Early Marine Diagenesis of Biogenic Aragonite and Mg-Calcite

Chemical Geology 175 2001.
221248
www.elsevier.comrlocaterchemgeo
Early marine diagenesis of biogenic aragonite and Mg-calcite:

new constraints from high-resolution STEM and AEM analyses
of modern platform carbonates
Victoria C. Hover a,) , Lynn M. Walter b, Donald R. Peacor b
a
Rutgers, the State Uniersity of New Jersey, Newark Campus, Department of Geological Sciences, 407 Boyden Hall, 195 Uniersity Ae.,
Newark, NJ 07102-1814, USA
b
Uniersity of Michigan, Department of Geological Sciences, 2534 C.C. Little Building, 425 E. Uniersity Ae.,
Ann Arbor, MI 48109-1063, USA
Received 23 February 2000; accepted 22 April 2000
Abstract
Prior studies of porewater compositions from modern shallow marine carbonates have established that dissolution and
recrystallization of metastable aragonite and Mg-calcites occur during the earliest stages of sedimentation. Yet, significant
microstructural and mineralogical changes in sediment allochems have not been observed. In part, this is due to the high
resolution required to identify diagenetic changes in these finely crystalline materials. Herein, we present ultrastructural and
microgeochemical evidence for early marine diagenesis using scanning electron microscopy SEM. and high resolution
scanning transmissionranalytical electron microscopy STEMrAEM. methods to characterize original biogenic materials
and sediment boxcores from modern deposits on the FloridanBahamas platform. We selected the two most common
sediment producers, a Mg-calcite foraminifer, Peneropolid, and an aragonitic green algae, Halimeda, for study. Both are
composed of submicron-sized crystallites, whose excess free energy could provide a thermodynamic driving force for
recrystallization.
STEM observations of grain mounts containing dispersed Mg-calcite and aragonite crystallites from gently disaggregated
individual Peneropolids and Halimeda segments indicate that living specimens contain euhedral prismatic crystals with
blunt terminations and smooth faces. Specimens from the sediment column show abundant evidence for alteration. The most
dramatic changes involve crystallite dissolution and precipitation of thin overgrowths, causing the overall aspect ratio of
crystallites to shorten and widen. Direct measurements of several hundred individual crystallites confirm that crystallite
length and width distributions differ significantly between original and altered materials. These changes are consistent with
crystal-growth processes that tend to minimize surface free energy by increasing overall crystal size and by producing more
equant shape.
The precipitated material has a composition and structure which is grossly similar to the host crystallite, as determined by
AEM and electron diffraction analyses. AEM analyses of hundreds of Mg-calcite crystallites from living specimens of
Peneropolid foraminifera indicate a composition of ; 1314 mol% MgCO 3 , whereas crystallites from altered tests are
; 13 mole% lower. Taken together, these data suggest that early diagenesis in shallow marine carbonates is indeed
)
Corresponding author. Tel.: q1-973-353-1139; fax: q1-973-353-1965.
E-mail address: vhover@andromeda.rutgers.edu V.C. Hover..
0009-2541r01r$ - see front matter q 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 9 - 2 5 4 1 0 0 . 0 0 3 2 6 - 0
222 V.C. Hoer et al.r Chemical Geology 175 (2001) 221248
manifested in the solids as well as the sediment pore waters, producing significant changes in biogenic Mg-calcite and
aragonite crystallite size and shape. This alteration would not produce changes in the mineral assemblage because dissolution
is accompanied by precipitation of compositionally similar overgrowths, under major element conditions not drastically
dissimilar from overlying seawater. However, crystallite recrystallization likely has implications for incorporation of minor
elements which undergo cycling via organic matter decomposition or redox changes e.g., uranium, cadmium, manganese,
rare earth elements.. q 2001 Elsevier Science B.V. All rights reserved.
Keywords: Carbonate diagenesis; Crystal growth; Dissolution and precipitation fabric; STEM; AEM
1. Introduction porewaters buffering pH to values near 7 Ben

Yaakov, 1973; Walter and Burton, 1990.. At sulfate
Geochemical investigations of shallow-water re- reduction levels of - 3 mM, carbonate dissolution is
cent tropical carbonate platforms in southern Florida the dominant process in sediment porewaters e.g.,
and the Bahama Banks indicates that significant Walter and Burton, 1990.. However, increases in
early diagenetic modification of both sediments and porewater Ca2q concentrations are commonly greater
porewaters occurs Berner, 1966; Rosenfeld, 1979; than can be generated from carbonic acid generated
Morse et al., 1985; Walter and Burton, 1990; Walter during SO42y reduction alone. Furthermore, many
et al., 1993; Rude and Aller, 1991; Patterson and carbonate platform porewaters, especially biotur-
Walter, 1994a; Ku et al., 1999.. A large proportion bated sediments, have low degrees of SO42y reduc-
of these platform sediments consists of metastable tion. These observations led Walter et al. 1993. to
biogenic aragonite and high-Mg-calcite allochems in propose that HSy oxidation by introduction of O 2 to
a mud-dominated matrix. Even though seawater the sediments during extensive bioturbation could
overlying carbonate platforms is oversaturated with supply the additional acid for carbonate dissolution.
respect to aragonite Morse et al., 1985; Walter and Previous studies of prepared substrates implanted
Burton, 1990., most shallow porewaters are near in Florida Bay sediments showed that dissolution of
saturation or are undersaturated with respect to arag- fresh, biogenic aragonite and high-Mg-calcite com-
onite and high Mg-calcite Berner, 1966; Morse et ponents occurred in ambient porewaters based on
al., 1985; Walter and Burton, 1990; Walter et al., weight loss measurements and SEM observations
1993.. Walter and Burton 1990. estimated that up to Walter and Burton, 1990; Patterson and Walter,
50% of the total annual carbonate sediment de- 1994a.. From these substrate experiments, the Ca2q
posited in such platforms undergoes dissolution in dissolution flux from Florida Bay sediments was
shallow porewaters, an amount comparable to car- determined to be ; 500 mmolrcm2 year on average
bonate dissolution in the deep-sea Milliman, 1993.. Walter and Burton, 1990.. These directly measured
Porewater isotopic and trace element compositions values compare well with porewater flux estimates
also suggest that significant carbonate precipitation of SO42y reduction and sulfide oxidation rates Walter
also takes place Rude and Aller, 1991; Patterson and Burton, 1990; Ku et al., 1999..
and Walter, 1994b; Ku et al., 1999.. Thus, shallow Although most porewaters show net dissolution,
carbonate platforms are significant components of at SO42y reduction levels greater than 3 mM, in-
the global cycling of CaCO 3 and CO 2 . creased alkalinity and increased Ca2q concentrations
Undersaturation of sediment porewaters, and con- from dissolution eventually result in aragonite and
comitant dissolution of aragonite and Mg-calcite, are Mg-calcite supersaturation in porewaters, and car-
driven by microbial sulfate reduction of organic mat- bonate precipitation occurs Walter et al., 1993; Ku
ter and production of excess dissolved CO 2 Berner, et al., 1999.. Rude and Aller 1991. showed that
1966; Aller, 1982a,b; Morse et al., 1985; Walter and pore-water Sr 2qrCa2q ratios and FyrCa2q ratios in
Burton, 1990; Walter et al., 1993.. The low-Fe con- Florida Bay sediments increase with depth, consis-
centrations in platform carbonate sediments inhibit tent with precipitation of a low Sr 2q- and Fy-bearing
Fe-sulfide formation and HSy accumulates in the low-Mg-calcite. Patterson and Walter 1994a. and
V.C. Hoer et al.r Chemical Geology 175 (2001) 221248 223
Walter et al. 1993. showed that stable C- and The goal of the present study is to reconcile the
O-isotope ratios of implanted substrates and associ- sediment porewater geochemical evidence for disso-
ated sediment allochems changed toward values ap- lution and precipitation in modern Florida Bay and
proaching equilibrium with porewaters and can only Bahama Banks sediments with the apparent lack of
be explained if both dissolution and precipitation bulk mineralogic change observed in all previous
occurs. Rapid 45 Ca2q exchange rates between sedi- studies. We use high-resolution scanning electron
ment and porewater also indicated that significant microscopy SEM. and scanning transmissionrana-
carbonate precipitation on the order of 400 lytical electron microscopy STEMrAEM. to char-
mmolrcm2 year must take place Walter et al., acterize dissolution and precipitation textures and to
1993.. determine the composition of the individual sub-mi-
Although significant modification of porewater cron elongate prismatic crystallites in several com-
within the first meter of sediment has been docu- mon biogenic carbonate grain types, aragonitic green
mented, no significant changes in bulk sediment or algae Halimeda. and high Mg-calcite 1214 mol%
- 45 mm fraction mineralogy has been reported MgCO 3 . benthic foraminifera Peneropolid .. This
based on X-ray diffraction XRD. analyses e.g., study provides the first direct ultratextural and ultra-
Berner, 1966; Walter and Burton, 1990; Patterson, geochemical evidence for early diagenetic alteration
1992; Patterson and Walter, 1994a.. The apparent of individual crystallites via dissolution and precipi-
homogeneity of the sediments may be due, in part, to tation within larger biogenic carbonate allochems.
rapid physical mixing via bioturbation Rude and
Aller, 1991; Patterson and Walter, 1994a.. However,
the lack of measurable mineralogic change with sedi- 2. Materials and methods
ment depth only implies that there is no net replace-
ment of aragonite by calcite or of high-Mg-calcite by 2.1. Field site characterization and sample collection
low-Mg-calcite in these sediments. It does not rule
out the possibility of isomineralogic diagenetic Carbonate sediments were collected at two sites in
changes. the Florida and Bahama Banks platforms Fig. 1..
The large surface area of these allochems results Samples were collected from Shell Key, Florida Bay
in dissolution rates that are commonly greater than Site F. during the winter of 1989 and from the
those of other biogenic components in carbonate Mores Island, Little Bahama Bank Site B. during
platform sediment Walter, 1985; Walter and Morse, the summer of 1992. The sediments consist of exten-
1984a,b.. Because the surface free energy of small sively bioturbated mud to muddy sand containing
crystallites is greater than that of larger crystals of 4570 wt.% aragonite, 2550 wt.% high-Mg-calcite,
the same composition, the solubility of small crystal- and less than 5 wt.% low-Mg-calcite Walter and
lites is greater than the solubility of large crystallites Burton, 1990; Patterson, 1992.. These two localities
in a crystal aggregate. Processes of crystal growth are part of a larger study that has sampled over 50
such as AOstwald ripeningB, in which the precipita- sites in these platforms Walter and Burton, 1990;
tion of material on larger grains takes place at the Walter et al., 1993; Patterson and Walter, 1994a,b;
expense of dissolution of smaller grains in an aggre- Ku et al., 1999.. Sampling efforts for this study were
gate e.g., Chai, 1974, 1975; Baronnet, 1982., may focussed on the collection of living biogenic carbon-
be an important driving force for grain alteration ate producers and their representative allochems from
during early diagenesis of these allochems Morse within the sediment column. These fresh materials
and Casey, 1988.. Such ripening processes, usually were compared to allochems extracted from the sedi-
applied to inorganic crystal growth, may be impor- ment to determine changes in crystallite microtexture
tant in the alteration of the elongate and prismatic and chemical composition.
crystallites with high surface free energy typical of Specimens of living Halimeda incrassata were
these allochems, to crystals with more equant shapes collected at the Bahama Banks site. Plants approxi-
and lower surface free energy during early diagene- mately 2050 cm tall were harvested and preserved
sis. frozen until analysis. Specimens of living Pen-
Fig. 1. Map of a portion of Florida Bay and the Bahama Banks showing the location of sampling sites: Shell Key Florida Bay. and Mores
Island Bahama Banks..
eropolid foraminifera Archaias sp.. were found on for the Florida Bay and Bahama Banks sites are
Penicillus algae in shallow subtidal waters at the shown in Fig. 2, illustrating the amount of organic
Florida Bay site during summer sampling. Penicillus matter oxidation DIC., the degree of sulfate reduc-
specimens with attached foraminifera were collected tion, and the increase in Ca2q. The combined SCO 2
and individual foraminifera were hand-picked from elevation and SO42y depletion in sediment porewa-
the algae, rinsed in ethanol, air-dried, and stored. ters are consistent with organic-matter oxidation and
When collected, the foraminifera had a lustrous sur- sulfate reduction, typical of other mud-rich sites in
face and greenish-tint due to the presence of symbi- Florida Bay and the Bahama Banks e.g., Burton and
otic photosynthetic algae. Walter, 1991; Walter et al., 1993; Ku et al., 1999;
The upper 24 cm of sediment was sampled via Walter, unpublished data.. The amount of Ca2q
diver-collected box cores. Sediments and porewaters released by net carbonate dissolution ranges up to
from 2-cm intervals were processed anoxically in an 1.4 mM in the Florida Bay site and 0.7 mM at the
N2-atmosphere as described by Walter and Burton Bahama Banks site.
1990. and Ku et al. 1999.. Both sites have typical Two intervals were chosen at each site for de-
porewater chemical evolution paths, which include tailed study of Halimeda algae and porcelaneous
organic-matter decomposition, sulfate reduction, in- Peneropolid foraminifera allochems. The surface in-
crease in dissolved inorganic carbon DIC., and interval from 02 cm from both sites F02, B02.,
crease in Ca2qrCly ratio. The variation of porewa- the 68 cm interval from the Florida Bay site F68.,
ter compositions within the upper 30 cm of sediment and the 1214 cm interval from the Bahama Banks
Sediment aliquots were refrigerated until they

could be closely inspected for representative al-
lochems. Intact Peneropolid foraminifera tests and
Halimeda segments were extracted from the mud-
dominated sediments by wet-sieving in ethanol to
remove adhering mud and to displace seawater.
Ethanol was chosen as the rinsing agent because it
does not alter calcareous biogenic components
Pingitore et al., 1993.. All biogenic allochems stud-
ied are from the greater than 400-mm size fraction.
The foraminifera tests and algal segments occur in
various stages of alteration from nearly fresh to
extensively altered. This was particularly evident for
the individual porcelaneous foraminifera tests. Within
any one sediment depth-interval, tests which retained
their smooth porcelaneous surface were found along-
side highly altered and chalky tests. Visibly altered
specimens were selected for further geochemical and
ultrastructural analyses.
2.2. Calcification in liing Peneropolid foraminifera

and Halimeda algae
Calcification of living Peneropolid foraminifera

and Halimeda algae is driven by chemical changes
in the local skeletal environment, brought about by
metabolic processes Bohm and Goreau, 1973;
Borowitzka, 1982a,b, 1986; Borowitzka and Larkum,
1976a,b; Hillis-Colinvaux, 1980; Duguay, 1983;
Duguay and Taylor, 1978; Multer, 1988; Lowenstam
and Weiner, 1989; ter Kuile, 1991; Debenay et al.,
1996.. The Mg-calcite crystallites in porcelaneous
Fig. 2. Variation of porewater compositions with depth. Composi- foraminifera form a semi-random three-dimensional
tions are normalized to Cly content to eliminate evaporation or
network resulting from spontaneous nucleation in a
dilution effects. The overlying water ratio is indicated by the solid
line. A. CO 2 rCly ratios increase with depth and B. SO42yrCly supersaturated environment e.g., Towe and Cifelli,
ratios decrease with depth consistent with bacterially mediated 1967.. Relatively uniform rod-shaped crystallites 12
organic matter oxidation and sulfate reduction; C. Ca2qrCly mm long and 0.1 mm wide first form in small
ratios increase with depth, consistent with carbonate dissolution. bundles in vesicles within the cytoplasm of the
Solid circles: Florida Bay site; open circles: Bahama Banks site.
foraminifera cell and are transported to the cell wall
and released by exocytosis Berthold, 1976; Angell,
1980; Hemleben et al., 1986; Lowenstam and Weiner,
site B1214. were selected to evaluate the degree of 1989.. The first layer of crystallites is arranged
alteration with depth in the sediment. Even though parallel to the outer organic surface of the cell.
the sampling sites are widely separated, sedimenta- Subsequent crystallites are arranged randomly within
tion rates are reasonably similar in the two locations the interior of the cell making the chamber pillars,
so that the sample intervals chosen approximately septal and basal layers described previously e.g.,
represent increasing age or residence time within the Towe and Cifelli, 1967; Angell, 1980; Hemleben et
sediment. al., 1986..
Aragonite crystals in Halimeda first form on tent e.g., Goldsmith et al., 1961.. Individual
fibrous material at the filament wall surfaces within foraminifera were ground, mixed with a fluorite
the interutricle spaces Wilber et al., 1969; Borow- internal standard, and mounted on a glass slide as an
itzka, 1986; Borowitzka and Larkum, 1977; Borow- acetone-smear. XRD analyses were carried out using
itzka et al., 1974; Nakahara and Bevelander, 1978; a Philips model XRG 5100 diffractometer operated
Hillis-Colinvaux, 1980.. Uptake of CO 2 during at 55 kV and 15 mA, using Cu K a radiation, a
photosynthesis from interutricle compartments in- scintillation detector with pulse-height analyzer, theta
creases pH and aragonite supersaturation results compensating slits, 0.5 mm 0.58. receiving slits, and
Borowitzka, 1986; Borowitzka and Larkum, 1977.. graphite-crystal monochromator. Peak positions were
The first-formed crystals are 1020 nm in size and corrected based on the internal fluorite standard and
randomly oriented. As calcification proceeds, arago- the mol% MgCO 3 determined using the nomogram
nite crystals act as nuclei for further aragonite pre- in Milliman 1974. after Goldsmith et al. 1961..
cipitation as significant rates of calcification could Because of their small size and addition of fluorite
be achieved even without photosynthesis, in the dark internal standard, the same foraminifera tests could
and in dead plants Borowitzka, 1982a, 1986; not be used for both XRD analyses and ICP analy-
Borowitzka and Larkum, 1976a,b.. As the segment ses.
ages, the number of crystals increases and crystal One large or two small Peneropolid foraminifera
length increases to 0.55 mm Wilber et al., 1969; tests and individual Halimeda segments were dis-
Borowitzka and Larkum, 1977; Hillis-Colinvaux, solved in 1 ml 10% nitric acid and analyzed for
1980; Multer, 1988.. Ca2q, Mg 2q, Sr 2q, and Naq by ICP-AES. Fresh
Textural changes in porcelaneous foraminifera Peneropolid foraminifera were rinsed in ethanol prior
tests and Halimeda algae segments have been shown to dissolution. Organic matter in fresh Halimeda
to begin while the organisms are still living Macin- segments was first removed by soaking in 5 wt.%
tyre and Reid, 1995, 1998, respectively.. Macintyre Na-hypochlorite overnight followed by several rinses
and Reid 1998. observed that the older portions of in doubly deionized H 2 O. The dissolved samples
living porcelaneous foraminifera Archaias angula- were analyzed using a combined simultaneousr
tus . are made up predominantly of anhedral, equant sequential Leeman Labs ICP-AES unit with 22 ana-
aggregates of crystals from 0.050.1 mm in diame- lytical channels. Raw mgrl data were converted to
ter, which they term AminimicriteB i.e., micrite ppm in solid material assuming Ca2q, Mg 2q, Sr 2q
- 1 mm in diameter; Folk, 1974.. Citing earlier were present as carbonate. Examination of the Naq
SEM observations of Debenay et al. 1996., Macin- data showed that contribution of Mg 2q or Sr 2q from
tyre and Reid 1998. interpreted this texture to result seawater was negligible relative to expected concen-
from the breakdown of original rod-shaped crystals trations in high Mg-calcite and aragonite, respec-
into the primary polycrystalline aggregates, which tively. It was assumed that Halimeda aragonite con-
originally formed the rods. Their interpretation im- tained less than 0.50 mol% MgCO 3 . Repeated checks
plies that crystal alteration results in a reduction of of standards resulted in a relative standard deviation
crystal size from rod shaped to equant minimicrite. in precision of 1.5% for Ca2q, 1.7% for Mg 2q, 4.9%
Similarly, Macintyre and Reid 1995. suggest that for Sr 2q, and 4.5% for Naq.
the elongate prismatic aragonite crystallites of Hal- Secondary electron SEM images were obtained on
imeda also undergo breakdown to their original com- ethanol-rinsed whole tests of fresh Peneropolid
posite polycrystalline aggregates. foraminifera tests and altered tests extracted from the
sediment to characterize outer surface features and
2.3. Geochemical and microbeam analyses diagenetic alteration. Individual foraminifera were
also broken open to image Mg-calcite crystallites on
Individual fresh and highly altered Peneropolid interior surfaces and cross-sections. Similarly,
foraminifera tests were analyzed by XRD methods to ethanol-rinsed individual segments of fresh Hal-
determine the composition mol% MgCO 3 . based on imeda from the growing tips and from the midsec-
change in lattice parameters as a function of Mg-con- tions of the plants were examined intact and along
broken and fractured cross-sections. Individual al- ments e.g., Mg. relative to heavier elements e.g.,
tered Halimeda segments were also broken open so Ca. occurs as grain thickness increases. Thus, the
that aragonite crystallites in the interior of the seg- apparent Mg-content of thick grains may be less than
ments could be examined in detail. The Peneropolid that of thin grains of the same composition by up to
tests and Halimeda segments were carbon-coated ; 10%. Also, the AEM-determined Mg composi-
and analyzed using a Hitatchi Model S-570 SEM. tions appeared to be systematically lower than XRD-
All secondary electron images were collected with or ICP-AES-determined compositions. Average
an accelerating voltage of 15 kV. Semi-quantitative mol% MgCO 3 and one-sigma standard error 1 sr6n.
energy-dispersive X-ray EDS. analyses were ob- were determined for each individual specimen ana-
tained using a Kevex Quantum energy dispersive lyzed.
X-ray analytical system operated at 15 kV accelerat- Length and width measurements were made on
ing voltage and ; 0.2 mA specimen current. After several hundred individual crystallites from fresh and
EDS analyses, some samples were gold-coated and altered Peneropolid foraminifera tests and Hal-
additional high-resolution secondary-electron images imeda algae segments using STEM photomicro-
were obtained. graphs of randomly selected crystallites on grain
Samples for STEM analyses were prepared as mounts. We assume that the sub-population of crys-
follows. Individual Peneropolid tests or single Hal- tallites measured is representative of the population
imeda segments were rinsed in ethanol and air-dried. of crystallites present in the whole allochem. In the
The individual tests or segments were gently crushed case of Peneropolid foraminifera, the measurements
and lightly disaggregated by ultrasonic vibration ; were made on four fresh individuals and on one or
15 s. in ; 2 ml of isopropyl alcohol. The dispersed two visibly altered individuals from each sediment
crystallites were collected onto a 3-mm lacy-C Cu- depth interval at the Florida Bay and Bahama Banks
grid. Grids were carbon coated and bright-field im- sites. In the case of Halimeda algae, measurements
ages were obtained on a Philips CM-12 STEM oper- were made on two segments taken from the midsec-
ated 120 kV. Dark-field images were obtained on tion of a living plant, and from two visibly altered
some foraminifera grain mounts to determine the segments from each of two sediment depth intervals
lattice continuity of overgrowth material see Peacor collected at the Bahama Banks Site. The average,
1992. and Busek 1992. for more detailed explana- median and the one-sigma standard error sr6n.
tion of TEM techniques.. were determined for combined data from all the
AEM chemical analytical data were obtained on specimens measured from each interval.
individual Mg-calcite crystallites in foraminifera tests
using a Kevex Quantum energy dispersive X-ray
analytical system in the scanning mode of the STEM, 3. Results
using a 5-nm diameter spot rastered over 50 nm2 .
Spectra were analyzed using the thin-film method of 3.1. Bulk allochem compositions
Lorimar and Cliff 1976.. K-ratios of Mg, Fe, and
Mn normalized to Ca were obtained using the CarSi, 3.1.1. ICP-AES analyses
MgrSi, FerSi and MnrSi K-values obtained on The Sr content of individual Halimeda algae
standards as described by Jiang et al. 1990.. Unfor- segments from live plants determined by ICP-AES
tunately, only semi-quantitative data for Sr concen- analyses range from 8485 to 9041 ppm averages
trations could be obtained due to spectral overlap of 8759 " 47. one-sigma standard error... These val-
Si-K a fluorescence from silica impurities in the car- ues are typical of green-algae compositions reported
bon grids. The grain mounts contained crystallites of in the literature e.g., Milliman, 1974; Rude and
somewhat variable thickness and the thin-film as- Aller, 1991.. The concentration of Sr in an altered
sumptions required for the K-ratio quantitative tech- Halimeda algae segment from the sediment column
niques may not hold for crystallites greater than is slightly lower 8288 ppm; Table 1. although not
; 300 nm thick e.g., Blake et al., 1984.. Preferen- substantially lower than the concentrations observed
tial adsorption of emitted X-rays from lighter ele- in the living specimens. More detailed study would
be required to determine whether significant Sr loss nifera tests from the sediment column generally have
occurs within altered Halimeda grains. The Sr con- lower Sr contents and the variability among analyses
tents of four fresh foraminifera tests average 1737 from a given interval increases relative to the fresh
ppm Sr "17. Table 1.. The most altered forami- specimens Table 1.. These results agree with the
data reported for Peneropolid foraminifera within
Table 1 analytical uncertainty e.g., Rude and Aller, 1991;
Compositions of Halimeda algae and Peneropolid foraminifera Carpenter and Lohmann, 1992..
determined by ICP-AES
The compositions of four individual fresh
Sample descriptions MgCO 3 mol%" Sr ppm" foraminifera tests determined by ICP-AES range from
standard error standard error
12.9 to 13.7 mol% MgCO 3 averages 13.2 " 0.2
A. Halimeda Algae mol%; Table 1.. This composition is in agreement
1. Living specimens
F1 - 0.50 8901
with compositions reported for Peneropolid forami-
F2 - 0.50 8779 nifera e.g., Rude and Aller, 1991; Carpenter and
F3 - 0.50 8898 Lohmann, 1992.. The compositions of individual
F4 - 0.50 8799 altered Peneropolid foraminifera tests from the sedi-
F5 - 0.50 8804 ment column exhibit a range in mol% MgCO 3 from
F6 - 0.50 8680
F7 - 0.50 8485
10.5 to 13.3 Table 1.. Within each interval, compo-
F8 - 0.50 8631 sitions of individuals vary by at least 12 mol%
F9 - 0.50 8661 suggesting an increase in compositional heterogene-
F 10 - 0.50 9041 ity as a result of variable degrees of alteration.
F 14 - 0.50 8661 Although there is no systematic trend in MgCO 3-
Average 8759"47
2. Sediment column specimens content with sediment depth Table 1., average
F 3032 cm - 0.50 8288 MgCO 3 content of altered foraminifera are 0.41.7
mol% lower than the average MgCO 3 content of
B. Peneropolid Foraminifera living foraminifera specimens Table 1..
1. Living specimens
F1 13.3 1708
F2 13.7 1710
F3 13.2 1779 3.1.2. XRD analyses
F4 12.9 1750 A single fresh Peneropolid test was found to
Average 13.3"0.2 1737"17 contain ; 14 mol% MgCO 3 Table 2., within the
2. Sediment column specimens
F 02 cm A 12.5 1571
compositional range reported for porcelaneous
F 02 cm B 11.7 1461 foraminifera based on similar kinds of XRD mea-
F 02 cm C 13.3 1629 surements Blackmon and Todd, 1959; Milliman,
F 02 cm D 11.6 1672 1974.. The average composition of altered foramini-
Average 12.3"0.4 1583"45 fera tests extracted from the sediment is slightly
B 02 cm A 10.5 2329
B 02 cm B 11.4 1800
lower than that of the fresh tests 10.513.1 mol%
B 02 cm C 11.7 1651 MgCO 3 . Table 2.. There is no consistent variation
B 02 cm D 12.7 1679 in MgCO 3 content with sediment depth Table 2., in
Average 11.6"0.4 1864"158 agreement with ICP-AES analyses. All of the XRD-
F 68 cm A 13.2 1609 based estimates of MgCO 3 content may be up to 0.5
F 68 cm B 12.8 1681
F 68 cm C 12.7 1689
mol% MgCO 3 too high because inhomogeneities and
F 68 cm D 12.9 1720 impurities in biogenic calcite cause shifts in lattice
Average 12.9"0.1 1675"23 parameters relative to synthetic high Mg-calcite stud-
B 1214 cm A 12.7 1732 ied by Goldsmith et al. 1961. e.g., Bischoff et al.,
B 1214 cm B 11.9 1861 1983.. The MgCO 3 compositions determined by
B 1214 cm C 11.7 1691
B 1214 cm D 12.5 1702
XRD agree with the average ICP-AES analyses for
Average 12.2"0.2 1746"39 foraminifera from a given interval within the esti-
mated errors in the analyses. Even though the XRD-
Table 2 are composed of a random intergrowth of indepen-

Comparison of Peneropolid foraminifera MgCO 3 composition dent prismatic rod-shaped. euhedral crystallites with
mol%.: ICP versus XRD
smooth crystal surfaces and blunt crystal termina-
Sample description Average ICP-AES" XRD a "5% error
tions Fig. 3D.. The rod-shaped crystallites range in
standard error
length from 0.5 to 1 mm and are less than ; 0.1 mm
Living specimen 13.3"0.2, ns 4 14.0"0.7, ns1
wide. The high-Mg-calcite composition of these
Altered: F 02 cm 12.3"0.4, ns 4 11.2"0.6, ns1
Altered: B 02 cm 11.6"0.4, ns 4 10.5"0.5, ns1 crystallites was verified by qualitative EDS analyses
Altered: F 68 cm 12.9"0.1, ns 4 13.1"0.6, ns1 on the SEM and by AEM analyses described in more
Altered: B 1214 cm 12.2"0.2, ns 4 12.5"0.6, ns1 detail below. Adjacent to the outer test surfaces and
a
interior chamber walls, the rod-shaped crystallites
After Goldsmith et al. 1961..
commonly form subparallel clusters with elongate
dimensions parallel to the wall surfaces. Similar
parallel arrangements of elongated crystallites were
and ICP-determined compositions do not agree abso- observed by Macintyre and Reid 1998..
lutely, both methods indicate the same trends in In other areas of the tests, also commonly adja-
MgCO 3 content of altered bulk foraminifera tests cent to chamber walls, the rod-shaped crystallites
from a given interval. Aragonite was not detected in form aggregates of grains up to 1 mm in diameter
any of the XRD scans of the foraminifera lower that appear to be lightly AweldedB together by an
detection limit of ; 0.51 wt.%; Peacor, personal intercrystalline overgrowth Fig. 3E.. Individual
communication.. rod-shaped crystallites, however, remain visible in
the aggregate in the samples examined in our study.
3.2. Ultratextural characterization Macintyre and Reid 1998. described similar aggre-
gates with variable evidence of original rod-shaped
3.2.1. Peneropolid foraminifera crystallites as AminimicriteB, and attributed the tex-
Peneropolid foraminifera are planispiral ture to progressive alteration and diagenesis of origi-
foraminifera, which grow up to 3 mm in diameter, nal rod-shaped crystals to more equant grains in
are covered with a smooth porcelaneous outer wall older sections of the living foraminifera.
punctuated with pseudopores 13 mm in diameter SEM images of altered foraminifera tests ex-
e.g., Towe and Cifelli, 1967; Blackmon and Todd, tracted from sediment show variable degrees of alter-
1959.. Secondary electron SEM images of the outer ation Fig. 3FJ.. The least-altered tests retain their
surface of fresh Peneropolid foraminifera tests show porcelaneous luster under the binocular microscope.
the smooth surface texture and the many fine pseu- At low magnification, the surface is smooth and the
dopores Fig. 3AC.. Even at the highest magnifica- fine pseudopore structure is visible. At higher magni-
tion, there is no evidence that the interiors of the fication, portions of the smooth outer test surface
tests are comprised of many individual elongate appear to have been partially removed as a result of
rod-shaped crystallites Fig. 3C.. The interior of the dissolution andror abrasion, revealing the interlock-
test is made up of many chambers separated by a ing meshwork of rod-shaped crystallites, which com-
lower basal layer, which formed on the preceding prise the test. Individual crystallites can be distin-
growth whorl, an upper septal wall, which forms the guished, but most grains appear to be lightly
roof of the last-formed growth whorl, and lateral AweldedB together by an intercrystalline over-
pillars, which divide the last-formed growth whorl growth. Extensively altered foraminifera tests Fig.
into smaller subchambers e.g., Hemleben et al., 3FJ. appeared chalky under the binocular micro-
1986.. These features have been described at the scope and portions of the outer surface are suffi-
SEM scale in some detail by Macintyre and Reid ciently eroded to reveal the inner chambered struc-
1998.. ture Fig. 3F,G.. At high magnification, individual
Secondary electron SEM images of fresh Pen- rod-shaped crystallites up to 1 mm long are visible;
eropolid tests, broken open to reveal cross-sections however, there is a greater amount of intercrystalline
of calcified interior walls, show that most of the tests material welding crystallites together. Some grains
have coalesced to form more equant aggregates 0.51 High magnification SEM images of highly altered
mm in diameter arrows, Fig. 3H.. foraminifera tests broken open to show interior
cross-sections show that the individual crystallites lightly welded together by a thin intercrystalline
are generally stubbier and more equidimensional than overgrowth are also present Fig. 4B.. A large range
in fresh specimens and crystal terminations are more in crystal length and smaller range in crystallite
rounded compare Fig. 3D with I.. There is also width is observed, as described in more detail below.
more intercrystalline material overgrowing and weld- Discrete spots in the SAED electron diffraction pat-
ing grains; individual rod-shaped grains are more terns inset, Fig. 4A. indicate that the rod shaped
difficult to distinguish and some grains coalesce to crystallites are well-ordered single crystals with
form aggregates ; 0.51 mm in diameter Fig. 3J.. elongated dimension parallel to the c )-crystallo-
Qualitative EDS analyses on SEM. and quantatative graphic direction.
AEM analyses on STEM. of individual crystallites Crystallites in altered Peneropolid foraminifera
described in more detail below, indicate that all the tests extracted from the sediment are still predomi-
crystallites and overgrowths are Mg-calcite. Reid et nantly rod-shaped but show evidence for dissolution
al. 1992. described similar diagenetic textures in in the irregular subhedral crystal shapes and rounded
Peneropolid foraminifera from the Belize shelf. Reid crystal terminations Fig. 4C,D.. The irregular dis-
and Macintyre 1998. further suggested that the al- solved crystallite surfaces are commonly overgrown
teration of rod shaped Mg-calcite crystallites to the by multiple layers of intercrystalline material - 510
more equant and welded AminimicriteB represented nm thick, which weld grains together to form larger
continued progressive diagenetic alteration initiated aggregates Fig. 4E,F.. The discrete spots in the
in older portions of living foraminifera e.g., Macin- SAED patterns of these dissolved grains are again
tyre and Reid, 1998.. consistent with well-ordered single crystals.
Grain mounts of gently disaggregated individual Dark-field images were obtained on several crys-
living and altered Peneropolid foraminifera tests tals with the concentric overgrowths to determine if
were examined by STEM methods to characterize the overgrowth grew in crystallographic continuity
the texture and structure of individual crystallites coherently. with the host Fig. 5.. The bright-field
comprising the tests. To our knowledge, this is the STEM image clearly shows the concentric over-
first study comparing fresh and altered crystallites at growth around the crystal Fig. 5A.. The absence of
this resolution. Bright-field STEM images of fresh multiple spots in the SAED pattern inset, Fig. 5A.
Peneropolid foraminifera tests show that crystallites indicates that the overgrowth must be coherent with
occur as euhedral, elongate rod-shaped to prismatic the host crystallite. This is confirmed by the dark-
grains -; 0.51 mm long, with smooth crystal field image Fig. 5B., which shows uniform illumi-
surfaces and blunt crystal terminations Fig. 4A,B.. nation across the entire crystal including the over-
Although individual crystallites are most common in growth. This uniform illumination requires that the
grain mounts, aggregates containing multiple grains overgrowth contributes to the observed diffraction
Fig. 3. Secondary electron SEM images of fresh AE. and altered FJ. Peneropolid foraminifera tests. A. Fresh Peneropolid test
Florida Bay site.. B. Enlargement shows the smooth outer porcelaneous surface covered by fine pseudo-pores. The ellipsoid shapes are
siliceous diatom epibionts. C. Even at highest magnification, the test surface and pore walls are smooth and no individual Mg-calcite
crystallites are visible. D. Broken interior surfaces of fresh Peneropolid tests are made up of individual independent Mg-calcite crystallites
with rod-like habits, smooth crystal surfaces and relatively blunt crystal terminations in random orientation. E. Fractured surface in a fresh
test near an interior chamber wall showing a subparallel interlocking network of euhedral Mg-calcite crystallites with many grains lightly
AweldedB together. F. Highly altered Peneropolid foraminifera test extracted from the sediment showing significant dissolution andrand
or abrasion of outer surface revealing inner chambered structure of the test. Bahama Banks site, 02 cm interval.. G. Enlargement of F.
showing complete absence of smooth outer test wall surface or fine pore structures observed in the living specimens. H. Further
enlargement shows interlocking meshwork of rounded subhedral stubby to equant Mg-calcite crystallites. Crystallites appear extensively
AweldedB together and some crystals have coalesced into larger irregular aggregates 0.51 mm in diameter arrow.. I. Broken interior
surface of altered Peneropolid test composed of stubby to equant subhedral Mg-crystallites with rounded crystal terminations Florida Bay
site, 68 cm interval.. J. Fractured surface in an altered test near an interior chamber showing that anhedral Mg-calcite crystallites are
strongly welded together and coalesce to form aggregates Florida Bay, 02 cm interval..
Fig. 4. TEM images of disaggregated Mg-calcite crystals from a fresh Peneropolid foraminifera tests AB. and from an altered
Peneropolid tests extracted from the sediments CF.. A. Mg-calcite crystallites in the fresh test are euhedral and prismatic with blunt
crystal terminations and smooth crystal surfaces. B. Cluster of euhedral elongate Mg-calcite crystallites from a fresh test lightly welded
together. The electron diffraction pattern inset in B. shows that the c ) crystallographic direction is parallel to the elongate direction of the
crystals. CD. Mg-calcite crystallites from altered tests are irregular in shape, and have rounded crystal terminations consistent with
dissolution. The c ) crystallographic direction is parallel to the elongate direction of the crystals electron diffraction pattern, inset in D.. E.
Some Mg-calcite crystals in altered tests show little evidence of dissolution, but are welded together by a thin rind of Mg-calcite - 10-nm
thick Florida Bay site, 68 cm interval.. F. In more highly altered tests, Mg-calcite crystals have irregular shapes consistent with
dissolution and are coated by a rind of Mg-calcite Bahama Banks site, 02 cm interval..
pattern. The combined bright field and dark field Mg-calcite crystallites are growing in lattice continu-
images indicate that overgrowths on the rod-shaped ity with the host and eliminates the possibility that
1980; Multer, 1988; Macintyre and Reid, 1995..

Secondary electron SEM images of the outer surface
of a fresh Halimeda segment with the outer organic
skin removed shows a series of bowl-shaped depres-
sions with a central channel that contained the utricle
filament. The depressions are lined with a network of
interlocking aragonite crystallites, which extend into
the interutricle pore space Fig. 6A,B..
Examination of cross-sections of broken segments
shows that crystals in the interutricle pore space are
euhedral with smooth, prismatic to bladed shapes
and blunt crystal terminations Fig. 6C.. Crystallites
are commonly pseudohexagonally twinned arrows,
Fig. 6C.. Aragonite crystallites from segments at the
growing tip of fresh Halimeda plants form random,
interlocking meshworks of euhedral, prismatic crys-
tals of fairly uniform size - 3 mm long and - 0.1
mm wide., all with sharp, blunt crystal terminations
Fig. 6D.. Crystallites in older plates from the mid-
sections of the plants retain the prismatic, blunt-ended
shape. However, there is a general increase in crys-
tallite lengths and widths, with some crystals attain-
ing 5 mm lengths and widths on the order of 0.10.5
mm compare Fig. 6C with D.. This increase in grain
size is considered to be the normal progression of
Fig. 5. A. Bright-field STEM image of Mg-calcite crystallites
calcification during maturation of older segments
from an altered Peneropolid foraminifera test with a thin over- Wilber et al., 1969; Borowitzka and Larkum, 1977;
growth of Mg-calcite determined by AEM.. The electron diffrac- Reid and Macintyre, 1998.. Clusters of small, euhe-
tion pattern inset. shows a single crystal calcite lattice with c ) dral, prismatic crystals - 0.5 mm long. are also
parallel to the elongate direction of the crystal. B. Dark-field associated with the larger crystals, and presumably
image of the crystallite shows uniform illumination across the
entire crystallite including overgrowth. indicating that the over-
form at new nucleation sites e.g., Wilber et al.,
growth is structurally continuous with the host crystal. 1969.. These textures and crystallite morphologies
are similar to those described for living Halimeda
specimens from the Bahama Banks Macintyre and
Reid, 1992. and Biscayne Bay, Florida Macintyre
the overgrowth is of different crystal structure e.g., and Reid, 1995.. Macintyre and Reid 1995. have
aragonite. or of significantly different chemical com- shown that aging of older segments in living Hal-
position e.g., low Mg-calcite.. imeda produces a range in aragonite grain size and
morphology similar to those observed here. How-
3.2.2. Halimeda algae ever, we did not observe the pervasive replacement
Halimeda algae consist of multiple calcified seg- of the elongate prismatic crystallites to more rounded
ments linked together by non-calcified filaments equant crystals - 0.5 mm. of minimicrite reported
utricles. and covered with a sheath of coalesced to be common in the mid-section and older segments
utricle filaments forming a thin organic skin. Calcifi- of living Halimeda by Macintyre and Reid 1995.
cation of the individual Halimeda segments involves and Reid and Macintyre 1998.. They interpreted this
filling of interutricle pore space with elongate pris- texture to be the result of alteration of original
matic aragonite crystallites Wilber et al., 1969; elongate prismatic aragonite crystallites while the
Borowitzka and Larkum, 1977; Hillis-Colinvaux, plant was still living.
Individual Halimeda segments extracted from the appearance and are extremely friable. Secondary
sediment show variable degrees of alteration under electron SEM images of the exposed surfaces of
the binocular microscope. Most grains have a chalky these altered Halimeda segments show that arago-
nite crystallites on the outer surface are generally show the euhedral, elongate, prismatic morphologies
finer grained - 1 mm, more stubby and equant, and and blunt crystal terminations identified by SEM
have rounded crystal terminations relative to crystal- Fig. 7A.. Individual crystallites have sharp, negative
lites on the surfaces of the living specimens. Individ- ALincoln LogB-like embayments Fig. 7A,B. that
ual Halimeda crystallites are sometimes welded to- were occupied by interlocking crystals in the intact
gether with overgrowths of subhedral ArhombsB of segment. There is a range in crystallite lengths and
carbonate forming aggregates -; 0.51 mm in di- widths described in more detail below. An enlarge-
ameter arrow, Fig. 6F.. Qualitative EDS analyses ment of an individual grain shows the smooth pris-
indicate Mg is present in many of these welded matic crystal surfaces, euhedral negative embay-
overgrowths and the welding material may be Mg- ments, blunt crystal terminations and absence of any
calcite. overgrowth Fig. 7B.. Individual aragonite crystal-
Examination of broken cross-sections of Hal- lites have uniform electron density down the length
imeda segments shows that in some areas, crystallite of the grain. Electron diffraction patterns are consis-
texture is indistinguishable from that of the living tent with single crystals and indicate the elongate
specimens. In other areas, the aragonite crystallites direction is parallel to the c )-crystallographic axis
show evidence of dissolution in the formation of and that crystallites lie generally with a ) in the
rounded to pointed crystal terminations, and pitted plane of the image.
grains with irregular surfaces Fig. 6G.. Interior Evidence for dissolution is ubiquitous in STEM
utricle surfaces, in particular, show the highest de- images of altered Halimeda segments extracted from
gree of alteration with severe rounding of aragonite the sediment Fig. 7CF.. Crystallites are more ir-
crystal terminations, etching of crystal surfaces, and regular, and are shorter and wider on average Fig.
precipitation of a Mg-free confirmed by EDS. over- 7C.. Individual crystallites show rounding of blunt
growth on the rounded and corroded aragonite crys- crystal terminations, and extensive dissolution along
tallites Fig. 6H.. No Mg-calcite was observed in the grain edges and embayments Fig. 7D.. Rare crys-
interior of altered aragonite segments. EDS analyses tallites of Mg-calcite with rhombohedral crystal
could not confirm whether the overgrowth was arag- surfaces are associated with some aragonite-crystal
onite or low Mg-calcite, but STEM analyses de- aggregates but do not directly replace aragonite crys-
scribed below indicate the overgrowth is aragonite. tallites. Other images show evidence of precipitation
Grain mounts of gently disaggregated fresh and Fig. 7E,F.. Subhedral grains with irregular shapes
altered Halimeda segments were examined by suggestive of dissolution are overgrown by several
STEM. The bright-field STEM images of aragonite concentric layers - 10-nm thick of crystalline mate-
crystallites from fresh Halimeda segments clearly rial that AweldB several grains together to make
Fig. 6. Secondary Electron SEM images of the fresh AD. and altered EH. Halimeda algal segments from the Bahama Banks site. A.
Image of the outer surface of a fresh Halimeda plate with the organic skin removed, showing interlocking network of aragonite crystals
filling interutricle pore spaces and lining utricle filament channels. B. Enlargement of A. showing random orientation of the aragonite
crystallites. C. Further enlargement shows aragonite crystallites are euhedral, prismatic to bladed, and have blunt crystal terminations and
smooth crystal surfaces. There is a range in crystal length and width in mature segments. Some grains are pseudohexagonally twinned
arrows.. D. Aragonite crystallites from the growing tip of a young segment of fresh Halimeda are uniform in size, euhedral and prismatic,
and have blunt crystal terminations and smooth surfaces. E. Low magnification image of the outer surface of an altered Halimeda segment
showing randomly oriented stubby to equant interutricle aragonite crystallites. Utricle pores are coated with similar crystals 02 cm
interval.. F. Magnification shows the short, stubby aragonite crystallites have rounded crystal terminations and irregular surfaces,
suggesting dissolution or replacement of originally prismatic grains. Rhombs of Mg-calcite crystals arrow. are sometimes observed.
Aragonite crystals coalesce to form anhedral clumps - 0.5 mm in diameter on the outer surface of some altered Halimeda grains 1214
cm interval.. G. Aragonite crystals from an altered Halimeda segment have rounded crystal terminations arrows. and irregular grains
shapes consistent with dissolution. There is a range in crystallites length and width similar to those of the fresh specimen shown in C. 02
cm interval.. H. Exposed utricle surface from the interior of an altered Halimeda segment with an aragonite overgrowth welding
crystallites together 1214 cm interval..
Fig. 7. TEM images of disaggregated aragonite crystals from midsection segments of fresh Halimeda AB. and from altered Halimeda
segments extracted from the sediments CF., Bahama Banks site. A. Aragonite crystallites from fresh Halimeda segments are euhedral,
prismatic, and have blunt crystal terminations and sharp ALincoln LogB-like embayments formerly occupied by interlocking crystals in the
living specimen arrows.. Note the wide range of crystal dimensions typical of moderately mature segments. B. A single, euhedral
aragonite crystal from a fresh segment, with smooth prismatic crystal surfaces and sharp embayments. The electron diffraction pattern inset
in B. is consistent with a single crystal which is elongated in the c ) crystallographic direction. C. Aragonite crystallites from altered
segments are generally stubbier, sub-to anhedral, and have rounded crystal terminations and irregular surfaces 1214 cm interval.. D. A
single aragonite crystallite from an altered segment showing significant dissolution at crystal terminations, along prismatic edges, and in
embayments 02 cm interval.. The electron diffraction pattern inset in D. is consistent with single crystal. E. Sub-to anhedral aragonite
crystal from an altered Halimeda segment showing evidence of dissolution, followed by overgrowth of concentric layers of aragonite - 10
nm thick. Single, sharp electron diffraction spots in the electron diffraction pattern inset. are consistent with an aragonite overgrowth in
lattice continuity with the host 1214 cm interval.. F. Aggregate of irregular dissolved aragonite crystallites from an altered Halimeda
segment showing several concentric layers of aragonite overgrowths 1214 cm interval..
aggregates Fig. 7F.. AEM analyses of these over- either aragonite or low-Mg-calcite. The absence of
growths did not detect any Mg, suggesting they are multiple diffraction spots in SAED patters of over-
grown grains inset, Fig. 7E., however, implies that ses is too large to resolve the - 10 nm thick over-
the overgrowths are coherent with the host and are, growths, which commonly rim crystallites in the
therefore, aragonite.
3.3. AEM analyses of Mg-calcite crystallites
The composition of hundreds of individual crys-

tallites from several specimens of fresh and altered
Peneropolid foraminifera were determined by AEM
methods. Individual analyses, expressed as mol%
MgCO 3 , are shown in the histograms in Fig. 8. The
averages of multiple analyses from individual speci-
mens and the overall averages for each interval are
reported in Table 3. Inspection of the data shows that
even though average compositions of the fresh and
the altered specimens from the sediment column are
not significantly different, there is an overall increase
in the variability of MgCO 3 content in altered Pen-
eropolid specimens relative to fresh specimens. This
increase in variability is measured as an increase in
the variance of the data Table 3., which is highest
for foraminifera from the deepest sample Fig. 8D..
Individual AEM analyses of Mg-calcite crystal-
lites in fresh specimens of Peneropolid foraminifera
range from 7 to 14 mol% MgCO 3 Fig. 8A.. This
wide range may reflect inhomogeneity among crys-
tallite compositions resulting from precipitation
within microenvironments within the living Pen-
eropolid with slightly different compositions. A small
component of the variance may be due to differences
in crystallite thickness as described in Section 2. The
overall average of 144 analyses from three individu-
als is 11.5 "0.2. mol% MgCO 3 .
The MgCO 3 content of Mg-calcite crystallites
from altered foraminifera extracted from the sedi-
ment column have a larger range in composition than
fresh samples Fig. 8BD; Table 3.. Crystallites with
nearly pure CaCO 3 compositions were present in
some altered tests Fig. 8B,D.. The average composi-
tions of the 02, 68 and 1214 cm intervals are
10.6 " 0.2, 11.6 " 0.3 and 11.3 " 0.4 mol% MgCO 3 , Fig. 8. Histograms showing the frequency distribution of the
respectively. Within each interval, individual tests mol% MgCO 3-content of individual crystallites in several fresh
A. and altered BD. Peneropolid foraminifera tests, as deter-
with average compositions of about 12 mol% MgCO 3
mined by AEM. Although the average MgCO 3 -content does not
coexist with individual tests with average crystallite vary significantly with burial depth, the variance or spread. in
compositions of about 10 mol% MgCO 3 . Unfortu- data increases significantly from the living specimens to the
nately, the 50 nm2 areas used to obtain AEM analy- altered specimens.
Table 3
Magnesium composition mol%. determined by AEM
Sample description No. of Average MgCO 3 " Standard Variance
analyses Standard error deviation
(1) Peneropolid liing specimens
FA 11 12.0 " 0.63 2.09 4.38
FB 55 12.0 " 0.25 1.87 3.50
FC 78 11.0 " 0.20 1.78 3.18
Average all specimens 144 11.5 " 0.16 1.89 3.57
(2) Peneropolid altered specimens

F 02 cm A 17 10.8 " 0.38 1.56 2.42
F 02 cm B 61 12.4 " 0.31 2.05 4.41
B 02 cm A 19 10.9 " 0.45 1.98 3.91
B 02 cm B 68 9.6 " 0.34 2.79 7.78
Average 02 cm interval 165 10.6 " 0.20 2.58 6.64
F 68 cm A 15 10.0 " 0.51 1.97 3.86
F 68 cm B 56 12.1 " 0.29 2.19 4.81
B 1214 A 25 11.9 " 0.39 1.93 3.75
B 1214 B 52 11.1 " 0.58 4.26 19.77
B 1214 C 11 10.5 " 0.60 1.98 3.94
(3) Mg-calcite with Halimeda specimens

Living specimen 1 13.6
F 02 3 11.3 " 0.84 1.46 2.14
B 1214 4 12.1 " 1.90 3.81 14.52
altered specimens. MgCO 3 contents up to 5 mol% A few AEM analyses of Mg-calcite crystallites in
lower than the interior of the grains were commonly grain mounts of fresh and altered Halimeda seg-
measured at the outer edges of individuals, however. ments were also obtained Table 3.. The average
Table 4
Dimensions of aragonite crystallites in Halimeda algae and Mg-calcite crystallites in Peneropolid foraminifera nanometers.
Sample description No. of No. of Average length" Median length" Average width" Median width "
individuals analyses standard error standard error standard error standard error
(A) Peneropolid Foraminifera
Living specimens 4 510 280 " 9 222 " 9 56 " 1 53 " 1
Altered: F 02 cm 2 236 270 " 12 209 " 12 78 " 3 68 " 3
Altered: B 02 cm 1 248 287 " 15 217 " 15 76 " 2 71 " 2
Altered: F 68 cm 2 210 254 " 14 192 " 14 72 " 2 67 " 2
Altered: B1214 cm 2 243 353 " 15 294 " 15 118 " 4 111 " 4
(B) Halimeda Algae

Living specimens 2 280 695 " 38 502 " 38 149 " 5 138 " 5
Altered: B 02 cm 2 101 786 " 102 521 " 101 192 " 11 167 " 11
Altered: B 1214 cm 2 367 462 " 17 382 " 17 174 " 5 154 " 5
compositions range from 11.3 to 13.6 mol% MgCO 3 , Mg-calcite crystallites in Peneropolid foraminifera
and are similar to the composition range reported for tests. No genetic relationship of the Mg-calcite to
Fig. 9. Histograms showing the frequency distribution of Mg-calcite crystallite lengths AD. and widths EH. measured on STEM
photographs of gently disaggregated Peneropolid foraminifera tests. A. Frequency distribution of crystallite lengths in living specimens.
BD. Frequency distribution of crystallite lengths in altered sediment-column specimens. E. Frequency distribution of crystallite widths in
living specimens. FH. Frequency distribution of crystallite width in altered sediment-column specimens. Living specimens were collected
at the Florida Bay Site and altered samples from the Florida and Bahama Banks Sites.
Halimeda alteration is implied, but the compositions minifera tests were determined and compared with
are typical of Mg-calcite cement inorganically pre- similar measurements obtained from highly altered
cipitated from present-day seawater e.g., Mucci, foraminifera tests Table 4.. Length and width data
1987.. are shown as histograms in Fig. 9. The size distribu-
tions are generally log-normal in general appearance.
3.4. Crystallite size distributions
Median and average crystallite lengths "one-sigma
3.4.1. Peneropolid foraminifera standard error. are reported in Table 4. The average
Length and width measurements of individual crystallite length is 280 " 9 nm Fig. 9A. and the
Mg-calcite crystallites from fresh Peneropolid fora- average width is 56 " 1 nm Fig. 9E.. Grains as long
Fig. 10. Histograms showing the frequency distribution of aragonite crystallite lengths AC. and widths DF. measured on STEM
photographs of gently disaggregated Halimeda algae segments. A. Frequency distribution of crystallite lengths in living specimens. BC.
Frequency distribution of crystallite lengths in altered sediment-column specimens. D. Frequency distribution of crystallite widths in living
specimens. EF. Frequency distribution of crystallite width in altered sediment-column specimens. All specimens were collected at the
Bahama Banks Site.
as 1400 nm and as short as 55 nm were present. The 4. Discussion

maximum width is ; 130 nm.
The average length of Mg-calcite crystallites in 4.1. Ultratextural eidence for dissolution and pre-
altered foraminifera tests from the 02 cm intervals cipitation
287 " 15 nm, B02; 270 " 15 nm, F02. and the
68 cm interval 254 " 14. are not statistically dif- Mg-calcite crystallites in Peneropolid foramini-
ferent from the average length of unaltered speci- fera tests show a large variety of dissolution and
mens Fig. 9, Table 4.. However, the average length precipitation textures when examined at the resolu-
of crystallites from foraminifera from the deepest tion of the STEM. Documentation of such features at
1214 cm interval increases to 353 " 14 nm Fig. this scale has not been previously described. Many
9D; Table 4.. The average Mg-calcite crystallite crystallites show evidence of dissolution; crystallite
width in altered foraminifera tests is larger than that terminations are more rounded, and crystallite sur-
of unaltered specimens. The average crystallite faces are pitted and irregular Fig. 4C,D.. Some of
widths in the two 02 cm interval samples are these crystallites lack significant overgrowths Fig.
76 " 2 nm B02. and 78 " 3 nm F02. and for the 4D.. Other grains appear relatively unaltered and
68 cm interval is 72 " 2 nm Fig. 9F,G; Table 4.. retain their smooth crystal surfaces Fig. 4E..
The average Mg-calcite crystallite width in the deep- Evidence of precipitation is found in the presence
est 1214 cm interval is increased to 118 " 4 nm of intercrystalline overgrowths welding crystallites
Fig. 9H; Table 4.. together, which are thicker than those observed in
living specimens Fig. 4E.. Some crystallites show
3.4.2. Halimeda little evidence of dissolution prior to development of
Length and width measurements of individual the overgrowths, whereas other crystallites have ob-
aragonite crystallites from fresh versus altered Hal- viously been partially dissolved and corroded prior
imeda segments from the Bahama Banks site are to overgrowth development Fig. 4F.. These varia-
compared in Table 4 and Fig. 10. The median arago- tions are consistent with observations at the SEM
nite crystallite length in fresh segments is 695 " 38 scale, which show that in a given test, a variety of
nm Fig. 10A.. The frequency distribution of crystal- alteration textures are present. The most highly
lite lengths ranges from 70 to 4000 nm, with a welded textures appear on the exterior surfaces of
maximum frequency at ; 200 nm. The average the tests Fig. 3H. or adjacent to interior chambers.
aragonite crystallite width is 149 " 4 nm Fig. 10D. The crystallites which make up the interior walls of
with a range from 58 to 450 nm. the test have greater degrees of preservation of origi-
The average aragonite crystallite length in highly nal rod-shaped crystallites and less intercrystalline
altered Halimeda segments extracted from the 02 material welding crystallites together Fig. 3I,J..
cm interval is larger 786 " 102 nm; Fig. 10B. than Similarly, the STEM observations of altered arag-
in the fresh sample. However, the relatively large onite Halimeda algae segments show dissolution and
error due to the small number of measurements precipitation textures analogous to those observed in
suggests that there is statistically no difference from Peneropolid foraminifera tests. In the most visibly
the unaltered specimens. The average crystallite altered segments, dissolution of aragonite crystallites
length of 462 " 17 in altered segments from the is evident in the rounding of originally blunt crystal
1214 cm depth interval is statistically smaller than terminations, the shortening of some crystals, and the
that of the fresh sample. However, large individual pitting of crystal surfaces Fig. 7DF.. Many of
crystallites up to 5000 nm are present in this sample. these corroded crystallites lack overgrowths e.g.,
The median crystallite width of crystallites from the Fig. 7D., whereas other crystallites with obvious
altered segments increase to 192 " 11 nm 02 cm dissolution textures are, in turn, overgrown by con-
interval. and 174 " 5 nm 1214 cm interval. Fig. centric layers of aragonite Fig. 7E,F.. Still other
10E,F; Table 4.. crystallites are little affected by dissolution, but in-
tercrystalline overgrowths weld several grains to- there is strong substrate control on the mineralogy of
gether. These morphological variations are also con- the precipitating overgrowths e.g., Alexandersson,
sistent with observations at the SEM scale, which 1972; Mucci and Morse, 1983; Walter, 1985; Burton
show that the highest degree of alteration, whether and Walter, 1987, 1991; Zhong and Mucci, 1989..
dissolution or precipitation, was observed either on On the larger scale, bioturbated sediments of the
external surfaces of Halimeda segments Fig. 6E,F., Florida Bay and Bahama Bank sites have porewater
or on utricle surfaces in grain interiors Fig. 6H.. microenvironments with variable mass transfer rates
Other areas of the same segments showed little depending on proximity to open burrows, organic
evidence for significant dissolution or precipitation. matter, and oxygenation e.g., Aller, 1982a,b.. Sedi-
The solubility of biogenic aragonite and Mg- ment allochems may alternatively be affected by
calcite with ; 1113 mol% MgCO 3 are approxi- sulfate reduction during isolation from overlying wa-
mately the same e.g., Walter and Morse, 1984a.. ter, or by sulfide oxidization when oxygen is intro-
The degree of crystallite alteration via dissolution or duced through sea grass roots or via burrow net-
precipitation within a foraminifera test or algae seg- works. The saturation state of the porewaters with
ment is controlled by mass transfer rates with exter- respect to aragonite and Mg-calcite varies with the
nal porewaters. The experiments of Walter and Morse extent of SO42y reduction or sulfide oxidation e.g.,
1985. showed that, despite the large total BET-de- Morse et al., 1985; Berner and Westrich, 1985;
termined surface areas of Peneropolid foraminifera Walter and Burton, 1990; Walter et al., 1993; Rude
2.5 m2rg. and Halimeda algae 2.04 m2rg., only and Aller, 1991.. The overall variability and appar-
; 3.5% and 8% of the total surface area in each ent decrease in AEM-determined MgCO 3-content of
allochem, respectively, participates in dissolution re- Mg-calcite crystallites in altered foraminifera tests
actions. Walter and Morse 1984b. suggested that may be due to increased PCO 2 within sediment pore
grain interiors may be isolated to varying degrees waters during microbial respiration. Burton and Wal-
and cannot exchange readily with bulk solutions. ter 1991. showed that increasing PCO 2 will result in
This supported by our SEM observations that it is a decrease in MgCO 3-content of precipitating Mg-
the outer surfaces and interior surfaces adjacent to calcite from a solution of given Mg 2qrCa2q ratio.
open chambers in Peneropolid foraminifera tests, or Decrease in MgCO 3 content is expected with de-
utricle surfaces in Halimeda algae segments, which crease in temperature Burton and Walter, 1987,
exhibit the greatest change in grain size and largest 1991; Mucci, 1987., again consistent with the ex-
proportion of intercrystalline material welding grains pected trend in sediment porewaters versus overlying
together. Interior portions of the grains removed waters. Taken together, the variety of dissolution and
from these surfaces generally appear least altered. precipitation textures observed by STEM methods is
Microenvironments of different carbonate solubil- completely consistent with the variation in the pore-
ity may exist within the sediment allochems. For water geochemical environment.
example, increase in PCO 2 in isolated interior com-
partments due to the decay of biologic tissues may 4.2. Implications for crystal growth
increase carbonate solubility. Eventually, the buildup
of alkalinity and dissolved Ca2q supersaturation pro- The length and width data of Mg-calcite crystal-
mote precipitation. Because of their similar solubili- lites in Peneropolid and aragonite crystallites in
ties or saturation states in these pore fluids, the Halimeda document significant changes in crystal
precipitation of either aragonite or Mg-calcite of dimensions, which occur during the earliest stages of
; 1113 mol% MgCO 3 may occur. The presence of sediment diagenesis. We hypothesize that during dia-
overgrowths of only Mg-calcite in Peneropolid genesis in these modified porewaters, original bio-
foraminifera tests and aragonite in Halimeda algae genic crystallites are transformed via inorganic crys-
segments, as confirmed by the combined tal growth processes which act to lower the surface
STEMrAEM and electron diffraction analyses of free energy of crystallites by producing more equant
individual crystallites and the SEM, XRD and ICP- and larger crystals e.g., Chai, 1974; Baronnet, 1982;
AES analyses of individual allochems, suggests that Morse and Casey, 1988..
Our STEM observations of relatively uniform genesis of these organisms, it is expected that smaller
electron density down the length of individual Mg- crystals will be consumed by dissolution and larger
calcite or aragonite crystallites in living specimens, crystals will grow by precipitation. It is also ex-
and the presence of sharp spots in electron diffrac- pected that that the elongated crystal habits of both
tion patterns, indicate that the original crystallites in the Mg-calcite and the aragonite will become more
both of these organisms are composed of well- equant in shape by dissolution at tips of grains and
ordered, coherent, single crystals. Our STEM obser- by precipitation on the planar crystal surfaces. These
vations further suggest that irregular and bumpy trends are required in order for the surface free
surfaces are the result of dissolution in portions of energy of the crystals to be reduced, especially in the
crystallites coupled with precipitation in other por- case of Mg-calcite where rhombohedral crystal habits
tions e.g., Figs. 4C and 6E. or as intercrystalline are typical.
welding overgrowths e.g., Figs. 4CF and 6EF.. If Ostwald ripening occurs, the frequency distri-
Our observations are consistent with those of Macin- bution of crystal sizes broadens, and the average
tyre and Reid 1995, 1998. who concluded that crystal-size increases with time e.g., Baronnet,
Mg-calcite crystallites in living porcelaneous 1982.. In the case of Peneropolid foraminifera, the
foraminifera and in living Halimeda algae display a frequency distributions of crystallite lengths mea-
range in textures from elongate crystallites to moder- sured for the living specimens and for the 02 and
ately welded aggregates. Our data, however, are not 68 cm depths are relatively constant at 270 " 20
consistent with their assertion that the normal pro- nm within the errors of measurement Fig. 9; Table
gression of alteration is toward decrease in size. 4.. In the deepest interval, the average length in-
creases significantly to 353 " 15 nm. Average crys-
4.2.1. Crystal growth during Peneropolid tallite widths increase from 56 " 1 nm in the living
foraminifera and Halimeda algae diagenesis specimens to 75 " 5 nm in the shallow intervals and
Inorganic crystal growth often follows an to 120 " 4 nm in the deepest interval Fig. 9; Table
AOstwald ripeningB process, in which the smaller 4.. The increase in both median length and width
crystals in an aggregate in contact with solution with increasing depth, coupled with observations of
dissolve and larger crystals grow e.g., Chai, 1974, alteration, suggests that carbonate material was added
1975; Baronnet, 1982; Morse and Casey, 1988.. The to both dimensions, consistent with crystal ripening
process is driven by thermodynamic constraints to processes. Furthermore, the increase in crystallite
minimize the surface free energy of crystals. The width is proportionately larger than the increase in
theory applies only to closed systems at constant length, indicating crystals were becoming more
temperature and pressure e.g., Baronnet, 1982 and equant in shape.
references therein.. Smaller crystals have higher sur- Similar trends were observed for crystal-size dis-
face free energies and increased solubilities in a tributions of aragonite in Halimeda algae segments.
given solution relative to larger crystals. In systems The average crystallite lengths in the living speci-
undergoing Ostwald ripening, crystals larger than a mens and the altered specimens from the shallow
the critical radius, which is in AequilibriumB with the 02 cm interval are approximately the same ; 700
saturation state of the solution, continue to grow at " 100 nm within error of measurement Fig. 10;
the expense of those crystals smaller than the critical Table 4.. However, in the deepest interval, the aver-
radius, which dissolve. age length decreases to 460 " 58 nm. The average
Although the nucleation processes, which first crystallite width increases from 150 " 5 nm in fresh
form the rod-shaped Mg-calcite crystallites in Pen- segments to 170190 " 10 nm in the altered speci-
eropolid foraminifera and elongate prismatic arago- mens from both depth intervals Fig. 10; Table 4..
nite crystallites in Halimeda, are poorly understood, The crystallite width distributions, in particular,
the subsequent growth of crystals in the living organ- broaden and flatten. The decrease in crystallite length
isms has been described as similar to inorganic with alteration is consistent with dissolution at the
crystal growth e.g., Lowenstam and Weiner, 1989.. tips of elongate crystals and the increase in crystal-
If Ostwald ripening processes control the early dia- lite width indicates that material is being precipitated
on planar crystal surfaces. This pattern cannot be the

result of simple physical breaking of the crystallites,
which would only result in shortening of the crystals.
The combined data suggest that aragonite crystallites
thicken and become more equant in shape, consistent
with reduction in surface free energy.
A necessary condition for Ostwald ripening is that
the normalized frequency distributions e.g., fre-
quencyrmaximum frequency versus sizeraverage
size. approach steady state with time Chai, 1974,
1975; Baronnet, 1982.. In other words, even though
the frequency distributions broaden and the absolute
average of the distribution increases, the distribution
normalized to the average size remains the same
shape. The average radius corresponds approxi-
mately to the critical radius, which was discussed
above. Information about the crystal growth mecha-
nism can be inferred from the shape of the frequency
distribution as shown by the theoretical curves plot-
ted in Fig. 11 Chai, 1974, 1975; Baronnet, 1982;
Morse and Casey, 1988.. Crystal growth mecha-
nisms governed by volume diffusion or first-order
kinetics have maximum frequencies at radius ratios
greater than one Fig. 11.. Growth mechanisms gov-
erned by second order kinetics screw-dislocation
growth. and higher-order kinetics have maximum
frequencies at radius ratios less than one Fig. 11..
Fig. 12. Normalized frequency distributions for Mg-calcite crystal-
lites plotted as a function of normalized lengths A. and normal-
ized widths B.. Fresh samples are compared with most altered
samples B1214 cm interval.. The curve for an ideal second-order
size distribution is shown for reference. The superposition of the
data from fresh and altered specimens suggests processes consis-
tent with inorganic crystal growth, which follows a second- or
higher-order kinetics, are responsible for the increases in both
crystal length and width with increasing burial depth.
Normalized frequency distributions of length and

width were calculated for both Mg-calcite crystallites
in Peneropolid foraminifera Fig. 12. and aragonite
crystallites in Halimeda algae Fig. 13.. For clarity,
only the data from the living specimens and the
1214 cm interval most altered. are plotted. The
Fig. 11. Ideal normalized frequency distributions plotted as a distributions of normalized size data of crystallites
function of normalized crystal radius for various growth mecha- from fresh and most altered specimens overlap and
nisms after Chai, 1975.. Note that the maximum in the frequency are reasonably consistent with steady-state size dis-
distribution for both diffusion and first order surface-kinetic con-
trolled growth plot at normalized radius ratios greater than one.
tributions required of inorganic Ostwald ripening
Second order screw dislocation. and higher order maxima plot at processes. In all cases, the frequency maximum oc-
radius ratios less than one. curs at values less than one, consistent with kinetics
precipitation kinetics resulted in reaction orders of

; 22.5 at temperatures of ; 25558C Burton and
Walter, 1987; Zhong and Mucci, 1989.. Experimen-
tal studies of dissolution kinetics give reaction orders
of ; 2.5 for biogenic Mg-calcite and of ; 2.5 for
aragonite Walter and Morse, 1984a,b, 1985; Walter,
1986..
The shapes of the normalized length and width
distributions obtained for Mg-calcite and aragonite
crystallites in both living and altered Peneropolid
tests Fig. 11. and Halimeda algae segments Fig.
12. are consistent with theoretical shapes of the
normalized frequency distribution for inorganic, sur-
face-controlled Ostwald-ripening reactions with reac-
tion orders of 2 or more. e.g. Chai, 1975; Morse and
Casey, 1988 and references therein.. The crystallite
length and width distributions are typical of distribu-
tions for inorganically precipitated synthetic calcite
and suggest that the organisms role in calcification
of these biogenic allochems is in provision of nucle-
ation sites and promotion of Mg-calcite or aragonite
supersaturation. Once crystals are nucleated in this
favorable environment, crystal ripening typical of
inorganic surface-controlled processes such as Ost-
wald ripening takes place. Even though there is a
change in the absolute crystallite length and width
dimensions in altered specimens as a result of both
Fig. 13. Normalized frequency distributions for aragonite crystal-
dissolution and precipitation during subsequent dia-
lites plotted as a function of normalized lengths A. and normal-
ized widths B.. Fresh samples are compared with most altered genesis, the normalized frequency distributions are
samples B1214 cm interval.. The curve for an ideal second-order constant within error of analysis. Thus, the necessary
size distribution is shown for reference. There is more scatter in steady-state requirements for size distributions re-
the data and deviation from the ideal crystal growth curve than quired of Ostwald ripening crystal growth are met.
was observed for Peneropolid data suggesting additional pro-
cesses such as crystal breakage might be occurring. The overall
superposition of fresh and altered specimen data suggests pro-
4.3. Implications for geochemical studies of carbon-
cesses consistent with inorganic crystal growth are responsible for
the increases in both crystal length and width with increasing ate diagenesis
burial depth. The normalized distributions are consistent with
inorganic ripening processes governed by second- or higher-order
The early alteration of biogenic allochems within
reactions.
the upper 25 cm of carbonate platform sediments as
shown by textural evidence for dissolution of and
with reaction orders greater than one Chai, 1974, precipitation on aragonite and Mg-calcite crystallites
1975; Baronnet, 1982; Morse and Casey, 1988 and in biogenic allochems determined by STEM, com-
references therein.. bined with the previously determined data char-
Experiments relating to reaction kinetics of pre- acterizing geochemical changes in substrate and
cipitation of Mg-calcite from seawater suggest that porewater composition, have several significant im-
reaction orders were ; 2.5 Mucci and Morse, 1983; plications for the study of sediment diagenesis. Dis-
Burton and Walter, 1991; Hartley and Mucci, 1996.. solution of the most abundant andror most reactive
Similarly, experimental determinations of aragonite sediment allochem at a given saturation state may
buffer both the trace element and isotopic composi- by the Robert B. Mitchell Fund, Department of
tions of porewaters. Precipitation of carbonate from Geological Sciences, University of Michigan.
these porewaters as overgrowths on individual crys-
tallites in biogenic components necessarily alters the
trace element and isotope composition of those com-
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Early Marine Diagenesis of Biogenic Aragonite and Mg-Calcite

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Early Marine Diagenesis of Biogenic Aragonite and Mg-Calcite

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Chemical Geology 175 2001.

Early marine diagenesis of biogenic aragonite and Mg-calcite:

1. Introduction porewaters buffering pH to values near 7 Ben

Sediment aliquots were refrigerated until they

2.2. Calcification in liing Peneropolid foraminifera

Calcification of living Peneropolid foraminifera

Table 2 are composed of a random intergrowth of indepen-

1980; Multer, 1988; Macintyre and Reid, 1995..

3.3. AEM analyses of Mg-calcite crystallites

The composition of hundreds of individual crys-

(2) Peneropolid altered specimens

(3) Mg-calcite with Halimeda specimens

(B) Halimeda Algae

as 1400 nm and as short as 55 nm were present. The 4. Discussion

on planar crystal surfaces. This pattern cannot be the

Normalized frequency distributions of length and

precipitation kinetics resulted in reaction orders of

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