Continental Shelf Research 244 (2022) 104807

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Continental Shelf Research

journal homepage: www.elsevier.com/locate/csr

Physical and biogeochemical controls of the carbonate system of the

Yucatan Shelf
Linda M. Barranco a, b, J. Martín Hernández Ayón a, *, Daniel Pech b, Cecilia Enriquez c, d,
Jorge Herrera e, Ismael Mariño c, Juan Carlos Herguera f
a
Instituto de Investigaciones Oceanológicas, Universidad Autónoma de Baja California, Transpeninsular Tijuana-Ensenada 3917, Fraccionamiento Playitas, CP, 22860,
Ensenada, Baja California, Mexico
b
Laboratorio de Biodiversidad Marina y Cambio Climático (BIOMARCCA), El Colegio de La Frontera Sur, 24500, Campeche, Mexico
c
Facultad de Ciencias, UMDI Sisal, Universidad Nacional Autónoma de México, Sisal, Yucatán, Mexico
d
Escuela Nacional de Estudios Superiores-Mérida, Universidad Nacional Autónoma de México, Tablaje Catastral 6998, Carretera Mérida-Tetiz 4.5 Km, Municipio de
Ucú, Yucatán, CP, 97357, Mexico
e
Departamento de Recursos Del Mar, CINVESTAV Mérida. Carretera Antigua a Progreso Km 6, CP, 97310, Mérida, Yucatán, Mexico
f
Departamento de Ecología Marina, Centro de Investigación Científica y de Educación Superior de Ensenada, Carretera Ensenada-Tijuana No. 3918, Zona Playitas, CP,
22860, Ensenada, BC, Mexico

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

Keywords: The dynamics and distribution of the carbonate system and the processes that regulate it over the Yucatan Shelf
Carbonate system (YS), a region of karst geology and high productivity that is influenced by submarine groundwater discharges
Karst environment (SGDs) and upwelling, were explored with data from two oceanographic cruises. The first oceanographic cruise
Yucatan continental shelf
was conducted in November 2015 during the Nortes season, a period of intense northerly wind activity, and a
Submarine groundwater discharge
Upwelling
second cruise was conducted during the rainy season in August/September 2016. Notable biogeochemical dif­
ferences were present between them. At the surface, Caribbean Surface Water (CSW) predominated over the shelf
in both periods. During the Nortes cruise, a surface nearshore-offshore gradient showed high dissolved inorganic
carbon (DIC; ~2470 μmol kg− 1) and total alkalinity (TA; ~2460 μmol kg− 1) values near the coast and average
pHTotal and pCO2 values of 7.42 ± 0.10 and 2206 ± 546 μatm, respectively. These geochemical characteristics
were attributed to the influence of SGDs, punctuated by relatively low δ13CDIC values between − 4.18‰ and
− 2.49‰, which reflects an important oxidation of organic carbon and the dissolution of carbonate minerals. The
presence of upwelled water on the eastern side of the YS showed average DIC and pHTotal values of 2260 ± 15
μmol kg− 1 and 7.69 ± 0.08, respectively, which were lower than coastal values. During the rainy cruise, the
advection of CSW by the Yucatan Current was traced by its thermohaline properties. However, the surface water
carbonate system was relatively homogeneous, with average DIC, TA, pHTotal, and pCO2 values of 2047 ± 16
μmol kg− 1, 2388 ± 11 μmol kg− 1, 8.02 ± 0.02, and 440 ± 27 μatm, respectively. Lastly, the δ13CDIC values
during this cruise ranged from − 1.21‰ to 1.25‰, which suggests that the carbonate system is mainly regulated
by organic matter production and respiration.

place between the land and sea (Liu et al., 2010). However, carbon
budgets from continental shelves remain poorly known and assessments
1. Introduction
are needed to understand the global carbon biogeochemical cycle and
ocean-atmosphere CO2 exchange (Liu et al., 2010; Dai et al., 2013).
Continental shelves are highly productive areas that play important
Furthermore, this information is critical to estimating the possible re­
roles in the global carbon cycle due to the biogeochemical interactions sponses of these systems to the effects of global climate change, such as
between the land, ocean, and atmosphere that occur in these zones
ocean acidification (Fennel et al., 2019; Cai et al., 2020) and surface
(Gattuso et al., 1998; Aufdenkampe et al., 2011; Dai et al., 2013). water warming. Some studies have been conducted to estimate the
Continental shelves function as carbon reservoirs in which materials
contributions of continental shelves to the global carbon cycle (Gattuso
react and transform and in which carbon and nutrient exchanges take

* Corresponding author.
E-mail address: jmartin@uabc.edu.mx (J. Martín Hernández Ayón).

https://doi.org/10.1016/j.csr.2022.104807
Received 2 February 2022; Received in revised form 30 June 2022; Accepted 1 July 2022
Available online 15 July 2022
0278-4343/© 2022 Published by Elsevier Ltd.
L.M. Barranco et al. Continental Shelf Research 244 (2022) 104807

portion of the peninsula (Enriquez et al., 2010; Bauer-Gottwein et al.,

Abbreviations 2011). In addition, the karst geology favors the outflow of fresh water
through an SGD network, both in specific areas and diffusely over the
absolute dynamic topography (ADT) entire area (Gallardo and Marui, 2006; Bauer-Gottwein et al., 2011:
absolute salinity (SA) Valle-Levinson et al., 2011; Enriquez et al., 2013). A denser concentra­
apparent oxygen utilization (AOU) tion of point discharge zones is present at the intersection of the outer
aragonite saturation state (Ωaragonite) ring of the Chicxulub crater and the sea (i.e., in the zone of the Celestun
average absolute dynamic topography (AADT) Lagoon and in Dzilam de Bravo). Nonetheless, there are many other
Caribbean Surface Water (CSW) groundwater outlets that remain poorly characterized along the YS
conservative temperature (Θ) (Valle-Levinson et al., 2011) that appear to notably contribute to the
dissolved oxygen (DO) SGD outflow of continental waters and likely play important roles in the
dissolved inorganic carbon (DIC) biogeochemistry of the coastal region.
Gulf Common Water (GCW) Furthermore, due to the karst features and growing anthropogenic
partial pressure of CO2 (pCO2) pressures in the region (e.g., aquifer contamination and the increasing
principal component analysis (PCA) demands for freshwater), a few local studies have been conducted in
submarine groundwater discharge (SGD) some coastal ecosystems of the YS with the aim of determining the in­
North Atlantic Subtropical Underwater (SUW) fluence of SGD on nitrogen and phosphorus concentrations, although
Total Alkalinity (TA) these studies have scantily addressed the carbonate system of the region
Tropical Atlantic Central Water (TACW) (Back et al., 1979; Null et al., 2014; Pain et al., 2020). Thus, the car­
Yucatan Shelf (YS) bonate system of the YS remains poorly understood, and an assessment
Yucatan Sea Water (YSW) of such would address the existing knowledge gap regarding the
biogeochemistry of the carbonate system of this important region.
Thus, the objectives of this study were to determine the distribution
of the carbonate system in the YS, identify the physical and biological
et al., 1998; McKee et al., 2004; Liu et al., 2010). Nonetheless, charac­ controls of the variations in the system, and evaluate the responses of the
terizations of these systems are complex because they are highly dy­ aragonite saturation state (Ωaragonite) and the partial pressure of CO2
namic and exhibit great spatial and temporal variability, in addition to (pCO2) to the identified controls.
being strongly influenced by local and regional anthropogenic distur­
bances (Duarte et al., 2013; Liu et al., 2010). 2. Materials and methods
The carbonate system depends on various biogeochemical and
physical processes that operate and interact over continental shelves 2.1. Study area
(Cao et al., 2011), such as the dissolution and precipitation of calcium
carbonate (CaCO3) and the production and respiration of organic matter The coastal sea of the Yucatan Peninsula extends over one of the most
(Gattuso et al., 1998). In addition, organic and inorganic inputs due to extensive (~250 km in length) and shallow continental shelves of the
surface river discharge and coastal upwelling regulate the dynamics and Gulf of Mexico (Fig. 1; Enriquez et al., 2010). The region has three cli­
distribution of the carbonate system in coastal seas (Cao et al., 2011; Dai matic seasons: the dry season (March to May), the rainy season (June to
et al., 2013). However, in karst environments, submarine groundwater October), and the Nortes season (November to February; Arandacirerol
discharge (SGD) also contributes to the transport of dissolved materials et al., 2011). Throughout the year, easterly winds prevail in the region
(Valiela et al., 1990; Null et al., 2014; Barrera and Robbins 2017; Pain (Pérez-Santos et al., 2010). However, during the Nortes season, a
et al., 2020). high-pressure system from the north is frequently present in the region
The Yucatan Shelf (YS) in the Gulf of Mexico is one of the most (Arandacirerol et al., 2011). The Nortes season is characterized by
extensive (~250 km; Enriquez et al., 2010) and productive (Medi­ intense northerly winds of the same name that induce water-column
na-Gómez et al., 2019) shelves in the world. Highly diverse ecosystems mixing and increase sediment resuspension (Hernández-Guevara et al.,
are present along the coastline of the YS (e.g., wetlands, coral reefs, and 2008).
numerous cenotes), making tourism the main economic activity of the Two oceanographic cruises were conducted along the YS. The first
region (Bauer-Gottwein et al., 2011). The oceanographic characteristics campaign took place during the Nortes season from 2 November to 20
of the YS are largely determined by the presence of various water November 2015, (hereinafter the Nortes cruise) aboard the vessel Riviera
masses. Caribbean Surface Water (CSW) is present throughout the year, Maya. A total of 59 stations were sampled during the Nortes cruise
while North Atlantic Subtropical Underwater (SUW) can appear from (Fig. 1a). A second cruise took place during the rainy season from 24
April to June (Merino 1997; Enriquez et al., 2013). In addition, Gulf August to 9 September 2016 (hereinafter the rainy cruise) on board the
Common Water (GCW) and Yucatan Sea Water (YSW) have been re­ vessel UAT 1 CIDIPORT. During this cruise, a total of 76 stations were
ported over the YS. YSW is a surface water mass that is generated locally sampled (Fig. 1b).
and is characterized by salinities >36.5 and high temperatures (26–32 At each station, vertical water-column profiles of temperature (◦ C),
◦
C; Enriquez et al., 2013). salinity, and dissolved oxygen (DO; μmol kg− 1) were generated from
The upwelling system characteristic of the southeastern corner of the data collected with a SeaBird 9plus CTD (Sea-Bird Electronics, Inc.,
YS is due to the interaction of the Yucatan Current, which is an intense Bellevue, USA). To measure carbonate system variables (DIC, TA, and
western boundary current, with the bathymetry. Once the upwelled δ13CDIC), unfiltered seawater samples were collected at the surface (5 m)
water is located over the YS, it is advected to the west and travels over and bottom (maximum depth of each station). The seawater samples
the shelf due to the combined action of the easterly trade winds and the were stored in 125-ml borosilicate bottles and preserved with 25 μL of
momentum received from the Yucatan Current (Merino 1997). Along saturated mercury chloride (HgCl2). The bottles were sealed with snap-
the coast, the bottom layer may be upwelled further by easterly trade on rubber stoppers (Wheaton® CN: W001008J) and aluminum seals
winds, which are most intense from April to June (Enriquez et al., 2010; (Wheaton® CN: W000906JA) to prevent evaporation and gas exchange
Enriquez and Mariño-Tapia 2014; Ruiz-Castillo et al., 2016; Varela et al., with the atmosphere, and the bottles were stored for subsequent ana­
2018). lyses. Prior to sample collection, this sample storage technique was
The highly permeable karst geology of the YS hinders the develop­ tested in the laboratory. In our tests, no significant differences were
ment of surface rivers; in fact, rivers are completely lacking in the north found between samples stored with this technique and those stored

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L.M. Barranco et al. Continental Shelf Research 244 (2022) 104807

Fig. 1. Sampling stations in a) November during the

Nortes season and b) August/September 2016 during
the rainy season. T1–T8 represent the transects par­
allel to the coastline, which are defined by blue cir­
cles and red squares. On the inner shelf, T1 and T5 are
located above the 20-m isobath, and T2 and T6 are
located above the 40-m isobath. On the outer shelf,
T3 and T7 are located above the 80-m and 100-m
isobaths, respectively, and T4 and T8 are located
over the 200-m isobath. The black circles surrounding
some stations indicate that discrete seawater samples
were collected. Yellow circles indicate the locations of
Celestun, Dzilam, and Cabo Catoche.

either in borosilicate bottles sealed with ground-glass stoppers and approximately the 50-m isobath as the inner shelf. On the inner shelf, T1
vacuum grease or those stored with the technique proposed by Dickson and T5 are located above the 20-m isobath, and T2 and T6 are located
et al. (2007). Additionally, Huang and Cai (2012) evaluated different above the 40-m isobath. On the outer shelf, T3 and T7 are located above
sample storage techniques for measuring TA and DIC in seawater and the 80-m and 100-m isobaths, respectively, and T4 and T8 are located
found no differences between samples stored in smaller volume boro­ over the 200-m isobath (Fig. 1). The T-S diagrams and vertical distri­
silicate bottles with screw caps and those stored with the technique of bution plots were generated with Ocean Data View using the ETOPO1 (2
Dickson et al. (2007); the concentrations did change in at least 148 days. × 2 min) global relief model and data interpolation using Data-
Interpolating Variational Analysis (DIVA; Schlitzer, 2018).
To characterize the biogeochemical conditions of the YS based on
2.2. Analytical methods
variations in the carbonate system and hydrological characteristics, a
procedure based on the methodology proposed by Oliver et al. (2004)
Dissolved inorganic carbon (DIC) was determined using a CO2/H2O
was applied. It is briefly described below. The database was analyzed to
LI-COR 7000 infrared gas analyzer (LI-COR, Inc., Lincoln, USA) with a
evaluate multicollinearity based on Pearson correlations. When a vari­
precision of ±2 μmol kg− 1. In addition, pHTotal was measured by spec­
able pair showed collinearity (r > ± 0.95), one variable was excluded
trophotometry with a precision of ±0.002 on the total proton scale, and
from subsequent analyses. The resulting database was normalized (i.e.,
total alkalinity (TA) was determined with a precision of ±2 μmol kg− 1
the mean was subtracted from the data and the result was divided by the
via open cell titration following the methodology of Hernández-Ayón
standard deviation) to reduce variance dissimilarity between factors and
et al. (1999). Measurement precision was evaluated using certified
eliminate the effects of different scales and measurement units.
reference material obtained from the Scripps Institute of Oceanography.
To characterize the environmental parameters that primarily drive
Isotopic determinations of DIC (δ13CDIC), expressed in parts per
the environmental variation along the YS, a principal component anal­
thousand relative to Pee Dee Belemnite, were carried out with a Thermo
ysis (PCA) was employed based on a correlation matrix. The components
Delta Plus Advantage mass spectrometer (Thermo Fisher Scientific,
with eigenvalues greater than 1.0 were selected as significant compo­
Waltham, USA) coupled to a GASBench-II (Thermo Fisher Scientific)
nents, and the variables with the highest loadings were used to describe
following the methodology of Torres et al. (2005) with modifications. A
each component (Quinn and Keough 2002; Zuur et al., 2007).
long-term precision of ±0.06‰ was determined based on the interna­
From the scores obtained with the significant components of the
tional standards NBS19 and LSVEC and three internal laboratory
PCA, a similarity matrix was generated based on Euclidean distances
references.
that was employed in the subsequent cluster analysis using the complete
In situ pH (total proton scale), pCO2, and Ωaragonite values were
linkage method (Legendre and Legendre 1998). The significance of the
derived from the DIC and TA values using CO2SYS software (Lewis and
resulting groups was evaluated with a similarity profile (SIMPROF)
Wallace 1998) and the dissociation constants of Lueker et al. (2000), the
analysis and a permutational analysis of variance (PERMANOVA) at a
sulphate constants of Dickson (1990), and the borate constant of
significance level of 5% with 9000 permutations. All analyses were
Uppström (1974). Additionally, Ocean Data View (Schlitzer, 2018) was
performed using PRIMER v.7 (Clarke and Warwick 2001).
used to obtain apparent oxygen utilization (AOU, μmol kg− 1) from DO
and temperature data. Finally, conservative temperature (Θ in ◦ C) and
3. Results
absolute salinity (SA in g kg− 1) were derived using the International
Thermodynamic Equation of Seawater – 2010 (TEOS-10).
3.1. Hydrographic characteristics of the Yucatan Shelf (YS)

2.3. Data analysis In general, five water masses were delimited in the YS: CSW, YSW,
SUW, GCW, and Tropical Atlantic Central Water (TACW; Fig. 2).
To determine the hydrological conditions of the YS, T-S diagrams The predominant water mass in the YS was CSW (Fig. 2). During the
were generated using Θ and SA with superimposed DO data. The water Nortes cruise, the temperature of this water mass ranged from 22.00 to
masses present in the YS were delimited based on the classifications of 29.00 ◦ C with salinity values between 36.28 and 36.70 g kg− 1. In the
Carrillo et al. (2016), Enriquez et al. (2013), and Portela et al. (2018). In stations closest to the coast, YSW was observed along the western side of
these studies, the water masses were characterized in the Mexican the shelf with temperatures of up to 29.22 ◦ C and salinity values of
Caribbean region where water enters the gulf from the eastern side of the 37.04 g kg− 1 (Transect 1, Fig. 3).
YS, the coastal zone of the YS, and the shelf break surrounding the YS Additionally, a water mass with temperatures from 20 to 25 ◦ C and
that belongs to the deep-water region of the gulf, respectively. salinity values from 36.82 to 37.05 g kg− 1 was observed in the study
In addition, vertical distribution plots of Θ, absolute salinity, and area. The AOU values of this water mass (35.00–75.00 μmol kg− 1) were
AOU were generated along transects parallel to the coastline, which indicative of the hydrographic characteristics that have been reported
were defined by the maximum station depth. The transects were for SUW (Fig. 2a). This water mass was first observed along the 40-m
numbered sequentially from the coast to the open ocean (T1–T8; Fig. 1). isobath (Transect 2) from the eastern end of the YS to Cabo Catoche
In this study, we refer to the portion of the shelf from the coastline to

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L.M. Barranco et al. Continental Shelf Research 244 (2022) 104807

Fig. 2. Conservative temperature (Θ)–absolute salinity (SA) diagrams with dissolved oxygen (DO) data from the oceanographic cruises conducted during a) the
Nortes season in November 2015 (Nortes cruise) and b) the rainy season in August/September 2016 (rainy cruise). The dotted lines delimit the different water masses
based on the characterizations of Carrillo et al. (2016), Enriquez et al. (2013), and Portela et al. (2018).

Fig. 3. Vertical distribution of the hydrological var­

iables recorded in the oceanographic cruise conduct­
ed during the Nortes season in November 2015 (Nortes
cruise). The plots represent the transects parallel to
the YS coastline, which were defined based on
maximum station depth. Transects were numbered
sequentially from the coast to the open ocean: Tran­
sect 1 (T1; 20 m), Transect 2 (T2; 40 m), Transect 3
(T3; 80 m), and Transect 4 (T4; 200 m). Note the
different depth scales from the top to the bottom
panels.

and was further distributed near the bottom up to ~ 88◦ W (Fig. 3). Over the nearshore portion of the western side of the YS, tempera­
An east-west temperature gradient (25.00 ◦ C to ~ 29.00 ◦ C) was tures higher than 28 ◦ C were observed at relatively shallow depths
observed along the coast with salinity values ranging from 36.50 to ~ (Transect 6, Fig. 4). In the coastal transect, the temperature of the water
37.0 g kg− 1. This gradient was not maintained in the DO data, and a column varied between 22.5 and 28.0 ◦ C, and the average salinity was
station located at 88.41◦ W near the eastern intersection of the Chic­ 36.60 g kg− 1. In this area, DO concentrations greater than 200 μmol kg− 1
xulub crater ring with the sea was identified with minimum DO and high were recorded over large portions of the water column. However, AOU
AOU values of 75 μmol kg− 1 and ~135 μmol kg− 1, respectively (Tran­ values over both the nearshore and offshore portions of the YS varied
sect 1, Fig. 3). between -25 and 25 μmol kg− 1 from the surface to ~50 m depth, indi­
During the rainy cruise, CSW and YSW were both observed in the cating that these waters had been in contact with the atmosphere
first 80 m of the water column (Fig. 2b), with their distributions and (Fig. 4).
properties differing between the nearshore and offshore portions of the Finally, it is important to note that waters with SUW properties (i.e.,
shelf. Over the offshore portion, a well-defined surface water layer was temperatures between 20 and 25 ◦ C and salinities >36.80 g kg− 1) were
observed with relatively high temperature values (average of ~30 ◦ C) only recorded in a station near the Yucatan Channel located at the
that extended to a depth of ~50 m. The lowest salinity values for CSW eastern end of the YS (21.30◦ N and 86.40◦ W) during the rainy cruise
(<36.50 g kg− 1 with values of 35.65 g kg− 1) were found in this surface (Fig. 2b).
layer on the eastern side of the YS (Transect 7 and 8, Fig. 4). Towards the
western side (88.5◦ W to 92.5◦ W) of the YS, the salinity values of the 3.2. Biogeochemical characterization of the YS
surface water increased to 36.90 g kg− 1 and were indicative of YSW
(Figs. 2b and 4). Additionally, a water core with DO concentrations The hydrological characteristics of the YS indicate that significant
ranging from 200 to 250 μmol kg− 1 was distributed at depths from 30 to differences were present between the Nortes and rainy seasons, which
60 m (Fig. 2b). was supported by the multivariate analysis results. The two significant

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L.M. Barranco et al. Continental Shelf Research 244 (2022) 104807

Fig. 4. Vertical distribution of the hydrological var­

iables recorded in the oceanographic cruise conduct­
ed during the rainy season in August/September 2016
(rainy cruise). The graphs were generated based on
transects parallel to the YS coastline, which were
defined based on maximum station depth. Transects
were numbered sequentially from the coast to the
open ocean: Transect 5 (T5; 20 m), Transect 6 (T6; 40
m), Transect 7 (T7; 100 m), and Transect 8 (T8; 200
m). Note the different depth scales between the top
and bottom panels.

components obtained from the PCA explained 76.50% of the variation in of the shelf (Fig. 6a1). The average hydrological characteristics of these
the data (see TS1 in Supplementary Material). The first component WTs were similar and correspond to CSW (see TS2 in Supplementary
explained 56.20% of the variance and was defined by the variables of the Material, Fig. 7). However, the WT distributed over the offshore portion
carbonate system. The Nortes cruise was distributed along this compo­ of the shelf (WT5) showed relatively lower DIC (2078–2136 μmol kg− 1)
nent (Fig. 5). The second component explained the remaining 20.30% of and higher pHTotal (7.88–8.06) values when compared to the WT
the variance and was defined by temperature and AOU. The stations of distributed over the nearshore portion of the shelf (WT6), which
the rainy cruise were distributed along this component (TS1, Fig. 5). exhibited DIC concentrations between 2149 and 2216 μmol kg− 1 and
Based on the clustering analysis, 10 water types (WTs) were identi­ pHTotal values of 7.76–7.90 (TS2, Fig. 8). Additionally, WT5 had an
fied in the YS, five of which (i.e., WT3, WT5, WT6, WT7, and WT10) average δ13CDIC of 0.17 (±0.39) ‰, pCO2 of 547 (±69) μatm, and
were only present during the Nortes cruise, while four WTs (i.e., WT1, Ωaragonite of 3.27 (±0.20). On the other hand, the δ13CDIC of WT6 was
WT2, WT4, and WT8) were only present during the rainy cruise (see lighter than WT5 (− 0.87 ± 0.43‰) with pCO2 of 755 (±92) μatm and
Fig. S1 in Supplementary Material). The PERMANOVA confirmed that Ωaragonite of 2.67 (±0.25; TS2, Fig. 8).
there were statistically significant differences between all groups WT3 was found along the eastern side of the YS, both at the surface
(pseudo-F = 171.9, Pperm = 0.0001) base on the SIMPROF analysis. The and bottom, and notably in coastal stations. Due to the characteristics
spatial distributions of the WTs are shown in Fig. 6. and distribution of this WT, it corresponds to SUW and consequently
During the Nortes cruise, a nearshore-offshore gradient was observed upwelled water. The average temperature of WT3 was 26.45 ± 1.44 ◦ C,
in the biogeochemical characteristics of surface water. Both WT6 and and its salinity and AOU ranged values from 36.26 to 36.85 and
WT5 were observed from the 40-m isobath towards the offshore portion 8.00–48.00 μmol kg− 1, respectively (Fig. 6a and b; TS2; Fig. 7). The DIC
values of the WT were higher compared to those of WT5 and WT6 at the
surface with concentrations between 2234 and 2290 μmol kg− 1 and an
average pHTotal value of 7.69 ± 0.08. The δ13CDIC of WT3 was − 1.55
(±0.43) ‰ and ranged from − 2.21 to − 1.08‰; pCO2 was 1101 (±260)
μatm and the average Ωaragonite value was 1.9 (±0.2; TS2, Fig. 8). Finally,
WT10 was observed over the nearshore, western portion of the YS at
both the surface and bottom, particularly at the most coastal stations
(Fig. 6a). This WT presents the thermohaline characteristics of YSW and
presented the highest DIC concentrations (2346–2470 μmol kg− 1) and
TA values (2386–2460 μmol kg− 1) of all WTs with pHTotal values < 7.5
and AOU values that ranged from 12 to 85 μmol kg− 1 (TS2, Fig. 8). Its
δ13CDIC was also the lightest of all WTs with an average value of − 3.15
(±0.54) ‰. In addition, pCO2 varied from 1499 to 3250 μatm, and
Ωaragonite values ranged between 0.8 and 1.4 (TS2, Fig. 8).
During the Nortes cruise, the biogeochemical conditions at the bot­
tom seemed to be relatively homogeneous and were represented by WT7
except for WT3 and WT10, which were distributed near the coast
(Fig. 6a2). Due to its distribution in the T-S diagrams, WT7 exhibited the
thermohaline characteristics of CSW, with low temperatures ranging
Fig. 5. Principal component analysis (PCA), which explained 76.50% of the from 18.43 to 25.73 ◦ C (see Fig. S2 in Supplementary Material) and
variation in the data. The PCA scores were extracted to generate the complete
higher AOU values (49–140 μmol kg− 1) with respect to those of WT5 and
linkage hierarchical clustering analysis shown in Fig. S1, which produced ten
WT6 (TS2, Fig. 7). In addition, WT7 was characterized by high DIC
significantly different clusters that were considered water types (WTs). The WTs
present during the Nortes cruise conducted during the Nortes season in concentrations (2222–2369 μmol kg− 1) and TA (2407–2428 μmol kg− 1)
November 2015: WT3, WT5, WT6, WT7, and WT10. The WTs present during values and low pHTotal values (7.52–7.85). Its δ13CDIC was − 1.28
the rainy cruise conducted during the rainy season in August/September 2016: (±0.61) ‰ with an average pCO2 of 1105 (±284) μatm and Ωaragonite
WT1, WT2, WT4, and WT8. values between 1.0 and 2.2 (TS2, Fig. 8).

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L.M. Barranco et al. Continental Shelf Research 244 (2022) 104807

Fig. 6. Maps of the spatial distributions of the water types (WTs) characterized in the Yucatan Shelf (YS) for the oceanographic cruises conducted during a) the Nortes
season in November 2015 (Nortes cruise) and b) the rainy season in August/September 2016 (rainy cruise).

Fig. 7. Box plots for the hydrological variables of the

water types (WTs) characterized in the Yucatan Shelf
(YS) during the oceanographic cruises conducted
during the Nortes season in November 2015 (Nortes
cruise), namely WT3, WT5, WT6, WT7, and WT10 (to
the right of the black dashed lines), and during the
rainy season in August/September 2016 (rainy
cruise), namely WT1, WT2, WT4, and WT8 (to the left
of the black dashed lines). The black lines represent
the medians, and the blue dashed lines represent the
average values. The black circles indicate extreme
data.

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L.M. Barranco et al. Continental Shelf Research 244 (2022) 104807

± 16 μmol kg− 1) was ~25 μmol kg− 1 higher than that of the surface
layer, although no differences were present with respect to pHTotal,
average TA, or δ13CDIC (TS3, Fig. 8). When compared with those of WT2,
the average temperature (22.90 ± 1.36 ◦ C), salinity (36.63 ± 0.40),
AOU (48 ± 13 μmol kg− 1), DIC (2123 ± 30 μmol kg− 1), and TA (2404 ±
8 μmol kg− 1) values of WT4 were higher. The average values for TW4 of
pHTotal, δ13CDIC, pCO2, and Ωaragonite were 8.00 (±0.05), 0.30 (±0.45)
‰, 468 (±74) μatm, and 3.09 (±0.29), respectively. This WT was mainly
observed over the offshore portion of the YS (TS3, Figs. 7 and 8). It is
important to mention that both WTs, WT2, and WT4 were also observed
at the surface, most notably in coastal stations (Fig. 6b1).
Finally, WT8 was observed at the bottom in stations near the edge of
the offshore portion of the YS along the 200-m isobath (Fig. 6b2). Due to
the thermohaline characteristics and distribution of WT8, it corre­
sponded to GCW and TACW (Fig. S2). The average temperature of this
WT was 18.30 ± 2.00 ◦ C, and relatively low average DO concentrations
(128 ± 9 μmol kg− 1) and high AOU values (102 ± 14 μmol kg− 1) were
observed (TS3, Fig. 7). The DIC concentration of WT8 ranged from 2149
to 2292 μmol kg− 1, and an average pHTotal value of 7.96 ± 0.09 was
present. The δ13CDIC ranged from − 1.21 to 0.53‰, and the average pCO2
and Ωaragonite values were 521 (±154) μatm and 2.46 (±0.5), respec­
tively. However, average TA (2396 ± 12 μmol kg− 1) was similar to those
of the remaining WTs present during the rainy cruise (TS2, Fig. 8).

4. Discussion

The biogeochemical characteristics observed in the YS suggest that

the advection and mixing of different water masses and the exchange
with continental water inputs, which are mainly the result of SGD, are
the primary mechanisms that modulate the variation and distribution of
the carbonate system in this region of the Gulf of Mexico. The contri­
butions of these mechanisms are influenced by the seasonal variability
of the region, which is reflected in the differences detected between the
two sampling periods.
Fig. 8. Box-plots for the carbonate system variables of the water types (WTs)
characterized in the Yucatan Shelf (YS) during the oceanographic cruises con­
ducted during the Nortes season in November 2015 (Nortes cruise), namely 4.1. Water mass advection
WT3, WT5, WT6, WT7, and WT10 (to the right of the black dashes lines), and
the rainy season in August/September 2016 (rainy cruise), namely WT1, WT2, 4.1.1. Caribbean Surface Water (CSW)
WT4, and WT8 (to the left of the black dashes lines). The black lines represent The Yucatan Current brings CSW into the Gulf of Mexico, which
the medians, and the blue dashed lines represent the average values of the enters the gulf along the eastern side of the shelf. Caribbean surface
parameters. The black circles are extreme data.
water constitutes the main body of water in the YS and can be found up
to 100 m depth. At the surface, this water mass exhibited thermohaline
In contrast, during the rainy cruise, the biogeochemical conditions of differences that are typical of the surface water of the Gulf of Mexico
the surface layer appeared to be more homogeneous compared to those (Zavala-Hidalgo et al., 2002, 2014). During the Nortes cruise, relatively
of the previous cruise. In particular, WT1 dominated the surface, low temperatures (<28 ◦ C) were recorded, while during the rainy cruise,
although it was also observed at the bottom towards the eastern stations maximum temperatures as high as 30.73 ◦ C were recorded (Fig. 2).
near the Yucatan Channel and near the western stations located on the During both cruises, an east-west salinity gradient was observed with
80-m isobath (Fig. 6b). Given its hydrological characteristics, this WT lower salinities on the eastern side of the offshore portion of the shelf
corresponds to CSW (Fig. S2). In addition, WT1 exhibited high tem­ (Fig. 3, Transect 3, 4; Fig. 4, Transect 7, 8). In particular, the variation
peratures that ranged from 25.07 to 30.55 ◦ C, high DO concentrations of during the rainy cruise was greater than that of the Nortes cruise given
178–215 μmol kg− 1, and an average AOU value of 1.2 (±6) μmol kg− 1 that salinities of 35.87–36.25 g kg− 1 were observed. Carrillo et al.
that reflected water in equilibrium with the atmosphere (see TS3 in (2016) also reported surface waters with low salinity during January
Supplementary Material, Fig. 7). The DIC, TA, pHTotal, and δ13CDIC 2007 in their study, which was conducted throughout the Mesoamerican
values of WT1 ranged from 2020 to 2097 μmol kg− 1, 2367–2413 μmol Barrier Reef System (MBRS). These authors concluded that this was due
kg− 1, 7.93–8.08, and 0.12–1.25‰, respectively. Lastly, the mean values to the dilution of water caused by SGD, which occurs in the northern
of pCO2 and Ωaragonite were 440 (±27) μatm and 3.8 (±0.2), respectively MBRS prior to the waters entering the Gulf of Mexico. However, dilution
(TS3, Fig. 8). of CSW occurs at lower latitudes (~12◦ N) near the Colombian Basin
A subtle nearshore-offshore gradient was observed at the bottom. where a notable dilution area is created by the combined runoff of
Both WT2 and WT4 were also present at the bottom along the YS several rivers and high rates of precipitation (Beier et al., 2017).
(Fig. 6b2) and both were characterized as CSW by their thermohaline Once over the YS, the CSW increases in salinity along its westward
characteristics (Fig. S2). When compared to WT4, WT2 showed greater trajectory (Figs. 3 and 4), which follows the circulation pattern of the YS
variation in biogeochemical characteristics and was found at shallower (Zavala-Hidalgo et al., 2006), due to the high evaporation rates in the
depths. The average temperature of WT2 was 25.4 ± 1.92 ◦ C, with DO region (Enriquez et al., 2013). The entry and modification of CSW over
and AOU values of 176 (±30) μmol kg− 1 and 29 (±26) μmol kg− 1, the offshore portion of the YS is also reflected in DIC and TA (TS1, TS2).
respectively (TS3, Fig. 7). The average DIC concentration of WT2 (2073 During the Nortes cruise, WT5 was observed along the eastern side of the

7
L.M. Barranco et al. Continental Shelf Research 244 (2022) 104807

1
offshore portion of the shelf with an average DIC value of 2114 (±19) μmol kg− and pHTotal (7.69 ± 0.08) values. The presence of SUW over
μmol kg− 1, and WT6 was found along the western side of the shelf with the shelf during the Nortes cruise constituted an additional source of
an average DIC value of 2184 (±23) μmol kg− 1, which resulted in a water with high DIC concentrations in the water column.
difference of 70 μmol kg− 1. During this cruise, the variation in average The presence and absence of SUW can be explained based on the
TA values between these two WTs was only 6 μmol kg− 1 (Fig. 6a1, TS2, position, intensity, and direction of the Loop Current (Jouanno et al.,
Fig. 8). During the rainy cruise, only WT1 was found at the surface from 2018; Varela et al., 2018). The interaction of the Loop Current with the
the 40-m isobath extending towards the offshore portion of the shelf. bathymetry of the shelf is also a key factor that determines the advection
The average DIC and TA values were 2047 (±16) μmol kg− 1 and 2388 of SUW (Enriquez et al., 2013; Jouanno et al., 2018; Merino 1997;
(±11) μmol kg− 1 (TS1), respectively. However, the lowest values for Varela et al., 2018). Based on a climatological analysis of 25 years of
both variables (i.e., ~2020 μmol kg− 1 and ~2380 μmol kg− 1, respec­ satellite data, Delgado et al. (2019) statistically determined that the
tively) were found in stations towards the eastern portion of the shelf. Loop Current retracts towards its southernmost position from October to
It should be noted that the DIC and TA concentrations registered March and extends and enters the Gulf of Mexico along a northwesterly
during the Nortes cruise were higher than those of the rainy cruise trajectory from May to September. From the average absolute dynamic
(Fig. 8). When considering the advection of water masses, the presence topography (AADT) generated from the AVISO database (http://www.
of SUW during the Nortes cruise explains these differences in the offshore aviso.alitmetry.fr/), it can be observed that the Loop Current extended
portion of the shelf, as the concentrations observed over the nearshore and penetrated the Gulf of Mexico towards its interior in November
portion of the shelf appear to depend on another mechanism, which is 2015 during the Nortes cruise. The Loop Current interacted with the
discussed in section 4.2. shelf during this period, which contributed to the presence of SUW
(Fig. 9a). Meanwhile in August/September 2016 during the rainy cruise,
4.1.2. Subtropical underwater (SUW) or upwelled water the Loop Current appeared retracted and was found towards the Florida
In the YS, SUW has been identified as upwelled water (Merino 1997; Straits (Fig. 9b).
Enriquez et al., 2013) and is distributed along the 25.5 kg m− 3 isopycnal
at ~200 m depth (Portela et al., 2018). The presence of SUW over the 4.1.3. Yucatan Sea Water (YSW)
shelf is attributed to isopycnal rise and the advection generated by the YSW locally acquires its thermohaline properties due to the heating
interaction between the Yucatan Current and the bathymetry of the shelf and evaporation of water in shallow, coastal environments and its sub­
near Cabo Catoche (~87◦ W; Enriquez et al., 2010, 2013; Jouanno et al., sequent exchange with the open sea; this water is characterized by
2018; Merino 1997; Varela et al., 2018). Once over the shelf, SUW can temperatures between 26 and 31 ◦ C and salinities of 36.4–36.8 (Enri­
either travel westward (Merino 1997) or emerge near the coast due to quez et al., 2013). During the rainy cruise, water with these thermo­
wind stress (Jouanno et al., 2018; Pérez-Santos et al., 2010; Reyes-­ haline characteristics was detected towards the western portion of the
Mendoza et al., 2016; Ruiz-Castillo et al., 2016; Varela et al., 2018). shelf, from the 40-m isobath towards the outer shelf (Figs. 2b and 4). In
These mechanisms are independent but not mutually exclusive fact, this water is CSW that has been modified on its westward path,
(Jouanno et al., 2018). In fact, upwelling in the YS is most intense from which is probably due to the high evaporation rates in the region
June to August when upwelled water is already available over the YS, (Enriquez et al., 2013). The resulting homogenization of DIC concen­
after which the easterly winds are capable of advecting colder water trations after normalizing with salinity supports this hypothesis.
near the shore in the western coastal region (Jouanno et al., 2018; During the rainy cruise, YSW was detected based on its thermohaline
Varela et al., 2018; Ruiz-Castillo et al., 2016; Enriquez and Mariño-Tapia (Figs. 2a and 3, Transect 1) and chemical properties (WT10) in the
2014). However, for the rainy cruise, SUW was not recorded over the coastal zone along the western portion of the shelf, both at the surface
shelf (Fig. 2b), but it may be present as residual SUW that modifies its and bottom (Fig. 6a), with average DIC and TA values of 2388 ± 39
thermohaline characteristics once over the shelf. On the other hand, μmol kg− 1 and 2435 ± 25 μmol kg− 1 values, respectively. These high
during the Nortes cruise, SUW was observed over the eastern side of the concentrations may be due to the additional contributions of carbon due
shelf. The presence of SUW can be traced by temperature and salinity to SGD over the YS (Bauer-Gottwein et al., 2011).
from 10 to 200 m depth (Fig. 3) and was also objectively characterized
as WT3 (Fig. 6a). The DIC and TA values for this WT were 2260 (±15)
4.2. Influence of submarine groundwater discharge (SGD)
μmol kg− 1 and 2409 (±19) μmol kg− 1, respectively. Both values were
higher than those of the surface water present over the offshore portion
SGD includes both fresh groundwater and recirculated seawater
of the shelf. This was also reflected in the average AOU (27.64 ± 13)
(Taniguchi et al., 2002). Also can contribute notable amounts of carbon

Fig. 9. Average absolute dynamic topography (AADT; m) of the Yucatan Shelf (YS) and the Loop Current during a) the oceanographic cruise conducted during the
Nortes season in November 2015 (Nortes cruise) and b) the rainy season in August/September 2016 (rainy cruise). The altimetry products were produced and
distributed by AVISO+ (https://www.aviso.altimetry.fr).

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L.M. Barranco et al. Continental Shelf Research 244 (2022) 104807

and nutrients to the coastal ocean (Moore 2010; Chaillou et al., 2014).
The flow of groundwater discharge has been associated with fracture
zones (Bauer-Gottwein et al., 2011) and other submarine springs along
the coast of the YS (ArandaCirerol et al., 2006; Valle-Levinson et al.,
2011). Regionally, the most important point discharge areas have been
associated near the Chicxulub crater, which was generated as a result of
an asteroid impact at the end of the Cretaceous period (Pope et al.,
1991). The Ring of Cenotes marks the outer edge of the Chicxulub crater
and intersects the continent and sea in the coastal region, and the closest
station near this area exhibited the highest DIC (2470 μmol kg− 1) and TA
(2450 μmol kg− 1) values were recorded during the Nortes cruise. The
water in this area has been found to have pHTotal, pCO2, and DO values of
7.25, 3250 μatm, and <65 μmol kg− 1, respectively. Salinity values at this
station ranged from 36.48 to 36.51 with practically no variation in the
water column because groundwater in this area can be composed of
either meteoric water or recirculated seawater.
The chemical characteristics of this water agree with those previ­
ously reported for the coastal surface water of the west-central Gulf of
Florida with pHTotal, TA, and pCO2 values of 7.78, 2870 μmol kg− 1, and Fig. 10. The DIC vs δ13CDIC relationship for the water types (WTs) character­
1193 μatm, respectively (Barrera and Robbins 2017), and with those ized in the Yucatan Shelf (YS) during the two sampling periods.
reported for submarine springs on the eastern coast of the YS with pH
and DIC values of 7.40 and ~3457 μmol kg− 1, respectively (Pain et al., During the Nortes cruise, the isotopic composition of the surface
2020). The groundwater of the YS principally acquires high DIC and TA water was lighter when compared to that of the rainy cruise and with
values due to organic matter remineralization and the dissolution of what has been previously reported for surface ocean waters (Kroopnick
carbonate minerals, as has been previously suggested for similar envi­ 1985). For example, upwelling water (WT3) showed an isotopic
ronments (Cai et al., 2003; Pain et al., 2020). Thus, groundwater with composition that ranged from − 2.21‰ to − 1.08‰ with high DIC (2260
high DIC and low pH values interacts with karst substrate, which results ± 16 μmol kg− 1) and AOU (27.64 ± 13.38 μmol kg− 1) values, which
in the dissolution of CaCO3 and subsequently increases TA (Cai et al., reflected a predominance of organic matter respiration. The isotopic
2003; Yamanaka 2012; Pain et al., 2020). composition of YSW (WT10), which was distributed in the stations
closest to the coast, varied between − 4.18‰ and − 2.49‰ (Fig. 10),
4.3. Processes that modulate the carbonate system in the Yucatan Shelf which reflects organic carbon oxidation and the dissolution of carbonate
(YS) minerals (Hu and Burdige 2007; Yamanaka 2012, Zeebe & Gladrow
2001).
Inputs of CO2 either from the atmosphere or due to organic matter In this sense, the δ13CDIC of fresh groundwater will initially have the
degradation and carbonate dissolution are the main contributors to DIC isotopic composition of the oxidation of organic matter and its associ­
in seawater. On the other hand, the removal of DIC from seawater is the ated pH. The values reported for this groundwater vary between − 20‰
result of photosynthesis, carbonate precipitation, and ocean-atmosphere and − 15‰ (Gonfiantini and Zuppi 2003; Yamanaka 2012). On its way to
exchange. The processes and mechanisms that control the amount of DIC the sea, the groundwater interacts with limestone, which results in
in seawater are complex (Zeebe and Wolf-Gladrow 2001; Liu et al., isotopic exchange due to substrate dissolution and the enrichment of 13C
2010a) and their relative contributions are difficult to assess from these in DIC given that the isotopic composition of limestone (0‰–2‰) is
variables alone. The isotopic composition of DIC (δ13CDIC) in seawater is heavier than that of the groundwater flowing through it (Gonfiantini
useful for determining different sources of inorganic carbon in coastal and Zuppi 2003), and mixes with seawater with lower DIC and positive
seas (Liu et al., 2010a). The δ13CDIC values depend on the isotopic δ13C values along its way to the open ocean. From our results, we were
composition of different carbon sources and sinks and the isotopic able to identify a typical ocean showing carbon isotopic compositions
fractionation that occurs as carbon is exchanged between them (Zeebe close to 1‰ and relatively low DIC concentrations (2000–2100 μmol
and Wolf-Gladrow 2001). kg− 1) and seawater showing negative δ13C values of up to − 4‰ and high
The δ13CDIC values in seawater from the YS ranged from − 4.18‰ to DIC concentrations of up to 2500 μmol kg− 1 that are most likely due to
0.87‰ during the Nortes cruise and − 1.21‰–1.25‰ (TS2, TS3) during the oxidation of light organic carbon and the dissolution of
the rainy cruise. The range of values observed in the rainy cruise agrees carbonate-rich host rocks.
with those that have been reported for surface waters from different
ocean basins that collectively range from − 1‰ to 2.2‰ (Kroopnick 4.4. Response of pCO2 and ωaragonite to variations in DIC and TA in the
1985). This variation in isotopic composition mainly corresponds to Yucatan Shelf (YS)
biological regulation due to photosynthesis and organic matter respi­
ration. During photosynthesis, organisms discriminate against the heavy The pCO2 is used as an indicator of the ocean-atmosphere CO2 ex­
isotope 13C in favor of the lighter 12C, thus favoring an increase in change, and Ωaragonite is used as an indicator of the availability of car­
δ13CDIC values in seawater. During organic matter degradation, 12C is bonate ions in the water column. Both pCO2 and Ωaragonite are affected
once again released into the water column, which favors a decrease in due to increases in anthropogenic CO2 emissions (Sabine et al., 2004;
δ13CDIC. This was observed in the YS during the rainy cruise. The isotopic Zeebe et al., 2008). During the Nortes cruise, the pCO2 values, particu­
composition of the surface water (WT1) varied from 0.12‰ to 1.25‰, larly those in the coastal zone, ranged between 1400 and 3250 μatm,
which was associated with low DIC concentrations (2020–2097 μmol which were well above the current average global concentration of at­
kg− 1) and an average AOU value of 1.0 ± 6 μmol kg− 1. In contrast, mospheric CO2 (~412 ppm as of 2020, NOAA Mauna Loa Observatory).
isotopically lighter values (− 1.21‰–0.60‰) were present in bottom Thus, a portion of the YS releases CO2 into the atmosphere at least
water (WT2, WT4, and WT8) that were associated with higher DIC during this season.
(2033–2292 μmol kg− 1) and AOU (~30.19–122 μmol kg− 1) values, Additionally, the water of the coastal zone had low pHTotal values
which reflects a predominance of organic matter respiration (TS3; (7.25–7.56) and values that were close to or below the saturation ho­
Figs. 8 and 10). rizon of Ωaragonite (0.76–1.45; TS2, Fig. 8). These conditions are

9
L.M. Barranco et al. Continental Shelf Research 244 (2022) 104807

considered stressful for organisms, particularly those that generate cal­ Acknowledgments
cium carbonate structures. The geochemical characteristics of this
coastal water were attributed to the influence of SGD, in addition to the We thank the cruise staff, especially Dr. Ana Aguilar, for their sup­
presence of upwelled water on the eastern side of the YS with average port in collecting samples.
DIC and pHTotal values of 2260 (±15) μmol kg− 1 and 7.69 (±0.08),
which resulted in the high pCO2 and low Ωaragonite values recorded Appendix A. Supplementary data
during this cruise.
In contrast, during the rainy cruise, relatively similar pCO2 Supplementary data to this article can be found online at https://doi.
(374–553 μatm), pHTotal (8.02 ± 0.02), and Ωaragonite (>3) values were org/10.1016/j.csr.2022.104807.
recorded over the entire shelf, with the exception of the values recorded
over the offshore portion of the shelf in deep water (WT8; TS3, Fig. 8). References
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HCl(aq), and the standard acidity constant of the ion HSO-4 in synthetic sea water
Energy (SENER) - National Council of Science and Technology of Mexico
from 273.15 to 318.15 K. J. Chem. Thermodyn. 22 (2), 113–127. https://doi.org/
(CONACyT) Hydrocarbon Fund through a Postdoctoral grant awarded to 10.1016/0021-9614(90)90074-Z. In this issue.
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ocean syndrome? Understanding anthropogenic impacts on seawater pH. Estuar.
Declaration of competing interest Coast 36, 221–236. https://doi.org/10.1007/s12237-013-9594-3.
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