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Genesis and Classification of Soils Containing Carbonates in a Toposequence of the Bambuí Group

ABSTRACT

The Bambuí Group, formed from siliciclastic sediments deposited on an extensive epicontinental platform at the end of the Neoproterozoic era, is characterized by limestones with fine to very fine texture. Limestone-derived soils in the southeast of Tocantins state, Brazil, are less notorious than similar soils in other regions of Brazil and their characterization could contribute to the Brazilian System for Soil Classification (SiBCS). Given that little is known of these soils, despitetheir agricultural potential, the objective of this study was to characterize their properties and the processes leading to soil of genesis, and also contribute to developing the Brazilian System of Soil Classification (SiBCS). Soils profiles were located on the summit (P1), shoulder (P2), backslope (P3), and footslope (P4) of a toposequence in the municipality of Lavandeira, Tocantins. Morphological, physical, chemical, and mineralogical properties of the profiles were determined. The soils were classified as: P1 - Chernossolo Rêndzico Lítico típico (Lithic Haplustolls); P2 - Cambissolo Háplico Ta Eutrófico léptico hipocarbonático (Lithic Haplustolls); P3 - Cambissolo Háplico Carbonático léptico (Lithic Haplustepts); and P4 - Luvissolo Háplico Órtico típico (Typic Rhodustalfs). All the profiles showed high contents of silt, calcium, and magnesium, which resulted in high pH and low exchangeable aluminum content. Base saturation and calcium carbonate equivalent contents were also high, and the horizons showed dark colors due to high organic matter content, which contained humin as the dominant fraction. Mineralogical analysis of the clay fraction indicated predominance of hydroxy-interlayered vermiculite, followed by illite, kaolinite, and quartz, whereas the sand fraction exhibited reflections characteristic of the quartz mineral. Given P4 contents of calcium carbonate equivalent above 50 g kg-1 and the relevance of this feature for agriculture, we propose the inclusion of hypocarbonate as a criterion for classification of Luvissolos Háplicos Órticos at the subgroup level.

karst environments; SiBCS; dry forest; carbonate character

INTRODUCTION

The Bambuí Group is a geological formation that covers 300 000 km2 of the São Francisco Craton (Dardenne, 1978Dardenne MA. Síntese sobre a estratigrafia do Grupo Bambuí e Macaúbas no Brasil central. In: Anais do 30º Congresso Brasileiro de Geologia da Sociedade Brasileira de Geologia; 1978; Recife. p.597-610.), located in the eastern portion of the Brasília fold belt (Dardenne, 2000Dardenne MA. The Brasília Fold Belt. In: Cordani UG, Milani EJ, Tomas Filho A, Campos DA, editors. Tectonic evolution of South America. In: Congress 31st International Geological; 2000; Rio de Janeiro. Rio de Janeiro: 2000. p.231-63.). On a geological time scale, pelagic carbonate sediments, followed by siliciclastic sediments (Dardenne, 1978Dardenne MA. Síntese sobre a estratigrafia do Grupo Bambuí e Macaúbas no Brasil central. In: Anais do 30º Congresso Brasileiro de Geologia da Sociedade Brasileira de Geologia; 1978; Recife. p.597-610.), were deposited in the area during inversion tectonics of the basin, ca. 790-600 Ma (Santos et al., 2000Santos RV, Alvarenga CJS, Dardanne MA, Sial AN, Ferreira VP. Carbon and oxygen isotope profiles across Meso-Neoproterozoic limestones from central Brazil: Bambuí and Paranoá Groups. Precambrian Res. 2000;104:107-22.).The Bambuí Group is characterized by argillite, limestone, siltstone and fossilized stromatolites (Santos et al., 2000Santos RV, Alvarenga CJS, Dardanne MA, Sial AN, Ferreira VP. Carbon and oxygen isotope profiles across Meso-Neoproterozoic limestones from central Brazil: Bambuí and Paranoá Groups. Precambrian Res. 2000;104:107-22.). The limestones are stratified and exhibit very fine to fine particles, are grayish in color, and contain calcite surrounded by hematite inclusions and diffuse carbonate materials (Embrapa, 1983Empresa Brasileira de Pesquisa Agropecuária - Embrapa. Serviço Nacional de Levantamento e Conservação de Solos. Levantamento de reconhecimento de média intensidade dos solos e avaliação da aptidão agrícola das terras da margem direita do Rio Paranã, Estado do Goiás (Área de atuação da SUDECO). Rio de Janeiro: 1983. (Boletim de pesquisa, 23).). Soils formed from limestone parent material cover a significant portion of the world’s agricultural lands (Chen and Barak, 1982Chen Y, Barak P. Iron nutrition of plants in calcareous soils. Adv Agron. 1982;35:217-40. doi:10.1016/S0065-2113(08)60326-0
https://doi.org/10.1016/S0065-2113(08)60...
).

In Brazil, the agricultural potential of most calcareous soils is related to high Ca and Mg contents, low Al activity, and high base saturation and pH. Soil classes formed from Bambuí Group limestones in Tocantins are Gleissolos, Nitossolos and Cambissolos. They exhibit slightly acidic pH, high Ca and Mg contents, and base saturation above 50 % (Embrapa, 1983Empresa Brasileira de Pesquisa Agropecuária - Embrapa. Serviço Nacional de Levantamento e Conservação de Solos. Levantamento de reconhecimento de média intensidade dos solos e avaliação da aptidão agrícola das terras da margem direita do Rio Paranã, Estado do Goiás (Área de atuação da SUDECO). Rio de Janeiro: 1983. (Boletim de pesquisa, 23).). In an area with similar geology in the state of Goiás, Cambissolos, Vertissolos, and Argissolos (similar to Inceptisols, Vertisols, and Ultisols/Alfisols, respectively) with high base saturation and medium to clayey texture were observed (Brasil, 1982Brasil. Ministério das Minas e Energia. Projeto RADAMBRASIL. Levantamento de recursos naturais. Folha Goiânia. Rio de Janeiro: 1982.).

The lower plateaus in Northeast Brazil exhibit Cambissolos and Vertissolos derived from Jandaíra Group limestones, with pH above 7 and base saturation above 90 % (Lemos et al., 1997Lemos MS, Curi N, Marques, JJGSM, Sobrinho FE. Evaluation of characteristics of Cambisols derived from limestone in low tablelands in northeastern Brazil: Implications for management. Pesq Agropec Bras. 1997;32:825-34.), as well as Organossolos (Histosols) (Silva et al., 2014Silva RC, Valladares GS, Pereira MG, Anjos LHC. Caracterização de Organossolos em ambientes de várzea do Nordeste do Brasil. Rev Bras Cienc Solo. 2014;38:26-38. doi:10.1590/S0100-06832014000100003
https://doi.org/10.1590/S0100-0683201400...
). Also in Northeast Brazil, Vertissolos with high-activity clay and high contents of Ca and Mg, originating from calcareous sediments, are found in the Fernando de Noronha Archipelago, Pernambuco (Marques et al., 2014Marques FA, Souza RAS, Souza JES, Lima JFWF, Souza Júnior VS. Caracterização de Vertissolos da Ilha de Fernando de Noronha, Pernambuco. Rev Bras Cienc Solo. 2014;38:1051-65. doi:10.1590/S0100-06832014000400002
https://doi.org/10.1590/S0100-0683201400...
). Limestone-derived soils with high base saturation and pH occur in the north of the state of Minas Gerais (MG), in the Jaíba Project area (Oliveira et al., 2000Oliveira CV, Ker JC, Duarte MN, Curi N, Fontes LEF. Atributos micromorfológicos de solos de projeto Jaíba, Norte de Minas Gerais. Rev Bras Cienc Solo. 2000;24:117-28. doi:10.1590/S0100-06832000000100014
https://doi.org/10.1590/S0100-0683200000...
), particularly Latossolos (Oxisols), Cambissolos, and Argissolos. In contrast, Latossolos formed from meta-limestone associated with gabbro, with a very clayey texture, low Ca and Mg contents, and low base saturation, are found in the south of Minas Gerais (Araújo et al., 2014Araújo MA, Pedroso AV, Amaral DC, Zinn, YL. Paragênese mineral de solos desenvolvidos de diferentes litologias na região Sul de Minas Gerais. Rev Bras Cienc Solo. 2014;38:11-25. doi:10.1590/S0100-06832014000100002
https://doi.org/10.1590/S0100-0683201400...
). The occurrence of Latossolos Vermelhos, with high base saturation, and Chernossolos Ebânicos (Mollisols), with pH near 6.0 and low Al activity, was described in the Serra do Paranoá, Goiás (Lynch, 2009Lynch LS. Gênese e geoquímica de solos em ambiente cárstico no cerrado da região de Planaltina de Goiás [tese]. Viçosa, MG: Universidade Federal de Viçosa; 2009.). Calcareous soils in the Serra da Bodoquena, Mato Grosso do Sul (MS), are represented by Organossolos (Histosols), Chernossolos (Mollisols), and Gleissolos Melânicos (Aquents) with high base saturation and Ca and Mg contents (Pereira et al., 2013Pereira MG, Schiavo JA, Fontana A, Dias Neto AH, Miranda LPM. Caracterização e classificação de solos em uma topossequência sobre calcário na Serra da Bodoquena, MS. Rev Bras Cienc Solo. 2013;37:25-36. doi:10.1590/S0100-06832013000100003
https://doi.org/10.1590/S0100-0683201300...
).

Limestone-derived soils in the southeast of Tocantins state, Brazil, are less notorious than similar soils in other regions of Brazil and their characterization could contribute to the Brazilian System for Soil Classification (SiBCS), as well as contributing for better evaluation of agricultural potential.

The objective of this study was to characterize the morphological, physical, chemical, and mineralogical properties of soils formed from Bambuí Group materials, in the municipality of Lavandeira, Tocantins; identify the processes underlying their pedogenesis; and contribute to developing the SiBCS.

MATERIALS AND METHODS

Study Area

The study area is located in the municipality of Lavandeira, in the southwest of Tocantins, within the Bambuí Group geological formation. The climate according to the Köppen classification system is C2wA’a’ (dry sub humid with moderate water deficit) and annual rainfall is 1,500 mm (Köppen, 1948Köppen W. Climatologia: comum estúdio de los climas de tierra. México: Fonda Cultura Económica; 1948.). Local vegetation is classified as “mata seca” (dry forest), a deciduous tropical forest (Ribeiro and Walter, 2008Ribeiro JF, Walter BMT. Fitofisionomias do bioma Cerrado. In: Sano SM, Almeida SP, Ribeiro JF editores. Cerrado: ambiente e flora. Planaltina: Centro de Pesquisa Agropecuária dos Cerrados; 2008. p.152-212.), which is typical of limestone areas (Silva and Scariot, 2003Silva LA, Scariot A. Composição florística e estrutura da comunidade arbórea em uma Floresta Estacional Decidual em afloramento calcário (Fazenda São José, São Domingos, GO, Bacia do rio Paranã). Acta Bot Bras. 2003;17:305-13. doi:10.1590/S0102-33062003000200012
https://doi.org/10.1590/S0102-3306200300...
). The topography is slightly rolling to rolling (Embrapa, 1983Empresa Brasileira de Pesquisa Agropecuária - Embrapa. Serviço Nacional de Levantamento e Conservação de Solos. Levantamento de reconhecimento de média intensidade dos solos e avaliação da aptidão agrícola das terras da margem direita do Rio Paranã, Estado do Goiás (Área de atuação da SUDECO). Rio de Janeiro: 1983. (Boletim de pesquisa, 23).), with apparent karstic features and limestone outcroppings with signs of carbonate dissolution.

The toposequence was selected in an area with slightly rolling topography. The soil profiles were observed and sampled in pits opened across the slope, on the summit (P1), shoulder (P2), backslope (P3), and (P4) footslope. The profiles studied (P1 to P4; Table 1) were described according to the Brazilian Field Handbook for Soil Sampling and Description (Santos et al., 2013a).

Table 1
Overall description of soil profiles (Prof) in the toposequence in Lavandeira, TO, Brazil

Laboratory soil analysis

The samples were processed into air-dried fine earth (ADFE) to analyze physical and chemical properties. Particle size was determined by the pipette method, using 0.1 mol L-1 NaPO3 and water, and soil bulk density (BD) was assessed by the Kopecky ring method. The Ca2+, Mg2+, and Al3+ were extracted with 1 mol L-1 KCl solution, and H+Al was extracted using a 0.5 mol L-1 solution of calcium acetate at a pH of 7. Soil P, Na+, and K+ were determined using the extraction solution of 0.0125 mol L-1 H2SO4 + 0.05 mol L-1 HCl; Ca2+ and Mg2+ contents were determined by titration with 0.0125 mol L-1 EDTA; Na and K by flame photometry; and Al3+ and H+Al by titration with 0.025 mol L-1 NaOH. Soil pH was determined in water and KCl (1:2.5 weight), in a direct reading potentiometer. The protocols were based on Claessen (1997)Claessen MEC, organizador. Manual de métodos de análise de solo. 2ª ed. Rio de Janeiro: Centro Nacional de Pesquisa de Solos; 1997.. P was extracted using an alkaline solution of 0.5 mol L-1 sodium bicarbonate (Olsen et al., 1954Olsen SR, Cole CV, Watenabe FS, Dean LA. Estimation of available phosphorus in soils by extraction with sodium bicarbonate. Washington: USDA; 1954. (Circular, 939).) and measured by colorimetric procedures. The results obtained were used to calculate sum of bases (SB), cation exchange capacity (CEC), base saturation (V), and Al saturation (m).

Sulfuric acid digestion was applied to extract Fe, Al, Ti, and silica (Claessen, 1997Claessen MEC, organizador. Manual de métodos de análise de solo. 2ª ed. Rio de Janeiro: Centro Nacional de Pesquisa de Solos; 1997.), which were expressed as oxides (Fe2O3, Al2O3, TiO2, and SiO2). Dithionite citrate bicarbonate solution was used to extract Fe from oxides with high and low crystallinity (Fed) (Mehra and Jackson, 1960Mehra OP, Jackson ML. Iron oxide removal from soil and clays by dithionite-citrate system buffered with sodium bicarbonate. Clays Clay Miner. 1960;5:317-27. doi:10.1346/CCMN.1958.0070122
https://doi.org/10.1346/CCMN.1958.007012...
), and acid ammonium oxalate solution to extract Fe from poorly crystalline compounds (Feo) (Claessen, 1997Claessen MEC, organizador. Manual de métodos de análise de solo. 2ª ed. Rio de Janeiro: Centro Nacional de Pesquisa de Solos; 1997.).

The CaCO3 contents were determined by sample digestion in 0.5 mol L-1 HCl in excess followed by titration of excess acid with standard NaOH solution (Claessen, 1997Claessen MEC, organizador. Manual de métodos de análise de solo. 2ª ed. Rio de Janeiro: Centro Nacional de Pesquisa de Solos; 1997.). The method was modified by applying a temperature of 250 °C for 10 min. CaCO3 was calculated by the expression:

mCaCO3 (g) = nCaCO3 (mmol) × M.M.CaCO3 (g mmol-1)

where

MNaOH × V3 = nNaOH = 1 nHCl in excess

nHCl added = MHCl added × V HCl aliquot

nHCl added - nHCl in excess = nHCl reacting

nCaCO3 = n CaO = ½ nHCl reacting with limestone

where M.M. is molar mass; V is volume; and n is normality.

The organic carbon (OC) contents and chemical fractioning of organic matter were measured according to Yeomans and Bremner (1988)Yeomans JC, Bremner JM. A rapid and precise method for routine determination of organic carbon in soil Commun Soil Sci Plant Anal. 1988;19:1467-76. doi:10.1080/00103628809368027
https://doi.org/10.1080/0010362880936802...
and Benites et al. (2003)Benites VM, Madari B, Machado PLOA. Extração e fracionamento quantitativo de substâncias húmicas do solo: um procedimento simplificado de baixo custo. Rio de Janeiro: Embrapa Solos; 2003. (Comunicado técnico, 16)..

Clay fraction minerals were identified by X-ray diffraction (XRD) from oriented slides mounted with total clay suspension (<2.0 µm), without eliminating Fe oxides (Claessen, 1997Claessen MEC, organizador. Manual de métodos de análise de solo. 2ª ed. Rio de Janeiro: Centro Nacional de Pesquisa de Solos; 1997.). Analyses were performed using a Rigaku D-Max ΠA diffractometer, with Kα radiation (λ = 0.015405 nm) emitted from a copper tube (20 to 25 kv and 10 mA), with a scanning range of 1°2θ min-1 (Claessen, 1997)Claessen MEC, organizador. Manual de métodos de análise de solo. 2ª ed. Rio de Janeiro: Centro Nacional de Pesquisa de Solos; 1997.. The sample was pretreated by heating it to 550 °C and saturating it with ethylene glycol and dimethyl sulfoxide, followed by X-ray irradiation. Samples of the sand fraction were ground in a ball mill, and the resulting crystalline powder was mounted on non-oriented slides. The slides were analyzed by XRD, using a Bruker AXS D8 Advance X ray diffractometer that emitted CuKα radiation (λ = 0.015405 nm) from a copper tube (40 kV and 40 mA), with a scanning range of 1°2θ min-1 (0.04°/s). To identify the minerals in the samples, the diffractograms were analyzed using the 2004.04.67 PROX powder software (available at http://www.xpowder.com).

The soil profiles were classified according to the Brazilian System of Soil Classification (SiBCS) (Santos et al., 2013aSantos HG, Jacomine PKT, Anjos LHC, Oliveira VA, Oliveira JB, Coelho MR, Lumbreras JF, Cunha TJF. Sistema brasileiro de classificação de solos. 3ª ed. Rio de Janeiro: Embrapa Solos; 2013a.) and Soil Taxonomy (Soil Survey Staff, 2014Soil Survey Staff. Keys to soil taxonomy. 12th. ed. Washington, DC: USDA, Natural Resources Conservation Service; 2014.).

RESULTS AND DISCUSSION

Morphological Properties

Surface horizons exhibited dark colors due to high organic matter content formed by deposition of plant residues and their interaction with the soil mineral fraction. Subsurface horizons exhibited hues from 2.5 to 7.5YR, ranging from red to orange. Profile P4 showed a hue of 2.5YR in the subsurface horizons, which is typical of soils formed under good drainage conditions and/or from parent materials with high mafic mineral content (Silva and Vidal Torrado, 1999Silva AC, Vidal-Torrado P. Gênese dos Latossolos Húmicos e sua relação com a evolução da paisagem numa área cratônica do sul de Minas Gerais. Rev Bras Cienc Solo. 1999;23:329-41. doi:10.1590/S0100-06831999000200017
https://doi.org/10.1590/S0100-0683199900...
). Reddish hues are associated with the presence of hematite, an iron oxide common to calcareous soils (Boero et al., 1992Boero V, Premoli A, Melis, P, Barberis E, Arduino E. Influence of climate on the iron oxide mineralogy of terra rossa. Clays Clay Miner. 1992;40:8-13. doi:10.1346/CCMN.1992.0400102
https://doi.org/10.1346/CCMN.1992.040010...
). Profiles P1, P2, and P3 ranged from reddish-yellow to yellow (5 to 10YR), indicating predominance of goethite over hematite. These colors are developed by a pedogenic process called brunificação (brown soil coloring) (Arnold, 1983Arnold RW. Conceitos of soils and pedology. In: Wilding LP; Smeck NE, Hall GF, editors. Pedogenesis and soil taxonomy - I. Concepts and interactions. Amsterdam: Elsevier; 1983. p1-21.; Kämpf and Curi, 2012Kämpf N, Curi N. Formação e evolução do solo (Pedogênese). In: Ker JC, Schaefer CEGR, Vidal- Torrado P, editores. Pedologia: fundamentos. Viçosa, MG: Sociedade Brasileira de Ciência do Solo; 2012. p.207-302.), which is favored by organic matter build-up (Almeida et al., 2000Almeida JA, Maçaneiro KC, Klamt E. Mineralogia da fração argila de solos vermelhos com horizontes superficiais brunados do planalto de Lages (SC). Rev Bras Cienc Solo. 2000;24:815-28. doi:10.1590/S0100-06832000000400014
https://doi.org/10.1590/S0100-0683200000...
), lower Fe content in the parent material, and poor drainage because of lithic or paralithic contact.

Surface horizons showed predominance of granular structure, and aggregation was improved by high organic matter content. A similar structure, with a moderate to strong degree of development, granular or angular shape, and subangular blocks, was observed in the subsurface horizons of all profiles. The most highly developed structure was associated with the presence of high activity clay (CEC ≥ 27 cmolc kg-1 of clay) and the aggregating effect of the cations calcium and magnesium. In the pedogenesis of calcareous soils of the Serra da Bodoquena, Mato Grosso do Sul, Silva (2013)Silva MB. Gênese e classificação dos solos em duas topossequências no sistema cárstico na Serra da Bodoquena (MS) [tese]. Seropédica: Universidade Federal Rural do Rio de Janeiro; 2013. attributed the aggregation events and the blocky structure formation to intense wetting/drying cycles and high clay content (>280 g kg-1).The waxy aspect covering the surface of aggregates in P4 (Table 2) is identified in the field as clay skins (Santos et al., 2013bSantos RD, Lemos RC, Santos HG, Ker JC, Anjos LHC, Shimizu SH. Manual de descrição e coleta de solo no campo. 6a.ed. Viçosa, MG: Sociedade Brasileira de Ciência do Solo; 2013b.).The Bt1k5 and Bt2k6 horizons had common and moderate clay skins, resulting from the multiple pedogenic processes of clay translocation (Kämpf and Curi, 2012)Kämpf N, Curi N. Formação e evolução do solo (Pedogênese). In: Ker JC, Schaefer CEGR, Vidal- Torrado P, editores. Pedologia: fundamentos. Viçosa, MG: Sociedade Brasileira de Ciência do Solo; 2012. p.207-302..

Table 2
Morphological properties of soil profiles in the toposequence in Lavandeira, TO, Brazil

The textural classes ranged from loamy to very clayey, and the contents of silt and clay fractions stood out. This is related to the parent material, which is mainly limestone with argillite and laminated siltstone (Embrapa, 1983Empresa Brasileira de Pesquisa Agropecuária - Embrapa. Serviço Nacional de Levantamento e Conservação de Solos. Levantamento de reconhecimento de média intensidade dos solos e avaliação da aptidão agrícola das terras da margem direita do Rio Paranã, Estado do Goiás (Área de atuação da SUDECO). Rio de Janeiro: 1983. (Boletim de pesquisa, 23).), in addition to the influence of sediments.

Physical and chemical properties

With respect to soil granulometry, observed by texture in the field, the content of silt is higher than the content of the other fractions, ranging from 310 to 530 g kg-1 (Table 3). High silt contents were found in other soil profiles in the study area (Embrapa, 1983Empresa Brasileira de Pesquisa Agropecuária - Embrapa. Serviço Nacional de Levantamento e Conservação de Solos. Levantamento de reconhecimento de média intensidade dos solos e avaliação da aptidão agrícola das terras da margem direita do Rio Paranã, Estado do Goiás (Área de atuação da SUDECO). Rio de Janeiro: 1983. (Boletim de pesquisa, 23).). The presence of laminated siltstone associated with limestone from the Bambuí Group (Dardanne, 1978; Santos et al., 2000Santos RV, Alvarenga CJS, Dardanne MA, Sial AN, Ferreira VP. Carbon and oxygen isotope profiles across Meso-Neoproterozoic limestones from central Brazil: Bambuí and Paranoá Groups. Precambrian Res. 2000;104:107-22.) explains the predominance of silt in the profiles. Clay contents ranged from 290 to 520 g kg-1 (Table 3), which usually increased in the B horizons and decreased towards the Ck5 horizon. In P4, clay values increased from 290 g kg-1 in the Apk1 horizon to 470 g kg-1 in Bt2k6. In general, the sum of clay and silt contents accounted for more than 70 % of the fine earth (smaller than 2.0 mm) fraction.

Table 3
Physical properties of soil profiles in a toposequence in Lavandeira, TO, Brazil

The wide variation in the sand fraction in each profile may be associated with the origin of the parent material, from sediment deposition. The variation from a coarse to fine sand ratio in horizons Ck5 and Bt2K6 of P2 and P4 could indicate lithological discontinuity, as established by the SiBCS (Santos et al., 2013aSantos HG, Jacomine PKT, Anjos LHC, Oliveira VA, Oliveira JB, Coelho MR, Lumbreras JF, Cunha TJF. Sistema brasileiro de classificação de solos. 3ª ed. Rio de Janeiro: Embrapa Solos; 2013a.). However, the possible association with sediment layering during limestone formation is a more plausible explanation. Likewise, the use of a silt/clay ratio above 0.6 to indicate low weathering (Santos et al., 2013aSantos HG, Jacomine PKT, Anjos LHC, Oliveira VA, Oliveira JB, Coelho MR, Lumbreras JF, Cunha TJF. Sistema brasileiro de classificação de solos. 3ª ed. Rio de Janeiro: Embrapa Solos; 2013a.) is not an adequate criterion in soils formed from sedimentary rocks and sediments. As suggested by Shinzato (1998)Shinzato E. O carste da área de proteção ambiental de Lagoa Santa (MG) e sua influência na formação de solos [dissertação]. Campos dos Goytacazes: Universidade Estadual do Norte Fluminense; 1998., this ratio may result from sediment weathering rather than the pedogenic process.

All the profiles showed an unusually low degree of flocculation (DF), along with high contents of exchangeable Ca and pH (Table 4). Nevertheless, the findings corroborate calcareous soil data from the Serra da Bodoquena, MS (Pereira et al., 2013Pereira MG, Schiavo JA, Fontana A, Dias Neto AH, Miranda LPM. Caracterização e classificação de solos em uma topossequência sobre calcário na Serra da Bodoquena, MS. Rev Bras Cienc Solo. 2013;37:25-36. doi:10.1590/S0100-06832013000100003
https://doi.org/10.1590/S0100-0683201300...
). In a study on soils affected by limestone sediments in floodplains in Sousa, Paraíba, Brazil, Corrêa et al. (2003)Corrêa MM, Ker JC, Mendonça ES, Ruiz HA, Bastos RS. Atributos físicos, químicos e mineralógicos de solos da região de várzeas de Souza (PB). Rev Bras Cienc Solo. 2003;27:311-24. doi:10.1590/S0100-06832003000200011
https://doi.org/10.1590/S0100-0683200300...
suggested that a low DF is associated with high Mg2+ and Na+ content in the soil, in addition to the presence of expanding 2:1 clay minerals. Marques et al. (2014)Marques FA, Souza RAS, Souza JES, Lima JFWF, Souza Júnior VS. Caracterização de Vertissolos da Ilha de Fernando de Noronha, Pernambuco. Rev Bras Cienc Solo. 2014;38:1051-65. doi:10.1590/S0100-06832014000400002
https://doi.org/10.1590/S0100-0683201400...
attribute the high clay contents in water to high Mg2+ contents in the sorptive complex.

Table 4
Chemical properties of soil profiles in a toposequence in Lavandeira, TO, Brazil

The P1 and P2 reaction class was neutral, while in P3 and P4, it was moderately acid, ranging from 6.02 to 6.74 (Table 4). The negative values of ∆pH indicate the dominance of negative charges in all soil profiles. The most significant ion in the sorptive complex throughout the profiles was Ca2+ (4.8 to 27.4 cmolc kg-1), followed by Mg2+ (5.3 to 11.1 cmolc kg-1), K+, and Na+ (maximum of 0.3 and 0.04 cmolc kg-1, respectively). This is in line with studies on calcareous soils in other regions of Brazil (Cunha and Ribeiro, 1998Cunha TJF, Ribeiro LP. Qualidade e relações pedogenéticas da matéria orgânica de alguns solos da região do Irecê (BA). Rev Bras Cienc Solo. 1998;22:693-704.; Ferreira, 2013Ferreira EP. Gênese e classificação de solos em ambiente cárstico na Chapada do Apodi [dissertação]. Seropédica: Universidade Federal Rural do Rio de Janeiro; 2013.; Silva, 2013Silva MB. Gênese e classificação dos solos em duas topossequências no sistema cárstico na Serra da Bodoquena (MS) [tese]. Seropédica: Universidade Federal Rural do Rio de Janeiro; 2013.). Unlike the present study, Marques et al. (2014)Marques FA, Souza RAS, Souza JES, Lima JFWF, Souza Júnior VS. Caracterização de Vertissolos da Ilha de Fernando de Noronha, Pernambuco. Rev Bras Cienc Solo. 2014;38:1051-65. doi:10.1590/S0100-06832014000400002
https://doi.org/10.1590/S0100-0683201400...
describe soils with a sorptive complex, where Mg2+ contents are higher than those of Ca2+. Exchangeable Al (Al3+) contents were close to zero (Table 4), and pH values were high. A similar pattern was observed in a study on Paleosols in karstic environments of the Bambuí Group (Vasconcelos et al., 2013Vasconcelos BNF, Ker JCK, Schaefer CEGR, Poirier AP, Andrade FV. Antropossolos em sítios arqueológicos de ambiente cárstico no norte de Minas Gerais. Rev Bras Cienc Solo. 2013;37:986-96. doi:10.1590/S0100-06832013000400016
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). Phosphorus contents were low in all the profiles, as also observed in Lagoa Santa Carste (Shinzato, 1998Shinzato E. O carste da área de proteção ambiental de Lagoa Santa (MG) e sua influência na formação de solos [dissertação]. Campos dos Goytacazes: Universidade Estadual do Norte Fluminense; 1998.) and Serra da Bodoquena (Silva et al., 2013Silva MB, Anjos LHC, Pereira MG, Schiavo JA, Cooper M, Cavassani RS. Gênese e classificação dos solos de uma Topossequência em área de carste na Serra da Bodoquena, MS. Rev Bras Cienc Solo. 2013;37:1464-80. doi:10.1590/S0100-06832013000600004
https://doi.org/10.1590/S0100-0683201300...
).

Sum of bases ranged from 11.62 to 36.57 cmolc kg-1, and base saturation was above 90 %, demonstrating the euthrophic character of the soils (Santos et al., 2013aSantos HG, Jacomine PKT, Anjos LHC, Oliveira VA, Oliveira JB, Coelho MR, Lumbreras JF, Cunha TJF. Sistema brasileiro de classificação de solos. 3ª ed. Rio de Janeiro: Embrapa Solos; 2013a.). Cation exchange capacity at pH 7 ranged from 13.13 to 27.88 cmolc kg-1. The clay fraction of all the profiles showed CEC above 27 cmolc kg-1, and corroborating mineralogical data indicates high clay activity (Santos et al., 2013aSantos HG, Jacomine PKT, Anjos LHC, Oliveira VA, Oliveira JB, Coelho MR, Lumbreras JF, Cunha TJF. Sistema brasileiro de classificação de solos. 3ª ed. Rio de Janeiro: Embrapa Solos; 2013a.). These results are in accordance with a study on calcic horizons in Northeast Jordan (Khresat, 2001Khresat SA. Calcic horizon distribution and soil classification in selected soils of north-western Jordan. J Arid Environ. 2001;47:145-52.). CTC

Calcium carbonate (CaCO3) contents ranged from 79.41 to 220.56 g kg-1 (Table 4), with the highest values found in the Ak̅ horizon of P1 (209.2 g kg-1) and the ABk̅ horizon of P3 (220.56 g kg-1), both soils showing lithic contact up to a depth of 0.30 m. These results are explained by weathering of the parent material, which releases ions that become soluble, and restricted drainage caused by proximity to rock, which hinders ion leaching in the solution, leading to the accumulation of secondary CaCO3, primarily in the soil layer immediately above.

In a study on soils formed from limestone in the Serra da Bodoquena, MS, Pereira et al. (2013)Pereira MG, Schiavo JA, Fontana A, Dias Neto AH, Miranda LPM. Caracterização e classificação de solos em uma topossequência sobre calcário na Serra da Bodoquena, MS. Rev Bras Cienc Solo. 2013;37:25-36. doi:10.1590/S0100-06832013000100003
https://doi.org/10.1590/S0100-0683201300...
attributed the lower CaCO3 contents to good drainage, which favored bicarbonate solubilizing and leaching. They found higher CaCO3 contents in the soils in lower areas, which they explained as the influx of ions from higher elevations and reduction of losses due to restricted drainage. In calcic horizons in Jordan, Khresat (2001)Khresat SA. Calcic horizon distribution and soil classification in selected soils of north-western Jordan. J Arid Environ. 2001;47:145-52. found an accumulation of secondary carbonate calcium at lower elevations, in contrast to the present study, where parent material was the determinant factor for CaCO3, which served as a carbonate source and structural control, restricting drainage.

Carbon and humic fractions of organic matter

Surface horizons showed higher contents of organic carbon - OC (7.2 to 50.7 g kg-1), which decreased with depth (Table 5). Distribution of the humic fraction followed the pattern observed for OC. Organic carbon contents were 1.4 to 8.2 g kg-1 in the fulvic acid fraction (C-FAF), 0.5 to 13.1 g kg-1 in the humic acid fraction (C-HAF), and 5.1 to 38.2 g kg-1 in humin. C-FAF represented the lowest portion of the fractions, followed by C-HAF. Both fractions correspond to the soluble portion in the alkaline extract (AE) and exhibit higher chemical reactivity (Benites et al., 2003Benites VM, Madari B, Machado PLOA. Extração e fracionamento quantitativo de substâncias húmicas do solo: um procedimento simplificado de baixo custo. Rio de Janeiro: Embrapa Solos; 2003. (Comunicado técnico, 16).). Soil C was mostly concentrated in humin, corroborating studies on humic substances of calcareous soils (Volkoff, 1980Volkoff B. Comparação do húmus de um Solontchak, uma Rendzina e um solo litólico da região semiárida do Rio Grande do Norte. Rev Bras Cienc Solo. 1980;4:49-56.; Ferreira, 2013Ferreira EP. Gênese e classificação de solos em ambiente cárstico na Chapada do Apodi [dissertação]. Seropédica: Universidade Federal Rural do Rio de Janeiro; 2013.). The authors attribute the predominance of humin to its high stability and polymerization, which results from its close interaction with the mineral fraction of the soil (Duchaufour, 1970Duchaufour P. Humification et ecologie. Cah ORSTOM Sér Pédol. 1970;8:1-12.; Cunha and Ribeiro, 1998Cunha TJF, Ribeiro LP. Qualidade e relações pedogenéticas da matéria orgânica de alguns solos da região do Irecê (BA). Rev Bras Cienc Solo. 1998;22:693-704.; Pereira et al., 2013Pereira MG, Schiavo JA, Fontana A, Dias Neto AH, Miranda LPM. Caracterização e classificação de solos em uma topossequência sobre calcário na Serra da Bodoquena, MS. Rev Bras Cienc Solo. 2013;37:25-36. doi:10.1590/S0100-06832013000100003
https://doi.org/10.1590/S0100-0683201300...
).

Table 5
Chemical fractioning of organic matter of soils in a toposequence in Lavandeira, TO, Brazil

The alkaline extract (AE), which is the sum of C-FAF and C-HAF, ranged from 2.6 to 16.7 g kg-1 along the toposequence, varying among the horizons in relation to C content. Similar results were found in calcareous soils from Irecê, Bahia, Brazil (Cunha and Ribeiro, 1998Cunha TJF, Ribeiro LP. Qualidade e relações pedogenéticas da matéria orgânica de alguns solos da região do Irecê (BA). Rev Bras Cienc Solo. 1998;22:693-704.). The C-HAF/C-FAF ratio ranged from 0.1 to 6.4, with the widest amplitude recorded in P2 and P4 (Table 5). The wide range indicates C mobility throughout the profiles and, as a result, loss of the most soluble fraction (C-FAF) (Volkoff et al., 1984Volkoff B, Cerri CC, Melfi AJ. Húmus e mineralogia dos horizontes superficiais de três solos de campo de altitude dos Estados de Minas Gerais, Paraná e Santa Catarina. Rev Bras Cienc Solo. 1984;8;277-283.).The values of the AE/humin ratio ranged from 0.1 to 0.6 (Table 5), indicating high organic matter stability. This was also observed in earlier studies on organic fractions in calcareous soils (Fontana et al., 2010Fontana A, Pereira MG, Anjos, LHC, Benites VM. Quantificação e utilização das frações húmicas como característica diferencial em horizontes diagnósticos de solos brasileiros. Rev Bras Cienc Solo. 2010;34:41-57. doi:10.1590/S0100-06832010000400023
https://doi.org/10.1590/S0100-0683201000...
; Pereira et al., 2013Pereira MG, Schiavo JA, Fontana A, Dias Neto AH, Miranda LPM. Caracterização e classificação de solos em uma topossequência sobre calcário na Serra da Bodoquena, MS. Rev Bras Cienc Solo. 2013;37:25-36. doi:10.1590/S0100-06832013000100003
https://doi.org/10.1590/S0100-0683201300...
).

Organic matter stability was described by Duchaufour (1970)Duchaufour P. Humification et ecologie. Cah ORSTOM Sér Pédol. 1970;8:1-12., who stated that the close relationship between organic matter and 2:1 clays is promoted by Ca and Fe ions. This was corroborated by other authors (Fanning and Fanning, 1989Fanning DS, Fanning MCB. Soil: morphology, genesis and classification. New York: John Wiley; 1989.; Bockheim and Gennadiyev, 2000Bockheim JG, Gennadiyev AN. The role of soil-forming processes in the definition of taxa in soil taxonomy and the world soil reference base. Geoderma. 2000;95:53-72. doi:10.1016/S0016-7061(99)00083-X
https://doi.org/10.1016/S0016-7061(99)00...
; Kämpf and Curi, 2012Kämpf N, Curi N. Formação e evolução do solo (Pedogênese). In: Ker JC, Schaefer CEGR, Vidal- Torrado P, editores. Pedologia: fundamentos. Viçosa, MG: Sociedade Brasileira de Ciência do Solo; 2012. p.207-302.), who report that the interactions between organic and mineral fractions are key factors in determining the dark color of chernozemic horizons. Other studies are more specific, suggesting that organic matter stability in calcareous soils results from the 2:1 clay mineral and Ca2+ and Mg2+ ion interactions with ionized carboxylic acid and hydroxide groups (Duchaufour, 1976Duchaufour P. Dynamics of organic matter in soils of temperate regions: its action on pedogenesis. Geoderma. 1976;15:31-40. doi:10.1016/0016-7061(76)90068-9
https://doi.org/10.1016/0016-7061(76)900...
; Cunha and Ribeiro, 1998Cunha TJF, Ribeiro LP. Qualidade e relações pedogenéticas da matéria orgânica de alguns solos da região do Irecê (BA). Rev Bras Cienc Solo. 1998;22:693-704.; Corrêa et al., 2003Corrêa MM, Ker JC, Mendonça ES, Ruiz HA, Bastos RS. Atributos físicos, químicos e mineralógicos de solos da região de várzeas de Souza (PB). Rev Bras Cienc Solo. 2003;27:311-24. doi:10.1590/S0100-06832003000200011
https://doi.org/10.1590/S0100-0683200300...
; Pereira et al., 2013Pereira MG, Schiavo JA, Fontana A, Dias Neto AH, Miranda LPM. Caracterização e classificação de solos em uma topossequência sobre calcário na Serra da Bodoquena, MS. Rev Bras Cienc Solo. 2013;37:25-36. doi:10.1590/S0100-06832013000100003
https://doi.org/10.1590/S0100-0683201300...
; Silva, 2013Silva MB. Gênese e classificação dos solos em duas topossequências no sistema cárstico na Serra da Bodoquena (MS) [tese]. Seropédica: Universidade Federal Rural do Rio de Janeiro; 2013.).

Weathering complexes and selective Fe dissolution (Fes, Fed, and Feo)

Along the toposequence, the main oxide in the ADFE was SiO2 (123.7 to 219.3 g kg-1), followed by Fe2O3 (60 to 102 g kg-1) (Table 6). In P1 and P2, however, Fe2O3 contents were slightly lower than in the other profiles. Profiles P1 and P2 were characterized by thinner soil horizons, with high organic matter content, which increases moisture retention and likely promotes Fe reduction, complexation, and removal from the system (Corrêa et al., 2003Corrêa MM, Ker JC, Mendonça ES, Ruiz HA, Bastos RS. Atributos físicos, químicos e mineralógicos de solos da região de várzeas de Souza (PB). Rev Bras Cienc Solo. 2003;27:311-24. doi:10.1590/S0100-06832003000200011
https://doi.org/10.1590/S0100-0683200300...
). The contents of Fe2O3, TiO2, and P2O5 were low, reflecting the nature of the parent material. Similarly, Fe oxide and Ti contents are in line with values described for calcareous soils in Serra da Bodoquena, MS (Pereira et al., 2013Pereira MG, Schiavo JA, Fontana A, Dias Neto AH, Miranda LPM. Caracterização e classificação de solos em uma topossequência sobre calcário na Serra da Bodoquena, MS. Rev Bras Cienc Solo. 2013;37:25-36. doi:10.1590/S0100-06832013000100003
https://doi.org/10.1590/S0100-0683201300...
; Silva, 2013Silva MB. Gênese e classificação dos solos em duas topossequências no sistema cárstico na Serra da Bodoquena (MS) [tese]. Seropédica: Universidade Federal Rural do Rio de Janeiro; 2013.).

Table 6
Chemical composition and ki and kr molecular relationship for soil profiles in a toposequence in Lavandeira, TO, Brazil

The molecular relationships ki (1.91 to 3.10) and kr (1.34 to 2.10) indicate that the soils underwent moderate to intense weathering. This is confirmed by the mineralogy of the clay fraction, particularly the occurrence of hydroxyl interlayered (HI) vermiculite and illite in P1, P2, and P3, and kaolinite in P4 (footslope). All the profiles exhibited higher SiO2 than Al2O3 contents, and the higher ki values indicate low silica solubilization and removal in the profile, with consequent formation of 2:1 clay minerals. In the subsurface horizons of calcareous soils in Serra da Bodoquena, Silva et al. (2013)Silva MB, Anjos LHC, Pereira MG, Schiavo JA, Cooper M, Cavassani RS. Gênese e classificação dos solos de uma Topossequência em área de carste na Serra da Bodoquena, MS. Rev Bras Cienc Solo. 2013;37:1464-80. doi:10.1590/S0100-06832013000600004
https://doi.org/10.1590/S0100-0683201300...
attributed ki values from 1.96 to 2.56 to the occurrence of 2:1 clay minerals. Similarly, Shinzato (1998)Shinzato E. O carste da área de proteção ambiental de Lagoa Santa (MG) e sua influência na formação de solos [dissertação]. Campos dos Goytacazes: Universidade Estadual do Norte Fluminense; 1998. observed a ki from 2.3 to 4.2 in soils from Lagoa Santa Carste, MG, due to dominance of 2:1 clay minerals.

The results for P3 (ki = 1.91 to 2.2; kr = 1.37 to 1.5) and P4 (ki = 2.03 to 2.20; kr = 1.37 to 1.54) are associated with previous processes in the parent material. The sediments might have already been weathered when they were deposited on the backslope and footslope.

With regards to selective Fe dissolution (Fes, Fed, and Feo), the most important fractions in all the profiles were Fed and Fes. A similar result was described for calcareous soils in Chapada do Apodi, Ceará, Brazil (Ferreira, 2013Ferreira EP. Gênese e classificação de solos em ambiente cárstico na Chapada do Apodi [dissertação]. Seropédica: Universidade Federal Rural do Rio de Janeiro; 2013.). Fed contents ranged from 9.53 to 29.11 g kg-1 (Table 7), confirming the low Fe level in the parent material. In an earlier study on calcareous soils in Irecê, Bahia, Cunha et al. (1999)Cunha TJF, Manzatto CV, Ribeiro LP, Palmieri F, Filho C. Diferenciação pedológica e alteração de rochas calcárias na região de Irecê, BA. Rio de Janeiro: Embrapa Solos; 1999. (Pesquisa em andamento, 6). attributed Fed values from 14.59 to 27.25 g kg-1 to the nature of the parent material. Moreover, a low Fe/clay relationship (0.05 to 0.12) reinforces the poor Fe participation in this fraction (Pereira and Anjos, 1999Pereira MG, Anjos LHC. Formas extraíveis de ferro em solos do estado do Rio de Janeiro. Rev Bras Cienc Solo. 1999;23:371-82. doi:10.1590/S0100-06831999000200020
https://doi.org/10.1590/S0100-0683199900...
). This pattern is consistent with the low Fes value and can be credited to low Fe content in the parent material. The Feo/Fed ratio reflects the dominance of oxide forms with low crystallinity and is usually higher in surface horizons, associated with higher organic carbon (Kämpf and Schwertmann, 1983Kämpf N, Schwertamann U. Goethite and hematite in a climosequence in southern Brazil and their application in classification of kaolinitic soils. Geoderma. 1983;29:27-39. doi:10.1016/0016-7061(83)90028-9
https://doi.org/10.1016/0016-7061(83)900...
; Anjos et al., 2007Anjos LHC, Pereira MG, Pérez DV, Ramos DP. Caracterização e classificação de Plintossolos no município de Pinheiro-MA. Rev Bras Cienc Solo. 2007;31:1035-44. doi:10.1590/S0100-06832007000500020
https://doi.org/10.1590/S0100-0683200700...
). Fe complexation by functional groups of organic matter decreases the crystallinity of pedogenic Fe oxides (Anjos et al., 2007Anjos LHC, Pereira MG, Pérez DV, Ramos DP. Caracterização e classificação de Plintossolos no município de Pinheiro-MA. Rev Bras Cienc Solo. 2007;31:1035-44. doi:10.1590/S0100-06832007000500020
https://doi.org/10.1590/S0100-0683200700...
).

Table 7
Iron forms (Fes, Fed and Feo) in soil profiles in a toposequence in Lavandeira, TO, Brazil

The Bt2k6 horizon of P4 contained 9.46 g kg-1 Feo, and the Bt1k5 horizon, 6.70 g kg-1. Some of the poorly crystalline Fe oxides were likely moved from the upper horizons. The Fed/Fes ratio ranged from 0.2 to 0.45, with the lowest value in P1. These results suggest that Fe was mostly associated with other groups of minerals, especially illite. This finding is corroborated by clay mineralogy.

Mineralogy of sand and clay fractions

The mineralogy of fine and coarse sand showed predominance of quartz (Table 8), a mineral with high weathering resistance. In fact, quartz is dominant in the sand fraction of a significant part of Brazilian soils (Shinzato, 1998Shinzato E. O carste da área de proteção ambiental de Lagoa Santa (MG) e sua influência na formação de solos [dissertação]. Campos dos Goytacazes: Universidade Estadual do Norte Fluminense; 1998.; Miranda and Ferreira, 1999Miranda CSS, Ferreira MGVX. Caracterização de solos com A chernozêmico na zona da mata do norte do estado de Pernambuco. Rev Bras Cienc Solo. 1999;23:107-20. doi:10.1590/S0100-06831999000100014
https://doi.org/10.1590/S0100-0683199900...
; Alencar, 2002Alencar ELL. Química e mineralogia de três pedons originários de calcário da Chapada do Apodi-CE [dissertação]. Fortaleza: Universidade Federal do Ceará; 2002.; Anjos et al., 2007Anjos LHC, Pereira MG, Pérez DV, Ramos DP. Caracterização e classificação de Plintossolos no município de Pinheiro-MA. Rev Bras Cienc Solo. 2007;31:1035-44. doi:10.1590/S0100-06832007000500020
https://doi.org/10.1590/S0100-0683200700...
; Silva, 2013Silva MB. Gênese e classificação dos solos em duas topossequências no sistema cárstico na Serra da Bodoquena (MS) [tese]. Seropédica: Universidade Federal Rural do Rio de Janeiro; 2013.; Vasconcelos et al., 2013Vasconcelos BNF, Ker JCK, Schaefer CEGR, Poirier AP, Andrade FV. Antropossolos em sítios arqueológicos de ambiente cárstico no norte de Minas Gerais. Rev Bras Cienc Solo. 2013;37:986-96. doi:10.1590/S0100-06832013000400016
https://doi.org/10.1590/S0100-0683201300...
). The mineralogy of the sand fraction was uniform, with a variation in crystallinity. Poorly crystalline quartz was found in P1 and P2, likely because of lower silica content resulting from weathering. Other studies report silica predominance in the sand fraction of calcareous soils (Ferreira, 2013Ferreira EP. Gênese e classificação de solos em ambiente cárstico na Chapada do Apodi [dissertação]. Seropédica: Universidade Federal Rural do Rio de Janeiro; 2013.; Pereira et al., 2013Pereira MG, Schiavo JA, Fontana A, Dias Neto AH, Miranda LPM. Caracterização e classificação de solos em uma topossequência sobre calcário na Serra da Bodoquena, MS. Rev Bras Cienc Solo. 2013;37:25-36. doi:10.1590/S0100-06832013000100003
https://doi.org/10.1590/S0100-0683201300...
; Silva et al., 2013Silva MB, Anjos LHC, Pereira MG, Schiavo JA, Cooper M, Cavassani RS. Gênese e classificação dos solos de uma Topossequência em área de carste na Serra da Bodoquena, MS. Rev Bras Cienc Solo. 2013;37:1464-80. doi:10.1590/S0100-06832013000600004
https://doi.org/10.1590/S0100-0683201300...
), a situation frequently observed in soils from the Bambuí Group (Embrapa, 1983Empresa Brasileira de Pesquisa Agropecuária - Embrapa. Serviço Nacional de Levantamento e Conservação de Solos. Levantamento de reconhecimento de média intensidade dos solos e avaliação da aptidão agrícola das terras da margem direita do Rio Paranã, Estado do Goiás (Área de atuação da SUDECO). Rio de Janeiro: 1983. (Boletim de pesquisa, 23).).

Table 8
Mineralogy of sand and clay fractions of selected horizons

In P1, P2, and P3, HI-vermiculite was found in the clay fraction, followed by illite, kaolinite, and quartz (Table 8). The reflections of samples subjected to the heating pretreatment tended to merge, suggesting the presence of vermiculite interlayered with Al hydroxide polymers. Although inter-stratified vermiculite is commonly found in wet and cold environments (Boero et al., 1992Boero V, Premoli A, Melis, P, Barberis E, Arduino E. Influence of climate on the iron oxide mineralogy of terra rossa. Clays Clay Miner. 1992;40:8-13. doi:10.1346/CCMN.1992.0400102
https://doi.org/10.1346/CCMN.1992.040010...
), it has been identified in Brazilian soils under different conditions (Anjos et al., 2007Anjos LHC, Pereira MG, Pérez DV, Ramos DP. Caracterização e classificação de Plintossolos no município de Pinheiro-MA. Rev Bras Cienc Solo. 2007;31:1035-44. doi:10.1590/S0100-06832007000500020
https://doi.org/10.1590/S0100-0683200700...
). According to this last author, alternate periods of intense rainfall and prolonged dry weather in Maranhão, Brazil, located in the equatorial region, preserves high activity clay minerals due to internal restriction to drainage, a condition that leads to the occurrence of minerals such as smectite and HI-vermiculite. It is important to underscore that the Al between the layers destabilizes vermiculite (Resende et al., 2005Resende M, Curi N, Ker JC, Rezende SB. Mineralogia de solos brasileiros: interpretação e aplicações. Lavras: UFLA; 2005.), making it more susceptible to transformation.

In P4, the well-defined kaolinite reflections suggest its dominance (Shinzato, 1998Shinzato E. O carste da área de proteção ambiental de Lagoa Santa (MG) e sua influência na formação de solos [dissertação]. Campos dos Goytacazes: Universidade Estadual do Norte Fluminense; 1998.; Cunha and Ribeiro, 1998Cunha TJF, Ribeiro LP. Qualidade e relações pedogenéticas da matéria orgânica de alguns solos da região do Irecê (BA). Rev Bras Cienc Solo. 1998;22:693-704.). Kaolinite may originate from the transformation of primary and/or secondary minerals or by neoformation through recombination of Si in solution. In a study on calcareous soils in Sardinia, Boero et al. (1992)Boero V, Premoli A, Melis, P, Barberis E, Arduino E. Influence of climate on the iron oxide mineralogy of terra rossa. Clays Clay Miner. 1992;40:8-13. doi:10.1346/CCMN.1992.0400102
https://doi.org/10.1346/CCMN.1992.040010...
identified illite and kaolinite minerals as the main constituents of the clay fraction, whereas in northwest Italy they observed vermiculite with Al hydroxide between the layers. In studies of soils in the Mediterranean region, Durn (2003)Durn G. Terra Rossa in the Mediterranean Region: parent materials, composition and origin. Geol Croatica. 2003;56:83-100. found a predominance of illite and kaolinite in the clay fraction.

Soil genesis and classification

The variation in soil properties along the toposequence was closely associated with the topography factor, which determines drainage and surface runoff. In addition, the parent material consisted primarily of weathered limestone, and after topography, it was an important factor in soil genesis, where the profiles were of allochthonous and autochthonous origin. Accordingly, Pereira et al. (2013)Pereira MG, Schiavo JA, Fontana A, Dias Neto AH, Miranda LPM. Caracterização e classificação de solos em uma topossequência sobre calcário na Serra da Bodoquena, MS. Rev Bras Cienc Solo. 2013;37:25-36. doi:10.1590/S0100-06832013000100003
https://doi.org/10.1590/S0100-0683201300...
, highlights topography as one of the main determinants of the genesis of calcareous soils in Serra da Boodoquena, MS.

Evidence of the pedogenic process of melanization in surface horizons of the profiles varied in intensity, and the darker colors resulted from the interaction of the mineral fraction with the functional groups of organic matter (Duchaufour, 1970Duchaufour P. Humification et ecologie. Cah ORSTOM Sér Pédol. 1970;8:1-12.; Arnold, 1983Arnold RW. Conceitos of soils and pedology. In: Wilding LP; Smeck NE, Hall GF, editors. Pedogenesis and soil taxonomy - I. Concepts and interactions. Amsterdam: Elsevier; 1983. p1-21.; Fanning and Fanning, 1989Fanning DS, Fanning MCB. Soil: morphology, genesis and classification. New York: John Wiley; 1989.; Bockheim and Gennadiyev, 2000Bockheim JG, Gennadiyev AN. The role of soil-forming processes in the definition of taxa in soil taxonomy and the world soil reference base. Geoderma. 2000;95:53-72. doi:10.1016/S0016-7061(99)00083-X
https://doi.org/10.1016/S0016-7061(99)00...
; Kämpf and Curi, 2012Kämpf N, Curi N. Formação e evolução do solo (Pedogênese). In: Ker JC, Schaefer CEGR, Vidal- Torrado P, editores. Pedologia: fundamentos. Viçosa, MG: Sociedade Brasileira de Ciência do Solo; 2012. p.207-302.). The presence of CaCO3 in the profiles may be evidence of calcification or that the CaCO3 was inherited from the parent material. Sources of Ca2+ and CO32− are required for CaCO3 precipitation and pedogenic formation of carbonates and bicarbonates. The designation of horizons varies according to the carbonate source, and the “k̅” suffix is used for secondary carbonates, where “k” indicates carbonates derived from the parent material (Santos et al., 2013bSantos RD, Lemos RC, Santos HG, Ker JC, Anjos LHC, Shimizu SH. Manual de descrição e coleta de solo no campo. 6a.ed. Viçosa, MG: Sociedade Brasileira de Ciência do Solo; 2013b.).

Evidence of eluviation and illuviation were observed in P4 (Kämpf and Curi, 2012Kämpf N, Curi N. Formação e evolução do solo (Pedogênese). In: Ker JC, Schaefer CEGR, Vidal- Torrado P, editores. Pedologia: fundamentos. Viçosa, MG: Sociedade Brasileira de Ciência do Solo; 2012. p.207-302.), such as the occurrence of common and moderate clay skins in the Bt1k5 and Bt2k6 horizons, followed by an increase in clay in the Bt2k6 horizon, both indications of clay translocation.

With respect to soil classification, due to organic carbon content below 80 g kg-1 and the fact that upper horizons did not meet SiBCS criteria for other horizon types, the surface diagnostic horizons of P2, P3, and P4 were identified as moderate A. In contrast, P1 met the requirements for classification as A chernozêmico (Santos et al., 2013aSantos HG, Jacomine PKT, Anjos LHC, Oliveira VA, Oliveira JB, Coelho MR, Lumbreras JF, Cunha TJF. Sistema brasileiro de classificação de solos. 3ª ed. Rio de Janeiro: Embrapa Solos; 2013a.). With respect to subsurface diagnostic horizons, P2 and P3 did not show a noticeably pedogenic process, i.e., they exhibited low pedogenic evolution. The subsurface horizons of P2 and P3 were thus classified as incipient B (Santos et al., 2013bSantos RD, Lemos RC, Santos HG, Ker JC, Anjos LHC, Shimizu SH. Manual de descrição e coleta de solo no campo. 6a.ed. Viçosa, MG: Sociedade Brasileira de Ciência do Solo; 2013b.). The pattern of clay skins, along with texture and structure, were sufficient to classify the subsurface horizon of P4 as textural B (Santos et al., 2013bSantos RD, Lemos RC, Santos HG, Ker JC, Anjos LHC, Shimizu SH. Manual de descrição e coleta de solo no campo. 6a.ed. Viçosa, MG: Sociedade Brasileira de Ciência do Solo; 2013b.). P1 did not show a subsurface diagnostic horizon. However, an AC transitional horizon was observed and identified using the suffix “r”, indicating slightly altered rock. The “r” suffix is exclusively for C horizons (Santos et al., 2013bSantos RD, Lemos RC, Santos HG, Ker JC, Anjos LHC, Shimizu SH. Manual de descrição e coleta de solo no campo. 6a.ed. Viçosa, MG: Sociedade Brasileira de Ciência do Solo; 2013b.), but in this profile, it was used for the transitional horizon. The suffix “k” was used in the horizons of all profiles to indicate the presence of CaCO3 inherited from the parent material. A number of horizons, however, were enriched with secondary CaCO3 and identified by the suffix “k̅”, according to Santos et al. (2013b)Santos RD, Lemos RC, Santos HG, Ker JC, Anjos LHC, Shimizu SH. Manual de descrição e coleta de solo no campo. 6a.ed. Viçosa, MG: Sociedade Brasileira de Ciência do Solo; 2013b..

The soil order of P1 was classified in the SiBCS (Santos et al., 2013aSantos HG, Jacomine PKT, Anjos LHC, Oliveira VA, Oliveira JB, Coelho MR, Lumbreras JF, Cunha TJF. Sistema brasileiro de classificação de solos. 3ª ed. Rio de Janeiro: Embrapa Solos; 2013a.) as a Chernossolo (equivalent to Mollisols) due to the lithic contact and more than 150 g kg-1 of CaCO3 equivalent in the A horizon, which was identified as chernozêmico (Santos et al., 2013aSantos HG, Jacomine PKT, Anjos LHC, Oliveira VA, Oliveira JB, Coelho MR, Lumbreras JF, Cunha TJF. Sistema brasileiro de classificação de solos. 3ª ed. Rio de Janeiro: Embrapa Solos; 2013a.). In the suborder level, it met the criteria of rêndzico, due to the carbonate content and parent material (Santos et al., 2013aSantos HG, Jacomine PKT, Anjos LHC, Oliveira VA, Oliveira JB, Coelho MR, Lumbreras JF, Cunha TJF. Sistema brasileiro de classificação de solos. 3ª ed. Rio de Janeiro: Embrapa Solos; 2013a.); the Great Group was lítico (lithic), due to the contact with limestone up to a depth of 0.50 m; and the subgroup was típico (typic). P1 was classified by the SiBCS criteria as a Chernossolo Rêndzico Lítico típico. According to Soil Taxonomy (Soil Survey Staff, 2014Soil Survey Staff. Keys to soil taxonomy. 12th. ed. Washington, DC: USDA, Natural Resources Conservation Service; 2014.), the mollic epipedon directly above the rock and the dry climate, which indicates an ustic soil moisture regime, resulted in its being classified as an Ustolls. The lithic contact up to a depth of 0.50 m and lack of any diagnostic subsurface horizon identified P1 as a Lithic Haplustolls.

The soil order of P2 and P3 was classified as a Cambissolo (equivalent to an Inceptisol) owing to the incipient diagnostic horizon. At the suborder level they were classified as háplico (haplic) because of the absence of a distinguishing trait that would characterize them as another suborder. At the Great Group level, P2 was identified as Ta eutrófico, due to high clay activity and base saturation. Since the CaCO3 content was between 50 and 150 g kg-1, and the profile had lithic contact from 0.50 to 1.00 m from the soil surface, P2 was classified at the subgroup level as léptico hipocarbonático. In the SiBCS, P2 was classified as a Cambissolo Háplico Ta Eutrófico léptico hipocarbonático. In Soil Taxonomy (Soil Survey Staff, 2014Soil Survey Staff. Keys to soil taxonomy. 12th. ed. Washington, DC: USDA, Natural Resources Conservation Service; 2014.), the concept of epipedon “may include part or all of an illuvial B horizon if the darkening by organic matter extends from the soil surface into or through the B horizon”; thus, surface horizons, including Ak1, ABk2, and BAk3, with total thickness of 0.18 m, are qualified as mollic epipedon. Since base saturation ranges from 91 to 95 %, the profile was classified as a Mollisol. Considering the local dry climate, cambic horizon, and shallow profile (A + B of 0.33 m), the profile was classified as a Haplustolls; at the subgroup level, the lithic contact at up to 0.50 m from the mineral soil surface identified P2 as a Lithic Haplustolls.

Profile P3 showed a CaCO3 content of 220 g kg-1 in the ABk̅ horizon, which characterizes it as carbonático (carbonatic), and at the subgroup level, the lithic contact between 0.50 and 1.00 m defines it as léptico (leptic). Therefore, in the SiBCS, P3 was classified as a Cambissolo Háplico Carbonático léptico. According to Soil Taxonomy, the color and thickness of the epipedon characterizes an ochric surface horizon, which associated with the cambic horizon and dry climate, identified P3 as an Ustepts. Although ABk̅ had high CaCO3 equivalent content (220.56 g kg-1), it was less than 0.15 m thick, not qualifying as a calcic horizon, and the lithic contact at 0.33 m classified P3 as a Lithic Haplustepts.

Profile P4 was classified as a Luvissolo (corresponding to an Alfisol) due to the diagnostic B textural horizon being associated with high-activity clay and base saturation. At the suborder level it was identified as háplico (haplic), and due to the shallow profile (A + B equal to 0.57 m), the Great Group was órtico (orthic). However, the high CaCO3 content (79.41 to 82.77 g kg-1) that meets the requirement for hipocarbonático (Santos et al., 2013aSantos HG, Jacomine PKT, Anjos LHC, Oliveira VA, Oliveira JB, Coelho MR, Lumbreras JF, Cunha TJF. Sistema brasileiro de classificação de solos. 3ª ed. Rio de Janeiro: Embrapa Solos; 2013a.) should be considered in the classification of this profile, since it is a relevant feature for management purposes, affecting parameters such as pH, available P, and soil micronutrient dynamics. Profile P4 was thus classified as a Luvissolo Háplico Órtico típico and a new class is proposed, Luvissolo Háplico Órtico hipocarbonático, with criteria similar to other subgroups with the same characteristics. In Soil Taxonomy, the epipedon is ochric due to the Apk1 color (5YR 4/4), the subsurface horizon is argillic, and the high base saturation and dry climate identify P4 as Ustalfs at the suborder level. In the lower half of the argillic horizon, the hue of 2.5YR, a moist value of 3, and chroma of 4 defined the profile as Rhodustalfs. Given the absence of detailed information on the variation of the soil moisture regime, the C2wA’a’ climate classified P4 as a Typic Rhodustalfs.

CONCLUSIONS

Soil variations in the toposequence, particularly in profile depth and horizon development, were determined by topography, which governed drainage and surface runoff. Secondarily, the parent material affected soil morphology, texture, and chemical properties. All profiles showed high silt and clay content, high Ca and Mg contents, high pH, and low exchangeable Al. Base saturation and calcium carbonate equivalent were also high, and the horizons showed dark color due to high organic matter, dominated by the humin fraction.

Profiles were classified according to the SiBCS and Soil Taxonomy, and the main difference at the soil order level was for P2, classified as a Cambissolo and Mollisol, respectively. With regards to the SiBCS, we proposea new subgroup level for Luvissolos Háplicos Órthicos which present hypocarbonate features, since a CaCO3 content above 50 g kg-1 is of great importance to soil management. Therefore, P4 would be classified as a Luvissolo Háplico Órtico hipocarbonático.

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Publication Dates

  • Publication in this collection
    2016

History

  • Received
    9 Sept 2015
  • Accepted
    6 Jan 2016
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