humic substances seminar v - northeastern universityhumic substances seminar v northeastern...

HUMICSUBSTANCESSEMINAR VNortheastern UniversityBoston, MA, USAMarch 21-23, 20010

Honorary Chair C. Edward Clapp with Seminar Chair GeoffreyDavies (right) and Co-Chair Elham Ghabbour (left)

P. MacCarthy and J. Burdon described HSs as intractablemixtures of substances (“supermixtures”) with characteristicaverage properties but no single molecular formula. E. Clapprecounted the science and personalities in his 45-year careeron the “Organic Matter Trail.” R. Wershaw showed narrowpeak spectra of the mobile components of live and senescentleaves obtained with a new type of NMR MAS probe. Y.Putsykin gave evidence for aggregation/disaggregation of1kDa HSs monomers from several kinds of measurements.

Humic Substances Seminar Vwas dedicated to PatrickMacCarthy, Professor ofChemistry and Geochemistryat the Colorado School ofMines and a co-founder ofIHSS. The Honorary Chair wasC. Edward Clapp, USDA-ARSand the University of Minne-sota, and the Honored Guestwas Morris Schnitzer. Alsovery welcome were RobertWershaw (USGS, Denver),who prompted and was Hon-orary Chair of HSs Seminar Iin 1997, Fritz Frimmel (Presi-dent, IHSS) and Donald Sparks(Immediate Past President, SoilScience Society of America).The Honorary Chairs of Semi-nars II (Wolfgang Ziechmann),

www.hagroup.neu.edu 1

III (Cornelius Steelink) and IV (Michael Hayes) were recog-nized. Also participating were IHSS President-Elect YonaChen, Past Presidents James Alberts, Russell Christman,Michael Hayes and Nicola Senesi, IHSS Treasurer C. Ed-ward Clapp, Board Member Maria De Nobili and the IHSSCoordinators of Canada, Egypt, Ireland, Israel, Italy and theUSA (Ming Huang, Elham Ghabbour, Michael Hayes, YonaChen, Nicola Senesi and James Rice). Industrial interest inthe Seminars is growing. The Abstract Book of Seminar Vcontained advertisements from the following organizations:Arctech, Inc. (Chantilly, VA, D. Walia), Actagro LLC (Biola,

CA, F. Shanahan), CropmasterR-UAS of America, Inc.(Hudson, FL, M. Pecsenka), Horizon Ag-Products, Inc.(Kennewick, WA, D. King), Luscar Ltd. (Edmonton, Canada,D. Ozdoba), Micromass UK Ltd. (Manchester, D. Church-man) and The Royal Society of Chemistry (Cambridge, UK,R. Andrews). A full day of HSs applications papers was in-cluded in the program of 50 presentations with nearly 126authors from 14 countries.

We followed the sequence HSs Principles, Genesis, Model-ing, Separation, Analysis, Solute and Metal Interactions,Coal-derived HSs and Plant Interactions. Two topics of highcurrent interest were HSs NMR/MS analysis and coal de-rived products, as presented by leaders of these fields. Thework ranged from aqueous NOMs to solid HAs. The Ab-stracts are available at <www.hagroup.neu.edu>. The pro-ceedings will be published as the book Humic Substances:Structures, Models and Functions, E. A. Ghabbour and G.Davies, Eds., by The Royal Society of Chemistry in Novem-ber 2001. Each paper will be abstracted by Chemical Ab-stracts. Research presented at Seminar V by the individualsnamed is summarized below.

Dedicatee, Patrick MacCarthy

Humic Substances Seminar VI will be held at Northeastern University, July 27, 2002immediately following the IHSS11 Conference at Northeastern University.The Honorary Chair is Dr. Maria De Nobili of the University of Udine, Italy.

Seminar VI registration and abstracts deadline is December 30, 2001. See you there!!!!

From left: Dagmar Gajdošová, Session Chair Patrick Hatcher,Cooper Langford and Amrith Gunasekara

From left: Kaijun Wang, Session Chair Robert Wershaw andRobert Cook

From left:Gunnar Buckau, Manfred Wolf, Ruben Kretzschmar,Session Chair Josef Havel and Andreas Scheinost

From left: Honorary Chair C. Edward Clapp, Dedicatee PatrickMacCarthy, Robert Wershaw, Session Chair James Rice, AlexanderShapovalov and Yury Putsykin

A. Simpson gave NMR evidence for aliphatic acids, ethers,esters, alcohols, polysaccharides, polypeptides and aromaticlignin fragments < 2kDa in different HSs samples. K. Wangconcluded that differences of spin-lattice relaxation times T1of HAs solutions in NaOD and DMSO indicate different con-figurations with aromatic components more mobile than ali-phatic units.

T. Shinozuka has used selective methylation methods to showthat the free radical spin concentration of a peat HA is relatedto its carboxyl group content. P. Hatcher has confirmed byelectrospray ioinization ESI-Qq-TOF mass spectrometry thatfatty acids in HSs samples are easily discernable from theirhigh mass discrimination and separation from the clusteredmasses. M. Spiteller reported that average masses of HSssamples are 5 times lower with Atmospheric Pressure Chemi-cal Ionization (APCI) than with ESI, and that it is possible toobtain daughter ion mass spectra of HSs by nanospray tan-dem mass spectrometry. A. Fataftah demonstrated that cur-rent HSs industry analysis methods give different HSs con-tents of the same commercial sample.

A. Scheinost compared HSs functional group chemistry de-termined by C1s near-edge X-ray absorption fine-structurespectroscopy (NEXAFS) with information from other meth-ods. M. Wolf emphasized the differences between HSs sizesand masses indicated by different experimental methods, con-cluding that HSs primary units weigh 1kDa or less. R.Kretschmar reported similar Cu2+ and Pb2+ binding isothermsfor different size HSs fractions obtained with a cross flowhollow fiber ultrafiltration technique.

According to C. Langford, semi-empirical quantum calcula-tions of a proposed HA building block’s lowest energy statesindicate “half-tennis ball” structures rather than the “helix”predicted by Sybil and MM+ molecular modeling. D.Gajdošová showed that HAs isolated from Antarctic soils havesome similarities to HAs from other continents. Work by A.Gunasekara indicates two distinct spin-spin proton relaxationtimes T2 in HSs samples due to multiple domains. J. Mao hasfound nanometer-sized aliphatic domains in peat HAs from2-D exchange NMR and chemical shift filter experiments,and R. Cook has applied the full arsenal of NMR techniquestoidentify small HSs molecules or highly mobile entities.

HUMIC SUBSTANCES SEMINAR V Northeastern University, Boston, MA, USA, March 21-23, 2001


L. Pokorná used capillary zone electrophoresis and MALDI-TOF mass spectrometry to study the stability of a Chemapexcoal-derived HA product and HAs from other sources inaqueous base.

D. Sparks, representing the Soil Science Society of America,summarized a vigorous effort in collaboration with othernational and international societies to increase public aware-ness of the importance of soils and water, and to encouragefunding for more basic and applied research.

G. Korshin is using differential spectroscopy to understandthe effects on HSs of pH, ionic strength and chlorination,which breaks them down. S. Hesse described the use ofbiofilm reactors and other methods to quantify the biologi-cal degradation potential of organic matter in wastewater.In a comprehensive study of seasonal variations in the NOMof six rivers in SE Georgia, USA, M. Takács and J. Albertshave found that the largest size fractions have the largestspecific absorbances, while the smallest sized matter hasthe largest relative fluorescence intensities.

From left: Amjad Fataftah, Session Chair Georg Haberhauer,Patrick Hatcher, Michael Spiteller and Lenka Pokorná

From left: Fritz Frimmel, Michael Hayes, Gregory Korshin,Session Chair Colin Graham, Monika Takács, James Alberts andAnca-Maria Tugulea

M. De Nobili is using 2-D electrophoresis to study proteinbinding by HSs, which is not destroyed by changes in pH andis strongest at low pH in acid soils. The latest studies re-ported by K. Nichols of the glycoprotein glomalin found insoils throughout the world indicate it is distinguishable fromFAs and HAs in soils. M. Diallo is pioneering the use of com-puter assisted structure elucidation, atomistic simulations andFlory-Huggins solution theory to predict the binding of sol-utes to dissolved FAs and HAs. G. Haberhauer is using den-sity functional theory to model the interactions of a modelpesticide with the common clay kaolinite and the functionalgroups of HSs.

J. Sonke and F. van Willert won Best Student PresentationAwards for their papers. Sonke showed how coupling capil-lary electrophoresis to a magnetic sector inductively coupleplasma mass spectrometer (CE-ICP-MS) can be used to mea-sure the low rates of metal release from HSs. Detection ofAl3+ over the concentration range 0.1 to over 50 mg/L as nega-tive peaks in CE experiments have enabled van Willert tostudy Al binding by DOM.

From left: Donald Sparks and Session Chair Nicola Senesi From Left: Kristine Nichols, Mamadou Diallo, Fritz Frimmel,Jeroen Sonke and Maria De Nobili



face coatings with characteristic shapes and dimensions. M.Nachtegaal has used diffuse reflectance, X-ray absorption nearedge and extended X-ray absorption spectroscopies to showthat the formation of hydroxonickel(II) precipitates on ka-olinite is not prevented by HA coating of the clay surface. Y.Chen gave clear evidence that a negatively charged HA coat-ing markedly reduces the tendency of clays to flocculate, asindicated by increased flocculation values (FVs).

D. Ussiri reported that solid-state 13C NMR reveals alkyl Cas the largest C fraction in both HAs and FAs in forest soils.Carboxyl content was twice as much in FAs than in HAs. In astudy of the effect of ground cover, G. Ding showed that hu-min (HU) has a very strong signal at about 30 ppm, which isassigned to long -CH2- chains. The aromaticity of HU is higherin Rye Alone plots with or without N fertilizer than the othertwo systems studied, showing that agricultural practices af-fect the compositions of HU, a large fraction of SOM. H.Shindo reported that the characteristics of HAs from charredplant residues are similar to those of HAs in volcanic ashsoils, indicating that burning vegetation is a mechanism forblack HAs formation in Japanese volcanic soils.

K. Nierop reported that precipitation of metal-HSs complexesdepends on the metal, the metal loading level and pH. Under-graduate T. Anderson used flow-field flow fractionation (flow-FFF) coupled to ICP-MS to measure the molecular weights(» 5 kDa, as reported last year), polydispersity, hydrodynamicdiameters and diffusion coefficients of metalated HSs frac-tions. Undergraduate L. Shifley reported further flow-FFF-ICP-MS studies of metal binding by fractions of HAs fromMexico, a temperate soil in Western Massachusetts and acontaminated sediment in the Blackstone River Valley, Mas-sachusetts. B. Jansen uses the technique of diffusion gradi-ents in thin films to assess strong complexation of Al, Cu,Fe(II) and Fe(III) by DOM as a function of metal/DOM ratioand pH in the absence and presence of competing ions.

M. Huang showed that humification of catechol on metaloxides decreases their surface areas and alters the pH of zerosurface charge due to aggregation of the HS-metal oxide com-posites. M. Tugulea has used contact mode atomic force mi-croscopy (AFM) to show that adsorption of IHSS standardFAs and HAs on freshly cleaved muscovite mica under dif-ferent solution conditions results in three dimensional sur-

Jeroen SonkeNational High Magnetic FieldLaboratory, Tallahassee, FL

From left: Session Chair Fritz Frimmel, Laura Shifley, Frankvon Willert, Thomas Anderson and Klaas Nierop

From left: Boris Jansen, Jingdong Mao, Ming Huang, SessionChair Donald Sparks, Anca-Maria Tugulea, MaartenNachtegaal, Guangwei Ding and Yona Chen

From left: David Ussiri, Session Chair Ming Huang, SebastianHesse, Haruo Shindo and Adam Zsolnay



Frank von WillertPennsylvania State University

University Park, PA

From left: Henri Dinel, Session Chair, Gunnar Buckau, MorrisSchnitzer, Stanislav Mikeska and Dale Ozdoba

From left: Mir-M Seyedbagheri, Thésphile Paré, Session ChairYona Chen and Nicola Senesi



Á. Zsolnay asked if an agricultural practice can have longterm effects on the relatively available humus (water extract-able organic matter, WEOM) and FAs. He found that WEOMis not dominated by FA and that FAs are not the truly mobilefraction of the soil’s humus.

J. Havel reported the use of HAs extracted from westernBohemian brown coals in the Czech Republic for agricul-ture, soil remediation, waste water treatment, ceramics manu-facturing, the paper industry and the military.

Opportunities exist to utilize high quality humified organicmatter products that are rich in HAs and FAs in agronomicproduction and reclamation practices. D. Ozdoba, M.Schnitzer, H. Dinel and T. Paré gave a comprehensive de-scription of the distribution, extraction, characteristics anduse with fertilizers of humics from range of coal sources minedby Luscar Ltd. Major peaks in FTIR spectra are found near

1600 cm-1 (COO-). 13C NMR spectra show prominent reso-nances near 32 ppm due to -(CH2)n- chains that appear todominate these materials, and at 130 ppm due to aromatic Cnot substituted by N or O. Pyrolysis-field ionization massspectrometry and principal-component analysis of the oresand HAs confirm relatively high concentrations of n-fattyacids (n-C16 to n-C33), unsaturated fatty acids (C16 to C23), n-alkanes (n-C18 to n-C25), alkenes (C18 to C25), lignin dimers,alkyl aromatics and n-alkyl diesters. T. Paré demonstratedthat in alfalfa production, Ca lignite produced 117 to 502%more root masses and 58 to 77% more shoot masses than didEDTA-Ca when sprayed.

M. Seyedbagheri used field bag tests to evaluate the amountof N mineralized from SOM in sugar beet and potato fields.He found a greater water holding capacity in HA treated soils.HSs affect the growth of plants and the influence of mutagenson plants, as shown in a detailed study summarized by N.Senesi.

Geoffrey Davies and Elham Ghabbour present a certificate torecognize and thank Daman Walia, President of Arctech, Inc.

Geoffrey Davies presents a certificate to recognize and thankJames Rice, Coordinator of the US chapter, IHSS

INTERNATIONAL HUMIC SUBSTANCES SOCIETY 20th ANNIVERSARY CONFERENCEHumic Substances – Nature’s Most Versatile Materials

July 21-26, 2002Northeastern University, Boston, MA, USA

Seminar V hosts: From left: Elham Ghabbour, Artur Zmiejko,Nadeem Ghali, Dina Sorour, Ludmila Shirshova and GeoffreyDavies

Certificates of recognition for financial support were presentedto Daman Walia (President, Arctech, Inc.) and James Rice(Coordinator, US Chapter of IHSS). The Seminar Banquetwas a nice opportunity to award Honorary Membership ofIHSS to Professor Russell F. Christman (University of NorthCarolina at Chapel Hill and IHSS President 1990-92). DulaAmarasiriwardena, Tom Anderson, Boris Jansen and LauraShifley won Northeastern souvenirs in the raffle run by thestudent participants. Among the special friends present wereJoan Burdon, Tanja Frimmel, Anne Graham, Katie Hayes,Helen and Mary MacCarthy, Betty and Yana O’Toole, RosellaSenesi and Joy Sparks.

From left: IHSS Past President and Honorary Member MichaelHayes, IHSS Treasurer Edward Clapp, IHSS Immediate PastPresident James Alberts, IHSS President-Elect Yona Chen, IHSSPast President and new IHSS Honorary Member RussellChristman, IHSS President Fritz Frimmel and IHSS HonoraryMember Morris Schnitzer


Editors: E. A. Ghabbour and G. Davies.S. Ghabour is acknowledged for technical assistance.Photo credits: C. E. Clapp and Jet Photography, Inc.© Barnett Institute, Northeastern University, 2001.

Seminar V Participants in the Curry Student Center, Northeastern UniversityFront row from left: Seminar VI Honorary Chair Maria De Nobili,

Seminar V Dedicatee Patrick MacCarthy, Seminar V Honorary Chair Edward Clapp, Seminars Honorary Guest Morris Schnitzer, Seminar I Honorary Chair Robert Wershaw, Seminar IV Honorary Chair Michael Hayes


Humic Substances Seminar V was sponsored by Arctech, Inc.,the US Chapter of IHSS, and the Barnett Institute of Chemi-cal and Biological Analysis, the Chemistry Department, theCollege of Arts and Sciences and the Office of the Provost atNortheastern University.

Publication of this report wasassisted by a grant fromLuscar Ltd.Specialty Products DivisionEdmonton T5L 3C1, Canada

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