Geochimica et Cosmochimica Acta, Vol.60, No. 18, pp.

3457-3470, 1996
Copyright 0 1996 ElsevierScienceLtd
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Comparative determinations of trace and minor elements in coral aragonite by ion

microprobe analysis, with preliminary results from Phuket, southern Thailand
N. ALLISON*
Department of Geology and Geophysics, Grant Institute, Kings Buildings, West Mains Road, Edinburgh EH9 3JW, UK

(Received July 7, 1995; accepted in revised form May 19, 1996)

Abstract-The ion microprobe technique was developed for semiquantitative analysis of trace and
minor elements in coralline aragonite. The size of the microprobe beam (ca. 30 pm diameter) allows
an examination of the spatial geochemical heterogeneity of coral skeletons on a much finer scale than
has previously been possible. Of the elements investigated magnesium, calcium, rubidium, strontium,
barium, and uranium appeared suitable for analysis under the operating conditions used although it was
not possible to unequivocally confirm that “Rb and 238Uwere not subject to molecular interferences. A
homogenous carbonate standard was only available for magnesium so some relative ion yields were
calculated using a standard silicate glass. Magnesium, rubidium, strontium, and barium concentrations
were in reasonable agreement with previously reported values. Uranium concentrations were considerably
lower, probably reflecting a miscalibration of the ion microprobe. Reproducibility of analysis was investi-
gated by comparing immediately adjacent pairs of analyses on coral material. Although analytical
accuracy was questionable, precision was good and concentration differences between samples reflect
true variations in geochemistry. High resolution time series analyses of magnesium, rubidium, strontium,
barium, and uranium in Porites lutea corals indicated that the aragonite was heterogeneous on a small
spatial scale (over distances attributed to less than one month’s skeletal growth). This heterogeneity
does not appear to reflect expected variations in seawater temperature or chemistry. It may reflect the
metal binding capacity of a heterogeneous organic matrix unevenly distributed throughout the coral
skeleton. Individual coral colonies deposited substantially different ranges of Mg and Ba, within and
between reef sites, which could lead to significantly different seawater:coral distribution coefficients
being calculated between individuals of the same coral species.

1. INTRODUCTION examination of the spatial heterogeneity of coral skeletons on

The incorporation of trace and minor elements in coral skele- a much finer scale than has previously been possible. An
tons has been examined in a variety of contexts: in the eluci- understanding of the extent of heterogeneity in coral skeletons
dation of calcification processes, in relation to polluting ac- could provide valuable insights into the mode of incorporation
of trace and minor elements and their likely reliability as
tivities and as a tracer of the chemistry and temperature of
tracers of past environmental conditions. In addition, if the
local seawater. For example, variations in skeletal strontium
microprobe beam is positioned accurately on thin sections,
content have been correlated with changes in seawater tem-
then only those elements intimately associated with the skele-
perature (Schneider and Smith 1982; Beck et al., 1992).
tal carbonate will be analysed. Particulate materials in skeletal
Coralline barium has been related to variations in seawater
pores and ions adsorbed onto the skeletal walls are avoided.
temperature, to variations in the Ba/Ca seawater ratio de-
Previous work (Allison and Tudhope, 1992) has shown that
pendant on oceanic upwelling (Lea et al., 1989; Shen et al.,
centres of calcification and microborings in the skeleton can
1992), and to terrestrial inputs from freshwater runoff or
contain elevated concentrations of certain elements, e.g., bar-
from river discharge (Shen and Sanford, 1990). Several
ium and magnesium, which do not accurately reflect the ele-
pathways exist for the incorporation of minor elements in
ment concentration in the surrounding aragonite.
the skeleton. Single atoms or whole metal complexes, e.g.,
Although the ion microprobe technique has been estab-
uranyl carbonates (Swart and Hubbard, 1982) may substitute
lished for some time, there is little published literature on
in place of calcium atoms or CaC03 groups in the aragonite
its application to carbonate minerals (Swart, 1990; Mason,
lattice. Metals may precipitate directly onto exposed skeleton
1987; Veizer et al., 1987). As a consequence, a considerable
if the overlying tissue becomes damaged or is retracted under
amount of time in this study was spent developing sample
stressful conditions (Brown et al., 1991). Other elements
preparation techniques and determining the reproducibility
may be incorporated in an organic phase, derived from the
of analyses.
matrix produced by the coral during calcification, which may
have a substantial metal binding capacity (Mitterer, 1978).
2. MATERLALS AND METHODS
During the present study, polished thin sections of coral
material were analysed using an ion microprobe. The size 2.1. Sample Preparation
of the microprobe beam (ca. 30 ,um diameter) allows an
Thin sections were prepared from several specimens of
the massive coral Porites lutea. Corals were collected in July
* Present address: Department of Pharmacy, University of Brigh- 1991 from three reefs around the Phuket Marine Biological
ton, Cockcroft Building, Moulsecoomb, Brighton BN2 4GJ, UK. Centre, southern Thailand. Two of the reefs, Porites Bay
3457
3458 N. Allison
(PB) and Aquarium Reef (AQ), occur on the southeastern
peninsula of Ko Phuket, while the third reef, Ko Racha
(KR) , fringes one of the offshore islands. A detailed descrip-
tion of the field area and reefs is not relevant to this study
but can be found in Brown et al. (1986).
Coral heads were soaked in a diluted solution of sodium
hypochlorite (ca. 3-4%) for 48 h after collection to remove
coral tissue and were rinsed in free-flowing water for a fur-
ther 48 h. Coral skeletal structures were examined by binocu-
lar microscope to aid species identification. All corals in-
cluded in this study exhibited morphological characteristics
of Porites lutea (using the keys of Veron, 1986), although
considerable variations in corallite structure were observed
between colonies of apparently the same species.
Corals were sectioned along the axis of vertical growth
into 1 cm thick slices using a rock saw and were photo-
graphed under UV radiation to record fluorescent banding
patterns. Bright-dull fluorescent couplets represent approxi-
mately annual growth in the corals in this area, with bright
band accretion beginning in approximately November (Scof-
fin et al., 1992). Cross-sections were cut through each slice,
along the axis of maximum growth and were made into thin
sections. Two cross-sections were prepared from coral AQ8,
called AQ8i and AQSii. All thin sections were produced
from carbonate deposited during the period approximately
November 1988-July 1991. Samples were fixed in Buehler
epo-thin low viscosity epoxy resin onto 25 mm diameter
glass discs and ground down to approximately 30 pm thick-
ness. Samples were finely polished using a variety of regimes
including mechanical polishing using Kemet industrial dia-
mond paste or alumina paste and polishing by hand using
diamond grit suspended in petroleum jelly. Analyses from
sections prepared by the different methods were compared
to assess the potential for sample contamination during prep-
aration and polishing. Detailed photographs were produced
of each thin section in transmitted light to record the place-
ment of microborings and centres of calcification. These
areas may be associated with geochemical anomalies and
were avoided during analysis. Polished sections were sput-
ter-coated with a thin even-thickness gold coat (ca. 20 nm
thick) to inhibit build up of charge on the sample during
analysis.
2.2. Ion Microprobe Analysis
Analyses were performed using a Cameca ims-4f ion microprobe
with Charles Evans and Associates interface and computer control.
Analysis was by Secondary Ion Mass Spectrometry (SIMS) in which
the specimen is bombarded with a focused primary ion beam and
the sputtered secondary ions produced are accelerated into a mass
spectrometer. As the elements studied here most readily form posi-
tive ions, a primary beam of 160- ions was used to enhance second-
ary ion formation. This primary beam was mass filtered to leave
an isotopically pure l6O- beam and avoid implantation of other
contaminants in the sample. The primary beam was accelerated by
a primary voltage of 10 kV and a voltage of +4.5 kV was applied
to the sample giving a total primary accelerating voltage of 14.5
kV. The primary beam current of ca. 5.0 nA was focused using a
series of electrostatic lenses to a diameter of about 30 pm on the
sample surface. Sputtered secondary ions consist of a complex mix-
ture of ionic and molecular species derived from the sample matrix,
the primary beam, and any gases present in the background of the
mass spectrometer, e.g., M’ (the desired signal), MO+, MOH’ ,
M2”, etc. Samples were maintained at high vacuum (between 2.10-a
and 5.10-’ Torr) to reduce any interferences caused by residual
water vapour in the system. Interferences caused by molecular ions
were removed or reduced by the energy filtering method as detailed
in Shimizu et al. (1978) and Zinner and Crozaz (1986). In brief,
the kinetic energy spectra for molecular ion species are usually
narrower and drop off in counts more rapidly than for atomic species.
By using an altered accelerating voltage (a voltage offset), data can
be collected from a segment of the energy spectrum which contains
proportionally less of these interfering species. Throughout this study
a voltage offset of -75 V and an energy window of 40 V was used.
This is discussed in more detail below.
Secondary ion counts were measured using an electron multiplier
by sequential stepping of the magnetic field through a cycle of
relative atomic mass. Counting times for each isotope varied ac-
cording to its abundance but did not exceed 30 s. Data were collected
for ten consecutive cycles in each analysis. Series of consecutive
cycles were averaged, the standard error calculated and the result
corrected for background counts (ranging from 0.00 to 0.06) and
deadtime. Data were collected during four sessions from December
1991-January 1993. Initially the following isotopes were analysed:
26Mg,27Al,?Si, “Ca, s4Fe, 55Mn,“Rb, 88Sr,“?Zd, “?Sn, ‘38Ba,13ta.
l4OCe,*08Pb, *?h, and 238U As discussed below, some of these
elements proved unsuitable for analysis due to possible contamina-
tion problems, molecular interferences, or poor counting statistics.
2.2.1. Poor counting statistics
Cadmium, tin, lanthanum, cerium, and thorium concentrations in
coral are low and the relevant isotopes for these elements were
frequently not detectable by this method.
2.2.2. Confaminafion problems
“Al and 28Sicounts exhibited an exponential decrease, tailing off
with time over the ten cycle analytical period, suggesting that these
isotopes or their isobars were present as contaminants on the surface
of the thin section. This contamination may be introduced from the
polishing compounds or may result from the smearing of the epoxy
resin fixative over the coral surface. ‘s’Ba and 138Bacounts also
decreased with time in the alumina polished samples but were stable
in those mechanically and hand polished with diamond paste. All
barium concentrations reported in this study were obtained from thin
sections polished with diamond paste.
A decrease of 2-4% was also observed in the counts of *6Mg
over a typical analysis of 20 min duration. However, this decrease
was approximately linear and showed no sign of tailing off even in
analyses which exceeded 1 h. This decrease may reelect the declining
signal of an interference which is either associated with the surface
of the thin section or migrates into the sputtering site during analysis.
This decrease may have been avoided by using a lengthy burn-in
time or by using a higher primary beam current. As the magnesium
decrease is of the same order of magnitude in all analyses, compari-
sons of magnesium concentration can be made between analyses
which are performed for the same time period.
No information on the trace element composition of the epoxy
resin was available from the manufacturer. In an attempt to gauge
the relative composition of the resin, two analyses were performed
approximately 50 pm apart on a thin section, one on coral material
and the other on epoxy resin (Table 1) . This table does not necessar-
ily reflect the trace metal composition of the two media, as isotope
counts may include any signal-produced by molecular interferences.
Counts of Z6Mp.“Ca, “Rb. *‘Sr, “*Ba, and 23*U(or their isobars)
in the epoxy a&lysis were a fraction of the values observed in the
coral analysis and it is unlikely that epoxy resin contamination will
increase the concentrations of these isotopes. Count rates of 27A1,
z8Si154Fe155MnI and *“‘Pb in the epoxy resin are similar to or greater
than the counts observed in the coral and it is possible that contami-
nation of coral analyses will significantly alter the concentrations of
these isotopes. These isotopes were not counted in subsequent analy-
ses and no attempt was made to assess their potential interferences.
2.2.3. Interfering species
Interfering species were minimised using the energy filtering tech-
nique @inner and Crozaz, 1986) at a voltage offset of -75 V and
 Comparative determinations of trace and minor elements in coral aragonite 3459

Table 1. Isotope counts per second on where

adjacent coral and epoxy resin analyses. X, = concentration of element i in the carbonate
Xc, = concentration of calcium in the carbonate
CPS, = counts per second for element i (corrected for deadtime,
Isotope Coral Epoxy background, interference and isotopic abundance)
Analysis Resin CPSc. = counts per second for calcium (corrected for deadtime,
background, interference and isotopic abundance)
“‘Mg 461 22 RIY, = ion yield of element i relative to that of calcium in standard.
2’Ai 373 648
The ion probe was calibrated for magnesium and strontium using
2*Si 110 128 a natural carbonate standard, Norman Cross Calcite (NCC), supplied
44Ca 77300 11 by A.E. Dickson, University of Cambridge. This standard has been
analysed by a variety of methods and workers and averages of several
“*Fe 1.05 0.76 of these values were used to calibrate the ion probe (2749 ppm Mg;
““Mn 1.48 1.14 40.08% Ca; 845 ppm Sr). The standard was used to determine
85Rb 0.42 0.07 relative ion yields (RIY, i.e., the ion yield of the element relative
to that of calcium in the standard) for these elements at the start of
@%r 26700 2 each of the four probe sessions (Table 3). The concentration of
‘38Ba 5.63 0.36 strontium in the standard is an order of magnitude less than that
observed in the samples; however, as RIY is independent of concen-
*“Pb 0.14 0.16
238 tration, extrapolating between the sample and standard should not
U 0.39 0.00 affect analytical accuracy. Multiple analyses were performed on the
standard to test its homogeneity for magnesium and strontium (Ap-
pendix A). The standard deviation between replicate analyses for
magnesium (6.0%) is in reasonable agreement with the analytical
anenergy window of 40 V. Under these conditions, trimers (molecu- error of each analysis calculated from counting statistics (5.4-
lar ions comprised of three atoms) are negligible (Schauer and Wil- 6.8%), suggesting that the standard is homogenous within analytical
liams, 1990). The major atomic and dimer interferences for the error for magnesium. However, the standard was heterogeneous with
isotopes studied are shown in Table 2. 26Mgis subject to few interfer- respect to strontium (the standard deviation of multiple analyses is
ences and Mason ( 1987) concluded that these amounted to an appar- 10.3% compared to an analytical error of 1.O- 1.6%). This heteroge-
ent signal equivalent to about 1 ppm magnesium at little or even no neity makes it impossible to ensure an accurate calibration of the
energy filtering. The conditions used in this study are sufficient to ion probe in any one session or to obtain comparable calibrations of
eliminate interferences for ‘*Sr (Swart, 1990). the instrument between sessions. To assess the extent of calibration
To assess possible interferences on barium, two isotopes ( 13’Ba differences between probe sessions, immediately adjacent strontium
and 13’Ba) were counted for several analyses. Assuming negligible analyses were performed on the same coral samples in different
molecular interferences, count rates for each isotope should occur probe sessions: i.e., some of the coral samples were themselves
in their relative isotopic proportions. Count rates did occur in the used as standards. Calculated element concentrations were averaged
expected proportions, within counting errors (2-7%), indicating between the analyses for each probe session and are shown in a
no significant interferences for these isotopes. The more abundant footnote to Appendix C. Variations in the calibration between ses-
isotope, 13’Ba,was counted for the remaining analyses. sions introduced an error of up to 0.9 mm01 Sr mol-’ Ca (ca. 10%).
It was not possible to check for molecular interferences on rubid- Correction factors were calculated which could be multiplied to each
ium or uranium. Although two isotopes of Rb exist, only “Rb was session of probe data to make results comparable between sessions.
counted as 87Sr produces a significant interference with *‘Rb. The All data were corrected relative to the March 1992 dataset.
largest expected dimer interference on 85Rb is ?a”Ca. Under the Carbonate standards were unavailable for calibration of the other
current operating conditions this species produces approximately elements due to the generally low concentrations of trace elements
0.008 counts s-’ , calculated from @Ca count rates and calcium isoto- in these minerals. Instead the ion probe was calibrated using the
pic abundances. This will not significantly interfere with “Rb counts standard silicate glass, NBS610 (nominal concentrations: 500 ppm
which are ca. 0.42 counts s-‘. Only one isotope of U (*“U) was Mg; 8.36% Ca; 512 ppm Sr; 426 ppm Rb; 500 ppm Ba; 461 ppm U).
sufficiently abundant for detection by the ion microprobe. No major RIYs were calculated from this standard several times throughout the
molecular interferences were expected for this isotope. fourteen month study period but essentially remained unchanged
In summary, “?d “*Sn ‘39La ‘@‘Ce,and 232Thin the corals were (Table 3). RIY s may differ between carbonates and silicates due to
frequently below the’limit of detection and “Al, “Si “Fe, s5Mn, and different matrix effects between the two media. However, barium
‘OsPbwere rejected from further analysis due to possible contamina- values from fragments of two corals analysed by atomic absorption
tion problems. The following isotopes appeared suitable for analysis, (3 and 10 ppm, A. Mennim, pers. commun., 1993) were in reason-
under the current operating conditions: 26Mg,?a, 85Rb,88Sr, “*Ba,
and 23sU.As it was not possible to unequivocally confirm that “Rb
and z38Uwere not subject to molecular interferences, data for these
isotopes should be viewed with some caution, TABLE 2. Isotopic abundances of analysed elements and their
major element interferences (all oxygen isotopes assumed to be
‘60).
2.2.4. Calibration
Isotope Abund.(%) Possible interferences
The sputtering and ionisation processes during analysis are poorly
understood and no physical model exists to adequately predict ion LbMg 11.29 ‘Y’%+
yields. To compensate for the effects of variations in analytical 44Ca 2.13 88Sr2’
conditions, e.g., beam density, beam current, and spot size between s5Rb 72.15 42Ca43Ca+'84,&'H+
analyses, trace element count rates are normalised to a reference
species, in this case ?Za. Concentrations are then calculated relative “Rb 27.85 *‘Sr+, 43Ca44Ca+
to a standard of known composition. The normal&d ratio, [“ill **Sr 82.56 44Ca44Ca+
[*Cal, is converted into a concentration using the following for-
mula: 13’Ba 11.32
13BLa+. 13SCe+
13’Ba 71.66
2X - CPS, x 1 238
U 99.28
(1)
XC, CPSC, RIY, ’
3460 N. Allison

Table 3. Relative ion yields (relative to Ca) for Mg and Sr calculated from the
carbonate standard, NCC, for each ion microprobe session and for all elements
calculated from the silicate standard NBS 610.

NCC 1 NBS 610

Element Dee 1991 Mar 1992 May 1992 Jan 1993

Mg 0.550 0.607 0.599 0.518 0.951

Ca 1.000 1.000 1.000 1.000 1.000
Sr 0.513 0.443 0.487 0.498 0.407
Rb _ 0.141
Ba 0.183
U _ 0.0692

able agreement with values obtained from single ion microprobe
analysis of adjacent coral material (6 and 11 ppm, respectively,
Allison, 1994). Although it was not possible to accurately calibrate
the ion probe using the silicate standard, detectable variations be-
tween samples proportionally mirror trace element variations and the
instrument can still be used to investigate geochemical heterogeneity.
2.2.5. Analytical reproducibility
The ion probe unit’s computer system calculates an analytical
error based purely on counting statistics which is calculated as fol-
lows:
% error (1~7) = 7 X 100,
(2)
where N = total number of counts for the isotope over the analytical
period. The ranges of counting statistic errors observed for each
element are shown in Table 4. As a function of the total number of
counts, these errors take no account of differences in beam focusing
or fluctuations in beam current between analyses and essentially
represent the smallest possible errors which can be expected. To
test analytical reproducibility under experimental conditions it is
necessary to perform multiple analyses on a homogeneous carbonate
material. The carbonate standard is homogeneous with respect to
magnesium but heterogeneous for strontium and does not contain
rubidium, barium or uranium in sufficiently high concentrations for
analysis. The next best way to assess reproducibility was to perform
immediately adjacent analyses on the coral samples and to assume
that the coral was homogeneous over this distance. The corals in
the Phuket area have typical linear extension rates of 15-20 mm
y -’ corresponding to an average growth of 40-55 pm day-‘. Al-
though corals do not extend linearly (they produce radiating fans of
aragonitic needles), the distance between adjacent analyses probably
accounts for no more than two or three days growth. It is unlikely
that local seawater chemistry or temperature will significantly alter
over this time. The calculated element concentrations for each pair
of analyses are shown in Appendix B. The reproducibility of each
pair was calculated as a concentration (half the concentration differ-
ence between the two values) and as a percentage (the concentration
reproducibility as a percentage of the lowest concentration of the
pair). The reproducibility ranges and averages for each element are
shown in Table 4. The reproducibility error obtained for magnesium
(5%) is in good agreement with the standard deviation observed
during multiple analyses on the carbonate standard, NCC, which
appeared homogeneous with respect to magnesium. Reproducibility
errors for the remaining elements are usually well in excess of count-
ing statistic errors. It is not possible to conclude whether this reflects
real small scale geochemical heterogeneity or instrumental varia-
tions. As such, the reproducibility errors calculated between analyti-
cal pairs are probably an overestimate of analytical errors.
2.3. Trace and Minor Element Concentrations in Corals
Analyses were performed vertically (with time) across each thin
section to produce a chronological record of trace and minor element
variations. Analyses were performed at spacings of approximately
500-1000 pm. The relative position of each sample in the annual
bright-dull fluorescent couplet was used to estimate the approximate
deposition time of the carbonate sampled in each analysis. Corals
were analysed over the three most recently deposited fluorescent
couplets, i.e., approximately November 1988-July 1991.
3. RESULTS
Although considerable time was dedicated to positioning
the primary beam on the sample, many of the analyses (about
10%) were subsequently excluded from the dataset as they

Table 4. The range of errors for analysis of each isotopef4Ca ratio calculated
from counting statistics (single analyses) and by comparing analyses between
adjacent pairs (n = number of pairs).

Isotope Range of Reproducibility range Mean reproducibility n

Counting Stat. between pairs of between n pairs (%)
Error (%) analyses (“A)
26Mg/Ca 0.3 - 1.2 o-14 5 27
s”Rb/Ca 11-22 o-37 13 15
88SrlCa 0.1 - 0.2 o-4 1 27
’j'Ba/Ca 2-7 o-14 5 27
238UICa 6 - 16 1 - 12 4 5
 Comparative determinations of trace and minor elements in coral aragonite
Table 5. Ranges of trace and minor element concentrations determined by ion
microprobe analysis (mmol mof’ Ca for Sr and Mg; pmol mof’ Ca for all other
elements). Approximate concentrations of each element in ppm (assuming Ca =
38 wt%) are also shown.
Observed Approximate
range of range
concentrations (ppm)
3.25 - 6.23 748 - 1435
0.06 - 0.81 0.05 - 0.66
7.42 - 9.07 6160 - 7529
1.51 - 8.61 2.0 - 11.2
0.00 - 0.40 0.0 - 0.90
’Howard and Brown 1987, Pocillopora spp.
2 Goreau 1977, Montastrea spp.
3 Sreekumaran and Gogate 1972, Porites spp.
’ Weber 1973, DipIoria spp.
’ Amiel et al. 1973, Diploria spp.
6 Shen et al. 1992, Pavona claws
’ Pingitore et al. 1989, Acropora palmata
* reviewed in Swart and Hubbard 1982
were contaminated by microborings and centres of calcifica-
tion. These areas are best visualised in transmitted light and
were difficult to distinguish using the reflected light micro-
scope attached to the ion microprobe. Microborings and cen-
tres of calcification can be associated with elevated concen-
trations of barium and magnesium (Allison and Tudhope,
1992). All uncontaminated analyses obtained over the four
ion probe sessions are shown in Appendix C.
The ranges of concentrations of each element are shown
in Table 5. The approximate concentrations of all elements
in ppm have been calculated to allow easier comparisons
with data produced by previous authors (also shown). Con-
centrations in ppm have been calculated assuming a nominal
calcium concentration of 38%. In pure CaC03, calcium com-
prises 40.08% of the compound mass. Coral aragonite con-
tains less calcium due to the inclusion of several contaminant
ions, primarily sodium (ca. 10000 ppm), strontium (ca. 7000
ppm), and magnesium (ca. 1000 ppm) .
Seasonal variations of magnesium, rubidium, strontium,
barium, and uranium in each coral are illustrated graphically
(Figs. l-5). Element concentrations are plotted against the
relative position of each analysis in the coral, i.e., the approx-
imate deposition date. In general, seasonal variations in ele-
ment concentrations were not apparent and for most corals
the data points appear randomly scattered across each graph.
However, variations in concentration between points far ex-
ceed analytical errors and reflect real geochemical variations.
Large variations in element concentration, which approach
the total range of values recorded, are frequently observed
over relatively small distances corresponding to less than
one month’s growth. In addition, almost all the corals exhibit
an increase in barium concentration in the outermost growth
3461
Concentrations
reported in the
literature (ppm)
1000’ - 21002
o.873
69004 - 78005
56 - 15’
1.5 - 3.08
interval, i.e., from approximately November 1990 to July
1991 (Fig. 4).
A comparison of the ranges of element concentrations
deposited by different coral colonies was not the aim of this
study. However, it is apparent that corals from the same reef
site deposit substantially different concentrations of some
elements. For example, coral AQ2 deposits a much higher
and wider range of barium concentrations (3.14-8.61 pmol
mol -’ Ca) than observed in coral AQSi ( 1Sl -3.16 pmol
mol-’ Ca) or AQ8ii (1.87-4.27 pmol mol-’ Ca). Coral
KR6 deposits a higher range of magnesium concentrations
(4.31-6.32 mm01 mol-’ Ca) than coral KR4 (3.25-5.15
pm01 mol-’ Ca).
4. DISCUSSION
Element concentrations for magnesium, rubidium, stron-
tium, and barium are in reasonable agreement with values
previously reported in the literature (see Table 5). The mag-
nesium concentrations determined here cover a slightly
lower range than has previously been reported. However, as
this study avoided the analysis of adsorbed ions, which may
account for up to 20% of skeletal magnesium (Amiel et al.,
1973), a lower range of concentrations was expected.
The uranium values obtained here are considerably lower
than those previously reported. It is most likely that this
represents a m&calibration of the ion microprobe due to
matrix differences affecting RIYs between the silicate stan-
dard and the aragonite samples. Although it is not possible
to estimate uranium concentrations using the ion microprobe,
differences between samples reflect true variations in geo-
chemistry.
3462 N. Allison

Probe Session: A Dee 1991 March 1992 * May 1992 ?? January 1993

Analytical error = +/- 5%

T 7

5.4 AQ8a
4.8
4.2
3.6 A

5.1 AQ8b
4.5
3.9
3.3
3 5.1 AQ2 A
U
4.5 * A

3.9
3.3
6.0 PBl
5.4
4.8
6.4 PB9
.
5.8
5.2
.
4.6 .

4.0
5.1 KR4
4.5
3.9
3.3
6.8
KR6 . .
6.2
5.6
5.0
4.4

Nov 1988 Nov 1989 Nov 1990

Approximate deposition dates determined from the dull-bright fluorescent banding

FIG. I. Magnesium chronologies in corals from Porites Bay (PB),Aquarium Reef ( AQ) , and Ko Racha (KR)

4.1. Spatial Variations in Trace and Minor Element
Concentrations
Significant variations in element concentration were ob-
served between the chronological analyses of all the ele-
ments studied here, i.e., magnesium, rubidium, strontium,
barium, and uranium. Large variations in element concentra-
tion, which approach the total range of values recorded, are
frequently observed over relatively small distances corre-
sponding to less than one month’s growth. This small scale
geochemical heterogeneity has not been recorded previously.
No seasonal variations in geochemistry were detected. In
particular, there is no evidence of the local annual seawater
temperature range (2-4°C) recorded in the skeletal stron-
tium concentration. According to Beck et al. (1992) this
temperature variation should correlate with an annual skele-
tal strontium range of ca. 0.2-0.3 mmol mol-’ Ca (186-
248 ppm) . Strontium concentrations in this study vary by as
much as 0.6 mm01 mall’ Ca (approximately 480 ppm) over
relatively small skeletal distances. It seems unlikely that this
small scale spatial geochemical heterogeneity of strontium
and other elements reflects short-term variations in seawater
chemistry and/or temperature. While it is possible that
warming and evaporation of the shallow water over the reef
flat may lead to some small variations in local water chemis-
try and temperature on a daily or weekly basis, I detected
 Comparative determinations of trace and minor elements in coral aragonite 3463

Probe Session: A Dee 1991 ?? March 1992 * May 1992 ?? January 1993

Analytical error = +/- 13%

0.3 AQ8a

0.2

0.6 AQ8b
0.5 ..
.
0.4 00
.
0.3 .
. .
0.2

0.1

AQ2

PBl

0.8 KR6
.
0.7

0.6
.
0.5 .
0.4 .

. .
0.3

0.2 . A A

Nov 1988 Nov 1989 Nov 1990

Approximate deposition dates determined from the dull-bright fluorescent bandin

FIG. 2. Rubidium chronologies in corals from Porites Bay (PB), Aquarium Reef (AQ), and Ko Racha (KR)

no significant variations in salinity or temperature along the ever, several possible explanations can be discussed. The
reef front at Porites Bay during the day (N. Allison, unpubl. incorporation of some elements in the aragonite may be
data) and it seems unlikely that any significant variations in affected by calcification rate (de Villiers et al., 1994) or
seawater composition occurred. In addition, daily variations the trace element composition of the dissolved inorganic
in seawater chemistry or temperature would have been re- carbonate pool available for calcification may be modified
corded in the skeleton over very small distances and should by the coral symbiotic zooxanthellae (Buddemeier et al.,
have been included in the estimates of analytical error, ob- 1981). However, it is likely that the largest variations in
tained by comparing pairs of analyses up to 50 pm apart. If calcification rate occur on a daily basis (day vs. night) and
the strontium vs. temperature relationship does occur in the geochemical heterogeneity attributed to this would have been
coral skeletons of this area, then it is effectively swamped included in the estimates of analytical error. Weekly or
by this smaller scale geochemical heterogeneity. The cause monthly variations in calcification rate or in algal efficiency
of this heterogeneity was not discovered in this study; how- may cause some geochemical heterogeneity.
3464 N. Allison

Probe Session: A Dee 1991 March 1992 * May 1992 ?? January 199

Analytical error = +/-I %

8.8
AQ8a
8.4

8.0

AQ8b ??

8.2

8.2

8.2

7.8

PB9

8.8
c
8.4

8.0

8.6 KR6

8.2
.
7.8

7.4

Nov 1988 Nov 1989 Nov 1990

Approximate deposition dates determined from the dull-bright fluorescent bandin

FIG. 3. Strontium chronologies in corals from Porites Bay (PB), Aquarium Reef (AQ), and Ko Racha (KR)

Barnes and Lough (1993) suggested that while calcifica- The geochemical heterogeneity may relate to the metal
tion is concentrated at the surface of the coral colony, thick- binding capacity of the organic matrix produced by the coral
ening of the skeletal elements occurs throughout the tissue tissue during calcification and disseminated throughout the
layer, which occupies skeleton deposited over a period of coral skeleton. The coral tissue may contain substantially
4- 13 months. This lateral thickening may account for up to higher concentrations of certain metals (e.g., barium and
50% of the total material deposited. Material deposited in uranium, Flor and Moore, 1977) than the associated coral
this fashion may have a substantially different geochemical skeleton and contamination of the skeleton with organic ma-
signature to the originally deposited material either because terial may result in substantial geochemical heterogeneity.
of changes in seawater chemistry or temperature between Mitterer ( 1978) suggested that the organic matrix itself is
the two deposition dates or due to the reduction in calcifica- heterogeneous, containing areas of varying metal binding
tion rate. However, once again, I expected any small scale capacity.
heterogeneity relating to this phenomena to be included in The small scale skeletal geochemical heterogeneity ob-
estimates of analytical error. served here does not appear to reflect variations in seawater
 Comparative determinations of trace and minor elements in coral aragonite 3465

Probe Session: A Dee 1991 ?? March 1992 * May 1992 ?? January 1993

Average analytical error = +/- 5%

3 AQ8a AA
A AA
1 A~

A
*
1
A
AL
A

6-1
I
m
.
i
??
.
??
?? II

8 KR6
A
i A
6 . .
. ?? .
.
. A
. . . A

0 8 A

Nov 1988 Nov 1989 Nov 1990

Approximate deposition dates determined from the dull-bright fluorescent bandin

FIG. 4. Barium chronologies in corals from Porites Bay (PB), Aquarium Reef ( AQ), and Ko Racha (KR)

temperature or chemistry. It seems most probable that the
heterogeneity reflects the binding of metals by a heteroge-
neous organic matrix which is itself distributed unevenly
throughout the skeleton.
Other authors have successfully reported excellent correla-
tions between coral geochemistry and seawater characteris-
tics. Either this heterogeneity did not occur in the corals they
analysed or the geochemical variations were averaged out
in the analysis of the larger sample sizes they used. Research-
ers in the field of coral palaeoclimatology generally assume
that the geochemical signature in the skeleton is directly
related to seawater characteristics. This does not appear to
be the case in this study. It is important to evaluate the extent
to which this small scale spatial heterogeneity affects corals
from other sites and to determine how it may influence the
geochemical signature of coral skeletons.
4.2. The Barium Increase in the Outermost Part of the
Skeletons
Almost all the corals exhibit an increase in barium concen-
tration in the outermost growth interval although no other
seasonal variations are apparent. This may be a reflection of
the coral bleaching event which occurred in the Phuket area
3466
Probe Session: . January 1993
Analytical error = +I- 4%
0.4
0.3
0.2
0.1
0.0
PB9
0.2
0.1
0.2
0.1
t
Nov 1988 Nov 1989
Approximate deposition date determined from the dull-bright fluorescent banding.
FIG. 5. Uranium chronologies in corals from Porites Bay (PB), Aquarium Reef (AQ), and Ko Racha (KR).
from early June 1991 onwards during a period of anoma-
lously high seawater temperatures. However, none of the
corals used in this study appeared visibly affected by the
bleaching event and there is no evidence of a significant
reduction in skeletogenesis over the outermost growth inter-
val (Allison, 1994). There is no evidence that local environ-
mental factors which may increase seawater barium concen-
trations, eg., freshwater runoff or coastal upwelling, were
more pronounced than compared to previous years (Allison,
1994; T. K&be, pers. commun., 1991; respectively).
Similar increases in skeletal barium have been observed
by S. Tudhope (pers. commun. 1993, coral from Oman) and
Hart and Cohen (1996, coral from South Africa) in corals
from areas unaffected by coral bleaching events. It seems
most probable that this barium is not skeletally bound but
is associated with some organic material which may age and
be removed from the skeleton in time.
4.3. Differences in Element Concentration between
Coral Colonies
It became apparent during the study Chatindividual corals,
of apparently the same species, deposit substantially differ-
ent ranges of magnesium and barium concentrations both
within and between reef sites. Variations within each site
are as large as those observed between sites and it is unlikely
N. Allison
.
00
.
.
.
.
Nov 1990
that these differences are due to variations in seawater chem-
istry or temperature. The geochemistry of the skeletons may
be influenced by the factors discussed above, i.e., variations
in calcification rate between colonies, in concentrations of
zooxanthellae or in quantity and composit?on of organics in
the skeleton. Alternatively the different element ranges may
reflect genetic differences between coral colonies which af-
fect trace and minor element distribution coefficients. All
corals exhibited skeletal characteristics of Porites lutea
(Veron, 1986) ; however, considerable variations in corallite
morphology were apparent between colonies.
The cause and extent of this geochemical anomaly be-
tween colonies should be further investigated. Distribution
coefficients, reflecting the extent to which an element in
seawater is incorporated into the skeleton, have previously
been calculated for several coral species and for several
elements. In this study, calculations of barium distribution
coefficients will vary by as much as 2-3 between corals
AQ2 and AQ8 although the corals appeared to be the same
species. Other researchers estimates of distribution coeffi-
cients may have incorporated this degree of error.
5. SUMMARY
1) The ion microprobe technique has been developed to
produce comparative determinations of certain elements
 Comparative determinations of trace and minor elements in coral aragonite
in coral aragonite. Magnesium, rubidium, strontium, and
barium concentrations were in reasonable agreement with
values previously reported in the literature. Uranium con-
centrations were considerably lower than previous esti-
mates probably reflecting a miscalibration of the ion mi-
croprobe.
2) The coral skeletons examined here are heterogeneous
with respect to magnesium, rubidium, strontium, barium,
and uranium on a very small scale. The whole concentra-
tion range of an element is frequently observed over
relatively short skeletal distances corresponding to less
than one months growth. Perhaps the most plausible ex-
planation for this heterogeneity is a heterogeneous metal-
binding organic matrix which is unevenly dispersed
throughout the skeleton.
3) Seasonal variations in element concentrations were not
apparent in any of the corals except for a general increase
in barium in the outermost growth interval of the skele-
ton. This may reflect an increase in skeletal organic mate-
rial or may be an anomaly caused by the coral bleaching
event in progress at the time.
4) Individual colonies deposited substantially different
ranges of magnesium and barium both within and be-
tween sites. The variation in these ranges could result
in significantly different distribution coefficients being
calculated between colonies.
Acknowledgments-I wish to thank John Craven for technical sup-
port with the ion microprobe, Sandy T&hope for assistance with
field work and Jane Foster and Mike Hall for preparation of thin
sections. I thank the director and staff at the Phuket Marine Biologi-
cal Center for the use of their facilities. Both Sandy Tudhope and
John Craven provided valuable comments on this manuscript. Ed
Boyle, Graham Layne, Stan Hart, and Rick Hervig reviewed the
manuscript and are thanked for their constructive criticisms. This
work was undertaken when the author was in receipt of a NERC
studentship (GT4/90/G3/47).
Editorial handling: M. A. McKibben
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3468 N. Allison

Appendix A. Multiple analyses of Sr and Mg on

the carbonate standard, NCC. % errors calculated
from counting statistics are included. Averages and
standard deviations of the 19 analyses are shown.

Analysis Mg Sr
No. ppm % ppm %
error error
1 2580 6.0 830 1.3
2 2850 6.6 820 1.3
3 2820 6.5 890 1.4
4 2870 6.6 640 1.0
5 2410 5.6 1010 1.6
6 2820 6.5 790 1.2
7 2750 6.4 860 1.3
8 2930 6.8 670 1.0
9 2850 6.6 700 1.1
10 2870 6.6 800 1.2
11 2700 6.2 840 1.3
12 2320 5.4 850 1.3
13 2640 6.1 890 1.4
14 2670 6.2 840 1.3
15 2520 5.8 750 1.1
16 2600 6.0 870 1.3
17 2790 6.4 800 1.2
18 2820 6.5 880 1.4
19 2790 6.4 830 1.3
Average 2716 819
S.D. (la) 162 83
S.D. (%) 6.0 1.0

Appendix B. Trace and minor element concentrations on adjacent pairs of analyses up to 50 pm apart.

Mg (mmol Rb (pmol mol-’ Ca: Sr (mm01 mokzoar) Ba (pmol mol-’ Ca) U (pm01 mol-’ Ca)
Analyses Analyses Error Aualyses Analyses Error Analyses Error

4.77 5.44 7 0.25 0.27 5 8.10 8.21 4.00 4.25 3 0.08 0.10 12
5.40 4.77 6 0.20 0.20 0 8.04 8.14 4.13 4.38 3 0.16 0.15 1
4.77 5.07 3 0.20 0.27 15 8.04 8.21 4.00 4.38 5 0.20 0.19 1
5.07 5.44 4 0.20 0.25 11 8.04 8.10 4.25 4.38 1 0.16 0.18 5
4.98 5.23 2 0.20 0.25 11 8.10 8.14 4.13 4.25 2 0.21 0.21 1
6.28 5.57 6 0.30 0.33 6 8.16 8.21 7.27 7.38 1
5.15 6.03 8 0.30 0.35 7 7.96 8.26 5.87 5.92 0
5.15 4.94 2 0.10 0.15 24 8.25 8.26 6.14 6.46 3
4.90 5.11 2 0.07 0.15 37 8.05 8.25 6.34 6.14 2
5.15 4.56 6 0.29 0.33 8 8.27 8.39 1.68 1.82 4
5.28 4.94 3 0.31 0.37 9 8.49 8.56 2.16 2.31 3
5.78 4.65 11 0.27 0.35 12 8.54 8.73 1.27 1.34 3
5.65 4.77 8 0.11 0.19 28 8.50 8.63 0.94 1.21 12
4.90 5.86 9 0.17 0.20 10 8.28 8.39 1.25 1.26 0
4.77 4.61 2 0.24 0.27 7 8.34 8.35 1.78 1.92 4
3.73 3.42 4 8.23 8.39 2.21 2.36 3
4.08 4.23 2 8.52 8.52 5.71 6.30 5
5.32 5.44 1 8.35 8.63 6.63 8.24 11
4.82 4.27 6 8.60 8.68 2.42 3.02 11
3.87 3.52 5 8.69 8.75 3.31 4.39 14
3.72 4.07 4 8.55 8.71 3.42 3.90 6
4.16 4.19 0 8.32 8.54 4.31 4.90 6
4.94 4.61 4 8.23 8.34 2.45 2.95 9
6.32 4.73 14 7.23 7.45 2.59 2.83 5
4.52 5.07 6 6.87 7.46 2.56 2.62 1
3.61 3.98 5 7.74 7.77 2.56 2.56 0
7.38 7.75 5.61 5.87 2

The reproducibility between each pair has been calculated as a % error (the concentration difference between the two analyses as a
percentage of the average concentration). Comparisons are only made between analyses from the same microprobe sessions. No
corrections to Sr data have been made.
 Comparative determinations of trace and minor elements in coral aragonite 3469

Appendix C. Seasonal trace and minor element variations expressed as mm01 mol-’ Ca (Sr and Mg) and pmol mol.-’ Ca (Rb, Ba, U).
Corr. Corr.
Sample RYP Mg Rb Sr Sr Ba U Sample RYP Mg Rb Sr Sr Ba U
December1991I March 1992
AQ8iA 3.63 5.07 0.30 7.42 8.31 2.94 PBlA 3.37 - 0.20 8.14 - 4.14
3.58 3.58 0.21 7.73 8.65 3.01 PBlB 3.59 4.86 0.43 8.19 - 5.99
3.42 1.23 0.18 7.41 8.30 2.12 3.50 4.94 0.28 8.05 - 5.61
3.11 1.44 7.41 8.30 2.29 3.50 5.74 0.17 7.98 - 5.06
2.90 4.48 7.21 8.08 2.40 3.53 4.98 0.16 8.16 - 7.39
3.20 4.90 7.25 8.12 1.71 3.58 4.82 0.23 7.96 - 5.88
AQ2A 3.73 3.61 0.25 7.75 8.68 5.88 3.58 5.57 - 8.26 - 5.93
3.66 4.82 0.16 7.53 8.43 8.09 3.53 5.23 - 8.21 - 7.28
3.12 3.98 7.38 8.26 5.62 3.51 5.15 - 8.25 - 6.15
3.68 3.25 7.63 8.55 8.61 3.52 6.03 - 8.26 - 6.47
3.52 4.73 7.64 8.56 6.82 KR4B 2.65 4.04 - 8.39 - 2.53
3.55 1.65 7.49 8.39 6.83 2.29 4.16 - 8.34 - 2.96
KR4A 3.51 4.01 7.54 8.44 2.97 2.31 4.19 - 8.23 - 2.45
3.61 4.69 7.45 8.34 7.72 2.26 3.72 - 8.54 - 4.31
3.59 3.82 7.34 8.22 6.23 2.25 4.07 - 8.32 - 4.91
3.56 4.15 7.48 8.38 4.47 2.38 3.87 - 8.55 - 3.90
KR6A 3.58 4.98 7.46 8.35 6.32 2.37 3.52 - 8.71 - 3.43
2.32 5.78 7.60 8.51 7.16 KR4B 2.63 4.73 - 8.42 - 3.47
2.18 4.56 7.48 8.38 4.40 KR4A 3.60 5.15 - 8.27 - 7.28
2.93 4.44 7.41 8.30 2.40 3.31 3.95 - 8.54 - 4.59
3.10 4.40 1.54 8.44 3.83 3.13 4.69 - 8.35 - 3.82
KR4A 2.33 3.82 1.42 8.31 3.97 PBlC 3.17 5.07 - 8.16 - 6.26
2.11 4.3s 7.60 8.51 3.70 3.29 5.11 - 8.63 - 6.26
AQ2A 3.44 4.40 7.54 8.44 6.67 3.30 5.69 - 8.31 - 5.16
3.30 4.27 7.35 8.24 5.58 May 1992
3.07 3.90 7.53 8.43 3.80 AQ8iiB 2.62 3.50 0.17 8.93 - 2.59
AQ2A 3.12 4.07 7.61 8.52 4.30 2.64 4.56 0.24 8.47 - 2.90
2.94 4.40 7.31 8.18 3.14 2.54 4.77 0.28 8.68 - 3.53
2.60 4.86 7.68 8.60 4.28 2.49 3.80 0.42 8.99 - 3.70
2.79 4.44 7.40 8.29 3.63 2.38 4.98 0.17 8.79 - 3.19
2.77 4.48 7.45 8.34 3.62 2.37 3.80 0.26 9.07 - 3.12
AQ8iB 2.66 4.61 7.57 8.48 2.90 2.34 4.82 0.07 8.18 - 2.79
2.59 4.31 1.47 8.31 2.72 2.23 4.40 0.06 8.99 - 2.78
2.55 4.94 7.31 8.25 3.16 2.17 4.07 0.10 8.76 - 3.22
2.43 4.04 7.35 8.24 2.66 AQSiiB 2.06 4.31 0.16 8.74 - 4.27
2.39 5.23 7.25 8.12 2.60 AQ8iiA 3.64 4.61 0.42 7.80 8.42 3.35
2.36 5.15 7.55 8.46 2.91 3.47 3.48 0.26 7.76 8.38 3.10
AQ8iB 2.19 5.23 7.39 8.28 2.76 3.69 3.84 0.58 7.76 8.38 2.37
2.18 4.44 7.47 8.37 2.52 3.67 4.44 0.27 7.46 8.06 2.42
AQ8iA 2.80 4.90 7.39 8.28 2.46
January 1993
3.30 4.23 7.30 8.17 1.51 3.79 0.45 7.76 8.38 2.04 0.30
AQ8iiA 3.43
3.36 4.82 7.40 8.29 2.09
3.64 4.31 0.57 7.99 8.63 3.77 0.18
KR4A 3.02 3.69 7.48 8.38 3.03
3.58 4.40 0.39 7.81 8.43 2.54 0.30
3.53 4.94 7.16 8.02 3.12
3.19 4.19 0.07 7.73 8.34 2.42 0.00
3.44 4.40 7.46 8.35 4.93
2.99 5.07 0.27 7.77 8.39 2.57 0.10
KR4B 2.99 3.25 7.41 8.30 3.15
3.27 - 0.62 7.91 8.54 2.33 0.18
March 1992
3.49 4.52 0.48 7.75 8.37 2.69 0.20
PBlA 3.69 5.65 0.35 1.95 - 3.65
3.34 3.45 0.38 7.97 8.61 2.78 0.22
3.52 5.53 0.26 8.10 - 5.93
3.26 4.52 0.23 7.92 8.56 2.48 0.19
3.50 5.19 0.29 7.98 - 5.61
2.99 4.52 0.24 7.74 8.36 2.56 0.08
3.37 5.07 0.24 8.10 - 4.26
AQSiiC 1.99 4.69 0.32 7.96 8.59 1.87 0.15
3.37 5.40 0.27 8.21 - 4.01
1.91 3.88 0.25 7.82 8.44 2.11 0.20
3.37 4.77 0.20 8.04 - 4.38
8.14 - 6.31 1.91 4.18 0.49 7.66 8.27 2.47 0.19
3.44 6.20 0.25
3.62 6.16 0.30 7.97 - 4.10 1.86 4.23 0.41 7.98 8.62 2.58 0.18
3.70 5.65 0.32 8.12 - 4.63 1.83 4.48 0.25 7.85 8.48 2.55 0.21
PBlC 3.56 6.45 0.42 8.23 - 7.17 AQSiiC 1.87 4.73 0.49 7.76 8.38 2.20 0.16
3.54 6.03 0.27 8.05 - 5.55 1.82 4.82 0.41 7.74 8.36 2.18 0.21
3470 N. Allison

Appendix C (continued)
-I-
Corr. Corr.
Sample RYP Mg Rb Sr Sr BP U Sample RYP, Mg Rb Sr Sr Ba IJ
AQSiiC l.73 4.23 0.45 7.82 8.44 3.03 0.30 KRQA 3.19 5.28 0.21 7.69 8.31 6.11 0.14
1.66 - 0.36 8.33 9.00 2.63 0.22 2.80 5.15 0.36 7.62 8.23 3.40 0.21
PB9A 3.51 3.95 0.53 7.68 8.29 2.16 0.23
1.61 4.73 0.31 7.53 8.13 2.49 0.12
3.43 4.19 0.31 7.91 8.54 2.02 0.19
2.00 4.27 0.34 7.59 8.19 2.27 0.16
5.19 0.48 7.68 8.29 3.72 0.21 3.29 4.86 0.43 7.68 8.29 1.80 0.15
KR6C 1.76
4.82 0.31 7.39 7.98 2.52 0.23 3.08 4.61 0.34 7.69 8.31 1.81 0.12
1.51
4.61 0.41 7.31 7.89 5.40 0.12 2.89 6.03 0.38 7.75 8.37 1.02 0.17
1.93
KR6B 2.58 4.94 0.56 7.23 7.80 2.83 0.12 3.59 4.35 0.39 7.78 8.41 2.68 0.23
2.48 4.31 0.36 7.34 7.93 3.49 0.11 *g;; ;;; 3.81 0.45 7.67 8.28 3.15 0.20
2.15 6.32 0.81 6.87 7.42 2.62 0.38 4.61 - 7.45 8.04 2.59 -
KR6A 3.63 5.36 0.73 7.12 7.69 5.13 0.11 2.15 4.73 - 7.46 8.06 2.56 -
3.44 5.07 0.52 7.26 7.84 5.22 0.18 2.72 6.45 - 7.57 8.18 4.18 -
3.27 4.98 0.32 7.59 8.19 6.07 0.21

Relative yearly positions (RYP) are calculated by dividing the distance of the
sample along the fluorescent couplet by the width of the couplet. Samples prefixed
by 1 were deposited in tbe couplet approx. Nov ‘88 - Nov ‘89; by 2 in the couplet
approx. Nov ‘89 - Nov ‘90 and by 3 in the couplet approx. Nov ‘90 -Nov ‘91.

Average strontium concentrations (mmol rnol-’ Ca) on adjacent pairs analysed in

different ion microprobe sessions were used to calculate correction factors
relative to the March 1992 data set.