Carbonatites from the Southern Brazilian platform: I

Sergio Speziale 1 , Francesca Castorina 2 , Paolo Censi 3 , Celso de Barros Gomes 4 , Leila Soares Marques 5  and Piero Comin-Chiaramonti 6
  • 1 Helmholz-Zentrum Potsdam Deutsches GFZ, Section 3.6, Chemistry and Physics of Earth Materials, 14473 Potsdam, Germany
  • 2 Geosciences Department, Rome University, “La Sapienza”, 00185 Rome, Italy
  • 3 Earth and Sea Science Department, Palermo University, 90123 Palermo, Italy
  • 4 Geosciences Institute, Department of Mineralogy and Geotectonics, University of São Paulo, Cidade Universitária, SP 05508-900, São Paulo, Brasil
  • 5 Instituto de Astronomia, Geofísica e Ciências Atmosféricas, Department of Geophysics –  Universidade de São Paulo, Cidade Universitária, SP 05508-900, São Paulo, Brasil
  • 6 Department of Mathematics and Geosciences, Trieste University, 34127 Trieste, Italy
Sergio Speziale
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  • Helmholz-Zentrum Potsdam Deutsches GFZ, Section 3.6, Chemistry and Physics of Earth Materials, 14473 Potsdam, Germany
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, Francesca Castorina, Paolo Censi, Celso de Barros Gomes
  • Geosciences Institute, Department of Mineralogy and Geotectonics, University of São Paulo, Cidade Universitária, São Paulo, SP 05508-900, Brasil
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, Leila Soares Marques
  • Instituto de Astronomia, Geofísica e Ciências Atmosféricas, Department of Geophysics –  Universidade de São Paulo, Cidade Universitária, São Paulo, SP 05508-900, Brasil
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and Piero Comin-Chiaramonti
  • Department of Mathematics and Geosciences, Trieste University, 34127 Trieste, Italy
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Abstract

We present a comprehensive overview of the geochemical characteristics and evolution of the carbonatites from the southern Brazilian Platform (Paraná Basin). The carbonatites from different complexes display large compositional variability in terms of abundances of incompatible and rare earth elements. This is in agreement with an origin from heterogeneous lithospheric sources, as confirmed by isotopic data (see Speziale et al., this issue). The characteristic major and trace element abundances of these carbonatites present compelling evidence for invoking liquid unmixing as the main mechanism of their formation and evolution albeit few exceptions. We propose an evolutionary trend for the Brazilian carbonatites, which can be summarized as following: exsolution of the primary Ca- or Mg-carbonatitic liquids systematically takes place at the phonolite-peralkaline phonolite stage of magma differentiation; this is followed by progressive Fe-enrichment and by final emplacement of fluorocarbonatites associated with hydrothermal fluids.

1 Introduction

The Paraná Basin is a part of the Paraná-Angola-Namibia (Etendeka) Province (PAEP [1]). It is characterized by Early Cretaceous flood basalts (tholeiites) and dyke swarms (130–135 Ma, according to refs. [2,3,4,5] and references therein) associated with alkaline and alkaline–carbonatite complexes of Early Cretaceous to Tertiary age [6,7,8,9,10,11,12,13,14]. The emplacement of these complexes, in and around the PAEP, occurred mainly along tectonic structures active at least since the Early Mesozoic (Figure 1), and up to present day, as indicated also by the distribution of the earthquakes in southern Brazil [15]. Molina and Ussami [16] and Ernesto et al. [3,4] pointed to a clear correlation between geoid anomalies and magmatic/tectonic provinces along southeastern Brazil and Uruguay.

Figure 1
Figure 1

Distribution of the tholeiitic magmatism in the Paraná Province (South American Platform, Western Gondwana) and location of the main alkaline–carbonatitic regions in a reconstruction corresponding to 110 Ma (after refs. [39,51] and Figure 1.11 of ref. [14]), where all the single alkaline outcrops are represented. ASU, Central-Eastern Paraguay magmatic province [38]. Inset: Main lineaments in the Paraná-Etendeka System (South American and African plates, Western Gondwana) at about 110 Ma; modified after refs. [40,52] corresponding to the main lineaments of the alkaline and alkaline–carbonatitic complexes (cf. Figures 2–4 of Ref. [53]). APC, Araguaia-Paranaìba-Cabo Friom; M, Mocâmedes Arch; PGA, Ponta Grossa Arch; RP, Rio Piquirì; TS, Torres Syncline; DB, Damara Belt; RGA, Rio Grande Arch.

Citation: Open Geosciences 12, 1; 10.1515/geo-2020-0050

The carbonatitic complexes from southern Brazilian Platform have been the subject of several studies focussing on their geology, petrology, geochemistry, and processes of liquid immiscibility [6,8,9,10,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36].

The numerous carbonatitic occurrences provide additional information about the geochemical characteristics of the source regions, which are complementary to those from the silicate rocks. Carbonatitic liquids have extremely fast ascent rate and emplacement, and their peculiar chemical and physical characteristics make carbonatitic liquids better suited than silicate ones as indicators of mantle sources [36,37]. Here, we present the overall picture of the geochemical evolution of carbonatite magmatism in the southern Brazilian Platform by using an extended dataset of major and trace elements compositions (see Appendix).

This article and another article dedicated to the isotopic data (Speziale et al., this issue) can be considered a compendium of a series of specific studies from the same group of authors [11,12,13,14,31,32,38,39,40,41,42].

2 Geographic location, tectonic setting, major geolithological characteristics, and classification of the carbonatitic complexes in the Southern Brazilian Platform

The carbonatitic complexes from southern Brazil and Paraguay are found mainly along the following alignments: (1) Araguaia-Alto Paranaíba (APIP; [6])-Cabo Frio; (2) Ponta Grossa Arch (e.g., Jacupiranga, Juquiá, Barra do Itapirapuã); (3) Piquirí lineament (mainly in Eastern Paraguay); (4) Torres syncline; and (5) Rio Grande Arch (Figure 1).

Based on their age relative to the flood basalts and their associated intermediate and acid lava flows [2], these occurrences are pretholeiitic (e.g., Cerro Chiriguelo and Cerro Sarambí; 136–143 Ma), syn-tholeiitic (e.g., Anitápolis, Jacupiranga, Juquiá; 130–133 Ma), and posttholeiitic (e.g., Sapucai, 128 Ma; Ipanema, 124 Ma; Barra do Itapirapuã, 115 Ma) [cf. refs. 1,13,28,43,44]. In addition, tertiary alkaline complexes (mainly 45–65 Ma) are also present and distributed along the Taiúva-Cabo Frio lineament (Serra do Mar igneous province; cf. ref. [44]).

The geochemical characteristics of the carbonatites appear to be strictly linked to the mineral assemblages in the various evolutionary stages in carbonatites (p. 662 in ref. [31]). The mineral associations in the four main evolutionary stages are presented in Table 1.

Table 1

Generalized evolution of carbonatites in the Brazilian platform (cf. also ref. [45]). Data source: [14,21,28,29,30,31,38,39,46,47,48,49,50]

Major mineralsRare metal-bearing minerals
I stageCalcite, diopside, forsterite, melilite, monticellite, nepheline, phlogopite-biotite, apatite I, Ti-magnetiteNb-perovskite (Nb), calzirtite (Zr, Nb), monazite (Ce, REE)
II stageMg-calcite ± dolomite, diopside, tetraferriphlogopite, apatite II Mg-magnetiteBaddeleyite (Zr), pyrochlore-I (Nb), hatchettoloite (Nb, Ta, U, Th), zirkelite (Zr, Nb)
III stageCalcite, dolomite (Fe-dolomite), tetrapherriphlogopite, apatite III, magnetite, titanitePyrochlore (Nb, Th, U), burbankite (Sr, Ba, REE)
IV stageDolomite (Fe-dolomite), ankerite, siderite, magnesite, fluorite rhodochrosite, K-feldspar, quartzPyrochlore (U, Th, Nb), bastnäesite (REE), parisite (REE), ancylite (Sr, REE), synchysite (REE), strontianite (Sr), celestine (Sr)

According to refs. [22] and [27], carbonatite occurrences are believed to be produced by processes of liquid immiscibility. The rock association present in the Juquiá complex represents the prototype of all the examined carbonatites, whose evolution, reproduced by mass-balance calculations [22], follows the same sequence of stages: (1) fractionation from a parental basanite melt to a phonotephritic (basanitic) magma by crystallization of olivine clinopyroxenite and minor cumulus of olivine alkali gabbro; (2) separation of the least differentiated mafic nepheline syenite from the essexitic magma through fractionation of syenodioritic assemblages; and (3) exsolution of carbonate liquid from the CO2-enriched nepheline syenite magma, which further fractionates producing ijolite–melteigite–urtite cumulates.

The line of evolution (alkaline gabbro to syenogabbro to nepheline syenite) is linked to the removal of large amounts of cumulitic material, mainly olivine and clinopyroxene, as indicated by the abundance of pyroxenitic and dunitic rocks in the field (cf. Figures 2 and 3 of ref. [31]). Clinopyroxene and olivine fractionation is required for the transition from olivine nephelinite/ankaratrite to phonolite/peralkaline phonolite. The exsolution of carbonatite liquids appears to be associated with the evolution of phonolite to peralkaline phonolite liquids [18].

2.1 Petrographic classification

The rock associations present in the alkaline complexes of Southern Brazil are described in detail in refs. [11,14,39]. On the basis of the petrographic associations [14], the carbonatitic occurrences of the Paraná Basin can be classified as follows:

  1. 1)Magmatic carbonatites
    1. (A)Occurrences associated with rock types of the urtite–ijolite–melteigite series, without the presence of extrusive nephelinites (Brazil: Vale do Ribeira: Anitápolis, Ipanema, Itapirapuã, Jacupiranga, Mato Preto and Juquiá; Goiás: Caiapó and Morro do Engenho; Paraguay: Cerro Sarambí and Sapucai).
    2. (B)Brazilian occurrences associated with only olivinites and pyroxenites as ultramafitites (±syenites) as Salitre I and Serra Negra, and with glimmerites as Araxá, Catalão I, Catalão II and Salitre II.
    3. (C)Brazilian occurrences with either intrusive ultramelilitolites in Tapira [54] or extrusive olivine melilitites as in Lages [55] based on the classification schemes presented in refs. [56,57].
  2. 2)Hydrothermal carbonatites: those originated at temperatures ≤375°C are present at different locations in the Brazilian Platform. Barra do Itapirapuã is located in Brazil [28], Cerro Chiriguelo in Paraguay [21], and Cerro Manomó in Bolivia [52].
  3. 3)Occurrences with unusual geometric relationships: A limited number of occurrences of carbonatitic rocks in the form of small dykes (Itanhaém in Brazil [58]) or ocelli-like aggregates (Valle-mí, Cerro Canãda, Cerro E Santa Elena in Paraguay [59]) in alkaline silicate rocks.

2.2 Major elements’ chemistry

If we neglect those containing SiO2 > 10 wt%, the investigated carbonatites vary from calciocarbonatites (CaO, 39–45; MgO, 0.4–8.1; FeO, 0.1–10.1 wt%) to magnesiocarbonatites (CaO, 0.9–29; MgO, 12.6–46.8; FeO, 1.1–10.9 wt%) and ferruginous (i.e., iron-rich) calciocarbonatites (CaO, 28–36; MgO, 4.3–13.4; FeO, 10.0–30.3 wt%; cf. ref. [11]). However, all the three rock types are rarely associated in the same complex (e.g., Araxá, Barra do Itapirapuã, Itapirapuã; cf. refs. [30,28]). Notably, the Cerro Manomó carbonatite (Bolivia) represents the only example of a ferrocarbonatite (CaO, 7.7; MgO, 0.34; FeO, 40.5; MnO, 7.1 wt% [33,52]). The molar ratio CaO/(CaO + MgO + FeOt + MnO) used as a differentiation index (DI) of carbonatites from Southern Brazil shows a general negative correlation with (MgO + FeOt + MnO) wt% due to Ca–Mg–Fe–Mn substitutions typical of the main carbonate minerals [11]. The data are well consistent with multistage carbonatite evolution associated with changes of the rock-forming mineral assemblages [45], with DI decreasing from the stage I to the stage 4 of Table 1.

2.2.1 Magmatic carbonatites

2.2.1.1 Carbonatites associated with rock types of the urtite–ijolite–melteigite series, without the occurrence of extrusive nephelinites

Whole-rock chemistry data were plotted in the carbonatite classification [60,61] and appear represented by calciocarbonatites followed by magnesiocarbonatites and by ferruginous carbonatites (Figure 2, IA and IB).

Figure 2
Figure 2

(I) Classification of carbonatitic associations (oxides are expressed in molar proportions, after Refs. [60,61] for the various complexes from the Brazilian Platform [31,62]). (a) Brazilian Early Cretaceous: Anitápolis, Ipanema, Itapirapuã, Jacupiranga, and Juquiá; it also includes the Early Cretaceous Paraguayan occurrences of Cerro Sarambí and Sapucai as shown in the figure IB. (b) Late Cretaceous: Caiapó, Morro do Engenho, Santo Antônio da Barra, and Mato Preto [31,62]. The full list of references is also reported in Table 1A of the Appendix. (II) Quaternary diagram showing compositional trends of exsolved carbonate liquids from a residual silicate magma [63]. The curves of 2 kb and 5 kb are theoretical isobaric-polythermal solvi [27], and the symbols are selected samples from the Appendix. Mineral abbreviations: Cpx, clinopyroxene; Mel, melilite; Ol, olivine; Ne, nepheline. (III) Classification of group B of Brazilian Late Cretaceous carbonatitic associations (Salitre, Serra Negra, Araxá, Catalão I, and Catalão II; cf. Table 1B of the Appendix).

Citation: Open Geosciences 12, 1; 10.1515/geo-2020-0050

In the region of Vale do Ribeira, alkaline carbonatite complexes are present in Anitápolis, Ipanema, Itapirapuã, Jacupiranga, and Juquiá (Figure 2, IA: Early Cretaceous age, 132–109 Ma; cf. ref. [39] and Table 1A of the Appendix). Early-stage magnesiocarbonatites are usually rich in apatite and phlogopite and are found in the same carbonatitic complex only at Jacupiranga, which is considered to be a primary carbonatite [25]. On the opposite, the Juquiá magnesiocarbonatites (the only rock type present in this complex) are modeled as the result of fractionation from exsolved calciocarbonatite magma [22]. This model [22] may represent a suitable picture for all the examined carbonatitic complexes, where various stages of evolution are identified, together with an additional late Fe-enrichment of carbonate liquids (Figure 2, IA and II). A similar picture applies to the genesis and evolution of the Eastern Paraguay carbonatites [27].

The Late Cretaceous (70–86 Ma) Goiás carbonatites from Caiapó, Morro do Engenho, and Santo Antônio da Barra are present in Ca and Mg variants, similar to the Early Cretaceous carbonatites of Cerro Sarambí (139 Ma) and Sapucai (121 Ma) in Paraguay (Figure 2, IB and Table 1A of the Appendix).

2.2.1.2 Alkaline–carbonatite complexes with only olivinite and pyroxenites as ultramafic rocks (±syenites) or with glimmerites

All the complexes of this group belong to the Late Cretaceous (81–86 Ma) episode of alkaline carbonatite magmatism. Both Salitre [64,65] and Serra Negra [66] are without glimmerites (cf. Figure 2, III). Conversely, the complexes of Araxá [67], Catalão I [68], and Catalão II [69] contain glimmerites. Serra Negra and Catalão II calciocarbonatites and magnesiocarbonatites are found in Salitre, whereas only magnesiocarbonatites are found in Araxá and Catalão I (Figure 2, III). Notably, the evolution from phonolite to peralkaline phonolite liquids trend is shown in Figure 2, II [18] and Figure 2 of ref. [12].

2.2.1.3 Carbonatites associated with melilitolites and melilitites

The Upper Cretaceous complexes of Tapira (70 Ma; [62,54]) and Lages (82 Ma; [30]) are the only two representatives of this group. Tapira complex contains calciocarbonatites and subordinate magnesiocarbonatites associated with ultramelilitolites, while in Lages, only ferruginous calciocarbonatites are present (Figure 3, IV) associated with olivine melilitites. According to ref. [70], complete or partial separation of carbonatites from the melite-rich silicate fractions (eventually producing intrusive melilitolites or extrusive melilitites) is related to carbonate–silicate immiscibility, probably occurred under pressure less than 14 kbar and temperature higher than 1,300°C. Subsequently, carbonatites might reach the surface as a separate eruption.

2.2.2 Hydrothermal carbonatites

The carbonatitic complex of Barra do Itapirapuã (115 Ma), according to ref. [28], is represented by rare calciocarbonatites and dominant magnesiocarbonatites with subordinate ferruginous calciocarbonatites (Figure 3, V). Notably, all the rock types formed under hydrothermal conditions at temperatures between 375°C and 80°C [28,71].

Figure 3
Figure 3

(IV) Classification of group C Brazilian Late Cretaceous carbonatitic associations (Tapira and Lages). Oxides are expressed as molar proportion (cf. Figure 2, and Table 1C of the Appendix). (V) Classification of the Early Cretaceous hydrothermal carbonatitic association of Barra do Itapirapuã in Brazil [28,71]. Oxides are expressed as molar proportion (cf. Table 2 of the Appendix). The plot also includes data for the complexes of Cerro Chiriguelo [21,41] and Cerro Manomó. (VI) Classification (occurrences with unusual geometric relationships) of the Early Cretaceous carbonatitic rocks from Itanhaém (129 Ma, [58]), Valle-mí (138 Ma; [37] and references therein), and Cerro Cañada and Cerro E Santa Elena (124 and 127 Ma, respectively [1,12]).

Citation: Open Geosciences 12, 1; 10.1515/geo-2020-0050

The complex of Cerro Chiriguelo (Figure 3, V, 128 Ma) [21,41] shows calciocarbonatites in the central part and veins of ferruginous carbonatite cutting the carbonatitic core.

Finally, Cerro Manomó (139 Ma), in Bolivia, contains carbonate blocks, interpreted by ref. [72] as ferrocarbonatites (Figure 3, V and Table 2 of Appendix). According to ref. [33], the latter rock types are made up of sideritic-ankeritic carbonate, altered at hydrothermal conditions and associated mainly with rare earth elements (REE) fluorocarbonates.

2.2.3 Occurrences with unusual geometric relationships

This group consists of extremely small carbonatite occurrences with geometries that are not present in other carbonatitic complexes in Southern Brazil. A 0.3 m thick fine-grained beforsitic (ferruginous calciocarbonatitic) dyke crosses tinguatic rocks in Itanhaém (Brazil [58]). Basanitic dykes are found in Valle-mí (Paraguay) patches (probably exsolved) of calciocarbonatite[37]. In Cerro Canãda and Cerro E Santa Elena (Paraguay), ocelli made of dolomite, phlogopite, clinopyroxene, olivine, magnetite, and amphibole are contained in trachyandesitic dykes [1,11,12] (Figure 4). Representative analyses are presented in Table 3 of the Appendix and plotted in Figure 3, VI.

Figure 4
Figure 4

Mineral association representative of an ocellus in ijolite from the Cerro E Santa Elena alkaline complex (127 ± 8 Ma), Central Eastern Paraguay; modified after refs. [11,12]. Am, amphibole; Bi-Phl, biotite-phlogopite; Cpx, clinopyroxene; Dol, dolomite; Mt, magnetite; Ol, olivine (cf. Figure 3-VI).

Citation: Open Geosciences 12, 1; 10.1515/geo-2020-0050

2.3 Incompatible elements (IEs)

The results discussed in this section is presented in the same order as the previous section, that is, (1) magmatic carbonatites, (2) hydrothermal carbonatites, and (3) occurrences with unusual geometric relationships (cf. Figures 2 and 3).

2.3.1 Magmatic carbonatites

IE concentrations, which are reported in the Appendix, are shown in Figures 5 (group A) and 6 (groups B and C) as spidergrams normalized to primitive mantle concentrations [73].

Figure 5
Figure 5

IE concentrations normalized to primitive mantle [73] for magmatic group A (cf. Figure 2) Early Cretaceous and Late Cretaceous carbonatites from Southern Brazil and Eastern Paraguay. Data sources in Appendix; Early Cretaceous: Anitápolis, [30]; Itapirapuã, [74]; Jacupiranga, [18,20,25,26,27,75]; Ipanema, [35]; Juquiá, [22,27]; Late Cretaceous: Mato Preto, [29]; Caiapó and Morro do Engenho, [46]; Santo Antônio da Barra, [6,8]. Ca, calciocarbonatite; Fe, ferruginous calciocarbonatite; Mg, magnesiocarbonatite.

Citation: Open Geosciences 12, 1; 10.1515/geo-2020-0050

Figure 6
Figure 6

IE normalized to primitive mantle concentrations [73] for magmatic group B Late Cretaceous carbonatites from Southern Brazil. Data sources: Appendix. Salitre, [64,65]; Serra Negra, [66]; Catalão I, [68]; Catalão II, [69]; Araxá, [67]. Magmatic group C Late Cretaceous carbonatites from Southern Brazil (cf. Appendix): Tapira, [54]; Lages, [30,55,76]. Ca, Mg, and Fe: calciocarbonatite, ferrocarbonatite, and ferruginous calciocarbonatite.

Citation: Open Geosciences 12, 1; 10.1515/geo-2020-0050

The normalized values of the Early and Late Cretaceous magmatic carbonatites appear strongly enriched in La, Ce, Nd, Sm, and Eu, whereas K and Ti are systematically the least enriched elements, or they are depleted. P and Zr present very large variations probably linked to the occasional presence of apatite or phlogopite. As a matter of fact, IE in Brazilian carbonatites typically shows very large variations in the normalized values from one carbonatite complex to another for any given incompatible element [26]. The IE scatter between the different carbonatites reflects to some extent the variable distribution and concentration of mineral phases, which have high contents of selected IE such as phosphates (e.g., apatite and monazite for REE), oxides (e.g., pyrochlore for Nb, REE, Th, and U; calzirtite for Ti and Zr; zirconolite for Ti, Zr, and Nb; and loparite for REE, Ti, and Nb), REE carbonates, and REE fluorocarbonates (e.g., ancylite, bastnäsite, burbankite, and parisite).

Experiments on natural and synthetic mixtures show that carbonatite melts might be enriched in K, P, Sr, Ba, Th, and REE, as well as in F and Cl ([77] and references therein). The presence of F in silicate–carbonate systems positively influences the fractionation of Nb (Ta, U, Th, and REE) in the carbonate phase. Partitioning of IE and REE into the carbonate melt is also supported by experimental results on Nb and light rare earth element (LREE) solubility in synthetic carbonate liquids [78].

Moreover, according to ref. [79], calciocarbonatite liquids can dissolve 5–7.5 wt% of Nb2O5 at 950–600°C. Crystallization of these liquids at first promotes the precipitation of a perovskite-type phase followed by pyrochlore together with calcite. Phase relationships in the join calcite-La-hydroxide of the CaCO3–Ca(OH)2–La(OH)3 system [77,80,81] show that, with the temperature variation from 610 to 700°C and increasing CO2/H2O ratio, the solubility of the LREE hydroxides in simplified carbonatite systems changes from 20% to 40% [81]. Bastnäsite may crystallize together with calcite from magmatic carbonate liquids with a temperature falling from liquidus (650–625°C) to eutectic (about 540°C) and under definite relations between carbon dioxide, water, and fluorine contents.

As shown in ref. [82], Brazilian carbonatites cover a wide range in a La versus La/Yb plot (cf. Figure 4 of ref. [37]), with the carbonate fractions of carbonatites displaying La/Yb ratios and La content two to three times higher than those of the parental rocks [11]. The La versus La/Yb trend of Rio Apa dykes was quantitatively modeled in ref. [37] by assuming that basanite was the carbonatites parental magma. The chemical evolution was described in terms of two main steps: (1) differentiation from basanite to trachyphonolite to phonolite by fractional crystallization and concentration of CO2-rich fluids and (2) exsolution of about 20% carbonatitic liquids from the differentiated phonolitic magma (Figure 7).

Figure 7
Figure 7

Evolutionary path of La/Yb ratio versus La, as determined for the Rio Apa dykes [37].

Citation: Open Geosciences 12, 1; 10.1515/geo-2020-0050

Phlogopite-picrite rocks associated with carbonatites in Tapira as well as in other alkaline–carbonatitic complexes in the APIP show a strong compositional affinity to kamafugites present in the northern part of the APIP [6,62,65,83]. Notably, ref. [54] show that liquid immiscibility was a common process (from early phlogopite-picrites to late syenites) in the evolution of the Tapira complex, indicating liquid immiscibility of carbonatitic pockets at the very early stages (Figure 2 of ref. [54]). An exhaustive description of the relationships between carbonatites and associated kamafugites was presented in [39].

The overall very large variability of IE contents between primary carbonatites (formed by early-stage liquid immiscibility) from the different complexes supports the hypothesis that the alkaline–carbonatitic magmatism was produced by local heterogeneous subcontinental mantle sources connected to metasomatic events attributed to Neoarchean to Neoproterozoic time based on isotopic systematics ([11,12]; see also the study by Speziale et al., this issue). Some of this complexity, especially in the pattern of REE contents, can be due to the process of carbonatitic magma unmixing that produce characteristic crossing between the patterns of carbonatites and associated silicate rocks [84].

2.3.2 Hydrothermal carbonatites

REE carbonates, REE fluorocarbonates, and oxides, which are the products of hydrothermal environments, represent to some extent the individual fenitizing fluids enriched in IE rather than the primary carbonates [37]. For instance, different generations of carbonatite dykes are present in the Barra do Itapirapuã complex (Figure 3, V) [28, 85, 86]. In Barra do Itapirapuã, carbonatites are present as dykes and veins stockwork in which at least three main carbonatitic phases are recognized (Figure 3, V), that is, prevailing magnesiocarbonatites, ferruginous calciocarbonatites, and subordinate calciocarbonatites (Figure 8). These carbonatites are generally overprinted by pervasive hydrothermal events at temperatures between 375°C and 80°C during which significant amounts of REE fluorocarbonate minerals, relatively Th- and Sr-rich were deposited. Synchysite, parasite, and bastnäsite may occur as single crystals and/or polycrystals. Textural and chemical relationships between the REE fluorocarbonates provide insights into the mobility of REEs during fluid–rock interaction [28,31,85].

Figure 8
Figure 8

IE normalized to primitive mantle concentrations [73] for Early Cretaceous hydrothermal carbonatites. Data sources: Barra do Itapirapuã, [28,71]; Cerro Chiriguelo, [21]; Cerro Manomó, [52]. Ca, calciocarbonatite; Fe, ferruginous carbonatite; Mg, magnesiocarbonatite.

Citation: Open Geosciences 12, 1; 10.1515/geo-2020-0050

At Cerro Chiriguelo (Figure 8), calciocarbonatites are the prevailing rock types and show relatively high contents of Ba, Ta, Th, and Nb. The subordinate ferruginous calciocarbonatites also display high contents of Nb, Ta, and REE. Nb and Th contents of these rocks appear related to the local abundance of uranpyrochlore [21].

Cerro Manomó presents rare blocks of ferrocarbonatite made up of altered sideritic–ankeritic carbonatite with subordinate goethite–limonite, apatite, and REE-F-carbonates [52]. The latter produces a strong REE enrichment clearly shown in Figure 8.

2.3.3 Occurrences with unusual geometric relationships

The Itanhaém carbonatite (129 Ma, according to ref. [58], is represented by fine-grained Fe-dolomite veins in tinguaitic dykes, particularly enriched in Th and LREE, which make this complex a Th source of economic interest [87]).

Basanitic dykes (about 139 Ma) with a microcrystalline groundmass consisting of about 20 vol% of primary calciocarbonates are present near the town of Valle-mí in Paraguay [41]. The carbonates show large enrichment of Th (Nb and Ta), REE, and Sr, and strong depletion of K and Ti with respect to mantle abundances (Figure 9).

Figure 9
Figure 9

IE normalized to primitive mantle concentrations [73] for early cretaceous carbonatites occurrences with unusual geometric relationships. Sources of data: Itanhaém [58,87], Valle-mí [41], and Cerro Cañada and Cerro E Santa Elena [59].

Citation: Open Geosciences 12, 1; 10.1515/geo-2020-0050

The ijolitic host rocks in Cerro Cañada and Cerro E. Santa Elena alkaline complexes (notional age, 126 Ma [88]) are characterized by ocelli containing dolomite (magnesiocarbonatite; Figure 4) highly enriched in Ba, Sr, and REE ([11,37] and references therein) as shown in Figure 9.

Notably, the IE spidergrams (Figures 5–9) display remarkable scattering even within individual complexes. This is particularly evident between samples of Ca, Mg, and ferroginous calciocarbonatite belonging to different stages of crystallization of the same complex (i.e., magmatic to late-magmatic and hydrothermal conditions).

Different types of distinctive behaviors emerge if we plot REE spidergrams. In Figure 10, we grouped the different carbonatites as a function of their age of emplacement. Here, we can identify three main types of distribution [31]:

  1. (1)Patterns with a strong decrease from La to Lu, which can be observed for instance in the rocks from Cerro Chiriguelo, Jacupiranga, and APIP [6,62] magnesiocarbonatites, Mato Preto, and Lages (both early and late carbonatites). It should be noted that the REE enrichment in Mato Preto and Lages appear to be controlled by late, secondary, carbonatite veins.
  2. (2)Patterns with a relative weakly decrease from La to Lu, as shown in Jacupiranga (calciocarbonatites), Juquiá (magnesiocarbonatites and calciocarbonatites), Anitápolis, and Barra do Itapirapuã (calciocarbonatites).
  3. (3)Concave patterns with a steady decrease from LREE to Dy and an HREE plateau, as found in Valle-mí and Barra do Itapirapuã occurrences. The carbonatites from the latter location contain the highest LREE concentrations due to the presence of REE fluorocarbonates [25,31,32,37,50,62]. Fluorite deposits are also present in Barra do Itapirapuã.

Figure 10
Figure 10

Spidergrams of REE normalized to chondritic contents [90] for selected Early and Late Cretaceous carbonatites (modified after ref. [31] cf. also Figures 5–9).

Citation: Open Geosciences 12, 1; 10.1515/geo-2020-0050

In conclusion, the different behaviors of the early-crystallized carbonatites, which are believed to be “primary” carbonatitic liquids (calciocarbonatites and magnesiocarbonatites), would reflect the chemical signatures of their parental melts (cf. primary calciocarbonatites and magnesiocarbonatites of the Jacupiranga and Juquiá complexes, respectively), as also outlined by ref. [89] and confirm the presence of local scale heterogeneous subcontinental mantle sources of possible due to metasomatic events dating back to the Neoarchean to Neoproterozoic based on radiogenic isotopes systematics [11,12]. The presence of late-crystallized ferruginous calciocarbonatites, variably enriched in fluorocarbonates, indicates hydrothermal processes, also supported by the observed low-temperature mineral associations (cf. [38,39]).

3 Concluding remarks

The alkaline–carbonatitic magmatism from the Southern Brazil is distributed along tectonic lineaments in both American and African continents.

The carbonatites mainly occur in the inner parts of circular/oval-shaped alkaline–carbonatitic complexes, being the rock bodies usually associated with evolved silicate rocks where liquid immiscibility processes played an important role in their genesis.

The geochemical data, major and trace elements, show that the genesis of the magmatism from the Southern Brazilian Platform requires heterogeneous mantle sources. As a matter of fact, the large variation of IE and REE appear related to hydrothermal processes, probably connected to metasomatic sensu lato events that occurred between Neoarchean and Neoproterozoic times [11,12].

The areal distribution of magmatism suggests that the alkaline–carbonatitic magmatism originated from large- to small-scale heterogeneous subcontinental mantle. All the results indicate that asthenospheric components derived from mantle plumes (i.e., Tristan da Cunha and Trindade hot spots [91]) did not significantly contribute to the genesis of the alkaline–carbonatitic magmatism, consistent with the conclusions reached by refs. [2,3,4,11,82,92] for the petrogenesis of the Paraná flood tholeiites

Regional thermal anomalies in the deep mantle, mapped by geoid and seismic tomography, support a nonplume-related heat source for the southern Brazil magmatism [4,93,96], where the hotspot tracks of Walvis Ridge and Rio Grande Rise, as well as the Victória–Trindade chain, might reflect the accommodation of stresses in the lithosphere during rifting rather than continuous magmatic activity induced by mantle plumes beneath the moving lithospheric plates (cf. also the study by Speziale et al., this issue), where the main conclusions relative to the Brazilian carbonatites are reported).

Acknowledgements

S.S. acknowledges support from the Deutsche Forschungsgemeinschaft DFG (FOR 2125). We thank the editor Dr. J. Barabach and an anonymous reviewer. F. Stoppa is thanked for his very detailed comments and suggestions which helped us to improve our manuscript. We also thank O. Gerel, V.A.V. Girardi and L. Kogarko for their comments.

Appendix

Magmatic carbonatites

Table 1A

Selected analyses of representative carbonatites of the urtite–ijolite–melteigite series without nephelinites extrusives. References: Brazil: Vale do Ribeira: Anitápolis [17,94]; Ipanema [35]; Itapirapuã [74]; Jacupiranga [25,31,32,62,75]; Mato Preto [29]; Juquiá [22]. Goiás: Caiapó and Morro do Engenho [46]. Paraguay: Cerro Sarambí [41,42]; Sapucai [95]

Anitápolis age: 131 (1) MaIpanema age: 124.9 (9.5) Ma
Sample SAN 1.014–4912–7811–10116A–50.549–82119.2
wt%
SiO20.310.202.451.200.473.003.97
TiO20.010.010.060.050.070.080.13
Al2O30.210.020.010.090.100.520.19
FeO0.082.592.032.954.495.967.61
MnO0.070.080.230.220.231.800.25
MgO1.552.304.131.831.7012.801.08
CaO53.5951.2549.3652.1551.8031.4347.60
Na2O0.050.160.340.010.071.510.37
K2O0.490.780.070.020.061.010.30
P2O50.481.312.372.891.802.121.73
L.O.I.42.0640.1338.7238.2538.3738.6435.68
Sum98.9098.8399.7799.66100.0699.0398.91
IE (ppm)
Rb3.26.16.56.95.53.228
Ba1052951157911218941106500
Th5.63.50.310.090.275.500.8
Nb5.28.97.810.48.36.324.0
Ta1.40.51.51.81.41.020.3
K4,0686,475581166498832,491
Sr2,4622,9836,8494,4622,7792,4625,950
P20,9505,71710,34312,6127,8555242,550
Hf0.40.41.80.80.380.671.4
Zr15.87.746.215.516.418.7454
Ti6060360300420480779
Y43.718.845.942.941.529.8120
REE
La67.141.2123.448.615897976.1
Ce142.390.3287106.53722,657170
Pr16.812.229.214.537.829123.9
Nd69.647.5115.753.5170.41,154196
Sm13.89.421.339.4429.2232622
Eu4.02.536.513.918.55129.46.24
Gd12.67.9119.838.9020.6147515.9
Tb1.871.352.171.593.4861.31.6
Dy9.627.6711.639.0412.177285.9
Ho1.741.392.441.642.11131.20.8
Er4.813.175.903.744.43155.71.9
Tm0.630.560.810.670.7123.760.25
Yb3.743.094.833.483.0725.001.5
Lu0.590.440.650.510.363.210.19
Mol%
CaO96.090.695.991.089.556.886.2
FeO + MnO0.23.73.54.36.411.011.1
MgO3.85.70.64.74.132.22.7
MatoPreto age: 70 (1) MaJuquiá age: 132 (3) Ma
Sample I—119.3I—84.0II—77.0III—70.0III—62.2III—622S16CS25S26AS26BSJT
Wt%
SiO20.300.230.521.912.283.220.240.300.270.360.29
TiO20.010.010.110.020.110.060.020.010.030.020.02
Al2O30.230.140.210.210.590.810.070.100.090.110.10
FeO1.810.922.231.7310.014.561.541.721.581.691.63
MnO0.190.190.220.210.730.390.380.520.430.470.45
MgO0.990.331.320.516.121.4912.5917.1117.5217.5516.49
CaO54.3554.8353.1355.0139.2149.7437.8330.9031.0530.3932.54
Na2O0.030.010.020.010.100.060.890.450.450.460.56
K2O0.100.070.090.310.581.090.020.020.020.020.04
P2O50.520.170.510.160.281.6713.255.475.575.286.14
L.O.I.41.2743.1541.3840.1638.8936.4033.1443.8842.9743.6140.90
Sum99.83100.0599.74100.2498.9099.4999.9799.9899.9899.9699.16
IE
ppm
Rb2.94.36.810.21.618945634.5
Ba1753,7981,1344498,3782,2261,7003,78012,5004,4905,618
Th44.819.982147811117.82.735.004.514.684.23
Nb251384239531525.1168201616
Ta9.418.70.86.311.81.40.742.130.741.701.33
K8305817472,5744,8159,049166166166166332
Sr8,7352,1348,7581,0533,6934,6528,4505,5405,7205,1905,985
P2,2697422,2266981,2227,28857,78323,87124,29123,04226,795
Hf2.97.70.23.72.44.91.252.621.553.242.18
Zr45.912323183123178167201615
Ti606065912065917912060180120120
Y74.312119222596673339402119202266
REE
La1981652413,6868521,11299.399.168.685.288.1
Ce3774617176,5101,5771,808262257177221232
Pr44.369.510158115523334.530.724.231.430.5
Nd15634146188435094816414997.9120148
Sm25.873.491174527931.529.5 18.923.226.8
Eu8.222.622.256.817.025.017.621.37.5411.512.4
Gd24.176.271161488866.772.621.532.149.9
Tb3.7412.08.323.16.914.412.312.24.17.69.2
Dy17.367.339.98630.29059.770.321.636.853.0
Ho2.8112.36.79.75.118.211.312.94.16.09.7
Er7.324.016.026.510.44727.632.210.517.025.8
Tm1.072.832.63.81.76.93.84.31.01.73.7
Yb4.7810.28.522.611.334.117.321.75.939.6916.8
Lu0.421.532.203.341.85.71.652.070.520.641.60
Mol%
CaO94.997.693.496.169.989.366.654.754.553.857.0
FeO + MnO2.71.63.42.615.07.02.63.12.83.02.8
MgO2.40.83.21.315.13.730.842.242.743.240.2
GoiásCaiapó age: 86 (6) MaMorro do Engenho age: 86 (6) MaSanto Antônio da Barra age: 86 (6) MaParaguay Cerro Sarambí age: 138.9 (0.9) Ma Paraguay Sapucai age: 128.6 (2) Ma
CR-09ME-CSAB-12GL-SAGL-SASA-958 TrachyphonolitePS72 Phonotephrite
Glimmerite-Carbonatite (whole rock)Carbonate Fraction (dolomite)Carbonate Fraction (dolomite)Carbonate Fraction (calcite 7%)Carbonate Fraction (24.3 wt%)
Wt%
SiO22.260.620.8828.82—-
TiO20.270.150.073.220.060.05
Al2O30.100.050.057.37
FeO4.713.143.538.711.494.252.51
MnO0.260.230.280.110.26
MgO3.784.7114.8519.2720.833.9520.17
CaO45.9446.3032.859.2330.2148.1230.04
Na2O0.280.190.050.290.25
K2O0.100.120.043.350.080.07
P2O57.701.012.290.310.390.33
L.O.I.33.0241.0442.3916.2147.1943.3746.77
Sum98.4297.5697.2897.99100.00100100.00
IE
ppm
Rb2.04.02.3138.16.716.90.21
Ba4,4544,87216,4692,08210136262
Th30110310412.526370.32
Nb53.111350.194931120.90
Ta12.94.44.57.76.89.20.76
K83099633227,812664581
Sr11,66910,54210,8511,3872,8604,066268
P33,6034,4085,0141,3531,7021,444
Hf8.92.232.237.16.65.4
Zr324125171289370292
Ti1,61989942019,304360300
Y377107129238.62323.75
REE
La4551,011909167513343239
Ce1,0931,6471,725319980654420
Pr14716210335.645.34146.8
Nd637513682123139138159.9
Sm11992.813314.720.118.319.1
Eu59.525.033.73.96.15.253.90
Gd14064.782.910.119.310.414.90
Tb19.86.547.961.032.141.652.12
Dy89.426.532.47.612.98.710.57
Ho14.94.894.991.12.511.92.05
Er22.76.047.222.96.274.85.40
Tm2.880.450.540.400.680.533.16
Yb10.02.072.551.703.282.5324.7
Lu1.110.920.350.230.430.340.32
Mol%
CaO83.483.559.021.550.184.549.9
FeO + MnO7.14.75.416.01.95.83.6
MgO9.511.835.662.548.09.746.5
Table 1B

Carbonatites associated with ultramafic rocks (olivinites and pyroxenites) ± syenites as Salitre I and Serra Negra and with glimmerites as Araxá, Catalão I, and Catalão II. References: Salitre [64,65], Serra Negra [66], Araxá [67], Catalão I [68], and Catalão II [69]

Sample Salitre I Age: 86.3 (4.2) Ma
C1C4ASL013ASL031ASL034ASL03609A-60A
Wt%
SiO20.061.340.220.330.420.240.26
TiO20.010.380.170.060.010.010.01
Al2O30.010.090.170.320.190.230.01
FeO1.462.352.883.090.661.670.18
MnO0.120.560.390.190.150.220.08
MgO0.7914.6518.4814.885.1719.351.57
CaO53.8428.7525.1335.4046.1129.7253.94
Na2O0.170.170.100.190.460.500.13
K2O0.110.220.030.050.010.160.11
P2O50.016.690.4310.160.010.660.99
L.O.I.40.7032.2046.1434.7744.7046.0441.20
Sum97.2599.0494.1499.4797.8998.7798.49
IE
ppm
Rb1.64.415.33.36.510.75.7
Ba3,1785,00728,3943232.6266326.5
Th10.557.81641.580.220.5155
Nb14.288.977.3629695161524
Ta0.100.51.13n.a.n.a.2.923.9
K9131,826249415831,328913
Sr17,56o26,48010,1476,6836,6617,1003,180
P4429,1951,87744,338832,8804,320
Hf0.113.00.24n.a.n.a.0.3725.1
Zr3.5097.34.244.114.96.71,071
Ti602,2781,019360606060
Y53.99566.55420.515.679.1
REE
La3736,3541,84626410785.1431
Ce7018,5413,4866842831811,203
Pr68.8700400n.a.n.a.7.8149
Nd2422,2041,45231912879566
Sm38.82012024417.711.072.3
Eu7.2844.855.4n.a.n.a.2.719.2
Gd21.1682.0125n.a.n.a.6.441.6
Tb2.278.7410.34n.a.n.a.0.705.66
Dy10.0430.426.04n.a.n.a.2.7018.14
Ho1.662.982.73n.a.n.a.0.322.51
Er4.026.664.91n.a.n.a.0.614.82
Tm0.600.760.70n.a.n.a.0.090.61
Yb3.484.274.84n.a.n.a.0.423.27
Lu0.530.450.68n.a.n.a.0.090.41
Mol%
CaO95.855.947.160.385.551.295.8
FeO + MnO2.24.44.84.41.22.50.4
MgO2.039.748.135.313.346.33.8
Sample Serra Negra age: 83(5) Ma
LG-03-70LG-14-28LG-06-32LG-13-125LG20-91.5LG32-63.80LG38-46-142
wt%
SiO20.540.880.650.740.200.920.14
TiO20.020.200.040.050.010.110.01
Al2O30.010.090.040.030.020.340.01
FeO1.985.291.804.191.112.961.69
MnO0.130.140.110.140.250.600.40
MgO3.603.152.974.5119.4418.9819.50
CaO48.8245.9448.6145.8729.3627.7129.23
Na2O0.030.060.100.070.060.090.13
K2O0.090.120.160.150.030.050.05
P2O50.483.323.622.590.350.260.09
L.O.I.43.1139.5240.2139.6946.7045.9047.82
Sum98.8198.7098.3198.0397.5397.9399.07
IE
ppm
Rb2.105.005.307.501.302.700.80
Ba2,7682,3142,3913,5159301,5022,187
Th2.3038.844.47.303141.211.6
Nb97.3373292129280299.45.30
Ta22.028.023.38.6016.73.300.05
K7479961,3291,245249415415
Sr13,26818,83316,12211,35412,0515,51710,003
P2,09514,48815,79811,3031,5271,134393
Hf6.401.601.202.100.400.100.05
Zr326.273.246.289.2139.201.80
Ti1201,1992403006065960
Y35.354.873.940.94.9072.49.10
REE
La29041449837482.4818135
Ce517783959699152.91,511201
Pr60.0493.82122.6685.6117.4121521.14
Nd202.6321.6427.9291.259.3080566.90
Sm24.3941.2554.9336.546.23103.327.80
Eu6.5210.8915.259.581.5627.302.36
Gd16.3128.0438.4224.093.6768.446.93
Tb1.803.034.242.530.377.020.93
Dy8.2812.7917.9910.541.4425.303.56
Ho1.261.932.601.450.182.770.38
Er2.744.215.763.000.354.100.53
Tm0.359.560.760.410.040.450.07
Yb2.033.274.122.230.272.190.32
Lu0.270.410.500.270.030.200.04
Mol%
CaO88.084.289.682.651.148.750.4
FeO + MnO3.07.82.86.11.84.92.8
MgO9.08.07.611.347.146.446.8
Sample Araxá age: 88 (10) MaCatalão I age: 87 (4) MaCatalão II age: 85 (6) Ma
AE 891 Phlo-richAR 892 Phlo- rich AR 893 C1- L1250C1CB02 C1C4C1C12B C1C14 C2-AA 165907C2A2C2B19C2B18C2B17
wt%
SiO29.749.932.151.750.250.644.670.228.954.023.4614.890.21
TiO22.862.901.920.080.010.020.250.010.440.050.880.120.01
Al2O32.762.812.790.080.110.050.130.020.200.060.030.280.01
FeO11.139.7510.348.895.401.8010.891.239.452.294.657.580.21
MnO0.190.160.180.280.220.370.850.610.250.100.110.090.07
MgO18.1016.5418.3114.6017.3619.2631.3046.812.562.822.518.120.56
CaO13.7014.6116.1623.2333.5925.4110.350.9239.9046.4946.0232.9953.56
Na2O0.210.110.140.050.060.070.010.010.820.100.060.140.11
K2O5.214.452.290.310.140.010.010.030.631.100.843.420.14
P2O50.220.190.184.340.101.042.590.091.491.082.7114.790.25
L.O.I.35.0738.8544.6431.2041.2041.9534.3550.8931.7038.5235.1113.9142.78
Sum99.19100.3099.1899.2499.0690.6095.39100.0796.4196.6596.3996.3697.89
IE
ppm
Rb1491381.119.51.736224.651562334
Ba1,2991,2031,6487,6221,57352,3003,9362334,1745,3053,0361,4304,531
Th18.2116–9723.118.312.12644.83.21587.54.629.51.4
Nb2,7502,51432.1306203231434931010912723814
Ta16.514.91.2273.548.7.0.16.90.131.60.703.47.50.20
K43,25336,94419,8122,7841,16283832495,2309,1326,97428,3931,162
Sr1,1501,2305,93718,97510,723>10,0006,1762,12013,981>10,000>10,0008,377>10,000
P96082978618,9404364,53911,3033936,5024,71311,82610,89131,091
Hf4.142.440.194.51.000.210.30.24.00.501.010.600.20
Zr1701007.817130.42139363131728156
Ti17,14617,38611,510480601201,499602,6383005,27671960
Y54449024.110.7312711993.534275628
REE
La5063514133981547292,000326643388398485398
Ce1,0836577518603751,6603,0007271,2007507841,060742
Pr131799195.746.01891,00085.412181.185.712376.2
Nd320225324362.7181.65692,000273422.5269224329189
Sm50.635.150.164.925.7586.353746.850.7632.932.54827.3
Eu12.57.7415.5011.486.3123.112111.512.18.748.2211.77.13
Gd35.1624.3934.8134.0511.3653.827726.235.8821.821.332.818.7
Tb4.602.814.532.601.084.624.32.34.662.32.03.21.8
Dy22.0013.4421.678.263.3414.476.77.021.878.97.313.57.2
Ho3.392.073.340.920.311.69.80.83.351.41.02.21.0
Er6.684.408.551.260.582.622.71.57.493.42.45.52.5
Tm0.790.521.010.150.08<0.05<0.05<0.060.930.410.260.680.29
Yb3.722.464.780.890.450.75.20.55.292.01.23.51.4
Lu0–470.260.740.100.060.040.050.040.720.250.120.430.16
Mol%
CaO28.732.232.445.754.147.116.41.478.288.986.865.698.2
FeO + MnO18.517.116.514.37.13.214.72.114.82.6.7.011.90.4
MgO52.850.751.140.038.849.768.996.57.07.56.522.51.4

na = not available.

Table 1C

Carbonatites with associated intrusive melilitic rock types, as Tapira and Lages. References: Tapira [54,62] and Lages [30]

Sample Tapira age: 70 (9) MaLages age: 82 (6) Ma
T 1T 2TPTAPSSB05ASB02
Wt%
SiO20.700.021.162.531.46
TiO20.330.050.100.05 0.04
Al2O30.200.070.060.870.83
FeO10.130.123.9610.2817.74
MnO0.170.060.111.062.39
MgO6.353.852.4414.1612.72
CaO38.4851.0050.7834.2729.41
Na2O0.040.020.090.020.02
K2O0.120.130.110.260.20
P2O50.050.104.250.030.04
L.O.I.45.1444.5637.0035.3333.16
Sum101.7199.99100.0698.8698.01
IE
ppm
Rb7.40.12.36.13.5
Ba2,36011,6001,97195113,528
Th5.730.684373.55.0
Nb6.142.029978.98.4
Ta1.400.531051.52.0
K9961,0799132,1591,660
Sr12,2009,57013,3642,9838,057
P24848621,097131175
Hf2.70.503.60.30.1
Zr11018.41127.714.3
Ti1,978399600300240
Y17.011.07418.845.5
REE
La90.262.247241.22,569
Ce112901,10490.35,236
Pr12.338.3212212.24551
Nd47.031.747747.542,184
Sm7.114.6862.59.43376
Eu1.561.2515.92.5380.1
Gd2.741.7145.57.91225
Tb0.550.334.281.3516.92
Dy2.721.6318.07.6756.91
Ho0.540.332.621.3918.92
Er1.851.085.413.1722.45
Tm0.170.060.670.568.29
Yb1.370.533.733.098.72
Lu0.130.060.490.440.86
Mol%
CaO69.590.288.554.550.4
FeO + MnO14.50.35.514.119.3
MgO16.09.56.031.430.3
Table 2

Hydrothermal carbonatites

Sample Barra do Itapirapuã age: 115 (10) Ma
I.A; I.B; II.AIV.A 3IV.B 5IV B 3II A 2IV A 5
wt%
SiO20.54 (0.37)1.4612.765.212.276.67
TiO20.01 (0.00)0.510.490.150.010.01
Al2O30.02 (0.01)0.221.201.690.231.83
FeO7.76 (1.32)7.645.801.3614.4812.28
MnO1.08 (0.16)0.940.300.081.911.19
68MgO15.23 (1.15)15.0614.822.6410.5510.51
CaO30.54 (1.18)28.9927.6451.5631.4927.23
Na2O0.08 (0.01)0.090.030.420.080.06
K2O0.02 (0.01)0.010.011.030.031.48
P2O51.27 (0.14)0.592.110.150.220.10
L.O.I.42.30 (2.20)43.3334.1935.5637.1137.26
Sum98.8598.8499.3599.8598.3898.62
ppm
Rb1.9 (0.6)3.02.9683.55.147.2
Ba1,252 (29)1,7301,828145.71,927456
Th122.5 (25.0)64.51857.9246114
Nb165 (48)38.14.348721
Ta1.5 (0.4)1.90.70.841.5
Sr1,743 (382)1,1503,0167822,9552,052
Hf0.51 (0.02)0.53.10.91.00.3
Zr145 (32)88.427.510.419.27.0
Y20.1 (1.4)43.5291.845.6764.3
La150 (45)73463335.441,070294
Ce347 (65)92393547.711,397457
Pr46 (14)78.41106.5718451
Nd123 (12)20838329.74826167
Sm25.4 (14.0)24.2058.746.3611716.67
Eu8.25 (2.92)6.7922.461.8130.24.02
Gd27.00 (10.2)18.077.377.8891.38.47
Tb4.15 (2.05)2.1014.101.3911.70.87
Dy25.2 (11.7)10.9084.036.8037.44.06
Ho3.46 (2.68)1.9217.231.403.720.86
Er4.22 (2.23)4.7144.204.0412.53.15
Tm0.78 (0.25)0.646.500.671.750.42
Yb6.74 (4.16)3.0438.854.4610.12.98
Lu0.97 (0.53)0.535.630.701.380.48
Mol%
CaO52.151.262.591.553.452.0
FeO + MnO11.811.810.82.021.720.1
MgO36.137.026.76.524.927.9
Sample Cerro Chiriguelo age: 128 (5) MaCerro Manomó age: 139 (3) Ma
3,4113,4143,4223,4343,4403,443PV-69C
wt%
SiO22.265.445.057.1810.556.253.02
TiO20.050.050.010.103.410.300.02
Al2O30.220.250.300.561.440.530.11
FeO3.252.843.192.9915.200.4040.49
MnO0.600.450.280.150.640.407.13
MgO0.100.150.410.502.801.001.34
CaO48.4547.1547.0046.9830.8944.627.68
Na2O0.080.080.030.040.030.100.08
K2O0.070.150.280.501.610.420.02
P2O50.800.950.690.480.541.200.10
L.O.I.40.9940.0738.2938.0531.9439.0835.28
Sum96.8797.5995.5397.5399.0597.1595.27
ppm
Rb24323936151590.1
Ba25,88523,98922,12310,3905,46419,5321,560
Th4029.71128812481
Nb1098117810026049525
Ta13.57.62037.60.29
K5811,2452,3254,15113,3663,487166
Sr2,8752,0315,2437,4411,7767,1032,342
P3,9714,7163,4252,3832,6815,957496
Hf5.110.011.60.19
Zr133872194305063915
Ti3003006060020,4421,799120
Y43.93.710295.049
REE
La1,3361,2571,1695903128892,570
Ce1,3051,2401,1026332271,0225,328
Pr12012810163.122.679787
Nd1511811781201101512,142
Sm9431.530.020.11229.2369
Eu3210.810.26.94.19.879
Gd10134.132.421.813.029.9221
Tb16.35.55.203.62.14.813
Dy9632.831.021.228.960
Ho18.36.095.874.065.6610
Er4414.714.29.914.524
Tm5.31.771.711.230.841.803
Yb17.18.688.046.034.429.029
Lu3.31.130.770.680.451.021
Mol%
CaO93.594.493.593.765.590.416.4
FeO + MnO6.25.25.44.926.26.879.6
MgO0.30.41.11.48.32.84.0

References: Barra do Itapirapuã [28,71], Cerro Chiriguelo [21], and Cerro Manomó [52]. Values for Barra do Itapirapuã I.A, I.B, II.A are averaged, with standard deviations in parentheses.

Table 3

Occurrences with unusual geometric relationships

SampleItanhaém Age:129 (5) MaValle-mí Age: 138.7 (0.2) MaCerro Cañada Age: 124.6 (0.7) MaCerro E Santa Elena Age: 127 (8)
IA-2VM1 Carbonate Fraction (15.56 wt%)Dolomite Fraction (15.5 wt%) In ijolite
wt%
SiO25.580.29
TiO20.920.050.010.02
Al2O31.840.010.89
FeO11.790.292.251.63
MnO0.620.010.200.45
MgO6.230.2018.2016.23
CaO36.066.6731.3032.54
Na2O0.370.010.250.40
K2O0.180.010.010.02
P2O54.640.080.010.44
L.O.I.30.708.1347.7946.92
Sum98.9115.56100.02100.00
ppm
Rb0.80.902.364.5
Ba1,5464352,9505,618
Th233202.824.23
Nb4486410.315.0
Ta24.44.81.111.32
K1,4948381166
Sr3,2481283,2466,225
P20,249349411,920
Hf0.8101.051.71
Zr17.0391218.8
Ti5,51530059118
Y5716.024.225.5
REE
La2,773155164188
Ce4,902340325409
Pr33743.536.530.2
Nd1,181168146.3184
Sm13227.722.4525.8
Eu29.710.668.214.4
Gd7933.1231.448.2
Tb6.45.243.35.1
Dy3730.030.547.1
Ho7.25.955.78.9
Er14.812.2713.621.8
Tm1.611.342.12.7
Yb11.75.9521.731.1
Lu0.900.670.771.22
Mol%
CaO66.292.853.549.9
FeO + MnO17.83.33.33.6
MgO16.03.943.246.5

References: Itanhaém [34], Valle-mí [37], and Cerro Cañada and Cerro E Santa Elena [11,12].

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    Distribution of the tholeiitic magmatism in the Paraná Province (South American Platform, Western Gondwana) and location of the main alkaline–carbonatitic regions in a reconstruction corresponding to 110 Ma (after refs. [39,51] and Figure 1.11 of ref. [14]), where all the single alkaline outcrops are represented. ASU, Central-Eastern Paraguay magmatic province [38]. Inset: Main lineaments in the Paraná-Etendeka System (South American and African plates, Western Gondwana) at about 110 Ma; modified after refs. [40,52] corresponding to the main lineaments of the alkaline and alkaline–carbonatitic complexes (cf. Figures 2–4 of Ref. [53]). APC, Araguaia-Paranaìba-Cabo Friom; M, Mocâmedes Arch; PGA, Ponta Grossa Arch; RP, Rio Piquirì; TS, Torres Syncline; DB, Damara Belt; RGA, Rio Grande Arch.

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    (I) Classification of carbonatitic associations (oxides are expressed in molar proportions, after Refs. [60,61] for the various complexes from the Brazilian Platform [31,62]). (a) Brazilian Early Cretaceous: Anitápolis, Ipanema, Itapirapuã, Jacupiranga, and Juquiá; it also includes the Early Cretaceous Paraguayan occurrences of Cerro Sarambí and Sapucai as shown in the figure IB. (b) Late Cretaceous: Caiapó, Morro do Engenho, Santo Antônio da Barra, and Mato Preto [31,62]. The full list of references is also reported in Table 1A of the Appendix. (II) Quaternary diagram showing compositional trends of exsolved carbonate liquids from a residual silicate magma [63]. The curves of 2 kb and 5 kb are theoretical isobaric-polythermal solvi [27], and the symbols are selected samples from the Appendix. Mineral abbreviations: Cpx, clinopyroxene; Mel, melilite; Ol, olivine; Ne, nepheline. (III) Classification of group B of Brazilian Late Cretaceous carbonatitic associations (Salitre, Serra Negra, Araxá, Catalão I, and Catalão II; cf. Table 1B of the Appendix).

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    (IV) Classification of group C Brazilian Late Cretaceous carbonatitic associations (Tapira and Lages). Oxides are expressed as molar proportion (cf. Figure 2, and Table 1C of the Appendix). (V) Classification of the Early Cretaceous hydrothermal carbonatitic association of Barra do Itapirapuã in Brazil [28,71]. Oxides are expressed as molar proportion (cf. Table 2 of the Appendix). The plot also includes data for the complexes of Cerro Chiriguelo [21,41] and Cerro Manomó. (VI) Classification (occurrences with unusual geometric relationships) of the Early Cretaceous carbonatitic rocks from Itanhaém (129 Ma, [58]), Valle-mí (138 Ma; [37] and references therein), and Cerro Cañada and Cerro E Santa Elena (124 and 127 Ma, respectively [1,12]).

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    Mineral association representative of an ocellus in ijolite from the Cerro E Santa Elena alkaline complex (127 ± 8 Ma), Central Eastern Paraguay; modified after refs. [11,12]. Am, amphibole; Bi-Phl, biotite-phlogopite; Cpx, clinopyroxene; Dol, dolomite; Mt, magnetite; Ol, olivine (cf. Figure 3-VI).

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    IE concentrations normalized to primitive mantle [73] for magmatic group A (cf. Figure 2) Early Cretaceous and Late Cretaceous carbonatites from Southern Brazil and Eastern Paraguay. Data sources in Appendix; Early Cretaceous: Anitápolis, [30]; Itapirapuã, [74]; Jacupiranga, [18,20,25,26,27,75]; Ipanema, [35]; Juquiá, [22,27]; Late Cretaceous: Mato Preto, [29]; Caiapó and Morro do Engenho, [46]; Santo Antônio da Barra, [6,8]. Ca, calciocarbonatite; Fe, ferruginous calciocarbonatite; Mg, magnesiocarbonatite.

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    IE normalized to primitive mantle concentrations [73] for magmatic group B Late Cretaceous carbonatites from Southern Brazil. Data sources: Appendix. Salitre, [64,65]; Serra Negra, [66]; Catalão I, [68]; Catalão II, [69]; Araxá, [67]. Magmatic group C Late Cretaceous carbonatites from Southern Brazil (cf. Appendix): Tapira, [54]; Lages, [30,55,76]. Ca, Mg, and Fe: calciocarbonatite, ferrocarbonatite, and ferruginous calciocarbonatite.

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    Evolutionary path of La/Yb ratio versus La, as determined for the Rio Apa dykes [37].

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    IE normalized to primitive mantle concentrations [73] for Early Cretaceous hydrothermal carbonatites. Data sources: Barra do Itapirapuã, [28,71]; Cerro Chiriguelo, [21]; Cerro Manomó, [52]. Ca, calciocarbonatite; Fe, ferruginous carbonatite; Mg, magnesiocarbonatite.

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    IE normalized to primitive mantle concentrations [73] for early cretaceous carbonatites occurrences with unusual geometric relationships. Sources of data: Itanhaém [58,87], Valle-mí [41], and Cerro Cañada and Cerro E Santa Elena [59].

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    Spidergrams of REE normalized to chondritic contents [90] for selected Early and Late Cretaceous carbonatites (modified after ref. [31] cf. also Figures 5–9).