Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 299^311

www.elsevier.com/locate/palaeo

Variations in Ce anomalies of conodonts through

the Frasnian/Famennian boundary of Poland
(Kowala ^ Holy Cross Mountains):
implications for the redox state of seawater and biodiversity
Catherine Girard
, Christophe Le¤cuyer
UMR 5125 CNRS ‘Pale¤oenvironnements p Pale¤obiosphe're’, UCB-Lyon 1, 27 Bd du 11 Novembre, F-69622 Villeurbanne, France
Accepted 6 December 2001

Abstract

Rare-earth element (REE) concentrations on Upper Devonian conodonts, distinguished by very low Color
Alteration Index, were measured by inductively coupled plasma mass spectrometry from a stratigraphic section across
the Frasnian/Famennian (F/F) boundary in the Holy Cross Mountains (Poland). The present data show a ‘hat-
shaped’ pattern of the REE spectra similarly to other Devonian conodont spectra already documented. However, our
sample composition suggests little to moderate alteration of the original oceanic pattern through the adsorption
mechanism in a context of ‘weak’ or ‘early’ diagenesis. All along the section, the magnitude of the Ce anomaly is
always negative, and there is an inverse correlation between the Ce anomaly and the (La/Sm)SN ratio. This has been
interpreted as an La enrichment due to a terrestrial input. A mathematical procedure was used in order to restore the
original Ce anomalies that would reflect the seawater environment not contaminated by terrestrial inputs. No
noticeable change is observed in the Frasnian with homogeneous values of 6(Ce) model but a sharp increase is
initiated just below the F/F boundary with maximum values in the lowermost Famennian. The measured (La/Sm)SN
ratios co-vary with the 6(Ce) model in agreement with the hypothesis of a terrigenous input. Finally, the inverse
correlation between the values of 6(Ce) model and the relative abundance of Palmatolepis during the Famennian
constitutes the first evidence known of a redox control on the presence of a conodont genus that is an indicator of
deep-water environment. : 2002 Elsevier Science B.V. All rights reserved.

Keywords: rare-earth elements; Frasnian/Famennian boundary; Ce anomaly; redox control

1. Introduction ancient sedimentary rocks, especially anomalies in

the abundance of the redox-sensitive elements, Ce
Reliably preserved seawater REE signatures in and Eu, contribute to the interpretation of ocean-
ic input sources and seawater chemistry. Such
data have important implications for understand-
* Corresponding author. Fax: +33-4-72-44-83-82.
ing secular changes in oceanic strati¢cation, test-
E-mail addresses: [email protected] (C. Girard), ing hypotheses of redox-related mass extinctions.
[email protected] (C. Le¤cuyer). In particular, the chemical behavior of REE in

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

PALAEO 2834 5-6-02

300 C. Girard, C. Le¤cuyer / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 299^311

seawater has been applied in paleoceanography veri¢ed by conclusions from whole-rock geochem-
using the REE content of marine biogenic phos- ical study, independently realized at this succes-
phates of Phanerozoic age. Several applications sion (Racki et al., 2002).
have been made such as the identi¢cation of dis- REE data were obtained by inductively coupled
tinct water masses (Grandjean et al., 1987, 1988; plasma mass spectrometry (ICP-MS) on single
Felitsyn et al., 1998), the redox state of paleo-sea- conodonts from layers straddling the Frasnian/
water using the Ce anomaly (Elder¢eld and Pa- Famennian (F/F) boundary in Poland. Conodonts
gett, 1986; Wright et al., 1987), the in£uence of are an extinct group of marine animals whose
detrital REE inputs on the REE budget of coastal most commonly preserved parts are microscopic
waters (Grandjean et al., 1987, 1988), and the elements made of apatite, and which are com-
secular evolution of the REE contents of the monly interpreted as feeding apparatus (Purnell
world’s oceans (Grandjean-Le¤cuyer et al., 1993). and Donoghue, 1997). The main goal of this
REE patterns of Palaeozoic biogenic apatites do study is to examine in what extent the REE rec-
not resemble those documented in Mesozoic ma- ord re£ects marine environmental variations that
rine sediments (Le¤cuyer et al., 1998; Reynard et could in£uence the biodiversity and abundance of
al., 1999). Bertram et al. (1992) have also shown conodonts across the F/F boundary. This limit
that Silurian conodont apatites are characterized materializes the most important marine anoxic
by REE fractionations that are most likely related event recorded during the Upper Devonian.
to chemical processes of diagenetic alteration.
Based on a thermodynamic model of crystal-
chemical controls on REE distribution between 2. Geological setting
apatite and water, Reynard et al. (1999) proposed
that the typical ‘bell-shaped’ REE patterns ob- Distinct specimens from populations of the
served in Devonian biogenic apatite have resulted Upper Devonian conodonts were extracted from
from recrystallization during extensive or late dia- limestone layers (sampled in 1992 by M.M. Joa-
genesis. They are characterized by strongly corre- chimski and W. Buggisch) from one F/F oxygen-
lated (La/Yb)SN and (La/Sm)SN that tend to be depleted succession in the active Kowala quarry
signi¢cantly lower than preserved samples (Rey- (section Ko; Holy Cross Mountains, Southern
nard et al., 1999). However some Ordovician (Le¤- Poland) (Fig. 1). The Holy Cross Mountains rep-
cuyer et al., 1998) and Silurian (Bertram et al., resent a relatively small area (90U30 km) of the
1992) biogenic apatites exhibit very homogeneous Mid Polish Uplands, where the Palaeozoic strata
ratios, compatible with limited fractionation dur- outcrop in a quarry, and are isolated by the Per-
ing adsorption mechanism, and that should re£ect mian and Mesozoic sedimentary series from the
the secular variation of seawater composition. other Palaeozoic exposures of Central Europe.
The possibility to identify preserved marine REE This area constitutes a part of the southern Lau-
records of Devonian age is an exciting challenge russian shelf.
since the end of this period has been characterized
by numerous marine biological crisis of anoxic 2.1. Lithology
origin. The contemporaneous £ourishing of vas-
cular plants certainly played an important role in The Kowala section is the most representative
the erosion of continents and transport of matter of the Upper Devonian in¢lling of the southern
to the oceans (Gensel and Andrews, 1984; Algeo intrashelf basin, adjacent to the central paleotopo-
et al., 1995). As conodonts from the Holy Cross graphic high. Within the dark to black bitumi-
Mountains (Poland) show a very low Color Alter- nous marly sequence of set H de¢ned by Szul-
ation Index (CAI), it is of particular interest to czewski (1971, 1995), the following three units
compare their REE contents with those already are distinguished in the F/F strata (Fig. 2, see
obtained in neighboring areas. In addition, infer- Racki et al., 2002 for details).
ences derived from conodont REE patterns are H-2. Thin-bedded marly limestones with shale

PALAEO 2834 5-6-02

 C. Girard, C. Le¤cuyer / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 299^311 301

Fig. 1. Simpli¢ed geological map of the Holy Cross Mountains with location of the Kowala (Ko) section.

interbeds comprise frequent irregular subnodular unit H-3 between beds Ko 23 and 24 with the ¢rst
intercalations, up to 45 cm thick. Less abundant appearance of Palmatolepis triangularis in bed
fossil assemblages include both planktic and 24b. Lower triangularis Zone exhibits distinct
benthic elements. thickness reduction (subtle hiatus in the basal
H-3. Platy limestones, with beds up to 50 cm part). The transition toward marly stagnant-water
thick and thinner (usually less than 5 cm) shale
interbeds. The calcareous set, 6 to 8 m thick, is
the main exception within the uniform marly suc-
cession. The beds are composed of the variably
alternating radiolarian-spiculitic micritic and
‘grained’ (sparstone) bands. Black cherts are fre-
quent in the lower half part. Crinoid-brachiopod
lenticular accumulations occur particularly in the
middle portion of the unit ; only scattered Buchio-
la shells and large non-skeletal algae (in the
uppermost part) are the only other macrofossils.
H-4. Thick monotonous series, above 100 m
thick, of thin- and rhythmically bedded marly
limestones and shales. With the exception of
sporadic bioclastic, mainly crinoidal partings, im-
poverished macrofauna is limited to Guerichia and
largely inarticulate brachiopods.

2.2. Stratigraphy

As discussed in Racki et al. (2002), unit H-2

certainly belongs to the rhenana Zone, but the
upper boundary of this zone is poorly established.
Recognized entry of Palmatolepis linguiformis in
the uppermost part of the set H-2 (bed Ko 10) is
probably facies controlled, and only records the Fig. 2. Stratigraphic column of the F/F boundary beds in
advance of the transgression pulse. The F/F Kowala (Holy Cross Mountains, Poland; see ¢g. 4 in Racki
boundary is placed in the lower segment of the et al., 2002).

PALAEO 2834 5-6-02

302 C. Girard, C. Le¤cuyer / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 299^311

Table 1
REE conodont content (ppm) in the Kowala section (Ko), Holy Cross Mountains, Poland
Sample La Ce Pr Nd Sm Eu Gd Tb Dy Er Yb (La/Sm)SN 6(Ce)31
(ppm)
K35B-4 248.90 479.25 101.13 480.98 106.15 23.36 107.62 14.03 65.04 21.41 8.08 0.44 30.30
K35B-3 50.25 88.51 17.68 82.47 18.01 3.70 19.08 2.58 12.96 4.28 1.41 0.53 30.33
K35B-2 69.06 122.22 24.50 112.61 24.63 5.08 25.93 3.52 17.16 5.60 2.16 0.53 30.32
K35B-1 46.57 81.58 16.61 76.55 16.69 3.54 17.50 2.33 11.36 3.56 1.30 0.53 30.33
K31-4 162.71 325.20 70.05 335.58 76.27 16.53 76.83 9.71 45.99 14.56 5.32 0.40 30.29
K31-3 115.98 230.72 50.50 242.22 54.84 11.64 54.04 7.00 32.03 9.99 3.86 0.40 30.30
K31-2 205.13 439.74 93.78 439.40 98.53 20.36 90.51 11.75 52.44 15.89 5.87 0.39 30.25
K31-1 177.27 371.79 81.08 393.90 89.38 18.57 89.65 11.65 53.64 16.81 6.77 0.37 30.28
K28-5 245.73 471.60 103.90 487.45 109.77 23.57 105.06 13.89 63.94 21.51 9.30 0.42 30.31
K28-4 339.14 650.94 142.91 681.20 154.89 33.43 155.05 20.46 95.09 31.78 14.14 0.41 30.31
K28-3 327.16 637.61 142.04 693.60 159.65 33.70 164.79 21.82 102.53 34.40 15.09 0.39 30.32
K28-2 239.81 443.72 98.23 452.28 102.30 21.45 96.80 12.76 60.18 20.54 8.97 0.44 30.33
K28-1 354.57 694.38 155.54 756.42 176.07 39.21 179.54 24.30 115.11 39.33 18.47 0.38 30.31
K26B-5 358.37 666.39 145.49 713.80 165.79 35.02 177.54 23.93 116.36 42.91 20.00 0.41 30.33
K26B2-4 318.56 602.91 131.93 644.47 148.81 32.93 157.92 21.18 101.74 36.35 16.15 0.40 30.33
K26B2-3 400.86 764.56 163.18 767.97 176.96 39.76 181.07 24.30 115.48 39.91 18.89 0.43 30.31
K26B2-2 232.21 389.11 84.73 429.34 100.51 22.25 116.46 15.58 75.68 29.92 13.47 0.44 30.38
K26B2-1 145.83 266.13 56.58 279.39 64.85 14.08 69.40 9.42 44.52 15.77 6.76 0.42 30.34
K25C-5 53.58 95.01 19.37 96.72 22.20 4.90 27.39 3.88 17.63 6.04 2.68 0.46 30.34
K25C-4 70.48 122.18 25.25 123.53 27.22 6.40 33.19 4.52 21.58 7.97 2.89 0.49 30.35
K25C-3 116.43 197.76 40.44 196.81 44.14 10.55 53.49 7.50 35.33 12.84 5.47 0.50 30.36
K25C-2 70.57 102.70 21.77 106.37 23.52 5.71 29.19 4.08 19.74 6.98 2.90 0.57 30.43
K25C-1 44.05 76.98 15.32 77.64 16.71 3.71 20.46 3.10 12.95 4.45 2.05 0.50 30.35
K25B-5 97.45 167.07 34.24 164.86 38.38 8.67 44.89 6.12 30.01 10.91 4.70 0.48 30.35
K25B-4 50.13 86.40 17.73 85.72 19.99 4.47 23.32 3.31 15.05 5.43 2.02 0.47 30.35
K25B-3 32.41 54.75 10.87 53.62 12.40 2.71 13.99 2.03 9.43 3.20 1.28 0.49 30.36
K25B-2 92.27 157.26 33.21 162.14 36.06 8.83 43.68 6.04 28.55 10.66 4.97 0.48 30.36
K25B-1 49.50 86.53 17.66 86.78 19.97 4.26 23.32 3.44 15.54 5.28 2.07 0.47 30.35
K25A-5 120.28 194.89 41.08 205.54 45.47 10.72 56.81 7.97 38.21 14.62 6.74 0.50 30.39
K25A-4 38.86 63.43 12.90 60.55 12.99 2.79 12.54 1.63 8.49 2.75 0.93 0.57 30.37
K25A-3 100.18 163.74 34.15 161.22 36.58 7.94 40.61 5.69 28.46 11.14 4.29 0.52 30.37
K25A-2 43.57 76.05 14.49 75.71 15.50 3.60 19.87 2.75 13.49 4.56 2.24 0.53 30.35
K25A-1 31.57 54.84 11.14 54.58 12.81 2.91 15.25 2.11 10.18 3.52 1.32 0.47 30.35
K24B3-5 188.41 325.29 67.82 330.67 76.34 18.40 91.65 12.60 61.96 23.92 10.60 0.47 30.36
K24B3-4 98.61 167.67 35.85 180.33 42.30 9.93 52.20 7.25 34.65 13.68 5.86 0.44 30.37
K24B3-3 224.14 391.91 81.12 398.04 92.54 22.15 109.21 15.62 75.98 30.24 15.37 0.46 30.35
K24B3-2 227.26 386.66 83.20 401.43 89.89 21.70 109.68 15.96 75.17 27.70 13.99 0.48 30.37
K24B3-1 245.19 419.79 89.07 432.57 99.27 21.52 110.32 15.60 75.56 29.45 12.64 0.47 30.36
K24B2-5 178.22 308.70 62.54 311.15 69.84 16.58 81.26 11.27 55.17 21.11 9.70 0.48 30.35
K24B2-4 139.51 239.78 49.09 235.36 49.70 11.23 53.49 7.18 37.11 12.42 5.84 0.53 30.35
K24B2-3 180.51 327.91 64.80 314.02 70.25 17.44 80.70 11.36 53.70 20.70 9.66 0.49 30.32
K24B2-2 164.91 295.27 57.70 283.68 62.76 15.30 73.51 10.05 51.82 19.75 8.61 0.50 30.33
K24B2-1 186.08 324.71 68.25 334.12 77.02 18.20 87.30 11.90 59.82 22.59 10.12 0.46 30.35
K24B1-5 215.44 391.30 64.75 304.36 65.26 15.62 74.74 10.21 50.76 20.38 9.27 0.62 30.27
K24B1-4 190.43 337.06 58.85 282.28 60.90 14.68 73.72 9.64 48.01 18.33 8.63 0.59 30.30
K24B1-3 186.96 347.09 56.84 262.09 54.45 12.72 59.88 7.83 40.41 15.39 6.16 0.65 30.25
K24B1-2 148.31 273.88 45.11 211.31 46.74 11.38 54.41 7.39 37.06 14.40 6.76 0.60 -0.26
K24B1-1 200.08 359.29 63.92 299.26 65.81 15.27 77.46 10.41 48.95 19.09 8.75 0.57 30.29
K23B-5 52.27 97.70 16.22 74.40 15.82 3.76 18.40 2.62 12.15 4.45 1.80 0.62 30.25
K23B-4 103.19 190.23 30.49 138.95 29.25 6.75 33.00 4.49 21.00 7.31 2.27 0.67 30.25
K23B-3 113.95 213.88 36.04 166.37 35.12 8.30 40.21 5.24 25.14 9.30 3.95 0.61 30.25
K23B-2 87.41 163.55 26.80 124.67 26.72 6.14 30.16 4.24 19.17 6.28 2.03 0.62 30.25
K23B-1 83.93 160.41 26.83 122.53 26.10 6.24 29.13 3.93 18.91 6.69 2.07 0.61 30.24

PALAEO 2834 5-6-02

 C. Girard, C. Le¤cuyer / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 299^311 303

Table 1 (continued).
Sample La Ce Pr Nd Sm Eu Gd Tb Dy Er Yb (La/Sm)SN 6(Ce)31
(ppm)
K18-5 74.26 172.70 27.83 127.86 28.11 6.04 29.75 3.96 16.64 4.51 1.00 0.50 30.13
K18-4 248.90 563.82 90.21 414.84 92.83 19.16 95.00 12.47 58.86 19.31 8.71 0.51 30.14
K18-3 43.76 100.27 15.85 72.49 16.00 3.58 16.49 2.15 9.53 2.47 0.61 0.52 30.13
K18-2 113.37 274.74 44.25 196.16 44.21 9.06 41.79 5.47 24.24 7.39 2.85 0.48 30.09
K18-1 61.98 144.39 22.95 101.82 23.23 4.74 22.40 2.94 12.96 3.66 1.32 0.50 30.11
K15-5 194.91 484.35 84.56 385.76 84.22 18.14 81.80 11.01 52.35 17.13 6.95 0.44 30.11
K15-4 190.76 481.19 84.70 391.69 89.09 18.92 86.11 11.77 56.49 19.27 8.45 0.40 30.11
K15-3 220.56 535.97 93.11 430.19 93.63 19.81 91.69 12.52 58.87 19.95 8.06 0.44 30.12
K15-2 301.91 727.65 127.99 590.41 129.95 26.31 127.99 17.26 81.26 27.50 11.20 0.44 30.13
K15-1 238.56 549.37 96.43 442.31 97.71 20.20 98.41 13.54 64.03 22.39 9.68 0.46 30.16
K13-5 142.78 354.03 62.61 289.35 67.14 15.03 67.91 9.53 47.71 17.26 8.25 0.40 30.12
K13-4 108.74 253.79 45.00 206.24 47.03 10.72 48.17 6.81 33.11 12.28 5.33 0.44 30.15
K13-3 277.59 689.24 119.85 553.83 127.88 26.17 125.20 17.69 88.34 32.39 15.50 0.41 30.11
K13-2 58.60 146.29 24.57 108.02 24.52 5.45 23.69 3.32 16.15 5.26 1.98 0.45 30.08
K13-1 64.03 172.03 29.19 128.39 30.07 6.88 30.86 4.36 20.91 8.20 3.74 0.40 30.04
K8-4 58.58 94.48 18.95 85.37 18.53 3.71 18.60 2.60 12.51 4.56 1.69 0.60 30.36
K8-3 52.87 86.25 17.46 79.65 17.17 3.52 17.67 2.50 12.28 4.11 1.66 0.58 30.36
K8-2 61.86 99.24 20.08 90.07 19.62 4.03 20.60 2.79 13.74 4.63 1.86 0.60 30.36
K8-1 56.53 92.24 18.62 82.03 17.79 3.50 16.97 2.40 11.52 3.74 1.08 0.60 30.35
K4-5 27.68 68.99 12.78 59.83 13.78 3.05 13.80 1.93 9.23 2.92 1.08 0.38 30.13
K4-4 33.05 78.63 14.24 66.36 15.57 3.39 16.66 2.27 10.81 3.75 1.44 0.40 30.15
K4-3 58.91 141.50 26.07 122.94 28.45 6.42 29.46 4.04 19.42 6.43 2.61 0.39 30.15
K4-2 37.49 98.02 17.78 81.16 19.14 4.15 19.62 2.75 12.70 4.87 2.37 0.37 30.09
K4-1 57.96 123.48 23.16 108.21 25.62 5.62 26.92 3.71 18.34 6.79 3.73 0.43 30.22
K1-5 73.77 194.86 36.22 172.28 41.23 8.24 40.24 5.51 25.01 7.75 3.04 0.34 30.10
K1-4 35.38 88.46 16.49 77.91 18.82 4.00 19.73 2.64 11.95 3.69 1.36 0.36 30.13
K1-3 78.72 206.98 38.87 184.16 42.94 9.54 42.42 5.65 25.71 7.94 3.59 0.35 30.11
K1-2 63.43 175.02 32.36 147.48 34.09 7.07 33.34 4.34 19.24 6.24 2.71 0.35 30.06
K1-1 65.38 174.96 32.90 159.03 37.76 8.04 38.65 5.09 23.04 6.73 2.79 0.33 30.10
The Ce anomaly 6(Ce) is calculated after the method described in Grandjean et al. (1987). Shale normalization values used here
are those from the average North American shale of Gromet et al. (1984).

deposition of unit H-4 is timed in the Late trian- tent of seawater. The resulting early Famennian
gularis Zone. deposits are dark, laminated and extremely poor
This sequence reveals a decreasing input of plat- in fossils. These conditions implied that the main
form-derived carbonate debris into the basinal de- anoxic Kellwasser event in the linguiformis Zone
position. Allodapic limestones containing stroma- is di⁄cult to recognize strictly within the hemi-
toporoid reef biota occur in the set H-2 (Racki pelagic sequence of the oxygen-de¢cient basin
and Szulczewski, 1996), but the carbonate plat- (see also Joachimski et al., 2001). The beginning
form persisted at least to the Famennian Late tri- of a rapid sea-level rise is predicted for the more
angularis Zone, as evidenced by distal turbidites. macrofossil-impoverished topmost segment of the
The Famennian succession is more lithologi- unit H-2. The sudden establishment of calcareous
cally monotonous (marls, shales, nodular lime- deposition of the set H-3 might have been caused
stones) and generally scarcely fossiliferous. It re- by a catastrophic sea-level fall and sustained shal-
veals, however, an upward increase of faunal lowing trend interrupted by higher-energy epi-
diversity, especially marked in its topmost part. sodes (Sandberg et al., 1988, 1992), but also by
The principal factor controlling this pattern of block uplifts. Furthermore, bloom of the peculiar
vertical distribution seems to be the oxygen con- siliceous sponge-radolarian biota are ascribed to

PALAEO 2834 5-6-02

304 C. Girard, C. Le¤cuyer / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 299^311

the initial phase of the submarine volcanism and 4. Results

hydrothermal activity (cf. Maksimova, 1979) and/
or climatic cooling (see Racki, 1999; Racki et al., Trace element contents were determined in four
2002). to ¢ve individual conodonts from the same layer.
In general, individual conodonts from the same
bed have similar REE contents. The REE data
3. Analytical techniques are given in Table 1 and reported in Fig. 3 nor-
malized to NASC (Gromet et al., 1984). From the
All studied fossil samples were extracted from upper Frasnian to the lower Famennian, there is
uppermost Frasnian to the lowermost Famennian no major di¡erence in the shape of REE patterns.
limestones. After complete processing of the ma- These Devonian REE patterns are typically ‘hat
trix with dilute formic acid (10%), conodonts were shaped’ similarly to those documented in the Or-
picked for the REE analyses. Only platform ele- dovician of Estonia (Le¤cuyer et al., 1998) and in
ments belonging to the genera Palmatolepis were the Silurian of Gotland (Bertram et al., 1992).
selected. When plotted on a (La/Yb)SN versus (La/Sm)SN
Following the protocol developed by Girard diagram (Fig. 4) de¢ned by Reynard et al. (1999),
and Albare'de (1996), the REE data were obtained the conodonts from the Kowala section fall
by ICP-MS in the Geology Department from the grouped and close to the domain de¢ned by pre-
Ecole Normale Supe¤rieure of Lyon, France. Sin- viously cited well-preserved Palaeozoic apatites.
gle conodont elements were rinsed twice in tridis- This con¢guration strongly contrasts with the lin-
tilled water and digested in 0.1 ml 15 N nitric ear scattering (Fig. 4) de¢ned by other Devonian
acid. All solutions were visually clear, with no conodonts (Grandjean, 1989; Grandjean-Le¤cuyer
residue apparent. 0.1 ml of 1 ppm solution of In et al., 1993; Girard and Albare'de, 1996). This
and Bi internal standards was added and the vol- trend towards very low (La/Yb)SN and (La/
ume taken to a ¢nal 5 ml, which is the approx- Sm)SN ratios has been interpreted by Reynard et
imate sample consumption for three runs of trace al. (1999) as a progressive mechanism of REE
element analysis. substitution in the apatite lattice during extensive
Calibration curves were generated against stan- recrystallization.
dards BEN and BCR-1. Addition of In and Bi Ce anomalies, calculated after Grandjean et al.
spikes to the samples was used to correct the (1987), are always negative throughout the F/F
beam intensity for ionization suppression. Series sequence, they vary from 30.4 to 30.01 (Fig. 5).
were made of two solutions of known concentra- However, they are more negative in the Famen-
tions, one standard rock, three blanks, and 10 nian (mean 6(Ce) = 30.31 U 0.04) compared to
samples. Analyzed mass counts were then normal- Frasnian (mean 6(Ce) = 30.14 U 0.09). Along the
ized with respect to the appropriate internal stan- section, there is an inverse correlation between the
dard intensity. Ce anomaly and the (La/Sm)SN ratio, except for
Repeated control of the 31 P/43 Ca ratio on con- the levels immediately succeeding the F/F bound-
odont solutions showed that the Ca/P ratio was ary (Fig. 5).
within few percent of the proportions in conodont
apatite as determined by Grandjean (1989) upon
repeated electron-probe measurements. The total 5. Discussion
number of counts on mass 43 Ca could therefore
be turned into an estimate of the sample weight. 5.1. Signi¢cance of Ce anomalies in Kowala
A mean concentration of 38 wt% Ca was used. conodonts
The uncertainties in the quanti¢cation of REE
abundances induced by this method are not crit- The REE contents of conodonts from the Ko-
ical for this study since only internal variations wala section of Poland do not seem to have been
within REE patterns will be discussed. seriously disturbed by a process of ‘late’ diage-

PALAEO 2834 5-6-02

 C. Girard, C. Le¤cuyer / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 299^311 305

Fig. 3. Representative selection of REE contents normalized to shales (NASC) of Frasnian (top) and Famennian (bottom) cono-
donts from the Kowala section (Poland).

netic alteration according to the terminology used oceanographic events. However, recent studies re-
by Reynard et al. (1999). In the framework of a vealed that, in some cases of diagenetic processes,
sedimentary sequence characterized by anoxic Ce anomalies are not reliable to track past redox
events and major changes in biodiversity, the states of seawater (Bertram et al., 1992; Holser,
use of the Ce anomaly as a proxy of seawater 1997; Le¤cuyer et al., 1998). Therefore, the search
redox conditions seems appropriate to track for a correlation between variations in Ce anoma-

PALAEO 2834 5-6-02

306 C. Girard, C. Le¤cuyer / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 299^311

Fig. 4. Compilation of normalized (La/Yb)SN ratios versus (La/Sm)SN ratios of biogenic phosphates of various ages after Reynard
et al. (1999). Conodonts from the Kowala section are compared with those coming from contemporaneous deposits: Coumiac,
La Serre, Causses-et-Veyrans (Montagne Noire, France) and Steinbruch Schmidt (Rheinisches Schiefergebirge, Germany), data
from Grandjean (1989).

lies of conodonts and their relative abundances of littoral inarticulate brachiopods. The specimens
will constitute an adequate test for the reliability sampled from an estuary are LREE enriched rel-
of this geochemical proxy. Another di⁄culty in ative to open sea analogs. A terrigenous source
interpreting the REE geochemical record is linked responsible for an LREE enrichment of cono-
to the platform environment which is known to donts will ‘arti¢cially’ change the amplitude of
be sensitive to detrital input from the continents the Ce anomaly. If the marine REE signature is
(Grandjean et al., 1987). The chemical erosion of mainly disturbed by an La enrichment as sug-
neighboring magmatic rocks is a potential source gested by the shape of some REE patterns (Fig. 3),
of REE that can scramble the REE signature of more negative Ce anomalies than expected should
the seawater mass. Le¤cuyer et al. (1998) have be observed. Such a plausible process may be
shown that the alteration of volcanic rocks in tested by the existence of a predicted inverse cor-
New Caledonia deeply disturb the REE signature relation between the (La/Sm)SN ratio and the Ce

PALAEO 2834 5-6-02

 C. Girard, C. Le¤cuyer / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 299^311 307

Fig. 5. Variations of the Ce anomaly and normalized (La/Sm)SN ratios recorded in conodonts across the F/F boundary in Kowa-
la (Poland).

anomaly as more or less observed in Fig. 5. The restoration of the original Ce anomalies that
occurrence of marked negative Ce anomalies in would re£ect the seawater environment not con-
sediments deposited in overall oxygen-depleted taminated by terrestrial inputs implies a subtrac-
conditions (Joachimski et al., 2001; Racki et al., tion of the La enrichment by a mathematical pro-
2002) constitutes a surprising paradox when ana- cedure. Excluding systematically La and Ce, REE
lyzing the REE record in Polish conodonts. The from all conodont samples have been ¢tted with a

Fig. 6. Comparison between the computed and measured REE pattern of conodont sample K13-2. The model has been obtained
by a ¢tting of REE data with a parabolic equation.

PALAEO 2834 5-6-02

308 C. Girard, C. Le¤cuyer / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 299^311

increase is initiated just below the F/F boundary

with maximum values in the lowermost Famen-
nian. The Famennian is characterized by an
abrupt change in Ce anomalies with values
down to 30.35 in the Ko 31 level (Fig. 7). The
measured (La/Sm)SN ratios (Fig. 5) co-vary with
the 6(Ce) model in agreement with the hypothesis
of a terrigenous input in the platform domain of
Poland and Germany. This siliciclastic £ux was
likely maximum close to the F/F boundary in
the Kowala and Steinbruch Schmidt sections.

5.2. Implications for the conodont biodiversity

Terrestrial input in the marine environment

may be responsible for the development of eutro-
phic conditions further leading to oxygen-depleted
waters. The abrupt appearance of anoxic condi-
tions may strongly disturb the marine food
chains. Algeo et al. (1995) have proposed that
the £ourishing of vascular plants at the end of
Fig. 7. Variations of the (6Ce)N model along the Kowala the Devonian enhanced continental erosion,
section (Poland).
brought huge £uxes of nutrients in epicontinental
seas, and ultimately disturbed marine ecosystems.
parabolic function to compute theoretical Ce con- In the Kowala succession, there is an inverse
tents. All the ¢tting procedures lead to correlation correlation between the values of 6(Ce) model
coe⁄cients equal to or higher than 0.95. For ex- and the relative abundance of Palmatolepis during
ample, modeling the REE pattern of sample the Famennian (Fig. 8). This relationship consti-
K13-2 (Fig. 6) reveals the existence of a positive tutes the ¢rst evidence known of a redox control
La anomaly. These computed Ce anomalies, on the presence of a conodont genus that is an
noted 6(Ce) model, are de¢ned as follows : indicator of a deeper shelf environment. The eco-
system stabilization, maybe determined by the on-
½Cemeasured set of better-oxygenated waters in a deepening
6 ðCeÞ model ¼ 31 ð1Þ platform environment, located in the level Ko
½Cecomputed
31, coincides with a bloom (Racki et al., 2002)
of the genus Palmatolepis whose relative abun-
Since the absolute magnitude of these computed dance jumps from 45% to more than 60%
Ce anomalies are model dependent, only the rel- (Fig. 8). According to Racki et al. (2002), the
ative variations will be discussed in relation with abrupt decrease of the biomass observed just
the stratigraphic succession and faunal changes. above the F/F boundary could be partly caused
Average values of 6(Ce) model for each level by both eutrophication pulse and oxygen deple-
have been reported along the stratigraphic column tion of seawater during an overall regressive
(Fig. 7). The distribution of these values through phase in the intrashelf basin.
time provides a drastically di¡erent pattern when
compared to uncorrected Ce anomalies that were
reported in Fig. 5. If no noticeable change is ob- 6. Conclusions
served in the Frasnian with homogeneous values
of 6(Ce) model ranging from 30.2^0, a sharp REE concentrations of conodonts across the

PALAEO 2834 5-6-02

 C. Girard, C. Le¤cuyer / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 299^311 309

Fig. 8. Relative abundance of the deep-water Palmatolepis indicator (data from Racki et al., 2002) versus (6Ce)N model for the
Famennian levels in the Kowala section. Error bars on the Y-axis correspond to standard deviations associated with the mean
values of (6Ce)N model, which were calculated for several conodont samples from the same bed. Error bars on the X-axis repre-
sent uncertainties associated with the counting procedure of conodonts.

F/F boundary in Poland, marked by very low gisch, 1993; Wang et al., 1996). The remaining
CAI, are used to track oceanic oxygenation question concerns the timing of the major anoxic
events. The inverse correlation observed between event relative to the F/F boundary. If at Kowala,
(La/Sm)SN ratio and the Ce anomaly has been the REE record in conodonts suggests that a ma-
interpreted as an La enrichment probably due to jor oxygen depletion of seawater occurred just
a detritical input. Corrected Ce anomalies lead to after the F/F boundary, Bratton et al. (1999) ob-
suspect the existence of a terrigeneous input which served in the Great Basin (USA) a similar event
may be responsible for the development of eutro- prior to the limit with a return to oxic conditions
phic conditions in the marine environment. The before the Famennian. Therefore, we cannot ex-
inverse correlation between the 6(Ce) model and clude the existence of a regional tectonic control
the relative abundance of conodont genus Palma- of the basin bathymetry that strongly in£uenced
tolepis suggests that its occurrence was likely con- both the distribution of the conodont genus Pal-
trolled by the redox state of the marine environ- matolepis and the redox state of seawater.
ment. We cannot exclude that the increasing
oxygenation of seawater could have been favored
by the deepening of the basin through a more Acknowledgements
e⁄cient mixing of the water mass. This possibility
raises questions about the regional versus global The authors are grateful to Patricia Grandjean
meaning of the REE geochemical record pre- for a first reading of the manuscript and valuable
served by the Kowala section. A drop in the oxy- discussions. Authors thank Grzegorz Racki, who
genation level of seawater at the vicinity of the provided us with the conodont collection (courtesy
F/F boundary followed by a progressive return of W. Buggish and M.M. Joachimski), and
to oxic conditions has been documented world- support for geochemical analysis (funded by the
wide (e.g. Wang et al., 1991; Joachimski and Bug- Committee of Scientific Research of Poland,

PALAEO 2834 5-6-02

310 C. Girard, C. Le¤cuyer / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 299^311

Grant 6 P04D 024 13). Reviews made by Jean-Alix Holser, W.T., 1997. Evaluation of the application of rare-earth
elements to paleoceanography. Palaeogeogr. Palaeoclimatol.
Barrat, Howard A. Armstrong and Bruno Rey-
Palaeoecol. 132, 309^324.
nard helped us to improve the scientific content of Joachimski, M.M., Buggisch, W., 1993. Anoxic events in the
this work. We acknowledge the assistance of late Frasnian ^ causes of the Frasnian-Famennian faunal
Philippe Telouk and Francis Albare'de (ENS, crisis? Geology 21, 675^678.
Lyon, France) during the ICP-MS measurements. Joachimski, M.M., Ostertag-Henning, C., Pancost, R.D.,
This research was funded by the CNRS and the Strauss, H., Freeman, K.H., Littke, R., Damste¤, J.S., Racki,
G., 2001. Water column anoxia, enhanced productivity and
program CRISEVOLE ‘-370-350: bioe¤ve¤nements concomitant changes in N13 C and N34 S across the Frasnian-
chez les Inverte¤bre¤s marins’. Famennian boundary (Kowala-Holy Cross Mountains/Po-
land). Chem. Geol. 175, 109^131.
Le¤cuyer, C., Grandjean, P., Barrat, J.A., Emig, C.C., Nolvak,
J., Paris, F., Robardet, M., 1998. N18 O and REE contents of
phosphatic brachiopods: A comparison between modern
References and lower Paleozoic populations. Geochim. Cosmochim.
Acta 62, 2429^2436.
Algeo, T.J., Berner, R.A., Maynard, J.B., Scheckler, S.E., Maksimova, S.V., 1979. Biogenic silicates, an indicator of
1995. Late Devonian oceanic anoxic events and biotic crises: the activity of deep-seated faults. Int. Geol. Rev. 21, 869^
‘rooted’ in the evolution of vascular land plants? GSA To- 876.
day 5, 45/65^66. Purnell, M.A., Donoghue, P.C.J., 1997. Architecture and func-
Bertram, C.J., Elder¢eld, H., Aldridge, R.J., Conway Morris, tional morphology of the skeletal apparatus of ozarkodinid
S., 1992. 87 Sr/86 Sr, 143 Nd/144 Nd and REEs in Silurian phos- conodonts. Philos. Trans. R. Soc. Lond. B 352, 1545^1564.
phatic fossils. Earth Planet. Sci. Lett. 113, 239^249. Racki, G., 1999. Silica-secreting biota and mass extinctions:
Bratton, J.F., Berry, W.N.B., Morrow, J.R., 1999. Anoxia pre- Survival patterns and processes. Palaeogeogr. Palaeoclima-
dates Frasnian-Famennian boundary mass extinction hori- tol. Palaeoecol. 154, 107^132.
zon in the Great Basin, USA. Palaeogeogr. Palaeoclimatol. Racki, G., Racka, M., Matyja, H., Devleeschouwer, X., 2002.
Palaeoecol. 154, 275^292. The Frasnian/Famennian boundary interval in the South
Elder¢eld, H., Pagett, R., 1986. Rare earth elements in ich- Polish-Moravian shelf basins: Integrated event-stratigraphi-
thyoliths: Variations with redox conditions and depositional cal approach. Palaeogeogr. Palaeoclimatol. Palaeoecol.,
environment. Sci. Total Environ. 49, 175^197. S0031-0182(01)00481-3.
Felitsyn, S., Sturesson, U., Popov, L., Holmer, L., 1998. Nd Racki, G., Szulczewski, M., 1996. Stop 4 Kowala railroad cut
isotope composition and rare earth element distribution in and quarry. In: Szulczewski, M., Skompski, S. (Eds.), Sixth
early Paleozoic biogenic apatite from Baltoscandia: A sig- European Conodont Symposium (ECOS VI). Excursion
nature of Iapetus ocean water. Geology 26, 1083^1086. Guide, Warszawa, pp. 27^33.
Gensel, P.G., Andrews, H.N., 1984. Plant Life in the Devo- Reynard, B., Le¤cuyer, C., Grandjean, P., 1999. Crystal-chem-
nian. Praeger, New York. ical controls on rare-earth element concentrations in fossil
Girard, C., Albare'de, F., 1996. Trace elements in conodont biogenic apatites and implications for paleoenvironmental
phosphates from the Frasnian/Famennian boundary. Pa- reconstructions. Chem. Geol. 155, 233^241.
laeogeogr. Palaeoclimatol. Palaeoecol. 126, 195^205. Sandberg, C.A., Ziegler, W., Dreesen, R., Butler, J.L., 1988.
Grandjean, P., 1989. Les terres rares et la composition isoto- Late Frasnian mass extinction: Conodont event stratigra-
pique du ne¤odyme dans les phosphates bioge'nes: Traceurs phy, global changes, and possible causes. Cour. Forsch.
des processus pale¤o-oce¤anographiques et se¤dimentaires. Un- Inst. Senckenb. 102, 263^307.
publ. Doctorat, INPL, Nancy. Sandberg, C.A., Ziegler, W., Dreesen, R., Butler, J.L., 1992.
Grandjean, P., Cappetta, H., Michard, A., Albare'de, F., 1987. Conodont biochronology, biofacies, taxonomy and event
The assessment of REE patterns and 143 Nd/144 Nd ratios in stratigraphy around Middle Frasnian Lion Mudmound
¢sh remains. Earth Planet. Sci. Lett. 84, 181^196. (F2h), Frasnes, Belgium. Cour. Forsch.-Inst. Senckenb.
Grandjean, P., Cappetta, H., Albare'de, F., 1988. The REE 150, 1^87.
and ONd of 40^70 Ma old ¢sh debris from the West-African Szulczewski, M., 1971. Upper Devonian conodonts, stratigra-
platform. Geophys. Res. Lett. 15, 389^392. phy and facial develoment in the Holy Cross Mts. Acta
Grandjean-Le¤cuyer, P., Feist, R., Albare'de, F., 1993. Rare Geol. Pol. 21, 1^129.
earth elements in old biogenic apatites. Geochim. Cosmo- Szulczewski, M., 1995. Stop 2: Kowala quarry. In: Evolution
chim. Acta 57, 2507^2514. of the Polish-Moravian Carbonate Platform in the Late
Gromet, L.P., Dymek, R.F., Haskin, L.A., Korotev, R.L., Devonian and Early Carboniferous: Holy Cross Mts, Kra-
1984. The North American Shale Composite: Compilation, kow Uplands, Moravian karst. XIII Int. Congr. Carbonif-
major and trace element characteristics. Geochim. Cosmo- erous-Permian, Krakow. Guide to Excursions B4, pp. 13^19.
chim. Acta 48, 2469^2482. Wang, K., Orth, C.J., Attrep, M., Chatterton, B.D.E.,

PALAEO 2834 5-6-02

 C. Girard, C. Le¤cuyer / Palaeogeography, Palaeoclimatology, Palaeoecology 181 (2002) 299^311 311

Hongfei, H., Geldsetzer, H.H.J., 1991. Geochemical evi- the Frasnian-Famennian extinction boundary, Alberta, Can-
dence for a catastrophic biotic event at the Frasnian/Famen- ada. Geology 24, 187^191.
nian boundary in south China. Geology 19, 776^779. Wright, J., Schrarder, H., Holser, W.T., 1987. Paleoredox var-
Wang, K., Geldsetzer, H.H.J., Goodfellow, W.D., Krouse, iations in ancient oceans recorded by rare earth elements in
H.R., 1996. Carbon and sulfur isotope anomalies across fossil apatite. Geochim. Cosmochim. Acta 51, 631^644.

PALAEO 2834 5-6-02