THE EFFECT OF SOIL FACTORS ON THE EXTRACTION OF SOIL ORGANIC MATTER BY ANHYDROUS FORMIC ACID

Twenty-five soils, having a wide range of organic matter contents, were extracted with anhydrous formic acid containing 10 per cent acetylacetone, and the extracted material precipitated in two fractions with diisopropyl ether. Precipitates comprised from 5.1 to 51.1 per cent of the original soil organic matter, the proportion extracted tending to be greatest from acid soils of fairly high organic matter content and least from neutral or slightly alkaline soils of low organic matter content. Soil clay content appeared to have no effect on the efficiency of organic matter extraction, but was the most important soil factor governing the proportion of the total soil-N extracted. Amounts of N extracted ranged from 10.2 to 57.8 per cent of the original soil N content, extraction efficiency being greatest with soils of low clay content and low pH. There was evidence to suggest that soil clay afforded some protection to N compounds against extraction. The results indicate that formic acid/acetylacetone is most effective with soils in which much of the organic matter is only partly humified.     

Amino acid composition of soil organic matter

This study investigated the amino acid composition of soil organic matter extracted from ten surface soils in addition to surface soils from two long-term cropping systems [continuous corn (CCCC), corn-soybean-corn-soybean (CSCS), and corn-oats-meadow-meadow (COMM)] at two sites in Iowa: the Clarion-Webster Research Center (CWRC) and the Galva-Primghar Research Center (GPRC). Results showed that, with the exception of asparagine pluse aspartic acid and glutamine plus glutamic acid, the other 13 amino acids studied, expressed as perecentages of total amino acids extracted, were generally very uniform among the soils. The total amino acids extracted from the ten soils were significantly correlated with organic carbon (C) ( and clay content (, but not with total nitrogen (N), pH, or sand content. Expressed as percentages or organic C and N in soils, the amounts extracted ranged from 10.9% to 32.4% and from 12.0% to 27.4%, respectively. The amino acid N identified, expressed as percentages of organic N extracted, ranged from 32% to 50% and the C/N ratios of the extracted organic matter ranged from 10.1 to 14.9. The type of rotation did not significantly affect the total amino acid content of the soils from the same N treatment, but it did affect the total amino acid content of soils from the control plots. The total amino acids measured under the different crop rotations at the CWRC site were in the order: COMM>CCCC>CSCS. The order for the GPRC site was: CSCS>COMM>CCCC. The amino acid N identified, expressed as percentages of organic N extracted from soils at the CWRC site, ranged from 33.1% to 50% and for the GPRC site ranged from 26.5% to 51.4%. The C/N ratios of the organic matter extracted ranged from 10.4 to 14.1 and from 6.5 to 14.3 for the soils from CWRC and GPRC sites, respectively. Received: 26 May 1997     

STUDIES OF SOIL ORGANIC MATTER USING FORMIC ACID SOLVENTS: FACTORS AFFECTING COMPOSITION AND DEGREE OF FORMYLATION OF ORGANIC ISOLATES

Two soils were extracted under reflux with formic acid/H₂O for 0.25 h, followed by formic acid/HF for 0.25 h. In one set of experiments ¹⁴C-labelled formic acid was used in the first extraction and unlabelled formic acid in the second: in a second set this labelling sequence was reversed. After separation from the soil residues, the soil extracts were further refluxed for up to 3.75 h. Organic matter was then precipitated from the various extracts by addition of di-isopropyl ether. Prolonged boiling of the extracts reduced the recovery of organic matter and nitrogen, and increased the inorganic contamination of the organic isolates. The degree of formylation of the isolates from the first extraction with formic acid/H₂O increased with reflux time to 0.50 h and thereafter decreased, but overall it was appreciably greater than that of the isolates from the second extraction with formic acid/HF. Formylation of the latter increased slowly with reflux time up to 4.00 h. In both solvents hydrolysis and formylation of organic solutes occur concurrently during refluxing. Treatment of formic acid/H₂O extracts with a TiCl₄/HCl/propan-2-ol reagent to precipitate organic matter and washing the precipitate in a hydrous HF medium resulted in lower yields than precipitation with di-isopropyl ether, but the final washed precipitate contained much less formyl groups and inorganic material.     

Protease extraction from soil by sodium pyrophosphate and chemical characterization of the extracts

Two arable soils and one pasture soil had previously been air-dried for 6 d and stored at room temperature. The enzyme activities remaining after this treatment were constant. The soils were then extracted with 140 mM sodium pyrophosphate at pH 7.1. Amino acid N and total organic C content of soils and soil extracts, together with humic and fulvic acids content of soil extracts were determined. Total organic C was determined in soil residues obtained after extraction. Chemical characterization of the organic matter of soils, soil extracts and soil residues was carried out by pyrolysis–gas chromatography (Py–GC). Protease activity was determined in soil extracts and soil residues by using three different substrates: N-benzoyl- -argininamide (BAA), specific for trypsin; N-benzyloxycarbonyl- -phenylalanyl -leucine (ZPL), specific for carboxypeptidases, and casein, essentially non-specific. Comparative studies between specific activities referred to organic C in soils, soil extracts and soil residues and their corresponding pyrogram composition, and also between total extracted or residual activity and the humine or unhumified organic matter content of the corresponding soil, allowed us to establish hypotheses about the type of organic matter the enzymes are associated with. From 12% to 21% of the soil organic C (33% to 39% of which were humic acids) and from 3% and 18% of amino acid N were extracted from soil using pyrophosphate. Py–GC analyses showed that pyrophosphate was effective in extracting condensed humic substances and glycoproteins and that the organic matter present in soil extracts was especially rich in intact or partially-decomposed fresh residues of carbohydrate origin and also in certain humus-associated proteins. Extracted BAA-hydrolysing activity accounted for 11% to 36% of the soil activity, depending on soil type. Extracted ZPL- and casein-hydrolysing activities were, with one exception, remarkably high, accounting for about 100% or even more of the soil activity, depending on soil type. According to the results BAA-hydrolysing proteases are probably mostly associated with highly condensed humus, ZPL-hydrolysing proteases with less condensed humic substances and casein-hydrolysing proteases with fresh organic matter.     

Free and HF-HO-extractable amino acids determined by high performance liquid chromatography in a loamy sand soil

Summary Amino acids were extracted from fertility plots of a loamy sand soil with 0.05 M HF-HCl and with a 10% ethanol solution (free amino acids) and analysed by reverse-phase high performance liquid chromatography (HPLC). The total quantities of amino-N compounds analysed were 4.4 g/g soil for the acid treatment and 22.6 g/g soil for the 10% ethanol extract. Glycine and glutamic acid were the most abundant of 15 amino-N compounds in the HF-HCl extracts, whereas glutamic acid and ornithine + NH⁺ ₄ were found in the highest concentration in the 10% ethanol extracts. The HF-HCI pretreatment is used to increase the efficiency of the extraction of soil organic matter. Although this pretreatment removed some amino acids, the acids extract less than 1% of the total amino-N content of the crude soil extracts. The pretreatment, therefore, was not overly destructive. Comparisons between the amino acids extracted from the fertility plots were not conclusive, except for glycine, which was greater in concentration in the higher fertilizer N plots of the same crop rotation.     

EFFECT OF ORGANIC CONSTITUENTS AND COMPLEXED METAL IONS ON AGGREGATE STABILITY OF SOME EAST ANGLIAN SOILS

Paired soils of high and low organic matter content from the East Anglian silts were used to determine the role of different organic constituents and complexed metal ions in relation to aggregate stability. Although leaching with periodate and borate caused some loss of stability for most of the soils, the changes were much less than those due to extraction of the soils with pyrophosphate or acetylacetone which were more effective in removing organic materials complexed with iron and aluminium. Amounts of iron and aluminium extracted were not well correlated with changes in stability. The results indicate that in these soils polysaccharides are less important to aggregate stability than organic matter bonded to the clay particles through association with aluminium or iron.     

三种黑土中有机碳、氮、磷的形态分布与肥力的关系

土壤腐殖质是土壤的重要组分。土壤的许多属性都直接或间接地与腐殖质的性质有关。我们曾指出^[2]黑土的腐殖物质及其组分与土壤的物理、化学及生物化学有显著的相关性,这表明它们对氮、磷等营养物质的转化、供应及贮存起着重要的作用。     

Chemical characteristics of glomalin-related soil protein (GRSP) extracted from soils of varying organic matter content

Glomalin is described in the literature as a N-linked glycoprotein and the putative gene product of arbuscular mycorrhizal fungi (AMF). Since the link between glomalin and various protein fractions in soil is not yet clearly defined, glomalin-related soil protein (GRSP) more appropriately describes glomalin's existence in natural organic matter (NOM). The objective of this study was to examine the chemical characteristics of GRSP present in several mineral and organic soils of varying organic carbon content. GRSP was isolated using high temperature sodium citrate extraction followed by either trichloroacetic acid (TCA) or hydrochloric acid (HCl) precipitation. GRSP was characterized by quantitative solid-state ¹³C DPMAS NMR, infrared (IR) spectroscopy, elemental analysis, and the Bradford assay for protein content. GRSP accounted for 25% and 52% of total C in the mineral soils and organic soil, respectively. Molar C/N and H/C ratios reveal that GRSP has less nitrogen than bovine serum albumin (BSA), and that GRSP extracted from the Pahokee peat soil possessed a more unsaturated, and thus aromatic character relative to the mineral soil GRSP, respectively. GRSP's high aromatic (42-49%) and carboxyl (24-30%) carbon contents and low aliphatic (4-11%) and carbohydrate-type carbon contents (4-16%) suggests that GRSP does not resemble a typical glycoprotein. In fact, the NMR spectra of GRSP closely resemble that of humic acid. GRSP extracted from mineral and organic soils possessed the same NMR fingerprint regardless of the precipitation method used (i.e., either TCA or HCl). It is likely that the current GRSP extraction methods, because of their similarity to the method used to extract humic acid, are coextracting both materials.     

The profile distribution of total and extractable zinc in selected Nigerian soils

Abstract

The profile distribution of total, DTPA‐ and 0.1 N HC1‐extractable Zn was determined in 11 Nigerian soil profiles formed on various parent Materials including the coastal plain sands, shales, basalt, granite and banded gneiss.

The total content ranged from 9 to 84 ppm. Generally soils developed on igneous rocks contained more Zn than those on sedimenatary deposits. Among the soils on sedimentary rocks, those on shale had more total Zn than those on sandstones. Total Zn was weakly correlated with organic matter but strongly associated vith clay content and free oxides of iron and manganese.

The amounts of Zn extracted by DTPA and 0.1 N HC1 ranged from 0.01 to 10.98 and from 0.23 to 6.25 ppm, respectively. The dilute acid generally removed more Zn from the soils than did the DTPA. The amounts extracted generally decreased vith depth especially vith DTFA extractant. Soils developed on basalt and shales contained the highest amounts of 0.1 N HCl‐extractable Zn while those on basement complex rocks gave the highest values of DTPA‐extractable Zn. Extractable Zn from soils on coastal plain sands remained relatively lev. The extractable Zn was more associated vith organic matter than vith clay content.     

SOIL ORGANIC MATTER STUDIES: EXTRACTION WITH FORMIC ACID/DIMETHYL SULPHOXIDE MIXTURES AND FRACTIONATION WITH Zr(IV)

Mixtures of the dipolar organic solvents formic acid (FA) and dimethyl sulphoxide (DMSO) were used to extract organic matter from soils. At 100 °C optimum extraction from a calcareous clay loam was with 80/20 v/v FA/DMSO, corresponding to a maximum in dielectric constant. Extraction of seven soils with boiling FA/H, O (107 °C) and FA/DMSO (112 °C) indicated that similar amounts of C and N are generally dissolved by the two solvent mixtures. However, FA/DMSO was about twice as efficient as FA/H₂O for the ver-miculite-rich, calcareous, organic clay loam, removing 66 per cent of its C and 54 per cent of its N. Zr(IV) hydroxide in acidic aqueous acetone was a better flocculant than Ti(IV) for the dissolved organic matter. Model compound studies, together with hydrolytic and NMR studies, indicated that Zr precipitates carbohydrate-like but not aromatic organic components. The quantity of Zr sorbed to the organic matter corresponds closely with its C.E.C. determined by Ba retention.     

有机质对红壤烤烟氮素累积分配特征的影响

利用15N示踪技术,研究了有机质含量对红壤烤烟氮累积分配特征的影响。结果表明,随着土壤有机质含量增加,烤烟氮素累积时期延长,且累积量增加。烤烟后期吸收的氮素,在低有机质含量红壤上来自土壤供氮,中有机质含量来自肥料供氮,高有机质含量来自肥料供氮与土壤供氮。烤烟吸收总氮量中29.07%~40.26%来自肥料供氮,59.74% ~70.93%来自土壤供氮,表明烤烟吸收氮素大部分来自土壤供氮。氮素在烟株不同部位分配量表现为:烟叶烟茎烟根;烟叶各部位中的分配量为:在低有机质含量的红壤,下、中、上3个部位分配量相等,中有机质含量和高有机质含量上则为上部叶中部叶下部叶。有机质含量对下部叶氮素分配量影响不大,其它部位均表现为有机质含量越高,氮素分配量越大。烤烟不同部位中肥料氮比例表现为下部叶中部叶烟根烟茎上部叶,土壤氮比例表现为上部叶烟茎烟根中部叶下部叶;并且土壤有机含量越高,各部位中土壤氮的比例越高,肥料氮的比例越低,上部叶受土壤供氮影响最大。红壤上烤烟氮肥利用率在25.42%~30.61%之间,低有机质含量土壤氮肥利用率较低,中、高有机质含量利用率相对较高。在施肥过程中,低有机质红壤上应在N 90 kg/hm2基础上适当增加氮肥施用量,中等有机质含量上保持不变,高有机质含量上应适当降低氮肥用量。     

Distribution of Zinc,Manganese, Copper,Cobalt, and Nickel in Andosols Profiles

The distribution of zinc, manganese, copper, cobalt, and nickel in Andosols was investigated. Sixty nine soil samples were collected from different horizons of an Andosols profile in Miyakonojo Basin in south Kyushu, Japan, The total contents of heavy metals were determined by digestion and four extraction solutions, 1 M NH₄Ac (ammonium acetate) pH 4.5, 0.1 M HCl, 0.01 M EDTA (ethylenediaminetetraacetic acid) pH 6.5, and 0.005 M DTPA (diethylenetri-aminepentaacetic acid) pH 7.3 were used to determine the contents of available Zn, Mn, Cu, Co, and Ni in Andosols in relation to the organic carbon content. The results of the extraction analysis showed that by the use of 0.1 M H Cl high value of extracted heavy metals in the upper layers of the humus horizons were obtained while EDTA extraction yielded a large amount of the above mentioned metals in the high humus horizons. The extractable heavy metals contents were high and these metals closely related to the organic carbon content mostly in the humus horizons in the profile. Where, biocycling process may play an important role in the concentration of heavy metals. Based on the study, it was found that the total content of Zn increased towards the C horizons or pumice layers in the soil profile. Such a trend was also found in the case of the Mn content. While the Cu content in the humus horizons was much higher in the upper part of each humus horizon. According to this study the distribution of heavy metals, Cu (organic matter complexes) in the Andosols profile was more stable than that of Zn (organic matter complexes) in soils. It was shown that Zn in the surface humus horizon was enriched but that some amount was leached under buried conditions. The same phenomenon was also observed in the distribution of Mn in the profile. The movement of Co and Ni in the soil profile was limited, as evidenced by the sharp reduction in the concentrations of these two metals in buried soils.

Hence, it is concluded that the distribution of Zn, Mn, Cu, Co, and Ni was considerably higher in the humus horizons of the Andosols profiles.     

水旱轮作条件下土壤有机无机复合状况的研究

在黄棕壤和灰潮土上进行水旱轮作条件下土壤有机无机复合状况变化的研究表明:1.水改旱有利于促进土壤有机质与土壤矿质部分的复合,增加土壤有机无机复合量,旱改水则使游离态有机质增多。2.水改旱后,土壤所复合的腐殖质中紧结态的相对较多,同时松结态和紧结态腐殖质的易氧化部分增多,能促使结合态腐殖质的氧化更新;旱改水后,松结态腐殖质相对增多,以及松结态和紧结态腐殖质的难氧化部分增多。3.水改旱后可导致土壤腐殖质组分上的差异,即HA-B/FA-B的比值升高;HA-A/FA-A的比值下降。4.水改旱后土壤碳、氮含量除细粘粒复合体中有增加外,其他粒径复合体中的都减少了,而磷、硫含量在粗粘粒和细粘粒复合体中均有明显增加,说明水改旱有利于缩短土壤有机质以及氮、磷、硫养分的循环周期,促进其易矿化性。     

Chemical fixation of ammonia to soil organic matter after application of urea

Chemical fixation of NH₃ to soil organic matter was studied in two Swedish soils with different contents of organic matter: a clay soil with 2.3% C and an organic soil with 36.6% C. ¹⁵N‐labelled urea was applied at different rates to both sterilized and non‐sterilized soils. After 10 days, the soils were extracted and washed with K₂SO₄ and determined for total N and atom% ¹⁵N excess. Urea N was recovered as non‐extractable N in sterilized soil corresponding to 9.7% of supplied ^l5N‐labelled urea in the organic soil and 2.2% in the clay soil. Since no biological immobilization is thought to occur in the sterile soil, this non‐extractable N is suggested to be chemically fixed to soil organic matter. Owing to urea hydrolysis in the clay soil, pH increased from 6.3 to 9.3 and in the organic soil from 5.7 to 6.9 and 8.8, respectively, at the low and high urea supply.     

Available organic nitrogen in temperate, subtropical, and tropical soils extracted with different solutions

Extraction of organic N by chemical solutions has been used to assess the amount of available N in soil. We tested the efficiency of several solutions in extracting organic N from tropical, subtropical and temperate soils. A conventional 0.067 M phosphate buffer successfully extracted organic N from all 23 soils examined. High-performance size exclusion chromatograms showed a single peak at about 7,800 Da for all phosphate buffer extracts irrespective of soil types. The peak area correlated with the organic N concentration of extracts. Tropical soils had lower retention of organic N than other soils according to the conventional and sequential extraction with phosphate buffer. Organic N extracted with sulfuric acid was significantly (P < 0.001) correlated with the amount of extracted Fe, suggesting that Fe might play a role in the retention of organic N in soil.     

Prediction of mineralizable nitrogen in soils on the basis of an analysis of extractable organic N

Most of the nitrogen (N) in agricultural soils is organically bound, while the N uptake by plants and also the N losses from the soil-plant system into the environment are as inorganic N. The electro-ultrafiltration (EUF) method and the extraction by a CaCl₂ solution extract an organic N fraction (Norg) that is thought to provide information about the amount of rapidly mineralizable N in soils. This paper aims to illustrate various aspects regarding the biological meaning of the Norgfractions extracted by these two extraction methods and also the opportunities and limitations for predicting the mineralizable N based on an Norg analysis. From an evaluation of numerous data on EUF and CaCl₂ extract-able Norg fractions we concluded that these methods extract N compounds which can be used as indices for easily mineralizable soil N. However, both methods extract only some of the rapidly mineralizable N in soils, and some of the Norg ecxtracted appears to be from the more recalcitrant soil organic N. This was particularly true for the EUF-method. It may therefore be desirable to improve both the extractability and the selectivity of the extraction methods. This may be achieved by measuring extractable amino-N compounds instead of the total extractable Norg. Evaluating the numerous field experiments done during the last decade shows that the calibration factors obtained for extractable Norg were not the same for different growing seasons, geographical regions and management practices. Theoretically, for each combination of these factors separate calibrations would be necessary. It is this inflexibility which appears to be the most serious drawback for the use of extractable Norg fractions in practice. A possible solution may be to combine the flexibility of a simulation model with additional information obtained by the analysis of extract-able soil organic N. Further work in this direction may be desirable.     

Amino-N compounds found in soil organic matter hydrolysates of a loamy sand using an immobilized protease reactor column

Summary Soil organic matter (OM) from seven different fertility plots of a loamy sand was extracted and fractionated into high- and low-molecular-weight (HMW, LMW) fractions using gel filtration. The fractions were acid-hydrolyzed to determine the amino sugar and amino acid contents. The same fractions were hydrolyzed with an immobilized protease reactor column. Reverse-phase high-performance liquid chromatography (HPLC) was used to identify the soil amino-N compounds. With the HMW fraction as substrate, the enzyme released less than 1% of 11 amino-N compounds determined by acid hydrolysis. Phenylalanine and leucine, however, were recovered in quantities of 2% and 4%, respectively. Immobilized protease hydrolysis of the LMW fraction recovered considerably more amino-N compounds compared with acid hydrolysis of the same fractions. Each system of hydrolysis produced some amino-N compounds not found in the other. We conclude that an immobilized enzyme reactor column will allow a researcher to perform time-course hydrolysis, so that hydrolysis intermediates, e.g. peptides, can be separated and identified.     

THE ORGANIC MATTER CONTENT OF THE SAVANNA SOILS OF WEST AFRICA

Published and unpublished data on the amounts of organic matter and nitrogen in the surface soils of the West African savanna are reviewed. In general, amounts are small; the mean carbon content of soils from 605 well-drained sites was 0.68 per cent. Two important factors governing amounts of organic matter in well-drained soils appear to be the clay content and a moisture factor related to the length of the wet season and represented here by mean annual rainfall. Multiple linear regression on soil clay content and rainfall accounted for 46.5 per cent and 57.2 per cent, respectively, of the observed variability of soil carbon and nitrogen contents. These findings suggest that the low levels of organic matter in savanna soils arise from their predominantly sandy nature and from the relatively low rainfall. In poorly drained soils organic matter levels are higher but are less significantly related to clay content and rainfall. The influence of human interference and of parent material and altitude on organic matter is demonstrated in the context of geographically limited areas within the savanna for which more detailed information was available.     

Optimizing soil dissolved organic matter extraction by grey relational analysis

Dissolved organic matter(DOM) in soil plays an important role in the fate and transport of contaminants.It is typically composed of many compounds,but the effect of different extraction factors on the abundance of different DOM components is unknown.In this study,DOM was extracted from three soils(paddy field,vegetable field and forest soils) with various extraction time,liquid to solid ratios(LSRs),extractant types,and extractant concentrations.The LSR had a significant effect on DOM content,which increased by 0.5–4.0 times among the three soils when LSR increased from 2:1 to 10:1(P 0.05).Dissolved organic matter content increased by 4%–53% when extraction time increased from 10 to 300 min(P 0.05).Extractant concentration had different effects on DOM content depending on the extractant.Higher concentrations of KCl promoted DOM extraction,while higher concentrations of KH_2PO_4 inhibited DOM extraction.Therefore,grey relational analysis was used to further quantitatively evaluate the effect of extraction time,LSR,and extractant concentration on DOM,using KCl as an extractant.For the paddy field and forest soils,the impact of these three factors on DOM extraction efficiency was in the following order:KCl concentration LSR extraction time.However,the effect was different for the vegetable field soil:LSR extraction time KCl concentration.Taking all these factors into account,1.50 mol L~(-1) KCl and an LSR of 10:1 with a shaking time of 300 min was recommended as the most appropriate method for soil DOM extraction.     

Method of extracting organic acid from flooded soil

Investigations on the extraction and determination of organic acids in flooded soil have been reported by TAKAI (1) and TAKIJIMA (2). TAKAI applied water to extract acids from soil and determined them by BULLEN's method (3). However, TAKIJIMA reported that organic acid could not be completely extracted by TAKAI's procedure, especially in soil with a high organic matter content such as muck and peaty soils, and proposed an extraction procedure with 0.5 N sulfuric acid. He also discussed the absorption of acids by soil.