Jéssica de F. Delgado
Fluminense Federal University - UFF, Niteroi, RJ, Brazil.
Leonardo da S. Lima
Fluminense Federal University - UFF, Niteroi, RJ, Brazil.
Khauê Vieira
Fluminense Federal University - UFF, Niteroi, RJ, Brazil.
José Antônio Baptista Neto
Estefan Monteiro da Fonseca
Fluminense Federal University - UFF, Niteroi, RJ, Brazil.
ABSTRACT
Water column variances in the aquatic environment, motivated by either natural or anthropogenic processes, may impact the stability of trace metals in the sediment of Santos Port Complex (SPC), located in southeast Brazil. Trace metals such as Cu, Zn, Ni, Pb, and Cd potentially negatively affect ecological and biological compartments in estuarine water. To evaluate the status of the sediment of the SPC, the present article investigated the geochemical fraction of sedimentary trace metals by applying the BCR (European Community Bureau of Reference) sequential extraction approach. Organic matter and fine grain size, characteristic of an estuarine environment, showed a direct influence on the concentration dynamics of trace metals in sediments, especially for Pb, Cd, and Ni. In the specific case of Zn and Cu, there was a potential source of contamination in the port. The largest fraction of the metals studied was non-residual, potentially mobilizable in an environment where variation in the physicochemical parameters of the water column is highly variable, something frequent in estuarine environments.
Keywords: trace metal speciation; Santos Harbor; sediment; environmental impact.
As a result of the nature of port activities, transport complexes are generally installed in geomorphologically protected areas, safe from strong open sea hydrodynamics. In addition, for the beneficiation, transformation, and circulation of transported raw materials and industrial products that arrive and leave the portuary site constantly, an industrial park is installed nearby, resulting in the consequent human settlement of the entire region. Thus, natural confined sites such as estuaries and bays are suitable environments for developing this type of activity (Iglesias et al., 2021). On the other hand, estuaries and bays, due to their strong water physic-chemical gradients derived from the transition between freshwater on the continent and salty marine waters, present a great biodiversity, representing one of the most productive ecosystems around the planet (Barbier et al., 2011; Pinto and Marques, 2015). Additionally, the calm water body works as a nursery for marine organisms that use this environment to reproduce and feed (Kotzé, 2016). Therefore, despite their great ecological importance and thus a high degree of sensitivity, port regions represent one of the environments most altered by human activities (Gillanders et al., 2011; Vermeiren and Sheaves, 2014; Kotzé, 2016). Among the most critical impacting factors existing in the day-to-day life of the ports are the constant dredging, waste disposal, constant transit of vessels, high population density, and waste generation, among others.
The natural characteristics of estuarine environments make these ecosystems even more complex from an ecological point of view (Sun et al., 2015; Zhang M. et al., 2017; Duggan et al., 2019; Izegaegbe et al., 2020). Their geomorphologically protected water, with low hydrodynamic fluxes and restricted water exchange with the adjacent sea, results in lower oxygen levels in the water column, which is propitious to the concentration of contaminants on its sediment, composed of fine-grained particles and high levels of organic matter (Guerra-García and García-Góme 2004). So, many ports are known as critically polluted sites, representing a real threat to the local living organisms (Galkus et al., 2012; Zaaboub et al., 2014).
The marine environment has become polluted due to a wide range of contaminants sourced from several anthropogenic activities, and this has prompted worldwide attention for a long time (Adekunle, 2012; Eliku and Leta, 2018). Trace metal pollution in estuarine ecosystems is an increasing challenge, as most trace metals beyond threshold concentrations are potentially toxic to living organisms (Prabhakaran et al., 2016). These elements can find their own ways to enter the food web in the environment. However, the toxicity and associated damage of individual metals are relatively well studied with established baselines (Yi et al., 2021).
Estuarine ecosystems are highly dynamic sites that are often coupled with seawater dilution effects and various anthropogenic inputs. All environmental parameters can then further affect trace metal bioassimilation since they influence interactions between heavy metals and the aquatic biota. Thus, the comprehension of trace metal bioavailability is not an easy task; it requires the integration of all major contributing factors, such as different environmental variables, multi-heavy metal mixtures, and their speciation (Gu and Gao, 2021), when attempting to investigate processes that dictate the relation between trace metals and the biota.
Total levels of trace metal recording in the sedimentary pool do not represent an effective indicator when the object is the evaluation between natural and anthropogenic sources (Relic et al., 2010, Passos et al., 2011, Okoro et al., 2012) and its potential bioavailability (Zhong et al., 2011). For this purpose, recent authors have applied sequential partial extraction approaches to evaluate the specific chemical forms associated with sedimentary phases and metal sources (Hang et al., 2009; Davutluoglu et al., 2011).
One commonly used sequential extraction approach is the BCR (European Community Bureau of Reference) method. The BCR method divides trace metals into four groups: exchangeable and easily soluble fractions, easily reducible fractions, oxidizable fractions, and residual fractions. The first three fractions theoretically represent the potentially available fractions that under physicochemical fluctuations of the water column, are made available. The last represents a difficult fraction to mobilize (Sahara et al., 2015), considered naturally inert.
The main object of the present study was to diagnose the status of sedimentary trace metals to allow the dynamic projection of the geochemical distribution under variations of the physicochemical parameters of the water column in the Santos Estuarine System (SES).
The SES (Figure 1) consists of a coastal region severely modified by countless human activities of the most diverse nature, resulting in several potential pollution sources, including a vast industrial complex, intensely populated areas, and agricultural, and portuary activities. One of the most significant sources is Cubatão industrial park, located in the Santos watershed basin (Azevedo Netto et al., 2022), which concentrates petrochemical, steel, chemicals, fertilizers, and logistics, as well as energy production and services and whose activities present potential punctual and diffuse sources of pollutants. Parallelly, the same region is under the influence of irregular depositions of industrial solid waste caused by port activities, sewage treatment stations, submarine outfalls, and clandestine discharges of domestic sewage and sanitary landfills. Finally, SUS is still the target of constant impacts generated by the maintenance of the Port of Santos, the largest port complex in Latin America, where periodical dredging activities are carried out (Figure 1). On the other hand, the coastal region receives many tourists during the summer (Azevedo Netto et al., 2022), with traditional fishing being an important economic activity in the region (Hortellani et al., 2008).
A sampling campaign was carried out on May 21. 32 sampling spots were distributed along the main estuarine channel, as shown in Figure 1. Water column physicochemical characterization was made at surface and bottom water depths during the ebb tide. Salinity was evaluated with a multiparameter Horiba U10 probe.
Additionally, with the same approach as Netto et al. (2021), past data was also used to reinforce the accuracy of the physical analysis of the waters. The average of all data groups used was compared with the trace metal concentrations and other environmental parameters (pH, Eh, dissolved oxygen, and salinity).
A stainless Van Veen grab was used to maintain sediment composition integrity and avoid contamination during sediment sample collection. Then the samples were properly packaged and stored under refrigeration (~-20 ºC) until analysis. The following analysis was carried out on the sediment samples: the sediment grain size, total organic carbon (TOC) levels, phosphorus concentrations, and metals (Ni, Cu, Zn, Cr, and Pb) were determined.
Trace metal samples were maintained in pre-acidified plastic bowls and transported to the laboratory for analysis. For the grain size evaluation, a pre-treatment process was used, degrading the organic matter with hydrogen peroxide (H2O2). Posteriorly, the grain size was measured by a Microtrac S3500 grain size analyzer. The results were classified into sand, silt, and clay according to the sediment composition.
Then, the fine material (below 0.063 mm) was used to extract the trace metals. Sequential extraction was performed using the BCR approach. After samples were centrifuged and further diluted, trace metals (Pb, Cu, Ni, Zn, and Cd) were analyzed by Inductively Coupled Plasma-Atomic Emission Spectrometry. The detection limits of the method are, respectively: Pb, 15 mg/kg; Cu, 1.5 mg.kg-1; Ni, 0.1 mg.kg-1; Zn, 0.4 mg.kg-1; and Cd, 0.4 mg.kg-1.
The normal distribution of the data was tested with the Shapiro-Wilk test. Spearman’s correlation was used to evaluate the relationship between trace metal data and environmental parameters.
Sediment trace metal levels represent potentially reasonable indicators of the state of an ecosystem (Forstner and Wittmann, 1981). Once trace metals enter the estuary, they promptly become associated with the particulate phase and sink to the subaquatic bottom (Hanson et al., 1983). The decantation process depends on several water column features, such as pH, Eh, ionic strength, organic and inorganic matrixes, and the available surface area for adsorption caused by variation in grain size distribution (Davis et al., 1991). The combination of trace metals with fine particles (silt and clay) is attributed to co-precipitation or complexation reactions of these elements on particle surfaces, determining the distribution pattern of trace metals in sedimentary pools (Ho et al., 2010). In the present study, grain size records are presented in Figure 2. Size is a fundamental property of sediment particles. It determines particle diffusion and deposition through the environment and thus provides relevant information about the sediment’s provenance, transport history, and depositional conditions (Kenneth Pye, 2004). In the present study, the finer grain size fraction was present along all the sampling stations, being more concentrated in the estuarine inward area, where the lower hydrodynamic conditions permitted its deposition.
Sediments consist of multi-phase matrixes composed of silicates, carbonates, hydroxides/oxides, sulfates, and organic substances as major components (Zhu, 2006). Organic matter, in turn, shows the capacity to retain, reduce mobility, and consequently reduce trace metal bioavailability (Impellitteri et al., 2002; Wolińska et al., 2018). Therefore, organic compounds play an important role in forming complexes and retaining heavy metals in a potentially mobilizable form (Aydinalp and Marinova, 2003).
In the present study, the organic matter levels varied between 3,5 and 22,5%. Contrary to expectations, the higher concentrations were in Santos’s channel due to the greater currents in this area. On the other hand, the water salinity, proper from open sea water, may promote estuarine flocculation and aggregation mechanisms, carrying the dissolved organic matter to the subaquatic bottom pool (Boyle et al., 1977; Sholkovitz, 1978; Davis, 1984; Gibbs, 1986). Thus, the estuarine physico-chemical particle settlement mechanism, together with the existence of a submarine outfall and the potentially active processes of flocculation, can explain this distribution.
Among the pollutants present in estuarine environments, a critical role is played by trace elements, which, under certain water column conditions, are potentially toxic to living species and are transmitted through the trophic chain (Rosado et al., 2016a, b; Tarnawski and Baran, 2018). Trace elements deposited in bottom sediments can potentially threat aquatic organisms. Moreover, in the case of improper sediment management, e.g., from the dredging of port evolution basin sediment, they can also pose the danger of having a toxic impact on land biota.
Some authors demonstrated that flocculation of dissolved organic matter in estuarine environments may enhance sedimentation of organic-metal complexes derived from terrestrial ecosystems (Sholkovitz, 1978; Sholkovitz et al., 1978; Wells et al., 2000; Turner et al., 2002; Stolpe and Hassellöv, 2007; Biati et al., 2010; Samani et al., 2014; Heidari, 2019). As seen in Figure 3, total trace metal concentration data revealed two distribution patterns. The first one was followed by Ni, Pb, and Cd, which showed the same appearance as organic matter levels. This data reveals the importance of the organic matter in the heavy metal accumulation in the Santos Estuarine System.
The second pattern, followed by Zn and Cu, did not follow the deposition pattern promoted by organic matter affinity and concentration. The similarity between these trace metals and their random character suggested port activity as a potential source for these trace metals. Copper mining and processing are fundamental for infrastructure development. As a result, highly industrialized areas use the present Cu contamination from metallurgical waste (Wang et al., 2015). More important than that, copper and zinc are used in antifouling paints as active ingredients and stabilizers, respectively (Bighiu et al., 2017).
Table 1 presents the statistical analysis results. According to the obtained data, hydrodynamic fluxes represent the main distribution parameter for local floating particles since fine grain size and organic matter have a significant correlation. The same can be said for Cu and Zn since both metals presented significant correlations with fine-grained particles. On the other hand, organic matter showed to be preponderant for Cd and Pb sediment accumulation.
Sedimentary trace metal fractionation reflects the metal binding processes in sediments. The dynamic of metal fractionation in these sediments is a result of the differences between each metal source and its particular affinity with environmental matrixes and particular physicochemical responses. Generally, metals sourced from human activities are presented in the potentially mobilizable fractions, whereas metals derived from natural geologic sources are in the residual fractions (Passos et al., 2010).
In the present study, a significant amount of all studied metals was associated with the non-residual phase, indicating that all trace metals are potentially bioavailable. In the non-residual sediment fraction, the speciation status and potential bioavailability of trace metals primarily depend on the binding of these elements to solid particles, their presence in ionic form in the water column, or their being adsorbed on the surfaces of sediment mineral/organic matter/microorganisms complexes. In this sense, the results showed that the subaquatic bottom’s stored trace metals may be remobilized from the sedimentary pool via natural or anthropogenic mechanisms. The first hypothesis may be the result of the water column’s physicochemical conditions variation (e.g., pH, redox potential, organic matter, and salinity) (Wu et al., 2015), as a result of estuarine tidal and saline wedge oscillations. On the other hand, the constant dredging work necessary to maintain the depths in the vessels' evolution basin can affect the stability of the bottom sediments and thus remobilize the pollutants deposited back into the water column (Monte et al., 2019). So, according to the present study, especially Cd and Pb showed less association with the most stable fraction.
In aquatic bodies, the non-residual trace metals are transported as dissolved, colloidal, or particulate elements or compounds associated with available natural matrixes like organic matter, Fe and Mn (oxyhydr) oxides, and clay particles, which are omnipresent in aquatic ecosystems and present a high metal sorption ability (Singh and Subramanian, 1984; Parker and Rae, 1998; Warren and Haack, 2001; Pokrovsky and Schott, 2002; Hassellöv and von der Kammer, 2008; Nystrand et al., 2012). According to the present study, the organic phase recorded omnipresence for all the studied trace metals as a result of the organic matter’s significant availability in estuarine areas, where the high productivity and the water exchange restriction permit its accumulation. After organic matter enters the environment, it produces trace metal organic complexes due to abundant carboxyl, hydroxyl, amine, and other organic particle surface reactive groups, increasing its adsorption capacity (Kulikowska et al., 2015; Zhou et al., 2015). Some authors have suggested that Cu is able to form complexes with organic matter (Manceau and Matynia, 2010; Moon and Peacock, 2012; Karlsson et al., 2006) or organic matter-copper mineral ternary complexes (Strawn and Baker, 2009). So, in the present study, sequential extraction analysis confirmed organic matter as an important matrix immobilizing local Cu. Recorded data in the present article suggested that the dynamic of the other studied trace metal mobility is also associated with high organic matter concentrations, as shown in Figure 4.
In the same way that Cu, Pb, and Zn have great affinity with the hydroxyl functional group available on mineral surfaces like kaolinite, oxides, oxyhydroxides, and Fe and Al hydroxides (Smith et al., 1995). According to Silveira et al. (2003), iron oxides are the most relevant soil constituents for retaining heavy metals. The authors' affirmation is applicable to the present case, except for Ni and Cd, trace metals that recorded negligible participation in the reducible phase in most sampling stations. According to Qion et al. (2020) and Ma et al. (2021), sediment minerals are the main constituents of solid sediment matrices, and clay minerals are the most impacting elements in sediments that primarily include layered silicate minerals and crystalline and amorphous oxide matrixes that significantly influence the immobility and diffusion of trace metals.
The most dangerous fraction of trace metals stays in the free ionic species, which are highly mobile and easily bioavailable (Sunda and Lewis, 1978; Luoma, 1983). In the present study, this fraction was shown to be less important for Cu. The other metals, on the other hand, recorded a significant contribution from the soluble or exchangeable fraction.
Heavy metals are increasingly present in the environment, representing risks to ecological health when in anomalous concentrations. Their total concentrations do not allow for the projection of the potentially deleterious effects these elements offer. Its toxicity is associated with the particular characteristics of each metal and the ligand matrices available in the environment since these will define the mobility of trace metals. In the present study, metals were present at unnatural levels in most sampling stations. Organic matter and fine grain size, characteristic of an estuarine environment, directly influenced the concentration dynamics of trace metals in sediments, especially for Pb, Cd, and Ni. In the specific case of Zn and Cu, there was a potential source of contamination in the port. The largest fraction of the metals studied was non-residual, potentially mobilizable in an environment where variation in the physicochemical parameters of the water column is highly variable, something frequent in estuarine environments. More studies are needed to assess the effective negative effects of metals on the Santos estuarine ecosystem.
This research was funded by Maricá Development Company (CODEMAR) and by the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq). The authors are also grateful to the Municipality of Maricá for infrastructure and administrative support.
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Received: June 2, 2023
Approved: June 2, 2023
DOI: 10.20985/1980-5160.2023.v18n1.1884
How to cite: Delgado, J.F., Lima, L.S., Vieira K., Baptista Neto, J.A., Fonseca, E.M. (2023). BCR sequential extraction for geochemical fractions and assessment of Zn, Ni, Cd, Cu and Pb in the coastal sediments – Santos Port Complex, Southeast Brazil. Revista S&G 18, 1. https://revistasg.emnuvens.com.br/sg/article/view/1884