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Carbonates Evaporites

DOI 10.1007/s13146-015-0283-0

ORIGINAL ARTICLE

A study of carbonate beach sands from the Yucatan Peninsula,


Mexico: a case study
J. J. Kasper-Zubillaga1 E. Arellano-Torres2 J. S. Armstrong-Altrin1
A. N. Sial3

Accepted: 16 November 2015


Springer-Verlag Berlin Heidelberg 2015

Abstract Sedimentological, geochemical, and X-ray


diffraction (XRD) analyses in addition to the determination
of biogenic fraction components (BFC) were performed in
mollusk shells from carbonate beach samples collected on
the northern coast of the Yucatan Peninsula, Mexico. The
most abundant components of the BFC were bivalves and
gastropods shells, ranging from 88.1 to 99.2 % and from 0.1
to 6.0 %, respectively, followed by minor percentages of
foraminifera, coral fragments, bryozoa, oolites, spicules,
and ostracods. A combination of major element, trace element, and XRD techniques were performed to show how
the Mg/Ca and Mg/Sr ratios determine the possibility of a
recrystallization process in bivalves and gastropods, which
may be attributed to early diagenetic mechanisms caused by
groundwater flows, subaerial exposure, high evaporation
rates, and neomorphism. The rare earth element analyses
gave the average anomalies for the following ratios (Pr/
Yb)PAAS and MuQ ratio [ 1, (Eu/Eu*)PAAS and MuQ and (Ce/
Ce*)PAAS and MuQ \ 1, suggesting little incorporation of sea
Electronic supplementary material The online version of this
article (doi:10.1007/s13146-015-0283-0) contains supplementary
material, which is available to authorized users.
& J. J. Kasper-Zubillaga
kasper@cmarl.unam.mx
1

Instituto de Ciencias del Mar y Limnologa, Unidad de


Procesos Oceanicos y Costeros, Universidad Nacional
Autonoma de Mexico, Circuito Exterior s/n, 04510 Mexico,
D.F., Mexico

Facultad de Ciencias, Universidad Nacional Autonoma de


Mexico, Circuito Exterior s/n, 04510 Mexico, D.F., Mexico

Nucleo de Estudos Geoqumicos e Laboratorio de Isotopos


Estaveis (NEG - LABISE), Departmento de Geologia,
Universidade Federal de Pernambuco, Caixa Posta 7852,
Recife, PE 50670-000, Brazil

water in the BFC of the shells from the Yucatan beach


sands. This is also supported by the flat pattern trends of
bivalves and gastropods based on the normalized patterns of
light rare earth element compared to heavy rare earth element concentrations. This paper is also a contribution to the
methodology of analysis of carbonate sands, i.e., whole
bulk composition isolation into their main biogenic components and the accumulation of major, trace, and rare earth
elements deposited into their shells, initially under subaquatic marine conditions and currently exposed to subaerial coastal influences based on the allochthonous
character of the shells.
Keywords Sedimentology  Biogenic fraction
components (BFC)  Geochemistry  X-ray diffraction 
Yucatan  Mexico

Introduction
In the Yucatan Peninsula, southeastern Mexico, carbonate
beach sands are mainly composed of biogenic fractions
ranging from 80 to 99 % (Nolasco-Montero and CarranzaEdwards 1987). Bivalves, gastropods, coral fragments,
calcareous algae, oolites, foraminifera, echinoderm, sponge
spicules, bryozoans, and ostracods have been identified.
Previous studies conducted in the Yucatan Peninsula
and other beach sands composed of carbonate worldwide
have analyzed carbonate content and the origin of carbonate detritus, the geomorphology of carbonate beach
sands, and carbonate deposits of eolianites (Folk and
Robles 1964; Logan et al. 1969; Ward 1975; Ward and
Brady 1979; Karisiddaiah et al. 1988; Caccia and Millero
vila 2009). Other stud2007; Cuevas-Jimenez and Euan-A
ies conducted in ancient limestones used the geochemical

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Carbonates Evaporites

fingerprint of major, trace, and rare earth elements as well


as stable isotopic analyses (Madhavaraju et al. 2010;
Armstrong-Altrin et al. 2011; Nagarajan et al. 2011;
Nagendra et al. 2011) to observe diagenetic processes that
took place in the past. However, there are no reports on
diagenesis or the physical/chemical/biological processes
observed among different BFC deposited as beach sediments. This paper is an important contribution to the
knowledge of diagenetic influences controlling BFC composition in the coastal area of Yucatan, Mexico. The
methodology of analysis of carbonate sands is addressed in
this work, i.e., whole bulk composition isolation into their
main biogenic components and the accumulation of major,
trace, and rare earth elements deposited into their shells,
initially under subaquatic marine conditions and currently
exposed to subaerial coastal influences and the possibility
of the neomorphism effects in the crystals of aragonite and
calcite in the BFC.
Study area
The Yucatan Peninsula is a large calcareous platform of
197,600 square km, situated on the Gulf of Mexico to the
West and the North, with the Caribbean Sea to the East
(Fig. 1). The peninsula has a mean breadth of approximately

320 km, and a coastline of about 1100 km. The peninsula


has been characterized as a low-lying coastal area, with
57 % comprising coastal lagoons with barrier islands and
43 % ocean front, of which 85 % is sandy coast. A wide
continental shelf of approximately 245 km is an important
characteristic in the area, with a slope of 1/1000 (Enriquez
et al. 2010). The average altitude in the northern region of
the Yucatan Peninsula is 50 m above sea level.
The peninsula is composed of a limestone platform
(Weidie 1985). Paleozoic metasediments form the basement strata at a variety of depths exceeding 2400 m. Early
Mesozoic red-bed sediments overlie these Paleozoic strata
unconformably, maintaining an average thickness of about
100 m. Limestone rocks were formed during the Cretaceous period with approximately 1300 m thickness due to
transgressive episodes. In the Tertiary period, carbonate
sediments were deposited with 1000 m of thickness.
The Yucatan Peninsula is characterized by a lack of
superficial fluvial systems, where only groundwater, water
caves, and karsts (cenotes) are present. Groundwater
aquifers flow seawards and discharge as submarine springs
(Ruiz-Rentera et al. 1998; Horta-Puga and Carriquiry
2012). The seaward mixing of groundwater reservoirs and
seawater plays a major role in the sculpting of the coastal
features that control the composition of BFC of the
Yucatan beach sands, determined by the relatively homogeneous surface of the Yucatan Platform (Perry and
Velazquez-Oliman 1996).
Climate, tides and nearshore marine currents

Fig. 1 Map of sampling sites A, Sc, Cb, Cr, T, Cx, P, S, geology


(taken and modified from Garca Gil and Graniel Castro 2010), and
physical oceanography of the northern coast of the Yucatan Peninsula
(taken from Fernandez-Eguiarte et al. 1992). Dotted arrows and light
arrows represent the prevailing wind direction (taken from PerezVillegas 1990) and nearshore marine currents, respectively, during the
sampling season along the northern coast of the Yucatan peninsula.
See text for explanation of wind, nearshore marine currents, average
velocities, and prevailing directions

123

The climate on the southeastern coast of Mexico varies


from tropical wet to dry savanna climate (Aw), with an
average maximum temperature of 30 C and an average
minimum temperature of 19 C.
Winds flow at average velocities of 2 m s-1 with a
northeasterly component with maximum frequencies of
*50 % from October to January (Perez-Villegas 1990)
and the Dzilam beaches were the first to be exposed to this
wind action. During the sampling work (i.e., the winter
season), nearshore marine current has a north by northwesterly direction with an average velocity along the
northern Yucatan coast of 2 cm s-1. Nearshore marine
currents have a north by northwesterly direction with an
average velocity of 7 cm s-1 during the summer (Fernandez-Eguiarte et al. 1992).
In the study area, the tidal regime is mixed, with a
diurnal dominance and a tidal range of 0.1 m for neap tides
and 0.8 m for spring tides (Cuevas-Jimenez and Euan vila 2009). The study area is subject to extreme wave
A
events throughout the year: high-pressure polar outbreak
systems called Nortes in the winter, and tropical storms and
hurricanes in the summertime (JuneNovember).

Carbonates Evaporites

Materials and methods


Sampling
Approximately 200 g of sand samples was collected by
hand from the inshore, foreshore, and backshore of the
beach; the material was taken from the uppermost centimeter of the following beaches: Dzilam, Santa Clara,
Chabihau, Telchac, San Crisanto, Chicxulub, Progreso, and
Sisal. The beach sampling covers *102 km of coastline
extension (88 400 89 550 W21 450 22 000 N). In all
samples collected, grain size parameters (n = 28) and BFC
(n = 28) were determined and geochemical analyses of
major, trace, and rare earth elements (REE) (n = 16) and
X-ray diffraction (XRD) observations (n = 4) were
performed.
Grain size parameters
Granulometric analysis of the beach sediments was performed with U.S. Standard sieves (0.25 mm) (Folk 1980)
(Fig. 2). To accurately assess the particle sizes and determine their frequency distribution, we calculated grain size
parameters (Folk 1980) using an Excel Worksheet
Gradistat v.8, based on the tabular classification of retained
weight (g) in the sieves, in terms of phi units (/) (e.g.,
-0.75 /, -0.5 /, -0.25 /, 0.25 /, 1.0 /, 1.25 /, 2 /, 2.5
/, 2.75 /, 3 /, 3.25 /, 3.5 /, 3.75 /, 4.25 /).
Biogenic fraction components (BFC)
BFC analyses were performed in thin sections of the whole
bulk beach sediment, each containing 250 grains. Particle
counting under the microscope was employed to determine

the BFC and to calculate their percentages in the samples.


The BFC in the sands are made up of, by more than 90 %,
decaying calcareous organisms (e.g., biogenic detritus of
mollusks, coral fragments, algae, oolites, foraminifera,
bryozoans, ostracods) (Fig. 3). The point counting was
based on the determination of the BFC raw data and percentages in the Yucatan beach sands (*90 %) which are
composed of decaying biogenic fractions observed semiquantitatively at the Yucatan Peninsula beaches. In this
study, with regard to particle counting, we obtained almost
97 % BFC in the sands (n = 7000 grains) for 28 thin
sections, producing an average and also confidence levels
of 95 %. The points taken in each particle counting were
done using the cross-hair intersection of each grain
observed. This method was applied to thin sections in the
entire bulk composition previously homogenized by the
stirring process to prevent bias. Thus, thin sections represented all of the bulk fractions (from *-0.75 to 4.25 /),
including the coarse and fine BFC made of broken shells
and complete specimens.
Furthermore, individual taxonomic identifications of the
most conspicuous, abundant, and well-preserved organisms
were performed to investigate the average living conditions
of the specimens found in the samples.
Geochemistry of the beach sands
Major and trace element analyses
Approximately 8 g of sample, mostly comprising bivalves,
i.e., one shell fragment and gastropods *n = 4, (sizes
*-4.0 to -5 /) was geochemically analyzed for each
beach site. Before each biogenic sample was crushed, it
was dry-cleaned with a small brush to prevent

Fig. 2 Grain size (Mz) versus


r (sorting) in phi units / for
sand samples from eight beach
sites on the northern Yucatan
coastline

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Carbonates Evaporites

Fig. 3 Average point counting data normalized to percentages and


confidence levels at q = 0.05 represented as pie charts for each
Yucatan beach site. Relative percentages are shown for the most

conspicuous BCF for each beach site as part of the total 100 %. See
text for explanation on the point counting method and bias. The map
shows the sampling beaches

contamination. The sieving of further sizes (other than


-4.0 and -5.0 /) was not accomplished due to the amount
of fragments (n = 4) found in the samples and the lack of
the entire sieve set.
After cleaning, the bivalve and gastropod shell fragments were crushed in a Spex 8000 mixer/mill to obtain
fine powders (particle size \75 lm) to further analyze
major and trace elements. Samples were dried at 110 C
and treated with lithium meta and tetraborate to make

pressed powder pellets. A Siemens SRS 3000 X-ray


fluorescence instrument was used for measurement of
major and trace elements. The performance of the
instrument is evaluated at a relative standard deviation of
\1 %.
Major and trace elements were normalized with PAAS
(Post Archaean Australian Shale) values, since beach sands
show consistent sea water patterns (Taylor and McLennan
1985; Nagarajan et al. 2011) (Figs. 4, 5).

123

Carbonates Evaporites
Fig. 4 Normalized patterns of
major elements (PAAS; Taylor
and McLennan 1985) for 7
beach sites on the Yucatan
coast. See text for more
explanation

Fig. 5 Normalized patterns of


trace elements (PAAS; Taylor
and McLennan 1985) for 7
beach sites on the Yucatan
coast. See text for more
explanation

Rare earth element (REE) analysis


Samples were digested with HF ml and *0.5 g of crushed
sample. Samples were stored in 4 ml HClO4 and eventually
evaporated by adding 5 ml HF with 2 ml HClO4. A second
evaporation process was performed by adding 2 ml HClO4
until desiccation was achieved, followed by dilution with
50 ml HNO3 (2 %).

Sample RRE analyses were performed in an Inductively


Coupled Plasma Mass Spectrometer (ICP-MS) model
iCAP Qc Thermo Scientific at the Instituto de Geofisica,
Universidad Nacional Autonoma de Mexico [Geophysics
Institute, National Autonomous University of Mexico]. The
instrument was optimized with certified High Purity Standard solutions with a wide range of Li, Co, In, Ba, Bi, Ce,
and U of 1 lg/L, respectively. The calibration curve was

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Carbonates Evaporites

plotted with 12 points (0, 0.1, 0.25, 0.5, 0.75, 1, 2.5, 5, 7.5,
10, 25, and 50 lg/L), starting with a multi-elemental stock
of 10 lg/ml of High Purity Standards (ICP-MS-B).
Instrumental drift was corrected using 115 In as an internal
standard, prepared from a certified stock solution of
1000 mg L-1 (Merck, Germany). Detection limits were
calculated as three times the blank filter standard deviation,
to ensure reproducibility.
The Pr/Yb ratio and Eu and Ce anomalies, i.e., (Pr/Yb),
(Eu/Eu*), and (Ce/Ce*), were calculated using both
PAAS (Taylor and McLennan 1985) and MuQ values
(average alluvial sediment in Queensland, representing a
compilation of the sedimentary composition of 25 rivers
in Queensland, Australia (Kamber et al. 2005; Lawrence
et al. 2006) with regard to the calculated anomalies and
the graphic normalized patterns for light rare earth elements and heavy rare earth elements (LREE or La to Eu,
and HREE or Gd to Tb, respectively) (Tables 1, 2;
Fig. 6a, b).

X-diffraction analysis
The mineralogy of four samples: bivalves (n = 1) and gastropods (n = 3) were determined with an Empyrean
diffractometer (Fig. 7a, b, c, d). Samples were ground with
an agate pestle and mortar to produce a fine powder for XRD
analyses. Diffractograms were recorded in step-scan mode at
0.003 intervals from a start angle (2h) of 5.0 up to an angle
(2h) of 70.0, with 40 s per step. Diffraction data were stored
after the initial X-ray exposure. No samples showed significant evidence of degradation with the X-ray beam.

Results
Grain size parameters
Medium size, moderately sorted, coarse-skewed, leptokurtic sands were found along the Yucatan coastline. The

Table 1 (Eu/Eu*), (Ce/Ce*), (Eu/Eu*), (Ce/Ce*), (Pr/Yb) PAA and (Pr/Yb)MuQ anomalies for bivalves from the Yucatan carbonate beach sands
(n = 9)
Bivalves

(Pr/Yb)

PAAS

(Pr/Yb)

MuQ

(Eu/Eu*)PAAS

(Eu/Eu*)MuQ

(Ce/Ce*)

PAAS

(Ce/Ce*)

MuQ

Samples
Di2B

4.73

5.69

0.74

0.825

0.86

0.80

Dm2B

1.54

1.86

1.16

0.004

0.80

0.26

Sci1B

3.88

4.68

0.67

0.001

0.83

0.21

Cbi1B

7.25

8.72

0.63

0.000

0.84

0.19

CrilB

0.55

0.66

0.70

0.000

0.60

0.08

Ti2B
Cxi2B

1.72
0.77

2.07
0.93

1.00
0.90

0.000
0.000

0.81
0.87

0.03
0.18

Pi1B

1.08

0.000

0.90

0.01

Sm2B

0.92

1.12

1.14

0.000

0.80

0.05

Average

2.67

2.86

0.89

0.092

0.81

0.20

Confidence levels

1.61

1.89

0.14

0.179

0.06

0.13

Anomalies based upon the Post Archean Australian Shale (PAAS) and average alluvial sediment in Queensland (MuQ) (Taylor and McLennan
1985; Bau and Dulski 1996; Kamber et al. 2005; Johannesson et al. 2007; Lawrence et al. 2006), i inshore; m foreshore. B bivalves

Table 2 (Eu/Eu*), (Ce/Ce*), (Eu/Eu*), (Ce/Ce*), (Pr/Yb)


sands (n = 5)
Gastropods

(Pr/Yb)

PAAS

(Pr/Yb)

MuQ

PAA

and (Pr/Yb)MuQ anomalies for gastropods from the Yucatan carbonate beach
(Eu/Eu*)PAAS

(Eu/Eu*)MuQ

(Ce/Ce*)PAAS

(Ce/Ce*)MuQ

Samples
DiG

1.64

2.00

0.92

0.000

0.81

0.20

Dm2G

2.28

3.11

0.85

0.000

0.83

0.13

Sci1G

0.44

0.53

0.87

0.000

0.82

0.49

Cbi1G

2.14

2.96

0.93

0.000

0.77

0.17

Tm2G

0.79

0.93

0.00

0.000

0.87

0.18

Average

1.46

1.91

0.71

0.000

0.82

0.24

Confidence levels

0.71

1.02

0.35

0.000

0.03

0.13

See Table 1 for explanation; G gastropods

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Carbonates Evaporites

the Chicxulub beach sands, respectively. The second most


abundant BFC are the gastropods, ranging from 0.1 to
6.0 % from Progreso to Dzilam, respectively. The rest of
the BFC include much lower abundances of carbonate
structures from a variety of calcareous organisms. Minor
average
abundances
are
represented
by
foraminifera [ bryozoans C ostracods, corals, and spicules. Among the BFC, only a few complete bivalve and
gastropod shells were preserved for taxonomic
identification.
Geochemistry of the carbonate beach sands
Major elements
The PAAS normalized major element values show
prominent peaks of Ca [ Mg [ P [ Mn at the seven
beaches. Fe concentrations were undetermined due to a
depletion of this element in the BCF.
Trace elements
Trace element concentrations were abundant in the following order: Sr [ Co [ Th = Nb [ Y, in all of the carbonate sands of the eight Yucatan beaches, showing no
significant difference between the carbonate beach samples, neither in those from the submerged environment, nor
in those from the bivalve and gastropod samples. Copper
was under the limit of detection.
REE data

Fig. 6 Normalized patterns of rare earth elements for the a bivalve


and b gastropod fractions (PAAS; Taylor and McLennan, 1985) for 7
beach sites on the Yucatan coast. See text for more explanation. (1)
REE patterns in sea water in the core of Mediterranean water (900 m)
(Elderfield and Greaves 1982); (2) REE sea water trends from the
Sargasso Sea in the Atlantic Ocean at 60 m to 2000 m depth (Piper
and Bau 2013)

sands are a mixture of fine (41 %), medium (37 %), coarse
(18 %), and very fine (4 %) fractions. A negative correlation between Mz (/) versus r (/) was observed in the
Yucatan carbonate sands (r = -0.74 at q = 0.05, n = 30).
BFC of the Yucatan beach sands
A lack of statistical significance between the grain size and
the bivalve and gastropod shells analyzed was observed
(r = 0.13; r = -0.07; q = 0.05; n = 28, respectively).
The most abundant components of the BFC (%) were the
bivalves, ranging from 88.1 to 99.2 %, from the Dzilam to

In general, our LREE and HREE studies showed a flat


pattern with the exception of samples Di2B and Cbi1B,
which tended to show slightly higher concentrations of
LREE compared to HREE concentrations. The (Pr/Yb)
PAAS and (Pr/YB) MuQ average anomalies were calculated to document the LREE depletion compared to the
HREE values (average 2.67 and 1.46 0.71 (PAAS);
2.86 1.89 and 1.91 1.02 (MuQ), respectively). The
average (Eu/Eu*) and (Ce/Ce*) anomalies normalized with
PAAS and MuQ show negative anomalies (\1.0). The REE
results from samples taken from beaches SCi1B, Cbi1B,
Ti2B, Pi1b, and Sm2B show depleted values for Tb, Ho,
and Yb, whereas samples from Dm2G and Tm2G are only
depleted in Tb.
X-ray diffraction patterns
The diffractograms show maximum peaks for aragonite
followed by a relatively equal composition of calcite and
probably vaterite (Jacob et al. 2008).

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Carbonates Evaporites

Fig. 7 X-ray diffractograms for samples a Di2B, i.e., Chione


cancellata (n = 1), b Di2G, i.e., Cerithium atratum (n = 1), c,
d Dm2G, i.e., Bulla striata and Solariella lacunella (n = 2).

B bivalves, G gastropods. Samples used for X-ray diffractograms


were selected from the Dzilam beach site where more well-preserved
bivalves and gastropods were collected

Discussion

BFC of the carbonate beach sands

Grain size parameters

Coarse-grained beach sands are recognized to be associated


with high shell input (e.g., bivalves and gastropods) and
depletion of terrigenous supply (Watson 1971; KasperZubillaga and Carranza-Edwards 2005). A high statistical
significance obtained between sorting and the combined
number of mollusks (bivalves plus gastropods) in the
Yucatan beach sands (r = -0.48; q = 0.05 with standard
error and student t test, n = 28; df = n - 2; t-critical = 205; r = 0.48 [ 0.35 is significant) (Swan and
Sandilands 1995) suggests a wide range of sorting values,
which may be a consequence of the variable concentration
of mollusks in the beach sands. Interestingly, the Dzilam
beach sands are those that could have experienced a less
selective sorting process, perhaps due to reduced wind
action and/or a greater average accumulation rate of foraminifera (4.0 %) less than 1 mm in size or [1.0 / (Pettijohn 1975), thereby increasing the fine-grained sand
fraction and the sorting value of the sediments at beach D
(average r = 1.16 0.49). The littoral drift can control
the input of large shell fragments onshore, along with

The negative correlation between Mz and r has also


been observed in many terrigenous beach and dune sands
elsewhere (Wang et al. 2003; Kasper-Zubillaga and
Carranza-Edwards 2005; Kasper-Zubillaga et al. 2007).
Poorly sorted sands are within the range of coarser
sands, while better-sorted sands are composed of fine
particles, suggesting the presence of coarser biogenic
fractions in the carbonate sands. Four Dzilam beach
samples are represented in the Mz (/) range sizes
between 0.00 and 1.00 (coarse sands) and r (/) between
0.50 to 1.80 (moderately well-sorted to poorly sorted
sands) followed by samples from Santa Clara, Telchac,
Progreso, Chicxulub, and Sizal. The following group of
samples: Ds2, Dm2, D2, and Di2; Sci1; Ti2; Pi1; Cxi2,
and Sm2, and especially the Dzilam beach sands clearly
suggest the effect of coarse fraction (%) deposition on
beaches with stable and depositional shorelines (Appendini et al. 2012).

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aeolian deflation, as two mechanisms able to concentrate


coarse and fine biogenic fractions by longshore transport
and the wind blow effect (Watson 1971). In terms of the
shells preservation, the majority of the organisms show
extreme abrasion, fragmentation, and evidence of physical
transportation. Therefore, we use the term allochthonous to
refer to such identifiable characteristics (Callender et al.
1992); all of them were present at the time of sampling,
i.e., broken shells, single valves, polished surfaces.
Geochemistry of the carbonate beach sands
Major elements: Ca, Mg, P, Mn, and Ti in the BFC
The BFC of the Yucatan beach sands are mostly composed
of bivalves and gastropods with aragonite followed by
calcite crystals in varying proportions (Figs. 6a, b, 7ad).
The Mg concentrations in the BFC may be associated with
the aragonite lattice in bivalves and gastropods, where Mg
can be part of the aragonite crystals, instead of being a real
substitution for Ca in shallow waters during the subaquatic
residence of the specimens. This statement is supported by
the higher concentration of Ca compared to Mg in the
shells, and the low Mg/Ca ratio \1, which provides
information on aragonite precipitation in the water
(Wilkinson and Algeo 1989; Hardie 1996; Morse et al.
1997). It is likely that the bivalves and gastropods of the
Yucatan beach sands have been influenced by modern sea
water signals based on the Mg/Ca ratio. This is supported
by reports made in the past when the Mg/Ca ratio of seawater was relatively low (Stanley and Hardie 1998). Some
carbonate organisms produce low-Mg calcite into their
skeletons which may suggest an increase in the Mg over
time, in which the influence of modern sea waters controls
the concentration of Mg in recent bivalves and gastropods
from the Yucatan beach sands (Lowenstein et al. 2001;
Stanley et al. 2002; Porter 2007).
The presence of some aragonite and calcite in the
bivalve and gastropod shells suggests the possible following interpretations based on the mineralogy and geochemistry of the shells: (a) aragonite and calcite may be
part of the original crystal structure of the shells, (b) a
mixture of marinehypersaline water and groundwater can
produce the presence of calcite crystals in the BCF, from
pre-existing aragonite (Warren 2000), (c) the presence of
non-ferroan calcite supports an early diagenetic processes
in the bivalves and gastropods from aragonite to calcite,
evidenced by Fe depletion, high Sr and low Mn concentrations in the shells as a form of neomorphism (Oldershaw
and Scoffin 1967; Sandberg and Hudson 1983; Hendry
et al. 2006). For instance, some areas such as Rio Lagartos
(a coastal lagoon east of the area studied), where salinity
values are between 49 and 62 psu and the influence of

seaward groundwater flows (Vega-Cendejas and de Santillana 2004) may favor the presence of early diagenesis
during subaerial conditions of high evaporation. Comparisons of the composition of carbonate beach sands close to
the Yucatan beach sands have been made between the
Alacran Reef System and the Yucatan coastline, a distance
of approximately 124 km. Bivalves and gastropods were
mainly composed of aragonite with calcite (Chave 1954),
which is similar to the results obtained in this study. XRD
results of muds as a whole bulk composition of different
carbonate organisms from the reef report an aragonite
proportion of 7988 % (Hoskin 1963).
The average value for P observed in the BFC of the
Yucatan beach sands ranged from 0.017 0.003 % to
0.023 0.006 %, and the majority of these values was
produced by gastropod shells. The incorporation of P by
filtering organisms such as bivalves was previously related
to the ingestion of phytoplankton, which in some bivalve
shells from freshwater environments ranges from 0.1 to
0.6 % (Swineheart and Smith 1979). In other freshwater
and marine bivalve studies (Swineheart and Smith 1979),
the exchange of Mn for Ca and P into the CaCO3 matrix
appears to reflect the absorption of P onto the surface of the
shells via iron oxyhydroxide coatings from the periostracum, to provide a defensive buffer against acidic attack
on the shell. Sholkovitz (1995) reported that sea water must
be a prime supply of phosphate replacement in biogenic
grains from shallow waters. This statement is also supported by the high correlation between CaO versus P2O5
(r = 0.95) in coastal dunes with shell fragments in northwestern Mexico (Kasper-Zubillaga et al. 2008).
Mn and Ti concentrations in the BFC of the samples
were the lowest in the major element analysis, which may
not exert a control on the diagenesis of the BFC. Ti may be
considered a trace element in carbonate-compound organisms (Keller et al. 2007).
Trace elements: Sr, Y, Nb, Co, and Th concentrations
in the BFC
Average Sr concentration values ranged from 1471 78 to
1242 11 with average Mg/Sr ratios of 0.87 and 1.53 in
bivalves and gastropods, respectively. Sr concentration in
gastropods from East Africa ranged from 822 to 1604 ppm
and their Mg/Sr ratio ranged from 0.05 to 0.39 (Foster and
Cravo 2003). The increase in the average Mg value in
gastropods from the Yucatan beach sands can only be
explained by the influence of modern sea waters that may
have an effect on the increase of Mg in some shell samples
(Stanley et al. 2002).
Strontium is generally found in higher concentrations in
aragonitic rather than calcitic shells (Stanley 2006), although
the range of concentrations in both mineralogical types is

123

Carbonates Evaporites

relatively similar in gastropods from East Africa and Yucatan (9503500 lg g-1 or ppm; 12421471 lg g1 or ppm,
respectively) (Harriss 1965; Foster and Cravo 2003).
The lower Mg/Sr ratio in the BFC in the Yucatan shells
compared to the Mg/Sr ratio found in gastropods from East
Africa may be due to the presence of shells composed of
calcite (Foster and Cravo 2003), echinoderms, and large
foraminifera from shallow waters (Turekian 1976). Conversely, aragonite is the main component of bivalves and
gastropods in the BFC in Yucatan according to the analysis
of the diffractogram. However, variable aragonitecalcite
composition in the Yucatan shells may influence the
incorporation of Sr into their crystal lattices in both mollusk types. This suggests an early diagenetic process in the
shells derived from the interaction between sea water and
subaerial exposure with meteoric influence and/or by possible geochemical signature changes as explained above;
i.e., neomorphism (Oldershaw and Scoffin 1967; Sandberg
and Hudson 1983; Budd 1988; Hendry et al. 2006).
Average Y concentration values in the BCF are
\1.0 ppm. The low Y concentrations in this study, i.e.,
\1.0 ppm, support the lack of terrigenous input seawards
into the Yucatan beach sands since this element is a reliable proxy of terrigenous influence (Lewis et al. 2007;
Nagarajan et al. 2011).
Concentrations of Nb, Co, and Th were \2 ppm in the
BFC; they are negligible trace elements in the subaquatic
and/or subaerial influence of the shells.
Rare earth elements (REE)
The LREE depletion compared to HREE values based on the
(Pr/Yb)PAAS and MuQ ratio [ 1 suggests three possibilities:
(a) little incorporation of LREE into the BFC (Johannesson
et al. 2007); (b) a longer time of residence of these organisms
exposed under subaerial conditions on the beach rather than
under subaquatic conditions; and/or (c) a large amount of
broken shells affecting the LREE signals of sea water
incorporated into their carapaces. Sea water signals elsewhere show a high concentration of HREE compared to
LREE as reported in modern sea water near the Caiman
Islands, i.e., the Caribbean Sea, which supports the depletion
of sea water signals incorporated into the flat-like patterns of
the bivalves and gastropods studied in the Yucatan beaches
from the Gulf of Mexico and in ancient limestones in
northwestern Mexico (Madhavaraju et al. 2010; Zhao and
Jones 2013). Furthermore, some carbonate exposed to sea
water influence may increase in LREE concentration compared to HREE concentration, producing a flat-like pattern
similar to those observed in the bivalves and gastropods of
the Yucatan beach sands, suggesting discrepancies with the
modern sea water influence in Yucatan shell composition
(Madhavaraju and Gonzalez-Leon 2012).

123

The (Eu/Eu*)PAAS and MuQ and (Ce/Ce*)PAAS and MuQ


\ 1 indicate modern shallow waters as part of their natural
habitat (Webb and Kamber 2000). The negative Eu
anomaly in the shells suggests (a) diminished remobilization of Eu compared to other REE in sea water; (b) less
reducing conditions in the BFC deposited on the beach; and
(c) early diagenetic environmental conditions (Lavoie and
Bergeron 1993; Kasper-Zubillaga et al. 2014).
The negative Ce anomaly may be related to (a) weathering
and/or inorganic aquatic processes; (b) the meteoric input by
rain and fresh water discharges running seawards along the
underground karst or cenote systems along the Yucatan
coastline (Sholkovitz 1995; Byrne and Sholkovitz 1996;
Lawrence et al. 2006; Horta-Puga and Carriquiry 2012); and
(c) modern shallow sea water environmental oxic conditions
(Webb and Kamber 2000; Kasper-Zubillaga et al. 2014).
Data from the negative Ce anomalies *1.0 may be
indicative of the effect produced by calculating the Ce
anomaly with an overabundance of La. Anomaly determinations based on the MuQ help to overcome the
anomalously inherited effect of several REE such as La,
Gd, and Lu (Lawrence et al. 2006).

Conclusions
The BFC were characterized by high levels of allochthonous bivalve and gastropod shells based on the isolation
technique from the whole bulk carbonate sand composition. Early diagenetic processes in the bivalves and gastropods studied are controlled by groundwater flows,
subaerial exposure, high evaporation rates, little sea water
influence, and possible neomorphism. This is supported by
the geochemical signals, i.e., major and trace elements,
REE trends, the (Pr/Yb) PAAS and MuQ, (Eu/Eu*) PAAS and
MuQ and (Ce/Ce*) PAAS and MuQ anomalies \1, and the
mineralogical content in the shells, i.e., aragonite, calcite,
and possibly vaterite. Additional evidence for this interpretation is found in the flat pattern trends of bivalves and
gastropods based on the normalized patterns of light rare
earth element (LREE) concentration compared to heavy
rare earth element (HREE) concentration, which indicates
dissimilar seawater-like signatures from different sea water
REE trends.
Acknowledgments We are grateful to Dr. Ofelia Morton-Bermea,
Elizabeth Hernandez-Alvarez, Rufino Lozano-SantaCruz, Patricia
Giron-Garca, and Dr. Teresa Pi-I-Puig, for the geochemical and
X-diffraction analysis. This research was supported by the Instituto de
Ciencias del Mar y Limnologa, UNAM (109), and by the SEPConacyt 238457 and PAPIIT (IA101213) Projects. We thank Mr.
Patrick Bennett Weill for English language review. All authors are
grateful to the Editor and three anonymous reviewers for the comments and corrections made to improve this paper.

Carbonates Evaporites

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