Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 111^125

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Geochemical analysis and paleoecological implications of

phosphatic microspherules (otoliths?) from Frasnian^
Famennian boundary strata in the Great Basin, USA
Katherine A. Giles
, Nancy J. McMillan, Brian L. McCarson 1
Department of Geological Sciences, New Mexico State University, Las Cruces, NM 88001, USA
Accepted 6 December 2001

Abstract

Phosphatic microspherules ( 6 1 mm diameter) recovered from the Upper Devonian (uppermost Frasnian)
Guilmette Limestone in eastern Nevada are interpreted here to be fish otoliths and thus provide insight into ocean
water chemistry just prior to the Frasnian^Famennian mass extinction boundary. Analysis by scanning electron
microscope (SEM) and electron microprobe indicates that they are apatite (francolite) and consist of radially aligned,
concentrically banded crystals around a central nucleus. This type of microspherule, previously interpreted to be
conodont pearls, has compositions more similar to fish teeth derived from the same unit than to conodonts.
Microspherules and fish teeth have consistently lower concentrations in wt% of P2 O5 (31.88^36.32), F (3.05^5.12),
SrO (0.15^0.34), and analysis totals (indicating higher concentrations of OH and/or CO3 ; 90.66^96.09) and higher
CaO (51.67^55.15), SO2 (0.50^0.90), MgO (0.09^0.15), and Fe2 O3 (0.11^0.21) than the associated conodonts (P2 O5 :
37.32^40.01; F: 4.99^6.89; SrO: 0.32^1.79; totals: 96.07^100.55; CaO: 52.32^53.06; SO2 : 0.05^0.21; MgO: 0.01^
0.05; Fe2 O3 : 0.02^0.11). These differences in composition are consistent from core to rim in all microfossils analyzed
and reflect primary biogenic compositions rather than diagenetic or metamorphic signatures. We interpret the apatite
microspherules to be genetically related to the fish teeth rather than to the conodonts based on the geochemical
analysis. The microspherules are morphologically similar to modern teleost fish otoliths. The fish teeth found
associated with the microspherules are from Acanthodian or Actinopterygian fish, which possessed otoliths in the
Devonian and are the distant ancestors to modern teleost fish. Modern fish otoliths normally have a calcium
carbonate composition, but their trace element composition is highly sensitive to ambient water temperature and
chemistry. We speculate that the stratigraphically restricted range and phosphatic composition of the Devonian
otoliths reflects secretion by fish under conditions of excess dissolved reactive phosphorus in the water column that
was most likely associated with upwelling and cooler-water conditions on the shelf during maximum
transgression. B 2002 Elsevier Science B.V. All rights reserved.

Keywords: Devonian; Frasnian; mass extinctions; phosphatic otoliths; geochemistry

1
1. Introduction
Present address: 6445 S. Maple Ave. #2134, Tempe, AZ
85283, USA.
* Corresponding author: Fax: +1-505-646-1056. A variety of microspherules ( 6 2 mm in diam-
E-mail address: kgiles@nmsu.edu (K.A. Giles). eter) have been identi¢ed in Frasnian^Famennian

0031-0182 / 02 / $ ^ see front matter B 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 3 1 - 0 1 8 2 ( 0 1 ) 0 0 4 7 5 - 8

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112 K.A. Giles et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 111^125
age strata in North America, Australia, China,
and Belgium (Leuteritz et al., 1972; Glenister et
al., 1976; Claeys et al., 1992; Claeys and Casier,
1994; Wang and Chatterton, 1993). Microtektite
microspherules are silica-rich, glassy, terrestrial
debris melted due to heat produced by the im-
pact of a large extraterrestrial body with the
earth. They commonly possess subspherical ‘splash
form’ morphologies (Wang and Chatterton, 1993)
and are amorphous with abundant gas vesicles
and fused-silica inclusions (Wang, 1992; Glass
and Wu, 1993; Wang and Chatterton, 1993). Cos-
mic microspherules are black, subspherical to
spherical in shape, have dendritic or polygonal
surface textures, and are composed of magnetic
iron. Cosmic microspherules are produced by
melting of incoming interplanetary dust and larg-
er bodies during atmospheric entry (Brownlee,
1985; Wang and Chatterton, 1993). Phosphatic
conodont pearls are organically produced micro-
spherules with dimpled morphologies composed
of radially aligned apatite crystallites that form
concentric layers around a central nucleus
(Glenister et al., 1976). The pearls have been
linked to conodonts because of their common
phosphatic composition, apparently con¢ned
stratigraphic range (Cambrian through Lower
Carboniferous) that partially overlaps with the
biostratigraphic range of conodonts (Cambrian
through Triassic), and because of their consistent
depositional association with conodonts (Young-
quist and Miller, 1948; Glenister et al., 1976;
Wang and Chatterton, 1993).
Phosphatic microspherules ( 6 1 mm diameter)
have been recovered from the Upper Devonian
(latest Frasnian) Guilmette Limestone in eastern
Nevada and western Utah. The Upper Guilmette
Limestone was deposited during a period of step-
wise protracted extinctions just prior to the Fras-
nian^Famennian boundary. This period of extinc-
tions is associated with an abrupt reduction in
global biomass and loss of up to an estimated
82% of the world’s marine tropical to subtropical
species (Jablonski, 1991). The extinction event has
variously been attributed to extraterrestrial im-
pacts (McLaren, 1970; Kerr, 1992; Claeys and
Casier, 1994; McGhee, 1994, 1996), global cool-
ing (McGhee, 1989), global warming (Thompson
PALAEO 2827 5-6-02
and Newton, 1988), sea-level change (Johnson,
1974), oceanic anoxic events (Wilde and Berry,
1984; House, 1985; Joachimski and Buggisch,
1993; Algeo et al., 1995), equatorial cold waters
(Copper, 1986) and multiple causes with biogeo-
chemical^climatic in£uences (Buggisch, 1991;
Racki, 1998; Murphy et al., 2000). In this study,
we analyze phosphatic microspherules from the
Upper Guilmette Limestone in order to determine
their origin and to interpret the geologic signi¢-
cance of their rare occurrence at this ecologically
critical time.
2. Area descriptions, methods, and material studied
Phosphatic microspherules were initially re-
ported from eastern Nevada and western Utah
by Goebel (1991) and Bocko (1997) within insolu-
ble residues of conodont biostratigraphic samples
acquired for sedimentologic and stratigraphic
studies. In those two studies, over 400 conodont
biostratigraphic samples were collected from 35
mountain ranges (Fig. 1). The samples were col-
lected from the uppermost beds of the Frasnian to
the top of the lower Osage section. The general
Upper Devonian to lower Mississippian stratigra-
phy in this area of study (Fig. 2) comprises the
Frasnian Guilmette Limestone (610^808 m) over-
lain regionally by a variety of Famennian strata
including the Pilot Shale (213^332 m), Cove Fort
Quartzite (50 m), West Range Limestone (192 m),
Pinyon Peak Limestone (131 m) and Fitchville
Limestone (10 m), and the lower Mississippian
(Kinderhook^Osage stages) Joana (100 m) and
Gardison (30 m) limestones. Though conodont
faunas were ubiquitous in all units studied, micro-
spherules were recovered exclusively from the
uppermost beds of the Frasnian Guilmette Lime-
stone (Fig. 2; uppermost Palmatolepis linguiformis
conodont Zone). The Frasnian^Famennian
boundary is locally placed either at the contact
between the Guilmette Limestone with the over-
lying Pilot Shale or a few meters above this within
the Pilot Shale (Sandberg et al., 1980, 1989; Goe-
bel, 1991; Bocko, 1997; Morrow, 1997; Bratton
et al., 1999).
The Guilmette Limestone comprises shallow to
 K.A. Giles et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 111^125
Fig. 1. Generalized Late Devonian paleogeographic map of
the study area in eastern Nevada and western Utah showing
location of microspherule sample sites and conodont bio-
stratigraphic sites.
deep subtidal carbonate facies deposited during a
continent-wide transgression (Johnson, 1970; Lar-
son et al., 1989; LaMaskin, 1995; LaMaskin and
Elrick, 1997). The regional depositional setting of
the Guilmette Limestone was a wide, low-energy,
westward-facing, gently sloping ramp^platform
along the passive margin of western North Amer-
ica (Sandberg et al., 1989; Johnson et al., 1991;
LaMaskin, 1995; LaMaskin and Elrick, 1997).
The uppermost beds of the Guilmette Limestone
may have been deposited during the earliest phase
of £exural subsidence of the Pilot back-bulge ba-
PALAEO 2827 5-6-02
113
sin in response to Antler orogenesis (Goebel,
1991; Giles, 1994; Giles and Dickinson, 1995).
For this study, microspherule-bearing strata
from Nevada and Utah were remeasured and re-
sampled in greater detail. Three sites in particular
bore proli¢c numbers of microspherules ( s 400
specimens) and were the focus of this study: (1)
Northern Pancake Range; (2) Ward Mountain;
and (3) Burbank Hills (Fig. 1). Samples of the
upper beds of the Guilmette Limestone were col-
lected at approximately half-meter intervals from
the Guilmette^Pilot contact downward to a depth
of 3 m below the contact (Fig. 3). Each 1 kg
sample was processed by standard conodont pro-
cessing techniques. Fossils collected from the in-
soluble residues included conodont elements, ¢sh
teeth, and silici¢ed foraminiferid, ostracod, bra-
chiopod, and echinoderm skeletal debris. Cono-
donts and ¢sh teeth were present in all the sam-
ples containing microspherules, but microspherules
were not found in all samples containing cono-
donts or ¢sh teeth. Conodont color alteration in-
dex (CAI) was determined for conodont speci-
mens from the three sites using the methodology
of Epstein et al. (1977).
Microspherules were separated and classi¢ed
according to their physical characteristics. Two
basic groups were recognized based on color
and relative diaphaneity and include a black-
opaque group and a clear-translucent group
with colors ranging from white, yellow, light
green, and orange. Microspherule colors are var-
iable within a particular sample and do not nec-
essarily match those of the conodont elements
present in the same sample, which con£icts with
the observations of Glenister et al. (1976). Repre-
sentative specimens were collected for analysis by
electron microprobe and SEM.
Microspherules, ¢sh teeth, and conodonts were
analyzed by electron microprobe in the Los Ala-
mos National Laboratory SX50 Probe Lab using
a beam of 5 Wm in diameter at 15 kV and 30 Na
probe current. Analyses were corrected using PAP
matrix corrections; cations were calculated based
on a total of 26 O+F+Cl. Images of the micro-
fossils were acquired in the Electron Microscopy
Lab at New Mexico State University on a Hitachi
S3200N SEM.
114 K.A. Giles et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 111^125

Fig. 2. Generalized Upper Devonian (part Frasnian to Famennian) through lower Mississippian (Kinderhookian) stratigraphic
column for eastern Nevada and central Utah showing major formational names, conodont zonation, and the coastal onlap curve
indication of third-order eustatic sea-level changes during the Late Devonian and earliest Mississippian. Coastal onlap for the
Late Devonian was derived from Johnson et al. (1991) and from Ross and Ross (1987) for the lower Mississippian. Conodont
zonation is derived from Ziegler and Sandberg (1990).

Fig. 3. Stratigraphic sections from three microspherule-bearing sites displaying lithology, sample locations, stratigraphic location
of recovered conodonts, microspherules, and ¢sh teeth, and conodont biostratigraphy.

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 K.A. Giles et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 111^125 115

3. Results and analyses these concentric bands represent progressive nu-

Analysis of the microspherules using petro-
graphic and scanning electron microscopy demon-
strates that the microspherules possess a shiny,
smooth to dull, rough pitted exterior surface.
Each microspherule consistently possesses a small
dimple on one side (Fig. 4A,B) and contains radi-
ally aligned apatite needles around a central core
(Figs. 5 and 6). The microspherules display multi-
ple (20^40) concentric bands that vary in color
and thickness (Fig. 6). It is not clear whether
cleation of crystal layers (similar to an ooid or a
pearl) or if they represent individual needles that
are compositionally zoned along their length.
SEM photographs of the conodont platform ele-
ments and ¢sh teeth, analyzed using the electron
microprobe are shown in Fig. 4C^F. The cono-
donts are all from the uppermost Frasnian Pa.
linguiformis Zone (formerly uppermost Pa. gigas
Zone. The ¢sh teeth have only generally been
identi¢ed as belonging to either the acanthodian
or actinopterygian groups (most likely actino-

Table 1
Electron microprobe analyses of microspherules
Burbank Hills Ward Mountain Average 1 S.D.
a
Depth : 0.0 0.0 0.0 6.0 6.0 6.0 0.0 0.0
core mantle rim core rim rim at dimple core rim
SiOb2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Al2 O3 0.01 0.01 0.02 0.01 0.03 0.02 0.02 0.02 0.02 0.01
Fe2 O3 0.18 0.20 0.17 0.20 0.16 0.14 0.11 0.11 0.16 0.03
MnO 0.00 0.05 0.00 0.03 0.03 0.00 0.01 0.00 0.02 0.02
MgO 0.13 0.12 0.11 0.13 0.11 0.10 0.09 0.09 0.11 0.02
CaO 53.78 53.71 53.50 55.12 54.28 53.45 53.75 53.20 53.85 0.60
SrO 0.19 0.21 0.22 0.20 0.18 0.15 0.20 0.18 0.19 0.02
Na2 O 0.67 0.64 0.79 0.59 0.58 0.71 0.65 0.62 0.66 0.07
P2 O5 36.32 33.96 33.24 34.55 35.24 34.43 32.43 31.89 34.01 1.46
F 3.93 3.99 4.34 3.32 4.93 4.09 4.03 4.83 4.18 0.52
Cl 0.02 0.02 0.04 0.02 0.01 0.02 0.02 0.05 0.02 0.01
SO2 0.87 0.81 0.90 0.67 0.64 0.71 0.50 0.53 0.70 0.15
O equiv. F 31.65 31.68 31.83 31.40 32.08 31.72 31.70 32.03 31.76 0.22
O equiv. Cl 0.00 0.00 30.01 0.00 0.00 0.00 0.00 30.01 30.01 0.00
Total 96.09 93.73 93.33 94.83 96.18 93.81 91.81 91.52 93.91
Cations based on 26 O+F+Cl
Si 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Al 0.0030 0.0022 0.0040 0.0018 0.0067 0.0037 0.0048 0.0055 0.0039
Fe3þ 0.0240 0.0277 0.0238 0.0280 0.0215 0.0200 0.0163 0.0165 0.0223
Mn 0.0000 0.0080 0.0006 0.0052 0.0039 0.0006 0.0011 0.0000 0.0024
Mg 0.0351 0.0347 0.0301 0.0352 0.0288 0.0279 0.0256 0.0263 0.0305
Ca 10.4373 10.8051 10.8350 10.9798 10.5855 10.7066 11.1257 11.0465 10.8107
Sr 0.0194 0.0228 0.0244 0.0213 0.0192 0.0164 0.0229 0.0198 0.0208
Na 0.2343 0.2344 0.2881 0.2134 0.2051 0.2556 0.2431 0.2318 0.2380
P 5.5706 5.3974 5.3206 5.4390 5.4316 5.4494 5.3032 5.2323 5.3951
F 2.2497 2.3696 2.5963 1.9503 2.8403 2.4200 2.4619 2.9581 2.4786
Cl 0.0052 0.0070 0.0138 0.0050 0.0025 0.0054 0.0056 0.0161 0.0075
S 0.1483 0.1428 0.1587 0.1160 0.1088 0.1245 0.0899 0.0954 0.1233
Total Pc 5.5706 5.3974 5.3206 5.4390 5.4316 5.4494 5.3032 5.2323 5.3951
Total Cad 10.7531 11.1268 11.2055 11.2795 10.8667 11.0301 11.4383 11.3463 11.1262
a
Depth (m) below contact between Pilot Shale and Guilmette Limestone.
b
SiO2 was analyzed to insure that analytical volume did not include material surrounding microfossils; major elements in
wt%.
c
Total P+CO3 should equal 6.0 in stoichiometric apatite. CO3 was not determined in this study.
d
Total Ca+Al+Fe+Mn+Mg+Sr+Na should equal 10.0 in stoichiometric apatite.

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116 K.A. Giles et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 111^125

Fig. 4. Scanning electron micrographs of microspherules, conodonts, and ¢sh teeth. (A) SEM image of microspherules from NP-
0 meters showing smooth, translucent texture and spherical^ovoid shape. (B) SEM image of single spherical microspherule show-
ing etched surface with dimple. (C) SEM image of Pa. linguiformis Zone, Palmatolepis sp. indet. from NP-0 meters. (D) SEM im-
age Pa. linguiformis Zone, Polygnathodus sp. from NP-0 meters. (E) SEM image of elongate ¢sh teeth from NP-0 meters. (F)
SEM image of stocky ¢sh teeth from NP-0 meters.

pterygians, M. Ginter, personal communication). Electron microprobe analyses of microspherules

SEM photographs showing the ‘burn trace’ of the
microprobe beam on one of the microsphere sam-
ples (WGN-G6.0) displays the three di¡erent
analyses positions (core, dimple margin, margin)
used in this study (Fig. 7).
(Table 1), ¢sh teeth (Table 2), and conodonts (Ta-
ble 3) demonstrate that all three species are com-
posed of francolite, a £uor-carbonate apatite. The
microspherules and ¢sh teeth share chemical sim-
ilarities, while signi¢cant di¡erences in major and

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 K.A. Giles et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 111^125
Fig. 5. Scanning electron micrograph of fractured surface of microspherule showing radially aligned, needle-form, apatitic crystal-
lites.
minor element composition exist between them
and the conodont elements. For instance, F con-
centrations typically exceed 3.0 wt% but are con-
sistently higher in conodonts than microspherules
and ¢sh teeth (Fig. 8B). The presence of carbon-
ate, which substitutes for phosphate in the tetra-
hedral site, is inferred from the low stoichiometric
totals of phosphorus. Total stoichiometric phos-
phorus is signi¢cantly higher in conodonts (aver-
age 5.75 cations per 26 O+F+Cl) than in the mi-
crospherules (average 5.40) or the ¢sh teeth
(average 5.48), suggesting that the conodonts con-
tain lower amounts of carbonate in solid solution
with phosphate. In addition, microspherules and
teeth analyses have consistently low totals (90.66^
96.18 wt%) and Ca in excess of the 10 stoichio-
metric cations per formula unit (10.67^11.35), in
contrast to conodont analyses, which have totals
near 100 (96.07^100.55 wt%) and stoichiometric
Ca values (average 10.01 cations per formula
unit). The combination of low wt% totals and
excess Ca suggests to us that the microspherules
and teeth contain calcium carbonate in the form
of submicroscopic inclusions in the apatite; the
conodonts lack this additional carbonate. The
link between microspherules and ¢sh teeth is re-
inforced by minor element analyses (Fig. 8). Mi-
crospherules and ¢sh teeth have lower concentra-
PALAEO 2827 5-6-02
117
tions of SrO and higher SO2 , MgO, and Fe2 O3
than conodonts. Thus, the major (Ca, P, F, CO3 )
and minor (Sr, S, Mg, Fe) element chemistry of
these microfossils shows that the microspherules
are quite similar to ¢sh teeth but signi¢cantly dif-
ferent from conodonts. The microspherules also
contain small inclusions of iron sul¢de within
the concentric layers.
Although the Guilmette Limestone has experi-
enced diagenesis and varying degrees of post-dia-
genetic heating, we interpret the di¡erences in
composition between microspherules/¢sh teeth
and conodonts to be the result of primary, bio-
genic crystallization rather than taphonomic, dia-
genetic, or metamorphic alteration for several rea-
sons. One of the fundamental di¡erences in these
two populations is in the P2 O5 concentration (Fig.
8). Phosphorus is tightly bound to oxygen in the
apatite crystal structure ; thus, P2 O5 contents
should not change markedly during diagenesis.
In addition, the excess calcium carbonate in the
microspherules and teeth probably would have
been released during recrystallization of the mi-
crofossils. To support these claims, we analyzed
the cores and rims of several microfossils ; these
analyses are joined by lines in Fig. 8. If the com-
positions were related to each other by di¡ering
degrees of recrystallization controlled by perme-
118 K.A. Giles et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 111^125

Fig. 6. Thin-section photomicrograph of one quarter of microspherule showing concentric layering around central core within mi-
crospherule.

ability or other factors during diagenesis or meta-
morphism, we would expect that the rims of the
microfossils would be more strongly a¡ected, and
would tend to be similar to each other. What we
found, however, is that changes in composition
between cores and rims are variable. For instance,
CaO and F concentrations can both increase and
decrease in the rims of these fossils. Furthermore,
compositions of apatite fossils are similar in the
three localities studied, although these have expe-
rienced varying thermal histories as demonstrated
by the di¡erent CAI for the three sites: Northern
Pancake Mountains (CAI = 2); Ward Mountain
(CAI = 4); and Burbank Hills (CAI = 3). Thus,
we conclude that the analyses re£ect primary dif-
ferences in composition, that the microspherules
are closely related in composition to the ¢sh teeth,
but not closely related to the conodonts, in refu-
tation of previous suggestions by Glenister et al.
(1976) and Wang and Chatterton (1993).

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 K.A. Giles et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 111^125 119

spherules are more likely to have a biological af-

¢nity with marine actinopterygian ¢sh than
conodonts.
Modern Teleost ¢sh possess earstones or oto-
liths. One of the three otoliths found in each Tele-
ost ¢sh is called lapilli and is of similar size to the
phosphatic microspherules of this study, has con-
centric laminations, and often displays a dimpled
spherical morphology (Campana and Neilson,
1985). Modern otoliths are composed of calcium
carbonate, typically aragonite, and the concentric
laminations are produced on a daily basis. Lam-
ination width and trace element chemistry is
closely tied to the ambient water temperature
and chemistry (Campana and Neilson, 1985;
Kingsmill, 1993). Some Paleozoic actinopterygian
Fig. 7. Scanning electron micrograph of microspherule show- ¢sh (the ancestors of the Teleost ¢sh) also pos-
ing core, margin, and dimple margin ‘burn’ marks of micro- sessed otoliths (Schultze, 1990; Maisey, 1996). We
probe analyses. suggest that the phosphatic microspherules of the
Guilmette Limestone closely resemble otoliths
4. Discussion and conclusions from teleostomi ¢sh based on the geochemical
similarity of the microspherules to teleostomi
The francolite composition, concentric lamina-
tion, and dimpled spherical morphology of the
Guilmette microspherules are consistent with the
characteristics of previously described conodont
pearls (Leuteritz et al., 1972; Glenister et al.,
1976; Wang and Chatterton, 1993). Glenister et
al. (1976) suggested that conodont pearls were
internally secreted by conodonts in a ‘pearl-like’
fashion as a response to an organic or particulate
irritant and are not part of the standard function-
ing morphology. Their interpretation was based
on the apparent internal concentric laminated
structure, on the regular replication of the dimple
structure and the lack of impure laminae such as
clay rinds. Based on the same arguments, we also
conclude that the Guilmette Limestone micro-
spheres had an organic accretionary origin within
tissue. However, we conclude that the microspher-
ules were part of the standard functioning mor-
phology of the organism that secreted them based
on the consistent size, spherical shape, thickness
and smoothness of concentric laminae, and pres-
ence of a dimple, which are not attributes of mod-
ern naturally occurring ‘pearls’. We also suggest Fig. 8. Covariant plots of microprobe analysis. (A) CaO^
that the geochemical similarity of the microspher- P2 O5 plot. (B) F^P2 O5 plot. (C) SO2 ^SrO plot. (D) Fe2 O3 ^
ules to ¢sh teeth implies that the Guilmette micro- MgO plot.

PALAEO 2827 5-6-02