Septarias

Sedimentology (2001) 48, 507±531
Septarian concretions from the Oxford Clay

(Jurassic, England, UK): involvement of original marine
and multiple external pore ¯uids
J. D. HUDSON*, M. L. COLEMAN , B. A. BARREIROà and N. T. J. HOLLINGWORTH§
*Department of Geology, University of Leicester, Leicester LE1 7RH, UK (E-mail: jdh4@leicester.ac.uk)
Postgraduate Research Institute for Sedimentology, University of Reading, Whiteknights, Reading RG6
6AB, UK
àNERC Isotope Geosciences Laboratory, Kingsley Dunham Centre, Keyworth, Nottingham NG12 5GG, UK
§Natural Environment Research Council, Polaris House, North Star Avenue, Swindon SN2 1EU, UK
ABSTRACT
Septarian concretions occur at several horizons within the Oxford Clay

Formation, a marine mudstone containing pristine aragonite and immature
biomarker molecules. They record the passage of at least four generations of
pore ¯uids, the ®rst of marine origin and the last still present in cavities.
Concretion bodies formed, cracked, and calcite and pyrite precipitated in and
around the cracks within the sulphate reduction zone, as demonstrated by C, O,
S and Sr isotopic composition (Pore ¯uid 1). Before major compaction,
sandstone dykes were intruded locally, and baryte precipitated, followed by
coarse calcite cements with isotopically light oxygen and radiogenic strontium,
indicating the introduction of meteoric-derived water (Pore ¯uid 2). Later,
coarse celestine within concretions has distinct sulphur-isotopic composition
and requires a further, geographically restricted, water source (Pore ¯uid 3).
Celestine-bearing concretions contain water in tight cavities whose isotopic
composition is close to that of modern precipitation. Its chemistry shows that it
is equilibrating with pre-existing minerals implying a relatively recent origin
(Pore ¯uid 4). The mineralogy of the Oxford Clay concretions shows that
complex results can follow from a simple burial and uplift history, and that
multiple generations of pore ¯uids can pass through a low-permeability clay.
Keywords Concretions, Oxford clay, Palaeo-hydrologeology.
INTRODUCTION (Hudson, 1978). Early formed concretions enclose

uncrushed ammonites, are brecciated internally,
The Peterborough Member of the Oxford Clay and may contain sulphate minerals as well as
Formation of central England has several advan- calcite in their crack-®llings; residual vugs some-
tages for studies of the formation and subsequent times contain trapped water. Other concretions
evolution of concretions. It is an organic-rich contain crushed fossils and started to form after
mudrock with well-controlled biostratigraphy some compaction. The depth of burial of the
from its abundant ammonite faunas (Callomon, Oxford Clay has been estimated as not exceeding
1968; Martill & Hudson, 1991). Aspects of its »500 m (Hudson, 1978). A maximum burial tem-
palaeoecology, clay mineralogy, organic, trace- perature of less than 50 °C is implied by preser-
element and isotopic geochemistry are well estab- vation of organic biomarkers (Hudson & Martill,
lished (Hudson & Martill, 1994). It has excellent 1994).
preservation of biominerals, especially aragonite. The mineralogy and geochemistry of recently
Various types of large calcareous concretions, discovered concretions from an area 20±40 km
generally with pyrite, occur at several horizons south-west of that investigated by Hudson (1978)
Ó 2001 International Association of Sedimentologists 507
508 J. D. Hudson et al.
are described in this paper, which adds new

data on Sr, S and sulphate oxygen isotopic
composition on some of the occurrences des-
cribed previously. These data elucidate the
diagenetic history of the concretions; they imply
that multiple generations of pore waters tra-
versed these low-permeability mudrocks since
their deposition. Hudson (1978) argued for
in®ltration of meteoric water into the marine
Oxford Clay and discussed its timing. Martill &
Hudson (1989) further argued, from the relation-
ship of concretions to an intrusive sandstone
dyke, that initial in¯ux took place beneath the
marine basin, while the higher parts of the
Oxford Clay were still being deposited, with
water being transmitted from the Kellaways
Sand palaeo-aquifer beneath. The new results
con®rm these interpretations. Analagous propos-
als for meteoric in¯uence on septarian ®lls have
been made for other concretions (Boles et al., Fig. 1. Outcrop map of Oxford Clay and associated
1985; Thyne & Boles, 1989), though usually Upper Jurassic clays (shaded area) in central and
without constraints on timing. southern England. Localities mentioned in the text: RG,
Rixon Gate; CAS, Cassington; C, Calvert; B, Bletchley;
S, Stewartby; P, Peterborough. For localities in the
Peterborough district see also Hudson & Martill (1994,
THE OXFORD CLAY CONCRETIONS ®g. 1b).
The localities studied are shown in Fig. 1. The

stratigraphical and geographical distribution of part of the Peterborough Member. The Àcutistri-
concretions in brickpits in the Peterborough atum concretions' occur uniquely within or
Member of the East Midlands was described by adjacent to the Acutistriatum Bed in the upper
Hudson (1978). Two main concretion types and part of the Member. They post-date some com-
levels were recognized. The `main concretions' paction, as they contain ¯attened ammonites.
are markedly septarian or brecciated (Fig. 2). Some Oxfordian age concretions from the overly-
They are found in distinct beds within the lower ing Ampthill Clay Formation, from the north of
Fig. 2. Field photograph of part of

a brecciated `main concretion'
from Calvert. Fragments of the
concretion body are margined by
pyrite (dark), shown by an arrow.
Grey material in the bottom centre
is ìntrusive clay'; small shells are
visible within it. White crystalline
material is spar calcite. Hand-lens
(4 cm) to right of photograph, for
scale.
Ó 2001 International Association of Sedimentologists, Sedimentology, 48, 507±531
Oxford Clay concretions 509
the study area, were also included in Hudson cavities, when cracked open, yielded trapped
(1978). These, and also one concretion from the water. Celestine occurs in concretions through
Oxford Clay itself, contained demonstrably early several metres of strata at Cassington, and nearby
brown calcite in their septarian cracks; they were at Calvert, but is not otherwise recorded from the
designated Èarly septarian concretions', a dis- Oxford Clay.
tinction maintained herein. At Rixon Gate, concretions in a bed of
The new locations are Cassington near Oxford, particularly organic-rich shale contain teuthoid
where concretions occur at several horizons with- cephalopods (mainly Belemnotheutis) with phos-
in the lower part of the Peterborough Member, and phatized soft mantle tissue, in small dark-
are notable for containing macroscopic celestine coloured, ellipsoidal concretions (up to 30 cm
and trapped water, and Rixon Gate near Ashton diameter and 10 cm thick). They are composed of
Keynes, Wilts. Although they are found within the calcite with minor clay, organic and pyrite
same ammonite subzone as the Acutistriatum content, and split evenly along laminations.
concretions, they are petrologically more similar Larger concretions, up to 1 m in diameter and
to the Main concretions of the East Midlands. 35 m thick, have strongly pyritic rims and contain
A concretion measuring 1á1 ´ 0.4 m from Cas- septarian fractures up to 1 cm wide that are
sington (Fig. 3) was excavated from »3 m beneath completely ®lled with white sparry calcite; these
the ¯oor of the pit, and immediately sampled. The disrupt the fossils. Both types of concretion
concretion body is of ®ne-grained grey calcite, contain ammonites which have three-dimension-
slightly argillaceous and pyritic, and contains al phragmacones, ®lled with sparry ferroan cal-
ammonite and bivalve shells. It is intensely cite, but ¯attened body chambers. Data presented
brecciated, with large and small septarian cracks. below show that the Rixon Gate concretions are
Pyrite increases in abundance towards the mar- not notably distinctive geochemically.
gins of brecciated fragments, which have a pyrite
lining. Small cracks, up to about 1 cm, are
completely ®lled with sparry calcite. Large ones ORIGIN OF SEPTARIAN CONCRETIONS:
are incompletely ®lled, with remaining voids BRIEF REVIEW
several centimetres across. The ®rst visible gen-
eration of the ®ll is white calcite with dog-tooth Concretion bodies
crystal terminations. Thin sections and scanning
Septarian concretions of calcite are believed to
electron micrographs reveal that this calcite con-
have commenced growth a few metres, at most,
tains small, euhedral crystals of baryte. Overlying
below the sea ¯oor. The porewaters were essen-
the calcite are centimetre-scale crystals of blue
tially sea water modi®ed by bacterial activity.
celestine, with rectangular cleavage but generally
This conclusion was argued for the Oxford Clay
not showing euhedral crystal faces. Some of the
Fig. 3. Photograph of a vug within

a partially ®lled large septarian
vein in a concretion from Cassing-
ton. Concretion body (dark) con-
tains an ammonite fragment (A)
preserved as nacreous aragonite;
the main crack in this is ®lled with
concretion-body material, smaller
cracks by spar calcite. Vug is part-
®lled by spar calcite (C) with
rhombohedral crystal termina-
tions. Blue celestine (CS) overlies
calcite in central part of vug. When
®rst broken, the vug contained
trapped water. This and similar
vugs from the same concretion
provided the material from Cas-
sington analysed for this paper.
Ammonite fragment is 2á5 cm
across.
by Hudson (1978). The question of concretion agree on formation of pyrite-bearing calcite con-
growth mechanisms has recently been reviewed cretions by bacterial activity in the sulphate
by Raiswell & Fisher (2000). Most early studies reduction zone of organic-rich sediments, but
assumed that concretions grow concentrically views diverge on the origin of the cracks and their
outwards, starting from a point of nucleation ®llings. Mechanisms have been discussed by,
(e.g. Hudson & Friedman, 1976). More recently, among others, Astin (1986), Hesselbo & Palmer
Coleman & Raiswell (1993, 1995) studied concre- (1992), Hounslow (1997) and Raiswell & Fisher
tions from the Jurassic Jet Rock shales in York- (2000). Resolution of the cracking process
shire, and proposed that they can grow by requires knowledge of the initial cement of the
pervasive cementation of a body of sediment of concretion body: complete or partial; calcite, high
essentially the same size as the ultimate concre- magnesium calcite, or an organic phase? The
tion, as previously proposed for siderite concre- discussion is further complicated by the possi-
tions by Mozley (1989). Their model further bility that the microspar calcite that now forms
postulates that the concretion grows in the near- the body of most concretions is a neomorphic
surface sediment during a period of reduced product (Dickson & Barber, 1976). Possibly not all
sedimentation; a similar circumstance is indica- septarian cracks form in the same way.
ted by a shell-bed above the concretion horizon in The ®llings of cracks are even more diverse,
several of the Oxford Clay examples. Also, initial because they record events which took place
cementation does not necessarily ®ll pore space either soon after the concretion body formed, or
within the concretion completely, so that concre- long afterwards. The succession of cements in
tions can grow by successive stages of pervasive septarian cracks clearly record a history of preci-
cementation without necessarily showing con- pitation episodes. However, it is not plausible to
centric zonation (e.g. Mozley, 1996; but see Boles invert the understanding of the process and to
et al., 1985 for a contrary example). Early studies compute precise chemical compositions of suc-
assumed, mostly implicitly, that the chemical and cessive pore waters. This is because mineral
isotopic composition of each concentric zone phases may not be precipitated in equilibrium
within a concretion was in equilibrium with the with the bulk composition of the parent waters
pore waters of the subsea ¯oor sediment at the (Coleman & Raiswell, 1995) and also the rate of
time of that zone's cementation (the equilibrium precipitation may control the extent of trace-
model), but Coleman & Raiswell (1995) proposed element substitution in a mineral (Dromgoole &
instead that the potential concretion was the site Walter, 1990). The effects of variation of rates of
of enhanced organic-matter concentration and/or precipitation are much smaller than those
bacterial activity, and that this determined the induced by signi®cant changes in water chemical
concretion's chemistry (the local equilibrium composition. Thus, it is still possible to gain
model). The nature of the bacterial communities valuable information on ¯uids from the mineral
in the case of modern siderite-dominated concre- phases. In particular, one can deduce trends of
tions has been described by Coleman et al. (1993), change in composition, as shown by Curtis et al.
though in a sedimentary setting very different (1986), or the in¯ux of successive generations of
from that in the Oxford Clay. A further possibil- pore waters (Marshall, 1982), even though precise
ity, mainly applying to the later stages of concre- quantitative evaluation of pore-water chemistry is
tion growth, is that mixing of depositional waters impossible. It follows that whereas concretion
with water from subjacent palaeo-aquifers pro- bodies formed in the sulphate reduction zone will
motes mineral precipitation (Hudson & Friedman, have common features through space and time,
1976; Hudson, 1978; Boles et al., 1985; Mozley & the history of septarian crack ®llings will differ
Burns, 1993); this is discussed later. depending on the later history of the basins in
which their host sediments occur (e.g. Hudson,
1978; Marshall, 1982; Dix & Mullins, 1987; Siegel
Septarian cracks and ®llings
et al., 1987; Thyne & Boles, 1989; Scotchman,
Many concretions display more or less regular 1991; Desrochers & Al-Aasm, 1993).
septarian cracks, whereas others, including many
Oxford Clay examples (Figs 2 and 3), are more
irregularly brecciated. The cracks are usually METHODS
®lled, completely or partially, by one or more
generations of mineral precipitates, most com- Electron microprobe analyses were carried out by
monly carbonates and sulphates. Most authors R. N. Wilson and L. Marvin using a JEOL JXA-
8600S at an accelerating voltage of 15 kV and a replicate analyses). All sulphur isotope composi-
current of 30 nA. The ®nal beam diameter was tions are reported relative to CDT. Oxygen isotope
increased to 15 lm to minimize thermal damage ratios in sulphates were determined by Dr A.
to the specimen. Peak and background counting Boyce at SURRC, East Kilbride, and are reported
times of 40 s were used for all elements analysed relative to SMOW.
in calcite. Celestine and baryte were analysed Sr isotopes were analysed at the NERC Isotope
with peak and background counting times of 20 s Geoscience Laboratory, Keyworth. Carbonates
for CaO and MnO and 60 s for SrO, BaO, MgO, (calcite crystals, concretion body samples, and
FeO and SO3. These conditions yielded the shells) were dissolved at room temperature in
values listed in the tables for analytical precision 10% acetic acid overnight. This attack is less
and minimum detection limit. Standards used likely to remove Sr from silicate phases or from
included both well-characterized natural miner- organic material than using stronger acids. The
als and synthetic oxides. Corrections for differ- solution was centrifuged and pipetted into a
ences in atomic number (Z), absorption (A) and clean Savillex beaker, then evaporated. The
¯uorescence (F) between standards and speci- sample was converted to chloride form with the
mens were applied using version 1á08 of JEOL's addition of 3 mL of 6 N HCl, evaporated again
ZAF quantitative analysis program. Minimum and redissolved in 2á5 N HCl.
detection limits (weight per cent oxides, 3 sigma Sulphates (baryte and celestine) were dissolved
above background) were CaO 0á04, MgO 0á03, FeO in 6 N HCl in a closed Savillex capsule for up to a
0á04, SrO 0á05, BaO 0á11 and SO3 0á04. week. Complete dissolution was not achieved but
Stable isotope analyses of C and O in carbonates suf®cient Sr was removed for analysis. After
used standard preparation techniques to produce centrifugation, the solutions were evaporated
carbon dioxide (McCrea, 1950) and oxygen iso- and converted to 2á5 N HCl.
tope analyses of water were performed according Shale and mudstone samples were leached in
to methods similar to those of Epstein & Mayeda 10% acetic acid to remove the exchangeable Sr, to
(1953) to produce carbon dioxide. The resultant check whether Sr from clays was liable to affect
gases were measured on a VG SIRA II isotope ratio results from impure carbonates such as concre-
mass-spectrometer using the correction factors for tion bodies. Extensive release of CO2 bubbles
the mass spectrometric analyses for CO2 of Craig occurred, implying that carbonates within the
(1957). Water samples were prepared for hydrogen shales were being dissolved. Data discussed
isotope analysis using the method of Coleman below indicate minimal contribution of Sr from
et al. (1982) and measured on the same mass- clay minerals. Conversion to 2á5 N HCl followed
spectrometer. Isotopic analyses of waters were as described above.
measured at least in duplicate and reported Once in solution in 2á5 N HCl, Sr was removed
relative to SMOW, and their standard deviations from the samples by cation exchange column
are quoted in Table 4 as total errors. Isotopic chromatography using Biorad at 50 ´ 8, 200±400
compositions of carbonate are reported relative to mesh cation exchange resin. The fraction con-
PDB. taining Sr was evaporated prior to mass specto-
Cation compositions of carbonates (measured metry.
on residual phosphoric acid after isotopic analy- High purity concentrated acetic, phosphoric
sis, Coleman et al., 1989) and of waters were and hydrochloric acids were used. 6 N HCl was
made by inductively coupled plasma spectrome- prepared in-house by sub-boiling distillation in a
try (ICP-AES) whereas anions in waters were quartz glass still, and 2á5 N HCl prepared by
determined by ion chromatography (IC). The total dilution of this acid with MilliQ deionized water
errors of these analyses were calculated by of better than 18á2 MegaOhm resistivity. The
combining the analytical uncertainties (2 sigma analytical blank measured during the study aver-
detection limits), the errors due to blank samples aged 260 pg Sr (n 5), orders of magnitude less
and their variability. than the amounts of Sr in the samples, so no
For isotopic measurements of sulphur, stand- blank corrections were applied to the reported
ard methods were used to prepare sulphur data.
dioxide for analysis from sulphide (Robinson & The Sr was loaded on to Ta ®laments along
Kusakabe, 1975) and from sulphate (Coleman & with 1 mL of 1 M H3PO4. The isotopic composi-
Moore, 1978). The resultant gases were measured tion of Sr was measured on a Finnegan MAT 262
on a modi®ed VG SIRA 12 mass spectrometer multicollector mass spectrometer operating in
with a precision of 0á2& (2 sigma for complete static mode. Measured 87Sr/86Sr ratios were
normalized to 86Sr/88Sr 0á1194 to correct for Early concretion bodies and their cracking
mass fractionation in the spectrometer. Normally
Results and initial interpretation
the internal precision of a single run on the mass
spectrometer is 0á000007 (one standard error of Hudson (1978) showed that the calcite microspar
the mean, n 150±250 measurements). The comprising the bulk of the concretion bodies
87/86 of NBS Sr isotope standard during the main must have an early marine origin, based on its
measurement period was 0á710231 0á000023 carbon and oxygen isotopic composition (Fig. 4).
(one standard deviation, n 12). Ten analyses of The microspar is uniformly non-ferroan, as
sea water gave 87Sr/86Sr 0á709162 0á000014 shown by staining, The bodies of the newly
(one standard deviation, n 10). This external sampled concretions from Cassington and Rixon
reproducibility of standards gives a better indica- Gate have similar petrography and stable isotopic
tion of the precision of the analyses than the compositions to those studied previously
internal precision based on counting statistics. (Table 1 and Fig. 4B). The oxygen isotopic com-
Data measured during a second analytical period position, which is indistinguishable from that of
were normalized to the NBS value of 0á710231. benthic and nekto-benthic fossils from the Peter-
All samples achieved the normal internal preci- borough Member, shows that the bulk of the
sion of c. 0á000007. microspar in the concretion bodies was formed
Sr isotopic ratios for two belemnites were near the sea¯oor. The negative carbon isotopic
determined by Dr R. Koepnick in the Mobil composition, together with the presence of pyrite,
laboratories, Dallas, according to their standard suggests formation in the sulphate reduction
procedures (Koepnick et al., 1990). These are zone. This also explains the non-ferroan compo-
used to estimate the 87Sr/86Sr ratio of local sition of the microspar, as iron was sequestered
Callovian sea water. into iron sulphides.
The new data include strontium isotopic com-
positions of concretion bodies (Table 1). These
RESULTS AND DISCUSSION are similar to Callovian sea water as given by
Jones et al. (1994) and by new belemnite analyses
Data on the Oxford Clay concretions are presen- (Table 1), but a little more radiogenic (Fig. 5).
ted in Tables 1±4. The sediment, the early forma- Strontium isotopic analyses of acetic acid
tion of concretions and later events are discussed leachates from mudstones (Fig. 5) are within the
in turn. range found for marine and diagenetic calcites, as
expected from the clay petrography, suggesting
minimal input of Sr from clay minerals. Propor-
The Oxford Clay sediment
tionally even less Sr from clays can have affected
The Oxford Clay sediment is described by Hud- analyses of concretion bodies as these contain
son & Martill (1991). Macquaker (1994), Norry over 80% diagenetic calcite.
et al. (1994) and Macquaker & Howell (1999) Tables 2 and 3 present data on the minor
describe its mineralogy and geochemistry. The element content of the concretion body calcite.
main detrital minerals present are, in order of It is not possible to analyse the microspar itself by
abundance, illite, quartz, kaolinite and chlorite microprobe, because of overlap of the beam on to
(Norry et al., 1994; Table 1). In general, concre-
tions occur in organic-rich, more or less silty,
clays or mudstones, often beneath shell-beds Fig. 4. Carbon and oxygen isotopic composition of
calcite from concretions in the Oxford and Ampthill
which are believed to mark pauses in sediment
Clays. Data from this paper (Table 1), Hudson (1978)
accumulation. Scanning electron microscopy and Martill & Hudson (1989). Field labelled `marine
(Macquaker, 1994) and examination of smear calcite' shows mean and standard deviation (1 sigma)
slides (Martill et al., 1994) shows that the mud- of well-preserved belemnites and Gryphaea from the
stones contain a mixture of primary calcite Oxford Clay (Anderson et al., 1994). Dashed lines
(mostly coccoliths) and diagenetic calcite cement. enclose groups of related analyses. In (A) the solid line
Pyrite occurs as framboids, equant grains and separates data from two different localities. Diagenetic
trends are consistently from light carbon-heavy oxygen
shell replacements (Fisher, 1986; Macquaker, concretion bodies to heavy carbon-light oxygen for spar
1994). The sediment is organic-rich, varying from calcites. Note close grouping of values for concretion
0á6% to 16á6% TOC, averaging »5% (Kenig et al., bodies and variation between localities for later phases,
1994). especially spar calcites.


Table 1. Carbon, Oxygen and Strontium isotopic composition of calcites from the Peterborough Member, Oxford
Clay Formation (except samples pre®xed P 595, from the Ampthill Clay Formation). Localities as in Fig. 1.
13
Sample Locality Classi®cation d CPDB d18OPDB 87/86
Sr
C1C1A Calvert ESC-CB )11á98 )0á60 0á707471

C1C2A Calvert ESC-EC )8á83 )2á14 0á707398
C1C2A-d Calvert ± )8á67 )2á48 0á707398
C1C3A Calvert ESC-SC-I )7á17 )3á59 0á709530
C1C3B Calvert ESC-SC-O )0á54 )5á35 0á709530
C3A953A Calvert MC-IC )0á06 )6á47 0á708706
C5951A Calvert MC-SC-I )1á02 )7á70 0á708880
C5951B Calvert MC-SC-O )0á86 )7á62 0á708880
C5952A Calvert MC-CB )14á80 )0á48 0á707289
CV351A Calvert AC-CB )8á00 )3á69 0á708333
CV9512A Calvert MC-SC +0á08 )6á59 0á708748
CV9512A-d Calvert ± +0á10 )6á56 0á708748
CV9513A Calvert MC-CB )14á72 )0á58 0á707298
CAS109564 Cassington MC-SC +1á16 )7á87 0á708680
CAS109564-d Cassington ± +1á13 )7á86 0á708680
CAS109565 Cassington MC-SC +1á08 )7á88 0á708680
CAS109574 Cassington MC-SC-I +0á96 )8á63 0á708683
CAS109575 Cassington MC-SC-O +0á96 )7á88 0á708683
CAS109583A Cassington MC-CB )14á95 )0á90 0á707079
P1AB1A Peterborough MC-SC )0á11 )9á59 0á709025
P1AB2A Peterborough MC-CB )15á93 )0á76 0á707907
P5951A Peterborough ESC-SC )3á11 )9á36 0á708330
P5952A Peterborough MC-EC )20á01 )0á54 0á706899
P5952A-d Peterborough MC-EC )19á98 )0á61 0á706899
P5953A Peterborough ESC-EC )13á04 )0á90 0á707423
RG5AA Rixon MC-CR )9á93 )2á49 0á707506
RG5CA Rixon MC-CB )12á30 )1á47 0á707033
RG5C2A Rixon MC-SC +0á38 )5á13 ±
BLCP120 Peterborough Belemnite +2á07 )1á26 0á706802
BLCP116 Peterborough Belemnite 2á27 )0á82 0á706852
Abbreviations: ESC, early septarian concretions; MC, main concretions; AC, Acustriatum concretions; CB, concretion
body; EC, early calcite; SC, spar calcite(I, inner; O, outer part of a single crystal-fringe); IC, intriusive clay cement;
belemnites from the Jason Zone, Bunting's Lane, Peterborough (Williams, 1988). Analysts: C, O Coleman; Sr, Bar-
reiro, except belemnites C, O from Williams (1988), Sr from R. L. Koepnick (Mobil, Dallas). d indicates duplicate
analysis.
clay particles, but small cavities in fossils such as solution from clay minerals or, for Fe, soluble
foraminifera are ®lled with apparently identical sulphides. The latter is suggested by a very high
but coarser calcite, shown to be non-ferroan by value obtained from a pyritic rim to a Rixon Gate
staining (unlike large cavities such as ammonite concretion.
chambers, which contain ferroan calcite like that Like many other calcitic concretions (e.g. the Jet
in the septarian cracks; see below). Microprobe Rock, Coleman & Raiswell, 1995), the Oxford Clay
analyses show that this calcite contains around examples have rims that are strongly pyritic. This
1á4 weight per cent MgO, and low values for FeO pyrite forms coalescent equant crystals, unlike
and SrO (Table 2). the framboids which are dominant in the sedi-
Less accurate data on the elemental composi- ment outside the concretions. The pyritic rim is
tion of the concretion body calcite are available cut, in some cases, by septarian fractures which
from ICP analyses of the phosphoric acid resi- taper and do not extend to the margin of the
dues from dissolution for stable isotope analysis concretion. In their inner parts, these cracks are
(Table 3, Fig. 6). The values obtained are in themselves margined by thinner rims of pyrite,
general agreement with those from the micro- which permeates the adjacent concretion body,
probe, although the Fe and Mg values may be particularly affecting faecal pellets (Hudson,
high because of contributions to the analysed 1978; Figs 3, 7A and B).
Fig. 5. Strontium isotopic evolution of concretions. Concretion bodies and early calcites are close to Callovian sea
water as indicated by similarity to the belemnite samples. Strontium in later phases is progressively more radiogenic.
Leachates from acetic acid treatment of shale samples fall within the range of separated calcite samples.
towards internal cracks as well as towards the

Discussion
outer margin; it is concentrated especially in
The new carbon and oxygen isotope results organic-rich pelletal structures (Fig. 7A). This
con®rm those of Hudson (1978) on the early shows that sea water sulphate could diffuse into
marine formation of concretion bodies. The new the already-formed but still porous concretion
data on Sr isotopes are consistent with this. They body to a depth of several millimetres, after the
contain slightly more radiogenic Sr than Callo- cracks had formed, implying that the concretion
vian sea-water, suggesting the incorporation of a body was not yet totally cemented. Equally, the
little later-precipitated cement. However, this intense brecciation into angular fragments shown
cannot be explained by simple admixture with by the Oxford Clay concretions (Fig. 2) does not
the spar cement present in septarian crack in®l- suggest slow fracturing of `cheese', even very hard
lings (see below), as that is ferroan, whereas the cheese (cf. Hesselbo & Palmer, 1992). Reptilian
concretion bodies are not. bones, which were always hard and brittle, are
Data collected in this study contribute to, but affected by septarian cracks; they have not merely
do not resolve, an on-going debate about the broken across the septaria but are shattered into
formation of septarian cracks. Hesselbo & Palmer angular shards (Barker et al., 1997; plate 1a).
(1992) believe that the original cement of concre- Hounslow's (1997) theory of crack formation
tions from the Lias of Dorset was not calcite, but depends on differential over-pressuring of pore
an organic `glue', on the basis of observations water in the concretion as opposed to the sur-
some of which also apply to the Oxford Clay. rounding clay. In the case of the Oxford Clay
These include the way the concretion body has main concretions it must have operated under a
evidently pulled away from an ammonite shell shallow overburden; Hounslow mentions less
(cf. Hudson, 1978; Fig. 5B), the curved nature of than 10 m as a minimum. It is hard to imagine
some of the septarian cracks, and the presence on such a process at such a shallow depth shattering
their sides of small, irregularly shaped ¯akes of bone. In addition, there is no evidence of outward
concretion body material. These observations are distortion of the adjacent sediment where septar-
hard to reconcile with the fracturing of a ian cracks extend to the concretion rim, but
completely cemented calcite concretion body. conversely there is evidence of intrusion of clay
Raiswell & Fisher (2000) suggest that early into the concretion after cracking (Hudson, 1978;
cementation of concretion bodies was by calcite, Fig. 2), and in some concretions the centre has
but was incomplete; see also Mozley (1996). In the collapsed under later compaction whereas the
brecciated Oxford Clay concretions, pyrite increases pyritic rim has proved resistant. In other words
516
Table 2. Electron microprobe analyses of minerals from a concretion from Cassington.

J. D. Hudson et al.
Weight % oxides, mean (range)
Sample Mineral N CaO MgO FeO SrO BaO SO3 Total
CAS 1095-6A Non-ferroan calcite 5 53á83 1á39 0á03 0á05 0á11 ND 55á42
(concretion body) (53á41±54á41) (1á30±1á48) (bd±0á08) (0á04±0á08) (bd±0á18) (oxides)
CAS 1095-6A, Ferroan calcite 20 53á86 0á38 1á53 0á05 bd ND 55á81
7A, 8A (septarian veins) (52á84±55á45) (0á11±0á51) (0á72±1á81) (bd±0á10) (oxides)
CAS 1095-7A Celestine 5 bd bd bd 56á53 0á31 43á37 100á26
(septarian veins) (56á48±56á69) (0á20±0á46) (43á13±43á51)
CAS 1095-8A Celestine 5 0á15 bd 0á22 55á75 0á29 43á09 99á55
(septarian veins) (0á14±0á19) (bd±1á03) (55á30±56á32) (0á23±0á39) (42á42±43á64)
CAS 1095-8A Baryte 10 0á15 bd bd 10á31 54á33 33á66 98á48
(inclusion in (bd±0á39) (8á85±11á75) (53á06±56á08) (32á65±34á55)
Fe-calcite)
CAS 1095-7A Baryte rim 0á08 bd bd 7á48 58á62 34á09 100á32
(traverse) (zoned crystal, inter bd bd bd 4á12 62á77 33á43 100á43
inclusion in core bd bd bd 2á77 64á55 33á04 100á42
Fe-calcite) inter bd bd bd 4á56 62á29 33á36 100á28
rim 0á08 bd bd 6á83 59á30 33á61 99á89
Minimum detection limit (3r) 0á04 0á03 0á04 0á05 0á11 0á04
Non-ferroan calcite sampled from the ®ll of a small foram. Other analyses of minerals from septarian veins and vugs (cf. Fig. 3). Analyst, R. N. Wilson, Leicester.
Typical precision (2r) values based on intensity data. CaO, 0á3 at 54%, 0á04 at 0á15%, 0á04 at 0á08%; MgO, 0á04 at 1á4%, 0á03 at 0á38%; FeO, 0á07 at 1á5%,
0á05 at 0á2%; SrO, 0á04 at 0á05%, 0á18 at 10%, 0á5 at 56%; BaO, 0á1 at 0á1%, 0á05% at 0á3%, 0á34% at 54%; SO3, 0á46% at 43%, 0á37 at 33%. bd, below
detection limit; ND, not determined; MnO measured, below detection limit of 0á07 wt% in all analyses.

Table 3. ICP analyses of phosphoric acid residues from the calcite samples used for C and O isotope analyses
reported in Table 1, expressed as molar fractions of cations.
Sample no. Ca Mg Fe Mn Sr Ba Si Al
C1C1A 0á93 0á055 0á0134 0á00017 0á00049 0 0á16 0á07

C1C2A 0á93 0á057 0á0072 0á00077 0á00078 0á00003 0á05 0
C1C2A-d 0á94 0á049 0á0068 0á00076 0á00075 0á000028 0á03 0
C1C3A 0á96 0á011 0á0241 0á00254 0á00026 0á000026 0á06 0
C1C3B 0á95 0á01 0á0382 0á00251 0á00037 0á000019 0á05 0
C3A953A 0á93 0á025 0á04 0á00134 0á00046 0á00003 0á16 0á1
C5951A 0á96 0á012 0á0242 0á00177 0á00047 0á000033 0á05 0
C5951B 0á97 0á012 0á0124 0á00143 0á00107 0á000055 0á03 0
C5952A 0á95 0á041 0á0046 0á0001 0á00036 0á000027 0á08 0á03
CV351A 0á96 0á027 0á0103 0á00226 0á00059 0á000026 0á11 0á06
CV9512A 0á97 0á013 0á0228 0á00149 0á0004 0á000019 0á03 0
CV9513A 0á94 0á055 0á0075 0á00013 0á00053 0á000022 0á1 0á05
CAS109564 0á94 0á015 0á0334 0á00165 0á00033 0 0á06 0
CAS109565 0á96 0á015 0á0278 0á00165 0á00031 0á000019 0á04 0
CAS109574 0á94 0á017 0á0372 0á00193 0á00053 0á000017 0á05 0
CAS109575 0á93 0á013 0á0172 0á00128 0á04089 0á000298 0á04 0
CAS109583A 0á93 0á056 0á0094 0á00035 0á00047 0á000017 0á09 0á04
CAS109583B 0á98 0á005 0á0138 0á00048 0á00198 0á000066 0á15 0
P1AB1A 0á94 0á016 0á0459 0á00161 0á001 0á000013 0á05 0
P1AB2A 0á94 0á05 0á00777 0á00012 0á00034 0á000029 0á1 0á04
P5951A 0á93 0á019 0á048 0á00656 0á00124 0á000037 0á06 0
P5952A 0á93 0á058 0á0089 0á0063 0á00044 0á000022 0á03 0
P5953A 0á93 0á064 0á0007 0á00006 0á00093 0á000058 0á03 0
RG5AA 0á71 0á043 0á2416 0á00076 0á00047 0á000033 0á07 0á03
RG5CA 0á93 0á048 0á0163 0á00068 0á00046 0á000022 0á08 0á01
RG5C2A 0á96 0á016 0á0257 0á00171 0á0008 0á000019 0á03 0
there is evidence of inward but not outward body, and led to pyrite precipitation along cracks.
pressure. The cracking mechanism, whatever it is, In some cases, a further stage of cracking followed
must depend on some property that concretions the formation of the pyritic rims on the brecciated
have or had, but other rigid bodies in shales do fragments.
not.
The most likely scenario is that most of the
Early brown calcites
concretion body calcite was precipitated, poss-
ibly preceded or accompanied by organic matter, Results
within the sulphate reduction zone, in discrete
Some of the concretions from the Oxford and
regions within the sediment that were the sites of
Ampthill Clays, like many concretions elsewhere
enhanced bacterial activity (cf. Pye et al., 1997).
(e.g. Boles et al., 1985; Astin & Scotchman, 1988;
Concretions grew rapidly, relative to their rate of
Hesselbo & Palmer, 1992) have an early genera-
burial, and the formation of their pyritic rims
tion of brown calcite that lines septarian cracks.
overlapped that of their calcitic centres. Cracking
Earlier studies (Hudson & Friedman, 1976; Hud-
of the concretions took place while they were
son, 1978) found that these calcites have carbon
largely, but initially not completely, cemented by
and oxygen isotopic compositions similar to
calcite. Some process speci®c to the concretion,
those of the concretion bodies (Fig. 4A). This
not visibly affecting the surrounding mud, led to
has been con®rmed by the new analyses
the cracking and brecciation of its interior,
(Table 1), which also show that the Sr isotopic
including shells and bones included in it, and
composition of one of these calcites is the least
in some cases of its margins too. Continuing
radiogenic (closest to sea water values) observed
sulphate reduction was promoted by concentra-
(Fig. 5). The early brown calcites contain a little
tion of metabolizable organic matter in faecal
more Mg on average compared with concretion
pellets within the now-brecciated concretion
bodies, and much more than later spar calcites
Fig. 6. Plots showing the elemental composition of

calcites from concretions against d18O as an index of
diagenetic evolution (cf. Fig. 4). Symbols as in Fig. 4.
Weight per cent oxides calculated from ICP analyses
reported in Table 3. Symbols to right of plots are
microprobe analyses from Hudson (1978) and Table 2
herein.
from septarian cracks (Fig. 6A). Iron contents are

highly variable, especially in the brown calcites
from the Ampthill Clay concretion: a probe
analysis reported in Hudson (1978) was the most
ferroan calcite observed at 3á0% FeO, whereas
one of our present ICP analyses has negligible
iron. Stain intensity is also variable.
Discussion
The isotopic compositions and Mg contents are
consistent with the formation of these calcites
from marine pore waters. The Ampthill Clay
concretion has high and variable Fe in both its
concretion body and its early calcite. It is prob-
able that this concretion and its early cements
formed near a ¯uctuating boundary between the
suboxic (Fe-reduction) and sulphate reduction
bacterial zones. A similar case is reported by
Scotchman (1991).
Syn- or post-compaction concretion bodies

Results
Based on petrographical criteria and crushing of
contained fossils, the distinctive concretions
present in the Acutistriatum Bed at Calvert,
Bletchley and Stewartby grew after some com-
paction of the clay. The concretion body calcite
has heavier carbon but lighter oxygen isotopic
composition than the pre-compaction concre-
tions, but is not as heavy in carbon or as light in
oxygen as the spar calcites discussed below
(Hudson, 1978; Fig. 4C). The Sr isotopic compo-
sition and the elemental composition of the
Acutistriatum concretions at Calvert are also
intermediate (Figs 5 and 8). There are no system-
atic differences in Sr content between the differ-
ent calcite generations.
Discussion
Hudson (1978) postulated that the pore water
from which these concretions grew was interme-
diate in isotopic composition between the ori-
ginal marine pore water and meteoric-derived
water rising from below; the presumed source of
Fig. 7. Scanning electron micrographs (back-scatter mode) of minerals from vugs in a concretion from Cassington
(cf. Fig. 3). (A, B) concretion body with pyrite margin (white), top left; baryte inclusions (white) in calcite (grey), to
right. (C) calcite (grey), left, celestine (white), to right. Void space between, with corroded edge of celestine crystals
adjacent to it. Scale bars: A, 300 lm; B, 150 lm; C, 600 lm.
later calcite in septarian cracks whose origin is These relationships suggest that the Oxford
discussed later. It is not clear from the data Clay sediment was invaded by meteoric-derived
whether the intermediate C, O and Sr isotopic waters of lighter oxygen but heavier carbon
composition results from an evolution of the pore isotopic composition than marine Pore-water 1.
waters, or whether the calcite in the Acutistria- Other mechanisms for producing the observed
tum concretions is a physical mixture of early and isotopic trends (Mozley & Burns, 1993) are not
late calcite. Stained thin sections (Dickson, 1965) likely in this case. Meteoric-derived water pene-
suggest that the ®rst interpretation is correct. The trated the compacting sediment in which the
microspar in the Acutistriatum concretions from Acutistriatum concretions formed, partially dis-
Calvert has a crystal size of 10±15 lm, and is placing the depositional pore water. It is probably
wholly non-ferroan. If it were a mixture of early related to the water (Pore-water 2) that deposited
and late calcite it should be partly ferroan, or minerals in the septarian cracks of the early
zoned. Late calcite ®lls septarian cracks in the formed concretions, which are now described and
concretions, and very tenuous offshoots from then discussed.
these, down to 4 lm across, are strongly ferroan.
The microspar in the Acutistriatum concretions
Filling of septarian cracks: sedimentological
from Stewartby is slightly ferroan but similarly
and petrographical evidence
shows no zonation by staining, nor in back-
scattered electron imaging. Assuming that the various occurrences of septar-
The compacted rims of some of the main ian crack ®llings in the Oxford Clay concretions
concretions, including the newly analysed one originated from a common sequence of events, a
from Rixon Gate, are similarly isotopically paragenetic sequence can be erected as follows
distinct from the centres of the concretion (cf. Fig. 3). Localities where a particular genera-
bodies, with heavier carbon, lighter oxygen, and tion is well developed are indicated. The succes-
more radiogenic strontium (Figs 4B and 8). The sive pore waters which affected the concretions
association of isotopically lighter oxygen with are noted here. They are de®ned and discussed
heavier carbon is different from the relationship later.
seen in concretions from the Jet Rock (Coleman
1 Intrusive clay, Calvert and Bletchley.
& Raiswell, 1995). By this stage in these samples
2 Baryte, Calvert and Cassington; sphalerite,
much organic matter had already been metabo-
Peterborough.
lized forming calcite with heavier oxygen iso-
3 Sand from an intrusive dyke, Peterborough
tope values. Thus, it seems improbable that the
(relationship to items 1 and 2 unknown).
light values result from rapid microbial proces-
4 White sparry calcite, all localities; cements
ses, which are known to be capable of precipi-
items 1±3. Formed from Pore-water 2.
tating carbonates out of equilibrium with their
5 Celestine, Calvert and Cassington. Formed
solutions (Mortimer & Coleman, 1997). There-
from Pore-water 3.
fore, the isotopic and elemental compositions of
6 Water in vugs, Cassington and Calvert. Pore-
these calcites re¯ect those of the ambient pore
water 4.
waters.
Fig. 8. Plot of strontium isotopic

composition of calcites from con-
cretions against d18O. Abbrevia-
tions for localities as in Table 1.
Note close grouping of values for
concretion bodies and early cal-
cites, and dispersal for spar cal-
cites from different localities.
Not all minerals or sediments are represented the clay, because its occurrence was con®ned to it.
in all concretions; examples of regional differ- The concretions from Cassington have so far not
ences will be discussed below. The indicated yielded either intrusive clay or visible baryte.
sequence does not apply to the Acutistriatum However, thin sections and SEM photomicro-
concretions which have only a single ®ll of spar graphs reveal small euhedral baryte crystals
calcite. enclosed within later spar calcite (Fig. 7A and
B). Therefore, baryte is con®rmed as an early
Ìntrusive clay' phase. Sphalerite occurs occasionally in Oxford
Clay concretions though never in large amounts.
The earliest material in septarian cracks, apart
Barker et al. (1997) record a case where it seals
from the early brown calcites discussed above, is
fractures in a bone fragment in a concretion and is
the ìntrusive clay' described by Hudson (1978)
associated with intrusive clay; it is itself overlain
from the main concretions at Calvert. This con-
by ferroan calcite cement. It, therefore, occupies a
sists of un-compacted internal sediment, inclu-
similar paragenetic position to baryte.
ding shells and fragments, that evidently entered
the fractured concretion from the surrounding
Sandstone dyke
sediment, which was then in the form of unce-
mented silty mud. The internal sediment is now Martill & Hudson (1989) described a sandstone
cemented by coarse spar calcite identical to that dyke from Dogsthorpe, Peterborough, which was
forming the main later ®ll of the cracks. intruded into the lower part of the Oxford Clay,
and also penetrated the septarian cracks in a
Baryte and sphalerite concretion (Fig. 9). The dyke originated from the
Kellaways Sand beneath. At the time of the dyke's
The intrusive clay at Cassington bears centimetre-
intrusion the clay was still only partially com-
scale plates of baryte. Hudson (1978) suggested
pacted: suf®ciently so as to fracture under the
that this baryte related closely to the intrusion of

Fig. 9. Schematic diagram showing sequence of events in the formation of a concretion at Peterborough, its intrusion
by a sand dyke, cementation and compaction. Modi®ed from Martill & Hudson (1989). Not to scale, but concretions
are »1 m across. Tracing from a peel (7 cm across) shows detail of a relationship between septarian cracks (here ®lled
by intrusive sand from the dyke), the pyritic rim of the main concretion body and the thin pyritic rims to the
septarian cracks, À' marks the position of an ammonite fragment within the concretion body. It is part ®lled with
faecal pellets and cemented by spar calcite similar to the cement of the sand in the dyke.
sudden stress, probably seismically induced, that similar to scalenohedra, but were determined as
caused the dyke to be intruded, but not so much positive rhombs (Hudson, 1978). The presence of
as to have crushed ammonite shells, because remaining voids, or in some cases later-precipi-
uncrushed examples are ®lled with sand. Septar- tated celestine, adjacent to the spar crystals,
ian cracks no thicker than the sand grains shows that the pore water must have ceased to
themselves, penetrating the pyritic margin of the be supersaturated with calcite, terminating their
concretion, are completely ®lled with sand growth.
(Fig. 9). The sand was subsequently cemented
by calcite identical in texture and isotopic com- Celestine
position to the white sparry calcite that ®lls
Celestine occurs as conspicuous blue crystals in
septarian cracks in other concretions nearby, and
concretions from Calvert and Cassington (Fig. 3),
this took place before further compaction of the
but has not been found in other areas. It overlies
Oxford Clay.
crystal terminations of spar calcite. The celes-
tine is believed to result from an in¯ux of new
White sparry calcite
pore water into the concretions: Pore-water 3.
The most widespread mineral in septarian cracks SEM observations show that the calcite-celestine
is coarse white sparry calcite, showing steep contact is marked by a thin void space, along-
crystal terminations in cavities that still retain side which calcite has a planar surface, but
void space. A typical example is that from celestine is deeply corroded into acute spires
Cassington (Fig. 3). The crystals are crudely (Fig. 7C).
single strontium isotope ratio determination is

Water in vugs
radiogenic to about the same extent as spar calcite
Water has been observed in vugs in freshly broken (Fig. 5).
concretions extracted from fresh clay at Calvert
and from Cassington (Fig. 3). The sample analysed Discussion. Because baryte is so insoluble in
(several cm3) came from well within a large low-temperature natural waters it must have
concretion. Because sampling followed immedi- resulted from transport to the precipitation site
ately after excavation of the hole and removal of the of either one or both of sulphate-rich and barium-
concretion from 3 m depth, there is no chance that rich solutions. The origin of the anion, therefore,
the water was contaminated with modern rain. needs to be considered separately from the cation.
The stable isotope results suggest that the
original source of sulphate was residual sea water
Minerals in septarian cracks: chemical
sulphate after substantial sulphate reduction:
and isotopic composition
bacterial sulphate reduction favours the light
In order to investigate further the origin of the isotope, more strongly for sulphur than for
septarian minerals, and determine the nature of oxygen, thus enriching the residuum in the heavy
the pore waters from which they formed, chem- isotopes (Holser et al., 1979). Data collected in
ical and isotopic analyses were undertaken this study plot close to the curve relating d34S to
(Tables 1±4). d18O for barytes from Japan plotted by Sakai
(1971), who gives a similar explanation.
Baryte Figure 10 illustrates how this effect may have
been produced, as regards sulphur isotopes, in the
Results. The earliest phase in the ®llings for
Oxford Clay. Sulphate reduction leads to succes-
which analytical data are available, apart from
sive generations of pyrite, ®rst in the sediment
the brown calcites previously discussed, is baryte:
generally and then in replaced fossils and in
microprobe analyses from Cassington (Table 2),
concretions. Early pyrite, formed under open-
and strontium, sulphur and oxygen isotopic
system conditions with constant replenishment
analyses from Calvert (Tables 1 and 4). The baryte
from sea water sulphate, was strongly 34S depleted
contains 3±6% strontium. One microprobe tra-
(Fisher & Hudson, 1987), but later pyrite genera-
verse shows Sr increasing towards the outer
tions became progressively 34S enriched because
margin of a crystal, another found no obvious
of Rayleigh fractionation in a closed system. Pyrite
trend. The sulphur isotopic composition is mark-
precipitation probably ceased as a result of
edly heavy at c. +40& CDT (Fig. 10), Jurassic sea-
exhaustion of reactive iron (Can®eld & Raiswell,
water being about +17&. Sulphate oxygen is also
1991). Finally, the precipitation of baryte from
consistently heavy at about +20& SMOW. Our
residual sulphate led to its being the most 34 S-rich
Table 4. Sulphur, oxygen and strontium isotopic analyses on minerals from concretions from the Peterborough
Member, Oxford Clay Formation.
Sample Location Mineralogy d34S&O, CDT d18O&O, SMOW 87

Sr/86Sr
CAS1095-6 Cassington Celestine 26á1, 25á7 17á4 0á708541

CAS1095-6 Cassington Celestine 25á6 30á4 0á708541
CAS1095-7 Cassington Celestine 22á1 23á3 0á708513
CAS1095-7 Cassington Celestine 21á9 20 0á708513
CAS1095-8 Cassington Celestine ± ± 0á708506, 0á708412
CV95-1 Calvert Celestine 23á4 ± 0á708861
C3A-95 Calvert Baryte 43á1, 45á4 20á6 0á708773
C3A-95 Calvert Baryte 50 ± 0á708773
C3A-98 Calvert Baryte ± 20á8
LEIUG71809 Calvert Baryte ± 19á8
CV95-1 Calvert Pyrite lining 22á8 ±
RG5A Rixon Pyrite rim )11á7 ±
Figures on the same line are duplicate analyses of the same sample. Figures sharing the same sample number are
closely adjacent subsamples. CAS samples all from the same concretion at Cassington; CV and C3 from the same
concretion at Calvert. Analysts: S, Coleman (Resding); O, Boyce (SURRC); Sr, Barreiro (NIGL).

Fig. 10. Sulphur isotopic compo-

sition of sulphides and sulphates
from the Peterborough Member,
Oxford Clay Formation, and con-
cretions within it, showing the
main diagenetic trend from Juras-
sic sea water sulphate, through
successive generatons of sedimen-
tary pyrite, to diagenetic baryte.
Note that later-diagenetic celestine
lies off this trend. Data for shales,
replaced shells and concretionary
pyrite (of wholly pyritic concre-
tions) from Fisher (1983), shown as
mean and range. Other analyses
from Table 4 herein. Numbers of
analyses shown.
phase. The degree of isotopic enrichment with the data from the concretion bodies, the
observed means that the SO4 content at the time spars are markedly heavier in carbon and lighter
of baryte precipitation was substantially less than in oxygen (Fig. 11).
that of sea water. Strontium isotope data were obtained for both
The isotopic composition of the strontium in new samples and a selection of those previously
the baryte, however, cannot be derived from analysed for stable isotopes (Table 1 and Figs 5
Jurassic sea water, and demands a source of and 8). All are markedly more radiogenic than
radiogenic Sr, presumably from the decay of Rb in early calcites or Jurassic sea water. The samples
clay minerals or feldspars included in the Oxford were pure calcite, so cannot have been contam-
Clay sediment or in adjacent formations. A inated by clay or other impurities; Rb contents are
Ba-bearing, sulphate-free solution may have very low so radiogenic Sr must be inherited, not
entered the reaction site as meteoric-derived ¯uid produced in situ.
rising from underlying palaeo-aquifers, as further Microprobe data were obtained for spar calcites
discussed below: it is Pore-¯uid 2. Shaw et al. from three sub-samples of the large concretion
(1998; and references therein) show that Ba-rich from Cassington (Table 2). All are similar ferroan
groundwaters discharge into the sea off the south- calcites. Elemental data were also obtained from
eastern United States. Whereas the details of the ICP analyses of the phosphoric acid residues from
setting are obviously different, this shows that preparation for stable isotopic analysis; these can
the mechanism is reasonable. In the Jurassic case be related directly to the C and O isotopic ratios
the groundwaters must have contained both Ba (Fig. 6). The spar calcites are generally more
and Sr; the trend to increasing Sr in baryte (if one ferroan than concretion bodies, but their iron
crystal is representative) suggests that relatively contents vary widely at Calvert and Cassington;
low-Sr baryte precipitated ®rst, so that as Sr built the two values from Peterborough are higher.
up in solution, later-precipitated baryte had more There is a crude negative correlation with d18O, as
Sr partitioned into it from the remaining solution. expected from the results of staining. Mg contents
However, no celestine precipitated at this stage, are low and show no obvious trend. Sr, like Fe,
and the next phase is spar calcite with unexcep- shows a crude negative correlation with d18O
tional Sr content (»0á05 wt% SrO; Table 3). (Fig. 6).
Spar calcite Discussion. The data collected show that the

isotopic and elemental compositions of the spar
Results. New data on the carbon and oxygen
calcites tends to be similar within a given
isotopic composition (Table 1 and Fig. 4B) are
locality, but vary markedly between localities.
generally similar to those reported in Hudson
This contrasts with the concretion bodies, which
(1978) and Martill & Hudson (1989). Compared
organic decay in the zone of methanogenesis

(review in Raiswell & Fisher, 2000). The fact that
the heaviest values are within the range of marine
fossils suggests the dominance of the former
source in the present case.
Hudson (1978) attributed the light oxygen in
the spar calcites to precipitation from isotopically
light meteoric-derived water, because the rocks
have never been deeply enough buried for iso-
topic depletion due to geothermal heating to
become signi®cant. Various other means of pro-
ducing light pore waters have been proposed
since, but do not appear to be adequate (see
Burns, 1998; Raiswell & Fisher, 2000; for
reviews), and the original interpretation is still
favoured. However, the Upper Jurassic formations
overlying the Oxford Clay are all marine, and by
far the most likely source for meteoric water
entering the Oxford Clay is by in®ltration from
uncon®ned palaeo-aquifers beneath the shallow
marine basin. There are such potential aquifers
metres to tens of metres below the Oxford Clay in
all areas (Kellaways Sands, Cornbrash, Blisworth/
White Limestones, generally thickening south-
westwards; Lincolnshire/Inferior Oolite Lime-
stones in the north and the south-west, but thin
or absent in the south-east, e.g. Emery et al., 1988;
®g. 2; Sumbler, 1996; ®gs 12 and 13).
The mode of intrusion of a sandstone dyke
originating from the underlying Kellaways Sand
Fig. 11. Summary of carbon and oxygen isotopic evo-
lution of calcites from concretions from the Oxford also implies water rising from a subjacent palaeo-
Clay (not including the Ampthill Clay). Main trends aquifer penetrating the Oxford Clay (Martill &
are: (1) sulphate reduction in sea water-derived pore Hudson, 1989). It is most probable that cement in
water, leading to concretion bodies of strongly negative the sand was precipitated from the water that
d13C that are similar across the region, (2) compaction, accompanied its emplacement. Thus, it appears
accompanied by meteoric water in¯ux, leading to that meteoric-derived pore waters (collectively
increasingly negative d18O, decreasingly negative d13C
Pore-water 2) penetrated semi-compacted Oxford
and increasing Fe content of calcites; these effects
operate differentially at different localities. Clay, and its concretions, at widely separated
localities. The timing of this event (or events) is
discussed below.
have rather uniform composition across the The radiogenic strontium in the spar calcites
region (Figs 4, 8 and 11). The probable explan- must involve input of radiogenic strontium from
ation is that pore waters beneath the sea ¯oor Rb-bearing minerals, micaceous clay minerals or
were rather uniform across the basin during the feldspars, in or surrounding the source for the
deposition of the Peterborough Member, whereas waters that precipitated the cements. Emery et al.
the palaeo-hydrogeology of the basin varied from (1987) discuss the origin of Sr in cements from
place to place, thus producing regional variations the Lincolnshire Limestone, one of the possible
in the septarian ®lls. source aquifers for the later Oxford Clay cements,
The trend in carbon isotopic composition in and come to a similar conclusion.
successive calcite generations, from light carbon The variability in elemental composition at
resulting from bacterial sulphate reduction to different localities (Fig. 6) is consistent with the
heavier values (Figs 4 and 11), records an implications of the isotopic data, that whereas
increasing in¯ux of carbon from dissolution of general trends can be observed (similar to those
marine carbonates (aragonite? Hudson, 1978; found by Boles et al., 1985; in a very different
Hendry, 1994) and/or carbonate generated from setting), the waters that deposited the spar
calcites varied across the region. It is notable that a burial-diagenetic origin for spar calcite must
calcites from Rixon Gate, Peterborough and the apply to the septarian ®lls in the Acutistriatum
Ampthill Clay, where celestine has not been concretions; because the concretions are post-
observed, tend to be high in strontium, whereas compactional, the septarian cracking and its
at the celestine localities (Calvert and Cassing- ®lling must be so also. It is unlikely that the
ton), it is generally low. These results imply that isotopic composition of the spar can be explained
the rate or the conditions under which calcite by uplift and exposure, because the overlying
precipitated in these areas favoured the incorpor- strata are all marine. The spar calcite in Acuti-
ation of Sr, thus leaving insuf®cient for the striatum concretions is lighter in carbon but
subsequent precipitation of celestine. heavier in oxygen than the spar in the main
The precipitation of the spar calcites from concretions (Fig. 4B). Hudson (1978), therefore,
meteoric-derived water is now well established, suggested that it had an earlier origin, relative to
but the time of their precipitation is still debat- time of deposition, than the main spar calcites. It
able. The sandstone dyke at Peterborough (Martill is now suggested that it is later, and that its
& Hudson, 1989) shows that water from below isotopic composition is determined by precipita-
was driving sand into the lower part of the Oxford tion from pore ¯uid with a lower proportion of
Clay while the later part was still being deposited meteoric water. This could result from the cir-
on the sea ¯oor. Because its cement, which is cumstance that at the time of formation of these
identical to the spar calcite in concretions, was concretions the Oxford Clay, being already some-
precipitated prior to compaction, the implication what compacted, was less permeable than at the
is that spar calcites were precipitated a few time when meteoric-derived water was able to
metres or tens of metres below the sea ¯oor, in penetrate the early formed concretions.
the Callovian. A possible recharge source for Undoubted burial cements in Jurassic carbonate
meteoric water in the Kellaways Sand lies in the rocks in the East Midlands Basin, such as the
Humber region, »130 km north of Peterborough. Lincolnshire Limestone (Emery et al., 1988), and
The Peterborough Member of the Oxford Clay the Blisworth (White) Limestone (Hendry, 1994)
Formation is overstepped northwards, and Stew- include ferroan calcite spar cements with carbon
artby Member rests directly on a sandy develop- and oxygen isotopic values similar to spar calcites
ment of the Kellaways Formation (Penn et al., described here, and in the case of the Lincolnshire
1986). Therefore, at the time of dyke intrusion Limestone radiogenic strontium also (Emery et al.,
Kellaways Sand could have been exposed at the 1987). Hendry (1994) presents an excellent exten-
surface. Its elevation, and hence the hydraulic ded discussion of the White Limestone cements,
head developed, is unknown. Alternatively, the which he argues were precipitated during an early
Kellaways Sand could have been recharged from Cretaceous period of exposure of the basin mar-
an underlying palaeo-aquifer, through the inter- gins. It follows that chemically, isotopically and
vening Kellaways Clay. petrographically similar calcites can have differ-
The proposed origin of baryte from mixing of ent origins in space and time, even in stratigraph-
waters extends the conclusion about the early ically close horizons within a single basin.
in¯uence of meteoric-derived water to Calvert
and Cassington, and it may apply to all the Celestine
Oxford clay pre-compactional concretions.
Results. Celestine does not occur as widely as
Recent research shows that at the present time
calcite, being so far known only from Calvert and
far more freshwater enters the sea via submarine
Cassington, and forms a distinct mineral genera-
sediments than used to be supposed, on the basis
tion; whereas baryte inclusions occur in calcite,
of element budgets for barium and radium
no calcite inclusions are known in celestine.
(Church, 1996; Shaw et al., 1998). This view of
Microprobe analyses (Table 2) show that the
the early origin of the spar calcites was one of two
celestine is rather pure SrSO4, with less than
alternative scenarios suggested by Hudson (1978).
0á5% BaO at maximum and no or just detectable
The alternative proposal that spar calcites in
CaO. Strontium isotopes are radiogenic and
concretions are late-diagenetic burial cements
within the range observed for spar calcites
(Hudson, 1978) was supported by Astin & Scotch-
(Fig. 5). Sulphur isotopes (Table 1) show a nar-
man (1988) and Scotchman (1991) in respect to
row range (®ve samples) at c. +21& CDT (Fig. 10).
their second-generation white cements from the
Sulphate oxygen is heavy and, more surprisingly,
Kimmeridge Clay concretions in the eastern
variable from +17 to +30& SMOW.
England basin. Within the Oxford Clay itself,
Discussion. The sulphur isotopic composition is The admittedly speculative scenarios for the
much lighter than that of baryte, demanding a two sulphate minerals imply that early baryte
different sulphur source. Sulphate oxygen only obtained its sulphate from in situ pore waters
exchanges extremely slowly with water oxygen, residual from Jurassic sea water (Pore-water 1),
so its isotopic composition is unchanged from the and its barium from meteoric-derived waters
sulphate source, unless S-O bonds are broken rising from palaeo-aquifers below (Pore-water 2).
(Holser et al., 1979; Bottrell & Raiswell, 2000). Celestine, conversely, obtained its strontium loc-
The observed heavy sulphate-oxygen values can- ally from residual Pore-water 2 and its sulphate
not derive from Jurassic or later sea water or from from water of uncertain origin as discussed above
evaporites, because sea water values have never (Pore-water 3).
been above +15& SMOW, and evaporites are only
slightly further enriched (Claypool et al., 1980; Water in vugs
Bottrell & Raiswell, 2001). Two possibilities
Results. Water collected from large, closed, cal-
could explain them:
cite- and celestine-lined vugs from Cassington
1 The variably 18O-enriched sulphate is resid- was analysed for hydrogen and oxygen isotopes
ual from sea water sulphate that has suffered and for dissolved ions. The isotopic composition
bacterial sulphate reduction to varying extents. (Table 5 and Fig. 12) is close to the meteoric
This is consistent with a source in connate waters water line which describes the composition of
at depth. The dif®culty here is that if oxygen recent precipitation worldwide, and also close to
isotopic composition varies, sulphur isotopic the position of modern lowland-British rain on
composition ought to co-vary with it, which is that line. Chemical analyses by ICP are presented
not observed. in Table 4. Calculations using Solmineq (Kharaka
2 The sulphate originates from varying degrees et al., 1988) show that the water is supersaturated
of oxidation of pre-existing sulphides by oxygen- for calcite but undersaturated for celestine
bearing pore waters of meteoric origin, its oxygen (Fig. 13).
isotopic composition being controlled by differ-
ing oxygen contents of the waters, and hence Discussion. The situation of the water in closed
differing rates of oxidation of the sulphide. vugs, in a concretion, in a clay which typically
This implies a nearer-surface site of sulphate could be expected to have very low matrix
generation, or penetration of meteoric water into permeability, implies that it cannot be present-
subsurface con®ned aquifers. The hypothesis day rain. It must be of meteoric origin and it
demands that the sulphide being oxidized was probably relates to the modern (Pleistocene±
itself 34S rich (because there is only small Holocene) cycle of erosion. However, it is not
fractionation of sulphur isotopes during oxida- possible to better de®ne its age. Presumably
tion of sulphide to sulphate), which is true of the water of similar origin must be present dis-
late pyrite generations present in the Oxford Clay persed in the clay sediment itself. Eggenkamp
but not of the volumetrically dominant early et al. (1999) found very low salinity water in
pyrite (Fig. 10). Also, there is no evidence of clays overlying the concretion horizon at Rixon
oxidation of pyrite within the Oxford Clay sedi- Gate, with no evidence from chlorine isotope
ment, or of dissolution of carbonates which distributions of diffusion of solutes through the
would be expected under the in¯uence of acid clay; therefore the water must be transported
waters produced by sulphide oxidation. advectively. Most sections in the Oxford Clay
show joints and minor faults: some of these may
The strontium in the celestine cannot be marine
be of super®cial origin related to the present
in origin because of its radiogenic isotopic com-
cycle of erosion and glaciation±deglaciation.
position. Following the discussion above, poros-
They are probably important in the transmission
ity in the Oxford Clay would have been occupied
of ¯uids.
by meteoric-derived Pore-water 2, at the time of
The solubility relationships accord with petro-
celestine precipitation. This contained radiogenic
graphical observation. There is a narrow void
strontium and had already precipitated low-Sr
space where calcite and celestine crystals are in
baryte and calcite. It may, therefore, have had
contact, along which a ragged edge to celestine
enhanced Sr content, suf®cient to precipitate
shows that it has been dissolved (Fig. 7C). Thus,
celestine if a sulphate-bearing ¯uid entered the
the water is coming to equilibrium with the
system.
minerals in the vugs, and cannot be the water

Only MLC3 was large enough for elemental analysis. Duplicate runs on MLC4 gave ¶D = )52á3, )52á8; ¶18O = )6á82, )6á66; mean quoted in Table.
Elements measured at less than 10 times the limit of detection, in mg l)1: Fe (0á21), Al (3á12), Mn (0á25), Pb (1á84), Si (0á45), Zn (0á07), Cr (0á06), Cu (0á04),
Sanions
23á58
Table 5. Hydrogen and oxygen isotopic composition, and elemental data from ICP, for water samples from vugs in a single concretion at Cassington.
Scations
meq l)1
29á34
617 (12á85) 585 (9á59)
3 )*
(HCOÿ
Fig. 12. Hydrogen and oxygen isotopic composition

of water from a vug in a concretion from Cassington
SO2ÿ
(cf. Fig. 3), plotted relative to the present-day meteoric

4
water line (MWL) that describes world-wide average

precipitation.
40á4 (1á14)
Cl)
8á5 (0á19)
Sr2+
491 (24á5)
Ca2+
Fig. 13. Saturation index of water from a vug in a

concretion from Cassington, for various minerals.
Calculated by Solmineq from data in Table 5. Note
27á5 (1á95)
near equilibrium with calcite but undersaturation with

celestine.
Mg2+
25á5 (0á65)
from which they precipitated. It is the last water

to penetrate the Oxford Clay; Pore-water 4.
mg l)1 (meq l)1)
K+
3 ) = alkalinity as bicarbonate. pH = 7á4.
IMPLICATIONS
47á3 (2á06)
This study demonstrates that, despite the belief

Na+
of many geologists that clays are ìmpermeable',

at least four pore waters have existed within the
Oxford Clay since its deposition. Further waters
d18O&o
SMOW
may have traversed the clay but left no record.

)6á74
)6á7
The pore waters successively displaced one

another, starting when the sediment was only
slightly compacted, and continuing to the pre-
Ba (0á14), Li (0á26).
SMOW
sent cycle of erosion, in clay that is substantially

dD&o
)43á3
)53á2
)52á6
)47á2
over-compacted. After the initial marine deposi-

tional water, the later waters were meteoric in
*(HCOÿ
origin, although derived by upward ¯ow from

Sample
MLC1
MLC3
MLC4
MLC5
palaeo-aquifers beneath the Oxford Clay. There is

every reason to suppose that a similarly long and
complex palaeo-hydrological history has affected water 2 is a complex of waters of varying

other clay formations in epicontinental basins, as composition across the region, because the pal-
postulated in previous studies (e.g. Marshall, aeo-hydrology varied regionally. Pore-water 2 is
1982). It is not claimed that meteoric-water characterized by isotopically light oxygen and
in¯ux is part of the history of all concretion negligible sulphate, relatively elevated Ba con-
bodies or septarian-crack ®llings (see Mozley & tents and radiogenic Sr.
Burns, 1993; and Burns, 1998 for a discussion of Within the early formed concretions:
other possibilities). It seems probable, however,
· Unconsolidated clay sediment is injected into
that it is a common process, given that many
some brecciated concretions. Baryte is precipita-
concretion-bearing mudrocks are deposited in
ted in this intrusive clay, and also in some
shallow water, not far from shore, as parts of
septarian cracks, as a result of mixing of Pore-
lithologically heterogeneous sedimentary succes-
waters 1 and 2. Its sulphate is derived from
sions.
residual sea water; its Ba and Sr from pore-water 2.
· At Peterborough, a sand dyke is intruded
from the underlying Kellaways Sand into only
CONCLUSIONS
slightly consolidated clay, and penetrates an
already cemented and brecciated concretion.
The results of this study can be summarized by
· Spar calcite cements the sand dyke to sand-
listing the most important events that happened
stone, prior to substantial compaction of the clay.
under the in¯uence of the successive generations
Similar calcite precipitates in septarian cracks
of waters that ®lled the pores of the Oxford Clay.
throughout the area, but leaves un®lled voids in
Not all observed effects can con®dently be placed
the wider ones.
in a time sequence.
Within the clay:
Pore-water 1 · A second generation of concretions forms
after compaction suf®cient to crush ammonite
Callovian sea water trapped within the unconsol-
shells, from mixtures of residual Pore-water 1 and
idated sediment and chemically modi®ed by
Pore-water 2.
bacterial activity.
· The concretions form regular septarian
· Concretion body forms in sulphate reduction cracks, not chaotic breccias, and calcite precipi-
zone, incompletely cemented by calcite, with tates within these, completely ®lling them.
pyritic rim.
· Concretion cracks internally and brecciates
Pore-water 3
into angular fragments.
· Marginal pyritisation of brecciated fragments Probably derived from formation waters in more
continues, implying continued ¯ux of seawater deeply buried strata beneath the Oxford Clay. It
through the shattered concretion. appears only to have affected the Calvert±Cas-
· Brown calcite precipitates in some concre- sington area. It contains sulphate with variably
tions, lining pre-existing cracks. heavy oxygen.
Textural, elemental and isotopic evidence · Celestine precipitates in large voids within
shows that all these events took place in uncon- brecciated concretions. Sulphate was from Pore-
solidated sediment, under shallow burial (metres), water 3; Sr was residual from Pore-water 2.
in pore water that had marine oxygen and
strontium isotopic composition but whose dis-
solved bicarbonate and sulphate was strongly Pore-water 4
affected by sulphate reduction.
Meteoric water from the present cycle of erosion,
with hydrogen and oxygen isotopic composition
Pore-water 2 similar to that of modern meteoric water.
Meteoric-derived water of Callovian age; it pen- · Water penetrates over-compacted Oxford
etrates the Oxford Clay sediment from palaeo- Clay, including closed vugs within concretions.
aquifers beneath, mixing with and displacing The water is currently equilibrating with the
Pore-water 1, and is particularly associated with minerals in the vugs.
open fractures such as septarian cracks. Pore-
The authors accept that they do not fully Astin, T.R. and Scotchman, I.C. (1988) The diagenetic history
understand concretions, but believe they have of some concretions from the Kimmeridge Clay, England.
Sedimentology, 35, 349±368.
shown that they help understanding of other Barker, M.J., Clarke, J.B. and Martill, D.M. (1997) Mesozoic
phenomena. reptile bones as diagenetic windows. Bull. Soc. GeÂol. Fr.,
168, 535±545.
Boles, J.R., Landis, C.A. and Dale, P. (1985) The Moeraki
ACKNOWLEDGEMENTS Boulders-anatomy of some septarian concretions. J. Sed.
Res., 55, 398±406.
Bottrell, S.H. and Raiswell, R. (2000) Sulphur isotopes and
Adrian Boyce and Tony Fallick (SURRC, East microbial sulphur cycling in sediments. In: Microbial
Kilbride) provided the analyses of oxygen iso- Sediments (Eds R. Riding and A. Awramik). Springer
topes in sulphates. Rob Wilson (Leicester) car- Verlag, Berlin, pp. 96±104.
ried out the microprobe analyses. Mike Isaacs Burns, S.J. (1998) Can diagenetic precipitation of carbonate
nodules affect pore-water oxygen isotope ratios? J. Sed. Res.,
operated the mass spectrometer for the isotope 68, 100±103.
analyses conducted in Reading. Sarah Gabbott Callomon, J.H. (1968) The Kellaways Beds and the Oxford
helped greatly in preparing the ®gures. Rob Clay. In: The Geology of the East Midlands (Eds
Raiswell is thanked for many discussions of P.C. Sylvester-Bradley and T.D. Ford), pp. 264±290. Lei-
concretions, for comments on an early version of cester University Press, Leicester, UK.
Can®eld, D.E. and Raiswell, R. (1991) Pyrite formation and
the manuscript, and for allowing us to see copies fossil preservation. In: Taphonomy, Releasing the Data
of his papers prior to publication. All members Locked in the Fossil Record (Eds P.A. Allison and D.E.G.
of the Oxford Clay Working Group are thanked Briggs), pp. 337±387. Plenum, New York.
for their contributions in the ®eld and in Church, T.M. (1996) An underground route for the water
discussions. Jim Boles, an anonymous referee cycle. Nature, 380, 579±580.
Claypool, G.E., Holser, W.T., Kaplan, I.R. and Zak, I. (1980)
and Peter Mozley are thanked for helpful re- The age curves of sulfur and oxygen isotopes in marine
views. This is PRIS contribution number sulfate and their mutual interpretation. Chem. Geol., 28,
807(M.L.C.), NIGL contribution number 360 199±260.
(B.A.B.). J.D.H.'s contribution was supported by Coleman, M.L. and Moore, M.P. (1978) A method for the direct
NERC grant GR9/0170. reduction of sulfates to sulfur dioxide for isotopic analysis.
Anal. Chem., 50, 1594±1595.
Coleman, M.L. and Raiswell, R. (1993) Microbial mineraliza-
tion of organic matter: mechanisms of self-organization and
NOTE ADDED IN PROOF inferred rates of precipitation of diagenetic minerals. Phil.
Trans. Roy. Soc. London, A344, 69±87.
The following papers have appeared while this Coleman, M.L. and Raiswell, R. (1995) Source of carbonate
and origin of zonation in pyritiferous carbonate concretions:
paper was in press: evaluation of a dynamic model. Am. J. Sci., 295, 282±308.
Green, P.F., Thomson, K. and Hudson, J.D. (2001) Coleman, M.L., Shepherd, T.J., Durham, J.J., Rouse, J.E. and
Moore, G.R. (1982) Reduction of water with zinc for
Recognition of tectonic events in undeformed hydrogen isotope analysis. Anal. Chem., 54, 993±995.
regions: contrasting results from the Midland Coleman, M.L., Walsh, J.N. and Benmore, R.A. (1989) Deter-
Platform and East Midlands Shelf, Central Eng- mination of both chemical and stable isotope composition
land. J. Geol. Soc. London, 158, 59±73 (the burial in milligramme-size carbonate samples. Sed. Geol., 65,
history of the Oxford Clay). 233±238.
Coleman, M.L., Lovley, D.R., Hedrick, D.B., White, D.C. and
Pratt, B.R. (2001) Septarian concretions: internal Pye, K. (1993) Reduction of Fe (III) in sediments by sul-
cracking caused by syn-sedimentary earthquakes. phate-reducing bacteria. Nature, 361, 436±438.
Craig, H. (1957) Isotopic standards for carbon and oxygen and
Sedimentology, 48, 189±213 (theory of septarian correction factors for mass spectrometric analysis of carbon
crack formation). dioxide. Geochim. Cosmochim. Acta, 12, 133±149.
Curtis, C.D., Coleman, M.L. and Love, L.G. (1986) Pore water
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Sedimentology (2001) 48, 507±531

Septarian concretions from the Oxford Clay

Septarian concretions occur at several horizons within the Oxford Clay

INTRODUCTION (Hudson, 1978). Early formed concretions enclose

are described in this paper, which adds new

The localities studied are shown in Fig. 1. The

Fig. 2. Field photograph of part of

Fig. 3. Photograph of a vug within

Ó 2001 International Association of Sedimentologists, Sedimentology, 48, 507±531

Ó 2001 International Association of Sedimentologists, Sedimentology, 48, 507±531

C1C1A Calvert ESC-CB )11á98 )0á60 0á707471

towards internal cracks as well as towards the

Table 2. Electron microprobe analyses of minerals from a concretion from Cassington.

Weight % oxides, mean (range)

Sample Mineral N CaO MgO FeO SrO BaO SO3 Total

Ó 2001 International Association of Sedimentologists, Sedimentology, 48, 507±531

C1C1A 0á93 0á055 0á0134 0á00017 0á00049 0 0á16 0á07

Fig. 6. Plots showing the elemental composition of

from septarian cracks (Fig. 6A). Iron contents are

Syn- or post-compaction concretion bodies

Fig. 8. Plot of strontium isotopic

Ó 2001 International Association of Sedimentologists, Sedimentology, 48, 507±531

single strontium isotope ratio determination is

Sample Location Mineralogy d34S&O, CDT d18O&O, SMOW 87

CAS1095-6 Cassington Celestine 26á1, 25á7 17á4 0á708541

Ó 2001 International Association of Sedimentologists, Sedimentology, 48, 507±531

Fig. 10. Sulphur isotopic compo-

Spar calcite Discussion. The data collected show that the

organic decay in the zone of methanogenesis

Ó 2001 International Association of Sedimentologists, Sedimentology, 48, 507±531

Fig. 12. Hydrogen and oxygen isotopic composition

(cf. Fig. 3), plotted relative to the present-day meteoric

water line (MWL) that describes world-wide average

Fig. 13. Saturation index of water from a vug in a

near equilibrium with calcite but undersaturation with

from which they precipitated. It is the last water

3 ) = alkalinity as bicarbonate. pH = 7á4.

This study demonstrates that, despite the belief

of many geologists that clays are `impermeable',

may have traversed the clay but left no record.

The pore waters successively displaced one

sent cycle of erosion, in clay that is substantially

over-compacted. After the initial marine deposi-

origin, although derived by upward ¯ow from

palaeo-aquifers beneath the Oxford Clay. There is

complex palaeo-hydrological history has affected water 2 is a complex of waters of varying

Ó 2001 International Association of Sedimentologists, Sedimentology, 48, 507±531

Ó 2001 International Association of Sedimentologists, Sedimentology, 48, 507±531

Ó 2001 International Association of Sedimentologists, Sedimentology, 48, 507±531

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