Geoderma 126 (2005) 225 239 www.elsevier.

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Lateritic crusts and related soils in eastern Brazilian Amazonia

A.M.C. Horbea,*, M.L. da Costab
a

Universidade Federal do Amazonas, Departamento de Geocie ncias, Av. Gal. Rodrigo O.J. Ramos, 3000, Coroado, 69077-000, Manaus, Amazonas, Brazil b Universidade Federal do Para , Centro de Geocie ncias, Campus Universita rio do Guama , 66075-110, Bele m, Para , Brazil Received 24 January 2003; received in revised form 16 September 2004; accepted 23 September 2004 Available online 27 October 2004

Abstract The upland soils of Caraja s and Paragominas in eastern Brazilian Amazonia are made up of yellow to reddish earthy-clayey to clayey materials, which cover ironaluminum, aluminumiron and aluminum lateritic crusts. These materials are closely related to each other and to lateritic evolution and are comprised by three horizons described from the base to the top as lower, intermediary and upper horizons that are identified by the type, amount and size of the lateritc fragments embedded into a matrix that increases towards the top. The three horizons show a strong lithological vertical transition into themselves and the degradation degree increases toward the top of the profiles where the main characteristics are the same geochemical signatures between the horizons of every profile, and the change in the mineralogical composition from hematite+gibbsite to gibbsite+Algoethite in the N5 and IB, and from gibbsite to kaolinite+quartz in Paragominas. These transformations support a lateritic crust chemical reworking, which allows for its transformation into a friable and soft in situ matrix and then into soil in a progressively weathering process, which started in Amazonia probably in the Miocene, after the formation and exposure of the main lateritic crusts to landsurface. D 2004 Elsevier B.V. All rights reserved.
Keywords: Trace elements; REE; Degradation process; Weathering

1. Introduction Three main soils occur in the Amazon region as Spodosols, Ultisols and Oxisols (Radambrasil, 1970). The first one is essentially sandy as it is characterized by quartz accumulation instead of clay minerals,
* Corresponding author. E-mail addresses: ahorbe@ufam.edu.br (A.M.C. Horbe)8 mlc@ufpa.br (M.L. da Costa). 0016-7061/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.geoderma.2004.09.011

especially kaolinite that is the main mineral of Amazonian Oxisol. The second one is a transition between the other two. The Oxisols consist of yellowish to reddish clayey materials and occur in the uplands, on the summit of plateaux. In the well-preserved lateritic profiles, these soils cover Fe, FeAl, Al, AlFe and SiFe crusts or saprolites and mottled horizons with stone line in the truncated profile. The relation of Oxisols with lateritic profiles was first reported in Brazilian Amazonia by

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Sombroek (1966), who stated that they were sedimentary material deposited on a big Amazonian lake and called them Belterra Clay on account of their homogeneous texture with no visible stratification and for being basically made up of kaolinite. Later, other authors suggested that these Oxisols were the result of mud deposited in areas of lower relief (Grubb, 1979; Truckenbrodt and Kotschoubey, 1981; Hieronymus et al., 1989; Truckenbrodt et al., 1991) or were intensively leached quaternary sediments (Dennen and Norton, 1977; Aleva, 1981; Kronberg et al., 1982) or the product of the lateritic crust in situ chemical degradation (Wolf and Silva, 1973; Boulange and Carvalho, 1989, 1997; Lucas et al., 1989; Nahon et al., 1989; Costa, 1991a,b; Costa et al., 1997). The in situ degradation is suggested by Leprun (1979), Thomas (1994) and Beauvais and Tardy (1993) for lateritic crust. The purpose of this study is providing more thorough mineralogical and geochemical data, which reinforce the strong relation between lateritic crust and Oxysol in the Amazonian region. A better understanding of this relationship is very important for the studies of the geological, geomorphological and pedological evolution of this region as far back as the Tertiary as well as for providing new insights on the soil formation and fertility in the Amazon tropical

rain forest. Two important lateritic regions covered with Oxisols, are chosen to carry out this study: Caraja s and Paragominas (Fig. 1). In these two regions, the lateritic profiles were developed during the lower Tertiary, forming FeAl lateritic crusts (Caraja s) and Al and AlFe lateritic crusts (Paragominas) (Truckenbrodt and Kotschoubey, 1981; Costa, 1991a,b; Vasconcelos et al., 1996; Ruffet et al., 1996; Costa, 1997). These two regions are very important ore producers in the Amazon region: on account of huge iron ore and bauxite deposits, respectively.

2. Study area, materials and analytical techniques The relief of the Caraja s region comprises several plateaus with altitude varying from 600 to 900 m cut with V-shaped valleys. The vegetation is a rain forest, with non-forested areas on the top of the plateau in consequence of lateritic crust outcrops. The climate is tropical with a mean annual temperature of 26 8C and a mean annual rainfall of 1600 mm. The rainy season increases from December to April. In this region five profiles in the top of the plateaux were selected to avoid colluvial material, all of them with FeAl lateritic crust developed from diabaseN5 (two

Fig. 1. Geographic location of the profiles studied in the Caraja s and Paragominas regions, Para , Brazil (1=profile with Al crustCamoa Mine, 2=profile with AlFe crust).

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227

profiles)- and over gold-bearing gossans with metavulcanic rocks with CuAusulphide mineralizationIgarape Bahia (IB, three profiles) (Lemos, 1982; Costa, 1991b). In the second region, Paragominas, the vegetation is predominantly forest that is currently intensively deforested. The relief is formed by a large plateau, 50180 m high composed of bauxite and caolin, cut with U-shaped valleys. The temperature is almost the same as in the Caraja s region but with a higher mean annual rainfall (2000 mm) and a rainy season extending from December to May. Two profiles are chosen also on the top of the plateaux, the first located in the Camoa Bauxite Mine (with Al lateritic crust) and the second along the Bele m-Bras lia highway, 53 km south of Paragominas (with AlFe lateritic crust) (Fig. 1). These complete lateritic profiles developed over Cretaceous arkoseous sandstones, pelites and mudstones parent rock (Itapecuru Formation) show nearly the same general physical characteristics. Representative samples from the base of lateritic crusts to the top of the Oxisols were collected. Two kinds of materials are identified: (a) a finer material (b0.2 cm in diameter)the soft matrix; (b) a coarser material (0.23 cm in diameter)the fragments. These fragments coming from the lateritic crusts, some being homogeneous (nodules) and others composed of pisoliths and nodules embedded in an indurated matrix. Fifty-one samples of crust, fragment crust and matrix were analyzed. The minerals were identified by X-ray diffraction (XRD) supplemented by electron microscope (EDAX XL-40 Phillips) analyses. The chemical analyses of the main elements were carried out in metaborate melt dissolved into triacid solution and analysed by

gravimetry (SiO2 and LOI), volumetry (Al2O3) and colorimetry (Fe2O3 and TiO2). The trace elements were analysed by optical spectrography (V, Cr, B, Mo, Zr, Ga, Y and Sc), AAS (Ni, Pb, Mn and Cu) and inductively coupled plasma (REE). An electron microprobe (Cameca SX-50) was used for chemical microanalyses. The mineralogical contents were obtained by conversion of the bulk chemical analyses in a weathering norm for the mineral identified by XRD analysis according to the process developed by Voicu et al. (1997). The goethite aluminum content was calculated by the Schulzes (1984) method using the c crystallographic parameter estimated according to the XRD analysis of (111) and (110) goethite reflections, which were displaced by the increasing Al contents. Two equations were used: c =((1/d 2(111))(1/d 2(110))1/2) and mol% AlOOH=1730572c .

3. The Caraja s region profiles (with FeAl lateritic crust) The five profiles at N5 (bauxite deposit) and IB (Igarape Bahia CuAu Mine) show three differentiated horizons, which correspond to a progressively upward physical and chemical degradation from iron lateritic crust to clayey to earthy soils in the profile (Fig. 2): 1. Lower horizon: indurated and massive ironaluminum lateritic crust. In the IB profiles fragments of gossans and metavolcanic rocks occur inside the lateritic crust, they are relicts of the parent-rock from which it was formed. Red earthy-clayey or

Fig. 2. Sketch of the profile and of the three facies of the lateritic crust.

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clayey matrix occurred in the veinlets and fractures between the blocks. 2. Intermediate horizon: with centimeter-sized, irregular to round shaped fragments (lateritic crust, and gossan and metavolcanic relicts) similar to those found on the lower horizons, embedded in a red earthy-clayey to clayey soft matrix. 3. Upper horizonthe soil: red earthy-clayey to clayey soft matrix with small nodules (b0.5 cm in diameter). The thickness of these horizons at N5 changes from 0.7 to 1.3 m in the lower, 0.5 to 0.8 m in the intermediate and 0.3 to 0.5 m in the upper horizon. At IB, the whole profile reaches 10 m (0.51.0 m in the lower, almost 6 m in the intermediate and 0.33 m in the upper horizon). The ironaluminum lateritic crust of the lower horizon shows three facies, called A, B and C (from

bottom to top). At N5, the A facies is massive and homogeneous without geometric elements, with a brown color and cut by veinlets filled with yellow to red soft matrix (Fig. 2). The B facies is characterized by pisoliths and nodules (12 cm in diameter), partially coalescent, embedded in an indurated yellow to red matrix. The pisoliths exhibit a brown aureole and a red to yellow nucleus, while the nodules have homogeneous textures with brown to red colors. The C facies, which was found only in N5, is composed by isolated nodules (0.20.5 cm in diameter) embedded in an indurated gibbsitic yellow matrix. The gossan and metavolcanic fragments are found in the lateritic crust, at IB. 3.1. Mineralogical composition The minerals of the N5 and IB profiles are hematite, goethite, kaolinite and gibbsite, with lower

Table 1 Mineralogical composition of the N5 and IB profiles (n=number of samples, s=standard deviation) N5 profile Horizon/n Quartz s Kaolinite 20 s 15 Gibbsite 41 s 14 Goethite 31 s 0.6 Hematite 4 s 0.6 Anatase 4 s 0 Upper horizon (soil) Matrix/3 Intermediary horizon Matrix/2 15 Fragment/2 Lower horizon FA/1 FB/2 FC/1 IB profile Upper horizon (soil) Matrix/3 7 Intermediary horizon Matrix/3 2 Metavolcanic/3 4 Gossan/2 Lower horizon Matrix/1 Metavolcanic/1 Gossan/1 FB/1 FA/1 6.1 16 15.8 33 8.7 36 4.7 5 3.2 4 1.2

13 32

8.5 3

39.5 8

9.2 4

21.5 20.5

4.9 20.5

7.5 37

0.7 14

3 1.5

1.4 0.7

43 35 32

0.7

2 1.5 26

0.7

22 40 15

30 19 23

7.1

2 4 2

2.9 6.4

29 23 5

10.4 17.5 1.4

22 43 2

7.8 21.4 1.4

36 44 46

5.1 4.0 14.1

5 13 46.5

6.7 10.6 14.8

4 3 1

0.6 1.5 0

25 21 5 6 32

26 18 4 1 10

22 41 22 48 3

20 17 68 43 53

3 2 1 1 1

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amounts of quartz and anatase. The main differences between crusts+fragments and matrix+soil is the higher content in hematite in the former and gibbsite in the latter although the kaolinite content decreases in N5 while quartz increases in IB toward the upper horizon (Table. 1). The other minerals display a variable amount. The increasing of gibbsite toward the matrix and consequently toward the soil in the Caraja s profiles is also evident when comparing the nucleus and the aureoles of the pisoliths and nodules. The nodules and nucleous of the pisoliths are homogeneous and constituted mainly by hematite while the edges are discontinuous with gibbsite in some of the dissolution cavities. The indurated yellow to red matrix, in which the nodules and pisoliths are embedded, is made of crypto to microcrystalline gibbsite and kaolinitic materials. The gossan relicts are massive, gray, with metallic luster and composed of hematite and goethite. Fractures and cavities are filled by gibbsite, kaolinite and goethite. In the upper horizon these fragments, with less than 0.5 cm in diameter, are irregular and show corroded features and thick aureole indicating dissolution process. The metavolcanic relicts are purple to red, sometimes with a nodular texture, and

composed of kaolinite, gibbsite, hematite and goethite. Gibbsite also occurs in the dissolution cavities and veinlets. These changes in the characteristics of the relicts are probably associated with the same process that modified the mineralogical composition of the lateritic crust neoforming soil. In goethite aluminum contents, estimated by the method of Schulze (1984), varies from 4 mol% in the gossan to 12 mol% AlOOH in most of the studied lateritic crust. On the other hand, in the goethite of the matrix there is an aluminum content reaching 3134% mol AlOOH, corroborating the increasing amount of gibbsite toward the top of the profiles and suggesting Al-goethite neoformation. 3.2. Chemical composition 3.2.1. Major elements The lateritic crust and its fragments at N5 and IB show large amounts of Fe2O3, while Al2O3 and LOI increase in the soft matrix of these fragments and in the soil (Fig. 3). The amount of SiO2 is variable in the profiles (from 1% to 24%) and TiO2 is less than 3%. Al2O3 and LOI increased from facies A to C, while Fe2O3 decreased. The profile of IB is characterized by

Fig. 3. Average bulk chemical composition of the Caraja s profiles.

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higher iron content in the whole profile as a consequence of the presence of gossan fragments, while N5 has a little more Al2O3 (Fig. 3). The gossan relicts maintain almost the same chemical composition throughout the profile, with high contents of Fe2O3. However, the metavolcanic relicts change from more ferruginous in the lower horizon to more aluminous in the intermediate horizon (Fig. 3). Microprobe analysis show higher Fe2O3 contents in the nucleus of the nodules than in the outer aureole, while SiO2 and Al2O3 increase toward the matrix of the crust fragments (Fig. 4), showing a gradual chemical transition between these two materials which is similar to that observed between the crust and the matrix. This trend from Fe2O3 and Al2O3 reflects the mineralogical transformation and represents the influ-

ences of weathering processes over the N5 and IB lateritic crust forming the soil. 3.2.2. Trace- and rare-earth elements (REE) The N5 horizons show higher content of V, Cr, Zr and Mn than that of the other analyzed trace elements and display a similar geochemical distribution pattern in every horizon along the profiles (Fig. 5). On the other hand, in IB horizons, the trace element pattern distribution shows higher variability than that at N5 in consequence of the different geochemical characteristics of the gossan and metavolcanic relicts found in the lateritic crust. The gossan relicts can be distinguished by the lower contents of B and Ga than that of the other trace elements, and by the slight increase of B, Pb and Au contents, from the relicts of the lateritic crust to those found in the intermediary

Fig. 4. Chemical composition of the nodules and plasma of the fragments of the Caraja s and Paragominas profiles (oSiO2, 5Al2O3, D Fe2O3, Pyellow matrix, RPred matrix, Bedges of the nodule, Iinner of the nodule, PNpink nodule, INiron nodule).

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Fig. 5. Average trace elements concentration of the Caraja s profiles (Hg in ppb).

231

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Table 2 REE contents in the N5 profile in ppm La Upper horizon Matrix (soil) 10.94 Intermediary horizon Matrix 27.40 Fragment 21.40 Lower horizon C facies 12.05 A facies 20.86 Ce 22.36 Nd 7.07 Sm 1.18 Eu 0.31 Gd 1.28 Dy 1.97 Ho 0.47 Er 1.70 Yb 2.04 Lu 0.31 LREE 41.86 HREE 7.77 REE 49.63

43.43 31.24

18.67 16.05

2.74 1.47

0.46 0.25

2.02 1.06

2.04 1.32

0.42 0.29

1.19 0.94

1.15 1.02

0.14 0.13

92.70 70.41

6.96 4.76

99.66 75.17

19.50 21.92

5.85 7.99

1.05 0.95

0.23 0.26

1.14 0.84

1.74 1.30

0.43 0.32

1.59 1.20

2.01 1.44

0.33 0.23

130.92 51.98

7.24 5.33

138.16 57.31

horizon (Fig. 5). The metavolcanic relicts that are also found inside the iron crust have higher Au contents than that of the gossan relicts and V, B, Mo, Y, Sc and Cu diminish toward the intermediary horizon of the profiles. Trace element contents in the A and B facies show intermediate contents between the gossan and metavolcanic relicts, except for Y, which has a lower content in these facies. The matrix and the soil are geochemically more similar to the metavolcanic relicts in trace element contents (Fig. 5) probably on account of these being representative of the main parent-rock lateritic crust of IB and still being present in larger quantity than the gossan relicts. In both profiles, the LREE, especially La, Ce and Nd are more abundant than HREE, especially in IB profile (Tables 2 and 3). Chondrite-normalized REE plots showed a similar slope pattern in the horizons of either profile with enrichment in LREE; nevertheless, the lateritic material shows lower LREE fractionation
Table 3 REE contents of the IB in ppm La Upper horizon Matrix (soil) 68.56 39.71 45.75 Ce 57.39 54.66 63.60 Nd 33.99 25.70 23.20 Sm 4.39 2.40 2.39 Eu 0.90 0.67 0.59 Gd 2.84 2.40 1.74

(9.813.81) than gossan and metavolcanic relicts (21.627.2), indicating their leaching, but no matrix and soil enrichment. A weak negative Eu anomaly is outlined in N5 (Fig. 6). These elements are probably associated with residual REE minerals as they do not have structural capacity to be captured by the hematite and goethite. In the progressive lateritic crust chemical degradation of N5 and IB, that also affects the gossan and metavolcanic relicts, most chemical elements do not show a clear differentiation from these materials to the matrix and soil. This probably occurs because only hematite decreases toward the matrix and soils, where gibbsite is the main mineral, which has low capacity to adsorb trace elements and REE. Although Algoethite is probably neoformed it might present almost the same content of the former elements as compared with the hematite of the crust. The absence of a clear mineralogical transformation upward the

Dy 3.24 3.23 1.92

Ho 0.74 0.70 0.39

Er 2.46 2.35 1.08

Yb 2.57 2.48 1.17

Lu 0.38 0.37 0.17

LREE 165.23 123.14 135.63

HREE 12.23 11.53 6.47

REE 177.46 134.67 142.10

Intermediary horizon Matrix 91.46 Gossan 449.30 Metapelite 304.40 Lower horizon A facies

96.87 300.20 235.10

26.56 111.80 67.55

3.70 13.07 7.04

0.85 2.34 1.38

2.98 6.50 3.76

3.52 4.89 2.83

0.77 1.07 0.62

2.42 3.35 1.93

2.38 3.34 2.04

0.33 0.49 0.33

219.44 876.71 615.47

12.40 19.64 11.51

231.84 896.35 626.98

44.66

56.03

21.50

2.04

0.50

1.65

2.37

0.52

1.41

1.19

0.18

124.73

7.32

132.05

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ranges from 2.0 m in the Al lateritic crust profile to 13.8 m in the other one. The Al lateritic crust of the lower horizon is approximately 3.6 m thick, pink to yellow, indurated and massive to porous with veinlets filled with yellow matrix. In the intermediate horizon, the fragments (3 cm in diameter) are concretionary, composed of pink to reddish ferruginous brown nodules embedded into a yellow indurate matrix (Fig. 2). The color intensity decreased from the nucleus to the periphery of the nodules showing a bleaching process. The lateritic crust of this profile is similar to that of the A facies while the concretionary fragment is similar to that in the C facies of Caraja s profiles. The lower horizon (1.0 m thick) of the AlFe lateritic profile is pink to reddish, with abundant brown to red ferruginisation portions. In the intermediate horizon there are two kinds of fragments: (1) isolated ferruginous nodules, with a maximum diameter of 2 cm; (2) concretionary fragments with maximum diameter of 5 cm and composed of brown to reddish and pinkish nodules embedded into a yellow indurate plasma correlated to the C facies of the other profiles. The color intensity of the nodules decreases from the nucleus toward the periphery. 4.1. Mineral composition
Fig. 6. Chondrite-normalized REE plots of the studied profiles (o matrix, 5lateritic fragment, Da facies, w C facies, * metavolcanic fragment/lateritic fragment of the Al profile, X gossan fragment).

profiles, probably being consequence of a weak weathering process, does not permit the total rearrangement of the elements as shown on the lateritic profiles with well developed horizons (Boulange and Carvalho, 1989, 1997; Lucas et al., 1989; Nahon et al., 1989; Truckenbrodt et al., 1991; Beauvais and Colin, 1993).

4. The Paragominas region profiles (with Al and AlFe lateritic crusts) The succession of the horizons in this area is similar to that of the Caraja s region (Fig. 2). The main difference is the thickness of the upper horizon that

The minerals of the Paragominas profiles are the same as those of N5 and IB but gibbsite is the main mineral in the crust and in their fragments, while kaolinite and quartz are more abundant in the matrix and soils (Table 1). Hematite and goethite show the lowest contents in the Al profile (Table 4). In the pink portion of the Al-lateritic crust and in the pink nodules of the concretionary fragments of this profile, gibbsite is cryptocrystalline with microcrystalline crystals on the walls of the voids, while the yellow indurated plasma is purely cryptocrystalline (Fig. 7a,b). Some of the gibbsite crystals show irregular edges (Fig. 7c) that are probably the result of chemical corrosion. The kaolinite crystals of the matrix in the upper part of the profile have less than 0.5 A in diameter (Fig. 7d), in contrast to that found in the crust or even in the saprolite, with bigger crystal forming stacks or bbooksQ (Fig. 7e). The decrease in the crystal size suggests its fragmentation but the crystal voids (Fig. 7f) also indicate dissolu-

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Table 4 Mineralogical composition of the AlFe and Al profiles (n=number of samples, s=standard deviation) Al profile Horizon/n Quartz s 0.7 Kaolinite 72.5 s 0.7 Gibbsite 13 s 1.4 Goethite+Hematite 3 s 0 Anatase 1.5 s 0.7 Upper horizon (soil) Matrix/2 9.5 Intermediary horizon Matrix/2 Fragment/1 5 Lower horizon Lateritic crust/2 AlFe profile Horizons/n Quartz s 10.8 Kaolinite 66 s 18.1 Gibbsite 15 s 11.5 Hematite+Goethite 9 s 0.5 Anatase 1 s 0.3

82.5 13

3.5

11 79

1.4

3.5 1

0.7

2.0 1

1.4

22.5

13.4

71

9.9

2.8

1.5

0.7

Upper horizon (soil) Matrix/5 8 Intermediary horizon Matrix/5 Fragmen/3 Lower horizon Lateritic crust/4

64 19

6.4 8.5

18 51

4.1 37.5

16 25.5

6.6 27.6

1 2.5

0.4 0.7

3.5

1.8

18

9.0

36

57.7

36

27.0

0.5

1.7

tion of the kaolinite and probable precipitation. Thus, the kaolinite increasing content toward the top of the profiles may be consequence of relicts portions as well as neoformation. Corrosion borders and dissolution cavities plus gibbsite and kaolinite size decreasing up the profile are indicative of mineralogical transformations. 4.2. Chemical composition 4.2.1. Major elements The lateritic crusts (the lower horizon) are characterized by high contents of Al2O3 and LOI related to gibbsite, while the matrix of the crust fragments and the soil has similar SiO2 and Al2O3 contents, due to the presence of kaolinite, quartz as well as gibbsite. The ferruginous fragments of the AlFe lateritic crust bring about an increase of iron in the matrix of this profile (Fig. 8). This chemical composition is different from that of the Caraja s region. The electron microprobe analysis show that Al2O3 decreases from 65%, which represents 100% of the gibbsite in the Al crust pink nodule concretionary

fragments, to 46% and 60% in the yellow indurated matrix showing the coexistence of kaolinite and gibbsite with the increase of SiO2 (Fig. 4). These chemical compositions and the cryptocrystalline texture of the yellow indurated matrix support the mineralogical data and suggest that this material represents the transition from the gibbsitic pink portion to the matrix, as Bardossy and Aleva (1990) and Lucas et al. (1989) reported in similar profiles. 4.2.2. Trace elements and REE The trace elements content of Paragominas profiles is lower than that of N5 and IB profiles, probably due to the sedimentary parent-rock composition (conglomeratic sandstones and pelitic rocks) and the scarcity of hematite and goethite in this lateritic environment, which are the main element-catching minerals. The Paragominas horizons show higher contents of Zr and Pb and lower of Mo and Cu as compared with the other trace elements (Fig. 9). This pattern reminds the same along the horizons in both weathering profiles. Only Mn and Cu show a slighter increase up the Al profile.

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235

Fig. 7. SEM analysis of the fragments in the Paragominas profiles (a=microcrystalline gibbsite of the Al-crust; b=cryptocrystalline gibbsite of the yellow endurated plasma of the concretionary fragments of the Al crust; c=corroded borders of the microcrystalline gibbsite; d=cryptocrystalline kaolinite of the matrix in the upper horizon; e=kaolinite crystal of the saprolite horizon of the Al profile; f=kaolinite crystal of the lateritic crust of the Al-profile.

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Fig. 8. Average bulk chemical compositions of the Paragominas profiles.

The LREE elements are more abundant than HREE in the Al profile (Table 5) and the chondritenormalized REE plots are very similar between the horizons, with slight Eu anomalies and LREE enrichment (Fig. 6). The higher REE contents found in Paragominas as compared with N5 and IB might be associated to zircon, a residual common mineral in the lateritic profiles of this region. These slight variations in trace elements and REE in Paragominas throughout the profile, that is also observed in the N5 and IB profiles, suggest the same geochemical signatures during the weathering of the

lateritic crust, on account of their exposure to the landsurface.

5. Discussion A weathering transformation of lateritic crusts into soils is easily recognized in the Caraja s and Paragominas regions: the crusts are massive to nodular; further up the profile there occur lateritic crust fragments embedded in a earthy-clayey to clayed matrix that become smaller and rounded in the upper

Fig. 9. Average trace element concentration of the Paragominas profiles.

A.M.C. Horbe, M.L. da Costa / Geoderma 126 (2005) 225239 Table 5 REE contents of the Al-profile in ppm La Upper horizon Matrix (soil) 23.45 35.63 Intermediary horizon Matrix 42.42 Matrix 39.94 Fragment 14.82 Fragment 46.84 Ce 45.21 67.17 Nd 15.80 28.37 Sm 1.48 2.47 Eu 0.31 0.47 Gd 1.49 2.24 Dy 2.07 3.21 Ho 0.44 0.70 Er 1.29 2.15 Yb 1.42 2.36 Lu 0.19 0.33 LREE 86.25 134.11 HREE 6.90 10.99

237

REE 93.15 145.1

68.83 60.84 26.35 52.46

35.01 12.06 13.65 13.56

2.75 2.18 1.09 2.16

0.50 0.44 0.21 0.39

2.85 2.47 0.82 2.04

5.38 3.67 1.78 2.94

1.28 0.83 0.44 0.69

4.43 2.69 1.58 2.51

5.73 3.32 1.89 3.13

0.84 0.47 0.26 0.46

149.51 56.12 115.46 115.41

20.51 6.77 13.45 11.77

170.02 62.89 128.91 127.18

horizon. This matrix, that fills fractures and fissures in the lower horizons, becomes more abundant in the upper horizons until it forms complete loose soils. This process is mainly demonstrated by the geochemical lithodependence among crusts, their fragments and derived matrix and soils that show almost the same pattern of trace elements and REE in every profile studied, supporting the reworking process on the underlying lateritic crust in consequence of their exposure to the landsurface. Fragments and matrix are the in situ product of the progressive transformation of the lateritic crust by tropical weathering similar to that observed in the transformation of the parent-rock into saprolite and mottled clay horizons in most tropical weathering profiles (Beauvais and Colin, 1993). This reworking decreases the contents of hematite and Fe2O3 in the Caraja s profiles, and gibbsite and Al2O3 in Paragominas profiles toward the top of the profiles, while there is an increase on gibbsite, Al-goethite and Al2O3 in the first, and kaolinite, quartz and SiO2 in the second. On the other hand, these mineralogical transformations do not modify the trace elements and REE general pattern from the lateritic crust to its weathering products as it occurs in the horizons of a classical and well developed tropical weathering profile. Only a small modification has been observed: Mn and Cu in Paragominas have a slight increase in the matrix and B, Pb and Au increase in the gossan relicts as well as V, B, Mo, Y, Sc and Cu decrease in the metavolcanic relict found in the lateritic crust from that in the intermediary horizon. These chemical changes are not reflected in the matrix. Thus, during this process, the soil maintains the same geochemical signature as the lateritic crust. In N5 and IB, the higher Al contents in the goethite of the matrix suggests that this mineral is neoformed

in this new weathering environment rich in this element. Thus, the Al-goethite would be able to capture trace elements being leached from the dissolution of hematite and not allow their decrease in the matrix. This mineralogical transformation can explain why the crust, fragments, matrix and soil have the same geochemical signature. In Paragominas with the low capacity to capture elements of kaolinite and gibbsite, the same pattern of trace elements in the horizons is probably a consequence of the similar hematite and goethite contents in the profiles. The maintenance of the REE patterns in every profile suggests that these elements could be mainly related to residual minerals, such as zircon, that show lower enrichment factor in a weak weathering process. This vertical transition between the three horizons of the weathering profiles is also supported by the morphological changes on gibbsite and kaolinite from micro to cryptocrystalline, by the nodule and gibbsite crystal edge corrosion and by the color fading intensity in the nodules of the Paragominas crust fragments as a consequence of the iron leaching. This progressive physical transformations is similar to the degradation process, which is observed in lateritic crusts in hot and humid climates in Africa (Boulange , 1984; Didier et al., 1985; Nahon et al., 1989; Bardossy and Aleva, 1990; Bilong et al., 1992; Beauvais and Colin, 1993; Beauvais and Tardy, 1993; Bitton and Volkoff, 1993) although the thickness of the loose top material studied here is much thicker than that on other ones from elsewhere. Although Tardy (1993) and Tardy and Roquin (1998) consider gibbsite and goethite to be the typical association in the degradation process of the lateritic crust in humid climate and well drenated environment, the high kaolinite content in the Paragominas soil

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suggests that in this region, this mineral might not only be a relict from the crust, but also a neoformed mineral since ferruginization and aluminization imply a desilication process (Nahon, 1991), which decreases its contents and does not account for the high amount found in the soil covering the Paragominas lateritic crusts,. The higher content in kaolinite in these soils is different from that which occurs by the same process in Central Africa where the tropical climate is less humid than that in the Amazonian region. Maybe the geochemistry of the lateritic crust and/or relief and rainfall characteristics are the reason for this different evolutionary process in Paragominas. Although the mean annual rainfall of 1600 mm is lower in Caraja s, the higher altitude (600900 m) and the lower iron content might bring about a more intense leaching favoring gibbsite and goethite formation, while in Paragominas, which is more humid (2000 mm mean annual rainfall) but with lower altitude (50180 m), may act as a less leached environment that enabled the crust resilicification and the kaolinite neoformation. This resilicification of gibbsite needs further studies even though Lucas et al. (1993) have already suggested this process in soil environment. The lateritic crusts tropical degradation in the Amazonian region can be related to the weathering process that started in this region in the Tertiary and extends up to recent times as a consequence of climatic changes. During this period, the tectonic activity allowed the dissection of the relief, enhancing the erosion of the profiles in the valleys and, consequently, stone lines could be formed at the expense of the lateritic crust, as the climate change to semi-arid conditions. These ideas have led some researchers, such as Sombroek (1966), Dennen and Norton (1977), Grubb (1979), Truckenbrodt and Kotschoubey (1981), Hieronymus et al. (1989) and Truckenbrodt et al. (1991), to conclude that the lateritic crust and the earthy-clayey and clayey matrix and the soil overburden or topsoils have a different origin especially when the crust is overlain with more then 10 m of soil. However, the geochemical evidence presented above shows strong interactions between the lateritic crust and the earthyclayey to clayey material, reddish to yellowish topsoil, suggesting an autochthonous process. These soils can be the product of more than one period of weathering of the previous exposed lateritic crusts. Several

profiles with typical lateritic crust in the Amazonia are ancient and dated from between 65 and 70 Ma (Vasconcelos et al., 1996; Ruffet et al., 1996) making the process of the topsoil formation very complex along the time mainly in the Amazon where hot and humid climate has occurred for a long time.

6. Conclusions The hot and humid climates in the Caraja s and Paragominas region act intensively on the lateritic crusts causing their weathering and transformation into soils. This leads to a progressive dissolution process, indicated by the fragmentation of lateritic crusts and the increasing amount of matrix toward the top of the profiles up to the completely loose soils. The signature of this transformation is the increase of gibbsite, Algoethite and Al2O3 in Caraja s, and kaolinite, quartz and SiO2 in Paragominas upward the weathering profiles and a similar trace element and REE pattern in the crust, crust fragments and matrix and then into the topsoils indicating an in situ transformation in a weak weathering environment. The presence of gibbsite and Al-goethite in the matrix and soils of N5 and IB suggests a greater leaching process in Caraja s, than that of the kaolinite in the matrix in Paragominas. Based on these characteristics, we can conclude that the topsoil is the product of a chemical weathering transformation of lateritic crust in response to the tropical climate that followed the establishment of these crusts and their exposure to the landsurface.

Acknowledgments This study was sponsored by CNPq (the Brazilian National Council for Scientific and Technological Development) and the Centro de Geocie ncias of the Universidade Federal do Para (CG-UFPa). We thank the anonymous referees that helped improve the manuscript with their helpful suggestions.

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