Sasaki et al., Annals of Environmental Science /2007, Vol

2, 17-22

HUMIC GROUP HYGROSCOPICPROPERTIES AND THEIRCHEMICAL STRUCTURE

Osamu Sasaki, Isamu Kanai, Yuuki

Yazawa and Tatsuaki Yamaguchi

Graduate School of Engineering, Chiba Institute of Technology, 2-17-1 Tsudanuma, Narashino, Chiba275-0016, JapanReceived June 9, 2006; in final form December 13,2006; Accepted January 2, 2007ABSTRACTWe investigated the relationship between the hygro-scopic properties and chemical structures of humic andfulvic acids. Humic and fulvic acids were extractedfrom andosol, Canadian peat and Chinese weatheredcoal using the IHSS method. Fulvic-like organicsproduced by the ozone oxidation of humic acid werealso prepared by a method reported previously. Theirmain chemical properties related to hygroscopicitywere also studied by elemental analysis and themeasurement of functional group contents. Humic andfulvic acids were allowed to stand under variousrelative humidity (RH) conditions and the amounts of water vapor adsorbed were measured by gravimetry.Water adsorption isotherms were similar for bothhumic and fulvic acids below RH 80%. Above 80%,water vapor adsorption of fulvic acids and fulvic-likeorganics increased considerably as compared withhumic acids. Deliquescence was observed for all fulvicacids and fulvic-like organics at higher RH. Theamount of water vapor adsorbed at 97% RH by humicsubstances from different sources was highly correlatedwith the ratio of oxygen to carbon contents.

Keywords:

Humic structure, hygroscopic properties,humidity, water retention1. INTRODUCTIONNatural humic materials have been used recently toameliorate degraded soils. Under low-moisture conditions,the hygroscopic properties of soil organic materials areimportant for soil wettability, microbial activity, and thedynamics of soil carbon [1-3]. Humic and fulvic acids areable to adsorb large amounts of water [4]. The hygroscopicproperties of humic materials have been well studied; inparticular, there have been comparisons between humic acid(HA) and fulvic acid (FA) and the effects of their functionalgroups and monovalent metal cations [4,5]. Recent studiesof the hygroscopic properties of humic materials have beenconducted in the fieldof atmospheric aerosols [6-8].However, these aerosol studies were mainly based on theinteraction of humic substances (and/or humiclikesubstances) and in organic salts with respect to the types of inorganic salts.Clarification of the relation betweenthe chemical structureof humic materials and their hygroscopic properties isimportant because it attempts to further address theinfluence of soil organic matter structure on water sorption,and thus its potential influence on soil wettability and otherimportant aspects. The purpose of this paper is to present anevaluation and discussion of water vapor adsorption byHAs and F As in order to clarify the relationship betweentheir chemical characteristics and their capacity for watervapor adsorption.2. MATERIALS AND METHODS

2.1. Humic Materials

The humic and fulvic acids used in this study were obtainedfrom Japanese andosol (AS), Canadaian peat (CP), andChinese weathered coal from Xinjiang, (XWC). Humic acid(HA) and fulvic acid (FA) were extractedwith theInternational Humic Substances Society (IHSS) method [9].AG'" MP-50 resin (Bio-Rad Laboratories, Inc) was used forcation exchange, and Amberlite'" XAD7HP resin (Rohm

Haas Co.) was used for the isolation of fulvic acid insteadof Amberlite '"XAD-8 resin, because the production of XAD-8 resin ceased some years ago and XAD7HP resin hasthe same chemical structure as XAD-8 resin(polymethylmethacrylate). Fulvic-like organics produced bythe ozone oxidation of HAs were also prepared as follows[10]. XWC-HA 1.0 g was dissolved in 250 mL of 0.1 NNaOH solution, and this solution was placed in a 500 mLgas-washing bottle as an oxidation reactor. Ozone gas (0.45mmoVL) was fed into the gaswashing bottle by bubbling ata flow rate of 50 Lib for 0.5, 1.0, 2.0 and 4.0 h, respectively.CP-HA was also used for fulvic-like organics

Sasaki et al., Annals of Environmental Science /2007, Vol

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production. 0.5 g CP-HA was dissolved in 250 mL of 0.1N NaOH solution and oxidized for 0.25,0.5, 0.75 and1.0 h using the same method as that used for XWC-HAoxidation. All oxidized samples were treated and isolatedusing the simplified IH$S method (Figure I). Fulvic-likeorganic acids produced by XWC-HA oxidation werenamed XWCS-0.5, XWCS1.0, XWCS-2.0, XWCS-4.0,and XWCS-0.5+ (Ozone gas, 1.15 mmoVL, 50 LibReaction time, 0.5 h), and those produced by CP-HAwere named CPS-0.25, CPS-0.5, CPS-0.75, and CPS-I.O, respectively.

DiSSolVed in 250mL 0

iN·NaOH

OxidlllionWIth 0, bUbOing lor

0 25-4.0M

pH 10 (HOI

C8rtJifUgation end filtration

Insoll.Ole

Hum~. Orglnic'

Ad~dby

x.AO-7HP reSin

Desorotd

0 1 N·NaOH

Figure 1 Fulvic-like organics production from humicacids by ozone oxidation.

~II

D M r ~ . . N . ~ . . . D M 5 , ~ . •

;1In1ng for O.Sh al room limp.'-SlImng under N

atmosphlre for 1 h

323K

i..

Methylsulflnyl carbanion (MSCA)

I = : ; : h l l r o o : n l l ~ . . . . . . . - . . . .

j . .

'~H.!I.

Umi

Slirring for 12h

room limp.

I( •.••

l h y 1 l l l o n )

DIalyzing by dlslliled

wallr

FI'HZI

drying

l l i 'f l l i t J l 1 Y l Q ~ ~ l ; m l

Figure 2 Pennethylation of fulvic acid by theHakomori method.All samples were freeze-dried and fmely ground,and were maintained in glass vessels in desiccators oversaturated LiCI solution at room temperature for wateradsorption measurements. The amounts of watervapor adsorbed were determined gravimetrically using anelectronic balance (Mettler-Toledo, Inc., AB204-S,Precision: O. I mg). Permethylated XWCS-O.5+(XWCS-0.5+methyl) was also prepared to examine theeffect of oxygen functional groups on the capacity forwater vapor adsorption of humic substances.Pennethylation was conducted with the Hakomorimethod [11,12] shown in Figure 2. The Hakomormethod is a rapid permethylation method catalyzed bymethylsulfmyl carbanion in dimethyl sulfoxide. Thismethod can be applied to methylate carboxyl anhydroxyl groups. Abbreviations of humic substances arelisted in Table I.Table 1 Abbreviation, Source, and Character of Humic SubstancesSource (Country)AbbreviationPeat(Canada)CP-HACP-FAWeathered coal (China, Xinjiang)XWC·HAXWC-FAAndosol (Japan)AS-HAAS-FAPeat HA (Canada)CPS-0.250.25CPS-0.500.5CPS-0.750.75CPS-I.OOICoal HA (China, Xinjiang)XWCS-O.5O.SXWCS·I.OIXWCS·2.02XWCS-4.04XWCS-O.S+O.S

XWCS-O.S+ (China, Xinjiang)XWCS-O.5+methyl

• Ozone, 1.15mmolfL.

Oxidation, h Character

FAFAFA

Pennethylated'2.2. Analysis of Fundamental PropertiesElemental analysis was perfonned with a Yanaco CHNCorder type MT-S (Yanaco Analytical Instruments Corp.,Japan). Carboxyl group content was measured with thecalcium acetate method [II,13]and phenolic hydroxylgroup content was measured with the Folin-Ciocalteumethod [11,14].The EJE6 ratio was calculated bmeasuring absorbance of the humic substances dissolvedin 0.1 N NaOH at 400 and 600 run using a spectrometer(Shimadzu, Model

1700).

Low moleculer/ FugavicFulvic-likeOrganic acids(XWCS/CPS)

Sasaki et aI., Annals of Environmental Science /2007, Vol

7-22

Table

2 Elemental and functional characteristics of humic substancesElemental analysis

wto/a-d.a.f.

Ash,Elemental ratio Functionalgroups, mmollgCHN

diff.

w t O lo

HlC

OIC

COOH

Phe-OH

CP-HA57.35.42.035.33.51.130.463.01n.d.CP-FA52.44.70.742.20.21.080.606.31n.d.XWC-HA64.13.61.530.83.60.670.364.531.41XWC-FA43.03.51.252.40.00.960.914.280.14AS-HA59.23.52.834.50.70.700.445.500.17AS-FA48.74.33.044.00.21.040.689.120.56CPS-0.2549.13.41.345.90.30.820.707.36n.d.CPS-0.5045.53.51.346.73.00.910.777.82n.d.CPS-0.7547.93.51.545.41.70.860.718.14n.d.CPS-1.046.03.61.646.91.80.940.778.69n.d.XWCS-O.538.12.71.657.62.20.851.147.810.82XWCS-1.036.82.71.359.22.00.871.218.310.81XWCS-2.043.03.21.752.11.10.890.916.52n.d.XWCS-4.046.03.51.848.61.10.910.798.991.09XWCS-o.5+50.13.71.450.12.70.870.679.100.93XWCS-o.5+methyl 54.14.21.640.12.90.560.933.111.00• Yanaco CHN Corder;

Calcium acetate method;

Folin-Chiocalteu method;ad.a.f: Dry ashfree basis; n.d.:Not detected.

Table

3 13C NMR estimates of carbon distribution, molecular weight, EJE6 ratio and BET surface area in humicsubstancesAbbreviationCarbon distribution,

EJE6 Sa

CarbonylCarboxylPhenolic AromaticSubstitutedAliphaticM

ratio

/ g

CP-HA7.514.05.214.322.236.817.3005.20.64CP-FAn.d15.43.219.036.126.32,60015.1n.a.XWC-HA10.79.65.939.113.021.68,8003.30.93XWC-FA12.320.914.77.620.424.1n.a.n.a.n.a.AS-HA12.018.015.027.016.012.014,0006.8n.d.AS-FAn.d31.40.030.66.131.91,20017.3n.a.CPS-0.257.919.64.021.322.324.88,80012.41.11CPS-0.50n.a.5;00013.3n.a.CPS-0.75n.a.3,20014.8n.a.CPS-l.On.a.90015.3n.d.XWCS-0.58.720.94.226.920.518.9n.a.8.9n.a.XWCS-1.0n.a.n.a.7.6n.a.XWCS-2.0n.a.n.a.6.6n.a.XWCS-4.06.620.7·3.420.925.922.51,8006.7n.a.XWCS-0.5+10.323.62.420.615.1.28.05007.20.95XWCS-0.5+methyl n.a. n.a. n.a. n.a.

• M

Number-averaged molecular weight;

Sa:

Surface area by BET method with nitrogen; n.a.: Not Carbon distributions were determined byCPIMAS 13C_NMR spectrometry (Broker, AVANCE 300; MAS frequency 6 kHz; contact time 2ms; repetition time 3 s; number of scans 2000-10000).Molecular masses were investigated by gel permeationchromatography (GPC) using pullulan as the calibrant.GPC was carried out at 70°C on a Shimadzu LC-lOA series apparatus equipped with two Plgel 5

J.UIl

Mixed-D GPC columns (Polymer Laboratories Ltd.;linear range of molecular weight,

200-400,000)

and arefractive index detector. The mobile phase consistedof DMSO at a flow rate of 0.5 mLlmin. The surfaceAbbreviation