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.

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.

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

Acquisition and Interpretation of Liquid-state 1H NMR Spectra of Humic and Fulvic Acids

1997 ◽  
Author(s):  
Jerry A. Leenheer ◽  
T. I. Noyes
Keyword(s):  
Humic Substances ◽  
1H Nmr ◽  
Liquid State ◽  
Nmr Spectra ◽  
Fulvic Acids ◽  
1H Nmr Spectra ◽  
Humic And Fulvic Acids ◽  
Nmr Spectrometry ◽  
Pure Compounds ◽  
High Concentrations

Fourier Transform nuclear magnetic resonance (NMR) spectrometers have become available to many researchers studying humic substances over the last decade. As a result, liquid-state proton (1H) NMR spectrometry has been commonly used to determine the nonexchangeable proton distribution in humic and fulvic acids. The high sensitivity of the 1H nucleus to NMR spectrometry allows spectra to be obtained on a relatively small quantity of sample (10-100 mg) in a short time (10-30 min). 1H NMR spectrometric profiles of humic substances are useful to environmental scientists in determining the source, properties, and degree of transformation (humification) of organic matter that is operationally classified as humic substances. These 1H NMR spectrometric profiles, which provide information about hydrogen distributions in humic substances, are more useful for structural and biogeochemical studies when combined with 13C NMR spectra, which provide information on carbon distributions, and infrared spectra, which provide information on oxygen distributions. These three spectra, in conjunction with elemental composition, molecular weight, and titrimetric data, can then be synthesized to provide average structural characteristics that can be related to source, properties, and degree of humification of the organic material being studied. Special challenges, that are not met when obtaining the spectra of pure compounds, are encountered in obtaining 'H NMR spectra of natural humic substances. These challenges include (1) lack of complete dissolution of macromolecular humic substances at the high concentrations required for NMR studies; (2) significant concentrations of exchangeable protons giving broad peaks that obscure portions of the spectrum; (3) broad peaks of non-exchangeable protons over the entire spectrum that cause difficulties in correct phasing; (4) unstable structures that oxidize, hydrolyze, and structurally rearrange at the high pH conditions under which humic substances are the most soluble; and (5) the presence of unusual structures that complicate straightforward assignment of structure from handbook data. The purposes of this chapter are to describe methods of sample preparation and to provide generally applicable structural assignments whereby 1H NMR spectra suitable for quantitative studies of humic substance structure may be obtained and interpreted.

Influence of humus acids on mobility and biological availability of iron, zinc and copper

2015 ◽  
Vol 2 (1) ◽  
pp. 73-78
Author(s):  
A. Fateev ◽  
D. Semenov ◽  
K. Smirnova ◽  
A. Shemet
Keyword(s):  
Trace Elements ◽  
Organic Matter ◽  
Soil Organic Matter ◽  
Humic Acids ◽  
Fulvic Acids ◽  
Sand Culture ◽  
Humic And Fulvic Acids ◽  
Cultivation Medium ◽  
Mobile Forms

Soil organic matter is known as an important condition for the mobility of trace elements in soils, their geo- chemical migration and availability to plants. However, various components of soil organic matter have differ- ent effect on these processes due to their signifi cant differences in structure and properties. Aim. To establish the role of humic and fulvic acids in the process of formation of microelement mobility in soils and their accu- mulation in plants. Methods. A model experiment with sand culture was used to investigate the release of trace elements from preparations of humic and fulvic acids and their uptake by oat plants. Results. It was found that among biologically needed elements humic acids are enriched with iron, fulvic acids – with zinc, and copper distribution between these two groups of substances may be characterized as even. These elements have un- equal binding power with components of soil organic matter, as evidenced by their release into the cultivation medium and accumulation in plants. In the composition of fulvic acids zink has the most mobility – up to 95 % of this element is in the form, accessible for plants; the lowest mobility was demonstrated by copper in the composition with humic acids, for which no signifi cant changes in the concentration of mobile forms in the substrate and in the introduction to the test culture were registered. Despite signifi cantly higher iron content in humic acids, the application of fulvic acids in the cultivation medium provides a greater increase in the con- centration of mobile forms of this element. Conclusions. The results confi rm the important role of organic sub- stances of fulvic nature in the formation of zinc and iron mobility in the soil and their accumulation in plants.

scholarly journals Determination of humic and fulvic acids in river waters by concentration with anion exchanger followed by centrifugation.

1989 ◽  
Vol 5 (3) ◽  
pp. 363-365 ◽  
Author(s):  
Tsutomu NOMIZU ◽  
Masaki SANJI ◽  
Masataka HIRAIDE ◽  
Atsushi MIZUIKE
Keyword(s):  
Anion Exchanger ◽  
Fulvic Acids ◽  
Humic And Fulvic Acids ◽  
River Waters

1H NMR spectra of humic and fulvic acids and their peracetic oxidation products

1980 ◽  
Vol 44 (4) ◽  
pp. 603-609 ◽  
Author(s):  
P Ruggiero ◽  
F.S Interesse ◽  
L Cassidei ◽  
O Sciacovelli
Keyword(s):  
1H Nmr ◽  
Nmr Spectra ◽  
Fulvic Acids ◽  
1H Nmr Spectra ◽  
Oxidation Products ◽  
Humic And Fulvic Acids

scholarly journals Biochar changes in soil based on quantitative and qualitative humus compounds parameters

2018 ◽  
Vol 69 (4) ◽  
pp. 234-242 ◽  
Author(s):  
Monika Mierzwa-Hersztek ◽  
Krzysztof Gondek ◽  
Michał Kopeć ◽  
Aleksandra Ukalska-Jaruga
Keyword(s):  
Humic Acid ◽  
Wheat Straw ◽  
Humic Acids ◽  
Fulvic Acids ◽  
Qualitative Composition ◽  
Humic And Fulvic Acids ◽  
Biochemical Processes ◽  
Alternative Sources ◽  
Higher Doses ◽  
Humic Acid Carbon

Abstract Due to the indisputable significance of humus in many biochemical processes as well as its increasing deficit particularly in light soils, alternative sources of substrates for the reproduction of this constituent should be sought. The aim of this study was to evaluate the effect of the addition of wheat straw and wheat straw biochar (in four rates) on quantitative and qualitative humus parameters. The following properties were determined in soil: pH, organic carbon, total nitrogen, humic and fulvic acids, carbon in the extract, non-hydrolysing carbon and spectrophotometric indexes for solution of humic acids including A2/6, A2/4, A4/6. After applying 1% and 2% additions of biochar to the soil, the Corg soil content significantly increased compared to the same doses of thermally unconverted straw. After 254 days of incubation, the addition of biochar to soil at higher doses, decreased the share of humic acid carbon (CHA, CFA) in the Corg content compared to treatments without organic additions and WS treatment. The nonhydrolysing carbon soil content was significantly increased by treatments with 1% and 2% additions of WSB, which indicates greater stabilisation of humus compounds and, at the same time, lower CO2 emission. Soil humic acids amended by treatment with biochar, especially at 1% and 2% doses, were characterised by lower A2/6 and A2/4 ratios. Recognition of changes that may occur in the quantitative and qualitative composition of soil humus after the application of biochar may in the future be helpful information for determining appropriate biochar dose.

scholarly journals A Comprehensive Biological and Physico-Chemical Characterization of Humic and Fulvic Acids Nanoparticles as a Perspective Drug

2021 ◽  
Author(s):  
Elena V. Valer'evna Uspenskaya ◽  
Tatiana Vadimovna Pleteneva ◽  
Tatiana Vladimirovna Grebennikova ◽  
Ilaha Vagifovna Kazimova ◽  
Irina Timofeevna Fedyakina ◽  
...  
Keyword(s):  
Humic Acids ◽  
Cell Model ◽  
Fulvic Acids ◽  
Test Method ◽  
Biological Study ◽  
Fluorescence Signal ◽  
Dry Matter Content ◽  
Humic And Fulvic Acids ◽  
X Ray ◽  
Physico Chemical

This work presents the results of a comprehensive physico-chemical and biological study of hu-mic substances samples &ndash; an extract of humic and fulvic acids. The performed loss on drying test showed a 22 times different dry matter content between EHS and FA. The morphology and dis-tribution of particles in the dry residue of the samples assessed using the methods of optical and digital microscopy demonstrated differences in the qualitative features of the microstructures of their surfaces and granulometries. Shimadzu X-ray fluorescence spectrometry revealed Si (8.1 and 1.7%), P (33.5 and 2.7%), S (4.3 and 59.5%), K (1.35 and 2.5%), Ca (10.9 and 3.2%), Mn (0.27 and 0.06%), Fe (11 and 0.05%), Cu (0.16 and 0.45%), Zn (0.06 and 0.02%) in the dry residues of the EHS and FA samples, respectively. A high intensity of the X-ray fluorescence signal for Fe atoms in the EHS sample was demonstrated. The FT-IR spectra for EHS and FA are characterized by simi-lar vibration frequencies that are characteristic of the chromone derivatives (1-benzopyran-4-one). The UV absorption spectrum is characterized by max = 281 nm for FA. The EHS solution showed a fluorescence maximum at em = 560 nm at ex = 280 nm. Using the DLS method, nanoparticles of 1 nm and 200 nm were detected in EHS and FA diluted solutions, which are likely to condition the biochemical and physical properties of humic acids. Using the Spiro-tox-test method, the absence of the toxic effect of humic acids on the cell model of ciliates Sp. am-bigua was established. When the cell model was incubated in a solution of a toxicant of the fluo-roquinolone group, a decrease in toxicity was demonstrated when diluted with the EHS solu-tion. The results of the study of the antiviral activity of EHS and FA showed that the study ob-jects in the culture of Vero-E6 cells, in doses non-toxic to cells, suppress the reproduction of the SARS-CoV-2 virus both in the study of the virucidal effect and in the study of the antiviral activ-ity according to the therapeutic and prophylactic model scheme of injection. The results obtained suggest that standardized drugs based on humic acids may open up new perspectives in their biomedical application as antiviral drugs.

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