Persistency and monosaccharide composition of polysaccharides of soil which received no plant materials for a certain period under field conditions

Abstract

The monosaccharides in acid hydrolysates were monitored in soil which was packed in a bag made of glass microfiber paper and buried in upland and paddy fields for up to 36 months. During the initial flush of decomposition, all constituent monosaccharides except for non cellulosic glucose were found to decrease. The amounts which disappeared were greater than the water extractable saccharides of the air dried soil or ground sample of the air dried soil. After the flush of decomposition, the changes in mannose, galactose, fucose and rhamnose were small, whereas cellulosic glucose, arabinose and xylose continued to decline in the upland field soil. The soil saccharides are classified into six groups and their relative persistency is discussed.

The monosaccharide composition did not change markedly, but the proportion of monosaccharides relating to plant materials declined with time after incubation. The molar ratios of hexoses to pentoses, deoxyhexoses to pentoses, and non-cellulosic glucose to cellulosic glucose increased gradually, whereas a gradual decline in the ratio of xylose to mannose was observed when the soil received no plant materials under field conditions.     

THE MONOSACCHARIDE COMPOSITION OF POLYSACCHARIDES IN ANDO SOILS

The monosaccharide composition of Ando soils, which originate from volcanic ash and have high organic matter content (8–21% carbon), was quite different from that of non-volcanic ash soils (1.2–1.9% carbon), being richer in mannose, fucose and ribose, whereas there was less glucose in cellulose-like form, arabinose, xylose and rhamnose. The Ando soils were also characterized by a lower percentage of organic carbon in the form of saccharide (4.4–7.4%) in comparison with non-volcanic ash soils (10.5%), though the former soils contain a greater amount of saccharides. The monosaccharide composition of Ando soils was unrelated to the vegetation, land usage, or climatic conditions, and is presumed to be a soil characteristic resulting from the preferential accumulation of microbial polysaccharides.     

Saccharides of ectomycorrhizal fungal sclerotia as sources of forest soil polysaccharides

ABSTRACT

The neutral monosaccharide composition of forest soils differs from that of non-forest soils suggesting there is an accumulation of microbial saccharides. Ectomycorrhizal (ECM) fungi can be responsible as the fungi are typical in forest soils. We investigated neutral saccharides of ECM fungal sclerotia to determine what part it might play in the origin of forest soil polysaccarides. Sclerotial grain (SG) was collected from the O, A1 and A2 horizons of a soil of subalpine forest of Mt. Ontake, central Japan. Neutral saccharides in soil and SG were analyzed by two step hydrolysis with sulfuric acid and gas-chromatography of alditol acetate derivatives. Saccharides accounted for 6.0?16% of the SG by carbon content. The SG contained predominantly easily hydrolysable (EH)-glucose, which accounted for 75–85% of the composition depending on grain size and the soil horizon, followed by mannose (7.7?15%), galactose (2.2?4.8%) and non-easily hydrolysable (NEH)-glucose (1.7?6.1%). The SG contained all of these sugars irrespective of its size. The SG collected from the A1 and A2 horizons contained all sugar components found in that from the O horizon, except for fucose in that from A2 horizon. The monosaccharide composition of SG indicates that accumulation of ECM fungal sclerotial polysaccharides might have been responsible for enlarging the molar ratios of (galactose + mannose) /(arabinose + xylose) and EH-glucose/NEH-glucose of forest soils. The proportions of SG saccharides relative to soil saccharides were 3.6, 1.2, and 0.83% for the O, A1 and A2 horizons, respectively. These levels of the proportion are considerable as ECM fugal sclerotia are the products of a limited species among hundreds and thousands of microbial species inhabiting forest soils. The sclerotia forming ECM fungal species such as Cenococcum geophilum may be key sources of forest soil polysaccharides.     

An automated anion-exchange chromatographic procedure for the estimation of saccharides in acid hydrolysates of soil

It is well known that the major neutral monosaccharide components released from soil by acid hydrolysis are glucose, galactose, mannose, arabinose, xylose, ribose, rhamnose and fucose. A colorimetric determination of the saccharide mixture released from soil is unsatisfactory for determining an accurate figure for soil saccharides. More precise information can be obtained by the determination of monosaccharides after separation by chromatography. Paper and thin-layer chromatography for quantitative analysis are rather time consuming and laborious. The gas chromatographic procedure was applied successfully for the analysis of sugars in soil hydrolysates by OADES et at. (7). Preparation of the various derivatives for gas chromatography still requires many steps, much handling of the sample, and considerable time, although final analysis of the product derivative is accomplished in an hour or two.     

Changes in the amount and distribution of neutral monosaccharides of savanna soils after plantation of Pinus and Eucalyptus in the Congo

In the Congo, near Pointe-Noire, Pinus and Eucalyptus were planted on the savanna for 30 years. We have characterized the effects of this change on land-use on the composition of carbohydrates in whole soil and particle-size fractions of the soil. Carbohydrates represent variable proportions of the total soil organic carbon (TOC) of various particle size fractions. The largest proportions of sugar-C were found in the savanna soil with as much as 250 mg g⁻¹ TOC in the coarsest plant remains and approximately 190 mg g⁻¹ TOC in the finest organo-mineral fractions, whereas there was always less sugar in plantation soils. The monosaccharide xylose and mannose have different distributions: xylose appears to be the marker of the vegetal inheritance, whereas the dominance of mannose in the clay fraction bears the signature of current microbial sugar synthesis. The quantitative and qualitative evolution of the whole soil carbohydrates was studied as a function of plantation age. Carbohydrate-C represents 131 mg g⁻¹ of the soil organic carbon in the savanna soil, but decreases to an average value of 75 mg g⁻¹ in plantations more than 6 years old. This appears to be due mainly to the stimulation of the mineralization of the glucose, which represented 60% of the total sugars in savanna soil and only 45–48% in tree plantations. The ratio [arabinose + galactose + fucose]/[rhamnose + xylose], which is the largest in the oldest plantations, is significant for evaluating the replacement of carbohydrates of the original grass savanna by those of the trees.     

The effect of oxidation by periodate on soil carbohydrate derived from plants and microorganisms

It has previously been shown that treatment of soil with periodate and tetraborate releases much of the carbohydrate and destroys an equivalent proportion of the soil aggregates. The residual carbohydrate is proportionately richer in glucose, arabinose and xylose, sugars characteristic of plant remains, than the whole soil. The effect of sodium periodate (0.02 M, 6–168 h) and sodium tetraborate (0.1 M, 6 h) treatment of soil on carbohydrates of different origin was examined using ¹⁴C-labelled soil in which the label was present in microbial products arising from 7 and 28 day incubations of ¹⁴C-glucose in soil, or in both plant and microbial materials resulting from 12 week incubations of ¹⁴C-labelled barley leaf and 1 year incubations of ¹⁴C-labelled ryegrass in soil. Arabinose and xylose were the sugars most resistant to periodate in the glucose incubated soil; in the ryegrass incubation arabinose, xylose and glucose were more persistent than galactose, mannose and rhamnose. In the barley leaf incubation arabinose was more persistent than galactose and rhamnose. Thus periodate oxidation did not distinguish between sugars of different origin in soil and it was concluded that in the case of arabinose and xylose the persistence related to differences in chemical structures rather than to physical factors such as particle size of the plant fragments. The composition of the more stable residue can therefore not be used as an indication of polysaccharide origin in any comparison of the relative effects of plant and microbially derived material as aggregating agents.     

Neutral sugars in melanins synthesized by actinomycetes from Brazilian soils

 Nine actinomycete melanins synthesized under various culture conditions, eight of them by actinomycete samples isolated from Brazilian topsoils under savanna (cerrado) vegetation and one from an ATCC sample, were subjected to a two-step hydrolysis procedure and the sugars released qualitatively and quantitatively determined by capillary gas-liquid chromatography (GLC). Humic acids (HAs) extracted from these soils, analysed previously, were used for comparison. The neutral sugars glucose, galactose, mannose, xylose, arabinose, ribose, rhamnose and fucose and the alcohol sugar inositol were present in varying amounts in most of the melanins analysed. The same sugars were present in the HAs used for comparison, except for ribose. Some qualitative and quantitative differences observed in the two types of macromolecules would be expected, considering their origins. The results indicate that the actinomycete melanins have a qualitative sugar distribution pattern similar to that of the HAs from Brazilian tropical soils and of HAs reported for soils from other climatic regions. The possible participation of actinomycete melanins in the formation of soil humic substances is discussed. Received: 4 April 1997     

土壤碳水化合物的研究

碳水化合物是土壤有机质的组成分之一.一般认为,它在土壤良好结构的形成中起着重要的作用^[1].根据Waksman和Stevens的“近似分析法",各种土壤的有机质中,“半纤维”的含量约在5-20%间,“纤维”的含量在0-5%间^[2].但是这种方法并不能提供关于土壤碳水化合物本性方面的资料.近年来,借助于分离的方法,已经证明各种土壤中都有微生物来源的多糖存在.     

Determination of neutral sugars in soil by capillary gas chromatography after derivatization to aldononitrile acetates

We have quantified ribose, rhamnose, arabinose, xylose, fucose, mannose, glucose, and galactose in soil by gas chromatography (GC) simultaneously after converting to aldononitrile acetate derivatives. A recommended single-hydrolytic step by 4 M trifluoroacetic acid (TFA) at 105 °C for 4 h was more effective for releasing soil neutral sugars from non-cellulosic carbohydrates and better suited to our purification procedure compared with the sulphuric acid hydrolysis. Linearity of the GC detection for each neutral sugar was in the range of 10-640 μg ml⁻¹ and the recovery of neutral sugars from the spiked soil samples ranged from 76% to 109.7%. The coefficients of variation of the neutral sugars in four soils were lower than 2.0% for the instrument and 4.6-7.6% for the whole determination procedures. Compared with the trimethylsilyl (TMS) derivatization, the recovery of our newly modified method was more satisfactory and the reproducibility of ribose was improved significantly. Moreover, the aldononitrile acetate derivative was more stable than TMS derivative. Therefore, it is a promising approach suitable for a routine use in the quantitative analysis of soil neutral sugars, since it is fast, sensitive, and reproducible.     

THE ORIGIN OF SOIL POLYSACCHARIDE: TRANSFORMATION OF SUGARS DURING THE DECOMPOSITION IN SOIL OF PLANT MATERIAL LABELLED WITH 14C

Incubation of soil with ¹⁴C-rye straw for 448 days resulted in the evolution of about 50 per cent of the carbon of the substrate as CO₂ The two main sugars of the straw, glucose and xylose, were degraded to approximately the same extent (70 per cent). The same results were obtained whether the soil was derived from granitic or basic igneous parent material. There was very little transformation of the substrate to galactose, mannose, arabinose, rhamnose, or fucose, and a much slower rate of degradation than with soil incubated with ¹⁴C-glucose over a similar period. Hydrolysis of the soil samples by a preliminary treatment with 5 N H₂SO₄, before treatment with 24 N H₂SO₄, followed by heating with N H₂SO₄ did not release significantly greater amounts of sugar than treatment with 24 N H₂SO₄ and N H₂SO₄ alone. Separate analysis of the hydrolysates showed that 90 per cent of each of galactose, mannose, arabinose, xylose, rhamnose, or fucose had been extracted by 5 N H₂SO₄, but only 50 per cent of the glucose. Fractionation of the straw-soil mixture after 224 days incubation showed that the specific activity of the glucose was higher in the humin fraction than in the fulvic acid, as would be expected if the remaining ¹⁴C were still in the form of unchanged plant material. This evidence that plant polysaccharide persists in soil could explain the presence of much of the xylose in the soil organic matter.     

Studies on the properties of organic matter in buried humic horizon derived from volcanic ash

To investigate the relationship between age and the sugar composition in hydrolysates of the surface horizon and buried humic horizons with age up to 28,000 years B.P., the neutral sugars and amino sugars in soil hydrolysates were determined.

The ratios of total sugar carbon content to total carbon content of soil ranged from 2.68 to 4.13 percent. These values showed no distinct relationship with age.

Rhamnose, fucose, arabinose, xylose, mannose, galactose, glucose, g1ucosamine and galactosamine were present in the hydrolysates of all soil samples.

The polysaccharides of soil samples which have been buried for shorter periods were dominated by glucose, while those of soil samples buried for longer periods were dominated by mannose.

The proportion of hexoses showed a tendency to increase with age, while that of pentoses showed a tendency to decrease with age.     

On the effect of tetraborate ions in the generation of colored products in thermally processed glycine-carbohydrate solutions

The effect of tetraborate ions on Maillard browning was investigated in a series of monosaccharide-glycine reactions in aqueous bis-tris buffer at pH 7.2. Addition of borax (sodium tetraborate) in catalytic amounts led to enhanced browning measured by absorbance at 420 nm in the order xylose > arabinose > galactose approximately = fructose > ribose > mannose > rhamnose, and the degree of browning with borax was uniformly greater than that produced by phosphate on an equimolar basis. A mechanism is proposed for borax catalysis in which monosaccharide-borate complexation shifts carbohydrate equilibria to favor open-chain (carbonyl) forms, thereby enhancing the rate of the Maillard reaction.     

Cadmium contamination of soils and rice plants caused by zinc mining

Characteristics of heavy metal contamination in paddy soils were discussed with respect to the soil and field conditions influencing the metal contents in rice.

1. In contaminated areas along the Kuzuryu River, the heavy metal contents of rice (expressed as the average of each area) were largely related to contents of paddy soils in 0.1 N HCl soluble forms as well as in total contents. A correlation was also found for the ratio of Cd to Zn in their soluble forms in the soil.

2. Within a given contaminated field plot, the heavy metal contents were not uniform, i.e: they were high around the irrigation inlet and decreased towards the outlet. However, these changes seemed to alter the Cd rice level much less than expected.

3. Soil pH and exchangeable Ca were negatively correlated with the Cd content of rice at a highly significant level. An un-drained field condition with a low soil Eh remarkably lowered the Cd content, particularly during rainy weather after the heading of the plant.

4. Based on a comparison of the extractable heavy metal contents in the waste ores and their contaminated soils, sulfide minerals derived from the mining appeared to be weathered more rapidly in the soil. With some extraction methods, the Cd origin was distinguished as the solubility of the metal in the soil among the waste products from the zinc mining and refinery.     

Changes of lignin phenols and neutral sugars in different soil types of a high-elevation forest ecosystem 25 years after forest dieback

Long-term effects of forest disturbance 25 yr ago on lignin and non-cellulosic polysaccharide pools in an unmanaged high-elevation Norway spruce (Picea abies L. [Karst.]) forest were investigated by comparing three dieback sites with three adjacent control sites with non-infested spruce on identical soils. Samples were taken from the forest floor and the mineral soil; one Ah horizon sample per site was physically fractionated into density and particle size fractions. Additionally, changes in the above- and belowground input of lignin and non-cellulosic polysaccharides after forest dieback were quantified. Lignin and its degree of structural alteration in plant and soil samples were assessed by CuO oxidation and subsequent analysis of the lignin phenols. Non-cellulosic polysaccharides were determined after hydrolysis with trifluoroacetic acid (TFA), derivatisation of their neutral sugar monomers by reduction to alditols, and subsequent acetylation. The total plant-derived input of lignin and non-cellulosic polysaccharides to the soil was similar for the dieback and the control sites. The chemical composition of the input has changed considerably after forest dieback, as shown by significantly higher syringyl/vanillyl (S/V) ratios and significantly lower (galactose+mannose)/(arabinose+xylose) (GM/AX) ratios. This indicates a changed plant input and a higher contribution of microbial sugars. Contents of lignin phenols in the forest floor and coarse particle size fractions of the A horizons were significantly smaller at the dieback sites (p<0.01). Moreover, larger acid-to-aldehyde ratios of vanillyl units (Ac/Al)_v indicated an increased degree of lignin phenol alteration. Also contents of neutral sugars were significantly (p<0.01) smaller in the forest floor, but not in the A horizons of the dieback sites. The GM/AX mass ratios as well as the (rhamnose+fucose)/(arabinose+xylose) (RF/AX) ratios in the forest floor and coarse particle size fractions of the mineral topsoil were significantly (p<0.01) larger after forest dieback, indicating a larger relative contribution of microbial sugars. In general, the lignin phenol and neutral sugar pools of all three soil types exhibited similar response patterns to the changed site conditions. Our results demonstrate that the lignin and neutral sugar pools of humic topsoil horizons are highly sensitive to forest disturbances. However, the two compounds show different patterns in the mineral soil, with the major neutral sugar pool being stabilized against changes whereas the lignin phenol pool decreases significantly.     

The turnover of carbohydrate carbon in a cultivated soil estimated by 13C natural abundances

Understanding the chemical composition of soil organic matter (SOM) requires the determination of the dynamics of each class of compounds. We measured the dynamics of carbon in neutral carbohydrates by use of natural ¹³C labelling in an experimental wheat and maize sequence extending over 23 years. The isotopic composition of individual neutral monosaccharides was determined in hydrolysed particle‐size fractions by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) of trimethylsilyl (TMS) derivatives. The sensitivity in terms of ¹³C/¹²C ratios ranged between 1 and 2‰ depending on the monosaccharide. The age distribution of neutral sugar carbon was very similar to that of total soil carbon. Particulate organic matter (POM) was characterized by the predominance of glucose and xylose of vegetal origin. In POM > 200 µm, the mean age of sugar‐C (5 years) was slightly less than that of total carbon (7 years). Xylose was younger than glucose. The fine fraction 0–50 µm contained mainly glucose, arabinose, galactose, xylose, fucose and mannose, which had predominantly microbial origins. The mean age of carbohydrate carbon in the fraction 0–50 µm was between 60 and 100 years and was similar to that of total organic carbon (OC). No difference in the age of carbon between the individual monosaccharides was found. The POM fraction 50–200 µm had an intermediate signature and turnover. Considering the typical lability of carbohydrates, the relatively great age of carbohydrate carbon may be explained by physical or chemical protection from degradation, as well as by recycling of soil organic matter carbon by soil microbes.     

STRUCTURAL STUDIES ON SOIL POLYSACCHARIDE

The polysaccharide extracted by alkali from a Countesswells series soil has been fully methylated and the hydrolysis products identified by GC-MS. The parent neutral sugars are galactose, glucose, mannose, arabinose, xylose, fucose and rhamnose and these constitute about 40 per cent of the polysaccharide. The analysis shows that hexose components are predominantly present in 1 → 3 and 1 → 4 linkages and pentose sugar in 1 → 4 linkages. About 20 per cent of the residues were in branching positions. From the number of non-reducing terminal groups present the average molecular weight of the methylated material has been calculated to be about 1460 compared with a value of 2700 obtained by vapour pressure osmometry. This contrasts with much higher values reported for unmethylated soil polysaccharides. The mixture of derivatives obtained supports the concept that soil polysaccharide originates in both plants and microorganisms.     

Functional properties and characterization of dietary fiber from Mangifera pajang Kort. fruit pulp

A dried high fiber product from bambangan (Mangifera pajang Kort.) fruit pulp was prepared and evaluated for proximate composition, functional properties, and soluble and insoluble dietary fiber composition. Mangifera pajang fibrous (MPF) consisted of 4.7% moisture, 0.8% fat, 4% protein, and 30 mg total polyphenol per g of dry sample, and 9, 79 and 88% soluble, insoluble and total dietary fiber, respectively. Water holding capacity, oil holding capacity, swelling, and solubility were found to be 9 g/g dry sample, 4 g/g dry sample, 16 mL/g dry sample, and 11%, respectively. The glucose dialysis retardation index of MPF was approximately double that of cellulose fiber. Soluble dietary fiber contained mannose, arabinose, glucose, rhamnose, erythrose, galactose, xylose, and fucose at 1.51, 0.72, 0.39, 0.16, 0.14, 0.05, 0.04, and 0.01%, respectively, with 5.8% uronic acid, while insoluble dietary fiber was composed of arabinose (18.47%), glucose (4.46%), mannose (3.15%), rhamnose (1.65%), galactose (1.20%), xylose (0.99%), and fucose (0.26%) with 15.5% uronic acid and 33.1% klason lignin. These characteristics indicate that MPF is a rich source of dietary fiber and has physicochemical properties which make it suitable as an added ingredient in various food products and/or dietetic, low-calorie high-fiber foods to enhance their nutraceutical properties.     

Coal Fly Ash and Phospho‐gypsum Mixture as an Amendment to Improve Rice Paddy Soil Fertility

Abstract

Rice is a plant that requires high levels of silica (Si). As a silicate (SiO₂) source to rice, coal fly ash (hereafter, fly ash), which has an alkaline pH and high available silicate and boron (B) contents, was mixed with phosphor‐gypsum (hereafter, gypsum, 50%, wt wt^?1), a by‐product from the production of phosphate fertilizer, to improve the fly ash limitation. Field experiments were carried out to evaluate the effect of the mixture on soil properties and rice (Oryza sativa) productivity in silt loam (SiL) and loamy sand (LS) soils to which 0 (FG 0), 20 (FG 20), 40 (FG 40), and 60 (FG 60) Mg ha^?1 were added. The mixture increased the amount of available silicate and exchangeable calcium (Ca) contents in the soils and the uptake of silicate by rice plant. The mixture did not result in accumulation of heavy metals in soil and an excessive uptake of heavy metals by the rice grain. The available boron content in soil increased with the mixture application levels up to 1.42 mg kg^?1 following the application of 60 Mg ha^?1 but did not show toxicity. The mixture increased significantly rice yield and showed the highest yields following the addition of 30–40 Mg ha^?1 in two soils. It is concluded that the fly ash and gypsum mixture could be a good source of inorganic soil amendments to restore the soil nutrient balance in rice paddy soil.     

Carbohydrate composition of hay and maize soils and their possible importance in soil structure

The soils of three fields under continuous maize culture for 2,4 and 15 yr, and the soil of an adjacent hayfield were analyzed for carbohydrates by gas chromatography. A sharp decrease (30%) in total carbohydrates, paralleled by a smaller decrease in organic matter (9%), was observed after 2 yr of maize cultivation. The 4-yr maize soil showed an upward trend in both organic matter and carbohydrate content but this was subsequently reversed. The 15-yr highly-compacted maize soil had 40% less organic matter and 40% less carbohydrates than the hay soil. When compared to the well structured 2-yr maize soil, this compacted soil had less arabinose, xylose, glucose, galactose and mannose; carbohydrates which are probably of plant root origin. These sugars are likely to be involved in the structural stability of soil aggregates. Conversely, neither the amino sugars nor the uronic acids seemed to contribute to good soil structure.     

Monosaccharide composition of sweetpotato fiber and cell wall polysaccharides from sweetpotato, cassava, and potato analyzed by the high-performance anion exchange chromatography with pulsed amperometric detection method

The cell wall materials (CWMs) from sweetpotato (Ipomoea batatas cv. Kokei 14), cassava (Manihot esculenta), and potato (Solanum tuberosum cv. Danshaku) and commercial sweetpotato fiber as well as their polysaccharide fractions were analyzed for sugar composition by the high-performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD) method. The separation of arabinose and rhamnose, and xylose and mannose, by this method has been improved using a CarboPac PA 10 column. Pretreatment of the CWMs and cellulose fractions with 12 M H(2)SO(4) was required for complete hydrolysis to occur. Commercial sweetpotato fiber was found to be mainly composed of glucose (88.4%), but small amounts of other sugars were also detected. Among the root crops, sweetpotato CWM had the highest amount of pectin and galacturonic acid. Fucose was detected only in cassava CWM and its hemicellulose fraction, while galactose was present in the highest amount in potato CWM. Among the polysaccharide fractions, it was only in the hemicellulose fraction where significant differences in the sugar composition, especially in the galactose content, were observed among the root crops.