Applied Geochemistry 141 (2022) 105321

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Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem

Geochemistry of marine sediments adjacent to the Los Tuxtlas Volcanic

Complex, Gulf of Mexico: Constraints on weathering and provenance
John S. Armstrong-Altrin a, *, Mayla A. Ramos-Vázquez b, Jayagopal Madhavaraju c,
Mario Emilio Marca-Castillo d, María Luisa Machain-Castillo a, Antonio Zoilo Márquez-García e
a
Unidad de Procesos Oceánicos y Costeros, Instituto de Ciencias del Mar y Limnología, Universidad Nacional Autónoma de México, Ciudad Universitaria, Ciudad de
México, 04510, CDMX, Mexico
b
División de Geociencias Aplicadas, Instituto Potosino de Investigación Científica y Tecnológica (IPICYT), Camino a la Presa San José 2055, San Luis Potosí, 78216,
Mexico
c
Estación Regional del Noroeste, Instituto de Geología, Universidad Nacional Autónoma de México, Hermosillo, Sonora, Mexico
d
Posgrado en Ciencias del Mar y Limnología, Universidad Nacional Autónoma de México, Ciudad Universitaria, Ciudad de México, 04510, CDMX, Mexico
e
Universidad Autónoma Metropolitana, Unidad Iztapalapa, Iztapalapa, 09340, CDMX, Mexico

A R T I C L E I N F O A B S T R A C T

Editorial handling by Dr M Liotta The provenance of GoM45 and GoM63 core sediments recovered in the deep-sea area (~1666 m–1672 m water
depth, respectively), in front of the Los Tuxtlas volcanic field, Gulf of Mexico was analyzed based on the textural,
Keywords: mineralogical, and geochemical variations. The radiocarbon age data of Globorotalia menardii group foraminiferal
Deep-sea sediments species varied from 17,709 to 20,711 calibrated years B.P for the sediment core GoM45, which represent
Continental shelf
Pleistocene/Holocene boundary. The core sediments were characterized by detrital components with enriched
Radiocarbon ages
SiO2, Al2O3, and Fe2O3 concentrations. The weathering indices like Chemical Index of Alteration (CIA), Chemical
Drilling
Mineralogy Index of Weathering (CIW), and Plagioclase Index of Alteration (PIA) revealed a low intensity of weathering for
the core sediments.
The V/Cr, Ni/Co, Cu/Zn, and V/Cr elemental ratios indicated an oxic depositional environment for the Gulf of
Mexico deep sea area. In addition, the geochemistry data indicated a passive margin setting, which is consistent
with the geology of the Gulf of Mexico. The trace and rare earth element concentrations, and Eu anomaly
indicated that the sediments were derived from the natural erosion of andesitic and basaltic rocks in the Los
Tuxtlas region, SW Gulf of Mexico. Los Tuxtlas region is partly influenced by the Papaloapan and Coatzacoalcos
Rivers, which discharges into the SW Gulf of Mexico.

1. Introduction
The provenance of deep-sea sediments can be analyzed through
textural, mineralogical, and geochemical compositions (Madhavaraju
et al., 2016a, 2021; Basu, 2020; Kasper-Zubillaga et al., 2021). Tracing
and quantifying the provenance of deep-sea sediments is particularly
useful to constraint the erosional history and palaeoenvironment (Liu
et al., 2020; Roddaz et al., 2021). The provenance and source-to-sink
sediment dispersal systems are controlled by the intrabasinal and
extrabasinal sources, lithology, source rock types, and sediment
pathway (Wang et al., 2020; Razum et al., 2021). Knowledge of sedi­
ment recycling and sediment transfer mechanism from land to sea pro­
vide important constraints on continental weathering and earth surface
processes (Li et al., 2016). The tectonic, climatic, and environmental
changes, affect the source-to-sink sediment transport pathway, which
eventually influence the depositional basin (Mason et al., 2017;
Schwestermann et al., 2021). Recent studies revealed the importance of
sediment composition to infer the provenance as well as to reconstruct
the paleoclimate of a particular region (Verma and Armstrong-Altrin,
2013; Anthony et al., 2019; Banerjee et al., 2020; Jamwal et al., 2020;
Krishnan et al., 2020; Chougong et al., 2021; Yang et al., 2021). The
deep-sea sediments are commonly classified as lithogenous, cosmoge­
nous, and biogenous. The redox state of both sea water and deep-sea
sediments is most important to understand the marine depositional
environment. Chemical changes in deep-sea sediments are controlled by
the oxygen concentration of the sea water. Similarly, the concentration

* Corresponding author.
E-mail addresses: armstrong@cmarl.unam.mx, john_arms@yahoo.com (J.S. Armstrong-Altrin).

https://doi.org/10.1016/j.apgeochem.2022.105321
Received 17 December 2021; Received in revised form 25 April 2022; Accepted 26 April 2022
Available online 29 April 2022
0883-2927/© 2022 Elsevier Ltd. All rights reserved.
J.S. Armstrong-Altrin et al.
Fig. 1. Map showing core locations in the SW Gulf of Mexico (modified after Anaya-Gregorio et al., 2018).
of metals in deep-sea sediments are controlled by redox conditions of sea
water and the availability of trace metals in the marine depositional
environment (Sato et al., 2012; Meinhardt et al., 2016; Ekoa Bessa et al.,
2018; Swain et al., 2021; Rasul and Al-Jaleel, 2022). Chemical compo­
sition of deep-sea sediments can be evaluated based on the major and
trace element concentrations, because compositional changes are
controlled by the relative proportions of sediment-forming minerals
related to their parent rocks. The immobile trace elements like rare earth
elements (REE), Cr, Hf, Nb, Ni, Th, and V are highly reliable indicators to
infer sediment provenance due to their resistance against geological
processes such as weathering, recycling, and sorting during transport
(Cullers 2000; Zaid et al., 2015; Madhavaraju et al., 2017; Velmurugan
et al., 2019; Subin et al., 2022). In addition, chondrite normalized REE
patterns and differences in Eu anomalies are extensively utilized in
various studies to infer source rock characteristics (Armstrong-Altrin
et al., 2017; Madhavaraju et al., 2019; Chaudhuri et al., 2020; Ramír­
ez-Montoya et al., 2021).
There are few studies, which discussed the sediment composition of
deep-sea sediments in the Gulf of Mexico (Armstrong-Altrin, 2015;
Armstrong-Altrin et al., 2015; Ramos-Vázquez et al., 2017; Anaya-­
Gregorio et al., 2018). These studies analyzed the geochemistry of
2
Applied Geochemistry 141 (2022) 105321
sediments recovered from the southern part of the Gulf of Mexico and
investigated the provenance and tectonic environment. In addition,
heavy metal contamination of estuary (Vera-Mendoza and Sal­
as-de-León, 2014; Botello et al., 2015; Rosales-Hoz et al., 2015; Arm­
strong-Altrin et al., 2019) and marine sediments near the Coatzacoalcos
area, Gulf of Mexico were investigated by few researchers (Arm­
strong-Altrin and Machain-Castillo, 2016; Ramos-Vázquez et al., 2018;
Ramos-Vázquez and Armstrong-Altrin, 2021a,b; Ayala-Pérez et al.,
2021; Mapel-Hernández et al., 2021).
Sediments are a potential source of trace metals in marine environ­
ments and play an important role in transmission of metals (Hill et al.,
2013; LeMonte et al., 2017; Horasan et al., 2020). Intermittent rivers
and their flow cessation occur naturally and spatiotemporally in these
systems. The majority of trace metals originate from natural sources
such as volcanic eruptions, rock weathering, erosion, and atmosphere.
Similarly, anthropogenic activities such as agriculture, industry, and
extensive urban development in a coastal environment are considered as
a threat to the human population (Sundararajan et al., 2017; Jha et al.,
2019; Liu et al., 2019; Shaheen et al., 2019; Tehna et al., 2019; Zhan
et al., 2020; Andráš et al., 2021; Armstrong-Altrin et al., 2021a).
This study provides a comprehensive major and trace element
J.S. Armstrong-Altrin et al. Applied Geochemistry 141 (2022) 105321

geochemistry data integrated with mineralogy and granulometric

analysis of two sediment cores GoM45 and GoM63 recovered in the SW
Gulf of Mexico. The objective of this study is to investigate the weath­
ering, provenance, and sedimentation rate.

2. Study area

Two sediment cores, GoM45 and GoM63 (~1666 m–1672 m water

depth, respectively; ~5 m long) were recovered 80 km off the coast in
front of Los Tuxtlas volcano, SW Gulf of Mexico (Fig. 1; 19◦ 10′ 12′′ N
94◦ 45′ 64′′ W and 19◦ 09′ 70′′ N 95◦ 09′ 57′′ W, respectively).
The core recovered areas were dominantly influenced by sediments
supplied by the Coatzacoalcos and Papaloapan Rivers. The Coat­
zacoalcos River is one of the major rivers supplying sediments to the
southern part of the Gulf of Mexico, drains between 17◦ 46′ -18◦ 10′ N and
92◦ 25′ -94◦ 31′ W. It is 325 km in length with a catchment area of 17,369
km2, and a mean surface runoff of 28,093 Hm3, which is located in the
coastal plain of the Gulf of Mexico, mostly in the Tabasco and Veracruz
states. The Papaloapan River basin (17◦ 19◦ N and 95◦ –97◦ 40′ W) is the
second largest hydrological basin in Mexico, drains 39,189 km2 of
catchment area before reaching the Gulf of Mexico with an annual
volume of discharge of 39,175 km3. The Papaloapan River flows into the
Gulf of Mexico through the Alvarado lagoon, Veracruz State. The
Papaloapan basin is divided into upper (above 1000 m.a.s.l.) and lower
Papaloapan. Los Tuxtlas area in Veracruz, forms part of the lower
Papaloapan, even though it includes an area higher than 1000 m.a.s.l.
(Tamayo, 1991). The Veracruz state is considered as one of the intensive
industrialized areas, second in the manufacture of iron and steel, and it
is fourth in the extraction of oil and gas (Jiménez-Orocio et al., 2015;
Rosales-Hoz et al., 2015; Cancino-Solórzano et al., 2016). There are
river tributaries originating from Tuxtla, Santa Marta, and San Martín
volcanoes, which spill their waters directly into the SW Gulf of Mexico.
Fig. 2. Photograph showing GoM45 core section recovered from the SW Gulf
2.1. Geology of Mexico.

Los Tuxtlas Volcanic Complex consists of various monogenetic

3. Methodology
erupted cones in the region between San Martín and Catemaco, Veracruz
State (Fig. 1). The volcanoes are younger in age, mostly less than 4000
The GoM45 and GoM63 sediment cores (~1666 m–1672 m water
years old (Ruiz-Mendoza et al., 2021; Verma et al., 2021). The area is
depth, respectively; ~5 m long) were retrieved on-board the research
almost completely covered by pyroclastic deposits and lava flows, and
vessel “Justo Sierra” on June 2017, which belongs to National Autono­
with a low proportion of marine sediments of Tertiary age. Other than
mous University of Mexico (UNAM). The recovered sediment cores were
the volcanic rocks, sedimentary rocks, such as limestone, clay and
sub-sampled at every cm for various analyses and kept in the Sedi­
sandstone are also present in the Los Tuxtlas area (Verma, 2000) (Fig. 1).
mentology Laboratory, ICML, UNAM (Fig. 2). The samples were dried
In general, the outcrops of the river draining areas in the central part of
for 24 h at 40 ◦ C and powdered using agate mortar. The sediment
the western Gulf of Mexico are composed of 1) alluvium and soils
samples were analyzed for 14C planktonic foraminifera, particle size
(Quaternary age), 2) volcanic rocks of mafic and intermediate types
distribution, mineralogy, and geochemistry including major, trace, and
(Cenozoic age), 3) clastic and calcareous sedimentary rocks (Cenozoic
rare earth element concentrations.
and Mesozoic age), and 4) metamorphic rocks comprising schists and
gneisses (Paleozoic and Precambrian age). Volcanic rocks are dominated
3.1. Foraminiferal analysis
by Miocene-Pliocene andesites of sub-alkaline, mafic, and intermediate
compositions (Verma, 2001; Armstrong-Altrin et al., 2021b) (Fig. 1).
Samples for foraminiferal analysis were sieved through an American
The volcanic units of the study areas belong to the overlap region of the
Society for Testing Materials (ASTM) sieve No. 230 (<62 μm), then
Mexican Volcanic Belt (MVB) and the Eastern Alkaline Province (Verma,
washed with running water, dried and picked under a stereoscopic mi­
2000).
croscope. All planktonic species were determined and counted based on
the methodology proposed by Martin and Liddell (1989). For biostrati­
2.2. Hydrology and oceanography
graphic analysis Globorotalia menardii group graphics were constructed.
For 14C analysis three samples (3 mg mixed planktonic foraminifera
The anticyclonic eddies that are separated episodically from the Loop
each) were sent to Beta Analytic Testing Laboratory for Accelerator Mass
current in the eastern Gulf of Mexico travel to the western limit of the
Spectrometer (AMS) dating. The conversion of 14C radiocarbon ages into
Gulf of Mexico, interacting with numerous accompanying cyclones and
calendar years BP was performed using the CALIB software (Stuiver and
significantly contributing to the variability of the upper layer (above
Reimer, 1993, version 5.0.2; http://calib.qub.ac.uk/calib). After cali­
500–1000 m depth) in the central and western regions. During summer,
bration, ages between dated sections were obtained by linear interpo­
when the winds over the Tamaulipas and Veracruz platforms have a
lation. The sedimentation rate in the SW Gulf of Mexico deep sea area
northward component, the currents are predominantly in that direction
was reported as ~0.0166 cm/year (Ramos-Vázquez et al., 2018).
and confluence occurs near the border with the United States (Mon­
real-Gómez et al., 1992).

3
J.S. Armstrong-Altrin et al.
14
Fig. 3. C ages of Globorotalia menardii planktonic foraminifera in the GoM45 and GoM63 sediment cores from the SW Gulf of Mexico.
3.2. Granulometric analysis
The textural characteristics were analyzed by Beckman Coulter
particle size analyzer (Coulter LS230), at the Sedimentology Laboratory,
ICML, UNAM (number of samples n = 20). Grain sizes were measured
based on the classification scale proposed by Wentworth (1922), as well
as described by Rząsa and Owczarzak (2013). The textural parameters:
grain size, sorting, skewness, and kurtosis were calculated by the
equations proposed by Folk and Ward (1957).
3.3. Mineralogy
In order to detect the mineralogical composition, 5 samples from
GoM45 and 5 from GoM63 were selected. The mineralogy of bulk sed­
iments was determined by a Siemens D5000 X-ray Diffractometer
(XRD). In addition, the chemistry of selected minerals was detected by
the PHILLIPS XL-30 scanning electron microscope (SEM) equipped with
EDAX spectrometer (EDS) system, located at the Institute of Geophysics,
UNAM, Mexico.
3.4. Geochemistry
For major, trace and REE geochemistry, 20 sediment samples were
selected at various intervals, i.e. 10 samples from GoM45 and 10 from
GoM63 cores.
3.4.1. Major element concentrations
For major element analysis, 20 g of sediment samples were powdered
by an agate mortar and were sieved through an American Society for
Testing Materials (ASTM) sieve No. 230 (<62 μm). Powdered samples
were heated to 110 ◦ C for 6 h followed by heating in a muffle furnace at
4
Applied Geochemistry 141 (2022) 105321
1000 ◦ C for 2 h to determine loss on ignition (LOI). Lithium tetraborate
was mixed with the samples and heated to 1000 ◦ C to form a fused
sample for XRF analysis with a Rigaku RIX-3000 equipped with a Rh
tube. Calibration curves were prepared by using international reference
materials and the geochemical standard JGB1 (GSJ) was used to cali­
brate data quality. The analytical accuracy was better than 5%.
3.4.2. Trace and rare earth element concentrations
The trace and rare earth element concentrations were quantified by
an Ultratrace - total acid digestion method using ICP-OES/ICP-MS at the
Activation Laboratories Ltd., Canada. All samples were determined in
triplicate and the analytical precision was described by relative standard
deviation (RSD), with a range of 5%–10%. The standard reference ma­
terials used were SY-2 (syenite CCRMP, Canada) and GSR-4 (sediment
IGGE, China). The REE data were normalized against chondrite
normalization factors listed in McDonough and Sun (1995) and Gromet
et al. (1984). The upper continental crust (UCC) values are from Taylor
and McLennan (1985). Eu anomaly (Eu/Eu*) was calculated based on
the equation Eu/Eu* = EuCN/[(SmCN)*(GdCN)]1/2, where CN represents
the chondrite normalized values.
Chemical index of alteration (CIA; Nesbitt and Young, 1982),
Chemical Index of Weathering (CIW; Harnois, 1988), and Plagioclase
Index of Alteration (PIA; Fedo et al., 1995) are calculated based on the
following equations. CIA = [Al2O3/(Al2O3 + CaO* + Na2O* + K2O)] *
100, CIW = [Al2O3/(Al2O3 + CaO* + Na2O*)] * 100, PIA =
[Al2O3–K2O/(Al2O3 + CaO* + Na2O*)] * 100, CaO* and Na2O* = Ca
and Na in silicate fractions.
J.S. Armstrong-Altrin et al. Applied Geochemistry 141 (2022) 105321

Table 1 4. Results
Textural parameters with mean grain size (Mz) for the GoM45 and GoM63
sediment cores from the Gulf of Mexico (after Folk and Ward, 1957). 4.1. Age assessment
Core GoM45

Interval (cm) Sand Silt Clay Mz (φ) (φ) SkI KG

For AMS 14C dates, CALIB software (Stuiver and Reimer, 1993,
version 5.0.2) was used to convert to calendar years BP. GoM45 reached
9–10 0.03 52.95 47.02 7.94 1.60 0.03 0.94
the Holocene/Pleistocene boundary around 180 cms, 20,711 cal yrs BP
40–41 0.00 46.50 53.50 8.19 1.52 0.02 0.92
110–111 0.00 49.85 50.15 8.06 1.57 0.02 0.90 at 330 cm, and 17,709 cal yrs BP at 478 cm; which reveals a block of
160–161 1.05 61.77 37.18 7.44 1.81 0.00 0.98 older sediments between 478 cm and 210 cm.
230–231 0.00 49.09 50.91 8.03 1.66 − 0.03 0.01 Armstrong-Altrin et al. (2015) reported an age of 26,500 years BP for
269–270 0.10 56.89 43.01 7.66 1.78 − 0.04 0.93 the nearby 5 m long core (GoM61). Similar age was also reported for
329–330 0.00 55.76 44.24 7.78 1.65 0.03 0.89
369–370 0.11 54.44 45.45 7.76 1.80 − 0.06 0.93
cores collected at the southwestern Gulf of Mexico (Anaya-Gregorio
440–441 0.00 48.30 51.70 8.07 1.64 − 0.02 0.89 et al., 2018; Machain-Castillo et al., 2020). Stratigraphic correlation
460–461 0.96 57.98 41.06 7.42 2.01 − 0.06 0.84 with Globorotalia menardii group for the 3 cores (Fig. 3) showed their
Core GoM63 base within the Upper Pleistocene and the Pleistocene/Holocene
Interval (cm) Sand Silt Clay Mz (φ) (φ) SkI KG
boundary at 150 cm, 190 cm, and 180 cm (for cores GoM61, GoM63, and
9–10 0.29 64.39 35.31 7.42 1.72 0.07 0.95
40–41 0.00 54.52 45.48 7.88 1.62 0.05 0.91 GoM45 respectively).
110–111 0.00 47.61 52.39 8.14 1.55 0.01 0.91
160–161 0.00 46.11 53.89 8.14 1.62 − 0.06 0.94
4.2. Granulometry
230–231 0.00 51.58 48.42 7.91 1.71 − 0.02 0.83
269–270 0.83 57.92 41.25 7.49 1.93 − 0.07 0.91
329–330 0.00 52.24 47.76 7.91 1.65 0.01 0.87 The textural parameters are calculated based on the methodology
380–381 0.47 55.79 43.73 7.68 1.83 − 0.04 0.92 proposed by Folk and Ward (1957) (Table 1). The sediments are very
440–441 0.00 50.61 49.39 7.56 1.69 − 0.02 0.86
fine (clay and silt; < 63 μm) in both cores and the amount of fine fraction
460–461 0.54 56.41 43.05 7.59 1.92 − 0.06 0.89
in most of the samples is >80%. The standard deviation in phi (φ) scale
varies from ~7.4 to 8.2 and ~7.4 to 8.1 for the GoM45 and GoM63 core
sediments, respectively. The variations in skewness and kurtosis

Fig. 4. SEM-EDS analysis for GoM45 core sediments. A) quartz and feldspar, B) barite, C) and D) magnetite, E) ilmenite, and F) cassiterite.

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J.S. Armstrong-Altrin et al. Applied Geochemistry 141 (2022) 105321

Fig. 5. SEM-EDS analysis for GoM63 core sediments. A) quartz, B) barite, C) zircon, and D) kaolinite.

Fig. 7. Major element concentrations of GoM45 and GoM63 core sediments

normalized against average upper continental crust values (Taylor and
Fig. 6. Geochemical classification of GoM45 an GoM63 core sediments based McLennan 1985).
on the log (SiO2/Al2O3) and log(Fe2O3/K2O) ratios (Herron, 1988).

4.4. Geochemistry
between the two core sediments are not significant (Table 1).
The major element concentrations of GoM45 and GoM63 sediment
4.3. Mineralogy
cores are listed in Table 1S (supplementary material). The SiO2 content
ranges from ~42.8 to 46.5 wt% and ~43.6 to 45.5 wt% in GoM45 and
At intervals between 269-270 cm and 460–461 cm, biogenic and
GoM63, respectively. The average Al2O3 content in GoM45 and GoM63
angular lithic grains are identified. In core GoM45, SEM-EDS reveals an
are similar (the mean with a standard deviation value is 13 ± 0.4 and 13
enrichment in Si, K, Na, Ca, Ba, Fe, Cr, Ti, and Sn contents (Fig. 4A–F).
± 0.3, respectively). Also, the variation in the distribution of Fe2O3,
This enrichment indicates the presence of minerals like quartz (Fig. 4A),
CaO, K2O, Na2O, and MgO in both cores are not significant (Table 1S).
feldspar (Fig. 4A), barite (Fig. 4B), magnetite (Fig. 4C and D), ilmenite
Based on the geochemical classification diagram of Herron (1988) the
(Fig. 4E), and cassiterite (Fig. 4F). Similarly, GoM63 sediments are
GoM45 and GoM63 core sediments are classified as shale (Fig. 6).
elevated with Si, K, Na, Ca, Al, Fe, Ba, and Zr contents, indicating the
The major element contents in core sediments are normalized against
presence of minerals such as quartz (Fig. 5A), barite (Fig. 5B), zircon
the average UCC values (Fig. 7). The concentration of MnO is higher in
(Fig. 5C), and kaolinite (Fig. 5D).
the core sediments than UCC, which is probably due to the concentration
of manganosite. Numerous studies addressed the occurrence of man­
ganosite in the Molango Upper Jurassic carbonate platform, located near
to the coastal region of the SW Gulf of Mexico (Okita, 1992; Okita and

6
J.S. Armstrong-Altrin et al.
Fig. 8. Trace element concentrations of GoM45 and GoM63 core sediments
normalized against average upper continental crust values (Taylor and
McLennan 1985).
Fig. 9. Chondrite-normalized REE patterns for GoM45 and GoM63 core sedi­
ments (Taylor and McLennan, 1985). 1 this study; 2 UCC (Taylor and McLennan,
1985). n = number of samples.
Shanks, 1992; Johnson et al., 2016; Anaya-Gregorio et al., 2018). Slight
enrichment in TiO2, Al2O3, Fe2O3, MgO, and CaO contents relative to
UCC is also noted (Fig. 7).
The trace element concentrations in the GoM45 and GoM63 core
sediments are listed in Table 2S (supplementary material). The trace
element patterns normalized against UCC are similar between GoM45
and GoM63 core sediments, except an enrichment in Cu content in two
GoM45 samples (Fig. 8). High field strength elements (HFSE) like Zr and
Hf in GoM45 (92.3–127.7 ppm and 2.2–3.4 ppm, respectively) and
GoM63 (94.5–152.8 ppm and 2.2–3.7 ppm) are lower than in UCC (190
and 5.8 ppm, respectively). Y content in a few samples from GoM63 are
slightly enriched compared with UCC. The large ion lithophile elements
(LILE; Ba, Rb, and Sr) in GoM45 (299–417 ppm, 81.4–107 ppm, and
315–561 ppm, respectively) and GoM63 (290–429 ppm, 72.6–104 ppm,
and 245–586 ppm, respectively) are almost similar. In addition, Sr
content in few samples are slightly enriched compared with UCC.
Compared with UCC, the transitional trace elements (TTE) such as Cr
and Ni contents are generally lower (<100 ppm), whereas V, Cu, Co, and
Sc contents in GoM45 and GoM63 are slightly enriched in few samples
(Fig. 8; Table 2S).
The REE content in GoM45 and GoM63 core sediments are listed in
Table 3S (supplementary material). The variations in REE content be­
tween GoM45 and GoM63 are not significant. The chondrite normalized
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Applied Geochemistry 141 (2022) 105321
Fig. 10. Al2O3 - (CaO + Na2O) – K2O (A–CN–K, in molecular proportion;
Nesbitt and Young, 1982) ternary diagram to infer the intensity of weathering.
Average concentration of upper continental crust (UCC; Taylor and McLennan,
1985) is plotted for comparison.
REE patterns of the core sediments are enriched in LREE and depleted in
HREE (Fig. 9). The Eu/Eu* ratios in the GoM45 and GoM63 core sedi­
ments vary between ~ 0.63–0.76 and ~ 0.64–0.74, respectively.
4.5. Elemental variations
The correlations between SiO2 versus K2O and Na2O in GoM45 (r =
0.76 and − 0.07, respectively) and GoM63 cores (r = 0.68 and r = 0.60,
respectively) are statistically significant, indicating the predominance of
aluminosilicates. The correlation of Al2O3 versus Rb and Ba for GoM45
(r = − 0.32 and 0.04, respectively, n = 10) and GoM63 (r = − 0.42 and r
= − 0.42, respectively, n = 10) are not statistically significant, indicating
that these elements are related to accessory phases (Armstrong-Altrin,
2020; Omar et al., 2021). Similarly, the correlation between Th and Zr is
statistically significant, but is not significant for Th versus Al2O3 for
GoM45 (r = 0.42 and r = − 0.59, respectively) and GoM63 (r = 0.77 and
r = − 0.46, respectively), which implies that its distribution is associated
with accessory phases such as zircon (Nagarajan et al., 2015; Ekoa Bessa
et al., 2021a; b, c). A negative correlation of Al2O3 versus Zr, Y, and Nb
for GoM45 (r = − 0.43, − 0.61 and 0.49, respectively) and GoM63 (r =
− 0.50, − 0.56 and − 0.15, respectively) also suggests that these elements
are integrated in accessory minerals (Bertrand et al., 2011; Hernán­
dez-Hinojosa et al., 2018; Janpou et al., 2022). The correlation of Al2O3
against V, Sc, and Cr for GoM45 (r = 0.47, − 0.44, and 0.26, respectively)
and GoM63 (r = 0.26, − 0.38, and 0.03, respectively) indicates that these
elements are not completely associated with phyllosilicates. Similarly,
the correlation between Al2O3 and Ba and Sr for GoM45 (r = 0.17 and
− 0.54, respectively) and GoM63 (r = − 0.42 and − 0.84, respectively)
are not significant, suggesting their concentrations are not controlled by
clay minerals.
The ΣREE content in GoM45 and GoM63 show a statistically signif­
icant correlation against Zr (r = 0.65 and r = 0.88, respectively; n = 10),
whereas it is not significant against Al2O3 (r = − 0.56 and r = − 0.51,
respectively, n = 10), which suggests that REEs are linked with detrital
minerals like zircon rather than clay minerals (Yu et al., 2016; Wang
et al., 2018). Similarly, a significant correlation observed between REE
and Y for the GoM45 (r = 0.94) and GoM63 (r = 0.96) also imply that
REEs are probably associated with accessory minerals. In general, the
elemental variations in sediments are indicating the association of major
and trace element concentrations with accessory detrital phases rather
J.S. Armstrong-Altrin et al.
Fig. 11. Major element based discriminant function diagram to infer sediment provenance (Roser and Korsch, 1988). The discriminant functions are:
Discriminant Function 1 = (− 1.773*TiO2) + (0.607*Al2O3) + (0.760*Fe2O3) + (− 1.500*MgO) + (0.616*CaO) + (0.509*Na2O) + (− 1.224*K2O) + (− 9.090);
Discriminant Function 2 = (0.445*TiO2) + (0.070*Al2O3) + (− 0.250*Fe2O3) + (− 1.142*MgO) + (0.438*CaO) + (1.475*Na2O) + (1.426*K2O) + (− 6.861) Data of
Papaloapan River sediments are from Armstrong-Altrin et al. (2015).
than phyllosilicates.
5. Discussion
5.1. Sediment weathering and recycling
The CIA and CIW values in GoM45 (~42–48 and ~44–53, respec­
tively) and GoM63 (~42–47 and ~44–51, respectively) indicate low
intensity of weathering in the source area. CIA values for the GoM45 and
GoM63 core samples are also plotted in the Al2O3 – (CaO + Na2O) – K2O
(A–CN–K) ternary diagram (Fig. 10), which permits to understand the
compositional variations (Fedo et al., 1995). On the A-C-NK diagram,
the samples are plotted together, indicating the intensity of weathering
is similar for the GoM45 and GoM63 core samples. The PIA is another
method to measure the intensity of weathering in clastic sediments. Less
weathered sediments have a value < 50, and depending on the intensity
of weathering the PIA value will increase (Fedo et al., 1995). The PIA
values of GoM45 and GoM63 vary from ~40.4 to 48.06 and ~40.37 to
46.4, respectively, which reveals a low intensity of weathering.
Fig. 12. Ni–Th*10-V ternary diagram (Bracciali et al., 2007) for the GoM45
and GoM63 core sediments. Average compositions of dacite, andesite, and
basalt from the adjacent area are also plotted for comparison.
8
Applied Geochemistry 141 (2022) 105321
The SiO2/Al2O3, Al2O3/Na2O, and K2O/Na2O ratios are used in
various studies to infer the textural maturity of sediments and high
values (>6, >5, and >1, respectively) indicate a high compositional
maturity (Cox et al., 1995; Madhavaraju et al., 2020; Al-Juboury et al.,
2021). The low SiO2/Al2O3, Al2O3/Na2O, and K2O/Na2O values in
GoM45 (~3.2–3.5, ~4.9–6.1 and ~0.65–0.95, respectively) and GoM63
(~3.3–3.5, ~4.8–6.1, and ~0.66–0.87, respectively) are also indicating
a low compositional maturity.
The accumulation of zircon in sediments increase the HREE content
in relation to LREE and decrease the LaNASC/YbNASC ratio less than 2
(Tawfik et al., 2018). The correlation between Zr and LaNASC/YbNASC is
statistically not significant for GoM45 (r = − 0.16) and GoM63 (r =
− 0.30), which indicates a moderate degree of sorting during sediment
deposition. In addition, concentration of minerals such as monazite and
allanite in sediments increase the P2O5 and LREE contents, which can
indicate the degree of sorting and sediment recycling. Concentration of
these minerals in sediments will significantly increase the (Gd/Yb)NASC
ratio, higher than the NASC (>2). The (Gd/Yb)NASC ratio in GoM45
Fig. 13. Chondrite-normalized rare earth element (REE) patterns of core sed­
iments are compared with probable source rocks from the southern Gulf of
Mexico. 1 this study; 2,3,4 andesite, basaltic andesite, and basalt are compiled
from Rosales-Lagarde et al. (2005), Verma (2001), Torres-Sánchez et al. (2019),
Verma et al. (2020, 2021); 5 Taylor and McLennan (1985). n = number
of samples.
J.S. Armstrong-Altrin et al.
Fig. 14. Major element (M)-based multidimensional tectonic discriminant function diagram for the discrimination of active (A) and passive (P) margin settings
(Verma and Armstrong-Altrin, 2016). The function (DF(A-P) M) is to be calculated from the equation DF(AP)M = (3.0005 * ilr1TiM) + (− 2.8243 * ilr2AlM) + (− 1.0596 *
ilr3FeM) + (− 0.7056 * ilr4MnM) + (− 0.3044 * ilr5MgM) + (0.6277 * ilr6CaM) + (− 1.1838 * ilr7NaM) + (1.5915 * ilr8KM) + (0.1526 * ilr9PM) − 5.9948.
varies from ~1.31 to 1.90 and for GoM63 it varies from ~1.29 to 1.19,
indicating moderate sorting and recycling.
5.2. Provenance
Textural classification reveals that the GoM45 and GoM63 sediments
are mostly silt and clayey silt types. The major element-based discrim­
inant function diagram of Roser and Korsch (1988) is widely used in
various studies to infer sediment provenance (Madhavaraju et al.,
2016a, b; Ramos-Vázquez et al., 2018; Ngueutchoua et al., 2019; Arm­
strong-Altrin et al., 2019, 2021a; Venu and Velmayil, 2021). This dia­
gram indicated an intermediate rock provenance for the GoM45 and
GoM63 core sediments (Fig. 11). On the other hand, the Al2O3/TiO2
ratio is widely used in various studies to infer source rock composition
(Armstrong-Altrin et al., 2018). According to Hayashi et al. (1997) the
Al2O3/TiO2 ratio varies from ~3 to 8 for mafic, ~ 8–21 for intermediate
and ~21–70 for felsic igneous rocks. The Al2O3/TiO2 ratio in GoM45
and GoM63 varies from 19 to 21, which indicates that the core sedi­
ments were derived from intermediate source rock like andesite.
The Cr, Ni, and V contents are very low, which could be the result of
the contribution of sediments derived from the intermediate source
rocks, probably andesite (supplementary Table 2S). This inference is
further supported by the Ni–Th*10-V ternary diagram (Fig. 12; Bracciali
et al., 2007). Similarly, the Th/Co vs La/Sc diagram also suggests an
intermediate rock as a possible source rock for the core sediments.
Furthermore, mafic rocks usually contain high LREE/HREE ratio with
positive Eu anomaly, whereas felsic rocks usually contain low
LREE/HREE ratio with high negative Eu anomaly (Cullers, 2000). Low
LREE/HREE ratio with a small negative Eu anomaly is observed in the
GoM45 and GoM63 core sediments, indicating that the sediments were
mostly derived from the intermediate igneous rocks. In addition, to infer
the provenance, the REE data of andesite, basalt, and basaltic andesites
exposed along the coastal areas of the southern Gulf of Mexico are
compiled from literatures (Rosales-Lagarde et al., 2005; Verma, 2001;
Torres-Sánchez et al., 2019; Verma et al., 2020, 2021). The chondrite
normalized REE patterns and Eu anomaly of core sediments are com­
parable with andesite and basaltic andesites (Fig. 13). This suggests that
the intermediate igneous rocks like andesite and basaltic andesite are
the probable source rocks for the GoM45 and GoM63 core sediments.
The geochemical composition of detrital sediments is reliable to infer
the tectonic setting of the source area (Madhavaraju et al., 2020; Critelli
et al., 2021; Roddaz et al., 2021). The tectonic discriminant function
diagrams based on major oxides proposed by Verma and
Armstrong-Altrin (2016) is applied to determine the tectonic setting. On
this diagram the samples are plotted in the passive margin field, indi­
cating a passive margin setting for the SW Gulf of Mexico sediments
(Fig. 14).
5.3. Depositional environment
Trace element contents in clastic sediments, particular elemental
ratios like V/Cr, Ni/Co, and Cu/Zn are highly useful to infer the depo­
sitional condition (Jones and Manning, 1994). The V/Cr ratio is
9
Applied Geochemistry 141 (2022) 105321
considered as a redox indicator, the V/Cr ratio >4.25 represents an
anoxic depositional condition, while <2 are indicative of a more
oxidizing condition. Jones and Manning (1994) also suggested that
Ni/Co ratio <5 indicate oxic, whereas ratios between 5.0 and 7.0 suggest
dysoxic conditions, and ratios above 7.0 indicative of suboxic and anoxic
environments. Similarly, Cu/Zn ratios increase from oxic (<1) to redox
(>1) depositional conditions (Hallberg, 1976). The V/Cr, Ni/Co, and
Cu/Zn ratios from GoM45 (1.63 ± 0.20, 2.26 ± 1.19 and 0.59 ± 0.60,
respectively) and GoM63 cores (1.75 ± 0.32, 1.41 ± 0.99 and 0.65 ±
0.31, respectively) indicate an oxic depositional condition.
6. Conclusions
The mineralogy and geochemistry of the GoM45 and GoM63 core
sediments in the SW Gulf of Mexico are analyzed. The core sediments are
dominated by silt and clay. The XRD data indicates that the distribution
of minerals in the GoM45 and GoM63 are similar and contains minerals
such as barite, gibbsite, kaolinite, magnetite, plagioclase, and chlorite.
The CIA, CIW, and PIA values of the core sediments indicate low
weathering in the source area. The major and trace element concen­
trations indicate the intermediate igneous rocks such as andesite and
basaltic andesite are the source rocks for the deep-sea sediments. The
trace elements and their elemental ratios suggest that the deep-sea
sediments are deposited in an oxic environment. The chondrite
normalized REE patterns and Eu anomaly also suggest that the sedi­
ments were derived from the andesite and basaltic andesitic rocks
located along the SW Gulf of Mexico coastal region. Major element
concentrations indicate deposition of sediments in a passive margin,
which is consistent with the geology of the Gulf of Mexico.
CRediT authorship contribution statement
John S. Armstrong-Altrin: Writing - original draft, Formal analysis,
Resources, Funding acquisition. Mayla A. Ramos-Vázquez: Investiga­
tion, Writing - review and editing. Jayagopal Madhavaraju: Methodol­
ogy, Formal analysis, editing. Mario Emilio Marca-Castillo: Logistic
fieldwork, Data curation, Methodology, Validation, Formal analysis.
María Luisa Machain-Castillo: Logistic fieldwork, Methodology, Formal
analysis, review and editing. Antonio Z. Márquez-García: Methodology,
Formal analysis.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
Ramos-Vázquez is thankful to CONACyT for the postdoctoral schol­
arship (CVU: 595593). Armstrong-Altrin is grateful to “Consejo Nacional
de Ciencia y Technología” (CONACyT; no: A1-S-21287) and PAPIIT
projects (no: IN107020) for financial assistance. We extend our sincere
J.S. Armstrong-Altrin et al. Applied Geochemistry 141 (2022) 105321

thanks to Patricia Girón García, Carlos Linares-López, Laura E. Gómez Johnsson, M.J. (Eds.), Sedimentary Provenance and Petrogenesis: Perspectives from
Petrography and Geochemistry, vol. 420, pp. 73–93. Geol. Soc. Amer. Special Paper.
Lizárraga, and Teodoro Hernández Treviño for analytical help. We are
Cancino-Solórzano, Y., Paredes-Sánchez, J.P., Gutiérrez-Trashorras, A.J., Xiberta-
grateful to our laboratory assistants Ricardo M. Domínguez, Eduardo Bernat, J., 2016. The development of renewable energy resources in the State of
Morales la Garza, Susana Santiago, and Arturo Ronquillo Arvizu for Veracruz, Mexico. Util. Pol. 39, 1–4.
powdering sediment samples. We are also grateful to the ICML Institu­ Chaudhuri, A., Banerjee, S., Prabhakar, N., Das, A., 2020. The use of heavy mineral
chemistry in reconstructing provenance: a case study from Mesozoic sandstones of
tional (no. 616) and FACIES-PEMEX-PEP (no: 420401851) projects for Kutch Basin, India. Geol. J. 55 (12), 7807–7817.
financial support for sample collection. Chougong, D.T., Bessa, A.Z.E., Ngueutchoua, G., Yongue, R.F., Ntyam, S.C., Armstrong-
Altrin, J.S., 2021. Mineralogy and geochemistry of Lobé River sediments, SW
Cameroon: implications for provenance and weathering. J. Afr. Earth Sci. 183,
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