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Sedimenrology (1991) 38,643-670

The diagenesis of the late Dinantian Derbyshire-East Midland carbonate shelf,


central England

G O R D O N M . W A L K D E N * and D A V I D 0. W I L L I A M S ?
*Department of Geology, Kings College, University of Aberdeen, Scotland
The Robertson Group plc, Llandudno, Gwynedd, Wales

ABSTRACT

Carbonate cements in late Dinantian (Asbian and Brigantian) limestones of the Derbyshire carbonate
platform record a diagenetic history starting with early vadose meteoric cementation and finishing with
burial and localized mineral and oil emplacement. The sequence is documented using cement petrography,
cathodoluminescence, trace element geochemistry and C and 0 isotopes.
The earliest cements (Pre-Zone 1) are locally developed non-luminescent brown sparry calcite below
intrastratal palaeokarsts and calcretes. They contain negligible Fe, Mn and Sr but up to 1000 ppm Mg.
Their isotopic compositions centre around 6 * 0 = - 8.5%,, 6I3C= -S.O%,. Calcretes contain less I3C.
Subsequent cements are widespread as inclusion-free, low-Mg, low-Fe crinoid overgrowths and are
described as having a dead-bright-dull cathodoluminescence. The dead cements (Zone 1) are mostly
non-luminescent but contain dissolution hiatuses overlain by finely detailed bright subzones that correlate
over several kilometres. Across dead/bright subzones there is a clear trend in Mg (500-900 pprn), Mn
( 1 0 0 4 0 ppm) and Fe (80-230 ppm). Zone 1 cements have isotopic compositions centred around 6 * 0 =
-S.O%, and 6I3C= -2.5%,. Zone 2 cement is bright, thin and complexly subzoned. It is geochemically
similar to bright subzones of Zone 1 cements. Dull Zone 3 cement pre-dates pressure dissolution and fills
70%or more of the pore space. It generally contains little Mn, Fe and Sr but can have more than 1000 ppm
Mg, increasing stratigraphically upwards. The 6*0 compositions range from - 5.5 to - 15%,and the 6C
+
range is - 1 to 3.2%,. Zone 4 fills veins and stylolite seams in addition to pores. It is synchronous with
Pb, Ba, F ore mineralization and oil migration. Zone 4 is ferroan with around 500 ppm Fe, up to 2500 ppm
Mg and up to 1500 ppm Mn. Isotopic compositions range widely; 6 l 8 0 = -2.7 to -9%, and 613C= - 3.8
to +2,5%,.
Unaltered marine brachiopods suggest a Dinantian seawater composition around 6I8O= O x , (SMOW),
but vital isotopic effects probably mask the original 6I3C (PDB) value. Pre-Zone 1 calcites are meteoric
vadose cements with light soil-derived 6I3C and light meteoric 6O. An unusually fractionated pIuviaI
6I8O(SMOW) value of around -6%, is indicated for local Dinantian meteoric water. Calcrete 6I8O values
are heavier through evaporation. Zone 1 textures and geochemistry indicate a meteoric phreatic
environment. Fe and Mn trends in the bright subzones indicate stagnation, and precipitation occurred in
increments from widespread cyclically developed shallow meteoric water bodies. Meteoric alteration of
the rock body was pervasive by the end of Zone 1 with a general resetting of isotopic values. Zone 3 is
volumetrically important and external sources of water and carbonate are required. Emplacement was
during the Namurian%arly Westphalian by meteoric water sourced at a karst landscape on the uplifted
eastern edge of the Derbyshire-East Midland shelf. The light 6*0 values mainly reflect burial temperatures
and an unusually high local heat flow, but an input of highly fractionated hinterland-derived meteoric
water at the unconformity is also likely. Relatively heavy 613C values reflect the less-altered state of the
source carbonate and aquifer.
Zone 4 is partly vein fed and spans burial down to 2000 m and the onset of tectonism. Light organic-
matter-derived 6l 3C and heavy 6*0 values suggest basin-derived formation water. Combined with
textural evidence of geopressures, this relates to local high-temperature ore mineralization and oil
migration. Low water-to-rock ratios with host-rock buffering probably affected the final isotopic
compositions of Zone 4, masking extremes both of temperature and organic-matter-derived C 0 2 .

643
644 G . M . Walkden and D . 0 . Williams

This cement sequence is typical of Dinantian shelves and platforms throughout England and Wales. We
consider that the introduction of unconformity-derived Zone 3 cement into Dinantian carbonates may
have been widespread in the late Carboniferous resulting in an early and comprehensive reduction in
porosity. This has significant implications for the hydrocarbon reservoir potential of these rocks and helps
to explain the generally non-prospective nature of the platform facies.

INTRODUCTION

Geological setting topped rimmed platform, a pattern that characterized


much of the British late Dinantian (Walkden, 1987).
The Derbyshire carbonate platform is a 500-1900-m- In a number of places on the Derbyshire carbonate
thick succession of shallow-water marine Dinantian platform, especially on the western and north-western
limestones and dolomites exposed over some 450 km2 margins, an unconformity is developed between the
of the southern Pennines (Fig. 1). This platform is in Dinantian and Namurian (Fig. 2). During the Na-
fact just the exposed western side of a far more murian the area as a whole became blanketed by
extensive carbonate body in the subsurface, the mostly northerly or north-easterly-derived fluvio-
Derbyshire-East Midland carbonate shelf, that un- deltaic clastics (Collinson, 1988; Guion & Fielding,
derlies much of eastern England (Strank, 1987; 1988; Ebdon et al., 1990). Initially these filled the
Walkden, 1987; Ebdon et al., 1990). Dinantian inherited basinal lows but soon regional subsidence
sedimentation across the Derbyshire-East Midland took over (Leeder, 1982; Aitkenhead et al., 1985;
carbonate shelf and elsewhere was strongly controlled Smith Lk Smith, 1989), with a new depocentre forming
by extensional faulting (Gawthorpe et al., 1989; Smith well to the north-west of the Derbyshire platform.
&Smith, 1989; Ebdon et al., 1990). Marked thickness This remodelling of the sedimentary basin was
variations occur across the shelf but the effects of accompanied by uplift in the south and east. Thus, on
faulting became less marked towards the end of the the northern margin of the former St Georges Land,
Dinantian. The best exposed rocks are of late Namurian sediments are thin or missing (Edwards &
Dinantian (Asbian and Brigantian) age, are up to Trotter, 1954; Hains & Horton, 1969; Fulton &
500 m thick (Fig. 2) and mostly accumulated as a flat- Williams, 1988) and for a while the area was a

Fig. 1. Location and late Dinantian palaeogeography of the Derbyshire-East Midland carbonate shelf. Inset right: outcrop
map of the Derbyshire carbonate platform and study area. Abbreviations: B, Bowland basin; D, Derbyshire platform; E,
Edale trough; GA, Gainsborough trough; GO, Goyt trough; W, Widmerpool trough.
Derbyshire-East Midland carbonate shelf, England 645

Fig. 2. Chronostratigraphy of the study area and location of sampled sections. Abbreviations: M, mud mound/knoll reef; V,
lava horizon; T, tuff horizon. Sample localities (all quarried exposures or cuttings): 1, Tissington Trail (national grid reference
SK 160575); 2, Hillhead (SK073694); 3, Hartington (SK 152652); 4, Longcliffe (SK238570); 5, Grangemill (SK24257S); 6,
Prospect (SK245575); 7, Intake (SK270550); 8, Middlepeak (SK282547); 9, Coalhills (SK28S553); 10, Dale (SK283542); 11,
Griffe Grange Valley (SK262564).

sediment source, with the stripping of most of its inversion and tectonism probably never 'exceeded
north-facing carbonate shelf prior to southward 2 km (e.g. Smith &Smith, 1989).
Westphalian overlap (Aitkenhead et al., 1985; Collin-
son, 1988). Similar events affected the now buried
eastern side of the Derbyshire-East Midland carbon- Diagenesis
ate shelf. Strank (1987) showed that within 100 km The calcite cementation history of late Dinantian
east of the Derbyshire outcrop, shelf carbonates wedge carbonates of the Derbyshire platform. has been
out subsurface at an unconformity, first with the documented using cathodoluminescence by Walkden
Namurian and then with the overlapping Westphalian & Berry (1984a). Cements typically occur as low-Mg
(Fig. 9a). non-ferroan syntaxial overgrowths on crinoid grains
As the eastern edge became eroded, the centre of with a zonal sequence consisting of non-luminescent
the shelf sagged so that the Namurian succession (Zone I), bright (Zone 2) and dull (Zone 3) calcite,
thickens to more than 0.5 km (Eden etal., 1957; Smith followed by a mostly bright (Zone 4) generation filling
et al., 1967) before thinning again eastwards and microfractures, stylolites and intercrystalline bound-
becoming condensed across the western edge of the aries. Zonal details within Zone 1 are locally correlat-
Derbyshire platform (Stevenson & Gaunt, 1971; able and the dark-bright-dull cement sequence is
Aitkenhead et af., 1985). This local sag was lost by the regionally extensive, occurring throughout the Der-
Westphalian when platform and basin evidently byshire outcrop area and in equivalent shallow-water
subsided uniformly. Deep burial is unlikely to have carbonates throughout southern Britain (Walkden,
affected the top surface of the Derbyshire-East 1987). Such cement sequences are geologically wide-
Midland platform and maximum depths before the spread (e.g. Meyers, 1978; Frank et al., 1982; Grover
onset of late Westphalian-early Permian (Variscan) & Read, 1983) and the pattern has been attributed to
646 G . M . Walkden and D. 0 . Williams

the tendency of major carbonate bodies to follow the Bee Low Limestones Formation (Asbian), the
similar diagenetic trends involving passage from well- Monsal Dale Limestones Formation (early Brigantian)
oxygenated near-surface conditions to reducing burial and the Eyam Limestones Formation (late Brigantian)
conditions. (Fig. 2).
Cements precipitated under these evolving condi- Asbian limestones are arranged in palaeokarst-
tions are exposed to changes in temperature and bound cyclical units that can usually be correlated for
groundwater geochemistry which should be directly tens of kilometres. Cycles are between 1 and 10 m in
reflected in their cation and stable isotope composi- thickness, and the principal lithology is a crinoidal
tions (e.g. Frank et a/., 1982; Meyers & Lohmann, peloidal packstone with subordinate grainstones and
1985). Changes in cement geochemistry were not wackestones. Emergent surfaces are karst-pitted and
documented in detail by Walkden & Berry (1984a), capped by calcretes and volcanic-ash-derived palaeo-
but their general diagenetic model involved a transi- sols (Walkden, 1972, 1974, 1987; Walkden & Walk-
tion from near-surface meteoric vadose to deep burial den, 1990). More than 30 exposure surfaces have been
conditions with pressure dissolution. This paper looks documented through a succession of up to 200m
at the geochemical evolution of a representative (Berry, 1984; Oakman, 1984) demonstrating the
portion of the carbonate platform during this transi- importance of early meteoric diagenesis. Brigantian
tion. The study employs cathodoluminescence, stable rocks are also cyclical but exposure surfaces are not as
isotope and microprobe data to test and refine the well developed. They are generally more than 200 m
models of Walkden & Berry (1984a). thick and are lithologically more variable, including
Cement Zones 1-4 (Table 1) represent successional muddier facies.
diagenetic environments and were individually exten-
sive in time and space. Included in this study, however,
are some earlier cements that are only locally devel-
oped. These are distinguished as Pre-Zone 1 and are METHODS A N D DATABASE
mostly non-luminescent calcite spar related to individ-
ual exposure surfaces similar to the pedogenic cements Samples suitable for geochemical investigation were
described from North Wales by Solomon & Walkden identified during routine petrographical inspection of
(1985). Other Pre-Zone 1 cements are inclusion-rich logged collections from quarries located throughout
with dullor brightluminescenceandoccur in platform- the study area (Fig. 1). These localities are listed in
margin situations and some mud mounds. They are Fig. 2 and details are in Williams (1988).,Samples
replacements of early fibrous or acicular marine were mostly open-textured grainstones/packstones
cements and are the subject of a separate investigation with accessible cements representative of each zone.
(Bingham, 1991). The effects of early compaction in these samples were
Several parts of the Derbyshire-East Midland generally minimal, with minus-cement porosities of
carbonate platform are affected by a late phase of F, 40-55%. These samples were therefore not typical of
Pb, and Ba vein mineralization. This also mainly all rocks and minus-cement porosities down to 20%
involves Asbian and Brigantian rocks and occurs are not unusual. Calcrete samples come from Asbian
during Zone 4. This mineralization is the subject of a palaeokarst surfaces overlain by clay palaeosols and
separate study and is not documented in detail here are identical to samples in Figs 9 and 10 of Walkden
(see Bingham, 1991). (1974).

Study area Cathodoluminescence


The study area comprises shallow-water back-reef Cathodoluminescence petrography employed a stand:
and lagoonal carbonate facies of the southern and ard Technosyn 2001 unit operating at c. 20 kV and
western part of the Derbyshire platform (Fig. 1). The 600 PA. More than 250 samples were cut for cathodo-
area provides a representative transect through a luminescence slides and these were thinned to 40 km
range of late Dinantian depositional environments. and polished on one side only. Cement stratigraphy is
The local stratigraphy is described in Aitkenhead & described as in Berry (1984) and Walkden & Berry
Chisholm (1982) and Aitkenhead ef al. (1985) and (1984a) and a few of the slides were the same as in
comprises the Griffe Grange Member (here regarded these previous studies. A small number of slides were
as mostly Asbian; Woo Dale Limestones Formation), carbon coated for use in the microprobe.
Derbyshire-East Midland carbonate she(f,England 647

Table 1. Sumnary of composition, appearance, distribution and interpretation of cements from Pre-Zone I to Zone 4
Zone Composition Characteristics Luminescence Substrate and location Interpretation
Pre-Zone 1 Low-Mg Light brown, Non-luminescent. Non-selective : Speleothem deposits,
calcite pseudopleochroic, Rare needle fibres primary voids, mainly vadose
inclusion-rich, (e.g. Solomon & calcretes,
columnar, bladed or Walkden, 1985) dissolution cavities
equant spar.
Gravitational and
surface-tension effects
or well terminated
crystals. Overgrown
by later cements

Zone 1 Low-Mg Colourless, usually Non-luminescent, Selective on crinoids Meteoric, phreatic-


calcite inclusion-free spar; with complex in grainstones and oxic with active
syntaxial on crinoid micrometre-sized packstones. cementation, and
grains; rare discrete luminescent Subzones reveal stagnant suboxic
equant crystals. subzones etch pits and with slow
Indistinguishable in anhedral-euhedral cementation
plane light. Normally growth trend with
overgrown by later time
cements

Zone 2 Low-Mg Colourless, inclusion- Bright yellow/orange Selective on Zone 1 Meteoric, shallow
calcite free; syntaxial on with complex cement. Fills burial beneath
Zone 1 cement. subzones and fractures and etch zone of active
Indistinguishable irregular growth. pits in earlier cementation
from Zone 1 cement Thin and commonly cements. Rarely
in plane light absent replaces non-
carbonate allochems

Zone 3 Low-Mg Colourless, inclusion- Dull brown/orange Non-selective. Shallow to deep


calcite free, equant calcite or with subtle Growth-rate suboxic meteoric
syntaxial on Zones 1 variations. substrate burial
or 2 cement. Occasional sector dependent.
Indistinguishable zoning. Form Occludes most
from Zones 1 or 2 changes; pores. Fills
cement in plane light pseudofaces compactive
(Walkden &Berry, fractures and
1984a) previously sealed
pores

Zone 4 Low-Mg Colourless, inclusion- Mostly bright yellow/ Non-selective. Fills Burial
calcite, free, equant, drusy orange but much veins, fractures,
commonly calcite or syntaxial on variation. stylolite seams,
ferroan Zones 1-3 cement. Dissolution effects intergranular pores
Indistinguishable and occasional and dissolutional
from Zones 1-3
cement in plane light
sector zonine - voids

Trace elements time. A total of 155 probe analyses from five selected
samples are included in this study. Results are reported
Trace element analyses were obtained using a wave- for Mg, Fe, Sr and Mn (wtx).
length-dispersive Cameca Camebax microprobe at Typical detection limits calculated for individual
Edinburgh University. This instrument permits highly spot analyses at the 95 and 99% confidence limits,
accurate spatial discrimination through the defocusing respectively, are : Mn, 200 and 300 ppm; Fe, 230 and
of the electron beam to view the specimen in 340 ppm; Sr, 230 and 340 ppm; Mg, 85 and 130 ppm.
cathodoluminescence. The instrument was operated The degree of variation between individual spot
at 20 kV using a 10-pm beam raster and a 15-s count analyses, and between means for the same cement
648 G.M . Walkden and D. 0. Williams

zone in different samples, can be gauged from the tion being those with obvious inhomogeneities in
scatter in the Mn/Fe cross-plots in Fig. 6(b). Here cathodoluminescence. The shells of the large spiriferid
mean values of all Mn/Fe spot data for each cement Davidsonina septosa were found by Berry (1984) to
zone are plotted by sample (numbered plots) as well show the least altered compositions and this species
as all the spot data for one zone in a single sample has been used in this study although it is only present
(plot 5). The field for plot 5 comprises seven spot in large numbers in the Asbian. Organic contaminants
analyses of Zone 1 bright subzones and shows were removed from samples by immersion in 1%
representative variance. The mean values for plot 5 sodium hypochlorite solution for 24 h (e.g. Irwin et
are: Mn, 119 ppm (mean deviation 56%) and Fe, al., 1977).
254 ppm (mean deviation 47%). These values lie The CO, was evolved using 100% orthophosphoric
within the quoted detection limits, but averaging spot acid at 25C and after purification was isotopically
data for identical cements improves detection limits analysed using a V.G. Micromass 903 mass spectrom-
so that for plot 5 the detection limits at the 95 and 99% eter. Standard correction procedures of Craig (1957)
confidence levels, respectively, drop to: Mn, 80 and were employed and the results are expressed in the
120 ppm; Fe, 85 and 125 ppm. The numbered plots in conventional 6 notation (x0) relative to the PDB
Fig. 6(b) therefore have differing reliability according standard.
to the number of spot analyses used in each mean (see
figure caption).
With the exception of Fig. 6(b), however, zonal C E M E N T P E T R O G R A P H Y A N D TRACE
means are not quoted by sample and the data used in
ELEMENT GEOCHEMISTRY
Table 2 and in Fig. 6(a) are all-sample means for each
zone derived by averaging all respective spot analyses Pre-Zone 1 cements
regardless of sample. Clearly such global figures are
only indicative and produce no additional improve- The Pre-Zone 1 cements sampled in this study are
ment in detection limits. In some instances figures are composed of brown, inclusion-rich, columnar, bladed
close to or below the nominal detection limits, but or equant sparry calcite crystals up to 10mm long
clear and consistent trends do emerge (Fig. 6a). (Fig. 3, Table I). They consist of non-luminescent
low-Mg non-ferroan calcite (average Mg =984 ppm,
Fe= 110 ppm, Mn = 114 ppm; Table 2). Inclusions
Stable isotopes
comprise amorphous unoxidized organic matter and
This study includes 139 stable isotope analyses, 74 fluid/gas and are micrometre-sized or less. These
from Asbian cements, calcretes and whole rocks, 46 commonly mark meniscus and planar accretion
from Brigantian cements or whole rocks and 19 from surfaces or individual crystal terminations.
Asbian brachiopod or crinoid grains. Analyses are The cements are locally abundant. In Asbian strata
displayed as 6'3C-6'80 bivariate plots in Figs 7 and they occur within small dissolution cavities beneath
8. Analyses were done at the Scottish Universities palaeokarst surfaces or within calcretes. In Brigantian
Research Reactor Centre at East Kilbride. strata they are present in shelter pores and dissolution
Sampling of certain cement zones was difficult cavities within platform-margin mud mounds. In both
owing to their syntaxial relationships and lack of cases they may show gravitational morphologies and
distinctiveness in ordinary light. Polished plaquettes may be associated with geopetal accumulations of
prepared from vetted samples were first mapped under calcite silt or clay minerals.
cathodoluminescence, then sampled under a binocular The growth fabrics and geochemistry of these
microscope using a scalpel or tungsten-tipped dental cements compare well with meteoric precipitates
drill. Most samples obtained in this way were well elsewhere (Kendall & Broughton, 1978; Braithwaite,
above a 3-mg minimum set for isotopic analysis. The 1979; Binkley et al., 1980; James & Choquette, 1984).
only cements that proved impossible to sample The Mg content may be attributable to local dissolu-
satisfactorily were Zones 1 and 4 in Brigantian rocks tion of metastable Mg-calcite grains as described by
and Zone 2 in all rocks. Benson & Matthews (1971) in Quaternary meteoric
Biogenic allochems were sampled more easily, but vadose cements from Barbados, but it can also arrive
previous studies by Berry (1984) have shown that late as a marine aerosol (Budd & Land, 1990). Williams
Dinantian brachiopod shells are variably altered, (1988) proposed that Pre-Zone 1 cements formed
those showing the greatest range in isotopic composi- contemporaneously with suprajacent emergent sur-
Derbyshire-East Midland carbonate shelf, England 649

Table 2. Summary of trace element geochemistry of cement zones.


~

Zone Mg Sr Fe Mn Samples Analyses


Pre-Zone 1
Asbian 0890 0255 009 1 0138 1 13
Brigantian 1063 0176 0125 0095 2 15
Average 0984 0214 01 10 01 14 3 28

Zone 1 Bright
Asbian 1239 0225 0230 0468 4 24
Brigantian none

Zone 1 Dark
Asbian 0496 0183 0088 0105 4 41
Brigantian none

Zone 2
Asbian 0774 0281 0154 0458 2 14
Brigantian 1216 0249 0101 0869 1 5
Average 089 1 0273 0140 0458 3 19

Zone 3
Asbian 1125 0336 0054 0143 3 22
Brigantian 0703 0255 01 10 0286 1 4
Average 1060 0324 0063 0165 4 26

Zone 4
Asbian 1069 0336 0495 0773 3 13
Brigantian 2539 0183 0515 1534 1 4
Average 1416 0300 0501 0952 4 17
Figures are element concentration (ppm) and are simple mean values of all spot analyses of the respective zones. Detection
limits and variance are discussed in the text.

faces (cf. Solomon & Walkden, 1985). Other types of subzones in Zone 1 cements have a composition
Pre-Zone 1 cement show textural and geochemical similar to Pre-Zone 1 cements, but with less Mg
evidence of a marine origin and are not included in (c. 500 ppm; Table 2, Fig. 6a). They are geochemically
this study. distinct from the brightly luminescent subzones of
Zone 1 which have more than double the Mg and Fe,
and over four times the Mn (c. 450 ppm; Table 2, Fig.
Zone 1-3 cements 6).
These cements typically consist of inclusion-free, Walkden& Berry (1984a) interpreted Zone 1 cement
sparry, low-Mg non-ferroan calcite (Figs 3 & 4, Tables as a shallow meteoric phreatic precipitate developed
1 & 2). They normally occur as a single cement during the emergent phases of sedimentary cycles.
generation and separate zones can only be distin- The blocky texture, substrate selectivity, dissolution
guished in cathodoluminescence. features, lack of luminescence and geochemistry
Zone 1 cement (Fig. 4, Table 1) is mostly non- compare well with meteoric phreatic cements from
luminescent, but contains thin micrometre-scale ancient and recent carbonates (e.g. Land et a/., 1967;
bright subzones commonly revealing anhedral growth Gavish & Friedman, 1969; Meyers, 1978; Longman,
patterns and dissolutional hiatuses (Walkden & Berry, 1980). The thin bright bands are believed to be related
1984b). It is strongly substrate selective, occurring to slow growth during the repeated stagnation or
almost exclusively within syntaxial overgrowths on replacement of meteoric groundwaters that accom-
echinoderm grains. It post-dates Pre-Zone 1 and the panied the submergent phases of the sedimentary
dissolution of aragonitic grains, and fills up to 25% of cycles (Berry, 1984; Walkden, 1987).
available pore space in Asbian rocks but much less in Zone 2 cement (Figs 3b & 4b, c, Table 1) is brightly
Brigantian rocks. luminescent but can be thin or absent. It is never
Containing very little Mn and Fe, non-luminescent found in sufficient quantities for isotopic analysis and
650 G . M . Walkden and D.0.Williams

Fig. 3. Pre-Zone 1 and later cements, Field of view of each frame = 2.5 mm. (a) Inclusion-rich bladed drusy calcite (vadose to
phreatic) overgrowing a dished vadose speleothem growth surface (arrowed) formed in equant sparry calcite. The initial
substrate is a marine allochem. Brigantian, Knoll Reef, Coalhills Quarry, Wirksworth. (b) Cathodoluminescence image of (a).
Two generations of non-luminescent Pre-Zone 1 cement are almost indistinguishable (boundary arrowed). Zone 1 cement is
missing or indistinguishable; the outer boundary of the non-luminescent cements is etched and repaired by bright Zone 2
cement; dull Zone 3 cement fills the remainder. (c) Inclusion-bearing bladed and equant drusy calcite fringes a brachiopod
shell fragment. No textural evidence of growth stages in plane light. Asbian, Longcliffe Quarry, Grangemill.
(d) Cathodoluminescence image of (c), A sweeping/planar vadose growth surface (arrowed) on early non-luminescent calcite
is revealed by a line of rhombohedra1 crystals with bright subzones. Subsequent crystals are unconfined and thus probably
phreatic. The boundary may separate Pre-Zone 1 and Zone 1 cements. Bright Zone 2 cement is poorly developed; dull Zone 3
cement fills the remainder.

so is not discussed in detail. The geochemistry of Zone that reveal euhedral crystals. It is not substrate-
2 cement is comparable with that of the bright selective and new crystals nucleate at this stage on
subzones within Zone 1 cement, showing significantly most grains. The cements show a return to low levels
more Mg, Fe and Mn than in non-luminescent Zone of Mn and Fe (Table 2, Fig. 6) and the dull
1 cements (Table 2, Fig. 6a). The zone probably luminescence is not attributable to Fe-quenching (e.g.
reflects slow cementation in a region of reduced Fairchild, 1983, cf. Grover & Read, 1983). The overall
carbonate supply below the reach of cement-bearing Mn content is the more likely control but there is
and well-oxygenated meteoric water (Walkden & considerable compositional overlap with the field of
Berry, 1984a). non-luminescent cements (Fig. 6b). The Mg content
Zone 3 cement (Figs 3b, 4a & Sa, b, Table 1) has exceeds earlier zones (< 1000 ppm; Table 2), but is
uniform dull luminescence with indistinct subzones still low. Analyses reveal a progressive rise in Mg
Derbyshire-East Midland carbonate shelf, England 65 1

Fig. 4. Zone 1 and later cements. All frames are syntaxial overgrowths on crinoid substrates in cathodoluminescence; field of
view of each frame= 2.5 mm. (a) Non-luminescent Zone 1 cement contains micrometre-sized bright subzones (arrowed, 1)
which typically overlie anhedral-subhedral syntaxial overgrowth surfaces with dissolutional irregularities. Bright subzones
can show complex internal detail and are best developed close to the c-axis. As growth progressed into Zone 3 cement (dull,
arrowed, 3), interfacial angles of scalenohedral fe.ces steadily increased and the termination became more acute (pseudofaces
phenomenon of Walkden & Berry, 1984b). Zone 2 cement (bright) is poorly developed. Asbian, Grangemill Quarry,
Grangemill. (b) An overgrowth from a locality near to that of (a) and from the same stratigraphic level shows a more complete
Zone 1 cement stratigraphy. The first six bright subzones probably correlate directly with (a) but later ones are poorly
represented or missing in (a). Zone 2 cement is also very much better developed in (b) and is likely to represent a condensed
sequence of Zone I-type bright subzones. Asbian, Prospect Quarry, Grangemill. (c), (d) Compactive fracturing of Zone 1
cement. Fractures immediately post-date Zone 1 cement and are healed syntaxially by Zones 2 and 3 cement, despite
considerable structural strain. Asbian, Prospect Quarry, Grangemill.

through Zone 3 and in one transect through a 1-mm & Berry (1984a) suggested a deeper more stable
Zone 3 crystal (six spot analyses) Mg rose from freshwater-cementing environment than for Zone 1. ,
560 ppm to more than 2500 ppm.
Zone 3 cement both pre-dates and post-dates
Zone cements
compactional fracturing, but is cut by pressure-
dissolution seams (Fig. jd). Volumetrically-it is the Zone 4 cements (Fig. 4, Table 1) generally consist of
most important zone, occupying about 70% of pore brightly luminescent, inclusion-free, low-Mg ferroan
space in Asbian rocks, and up to 100% in Brigantian calcite. Zone 4 occurs as an occluding syntaxial cement
rocks. Petrographical evidence again indicates a within primary or dissolutional secondary pores and
meteoric phreatic origin for Zone 3 cement. Walkden is found along stylolite seams, veins, microfractures
652 G . M . Walkdenand D . 0 . Williams

Fig. 5. Zones 3 and4 cements, fractures and stylolites. All frames in cathodoluminescence; field of view of each frame = 2.5 mm.
(a) Zone 3 cement crystals (dull) were selectively etched (arrowed) prior to the introduction of Zone 4 cement (bright).
Patchiness in Zone 3 cement is attributable to sector zoning. Asbian, Longcliffe Quarry, Grangemill. (b) Fractures penetrate a
Zone 1 and sectored Zone 3 cement sequence (arrowed). These are filled by Zone 4 (bright) cement which connects with pores
occluded by the same cement. Fine detail indicates that fracturing occurred on more than one occasion but in this sample was
not accompanied by much dissolution. (c) Stress-related vein festoons filled by Zone 4 (bright) cement are associated with a
late stylolite. The stylolite cuts a Zone 3-cemented pelsparite and has evidently reopened in response to shear. Conjugate veins
along its length are filled by Zone 4 cement. Asbian, Hillhead Quarry, Buxton. (d) A residue-tipped early stylolite intersects
Zone 1 and Zone 3 cement in a calcrete. There is no associated Zone 4 cement. Asbian, Hillhead Quarry, Buxton.

and intercrystalline boundaries. Fluorite is sometimes 1967; Moore, 1985), but individual analyses of bright
associated with Zone 4 cement, indicating that the cements show more than 2000ppm Fe (mean of
important phase of carbonate-hosted ore mineraliza- 900 ppm, Fig. 6a). Average compositions as used in
tion found in a number of places across the platform Fig. 6(b) therefore hide considerable subzonal varia-
occurred roughly contemporaneously. Hydrocarbons, tion, but the bright cathodoluminescence of Zone 4
in the form of dense bitumen, sometimes occlude cement occurs generally in spite of the elevated Fe,
pores lined with Zone 4 cement. Zone 4 cement is commonly regarded as a quencher of luminescence
volumetrically unimportant, amounting to only zz 5% (Fairchild, 1983). More recent work by Mason (1987)
of pore-filling cement. and Hemming et al. (1989) shows that both absolute
Zone 4 cements have the highest average levels of concentrations of Fe and Mg and the Fe/Mg ratio
both Fe and Mn (Table 2, Figs 5b & 6a). They usually may control luminescence in calcites. Fe/Mn ratios of
stain readily using potassium ferricyanide (e.g. Dick- averaged Zone 4 cement samples vary from 1.5 to 2.9
son, 1965) which is effective at Fe contents of a few and we find no simple relationship between Fe and
hundred parts per million (e.g. Oldershaw & Scoffin, Mn trends to account for the luminescence, either
Derbyshire-East Midland carbonate shelf, England 653

10 000 10000
a b

RANGF OF / I
1000 1000

7
f B
Sr ka
Mn
100 Fe 100

I 1 1 1 I I 10
10 100 1000
PZ1 Z1B Z1D Z2 23 24
P P Fe
~
Fig. 6. (a) Variation in trace element geochemistry by cement zone. Mean compositions of successive cement zones for Mg, Sr,
Mn and Fe are plotted using the probe data in Table 2. Shaded areas indicate the range of individual sample means prior to
calculation of global averages (individual sample data not included in Table 2). Abbreviations: PZ1, Pre-Zone 1; ZlB, Zone 1
bright subzone; Z l D , Zone 1 non-luminescent subzone; 22, Zone 2; 23, Zone 3; 24, Zone 4. (b) Mn/Fe cross-plots for all
cement zones. Data comprise the mean compositions of individual samples (numbered and listed below). Abbreviations as in
(a). The fields of brightly luminescent cements (Zone 1 bright, Zone 2 and Zone 4) are overlapping but well separated from
non-luminescent cements (Pre-Zone 1 and Zone 1). The trend is broadly covariant. The numbered plots repregent the mean
values of all spot analyses, by zone, for each sample as specified below. For plot 5 only, individual analyses are also plotted to
indicate the degree of analytical variation. Plot numbers relate to samples and localities as follows (sample no., followed by
locality name, then a group of two numbers comprising the plot no. and, in parentheses, the no. of spot analyses used in the
plotted mean: Fig. no. refers to an illustration of the sample). Sample LCD, Brigantian Knoll Reefs, Wirksworth: 3(5), 4(16),
15(5), 19(4), 22(4); Fig. 3(a,b). Sample LCJ, Asbian of Longcliffe Quarry, Grangemill: 2(13), 8(1), 12(4), 18(7), 23(6); Figs
3(c,d) & 5(a,b). Sample L33, Asbian of Longcliffe Quarry, Grangemill: 5(7), 9(18), 20(4). Sample HH 25, Asbian of Hillhead
Quarry, Buxton: 7(7), 11(4), 14(6), 17(7). Sample G79, Asbian of Grangemill Quarry, Grangemill: 6(9), 10(12), 13(8), 16(8),
21(3); Fig. 4(a).

among Zone 4 cements or in comparison with other it to tectonism. Zone 4 cement is an impressive and
zones. Evidently the absolute amount of Mn is mare widespread marker of late diagenesis and probably
important than the Fe/Mn ratio. The average Mg spans the deepest phase of burial of the platform from
content of Zone 4 cements is variable in relation to the onset of widespread stylolitization to Variscan
Zone 3 cements, being lower in all Asbian rocks and inversion and tectonism that began in the ,late
higher in one Brigantian sample. N o consistent Mg Westphalian.
trends through Zone 4 have been noted.
Zone 4 cement was probably precipitated under a
S T A B L E ISOTOPE A N A L Y S I S
wide range of late diagenetic conditions but was
largely fracture-fed in an already near-tight limestone.
Pre-Zone 1 cement data (Fig. 7)
Its occurrence along pressure-dissolution seams and
intercrystalline boundaries suggests hydrostatic effects Asbian 613C values for Pre-Zone 1 cements lie within
and its appearance in conjugate vein systems relates the range - 3.6 to - 5.6%,, and 6"O values in the
654 G . M . Walkden and D . 0 . Williams

8
a Asbian 613c 7
PDB
6

Dinantian I 5
Marine ?
Carbonate
. I
4

-1

-2

-3

-4

-5

-6
I I I I I I I I I I I I I I ~
-7 ~

6" 0 PDB
I I I I I I I I I I I I I I I
-15 -14 -13 -12 -11 -10 -9 -8 -7 -6 -5 -4 -3 -2 -1 0
Fig. 7. Carbon-oxygen isotope cross-plots of Asbian (a) and Brigantian (b) cements and whole rocks: Derbyshire platform.
Envelopes define the fields.

range -7.9 to -8.8%, (six analyses). In Brigantian Calcrete data (Fig. 7)


rocks the 6I3C values are - 1.7 to -2.9%,, and 6 l 8 0
values -6.9 to -7.7%, (five analyses). Whilst the The 6I3C values of Asbian calcretes lie within the
6' ' 0 compositions show no significant departures range - 3.2 to -4.5%,, and 6 l 8 0 values in the range
from most other cements, all 6' 3C values show relative -6.7 to -8.2%,. The four analyses represent two
'3C-depletion, and Asbian values are particularly types of sample from each of two specimens, namely
light. Brigantian Pre-Zone 1 cement 6I3C and 6I8O dark, micritic carbonate and light, peloidal or brec-
compositions are comparable with those of Zone 1 ciated carbonate. N o clear compositional difference
cements from the .4sbian. was revealed and the field is similar to Pre-Zone
Derbyshire-East Midland carbonate shelf, England 655

1 cements but a little heavier, notably in the 6"O ingly light 6 l 8 0 extreme reflecting the lightest Zone 3
value. cements. In Brigantian rocks the whole-rock field
coincides quite closely with that of Zone 3 cement and
Zone 1 cement data (Fig. 7) is isotopically indistinguishable.

Only Asbian Zone 1 cements are present in sufficient


quantities for sampling (13 analyses). Their 6I3C Biogenic grain data (Fig. 8)
values range between - 1.7 and - 3.4%,, and 6"O All the Davidsonina septosa shells analysed were non-
values between -6.8 and -9.6%,. The 6I3C values luminescent with an apparently unaltered microstruc-
are less depleted than the corresponding Pre-Zone 1 ture. Nine samples cluster around 6I3C= 5.5%,, +
cements, but the 6I8O values show no significant 6"0= -3.0%,, but the remainder occupy a limited
difference. field that stretches in the direction of 6' 3C= - 2.5%,,
6lSO= - 7.5%,. This extreme range of values suggests
Zone 3 cement data (Fig. 7) that some alteration has occurred, but the heavier
values are quite distinct from any other analyses in
A relatively large number of Zone 3 cements were this study and may be closest to the original carbonate.
analysed because of their volumetric importance ; the The light isotopic values extend into the fields of the
results show marked contrasts with older cements. In Pre-Zone 1 and Zone 1 cements. The two crinoid
Asbian rocks (20 analyses) their 613C values range analyses lie close to one another, but outside the range
between - 1.0 and +2.5%,, and 6 l 8 0 values between of brachiopod alteration. They lie within the range of
- 7.0 and - 15.0%,. Brigantian Zone 3 cements (27
Zone 3 cements.
analyses) have 6I3Cvalues between -0.6 and + 3.2%,
and 6"O values between - 5.5 and - 12.3:&,. These
results show significant departures from Pre-Zone 1 D I S C U S S I O N AND INTERPRETATION
and Zone 1 cements with average 613C values The isotopic trend from Pre-Zone 1 to Zone 3 cements
becoming positive and a considerable spread of 6lXO starts with light 6I3C values and finishes with light
values, some very light. In general, Asbian cements
have a greater range of 6' '0 values whereas Brigantian
cements have more variable 613C compositions.

Zone 4 cement data (Fig. 7)


Zone 4 cement compositions have only been obtained
for Asbian rocks (10 analyses). Their 613C values
range between -3.8 and +2.3%,, and 6"O values
between - 2.7 and - 9.0%,. These compositions show
the greatest variation of all cements, although most
seem to lie within the range of Zone 1 cements.

Whole-rock data (Fig. 7)


Most samples will include highproportionsof biogenic
and non-biogenic allochems together with Zone 3
cement, but the proportions of Pre-Zone 1 and Zone
4 cements are insignificant. Zone 1 cement should be
more important in Asbian than in Brigantian rocks. 0 -4

Asbian 613Cvalues range between - 2.0 and + 1.6%,, 1 1 1 1 1 1 1 1 1 1 1 1 -5


12 -11 -10 9 -8 -7 6 -5 -4 -3 -2 -1 0
and 6 l 8 0 values between -7.5 and -9.6%, (21
analyses). Brigantian 6l 3C values range between Fig.8. Carbon-xygen isotope cross-plots for biogenicgrains:
-0.5 and +2.0%,, and 6 I 8 0 values between -6.0 Derbyshire platform. The D.seprosu data suggest a mixing
line (shown) between an original shell composition and early
and - 9.5%".The range of Asbian whole-rock analyses meteoric cements. Our brachiopod data agree with those of
has considerable overlap with the fields of both Zone Berry (1984). Crinoid data are inadequate but closely
1 and Zone 3 cements although there is no correspond- resemble Zone 3 cement values.
656 G. M . Walkden and D. 0. Williams

6I8Ovalues. The work of Dickson & Coleman (1980), The least-altered 6I3C value for marine carbonates
Allan & Matthews (1982), Moore (1985), Meyers & of + 7.3%, is heavy, and not predicted, for example,
Lohmann (1985) and others shows that such a trend by the 6l3C age curve of Veizer et al. (1980) which
can result from the interplay of a number of factors was constructed on the basis of whole-rock analyses.
ultimately related to progressive burial. The trend is Less 13C-enriched values have been suggested by
therefore broadly compatible with the shallow meteo- Meyers & Lohmann (1985), Popp et a/. (1986) and
ric to deep burial model of Walkden & Berry (1984a), Veizer et al. (1986). It seems reasonable to assume
but in order to model realistically the compositions of that the D. septosa data represent a better estimate
fluids affecting the limestones during the various of Dinantian values than that taken from the curve
stages of diagenesis, it is important to try to establish of Veizer et a/. (1980), but the I3C-enrichment in
the probable isotopic composition of the ultimate these shells could be partially or entirely due to a
source of these fluids, contemporaneous seawater. vital fractionation during growth (e.g. Popp et a/.,
1986). Regrettably, the existence or magnitude
of such biological effects cannot be judged from
our data.
Brachiopod shell compositions and Carboniferous
seawater
Pre-Zone 1 cements
The D. septosa data presented in Fig. 8 show
considerable scatter, but the plots lie close to a simple The I3C-depleted compositions of the Pre-Zone 1
regression line that extends in the direction of Pre- cements clearly distinguish them from other zones
Zone 1 and Zone I cements. Alteration of biogenic (Fig. 7). Their light 6C values fall within the range
components can take place in a variety of diagenetic of meteorically-altered Pleistocene limestones and can
environments (e.g. Kendall, 1975; Pingitore, 1976; be attributed to the effects of soil-derived CO, (e.g.
Lohmann, 1988), and the trend of this line strongly Gross, '1964; Deines et a/., 1974; Allan & Matthews,
suggests that some alteration of D. septosa shells took 1977,1982; Lohmann, 1988).
place during early diagenesis. Although the shells Plant metabolism and decay can produce a soil COz
were selected for their apparently unaltered (uniformly reservoir with a very light 613C value similar to that
non-luminescent) state, the early cements are also of the plants themselves (Craig, 1953; Park & Epstein,
non-luminescent and contamination by these must 1960).After dissolution in water and subsequent rock-
similarly fail to show. water interaction, this light signature is progressive8
Defined on the basis of the heaviest, and therefore lost through the vadose zone and cements assume
probably the least altered 6I8O value, the best value intermediate 6I3C values depending upon the degree
for marine carbonate that can be deduced from these of openness of the C0,-H,O-rock system (Deines et
brachiopod data is 6 l 8 0 = - 2.4%,. This corresponds al., 1974; Wigley, 1976; Wigleyetal., 1978; Michaelis
to precipitation from seawater of 6 l 8 0 (SMOW) = O x , eta/., 1984; Meyers & Lohmann, 1985). Our Pre-Zone
(present day) at 27,5"C, or from seawater of 6I8O I cement 6' 3C values of - 1.7 to -5.6%, are light but
(SMOW)= - 1.2x0 (ice-free oceans) at 22.5% Both fall short of the extremes (- lo%,) noted in some near-
temperatures fall within the range of present-day surface carbonates (Gross, 1964; Deines et al., 1974;
equatorial near-shore ocean surface waters (e.g. James & Choquette, 1984). This could reflect rock
Milliman 1974), but the higher temperature may be a buffering, perhaps most pronounced in our Brigantian
better estimate of local Dinantian marine conditions samples that came from the interiors of mud-mounds.
(e.g. Berry, 1984). Nevertheless, following Niemann & Read (1988) it is
The 6l8O (SMOW) value inferred here for late worth noting that our carbon values for Pre-Zone 1
Dinantian seawater implies a negligible departure cements, relatively heavy in relation to present-day
from the present day and is in agreement with the O x , 613C extremes in equivalent settings, would be
of Berry (1984) derived from a similar study. Our proportionally more extreme if Carboniferous sea-
value compares with the -1.5 to -2%, values of water had a heavy 6I3C (SMOW) value as our
Brand (1982) and the -1.5%, values of Meyers & brachiopod data might be used to indicate.
Lohmann (1985). In contrast, Dickson & Coleman Precipitation from meteoric fluids also satisfactorily
(1980) suggested that Dinantian seawater might be as explains the 6 l 8 0 values of Pre-Zone 1 cements. They
light as -6%,, whilst the data of Popp et al. (1986) are too light to suggest precipitation from seawater at
indicate a late Dinantian mean around - 3%,. surface temperatures and must reflect crystal growth
Derbyshire-East Midland carbonate shelf, England 657

within an "0-depleted fluid such as meteoric water cements at around -2.5%, are heavier than Pre-Zone
(e.g. Allan & Matthews, 1982). 1 cements but still lie within the range of meteorically
Based upon this conclusion, the 6 ' * 0 values of Pre- altered Pleistocene limestones affected by soil COz.
Zone 1 cement provide an opportunity to estimate the However, the stratigraphic and geochemical charac-
oxygen isotopic composition of Carboniferous meteo- teristics of Zone 1 cements indicate that they formed
ric porewaters. Because porewater oxygen isotope in a deeper environment than Pre-Zone 1 cements.
composition is independent of rock-porewater inter- Bright subzonal detail within the largely non-lumines-
action in a water-dominated reaction system (Meyers cent Zone 1 cements (e.g. Fig. 4) can be correlated for
& Lohmann, 1985), it should closely reflect the several metres vertically and for several kilometres
contemporaneous meteoric input. Of critical impor- horizontally, and the cements represent areally exten-
tance in the calculation is the likely ambient temper- sive phreatic water bodies (Berry, 1984; Walkden &
ature within the uppermost regions of the rock body. Berry, 1984a; Walkden, 1987; Williams, 1988). In
According to Zonenshain et al. (1985), Britain was such a situation the effects of soil CO, on isotopic
within 10" of the equator during the early Carbonifer- composition should be much reduced (e.g. Allan &
ous. Using the palaeotemperature equation of Epstein Matthews, 1982).
et al. (1953) and assuming a surface groundwater The precipitation model for Zone 1 cement (Walk-
temperature of 25C (k2.5"C seasonal fluctuations), den & Berry, 1984a; Walkden, 1987; Horbury &
a range of values for the 6 l 8 0 composition of the Adams, 1989) involves establishment of a new
fluids that precipitated the Pre-Zone 1 cements can be meteoric water body during each cyclical emergent
calculated. Asbian values fall in the range -5.5 to event, with intervening stagnation and possible
- 7.4%, (SMOW), whilst Brigantian values lie be- marine recharge of pores during periods of inundation.
tween -4.4 and - 6.4%, (SMOW). These figures lie The dark-bright couplets within individual over-
at the depleted end of the range of present-day 6"O growths are diachronous up section, each successive
values for equatorial meteoric waters (Yurtsever & bright subzone (e.g. Fig. 4a) tending to occupy a
Gat, 1981), and are lighter than the -4%, for slightly higher stratigraphic range than the last
Dinantian meteoric waters in South Wales (Searl, (Walkden, 1987). The trace element trend from non-
1988) and for Mississippian low-latitude coastal luminescent to bright subzones (Fig. 6a, Table 2)
meteoric water of Kentucky (Niemann & Read, 1988). shows a rise in Mn and Fe consistent with a decrease
Our light value for late Dinantian meteoric water is in redox conditions. During stagnation of the water
unlikely to be attributable to a locally higher surface body crystal growth would have been curtailed, but
temperature, for which around 10C would be re- some growth would have occurred through dissolution/
quired, and it is more likely that contemporaneous reprecipitation effects including 'Ostwald ripening'
meteoric water was locally more fractionated, perhaps where large crystals can continue to grow at the
as a result of higher and more intense rainfall (e.g. expense of smaller ones (Walkden & Berry, 1984a).
Yurtsever, 1975; Yurtsever & Gat, 1981). The marked increase in Mn in bright subzones
( > 400%) may have been assisted by the effect of slow
crystal growth on the Mn distribution coefficient noted
Calcretes by Lorens (1981) & ten Have & Heijnen (1985).
The calcrete field clearly overlaps with that of Pre- Increased Mg in bright subzones, however, is probably
Zone 1 cements but is generally heavier. The differ- not an effect of growth rate (e.g. Mucci & Morse,
ence, with so few data points, has limited reliability 1983) and is more likely to be attributable to changes
but calcretes reflect specific evaporation-dominated in porewater composition through effects such as
conditions, and their generally heavier 6"O values magnesian calcite or aragonite stabilization (e.g.
than Pre-Zone 1 cements are consistent with this Lohmann, 1988), incongruent dissolution of crinoids
(Lohmann, 1988). or marine contamination of the porewaters (e.g.
Meyers & Lohmann, 1985). Mixing of marine and
meteoric water during marine transgressions and
Zone 1 cements
regressions might also explain the dissolution effects
The 6 l 8 0 values of Zone 1 cements (c. -8.0%,) are commonly associated with bright subzones in Zone 1
similar to those of Pre-Zone 1 cements and can also cement and also observed between Zones 1 and 2 (e.g.
be attributed to precipitation from isotopically light Figs 3b & 4a).
meteoric groundwater. The 613C values of Zone 1 Zone 1 meteoric cements were therefore precipi-
658 G . M . Walkden and D . 0. Williams

tated intermittently at successively increasing depths and mudstones where cements were not grown
as the sediment pile developed, and this model syntaxially on crinoids and occlusion was relatively
provides a possible explanation of the light carbon late. Such locations may include large quantities of
values in Zone 1 cements. It is likely that the earliest late Zone 3 cement precipitated at greater depths of
cement on any grain, having been precipitated in a burial and hence higher temperatures.
situation closest to a surface soil, would be consider- The actual depths implied by the light 6"O values
ably depleted in the I3C isotope, and samples may depend upon the derivation of the precipitating water
even have included some unrecognized Pre-Zone 1 composition. The trace element geochemistry of Zone
cement. Subsequent subzones, precipitated following 3 cements is compatible with a meteoric origin (e.g.
deposition of further cyclothems, should contain Meyers & Lohmann, 1985; Moore, 1985) and only in
progressively more I3C because they grew within its Mg content does Zone 3 cement differ to any extent
deeper water bodies away from the influence of light from the meteoric Pre-Zone 1 and Zone 1 cements.
soil CO,. Noting rare up-dip calcites with 6I8O values as light
A similar problem of particularly light 613C values as -10.7%,, Niemann & Read (1988) suggest that
in shallow burial cements (down to - 8.7%,)was noted some Mississippian meteoric waters may have been
by Niemann & Read (1988) who attributed the as light as -8.7%, (SMOW) through monsoonal or
anomaly to a rich supply of soil gas beneath coal orographical effects. However, taking meteoric water
swamps. Coals are rarely associated with the palaeo- with our own average 6I8O value of -6%, (SMOW)
sols on emergent surfaces in Derbyshire, but rhizocre- (derived earlier from Pre-Zone 1 cements) and
tions are common (Williams, 1988), indicating that assuming an average geothermal gradient of 30C
the humid conditions that promoted the palaeokarsts km- and a surface temperature of 25"C, the lightest
also encouraged plant cover. Zone 3 cement value of -15%, requires 70C,
representing 1.5 km of burial.
Alternatively, for the sake of comparison, using a
Zone 3 cements
marine water 6I8O value close to OX, (SMOW) the
In Asbian rocks the average 613C value of Zone 3 lightest Zone 3 cement value corresponds to 110C
cements departs significantly from those from Pre- and approximately 2.8 km. This is marginally greater
Zone 1 cement and is slightly positive. In Brigantian than the known maximum depth of burial of the shelf
rocks the average is heavier still, around l.O%,. These (e.g. Smith & Smith, 1989; Ebdon et al., 1990), but
heavier values indicate isolation from the usual sources more importantly, the trace element geochemistry of
of soil-derived or diagenetically-released *C (e.g. Zone 3 cement is incompatible with an origin from
Curtis, 1977; Irwin er al., 1977; Meyers & Lohmann, waters of a normal seawater composition (e.g. Moore,
1985). The only remaining significant carbon reser- 1985). The Sr content is low and the Mg content, at
voir, therefore, is the rock body itself; however, the around 1000 ppm, is far too low, especially if elevated
whole-rock 613C values (Fig. 7), which must reflect temperatures were involved.
the then-available reservoir, are generally too light to Concentrated brines within the Smackover For-
provide a satisfactory source. Zone 3 cements are mation of the southern USA have very low Mg/Ca
therefore allochthonous and were brought in with a ratios that could precipitate cements with the observed
new source of porewater from elsewhere. Neverthe- Mg levels of Zone 3 cements (Moore, 1985) but they
less, local interaction and buffering may still be have heavy 6 l 8 0 (SMOW) values of +5.5%,. Such
revealed by the degree of overlap between the fields of heavy, isotopically evolved 6 ' * 0 (SMOW) values have
Zone 3 cement and whole rock (Fig. 7), especially in been reported from a number of present-day formation
the Brigantian data. waters (e.g. Kharakaetal., 1977; Millikenetal., 1981)
The 6"O values of the Zone 3 cements, with their and result from reactions within the rock body (Coplen
marked scatter encompassing some very light values, & Hanshaw, 1973; Lawrence et al., 1976). Precipita-
are similar to other 'late' cements (Dickson & tion of the lightest cements of Zone 3 from water such
Coleman, 1980; Marshall, 1981, 1982; Meyers & as this would require temperatures around 170C,
Lohmann, 1985; Moore, 1985). Light 6 l 8 0 values are representing more than 4.5 km burial. Set against this,
commonly attributed to elevated temperature during direct evidence for only relatively shallow burial
burial, and although we have been unable to sample during Zone 3 cementation stems from the fact that
specifically to test this, our lightest cements were taken the cements are cut by pressure-dissolution seams.
from relatively large pores in fenestral wackestones The onset of Zone 3 cementation predates burial to
Derbyshire-East Midland carbonate shelf, England 659

pressure-dissolution depths so that extremes of burial quette & James, 1987). As noted, dissolution is
are ruled out and with them a marine-derived origin common immediately prior to Zone 4 cement in some
for Zone 3 cement. samples, and pores lined with Zone 4 cement are
The best model for precipitation of Zone 3 cement occasionally occluded by bitumen consistent with
on petrographical and geochemical grounds is there- immediately ensuing oil migration. The association of
fore an initially shallow meteoric environment, becom- fluorite mineralization with some Zone 4 cement has
ing progressively deeper with burial. A potentially also already been noted and the source of this
useful independent geochemical indicator of progres- mineralization is now believed to have been the
sive burial stems from the work of Katz (1973) who basinal shales adjacent to the Derbyshire-East Mid-
demonstrated temperature dependence for the distri- land shelf (Jones & Plant, 1989). This fluid conduit
bution coefficient of Mg in calcite. Subsequent work may have been open for much of the Zone 4
has refined the value of the distribution coefficient in cementation.
marine waters (Mucci & Morse, 1983; Mucci, 1987), Nevertheless, in circumstances where organic-
but using Katz's more applicable data, and assuming matter-derived CO, is freely available from expelled
a steady Mg/Ca ratio, rising temperature should lead porewaters, cements precipitated from these can be
to 2 progressive increase in Mg content in calcite. strongly depleted in I3C, far more so than is seen in
Such an increase has been noted in Zone 3 cement, Zone 4 cement (e.g. Donovan, 1974; Irwin et al.,
but calculation (e.g. Moore, 1985)shows that only half 1977). Either the 13C-depletedcarbon was available
of the noted increase could be attributed to a only in limited quantities, or the incoming CO, had
temperature rise proportional to 2 km of burial. its 6I3C values buffered by the carbon in the rock
Progressive change in the Mg/Ca ratio of the body itself. In a system where there is a low water-to-
porewater during precipitation of Zone 3 cement is rock ratio the latter conditions are met. Precipitating
therefore necessary to account for all of the Mg calcite can have its isotopic composition controlled by
increase. the dissolving mineral rather than the water or the
Zone 3 cements are probably 'late' only in that they ambient temperatures (Czerniakowski et al., 1984;
appeared after shallow meteoric diagenesis of the Suchecki & Hubert, 1984; Lohmann, 1988). Zone 4
limestones. The fact that emplacement started before cement constitutes only a small proportion of the rock
there was a sufficient overburden to induce pressure body and some of the sites and textures of the cement
dissolution leads to the obvious but important conclu- clearly indicate that local dissolution/precipitation
sion that cementation of the platform was substantially reactions were in operation. The diagenetic environ-
complete at a relatively early stage in its burial history. ment of Zone 4 cement is therefore likdy to have
This conclusion has far reaching economic implica- approached the system above and any incoming 13C-
tions. The nature, source and timing of the water that depleted water could have become considerably
precipitated Zone 3 cements are therefore important buffered.
topics which are considered separately. The 6"O values of Zone 4 cement are heavier than
might be expected for a burial cement that probably
formed at high temperatures. This paradox has been
Zone 4 cements
encountered with other late cements (e.g. Marshall,
The 613Cvalue of most Zone 4 cements shows a return 1982; Moldovanyi & Lohmann, 1984) and can be
to the light ratios of some of the Pre-Zone 3 cements. explained by rock buffering under low water-to-rock
If, as the petrographical evidence indicates, some ratios, as discussed above, or by the introduction of
Zone 4 cements are stylolite-related then this 13C- 80-enriched water from independent sources.
depletion might be due to the redistribution of light Possible sources include clay-rich degraded volcanic
carbonate associated with calcrete and rhizolith horizons within the platform (e.g. Walkden, 1972)
horizons where some of the most prominent stylolites which, following isotope ultrafiltration, might release
are seen. However, a volumetrically more significant ' 80-enriched water during deep buria! (e.g. Marshall,
source of isotopically-light C during burial diagenesis 1982). A volumetrically more realistic source, how-
is from the CO, released through organic reactions ever, is the adjacent basins. Porewaters in some
such as kerogen decarboxylation (Irwin et al., 1977). sedimentary basins have 6"O values up to +7%,
Large volumes of C 0 2 are generated in this way and (SMOW) due to high-temperature clay-water reac-
can result in porewater acidification and carbonate tions (Kharaka et al., 1977). Colman et a / . (1989),
dissolution (Curtis, 1983; Burley et al., 1985; Cho- considering derivation of Pennine ore fluids from the
660 G . M . Walkden and D . 0 . Williams

basinal shales, note characteristic I80-enrichment. in the same way and conclude that pervasive diage-
They point to catastrophic dewatering of basinal netic alteration, including neomorphism of grains and
shales accompanying E-W-directed stress during the growth of microspar, occurred during Zone 1 cemen-
latter stages of the Variscan orogeny with the pumping tation. This points to a further trend in these late
of very hot overpressured fluids into fracture systems Dinantian carbonates comprising the loss of C in a
in the limestone. This accords with our own observa- continuum of values from Pre-Zone 1 into Zone 1
tions of the creation of fractures, the jacking of cements, and resumed in Zone 3 cements. This trend
stylolites and the opening of intercrystalline bounda- is the equivalent of the vertical limb of the inverted j
ries during Zone 4 cementation indicating that at least of Meyers & Lohmann (1989, that represents increas-
some Zone 4 cement was precipitated in a geopres- ing water-rock interaction with burial under meteoric
sured setting. conditions.
We conclude that both the heavy 6 l 8 0 values and The slightly heavier Brigantian 6 3C whole-rock
the light 6l C values of Zone 4 cement result from the values seem to reflect accurately the less pervasive
arrival of very hot but I80-enriched and 13C-depleted early meteoric diagenesis experienced by these rocks,
basin-derived water which was then buffered through but the values still lie on a definable meteoric water
local dissolution/precipitation reactions. Such water line (e.g. Lohmann, 1988). We have already noted the
may have arrived in phases between the late West- rarity of well-developed Zone 1 cement in Brigantian
phalian and early Permian. limestones and the less frequent and less well-
Although Zone 4 cements give no direct evidence developed palaeokarsts. Instead, the Brigantian
of the final burial temperature and depth of Dinantian whole-rock compositions are far closer to the values
carbonates, other independent indicators can be used. for Zone 3 cement, suggesting that the main alteration
One is the conversion of the volcanic-derived clays in of these rocks occurred during Zone 3 early burial.
the platform to mixed-layer illite-smectites with
between 35 and 10% expandable layers (Walkden,
1972). The evident ordering of these clays suggests T H E O R I G I N OF Z O N E 3 C E M E N T
temperatures of at least 100C (cf. Velde, 1983; WATERS
Pearson & Small, 1988). Evidence of somewhat higher
temperatures, at least locally, comes from the presence
The problem of volume
of solid bitumens within remnant pores following
Zone 4 cementation. These are especially common at The origin of the water that mobilized and reprecipi;
platform margins and indicate thermal degradation tated the meteoric cement in Zone 1 and Pre-Zone 1
of oil at temperatures well above 100C. is self evident and needs no further consideration. For
Zone 3 cement, however, which is volumetrically
important with a dull luminescence, we have cited the
Whole-rock compositions relatively heavy 6I3C values as evidence of external
The 6C and 6 l 8 0 values of Asbian and Brigantian derivation, but a source has not been discussed. An
whole-rock analyses lie within the broad range for exact figure for the total rock volume occupied by
typical ancient marine limestones (Hudson, 1977),but Zone 3 cement, including microporosity, is hard to
they show a significant departure away from our determine in cathodoluminescence owing to the
postulated original marine carbonate value based on similar luminescence exhibited by both allochems and
the analysis of Davidsonina septosa shells (Fig. 8). In cement, but a figure of 20-30% is reasonable. From
addition, there is a difference of some 2%, between this, a general estimate of the total volume of Zone 3
Asbian and Brigantian 613C values. in the exposed portion of the Derbyshire-East
The Asbian whole-rock field (Fig. 7a) lies closer to Midland shelf (25% of 30 x 15 x 0.5 km) is roughly
Zone 1 cement, but the amount of displacement from 50 km3. Borehole samples show that down-dip Zone
our postulated marine composition seems far greater 3 cement could occupy at least an order of magnitude
than the contribution that this cement alone could more volume. The potential for supply through
make as a whole-rock component (c. 12%). In our internal redistribution by mineral re-equilibrium was
study of D.septosa shell compositions we suggested probably negligible by the time of Zone 3 cementation
that the covariant trend of 613C and 6*0 towards and pressure dissolution had not yet begun, so that to
lighter values (Fig. 8) indicated early meteoric cement the entire Derbyshire-East Midland Platform
alteration. We interpret the Asbian whole-rock value with Zone 3 cement required some 500km of
Derbyshire-East Midland carbonate shelf, England 661

carbonate from an external source. Furthermore, since rock volume occupied by Zone 3 cement, there would
Zone 3 cement evidently predates pressure dissolu- be a substantial shortfall of calcite which must have
tion, it was obviously emplaced during early burial originated from elsewhere. Stronger evidence against
and therefore quite quickly. local derivation comes from the 6I3C values of Zone
The water volume required to mobilize and emplace 3 cement that do not reflect the local whole-rock
this cement, adopting Bathursts (1975) figure of compositions.
10000-50000 pore volumes of water per fully ce- Similarly doubtful is the origin of the cement by
mented pore, was proportionally colossal, between 5 pressure dissolution of underlying limestone. Cores
and 25 x lo6 km3, and this water must at some stage show no evidence that stratal loss by pressure
have been either hot or isotopically light to account dissolution is any greater at depth than at the surface,
for the light 6I8O values of Zone 3 cements. It was and some rocks are in any case dolomite (e.g.
also of sufficiently consistent supply and uncontami- Aitkenhead et al., 1985). On this basis, sufficient
nated condition to give rise to geochemically clean, carbonate could only have been derived from rocks at
almost subzone-free calcite. As discussed above, these depth where there was a donor-to-receptor thickness
conditions are best met in a burial meteoric setting. ratio of 2.5: 1 (fully cemented donor), or 8.6: 1 (25%
One obvious relatively late meteoric source would porous donor becoming fully cemented). Thus the
be the unconformity seen in places on the western minimum average stratal thickness required is around
margin of the platform (Fig. 2) beneath Namurian 1500 m and this is difficult to find. Geophysical and
clastics (e.g. Aitkenhead et al., 1985). However, this borehole evidence shows that in many areas the
unconformity can be discounted on both geochemical thickness of the underlying succession is little more
and petrographical grounds because samples from +
than the observed Asbian Brigantian thickness, and
nearby show normal Zone 3 cement burial character- even at its maximum within hanging-wall successions
istics, including the light 6 l 8 0 values and typical dull the underlying sequence is only three times this (Cope,
luminescence with uninterrupted growth (Walkden & 1973; Dunham, 1973; Aitkenhead & Chisholm, 1982;
Berry, 1984a; this study). The unconformity can also Smith et a/., 1985; Gawthorpe et al., 1989; Smith &
be discounted on volumetric grounds because the Smith, 1989). Modelling therefore suggests that deri-
degree of erosion involved was insufficient to provide vation of Zone 3 cement carbonate through local or
the necessary volume of calcite. Zone 3 cements must nearby pressure dissolution is improbable, but the
therefore post-date this end-Dinantian uplift, but possibility remains that intersection by stylolites is
alternative scenarios, such as an origin by local or not conclusive evidence that all stylolitization post-
underlying pressure dissolution or from adjacent dates Zone 3 cementation.
basins during compaction, move away from the
preferred meteoric model.
Sourcing through basinal compaction
A compaction fluid model involves deriving the
Sourcing through pressure dissolution necessary carbonate-charged waters from adjacent
Little is certain about the depth at which pressure basinal areas (Fig. 9). Porewaters within Dinantian
dissolution can begin (e.g. Scholle & Halley, 1985; basinal sediments would have been marine-derived,
Walls & Burrowes, 1985)and we adopt here a threshold but Namurian and later waters would have had mixed
of 1 km or less. The process has long been regarded as origins and their composition could only be guessed
a likely source of calcium carbonate for cementation at. There is no geochemical evidence to suggest that
during burial (Bathurst, 1975; Mattes & Mountjoy, Zone 3 cement was derived from basinal formation
1980; Wanless, 1983). Although Zone 3 cement is cut waters but a practical obstacle to basin sourcing is the
by stylolites and evidently predates pressure dissolu- necessary volume. Even if all interstitial and structural
tion, the possibility must be examined that the cement water became available to the shelf at a single stage in
was actually contemporaneous with local pressure its diagenesis, the cumulative total of fluid in the
dissolution. Growing stylolite seams might have surrounding basins could not have exceeded 75% of
cannibalized cements precipitated in nearby pores 15 km (completely decompacted maximum thickness
during their own earlier development. However, of basinal sediments ) x 100 km x 200 km (maximum
Walkden (1974) and Berry (1984) concluded that the possible area of surrounding basins) which gives
loss to the succession by pressure dissolution was 225 000 km3. Given the figure of 5 to 25 x lo6 km3 of
around 10%. Set against the approximately 20-30% of water required to emplace Zone 3 cement, the
662 G . M . Walkden and D . 0 . Williams

subsided, the east side became emergent, inevitably


creating a karst landscape (Fig. lob). This created the
ideal configuration for a meteoric aquifer system in
which almost limitless volumes of meteoric water
could gain access to the shelf in the east and be driven
westwards, down dip, by piezometric head. Compa-
rable conditions are found in the present-day Floridan
limestone aquifer where meteoric water from a
limestone hinterland flows for up to 100 km seawards

Chad'an
TO"," w r
Of the Meman Highlands
beneath an area of active sedimentation before
discharging on the sea bed (Kohout, 1967; Manheim,
1967; Johnson, 1983).
Strank (1987)points to considerable post-Dinantian
erosion at the unconformity beneath the East Mid-
lands, much of which could have eventually found its
way down dip in solution. This fits well with the post-
Dinantian to pre-stylolite window for the onset of
Zone 3 cementation and with its meteoric origin.
Wholesale dissolution of only relatively small tracts of
landscape would have been sufficient to provide the
necessary volume for Zone 3 cement.

Geochemical implications of the meteoric aquifer


model
The post Dinantian meteoric aquifer model is consist-
ent with the trace element and luminescence charac-
Fig. 9. The Derbyshire-East Midlands carbonate shelf in the
teristicsof Zone 3 cements. Water in meteoric aquifers
Silesian. (a) The Dinantian/Silesian unconformity across the commonly becomes reducing down dip as a result of
East Midlands carbonate shelf (from Strank, 1987), and (b) redox reactions and microbial activity (Champ etpl.,
general Silesian palaeogeography and drainage trends (after 1979; Grover & Read, 1983; Choquette & James,
Aitkenhead, 1985; Collinson, 1988; Guion&Fielding, 1988). 1987; Niemann & Read, 1988). A lowered redox
Letters on (b) refer to localities on (a) as follows: B, Boston;
T, Tuxford; E, Eyam. would explain the slight Mn increase and enhanced
luminescence seen in Zone 3 compared with Zone 1
meteoric cements (Fig. 6a). The rising trend of Mg
discrepancy is more than an order of magnitude. Basin noted in Zone 3 cement may also be a consequence of
sourcing can be eliminated and a very much larger, passage through a large aquifer where increased
and non-saline, source for the Zone 3 cement waters residence time resulting from progressive sealing
must be sought. through burial could have provided greater opportu-
nity for water-rock reaction. However, the effect of
progressive increase in burial temperature on the
Sourcing from a post-Dinantian meteoric system
distribution coefficient of Mg is also a possible
A more promising scenario derives from the effects of contributor (already noted), as is contamination by
the Namurian-Westphalian tectonic history of the basin-derived porewater.
Derbyshire-East Midland shelf, outlined above and The meteoric aquifer model is also consistent with
summarized in Fig. 10. The remodelled subsidence at the C and 0 isotopic compositions of Zone 3 cement.
the end of the Dinantian led to some parts of the We have cited the heavy 6I3C values seen in Zone 3
carbonate bodies becoming buried by clastics whilst cement as evidence for external derivation, and the
others were uplifted, with consequent profound effects unconformity provides an ideal source. Rocks for-
upon hydrology. The key change concerns the eastern merly exposed at this unconformity and throughout
side of the Derbyshire-East Midland shelf. As the the aquifer (Fig. 9a) include limestones earlier than
central and eventually the western parts of the shelf the Asbian and Brigantian, which, if they resemble
Derbyshire-East Midland carbonate shelf, England 663

,unI I , I I I , I I I ,
lmYm

Fig. 10. The structural, palaeo-environmental and diagenetic evolution of the Derbyshire-East Midlands carbonlate shelf. (a)
Early Asbian. The shelf is undergoing periodic fau!ting. General eustatic fall permits development of local meteoric water
bodies (dashed) beneath emergent areas. Pre-Zone 1 cements form in vadose sites, Zone 1 cements form in deeper meteoric
phreatic environments, and Zone 2 cements develop intermittently in generally stagnant conditions at depth below the actively
cementing region. Abbreviations: D, Derbyshire platform; E, Eyam; L, Lincoln; S, Sheffield. (b) Mid-Namurian. The central
shelf sags and the east flank becomes uplifted and eroded. The west flank remains near the surface with condensed deposition.
Meteoric water is introduced in the east and carried down dip (arrows). The input is both direct from the atmosphere and
indirect from Namurian river systems. Zone 3 cementation is underway down dip. (c) Mid-Westphalian. Subsidence of the
shelf is now more uniform and the unconformity is largely sealed. Indirect input of meteoric water is still possible through the
subcrop, comprising fluvially derived isotopically light groundwater. Burial is increasing the temperature of water migrating
down dip and this water convects upwards distally through anisotropies in the cover.

their Derbyshire counterparts, had not experienced Namurian was little more than 0.5 km which could
pervasive meteoric alteration of the type seen in Zone only account for the lower end of the inferred
1 cement. The whole-rock 613Cvalues of these earlier palaeotemperature range of Zone 3 cements. In fact
rocks would therefore have been closer to their original throughout this early burial, the critical western edge
marine ratios, and following dissolution, mixing and of the shelf where the study was undertaken remained
transfer, the resultant cement should show heavier close to the surface(Fig. 1Ob). Even by mid-Namurian,
6' 3C values than its well-altered Asbian or Brigantian Kinderscoutian (Rl), times there was a submarine
host. escarpment here controlling the eastward spread of
As regards the 6I8O values, the maximum depth of deltaic sands in the adjacent basin (Aitkenhead et al.,
water drive at the top of the limestone during the 1985). Nonetheless the aquifer could have been fully
664 G. M . Walkden and D.0. Williams

active at this early stage, with water from the east thinned crust, local volcanicity and radiogenic basin
being vented at the western edge onto the sea bed. fills. A high heat flow beneath the aquifer would
For the lighter end of the 6 ' * 0 range seen in Zone enable the refinement of the model involvingenergetic
3 cements, burial temperature, down-dip evolution convective expulsion of hot groundwater through
within the aquifer, and an input of isotopically light anisotropies in the clastic cover before this became
water at the unconformity are each possible contribu- sufficiently thick to suffocate the system (Fig. 1Oc).
tors. Ingress of isotopically light water is practical,
derived from the fluvio-deltaic systems that brought
in much of the sediment (e.g. Guion &Fielding, 1988). S U M M A R Y A N D CONCLUSIONS
This water was sourced in a substantial inland, upland,
region of high rainfall to the north. Comparison with Diagenetic sequence
the data of Yurtsever & Gat (1981) suggests that this
The Pre-Zone 1 to Zone 4 cement sequence represents
water could have been especially "0-depleted (e.g.
three important stages in the geochemical and diage-
Niemann & Read, 1988).
netic history of the shelf.
Nevertheless depletion alone cannot account for
Stage (A) reflects the original depositional setting
the lightest Zone 3 cement d'*O values of - 15%,, and
and records the cyclical subaerial exposure of the
either Zone 3 cement emplacement needs to have
continued with burial well into the Westphalian, or
heat flows must have been considerably greater than
modelled. Support for higher heat flows comes from
the structural history of the area as a region of recently
extended but cooling crust (Leeder, 1982; e.g. Nunn,
1984), but a more obvious source of locally high heat
flow is the basic volcanic activity which was episodic
on and around the shelf (e.g. Fig. 2) from the
Dinantian into the Westphalian (Colman et a f . , 1989;
Webb & Brown, 1989). In addition, from the Namu-
rian onwards, the basins filled with shalesof high heat
productivity and low conductivity (Jones & Plant,
1989). The combined geothermal effects of these three
factors (Fig. 11) could have created gradients of more
than 50C km- in places (Colman el al., 1989).
This high geothermal gradient is nevertheless
insufficient to achieve the target temperature through
burial during the Namurian only, and may in any case
apply only to peak burial in the late Westphalian. By
this time the maximum sediment cover over the
central parts of the shelf was 2000 m and would have
been more than sufficient to achieve the 70C needed
to precipitate the lightest Zone 3 cements using only
'
the lower gradient of 30C km- . A lasting obstacle D lNlWlSl \
150C
to this degree of burial, however, is that pressure
CARBONIFEROUS [PERMIAN] TRIASSIC
dissolution should have been well underway at such
depths, and yet the evidence is that Zone 3 cements Fig. 11. Burial curves, geothermal gradients and diagenetic
sequence for the Derbyshire platform. Burial curves relate to
may have been entirely emplaced prior to the
the Dinantian/Namurian contact : a, basinal sequence, Edale
generation of the first stylolite seams. In order to trough (from Colman ef al., 1989); b, generalized platform
emplace Zone 3 cements before stylolitization the sequence (decompaction estimated from Colman et al.
additional factors capable of producing light oxygen (1989).The suggested high geothermalgradientsaremodified
values, already discussed, need to have been in from Colman er al. and peak only with maximum basin fill.
They result from igneous, crustal and radiogenic sources.
operation. Thus the up-dip ingressing water may have Calcite cementation history is summarized in terms of time-
been unusually light, and burial may have coincided depth relations. Abbreviations: P1,Pre-Zone 1; Z1, Zone 1;
with a high geothermal gradient related to a previously 2 2 , Zone 2; 23,Zone 3 ; 24, Zone 4.
Derbyshire-East Midland carbonate shelf, England 665

shelf. Meteoric water directly entering the shelf during but with much variation. The fluids were associated
emergence mobilized local carbonate and reprecipi- with high-temperature oil or mineral emplacement,
tated it as non-luminescent vadose (Pre-Zone 1) and but local dissolution/precipitation reactions under low
phreatic (Zone 1) cements (Fig. 11). These are low- water-to-rock ratios, affecting both carbon and oxy-
Mg and low-Fe, non-luminescent, substrate-selective gen, mask their clear identity. The light carbon could
calcites with typical meteoric textures and stable reflect basin-derived organic COz, which probably
isotope values. Submergent phases are represented by also led to local pore enlargement, and the heavy
irregular luminescent bands within Zone 1 cements oxygen values were probably boosted by incoming
with increased Fe, M n and Mg attributable to water "0-enriched basinal water.
stagnation, slow growth and either equilibration of
high-Mg allochems or marine contamination. With
continued build up of the shelf, earlier deposits passed
Isotopic trends
below the reach of well-oxygenated cementing meteo-
ric water bodies and into a more persistently reducing Several useful isotopic trends involving water bodies,
region with little or no cementation (Zone 2, Fig. 11). whole-rock evolution and cement compositions have
These cements are luminescent and similar in detail been identified and these are summarized in Fig. 12.
and geochemistry to Zone 1 bright subzones. The first involves the meteoric alteration of initially
Stage (B) was the introduction of large quantities of marine Asbian (la) and Brigantian (lb) whole rocks
porewater and dissolved carbonate from an external during Pre-Zone 1 and Zone 1 cementation to produce
source. Burial was initially shallow, above the pres- light 6l'O and 613C values. The difference between
sure-dissolution threshold, but deep enough for com- them reflects the lower degree of meteoric alteration
pactive breakage of grains. The cements (Zone 3, Fig. in Brigantian rocks, and Asbian whole rocks nolonger
11) have dull luminescence, euhedral growth and no lie on this trend owing to the later effect of Zone 3
substrate preference. Their stable isotope and trace cements. Ambient meteoric water was unusually
element geochemistries indicate a major meteoric fractionated, perhaps owing to seasonal or climatic
aquifer, and some light 6l'O values suggest burial effects (2a) but the near-surface environment experi-
temperatures equivalent to 1.5 km. Such depths are enced fluctuations through evaporation which led to
unlikely for this evidently pre-stylolite cement and "0-enrichment in the calcretes (2b). With increasing
locally higher geothermal gradients (Fig. 11) and a depth in the meteoric phreatic environment and more
source of unusually 6l'O-depleted water are more water-rock interaction, soil influences were lost and
'
probable. The cements are Namurian to Westphalian, cements became less 13C-depleted(3).
derived from a karstified terrain on the subaerially The effects of rock body interaction remain appar-
exposed eastern flank of the shelf. Some of the water ent in Zone 3 cements, but the water was arriving
entering the aquifer here may have been fluvial with fully charged with carbonate from elsewhere and no
a northerly, upland and/or monsoonal source and a continuum exists with Zone 1 cements. Zone 3 cement
light 6l'O (SMOW) signature. The bulk transfer of waterscompleted the meteoric alterationof Brigantian
carbonate from outcrops in the east to the more marine allochems, generally decreasing their 6l ' 0
meteorically altered rocks in the west accounts for the values (4a), and the addition of Zone 3 cements to
heavy 613C values of Zone 3 cement which contrast Asbian rocks drew them in the direction of lighter
with local whole rocks. This stage marks the Namurian 6 l 8 0 and heavier 6I3C (4b). This arriving Zone 3
remodelling of subsidence patterns and the cements cement water was relatively 13C-enriched owing to
reflect the first influence of tectonism on the diagenetic reaction with less meteorically altered carbonate at
sequence. source ( 5 ) , but with increasing temperature and
Stage (C) represents continued burial to a likely perhaps the addition of "0-depleted meteoric water
maximum of 2000 m. As Westphalian onlap progres- at the surface, cements became light on a covariant
sively sealed both unconformity and platform, meteo- trend (6). The lighter 613C values suggest increased
ric flow was curtailed and basin-derived fluids took water-rock interaction during burial. The final trend
over. Pore enlargement and pressure dissolution were (7) reverses towards light 6l'O values and involves a
widespread, and the cements (Zone 4, Fig. 11) relate renewed depletion in 13C. This represents the arrival
to tectonic veins. Calcite is mostly ferroan but is of basin-derived light carbon and heavy oxygen,
brightly luminescent. A return to relatively light 6I3C together with high temperatures and much water-
and heavy 6 l 8 0 values characterizes Zone 4 cement rock interaction.
666 G . M . Walkdenand D. 0. Williams

whole rock
7trends
- 4

- 3

- 2

- 1

-0
- -1

- -2
- -3

-
-4

- -5
- -6

I I I I I I I -7
-16 -15 -14 -13 -12 -11 -10 -9 -8 -7 -6 -5 -4 -3 -2 -1 0
Fig. 12. Isotopic trends for water bodies, whole rocks, and cements: Derbyshire platform. The normal meteoric line is based
upon the Key Largo Limestone, Florida (Lohmann, 1988). The pluvial meteoric line (beneath trend 3) is the proposed line
for the late Dinantian. The term implies a climatic or seasonal effect. For explanation of numbered trends see Summary and
Conclusions.

Implications commonplace during the Late Carboniferous and


similar unconformities probably supplied other car-
The general diagenetic sequence demonstrated in the
bonate shelves and platforms. Second, unfractured
late Dinantian of the Derbyshire carbonate platform
shelves and platforms and their subsurface extensions
is repeated in contemporaneous shallow-water shelf
must remain unpromising exploration targets at levels
limestones throughout northern Britain. The palaeo-
as high as the Asbian and Brigantian unless areas can
environmental and structural setting of some of these
be found where they were adequately protected from
carbonate bodies should create good hydrocarbon
the late meteoric influx represented by Zone 3 cements.
plays, but prospective reservoirs have been difficult to
Both ore mineralization and hydrocarbon influx occur
locate. The detailed history we now demonstrate
with tectonism during Zone 4 cementation and can be
enables us to suggest a reason why.
reasonably well constrained to the late Westphalian-
Zone 1 created an ideal early cemented framework
early Permian.
that could resist compaction and remain adequately
porous at depth. Zone 4 cement shows that the
necessary maturation levels had been achieved in the ACKNOWLEDGMENTS
adjacent basins and that hydrocarbon sources were
accessible and pathways clear. What intervened, The authors thank Tony Fallick and the Scottish
however, was a comprehensive filling of most acces- Universities Research Reactor Centre at East Kilbride
sible porosity (Zone 3 cement). Identical cements are for providing facilities for the stable isotope work.
found in Dinantian shelves and platforms throughout Gail Bingham (Aberdeen) kindly undertook the
northern England and North Wales and two implica- calcrete analyses. Tony Fallick and Maurice Tucker
tions arise. First, external sourcing of cements of Zone read and commented most helpfully upon earlier
3 type in Lower Carboniferous rocks may have been versions of the manuscript. We especially thank Bill
Derbyshire-East Midland carbonate shelJ England 667

Meyers for his painstaking review which led to better CHOQUETTE, P.W. & JAMES,N.P. (1987) Diagenesis in
presentation of our ideas. Peter Hill and Stuart Kearns limestones-3. The deep burial environment. Geosci. Can.,
14, 3-35.
provided valued advice and expertise at the NERC- COLLINSON, J.D. (1988) Controls on Namurian sedimenta-
funded probe unit at Edinburgh University, the use of tion in the Central Province basins of Northern England.
which we gratefully acknowledge. The paper is based In : Sedimentation in a Synorogenic Basin Complex, the
upon work started under NERC grants GT14/82/TS/ Upper Carboniferous of Northwest Europe (Ed. by B.M.
Besley & G. Kelling), pp. 3842. Blackie & Son, London.
2 and GR3/5974.
COLMAN, T.B., JONES,D.G., PLANT,J.A. & SMITH,K. (1989)
Metallogenic models for carbonate-hosted mineral depos-
its. In: Metallogenic Models and Exploration Criteria Jor
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(Manuscript received 15 November 1989; revision received 16 January 1991)

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