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᭧ 2001 Geological Society of America 1092
GSA Bulletin; August 2001; v. 113; no. 8; p. 1092–1104; 12 figures; 5 tables.
Origin of illite in the lower Paleozoic of the Illinois basin:
Evidence for brine migrations
Georg H. Grathoff*
Department of Geology, Portland State University, Portland, Oregon 97207-0751, USA
Duane M. Moore
Illinois State Geological Survey, 615 East Peabody Drive, Champaign, Illinois 61820, USA
Richard L. Hay
Department of Geosciences, University of Arizona, Tucson, Arizona 85721, USA
Klaus Wemmer
Institut fu¨r Geologie und Dynamik der Lithospha¨re, Goldschmidtstrasse 3, Universita¨t Go¨ttingen, D-37077 Go¨ttingen, Germany
ABSTRACT
In the lower Paleozoic of the Illinois Ba-
sin, three illite polytypes are found: 2M
1
of
detrital origin, and 1M
d
and 1M of diage-
netic origin. Illite polytype quantification of
detrital 2M
1
illite and diagenetic 1M
d
and
1M illite, combined with K-Ar age dating,
allows extrapolation to apparent detrital
and diagenetic illite ages. Kinetic modeling
of smectite illitization, combined with the
calculated age of illitization, can evaluate
different origins of illite. The diagenetic il-
lite in the lower Paleozoic of the Illinois Ba-
sin is interpreted not to have formed solely
by burial diagenesis but mainly during
multiple brine events.
The Upper Ordovician Maquoketa
Group contains diagenetic illite (dominant-
ly 1M
d
with minor 1M) with an extrapolat-
ed age of ϳ360 m.y. (356–377 m.y.) and
formed from smectite at temperatures of
50–100 ؇C. This age falls within the span of
dates for illite/smectite (I/S) in K-bentonites
from the Upper Mississippi Valley and is
interpreted to be a combined result of illi-
tization by burial diagenesis and either a
hydrothermal brine from the southern and
deeper part of the basin or a K-rich brine
from the Michigan Basin, Upper Mississip-
pi Valley area, or Forest City Basin.
In Ordovician and Cambrian shale part-
ings and sandstone older than the Maquo-
keta Group, the diagenetic illite (1M
d
in
shale and 1M in sandstone) has an age of
*E-mail: grathoffg@pdx.edu.
ϳ300 m.y. and formed at temperatures
Ͻ140 ؇C. This late Paleozoic age falls with-
in the range of illites from sandstone in the
Upper Mississippi Valley and K-bentonites
of the Appalachian Basin; it coincides with
the Alleghany orogeny and is interpreted as
having formed by gravity-driven flow from
the uplifted Alleghanian-Ouachita orogenic
belt that drove hot (Ͻ140 ؇C) fluids
through the Illinois Basin.
Keywords: Illinois basin, illite, K/Ar, kinet-
ics, Maquoketa Group, polytypes.
INTRODUCTION
Understanding the nature, origin, and age of
illite helps unravel the depositional and dia-
genetic history of sedimentary basins. The
burial diagenetic reaction of smectite to illite
has been studied in many basins, including the
U.S. Gulf Coast (Hower et al., 1976), Paris
Basin (Mathieu and Velde, 1989), and central
Poland (S
´
rodon´ and Eberl, 1984). The distri-
bution of illite and smectite in the Illinois Ba-
sin (for geologic setting see Fig. 1) is different
from that of these basins. Hughes et al. (1987)
noted that illite in the Upper Ordovician Ma-
quoketa Group is mainly the 2M
1
illite poly-
type, whereas the older Ordovician and Cam-
brian sandstone and carbonate contained
principally the 1M illite polytype (for stratig-
raphy see Fig. 2). This observation is opposite
of what would be expected if illite formed
solely by burial diagenesis of smectite. If the
2M
1
illite is detrital in origin, like most 2M
1
illite in shale including ours, the change co-
incides with the change in the source area.
Bailey et al. (1962) recognized that illite in
shale is a mix of detrital mica, its weathering
products, and diagenetic illite. Later workers
concluded that the detrital mica or illite is of
the 2M
1
polytype, whereas the 1M and 1M
d
are diagenetic. Five observations support
these conclusions. First, as grain size decreas-
es, the amount of 2M
1
illite polytype decreases
in proportion to the 1M and 1M
d
illite poly-
types (Pevear, 1992; Grathoff et al., 1998).
Second, the ages of the progressively smaller
size fractions decrease (Hower et al., 1963;
Pevear, 1992; Grathoff et al., 1998). Third, the
2M
1
polytype is clearly established as the most
stable of these three polytypes (Yoder and
Eugster, 1955; Velde, 1965; Weaver and
Broeckstra, 1984). Fourth, bentonites that
have undergone diagenesis to I/S or illite, or
both, may contain biotite as phenocrysts, but
contain no detrital 2M
1
dioctahedral illite; all
I/S and illite in bentonite are 1M and 1M
d
,
unless they have been changed by metamor-
phism. Fifth, additional support for the con-
clusion that 1M and 1M
d
are diagenetic comes
from the observation that illite with morphol-
ogy indicating that it grew in the pore space
of clean sandstone is exclusively 1M (Pevear,
1999).
Others who have attempted to date illite in
shale (Hurley et al., 1961, 1963; Bailey et al.,
1962; Hower et al., 1963; Zhao et al., 1997;
Grathoff and Moore, 1996) have recognized
detrital and diagenetic components with the
detrital age older than the stratigraphic age
and the diagenetic age younger. It has not been
Geological Society of America Bulletin, August 2001 1093
ORIGIN OF ILLITE IN THE LOWER PALEOZOIC OF THE ILLINOIS BASIN
Figure 1. Geologic setting of the Illinois Basin showing locations of the cores that were
sampled, La Salle anticlinorium, Hicks Dome, and surrounding structures. For explana-
tions of the core abbreviations, core information, and sample interval, see Table 1.
Figure 2. General stratigraphic column of
the lower Paleozoic rocks of the Illinois Ba-
sin. From Kolata (1991) and Willman et al.
(1975).
universally recognized that all size fractions
contain some detrital material, but Pevear
(1992), Girard and Barnes (1995), and this
study show that even the Ͻ0.2 ␮m size frac-
tion contains some detrital 2M
1
polytype.
Gharrabi and Velde (1995) suggested that
diagenetic illite in the Illinois Basin formed
solely by burial diagenesis. However, another
explanation could be that the hot Upper Mis-
sissippi Valley ore-bearing fluids proposed to
have migrated through lower Paleozoic sedi-
ments in the Illinois Basin could also have
formed some or all of the illite (e.g., Bethke,
1985). The Upper Ordovician Maquoketa
Group, the oldest low-permeability unit that is
present uniformly across the basin, may have
confined these long-range brine migrations.
Today, the Maquoketa Group is a confining
layer or hydrologic boundary to groundwater
flow in northern Illinois and southern Wiscon-
sin (Siegel, 1990) and most likely would have
behaved as a confining layer in the past as
well. Long-range brine migrations through Pa-
leozoic strata below the Maquoketa Group are
thought to be responsible for producing re-
gional K metasomatism (Hay et al., 1988), Pb-
Zn ore deposits (Heyl et al., 1959; Bethke,
1985; Bethke and Marshak, 1990), and petro-
leum migrations (Bethke et al., 1991). Potas-
sic alteration in the U.S. Midcontinent has
produced widespread authigenic K-feldspar
and illite (Hay et al., 1988; Matthews, 1988;
Liu, 1997). Although the areal extent is still
unknown, the potassic alteration (authigenic
K-feldspar and illite) occurs in all units older
than the Upper Ordovician Maquoketa Group,
from the Precambrian through the Ordovician
(for review, see Matthews, 1988; Liu, 1997).
This study is the first to date illite in shales
in the Illinois Basin. In this paper, we delimit
the nature and origin of illite in the lower Pa-
leozoic strata of the Illinois Basin by using
illite polytype quantification (Grathoff and
Moore, 1996), combined with dating by K-Ar
age (Grathoff et al., 1998). These results show
that both multiple brine migration events and
burial diagenesis are responsible for illitiza-
tion in the Illinois Basin.
GEOLOGIC SETTING AND SAMPLE
LOCATIONS
The Illinois Basin began as a failed rift dur-
ing the breakup of a supercontinent during
Early and Middle Cambrian time and was
closed off at its southern end by the uplift of
the Pascola Arch some time after the Late
Pennsylvanian and before the Late Cretaceous
(Fig. 1; Kolata and Nelson, 1991). It is bound-
ed by the Kankakee Arch to the northeast and
the Cincinnati Arch to the east. It is now an
oval depression, deepest in the south and shal-
lowing northward, containing Cambrian
through Permian sedimentary rocks noncon-
formably overlying Precambrian granite and
rhyolite. The source area for sediments older
than the Maquoketa Group was the Canadian
shield and, to a minor extent, the Ozark dome
to the southwest (Kolata and Graese, 1983).
With onset of the Taconic orogeny, the source
area changed to an easterly Appalachian
source for the Upper Ordovician (Cincinna-
tian) Maquoketa Group. During the Alleg-
hany-Ouachita orogeny, the Illinois Basin was
subjected to intrusion, mineralization, and
compressional stresses related to major reac-
tivation of faults and structural activity (Beth-
ke and Marshak, 1990; Buschbach and Kolata,
1991; Kolata and Nelson, 1991; Nelson, 1995;
Marshak and Paulsen, 1996). In southern Il-
linois, the Hicks dome developed ca. 270 Ma
(Snee and Hayes, 1992; Zartman et al., 1967).
The Upper Mississippi Valley Pb-Zn ores and
the fluorspar district of southern Illinois are
also dated at 270–280 Ma (Chesley et al.,
1994; Brannon et al., 1992; Zartman et al.,
1967). See Leighton et al. (1991) for more de-
tails on all other geologic aspects of the Illi-
nois Basin.
The Maquoketa Group is a clastic wedge
that progrades westward from the Taconic up-
lands. The sediments of this major transgres-
sive cycle were deposited within a shallow
epicontinental sea at about latitude 10Њ–20ЊS
and have a constant thickness of about 60 m
across the Illinois Basin. They thicken to 300
m in eastern Indiana and to about 1800 m in
Pennsylvania (Witzke, 1980; Kolata and
Graese, 1983). The Maquoketa has a total or-
ganic carbon content (TOC) of up to 9.5%
1094 Geological Society of America Bulletin, August 2001
GRATHOFF et al.
TABLE 1. LOCATIONS OF THE SAMPLED CORES, THE SAMPLED INTERVAL, THE NUMBER OF
SAMPLES COLLECTED, AND THE UNITS SAMPLED
Core ISGS Illinois Location Number of Sampled interval Units sampled
core county samples (m) (from → to)
number
CL C228 Clinton Sec. 3, T. 2 N., R. 3 W. 60 999.0–1234.5 MAQ → SPS
G C7608 Fulton Sec. 5, T. 8 N., R. 1 E. 43 174.0–242.7 MAQ → GAL
IQ C3904 Iroquois Sec. 11, T. 26 N., R. 13 W. 29 186.0–1010.1 MAQ → MSS
ϩSS35648
W C2740 White Sec. 27, T. 4 S., R. 14 W. 7 1827.6–2252.4 MAQ and KNX
UPH3 C12996 Stephenson Sec. 7, T. 28 N., R. 6 E. 3 570.0–644.1 MSS
Total 142
Notes: ISGS—Illinois State Geological Survey, MAQ—Maquoketa Group, SPS—St. Peter Sandstone, GAL—
Galena Group, MSS—Mt. Simon Sandstone, KNX—Knox Group.
Figure 3. Illite crystallinity (IC) plotted against depth for the Ͻ1 ␮m size faction (CL
core) collected from XRD traces (glycol solvated). The solid symbols represent shale and
shale partings, and the open symbols represent carbonates.
Figure 4. IR (S
´
rodon´ , 1984) of the Ͻ1␮m size fraction (Clinton County core) collected
from XRD traces from oriented aggregates is plotted against depth. IR is the intensity
ratio of the air-dried illite 001/003 peaks, divided by the glycolated 001/003 peak ratio.
The solid symbols represent shale and shale partings, and the open symbols represent
carbonates. Asterisk denotes a sample that contains large amounts of corrensite (chlorite/
smectite), therefore increasing the error of the IR calculation.
(Hatch et al., 1991) and is a good source rock
for petroleum (Guthrie and Pratt, 1994; Guth-
rie, 1996).
Cambrian and Ordovician rocks below the
Maquoketa Group consist of the Galena-Plat-
teville Group carbonates, St. Peter Sandstone,
the thick Knox Supergroup carbonates, and
the Mt. Simon Sandstone (Fig. 2). The Cam-
brian Mt. Simon Sandstone, at the base of the
Paleozoic section, and the Ordovician St. Pe-
ter Sandstone are the two main aquifers in the
basin. See Willman et al. (1975) and Kolata
(1991) for more details on the Illinois Basin
stratigraphy.
The samples analyzed in this study were
collected from five cores within the basin (Ta-
ble 1; Fig. 1). We sampled different lithologic
units, concentrating on shale and shale part-
ings. Other than the Maquoketa Group, we
sampled the Ordovician Galena Group, Platte-
ville Group, Joachim Formation, St. Peter
Sandstone, and Everton Formation, as well as
the Cambrian Eau Claire Formation and Mt.
Simon Sandstone. The Maquoketa Group
samples from the G core are from a subset
studied for organic geochemistry and carbon
isotopic compositions (Guthrie, 1994; Guthrie
and Pratt, 1994; Guthrie, 1996). See Appendix
1 for analytical methods.
RESULTS
Illite Crystallinity Index, Intensity Ratio
(IR), and (001) Decomposition
Illites in rocks of the lower Paleozoic in the
Illinois Basin contain few expandable inter-
layers, on the basis of X-ray diffraction
(XRD) patterns of oriented mounts exhibiting
minimal illite peak shifts after glycolation and
no low-angle reflection (2–8Њ 2 ⌰, CuK␣ ra-
diation). Three methods were used to deter-
mine the percentage of smectite: full width at
half maximum (FWHM) of the 001 reflection,
known as illite crystallinity index (IC) (Ku¨-
bler, 1964), Jan S
´
rodon´’s intensity ratio (IR)
(S
´
rodon´, 1984, S
´
rodon´ and Eberl, 1984), and
peak decomposition of the 001 reflection
(Lanson and Champion, 1991; Velde et al.,
1986).
The IC index of the Maquoketa Group shale
(Ͻ1 ␮m size fraction) has an average of 0.53Њ
2 ⌰ (Ϯ0.03); the underlying Ancell Group
shale partings show a larger IC index, with an
average of 0.85Њ 2 ⌰ (Ϯ0.04) (Fig. 3). The IR
of the Maquoketa has an average of 1.24
(Ϯ0.10), and the Ancell shale partings have a
larger IR, averaging 1.39 (Ϯ0.14) (Fig. 4). As-
suming similar iron and water content per
smectite layer, the larger IR of the underlying
Geological Society of America Bulletin, August 2001 1095
ORIGIN OF ILLITE IN THE LOWER PALEOZOIC OF THE ILLINOIS BASIN
Figure 5. Different size fractions of the G 26–1 sample showing an increase in detrital
2M
1
with increasing size fraction. The 1–2 ␮m and 2–4 ␮m size fractions are not shown
here but contain 40% and 50% detrital 2M
1
illite, respectively. With increasing percentage
of 2M
1
illite, the illite hump (1M
d
illite) decreases in area. Dashed lines show the position
of 1M (trans-vacant) illite polytype-specific peaks, and triangles indicate peaks specific to
the detrital 2M
1
polytype; Q—quartz; F—K-feldspar; A—anatase.
units indicates that these units contain more
smectite. Using NEWMOD

(Reynolds,
1985) modeling, both units contain more than
95% illite in illite/smectite (I/S), and illite of
the Maquoketa Group contains ϳ2% less
smectite than illite of the underlying Ancell
Group. The results of the decomposition
method of Lanson and Champion (1991) and
Velde et al. (1986) show that the d-spacing for
the Maquoketa Group I/S peak is 10.65 A
˚
and
for the underlying units 10.90 A
˚
, indicating
that illite of the underlying units contains
more smectite than that of the Maquoketa
Group. Use of a graph in Velde et al. (1986)
shows that the Maquoketa Group contains
91% illite in I/S and the Ancell Group 88%
illite in I/S.
All three methods indicate that the lower
Paleozoic strata of the Illinois Basin contain
at least 88% illite in I/S and that the Maquo-
keta Group contains about 3% more illite than
that of the underlying Ancell Group. This is
opposite to what would be expected if increas-
ing smectite illitization with depth were the
only explanation for the origin of these illites,
but it can be explained using data from ran-
dom powder XRD.
Random Powder X-Ray Diffraction (XRD)
and Illite Polytype Quantification
Illite in all lower Paleozoic shales and shale
partings throughout the basin is mainly com-
posed of the 1M
d
polytype. The only differ-
ence is that the Maquoketa contains a higher
percentage of 2M
1
illite than the older under-
lying units. On average, the Ͻ1 ␮m size frac-
tion of the Maquoketa from the CL core con-
tains 68% 1M
d
, 23% 2M
1
, and 9% 1M,
whereas the shale partings below the Maquo-
keta contain Ͼ90% 1M
d
, Ͻ5% 1M, and Ͻ5%
2M
1
. Illite in Mt. Simon Sandstone is mainly
the 1M polytype. The Glenwood Formation
sandstone illite is a mixture of the 1M and 1M
d
polytypes.
The 2M
1
polytype increases in abundance
with increasing size fraction (Fig. 5). Sample
G 26–1shows an increase from 10% 2M
1
in
the Ͻ0.2 ␮m size fraction to 30 % 2M
1
in the
0.5–1 ␮m size fraction to 50% 2M
1
in the 2–
4 ␮m size fraction. Polytype 1M
d
decreases in
abundance with increasing grain size, and the
1M polytype remains about constant.
In summary, the Maquoketa Group contains
a higher percentage of detrital 2M
1
illite (23%
2M
1
in the Ͻ1 ␮m size fraction) than the un-
derlying units (Ͻ5% 2M
1
in the Ͻ1 ␮m size
fraction). Because 2M
1
illite contains no smec-
tite layers, only 77% of the illite (percent 1M
d
ϩ percent 1M) in the Maquoketa Group con-
tains smectite interlayering, compared to
Ͼ95% for the underlying units; this finding
explains the higher percentage of smectite in
the units underlying the Maquoketa Group.
Associated Minerals
Illite in the Maquoketa Group is associated
with chlorite, quartz, calcite, dolomite, fluor-
apatite, pyrite, and small amounts of K-feld-
spar. Chlorite was present in all samples ex-
cept at the base in the Parrish (G) core, where
chlorite disappears and fluorapatite appears.
Illite in the underlying units is associated
with chlorite, chlorite/smectite (including cor-
rensite), dolomite, calcite, quartz, anhydrite,
and abundant monoclinic K-feldspar. The
monoclinic K-feldspar is commonly euhedral
and authigenic in origin (Gruner, 1937; Matth-
ews, 1988). It decreases in abundance with de-
creasing grain size in the clay size fractions
and is usually absent from the Ͻ0.2 ␮m size
fraction. Chlorite was generally less abundant
in units below the Maquoketa Group. Mixed-
layered chlorite/smectite including corrensite
was found in the Ordovician Joachim Dolo-
mite of the Ancell Group in the CL core. Thin
layers of anhydrite are abundant in the interval
with the chlorite/smectite.
K-Ar Dating
The extrapolated K-Ar dates of the diage-
netic illite in the Maquoketa Group are close
to 360 Ma, and the underlying unites give
dates of close to 300 Ma (Table 2). K-Ar dates
of three different size fractions of two Ma-
quoketa Group samples (CL 3391 and G 26–
1) indicate that the Maquoketa Group 2M
1
il-
lite has a common detrital age of 520 m.y.
(Fig. 6). Assuming this detrital age of 520
m.y. for all Maquoketa Group samples, the re-
sulting apparent diagenetic ages range from
356–377 m.y., averaging around 360 m.y. The
exceptions are G 26–1 and G 27, which were
deposited at the contact with the underlying
Galena Group and have an apparent diagenetic
age of 321 m.y., ϳ40 m.y. younger than the
other Maquoketa samples (Fig. 6). It is as-
sumed that the 2M
1
illite is the only detrital
K-bearing component and that the 1M and
1M
d
illite are both diagenetic (for reasoning,
see Discussion). A second assumption is that
the extrapolation to detrital and diagenetic
end-member ages is a straight line; this is a
good assumption as long as the detrital and
diagenetic ages are not too far apart, and the
K content of the two illites is similar, which
is the case for our samples. For more discus-
sion on the extrapolation, see Grathoff et al.
(1998).
The dated samples from below the Maquo-
keta (Table 2) also have a common apparent
diagenetic age, 293–307 m.y., averaging about
300 m.y. The age for the Eau Claire shale (400
1096 Geological Society of America Bulletin, August 2001
GRATHOFF et al.
TABLE 2. K/AR DATES FROM THIS STUDY, INCLUDING SIZE FRACTION (s.f.), PERCENT DETRITAL ILLITE (2M
1
), MEASURED K/AR DATE, AND THE
CALCULATED DATE USING THE AMOUNT OF DETRITAL COMPONENT AND ITS AGE (520 Ma, FROM FIG. 6)
Sample Age Depth Core Unit Lith. s. f. K/Ar age Error Ma K
2
O
40
Ar*
40
Ar* %2M
1
Diagenetic Diagenetic age
(ft) (m)
(␮m) (Ma) (2␴) (wt%) nl/g STP (%) polytype (Ma)
IQM Ord 690 210 IQ MAQ sh Ͻ0.2 391 8.1 6.88 96.75 97.51 10% 1M
d
ϩ 1M} 377
CL 3391 Ord 3391 1034 CL MAQ sh Ͻ0.2 380 8.3 6.51 88.74 97.14 12% 1M
d
ϩ 1M} 365
CL 3391 Ord 3391 1034 CL MAQ sh Ͻ0.5 407 9.2 5.77 84.94 97.35 20% 1M
d
ϩ 1M
CL 3391 Ord 3391 1034 CL MAQ sh Ͻ2 441 9.1 4.60 74.04 98.61 52% 1M
d
ϩ 1M
W 6100 Ord 6100 1859 W MAQ sh Ͻ0.2 362 9.5 5.63 72.69 94.76 ** 1M
d
Ϯ 1M (362)
G-19 Ord 660 201 G MAQ sh Ͻ0.2 369 9.9 7.19 94.75 96.59 8% 1M
d
ϩ 1M} 356
G-25–1 Ord 759 231 G MAQ sh Ͻ0.2 377 7.8 6.12 82.50 96.60 13% 1M
d
ϩ 1M} 356
G 26–1 Ord 774 236 G MAQ sh Ͻ0.2 340 7.2 6.92 100.68 97.46 10% 1M
d
ϩ 1M} 321
G 27 Ord 775 236 G MAQ sh Ͻ0.5 372 9.7 6.57 87.43 96.79 25% 1M
d
ϩ 1M
G 26–1 Ord 774 236 G MAQ sh Ͻ2 403 9.7 6.95 83.85 96.77 42% 1M
d
ϩ 1M
IQGL Ord 1202 366 IQ GLW ss Ͻ0.5 364 7.7 7.68 99.76 96.81 b.d. ?
CLJ Ord 3969 1210 CL JOA sh Ͻ0.2 307 4.1 6.78 73.04 95.55 b.d. 1M
d
307
CLJ Ord 3969 1210 CL JOA sh 2–4 474 9.7 7.27 127.04 98.04
W7508 Ord 7508 2288 W KNX sh Ͻ0.2 345 8 8.14 99.68 97.80 17% 1M
d
ϩ 1M} 303
IQE Cam 3243 988 IQ EC sh Ͻ0.2 400 9.2 7.35 109.14 98.64 b.d. 1M
d
?
IQE Cam 3243 988 IQ EC sh 2–4 669Ma 13.8 8.53 222.64 98.95 Ͼ10%
IQMTS Cam 3367 1026 IQ MSS ss Ͻ0.5 293 9.3 8.81 90.42 98.95 b.d. 1M 293
Duffin et al. (1989) Cam 1900 579 UPH3 MSS ss Ͻ1 254 (Ϯ5) 11% 1M
Notes: b.d.—below detection limit (Ͻ5%), MAQ—Maquoketa Group, MSS—Mt. Simon Sandstone, JOA—Joachim Formation, KNX—Knox Group, EC—Eau Claire Group,
GLW—Glenwood Formation.
*Too little sample to quantify the polytypes.
Figure 6. Three size fractions of the Maquoketa from two different cores (CL and G);
both samples show a common extrapolated detrital age for the Maquoketa Group at 520
Ma.
m.y., Ͻ0.2 ␮m) may be a mixed age reflecting
minor amounts (not detectable by XRD) of
very old (Ͼ1 b.y.) mica or K-feldspar; the 2–
4 ␮m size fraction gives a K-Ar age of 669
m.y. and contains illite and K-feldspar.
Kinetics
The smectite to illite reaction is a function
of temperature (Hower et al., 1976; Boles and
Franks, 1979; Pytte and Reynolds, 1988), K
concentration (Altaner, 1985, 1989; Huang et
al., 1993), and time (Velde and Vasseur,
1992). We tested three models for the origin
of diagenetic illite: (1) pure burial diagenesis
(Fig. 7), (2) pure brine migration–hydrother-
mal at 100 ЊC and K-rich at 50 ЊC (Table 3),
and (3) a combination of burial diagenesis and
brine migration (Fig. 8). The kinetic calcula-
tions were compared with 90% illite in I/S and
the diagenetic illite age of 360 m.y. for the
Maquoketa. Our illitization age was calculated
using a method similar to that described in
Elliott and Matisoff (1996). It is the sum of
the product of the fraction of illite that formed
at each time step (10 m.y.) and the date of that
time step. For example, if 2% illite of the total
87% illite in I/S formed between 250 and 240
Ma, the contribution to the calculated date for
this time step would be 0.02 ϫ 245 Ma. The
summed calculated age is then normalized
(sum/0.87) to the final percentage of illite
(87% illite in I/S).
The first model assumes that illite formed
solely by burial diagenesis. The calculations
of the two end members, early (at 240 Ma)
and late (at 10 Ma) erosional stages, produce
83%–92% illite and a calculated time of illi-
tization of 301–311 Ma (Fig. 7, A and B).
Both calculations use a geothermal gradient of
30 ЊC/km (Cluff and Byrnes, 1991). Smaller
geothermal gradients (20 ЊC/km) produce too
little illite in I/S (67%–82%). Both the fast
and slow erosion models assume slow burial
(8.5 m/m.y.) from the Ordovician to the Penn-
sylvanian (450–300 Ma) and fast burial (30
m/m.y.) up to the Permian (300–250 Ma). The
fast burial is based on the 1.5 km of additional
sedimentary overburden postulated by Dam-
berger (1991) and others. If 1.5 km of rock is
not added, only 72% illite in I/S is formed. If
we assume that 20% of the illite is inherited,
as Hower et al. (1976) interpreted for the U.S.
Gulf Coast, the kinetic and age calculations
show that no additional illite is being pro-
duced and that the inherited illite must be old-
er than the detrital 520 Ma 2M
1
illite (Fig.
7C). We therefore conclude that even if some
1M
d
illite is inherited, which cannot be ruled
out, burial diagenesis alone cannot account for
both the highly illitic I/S and the age of the
1M
d
illite.
Geological Society of America Bulletin, August 2001 1097
ORIGIN OF ILLITE IN THE LOWER PALEOZOIC OF THE ILLINOIS BASIN
Figure 7. The pure burial diagenesis kinetic model. The model assumes an additional
1.5 km of overburden, deposited during the Pennsylvanian and Permian, as suggested
by Damberger (1991). The difference between A and B is the time of erosion. Erosion
in A occurred within the first 10 m.y. after maximum burial. Erosion in B has occurred
within the past 10 m.y. In model C, 20% of the K that formed the illite is assumed to
be old, 520 m.y. In A and B: 1—slow burial to 1.5 km, 2—fast burial to 3.0 km. In A,
3—erosion of 1.5 km, 4—isothermal (at 1.5 km). In B, 3—isothermal (at 3 km), 4—
erosion of 1.5 km.
TABLE 3. TIME REQUIRED TO PRODUCE 90% AND 80% ILLITE IN I/S USING THE KINETIC MODEL OF
HUANG ET AL. (1993) WITH DIFFERENT K CONCENTRATIONS AND TEMPERATURES
200 ppm 1000 ppm 2000 ppm 2000 ppm 10,000 ppm 20,000 ppm
100 ЊC 100 ЊC 100 ЊC 50 ЊC 50 ЊC 50 ЊC
(m.y.) (m.y.) (m.y.) (m.y.) (m.y.) (m.y.)
90% illite in I/S 17.3 3.5 1.7 601 120 60
80% illite in I/S 7.7 1.6 0.77 267 53 27
The pure brine migration models assume
that all the illitic I/S was formed in the Ma-
quoketa Group during a hydrothermal or K-
rich event at 360 Ma. Oxygen isotope data and
organic maturity indices indicate a tempera-
ture range of 50 to 100 ЊC for the Maquoketa.
Therefore, for the hydrothermal calculations
we assumed a maximum temperature of 100
ЊC, and for the K-rich brine event we assumed
a temperature of 50 ЊC. For the hydrothermal
calculations (100 ЊC), K
ϩ
pore-fluid concen-
trations must exceed 2000 ppm to form highly
illitic I/S over a short period (ϳ1 m.y.). For
the K-rich event calculations, to form 90% il-
lite in I/S at 50 ЊC, K
ϩ
pore fluid concentra-
tions must be extremely high (20 000 ppm),
and the reaction time is very long (60 m.y.)
(Table 3). Our conclusion is that a hydrother-
mal event or a low-temperature K-rich brine
event alone is unlikely to produce the highly
illitic I/S in the Maquoketa.
The mixed models are constructed to sim-
ulate illitization by burial diagenesis with ei-
ther a hydrothermal or K-rich brine event (Fig.
8). A 1-m.y.-long hydrothermal event at 360
Ma of 100 ЊC (K
ϩ
concentration of 2000
ppm), combined with burial diagenesis, pro-
duces 87% to 93% illite in I/S with an age of
347 to 359 m.y. A K-rich brine event (20 000
ppm K
ϩ
, 50 ЊC) at 360 Ma, combined with
burial diagenesis, produces 85% to 93 % illite
in I/S with an age of 329 to 344 m.y. Both
the hydrothermal event and K-rich brine alone
produce about 80% of the illite; the rest is
produced by burial diagenesis. Burial diagen-
esis of smectite is needed to form Ͼ90% illite.
We assume for the K-rich brine that the total
reaction time was about 16 m.y. until the K
ϩ
was depleted enough to slow down the reac-
tion, and kinetics of burial diagenesis took
over. (Table 4)
Oxygen Isotopic Composition
The ␦
18
O of three samples were analyzed,
two from the Maquoketa Group (G 19, Ͻ0.2
␮m, 17.6‰; CL 3391, Ͻ0.2 ␮m, 18.1‰) and
one from the Mt. Simon sandstone of the IQ
core (IQMTS, Ͻ0.5 ␮m, 15.3‰). The illiti-
zation temperatures of 50–100 ЊC for the Ma-
quoketa Group and 95–145 ЊC for the under-
lying Mt. Simon Sandstone were calculated
using the fractionation equation of Savin and
Lee (1988). We assumed a fluid composition
0‰–6‰ SMOW (standard mean ocean water)
and adjusted the ␦
18
O values of the Maquoketa
Group for detrital 2M
1
illite. The heavy iso-
topic composition of the brines (Ͼ0‰) was
based on fluid-inclusion data of dolomite in
the St. Peter Sandstone (Pitman and Spo¨tl,
1098 Geological Society of America Bulletin, August 2001
GRATHOFF et al.
Figure 8. The mixed-brine burial kinetic model. The kinetic model assumes a 100 ؇C brine
for 1 m.y. for model A and 20 000 ppm K for 16 m.y. for model B. The assumptions for
the burial part are the same as in Figure 7. 1—slow burial to 0.4 km, 2—hydrothermal
event (in A) and K-rich (in B), 3—fast burial to 3 km, 4—erosion of 1.5 km, 5—isothermal
(1.5 km).
1996) indicating high salinities (15–20 wt%
NaCl) for the Illinois Basin. In support of this,
we found anhydrite in the Ancell Group, a
diagenetic mineral that forms in highly saline
environments. For the upper limit ϩ6‰ was
used, on the basis of data from Clayton et al.
(1966) and Stueber and Walter (1991), who
analyzed deeper formation brines from the Il-
linois Basin. The ␦
18
O values of the Maquo-
keta Group illite were adjusted according to
the amount of detrital 2M
1
illite, assuming that
2M
1
illite forms at higher temperatures with
lower ␦
18
O values [e.g., ϩ10.4‰–13.3‰ for
muscovite (2M
1
) from metasedimentary strata
of southeastern New York (Garlick and Ep-
stein, 1967)]. Assuming the range of
ϩ10.4‰–13.3‰ for the 2M
1
illite (10%), the
diagenetic illite (90%) changes from 17.6‰–
18.1‰ to about 18.4‰–19.0 ‰.
Morphology
The illite morphology for three samples of
almost pure diagenetic illite [CL core Maquo-
keta Group (CL 3391, Ͻ0.2 ␮m), CL core Jo-
achim Formation (CLJ, Ͻ0.2 ␮m), IQ core
Mt. Simon Sandstone (IQMTS, Ͻ0.5 ␮m)]
was examined using an atomic force micro-
scope. On the basis of these three samples,
illite in the Maquoketa Group is morphologi-
cally distinct from that of illite in the units
older than the Maquoketa Group. The Maquo-
keta Group (Ͻ0.2 ␮m size fraction) contains
no laths, only very thin flakes (1–2 nm thick).
The Ancell and Mt. Simon samples contain
primarily laths that are relatively thick (130–
200 A
˚
).
DISCUSSION
The diagenetic illite in the Maquoketa
Group and that of the underlying units are of
different origin and did not form by burial dia-
genesis alone but were formed mainly during
two brine induced events, one 360 m.y. ago
and one 300 m.y. ago. This conclusion is
based on the different apparent ages of illiti-
zation, kinetic modeling, different illite poly-
types, different oxygen isotopic compositions,
and different morphologies.
An assumption made throughout the dis-
cussion is that the 1M and 1M
d
illites in both
the Maquoketa and the older underlying units
are diagenetic and that the apparent age of the
extrapolated pure (1M and 1M
d
) end-members
is not contaminated by detrital illite. Aronson
and Hower (1976) inferred the presence of de-
trital K and Ar in U.S. Gulf Coast shale. How-
ever, they did not determine or quantify the
illite polytypes. A possibility is that small
amounts of 2M
1
illite account for the detrital
K and Ar. For our samples, it cannot be ruled
out that the illite classed as diagenetic con-
tains some detrital admixture. However, the il-
litization age determined by our kinetic cal-
culations starting with 80% smectite (Fig. 7C)
shows that the detrital K must be older than
the detrital 2M
1
illite (520 m.y.) to account for
the extrapolated K-Ar age. We therefore think
we are justified in assuming that the starting
composition was close to 100% smectite and
that detrital 1M and 1M
d
illite is insignificant.
Timing of Illitization
The timing of illitization in lower Paleozoic
shales and shale partings of the Illinois Basin
is similar to some extent to the timing of il-
litization in lower Paleozoic K-bentonite and
sandstone of eastern North America and the
Upper Mississippi Valley (Fig. 9). Three
groups of illitization dates can be recognized
(Fig. 10). These are the same as the three ep-
isodes of illitization that Lee and Aronson
(1991) first reported for the Upper Mississippi
Valley: 215–230 Ma, 300–310 Ma, and 340–
360 Ma.
The oldest group is mid-Paleozoic, around
360 Ma, and occurs only in the northern part
of the U.S. Midcontinent, such as in the Ma-
quoketa Group within the Illinois Basin (this
study), the Upper Mississippi Valley (Hay et
al., 1988; Lee and Aronson, 1991) and the
Michigan Basin (Girard and Barnes, 1995).
The second group is late Paleozoic, 250–
310 Ma, and interpreted to be associated with
the Alleghany-Ouachita orogeny and possibly
with the Upper Mississippi Valley ore depo-
sition. These illitization dates are apparent
throughout a much wider area, from the Ap-
palachian Basin, through the Illinois Basin,
northeastern Missouri, to the Forest City Ba-
sin in Iowa (Fig. 10). The Upper Mississippi
Valley ore deposits were dated at 270 Ϯ 5 Ma
(Brannon et al., 1992) and the Illinois-Ken-
tucky fluorspar district at 277 Ϯ 16 Ma (Ches-
ley et al., 1994), and the Hicks dome devel-
oped around 270 Ma (Snee and Hayes, 1992;
Zartman et al., 1967).
The third group (215–230 Ma) has been
documented only in northwestern Illinois,
close to the Upper Mississippi Valley ore de-
posits (Lee and Aronson, 1991; Duffin et al.,
1989). Duffin et al. (1989) reported three dates
on illite in the Cambrian Mt. Simon Sandstone
in the Upper Mississippi Valley as 214, 254,
Geological Society of America Bulletin, August 2001 1099
ORIGIN OF ILLITE IN THE LOWER PALEOZOIC OF THE ILLINOIS BASIN
TABLE 4. SUMMARY OF KINETIC MODELING RESULTS AND MEASURED RESULTS
I in I/S formed Calculated Extrapolated K-Ar
(%) illitization age illitization age
(Ma) (Ma)
Solely burial diagenesis and early erosion 83 311
Solely burial diagenesis and late erosion 92 301
Hydrothermal and early erosion 87 359
Hydrothermal and late erosion 93 347
K-rich brine and early erosion 85 344
K-rich brine and late erosion 93 329
Burial diagenesis with 20% 520-m.y.-old K and early erosion 83 350
Burial diagenesis with 20% 520-m.y.-old Kand late erosion 92 336
Maquoketa Group diagenetic illite Ն90 360
Figure 9. Map of the K/Ar dates of diagenetic illite of Cambrian and Ordovician sediments
in and close to the Illinois Basin. For the dates in the Illinois Basin (inside the dashed
line), dates above the horizontal lines are from the Maquoketa Group and dates below
are from the underlying units. References: 1—This study; 2—Duffin et al. (1989); 3—
Elliott and Aronson (1993); 4—Hay et al. (1988); 5—Girard and Barnes (1995); 6—Duffin
(1990). Modified from Nelson (1995).
and 271 Ma. They concluded that the illite and
K-feldspar formed in multiple episodes of K
metasomatism. Our XRD results of the 254
Ma sample shows that it contains 11% 2M
1
illite (Table 2). When we adjust the age for
the presence of this detrital 2M
1
, we see that
the diagenetic age of the 1M illite must be
much younger, possibly as young as 214 m.y.
If the detrital 2M
1
illite has an age of 577 m.y.,
the resulting diagenetic age would be 214 m.y.
Therefore the Duffin et al. (1989) data might
indicate only two episodes of illitization, one
around 214 Ma and one around 271 Ma.
The K-Ar results from this study are inter-
preted to represent two basin-wide illitization
events, one at about 360 Ma affecting the Ma-
quoketa Group and one at around 300 Ma af-
fecting the underlying units. At the contact of
the Maquoketa Group and the underlying Ga-
lena Group, the diagenetic illite has an inter-
mediate age of 320 m.y. (Fig. 11). This raises
the question, Why is the illite younger in the
stratigraphically older units? Four explana-
tions can be offered: (1) The dates were reset;
(2) during the 360 Ma event, illite was not the
geochemically stable phase to precipitate in
the underlying units; (3) the 360 Ma event
never reached the underlying units; (4) a pro-
portion of the Maquoketa Group 1M
d
illite
contains detrital K.
The possibility that the ages in the under-
lying units were reset at 300 Ma is unlikely,
because the coarser size fractions, which con-
tain some 2M
1
illite, are older and would prob-
ably have been reset as well and because the
maximum temperature the sediments were ex-
posed to was significantly lower than the re-
setting temperature of at least 250 ЊC (e.g.,
Hunziker et al., 1986; Wemmer and Ahrendt,
1997).
The second explanation, that the chemical
conditions were not right to precipitate illite,
is more likely. Authigenic K-feldspar formed
before 400 Ma in lower Paleozoic sediments
surrounding the Illinois Basin (Hay et al.,
1988, 1993; Duffin et al., 1989; Liu 1997).
Therefore, the chemical conditions might have
been such that K-feldspar was stable and not
illite until ca. 360 Ma. The 360 Ma event
could have supplied heat, K, or both to form
illite, but did not change the fluid chemistry
to make illite the stable phase in the under-
lying units.
The third explanation, that the 360 Ma
event might not have reached the underlying
units, is only possible if dense K-rich brines
are introduced into the rocks overlying the
Maquoketa Group, which served as a semi-
permeable membrane.
The fourth explanation, that the 1M
d
illite
contains detrital K, is viable only if the orig-
inal smectite contained 20% or more old K
(illite layers), if the K retained an age older
than the detrital 2M
1
illite of more than 520
m.y. (see kinetics results), and if the Ar was
retained during illitization.
Pitman and Spo¨tl, (1996), reporting on the
St. Peter Sandstone, and Fishman (1997), re-
porting on the Mt. Simon Sandstone, found
two textural types of illite. One type coats
grains and the other one fills pores. Both types
of illite are diagenetic, according to Pitman
and Spo¨tl, (1996) and Fishman (1997). The
pore-filling illite formed later and is much
more abundant. This raises the question
whether our samples and all Mt. Simon Sand-
stone samples that were K-Ar dated contain
both or just one type of diagenetic illite. We
were not able to detect two types of diagenetic
illite with XRD in the Mt. Simon Sandstone.
However, there are differences in ages of 1M
d
illite. The illite (Ͻ0.2 ␮m) in the Eau Claire
shale is of the 1M
d
polytype and has a K-Ar
age of 400 m.y. This age could either be due
1100 Geological Society of America Bulletin, August 2001
GRATHOFF et al.
Figure 10. Map showing the summary and interpretation of K/Ar dates of diagenetic illite of Cambrian and Ordovician sediments (sh—
shale; ss—sandstones; b—K-bentonites) in and close to the Illinois Basin. The 254 Ma date from Duffin et al. (1989) is from illite that
contains 11% 2M
1
illite, which is likely to be detrital. Therefore, the diagenetic illite is possibly as young as 214 m.y. and is not correlated
with the Alleghany orogeny.
to small amounts of contamination by unde-
tected K-feldspar and 2M
1
illite or reflect the
age of the older type of illite that Pitman and
Spo¨tl, (1996) and Fishman (1997) reported.
The K-Ar age of the illite in the Glenwood
Sandstone of 364 m.y. could reflect a mixture
of 300-m.y.-old 1M Mt. Simon illite and 400-
m.y.-old 1M
d
Eau Claire illite, because the
random powder XRD from the Glenwood
sandstone shows a mixture of 1M
d
and 1M
illite.
The apparent detrital age of the Maquoketa
Group (520 m.y.) is not interpreted as a date
of an orogeny. The source of the 2M
1
illite
is the Taconic uplands along the eastern mar-
gin of Laurentia and not the Precambrian Ca-
nadian shield. As a result of the Taconic
orogeny, metasedimentary strata, possibly
mica schist containing 2M
1
muscovite, were
uplifted and eroded, and their detritus was
transported into the U.S. Midcontinent. The
520 m.y. age might be an average age, or it
might give the date of maximum burial of the
metasediments. The age is similar to the age
of the 6–62 ␮m size fraction (540 m.y.) of
the Upper Ordovician Sylvan Shale deter-
mined by Hower et al. (1963). The Sylvan
Shale, present to the southwest of the Illinois
Basin, is equivalent to the Maquoketa Group
(Willman et al., 1975). The 520 m.y. age is
also close to the age of the coarse illite of
the St. Peter Sandstone in the Michigan Ba-
sin, dated at 544–570 Ma (Girard and
Barnes, 1995).
Thermal Conditions of Illitization
The maximum temperature of illitization
was estimated three ways, from illite crystal-
linity, the presence of the 1M
d
illite polytype,
and the oxygen isotopic composition of the
illite. These results were then compared with
fluid-inclusion data, organic maturity indices,
and conodont alteration index (CAI) data cited
in the literature.
Illite crystallinity index averages of the Ma-
quoketa Group (0.53 Њ 2 ⌰) and the units older
than the Maquoketa Group (0.85Њ 2 ⌰) all lie
Geological Society of America Bulletin, August 2001 1101
ORIGIN OF ILLITE IN THE LOWER PALEOZOIC OF THE ILLINOIS BASIN
Figure 11. Summary stratigraphic column
of extrapolated K/Ar dates of diagenetic il-
lite in the Illinois Basin.
TABLE 5. RANGE OF TEMPERATURES DETERMINED FROM VITRINITE REFLECTANCE (R
0
) USING A
GRAPH IN DAMBERGER (1991) AFTER BOSTICK ET AL. (1979)
Age R
0
50 Ma* 200 Ma*
(ЊC) (ЊC)
Herrin Coal Pennsylvanian 0.4–0.7

Ͻ40–100 Ͻ30–80
New Albany Devonian 0.5–0.8
§
65–110 50–95
Maquoketa Ordovician Ͻ0.6–0.8
#
Ͻ85–110 Ͻ70–95
Note: The range in the vitrinite data does not include the bull’s-eye close to Hicks dome, which has higher
vitrinite reflectance.
*Refers to effective time of maximum burial. Effective time is the time that the sediment was within 15 ЊC of
the maximum temperature. To determine the temperatures, we used Damberger (1991) after Bostick et al. (1979).

Data from Cluff and Byrnes (1991).
§
Data from Hasenmueller and Corner (1994).
#
Estimated by Guthrie (1994) using Rock-Eval and Tmax data.
in the diagenesis zone of Weaver and Broeck-
stra (1984) (Ͼ0.42Њ 2 ⌰). The temperatures
did not reach the anchizone, which begins
with an illite crystallinity index of 0.42Њ 2 ⌰
and ends with the start of the epizone at 0.25Њ
2 ⌰. In addition to determining the illite crys-
tallinity index, Weaver and Broeckstra (1984)
defined the end of the diagenesis zone and be-
ginning of the anchimetamorphic zone as the
first occurrence of authigenic 2M
1
illite. Illite
of 2M
1
type in the Illinois Basin is inferred to
be detrital because the K-Ar age of this illite
is older than the depositional age. Type 2M
1
illite forms at temperatures of about 200–250
ЊC (Velde, 1965), and if the diagenetic reac-
tion sequence from 1M
d
to 1M and finally to
2M
1
from the laboratory experiments of Velde
(1965) holds true for shales, the high concen-
tration of 1M
d
illite in the Illinois Basin can
be used as another indicator of temperature
(ϽϽ200 ЊC).
The temperature of illitization was further
constrained by means of oxygen isotope data
indicating that the illite in the Maquoketa
Group formed at 50–100 ЊC and that the illite
from the underlying Mt. Simon Sandstone
formed at 95–145 ЊC. Organic maturity indi-
ces all indicate low temperatures as well. The
organic matter for the Maquoketa Group is
immature to early mature (Guthrie, 1994). Vi-
trinite reflectance values (R
0
) for a Pennsyl-
vanian coal are 0.4–0.7 (Cluff and Byrnes,
1991), for the New Albany shale are 0.5–0.8
(Hasenmueller and Comer, 1994), and for the
Maquoketa Group are Ͻ0.6–0.8 (Guthrie,
1994) (Table 5). The reflectance values for the
Maquoketa Group were estimated using Rock-
Eval data and T
max
(Guthrie, 1994). The re-
flectance data for the Herrin Coal and the New
Albany shale do not include higher reflectance
associated with the intrusion of the Hicks
dome. Vitrinite reflectance is a function of
temperature and effective time of heating.
Damberger (1991) (after Bostick et al., 1979)
estimated temperatures by using effective time
of heating, which refers to the time the sedi-
ment was within 15ЊC of the maximum tem-
perature. The resulting temperatures for the
Pennsylvanian to the Upper Ordovician Ma-
quoketa Group section seem to be no higher
than 110ЊC, if we assume Ͼ50 m.y. of effec-
tive time of burial (Table 5).
For Ordovician carbonates underlying the
Maquoketa Group, unpublished CAI data
from the central and northern part of the Illi-
nois Basin indicate indexes between 1 and 2
(Rodney D. Norby, Illinois State Geological
Survey, 1996, personal commun.); these de-
crease toward the north, indicating tempera-
tures of Ͻ50 to 140 ЊC (Harris, 1979).
Illite crystallinity, illite polytype, and oxygen
isotope data agree with the interpretation of the
published data all indicating that maximum
temperatures in the Maquoketa Group were be-
tween 50 and 100 ЊC and that the units under-
lying the Maquoketa Group formed at higher
temperatures, but not higher than 140 ЊC.
Evaluation of Origins of Diagenetic Illite
Diagenetic illite in the Maquoketa Group
consists of highly illitic I/S with an extrapo-
lated age of 360 m.y. Is the origin of diage-
netic illite due to the long burial time, as in-
terpreted by Gharrabi and Velde (1995), to a
brine event (hydrothermal or low-T K-rich),
or some combination of the above?
Our results indicate that only a combination
of burial diagenesis and a hydrothermal or a
K-rich brine event can explain both the 360
m.y. age of the 1M and 1M
d
illite and the per-
cent illite in I/S in the Maquoketa Group.
Gharrabi and Velde (1995) interpreted their I/
S quantification data as being caused solely by
burial diagenesis, with the addition of 1.5 km
of additional overburden, eroded after the
Permian. Our kinetic modeling indicates that
highly illitic I/S can be a product of several
origins: burial diagenesis alone, a hydrother-
mal event, a K-rich brine event, or a combi-
nation of the three. However, determining the
calculated age of illite from kinetic modeling
and comparing these data with observed age
data can distinguish whether burial diagenesis
alone or a combination of processes formed
the illite. Currently, we are not able to distin-
guish which process, the hydrothermal or low-
T K-rich brine, is more likely.
The hydrothermal event from the south
could have been triggered by fault move-
ments, for which Nelson and Marshak (1996)
found evidence during the Devonian. In ad-
dition the Ozark dome, the Sangamon Arch,
and the Sparta shelf were also uplifted during
the Devonian (Kolata and Nelson, 1991). Mar-
shak and Paulsen (1996) suggested that in the
U.S. Midcontinent, reactivated fault zones act-
ed as fluid conduits to drive fluids from the
basement into shallower sediments, depositing
ore bodies. A similar mechanism, combined
with gravity-driven regional brine migrations,
could have caused the 100 ЊC hot fluids to
migrate from the deeper part of the basin into
the shallower and younger sediments, heating
the Maquoketa Group to 100 ЊC for 1 m.y. or
less (Fig. 12).
The hypersaline brines flowing from the
north into the Illinois Basin could have come
from the Michigan Basin, the Forest City Ba-
sin, or the Upper Mississippi Valley area. The
heavy hypersaline brine flowed into the Illi-
nois Basin on top of the Maquoketa Group
(Fig. 12). Movement of these brines could
have been caused by uplift of the Wisconsin
and/or Kankakee arches. Both arches were up-
lifted during the Silurian and Devonian (Nel-
son, 1995; Kolata and Nelson, 1991). These
gravity-driven brines would flow into the Si-
1102 Geological Society of America Bulletin, August 2001
GRATHOFF et al.
Figure 12. Model of two different brines migrating though the Illinois Basin during the
deposition of the New Albany shale (360 Ma). The filled arrows point toward the fluid
flow direction for the hydrothermal brines. A representative fault is depicted by the half
arrows, which point toward the direction of fault movement. The driving force would be
the uplift of the Ozark dome, the Sangamon Arch, or the Sparta shelf. The white arrows
point toward the fluid flow direction for the K-rich brines, which migrated from north of
the Illinois Basin into the basin on top of the Maquoketa Group. The driving force would
be the uplift of the Kankakee arch or the Wisconsin arch.
lurian and Devonian carbonates in the Illinois
Basin and migrate downward, owing to the
density of the brine. The Maquoketa would
serve as an aquitard to these dense hypersaline
brines. The brines would slowly flow through
the Maquoketa Group, forming illite from
smectite and depleting the brine of K.
The illite in the underlying units with a K-
Ar age of ϳ300 m.y. is likely to have formed
by means of a hydrothermal event, which
originated in the Alleghany-Ouachita orogenic
belts. The reasons for our interpretation are (1)
the temperature of illitization is higher, ϳ140
ЊC, reducing the time to form 90% illite from
pure smectite to less that 0.5 m.y. with K con-
centrations of 200 ppm (we used an equation
of Huang et al., 1993); (2) the age of the illite
is similar to other dated illite in the U.S. Mid-
continent and the Appalachian basin, and it
corresponds to the Alleghany-Ouachita orog-
eny; and (3) the morphology of the illite is
laths, suggesting direct precipitation.
CONCLUSIONS
The diagenetic illite in the lower Paleozoic
of the Illinois Basin did not form by burial
diagenesis alone, but was formed mainly dur-
ing two events, one at 300 Ma and one at 360
Ma. This conclusion is based on comparing
analytical results (percentage of smectite in il-
lite/smectite and extrapolated K-Ar ages of the
diagenetic illite) with kinetic modeling results
(percentage of smectite in I/S and calculated
age of illitization). The late Paleozoic 300 Ma
event might have been associated with the Al-
leghany-Ouachita orogeny. During the
Alleghany-Ouachita event, the Maquoketa
Group served as an aquitard to brines that
formed the illite in the underlying units. The
360 Ma event that formed most of the diage-
netic illite in the Maquoketa Group might
have been caused by either a hydrothermal
event (100 ЊC) from the southern and deeper
part of the Illinois Basin, possibly due to uplift
of the Ozark dome, Sangamon Arch, and
Sparta shelf, or a K-rich brine from north of
the Illinois Basin (Michigan Basin, Upper
Mississippi Valley, Forest City Basin) induced
by uplift of the Wisconsin Arch or Kankakee
Arch.
The Upper Ordovician Maquoketa Group
contains less smectite than the underlying
units, which is opposite of what would be ex-
pected if burial diagenesis of smectite were
the only explanation for the origin of the illite.
This anomaly can be explained using illite po-
lytype quantification. The Maquoketa Group
contains an average of 23% detrital 2M
1
illite
(Ͻ1 ␮m size fraction), which has no smectite
interlayers and forms larger crystallites than
the diagenetic 1M and 1M
d
illite. The under-
lying units contain on average less than 5%
detrital 2M
1
illite (Ͻ1 ␮m size fraction).
Therefore, the Maquoketa Group contains
only apparently less smectite.
The temperature of illitization in the Ma-
quoketa Group was 50–100 ЊC. For the units
underlying the Maquoketa Group, the temper-
ature of illitization was higher, but not as high
as 140 ЊC. The illite in the units underlying
the Maquoketa Group formed at higher tem-
peratures, which were caused by uplift and
subsequent flushing of warmer brines from the
deeper part of the basin.
APPENDIX 1. METHODS
For X-ray diffraction (XRD) analysis of oriented
aggregates, we separated the Ͻ0.2 ␮m and Ͻ1 ␮m
size fractions, using a centrifuge, and collected a
size fraction with a Millipore௢ filter and transferred
it onto a glass slide (Moore and Reynolds, 1997).
Then FWHM of the 001 reflection, known as the
illite crystallinity index (Ku¨bler, 1964), Jan S
´
ro-
don´’s IR (S
´
rodon´, 1984; S
´
rodon´ and Eberl, 1984),
and peak decomposition of the 001 reflection were
determined. IC is a function of crystallite size (or,
more appropriately, X-ray diffracting domain size)
and smectite content. The IR is a function of the
smectite content, the number of water layers in the
air-dried samples, and the iron content. Selected
samples were sent to Bruce Velde’s laboratory at
the Ecole Normale Supe´rieure, Paris, where Dr.
James Matthews decomposed the XRD traces in the
region of the illite 001 peak, using the same method
as Lanson and Champion (1991) and Velde et al.
(1986). Their method decomposes the illite 001
peak (air-dried treatment) into an illite peak, a mica
peak, and an I/S peak. The d-spacing of the inter-
preted I/S peak component is proportional to the
smectite content of the I/S. The larger the d-spacing
is, the larger the smectite content in the I/S.
For random powder XRD, we separated the Ͻ0.2
␮m, 0.2–0.5 ␮m, 0.5–1 ␮m, 1–2 ␮m, and 2–4 ␮m
size fractions using a centrifuge, flocculated the
size-separated suspensions, dialyzed the suspen-
sions, and then evaporated them. Chlorite and car-
bonate were removed using 1 M HNO
3
. The organic
material was removed using household bleach (so-
dium hypochlorite) (1 part bleach to 2 parts distilled
water). These treatments were also followed by di-
alysis and evaporation.
Using the method described in Grathoff and
Moore (1996), we quantified the amount of each
illite polytype from all the units studied. An ex-
ample of the method is shown in Figure A1, where
an experimental pattern of the Maquoketa Group
sample G 26–1, 0.2–0.5 ␮m size fraction, is plotted
together with the mixed WILDFIRE

-calculated
pattern (Reynolds, 1993). XRD data were obtained
using a Scintag

theta-theta diffractometer with a
DMS

operating system and operating conditions of
40 kV and 30 mA. This diffractometer uses CuK

radiation, a liquid N
2
-cooled germanium solid state
detector, two Soller slits, a 2 mm divergence slit,
and a 0.5 mm slit at the detector.
The K-Ar age, oxygen isotopic composition, and
morphology of illites were determined for selected
samples. K-Ar dating of the illites was obtained at
the Institut fu¨r Dynamik der Lithospha¨re at the
Georg August Universita¨t, Go¨ttingen, Germany. For
details of the analytical procedures, see Wemmer
Geological Society of America Bulletin, August 2001 1103
ORIGIN OF ILLITE IN THE LOWER PALEOZOIC OF THE ILLINOIS BASIN
Figure A1. Experimental and calculated trace of the 0.2–0.5 ␮m size fraction of G 26–1,
Maquoketa Group sample (G core) taken at a depth of 232.2 m. Dashed lines show the
position of 1M (trans-vacant) illite polytype-specific peaks, triangles indicate peaks specific
to the detrital 2M
1
polytype; Q—quartz; A—anatase.
and Ahrendt (1997) or Grathoff et al. (1998). Ox-
ygen isotopic composition was determined in Sam-
uel Savin’s laboratory, Case Western Reserve Uni-
versity, by Robert Ylagan. The morphology was
examined with an atomic force microscope at the
Beckman Institute, University of Illinois, with the
help of Javier Cuadros.
For the kinetic modeling of smectite illitization
through burial diagenesis, we used a computer pro-
gram developed by Bill Benzel, Marathon Oil Co.,
Littleton, Colorado, and Stephen Altaner, Depart-
ment of Geology, University of Illinois; the program
is based on the kinetic equation of Pytte and Reyn-
olds (1988). For smectite illitization in hydrother-
mal and K-rich brine systems, we used the kinetic
equation of Huang et al. (1993). Kinetic parameters
for both equations were the same as Elliott and Ma-
tisoff (1996), who compared these kinetic models.
For the Pytte and Reynolds equation, the input var-
iables were a fifth-order reaction, activation energy
of 30 000 cal/mol, and a frequency factor of 90 000/
s. For Huang et al.‘s (1993) third-order equation,
the input variables were an activation energy of 28
000 cal/mol, a frequency factor of 80 800/s, and K
concentrations of 1000, 2000, and 20 000 ppm. Oth-
er assumptions included (1) a K/Na ratio for Pytte
and Reynolds (1988) that was controlled by K/Na
feldspar equilibrium; (2) a burial rate of 8.5 m/m.y.
[from Gharrabi and Velde (1995) for a core about
32 km south of the CL core; Fig. 1]; (3) a geother-
mal gradient of 30 ЊC/km (Cluff and Byrnes, 1991);
and (4) that an additional overburden of 1.5 km was
eroded after the Permian [based on Damberger
(1991), Cluff and Byrnes (1991) and Gharrabi and
Velde (1995), using, respectively, coal-seam mois-
ture, kinetic modeling of organic maturation, and
kinetic modeling of smectite illitization].
ACKNOWLEDGMENTS
This research was part of Georg Grathoff’s Ph.D.
thesis, completed at the University of Illinois at Ur-
bana/Champaign and supported in part by the Illi-
nois State Geological Survey and by a research
grant from the Clay Minerals Society. We thank
Elizabeth Burton, Eric Daniels, and W. Crawford
Elliott for their review comments on our
manuscript.
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MANUSCRIPT RECEIVED BY THE SOCIETY AUGUST 25, 1999
REVISED MANUSCRIPT RECEIVED AUGUST 8, 2000
MANUSCRIPT ACCEPTED NOVEMBER 27, 2000
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