Source: UNIVERSITY OF MAINE submitted to NRP
CHEMICAL CHARACTERIZATION OF THE HYDROPHILIC FRACTION OF ORGANIC MATTER ISOLATED FROM SOILS AND ORGANIC AMENDMENTS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
HATCH
Reporting Frequency
Annual
Accession No.
0204931
Grant No.
(N/A)
Cumulative Award Amt.
(N/A)
Proposal No.
(N/A)
Multistate No.
(N/A)
Project Start Date
Oct 1, 2005
Project End Date
Sep 30, 2010
Grant Year
(N/A)
Program Code
[(N/A)]- (N/A)
Recipient Organization
UNIVERSITY OF MAINE
(N/A)
ORONO,ME 04469
Performing Department
PLANT, SOIL, & ENVIRONMENTAL SCIENCES
Non Technical Summary
The hydrophillic fraction of organic matter have not been investigated in detail by soil chemists. This project will determine the characteristics of the hydrophillic fraction of organic matter and how it reacts will soils.
Animal Health Component
10%
Research Effort Categories
Basic
90%
Applied
10%
Developmental
(N/A)
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
10101102000100%
Knowledge Area
101 - Appraisal of Soil Resources;

Subject Of Investigation
0110 - Soil;

Field Of Science
2000 - Chemistry;
Goals / Objectives
1. Determination of the chemical characteristics of a range of organic soil amendments. Organic amendments such as crop residues and animal manures are complex materials which contain carbon in a multitude of structural forms. The hydrophilic fraction of soil organic matter and soil amendments will be investigated using fluorescence spectroscopy with multi-way parallel factor analysis and magnetic resonance spectroscopy. In addition, macroscopic parameters such as the acid-base character of the organic matter will be determined using potentiometric titration and molecular weight determined by size-exclusion HPLC. 2. Truthing of parallel analysis derived fluorophores with organic functional classes. The deconvoluted fluorophores derived from multi-way parallel analysis are in one sense,quasi-particles, a hypothetical mathematical construct which give the best fit to an observed spectra. Inclusion of multiple spectroscopic methods and organic matter sources will allow the use of statistical methods to assign fluorophores to functional classes. This knowledge can then be used to semi-quantitatively characterize dissolved organic matter using fluorescence which can be obtained with less effort than other means of organic matter analysis. The result will be improved analytical methodology for studying soil organic matter. 3. Effects of hydrophilic dissolved organic matter properties on its sorption to soil surfaces. Soluble organic matter sorbs to mineral and oxide surfaces in soils. The effects of functional group content of the hydrophilic fraction, as determined by fluorescence and magnetic resonance spectrometry, on sorption to soil component surfaces will be investigated. It has been well documented that the higher molecular weight fractions of organic matter sorb preferentially to surfaces. This study will allow a more detailed description of what chemical groups are involved in these sorption processes.
Project Methods
The hydrophilic fraction of the water-soluble fraction of the soil and soil amendments will be extracted using a modified International Humic Substance Society method (Swift, 1996). The filtrate will be acidified to pH 1.5 by the addition of 6 N HCl and allowed to stand for 24 h to precipitate the humic acid. The solution will be centrifuged and filtered again through fiber glass filters to separate the FA from the precipitated humic acid. The filtrate containing the FA will be purified by passing it through a 25 mL column of purified XAD-7 resin. The resin will be purified by five batch extractions with 0.1 N NaOH stirred for 1 h, followed by three repeated Soxhlet extractions with methanol for 4 h. The resin will be packed in a column and eluted with 5 column volumes each of 0.1 N NaOH, 0.1 N HCl, and DI-H20. The absorbance at 225 nm will be measured for the 0.1 N NaOH elutent, and with <0.008 absorbance units indicating effective purification of the resin. The solution in the elutant will be collected to isolate the hydrophilic fraction. The sorbed FA will desorbed in batch mode by raising the pH of solution to pH 7 to collect the hydrophobic fraction (Gregor and Powell, 1986). Both the hydrophilic and hydrophobic solutions will be passed through a H+-saturated cation exchange column to protonate the fractions and then freeze-dried. Excitation-emission matrix fluorescence spectroscopy will be used to probe the structural chemistry of the isolated organic material (Ohno, 2002; Senesi, 1992; Alberts and Takacs, 2004). Chemometrics is the use of multivariate and multi-way statistical methods to extract useful information from chemical measurements (Beebe et al., 1998). Chemometrics is useful in discerning relationships between chemical properties and composition and identifying classes of objects with given properties of interest. It has been shown to be useful in classifying soil systems (Kalahne et al., 2000; Haberhauer et al., 1998; 2000). The fluorescence spectroscopic characterization of organic matter we propose will result in a data set (i.e. spectra over a range of wavelength) which provides considerable chemical information; however, the extent and detail of the data makes the analysis and synthesis of that information difficult. The use of multi-way deconvolution methods, such as PARAFAC, can decompose the excitation-emission landscape into fluorophores characterized by unique excitation and emission spectra as well as a distribution profile of fluorophore concentration for each sample (Andersen and Bro, 2003; Stedmon et al., 2003; Smilde et al., 2004). The decomposition method is implemented using the n-way toolbox (Andersson and Bro, 2000) for the matrix mathematics software MATLAB. The ability of multi-way methods to decompose the complex landscape into independent fluorescent components should allow the tracing of the different fractions in the dissolved organic matter pool during the sorption process.

Progress 10/01/05 to 09/30/10

Outputs
OUTPUTS: The objectives of this proposal was to improve our chemical understanding of the hydrophilic fraction of both water-soluble and base-soluble organic matter isolated from carbon-rich soil amendments and soils. The principle methodology will be spectroscopic, using total luminescence fluorescence spectroscopy, ultrahigh resolution mass spectrometery,and magnetic resonance spectrometry. Chemometric deconvolution techniques will be used to extract information present in data intensive spectra produced by these methods. Spectra of different fractions of soil carbon were investigated using these spectroscopic methods to characterize the changes in soil organic matter structure as a function of humification. These studies provided a mechanistic understanding of how soluble organic matter from these materials interacts with and become sequestered to soil surfaces. The results from these studies were presented at American Chemical Society and American Geophysical Union annual meetings. Due to the adoption of these chemoinformatic methods, training of graduate students and collaborators on how to conduct these analysis has been conducted. PARTICIPANTS: Nothing significant to report during this reporting period. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Results of studies conducted have shown that multivariate approaches to data-intensive spectroscopic techniques is able to assist in interpreting the data in a chemically significant manner. The publication of these works has led to acceptance of these methods as a way to efficiently analyze these data-rich spectra.

Publications

  • Simon, K.S., T. Pipan, T. Ohno, and D.C. Culver. 2010. Spatial and temporal patterns in abundance and character of dissolved organic matter in two karst aquifers. Fundamental Appl. Limnol. 177:81-92.
  • He, Z., T. Ohno, D.C. Olk, and F. Wu. 2010. Capillary electrophoresis profiles and fluorophore components of humic acids in Nebraska corn and Philippine rice soils. Geoderma 156:143-151..
  • Ohno, T., and A. Amirbahman. 2010. Phosphorus availability in boreal forest soils: A geochemical and nutrient uptake modeling approach. Geoderma 155:46-54.
  • Ohno, T., Z. He, I.A. Tazisong, and Z.N. Senwo. 2009. Influence of tillage, cropping, and nitrogen source on the chemical characteristics of humic acid, fulvic acid, and water soluble organic matter fractions of a long-term cropping system study. Soil Sci. 174:652- 660.
  • He, Z., T. Ohno, F. Wu, D.C. Olk, C.W. Honeycutt, and M. Olanya. 2008. Capillary electrophoresis and fluorescence excitation-emission matrix spectroscopy for characterization of humic substances. Soil Sci. Soc. Am. J. 72:1248-1255.
  • Hunt, J.F., T. Ohno, and I.J. Fernandez. 2008. Influence of foliar phosphorus and nitrogen content on chemical properties of water extractable organic matter derived from fresh and decomposed sugar maple leaves. Soil Bio. Biochem. 40:1931-1939.
  • Ohno, T., Z. Wang, and R. Bro. 2008. PowerSlicing to determine fluorescence lifetimes of water-soluble organic matter derived from soils, plant biomass, and animal manures. Anal. Bioanal. Chem. 390:2189-2194.
  • Ohno, T., A. Amirbahman, and R. Bro. 2008. Parallel factor analysis of excitation-emission matrix fluorescence spectra of water-soluble organic matter as basis for the determination of conditional metal binding parameters. Environ. Sci. Technol. 42:186-192.
  • Hunt, J.F., T. Ohno, Z. He, and D.B. Dail. 2007. Inhibition of phosphorus sorption to goethite, gibbsite, and kaolin by fresh and decomposed organic matter. Biol. Fertility Soils 44:277-288.
  • Ohno, T., B.R. Hoskins, and M.S. Erich. 2007. Soil organic matter effects on plant available and water soluble phosphorus. Biol. Fertility Soils 43:683-690.
  • Ohno, T., I.J. Fernandez, S. Hiradate, and J.F. Sherman. 2007. Effects of soil acidification and forest type on water-soluble soil organic matter properties. Geoderma 140:176-187.
  • Hunt, J.F., and T. Ohno. 2007. Characterization of fresh and decomposed dissolved organic matter using excitation-emission matrix fluorescence spectroscopy and multiway analysis. J. Agric. Food Chem. 55:2121-2128.
  • Ohno, T., J. Chorover, A. Omoike, and J. Hunt. 2007. Molecular weight and humification index as predictors of adsorption of plant- and manure-derived dissolved organic matter to goethite. Eur. J. Soil Sci. 58:125-132.
  • Hunt, J.F., T. Ohno, Z. He, C.W. Honeycutt, and D.B. Dail. 2007. Influence of decomposition on chemical properties of plant- and manure-derived dissolved organic matter and sorption to goethite. J. Environ. Qual. 36:135-143.
  • Banaitis, M.R., H. Waldrip-Dail, M.S. Diel, B.C. Holmes, J.F. Hunt, R.P. Lynch, and T. Ohno. 2006. Investigating sorption-driven dissolved organic matter fractionation by multi-dimensional fluorescence spectroscopy and PARAFAC. J. Colloid Interface Sci. 304:271-276 .
  • Ohno, T., and R. Bro. 2006. Dissolved organic matter characterization using multi-way spectral decomposition of fluorescence landscapes. Soil Sci. Soc. Am. J. 70:2028-2037.
  • He, Z., T. Ohno, B.J. Cade-Menun, M.S. Erich, and C.W. Honeycutt. 2006. Spectral and chemical characterization of phosphates associated with humic substances. Soil Sci. Soc. Am. J. 70:1741-1751.
  • Sherman, J., I.J. Fernandez, S.A. Norton, T. Ohno, and L.E. Rustad. 2006. Soil aluminum, iron, and phosphorus dynamics in response to long-term experimental nitrogen and sulfur additions at the Bear Brook Watershed in Maine, USA. Environ. Monitoring Assessment 121:419-427.
  • Montgomery, M., T. Ohno, T.S. Griffin, C.W. Honeycutt, and I.J. Fernandez. 2005. Phosphorus mineralization and bioavailability in soils amended with biosolids and manures. Biol. Agric. Hort. 22:321-334.
  • Ohno, T., T.S. Griffin, M. Liebman, and G.A. Porter. 2005. Green- and animal-manure based cropping systems effects on soil phosphorus and organic matter. Agric. Ecosystem Environ. 105:625-634.


Progress 10/01/08 to 09/30/09

Outputs
OUTPUTS: OUTPUTS:Our experimental results have been discussed with other researchers in the area of soil organic matter research. We have discussed future experiments in this line of work. The target audience for this work is basic researches working on the structure of soil organic matter and its role in ecosystem processes, as well as as researchers interesting in the development of management systems which can reduce adverse environmental impacts from farming activities PARTICIPANTS: Tsutomu Ohno Zhongqi He, USDA-ARS TARGET AUDIENCES: Basic researchers working on the structure of soil organic matter and its role in ecosystem processes. PROJECT MODIFICATIONS: none

Impacts
Change in knowledge & actions: The work conducted this year has developed rapid and sensititve chemometric methods to analyze ultrahigh resolution mass spectrometric data. This will allow researchers a systematic and statistcally sound methodology for the interpretation of mass spectrometery data.

Publications

  • He, Z., J. Mao, C.W. Honeycutt, T. Ohno, J.F. Hunt, B.J. Cade-Menum. 2009. Characterization of plant-derived dissolved organic matter by multiple spectroscopic techniques. Bio. Fertility Soils 45:609-616.


Progress 10/01/07 to 09/30/08

Outputs
OUTPUTS: The knowledge generated from the experimental studies conducted this year has been discussed with peer researchers at scientific conferences and visits. These interactions have led to fruitful planning sessions of future research plans and alliances. PARTICIPANTS: Tsutomu Ohno, PI James Hunt, graduate student Rasmus Bro, University of Copenhagen, Denmark, Collaborator Zhiming Wang, Molecular Science Laboratory, Battelle Labs, Collaborator TARGET AUDIENCES: The target audience for this work is basic researches working on the structure of soil organic matter and its role in ecosystem processes, as well as as researchers interesting in the development of management systems which can reduce adverse environmental impacts from farming activities. PROJECT MODIFICATIONS: Not relevant to this project.

Impacts
Change in knowledge & actions: The work conducted this year has developed rapid and sensititve chemometric methods to characterize the interaction of natural organic matter with metals. This led to better understand how soil organic matter can impact the bioavailabilty of phosphorus in soils. This research can lead to management systems which reduce the need for annual phosphorus fertilization. This would reduce the purchase costs for farmers and also reduce the potential for adverse environmental impacts as result of phosphorus loading to fields.

Publications

  • He, Z., T. Ohno, F. Wu, D.C. Olk, C.W. Honeycutt, and M. Olanya. 2008. Capillary electrophoresis and fluorescence excitation-emission matrix spectroscopy for characterization of humic substances. Soil Sci. Soc. Am. J. 72:1248-1255.
  • Hunt, J.F., T. Ohno, and I.J. Fernandez. 2008. Influence of foliar phosphorus and nitrogen content on chemical properties of water extractable organic matter derived from fresh and decomposed sugar maple leaves. Soil Bio. Biochem. 40:1931-1939.
  • Ohno, T., Z. Wang, and R. Bro. 2008. PowerSlicing to determine fluorescence lifetimes of water-soluble organic matter derived from soils, plant biomass, and animal manures. Anal. Bioanal. Chem. 390:2189-2194.
  • Ohno, T., A. Amirbahman, and R. Bro. 2008. Parallel factor analysis of excitation-emission matrix fluorescence spectra of water-soluble organic matter as basis for the determination of conditional metal binding parameters. Environ. Sci. Technol. 42:186-192.
  • Hunt, J.F., T. Ohno, Z. He, and D.B. Dail. 2007. Inhibition of phosphorus sorption to goethite, gibbsite, and kaolin by fresh and decomposed organic matter. Biol. Fertility Soils 44:277-288.


Progress 10/01/06 to 09/30/07

Outputs
The activities included continual development of multi-way chemoinformatic methods to analyze second order spectroscopic data. New methods were discussed at the 2007 American Chemical Society National Meeting.

Impacts
Change in knowledge include development of the method to use a combined excitation-emission matrix fluorescence spectroscopy and parallel factor analysis to determine the stability constants of chemically meaningful soil organic matter components modeled by PARAFAC.

Publications

  • Ohno, T., A. Amirbahman, and R. Bro. 2007. Parallel factor analysis of excitation-emission matrix fluorescence spectra of water-soluble organic matter as basis for the determination of conditional metal binding parameters. Environ. Sci. Technol. (in press).
  • Hunt, J.F., T. Ohno, Z. He, and D.B. Dail. 2007. Inhibition of phosphorus sorption to goethite, gibbsite, and kaolin by fresh and decomposed organic matter. Biol. Fertility Soils (in press).
  • Ohno, T., B.R. Hoskins, and M.S. Erich. 2007. Soil organic matter effects on plant available and water soluble phosphorus. Biol. Fertility Soils 43:683-690.
  • Ohno, T., I.J. Fernandez, S. Hiradate, and J.F. Sherman. 2007. Effects of soil acidification and forest type on water-soluble soil organic matter properties. Geoderma 140:176-187.
  • Hunt, J.F., and T. Ohno. 2007. Characterization of fresh and decomposed dissolved organic matter using excitation-emission matrix fluorescence spectroscopy and multi-way analysis. J. Agric. Food Chem. 55:2121-2128.
  • Ohno, T., J. Chorover, A. Omoike, and J. Hunt. 2007. Molecular weight and humification index as predictors of adsorption of plant- and manure-derived dissolved organic matter to goethite. Eur. J. Soil Sci. 58:125-132.
  • Hunt, J.F., T. Ohno, Z. He, C.W. Honeycutt, and D.B. Dail. 2007. Influence of decomposition on chemical properties of plant- and manure-derived dissolved organic matter and sorption to goethite. J. Environ. Qual. 36:135-143.


Progress 10/01/05 to 09/30/06

Outputs
Dissolved organic matter (DOM) plays an important role in many soil ecosystem functions. Multi-dimensional fluorescence spectroscopy of DOM with parallel factor analysis (PARAFAC) of the resulting spectral landscape has been successful in characterizing DOM from a variety of aquatic sources. This study was conducted to asses the multi-way the PARAFAC approach for quantitatively characterizing the fluorescent landscape of DOM from aqueous extracts of soils and soil amendments. The DOM was extracted from plant biomass representative of crop, wetlands, and tree species; animal manures; and soils from controlled cropping systems studies with know history of organic amendments. The PARAFAC results revealed that the plant biomass and animal manure derived DOM contained five fluorescing components: tryptophan-like, tyrosine-like, fulvic-like,and two humic-like fluorophores. The DOM extracted from soils contained three fluorescing components which were in the landscape regions typical of humic substances. The capability of PARAFAC to identify the components present in the DOM extracts, as well as the fluorescent signal based concentrations of the components represents a significant advance in the chemical characterization of soil organic matter. Sorptive retention of organic matter is important in maintaining the fertility and quality of soils in agricultural ecosystems. However, few sorption studies have been conducted which use dissolved organic matter (DOM) characteristic of agricultural amendments. We investigated the sorption to goethite of DOM extracted from: 1) above-ground biomass of wheat straw (Triticum aestivum L.), maize residue (Zea mays L.), soybean residue (Glycine max (L.) Merr.), and hairy vetch residue (Vivia billosa L.); 2) below-ground biomass from maize, soybean, canola (Brassica napus L.), and green bean (Phaseolus vulgaris L.); and 3) beef, dairy, poultry, and pig animal manures. The apparent molecular weight (MWAP) of the DOM was measured by high performance-size exclusion chromatography and ranged from 312 to 1074 g mol-1. The carboxyl-group content of the DOM measured by potentiometric titration ranged from 4.84 to 21.38 mmol(-) g -1 carbon. The humification index (HIX) determined by fluorescence spectrometry varied from 1.15 to 4.33. Sorption was directly related to both MWAP and HIX values of the DOM. Molecular weight analysis of the solution prior to and after sorption indicated that the DOM molecules >1800 g mol-1 were preferentially sorbed resulting in fractionation of the DOM upon reaction with goethite. The multiple regression equation, based only on MWAP and HIX parameters, explained 76% of the variance in amount of DOM sorbed. The results indicate that MWAP and HIX are important factors in controlling the sorption of DOM to mineral surfaces. Amendment with materials that release DOM of higher molecular weight and greater humification will result in enhanced initial sorption of DOM to soil solids, thereby contributing to accumulation of a larger soil organic C pool.

Impacts
This research has the goal of better understanding how soil organic matter affects the availability of phosphorus to crops. Better knowledge of the interaction will allow development of management practices which reduce the quantity of fertilized used by growers

Publications

  • Hunt, J.F., T. Ohno, Z. He, C.W. Honeycutt, and D.B. Dail. 2006. Influence of Decomposition on Chemical Properties of Plant- and Manure-DerivedDissolved Organic Matter and Sorption to Goethite. J. Environ. Qual. (in press)
  • Ohno, T., B.R. Hoskins, and M.S. Erich. 2006. Soil organic matter effects on plant available and water soluble phosphorus. Bio. Fertility Soils (in press)
  • Banaitis, M.R., H. Waldrip-Dail, M.S. Diel, B.C. Holmes, J.F. Hunt, R.P. Lynch, and T. Ohno. 2006. Investigating sorption-driven dissolved organic matter fractionation by multi-dimensional fluorescence spectroscopy and PARAFAC. J. Colloid Interface Sci. 304:271-276 .
  • Ohno, T, and R. Bro. 2006. Dissolved organic matter characterization using multi-way spectral decompositon of fluorescence landscapes. Soil Sci. Soc. Am. J. 70:2028-2037.
  • He, Z., T. Ohno, B.J. Cade-Menun, M.S. Erich, and C.W. Honeycutt. 2006 Spectral and chemical characterization of phosphates associated with humic substances. Soil Sci. Soc. Am. J. 70:1741-1751.
  • Ohno, T., J. Chorover, A. Omoike, and J. Hunt. 2006. Molecular weight and humification index as predictors of adsorption of plant- and manure-derived dissolved organic matter to goethite. Eur. J. Soil Sci. (in press)
  • Sherman, J., I.J. Fernandez, S.A. Norton, T. Ohno, and L.E. Rustad. 2006. Soil aluminum, iron, and phosphorus dynamics in response to long-term experimental nitrogen and sulfur additions at the Bear Brook Watershed in Maine, USA. Environ. Monitoring Assesment 121:419-427.