Characterization Of Humic Substances Research Articles

Characterization of humic substances in waters and their therapeutic applications – a review

Aim: In this review, the authors characterise bioactive ingredients of humic waters, the chemical structure of humic acids and their properties, methods of their analysis and isolation. The aim of the study is also to review the application of humic waters and humic acids in different fields such as medicine and balneology. Materials and Methods: A literature review was done based on the available PubMed bibliographic database from 1994-2023. Articles in Polish and English were included. During the search the keywords such as humic waters, humic acids, peloids, balneotherapy and balneology were used. The authors also used other sources for the search, such as books and internet websites. Conclusions: Humic acids have a very high sorption capacity and a variety of biological properties including anti-inflammatory, antioxidant, antibacterial, antiviral, which can be successfully applied in different fields of medicine: dermatology, gastrology, diabetology and balneotherapy. The multitude of biological properties of humic waters and humic substances raises the question of whether or not they should be considered natural medicinal resources.

Aplicabilidad de las determinaciones de absorción en el UV-visible para la caracterización de las sustancias húmicas en ambientes acuáticos

The applicability of UV-visible absorption measurements was analyzed as a rapid and easy way for the determination and characterization of humic substances in aquatic environments taking into account their ecological meaning. Samples for these studies were taken from Río Samborombón, Arroyo Vitel and Laguna de Chascomús (Provincia de Buenos Aires, Argentina). In spite of the different absorption of humic and fulvic acids at the wavelengths employed, the method proved to be useful to account for the relative proportion of them, to make comparisons betwcen different ecosystems and to give the possibility of using it to follow the dinamycs of these substances in a given water body. In an attempt to use absorbance determinations as a measure of soluble organic matter content, correlation between Chemical oxygen demand and absorbance at 250 nm and at 365 nm was analyzed. Good results were obtained for Río Samborombón at both wavelengths, while in the other cases correlation was more significative at 365 nm.

Characterization of Humic Substances from Taiga and Tundra Soils by EPR Spectroscopy

Paramagnetic activity is a fundamental property of humic substances (HSs). The agricultural use of soils does not only affect the qualitative and quantitative compositions of HSs, but also the content of free radicals (FRs) in their structure. Changes in the composition of incoming plant residues and hydrothermal conditions have an effect on soil humification rates and the paramagnetic properties of humic (HAs) and fulvic acids (FAs). Data on the influence of various factors on the content of FRs in HAs and FAs are not enough. Therefore, the purpose of this study was to examine the influence of the degree of hydromorphism and agricultural use on the paramagnetic properties of HA and FA samples obtained from taiga and tundra soils. Studies have shown that the increased hydromorphism in taiga soils leads to the growing concentration of FRs in the HA molecular structure. HAs in virgin tundra soils exhibit a lower content of unpaired electrons when shifting from automorphic soils to hydromorphic ones. Going from the south to the north, the paramagnetic activity of both HAs and FAs tends to decrease due to the overall reduction of the number of polyconjugated systems in the tundra soil HSs. The comparative analysis of the paramagnetic properties in HAs and FAs of virgin and arable soils revealed that their agricultural use reduces the FR concentration in the structure of HSs, in other words it leads to the accumulation of biothermodynamically stable and more humified compounds in the arable horizons. This contributes to the stabilization of SOM in arable soils.

Characterization of humic substances from five macrophyte species decomposed under different nutrient conditions

Characterization of humic substances from five macrophyte species decomposed under different nutrient conditions

Characterization of Humic Substances in the Soils of Ophiocordyceps sinensis Habitats in the Sejila Mountain, Tibet: Implication for the Food Source of Thitarodes Larvae.

Humic substances in soil are considered to be an alternative food to the tender plant roots for Thitarodes larvae in the habitats of Ophiocordyceps sinensis in the Qinghai-Tibetan Plateau. However, there is no report involving the evaluation of their potential as a food source from the composition and structure of habitat soils. In this work, the composition and structure of humic substances in habitat soils from the Sejila Mountain, Tibet were characterized by diverse techniques for evaluating the nutritional value and possibility of humus as the food source for Thitarodes larvae. Fourier transform infrared spectroscopy revealed that humic acid may possess superior ability to provide the molecular segments for biosynthesizing lipids more than other humic fractions. Combining with the analysis of solid-state 13C nuclear magnetic resonance spectrum, the fractions of hydrophobic fulvic acid and hydrophilic fulvic acid are further considered as a potential food source for Thitarodes larvae. Overall, humic substances in habitat soils are rich in the molecular segments for biosynthesizing lipids and other important nutrients, which may provide the energy and material sources for maintaining the survival of Thitarodes larvae in the absence of tender plant roots, particularly in the annual cold winter. Combining with the evidence of physico-chemical parameters of habitat soils and stable carbon isotopic composition of major tender plant roots in the Sejila Mountain, the composition and structure of humic substances in habitat soils may provide a novel idea for the eco-friendly and semi-wild cultivation of Thitarodes larvae with low cost.

Characterization of Humic Substances and their Distribution of XAD Fractions by Absorption Spectroscopy in the Godavari Estuary, India

Humic substances (HS) are formed in estuarine regions by biogeochemical processes of terrestrial and in situ produced organic matters. Their structure and distribution may vary seasonally and spatially. To examine this, HS were isolated from Godavari estuarine waters using ion-exchange resins XAD-8 followed by XAD-4 during 2014-2015. The structural differences between the two fractions were characterized by E 2 /E 3 ratio (α 250 /α 365 ), spectral slope (S 275-295 ), and spectral slope ratio (S R , S 275-295 /S 350-400 ), which were derived from UV-visible absorbance spectra. Lower values of E 2 /E 3 ratio, S 275-295 and S R for XAD-8 fractions than XAD-4, indicate higher aromaticity and higher molecular weight of dissolved organic compounds retained on the former resin. The E 2 /E 3 ratio for XAD-8 and SR for XAD-4 fractions were found to decrease gradually from post-monsoon to monsoon, indicating that the biological process controls the production of organic matter in upstream waters. Lower molecular weight organic compounds formed by bacterial decay and photodegradation during pre-monsoon and higher molecular weight organic compounds formed during the post-monsoon season was attributed to the freshly exudated organic matter from phytoplanktons dominated at the mouth of the estuary.

Evaluation of optical techniques for characterising soil organic matter quality in agricultural soils

Soil organic matter (SOM) is one of the main global carbon pools. It is a measure of soil quality as its presence increases carbon sequestration and improves physical and chemical soil properties. The determination and characterisation of humic substances gives essential information of the maturity and stresses of soils as well as of their health. However, the determination of the exact nature and molecular structure of these substances has been proven difficult. Several complex techniques exist to characterise SOM and mineralisation and humification processes. One of the more widely accepted for its accuracy is nuclear magnetic resonance (NMR) spectroscopy. Despite its efficacy, NMR needs significant economic resources, equipment, material and time. Proxy measures like the fluorescence index (FI), cold and hot-water extractable carbon (CWC and HWC) and SUVA-254 have the potential to characterise SOM and, in combination, provide qualitative and quantitative data of SOM and its processes. Spanish and British agricultural cambisols were used to measure SOM quality and determine whether similarities were found between optical techniques and 1H NMR results in these two regions with contrasting climatic conditions. High correlations (p<0.001) were found between the specific aromatic fraction measured with 1H NMR and SUVA-254 (Rs=0.95) and HWC (Rs=0.90), which could be described using a linear model. A high correlation between FI and the aromatics fraction measured with 1H NMR (Rs=−0.976) was also observed. In view of our results, optical measures have a potential, in combination, to predict the aromatic fraction of SOM without the need of expensive and time consuming techniques.

Off-line TMAH-GC/MS and NMR characterization of humic substances extracted from river sediments of northwestern São Paulo under different soil uses

Humic substances (HS) vary according to the physical and chemical factors present in the environment. Thus, the characterization of HS is very important because it improves the understanding of the groups that comprise the chemical structure. Sediment HS were extracted from four locations representative of sugar cane cultivation, pasture, urban area and the impoundment of the Água Vermelha Hydroelectric Power Plant. Characterization using nuclear magnetic resonance (NMR) allowed us to infer that the HS from an area predominantly characterized by sugar cane cultivation (41.9%) and a typical rural area (35.0%) showed the highest aromaticity percentage. Using the off-line TMAH-thermochemolysis-GC-MS, we inferred that the HS of a typical rural area had a structure rich in plant waxes, plant biopolyester and a large amount of fatty acid methyl ester, which are related to the large amount of humic acid in the structure. The HS samples from the sugar cane cultivation area and the impoundment receiving all of the pollution load from the Turvo/Grande Hydrographic Basin (Bacia Hidrográfica do Turvo/Grande—BHTG) contained contributions from compounds rich in lipids and fatty acid methyl esters, highlighting the presence of the breakdown of petroleum-derived hydrocarbons in the area receiving the entire pollution load. We conclude that the HS extracted from the sediments of the Preto, Turvo and Grande rivers showed well-defined characteristics that varied depending on soil use and occupation, especially the HS extracted from sediments sampled in areas typically planted with sugar cane and rural areas, whose structures contained more aromatic groups.

Characterization of humic substances in bio-treated municipal solid waste landfill leachate

Considerable organic matter remains in municipal solid waste landfill leachate after biological treatments. Humic substances (HSs) dominate the organic matter in bio-treated landfill leachate. In this study, the HSs from landfill leachate treated by membrane bioreactor (MBR-HSs) were analyzed via elemental analysis, ultraviolet-visible spectroscopy, Fourier transform infrared spectroscopy, and charge polarized magic-angle spinning-13C-nuclear magnetic resonance. The characteristic absorption in the UV wavelength range indicated the presence of high C=C and C=O double bonds within the MBR-HSs. Compared with commercial HSs, MBR-HSs had lower carbon content [48.14% for fulvic acids (FA) and 49.52% for humic acids (HA)], higher nitrogen content (4.31% for FA and 6.16% for HA), lower aromatic structure content, and higher carbohydrate and carboxylic atoms of carbon content. FA predominantly had an aliphatic structure, and HA had less condensed or substituted aromatic ring structures than natural HA. The aromatic carbon content of MBR-HSs was lower than that of humus-derived HSs but higher than that of waste-derived HSs, indicating that MBR-HSs appeared to be more similar to humus-derived HSs than waste-derived HA.

Characterisation of humic substances formed during co-composting of grass and wood wastes with animal grease

Meat processing grease wastes were composted with lignocellulosic material. Judging by the reduction in the yield of compost lipophilic extract, grease was degraded during the first 20 days of composting. Compost humic acids (HA) and fulvic acids (FA) were characterized by elemental analysis, Fourier transform infrared (FT-IR) spectroscopy and analytical pyrolysis. The compost HA and FA fractions contained a ligno-protein complex. The presence of grease (6.7% dry weight) during composting had a slight influence on the chemical composition of HA and FA. Analytical pyrolysis indicated that, during composting, major changes were observed in the FA fraction, namely, the proportion of nitrogen-bearing compounds increased and carbohydrate-derived products decreased drastically in the final compost. In addition, the shortening of the aliphatic chains of lignin-derived compounds was observed with an increase in the C6C(0−2)/C6C3 ratio in pyrolysates.

Effects of Ozonation on Natural Organic Matter Reactivity in Adsorption and Biodegradation Processes – A Case Study: The Úzquiza Reservoir Water

In this paper the influences of preozonation on the effectiveness of NOM adsorption and biodegradation processes are studied. Three different types of water have been used in this study: A natural water from the Úzquiza Reservoir (Burgos, Spain), synthetics waters prepared using natural humic substances (fulvic and humic acids extracted from the Úzquiza Reservoir) and a synthetic water prepared using a commercially supplied humic acid. The effect of preozonation on NOM adsorption by activated carbon is evaluated: adsorption of humic acids (hydrophobic, high molecular weight compounds) is improved following preozonation; however, for the fulvic acids (hydrophilic, low molecular weight compounds), no net appreciable effect of preozonation on adsorption was observed. Preozonation increases the biodegradability of NOM: biodegradable dissolved organic carbon (BDOC), which was determined using two different bioassays (Billen-Servais method and Joret-Lévi method), increases with increasing ozone dosage. A characterization of humic substances based on their adsorption and biodegradability properties is also reported, showing the effect of ozone.

Atributos químicos, carbono orgânico e substâncias húmicas em Organossolos háplicos de várias regiões do Brasil

A dinâmica e os atributos da matéria orgânica do solo (MOS) há muito vêm sendo estudados em solos minerais. Entretanto, em condições tropicais, poucos estudos envolvem os solos orgânicos e a caracterização das substâncias húmicas (SH), ou sua relação com atributos químicos relevantes, para avaliar o potencial agrícola. Os objetivos deste estudo foram: avaliar atributos químicos de Organossolos Háplicos de diferentes regiões do Brasil; quantificar o teor de C orgânico no solo e nas frações da MOS; e avaliar as relações entre esses atributos em cada ambiente de formação. Foram avaliados os atributos químicos e quantificados os teores de C orgânico total e das frações da MOS (ácido fúlvico - C-FAF, ácido húmico - C-FAH e humina - C-HUM), bem como as relações C-FAH/C-FAF, C-EA/C-HUM, em que C-EA (carbono do extrato alcalino) é obtido pelo somatório de C-FAF e C-FAH. Os Organossolos apresentaram elevada acidez, saturação por bases abaixo de 50 % e elevada capacidade de troca catiônica potencial (T), embora com valores altos de Ca2+ e Mg2+ e de soma de bases, na maioria dos perfis. Os teores de C nas frações húmicas apresentaram correlação significativa com diferentes atributos dos solos, como entre os valores de C-FAH e de C-HUM e os teores de N, H+ e T. O C-HUM e o C-FAH predominaram sobre o C-FAF. A relação C-FAH/C-FAF foi menor nos horizontes mais superficiais, dos perfis com maior intensidade de uso ou efeito de queimadas, assim como os teores de matéria orgânica, C-HUM e C-FAH. Os atributos químicos e os teores de C nas substâncias húmicas refletiram o grau de transformação da MOS e alterações pelo uso agrícola, indicando a vulnerabilidade dos Organossolos.

Abstracts of Nippon Dojo-Hiryogaku Zasshi

Abstracts of Nippon Dojo-Hiryogaku Zasshi

Characterization of humic substances and polyacrylic acid: A high precision conductimetry study

The size and the charge of humic substances are key parameters to access their transport properties and their potential ability of complexation in the soil. The purpose of this paper is to show that high precision conductimetry coupled to a suitable transport theory give access, at various pH, to the size and charge of reference humic and fulvic acids, reference natural organic matter (NOM) and polyacrylic acids. The obtained results are compared and confirmed by two independant techniques: atomic force microscopy and dynamic light scattering. Whatever their geological origins, the studied humic acids (HA) seem to have the same charge and also the same diameter of approximately 2 nm. The pH has an effect on the effective charge of these environmental colloids but not on their size. Polyacrylic acid (5100 g/mol) can be considered as a good analogue of these humic acids concerning size and charge in solution. In comparison to these colloids, reference fulvic acid and NOM are smaller with a diameter around 1–1.5 nm and also have a lower effective charge.

Recent progresses in the analytical methods of humic substances : 3. Characterization of humic substances by thermochemolysis-gas chromatography in the presence of organic alkali

Recent progresses in the analytical methods of humic substances : 3. Characterization of humic substances by thermochemolysis-gas chromatography in the presence of organic alkali

Characterization of humic substances in landfill leachate and impact on the hydraulic conductivity of geosynthetic clay liners

A detailed characterization was performed on the humic substances present in landfill leachate derived from the older (10-year) and younger (6-month) municipal landfill cells at a site in Inchion, Korea. The characterization focused on the humic and fulvic acid components of the leachate, relying on information gleaned from the UV/visible spectroscopy, molecular weight distribution, and Fourier transform infrared spectroscopy. The effect of the leachates, and specific components of the leachates, on the hydraulic conductivity of a geosynthetic clay liner (GCL), was evaluated. The humic acid extracted from the older leachate was composed primarily of high molecular weight and aromatic compounds, which is typical for humic acids. However, the humic acid extracted from the younger leachate showed characteristics more similar with fulvic acids, indicating that the younger humic acid was at the initial stage of humification. The hydraulic conductivity of the GCLs to the humic and fulvic acids of the older and younger leachate was similar to those permeated with the distilled deionized water (DI). However, the hydraulic conductivity of the samples tested with the raw leachate was more than 200 times the DI value. This fact suggests that cations present in leachate, rather than humic substances, are the key factor in the increase of the permeability.

Characterization of humic substances in salt marsh soils under sea rush ( Juncus maritimus)

Humic substances (HS) from salt marsh soils were characterized and the relationships among HS composition and some geochemical factors were analysed. For this, three salt marshes with the same vegetation cover ( Juncus maritimus), but with different geochemical characteristics, were selected. The qualitative characterization of the soil humic acids and fulvic acids was carried out by elemental analysis, FTIR spectroscopy, fluorescence spectroscopy and VACP/MAS 13C NMR spectroscopy. HS from salt marsh soils under sea rush ( Juncus maritimus) displayed some shared characteristics such as low degree of humification, low aromatic content and high proportion of labile compounds, mainly polysaccharides and proteins. However, although the three salt marsh soils under study were covered by the same type of vegetation, the HS showed some important differences. HS composition was found to be determined not only by the nature of the original organic material, but also by environmental factors such as soil texture, redox conditions and tidal influence. In general, an increase in the humification process appeared to be related to aerobic conditions and predominance of sand in the mineral fraction of the soil, while the preservation of labile organic compounds may be associated with low redox potential values and fine soil texture.

Development of an automated system for isolation and purification of humic substances

Characterization of humic substances (HS) in environmental samples generally involves labor-intensive and time-consuming isolation and purification procedures. In this paper, the development of an automated system for HS isolation and purification is described. The novelty of the developed system lies in the way the multiple liquids and columns used in the isolation/purification procedure are handled in both forward and back-elution mode by solenoid valves. The automated procedure significantly reduces the total throughput time needed, from 6-7 days to 48 h, and the amount of labor to obtain purified HS for further characterization. Chemical characterization of purified HS showed that results were in good agreement with previously published values for HS from a variety of sources, including the IHSS standard HS collection. It was also shown that the general properties of HS were consistent among the different source materials (soil, waste, aquatic) used in this study. The developed system greatly facilitates isolation and characterization of HS and reduces the risk of potential (time-dependent) alteration of HS properties in the manual procedure.

High-performance size-exclusion chromatography of humic substances on the hydroxyethyl methacrylate column

HEMA, the copolymer of 2-hydroxyethyl methacrylate and ethylene dimethacrylate, has proven to be a suitable stationary phase for the size-exclusion chromatographic (SEC) characterization of humic substances in a wide pH range. The SEC measurements were performed typically with alkaline borate-based mobile phase: 0.025 mol/l Na 2B 4O 7, 0.025 mol/l NaCl, 0.001 mol/l Na 4P 2O 7, pH 9.1. After calibrating with globular protein standards, apparent molecular weights of typical peat- and coal-derived humic acids were estimated. The average molecular weights determined with the aid of the HEMA column were quite comparable with the values obtained previously by the method of low-pressure gel-permeation chromatography on the Sephadex column.

Reduction in vegetative growth of the water mold Saprolegnia parasitica (Coker) by humic substance of different qualities

Humic substances (HS) account for 50–80% of the dissolved organic matter in non-eutrophicated freshwater ecosystems. HS are not inert, but are taken up by and may interact with aquatic organisms. However, at present no information is available on the interaction of HS with fungi, for instance, the fish-pathogenous species Saprolegnia parasitica. To fill this gap, we tested effects of HS on S. parasitica growth in-vitro using 25–500 mg L −1 carbon of HS on GY-agar. We investigated 20 HS including natural organic matter (NOM) samples, two lignite derived HS, and one synthetic HS. The aim was (1) to find out, if there are inhibiting effects and (2) if potential effects can be explained by humic matter properties by structure activity relationships. The growth of S. parasitica was related to the growth on HS-free agar controls. Characterization of HS and NOMs included elemental analysis, high-pressure size exclusion chromatography (HPSEC), UV/VIS, FTIR-, and EPR-spectroscopy in order to obtain information on elemental and structural composition including various metals, molecular weights of the HS fraction, aromaticity, free organic radicals, and functional groups. NOMs with high moieties of high-molecular carbohydrates supported the growth of S. parasitica, all other HS and NOMs reduced it. However, no inhibition of the development of the sporangia and primary zoospores was found. Therefore, the impact of the HS on S. parasitica has to be classified as fungistatic, rather than fungicidal. Synthetic and lignite-derived HS were among the most efficient HS sources. Growth inhibition was correlated ( p < 0.05) with the molecular weights of the HS-fraction, sUVa, COOH groups, C and H. Our results suggest that especially HS with higher molecular weights and aromaticity which contain a high number of organic radicals are the most efficient in reducing fungal growth. Furthermore, highly functionalized HS seem to be important for the observed effect. The development of internal oxidative stress could be a mechanism explaining the observed growth inhibition of S. parasitica.