RADIOCARBON DATING OF PALEOSOLS USING SOIL ORGANIC MATTER COMPONENTS

Soil organic matter components of classical humic acid and humic fractions were extracted from two paleosols using 0.1 M Na₄ P₃ O₂:0.1 M NaOH. These fractions were subjected to chemical treatment with 6 M HC1 or 70 per cent HNO, before radiocarbon assay, and their radiocarbon dates were compared with those of similar but untreated fractions, untreated buried soils, and previously published charcoal dates. Hydrolysis of humic acid and humin fractions with mineral acids, particularly 70 per cent HNO₃ led to older radiocarbon dates, comparable to, though slightly older than, those of charcoal derived from the same buried layers. In contrast, the dates of soils and their humic acid and humin fractions before acid hydrolysis were younger and therefore less reliable. The application of this procedure to studies of paleosols in New Zealand is discussed.     

EXPERIMENTAL CONDITIONS CONCERNING POTENTIOMETRIC TITRATION OF HUMIC ACID

The humic acids of four soils from Denmark have been extracted by EDTA. The humic acids were separated from EDTA by precipitation with Ba²⁺. The ash content was lowered by treatment with HF and HC1. The ash content in the four humic acids was less than 0.6 per cent. Chemical analysis of the humic acids supply some evidence for the suggestion that EDTA extracted organic matter is a more definite fraction than humic acid extracted by NaOH. It was shown that an alkaline humate solution stored in sterile, sealed ampoules under N₂ does not change its initial pH, indicating that the protolytic equilibrium is established instantly. It is therefore proposed that the titration of humic acid should be carried out as quickly as a normal acid-base titration.     

CHANGES IN THE CHEMICAL NATURE OF SOIL ORGANIC PHOSPHATE DURING PEDOGENESIS

In two chronosequences of soils, total organic phosphate (P₀) accumulated rapidly during the first 50 years of soil development, when organic matter increased and pH decreased. The rate of P₀ accumulation then declined with age of soil until a ‘steady state’ was reached. The amounts of phospholipid, inositol phosphates and humic acid—P₀ followed the same trends as the total P₀. Parent materials and very young soils contained largely citric acid-soluble P₀, but after less than 50 years, surface horizons accumulated sufficient organic matter to complex a considerable proportion of the P₀. An upper limit of 20–5 per cent citric acid-soluble P₀ and 70–80 per cent NaOH-soluble P₀ was attained within 50 years of soil formation in the surface layers, and this slowly extended down the profile so that, after 10000 years, the soil had 20 per cent citric acid soluble-P₀ and 70 per cent NaOH-soluble P₀ to a depth of 1 m.     

The distribution of PG (green fraction of P type humic acid) and the degree of humification of PB (brown fraction of P type humic acid) in soils of central Japan

Abstract

Pg contents of soils chosen from the major soil groups occurring in the mountain area of Central Japan were measured by the method presented by the author in a previous paper. The Pg contents of the soils ranged from 0 to 0.58 per cent of the dry soils. In podzolic soils, Pg contents were high in A horizons and gradually decreased with depth and in some cases of brown forest soils, Pg contents were highest in B horizons. The percentage of Pg in humic acid ranged from 0 to 8.6 per cent, and the highest value was observed in the C horizon of Dando Bo soil, Pg contents were high in humid and acidic soils containing much humic acid. Humidity, soil pH and humus content may affect the Pg accumulation by controlling the activity of Pg-producing fungi. ? log K values of Pb were calculated to estimate the degree of humification of P type humic acids and indicated that Pb's were relatively immature.     

Further investigations on the chemistry of fungal “humic acids”

In view of the considerable interest in laboratory-prepared fungal “humic acids” as possible precursors or incorporated structural components of soil humic substances, we degraded four fungal “humic acids” by the relatively mild alkaline cupric oxide oxidation. The oxidation products were extracted into organic solvents, methylated, separated by thin-layer chromatography and identified on a gas chromatographic-mass spectrometric-computer system.Average yields of major degradation products were: (a) aliphatic compounds, 38 per cent; (b) benzene-carboxylic compounds, 25 per cent; and (c) phenolic compounds, 21 per cent. The remaining 16 per cent consisted of a number of dialkyl phthalates. Our data agree with those that we reported earlier when we degraded a number of fungal “humic acids” by the more drastic alkaline permanganate oxidation and show that fungal “humic acids” are enormously complex organic materials containing aliphatic and aromatic structures, (some of which contain N), but only a relatively small proportion of which is phenolic. Most of the aliphatics isolated consisted of alkanes and fatty acids, which are known to persist in soils over long periods of time and are frequently firmly retained by soil humic substances.     

THE ACCUMULATION OF SOIL ORGANIC MATTER AND ITS CARBON ISOTOPE CONTENT IN A CHRONOSEQUENCE OF SOILS DEVELOPED ON AEOLIAN SAND IN NEW ZEALAND

Soil organic matter was extracted by a mixture of O.IM Na₄P₂O: O.IM NaOH from a chronosequence of weakly weathered soils developed on aeolian sand, and fractionated into humin (non-extractable), humic acid, and fulvic acid. The mass of total organic carbon in the profiles, the ¹⁴C content and the ¹³C/12C ratios were also determined. The weight of total carbon increased rapidly at first and then gradually without attaining a steady state. This trend was also shown by the humin and fulvic acid fractions, but the humic acid fraction appeared to have reached a maximum after about 3000 years. The order of total weights of the organic fractions was humin > fulvic acid > humic acid. The evidence suggests that the proportions of the humic fractions formed by decomposition are related to soil differences but not to vegetation. The greater part of the plant material found in the soils appears in the humin and fulvic acid fractions.     

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。     

ADSORPTION OF HERBICIDE-DERIVED p-CHLOROANILINE RESIDUES IN SOILS: A PREDICTIVE EQUATION

Relationships between the adsorption of p-chloroaniline and the original adsorbate concentration were investigated for five soils ranging in organic matter content from 1.7 to 8.1 per cent and in clay content from 0.5 to 21 per cent. Adsorption data were analyzed applying the linear form of the Freundlich equation. To evaluate the general relationship between adsorption of p-chloroaniline by soils and the solution concentration (C₀), values of partition coefficient (Kp), reflecting the magnitude of distribution of chemical at equilibrium between soil colloids and solution were calculated. The experiments showed that the regression parameters were significantly correlated with the soil organic matter content. A comparison of the experimental results obtained with other soils and the calculated values gave satisfactory agreement.     

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.     

覆膜对有机物料的腐解及土壤有机质特性的影响

砂滤管长期培养试验结果表明,有机物料和农肥施入土壤后,腐解残留率(Yt)与有机物料施入后的时间(t)遵循Yt=Y^λ.t_oe方程式,式中Yo为有机物料缓分解成分的碳理占加入总碳量的百分数,λ为缓解成分的分解速率。覆膜使Yt和Yo值明显降低。田间试验结果表明,覆膜降低了有机质的活性,使PQ值(胡敏酸占可提取腐殖酸的百分数)和A2/A3比值(胡敏酸在波长200nm和300nm处吸光度之比)增高,胡敏酸对光吸收增强。     

SOME EFFECTS OF FERTILIZERS AND FARMYARD MANURE ON THE ORGANIC PHOSPHORUS IN SOILS

The amounts of P applied cumulatively to a neutral arable soil (pH 7.1–7. in 0.01M CaCl₂) at Rothamsted, as farmyard manure, alone or with superphosphate, which were converted to organic P in 100 years ranged from 18 to 44 μg P/g of soil (0–23 cm). Superphosphate alone (3300 kg P/ha) slightly lessened the total organic P in the soil. Neither farmyard manure nor super-phosphate significantly changed the amounts (38 to 42 μg P/g) of inositol penta- and hexaphosphate in these soils. In the surface layers (0–7.5 cm) of soils from permanent grassland at Rothamsted, superphosphate (3370kg P/ha) increased organic P by 134 μg P/g at pH 4.5 and 19 μg P/g at pH 6.5, about 6 and 1 per cent respectively of the P remaining from superphosphate applied cumulatively since 1858. In the sub-surface layers (7.5–23 cm) superphosphate increased organic P by 93 μg P/g at pH 4.5 and 62 μg P/g at pH 6.2, about 18 and 10 per cent respectively of the P remaining from superphosphate. The sum of inositol penta- and hexaphosphates accounted for 32 per cent at pH 4.5 and 21 per cent at pH 6.5 of the increases in organic P in the surface layers and 45 per cent and 26 per cent in the sub-surface layers at pH 4.5 and 6.5 respectively. Superphosphate (1260–2100 kg P/ha) applied intermittently or cumulatively increased total organic P by 19 to 52 μg P/g and inositol penta- and hexaphosphates by 13 to 17 μg P/g in acid tea soils (pH 3.2–3.4) from Georgia, U.S.S.R. Rock phosphate (510–1020kg P/ha) applied cumulatively had no effect on either the total organic P or the inositol P in acid tea soils (PH 3.6–3.7) from Ceylon.     

CONTENT OF INOSITOL PENTA- AND HEXAPHOSPHATES IN SOME CANADIAN SOILS

The combined amounts of inositol penta- and hexaphosphates in a number of Canadian soils of differing origin have been measured. The esters were precipitated as barium salts from alkali extracts and purified by anion-exchange chromatography; their identity was confirmed by paper-partition chromatography. An alternative method involving precipitation of the esters as ferric salts in acid medium was found to give much lower values, probably because of incomplete precipitation. Values for eighteen surface soils ranged from 20 to 71 and for twelve subsoils from 18 to 43 ppm P. The amounts found were related to the contents of both total phosphate and total organic phosphate, and accounted, on average, for 6 per cent of the former and 17 per cent of the latter. A correlation of +0.67 (P < 0.01) was found with orthophosphate retention capacity but correlations with soil N and C contents were poor. Amounts of the esters were higher in forest soils than in grassland soils.     

Decomposition and distribution of residual activity of some 13C-microbial polysaccharides and cells,glucose, cellulose and wheat straw in soil

Studies were made to determine the rate of decomposition of some ¹⁴C-labeled microbial polysaccharides, microbial cells, glucose, cellulose and wheat straw in soil, the distribution of the residual ¹⁴C in various humic fractions and the influence of the microbial products on the decomposition of plant residues in soil. During 16 weeks from 32 to 86 per cent of the C of added bacterial polysaccharides had evolved as ¹⁴CO₂. Chromobacterium violaceum polysaccharide was most resistant and Leuconostoc dextranicus polysaccharide least resistant. In general the polysaccharides, microbial cells, and glucose exerted little effect on the decomposition of the plant products. Upon incubation the ¹⁴C-activity was quickly distributed in the humic. fulvic and extracted soil fractions. The pattern of distribution depended upon the amendment and the degree of decomposition. The distribution was most uniform in the highly decomposed amendments. After 16 weeks the bulk of the residual activity from Azotobacter indicus polysaccharide remained in the NaOH extracted soil. From C. violaceum polysaccharide both the extracted soil and the humic acid fraction contained high activity. About 50–80 per cent of the residual activity from the ¹⁴C-glucose, cellulose and wheat straw amended soils could be removed by hydrolysis with 6 n HCl. The greater part of this activity in the humic acid fraction was associated with the amino acids and that from the fulvic acids and residual soils after NaOH extraction with the carbohydrates. About 8 16 per cent of the activity of the humic acid fraction was present in substances (probably aromatic) extracted by ether after reductive or oxidative degradation.     

THE OCCURRENCE OF COPPER-PORPHYRIN COMPLEXES IN SOIL HUMIC ACIDS

Electron paramagnetic resonance (e.p.r.) spectroscopy has been used to show that humic acids, which were isolated from a range of soils and from which most of the iron was removed by boiling with hydrochloric acid, contain copper in the form of porphyrin complexes. The amounts of porphyrin-bound copper in the acid-boiled humic acids were estimated to be ≤ 20 mg/kg (equivalent to 0.05-0.9 mg/kg in the soils). The acid-boiled humic acids from cultivated mineral soils showed no great capacity for further uptake of copper as copper porphyrin when treated with CuSO₄, most of this additional copper being held by groups not involving N-donor groups. In contrast, copper treatment of the acid-boiled humic acid from a raised bog peat produced a large increase in copper-porphyrin signal strength, indicating that in the peat there are considerable amounts of porphyrin by which added copper could be complexed. It is suggested that porphyrin groups may be involved in the fixation of copper by organic matter in soils.     

Alkaline cupric oxide oxidation of a methylated fulvic acid

Fulvic acid, (FA), extracted from the Bh horizon of a Podzol soil, was methylated and then oxidized with alkaline cupric oxide. The oxidation products were extracted into organic solvents, remethylated and separated by column-, thin layer-, and preparative gas chromatography into relatively pure components, which were identified by matching their mass and i.r. spectra and gas Chromatographic retention times with those of authentic specimens.The degradation products isolated and identified accounted for approximately 18 per cent of the weight of the initial methylated FA. Major oxidation products were: (a) methylated phenolic aldehydes and esters (66.9 per cent): (b) benzenecarboxylic acid methyl esters (14.6 per cent): (c) aliphatic dicarboxylic acid methyl esters (2.7 per cent): and (d) adsorbed materials such as n-alkanes (0.3 per cent), n-fatty acid methyl esters (0.3 per cent) and dioetyl adipate (15.2 per cent). The oxidalive degradation of methylated FA indicates the presence of two types of basic structural units: (1) those yielding phenolic aldehydes and esters, and (2) those producing benzenecarboxylic acids. Alkaline cupric oxide oxidation of methylated FA is relatively selective for the isolation of the phenolic components and appears to be a promising technique for structural investigations on humic substances.     

ELECTRON-SPIN RESONANCE OF HUMIC ACIDS FROM CULTIVATED SOILS

An examination has been made of the electron-spin resonance spectra of humic acids from (i) two groups of cultivated soils from the north-east of Scotland, and the related natural soils from which the cultivated soils are considered to be derived, and (ii) some Rothamsted soils. With the Scottish soils the humic acids from the more acid natural soils (pH <4.6) show e.s.r. spectra with a four-peak structure (class I), and those of the less acid soils (pH >4.6) almost structureless spectra (class II). The cultivated soils contain humic acids with the same class of spectrum as that of the soils from which they are derived, even though they are now much less acid (_PH 5.9 –6.5). Humic acids from Rothamsted soils, sampled recently, were compared with those from the same site sampled 80 years previously. Where the soil has been allowed to revert towards a natural state but still contains free calcium carbonate the pH remained high (7.8–7.9) and the spectrum of the humic acid remains class II. Where the soil contained no free calcium carbonate the pH has fallen from 7.1 to 4.5 on reversion and the spectrum class of the humic acid has changed from II to I. The results support the hypothesis that the class of spectrum of the humic acid depends on the pH at which it is formed.     

MOLECULAR WEIGHT DISTRIBUTION OF SOIL ORGANIC MATTER AS AFFECTED BY ACID PRE-TREATMENT AND FRACTIONATION INTO HUMIC AND FULVIC ACIDS

Effects of acid pre-treatment and fractionation on the molecular weight distribution of OIM Na₄P₂O₇ organic matter extracts were investigated in a chronosequence of weakly weathered soils developed on aeolian sand in New Zealand. Acid pre-treatment of soils with OIM HCl followed by OIM HCI:03M HF was found to enhance the polydispersion in the nominal molecular weights of the extracts. The same treatment resulted in significant increases in yield and reduction in ash content. However, prolonged standing of extracts in the acids led to acid-induced polymerization, resulting in a predominance of organic matter in the higher nominal molecular weight ranges. Fractionation of organic matter extracts by acid precipitation into humic and fulvic acids did not separate them according to molecular weight as commonly believed. Instead, fulvic acids from most soils were found to have similar nominal molecular weight distributions to those of their humic acid counterparts. A large proportion of soil fulvic acid compounds was in the > 100 000 nominal molecular weight range.     

SULPHUR, CARBON, AND NITROGEN CONTENTS OF ORGANIC FRACTIONS FROM ACETYLACETONE EXTRACTS OF SOILS

Ultrasonic dispersion of acid-pretreated soils in aqueous acetylacetone at pH 8, and at a solvent: soil ratio of about 45: I, extracted from 61 to 97 per cent of the organic sulphur from five Scottish soils. Narrowing the ratio to about 9:1 reduced the proportion extracted but was more convenient for the subsequent isolation of the organic components. Gel permeation chromatography of the extracts yielded materials containing from 14 to 60 per cent of the soil organic sulphur. Most of the soils gave four distinct fractions which contained from 21 to 38 per cent carbon, 0.2 to 2.1 per cent nitrogen, and 0.1 to 0.8 per cent sulphur. There was no consistent similarity between corresponding fractions of the various soils. Considerable amounts of iron and aluminium were extracted, presumably incorporated in organic complexes. Since they were obtained under very mild conditions, the fractions should provide useful starting materials for qualitative investigations on the nature of soil organic sulphur.     

THE HUMIC ACIDS EXTRACTED BY VARIOUS REAGENTS FROM A SOIL

Solutions of o.5N NaOH, o.1M pyrophosphate (pH 7), and o.5N Na(CO^2?₃/HCO^?₃) [2:1] extract humic acid and organic matter from a soil with decreasing effectiveness. Pre-treating the soil with o.1N HC1 increased the yield of humic acid obtained with the alkaline extractants. An additional pre-treatment with a mixture, which was normal with respect to HC1 and HF, gave a slight reduction in yield. Increasing the temperature of extraction increased the yield of humic acid. The total C extracted was usually in excess of the humic acid recovered. The difference was obtained as ‘humins’. The sum of the Fe₂O₃, SiO₂, and A1₂O₃ contents of the humic acids was always less than 2 per cent. Where the extraction was carried out at room temperatures the SiO₂/Al₂O₃ ratio suggested that they might be present as clay mineral. When extraction was carried out at an elevated temperature this ratio was altered. Humic acids of low ash content (0.1–0.5 per cent) could be obtained by the use of hot reagents. Of all the extractants used at room temperature, pyrophosphate produced the humic acid of lowest ash content (～ 0.2 per cent). The Fe₂O₃ content of the humic acids was not correlated with their SiO₂ or A1₂O₃ content. The N-content of the humic acids was substantially independent of the method of extraction. The cation-exchange capacities (C.E.C.), average pK values and range of pK values, have been determined from the titration curves of the humic acids. These quantities vary with the method of extraction. There are good correlations between cation exchange capacity and both average pK values and the range of pK values. The within-molecule variation of pK values appears to be greater than the between-molecule variation. No correlation exists between C.E.C. and Fe, Al, Si, and N content of the humic acids.     

THE VOLATILISATION, FROM SOILS AND MIXTURES OF SOIL COMPONENTS, OF IODINE ADDED AS POTASSIUM IODIDE

Iodine, as potassium iodide in solution, was added to samples of 24 surface soils, 15 subsoils and 16 mixtures of sand with other materials representing soil components, at 10 μg iodine/g soil. The extent of volatilisation of the added iodine was measured after 30 days' exposure in a well-ventilated room. With many of the surface soils volatilisation was negligible although with an acid sandy podsol it amounted to 57 per cent of the iodine added. Eleven of the subsoils induced volatilisation amounting to > 10 per cent of that added. With sand alone, having a pH of 5.7, volatilisation amounted to 100 per cent, and with the mixtures it ranged from nil to 100 per cent. Organic matter reduced volatilisation, probably by retaining the iodine in bound form. Montmorillonite, kaolinite and ferric oxide also reduced volatilisation in comparison with sand alone, but had less effect than did organic matter. Calcium carbonate, although in general reducing volatilisation, probably through its influence on pH and hence on retention by other materials, caused no reduction when added to sand alone.