Geochimica et Cosmochimica Acta 356 (2023) 14–37

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Geochimica et Cosmochimica Acta

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Reactive vanadium and iron fluxes in different modern

sedimentary environments
Jonathan Garcia-Orozco a, Miguel Angel Huerta-Diaz b, *, Xosé L. Otero c, d,
Karla Gabriela Mejia-Piña e, Jacob Alberto Valdivieso-Ojeda b, Daniel David Gregory f,
Margarita Díaz-de-Alba g, D. Arenas-Islas e, Roxana Cervantes-Flores a
a
Posgrado en Oceanografía Costera, Instituto de Investigaciones, Oceanológicas/Facultad de Ciencias Marinas, Universidad Autónoma de Baja California, Apdo. Postal
76, Ensenada, Baja California 22800, Mexico
b
Instituto de Investigaciones Oceanológicas, Universidad Autónoma de Baja California, Department of Marine Biogeochemistry and Global Change, Carretera
Transpeninsular Ensenada-Tijuana No. 3917, Fraccionamiento Playitas, C.P. 22860 Ensenada, B.C., Mexico
c
CRETUS, Department of Edaphology and Agricultural Chemistry, Faculty of Biology, University of Santiago de Compostela, Santiago de Compostela, Spain
d
REBUSC. Rede de Estacións Biolóxicas da Universidade de Santiago de Compostela, Estación de Bioloxía Mariña A Graña, Ferrol, Spain
e
Facultad de Ciencias Marinas, Universidad Autónoma de Baja California, Carretera Transpeninsular Ensenada-Tijuana No. 3917, Fraccionamiento Playitas, C.P.
22860 Ensenada, Baja California, Mexico
f
Department of Earth Sciences, University of Toronto, 22 Ursula Franklin Street, Toronto, Ontario M5S3B1, Canada
g
Department of Analytical Chemistry, Institute of Biomolecules (INBIO), Faculty of Sciences, CEI-MAR, Campus Río San Pedro, University of Cadiz, ES-11510 Puerto
Real, Cadiz, Spain

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

Associate editor: Natascha Riedinger This study evaluated the removal of the metals (Me) vanadium and iron associated with the operationally defined
HCl-extractable (MeHCl), pyrite (Mepyr), and reactive (Mereac = MeHCl + Mepyr) fractions in the sediments of five
Keywords: contrasting sedimentary environments: (1) the oxygen minimum zone (OMZ; San Lázaro and San Blas basins); (2)
Reactive trace metal the anoxic/anoxic-sulfidic sediments of the California Continental Borderland basins and Todos Santos Bay
Pyrite
Canyon; (3) the oxic sediments of the Patton Escarpment, Baja California continental shelf, and deep sediments of
Vanadium mass accumulation rates
the Gulf of Mexico (GoM); (4) the Guerrero Negro Hypersaline System (GNHS) in Baja California Sur, Mexico;
Degree of trace metal pyritization
Geochemical fractions and (5) the turbiditic deposits of the GoM. The average VHCl concentration ranged from 8 ± 15 nmol g− 1 in
turbidites to (7.9 ± 4.3) × 102 nmol g− 1 in the OMZ, respectively. The Vpyr concentrations were within the
narrow range of 6.6 ± 4.2 nmol g− 1 (oxic sediments) to 8.6 ± 5.4 nmol g− 1 (turbidites), which indicates that the
pyrite fraction is not an important reservoir of reactive V. The relative consistency of the Vpyr concentrations (7.2
± 5.2 nmol g− 1; n = 1098), regardless of the sedimentary environment and redox state of the system, allowed us
to calculate a global burial value for oceanic sediments of 4.2 ± 3.0 Gg y–1. The VHCl enrichment observed in
OMZ and anoxic/anoxic-sulfidic sediments may be due to its incorporation into acid volatile sulfide. The lowest
average values of the degree of V pyritization corresponded to the OMZ (0.98 ± 0.68%) while the highest
average values corresponded to turbidites (69 ± 32%), with the latter being due to their extremely low VHCl
values. The mass accumulation rate (MAR) calculations for reactive Fe and V show that the sediments of all OMZ
regions could annually incorporate (12.1 ± 8.6) × 104 Gg and (6.3 ± 3.8) × 102 Gg of reactive Fe and V,
respectively. Although the GNHS exhibited the greatest MAR value of reactive Fe and V [(32 ± 28) × 102 g m− 2
ky− 1 and 35 ± 35 g m− 2 ky− 1, respectively], this environment currently does not contribute an important
percentage of the MAR at the global level due to its small geographical area. However, in the geological past
when its geographical area was much greater, the MAR values of reactive Fe and V may have been more
important. Although deep sediments (>1000 m water depth) cover a substantial area, they contribute a relatively
small, yet significant proportion of the total vanadium (V) deposited in ocean sediments, ranging from 9.7% to
24.8%.

* Corresponding author.
E-mail address: huertam@uabc.edu.mx (M.A. Huerta-Diaz).

https://doi.org/10.1016/j.gca.2023.07.006
Received 30 January 2023; Accepted 7 July 2023
Available online 8 July 2023
0016-7037/© 2023 Elsevier Ltd. All rights reserved.
J. Garcia-Orozco et al.
1. Introduction
Vanadium is relatively abundant in seawater (29.8–37.4 nmol kg− 1;
Wang and Sañudo Wilhelmy, 2009; Smrzka et al., 2019) and is essential
for metabolic processes such as chlorophyll synthesis (Wilhelm and
Wild, 1984) and photosynthesis (Gilmore et al., 1985). Vanadium ex­
hibits a conservative distribution in oceanic waters and tends to be
scavenged by mineral (e.g., manganese oxides) and/or biogenic parti­
cles in coastal waters (Wang and Sañudo Wilhelmy, 2009). In the surface
layer, V concentrations are ~10% lower than those in the rest of the
water column (Collier, 1984). Generally, V is found as V(V) in the form
of the oxyanion H2VO–4 in oxic waters, whereas V is found as V(IV) in the
form of the oxycation VO2+ in reduced environments (Breit and Wanty,
1991; Wanty and Goldhaber, 1992). The pentavalent form of V is the
most soluble and mobile V species in oxic waters (Moore, 1991). Given
that this species easily associates with Mn oxyhydroxides (Wehrli and
Stumm, 1989), pentavalent V is closely associated with the Mn redox
cycle (Hastings et al., 1996). This cycle is the most effective mechanism
by which V is transported to sediments (Brumsack, 1986; Auger et al.
1999; Scholz et al., 2017).
Once dissolved in the interstitial waters of sediments, V can exhibit
three oxidation states (Breit and Wanty, 1991): (1) V(V) in the form of
vanadate (e.g., H2VO−4 ), which is the most abundant species under oxic
conditions and at the pH of natural marine environments; (2) V(IV) in
the form of the vanadil ion (i.e., VO2+), which is the predominant spe­
cies under reducing conditions and the species that usually forms strong
bonds with organic complexes (Wehrli and Stumm, 1989; Breit and
Wanty, 1991); and (3) V(III), which precipitates as an oxyhydroxide (e.
g., V(OH)3) due to its low solubility at natural seawater pH. Thus, V(V)
and V(IV) represent the dominant oxidation states under oxidizing (Eh
> 600 mV) and moderately reducing conditions (0 mV ≤ Eh ≤ 600 mV),
respectively, whereas V(III) exists only under reducing conditions (Eh <
0 mV), although it is easily oxidized in the presence of low oxygen
concentrations (Shaheen et al., 2019). Under reducing conditions, Mn
and Fe oxides dissolve, which favors the release of the associated V into
interstitial waters in the form of V(IV) (Wright et al., 2014; Shaheen
et al., 2019). Vanadium species can be removed from interstitial waters
by adsorption processes on mineral surfaces or by chelate formation
with organic ligands (Emerson and Huested, 1991; Morford and Emer­
son, 1999). Finally, in the case of anoxic-sulfidic conditions in sediments
or euxinic conditions in the water column, the H2S produced by bacterial
sulfate reduction may reduce V(IV) to V(III) (Breit and Wanty, 1991).
Given that V occurs in natural environments under different oxida­
tion states (Wehrli and Stumm, 1989; Gustafsson, 2019; Nielsen, 2020),
it is sensitive to redox changes within sediments (Tribovillard et al.,
2006; Scholz, 2018). The ability of V to have two oxidation states makes
it suitable as a proxy for paleoredox conditions in marine sediments (e.
g., Wanty and Goldhaber, 1992; Algeo and Maynard, 2004, 2008;
Smrzka et al., 2019), since it is present as V(V) and V(IV) in oxic and
reduced marine environments, respectively (Wehrli and Stumm, 1989;
Wang and Sañudo-Wilhelmy, 2008). Additionally, V isotopes have been
utilized as indicators of low-oxygen marine conditions (e.g., Ventura
et al., 2015; Wu et al., 2019b, 2020; Schauble et al., 2001; Chen et al.,
2022; Wei et al., 2023). Thus, the concentrations of V (e.g., Scott et al.,
2017; Kunert et al., 2020) or V/Al ratios (e.g., Bennett and Canfield,
2020) can be used to infer the redox state of ancient marine environ­
ments. According to Scott et al. (2017) and Kunert et al. (2020), V can be
used as a proxy for anoxic-sulfidic and hypersulfidic conditions (H2S ≥
10 mM) in ancient environments rich in organic matter. Furthermore,
Wu et al. (2019a) suggest using V over other available redox proxies (e.
g., Mo, Fe, and U), as this transition metal is more sensitive to subtle
changes in dissolved oxygen concentrations and, therefore, could be
used to identify the conditions that control the redox state of sedimen­
tary systems (e.g., Calvert and Pedersen, 1993; Hastings et al., 1996).
Numerous studies have described the patterns of V concentrations in
marine sediments in both coastal (e.g., Wu et al., 2019a, 2020; Nameroff
15
Geochimica et Cosmochimica Acta 356 (2023) 14–37
et al., 2002; Wang and Sañudo Wilhelmy, 2009) and oceanic (e.g.,
Collier, 1984) environments. These studies have covered a wide di­
versity of sediments, including oxygen minimum zones (OMZs; e.g.,
Brumsack, 1986), restricted basins (e.g., Brumsack, 1989; Lüschen,
2004), and oxic (e.g., Morford and Emerson, 1999) and euxinic (e.g.,
Brumsack, 1986; Ravizza et al., 1991) environments. In addition, recent
studies have focused on investigating the availability and chemical
speciation of V sulfides in different geological environments using
geochemical models such as the one proposed by Moore et al. (2020).
One such research area of particular importance is V enrichment in
OMZs (e.g., Böning et al., 2004; Scholz et al., 2011; Scholz, 2018; Ben­
nett and Canfield, 2020), as these zones appear to be expanding due to
climate change (e.g., Whitney et al., 2007; Duce et al., 2008; Stramma
et al., 2008; Fuenzalida et al., 2009). However, the roles that reactive
geochemical fractions play in V sequestration in marine sediments and
the mass accumulation rate magnitudes of these fractions in deep oxic,
anoxic-sulfidic, hypersaline, turbiditic and OMZ sediments have not yet
been evaluated.
The development of biogeochemical models to study the V cycle and
the possible effects of climate change on this cycle, requires a proper
analysis of the most reactive V fractions and their mass accumulation
rate magnitudes on a global scale. In addition, a better understanding of
the behavior of reactive V fractions in different sedimentary environ­
ments and during the processes of early diagenesis is necessary to
evaluate their potential use as proxies of paleoredox conditions. To
achieve these objectives, the degree of association of this element with
the HCl-extractable fraction (which includes the V associated with acid
volatile sulfide and Fe/Mn oxyhydroxides) and the sedimentary pyrite
fraction were evaluated. Finally, the mass accumulation rates of these
two geochemical fractions were calculated or approximated when
possible. This study was conducted in five contrasting sedimentary en­
vironments: (1) the anoxic/anoxic-sulfidic sediments of the California
Continental Borderland (CCB) basins and Todos Santos Bay Canyon; (2)
the OMZ of the San Lázaro and San Blas basins; (3) the oxic sediments of
the Patton Escarpment, Baja California continental shelf, and deep
sediments of the Gulf of Mexico (GoM); (4) the Guerrero Negro Hyper­
saline System (GNHS) in Baja California Sur; and (5) the turbiditic de­
posits of the GoM.
2. Materials and methods
2.1. Study area
The study area includes two major regions: the eastern Pacific Ocean
and the GoM. The first region extends from the San Pedro basin
(33◦ 30.36′N, 118◦ 24.54′W) offshore of Los Angeles (USA) to the San Blas
basin (21◦ 17.91′N, 105◦ 59.97′W) offshore of the state of Nayarit
(Mexico; Fig. 1, Table 1), while the second region covers the deep sed­
iments (>950 m water depth) of the southern GoM. The characteristics
of the different sedimentary environments in each of the two major re­
gions are described in Sections 2.2, 2.3, 2.4, 2.5 and 2.6.
2.2. Anoxic and anoxic-sulfidic sediments in the San Pedro, Santa
Catalina, San Clemente basins, and Todos Santos Bay Canyon
The CCB basins of San Pedro, Santa Catalina, and San Clemente are
located off the coast of Los Angeles on the western edge of the California
Current (Fig. 1, Table 1) at water depths of ~900 m (San Pedro) to
~2068 m (San Clemente). These basins are important accumulation
sites for sediments and organic particulate matter from natural and
anthropogenic sources (National Research Council, 1990). The bottom
waters of these basins are seasonally or permanently anoxic (Emery,
1960); therefore, their sediments are not bioturbated by benthic or­
ganisms (National Research Council, 1990). However, the research
previously conducted throughout this region has mainly focused on
evaluating anthropogenic contamination by analyzing total trace metals
J. Garcia-Orozco et al.
in the water column and sediments (e.g., Chow et al., 1973; Bruland
et al., 1974; Bertine and Goldberg, 1977; Huh et al., 1992; Morford and
Emerson, 1999; Schiff, 2000).
The Todos Santos Bay Canyon (Fig. 1, Table 1) is located on the
Pacific coast of Baja California in the bay of the same name. The canyon
has a water depth of ~400 m (Sánchez et al., 2009; Delgadillo-Hinojosa
et al., 2015), fine grain-sized silt sediments, and current speeds <0.30 m
s− 1 (Sánchez et al., 2009). The environment of the canyon is conducive
to anoxic-sulfidic processes due to its high concentration of organic
carbon (3.21 ± 0.59%; Canedo-López, 2009), which is approximately
double those commonly reported for the coastal sediments of the region
(Smith et al. 2008). In fact, the color of the sediment of the canyon was
black and was accompanied by a pronounced H2S odor.
2.3. Oxygen minimum zone: San Lázaro and San Blas basins
The San Lázaro Basin, which is also known as the Soledad Basin
(25.1◦ N, 112.7◦ W), is located approximately 45 km off the western coast
of the Baja California Peninsula near the continental shelf of the Mexican
state of Baja California Sur (Fig. 1, Table 1). This semi-enclosed basin,
which exhibits a maximum water depth of ~547 m (Silverberg et al.,
2004) and a sill depth of 290 m, is located within the Pacific Ocean OMZ
(van Geen et al., 2003). Given that the degradation of organic matter
within OMZs is mainly mediated by nitrate reduction (Lam and Kuypers,
2011; Thamdrup et al., 2012; Scholz, 2018), these zones may account for
~40% of nitrate reduction worldwide (Gruber, 2004). These conditions
cause most redox processes, such as the oxidation and removal of Fe
induced by nitrate reducing microorganisms (Scholz et al., 2016) and
the chemolithoautotrophic oxidation of sulfides with NO–3 (Schunck
et al., 2013), to be mediated by the nitrogen cycle. The low concentra­
tion of dissolved oxygen in the bottom water of the basin (3–5 µM; van
Geen et al., 2003) causes millimeter-scale fine laminations to appear in
the sediments due to the absence of bioturbation and the alternating
seasonal input of organic and detritic material. The San Blas station is
located in the basin of the same name (sill depth of 300 m) and near the
Tres Marías Islands. Low oxygen concentrations in the bottom water (~1
µM or less) and sulfate depletion in interstitial sediment water have been
reported for this basin (McManus et al., 2006). In addition, Berelson
et al. (2005) reported that San Blas sediments also show laminations that
are occasionally interrupted by turbidites.
2.4. Deep oxic sediments of the Gulf of Mexico, Patton Escarpment, and
Baja California continental shelf
The GoM (Fig. 1; Table 1) is a semi-enclosed ocean basin that hosts
diverse temperate, subtropical, and tropical coastal environments along
its ~6100-km coastline (Moody, 1967; Biggs, 1992). The area of the
16
Geochimica et Cosmochimica Acta 356 (2023) 14–37
Fig. 1. Locations of the sampling stations, which
include the following sedimentary environments:
eastern North Pacific Ocean oxygen minimum zone
represented by the San Lázaro (SL1 to SL5) and San
Blas (SAB) basins; anoxic and anoxic-sulfidic sedi­
ments that include the Santa Catalina (SCB), San
Clemente (SCLB), and San Pedro (SPB) basins and
Todos Santos Bay Canyon (METOX1); oxic sediments
of the Gulf of Mexico (GoM), Patton Escarpment (PE),
and Baja California continental shelf (METOX2 and
METOX3); Guerrero Negro Hypersaline System
(GNHS; F1 to F6); and the sediments influenced by
turbidities in the GoM (Turbidites). Insert map data
GNHS: Google.
GoM measures ~1.5 × 106 km2, of which 32% (~480,000 km2) and 41%
(~615,000 km2) correspond to the continental shelf and slope, respec­
tively (Darnell and Defenbaugh, 1990). The total water volume of the
GoM is ~2.4 × 106 km3 and its average depth is 1,615 m, although
~24% (~360,000 km2) of the gulf exhibits depths >3,000 m (Ward and
Tunell, 2017). The abyssal zone, which is located in the central portion
of the basin, reaches 4,384 m of water depth, while the shallow areas
show depths <180 m with widths of ~100–200 km (Love et al., 2013).
High rainfall (600–3,000 mm; Ward and Tunell, 2017) promotes the
contribution of dissolved and particulate materials and associated trace
metals from major river basins, such as the Mississippi River and
Grijalva-Usumacinta river system that dominate the drainage systems of
the northern and southern GoM, respectively (Kumpf et al., 1999). These
two river systems are currently the main contributors of sediments to the
GoM, although the Rio Bravo provided particulate matter to the gulf at a
rate of ~27 × 104 ton a− 1 before being dammed (Galloway et al., 2011).
Finally, the GoM is dominated by three depositional environments
(Ward and Tunell, 2017): (1) carbonate deposits of the Yucatan Penin­
sula, northwestern Cuba, and southwestern Florida; (2) deposits of
terrestrial material in the northern GoM; and (3) mixed deposits of fine-
grained and carbonated terrestrial sediments along the western GoM
due to fluvial inputs.
Currently, there is no reported information on the biogeochemistry
of trace metals in sediments of the Patton Escarpment (3,762 m water
depth). However, its characteristics may be similar to those of other
deep sediments (>3500 m; e.g., D’Hondt et al., 2015; Taillefert et al.,
2017) with low inputs of reactive organic matter and high oxygen
penetration (e.g., Emerson et al., 1985; Orcutt et al., 2013). The coastal
region of Baja California is mostly covered by beaches or cliffs, and
terrestrial contributions are mainly due to occasional runoff during
seasonal rains given that there are no major rivers in the region (Pou-
Alberú and Pozos-Salazar, 1992). The continental shelf is narrow in this
region (70–80 km) with depths that are typical of the eastern Pacific
(~180 m; Avilés and Arredondo, 1999). Geochemical research in this
region has mainly focused on assessing the distributions of total metals
in sediments. Nava-López and Huerta-Díaz (2001) conducted the first
evaluation of reactive sediment fractions along the northwestern coast
of Baja California.
2.5. Turbidites of the GoM
Turbidity events produced by currents, tides, and gravitational pro­
cesses (Ward and Tunell, 2017) occur over the Yucatan Continental
Shelf. These events are particularly notable in the Campeche Escarpment
(CE; Lindsay et al., 1975) and can transport sediments to the abyssal
plain of the GoM (Davies, 1968; Ostermeier, 1995). Indeed, the CE
serves as a sediment trap in which turbiditic transport may be
J. Garcia-Orozco et al. Geochimica et Cosmochimica Acta 356 (2023) 14–37

Table 1 region of the Baja California Peninsula (Bermúdez-Almada, 2003; Fig. 1;

Geographic location, collection date, and water-column depth of the sedimen­ Table 1), is characterized as a shallow (average depth of 15 m) and
tary cores collected in this study: Pacific Ocean off the Baja California Peninsula, hypersaline (S = 40) water body (Holser et al., 1981). Low rainfall
Mexico (METOX-1 to METOX-3); Santa Catalina Basin (SCB), San Clemente (annual average of 30–80 mm y− 1) and intense winds result in aridity
Basin (SCLB); and San Pedro Basin (SPB); the oxygen minimum zone (OMZ) and a high evaporation rate of ~1700 mm y− 1 around the lagoon
represented by the San Lázaro Basin (SL1 to SL5) and San Blas Basin (SAB); deep
(Ortlieb and Pierre, 1981). This high evaporation rate is reflected in the
sediments of the Gulf of Mexico (X1-3 to X7-38); Patton Escarpment (PE), and
surrounding tidal flats and sediments, where sodium chloride, potas­
Guerrero Negro Hypersaline System (F1 to F6) in Baja California Sur, Mexico.
sium, magnesium, and bromide saturations have been reported (Holser,
Station Latitude Longitude Collection date (mm/ Water depth
1966). Part of the inland area surrounding the OLL, which was originally
(N) (W) dd/yyyy) (m)
composed of intertidal areas, flood plains, and evaporitic tidal flats, has
METOX1 31.7858 − 116.7506 12/11/1996 225 been modified to construct evaporation and crystallization ponds from
METOX2 32.4917 117.4717 12/08/1996 1257
marine brines by the salt company Exportadora de Sal S.A. of Guerrero
−
METOX3 30.3500 − 117.3167 12/10/1996 2500
SCB 33.3042 − 118.6062 05/24/2018 1315 Negro (Ortlieb and Pierre, 1981), which is located near the town of the
SCLB 32.6217 − 118.1357 05/26/2018 2068 same name (Fig. 1). This company is considered one of the largest
SPB 33.5060 − 118.4090 05/23/2018 902 producers of evaporative salt in the northern hemisphere, with its fa­
SL1 25.0747 112.6272 02/11/2012 315
−
cilities covering ~300 km2 (Dilon et al., 2013).
SL2 25.1531 − 112.7069 02/16/2011 541
SL3 25.1970 − 112.7002 05/30/2018 547
The study area included a series of 13 evaporation ponds that are
SL4 25.2153 − 112.7228 02/11/2012 315 connected by gates and exhibit limited pyrite production in their sedi­
SL5 25.2292 − 112.7183 02/17/2011 542 ments due to low concentrations of reactive Fe (Huerta-Diaz et al., 2011,
SAB 21.2985 − 105.9995 06/02/2018 415 2012; Valdivieso-Ojeda et al., 2014). The network of connected ponds
X1-3 23.021 − 95.028 11/16/2010 3535
begins with Pond 1, which receives water that is pumped in from the
X1-31 24.006 − 90.000 11/13/2010 3727
X1-33 23.0183 − 91.015 11/17/2010 3801 OLL and then sequentially transferred to the remaining ponds, which
X1-36 21.0165 − 92.927 11/20/2010 2873 causes salinity to increase in each successive pond (López-de los Santos,
X1-40 20.0217 − 95.010 11/21/2010 2831 2008). At the bottoms of some ponds microbial mats can be found,
X1-43 21.9718 − 93.033 11/18/2010 3546
where cyanobacteria constitute important components (López-Cortés
X2-2 23.0185 − 96.719 07/03/2011 1765
X2-10 24.0062 − 93.749 07/09/2011 3753
et al., 2001). These microbial communities proliferate mainly in Ponds
X2-24 24.9532 − 87.033 07/06/2011 3416 4, 5, and 6, in which salinities can reach > 105‰ (Des Marais et al.,
X3-7 21.9969 − 94.004 03/07/2013 3559 1992).
X3-38 21.0125 − 95.086 03/09/2013 3087
X3-43 21.8715 − 93.491 03/08/2013 2960
X3-44 22.997 − 92.985 03/04/2013 3741
2.7. Sedimentary core collection and processing
X3-46 20.0293 − 96.018 03/10/2013 1739
X3-47 22.4889 − 92.017 03/03/2013 3551 The material used to process and analyze samples was always plastic
X4-1 25.0089 − 95.539 08/28/2015 2429 that had been washed with 2% Micro® detergent, rinsed once with tap
X4-7 24.9604 − 90.014 08/31/2015 3534
water, and once with deionized water. Subsequently, the material was
X4-14 24.0044 − 92.316 09/05/2015 3734
X4-31 21.5076 − 96.527 09/07/2015 1549 immersed in a 10% HCl solution for at least 72 h, rinsed twice with Milli-
X4-34 21.484 − 93.502 09/12/2015 3146 Q grade water to remove excess acid, and dried in a convection oven at
X4-40 20.484 − 95.997 09/13/2015 1930 50 ◦ C. All reagents used were reagent grade or better.
X4-45 19.987 − 95.608 09/16/2015 2159 A total of 59 sedimentary cores were collected (Fig. 1, Table 1), of
X4-47 20.000 − 94.017 09/15/2015 1342
X5-1 25.741 − 95.541 06/15/2016 1355
which 13 were collected in the Pacific Ocean at water depths ranging
X5-3 25.050 − 94.013 06/15/2016 3685 from 225 to 3762 m during four cruises of the oceanographic vessels R/V
X5-5 25.124 − 92.01 06/17/2016 3513 Francisco de Ulloa (December 1996, METOX1 to METOX3), R/V Alpha
X5-8 25.124 − 89.053 06/18/2016 3477 Helix (February 2011, SL2 and SL5; February 2012, SL1 and SL4), and
X5-11 24.058 − 95.945 06/14/1206 2298
R/V Oceanus (May 2018, SL3, PE, SAB, SCB, SCLB, and SPB; Table 1). In
X5-15 23.977 − 91.024 06/20/2016 3708
X5-18 23.977 − 86.727 06/19/2016 1242 the GoM, 40 sedimentary cores were collected at water depths ranging
X5-22 22.988 − 94.557 06/22/2016 3717 from 966 to 3801 m during seven oceanographic cruises (XIXIMI-1 to
X5-28 21.984 − 95.06 06/24/2016 3721 XIXIMI-7) conducted from November 2010 to June 2019 on board the
X5-44 20.536 − 92.517 06/11/2016 2353 R/V Justo Sierra (Fig. 1, Table 1). The GoM cores were collected with a
X6-12 24.06 − 95.123 08/28/2017 3508
X6-26 22.025 − 97.127 08/18/2017 966
multi-corer fitted with 9.4-cm i.d. acrylic core liners or with a Soutar box
X6-27 22.000 − 96.006 08/31/2017 2722 sampler (40 × 40 cm). Once on board, the samples collected with the
X6-33 21.484 − 94.509 08/30/2017 3431 Soutar box sampler were subsampled using 8.0-cm i.d. acrylic core liners
X6-48 20.021 − 93.023 08/27/2017 1201 (Table 1). The cores from the GNHS were collected in September 2007
X7-29 22.992 − 94.011 06/08/2019 3564
by free diving using 7.2-cm i.d. polycarbonate core liners. Samples were
X7-38 21.008 − 94.498 06/08/2019 2822
PE 32.3970 − 120.5953 05/27/2018 3762 only collected from evaporation ponds 1–6 (F1–F6; Fig. 1, Table 1), as
F1 27.64822 − 113.92460 09/24/2007 ≤1.5 the presence of thick layers of gypsum on the sediment surface pre­
F2 27.59091 − 113.89429 09/24/2007 ≤1.5 vented collection from the remaining ponds (7–13). Upon collection, the
F3 27.59229 − 113.88780 09/24/2007 ≤1.5 cores were promptly sectioned at intervals of 1 or 2 cm under conditions
F4 27.65096 113.91845 09/25/2007
of air exposure using a plastic spatula to prevent any potential trace
− ≤1.5
F5 27.73791 − 113.90990 09/25/2007 ≤1.5
F6 27.74276 − 113.90855 09/25/2007 ≤1.5 metal contamination. Each sediment section was placed into Ziplok®
bags with the exception of the GNHS samples, which were placed in 50-
mL plastic centrifuge tubes. Samples were labeled and immediately
responsible for the reducing conditions that are surely present in this frozen at − 4 ◦ C until laboratory analysis. No changes were observed in
area (Davies, 1968; Ward and Tunell, 2017). the samples that suggested the oxidation of anoxic sediments. Once in
the laboratory prior to processing, the samples were thawed, placed in
2.6. Guerrero Negro Hypersaline System pre-weighed plastic vessels, and dried in a convection oven at 50 ◦ C until
reaching a constant weight (42–72 h). Once dried, the samples were
The Ojo de Liebre Lagoon (OLL), which is located in the central weighed again, and their water contents was calculated from the

17
J. Garcia-Orozco et al.
difference between their wet and dry weights. The water content was
then used to calculate the equivalent dry weight of the wet sample to
determine the operationally defined HCl-extractable and pyrite fractions
(see section 2.8).
2.8. HCl-extractable and pyrite fractions
The extraction of the metals (Me) Fe and V associated with the
operationally defined HCl-extractable (FeHCl and VHCl) and pyrite (Fepyr
and Vpyr) fractions was conducted following the method developed by
Huerta-Diaz and Morse (1990). An operationally defined fraction refers
to a specific portion of a sediment sample that is isolated and analyzed to
determine the distribution of trace metal constituents in that portion.
Operationally defined fractions are useful tools in geochemistry, but
their use requires careful consideration of the potential limitations and
sources of error through careful experimental design, appropriate
analytical techniques, and critical interpretation of the results. Briefly, a
wet sample with an equivalent dry weight of 2.5 g was digested under
constant agitation with 20 mL HCl 1 M for 16 h at room temperature.
This fraction will be defined as the HCl-extractable fraction (i.e., FeHCl
and VHCl), which includes the amorphous and crystalline oxyhydroxides
of Fe and Mn, carbonates, and acid volatile sulfide (AVS) which includes
the metastable forms of iron sulfides such as mackinawite (FeS), greigite
(Fe3S4), and dissolved S(-II) species (H2S, HS–, FeHS+, FeS clusters and
FeS nanoparticles) defined as those that pass through a 0.4 µm filter
(Rickard and Morse, 2005; Luther, 2005; Rickard, 2012). Since the wet
sediment samples were digested in HCl 1 M without an oxygen-free at­
mosphere, then the dissolved fraction of the AVS was probably trans­
formed to Fe oxyhydroxide (FeOOH(s)) and elemental sulfur (S0(s) 8 )
(Burton et al., 2006), with a slow oxidation of S0(s) 2−
8 to SO(aq)
4 (Hong et al.,
2011). However, the contribution of this dissolved fraction of the AVS
can generally be disregarded since it becomes important only when its
concentrations are >1000 µM (Rickard, 2012). Cold extraction of the
AVS fraction with 1 M HCl does not extract metals associated with the
pyritic fraction as occurs when higher concentrations of HCl (cold or hot
6 M) are used, or certain reductants (SnCl2, Ti) are incorporated
(Cornwell and Morse, 1987; Rickard and Morse, 2005). Following
digestion with 1 M HCl, the sample underwent centrifugation at 10000
rpm for 30 min. The residue obtained from the preceding fraction was
then subjected to two successive digestions using 30 mL of 10 M HF,
with the first digestion lasting for 1 h and the second for 16 h. This
particular digestion step accounts for the silicate fraction, which was
discarded as trace metals associated with silicates are considered as
“non-reactive” during early diagenesis processes (Huerta-Diaz and
Morse, 1992). The resulting residue was finally digested for 1 h with 10
mL of concentrated HNO3 to obtain the pyrite fraction (i.e., Fepyr and
Vpyr). The sum of the HCl-extractable and pyrite fractions hereinafter
will be referred to as the reactive fractions (Fereac and Vreac). Once these
fractions are obtained, it is then possible to calculate the degree of
pyritization (DOP; Berner, 1970) and the degree of trace metal pyriti­
zation (DTMP-Me; Huerta-Diaz and Morse, 1990) using the following
equations:
Fepyr Fepyr
DOP = × 100 = × 100, (1)
Fepyr + FeHCl Fereac
Mepyr Mepyr
DTMP − Me = × 100 = × 100. (2)
Mepyr + MeHCl Mereac
It is important to clarify that for the specific case of the GNHS, the
fraction extracted with HNO3 will be referred to as the pyrite fraction
(Fepyr and Vpyr), whether or not Fe and V associated with organic matter
may also be extracted in this fraction (Huerta-Diaz and Morse, 1990;
Valdivieso-Ojeda et al., 2014). This characteristic is particular to the
GNHS given the high organic matter content (0.24–13%; Huerta-Diaz
et al., 2011) present in some samples, especially those including mi­
crobial mats.
18
Geochimica et Cosmochimica Acta 356 (2023) 14–37
2.9. Trace metal analysis
The Fe and V concentrations in the samples collected in the Pacific
Ocean (excluding those from the GNHS) were determined by flame
(Agilent 200 series AA) and graphite furnace (GTA 120 graphite
furnace) atomic absorption spectrophotometry (AAS), respectively. The
detection limits (DL; all in ng mL− 1) were calculated as three times the
standard deviation of the procedural blanks. Depending on the AAS
equipment used and the batch of the numerous samples analyzed, the
DLs ranged from 14 to 83 (Fe) and 1.0–12 (V) for the MeHCl fractions and
between 9.0 and 59 (Fe) and 0.19–7.1 (V) for the Mepyr fraction. The Fe
and V concentrations from the GNHS samples were determined by
Inductively Coupled Plasma Mass Spectrometry (ICP-MS; Agilent
7700x) at the University of Santiago de Compostela (Spain), with DLs
that ranged from 0.00015 to 0.0056 (Fe) and 0.22 to 1.0 (V) for the
MeHCl fractions and 0.095–0.23 (Fe) and 0.0052–0.0060 (V) for the
Mepyr fraction. Finally, the GoM samples were analyzed by AAS (Agilent
280Z AA with graphite furnace, XIXIMI-1 to XIXIMI-4; Agilent 200 series
AA GTA 120 with graphite oven, XIXIMI-5 to XIMI-7), with DLs that
ranged from 16 to 95 (Fe) and 1.0 to 25 (V) for the MeHCl fractions and
21–90 (Fe) and 1.0–27 (V) for the Mepyr fractions.
No certified reference materials (CRM) were used to calculate the
accuracy of the measurements since there are no CRMs for operationally
defined fractions. However, the precision values that were calculated
based on the analysis of five replicates of the same sample were 97%
(FeHCl), 91% (Fepyr), 96% (VHCl), and 91% (Vpyr). Furthermore, Huerta-
Diaz and Morse (1990) carried out an extensive validation of the
method, including: (1) comparison of pyrite concentrations obtained by
our method with those measured by an independent method that
demonstrated quantitative extraction, and (2) successful comparison of
total extractions with the sum of the metal concentrations of the three
fractions (HCl + silicate + pyrite). Procedural blanks were routinely
included in each sample set, and their Fe and V concentrations were
below their respective DLs in all cases.
2.10. Organic carbon, inorganic carbon and calcium carbonate analysis
Inorganic (Ci) and total (Ct) carbon concentrations of sediments were
determined using a coulometer (UIC, Inc. Model CM150) equipped with
acidification and combustion modules. For Ci, ~25 mg of sample were
treated in the acidification module adding 5 mL of 2 M HClO4 to obtain
CO2(g). In the case of Ct, ~20 mg of sediment was introduced into the
combustion module at a temperature of 930 ◦ C in an oxygen-rich envi­
ronment. The CO2(g) generated in both modules was transported using
N2 as the carrier gas of the coulometer for its quantification in the re­
action cell inside the analyzer. Organic carbon (Corg) was then calcu­
lated as the difference between total and inorganic carbon (Corg = Ct −
Ci). Although the CO2 coulometer does not require calibration, a
powdered CaCO3 standard (Mallinckrodt® 4072) was used, with an
average recovery of 100.1 ± 1.9% (n = 12). The blanks were always
below the DL of the method (0.73 µmol g− 1). Coulometric analysis was
conducted for all samples except those collected in the GoM, where Ca
concentrations measured by X-ray fluorescence were used to estimate
CaCO3 concentrations using the equations developed by Garcia-Orozco
et al. (2020). Coulometric Ci measurements were converted to CaCO3
concentrations using the equation Ci * 8.33 = CaCO3, where 8.33 rep­
resents the ratio of the molecular weight of calcite (100.1 g mol− 1) to the
atomic weight of carbon (12.0107 g mol− 1). Subsequently, the obtained
CaCO3 concentrations were utilized to calculate the carbonate-free
concentrations of V and Fe in the operationally defined MeHCl, Mepyr,
and Mereac fractions.
2.11. Calculation of mass accumulation rates of Fe and V
The mass accumulation rate (MAR) of a trace element (e.g., Fe, V),
defined as the net rate of mass addition to the seafloor, can be calculated
J. Garcia-Orozco et al.
from the sedimentation rate (SR; vertical flux of sediment to the sea­
floor; Syvitski, 1978) and the dry bulk density (DBD; mass of the dry
solids divided by the total volume of the wet sample; Dadey et al., 2006)
of the sediment, using the following equation:
MAR = SR*DBD. (3)
And the mass accumulation rate of a trace element (MARMe) can then
be calculated from its sediment concentration (MeHCl, Mepyr, or Mereac)
and the sediment MAR value:
MARMe = MeHCl *MAR; MARMe = Mepyr *MAR; MARMe
= Mereac *MAR. (4)
The Fe and V MAR of the MeHCl, Mepyr, and Mereac fractions were
only calculated for cores whose sedimentation rates or sediment MAR
values were known using the average concentration of each fraction in
each core. For the OMZ and CCB basins, Fe and V MARs were approxi­
mated using the values reported by McManus et al. (2006), while the
MARMe for the GNHS were calculated from the DBD values of their
sediments, approximating the sedimentation rates with the microbial
mat accretion rates reported by Des Marais et al. (1992). In the case of
the GoM, the MAR values were taken from Garcia-Orozco et al. (2022)
for 23 of the 40 cores included in this study. Additionally, all MARMe
values were calculated on a carbonate-free basis following the conven­
tion of Raiswell (2006).
To approximate the annual MAR values of Fe and V, the geographic
areas reported for OMZ environments (32.14 × 106 km2; Fuenzalida
et al., 2009) and the GNHS (109 km2; Valdivieso-Ojeda et al., 2014)
were used. For the GoM, the geographic area covering the deep sedi­
ments of the gulf (>1000 m water depth; 0.75 × 106 km2) was calculated
using the polygon tool of Google Earth Pro®. It is important to mention
that when calculating the OMZ global Fe and V MARs, we assumed that
the concentrations and conditions found in our two cores were similar to
those of all OMZ regions. As such, these calculations should be consid­
ered with caution given that they are approximations.
2.12. Framboidal pyrite analysis
LA-ICPMS analyses were conducted at the University of Tasmania on
the same samples (from different sediment depths from the Black Sea
and Cariaco Basin) described in Gregory et al. (2022b). Complete
methodologies are given in Gregory et al. (2022b) but a brief summary is
provided here. Pyrite framboids were ablated using a 193 nm ArF
excimer ATL Atlex ILR laser and analyzed using an Agilent 7700 ICP-MS.
A 13 µm spot size and 5 Hz pulse rate were used in a He atmosphere with
an Ar carrier gas (0.85 L/min) mixed with the ablated material imme­
diately past the ablation point. The laser ablation standard GSD-1 g
(Guillong et al., 2005) was used for quantification of V using the
methods of Longerich et al. (1996) and 57Fe as an internal standard.
3. Results
3.1. Anoxic and anoxic-sulfidic sediments: California Continental
Borderland basins and Todos Santos Bay Canyon
3.1.1. Vanadium
The sedimentary VHCl profiles of the CCB basins and METOX1
(Fig. S1, Supplementary Data) exhibited subsurface maxima, which may
have been due to the presence of oxidation fronts that coincided with
these maxima in which the precipitation of Fe oxyhydroxides favored
the association of vanadate with this mineral phase (Blackmore et al.,
1996). Oxidation fronts can be observed in the FeHCl and Fepyr profiles
(Fig. S1, Supplementary Data), in which the steepest declines of the
former were associated with notable increases in Fepyr. The average VHCl
concentrations (Table 2) ranged from (2.5 ± 4.2) × 102 nmol g− 1 (SCB)
to (5.8 ± 2.0) × 102 nmol g− 1 in San Clemente (SCLB). The average
19
Geochimica et Cosmochimica Acta 356 (2023) 14–37
value of (4.1 ± 2.3) × 102 nmol g− 1 for these sedimentary environments
was the second highest after that obtained for the OMZ cores (Fig. 2a),
which was possibly the result of similar processes of V incorporation into
sediments as those described for the OMZ. However, there are important
differences between anoxic-sulfidic and OMZ environments: (1) AVS
concentrations in anoxic-sulfidic environments are approximately 100
times lower (<0.003 µmol g− 1 to 0.46 µmol g− 1; Nava-López and
Huerta-Díaz, 2001) than those reported for the Carmen Basin, an area of
the Gulf of California influenced by the OMZ (0.94–13 µmol g− 1;
Goldhaber and Kaplan, 1980); (2) for anoxic/anoxic-sulfidic environ­
ments, the redox boundary is generally found within the sedimentary
column (König et al., 1999; Nava-López, 2002) unlike in OMZs, where
this boundary may be found in the water column or near the sed­
iment–water interface (Scholz et al., 2017); and (3) hydrographically
restricted basins tend to have lower rates of sedimentation and deep
water renewal, which can limit the accumulation of V in these envi­
ronments (Bennett and Canfield, 2020).
The Vpyr fraction (Table 2) values ranged from 6.1 ± 1.8 nmol g− 1 in
San Clemente (SCLB) to 8.9 ± 3.0 nmol g− 1 in San Pedro (SPB), with an
average concentration of 7.2 ± 2.4 nmol g− 1 (Table 2). Indeed, the Vpyr
fraction did not show significant differences (P = 0.05) between the
cores of these sedimentary environments or when compared with the
rest of the different sedimentary environments considered in this study.
3.1.2. Iron
Overall, the FeHCl concentration profiles decreased slightly as sedi­
ment depth increased (Fig. S1, Supplementary Data), which was most
likely associated with the reductive dissolution of Fe oxyhydroxides. The
maximum FeHCl concentrations were usually located near or at the
water–sediment interface and were associated with the diffusion of Fe2+
toward this interface and subsequent reprecipitation as Fe oxy­
hydroxides (Kraal et al., 2012). The average FeHCl concentration for
anoxic and anoxic-sulfidic environments was 167 ± 60 µmol g− 1 (n =
166; Table 3; Fig. 3a) and ranged from 79.3 ± 5.4 µmol g− 1 (METOX1)
to 224 ± 39 µmol g− 1 (SCB). This range of values is similar to those
reported for anoxic/anoxic-sulfidic sediments from the Mexican ports of
Ensenada and El Sauzal, which are located in the northeastern Pacific
(190 ± 81 μmol g− 1 and 148 ± 70 μmol g− 1, respectively; Díaz-de-Alba
et al., 2016), the Pescadero and Carmen basins in the Gulf of California
(119 ± 23 μmol g− 1 and 80 ± 16 μmol g− 1, respectively; Mejía-Piña,
2016), and the Pacific coast of Baja California (106 ± 26 μmol g− 1;
Nava-López and Huerta-Díaz, 2001). The concentrations of the Fepyr
fraction increased with sediment depth (Fig. S1, Supplementary Data) as
a consequence of the pyritization of Fe oxyhydroxides. The values for
anoxic/anoxic-sulfidic environments ranged from 8.8 ± 3.7 μmol g− 1
(SCLM) to 40 ± 19 μmol g− 1 (METOX1) with an average of 26 ± 23
μmol g− 1 (Table 3), which is similar to the values reported for coastal
sediments such as those in Ensenada and El Sauzal (32 ± 20 μmol g− 1
and 50 ± 23 μmol g− 1, respectively; Díaz-de-Alba et al., 2016) and the
Pescadero and Carmen basins in the Gulf of California (49 ± 20 μmol g− 1
and 49 ± 17 μmol g− 1, respectively; Mejía-Piña, 2016; Fig. 3b).
3.2. Eastern North Pacific OMZ
3.2.1. Vanadium
The VHCl concentrations as a function of sediment depth (Fig. S2,
Supplementary Data) in stations influenced by the OMZ showed rela­
tively consistent values. However, some subsurface minimum and
maximum values were observed, potentially attributed to fluctuations in
the depth of the OMZ. In the particular case of San Blas (SAB; Fig. S2),
the VHCl values decreased with depth, which suggests the dissolution or
transformation of some of the mineral phases associated with this
geochemical fraction. The average VHCl concentration in the OMZ
(Table 2) was (7.9 ± 4.3) × 102 nmol g− 1 (n = 198), with a range from
(4.8 ± 1.1) × 102 nmol g− 1 (SL4) to (12.0 ± 5.1) × 102 nmol g− 1 (SAB).
These average values were the highest among all eastern North Pacific
J. Garcia-Orozco et al. Geochimica et Cosmochimica Acta 356 (2023) 14–37

Table 2
Average (±1 standard deviation), number of values considered (n), and range of vanadium concentrations in the geochemical fractions operationally defined as HCl-
extractable (VHCl), pyrite (Vpyr), and reactive (Vreac) as well as degree of pyritization of V (DTMP-V) for each sedimentary core collected in this study. Abbreviations of
cores are defined in Table 1.
Station VHCl (nmol g− 1)×102 Vpyr (nmol g− 1) Vreac (nmol g− 1)×102 DTMP-V (%)

Average n Range Average n Range Average n Range Average n Range

Anoxic and anoxic-sulfidic sediments: California Continental Borderland basins and Todos Santos Bay Canyon
METOX1 2.77 ± 0.35 20 2.2–3.7 7.2 ± 1.9 20 4.0–10.4 2.8 ± 0.35 20 2.3–3.8 2.63 ± 0.87 20 1.36–4.38
SCB 2.5 ± 4.2 30 1.5–3.2 7.3 ± 1.9 30 3.2–10.8 2.62 ± 0.42 30 1.6–3.3 2.85 ± 0.94 30 1.12–4.60
SCLB 5.8 ± 2.0 39 1.3–9.4 6.1 ± 1.8 38 2.5–10.2 5.8 ± 2.0 39 1.3–9.5 1.09 ± 0.42 39 0.38–2.71
SPB 4.5 ± 2.7 28 2.6–16.7 8.9 ± 3.0 28 4.6–20.8 4.6 ± 2.8 28 2.7–17.0 2.13 ± 0.72 28 0.98–3.60
Average 4.1 ± 2.3 117 1.3–16.7 7.2 ± 2.4 116 2.5–20.8 4.2 ± 2.3 116 1.3–17.0 2.1 ± 1.0 116 0.38–4.60

Eastern North Pacific Ocean oxygen minimum zone

SL1 7.4 ± 2.7 17 1.9–11.8 5.8 ± 1.2 17 3.6–9.1 7.4 ± 2.7 17 2.0–11.9 0.90 ± 0.53 17 0.54–2.84
SL2 5.0 ± 2.5 26 1.9–9.8 4.62 ± 23 <2.6–6.5 5.0 ± 2.5 26 2.0–9.9 1.10 ± 0.61 26 0.14–2.37
0.86
SL3 8.7 ± 2.2 40 5.1–15.2 13.1 ± 4.1 40 4.6–22.5 8.8 ± 2.3 40 5.3–15.4 1.50 ± 0.44 40 0.70–2.53
SL4 4.8 ± 1.1 40 1.8–6.8 4.0 ± 1.5 40 2.1–7.7 4.8 ± 1.1 40 1.8–8.6 0.93 ± 0.35 40 0.51–1.81
SL5 7.6 ± 3.9 35 1.7–17.1 5.5 ± 2.3 29 <1.4–11.2 7.7 ± 4.0 35 1.8–17 0.76 ± 0.80 35 0.00–4.80
SAB 12.0 ± 5.1 40 1.3–32.9 8.4 ± 7.1 40 4.3–47.9 12.6 ± 5.4 40 1.5–33 0.77 ± 0.84 40 0.27–5.68
Average 7.9 ± 4.3 198 1.3–32.9 7.3 ± 5.1 189 2.1–47.9 7.9 ± 4.3 198 1.4–33.1 0.98 ± 0.68 198 0.00–5.68

Oxic sediments: Gulf of Mexico (GoM), Patton Escarpment and continental shelf of Baja California
X1-3 0.44 ± 0.14 16 0.21–7.7 5.1 ± 1.5 16 0.89–7.1 0.49 ± 0.14 16 0.26–0.83 11.0 ± 4.9 16 2.7–21.4
X1-36 1.12 ± 0.81 15 0.20–3.11 3.2 ± 1.4 15 0.73–4.8 1.15 ± 0.81 15 0.24–3.1 4.9 ± 4.7 15 0.37–18.8
X1-40 2.69 ± 0.98 19 1.00–5.08 6.7 ± 1.5 19 4.7–10.6 2.27 ± 0.98 19 1.1–5.1 2.8 ± 1.7 19 1.2–9.31
X1-43 0.55 ± 0.37 16 0.17–1.63 <0.18 0 <0.18 0.55 ± 0.37 16 0.17–1.63 0.058 ± 16 0.006–0.1
0.042
X2-2 0.098 ± 0.044 14 0.009–0.14 4.5 ± 1.7 15 2.0–7.2 0.139 ± 15 0.02–0.19 36 ± 20 15 17–87.1
0.048
X3-7 0.97 ± 0.47 13 0.65–2.13 6.7 ± 1.0 13 4.7–8.2 1.03 ± 0.47 13 0.72–2.2 7.2 ± 1.9 13 3.7–9.45
X3-38 1.64 ± 0.32 15 1.20–2.23 7.0 ± 1.5 15 4.6–9.4 1.71 ± 0.31 15 1.2–2.3 4 ± 97 15 2.3–7.50
X3-43 1.11 ± 0.60 11 0.46–2.61 7.4 ± 1.6 11 5.1–1.0 1.18 ± 0.60 11 0.52–2.7 7.0 ± 2.2 11 3.4–12.7
X3-46 1.19 ± 0.82 16 0.17–2.38 7.6 ± 2.3 16 5.0–1.3 1.22 ± 0.81 16 0.23–2.5 13 ± 14 16 2.4–44.1
X4-1 3.5 ± 1.2 17 1.60–6.29 9.6 ± 4.4 17 4.0–1.8 3.6 ± 1.2 17 1.66–6.4 2.8 ± 1.4 17 1.2–5.62
X4-7 2.52 ± 0.74 16 0.93–3.41 5.0 ± 2.6 16 1.9–1.0 2.56 ± 0.74 16 0.95–3.4 2.1 ± 1.3 16 1.0–6.40
X4-14 1.6 ± 1.3 15 0.027–3.63 8.4 ± 3.7 15 4.2–1.8 1.6 ± 1.4 15 0.11–3.7 15 ± 22 15 2.3–75.9
X4-31 1.58 ± 0.58 39 0.63–3.10 2.5 ± 2.3 35 <0.17–1.2 1.60 ± 0.57 39 0.66–3.1 1.5 ± 1.7 39 0–8.78
X4-34 2.3 ± 2.2 26 <0.0016–9.06 6.2 ± 3.6 28 1.0–1.3 2.2 ± 2.2 28 0.027–9.0 5.8 ± 5.5 28 0.37–21.0
X4-40 1.5 ± 1.0 28 0.20–5.35 6.8 ± 3.3 27 <0.17–1.7 1.5 ± 1.1 28 0.23–5.5 6.1 ± 5.9 28 0–30.4
X4-45 1.7 ± 1.0 29 0.51–5.50 5.8 ± 2.4 21 <0.17–1.1 1.8 ± 1.0 29 0.54–5.56 2.5 ± 2.2 29 0–7.97
X4-47 3.9 ± 2.3 27 1.20–9.85 8.5 ± 3.2 27 1.7–1.5 3.9 ± 2.5 27 0.063–9.9 2.6 ± 1.5 27 0.37–5.90
X5-1 3.69 ± 0.68 17 2.70–5.08 2.1 ± 5.0 10 <1.2–2.7 3.71 ± 0.64 17 2.65–5.1 0.33 ± 0.25 17 0–0.722
X5-3 2.67 ± 0.24 17 2.10–2.96 5.3 ± 1.8 14 <1.8–8.8 2.70 ± 0.23 17 2.17–3.0 1.73 ± 0.87 17 0.28–3.27
X5-5 4.09 ± 0.42 16 3.00–4.65 2.3 ± 1.4 10 <1.2–5.9 4.10 ± 0.43 16 2.97–4.6 0.39 ± 0.31 16 0–1.29
X5-8 1.0 ± 1.3 13 0.074–3.48 4.0 ± 1.8 10 <1.2–7.0 1.1 ± 1.3 13 0.10–3.5 8 ± 11 13 0–36.5
X5-11 2.93 ± 0.60 14 2.30–4.53 4.7 ± 2.1 10 <1.2–8.4 2.96 ± 0.61 14 2.31–4.6 1.10 ± 0.83 14 0–1.76
X5-15 2.71 ± 0.59 13 1.80–3.92 3.0 ± 1.2 8 <1.2–4.9 2.72 ± 0.53 13 1.78–3.9 0.75 ± 0.54 13 0–1.76
X5-18 1.20 ± 0.74 12 0.059–2.55 <3.5 0 <3.5 1.20 ± 0.74 12 0.058–2.5 0.8 ± 1.3 12 0–3.55
X5-22 1.4 ± 1.6 17 1.70–4.38 7.6 ± 2.9 8 <2.6–13.0 1.5 ± 1.7 17 0.16–4.4 5.4 ± 7.9 17 0–24.5
X5-28 2.15 ± 0.46 17 1.20–2.86 6.0 ± 1.5 17 3.4–9.0 2.20 ± 0.46 17 1.24–2.9 2.81 ± 0.96 17 1.6–4.77
X5-44 1.77 ± 0.92 17 1.20–3.43 4.5 ± 1.3 8 <2.5–6.3 1.79 ± 0.85 17 0.12–3.5 1.9 ± 2.3 17 0–8.90
X6-12 1.21 ± 0.23 40 0.85–1.71 5.4 ± 1.3 19 <3.0–7.9 1.233 ± 40 0.84–1.7 3.2 ± 1.7 40 1.3–8.18
0.089
X6-26 1.92 ± 0.57 30 0.94–3.48 5.5 ± 1.8 28 <2.6–9.0 1.97 ± 0.58 30 0.98–3.5 2.81 ± 0.81 30 1.1–4.27
X6-27 0.73 ± 0.55 35 0.24–2.71 5.6 ± 1.1 34 <3.3–8.3 0.79 ± 0.56 35 0.30–2.7 9.4 ± 4.7 35 2.8–19.5
X6-33 0.54 ± 0.43 29 <0.037–2.07 10.2 ± 2.2 7 <4.2–14.6 0.56 ± 0.45 30 0.14–2.2 10.4 ± 6.1 30 2.8–34.9
X6-48 2.50 ± 0.88 40 1.10–5.00 4.9 ± 1.6 6 <0.36–0.80 2.51 ± 0.89 40 1.0–5.2 0.9 ± 1.1 40 0–5.68
X7-29 0.48 ± 0.22 20 0.12–1.22 21.9 ± 5.0 20 0.14–32.7 0.69 ± 0.24 20 0.31–1.5 33 ± 11 20 16–64.3
X7-38 1.64 ± 0.73 20 0.80–3.51 11.4 ± 1.1 20 8.8–13.4 1.80 ± 0.72 20 0.91–3.6 7.5 ± 2.9 20 2.4–13.1
PE 1.69 ± 0.96 21 0.48–5.2 7.3 ± 2.2 21 4.0–14.1 1.82 ± 0.99 21 0.50–5.3 4.8 ± 2.0 21 1.72–10
METOX2 2.58 ± 0.53 25 1.9–3.8 8.0 ± 1.4 25 5.9–10.8 2.6 ± 0.54 25 2.0–4.0 3.08 ± 0.64 25 1.82–4.78
METOX3 5.2 ± 2.3 24 2.6–9.6 5.0 ± 1.9 24 1.5–9.3 5.2 ± 2.4 24 2.7–9.7 1.22 ± 0.80 24 0.24–3.35
Average 1.9 ± 1.5 769 0.009–9.85 6.6 ± 4.2 605 <0.16–32.7 2.0 ± 1.5 773 0.027–9.9 6 ± 11 773 0–87.1
AverageGoM 1.8 ± 1.4 716 0.009–9.85 6.4 ± 4.4 559 <0.16–32.7 1.8 ± 1.4 718 0.027–9.9 6 ± 11 716 0–87.1

Gulf of Mexico turbidites

X1-31 0.010 ± 0.030 13 0.0070–0.0190 9.9 ± 2.7 13 5.0–14.2 0.109 ± 13 0.060–0.15 89.7 ± 4.5 13 83–94.6
0.026
X1-33 0.031 ± 0.018 15 0.0090–0.0789 11.9 ± 6.5 15 3.9–20.3 0.147 ± 15 0.048–0.25 77 ± 13 15 45–90.5
0.069
X2-10 0.095 ± 0.080 13 0.0083–0.224 3.3 ± 2.1 13 1.3–9.1 0.127 ± 13 0.032–0.25 37 ± 30 13 11–91.6
0.074
(continued on next page)

20
J. Garcia-Orozco et al. Geochimica et Cosmochimica Acta 356 (2023) 14–37

Table 2 (continued )
Station VHCl (nmol g− 1)×102 Vpyr (nmol g− 1) Vreac (nmol g− 1)×102 DTMP-V (%)

Average n Range Average n Range Average n Range Average n Range

X2-24 0.068 ± 0.070 13 0.0040–0.170 6.5 ± 4.3 13 2.3–13.7 0.132 ± 13 0.041–0.21 58 ± 36 13 18–96.3
0.055
X3-44 0.26 ± 0.28 10 <0.000078–0.597 5.9 ± 1.9 12 3.7–11.2 0.27 ± 0.27 12 0.041–0.65 55 ± 39 12 6.0–90.3
X3-47 (2.9 ± 2.4)× 1 <0.000078–0.0100 12.1 ± 6.5 13 4.3–21.8 0.121 ± 13 0.043–0.218 97.0 ± 2.3 13 91–100
10− 4 0.065
Average 0.08 ± 0.15 65 0.0070–0.597 8.6 ± 5.4 79 1.3–21.8 0.16 ± 0.13 79 0.032–0.65 69 ± 32 79 6.0–100

Guerrero Negro Hypersaline System

F1 1.9 ± 2.1 18 0.04–6.86 5.4 ± 5.4 18 0.8–18.7 1.9 ± 2.1 18 0.04–6.88 31 ± 41 18 0.2–96.2
F2 1.30 ± 0.40 18 0.20–1.94 5.0 ± 9.2 16 0.01–28.2 1.35 ± 0.40 18 0.49–1.97 7.5 ± 16.5 18 0.1–57.9
F3 6.5 ± 3.1 24 6–10.9 9.5 ± 6.2 23 0.01–23.8 6.6 ± 3.1 24 8.0–10.9 7 ± 17 24 0.4–74.1
F4 1.9 ± 1.9 17 0.001–7.08 10.6 ± 4.1 18 5.1–22.4 2.1 ± 1.9 18 0.25–7.2 31 ± 38 18 1.5–93.6
F5 1.0 ± 1.3 17 0.04–5.59 18 ± 15 17 48–63.9 1.2 ± 1.3 17 0.06–7.2 25 ± 26 17 2.9–89.5
F6 1.31 ± 0.40 18 0.38–2.40 8.7 ± 6.9 18 9–20.6 1.39 ± 0.47 18 0.38–5.7 6.5 ± 5.8 18 0.7–23.5
Average 2.2 ± 2.5 112 0.001–10.9 7.8 ± 8.7 110 0.01–63.9 2.9 ± 3.0 113 0.45–11.0 14 ± 27 113 0.1–96.2

and GoM cores (Fig. 2a, Table 2). Indeed, the dendrogram categorization
(Fig. S3, Supplementary Data) of all samples in this study that was used
to evaluate the similarity of VHCl concentrations indicated that the
values of the OMZ (SL1 to SL5, SAB) were different from those of all
other analyzed samples. These results are consistent with those of Ben­
nett and Canfield (2020), who reported that median total V enrichment
for OMZ sediments was 7.7 times higher than the average value of the
Earth’s crust. Bennett and Canfield (2020) also suggested that this
enrichment is associated with high fluxes of reactive solid phases such as
Fe oxyhydroxides.
The Vpyr profiles indicated that their concentrations generally
remained constant as the sediment depth increased (Fig. S2, Supple­
mentary Data). The average concentrations in this fraction ranged from
4.0 ± 1.5 nmol g− 1 to 13.1 ± 4.1 nmol g− 1, with both concentrations
present in the San Lázaro Basin (SL4 and SL3, respectively; Table 2,
Fig. 2b). The average Vpyr value for all the OMZ cores (7.3 ± 5.1 nmol
g− 1; n = 189; Table 2, Fig. 2b) was ~100 times lower than that obtained
for VHCl and statistically similar (P = 0.05) to those of the eastern North
Pacific and GoM cores.
3.2.2. Iron
The FeHCl concentrations (Fig. S2, Supplementary Data) for the OMZ
showed no relevant changes with sediment depth except for the occa­
sional presence of a few subsurface maxima, particularly in the San
Lázaro Basin. The observed variability and subsurface maxima could
result from changes in the input rates of terrestrial materials (van Geen
et al., 2003; Berelson et al., 2005), as the low oxygen conditions of the
San Lázaro Basin likely limit bioturbation processes. FeHCl exhibited an
average value of 47 ± 34 µmol g− 1 (n = 198), and its values ranged from
20.3 ± 4.6 µmol g− 1 (SL5) to 85 ± 23 µmol g− 1 (SL3). These concen­
trations were among the lowest values of all sedimentary environments
considered in this study (Table 3). This behavior may be due to the
remobilization of Fe in the superficial sediment layer, which results in a
flux of Fe to the water column and consequently the impoverishment of
Fe oxyhydroxides in OMZ sediments (<180 µmol g− 1; Scholz et al.,
2014).
The average concentration of the Fepyr fraction was found to be high
(Table 3), with a value of 66 ± 41 µmol g− 1 (n = 198) and values in the
range 37 ± 19 µmol g− 1 (SL2) to 87 ± 15 µmol g− 1 (SL4). The average
Fepyr concentrations of OMZ stations were always higher than those of
the other sedimentary environments (Fig. 3b; Table 3), which is
consistent with the almost complete conversion of Fe oxyhydroxides into
Fe sulfides (Scholz et al., 2014). This behavior was reflected in the high
degree of pyritization (DOP; Eq. (1)) observed in this study, which
ranged from 39 ± 26% to 75.3 ± 4.0% (Table 3). These results are
consistent with those obtained by Kraal et al. (2012), who reported that
pyrite could become a sink for nearly 40% of the total reactive Fe in OMZ
sediments.
3.3. Oxic sediments: Gulf of Mexico, Patton Escarpment, and Baja
California continental shelf
3.3.1. Vanadium
A description and discussion of the biogeochemical behavior of
FeHCl, Fepyr, and Fereac in deep GoM sediments was provided by Garcia-
Orozco et al. (2022), thus this section only presents the results for va­
nadium (Figs. S4–S8, Supplementary Data). The average VHCl concen­
tration for predominantly oxic cores (GoM and Patton Escarpment) was
(1.9 ± 1.5) × 102 nmol g− 1 (n = 769; Table 2) and ranged from (0.098
± 0.044) × 102 nmol g− 1 to (5.2 ± 2.3) × 102 nmol g− 1 for the X2-2 and
METOX3 cores, respectively. These values were the lowest obtained in
this study, with the exception of those of the turbiditic deposits in the
GoM (Fig. 2a; Table 2). The Vpyr concentrations generally remained
constant as sediment depth increased (e.g., X1-3, X1-40, X6-27;
Figs. S4a, e, S7f, Supplementary Data), with concentrations ranging
from <0.18 nmol g− 1 (X1-43) to 21.9 ± 5.0 nmol g− 1 (X7-29), and an
average concentration of 6.6 ± 4.2 nmol g− 1 (n = 605; Table 2). The
relative standard deviation (RSD = 64%) of the average concentration
was relatively low considering that the sedimentary cores included in
this study were distributed across a surface of ~5 × 105 km2.
3.4. Guerrero Negro hypersaline system
3.4.1. Vanadium
The average VHCl concentration was (2.2 ± 2.5) × 102 nmol g− 1 (n =
112; Table 2) and ranged from (1.0 ± 1.3) × 102 nmol g− 1 (F5) to (6.5 ±
3.1) × 102 nmol g− 1 (F3). On the other hand, the Vpyr concentration
ranged from 5.0 ± 9.2 nmol g− 1 (F2) to 18 ± 15 nmol g− 1 (F5) with an
average value of 7.8 ± 8.7 nmol g− 1 (n = 110; Table 2; Fig. S9, Sup­
plementary Data).
3.4.2. Iron
The average FeHCl value of the GNHS (Table 3; Fig. S9, Supplemen­
tary Data) was 18 ± 30 µmol g− 1 (n = 113), with values that ranged from
6.1 ± 5.8 µmol g− 1 (F5) to 43.5 ± 6.6 µmol g− 1 (F3). The average value
obtained in this study was 5–8.5 times lower than those of other sedi­
mentary environments such as the anoxic-sulfidic sediments of Orca
Basin (154 ± 27 µmol g− 1; Huerta-Diaz and Morse, 1992) as well as
those of the oxic environments of the Pacific coast of Baja California
(106 ± 26 µmol g− 1; Nava-López and Huerta-Díaz, 2001) and GoM shelf
and slope (87 ± 25 µmol g− 1; Huerta-Diaz and Morse, 1992). However,
the average FeHCl concentration of the GNHS was very similar to that
reported for the turbidites of the GoM (16 ± 40 µmol g− 1), in which
pyrite production is limited by the availability of FeHCl (Garcia-Orozco

21
J. Garcia-Orozco et al.
et al., 2022). The average value of Fepyr was only 4.6 ± 4.3 µmol g− 1 (n
= 110), with values that ranged from 1.5 ± 1.3 µmol g− 1 (F1) to 10.1 ±
8.6 µmol g− 1 (F3) (Table 3). These values were generally lower than
those reported for other hypersaline environments such as the hyper­
saline basins of Tyro (79–149 μmol g− 1; Henneke et al., 1997), Bannock
(28–178 μmol g− 1; Henneke et al., 1997), and Orca (2.0–134 μmol g− 1;
Hurtgen et al., 1999). This difference is mainly due to pyrite formation
in the GNHS being limited by the availability of reactive Fe (Huerta-Diaz
et al., 2011; Valdivieso-Ojeda et al., 2014).
3.5. LA-ICPMS analyses of framboidal pyrite
The complete data set of the 176 LA-ICPMS analyses of pyrite
framboids from the Cariaco Basin and Black Sea are given in the Sup­
plementary Data. Generally, the results of the euxinic Cariaco Basin, the
euxinic Black Sea, and the sulfide diffusion zone of the Cariaco Basin
were similar, having median V concentrations of 0.980 nmol µmol− 1,
22
Geochimica et Cosmochimica Acta 356 (2023) 14–37
Fig. 2. Box and whisker plots and average values of
the (a) concentrations of the HCl-extractable fraction
(VHCl), (b) pyrite fraction (Vpyr) and (c) degree of
pyritization of V (DTMP-V) grouped by the type of
environment or sedimentary deposit: (1) turbidities,
(2) hypersaline, (3) oxic, (4) anoxic/anoxic-sulfidic,
and (5) oxygen minimum zone (OMZ). Non-hatched
and hatched boxes of the hypersaline environment
correspond to sediment (S) and microbial mat (M)
values, respectively. The shaded area in (b) represents
the upper and lower limits that define the general
average ± 1 standard deviation of Vpyr (7.2 ± 5.2
nmol g− 1; n = 1098). Abbreviations of cores are
defined in Table 1. Insert shows the same figure but
with vertical log scale.
0.297 nmol µmol− 1, and 0.222 nmol µmol− 1, respectively.
4. Discussion
4.1. Behavior of iron in Eastern North Pacific OMZ
The Fepyr profiles showed an increase in concentration as sediment
depth increased (Fig. S2, Supplementary Data) due to the gradual con­
version of FeHCl and AVS to pyrite (Suits and Arthur, 2000; Kraal et al.,
2012), although part of this AVS can dissolve at depth (Rickard, 2012).
However, certain instances were observed in which Fepyr concentrations
increased with depth while FeHCl concentrations did not exhibit any
decreases (e.g., cores SL2, SL3, and SL4; Fig. S2, Supplementary data).
Similar behavior has been documented in sediments influenced by OMZs
(e.g., McKay et al., 2007). One potential explanation for this behavior is
that a portion of the FeHCl may exist in the form of AVS, which is known
to occur at elevated concentrations (0.94 to 13 µmol g− 1; Goldhaber and
J. Garcia-Orozco et al. Geochimica et Cosmochimica Acta 356 (2023) 14–37

Table 3
Average (±1 standard deviation), number of values considered (n), and range of Fe concentrations in the geochemical fractions operationally defined as HCl-
extractable (FeHCl), pyrite (Fepyr), and reactive (Fereac) as well as degree of pyritization (DOP) for each sedimentary core collected in this study. The average
values of the different fractions of Fe and DOP for the Gulf of Mexico (GoM) and its turbidites were taken from Garcia-Orozco et al. (2022). Abbreviations of cores are
defined in Table 1.
Station FeHCl (μmol g− 1) Fepyr (μmol g− 1) Fereac (μmol g− 1) DOP (%)

Average n Range Average n Range Average n Range Average n Range

Anoxic and anoxic-sulfidic sediments: California Continental Borderland basins and Todos Santos Bay Canyon
METOX1 79.3 ± 5.4 20 69–88 40 ± 19 20 11–73 119 ± 18 20 88–143 32 ± 12 20 12–51
SCB 224 ± 39 30 149–348 26 ± 22 30 4–86 250 ± 28 30 203–356 10.7 ± 9.0 30 2–35
SCLM 141 ± 28 39 82–204 8.8 ± 3.7 39 5–21 150 ± 30 39 88–218 5.8 ± 1.8 39 4–13
SPB 204 ± 31 28 146–284 28 ± 27 28 11–105 242 ± 34 28 177–307 15.2 ± 9.3 28 5–36
Average 167 ± 60 117 69–348 26 ± 23 117 4–105 193 ± 62 117 88–356 14 ± 12 117 2–51

Eastern North Pacific Ocean oxygen minimum zone

SL1 28.9 ± 3.4 17 23–36 56 ± 34 17 12–129 84 ± 34 17 40–162 60 ± 16 17 29–79
SL2 36.3 ± 5.3 26 29–48 37 ± 19 26 9–82 73 ± 20 26 40–116 47 ± 14 26 23–71
SL3 85 ± 23 40 41–132 85 ± 47 40 16–194 170 ± 38 40 86–247 47 ± 18 40 12–81
SL4 30.8 ± 5.7 40 24–51 87 ± 15 40 58–112 118 ± 17 40 87–148 73.8 ± 4.0 40 64–79
SL5 20.3 ± 4.6 35 12–29 49 ± 15 35 15–80 85 ± 11 35 64–102 75.3 ± 4.0 35 67–82
SAB 70 ± 46 40 15–265 54 ± 50 40 7–200 125 ± 63 40 57–289 39 ± 26 40 8–84
Average 47 ± 34 198 12–265 66 ± 41 198 7–200 110 ± 50 198 38–289 56 ± 21 198 8–84

Oxic sediments: Gulf of Mexico, Patton Escarpment and continental shelf of Baja California
GoM 79 ± 43 702 0.079–641 1.54 ± 0.65 702 0.026–7.66 81 ± 43 702 0.34–643 3.1 ± 2.8 702 0.053–96
METOX2 76 76 ± 17 25 60–115 5.3 ± 2.1 25 3–10 81 ± 16 25 65–119 6.8 ± 3.2 25 3–13
METOX3 91 ± 22 24 57–123 3.18 ± 0.80 24 2–5 94 ± 22 24 59–127 3.43 ± 0.69 24 2–5
PE 154 ± 30 21 109–220 7.2 ± 1.8 21 4–10 161 ± 30 21 115–228 4.5 ± 1.1 21 3–7
Average 82 ± 43 772 0.079–641 1.9 ± 1.4 772 0.026–10 83 ± 44 772 0.34–643 3.0 ± 5.4 772 0.053–96

Gulf of Mexico turbidites

Average 0.6 ± 2.0 62 0.065–10.1 2.6 ± 1.1 62 0.46–5.56 3.2 ± 2.0 62 0.55–12.3 89 ± 20 62 6.8–98.5

Guerrero Negro Hypersaline System

F1 10 ± 11 18 0.007–33 1.5 ± 1.3 18 0.35–5.4 10 ± 10 18 0.54–34 51 ± 46 18 2.2–99.8
F2 10.1 ± 5.1 18 0.02–16 1.9 ± 2.7 16 0.33–11 11.8 ± 3.9 18 3.8–17.9 21 ± 36 18 2.8–99.5
F3 43.5 ± 6.6 24 28–54 10.1 ± 8.6 23 3.5–34 53.2 ± 7.9 24 33–71 17 ± 12 24 6.0–47.7
F4 13 ± 11 18 0.0008–33 4.8 ± 2.5 18 1.5–11 18.3 ± 6.7 18 1.5–40 50 ± 35 18 15.4–99.9
F5 6.1 ± 5.8 17 0.09–24 4.3 ± 1.3 17 1.5–9 10.5 ± 7.2 17 4.1–33 46 ± 24 17 22.2–98.7
F6 12.8 ± 3.1 18 6–19 4.7 ± 1.3 18 2.9–8 17.5 ± 3.3 18 9.9–23.5 27.4 ± 7.4 18 13.8–38.5
Average 18 ± 30 113 0.0008–54 4.6 ± 4.3 110 0.33–34 22 ± 18 113 0.53–71 29 ± 30 113 2.2–99.9

Kaplan, 1980). Additionally, it is possible that the iron monosulfide to
pyrite reaction can be limited in iron dominated systems (Riedinger
et al., 2017).
4.2. Behavior of vanadium in deep, oxic sediments
The low VHCl concentrations measured in the predominantly oxic
sediments may have been due to the low V inputs to deep sediments that
reflect the large distances that separate the sediments from the main
sources of this element, such as rivers (~1640 × 109 g y− 1; Shiller and
Mao, 1999; Hope, 2008), runoff, and atmospheric particles (~60 × 109 g
y− 1; Schlesinger et al., 2017), which represent ~96% of the total V input
to marine sediments (Schlesinger et al., 2017).
It was also observed that as the depth increased in the sedimentary
column, the VHCl concentration in oxic sediments exhibited three
different behaviors (Figs. S4–S8, Supplementary Data): (1) the concen­
trations of VHCl decreased; (2) the VHCl values remained relatively con­
stant; and (3) the VHCl profiles exhibited surface or subsurface maxima.
If it is assumed that sediment input rates have not changed significantly
over time for this sediment type, then the changes observed in the
profiles should be mainly caused by diagenetic changes, bioturbation
processes, or physical disturbances (e.g., turbiditic events). For the cores
with reported thickness of the mixed layer (Díaz-Asencio et al., 2019,
2020), we considered the shape of the profile downward from the bot­
tom of this layer, which essentially resets the diagenetic processes in the
sediments (Peng and Broecker, 1984).
Behavior (1) of the VHCl concentrations may have been due to the
gradual reductive dissolution of Fe oxyhydroxides (Garcia-Orozco et al.,
2022) accompanied by the subsequent release of V into interstitial water
(e.g., X1-43, X3-38, X3-46; Fig. S4f, S5a, d, Supplementary Data).
Behavior (2) is due to the absence of changes in the redox conditions that
could affect the VHCl (e.g., X5-3, X5-5, X6-26; Figs. S6e, f, S7e, Supple­
mentary Data) and FeHCl (Garcia-Orozco et al., 2022) concentrations. In
the case of behavior (3), the surface and subsurface maxima may have
been caused by the formation of oxidation fronts. These fronts would
then represent the sediment depths at which Fe2+ diffusing from iron-
reducing zones located in the deepest parts of the sediments oxida­
tively precipitated (Garcia-Orozco et al., 2022), with V coprecipitating
during this process (e.g., X1-36, X4-34, X5-11; Figs. S4d, S5j, S6h,
Supplementary Data). For example, Nava-López and Huerta-Díaz (2001)
reported substantial increases in crystalline Fe oxyhydroxides in the first
8 cm of the METOX2 core, the depths of which coincide with the VHCl
maximum observed in this core. Another possibility is that the presence
of important concentrations of AVS are responsible for the VHCl sub­
surface maxima; however, the observed subsurface maximum of VHCl in
METOX2 is located precisely in the zone in which Nava-López and
Huerta-Díaz (2001) reported the minimum AVS concentrations. Finally,
no trend was observed in the VHCl profiles within the mixed layers due to
bioturbation processes that altered and disturbed the sediment and
resulted in highly variable concentrations of VHCl (e.g., X4-1, X4-7, X5-1;
Figs. S5f, S5g, S6d, Supplementary Data) and FeHCl (Garcia-Orozco et al.,
2022).
The constancy in the concentrations of Vpyr as sediment depth
increased is mainly due to the low sedimentation rates (2.7–24.6 cm

23
J. Garcia-Orozco et al.
ky− 1; Díaz-Asencio et al., 2019, 2020) and low inputs of organic matter
(Jahnke, 1996), which commonly occur in deep sediments (>1,000 m
water depth). The combination of these two factors results in molecular
oxygen in the water column penetrating centimeters to meters into the
sedimentary column (D’Hondt et al., 2015). As a result, diagenetic
processes beyond the aerobic oxidation of organic matter may not occur,
especially in the sediment depth range covered in the GoM cores (13–35
cm).
4.3. Transport mechanisms of vanadium to sediments in OMZs
Three mechanisms of vanadium transport to sediments have been
proposed for OMZ regions: (1) removal of V via coprecipitation with Fe
sulfides (mainly as AVS fraction; Ohnemus et al., 2017); (2) reductive
dissolution of Fe oxyhydroxides in sediments, release of reduced Fe2+
into the the oxygen depleted overlying bottom water, and reprecipita­
tion of Fe oxyhydroxides (along with the adsorption/coprecipitation of
24
Geochimica et Cosmochimica Acta 356 (2023) 14–37
Fig. 3. Box and whisker plots and average values of
the (a) concentrations of the HCl-extractable fraction
(FeHCl), (b) pyrite fraction (Fepyr), and (c) degree of
pyritization (DOP) grouped by the type of environ­
ment or sedimentary deposit: (1) turbidities, (2) hy­
persaline, (3) oxic, (4) anoxic/anoxic-sulfidic, and (5)
oxygen minimum zone (OMZ). Non-hatched and
hatched boxes of the hypersaline environment corre­
spond to sediment (S) and microbial mat (M) values,
respectively. Abbreviations of cores are defined in
Table 1. Inserts show the same figure but with vertical
log scale.
vanadate) in the oxycline (Telfeyan et al., 2015; Scholz et al., 2017); and
(3) V incorporation by denitrifying prokaryotes and subsequent trans­
port to sediments (Ohnemus et al., 2017). The redox cycle described by
mechanism (2) may possibly occur in a cyclic and continuous manner,
transporting V directly from the water column to the sediments. As these
sedimentary environments become enriched with V and Fe oxy­
hydroxides are reductively dissolved, V could then be retained in the
sediments by a mineral phase and/or by organic matter (Gustafsson,
2019). The elevated concentrations of VHCl suggest that the mineral
phases present in this fraction, which could incorporate V in sediments
under the influence of OMZs, are Fe and Mn oxyhydroxides, or the
operationally defined fraction AVS. Considering that the first two min­
eral phases may only be stable in sediments in contact with the water
column (concentration of O2 < 20 µmol kg− 1, Gilly et al., 2013) but
unstable below this zone, it is unlikely that Fe and Mn oxyhydroxides
play relevant roles in V enrichment in OMZ sediments. Our results
suggest that the mineral phase responsible for V enrichment in OMZ
J. Garcia-Orozco et al.
sediments is the AVS (which includes mackinawite and greigite) for the
following reasons: (1) sediment digestion with HCl 1 M (conducted in
this study) extracts AVS, thus it is reasonable to expect that this diges­
tion produces V enrichment in the HCl-extractable fraction (e.g.,
Fig. 2a); (2) digestion with HCl 1 M does not generally affect organic
matter (Huerta-Diaz and Morse, 1990), and the correlation between
organic carbon (Corg) and VHCl was weakly significant (r = 0.39; n = 13);
(3) according to Ho et al. (2018), the presence of nitrate reductase in the
ocean is yet unknown; (4) although large differences in average con­
centrations of VHCl exist depending on the type of sedimentary envi­
ronment (Fig. 2a), these differences are not observed for Vpyr, which
suggests that pyrite does not play a relevant role in V mobility.
Hence, it is very possible that AVS is responsible for the V enrichment
in the OMZ. Previous studies have shown that this element is associated
to a great extent with mackinawite, which has the potential to adsorb
and reduce metals like V (Scheinost and Charlet, 2008). This association
is the result of the incorporation of V(IV) and V(III) into the tetragonal
structure of this mineral (Kunert et al., 2020). Moreover, Vessey (2019)
and Vessey and Lindsay (2020) conducted controlled experiments which
demonstrated that the incorporation of H2VO−4 into mackinawite was
nearly 100%, while V removal by pyrite under the experimental con­
ditions was fairly limited. Although the possibility that greigite could
also contribute to the V enrichments cannot be ruled out, currently there
is no evidence reported in the literature suggesting that V associates to a
great extent with greigite. Therefore, it is quite possible that Fe and Mn
oxyhydroxides transport V to the sediments of the OMZ (mechanism 2),
but that the sedimentary fraction responsible for V enrichment in sedi­
ments is AVS (mechanism 1), with pyrite playing a minor role in V
sequestration. Alternatively, vanadium could precipitate as V(OH)3
through the reduction of V(IV) to V(III) by H2S, which is thermody­
namically capable of reducing V(IV) (Wanty and Goldhaber, 1992). In
this way, the presence of V(OH)3 in OMZ sediments could also increase
the concentration of V in the HCl-extractable fraction given that it is
soluble in acid solutions (Wanty and Goldhaber, 1992; Schweitzer and
Pesterfield, 2010; Wright et al., 2014).
Few AVS measurements have been conducted for sediments under
OMZ influence; however, Goldhaber and Kaplan (1980) reported rela­
tively high concentrations of FeS and H2S in the Carmen Basin, which is
within the OMZ, with values ranging from 0.94 µmol g− 1 to 13 µmol g− 1
and 0.003 mM to 1.78 mM, respectively. Finally, it should be noted that
the results obtained by Vessey (2019) and Vessey and Lindsay (2020)
agree with the results obtained in this study, in which V concentrations
associated with the pyrite fraction were extremely low. Thus, our results
suggest that the predominant process of V transport to OMZ sediments is
represented by the combination of mechanisms (1) and (2), with a
second and much less important path involving mechanism (3).
4.4. Vanadium transport by turbidites
Garcia-Orozco et al. (2022) reported that six (X1-31, X1-33, X2-10,
X2-24, X3-44, and X3-47) of the 40 cores collected in the GoM contained
zones that were either totally or partially influenced by turbiditic events
and widely pyritized, with DOP values ranging from 68 ± 36% to 94.0
± 1.6%. As in the case of Fe, sediments affected by turbiditic events
showed very low VHCl concentrations, with an average of 8 ± 15 nmol
g− 1 (n = 65; Table 2). This value was ~14 times lower than the value of
(1.2 ± 1.5) × 102 nmol g− 1 (n = 720) obtained for the remaining GoM
cores. In the case of the Vpyr fraction, an average value of 8.6 ± 5.4 nmol
g− 1 (n = 79) was obtained, which was statistically similar (P = 0.05) to
any of the average values obtained for the other sedimentary environ­
ments included in this study (Fig. 2b). In this way, the extremely high
degree of trace metal pyritization values (DTMP-V; Equation (2))
observed in the sediment zones influenced by turbidites (37 ± 30% to
97.0 ± 2.3%; Table 2) were a consequence of the low VHCl values, as the
Vpyr concentrations were practically constant (7.2 ± 5.2 nmol g− 1; n =
1098) in all sedimentary environments.
25
Geochimica et Cosmochimica Acta 356 (2023) 14–37
The turbidite results suggest the presence of reducing conditions in
the CE, which have been previously reported for the Florida Escarpment
(FE), which is geologically similar to the CE (Paull et al., 2014; Davis,
2017). Important amounts of pyrite have been reported for the FE (46 ×
102–59 × 102 µmol g− 1; Paull et al., 1984; Commeau et al., 1987) due to
the abundance of H2S (>5.7 mM; Chanton et al., 1991), which is mainly
produced by non-microbial (thermochemical) sulfate reduction (Orr,
1975; Amrani et al., 2019). This sulfate is supplied by the dissolution of
the evaporites present in the FE (e.g., anhydrite; Commeau et al., 1987;
Chanton et al., 1991). On the other hand, the Fe2+ necessary for the
formation of pyrite and AVS would be obtained from the reductive
dissolution of Fe oxyhydroxides (Commeau et al., 1987), which are
abundant in GoM sediments (~110 ± 61 µmol g− 1; Garcia-Orozco et al.,
2022). The high concentrations of dissolved sulfide present in the FE (up
to 5.7 mM; Commeau et al., 1987; Chanton et al., 1991) make Fe oxy­
hydroxides thermodynamically unstable and result in the precipitation
of Fe sulfides in the form of pyrite and AVS. However, the AVS fraction
can dissolve at depth (e.g., Rickard, 2012) or it can eventually transform
to pyrite (Goldhaber and Kaplan, 1980; Commeau et al., 1987), possibly
in the first millimeters of sediment depth if the low sedimentation rates
reported for deep GoM sediments are considered (2.7–24.6 cm ky− 1;
Díaz-Asencio et al., 2019, 2020). Despite these low sedimentation rates,
it has been reported that sediment zones influenced by turbidites could
remain reduced between 2 ky and 15 ky until the diffusion of molecular
oxygen begins to oxidize the pyrite and organic material available in the
turbidite (Buckley and Cranston, 1988).
To quantify the contributions of VHCl, Vpyr, and Vreac caused by tur­
bidites to the deep area of the GoM, two prisms were built (Fig. S10,
Supplementary Data) using the distances between stations X3-47 to X3-
44 (Prism 1) and X3-44 to X2-10 (Prism 2), the depths of the profiles
under turbidite influence (Figs. S5e, c, S4h, Supplementary Data), and
their widths (see Supplementary Data). As it was not possible to obtain
the width of the turbidite located in the CE, the mass transport values of
the different V fractions were calculated by taking into account turbidite
widths of 25 km, 75 km, and 100 km reported for other geographical
areas by Elmore et al. (1979), Yücel et al. (2010) and Kraal et al. (2019),
respectively (Table S1, Supplementary Data). The average concentra­
tions of the different geochemical fractions for prisms 1 and 2 were
calculated based on the concentrations of the sediments affected by the
turbidites from cores X3-47 and X3-44 (Prism 1) and X3-44 and X2-10.
(Prism 2) (yellow symbols in Figs. S4 and S5, values in Tables 4 and S1).
The background values, represented by the average concentrations of all
the samples not affected by turbidites from the entire Gulf of Mexico
(GoM Average in Table 2), were subtracted from the prisms concentra­
tions to calculate their above background concentrations. A detailed
description of the equations and parameters used to calculate the surplus
or deficit of mass contributed by the turbidite can be found in Supple­
mentary Data.
The results showed a deficit of VHCl (mainly associated with Fe/Mn
oxyhydroxides, as AVS is absent in these sediments), which ranged from
− 3.3 Gg to − 13.3 Gg depending on the width considered for the turbi­
dite, while a surplus ranging from 0.043 Gg to 0.17 Gg was obtained for
Vpyr and a deficit of − 3.3 Gg to − 13.2 Gg was obtained for Vreac
(Table 4). The VHCl deficit and Vpyr surplus calculated for these sedi­
mentary deposits were due to the reducing conditions present in the
turbiditic sediments of the CE, as the reactive V in these zones is almost
entirely associated with the pyrite fraction (DTMP-V values ranging
from 37 ± 30% to 97.0 ± 2.3%; Table 2). The organic carbon analysis
conducted by Garcia-Orozco (2019) found no important differences in
their concentrations between the samples of turbiditic deposits and
those of the remaining GoM cores, which indicates that V is not asso­
ciated with organic matter in this case. Finally, these turbiditic events
are of paramount importance for environments with low deposition
rates, such as deep GoM sediments, as a single turbiditic event can
represent between 2.9 and 12 years of Vpyr accumulation due to sedi­
mentary deposition [(1.8 ± 1.1) × 10− 2 Gg y− 1] in the 750,000 km2 of
J. Garcia-Orozco et al. Geochimica et Cosmochimica Acta 356 (2023) 14–37

Table 4
Mass of vanadium associated with the geochemical fractions operationally defined as pyrite (Vpyr), HCl-extractable (VHCl), and reactive (Vreac) transported by a
turbiditic event. Calculations were made assuming turbidite widths (w) of 25 km (Kraal et al., 2019), 75 km (Yücel et al., 2010), and 100 km (Elmore et al., 1979).
Prisms 1 and 2 (Fig. S14) refer to the geometrical volumes built from the turbidite width, the geographical distance from core X3-47 to X3-44 (120 km) and X3-44 to X2-
10 (144 km), respectively, and the heights of the profiles influenced by the turbiditic event in cores X3-47, X3-44, and X2–10. Average concentrations of the oper­
ationally defined fractions were calculated as the average of the turbidite-influenced sediment samples from cores X3-47 and X3-44 (Prism 1) and X3-44 and X2-10
(Prism 2). Positive and negative mass values imply an elemental surplus or deficit, respectively. For an explanation of these assumptions, geometrical volumes, and the
equations involved in the calculations, see the Supplementary Data.
Turbidite width Prism Volume of prism Average concentration (µmol g− 1) Mass of Vpyr Mass of Mass of
(km) number (km3) VHCl Vreac

Vpyr VHCl Vreac (Gg)

− 3
25 1 0.420 (10.0 ± 5.9)×10 (4.3 ± 8.3) × (11.6 ± 7.0) × 0.047 − 2.3 − 2.2
10− 3 10− 3
− 3 3
25 2 0.198 (5.7 ± 2.5) × 10 (3.4 ± 6.6) × (8.8 ± 6.7) × 10− − 0.0042 − 1.1 − 1.1
10− 3
25 1+2 0.618 – – – 0.043 − 3.3 − 3.3

75 1 1.260 (10.0 ± 5.9) × (4.3 ± 8.3) × (11.6 ± 7.0) × 0.14 − 6.8 − 6.7
10− 3 10− 3 10− 3
3 3
75 2 0.594 (5.7 ± 2.5) × 10− (3.4 ± 6.6) × (8.8 ± 6.7) × 10− − 0.013 − 3.2 − 3.2
10− 3
75 1+2 1.854 – – – 0.13 − 10.0 − 9.9

100 1 1.680 (10.0 ± 5.9) × (4.3 ± 8.3) × (11.6 ± 7.0) × 0.19 − 9.1 − 8.9
10− 3 10− 3 10− 3
3 3
100 2 0.792 (5.7 ± 2.5) × 10− (3.4 ± 6.6) × (8.8 ± 6.7) × 10− − 0.017 − 4.3 − 4.3
10− 3
100 1+2 2.472 – – – 0.17 − 13.3 − 13.2

the GoM that were considered. In the case of VHCl, between 6.4 and 26
years of sedimentation would be required to compensate for the deficit
produced by the turbidite. These results illustrate the importance of
turbidites to transport (or impoverish) reduced (Vpyr) or oxidized (VHCl)
vanadium to GoM deep sediments through events that occur over very
short time periods in geological terms.

4.5. Guerrero Negro hypersaline system

A high and significant correlation between VHCl and FeHCl was pre­
sent in the GNHS (r = 0.96; P < 0.001; n = 107; Fig. 4), which suggests
that an association between V and the minerals included in the FeHCl
fraction is present. One possible explanation for this association would
be the presence of Fe oxyhydroxides in this fraction, to which V can be
associated (Breit and Wanty, 1991; Wehrli and Stumm, 1989). However,
the low Fe and Mn oxyhydroxide concentrations reported in this envi­
ronment (20 ± 15 μmol g− 1 and 2.3 ± 5.0 μmol g− 1, respectively;
Reimer, 2011) and the presence of anoxic-sulfidic conditions very close
to the sediment–water interface (Canfield and Des Marais 1991; Jonkers
et al. 2005) suggest that the potential roles of these minerals as entities
of V sequestration may be quite limited. Another possible explanation
may be the presence of high AVS concentrations (1.07 ± 0.57–13.3 ±
5.9 μmol g− 1; Reimer, 2011), presumably including mackinawite, whose
affinity for V has been previously discussed (Ohnemus et al., 2017; Fig. 4. Concentrations of Fe in the HCl-extractable fraction (FeHCl) vs. V con­
Vessey, 2019; Vessey and Lindsay, 2020). Thus, the correlation between centrations in the same fraction (VHCl) of samples collected in the evaporation
VHCl and FeHCl could be the combined result of the affinity of V for AVS ponds of the Guerrero Negro Hypersaline System (F1 a F6). The star-shaped
(presumably including mackinawite) and Fe/Mn oxyhydroxides (to a symbols indicate the samples corresponding to microbial mats (Mat). The
blue line represents the best fit line of the data.
lesser extent) in the oxic zones of microbial sediments and mats (Fig. 4).
The concentrations of VHCl and FeHCl showed no particular trend as
sediment depth increased, with the exception of cores F4 and F5, which with the increase in Vpyr concentrations. This suggests that V was
exhibited subsurface maxima at ~5 cm depth (Fig. S9, Supplementary transferred from the HCl-extractable fraction to the pyrite fraction.
Data). These peaks appear to coincide with the high AVS concentrations The Vpyr concentrations in the GNHS were not significantly different
(e.g., mackinawite) of these depths, at least for F5 in which Huerta-Diaz (P = 0.05) from those of the other sedimentary environments, even
et al. (2011) reported maximum AVS values (12–22 µmol g− 1) between 5 when considering the Vpyr values of the portions influenced by microbial
and 7 cm depth. This provides additional evidence that V is preferen­ mats (F4M, F5M, and F6M; Fig. 2b). Organic matter has been reported to
tially associated with AVS. For the specific cases of cores F1, F2, and F3 include appreciable amounts of V (e.g., Breit and Wanty, 1991; Algeo
(Figs. S9a–c, Supplementary Data), it can be seen that their VHCl con­ and Maynard, 2004). Thus, the concentrations of Vpyr in the microbial
centrations decreased abruptly below 15 cm depth, which coincides mats of the GNHS should be higher than those in the sediments or in the

26
J. Garcia-Orozco et al.
other sedimentary environments included in this study, as metals asso­
ciated with organic matter are also extracted in the pyrite fraction. This
is generally not a problem for sediments with concentrations < 3% by
weight (<2.5 mmol g− 1) of Corg (Huerta-Diaz and Morse, 1990),
although GNHS microbial mats can have values of up to 13% (Huerta-
Diaz et al., 2011; Reimer, 2011). Despite these high Corg values, no
significant differences (P = 0.05) between Vpyr concentrations in mi­
crobial mats and those in GNHS sediments or other modern sedimentary
environments were found (Fig. 2b), which indicates that organic matter
does not play a relevant role as a V sink, as has been suggested in other
studies (e.g., Breit and Wanty, 1991; Algeo and Maynard, 2004).
4.6. Degree of pyritization and degree of V pyritization
The DTMP-V values (Figs. S11–S16, Supplementary Data), as
opposed to the DOP values (Figs. S11 and S16, Supplementary Data),
may be strongly influenced by the relative concentrations of the AVS
fraction (especially mackinawite; Vessey, 2019; Vessey and Lindsay,
2020), and these concentrations may be very different from those of Fe/
Mn oxyhydroxides, to which V is also associated. However, the Vpyr
concentrations will not significantly influence DTMP-V, as these con­
centrations remain essentially constant, at least in all sedimentary en­
vironments considered in our study (see also Vessey, 2019). In this way,
a sedimentary environment with AVS concentrations that are notably
lower or much higher than those of Fe oxyhydroxides will result in low
DTMP-V values (see Eq. (2)). Considering that the primary source of V in
the VHCl fraction is typically from iron oxyhydroxides, while the Vpyr
fraction makes only minor contributions, it follows that low or high
concentrations of AVS-associated HCl-extracted V will lead to low
DTMP-V values. This is because the VHCl term in Eq. (2) will consistently
dominate under such conditions. It is possible that either of these two
cases may be represented by OMZ, anoxic/anoxic-sulfidic, or oxic
sedimentary environments. In the first case, extremely low average
DTMP-V values were obtained (0.98 ± 0.68%; n = 198; Table 2, Fig. 2c),
although their DOP values were high (56 ± 21%; Table 3, Fig. 3c). This
behavior may have been due to the high availability of Corg (2.4 mmol
g− 1 to 4.5 mmol g− 1) and H2S (0.003 mM a 1.78 mM) in this environ­
ment (Goldhaber and Kaplan, 1980), conditions that favor sedimentary
pyrite formation (Berner, 1970; Canfield, 1989). Thus, both AVS and Fe
oxyhydroxides may be important components of the VHCl fraction. For
example, AVS values ranging from 1.11 ± 0.92 µmol g− 1 (McKay et al.,
2007) to 50 ± 29 µmol g− 1 (Goldhaber and Kaplan, 1980) and con­
centrations of Fe oxyhydroxides of 27.3 ± 8.3 µmol g− 1 (McKay et al.,
2007) have been reported for OMZ sediments. These concentrations
could potentially be responsible for the low DTMP-V values obtained in
this study. As such, it is possible that sedimentary environments exist in
which V presents high degrees of sulfidization (i.e., high V content
associated with the AVS fraction) but low DTMP-V values.
In addition to the OMZ, anoxic/anoxic-sulfidic (2.1 ± 1.0%, n = 116;
Table 2; Fig. 2c) and oxic (6 ± 11%, n = 773; Table 2; Fig. 2c) envi­
ronments also exhibited low DTMP-V values that ranged from 1.09 ±
0.42% (SCLB) to 2.85 ± 0.94% (SCB) and 0.058 ± 0.042% (X1-43) to 36
± 20% (X2-2), respectively. As no measured AVS values are available for
these two sedimentary environments, it is not possible to establish which
factor (AVS or Fe/Mn oxyhydroxides) was responsible for the low
DTMP-V values. However, for anoxic-sulfidic sediments, it is generally
accepted that AVS concentrations in the sediments of Southern Cali­
fornia basins are very low when compared to those of Fepyr (<1 × 10− 3
wt% S; Leslie et al., 1990), with average values of 6.5 ± 6.7 µmol g− 1,
19.3 ± 9.3 µmol g− 1, and 0.43 ± 0.16 µmol g− 1 reported for the Santa
Barbara, Santa Monica, and Santa Catalina basins, respectively (Kaplan
et al., 1963). In contrast, the concentrations of Fe oxyhydroxides re­
ported for CCB basins oscillate between 4 µmol g− 1 and 233 ± 36 µmol
g− 1 (Murnane et al., 1989; Leslie et al., 1990; Wang et al., 2019; Burdige
and Komada, 2020), with important concentrations (>60 µmol g− 1)
even in the anoxic-sulfidic portions of the sediment column (Murnane
27
Geochimica et Cosmochimica Acta 356 (2023) 14–37
et al., 1989; Wang et al., 2019; Burdige and Komada, 2020). The low
DTMP-V values (6 ± 11%; Table 2; Fig. 2c) in oxic sediments were
mainly caused by the low AVS (<5 µmol g− 1; Lin and Morse, 1991) and
pyrite (6.6 ± 4.2 nmol g− 1; Table 2) concentrations present due to the
low sedimentation rates (2.7–24.6 cm ky− 1; Díaz-Asencio et al., 2019,
2020) and low Corg content in the GoM (0.67 ± 0.29 mmol g− 1; García
Orozco, 2019) and Patton Escarpment. Therefore, it is reasonable to
assume that V is preferentially associated with Fe oxyhydroxides, which
resulted in the low DTMP-V values obtained in this study.
In contrast to the aforementioned sedimentary environments, the
highest DTMP-V values were found in the GNHS (14 ± 27%; n = 113;
Table 2, Fig. 2c) and in turbiditic deposits (69 ± 32%, n = 79; Fig. 2c,
Table 2). In the GNHS, pyrite concentrations have been found to be low
(0.12 µmol g− 1 to 21 µmol g− 1) because its formation is limited by the
availability of reactive Fe (Huerta-Diaz et al., 2011). It is precisely this
limitation combined with the low values of Fe and Mn oxyhydroxides
(7.4 ± 4.3 µmol g− 1 and 2.3 ± 5.0 µmol g− 1, respectively; Reimer, 2011)
to which V are normally associated that likely resulted in the relatively
high DTMP-V values in the GNHS (Fig. 2c, Table 2). Thus, it is reason­
able to assume that the V in these microbial sediments and mats would
tend to be associated with AVS. Finally, in the case of GoM turbiditic
deposits, the VHCl concentrations were extremely low (1.0 ± 3.0 nmol
g− 1 to 26 ± 28 nmol g− 1, average of 8 ± 15 nmol g− 1; Table 2, Fig. 2a),
indicating that the contributions of Fe oxyhydroxides and AVS were not
important. In turn, this increases the relative importance of pyrite,
which results in high DTMP-V values (Fig. 2c, Table 2).
In summary, the average DTMP-V values increased as determined by
the availability of V in the HCl-extractable fraction as follows (Table 2):
OMZ (0.98 ± 0.68%; n = 198) < anoxic/anoxic-sulfidic sediments (2.1
± 1.0%; n = 116) < oxic sediments (6 ± 11%; n = 773) < GNHS (14 ±
27%; n = 113) < turbiditic deposits (69 ± 32%; n = 79). For Fe, the
average DOP values increased as follows (Table 3): oxic sediments (3.0
± 5.4%; n = 772) < anoxic/anoxic-sulfidic sediments (14 ± 12%; n =
117) < GNHS (29 ± 30%; n = 113) < OMZ (56 ± 21%; n = 198) <
turbiditic deposits (89 ± 20%; n = 62).
4.7. DOP vs. DTMP-V
If the average DOP values are combined with those of DTMP-V for all
sedimentary environments, a linear trend emerges, yet the environments
of the OMZ (and to a lesser extent those of anoxic-sulfidic sediments) do
not follow this trend. In fact, if these last two environments are excluded
from the calculation, a highly significant linear regression is obtained (r
= 0.94; P < 0.001; n = 53; Fig. 5a). Moreover, an analysis of each
sedimentary environment resulted in significant correlations for only
oxic and turbiditic sediments (r = 0.97, P < 0.001, n = 43; Fig. 5b) and
GNHS sediments (r = 0.98; P < 0.001; n = 6; Fig. 5c). It is possible that
the lack of linearity observed for the OMZ and CCB basins is caused by
the non-quantifiable contribution of V associated with AVS, which is
apparently high in these two sedimentary environments (e.g., Goldhaber
and Kaplan, 1980; Leslie et al., 1990), while being very low or absent in
oxic sediments and turbiditic deposits. Finally, the GNHS shows that
when pyrite, AVS, and Fe oxyhydroxide concentrations are similar
(Huerta-Diaz et al., 2011; Reimer, 2011), the possible contributions of V
associated with AVS do not significantly affect the linear trend of the
data (Fig. 5c).
4.8. Fe and V reactive mass accumulation rates
Considering the results obtained, we calculated reactive Fe and V
MARs (i.e., excluding geochemically recalcitrant forms, such as the V
associated with the silicate fraction), as well as their relevance to each of
the sedimentary environments considered in this study.
4.8.1. California Continental Borderland basins
The average carbonate-free MARs in CCB basins, approximated using
J. Garcia-Orozco et al. Geochimica et Cosmochimica Acta 356 (2023) 14–37

Fig. 5. Average degree of pyritization (DOP) vs. the average degree of pyritization of V (DTMP-V) for (a) all cores included in this study, (b) cores from oxic and
turbiditic environments, and (c) the cores from the Guerrero Negro Hypersaline System. The blue lines represent the best fit lines of the data, which for (a) do not
include oxygen minimum zone cores. Abbreviations of cores are defined in Table 1.

Fig. 6. Box and whisker plots of the values of V

content of sedimentary pyrite grouped by the type of
environment or sedimentary deposit: (1) turbidities,
(2) hypersaline, (3) oxic, (4) anoxic/anoxic-sulfidic,
and (5) oxygen minimum zone (OMZ). Non-hatched
and hatched boxes of the hypersaline environment
correspond to sediment (S) and microbial mat (M)
values, respectively. The values of the euxinic basins
were obtained from measurements made directly in
pyrite framboids from sediments collected in the
Black Sea (BLKSea) and in the euxinic (CAR-Euxin),
transitional to oxic (CAR-Trans), and bioturbated oxic
(CAR-Oxic) zones of the Cariaco Basin. Abbreviations
of cores are defined in Table 1.

the values reported by McManus et al. (2006) for the SCB, SPB, and SCLB obtained for the OMZ. However, the MAR of (2.9 ± 3.6) × 102 g m− 2
basins (14 g cm− 2 ky− 1, 29 g cm− 2 ky− 1, and 15 g cm− 2 ky− 1, respec­ ky− 1 obtained for Fepyr was among the lowest in this study, although it
tively) were (22.0 ± 9.9) × 102 g m− 2 ky− 1 and (25 ± 12) × 102 g m− 2 was 195 times higher than the value of (0.0149 ± 0.0095) × 102 g m− 2
ky− 1 for FeHCl and Fereac, respectively, which were similar to those ky− 1 reported for the GoM (Garcia-Orozco et al., 2022; Table 5).

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J. Garcia-Orozco et al. Geochimica et Cosmochimica Acta 356 (2023) 14–37

Table 5 Table 6
Mass accumulation rates (MAR) and average (±1 standard deviation) mass Mass accumulation rates (MAR) and average mass accumulation rates (±1
accumulation rates of Fe in the geochemical fractions operationally defined as standard deviation) of V in the geochemical fractions operationally defined as
HCl-extractable (FeHCl), pyrite (Fepyr), and reactive (Fereac) with and without HCl-extractable (VHCl), pyrite (Vpyr), and reactive (Vreac) with and without
normalization to a carbonate-free basis. The MAR values for the California normalization to a carbonate-free basis. The MAR values for the Gulf of Mexico
Continental Borderline basins and northeastern Pacific Ocean oxygen minimum were calculated based on sedimentation rates reported by Díaz-Asencio et al.
zones were obtained from McManus et al. (2006), while those for the Guerrero (2019, 2020) and our values of dry bulk density (DBD). The MAR values of the
Negro Hypersaline System were calculated from the microbial mat accretion rate California continental borderline basins and northeastern Pacific Ocean oxygen
reported by Des Marais et al. (1992) and our values of dry bulk density. Average minimum zones were obtained from McManus et al. (2006), while those of the
MAR values and mass accumulation rates for the Gulf of Mexico were obtained Guerrero Negro Hypersaline System were calculated from the microbial mat
from Garcia-Orozco et al. (2022). Abbreviations of cores are defined in Table 1. accretion rates reported by Des Marais et al. (1992) and our DBD values. Ab­
Core MAR (g Mass accumulation rate Carbonate-free mass
breviations of cores are defined in Table 1.
cm− 2 (×102) accumulation rate (×102) Core MAR (g Average mass accumulation Average carbonate-free mass
ky− 1) cm− 2 rate accumulation rate
FeHCl Fepyr Fereac FeHCl Fepyr Fereac
ky− 1)
2 VHCl Vpyr Vreac VHCl Vpyr Vreac
(g m− ky− 1) (g m− 2
ky− 1)
2
(g m− ky− 1) (g m− 2
ky− 1)
California continental borderland basins
SCB 14 17.5 2.0 ± 19.6 20.4 2.4 ± 22.8 California Continental Borderland basins
± 3.1 1.7 ± 2.3 ± 3.3 2.1 ± 2.5 SCB 14 1.99 0.056 ± 2.04 2.32 0.066 ± 2.39
SPB 29 33.1 6.2 ± 39.2 35.5 6.6 ± 42.0 ± 0.015 ± ± 0.018 ±
± 5.1 4.4 ± 5.6 ± 5.7 4.6 ± 6.0 0.33 0.33 0.38 0.38
SCLB 15 11.8 0.73 ± 12.6 13.6 0.35 ± 14.4 SPB 29 7.3 0.143 ± 7.5 7.9 0.154 ± 8.1
± 2.4 0.30 ± 2.5 ± 2.8 0.35 ± 3.0 ± 4.5 0.049 ± 4.5 ± 5.0 0.055 ± 5.1
Average 19.3 ± 19.7 2.7 ± 22 ± 22.0 2.9 ± 25 ± SCLB 15 4.8 0.050 ± 4.9 5.6 0.058 ± 5.8
8.4 ± 9.5 3.4 11 ± 9.9 3.6 12 ± 1.7 0.015 ± 1.7 ± 1.9 0.018 ± 1.9
Average 19.3 ± 4.3 0.072 ± 4.4 4.8 0.081 ± 4.9
8.4 ± 3.0 0.045 ± 3.1 ± 3.4 0.048 ± 3.4
Northeastern Pacific Ocean oxygen minimum zone
Northeastern Pacific Ocean oxygen minimum zone
SAB 21 8.3 6.4 ± 14.7 8.6 6.6 ± 15.2
SAB 21 14.7 0.098 ± 14.8 15.2 0.102 ± 15.3
± 5.5 6.0 ± 7.4 ± 5.8 6.1 ± 7.8
± 6.3 0.083 ± 6.3 ± 6.7 0.088 ± 6.7
SL 50 23.9 24 ± 13 48 ± 31.6 32 ± 18 63 ±
SL 50 21 ± 0.153 ± 21 ± 28 ± 0.201 ± 30 ±
± 6.5 11 ± 8.5 15
11 0.064 11 14 0.083 14
Average 36 ± 15.6 15 ± 13 30 ± 19 ± 18 ± 18 38 ±
Average 36 ± 16.2 0.110 ± 16.6 19 ± 0.131 ± 20 ±
20 ± 9.8 19 14 27
21 ± 8.5 0.073 ± 8.5 11 0.089 12
Gulf of Mexico oxic sediments
Gulf of Mexico oxic sediments X3-7* 3.53 ± 0.19 0.013 ± 0.20 0.22 0.0159 0.24
Average 7.0 ± 6.1 0.0113 6.2 ± 8.2 0.0149 8.4 ± 0.33 ± 0.034 ± ± ± ±
3.8 ± 4.7 ± 4.8 ± 6.5 ± 6.6 0.51 0.53 0.11 0.0022 0.10
0.0075 0.0095 X3-38* 4.77 ± 0.44 0.018 ± 0.45 0.51 0.0217 0.53
0.44 ± 0.036 ± ± ± ±
0.85 0.88 0.10 0.0046 0.10
Guerrero Negro Hypersaline System X3-43* 4.15 ± 0.26 0.017 ± 0.27 0.31 0.0208 0.33
F1 87 ± 5.1 1.0 ± 6.2 ± 6.1 1.2 ± 7±
0.38 ± 0.038 ± ± ± ±
59 ± 7.2 1.5 8.2 ± 8.6 1.7 10
0.59 0.61 0.16 0.0046 0.17
F2 97 ± 5.0 1.6 ± 6.8 ± 5.2 1.7 ± 7.2 ± X3-46* 4.46 ± 0.30 0.018 ± 0.31 0.41 0.0214 0.43
49 ± 4.2 2.9 4.9 ± 4.3 2.9 4.8 0.41 ± 0.039 ± ± ± ±
F3 136 ± 34.4 4.6 ± 39.0 35.6 4.8 ± 40 ± 0.65 0.65 0.19 0.0070 0.19
27 ± 8.4 1.5 ± 9.6 ± 8.8 1.5 10 X4-7 12.2 ± 1.71 0.033 ± 1.74 2.44 0.048 ± 2.48
F4 (5.5 ± 35 ± 13.9 ± 49 ± 37 ± 14 ± 10 51 ± 1.2 ± 0.017 ± ± 0.023 ±
2.2) × 32 9.5 39 33 41 0.53 0.17 0.76 0.76
102
X4-14 6.03 ± 0.53 0.028 ± 0.55 0.74 0.039 ± 0.78
F5 (6.0 ± 20 ± 14.5 ± 35 ± 21 ± 15.0 ± 36 ±
0.52 ± 0.012 ± ± 0.018 ±
1.5) × 20 8.6 24 20 9.0 25 0.45 0.48 0.63 0.64
102 X4-31 7.2 ± 0.63 0.0099 0.64 0.73 0.010 ± 0.74
F6 515 ± 37 ± 12.9 ± 50 ± 38 ± 13.3 ± 51 ± 1.2 ± ± ± ± 0.011 ±
85 11 4.3 13 11 4.4 13 0.26 0.0095 0.11 0.25 0.25
Average (3.2 ± 23 ± 8.1 ± 31 ± 24 ± 8.5 ± 32 ± X4-34 15.3 ± 1.9 0.052 ± 1.96 2.3 0.066 ± 2.4
2.5) × 21 8.1 27 22 8.5 28 2.3 ± 1.9 0.031 ± ± 2.6 0.036 ± 2.6
102
0.29
X4-40 6.1 ± 0.50 0.023 ± 0.52 0.58 0.026 ± 0.60
1.1 ± 0.012 ± ± 0.014 ±
For the CCB basins, it is possible that the MAR values of Vreac 0.37 0.92 0.40 0.40
(Table 6) towards this type of sediment may have been greater during X4-47 6.30 ± 1.39 0.029 ± 1.41 1.47 0.031 ± 1.50
the Precambrian (i.e., 2.5–1.0 Ga) when the seas were ferruginous, 0.82 ± 0.012 ± ± 0.012 ±
0.81 0.18 0.86 0.85
especially considering that the formation and deposition of Fe minerals
X5-1 3.62 ± 0.75 0.0040 0.75 0.81 0.0046 0.81
(and quite possibly their associated trace metals) in sediments were 0.67 ± ± ± ± ± ±
favored under these conditions (Canfield et al., 2007, 2008; März et al. 0.20 0.0012 0.13 0.16 0.0013 0.16
2008; Poulton and Canfield, 2011). The reducing conditions in ferru­ X5-5 4.16 ± 0.95 0.0052 0.95 1.19 0.0054 1.19
ginous seas may have promoted the formation and deposition of sig­ 0.46 ± ± ± ± ± ±
0.14 0.0033 0.10 0.12 0.0047 0.13
nificant amounts of AVS in zones with appreciable concentrations of X5-8 4.19 ± 0.24 0.0094 0.25 0.32 0.0101± 0.33
H2S, which produced conditions similar to those that are currently 0.33 ± ± ± ± 0.0081 ±
present in the CCB basins. The existence of V enrichments reported by 0.30 0.0042 0.20 0.39 0.40
Tang et al. (2017) for sediments deposited under ferruginous conditions (continued on next page)
could support this hypothesis. Under anoxic, ferruginous oceanic con­
ditions, concentrations of sulfate were low (<2.5–200 μM; Habicht et al.,

29
J. Garcia-Orozco et al. Geochimica et Cosmochimica Acta 356 (2023) 14–37

Table 6 (continued ) CCB basins (4.8 ± 3.4, 0.081 ± 0.048 g m− 2 ky− 1 and 4.9 ± 3.4 g m− 2
Core MAR (g Average mass accumulation Average carbonate-free mass ky− 1, respectively) and deep sediments of the GoM (0.96 ± 0.75 g m− 2
cm− 2 rate accumulation rate ky− 1, 0.022 ± 0.015 g m− 2 ky− 1 and 0.98 ± 0.76 g m− 2 ky− 1, respec­
ky− 1)
VHCl Vpyr Vreac VHCl Vpyr Vreac
tively), which ranked last (Table 6).
− 2 − 1 − 2 − 1
The annual burial of the different geochemical fractions of Fe and V
(g m ky ) (g m ky )
at the level of all OMZ regions can be approximated considering their
X5-15 10.9 ± 1.65 0.0185 1.67 2.82 0.0193 2.84 area (33.48 × 106 km2; Fuenzalida et al., 2009; Zhou et al., 2022) and
2.3 ± ± ± ± ± ±
the average MARs shown in Tables 5 and 6. For this calculation, we
0.51 0.0083 0.35 0.43 0.0013 0.43
X5-18 2.88 ± 0.19 0.0053 0.20 0.74 0.0056 0.74
assumed that the MAR values reported by McManus et al. (2006) for the
0.47 ± ± ± ± two stations in the OMZ of the Mexican margin (21 and 50 g cm− 2 ky− 1;
0.12 0.32 0.45 0.46 Table 6) and the MARs of the different geochemical fractions of V were
X5-22 3.98 ± 0.32 0.0167 0.34 0.42 0.022 ± 0.43 representative of all OMZ regions worldwide. It is likely that these as­
0.51 0.012
sumptions are not entirely valid; however, this approximation may offer
± ± ± ± ±
0.36 0.0068 0.43 0.48 0.48
X5-28 3.87 ± 0.47 0.0128 0.47 0.57 0.0155 0.59 an idea of the relative importance of different sedimentary environ­
0.86 ± ± ± ± ± ± ments as Vreac sinks. This analysis can estimate the approximate order of
0.14 0.0043 0.10 0.12 0.0044 0.12 magnitude of reactive V MARs within global OMZs. Furthermore, due to
X5-44 12.0 ± 1.19 0.030 1.21 1.36 0.039 ± 1.38 the constancy in Vpyr concentration, it provides a higher level of preci­
2.3 ± ±0.010 ± ± 0.017 ±
0.66 0.23 0.71 0.71
sion in MAR estimation for this specific fraction compared to the other
X6-12 4.64 ± 0.31 0.0090 0.33 0.34 0.0110 0.35 geochemical fractions. The resulting approximation suggests that on a
0.59 ± ± ± ± ± ± carbonate-free basis (64 ± 47) × 103 Gg of FeHCl, (60 ± 60) × 103 Gg of
0.70 0.0038 0.42 0.10 0.0051 0.10 Fepyr, and (127 ± 90) × 103 Gg of Fereac are deposited annually in OMZ
X6-26 13.2 ± 1.41 0.031 ± 1.45 1.45 0.039 ± 1.36
sediments (Table 7). Our results suggest that the two areas that
2.0 ± 0.013 ± ± 0.014 ±
0.47 0.21 0.48 0.44 contribute the highest percentages to the deposition of Fereac are those
X6-27 11.0 ± 0.45 0.0344 0.49 0.50 0.039 ± 0.54 located in the North Pacific (31%) and Equatorial Pacific (36%). The
2.1 ± ± ± ± 0.013 ± OMZ located in the South Pacific also represents a major sink (17%),
0.35 0.0094 0.92 0.39 0.39 although it is considerably less important than those in the North Pacific
X6-33 5.6 ± 0.17 0.0159 0.20 0.18 0.0170 0.20
1.2 ± ± ± ± ± ±
and Equatorial Pacific. For V, the average annual carbonate-free MARs
0.14 0.0094 0.43 0.13 0.0096 0.14 to the OMZ were (6.4 ± 3.7) × 102 Gg of VHCl, 4.4 ± 3.0 Gg of Vpyr, and
X6-48 11.6 ± 1.62 0.031 ± 1.65 1.65 0.034 ± 1.67 (6.7 ± 4.0) × 102 Gg of Vreac (Table 8), with the last fraction constituting
1.9 ± 0.011 ± ± 0.027 ± ~46% of the global MAR of total vanadium (VT; 1460 Gg y− 1) to the
0.63 0.27 0.57 0.58
sediments (Schlesinger et al., 2017). In a manner similar to that of Fe,
Average 7.0 ± 0.69 0.017 ± 0.71 0.96 0.022 ± 0.98
3.8 ± 0.011 ± ± 0.015 ± the North Pacific (31%) and Equatorial Pacific (36%) exhibited the
0.52 0.53 0.75 0.76 highest deposition values of Vreac.
Guerrero Negro Hypersaline System Overall, the MAR of the reactive fraction is particularly significant
F1 87 ± 8.9 0.35 ± 9.3 10 ± 0.40 ± 10 ± concerning the global fluxes of V, considering the constant and inten­
59 ± 2.1 0.49 ± 1.4 14 0.59 17
F2 97 ± 6.5 0.49 ± 7.0 6.9 0.50 ± 7.7
sified growth of global OMZs since the 1960s due to the increase in
49 ± 4.1 0.89 ± 4.0 ± 4.0 0.91 ± 4.1 ocean temperatures (Stramma et al., 2008; Ito and Deutsch, 2013; Zhou
F3 136 ± 61 ± 0.54 ± 62 ± 63 ± 0.55 ± 64 ± et al., 2022). Zhou et al. (2022) used climate models to estimate that
27 25 0.17 25 25 0.18 27 OMZ areas in the Pacific and Atlantic oceans with dissolved oxygen
F4 (5.5 ± 51 ± 3.2 ± 55 ± 54 ± 3.4 ± 58 ±
concentrations < 20 µmol kg− 1 (OMZ20) and < 60 µmol kg− 1 (OMZ60)
2.2) × 50 1.9 49 53 1.9 53
102 have increased 60–359% and 36–146% from 1960 to 2019, respectively,
F5 (6.0 ± 35 ± 6.2 ± 42 ± 36 ± 6.4 ± 43 ± solely due to increases in temperature. These increases in OMZ areas
1.5) × 43 5.4 42 44 5.6 44 thus involve greater MARs of V and Fe, which can be approximated
102 based on the MAR values shown in Tables 5 and 6 and the data published
F6 515 ± 38 ± 2.4 ± 40 ± 39 ± 2.5 ± 42 ±
85 15 2.1 16 15 2.2 17
by Zhou et al. (2022). These authors estimated that for the Global Ocean,
Average (3.2 ± 30 ± 2.0 ± 33 ± 32 ± 2.0 ± 35 ± the rate of increase of all OMZ20s is (21.5 ± 5.3) × 104 km2 y− 1. Ac­
2.5) × 32 2.9 33 34 3.0 35 cording to this information and the combined areas of all OMZ20 zones
for 2019 (33.48 × 106 km2; Tables 7 and 8) reported by Zhou et al.
2
10
(2022) and Fuenzalida et al. (2009), it is possible to calculate that the
global increase in OMZ20 areas from 1960 to 2019 was ~61%. This
2002; Crowe et al., 2008; Bauer et al., 2022). Although anoxic condi­
percentage suggests that compared to 1960, in 2019 these OMZs buried
tions and Fe2+-enrichment can promote the formation of FeS and FeS2
an additional (carbonate-free value in parenthesis) 14 × 103 Gg y− 1 (18
(Canfield et al., 2008), prevailing low sulfate concentrations limited the
× 103 Gg y− 1), 20 × 103 Gg y− 1 (24 × 103 Gg y− 1), and 34 × 103 Gg y− 1
production of H2S, which in turn limited the conversion of FeS to FeS2 (e.
(43 × 103 Gg y− 1) of FeHCl, Fepyr, and Fereac, respectively, and an
g., Boesen and Postma, 1988; Crowe et al., 2008; Boyko et al., 2021).
additional 2.1 × 102 Gg y− 1 (2.5 × 102 Gg y− 1), 2.0 Gg y− 1 (2.4 Gg y− 1),
and 2.1 × 102 Gg y− 1 (2.5 × 102 Gg y− 1) of VHCl, Vpyr, and Vreac,
4.8.2. Oxygen minimum zone
respectively. These results suggest that the aforementioned increase in
The high average carbonate-free MARs of Fepyr and Fereac in the OMZ
area substantially modified the overall MAR of Fe and V to OMZ sedi­
[(18 ± 18) × 102 g m− 2 ky− 1 and (38 ± 27) × 102 g m− 2 ky− 1,
ments, although this last MAR value does not substantially affect con­
respectively, Table 5] were caused by the high average concentrations of
centrations of V in sea water (29.8–37.4 nmol kg− 1; Wang and Sañudo
these two geochemical fractions, which were the highest of all sedi­
Wilhelmy, 2009; Smrzka et al., 2019), as this is equivalent to an annual
mentary environments considered in this study (Fig. 3b, Table 3). In the
loss of 0.010% to 0.012% of dissolved V in the oceans. Furthermore,
case of the OMZ, the magnitude of carbonate-free MAR values of VHCl,
depletion of dissolved V in the water column of oxygen minimum zones
Vpyr, and Vreac ranked second, with average values of 19 ± 11 g m− 2
is highly improbable, since they exhibit high rates of water renewal (e.
ky− 1, 0.131 ± 0.089 g m− 2 ky–1, and 20 ± 12 g m− 2 ky− 1, respectively
g., Emerson and Huested, 1991; Scholz et al., 2017; Bennett and Can­
(Table 6). These values were much higher than those obtained for the
field, 2020), thereby ensuring a continuous supply of dissolved V.

30
J. Garcia-Orozco et al. Geochimica et Cosmochimica Acta 356 (2023) 14–37

Table 7
Average annual mass accumulation rates (±1 standard deviation) of Fe of the geochemical fractions operationally defined as HCl-extractable (FeHCl), pyrite (Fepyr), and
reactive (Fereac) with and without normalization to a carbonate-free basis. The areas of the oxygen minimum zones (OMZ; dissolved oxygen < 0.20 µmol kg− 1) were
obtained from Zhou et al. (2022), with the exception of that of the South Pacific, which was obtained from Fuenzalida et al. (2009). The areas of the evaporation ponds
of the Guerrero Negro Hypersaline System were obtained from Valdivieso-Ojeda et al. (2014). The annual mass accumulation rates of Fe in the operationally defined
fractions of FeHCl, Fepyr, and Fereac in the different OMZs were approximated from the average Fe mass accumulation rates calculated in this study for the OMZ. The
mass accumulation rates of FeHCl, Fepyr, and Fereac in the Gulf of Mexico (GoM) were obtained from Garcia-Orozco et al. (2022).
Location Area (km2) Average mass accumulation rate Average carbonate-free mass accumulation rate

FeHCl Fepyr Fereac FeHCl Fepyr Fereac

Oxygen minimum zone (×103 Gg y–1)

Arabian Sea 2.30 × 106 3.6 ± 2.3 3.5 ± 3.0 6.9 ± 4.4 4.4 ± 3.2 4.1 ± 4.1 8.7 ± 6.2
Bay of Bengal 1.85 × 106 2.9 ± 1.8 2.8 ± 2.4 5.6 ± 3.5 3.5 ± 2.6 3.3 ± 3.3 7.0 ± 5.0
South Indian 0.020 × 106 0.031 ± 0.020 0.030 ± 0.026 0.060 ± 0.038 0.038 ± 0.028 0.036 ± 0.036 0.076 ± 0.054
North Atlantic 0.040 × 106 0.062 ± 0.039 0.060 ± 0.052 0.120 ± 0.076 0.076 ± 0.056 0.072 ± 0.072 0.15 ± 0.11
Equatorial Atlantic 1.02 × 106 1.6 ± 1.0 1.5 ± 1.3 3.1 ± 1.9 1.9 ± 1.4 1.8 ± 1.8 3.9 ± 2.8
South Atlantic 0.17 × 106 0.27 ± 0.17 0.26 ± 0.22 0.51 ± 0.32 0.32 ± 0.24 0.31 ± 0.31 0.65 ± 0.46
North Pacific 10.22 × 106 16 ± 10 15 ± 13 31 ± 19 19 ± 14 18 ± 18 39 ± 28
Equatorial Pacific 12.05 × 106 19 ± 12 18 ± 16 36 ± 23 23 ± 17 22 ± 22 46 ± 33
South Pacific 5.81 × 106 9.1 ± 5.7 8.7 ± 7.6 17 ± 11 11.0 ± 8.1 11 ± 11 22 ± 15
Total or average 33.48 × 106 52 ± 33 50 ± 44 100 ± 64 64 ± 47 60 ± 60 127 ± 90

Gulf of Mexico oxic sediments (×102 Gg y–1)

Gulf of Mexico 0.75 × 106 2.6 ± 2.0 0.047 ± 0.031 2.6 ± 2.0 3.5 ± 2.7 0.062 ± 0.040 3.5 ± 2.8

Guerrero Negro Hypersaline System (×10–2 Gg y–1)

Pond 1 19 0.98 ± 1.38 0.19 ± 0.28 1.1 ± 1.6 1.2 ± 1.7 0.23 ± 0.34 1.4 ± 1.9
Pond 2 7.9 0.39 ± 0.33 0.12 ± 0.22 0.54 ± 0.38 0.41 ± 0.34 0.13 ± 0.23 0.57 ± 0.38
Pond 3 9.7 3.30 ± 0.81 0.45 ± 0.14 3.8 ± 0.92 3.45 ± 0.85 0.47 ± 0.15 3.92 ± 0.97
Pond 4 22 7.4 ± 6.8 2.9 ± 2.0 10 ± 8.3 7.9 ± 7.3 3.2 ± 2.2 11.1 ± 8.8
Pond 5 24 4.8 ± 4.7 3.4 ± 2.0 8.3 ± 5.7 5.0 ± 4.9 3.6 ± 2.2 8.6 ± 5.9
Pond 6 26 9.7 ± 2.8 3.3 ± 1.1 13 ± 3.4 10.0 ± 2.9 3.5 ± 1.2 13.5 ± 3.5
Total or average 109 24 ± 23 8.8 ± 8.7 34 ± 29 26 ± 24 9.2 ± 9.2 35 ± 31

4.8.3. Deep sediments of the Gulf of Mexico
The data reported by Garcia-Orozco et al. (2022) indicate that the
lowest carbonate-free Fe MARs for all geochemical fractions correspond
to the oxic sediments of the GoM, with values of (8.2 ± 6.5) × 102 g m− 2
ky− 1, (0.0149 ± 0.0095) × 102 g m− 2 ky− 1, and (8.4 ± 6.6) × 102 g m− 2
ky− 1 for FeHCl, Fepyr, and Fereac, respectively (Table 5). These results are
reasonable considering the low sedimentation rates of deep GoM sedi­
ments (4.2 ± 0.5 cm ky− 1 to 24.6 ± 4.2 cm ky− 1; Díaz-Asencio et al.,
2019, 2020) and in the case of Fepyr, its low concentrations in these
sediments (0.117 ± 0.088 µmol g− 1 to 2.4 ± 1.9 µmol g− 1; Garcia-
Orozco et al., 2022).
Garcia-Orozco et al. (2022) reported an average annual carbonate-
free MAR of Fereac of (3.5 ± 2.8) × 102 Gg for deep GoM sediments,
which is ~346 times lower than what was calculated for all OMZ regions
(Table 7). This large difference is mainly due to the fact that despite its
considerable extension (0.75 × 106 km2; Table 7), this area exhibits
average MAR (7.0 ± 3.8 g cm− 2 ky− 1; Table 6) and Fereac (81 ± 43 µmol
g− 1; Garcia-Orozco et al., 2022) values that are considerably lower than
those of the OMZ, which exhibits MAR values of 21 g cm− 2 ky− 1 to 50 g
cm− 2 ky− 1 (McManus et al., 2006) and average Fereac concentrations of
110 ± 50 µmol g− 1 (Table 3). In addition, the OMZ region covers a larger
area (33.48 × 106 km2; Table 7) than the one covered by the deep
sediments of the GoM. Thus, annual carbonate-free MAR values
(Table 8) of VHCl (0.72 ± 0.57 Gg), Vpyr (0.018 ± 0.011 Gg), and Vreac
(0.74 ± 0.57 Gg) for the GoM represent 0.05% of global MARs, which
represents a negligible fraction of the VT MAR (1460 Gg y− 1; Schlesinger
et al., 2017).
It is possible to approximate the average MAR of VT in GoM sedi­
ments using its average MAR value of 7.0 ± 3.8 g cm− 2 ky− 1 (Table 6)
and the VT concentrations reported for its continental shelf (2.53 μmol
g− 1; Hope, 2008), its continental margin (2.7 ± 1.1 μmol g− 1; Bennett
and Canfield, 2020), or the average value of 2.35 μmol g− 1 for pelagic
clay reported by Turekian and Wedepohl (1961). This last value was
used in this study, as it is the one that best represents the type of sedi­
ments collected in the GoM, in addition to being similar to the other two
values considered. In this way, it was possible to calculate that the
average accumulation rate of VT for the GoM was 8.4 ± 4.5 g m− 2 ky− 1,
so it can be inferred that the average MAR values of carbonate-free Vreac
and Vpyr (0.98 ± 0.76 g m− 2 ky− 1 and 0.022 ± 0.015 g m− 2 ky− 1,
respectively; Table 6) represent 12% and 0.26% of VT burial, respec­
tively. However, it is important to consider that although the Vreac
contribution was relatively low, this fraction is one of the most impor­
tant from a diagenetic point of view.
To estimate annual MARs of V to deep sediments (i.e., >1000 m
water depth) at the global level for the most geochemically reactive
fractions, as well as VT, we used the sediment flux values of 1100 Tg y− 1,
1500 ± 500 Tg y− 1, and 2800 Tg y− 1 reported by Martin and Windom
(1991), Raiswell (2006), and Hay (1994), respectively. By extrapolating
the average concentrations of the geochemical fractions obtained for the
34 cores collected in the GoM to all deep sediments, the annual MARs at
the global level were estimated to be 15 Gg y− 1, 20 ± 11 Gg y− 1, or 38
Gg y− 1 for VHCl; 0.39 Gg y− 1, 0.53 ± 0.22 Gg y− 1, or 0.98 Gg y− 1 for Vpyr;
and 15 Gg y− 1, 21 ± 11 Gg y− 1, or 39 Gg y− 1 for Vreac. These results
suggest that deep GoM sediments could represent between 1.7 and 4.3%
of the global deposition of Vreac. For the special case of VT, the average
concentration of this element for deep sediment clays (2.35 μmol g− 1;
Turekian and Wedepohl, 1961) was used again to calculate that 142 Gg
y− 1 to 363 Gg y− 1 of VT are deposited in deep sediments globally. This
value is equivalent to 9.7 to 24.8% of the 1460 Gg y− 1 that is deposited
in all oceanic sediments (Schlesinger et al., 2017). The MAR of 363 Gg
y− 1 of VT is a bit high and implies that the value reported by Hay (1994)
was possibly overestimated.
4.8.4. Guerrero Negro Hypersaline System (GNHS)
The Fereac, FeHCl, and Fepyr MAR values of the GNHS were calculated
based on the accretion rate of 0.45 cm y− 1 reported by Des Marais et al.
(1992) for the microbial mats in this area, which was considered
equivalent to the sedimentation rates of the ponds free of microbial
mats. This assumption is reasonable considering that microbial mats
compensate sediment accumulation on their surfaces with growth (Des

31
J. Garcia-Orozco et al. Geochimica et Cosmochimica Acta 356 (2023) 14–37

Table 8 Marais et al., 1992; Hawes et al, 2019).

Average annual mass accumulation rates (±1 standard deviation) of V of the The average carbonate-free MAR values of Fereac and FeHCl calcu­
geochemical fractions operationally defined as HCl-extractable (VHCl), pyrite lated for the GNHS were the largest of all sedimentary environments
(Vpyr), and reactive (Vreac) with and without normalization to a carbonate-free considered in this study, with average values of (32 ± 28) × 102 g m− 2
basis. The areas of the oxygen minimum zones (OMZs; dissolved oxygen < ky− 1 and (24 ± 22) × 102 g m− 2 ky− 1, respectively (Table 5). The MAR
0.20 µmol kg− 1) were obtained from Zhou et al. (2022), with the exception of
of (8.5 ± 8.5) × 102 g m− 2 ky− 1 of Fepyr, although important, was not
that of the South Pacific, which was obtained from Fuenzalida et al. (2009). The
the highest obtained in this study given that the OMZ showed a value of
areas of the evaporation ponds of the Guerrero Negro Hypersaline System were
obtained from Valdivieso-Ojeda et al. (2014). The annual mass accumulation (18 ± 18) × 102 g m− 2 ky− 1 (Table 5).
rates of V of the geochemical fractions of VHCl, Vpyr, and Vreac in the different Similar to the case of Fe, the highest average carbonate-free MARs of
OMZs were approximated from the average V mass accumulation rates calcu­ VHCl, Vreac, and Vpyr were present in the GNHS, with values of 32 ± 34 g
lated in this study. m− 2 ky− 1, 35 ± 35 g m− 2 ky− 1, and 2.0 ± 3.0 g m− 2 ky− 1, respectively
Location Area Average annual mass Average annual carbonate-
(Table 6). The results of Vpyr MARs were particularly interesting given
(km2) accumulation rate free mass accumulation that they were ~15 times higher than those calculated for the OMZ,
rate which ranked second in magnitude after the GNHS (Table 6). The high
VHCl Vpyr Vreac VHCl Vpyr Vreac productivity of the GNHS and the high accretion rate (sedimentation
rate) of the evaporation ponds, especially in the presence of microbial
Oxygen minimum zone (Gg y–1)
Arabian 2.30 37 ± 0.25 ± 38 ± 44 ± 0.30 ± 46 ±
mats (Canfield and Des Marais, 1991; Jonkers et al., 2005), are
Sea × 106 20 0.17 20 25 0.20 28 responsible for the high MAR values of Fe and V in the GNHS.
Bay of 1.85 30 ± 0.20 ± 31 ± 35 ± 0.24 ± 37 ± For the GNHS, (35 ± 31) × 10− 2 Gg of carbonate-free Fereac (Table 7)
and (38 ± 38) × 10− 4 Gg of carbonate-free Vreac are deposited annually
6
Bengal × 10 16 0.14 16 20 0.16 22
South 0.020 0.32 0.0022 0.33 0.38 0.0026 0.40
6 (Table 8), which are negligible values when compared to those calcu­
Indian × 10 ± ± ± ± ± ±
0.17 0.0015 0.17 0.22 0.0018 0.24 lated for the OMZ and GoM. The low values obtained for the GNHS are
North 0.040 0.65 0.0044 0.66 0.76 0.0052 0.80 due to the small, combined area of its evaporation ponds (109 km2;
Atlantic × 106 ± ± ± ± ± ± Table 7) when compared to those of the other sedimentary environments
0.34 0.0029 0.34 0.44 0.0036 0.48
considered in this study. However, it is important to consider that hy­
Equatorial 1.02 16.5 0.112 16.9 19 ± 0.134 20 ±
Atlantic × 10 6
± 8.7 ± 0.074 ± 8.7 11 ± 0.091 12
persaline areas were much more extensive in the geological past than
South 0.17 2.8 0.019 2.8 3.2 0.022 3.4 they are today. For example, 116 Ma ago during the Early Cretaceous, an
Atlantic × 106 ± 1.4 ± 0.012 ± 1.4 ± 1.9 ± 0.015 ± 2.0 evaporation basin was formed between Africa and South America with
North 10.22 166 1.12 ± 170 (1.9 1.34 ± (2.0 an area covering ~106 km2 (Wortmann and Chernyavsky, 2007).
Pacific × 106 ± 87 0.75 ± 87 0.91
Assuming that the sources or inputs of V and Fe, along with the annual
± ±
1.1) 1.2)
× × MARs of Fereac and Vreac, were comparable to those presently calculated
102 102 for the GNHS (although this assumption may be unlikely), an estimation
Equatorial 12.05 (2.0 1.33 ± (2.0 (2.3 1.6 ± (2.4 of the MARs for this basin would be approximately (33 ± 28) × 102 Gg
Pacific × 106 0.88 1.1
± ± ± ±
y− 1 and 35 ± 35 Gg y− 1, respectively. The first value is more than ten
1.0) 1.0) 1.3) 1.5)
× × × ×
times the current value of Fereac deposition in GoM sediments while the
102 102 102 102 second would have represented ~2.4% of the VT deposited globally.
South 5.81 94 ± 0.64 ± 96 ± 110 0.76 ± 116
Pacific × 106 49 0.2 49 ± 64 0.52 ± 70 4.9. Global mass accumulation rates of Vpyr
Total or 33.48 (5.4 3.7 ± (5.6 (6.4 4.4 ± (6.7
average × 106 ± 2.4 ± ± 3.0 ±
2.9) 2.9) 3.7) 4.0) Considering that Vpyr concentrations remain relatively constant
× × × × regardless of the sedimentary environment, as demonstrated in this
102 102 102 102 study, it is possible to establish the average annual MAR of Vpyr to all
oceanic sediments. It is important to clarify that for Fepyr, FeHCl, and
Gulf of Mexico oxic sediments (Gg y–1) VHCl, this calculation cannot be made given that their concentrations
Gulf of 0.75 0.52 0.0132 0.54 0.72 0.018 0.74 vary according to the sedimentary environment in which they are
Mexico × 106 ± 0.011
deposited. If we use our global average Vpyr concentration (7.2 ± 5.2
± ± ± ± ±
0.39 0.0084 0.40 0.57 0.57
nmol g− 1; n = 1098) and the sediment inputs to the oceans on a global
scale (11.3 × 1015 g y− 1; Rea and Ruff, 1996; Schlesinger et al., 2017),
Guerrero Negro Hypersaline System (×10–4 Gg y–1)
Pond 1 19 1.6 0.061 1.6 1.8 0.071 1.9
then it is possible to calculate that the annual MAR value of Vpyr
± 2.2 ± 0.087 ± 2.5 ± 2.6 ± 0.10 ± 3.0 throughout all oceanic sediments is 4.2 ± 3.0 Gg y− 1. Although this
Pond 2 7.9 0.47 0.035 0.53 0.49 0.036 0.56 value is high, it represents only 0.29% of the global average VT MAR
± ± 0.065 ± ± ± 0.066 ± (1460 Gg y− 1; Schlesinger et al., 2017), which implies that sedimentary
0.29 0.29 0.29 0.29
pyrite is not the main V sink at the global level.
Pond 3 9.7 5.4 0.047 5.5 5.6 0.049 5.7
± 2.2 ± 0.015 ± 2.3 ± 2.3 ± 0.016 ± 2.4
Pond 4 22 10.1 0.63 ± 10.7 11 ± 0.67 ± 11 ± 4.10. Vanadium content of sedimentary pyrite: A potential new
± 9.8 0.36 ± 9.8 10 0.39 10 paleoredox proxy?
Pond 5 24 7.8 1.4 ± 9.1 8.1 1.4 ± 9.5
± 9.4 1.2 ± 9.3 ± 9.8 1.2 ± 9.7
Pond 6 26 9.1 0.56 ± 9.7 9.4 0.59 ± 9.9
Trace metal concentrations in framboid pyrites have been used as
± 3.6 0.50 ± 3.9 ± 3.7 0.52 ± 3.9 proxies of seawater concentrations at the time of framboid formation (e.
Total or 109 33 ± 2.2 ± 36 ± 35 ± 2.3 ± 38 ± g., Large et al., 2009; Parnell et al., 2018; Mukherjee et al., 2019;
average 35 3.2 36 37 3.3 38 Gregory et al., 2017). At this point it is important to remember that the
Vpyr value is the amount of V associated with the pyrite fraction per mass
unit of sediment, whereas the V content of sedimentary pyrite represents
the amount of V associated with pyrite per mass of FeS2. The results
obtained from the V content in sedimentary pyrite in the environments
evaluated in this study suggest that these concentrations could also be

32
J. Garcia-Orozco et al.
used as proxies of paleoredox conditions. The V content in sedimentary
pyrite can be calculated using the concentrations of Vpyr and Fepyr ob­
tained in this study and that of Fepyr in the GoM reported by Garcia-
Orozco et al. (2022). The results of this exercise show that the envi­
ronments can be separated into three groups: (1) anoxic/anoxic-sulfidic
sediments; (2) sediments influenced by the OMZ; and (3) oxic sediments,
turbidites, and the GNHS (Fig. 6). These results agree with the V values
obtained via LA-ICPMS analysis of sedimentary pyrite framboids of the
Black Sea and Cariaco Basin (Gregory et al., 2022a, b). All Black Sea
samples were deposited under euxinic conditions while Cariaco basin
samples were deposited either under euxinic conditions or under oxic
conditions that were later overprinted by diffusion of H2S after euxinic
conditions were established in the basin (Lyons et al., 2003). These
reducing environments are relatively similar to groups (1) and (2). These
results (Fig. 6) suggest that the Vpyr concentrations obtained using the
sequential chemical extraction of Huerta-Diaz and Morse (1990) could
be comparable to those obtained directly from pyrite framboids by Laser
Ablation-Inductively Coupled Plasma Mass Spectrometry (e.g., Large
et al., 2009; Parnell et al., 2018; Mukherjee et al., 2019; Gregory et al.,
2022a,b). It is possible that the use of V content in sedimentary pyrite as
a proxy of paleoredox conditions could be substantially improved if used
in combination with the contents of other redox-sensitive elements such
as U or Mo. Additionally, the differences in V content in pyrite (Fig. 6)
could explain the constancy of the Vpyr concentrations in this study (7.2
± 5.2 nmol g− 1; Fig. 2b), as the environments with the highest V content
in pyrite were also those with the lowest concentrations of Fepyr (e.g.,
oxic environments), while those with the lowest V content exhibited the
highest concentrations of Fepyr (e.g., anoxic/anoxic-sulfidic and OMZ;
Fig. 3b).
Another interesting aspect that was reported by Rickard (2012) is
that the contents of trace elements (As, Cd, Co, Cr, Cu, Hg, Mn, Mo, Ni,
Pb, and Zn) in sedimentary pyrite for the GoM shelf and slope obtained
by Huerta-Diaz and Morse (1992) decreased as sediment depth
increased. This behavior was also observed for V, although it occurred
only in the sedimentary environments of the OMZ, CCB basins, Todos
Santos Bay Canyon, GNHS core F3, and in 12 (36%; X1-36, X1-40, X4-
34, X4-40, X4-45, X4-47, X5-11, X5-15, X5-22, X5-44, X6-48, and
METOX2) of the 36 oxic sediment cores for which it was possible to
partially or completely establish these profiles (Figs. S17–S19). These
results, along with findings from other trace elements studies (e.g.,
Rickard, 2012), suggest that the pyrite formed in the uppermost layer of
the sediment has the highest content of V (and other trace elements),
while the subsequently formed pyrite approaches the composition of
pure mineral FeS2, as observed in the deepest sections of cores SL3, SAB,
SCB, SPB, and METOX1. The mechanism or mechanisms involved in this
process remain unknown, although nucleation, pyrite growth (Rickard,
2012), and framboid recrystallization to euhedra (Sawlowicz, 1993)
have been proposed as possible processes. Trace element depletion of
pyrite is not a reasonable mechanism, as the low values of DTMP-V
obtained (0.33 ± 0.25%–36 ± 20%, excluding the turbiditic deposits)
indicate the presence of abundant available concentrations of reactive V.
It is interesting to note that V content in pyrite generally does not
decrease and may even increase with sediment depth as can be observed
in GoM, PE, and GNHS sediments. This behavior appears to support the
hypothesis of trace element depletion resulting from newly nucleated
pyrite, pyrite growth, and framboid recrystallization to euhedra (Ost­
wald and England, 1979; Sawlowicz, 1993; Merinero et al., 2008;
Rickard, 2012; Soliman and El Goresy, 2012; Zhao et al., 2018; Chang
et al., 2022). The low FeHCl concentrations in the GNHS and of organic
matter in the GoM and PE may tend to limit the nucleation, growth, or
recrystallization of this mineral. In contrast, in sedimentary environ­
ments where pyrite formation is not limited (except due to sulfate
depletion in the deeper parts of the sediment), the conditions favoring
newly nucleated pyrite, pyrite growth, or recrystallization processes
would also favor trace element depletion as the sediment depth
increases.
33
Geochimica et Cosmochimica Acta 356 (2023) 14–37
5. Conclusions
The concentrations and MARs of reactive vanadium (Vreac) were
determined, including those associated with diagenetic pyrite, in five
different sedimentary environments. Our results indicate that the V
incorporated in sediments in association with diagenetic pyrite (Vpyr)
does not represent a significant reservoir of reactive V and, unlike VHCl,
its concentration remains relatively constant (7.2 ± 5.2 nmol g− 1)
regardless of the redox state of the depositional environment. This
feature was advantageously used to estimate that the MAR of Vpyr to
oceanic sediments on a global scale is 4.2 ± 3.0 Gg y− 1, which represents
a very small percentage (0.29%) of the average global MAR of VT.
The constancy of Vpyr concentrations implies that the variability in
DTMP-V values is fundamentally a function of the V concentration in the
geochemical VHCl fraction, in which it is associated with Fe/Mn oxy­
hydroxides and, quite possibly, to AVS. This could be the reason why
environments influenced by OMZs and anoxic-sulfidic sediments (e.g.,
CCB basins) are the main sinks of reactive V. The affinity of V for Fe/Mn
oxyhydroxides and AVS (and especially mackinawite) could explain the
enrichments observed in this study in the VHCl fractions of the sedi­
mentary cores of the OMZ, whose (4.1 ± 2.3) × 102 nmol g− 1 average
concentration was ~57 times greater than that of Vpyr (7.2 ± 2.4 nmol
g− 1). These results have important implications for the use of V as a
proxy for paleoredox conditions in sedimentary environments as well as
for calculations of its reactive MAR values on a global scale. In addition,
the effects of global change that affect the extent of OMZs intensified the
V and Fe MARs towards these areas, which in turn increased their
importance as reservoirs for both elements and modified their global
fluxes to the sediments.
The average MAR of carbonate-free Vreac of the GNHS (35 ± 35 g
m− 2 ky− 1) was the highest followed by that of the OMZ (20 ± 12 g m− 2
ky− 1); however, due to the small spatial area of hypersaline environ­
ments at present, their importance at the global level is quite small.
Nonetheless, during the Early Cretaceous (~145–100 My) and especially
during the Permian (~300–252 My), extensive hypersaline areas were
present (Warren, 2006; Ziegler et al., 2003) that may have notably
increased the flux of reactive Fe and V to these areas. For the specific
case of Vreac, the MAR values calculated for the GNHS (30 ± 32 g m− 2
ky− 1) in this study were approximately 1.9 times higher than those
obtained for OMZs (16.2 ± 8.5 g m− 2 ky− 1). Hence, the existence of
large areas with microbial mats may have modified the fluxes of this
element on a global scale.
Despite the large geographical extension of the GoM, the annual
MARs of VHCl (0.72 ± 0.57 Gg), Vpyr (0.018 ± 0.011 Gg), and Vreac (0.74
± 0.57 Gg) to this region represent a very small fraction (0.05%) of the
global MARs of VT. Finally, our results suggest that mass transport by
turbidites can provide important amounts of reduced V in the form of
Vpyr (0.043–0.17 Gg) and produce notable deficits of oxidized V in the
form of VHCl (3.3–13.3 Gg) in every turbiditic event. It is possible that
similar mass transports may be present in other sedimentary environ­
ments with turbiditic activities.
The use of V content in sedimentary pyrite represents a promising
alternative as a proxy for paleoredox conditions, although further
studies are recommended to determine its usefulness in combination
with other redox-sensitive elements such as Mo or U. The decrease in V
content in pyrite as sediment depth increases appears to occur prefer­
entially in sedimentary environments in which pyrite formation is not
limited by the availability of reactive Fe or labile organic matter.
Data availability
The data supporting the findings of this study are available within
the article and Supplementary Material.
J. Garcia-Orozco et al.
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.
Acknowledgments
The authors thank the captains and the crew of the oceanographic
vessels Francisco de Ulloa, Alpha Helix, Justo Sierra and Oceanus for
their help in sample collection. We also thank Virginia Martínez,
Gabriela Cervantes, Alexandro Orozco, and Ramón Martínez for sample
analysis. Special thanks to Silke Severmann, who made it possible to
obtain samples of the California Continental Borderland basins and San
Blas Basin through her cruise 1805C. This research was supported by the
Consejo Nacional de Ciencia y Tecnología (CONACYT) and the Secre­
tariat of Energy through the Fondo Sectorial CONACYT-Secretaría de
Energía-Hidrocarburos (project 201441). This work represents a
contribution of the Gulf of Mexico Research Consortium (CIGoM).
Support in the form of graduate and terminal scholarships granted to J.
G.O. by CONACYT and CIGoM, respectively, is also greatly appreciated.
We also acknowledge the valuable comments made by three anonymous
reviewers and the Associate Editor.
Appendix A. Supplementary material
Supplementary material related to this manuscript includes profiles
showing the degrees of trace metal pyritization, profiles depicting the
concentration of vanadium in diagenetic pyrite, and concentration
profiles of both vanadium and iron associated with the operationally
defined fractions HCl-extractable and pyrite for all cores included in this
study, a dendrogram constructed to assess the similarity in reactive
vanadium concentrations across various sedimentary environments
under investigation, and an explanation of the calculation and param­
eters used to estimate the mass transport of vanadium by turbidites. An
Excel file is also included, containing the median data and the median
absolute deviation of the vanadium concentrations in diagenetic pyrite.
Supplementary material to this article can be found online at htt
ps://doi.org/10.1016/j.gca.2023.07.006.
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