A characteristic study of humic acids isolated from Arctic fjord sediments
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摘要
Humic substances are ubiquitous natural materials found in sediments as a product of biochemical transformation reactions representing a significant proportion of organic carbon cycle on earth. This study involves the analysis of humic substances with special emphasis on humic acids(HAs) in sediments collected from the Kongsfjorden System of Arctic region in June, 2017. The characterization of the isolated HAs were done using various spectroscopic techniques viz. UV-visible, Fluorescence, FTIR and NMR. Isolated HAs were also undergone for elemental analysis along with other characterization. The UV spectral analysis results with a lower E4/E6 ratio suggesting the presence of HAs with high degree of aromaticity and condensation. Indications for the presence of hydroxyl, methyl, methylene, carbonyl, carboxyl, phenol, alcohol and amide groups were obtained from the FTIR spectrums of HAs. NMR spectral characteristics also confirm the presence of OH group as well as the presence of CH protons adjacent to C=X, were X can be any electronegative element. This also confirms the presence of carbonyl group which is also evident in the FTIR spectral studies. Presence of aliphatic regions slightly more dominated with long chain and/or alicyclic moieties rather than methyl groups was also inferred from the results of NMR.
Humic substances are ubiquitous natural materials found in sediments as a product of biochemical transformation reactions representing a significant proportion of organic carbon cycle on earth. This study involves the analysis of humic substances with special emphasis on humic acids(HAs) in sediments collected from the Kongsfjorden System of Arctic region in June, 2017. The characterization of the isolated HAs were done using various spectroscopic techniques viz. UV-visible, Fluorescence, FTIR and NMR. Isolated HAs were also undergone for elemental analysis along with other characterization. The UV spectral analysis results with a lower E4/E6 ratio suggesting the presence of HAs with high degree of aromaticity and condensation. Indications for the presence of hydroxyl, methyl, methylene, carbonyl, carboxyl, phenol, alcohol and amide groups were obtained from the FTIR spectrums of HAs. NMR spectral characteristics also confirm the presence of OH group as well as the presence of CH protons adjacent to C=X, were X can be any electronegative element. This also confirms the presence of carbonyl group which is also evident in the FTIR spectral studies. Presence of aliphatic regions slightly more dominated with long chain and/or alicyclic moieties rather than methyl groups was also inferred from the results of NMR.
Humic substances are ubiquitous natural materials found in sediments as a product of biochemical transformation reactions representing a significant proportion of organic carbon cycle on earth. This study involves the analysis of humic substances with special emphasis on humic acids(HAs) in sediments collected from the Kongsfjorden System of Arctic region in June, 2017. The characterization of the isolated HAs were done using various spectroscopic techniques viz. UV-visible, Fluorescence, FTIR and NMR. Isolated HAs were also undergone for elemental analysis along with other characterization. The UV spectral analysis results with a lower E4/E6 ratio suggesting the presence of HAs with high degree of aromaticity and condensation. Indications for the presence of hydroxyl, methyl, methylene, carbonyl, carboxyl, phenol, alcohol and amide groups were obtained from the FTIR spectrums of HAs. NMR spectral characteristics also confirm the presence of OH group as well as the presence of CH protons adjacent to C=X, were X can be any electronegative element. This also confirms the presence of carbonyl group which is also evident in the FTIR spectral studies. Presence of aliphatic regions slightly more dominated with long chain and/or alicyclic moieties rather than methyl groups was also inferred from the results of NMR.
引文
Aiken G R,McKnight D M,Wershaw R L,et al.1985.Humic substances in soil sediment and water.New York:Wiley.
Amir S,Hafidi M,Merlina G,et al.2004.Elemental analysis,FTIR and13C-NMR of humic acids from sewage sludge composting.Agronomie,24(1):13-18.
Anuradha V,Nair S M,Kumar N C.2011.Humic acids from the sediments of three ecologically different estuarine systems-a comparison.Int J Environ Sci,2(1):174.
Bergamaschi B A,Tsamakis E,Keil R G,et al.1997.The effect of grain size and surface area on organic matter,lignin and carbohydrate concentration,and molecular compositions in Peru Margin sediments.Geochim Cosmochim Ac,61(6):1247-1260.
Bird J O,May A J C.1981.Statistics for technicians,gen editor,math.Science,95-96.
Chen Y,Senesi N,Schnitzer M.1977.Information provided on humic substances by E4/E6 ratios 1.Soil Sci Soc Am J,41(2):352-358.
Chukov S N,Ejarque E,Abakumov E V.2017.Characterization of humic acids from tundra soils of northern Western Siberia by electron paramagnetic resonance spectroscopy.Eurasian Soil Sci,50(1):30-33.
Dubois M,Gills K A,Hamilton J K,et al.1956.Colorimetric study by phenol-sulphuric acid method.Anal Chem,26:350.
Dziadowiec H,Gonet S,Plichta W.1994.Properties of humic acids of Arctic tundra soils in Spitsbergen.Pol Polar Res,15(1-2):71-81.
Francioso O,Sanchez-Cortes S,Tugnoli V,et al.2001.Spectroscopic study(DRIFT,SERS and 1H NMR)of peat,leonardite and lignite humic substances.J Mol Struct,565:481-485.
Garcia I,Polo A.1985.Influence of vegetation on the characteristies of the organic matter of the soils of Alfagnara(Sierra de Alfacar-Granada,Spain).Anales Edafol Agrobiol,44b:81-82.
Graham B,Mayol-Bracero O L,Guyon P,et al.2002.Water-soluble organic compounds in biomass burning aerosols over Amazonia 1.Characterization by NMR and GC-MS.J Geophys Res-Atmos,107(D20):8047-8062.
Hassink J.1994.Effects of soil texture and grassland management on soil organic C and N and rates of C and N mineralization.Soil Biol Biochem,26(9):1221-1231.
International Humic Substances Society(IHSS).2010.Natural organic matter research,Isolation of IHSS samples.http://www.humicsubstances.org/isolation.html.
IHSS.2010.Natural organic matter research,Elemental composition and stable isotopic ratios of IHSS samples.http://www.humicsubstances.org/elements.htm.
Jayasree G,Chandramohanakumar N.1993.Influence of humic acid on metal sorption by estuarine sediments.Environmental Chemistry,Chemical Oceanography Division.
Kononova A M M.1966.Soil organic matter.Oxford:Pergamon Press,40-41.
Lipson D A,Jha M,Raab T K,et al.2010.Reduction of iron(III)and humic substances plays a major role in anaerobic respiration in an Arctic peat soil.J Geophys Res-Biogeo,115(G4):G00I06.
Lipson D A,Raab T K,Goria D,et al.2013.The contribution of Fe(III)and humic acid reduction to ecosystem respiration in drained thaw lake basins of the Arctic Coastal Plain.Global Biogeochem Cy,27(2):399-409.
Pavia D L,Lampman G M,Kriz G S,et al.2008.Introduction to spectroscopy.Cengage Learning.
Schnitzer M,Preston C M.1983.Effects of acid hydrolysis on the 13CNMR spectra of humic substances.Plant Soil,75(2):201-211.
Sierra M M D,Giovanela M,Parlanti E,et al.2005a.Structural description of humic substances from subtropical coastal environments using elemental analysis,FT-IR and13C-solid state NMR data.J Coastal Res,42:370-382.
Sierra M M D,Giovanela M,Parlanti E,et al.2005b.Fluorescence fingerprint of fulvic and humic acids from varied origins as viewed by single-scan and excitation/emission matrix techniques.Chemosphere,58(6):715-733.
Silverstein R M,Bassler G C,Morrill T C.1991.Spectrometric identification of organic compound.New York:John Wiley&Sons.
Singhal R M,Sharma S D.1983.Comparative studies of infra-red spectra of soil humic acids of Doon Valley Forests.J Indian Society Soil Sci,31(2):182-186.
Stevenson F J.1994.Humus chemistry:genesis,composition,reactions.New York:John Wiley&Sons.
Uyguner C S,Bekbolet M.2004.Photocatalytic degradation of natural organic matter:Kinetic considerations and light intensity dependence.Int J Photoenergy,6(2):73-80.
Amir S,Hafidi M,Merlina G,et al.2004.Elemental analysis,FTIR and13C-NMR of humic acids from sewage sludge composting.Agronomie,24(1):13-18.
Anuradha V,Nair S M,Kumar N C.2011.Humic acids from the sediments of three ecologically different estuarine systems-a comparison.Int J Environ Sci,2(1):174.
Bergamaschi B A,Tsamakis E,Keil R G,et al.1997.The effect of grain size and surface area on organic matter,lignin and carbohydrate concentration,and molecular compositions in Peru Margin sediments.Geochim Cosmochim Ac,61(6):1247-1260.
Bird J O,May A J C.1981.Statistics for technicians,gen editor,math.Science,95-96.
Chen Y,Senesi N,Schnitzer M.1977.Information provided on humic substances by E4/E6 ratios 1.Soil Sci Soc Am J,41(2):352-358.
Chukov S N,Ejarque E,Abakumov E V.2017.Characterization of humic acids from tundra soils of northern Western Siberia by electron paramagnetic resonance spectroscopy.Eurasian Soil Sci,50(1):30-33.
Dubois M,Gills K A,Hamilton J K,et al.1956.Colorimetric study by phenol-sulphuric acid method.Anal Chem,26:350.
Dziadowiec H,Gonet S,Plichta W.1994.Properties of humic acids of Arctic tundra soils in Spitsbergen.Pol Polar Res,15(1-2):71-81.
Francioso O,Sanchez-Cortes S,Tugnoli V,et al.2001.Spectroscopic study(DRIFT,SERS and 1H NMR)of peat,leonardite and lignite humic substances.J Mol Struct,565:481-485.
Garcia I,Polo A.1985.Influence of vegetation on the characteristies of the organic matter of the soils of Alfagnara(Sierra de Alfacar-Granada,Spain).Anales Edafol Agrobiol,44b:81-82.
Graham B,Mayol-Bracero O L,Guyon P,et al.2002.Water-soluble organic compounds in biomass burning aerosols over Amazonia 1.Characterization by NMR and GC-MS.J Geophys Res-Atmos,107(D20):8047-8062.
Hassink J.1994.Effects of soil texture and grassland management on soil organic C and N and rates of C and N mineralization.Soil Biol Biochem,26(9):1221-1231.
International Humic Substances Society(IHSS).2010.Natural organic matter research,Isolation of IHSS samples.http://www.humicsubstances.org/isolation.html.
IHSS.2010.Natural organic matter research,Elemental composition and stable isotopic ratios of IHSS samples.http://www.humicsubstances.org/elements.htm.
Jayasree G,Chandramohanakumar N.1993.Influence of humic acid on metal sorption by estuarine sediments.Environmental Chemistry,Chemical Oceanography Division.
Kononova A M M.1966.Soil organic matter.Oxford:Pergamon Press,40-41.
Lipson D A,Jha M,Raab T K,et al.2010.Reduction of iron(III)and humic substances plays a major role in anaerobic respiration in an Arctic peat soil.J Geophys Res-Biogeo,115(G4):G00I06.
Lipson D A,Raab T K,Goria D,et al.2013.The contribution of Fe(III)and humic acid reduction to ecosystem respiration in drained thaw lake basins of the Arctic Coastal Plain.Global Biogeochem Cy,27(2):399-409.
Pavia D L,Lampman G M,Kriz G S,et al.2008.Introduction to spectroscopy.Cengage Learning.
Schnitzer M,Preston C M.1983.Effects of acid hydrolysis on the 13CNMR spectra of humic substances.Plant Soil,75(2):201-211.
Sierra M M D,Giovanela M,Parlanti E,et al.2005a.Structural description of humic substances from subtropical coastal environments using elemental analysis,FT-IR and13C-solid state NMR data.J Coastal Res,42:370-382.
Sierra M M D,Giovanela M,Parlanti E,et al.2005b.Fluorescence fingerprint of fulvic and humic acids from varied origins as viewed by single-scan and excitation/emission matrix techniques.Chemosphere,58(6):715-733.
Silverstein R M,Bassler G C,Morrill T C.1991.Spectrometric identification of organic compound.New York:John Wiley&Sons.
Singhal R M,Sharma S D.1983.Comparative studies of infra-red spectra of soil humic acids of Doon Valley Forests.J Indian Society Soil Sci,31(2):182-186.
Stevenson F J.1994.Humus chemistry:genesis,composition,reactions.New York:John Wiley&Sons.
Uyguner C S,Bekbolet M.2004.Photocatalytic degradation of natural organic matter:Kinetic considerations and light intensity dependence.Int J Photoenergy,6(2):73-80.