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Application of LA-ICP-MS to sedimentary phosphatic particles from Tunisian

phosphorite deposits: Insights from trace elements and REE into paleo-
depositional environments

Article  in  Chemie der Erde - Geochemistry · June 2012

DOI: 10.1016/j.chemer.2012.02.001

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 Chemie der Erde 72 (2012) 127–139

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Chemie der Erde

journal homepage: www.elsevier.de/chemer

Application of LA-ICP-MS to sedimentary phosphatic particles from Tunisian

phosphorite deposits: Insights from trace elements and REE into
paleo-depositional environments
Hechmi Garnit a,b,∗ , Salah Bouhlel a,b , Donatella Barca c , Chaker Chtara d
a
Department of Geology, Faculty of Sciences of Tunis, El Manar University, 2092 Tunis, Tunisia
b
Laboratoire de Biotechnologie et Valorisation des Bio-Géo Ressources, Institut Supérieur de Biotechnologie de Sidi Thabet, Université de la Manouba, Tunisia
c
Department of Earth Sciences, University of Calabria, Via Ponte Bucci 4, Cubo 15B, 87036 Arcavacata di Rende (CS), Italy
d
Groupe Chimique Tunisien (G.C.T.). 110, Rue Habib Chagra, 6002 Gabes, Tunisia

a r t i c l e i n f o a b s t r a c t

Article history: Laser ablation ICP-MS was used to determine trace (TE) and rare earth element (REE) contents of sedimen-
Received 30 November 2010 tary phosphatic pellets and coprolites collected from late Paleocene-early Eocene phosphorite deposits
Accepted 6 February 2012 in Tunisia. TE and REE contents in the investigated deposits exhibit a close relationship with grain types

Keywords:
and paleogeography. Phosphatic pellets seem to concentrate more TE and REE than co-existing  copro-
lites. Both particle types display modern oxic-suboxic seawater patterns. In most coprolites, REE, Y,
Laser ablation ICP-MS
Cr, Ni, Th, and V show an increase from core to rim, whereas Ba, Cd, Cu, and U abundances decrease from
Trace and rare earth elements
core to rim, reflecting adsorption processes during early diagenesis consistent with changing redox and
Phosphatic pellets
Coprolites
productivity conditions.
Paleoenvironments The northern basins (Sra Ouertane) within open marine and platform settings tended to be more oxic-
Tunisia suboxic with relative high organic matter flux, while the eastern basins (Jebel Jebs) and Gafsa-Metlaoui
basin are characterized by semi-restricted situation associated with suboxic-oxic conditions. This result
is consistent with previous reconstructions which suggest that phosphorites of northern basins had a
more direct connection to the open ocean than those to the south and east of the emerged area.
This study highlights the potential for using laser ablation ICP-MS as a tool to reconstruct phosphorite
depositional paleoenvironments.
© 2012 Elsevier GmbH. All rights reserved.

1. Introduction
The aim of this research was to investigate the laser ablation-
ICP-MS (LA-ICP-MS) method for the elemental analysis of
phosphatic pellets and coprolites for the purpose of increasing our
knowledge regarding environmental controls on trace elements
(TE) and rare earth elements (REE) in Tunisian phosphorites.
TE and REE have been recognized as generally being enriched
in phosphorites compared to “average” shale and other sedimen-
tary rock types (Gulbrandsen, 1966; Altschuler, 1980; Prévôt, 1990;
Jarvis et al., 1994). The bulk chemistry of phosphorite reflects both
the composition of francolite (CFA), the main mineral in sedi-
mentary phosphorites, and that of accessory minerals (silicates,
carbonates, sulfates, organic matter and heavy minerals), which
incorporate TE and REE disproportionately and unpredictably, and
∗ Corresponding author at: Department of Geology, Faculty of Sciences of Tunis,
El Manar University, 2092 Tunis, Tunisia. Tel.: +216 96166643; fax: +216 71885408.
E-mail address: garnit1hechmi@yahoo.fr (H. Garnit).
such accessory phases must be ruled out in order for TE and REE data
to be interpreted properly. However the composition of separated
constituents, especially authigenic phosphatic particles, allows a
better understanding of the diagenetic processes which lead to the
incorporation of particular elements in phosphorites in different
depositional environments.
Analyses of pure phosphatic particles require purification and
concentration processes such as washing followed by granulomet-
ric fractionation, hand-picking under a binocular microscope and
heavy liquid separation. While these methods result in the isolation
of pure phosphate phases, there are complications related to: par-
ticle size, risk of contamination of small samples during separation,
and difficulties in measuring amounts of trace elements.
LA-ICP-MS has been widely reported as a powerful in situ ana-
lytical technique. This method has a wide range of applications
in geological (Axelsson et al., 2002; Donelick et al., 2006; Kosler,
2007; Apollaro et al., 2009; Bertelli et al., 2009; Cook et al., 2009;
Tóth et al., 2010), geoarcheological (Barca et al., 2007), archeomet-
ric (Vlachou-Mogire et al., 2007; Barba et al., 2009) environmental
(Scarciglia et al., 2009; Barca et al., 2010) and paleontological

0009-2819/$ – see front matter © 2012 Elsevier GmbH. All rights reserved.
doi:10.1016/j.chemer.2012.02.001
128 H. Garnit et al. / Chemie der Erde 72 (2012) 127–139
(Koenig et al., 2009; Rogers et al., 2010) studies. It provides direct
and element-selective analysis and forms a good alternative to
wet-chemical analysis of solids as it solves many of the problems
associated with conventional acid-digestion method (destructive,
time consuming, relatively complex, costly and suffers from spec-
troscopic interferences).
Advantages of in situ microanalysis include the possibility
to determine micrometric compositional variations. In geological
applications, LA-ICP-MS is one of the dominant techniques capa-
ble of generating multi-element analyses with very low detection
limits for mineral and other geological samples.
No attempt has been made previously to study the TE and REE
geochemistry of Tunisian phosphorites on a regional scale with an
in situ technique. The present study reports the results of LA-ICP-
MS analyses on phosphatic pellets and coprolites collected from
different deposits and layers spaced in both geographic location
and time, in order to discuss their significance on contemporary
seawater chemistry, diagenetic processes and paleodepositional
environments. For this propose, phosphorite sampling was carried
out at five different locations corresponding to variable pale-
oenvironmental conditions: Sra Ouertane (northern basins), Jebel
Jebs (eastern basins), Mzinda, Kef Eddour Centre and Naguess
located east, center and west of Gafsa-Metlaoui basin, respectively.
As revealed by previous mineralogical, geochemical, sedimento-
logical studies and paleogeographic reconstructions (Sassi, 1974;
Belayouni, 1983; Chaabani, 1995; Béji-Sassi, 1999; Zaïer, 1999),
the genesis, development and extension of phosphorites were con-
trolled by structural basin evolution (geometry and subsidence),
eustatic and sea level fluctuations and climatic variations, reflected
in facies, mineralogical and geochemical differences between
Fig. 1. (A) Geographic position of the studied area in Tunisia. (B) Paleogeographical situation of Tunisia during the early Eocene with position of studied areas (after Sassi,
1974; Winnock, 1980; Zaïer et al., 1998).
phosphorites of the more open marine waters to the north and
those formed in relatively restricted basins south and east of the
emerged area.
2. Geology
Tunisian sedimentary phosphorites are part of the “Late
Cretaceous-Eocene Giant Phosphorite Belt” stretching from the
Caribbean in the west to Middle East, through North Africa (Notholt,
1980; Notholt et al., 1989; Sheldon, 1987; Glenn et al., 1994;
Lucas and Prevot-Lucas, 1995). During this period large amounts
of phosphorites were deposited in the area now known as Tunisia
by phosphogenesis in the Tethyan Ocean. Tunisian phosphorites
occur in marine sediments of late Paleocene-early Eocene age that
were deposited on the borders of Kasserine Island in three large
basins: the northern basin situated to the north, which represents
a shallow platform setting. The Gafsa-Metlaoui basin and eastern
basins (Meknassy-Mezzouna basins) situated south and east of the
Kasserine Island, respectively, which corresponds to a more basinal,
depositional environment (Fig. 1).
The Gafsa-Metlaoui basin is an intracratonic basin with sub-
sidence controlled by major NW-SE and W-E oriented faults
(Chaabani, 1995). Sedimentation in the Gafsa basin occurred
in a relatively restricted basin, which fluctuated between
littoral-lagoonal environments, resulting in rhythmic or episodic
sedimentation. The consequence is a significant variation of facies
in this basin (phosphorites, diatom rich-facies, shales, marls, car-
bonates, and gypsum). The phosphorite-bearing series belongs to
the Eocene Metlaoui Group which lies above the Paleocene series of
El Haria Formation (green shales interbedded with thin limestone
 H. Garnit et al. / Chemie der Erde 72 (2012) 127–139
beds) and is overlain by the late Eocene Jebs Formation (massive
bedded gypsum and dolomite). The Metlaoui Group can be divided
into three members. The lower member corresponds to the Thelja
Member and ranges in thickness from 10 to 100 m consisting of
marl, bioturbated and chalky dolomite, shelly and bioclastic car-
bonates and thick layers of gypsum. A major discontinuity occurs
at the top of this unit.
The real ore beds belong to the middle member or Chouabine
Member and consist of gray-brown, friable, pelletal phosphorite
interbedded with diatom-rich facies, marls, shales and carbonates
with apparent stratification. A total of nine phosphorite beds (num-
bered downwards 0 to IX), have been distinguished. Individual beds
may be absent or vary in thickness and grade from place to place.
The Chouabine Member is overlain by Kef Eddour Member (third
member) which consists of two thick carbonate units, made up of
massive bioturbated and laminated dolomitic limestone interbed-
ded with phosphate-poor thin beds named “phosphate du toit”
meaning Phosphate of the roof.
The Eastern basins correspond to small isolated basins which lie
parallel to the main North-South (Nosa axis) structural lineament,
separated by elevated or low-subsidence paleo-highs (Béji-Sassi,
1999; Zaïer et al., 1998). In the eastern basins, sedimentation was
mainly carbonaceous and evaporitic, typical of lagoonal environ-
ments deposited in depressions and tilted blocks born in the axis of
those Cretaceous high-shoals, showing several thickness and facies
variations, partly caused by Ypresian tectonic, but principally by
extrusive tectonics of Triassic salt (Béji-Sassi, 1999; Zaïer et al.,
1998). Within these basins the lithostratigraphic succession of the
Metlaoui Group varies considerably from basin to basin and the
phosphorites and their lateral equivalents are less well developed
and lower in grade than those found in the Gafsa-Metlaoui basin. In
general, the Metlaoui Group can be divided into three main units,
a lower unit, which is generally dolomitic, the second unit which
corresponds to the main phosphorite series and the upper unit
which is composed mainly of dolomitic gypsum and fine-grained
phosphorite layers. In Jebel Jebs, the phosphorite-bearing unit con-
tains three phosphorite beds (CI, CII and CIII), separated by clay and
dolomite interlayers. The Metlaoui group is overlain by thick and
massive gypsum and/or dolomitic beds of the Jebs Formation.
The Northern basins are characterized by a system of blocks
tilted with mainly carbonaceous open marine sedimentation. Phos-
phorites of the northern basins are more diverse in character than
the corresponding Gafsa-Metlaoui phosphorites. Typically, they are
fine-grained, hard, compact and glauconite-rich. Usually they form
two main units separated by a thin marl bed (Zaïer, 1999). In Sra
Ouertane, the Metlaoui Group can be subdivided in 4 units: lower
unit “Unit A”, ranges in thickness from 0.3 to 63 m and consists
of alternating marly-phosphatic and carbonate-phosphorite beds.
Depending on the abundance of carbonate layers, this unit can
be subdivided into two subunits: carbonate-phosphorite “A1” and
marly-phosphorite “A2”. The upper unit “C” is separated from the
lower unit by a 1 m marly layer and consists of phosphorite which
reaches 15 m in thickness, grading upwards into a corprolite-rich
layer overlying bioturbated carbonate. The Nummulitic limestone
of the El Garia Formation is separated from unit C by alternations
of dominantly carbonate with thin beds of phosphorite, marls and
cherts of unit “D”.
3. Samples and analytical methods
3.1. Sampling and preparation
Bulk phosphorite samples were collected from several cross-
sections representing phosphorites from the three basins, worked
open-cast mines in the Gafsa-Metlaoui basin (Mzinda, Kef Eddour
Centre and Naguess) and outcrops in Sra Ouertane (Jebel Ayata and
129
Oued Echerchara) and Jebel Jebs. Although from different layers,
all samples are late Paleocene-early Eocene in age (Fig. 2). These
sites were chosen both for the variety of facies and paleogeographic
settings.
The phosphatic pellets and coprolites were separated from
their matrix by granulometric fractionation after hand processing
the bulk samples under water and hand-picking under binocular
microscope. Polished sections were prepared and checked for min-
eral inclusions. Only homogenous grains were employed for laser
analyses and about 100 mg of sample powdered was employed for
solution ICP-MS.
3.2. Analytical methods
Polished sections were prepared and studied under a metal-
lographic microscope. Scanning electron microscopy and energy
dispersive spectroscopy (SEM-EDS) were performed on polished
sections, using a scanning electron microscope (ESEM FEG, QUANTA
200, Philips), equipped with an energy dispersive x-ray analyzer
with a Si/Li crystal detector (GENESIS-4000, EDAX). In situ analysis
was performed by LA-ICP-MS from individual grains (phosphatic
pellets and coprolites) mounted on polished sections. Additionally,
6 samples were also analyzed with solution ICP-MS to evaluate
possible errors and/or differences with each analytical technique.
LA-ICP-MS analyses were carried out at the Department of Earth
Sciences, Università della Calabria, Italy, using an Elan DRCe (Perkin
Elmer/SCIEX), operating either in normal mode as a standard ICP-
MS instrument or in a dynamic reaction cell(DRC), connected to a
New Wave UP213 solid-state Nd-YAG laser probe (213 nm). Sam-
ples were ablated by laser beam in a cell, and the ablated material
flushed in a continuous flow of an argon and helium mixture
(Gunther and Heinrich, 1999) to the ICP, where it was atomized and
ionized for quantification in the mass spectrometer. In this study,
ablation was performed with spots of 50 ␮m, a constant laser repe-
tition rate of 10 Hz and fluence of 20 J/cm2 . The details of operating
conditions are given in Table 1.
Two to three point analyses were carried out. All TE and REE
data presented in tables are mean concentrations. For each analysis,
background levels for all elements were established by acquiring
data for about 60 s (acquisition of gas blanks) before starting the
60 s of ablation. Data were transmitted to a PC and processed by the
GLITTER program; calibration was performed using the glass refer-
ence material NIST 612-50 ppm (Pearce et al., 1997) in conjunction
with internal standardization applying CaO (usually ∼50 ± 2 wt.%)
concentrations (Fryer et al., 1995) from SEM-EDX (Francesco et al.,
2005). In order to evaluate possible errors within each analyti-
cal sequence, determinations of trace elements were also made
on a BCR 2G glass reference material as an unknown sample, and
Table 1
Summary of LA-ICP-MS operating conditions.
Plasma conditions
Plasma gas flow 14–15 L min−1
Auxiliary gas 1.0–1.2 L min−1
He carrier gas flow 0.6–0.7 L min−1
Ar gas flow 0.7–0.8 L min−1
Rf power 1250 W
Laser Nd-YAG
Acquisition parameters
Wavelength 213 nm
Mode Q-switched
Laser energy 18.29 J cm−2
Shot repetition rate 10 Hz
Pattern Point
Spot size 50 ␮m
Background acquisition time 60 s
Acquisition time 60 s
Wash out 60 s
130 H. Garnit et al. / Chemie der Erde 72 (2012) 127–139

Fig. 2. Location map and synthetic cross-sections of the Metlaoui Group in Gafsa-Metlaoui basin, Jebel Jebs (after Béji-Sassi, 1999), and Sra Ouertane (after Zaïer, 1999)
showing lateral variations.

element concentrations were compared with reference values from
the literature (Gao et al., 2002). Accuracy, calculated as the differ-
ence from reference values, was always better than 10%, and most
elements had values in the range of 5%. Each spot analysis showing
spectra with sharp drops was eliminated and not considered for
data elaboration.
For ICP-MS analyses, phosphatic pellets and coprolites were
powdered in an agate mortar and the resulting powder were
dissolved by microwave digestion using a Mars5 microwave appa-
ratus (CEM technologies). About 100 mg (±0.01 mg) of powder was
placed in a microwave vessel with a mixture of Merck “suprapur”
quality hydrofluoric acid (5 ml HF) and nitric acid (5 ml HNO3 ), cov-
ered and sealed with a cap and subjected to an oven method that
consisted of a 15 min ramp to 230 ◦ C and pressure of 800 PSI, then
held at temperature for 15 min and then a 30 min cool down, result-
ing in a clear, colorless solution. After digestion, the content of each
 H. Garnit et al. / Chemie der Erde 72 (2012) 127–139 131

vessel was allowed to heat up to 200 ◦ C. Before the complete evap-

249.26

105.89

117.57

204.49
325.99

267.59
172.64
175.12
115.20
218.5

63.8

158.4
oration of acid we added 2 ml of nitric acid (5%) to ensure complete

Zn
removal of nitrofluoric acid. In order to obtain the mother solutions
they were let to cool down gently and made up to a standard volume
in a 100 ml volumetric flask with Millipore water. External cali-

153.12

77.92

46.59
54.21

60.43
102.10

30.09
41.80
58.70
bration curves were prepared using Perkin Elmer “multi-element

51.6

63.4

38.5
Calibration Standard 2 solution” to analyze trace and rare earth

V
elements. Standard reference materials Micaschist (SDC1) were
prepared in the same way and were used as unknown samples

32.585
during the analytical sequence as suggested by Eggins et al. (1997);

34.88

15.82
17.84

33.95
38.20

29.07

36.05

21.01
41.1

37.3

33.3
concentrations of the elements were compared with certified val-

U
ues to evaluate accuracy and precision of analytical data.

3215.95

3101.64

2195.33
2281.43
2221.93

2269.79
3477.01

2316.05
2376.80
2292.5

2429.3

2068.6
4. Results

Concentration (ppm) of some selected TE determined by LA-ICP-MS(1) and ICP-MS(2) for phosphatic pellets and coprolites from Metlaoui (Gafsa-Metlaoui basin) nd: not detected.

Sr
4.1. Mineralogy and petrography

The analyzed phosphatic pellets and coprolites are composed

8.53

9.78

21.37
13.58
17.23
12.56
12.13
14.56
6.50
20.3

13.8

10.7
almost entirely of cryptocrystalline CFA but display differences

Ni
in size, external morphology and nanostructure. Pellets dominate
over other types of phosphatic grains. Their sizes range between 0.1

4.035
and 0.5 mm. They are structureless, well-rounded to sub-rounded

2.94

5.82

5.72

6.63
5.42

6.98
3.09

5.07
Mo

3.2

8.7

4.7
and are yellowish to dark brown. Internally, phosphatic pellets
are homogenous and consist of microbial and filament structures
(Fig. 3A). They exhibit a porous nanostructure corresponding to

8.94

6.47

12.49
6.36
17.34
10.86

4.71
13.09

4.08
spherical to ovoid cavities ranging from 0.5 to 1 ␮m in diameter

8.6

15.5

3.2
Mn
(Fig. 3B). Secondary dolomite and sulfide inclusions (framboidal
pyrite and Cd-rich sphalerite) occur in some pellets (Fig. 3D–F).
Coprolites are the mineralized remains of originally organic fecal

3.29

5.18

4.29

9.62
5.37
6.78
4.64
8.18
6.71
10.6

6.8

10.2
matter mainly of crustaceans and/or fish and the phosphatization

Cu
of these excrements is related to microbial processes controlled by
the microenvironment (Lamboy et al., 1994). Coprolites display dif-
ferent morphologies (amphipolar spiral showing pre-lithification
151.87

159.67
33.18

40.56
180.60

170.09

138.70

150.40
35.80
174.0

231.8

134.7
unspiraling, straight, narrow amphipolar straight) reflecting the
Cr

structure of the gut wall, but usually appear sub-rounded or cylin-

drical in shape and range in diameter from 0.5 to a few millimeters
across. Coprolites exhibit a homogeneous porous apatite structure
17.84

11.57

14.54

2.14

5.94
0.69

0.53
5.40
0.50
with well formed hexagonal crystals of francolite piled upon one
0.6

0.1
nd
Co

another (Fig. 3C).

Generally, the phosphatic pellets and coprolites are composed
of CFA with contents of CaO ranging from 49.5 to 54.8 wt.% and
22.325
50.045
51.38

20.45

21.64

45.12
23.26
62.02

29.06
those of P2 O5 from 30 to 34 wt.%. Except SiO2 , other oxide concen-
62.9

18.5

18.4
Cd

trations are general less than 0.5 wt.%. Microscopic observations,

degree of crystallinity and the major element composition of both
particles support good preservation, thus allow us to use the TE
20.665
23.26

19.41

18.27
21.45

25.21
22.03

17.09
17.90

and REE contents of both particles for comparing the depositional

19.1

22.6

14.3
Ba

environments.

4.2. TE-bearing accessory phases in phosphatic particles

4.14

3.48

1.71
2.16
5.57
3.51
1.48
3.13
6.03
0.9

1.5

nd
As

In order to evaluate the influence of some mineral fractiona-

tions on TE and REE geochemistry, TE and REE concentrations were
Sample reference

determined by both LA-ICP-MS and ICP-MS. Tables 2 and 3 illustrate

comparative data of some selected TE and REE analyzed by both
C-ME1 (1)
C-ME1 (2)
C-ME2 (1)
C-ME2 (2)
C-ME3 (1)
C-ME3 (2)
P-ME1 (1)
P-ME1 (2)
P-ME2 (1)
P-ME2 (2)
P-ME3 (1)
P-ME3 (2)

techniques for three phosphatic pellets and three coprolites from

Metlaoui (Gafsa-Metlaoui basin). When evaluating the accuracy of
the LA-ICP-MS results by comparison with ICP-MS data, two param-
eters should be kept in mind. First, the concentrates obtained for
phosphorite digestion may contain few-␮m TE and/or REE-bearing
Phosphatic pellets

phases, which can affect bulk concentrations. On the other hand,

laser data can be affected by the nanostructure and internal chemi-
Description

cal zoning. The results indicate that LA-ICP-MS produces TE (e.g. As,
Coprolites

Cd, Cu, Zn) values up to two orders of magnitude lower than the bulk
Table 2

analyses. This suggests that submicroscopic TE-bearing phases are

distributed within phosphatic particles. Regarding REE contents,
132 H. Garnit et al. / Chemie der Erde 72 (2012) 127–139

Fig. 3. High resolution SEM images of phosphatic particles from the studied area illustrate the nanostructure and some mineral inclusions occur in CFA pellet. (A) Filamentous
morphology suggests bacterial affinity (B) porous nanostructure corresponding to spherical and ovoid nanocavities approximately 2–4 ␮m in diameter. (C) Euhedral, hexagonal
CFA crystallites approximately 0.4–0.8 ␮m in diameter (a-axis direction) and 0.2–0.5 ␮m in length (c-axis direction) (D) well developed ␮m-rhombs of dolomite, indicating
of in situ growth during diagenesis enhanced by high alkalinity of the pore waters, generated by the microbial respiration of sedimentary organic matter or favored by
precipitation within these organic rich-sediments in low-sulfate or sulfate free diagenetic environments (E) framboidal pyrite in phosphatic pellet (F) sphalerite microcrystal
inclusion (radiolarian test?) occurring in the core of phosphatic pellet.
 H. Garnit et al. / Chemie der Erde 72 (2012) 127–139 133

(Dy/Yb)N
variations were recorded for LREE (La, Ce) concentrations, but are
insignificant for MREE and HREE. Ce anomalies and other elemen-

1.24
1.12
0.74
0.91
0.66
0.85

1.15

0.59
0.89
0.93
0.89
1.07
tal ratio data obtained by both techniques do not reveal significant
differences.

(La/Yb)N
Dolomite, pyrite, sphalerite and iron oxides are the most com-

1.46
0.61
0.76

0.76

0.94
0.96
0.74
0.84
0.92
0.86
1.06

0.70
mon authigenic minerals. They occur as ␮m-scale intragranular
(La/Sm)N inclusions and/or as free crystals in the matrix, whereas detrital
0.84 accessory minerals such as zircon and ilmenite are only found as
1.35
1.18

1.36
1.15

0.93
1.31
1.18

1.17
1.03

1.07

1.10
free crystals (Fig. 4A and B). From these, zircon is a potential REE-
bearing phase that can contribute to the REE content of phosphatic
Pr/Pr*

particles. In the studied samples, Zr concentration ranges from 12

0.78
1.19
1.12

1.11

1.13

1.19
1.05

1.20

1.06
1.06

1.09

1.09
to 36 ppm and do not correlate with HREE (R2 = 0.02), this sug-
gests that the REE contribution from zircon is minimal. In addition,
Ce anom

zircons were only found as free crystal in the matrix; we did not
−0.15

−0.24

−0.17
−0.12
−0.23

−0.24
−0.18
−0.10
−0.30
−0.20
−0.30

−0.20
observe zircon occurring as inclusions inside phosphatic particles.
Therefore, the zircon contribution to the REE in phosphatic par-
Ce/Ce*

ticles can be excluded. Dolomite and quartz contain insignificant

0.71
0.79
0.51
0.63

0.58

0.68
0.77
0.59
0.63
0.57
0.66
0.50

amounts of REE compared to CFA and clay minerals, their con-

tribution to normalized
 REE patterns to phosphatic particles are
REE

384.45

114.13

80.94
83.21
55.45
57.67
41.12
377.07
108.10
74.30

141.40

45.90

insignificant. REE correlate against detrital proxies such as Sc



(R2 = 0.68) and this could be explained by mixing with the detri-
tal silicate fraction as laser ablation will also incorporate those
0.969
0.73
0.61
0.29
0.48
0.59

0.28
0.23
0.34
0.22

0.17
0.20

minerals.
Lu
Concentration (ppm) of REE determined by LA-ICP-MS(1) and ICP-MS(2) for phosphatic pellets and coprolites from Metlaoui (Gafsa-Metlaoui basin).

Results of LA-ICP-MS in some  sphalerite and pyrite crystals

6.37
4.76

1.79
3.56
3.64

1.62
1.45
1.62
1.33
0.96
3.80

1.01

(Fig. 4C and D) show that the REE concentrations in both min-

Yb

erals do not exceed 3 ppm, however concentrations of chalocphilic

1.041

TE like As, Cd, Cr, Cu, and Ni are more significant (e.g. As, Cd and
0.72
0.47
0.27
0.37
0.55

0.23
0.22
0.25

0.19
0.15
0.20
Tm

Cu contents in sphalerite averages 50 ppm, 4.1 wt.% and 50 ppm,

respectively, compared to pyrite averages 300, 5 and 2 ppm, respec-
8.22
5.46
4.17
1.92
3.87
3.88

1.76
1.62
1.56
1.44

1.13
1.10
Er

tively). Although they have low REE contents, we suppose that they
contribute substantially to the TE content of phosphatic grains.
2.31
1.82

0.62
1.17
1.23

0.54
0.53
0.48
0.46
0.42
0.35
1.06
Ho

This sheds light on the high Zn and Cd contents that are generally
recorded using conventional acid digestion.
8.83
4.69
2.69

5.14

2.58
1.58
1.97
1.47
13.09

3.90

3.10

1.50
Dy

4.3. REE + Y contents

1.85
1.58
0.65
0.44
0.59
0.85

0.37
0.46
0.25
0.33
0.16
0.25
Tb

REE + Y concentrations (ppm) and elemental ratios are given in

13.48
12.98
3.85
3.53
3.27
6.68

2.75
3.79
1.71

1.49
2.60

2.02

Table 4 in the Supplementary data and reported in Fig. 5 normal-

Gd

ized to PAAS (McLennan, 1989). The concentration values are the

average of several spot analyses on the individual samples as they
2.97
2.38
0.68
0.64
0.84
1.19

0.65
0.78
0.45
0.51
0.28
0.38
Eu

yielded very similar values. It shows that the Sra Ouertane particles
have higher REE contents  (average REE = 570.56 ppm) compared
15.73
10.16
3.88

3.59
4.74

2.79
2.94
1.81
1.86
1.57
1.46
2.60

to the Jebel Jebs (average REE = 547.79 ppm) and Gafsa Metlaoui
Sm

(average REE = 162.3 ppm). The Sra Ouertane samples have rela-
76.71
72.57
18.36
14.32
21.56
26.74

15.21
16.12

10.69
6.92
8.47
9.10

tively high Y contents (166.6–721.33 ppm), while the Jebel Jebs and
Nd

Gafsa-Metlaoui have low Y contents (20–288.6 ppm). PAAS nor-

malized REE patterns for all samples show that HREE are slightly
18.22
13.66
4.79
3.53
5.47
6.46

3.72
3.99
2.44
2.63

2.11
1.90

enriched with (La/Yb)N of 0.49–1.28 and (La/Sm)N of 0.79–1.66.

Pr

Compared to existing data, these values are in the range of those

132.38
147.35
29.49
23.13
31.79
42.24

27.39

17.57
18.44
12.54
15.14
29.70

already reported for Tunisian phosphorites (Tlig et al., 1987; Béji-

Ce

Sassi, 1999; Béji-Sassi et al., 2005; Ounis et al., 2008), and Meso-
and Cenozoic phosphorites of the Tethyan province (McArthur and
91.11

18.53
33.66
37.47

20.57

16.29

11.91
11.76
94.06
31.60

18.80

15.01

Walsh, 1984) in both their REE contents and  distribution patterns.

La

In all samples, the average content of REE is around 458 ppm

Sample reference

in phosphatic pellets whereas the coprolites

 contain approximately
429 ppm. Coprolite rims have higher REE concentration than the
core. However, the REE patterns inner and outside are very similar.
C-ME1 (1)
C-ME1 (2)
C-ME2 (1)
C-ME2 (2)
C-ME3 (1)
C-ME3 (2)
P-ME1 (1)
P-ME1 (2)
P-ME2 (1)
P-ME2 (2)
P-ME3 (1)
P-ME3 (2)

Ce anomalies, calculated after Wright et al. (1987), are always

negative; they vary from −0.71 to −0.12. However, they are more
negative in the Sra Ouertane (−0.71 to −0.29) compared to Jebel
Phosphatic pellets

Jebs and Gafsa-Metlaoui (−0.34 to −0.12). Through the sections,

there is an inverse correlation between the Ce anomaly and the
Description

(La/Sm)N , (Dy/Sm)N ratio and Y/Y* (Fig. S1, supplementary data).

Coprolites

Slight positive Eu anomalies appear in the Sra Ouertane (0.77–2.29)

Table 3

and Jebel Jebs (1.17–1.89), while less Eu anomalies were reported

for Gafsa-Metlaoui (0.39–1.12). All particles have slightly positive Y
134 H. Garnit et al. / Chemie der Erde 72 (2012) 127–139

Fig. 4. BSE images showing some accessory minerals associated to phosphorites (A) Free zircon crystal in phosphorite sample from Sra Ouertane (Jebel Ayata). (B) Ilemnite
crystal in phosphorite sample from Sra Ouertane (Jebel Ayata). (C) Pyrite in Gafsa-Metlaoui sample occurring as intergranular cement and (D) Free Cd-rich sphalerite crystal
recognized in a heavy fraction ( > 2.89 g/cm3 ), ablation crater of LA-ICP-MS analysis is visible on the left side of the crystal.

anomalies with Y/Y* of 1.27–2.42 and high Y/Ho ratios of 35.5–66,
which have an average value of 47.85.
Some coprolites show a slight increase of Ce/Ce* and Eu/Eu* and
decrease of Y/Y* values from the cores to rims, whereas the varia-
tion of Ce/Ce* in phosphatic pellets are less significant. Apart from
the magnitude of Ce anomalies, the shape of the phosphatic pellet
and coprolite-REE patterns are mostly similar. They are, in general
HREE-enriched; although in detail they are characterized by sys-
tematic REE enrichment relative to shale up to Gd with a variable
depletion between Tb and Yb.
Phosphatic pellets and coprolites are characterized by (Dy/Yb)N
ratios varying between 0.72 and 1.37, which is close to that of
modern seawater values (0.8–1.1; Shields and Webb, 2004). Binary
cross-correlation plots of various parameters calculated from the
shale-normalized REE abundance show two clusters of values, one
corresponding to the samples from the Sra Ouertane, the other cor-
responding to the samples from the Jebel Jebs and Gafsa-Metlaoui
(Fig. S1, supplementary data).
4.4. TE contents
The TE data (ppm) are given in Table 5 in the Supplementary data
and reported in Fig. S2, supplementary data to explore the dis-
tribution of the TE contents versus average shale (adapted from
Wedepohl, 1971, 1991) according to particle types and localities. In
order to examine enrichment, depletion and normality, enrichment
factors are calculated as mean elemental concentration/average
shales. It is considered here, as in Bech et al. (2009), that there
is enrichment for ratios >2; normal concentrations are associated
with ratios ranging from 0.5 to 2; and ratios under 0.5 indicate
depletion.
For all samples from the three areas Cd, Cr, Sr and U exhibit mod-
erate to high enrichments compared to average shales, Mo and Zn
show ‘normal’ concentrations, while As, Ba, Co, Cu, Mn, Ni, Pb, Sc,
Th, V, and Zr are generally depleted. All sections exhibit similar-
ities in TE abundance patterns displayed as U > Cd > Sr > Cr for Sra
Ouertane (Fig. S2, supplementary data), as Cd > U > Sr > Cr for Jebel
Jebs (Fig. S2, supplementary data), and as Cd > U > Sr > Zn > Cr for
Gafsa-Metlaoui (Fig. S2, supplementary data).
Comparison between the enrichment, depletion and normal-
ity data for pellets, coprolite cores and rims shows analogous
in TE abundance patterns. However, phosphatic pellets show
slight enrichment in TE compared to coexisting coprolites. Slight
increases in Cr, Ni, Th, and V concentrations from core to rim are
observed in some coprolites, while decreases are observed for Ba,
Cd, Cu and U.
Phosphatic particles from the Sra Ouertane show the highest
contents of Ba, Cu, Ni, and U, whereas phosphatic particles from
 H. Garnit et al. / Chemie der Erde 72 (2012) 127–139
Fig. 5. PAAS-normalized REE + Y patterns exhibit general consistency (Y inserted between Dy and Ho according to its ionic radius, as was predicted by Byrne and Lee, 1993).
(A) The Sra Ouertane patterns are characterized by pronounced negative Ce anomalies and relative enrichment of HREE. (B) Jebel Jebs, (C) Gafsa-Metlaoui, and (D) box plot
comparing REE content of phosphatic particles from three basins.
the Jebel Jebs and Gafsa-Metlaoui show the highest Cd, Mo, Sr and
Zn. The values obtained for As, Co, Mn, and Pb are mainly lower
than in average shales and do not allow a clear sample distinction
according to particle types and locality.
Some pairs of elements show positive correlations reflecting
geochemical affinities, namely Cu-Ba (R2 = 0.62), Cu-U (R2 = 0.55),
Zn-Cd (R2 = 0.62), U-Sc (R2 = 0.82), and U-Ba (R2 = 0.69), which point
to their probable common sources and enrichment processes in
phosphatic particles.
TE contents in the studied samples varied slightly in the different
deposits even within different levels of the same deposit. In gen-
eral, phosphatic particles from Gafsa-Metlaoui and Jebel Jebs have
homogenous TE levels and trends. Binary cross-correlation plots of
various TE show two clusters of values, one corresponding to the
samples from the Sra Ouertane, and the other corresponding to the
samples from the Jebel Jebs and Gafsa-Metlaoui (Fig. S3, supple-
mentary data).
5. Discussion
5.1. Do REE contents in the two archives record seawater
compositions?
REE concentrations, REE patterns, Ce and Eu anomalies in marine
phosphorites are useful indicators of marine depositional environ-
ments (e.g. Jarvis et al., 1994; Ilyin, 1998). However, REE signatures
135
can be altered by diagenesis (Shields and Stille, 2001). Therefore,
using REE signatures of phosphorites to reconstruct paleoenviron-
ments should be done with caution.
Phosphatic pellets and coprolites mineralize, after their for-
mation, at the seafloor and/or in the upper part of sediment.
Such particles form close to the seawater-sediment interface, and
become phosphatized relatively rapidly in most marine environ-
ments which ensures early exposure to seawater. Accepting that
no late alteration and no large-scale reworking occurred, preserved
particles (as they retain the external original morphology and inter-
nally mineralized bacterial shapes), constitute a better alternative
as a proxy material for seawater REE composition.
The effects of diagenesis on our samples were tested using
the diagram proposed by Reynard et al. (1999). All samples from
these three basins have (La/Yb)N ratio between 0.49 and 1.28 and
the (La/Sm)N ratios between 0.79 and 1.66. Compared with data
for modern oceanic water: 0.2–0.5 for (La/Yb) and 0.6–1.6 for
(La/Sm), provided by Reynard et al. (1999), all samples from these
three basins have high (La/Yb)N ratios compared to the modern
ocean. Phosphatic pellets and coprolites group together, close to
the domain defined by well-preserved Tertiary apatites. The trend
toward higher (La/Yb)N ratios has been interpreted by Reynard
et al. (1999) as a progressive mechanism of REE adsorption onto
the apatite lattice during early diagenesis (Fig. 6).
Shields and Stille (2001) indicated values between 1.5 and 2.3 for
Y anomaly and 0.8–1.3 for La/Nd ratio in modern water. The yttrium
136 H. Garnit et al. / Chemie der Erde 72 (2012) 127–139
Fig. 6. Compilation of normalized (La/Yb)N ratios versus (La/Sm)N ratios of Tunisia
phosphatic particles reported in the diagram proposed by Reynard et al. (1999).
(La/Sm)N ratios are similar to modern seawater, whereas their (La/Yb)N ratios are
globally higher as indicating by value shifting along vertical adsorption arrow.
anomaly in our samples varies from 1.2 to 2.4 and La/Nd ratio
varies from 1.03 to 2.04. Most values found in the analyzed par-
ticles are equivalent to those of seawater, indicating that Tunisian
phosphatic particles did not undergo intense diagenesis. Coprolites
show decreases in the Y anomaly and La/Nd ratio from core to rim,
possibly resulting from changed redox conditions during coprolite
growth.
Thus we assume that the REE pattern in our samples is the
result of primary precipitation from seawater or porewater in the
sediment during early diagenesis and provides a powerful source
of information regarding the geochemistry of the environment of
deposition.
5.2. REE distributions
The REE patterns are highly consistent despite representing
samples widely spaced in both geographic location and time. The
seawater-like REE patterns of the phosphatic particles strongly
support an origin for the REE ultimately from seawater with no
significant fractionation. The identical REE patterns from differ-
ent phosphorite sample types and deposit suggest a common REE
source. Negative Ce anomalies and weakly positive Eu anomalies
show that weathering did not obviously contribute to an increase
in REE. Lower REE contents in the Gafsa-Metlaoui samples could
be explained by low pore water enrichment in bottom sediments
with REEs and/or minimal incorporation of detrital REE from clastic
phases in the CFA-fraction.
Independently of depositional environment, phosphatic pellets
seem to be more REE-enriched relative to the coexisting coprolites.
This observation is in agreement with our knowledge that pellets
have a higher specific surface area and their nanostructure is more
porous than coprolites. Coprolite has a compact structure com-
posed of hexagonal apatite crystals arranged in all directions. Such
structure close intracrystalline pore spaces, limiting permeability
and preventing further diffusion of REE + Y within coprolite.
Our data show also that the total REE concentrations in copro-
lites are slightly higher in the rims than in the cores. Concentrations
of LREE rises more quickly than those of HREE, reflecting differences
in adsorption coefficient and indicating that REE are fractionated
from one another during uptake within coprolite. This result is
broadly similar to the results obtained for phosphatic nodules from
black shales of the a Pennsylvanian-Mississippian age deposit in the
USA (Kidder et al., 2003) and phosphatic nodules from the lower
Cambrian black shale sequence in the Mufu mountain of Nanjing
in China (Jiang et al., 2007). According to Jiang et al. (2007) the rim
REE-enrichment is possibly from the result of significant diagenetic
effect, with REE-rich pore fluid deriving after organic decay dur-
ing later diagenesis, expressed by MREE-rich and HREE-depleted
patterns, whereas nodules cores record the original seawater like
patterns.
In our case, seawater-like REE patterns are common in copro-
lite cores and rims, suggests that coprolite cores and rims have
recorded the seawater REE characteristics that did not altered by
post depositional diagenetic exchange, therefore higher total REE
concentrations in rims could support an adsorption, or substitution
or recrystallization processes. Regarding (La/Yb)N and (La/Sm)N
ratios for coprolite, it is found that (La/Sm)N are similar to mod-
ern seawater, whereas their (La/Yb)N ratios are globally higher and
shifting along vertical adsorption arrow.
5.3. Ce and Eu anomalies as paleoseawater redox indicators
Cerium anomalies in phosphorites have been used in previous
studies to infer redox conditions during early diagenesis, with the
premise that negative anomalies indicate oxidizing conditions at
the time of REE uptake (German and Elderfield, 1989). Positive Ce
anomalies suggest diagenesis under more reducing conditions or in
the presence of saline alkaline-rich waters (German and Elderfield,
1989; Möller and Bau, 1993). Therefore, if the marine sediments
have inherited the Ce-anomaly from the seawater without serious
modifications, the obtained information can be used as a tracer to
distinguish between anoxic and oxic water columns in the geolog-
ical past (Wright et al., 1987; Grandjean et al., 1987).
Following the method of Bau and Dulski (1996), both Ce and
Pr anomalies were calculated for all samples. Using this method
to evaluate the effect of lanthanum enrichment, we find that our
samples all plot in area IIIb, although exceptions exist for two
samples from the Gafsa-Metlaoui basin, which suggests that the
negative Ce anomalies are real in most samples and can there-
fore be used for paleo-redox interpretations (Fig. 7). Ce anomalies,
calculated for all studied samples, are always negative and they
vary from −0.09 to −0.71. However, they are more negative in
the Sra Ouertane samples (mean Ce anomaly = −0.54) compared to
Gafsa-Metlaoui (mean Ce anomaly = −0.23) and Jebel Jebs (mean
Ce anomaly = −0.19). Cross
 plots of Ce/Ce* versus La/Yb, (Dy/Sm)N ,
(La/Sm)N , Y/Y* and REE show two clusters of values, one
corresponding to the samples from the Sra Ouertane, the other cor-
responding to the samples from the Jebel Jebs and Gafsa-Metlaoui,
suggesting that the oceanographic conditions under which the
eastern and Gafsa-Metlaoui deposits accumulated were likely sim-
ilar. If all Ce anomalies are comparable in amplitude to modern
surface seawater values for the Pacific and Atlantic oceans (Ce
anomaly = −0.8 to −0.3), the weak Ce anomalies recorded within
Jebel Jebs and Gafsa-Metlaoui samples (mean = −0.21) could sug-
gest the onset of more reducing conditions in the southern and
eastern basins. Some coprolite cores show pronounced negative
Ce anomalies, while their rims display less a lesser Ce anomaly.
It is likely that the early stage of coprolite mineralization may
occur with direct contact with the seawater, and more likely leads
to retention of a seawater-like Ce anomaly. The later stage tends
to undergo additional adsorption process and reducing conditions
during REE scavenging.
Europium anomalies are negligible in the Gafsa-Metlaoui sam-
ples ranging from 0.39 to 1.12 and averaging 0.76. However, more
positive Eu anomalies characterize all samples of the Jebel Jebs
(range from 1.17 to 1.89 and average 1.50) and Sra Ouertane (range
 H. Garnit et al. / Chemie der Erde 72 (2012) 127–139
Fig. 7. Ce/Ce* vs. Pr/Pr* diagram after Bau and Dulski (1996). Field I: no anomaly;
Field IIa: positive La anomaly causes apparent negative Ce anomaly; Filed IIb: neg-
ative La anomaly causes apparent positive Ce anomaly; Field IIIa: real positive Ce
anomaly; Field IIIb: real negative Ce anomaly; Field IV: positive La anomaly disguises
positive Ce anomaly. Except two samples from Gafsa-Metlaoui basin, all samples dis-
play real, negative Ce anomalies. Sra Ouertane samples clearly show higher Pr/Pr*
and lower Ce/Ce* ratios. Gafsa-Metlaoui and Jebel Jebs samples are tightly grouped.
from 0.77 to 2.29 and average 1.61), which also shows Ce depletion;
exhibit seawater-like HREE enrichment and a positive Y anomaly.
The positive Eu anomalies are normally interpreted as having
resulted from precipitation of sediment under extremely reduc-
ing and alkaline conditions (Ogihara, 1999; Kidder et al., 2003;
Jiang et al., 2007) or alternatively, may represent a detrital sig-
nature inherited from Eu-rich feldspar (Shields and Stille, 2001)
where Eu2+ may replace Sr2+ due to their similar ionic radii. In
the absence of any hydrothermal influence, detrital feldspar and/or
aeolian input, we believe that the positive Eu anomalies were more
likely caused by reducing conditions where Eu2+ can replace Ca2+
in the CFA lattice and this interpretation is consistent with the rel-
ative increase of Eu/Eu* values from the cores to rims in coprolites.
If this were the case, the degree of the Eu anomaly would indicate
that the sedimentary environment had changed from suboxic to
anoxic conditions.
5.4. Paleoredox and paleoproductivity proxies
In order to use TE as redox and productivity proxies to recon-
struct paleoenvironmental conditions, one must assess whether
they are enriched or depleted (Tribovillard et al., 2006). Commonly,
the degree of enrichment or depletion of a TE in a sample is evalu-
ated relative to its concentration in average shale (Wedepohl, 1971,
1991). Among the redox-sensitive elements such as Cr, Mn, Mo, U,
and V only Cr, Mo and U show moderate to high enrichment. In
addition, among the trace metals usually considered to be influ-
enced by the organic matter supply such as Cd, Co, Cu, Ni, and Zn,
only Cd and Zn are enriched in these samples.
In general, all phosphatic particles analyzed do not present any
enrichment in V and only moderate enrichments for Mo and Cr
with respect to average shale, suggesting the absence of severely
reducing conditions during deposition.
Accordingly, the relatively higher concentrations of Cr and Mo
in Jebel Jebs and Gafsa-Metlaoui samples suggest more reducing
conditions during the deposition of these phosphorites compared
to those of the Sra Ouertane area. The high U concentrations in
the Sra Ouertane (average of 114 ppm) compared to those of the
137
Jebel Jebs (average of 39 ppm) and those from the Gafsa-Metlaoui
(average of 29 ppm) contrast with the above-mentioned conclusion
that the Jebel Jebs and Gafsa-Metlaoui were deposited under more
reducing conditions compared to those for Sra Ouertane.
Uranium content in all samples has been shown to track the
Ce anomaly in an inverse fashion (R2 = 0.78), with greater Ce
depletion related to greater U concentration (Fig. S3G, supple-
mentary data). This inverse correlation reflects the fact that U is
more mobile in its oxidized state, and is apparently more readily
incorporated into CFA undergoing diagenesis in well-oxygenated
settings.
The relative Mo enrichment observed in Gafsa-Metlaoui sam-
ples advocates for more reducing conditions, whereas all the other
parts of the two sections studied indicate suboxic conditions (no
Mo-enrichment but relative enrichment in U). Mo enrichment
appears to require lower O2 levels or higher H2 S levels than V
enrichment, possibly because precipitation of V-oxyhydroxides
commences in the semi-reduced state (e.g., V (IV)) or because
free H2 S is required for complete reduction of thiomolybdates to
MoS4 2− prior to uptake by authigenic Fe-sulfides. In the studied
sample from the three area there is no significant enrichment of Mo
(except for a few samples from Jebel Jebs and Gafsa-Metlaoui where
5.1 < Mo < 7.6 ppm), which suggests that sediments never attained
truly anoxic conditions during this time.
Ba, as well as Cu, and Ni show noticeable variations from the
northern basin to eastern and Gafsa-Metlaoui basins. In Sra Ouer-
tane, the concentrations of U, as well as markers of productivity
(Ba) and organic matter-related trace elements (Cu, Ni), are gener-
ally elevated throughout the Gafsa-Metaloui and Jebel Jebs. The Sra
Ouertane samples richest in Ba are not necessarily those recording
the highest productivity. However, the Ba and Cu enrichments are
observed in the same samples. As Cu in not known to be moved
during early diagenesis, the good Ba-Cu covariations (R2 = 0.61) are
an indication that Ba content was probably not deeply affected by
post-deposition migrations.
Cadmium contents are higher at Jebel Jebs and Gafsa-Metlaoui,
and these high concentrations suggest anoxic conditions. In con-
trast, the low Cd contents at Sra Ouertane probably suggest
sedimentation in suboxic conditions.
5.5. Paleoenvironmental interpretations
Although the same paleo-oceanographic processes were likely
involved in phosphorite deposition across the three basins, a cer-
tain degree of spatial variability in nutrient availability, intensity
of anoxia, and stratification of the water-column is evident due to
different basin configuration and connection with Tethyan waters.
From the above-mentioned results, it can be observed that the dis-
tribution of the TE and REE + Y in the late Paleocene-early Eocene
phosphorites possesses a spatial distribution although the phos-
phatic constituent in the studied three localities is the same. Binary
cross correlation of various TE and REE + Y parameters reveal that
phosphorite deposition in the Eastern and Gafsa-Metlaoui basins
occurred under nearly similar paleo-oceanographic conditions.
The REE contents of our samples do not seem to have been seri-
ously disturbed by a process of late diagenetic alteration according
to the terminology used by Reynard et al. (1999). The seawater-like
REE patterns of phosphatic particles strongly support an origin of
the REE (and probably also other elements) ultimately from seawa-
ter. Sra Ouertane samples are characterized by higher REE contents
and significantly more pronounced negative anomalies and this
suggests that oxidation was more pervasive within the early dia-
genetic environment of the northern basins. This reconstruction
is consistent with the sedimentology of the phosphorite series
of Sra Ouertane, which is characterized by abundant carbonate
nodules (CaCO3 ) a relative dearth of macroscopic phosphatic and
138 H. Garnit et al. / Chemie der Erde 72 (2012) 127–139
carbonaceous debris and abundant galuconite and smectite. In con-
trast, the Gafsa-Metlaoui phosphorites which are characterized
by facies that shows more indication of reduction in the form of
abundant phosphatic and carbonaceous debris and precipitation of
Zn-Cd and Fe sulfides.
Higher positive Eu anomalies suggest large contributions of
hydrothermal fluids to the seawater involved in CFA formation.
However, the Gafsa-Metlaoui samples exhibit much lower and
more constant Eu/Eu* values. This implies that the REE chemistry of
the basin water was mainly influenced by redox conditions, but we
cannot totally rule out the contribution of hydrothermal fluid to the
phosphorite formation, since a number of studies have suggested
Paleocene-early Eocene alkaline volcanic supply for a number of
minerals and dissolved elements (Clocchiatti and Sassi, 1972; Béji-
Sassi et al., 2001).
The difference in Ce and Eu anomaly amplitude can be explained
by the paleogeographical position of the studied basins. The Gafsa-
Metlaoui basin is an intracratonic basin situated between two
emerged areas, the Kasserine Island to the north and the Jeffara
Island to the south. This basin was to some extent isolated from the
ocean and the nearby emerged areas, whereas the northern basins
were directly connected with Tethyan water, which was the dom-
inant source of REEs and therefore pellets and coprolites inherited
the typical features of that seawater.
Ba, Cu, Ni, and U are enriched in phosphatic particles from
Sra Ouertane whereas Cd, Mo, Sr, and Zn contents are higher in
phosphatic particles from Jebel Jebs and Gafsa-Metlaoui. The con-
trasting record of paleoproductivity between the northern and
Gafsa-Metlaoui basins may be explained by organic productiv-
ity on platforms may be high as a consequence of an enhanced
nutrient flux from upwelling, which may favor the onset of sub-
oxic conditions and organic matter burial. Nevertheless, largely
unstratified and well oxygenated do not allow good accumulation
and preservation of organic matter. In basins, where terres-
trial inputs are lower, primary productivity was seemingly high.
Organic matter preservation was high due to a marked oxygen
deficiency, increased contents of Cd and Zn, as well the pres-
ence of sulfide minerals point to sulfate reduction and episodic
anoxic, formed secondarily followed the degradation of organic
matter.
Although close to terrigenous sources, the relative low abun-
dance and uniform distributions of Ti and Zr could reflect a fair
eolian input during the deposition. This interpretation is sup-
ported by oxygen isotope compositions of the structural phosphate
(␦18 PO4 ) in coprolites and shark teeth from Gafsa-Metlaoui basin,
which indicate a stable and warm climate, during the Paleocene-
Eocene time (Ounis et al., 2008). The relatively low detrital influx
is suggestive also of a low-relief hinterland in the Kasserine
Island.
The similarity of lithology in Gafsa-Metlaoui and Jebel Jebs
suggests that these deposits accumulated under similar oceano-
graphic conditions, relatively moderate primary productivity and
O2 depletion in the suboxic to seldom anoxic bottom waters.
The geochemical interpretation inferred from TE and REE is also
consistent with data from clay minerals. The more restricted
(littoral-lagoonal) environments to the south and east of the
emerged area are indicated by occurrence of evaporites, cherts,
and a clay mineral assemblage represented by smectite, attapulgite
and sepiolite. In the less restricted depositional environments to
the north the clay mineral assemblage is composed of smectite-
glauconite. The existence of shallow restricted basins between
emerged areas is favorable to the neoformation of palygorskite
and sepiolite during warm and arid climatic conditions where alka-
line waters are concentrated by evaporation, leading to solutions
enriched in Si and Mg which favor the formation of palygorskite
and/or smectite.
6. Conclusions
Phosphatic pellets and coprolites from the main phosphorite
occurrences in Tunisia were analyzed using LA-ICP-MS. The results
show general consistency with previous work based on standard
acid digestion techniques which illustrates the great potential of
applying laser ablation technique for microscale spectrometric
measurement in sedimentary phosphatic particles.
Normalized REE + Y patterns exhibit general consistency within
localities and grain types indicating that phosphatic pellets and
coprolites experienced the same early diagenetic environments.
The relatively high REE and TE contents correlate with porosity and
the specific surface area of cryptocrystalline apatite.
According to the TE and REE data the paleodepositional envi-
ronment in northern basins was different from eastern basins and
Gafsa-Metlaoui basins. The former basins likely had a more direct
connection with the open sea resulting in high REE + Y contents,
marked negative Ce anomalies, and Ba, Cu and U enrichment.
Acknowledgements
First author is grateful to all the Gafsa Phosphate Company (CPG)
geologists who assisted field work in Gafsa-Metlaoui basin. Gra-
ham Shields is thanked for improvements of an earlier version of
the manuscript. We are grateful to Editor-in-Chief Klaus Heide and
other anonymous reviewers for their constructive comments which
improved the quality of the paper.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.chemer.2012.02.001.
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