Molecular Structure Of Humic Acids Research Articles

Molecular Composition of Humic Acids of Different Aged Fallow Lands and Soils of Different Types of Use in Northwest of Russia

Post-agrogenic transformation of fallow soils leads to changes in soil carbon content, the molecular composition of humic substances, and rates of organic matter stabilization, which can affect climate change on the planet. In this regard, we analyzed the molecular composition of humic acids isolated from natural and fallow soils in the southern Taiga zone of northwest Russia. Different-aged soils on fallow lands represent a model of soil transformation in time, and data on the transformation of soil humic acid molecular composition make a significant contribution to the understanding of soil organic matter stabilization aspect issues. In this case, the molecular structure of humic acids isolated from natural and fallow soils in northwest Russia was analyzed. To study the molecular composition of HAs, the elemental composition was analyzed, and 13C (CP/MAS) NMR spectroscopy of HAs isolated from different aged abandoned soils and soils of different types of use was carried out. The obtained data showed that with the increasing age of soils in the fallow state, there is an increase in the carbon content of humic acids as well as a decrease in nitrogen content. As a result of the increasing age of soils in the fallow state, there are dynamics in the content of aromatic structural fragments in humic acids: 34% for 40 years old, 28% for 80 years old, and 31% for 120 years old. This is due to changes in the precursors of humification and the further transformation of plant residues in the soil. Re-involved fallow land soils lead to an increase in the content of aromatic structural fragments in the composition of HA in relation to HA extracted from mature soils. The lowest content of aromatic structural fragments was observed in the humic acids of 130-year-old agricultural soil, which is associated with the long-term application of organic fertilizers.

Interactions of humic acid with pristine poly (lactic acid) microplastics in aqueous solution

Microplastics and natural organic matter are present in the aquatic environment and their reciprocal interaction plays important roles in the transport and behavior of nutrients and contaminants. Nevertheless, we lack mechanistic understanding on these interactions, especially in the case of biodegradable plastics. Here we investigate the adsorption of a commercial humic acid onto poly (lactic acid) (PLA) microplastics in aqueous solution. While the pseudo-second order kinetic model provided a more accurate representation of the adsorption kinetics, the Elovich model also produced a good fit, suggesting that chemisorption may be the rate-limiting step. The equilibrium data was better fit by the Langmuir model, that provided a maximum adsorption capacity of 0.118 ± 0.006 mg·g−1. The obtained values for the separation factor (RL) and free energy (E) suggest that adsorption of humic acid onto PLA is controlled by physisorption. We studied the effects of pH, ionic strength, and PLA concentration on the adsorption of humic acid onto PLA and demonstrated that electrostatic interactions and aggregation are important. The humic acid was characterized by Fourier-transform infrared (FTIR) spectroscopy, excitation-emission matrix (EEM) fluorescence spectroscopy, and parallel factor analysis (PARAFAC), before and after interacting with PLA. This set of analyses demonstrated that PLA caused alterations in the molecular structure of humic acid, primarily attributed to modifications in hydrogen bonding and hydrophobic interactions. Therefore, we hypothesize that the carboxylic groups of humic acid formed dimers in contact with PLA. This study provides new insights into the interactions between organic matter and a biodegradable microplastic in aqueous systems.

Changes in Molecular Structure of Humic Substances in Cambisols under Agricultural Use

Soil organic matter stability and transformation affected by agriculture is a global problem of great concern. This study aimed to reveal structural changes in humic molecules under conventional soil tillage in Cambisols of the Transbaikal area. Humic acids were isolated from the humus horizons of native and arable variants of Eutric Cambisol Cryic (gleyic, humic, loamic) from the forest steppe, and Haplic Cambisol (arenic, humic, protocalcic) from the steppe zone. The changes in the humic substances’ quality were evaluated by means of an elemental analysis and 13C nuclear magnetic resonance spectroscopy. The results indicate that different agronomic management affected the changes in the composition and molecular structure of humic acids. Soil tillage induced an increase in the carbon content, the proportion of aromatic compounds and carboxyl groups and the depletion in nitrogen. As measured by 13C NMR spectroscopy, the intensity of these changes was determined by soil properties and the hydrothermal regime. Organic matter from Eutric Cambisol Cryic was suggested as providing significant environmental resistance to the agricultural impact due to the optimization of the water regime and a loamy texture. Prolonged ploughing of sandy Haplic Cambisol under the arid conditions promoted deep changes in the humic substances’ composition and chemical structure.

Extraction of humic acid from peat and lignite and the thermal behavior of their mixtures with ammonium nitrate

Due to the positive effect on soil structure and the influence on improving the efficiency of plant roots nutrient uptake, humic acids (HA) are widely considered for fertilizer production. Especially, it seems to be particularly promising to use them as additives in technologies of mineral fertilizer production. One of the common mineral fertilizer components, due to its good water solubility and the presence of nitrogen in two forms, is ammonium nitrate (AN). The aim of this study was to determine the influence of the humic acids extracted from peat and lignite on the thermal decomposition of HA and the thermal decomposition of ammonium nitrate and humic acids mixtures. For the quality assessment of HA, spectroscopic methods (FTIR/ATR and CP/MAS 13C NMR) and analysis of elemental composition were used. The analysis of the spectra showed differences in the degree of humification of humic acids extracted from various raw materials. HA isolated from peat were distinguished by the presence of peptides, polysaccharides, and lignin residues. Elemental analysis showed the higher carbon and sulfur content in the extracted HA compared to the reference samples. The results of the TG-DTA-MS analysis confirmed the influence of differences in the molecular structure of humic acids, especially in the aliphatic and aromatic carbon content, on the thermal decomposition process. Total content of carboxylic and/or hydroxylic functional groups had a significant impact on the start of the decomposition temperature. Their increase visibly influenced the acceleration of the exothermic decomposition of AN.

Effects of Corn Straw and Biochar Returning to Fields Every Other Year on the Structure of Soil Humic Acid

Returning straw and biochar to the fields can change the structure of humic acid in soil and affect the content of soil organic matter. However, returning straw and biochar to the fields in successive years also increases the insect pests of crops and causes nitrogen competition, thus increasing the soil burden. Therefore, to provide a theoretical basis for the study of the time effect of returning fields, three treatments were set in this paper to study the effects of straw and biochar returning every other year on the soil organic matter and humic acid (HA) structure. Elements, Fourier transform infrared spectroscopy (FTIR), thermogravimetric spectroscopy (TG), three-dimensional fluorescence spectroscopy, and solid state 13C-NMR spectroscopy were used to comprehensively investigate the structural characteristics of humic acid in soil. The results showed that after straw and biomass charcoal are returned to the field every other year, compared with 2018, after planting in 2020, the average content of soil organic carbon will increase by 29.49% and 36.14%, respectively. HA showed a phenomenon of increased aliphatic property and decreased aromaticity; aromatic carbon of HA decreased, while alkyl carbon and alkoxy carbon increased; the molecular structure of HA developed toward simplification. In the short term, the effect of biomass charcoal returning was more significant. This study can be used as a reference for the research on the time effect of returning straw and biomass carbon to the fields, and can also provide a basis for the research on the composition of humus after returning organic materials to the fields.

The Molecular Composition of Humic Acids in Permafrost Peats in the European Arctic as Paleorecord of the Environmental Conditions of the Holocene

The purpose of our research is focused on examination of the transformation regularities of molecular composition of humic acids (HAs) in the hummocky frozen peatlands of the European Arctic as a marker of climatic changes in the Holocene, and assessment of the stabilization of soil organic matter under the conditions of modern climatic warming. Histosols located in the two subzones of the European Arctic served as the research subjects. This territory is actively used for reindeer breeding, which is a vital agricultural branch in the Far North of the Russian Federation. The data obtained reveal the main trends in the formation of HAs from Arctic peatlands under different environmental conditions. Modern peat sediments (top layers) in the middle and late Holocene period formed out of bryophyte residues and contained HAs with long-chain carbohydrate and paraffin structures in their composition. These structures enlarged the dynamic radii of HA molecules, and, thus, caused high average molecular weight values. The more favorable climatic conditions of the early Holocene (the Atlantic optimum) defined the botanical composition of peat, which was dominated by tree and sedge communities with high contents of lignin components and, as a consequence, a larger share of aromatic fragments, characterized by thermo-biodynamic resistance in HAs of horizons in the lower and central profile parts. The molecules of HAs are an archive of paleoclimatic records. The Subboreal and Subatlantic climatic conditions determined the specifics of vegetation precursors and, as a result, the molecular structure of HAs in seasonally thawed layers, with a predominance of long-chain aliphatic fragments. The conversion of HAs from Histosols led to an increase in the proportion of carbon in branched and short-chain paraffinic structures with their subsequent cyclization and aromatization. The results of this process are most clearly manifested in layers formed during the Holocene I and II climatic optima. Higher biologically active temperatures of the seasonally thawed layer of soils at bare spots (without vegetation) determined the accumulation of thermodynamically more stable HA molecules with a high content of aromatic fragments. This contributed to both the stabilization of the SOM and the conservation of peatlands in general.

The broad application and mechanism of humic acids for treating environmental pollutants: Insights from bibliometric analysis

Humic acids (HAs) are macromolecular substances that play important roles in different areas of soil, atmosphere, water, and ecological environment restoration. Here, we applied bibliometric analysis to systematically evaluate HAs applications in the environmental field. In-depth analysis of the publication characteristics of 9145 articles published from 1980 to 2020 revealed that the number of articles published on HAs increased rapidly, with China having the largest number of publications (3109), followed by the United States (1949) and Germany (679). Specifically, the Chinese Academy of Sciences had the largest number of publications (647) and was the center of the most productive institutional cooperation network. HAs applications and mechanisms for treating organic pollutants and heavy metals are important research topics in the environmental field. HAs could reduce the toxicity of a variety of organic pollutants or eliminate pollutants through photodegradation and adsorption. These pollutants include antibiotics, herbicides pesticides, fungicides, and other phenolic compounds. Additionally, HAs might be also used to treat heavy metal pollutants, such as mercury, copper, cadmium, uranium, and aluminum. HAs could adsorb heavy metals, thereby reducing their mobility in the environment and toxicity. HAs also have the potential to degrade microplastics and contribute to climate change adaptation. However, bibliometric analysis showed that the molecular structure of HAs remains unclear, thereby limiting clarification of mechanisms and further applications for decontamination. These findings highlight the interaction between HAs and the environment and offer critical insight to support further development of HAs for environmental applications.

Adsorption behaviors of Au(Ⅲ) onto humic acid extracted from gold ore: Adsorptive kinetics, isotherm and mechanism

Humic acid is an important component of carbonaceous matters in the carbon-containing gold ores, which possesses gold-adsorbing capability and leads to the gold loss due to its structural characterization and physicochemical properties. In this paper, the adsorption characteristics of humic acid extracted from refractory carbon-containing gold concentrate were investigated, the adsorption kinetic and isotherm models were established. Simultaneously, the gold-adsorbing process was analyzed employing FTIR, UV–VIS, Raman spectra and XPS. Results showed that the extracted humic acid had the maximum adsorption rate at pH 3.0 and 35 ℃. The relationship between the amount of adsorption and time was found to be consistent with the pseudo-second-order model, and qe was closer to the measured value. The experimental data were found to conform to the Freundlich model which could better explain humic acid’s adsorbing capability for gold. Thermodynamic study indicated that gold-adsorbing process was spontaneous and endothermic. Isosteric heat of adsorption measured by using Clausius-Clapeyron equation increased with increase in adsorption amount showing that the extracted humic acid possessed heterogeneous surface. The study indicated that the gold-adsorbing behavior of the extracted humic acid was a predominantly chemisorption-driven process corresponding to the complexation between Au (Ⅲ) and N-, O- containing and other functional groups. Changes in the molecular structure of humic acid were detected as a result of adsorption. More importantly, a part of gold went from a trivalent state to a monovalent state during adsorption.

Influence of Drainage on Peat Organic Matter: Implications for Development, Stability, and Transformation.

The agricultural use of peatlands, the stabilization of the substrate for building or road construction or for increasing the capacity of soil to support heavy machinery for industrial activities (peat and petroleum extraction), harvesting to provide peat for energy, and the growing media and initiation of chemical processes must be preceded by drainage. As a consequence of drainage, peat underwent an irreversible conversion into moorsh (secondary transformation of the peat). The object of the study was to investigate comparatively the organic matter composition and molecular structure of humic acids (HAs) in the raised bog, fen, and peat-moorsh soils developed in various compositions of botanical cover, peat-forming species, and oxic and anoxic conditions as a result of the oscillation of ground water during drainage as well as to evaluate the vulnerability of soil organic matter (SOM) to decomposition. Drainage was shown to be the principal factor causing the various chemical compositions and physicochemical properties of HAs. Large and significant differences in chemical composition of peat and the properties of HAs were found to be related to the degree of decomposition. The HAs from drained peatlands were less chemically mature. In contrast, the HAs from fen and raised bog were found to be more mature than that of the corresponding drained peatlands. The above findings showed the distinguishable structure of HAs within the soil profile created by the plant residue biodegradation and formed in both oxic and anoxic conditions. The analytical methods of thermal analysis together with the optical densities and paramagnetic behaviour are suitable and effective tools for studying structure–property relationships characterizing the origin and formation process of HAs in various environmental conditions.

Hyperthermophilic composting of sewage sludge accelerates humic acid formation: Elemental and spectroscopic evidence

Application of thermophilic composting (TC) is limited due to poor efficiency and long composting period. Hyperthermophilic composting (HTC) could effectively overcome this defect. Here, the transformation of humic acid (HA) in both HTC and TC was characterized and compared to investigate the roles of HTC toward accelerating the formation of HA. In HTC, the highest temperature was 96.6 °C, and the hyperthermophilic and thermophilic phases exceed 18 days. The degree of polymerization (DP) in HTC increased to 1.27 on day 27, while it only increased to 1.15 at the end of TC. The elemental composition of the HA in HTC showed higher O atomic content (36.3%) and lower C/N atomic ratio (6.5) compared with TC. These changes indicated that HTC could significantly accelerate oxidized and polycondensed reactions for HA formation, which resulted in the shortening of composting period to 27 days. The maximum fluorescence intensity (Fmax) of humic-like components were achieved faster in HTC (Fmax = 1649.9) than in TC (Fmax = 1316.9), implying that HTC promoted the polycondensation of small molecular components to form HA with larger molecular weight and higher degree of aromatization. Two-dimensional FTIR correlation spectroscopy (2D-FTIR-COS) analysis demonstrated that HTC prevented the HA precursor from condensing before it was deeply oxidized, and increased the content of small molecules rich in carboxyl moieties. Based on the evolution of the molecular structure of HA, the level of oxidation of HA precursors was a key factor to determine the degree of polymerization and the degree of HA humification.

Effects of Organic Material Types on Temporal Changes in Characteristics of Humic Acids Extracted from a Chernozem

Returning organic materials to fields is an effective management practice for improving soil quality in agroecosystems. In the case of scarce organic material resources, choosing the optimal material type for improving the quality of a soil type is an urgent problem to be solved. The objective of this study was to evaluate the temporal variations in the spectroscopic characterization of humic acids (HAs) over a period of 90 days after applying biotechnologically extracted fulvic acid (BFA), well-decomposed sheep manure (M), corn stover pellets (Ps) and corn stover powder (Pr) at equal C amount to a chernozem under laboratory conditions, measured by Fourier transform infrared (FTIR) spectroscopy and ultraviolet-visible spectrophotometry (UV–Vis). The results indicated that the BFA and Pr with higher C contents (68.9 and 59.8 g kg−1, respectively) were more beneficial to the C mineralization of HAs. M, applied in the largest amount, together with the highest available N, P, and K contents (575.4, 160.1, 478.9 mg kg−1, respectively), and its more easily consumed carbohydrates as well as well-decomposed status, was more likely to promote the condensation of HAs. BFA carried more hydrophilic groups into the HAs, while Ps did not introduce high levels of adsorbed H2O molecules and aromatic C=C (or C=O) groups. Ps did not affect the molecular structure of HAs after incorporation into the chernozem. At the equal C input amount, M had the greatest benefit, whereas the beneficial effect of Ps was the least, in improving the chernozem quality.

Impacts of Long-term Fertilization on the Molecular Structure of Humic Acid and Organic Carbon Content in Soil Aggregates in Black Soil

Soil aggregates are the basic units of soil structure, and their composition and carbon (C) stability directly affect soil fertility. As cementing agents, humic substances play an important role in the formation and stability of soil aggregates. Long-term fertilization not only changes the structure of humic acid (HA), but also affects the content and stability of organic C in soil aggregates. In this study, based on a long-term fertilization experiment, the relationship between the molecular structure of HA and the stability of organic C in the aggregates was examined. Compared with the non-fertilization control (CK), both the application of organic manure alone (M) and organic manure combined with inorganic fertilizer application (MNPK) increased organic C content in the bulk soil and in HA. In addition, the application of organic manure (M, MNPK) favored the formation of macroaggregates (>0.25 mm) and showed a higher organic C contents of soil aggregates with different sizes than the CK. Moreover, the content of aliphatic C, the ratios of aliphatic C/aromatic C and alkyl C/O-alkyl C was increased with the application of organic fertilizer. A significant negative correlation was observed between aromatic C and organic C content of the aggregates with sizes of >2 mm, 2–0.25 mm, and 0.25–0.053 mm (P < 0.05). The findings indicated that organic fertilization treatments (M and MNPK) increased the aliphatic C content of HA, which favored the increase in the organic C content and stability of the aggregates.

Preferential binding properties of carboxyl and hydroxyl groups with aluminium salts for humic acid removal

To systematically elucidate the removal characteristics of humic acid (HA), which are highly dependent on the molecular structure of HA, a series of representative HA model compounds containing different numbers and positions of carboxyl and hydroxyl groups were selected, and the chemical reaction behaviour between HA and aluminium coagulants was investigated. The results indicated that the number of carboxyl groups in the benzene ring and binding environment had great effects on the Al-binding properties of HA molecules. Under weakly acidic conditions, coordination occurred between carboxyl and Al ions, and the complexing capacity was restricted by the substituted position of hydroxyl groups. Under neutral conditions or at higher coagulant dosages, sweep coagulation occurred by surface complexation of aluminium hydroxide by carboxyl groups and hydrogen bonding between the hydroxyl group and aluminium hydroxide; this process was dependent on the substitutive pattern of the functional groups. Moreover, increased aliphatic chain length and benzene ring size could enhance hydrophobicity, and hence resulted in higher coagulation efficiency. This study provided new insight into the mechanism of the interaction between HA and aluminium coagulants.

Paramagnetic Properties of Humic Substances in Taiga and Tundra Soils of the European Northeast of Russia

The study of paramagnetic activity of humic substances in taiga and tundra soils of the Komi Republic and the assessment of the influence of soil hydromorphism on concentrations of free radicals in the structure of humic acids (HAs) and fulvic acids (FAs) have been performed. The concentration of free radicals in HA specimens was up to 11 times higher than that in FA specimens due to a higher content of aromatic and other condensed structures in HA molecules. This fact attests to the high capacity of HAs to polymerization and complexation reactions with participation of radicals. The average value of g-factor is higher for FA specimens than for HA specimens, which attests to a greater electron density shift of unpaired electron to oxygen atom in the structure of FAs because of its spin-orbital interaction with oxygen-containing functional groups, the concentrations of which are significantly higher in FAs than in HAs. An increase in the concentration of free radicals in the molecular structure of HAs is observed in taiga soils with an increase in the degree of their hydromorphism (from automorphic to semihydromorphic soils), which is related to the biohydrothermal conditions of humus formation in bog-podzolic soils with retarded biochemical processes and low degree of plant litter humification. As a result, HAs with the high content of free radicals in their structure are formed. An opposite situation is observed for HAs in tundra soils with a decrease in the content of unpaired electrons under conditions of the increased hydromorphism. The difference in the character of changes in the paramagnetic activity of HAs in taiga and tundra soils with different degrees of hydromorphism may be related to different natures of plant residues participating in humification processes. A tendency for a decrease in the paramagnetic activity in both HAs and FAs from the south to the north is observed, which may be related to a general decrease in the content of poly-conjugated systems in the structure of humic substances in tundra soils.

Optical properties of gumus acids of chernozem podzolized after applying litter and compostes on its basis

Investigation of electronic absorption spectra of humic acids (HA) is considered as one of their objective diagnostic features and indicators of transformation of HA components. Electron absorption spectra of the HA in the visible and ultraviolet range, in general, are gentle curves, which monotonically decrease with increasing wavelength. However, even such spectra reveal the difference in the spectral properties of the HA not only of different soils, but also of one type under excellent soil conditions, which allows the use of spectrophotometric analysis as a sensitive method for the study of humic acids. A thorough study of the properties and nature of humus substances using modern methods helps to understand the features the formation of humus substances in different natural conditions. The purpose of the study is to determine the change in the qualitative composition of humic acids extracted from chernozem podzoled after application of the litter and compost on its basis by spectrophotometry. To achieve this goal, the following methods were used: modeling, laboratory analysis, mathematical and statistical. Field studies have been carried out to determine the effect of litter and compost on its basis on the formation of the molecular structure of humic acids from chernozem podzoled. The studies carried out by us, the electronic absorption spectra of humic acids of chernozem podzoled correspond to the curves typical for a class of humus, the shape of the spectrum does not change, which indicates the similarity in the molecular structure of humic acids, but differ in the angle of incidence in the region of the ultraviolet range. The qualitative composition of structural elements of humic acids is determined on the basis of the analysis of electron absorption spectra of humic acids in the spectral range of 200–800 nm. The change of optical characteristics of humic acids extracted from chernozem of podzolized after introduction of the litter and compost on its basis was determined. The application of chicken litter and compost (scent + husk) contributes to enhancing the aroma of humic acids and increasing their resistance to mineralization. It has been established that composting has a longer-lasting effect on the formation of the structure of humic acids of black podzolized soils on the introduction of non-composting litter. In the UV range (200–400 nm), we note the characteristic intensive absorption of light for humic acids extracted from chernozem podzolized after the introduction of chicken litter and compost (scent + husk), due to the loss of weakly colored peripheral chains of molecules. The character of the inclination of the curves determined by the ratio D 465/665 allows us to conclude that the humic acids extracted from the chernozem podzolized after composting (laced + husk) have a more condensed nucleus than the introduction of chicken litter and compost (laced + husk). It is determined that the intensity of the influence on the mobility of the aromatic electronic system of humic acids depends on the period of composting of the source material and is manifested in absorption spectra in the ultraviolet light range.

Effects of long-term fertilization on soil humic acid composition and structure in Black Soil.

The composition and structure of humic acid (HA) can be affected by fertilization, but the short-term effects are difficult to detect using traditional analysis methods. Using a 35-year long-term experiment in Black Soil, the molecular structure of HA was analyzed with Fourier transform infrared spectroscopy (FTIR), 13C nuclear magnetic resonance spectroscopy (NMR), and fluorescence spectroscopy. Variation in HA was analyzed after long-term fertilization, including fertilization with manure (M), inorganic N, P and K fertilizer (NPK), manure combined with inorganic N, P, and K fertilizer (MNPK), and a no-fertilizer control (CK). The application of each fertilizer treatment increased crop yields compared with the CK treatment, and the MNPK treatment increased crop yield the most. The ratio of main IR absorption peak of HA at 2,920 cm−1 compared with the peak at 2,850 cm−1 (2920/2850) was higher in the NPK and MNPK treatments compared with the CK treatment. The application of manure (MNPK and M treatments) increased the ratio of hydrogen to carbon (H/C) in HA, and raised the ratio of the main IR absorption peak of HA at 2920 cm−1 to that at 1720 cm−1 (2920/1720). Manure treatments also raised the ratio of aliphatic carbon (C) to aromatic C, alkyl C to alkoxy C and hydrophobic C to hydrophilic C and the fluorescence index (f 450/500), but decreased the degree of aromatization of HA, when compared with the CK treatment. The ratio between each type of C in HA was similar among all the fertilizer treatments, but NPK had a lower ratio of H/C and a lower content of aliphatic C compared with the CK treatment. These results indicated that the molecular structure of HA in Black Soil tends to be aliphatic, simpler, and younger after the application of manure. While the application of inorganic fertilizers increased in the degree of condensation of HA and made HA structure complicated. The application of manure alone or combined with inorganic fertilizers may be an effective way to increase crop yield and improve the structure of soil organic matter.

Molecular Features of Humic Acids and Fulvic Acids from Contrasting Environments.

Insight in the molecular structure of humic acid (HA) and fulvic acid (FA) can contribute to identify relationships between their molecular properties, and further our quantitative abilities to model important organic matter functions such as metal complexation and association with mineral surfaces. Pyrolysis gas chromatography/mass spectrometry (Py-GC-MS) is used to compare the molecular composition of HA and FA. A systematic comparison was obtained by using samples from different environmental sources, including solid and aqueous samples from both natural and waste sources. The chemical signature of the pyrolysates was highly variable and no significant difference between HA and FA was found for major chemical groups, that is, carbohydrates, phenols, benzenes, and lignin phenols, together accounting for 62-96% of all quantified pyrolysis products. However, factor analysis showed that within each sample, FAs consistently differed from corresponding HAs in a larger contribution from mono- and polyaromatic hydrocarbons and heterocyclic hydrocarbons, together accounting for 3.9-44.5% of the quantified pyrolysis products. This consistent difference between FAs and corresponding HAs, suggests that their binding properties may, in addition to the carboxyl and phenolic groups, be influenced by the molecular architecture. Py-GC-MS may thus contribute to identify relationships between HA and FA binding- and molecular-properties.

Characterization of soil organic matter with different degrees of humification using evolved gas analysis-mass spectrometry

Evolved gas analysis-mass spectrometry (EGA-MS) provides a direct connection between the pyrolyzer and mass spectrometer through a deactivated capillary tube, and provides both a thermal profile relating to the differential thermogravimetric curve of the sample and a mass spectrum of evolved gas from the sample. In this study, EGA-MS was performed to obtain thermal profiles and identify the pyrolysis products of 12 humic acids (HAs) with different degrees of humification extracted from 5 Andisols, 3 Entisols, and 3 Inceptisols, as well as soil samples. All HAs were thermally decomposed gradually over a wide temperature range (100–700°C), and the EGA curves showed four peaks and shoulders at around 250, 350, 450, and 550°C. The peaks at around 550°C were observed for the Andisol HAs only. Carboxyl groups, carbohydrates, and short chain alkanes and alkenes of the HAs and bulk soil samples evolved at a relatively low-temperature region (200–300°C). On the other hand, aromatics including benzenes and lignin derivatives evolved at a relatively high-temperature region (300–600°C). While the shapes of the EGA curves were different between the soils and extracted HAs, the major components of the evolved gas and the pyrolysis behavior of the constituents in the HAs and soil samples were similar. The amount of evolved gas from the Andisol HAs, which mainly consisted of CO2, was very low in comparison to that from the Entisol and Inceptisol HAs. The amount of evolved gas and the molecular weight of the pyrolysis products decreased as humification progressed, but the proportion of CO2 in the total area of the EGA curves increased. The results demonstrated that humification reduces the proportion of volatile components and increases the amount of carboxyl groups. As a result, the molecular structure of HAs is found to be mainly composed of non-volatile components and carboxyl groups. Since EGA-MS can provide information about the chemical structure and pyrolysis characteristics of a small sample without pretreatment, it is a useful tool for soil organic matter research.

Structural Alteration of Humic Acids by Pseudomonas spp. from Deep Terrestrial Subsurface Diatomite Formations in Northernmost Japan

Bacterial utilization of humic acids (HAs) was examined under aerobic conditions using Pseudomonas spp. from diatomite from a depth of 250 m below ground level in the Horonobe Underground Research Laboratory. HA decolorization and bacterial aggregation were observed during cultivation when an auxiliary carbon source was added. High-performance size-exclusion chromatography showed that high-molecular-weight HAs were produced. Fourier transform infrared spectroscopy indicated that carboxyl groups and polysaccharide-related substances in HAs were eliminated, while aliphatic structural units and amide groups were added to HAs. These results suggested that Pseudomonas spp. utilize and alter the molecular structure of HAs under aerobic conditions caused by the construction of underground facilities.

Combined application of non-discriminated conventional pyrolysis and tetramethylammonium hydroxide-induced thermochemolysis for the characterization of the molecular structure of humic acid isolated from polluted sediments from the Ravenna Lagoon

Humic acid (HA) isolated from highly polluted sediment from the Ravenna Lagoon (Italy) was subjected to pyrolysis/tetramethylammonium hydroxide (TMAH)-induced thermochemolysis to reveal the impact of industrial activities on humification. Special effort was made to distinguish between analytes originating from the polymeric humic organic matter network along with sequestered compounds (which cannot be released by solvent extraction), and the solvent-extractable lipid fraction sorbed onto the organic matrix. Exhaustive solvent extraction of the isolated HA proved mandatory to avoid biased results when identifying the origin of the pyrolyzates of untreated samples. Conventional pyrolysis at 750 °C of the “degreased” HA revealed a characteristic polycyclic aromatic hydrocarbon (PAH) pattern, which was significantly different than patterns obtained from the pyrolysis of natural humic acids. TMAH-induced thermochemolysis at 500 °C provided information on carboxylic acids covalently bound inside the HA network via ester bonds. Thermochemolysis of the “degreased” matrix at 750 °C, resulting in the cleavage of C–O and C–C bonds, revealed a significant PAH pattern very similar to that obtained by conventional pyrolysis. The uncommon PAH pattern points to the formation of bound residues as the humification/detoxification pathway. Recalcitrant hopane hydrocarbons showed very similar patterns for both the untreated and exhaustively solvent-extracted samples, which points to hopanes being linked inside the humic network via C–C bonds. The technique of non-discriminating flash pyrolysis used in this study, based on extremely rapid capacitive discharge heating in a Silcosteel capillary, proved to be an excellent method to obtain high-boiling pyrolyzates (PAHs beyond 252 Da molecular weight, C 29–C 31-hopanes).