Physico-chemical characteristics of humic substances of major soil associations of Bihar (India)

Humic acid (HA) and fulvic acid (FA) extracted from fourteen surface soil samples (0–20 cms) belonging to nine major Soil Association Groups scattered over different agro-climatic situations, were characterized by elemental and functional group analysis, E₄/E₆ ratios, coagulation behaviour and distribution of carbon in different soil humus fractions. The E₄/E₆ ratio of FA extracted from different soils was wider than that of HA. The coagulation behaviour of HA and FA fractions and also of cultivated and forest soils showed marked differences. The variations in the ratios of HAC:FAC (0.31 to 1.0) among different soils were indicative of the degree of humification under the influence of vegetation and agroclimatic conditions. The elemental composition of HA and FA, in general, indicated a higher carbon and nitrogen content and C/N ratio in the former than in the latter fraction. On the contrary, the oxygen content of FA was higher compared to that of HA. The carbon contents of HA extracted from the cultivated and forest soils of Hazaribagh were almost equal, as were also the carbon contents of HA from the cultivated and forest soils from Ranchi. Total acidity of FA of the soils selected in the present study was higher than that of HA. The functional groups such as carboxyl, phenolic hydroxyl and carbonyl were present in the two fractions in varying proportions.     

Comparison between UV spectroscopy and Nirs to assess humification process during sewage sludge and green wastes co-composting

The humification of organic matter during composting was studied by the quantification and monitoring of the evolution of humic substances (Humic Acid-HA and Fulvic Acid-FA) by UV spectra deconvolution (UVSD) and near-infrared reflectance spectroscopy (NIRS) methods. The final aim of this work was to compare UVSD to NIRS method, already applied on the same compost samples in previous studies. Finally, UVSD predictions were good for HA and HA/FA (r² of 0.828 and 0.531) but very bad for FA (r² of 0.092). In contrary, all NIRS correlations were accurate and significant with r² of 0.817, 0.806 and 0.864 for HA, FA and HA/FA ratio respectively. From these results, HA/FA ratio being a well-used index of compost maturity, UVSD and NIRS represent two invaluable tools for the monitoring of the composting process. However, we can note that NIRS predictions were more accurate than UVSD calibrations.     

Interactions of Cu (II) and Fe (III) with mangal humic substances studied by synchronous fluorescence spectroscopy and potentiometric titration

Humic (HA) and fulvic (FA) acids isolated from mangrove sediments of Sundarban, the largest delta on earth in the estuarine phase of the river Ganges, were studied and attempts were made to characterize their binding sites by quenching of Synchronous fluorescence (SyF) bands with Fe (III) and Cu (II). A modified Stern-Volmer relationship applicable for static quenching was applied for the determination of conditional stability constants and the data were compared with those determined by potentiometric titration. In the excited state HA and FA showed different acidity constant compared to the ground state. Values of the conditional stability constant (log K_c) for Fe (III) and Cu (II) indicated that binding sites were bidentate in nature. FA were better chelators than the HA fractions. High energy binding sites of both FA & HA were occupied by Fe(III) and the low energy binding sites, mainly responsible for mobilization and immobilization of metal, were occupied by Cu(II).     

Electrofocusing the compost organic matter obtained by coupling SEC-PAGE

Humic acids (HA)-like extracted from compost at the beginning (t(0)) and after 130 days of composting (t(130)) were fractionated by coupling size exclusion chromatography to polyacrylamide gel electrophoresis (SEC-PAGE). HA-like fractions with the same molecular size (MS) and electrophoretic mobility were pooled and further characterised by analytical polyacrylamide gel electrofocusing (EF) and compared with HA separated from a Typic Chernozem soil. During the composting process all fractions were subjected to quantitative and qualitative modifications: the high MS fraction was degraded, the mid MS fractions were qualitatively changed, the content of low MS fractions increased and changed qualitatively. The main changes in EF pattern of the non fractionated HA-like t(130) were associated to low MS fractions. Such data seem to be reliable for explanation what mechanisms and monitoring of the evolution of the compost organic matter for their agricultural uses.     

Transformation of organic matter during co-composting of pig manure with sawdust

Co-composting of pig manure with sawdust was studied in order to characterize the organic transformation during the process, using both chemical and spectroscopic methods. Humic acids (HA) and fulvic acids (FA) were fractionated from immature and mature pig manure compost, and characterized. After 63 days of composting, the ratio of total organic carbon and soluble organic carbon decreased to a satisfactory low level and the solid and soluble C/N ratios decreased rapidly for the first 35 days before attaining a constant value, indicating compost maturity. Humification could be responsible for the increase in humic acid proportion during composting. The increase in the aromatic bonds after composting, as indicated by the reduction of C/H and C/O ratios of HA and FA, resulted in a more stabilized product. A substantial increase in high molecular weight compounds along with a small increase in low molecular weight compounds was found in mature compost. Moreover the HA also had more complex organic compounds at this stage. Fluorescence spectral analysis showed an increase in the maximum wavelength of HA associated with the contents of aromatic structures in solution. A decrease in relative absorbance of HA at 1160 cm(-1), 2950 cm(-1) and 2850 cm(-1) was seen in the FTIR spectra indicating the decomposition of complex organic constituents, into simpler ones. Increase in the aromatic compounds with higher stability could account for the relative increase in the absorbance of HA at 1650 cm(-1) and 1250 cm(-1) of the mature compost. The composition of FA was not much altered, indicating most of the degradation of organic matter occurred in HA. Data from organic carbon, C/N ratio, elemental analysis, E(4)/E(6) ratio, gel chromatography, fluorescence and FTIR spectra indicated an increase in polycondensed structures and the presence of more stable organic matter in the mature compost.     

Monitoring of green waste composting process based on redox potential

Among compostable matrices, green wastes represent a significant fraction which can be used as an amendment after composting. Several indicators, e.g. C(HA)/C(FA) or C/N ratios give information on evolution of the organic matrix during composting. However, measurement of these parameters is complex and requires laboratory conditions. The aim of this study was to propose on site easy-to-measure parameters to monitor composting process, such as redox potential (Eh), related to complex indices such as C(HA)/C(FA), C/N, A(210 nm)/A(280 nm), NH(4)(+)/NO(3)(-) ratios, and total organic matter (OM). Windrows were consisting in a mixture of green wastes such as palm, olive, cypress, pine, mimosa, and bay residues. By using covariance analysis, an opposite correlation between Eh and C(HA)/C(FA) ratio was found. Linear regression of this parameter with Eh was chosen to monitor the composting process. Therefore, Eh can be used to monitor green wastes composting.     

Influence of humic substances on bioavailability of Cu and Zn during sewage sludge composting

Influence of humic substances (HS) on bioavailability of Cu and Zn was characterized during 120 days co-composting of sewage sludge and maize straw. At the initial stage of composting, Cu and Zn in sewage sludge were released as organic matter was degraded, and water soluble Cu and Zn increased markedly. Water soluble Cu and FA content decreased after 21 days whereas water soluble Zn increased during the whole process. Both HA-Cu and HA-Zn were significantly and positively correlated with HA and H/F, respectively. At the end of composting, the distribution coefficients of HA-Cu and HA-Zn reached 27.50% and 3.33% respectively with HA-Cu/HA-Zn ratio increased from 1.29 to 2.73. The results suggest that Cu combined with HA more strongly than Zn, and composting treatment could decrease bioavailability of Cu markedly.     

Microbiological parameters as indicators of compost maturity

AIMS: The objectives of this study were to determine the changes of microbial properties of pig manure collected from pens with different management strategies and composted using different turning and moisture regimes; relate their association with humification parameters and compost temperature; and identify the most suitable microbial indicators of compost maturity. METHODS AND RESULTS: Six different microbial parameters, including total bacterial count, oxygen consumption rate, ATP content, dehydrogenase activity, and microbial biomass C and N, along with humification parameters [humic acid (HA), fulvic acid (FA) and HA : FA ratio] and compost temperature were monitored during composting. Significant positive correlations were found between temperature and microbial properties, including O2 consumption rate, ATP content, dehydrogenase activity, and microbial biomass N. The humification parameters also showed significant correlations with microbial properties of the manure compost. For instance, HA contents of pig manures was positively correlated with total aerobic heterotrophs, and microbial biomass N and C; and negatively correlated with O2 consumption rate, ATP content, and dehydrogenase activity. Among the six microbial parameters examined, dehydrogenase activity was the most important factor affecting compost temperature and humification parameters. Composting strategies employed in this study affected the speed of composting and time of maturation. If the moisture content is maintained weekly at 60% with a 4-day turning frequency, the pig manure will reach maturity in 56 days. CONCLUSIONS: The composting process went through predictable changes in temperature, microbial properties and chemical components despite differences in the initial pig manure and composting strategies used. Among the six microbial parameters used, dehydrogenase activity is the most suitable indicator of compost maturity. Compared with respiration rate, ATP content and microbial biomass procedures, dehydrogenase activity is the simplest, quickest, and cheapest method that can be used to monitor the stability and maturity of composts. SIGNIFICANCE AND IMPACT OF THE STUDY: The results presented here show that microbial parameters can be used in revealing differences between composts and compost maturity. The statistical relationship established between humification parameters and microbial parameters, particularly dehydrogenase activity, demonstrates that it is possible to monitor the composting process more easily and rapidly by avoiding longer and more expensive analytical procedures.     

Effects of the maturity of wood waste compost on the structural features of humic acids

An analytical scheme for the separation of humic substances (HSs) and non-humic substances (non-HSs) was established to estimate the humification index (HI), which was defined as the ratio of HS carbon content to non-HS carbon content. The alkaline compost-extract contained a mixture of HSs and non-HSs, while acidification of the compost-extract resulted in precipitation of humic acid (HA). The acidified supernatant contained fulvic acid (FA) and non-HSs. In the present study, DAX-8 resin was used to separate FA and non-HSs. HI values, which were estimated to evaluate the maturity of wood waste compost, increased with composting duration. To determine the effects of compost maturity on HA structural features, correlations between HI and indicators of the degree of HA humification (atomic ratios, acidic functional group contents, spectroscopic parameters and molecular weight) were investigated. HI values were significantly related to the indicators of the extent of HA humification during composting.     

Chemical characterization of humic substances extracted from organic-waste-amended soils

Humic substances were extracted from a soil treated, in a 4-year experiment, at different rates with a sludge from anaerobic treatment of combined civil and industrial wastes, and with agricultural manure. Elemental and chemical analyses, molecular weight (MW) distribution and infrared (IR) spectroscopy were performed on the purified humic acids (HA). Organic wastes significantly increased the HA content of the treated soils and improved CEC. The C/N, C/H and C/O ratios of HA extracted from the original wastes showed a higher degree of humification for sludge than for manure. This difference was also noticed for the C/N ratio of soil humic extracts, indicating a faster humification process for the sludges in soil. The content of oxygen-containing functional groups was lower than the ‘model’ HA reported in the literature, and even more so for HA from sludges, reflecting their anaerobic formation. MW distribution and E₄/E₆ ratios showed that the sludge material had a higher molecular complexity than manure, supporting the high degree of humification attributed to the former. HA extracted from sludge-treated soils revealed a molecular dimension increasing with the application doses of waste material. Infrared spectra showed that HA formed in soils after waste additions reflected the chemical composition of the original organic material, which was rich in aliphatic groups and peptides for sludge and in carbohydrates for manure. On the basis of this study, it is concluded that not only are organic waste additions able to build up the HA content in soils but the HA formed assume the chemical characteristics and the degree of humification of the original material.     

The effect of humic substances on germination and early growth of Lamb’s Quarters (<Emphasis Type="Italic">Chenopodium album</Emphasis> agg.)

In order to understand the biological activity of humic substances (HS), the effect of four humic acids (HA) and one fulvic acid (FA) on seed germination and early growth of cosmopolitan weed Chenopodium album agg. were tested. Humic substances of diverse origin were used, namely purified commercial HA, HA isolated from lignite, cambisol and podzol, and FA from mountain spruce forest soil. Data processing by two-way ANOVA has shown that type of the tested substances was a more important factor on seed development than used concentration. The major differences in germination and length of shoots were found in the first days of the experiment. Commercial and lignite HA stimulated the seed germination and growth, while podzol HA inhibited them. After this initial phase, all humic substances stimulated the seed development, but these stimulations were not significant (P < 0.05). At the end of germination test, the greatest stimulation effect (up to 20%) was achieved with the lignite HA.     

The influence of topography on the nature of humic substances in soil organic matter at a site in the Atlantic Coastal Plain of South Carolina

The effect of topography on the nature of humic substances, isolated as water soluble organic carbon (WSOC), fulvic acid (FA), and humic acid (HA) was evaluated by comparing relative proportion and chemical characteristics of these fractions in upland and bottomland Coastal Plain soils in South Carolina. The fractions were characterized by elemental analysis and¹³C cross-polarization magic angle spinning nuclear magnetic resonance (CPMAS NMR) spectroscopy. The majority of humic substances occur as humic acids, with bottomland soils having higher HA/FA ratios when compared to upland soils. We found no significant differences between upland and bottomland humic substances with respect to yields of WSOC and fulvic acids, and in the C and N content of humic and fulvic acids. Carbon-13 CPMAS NMR spectroscopy revealed that the WSOC and fulvic acid fractions were composed largely of O-alkyl-C structures with bottomland soils having higher amounts of these groups. Humic acid C distribution was similar between upland and bottomland soils and was largely composed of aromatic groups. Our results demonstrate that topography influences the formation of humic acid and the structural and chemical properties of the various humic fractions.requests for offprints     

Organic matter transformations and kinetics during sewage sludge composting in a two-stage system

The use of different proportions of rape straw and grass as amendments in the composting of dewatered sewage sludge from a municipal wastewater treatment plant was tested in a two-stage system (first stage, an aerated bioreactor and second stage, a periodically turned windrow). The composition of feedstock affected the temperature and organic matter degradation in the bioreactor and the formation of humic substances, especially humic acids (HA), during compost maturation in the windrow. The total HA content (the sum of labile and stable HA) increased according to first-order kinetics, whereas labile HA content was constant and did not exceed 12% of total HA. Δlog K of 1.0–1.1 indicated that HA was of R-type, indicating a low degree of humification. Temperature during composting was the main factor affecting polymerization of fulvic acids to HA and confirmed the value of the degree of polymerization, which increased only when thermophilic conditions were obtained.     

Differential decomposition of humic acids by marine and estuarine bacterial communities at varying salinities

Humic substances (HS) constitute 50–80% of total dissolved organic matter (DOM) in freshwaters but in the open ocean <3%, indicating that large fractions of DOM and HS are removed in the estuarine and coastal zone. In order to assess the role of bacteria in this removal, we conducted experiments in flow-through cultures to examine the decomposition of peat bog-born humic acids (HA) by marine (salinity 30, Exp1) and estuarine (salinity 10, Exp2) bacterial communities. After ~70 days 40–>60% of the HA were decomposed. Highest fractions were decomposed in treatments in which the bacterial communities were fed by HA media of a foreign salinity, e.g., of 14 in Exp1 and of 28 in Exp2. Some of the HA material was not decomposed but broken down to smaller moieties entering the fulvic acid (FA) fraction. The analysis of the HA media and their residuals after bacterial decomposition by pyrolysis GC/MS showed that individual organic compounds were decomposed. In Exp1, 32 aliphatic and aromatic compounds, including lignin biomarkers, were detected in the HA medium of which mainly aliphatic compounds were decomposed. In Exp2, 49 compounds were detected of which ~40–60% were not detected any more after bacterial decomposition in the HA fraction but still in the FA fraction. The results show that estuarine and marine bacterial communities can decompose large amounts of HA and that this process is important in reducing the amount of terrestrial HS and DOM entering the estuarine and coastal region.     

Chemical and structural evolution of humic acids during organic waste composting

The effects of the composting process on the chemical and structural properties of humic acids have been studied in seven different organic waste mixtures from different origin. Only slight changes in elemental composition have been found in the humic acids after the composting process pointing to a more aromatic structure with higher proportions of oxygen and nitrogen. Functional groups were the most sensitive to the changes caused by the composting process showing a marked increase in the total acidity and phenolic, carboxyl and carbonyl groups. Gel permeation chromatography showed a slight increase in the average molecular weight of the humic acids. Infrared spectroscopy did not show important differences in humic acid structure but a clear decrease in the intensity of the bands in the region 3000–2850 cm^-1 corresponding to the aliphatic fractions. As a general result, the composting process yields humic acids in which the elemental and functional composition are closer to that of the more humified soil humic acids.     

Description of characteristics of humic substances from different waste materials

Humic acids (HAs) extracted from different organic wastes have been characterised by chemical methods. The chemical properties of HAs showed differences depending on the source from which they were obtained. The C content in HAs from organic wastes (41.1-63.2%) fluctuated around the C value in soil HA with the exception of composted bark and tobacco dust. Compared with soil HA, the N contents of HAs from sewage sludge and brewery sludge were found much higher than the others. E4:E6 ratios for HAs in organic wastes were generally greater than that for soil HA, which indicated a low degree of condensation and humification. The carboxyl and phenolic-OH group contents ranged 0.51-2.23 and 11.1-20.7 meq g(-1), respectively. High values of carboxyl and phenolic-OH contents indicated that these materials were still within early stages of humification.     

Study on dynamic changes of microbial community and lignocellulose transformation mechanism during green waste composting

There are few reports on the material transformation and dominant microorganisms in the process of greening waste (GW) composting. In this study, the target microbial community succession and material transformation were studied in GW composting by using MiSeq sequencing and PICRUSt tools. The results showed that the composting process could be divided into four phases. Each phase of the composting appeared in turn and was unable to jump. In the calefactive phase, microorganisms decompose small molecular organics such as FA to accelerate the arrival of the thermophilic phase. In the thermophilic phase, thermophilic microorganisms decompose HA and lignocellulose to produce FA. While in the cooling phase, microorganisms degrade HA and FA for growth and reproduction. In the maturation phase, microorganisms synthesize humus using FA, amino acid and lignin nuclei as precursors. In the four phases of the composting, different representative genera of bacteria and fungi were detected. Streptomyces, Myceliophthora and Aspergillus, maintained high abundance in all phases of the compost. Correlation analysis indicated that bacteria, actinomycetes and fungi had synergistic effect on the degradation of lignocellulose. Therefore, it can accelerate the compost process by maintaining the thermophilic phase and adding a certain amount of FA in the maturation phase.     

Snow vole (Chionomys nivalis Martins) affects the redistribution of soil organic matter and hormone‐like activity in the alpine ecosystem: ecological implications

In alpine environments, colonies of snow vole (Chionomys nivalis Martins) cause strong pedoturbation, which may affect humification process and soil organic matter (SOM) cycling, with repercussions on the hormone‐like activity of organics. We investigated the effect of snow vole pedoturbation on the chemical and spectroscopic features of soil organic fractions, and the potential hormone‐like activity of humic and fulvic acids (HA, FA). The study site was located on the high‐mountain environment of the Majella massif (central Italy). Pedoturbated and regular soils were morphologically described and characterized for pH and content of total organic carbon, total extractable carbon, HA, and FA. Both HA and FA were extracted and investigated using attenuated total reflectance/Fourier transform infrared (ATR/FTIR), nuclear magnetic resonance with high‐resolution magic angle spinning (HRMAS‐NMR), and ¹H‐¹³C heteronuclear single quantum coherence (HSQC). HA and FA were also tested for their auxin‐like and gibberellin‐like activities. Results provide evidences that bioturbated and regular soils contain a poorly decomposed SOM, but HA and FA with a well‐defined molecular structure. The HA and FA from both bioturbated and regular soils show a hormone‐like activity with a different allocation along the soil profile. In the regular soil, the highest auxin‐like activity was shown by HA and FA from Oe1 horizon, while gibberellin‐like activity was expressed by FA from Oe2 horizon. Burrowing activity determines a redistribution of organics throughout the profile with a relatively high auxin‐like activity in the FA from straw tunnel wall (STW) and gibberellin‐like activity in the HA from vole feces (VF). The relative high presence of carboxylic acids, amides, proteins, and amino acids in the FA from STW and the aromatic moieties in the HA from VF put evidences for their different behavior. The fact that snow vole activity has modified the chemical and biological properties of SOM in these soils otherwise considered governed only by low temperature has important ecological implications such as the preservation of soil fertility and vegetal biodiversity.     

Molecular-sieve chromatography of humic substances extracted with chelating resin from chernozemic Ah horizons

Summary Humic substances extracted with chelating resin from a Dark Brown Chernozem (Typic Haploboroll) Ah, a Black Chernozem (Udic Haploboroll) Ah, and a Dark Gray Luvisol (Typic Cryoboralf) Ahe were fractionated by Bio-Gel P. The eluted material was combined to form three or four fractions for further characterization.Most of the extracted polydisperse humic substances of the three soils were eluted near V₀ and distributed around a single mean value. The ash content of this material varied from 1.36 to 1.78 per cent. Carboxyl acidity may thus be obtained without interference from any cations.The humic substances from the Dark Brown and Black Chernozem Ah gave similar elution profiles, whereas those from the Dark Gray Luvisol Ahe were less aliphatic and more aromatic in nature. The materials of low molecular weight had the highest content of ash, C, and carboxyl groups. They represented only 3.6 to 14.1 per cent of the C extracted and were considered, on the basis of increased C content, decreased optical density, and infrared spectral configurations, to consist of polynuclear, fused-ring, aromatic structures.     

广泛性焦虑障碍血清25-羟维生素D、维生素B12与认知功能和临床疗效的关系

摘要 目的：探讨广泛性焦虑障碍（GAD）患者血清25-羟维生素D[25（OH）D]、维生素B12（VB12）与认知功能和临床疗效的关系。方法：选择2018年4月~2022年6月期间空军军医大学第一附属医院心理科门诊收治的186例GAD患者作为GAD组。另选取同期于我院体检健康的志愿者120例作为对照组。采用威斯康星卡片分类测验（WCST）评估并对比两组患者的认知功能，检测并对比两组患者的血清25（OH）D、VB12水平。采用Pearson相关性分析血清25（OH）D、VB12与认知功能的相关性。GAD组给予常规治疗，按照治疗效果分为有效组和无效组，对比有效组和无效组在治疗前后血清25（OH）D、VB12水平变化。结果：GAD组的血清25（OH）D、VB12水平低于对照组（P<0.05）。对照组完成总分类数、正确反应数、总反应数均多于GAD组，错误应答数、持续性错误数少于GAD组（P<0.05）。Pearson相关性分析结果显示，血清25（OH）D、VB12水平与错误应答数、持续性错误呈负相关；而与总分类数、正确反应数、总反应数呈正相关（P<0.05）。186例患者中，痊愈36例，疗效显著53例，有效62例，无效35例。按照治疗情况将患者分为有效组（n=151）和无效组（n=35）。两组治疗后血清25（OH）D、VB12水平均升高，且有效组高于对照组（P<0.05）。结论：GAD患者的25（OH）D、VB12水平下降，且与其认知功能下降有关，25（OH）D、VB12水平较低的GAD患者其治疗效果也相对更差，提示临床诊疗过程中应密切关注患者25（OH）D、VB12水平以制定相应的治疗措施。