Reduction of Cr(VI) by soil humic acids

The rate of hexavalent chromium reduction by a soil humic acid (SHA) was investigated in aqueous solutions where concentrations of Cr(VI), H⁺, and SHA were independently varied. Rate experiments were done with a large excess of SHA over Cr(VI). Rates of reduction depend strongly on [H⁺], increasing with decreasing pH. Typical Cr(VI)-SHA reactions display a nonlinear reduction of Cr(VI) with time that cannot be modelled with simple first- or second-order rate equations. An empirical rate equation is developed for Cr(VI)-soil humic acid reactions over a range of experimental conditions. The model is in part based on a reactive continuum concept developed for soil fulvic acids. The rate equation describing Cr(VI) reduction by SHA is: R= -(k₀+k[H⁺]^1/2)[HCrO₄^?]^1/2X_e^?1, where k₀ is (8·3 ± 1·2) × 10^?12, s^?1k is (2·04 ± 0·05) × 10^?9 l^1/2 mol^?1/2 s^?1, and X_e is the equivalent fraction of SHA oxidized. The rate equation adequately models Cr(VI) reduction in an experiment with [Cr(VI)]₀ four times greater than the maximum concentration used in its derivation. Cr(VI) reduction at pH 3 by two other SHAs can also be modelled using the rate equation. The difference between the rate coefficients for the humic acid and the fulvic acid from the same soil was greater than the difference in the rate coefficients for humic acids from different soils.     

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.     

Wechselwirkungen zwischen Boden-Huminstoffen und Metall-Ionen I. Isolierung und Charakterisierung der Boden-Huminstoffe

Interactions between soil humic substances and metal ions I. Isolation and characterization of the soil humic substances From two horizons of a podzol humic acids and fulvic acids were isolated by two different methods. The obtained samples were characterized by elemental analysis, the determination of the ash and moisture content, functional group analysis as well as FTIR-, ¹H-NMR-, and ¹³C-NMR-spectroscopic examinations. In spite of the different isolation methods humic and fulvic acids show great similarities. A higher oxidized state and a lower content of aromatic structural features are clearly observed in the fulvic acids in contrast to humic acids. Besides aromatic structural elements, distinct aliphatic sections were detected in the investigated samples, which showed a lower concentration in the less transformed fractions of the Ahe-horizon.     

Effect of continuous compost application on humus composition and nitrogen fertility of soils in a field subjected to double cropping

We investigated the effect of continuous compost application on humus composition and N fertility of soils in a field subjected to double cropping (paddy rice and barley) for 25 years. Soil samples were collected from three different plots: (a) No-NF, fertilizer containing P and K but no N; (b) F, fertilizer containing N, P, and K; and (c) F+C, fertilizer plus compost. The amounts of total humus, extracted humus, and humic and fulvic acids increased in the order No-NF<F≪F+C. The amounts of humic and fulvic acids were 2.7 and 1.7 times larger in the F+C plot than in the F plot, respectively. The degree of humification of the humic acids decreased in the order No-NF<F<F+C. The absorption curves and ¹³C-NMR spectra (TOSS method) of the humic acids indicated the presence of lignin-like structure, and its degree was the strongest in the F+C plot. The ¹³C-NMR spectra showed distinct differences in the distribution of carbon species between humic and fulvic acids. In humic acids, the content of aromatic-C, ranging from 37 to 44%, was the highest among carbon species. In fulvic acids, the content of O-alkyl-C, ranging from 45 to 51%, was the highest. The amounts of phosphate buffer-extractable N (PEON) and total N (TN) increased in the order No-NF<F<F+C. The amounts of PEON and TN were 1.2 and 1.7 times larger in the F+C plot than in the F plot, respectively. Present and previous findings indicated that continuous compost application could improve various properties of soils in a field subjected to long-term double cropping.     

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.     

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.     

Physiological action of humic substances on microbial cells

By incorporating molecular weight fractions of humic acids of various origins into selective substrates designed for the enumeration of physiological groups of microorganisms, it was found that the presence of humic acids at concentrations of up to 30mgl^?1 normally resulted in increased numbers of soil microbes active within a particular physiological group. Observed increases could be as much as 2000-fold. Microbes in an organic humus-rich soil were more stimulated by humic substances than organisms from a sandy soil.In certain microbes humic substances appeared to induce a change in metabolism, allowing the organisms to proliferate on substrates which previously they could not utilize. Indications were obtained that within the 10–30 mgl^?1 concentration range lower molecular weight humic fractions (approx. 5500 dallons) were more effective than higher molecular weight material. At higher concentrations the reverse was sometimes noticed. Similarly, fulvic acids at concentrations of up to approximately 50mgl^?1 would appear to have a more pronounced physiological effect than humic acids, whereas the latter might be more effective at higher concentrations.The response of certain physiological groups to humic products of natural origin appeared to be comparable to that of surfactants such as Tween and Brij. This would suggest that the physiological action of humic substances is, at least partly, the result of their surface activity, making the membrane one of the prime targets of the physiological action of humics on living cells.     

Effect of soil invertebrates on the formation of humic substances under laboratory conditions

The complete polymerization of phenols and proteins (one of the processes involved in the formation of humic substances) was explained. It was shown that fly (Bibio marci) larvae and earthworms (Aporrectodea caliginosa) participate in the complete polymerization of phenols and proteins. In a laboratory experiment, invertebrates participated in the degradation of organic matter and the synthesis of humic substances, which was proved in experiments with ¹⁴C-labeled phenols and proteins. The same organic substances (phenols and proteins) without the impact of invertebrates were used as the control substances. The distributions of the ¹⁴C isotope in alkaline extracts separated by solubility in acids (humic and fulvic acids) was compared to those of the control substances. The portion of the ¹⁴C isotope in the humic acids in the excrements of Bibio marci was higher than that in the control substances. The content of ¹⁴C-labeled humic substances in the excrements of the earthworm Aporrectodea caliginosa exceeded the control values only in the experiment with proteins. When clay material was added to the organic substances, the portion of the ¹⁴C isotope in the humic acids increased in both experiments with phenols and proteins. When these substrates passed through the digestive tracts of the invertebrates, the polymerization of organic substances and the inclusion of proteins and phenols into humic acids occurred.     

Acid pyrophosphate extraction of soil fulvic acids

A simple three step method is described for isolation of soil fulvic acids in high yield. The complexing agent H₂P₂O₇^2? (at pH 2) is used to release soil-bound fulvic acids. Extraction of humic acids is minimal. Selective separation of the protonated fulvic acids from the ionic extractant is achieved on a non-ionic polyacrylate resin (Amberlite XAD-7); after washing the resin, fulvic acids were retrieved in >98% yield by adjusting the pH to 6.5. Two problems associated with the classical alkali extraction method are avoided: possible alkaline oxidation of phenolic components, and their oxidation by Fe³⁺ under the acidic conditions employed to precipitate humic acids. The product typically has an ash weight of <0.6% after one XAD treatment. The method has been applied to three soils and one IHSS peat sample.     

Chemical–structural information from solid-state 13C NMR studies of a suite of humic materials from a lower montane forest soil,Colorado, USA

Chemically and physically fractionated samples extracted from the surface horizon of a soil developed under a mix of coniferous and deciduous vegetation in southwestern Colorado were studied. ¹³C NMR data on this soil's organic matter and its HF(aq)-washed residue, as well as the classic acid/base-separated humic fractions (humic acid, fulvic acid, humin), were examined for chemical–structural detail, e.g., the various structural functionalities present (especially lipids, carbohydrates, aromatics, polypeptides and carbonyl/carboxyls). Among the humic fractions, it was found that the lipid concentrations are in the order humic acid>fulvic acid= humin; for carbohydrates the order is fulvic acid>humin>humic acid; for aromatic carbons the order is humic acid>humin>fulvic acid; for polypeptides it is humic acid>fulvic acid>humin and for carbonyl/carboxyl species it is humin>humic acid>fulvic acid, but the differences are small. ¹³C spin–lattice relaxation times indicate that at least two types of “domains” exist in each, corresponding to “higher” and “lower” concentrations of paramagnetic centers, e.g., Fe³⁺.     

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.     

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.     

PROTON-DECOUPLED PULSE FOURIER-TRANSFORM 13C MAGNETIC RESONANCE OF SOIL ORGANIC MATTER

The structure of some humic acids, fulvic acids and lipid fractions of soil organic matter have been investigated by ¹³C-n.m.r. spectroscopy. Signals from aromatic groupings were normally absent in humic and fulvic acids. There were differences in spectra from extracts prepared from different sources or by different techniques. ^{1 3}C-n.m.r. spectra of lipid fractions were generally similar to each other but there were some distinct differences that may be used to a ‘fingerprint’ the lipids.     

施用生物质炭对黑土腐殖质组成及水稳性团聚体分布的影响

为探究生物炭对土壤腐殖质组成和团聚体特征的影响，以东北黑土区植烟土壤为研究对象，设置了3个处理，2019-2020年连续施用低量生物炭5t/hm2（C1）；高量生物炭25t/hm2（C2）和不施生物炭（CK），分析了不同用量生物炭对土壤腐殖质组分及水稳性团聚体分布的影响，并利用傅里叶红外光谱(FTIR)和13C核磁共振光谱(13C-NMR)对土壤胡敏酸化学结构进行表征。结果表明：C1和C2处理分别使富里酸减少了16.90%和40.85%，胡敏酸含量显著增加了14.86%和33.78%，胡敏酸在腐殖酸中所占比例（PQ值）也显著增加；FTIR和13C-NMR分析表明，C2处理的土壤胡敏酸的2920/1620值降低了11.82%，脂族C/芳香C比值降低了13.04%，表明高量生物炭使胡敏酸芳构化程度增强，脂肪结构比例降低；生物炭的添加促使土壤大团聚体（>0.25mm）比例增加，C2处理提升大团聚体的作用更显著。结合相关性分析发现，胡敏酸含量与2~0.25mm大团聚体含量显著正相关，胡敏酸分子的脂肪族官能团特征与>2mm粒级团聚体显著正相关。此外，C1和C2处理显著提高了烟叶产量。从而表明，生物炭能提升土壤腐殖质中胡敏酸含量和结构，有利于土壤大团聚体形成，提高土壤固碳潜力，对作物有一定的增产效果。     

Application of Near Infrared Reflectance Spectroscopy for the Assessment of Soil Quality in a Long‐Term Pasture

Abstract

The objective of the present study was to assess the ability of near infrared reflectance spectroscopy (NIRS) to analyze chemical soil properties and to evaluate the effects of different phosphorus (P) and potassium (K) fertilization rates on soil quality in different layers of a long‐term pasture. The NIRS calibrations were developed for humus, total Kjeldahl nitrogen (N_Kjeldahl), and several humic substances (HA1, “mobile” humic acids fraction; ΣHA, sum of humic acids; FA1, “mobile” fulvic acids; ΣFA, sum of fulvic acids, etc.) using soil samples of rather heterogeneous origin, collected during 1999–2003. Different spectral preprocessing and the modified partial least squares (MPLS) regression method were explored to enhance the relation between the spectra and measured soil properties. The equations were employed for the quality prediction of a sod gleyic light loam (Cambisol) in five PK fertilization treatments. The soil was sampled in 2000 and 2003 in three field replicates at depths of 0–10, 10–20, 20–30, and 30–50 cm, n=60 samples yr^?1. The best coefficients of correlation, R², between the reference and NIRS‐predicted data were as follows: for N_Kjeldahl, 0.965; humus, 0.938; HA1, 0.903; HA2, 0.905; HA3, 0.924; ΣHA, 0.904; and FA1, 0.911; and ΣFA, 0.885. Our findings suggest that it is feasible to use NIRS for the assessment of the effects of the inorganic PK fertilizer on the soil quality in different depths of a long‐term pasture.     

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.     

Influence of humic acids on laurel growth,associated rhizospheric microorganisms,and mycorrhizal fungi

Summary Increasing concentrations of humic acids were tested in order to determine their effects on the microbial rhizosphere and the growth of laurel (Laurus nobilis L.). Plants that were treated with 300 mg kg^-1 of humic acids had the heaviest weights of both fresh and dry shoots; however, doses of 3000 mg kg^-1 were highly phytotoxic and inhibited the growth of laurel. Total aerobic bacteria and actinomycetes were stimulated by doses of 1500 and 3000 mg kg^-1 of humic acids at the first harvest. Nevertheless, at the end of the experiment no significant differences were found among the different doses. The number of fungi living in the laurel rhizosphere was not affected by any concentration of humic acids. Vesicular-arbuscular mycorrhizal (VAM) colonization was only slightly affected by the addition of increasing concentrations of humic substances to the soil, while the hyphal growth of Glomus mosseae was reduced.     

Effects of humic and fulvic acids on growth of tobacco. 2. Tobacco growth and ion uptake 1

Experiments were conducted in growth chambers of the Phytotron to evaluate the effects of humic and fulvic acids on growth and ion uptake by tobacco plants grown to flowering.

When small amounts of humic or fulvic acids were added to media used to grow seedlings, the dry weight of roots and tops and the height of the plants subsequently grown in a nutrient solution with small amounts of humic or fulvic acids increased, while at high rates of humic acids they decreased. Generally, there was a trend for low rates of humic acids to increase concentration of Ca and Mg in roots and leaves and to decrease Fe concentration in roots.

The total content of N, K, P, Ca, Mg and Fe in the stalk and leaves increased in the presence of small amounts of humic or fulvic acids in the nutrient solution. Low rates of humic or fulvic acids in the growth medium facilitated the adsorption of Ca, Mg and Fe and their translocation within the plant. For high rates of humic acids there was a trend to decrease the total content of N, K, P, Ca and Fe in the roots and leaves of the plant.     

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.