ALBERT

Notes: Pervasive dolomites occur preferentially in the stromatoporoid biostromal (or reefal) facies in the basal Devonian (Givetian) carbonate rocks in the Guilin area, South China. The amount of dolomites, however, decreases sharply in the overlying Frasnian carbonate rocks. Dolostones are dominated by replacement dolomites with minor dolomite cements. Replacement dolomites include: (1) fine to medium, planar-e floating dolomite rhombs (Rd1); (2) medium to coarse, planar-s patchy/mosaic dolomites (Rd2); and (3) medium to very coarse non-planar anhedral mosaic dolomites (Rd3). They post-date early submarine cements and overlap with stylolites. Two types of dolomite cements were identified: planar coarse euhedral dolomite cements (Cd1) and non-planar (saddle) dolomite cements (Cd2); they post-date replacement dolomites and predate late-stage calcite cements that line mouldic vugs and fractures. The replacement dolomites have δ18O values from −13·7 to −9·7‰ VPDB, δ13C values from −2·7 to + 1·5‰ VPDB and 87Sr/86Sr ratios from 0·7082 to 0·7114. Fluid inclusion data of Rd3 dolomites yield homogenization temperatures (Th) of 136–149 °C and salinities of 7·2–11·2 wt% NaCl equivalent. These data suggest that the replacive dolomitization could have occurred from slightly modified sea water and/or saline basinal fluids at relatively high temperatures, probably related to hydrothermal activities during the latest Givetian–middle Fammenian and Early Carboniferous times. Compared with replacement dolomites, Cd2 cements yield lower δ18O values (−14·2 to −9·3‰ VPDB), lower δ13C values (−3·0 to −0·7‰ VPDB), higher 87Sr/86Sr ratios (≈ 0·7100) and higher Th values (171–209 °C), which correspond to trapping temperatures (Tr) between 260 and 300 °C after pressure corrections. These data suggest that the dolomite cements precipitated from higher temperature hydrothermal fluids, derived from underlying siliciclastic deposits, and were associated with more intense hydrothermal events during Permian–Early Triassic time, when the host dolostones were deeply buried. The petrographic similarities between some replacement dolomites and Cd2 dolomite cements and the partial overlap in 87Sr/86Sr and δ18O values suggest neomorphism of early formed replacement dolomites that were exposed to later dolomitizing fluids. However, the dolomitization was finally stopped through invasion of meteoric water as a result of basin uplift induced by the Indosinian Orogeny from the early Middle Triassic, as indicated by the decrease in salinities in the dolomite cements in veins (5·1–0·4 wt% NaCl equivalent). Calcite cements generally yield the lowest δ18O values (−18·5 to −14·3‰ VPDB), variable δ13C values (−11·3 to −1·2‰ VPDB) and high Th values (145–170 °C) and low salinities (0–0·2 wt% NaCl equivalent), indicating an origin of high-temperature, dilute fluids recharged by meteoric water in the course of basin uplift during the Indosinian Orogeny. Faults were probably important conduits that channelled dolomitizing fluids from the deeply buried siliciclastic sediments into the basal carbonates, leading to intense dolomitization (i.e. Rd3, Cd1 and Cd2).

Notes: Two types of ‘pseudobreccia’, one with grey and the other with brown mottle fabrics, occur in shoaling-upward cycles of the Urswick Limestone Formation of Asbian (Late Dinantian, Carboniferous) age in the southern Lake District, UK. The grey mottle pseudobreccia occurs in cycle-base packstones and developed after backfilling and abandonment of Thalassinoides burrow systems. Burrow infills consist of a fine to coarse crystalline microspar that has dull brown to moderate orange colours under cathodoluminescence. Mottling formed when an early diagenetic ‘aerobic decay clock’ operating on buried organic material was stopped, and sediment entered the sulphate reduction zone. This probably occurred during progradation of grainstone shoal facies, after which there was initial exposure to meteoric water. Microspar calcites then formed rapidly as a result of aragonite stabilization. The precipitation of the main meteoric cements and aragonite bioclast dissolution post-date this stabilisation event. The brown mottle pseudobreccia fabrics are intimately associated with rhizocretions and calcrete, which developed beneath palaeokarstic surfaces capping cycle-top grainstones and post-date all depositional fabrics, although they may also follow primary depositional heterogeneities such as burrows. They consist of coarse, inclusion-rich, microspar calcites that are always very dull to non-luminescent under cathodoluminescence, sometimes with some thin bright zones. These are interpreted as capillary rise and pedogenic calcrete precipitates. The δ18O values (−5‰ to −8‰, PDB) and the δ13C values (+2‰ to −3‰, PDB) of the ‘pseudobreccias’ are lower than the estimated δ18O values (−3‰ to −1‰ PDB) and δ13C values of (+2‰ to +4‰ PDB) of normal marine calcite precipitated from Late Dinantian sea water, reflecting the influence of meteoric waters and the input of organic carbon.

Notes: Rare earth elements (REE) were determined in fine, medium and coarse crystalline replacement dolomites, and for saddle dolomite cements from the Middle Devonian Presqu'ile barrier from Pine Point and the subsurface of the Northwest Territories and north-eastern British Columbia. REE patterns of the fine crystalline dolomite are similar to those of Middle Devonian limestones from the Presqu'ile barrier. Fine crystalline dolomite occurs in the back-barrier facies and may represent penecontemporaneous dolomitization at, or just below, the sea floor. Medium crystalline dolomite is widespread in the lower southern and lower central barrier. Medium crystalline dolomite is slightly depleted in heavy REE compared with Devonian marine limestones and fine crystalline dolomite, and has negative Ce and Eu anomalies. Medium crystalline dolomites replaced pre-existing limestones or were recrystallized from earlier fine crystalline dolomites. During these processes, the REE patterns of their precursors were modified. Late stage, coarse crystalline replacement dolomite and saddle dolomite cements occur together in the upper barrier and have similar geochemical signatures. Coarse crystalline dolomites have negative Eu anomalies, and those from the Pine Point area also have positive La anomalies. Saddle dolomites are enriched in light REE and have positive La anomalies. The REE patterns of coarse crystalline dolomite and saddle dolomite differ from those of marine limestones and fine and medium crystalline dolomites, suggesting that different diagenetic fluids were responsible for these later dolomites.Although massive dolomitization requires relatively large volumes of fluids in order to provide the necessary amounts of Mg2-. dolomitization and subsequent recrystallization may not necessarily modify the REE signatures of the precursor limestones because of the low concentrations of REE in most natural fluids. Thus, relative fluid-rock ratios during diagenesis may be estimated from REE patterns in the diagenetic and precursor minerals. Fine crystalline dolomites retain the REE patterns of their limestone precursors. In the medium and coarse crystalline dolomites the precursor REE patterns were apparently altered by large volumes of fluids involved during dolomitization. This study suggests that REE compositions of dolomites and their limestone precursors may provide important information about the relative amounts of fluids involved during diagenetic processes, such as dolomitization.

Notes: The petrography and geochemistry of fine- and medium-crystalline dolomites of the Middle Devonian Presqu’ile barrier at Pine Point (Western Canada Sedimentary Basin) are different from those of previously published coarse-crystalline and saddle dolomites that are associated with late-stage hydrothermal fluids. Fine-crystalline dolomite consists of subhedral to euhedral crystals, ranging from 5 to 25 μm (mean 8 μm). The dolomite interbedded with evaporitic anhydrites that occur in the back-barrier facies in the Elk Point Basin. Fine-crystalline dolomite has δ18Ο values between −1·6 to –3·8‰ PDB and 87Sr/86Sr ratios from 0·7079–0·7081, consistent with derivation from Middle Devonian seawater. Its Sr concentrations (55–225 p.p.m., mean 105 p.p.m.) follow a similar trend to modern Little Bahama seawater dolomites. Its rare earth element (REE) patterns are similar to those of the limestone precursors. These data suggest that this fine-crystalline dolomite formed from Middle Devonian seawater at or just below the sea floor.Medium-crystalline dolomite in the Presqu’ile barrier is composed of anhedral to subhedral crystals (150–250 μm, mean 200 μm), some of which have clear rims toward the pore centres. This dolomite occurs mostly in the southern lower part of the barrier. Medium-crystalline dolomite has δ18O values between −3·7 to −9·4‰ PDB (mean −5·9‰ PDB) and 87Sr/86Sr ratios from 0·7081–0·7087 (mean 0·7084); Sr concentrations from 30 to 79 p.p.m. (mean 50 p.p.m.) and Mn content from 50 to 253 p.p.m. (mean 161 p.p.m.); and negative Ce anomalies compared with those of marine limestones. The medium-crystalline dolomite may have formed either (1) during shallow burial at slightly elevated temperatures (35–40 °C) from fluids derived from burial compaction, or, more likely (2) soon after deposition of the precursor sediments by Middle Devonian seawater derived from the Elk Point Basin.These results indicate that dolomitization in the Middle Devonian Presqu’ile barrier occurred in at least two stages during evolution of the Western Canada Sedimentary Basin. The geochemistry of earlier formed dolomites may have been modified if the earlier formed dolomites were porous and permeable and water/rock ratios were large during neomorphism.

Notes: Peritidal carbonates of the Lower Jurassic (Liassic) Gibraltar Limestone Formation, which form the main mass of the Rock of Gibraltar, are replaced by fine 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 fine crystalline dolomite has δ18Ο values either similar to, or slightly higher than, those expected from Early Jurassic marine dolomite, and δ13C values together with 87Sr/86Sr ratios that overlap with sea-water values for that time, indicating that the dolomitizing fluid 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 72–199‰). The medium crystalline dolomite has some δ18Ο and δ13C values and 87Sr/86Sr ratios similar to those of Early Jurassic marine dolomites, which indicates that ambient sea water was again a likely dolomitizing fluid. However, the spread of δ18Ο, δ13C 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 modified sea water with a wide range of salinities (normal, penesaline to hypersaline), provided that there is a driving mechanism for fluid migration. The Gibraltar dolomites confirm other reports of significant Early Jurassic dolomitization in the western Tethys carbonate platforms.