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DOI 10.1007/s13146-015-0283-0
ORIGINAL ARTICLE
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
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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
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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
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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
(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
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Carbonates Evaporites
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
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Carbonates Evaporites
Discussion
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Carbonates Evaporites
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
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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
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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