Clay Minerals (2003) 38, 187199

Palygorskite genesis through silicate transformation in Tunisian continental Eocene deposits

F . J A M O U S S I 1, A . B E N A B O U D 2
1

AND

A . L O P E Z - G A L I N D O 2,*

Laboratoire Georessources, INRST BP 95, 2050 Hamam-Lif, Tunisia, and 2 Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Facultad de Ciencias, Fuentenueva s/n, 18002 Granada, Spain

(Received 30 April 2002; revised 21 October 2002) A B S T R A C T : The mineralogical and geochemical characteristics of Eocene continental sediments in south central Tunisia (Chebket Bouloufa and Jebel Hamri) and in north central Tunisia (Jebel Lessouda and Jebel Rheouis), which contain considerable amounts of palygorskite, were studied. The clay fraction of the sediments also comprises illite, kaolinite, Mg smectite and Al smectite, together with carbonates (calcite and/or dolomite), quartz, gypsum and feldspars, all of which are present in extremely variable proportions. The textural characteristics of the samples containing most palygorskite, as well as the chemical composition of the fibres and the contents of certain trace and rare earth elements suggest that the genesis of this fibrous clay is intimately linked to the diagenetic transformation of illite, mixedlayered minerals and/or Al smectite, as has also been observed in contemporaneous deposits in Morocco.

KEYWORDS: palygorskite, illite, Tunisia, Eocene.

With the aim of drawing a map of potentially useful clays in Tunisia, a systematic survey of the Palaeozoic to Quaternary sediments has been performed over the last few years by one of the authors (F.J.). The survey showed numerous palygorskite-rich Eocene levels that might be of economic interest. In Tunisia, Eocene sediments present important facies variations from South to North, changing from continental to deep marine deposits (Bishop, 1988; Jamoussi et al., 2001a; Fig. 1). These changes in facies and thickness are mainly due to Alpine compressive tectonic events and the halokinetic movements of Triassic materials affecting the Central Atlas domain during the Eocene (Bedir, 1995; Boukadi & Bedir, 1996).

* E-mail: alberto@ugr.es DOI: 10.1180/0009855033820088

Continental Eocene facies, studied by numerous authors, are deposited in two main areas: in central Tunisia, around the so-called Kasserine island (Burollet, 1956), and to the south of the Gulf of Gabes and the northern part of Jeffara. In central ` Tunisia, Truc (1981) and Zouari (1984) found Eocene sediments at Jebel (J.) Chaambi and Sassi et al. (1984) found them on the south-eastern flank of the J. Kebar. In the J. Lessouda and Koumine, Kadri et al. (1986) and Kadri (1988) detected the same facies, but Jamoussi (2001) pointed out that they were not immediately above the Ypresian carbonate bar. In the northern area of the Chotts belt, Abdeljaoued (1983, 1991, 1997) defined the continental formation of Bouloufa, dated by bulimes (continental gastropods) as Lower Eocene; in J. Rheouis and Boudinar, around the Kasserine island, continental deposits were also discovered and in J. Chamsi such sediments have been suspected (Jamoussi, 2001; Jamoussi et al., 2001a). Finally,

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ALG ERI A

Tunis

Mahdia
J. Rhouis

J. Lessouda

Gafsa
J. Bouloufa

* *J. Boudinar Sfax ** J. Hamri

Gabs Jerba

Kerkennah Island

N
0 50 100 km

Medenine

Emerged area

Tidal zone (Sebkha) Supratidal to tidal zone Nummulitic limestone Marine deposits

Sections investigated

FIG. 1. Lithofacies map of the Lower Eocene in Tunisia (modified from Jamoussi et al., 2001) and the locations of the sections studied.

the first oil drilling carried out in the southern part of the Gulf of Gabes, as well as some drilling in the ` northern part of Jeffara, found continental Eocene deposits known as the Tanit Formation (Pochitaloff, 1968). The mineralogy of some of these deposits has been described by, among others, Abdeljaoued (1997), Srasra et al. (1995), Ben Aboud (1998), Hachi (1998), Ben Aboud et al. (1999), Fakhfakh (1999) and Jamoussi (2001). In this paper we study the mineralogy, geochemistry and microtexture of palygorskite-rich Eocene

samples in Tunisia. The better sequences are located in some of the above-mentioned areas (Chebket Bouloufa, J. Hamri, J. Lessouda and J. Rheouis). Some samples from J. Boudinar were also studied.

GEOLOGICAL SET TING

The end of the Cretaceous is marked in central and southern Tunisia by important palaeogeographical and sedimentological modifications. Marine sedi-

LIB YA

Phosphate deposits

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mentation, represented by white limestones with inoceramids and echinoderms, known as the Abiod Formation (Burollet, 1956), changes towards a more detrital, clayey sediment during the Palaeocene. After compressive tectonic movements of transverse faults during the Upper Cretaceous (Zargouni, 1985; Boukadi, 1994; Bedir, 1995) some emerged areas appeared, such as the above-mentioned Kasserine Island. Tertiary sequences are particularly well represented in the North Chain of the Chotts, and include several lithostratigraphic units, such as Beglia and Segui Formations, consisting of sand, clay and conglomerates. One particular lithological member was defined by Abdeljaoued (1983) as the Bouloufa Formation, extending over a wide area on the southern edge of the Gafsa-Metlaoui phosphate basin. This formation appears, in most cases, as calcretes and dolocretes, with vacuolar appearance. At J. Chambi, Sassi et al. (1984) found one faunal assemblage consisting of continental gastropods (R oma nella hopii, Vidaliella) and helicids (Paleocyclotus) that allowed this formation to be dated as Lutecian-Bartonian. The most representative sequences of the Bouloufa Formation crop out 25 km northwest of El Hamma town, at J. Bouloufa and J. Hamri. They are ~150 m thick and are made up of alternating conglomerates, marls and limestones, white and red in colour, with some gypsum and silex nodules. The Eocene deposit located at J. Rheouis, close to a Triassic diapir (Soussi et al., 1996), is situated in central Tunisia, 10 km to the south of Fad, on the boundary between the Sidi Bouzid and J. Goubrar 1:50,000 topographic maps. It appears in the intersection of NE SW structures of the North South Axis, known as J. Goubrar and Boudinar, and the NW SE fold of J. Ksara (Boukadi and Bedir, 1996). Triassic halokinetic movements along transverse faults led to cropping out of these structures, particularly during the Eocene (Boukadi and Bedir, 1996). The sequence is ~40 m thick, and is made up of white and grey limestones and marly limestones, marls and clayey marls. Some fine gypsum intercalations appear occasionally. Finally, J. Lessouda is situated ~10 km to the North of Sidi Bouzid town, at the western part of the NorthSouth Axis. It constitutes a N40E anticline superimposed on an Upper Cretaceous diapiric dome (Creuzot and Ouali, 1989), emerging in the centre of a vast plain. It is fractured by kmlong N S, NW SE and E W faults, which have

synsedimentary influences on the distribution of facies and their thickness from Upper Cretaceous until Middle Miocene (Kadri, 1988). The sequence, ~20 m thick, is made up of alternating white, red and green marls, with fine intercalations of gypsum. Although the presence of bulimes in these continental Eocene deposits clearly indicates a Lower Eocene age, recurrences of continental facies seem to be diachronic and closely influenced by local tectonic conditions of the geological substratum. The mineralogy of the clay fraction, and particularly the presence of palygorskite, could be an element of identification and inter-relationship between these series, which have been marked by compressive movements and halokinetics of Triassic rocks.

ME THODOLOGY
The mineral phases were determined by X-ray diffraction (XRD), using Philips PW 1710 and Siemens Kristalloflex 810 diffractometers, Cu-Ka radiation at a scan speed of 2 to 62y min 1. Analysis was performed on both the whole sample and the clay fraction. Oriented aggregates were prepared for clay mineral analysis and were then treated with ethylene glycol, dimethyl-sulphoxide and heating to 550C for 1 h. The reflecting powers of Schultz (1964), Biscaye (1965) and Barahona (1974) were used to quantify the different mineral phases detected, as well as the chemical compositions of samples (Lo pez-Galindo et al., 1996). Major elements were analysed by atomic absorption spectrometry, using Perkin Elmer equipment with acetylene or protoxide acetylene flame t. Trace and rare earth elements (REE) were measured using an ICP-MS Perkin Elmer SCIEX Elan-5000 device. The detection limits of the elements were 10 ppb for REE and Th, 100 ppb for transition elements and Cs, Rb, Sr, Ba and Pb, and 1000 ppb for Li and B. The scanning electron microscope (SEM) observations were performed using a Zeiss DSM 950 (equipped with LINK microanalysis system). The transmission electron microscope (TEM) observations and microanalyses were carried out on the clay fraction of selected samples, using a Philips CM 20 (equipped with an EDAX microanalysis system). Factor analysis (Principal Components Analysis, PCA) was used to establish the relation between the different minerals and major and trace element

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contents. The factors (principal components, Pcs) were selected for eigenvalues >1 (Swan & Sandilands, 1995) applying a Varimax rotation.

RESULTS Mineralogy
In Fig. 2 the bulk and clay mineralogy of the four most representative sequences mentioned above are given. Table 1 contains the average geochemical characteristics of these.

Two clearly distinguished groups of palygorskiterich outcrops can be established: those located in south central Tunisia (J. Bouloufa and J. Hamri), which contain considerable amounts of quartz, calcite and kaolinite, and those located in north central Tunisia (J. Rheouis and J. Lessouda), with dolomite as the most distinctive mineral. Thus, at J. Bouloufa the samples comprise phyllosilicates, carbonates, quartz, gypsum and traces of feldspar. With the exception of the bottom of the sequence, where quartz and gypsum are the main phases, carbonates (calcite and

TABLE 1. Average geochemical data for the sequences studied. J. Bouloufa J. Hamri Major components in the clay fraction SiO2 53.88 53.17 58.44 Al2O3 16.59 21.34 10.68 Fe2O3 3.52 3.51 3.35 MgO 7.24 5.21 9.41 CaO 0.29 0.47 0.33 Na2O 0.20 0.40 0.17 K2O 2.25 3.13 1.41 TiO2 0.18 0.28 0.14 Mn2O3 0.04 0.04 0.04 LOI 15.39 12.28 15.58 J. Rheouis J. Lessouda 56.72 14.28 3.47 7.77 0.33 0.21 2.29 0.19 0.04 14.32 J. Bouloufa J. Hamri J. Rheouis J. Lessouda 20.54 32.43 3.36 10.80 1.71 0.37 1.21 0.20 1.23 0.25 0.71 0.12 0.72 0.12

Trace element contents in the clay fraction Ni 28.7 38.2 13.1 13.3 Co 7.4 9.7 5.2 6.9 Sr 98 219 50 106 Ba 142 194 82 76 V 107 119 69 95 Cr 101 107 80 92 Zn 118 165 78 108 Cu 14.9 26.6 7.2 10.4 Li 40 74 78 86 Y 5.3 7.7 5.0 9.2 Rb 115 124 84 93 Zr 119 136 154 192 Nb 21.9 24.1 29.4 36.2 Cs 5.8 5.9 4.0 4.7 Hf 3.1 3.6 3.7 4.8 Th 6.6 7.8 4.5 8.6 U 1.2 1.4 1.0 3.6 Be 2.5 2.8 1.7 1.8 Sc 11.7 13.8 8.0 10.5 Ga 25.1 26.7 18.0 22.2 Ta 1.6 1.8 2.0 5.1 Mo 2.0 2.0 0.8 1.5 Sn 2.1 2.3 1.7 1.8 Pb 9.3 13.4 0.3 0.4 Tl 0.6 0.9 6.4 9.4

REE contents in the clay fraction La 24.45 29.64 21.58 Ce 38.42 59.62 32.31 Pr 3.92 4.60 3.35 Nd 12.25 14.50 10.77 Sm 1.83 2.25 1.62 Eu 0.35 0.41 0.33 Gd 1.26 1.58 1.16 Tb 0.19 0.25 0.18 Dy 1.14 1.45 1.06 Ho 0.23 0.30 0.21 Er 0.65 0.87 0.58 Tm 0.11 0.14 0.10 Yb 0.71 0.92 0.64 Lu 0.11 0.14 0.10

Structural formula of palygorskites (AEM data) Si 7.65 7.70 7.85 7.64 Al IV 0.35 0.30 0.15 0.36 Mg 1.91 1.54 1.76 2.04 Fe3+ 0.51 0.53 0.45 0.58 Al VI 1.48 1.73 1.64 1.35 Ca 0.09 0.07 0.06 0.08 Mn 0.03 0.03 0.01 0.02 Ti 0.04 0.02 0.02 0.05 K 0.11 0.17 0.13 0.11 Granulometry of samples (%) <1 mm 78.26 76.14 1 2 mm 15.84 16.61 2 3 mm 2.79 2.86 3 4 mm 1.59 2.14 4 5 mm 0.81 1.06 5 7 mm 0.60 0.87 7 10 mm 0.11 0.23 10 20 mm 0.00 0.10 >20 mm 0.00 0.00 Mean 1.02 1.07 71.83 19.07 4.09 2.12 1.56 0.93 0.26 0.14 0.01 1.13 74.58 17.35 3.73 2.06 1.06 0.92 0.20 0.11 0.01 1.09

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FIG. 2. Bulk and clay mineralogy of the Tunisian Eocene sediments studied.

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Calcite + Dolomite

F. Jamoussi et al.
Illite + Kaolinite

J. Bouloufa J. Hamri J. Rheouis

50

J. Lessouda J. Boudinar

50

50

Phyllosilicates

50

Quartz + Feldspar

Al smectite

50

Palygorskite + Mg smectite

FIG. 3. Mineralogical composition of the samples studied.

dolomite) are generally the most abundant phases, sometimes reaching up to 77%, and quartz represents ~10% (Fig. 2). The clay minerals detected in the <2 mm fraction are palygorskite, illite, Al smectite and kaolinite. Palygorskite, with contents of ~50 70%, is the most important phyllosilicate; illite contents range from 11 to 36%, smectite and kaolinite do not represent more than 10%, although at the bottom, there is up to 27% kaolinite. The mineral phases found at J. Hamri are the same, but in different proportions. Quartz (up to 54%), phyllosilicates and calcite are the main components. In the clay fraction, illite is the most abundant phase (38 59%), followed by palygorskite (14 40%). Kaolinite normally appears in small amounts (5 10%) and Al smectite is systematically present, reaching 28% at times. On the other hand, J. Rheouis and J. Lessouda show rather similar compositions, which are different from the southern sequences. They consist almost exclusively of phyllosilicates and dolomite in varying proportions, with quartz and feldspars as trace minerals. In addition, in J. Rheouis some samples contain small quantities of clinoptilolite (<3%). The clay fraction is more variable, containing palygorskite (38 96%) and illite (3 23%) as major components. Mg-smectite (not present in the southern sequences), Al smectite, kaolinite (at J. Lessouda) and opal are also present, but never in significant quantities (up to 10%). Figure 3 shows the mineralogical composition of all the samples studied. Even in the same sequence, this composition is very diverse, as shown by the breadth of the fields, indicating highly variable conditions of the depositional environment,

regarding both the sediment supplies and their chemical characteristics.

Geochemistry
The average major component, trace element and REE contents of the clay fraction of selected samples are presented in Table 1. Southern sequences (J. Boloufa and J. Hamri) are richer in Al2O3 (J. Hamri also in K2O), corresponding to their higher illite content. MgO content ranges from 5.21 to 9.41%, while the central sequences are richest in Mg. We obtained the correlation matrices of all the mineralogical and geochemical variables (major elements and the complete set of trace and rare earth elements). The results obtained show that Al2O3 is closely linked to Fe2O3 (r = 0.97), K2O (r = 0.98), TiO2 (r = 0.98) and Mn2O3 (r = 0.70), as well as to the phyllosilicates of clearly detrital origin, with r >0.8 (illite, interstratified illitesmectite, Al smectite and kaolinite). The REE and, among others, transition elements (TRTE) Ni, Co, V, Cr, Cu, Sc behave in a similar fashion, presenting r >0.8 among themselves and with the aforementioned variables. In view of the good correlations and considering the calculation established by Lo pez Galindo et al. (1996), we determined from the theoretical REE and TRTE contents that pure palygorskite would be present in these deposits (Fig. 4). Thus, the REE contents would be ~40 ppm (Bou-Loufa and J. Hamri), 50 ppm (J. Rheouis) and 70 ppm (J. Lessouda). Likewise, the amount of TRTE in this pure palygorskite would vary from 125 to 175 ppm. When the REE contents of the different Tunisian deposits are normalized to NASC, we find an

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FIG. 4. REE and TRTE content of the studied samples as a function of the percentage of detrital phyllosilicates.

essentially horizontal pattern, containing between 25 and 100% of the NASC contents and that there is a slight enrichment in light rare earth elements (LREE) (2 La/Lu 4.5). No significant anomalies were detected, except for one case in the J. Hamri deposit, where the richest palygorskite sample had a clear positive anomaly in Ce. Principal component analysis was applied to mineralogical and chemical variables. Three factors explaining the 80% of the total variance were obtained (Fig. 5). Factor 1 (40%) and factor 2 (24%) are clearly interpretable as genetic factors, and separate the clearly detrital minerals and associated chemical elements from those components of presumably different origin (palygorskite, amorphous silica and Mg smectite). Factor 3 (16%) discriminates between silicates and carbonates.

0.05 atoms per structural formula), and there is a systematic presence of K and Ca in the interlayer with predominance of the former (at times up to 0.4 K atoms are found per unit cell). It is interesting to note that the J. Hamri deposit, which contains the most clearly detrital mineral assemblage, also has the palygorskites richest in Al and with the largest amount of K in the interlayer.

Micromorphology
The microtexture observed by SEM varies from one sequence to another, or even within the same sequence. The most frequent manner in which palygorskite appears is as chaotic arrangements of short fibres (<2 mm, Fig. 7a), or in more or less

Chemical composition
Table 1 summarizes the mean compositions of the palygorskite analysed by AEM in the different sequences. Figure 6, representing the composition of the octahedral layer, shows the wide variability existing even between samples from the same deposit. Practically all the particles analysed present compositions intermediate between dioctahedral and trioctahedral (this is particularly clear when compared with the compositional field of the different types of smectites, Fig. 6c). We should also point out that substitution of Si by Al in the tetrahedral sheet is relatively moderate (0.15 0.35 atoms per unit cell), there is a weak presence of Ti and/or Mn in the octahedral sheet (never more than

FIG. 5. R-mode factor analysis showing the contribution of statistically dominant variables (Factors 1 and 2).

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FIG. 6. Composition of the palygorskite octahedral sheet: (a) south central sequences; (b) north central sequences; (c) comparison with smectite composition; (d) REE distribution of a pure palygorskite normalized to NASC.

planar structures with filamentous edges (Fig. 7b) consisting of particles which, on a small scale, present some preferential orientation (Fig. 7c). Longer fibres (up to 5 mm) are also found arranged in bundles or sheaves and which, taken as a whole, have the appearance of a mat or rug (Fig. 7d). The presence of idiomorphic dolomite crystals covered by palygorskite fibres (Fig. 7e) or growing on such fibres (Fig. 7f) illustrates the different growth generations of this fibrous clay, depending on the physical-chemical variations of the environment. The average size-range of the clayey particles, measured both by laser granulometer and by image analysis of photomicrographs obtained by TEM, is summarized in Table 1, where we can see that >90% of the fibres are <2 mm.

DISCUSSION
There are numerous studies of the genesis of palygorskite in continental environments (e.g. Millot, 1964; Singer, 1984; Velde, 1985; Jones & Galan, 1988, among others). As is known, this fibrous clay is found especially in soils, calcretes and lacustrine deposits and there is general agreement that its formation requires alkaline conditions, high Si and Mg activity and an arid or semi-arid climate, with marked dry and wet seasons. Bearing in mind the nature of the clay paragenesis (cf. Chamley, 1989), most of the clays found in the Tertiary continental deposits of Tunisia are basically detrital and their accumulation is undoubtedly linked to water and/or wind supply in

FIG. 7 (facing page). Microtextures of the samples studied. (a) Chaotic arrangements of short fibres (J. Rheouis). (b) Planar structures with filamentous edges (J. Lessouda). (c) Detail from the edge of a planar aggregate (J. Rheouis). (d) Imbricated fibres of palygorskite with a mat aspect (J. Bouloufa). (e) Idiomorphic dolomite crystals covered by palygorskite fibres (J. Bouloufa). (f) Dolomite growing on palygorskite fibres (J. Bouloufa).

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closed, lacustrine-type basins or in playa-lakes accumulated during flooding episodes (Jamoussi et al., 2001a,b). The source area for the Tertiary deposits must have been the surrounding formations (Jamoussi, 2001), because they contain considerable amounts of clays, particularly Al smectite, illite, kaolinite and, as is the case for the Triassic diapirs, chlorite, the alteration of which could have provi ded additional Mg (Jamoussi , 2001). Moreover, the genesis of both primary and diagenetic carbonates, as well as the precipitation of gypsum (present in all the sequences studied) increases the Mg/Ca ratio of the interstitial water, guaranteeing an alkaline pH. Finally, in a recent study on climatic evolution in the Tethys during the Palaeocene-Eocene, Bolle & Adatte (2001) showed the progressive development of arid climatic conditions in southern Tunisia during this period. The REE and trace elements data, particularly those for the first transition series (TRTE) provide interesting clues to explain the genesis of palygorskite in these continental Tertiary deposits. In fact, most of the natural water has extremely low REE concentrations of ~10 7 10 2, in comparison with the values found in the rocks (McLennan, 1989). This is mainly due to the fact that mobility and fractionation of the REE are very unlikely at the fluid/rock level (Taylor & McLennan, 1985), i.e. the REE move from the alteration profile to the sedimentary basins without being affected by any chemical process during transport (Fleet, 1984). The behaviour of the REE during the different alteration processes is mainly controlled by inheritance and their pattern in clayey sediments is clearly related to that of the mother rock (Cullers et al., 1975; Bonnot-Courtois, 1981; Fleet, 1984). The REE are essentially adsorbed by the clays and are found in considerable quantities in clearly detrital clays and in very small amounts in clearly neoformed clays, such as sepiolite and/or stevensite (~250 ppm in the former and <20 ppm in the latter, Torres Ruiz et al., 1994). In low-temperature aqueous solutions, transition elements, such as Ni, Co, V, Cr, Cu and Sc, behave in similar fashion to the REE and usually appear in equally low concentrations (McLennan, 1989). In Spanish deposits, this quantity has been determined at ~450 ppm in detrital minerals and <80 ppm in neoformed phases (Torres-Ruz et al., 1994). The REE and TRTE contents found in the palygorskite from Tunisian deposits vary from 40 to 70 ppm and from 125 to 175 ppm, respectively.

These values coincide on the whole with those determined in other Spanish and Moroccan deposits (Ben Aboud, 1998) and which are intermediate between those of the two mineral groups mentioned above. The REE distribution model of a threoretical pure palygorskite (Fig. 6d) shows a slight impoverishment in heavy REE (Gd Lu, HREE), that can be attributed to the pH of the interstitial solutions, which aids accumulation of light REE (La Eu, LREE) in alkaline conditions (Nesbitt, 1979), as well as to the mobility of the HREE in natural solutions because of their ability to form bicarbonated and organic solutions more soluble than the LREE (Fleet, 1984; McLennan, 1989), or also because of differential adsorption of lanthanides onto hydrogenous particle surfaces due to their different polarizing power (Turner & Whitfield, 1979). As regards chemical composition, palygorskite is a clay that accepts quite considerable substitutions in the octahedral sheet, its composition typically being intermediate between the dioctahedral and trioctahedral end-members (Weaver & Pollard, 1973). Later studies by Paquet et al. (1987), Duplay (1988) and Gala n & Carretero (1999) have shown that the variation interval in the composition of palygorskite is even larger than first thought, with many analyses clearly falling within the dioctahedral domain, as is frequently the case with the Tunisian samples, especially from J. Hamri and J. Rheouis. Regarding the average compositions summarized in Table 1, we should point out the high Fe and Al contents present in the octahedral sheet, as well as the high K and Ca values in the interlayer, the proportions of which are similar to that detected in other aluminosilicates, such as illite and/or Al smectite. As in the cases of other palygorskites from Spain and Morocco described in previous studies (Ben Aboud et al., 1997; Ben Aboud, 1998), the geochemical and textural data suggest that the genesis of this fibrous clay is intimately linked to the transformation of a detrital aluminosilicate precursor, especially smectite and interstratified illite-smectite. On this point we should mention that, when studying the mineral assemblages throughout the geological record in Tunisia (Jamoussi et al., 2001b), it can be seen that, during the Eocene, the proportion of smectite falls dramatically in sequences where palygorskite is present. This type of mechanism has often been

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suggested as the most probable cause of the presence of palygorskite, e.g. the papers by Martn de Vidales et al. (1988) on lacustrine-palustrine Miocene sediments in the Madrid basin, who suggest alteration of the structure of pre-existing montmorillonite in a mechanism of dissolution-precipitation due to the presence of magnesian waters during the carbonatation processes involving calcrete formation; by Sua rez et al. (1994) on the Bercimuel deposit (Segovia, Spain), who suggested mechanisms of dissolution of detrital mica with K and Al loss and Si and Mg gain, giving rise to structural formulae very similar to those described here; or by De Pablo (1996) on Eocene palygorskiterich mudstone in the Yucatan Peninsula, where palygorskite formed in a tranquil marine back-reef lagoon environment of high Mg, Si and Al activity, by diagenesis of precursor montmorillonite, from reaction between montmorillonite, dolomitic limestone and silicic acid. On the other hand, in his study of the manner of genesis of an Al and Mg pal ygorski t e i n the B oul oufa Format i on, Abdeljaoued (1997) showed that this mineral can appear both as direct precipitation from solution, and as recrystallization of smectites, with no particular predominance of either of these mechanisms. The fact that idiomorphic crystals of dolomite similar to those described by Karakas & Kadir (1998) were found covered with palygorskite fibres or resting on a fibre mat (their photos A and B) indicates that small chemical changes, due to cl imatic fluctuations, gypsum precipitation (Khademi & Mermut, 1998) or as a result of early diagenetic transformations in the superficial layers of sediment could have affected the chemical characteristics of the lake water, thus altering the Mg/Ca ratio and the pH of the environment and causing different generations of carbonates and the appearance of palygorskite.

contents of Tunisian pure palygorskite are also intermediate between clearly authigenic clays, such as sepiolite (<50 ppm), and detrital clays, such as illite, mixed-layer I-S and Al smectite (>400 ppm). We suggest that this fibrous clay originated during the first stages of diagenesis, due to the destabilization of the existing aluminosilicates, in a mechanism of dissolution-precipitation that could be due to the presence of magnesian waters during post-depositional carbonation processes.
ACKNOWLEDGMENTS

This research is part of the projects Identification, cartographie et valorisation des mate riaux utiles en Tunisie (SERST, Tunisia), and CSIC 1999TN002, DGI-BTE2000-0777 and research group RNM-0179 of the Junta de Andaluca (Spain). The authors are grateful for the helpful comments by Prof. Herve Chamley (Universite Strasbourg) and Prof. M.D. Ruz Cruz (Universid ad de Ma laga) which helped to impr ove our paper. We also thank Prof. Ian MacCand less (Depart m ent Filolo g a In gl esa, Universidad de Granada) for assisting us with the English grammar.
REFERENCES

CONCLUSIONS
The clay fraction of Tunisian Eocene continental sediments contains considerable quantities of palygorskite (up to 96%). Its average mineralogical formula is intermediate between the dioctahedral and trioctahedral end-members, as follows: (Si7.71Al0.29)O20(Mg1.81Al1.55Fe3+ 0.52 Mn0.02Ti0.03)(OH)2 (K0.13Ca0.07)(OH2)4.4H2O As observed in similar Spanish and Moroccan deposits, the transition trace element and REE

Abdeljaoued S. (1983) Etude se dimentologique et structurale de la partie est de la Chagne Nord des Chotts (Tunisie me ridionale ). Special thesis, Universite Tunis, Tunisia. `tes ` Abdeljaoued S. (1991) Les dolocre et les calcre tes du Paleoce ne-Eoce ` `ne: Tunisie meridionale . PhD thesis, Universite Tunis II, Tunisia. Abdeljaoued S. (1997) Mode de gene des palygors`se kites dans la serie continentale eoce de Tunisie `ne meriodionale. Notes du Service Geologique de Tunisie, 63, 15 27. Barahona E. (1974) Arcillas de ladrillerg a de la provincia de Granada: evaluacio n de algunos en say o s d e ma ter ia s pr imas . Ph D the sis , Universidad de Granada, Spain. Bedir M. (1995) Mecanismes ge odynamiques des bassins associe s aux couloirs de coulissement de la marge Atlasique de la Tunisie. Seismo-stratigraphie, seismo-tectonique et implications petrolie `res. PhD thesis, Universite Tunis II, Tunisia. Ben Aboud A. (1998) Depots tertiaires de palygorskite ens (Maroc, dans des bassins circum-me diterrane Espagne, Tunisie). Mineralogie, geochimie et genese. PhD thesis, Universidad de Granada, Spain. ` Ben Aboud A., Lo pez-Galindo A., Fenoll Hach-Al P. & Chella E.H. (1997) Caracte ristiques mineralogiques et geochimiques des palygorskites tertiaires dIda Ou

198

F. Jamoussi et al. istry of the rare earth elements. Pp 343 373 in: Rare Earth Element Geochemistry (P. Henderson, editor). Elsevier Science Pubs., Amsterdam. Foster M.D. (1960) Interpretation of the composition of trioctahedral micas. USGS Professional Paper, 354-B, 11 49. Galan E. & Carretero I. (1999) A new approach to compositional limits for sepiolite and palygorskite. Clays and Clay Minerals, 47, 399 409. Hachi A. (1998) Identification, caracte risation et valorisation des argiles Eocene-Mioce des regions ` `ne de Kasserine, Feriana et Sebeitla. DEA thesis, Universite Tunis II, Tunisia. Jamoussi F. (2001) Les argiles de Tunisie: etude mineralogique, geochimique, geotechnique et utili sations industrielles . PhD thesis, Universite Tunis El Manar, Tunisia. Jamoussi F., Abbes Ch., Fakhfakh E., Bedir M., ` Kharbachi S., Soussi M., Zargouni F. & Lopez Galindo A. (2001a) Decouverte de lEoce `ne continental autour de larchipel de Kasserine, aux Jebels Rheouis, Boudinar et Chamsi en Tunisie centro meridionale: nouvelles implications pale ographi oge ques. Comptes Rendu de lAcademie des Sciences Paris, 333, II, 329 335. Jamoussi F., Lopez-Galindo A., Morales S. and Zargouni F. (2001b) The chart of Tunisian clays. Mineralogica Polonica, 32, 79 86. Jones B.F. & Galan E. (1988) Sepiolite and palygorskite. Pp. 631 674 in: Hydrous Phyllosilicates (Exclusive of Micas) (S.W. Bailey, editor). Reviews in Mineralogy, 19. Mineralogical Society of America, Washington, D.C. dimentaire (AptienKadri A. (1988) Evolution tectono-se Quaternaire) des Dj. Koumine, Hamra et Lessouda (Tunisie centrale). Thesis 3rd cycle, Universite Paris X, Orsay, France. Kadri A., Matmati F., Ben Ayed N. & Ben Haj Ali M. (1986) Decouverte de lEoce infe `ne rieur continental au Jebel Lessouda (Tunisie centrale). Notes du Service Geologique de Tunisie, 51, 53 59. Karakas Z. & Kadir S. (1998) Mineralogical and genetic relationships between carbonate and sepiolite-palygorskite formations in the neogene lacustrine Konya Basin, Turkey. Carbonates and Evaporites, 13, 198 206. Khademi H. & Mermut A.R. (1998) Source of palygorskite in gypsiferous arid soils and associated sediments from central Iran. Clay Minerals, 33, 561 578. Lo pez-Galindo A., Torres-Ruiz J. and Gonza lez-Lo pez J.M. (1996) Mineral quantification in sepiolitepalygorskite deposits using X-ray diffraction and chemical data. Clay Minerals, 31, 217 224. Martn de Vidales J.L., Pozo M., Medina J.A. & Leguey S. (1988) Formacio de sepiolita-paligorskita en n litofacies luttico-carbona ticas en el sector de Borox-

Galal (nord-est de Taroudannt et de Toundout (nord-est de Ouarzazate). Implications genetiques. Comptes Rendu de lAcademie des Sciences Paris, 324, IIa, 189 195. Ben Aboud A., Lopez-Galindo A., Fenoll Hach-Al P., Jamoussi F., Bedir M., Abdeljaoued S. & Setti M. (1999) Mineralogy and geochemistry of some Tunisian palygorskitic outcrops. Pp. 1073 1076 in: Mineral Deposits: Processes to Processing (C.J. Stanley et al., editors). Balkema, Rotterdam. Biscaye P.E. (1965) Mineralogy and sedimentation of recent deep-sea clay in the Atlantic Ocean and adjacent seas and oceans. Geological Society of America Bulletin, 76, 803 832. Bishop W.P. (1988) Petroleum geology of east-central Tunisia . American Associat ion of Petrole um Geologists Bulletin, 9, 1033 1058. Bolle M.P. & Adatte T. (2001) Palaeocene-early Eocene climatic evolution in the Tethyan realm: clay mineral evidence. Clay Minerals, 36, 249 261. Bonnot-Courtois C. (1981) Geochimie des Terres Rares dans les principaux milieux de formation et de sedimentation des argiles. PhD thesis, Universite de Paris-Sud, France. Boukadi N. (1994) Structuration de lAtlas de Tunisie: signification geometrique et cinematique des nuds et des zones dinterfe rences structurales au contact de grands couloirs tectoniques. PhD thesis, Universite Tunis II, Tunisia. Boukadi N. & Bedir M. (1996) Lhalocine en Tunisie: `se contexte tectonique et chronologie des evenements. Comptes Rendu de lAcademie des Sciences Paris, 322, IIa, 587 594. ` Burollet P.F. (1956) Contribution a letude stratigraphique de la Tunisie Centrale. Annales des Mines et Geologie, 18, Tunisia. Chamley H. (1989) Clay Sedimentology , pp. 75 94. Springer-Verlag, Berlin. Creuzot G. & Ouali J. (1989) Extension, diapirisme et compression en Tunisie centrale: le Jebel Es souda. Geodynamique , 4, 39 48. Cullers R.L., Chaudhuri S., Arnold B., Lee M. & Wolf C.W. (1975) Rare earth distributions in clay minerals and in the clay-sized fraction of the Lower Permian Havensville and Eskridge shales of Kansas and Oklahoma. Geochimica et Cosmochimica Acta, 39, 1691 1703. De Pablo L. (1996) Palygorskite in Eocene-Oligocene lagoonal environment, Yucatan, Mexico. Revista Mexicana de Ciencias Geolo gicas, 13, 94 103. Duplay J. (1988) Geochimie des argiles et geothermometrie des populations monomine rales de particules . PhD thesis, Universite Strasbourg, France. risation des Fakhfakh E. (1999) Identification et caracte argiles fibreuses du centre et du Sud de la Tunisie. DEA thesis, Universite Tunis II, Tunisia. Fleet A.J. (1984) Aqueous and sedimentary geochem-

Palygorskite in Tunisian sediments Esquivias (Cuenca de Madrid). Estudios Geolo gicos, 44, 7 18. McLennan S.M. (1989) Rare earth elements in sedimentary rocks: influence of provenance and sedimentary processes. Pp. 169 200 in: Geochemistry and Mineralogy of Rare Earth Elements (B.R. Lipin & G.A. McKay, editors). Reviews in Mineralogy, 21. Mineralogical Society of America, Washington, D.C. Millot G. (1964) Geologie des Argiles. Masson, Paris, pp. 163 209. Nesbitt, H.W. (1979) Mobility and fractionation of rare earth elements during weathering of a granodiorite. Nature, 279, 206 210. Paquet, H., Duplay, J., Valleron-Blanc, M.M. & Millot, G. (1987) Octahedral compositions of individual particles in smectite-paly gorskite assemblages. Proceedings of the International Clay Conference , Denver, 1985, 73 77. Pochitaloff A. (1968) Rapport de fin du sondage Tanit 1 (Rapport SEREPT, unpublished). 15 pp. Sassi S., Triat J.M., Truc G. & Millot G. (1984) Decouverte de lEoce `ne continental en Tunisie centrale: la formation du Djebel Gharbi et ses encrou tements carbonate s. Comptes Rendu de lAcademie des Science Paris, 299, II, 357 364. Schultz L.G. (1964) Quantitative interpretation of mineralogical composition from X-ray and chemical data for the Pierre Shale. United States Geological Survey Professional Paper, 391-C, 31 pp. Singer A. (1984) Pedogenic palygorskite in the arid environm ent. Pp. 169 177 in: Palygor skiteSepiolite. Occurrences, Genesis and Uses (A. Singer & E. Galan, editors). Developments in Sedimentology, 37, Elsevier, Amsterdam. Soussi M., Abbes Ch., Belayouni H. & Boukadi N. ` (1996) Sedimentologie, stratigraphie sequentielle et caracte ristiques geochimiques des series du Trias moyen et supe rieur de lAxe nord-sud (Tunisie centrale). Proceeding of the 5th Tunisian Petroleum Exploration Conference , 10, 275 285.

199

Srasra E., Jamoussi F., Zargouni F. & Ferid M. (1995) Etude physico-chimique de la palygorskite carbonatee de lEoce continental de Chebket Bouloufa. `ne Revue du Service Geologique de Tunisie, 61, 109 119. Suarez M., Robert M., Elsass F. & Martn-Pozas J.M. (1994) Evidence of a precursor in the neoformation of palygorskite. New data by analytical electron microscopy. Clay Minerals, 29, 255 264. Swan A.R.H. & Sandilands M. (1995) Introduction to Geological Data Analysis. Blackwell Science, Oxford, UK, pp. 328 397. Taylor S.R. and McLennan S.M. (1985) The Continental Crust: its Composition and Evolution. Blackwell, Oxford, UK, 312 pp. Torres-Ruz J., Lopez-Galindo A., Gonza lez-Lo pez J.M. & Delgado A. (1994) Geochemistry of Spanish sepiolite-palygorskite deposits: genetic considerations based on trace elements and isotopes. Chemical Geology, 112, 221 245. Truc G. (1981) Encrou `te) de tement calcaire (calcre ` Tunisie. Premier Congre s National des Sciences de la Terre, Tunis, pp. 102 103. Turner D.R. & Whitfield M. (1979) Control of seawater composition. Nature, 281, 468 469. Velde B. (1985) Clay Minerals. A Physico-chemical Explanation of their Occurrences. Developments in Sedimentology, 40. Elsevier, Amsterdam. Weaver C.E. & Pollard L.D. (1973) The Chemistry of Clay Minerals. Developments in Sedimentology, 15. Elsevier, Amsterdam. Zargouni F. (1985) Tectonique de lAtlas meridional de Tunisie. Evolution geometrique et cine matique des structures en zone de cisaillement . PhD thesis, Universite Louis Pasteur, Paris. Zouari H. (1984) Etude structurale du Jebel Chaambi (Tunisie centrale). Relation entre la mineralisation et la structure . Thesis 3rd cycle, Universite Franche Compte , Besanc on, France.