of HAs differed among the four soils, and the total yield for HAs extracted at pH values extending from the acid to neutral region (3-7) was equal to or higher than that in the alkaline region (9-13), except for the Histosol. In particular, the yield of buried Andosol HAs at pH values of 3, 5, and 7 was remarkably high, ca. 25-30% of total HAs with pyrophosphate extractants. Sequential extraction with the pyrophosphate solutions gave sufficient amounts of HAs extracted for wide-ranging pH values extending from the acid to alkaline region to compare the properties of individual HAs based on the difference in pH values. Particle size distribution analysis of each HA determined by gel permeation chromatography (GPC) suggested that the proportion of components with a larger particle size differed among the HAs extracted from the four soils for the same pH value. It is, however, interesting to note that the proportion of components of HAs with a larger particle size in the four different soils increased gradually and regularly with the increase of the pH value. These results suggest that this sequential extraction technique is suitable for obtaining a series of HAs differing in particle size.
JAPANESE SOC SOIL SCIENCE PLANT NUTRITION, Jun. 1998, SOIL SCIENCE AND PLANT NUTRITION, 44 (2), 253 - 260, English[Refereed]
Scientific journal
Four bianthraquinones and two monoanthraquinones were isolated as the major soil anthraquinones from a volcanic ash soil in Japan. They were identified as a new natural product 5,5'-biphyscion (named hinakurin) (3) and five known compounds, chrysotalunin (1), (-)-7,7'biphyscion (2), microcarpin (4), chrysophanol (5), and physcion (6) using MS, 1D NMR, and 2D NMR techniques. Although the dimers (1-4) are rarely found as natural products, they, along with 5 and 6, were ubiquitous and predominant over other anthraquinones in various soils from Japan and Nepal.
AMER CHEMICAL SOC, Feb. 1998, JOURNAL OF NATURAL PRODUCTS, 61 (2), 189 - 192, English[Refereed]
Scientific journal
Humic acids (HAs) extracted from an Umbric Andosol (UA) and a Dystric Cambisol (DC) were fractionated into 7 fractions by successive gel permeation chromatography (GPC) and their fractions were studied by spectral analysis. With increasing particle sizes, the absorption of methylene groups and amide of peptides increased in the IR spectra of both HAs and that of carboxylic groups decreased in the IR spectra of UA, the HA obtained from an Umkric Andosol. Based on the H-1 NMR data in UA, there was a significantly negative linear correlation (-0.950, p<0.001) between H-ar (delta 6.0-9.0 ppm) and H-c-o (delta 3.0-4.3 ppm). Such a negative linear correlation (-0.868, p<0.01) was also observed between H-ar and H-beta (delta 0.9-1.6 ppm). In addition, with increasing particle sizes, the percentage of aromatic protons decreased (from 30.6 to 4.2%). These results suggest that the increase in HA particle sizes depends on the length of aliphatic groups and the bond of methoxyl groups, and HAs were composed of HA molecules of homologous series. On the other hand, in DC, HA obtained from Dystric Cambisol, no significant relationships were observed between each type of protons and aromatic protons. It is suggested that a mixture of non-humic substances smeared the spectral data of DC.
JAPANESE SOC SOIL SCIENCE PLANT NUTRITION, Jun. 1996, SOIL SCIENCE AND PLANT NUTRITION, 42 (2), 355 - 360, English[Refereed]
Scientific journal
The separation and quantitation of the five main hydroxyanthraquinones in soils has been performed by TLC with two development steps and densitometric scanning. The five hydroxyanthraquinones were completely resolved both from each other and from other accompanying compounds and were quantified hy densitometry in reflectance mode at a sample wavelength of 445 nm and a reference wavelength of 540 nm. The detection limit of the method was in the lower nanogram range (5-10 ng) and the peak area response was linearly dependent on quantity in the range 1-300 ng.
SPRINGER HUNGARICA KIADO KFT, Jan. 1996, JPC-JOURNAL OF PLANAR CHROMATOGRAPHY-MODERN TLC, 9 (1), 48 - 51, English[Refereed]
Scientific journal
The distribution of CLN (a dimer of chrysophanol), which is a common pigment, was determined by HPLC in a variety of soils from widely separated locations in Japan: (1) CLN had a widespread distribution among Japanese soils (2) in soils of A-type humic acid (HA), CLN contents were higher than those in soils of other types (3) for an ando soil CLN was mainly found in the HA and humin (HM) fractions rather than in fulvic acid (4) it is suggested that the distribution of CLN in this profile depends on that in the HA fractions (5) distribution of CLN in HN fractions and its presence in buried humus horizon (6400-10200 YBP) suggests its high stability. © 1992.
30 May 1992, Science of the Total Environment, The, 117-118 (C), 219 - 226, English[Refereed]
Scientific journal
The contents of chrysotalunin (CLN) in Japanese surface soils were first measured by isolative determination using high performance liquid chromatography (HPLC). These soil samples (N = 67) which consist of red soils, yellow soils, dry podzolic soils, brown forest soils, black soils, and immature soils, were taken from various locations in Japan extending from the southern subtropical to the northern subarctic regions. All the soil samples (N = 67) gave CLN contents ranging from 0.1 to 29.1 ppm. The average CLN content of the black soils which was 10.2 (+/- 1.4, S.E.) ppm (N = 36), was about two times as high as that of the brown forest soils (4.8 +/- 1.2 ppm, N = 19). A significant difference was found in the CLN contents among black soils, brown forest soils, and the soils belonging to other types (p < 0.05). Although no relationship between the CLN contents and soil properties (cf. soil pH, organic carbon contents, Fe and Al contents, etc.) was observed, an obvious difference in the frequency distributions of log-transformed CLN contents was detected among the soil groups under different land uses, for example grasslands with bamboo grass (Sasa sp. or Neosasamorpha sp.) and/or eulalia (Miscanthus sinensis) (19.0 +/- 2.6 ppm, N = 10), forests with bamboo grass and/or eulalia (9.9 +/- 1.4 ppm, N = 15), paddy fields (1.8 +/- 0.1 ppm, N = 5), etc.
JAPANESE SOC SOIL SCIENCE PLANT NUTRITION, Dec. 1991, SOIL SCIENCE AND PLANT NUTRITION, 37 (4), 619 - 627, English[Refereed]
Scientific journal
A high-performance liquid chromatographic method for the determination of chrysotalunin (1,1', 8,8'-tetrahydroxy-3,3'-dimethyl-7,7'-bianthraquinoyl), the main hydroxyanthraquinone pigment in soils, is proposed. This method is based on the acetylation of chrysotalunin, and separation and determination of its tetraacetate by liquid chromatography. The minimum detectable amount of chrysotalunin expressed as chrysotalunin acetate was 10 pg. Seventeen samples of different soil types in Japan containing various amounts of carbon were examined. Chrysotalunin amounts ranged from 0.5 ppm (Orthic Acrisols) to 27.7 ppm (Humic Andosols). In addition, for comparison, all samples were assayed using a colorimetric method. From the results of these analyses, the chromatographic method was found to be suitable for the determination of chrysotalunin in soils of various types.
ELSEVIER SCIENCE BV, Apr. 1991, GEODERMA, 48 (1-2), 83 - 91, English[Refereed]
Scientific journal
[Invited]
Introduction scientific journal
[in Japanese]
THE JAPANESE FORESTRY SOCIETY, 2015, The Japanese Forest Society Congress, 126 (0), Japanese京都議定書における温室効果ガス削減目標が設定されて以来,エネルギー消費への関心が広がるとともに炭素動態に関するデータが蓄積されてきた。我が国で削減目標('90年比6%減)に対する約束期間(2008~2012)内の達成見込みが得られた(2012年12月現在)背景には詳細なデータの積み上げがあった。その膨大なデータには各土地利用における土壌炭素変化量の算出も大きく貢献している。土壌炭素の変化量を算出するためには土壌炭素賦存量が必要であり,そのデータベースの構築と算出法の開発は大きな成果といえる。この成果は,さらに続く排出削減目標に対し,算出法の最適化を図るための基盤になると考えられる。そこで,本シンポジウムでは,国土面積の占有割合が高い森林と農地での土壌炭素賦存量と変化量の算出結果と今後の課題を取り上げた。一方,それら土地利用に含まれない領域として都市域の土壌炭素賦存量算出の問題点も指摘した。さらに,土壌炭素変化量に影響する土壌有機物の分解特性と存在形態に関する話題を挙げた。また,様々な土壌における有機物の多様性を質的データで示し,さらにその変化の方向性についても論及した。土壌炭素に関する量的・質的な取扱いの両面から日本の土壌炭素賦存量について論議を行った。
Japanese Society of Soil Science and Plant Nutrition, Jun. 2013, Japanese Journal of Soil Science and Plant Nutrition, 84 (3), 224 - 229, Japanese[Refereed][Invited]
Introduction scientific journal
典型的な黒ボク土は黒く厚いA層をもつ。この黒さは言うまでもなく腐植によるものであり,黒ボク土が広く分布する我が国ではひときわこの黒い腐植についての関心が高く,化学構造特性や生成過程(腐植化過程)に関する多くの研究がおこなわれてきた。近年では陸域生態系における炭素貯留庫としての土壌の役割が認知されるようになりチェルノーゼムと双璧をなす黒ボク土の腐植集積メカニズムに対してより多くの関心が寄せられている。そこで本講演では黒く多量の炭素を蓄積している黒ボク土の腐植層は他の土壌の腐植と何が違うのか,どのようにしてそれらが生成されるのか,なぜ長期にわたって蓄積するのか,という話題にそって現況を概説する。なお,黒ボク土の土壌腐植の性質をもっとも反映するのは腐植酸であるため,主に腐植酸に焦点を絞って話を進める。
ペドロジスト編集部, Dec. 2011, ペドロジスト, 55 (2), 93 - 98, Japanese[Invited]
Introduction scientific journal
Summary national conference
Summary international conference
[Refereed]
Introduction scientific journal
The vertical distribution of the content of the chloroform-extractable green fraction (CEGF) in the soil profiles of four Japanese Andosols, one Japanese Cambisol and one Nepalese Cambisol was examined using a colorimetric method with an ultraviolet and visible spectrophotometer. In addition, the relationship between the CEGF content and the soil chemical properties was examined by statistical analysis. CEGF was detected in all the soil samples, and the content ranged from 0.02 to 1.16 g kg(-1). The CEGF content in the surface A horizon of the Andosol tended to be higher than in the Cambisol. The vertical distribution of the CEGF content in three soil profiles (two Andosol profiles and one Nepalese Cambisol) revealed maximum values in the subsurface horizon. In the Japanese Cambisol, the content of the CEGF was highest in the surface horizon. In the remaining two Andosol profiles containing a buried humus horizon, the content of the CEGF was highest in the buried humus horizon and the distribution was considerably different from that of organic carbon. Statistical analysis showed that the content of the CEGF displayed a significant positive correlation (P < 0.001, n = 36) with the contents of dithionite-citrate-bicarbonate-extractable Al (Ald), and with oxalate-oxalic acid-extractable Fe and Al (Feo and Alo, respectively). Furthermore, the content of the CEGF showed a significant positive correlation with the content of Alo (r = 0.944, P < 0.01, n = 6) in the soil with the highest content of CEGF in the profile. It was, therefore, suggested that CEGF is actively produced in humus-rich soils like Andosols, and that Ald, Feo and, in particular, Alo were associated with the vertical distribution of CEGF in the soil profiles.
BLACKWELL PUBLISHING, Jun. 2006, SOIL SCIENCE AND PLANT NUTRITION, 52 (3), 274 - 283, EnglishOthers
Summary international conference
Summary international conference
The pumice layer was derived from the northwest fringe of Taal Volcano somma in Kaybagal, Tagaytay City in the Philippines. It has a gravel diameter of 3 to 5 centimeters (cm). The pumice gravel has a yellow surface color and a black inner color. These were observed using an optical microscope and scanning electron microscope (SEM). The chemical and mineralogical constituents were determined using a electron probe micro analyzer (EPMA), and X-ray diffraction apparatus. The results obtained from the optical microscope and SEM showed bubbles in the black or inner part of the pumice, while the surface showed weathered fine particles. Some of the bubbles observed were also partly weathered. The X-ray diffraction pattern showed smectite as the predominant mineral in the yellow surface layer, while amorphous materials were predominate in the black inner part. We speculate that smectite of the pumice may result from the weathering of amorphous glass in the inner part of pumice.
Japanese Society of Pedology, 30 Jun. 1999, ペドロジスト, 43 (1), 22 - 27, EnglishChanges of soil profiele, soil physico-chemical properties and micro organism biomass with years were observed in man-made forests formed by close planting of nursery stocks of laurel trees and in a natural forest. Ages of the man-made forests were 1 year (ZR), 11 years (TN) and 18 years (TW) after planting trees respectively. Soil profiles showed the development of organic and humic layers with years as the increase of the depths of O and A horizon, darkness of soil colors, contents of roots and compactness. Though soil texture of man-made forest soils and a natural forest soil were loamy sand to sandy loam and clay loam respectively, it was difficult to recognize that soil texture changed for 10-20 years in man-made forest soils. Decreasing of bulk density and increasing of pore volume were observed with years except for some layers of TN. The starting depths of the constant lower values of softness decreased with years except TN and the values of softness in the subsoil of TN was lower than those of others. Total carbon, total nitrogen, CEC and microorganism biomass in soils increased with years and they were supposed to be caused from the increasing of plant residue with plant growth.
Japanese Society of Pedology, 30 Jun. 1998, ペドロジスト, 42 (1), 33 - 43, JapaneseChanges of plant vegetation with years were observed in man-made forests formed by close planting of laurel nursery trees and in a natural forest. Ages of the man-made forests were lyear (ZR), 11 years (TN) and 18 years (TW) after planting trees and that of the natural forest (NF) was more than 100 years. 1) The height and structure of vegetation of TN and TW were 7. 5 to 10 m and 3 layers respectively and they were smaller than those of NF. 2) Though the numbers of trees per unit area in man-made forests were 2 to 4 times more than that of NF, the basal area (BA) and the D^2H of TN and TW were only 30% and 10% of NF by per tree respectively. 3) Number and D^2H of trees were occupied by a few kinds of dominant species in ZR, TN and NF in contrast with by several ones in TW. 4) Though the maximum frequency was 4-6 m in both TN and TW, TW also had the secondary maximum in 1.3-2 m. The frequency of NF decreased from gradually 30% in 1.3-2 m with increasing of heights. 5) Its is supposed that the man-made forests are on the way to a natural forest and they develop their vegetation with increasing stratification and/or biomass, e. g. D^2H in accordance with decreasing of numbers of trees by the natural selection.
Japanese Society of Pedology, 30 Jun. 1998, ペドロジスト, 42 (1), 21 - 32, JapaneseOthers
Electromagnetic scattering (e.g., light scattering, small-angle X-ray scattering, and small-angle neutron scattering) provides information on the size and shape of colloidal particles in a highly dispersed system (Feigin and Svergun 1987). The technique has been applied to various materials including biological macromolecules, synthetic polymers, amorphous solids, and other colloidal compounds (Feigin and Svergun 1987). Several attempts have also been made to evaluate the size and shape of humic acid in solution using the scattering techniques (Wershaw and Pinckney 1989; Osterberg et al. 1993). Small-angle X-ray scattering (SAXS) was first applied to sodium humate by Wershaw et al. (1967) and they estimated the molecular weight, molecular volume, radius of gyration (R(g)), and shape factor of the sodium humate. Thereafter, based on studies of humic substances by SAXS, R(g) which can be estimated independently from the SAXS data of humic substances was obtained as the sole parameter because of the lack of information on the chemical structure of humic substances (Lindqvist 1970; Wershaw and Pinckney 1971, 1973, 1977; Thurman et al. 1982). In principle, however, it is possible to evaluate the shape of particles by analyzing the profile of the SAXS data, because the scattered intensity and profile reflect the number and spatial distribution of the scattering units composing colloidal particles. The excess scattered intensity is Fourier-transformed into the distance distribution function which represents the electron density distribution in a particle (Kajiwara et al. 1991). The shape of humic acid can be deduced approximately from the distance distribution function without any chemical information. In addition to the distance distribution function, various methods can be used to analyze the shape of objects from the scattering profile.; Fer example, the Kratky plot yields information on the chain stiffness of polymers or in some cases on the architecture of a molecule (Donkai et al. 1985). The purpose of this study is to analyze the size and shape of humic acid by using the SAXS data from the solution.
JAPANESE SOC SOIL SCIENCE PLANT NUTRITION, Jun. 1995, SOIL SCIENCE AND PLANT NUTRITION, 41 (2), 363 - 366, EnglishIntroduction scientific journal
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