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This chapter shows the results of the determination of the levels of Copper (Cu), Iron (Fe), Magnesium (Mg), Manganese (Mn), and Cadmium (Cd) in sediments of the “Palizada River”; evaluated by atomic absorption. The results show high levels of Fe, Mg, and Mn concerning previous studies and are directly related to agricultural and livestock activities in the area. The metal-metal correlation analysis show significant values, suggesting that the generation source is the same. Some of the pollutants produced by industrial or population centers; end up in natural water bodies; by different physical processes, such as precipitation, complex formation, and others. These contaminants can bioaccumulate in aquatic organisms and reach humans through the food chain. Certain heavy metals such as cadmium (Cd) produced by human activities have been found in the oceans and the tissues of different organisms; which constitutes a risk for consumption; Cd is classified as an element that predisposes to the presence of Cancer. Therefore, the study of sediments is fundamental for determining the degree of contamination of an ecosystem.
Faculty of Chemical Sciences, Autonomous University of San Luis Potosí, Mexico
Ruby S. Gines
Technological Institute of Orizaba, Mexico
Rosa M. Cerón
Autonomous University of Carmen, Mexico
*Address all correspondence to: cmontalvo@pampano.unacar.mx
1. Introduction
Currently, coastal ecosystems are exposed to a large load of pollutants from urban activities; this problem is because significant amounts of waste are dumped that generally has no treatment, which contributes to increasing the concentration of certain pollutants as heavy metals are of particular interest because they are highly persistent, toxic and can bioaccumulate in exposed organisms.
The sediments allow lies to determine, from the geochemical point of view, the content of trace metals, their possible origin (anthropogenic or natural), and the mobility that serves to infer the potential risks of toxicity for the biota. The study of sediments in an aquatic ecosystem allows a comprehensive estimation of pollution; metals associated with the organic fraction can form solutions and remain available to aquatic organisms [1].
An earlier study [2] shows the behavior of heavy metals; copper (Cu), nickel (Ni), chrome (Cr), lead (Pb), cadmium (Cd), and zinc (Zn) in sediments and organisms in Terminos Lagoon, Campeche, Mexico. The results for the sediments showed that the total levels of metals were higher on the west side of the lagoon, except for Cd and Pb, which had a high level on the east side. For the oyster (Crassostrea Virginica), metal levels increase in the rainy season except for Pb, which presents higher values during the northern season. The results show a tendency to increase in the levels of Cr and Pb and are related to human and industrial activities.
Petroleum hydrocarbons, heavy metals, and pesticides are the main contaminants in Mexican coastal [3]. These elements have generated harmful effects for the organisms, coastal ecosystems, and public health; however, certain metals are part of the biochemistry of living beings, are required by organisms, and are part of various metabolic processes. Some metals, such as Fe, Cu, Zn, and others, are essential elements. The problem arises when these essential elements and other nonessential elements such as Hg, Pb, and Cd are found at high levels in the organs or tissues of aquatic organisms.
Another studio [4] showed levels of heavy metals in water and sediment samples; the water samples were within the national standards for river water. However, the presence of all metals considered in the study was confirmed in the sediments, which indicates that the sediments are a reserve source of pollutants. In this same study, Cr, Pb, Fe, Ni, and Cu were very high in the sediments, mainly in summer and winter.
In Mexico, other studies [5] determined levels of Cu, Mn, Fe, Ni, Cd, Pb, and Zn in samples of oysters, water, and sediments from “San Andrés”, lagoon to determine and understand the bioaccumulation mechanisms of the species and identify the potential risk for the consumption of oysters.
Several factors can predispose to the presence of heavy metals in certain studies [6], the bioavailable contents of Zn, Fe, Mn, Cu, Cr, Cd, Pb, and Ni in superficial sediments of the “Bocaripo” coastal lagoon were evaluated in two climatic periods. Showing the importance of the size and diameter of particles, the content of organic matter (OM), and the pH of the sediments.
Finally, the authors conclude that the bioavailable content of Cu may represent a potential risk of contamination and affect the mobility of other metals.
Studies carried out in the Bay of “Chetumal”, Mexico [7] confirm that organic matter and other physicochemical parameters are essential in a global study of heavy metals; the authors determined the levels of Cd, Pb, Hg, and As, in surface sediments as well as organic matter and nutrients. The environmental disturbance was related to discharges of water from the “Deep River” and from the city. In spring, the highest levels were for Cd, Pb, Hg, and As. The parameters analyzed: PO4, NO3, CO3, and organic matter (OM), did not show significant variation concerning reference values of the official Mexican standards.
The study of contamination in sediments must include the analysis of the texture and determine the relationships with the levels of heavy metals; In this sense, in studies carried out in Chile [8], the granulometric and geochemical aspects of superficial and subsurface marine sediments were analyzed; with this value, the authors determined the environmental quality of the sediments. In this sense, areas with environmental deterioration were established, generated by enrichment or contamination of some metals such as Ni, Zn, Pb, Cd, Cu, Hg, and As. The main textural fractions: are silt, sand, and clay. In this same study, high values of OM were found. The authors conclude that this area is susceptible to contamination due to its sedimentological characteristics and geomorphology.
Gonzalez et al. [9] determined significant components such as organic and inorganic matter (IM), silica, and carbonates, as well as heavy metals (Al, Fe, Mn, Cu, Zn, Pb, Cr, and Ni), sedimentation, and texture studies. The authors conclude; that the environmental problems presented by the “Copper River”, like most water bodies, are due to the contributions of residual waters (the majority without treatment). One of the sources of contamination has been the “Large Copper Mine”, which continues to have an impact although it is not currently being exploited. A clear example is that sediments are a reservoir of heavy metals and other pollutants.
Several authors [10] have studied the spatial and seasonal distribution of heavy metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in the dissolved fractions and particles of the Port of Mazatlán (a lagoon system coast in northwestern Mexico). The authors emphasize the effect of the anthropogenic contributions of heavy metals on the concentrations in the port and the adjacent seawater, finding that the effect of said agents in both fractions is limited to the immediate area of the discharge, with concentrations from outside of the port indistinguishable about the coastal waters. It is a verifiable fact that the sediments are temporary integrators of pollution [9, 10, 11] and are affected by different physical and chemical processes, which makes the concentration of the pollutant vary between climatic seasons.
Aguilar et al. [12] demonstrated in their studies that the climatic season has a great influence on metal levels; the contents of Cd, Cu, Zn, and Fe were analyzed in surface sediments of a “The Caleta” stream in the City of Carmen, Campeche. The experimental results indicated that there was no significant difference by time and sampling site, which was an expected behavior pattern since in the dry season there are no significant contributions of water.
Certain metals such as Pb, Cd, Hg, and Ni; are a significant risk to human health, are not classified as essential, and are often toxic at low concentrations. The Cd is considered a potent carcinogen according to the International Agency for Research on Cancer (IARC) [13]. These elements are found in the soil, air, and water and can reach man through the food or water he consumes.
The damage they cause is so severe that many species show no symptoms, but they accumulate large amounts in their internal tissues and organs [14, 15, 16, 17], from this fact derives the importance of studying marine sediments and classifying pollution and the risk to which aquatic organisms are exposed; Likewise, sediments reflect the environmental quality of an ecosystem [18, 19].
This chapter shows the results of determining the levels of Cr, Cd, Fe, Cu, Zn, and their relationship to climatic seasons in the fluvial lagoon system of the “Palizada” river, which flows into the “Terminos” lagoon.
This area constitutes one of the Natural Protected Areas of Mexico and is the habitat of various species of flora and fauna endemic to Mexico.
Physical environment: Carmen City (Figure 1), is located southwest of the state of “Campeche”, bordered to the north by the Gulf of Mexico and the municipality of “Champotón”, to the south by the state of Tabasco, to the east by the municipalities of “Escarcega and Candelaria” and to the west by the municipality of “Palizada” [20].
Figure 1.
The geographical location of the City of Carmen and “Terminos” lagoon.
The area of the “Terminos” lagoon includes Terminos lagoon and the adjacent fluvial -lagoon systems (“Palizada” from the east, “Chumpan-Balchacah”, “Candelaria-Palau”), the lagoon complex of “Pom Atasta”, “Puerto Rico”, “Los Negros” and the estuary of “Sabancuy”, the “Chacahito” lagoon, Carmen Island, and estuary Pargo. The study area is shown in Figure 2. The “Palizada” river delta-lagoon fluid system (SLFS) is in the southwestern portion of the Terminos lagoon hydrological basin between geographic coordinates 18°19′13″ and 18°29′04″ north latitude and 91°44′36″ and 91°51′31″ west longitude [20].
Figure 2.
The geographical location of the “Palizada” river.
To carry out this study, ten points were included in the extraction of sediment samples, during two climatic seasons (2: rainy, 3: dry) in the year, which allowed obtaining significant information on the state of contamination of this important ecosystem (Table 1).
Sampling sites
Name
Geographical coordinates
1
“Boca Chica”
18° 29′ 22″ North Latitude and 91° 47′ 37″ West Longitude.
2
“San Francisco”
18° 26′ 15″ North Latitude and 91° 45′ 27″ West Longitude.
3
“Punta Cochinos”
18° 26′ 14″ North Latitude and 91° 47′ 06″ West Longitude.
4
“Laguna del Este”
18° 23′ 39″ North Latitude and 91° 47′ 02″ West Longitude.
5
“Santa Gertrude”
18° 22′ 06″ North Latitude and 91° 44′ 17″ West Longitude.
6
“Laguna vapor”
18° 22′ 21″ North Latitude and 91° 49′ 32″ West Longitude.
7
“Botijuela”
18° 19′ 21″ North Latitude and 91° 50′ 06″ West Longitude.
8
Cañaveral
18° 24′ 59″ North Latitude and 91°50′ 16″ West Longitude.
9
“Porvenir”
18° 22′ 20″ North Latitude and 91° 51′ 46″ West Longitude.
10
“Puerto Arturo”
18° 20′ 27″ North Latitude and 91° 52′ 41″ West Longitude.
Table 1.
Sediment sampling points of the “Palizada” river.
2.2 Selection of sampling sites
The selection of the ten sampling points was representative of the system, both in number and location. Given the influence of seasonal variability [2]. A standardized collection study was performed; that is the entire study area during a similar period at the same depth, of a similar substrate [21]. Samples (sediment and water) were taken according to standardized methods [22].
2.3 Sample treatment
2.3.1 Treatment of glassware and preparation of standards
The glassware was treated with a 10% nitric acid (HNO3) mixture, as suggested by US-EPA method 3050B [23], and dried at a temperature of 105°C for later use. Calibration standards for Cu, Pb, Cd, Fe, Mg, and Mn (Table 2), at 50 or 100 mL, were prepared. The calibration blank was a 5% solution of HNO3.
Element
Wavelength (α)
Working range (μg/mL)
Copper
327.4
0.1–180
Cadmium
228.8
0–1.8
Lead
217
0.2–20
Iron
386
2–145
Magnesium
322.5
0–1.150
Manganese
219
0.2–20
Table 2.
Working ranges and wavelengths (α), used in the analysis of heavy metals.
2.3.2 Sediment sample treatment for heavy metal analysis
The sediment samples were dried at a temperature of 105°C for 24 hours, later they were treated in digestion with nitric acid (HNO3), hydrochloric acid (HCl), and hydrogen peroxide (H2O2) [23]. The resulting solution is filtered, and deionized water is added to it up to 100 mL, as suggested by EPA method 3050B [23]. The equipment used for the analysis was an atomic absorption spectrum Mark Thermo Scientific, the model is ICE 3500.
2.3.3 Sediment texture and Organic Matter (OM)
Granulometry analyses were carried out using the hydrometer of the Bouyocos Technique [24], OM was analyzed by the method suggested in NMX-AA-034-SCFI-2001 [25]; The principle of this method is based on the quantitative measurement of OM contained in water by evaporation and calcination of the samples and is summarized by the following steps: the dry sediment sample, previously pulverized, is sieved to obtain a specific particle size. This method requires constant weight measurements of porcelain vessels (crucibles), and sample calcination at 550°C to measure organic matter by weight difference with the following Eq. (1):
E1
Where:
OM: organic matter in mg/L
GI: is the weight of the crucible with the sample, before calcination (mg)
G: is the total weight of the crucible with the sample after calcination, in mg
2.4 Statistical analysis
To determine the variations by climatic season and by site, a one-way analysis of variance (ANOVA) was used. To establish the relationships between sediment texture, OM, and heavy metals, a Pearson correlation and multiple correlations (Software: Statistical 7.1) were used [26]. The normality of the data was verified using the Shapiro-Wilks statistical test (Software: Statistical 7.1).
3.1 Heavy metals, texture, and organic matter in sediments
The results of heavy metals are shown in Table 3 during the dry (1) and rainy (2) climatic seasons. These results confirm that Fe is one of the most abundant elements during the dry season (216.03–224.75 μg/g), suggesting evaporation phenomena and low sediment mobility. During the rainy season, the values decrease considerably (12.90–34.60 μg/g). During the dry season, the Mg (14.93–17.91 μg/g) did not show significant variations. In the rainy season (5.18–24.20 μg/g) the behavior pattern shows variations by the site. The Mn presents variations in both climatic seasons: dry season (6.89–13.44 μg/g), and rainy season (2.77–15.09 μg/g). Cu and Cd do not show a variable behavior. Although it is very difficult to differentiate between anthropogenic and natural contributions, the variations that occur during the climatic seasons; are an important element for contamination analysis.
Site
Climatic season
Metallic elements analyzed
Cu
Cd
Mg
Fe
Mn
1
1
0.19
1.01
17.24
216.06
9.82
2
1
0.19
1.05
16.97
222.20
13.44
3
1
0.19
1.13
16.62
215.40
11.70
4
1
0.19
1.20
17.74
224.75
12.90
5
1
0.19
1.28
14.93
222.73
6.89
6
1
0.19
1.48
17.70
219.17
8.07
7
1
0.19
1.52
14.69
219.67
8.85
8
1
0.19
1.53
17.52
222.54
9.54
9
1
0.19
1.55
17.72
219.62
7.15
10
1
0.19
1.60
17.91
217.34
9.00
1
2
1.13
2.25
5.18
33.31
7.58
2
2
1.23
2.30
5.97
18.05
15.09
3
2
1.18
2.30
7.81
20.63
7.12
4
2
1.10
2.34
9.36
20.63
5.25
5
2
1.10
2.20
21.05
12.90
2.77
6
2
1.18
2.26
10.10
34.60
6.90
7
2
1.21
2.26
22.16
19.89
5.18
8
2
1.17
2.25
6.26
28.71
8.01
9
2
1.13
2.19
24.20
19.52
6.56
10
2
1.11
2.26
10.29
29.45
5.40
Table 3.
Levels of heavy metals during the two climatic seasons: dry (1) and rainy (2) in μg/g.
The highest Cd values were in the rainy season at the “Laguna del Este” site with 2.34 μg/g. For Mg, the highest values occurred during the rainy season at the “El Porvenir” site with 24.20 μg/g. The results for Fe in the rainy season were higher at the “El Porvenir” site with 224.75 μg/g.
To analyze a contaminated site, it is important to establish correlations with the physical and chemical characteristics of the sediments, because different contaminants are related to organic matter and fine fractions. In this study, the texture of the sediments, organic matter, and their relationships with heavy metals (Table 4). The organic matter content is high and is related to the extensive area of mangroves, various species of macrophytes, and human settlements, which contributes to the variability of organic matter.
Results of analysis of variance (ANOVA) for Cu, Cd, Fe, Mg, and Mn.
Significant with a confidence value of 95%.
For Cu (p = 0.5136, p > 0.05) it shows that there are no statistically significant differences by site, however, for the climatic season, the statistical results show that there is a highly significant difference (p = 0.000, p < 0.05). The climatic season has a great influence on Cu abundance, as shown by a recent study [11, 27]. The maximum levels of Cu were recorded during the rainy season, which can be related to the very particular circulation mechanisms of the coastal zone at this time [2]. In previous studies [19, 28] similar levels of Cu were reported. Cu is associated with fine particles and OM [29] its high levels come from wastewater discharges and the hydrocarbon industry [30, 31]. In this study, no significant relationships between Cu, texture, and OM are shown (Table 6).
Test stats
Sand
Slime
Clay
OM
Correlation coefficient (r)
0.1627
−0.20821
0.120697
0.418
p-value
0.493
0.3939
0.6122
0.066*
Table 6.
Correlation values of texture and organic OM with Cu.
Significant at 95% confidence level.
For Cd (Table 5) there is no significant difference for the site (p = 0.0531, p > 0.05). But there is a statistically significant difference in the climatic season (p = 0.000, p < 0.05), the greatest influence on the presence and distribution of heavy metals is due to the climatic season. Table 7 shows the correlation results; none of the values show a significant relationship.
Test stats
Sand
Slime
Clay
OM
Correlation coefficient (r)
0.0376
−0.0780
0.1871
−0.466
p-value
0.8749
0.7436
0.4295
0.0383
Table 7.
Correlation values of texture and OM with Cd.
For Fe, only the climatic season influences the variation of the data (Table 5); Table 8 shows the correlation analyses; there is no evidence of relationships between heavy metals and sediment texture. There is a significant relationship between organic matter and Fe, which can be found forming oxides.
Mg is a natural element of the sediments and forms part of the hardness of the waters, it is abundant in calcareous sediments and is a source of available minerals. The statistical results are shown in Table 5 and confirm that only the climatic season influences the presence and availability.
The results of the relationships between sediment texture and OM with Mg are presented in Table 9. (No significant relationships are shown).
Test stats
Sand
Slime
Clay
OM
Correlation coefficient (r)
0.3101
−0.274
−0.3706
0.063
Value of the p statistic of the model
0.1832
0.2410
0.1077
0.7909
Table 9.
Values of the correlations of texture and organic matter with Mg.
For Mn, the results show that only the climatic season influences the presence and distribution of the metal (Table 5), The relationships between sediment texture and organic matter are shown in Table 10 (No significant relationships shown).
Test stats
Sand
Slime
Clay
OM
Correlation coefficient (r)
0.01320
−0.0426
0.1607
0.4063
p-value
0.9559
0.8584
0.4984
0.0755
Table 10.
Correlation values of texture and OM with Mn.
A correlation analysis (Table 11) between metal-metal was performed to determine the degree of relationship and if they have sources of generation in common.
In this study, the levels of heavy metals showed significant variations only due to the climatic season; the dry season has a more significant influence on the increase in levels of all the metals included in this study. As discussed throughout the chapter, high temperatures in the area cause phenomena of evaporation, concentration, and precipitation of pollutants from the water column to the sediments. The organic matter levels have a high relationship with Fe. Likewise, this metal shows significant associations with Cd and Cu, which indicates that the generated source is the same. It is concluded that the contributions of Fe, Mg, and Mn come from the agricultural and livestock activities carried out along the “Palizada” river, where its high agricultural and livestock productivity is an essential characteristic of the municipality.
Likewise, the absence of effective programs for monitoring and controlling pollutants in the Mexican coastal environment, the growing industrialization, and urbanization have caused more than 30% of the rivers and lagoons in the Gulf of Mexico to be contaminated. The sediments represent a reservoir of heavy metals that contributes significantly to the bioavailability of aquatic organisms. On the other hand, the levels of organic matter in some sites exceed the criteria that have been established for marine areas where these levels should not be greater than 10%. These high levels of organic matter corroborate that the “Palizada” river directly influences anthropogenic discharges and rain slides.
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Written By
Carlos Montalvo, Claudia A. Aguilar, Yunuen Canedo, Alejandro Ruiz, Brenda Zermeño, Ruby S. Gines and Rosa M. Cerón
Submitted: 03 March 2022Reviewed: 24 March 2022Published: 17 May 2022
Open access peer-reviewed chapter
