Metals and metalloid contamination and geochemical normalization factors in surface sediments from an important estuarine system in Southern Brazil

doi:10.21203/rs.3.rs-3100971/v1

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Metals and metalloid contamination and geochemical normalization factors in surface sediments from an important estuarine system in Southern Brazil

https://doi.org/10.21203/rs.3.rs-3100971/v1

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Estuarine areas usually suffer significant trace element contamination effects, resulting in significant environmental risks. This is the case of the Paranaguá Estuarine System (PES), located in Southern Brazil, home to one of the largest ports in Latin America and it still boasts of a remarkable biodiversity surrounding by threatened mangrove areas. In this context, this study aimed to assess the quality of sediments concerning metals and metalloid As contamination and comparison to sediment contamination guidelines. In addition, biochemical normalization factors were applied to find out if the sources of the investigated elements were natural or anthropogenic. In 2018, 38 surface sediment samples were sampled seasonally from different PES areas to the determination to metals, metalloid As, and geochemical characteristics. Higher element values analyzed were detected close to the cities of Antonina and Paranaguá and near river mouths, potentially associated with port activities and anthropogenic throughout the surrounding drainage basins. The results revealed concentrations above the Threshold Effect Level (TEL) for Cr, Cu, and metalloid As. The Principal Component Analysis of the analyzed variables showed a strong interaction involving metals/metalloids, organic matter, nutrients, total organic carbon and the fine fraction of sediments. Metals and metalloid As concentrations were lower than in other tropical estuaries, which may indicate water column desorption or aquatic organism absorption, potentially associated to physicochemical water variations or sediment remobilization and resuspension due to dredging activities. The applied geochemical indices indicate low to moderate PES sediment contamination, although some areas presented high values, leading to ecological concerns.

Metals

metalloids

estuarine sediments

contamination

estuary

Estuaries comprise semi-enclosed coastal environments connected to the ocean, where marine water is mixed with freshwater (Day Jr et al., 2012; Pritchard, 1952). These areas are highly productive and sheltered environments, used by many coastal and marine species worldwide as reproduction and feeding areas, even though they display the potential to retain dissolved and particulate material and are highly exposed to anthropic activities (Santana et al., 2013; Wang et al., 2013; Yang et al., 2006).

Anthropic impacts in estuarine ecosystems can lead to sediment contaminant accumulation, such as metals and metalloids (Cunha et al., 2021; Fonseca et al., 2014; Fernandes et al., 2020). These contaminants have become a global concern due to their toxicity, bioaccumulation and biomagnification potential, persistence, and non-degradability (Nobi et al., 2010). They are, however, also naturally present in the earth's crust, so understanding their distribution and source apportionment in environmental matrices is important to be able to differentiate natural and anthropogenic sources and identify potentially polluting sources (Castillo et al., 2013; Nobi et al., 2010; Duodu et al., 2017). Furthermore, several biotic and abiotic processes directly affect metals/metalloids remobilization processes, such as turbations, both biological (i.e., benthic organism feeding behavior) and anthropogenic (i.e., dredging activities), which may result in these elements' resuspension, increased bioavailability and trophic chain entry, leading to ecological risks (Bevilacqua et al., 2009; Jesus et al., 2004; Tessier et al., 2011).

In this context, the aim of the present study was to analyze the quality of surface sediments at the Paranaguá Estuarine System (PES), in Southern Brazil, regarding metals and metalloid As contamination. This estuary is home to the largest port in Latin America and is located in a highly industrialized area (Vieira et al., 2021), and, thus, highly vulnerable to elemental contamination. Even so, it still boasts a remarkable biodiversity surrounded by threatened mangrove areas, well-preserved Atlantic Rainforest fragments and several conservation units (Garcia & Martins, 2021), and was listed by UNESCO as a world heritage of biodiversity in 1999, thus requiring directed conservation efforts.

Study area

The PES, located on the Paraná coastal plain, on the southern coast of Brazil, comprises about 612 km², categorized in an east-west section home to the Paranaguá and Antonina bays and a north-south section home to the Laranjeiras, Guarquêba and Pinheiros bays and the Benito and Itaqui coves (Martins et al., 2010). The estuary is connected to the ocean through three tidal channels, with the Galheta channel comprising the main access route to the Paranaguá port. The PES displays significant socio-economic importance, in the form of several fishing, tourism and industrial activities, also home to port areas containing fuel terminals, fertilizer industries and the main grain terminal in South America (Martins et al., 2010; Mizerkowski et al., 2012). The surrounding estuary area is also home to two of the most important cities in the region, namely Paranaguá (156,174 inhabitants) and Antonina (18,949 inhabitants), further contributing to PES contamination in the form of domestic effluents and solid waste inputs. In this regard, the sewage systems of both cities are very precarious, and most effluents are released directly into the water bodies that flow into the estuary without adequate treatment (Kolm et al., 2002). In addition, many agricultural activities are carried out upstream of Antonina Bay, leading to agrochemical inputs in PES tributaries (Souza et al., 2018; Trevizani et al., 2019).

Sediment sampling

A total of 38 surface sediment samples (0–10 cm) were collected seasonally in March, June, September, and November of 2018 (Fig. 1). The sampling pointswere selected considering estuary morphology and the location of different human activities, such as industries and urban and port activities, range from the inner areas of the estuary to its mouth connected to the ocean,at depths of over 35 m.

Surface sediment samples were collected employing a Van Veen sampler, transferred to polyethylene plastic bags, transported to the laboratory on ice, and maintained chilled until further analyses.

Physicochemical water parameters

Physicochemical water column parameters (pH, dissolved oxygen (DO) and salinity) were analyzed in situ at the ebb tide close to the bottom using a multiparameter Horiba U-51probe. Fine sediment granulometric distribution was analyzed by laser diffraction employing a Mastersize 2000 Malvern Panalytical® equipment. The Gradistat software was used to determine granulometric statistical parameters (average diameter and selection degree) (Blott & Pye, 2001). Organic matter (OM) concentrations were estimated by the weight loss method following ignition. Total organic carbon (TOC) and total nitrogen (TN) levels were determined following sediment treatment with 10% HCl to exclude carbonates employing a 2400 Series II CHNS/O PerkinElmer® analyzer. Total phosphorus (TP) concentrations were determined after sample ignition at 550°C for 12 hours.

Metals and metalloid As analyses

Metals Al, Ba, Cd, Cr, Cu, Fe, Mn, Pb, Zn, and metalloid As were determined in HNO₃-digested samples following the United States Environmental Protection Agency 3050B method (US EPA, 1996) through inductively coupled plasma mass spectrometry (ICP-MS), according to US EPA method 200.8 (US EPA, 1994). A certified reference material (MESS-2, marine sediment, NRC Canada) was used for analytical certification. Quantitative recoveries of elements in sediments ranged from 93.25 to 111% and the limits of detection for Al, Ba, Cd, Cr, Cu, Fe, Mn, Pb, Zn and As were 0.275; 0.02; 0.001; 0.006; 0.05; 0.355 0.009; 0.02; 0.549 and 0.001 ug kg^− 1, respectively.

The Past statistical software v. 3.0 integrated with Excel spreadsheets (Microsoft®) was used for all analyses. The Shapiro-Wilk test was first performed to assess data normality. As most of the data did not follow a normal distribution, non-parametric tests were chosen. The non-parametric Kruskal-Wallis test was performed to verify significant variable differences. Spearman correlations (r) were calculated between investigated variables to assess the potential relationship between the determined metals/metalloid and physicochemical water parameters. Correlation strengths were considered according to Dancey and Reidy (2006), r values < 0.4 show a weak correlation, 0.4 ≤ r < 0.7 moderate, and r ≥ 0.7 strong. Correlations above 0.7 (p < 0.05) were considered significant.

A Principal Component Analysis (PCA) was employed to further investigate associations between the variables. Variables already strongly correlated with each other, either directly or inversely (Spearman coefficient > 0.9 or < − 0.9), were removed to avoid a double weight of variables that explain themselves or that are closely related. The exceptions were coarse and fine granulometric fractions. In this sense, organic matter was considered instead of total organic carbon. The Kaiser rule was not considered. The points were divided into saline sectors to facilitate data visualization - blue/euhaline, green/polyhaline and yellow/mesohaline. Thus, the PCA was run with a total of 19 variables.

Geochemical Normalization Factors

To assess PES sediment metals and metalloidAscontamination, the enrichment factor (EF), the contamination factor (FC) and the geoaccumulation index (Igeo) were determined, as follows:

Enrichment factor (EF)

The EF differentiates metals and metalloid As sources as anthropogenic or natural. Iron (Fe) was used for normalization purposes, due to the lack of evidence of anthropogenic sources of this element, in addition to its naturally high environmental concentrations (Arisekar et al., 2022; Dung et al., 2013; Silva et al., 2017; Turekian & Wedepohl, 1961). The EF was obtainedthrough the ratio between each determined element (M) and the normalizing element (N) divided by the same background ratio (standard shale), according to Eq. 1 (Ergin et al., 1991). EF < 1.0 suggests lithological element origins, while values ≥ 1.0 indicate anthropogenic origin.

FE = \(\frac{\text{M}/\text{N} sample}{\text{M}/\text{N} background}\) Eq. 1

Contamination Factor (CF)

The CF comprises the ratio between each sediment element concentration and their respective reference values, according to Eq. 2. According to Hakanson (1980), CF < 1.0 indicate low contamination, 1.0 ≤ HR < 3.0, moderate contamination, 3.0 ≤ HR < 6.0, considerable factorcontamination and HR ≥ 6, very high contamination.

FC =\(\frac{\text{C} trace elements}{\text{C} backgound}\) Eq. 2

Geoaccumulation Index (Igeo)

The Igeo determined metals and metalloid As sediment contamination compared to background levels, according to Eq. 2 (Müller, 1969), where Cn is the determined concentration of a certain element in the sediment and Bn is the reference value of said element in the sediment. A 1.5 constant is used as a matrix correction, introduced to minimize the effect of possible variations in background values caused by lithogenic effects. Igeo ≤ 0 indicates unpolluted sediments, 0 < Igeo ≤ 1, unpolluted to moderately polluted, 1 < Igeo ≤ 2, moderately polluted, 2 < Igeo ≤ 3, moderately to heavily polluted, 3 < Igeo ≤ 4 heavily polluted, 4 < Igeo ≤ 5, heavily to extremely polluted and Igeo > 5, extremely polluted (Müller, 1969).

\(\text{I}\text{g}\text{e}\text{o}=\text{l}\text{o}\text{g}2[\text{C}n/1.5 \text{B}n]\) Eq. 3

Physicochemical water parameters

Water pH is an important environmental quality indicator, essential in controlling contaminant behavior in aquatic environments (Cai et al., 2017; Glaspie et al., 2018). This variable directly influences metals and metalloids solubility, bioavailability, bioaccumulation and toxicity through cation and anion partitioning (Zhang et al., 2014). Lower pH values hinder sediment element retention, reducing the surface charge of fine particles and Fe, Al and Mn hydroxides. This leads to increased cation concentrations, such as H⁺, Fe³⁺ and Al³⁺, which may compete with other cations for negative sediments sorption sites. High pH values, in turn, promote sediment adsorption and precipitation processes (Guan et al., 2018; Warren & Haack, 2001). Herein, pH values ranged from 7.02 to 8.85 in March (Supplementary Table S1), increasing in June (7.81 to 9.20), September (7.60 to 8.30) and November (7.20 to 8.50). The basic pH values observed at the PES suggest an interaction with the ocean carbonate system (Millero, 2000).

Dissolved oxygen is an important estuarine parameter to be evaluated (Decker et al., 2014), as decreased levels in coastal systems have become a global phenomenon (Kemp et al., 2009), mainly due to eutrophication processes (Iriarte et al., 2010). Low DO levels were noted near the city of Paranaguá (point 8 in November and point 11 in March, June, and September), already expected due to high untreated domestic effluent discharges (Supplementary Table S1). Higher DO levels at the other sampling points can be attributed to greater saline influence from the ocean, corroborating previous assessments in the same area (Machado, 2011).

As transitional continental-oceanic environments, estuaries present major salinity alterations (Telesh & Khlebovich, 2010), which in turn play an important role in element mobility and sorption (Du Karbassi et al., 2014; Laing et al., 2008). High salinity values are associated with higher levels of Na, K and Ca cations that compete with metals/metalloids for sorption sites, also hindering the activity and growth of sulfate-reducing bacteria, influencing organic matter (OM) sediment decomposition, resulting in increased bioavailability of these elements (Hou et al., 2013; Peng et al., 2019). In the present study, salinity PES values ranged from 8.3‰ in November to 20.8‰ in June in most of the innermost sampling points, while values at external points ranged from 34.2‰ in September to 36.5‰ in June (Supplementary Table S1).

Significant differences (p < 0.01) were observed for the dry and rainy seasons for pH, salinity and dissolved oxygen, suggesting that the observed spatial differences are due to seasonality. Increased rainfall rates and consequent increases in continental drainage in November resulted in lower salinity values, for example, which lead to decreased dissolved salts and lower water column salinity. In contrast, low rainfall rates in September led to a greater influence of marine waters in the inner part of the estuary. Points 1 and 11 presented the lowest salinity values due to their location at the mouth of the main rivers in the estuary.

The sampled surface sediments from the PES are basically composed of sand with the predominance of fine silt and clay fractions in some areas (Fig. 2). Higher levels of coarse to fine silt were observed close to Antonina, except at the mouth of Cachoeira River (point 1), similar to the findings reported by Lamour et al. (2004). Granulometric changes at the mouth of the Faisqueira and Cachoeira rivers may be associated with the Cachoeira River transposition that took place in the 1970s (Branco, 2008). The average sediment diameter ranged from fine sand to siltin areas adjacent to the Paranaguá port. Fine sand was predominant at the southern PES mouth, with coarse sand increasing to the outermost points, similar to that reported by Negrello-Filho et al. (2018). A predominance of poorly selected sediments was observed mainly in the innermost points of the estuary, while sediments were moderately well to well selected near Mel Island. Sediment granulometry is directly associated to metals/metalloids contamination and OM content, which tend to increase in finer sediments (Coringa et al., 2016; Yao et al., 2015), due to larger contact surfaces and high surface adsorption (Zhang et al., 2009).

Organic Matter contents ranged from 0.73 g kg^− 1 to 167.68 g kg^− 1in the dry season and from 0.30 g kg^− 1 to 96.84 g kg^− 1in the rainy season, averaging 22.99 g kg^− 1and 23.39 g kg^− 1, respectively. The highest values were detected in June, consistent with local mixing/dilution processes. The highest concentrations were detected at points 10 and 11, located respectively at the Paranaguá port and the mouth of the Itiberê river, suggesting high sewage contributions at these points and corroborating Martins et al. (2010), who also detected sewage-contaminated areas close to the city of Paranaguá.

High TOC concentrations are commonly found in low-energy environments with a predominance of fine sediments, such as estuaries (Siqueira & Aprile, 2013). In this regard, TOC concentrations were higher in areas close to the municipalities of Antonina, ranging from 0.42% (September) to 5.06 (March) and Paranaguá, 4.25 (March) to 7.77% (June) (Fig. 3). The external estuarine areas presented lower concentrations, possibly due to the predominance of a coarse sediment fraction. Other studies carried out in bays and estuaries worldwide report similar levels (Table 1).

Table 1

Total Organic Carbon (TOC) in superficial Paranaguá estuary sediments compared to other estuarine environments worldwide.
TOC (%)	Area	Reference
0.42–7.77	Paranaguá	Present study
0.06–4.79	Sepetiba Bay	Rodrigues et al. (2017)
0.80–8.60	São Vicente (Estuary)	Perina et al. (2018)
1.00–6.10	Guanabara Bay	Martins et al. (2018)
0.30–7.70	Toulon Bay	Tessier et al. (2011)
5.35–24.88	Port Klang	Sany et al. (2013)
0.20–9.00	Guadiana River Estuary	Camacho et al. (2015)
0.36–5.33	Sungai Pinang	Chuan et al. (2016)

The PT results from this study are shown in Fig. 4, ranging 2.66 mg kg^− 1 at point 32 to 880.15 mg kg^− 1 at point 11 TN concentrations followed TOC patterns, with higher concentrations in points adjacent to the cities of Antonina and Paranaguá, ranging from 0.60 mg kg^− 1 at point 4 to 3,484.90 mg kg^− 1 at point 11, demonstrating the influence of continental drainage on this parameter, which increases during rainy periods, highlighting interannual variability, as described by Machado (2011). In the present study, representative values were also found at the mouth of the estuary.

Many estuarine environments are heavily affected by high nutrient inputs from anthropogenic sources, mainly nitrogen and phosphorus (Lu & Tian, 2017). Most of these nutrients are used in crops and modify N:P ratios through atmospheric nitrogen deposition or runoff from fertilizer applications (Vuuren et al., 2010). Previous studies have reported that the internal and intermediate areas of the PES are classified as eutrophic, while the external part is classified as oligotrophic (Lana et al., 1997; Sá et al., 2015), due to local hydrodynamics. In this regard, the outer part of the estuary may have presented higher nutrient concentrations due to the river flow in the Cotinga channel and later in the Galheta channel (Knoppers et al., 1987; Machado et al, 1997). Furthermore, Noenrberg et al., (2007) indicated sediment deposition in the outlet channel, which corroborates the concentration of these nutrients detected in that area.

Metals and metalloids

The US EPA method 3050B was employed to determine bioavailable sediment elements. The concentrations of these contaminants in the surface sediments of the SEP (minimum and maximum) are presented in Table 2 and they were compared with other studies in the literature.

Table 2

Concentration of metals and the metalloid As (ug kg^− 1) in superficial Paranaguá estuary sediments (minimum - maximum) compared to to other estuarine environments worldwide.
	Al	Ba	Cd	Cr	Cu	Fe	Mn	Pb	Zn	As
This study	183.92–17707.41	nd – 180.38	nd – 0.21	nd – 55.8	nd – 72.62	350.03–36854.4	9–791.98	0.29–25.48	nd – 117.1	nd – 12.12
Santos Estuary¹	-	-	0.14	20.52	11.14	17188.0	63.06-879.56	15.55	58.40	9.07
Paranaguá Estuary²	-	-	-	-	1.1–12.1	-	-	nd – 12.1	-	-
Paranaguá Estuary³	-	-	< 0.001	14.50–58.00	< 0.04–16.20	-	-	< 0.30-29.75	26.95–80.50	-
Guanabara Bay⁴	-	-	-	86.6–234.6	45.3–123	24451–45379	301.6–821	51.7–101.8	200.8–424.9	-
Guanabara Bay⁵	-	-	1.1–3.7	50.5-170.4	69.3-280.4	-	-	52.3-264.7	209.8-681.9	6.7–8.7
Bestari Jaya Malasia⁶	-	-	-	12.53–31.97	3.7–14.29	-	-	11.81–15	17.59–62.8	0.10–0.22

¹Netto et al., (2022); ²Rocha et al., (2017); ³Choueri et al., (2009); ⁴Fonseca et al., (2009); ⁵Silveira et al., (2017); ⁶Ashraf et al., (2011).

nd: Not detected.

In general, higher concentrations of the analyzed metals and metalloid As were detected in the internal PES area, close to Antonina and in areas adjacent to the port of Paranaguá, while the lowest values were found at the mouth of the estuary and at external points. This is expected, due to the determined granulometric composition, the presence of OM and the drainage flow of the watersheds that receive industrial and domestic waste.

Figure 5 presents the seasonal concentrations of metals and metalloid As in sediments determined at the PES compared to current Sediment Quality Guidelines (SQGs) employed to assess sediment contaminant impacts, aiming to protect benthic organisms and surface water quality. These SQG define two sediment quality limits based on ecotoxicological studies (Cunha et al., 2021; Kwok et al., 2014), the Threshold Effect Level (TEL), which indicates safe contaminant concentrations that do not result in adverse biological community effects, and the Probable Effect Level (PEL), which indicates likely adverse biological community effects (Aguiar et al., 2018; Hortellani et al., 2008; Okbah et al., 2014).

Herein, Cu, Cr and As surpassed TEL limits of 18.7 ug kg^− 1, 52.3 ug kg^− 1 and 7.24 ug kg^− 1 at several points throughout the PES. Regarding Cu, the TEL was surpassed at points 3 (June) and at points 5, 11, 23 and 25 (November). Point 3, where the highest Cu concentration was observed (72.62 ug kg^− 1), is located at the mouth of the Nhudiaquara River, whose watershed is in an environmental protection area occupied by agricultural properties with pastures and low-density urbanized areas. For Cr, concentrations above the TEL were observed only at point 2 (March), while concentrations at sampling points 5, 6 and 7, although high, did not exceed the TEL. Finally, As concentrations were higher than the TEL at points 2, 11, 23 and 26 in June, at points 1, 5, 6, 7, 11 and 24 in September and at points 2, 5, 11, 23 and 25 in November. Other studies have recorded As enrichments close to the city of Antonina, potentially be associated with the agricultural and port activities developed therein (Angeli et al., 2020; Rocha et al., 2017). Several compounds containing this element are also present in herbicides, defoliants, and insecticides (Barra et al., 2000), suggesting the local fertilizer industries as a potential source.

The other determined elements did not surpass TEL guidelines. Zn concentrations were higher at points 11, 16 and 2, close to the Paranaguá and Antonina ports. As Zn is widely used in sacrificial anodes, with the aim of preventing corrosion in the metallic structures of the vessels, higher concentrations in port areas are expected (Zhang et al., 2009). With regard to Cd, the highest Cd values were found at point 11, near the Paranaguá container terminal, while the highest Pb values were observed at points 2 and 11, near the cities of Antonina and Paranaguá respectively. Sediment Pb and Cd contents may originate from leaching from fertilized soils. In this regard, phosphate fertilizers are widely used in the drainage basins adjacent to the PES. Furthermore, points 2 and 11 receive also effluent discharge contributions from streams that cross the urban center of Antonina and Paranaguá. Similar distributions for both Fe and Mn were observed throughout the PES, with the highest Fe concentrations observed at points 2, 5 and 6 in March. Mn concentrations were also higher in March, at points 4, 5 and 6. Both Fe and Mn are traditionally derived from continental rock erosive processes and are generally used as indicators of the entry of continental sediments into coastal environments (Rothwell & Croudace, 2015). Regarding Ba, which is found in igneous and sedimentary rocks associated with minerals that contain K and becomes environmentally available through chemical rocks and mineral weathering (Liguori et al., 2016), concentrations were highest in November. Finally, Al concentrations were the highest at point 2 during the rainy season.

The average values observed herein were similar to those reported by Choueri et al. (2009) for As (8.33 ug kg^− 1), Cr (58 ug kg^− 1) and Pb (29.75 ug kg^− 1), in contrast to Cu (16.20 ug kg^− 1) and Zn (80.5 ug kg^− 1), which were much lower. Recently, Angeli et al. (2020) analyzed 16 metals, seven of which were also evaluated in this study in over 100 sediment samples collected along the SEP from Antonina Bay to the mouth of the estuary. The most abundant elements were Fe at Antonina Bay and Al in Paranaguá Bay, and Cu, Ni, Pb and Zn were found at high concentrations both in Paranaguá Bay and in Antonina, but none were significantly higher than the average for the Earth's crust. In addition, Al, Cr, Cu, Fe, Mn and Pb values observed were lower than those detected herein.

Significant correlations between Fe and Mn were detected, although no significant differences between sampling seasons were noted between these elements, which exhibited similar distributions throughout the estuary. Strong correlations were also noted between Mn and Fe, Zn and Pb and between Cr, Al, Fe and Pb (Table 3). Correlations with Fe suggest that Al, Cr, Pb and Zn are strongly associated with the iron oxyhydroxide phase or present a common origin (Reitermajer et al., 2011). It is important to note that Fe is an important mobility factor for these elements (Machado et al., 2014).

Table 3. Spearman correlation coefficient showing significant correlations between different metals, metalloid As, OM, TP, TN and TOC in the sediments from the Paranaguá Estuarine System.

	Al	Ba	Cd	Cr	Cu	Fe	Mn	Pb	Zn	As	OM
Cr	0.95	0.47	0.53	1
Cu	0.62	0.66	0.71	0.58	1
Fe	0.95	0.53	0.51	0.95	0.59	1
Mn	0.86	0.50	0.40	0.86	0.50	0.91	1
Pb	0.96	0.57	0.59	0.96	0.68	0.96	0.87	1
Zn	0.85	0.51	0.62	0.86	0.75	0.85	0.76	0.90	1
As	0.82	0.47	0.57	0.81	0.63	0.81	0.76	0.83	0.79	1
OM	0.83	0.51	0.60	0.81	0.62	0.81	0.71	0.84	0.72	0.73	1
TP	0.76	0.68	0.52	0.71	0.55	0.78	0.75	0.77	0.66	0.74	0.67
TN	0.51	0.74	0.49	0.46	0.51	0.48	0.42	0.51	0.40	0.48	0.43
TOC	0.79	0.46	0.60	0.78	0.58	0.77	0.67	0.81	0.71	0.69	0.94

Grain size and OM directly interfere with contaminant sediment distributions. OM in particular displays a high sorption capacity in relation to metals and metalloid As, regulating metal sediment retention (Harter & Naidu, 1995; Lair et al., 2007). Al, Cr, Fe, Mn, Pb, Zn and As presented more significant correlations with OM than the other determined parameters. Weaker correlations were found between elements Ba, Cd and Cu and the fine sediment fraction.

Significant differences between the dry and rainy seasons were detected only for Fe and Mn and for N and P (Table 4). This suggests more significant weathering and leaching processes in drainage basins adjacent to the estuary for Fe and Mn, also influenced by extreme rainfall leading to a higher enrichment factor for Fe and Mn oxides (Rocha et al., 2017). Regarding N and P, high discharges into the PES are due to human activities, including agriculture and domestic effluent inputs,as well as high watershed flows (Noriega & Araujo, 2011).

The Principal Component Analysis (PCA) is a multivariate statistical technique widely used in examining variability information and frequently applied to biota environmental and biota data (Yawei et al., 2005), as well as sediments (Fernandes et al., 2020) and superficial water (Chen et al., 2018). In the present study, two PCA were carried out with the sediment matrices to evaluate the spatial and temporal variables. The PCA (Fig. 6) associating all determined variables, except for CaCO₃, resulted in a total variance of 64.56%, with 55.09% referring to PC 1 and 9.47% to PC 2 (vertical axis). A strong interaction involving metals/metalloids, OM, nutrients, TOC and the fine fraction of sediments was noted, explain in over half of the data set variation. The distribution of metallic elements was more associated with the rainy season.

Grain size and organic matter play a more significant role in metallic element variability (Abrahim & Parker, 2008; Fonseca et al., 2014; Lima et al., 2023). The influence of OM is apparent in the two PCAs, particularly in the high loading of this variable in Principal Component 1 (Table 4).

The influence of anthropogenic sources comprises another relevant variable, given the positive loads of Cr, Pb, Zn and As in Principal Component 1. The positive loads of Al, Fe and Mn associated with leaching are also noteworthy. The salinity gradient presented a lesser effect on metal concentrations, represented by -0.15 in Principal Component 1.

Table 4

Factor loadings from the Principal Component Analysis (PCA).
	Factor 1	Factor 2
Variance explained	55.09%	9.47%
Al	0.28	0.15
Ba	0.16	-0.09
Cd	0.20	-0.11
Cr	0.28	0.17
Cu	0.17	-0.13
Fe	0.29	0.15
Mn	0.23	0.22
Pb	0.30	0.12
Zn	0.28	0.06
As	0.26	0.17
Organic Matter	0.26	0.06
Phosphorus	0.27	-0.07
Nitrogen	0.22	-0.10
Salinity	-0.15	0.54
Coarse Fraction	-0.21	0.32

The PCA analyzing spatial variation (Fig. 7) revealed segregation of the internal and intermediate sectors, which presented higher concentrations of metallic elements, as well as nutrients. The external, oceanic and outer sectors were the most similar, more associated with high salinity, oxygen, pH and the coarse granulometric fraction.

Geochemical Indices

The EF and CF indices are presented in Table 6. EF values below 1 were observed only for Al, demonstrating the anthropic contribution of the other determined elements. The EF values for Ba and Pb indicated moderate enrichment, while Cd, Cr, Cu, Mn, Zn and As displayed significant enrichment in relation to background values. Concerning the CF, all sampling points in the present study were categorized as presenting low contamination for Al, Ba, Cd, Cr, Fe, Mn, and As. Point 3 displayed a moderate CF for Cu and point 11, for Pb and Zn.

Table 6

Enrichment factor (EF) and contamination factor (CF) in surface sediments of the 38 sampling points in the Paranaguá Estuarine System.
Enrichment Factor
	Al	Ba	Cd	Cr	Cu	Fe*	Mn	Pb	Zn	As
Max	0.90	3.61	6.85	7.01	6.98	-	6.95	3.52	10.39	12.01
Min	0.02	0	0	0	0	-	0.27	0.10	0	0
Mean	0.28	0.28	0.27	0.83	0.45	-	1.21	1.76	1.54	1.82
Contamination Factor
	Al	Ba	Cd	Cr	Cu	Fe*	Mn	Pb	Zn	As
Max	0.22	0.31	0.71	0.62	1.61	0.78	0.93	1.27	1.23	0.93
Min	0	0	0	0	0	0.01	0.01	0.01	0	0
Mean	0.05	0.04	0.05	0.14	0.08	0.18	0.18	0.31	0.23	0.24

*Fe is used as a normalizing factor in the EF calculation (Abrahim & Parker, 2008).

The current PES contamination status was assessed by the Igeo (Fig. 8). Concerning Cd, Pb and As, sediments at all sampling points are not contaminated by these elements (calculated as zero). For Al, Ba, Fe and Mn, the average values indicate a class 5 category, or contaminated, although these elements are traditionally derived from the erosive processes of continental rocks. For Cr, Cu and Zn, calculations indicate classes 1 and 2, or moderately contaminated sediments (Fig. 8).

Monitoring of potentially toxic metals/metalloids in coastal areas is paramount for the preservation of estuarine biota and ecosystems. The data reported herein comprise novel information on the environmental of the SEP, contributing to the development of public policies. In this regard, although the PES presents significant economic and environmental importance, it is subject to several anthropic pressures. The findings reported herein indicate that PES sediments are differentially contaminated by metals and metalloid As, with several elements above SQGs guidelines, indicating adverse biological effects. Copper, Cr and As levels in surface sediments along the estuarine Paranaguá system were above the TEL. The presence of As may be related to the local geology, as high concentrations of As have been detected in several regions along the Brazilian coastline. Furthermore, Fe and Mn concentrations were higher in the rainy season. Cr behaved similarly, with a significant increase in the rainy season, perhaps due to runoff in port areas. Higher Pb contents were detected in the inner portion of the estuary, close to the port terminals, which may be associated with the lead oxide used in ship paints. Despite anthropic pressures, P and N were in the same range of variation as other coastal ecosystems.

Authors’ Contributions: Leonardo da Silva Lima: Conceptualization; Formal analysis; Methodology; Writing - original draft; and, Writing – review and editing. Khaue Vieira, Jéssica de Freitas Delgado and Danieli Lima da Cunha: Formal analysis; and Writing – review and editing. Rachel Ann Hauser-Davis: Writing review and editing; and, Translating to English. José Antônio Baptista Neto and Estefan Monteiro da Fonseca: Formal analysis; Writing review and editing; Supervision.

Conflicts of interest: The authors declare that they have no conflicts of interest.

Availability of data and material: The authors declare that they provide all the necessary information for this study.

Funding: No funding was obtained for this study.

Acknowledgments: Authors are thankful for the Secretaria Nacional dos Portos, Departamento de Geologia e Geofísica at Universidade Federal Fluminense, and Coordenação e Aperfeiçoamento de Pessoal de Nível Superior (CAPES) for the infrastructure and administrative support.

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Metals and metalloid contamination and geochemical normalization factors in surface sediments from an important estuarine system in Southern Brazil

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Abstract

Figures

Introduction

Material and methods

Study area

Sediment sampling

Physicochemical water parameters

Metals and metalloid As analyses

Geochemical Normalization Factors

Enrichment factor (EF)

Contamination Factor (CF)

Geoaccumulation Index (Igeo)

Results and discussion

Physicochemical water parameters

Metals and metalloids

Geochemical Indices

Conclusions

Declarations

References

Additional Declarations

Supplementary Files

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