Sedimentology (2001) 48, 153163

Dolomitization by penesaline sea water in Early Jurassic peritidal platform carbonates, Gibraltar, western Mediterranean
H AIRUO QING 1 , DANIEL W. J. BOSENCE and EDWARD P. F. ROSE Department of Geology, Royal Holloway, University of London, Egham, Surrey TW20 0EX, UK (E-mail: [email protected]; [email protected])
ABSTRACT

Peritidal carbonates of the Lower Jurassic (Liassic) Gibraltar Limestone Formation, which form the main mass of the Rock of Gibraltar, are replaced by ne and medium crystalline dolomites. Replacement occurs as massive bedded or laminated dolomites in the lower 100 m of an 460-m-thick platform succession. The ne crystalline dolomite has d18O values either similar to, or slightly higher than, those expected from Early Jurassic marine dolomite, and d13C values together with 87Sr/86Sr ratios that overlap with sea-water values for that time, indicating that the dolomitizing uid was Early Jurassic sea water. Absence of massive evaporitic minerals and/or evaporite solution-collapse breccias in these carbonate rocks indicates that the salinity of sea water during dolomitization was below that of gypsum precipitation. The occurrence of peritidal facies, a restricted microbiota and rare gypsum pseudomorphs are also consistent with penesaline conditions (salinity 72199&). The medium crystalline dolomite has some d18O and d13C values and 87Sr/86Sr ratios similar to those of Early Jurassic marine dolomites, which indicates that ambient sea water was again a likely dolomitizing uid. However, the spread of d18O, d13C and 87Sr/86Sr values indicates that dolomitization occurred at slightly increased temperatures as a result of shallow (500 m) burial or that dolomitization was multistage. These data support the hypothesis that penesaline sea water can produce massive dolomitization in thick peritidal carbonates in the absence of evaporite precipitation. Taking earlier models into consideration, it appears that replacement dolomites can be produced by sea water or modied sea water with a wide range of salinities (normal, penesaline to hypersaline), provided that there is a driving mechanism for uid migration. The Gibraltar dolomites conrm other reports of signicant Early Jurassic dolomitization in the western Tethys carbonate platforms. Keywords Carbonate platform, C-O-Sr isotopes, dolomitization, Early Jurassic, Gibraltar, western Tethys.

INTRODUCTION The origin of massive replacement dolomite has long been an enigma to geologists, and many models have been presented to account for it (e.g.

Present address: Department of Geology, University of Regina, Regina, Saskatchewan, Canada, S4S 0A2 (E-mail: [email protected])

Land, 1985; Purser et al., 1994). Current understanding is that dolomite can be produced by various uids in different environments, e.g. evaporitic marine brines in sabkhas, evaporative brines during basinal evaporite drawdown, normal sea water in subtidal environments, freshwater/sea water in mixing zones and deep basinal uids during burial. Such different dolomites can be recognized from their spatial distribution, facies associations and petrography and in their 153

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H. Qing et al. from eastward-dipping, right-way-up strata in the Southern Plateaux (Fig. 1). The 460-m-thick Gibraltar Limestone Formation, which forms the main mass of the Rock, has been subdivided into four members on the basis of colour, bedding characteristics and degree of dolomitization (Rose & Rosenbaum, 1990, 1991a,b; Rose, 2000; Fig. 2). An Early Jurassic (Sinemurian) age for the upper part of the Gibraltar Limestone Formation has been veried on the basis of rare brachiopods (Owen & Rose, 1997) and from strontium isotope values from these same brachiopods (Bosence et al., 2000). Recent facies analysis by Bosence et al. (2000) shows that the Gibraltar Limestone Formation consists of restricted, shallow-marine peritidal carbonate facies, arranged in high-frequency metre-scale, shallowing-up cycles of restricted inner platform facies with subtidal and intertidalsupratidal components. These cycles are superimposed on low-order (third?) cycles of relative sea-level change. The subtidal sediments are characterized by peloidal mudstonespackstonesgrainstones, peloidalskeletal grainstones and intraformational intraclastic rudstones. Periodic subaerial exposure is indicated by laminar calcretes, fenestrae, shrinkage cracks, tepee structures and pisoids. Normal marine bioclasts are absent for most of the succession, but restrictedmarine biota of dasycladacean algae and benthic foraminifera occur locally in the Keightley and Buffadero member limestones (Bosence et al., 2000; Boudagher-Fadel et al., 2001). The ubiquitous presence of restricted, inner-platform peritidal carbonates and the absence of massive evaporitic minerals (e.g. gypsum/anhydrite) and/ or evaporite solution-collapse breccias suggest a slightly restricted evaporitic environment, i.e. penesaline sea water, with a maximum salinity that only rarely reached gypsum saturation, as indicated by the presence of very rare gypsum pseudomorphs in the Main Ridge succession (Bosence et al., 2000). METHODS The petrographic and isotopic data are derived from samples collected during detailed logging of two composite sections (Figs 1 and 2) through the accessible lower and middle parts of the Formation: a 217-m right-way-up sequence through the Southern Plateaux, and a 314-m inverted sequence through the Main Ridge (Fig. 2), as described by Bosence et al. (2000). Approxi-

geochemical and isotopic signatures, which are controlled by variations in the temperature, salinity and composition of the dolomitizing uids. Classic examples of hypersaline dolomitization (e.g. Adams & Rhodes, 1960; McKenzie et al., 1980) require the generation of saline brines by the evaporation of sea water to the point at which gypsum/anhydrite is precipitated, necessarily increasing the Mg/Ca ratio of the residual brine. The lateral and vertical movement of such brines can result in dolomitization of supratidal and underlying intertidal and subtidal carbonates. However, this model cannot be applied directly to extensive dolomitization of carbonates that are not associated with extensive gypsum/anhydrite deposits. In a recent review of the global, temporal and sedimentological settings of early dolomitization, Sun (1994) hypothesized that, in greenhouse (i.e. ice-cap free) periods of Earth history, dolomitization of extensive, cyclic peritidal carbonates could occur from the ooding and reux of sea water of slightly increased salinities. As indicated by preliminary studies (Qing et al., 1998), the dolomites from the Rock of Gibraltar provide petrographic and isotopic data in support of Sun's hypothesis. It is proposed that such dolomites be called penesaline dolomites using Adams & Rhodes's (1960) term for evaporated sea water with salinities varying from 72& to 199&. Such salinities are indicated by the presence of restricted marine carbonate facies and marine biota and the absence of associated evaporites. Early Jurassic dolomites are common within Tethyan carbonate platforms (e.g. Colacicchi et al., 1975; Martn, 1979; Flugel, 1 1983; Crevello, 1991; Soussi & M'Rabet, 1994; Barattolo & Bigozzi, 1996; Rey, 1997; Ronchi 2 et al., 2000; Scherreiks, 2000), and this is consistent with the high global abundance of dolomite in carbonate rocks of this time (Given & Wilkinson, 1987). GEOLOGICAL SETTING The Rock of Gibraltar dominates a narrow peninsula that juts south from Spain at the western entrance to the Mediterranean Sea (Fig. 1). Two topographic regions can be distinguished: the Main Ridge, which forms a northsouth scarp with peaks over 400 m high; and the Southern Plateaux, where the Rock is truncated to the south by two Quaternary wave-cut platforms. Inverted and westward-dipping carbonate strata in the Main Ridge have recently been distinguished

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Fig. 1. Pre-Quaternary geological map of Gibraltar, with stratigraphic column showing the position of the Bleak, Europa, Keightley and Buffadero members and the location of logged sections in Fig. 2. (Map simplied after Rose & Rosenbaum, 1990, 1991a,b; logged sections after Bosence et al., 2000).

mately 300 thin sections and peels were studied. All thin sections were stained with Alizarin-Red S and potassium ferricyanide (Dickson, 1965). Forty-six thin sections were also examined using a cathodoluminescence (CL) microscope. Forty-one samples from the logged sequences of the two sections were analysed for d18O and d13C, and 14 for 87Sr/86Sr (Table 1). These samples were obtained from limestones and dolomites using a dental drill after petrographic study. Stable O and C isotopes were analysed in the VG Prism mass spectrometer laboratory, and the strontium isotopes in the Thermal Ionization Mass Spectrometer (TIMS) laboratory, both in the Department of Geology at Royal Holloway, University of London. The precision of carbon and oxygen isotope values from replicate analysis of standards (NBS 19 and internal standards) is within 01& for C and 02& for O. Strontium isotope results are standardized to SRM 987 values of 0710248.

DOLOMITE PETROGRAPHY AND STRATIGRAPHIC DISTRIBUTION Two types of massive replacement dolomite can be recognized in the Gibraltar Limestone Formation: 1 Fine crystalline dolomite (Fig. 3A). This is either brown or grey in hand specimen with wellpreserved fossil and sedimentary features. Microscopically, it consists of subhedral to anhedral dolomite crystals with a size range from 20 to 100 lm (mean 50 lm). These have a planar-S texture (cf. Gregg & Sibley, 1984) and lack undulatory extinction. Fine crystalline dolomite is generally non-luminescent under CL. 2 Medium crystalline dolomite (Fig. 3B). This is also brown or grey in hand specimen. However, precursor fossils and/or ne-scale sedimentary textures are partially to completely obliterated (Fig. 3B and D). This fabric is composed of

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Fig. 2. Summary logged sections of Gibraltar Limestone Formation from the Main Ridge and Southern Plateaux regions of the Rock of Gibraltar indicating members, lithologies, dolomite occurrence and horizons sampled for analyses in Table 1 and corresponding micrographs in Fig. 3. Scale in metres. (For stratigraphic database, see Bosence et al., 2000). Table 1. d18O, d13C and carbonates. Sample G29-2 G29-1 G16-2 G16-1 F20-2 F20-1 F17-3 F17-2 F17-1 Mean P5 J8-1 J6-1 F19-2 F19-1 F16-3 F16-2 F16-1 C14-5 C14-4 C14-1 C13-2 C1-4 B17 B15 B6 A2-2 A2-1 A2-1 Mean K2-1 K1-1 P6 P1 N19-1 N18-2 N14-1 N7-1 N5-1 J1-1 C11 B14 B1 Mean Lithology LS LS LS LS LS LS LS LS LS FCD FCD FCD FCD FCD FCD FCD FCD FCD FCD FCD FCD FCD FCD FCD FCD FCD FCD FCD MCD MCD MCD MCD MCD MCD MCD MCD MCD MCD MCD MCD MCD
87

Sr/86Sr values for Gibraltar d13C 235 233 230 240 193 232 220 215 221 22433 163 264 209 198 198 235 257 235 189 250 292 199 254 275 251 159 183 169 163 21805 208 190 )079 189 338 063 357 220 370 )062 172 224 228 186
87

d18O )244 )231 )397 )363 )231 )205 )292 )298 )292 )284 126 159 235 159 270 192 115 135 187 167 071 040 009 056 049 064 080 135 114 124 )122 )190 )031 )242 )043 )167 005 )165 027 010 )071 099 154 )057

Sr/86Sr

070856 070850

070787 070831 070777 070798 070776

070809 070759

070794 070782 070804 070787 070950

070787

070775 070837

Sample letter numbers refer to locations on logs in Fig. 2. LS, limestones; FCD, ne crystalline dolomite; MCD, medium crystalline dolomite.
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Fig. 3. Thin-section photomicrographs (in plain polarized light) of dolomite from the Gibraltar Limestone Formation. (A) Fine crystalline dolomite comprising subhedral to anhedral dolomite crystals ranging in size from 20 to 100 lm (mean 50 lm) and a planar-S texture (sample no. J8). (B) Medium crystalline dolomite composed of anhedral to subhedral dolomite crystals ranging in size from 100 to 300 lm (mean 150 lm). Some crystals have a cloudy centre and a clear rim (arrow) (sample no. C11). (C) Fine crystalline dolomite precipitated in the centre of bird's eye fenestra following radiaxial calcite cement. Crystal rhombs of the dolomite also replace the fenestrate peloidal packstone wackestone. Dolomitization has therefore post-dated radiaxial and ne equant calcite cements (sample no. F11). (D) Peloidal grainstone cemented by ne equant calcite cement, both replaced (and therefore post-dated) by medium crystalline dolomite (sample no. L4).

anhedral to subhedral dolomite crystals, ranging from 100 to 300 lm (mean 150 lm) that either replace precursor grains and cements or inll pores after marine radiaxial calcite (Fig. 3C). Like the ne crystalline dolomite, crystals have a planar-S texture and lack undulatory extinction. Some medium crystalline dolomites have a cloudy centre and a clear rim (Fig. 3B). Although medium crystalline dolomite is generally nonluminescent under CL, some samples show blotches of dull-orange luminescence, suggesting possible neomorphism by later diagenetic uids and/or two-stage dolomitization. Massive replacement dolomites have the same stratigraphic occurrence in both the Southern Plateaux and the Main Ridge regions of the Rock (Fig. 2), although these are separated by a major NWSE fault zone and the Main Ridge succession

is inverted. Both ne and medium crystalline types are abundant in the lower part of the Formation and decrease stratigraphically upwards (Figs 1 and 2). The lowest two members, Bleak and Europa, are completely dolomitized and consist of thick to thin-bedded and/or laminated dolomites. The overlying Keightley Member has massive replacement dolomites in the lower part, but these are succeeded stratigraphically by increasing amounts of limestone. The uppermost and thickest member, the Buffadero, consists mainly of limestone with scattered dolomite rhombs, patches and beds. The dolomitization clearly predated tectonic overturning of the Main Ridge strata, because the dolomite occurs in the stratigraphically lower levels both in the right-way-up Southern Plateaux section and in the inverted Main Ridge section (Fig. 2; Bosence et al., 2000).

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A recent study of cyclicity within the succession (Bosence et al., 2000) indicates that the dolomitized portion of the succession relates to thinner than average high-frequency cycles interpreted to have formed during the falling stage and lowstand period of a low-frequency cycle (Bleak and Europa members). Thicker than average high-frequency cycles, which formed during a low-frequency transgressive phase, correlate with the up-section reduction in degree of dolomitization and the arrival of marine biota (Keightley and lower Buffadero members). Diagenetic cements in the Gibraltar Limestone Formation include micrite, microspar, brous and radiaxial brous calcite cements (Fig. 3C), which are inferred to have precipitated from sea water in a submarine environment (cf. Tucker & Wright, 1990). Fine and medium crystalline dolomites post-date these marine cements, lling the centres of pore spaces (Fig. 3C) or occurring as detrital internal sediments in geopetal structures, suggesting that dolomitization was also relatively early but post-dated marine CaCO3 cements. The ne and medium replacement dolomites are cross-cut by stylolites (Fig. 3C) and by fractures that are lled with later stage calcite and dolomite cements that have not been investigated. ISOTOPIC SIGNATURE OF EARLY JURASSIC SEA WATER Because sea water shows secular variation in oxygen, carbon and strontium isotopic composition through geologic time (e.g. Burke et al., 1982; Veizer et al., 1997), it is critical to establish the isotopic signatures for Early Jurassic sea water before interpreting isotopic data from the Gibraltar dolomites. The d18O and d13C values of calcites precipitated from Early Jurassic sea water range from 3& to 1& PDB and 14& PDB, respectively (Fig. 4), according to analyses of pristine brachiopod shells and other calcitic fossils (Veizer et al., 1997). Major et al. (1992) suggested that the oxygen isotopic fractionation between calcite and dolomite varies from 15& to 35& PDB. Taking a mean of 25& as the fractionation between dolomite and calcite, dolomites precipitated from normal Early Jurassic sea water should have d18O values from 05& to 15& PDB (Fig. 4). Dolomites formed by slightly evaporated Early Jurassic sea water before gypsum precipitation should therefore have d18O values slightly higher than 15& PDB (Figs 4 and 5). Dolomites

Fig. 4. A cross-plot of d13C against d18O for Gibraltar limestones and ne/medium crystalline dolomites, shown relative to elds plotted from the literature for Early Jurassic marine calcite (Veizer et al., 1997) and calculated (cf. Major et al., 1992) for Early Jurassic marine dolomite.

associated with present-day sabkha evaporites in Abu Dhabi have d18O values ranging from 14& to 40& (McKenzie, 1981). Based on the analyses of whole carbonate rocks (Burke et al., 1982) and belemnites (Jones et al., 1994), the estimated 87Sr/86Sr ratios of Early Jurassic sea water range from 07071 to 07078 (Fig. 5). Diagenetically unaltered brachiopods collected from the upper parts of the Gibraltar Limestone Formation have 87Sr/86Sr ratios of 070750400707570 (Fig. 5; Bosence et al., 2000). This equates to the Sinemurian stage of the Early Jurassic (19791997 Ma).

Fig. 5. A cross-plot of 87Sr/86Sr against d18O for Gibraltar limestones and ne/medium dolomites, shown relative to the range of 87Sr/86Sr values from Gibraltar brachiopod shells (Bosence et al., 2000) and for Early Jurassic sea water (Jones et al., 1994), with indication of apparent trends resulting from diagenetic alteration.

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Dolomitization of Liassic platform carbonates, Gibraltar ISOTOPE GEOCHEMISTRY OF GIBRALTAR DOLOMITES The d18O values display a gradual increase from the limestones to the medium crystalline to the ne crystalline dolomite (Fig. 4). The ne crystalline dolomite has the highest d18O values, ranging from 01& to 27& PDB (mean 12& PDB), which are either similar to or slightly higher than the expected values for dolomites formed by Early Jurassic sea water (Fig. 4). The d18O values of the medium crystalline dolomite vary from 24& to 15& PDB (mean 057& PDB; Fig. 4). Some of these values are slightly lower than those expected from dolomites formed by Early Jurassic sea water, whereas others are similar to the expected values and overlap with those of ne crystalline dolomites (Fig. 4). The d18O values for the limestones range from 40& to 21& PDB (mean 28& PDB), falling in the eld of Early Jurassic marine calcite, except for two slightly lower values (Fig. 4). The d13C values range from 16& to 29& PDB (mean 22& PDB) for ne crystalline dolomites, and from 08& to 36& PDB (mean 19& PDB) for medium crystalline dolomites. These fall within the range of published values for precipitates from Early Jurassic sea water except for three slightly lower values for medium crystalline dolomites (Fig. 4). Five strontium isotope analyses taken from nonluminescent, matrix-free brachiopod valves from the upper part of the Buffadero Member vary from 0707504 to 0707570 (Bosence et al., 2000; Fig. 5). Bulk strontium values from drilled limestone samples are higher and range from 070787 to 070856 (Fig. 5). The 87Sr/86Sr ratios of eight ne crystalline dolomites range from 07076 to 07081 (mean 07079). Four of these ratios are similar to the estimated values of Early Jurassic sea water (0707107078), and the remainder are slightly higher (Fig. 5). The 87Sr/86Sr ratios of three medium crystalline dolomites are highly variable, ranging from 07077 to 07095 (mean 07084): one falls within the range of Early Jurassic sea water, one is close to but slightly higher than that range, and one is signicantly more radiogenic. DOLOMITIZATION MODEL

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mon occurrence there of restricted-marine, but moderate-energy peritidal carbonate facies, and the appearance of a restricted-marine biota of calcied green algae and agglutinated benthic foraminifera at horizons only where dolomite abundance decreases (i.e. at the top of the Keightley Member; Bosence et al., 2000), all suggest waters of variable or elevated salinity during the deposition of the lower part of the succession. However, the absence of massive gypsum/anhydrite and/or evaporite solutioncollapse breccias suggests that evaporated sea water did not reach the salinity required for abundant gypsum precipitation.

Isotopic evidence
The oxygen isotopes of the replacement ne crystalline dolomites are either similar to or slightly higher than those expected from Early Jurassic marine dolomite (Fig. 4). The highest d18O value is 27& PDB, about 12 to 32& higher than the estimated values for Early Jurassic marine dolomite (05 to 15& PDB), indicating that the dolomitizing uids were slightly evaporated Early Jurassic sea water. In addition, the d13C and 87Sr/86Sr ratios of some ne crystalline dolomites fall within the range of expected values for Early Jurassic sea water (Figs 4 and 5), supporting the inference that this was the uid responsible for dolomitization. The presence of a restricted marine biota and the rare gypsum pseudomorphs within parts of the Main Ridge succession is consistent with the penesaline rather than the normal marine salinity range for formation of the Gibraltar dolomites (Fig. 6). The spread of d18O values from 01& to 27& (PDB) seen in the ne crystalline dolomites might result from factors such as: (1) mixing of evaporated sea water with fresh water; (2) variation in salinity resulting from different degrees of evaporation; and (3) diagenetic alteration during burial. The lack of negative d13C values and the absence of positive co-variation of d13C and d18O, typical of dolomites formed by mixed evaporative brines and fresh water (Meyers et al., 1997), make the rst possibility unlikely. Although dolomitizing uids that originated from Early Jurassic sea water may have been subject to different degrees of evaporation and produced variable d18O values, the decrease in d18O values with a corresponding increase in 87Sr/86Sr ratios (Fig. 5) is better explained by diagenetic alteration during burial. On this assumption, the primary composition of the ne crystalline dolomite was origin-

Petrographic evidence
The lack of normal marine biota from the lower dolomitized portion of the succession, the com-

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Fig. 6. Diagram indicating model for dolomitization of peritidal carbonates by slightly evaporated (penesaline) sea water in a restricted platform setting driven by high-frequency sea-level changes (after Adams & Rhodes, 1960; Tucker & Wright, 1990.).

ally in the range for dolomite formed by penesaline sea water (Fig. 5). Diagenetic alteration has produced a trend of decreasing d18O values with a corresponding increase in 87Sr/86Sr ratios, a trend also suggested by the limestone samples and the predicted Jurassic marine calcite eld (Fig. 5). Although some medium crystalline dolomites have oxygen, carbon and strontium isotopic values overlapping with those predicted for Early Jurassic marine dolomites, the remainder have lower d18O and d13C but higher 87Sr/86Sr ratios (Figs 4 and 5). The wider range of d18O, d13C and 87 Sr/86Sr in the medium crystalline dolomite, compared with those of the ne crystalline dolomite, might be interpreted as the result of: (1) dolomitization at slightly higher temperatures during shallow burial; or (2) multistage dolomitization. A 18& (PDB) difference between the average d18O values of ne and medium crystalline dolomites indicates that the temperature of dolomitizing uids was about 8 C higher for medium crystalline dolomite if the d18O values of dolomitizing uids were the same (equation of Land, 1985). The estimated thickness of the Gibraltar Limestone Formation is at least 460 m (Bosence et al., 2000) with the younger Catalan Bay Shale of unknown thickness. Burial at 500 m depth would have been enough to raise the temperature of pore waters sufciently to effect dolomitization of at least the lower parts of the formation (i.e. the Bleak and Europa members). For the second interpretation to be true, measured isotopic values should represent a mixture of early-stage ne crystalline dolomite with a later stage dolomite. This is supported by the cloudy centres with clearer rims and blotches of dull-orange luminescence seen under CL in some medium crystalline dolomite crystals (Fig. 3B). In both interpretations, Early Jurassic sea water is the presumed dolomitizing uid.

Hydrology of dolomitizing uids

The hydrological system of dolomitizing uids with a slightly elevated marine (i.e. penesaline) salinity in a marginal marine setting is most similar to the reux model described by McKenzie et al. (1980), i.e. a ow of denser saline waters from an inner platform outwards towards a less saline marine basin (Fig. 6). A revision to this classic reux model has recently been proposed by Sun (1994) to explain the metrescale, dolomitized, peritidal cyclic carbonates without associated evaporites that characterize greenhouse periods of Earth history. He proposed that dolomitization could occur in laterally extensive platform-top environments from repeated ooding and reux of marine waters of slightly increased salinity. The combination of high-frequency, metre-scale cyclicity superimposed on low-frequency (third-order?) cycles within the Gibraltar Limestone indicates an additional mechanism whereby marine or elevated marine pore waters may be driven through the peritidal carbonates during high-frequency sea-level changes during low-frequency falling stages. Petrographic and isotopic data from this study, therefore, provide evidence for the validity of Sun's model. The volumetric ow model proposed by Shields & Brady (1995) also suggests that regional-scale reux is a viable mechanism for regional-scale dolomitization during shallow burial (<500 m). On the Great Bahamas Bank, sea water of elevated salinity develops on the platform interior (e.g. Simms, 1984) and can be reuxed into the platform, resulting in massive dolomitization (Whitaker & Smart, 1990). Work undertaken on the Cretaceous of Israel (Sass & Katz, 1982) interprets massive dolomitization of evaporite-free, shallow-water carbonates with stable isotope values similar to those estimated

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Dolomitization of Liassic platform carbonates, Gibraltar for Cretaceous sea water (d18O 25 to +07 and d13C 09 to +25). Reux of penesaline sea water driven by high-frequency sea-level changes could therefore produce a large-scale ow system that affects thousands of square kilometres on ancient carbonate platforms during periods of hydrographic restriction and climatic aridity, resulting in massive dolomitization. The maximum abundance of replacement dolomite is within the rst falling and lowstand phase of low-frequency (third-order?) cycles that affected the stratigraphically lowest portion of the Gibraltar Limestone (Bosence et al., 2000) in the Bleak and Europa members. Reux dolomitization has previously been argued to characterize sea-level falls in arid climate settings (Purser et al., 1994) as brines are driven into previously deposited limestones. However, a second phase of falling and lowstand conditions in the uppermost part of the Gibraltar Limestone (Buffadero Member) is not affected by dolomitization. The Little Bay Shale Formation that underlies the Gibraltar Limestone Formation (Fig. 1) would probably have acted as a basal aquitard constraining uid ow to within the overlying peritidal carbonates and thereby promoting dolomitization. Higher in the sequence, the Buffadero Member carbonates have coarser textures and are not underlain by an aquiclude, and the falling stage and lowstand carbonates are not dolomitized.

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Clearly, these widespread Early Jurassic dolomites formed in different geological environments, and more studies are required before a regional model for dolomitization can be proposed. SUMMARY AND CONCLUSIONS Peritidal carbonates of the lower part of the Lower Jurassic Gibraltar Limestone Formation have been replaced by ne and medium crystalline dolomites. The dolomitizing uid responsible for the ne crystalline dolomite is inferred to have been penesaline Early Jurassic sea water that reuxed through the primary carbonate sediments during high- and low-frequency sea-level changes. This is supported by d18O values that are either similar to, or slightly higher than, those expected for Early Jurassic marine dolomite, and d13C values and 87Sr/86Sr ratios that overlap those of Early Jurassic sea water. The absence of massive evaporitic minerals and/or solution-collapse breccias in these inner-platform carbonates indicates that evaporation of sea water during dolomitization did not attain the concentration at which massive deposits of gypsum would precipitate. Some of the medium crystalline replacement dolomite has oxygen, carbon and strontium isotopic values similar to those of Early Jurassic marine dolomites, whereas others have lower d18O and d13C but higher 87Sr/86Sr. Early Jurassic sea water is interpreted as the possible dolomitizing uid for the medium as well as the ne crystalline dolomite. The wider ranges of oxygen, carbon and strontium isotopes of the medium crystalline replacement dolomite, however, might indicate: 1 dolomitization during shallow (500 m) burial and consequently slightly higher temperature; or 2 multistage dolomite generation, as suggested by cloudy centres with clear rims and blotches of dull-orange luminescence in some medium crystalline dolomite. Contrary to some classic models of dolomite formation, which infer the action of hypersaline brines, isotopic data from this study indicate that massive dolomitization may also occur in peritidal carbonates through the reux of penesaline sea water driven by a combination of high- and low-frequency sea-level changes. This study, together with previously published dolomitization models, indicates that replacement dolomites

Global and regional comparisons

Dolomites are common in the Early Jurassic of western Tethys, and this is consistent with their recorded global abundance (6065%) for this period (Given & Wilkinson, 1987). Early Jurassic dolomites from western Tethys are reported from the Betic Mountains of Spain (e.g. Martn, 1979; Rey, 1997), the Atlas Mountains of Morocco (e.g. Crevello, 1991), central Tunisia (e.g. Soussi & M'Rabet, 1994), Greece (e.g. 3 Flugel, 1983; Scherreiks, 2000), the Apennines (e.g. Colacicchi et al., 1975; Barattolo & Bigozzi, 1996) and the Iblean Plateau (Ronchi et al., 2000) of Italy. Few of these studies include detailed geochemical analyses for the dolomite enabling environments of dolomitization to be established. Exceptions are Soussi & M'Rabet (1994) and Ronchi et al. (2000) who both interpret a deep burial environment for dolomitization of cyclic peritidal carbonates. This is in contrast to the shallow post-depositional environment proposed here for the dolomites of the Gibraltar Limestone.

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U Manuscript received 13 July 1999; revision accepted 3 July 2000.

2001 International Association of Sedimentologists, Sedimentology, 48, 153163