Composi t i on and St ruct ure of

Agent s Responsi bl e for Devel opment

of Wat er Repel l ency i n Soi l s
fol l owi ng Oi l Cont ami nat i on
M A R I N A L I T V I N A ,
T I O N A R . T O D O R U K , A N D
C O O P E R H . L A N G F O R D *
Department of Chemistry, University of Calgary,
2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4
Soil fromtheEllersliesiteof experimental oil contamination
in Alberta developed water repellency some years after
initial remediation. Thewater-repellent soils werecompared
tocleansoils andcontaminatedbut wettablesoils bysolid-
state nuclear magnetic resonance (NMR). The effects
of extraction with CH
2
Cl
2
(for petroleumhydrocarbons),
NaOH(for natural organic matter), and2-propanol/ammonia
(IPA/NH
3
) on wettability were evaluated by the molarity
of the ethanol droplet (MED) test. Soil extracts and whole
soils, after extraction, were examined using NMR and
Fourier transforminfraredspectroscopy(FTIR). Onthe basis
of the structure-MED correlations, a model of a thin-
layer natural organic matter-petroleumproducts complex
formed under strong drying conditions is proposed to
account for the development of water repellency. Studies
of twosimilar soils fromaccidental oil spills aresupportive.
I nt roduct i on
Water repellency is a phenomenon that develops both
naturally (1-3) and in petroleum-contaminated soils (1-3).
It is the latter case that is most problematic because of the
seemingly random nature of its appearance. Specifically, it
can arise following the seemingly successful remediation of
the site using a variety of methods. Roy and McGill (1, 2)
have proposed that the phenomenon arises from residual
contaminants. It is postulatedthat thesecontaminants extend
from the surface of soil particles following a rearrangement
toexposehydrophobic moieties. This approachhowever fails
toidentify the specific agents that are causative anddoes not
consider the role of the natural organic matter (NOM) that
is well-known to interact with organic contaminants. The
use of nuclear magnetic resonance (NMR) toelucidate tothe
structurally significant components provides an approach
to this problem. The most significant samples studied are
the series of Ellerslie (ELL) soils, which are collected from a
site experimentally contaminatedin1973. The phenomenon
of water repellency developed some time following an
apparently successful remediation of the site. The patches
that developed the phenomenon were those most highly
contaminated (4). A clean, uncontaminated soil (ELL-PW),
contaminated but wettable soil (ELL-CW), and a water-
repellent soil (ELL-NW) fromthis site are available for study.
Thus, it may be possible to identify structures that can
negatively impact soil wettability.
NMR (5, 6) is a powerful tool for characterization of soil
components. Specifically, humic and fulvic acids and whole
soils have been studied (7). It provides a nondestructive
method of sample analysis. In 1981, Wilson et al. reported
spectra of whole soils obtained using
13
C cross polarization-
magic angle spinning (CP-MAS) NMR (8). This solid-state
technique quickly became the standard. Since then, the
developments in CP-MAS NMR spectroscopy have made it
amajor tool for investigations of soil organic matter (7, 9-13).
NMR methods are used here for structural investigation of
water-repellent soils that were previously contaminatedwith
petroleum and subsequently remediated.
Soil organic matter (SOM) is a structurally diverse,
heterogeneous mixture thought to be composed of bio-
geopolymers. The polymers themselves have a wide range
of apparent molecular weights. SOMis oftenstrongly bound
to mineral particles. Solid-state NMR on intact, whole soil
samples is not always successful for this reason. Goodspectra
were obtained for all samples considered in this study.
13
C
CP-MAS NMR is useful for the comparison of functional
groups in related samples without requiring the use of more
complicated and time-consuming methods. Errors arising
fromdifferences inthe Hartmann-Hahnmatchandvariable
relaxation times can cancel each other in a comparative
analysis of samples. To reduce the effect of dipolar-dipolar
interactions betweenprotons andbetween
13
Cand
1
Hnuclei
high power proton decoupling was used.
The quantitative reliability of
13
CCP-MASanalysis of SOM
and whole soils has been discussed by several authors (12-
15). There are at least three factors. First, carbon atoms in
different functional groups have varying efficiencies of cross-
polarization. These variations arise because of nonuniform
cross-polarizationandvariableprotonspin-latticerelaxation
time(T1) inheterogeneous organicmatter. Usuallythis results
incarbonatoms that areincloseproximitytoprotons gaining
energy faster. Second, carbon atoms in close proximity to
paramagnetic centers (such as Fe
3+
) may not be observed
because protonrelaxationis rapid, minimizing CPefficiency.
If distribution of paramagnetic species is homogeneous
throughout the sample, however, quantification is not
affected. Third, some types of carbon atom signals can
produce side bands that can interfere with other signals.
These problems can be adequately minimized to allow
comparative analysis of related samples using proper ex-
perimental parameters (12). For reasonable quantitative
representationof solidhumic substances, the sample should
be spunat arate exceeding7MHz ina300MHz spectrometer
(15). The present study presents CP-MAS spectra that allow
quantitativecomparisonbetweenfunctional groups insimilar
samples but do not necessarily provide absolute values of
functional group distribution.
The use of solid-state
13
C CP-MAS technique allows for
the collection of well-resolved
13
C spectra of whole soils and
soil organic matter with sufficient signal-to-noise ratio in
reasonable experimental time frames. The time required to
recordgoodqualityspectrais significant for extendedstudies.
Spectra reported here required 29 h for acquisition.
The purposes of this study are (i) to compare the
differences infunctional groupdistributionbetweena series
of clean, contaminated, but wettable and water repellent
soils. The most important series of soils to be studied are the
ELL soils. (ii) to attempt identification of structural com-
ponents that are associated with the development of water
repellency using
13
C CP-MAS NMR. (iii) to attempt to
elaborate upon the proposed mechanisms for the develop-
ment of water repellency using extraction work.
* Correspondingauthor phone: (403)220-3228; fax: (403)289-0344;
e-mail: chlanfo@ucalgary.ca.
Environ. Sci. Technol. 2003, 37, 2883-2888
10.1021/es026296l CCC: $25.00 2003 American Chemical Society VOL. 37, NO. 13, 2003 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 2883
Published on Web 05/31/2003
Experi ment al Sect i on
Soil Samples. The main soil samples used in this study were
collected from the Ellerslie site in Alberta, 18 km south of
Edmonton (245125 NE, 4 W). The site was the subject of
an experimental oil contamination in 1973 (16). Three
samples fromthis site are reported on here. Ellerslie pristine
wettable(ELL-PW) is acleansoil fromoutsidetheboundaries
of the experimental contamination. Ellerslie control wettable
(ELL-CW) is awettablesoil contaminatedinamanner similar
tothe water-repellent soil. Ellerslie water-repellent soil (ELL-
NW) is a contaminated, water-repellent soil that developed
the phenomenon some years following remediation of the
site. The detailed history of these samples is given in the
accompanying paper (17). The soil is an Eluviated Black
Chernozem of the Malmo silty clay loam series (1). These
samples have beenstudiedextensively by Roy andMcGill (1,
2). Extensivepodological characterizationof thesoils is found
in refs 1-3 and the several earlier studies sited therein. The
notationandnomenclatureusedfor thesamples inthis study
is consistent with that used by Roy and McGill in order to
allow easy comparison of studies. The results obtained with
these samples are supplemented by samples from oil spill
sites in Devon, AB (DEV), and Stettler, AB (STE), where NW
and CWsamples could be obtained. Less information about
the history of these sites is available than for the ELL spill
site. The DEV soil is a Gleyed Eluviated Black Chernozemic
soil developed on alluvial parent material. Patches of water-
repellent soil were first reported over 30 yr ago (3). The high
C content (Table 1) of the CW soil reflects consequences of
cultivation and recent fertilization on the site. The STE site
has a Gleyed Black Chernozem soil developed on an alluvial
parent. The site has rolling topography. Contamination
occurred in 1970 (3). Substantial information on these two
sites is presented in the Supporting Information.
Soil Samples Characterization. Total carbon, hydrogen,
and nitrogen content were determined using a combustion
elemental analyzer (440CHN-O/Selemental analyzer, Exeter
Analytics, Chelmsford, MA) onair-driedsamples. Results are
shown in Table 1. Iron content and exchangeable cations
were obtained using an inductively coupled plasma (ICP)
atomic emission spectrometer Atom/Scan 16/25 (Thermo
Jarrell Ash Corp., Franklin, MA). For ICP analysis of iron,
1.000 g of air-dried soil was boiled in 10 mL of concentrated
HCl for 30 min. The slurry was filtered, diluted to 100.0 mL,
and then analyzed. Exchangeable cations were determined
by saturating soil cation-exchange sites with NH
4
+
by 1 M
NH4
+-
OOCCH3 (pH 7). The solution obtained was analyzed
for Ca
2+
, Mg
2+
, K
+
, and Na
+
. In all cases, 18 M of water
(Barnstead Nanopure system) was used. Soil pH was mea-
sured in water at a soil:water ratio of 1:2 after 30 min of
mixing. A Fisher Accumet meter was used. Results are
presented in Table 1.
Empirical Measurement of Soil Water Repellency (MED
Test. Soil water repellency assessment was performed on
the set of water-repellent and corresponding CW soils using
the widely exploited Molarity of Ethanol Droplet (MED) test
(18). The practical field reference for wettability is the MED
value. The MED test is conceptually based on the reduction
of the surface tension of water in ethanol solutions but is
essentially an empirical measure validated by correlation
with field behavior. Ethanol solutions with concentrations
ranging from 0 to 5 M increasing in 0.2 M increments were
prepared. HPLC-grade ethanol, purchasedfromAldrich, and
distilledwater withresistanceof 18M(BarnsteadNanopure
system) were used.
To assess soil water, repellency droplets of ethanol
solutions of different concentrations were placed on a
smoothed soil surface. The molarity of the droplets of the
lowest ethanol concentration that are completely absorbed
within 10 s is considered to be MED index of the soil. Soils
with0 <MEDindex <1 Mare consideredto be slightly water
repellent. Soils withanMEDindex >2.2 Mare severely water
repellent (18). The test was performed on soil samples air-
driedtoconstant mass. At higher soil moisture content (field-
moist soil), cohesiveforces betweenthewater initiallypresent
in the soil and the water placed on the surface make MED
values unreliable. It has been shown that the MED indices
are essentially the same for air-dried and oven-dried soils
(3). MEDresults for NWand CWsoils are presented in Table
1. None of the CW soils has an MED significantly different
from zero. All identified NW soils have values near 4.
13
C CP-MAS NMR. Samples were tightly packed into a
cylindrical 4/18 mm zirconia rotor with Kel-F caps. Solid-
state NMRmeasurements were performedona Bruker AMX-
300 spectrometer with a BL4 probe, operating at 300 MHz
for
1
H and 75.5 MHz for
13
C. Solid-state
13
C CP-MAS spectra
were obtained(15) with80 000-100 000 scans witha contact
time of 1 ms and a spinning rate of 8 kHz. Calibration used
the [
13
C]glycine ketonic signal at 176.32 ppm. Processing of
spectra withBruker 1DWINNMRsoftware includedphasing
and background correction (15). Solid-state spectra were
processed with 100 Hz line broadening.
The wide range of chemical structures in soil organic
matter result in broad overlapping bands in the solid-state
NMR spectra. Because of this, the intensity is integrated
within a region corresponding to similar types of carbon
atoms. Chemical shift regions were assigned to carbontypes
as follows (19): 0-50 ppmwere assigned to aliphatic carbon
atoms; 50-96ppmwereassignedtocarbohydrate-likecarbon
atoms; 96-108ppmwere assignedtoO-C-Olinkages; 108-
162 ppm were assigned to aromatic carbon atoms; 162-190
ppmwere assignedto carboxyl carbonatoms; 190-220 ppm
were assigned to ketonic carbon atoms.
Liquid-State
1
H NMR. Liquid-state NMR spectra were
acquired on a Bruker AMX-300 spectrometer with a BBI5
probe, operating at 300 MHz. Glass NMR tubes with 5 mm
diameter were used. For NMRanalysis, samples of Redwater
crude oil (RW) and dried material extracted from soil were
dissolved in deuterated chloroform, CDCl3 (purchased from
Aldrich). Chemical shift assignments for various types of
protons were made as follows (19, 20): 0.4-1.0 ppm were
assigned as terminal methyl protons of methylene chains;
1.0-2.0 ppm were assigned as protons on aliphatic carbons
that are two or more carbons removed from an aromatic
ring; 2.0-4.2ppmwereassignedas protons boundtoaliphatic
carbon (methyl and methylene groups) that are assigned to
an aromatic ring or electronegative functional group; and
6.0-9.0 ppm were assigned as aromatic protons.
Extractions andTreatment withSolvents. For extractions
under Soxhlet reflux conditions, an air-dried sample of soil
(20-30 g) in a cellulose thimble was placed into a Soxhlet
apparatus with a capacity of 50 mL and extracted with 150
mL of reagent-grade solvent for 6 h. The approximate
extraction rate was 20 cycles per hour. It was possible to
achieve this rate due to the small apparatus capacity. The
TABLE 1. Tot al Carbon, Hydrogen, Ni t rogen, I ron Cont ent
(% w/w), pH, MED Val ues, and Exchangeabl e Cat i ons of t he
Soi l s Exami ned
soil C H N Fe pH
MED
value Ca
2+
Mg
2+
Na
2+
K
+
ELL-NW 5.6 0.5 0.4 1.3 5.0 3.8 ( 0.1 27.7 9.0 0.7 0.3
ELL-CW 4.8 0.8 0.4 5.6 0.0 ( 0.1 32.7 12.2 0.7 0.4
ELL-PW 4.7 0.8 0.4 5.4
DEV-NW 4.5 0.5 0.2 1.4 6.4 4.2 ( 0.1 31.0 11.8 1.0 1.6
DEV-CW 5.7 0.6 0.4 7.2 0.0 ( 0.1 55.3 21.2 0.7 2.0
STE-NW 2.3 0.5 5.1 4.4 ( 0.1 5.3 2.4 0.7 0.3
STE-CW 1.6 5.7 0.0 ( 0.1 6.5 1.6 0.6 0.2
2884 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 13, 2003
apparatus capacity is defined as the maximum solvent
volumeaccumulatedinthesamplecompartment of anupper
vessel before the solvent returns to the bottomheated vessel
with bulk solvent. Poly(tetrafluoroethylene) boiling chips
(Teflon) were placed into the heated vessel of the Soxhlet
apparatus.
The quantity of extracted material was determined
gravimetrically. Solvent with extracted material was con-
centratedonarotaryevaporator andplacedintopreweighted
aluminum dishes. After being air-dryed to constant mass in
the fume hood, the mass of extracted material was obtained
and its concentration calculated. The extracted soil samples
were air-dried for 7 d, and then soil water repellency was
assessed using the MED test.
Chloroform and 2-propanol/ammonia (IPA/NH3) treat-
ment of soil consisted of saturating a sample with a
corresponding solvent, removing the solvent from the
particulate, andvortex spinning until the solvent evaporated.
The treated samples were air-dried for several days before
soil water repellency was assessed using the MED test.
Fourier TransformInfrared(FTIR) Spectroscopy of Soil
Extracts. FTIR spectra were obtained on a Nicolet Nexus-
470 FTIR spectrometer. The extract from soil material was
air-dried, quantitated, andthenredissolvedinasmall volume
of CH2Cl2. This solution was placed dropwise on a 4 mm
thick KBr windowandsolvent evaporatedunder a flowof N2.
After complete solvent evaporation, the KBr window was
covered with the second window, and FTIR analysis of the
filmwas performed. All organic solvent solutions were dried
withadryingagent (anhydrous Na2SO4) before FTIRanalysis.
Nonpolar fractions of soil extracts were also analyzed by
FTIR spectroscopy. To obtain these fractions, CH2Cl2 soil
extracts were sorbed on a cartridge (Varian Bond Elute PCB,
Varian) that containedapolar sorbent. The nonpolar fraction
of the extract was eluted from the cartridge using several
milliliters of CH2Cl2, while a polar fraction was left in the
cartridge. Results arereportedintheSupportingInformation.
The IPA/NH3 soil extracts were air-dried, redissolvedinCH2-
Cl2, filtered, and separated on the cartridge as described
above. Band assignments are presented below where the
spectra are discussed.
Gas Chromatography (GC) Analysis. CH2Cl2 extracts and
a sample of Redwater oil, which was the type of oil used in
the experimental contamination, were analyzed by conven-
tional GCanalysis of oils at Enviro-Test Laboratory, Calgary,
AB.
Resul t s and Di scussi on
Soil Composition. Toobtainbackgroundinformation, some
chemical properties of the selected soils were characterized.
These complement data fromrefs 1-3. Total carboncontent
tends to be higher for the NWsamples thanthe CWsamples.
This is probably a result of the higher content of the oil and
diagenetic products from the contamination event. This is
confirmed by the darker color of the extracts obtained in
petroleum hydrocarbons extractant CH2Cl2 solution. The
concentration of iron in soil was also quantified since it is
commonly a factor in line-broadening in solid-state NMR
spectroscopy. Quantificationproblems aregenerallyobserved
in soils with a C/Fe ratio <1 (w/w) (22). Results of elemental
analysis are found in Table 1. Iron analysis of ELL-NW
indicates iron content is approximately 1.3% (w/w). The
resulting C/Fe ratio is approximately 4.
Concentrations of exchangeablecations arealsopresented
in Table 1. ELL-NW soil has concentrations of Ca
2+
, Mg
2+
,
and K
+
lower than ELL-CW. This is indicative of a lower
density of surface negative charge. Since ELL-NW and ELL-
CW samples are from locales in close proximity, this
difference can probably be attributed to the effects of SOM
and contamination rather than to mineral constituents.
13
CCP-MAS and Related NMR. Spectra of ELL-NW, ELL-
CW, and ELL-PW soils, shown in Figure 1, gave five well-
resolved peaks: an aliphatic peak centered at 23 ppm, a
carbohydrate peak centered at 73 ppm, an O-C-O peak in
the 96-108 ppm range, an aromatic peak centered at 130
ppm, and a carboxyl peak centered at 175 ppm. The ketonic
chemical shift region (190-220 ppm) has much lower
intensity andsignal-to-noise. Comparablespectraof theDEV
and STE samples are shown in the Supporting Information.
The integrated area of each region in the spectrum is
expressedas a fractionof the total carbonsignal andis shown
in Figure 2. The distribution of relative intensities for main
types of carbon varies among ELL-PW, ELL-CW, and ELL-
NW. Key observed trends are as follows: the percentage of
aliphatic, aromatic, andO-C-Ocarbons decreases fromELL-
NW to ELL-CW to ELL-PW soil. The percentage of carbo-
hydrate-like and carboxyl carbons decreases from ELL-PW
to ELL-CW to ELL-NW. These findings are consistent with
the water-repellent characteristics of ELL-NWsince aliphatic
and aromatic functional groups are more hydrophobic than
carbohydrates and carboxyl groups. It should be noted that
the percentage compositions may reveal only the effect on
ratios of extra carbon introduced by the oil spill.
FIGURE1. Ellersliesoil solid-state
13
CCP-MASNMRspectra: (A)
ELL-NW, (B) ELL-PW. ELL-CW is included in the Supporting
Information.
FIGURE2. Carbonfunctional groupdistributionintwoEllerslie
soils as revealedbysolid-state
13
CCPMASNMR. Chemical shift
assignment for carbon functional groups: aliphatic 0-50ppm;
carbohydrate-like50-96ppm;O-C-O96-108ppm;aromatic108-
162ppm; carboxyl 162-190ppm; ketonic 190-220ppm.
VOL. 37, NO. 13, 2003 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 2885
Residual petroleum hydrocarbons are observed in ELL-
NWsoil. The CH2Cl2 extraction for petroleumhydrocarbons
described below provided a sample of extract for NMR
analysis. The extract, dissolved in CDCl3, gives
1
H and
13
C
NMRthat closely resemble the spectra of RW. RWis the type
of crude used in the experimental contamination. An
important point is that all spectra display minimal aromatic
signal. This is surprising and is not suggested by the
percentage contribution distribution shown in Figure 2.
An increase in the content of one functionality reduces
the share of other functionalities when a C distribution is
calculated. Absolute intensities cannot be reliably obtained
for the individual components, and as such, a peak to use
for normalization of the spectra must be identifiedtoallow
for changes tobe clearly observed. Twopeaks are candidates
for normalization. Since the oil and CH2Cl2 extracts of the
soils are bothlowinaromatics andlack-COOHfunctionality,
the idea that aromatics or carboxylates are constants of the
soil offer a basis for normalization. It is possible that -COOH
content may increase during weathering from oxidation
products. In both cases, interactions (e.g., those reducing
mobility of groups) that could decrease NMR intensities in
soil as a result of changes inparameters (e.g., relaxationtime)
must be considered. Figure 3 shows the relative intensities
of peaks fromELL-NW, ELL-CW, and ELL-PWnormalized to
each of the aromatic the -COOH peaks.
In this figure with a log scale, negative values indicate a
ratio of the peak considered to those assumed a constant are
less than one. A positive value means a ratio greater than
one. A negative value implies less of that functionality from
ELL-CWtoELL-NWif the assumptionis valid. Normalization
to the aromatic peak emphasizes what is indicated from C
distributions, that the carbohydrate signal is low in NW. It
reinforces the conclusion that there is minimal difference
between CW and NW soils. Normalization to the -COOH
signal emphasizes the variations betweenaliphatic contents
insoils and, strangely, seems tode-emphasizethedifferences
in carbohydrate. The two normalization approaches show
differences in the soil that suggest that more than simple
compositionchanges areat work. Interactions affectingNMR
signal intensities, not concentrations (especially relaxation
times), appear to be involved.
The most reasonable interpretation of both the distribu-
tion diagramand the normalized plots is that carbohydrates
and -COOH, which likely remain constant throughout the
soils, areconsiderablyunder-representedinsignals fromELL-
NW. This does not appear to be the case in ELL-CW (and
ELL-PW). This suggests that carbohydrate and -COOH
functionalities may be complexed in NW soils to give rigid
structures, resulting in short relaxation times, producing an
overall reduction in signal intensities.
Figure4shows theCdistributionamongfunctional groups
calculatedfrom
13
CCP-MAS spectra of ELLsoils after Soxhlet
extraction with the conventional petroleum hydrocarbon
extractant, CH2Cl2. The NW excess of aliphatic C is reduced,
but the excess of aromatic lies belowCWwhere the aliphatic
lies above the control. As has been noted before (1-3) and
will be confirmed below, CH2Cl2 extraction alone does not
reduce MED to wettable condition. However, the aromatic
and carbohydrate signals respond differently withrespect to
the controls. This is consistent with a process masking
carbohydratesignals. Thesehints fromtheNMRspectraserve
as a motivation for the sequence of extraction experiments
described below.
GC and FTIR Analysis of RW and CH2Cl2 Extracts. The
gas chromatogram of RW displays the sharp peaks of a
homologous series of linear n-alkanes from C12 to C38 along
with broad unresolved signals from a mixture of other
hydrocarbons. The distribution has a maximum at C17. In
contrast, the CH2Cl2 extract from ELL-NW exhibits a large,
broad band with small sharp peaks distributed mainly in the
region for C20-C60. Light hydrocarbons are largely absent.
This is not surprising since lighter fractions are more volatile
and also more easily metabolized by biota.
The FTIR of RWshows an intense band in the 2800-3050
cm
-1
assignedtoC-Hstretchandsymmetricandasymmetric
vibrations of CH2 and CH3 groups. Sharp bands at 1454 and
1373cm
-1
are assignedtoC-Hbending vibrations. The weak
band at 1600 cm
-1
is a ring CdC stretch, and the weak 743
cm
-1
band corresponds to a ring C-Hout of plane bending.
The FTIR of the CH2Cl2 extracts from the ELL-NW show all
of these bands plus a broad weak band in the 3390 cm
-1
region assigned to O-H vibrations and a CdO band at 1706
cm
-1
. Accompanied by an increase of the 1600 cm
-1
band
as comparedtotheoil, thespectrumsuggests that theextracts
contain some oxidized material in addition to the oil-like
constituents.
Separationof the polar fromnonpolar constituents of the
CH2Cl2 extract using the Varian cartridge confirms the
presence of more oxidized constituents in the extract from
ELL-NW. The O-Hstretch near 3390 cm
-1
, the CdOstretch,
ring CdC stretch, and ring C-H bending bands are signifi-
cantly decreased in the spectra of nonpolar fractions as
compared to the original CH2Cl2 extracts fromboth ELL-NW
and DEV-NW soils. The continued presence of these bands
in even the least polar fractions underlines variations in the
extract and RW.
Effects of Extractions on MED Values. Roy et al. (1)
reported that extraction of NW soils with CH2Cl2 did not
significantly reduce MED values. Results shown in Table 2
confirmthis, despite the large amount of material extracted.
Extractions with aqueous NaOH and with IPA/NH3 signifi-
cantly reducedMEDvalues. Surprisingly, MEDvalues of IPA/
NH3 extractedsoils couldbe restoredby a subsequent CH2Cl2
extraction (1). These results clearly demonstrated that a
simple excess of petroleum and its diagenesis products is
not theuniquecauseof water repellency. Roy et al. (1) suggest
that water repellencyis causedbyarearrangement of acritical
FIGURE3. Logof ratioof NMRsignal intensity(area)forELL-CW
over ELL-NWwith two choices of normalization. In one case,
aromaticisassumedconstantsothatthearomaticratiois1.Inthe
othercase, thecarboxyl contentisassumedconstantsothatthe
carboxyl ratiois 1.
FIGURE 4. Percentage distributionof carbonfunctional groups
determinedbysolid-state
13
CCP-MASNMRspectroscopyforELL-
NWsoil extractedwithDCMinaSoxhletapparatusandEll-NW
andEll-CWsoils.
2886 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 13, 2003
fraction of organic matter. Our results confirm and extend
their observations and offer an opportunity to render their
hypothesis more concrete.
As shown in Table 3, treatment with IPA/NH3 increases
the N content of the samples. These results and the benefits
of NaOH treatment can be explained if we postulate a
neutralization reaction for the -COOHgroups. These groups
areamajor constituent of SOMandareexhibitedprominently
in the
13
C NMR spectra. The NH3 effect on MED may then
be attributed to the reaction:
A parallel neutralization of the acid can occur with NaOH,
leaving Na
+
cations exchanged into SOM. The reversal of
effects on MED caused by subsequent treatment with CH2-
Cl2 must then be a consequence of the shifting of the
equilibrium in eq 1 to the left that results from the major
reduction of the dielectric constant. As the equilibrium is
shifted left, neutral ammonia can be washed out.
It is interesting that the FTIR spectra of the extracts
obtained with IPA/NH3 after after extraction with CH2Cl2
appear to represent SOM. This extraction sequence is that
which strongly reduced MED values. The intensity of the
CdO stretch band is considerably greater than the intensity
of the CHstretch in the CH2Cl2 extract. The relative intensity
of the O-H band is greatly enhanced, although residual
alcohol cannot be rigorously excluded as a contributor.
We next confront the significance of the failure of CH2Cl2
to reduce MED. The data above implies that a large fraction
of residual petroleum and diagenesis products are removed
with the extraction.
This extracted product is still NW. The most attractive
explanation for this behavior is that the NW property is
conferred by a complex of petroleum residues with natural
organic matter that involves -COOH groups. This suggests
that only a very small fraction of the petroleum residues are
needed to contribute to the water repellent structures. The
rearrangement proposed by Roy and McGill (1-3) must
involve opening of this complex. When the sample is NW,
the -COOH groups of natural organic matter are oriented in
aninaccessiblefashioninacomplex withoxidizedpetroleum
residues and/or other H-bond acceptors contained within
SOM. Upon ionization and charge development (NaOH or
NH3 treatment), hydrogen bonds re-orient, breaking up the
complex, allowing for interactions with water to occur. High
activation energies reported in the accompanying paper
supports this suggestion (17). This model also accounts for
weak NMR signals observed in the spectra. This is likely a
consequence of significant increases in relaxation times for
both the polarizing protons and the
13
C nuclei observed as
carboxylate groups and H-bonding components of the
carbohydrates as they enter into rigid complexes. The
NMR spectra of the CH2Cl2 solutions show compositions
closely related to RW (see
1
H and
13
C NMR of the extracts
in the Supporting Information). This includes the low
aromatic signal. There is no indication of extraction of
SOM rich in oxygen. The
13
C CP-MAS NMR of ELL-NW
following extractionstill displayed some of the soils original
characteristics.
These findings are consistent with the findings reported
for the formation hydrophobic aggregates from humic
substances. It is well-documented (23) that, after rigorous
drying of humic substances, rewetting of the system is very
difficult. This has been shown to be especially true in the
presenceof metals insolutionbeforedrying, whereit appears
that the formation of hydrophobic micelles is induced by
metal chelation in the solution. Since this is a well-defined
cause of water repellency, it is not unlikely that hydrophilic
functionality in petroleum contaminated sites such as a
carboxyl group likely accounts for the development of this
phenomenon (23).
The model proposedis fully consistent withthe extraction
sequence that demonstrates irreversible reduction of MED.
We see, in Figure 5, that an extraction sequence of CH2Cl2
followed by IPA/NH3 is not reversible as are extractions with
IPA/NH3 followedby CH2Cl2. Indeed, repeating the sequence
rapidly reduces MED values to near zero. Here, the excess
petroleumresidues havebeenremovedfirst, leavingalimited
supply for reformation of the critical complex.
The critical complex described is also the reasonable
product of the environmental conditions that the ac-
companying paper (17) indicates lead to development of
water-repellent behavior. The combination of high temper-
atures and low rainfall create dehydration conditions neces-
sary to force formation of H-bonds between the petroleum
compound diagenesis products and SOM. This dehydration
also serves to force intramolecular H-bonding in SOM to
create an outer surface suitable for petroleum residue
solvation.
TABLE 2. Effect of Ext ract i ons on MED Val ues
soil extractant
extractable
material (g/kg)
MED
before
MED
after
ELL-NW DCM* 8.1 ( 0.5 3.8 ( 0.1 3.6 ( 0.1
ELL-CW DCM 0.20 ( 0.06 0.0 ( 0.1 0.0 ( 0.1
ELL-NW NaOH 3.8 ( 0/1 0.4 ( 0.1
ELL-CW NaOH 0.0 ( 0.1 0.0 ( 0.1
ELL-NW IPA/NH3 12.9 ( 0.8 3.8 ( 0.1 0.3 ( 0.1
TABLE 3. El ement al Anal ysi s and MED Val ues aft er Ext ract i ons
wi t h CH
2
Cl
2
(DCM) and Subsequent l y 2-Propanol /Ammoni a
(I PA/NH
3
)
a
soil andextractions %C %H %N MED(M)
ELL-NW 5.6 0.5 0.4 3.8
ELL-NW DCM 5.3 0.4 0.3 3.6
ELL-NW DCM + IPA/NH3 air-dry 5.2 0.6 0.6 1.8
a
Similar results were obtained for the DEV-NW sample. C, H, and
Nanalyseswithestimateduncertaintyof 0.02%wereroundedtonearest
0.1% to express significance conservatively.
RCOOH + NH
3
h RCOO
-
NH
4
+
(1)
FIGURE5. Effectsofsequentialextractionsonthewaterrepellency
of soils. (A) Water repellencyof ELL-NWsoil duringa six-step
sequentialextractionwithIPA/NH3andDCM(2).(B)Waterrepellency
ofELL-NWandDEV-NWsoilsinthecourseoffive-stepsequential
extractionwithDCMandIPA/NH3.
VOL. 37, NO. 13, 2003 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 2887
Figure 6 shows our impression of the structure on a NW
soil particle. The model is fully consistent with NMR,
extraction studies, and analysis of the wetting process and
the climatic conditions responsible for development of NW
behavior elucidatedinthe accompanying paper (17). As well,
computational modeling of a structure representative of
humic substances shows that a conformational rearrange-
ment of the type proposed is expected between wet and dry
states (24).
Acknowl edgment s
We would like to thank Dr. Julie Roy, Dr. Aldo Bruccoleri, Dr.
Donald Gamble, Dr. Robert Cook, and Florence Manalo for
valuable discussions. We would also like to thank NSERCfor
support under a strategic grant and Imperial Oil Ltd. for
consultation and funding. M.L. acknowledges an NSERC
industrial fellowship co-sponsored by Imperial Oil.
Support i ng I nformat i on Avai l abl e
Additional figures andinformationonthe DEVandSTEsites.
This material is available free of charge via the Internet at
http://pubs.acs.org.
Li t erat ure Ci t ed
(1) Roy, J. L.; McGill, W. B.; Rawluk, M. D. Can. J. Soil Sci. 1999, 79,
367.
(2) Roy, J. L.; McGill, W. B. Can. J. Soil Sci. 2000, 80, 595.
(3) Roy, J. L. Soil Water Repellency at Old Crude Oil Spill Sites.
Ph.D. Thesis, University of Alberta, Edmonton, AB, 1997.
(4) Todoruk, T. R. NMR Study of the Role of Water in Contaminant
Uptake into Clean and Contaminated Soils, Ph.D. Thesis,
University of Calgary, Calgary, AB, 2003.
(5) Sanders, J. K. M.; Hunter, B. K. Modern NMR Spectroscopy, 2nd
ed.; Oxford University Press: Oxford, 1993.
(6) Nanny, M. A.; Minear, R. A.; Leenheer, J. A. Nuclear Magnetic
Resonance Spectroscopy in Environmental Chemistry; Oxford
University Press: New York, 1997.
(7) Preston, C. M. Soil Sci. 1996, 161, 144.
(8) Wilson, M. A.; Pugmire, R. J.; Zilm, K. W.; Goh, K. M.; Heng, S.;
Grant, D. Nature 1981, 294, 648.
(9) Hatcher, P. G.; Breger, I. A.; Dennis, C. W.; Maciel, G. E. In
Aquatic and Terrestrial Humic Stubstances; Christman, R. F.,
Gjessing, E. T., Eds.; Ann Arbor Science: Ann Arbor, MI, 1983;
Chapter 3.
(10) Thurman, E. M.; Malcolm, R. L. InAquatic andTerrestrial Humic
Substances; Christman, R. F., Gjessing, E. T., Eds.; Ann Arbor
Science: Ann Arbor, MI, 1983; Chapter 1.
(11) Wilson, M. A. NMRTechniques andApplications inGeochemistry
and Soil Chemistry; Pergamon Press: Oxford, 1987.
(12) Cook, R.; Langford, C. H. Environ. Sci. Technol. 1998, 32, 719.
(13) Kogel-Knabner, I. Geoderma 1997, 80, 243.
(14) Kinchesh, P.; Powlson, D. S.; Randall, E. W. Eur. J. Soil Sci. 1995,
46, 125.
(15) Cook, R. L.; Langford, C. H.; Yamdagni, R.; Preston, C. M. Anal.
Chem. 1996, 68, 3979.
(16) Toogood, J. A. The Reclamation of Agricultural Soils after Oil
Spills; Department of Soil Science: The University of Alberta,
1977; A.I.P. No. M-77-11,
(17) Todoruk, T. R.; Litvina, M.; Kantzas, A.; Langford, C. H. Environ.
Sci. Technol. 2003, 37, 2878-2882.
(18) King, P. M. Aust. J. Soil Res. 1981, 19, 275.
(19) Malcolm, R. L. Anal. Chim. Acta 1990, 232, 19.
(20) Kingery, W. L.; Simpson, A. J.; Hayes, M. H. B.; Locke, M. A.;
Hicks, R. P. Soil Sci. 2000, 165, 483.
(21) Silverstein, R. M.; Bassler, G. C.; Morrill, T. C. Spectrophotometric
Identification of Organic Compounds, 4th ed.; John Wiley and
Sons: New York, 1981.
(22) Randall, E. W.; Mahieu, N.; Powlson, D. S.; Christensen, B. T.
Eur. J. Soil Sci. 1995, 46, 557-565.
(23) Engebretson, R. R.; Von Wandruszka, R. Environ. Sci. Technol.
1998, 32, 488.
(24) Bruccoleri, A. G.; Sorensen, B. T.; Langford, C. H. In Humic
Substances, Structures, Models, and Functions; Ghabbour, E. A.,
Davies, G., Eds.; Special Publication 273; Royal Society of
Chemistry: Cambridge, 2001; pp 193-208.
Received for review November 2, 2002. Revised manuscript
received April 8, 2003. Accepted April 29, 2003.
ES026296L
FIGURE6. Model of theinteractionbetweennatural soil organic
matter(NOM)andthediageneticproductsofpetroleumcontamina-
tionthatgenerates water repellency.
2888 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 13, 2003