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0. Sasaki et al., Annals of Environmental Science /2007, Vol 2, 17-22

HUMIC GROUP HYGROSCOPIC ameliorate degraded soils. Under low -moisture conditions,
the hygroscopic properties of soil orga nic materials are
PROPERTIES AND THEIR important for soil wettability, microbial activity, and the
CHEMICAL STRUCTURE dynamics of soil carbon [1 -3]. Humic and fulvic acids are
able to adsorb large amounts of water [4]. The hygroscopic
properties of humic materials have been well studied; in
particular, there have been comparisons between humic acid
Osamu Sasaki, Isamu Kanai, Yuuki
. (HA) and fulvic acid (FA) and the effects of their functional
groups and monovalent metal cations [4,5]. Recent studies
Yazawa and Tatsuaki Yamaguchi
of the hygroscopic properties of humic materials have been
Graduate School of Engineering, Chiba I nstitute of conducted in the field of atmospheric aerosols [6 -8].
Technology, 2-17-1 Tsudanuma, Narashino, Chiba However, these aerosol studies were mainly based on the
275-0016, Japan interaction of humic substances (and/or humic like
substances) and in organic salts with respect to the types of
Received June 9, 2006; in final form December 13, inorganic salts.
2006; Accepted January 2, 2007
Clarification of the relation between the chemical structure
of humic materials and their hygroscopic properties is
important because it attempts to further address the
ABSTRACT
influence of soil organic matter structure on water sorption,
and thus its potential influence on soil wettability and other
We investigated the relationship between the hygro -
important aspects. The purpose of this paper is to present an
scopic properties and chemical struct ures of humic and
evaluation and discussion of water vapor adsorption by
fulvic acids. Humic and fulvic acids were extracted
HAs and F As in order to clarify the relationship between
from andosol, Canadian peat and Chinese weathered
their chemical characteristics and their capacity for water
coal using the IHSS method. Fulvic -like organics
vapor adsorption.
produced by the ozone oxidation of humic acid were
also prepared by a method reported p reviously. Their
main chemical properties related to hygroscopicity 2. MATERIALS AND METHODS
were also studied by elemental analysis and the
measurement of functional group contents. Humic and 2.1. Humic Materials
fulvic acids were allowed to stand under various
relative humidity (RH) conditions and t he amounts of The humic and fulvic acids used in this study were obtained
water vapor adsorbed were measured by gravimetry. from Japanese andosol (AS), Canadaian peat (CP), and
Water adsorption isotherms were similar for both Chinese weathered coal from Xinjiang, (XWC). Humic acid
humic and fulvic acids below RH 80%. Above 80%, (HA) and fulvic acid (FA) were extracted with the
water vapor adsorption of fulvic acids and fulvic -like International Humic Substances Society (IHSS) method [9].
organics increased considerably as compa red with AG'" MP-50 resin (Bio-Rad Laboratories, Inc) was used for
humic acids. Deliquescence was observed for all fulvic cation exchange, and Amberlite'" XAD7HP resin (Rohm &
acids and fulvic-like organics at higher RH. The Haas Co.) was used for the isolation of fulvic acid instead
amount of water vapor adsorbed at 97% RH by humic of Amberlite '" XAD-8 resin, because the production of
XAD-8 resin ceased some years ago and XAD7HP resin has
substances from different sources was highly correlated
the same chemical structure as XAD -8 resin
with the ratio of oxygen to carbon co ntents.
(polymethylmethacrylate). Fulvic -like organics produced by
Keywords: Humic structure, hygroscopic properties, the ozone oxidation of HAs were also prepared as follows
humidity, water retention [10]. XWC-HA 1.0 g was dissolved in 250 mL of 0.1 N
1. INTRODUCTION NaOH solution, and this solution was placed in a 500 mL
gas-washing bottle as an oxidation reactor. Ozone gas (0.45
Natural humic materials have been used recently to mmoVL) was fed into the gas washing bottle by bubbling at
a 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
,
,
-'

0. Sasaki et al., Annals of Environmental Science /2007, Vol 2, 17-22

production. 0.5 g CP-HA was dissolved in 250 mL of 0.1 vapor adsorbed were determined gravimetrically using an
N NaOH solution and oxidized for 0.25, 0.5, 0.75 and electronic balance (Mettler-Toledo, Inc., AB204-S,
1.0 h using the same method as that used for XWC -HA Precision: O. I mg). Permethylated XWCS -O.5+
oxidation. All oxidized samples were treated and isolated (XWCS-0.5+methyl) was also prepared to examine the
using the simplified IH$S method (Figure I). Fulvic -like effect of oxygen functional groups on the capacity for
organic acids produced by XWC-HA oxidation were water vapor adsorption of humic substances.
named XWCS-0.5, XWCS1.0, XWCS-2.0, XWCS-4.0, Pennethylation was conducted with the Hakomori
and XWCS-0.5+ (Ozone gas, 1.15 mmoVL, 50 Lib; method [11,12] shown in Figure 2. The Hakomori
Reaction time, 0.5 h), and those produced by CP -HA method is a rapid permethylation method catalyzed by
were named CPS-0.25, CPS-0.5, CPS-0.75, and CPS- methylsulfmyl carbanion in dimethyl sulfoxide. This
I.O, respectively. method can be applied to methylate carboxyl and
hydroxyl groups. Abbreviations of humic substances are
listed in Table I.
0, Table 1 Abbreviation, Source, and Character of
DiSSolVed in 250mL 0 iN·NaOH Oxidlllion Humic Substances
WIth 0, bUbOing lor 0 25-4.0M
pH 10 (HOI
C8rtJifUgation end filtration Source (Country)
Abbreviation Peat Oxidation, h Character
Insoll.Ole
(Canada)
I Hum~. +Orglnic' I Desorotd Dy 0 1 N·NaOH
CP-HA HA
Ad~dby x.AO- CP-FA FA
7HP reSin
Weathered coal (China, Xinjiang)
XWC·HA HA
XWC-FA FA
Fulvic-like Organic acids
Low moleculer / Fugavic
(XWCS/CPS) Andosol (Japan)
acid
AS-HA HA
AS-FA FA
Figure 1 Fulvic-like organics production from humic Peat HA (Canada)
acids by ozone oxidation. CPS-0.25 0.25 FA
CPS-0.50 0.5 F
CPS-0.75 0.75 A
~I I DMr~.. N.~... DM5,~ .• CPS-I.OO
Coal HA (China, Xinjiang)
XWCS-O.5
I

O.S
F
A
FA
;1In1ng for O.Sh al room limp.' - SlImng under N I
XWCS·I.O I FA
i + atmosphlre for 1 h II 323K
XWCS·2.0 2 FA
i.. j Methylsulflnyl carbanion (MSCA)
XWCS-4.0 4 FA
I=:;:hllroo:nll~. ..... . - .... XWCS-O.S+ O.S a F
XWCS-O.S+ (China, Xinjiang) A
j.. '~H.!I. XWCS-O.5+methyl Pennethy
Umi
• Ozone, 1.15mmolfL. lated
I
lhy1lllon)
f Slirring
( •.••
for 12h II room limp.

'2.2. Analysis of Fundamental Properties


I DIalyzing by dlslliled wallr
1 FI'HZI drying
Elemental analysis was perfonned with a Yanaco CHN
lli'fllitJl1YlQ~~l;ml Corder type MT-S (Yanaco Analytical Instruments Corp.,
Japan). Carboxyl group content was measured with the
Figure 2 Pennethylation of fulvic acid by the calcium acetate method [II, 13] and phenolic hydroxyl
group content was measured with the Folin -Ciocalteu
Hakomori method. method [11, 14]. The EJE6 ratio was calculated by
measuring absorbance of the humic substances dissolved
All samples were freeze-dried and fmely ground, in 0.1 N NaOH at 400 and 600 run using a spectrometer
and were maintained in glass vessels in desiccators over (Shimadzu, Model UV1700).
saturated LiCI solution at room temperature for wa ter
adsorption measurements. The amounts of water

1
8
0. Sasaki et aI., Annals of Environmental Science /2007, V ol 2, J 7-22

Table 2 Elemental and functional characteristics of humic substances


d
Elemental analysis s, wto/a-d.a.f. Ash, Elemental ratio Functional
Abbreviatio groups, mmollg
n C H N 0, diff. wtOlo HlC OIC COOH b Phe-OH C
CP-HA 57.3 5.4 2.0 35.3 3.5 1.13 0.46 3.01 n.d.
CP-FA 52.4 4.7 0.7 42.2 0.2 1.08 0.60 6.31 n.d.
XWC-HA 64.1 3.6 1.5 30.8 3.6 0.67 0.36 4.53 1.41
XWC-FA 43.0 3.5 1.2 52.4 0.0 0.96 0.91 4.28 0.14
AS-HA 59.2 3.5 2.8 34.5 0.7 0.70 0.44 5.50 0.17
AS-FA 48.7 4.3 3.0 44.0 0.2 1.04 0.68 9.12 0.56
CPS-0.25 49.1 3.4 1.3 45.9 0.3 0.82 0.70 7.36 n.d.
CPS-0.50 45.5 3.5 1.3 46.7 3.0 0.91 0.77 7.82 n.d.
CPS-0.75 47.9 3.5 1.5 45.4 1.7 0.86 0.71 8.14 n.d.
CPS-1.0 46.0 3.6 1.6 46.9 1.8 0.94 0.77 8.69 n.d.
XWCS-O.5 38.1 2.7 1.6 57.6 2.2 0.85 1.14 7.81 0.82
XWCS-1.0 36.8 2.7 1.3 59.2 2.0 0.87 1.21 8.31 0.81
XWCS-2.0 43.0 3.2 1.7 52.1 1.1 0.89 0.91 6.52 n.d.
XWCS-4.0 46.0 3.5 1.8 48.6 1.1 0.91 0.79 8.99 1.09
XWCS-o.5+ 50.1 3.7 1.4 50.1 2.7 0.87 0.67 9.10 0.93
XWCS-o.5+methyl 54.1 4.2 1.6 40.1 2.9 0.56 0.93 3.11 1.00
• Yanaco CHN Corder; 6 Calcium acetate method; C Folin-Chiocalteu method; a d.a.f: Dry ash free basis; n.d.:
Not detected.

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

Carbon distribution, % EJE6 Sa b


Abbreviation
Carbonyl Carboxyl Phenolic Aromatic Substituted Aliphatic MnQ ratio m2/g
CP-HA 7.5 14.0 5.2 14.3 22.2 36.8 17.300 5.2 0.64
CP-FA n.d 15.4 3.2 19.0 36.1 26.3 2,600 15.1 n.a.
XWC-HA 10.7 9.6 5.9 39.1 13.0 21.6 8,800 3.3 0.93
XWC-FA 12.3 20.9 14.7 7.6 20.4 24.1 n.a. n.a. n.a.
AS-HA 12.0 18.0 15.0 27.0 16.0 12.0 14,000 6.8 n.d.
AS-FA n.d 31.4 0.0 30.6 6.1 31.9 1,200 17.3 n.a.
CPS-0.25 7.9 19.6 4.0 21.3 22.3 24.8 8,800 12.4 1.11
CPS-0.50 n.a. 5;000 13.3 n.a.
CPS-0.75 n.a. 3,200 14.8 n.a.
CPS-l.O n.a. 900 15.3 n.d.
XWCS-0.5 8.7 20.9 4.2 26.9 20.5 18.9 n.a. 8.9 n.a.
XWCS-1.0 n.a. n.a. 7.6 n.a.
XWCS-2.0 n.a. n.a. 6.6 n.a.
XWCS-4.0 6.6 20.7 ·3.4 20.9 25.9 22.5 1,800 6.7 n.a.
XWCS-0.5+ 10.3 23.6 2.4 20.6 15.1 .28.0 500 7.2 0.95
XWCS-0.5+methyl n.a. n.a. n.a. n.a.
• Mn: Number-averaged molecular weight; 6 Sa: Surface area by BET method with nitrogen; n.a.: Not
analyzed; n.d.: Not
detected.

Carbon distributions were determined by GPC was carried out at 70°C on a Shimadzu LC -
CPIMAS 13C_NMR spectrometry (Broker, A lOA series apparatus equipped with two Plgel 5 J.UIl
VANCE 300; MAS frequency 6 kHz; contact time 2 Mixed-D GPC columns (Polymer Laboratories Ltd.;
ms; repetition time 3 s; number of scans 2000 -10000). linear range of molecular weight, 200-400,000) and a
Molecular masses were investigated by gel permeation refractive index detector. The mobile phase consisted
chromatography (GPC) using pullulan as the calibrant. of DMSO at a flow rate of 0.5 mLlmin. The surface
1
9
0. Sasaki et al., Annals of Environmental Science /2007, Vol 2, 17-22

areas were measured by the BET method with nitrogen adsorption were similar for humic and fu lvic acids
using a surface area anal yzer (Micromeritics ASAP below 75% RH. Above 75% RH, water vapor
2020). The analytical characteristics of HAs, F As and adsorption of F As and fulvic -like organics increased
fulvic-like organics are shown in Tables 2 and 3. considerably as compared humic acids. These marked
increases in the amount of water vapor adsorbed at
high RH are similar to those in previous reports [4, 6-
2.3. Analysis of Amount of Water Vapor Adsorbed 8]. As deliquescence could be observed for all fulvic
acids and fulvic-like organics at higher RH values,
Water vapor adsorption experiments were performed deliquescent properties may be important in explaining
on 200 mg samples maintain ed in weighting bottles in the hygroscopicity of humic substances.
desiccators at different RH values (33 -97%) at 303 K.
RH was controlled using selected aqueous saturated 3.3. Relationship between Chemical Characteristi cs
salt solutions (MgClz, NaHS0 4, NaCI, KCI, KN0 3, and and Amount of Water Vapor Adsorbed by Humic
K2S04) [15]. Samples were withdrawn from the Substances
desiccators and weighed un~ il constant weights were
obtained. At the end of this period, increases in The relationship between the amount of water vapor
moisture were expressed as grams of H 20 per gram of adsorbed at 97% RH and the amount of carboxyl
initial HAs and FAs that were heat -dried at 378K for carbon (carboxyl C) as a percentage of total carbon
24 h. The amount of water vapor adsorbed was (total C) is shown in Figure 5, and that between the
calculated as follows: water vapor adsorption and the elemental O/C ratio is
shown in Figure 6.
(amount of water vapor adsorbed) = ([wet sample
mass] - [dry sample mass])/(dry sample mass) (I) :; 1.0
Cl
~ f', XWcs-o.5i
l:
~ 0.8 lJ XWe-H~J
3. RESULTS AND DISCUSSION J:o--- .-(S' .'
g
-g 0.6
3.1. Characteristics of Humic Materials
8-
~ 0.4
The analytical characteristics of the HAs, F As and ~
S
III
fulvic-like organics are shown in Table 2. The ~ {}--- ---0- . n-
'0 0.2
carboxyl and oxygen contents of fulvic -like organics 'E
produced by ozone oxidation increased from 4.53 "E
0
mmol COOWg (30.8 wt%) for XWC -HA and 3.01 0 [
« 0 5 10 1
mmol COOWg (35.3 wtOlo) for CP-HA to 6.52-9.10 5
mmol COOWg (40.1-59.2 wt%) for XWCS and 7.36 - Time (day)
8.69 mmol COOWg ( 45.4-46.9 wt%) for CPS,
depending on the oxidation time. The carboxyl and . Figure 3 Time courses of the weight changes on water
oxygen contents of permethylated XWCS decreased vapor adsorption by hurnic substances.
from 9.10 mmol COOWg (50.1 wt%) for XWCS -0.5
to 3.11 mmol COOWg (40.lwt%) for XWCS -
0.5+methyl, on permethylation.
b.
s
c: o ~A

3.2. Water Vapor Adsorption


i
0.8 -Ir .. CP-
OJ
i HA
I
o 11 CP-FA
The time courses of weight change on water vapor 0.6
adsorption by humic substances are shown in Figure 3. o CPs.o.25
Weights of humic substances increased rapidly at an
early stage. Reaching a constant weight took about 2 J 0.4

weeks for HAs and 3 weeks for F As. De liquescence f


'll 0.2
() ~.5+

was observed for all F As and fulvic -like organics 1: 20 40 60 60


above 80% RH. j 0 100
Water vapor adsorption isotherms, measured at 0
Relative humldlly (%RH)

303K for HAs, FAs and fulvic -like organics are shown Figure 4 Isotherms for water vapor adsorption by
in Figure 4. Isotherms of water vapor humic substances at 303 K.

2
0
O. Sasaki et aI., Annals of Environmental Science /2007, Vol 2, 17-22

Table 2 Elemental and functional characteristics of humic substances

Elemental analysis·, wto/o -d.a.f.dAsh, Elemental ratio Functional


Abbreviation groups, mmoVg
C H N 0, iliff. wt% HlC O/C COOH b Phe-OH C
CP-HA 57.3 5.4 2.0 35.3 3.5 1.13 0.46 3.01 n.d.
CP-FA 52.4 4.7 0.7 42.2 0.2 1.08 0.60 6.31 n.d.
XWC-HA 64.1 3.6 1.5 30.8 3.6 0.67 0.36 4.53 1.41
XWC-FA 43.0 3.5 1.2 52.4 0.0 0.96 0.91 4.28 0.14
AS-HA 59.2 3.5 2.8 34.5 0.7 0.70 0.44 5.50 0.17
AS-FA 48.7 4.3 3.0 44.0 0.2 1.04 0.68 9.12 0.56
CPS-0.25 49.1 3.4 1.3 45.9 0.3 0.82 0.70 7.36 n.d.
CPS-0.50 45.5 3.5 1.3 46.7 3.0 0.91 0.77 7.82 n.d.
CPS-0.75 47.9 3.5 1.5 45.4 1.7 0.86 0.71 8.14 n.d.
CPS-1.0 46.0 3.6 1.6 46.9 1.8 0.94 0.77 8.69 n.d.
XWCS-O.5 38.1 2.7 1.6 57.6 2.2 0.85 1.14 7.81 0.82
XWCS-1.0 36.8 2.7 1.3 59.2 2.0 0.87 1.21 8.31 0.81
XWCS-2.0 43.0 3.2 1.7 52.1 1.1 0.89 0.91 6.52 n.d.
XWCS-4.0 46.0 3.5 1.8 48.6 1.1 0.91 0.79 8.99 1.09
XWCS-o.5+ 50.1 3.7 1.4 50.1 2.7 0.87 0.67 9.10 0.93
XWCS-0.5+methyl 54.1 4.2 1.6 40.1 2.9 0.56 0.93 3.11 1.00
·Yanaco CHN Corder; 6 Calcium acetate method; cFolin -Chiocalteu method; dd.a.f: Dry ash free basis; n.d.: Not
detected.

Table 3 J3C NMR estimates of carbon distribution, molecular weight, EJE6 ratio and BET surface area in humic
substances

Carbon distribution, % EJE6 Sa b


Mo Q
Abbreviation Carbonyl Carboxyl Phenolic Aromatic Substituted Aliphatic ratio m2 /g
CP-HA 7.5 14.0 5.2 14.3 22.2 36.8 17,300 5.2 0.64
CP-FA n.d 15.4 3.2 19.0 36.1 26.3 2,600 15.1 n.a.
XWC-HA 10.7 9.6 5.9 39.1 13.0 21.6 8,800 3.3 0.93
XWC-FA 12.3 20.9 14.7 7.6 20.4 24.1 n.a. n.a. n.a.
AS-HA 12.0 18.0 15.0 27.0 16.0 12.0 14,000 6.8 n.d.
AS-FA n.d 31.4 0.0 30.6 6.1 31.9 1,200 17.3 n.a.
CPS-0.25 7.9 19.6 4.0 21.3 22.3 24.8 8,800 12.4 1.11
CPS-0.50 n.a. 5,000 13.3 n.a.
CPS-0.75 n.a. 3,200 14.8 n.a.
CPS-1.0 n.a. 900 15.3 n.d.
XWCS-0.5 8.7 20.9 4.2 26.9 20.5 18.9 n.a. 8.9 n.a.
XWCS-I.O n.a. n.a. 7.6 n.a.
XWCS-2.0 n.a. n.a. 6.6 n.a.
XWCS-4.0 6.6 20.7 ·3.4 20.9 25.9 22.5 1,800 6.7 n.a.
XWCS-0.5+ 10.3 23.6 2.4 20.6 15.1 28.0 500 7.2 0.95
XWCS-O.5+methyl n.a. n.a. n.a. n.a.
• Mn: Number-averaged molecular weight; 6 Sa: Surface area by BET method with nitrogen; n.a.: Not analyzed;
detected.
n.d.: Not

Carbon distributions were determined by CP/MAS GPC was carried out at 70°C on a Shimadzu LC lOA
13C_NMR spectrometry (Bruker, A VANCE 300; MAS series apparatus equipped with two Plgel 5 IlIIl Mixed-D
frequency 6 kHz; contact time 2 ms; repetition time 3 s; GPC columns (Polymer Laboratories Ltd.; linear range of
number of scans 2000-10000). Molecular masses were molecular weight, 200-400,000) and a refractive index
investigated by gel permeation chromatography (GPC) detector. The mobile phase co nsisted of DMSO at a flow
using pullulan as the calibrant. rate of 0.5 mL/min. The surface
1
9
-- ~---------

0. Sasaki et aI.. Annals of Environmental Science /2007. Vol 2, 17-22

areas were measured by the BET method with nitrogen adsorption were similar for humic and fulvic acids
using a surface area analyzer (Micromeritics ASAP below 75% RH. Above 75% RH, water vapor
2020). The analytical characteristics of HAs, F As and adsorption of F As and fulvic-like organics increased
fulvic-like organics are shown in Tables 2 and 3. considerably as compared humic acids. These marked
increases in the amount of water vapor adsorbed at
high RH are similar to those in previous reports [4, 6-
2.3. Analysis of Amount of Water Vapor Adsorbed 8]. As deliquescence could be observed for all fulvic
acids and fulvic-like organics at higher RH values,
Water vapor adsorption experiments were performed deliquescent properties may be important in explaining
on 200 mg samples maintained in weighting bottles in the hygroscopicity of humic substances.
desiccators at different RH values (33-97%) at 303 K.
RH was controlled using selected aqueous saturated 3.3. Relationship between Chemical Characteristics
salt solutions (MgCh, NaHS0 4, NaCl, KCl, KN03, and and Amount of Water Vapor Adsorbed by Humic
K2S04) [15]. Samples were withdrawn from the Substances
desiccators and weighed un~l constant weights were
obtained. At the end of this period, increases in The relationship between the amount of water vapor
moisture were expressed as grams of H20 per gram of adsorbed at 97% RH and the amount of carboxyl
initial HAs and F As that were heat-dried at 378K for carbon (carboxyl C) as a percentage of total carbon
24 h. The amount of water vapor adsorbed was (total C) is shown in Figure 5, and that between the
calculated as follows: water vapor adsorption and the elemental O/C ratio is
shown in Figure 6.
(amount of water vapor adsorbed) = ([wet sample
mass] - [dry sample mass])/(dry sample mass) (1) f" 1.0
Cl
.9
c: I XWcs-o.51
/I

3. RESULTS AND DISCUSSION ~ 0.8 [lJ XWC-HA


0
II)
"0
IV 0.6
3.1. Characteristics of Humic Materials 5
a.
IV
> 0.4
The analytical characteristics of the HAs, F As and '-
I~V
fulvic-like organics are shown in Table 2. The ~
'0 0.2
carboxyl and oxygen contents of fulvic-like organics
;:
produced by ozone oxidation increased from 4.53 0
:l

mmol COOHlg (30.8 wt%) for XWC-HA and 3.01 E o l(


« 0 5 1 1
mmol COOHlg (35.3 wt%) for CP-HA to 6.52-9.10 0 5
mmol COOHlg (40.1-59.2 wt"1o) for XWCS and Time (day)
7.368.69 mmol COOHlg (45.4--46.9 wt%) for CPS,
depending on the oxidation time. The carboxyl and . Figure 3 Time courses of the weight changes on water
oxygen contents of permethylated XWCS decreased vapor adsorption by humic substances.
from 9.10 mmol COOHlg (50.1 wt%) for XWCS-0.5
to 3.11 mmol COOHlg (40.1wt%) for XWCS-
0.5+methyl, on permethylation. -b o
.9 to
. o f>S.FA
o
3.2. Water Vapor Adsorption 0.8

t
0
,
I
,
o (, CP-FA
The time courses of weight change on water vapor
0.8
adsorption by humic substances are shown in Figure 3. o CPS-O.25
Weights of humic substances increased rapidly at an
l
early stage. Reaching a constant weight took about 2 ~ 0.4 o XWCS-O.5+
weeks for HAs and 3 weeks for F As. Deliquescence
was observed for all F As and fulvic-like organics
I
'8
20 40 80 80
above 80% RH. 0.2 100
Water vapor adsorption isothenns, measured at
303K for HAs, F As and fulvic-like organics are j Relative ""mldlly (%RH)

Figure 4 Isothenns for water vapor adsorption by


0
shown in Figure 4. Isothenns of water vapor humic substances at 303 K.
0

20
----------_._-----~---~----~~~~~~~~~----~-- - ---~~~~~~-

O. Sasaki et al., Annals of Environmental Science /2007, Vol 2, J 7-22

The amounts of water vapor adsorbed at 97% RH by


2.5 • CP·HA
humic substances increased with increasing carboxyl o CP·FA
content and O/C ratio, and the O/C ratio showed a • xwC·HA
stronger correlation (r
= 0.83) than the carboxyl content
AAS-HA
(:, AS-FA
(r = 0.67) for the differ~nt sources. XWCS-O.5+methyl Y' 0.073 •. 0.35
R'. 0.67
t CPS-C.25
+ CPS-C.50
+ CPS-C.75
(the permethylated fulvic-like organic sample) adsorbed t CP5-1.00
less water vapor than the other XWCSs, related to the x XWCS-C.5 x
XWC5-1.0 )(
decreased O/C ratio and carboxyl content. This result XWC5-2.0 )(
XWCS-4.O )(
shows that the O/C ratio and the carboxyl group directly XWCS-C.5+
influence the water vapor adsorption capacity of hurnic o XWCS-c.5+methyt
----- -. "-- ....
substances.
10 20 30
Carboxyl C I Total C (%)

• CP·HA
2.5 o CP·FA
• xwC·HA Figure 6 Relationship between the carboxyl content
6.
.9 2 y·2.33X-D.n A AS-HA and the amount of water vapor adsorbed by humic
c R'·o.83 (:, AS-FA
.2 + CPS-c.25 substances .
"eo 1.5 + CPS-c.50
51 + CPS-c.75
+ CPS·l.00
~
x XWCS-c.5 2.5 • CP·HA
o CP.FA
[ x XWCS.l.0
• XWC-HA
)( XWCS·2.0 ~ 2 .AS-HA
~ 0,
. y·0.1611·127 6 !'SofA
)( XWCS-4.0
c
9 R'. 0.74 + CPS-O.25
0.5
;
)( XWCS-c.5+
1 1.5 + CPS-O.50

, 0

0 0.5
O/C ratio
1.5
o XWCS-c.5+melhyt

~
6
c.
••
>
~
0.5
I
If/'
I
I

y • O,05x + 0.05

R'. 0.911
1- CPS-O.75

+ CP5-1.00
x XWCS-O.5
;( XWC5-1.0
;( XWC5-2.0
)( XWC5-4.0

;( XWCS-o.5+
Figure 5 Relationship between the elemental O/C ~ 0
ratio and the amount of water vapor adsorbed by 0 5 10 15 20
humic substances. E41E6 ratio

The EJE6 ratio is an index of light absorption in the Figure 7 Relationship between the E.JE6 ratio and the
visible range. A high E.JE6 ratio corresponds to a amount of water vapor adsorbed by humic substances.
relatively low molecular weight, and a low ratio
corresponds to a relatively high molecular weight [16,
17]. Figure 7 shows that, although the E.JE6 ratios were 4. CONCLUSIONS
correlated with the amount of water adsorbed within the
natural humic substances or in XWCSs or in CPSs, the We aimed to clarify the relationship between the water
E.JE6 ratios varied among the different sources of humic vapor adsorption capacities of various humic substances
substances. This variation suggests that water vapor and their chemical characteristics. In our studies we used
adsorption capacity depends on oxygen functional group, humic materials from several sources and th~ir oxidized
and not on the molecular products, which have fulvic-like
weight. . . characteristics. Although the amoUnt of water vapor
Schnitzer [4] reported that oxygen functtonal groups adsorbed varied among the various sources of humic
affect water vapor adsorption capacity by HA and FA substances, the water vapor adsorption of the humic
obtained from Podzol. In our experiment, we confirmed substances was well correlated with their O/C ratio.
that the O/C ratio is an important factor affecting the Humic substances differ in hygroscopicity, and this
water adsorption capacity of several kinds of humic difference might affect the wettability, the microbial
substances extracted with the IHSS method from peat
activity and carbon sequestration when degraded soils in
(Canada), weathered coal (China) and Andosol (Japan) at
arid lands are ameliorated with humic substances from
higher humidities, and that the water adsorption capacity
of humic substances roughly could be explained only by different sources.
the O/C ratio.

21
0. Sasaki et al., Annals of Environmental Science /2007, Vol 2, J 7-22

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