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The Seasonal Dynamics of Organic and Inorganic Carbon along the Tropical
Usumacinta River Basin Mexico

Article in Water · August 2022

DOI: 10.3390/w14172703

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 water
Article
The Seasonal Dynamics of Organic and Inorganic Carbon along
the Tropical Usumacinta River Basin (Mexico)
Ismael Soria-Reinoso 1 , Javier Alcocer 2, * , Salvador Sánchez-Carrillo 3 , Felipe García-Oliva 4 ,
Daniel Cuevas-Lara 1 , Daniela Cortés-Guzmán 1 and Luis A. Oseguera 2

1 Posgrado en Ciencias del Mar y Limnología, Universidad Nacional Autónoma de México,

Av. Universidad 3000, Alcaldía Coyoacán, C. P., Mexico City 04510, Mexico
2 Grupo de Investigación en Limnología Tropical, FES Iztacala, Universidad Nacional Autónoma de México,
Av. De los Barrios N◦ 1, Los Reyes Iztacala, Tlalnepantla 54090, Mexico
3 Departamento de Biogeoquímica y Ecología Microbiana, Museo Nacional de Ciencias Naturales (CSIC),
Serrano 115 dpdo, 28006 Madrid, Spain
4 Instituto de Investigaciones en Ecosistemas y Sustentabilidad, Universidad Nacional Autónoma de México,
AP 27-3, Santa María de Guido, Morelia 58090, Mexico
* Correspondence: [email protected]; Tel.: +52-55-5623-1333 (ext. 39719)

Abstract: Rivers are important sites for carbon (C) transport and critical components of the global C
cycle that is currently not well constrained. However, little is known about C species’ longitudinal
and temporal changes in large tropical rivers. The Usumacinta River is Mexico’s main lotic system
and the tenth largest in North America. Being a tropical river, it has a strong climatic seasonality. This
study aims to evaluate how organic (DOC and POC) and inorganic (DIC and PIC) carbon change
spatially and seasonally along the Usumacinta River (medium and lower basin) in rainy (RS-2017) and
Citation: Soria-Reinoso, I.; Alcocer, J.;
dry (DS-2018) seasons and to estimate C fluxes into the southern Gulf of Mexico. Concentrations of
Sánchez-Carrillo, S.; García-Oliva, F.;
DOC, POC, DIC, and PIC ranged from 0.88 to 7.11 mg L−1 , 0.21 to 3.78 mg L−1 , 15.59 to 48.27 mg L−1 ,
Cuevas-Lara, D.; Cortés-Guzmán, D.;
and 0.05 to 1.51 mg L−1 , respectively. DOC was the dominant organic species (DOC/POC > 1). It
Oseguera, L.A. The Seasonal
was ~doubled in RS and showed a longitudinal increase, probably through exchange with wetlands
Dynamics of Organic and Inorganic
Carbon along the Tropical
and floodplains. Particulate carbon showed a positive relationship with the total suspended solids,
Usumacinta River Basin (Mexico). suggesting that in RS, it derived from surface erosion and runoff in the watershed. DIC is reported
Water 2022, 14, 2703. for the first time as the highest concentration measured in tropical rivers in America. It was higher in
https://doi.org/ the dry season without a longitudinal trend. The C mass inflow–outflow balance in the RS suggested
10.3390/w14172703 net retention (DOC and POC sink) in floodplains. In contrast, in the DS, the balance suggested that
Academic Editors: Yijun Xu
floodplains supply (C source) autochthonous DOC and POC. The lower Usumacinta River basin is a
and Siyue Li sink for DIC in both seasons. Finally, the estimated annual C export for the Usumacinta-Grijalva River
was 2.88 (2.65 to 3.14) Tg yr−1 , of which DIC was the largest transported fraction (85%), followed
Received: 30 June 2022
by DOC (10%), POC (4%), and PIC (<1%). This investigation is the first to present the C loads in a
Accepted: 26 August 2022
Mexican river.
Published: 30 August 2022

Publisher’s Note: MDPI stays neutral Keywords: carbon biogeochemistry; dissolved organic carbon; dissolved inorganic carbon; particu-
with regard to jurisdictional claims in late organic carbon; Centla wetlands; tropical river; Usumacinta-Grijalva Rivers
published maps and institutional affil-
iations.

1. Introduction
Copyright: © 2022 by the authors.
Inland waters cover only a tiny fraction (about 1%) of the Earth’s surface [1] but play
Licensee MDPI, Basel, Switzerland. disproportionate roles in the global carbon (C) cycle [2–4]. Rivers are functional interfaces
This article is an open access article for the transport, processing, and exchange of C between terrestrial ecosystems [5–7];
distributed under the terms and the atmosphere [8,9]; and the marine environment [10–12] throughout the aquatic contin-
conditions of the Creative Commons uum [13–15]. Over the last decade, the annual rate of C transported by rivers globally to
Attribution (CC BY) license (https:// the oceans (1.06 Pg C yr−1 ; 1 Pg = 1015 g) [16] is on the same order of magnitude as the rate
creativecommons.org/licenses/by/ of C sequestration by land (3.4 ± 0.9 Pg C y−1 ) or than the oceanic uptake of atmospheric
4.0/). CO2 (2.5 ± 0.6 Pg C yr−1 ) [17]. The total annual C exported by worldwide rivers includes

Water 2022, 14, 2703. https://doi.org/10.3390/w14172703 https://www.mdpi.com/journal/water

Water 2022, 14, 2703 2 of 30

0.41 Pg of dissolved inorganic C (DIC), 0.24 Pg of dissolved organic C (DOC), 0.24 Pg of

particulate organic C (POC), and 0.17 Pg of particulate inorganic C (PIC) [16].
Riverine C originates from natural and anthropogenic sources; however, anthro-
pogenic influences are complex and difficult to quantify [5]. The lateral transport of
terrestrial net PP (plant and litter detritus or leached material) and the export of terrestrial
inorganic C (chemical weathering of silicate and carbonate minerals and soil respiration,
as well as erosion of carbonate rocks) are the principal pathways through which C enters
the fluvial systems [5]. However, the biogeochemical processes involved in river C fluxes
are still unclear because physical and biological factors vary widely along the hydrological
continuum [14,15].
Inputs of organic C (OC) alter the metabolism of both river and connected downstream
water bodies and are vital for sustaining coastal heterotrophy [18]. Both DOC and POC
play significant roles in the river C cycle. However, DOC is the primary energy source
sustaining the heterotrophic aquatic metabolism, resulting in a large amount of CO2
outgassing to the atmosphere [19]. Riverine DOC results from the balance between both
allochthonous terrestrial (leaching of dissolved organic matter -OM- from soils through
runoff) and autochthonous (derived from fluvial productivity -PP-) contributions and
microbial consumption, flocculation, and photodegradation processes [19,20]. DOC fluxes
are determined by several factors (e.g., hydrological events, basin slope, soil C), showing
considerable spatial and seasonal variation within a catchment [16,20], with higher values
in wetlands and around rainfall events [21,22]. Otherwise, POC originates from fresh leaf
litter, PP, and wastewater discharges and the weathering and oxidation of OC contained
in sedimentary rocks (or petrogenic OC [12,23]). DOC/POC ratios vary widely between
rivers, from 10:1 in temperate forests to 1:1 in grassland areas [24]. In low-relief tropical
basins with wetland presence, the DOC/POC ratio is >1 [25]. In contrast, in humid regions
with mountainous relief, such as the Asian monsoon basins or the upper Amazon River
basin, the DOC/POC ratio is <1 [12]. As a result of gravitational settling, hydrodynamic
lift, and drag forces [19], a strong correlation between POC concentration, total suspended
solids (TSS), and discharge has been found for most worldwide river systems [12,26].
Over geologic time, rivers have transported C due to the chemical weathering of
carbonate and silicate rocks to storage in marine sinks [27,28]. DIC is the most significant
part of river C entering the oceans [11,26] and consists of bicarbonate (HCO3 − ) and car-
bonate (CO3 2− ) as well as CO2 dissolved in riverine water, with the chemical equilibrium
depending on temperature and pH [29]. When river water pH oscillates from 6 to 8.5,
HCO3 − is the dominant component, the most usual form in which DIC appears [20,30]. DIC
concentration is controlled by: (i) the lithology and the weathering of carbonate/silicate
rocks, (ii) the soil CO2 released by the terrestrial OM decomposition and transported to
the river, (iii) the exchange of CO2 at the water–air interface, and (iv) the internal river
processes that release CO2 through the decomposition of allochthonous and autochthonous
OM and trigger the C uptake by the PP [31–33]. Carbonated river basins display a DIC
concentration an order of magnitude greater than that of non-carbonated crystalline basins
(volcanic or plutonic rocks) [12]. PIC originates from the mechanical erosion of carbonate
rocks (limestone, slate). However, it can be dissolved as DIC downstream [34] or gradually
precipitate, trapped in floodplains and estuaries before reaching the coastal waters [35].
Despite its significant effect on DIC, PIC usually does not account for the overall C budget
because it is considered a transfer of carbonate minerals from the river headwaters to the
oceans [11].
Tropical regions account for 42.7% of global area, but they contribute the highest per-
centage of freshwater (~66%), sediment (~73%), and C (~50%) discharging to the worldwide
oceans [11,16]. Tropical rivers are hotspots of C export to the sea, displaying a high hydro-
logical seasonality according to rainy and dry seasons [36,37]. Nevertheless, magnitude
and C processing have been poorly studied in tropical rivers despite their disproportion-
ate importance compared with rivers from other latitudes [15]. During the past decade,
Water 2022, 14, 2703 3 of 30

research on C in low-latitude areas has been strongly encouraged in America [23,38–44],

Africa [45–51], and Asia [52–57], but it is not enough yet.
In tropical America, a lack of knowledge about the role of river systems in the re-
gional C cycle is evident [58–60]. Mexico has the largest rivers in Central America, but
scientific knowledge of these rivers is still incipient. The Usumacinta River is Mexico’s
most important lotic system and the tenth largest in North America [61,62]. It drains into
the southern Gulf of Mexico under a tropical seasonality defined by a rainy season in
summer and a dry season in winter [63]. It is assumed that the Usumacinta River plays an
essential role in the regional C balance, particularly in DIC fluxes to the Gulf of Mexico,
due to carbonaceous lithology [61]. However, this has been poorly studied compared with
other South American [41,64,65] and North American rivers [66–68]. A recent study [42]
on the POC dynamics in the Usumacinta River revealed a strong seasonality in sources,
concentrations, and fluxes. Furthermore, during the dry season, the wetlands of the lower
basin function as a POC source, while in the rainy season, they are a sink for POC, mainly
allochthonous [42]. Nevertheless, the spatial and temporal variation of dissolved C and the
role of floodplains on the retention or delivery of DOC, DIC, and POC to the mainstem are
still unknown. The present study is an effort to fill this gap in our knowledge.
This research aims to generate baseline information on the seasonal and spatial changes
in the C concentration and fluxes in the Usumacinta River basin, along with the river’s
hydrochemistry parameters. This work pursued evaluating the longitudinal pattern of
C concentrations and fluxes in the middle and lower basin of the Usumacinta River to
identify the variability in C fractions according to tropical climatic seasonality (rainy vs.
dry season) and to estimate the C fluxes and quantify the C discharged to the southern
Gulf of Mexico. Since this investigation was exploratory in nature, it tested no hypothesis.
However, based on the basin’s dominant carbonaceous lithology and its tropical location,
we expected DIC to be the dominant C fraction and that large changes in C concentration
and fluxes would mirror the strong seasonality.

2. Materials and Methods

2.1. The Usumacinta River
This study was carried out in the Mexican portion (medium and lower basin) of the
Usumacinta River, southeast Mexico. The Usumacinta River is part of the Usumacinta-
Grijalva Hydrological Region 30 (HR-30), which is Mexico’s most extensive river system [62]
and the tenth largest in North America [61]. HR-30 is the largest discharge in Mexico and the
second-largest overall to the Gulf of Mexico after the Mississippi River [69]. The drainage
basin is ~112,550 km2 , and the flow range is between 3000 and 6000 m3 s−1 , equivalent
to around 30% of the total surface runoff of Mexico [63,70]. The Usumacinta River basin
extends over Guatemala (58% of the total area) and Mexico (42%). It covers an area of
77,743.6 km2 between longitudes 89–92◦ W and latitudes 14–18◦ N [61]. The Usumacinta is
the largest river in Mesoamerica (~1100 km). It originates in the Sierra de Los Cuchumatanes
Mountain range in Guatemala (3800 m a.s.l), then enters Mexican territory through the
Lacandona rainforest and flows through the Mexican states of Chiapas and Tabasco. The
Grijalva River, in a parallel contiguous basin, artificially joins the Usumacinta River 15 km
before the river’s mouth at the southern Gulf of Mexico [71], forming a large (20,000 km2 )
freshwater wetland known as Pantanos de Centla Biosphere Reserve [61,69]. The mainstem
remains unimpounded and is fed by the waters released from the following catchments:
the Chixoy-Salinas (13,643 km2 ), La Pasión (11,795 km2 ), Lacantún (19,980 km2 ), and San
Pedro rivers (13,964 km2 ) [69].
The climate in the region is tropical humid, characterized by a tropical monsoon rainfall
schedule set up by a rainy season (June to November; RS; ~2500 mm yr−1 ) in summer and a
dry season (December to May; DS; ~800 mm yr−1 ) in winter [72,73]. Moreover, heavy rains
and windy episodes called nortes occur between October and March [71,74]. The climate
is controlled by the Intertropical Convergence Zone (ITCZ) and El Niño/La Niña events
that affect the Atlantic and Pacific Ocean surface temperatures [73,75]. In some areas of
 Water 2022, 14, x FOR PEER REVIEW 4 of 31

Water 2022, 14, 2703 rains and windy episodes called nortes occur between October and March [71,74].4 The of 30 cli-
mate is controlled by the Intertropical Convergence Zone (ITCZ) and El Niño/La Niña
events that affect the Atlantic and Pacific Ocean surface temperatures [73,75]. In some ar-
the eas of the highlands,
highlands, the rainfallthereaches
rainfallupreaches
to 6000up to 6000
mm, mm, considered
considered one of theone of thelevels
highest highest
levels in Mexico and Mesoamerica [71]. The average annual temperature
in Mexico and Mesoamerica [71]. The average annual temperature (~23 C) varies from ◦ (~23 °C) varies
from
◦ 8–12 °C in the Altos Cuchumatanes (Guatemala) up to
◦ 29–32
8–12 C in the Altos Cuchumatanes (Guatemala) up to 29–32 C in the lower basin [61]. °C in the lower basin
[61]. The only gauging station in the Usumacinta River basin is at Boca
The only gauging station in the Usumacinta River basin is at Boca del Cerro (Figure 1; del Cerro (Figure
1; M10).
M10). It covers
It covers a drainage
a drainage area ofarea of 47,697
47,697 km2 [76,77]
km2 [76,77] with
with an an average
average annualannual flowofrate
flow rate
2085ofm2085
3 s m[78].
− 1 3 s [78].
−1

Figure
Figure 1. Map
1. Map (left)
(left) andand diagram
diagram (right)
(right) of the
of the Usumacinta
Usumacinta River
River basin
basin indicating
indicating the the sampling
sampling
stations. (M = middle basin and B = lower basin stations). MABR = Montes Azules Biosphere Re-
stations. (M = middle basin and B = lower basin stations). MABR = Montes Azules Biosphere Reserve;
serve; SLNP = Sierra de Lacandon National Park; WS = wetland system; CWBR = Pantanos de Centla
SLNP = Sierra de Lacandon National Park; WS = wetland system; CWBR = Pantanos de Centla
Biosphere Reserve.
Biosphere Reserve.
The vegetation in the middle basin is mainly composed of tropical and subtropical
The vegetation in the middle basin is mainly composed of tropical and subtropical
forests [61].[61].
forests Recently,
Recently, the the evergreen,
evergreen, coniferous,
coniferous, andand
oakoak forests
forests thatthat covered
covered ~85%~85% of the
of the
middle basin have been reduced due to agricultural activities and extensive
middle basin have been reduced due to agricultural activities and extensive livestock [79]. livestock [79].
The lower basin is integrated with mangrove swamps, marshes, and
The lower basin is integrated with mangrove swamps, marshes, and hydrophytic vege- hydrophytic vegeta-
tion[80,81].
tation [80,81].The
Themountainous
mountainousarea area (middle)
(middle) and
and thethe coastal
coastal plain
plain (lower)
(lower) areare
thethe
main main
distinctive geomorphological units along the Usumacinta River basin
distinctive geomorphological units along the Usumacinta River basin [82]. The mountain-[82]. The mountain-
ousous region
region is composed
is composed of the
of the Sierra
Sierra de Los
de Los Cuchumatanes-Guatemala
Cuchumatanes-Guatemala (extensive
(extensive folded
folded
block of Cretaceous limestone and dolomites), the Sierra Madre de Chiapas-Mexico
block of Cretaceous limestone and dolomites), the Sierra Madre de Chiapas-Mexico (dior- (dio-
rites and granites from the Paleozoic), and the Altos de Chiapas (marine
ites and granites from the Paleozoic), and the Altos de Chiapas (marine and continental and continental
carbonates
carbonates fromfrom the Mesozoic
the Mesozoic with volcanic
with volcanic deposits
deposits from
from the the Cenozoic).
Cenozoic). The CoastalThePlain
Coastal
is a low-relief area (slope from 0 to 3%) where the river delta develops through diverse
freshwater and coastal wetlands. The landscape geology is dominated by sedimentary
Cenozoic rocks of alluvial and lacustrine origin [71,83,84]. According to Olea [85], the domi-
Water 2022, 14, 2703 5 of 30

nant chemical water type in the Usumacinta River is Ca-Mg-SO4 -HCO3 in the dry season
and Ca-Mg-HCO3 -SO4 in the rainy season.

2.2. Sampling
Two sampling campaigns were carried out, during the 2017 rainy season (October)
and the 2018 dry season (April), at 18 sampling sites covering the middle (M1 to M10)
and lower (B1 to B8) Usumacinta River basins, including the main tributaries. Sampling
sites were the Ixcán (M1) and Chajul (M2) rivers that originate in Guatemala and drain
toward the Lacantún River (M3), which receives the waters of the Tzendales River (M4).
This site is in the central part of the Montes Azules Biosphere Reserve (MABR, a protected
area within the Lacandona Forest). Additionally, sampling was conducted of the Lacantún
(M5), Chixoy (M6), La Pasión (M7), San Pedro (B1), and Grijalva (B6) rivers, as well in
the mainstem of the Usumacinta River (M8, M9, M10, B2, B3, B5, B7). Finally, the San
Pedro-San Pablo River (B4 and B8) was sampled at the lower basin, accounting for the
smaller river mouth of the Usumacinta River (Table S1; Figure 1).
A river cross-section was recorded at each site using a Garmin echo-sounder (model
GPSMap 526S Sounder). Then, three vertical profiles along the sampling section (one center
point and two more equidistant from both sides) were compiled, measuring water temper-
ature, dissolved oxygen (DO), pH, electrical conductivity at 25 ◦ C (K25 ), turbidity, and oxi-
dation/reduction potential (ORP) using a Hydrolab DS5 Multiparameter sonde equipped
with a data logger (Surveyor 4a). The DS5 probe recorded a vertical profile from the surface
to the maximum depth with a vertical resolution of one meter. The nominal precisions
were as follows: temperature ±0.10 ◦ C; DO ±0.2 mg L−1 ; pH ±0.2; K25 ±0.001 mS cm−1 ;
turbidity ±1 NTU and ORP ±20 mV. Water flow was measured at each site using a Swoffer
3000 current meter (1% accuracy). Five successive speed measurements were made of
each vertical profile at 1/3 of the maximum depth to obtain a mean representative value.
Water samples were taken from each vertical profile at 1/3 of the maximum depth for
each sampling station, using a horizontal Van Dorn bottle [42]. The water samples were
filtered in situ, and the filters were transported in dark and cold conditions until they
were analyzed at FES Iztacala Laboratory–UNAM for total suspended solids (TSS) and
chlorophyll-a (Chl-a) and at the Center for Marine Science at UNC Wilmington (for DOC,
POC, DIC).

2.3. Analytical Methods

Water samples for TSS, POC, and total particulate carbon (TPC) analysis were first
passed through a 100 µm mesh to remove large particles. Two replicates of each vertical
water profile were filtered (TSS: 200 to 2000 mL; POC and TPC: 20 to 100 mL) with a
vacuum pump (0.3 to 0.5 atm) through pre-combusted (550 ◦ C, four hours) Whatman
GF/F filters (TSS: 47 mm diameter, pore size: 0.7 µm; POC and TPC: 13 mm, 0.7 µm). TSS
concentrations were obtained gravimetrically after filter desiccation (60 ◦ C, 24 h) with a
Mass Comparator Balance (Mettler Toledo). The precision of the weight measurements was
0.1 mg. POC filters were first acidified using 10% HCl to remove carbonates before analysis
and then oven-dried (50 ◦ C, 24 h). Subsequently, the dried filters were packed in aluminum
foil for analysis on a CHN analyzer Carlo Erba NC2100. This procedure was similar for
measuring TPC, but the filters were not acidified after filtration. The difference between the
POC and TPC concentrations was assumed to be the concentration of particulate inorganic
carbon (PIC) [42].
For the DOC analysis, samples for each vertical profile were filtered in duplicate
through a GF/F (0.7 µm nominal pore size) filter previously combusted (550 ◦ C, four
hours) and stored in 40 mL amber glass vials with polytetrafluoroethylene (PTFE)-coated
septa. The filtered sample was acidified with H3 PO4 (40%) to make the pH < 2 for the
removal of DIC. DOC concentrations were analyzed with high-temperature combustion
using a Shimadzu TOC 5000 total organic carbon analyzer equipped with an ASI 5000
Water 2022, 14, 2703 6 of 30

autosampler. We also calculated the total organic carbon (TOC) as the sum of the dissolved
and particulate OC in each vertical profile.
Water samples for the DIC in each vertical profile were filtered in duplicate (GF/F;
0.7 µm) and recovered in 60 mL (BOD Wheaton) borosilicate glass bottles at once; then,
25 µL of saturated (50%) aqueous mercuric chloride (HgCl2 ) solution was added to inhibit
any biological activity. Bottles were filled (without any air left) to avoid exchanges with
ambient air CO2 and sealed with grease on the ground glass stopper. A rubber band on
the stopper was then secured with tape. DIC concentrations were analyzed in a Shimadzu
TOC 5000 Analyzer.
Triplicate water samples (20 to 100 mL) for each vertical profile were filtered (Whatman
0.7 µm GF/F) for Chl-a analysis. The pigments were extracted with 10 mL acetone (90%)
at 4 ◦ C overnight. Chl-a was analyzed in a Turner Designs TD. 10-AU fluorometer (EPA
method 445.0) [86].

2.4. Data Analysis and Statistical Methods

The water discharge (m3 s−1 ) was calculated using the area–velocity method. Instanta-
neous C fluxes of each fraction (DOC, POC, TOC, DIC, PIC) were obtained by multiplying
the measured water discharges by the corresponding C fraction concentration at each
station (t d−1 ). The total carbon (TC) was calculated as the sum of the dissolved and
particulate chemical species (TC = DOC + POC + DIC + PIC).
The mass inflow–outflow balance of C fractions in the lower basin was calculated
according to [68,87]. We calculated the difference between the last site of the middle basin
(M10, input) and the two Usumacinta River mouths (B5 and B8, output) at the lower basin
(Figure 1). We chose these sampling points because B5 represents the mainstem before its
merge with the Grijalva River (B6), and B8 is the freshwater end-member in the second
mouth after crossing the Pantanos de Centla Biosphere Reserve, as mentioned by Cuevas-
Lara [42]. Thus, the difference (M10 − (B5 + B8)) determines whether the lower basin
river stretch was either a C retention area (sink, M10 − (B5 + B8) > 0) or a source area
(M10 − (B5 + B8) < 0) for the different C fractions. However, this C balance does not
recognize the involved C processes, transformations, or fate, such as CO2 evasion or C
storage in floodplains or sediments (including outgassing to the atmosphere in the case of
DIC) [87]. Similarly, the flux difference was also expressed as a percentage of the upstream
change at Boca del Cerro (M10).
Averages, standard deviations, and ranges were calculated for each variable. We com-
puted the distance to the river mouth (Table S1) with a map projection using the WGS84
data. All variables were plotted for distance to the mouth to define longitudinal trends.
ANOVA (Shapiro–Wilk normality test passed) and the nonparametric Kruskal–Wallis
ANOVA (normality test failed) were used to assess significant differences in seasonal
variability among the physicochemical variables, C concentrations, and fluxes. The non-
parametric Spearman rank-order correlations were used to evaluate relationships between
C concentrations and environmental variables in the RS and the DS of the Usumacinta
River. All statistical analyses were performed using Sigmaplot v14.0, and an α level of 0.05
was used to determine significance.

2.5. Annual Flux Calculation

Excepting POC [42], no data are available on C transport in the Usumacinta River;
therefore, we used our database for a rough estimate of the annual dissolved and par-
ticulate C discharge following the proposed method by [50] for the Senegal River, West
Africa. We used the daily flows from Banco Nacional de Datos de Aguas Superficiales
(BANDAS) [76] of the Boca del Cerro gauging station (M10) corresponding to our study pe-
riod between July 2017 and July 2018. Additionally, the C concentration (average, minimum,
and maximum) was measured in M10 in the RS and DS. The daily Q from June to December
(high flow period) was multiplied by the C concentration of the RS. Meanwhile, the daily Q
from January to May (low flow period) was multiplied by the C concentration of the DS [50].
Water 2022, 14, 2703 7 of 30

However, due to the high flow recorded in February 2018 (see Section 3.1), the annual
average (2456 m3 s−1 ) was considered the limit for the calculation. That is, daily flow values
higher than the average were used within the RS and lower in the DS. Daily flows were
summed and expressed in Tg yr−1 . However, the Boca del Cerro (M10) gauging station
has a distance to the mouth of ~385 km, and the channel flows through a wetland and
floodplain system in the lower basin that reduces Q (see Figure S1) and modifies C loads
(see Sections 3.2 and 3.4). In addition, the Grijalva River (B6) influences the final discharge.
For these reasons, a re-estimation of the C flux was performed considering the sampling
stations at the mouth (B7 + B8). We also calculated the C yields using (t C km2 yr−1 ) Q × C
concentration/watershed area for the entire Usumacinta-Grijalva River basin. While this
approach is widely used in flux calculation for large rivers, inevitable error exists in the
estimation, mainly due to the large variability of discharge across the year.

3. Results
3.1. Discharge and Physical and Chemical Variables of the Usumacinta River
The Usumacinta River showed significant temporal variations in its environmental
variables. Tables S2 and S3 show the average values of the physical and chemical parameters
measured at the 18 sampling sites in the middle and lower basins of the Usumacinta River.
Most parameters changed significantly over the two seasons.
The Q was approximately 6 times higher during the RS (from 141 m3 s−1 to 5970 m3 s−1 )
than in the DS (from 15 m3 s−1 to 1080 m3 s−1 ), with significant differences between
sampling campaigns (H = 9.42; p = 0.002). Q in the mainstem evidenced an increasing
trend in the middle basin and a decrease toward the mouth (Figure S1). Comparing the Q
of Boca del Cerro (M10) with the mainstem of the lower basin and San Pedro-San Pablo
(B5 + B8), the Q decreased ~49% in the RS and ~18% in the DS (Tables S2 and S3). However,
the Grijalva River (B6) inflow increased Q (50% in the RS and 35% in the DS; Figure S1).
The final discharge (B7 + B8) from the Usumacinta River to the Gulf of Mexico was five
times greater in the rainy (5748 m3 s−1 ) than in dry seasons (1194 m3 s−1 ).
Based on the gauging data recorded at Boca del Cerro (M10) [76], we constructed the
hydrograph from July 2017 to July 2018 (Figure 2). The average flow for this period was
2456 m3 s−1 and ranged from 678 m3 s−1 (8 May 2018) to 6722 m3 s−1 (30 October 2017).
The discharge in the RS (5970 m3 s−1 ) doubled the historical average for the rainy season
Water 2022, 14, x FOR PEER REVIEW(~2851 m3 s−1 ). The flow at DS (998 m3 s−1 ) was ~1.5 times higher than the historical
8 of 31 Q for
3 −
this season (~678 m s ). 1

Figure 2. Variations in the historical (1948–2014) average daily flow (grey area) and the 2017 (RS) to
Figure 2. Variations in the historical (1948–2014) average daily flow (grey area) and the 2017 (RS) to
2018 (DS) flow measured at the hydrometric station at Boca del Cerro (M10), Tabasco.
2018 (DS) flow measured at the hydrometric station at Boca del Cerro (M10), Tabasco.
High water temperatures (mean 26.5 ± 2.3 °C) prevailed in both sampling campaigns,
ranging between 20.8 °C (M1, RS) and 29.8 °C (M7, DS). The DO of the Usumacinta River
ranged from 1.4 mg L−1 (B6, RS) to 10.8 mg L−1 (M1, DS), with a mean of 6.8 ± 2.4 mg L−1.
The pH was slightly alkaline, from 7.3 (M7, RS) to 8.3 (M2, DS) with an average of 7.8 ±
0.3. Overall, the Usumacinta River behaved as an oxidizing environment (349 ± 43 mV)
Water 2022, 14, 2703 8 of 30

Average water temperature (H = 20.5, p < 0.001), DO (H = 10.4, p = 0.001), pH (F = 12.7,

p = 0.001), and electrical conductivity (H = 20.8, p < 0.001) were higher in the DS than in the
RS (Tables S2 and S3). Meanwhile, ORP (H = 37.3, p < 0.001), and TSS (H = 17.2, p < 0.001)
concentrations were higher in the RS. Similarly, all sampling stations had significantly
higher turbidity in the RS than the DS, except B3 (Usumacinta and San Pedro confluence;
U = 1213, p = 0.112) and B8 (San Pedro-San Pablo; U = 433, p = 0.260). Chlorophyll-a
concentration was higher in the DS (p < 0.05) in all sampling sites, except in Lacantún (M3;
p = 0.5), Chixoy (M6; p = 0.5), and the Usumacinta-Grijalva confluence (B7; p = 0.29).
High water temperatures (mean 26.5 ± 2.3 ◦ C) prevailed in both sampling cam-
paigns, ranging between 20.8 ◦ C (M1, RS) and 29.8 ◦ C (M7, DS). The DO of the Usumac-
inta River ranged from 1.4 mg L−1 (B6, RS) to 10.8 mg L−1 (M1, DS), with a mean of
6.8 ± 2.4 mg L−1 . The pH was slightly alkaline, from 7.3 (M7, RS) to 8.3 (M2, DS) with an
average of 7.8 ± 0.3. Overall, the Usumacinta River behaved as an oxidizing environment
(349 ± 43 mV) and ranged from 226 mV (M4, DS) to 428 mV (M10, RS). Electrical conduc-
tivity (K25 ) ranged from 241 µS cm−1 (M2, RS) to 37,144 µS cm−1 (B8, DS) with an average
of 375 ± 109 µS cm−1 in the RS and 6117 ± 11,325 µS cm−1 in the DS. K25 showed behavior
associated with seawater intrusion in the closest stations to the river’s mouths and only in
the DS. In the RS, K25 did not exceed 1000 µS cm−1 at any site.
The turbidity measurements show a wide range, between 5 NTU (B1, RS) and 102 NTU
(M1, RS) and averaging 48 ± 23 NTU. The Usumacinta River TSS concentration
(42.4 ± 36.6 mg L−1 ) ranged from 3.2 mg L−1 (M4, DS) to 119.0 mg L−1 (M3, RS). The con-
centration of TSS in the mainstem decreases downstream in both seasons (Tables S2 and S3).
Chlorophyll-a concentrations ranged between 0.12 µg L−1 (M4; RS) and 13.4 µg L−1
(B8, DS), with a mean of 1.8 ± 1.40 µg L−1 in the RS and 3.24 ± 3.30 µg L−1 in the DS. There
was a significant Chl-a concentration increasing trend following the distance to the river
mouth in both seasons (Tables S2 and S3, and Figure S2).

3.2. Temporal and Spatial Variation of Carbon Concentration

Table 1 shows the average concentrations of DOC, POC, TOC, DIC, and PIC measured
at the 18 sampling sites in the middle and lower basins of the Usumacinta River.

Table 1. Carbon concentrations at the Usumacinta River sampling stations during the rainy (RS) and
dry seasons (DS). (For all variables, the average is in the first grey row, and the standard deviation is
in the second, “-” indicates no data).

DOC (mg L−1 ) POC (mg L−1 ) TOC (mg L−1 ) DIC (mg L−1 ) PIC (mg L−1 )
Code
RS DS RS DS RS DS RS DS RS DS
1.10 0.88 1.74 0.35 2.85 1.23 23.69 26.84 1.42 0.05
M1
0.01 0.02 0.38 0.05 0.36 0.07 0.23 1.26 0.18 0.04
1.34 1.44 2.02 0.21 3.36 1.64 22.91 15.59 1.51 0.12
M2
0.34 0.49 0.63 0.01 0.29 0.48 0.11 0.15 0.38 0.10
1.54 1.30 3.78 0.36 5.32 1.66 34.25 31.64 1.38 0.09
M3
0.60 0.10 0.73 0.08 0.78 0.07 0.99 0.21 0.53 0.04
1.39 1.00 1.27 0.30 2.67 1.30 47.19 35.19 0.27 0.08
M4
0.07 0.18 0.06 0.02 0.07 0.15 0.17 2.85 0.19 0.01
1.98 0.96 2.32 0.27 4.30 1.23 31.41 31.38 1.42 0.07
M5
0.06 0.11 0.73 0.02 0.64 0.06 5.82 0.56 0.27 0.01
2.72 1.82 1.27 0.97 3.96 2.79 23.38 23.83 1.17 0.24
M6
0.15 0.22 0.26 0.17 0.34 0.16 1.54 3.25 0.25 0.09
4.68 1.50 0.44 0.36 5.12 1.87 31.13 48.27 0.09 0.06
M7
0.22 0.21 0.05 0.05 0.11 0.13 2.47 0.29 0.06 0.03
3.72 1.66 1.02 0.79 4.74 2.44 28.63 36.11 0.71 0.18
M8
0.49 0.23 0.09 0.17 0.42 0.16 0.94 1.51 0.35 0.14
2.78 1.82 1.07 0.89 3.86 2.71 28.34 28.76 0.25 0.17
M9
0.26 0.51 0.15 0.09 0.17 0.50 0.93 1.67 0.10 0.10
Water 2022, 14, 2703 9 of 30

Table 1. Cont.

DOC (mg L−1 ) POC (mg L−1 ) TOC (mg L−1 ) DIC (mg L−1 ) PIC (mg L−1 )
Code
RS DS RS DS RS DS RS DS RS DS
3.00 1.45 0.96 0.61 3.97 2.06 31.16 37.58 0.48 0.26
M10
0.13 0.32 0.05 0.03 0.19 0.22 0.28 1.31 0.42 0.10
7.11 3.26 0.64 0.75 7.75 4.02 29.91 37.44 0.11 -
B1
0.32 0.40 0.04 0.02 0.29 0.38 0.44 0.50 0.03 -
3.02 1.60 1.09 0.93 4.14 2.53 30.16 38.58 0.48 0.14
B2
0.16 0.08 0.42 0.12 0.35 0.22 0.95 0.05 0.16 0.15
3.18 1.87 0.81 0.85 4.04 2.71 30.59 39.96 0.38 0.16
B3
0.59 0.41 0.17 0.08 0.62 0.30 0.14 0.71 0.31 0.07
3.73 1.94 1.40 1.18 5.13 3.12 30.80 35.61 0.32 0.40
B4
0.06 0.12 0.02 0.26 0.08 0.14 0.0 1.51 0.09 0.08
3.30 1.62 1.62 0.79 4.92 2.41 29.86 34.52 0.27 0.26
B5
0.26 0.30 0.54 0.18 0.41 0.14 0.26 3.37 0.30 0.10
5.23 2.02 2.42 0.60 7.65 2.63 29.04 31.74 0.37 0.22
B6
0.35 0.29 0.44 0.07 0.43 0.30 1.07 0.06 0.10 0.05
4.73 1.62 2.57 0.52 7.30 2.15 29.17 31.27 0.53 0.10
B7
0.70 0.22 1.00 0.09 1.70 0.19 0.19 2.26 0.29 0.05
6.90 2.86 2.24 1.45 9.14 4.31 30.50 31.61 0.82 0.21
B8
0.87 0.52 0.46 0.16 0.50 0.19 0.13 1.55 0.41 0.01
Average 3.42 1.70 1.59 0.68 5.01 2.38 30.12 33.11 0.67 0.17
SD 1.77 0.60 0.84 0.34 1.81 0.86 5.20 6.99 0.49 0.09
Minimum 1.10 0.88 0.44 0.21 2.67 1.23 22.91 15.59 0.09 0.05
Maximum 7.11 3.26 3.78 1.45 9.14 4.31 47.19 48.27 1.51 0.40

3.2.1. Dissolved Organic Carbon

During the RS, the DOC concentration averaged 3.42 ± 1.77 mg L−1 (n = 71), with the
minimum recorded in the Ixcán River (M1; 1, 1 ± 0.01 mg L−1 ) and the maximum in the San
Pedro River (B1; 7.11 ± 0.32 mg L−1 ). There was an increasing trend of DOC downstream
(r2 = 0.47; p < 0.005; Table 1; Figure 3a), with the highest values in the La Pasión (M7), San
Pedro (B1), and San Pedro-San Pablo (B8) rivers. There were significant positive correlations
between DOC and temperature (r = 0.95, p < 0.001), Chl-a concentration (r = 0.83, p < 0.001)
and ORP (r = 0.64, p < 0.001), as well as inverse correlations with DO (r = −0.89, p < 0.001),
pH (r = −0.85, p < 0.001), and turbidity (r = −0.57, p = 0.01). During the DS, the DOC
average concentration was significantly (H = 9.6, p = 0.002) lower (1.7 ± 0.59 mg L−1 ;
n = 83) compared to the RS. The minimum and maximum values were found in the Ixcán
(M1; 0.88 ± 0.02 mg L−1 ) and the San Pedro rivers (B1; 3.26 ± 0.4 mg L−1 ). DOC correlates
positively with Chl-a concentration (r = 0.52, p = 0.02), TSS (r = 0.69, p < 0.01) and the K25
(r = 0.52, p = 0.02), and inversely with the DO (r = −0.63, p < 0.01). The DOC increased
downstream, but the longitudinal trend was weaker compared with the RS (r2 = 0.33,
p < 0.05; Figure 3a).
The DOC concentration of the mainstem (M6, M8, M9, M10, B2, B3, B5, and B7) of
both seasons was positively correlated with the discharge (r = 0.53, p < 0.005), and it is
adjusted to a linear regression (y = 1.46 + 0.0004x; r2 = 0.67, p < 0.001; Figure 3b).
 average concentration was significantly (H = 9.6, p = 0.002) lower (1.7 ± 0.59 mg L−1; n = 83)
compared to the RS. The minimum and maximum values were found in the Ixcán (M1;
0.88 ± 0.02 mg L−1) and the San Pedro rivers (B1; 3.26 ± 0.4 mg L−1). DOC correlates posi-
tively with Chl-a concentration (r = 0.52, p = 0.02), TSS (r = 0.69, p < 0.01) and the K25 (r =
Water 2022, 14, 2703 0.52, p = 0.02), and inversely with the DO (r = −0.63, p < 0.01). The DOC increased down-
10 of 30
stream, but the longitudinal trend was weaker compared with the RS (r2 = 0.33, p < 0.05;
Figure 3a).

Figure
Figure3.3.(a)
(a)Longitudinal
Longitudinalvariations
variationsinin
the DOC
the concentration
DOC (±SD)
concentration according
(±SD) to distance
according fromfrom
to distance the
Usumacinta River’s mouth during the rainy (RS) and dry (DS) seasons; (b) DOC adjustment regard-
the Usumacinta River’s mouth during the rainy (RS) and dry (DS) seasons; (b) DOC adjustment
ing discharge into the mainstem of the Usumacinta River in the rainy (RS) and dry (DS) seasons.
regarding discharge into the mainstem of the Usumacinta River in the rainy (RS) and dry (DS) seasons.
The mainstem differs in both seasons from the tributaries.
The mainstem differs in both seasons from the tributaries.

3.2.2.The DOC concentration

Particulate of the mainstem (M6, M8, M9, M10, B2, B3, B5, and B7) of
Organic Carbon
both seasons was positively correlated with the discharge (r = 0.53, p < −0.005), and it is
During the RS, the POC registered an average of 1.59 ± 0.85 mg L 1 (n = 72), with
adjusted to a linear regression (y = 1.46 + 0.0004x; r2 = 0.67, p <−10.001; Figure 3b).
the minimum in the La Pasión River (M7; 0.44 ± 0.05 mg L ) and the maximum in the
Lacantún River (M3; 3.78 ± 0.73 mg L−1 ). There was only a positive correlation of POC
3.2.2. Particulate Organic Carbon
with turbidity (r = 0.63, p < 0.01) and TSS (r = 0.7, p < 0.001). The POC in the RS was adjusted
During the
to a quadratic RS, the(rPOC
function registered
2 = 0.42, anFigure
p < 0.05; average4a)ofconcerning
1.59 ± 0.85the L−1 (n = 72),
mgdistance with
to the the
mouth.
minimum in the La Pasión River (M7; 0.44 ± 0.05 mg L −1) and the maximum in the La-
The maximum values were in the Lacantún River and tributaries (M1, M2, M3, and M5),
Water 2022, 14, x FOR PEER REVIEW 11 of 31
cantún Riverhigh
which have (M3;turbidity
3.78 ± 0.73
andmgTSS.
L−1).Downstream,
There was only POC a positive
increasescorrelation of POC
in the stations with
near the
turbidity (r = (B5,
river mouth 0.63,B6,
p <B7,
0.01)
andand
B8;TSS (r =1;0.7,
Table p < 0.001).
Figure 4a). The POC in the RS was adjusted to
a quadratic function (r2 = 0.42, p < 0.05; Figure 4a) concerning the distance to the mouth.
The maximum values were in the Lacantún River and tributaries (M1, M2, M3, and M5),
which have high turbidity and TSS. Downstream, POC increases in the stations near the
river mouth (B5, B6, B7, and B8; Table 1; Figure 4a).

Figure4.4.(a)
Figure (a)Longitudinal
Longitudinalvariations
variationsininthe
thePOC concentration(±
POCconcentration SD) according
(±SD) according totodistance
distanceto
tothe
the
Usumacinta River’s mouth during the rainy (RS) and dry (DS) seasons; (b) POC ( ± SD)
Usumacinta River’s mouth during the rainy (RS) and dry (DS) seasons; (b) POC (±SD) adjustment adjustment
regardingtotal
regarding totalsuspended
suspendedsolids
solidsconcentration
concentrationin inthe
theUsumacinta
UsumacintaRiver
Riverininthe
therainy
rainy(RS)
(RS)and
anddry
dry
(DS) seasons. The mainstem differs in both seasons from the tributaries.
(DS) seasons. The mainstem differs in both seasons from the tributaries.

The POC concentration was significantly lower (H = 15.1, p < 0.001) in the DS (0.68 ±
0.34 mg L−1; n = 85) compared with the RS. The minimum and maximum values were
found in the Chajul River (M2; 0.21 ± 0.01 mg L−1) and the San Pedro-San Pablo River (B8;
1.45 ± 0.16 mg L−1), respectively. The POC in the DS increased downstream (r2 = 0.38, p <
0.01; Figure 4a) and presented positive correlations with the Chl-a concentration (r = 0.78,
p < 0.001), TSS (r = 0.73, p < 0.001), DOC (r = 0.74, p < 0.001), and ORP (r = 0.6, p < 0.01).
Water 2022, 14, 2703 11 of 30

The POC concentration was significantly lower (H = 15.1, p < 0.001) in the DS (0.68
± 0.34 mg L−1 ; n = 85) compared with the RS. The minimum and maximum values
were found in the Chajul River (M2; 0.21 ± 0.01 mg L−1 ) and the San Pedro-San Pablo
River (B8; 1.45 ± 0.16 mg L−1 ), respectively. The POC in the DS increased downstream
(r2 = 0.38, p < 0.01; Figure 4a) and presented positive correlations with the Chl-a concentra-
tion (r = 0.78, p < 0.001), TSS (r = 0.73, p < 0.001), DOC (r = 0.74, p < 0.001), and ORP (r = 0.6,
p < 0.01).
In both seasons, POC showed a high dependence on the TSS concentration (r2 = 0.65,
p < 0.001; Figure 4b). The %POC (content in the TSS) in the Usumacinta River varied
between 1.3% and 13.4% and was significantly (H = 11.5, p < 0.001) lower during the RS
(2.9 ± 2.0%) compared with the DS (5.7 ± 3%). The variation that explains 60% of the
variance of the % POC and TSS was fitted to a logarithmic function (Table S4; Figure S3).
The POC/Chl-a (mg C mg Chl-a−1 ) ratio fluctuated between 107 and 10,362 (~1464
± 2605), with significantly higher values (H = 8.7, p = 0.003) during the RS (Table S4).
The POC/Chl-a ratio showed a decreasing trend until the river’s mouth in a linear manner,
both in the RS (r2 = 0.34, p < 0.05), and in the DS (r2 = 0.51, p < 0.001; Figure S4).

3.2.3. Total Organic Carbon

The TOC concentration during the RS ranged from 2.67 ± 0.07 mg L−1 in the Tzendales
River (M4) to 9.14 ± 0.50 mg L−1 in the San Pedro-San Pablo River (B8), with an average of
5.01 ± 1.84 mg L−1 . A positive correlation was found with temperature (r = 0.75, p < 0.001),
Chl-a (r = 0.71, p < 0.001), DO (r = −0.66, p < 0.01), and pH (r = −0.6, p < 0.01). During the DS,
the TOC concentration was significantly (H = 19.9, p < 0.001) lower (2.38 ± 0.86 mg L−1 )
than the RS. The minimum and maximum values were found at the confluence of the
Lacantún with the Tzendales River (M5; 1.23 ± 0.06 mg L−1 ) and the San Pedro-San Pablo
River (B8; 4.31 ± 0.19 mg L−1 ), respectively. In the DS, TOC was significantly correlated
with TSS (r = 0.77, p < 0.001), Chl-a (r = 0.75, p < 0.001), and DO (r = −0.53, p < 0.05).
As shown in Figure 5a, TOC concentration increased downstream in both seasons,
although the mainstem stations had a relatively constant concentration of TOC down-
stream. DOC was the most abundant TOC fraction in the Usumacinta River (Table S4).
DOC represents ~66 ± 17% (29 to 92%) of TOC in the RS and ~72 ± 7% (62 to 87%) in the
DS. During the RS, the POC in the Lacantún River (M3 and M5) and the Ixcán (M1), Chajul
(M2), and Tzendales (M4) tributaries was the dominant fraction, while in the DS at the
same stations, this proportion changed, dominated by the dissolved fraction (Figure 5b). In
the middle (M6-M10) and lower basin (B1-B8), the DOC/POC ratio was >1, both for the
RS (1.84–11.07) and for the DS (1.64–4.33), which shows that DOC is the main organic C
fraction (Table S4). Additionally, the DOC/POC ratio was not statistically different between
seasons (H = 0.4, p = 0.53). It did not present a longitudinal variation (p > 0.05) from the
middle basin to the mouth in any sampling season.
 same stations, this proportion changed, dominated by the dissolved fraction (Figure 5b).
In the middle (M6-M10) and lower basin (B1-B8), the DOC/POC ratio was >1, both for the
RS (1.84–11.07) and for the DS (1.64–4.33), which shows that DOC is the main organic C
fraction (Table S4). Additionally, the DOC/POC ratio was not statistically different be-
Water 2022, 14, 2703 12 of 30
tween seasons (H = 0.4, p = 0.53). It did not present a longitudinal variation (p > 0.05) from
the middle basin to the mouth in any sampling season.

Figure5.
Figure 5. (a)
(a) Longitudinal
Longitudinalvariations
variationsin
inthe
theTOC
TOCconcentration
concentration(±(±SD) according to
SD) according to distance
distance from
from the
the
UsumacintaRiver’s
Usumacinta River’smouth
mouthduring
duringthe
therainy
rainy(RS)
(RS)and
and dry
dry (DS)
(DS) seasons;
seasons; (b)(b) longitudinal
longitudinal variations
variations in
in the
the DOC/POC
DOC/POC ratio
ratio according
according to distance
to distance fromfrom the mouth
the mouth of theofUsumacinta
the Usumacinta
River River
duringduring the
the rainy
rainy (RS) and dry (DS) seasons. The mainstem differs in both seasons from the tributaries.
(RS) and dry (DS) seasons. The mainstem differs in both seasons from the tributaries.

3.2.4. Dissolved
3.2.4. Dissolved Inorganic
Inorganic Carbon
Carbon
During the RS, the
During the average
average concentration
concentrationofofDIC DICwaswas30.1 ± 5.2
30.1± 5.2 mgmg (n−=1 43),
L−1 L (n =with
43),
with the minimum
the minimum valuevalue
in theinChajul
the Chajul
RiverRiver
(M2; (M2; 22.9Lmg
22.9 mg −1 − 1
L )the
) and and the maximum
maximum in the in the
Tzen-
Tzendales River −1 ). In the RS, there was only a positive correlation between
dales River (M4;(M4;
47.247.2
mg L mg−1).LIn the RS, there was only a positive correlation between DIC
DIC
and and
K25 (rK=250.74,
(r = p0.74, p < 0.001).
< 0.001). For the For the
DS, theDS,DICtheaverage
DIC average concentration
concentration was slightly
was slightly higher
−1 ; n = 35), with the minimum in the Chajul River (M2; 15.6
higher
(33.1 ±(33.1
7.0 mg ± 7.0
L−1;mg
n =L35), with the minimum in the Chajul River (M2; 15.6 mg L−1)mg andL− 1)
the
and the maximum in Pasión
the La Pasión River48.3
(M7;mg 48.3 − 1
maximum in the La River (M7; L−1mg L ) (Table
) (Table 1; Figure1; Figure
6a). In6a).
theIn thethere
DS, DS,
there was a positive correlation between DIC and temperature
was a positive correlation between DIC and temperature (r = 0.66, p = 0.001). (r = 0.66, p = 0.001). The DIC
DIC
concentration
concentrationin inthe
thetwotwoseasons
seasonswas wasstatistically
statisticallydifferent
different(H 6.56,pp<< 0.01)
(H==6.56, 0.01) and
and did
did not
not
vary
vary longitudinally
longitudinally (p (p >>0.1;
0.1;Figure
Figure6a).6a).InInaddition,
addition, with
with a 95%
a 95% confidence
confidence interval
interval for for
the
the −1
datadata
meanmean (n (n = 36),DIC
= 36), DICvalues
valuesfluctuated
fluctuatedbetween
between 29.9
29.9 and
and 31.7
31.7 mg
mgLL−1.. The
The mean
mean
DIC/DOC
DIC/DOC ratio ratiowas
wassignificantly
significantlylower lower(H(H= 12.6, p <p0.001)
= 12.6, < 0.001) during
during the the ± 7.7)±com-
RS (11.7
RS (11.7 7.7)
compared with the DS (21.4 ± 7.7). In both seasons, there was a
pared with the DS (21.4 ± 7.7). In both seasons, there was a decrease in DIC/DOC ratios decrease in DIC/DOC
ratios
toward toward the river’s
the river’s mouthmouth(Table(Table S4; Figure
S4; Figure S5). S5).
3.2.5. Particulate Inorganic Carbon
The average concentration of PIC was higher in the RS (0.67 ± 0.49 mg L−1 ) and
lower in the DS (0.17 ± 0.09 mg L−1 ), with statistically significant differences between
sampling campaigns (H = 16.2, p < 0.001). During the RS, we measured the maximum
(1.51 ± 0.38 mg L−1 ) in the Chajul River (M2) and the minimum in the La Pasión River
(M7; 0.09 ± 0.06 mg L−1 ). PIC presented a decreasing trend downstream (r2 = 0.29, p < 0.05)
in the RS, but in the DS, PIC increased downstream (r2 = 0.34, p < 0.05; Table 1; Figure 6b).
The concentration of PIC was not related to the variation in the river flow in any season
(p > 0.05), but it presents the same pattern of variation as the TSS (Figure S6). DIC was
the dominant inorganic C in the Usumacinta River. It represents almost entirely dissolved
inorganic C (97.7 ± 1.8% during the RS and 99.5 ± 0.3% in the DS).
Water
Water2022, 14,14,
2022, 2703
x FOR PEER REVIEW 1313
ofof3130

Figure 6. (a) Longitudinal variations in the DIC and (b) PIC concentrations (±SD) according to the
distance to the Usumacinta River’s mouth during the rainy (RS) and dry (DS) seasons. The mainstem
differs in both seasons from the tributaries.

3.2.5. Particulate Inorganic Carbon

The average concentration of PIC was higher in the RS (0.67 ± 0.49 mg L−1) and lower
in the DS (0.17 ± 0.09 mg L−1), with statistically significant differences between sampling
campaigns (H = 16.2, p < 0.001). During the RS, we measured the maximum (1.51 ± 0.38
mg L−1) in the Chajul River (M2) and the minimum in the La Pasión River (M7; 0.09 ± 0.06
mg L−1). PIC presented a decreasing trend downstream (r2 = 0.29, p < 0.05) in the RS, but in
the DS, PIC increased downstream (r2 = 0.34, p < 0.05; Table 1; Figure 6b). The concentra-
tion of PIC was not related to the variation in the river flow in any season (p > 0.05), but it
presents the same pattern of variation as the TSS (Figure S6). DIC was the dominant inor-
Figure6.6.(a)
Figure (a)Longitudinal
Longitudinal variations
variations in
in the
the DIC
DIC and
and (b)
(b) PIC
PIC concentrations
concentrations (±SD)
(±SD)according
accordingtotothe
the
ganic Ctointhe
distance theUsumacinta
Usumacinta River.
River’s It represents
mouth almost(RS)
during the entirelydry
dissolved inorganic C (97.7
distance to the Usumacinta River’s mouth during the rainy
rainy (RS) and
and dry(DS)
(DS)seasons.
seasons.The
Themainstem
mainstem
± 1.8%induring
differs the RSfrom
both seasons andthe
99.5 ± 0.3% in the DS).
tributaries.
differs in both seasons from the tributaries.
3.2.6.Total
3.2.5.
3.2.6. TotalCarbon
Carbon
Particulate Inorganic Carbon
DIC
DIC was
The was the
average dominantfraction
the dominant fraction
concentration inin
of PIC both
was
both sampling
higher in the
sampling seasons,
RS (0.67
seasons, followedby by
± 0.49 mg
followed L−1DOC,
DOC,) and POC,
lower
POC, and
and finally
in the PIC
finally PIC
DS (0.17 (DIC
(DIC±>0.09
DOC>
mgDOC >POC
L ), with
>POC
−1 >
> PIC) PIC) (Figure
statistically 7).
(Figure 7).significant differences between sampling
campaigns (H = 16.2, p < 0.001). During the RS, we measured the maximum (1.51 ± 0.38
(a) mg L−1) in the Chajul River (M2) and the(b)minimum in the La Pasión River (M7; 0.09 ± 0.06
mg L−1). PIC presented a decreasing trend downstream (r2 = 0.29, p < 0.05) in the RS, but in
the DS, PIC increased downstream (r2 = 0.34, p < 0.05; Table 1; Figure 6b). The concentra-
tion of PIC was not related to the variation in the river flow in any season (p > 0.05), but it
presents the same pattern of variation as the TSS (Figure S6). DIC was the dominant inor-
ganic C in the Usumacinta River. It represents almost entirely dissolved inorganic C (97.7
± 1.8% during the RS and 99.5 ± 0.3% in the DS).

3.2.6. Total Carbon

DIC was the dominant fraction in both sampling seasons, followed by DOC, POC,
and finally PIC (DIC > DOC >POC > PIC) (Figure 7).

(a) (b)

Figure7.7.Percentage
Figure Percentagevariations
variations in
in C
C chemical
chemical fractions
fractions in
in the
the Usumacinta
UsumacintaRiver
Riverduring
duringthe
the(a)
(a)rainy
rainy
and (b) dry seasons.
and (b) dry seasons.

In the RS, the DIC averaged ~84 ± 4% (between 75% and 94%), followed by DOC
(average of ~9.5 ± 4.5%, between 3% and 19%) and particulate fractions. However, in the
Ixcán (M1) and the Chajul (M2) rivers, particulate C fractions were more abundant than
DOC (DIC > POC > PIC > DOC). POC was the dominant organic fraction (DIC > POC >
DOC > PIC) only in the Lacantún River (M3) and at the confluence with the Tzendales
River (M5; Figure 7a). During the DS, the DIC averaged ~92.7 ± 2.6% (between 87% and
96%), followed by the DOC with ~4.9% ± 1.8% (between 3 and 7.9%). The particulate
fractions measured a lower percentage (average of 1.9 ± 0.9% for the POC and ~0.5 ± 0.3%
for the PIC; Figure 7b).
Figure 7. Percentage variations in C chemical fractions in the Usumacinta River during the (a) rainy
and (b) dry seasons.
Water 2022, 14, 2703 14 of 30

3.3. Instantaneous Carbon Fluxes

Calculated C fluxes were significantly higher in the RS: TOC (H = 15.8, p < 0.001), DOC
(H = 14.1, p < 0.001), POC (H = 13.2, p < 0.001), and DIC (H = 9.2, p = 0.002). In addition, C
fluxes showed a high correlation with Q (r = 0.9, p < 0.001), demonstrating that C export is
highly conditioned by water discharge rather than by the concentration of each C fraction.
Table S5 shows the averages (±SD) of the DOC, POC, TOC, and DIC fluxes calculated at
the 18 sampling sites of the Usumacinta River.
During the RS, the mean TOC flux (1032 ± 956 t d−1 ) was two orders of magnitude
higher than in the DS (93 ± 84 t d−1 ). Notably, in the La Pasión River sub-basin (M7), the
TOC flux was ~20 times greater in the RS than in the DS. The DOC flux represents ~66 to
72% of the TOC flux (Table S4). However, in the Lacantún River (M1-M5), POC represents
~70%, although during the DS, the DOC flux is again dominant (~71% to 87%). The Chixoy
(M6) and San Pedro (B1) rivers are the tributaries that contribute the highest and lowest OC
loads, respectively (Table S5). Specifically in the DS, the Chixoy River (M6) has a TOC flux
contribution ~four times higher than the other major tributaries. The highest OC fluxes
during the RS occurred at the confluence of the Grijalva River (B7) with the Usumacinta
River, despite having a lower Q than the Boca del Cerro station (M10; Table S2). In the DS,
the maximum OC flux occurs at the confluence of the San Pedro River (B3; highest flow
measured) with the Usumacinta River and decreases until the river’s mouth.
DIC flux accounted for the most significant percentage of total C load in both the
RS (~84 ± 4%) and the DS (~93 ± 3%). The Chixoy River sub-basin (M6) contributed
the highest amount of DIC flux into the mainstem in both the RS and DS. However, DIC
transport was ~6 times higher in the rainy season (Table S5) even though the concentration
measured between both seasons was practically similar (23.4 mg L−1 versus 23.8 mg L−1 ).
This behavior corroborates the importance of hydrology in transport. The Tzendales River
(M4) has peculiar comportment because DIC flux was ~15 times higher in the RS (Table S5)
compared with the remaining stations (~5 times more). In addition, M4 transported the
highest percentage of DIC (94% at RS and 96% at DS) relative to the OC fractions.

3.4. C Balance in the Lower Basin of the Usumacinta River

The C inflow–outflow mass balance in the RS was positive for all C species, showing
net retention (C sink) within the river reach. DOC, POC, TOC and DIC fluxes decreased
downstream with respect to Boca del Cerro (M10), approximately ~36%, ~9%, ~30%, and
~50%, respectively (Table 2).

Table 2. Balance of water discharge (Q) and C fluxes in the Usumacinta River basin and the total C
export to the Gulf of Mexico in the rainy (RS) and dry (DS) seasons. (See Figure 1 and Table S1 for the
detailed locations of the sampling sites).

Q DOC Flux POC Flux TOC Flux DIC Flux

Code (m3 s−1 ) (t d−1 ) (t d−1 ) (t d−1 ) (t d−1 )
RS DS RS DS RS DS RS DS RS DS
Input M10 5970 998 1549.0 124.8 497.7 52.8 2046.8 177.7 16,073.4 3240.4
B5 2709 677 771.8 94.6 380.0 46.0 1151.8 140.6 6988.9 2018.0
Output
B8 368 146 219.7 36.0 71.2 18.3 290.9 54.3 970.4 398.5
Balance (input−output) M10 − (B5 + B8) 2893 175 557.5 −5.8 46.5 −11.5 604.1 −17.2 8114.1 823.9
Usumacinta basin export B5 + B8 3077 823 991.5 130.6 451.2 64.3 1442.7 194.9 7959.3 2416.5
Usumacinta-Grijalva B7 5380 1048 2198.8 146.9 1192.9 47.5 3391.8 194.4 13,557.9 2830.2
Usumacinta-Grijalva
B7 + B8 5748 1194 2418.5 182.9 1264.1 65.8 3682.7 248.7 14,528.3 3228.7
basin export

In contrast, in the DS, the balance was negative. DOC, POC, and TOC fluxes increased
(~5%, ~22%, and ~10%, respectively) from the middle basin (M10) to the lower basin (B5
plus B8). Differently, the DIC flux in the DS decreased ~25% concerning the gauging station
 RS DS RS DS RS DS RS DS RS DS
Input M10 5970 998 1549.0 124.8 497.7 52.8 2046.8 177.7 16,073.4 3240.4
B5 2709 677 771.8 94.6 380.0 46.0 1151.8 140.6 6988.9 2018.0
Output
B8 368 146 219.7 36.0 71.2 18.3 290.9 54.3 970.4 398.5
Balance (input − output) M10 − (B5 + B8) 2893 175 557.5 −5.8 46.5 −11.5 604.1 −17.2 8114.1 823.9
Water 2022, 14, 2703 15 of 30
Usumacinta basin export B5 + B8 3077 823 991.5 130.6 451.2 64.3 1442.7 194.9 7959.3 2416.5
Usumacinta-Grijalva B7 5380 1048 2198.8 146.9 1192.9 47.5 3391.8 194.4 13,557.9 2830.2
Usumacinta-Grijalva basin export B7 + B8 5748 1194 2418.5 182.9 1264.1 65.8 3682.7 248.7 14,528.3 3228.7
M10 (Table 2). The lower Usumacinta River basin is a sink for DIC in both seasons, with
this function being greater in the RS.
The Grijalva River (B6) contributes significant amounts of C to the Usumacinta River
The Grijalva River (B6) contributes significant amounts of C to the Usumacinta River
that further discharges to the southern Gulf of Mexico. During the RS, the daily fluxes of
that further discharges to the southern Gulf of Mexico. During the RS, the daily fluxes
DOC, POC, TOC, and DIC from the Grijalva River (B6) represents ~59%, ~64%, ~61%, and
of DOC, POC, TOC, and DIC from the Grijalva River (B6) represents ~59%, ~64%, ~61%,
~45%,
and respectively,
~45%, of theofdischarge
respectively, of theof
the discharge entire basin (B7
the entire + B8;
basin (B7Table
+ B8;2;Table
Figure
2; 8a). On 8a).
Figure the
contrary, in the DS, the percentage of the Grijalva River (B6) contribution decreases
On the contrary, in the DS, the percentage of the Grijalva River (B6) contribution decreases sub-
stantially, with
substantially, ~29%,
with ~2%,
~29%, ~22%,
~2%, and and
~22%, ~5%~5%
of the
of DOC, POC,
the DOC, TOC,
POC, andand
TOC, DICDICfluxes, re-
fluxes,
spectively (Table 2; Figure 8b).
respectively (Table 2; Figure 8b).

Figure 8. Application of the conceptual framework to the carbon flux (t d−1) balance during the (a)
Figure 8. Application of the conceptual framework to the carbon flux (t d−1 ) balance during the
rainy and (b) dry seasons in the lower basin of the Usumacinta River. The widths of the lines, pro-
(a) rainy and (b) dry seasons in the lower basin of the Usumacinta River. The widths of the lines,
portional to the magnitude of the fluxes, are consistent within one season but not between the dif-
proportional to the magnitude of the fluxes, are consistent within one season but not between the
ferent seasons.
different seasons.
In the RS, the DOC export to the southern Gulf of Mexico was ~13 times higher
In the RS, the DOC export to the southern Gulf of Mexico was ~13 times higher
(2418.5 t C d−1), ranging from 1914 to 2954 t C d−−11. Meanwhile, in the DS, the DOC flux
(2418.5 t C d−1 ), ranging from 1914 to 2954 t C d . Meanwhile, in the DS, the DOC flux
averaged 182.9 t C d−1 (from 155 to 229 t C d−1). On the other hand, the daily POC efflux
averaged 182.9 t C d−1 (from 155 to 229 t C d−1 ). −1On the other hand, the−1 daily POC
can increase up to ~19 times higher at RS (1264.1 t C d ; from 904 to 1970 t C d ) compared
efflux can increase up −1to ~19 times higher at RS (1264.1 t C d−1 ; from 904 to 1970 t C d−1 )
with the DS (65.8 t C d ; from 50 to−181 t C d−1). Finally, the−DIC efflux to the Gulf of Mexico
compared with the DS (65.8−1t C d ; from 50 to 81 t C d 1−1). Finally, the DIC efflux to the
in the RS was 14,528.3 t C d (from 14,447 to 14,593 t C d ), which was almost 4.5 times
Gulf of Mexico in the RS was 14,528.3 t C d−1 (from 14,447 to 14,593 t C d−1 ), which was
higher than
almost the DS
4.5 times (3228.7
higher thantC d DS
the
−1 (from 3074t C
(3228.7 tod3391 t C d3074
−1 (from −1 ) (Table 2). t C d−1 ) (Table 2).
to 3391
According to the C flux balance (Table 2; Figure 8) between the gauging
According to the C flux balance (Table 2; Figure 8) between the gauging station
station (M10)
(M10)
and the outlet (B7 + B8), the fluxes of DOC (1.5 to 1.6 times), POC
and the outlet (B7 + B8), the fluxes of DOC (1.5 to 1.6 times), POC (1.2 to 2.5 times),(1.2 to 2.5 times), and
and
TOC (1.4 to 1.8 times) increase at the river mouth. Meanwhile, the final
TOC (1.4 to 1.8 times) increase at the river mouth. Meanwhile, the final DIC flux decreasesDIC flux decreases
slightly (0.9
slightly (0.9times)
times)concerning
concerningBoca Bocadeldel Cerro
Cerro (M10).
(M10). TheThe previous
previous balance
balance (M10 (M10 vs.+B7
vs. B7 +
B8)
B8) indicates
indicates thatthat the dynamics
the dynamics of lower
of the the lower
basinbasin
(with(with wetland
wetland and and floodplain
floodplain systems)
systems) and
the contribution of the Grijalva River (B6) are fundamental to quantifying the final final
and the contribution of the Grijalva River (B6) are fundamental to quantifying the C loadC
to the Gulf of Mexico. However, it must be considered that in the dry season, the seawater
intrusion could modify the C export to the sea of the Usumacinta River; nonetheless, the
seawater intrusion reaches only the stations closest to the river’s mouth. On rainy season,
there is no seawater intrusion.

3.5. Annual C Loads Estimates

The Usumacinta River at Boca del Cerro (M10) transports an estimated total of 0.194 ±
0.015 Tg DOC (0.180 to 0.215), 0.066 ± 0.004 Tg POC (0.062 to 0.070), 2.571 ± 0.076 Tg DIC
(2.541 to 2.606), and 0.032 ± 0.024 Tg PIC (0.016 to 0.064) for the study period (2017–2018).
Considering the balance between Boca del Cerro (M10) and the rivers’ mouths (B7 and
B8; Table 2; Figure 8), the Usumacinta-Grijalva system (HR-30) discharges to the Gulf of
Mexico ~0.294 ± 0.013 Tg DOC yr−1 (0.265 to 0.336), ~0.125 ± 0.06 Tg POC yr−1 (0.077 to
0.180), ~2.443 ± 0.167 Tg DIC yr−1 (2.297 to 2.596), and 0.026 ± 0.012 Tg PIC yr−1 (0.008
to 0.034). Overall, the annual C export of HR-30 during the study period was estimated
Water 2022, 14, 2703 16 of 30

at ~2.879 Tg C yr−1 (2.648 to 3.146), of which DIC accounts for 85% of the total flux,
followed by DOC (10%), POC (4%) and a minimal fraction (<1%) corresponding to PIC.
The calculated yields of DOC, POC, and DIC for the Usumacinta-Grijalva system were
2.61 t km2 yr−1 (2.36 to 2.99), 1.11 t km2 yr−1 (0.69 to 1.59), and 21.70 t km2 yr−1 (20.41 to
23.07), respectively. The latter is the first estimate of C transport (organic and inorganic) to
the ocean for a Mexican tropical lotic system. The results can be incorporated as a baseline
for further, more elaborate, more accurate studies and for modeling the regional C budget.

4. Discussion
4.1. Temporal and Spatial Variation of C in the Usumacinta River
4.1.1. Comparison with Other Large Rivers
The average concentrations of DOC measured in the Usumacinta River in the RS
(3.4 ± 1.8 mg L−1 ) and the DS (1.7 ± 0.6 mg L−1 ) were lower than the estimate of the
world DOC average (~5.75 mg L−1 ) [88]. The rivers of the tropical zone usually have DOC
values between 2 and 15 mg L−1 , with average values of 7.4 mg L−1 in Africa, 4.9 mg L−1
in America, 5.2 mg L−1 in Asia, and 4.8 mg L−1 in Oceania [11]. In rivers that drain
carbonate rocks, such as the Usumacinta River, the concentration of DOC is more limited
(~1 mg L−1 ) [12]. Other tropical rivers report similar DOC values to this study (Table 3),
for example the Zambezi, southern Africa (1.2 to 4.9 mg L−1 ) [89]; the Tana, Kenya (0.2 to
6.9 mg L−1 ) [47]; and the Orinoco, Venezuela (1.7 at 4.1 mg L−1 ) [38]. Higher DOC values
in rivers are associated with larger wetlands and conserved forests [25]. Certain tropical
rivers have DOC values greater than 10 mg L−1 , for example the Negro River, Brazil
(12.7 mg L−1 ) [25], and the Nyong River, Cameroon (6.4–51.0 mg L−1 ). These colored waters
have large amounts of humic substances and high dissolved OM content [90].

Table 3. C concentrations in tropical rivers around the world. The temperate Mississippi River, which
also discharges into the Gulf of Mexico, was included for comparative purposes. (* Data from [91].
The average and range are shown).

Watershed Area × Q* C (mg L−1 )

River Reference
106 (km2 ) (m3 s−1 ) DOC POC DIC
Usumacinta 0.07 15 to 5970 2.56 (0.88–7.11) 1.14 (0.21–3.78) 31.6 (15.6–47.2) This study
Amazon 6.30 209,000 5.65 (3.4–10.25) 1.25 (0.44–4.46) 1.4 [25,92]
Congo/Zaire 3.80 42,000 7.78 (3.5–11.8) 1.57 (0.7–2.3) 3.1 [25,93]
Mississippi 3.30 18,074 3.7 (2.9–4.1) 4.3 (1.9–9.7) 29.1 (19.2–41.4) [18,31]
Orinoco 1.10 34,880 2.92 (1.75–4.12) 0.91 (0.24–2.29) 2.0 [38,77]
Irrawaddy 0.43 12,049 1.2–2.9 1.2–5.2 23.6 [45,77]
Negro 0.68 28,400 12.7 (3–18) 0.72 (0.26–1.09) [92]
Zambezi 1.30 3171 1.2–4.9 6.3 [77,89]
Godavari 0.31 2917 1.3–4 7.2 (0.3–20) 34.8 (6–53) [94,95]
Red 0.15 2109 2.0 (0.1–8.5) 1.5 (0.1–9.0) 19.6 (9.1–29.9) [54,55]
Senegal 0.27 697 2.1 (1.25–3.25) 0.2–4.0 [50,77]
Nyong 0.03 193 16.0 (6.4–51) 3.77 (1.6–8.1) [96]
Maroni 0.07 1807 5.8 (2.12–11.34) 1.8 (0.45–4.5) [97]
Tana 0.04 150 0.2–6.9 0.3–120 13.2 (2.4–57.6) [47,48]

The average POC of the Usumacinta River ~1.1 mg L−1 (0.2 to 3.8 mg L−1 ) is lower than
that reported for North American rivers with ~2.5 mg L−1 (1 to 10 mg L−1 ) but like other
tropical rivers (Table 3) such as the Maroni, French Guiana [97], and the Apure and Orinoco,
Venezuela [38]. Some highly turbid tropical rivers with high TSS loads (>100 mg L−1 ) have
higher POC concentrations than the Usumacinta River. This is the case for the Tana, Kenya
(0.8 to 141.9 mg L−1 ) [49]; and the Yellow, China (4.6 to 92.4 mg L−1 ) [98] (Table 3).
DIC in the Usumacinta River averaged 31.6 ± 6.3 mg L−1 (15.6 to 48.3 mg L−1 ;
Table 1). According to Cai [99], the maximum DIC (as HCO3 − ) of large rivers globally is
~3115 µmol L−1 (37.4 mg L−1 ), for the Danube River, Central Europe. Other large rivers
on carbonate lithology such as the Yellow (~2591 µmol L−1 , 31.1 mg L−1 ), the Mississippi,
Water 2022, 14, 2703 17 of 30

USA (~2421 ± 480 µmol L−1 , 29.0 ± 5.8 mg L−1 ), and the Godavari, India (~2156 µmol L−1
or 25.9 mg L−1 ), have DIC values greater than 25 mg L−1 [18,99] (Table 3).
The DIC values for the tropical zone are low due to the lower percentage of carbonate
rocks [11]. The average riverine DIC for tropical America is 434 µmol L−1 (5.2 mg L−1 ).
In Africa (395 µmol L−1 or 4.74 mg L−1 ) and equatorial Asia (1064 µmol L−1 or 12.8 mg L−1 ),
DIC values are also low but increase toward high latitudes (>30◦ N) [11]. Our DIC results
place the Usumacinta River among the highest concentrations reported in the world’s large
rivers [12]. Considering that the Mississippi River is not included as a tropical river [11],
the present study reports that the highest DIC loads in rivers of tropical America are
represented by the middle and lower basin of the Usumacinta River. This value is higher
than other large tropical rivers (Table 3), such as the Amazon, Brazil (4.1 mg L−1 ) and the
Orinoco (2.0 mg L−1 ) and Paraná, in the south of south America (3.4 mg L−1 ), which have
less than 4% carbonate rocks [100,101].
Our DIC results are higher than those reported in the global river discharge database
(GEMS-GLORI) for the Usumacinta (value at Boca del Cerro–M10; 27.7 mg L−1 ) and the
Grijalva (25.4 mg L−1 ) [77]. Although there are scarce and scattered DIC reports from other
Mexican rivers [e.g., Ameca (17.7 mg L−1 ), Balsas (32.7 mg L−1 ), Pánuco (35.0 mg L−1 ),
Grande/Bravo (31.4 mg L−1 ) [77]], the present investigation is the first describing the
spatiotemporal patterns of DIC concentrations in a Mexican river and its most impor-
tant tributaries.
The Tzendales (M4; 41.2 mg L−1 ) and La Pasión (M7; 39.7 mg L−1 ) rivers presented the
highest DIC averages in the two sampling seasons. The preceding can be directly associated
with the lithological characteristics of each sub-basin: the La Pasión River (M7) has ~66%
Cretaceous carbonates, and agricultural activities in the Guatemalan part possibly increase
the DIC due to liming. Meanwhile, the Tzendales (M4) drains from a steeply sloping
limestone zone. High and similar ranges of DIC have been reported in rivers from small
karst basins such as the Houzhai River, China (30.2 to 70.2 mg L−1 ) [57], and the Mascouche
River (19.0 to 61.4 mg L −1 ; a tributary of the St. Lawrence River, Canada) [102].

4.1.2. Correlation between DOC, POC, and DIC and Water Discharge
According to Degens [103], DOC increases during the rainy season due to (i) the
processes of leaching and dragging of OM through surface soil erosion (“flushing effect”),
(ii) the infiltration of OM and the microbial degradation of the flooded terrestrial vegetation,
and (iii) by the C processing from the floodplain. DOC in the RS should be primarily
allochthonous. Thus, in the DS, the input of allochthonous OC must decrease enormously,
and the DOC loads would be dominated by the in situ contribution and POC transforma-
tions [12]. This hypothesis, which seems feasible, must be verified using stable isotopes.
The increase in DOC as rainfall increases (Figure 3b) has been seen in several rivers world-
wide, such as the Nyong [96], Zambezi [89], Senegal, West Africa [50], Mississippi, [18],
Maroni [97], Orinoco, [38], Amazon, and Congo, the Democratic Republic of Congo [25,43].
The POC in the Usumacinta River showed a positive relationship with the TSS (Figure 4b),
like that previously reported by Cuevas-Lara [42] in 2017. According to Seyler [25], the
variation of TSS and POC depends on the hydrology and land use of the drainage basin.
Mechanical erosion increases during precipitation events and mobilizes particulate material
from riparian zones or associated with soil clay minerals. The increased discharge also removes
sediment and C from the bottom of the channel, thus increasing turbidity [12]. According to
Muñoz-Salinas [71], cyclonic storms during the rainy season in the Usumacinta-Grijalva
system promote the entrainment of large volumes of OM and sediments due to episodes of
high erosion around the watershed.
The positive relationship between POC and TSS (Figure 4b) has been reported in most
lotic systems worldwide [12,26], both in tropical rivers of South America [38,92,97,100],
Asia [55,98], Africa [25,43,49] and in rivers of temperate zones [104]. Few studies report a
PIC–TSS relationship such as in the Usumacinta River (Figure S6). However, PIC shows a
similar trend to POC in rivers worldwide [34,103].
Water 2022, 14, 2703 18 of 30

Several river systems [38,52,92,97] reported a decrease in %POC with increasing TSS
loads, as was observed in the Usumacinta River (Figure S3). This variation may depend
on various processes such as POC dilution by increasing mineral material in highly turbid
rivers. At the beginning of the rainy season, erosive processes occur in the surface horizons
of the soil with high OC content. Meanwhile, sediments are removed from the deepest soil
horizons (refractory OC) if erosion rates increase, generating a lower % POC in TSS [52].
Thus, if the concentration of TSS is low (dry season), the POC must come from the superficial
horizons of the soil and aquatic PP [42]. On the other hand, when the TSS loads are higher
(rainy season), the POC must come from deep soils and sedimentary rock, generating a
lower % POC [105].
Previous studies [29,35,103] have demonstrated an inverse relationship between DIC
concentrations and discharge rates in many rivers. This pattern is explained by a dilution
effect, variations in C sources, and the balance between rainfall and evaporation [106]. In
most of the sampling stations on the Usumacinta River, the DIC was higher during the
DS, except in the Lacantún River sub-basin (M2, M3, M4, and M5; Table 1). Thus, DIC’s
concentration effect is generated during the DS due to low rainfall and higher temperature
and evaporation. A similar pattern has been reported in tropical [65,99,107,108] and
subtropical [109] rivers. According to Cai [99], the concentration of HCO3 − in the principal
worldwide rivers is negatively correlated with the discharge. This pattern suggests that
the DIC concentration is more related to the balance of precipitation–evaporation in the
drainage basin. In addition, the Mississippi River, which has a low content of carbonate
rocks (18%), has a high concentration of dissolved HCO3 − in the water and moderate
DIC fluxes. Consequently, it is inferred that the high concentration of DIC results at least
partially from the loss of water by evaporation [99]. Similarly, in the Changjiang River,
China, the highest concentrations of ions (Ca+2 , Mg+2 , and HCO3 − ) occur during the lowest
discharges. The latter is important to mention because the increase in discharge into the
Usumacinta River, up to six times more during the rainy season, would be expected to
dilute the concentrations of these main ions significantly, and in fact, Olea-Olea et al. [85]
reported significantly higher ion values during the dry season. In addition, they mention
that geochemical models show that the main weathering of carbonate rocks in the dry
season and carbonate and silicate rocks in the rainy season handle the chemistry of the
Usumacinta River.
The studies that prove a corresponding seasonal increase in DIC loads with river
discharge are limited [110]. In the Chajul (M2), Lacantún (M3 and M5), and Tzendales
(M4) rivers, the DIC was higher in the RS. Hence, the concentration of DIC may depend
on the frequency and intensity of precipitation in specific karst basins. Qin [57] recorded
higher DIC values in the rainy season of the Houzhai River Basin, China. These results
highlight that rainfall promoted the exchange between surface water and groundwater
(increased contribution of CO2 from the soil) through the highly transmissive karst aquifers
with underground drainages [111].

4.1.3. Spatial Variation of DOC, POC, and DIC Concentrations

In the Usumacinta River basin, the general trend in DOC is to increase from the
middle basin toward the river’s mouth, in the RS (Figure 3a), as reported in the Amazon
River basin by Hedges [112], who mentions that DOC has an inverse relationship with
altitude. In the Cuibá River basin, Brazil, [113] reported a longitudinal increase in DOC
concentration from the upper region (plateau river) to the El Pantanal wetland zone. Due
to the hydrological connectivity, this trend was more pronounced in the rainy than in the
dry season. Another similar case is the Zambezi River [89], which presented a longitudinal
increase in DOC concentration from the upper part to the mouth at the Indian Ocean
during the rainy season, associated with a high correlation with the wetland extension.
During the dry season, when there is low hydrological connectivity, the DOC gradually
decreases toward the river’s mouth [89]. In other rivers, such as the Mississippi, the DOC
gradually decreases downstream because of constant dilutions of the tributaries that have
Water 2022, 14, 2703 19 of 30

lost wetlands due to changes in land use [67]. According to Meybeck [12], shallow wetlands
and peat bogs are the primary sources of riverine DOC. Although there is a DOC increasing
trend downstream, the DOC concentration in the mainstem remains relatively constant
until the confluence with the Grijalva River, which increases the concentration of DOC,
mainly in the RS.
The flooding zone in the lower basin of the Usumacinta River and the wetland complex
(La Libertad, Catazajá, and Pantanos de Centla-CWBR) [114] have significant effects on the
increase in DOC in the RS. The highest DOC values (Table 1; Figure 3) in the San Pedro
River (B1) are associated with Laguna del Tigre National Park (Guatemala, RAMSAR site
N◦ 488). It is an extensive alluvial plain of wetlands (temporal ponds and permanent
lakes) and the rainiest part of the Yucatán Peninsula [115]. Similarly, in the La Pasión River
sub-basin (M7), the DOC is likely to increase because El Pucté Wildlife Refuge (167 km2 ) is
near the sampling station. It is part of the protected areas of southern Petén, characterized
by floodplains, forests, lowlands, wet marshy areas, and water springs [116].
The stations of the Lacantún River (M1, M2, M3, M4, M5) have the lowest DOC
values (<2 mg L−1 ; Table 1; Figures 3a and 7). These sub-basins have a limestone lithology
(~50%) and rainforest cover (~65%) associated with the Lacandona forest and the RBMA.
Leptosol is the most abundant soil group. These soils are shallow, rocky, and poorly
developed, with a large amount of calcareous material and low amounts of OM [117,118].
These characteristics of the sub-basin explain the lowest DOC concentrations recorded,
considering that pristine rivers [119] from carbonate basins [12] and with low soil OC
content [16] usually have low DOC concentrations (1 to 3 mg L−1 ).
Meybeck [12] uses the relationship between %POC and TSS to differentiate fluvial POC.
The autochthonous POC may be more meaningful if the TSS concentration is <10 mg L−1 .
In addition, the POC/Chla-a ratio can be a good indicator of fluvial OC sources. For
example, if the ratio POC/Chl-a is ~50 (30–100; average value for phytoplankton), the POC
is autochthonous, but if the ratio is >200, the POC originates from erosion and runoff from
the basin [105,120]. The average POC/Chl-a ratio in the Usumacinta River was 1465 ± 2605
(from 108 to 10,362), with higher values in the RS (~6 times higher) and a decreasing trend
toward the river’s mouth (Figure S4). Our results indicate that the POC is typically soil-
derived. Some tropical rivers present more extreme POC/Chl-a ranges, such as the Tana (75
to 40,781) [47] and Red, Vietnam (23 to 9413) [55], reflecting, in the same way, the terrestrial
sedimentary origin.
The La Pasión (M7) and San Pedro rivers (B1) showed low TSS values (<10 mg L−1 ;
Tables S2 and S3) and a POC/Chl-a ratio (342 and 158, respectively) at the other sampling
stations (Table S4; Figure S4). M7 and B1 have a comparatively higher autochthonous
contribution in the rainy season. On the other hand, at the Lacantún River stations (M1,
M2, M3, M4, and M5), the POC/Chl-a ratio presented the highest values. These results
show that the more significant drag of terrestrial material during precipitation events
generates an increase in turbidity and a reduction in aquatic PP [121]. In contrast, the
POC/Chl-a ratio at the stations near the river’s mouth (B5, B6, B7, and B8) shows that the
autochthonous contribution (phytoplankton) is essential, comprising up to 50% of the POC
during the dry season, due to the marine contribution and the lower turbidity that favors
the PP [42]. Something similar occurs in the Senegal River’s marine-influenced area, where
high concentrations of phytoplankton were found [50]. However, it is necessary to identify
the POC sources using stable isotopes of C (δ13 C), as reported in other river systems.
According to Wetzel [122], the riverine DOC/POC ratio depends on the relief of the
basin, and it is usually between 6:1 and 10:1. This ratio shows that most of the transported
riverine OC is dissolved. Globally, the mean DOC/POC ratio is ~1.2 [26], with minimum
values (<1) for mountain or highly turbid streams [98] and maximum (>20) for highly
polluted rivers or with minimal contributions of particulate matter [88].
At the Lacantún River stations (M1, M2, M3, M4, and M5) during the RS, the DOC/POC
ratio is <1 (Table S4; Figure 5b). In particular, the Tzendales River (M4) has the lowest
amount of DOC (~29%). In humid tropical regions with mountainous relief, such as the
Water 2022, 14, 2703 20 of 30

upper basin of the Amazon River [12], or some Asian monsoon rivers [123], the DOC/POC
ratio is <1. The steep slopes (30–65%) and precipitation (~3000 mm yr−1 ) [124] of the Lacantún
River are the principal erosivity factors. That influences our study’s highest concentration
of sediments (Table S2) and POC (Figure 4a).
In the remaining stations in the middle (M6–M10) and lower (B1–B8) basins, the DOC/
POC ratio in both seasons was >1 (Table S4; Figure 5b). This ratio is like in other tropical
rivers, such as the Congo and the Amazon, which have a significant contribution (~80%) of
DOC derived from the decomposition of OM in wetlands and natural forests [25]. Notably,
the La Pasión River (M7) and the San Pedro River (B1) presented the highest DOC/POC
ratios in the entire basin (Table S4; Figure 5b). These ranges suggest similar behavior to
the Negro River [25], which has high DOC (93%) with humic substances from highlands
and flooded forests [125] as well as acidic pH (3.0 to 5.5). However, the La Pasión (M7) and
San Pedro rivers (B1) presented a pH of ~7.4, so it could be inferred that there is no high
concentration of humic substances. Still, due to wetlands and grassland areas, the DOC
was higher (~86%) than in the mainstem and other tributaries of the Usumacinta River.
The DIC concentration did not present a pattern of longitudinal variation in the
Usumacinta River. However, the seasonal variation was more marked in the middle
basin than in the stations near the rivers’ mouth (Figure 6a), possibly due to the higher
precipitation and slope promoting greater weathering. In other rivers, such as the Rhône,
France [126], or the Tana [48], there is an increase in DIC from the headwaters to the river’s
mouth. This longitudinal variation depends on lithology (a higher percentage of carbonate
rocks in the lower catchment) and erosion in the drainage basin. DIC loads may also
decrease downstream due to the dilution effects of tributaries with less carbonate rock
cover (Yangtze River, China) [123].
The dynamics of a tropical river are highly dependent on precipitation and flow
rates [36]. In our study, there was an increase in Chl-a (>PP) during the DS (Figure S2)
associated with lower TSS input (Tables S2 and S3), turbidity, and flow velocity. For this
reason, an increase in DIC consumption from photosynthetic activity in the dry season (low
DIC/DOC) would be expected. However, in the Usumacinta River, the variables of river
metabolism seem to have little importance in regulating DIC, with more influence on the
rainfall–evaporation balance or CO2 evasion. The DIC’s biological (PP or R) contribution in
karst catchments is considerably lower than in non-karst systems [57].

4.2. C Balance in the Usumacinta Lower Basin

According to the mass balance (Figure 8), the wetland and floodplain system of the
lower basin (CWBR, Figure 1) is a C sink during the RS, retaining 557.5 t d−1 DOC and
46.5 t d−1 POC. Contrarily, the lower basin during the DS acts as a source of C, mobilizing
5.8 t d−1 DOC and 11.5 t d−1 POC (Table 3). The DIC flux balance is positive and indicates
that the lower Usumacinta River basin acts as a net sink of DIC in both seasons (8114.1 t d−1
in the RS and 823.9 t d−1 in the DS).
Floods can overflow the Usumacinta River’s mainstem, and a significant fraction of
the OC can be retained in the adjacent floodplains. According to [127], flow connectivity
with adjacent lakes and wetlands increases strongly in the lower basin of the Usumacinta
River during the RS. Estrada et al. [128] mention that during floods, the area of wetlands in
the lower basin around the Usumacinta and San Pedro rivers (B1) increases up to 2.48 times
compared with the driest season. Few studies have addressed the ecological functioning
of the Usumacinta River floodplain lakes [129,130]. Nevertheless, according to [130],
differences in water quality (nutrients, sediments, and Chl-a) suggest that floodplains may
be sediment sink areas and contribute OM to the river.
During the rainy season, the organic C can be deposited in the floodplains (POC) or
mineralized (DOC), emitting considerable amounts of CO2 into the atmosphere, as observed
in other rivers [68,106]. The downstream decrease of ~50% of DIC fluxes (Figure 8) indicates
a greater amount of CO2 evasion in this zone, supporting the latter assumption. On the
other hand, during the dry season, the lower basin of the Usumacinta River acts as a
Water 2022, 14, 2703 21 of 30

DOC and POC source. In addition, since the Chl-a concentration increases downstream
(Figure S2) and the POC/Chl-a ratio decreases (Figure S4), the autochthonous contribution
of organic C in the dry season must be an essential contributor to the C fluxes, mainly POC,
as previously mentioned [42]. However, it is important to mention that the DIC/DOC ratio
(Figure S5) also decreases downstream in the dry season. The latter may be related to the
PP processes that consume inorganic C.
Rivers can store sediment and OM in the channel, floodplains, and other depositional
areas [131]. For example, [51] mention that the Tana River retains TSS and C (DOC, POC, and
DIC) over 385 km between sampling stations. Moreover, as flow increases, POC retention also
increases, and DOC retention decreases, although the fate of the retained C is unknown. Re-
cently, wetlands in the Amazon River basin were found to accumulate significant amounts
of C and are an essential component of the fluvial C budget of tropical rivers [132]. Future
work in the Usumacinta River must analyze C’s fate and the wetland zone’s importance
(CWBR) in the C budget.

4.3. Global C Export from the Usumacinta-Grijalva River to the Gulf of Mexico
The total estimated C loading into the southern Gulf of Mexico calculated for the
Usumacinta-Grijalva was 2.879 Tg C yr−1 . This value represents the first estimate of C flux
from the largest tropical river in Mesoamerica. Li [16] re-estimated the C flux in 263 river
systems globally and determined that flow is the main factor modifying the fluxes of DOC,
POC, and DIC. This model does not consider the impact of human activities (e.g., land-use
changes, dams, water consumption, sewage input, and sediment dredging) in the drainage
basin, so there may be uncertainties in the estimates of C fluxes. However, it is essential
background for our study.
The DOC flux calculated for 2017–2018 in the Usumacinta-Grijalva system was higher
than the [16] model (0.29 Tg C yr−1 versus 0.25 Tg C yr−1 ). This behavior can be associated
with the increase in DOC concentration in the lower basin due to the contribution of the
wetlands systems such as the Pantanos de Centla, as previously described. In addition, the
Grijalva River (B6) contributes considerably more DOC than the Usumacinta River during
the RS (Table 2). This supply may be associated with a higher degree of deforestation
and extensive agricultural and livestock activities in the middle and lower Grijalva River
basins [133], as well as the presence of two large cities (Tuxtla Gutierrez and Villahermosa)
that modify the water quality of the Grijalva River [74,134].
The POC flux in this study is ~three times lower than the [16] model (0.07 to 0.18 Tg C yr−1
versus 0.25 to 0.5 Tg C yr−1 ). In the C mass balance (Table 2), it was observed that POC
input from the Grijalva River (B6) is high in the RS (64%) but decreases markedly in the DS
(2%). The Grijalva River has had substantially reduced TSS flux (~95%) in recent years due
to the construction and operation of four dams (Complejo Hidroeléctrico Grijalva) since
1987 [91]. It is probable that POC transport to the Gulf of Mexico had a significant decrease
of up to 70% compared with the natural condition proposed by the [16] model. The effects
of dams and reservoirs on TSS and POC retention have been studied in several rivers
globally [135]. For example, Shi [136] mentions that dams in the Wujiang River, China, have
a POC interception rate between 43% and 65%, thus significantly affecting downstream C
sources and fluxes. It is also probable that the effect will be more significant if the number
of reservoirs in the longitudinal profile of the river is increased [135]. The damming effect
in the Grijalva River (B6) is the same as or greater than in other dammed rivers, such as the
Nile (Egypt), Rio Grande (USA), Yellow, or Mississippi [91]. The DIC flux in this study was
higher than the [16] model but fitted the proposed range (2.44 Tg C yr−1 vs. >2 Tg C yr−1 ).
The C fluxes of the Usumacinta-Grijalva River system are lower than those estimated
for large tropical and temperate rivers (e.g., Amazon, Congo, Orinoco, and Mississippi),
which is associated with the significantly smaller flow and drainage area of the Usumacinta-
Grijalva River basin. Nonetheless, our estimate is comparable to the transport of several
tropical (Niger, Zambezi, Godavari, Maroni, and Senegal) and temperate rivers (Danube
and Yellow) with similar flows or catchment areas (Table 4).
Water 2022, 14, 2703 22 of 30

Table 4. Comparison of the C flux in the Grijalva-Usumacinta system (estimated at the mouth) with
the principal rivers of the world. (The Mississippi, Danube, and Yellow rivers are temperate, and the
rest are tropical. The area and Q are from [91] data. Flows in parentheses indicate the previous values
before the flow reduction due to the construction of reservoirs and irrigation. The C flux for the Tana
River is in Gg yr−1 , 1 Gg = 103 t. 1 Tg = 106 t).

Area Q C Flux (Tg C año−1 ) Yield (t C km2 yr−1 )

River
6 2 3
10 (km ) (km año−1 ) DOC POC DIC DOC POC DIC
0.29 0.12 2.44 2.61 1.11 21.70
Usumacinta-Grijalva 0.112 120–147
(0.26–0.33) (0.07–0.18) (2.29–2.59) (2.36–2.99) (0.69–1.59) (20.4–23.1)
[92] Amazonas 6.30 6223 26.9 13.2 29.4 5.8 5.5 4.3
[25,93] Congo 3.80 1300 12.4 2.0 3.5 3.5 0.6 1.0
[26,34] Orinoco 1.10 1135 5.0 1.7 5.7 4.8 1.6 5.5
[18,99,137] Mississippi 3.30 570 3.95 2.3 12.25 1.4 2.3 4.2
[52,99,103] Yellow 0.75 15 (43) 0.06 0.41 1.05 0.1 0.54 1.632
[45] Irrawaddy 0.43 380 (430) 0.9 2.3–4.3 - 2.2 5.5–10.4 -
[26,77] Danube 0.79 210.0 0.6 - 7.5 1.2 7.7–12.6 9.6
[26,34,89] Zambezi 1.31 109.0 0.6 0.5 - 0.1–0.2 0.1 0.7
[99,103] Niger 1.2 152 0.53 0.66 1.24 0.6 0.5 0.56
[34,94] Godavari 0.31 92 (120) 0.76 0.28 2.27 - - 8.0
[97] Maroni 0.07 63.7 0.34 0.11 - 5.6 1.9 -
[50,77] Senegal 0.27 24.4 0.1 0.1 - 0.2 0.1 -
[49,51,77] Tana 0.04 15 11.2 113.3 73.4 0.1 1.4 0.9
[11] Tropics 63.8 25,123 136.0 131 210.0 2.05 2.13 3.3
[11] Global 150.0 37,400 215 205 385 1.4 1.3 2.2

DOC and POC fluxes in the Usumacinta-Grijalva River system accounted for just
~7% and ~5.4% of the C flux from the Mississippi River (USA), respectively. However,
the Mississippi has a drainage basin ~30 times larger and an annual flow ~five times
greater. Despite this, the DOC flux yield of the Usumacinta-Grijalva River system is
greater than that calculated by [137] for the Mississippi River (1.72 t C km2 yr−1 versus
1.4 t C km2 yr−1 ). The Mississippi POC flux yield is ~twice as high (2.3 t C km2 yr−1 versus
1.1 t C km2 yr−1 ) [18] because of the effect of watershed size (Table 4).
The TOC fluxes in the Usumacinta-Grijalva River system (0.35 to 0.49 Tg C yr−1 ) are
lower than that reported for the Zambezi River (1.1 Tg C yr−1 ; ~109 km3 yr−1 ) and Niger
River (1.19 Tg C yr−1 ; ~152 km3 yr−1 ). Comparatively, TOC fluxes are similar to the Maroni
River (0.4 Tg C yr−1 ) and slightly higher than the Senegal River (0.2 Tg C yr−1 ), whose
discharges are 63.7 km3 yr−1 and 24.4 km3 yr−1 respectively. Surprisingly, the DOC and
POC yield rates from the Usumacinta-Grijalva were higher than in large rivers such as
the Yellow, Zambezi, Niger, and Senegal. However, the DOC and POC yield rates of the
Maroni River are higher, which can be associated with a smaller drainage area and high
forest cover [97].
The Usumacinta-Grijalva River system DIC flux (~2.44 Tg C yr−1 ) represents one of
the highest values of those reported globally (>2 Tg C yr−1 ) [16]. Thus, this system exports
more DIC than the Yellow, Niger, and Godavari and slightly less than the Congo River. The
estimated yield (21.7 t C km2 yr−1 ) exceeds the large rivers whose drainage area is superior
to 400 km2 (Table 4), such as the Amazon (4.3 t C km2 yr−1 ), Congo (1.0 t C km2 yr−1 ),
Orinoco (5.5 t C km2 yr−1 ), and Mississippi (4.2 t C km2 yr−1 ).
Only a few DIC yield data similar to this study have been reported, for example in the
Brahmaputra River, India-Bangladesh (14.4 t C km2 yr−1 ); Xijiang, China (15.38 t C km2 yr−1 );
and Pearl, China (13.2 t C km2 yr−1 ) [99], as well as in other small monsoon rivers in India,
such as the Netravati (17.8 t C km2 yr−1 ) and Baitarani (20.7 t C km2 yr−1 [138]. Higher DIC
yields have been reported in the tropical mountainous watersheds of western India, such as
the Ulhas River (48.5 t C km2 yr−1 [139] or the Kikori River, New Guinea (74.6 t C km2 yr−1 ),
which has the highest value globally [34]. Therefore, carbonate dissolution is particularly
important in the Usumacinta River basin, which exports a higher amount of DIC per unit
area than the 25 largest rivers worldwide reported by [99].
Ideally, C concentrations and discharge should be measured simultaneously, at least
weekly or monthly, for a robust estimate. The latter would ensure that C export during
peak discharge and basal flow would be captured. Therefore, the calculation of the annual
Water 2022, 14, 2703 23 of 30

C fluxes is based on: (a) only two dates reflecting the extreme tropical seasonality and (b)
the fact that the study year turned out to be wetter than a typical year (i.e., higher flows
and higher mass exports of C) and leaves considerable uncertainties. Nonetheless, the
obtained data are consistent with those observed in other tropical rivers and with the model
reported by [16], and they constitute the urgently needed baseline of the annual C fluxes in
the Usumacinta-Grijalva River system.
Moreover, the large spatial scale involved in the present study (~800 km distance to
the mouth) and all the variables considered (physicochemical parameters, TSS, Chl-a, and
the dissolved and particulate forms of C) provide unique information on the magnitude of
the seasonal fluvial contribution in the most important lotic system in Mexico and can be
considered a first approximation of the C balances of rivers in the country.

5. Conclusions
This study is the first to estimate the seasonal and spatial variations of the concen-
trations and export fluxes in DOC, POC, DIC, and PIC in response to hydrologic regimes
in the tropical Mexican Usumacinta River during the rainy (2017) and dry (2018) seasons.
Seasonal variations played an important role in the C dynamics in the Usumacinta River.
The Pantanos de Centla Biosphere Reserve played a crucial and seasonally variable
role in the C fluxes from the Usumacinta River to the Gulf of Mexico. The C balance
suggested net retention (C sink) in the floodplains during the rainy season. DOC (~36%),
and POC (~9%) fluxes decreased downstream concerning Boca del Cerro (M10). In contrast,
in the dry season, the balance showed an increase (C source) of DOC (~5%) and POC
(~22%) fluxes. The lower Usumacinta River basin is a sink for DIC in both seasons, with
this role being greater in the rainy (~50%) than in the dry (~25%) season. These results are
particularly interesting due to changes in riverine C transport and processing concerning
the changing climate.
The DOC and POC concentrations showed maximum values during the rainy season,
with an increase of approximately two times that during the dry season due to surface
erosion and the washing of allochthonous organic matter during the rainfall events. The
POC/Chl-a ratios show that organic matter of autochthonous origin can account for a con-
siderable amount of POC during the dry season, mainly in the lower basin. The DOC/POC
ratio in both seasons was greater than one, except in the Lacantún River sub-basin, which
had a higher POC content during the rainy season. The DOC concentration increases
downstream and represents ~66 ± 17% of the TOC in the rainy season and ~72 ± 7% of the
TOC in the dry season.
The DIC is the most important C fraction in the Usumacinta River, and its concentration
is the highest measured for tropical rivers in America. DIC did not present a longitudinal
variation but rather remained similar along the mainstem. At most of the sampling sites
(except in the Lacantún river sub-basin), the DIC concentration was higher in the dry
season, possibly due to a dilution effect in the rainy season and the negative balance of
precipitation–evaporation in the dry season.
There is an evident seasonal variation in the C flux into the Gulf of Mexico. The TOC
flux during the rainy season was ~15 times higher (~3683 ± 804 t d−1 versus 249 ± 20 t d−1 )
and was mainly represented by the dissolved fraction (65% in the rainy season and 75% in
the dry season). On the other hand, due to the lithology, the DIC was the main fraction trans-
ported to the ocean and was ~4.5 times higher (~14,528 ± 91 t d−1 versus 3228 ± 224 t d−1 )
during the rainy season.
The annual C flux for the Usumacinta River is consistent with the Li model [16].
The total carbon flux at the river mouth for the whole Grijalva-Usumacinta River ranged
between 2.648 and 3.146 Tg C yr−1 (mean 2.879 Tg C yr−1 ), of which DIC was the most
significant fraction transported (85%), followed by DOC (10%), POC (4%), and PIC (<1%).
Surprisingly, the estimated yield (21.7 t C km2 yr−1 ) of DIC in the Usumacinta-Grijalva River
exceeds that of other large rivers such as the Amazon, Congo, Orinoco, and Mississippi.
Water 2022, 14, 2703 24 of 30

Supplementary Materials: The following supporting information can be downloaded at: https:
//www.mdpi.com/article/10.3390/w14172703/s1; Table S1: Sampling sites in the middle and lower
basin of the Usumacinta River; Table S2: Summary of the physicochemical variables of the Usumacinta
River in the rainy season; Table S3: Summary of the physicochemical variables of the Usumacinta
River in the dry season; Table S4: Average values of C ratios (DOC/POC, POC/Chl-a, DIC/DOC) and
percentages (DOC/TOC, POC/TSS) in the Usumacinta River during the rainy and the dry seasons;
Table S5: C fluxes in the Usumacinta River during the rainy and dry seasons; Figure S1: Discharge
variation along the Usumacinta River during the rainy and dry seasons; Figure S2: Chlorophyll-a
concentrations along the Usumacinta River during the rainy and dry seasons; Figure S3: Adjustment
of the percentage of POC (%) contained in the TSS concerning the TSS concentration of the Usumacinta
River in the rainy and dry seasons; Figure S4: Longitudinal variation of the POC/Chl-a ratio with
respect to distance from the mouth of the Usumacinta River during the rainy and dry seasons;
Figure S5: Longitudinal variation of the DIC/DOC ratio with respect to distance from the mouth of
the Usumacinta River during the rainy and dry seasons; Figure S6: PIC adjustment regarding total
suspended sediments concentration of the Usumacinta River in the rainy and dry seasons.
Author Contributions: Conceptualization, I.S.-R., J.A., D.C.-L., D.C.-G. and L.A.O.; Data curation,
I.S.-R., D.C.-L. and D.C.-G.; Formal analysis, I.S.-R., J.A., S.S.-C., F.G.-O., D.C.-L., D.C.-G. and L.A.O.;
Funding acquisition, J.A.; Investigation, I.S.-R., J.A., D.C.-L., D.C.-G. and L.A.O.; Methodology, I.S.-R.,
J.A., D.C.-L., D.C.-G. and L.A.O.; Project administration, J.A. and L.A.O.; Resources, J.A.; Software,
I.S.-R., D.C.-L. and D.C.-G.; Supervision, J.A.; Validation, I.S.-R., J.A., S.S.-C., F.G.-O., D.C.-L., D.C.-G.
and L.A.O.; Visualization, I.S.-R., J.A., and L.A.O.; Writing–original draft, I.S.-R., J.A., D.C.-L., D.C.-
G. and L.A.O.; Writing–review & editing, I.S.-R., J.A., S.S.-C., F.G.-O., D.C.-L., D.C.-G. and L.A.O.
All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the FORDECYT-CONACYT Project 273646 “Fortalecimiento
de las capacidades científicas y tecnológicas para la gestión territorial sustentable de la Cuenca del
Río Usumacinta y su Zona Marina de Influencia (CRUZMI), así como su adaptación ante el cambio
climático”, the UNAM-PAPIIT Project IN216818 “Flujos de carbono, nutrientes y sedimentos en
un sistema lótico tropical”, the Programa de Investigación en Cambio Climático, UNAM, Projects
PINCC 2020 & PINCC 2021 “Cuerpos acuáticos epicontinentales: papel en la dinámica del carbono y
emisiones de gases de efecto invernadero en México”, and the Ministerio de Ciencia e Innovación,
Consejo Superior de Investigaciones Científicas de España Project COOPA20433 “Contribución del
neotrópico acuático continental a las emisiones de gases de efecto invernadero” and COOPA20472
“Los grandes ríos del neotrópico y su contribución al ciclo de carbono global”.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data supporting this study’s findings are available from the
corresponding author (J.A.) upon reasonable request.
Acknowledgments: We would like to thank the “Posgrado en Ciencias del Mar y Limnología,
UNAM”, and CONACYT grants awarded to I.S.-R. Also, Ismael Soria-Reinoso received support from
the Ecuadorian Secretariat for Higher Education, Science, Technology, and Innovation (SENESCYT,
Award No. CZ03-380-2018). Jorge Ramírez and Julio Díaz helped with fieldwork and data collecting.
Natura y Ecosistemas Mexicanos AC foundation supported with logistic services at the Chajul
Biological Station.
Conflicts of Interest: The authors declare no conflict of interest.

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