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Article history: The elemental content (major, trace and rare earth elements) of 35 AptianeAlbian limestone samples
Received 8 May 2008 from the Mural Formation has been determined to provide information on depositional conditions and
Accepted in revised form 14 May 2010 provenance. The limestones of the Mural Formation show large variations in terrigenous and carbonate
Available online 20 May 2010
contents (1.2 to 42.3% and 57.7 to 98.8% respectively). Small variations are observed in CaO concentra-
tions in the Tuape Shale, Cerro La Puerta and Mesa Quemada members whereas large variations are
Keywords:
found in the Cerro La Ceja, Los Coyotes and Cerro La Espina members. The majority of the limestones
Geochemistry
show high values of Th, Sc and Zr. Large variations in SREE content are observed among different
Rare Earth Element
Provenance
members of the Mural Formation. Most limestones from the Mural Formation record non-seawater-like
AptianeAlbian Limestone REEþY signatures. The limestones show large variations in Ce anomalies which may be due to mixing of
Mural Formation sediment components (biogenic and authigenic phases) and detrital materials including Fe-colloids from
Northern Sonora fluvial input. Most of the limestones show positive Eu anomalies, but some samples show negative Eu
México anomalies (Eu/Eu*: 0.42 to 2.62).
The large variations in terrigenous percentage, high Al2O3 and SREE contents, high LaN/YbN ratios, low
Y/Ho ratios and non-seawater-like REE patterns suggest that the observed variations in SREE contents
are mainly controlled by the amount of detrital sediments in the limestones of the Mural Formation. The
limestones of the Mural Formation were deposited under both coastal and open shelf environments, and
they exhibit non-seawater-like REE þ Y patterns. The presence of terrigenous materials in these
carbonates as contaminants effectively masks the seawater signature due to their high concentration of
the REE. Thus, trying to decipher the palaeoceanographic conditions represented by ancient carbonate
rocks should be done cautiously since limestones deposited under open marine environments may also
be contaminated by some amount of terrigenous particles. The presence of small quantities of terrige-
nous materials in the limestones can also reveal source rock information. The La/Sc, La/Co, Th/Sc, Th/Cr,
Th/Co and Cr/Th ratios suggest that the terrigenous materials present in the limestones were mainly
derived from a nearby exposed basement of intermediate to felsic igneous rocks.
Ó 2010 Elsevier Ltd. All rights reserved.
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doi:10.1016/j.cretres.2010.05.006
J. Madhavaraju et al. / Cretaceous Research 31 (2010) 400e414 401
The distribution of REEs and Ce anomalies in marine sediments 2. Geology and Stratigraphy
may be influenced by depositional environments such as proximity
to source area (Murray et al., 1991a), widespread marine anoxia (Liu The Lower Cretaceous sedimentary succession assigned to the
et al., 1988; German and Elderfield, 1990; Murray et al., 1991b), Bisbee Group is well exposed in the north-central part of the state
surface productivity variation (Toyoda et al., 1990), oceanic redox of Sonora, Mexico. This succession has similar stratigraphic and
conditions (Liu et al., 1988; German and Elderfield, 1990) and lithologic characteristics to the younger formations of the Bisbee
lithology and diagenesis (Nath et al., 1992; Madhavaraju and Group (Ransome, 1904) of southern Arizona and New Mexico in the
Ramasamy, 1999; Armstrong-Altrin et al., 2003; Madhavaraju and United States of America, and is correlative with strata exposed in
Lee, 2009). Ce anomalies in marine sediments are considered by northern Mexico (Cantu-Chapa, 1976; Bilodeau and Lindberg, 1983;
some as reliable indicators for understanding the paleoredox Mack et al., 1986; Dickinson et al., 1989; Jacques-Ayala, 1995;
conditions (Liu et al., 1988), although several workers have raised Lawton et al., 2004). In Arizona the Bisbee Group consists of the
doubts about their effectiveness (German and Elderfield, 1990; Glance Conglomerate and the Morita, Mural and Cintura Forma-
Murray et al., 1991b; Nath et al., 1992, 1997). tions that were deposited in a rift basin, termed the Bisbee Basin.
The REE signatures in ancient marine environment provide The older unit is the Glance Conglomerate composed of cobble- to
information on secular changes in detrital influx and oxygenation boulder-conglomerate with local interbeds of volcanic flows and
conditions in the water column (e.g. Holser, 1997; Kamber and tuffs, which represent syntectonic rift deposits (Bilodeau et al.,
Webb, 2001). The seawater signatures are, however, completely 1987; Lawton et al., 2004).
masked by the incorporation of terrigenous materials, which have The Morita and Cintura Formations are composed of reddish
relatively high, non-seawater-like REE contents (Murray et al., 1992; brown siltstone and lenticular beds of arkose and feldspathic
Webb and Kamber, 2000; Nothdurft et al., 2004; Madhavaraju and arenite (Dickinson et al., 1986; Klute, 1991) that were deposited
Lee, 2009). The identification of the terrigenous particles present under fluvial conditions. These two formations are difficult to
in the marine carbonate rocks as contaminants is an important distinguish based only on their lithological characteristics. Hence,
aspect to understand the geochemistry of carbonate rocks. the intervening marine Mural Formation is key to understanding
The Lower Cretaceous, shallow marine siliciclastic and calcar- Lower Cretaceous stratigraphy and basin configuration in the area.
eous strata of the Mural Formation are exposed in northern Sonora, The fossiliferous clastic and carbonate strata of the Mural
northwest Mexico in a 300 km long transect that extends from Formation were deposited during a major marine transgression
Sierra El Chanate (westernmost part) to Cerro El Caloso Pitaycachi during AptianeAlbian time (Scott, 1987) in the region of Sonora and
(northeastern most outcrop). Along this transect, González-León Arizona where it overlies the Morita Formation on a sharp ravine-
et al. (2008) reported the stratigraphy and biostratigraphy of ment surface and grades upward into the Cintura Formation.
several sections, including the Cerro Pimas and Sierra San José Lawton et al. (2004) defined six members in the Mural Formation in
sections (Figs. 1 and 2) of which we discuss herein the major, trace north-central Sonora (Fig. 2), which from the base upwards are the
and REE geochemistry of their limestone beds. The aims of our Cerro La Ceja, Tuape Shale, Los Coyotes, Cerro La Puerta, Cerro La
study are to determine the influence of terrigenous materials on the Espina and Mesa Quemada members. The lithostratigraphic studies
REE characteristics of carbonate rocks, to document the variations of different members of the Mural Formation show minor facies
in Ce anomalies and to unravel the probable reason for significant changes from west to east. The facies characteristics and regional
positive Eu anomalies in the limestones of the Mural Formation. correlation of different members of the Mural Formation indicate
that the depositional environments of this formation varied from
restricted shelf with deltaic and fluvial influence to open shelf with
San Luis 113 00 110 00 coral rudist buildups, to offshore shelf. For the present study, we
R. C.
have collected limestone samples from the western part (Cerro
SONORA ARIZONA Pimas e CP) and the eastern part (Sierra San José e SSJ) of the
Sonoita
Bisbee Basin in northern Sonora. Here the limestones of the Mural
Naco Agua Prieta
Nogales Formation were deposited in a nearshore environment with deltaic
Cananea 31 00
and fluvial influence to open marine environments (González-León
Sierra
Caborca Santa Ana San Jose
et al., 2008). Most of the limestone samples contain varied amounts
of terrigenous materials.
Cerro The Cerro La Ceja (CLC) Member consists of interbedded bio-
Pimas
clastic limestone, siltstone and calcareous sandstone. The limestone
beds are grey, brown and dark yellowish brown, bioturbated and
locally sandy. Siltstone beds are grey, green and reddish brown with
calcareous nodules. The Tuape Shale (TS) Member is mainly
HERMOSILLO 29 00
composed of grey to black mudstone and shale, shaly limestone and
0 20 60 120
subordinate amount of siltstone and fine grained sandstone.
Km Limestone occurs as thin beds which contain oysters and ammo-
nites. The Los Coyotes (LC) Member consists of thin beds of brown
Guaymas
mudstone, calcareous siltstone, shaly limestone, massive brown
siltstone, fine-grained sandstone and bioclastic limestone. This
Obregon
member contains abundant fossils such as oysters, trigoniids,
Navojoa gastropods, bivalves and echinoderms. The Cerro La Puerta (CLP)
27 00
Member is composed of mostly black shale and thin beds of fine-
Mexico grained sandstone and fossiliferous limestone. The limestone
exhibits distinct bedding-parallel burrows on the upper bed
surfaces, and it contains fossils including oysters and Orbitolina; the
black shale contains calcareous nodules. The Cerro La Espina (CLE)
Fig. 1. Location map of the studied sections of the Mural Formation. Member consists mainly of massive limestone with thin beds of
402 J. Madhavaraju et al. / Cretaceous Research 31 (2010) 400e414
Fig. 2. Lithostratigraphic sections of the Mural Formation in Cerro Pimas and Sierra San José areas (modified after González-León et al., 2008).
J. Madhavaraju et al. / Cretaceous Research 31 (2010) 400e414 403
Table 2
Major oxides (wt%), trace and rare earth elements (ppm) concentrations for limestones of the Mural Formationa.
Member/Sample no Clastic % Carbonate % SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O MnO TiO2 P2O5 LOI Total Co Cr Sc Y Zr Sr
Cerro Pimas section
Mesa Quemada
CP47 10.8 89.2 9.1 0.50 0.80 49.9 0.20 0.03 0.13 0.08 0.03 0.05 39.0 99.82 4.2 11.3 1.00 5.1 1.0 425
CP45 5.1 94.9 3.5 0.86 0.41 53.0 0.31 0.16 0.09 0.05 0.04 0.02 41.3 99.74 2.9 10.4 1.00 4.7 1.0 631
Cerro La Espina
CP43 29.5 70.5 23.7 2.99 1.46 38.7 0.67 0.82 n.d. 0.15 0.12 0.03 31.4 100.00 4.3 9.1 2.21 6.1 24.1 554
CP41 4.8 95.2 3.0 0.27 0.34 53.3 0.35 0.05 n.d. 0.06 0.02 0.02 42.0 99.41 2.8 1.0 0.41 5.2 0.6 405
CP38 11.0 89.0 7.8 1.10 1.27 48.7 1.26 0.07 n.d. 0.12 0.05 0.02 39.1 99.49 6.9 4.9 1.40 10.7 9.4 544
CP36 5.2 94.8 3.3 0.58 0.56 53.0 0.68 0.08 n.d. 0.09 0.02 0.02 41.4 99.73 4.6 3.5 1.20 14.1 2.6 529
CP33 7.7 92.3 5.6 0.46 0.66 51.2 0.73 0.01 n.d. 0.08 0.03 0.02 40.8 99.59 3.2 4.6 0.60 9.5 2.8 746
Los Coyotes
CP28 2.8 97.2 1.8 0.14 0.28 54.1 0.35 0.01 n.d. 0.06 0.01 n.d. 42.7 99.45 2.9 1.4 0.20 1.7 1.0 540
CP26 5.5 94.5 3.9 0.65 0.65 52.0 0.41 0.14 n.d. 0.08 0.04 0.02 41.3 99.19 3.7 11.0 0.60 4.1 4.4 428
CP24 3.9 96.1 2.9 0.48 0.65 53.2 0.26 0.10 n.d. 0.06 0.03 0.02 41.9 99.60 4.3 6.0 0.60 4.4 4.2 440
CP22 1.9 98.1 1.5 0.10 0.25 54.9 0.09 0.01 n.d. 0.07 0.01 0.01 42.4 99.34 3.0 3.5 0.20 10.3 1.0 218
CP18 6.1 93.9 3.4 0.48 1.81 51.9 0.51 0.08 n.d. 0.25 0.02 0.02 41.1 99.57 10.1 7.7 0.60 6.0 2.6 368
CP15 6.6 93.4 5.4 0.47 0.78 51.5 0.18 0.12 n.d. 0.25 0.02 0.01 40.5 99.23 4.5 6.3 0.60 6.5 4.4 471
Tuape Shale
CP12 19.6 80.4 14.2 2.75 1.66 44.2 0.69 0.44 n.d. 0.15 0.12 0.05 35.5 99.76 4.6 10.8 1.79 7.1 14.4 866
CP10 14.9 85.1 9.9 1.73 1.33 46.8 1.20 0.20 0.02 0.12 0.08 0.04 37.7 99.12 3.6 13.6 1.39 18.2 42.1 1116
CP9 17.0 83.0 13.1 1.33 1.37 46.1 0.32 0.14 0.26 0.16 0.07 0.05 36.6 99.50 3.0 9.0 0.81 8.4 5.9 503
CP6 20.8 79.2 16.9 2.04 1.36 43.5 0.45 0.45 0.03 0.08 0.10 0.02 34.6 99.53 3.2 15.3 2.19 13.2 24.1 705
Cerro La Ceja
CP4 3.9 96.1 2.0 0.49 0.26 53.3 0.38 0.10 n.d. 0.01 0.03 0.02 42.5 99.09 2.2 7.7 0.61 2.5 1.6 510
CP3 5.8 94.2 3.1 0.77 0.41 53.3 0.23 0.17 0.02 0.07 0.04 0.04 41.4 99.55 5.3 6.8 0.87 6.6 1.9 391
CP1 29.3 70.7 23.3 2.84 1.59 38.0 0.52 0.29 0.66 0.69 0.12 0.06 31.1 99.17 3.4 9.1 1.78 9.5 24.8 298
Member/Sample no Th Pb La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu SREE
Cerro Pimas section
Mesa Quemada
CP47 0.25 8 5.57 5.63 0.98 4.68 0.86 0.23 1.07 0.13 0.74 0.14 0.39 0.04 0.28 0.04 20.78
CP45 0.39 29 5.91 10.27 1.52 7.46 1.15 0.23 1.24 0.15 0.83 0.16 0.45 0.05 0.35 0.04 29.81
Cerro La Espina
CP43 1.55 254 6.16 12.44 1.38 7.28 1.31 0.39 1.62 0.21 1.03 0.22 0.62 0.09 0.59 0.09 33.43
CP41 0.23 47 3.25 6.21 0.69 3.73 0.70 0.18 1.00 0.14 0.75 0.16 0.45 0.06 0.39 0.06 17.77
CP38 1.01 22 7.75 17.38 1.85 10.06 1.67 0.43 2.38 0.32 1.62 0.33 0.91 0.12 0.77 0.11 45.70
CP36 0.81 58 8.62 19.69 2.07 11.45 1.98 0.43 2.91 0.40 2.06 0.42 1.16 0.16 1.02 0.15 52.52
CP33 0.64 43 6.78 13.62 1.49 8.07 1.39 0.36 2.07 0.28 1.40 0.28 0.76 0.10 0.61 0.09 37.27
Los Coyotes
CP28 e 93 1.07 1.70 0.19 1.03 0.20 0.06 0.30 0.04 0.22 0.05 0.14 0.02 0.12 0.02 5.22
CP26 0.33 49 3.66 6.45 0.73 3.87 0.68 0.20 0.89 0.12 0.56 0.12 0.32 0.04 0.26 0.04 17.94
CP24 0.39 135 3.19 5.65 0.66 3.52 0.67 0.18 0.90 0.13 0.66 0.14 0.39 0.05 0.34 0.05 16.53
CP22 0.09 18 2.23 2.69 0.38 1.92 0.44 0.14 0.57 0.08 0.44 0.10 0.27 0.04 0.21 0.03 9.54
CP18 0.57 25 4.74 9.17 1.04 5.51 1.10 0.37 1.34 0.18 0.92 0.18 0.55 0.07 0.43 0.06 25.66
CP15 0.50 46 5.31 9.18 1.04 5.60 1.12 0.36 1.40 0.19 0.93 0.19 0.50 0.06 0.39 0.06 26.33
Tuape Shale
CP12 1.27 40 9.18 18.68 2.04 10.97 1.78 0.69 2.12 0.26 1.19 0.23 0.65 0.08 0.53 0.08 48.48
CP10 1.68 117 11.98 27.18 3.26 17.25 2.42 0.78 2.94 0.35 1.42 0.26 0.70 0.08 0.54 0.08 69.24
C P9 1.44 79 20.88 50.49 4.53 26.72 2.87 1.03 3.69 0.40 1.52 0.28 0.82 0.09 0.56 0.08 113.96
CP6 2.34 14 7.72 14.32 2.01 10.33 1.94 0.47 2.43 0.35 1.98 0.41 1.21 0.16 1.09 0.17 44.59
Cerro La Ceja
CP4 1.51 19 4.63 7.40 1.03 5.05 0.75 0.17 0.89 0.12 0.45 0.09 0.24 0.04 0.19 0.03 21.08
J. Madhavaraju et al. / Cretaceous Research 31 (2010) 400e414 405
Table 2 (continued )
Member/Sample no Th Pb La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu SREE
CP3 1.13 67 6.49 11.50 1.59 8.04 1.32 0.36 1.57 0.20 1.07 0.21 0.58 0.07 0.48 0.07 33.55
CP1 1.34 41 13.51 28.94 3.05 16.52 2.17 0.49 2.77 0.33 1.45 0.28 0.85 0.12 0.77 0.12 71.37
more enriched in silicate minerals than the CLP and CLE members. linear plots emanating slightly above the intersects of the X and Y
In contrast, the CLP and CLE members are more enriched in axes (Fig. 4aed). This suggests that these elements are mainly
carbonate minerals than the CLC, TS, LC and MQ members. The housed in the clastic materials. Likewise, Sm, Eu, Tb, Yb, and Lu
observed variations in the major oxides concentrations within the show a positive correlation with S(SiO2 þ Al2O3 þ Fe2O3 þ MgO þ
same member from different localities may be due to the amount of Na2O þ K2O þ TiO2) which suggest that these elements are mainly
clastic materials included in them. associated with terrigenous particles (statistically significant at
The bivariate plots of major oxides including certain trace a strict significance level of 0.001; linear correlation coefficient
elements vs the percentage of clastic materials present in the r ¼ 0.64; 0.63; 0.71; 0.78; 0.79; respectively, n ¼ 35). These results
carbonate rocks provide useful information regarding the source of are consistent with the other published studies (Parekh et al., 1977;
these materials (Parekh et al., 1977; Cullers, 2002). In addition, Cullers, 2002).
statistical approach will also useful to understand the statistically The enrichment and depletion of REE in the sediment are
valid or invalid correlation (Verma et al., 2006). A Plot of the controlled by the major processes such as the terrigenous input
S(SiO2 þ Al2O3 þ Fe2O3 þ MgO þ Na2O þ K2O þ TiO2) vs the per- from the continental area, authigenic removal of REE from the
centage of clastic materials show excellent linear correlation and water column and early diagenesis (Sholkovitz, 1988). Seawater
also the linear plot extending from the origin (Fig. 3a). This suggests contributes lesser amount of REE to the sediments where as the
as expected that these oxides are mainly incorporated into the sediments contain high REE concentration show non-seawater-like
clastic materials rather than the calcite. In contrast, CaO and LOI pattern (Nothdurft et al., 2004). The PAAS normalized Seawater REE
have a perfect negative correlation with the percentage of clastic patterns (Fig. 5) are characterized by (1) uniform light REE deple-
materials, suggesting that they are incorporated into the carbonate tion, (2) a negative Ce anomaly, and (3) a slight positive La anomaly
phase (Fig. 3b and c). These results are consistent with the other (e.g., De Baar et al., 1991; Bau and Dulski, 1996) and higher Y/Ho
published studies (Parekh et al., 1977; Cullers, 2002). ratios (e.g., Bau, 1996). The limestones from the CP and SSJ
Trace elements concentrations and their ratios are given in sections show non-seawater-like REE þ Y patterns (CLC:
Tables 2 and 3. The high field strength elements (HFSE), namely Zr, NdN/YbN ¼ 1.52 0.42, n ¼ 5; TS: 1.95 1.17, n ¼ 6; LC: 1.18 0.65,
Y and Th, are resistant to weathering and alteration processes when n ¼ 8; CLP: 0.97 0.08, n ¼ 3, CLE: 0.92 0.15, n ¼ 10; MQ:
compared with other trace elements (Taylor and McLennan, 1985). 1.57 0.19, n ¼ 3; Fig. 6aef). Most of the samples contain positive La
The limestones from the LC and MQ members contain a low and negative Ce anomalies although some samples show slightly
concentration of Zr when compared with other members at the positive La and negative Ce anomalies to no anomalies. Most of the
Cerro Pimas section (Table 2). The CLC, TS and LC members have limestones from the CP and SSJ sections contain chondritic Y/Ho
higher concentrations of Zr than the CLP, CLE and MQ members at ratios (CLC: 30.1 2.7, n ¼ 5; TS: 34.2 5.0, n ¼ 5; LC: 32.1 2.4,
Sierra San José section (Table 2). Maximum concentrations of Y are n ¼ 7; CLE: 35.4 6.1, n ¼ 10; MQ: 32.5 3.3, n ¼ 3; respectively,
found in the CLC, TS, LC and CLE members whereas low concen- Y/Ho Chondritic ratio: w28), but the limestones of the CLP member
trations are found in the MQ Member at Cerro Pimas section from the SSJ section contain slightly higher Y/Ho ratios (CLP:
(Table 2). In the Sierra San José section, the higher concentrations of 41.8 6.4, n ¼ 3). Two samples contain high Y/Ho ratios (CP10:
Y are observed in the CLC, TS, LC and MQ members than the CLP and 70.15 and CP22: 102.5) which have been statistically proved as
CLE members. Overall, the limestones of the Mural Formation outliers using the method proposed by Verma and Quiroz-Ruiz
contain high Sr content (Table 2). (2006a,b). So, we have not included those samples with discor-
Plots of La, Ce, Sc and Th vs S(SiO2 þ Al2O3 þ Fe2O3 þ MgO dant outliers while calculating the mean and standard deviation to
þ Na2O þ K2O þ TiO2) yield significant positive correlation with the improve the authenticity of the data set (Verma et al., 2008).
406 J. Madhavaraju et al. / Cretaceous Research 31 (2010) 400e414
Table 3
Elemental ratios for limestones of the Mural Formation.
Member/Sample no La/Sc La/Co Th/Sc Th/Co Th/Cr Cr/Th Ce/Ce* Eu/Eu* LaN/YbN NdN/YbN Y/Ho
Cerro Pimas section
Mesa Quemada
CP47 5.57 1.33 0.25 0.06 0.02 45.00 0.56 1.13 1.47 1.39 36.07
CP45 5.91 2.05 0.39 0.14 0.04 26.69 0.79 0.91 1.25 1.77 29.56
Cerro La Espina
CP43 2.79 1.44 0.70 0.36 0.17 5.89 0.99 1.26 0.77 1.10 27.68
CP41 7.93 1.17 0.56 0.08 0.23 4.43 0.95 1.01 0.62 0.80 32.75
CP38 5.54 1.12 0.72 0.15 0.21 4.84 1.05 1.02 0.74 1.09 32.33
CP36 7.18 1.89 0.68 0.18 0.23 4.32 1.07 0.84 0.62 0.93 33.45
CP33 11.3 2.13 1.07 0.20 0.14 7.14 0.99 1.00 0.82 1.10 33.96
Los Coyotes
CP28 5.35 0.37 e e e e 0.84 1.17 0.44 0.70 33.60
CP26 6.10 0.99 0.55 0.09 0.03 33.27 0.91 1.21 1.04 1.24 34.00
CP24 5.32 0.73 0.65 0.09 0.07 15.26 0.89 1.09 0.69 0.86 31.57
CP22 11.15 0.74 0.45 0.03 0.03 38.78 0.67 1.33 0.78 0.77 102.50
CP18 7.90 0.47 0.95 0.06 0.07 13.44 0.95 1.44 0.82 1.07 33.28
CP15 8.85 1.17 0.83 0.11 0.08 12.54 0.89 1.35 1.01 1.20 34.05
Tuape Shale
CP12 5.13 2.02 0.71 0.28 0.12 8.47 1.00 1.67 1.28 1.72 31.04
CP10 8.62 3.32 1.21 0.47 0.12 8.10 1.00 1.38 1.64 2.66 70.15
C P9 25.78 7.01 1.78 0.48 0.16 6.23 1.20 1.49 2.75 3.96 29.89
CP6 3.53 2.40 1.07 0.73 0.15 6.54 0.84 1.02 0.52 0.79 32.12
Cerro La Ceja
CP4 7.59 2.10 2.48 0.68 0.20 5.09 0.78 0.98 1.81 2.22 28.00
CP3 7.46 1.22 1.30 0.21 0.17 6.01 0.82 1.17 0.99 1.39 31.48
CP1 7.59 4.01 0.75 0.40 0.15 6.81 1.04 0.94 1.30 1.78 34.00
5.2. Behaviour of Europium Positive Eu anomalies have been reported from Amazon fan
muds in which Eu2þ is precipitated from pore waters during
The limestones from Cerro Pimas and Sierra San Jose sections diagenesis (MacRae et al., 1992). Unlike Ce which can undergo
show large variations in Eu anomalies (Eu/Eu*: 0.84 to 1.67; 0.42 to oxidation state changes in ambient seawater conditions, redox
2.64; respectively). Most of the limestone samples contain positive transformations from Eu3þ to Eu2þ require low oxidation-reduction
Eu anomalies, whereas few samples contain negative Eu anomalies. potentials (pH 2e4) and high temperatures (>200 C) (Sverjensky,
Positive Eu anomalies are mainly found either in sediments affected 1984; Bau, 1991). These conditions are generally absent in shallow
by hydrothermal solutions (Michard et al., 1983; German et al., marine environments. Petrographic and geochemical studies,
1993; Siby et al., 2008); intense diagenesis (Murray et al., 1991b; suggest that the studied limestones were not subjected to intense
MacRae et al., 1992) or variations in plagioclase content (Nath diagenesis. The positive correlation between Eu and the immobile
et al., 1992). Positive Eu anomalies are not common in seawater, elements such as Y, Th and Zr (statistically significant at a strict
which resulted due to hydrothermal discharges along mid-ocean significance level of 0.001; linear correlation coefficient r ¼ 0.69;
ridges (Klinkhammer et al., 1983, 1994). Positive Eu anomalies have 0.74; 0.53; respectively) supports the nondiagenetic influence on
been well documented for hydrothermal vent fluids and sediment this element. The inclusion of small amount of feldspars may lead
particulates in active ridge system (Michard et al., 1983; German to positive Eu anomalies in the bulk sediments (Murray et al.,
et al., 1990, 1999; Douville et al., 1999). Hydrothermal solutions 1991b). In the present study, Eu contents show significant posi-
mainly originate in the deep marine environments but such an tive correlation with Al2O3 which suggest the detrital origin of this
origin is unlikely for the limestones of the Mural Formation which element. Hence, the observed variations in Eu anomalies in the
were deposited in shallow marine environments (Lawton et al., limestones of the Mural Formation may be due to the presence of
2004; González-León et al., 2008). feldspar content rather than hydrothermal events and diagenesis.
408 J. Madhavaraju et al. / Cretaceous Research 31 (2010) 400e414
10
Seawater/PAAS x 10-6
1
0.1 NPSW
Coral Sea
South Fiji basin
Bay of Bengal
Andaman Sea
0.01
La Ce Pr Nd Sm Eu Gd Tb Dy Y Ho Er Tm Yb Lu
Elements
Fig. 5. PAAS normalized REE patterns of modern seawaters (NPSW: North Pacific
shallow water, Sagami trough (Alibio and Nozaki, 1999), Coral Sea: Coral sea (South
Pacific shallow seawater, Zhang and Nozaki, 1996), South Fiji Basin: South Fiji Basin e
Station SA12 (Zhang and Nozaki, 1996), Bay of Bengal: Bay of Bengal shallow water
(Nozaki and Alibio, 2003) and Andaman Sea: Andaman Sea shallow water (Nozaki and
Alibio, 2003).
a 1
d 1
SSJ9 SSJ10 SSJ11
Sample/PAAS
Sample/PAAS
0.1 0.1
CP1 CP3 CP4
SSJ2 SSJ3
0.01 0.01
La Ce Pr Nd Sm Eu Gd Tb Dy Y Ho Er Tm Yb Lu La Ce Pr Nd Sm Eu Gd Tb Dy Y Ho Er Tm Yb Lu
Elements Elements
b 10 e 10
CP33 CP36 CP38 CP41 CP43
CP6 CP9 CP10 SSJ16 SSJ18 SSJ21 SSJ23 SSJ25
CP12 SSJ4 SSJ5 1
Sample/PAAS
Sample/PAAS
1 0.1
0.01
0.1 0.001
La Ce Pr Nd Sm Eu Gd Tb Dy Y Ho Er Tm Yb Lu La Ce Pr Nd Sm Eu Gd Tb Dy Y Ho Er Tm Yb Lu
Elements Elements
1
c 1
f CP45 CP47 SSJ27
Sample/PAAS
Sample/PAAS
0.1 0.1
Elements Elements
Fig. 6. a, REE patterns of limestones of the CLC Member. b, PAAS normalised REE patterns of the TS Member. c, REE patterns of the LC Member. d, REE patterns of limestones of the
CLP Member. e, REE patterns of limestones of the CLE Member. f, PAAS normalized REE patterns of limestones of the MQ Member.
0.001; linear correlation coefficient r ¼ 0.70). The average Fe2O3 these limestones may be due to contamination by terrestrial detritus
concentrations (0.27%, n ¼ 35) of the present study is within the (Webb and Kamber, 2000). In the present study, most of the lime-
range of average carbonate (0.38%, Veizer, 1983) which suggest that stones of the Mural Formation show high values of Th, Sc and Zr and
the diagenetic Fe2O3 does not play a significant role in controlling chondritic Y/Ho ratios, which suggests that these limestones appear
the REE patterns in these limestones. to have been contaminated by terrigenous materials.
Phosphates mainly incorporate REE disproportionally and they The different members of the Mural Formation show slight
are altered easily by diagenesis (Reynard et al., 1999). The lime- variations in LaN/YbN ratios (Table 4). The LaN/YbN ratios of the CLC,
stones of the present study show a positive correlation between TS and MQ members are more or less similar to the values proposed
P
REE and P2O5 (statistically significant at a strict significance level by Condie (1991; about 1.0) and Sholkovitz (1990; about 1.3) for
of 0.001; linear correlation coefficient r ¼ 0.74). A poor correlation terrigenous materials whereas the LC, CLP and CLE members show
has been observed between P and NdN/YbN ratios (statistically lower LaN/YbN ratios. The observed variations in the LaN/YbN ratios
significant at a strict significance level of 0.01; linear correlation in the limestones of the Mural Formation suggest that the REE
coefficient r ¼ 0.42) in the limestones of the Mural Formation. signals were mainly influenced by the incorporation of terrigenous
Hence it is unlikely that the presence of minor quantity of P2O5 materials into them. The LaN/YbN ratios of the Mural Formation are
could affect the REE patterns of limestones of the Mural Formation. more or less similar to the Arabian Sea carbonate sediments (Nath
Thus, our data suggest that contamination by phosphate minerals et al., 1997) and Indian Ocean carbonate sediments (Nath et al.,
or ferromanganese coatings is not likely. 1992) and lower than the shallow marine Albian and Maas-
Yttrium is not removed from the seawater effectively when trichtian limestones (Madhavaraju and Lee, 2009; Madhavaraju and
compared with its geological twin Ho, due to differing surface Ramasamy, 1999; Table 4) of the Cauvery Basin and Kudankulam
complex stabilities, thereby leading to a significant superchondritic Formation (Armstrong-Altrin et al., 2003) of South India (Table 4).
marine Y/Ho ratio (Hogdahl et al., 1968; Zhang et al., 1994; Bau et al., The limestones from the Mural Formation show non-seawater-
1995; Bau, 1996; Nozaki et al., 1997). The chemical sediments free like patterns. The representative samples of the present study were
from contamination generally display Y/Ho ratios between 44 and 74. compared with the limestones having non-seawater-like patterns
But contaminations due to terrestrial detritus and volcanic ash have (Fig. 7; Late Devonian coastal fringing reef, Nothdurft et al., 2004;
fairly constant chondritic Y/Ho values of w28. The limestones of the Albian limestone, Madhavaraju and Lee, 2009; Maastrichtian
Mural Formation contain large variations in Y/Ho ratio (27.34 to limestone, Madhavaraju and Ramasamy, 1999; Miocene limestone,
102.50). Like the Y/Ho ratio, Th and Sc also show significant variations Armstrong-Altrin et al., 2003) which suggests that the inclusions of
among different members of the Mural Formation. Such variations in terrigenous materials in the carbonates as contaminants will mask
410 J. Madhavaraju et al. / Cretaceous Research 31 (2010) 400e414
10
Indian Ocean
CP1 CP4 CP9 CP10
sedimentsl
carbonate
CP33 SSJ2 SSJ3 SSJ6
AL DCFR MAL ML
0.56
1.03
36.6
e
e
1
Sample/PAAS
Arabian Sea
sedimentsk
carbonate
0.84 0.1
0.8 0.2
1.15 0.1
29 12
78 40
0.1
Kudankulam
0.01
Formationj
0.9 0.1
2.7 1.4
0.78 0.3
80 40
La Ce Pr Nd Sm Eu Gd Tb Dy Y Ho Er Tm Yb Lu
49 3
Elements
Devonian coastal fringing reef (Nothdurft et al., 2004), AL: Albian limestone
(Madhavaraju and Lee, 2009), MAL: Maastrichtian limestone (Madhavaraju and
limestonei
0.76 0.2
1.8 0.5
0.58 0.1
73 20
42 8
1.2 0.08
limestoneh
39 25
Th and Sc, chondritic Y/Ho ratios, high LaN/YbN ratios and non-
seawater-like REE patterns indicate that the terrigenous contami-
nations in the limestones of the Mural Formation are responsible
for such variations in REE signals.
Formationg
0.91 0.13
1.0 0.45
1.16 0.34
(average)
35 28
1.6 0.9
1.0 0.24
23 19
whereas the limestones from CLE (at CP section) and LC (at SSJ
e
CLE
1.12 0.03
52 0.5
12 1
the limestones deposited under both coastal and open shelf envi-
ronments exhibit non-seawater-like REE þ Y patterns.
d
CLP
1.17 0.22
1.3 0.29
are higher in silicic than in basic igneous rocks (Cullers, 1995). The
b
Mural Formationaef
TS
felsic and mafic rocks show significant variations in La/Sc, La/Co, Th/
Sc, Th/Co and Th/Cr ratios which are most useful in understanding
Nath et al., 1997, n ¼ 9.
Nath et al., 1992, n ¼ 4.
0.93 0.12
1.12 0.40
1.1 0.14
Present study, n ¼ 5.
Present study, n ¼ 6.
Present study, n ¼ 8.
Present study, n ¼ 3.
Present study, n ¼ 3.
SREE
CaO
S(SiO2 þ Al2O3 þ Fe2O3 þ MgO þ Na2O þ K2O þ TiO2) (Fig. 8). Our
a
i
j
k
l
b
f
c
d
Fig. 8. Bivariate plots for the limestones of the Mural Formation. a, S(SiO2 þ Al2O3 þ Fe2O3 þ MgO þ Na2O þ K2O þ TiO2) vs La/Sc. b, S(SiO2 þ Al2O3 þ Fe2O3 þ MgO þ Na2O þ K2O þ TiO2)
vs La/Co. c, S(SiO2 þ Al2O3 þ Fe2O3 þ MgO þ Na2O þ K2O þ TiO2) vs Th/Sc. d, S(SiO2 þ Al2O3 þ Fe2O3 þ MgO þ Na2O þ K2O þ TiO2) vs Th/Co. e, S(SiO2 þ Al2O3 þ Fe2O3 þ MgO þ Na2O
þ K2O þ TiO2) vs Th/Cr. f, S(SiO2 þ Al2O3 þ Fe2O3 þ MgO þ Na2O þ K2O þ TiO2) vs Eu/Eu*.
Table 5
Range of elemental ratios of the Mural Formation compared to felsic rocks, mafic rocks, Upper Continental Crust (UCC) and Post-Archaean Australian Shale (PAAS).
Range of Mural Formationa Range of sedimentsb Upper Continental Crustc Post-Archaean Australian
average shalec
Felsic rocks Mafic rocks
Eu/Eu* 0.42e2.64 0.40e0.94 0.71e0.95 0.63 0.66
La/Sc 2.65e25.78 2.50e16.3 0.43e0.86 2.21 2.40
La/Co 0.25e8.66 1.80e13.8 0.14e0.38 1.76 1.65
Th/Sc 0.05e2.48 0.84e20.5 0.05e0.22 0.79 0.90
Th/Co 0.03e1.38 0.67e19.4 0.04e1.40 0.63 0.63
Th/Cr 0.02e0.36 0.13e2.7 0.018e0.046 0.13 0.13
Cr/Th 2.76e45.0 4.00e15.0 25e500 7.76 7.53
a
Present study, n ¼ 35.
b
Cullers (1994, 2000); Cullers and Podkovyrov (2000); Cullers et al. (1988).
c
Taylor and McLennan (1985).
The La/Sc, La/Co, Th/Co, Th/Cr, Cr/Th, and Th/Sc ratios of the lime- limestones of the Mural Formation indicate that the terrigenous
stones of the Mural Formation have been compared with felsic and contaminations is responsible for the variations in REE signals. The
mafic rocks (fine fraction) as well as to upper continental crust limestones of the Mural Formation were compared with the lime-
(UCC) and PAAS values (Table 5) which suggest that these ratios are stones having non-seawater-like patterns that indicate the inclu-
within the range of intermediate to felsic rocks. sion of terrigenous materials in the carbonates, as contaminants
will mask the seawater signature due to their high concentration of
6. Conclusions the REE in them. The limestone samples from CLP member show
negative Ce anomalies (Ce/Ce*: 0.77 to 0.83, ave. 0.80 0.03, n ¼ 3)
The high content of Al2O3, SREE, Th and Sc, low Y/Ho ratios, high whereas CLC, TS, LC, CLE and MQ members show both negative and
LaN/YbN ratios and non-seawater-like REE patterns in the positive Ce anomalies (Ce/Ce*: 0.78 to 1.04, ave. 0.93 0.12, n ¼ 5;
412 J. Madhavaraju et al. / Cretaceous Research 31 (2010) 400e414
0.82 to 1.20, ave. 0.96 0.14, n ¼ 6; 0.67 to 1.05, ave. 0.90 0.12, northern Italy): assessing REE sensitivity to environmental changes. Chemical
Geology 141, 141e152.
n ¼ 8; 0.73 to 1.07, ave. 0.93 0.12, n ¼ 10; 0.56 to 1.00, ave.
Bertram, C.J., Elderfield, H., 1993. The geochemical balance of the rare earth
0.78 0.22, n ¼ 3; respectively). The observed variations in Ce elements and neodymium isotopes in the oceans. Geochimica et Cosmochimica
anomalies resulted from the inclusion of terrigenous materials as Acta 57, 1957e1986.
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Acknowledgements
siltstones and sandstones of Ordovician to Tertiary age in the Wet Mountain
region, Colorado, U.S.A. Chemical Geology 123, 107e131.
The first author would like to thank Dr. Thierry Calmus, ERNO, Cullers, R.L., 2000. The geochemistry of shales, siltstones and sandstones of Penn-
Instituto de Geología, Universidad Nacional Autónoma de Mexico sylvanianePermian age, Colorado, U.S.A.: implications for provenance and
metamorphic studies. Lithos 51, 305e327.
for his support and encouragement during this work. We would Cullers, R.L., 2002. Implications of elemental concentrations for provenance, redox
like to thank Prof. S.P. Verma and Prof. R.L. Cullers for their critical conditions, and metamorphic studies of shales and limestones near Pueblo, CO,
reviews and constructive comments. We would like to thank Dr. USA. Chemical Geology 191, 305e327.
Cullers, R.L., Basu, A., Suttner, L., 1988. Geochemical signature of provenance in
Hannes Löser for his help during the field work. We acknowledge sand-size material in soils and stream sediments near the Tobacco Root bath-
the support rendered by Universidad Nacional Autónoma de olith, Montana, USA. Chemical Geology 70, 335e348.
Mexico through PAPIIT Project No.IN121506-3. The field study of Cullers, R.L., Podkovyrov, V.N., 2000. Geochemistry of the Mesoproterozoic
Lakhanda shales in southeastern Yakutia, Russia: implications for mineralogical
this work is partly supported by PAPIIT Project No. IN107803-3. We and provenance control, and recycling. Precambrian Research 104, 77e93.
thank Mr. Pablo Peñaflor for powdering of limestone samples for De Baar, H.J.W., Schijf, J., Byrne, R.H., 1991. Solution chemistry of the rare earth
geochemical studies. We also thank Dr. Teresa Pi I Puig, Instituto de elements in seawater. European Journal of Solid State Inorganic Chemistry 28,
357e373.
Geología, Universidad Nacional Autónoma de México, México for Dickinson, W.R., Klute, M.A., Swift, P.A., 1986. The Bisbee Basin and its bearing on
her help in XRD analysis. This research was partly supported by late Mesozoic paleogeographic and paleotectonic relations between the
Korea Science and Engineering Foundation (KOSEF) grants (R01- Cordilleran and Carribean regions. In: Abbott, P.L. (Ed.), Cretaceous Stratigraphy,
vol. 46. Pacific Section (SEPM) Book, Western North America, pp. 51e62.
2000-000-00056-0 to YIL).
Dickinson, W.R., Klute, M.A., Swift, P.A., 1989. Cretaceous strata of southern Arizona.
In: Jenney, J.P., Reynols, S.J. (Eds.), Geologic Evolution of Arizona. Arizona
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