Tec#onophysjcs, 184 (1990) 21-33

Elsevier Science Publishers B.V., Amsterdam

21
40Ar/39Ar laser dating of a single grain of magnetite
6zden 6zdemir and Derek York
Department of Physics, University of Toronto, Toronto, Ont. M5S I A7 (Canada)
(Received November 25,1989; revision accepted March 7, 1990)
ABSTRACT
&demir, ii. and York, D., 1990. Ar/39Ar laser dating of a single grain of magnetite. In: R. Van der Voo and P.W. Schmidt
(Editors), Reliability of Paleomagnetic Data. Tectonophysics, 184: 21-33.
We have determined an 40Ar/39Ar age spectrum for a single grain of magnetite using laser step-heating. A 300 pm
magnetite gram from a Grenville Front gneiss was heated in 14 steps to 16OOC. Excess 40Arf resulted in a saddle-shaped age
spectrum with an integrated age of 1962 f 39 Ma. However, the minimum of the saddle gave an age of 1144 f 107 Ma,
consistent with typical Grenvillian cooling ages of llOO-900 Ma. We have also dated a single gram of biotite from the same
hand sample as the may&e. The spectrum yielded an integrated age of 1261 + 3.6 Ma. The thermal release patterns of *OAr*
and of Ca/K ( 37Ar/3 Ar) were very different for the magnetite and biotite. Thus 40Ar* can be retained in measurable
quantities in magnetite. Our results are a fit step toward the attempted direct dating of different components of NRM in
paleomagnetism.
Introduction
The iron-oxide minerals can carry a faithful
record of the geomagnetic field at the time of
original cooling of an igneous rock or deposition
of a sedimentary rock. The direction of the natural
remanent magnetization (NRM) derived from
paleomagnetic analysis may indirectly provide the
age of the magnetization by comparison with
established apparent polar wander paths (APWPs).
However, it often happens that the APWP is am-
biguous (that is, paleopoles of different ages have
similar directions) or poorly established. This is
particularly the case for Paleozoic or Precambrian
cratonic rocks and for rocks of any age from
accreted terranes. For these rocks, we need an
independent method of dating NRMs.
The K/ Ar and more recently the ?Ar/ 39Ar
radiometric methods, have been widely used for
the direct dating of potassium-bearing minerals.
Because of the parallels between magnetic and
argon blocking temperatures, it has sometimes
been possible to infer ages of magnetization from
cooling histories determined from 49Ar/ 39Ar
analyses (Buchan et al., 1977; Berger et al., 1979;
York, 1984; Layer et al., 1989). All such compari-
sons between paleomagnetic and 4oAr/ 39Ar
analyses make the assumption that the iron oxides
and the potassium-bearing minerals such as bio-
tite, hornblende and K-feldspar formed effectively
simultaneously and experienced the same cooling
history. However, magnetite, which is the most
common iron-oxide mineral in continental ig-
neous, sedimentary or metamorphic rocks, is fre-
quently secondary, diagenetic, hydrothermal or
deuteric in origin. Hence the cooling curve derived
from the ages of the potassium-bearing minerals
can not necessarily be used to determine the age
of formation and magnetization of magnetite.
Magnetite can form at temperatures below the Ar
blocking temperature of micas and amphiboles,
i.e. <300C.
Ideally one would like to be able to check the
formation age of magnetite directly. Any mineral
which contains enough potassium is potentially
suitable for Ar/ 39Ar dating. The potassium may
be either an integral cation in the mineral lattice
or an impurity in the mineral (D~~mple and
0040-1951/90/$03.50 6 1990 - Elsevier Science Publishers B.V.
22
0.6ZDEMIR AN11 D. YORK
Lanphere, 1969). It should be possible to date
magnetite provided that sufficient potassium is
present, either in the lattice, or in the form of
small inclusions of another mineral within the
magnetite grain under the assumption that the
encapsulating mineral act as a barrier to Ar and K
exchange.
The possibility of applying the 40Ar/39Ar
method to dating magnetite has attracted very
little interest previously. This lack of interest has
been due to magnetites very low potassium con-
tent and the likelihood of excess argon contamina-
tion. These two factors can have a dramatic effect
on the precision and accuracy of the ages mea-
sured. Harrison and ~cDougal1 (1981) reported
an anomalously old single-fusion K-Ar age of
3653 + 40 Ma for magnetite from mafic rocks
from Broken Hill, Australia. This magnetite is
contaminated by excess argon and, as a result, its
K-Ar date is much older than 1660 Ma, the age of
high-grade metamo~~sm in the Broken Hill
block. Harrison and McDougall studied the equi-
librium concentration of excess Ar in magnetite in
order to estimate the ambient argon pressure dur-
ing this event.
Magnetite occurs as a low-temperature mineral
in chondritic meteorites and may have trapped
noble gases during its formation (Larimer and
Anders, 1967; Mazor et al., 1970). Several labora-
tory experiments have been carried out on mag-
netite grown in an Ar environment in an effort to
understand the environmental conditions in the
early solar system when the meteorites trapped
rare gases (Lancet and Anders, 1973; Honda et al.,
1979; Yang et al., 1982).
The present investigation has a different pur-
pose from those mentioned above. In our study, a
single gram of magnetite has been examined by
the OAr/Ar laser step-heating technique in an
effort to test the dateability of magnetite, which as
far as paleomagnetism and rock magnetism are
concerned is a uniquely important mineral.
The sample used in the present study was from
a metamorphic gneiss of the Red Cedar Lake
formation from 3 km south of the Grenville Front.
The Grenville Front is one of the major features
of the Canadian Precambrian Shield and forms
the boundary between the Grenville and Superior
Structural Provinces. Metamo~~c cooling ages.
in the range 90%1100 Ma, are typical of the
Grenville Province. Rocks near the Grenville Front
tend to give the older ages in this range (Harper,
1967; Anderson, 1988). Harper (1967) and Baer
(1976) interpreted this age gradient to be a result
of differential uplift away from the Front. How-
ever, it is also known that rocks near the Front are
particularly affected by excess argon (Wanless et
al., 1970).
Experimental procedure
The crushed and sieved gneiss sample was ul-
trasonically cleaned several times with distilled
water and methanol. Mineral separates of biotite
in the range 300-500 pm and magnetites in the
range 200-500 pm were hand picked under a
microscope. Composite grams, containing biotite
and quartz as well as magnetite, were removed,
leaving a 99.9% pure magnetite separate. Mag-
netite grains from this separate were used for the
Ar/39Ar, X-ray and SEM analyses. X-ray powder
pictures, using a Gandolfi camera with Cu-Ka:
radiation and a silicon standard, gave numerous
lines typical of magnetite. Best resolved were the
low-angle reflections (220), (311), (222), (400),
(422), (5ll), (440) and (533). The X-ray cell-edge
parameter was 8.39 + 0.01 A, in close a~eement
with the standard value of u = 8.396 A (ASTM
data file 19-629).
The &Ar/Ar analyses were made using a con-
tinuous laser fusion system at the University of
Toronto. The system consists of a continuous
argon-ion laser (Spectra-Physics 171-18, 18 W)
and a VG-1200 S mass spectrometer (Layer et al.,
1987). The single grains of magnetite and biotite
together with single grams of standard hornblende
Hb3gr within a high-purity aluminum sample
holder were irradiated at McMaster University to
transform a portion of the 39K atoms to 39Ar
through the interaction of fast neutrons. Follow-
ing the irradiation, indi~dual grams were heated
by the laser through a sapphire window for 30 s in
an ultra-high vacuum system evacuated to = lo-*
Torr. The beam size was larger than the grain in
order to obtain uniform heating. The single grains
of magnetite and biotite were heated in 14 and 17
4oAr/9Ar LASER DATING OF A SINGLE GRAIN OF MAGNETITE
23
steps and fused at 1600C and 1400C respec-
tively. After the extracted gas had been purified
by a getter and cold finger for 3 mm it was
introduced into the mass spectrometer. Five argon
isotopes (8 scans for biotite and 10 scans for
magnetite) were measured by peak-hopping. The
~imum detectable signal is about 2 X lo- cm3
STP. Typical background values for the extraction
line were 7 x lo-l4 cm STP for mass 36,1 X lo-l3
cm3 STP for mass 39, and 1.8 x lo-* cm3 STP for
mass 40. During the analysis the background was
monitored (about every third and fifth step for
magnetite and biotite respectively) and the back-
ground values were subtracted from the fractions
that followed. A Barnes RM-2A infrared micro-
scope was used to estimate the temperature during
each laser step-heating. The uncertainty in the
temperature estimate was + 5C. The e~ssi~ties
of the biotite and magnetite grams were measured
and found to be 70% and 78% respectively of the
black-body emissivity. The technical aspects of the
OAr/3gAr dating are described in detail elsewhere
(Layer et al., 1987).
The 40Ar/39Ar age spectrum of the single-grain
magnetite is shown in Fig. 1. The spectrum ex-
hibits a saddle-shape and yields an integrated age
of 1962 rf 39 Ma. This age is much older than the
age of Grenvillian metamo~~sm (e.g., Dallmeyer
and Rivers, 1983) and must reflect the presence of
an excess argon component. The high low-temper-
ature ages decrease to a minimum and then the
TABLE 1
Argon data for magnetite
Temperature
(0
Vol. Ar
(X*O-1z~m3 STP)
Atmospheric
contamination (W)
Age (Ma)
*la
Hb3gr b, J =2.313 x 1O-2 rf: 0.009 x 1O-2
360
400
500
550
600
700
750
800
900
1000
1050
1150
1400
1600
I ntegrated results
0.0145 64.63 0.670 94.70 2093 + 824
0.0200 59.13 0.111 60.63 1581-f 630
0.0699 39.38 0.848 54.49 1472+ 264
0.0142 76.85 2.175 33.87 1044 f 1911
0.0341 56.97 0.651 39.97 1181 f 659
0.1703 52.59 1.4436 44.79 1283 rt 134
0.1933 52.90 1.0479 38.29 1144f 107
0.1249 35.53 0.1379 38.98 1159* 142
0.1776 12.73 0.4129 48.81 1363 + 117
0.3247 5.82 0.5709 60.27 1575 f 54
0.2285 1.06 0.2304 63.78 1635 ?z 85
0.0448 (32.63) 10.5621 89.52 2024 f 334
0.0134 48.27 2.9339 58.51 1544 f 1358
0.4014 0.181 0.2807 199.27 3111 f 28
37Ar/39Ar = 0.8335 f 0.0377
.^
Total atmospheric ?Ar vol. = 3.2121 X lo-cm3 STP
Total 39Ark vol. = 1.8318 X lo-l2 cm3 STP
mAr*/39Ar,c = 85.02 k 2.17
Age==l%2&39MaC
a Ages were cafcufated using the decay constants of Steiger and figer (1977).
b Hb3gr is a standard hornblende with an age of 1071 Ma (Turner et al., 1971; Roddick, 1983). J =(eA* - l),/(40Ar*/s9Ar),; where s
refers to the standard.
The K concentration of the single gram magnetite was determined from
3gAr, and age using the relation t = (l/h)ln[l +
(X/&)(taAr*/40K)J where h = 5.543 X lo- yr-, h, = 0.581 X 10-r yr-, t = 1.9616 X lo9 yr, oAr* = 0.695 X lo-l4 mol and
*K = 3.371 X lo-l4 mol. The potassium content was 0.0018% or 18 ppm.
24
i i . 6ZDEMI R AND D. YORK
Mognetfte
16
3000
-$ 2500
z
& 2000
P
1500
Fmtion of Oar rehosed
Fig. 1. Age spectrum and Ca/K and Cl/K ratio for the single-grain magnetite from a gneiss sampled 3 km south of the Grenville
Front (Ontario, Canada). Shaded areas indicate the + lo errors.
ages rise to a maximum of 3111 + 28 Ma in the argon (Lanphere and Dalrymple, 1976). The
final fraction released. This shape of age spectrum minimum of the saddle (usually considered to give
has been observed previously in other mineral a maximum estimate for the true age) gives an age
types and attributed to the presence of excess of 1144 f 107 Ma (Table 1 ). This is in reasonable
4VAr,yAr LASER DATING OF A SI NGLE GRAI N OF MAGNETI TE
agreement with typical Grenvillian cooling ages of
1100 Ma near the Grenville Front.
Figure 1 also shows a plot of the variation in
the Ca/K and Cl/K ratios calculated from
3Ar/3Ar and 38Ar/3pAr ratios of the magnetite
grain during gas release. Ca/K values decrease
after about 30% of gas release, then remain rela-
tively constant in the 30-75s release range. How-
ever, the Ca/K ratio increases dramatically at
about 75% of 39Ar release (in the 115OC heating
step), then decreases to its original level. This
effect may be due to some impurity and is associ-
ated with an age of 2024 + 334 Ma in the age
spectrum.
Figure 2 shows the OAr/39Ar age spectrum of
the single grain of biotite. The grain was extracted
from the same hand sample as the magnetite. The
release spectrum exhibits a stepwise age increase
over the first 20% of gas release, presumably indi-
cating a partial loss of argon at some time during
the samples history. The age spectrum reaches a
well defined plateau of age 1260 Ma (Table 2).
The spectrum yields an integrated age of 1261 & 4
Ma. These ages are somewhat in excess of ex-
pected Grenvillian ages. However, biotites located
25
just south of the Grenville Front have been found
to have accumulated excess quantities of radio-
genie argon (Wanless et al., 1970; Dallmeyer and
Rivers, 1983; Anderson, 1988), so although the
spectrum yields an apparently well-defined
plateau, it is most probably a false plateau (Hy-
odo, 1989), because of the excess argon compo-
nent. Figure 2 also shows the plot of Ca/K ratios
of the same biotite. The Ca/K values are almost
constant up to 70% of the gas release, whereupon
an increase in the Ca/K ratio begins at the 900C
heating step, possibly because of argon release
from new sites in the biotite.
Discussion
Thermal release patterns
The various argon isotopes 36Ar, 37Ar, *Ar and
Ar together with radiogenic ?Ar* degassed at
each temperature step from the single grain of
magnetite are shown in Fig. 3. The release pat-
terns of 36Ar, 37Ar, 38Ar, Ar and 40Ar* are very
similar between 400C and 1150C and indicate
that the isotopes are released in three distinct
phases with release peaks at approximately
I I I I I I , I ,
1400 - Age =I 261 f3.6Aia
I , I
0 0.1 0.2 0.3 0.4
0.5 0.6 0.7 0.0 0.9 1.0
Fmfim OF 3s& retawe@
Fig. 2. Age spectrum and G/K ratio for the single-grain biotite from the same hand sample as the magnetite. Shaded areas indicate
f 113 errors.
26
0. OZDEMIR ANI) D. YORK
TABLE 2
Argon data for biotite
Temperature Vol. 39Ar,
(C)
(X lo- cm3 STP)
Hb3gr b, J= 2.313 x lo-* & 0.009 x 1O-2
Atmospheric
contamination (R;)
Ar/Ar *OAr*/9Ar, Age (Ma)
flu
450 2.503 15.31 ( - 0.0031) 34.61 1061+ 8
500 1.105 11.86 0.0279 31.32 983 + 21
550 2.638 5.43 0.0034 39.47 1170 f 10
600 5.761 1.31 0.0056 42.81 1242 + 5
650 10.189 0.69 0.0046 43.38 1254rfr 4
700 17.464 0.49 0.0027 43.66 1259 + 3
750 22.839 0.35 0.0013 43.63 1259 + 2
800 22.142 0.18 0.0029 43.83 1263 f 3
850 13.948 0.51 0.0028 43.89 12645 4
900 5.748 0.55 0.006 44.44 1276 f 4
950 4.091 ( - 0.54) 0.0094 45.87 1305+ 7
1000 3.783 0.041 0.0115 46.34 1314+ 8
1050 3.643 0.055 0.0119 46.36 1315* 6
1100 3.587 0.81 0.0189 46.17 1311 f 9
1150 2.934 ( - 0.96) 0.0484 46.35 1315 + 10
1250 3.155 1.31 0.0960 45.01 1287f 8
1400 2.705 0.19 0.0938 45.76 1303+ 6
Integrated results
3Ar/39Ar, = 0.0095 f 0.0007
Total atmospheric 40Ar = 4.7615 X 10-l cm3 STP
Total 39Ar, = 1.2823 X lo- cm3 STP
40Ar*/9Ar, = 43.15 * 0.06
Age = 1261 + 4 Ma
a Ages were calculated using the decay constants of Steiger and J&ger (1977).
h Hb3gr is a standard hornblende with an age of 1071 Ma (Turner et al., 1971; Roddick, 1983).
5Op, 700 and 1000C. The three pulses may also
reflect varying radii of diffusion or mechanisms
for Ar release. These three phases have three dis-
tinct corresponding linear segments in the
Arrhenius plot (Fig. 5).
A fourth large phase of 38Ar, 39Ar and 40Ar* is
released in the final step at about 1600C, whereas
virtually no 36Ar is seen here.
The fractions of 38Ar, 39Ar and ?Ar* released at
each temperature step for the single-grain biotite
are plotted against temperature in Fig. 4. The
release pattern of biotite shows only one peak,
located at about 75OC. The release patterns for
@Ar*, 39Ar and 38Ar are almost identical and indi-
cate that they are released from similar trapping
sites.
The second maximum in the magnetite release
pattern occurred at 7OOC, not far from that of
biotite.
Arrhenius diagram
The diffusion parameters E and Do/a2 in the
expression:
D Do - E/ k7
- _=- - - _e
a2 a*
were calculated from least-squares fitting of mea-
sured diffusion coefficients D/a* to a straight
line in an Arrhenius diagram (Fig. 5). In the
equation, Do is the frequency factor, a is the
diffusion dimension, k is Boltzmanns constant
and E is the activation energy required to transfer
ulAr,yAr LASER DATING OF A SINGLE GRAIN OF MAGNETITE
27
%*
I jgar
10000 - -200
e 7500-150-
2
2
u 5000-loo-
2500- 50-
..+.. 3?Af
..q.....
fiir
___o___ ?4,
-._.&_ _ %Ar
OL OL
Temperature PC1
Fig. 3. Thermal release patterns of the various argon isotopes 36Ar,
Ar, 38Ar and 39Ar, together with %r*, for the single-grain
magnetite. %r* was obtained from the equation WAr* = (40Ar)r - 295.5 X ( 36Ar)A,
where (%r)r and (36Ar)A are total and
atmospheric argon concentrations respectively. The number of counts for *Ar*, 39Ar, *AI, Ar and 36Ar after fusion at 1600C were
S1290,243,110,16 and - 9 respectively. 1 count = 2 X IO-t5 cm3 STP.
an Ar atom from one site to another. The slope of frequency factor Q/a*. Errors shown in the data
the best fitting line yields an experimental activa- points are f la. If Ar diffuses by a single mecha-
tion energy E and the Y-intercept gives the nism and all sites are identical, diffusion can be
600 -120-
500-IOO-
C
200-40-
100-20-
?T9mpem#un9 fcl
Fig. 4. Thermal release patterns of %r*, 39Ar and %r for the single-grain biotite. %r* was obtained from the equation
OAr = (%r)r - 295.5 x (36Ar),. The rekase patterns for %r*. 39Ar and %r are almost identical, but are quite different from the
release patterns for &&-grain magnetite (Fig. 3). 1 count = 2 X lo- cm3 STP.
28
0.6 0.6 I .o I .2 1.4 I .6 I.6
1ooO/ TPK.l
Fig. 5. Arrhenius diagram for the single-grain magnetite. Treat-
ing each linear segment as a distinct argon phase. activation
energies of 34 It 6, 66 f 8 and 68 + 5 kcal/mol were found for
?Ar reteased in the temperature ranges 360-500. 550-750
and 800-1050C respectively. The numbers denote the release
temperatures (Ct. The slope of each best-fit line defines an
activation energy E and the Y-intercept yields a frequency
factor Do/ a2. Errors in the data points are + lo.
modelled with a single E (Dalrymple and
Lanphere, 1969). However, this is not the case for
the present magnetite. Ar diffusion is a function
of several different activation energies and these
energies apply to different temperature ranges.
The graph of log(D/a) versus l/T for the single
grain of magnetite defines three straight lines (Fig.
5). The three lines are interpreted to represent
three distinct phases within the magnetite and are
therefore treated as three independent reservoirs.
The first three points, in the range 360-550C
0. OZDEMIR ANT) D. YORK
yield an activation energy of 34 + 6 kcal/mol
(Table 3). The second line, in the range 550-800C.
gives E = 66 t- 8 kcal/mol. These data points cor-
respond to the plateau in the age spectrum shown
in Fig. I. The ~~-temperature line segment is
approximately parallel to the second line and
yields an activation energy of 68 + 5 kcal/mol. As
noted above, the observed line segments in the
Arrhenius diagram of the single grain of magnetite
are associated with the three peaks in the thermal
release patterns and also correspond to three seg-
ments of the age spectrum (Fig. 1): the decreasing-
age low-temperature portion, the saddle minimum
and the mid high-temperature rising-age section,
respectively.
The data points for the biotite grain in the
temperature range from 500 to 800C lie on a
line in an Arrhenius diagram and give an activa-
tion energy of 42 f 2 kcal/mol (Fig. 6). This value
is close to the hydrothermal value for E of 47 -+_ 2
kcal/mol for biotite (Harrison et al., 1985). A
transition occurs in the range 800-1000C where
log(D/aZ) decreases with increasing temperature.
This peculiar behaviour has been observed by
many workers and has been attributed to the
breakdown of biotites when heated in vacuum
(Berger and York, 1981) or to the two-phase na-
ture of biotite (York and Lopez-Martinez, 1986).
The data follow a straight line for the gas fractions
released between 950 and 1250C and yield an
activation energy of 34 I~I 3 kcal/mol. The release
TABLE 3
Activation energies and diffusion coefficients for 39Ar, from magnetite and biotite
Sample Step a Eb D, , / at c
TB
d
n/SUMS
(C)
(kcal/mol) (SK)
(C)
Magnetite 360- 500 33.9 i 6 (2.9;&) x 10 53 f 34 3/0.004
550- 750 65.7 + 8 (4.61;3,,s) x IO 256 i 30 4/0.55
800-1050 68.2 + 5 (1.3+&J x 109 330 f 23 4/0.89
Biotite 500- 800 41.9 + 2 (2.6;:;) x IO6 151 i 11 X/1.9
950-1250 33.7 * 3 (5.9::) x 102 137 + 23 5/0.39
This column gives the temperature (C) of the first and Iast steps of the range of those fractions fitted to a straight line.
b E is a experimental activation energy. Errors in this table are lo.
This is the pre-exponential frequency factor derived from an Arrhenius plot.
d Ta is the isotopic btocking temperature calculated with Dodaons (1973) formula. The blocking temperatures for the magnetite and
biotite were calculated with a cooling rate of SW/Ma.
SUMS is a statistical parameter (York, 1969); n is the number of points fitted to a straight line.
Ar/39Ar LASER DATING OF A SINGLE GRAlN OF MAGNETITE
of argon in this higher-temperature range may be
due to the decomposition or phase change of
biotite or to a second diffusion process. This sec-
ond segment in the Arrhenius plot corresponds to
the high Ca/K ratios and high ages in the age
spectrum (Fig. 2).
The activation energy of the low-temperature
segment of magnetite is probably lower (E = 34 +
6 kcal/mol) than that of biotite (E =42 + 2
kcal/mol). It should also be pointed out that the
second linear segment in the Arrhenius plot of
magnetite gave an activation energy of 66 & 8
kcal/mol, which is much higher than that of bio-
tite apparently. Argon diffuses with different
activation energies in biotite and magnetite.
This suggests that the saddle region of the
magnetite age spectrum (Fig. 1) is not due to
argon released from a biotite inclusion. It does not
prove this, however, because presumably argon
released from such an inclusion still has to diffuse
through the imprisoning magnetite lattice before
finally escaping.
A single grain of magnetite 150 pm in size was
prepared for microstructural examination. The
grain was mounted in transparent epoxy on a
glass slide. The epoxy and embedded magnetite
were mechanically polished to a thickness of - 80
pm for scanning electron microscope (SEM,
Hitachi S-570) and X-ray energy dispersive analy-
sis. Figure 7 a shows the scanning electron micro-
graph of the single magnetite grain. An X-ray
microanalyser (LINK AN-1~~ was used to ex-
amine the grain in the SEM and then perform
rapid analysis of selected features within the
imaged area. The unique position beam mode
conveniently combines the electron image with
spectral data on the single-system display. The
beam current was 100 pA at 20kV. The beam
diameter could be adjusted as small as 35-40 A.
Figure 7b shows the results of the X-ray energy
dispersive analysis of the examined areas on the
magnetite grain. Two inclusions, about 7 x 25 pm
and 5 X 40 pm, can be seen in the electron micro-
graph. X-ray microanalysis indicates that the in-
clusion labelled B contains minor amounts of Mg,
29
Si and Al and inclusion C is probably ilmenite
with Mn impurity. Neither of the inclusions con-
tains significant quantities of potassium as an
impurity. However, this observation should not be
generalized to the single magnetite grain which we
dated by 40Ar/39Ar.
Locations for argon
We can speculate as to the trapping sites in
magnetite. Imperfections such as crystallographic
point defects and dislocations could act as traps
for argon in the magnetite crystal. Crystallo-
graphic point defects are lattice errors at isolated
points in the crystal. They can be vacancies where
atoms are missing or impurity atoms occupying a
lattice site (Wert and Thompson, 1970). Vacancies
are generally present in magnetite crystals. The
cation vacancies are mainly located in octahedral
sites @Donovan and OReilly, 1978) and are not
large enough to contain either a K or an Ar atom
(Fig. 8). In contrast, anion vacancies in magnetite
seem more likely to hold a potassium or an argon
atom (DuFresne and Anders, 1962). Castle and
Surman (1967, 1969) have studied the self-diffu-
sion of oxygen in magnetite and the effect of
anion vacancies. They have determined that the
activation energy for creating a vacancy by oxygen
Fig. 6. Arrhenius diagram for the single-grain biotite. Treating
each linear segment as a distinct argon phase, activation en-
ergies of 42% 2 and 34& 3 kcal/mol were found for Ar
released in the temperature ranges 500-800 and 950-1250C
respectively. The error bars are flu. Note the different pat-
terns and activation energies compared to magnetite (Fig. 5).
30
diffusion is 7-8 kcal/mol, which leads to an equi-
librium concentration of 4 x 10 vacancies/g.
Crystallographic point defects can also be
caused by bombardment by fast neutrons in the
nuclear reactor. The number of point defects pro-
duced in this way is dependent on the nature of
the magnetite crystal. A significant concentration
of displaced atoms can be created by this
bombardment and it is possible that significant
changes in the properties of magnetite can be
produced (Hutch&on and Baird, 1967; McDougall
and Harrison, 1988).
Naturally occurring magnetite also contains
dislocations. Heider et al. (1987) studied a natural
2
4 4000-
3
2000-
8000
Si
8000
6000
Fig. 7. (a) Scanning eiectron micrograph of a single magnetite grain from the same hand sample as the single grains of magnetite and
biotite on which 40Ar/39Ar analysis was carried out. Light areas (A) are magnetite, grey areas in the right corner of the grain (3 and
C) are inclusions. (b) X-ray energy dispersive analysis of areas A,
B and C shown in (a). The analysis was carried out with an
AN-10000 X-ray microanalyser at the University of Toronto.
i l Ar ,39Ar LASER DATING OF A SINGLE GRAIN OF MAGNETITE
31
Fig. 8. Crystal structure of magnetite, after Morrish (1965).
Magnetite has a spine1 crystal lattice. The large oxygen anions
form a close-packed face-centred cubic lattice. The ionic radius
of the oxygen anions is about 1.32 A which is much larger than
that of metal cations (Fe+ and Fe3+, 0.83 and 0.67 A
respectively). In this oxygen lattice, two kinds of interstitial
sites occur, the tetrahedral (A) and the octahedral (B) sites
which are surrounded by 4 and 6 oxygen ions respectively. In
this cubic unit cell, 64 tetrahedral and 32 octahedral sites are
present, of which only 8 and 16 respectively are occupied by
Fe*+ and Fe3+ cations. The cation distribution of magnetite
can be written Fe3+[Fe3* Fe 2+ IO,, where cations outside the
bracket are in the tetrahedral sites and those inside the bracket
are in octahedral sites. In addition to the octahedral and
tetrahedral sites, vacant lattice sites can also occur owing to
missing oxygen ions in this cubic close-packed structure. The
unoccupied octahedral and tetrahedral sites are not large
enough to contain an Ar atom (1.54 A).
single crystal of magnetite whose dislocation den-
sity was (1.0 f 0.8) X 10 m-. The dislocation
density, which is the number of dislocation lines
that intersect a unit area in the crystal, was de-
termined by counting etch pits. Stacking faults,
associated with partial dislocations have also been
reported in magnetite (Jakubovics et al., 1978).
Figures 8 and 9 of their study show a high density
of stacking faults lying on (110) planes of mag-
netite crystals, with fault vectors of l/4 (110).
It seems reasonable to suppose that the prin-
cipal trapping sites for argon in magnetite are
anion vacancies and dislocations. Oxygen diffu-
sion in water vapour seems likely to occur along
paths such as grain boundaries, dislocations or
micropores (Castle and Surman, 1969).
Summary and future study
In the single magnetite grain analysed, ages in
the low- and high-temperature portions of the gas
release exceed typical Grenvillian cooling ages.
However, the central portion of the age spectrum
reveals a geologically not unreasonable age. Before
making a statement about whether or not mag-
netite is suitable for OAr/39Ar dating, there are
two questions to be answered. First, is the plateau
age of Fig. 1 due to the magnetite itself? In other
words, is the associated potassium a cation impur-
ity in the magnetite lattice? Interestingly enough, a
potassium ferrite of composition KFe,,O,, has
been reported (Gorter, 1954), showing that potas-
sium can be incorporated in a hexagonal ferrite
lattice at least. Secondly, is the potassium associ-
ated with inclusions in the magnetite grain? At
present, both questions are difficult to answer.
Ideally, one would like to carry out microstruc-
tural studies before OAr/39Ar step-heating experi-
ments. We have already analysed one single grain
of magnetite and did not discover any biotite
inclusions (Fig. 7). However, we were not able to
do a similar SEM study on the single magnetite
grain on which the Ar/Ar experiment was car-
ried out. In the future, we will repeat our experi-
ments using larger single crystals of magnetite.
This will allow us to carry out *Ar/39Ar and
SEM/X-ray energy dispersive analyses on the
same grain.
Conclusions
We draw the following conclusions:
(1) @Ar* was trapped in measurable quantities
in a 300 pm magnetite grain.
(2) The central portion of the age spectrum
gave an age of 1144 f 107 Ma which is consistent
with typical Grenvillian cooling ages of 1100-900
Ma.
(3) Our results are preliminary but they are a
first step toward the direct dating of magnetite
and of its NRM.
Acknowlqfgements
We would like to thank Drs. Paul Layer and
Chris Hall for their experimental assistance and
32
Dr. Mike Easton of the Ontario Geological Survey
for supplying the gneiss sample. Malcolm Back of
the Royal Ontario Museum and Fred Neub of the
MetaBurgy and Materiat Science Department
kindly carried out X-ray and SEM analyses. We
are grateful to Drs. David Dunlop and Minor-u
Ozima for their inspiration and valuable discus-
sions and to Dr. Tulhs Onstott for reviewing and
co~ent~g on the manuscript. We also thank
Carolyn Moon for typing the manuscript. The
project was supported by grants to D.Y. from the
Ontario Geological Survey and Natural Sciences
and Engineering Research Council of Canada.
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