Changes In Humic Acids Research Articles

Characterization of the volatile fraction of laboratory-generated aerosol particles by thermodenuder-aerosol mass spectrometer coupling experiments

An aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) combined with a thermodenuder (TD) was used to investigate laboratory-generated aerosol particles with regard to their volatility and chemical content. The performance of the setup was tested first by using ammonium sulfate particles. Organic compounds have been measured including humic acid, fulvic acid, succinic acid and its disodium salt, 2-methylsuccinic acid, fumaric acid, α-ketoglutaric acid, and glutaric acid. Among them, humic acid, fulvic acid, and disodium succinate show a non-volatile fraction at 300 °C, while the other organic compounds are more volatile. Comparisons of mass spectra at different temperatures showed that significant differences in mass spectra of humic and fulvic acids are observed, indicating that their molecules changed during or after volatilization. At lower temperatures, the changes in humic acid are more likely due to the evaporation of small organic molecules or decomposition of aliphatic groups. The mass losses of the CO 2 + fragment for both humic and fulvic acids at higher temperatures may arise from decarboxylation processes. The different mass spectra for humic and fulvic acids before and after TD also suggest that one should be careful in interpretation of volatility measurements because some molecule structures may change after being heated, especially for the non-volatile multifunctional compounds.

Spectroscopic behaviour of 14C-labeled humic acids in a long-term field experiment with three cropping systems

The stabilisation of 14C-labelled farmyard manure was investigated under different cropping systems (crop rotation, monoculture, and bare fallow) in a long-term field experiment established in 1967. Solid-state 13C-NMR of bulk soils yielded a gradient of increasing aromatic properties in the order: straw manure–crop rotation < straw manure–monoculture < straw and farmyard manure–bare fallow. The opposite trend was observed for O-alkyl groups. The farmyard manure–bare fallow treatment was used to investigate changes of humic acids (HAs) with time. The FT-IR bands of aromatics, carbonyl groups, and a band of methyls and benzene rings increased over the 36 years of the experiment, whereas 2 amide bands and a band of sulfone and/or ester groups decreased. Fluorescence spectroscopy verified the increase in aromatic properties with age. Consequently, during soil organic matter stabilisation, HAs showed increasing properties of carbonyl and aromatic groups, whereas amidic groups decreased. The dynamic character of HAs, as shown by 14C, was also reflected by distinct spectroscopic changes over the period of investigation.

Analysis of humic acids from various soils using acid hydrolysis

Structural changes in humic acids from various soils, produced by acid hydrolysis, are studied by elemental and thermal analyses and by IR and NMR spectroscopy.

Humic Acid Fractionation upon Sequential Adsorption onto Goethite

Mineral-humic complexes are commonly distributed in natural environments and are important in regulating the transport and retention of hydrophobic organic contaminants in soils and sediments. This study investigated the structural and conformational changes of humic acid (HA) and mineral-HA complexes after sequential HA adsorption by goethite, using UV-visible spectroscopy, high performance size exclusion chromatography (HPSEC), Fourier transform infrared (FT-IR) spectroscopy, and solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. The HA remaining in the solution after adsorption showed low polarity index values ((N+O)/C), which indicates that polar functional moieties are likely to adsorb on the goethite surface. In addition, we observed decreased E4/E6 and E2/E3 ratios of unbound HA with increasing number of coatings, implying that aliphatic rich HA fractions with polar functional moieties readily adsorb to the goethite surface. According to IR spectra, carbohydrate carbon would be the important fractions associated with goethite. NMR spectra provided evidence for HA fractionation during adsorption onto the mineral surface; that is, aliphatic fractions were preferentially adsorbed by goethite while aromatic fractions were left in solution. Relatively small molecular weight (MW) HA fractions had a greater affinity for the goethite surface based on analyses of the HPSEC chromatograms, which differs from the results reported in the literature. Finally, our results suggest that the polar aliphatic fractions of HA were mainly adsorbed to goethite via electrostatic attraction and/or ligand exchange reactions.

Bioconversion of Wastes from the Olive Oil and Confectionary Industries: Spectroscopic Study of Humic Acids

Structural changes in humic acids extracted from composted mixtures of sesame bark with the paste of olive mill wastewater or exhausted olive cake, were investigated using FTIR spectroscopy and solid state 13C CP/MAS techniques. The C/N ratio and organic matter degradation decreased significantly after 6 months of composting. The FTIR spectra of humic acids content showed an increase in the aromatic compounds content and a degradation of aliphatic chains. During composting, nuclear magnetic resonance 13C spectral analyses confirmed that aromatic groups exhibited a slight increase while the aliphatic groups decreased and disappeared at the end of the composting process. These results showed that during composting, aliphatic chains were preferentially oxidized, while aromatic macromolecules were bio converted into highly functionalized compounds.

Temporal changes in humic acids in cultivated soils with continuous manure application

Although the application of manure to upland fields is believed to induce changes in the quality of humic substances in soil as well as the quantity, the direction and extent of these changes have not been elucidated. To understand temporal variations in humic acids, periodically collected soil samples from two fields, a Typic Hapludult (Togo) and a Pachic Melanudand (Kuriyagawa), with cattle manure and chemical fertilizer (CF) were examined. The content and degree of humification (darkening) of the humic acids were distinctly greater in Kuriyagawa than in Togo soil. Corresponding to the difference in the degree of humification, molecular size distribution, elemental composition, infrared (IR) spectra, and 13C cross polarization/magic angle spinning nuclear magnetic resonance (CPMAS NMR) spectra of humic acids differed between the two soils. Manure application at 40 Mg ha−1 year−1 for 16 years (Togo) and at 80 or 160 Mg ha−1 year−1 for 19 years (Kuriyagawa) resulted in greater humic acid content compared with plots with CF only because of its increase in the manured plots and/or decrease in the CF plots. Manure application at an extremely high rate (160 Mg ha−1 year−1) resulted in higher H content and greater signal intensities of alkyl C, O-alkyl C and amide C=O in the 13C CPMAS NMR and/or IR spectra. Although humic acids with larger molecule sizes increased in all the manured plots, differences between the humic acids from the plots with and without manure applied at practical levels in the elemental and spectroscopic analyses were small or scarce. These results were considered to be because of the similarity between the indigenous soil humic acids and the manure-derived ones in Togo soil (a low degree of humification) and because of the abundance of highly-humified humic acids in Kuriyagawa soil.

Characterization of Soil Organic Carbon in Long‐Term Amendment Trials

In the current study, total organic carbon (TOC) analysis and spectroscopic characterization (IRMS, DRIFT, and SERS) are applied to investigate the molecular changes in humic acids (HA) extracted from soil samples amended for more than 30 years with cattle manure (CM), cow slurries (CS), and crop residues (CR). All samples are compared to the unamended (T) sample. A variation in soil TOC percentage occurs in all samples, but a significant (P<0.05) accumulation of C is observed only in CM. The TOC δ 13C values appeared progressively less negative in all samples with respect to T. The DRIFT and SERS analyses of HA revealed a change in oxygenate groups (such as COO− and OH) in the amendment with CS and CR. These results suggest how amendment might affect both C accumulation and the HA structure. This paper was by special invitation as a contribution to a special issue of the journal entitled “Application of Spectroscopic Methods to Environmental Problems.” The special issue was organized by Professor Peter A. Tanner, Professor in the Department of Biology and Chemistry at City University of Hong Kong.

Evaluation of humic acid photocatalytic degradation by UV–vis and fluorescence spectroscopy

Photodegradation of humic substances causes drastic changes in the UV–vis absorption and fluorescence properties of humic acids. In this study it is intended to fulfill the lack of knowledge about the spectral changes of humic acids during photocatalytic oxidation process es and elucidate the effects observed on the molecular size distribution of humic acid focusing on their analysis by UV–vis and fluorescence spectroscopy. As confirmed by the spectroscopic evaluation of the molecular size distribution data, photocatalytic degradation of humic acid leads to the formation of lower molecular size (small fractions) and higher UV absorbing compounds. For fractions less than 10 kDa, UV 254 absorbing moieties in treated humic acid samples become higher than that of raw humic acid designating the generation of new species during photocatalysis. UV–vis spectroscopic changes were also evaluated by the parameters relating to the concomitant removal of the total organic carbon as well as by the ratios using absorption values at discrete wavelengths. Moreover, the fluorescence spectra of treated humic acid samples show decreasing intensity profiles with increasing photocatalytic irradiation time.

Structural changes in lipid-free humic acids during composting of sewage sludge

Structural changes in humic acids (HAs), extracted after lipid removal from sewage sludge during composting, were investigated using various chemical methods (elemental analysis, Fourier transform infrared spectroscopy and 13C-nuclear magnetic resonance (NMR) spectroscopy). Compared to non-purified HAs, lipid-free HAs (LFHAs) exhibit higher C and N contents and high absorbance around 1652, 1540 and 1230 cm1, which indicates the intensity of the etherified aromatic structures and nitrogencontaining components. Less absorbance around 2920, 1600, 1414 and 1100 cm1 could be assigned to their low level of aliphatic compounds, mainly those with a carboxyl group. According to 13C-NMR spectroscopy, almost 45% of aliphatic structures are removed by lipid extraction and these correspond mainly to long-chain fatty acids. During composting, significant decomposition of non-substituted alkyl structures and N-containing components occurred, increasing the relative intensity of etherified aromatic structures.

Structural and Sorption Characteristics of Adsorbed Humic Acid on Clay Minerals

Clay-humic complexes are commonly distributed in natural environments. They play very important roles in regulating the transport and retention of hydrophobic organic contaminants in soils and sediments. This study examined the structural changes of humic acid (HA) after adsorption by clay minerals and determined phenanthrene sorption by clay-humic complexes. Solid- and liquid-state 13C nuclear magnetic resonance (NMR), for the first time, provided direct evidence for HA fractionation during adsorption on mineral surfaces, that is, aliphatic fractions were preferentially adsorbed by clay minerals while aromatic fractions were left in the solution. The ratio of UV absorbance of HA at 465 and 665 nm (E4 to E6 ratio), which is related to aromaticity, corroborated with the NMR results. For both montmorillonite and kaolinite, adsorbed HA fractions had higher sorption linearity (N) and affinity (K(oc)) than the source HA. The K(oc) of adsorbed HA for the clay-humic complexes could be up to several times higher than that of the source HA. This large increase may be contributed by the low polarity of the bound HA. Moreover, for each mineral, the N values of adsorbed HA increased with increasing HA loading. It is believed that HA may develop a more condensed structure on mineral surface at lower HA loading level due to the stronger interactions between HA and mineral surface as a result of close contacts.

Pyrolytic descriptors responsive to changes in humic acid characteristics after long-term sustainable management of dryland farming systems in Central Spain

Structural changes in humic acids from a semiarid soil of an experimental farm in Central Spain have been studied by Curie-point pyrolysis. Soil has received periodic inputs of farmyard manure or crop wastes for the last 16 years, and mineral nitrogen fertilisation in 50% of the plots. Analytical pyrolysis suggested substantial differences in terms of the effect of soil management on the accumulation mechanisms of the humic acid fraction. When compared with control plots, humic acids from plots amended with crop wastes displayed well-defined methoxyphenol assemblages, indicating that the diagenetic transformation of lignin could be a dominant mechanism of organic matter stabilisation. The greatest yields of methoxyphenols after organic inputs were obtained in plots receiving nitrogen fertilisation, what agrees with the expected higher performance of the lignin biodegradation in nitrogen-limited media. Increased yields of lignin-derived methoxyphenols were also observed in plots treated with manure, which released in addition a conspicuous series of alkyl compounds suggesting recalcitrant wax-derived lipids incorporated to the humic acids. Highest yields of pyrolytic fatty acids were observed in humic acids from manure-amended plots without nitrogen fertilisation. Alkylbenzene proportions were also pyrolytic descriptors responsive to mineral nitrogen inputs, showing very significant differences ( P<0.01) in both control and amended plots. Results suggested that continued organic inputs can not be considered to increase soil organic matter quality, since microbial reworking of lignins became the dominant mechanism of accumulation of humic acid-type substances, even when nitrogen inputs were applied.

NMR Study of Structural Changes in Humic Acids of Meadow Soddy Soils

Quantitative and qualitative changes in humic acids of meadow soddy soils, occurring under the action of various fertilizer systems, were studied by 13C and 31P NMR.

Structural Changes of Humic Acids During Olive Mill Pomace Composting

The aim of this work was to characterize the humic acids during composting using both chemical and spectroscopic analytical methods. Humic acids (HA) were extracted from olive mill pomace (OMP) after 5, 10, 21, 32, 48, 60, 84, 95, 109 and 153 days of composting and their elemental composition, functional groups, molecular weight, 13C CP-MAS NMR and FTIR spectra were determined. Elemental composition of HA showed a decrease of carbon content from 56.8% to 47.1% and an increase of oxygen content from 32.7 % to 43.3%. A slight increase of carboxylic groups was observed with no variation of phenolic groups. The molecular weight of HA determined by gel chromatography showed that after 95 days of composting the molecular weight of about 40% of the polymers was greater than 102 KDalton. The 13C CPMAS NMR and FTIR spectra of HA showed compositional and structural changes indicating a slight increase of polysaccharides and aromatic groups and a decrease of long aliphatic chains during the composting.

SIZE EXCLUSION CHROMATOGRAPHY OF HUMIC SUBSTANCES: COMPLEXITIES OF DATA INTERPRETATION ATTRIBUTABLE TO NON-SIZE EXCLUSION EFFECTS

The use of size exclusion chromatography (SEC) to support a theory of conformational changes in humic acids induced by organic acids is reviewed. Particular attention is given to an evaluation of the role of non-size exclusion effects in SEC experiments. In this review, results from SEC studies are interpreted in terms of electrostatic, salt, and specific sorption effects that influence the behavior of the HS on the gel. That interpretation has been proven by experimental results from SEC-fractionation of HS in the absence of organic acids, and this has revealed similar interactions between the HS and the gel. The preference here is for the theory of non-size exclusion effects based on considerations of HS as natural polyelectrolytes.

Structural changes in humic acids during the coalification process

Humic acids from four coals, varying in rank from peat to subbituminous coal, have been characterized by elemental analysis, acidic groups, molecular weight, electrophoresis and visible, FT-i.r. and CP/MAS 13C n.m.r. spectroscopy. The humic acids increase in carbon content, molecular weight, condensation degree and aromaticity ( f a ) with increasing maturation of the parent coals, while the oxygen content decreases with a loss of oxygen functional groups. The presence of lignin-like polymers, poly-saccharides and peptidic materials in humic acids from peat was established using i.r. and 13C n.m.r. spectroscopy. The structural changes observed in humic acids are in agreement with the recognized coalification theory and tend to support the hypothesis of condensation of humic acids into insoluble humin of coal.

INFRARED SPECTRA OF HUMIC ACIDS

Heating preformed KBr pellets effectively eliminated interference arising from hygroscopic moisture in infrared studies of humic acids. Structural changes in humic acid during heating were confined to the formation of cyclic anhydrides from carboxy1 groups. The use of thallous bromide as a nonhygroscopic pelleting matrix and perfluorokerosene as a mulling agent can be recommended in infrared investigations of humic substances.