Natural Selenium Levels in Subtropical Soils of Southern Brazil

doi:10.21203/rs.3.rs-5165863/v1

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Natural Selenium Levels in Subtropical Soils of Southern Brazil

https://doi.org/10.21203/rs.3.rs-5165863/v1

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Selenium is an essential micronutrient for humans; however, in high quantities, it can become toxic. The aim of this study was to evaluate the natural Se levels in soils from southern Brazil. Fifty sampling locations were selected for their minimal anthropogenic interference and high pedological and geological diversity. Soil samples were collected from the A horizon up to a depth of 20 cm. Analyses of Ca, Mg, K, P, TOC, acidity, and texture followed standardized methods, while Se was analyzed after acid digestion and measured using ICP-OES. The natural Se levels ranged from 0.34 mg kg^− 1 in a typical Alitic Haplic Cambisol to 11.25 mg kg^− 1 in an organosolic Dystrophic Humic Cambisol. Se behavior in the soil is influenced by pH, P, Fe, Al, and Mn oxides, clay, and organic matter. Metamorphic rocks contain higher Se levels due to mineral recrystallization and trace element mobilization during metamorphism. Background values are crucial as they provide data for decision-making and area management.

Selenium

Background values

Soil science

Trace elements are naturally found in low concentrations in the environment, but anthropogenic activities can lead to the contamination of natural resources with these elements (CAMPOS et al., 2020). Selenium (Se) is a metalloid that is essential for human and animal health in small amounts but becomes toxic at high concentrations (HASANUZZAMAN; BHUYAN, 2020). When Se levels in the soil are elevated, it is often accumulated in plants, potentially causing toxicity to animals and humans who consume these plants. Monitoring and understanding these levels is crucial to avoid negative impacts on health and the environment. Conversely, deficiency symptoms in animals and humans occur in areas where the natural bioavailability of Se in soils is low (RUSZCZYŃSKA et al., 2017).

The behavior of Se in soil is complex, as it is found in soil solution in the forms of selenite (SeO₃²⁻), selenate (SeO₄²⁻), or selenide (Se²⁻). Selenate is more common in aerated soils, is less retained by soil colloidal surfaces, and thus more available to plants, being also considered the Se species with the highest toxicological potential. Selenate preferentially forms outer-sphere complexes, with a water molecule between the anion and the soil surface, whereas selenite forms inner-sphere complexes (POKHREL et al., 2020). In general, the fundamental factors controlling the forms and behavior of Se in soils are redox potential and pH, but other factors such as oxides/hydroxides (mainly of Fe, Al, and Mn), clay, organic matter, and other ions also play significant roles (DINH et al., 2019; LI et al., 2017).

The natural concentrations of Se in soils, or background values, refer to the typical levels of this element found in different regions, which vary according to local geology, soil mineral composition, climate, vegetation, and other environmental factors. This information allows for the assessment of whether the levels found fall within ranges considered safe and appropriate for human activities and local ecosystems. Additionally, it provides important insights into soil contamination by anthropogenic activities over time. Therefore, considering the geomorphological and pedological diversity of the southern region of Brazil, the objective of this study was to determine the background values of Se in different soil classes and relate them to physical and chemical variables and formation processes.

The state of Santa Catarina is located in the southern region of Brazil, within the Atlantic Forest biome. The climate in Santa Catarina is characterized by notable diversity, ranging from humid subtropical with warm summers (Cfa) to humid with mild summers (Cfb), influenced by its latitude and varied topography. Rainfall is well distributed throughout the year. Coastal and low-altitude areas exhibit a humid subtropical climate with hot summers, mild winters, and well-distributed rainfall year-round. In higher altitude regions, such as the Planalto Serrano, the climate is temperate with harsher winters, frequent frosts, and potential snowfall, while the summers are milder.

The geology of Santa Catarina is marked by a variety of geological formations. In the western part of the state, ancient metamorphic and granitic rocks of the Precambrian Crystalline Complex prevail. The central and eastern regions are characterized by the Paraná Basin, composed of sedimentary rocks such as sandstones, and layers of basalts resulting from ancient volcanic activities. The Serra Geral, a significant volcanic formation, covers areas of the Planalto Catarinense with thick layers of basalt, shaping the relief and contributing to the region's mineral wealth and soil diversity (IBGE - Brazilian Institute of Geography and Statistics, 2010).

Fifty soil samples were collected throughout the state of Santa Catarina between June and December 2021 (Table 1). The soil profiles were collected according to the classifications by Almeida et al., 2003; Correa, 2003; Almeida and Erhart, 2009; Paes Sobrinho et al., 2009; Bringhenti et al., 2012; Costa et al., 2013; Ferreira, 2013; Lunardi Neto and Almeida, 2013; Teske et al., 2013.

Table 1

Classification of soils and material of origin at the collection site
Point	Classification	Material of origin
P1	Typical Alitic Yellow Argisol	Garnet Muscovite Shale
P2	Latossolic Dystrophic Yellow Argisol	Magmatics
P3	Typical Dystrophic Yellow Argisol	Granites and granulites
P4	Typical Dystrophic Yellow Argisol	Hornblendite
P5	Typical Alithic Bruno-Greyish Argisol	Mudstones and siltstones
P6	Dystrophic Red Argisol	Siltstones and sandstones
P7	Abrúptico Dystrophic Red Argisol	Fine siltstones and sandstones
P8	Typical Alithic Red-Yellow Argisol	Mafic granulite
P9	Typical Red Yellow Aluminum Argisol	Metasandstone
P10	Typical Red Yellow Aluminum Argisol	Mafic granulite
P11	Dystrophic Red Yellow Argisol	Sandstones and siltstones
P12	Dystrophic Red Yellow Argisol	Migmatites
P13	Typical Dystrophic Red Yellow Argisol	Granite
P14	Typical Alitic Haplic Cambisol	Rhyodacite
P15	Typical Alitic Haplic Cambisol	Red rhyodacite
P16	Typical Alitic Haplic Cambisol	Red rhyodacite
P17	Typical Aluminic Haplic Cambisol	Porphyritic phonolite
P18	Umbrian Haplic Aluminic Cambisol	Phonolite
P19	Umbrian Haplic Aluminic Cambisol	Basalt
P20	Umbrian Haplic Aluminic Cambisol	Rhyodacite
P21	Typical Haplic Ta Eutrophic Cambisol	Basalt
P22	Haplic Cambisol Tb Typical Dystrophic	Granite
P23	Histic Cambisol	Shales
P24	Typical Humic Aluminic Cambisol	Syenite
P25	Typical Distroferric Humic Cambisol	Basalt
P26	Organosolic Dystrophic Humic Cambisol	Basalt
P27	Typical dystrophic humic cambisol	Red rhyodacite
P28	Humic Distroferric Red Latosol	Basalt
P29	Umbrian Retractable Dystrophic Red Latosol	Basalt
P30	Typical Eutrophic Regolithic Neosol	Granite
P31	Typical Humic Regolithic Neosol	Phonolite
P32	Typical Bruno Dystroferric Nitisol	Amygdaloid basalt
P33	Humic Dystrophic Bruno Nitisol	Rhyodacite
P34	Nitisol Bruno Dystrophic humic latosol rubric	Rhyodacite
P35	Rubric Dystrophic Bruno Nitisol	Basalt
P36	Typical Dystrophic Bruno Nitisol	Basalt
P37	Typical Dystrophic Haplic Nitisol	Basalt
P38	Typical Alitic Red Nitisol	Basalt
P39	Typical Dystroferric Red Nitisol	Basalt
P40	Typical Eutrophic Red Nitisol	Basalt
P41	Typical Haplic Tb Dystroferric Cambisol	Rhyodacite
P42	Cambisolic Folic Sapric Organosol	Rhyodacite
P43	Typical Sapric Folic Organosol	Rhyodacite
P44	Typical Eutroferric Red Nitisol	Amygdaloid basalt
P45	Typical Eutrophic Yellow Argisol	Basalt
P46	Eutrophic chernosolithic litholic neosol	Basalt
P47	Eutroferric chernosolic Red Nitisol	Basalt
P48	Typical Ferric Argiluvic Chernosol	Basalt
P49	Typical Ferric Haplic Chernosolo	Amygdaloid basalt
P50	Typical Eutroferric Haplic Cambisol	Basalt

For soil sampling, the Dutch auger method was employed to collect samples from the 0–20 cm depth in the A horizon. Subsequently, the samples were disaggregated and dried in an oven (EMBRAPA, 2017) (Fig. 4). Following drying, the soils were sieved through a 2 mm sieve to separate the fine earth fraction (FEF). Analyses of Ca, Mg, K, Na, P, Al, organic matter, and potential acidity were conducted according to the procedures outlined by Tedesco et al. (1995). Furthermore, soil pH and texture were assessed following EMBRAPA guidelines (TEIXEIRA et al., 2017).

For Se analysis, the soil was sieved to 0.074 mm. The sample digestion procedure was conducted following the USEPA SW 846 3051A method (USEPA, 2007), employing a mixture of nitric acid and hydrochloric acid in a 3:1 ratio, using a Multiwave 3000 microwave model from Anton Paar. The microwave was calibrated with a power range of 650W to 1000W, an approximate pressure of 130 psi, an approximate temperature of 175ºC, a ramp time of 5 minutes and 30 seconds, and 4 minutes and 30 seconds of pressurized time (FEAM-MG, 2013) (Fig. 1).

Subsequently, the soil samples were centrifuged, followed by the addition of sulfuric acid to the solution, and then readings were performed using Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) with hydride generation, within its spectral reading range of 196.03 nm (ROCHA et al., 2013). Sodium borohydride (NaBH₄) at 0.5% and sodium hydroxide (NaOH) at 0.05% were utilized as reducing agents. The calibration standard for Se ranged from 0.5 to 20 µg L^− 1. The mean of blank sample readings and the standard deviation were used to calculate the limit of detection (LOD) and multiplied by 3.3 to determine the limit of quantification (LOQ). The LOD was found to be 0.001 mg kg^− 1 and the LOQ 0.003 mg kg^− 1. For every five samples, a 5-ppm Se solution was tested, with an expected recovery rate between 80% and 120%. Additionally, the average recovery rate from the NIST standard was 98.18%.

The mean, median, standard deviation (SD), minimum, maximum, and kurtosis were calculated using Excel. Statistical analyses were conducted using Sisvar software version 5.6, employing the Tukey test at a 5% significance level to compare means across distinct groups according to each component (e.g., classes, material of origin, organic matter content, and base saturation). Se levels were also correlated with pH, base saturation, clay content, total organic carbon, and phosphorus variables. Multivariate analysis was performed using the Principal Component Analysis (PCA) test in Minitab software.

The Se contents ranged from 0.34 mg kg^− 1 in the typical Alitic Haplic Cambisol to 11.25 mg kg^− 1 in an organossolic Dystrophic Humic Cambisol, which contains 12.7% organic matter. Generally, precipitation and parent material are the primary factors influencing the distribution of Se in soils. In the regional distribution of soil Se, clay and organic matter contents influence Se levels (NASCIMENTO et al., 2021).

In the soils of Santa Catarina, the mean content of Se was 1.60 mg kg^− 1 with a median of 1.20 mg kg^− 1 (Table 2). The Se content in Santa Catarina was higher than the global average of 0.33 mg kg^− 1 (Kabata-Pendias & Pendias, 2000) and 0.44 mg kg^− 1 (Song et al., 2020). According to the classification proposed by Song et al. (2020), none of the soils are deficient in Se (< 0.125 mg kg^− 1) nor do they have low content (0.125–0.175 mg kg^− 1). Only one soil was classified with moderate content (0.175–0.4 mg kg^− 1), and 44 soils have high Se content (0.4–3.0 mg kg^− 1). Furthermore, it was possible to identify five soils with excessive Se content (> 3.0 mg kg^− 1).

Table 2

– Data statistical analyses.
	TOC	pH	CTC	Areia	Argila	Silte	Al₂O₃	Fe₂O₃	MnO	P	Se
Mean	41.70	5.48	22.60	272.2	406.3	321.6	229941	189798	1745	9.26	1.60
Median	28.63	5.37	20.22	181.6	429.5	329.6	219003	151585	1030	4.89	1.20
SD	44.52	0.54	11.85	184.3	167.1	101.5	59224	110948	1809	14.79	1.65
Min.	9.05	4.55	4.89	26.3	124.1	128.3	103205	27810	50	2.78	0.34
Max.	249.00	6.70	61.38	713.3	752.7	508.1	402280	364735	8465	94.35	11.25
Kurtosis	13.21	-0.62	2.63	-0.70	-1.07	-0.87	1.02	-1.54	3.52	24.56	24.56

In a study conducted in Piauí, located in the northeastern region of Brazil, soil Se levels ranged from 0.002 to 4.78 mg kg^− 1 (LEITE et al., 2024). In Minas Gerais, the average Se levels were 0.38 mg kg^− 1, in Goiás 0.04 mg kg^− 1 (CARVALHO et al., 2019), and in São Paulo 0.18 mg kg^− 1 (GABOS; ALLEONI; ABREU, 2014). It is evident that in semi-arid environments underlain by crystalline rocks, where clay and organic carbon contents are low, pedogenesis and climate conditions result in lower Se concentrations compared to the southern region of Brazil (NASCIMENTO et al., 2021).

Compared to other soil classes, Argisols exhibited higher Se levels (Fig. 2). Argisols often develop from acidic magmatic rocks. Generally, acidic magmatic rocks such as granite and gneiss, and their metamorphic counterparts, possess naturally higher levels of Se. During the aging of Argisols, the formation and increase in concentrations of Fe and Al oxides occur. These oxides have a high affinity for oxyanions such as selenite (SeO₃²⁻) and selenate (SeO₄²⁻), which are common forms of Se in soil solution. In weathered soils, there is little to no presence of 2:1 clay minerals. This makes kaolinite (1:1) and Fe and Al oxides important in the adsorption process. Fe and Al oxides are effective in adsorbing Se. These oxides act as colloids that retain Se oxyanions, preventing their leaching and promoting their concentration in the soil. Therefore, the high Se content in Argisols may be related to the adsorption of these molecules by soil colloids (GOH; LIM, 2004).

The average Se content in soils derived from sedimentary rocks was 1.172 mg kg^− 1; in soils from igneous rocks, it was 1.528 mg kg^− 1; and in soils from metamorphic rocks, it was 2.127 mg kg^− 1. The soil originating from shale showed the highest Se content (11.254 mg kg-1), which is consistent with the findings of Nascimento et al. (2021). Soils derived from different parent materials exhibited statistically significant differences in Se content (Table 3 and Fig. 3).

Table 3

– Comparison of the mean Se in different origin materials
Origin material	Se (mg kg^− 1)
Andesite	0.848	a
Claystone	0.913	a
Siltstone	1.078	ab
Syenite	1.144	ab
Phonolite	1.145	ab
Granite	1.156	ab
Hornblendite	1.202	ab
Rhyodacite	1.231	ab
Sandstone	1.305	ab
Basalt	1.337	ab
Metasandstone	1.565	ab
Granulite	1.724	ab
Migmatite	2.367	ab
Garnet Muscovite Shale	4.414	b
Shales	11.254	c

The principal component analysis indicated that the first principal component (PC1) and the second principal component (PC2) accounted for 90.7% of the variance (Fig. 4). Soils derived from metamorphic rocks exhibited the highest Se concentrations.

Metamorphic rocks may contain higher Se levels due to various geological and chemical factors that influence their mineral composition and trace element concentration. During the metamorphic process, preexisting minerals in sedimentary or igneous rocks can recrystallize or form new minerals under high pressures and temperatures. Some of these minerals can incorporate Se into their crystalline structure, especially if the original material already contained Se (GONG et al., 2022). Additionally, metamorphism can cause the mobilization of trace elements, including Se. During metamorphic processes, hydrothermal fluids can percolate through the rocks, transporting and redistributing chemical elements. This transport can result in the concentration of Se in certain minerals or zones of the metamorphic rock. During metamorphism, sulfurous minerals, such as pyrite (FeS₂), can incorporate Se, thus increasing the Se content in metamorphic rocks. Metamorphic processes can also lead to the formation of denser and more stable minerals that retain Se more effectively than the minerals found in sedimentary rocks. This occurs because recrystallization during metamorphism can result in a mineralogical matrix that is chemically more compatible with the incorporation of Se (GONG et al., 2022).

It was also observed that the Se content is highly related to the increase in P content. The Se content in the soil may have a complex relationship with P, as both are essential nutrients for plants, but their interaction can influence their availability and mobility in the soil. Both Se and P can be adsorbed by Fe and Al oxides present in the soil. The increase in the concentration of one of these elements can reduce the adsorption of the other, thus increasing its availability. The presence of high levels of P can alter the chemical form of Se, transforming it into more soluble species, such as selenates. The biogeochemical cycles of Se and P may be interconnected through biological and chemical processes in the soil. Soil microorganisms involved in the mineralization and immobilization of P can also influence the form and availability of Se (JIANG et al., 2022).

The relationship between total organic carbon and Se in the soil influences the adsorption, mobility, and complexation of Se, directly affecting its availability. Se is more mobile and available under alkaline conditions (Fordyce et al., 2010). The correlation between Se and organic matter was found to be 0.27. Numerous studies correlate Se with Al₂O₃, clay, and organic matter (Coppin, Chabroullet, Martin-Garin, 2009). However, some studies did not observe a correlation between Se and organic matter in soils from the Midwest and Southeast regions of Brazil (Carvalho et al., 2019).

Given this context, it is evident that background values are essential in assessing soil quality, as they represent the natural concentrations of chemical elements prior to intense human intervention. They are fundamental for identifying contamination, differentiating between natural and anthropogenic concentrations, and guiding remediation strategies to ensure soils return to a safe state. Furthermore, they serve as a basis for the creation of environmental standards, facilitate geochemical studies, and contribute to sustainable agricultural practices, preventing agricultural pollution and ensuring environmental protection and public health.

The results revealed a variation in Se levels, influenced by a range of geological, pedological, and environmental factors. The complex behavior of Se in the soil reflects its dynamic interaction with pedological components, highlighting the importance of considering multiple factors when assessing Se levels in different contexts. The influence of local geology on the distribution of Se was evident, with soils derived from metamorphic rocks showing higher levels compared to soils derived from sedimentary or igneous rocks.

Furthermore, the relationship between Se and other elements, such as P and total organic carbon, has highlighted the complexity of biogeochemical interactions influencing the availability and mobility of this micronutrient in the soil

The Se background values provided by this study are indispensable for assessing soil quality, identifying potential contaminations, and guiding sustainable agricultural practices. They represent a crucial reference point for monitoring changes in Se levels over time and providing vital insights for environmental management and decision-making related to the protection of public health and the environment.

NOVELTY STATEMENT

This study presents a pioneering analysis of natural selenium (Se) levels in the subtropical soils of southern Brazil, specifically focusing on the state of Santa Catarina. Utilizing a comprehensive sampling approach across fifty diverse locations with minimal anthropogenic interference, this research is the first of its kind to provide detailed background Se values in this region. The findings highlight significant variability in Se concentrations, influenced by geological and pedological factors, particularly noting the high Se levels in soils derived from metamorphic rocks. The study also explores the intricate relationships between Se and other soil components such as pH, organic matter, and phosphorus. These insights are critical for environmental monitoring, sustainable agricultural practices, and public health protection, offering a foundational reference for future soil quality assessments and geochemical studies in subtropical regions.

AUTHORS CONTRIBUTIONS

All authors developed for the article and consent to publish the article in this journal. All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by Rosini, Delfino, Machado and Campos. The first manuscript was written by Rosini and all authors commented on previous versions of the manuscript. All authors: Rosini, Cavalcante, Matias, Delfino, Machado and Campos read and approved the final manuscript.

FUNDING

UDESC (Santa Catarina State University), PROAP (Postgraduate Support Program), UNIEDU (Santa Catarina University Scholarship Program), IMA-SC (Santa Catarina Environmental Institute), FAPESC (Santa Catarina State Research and Innovation Support Foundation) and CAPES (Coordination for the Improvement of Higher Education Personnel).

ETHICAL APPROVAL

The manuscript was not submitted to more than one journal for simultaneous consideration. It is original and was not published elsewhere. The article is my own authorship and uses data correctly. References are citations honestly. The article meets all of the journal's ethical requirements.

COMPETING INTERESTS

This study does not have competing interests.

DATA AVAILABILITY STATEMENT

The data that supports the findings of this study are available on request from de corresponding author: Rosini, D. N.

DECLARATION OF USE OF AI

This study did not use AI Technologies

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No competing interests reported.

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Natural Selenium Levels in Subtropical Soils of Southern Brazil

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Abstract

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1. INTRODUCTION

2. METHODOLOGY

3. RESULTS AND DISCUSSION

4. CONCLUSION

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