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Elemental geochemistry of sedimentary rocks – A review

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2nd International Symposium on Geosciences
(ISG2021)
1st April 2021
Proceeding Book
 ELEMENTAL GEOCHEMISTRY OF SEDIMENTARY ROCKS – A REVIEW
Osama R. Shaltami1 and Ilas Bustany2
1Department of Earth Sciences, Faculty of Science, Benghazi University, Libya
2Guanabara Bay Company, Rio de Janeiro, Brazil

Abstract rare earth elements in coal and shale has extensively been
The chemical composition of sediments and sedimentary analyzed and described (Liu and Lee, 2001; Dai et al., 2008;
rocks is extremely diverse, reflecting the variability of the Baioumy et al., 2014; Dianshi et al., 2019).
mineralogical composition. Sediments may be classified
according to the origin of the minerals composing the bulk 2. Chemostratigraphy
sediment. End members are designated as terrigenous Chemostratigraphy is the study of the inorganic/organic
(siliciclastic), biogenic, and metalliferous. Terrigenous chemical variations within the sedimentary sequences, either
sediments are products of physical and chemical weathering based on the elemental or isotopic composition of the rock. It
and erosion of upper crustal rocks exposed at Earth’s surface. provides a useful tool for unconventional resource exploration
During these processes, major changes in mineralogy and and development. The chemistry of a rock varies with its
chemistry occur, because primary igneous and metamorphic mineral composition. Rock chemistry is relatively easy to
rocks formed and equilibrated at elevated temperatures and measure, so quantifiably, the rocks can be placed in a
pressures are thermodynamically unstable at surface chemostratigraphic sequence framework. Chemofacies are
conditions. Biogenic sediments result from the production, analogous to lithofacies in stratigraphy (Ramkumar, 2015).
preservation, and diagenetic transformation of minerals
initially produced by living organisms. Metalliferous 3. Chemical Classification
sediments commonly result from exhalative processes along The chemical and mineralogical compositions of
mid-ocean ridges and are enriched in Fe, Mn, Zn, Cu, and sediments and sedimentary rocks are extremely diverse.
other metallic elements. However, sedimentary rocks can be divided depending on the
Keywords: Elemental Geochemistry of Sedimentary Rocks, chemical composition as shown in Figs.1-3 and Tables 1-3.
Geochemistry.
4. Provenance
1. Introduction McLennan et al., (1993) have defined five distinct
Elemental geochemical parameters and their ratios are provenance components on the basis of geochemical
widely used to assess paleoenvironmental conditions, ancient compositions. These components include the following: Old
water compositions, paleotectonic settings, and the Upper Continental Crust (OUC), Recycled Sedimentary Rocks
provenance of sedimentary rocks (Sun et al., 2012; Shaltami et (RSR), Young Undifferentiated Arc (YUA), Young
al., 2016; Claes et al., 2019). The composition of source Differentiated Arc (YDA) and Exotic components. The Old
rocks, degree of weathering in the source area, depositional Upper Continental Crust components constitute the old, well-
setting and post-depositional modifications are some of the differentiated upper continental crust that is characterized by a
factors that influence the chemical and mineralogical substantial Eu anomaly. The Recycled Sedimentary Rocks
composition of sedimentary rocks (Nesbitt et al., 1980, Roser component includes recycled sedimentary and meta-
and Korsch, 1988; McLennan et al., 1993). In recent years, the sedimentary rocks. The Young Undifferentiated Arc
distribution of major and trace elements, including those of component represents the young (dominantly mantle derived)

ISG2021 93
igneous arc material (volcanic or plutonic) that has not (Lindsey, 1999). The degree of source rock weathering is
undergone significant intracrustal differentiation (i.e., it has quantified variously. A few indices of weathering have been
not undergone plagioclase fractionation and therefore show no proposed based on molecular proportions of mobile and
Eu anomalies). The Young Differentiated Arc provenance immobile element oxides (Na2O, CaO, K2O and Al2O3).
component constitutes the young (mantle derived) volcanic or Among the known indices of weathering/alteration the
plutonic igneous rocks from island and continental arcs that Chemical Index of Alteration (CIA; Nesbitt and Young, 1982)
have undergone significant intracrustal differentiation. The is well established as a method of quantifying the degree of
general geochemical characteristics of sediments derived from source weathering. Source weathering and elemental
these four provenance types are summarized in Table 4. redistribution during diagenesis also can be assessed using
Plagioclase Index of Alteration (PIA; Fedo et al., 1995) and
The geochemical signatures of clastic sediments have been Chemical Index of Weathering (CIW; Harnois, 1988). For
used to find out the provenance characteristics (Taylor and quantifying source weathering of carbonate-bearing
McLennan, 1985; Condie et al., 1992; Cullers, 1995; siliciclastic rocks, a modified version of CIW (CIW´; Cullers,
Madhavaraju and Ramasamy, 2002). Al2O3/TiO2 ratios of 2000) is also considered. The equations of the above indices
most clastic rocks are essentially used to infer the source rock are:
compositions, because the Al2O3/TiO2 ratio increases from 3 CIA = {Al2O3 / (Al2O3 + CaO* + Na2O + K2O)} x 100
to 8 for mafic igneous rocks, from 8 to 21 for intermediate PIA = {(Al2O3 – K2O) / ((Al2O3 - K2O) + CaO* + Na2O)} x
rocks, and from 21 to 70 for felsic igneous rocks (Hayashi et 100
al., 1997). Moreover, many authors used La/Sc, Th/Cr, Th/Sc CIW = {Al2O3 / (Al2O3 + CaO* + Na2O)} x 100
and Th/Co ratios to determine the source of sediments (Table CIW´ = {Al2O3 / (Al2O3 + Na2O)} x 100
5). In addition, there are several models that can be used to
determine the provenance of sediments (Figs. 4-9). In the above equations the major oxides are expressed in
molar propotions and CaO* is the content of CaO incorporated
5. Paleoweathering in silicate fraction. McLennan et al., (1993) proposed an
Intensity of chemical weathering of source rocks is indirect method for quantifying CaO content of silicate
controlled mainly by source rock composition, duration of fraction assuming reasonable values of Ca/Na ratios of silicate
weathering, climatic conditions and rates of tectonic uplift of material. Procedure for quantification of CaO content (CaO*)
source region (Wronkiewicz and Codie, 1987). About 75% of of silicate fraction involves subtraction of molar proportion of
the labile material of the upper crust is composed of feldspars P2O5 from the molar proportion of total CaO. After
and volcanic glass and chemical weathering of these materials subtraction, if the “remaining number of moles” is found to be
ultimately results in the formation of clay minerals (Taylor less than the molar proportion of Na2O, then the “remaining
and McLennan, 1985; Fedo et al., 1995). During chemical number of moles” is considered as the molar proportion of
weathering Ca, Na and K are largely removed from source CaO of silicate fraction. If the “remaining number of moles” is
rocks. The amount of these elements surviving in soil profiles greater than the molar proportion of Na2O, then the molar
and in sediments derived from them is a sensitive index of the proportion of Na2O is considered as the molar proportion of
intensity of chemical weathering (Nesbitt et al., 1997). If the CaO of silicate fraction (CaO*).
siliciclastic sedimentary rocks are free from alkali-related
post-depositional modifications, then their alkali contents During the initial stages of weathering, Ca is quickly
(K2O+Na2O) and K2O/Na2O ratios are considered as reliable leached than Na and K. With increasing weathering, the total
indicators of intensity of weathering of source material alkali content (K2O+Na2O) decreases with increase in

ISG2021 94
K2O/Na2O ratio. This is due to destruction of feldspars among (Bau and Alexander, 2009). The B/Ga ratio is one of the
which plagioclase is more favorably removed than K-feldspars parameters used to define the paleosalinity of sediments (Deng
(Nesbitt and Young, 1984). Feldspathic materials in the and Qian, 1993). High B/Ga value (>4.2) indicates salt water,
sandstones and shales were subjected to variable intensities of B/Ga values from 3.3 and 4.2 suggest brackish water, and
weathering during the different evolution stages. Mobility of B/Ga ratio lower than 3.3 points to fresh water (Deng and
elements during the progress of chemical weathering of source Qian, 1993). Sr and Ba are two elements with different rate of
material and post-depositional chemical modifications of immigration following changes in paleosalinity. Sr/Ba ratio is
sediments can be evaluated by plotting the molar proportions widely regarded as an indicator of paleosalinity. The high
of Al2O3-(Na2O+CaO*)-K2O in A-CN-K ternary diagram (Fig. Sr/Ba ratio reflects a high salinity in the ambient water, and
10). the low ratio, a low salinity (Epstein and Mayeda, 1953). This
ratio increases in samples deposited under warm and humid
6. Paleoclimate and Maturity conditions (Cao et al., 2015). However, models used to define
The original character and maturity of sediments as well as the depositional environment are illustrated in Figs. 14 and 15.
the prevailed climatic conditions can be determined by
calculating the index compositional variation (ICV) proposed Trace element ratios such as Ni/Co, V/Cr, V/Sc, V/(V+Ni)
by (Cox et al., 1995). According to Baiyegunhi et al., (2017) and U/Th as well as authigenic U (AU = U-(Th/3)) and δU
the ICV tends to be highest in minerals that are high in (δU = 2U/(U+Th/3)) have been used in many studies to
weathering intensity and decreases in more stable minerals determine the redox conditions of sediments. Table 6
(less weathered minerals). The ICV decreases further in the illustrates the standards for these parameters.
montmorillonite group clay minerals and lowest in the
kaolinite group minerals (Cox et al., 1995). In addition, more 8. Paleotectonic Setting
mature shale tends to have low ICV values (<1). The ICV Several studies have shown that the chemical compositions
were calculated as: of siliciclastic sedimentary rocks are significantly controlled
ICV = (Fe2O3+K2O+Na2O+CaO+MgO+MnO)/Al2O3 by plate tectonic settings of their provenances and depositional
basins, and as a result, the siliciclastic rocks from different
The K2O/Na2O and TiO2/Zr ratios are used as a maturity tectonic settings posses terrain-specific geochemical
parameter in many studies (e.g., Garcia et al., 1994, Asiedu et signatures (Bhatia, 1983; Roser and Korsch, 1986). Many
al., 2000; Shaltami, 2012). Mature sediments show a wide types of discrimination diagrams of tectonic settings that use
range of K2O/Na2O and TiO2/Zr variations whereas immature major oxides and trace elements chemistry have been
sediments show a more limited range of K2O/Na2O and proposed for clastic sediments (Figs. 16 and 17). The tectonic
TiO2/Zr variations. Furthermore, the chemical maturity of diagrams discriminate between Oceanic Island Arc (A),
sediments can be determined using several models (Figs. 11- Continental Island Arc (B), Active Continental Margin (C)
13). and Passive Continental Margin (D).

7. Depositional Environment 9. Conclusions

Many authors used trace element ratios to determine the The geochemistry of sedimentary rocks bears much
depositional environment of clastic rocks. The most common important information about how the crust has evolved
ratios are Zr/Hf, Hf/Ta and Zr/Ta (Bau and Alexander, 2009). through geological history. The sedimentary rocks are very
In the marine environment, the Zr/Hf, Hf/Ta and Zr/Ta ratios complicated in chemical composition because of the influence
range from 56 to 207, 1.3 to 2.5 and 115 to 688, respectively of weathering, erosion, transport, deposition and diagenesis.

ISG2021 95
But many studies indicate that some elements including REE, the redox level of the Neoarchean ocean. Precambrian
Th and Sc in terrigenous sediments can be transported in large Research; 174: 337-346.
quantities because the distribution of these elements is rarely
affected by secondary processes such as diagenesis and Cao, H.; Guo, W.; Shan, X.; Ma, L. and Sun, P. (2015):
metamorphism. As a result, they are the best candidate for Paleolimnological environments and organic accumulation of
studying the crustal evolution. Although the representative the Nenjiang Formation in the southeastern Songliao Basin,
elements are only limited in number, they can provide reliable China. Oil Shale; 32 (1): 5-24.
indices for the study of crustal composition.
Claes, H., Huysmans, M., Soete, J., Dirix, K., Vassilieva, E.,
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Fig. 1: Binary plot of log(SiO2/Al2O3) vs. log(Na2O/K2O) showing the chemical classification of sandstones (after Pettijohn et al.,
1972).

Fig. 2: Binary plot of log(SiO2/Al2O3) vs. log(Fe2O3/K2O) showing the chemical classification of sandstones (after Herron, 1988).

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 SiO2

Iron formations

Ironstones

FeO + MgO Fe2O3

Fig. 3: Ternary plots of SiO2-FeO+MgO-Fe2O3 showing the difference between Precambrian iron formations and Phanerozoic
ironstones (after James, 1992).

Fig. 4: Binary plot of La/Sc vs. Th/Co showing the provenance of sediments (after Cullers, 2002).

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 Fig. 5: Binary plot of Zr vs. TiO2 showing the provenance of sediments (after Hayashi et al., 1997).

Fig. 6: Binary plot of Ni vs. TiO2 showing the provenance of sediments (after Floyd et al., 1989).

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 Fig. 7: Binary plot of Hf vs. La/Th showing the provenance of sediments (after Floyd and Leveridge, 1987).

Fig. 8: Binary plot of La/Sc vs. Co/Th showing the provenance of sediments (after McLennan et al., 1993).

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 Fig. 9: Binary plot of Sc vs. Th showing the provenance of sediments (after McLennan et al., 1993).

CIA % Al2O3 %
100 Kaolinite, Gibbsite, Chlorite

Smectite Illite

Muscovite

Weathering Biotite
trend
50 Plagioclase K-feldspar

Feldspar join

Hornblende

Clinopyroxene
0
(Na2O + CaO*) % K2O %

Fig. 10: Ternary plot of A-CN-K showing the paleoweathering of sediments (after Nesbitt and Young, 1982).

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 Fig. 11: Binary plot of CIA vs. ICV showing the maturity for sediments (after Baiyegunhi et al., 2017).

Fig. 12: Binary plot of (Al2O3+K2O+Na2O) vs. SiO2 showing the paleoclimate conditions for sediments (after Suttner and Dutta,
1986).

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 Fig. 13: Binary plot of K2O/Al2O3 vs. Ga/Rb showing the paleoclimate conditions for sediments (after Roy and Roser, 2013).

Fig. 14: Binary plot of (La/Sm)N vs. (La/Yb)N showing the depositional environment of sediments (after Cook and Trueman, 2009).

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 Fig. 15: Binary plot of Vi/Ni vs. Co/Ni showing the depositional environment of sediments (after Galarraga et al., 2008).

A
Ti/Zr

B C

La/Sc

Fig. 16: Binary plot of La/Sc vs. Ti/Zr showing the paleotectonic setting of sediments (after Bhatia and Crook, 1986).

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 Th

D
B

A
Sc Zr/10

Fig. 17: Ternary plot of Th-Sc-Zr/10 showing the paleotectonic setting of sediments (after Bhatia and Crook, 1986).

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 Table 1: Classification of limestones according to CaCO3 content (after Lorenz and Gwosdz, 2003)

Category Chemical composition (%)

Highly pure limestone >98.5
Pure limestone >97–98.5
Limestone, standard quality >93.5–97
Limestone, low quality 85–93.5
Impure limestone <85

Table 2: Classification of limestones according to CaCO3 content (after Lorenz and Gwosdz, 2003)
CaCO3 content (%) Classification of hard rock
100–95 Limestone
95–85 Marly limestone
85–75 Marlaceous limestone
75–65 Calcareous marlstone
65–35 Marlstone
35–25 Clay marlstone
25–15 Marlaceous claystone
15–5 Marly claystone
5–0 Claystone

Table 3: Chemical classification of phosphate bearing rocks according to P2O5 content (after PettiJohn, 1957)
Category P2O5 (%)
Phosphatized rocks 3-9.8
Phosphatic rocks 9.8-19.5
Phosphorite rocks >19.5

Table 4: Geochemical characteristics of sediment derived from different provenance types (after McLennan et al., 1993)
Provenance type Eu/Eu* Th/Sc Th/U Others
Evolved major element composition
Old upper continental
0.6-1.1 1.0 >3.8 (e.g. high Si/Al, CIA) high LILE
crust
abundance, uniform compositions
Evidence of heavy minerals
Recycled sedimentary
0.6-1.1 ≥ 1.0 >3.8 concentration from trace elements
rocks
(e.g. Zr,Hf for zircon)
Evolved major element composition
Young differentiated arc 0.5-0.9 1.0 to <0.01 <3.0 (e.g. high Si/Al, CIA) high LILE
abundance variable compositions
Unevolved major element
Young undifferentiated composition (e.g. low Si/Al, CIA) low
1.0 1.0 to <0.01 <3.0
arc LILE abundance variable
compositions

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 Table 5: Range of elemental ratios derived from felsic rocks, mafic rocks and Post-Archean Australian Shale (after Taylor and
McLennan, 1985; Cullers and Podkovyrov, 2000)
Rocks La/Sc Th/Sc Th/Cr Th/Co
Felsic rocks 2.5 - 16.3 0.84 - 20.5 0.13-2.70 0.67 - 19.4
Mafi c rocks 0.43 - 0.86 0.05 - 0.22 0.02-0.05 0.04 - 0.4
PAAS 2.40 0.90 0.13 0.63

Table 6: Redox classification using trace element ratios (after Jones and Manning, 1994, Nath et al., 1997, Nagarajan et al., 2007 and
Yao et al., 2017)
Ratio Oxic conditions Anoxic conditions
Ni/Co <5 >5
V/Cr <2 >2
V/Sc <9 >9
V/(V+Ni) <0.46 >0.46
U/Th <1.25 >1.25
AU <5 >5
δU <1 >1

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