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Use and limitations of second-derivative diffuse reflectance

spectroscopy in the visible to near-infrared range to identify and
quantify Fe oxides in soils

Article in Clays and Clay Minerals · October 1998

DOI: 10.1346/CCMN.1998.0460506

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Clays and Clay Minerals, Vol.46. No. 5. 528-536, 1998.

U S E A N D LIMITATIONS OF S E C O N D - D E R I V A T I V E D I F F U S E
R E F L E C T A N C E S P E C T R O S C O P Y IN T H E V I S I B L E TO
N E A R - I N F R A R E D R A N G E TO I D E N T I F Y A N D
Q U A N T I F Y Fe O X I D E M I N E R A L S IN SOILS

A . C. SCHEINOST,]~ " A. CHAVERNAS, 2 V. BARRON 2 AND J. TORRENT 2

~Agronomy Department, Purdue University, West Lafayette, Indiana 47907, USA
2Departamento de Ciencias y Recursos Agrfcolas y Forestales, Universidad de C6rdoba,
Apdo. 3048, 14080 C6rdoba, Spain

Abstract--We measured the visible to near-infrared (IR) spectra of 176 synthetic and natural samples of
Fe oxides, oxyhydroxides and an oxyhydroxysulfate (here collectively called "Fe oxides"), and of 56
soil samples ranging widely in goethite/hematite and goethite/lepidocrocite ratios. The positions of the
second-derivative minima, corresponding to crystal-field bands, varied substantially within each group of
the Fe oxide minerals. Because of overlapping band positions, goethite, maghemite and schwertmannite
could not be discriminated. Using the positions of the 4Tl<----6AI, 4T2<----6AI, (4E;4AI)4---6AI and the electron
pair transition (4T~h-4Ti)<----(6Ai q-6ml), at least 80% of the pure akaganeite, feroxyhite, ferrihydrite, hematite
and lepidocrocite samples could be correctly classified by discriminant functions. In soils containing
mixtures of Fe oxides, however, only hematite and magnetite could be unequivocally discriminated from
other Fe oxides. The characteristic features of hematite are the lower wavelengths of the 4"171transition
(848-906 nm) and the higher wavelengths of the electron pair transition (521-565 nm) as compared to
the other Fe oxides (909-1022 nm and 479-499 nm, resp.). Magnetite could be identified by a unique
band at 1500 nm due to Fe(II) to Fe(III) intervalence charge transfer. As the bands of goethite and hematite
are well separated, the goethite/hematite ratio of soils not containing other Fe oxides could be reasonably
predicted from the amplitude of the second-derivative bands. The detection limit of these 2 minerals in
soils was below 5 g kg t, which is about 1 order of magnitude lower than the detection limit for routine
X-ray diffraction (XRD) analysis. This low detection limit, and the little time and effort involved in the
measurements, make second-derivative diffuse reflectance spectroscopy a practical means of routinely
determining goethite and hematite contents in soils. The identification of other accessory Fe oxide min-
erals in soils is, however, very restricted.
Key Words---Crystal Field Bands, Diffuse Reflectance Spectroscopy, Goethite, Hematite, Intervalence
Charge Transfer, Iron Oxides, Magnetite.

INTRODUCTION as M u n s e l l or L * a * b * ( W y s z e c k i a n d Stiles 1982).

D i f f u s e r e f l e c t a n c e s p e c t r o s c o p y in t h e v i s i b l e
( 4 0 0 - 7 0 0 n m ) a n d e x t e n d e d visible r a n g e ( 4 0 0 - 1 2 0 0
n m ) h a s b e e n used as a n a n c i l l a r y m e t h o d to identify
a n d s e m i q u a n t i t a t i v e l y e s t i m a t e F e oxides in clays,
soils a n d s e d i m e n t s ( C o r n e l l a n d S c h w e r t m a n n 1996,
a n d r e f e r e n c e s therein). A l t h o u g h spectra o f s a m p l e s
with unknown mineralogy may simply be compared
w i t h spectra o f r e f e r e n c e m i n e r a l s ( S i n g e r 1982; Mor-
ris et al. 1989), the p a r a m e t r i z a t i o n o f t h e s e spectra
a l l o w s for a q u a n t i t a t i v e a p p r o a c h (Torrent a n d B a r r 6 n
1993). T h e m o s t f r e q u e n t l y u s e d p r o c e d u r e s for the
p a r a m e t r i z a t i o n are:
1) C a l c u l a t i o n o f the tristimulus values (X, Y, Z) o f
the C I E c o l o r s y s t e m ( C I E 1978). T h e tristimulus val-
ues are c o m p u t e d f r o m the spectral reflectance a n d en-
ergy o f the light source for e a c h w a v e l e n g t h , a n d c a n
b e c o n v e r t e d , b y m e a n s o f a p p r o p r i a t e f o r m u l a s or
graphs, to the p a r a m e t e r s o f o t h e r color systems, such
I Present address: Department of Plant and Soil Science,
University of Delaware, Newark, Delaware 19717-1303
USA.
Several indices b a s e d o n s u c h p a r a m e t e r s h a v e b e e n
correlated, for instance, with the h e m a t i t e content, pro-
v i d i n g a s e m i q u a n t i t a t i v e e s t i m a t i o n o f this m i n e r a l in
soils (Torrent et al. 1980; B a r r 6 n a n d Torrent 1986;
N a g a n o et al. 1992, 1994).
2) A p p l i c a t i o n o f the K u b e l k a - M u n k theory. W i t h
this m e t h o d , the reflectance values, R, are u s e d to ob-
tain the r e m i s s i o n f u n c t i o n F ( R ) = (1 - R ) V ( 2 R ) ,
w h i c h allows, in turn, c a l c u l a t i o n o f the coefficients
o f a b s o r p t i o n (K) a n d scattering (S) c o r r e s p o n d i n g to
the 2 p h e n o m e n a i n v o l v e d in the s a m p l e - l i g h t inter-
action process. It h a s b e e n s h o w n that K a n d S are
additive in a m i x t u r e o f p i g m e n t s . Therefore, o n e c a n
e s t i m a t e the c o n c e n t r a t i o n o f an F e o x i d e in the m i x -
ture b y k n o w i n g the color characteristics o f e a c h o f
the c o m p o n e n t s o f the mixture, a n d a s s u m i n g a stan-
d a r ar color for the Fe oxides i n v e s t i g a t e d ( B a r r 6 n a n d
Torrent 1986; Fernfmdez a n d S c h u l z e 1992).
3) C a l c u l a t i o n o f d e r i v a t i v e s o f the reflectance or
the r e m i s s i o n f u n c t i o n to derive the p o s i t i o n a n d in-
tensity o f the a b s o r p t i o n b a n d s . T h e s e b a n d s are pro-
d u c e d b y crystal-field transitions o f Fe(III) in an oc-

Copyright 9 1998, The Clay Minerals Society 528

Vol. 46, No. 5, 1998 Use and limitations of 2nd-derivative diffuse reflectance spectroscopy 529

Table 1. References, origin (syn = synthetic, nat = natural), number (N) and A1 substitution (Ai-subst.) of the Fe oxide
samples.
A|-subst.
Fe oxide (abbreviation) Origin (N) (mole-fraction) References

Akaganeite (Akag) syn (7) 0 Bigham et al. (1990, 1996); Schwertmann et al. (1995)
Feroxyhyte (Feroxy) syn (5) 0 Carlson and Schwertmann (1980)
Ferrihydrite syn (11) 0 Schwertmann and Fischer (1973); Schwertmann et al. (1982);
(Ferrih) nat (11) Schwertmann and Kiimpf (1983); Carlson and Schwert-
mann (1981, 1987)
Goethite (Goeth) syn (25) 0-0.32 Schulze and Schwertmann (1984); Schwertmann et al.
nat (36) (1985)
Hematite (Hem) syn (26) 0-0.16 Stanjek (1991); Stanjek and Schwertmann (1992); Murad
nat (20) and Schwertmann (1986); Torrent and Schwertmann
(1987)
Lepidocrocite (Lepido) syn (14) 0-0.14 Schwertmann and Fitzpatrick (1977); Carlson and Schwert-
nat (3) mann (1990); Scbwertmann and Wolska (1990); Murad
and Schwertmann (1984)
Maghemite (Magh) nat (3) 0-0.7 Taylor and Schwertmann (1974)
Magnetite (Magn) syn (5) 0-0.17 Schwertmann and Murad (1990)
Schwertmannite (Schwt) syn (4) 0 Bigham et al. (1990, 1996); Schwertmann et al. (1995)
nat (6)

tahedral ligand field (Sherman and Waite 1985). Due MATERIALS A N D M E T H O D S

to the combination of several polarization planes and
particle-dependent scattering, the diffuse reflectance
spectra of powders show broad, strongly overlapping
bands (Kortiim 1969; Morris et al. 1982). To deter-
mine the positions of these bands, the resolution may
be mathematically enhanced by calculating the deriv-
atives of the measured spectra (Huguenin and Jones
1986). Deaton and Balsan (1991) used the first deriv-
ative, and Kosmas et al. (1984, 1986) and Malengreau
et al. (1994, 1996) used the second derivative to detect
and quantify different Fe oxides in soils or mineral
mixtures. In a similar approach, Coyne et al. (1990)
found that second-derivative spectra were superior to
first derivative or untransformed spectra in predicting
the amount of structural or interlayer Fe(HI) in mont-
morillonite.
Recent studies have suggested very low detection
limits for Fe oxides and the possibility of unequivo-
cally differentiating between the various Fe oxides
based on crystal field band positions (Malengreau et
al. 1994, 1996). Since these studies were carried out
for relatively simple mineral mixtures and with a lim-
ited number of Fe oxide samples, a closer examination
of the potential of second-derivative reflectance spec-
troscopy seemed necessary. Thus, the objective of this
work was to examine the ability of the second-deriv-
ative spectra to: 1) discriminate among different Fe
oxides, and 2) help semiquantitatively estimate Fe ox-
ide contents in soils, using a substantially larger col-
lection of samples than those used in previous studies.
We restricted this study to the evaluation of crystal
field bands. The OH and H20 vibrational bands in the
IR constitute, however, another possibility for char-
acterizing Fe oxides (Bishop et al. 1995; Bishop and
Murad 1996).
Synthetic and Natural Fe Oxides, and Soils
The origins of the Fe oxide samples are given in
Table 1. The samples from natural environments in-
clude precipitates in spring waters, lake ores, concre-
tions, NaOH-enriched soil fractions and whole soils.
Forty soil samples with variable hematite-to-goethite
ratios come from A or B horizons of soils from several
countries of the European Union and Brazil, including
Vertisols, Luvisols, Nitosols, Acrisols and Ferralsols.
Determination of citrate/bicarbonate/dithionite-extract-
able iron (Fed) (Mehra and Jackson 1960), and acid
oxalate-extractable iron (Feo) (Schwertmann 1964) and
differential X RD (Schulze 1981) were carried out to
estimate their hematite and goethite contents, which
ranged between 0 and 150 g kg -~. Sixteen samples
with different lepidocrocite-to-goethite ratios are from
crusts, pipestems and other Fe-oxide-enriched soil ma-
trices from South Africa (Schwertmann and Fitzpat-
rick 1977).
Spectral Measurements
Diffuse reflectance spectra were obtained from dry
and ground powders. For the hematitic soils, spectra
were taken from 380 to 750 nm at 1-nm increments,
using a Perkin-Elmer Lambda 3 spectrophotometer fit-
ted with a reflectance attachment (Perkin Elmer, Nor-
walk, Connecticut, USA). BaSO4 was used as a white
standard. All other samples were measured between
200 and 2500 nm at 1-nm increments with a 20-cm
integrating sphere (Labsphere, Inc., USA) attached to
a Perkin-Elmer Lambda 19 (f3berlingen, Germany). A
Spectralon standard (Labsphere, Inc., USA) was used
as reflectance reference. The wavelength-dependent
reflectance functions were transformed into remission
530 Scheinost, Chavernas, Barr6n and Torrent Clays and Clay Minerals

Wavelength / nrn Electronic Transition

1100

1000 . . . . .

900 . . . . . . . 9 . . . . . . . 9 . . . . . . . .i . . . . . . . . i . . _ i . . J . . . . . . . ,a . . . . . . . .i . . . . . . . .

800
i

700 . . . . . . . , . . = . . ~ . . , ~ . . , ....... , ..... ~. . . . . . . , . . .

= Z t :: = :: .[ ..... I
i i ,

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 . . . . . . . - . . . . . . . . !. . . . . . . .
600

500 "------,------,--.--,--, . . . . . . . . . . . . . -~zi"":" "",~,'" ".""",~.""" EPT

4-". 4 A 6A
400 _.,...i...=....,...I...:....z. ..... _z... ._.~... . . . ~
. . . . . q. . . . . . . q

300 I

"0

9 E s 9 m
~, t-
o = E
O
w.-
~
o E 9
-- f-

~o

Figure 1. Median and range of the crystal field band positions determined by second-derivative minima.

functions. The first and the second derivatives were the 3 single-electron transitions 4Tle---6AI, 4T2e--6A I and
calculated using a cubic spline fitting procedure (Press (4E;aA1)e'6A l, and the e l e c t r o n pair transition
et al. 1992). Briefly, a cubic spline consists of a num- (41", +4T~)e--(6A~ +6A~), in the following abbreviated by
ber o f cubic polynomial segments j o i n e d end to end " E P T " (Figure 1).
with continuity in first and second derivatives in the The EPT, as the most intense absorption band, de-
joints. A crucial input parameter in the program is the termines the position of the absorption edge which, in
n u m b e r of points taken for each segment, which de- turn, is closely related to the hue. The EPTs for the
termines the goodness of fitting (r 2) and the degree of hematites occur at 521 to 565 nm, clearly separated
smoothing of the curve. Several tests showed 15 to be from the EPTs of the other, m o r e yellowish Fe oxides
the o p t i m u m number of points to obtain smooth curves (479 to 499 nm) (Table 2). The difference in E P T and
with high r 2 values; therefore, this number was adopt- color between hematite and the other Fe oxides has
ed for the systematic calculation of the second-deriv- been explained by the presence o f face-sharing octa-
ative curves. The selected smoothing parameters are hedra in the hematite structure leading to an increase
not valid in general, but must be adjusted when the of the magnetic coupling between neighboring Fe(III)
spectra are taken with different scan parameters. centers (Sherman and Waite 1985). In contrast to the
results of Malengreau et al. (1994), however, the rang-
RESULTS AND DISCUSSION
es of the E P T of all other Fe oxides generally over-
Discrimination between Single-Phase Fe Oxides lapped, that is, the discrimination o f these Fe oxides
The second-derivative spectra revealed 4 bands in could not be performed with the E P T only.
the range from 350 to 1050 nm. These bands were A similar separation of hematite f r o m the other Fe
assigned, according to Sherman and Waite (1985), to oxides is given by the 4Tle-'-6A I transition (Figure 1).
Vol. 46, No. 5, 1998 Use and limitations of 2nd-derivative diffuse reflectance spectroscopy 531

Table 2. Median and range of crystal field band positions (nm).

4T l 4T2 EPT (4E; 4Al)

Akaganeite 946 659 492 410

(N = 7) 932-975 652-671 490-493 408-411
Feroxyhyte 933 707 493 417
(N = 5) 926-940 700-710 492-495 413-421
Ferrihydrite 972 7161" 492 410t
(N = 22) 947-990 698-734 484-499 386-410
Goethite 953 665 488 413
(N = 61) 929-1022 654-691 479-493 409-427
Hematite 877 682 531 423t
(N = 46) 848-906 664-695 521-565 416-442
Lepidocrocite 973 687 488 413
(N = 17) 943-997 673-692 485-490 408-418
Maghemite 948 675 489 418
(N = 3) 909-963 648-675 486-490 417-423
Schwertmannite 952 655 489 416~-
(N = 10) 942-962 648-688 488-491 410-416

t Band not always determinable (no minimum of the second-derivative spectrum).

T h e significantly l o w e r w a v e l e n g t h o f this transition To evaluate the d i s c r i m i n a t i v e p o w e r o f the posi-

for h e m a t i t e ( 8 4 8 - 9 0 6 n m ) is the result o f the l o w e r
crystal field splitting e n e r g y o f h e m a t i t e (14,000 c m t)
as c o m p a r e d to that o f g o e t h i t e (15,320 c m t), m a g h -
e m i t e (15,410 c m -1) and l e p i d o c r o c i t e (15,950 c m 1)
(Burns 1993). Again, strongly o v e r l a p p i n g b a n d po-
sitions p r e v e n t a p r o p e r d i s c r i m i n a t i o n o f the n o n - h e -
matite F e o x i d e s b y only this band.
With the 4T2~---6A1 transition at 698 to 734 nm, the
ferrihydrite and f e r o x y h i t e s a m p l e s are distinct f r o m
the o t h e r F e oxides, w h e r e this transition occurs at
l o w e r w a v e l e n g t h s (648 to 695 n m ) (Figure 1, Table
2). Sixteen out o f 22 ferrihydrite s a m p l e s did not
s h o w , however, a s e c o n d - d e r i v a t i v e m i n i m u m , so that
the b a n d position could not b e determined. The
(4E;4A1) <'--6A 1 transition o f all F e oxides ranged f r o m
386 to 442 nm. This b a n d was not visible in the de-
rivative spectra o f 25 hematites.
tions o f all 4 b a n d s c o m b i n e d , a s t e p w i s e d i s c r i m i n a n t
analysis was p e r f o r m e d (StatSoft Inc. 1996). T h e a
priori probabilities w e r e a s s u m e d to b e equal for all
F e o x i d e minerals, in o r d e r to avoid the p r e d o m i n a n t
classification o f minerals with the larger n u m b e r s o f
s a m p l e s which, in turn, w o u l d d e c r e a s e the sensitivity
o f classification for the small mineral groups. To allow
for the inclusion o f all samples, w e split the groups o f
b o t h ferrihydrite and h e m a t i t e into s u b g r o u p s contain-
ing all 4 bands, and into subgroups w h e r e 1 b a n d w a s
m i s s i n g and set to zero. Table 3 s h o w s that all ferox-
yhite, ferrihydrite and h e m a t i t e s a m p l e s w e r e correctly
classified b y using the 4 bands, and m o r e than 80% o f
the akaganeite and l e p i d o c r o c i t e s a m p l e s w e r e cor-
rectly discriminated. The b a n d positions o f goethite,
m a g h e m i t e and s c h w e r t m a n n i t e are, however, too s i m -
ilar to allow for a reliable d i s c r i m i n a t i o n (Table 3).

Table 3. Classification of Fe oxides by 4T~, 4T2, EPT and (4E; 4Al). Rows: observed classifications; columns: predicted
classifications.
Percent Ferrih Ferrih Hem Hem
correct Akag Feroxy - 4T2 + 4T2 Goeth + (E;A) - (E;A) Lepido Magh Schwt

Akaganeite 83 5 0 0 0 0 0 0 0 1 0
Feroxyhite 100 0 5 0 0 0 0 0 0 0 0
Ferrihdyrite -4T2-~ 100 0 0 16 0 0 0 0 0 0 0
Ferrihdyrite +4T2-~ 100 0 0 0 6 0 0 0 0 0 0
Goethite 23 8 0 0 0 14 0 0 3 13 22
Hematite +(4E;4A07 100 0 0 0 0 0 21 0 0 0 0
Hematite -(4E;aA~)t 100 0 0 0 0 0 0 22 0 0 0
Lepidocrocite 81 0 0 0 0 0 0 0 13 3 0
Maghemite 33 0 0 0 0 0 0 0 1 1 1
Schwertmannite 50 1 0 0 0 2 0 0 1 0 4
Total 66 14 5 16 6 16 21 22 18 18 27

t Ferrihydrite -4T2: ferrihydrite samples without the 4T2 band, Ferrihydrite +4T2: ferrihydrite samples with the 4T2 band.
Hematites resp. with and without the (4E;aA1) band.
532 Scheinost, Chavernas, Barr6n and Torrent Clays and Clay Minerals

Table 4. Coefficients of the classification function (see text).

Akag Feroxy Ferrih +4T2 Goeth Hem +(E;A) Lepid Magh Schwt

a~ 14.92 15.80 16.02 14.98 15.43 15.36 15.09 14.92

bx 26.21 26.43 26.53 26.09 27.61 26.24 26.09 26.16
c, 0.26 0.25 0.22 0.26 0.26 0.26 0.26 0.26
d~ 8.62 8.57 8.86 8.67 8.33 8.78 8.59 8.68
e, -15,504 -16,158 -16,640 -15,527 -16,295 -15,961 -15,529 -15,535

A set of classification functions to determine the Fe
oxide mineralogy of further samples is given by:
Sx = ax. 4T2 + b x . E P T + c . , . ( 4 E ; 4A1) + dx. aTl -b e~
[1]
with the scores for each group o f minerals, Sx, and the
coefficients for each group, ax, b~, cx, d~ and ex as
defined in Table 4. Within the limitations shown be-
fore, the highest number of Sx gives the Fe oxide min-
eral o f the e x a m i n e d sample. As second-derivative
spectra without a m i n i m u m in the 4T2<---6A 1 range un-
equivocally indicated ferribydrite, and those without a
m i n i m u m in the ( h E ; h A 1)<---6A 1 range unequivocally in-
dicated hematite, no classification functions are nec-
essary for these subgroups. As the band positions de-
rived from the second derivatives depend on the x and
y units of the spectra, and on the smoothing of the
spectra, it is indispensable to follow the procedure giv-
en under Materials and Methods before calculating the
scores.
Identification of Mixtures o f Fe Oxides
Because o f the well-separated EPTs of goethite and
hematite, both phases are clearly detectable from the
derivative spectra o f soils (Figure 2). The intensity of
the m i n i m a depends on the goethite-to-hematite ratio
(see below).
Although lepidocrocite and goethite could be dis-
criminated in pure phases (Table 2), the derivative
spectra of soils containing both Fe oxides did not re-
solve the slightly different band positions (Figure 3).
Using the classification functions given in Table 4,
soils with l e p i d o c r o c i t e / ( l e p i d o c r o c i t e + g o e t h i t e )
~ 0 . 3 7 were classified as lepidocrocites, while those
with a ratio -<0.37 were classified as goethite or mag-
hemite. In the same way, the derivative spectra of fer-
rihydrite/goethite and ferrihydrite/lepidocrocite
mixtures did not resolve the bands of both phases (data
not shown). That is, second-derivative spectroscopy is
not suited to detect small amounts o f ferrihydrite or
lepidocrocite in addition to a major goethite p h a s e - - a
situation which should frequently occur in soils due to
t h e r m o d y n a m i c inequilibria (Cornell and Schwert-
mann 1996). A l t h o u g h not tested experimentally, it
may be concluded that spectra o f other combinations
of Fe oxides with band positions in the same or strong-
ly overlapping regions w o u l d not allow the single con-
tributions to be resolved, either.
Besides the band wavelengths, absolute and relative
band intensities and bandwidths m a y be used to dis-

4e-6 2e-6

~ lepid/(lepid+goeth)
I.~ ~ 1.00
le-6 ll~ m- 0.72
UJ
--> 2e-6 / ~ hematite/(hematite+oo~
~ .~ A gt ~ --- 0.37
,~ -- 0.00

o"'
Y0,,j
~- o.1
-2e-6 0,0

goethite EPThematite
-4e-6 . . . . . . . . . . . . . . . . . -2e-6
450 500 550 600 400 500 600 700 800 900 I000

WAVELENGTH / nm WAVELENGTH [nm]

Figure 2. Second-derivative spectra of soils with various he- Figure 3. Second-derivative spectra of soils with various
matite/(hernatite + goethite) ratios. lepidocrocite/(lepidocrocite + goethite) ratios.
Vol. 46, No. 5, 1998 Use and limitations of 2nd-derivative diffuse reflectance spectroscopy 533

100

8oll w/o mtgnetlte 10

m-
80
ua 5
>
IJJ
O

Y
z 60
-->
tr 0
0 lit
UJ
CI
--J

u. 4o
w
I1: A
t r

20 -10
9 . , . . . . , . . . . , . . . . , . . .

400 500 600 700

WAVELENGTH (nm)
500 1000 1500 2000
Figure 6. Position and amplitude of the bands selected for
WAVELENGTH / nm the quantification of goethite (YI) and hematite (Y2) in soil
samples.
Figure 4. Reflectance spectra of pure magnetite, magnetite
+ maghemite and soils with various concentrations of mag-
netite.
criminate Fe oxides. Although such differences were
evident with synthetic, single-phase samples, for ex-
ample, sharper bands for goethite than for ferrihydrite,
these differences were generally less expressed for nat-
ural Fe oxides, and could not be used to differentiate

'l/,+~/ a
10 the origin of overlapping bands in mixtures and soils.
Band amplitudes of the second-derivative spectra were
higher for hematite, but no significant differences were
found between the amplitudes of the other Fe oxides.
The reflectance of the magnetite samples was very
low and, because of that, the spectra were too noisy
>o
to allow for the determination of their crystal field
bands. This low reflectivity is caused by a strong ab-

-10
40O 420
2:,2
44O
WAVELENGTH (rim)
460 480 5O0
sorption band which has its maximum in the near-IR
at about 1500 nm, but extends across the visible range
(Figure 4). It is caused by the presence of Fe(II) and
Fe(III) in neighboring octahedra in the magnetite
structure, leading to the delocalization of electrons due
to intervalence charge transfer (IVCT) (Sherman and
Waite 1985; Burns 1981). Strens and Wood (1979) de-
termined the position of the IVTC of magnetite from
~,, b
diffuse reflectance spectra at 1400 nm, and Sherman
5 I% (1987) derived an energy of 1475 nm from molecular
orbital calculations assuming equal sites for Fe(II) and
Fe(III) (q = 0). Both values correspond with ours, con-
z.o sidering the low precision with which the position of
such broad bands could be determined. The shape of
this IVCT band is more pronounced in samples of
maghemite-magnetite mixtures, or in soils containing
magnetite, because of the generally higher reflectivity
of these samples (Figure 4). Even trace amounts of
-10
540 560 580 600 820 640 magnetite are detectable.
WAVELENGTH (nm)
Quantification of Hematite and Goethite in Soils
Figure 5. Second-derivative spectra of the remission func-
tion f(R) in selected spectrum bands for mixtures of a defer- The well-separated EPTs of goethite and hematite
rated soil material with different quantities of (a) goethite and allow one to identify very small amounts of goethite
(b) hematite. and hematite. Figure 5 shows selected parts of the sec-
534 Scheinost, Chavernas, Barr6n and Torrent
,,,~ 1 y = -0.068 + 1.325 x 9 J
I.-
~-r = 9
0 e x t r a c t a b l e Fe to h e m a t i t e a n d goethite.
0.8
§ CONCLUSIONS
0.6
tu
"r" 0.4
0.2
"I"
0 m e a s u r e m e n t s is fast ( < 5 m i n ) a n d n o n d e s t r u c t i v e .
' .6
0 0.2 0,4 0 0.8
Y~(Y2+Y1)
Figure 7. The relationship between the hematite/(hematite
+ goethite) ratio as determined by differential XRD, and the
112/(I"1 + Y2) ratio as determined by diffuse reflectance spec-
troscopy (see Figure 6 for explanation of Yj and 112).
o n d - d e r i v a t i v e c u r v e o f the reflectivity f u n c t i o n for
m i x t u r e s o f a d e f e r r a t e d soil m a t r i x (treated with ci-
t r a t e / b i c a r b o n a t e / d i t h i o n i t e to r e m o v e Fe oxides) a n d
s y n t h e t i c h e m a t i t e a n d goethite; c o n c e n t r a t i o n s as low
as 0.5 g k g - t p r o d u c e a significant c h a n g e in the curve.
In Vertisol s a m p l e s c o n t a i n i n g only goethite as F e ox-
ide, the d e t e c t i o n limit for this m i n e r a l was a b o u t 3 g
k g -~ (results not s h o w n ) . In s u m m a r y , the detection
limit s e e m s to b e at least 1 o r d e r o f m a g n i t u d e smaller
t h a n that o f o r d i n a r y X R D .
To o b t a i n an i n d e x o f the b a n d intensity in the sec-
o n d - d e r i v a t i v e c u r v e s for goethite a n d hematite, we
u s e d the a m p l i t u d e b e t w e e n the - 4 1 5 - n m m i n i m u m
((4E;aAI)~---6At) a n d the - - 4 4 5 - n m m a x i m u m for goe-
thite ( d e n o t e d as Y1), a n d b e t w e e n the - - 5 3 5 - n m m i n -
i m u m (EPT) a n d the - 5 8 0 - n m m a x i m u m for h e m a t i t e
( d e n o t e d as I12) (Figure 6). F o r the 4 0 soils used, w h i c h
g e n e r a l l y c o n t a i n e d less t h a n 150 g k g -~ h e m a t i t e a n d
goethite, a h i g h l y significant c o r r e l a t i o n was f o u n d be-
t w e e n g o e t h i t e c o n t e n t a n d Y~ ( G o e t h i t e [g kg -~] =
- 0 . 0 6 + 268111; r 2 = 0.86; P < 0.001), a n d h e m a t i t e
c o n t e n t a n d I12 ( H e m a t i t e [g k g ~] = - 0 . 0 9 + 402Y2;
r: = 0.85; P < 0.001). M u l t i p l e r e g r e s s i o n u s i n g b o t h
a m p l i t u d e s did not i m p r o v e the c o r r e l a t i o n coefficient.
F o r the s a m e soils, the r e d n e s s rating, (ROE), p r o p o s e d
b y B a r r 6 n a n d Torrent (1986) p r o v i d e d a h i g h e r cor-
r e l a t i o n with the h e m a t i t e c o n t e n t (r 2 = 0.94). H o w -
ever, the p r o c e d u r e s b a s e d on the s e c o n d - d e r i v a t i v e
c u r v e h a v e the a d v a n t a g e o v e r r e d n e s s ratings in that
they help s i m u l t a n e o u s l y predict h e m a t i t e a n d goethite
contents. In practice, o n e c a n use the r e l a t i o n s h i p be-
t w e e n the h e m a t i t e / ( h e m a t i t e + goethite) ratio (derived
f r o m X - r a y or differential X R D m e a s u r e m e n t s ) and
the Y2/(Y~ + }'2) a m p l i t u d e ratio for that p u r p o s e (Fig-
ure 7). T h e a b s o l u t e quantities o f h e m a t i t e a n d g o e t h i t e
are c a l c u l a t e d f r o m the p r e d i c t e d h e m a t i t e / ( h e m a t i t e +
Clays and Clay Minerals
goethite) ratio, b y a s s i g n i n g the d i f f e r e n c e b e t w e e n ci-
t r a t e / b i c a r b o n a t e / d i t h i o n i t e - e x t r a c t a b l e Fe a n d oxalate-
M o d e r n s p e c t r o p h o t o m e t e r s allow the fast acquisi-
tion o f reflectance spectra (typically less than 10 min,
only a few s e c o n d s with n e w diode array detectors),
and calculations of derivatives and band amplitudes
c a n b e d o n e easily w i t h the a p p r o p r i a t e software. In
addition, s a m p l e p r e p a r a t i o n for s p e c t r o p h o t o m e t r i c
T h e s e a d v a n t a g e s m a k e s e c o n d - d e r i v a t i v e diffuse re-
flectance s p e c t r o s c o p y well suited for routine mea-
s u r e m e n t s o f goethite a n d h e m a t i t e in soils a n d m i n -
eral mixtures. W i t h the e x c e p t i o n o f h e m a t i t e a n d
magnetite, however, the u n e q u i v o c a l d i s c r i m i n a t i o n o f
Fe o x i d e m i n e r a l s c a n n o t b e p e r f o r m e d b y u s i n g the
positions o f the crystal field b a n d s only. A b e t t e r result
m a y b e a c h i e v e d b y i n c l u d i n g the v i b r a t i o n a l b a n d s
into the d i s c r i m i n a n t analysis ( C o y n e et al. 1990; B i s h -
op et al. 1995; B i s h o p a n d M u r a d 1996).
ACKNOWLEDGMENTS
ACS acknowledges the research grant by the Deutsche For-
schungsgemeinschaft, and thanks D. G. Schulze (Purdue Uni-
versity) who gave the visiting scientist a warm welcome and
provided the equipment, R. V. Morris (NASA, Houston, Tex-
as) for his introduction into the secrets of diffuse reflectance
spectroscopy and U. Schwertmann (Technische Universit~it
Mtinchen, Germany) who generously provided his large col-
lection of Fe oxides.
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(Received 28 August 1997; accepted 23 January 1998; Ms.
97-084)

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