HUMIC AND FULVIC ACIDS IN

SEDIMENTS AND SOILS OF AGRICULTURAL WATERSHEDS

L. M. WHITBY and M. SCHNITZER
Soil Research Institute, Agriculture Canada, Ottawa, Ontario Kl A 0C6. Contribution no. 673,
received 2 Nov. 1977, accepted 9 Jan. 1978'

Wnrrev, L. M. axo ScsNrrzr,n, M. 1978. Humic and fulvic acids in sediments

and soils ofagricultural watersheds. Can. J. Soil Sci. 58: 167-178

Humic and fulvic acids were extracted from suspended and bottom sediments and
soils of small agricultural watersheds of Southern Ontario and characterized by
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chemical and spectrophotometric methods and by chemical degradation. Soil humic

and fulvic acids were found to be similar to sediment humic and fulvic acids,
respectively, in elemental and functional group composition and in surface structural
features. Metal-binding capacities of sediment and soil humic and fulvic acids were
estimated from their CO2H and phenolic OH group contents. Because watershed
soils contained per unit weight considerably more humic materials than did adjacent
bottom sediments, the metal-binding capacity due to humic and fulvic acids in the
watershed soils was considerably higher than that due to humic and fulvic acids in
the sediments. Major products resulting from the alkaline KMnOa oxidation of soil
and sediment humic and fulvic acids were benzenecarboxylic and phenolic acids.
The chemical, spectrophotometric and degradation data indicated that sediment and
soil humic substances had similar chemical structures.

Les acides fulviques et humiques ont 6t6 extraits des charges en suspension, des
s6diments de fond et des sols adjacents de petits bassins hydrographiques agricoles
du sud de I'Ontario. On les a caractdris6s par analyses chimique et spec-
trophotom6trique et par d6gradation chimique. La composition 6l6mentaire, la
nature des groupements fonctionnels et les caract6ristiques structurales de surface
sont les mOmes dans les acides humiques et fulviques des sols et des s6diments,
respectivement. La capacit6 de fixation des m6taux par les acides humiques et
fulviques des sols et des s6diments a 6t6 6valu6e h partir des teneurs en groupements
COzH et OH ph6nolique. Puisque les sols des bassins hydrographiques renferment,
en poids, beaucoup plus de matibres humiques que les s6diments de fond adjacents,
la capacit6 de fixation due aux acides humiques et fulviques y est plus 6lev6e que
dans les s6diments. L'oxydation par le KMnOa en milieu alcalin des acides
humiques et fulviques des sols et des s6diments produit principalement des acides
benzdne-carboxyliques et ph6noliques. Les r6sultats des analyses chimiques, de la
spectrophotom6tde et de la d6gradation r6vdlent que les mat6riaux humiques des sols
et des s6diments possddent des structures chimiques semblables.

Humic substances, the major organic com- low-molecular weight humic substances
ponents of soils and sediments, arise from (fulvic acids, FA's) are water-soluble,
the chemical and biological degradation of whereas higher-molecular weight fractions
plant and animal residues and from syn- (humic acids, HA's) are no longer soluble
thetic activities of microorganisms. The in water.Important characteristics of all
products so formed tend to associate into humic substances are their ability to form
polymeric structures that are rnore resistant stable complexes with metal ions and
to microbial degradation than are the hydrous oxides and to interact with minerals
starting materials. In free acid forms, (clays) and hydrophobic organic com-
Can J. Soil Sci. 5E: 167-17E (May 197E) pounds (Schnitzer and Khan 1972; Flaig et
167
 168 CANADIAN JOURNAL OF SOIL SCIENCE

al. 1975). Of special interest is the forma- contributed by the terrestrial and aquatic com-
tion of water-soluble complexes of FA's munities. The soils adjacent to the sediments
with toxic metals and organics which can were mainly Orthic Humic Gleysols or Orthic
increase concentrations of these con- Gray Brown Luvisols developed on basic glacial
stituents in natural waters and soil solutions
till of varying depths (Whitby et al. 1917).
Investigations were made of the most common
to levels which are far in excess of their soils in each watershed those which could be
normal solubilities. - most soil material to
expected to contribute the
Our major objective was to characteize the sediment. Twenty separate surface soil
humic materials extracted from susoended samples were composited for analysis of each
and bottom sediments and from adjacent soil type.
soils and to compare the results with each
Extraction of HA's and FA's
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other and with "mean" humic materials Soil and bottom sediment samples were trans-
(Schnitzer L977). A second objective of our ported to the laboratory, air-dried, passed
investigation was to estimate, on the basis through a 2-mm nylon sieve and analyzed for
of their analytical characteristics, metal- total C, carbonate-C, total S, total N andpH.
binding capacities of HA's and FA's in soils For the extraction of HA's and FA's, 300 g of
and sediments. air-dried sediment or soil were placed in a 4- Q
beaker to which 0.1 N HCI was added to
decompose carbonates which could have inter-
MATERIALS AND METHODS fered with the extraction of the humic sub-
Sampling Procedures stances. Once the evolution of CO: had ceased,
Six small watersheds of different agricultural the sediment or soil was centrifuged and washed
uses in Southem Ontario were identified for twice with distilled water by centrifugation.
intensive study by the International Reference Carbonate-free sediment or soil was placed in a
Group on Pollution from Land Use Activities narrow-necked polypropylene flask and 3 Q of
(PLUARG). Some characteristics of the water- 0.5 N NaOH added. The air in the flask and
sheds and their geographical locations are listed sample was displaced by N2 and the system left
in Table I and Fig. l, respectively. 'Ihe rationale to stand for 24 h with intermittent shaking.
for selecting these watersheds and further details Following this, the supematant was separated
of the agricultural activities in each watershed from the residue by centrifugation at 2,000 rpm
are available in the Detailed Study Plan for 30 min and the supematant retained. ThepH
(PLUARG 1974). of the supernatant was adjusted to 2 by the
ln 1975 and 1976, bottom sediments were addition of 6 N HCl, and HA allowed to
collected from the mouths of each of the six coagulate for 24h. The HA was separated from
watersheds, using a hand-held plastic corer the supematant (FA) by centrifugation and both
(Sutton 1974). Bottom sediments ranged in fractions were freeze-dried.
depth from 5 to 20 cm and were collected across At this point, the HA's still had very high ash
the underwater width of the stream. Samoles for contents. To lower the ash, HA's were shaken
organic matter determinations were composites for 24 h with an aqueous solution containing
of these sediments. As in many other studies, O.5Va (wlv) HCI + 0.5Va (w/v) HF. Less than
bottom sediments were assumed to be a matrix l.OVaof the HA was lost under these conditions.
of soil, rock, plant and animal components Following this treatment, the residues were

Table 1. Agricultural watersheds selected for this study

Watershed Name County Soil type Area (km2) Agricultural activity

1 Big Creek Essex Tile-drainedclay 5I .8 Cash crops

3 Little Ausable River Huron Clay, loam 54.1 Pasture & forage crops
CanagagigueCreek Wellington Silt loam, clay loam 18.9 Pasture & small grains
5 Holiday Creek Oxford Loam 29.5 Pasture & forage crops
10 North Creek Lincoln Clay 29.8 Pasture
t3 Hillman Creek Essex l-oamy fine sand 20.7 Horticultural & cash croPs
 WHITBY AND SCHNITZER AGRICULTURAL WATERSHEDS 169
-
centrifuged, washed free of Cl- and freeze- humic materials were precipitated by adding an
dried. excess of Pb(NOjr)r, and the resulting lead
At this stage, the FA's also were high in ash. humates separated by centrifugation at 2,000
To lower the ash, several procedures were tried: rpm for 1 5 min (Weber and Wilson 1975) .
(1) dissolution in methanol and butanol (Griffith To remove the lead, the lead humates were
and Schnitzer 1975a); suspended in distilled water, an excess of
(2) stepwise pH adjustment from 2.5 to 10.5, sodium sulphide added, and thepH lowered to 9
followed by centrifugation to remove insolu- with HCI . After stiring for I h, the lead
ble residues (Holtzclaw etal. 1976); sulphide was removed by filtration and thepH of
(3) repeated passage over the cation exchange the filtrate adjusted to I with HCl. Nitrogen was
resin Rexyn 101 in H+ form (Wright and bubbled through the solution to remove excess
Schnitzer 1959); and H2S. Colloidal sulfur compounds were filtered
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(4) dialysis (Schnitzer et al. 1959). off. and the clear filtrate freeze-dried.
Most of these procedures tended to produce After drying, the humate was extracted with
either FA fractions in small yields or did not isopropanol-distilled water (5:2) (Sowden and
lower the ash content of the bulk of the FA. Only Deuel 1961). Any precipitate was removed by
dialysis produced purified FA that had properties centrifugation and the supematant dried on a
similar to those already described for FA rotary evaporator. Dissolution in isopropanol
(Schnitzer and Khan 1972; Kononova 1966). was repeated several times until no further sulfur
Between 3 and 57a of the weights of the FA's precipitated. Only FA was recovered, as the HA
was lost during dialysis. The. other three was precipitated and removed by filtration with
methods produced FA's with chemical composi- the colloidal sulfur.
tions similar to that of HA. The tenacity with
which the FA's retained the metals suggested
that the metals were strongly complexed or Analytical Methods
otherwise firmly retained by some yet unknown Moisture and ash were determined on all HA's
mechanism by the FA's. and FA's by drying for 24 h at I 05"C and heating
Suspended sediments were obtained from the for 4 h at 750'C, respectively. The HA's and
same sites and at the same times as the bottom FA's were analyzed for C and H by dry
sediments. Since most of the organic C in the combustion,, for N by Dumas method, for S by
streamwater was in the dissolved form (Whitby oxygen flask combustion and O was calculated
et al. 19'77), a different method was used to by difference. Total acidity, carboxyl groups,
obtain humic materials from streamwater and phenolic OH groups andF,alE6 ratios (Schnitzer
suspended sediments. Suspended and dissolved 1975) were determined on the HA's and FA's

Fig. I Location of watersheds

 170 CANADIAN JOURNAL OF SOIL SCIENCE

when sufficient material was available. All the original soil organic matter. Percentages
elemental analyses were expressed on a mois- of the initial organic matter extracted as
ture- and ash-free basis. Results are exoressed as
means for all HA's and FA's in each wirershed.
HA's * FA's were as follows: watershed 1,
52.4Vo; watershed 3, 20.27o; watershed 4,
EalE6 ratios were determined by dissolving
36.9Vo; watershed 5, 55.8Vo; watershed 10,
2-4 mg of sample in l0 ml of 0.05 N NaHCO3
and measuring optical densities at 465 and 665 9.3Vo; and watershed 13, 4l .l%o. The
nm. IR spectra were recorded on I mg of average extraction efficiency was 41 .37o,
material pelleted with 400 mg KBr. excluding watershed 10. These data show
that there was considerable variability in the
Alkaline KMnO+ Oxidation, Separation and capacity of 0.5 N NaOH to extract organic
Identification of Oxidation Products matter from the different soil samples.
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The alkaline KMnO. oxidation was done by the

same method as that described earlier (Khan and HA's and FA's extracted from soils
Schnitzer 1971). The HA's and FA's were The elemental composition of the HA's
methylated prior to oxidation with diazomethane
extracted from the six soils is shown in
generated from Diazald. Detailed descriptions of
solvent extractions, chromatographic separa- Table 3. The widest variations were in C
tions and gas chromatographic-mass spec- (47.9-56.0Vo) and O (33.6-39.87o) con-
trometric-computer identifications of the oxida- tents. When the C analysis for soil 3 was
tron products have been published previously omitted, the average Vo C for the soil HA's
(Neyroud and Schnitzer 1974). analyzed increased to 53.8Vo. Data for the
remaining elements varied over naffower
RESULTS AND DISCUSSION ranges. Average elemental analyses for the
Characteristics of Soil Samples six HA's were similar to those of a ''mean' '
A number of soil chemical characteristics soil HA, which is the composite of
are summarized in Table 2. The pH's numerous analyses done on large numbers
ranged from 6.8 to 7.5. From the orga;ic C of HA's extracted from soils from widely
content, it is possible to estimate the differing climatic and geologic environ-
organic matter content by multiplying Vo C ments (Schnitzer 1977).
by 1.724 and to calculate the extraction The elemental composition of the soil
efficiency. Thus, the organic matter content FA's (Table 3) resembled that of the
of the soils analyzed ranged from 21.4 to "mean" soil FA.
50.5 gikg. Extracted and purified HA's Data for major oxygen-containing func-
accounted for between 6.}Vo (watershed 10) tional groups in the HA's and FA's
and 36.5Vo (watershed l) of the initial extracted from the soils in the watersheds
organic matter, whereas extracted and are shown in Table 4. Averages for total
purified FA's constituted between 3.3Vo acidity, carboxyls and phenolic hydroxyls
(watershed l0) and 19.97o (watershed 5) of for HA's tended to be somewhat hieher than

Table2. Soils used for the extraction of HA's and FA's

Total org Total Total

Watershed pH C C N SHA FA
g/kg soil

1 6.9 21.1 20.8 2.2 4.O 13.1 5.'7

3 1 31 .8 29.3 2.6 3.0 3.6 6.6
4 7 lt.o 26.9 2.5 ).I tl.2 J.9
5 '7 2'.7.9 26.8 2.'7 -r. -l r6.6 9.2
10 1 27.0 26.2 2.8 3.8 2.7 1.5
t-l 6.8 12.4 t2.4 1.2 J.l 6.3 2.8
 WHITBY AND SCHNITZER AGRICULTURAL WATERSHEDS 171
-
Table 3. llltimate analysis and ash content of HA's and FA's extracted from soils in agricultural watenheds

CH N S O Ash
Watenhed Va Vo Vo Vo Vo Vo

HA's
I 54.3 6.4 3.5 1.0 34.9 1.5
3 4'7.9 6.5 5.0 0.6 39.8 2.0
<^ 1
5.3 2.8 1.2 36.7 3.0
5 52.6 6.7 3.4 0.9 36.5 l.)
10 52.2 6.0 4.0 0.9 37.0 1.8
IJ 56.0 6.1 J.l 1.0 33.6 2.0
Avg watershed
soil HA 52.9 6.2 3.6 0.9 36.4
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Mean soil HAt 56.2 11 J.L 0.8 35.5

FA'S
I 45.0 6.8 J. I .1 42.8 6.0
3 46.5 7.0 4.O .o 36.7 6.5
46.5 6.0 J.l .2 43.6 1.0
5 43.3 6.5 4.0 .3 44.9 9.0
l0 41.'7 6.2 3.4 .2 47.5 7.0
13 45.4 6.) 4.1 .5 4r.6 6.8
Avg watershed
soil FA 44.7 b.) 3.7 1.6 43.5
Mean soil FAt 45.'1 <A 2.1 1.9 44.8

tFrom Schnitzer ( 1977).

Table 4. Functional group analysis and EalE6 ratios of HA's and FA's extracted from soils in agricultural
watersheds

Total Phenolic
acidity Carboxyl OH
Watershed (meq/g) lmeq/g) (meq/g) EnlEu

HA'S
I 9.7 4.6 5.1 4.9
3 9.6 3.0 6.6 4.4
4 9.3 ).t J.r} 4.1
9.0 4.8 A1 4.8
IJ 8.9 6.8 2.1 4.4
Avg watershed
soil HA 9.3 5.0 4.3 4.5
Mean soil HAt 6.'7 J.O 3.9 4.8
FA'S
I '1.6 1.1 4.8
3 9.0 4.3 A1 ).L
4 13.5 7.0 6.5 t.J
5 11.5 6.6 4.9 5.1
l3 t1 A
5.3 6.8
Avg of 6
watenhed FA's t2.2 6.5 5.'7 ).1
Mean soil FAt 10.3 8.2 3.0 9.6
Insufficient sample for analysis of watershed 10
fFrom Schnitzer (1977).
 t'72 CANADIAN JOURNAL OF SOIL SCIENCE

Table 5. Characteristics ofbottom sediments

Total Organic Total Total

Watershed pH c C N S HA FA

I 7.1 23.'7 3.7 0.8 -t. -l 0.9 o

3 6.6 51 .1 0.5 4.3 2.8 .8
4 /.o /1 < 2.8 0.1 4.6 1.1 .4
5 1.1 47.0 5.8 3.3 3.1 2.5 .2
l0 7.1 33.4 1t 0.8 3.'.7 1.2 .0
13 7.1 1 8.5 3.5 0.7 1.8 2.9 .8
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the corresponding data for the "mean" soil 13) of the initial organic matter, whereas
HA (Table 4). Similar observations were FA's constituted between 22.0 and 30.j%o
made on the FA's (Table 4), except for of the original sediment organic matter.
carboxyl groups, which were lower than Between 43.1 and 78.37o of the initial
those for the "mean" soil FA. Ea/Ee ratios sediment organic matter was extracted as
of watershed soil HA's and FA's resembled HA's and FA's. The average extraction
that of the mean soil HA. efficiency was 56.07o, which was higher
than that for humic substances from
Characteristics of Bottom Sediments watershed soils.
ThepH's of the bottom sediments (Table 5)
were similar to those of adjacent soils HA's and FA's Extracted from Bottom
(Table 2), but the organic C content per unit Sediments
weight was much lower. HA's extracted Elemental analyses for HA's extracted from
from the sediments accounted for between bottom sediments collected in 7915 are
14.07o (watershed l) and 48.3Vo (watershed shown in Table 6. In general, the N and S
Table 6. Ultimate analysis of HA's and FA's extracted fiom bottom sediments in agricultural watersheds and of
FA's isolated from suspended sediments

H N S o ASh
Watenhed 7o Vo 7a Vo 7o Vo

HA's
3 55. 8 6.1 5.5 1.9 29.8 L.)
4 55. 1 6.1 5.6 1.9 30.6 4.1
5 55.1 o. -t 4.9 1.8 31.1 1.8
l0 '7.1 6.2 )/ 1 t.-)
56.3 6.0
13 56.8 6.3 6.3 1.8 28.6 1.8
Average 560 6.1 5.1 2.'7 28.9 z.)
Mean soil HAt 56.2 A1 J.L 0.8 -'tt. )
FA's
3 38.2 o. / 4.5 0.9 49.'7 12.6
4 31 .9 6.1 +.3 0.9 50.8 r3.3
5 39.2 4.7 +. -1 l.l 49.7 1"6
A1 /
l0 38.5 6.4 4.8 2.9 18.'7
13 39.8 6.4 4.2 1.1 48.5 30.'7
Average 38.7 6.3 4.4 l-+ 49.6 16.6
Suspended sediment
tavgl 40.9 4.9 1.5 7.8 44.9 6.9
Mean soil FAt 45.'7 5.4 2.1 1.9 44.8

Insufficient sample for analysis of watershed i

tFrom Schnitzer (1977).
 WHITBY AND SCHNITZER AGRICULTURAL WATERSHEDS 173
-
contents of sediment HA's were hieher than These differences are probably related to
that of soil HA's (cf. Tables 3 and 6), the relatively high ash content of the soil
whereas the O content tended to be lower, and sediment FA's which consisted mainly
but there was good agreement for %o C. of silicates. Fe and Al. and which we were
Elemental analyses of FA's from sus- unable to lower. The ash content of the
pended sediments resembled more closely FA's, especially from the bottom sediments
those of bottom sediment FA's (Table 6) (Table 6), remained high, despite repeated
than elemental analyses of FA's extracted efforts to reduce it. It seems that the
from soils in the watersheds (cf. Tables 3 inorganics were so strongly associated with
and 6). the organics that it was practically impossi-
The total acidity, carboxyls, phenolic ble to reduce them without sacrificing most
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hydroxyls and EalEe ratios of HA's and of the organic materials, so that it was
FA's extracted from bottom sediments considered preferable to proceed with
(Table 7) were, in general, similar to those further characterization on materials that
of HA's and FA's extracted from watershed had some inorganics attached to the or-
soils (Table 4). There were, however, a ganics (see also Griffith and Schnitzer
number of differences: (a) total acidities of 1975b for tropical volcanic soils; Chen et
the bottom sediment FA's were lower than aI. 1917 for Mediterranean soils). Examina-
that of the "mean" soil FA; (b) the tion of the ashes showed that these con-
carboxyl content of the FA's extracted from sisted primarily of silicates and much
sediments was lower than that of FA's from smaller quantities of Fe and Al and other
soils, while the phenolic hydroxyl content metals. This strong association between
of the sediment and watershed soil FA's organics and inorganics demonstrates the
was similar but higher than that of the importance of humic materials in the
"mean" soil FA; and (c) EalE6 ratios of mobilization and immobilization of inor-
sediment and watershed soil FA's were ganics in aquatic and terrestrial environ-
lower than that of the "mean" soil FA. ments.

Table 7. Functional group analysis and EalE6 ratios of HA's and FA's extracted from bottom sediments (1976
samples)
-j:.---:

Total Phenolic
acidity Carboxyl OH
Watershed (meq/g) (meq/g) (meq/g) E/E

HA's
3 7.2 2.8 4.4 3.8
4 6.6 2.8 3.8 4.3
5 7.2 2.8 4.4 3.8
10 5.0 2.0 3.0 3.5
13 8.0 3.8 -).I
Avg sediment HA 6.8 3.9 3.9 3.8
Mean soil HAt o./ 3.6 3.9 4.8
FA's
3 8.3 2.7 5.6 4.5
4 '7.4 2.0 5.4 4.6
5 6.9 z. -) 4.6 4.9
l0 9.2 2.5 b. / 3.4
l3 8.8 2.8 6.0 4.8
Avg FA's 8.1 2.5 5.6 4.4
Mean soil FAf 10.3 8.2 3.0 9.6

fFrom Schnitzer (1977)

 174 CANADIAN JOURNAL OF SOIL SCIENCE

IR Spectra chemical methods in that they showed that

The main infrared (IR) absorption bands of sediment HA's and FA's contained appre-
soil and sediment HA's and FA's were in ciable amounts of oxygen-containing func-
the regions of 3,400 cm r (hydrogen- tional groups which interacted with metal
bonded OH). 2.960-2.850 cm-r (aliphatic ions, metal oxides and metal hydroxides to
C-H stretch), 1,130-1,715 cm*1 (C:O of form stable metal-organic complexes. In-
CO2H, C:O of ketonic carbonyl), 1,620 teractionsof the humic materials with
cm-r (aromatic C:C, COO , hydrogen- silicates were also indicated.
bonded C:O) and 1,050 cm-1 (Si-O of Our chemical and spectrophotometric
silicates). Smaller bands were visible near data show that HA's and FA's in suspended
1,520 cm 1 (aromatic C:C), 1,440 cm-' and bottom sediments resembles soil HA's
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(CHr), 1,400 cm-l (COO-), 1,230 cm-1 and FA's in surface structural features and
(OH or C-O stretch), 800, 670-660, 570, in ability to form strong metal-organic
530 and 4'70 cm-1 , most likely due to Si-O complexes and to interact with silicates"
valence and deformation vibrations (Grif-
Oxidation of HA's and FA's
fith and Schnitzer 1916) and to the presence
of iron oxides (Kodama et al. 1977) and Yields of major types of oxidation products
aluminum oxides. resulting from the different HA's and FA's
are summarized in Table 8. Only small
IR spectra of watershed soil HA's amounts of aliphatics were isolated from the
showed a preponderance of OH and COO different degradation products. The major
and, to a minor extent, of COzH groups as compounds produced were benzenecar-
well as of aliphatic CH2 groups and silicates boxylic and phenolic acids. Similar but
(Si-O). IR spectra of watershed soil FA's somewhat lower amounts of benzenecar-
indicated the presence of substantial con- boxylic acids were formed from the oxida-
centrations of OH and CO2H groups and of tion of I g of methylated soil HA and soil
silicates, which appeared to be strongly FA. Also, similar but lower yields of these
associated with the organic matter. IR acids were isolated frorn bottom sediment
spectra of HA's and FA's extracted from the HA's and from organic matter in suspended
sediments were very similar to those of soil sediments. Bottom sediment FA's produced
HA's and FA's. In general, the IR data the lowest yields of benzenecarboxylic
confirmed the information provided bv acids.

Table 8. Major compounds (mg) produced by the KMnOa oxidation of I .0 g of methylated humic material

Bottom Bottom
Soil sediment Soil sediment Suspended
Type of compound HA's HA's FA's FA's sediment

Aliphatic
Alkanes 5.8 0.0 z. -) 2.2 2.',l
Fatty acids 2.'7 1.1 0.'1 0.8 1.8
Carboxylic acids 1.0 0.1 2.9 5.1 0.0
Phenolic 28.2 12.4 12.'7 b. / 1.4
Benzenecarboxylic 61.2 43.9 51.2 22.6 44.0
A'
Furan 4.8 1.9 3.0 1.2
Dialkyl phthalates 4.6 29.5 4.3 36.'7 5.5
Total 1tt.2 81.7 78.1 '70.2 66.1
Wt ratio benzene-
carboxylic/phenolic 2.2 3.5 A< 2.5 5.9
70 aromaticityt 83.9 7 5.4 s4.o 61 .5 84.8

tExcluding dialkyl phthalates from total weights

 WHITBY AND SCHNITZER AGRICULTURAL WATERSHEDS 175
-
As far as phenolic acids were concerned, oo
i-o. /\t'o-t-o"**'
the oxidation of soil HA's produced the "*. H,o : trj
largest amount, while lower but similar 2
amounts were formed from soil FA's and o-'.-oH c--..oH^
bottom sediment HA's. Schnitzer (1915..
1977) reports that the major compounds
,\i-o- *"" ,\E_.
produced by the KMnOa oxidation of |
,/)^oH
lM
"'2^o'
methylated HA's and FA's extracted from -li+H+(21
o.t ,o H
surface and subsurface soils formed under .r\s_o-
widely differing geological and climatic _lO
+ M2+

conditions were benzenecarboxylic and //7

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phenolic acids. He considers these com- Frg. 2. Reaction mechanisms in water near pH
pounds major humic "building blocks." 7.0 between divalent metal ion M2+ and HA's
The data presented herein show that sedi- and FA's.
ment HA's and FA's have the same
"building blocks" as soil humic sub-
stances. Weight ratios of benzenecarboxylic
one adjacent OH group react simultane-
ously with the metal ion to form a bidentate
to phenolic acids, which may be considered
complex or chelate. According to equation
to reflect the interrelationship between 3, two adjacent CO2H groups interact
major "building blocks", are also listed in
simultaneously with the metal ion to also
Table 8. The ratios ranged from2.2 (for soil
form a bidentate chelate. Chelation accord-
HA's) to 5.9 (for suspended sediments). ing to equations 2 and 3 has been discussed
From the data in Table 8, we approximated
the aromaticity of each set of HA's and
in considerable detail by Gamble and
Schnitzer (1973).
FA's by expressing weights of benzenecar-
From the data in Table l, it is now
boxylic * phenolic acids as percentages of possible to estimate metal-binding
total yields. Because we did not consider capacities on the basis of each of the three
that dialkyl phthalates were structural com-
reaction mechanisms described above.
ponents, we subtracted yields of dialkyl
These data are shown in Table 9. First, the
phthalates from total yields for the purpose
average HA and FA content per kilogram of
of estimating aromaticities. As shown in sediment and watershed soil was calculated
Table 8, aromaticities of the organic matter
from the data in Tables 5 and 2. resDec-
from the suspended sediments were similar tively. These values were then multiplied
to those of soil HA's, whereas aromaticities
by the CO2H and phenolic OH contents per
of bottom sediment HA's and FA's were of
the same general orderof magnitude.
gram of HA or FA. For example, the
average bottom sediment contained, per
kilogram, 2.0 g of HA and 1. 6 g of FA . The
Metal-binding Capacities of Sediment average COzH and phenolic OH contents
HA's and FA's for these materials were 2.9 and2.5 meqlg,
Reactions in water near pH 7.0 between di- respectively (Table 7). Thus, the CO2H and
and trivalent metal ions and HA's and FA's phenolic OH contents in the average HA in
are likeiy to proceed by either one, two or 1 kg of bottom sediment were 2.0 x 2.9 :
simultaneously all three of the reaction 5.8 meq/kg and 2.0 x 2.5 : 5.0 meq/kg,
mechanisms shown in Fig. 2, taking respectively. Similar concentrations in the
divalent metal ion M2+ as an example. average FA in 1 kg of bottom sediment were
According to reaction l. one CO2H grbup 1.6 x 2.5 : 4.0 meq/kg CO2H groups and
reacts with one metal ion to form an organic 1.6 x 5.6 : 9.0 meq/kg phenolic OH
salt or monodentate complex. Equation 2 groups. The same types of calculations
describes a reaction in which one CO"H and were also made for the watershed soil HA's
 r76 CANADIAN JOURNAL OF SOIL SCIENCE

and FA's and these are also shown in Table equations l-3. The major reason for these
9. From functional group analysis data on differences was variation in the concentra-
FA's available in the literature (Schnitzer tions of HA's and FA's in the soils (total :
and Khan 1912), it was apparent that the 14.2 glkg) and bottom sediments (total :
COrH content of the average bottom 3.6 glkg. We have no indications that the
sediment FA was too low and should be at binding efficiencies of the humic materials
least two or three times as high. Our low in the two environments were different.
CO2H values were clearly the result of most As far as suspended sediments were
of theCO2H groups in bottom sediment concerned, we were unable-to collect suffi-
FA's being firmly blocked by metals (see cient materials for more comprehensive
high ash contents in Table 6 and paragraphs analyses. The only measurements we did on
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on IR spectra). these materials were ultimate analyses

As has been shown by Griffith and (Table 6). From our data, it appeared that
of the dry,
Schnitzer (1975a), about J5Vo the suspended organics resembled FA's
ash-free weights of organic matter in from bottom sediments. Similar findings
inorganic soils consists of humic materials, were reported by Weber and Wilson (1975)
while the remaining 257o are carbohydrates who isolated organics from highly-colored
and protein-like substances. Because only water and noted that these resembled soil
56.0 and 41 .3Vo of the initial organic matter HA's and FA's as far as could be judged
in bottom sediments and soils was ex- from chemical and functional group
tracted, we multiplied HA and FA values analyses. In both our case and that of Weber
for CO2H and phenolic OH groups extracted and Wilson (1975), the organics were
from bottom sediments and soils by 1.34 isolated primarily from the dissolved frac-
(75.0/56.0) and 1.82 (15.0141.3), respec- tion of the streamwater, the same fraction
tively, to include unextracted HA's and that contains the greatest percentages of
FA's. The corrected values for COzH and metals such as Cu, Hg, Ni, Pb, Se, etc.
phenolic OH groups are listed in Table 9. (Whitby et al. 1977; Ramamoorthay and
The corrected data were used for calculat- Kushner 1975). Future work should be
ing metal-binding capacities according to concerned with more detailed characteiza-
equations 1,2 and 3. As shown in Table 9, tions of organics in streamwaters.
metal-binding capacities of HA's and FA's
in 1 kg of watershed soil were about l0-12 CONCLUSIONS
times as high as those of HA's and FA's in I The data presented herein show that humic
kg of bottom sediments, according to substances extracted from sediments and

Table 9. Estimated metal-binding capacities of bottom sediment and watershed soil HA's and FA's (units are
meq/kg of sediment or soil)

Avg Corrected Metal-binding

Avg Corrected phenolic phenolic capacities (meq/kg)
CO,H CO,H OH OH according to equations
content content content content
Type of material lmeq/ks) (meq/kg) lmeq/ke) (meq/kg)
Bottom sediment HA's ).6 7.8 5.0 6.7 7.8 6.7 3.9
Bottom sediment FA's 4.0 5.4 9.0 12.1 5.4 5.4 2.'7
Sumof HA's * FA's 9.8 13.2 J4.0 18.8 13.2 12.1 6.6
Watershed soil HA's 44.5 81.0 38.3 69.7 81 .0 69.7 40.5
Watenhed soil FA's 34.4 62.6 30.2 s5.0 62.6 55.0 31.3
Sum of HA's f FA's 78.9 143.6 68.5 r24.7 143 .6 124.'1 71 8 .
 AGRICULTURAL WATERSHEDS t7'7

adjacent soils have similar surface charac- REITZ, E. 1975 Chemical composition and
teristics and chemical structures. Chemical physical propefties of humic substances. Pages
degradation experiments show that the 1-2ll in J. E. Gieseking, ed. Soil components.
chemical structure of the organic matter in I. Organic components. Springer Verlag, New
sediments resembles that of soil HA's and York, N.Y.
GAMBLE, D. S. and SCHNITZER, M. 1973.
FA's. Thus, from our analytical and degra- The chemistry of fulvic acid and its reactions
dation data, it appears likely that humic with metal ions. Pages 265-302in P. C. Singer,
substances in the bottom. sediments of ed. Trace metals and metal-organic interactions
agricultural streams originate lrom adjacent in natural waters. Ann Arbor Science Pub-
soils. lishers, Ann Arbor, Mich.
It is known that runoff that enters streams GRIFFITH, S. M. and SCHNITZER, M. 1975a.
from soils carries with it inorganic and Analytical characteristics of humic
Can. J. Soil. Sci. Downloaded from cdnsciencepub.com by 116.71.165.209 on 09/05/23

and fulvic
organic materials, among which humic acids extracted from tropical volcanic soils. Soil
materials are prominent. The high capacity Sci. Soc. Amer. Proc. 39:861-867.
of HA's and FA's for binding heavy metals GRIFFITH, S. M. and SCHNITZER, M. 1975b.
The isolation and characterization of stable
and organic toxicants such as pesticides metal-organic complexes from tropical volcanic
makes them impoftant vehicles for pollutant soils. Soil Sci. 120: 126-131.
transfer, because once the material reaches GRIFFITH, S. M. and SCHNITZER, M. 1976.
streams,it can be expected to eventually Isolation and characterization of metal-organic
reach lakes and oceans. As has been complexes from tropical volcanic soils. Pages
mentioned above, we have in fact, observed I 17-130 in J. O. Nriagu, ed. Environmental
an accumulation of dialkyl phthalates (plas- biogeochemistry L Ann Arbor Science Pub-
ticizers), some of which are toxic, in lishers. Inc.. Ann Arbor. Mich.
bottom sediment humic materials. Our data, HOLTZCLAW, K., SPOSITO, G. and BRAD-
showing relatively low concentrations of FORD, G. R. 1976. Analytical properties of the
soluble, metal-complexing fractions in sludge-
HA's and FA's in stream bottom sediments, soil mixtures: I. Extraction and purification of
suggest that these materials have been fulvic acid. Soil Sci. Soc. Amer. J.40:
moving out of the watersheds, as both 254-258.
soluble (especially FA) and particulate INTERNATIONAL REFERENCE GROUP ON
(HA's and FA's coating soil particles) GREAT LAKES POLLUTION FROM LAND
fractions. USE ACTIVITIES. 1974. Detailed study plan to
assess Great Lakes pollution from land use
ACKNOWLEDGMENT activities. International Joint Commission.
This study was carried out as part of the Task C Windsor, Ont.
activities of the Pollution from Land Use KHAN, S. U. and SCHNITZER, M. 1971.
Activities Reference Group, International Joint Further investigations on the chemistry of fulvic
Commission, established under the Canada- acid, a soil humic fraction. Can. J. Chem. 49:
U.S. Great Lakes Water Quality Agreement of 2302-2309.
1972. Funding was provided through Agricul- KODAMA, H., McKEAGUE, J A.,
ture Canada. Findings and conclusions are those TREMBLAY, R. J., GOSSELIN, J. R. and
of the authors and do not necessarily reflect the TOWNSEND, M. G. 19'77. Characterization of
views of the Reference Grouo or its recommen- iron oxide compounds in soil by Mossbauer and
dations to the Commission. ihe authors wish to other methods. Can. J. Earth Sci. 14: 1-15.
acknowledge the technical assistance of D. S. KONONOVA. M. M. 1966. Soil organic
Skinner. matter. Pergamon Press, Oxford, England.
NEYROUD, J. A. and SCHNITZER, M. l9'74.
CHEN, Y., SENESI, N. and SCHNITZER, M. The chemistry of high-molecular weight fulvic
7977. Chemical and physical characteristics of acid fractions. Can. J. Chem. 52 4123-4132.
humic and fulvic acids extracted from soils in RAMAMOORTHY, S. and KUSHNER, D. J.
the Mediterranean region. Geoderma (in press) . 1975. Heavy metal-binding sites in river water.
FLAIG, W., BEUTELSPACHER, H. ANd Nature 256: 399-401.
 178 CANADIAN JOURNAL OF SOIL SCIENCE

SCHNITZER, M. 1975. Chemical, spectro- SOWDEN, F. J. and DEUEL, H. 1961.

scopic and thermal methods for the classification Fractionation of fulvic acids from the B horizon
of humic substances. Pages 293-310 in D. of podzol. Soil Sci. 9l: 44-48.
a
Povoledo and H. L. Golterman., eds. Humic SUTTON, R. C. 1974. An inexpensive hand-
substances. Centre for Agricultural Publishing operated sediment corer. J. Sed. Petrol. 44:
and Documentation, Wageningen, The Nether- 928-930.
lands. WEBER, J. H. and WILSON, S. A. 1975. The
SCHNITZER, M. l9'l'7. Recent findings on the isolation and characterization of fulvic acid and
characterization of humic substances extracted humic acid from river water. Water Res. 9:
from soils from widely differing climates. Pages 1079- 1084.
ll7-I32 in Soil organic matter studies II. WHITBY, L. M., MacLEAN, A. J.,
Intemational Atomic Energy Agency, Vienna. SCHNITZER, M. and GAYNOR, J. D. 1977.
SCHNITZER, M. and KHAN, S. U. 1972. Sources, storage and transport of metals in
Can. J. Soil. Sci. Downloaded from cdnsciencepub.com by 116.71.165.209 on 09/05/23

Humic substances in the environment. Marcel agricultural watersheds. International Joint

Dekker Inc., New York, N.Y. Commission Technical Report (in preparation).
SCHNITZER, M., SHEARER, D. A. and WRIGHT, J. R. and SCHNITZER, M. 1959.
WRIGHT, J. R. 1959. A study in the infrared of Oxygen-containing functional groups in the
high-molecular weight organic matter extracted organic matter of a podzol soil. Nature 184:
by various reagents from a podzolic B horizon. 1462-1463.
Soil Sci. 87:252-257.