Cyanidadsorption an Sesquioxiden,Tonmineralen und Huminstoffen

Cyanide adsorption on sesquioxides, clay-minerals and humic substances The adsorption of cyanide (KCN) on sesquioxides, clay minerals, and humic substances at different pH-values was studied. Moreover we looked for the CN-adsorption on L-layers of the humus forms mull, moder and mor. Cyanide was only adsorbed by humic acid. The amount of CN adsorbed increased with increasing pH of the reaction solution. IR-spectroscopic investigations of CN treated humic acids revealed that the cyanide was adsorbed at low pH (<7) as HCN-molecules by formation of hydrogen bonds with COOH-, COH-, OH- and NH₂-groups of the humic acid. At pH > 7 the cyanide was mainly adsorbed as CN^? by charge transfer with acceptor-molecules such as chinones. The cyanide adsorption of L-layers of humus forms decreased in the order mor > mull > moder. It is surmised that the HCN-molecules were not only adsorbed by humic acids in these layers but also by oxidation products of lignin, pectin, protein, cellulose, and carbon-hydrates of fulvic acids. Solutions of K₂HPO₄ did not desorb cyanides from humic acids to any great extent.     

Influence of natural and synthetic humic substances on the activity of urease

The activity of a purified urease, obtained from Bacillus pasteurii, was inhibited by humic and fulvic acids obtained from an agricultural soil. Enzyme kinetic studies showed that the humic substances affected the affinity of the enzyme for its substrate (K_m) and the maximum velocity of the reaction (V_max). The V_max was inhibited to the same extent by both humic (HA) and fulvic (FA) acids, the precise effect depending on the pH and concentration of humic substance. At pH 4.0, HA concentrations of 25 pg cm^?3 and 10 μg cm^?3 inhibited the V_max by 38.5% and 20% respectively. HA and FA had similar effects on the K_m but in this case the lowering of the affinity of the enzyme for its substrate was not concentration dependent in the range 0–25 μg cm^?3 of humic substance. Typically, the affinity was decreased from a K_M of 50 mM in the control to 67 mM in the presence of HA and FA. The effects were not due primarily to the ash or N contents of the humic substances because de-ashed humic acid and synthetic model humic (made from catechol, guaiacol, pyrogallol, resorcinol and protocatechuic acid) and fulvic acid (made from polymaleic acid), containing virtually no ash or N, were equally as effective. The effect was not related to the phenolic monomers which, before polymerization, had no effect on urease activity.     

The chemistry of humic and fulvic acids extracted from argentine soils—II. Permanganate oxidation of methylated humic and fulvic acids

Five humic and three fulvic acids, extracted from Argentine soils, were methylated and oxidized with KMnO* solution. The oxidation products were extracted into ethyl acetate, remethylated, separated by preparative gas chromatography and identified by comparing their mass and micro-IR spectra with those of authentic specimens.The major oxidation products from the humic acids were benzenetetra, -penta-, and -tricarboxylic and hydroxybenepentacarboxylic acid. The major compounds isolated from the fulvic acid oxidation products were aside from benzenecarboxylic and phenolic acids, substantial amounts of ethyl-benzylsulfonate and N-methyl-benzylsulfonamide, one complex aromatic ester and two anhydrides. The origin of the S-containing compounds is uncertain; they could be impurities. Weight ratios of benzenecarboxylic to phenolic acids averaged 5·8 for humic acids but only 0·9 for fulvic acids, suggesting an enrichment in phenolic structures in the fulvic acids. Possible structural arrangements for humic and fulvic acids are discussed.     

Transformation of 15N-labelled leguminous plant material in three contrasting soils

Summary Two soils from Pakistan (Hafizabad silt loam and Khurrarianwala silt loam) and one from Illinois, USA (Drummer silty clay loam) were incubated with ¹⁵N-labelled soybean tops for up to 20 weeks at 30°C. Mineralization of soybean ¹⁵N was slightly more rapid in the Pakistani soils, and after 20 weeks of incubation, 50%, 53%, and 56% of the applied ¹⁵N was accounted for as (NH₄ ⁺+NO₃ ^–)-N in Drummer, Hafizabad, and Khurrarianwala soils, respectively. Potentially mineralizable N (determined by anaerobic incubation) varied between 1.5% and 10% of the applied ¹⁵N in the three soils at different stages of incubation; somewhat higher percentages were mineralizable in the Pakistani soils than in the Drummer soil. From 3.7% to 9% of the applied ¹⁵N was accounted for in the microbial biomass. From 10% to 32% of the applied N was recovered in the humic acid and fulvic acid fractions of the organic matter by sequential extraction with Na₄P₂O₇ and NaOH; from 12% to 49% was recovered in the humin fraction. Of the three soils, Drummer soil contained more ¹⁵N as humic and fulvic acids. In all cases, the ¹⁵N was approximately equally distributed between the humic and fulvic acid fractions. A significant percentage of the humin ¹⁵N (52%–78%, equivalent to 8%–34% of the applied ¹⁵N) occurred in non-hydrolyzable (6 N HCl) forms. Of the hydrolyzable ¹⁵N, 42%–51% was accounted for as amino acid-N followed in order by NH₃ (17%–30%), hydrolyzable unknown forms (20%–22%), and amino sugars (6%–2%). The recovery of applied ¹⁵N for the different incubation stages was 87±22%. Recovery was lowest with the Khurrarianwala soil, presumably because of NH₃ volatilization losses caused by the high pH of this soil.     

Composition of organic C fractions in soils of different texture affected by sugarcane monoculture

ABSTRACT

Sugarcane is a strategic commodity in Indonesia. It is usually raised in a monoculture system. There is a lack of information about the effects of extended sugarcane monoculture on the soil carbon fraction. The aim of this study was to determine the relative changes in the soil organic C fractions in response to the duration of sugarcane monoculture on Entisols, Inceptisols, and Vertisols. The measured variables were the percentages of sand, silt, and clay, organic matter (OM), total nitrogen (TN), pH (H₂O), cation exchange capacity (CEC), NH₄ ⁺, NO₃ ^-, labile carbon fraction (soil carbon mineralization (C-Min), soil microbial carbon (C-Mic), and carbon particulate organic matter (C-POM)), and stable carbon fraction (humic and fulvic acids). Soil type with sugarcane monoculture period had significant influences on the percentages of clay, sand, silt, CEC, and pH (H₂O). Soil type and sugarcane monoculture period had no apparent significant effect on C-Min or C-POM but did significantly influence C-Mic. The humic and fulvic acid levels in all three soil types were affected by the duration of sugarcane monoculture. To establish the impact of long-term sugarcane monoculture on the physicochemical properties of soils with various textures, it is more appropriate to measure the soil stable carbon fractions such as humic and fulvic acid rather than the soil labile carbon fractions such as C-Min, C-POM, or C-Mic.     

Assessment of degradation and generation of humus in a coffee soil affected by weed cover by means of a stable carbon isotopic ratio

We evaluated the effect of soil conservation by weeds on the degradation and generation of humic acids, fulvic acids, and water‐soluble non‐humic substances (WS‐NHS) in a red‐acid soil (Vertic Dystrudept) (Indonesia) from the changes in humus composition and stable carbon isotopic ratio (δ¹³C). Three plots, a weeded plot (T‐1; the common practice), a plot covered with Paspalum conjugatum Berg., a C₄ plant (T‐2), and a plot in which native weeds were allowed to grow (T‐3), were prepared. An incubation experiment determined the δ¹³C values of the humus fractions generated from Paspalum in soil. Based on the increase in δ¹³C value, the proportion of total C that originated from Paspalum C after 4 years under coffee was 16 ± 4% in the T‐2 topsoil (0–10 cm). Humic and fulvic acids in the T‐1 topsoil decreased to 46 and 84%, respectively, whilst both increased or remained constant in the T‐2 and T‐3 soils. The WS‐NHS content varied little and was independent of land management. The preferential loss of the humic acids with a smaller degree of humification as assessed by their darkness in colour was shown in T‐1. The decrease in the degree of humification suggested the accumulation of the weed‐derived humic acids in T‐2 and T‐3. In the T‐2 topsoil, 36 ± 2%, 13 ± 3% and 15 ± 2% of C in the humic acids, fulvic acids and WS‐NHS, respectively, were estimated to be Paspalum‐derived after 4 years. The estimated initial C loss during the same period was 17 ± 3%, 14 ± 2% and 7 ± 2%, respectively, for those fractions, which suggests the fastest turnover rate for the humic acids and significant retardation of their degradation in soil colonized by weeds.     

Effects of humic and fulvic acids on release of fixed potassium

Release of potassium fixed by expanding silicate clays is considered of practical importance in soil fertility. Humic and fulvic acids are expected to play a definite role in liberating this fixed K, because of their chelating power, but not much is known in this respect. The following investigation was conducted to study release of fixed K by montmorillonite and illite, using humic and fulvic acids isolated from the surface horizon of a Cecil soil (Typic Hapludult, Red Yellow Podzolic soil) as extractants. For comparison, extraction was also done with 1 N neutral NH₄ -acetate, a mixture of 0.05 N HCl and 0.025 N H₂SO₄ or H₂ O. Supporting analyses of clays were carried out with X-ray diffraction to establish changes, if any, in crystal structure due to fixation, release of K, or adsorption of humic compounds. The results indicated that humic and fulvic acids released some of the K fixed by montmorillonite or illite. In terms of percentage of the total K fixed, 9 to 28% were released by the various extractants. The percentages K released by humic and fulvic acids were similar from both montmorillonite and illite, but based on absolute values, humic and fulvic acids extracted less K (mg/100 g) from illite than montmorillonite. Although statistically significant at the 5% level of probability, the capacity of humic compounds to liberate fixed K was not different markedly from those of NH₄ -acetate and the double acid mixture. Differences in pH of humic solutions had no influence on extraction of fixed K. X-ray diffraction analysis yielded curves showing an increase in spacing from 10.4 Å for K-montmorillonite to 13.2 Å as a result of extraction with the double acid mixture.     

Effect of soil depth on acid properties of humic substances extracted from an ombrotrophic peat bog in northwest Spain

The most southerly ombrotrophic peat bogs in Europe are in Galicia (northwest Spain). The humic matter in them originates from chemical processes in anaerobic conditions. We studied the acid properties of fulvic acids and humic acids isolated from two peat horizons of an ombrotrophic peat bog by potentiometric titration. Solutions containing 25, 50 and 100 mg l⁻¹ of each humic substance were titrated at ionic strengths 0.005 m , 0.01 m and 0.1 m (with KNO₃ as the inert electrolyte). Charge curves were analysed with a Donnan model to determine the intrinsic proton binding parameters. The concentration of the humic substance affected the charge curves more significantly at pH exceeding 6, and tended to disappear at greater concentrations. The proton binding conditional constants decreased with increasing ionic strength, this effect being more significant in the carboxylic groups with less affinity for protons. The proton binding constant of the carboxyl groups in a fulvic acid was one order of magnitude less than the value for the corresponding humic acid, whereas for the phenolic groups the values for both fractions were similar. The total content of acid groups was approximately 2 mol kg⁻¹ greater in the fulvic fraction than in the humic fraction. Both humic fractions from the lower horizon contained more acid groups than those from the upper horizon, mainly because the content of carboxyl groups increases with soil depth. Therefore, the humic substances in the lower horizon of the peat will be more negatively charged, which will affect their solubility and the binding of metal ions.     

The origin of oxygen in soil humic substances

The ¹⁸O/¹⁶O ratios of a number of soil humic and fulvic acids were measured and compared with those of lignin and cellulose samples originating from the same area. The average enrichments above ground water were: cellulose 32%₀ humic and fulvic acid 29%₀ and lignin 14%₀, suggesting that the oxygen in humic and fulvic acid originates pricipally from cellulose or other plant carbohydrates and not lignin as has been suggested.     

Sequential exhaustive extraction of a Mollisol soil, and characterizations of humic components, including humin, by solid and solution state NMR

A comprehensive sequential extraction procedure was applied to isolate soil organic components using aqueous solvents at different pH values, base plus urea (base‐urea), and finally dimethylsulfoxide (DMSO) plus concentrated H₂SO₄ (DMSO‐acid) for the humin‐enriched clay separates. The extracts from base‐urea and DMSO‐acid would be regarded as ‘humin’ in the classical definitions. The fractions isolated from aqueous base, base‐urea and DMSO‐acid were characterized by solid and solution state NMR spectroscopy. The base‐urea solvent system isolated ca. 10% (by mass) additional humic substances. The combined base‐urea and DMSO‐acid solvents isolated ca. 93% of total organic carbon from the humin‐enriched fine clay fraction (<2 μm). Characterization of the humic fractions by solid‐state NMR spectroscopy showed that oxidized char materials were concentrated in humic acids isolated at pH 7, and in the base‐urea extract. Lignin‐derived materials were in considerable abundance in the humic acids isolated at pH 12.6. Only very small amounts of char‐derived structures were contained in the fulvic acids and fulvic acids‐like material isolated from the base‐urea solvent. After extraction with base‐urea, the 0.5 m NaOH extract from the humin‐enriched clay was predominantly composed of aliphatic hydrocarbon groups, and with lesser amounts of aromatic carbon (probably including some char material), and carbohydrates and peptides. From the combination of solid and solution‐state NMR spectroscopy, it is clear that the major components of humin materials, from the DMSO‐acid solvent, after the exhaustive extraction sequence, were composed of microbial and plant derived components, mainly long‐chain aliphatic species (including fatty acids/ester, waxes, lipids and cuticular material), carbohydrate, peptides/proteins, lignin derivatives, lipoprotein and peptidoglycan (major structural components in bacteria cell walls). Black carbon or char materials were enriched in humic acids isolated at pH 7 and humic acids‐like material isolated in the base‐urea medium, indicating that urea can liberate char‐derived material hydrogen bonded or trapped within the humin matrix.     

Method for characterization of inert organic carbon in Urbic Anthrosols

Abstract

Organic matter in Urbic Anthrosols often contains chemically and biologically inert organic carbon. This material, called black carbon (BC), originates from municipal wastes, coal‐mine deposits and/or fly ash. This black carbon needs to be differentiated from the other soil organic substances because of its very different physical and chemical nature. In this paper, we propose a new method for determining BC, integrated into the humic fractionation procedure. The remaining organic carbon in the soil residue left after lipid extraction, alkaline extraction [0.5 M sodium hydroxide (NaOH)], and further oxidation with 30% hydrogen peroxide (H₂O₂) is defined as inert organic carbon or BC. The common fractions of soil organic matter, such as lipids, fulvic and humic acids, and humins are thus supplemented with a new fraction, BC. According to our results by ¹³C‐NMRspectroscopy, this fraction consists mainly of polyaromatic hydrocarbons with few functional groups.     

CHEMICAL DEGRADATION OF HUMIC AND FULVIC ACIDS EXTRACTED FROM MEDITERRANEAN SOILS

Humic and fulvic acids were extracted from two Israeli and tour Italian soils and oxidized with alkaline permanganate solution after methylation. Following oxidation, the degradation products were separated by solvent extraction and chromatographic methods and identified by gas chromatography-mass spectrometry. Major oxidation products were aliphatic, phenolic and benzenecarboxylic acids. In toto, 33 oxidation products were identified. These were essentially the same compounds as those produced by the permanganate oxidation of methylated humic and fulvic acids extracted from soils formed under widely differing climatic and geologic conditions, except that yields of phenolic acids from Mediterranean humic and fulvic acids were lower than those produced under similar conditions from humic materials extracted from other soils. The information provided by chemical degradation suggests that humic and fulvic acids from widely differing soils have similar chemical structures.     

The distribution of nitrogen in some highly organic tropical volcanic soils

The qualitative and quantitative distribution of N-compounds in 10 tropical soils, and in a number of humic materials extracted from representative samples thereof, was determined after 6 N HCl hydrolysis.Eighty to 98% of the total N in the soils and humic materials was hydrolysable by 6n HCl. Slightly less than one half the hydrolysable N in the soils and humic fractions consisted of amino acids. Well-drained soils and fulvic acids extracted from them contained unusually high concentrations of the acidic amino acids, aspartic and glutamic acids. Between 80 and 95% of the amino acids in the soils was accounted for in the humic materials + NaOH-insoluble organic residues. NH⁺₄-N released by acid hydrolysis was generally higher for the soil samples than for the humic materials. Amino sugar-N constituted relatively small proportions of the total N in the soils and humic fractions.Our data suggest that large quantities of amorphous allophanic materials coupled with relatively high enzymic activity are responsible for the observed accumulation of acidic amino acids in the well-drained tropical volcanic soils.     

Acid properties of fulvic and humic acids isolated from two acid forest soils under different vegetation cover and soil depth

We studied the acid‐base properties of 16 fulvic acids and 16 humic acids isolated from the surface (3–15 cm) and subsurface (> 45 cm) horizons of two types of acid forest soils, derived respectively from amphibolite and granite rocks, under five different types of vegetation. The observed differences between the contents of humic substances in the two types of soils were related to the degree of Al‐saturation of the soil organic matter, as indicated by the molar ratio between pyrophosphate extractable Al and C. Humic fractions were characterized in terms of elemental composition, and CPMAS ¹³C NMR spectrometry. The contents of carboxylic and phenolic groups were estimated by potentiometric titrations conducted in 0.1 m KNO₃ in a nitrogen atmosphere. The fulvic acids contained more carboxylic groups but less phenolic groups than the humic acids: the ratio of phenolic to carboxylic groups in the humic acids was 0.48 ± 0.10 and in the fulvic acids 0.23 ± 0.05. The mean values of the protonation constants of each of the humic substance fractions can be used as generic parameters for describing the proton binding properties. The fulvic acids isolated from the subsurface horizon of the soil contained between 2.6 and 23% more carboxylic groups, and the humic acids between 8 and 43% more carboxylic groups than those isolated from the surface horizon of the same soil.     

Effect of humic amendments on inorganic N, dehydrogenase and alkaline phosphatase activities of a Mediterranean soil

Dehydrogenase activity, alkaline phosphatase activity and NH₄ ⁺, NO₂ ⁻ and NO₃ ⁻ concentrations were monitored in an aridisol treated with three commercially available humic amendments. The materials were of plant residue, lignite and peat origins. The humus plant residues, fulvic acids, with a high content of Kjeldahl-N, sustained high enzyme activities and highest levels of NH₄ ⁺, NO₂ ⁻ and NO₃ ⁻. Humus lignite (mainly humic acids) produced the highest dehydrogenase activity, whereas the alkaline phosphatase activity was not as high as that amendment with humus plant residues. The lower activity of alkaline phosphatase could not be attributed to the higher P content of humus lignite. Nitrification was also low, probably due to the low N content of this fertilizer. The amendment of humus peat origin (only humic acids) did not increase enzyme activity or inorganic N concentrations of soil. Our results show that although these materials are widely utilized and recommended as microbial and plant activators, they all behave very differently, and the effects on soil microbiological activity cannot be predicted solely on the basis of their humic and/or fulvic acid contents.     

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.     

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 chemistry of humic and fulvic acids extracted from argentine soils—I. Analytical characteristics

Five humic and three fulvic acids were extracted from Argentine Chestnut, Brunizem, Solod and Solonetz soils and analysed by electrometric, spectroscopic and spectrometric methods. There were great similarities in elementary analysis, functional group content, absorption characteristics in the visible region and in the IR, and in the ESR measurements between the humic acids and, similarly, between the fulvic acids. There were distinct differences between the humic and fulvic acids in C, H, N and O content, distribution of oxygen in functional groups, E₄/E₆ ratios and free radical content.