Quantitative elemental and structural analysis of dissolved organic carbon fractions from lakes near Sudbury, Ontario

1996 ◽  
Vol 74 (12) ◽  
pp. 2460-2470 ◽  
Author(s):  
Roy Carl Boerschke ◽  
Elizabeth Ann Gallie ◽  
Nelson Belzile ◽  
Richard Neville Gedye ◽  
James Robert Morris
Keyword(s):  
Organic Carbon ◽  
Dissolved Organic Carbon ◽  
Organic Acids ◽  
Humic Substances ◽  
Humic Acids ◽  
Nmr Spectra ◽  
Fulvic Acids ◽  
Published Data ◽  
Organic Carbon Fractions ◽  
C Nmr

Dissolved organic carbon (DOC) was quantitatively isolated as five separate fractions from two Sudbury area lakes (Ontario, Canada) using the tandem XAD-8/XAD-4 resin technique. Fulvic acids made up ≈ 48% of the total, humic acids ≈ 8%, hydrophobic neutrals ≈ 8%, XAD-4 acids ≈ 11%, and XAD-4 acetonitrile extracts ≈ 13%. Hydrophobic:hydrophilic ratios were about 65:35. Solid-state CPMAS 13C NMR indicated a primarily aliphatic nature in all fractions. Percent aromaticity was in the order humic acids > fulvic acids > XAD-4 acetonitrile extracts ≈ XAD-4 acids ≈ hydrophobic neutrals. Titration analysis showed that the 13C NMR peaks of fulvic acids, humic acids, and XAD-4 acids from 160–190 ppm were primarily carboxyl in nature. The XAD-4 acids were the most acidic, suggesting that they may be important geochemical agents. 13C NMR indicated that polysaccharides formed < 20% of any fraction. The two neutral fractions (hydrophobic neutrals and XAD-4 acetonitrile extracts) had relatively high N contents, possibly due to the acetonitrile used to extract them. However, the 13C NMR spectra did not show significant quantities of acetonitrile. The elemental and structural composition covaries in the three acid fractions, such that if one acid is enriched or depleted, so are the others. This suggests that the humic and non-humic acids form a continuum in which all fractions are affected by the same formative processes. Compared to published data for other freshwater samples, the three acid fractions from the Sudbury area lakes have low or very low aromaticity. This may indicate that the acid and metal loadings in the Sudbury area have affected the structure of the organic acids, despite the circumneutral character of the study lakes. These are the first quantitative 13C NMR results published for the hydrophobic neutrals and XAD-4 acetonitrile extracts, so comparisons are not possible. Key words: aquatic DOC, organic acids, 13C NMR, humic substances, non-humic substances.

scholarly journals New possibility for characterization of dissociation behaviour of supramolecular electrolytes: results obtained for the International Humic Substances Society standard and reference samples by coulometry

2021 ◽  
Vol 8 (1) ◽  
Author(s):  
Martina Klučáková
Keyword(s):  
Organic Carbon ◽  
Dissolved Organic Carbon ◽  
Humic Substances ◽  
Functional Groups ◽  
Dissociation Constants ◽  
Fulvic Acids ◽  
Molecular Organization ◽  
Humic And Fulvic Acids ◽  
Acid Base ◽  
Reference Samples

Abstract Background Humic substances can be considered as polyelectrolytes with supramolecular character and complicated behaviour in water environment. The fractions of humic substances dissolved in water are the most active ones and determinative for their functioning in nature, where the proton-binding and dissociation ability play a crucial role. The dissociation behaviour of humic and fulvic acids can be affected by different circumstances including their concentration which is directly connected with the molecular organization of humic particles in solution and the accessibility of their ionizable functional groups. This study is focused just on these active fractions and their dissociation behaviour in the dependence on their content in studied system. Results Standards and reference samples of International Humic Substances Society were used. Flow-through coulometry was used to determine the total content of acidic functional groups in fulvic solutions and humic leachates. The amount of dissociated acidic groups was determined on the basis of potentiometry. Several differences between the behaviour of humic and fulvic acids were found. While whole samples of fulvic acids including the weakest functional groups were analysed, only the active dissolved humic fractions containing stronger acidic functional groups were characterized. The fractions containing higher amounts of the weakest functional groups remained insoluble. The dissociation degree of fulvic acids decreased with their increasing content, but a maximum on its concentration dependence obtained for humic acids was observed. Conclusions Two different values of dissociation constants were determined for each sample. The first was determined on the basis of the extrapolation of infinite dilution, second was determined as their average value in the region of high concentrations in which it was constant. Obtained values characterize the functioning of dissolved humic substances from point of view of their dissociation ability. The results obtained by this approach can help to predict the acid–base behaviour of dissolved organic carbon in soil and generally in nature. The acid–base behaviour of dissolved organic carbon depends on its ratio to water. It behaves differently in soil which is dry and in soil which is wet or saturated by water.

Variation of Δ14C and δ13C Values of Dissolved Humic and Fulvic Acids in the Tokachi River System in Northern Japan

Radiocarbon ◽  
2013 ◽  
Vol 55 (2) ◽  
pp. 1007-1016
Author(s):  
Seiya Nagao ◽  
Takafumi Aramaki ◽  
Nobuhide Fujitake ◽  
Hiroki Kodama ◽  
Takayuki Tanaka ◽  
...  
Keyword(s):  
Humic Acids ◽  
Nmr Spectra ◽  
River System ◽  
Fulvic Acids ◽  
Residence Times ◽  
Humic And Fulvic Acids ◽  
Transport Pathways ◽  
River Waters ◽  
C Nmr ◽  
Northern Japan

Characteristics of dissolved humic and fulvic acids in river waters were studied during 2003–2005 at 4 sites located in the headwaters and in the upper and lower Tokachi River, including a lowland tributary site. Fulvic acids from the headwaters to downstream areas have similar elemental composition and 13C-NMR spectra. Humic acids have similar characteristics in the Tokachi River system. In contrast, δ13C and Δ14C values exhibit a decreasing trend from the upper to the lower and tributary sites, although the headwater site has heavier δ13C and lower Δ14C values than the upper site. Fulvic acids had similar δ13C values from the upper to lower sites, but 123′ higher in Δ14C than those of humic acids on average. The δ13C and Δ14C values exhibited differences in downward variation for humic and fulvic acids. In the Tokachi River system, these results suggest that differences in transport pathways and residence times of humic and fulvic acids reflect differences in the δ13C and Δ14C values in a single river basin.

scholarly journals Characterization of Soil Organic Matter Individual Fractions (Fulvic Acids, Humic Acids, and Humins) by Spectroscopic and Electrochemical Techniques in Agricultural Soils

Agronomy ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 1067
Author(s):  
Aleksandra Ukalska-Jaruga ◽  
Romualda Bejger ◽  
Guillaume Debaene ◽  
Bożena Smreczak
Keyword(s):  
Molecular Weight ◽  
Organic Matter ◽  
Soil Organic Matter ◽  
Humic Substances ◽  
Humic Acids ◽  
Agricultural Soils ◽  
Fulvic Acids ◽  
Sorption Properties ◽  
Aliphatic Chains

The objective of this paper was to investigate the molecular characterization of soil organic matter fractions (humic substances (HS): fulvic acids-FAs, humic acids-HAs, and humins-HNs), which are the most reactive soil components. A wide spectrum of spectroscopic (UV–VIS and VIS–nearIR), as well as electrochemical (zeta potential, particle size diameter, and polydispersity index), methods were applied to find the relevant differences in the behavior, formation, composition, and sorption properties of HS fractions derived from various soils. Soil material (n = 30) used for the study were sampled from the surface layer (0–30 cm) of agricultural soils. FAs and HAs were isolated by sequential extraction in alkaline and acidic solutions, according to the International Humic Substances Society method, while HNs was determined in the soil residue (after FAs and HAs extraction) by mineral fraction digestion using a 0.1M HCL/0.3M HF mixture and DMSO. Our study showed that significant differences in the molecular structures of FAs, Has, and HNs occurred. Optical analysis confirmed the lower molecular weight of FAs with high amount of lignin-like compounds and the higher weighted aliphatic–aromatic structure of HAs. The HNs were characterized by a very pronounced and strong condensed structure associated with the highest molecular weight. HAs and HNs molecules exhibited an abundance of acidic, phenolic, and amine functional groups at the aromatic ring and aliphatic chains, while FAs mainly showed the presence of methyl, methylene, ethenyl, and carboxyl reactive groups. HS was characterized by high polydispersity related with their structure. FAs were characterized by ellipsoidal shape as being associated to the long aliphatic chains, while HAs and HNs revealed a smaller particle diameter and a more spherical shape caused by the higher intermolecular forcing between the particles. The observed trends directly indicate that individual HS fractions differ in behavior, formation, composition, and sorption properties, which reflects their binding potential to other molecules depending on soil properties resulting from their type. The determined properties of individual HS fractions are presented as averaged characteristics over the examined soils with different physico-chemical properties.

THE EXTRACTION OF ORGANIC MATTER FROM SELECTED SOILS AND PARTICLE SIZE FRACTIONS WITH 0.5 M NaOH AND 0.1 M Na4P2O7 SOLUTIONS

1989 ◽  
Vol 69 (2) ◽  
pp. 253-262 ◽  
Author(s):  
M. SCHNITZER ◽  
P. SCHUPPLI
Keyword(s):  
Molecular Weight ◽  
Organic Matter ◽  
Humic Acids ◽  
Nmr Spectra ◽  
Attractive Alternative ◽  
Particle Size Fractions ◽  
Molecular Weights ◽  
Naoh Solution ◽  
C Nmr ◽  
Medium Silt

Organic matter (OM) in the Bainsville and Melfort soils, and in coarse clay and medium silt fractions separated from these soils, was extracted under N2 with 0.5 M NaOH and unadjusted 0.1 M Na4P2O7 solutions. pH ranges of the soils and fractions in contact for 24 h with 0.5 M NaOH and 0.1 M Na4P2O7 solutions extended from 12.2 to 12.6 and 9.0 to 9.4, respectively. Slightly greater proportions of the soil-carbon were extracted by 0.5 M NaOH than by 0.1 M Na4P2O7 solution. The differences, however, did not appear to be significant and may vary from soil to soil. The efficiency of extraction and the characteristics of the extracted materials were assessed on humic acids (HAs), which were isolated from the extracts. From the Bainsville soil and fractions, 0.1 M Na4P2O7 solution extracted more high-molecular weight and more deeply colored HAs than did 0.5 M NaOH solution. But HAs extracted from the Melfort soil and fractions had similar molecular weights and colours. 13C NMR spectra showed that HAs extracted by 0.1 M Na4P2O7 solution tended to be more aromatic than HAs extracted by 0.5 M NaOH solution. Well defined solid-state 13C NMR spectra of HAs, containing up to 69.0% ash, could be recorded. Unadjusted 0.1 M Na4P2O7 solution under N2 was found to be an attractive alternative to 0.5 M NaOH solution as an extractant for soil OM. Key words: Humic acids, E4:E6 ratios, IR spectra, 13C NMR spectra, aromaticity

Mean residence times and characteristics of humic substances extracted from a Taiwan soil

2001 ◽  
Vol 81 (3) ◽  
pp. 299-307 ◽  
Author(s):  
M C Wang ◽  
S H Chang
Keyword(s):  
Humic Substances ◽  
Soil Profile ◽  
Fulvic Acids ◽  
Spectroscopic Properties ◽  
Residence Times ◽  
Spin Resonance ◽  
Profile Depth ◽  
Mean Residence Times ◽  
High Degree ◽  
C Nmr

Humic substances are well known for their long-term persistence in soil environments. The relationship between the mean residence times (MRT) and characteristics of humic substances extracted from a soil with highorganic matter (OM) content in Taiwan was investigated. The MRTs of the soil organic matter (SOM) and its humic substances extracted from the soil samples taken from three depths (0–20, 40–60, and 70–150 cm) of a soil profile were determined by 14C-dating procedures. Moreover, the humic substances were subjected to elemental analysis and investigation by electron spin resonance (ESR), Fourier transform infrared (FTIR), and solid-state 13C nuclear magnetic resonance (13C NMR) spectroscopies. The ranges of the MRT of fulvic acids (FA) (MW < 1000), FA (MW > 1000), humic acid (HA) (MW > 1000), and humins (MW > 1000) were 143 ± 110 to 1740 ± 60, 213 ± 120 to 1690 ± 200, 253 ± 60 to 2200 ± 40, and 293 ± 40 to 2173 ± 70 yr, respectively. The higher standard deviations of the means of determined MRTs of FA (MW < 1000) and FAs (MW > 1000) may be due to their lability. Further, the MRTs of the FAs (MW < 1000), FAs (MW > 1000), HAs (MW > 1000), and humins (MW > 1000) increased with increasing soil profile depth, indicating the slow biological and chemical degradations of humic substances in the deeper layers. The elemental composition and spectroscopic properties of FTIR, 13C NMR, and ESR of humic substances did not change significantly with their MRTs. The MRTs in the range observed in this study were apparently long enough to render humic substances a high degree of chemical stability. Key words: Humic substances, mean residence times, ESR, FTIR, 13C NMR, humin

Contributions of humic substances to the dissolved organic carbon pool in wetlands from different climates

Chemosphere ◽  
2012 ◽  
Vol 88 (10) ◽  
pp. 1265-1268 ◽  
Author(s):  
Akira Watanabe ◽  
Kunio Moroi ◽  
Hiromu Sato ◽  
Kiyoshi Tsutsuki ◽  
Nagamitsu Maie ◽  
...  
Keyword(s):  
Organic Carbon ◽  
Dissolved Organic Carbon ◽  
Humic Substances ◽  
Carbon Pool ◽  
Organic Carbon Pool ◽  
Different Climates
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