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Andic properties in soils with histic horizon “O” in the highlands of Southern Brazil

ABSTRACT

Soils with andic properties are characterized by a low apparent density, variable charges, large amounts of allophanes, imogolite, ferrihydrite, and/or organo-metallic complexes with Al, and present high phosphate retention. Soils derived from non-pyroclastic materials rich in silicates, formed under a cold and humid climate, a large amount of organic carbon, acid weathering, andic properties can manifest when a large amount of Al is present in the form of organo-metallic complexes. This study aimed to evaluate the characteristics and geographical expression of soils with such properties in areas of altitude in the extreme south of Brazil, on the escarpment edges of the Serra Geral Formation, under a cold and humid climate. The sampling points were selected based on environmental characteristics such as geomorphology, geology, the coloration of the superficial horizon of the soil, and position in the landscape, covering a linear distance of approximately 185 km at the escarpment edge between the states of Santa Catarina and Rio Grande do Sul. Soil samples were described and collected from ten soils with histic horizon O, three soils with humic horizon, and one soil with histic horizon H. The undisturbed soil samples were collected using volumetric metallic cylinder to determine the soil bulk density. Organic matter, pH(H2O), P retention, and selective dissolutions of Al, Fe, and Si analyses were performed. The Cambissolos Hísticos and Organossolos Fólicos showed andic properties, while the Cambissolos Húmicos and Organossolo Háplico did not meet one or more criteria, as required by the Brazilian Soil Classification System and the World Reference Base for Soil Resources. The horizons with andic properties were classified as aluandic, based on the predominance of Al associated with organic complexes. The cold climate and high cloudiness of the highest altitude areas in the extreme south of Brazil, occurring in a narrow strip of the escarpment of the Serra Geral Formation in the states of Santa Catarina and Rio Grande do Sul, allow the formation of a constantly humid environment. This environment favors the acid weathering of the source material, accumulation of organic matter in the soil, and its stabilization by the formation of organo-metallic complexes, mainly Al-humus. The combination of these factors gives the soils with histic horizons O a low bulk density, high phosphate retention, and Alo + ½Feo ≥2 % values, meeting the criteria required for andic properties.

pedology; pedogenesis; organic matter; organo-metallic complexes

INTRODUCTION

Soils with andic properties are characterized by low bulk density, variable charges, large amounts of allophanes, imogolite, ferrihydrite, and/or organo-metallic complexes with Al, in addition to high phosphate retention (Soil Survey Staff, 2014Soil Survey Staff. Keys to soil taxonomy. 12th ed. Washington, DC: United States Department of Agriculture, Natural Resources Conservation Service; 2014.; IUSS Working Group WRB, 2015IUSS Working Group WRB. World reference base for soil resources 2014, update 2015: International soil classification system for naming soils and creating legends for soil maps. Rome: Food and Agriculture Organization of the United Nations; 2015. (World Soil Resources Reports, 106).). The presence of short-range-order minerals and/or organo-metallic complexes in soils with andic properties generally results from part of the moderate weathering sequence of pyroclastic materials (IUSS Working Group WRB, 2015IUSS Working Group WRB. World reference base for soil resources 2014, update 2015: International soil classification system for naming soils and creating legends for soil maps. Rome: Food and Agriculture Organization of the United Nations; 2015. (World Soil Resources Reports, 106).). However, andic properties can also manifest in soils with large amounts of Al in the form of organo-metallic complexes and non-pyroclastic materials rich in silicates in cold and humid climates, with a large amount of organic carbon (IUSS Working Group WRB, 2015IUSS Working Group WRB. World reference base for soil resources 2014, update 2015: International soil classification system for naming soils and creating legends for soil maps. Rome: Food and Agriculture Organization of the United Nations; 2015. (World Soil Resources Reports, 106).) formed under weathering in acidic conditions (Driessen et al., 2001Driessen P, Deckers J, Spaargaren O, Nachtergaele F. Lecture notes on major soils of the world. Rome: Food and Agriculture Organization of the United Nations; 2001. (World Soil Resources Reports, n. 94).).

There is growing evidence of soils’ occurrence with andic properties formed on non-pyroclastic material, indicating that their characteristics are mostly due to organo-metallic complexes instead of short-range-order minerals (Caner et al., 2000Caner L, Bourgeon G, Toutain F, Herbillon AJ. Characteristic of non‐allophanic andisol derived from low‐activity regoliths in Nilgiri Hills (Southern India). Eur J Soil Sci. 2000;51:553-63. https://doi.org/10.1111/j.1365-2389.2000.00344.x
https://doi.org/10.1111/j.1365-2389.2000...
). The rapid weathering of volcanic glass can result in the accumulation of stable organo-metallic complexes or the formation of short-range-order minerals, such as allophanes and imogolite, additionally forming ferrihydrite. However, the weathering of other materials rich in silicates in a humid climate also leads to the formation of stable organo-mineral complexes (Garcia-Rodeja et al., 1987Garcia-Rodeja E, Silva BM, Macias F. Andosols developed from non‐volcanic materials in Galicia, NW Spain. J Soil Sci. 1987;38:573-91. https://doi.org/10.1111/j.1365-2389.1987.tb02156.x
https://doi.org/10.1111/j.1365-2389.1987...
; IUSS Working Group WRB, 2015IUSS Working Group WRB. World reference base for soil resources 2014, update 2015: International soil classification system for naming soils and creating legends for soil maps. Rome: Food and Agriculture Organization of the United Nations; 2015. (World Soil Resources Reports, 106).).

The genesis of the andic properties depends essentially on the rapid weathering of the porous, permeable, and fine-grained mineral material in the presence of organic matter. The ions released in the hydrolysis of primary minerals, especially Fe2 and Al3, can form stable complexes with organic substances. However, the iron quickly oxidizes, and not all ions form complexes, allowing their precipitation as ferrihydrite. The concentration of silica in the soil solution increases if most or all the aluminum is stabilized in the complexes with organic substances. Part of this silica is leached, while another part precipitates as opaline silica. If a considerable proportion of released aluminum is not complexed, it can co-precipitate with silicon to form allophanes of varying composition, often in association with imogolite (Driessen et al., 2001Driessen P, Deckers J, Spaargaren O, Nachtergaele F. Lecture notes on major soils of the world. Rome: Food and Agriculture Organization of the United Nations; 2001. (World Soil Resources Reports, n. 94).).

When most or all of the aluminum is complexed with organic compounds, the silica concentration in the soil solution increases (Driessen et al., 2001Driessen P, Deckers J, Spaargaren O, Nachtergaele F. Lecture notes on major soils of the world. Rome: Food and Agriculture Organization of the United Nations; 2001. (World Soil Resources Reports, n. 94).); and while part of the silica is lixiviated, another part precipitates as opaline silica. If not, all aluminum is bound in complexes, the rest can co-precipitate with silicon to form minerals of low structural order, such as allophanes and imogolites. The formation of Al-humus complexes and the formation of allophanic associations are competitive. While allophanes and imogolites are stable under moderately acidic to neutral conditions, Al-humus complexes prevail in more acidic environments.

With excess aluminum available under such acidic conditions, it can combine with silicon to form 2:1 and 2:1:1 phyllosilicate clay minerals, which are often found in association with Al humus complexes (Ndayiragije and Delvaux, 2003Ndayiragije S, Delvaux B. Coexistence of allophane, gibbsite, kaolinite and hydroxyl‐Al‐interlayered 2:1 clay minerals in a perudic Andosol. Geoderma. 2003;117:203-14. https://doi.org/10.1016/S0016-7061(03)00123-X
https://doi.org/10.1016/S0016-7061(03)00...
). The occurrence of 2:1 and 2:1 of hydroxy-Al interlayer silicates in Andosols has often been associated with the presence of Al-humus complexes in non-allophanic Andosols (Shoji et al., 1993Shoji S, Dahlgren RA, Nanzyo M. Genesis of volcanic ash soils. In: Shoji S, Nanzyo M, Dahlgren RA, editors. Volcanic ash soils: genesis, properties and utilization. Amsterdam: Elsevier; 1993. p. 37-72.). The incorporation of Al in the organic complexes and / or in the intermediate Al layers of 2:1 clay minerals can induce an anti-antibiotic effect and inhibit the formation of allophane and imogolite (Shoji et al., 1993Shoji S, Dahlgren RA, Nanzyo M. Genesis of volcanic ash soils. In: Shoji S, Nanzyo M, Dahlgren RA, editors. Volcanic ash soils: genesis, properties and utilization. Amsterdam: Elsevier; 1993. p. 37-72.), as observed by Dahlgren et al. (1993)Dahlgren RA, Shoji S, Nanzyo M. Mineralogical characteristics of volcanic ash soils. In: Shoji S, Nanzyo M, Dahlgren RA, editors. Volcanic ash soils: genesis, properties and utilization. Amsterdam: Elsevier; 1993. p. 101-43. and Ndayiragije and Delvaux (2003)Ndayiragije S, Delvaux B. Coexistence of allophane, gibbsite, kaolinite and hydroxyl‐Al‐interlayered 2:1 clay minerals in a perudic Andosol. Geoderma. 2003;117:203-14. https://doi.org/10.1016/S0016-7061(03)00123-X
https://doi.org/10.1016/S0016-7061(03)00...
. The abundance of organo-metallic associations resulting from pedogenetic processes, presenting high physical and biological stability, low mobility, and high accumulation of organic matter, constitutes an original characteristic of soils with non-allophanic andic properties (Aran et al., 2001Aran D, Gury M, Jeanroy E. Organo-metallic complexes in an Andosol: a comparative study with a Cambisol and Podzol. Geoderma. 2001;99:65-79. https://doi.org/10.1016/S0016-7061(00)00064-1
https://doi.org/10.1016/S0016-7061(00)00...
).

In Brazil, the possibility of the contribution of allophanes in the manifestation of properties that would resemble andic soils in an altitude environment in areas of effusive rocks in the southern region of the country is briefly discussed by Bennema and Camargo (1964)Bennema J, Camargo MN. Segundo esboço parcial de classificação de solos brasileiros: subsídios a IV Reunião Técnica de Classificação de Solos. Rio de Janeiro: Ministério de Agricultura. Divisão de Pedologia e Fertilidade do Solo; 1964.. Fasolo et al. (1980)Fasolo PJ, Potter RO, Hochmuller DP, Cardoso A, Jacomine PKT, Larach JOI, Camargo MN, Carvalho AP. Estudo expedito de solos do Estado de Santa Catarina, para fins de classificação, correlação e legenda preliminar. Rio de Janeiro: Embrapa Solos; 1980. (Boletim Técnico, 65). also mention soils with potential andic properties in the state of Santa Catarina. However, these soils had no such properties (Ker, 1988Ker JC. Caracterização química, física, mineralógica e micromorfológica de solos Brunos subtropicais [dissertação]. Viçosa, MG: Universidade Federal de Viçosa; 1988.; Ker and Resende, 1990Ker JC, Resende M. Caracterização química e mineralógica de solos Brunos subtropicais do Brasil. Rev Bras Cienc Solo. 1990;14:215-25.). Volkoff et al. (1984)Volkoff B, Cerri CC, Melfi JA. 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;8:277-83. studied humus and mineralogy of altitude field soils in the states of Minas Gerais, Paraná, and Santa Catarina, focusing on the mobility of fulvic and humic acids, and found that the humus in these environments is similar to the humus of andic soils, of which properties were attributed to organo-metallic complexes, mainly with Al.

Studies of the soils from Trindade Island, in Brazil, indicate the presence of volcanic glass, amorphous materials, and low bulk density and high pH values in NaF, suggesting the presence of andic properties (Clemente, 2006Clemente EP. Ambientes terrestres da Ilha da Trindade, Atlântico Sul: caracterização do solo e do meio físico como subsídio para a criação e uma unidade de conservação [tese]. Viçosa, MG: Universidade Federal de Viçosa; 2006.; Clemente et al., 2009Clemente EP, Schaefer CEGR, Oliveira FS, Albuquerque Filho MR, Alves RV, Sá MMF, Melo VF, Corrêa GR. Topossequência de solos na Ilha da Trindade, Atlântico Sul. Rev Bras Cienc Solo. 2009;33:1357-71. https://doi.org/10.1590/S0100-06832009000500028
https://doi.org/10.1590/S0100-0683200900...
; Sá, 2010Sá MMF. Caracterização ambiental, classificação e mapeamento dos solos da Ilha da Trindade, Atlântico Sul [dissertação]. Viçosa, MG: Universidade Federal de Viçosa; 2010.; Machado, 2016Machado MR. O papel da avifauna na transformação geoquímica de substratos na Ilha da Trindade, Atlântico Sul [dissertação]. Belo Horizonte: Universidade Federal de Minas Gerais; 2016.; Machado et al., 2017). The presence of soils with andic properties in this location was later confirmed by Mateus et al. (2020)Mateus ACC, Varajão AFDC, Oliveira FS, Petit S, Schaefer CEGR. Non-allophanic Andosols of Trindade Island, south Atlantic: a new soil order in Brazil. Rev Bras Cienc Solo. 2020;44:e0200007. https://doi.org/10.36783/18069657rbcs20200007
https://doi.org/10.36783/18069657rbcs202...
. Furthermore, soils with andic properties in Brazil were described for the first time, by Dümig et al. (2008)Dümig A, Schad P, Kohok M, Beyerlein P, Schwimmer W, Kögel-Knabner I. A mosaic of nonallophanic Andosols, Umbrisols and Cambisols on rhyodacite in the southern Brazilian highlands. Geoderma. 2008;145:158-73. https://doi.org/10.1016/j.geoderma.2008.01.013
https://doi.org/10.1016/j.geoderma.2008....
, in the municipality of São Francisco de Paula, Rio Grande do Sul. This was the first confirmation of andic soils in South America outside the areas of recent volcanism in the Andes. This occurrence is mentioned in the World Reference Base for Soil Resources (IUSS Working Group WRB, 2015IUSS Working Group WRB. World reference base for soil resources 2014, update 2015: International soil classification system for naming soils and creating legends for soil maps. Rome: Food and Agriculture Organization of the United Nations; 2015. (World Soil Resources Reports, 106).).

There is an expressive area of soils that resemble those studied by Dümig et al. (2008)Dümig A, Schad P, Kohok M, Beyerlein P, Schwimmer W, Kögel-Knabner I. A mosaic of nonallophanic Andosols, Umbrisols and Cambisols on rhyodacite in the southern Brazilian highlands. Geoderma. 2008;145:158-73. https://doi.org/10.1016/j.geoderma.2008.01.013
https://doi.org/10.1016/j.geoderma.2008....
along the escarpment edge of the Serra Geral Formation in southern Brazil. The cold and humid climate of this environment favors the high accumulation of organic matter in the soil, which, associated with the acid weathering of the source material, rich in silicates, can generate andic properties on soils in a much more extensive area than that studied by Dümig et al. (2008)Dümig A, Schad P, Kohok M, Beyerlein P, Schwimmer W, Kögel-Knabner I. A mosaic of nonallophanic Andosols, Umbrisols and Cambisols on rhyodacite in the southern Brazilian highlands. Geoderma. 2008;145:158-73. https://doi.org/10.1016/j.geoderma.2008.01.013
https://doi.org/10.1016/j.geoderma.2008....
. However, this phenomenon can be restricted to a stretch on the escarpment edges, where the climate conditions favor the formation of histic horizons.

The general objective of this study was to evaluate the presence, characteristics, and extent of the occurrence of andic properties in soils with significant carbon content, formed on the escarpment edges of the Serra Geral Formation, in the southern plateau of the state of Santa Catarina (SC) and northeast plateau of the state of Rio Grande do Sul (RS).

MATERIALS AND METHODS

Study area

The study area includes the Serra Geral Formation’s escarpment edge in the southern plateau of Santa Catarina, and the extreme northeast plateau of Rio Grande do Sul (Figure 1). The studied environment is predominated by undulating relief areas, with smoothly wavy and flat parts, which contrast sharply with adjacent rugged reliefs that characterize the entire escarpment of the Serra Geral Formation in the extreme south of Brazil. Such areas are mainly in the municipalities of São Francisco de Paula, Cambará do Sul, and São José dos Ausentes, in RS, and Bom Jardim da Serra, Urubici, and Urupema, in SC.

Figure 1
Soil profiles with andic properties in southern Brazil.

The Serra Geral Formation of the Lower Cretaceous is the record of a fissure extensive volcanic event that covered approximately 75 % of the Paraná Sedimentary Basin (Stewart et al., 1996Stewart K, Turner S, Kelley S, Hawkesworth C, Kirstein L, Mantovani M. 3-D, 40 Ar-39 Ar geochronology in the Paraná continental flood basalt province. Earth Planet Sci Lett. 1996;143:95-109. https://doi.org/10.1016/0012-821X(96)00132-X
https://doi.org/10.1016/0012-821X(96)001...
; Milani et al., 1998Milani EJ, Faccini UF, Scherer CMS, Araújo LM, Cupertino JA. Sequences and stratigraphic hierarchy of the Paraná Basin (Ordovician to Cretaceous), Southern Brazil. Bol IG USP. 1998;29:125-73. https://doi.org/10.11606/issn.2316-8986.v29i0p125-173
https://doi.org/10.11606/issn.2316-8986....
; Nardy et al., 2002Nardy AJR, Oliveira MAF, Betancourt RHS, Verdugo DRH, Machado FB. Geologia e estratigrafia da Formação Serra Geral. Geociências. 2002;21:15-32.). This event was caused by the rupture of Gondwana, which formed after the Pan-African/Brazilian orogenic cycle and remained stable in its southern portion for approximately 400 million years, giving rise to the South Atlantic Ocean (Peate, 1997Peate DW. The Paraná-Etendeka Province. In: Mahoney JJ, Coffin M, editors. Large igneous provinces: Continental, oceanic and planetary flood volcanism. Washington: American Geophysical Union; 1997. p. 217-45.; Roisenberg and Viero, 2000Roisenberg A, Viero AP. O vulcanismo mesozóico da Bacia do Paraná no Rio Grande do Sul. In: Holz M, Ros LF, editors. Geologia do Rio Grande do Sul. Porto Alegre: CIGO/ UFRGS; 2000. p. 335-54.; Orlandi Filho et al., 2009).

The escarpment of the Serra Geral Formation extends diagonally across southern Brazil, with an abrupt east face, slowly declining to the west towards the Paraná and Uruguay rivers. Close to the border between the states of Santa Catarina and Rio Grande do Sul, the Serra Geral Formation rises and approaches the coast, bending in the north-northeast (NEE) direction for approximately 230 km following the coastline (Besser et al., 2015Besser ML, Vasconcellos EMG, Nardy AJR. Platô de São Joaquim, Província Magmática do Paraná: feições de campo e questões genéticas. Bol Paran Geocien. 2015;72:13-28. https://doi.org/10.5380/geo.v72i0.35875
https://doi.org/10.5380/geo.v72i0.35875...
). It consists of a series of rocks originating from basaltic spills, interspersed with andesitic spills, and the most recent spills of more acidic characteristics, resulting in the formation of more siliceous rocks, such as rhyodacite, dacites, and rhyolites (Bellieni et al., 1986Bellieni G, Comin-Chiaramonti P, Marques LS, Melfi AJ, Nardy AJR, Papatrechas C, Piccirillo EM, Roisemberg A, Stolfa D. Petrogenetic aspects of acid and basaltic lavas from the Paraná plateau (Brazil): Geological, mineralogical and petrochemical relationships. J Petrol. 1986;27:915-44. https://doi.org/10.1093/petrology/27.4.915
https://doi.org/10.1093/petrology/27.4.9...
).

The region’s climate, according to the Köppen classification system, is Cfb, wet temperate (C), with well-distributed rains throughout the year (f), and an average temperature of the hottest month below 22 °C (b) (Mota, 1951Mota FS. Estudos do clima do estado do Rio Grande do Sul segundo o sistema de W. Koeppen. Rev Bras Geogr. 1951;13:275-84.; Kuinchtner and Buriol, 2001Kuinchtner A, Buriol GA. Clima do estado do Rio Grande do Sul segundo a classificação climática de Köppen e Thornthwaite. Discip Sci Ser Cienc Exatas. 2001;2:171-82. https://doi.org/10.37779/nt.v2i1.1136
https://doi.org/10.37779/nt.v2i1.1136...
; Potter et al., 2004Potter RO, Carvalho AP, Flores CA, Bognolo I. Solos do Estado de Santa Catarina. Rio de Janeiro: Embrapa Solos; 2004. (Boletim de Pesquisa e Desenvolvimento n. 46).). There is a high water condensation in the highest portions of the escarpment, with daily fog formation near the top of the slopes and at the edges of the escarpments. These fogs can last up to weeks (Falkenberg, 2003Falkenberg DB. Matinhas nebulares e vegetação rupícola dos Aparados da Serra Geral (SC/RS), sul do Brasil [tese]. Campinas: Universidade Estadual de Campinas; 2003.).

Soil characterization

The sampling points were selected based on environmental characteristics such as geomorphology, geology, coloring of the superficial horizon of the soil, and position in the landscape, covering a stretch at the escarpment edge of the Serra Geral Formation, to the east from the municipality of São Francisco de Paula (RS) to Urupema (SC), in a linear distance of approximately 185 km (Figure 1 and Table 1).

Table 1
Lithology and position in the landscape of soils in the highlands in southern Brazil

Soil samples were described and collected from ten soils profiles with diagnostic histic horizon O (P2, P3, P4, P6, P8, P9, P10 P11, P12, and P13), three soils profiles with diagnostic humic horizon A (P1, P5, and P7), and one soil profile with histic horizon H (P14). The diagnostic histic horizon O is formed from deposited organic materials under free drainage conditions, without stagnant water, and occurring closer to the escarpment edge. The diagnostic humic horizon A occur a little further from the escarpment. The histic horizon H formed from organic materials deposited under excess water conditions in a small depression surrounded by soils with the histic horizon O. In 14 soil profiles were evaluated the possible presence of andic properties in this environment.

The basic characterization of all soil profiles, including the analysis of the main physical and chemical properties, are in tables 2 and 3. Details of these soils can be found in Santos Junior (2017).

Soil classification

The determination of superficial and subsurface diagnostic horizons was carried out according to the criteria defined in the 5th edition of the Brazilian Soil Classification System – SiBCS (Santos et al., 2018Santos HG, Jacomine PKT, Anjos LHC, Oliveira VA, Lumbreras JF, Coelho MR, Almeida JA, Araújo Filho JC, Oliveira JB, Cunha TJF. Sistema brasileiro de classificação de solos. 5. ed. rev. ampl. Brasília, DF: Embrapa; 2018.). The most acidic spills originated the rhyodacite and constituted the dominant source material of the soils in the studied area. The studied soils were classified according to the criteria established by the SiBCS (Santos et al., 2018Santos HG, Jacomine PKT, Anjos LHC, Oliveira VA, Lumbreras JF, Coelho MR, Almeida JA, Araújo Filho JC, Oliveira JB, Cunha TJF. Sistema brasileiro de classificação de solos. 5. ed. rev. ampl. Brasília, DF: Embrapa; 2018.) and the World Reference Base for Soil Resources (IUSS Working Group WRB, 2015IUSS Working Group WRB. World reference base for soil resources 2014, update 2015: International soil classification system for naming soils and creating legends for soil maps. Rome: Food and Agriculture Organization of the United Nations; 2015. (World Soil Resources Reports, 106).).

The diagnostic criteria used to identify andic properties in the WRB system (IUSS Working Group WRB, 2015IUSS Working Group WRB. World reference base for soil resources 2014, update 2015: International soil classification system for naming soils and creating legends for soil maps. Rome: Food and Agriculture Organization of the United Nations; 2015. (World Soil Resources Reports, 106).), which were recently adopted by the SiBCS (Santos et al., 2018Santos HG, Jacomine PKT, Anjos LHC, Oliveira VA, Lumbreras JF, Coelho MR, Almeida JA, Araújo Filho JC, Oliveira JB, Cunha TJF. Sistema brasileiro de classificação de solos. 5. ed. rev. ampl. Brasília, DF: Embrapa; 2018.), as suggested by Santos Junior (2017), are (a) soil density ≤0.9 kg dm-3; (b) phosphate retention ≥85 %; and (c) Alo + ½ Feo ≥2 %. The nature of the andic properties was defined based on the criteria of Poulenard and Herbillon (2000)Poulenard J, Herbillon AJ. Sur l’existence de trois categories d’horizons de réference dans les Andosols. C R Acad Sci. 2000;331:651-7. https://doi.org/10.1016/S1251-8050(00)01467-1
https://doi.org/10.1016/S1251-8050(00)01...
, described in the WRB IUSS Working Group (2015): a) silandic = Sio ≥0.6 % or Alp/Alo <0.5 (predominance allophane, imogolite, and similar minerals); b) aluandic = Sio <0.6 % and Alp/Alo ≥0.5 (predominance of Al complexed by organic acids); and c) alusilandic = Sio ≥0.6 % and <0.9 % and Alp / Alo ≥0.3 and <0.5 (transition condition considered a particular case of silandic property).

Laboratory analyses and other determinations

The soil samples were oven-dried at 40 °C, ground, and sieved to separate the fractions with a diameter smaller than 2.0 mm. Undisturbed soil samples were collected from the studied horizons using volumetric metallic cylinders to determine the soil bulk density (BD).

Organic carbon (Corg), pH(H2O), selective dissolution of Al, Fe, and Si, and P retention were analyzed using the air-dried fine earth fraction (ADFE). Hydrogen potential was measured using a combined electrode immersed in soil:water suspension in the proportion of 1:2.5, while Corg was quantified via muffle-drying by incineration, both according to methodologies described by Teixeira et al. (2017)Teixeira PC, Donagemma GK, Fontana A, Teixeira WG. Manual de métodos de análise de solo. 3. ed. rev e ampl. Brasília, DF: Embrapa; 2017.. The contents of Al, Fe, and Si in the soil were determined through selective dissolutions, being extracted by ammonium acid oxalate solution (Alo, Feo, and Sio), according to McKeague and Day (1966)McKeague JA, Day JH. Dithionite and oxalate extractable Fe and Al as aids in differentiating various classes of soils. Can J Soil Sci. 1966;46:13-22. https://doi.org/10.4141/cjss66-003
https://doi.org/10.4141/cjss66-003...
, described by Teixeira et al. (2017)Teixeira PC, Donagemma GK, Fontana A, Teixeira WG. Manual de métodos de análise de solo. 3. ed. rev e ampl. Brasília, DF: Embrapa; 2017., and sodium pyrophosphate (Alp), according to Bascomb (1968)Bascomb CL. Distribution of pyrophosphate - extractable iron and organic carbon in soils of various groups. Eur J Soil Sci. 1968;19:251-68. https://doi.org/10.1111/j.1365-2389.1968.tb01538.x
https://doi.org/10.1111/j.1365-2389.1968...
, described by Teixeira et al. (2017)Teixeira PC, Donagemma GK, Fontana A, Teixeira WG. Manual de métodos de análise de solo. 3. ed. rev e ampl. Brasília, DF: Embrapa; 2017., using an optical emission spectrometer with ICP-OES plasma. Phosphorus retention was determined according to the methodology described by Van Reeuwijk (2002)Van Reeuwijk LP. Procedures for soil analysis, 6th. ed. Wageningen: International Soil Reference and Information Center; 2002., adapted from Blakemore et al. (1987)Blakemore LC, Searle PL, Daly BK. Methods for chemical analysis of soils. Wellington: New Zealand Soil Bureau; 1987. (Scientific Reports, 80)..

RESULTS

The lithologies, location of the soils in relation to the hillside, slope, altitude, and distance to the edge of the escarpment are shown in table 1. Except P7 and P8, which were developed on basalt and andesite / basalt, respectively, the other studied soils are on rhyodacites. Three pedons are below 1000 m altitude (P1, P2, and P3), two pedons (P11 and P13) are above 1500 m, and the others are within this range of altitudes. The pedons P1, P5, P7, and P14 are in places with a slope less than or equal to 10 % and have the greatest distances to the Serra Geral Formation’s escarpment edge.

The physical and morphological properties of the 14 soil profiles surveyed are shown in table 2. According to the soil depth classes established by Santos et al. (2018)Santos HG, Jacomine PKT, Anjos LHC, Oliveira VA, Lumbreras JF, Coelho MR, Almeida JA, Araújo Filho JC, Oliveira JB, Cunha TJF. Sistema brasileiro de classificação de solos. 5. ed. rev. ampl. Brasília, DF: Embrapa; 2018., these soils can be classified as shallow (P13 and P14), fairly deep (P4, P10, and P12), and deep (P1, P2, P3, P5, P6, P7, P8, P9, and P11). The superficial horizons have a dark color and low BD ranging from 0.44 to 0.83 Mg m-3 (Table 4). The subsurface horizons are predominantly clayey with 100 % flocculation degree and at least incipient structure development, and with considerable variations in consistency: from slightly hard to extremely hard, very friable to firm, non-plastic to plastic, and non-sticky to sticky.

Table 2
Physical and morphological properties of soils in the highlands in southern Brazil
Table 4
Andic properties of soils in the highlands in southern Brazil

Table 3 shows the chemical properties of the soils. They are chemically poor soils, with low nutrient reserves, from strong to extremely acidic, according to the definitions of the soil reaction classes (Santos et al., 2018Santos HG, Jacomine PKT, Anjos LHC, Oliveira VA, Lumbreras JF, Coelho MR, Almeida JA, Araújo Filho JC, Oliveira JB, Cunha TJF. Sistema brasileiro de classificação de solos. 5. ed. rev. ampl. Brasília, DF: Embrapa; 2018.), with very low base saturation, containing high levels of extractable aluminum and consequently with high aluminum saturation. The pH(H2O) of the soil samples varied between 4.1 and 5.3 and the pH(KCl) varied between 3.4 and 4.7, however, in most horizons the pH(H2O) was below 5.0. and the pH(KCl) varied between 3.4 and 4.7. Extremely low P assimilable and Corg of surface horizons relatively high.

Table 3
Chemical properties of soils in the highlands in southern Brazil

Table 4 shows the values of BD, P retention, melanic index, and the results of the selective dissolution of Alo, Feo, Sio, Alp, in addition to Alo + 0.5Feo and the Alp / Alo ratio of the superficial genetic horizons (O, A, and H) of the surveyed soils. These items are part of the criteria for andic properties according to IUSS Working Group WRB (2015)IUSS Working Group WRB. World reference base for soil resources 2014, update 2015: International soil classification system for naming soils and creating legends for soil maps. Rome: Food and Agriculture Organization of the United Nations; 2015. (World Soil Resources Reports, 106).. There was a great variation in BD with very low values as in O1 and O2 of P4 with 0.44 and 0.54 kg dm-3, respectively, up to higher values as in horizons A1 and A2 of P1 with 0.75 and 0.83 kg dm-3, respectively. However, all surface horizons met the requirement of BD ≤0.9 Mg m-3, required for andic properties. The other horizons were not analyzed to verify all the criteria because they no longer met this BD requirement, making it impossible to frame these horizons as soils with andic properties.

The requirements for Alo + 0.5Feo ≥2 % did not meet the horizons of P1, P5, P7, and P14. For the retention of P ≥85 %, the horizons A1 and A2 of P1, A1 of P5, O and A of P7, and H1 and H2 of P14 did not achieve the requirement. All surface horizons of the studied soils showed Sio values <0.6 % and Alp / Alo ratio ≥0.5, so the soils with andic properties were classified as aluandic, with a predominance of Al forming complexes with organic acids (IUSS Working Group WRB, 2015IUSS Working Group WRB. World reference base for soil resources 2014, update 2015: International soil classification system for naming soils and creating legends for soil maps. Rome: Food and Agriculture Organization of the United Nations; 2015. (World Soil Resources Reports, 106).).

The soil classification is presented in table 5. The soils classified by the SiBCS criteria (Santos et al., 2018Santos HG, Jacomine PKT, Anjos LHC, Oliveira VA, Lumbreras JF, Coelho MR, Almeida JA, Araújo Filho JC, Oliveira JB, Cunha TJF. Sistema brasileiro de classificação de solos. 5. ed. rev. ampl. Brasília, DF: Embrapa; 2018.) can be grouped as follows: Cambissolos Húmicos (P1, P5, and P7); Cambissolos Hísticos (P2, P3, P6, P8, and P10); Organossolos Fólicos (P4, P5, P11, P12, and P13); and Organossolos Háplicos (P14). As for the WRB criteria (IUSS Working Group WRB, 2015IUSS Working Group WRB. World reference base for soil resources 2014, update 2015: International soil classification system for naming soils and creating legends for soil maps. Rome: Food and Agriculture Organization of the United Nations; 2015. (World Soil Resources Reports, 106).) it has: Cambic Umbrisol (P1, P5, and P7); Aluandic Andosol (P2, P3, P4, P6, P8, P10, P11, and P12); Folic Histosol (P9 and P13) and Leptic Umbrisol (P14). Soils with superficial diagnostic horizons O histic (Figure 2) has andic properties in its superficial genetic horizons.

Table 5
Soil classification in the highlands in southern Brazil

Figure 2
Soil profiles with andic properties in southern Brazil. (a) P2 - Cambissolo Hístico Alumínico típico, aluândico / Hyperdystric Umbric Aluandic Andosol (Clayic); (b) P3 - Cambissolo Hístico Alumínico típico, aluândico / Hyperdystric Umbric Aluandic Andosol (Clayic, Colluvic, Fulvic); (c) P4 - Organossolo Fólico Sáprico típico, aluândico / Umbric Leptic Aluandic Andosol (Hyperdystric, Siltic, Fulvic); (d) P6 - Cambissolo Hístico Alumínico típico, aluândico / Hyperdystric Umbric Aluandic Andosol (Clayic, Melanic); (e) P8 - Cambissolo Hístico Distrófico típico, aluândico / Hyperdystric Umbric Aluandic Andosol (Loamic, Colluvic, Fulvic); (f) P9 - Organossolo Fólico Sáprico cambissólico, aluândico / Ombric Sapric Folic Histosol (Andic, Hyperdystric); (g) P10 - Cambissolo Hístico Alumínico léptico, aluândico / Umbric Folic Aluandic Andosol (Hyperdystric, Clayic, Colluvic); (h) P11 - Organossolo Fólico Sáprico típico, aluândico / Umbric Folic Aluandic Andosol (Siltic, Fulvic, Melanic); (i) P12 - Organossolo Fólico Sáprico típico, aluândico / Umbric Leptic Aluandic Andosol (Hyperdystric, Siltic, Fulvic); (j) P13 - Organossolo Fólico Sáprico lítico, aluândico / Leptic Sapric Folic Histosol (Ombric, Andic, Hyperdristric).

DISCUSSION

The studied soils presented structures with moderate to strong degree of development with a yellowish color in the subsurface horizons, were clayey, acidic, with low natural fertility, and had superficial horizons (O, H, and A) of dark coloration with relatively high Corg values, low BD, and high P retention (Tables 2, 3, and 4).

The large variability of the morphological, physical, and chemical characteristics of soils with andic properties is evident when analyzing studies from different parts of the world (Bech-Borras et al., 1977Bech-Borras J, Fedoroff N, Sole A. Etude des andosols d’Olot (Gerona, Espagne) - 3e partie: Micromorphologie. Cah ORSTOM. 1977;XV:381-90.; Shoji and Saigusa, 1977Shoji S, Saigusa M. Amorphous clay materials of Towada ando soils. Soil Sci Plant Nutr. 1977;23:437-55. https://doi.org/10.1080/00380768.1977.10433063
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; Quantin et al., 1985Quantin P, Dabin B, Bouleau A, Lulli L, Bidini D. Characteristics and genesis of two Andosols in Central Italy. In: Fernandes-Caldas E, Yaalon DH, editors. Catena Supplement. 1985;7:107-17.; Wada, 1985Wada K. The distinctive properties of Andosols. In: Stewart BA, editor. Advances in soil science. New York: Springer-Velag; 1985:173-29. https://doi.org/10.1007/978-1-4612-5088-3_4.
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; Bäumler and Zech, 1994Bäumler R, Zech W. Characterization of Andisols developed from nonvolcanic material in Eastern Nepal. Soil Sci. 1994;158:211-7. https://doi.org/10.1097/00010694-199409000-00007
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; Arnalds et al., 1995Arnalds O, Hallmark CT, Wilding LP. Andisols from different regions of Iceland. Soil Sci Soc Am J. 1995;59:161-9. https://doi.org/10.2136/sssaj1995.03615995005900010025x
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; Johnson-Maynard et al., 1997Johnson-Maynard JL, McDaniel PA, Falen AL, Ferguson DE. Chemical and mineralogical conversion of Andisols following invasion by bracken fern. Soil Sci Soc Am J. 1997;61:549-55. https://doi.org/10.2136/sssaj1997.03615995006100020025x
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; Caner et al., 2000Caner L, Bourgeon G, Toutain F, Herbillon AJ. Characteristic of non‐allophanic andisol derived from low‐activity regoliths in Nilgiri Hills (Southern India). Eur J Soil Sci. 2000;51:553-63. https://doi.org/10.1111/j.1365-2389.2000.00344.x
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; Takahashi and Shoji, 2002Takahashi T, Shoji S. Distribution and classification of volcanic ash soils. Glob Environ Res. 2002;6:83-97.; Armas-Espinel et al., 2003Armas-Espinel S, Hernandez-Moreno JM, Muñoz-Carpena R, Regalado CM. Physical properties of “sorriba” – cultivated volcanic soils from Tenerife in relation to andic diagnostic parameters. Geoderma. 2003;117:297-311. https://doi.org/10.1016/S0016-7061(03)00130-7
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; Ndayiragije and Delvaux, 2003Ndayiragije S, Delvaux B. Coexistence of allophane, gibbsite, kaolinite and hydroxyl‐Al‐interlayered 2:1 clay minerals in a perudic Andosol. Geoderma. 2003;117:203-14. https://doi.org/10.1016/S0016-7061(03)00123-X
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; Pigna and Violante, 2003Pigna M, Violante A. Adsorption of sulfate and phosphate on Andisols. Commun Soil Sci Plant Anal. 2003;34:2099-113. https://doi.org/10.1081/CSS-120024051
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; Delvaux et al., 2004Delvaux B, Strebl F, Maes E, Herbillon AJ, Brahy V, Gerzabek M. An Andosol–Cambisol toposequence on granite in the Austrian Bohemian Massif. Catena. 2004;56:31-43. https://doi.org/10.1016/j.catena.2003.10.003
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; Ndayiragije and Delvaux, 2004Ndayiragije S, Delvaux B. Selective sorption of potassium in a weathering sequence of volcanic ash soils from Guadeloupe, French West Indies. Catena. 2004;56:185-98. https://doi.org/10.1016/j.catena.2003.10.010
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; Pinheiro et al., 2004Pinheiro J, Tejedor-Salguero M, Rodriguez A. Genesis of placic horizons in Andisols from Terceira Island Azores, Portugal. Catena. 2004;56:85-94. https://doi.org/10.1016/j.catena.2003.10.005
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; Bäumler et al., 2005Bäumler R, Caspari T, Totsche KU, Dorji T, Norbu C, Baillie IC. Andic properties in soil developd from nonvolcanic materials in Central Bhutan. J Plant Nutr and Soil Sci. 2005;168:703-13. https://doi.org/10.1002/jpln.200521793
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; Lowe and Palmer, 2005Lowe DJ, Palmer DJ. Andisols of New Zealand and Australia. JIFS. 2005;2:39-65.; Buytaert et al., 2006Buytaert W, Deckers J, Wyseure G. Description and classification of nonallophanic Andosols in south Ecuadorian alpine grasslands (páramo). Geomorphology. 2006;73:207-21. https://doi.org/10.1016/j.geomorph.2005.06.012
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; Msanya et al., 2007Msanya BM, Otsuka H, Araki S, Fujitake N. Characterization of volcanic ash soils in southwestern Tanzania: Morphology, physicochemical properties, and classification. Afr Stud Monogr. 2007;34:39-55. https://doi.org/10.14989/68484
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; Acevedo-Sandoval et al., 2008Acevedo-Sandoval O, Prieto-Garcia F, Gordillo-Martínez A. Identificar las fracciones de aluminio en un Andosol del estado de Hidalgo, México. Rev Soc Geol Esp. 2008;21:125-32.; Dümig et al., 2008Dümig A, Schad P, Kohok M, Beyerlein P, Schwimmer W, Kögel-Knabner I. A mosaic of nonallophanic Andosols, Umbrisols and Cambisols on rhyodacite in the southern Brazilian highlands. Geoderma. 2008;145:158-73. https://doi.org/10.1016/j.geoderma.2008.01.013
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; Kubotera et al., 2013Kubotera H, Kusaba T, Shishibe I. Distribution and horizons sequence of non-allophanic Kuroboku soils in Kuju Plateau, Kyushu, Japan. Pedologist. 2013;57:72-80. https://doi.org/10.18920/pedologist.57.2_72
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). However, some characteristics are commonly shared between these soils.

The pedons located closer to the edge of the escarpment in greater slopes are the ones that presented the highest Corg values, superficial diagnostic horizon O histic, and in these, there is the presence of the andic properties (Table 4). The data presented in table 1 suggested that the occurrence of the andic properties is somehow more related to the distance from the edge of the escarpment and the slope of the terrain than in relation to the altitude and hillside position. Pedons with andic properties are in slopes greater than 10 % at variable altitudes and hillside position; however, they are closest to the Serra Geral Formation’s escarpment edge.

According to the criteria of IUSS Working Group WRB (2015)IUSS Working Group WRB. World reference base for soil resources 2014, update 2015: International soil classification system for naming soils and creating legends for soil maps. Rome: Food and Agriculture Organization of the United Nations; 2015. (World Soil Resources Reports, 106). and Santos et al. (2018)Santos HG, Jacomine PKT, Anjos LHC, Oliveira VA, Lumbreras JF, Coelho MR, Almeida JA, Araújo Filho JC, Oliveira JB, Cunha TJF. Sistema brasileiro de classificação de solos. 5. ed. rev. ampl. Brasília, DF: Embrapa; 2018., the horizons O histic of the soils these study have andic properties. The occurrence of andic properties are associated with the highland environment with high humidity and low temperatures, favored by a relatively fast weathering, in an acid environment, rich in organic material, associated with the formation of organometallic complexes, with a predominance of Al in these forms (as suggested by the low Sio values and the high Alp / Alo ratio in table 4), therefore, these are non-allophanic andic soils with organometallic complexes or aluandic soils. Soils with andic properties of the aluandic type are generally dark, rich in organic matter in surface (topsoil), present varied morphology according to McDaniel et al. (2012)McDaniel PA, Lowe DJ, Arnalds O, Ping CL. Andisols. In: Huang PM, Sumner ME, editors. Handbook of soil science. 2nd ed. Boca Raton: CRC Press (Taylor & Francis); 2012. p. 33.29-33.48., and generally have pH(H20) <4.5, according to IUSS Working Group WRB (2015)IUSS Working Group WRB. World reference base for soil resources 2014, update 2015: International soil classification system for naming soils and creating legends for soil maps. Rome: Food and Agriculture Organization of the United Nations; 2015. (World Soil Resources Reports, 106)..

The pH(H20) of the horizons with andic properties of the surveyed soils ranged from 4.3 to 5.2, with most samples with values ≤5.0. Considering that the formation and maintenance of allophanes occurs at pH(H20) >4.9 (Shoji and Fujiwara, 1984Shoji S, Fujiwara T. Active aluminum and iron in the humus horizons of Andosols from northeastern Japan: Their forms, properties, and significance in clay weathering. Soil Sci. 1984;137:216-26. https://doi.org/10.1097/00010694-198404000-00002
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), the environment of this study does not favor the occurrence of these minerals, but the formation of organometallic complexes with a predominance of Al complexed by organic acids, such as was evidenced by the high Alp / Alo ratio.

In non-allophanic andic soils, a large part of Al complexed with humus can be preferentially dissolved by sodium pyrophosphate; therefore, the Alp / Alo ratio is often used to identify these soils (Dümig et al., 2008Dümig A, Schad P, Kohok M, Beyerlein P, Schwimmer W, Kögel-Knabner I. A mosaic of nonallophanic Andosols, Umbrisols and Cambisols on rhyodacite in the southern Brazilian highlands. Geoderma. 2008;145:158-73. https://doi.org/10.1016/j.geoderma.2008.01.013
https://doi.org/10.1016/j.geoderma.2008....
). According to the criteria of Nanzyo et al. (1993)Nanzyo M, Shoji S, Dahlgren R A. Physical characteristics of volcanic ash soils. In: Shoji S, Nanzyo M, Dahlgren R A, editors. Volcanic ash soils: genesis, properties and utilization. Amsterdam: Elsevier; 1993. p. 189-201., this ratio should be between 0.1-0.4 for allophanics and between 0.8-1.0 for non-allophanics. Aran et al. (2001)Aran D, Gury M, Jeanroy E. Organo-metallic complexes in an Andosol: a comparative study with a Cambisol and Podzol. Geoderma. 2001;99:65-79. https://doi.org/10.1016/S0016-7061(00)00064-1
https://doi.org/10.1016/S0016-7061(00)00...
found non-allophanic andic soils in northeastern France, on ancient volcanic rocks, with a large accumulation of organic matter and low pH, and considered the Alp / Alo ratios >0.8 relatively high, also suggesting that Al was complexed mainly with organic compounds.

In soils with andic properties, aluminum protects the organic part of Al-humus complexes against biodegradation. These complexes have limited mobility and moderate solubility; and this combination promotes the accumulation of organic matter in the topsoil, culminating in the formation of a surface horizon with intense dark color and high content of organic matter (Driessen et al., 2001Driessen P, Deckers J, Spaargaren O, Nachtergaele F. Lecture notes on major soils of the world. Rome: Food and Agriculture Organization of the United Nations; 2001. (World Soil Resources Reports, n. 94).), giving to these soils high porosity of strongly developed aggregate structures, which is mainly responsible for the low BD of non-allophanic andic soils, and a high water retention capacity (Nanzyo, 2002Nanzyo M. Unique properties of volcanic ash soils. Glob Environ Res. 2002;6:99-112.; McDaniel et al., 2012McDaniel PA, Lowe DJ, Arnalds O, Ping CL. Andisols. In: Huang PM, Sumner ME, editors. Handbook of soil science. 2nd ed. Boca Raton: CRC Press (Taylor & Francis); 2012. p. 33.29-33.48.).

The high phosphate retention in soils with andic properties occurs due to the large specific surface area and strong affinity of allophanes, imogolite, ferrihydrite and/or organometallic complexes with phosphorus (Parfitt, 1990Parfitt RL. Allophane in New Zealand - a review. Aust J Soil Res. 1990;28:343-60. https://doi.org/10.1071/SR9900343
https://doi.org/10.1071/SR9900343...
; Nanzyo, 2002Nanzyo M. Unique properties of volcanic ash soils. Glob Environ Res. 2002;6:99-112.). Phosporous retention occurs through the formation of internal sphere complexes at sites of high and low affinity and precipitation of Al-phosphate minerals (McDaniel et al., 2012McDaniel PA, Lowe DJ, Arnalds O, Ping CL. Andisols. In: Huang PM, Sumner ME, editors. Handbook of soil science. 2nd ed. Boca Raton: CRC Press (Taylor & Francis); 2012. p. 33.29-33.48.).

In summary, according to the criteria recently adopted in SiBCS (Santos et al., 2018Santos HG, Jacomine PKT, Anjos LHC, Oliveira VA, Lumbreras JF, Coelho MR, Almeida JA, Araújo Filho JC, Oliveira JB, Cunha TJF. Sistema brasileiro de classificação de solos. 5. ed. rev. ampl. Brasília, DF: Embrapa; 2018.), as suggested by Santos Junior (2017) based on IUSS Working Group WRB (2015)IUSS Working Group WRB. World reference base for soil resources 2014, update 2015: International soil classification system for naming soils and creating legends for soil maps. Rome: Food and Agriculture Organization of the United Nations; 2015. (World Soil Resources Reports, 106)., there are Cambissolos Hístico (P2, P3, P6, P8, and P10) and Organossolo Fólico (P4, P9, P11, P12, and P13), all with a superficial diagnostic horizon O hystic, with andic properties, aluandic, while Cambissolos Húmicos (P1, P5, and P7) and Organossolo Háplicos (P14) did not meet one or more of the required criteria.

CONCLUSIONS

The Cambissolos Hísticos and Organossolos Fólicos that occur in a narrow band on the escarpment edges of the Serra Geral Formation in the southern Santa Catarina plateau and northeastern plateau of the state of Rio Grande do Sul, above 900 m altitude, have andic properties.

The cold climate and high cloudiness of these high-altitude areas favor the formation of a constantly humid environment and the acid weathering of the source material, accumulation of organic matter in the soil, and its stabilization by the formation of organo-metallic complexes, especially Al-humus. The combination of these factors gives the diagnostic histic horizons low density, high phosphate retention, and Alo + ½Feo ≥2 % values, meeting the criteria required for andic properties.

ACKNOWLEDGMENTS

Our thanks to CAPES/FAPESC for granting the scholarship to the first author and to Embrapa Solo, for the financial contribution and for carrying out the soil characterization analyses of this study, through the SiBCS Project (PA 02.14.01.008.00.03).

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Edited by

Editors: José Miguel Reichert 0000-0001-9943-2898
Pablo Vidal Torrado 0000-0001-9228-9910
Marcos Gervasio Pereira. 0000-0002-1402-3612

Publication Dates

  • Publication in this collection
    09 Apr 2021
  • Date of issue
    2021

History

  • Received
    30 Sept 2020
  • Accepted
    25 Jan 2021
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