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International Geology Review

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Sequential opening and filling of cavities forming

vesicles, amygdales and giant amethyst geodes in lavas
from the southern Paraná volcanic province, Brazil and
Uruguay
a b c
Léo Afraneo Hartmann , Lauren da Cunha Duarte , Hans-Joachim Massonne , Cassiana
a a d c
Michelin , Leonardo Manara Rosenstengel , Magda Bergmann , Thomas Theye ,
a a a a e
Juliana Pertille , Karine Rosa Arena , Sandro Kucera Duarte , Viter Magalhães Pinto ,
a a d
Eduardo Guimarães Barboza , Maria Luiza C.C. Rosa & Wilson Wildner
a
Instituto de Geociências, Universidade Federal do Rio Grande do Sul, Avenida Bento
Gonçalves, Porto Alegre, Rio Grande do Sul, Brazil
b
Departamento de Materiais, Escola de Engenharia, Universidade Federal do Rio Grande do
Sul, Porto Alegre, Rio Grande do Sul, Brazil
c
Institut für Kristallchemie und Mineralogie, Universität Stuttgart, Stuttgart, Germany
d
Geological Survey of Brazil (CPRM), Rua Banco da Província, Porto Alegre, Rio Grande do
Sul, Brazil
e
Departamento de Geologia, Universidade Federal da Roraima, Rio Branco, Roraima, Brazil
Published online: 06 Aug 2010.

To cite this article: Léo Afraneo Hartmann , Lauren da Cunha Duarte , Hans-Joachim Massonne , Cassiana Michelin , Leonardo
Manara Rosenstengel , Magda Bergmann , Thomas Theye , Juliana Pertille , Karine Rosa Arena , Sandro Kucera Duarte , Viter
Magalhães Pinto , Eduardo Guimarães Barboza , Maria Luiza C.C. Rosa & Wilson Wildner (2012) Sequential opening and filling
of cavities forming vesicles, amygdales and giant amethyst geodes in lavas from the southern Paraná volcanic province, Brazil
and Uruguay, International Geology Review, 54:1, 1-14, DOI: 10.1080/00206814.2010.496253

To link to this article: http://dx.doi.org/10.1080/00206814.2010.496253

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 International Geology Review
Vol. 54, No. 1, January 2012, 1–14

Sequential opening and filling of cavities forming vesicles, amygdales and giant amethyst geodes
in lavas from the southern Paraná volcanic province, Brazil and Uruguay
Léo Afraneo Hartmanna *, Lauren da Cunha Duarteb , Hans-Joachim Massonnec , Cassiana Michelina , Leonardo Manara
Rosenstengela , Magda Bergmannd , Thomas Theyec , Juliana Pertillea , Karine Rosa Arenaa , Sandro Kucera Duartea ,
Viter Magalhães Pintoa,e , Eduardo Guimarães Barbozaa , Maria Luiza C.C. Rosaa and Wilson Wildnerd
a Instituto de Geociências, Universidade Federal do Rio Grande do Sul, Avenida Bento Gonçalves, Porto Alegre, Rio Grande do Sul,
Brazil; b Departamento de Materiais, Escola de Engenharia, Universidade Federal do Rio Grande do Sul, Porto Alegre, Rio Grande do
Sul, Brazil; c Institut für Kristallchemie und Mineralogie, Universität Stuttgart, Stuttgart, Germany; d Geological Survey of Brazil
(CPRM), Rua Banco da Província, Porto Alegre, Rio Grande do Sul, Brazil; e Departamento de Geologia, Universidade Federal da
Roraima, Rio Branco, Roraima, Brazil
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(Accepted 17 May 2010)

The opening and filling of cavities in rocks are the major processes related to the generation and sealing of porosity in ore
deposits. This study documents three stages of opening and filling of vesicles and geodes in the basalts and rhyodacites of the
southern Paraná volcanic province. Each step detailed here is actually part of a sequence of minor hydrothermal events. First,
lava degassing at high temperature (1150◦ C) formed small (<4 cm) vesicles in the crusts of flow units. In sequence, these
vesicles were partly to fully filled at low temperature (30–150◦ C) by hydrothermal minerals, particularly clays and zeolites;
this process also sealed the porosity of the lava. Second, the injection of fluidized sand generated new cavities, which were
partly filled with sand; the newly formed porosity was sealed by the low-temperature fluid. Third, intense alteration of
the basalt or rhyodacite core into a claystone favoured the opening of small to giant protogeodes (0.1 mm to 4 m) by
dissolution; cooling of the fluid led to the precipitation of hydrothermal minerals, particularly the spectacular amethyst,
calcite, and gypsum-bearing geodes.
Keywords: vesicles; amygdales; giant geodes; amethyst-quartz; Serra Geral Group

Introduction The filling of vesicles with zeolites and geodes with

The opening and filling of cavities in rocks are the major
processes related to the generation and sealing of poros-
ity in ore deposits. The Paraná volcanic province of South
America (Figure 1) constitutes one of the largest conti-
nental flood basalt provinces in the world and has large
deposits of amethyst and agate (calcite, gypsum) geodes.
Specimen-quality minerals, including several zeolites, are
also abundant in the amygdales of the volcanic rocks. The
investigation of these different cavities is therefore a major
topic in the geology of volcanic rocks.
Basalts and rhyodacites (including some andesites)
from the Cretaceous (133 Ma) Paraná volcanic province
are included in the Serra Geral Group. These units cover
1,300,000 km2 of South America, not only in Brazil
but also in Uruguay, Argentina, and Paraguay (Bellieni
et al. 1984). Monthly production of geodes from under-
ground mines is nearly 400 tons, mostly from Ametista do
Sul (Brazil) and Los Catalanes (Uruguay), with commerce
concentrated in Soledade, Brazil.
quartz and amethyst is recognized as a low-temperature
process (50◦ C) (see, for example, Juchem (1999), Gilg
et al. (2003), Duarte et al. (2009), Morteani et al. (2010),
and Commin-Fischer et al. (2010)), and generally it is
considered to represent a single hydrothermal event. For
instance, Commin-Fischer et al. (2010) observed that the
small cavities (amygdales) are rarely filled with SiO2
phases, and attributed this feature to restricted water cir-
culation. The opening of vesicles in the upper and lower
crust of lavas has long been regarded as the result of lava
degassing at high temperature (1150◦ C) (see, for exam-
ple, Aubele et al. (1988) and Sahagian et al. (1989)). The
economically significant large cavities (geodes) present in
the massive core of the lavas have also been attributed
to lava degassing at 1150◦ C (Proust and Fontaine 2007a).
However, Duarte et al. (2009) showed that these cavities
were formed at low temperature (150◦ C) and therefore
have an epigenetic origin. The hydrothermal processes
were also evaluated by Hartmann (2008).

∗ Corresponding author. Email: leo.hartmann@ufrgs.br

ISSN 0020-6814 print/ISSN 1938-2839 online

© 2012 Taylor & Francis
http://dx.doi.org/10.1080/00206814.2010.496253
http://www.tandfonline.com
 2 L.A. Hartmann et al.
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Figure 1. Geological map of the Serra Geral Group volcanics in South America, including the distribution of sedimentary cover rocks.
Palaeozoic–Mesozoic sedimentary rocks (not shown) of the Paraná basin underlie the volcanic group. Precambrian basement is also
included in the white area. Modified after Peate et al. (1992).

The volcanic province is at the top of the sedimen-
tary Paraná Basin, which contains the very large Guarani
aquifer directly below the lavas (Araújo et al. 1999). This
aquifer mostly consists of sandstones of the Botucatu
Formation (Scherer 2000). Heating by volcanism provided
a widespread, nearly infinite volume of hot water and
vapour for basalt alteration and related processes of cavity
formation and filling. This aqueous fluid was essentially
infinite because only a minor volume of the aquifer was
required for the mineralization process, and because the
aquifer was continually replenished from the borders of
the Paraná Basin where the Botucatu Formation is well
exposed (Araújo et al. 1999).
Two main questions remain unanswered (Commin-
Fischer et al. 2010) concerning the processes of cavity
filling in mineralized Paraná basaltic rocks: (1) the pres-
ence of silica minerals is mostly restricted to geodes
(not in amygdales); and (2) mineral zoning (chalcedony
to amethyst) only occurs at the scale of the geode and
not along the lava flows. The epigenetic, low-temperature
(∼150◦ C) geological environment of basalt alteration and
cavity opening reported by Duarte et al. (2009) is consid-
ered by Commin-Fischer et al. (2010) to be an adequate
description of the mineralization process. The state-of-the-
science calls, therefore, for an evaluation of the sequence
of the formation of two different types of cavities present
 International Geology Review
in the volcanic rocks, the high-temperature vesicles and the
low-temperature protogeodes. We also evaluate the filling
of cavities with silicates, carbonates, sulphates, and native
copper. We mainly use field observations over a large area
(500 × 500 km) of the basaltic-dacitic province in south-
ern Brazil and Uruguay. These are supported by scanning
electron microscopy, X-ray diffractometry, and electron
microprobe data.
This investigation is most significant for the under-
standing of the origin of the world-class amethyst geode
deposits of southern Brazil and Uruguay, and of the inter-
action of the huge Guarani aquifer with one of the largest
volcanic provinces in the world.
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Methods of investigation
Previous investigations of the minerals present in the amyg-
dales and geodes were initially evaluated, and these include
several unpublished doctoral and master’s theses (Borget
1980; Gomes 1996; Scopel 1997; Juchem 1999; Augustin
2007; Michelin 2007; Frank 2008), a few articles (Murata
et al. 1987; Scopel et al. 1990), and many abstracts pub-
lished in regional symposia (e.g. Bossi and Caggiano
1974). Them main observations regarding the sequence
of filling of cavities in basalts are well summarized in
Gustavson (2006), and significant observations are also
made by Flóvenz and Saemundsson (1993) and Neuhoff
et al. (2006). This is the first description of the sequence of
filling of cavities in the Paraná basalts.
Field and laboratory works were undertaken over a
6-year period (2004–2009). Efforts were concentrated both
in amethyst-mining districts, for example, Ametista do Sul
in Brazil and Los Catalanes in Uruguay, and in many
unmineralized road cuts and quarries. Much field work was
done jointly with the Geological Survey of Brazil (CPRM),
for example, Magda Bergmann (2009, unpublished data).
Scanning electron microscopy, X-ray diffractometry, and
electron microprobe analyses of hydrothermal minerals
were carried out mostly at the Institut für Mineralogie und
Kristallchemie, Universität Stuttgart, Germany, whereas
those related to copper mineralization were made at the
University of Western Australia in Perth.
Field description
Every basalt lava or rhyodacite unit (including basaltic
andesite, andesite, and rhyolite) in the Paraná vol-
canic province has cavities (amygdales and geodes)
partly or completely filled with hydrothermal minerals
(Figures 2–11). The internal structure of the lavas (Figures
2–4) is typical of inflated pahoehoe lobes in Ametista do
Sul, but is more complex in Quaraí (Hartmann et al. 2010),
because some of the lavas (particularly lava 2, colada
Catalán) have the structure of aa lavas with blocky crusts
and massive core. In many outcrops, the upper crust of
3
the lavas is a stockwork breccia of sand and amygdaloidal
basalt. There is a large number (possibly 120) of lava units
in the Serra Geral Group, whose total thickness is near
1800 m in the depocentre (300 km N of Ametista do
Sul), and each lava unit has a thickness between 5 and
70 m. In a carefully measured sequence of 16 basalt lava
flows along the Serra do Rio do Rastro cuesta on the east-
ern border of the volcanic group (Vargas 2006), the total
lava thickness is 700 m, which leads to an estimate of
120 lava flows in the depocentre farther northwest. Rock
types are bimodal basic-acid and include basalt, basaltic
andesite, andesite, dacite, trachyte, rhyodacite, and rhyo-
lite, here simply referred to as basalt and rhyodacite, the
two most abundant rock types in the volcanic province.
In the Ametista do Sul mining district, there are 13
basalt lavas (Pinto et al. 2010) exposed in the hills between
250 and 600 m elevation above sea level (4 lavas imme-
diately below Ametista do Sul town), but an additional
sequence of 800 m of basalt and intercalated rhyodacite
was recognized below the surface during drilling for under-
ground water by the Geological Survey of Brazil. Aeolian
sandstones of the Botucatu Formation were reached at the
bottom of the drill core. On the other hand, in the Los
Catalanes gemological district, only 1–4 lava flows are
present above the aeolian sandstones, and these are one
basal basalt, one andesite, and two basaltic andesites (e.g.
Duarte et al. 2009; Hartmann et al. 2010).
Rhyodacite units (including rhyolite and trachyte)
occur in the middle portion of the Serra Geral Group and
have the structure of rheoignimbrites (Nardy et al. 2008).
Each unit has a thickness of nearly 50 m and attains great
lengths, for example, 30 km. These silicic units have a
total thickness of approximately 250 m. An upper vesicu-
lar crust is common in the upper part of the unit, whereas
amethyst and agate geodes, when present, always occur
below the upper amygdaloidal crusts in the upper portion
of the volumetrically dominant (70%) massive core.
In the Los Catalanes gemological district, an are-
ally restricted basalt (colada Mata Olho) and an andesite
(57.5 wt.% SiO2 ), colada Catalán of Duarte et al. (2009),
erupted in the Lower Cretaceous directly over an active
sand desert (erg). Colada Catalán has the structure of an aa
lava. This unit is most important because it hosts the giant
amethyst geodes and smaller agate geodes that constitute a
world-class deposit.
The great majority, some 94%, of the lavas are basalts
and basaltic andesites in the Paraná volcanic province with
the classical structure of pahoehoe lavas and lobes with
upper and lower amygdaloidal crusts and massive core.
Thicker lavas (30–70 m) display vertical joints in the core,
whereas thinner lavas do not have cooling joints (Gomes
1996). These internal structures of the basalts are similar to
the Columbia River basalts (Long and Wood 1986). In con-
trast, in the Los Catalanes gemological district, some of the
more siliceous lavas (andesite and basaltic andesite) have
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Figure 2. Model sections of lava units in the two main mining districts in the Serra Geral Group, showing the local stratigraphy and
internal structure of lavas; every lava unit displays upper and lower amygdaloidal crusts (not shown), and the sequence of hydrothermal
events H1, H2, and H3. (A) Los Catalanes gemological district (Artigas) and Quaraí region; lava 1 is a basalt present 30–50 km N of
Quaraí; lava 2 is an andesite, has the structure of aa lava and covers aeolian sandstone in Quaraí; sand is present in dikes, sills, and flows,
and also in intertrap dunes; amethyst geodes occur in massive portions of basalt and andesite lavas; lavas 3 and 4 are basaltic andesites.
(B) Four basalt lava units under Ametista do Sul town; lava 3 (derrame Veia Alta) is the most intensely mined for amethyst geodes, most
mines at elevation 430 m; an additional sequence of 800 m of basalt and dacite lavas underlies the four locally exposed lavas.

Figure 3. Model section of colada Catalán, Los Catalanes gemological district, and Quaraí region. Silicified sandstone layers and
stockwork breccias (amygdaloidal andesite blocks) detailed as H2 events, amethyst geode as H3 event. Core type I (no columnar jointing,
mineralized) occurs in thinner flows (<30 m), core type II (columnar jointing present, unmineralized) in thicker flows (>30 m).
 International Geology Review 5
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Figure 4. Model cross-section of colada Cordillera, Los Catalanes gemological district, and Quaraí region. Silicified sandstone layers
and breccias occur at the top of the flow and at the base of core type II. Amethyst geode ore restricted to core type I. More intensely
silicified core type I constitutes erosional remnants. Box indicates the opening of vesicles during magmatic event M, followed after
cooling by hydrothermal event H1 which filled the amygdales with zeolites. Later, event H3 opened and filled cavities with amethyst.

Figure 5. Musem mine, Ametista do Sul. Classical profile of mine entrance in massive type I core basalt, capped by igneous breccia
and amygdaloidal basalt, covered by intrusive, silicified sandstone breccia and extrusive, silicified sandstone layer. Unmineralized upper
basalt flow with massive, type II core with vertical joints.

the structure of aa lavas. A novel type of structure is the
presence of two types of massive core in the same lava flow.
Core type I does not have vertical cooling joints and may
be mineralized with amethyst geodes, whereas core type II
shows vertical cooling joints and does not contain ore.
All rocks in the Serra Geral Group display subver-
tical fractures and faults spaced a few millimetres to a few
metres, formed after cessation of hydrothermal activity.
These fractures do not contain low-temperature minerals.
Sequence of events
The initial geological event M (Table 1) involved the
flow of lavas over the erg surface; for example, the Los
Catalanes gemological district and Quaraí mining district
where the contact of the lavas with sand is exposed over
a large distance of more than 100 km. In the depocentre
of the Paraná basin, the lava sequence is up to 1800 m
thick; for example, 1100 m in Ametista do Sul mining
district. The initial cooling, from magmatic temperatures
of 1150◦ C, caused degassing and the formation of vesi-
cles at magmatic temperature in both the upper and lower
crusts. Aa lavas have a more complex crust and a vesic-
ular portion is also present. The core of the pahoehoe or
aa lava is commonly more than 70% of the total thickness
and contains a massive core in thinner lavas. In the thinner
lavas, the core does not have a columnar jointing, which
is well developed in thicker lavas. All units are presumed
to be highly porous (30%) after cooling to ambient tem-
perature, analogous to fresh basaltic lava found in Iceland
 6 L.A. Hartmann et al.
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Figure 6. (A) Miolo agate mine, São Martinho da Serra, RS; H2 event, silicified sandstone dike with opening of H2 cavity and its filling
with quartz. (B) La Bolsa mine, Los Catalanes gemological district, showing brecciated andesite which either opened into a geode (right)
or remained closed (left); (C) and (D) Musem mine, Ametista do Sul, RS; amethyst geodes, positioned above a subhorizontal flat-lying
fracture, filled with quartz and amethyst geode above the fracture in (C); amethyst geode along and above flat-lying fracture in (D).

(Flóvenz and Saemundsson 1993), because of the presence
of micro-fractures and vesicles.
In the Paraná volcanic province, no high-temperature
minerals are present in the vesicles or in the altered basalt,
andesite, or dacite. Clinoptilolite is fairly common in
amygdales and in the matrix of altered rocks (Duarte et al.
2009), whereas apophyllite is rare and only present in a
few amygdales (Frank 2008). According to Frank (2008),
it was considered that the formation of higher tempera-
ture minerals was due to the thermal effect of the upper
flow. Therefore, the highest temperature of the hydrother-
mal event seems to be lower than 150◦ C. The vesicles
are therefore presumed to have remained unfilled down
to surface temperature after solidification of the lavas.
Such unfilled vesicles are dominant in basalt lavas from
Hawaii and from the Moon. Stable isotopes indicate that
all hydrothermal minerals in fractures, filled vesicles (now
amygdales), and geodes precipitated from meteoric fluid
(nearly pure water) (see, for example, Matsui et al. (1974),
Juchem (1999), Gilg et al. (2003), Morteani et al. (2010),
and Commin-Fischer et al. (2010)). There is no indica-
tion that magmatic water remained in the rock during the
time required to cool the lava from 1150◦ C to 150◦ C,
only to deposit minerals in the pores at 100–130◦ C. A
new event of hot water percolation was required to fill
the fractures and cavities with minerals. According to the
observation of Commin-Fischer et al. (2010), Morteani
et al. (2010), and this work, the geodes exhibit in all cases
the same sequence of silica minerals from the wall to the
centre (Figure 10); a thin (0.1–20.0 mm) celadonite rim
is succeeded by chalcedony (agate), followed by colourless
quartz and amethyst, and in a few mines in Ametista do
Sul (3 out of 300) by an overgrowth of gypsite. In the Los
Catalanes geodes, sulphates such as anhydrite, gypsum,
and barite were neither found nor described in the literature
(Morteani et al. 2010). Rare fluorite occurs in both mining
districts. None of these minerals has been described inside
amygdales.
The following hydrothermal events, H, occurred during
a complex succession (Figure 11) of porosity sealing and
opening (fault-valve action). The water-rich fluid was prob-
ably overpressured during the entire hydrothermal event,
but a sequence of structural and mineralogical overprints
can be recognized as H1, H2, and H3 events (Figures 3–
10). Two main sealing events occurred after the completion
of H1 and H2 and led to the overpressuring of water vapour.
The source of water for the hydrothermal events was the
Guarani aquifer that underlies the volcanic sequence, as
indicated by stable isotopes (Gilg et al. 2003; Morteani
et al. 2010). It is the largest freshwater aquifer in the world
 International Geology Review 7
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Figure 7. Highway exposures, Três Passos, RS; structures related to H1, H2, and H3; (A) H2 sand dike (indicated by arrow) intruded
into M; H1 amygdaloidal basalt and extrudite of sand over the lava, possibly sand volcano above dike; (B) H2, silicified sandstone sills
intruded into the lava, which is covered by sand extrudite; (C) H2 stockwork of sand, injected into M, H1 amygdaloidal basalt; massive
basalt above the sand is a new lava; (D) H2 stockwork of silicified sandstone, containing blocks of amygdaloidal basalt; (E) H2 sand
sill (indicated by arrow) emanating from sand dike; (F) H3 quartz-filled, vertical fracture (indicated by arrow), feeding a small H3 quartz
geode; (G) three H3 quartz-filled, vertical fractures, feeding three small H3 geodes (indicated by arrows); (H) H1, H2, and H3 stockworks;
H1 is an interconnected structure of amygdales and micro-fractures (visible in the field or under the microscope); H2 is a sand breccia
containing M, H1 amygdaloidal basalt fragments; H3 consists of interconnected quartz veins; this figure represents the entire sequence of
opening and filling of cavities in the Serra Geral Group.
 8 L.A. Hartmann et al.
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Figure 8. Sequence of formation and filling of cavities in Quaraí mining district. (A) Sanga do Tigre, 15 km east of Quaraí town, 500 m
south of dirt road; M vesicles (now amygdales) filled with H1 zeolites inside the circle and filled with H3 quartz outside the circle; H2
sand dike indicated by arrows; presence of large H3 geode (possibly 1 m) under the surface, marked by the circle, indicated by georadar
scanning of the surface; host rock is an andesite (lava 2, colada Catalán). (B) Same outcrop, showing small amygdales and larger H3
geode, both filled with quartz; H1 zeolites dissolved from the amygdales before deposition of H3 silica minerals. (C) Garimpo do Vivi, at
the margin of Rio Quaraí; H3 amethyst filling geode. (D) Garimpo do Vivi, with numerous H3 quartz and amethyst geodes contained in
altered andesite (lava 2, colada Catalán).

Figure 9. Sequence of formation and filling of cavities in São Martinho da Serra; Miolo agate geode deposit. (A) H2 sand dike changes
into H3 agate-filled fracture; (B) H1 zeolite (clinoptilolite, mordenite)-filled amygdales, H2 sand dike and H1 amygdales replaced by H3
agate; H3 quartz-filled geode; (C) H2 sand dike cut by a vein of H3 agate; (D) Quartz grains from a sand dike silicified by agate cement.
 International Geology Review
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Figure 10. Drawing of an H3 geode on a mine wall, hosted in
smectite basalt. Only silica minerals present, except for some late
calcite and gypsite. Feeding channel displayed. Model based on
occurrences in several mines, Ametista do Sul, and Cordillera
mines, Los Catalanes gemological district (Artigas).
and comprises the aeolian sandstones of the Botucatu
Formation and underlying Triassic–Jurassic, sedimentary
formations of the Paraná basin (Zalán et al. 1990; Araújo
et al. 1999). Warming of this unique aquifer either by
the Tristan plume or by the concentration of heat beneath
Gondwana supercontinent (Coltice et al. 2007) provided
Figure 11. Evolutionary curves of temperature and water vapour pressure (A) during hydrothermal alteration and mineralization of
basalt (e.g. Ametista do Sul), basaltic andesite and andesite (e.g. Los Catalanes), and rhyodacite (e.g. Caxias do Sul); (B) inset displaying
temperature evolutionary curve from magmatism to the studied hydrothermal temperatures.
9
the mechanism responsible for the huge circulation cell of
hot water in the basalts and dacites. Field evidence indi-
cates that each pulse of lava generation in the mantle and its
ascent and extrusion at the surface resulted in a sequence
of three main hydrothermal events, possibly a continuum
of fluid overpressure under each basalt flow. These pro-
cesses may be similar to those described by Flóvenz and
Saemundsson (1993) for Iceland.
Event H1 was the first major hydrothermal process
to seal the high initial porosity of the volcanic rock.
Micro-fractures and vesicles were sealed by voluminous
deposition of clay minerals (smectites), zeolites, including
heulandite, clinoptilolite, and mordenite indicative of
temperature near 150◦ C. Similar to the description of
Gustavson (2006), small vesicles were entirely filled with
the first mineral phase to deposit, leaving no room for the
next mineral to precipitate. Larger vesicles have a rim of
the first clay minerals (smectites), zeolite, succeeded by a
layer of the next mineral to precipitate. The largest vesicles
display the entire sequence of deposition of hydrothermal
minerals in H1. The core of vesicles from a few flows
is filled with native copper. The thickness of the mineral
layer is the same in both small and large vesicles. It is
important to notice that silica minerals are nearly absent in
vesicles filled during H1. Although the same minerals were
deposited in the vertical cooling joints, these wide open
(1–2 mm) structures remained open after H1, so the cores
type II of thicker basalt lavas were not sealed in this event.
Successive fluid pulses did not become overpressured in
thicker lavas and ascended freely along the fractures to the
surface.
In a similar way as described by Gustavson (2006), the
filled vesicles are interconnected by thin (<0.1 mm) frac-
tures that were also filled with clay minerals and zeolites
during H1. The fractures may be visible in the outcrop and
are readily apparent under the microscope.
 10 L.A. Hartmann et al.

Table 1. One magmatic (M) and three hydrothermal (H) events related to cavity opening and filling in Serra Geral Group basalts and
dacites, southern Brazil, and northwestern Uruguay. Position of sealing events 1 and 2 is indicated in the sequence of hydrothermal
processes.

Porosity (P) –
Event Process Structures permeability (p) Cavity formed

M Magmatism, 1150◦ C Lava flows, dikes, sills High Vesicle

H Hydrothermalism,
30–150◦ C
H1 Basalt alteration, zeolites,
and native copper
formation, <100–30◦ C
H2 Fracturing of basalt,
injection of stockwork of
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Polygonal faults – Fault seal action, high Geode
hexagonal, irregular P-p evolving to low
P-p
Filling of vesicles to form Sealing of P-p None
amygdales
Sealing of lava, event 1
Dikes, sills, flows of sand; Initially high, Geode
filling of geodes with evolving to low P-p

fluidized sand, and sand

silicification, ∼100◦ C
H3 Alteration of basalt and
silicified sandstone,
opening of cavities
following explosive
lifting of upper part of
lava, 100–30◦ C,
dissolution of zeolites
F Subvertical, transcurrent
faulting
G Weathering, soil, gossan,
supergene alteration of
amethyst deposits and
native copper
occurrences
Sealing of lava, event 2
Horizontal fractures, Very low P-p Giant geode
feeding channels to
protogeodes, filling of
geodes with quartz and
amethyst
Fault zones, no High P-p None
hydrothermal minerals
Polygonal blocks at – –
surface, tainted either
brown or light green

Event H2 is notable, because it consists of the open-
ing of a few cavities and injection of fluidized sand into
the basalt lavas or dacite units. The forceful injection
formed dikes (0.1–1.0 m wide) and sills that evolved
into stockwork breccias of sand and amygdaloidal basalt
in the upper crusts of the lavas. Some dikes and stock-
works reached the surface of the sand volcanoes and spread
thin sand sheets over the surface. The lava units have in
places a thin (0.5–2.0 m) layer of silicified sandstone on
top, observed in several positions in the stratigraphy; that
is, in the 1700 m of volcanic rocks. Overpressured fluid
opened some cavities and partly filled them with sand. The
continued fluid flow in these high-permeability channels
(sand dikes and sills) turned loose, injected sand into very
cohesive sandstone, a rock once used by native Indians to
make arrowheads. Thus, at the end of event H2, the lava
was sealed again. A large volume of silica thus became
available for dissolution and reprecipitation during the later
hydrothermal events, although some of the silica may be
originated from the alteration of the basalts as envisaged
by Proust and Fontaine (2007b).
Pore fluid again became overpressured under the
volcanic unit and generated the hydrothermal event H3,
whose intense alteration of the lava turned it into a
claystone with more than 60 vol.% of clay (celadonite,
smectite). When the water vapour ascended to a depth of
10–20 m under the surface, the top of the flow was lifted
and the vapour exploded laterally generating a horizontal
fracture. In some well-exposed mine walls, this fracture
is associated with another fracture that runs up into the
rock at a 40◦ inclination. Geodes in basalt and andesitic
basalt are at the tips of these inclined fractures, which are
feeding channels of fluid into the cavity. The fractures
remained open to be filled with the same hydrothermal
minerals present in the geodes. In aa lavas, on the contrary,
horizontal fractures and inclined feeding channels are
also present but are more irregular and are filled with a
thin veneer of hydrothermal minerals. The fractures and
geodes are filled mostly with silica minerals, including
chalcedony along rim, followed by fine quartz, coarse
quartz, and then amethyst. Calcite also occurs in some
geodes. Gypsite may occur with calcite although it fills the
geodes entirely in some of the mines in Ametista do Sul. It
is very significant that zeolites and native copper are very
rare in the giant amethyst geodes of both the Ametista do
Sul mining district and Los Catalanes gemological district;
 International Geology Review
they only occur in amygdales filled during H1. A few
geodes are present in the silicified sandstones.
During H3, the fluid dissolved the minerals (particu-
larly zeolites) in many amygdales previously filled during
H1 and then filled them with silica minerals. This is the
only case where magmatic vesicles were filled with silica
minerals. This was observed in many places as a hetero-
geneous process, because some amygdales remain filled
with zeolites whereas others now exhibit silica minerals.
The key to the understanding of the outcrop distribution
of remnant H1 or newly filled H3 amygdales (both cavities
formed by degassing during M) is the access of H3 to the
H1-filled amygdales.
In an unfractured rock, the H1-filled amygdales remain
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unmodified. This relationship is also well seen at Ribeirão
do Tigre (Figure 8A and 8B), located 300 m south of the
road, 15 km E of Quaraí, including the formation of large
quartz-amethyst geodes during H3. In this outcrop, lava 2
(colada Catalán) has H1 amygdales filled with zeolites that
were injected by H2 sand dikes, followed by H3 dissolu-
tion of zeolites and refilling of the vesicles with quartz and
amethyst; new cavities (geodes) were also filled with H3
quartz at this time.
Colada Catalán is mineralized in the massive core
(Figure 8C and 8D) with H3 amethyst geodes in the
Vivi quarry, 30 km south of Quaraí, on the border
with Uruguay. The andesite is intensely altered to low-
temperature minerals.
The sequence of cavity opening and filling in the south-
ern Paraná volcanic province can be modelled (Figure 11)
as a continuous process of rock alteration, sealing, cavity
opening and filling. The main process occurred shortly
(possibly within 1 million years) after cooling of the lava,
followed by a main peak at 60 Ma (75 million years after
lava extrusion) related to reheating of the lava pile dur-
ing alkaline magma intrusion. Minor filling of the cavities
continued to this day.
After cessation of the hydrothermal activity, large sub-
vertical, transcurrent faults of event F cut the Serra Geral
Group as observed in satellite images. In the field, the faults
are brittle and the fault zone is commonly 20 m wide or
more, made up of thin (1–50 cm) blocks of volcanic rock.
No hydrothermal minerals are present in the major fault
planes, so the faulting must have occurred after cessation
of major hydrothermal activity. There is a significant lack
of relationships between the faults and the conduits for the
filling of the geodes.
Intense weathering formed thick (1–30 m) soils in the
region during event G, which also formed gossans over
the amethyst deposits and native copper occurrences. The
gossans are observed both in the satellite images and in
the field as brown polygonal structures surrounded by light
green low-lying (1–5 m) regions. The brown portions are
the oxidation zone (Fe3+ minerals) and the green portions
are the cementation zone (Fe2+ minerals).
11
Interpretation
No evidence has been described to support a magmatic
origin for the water responsible for the deposition of the
hydrothermal minerals in the province. All evidence (e.g.
stable isotopes) indicates meteoric water for the process,
which probably originated in the aeolian sandstones of
the Botucatu Formation (Guarani aquifer). Only minerals
formed below 150◦ C are described in the province; for
example, no epidote or chlorite.
The main point of this investigation is that the sequence
of formation and filling of cavities is the same over a large
portion (500 × 500 km) of the Serra Geral Group of
the volcanic rocks. Vesicles formed at magmatic temper-
atures (1150◦ C) by lava degassing were later filled during
the hydrothermal event H1 mostly with zeolites and clays
(some native copper). Zeolites are nearly absent from the
giant and small geodes just like silica minerals are nearly
absent from the filled vesicles (amygdales). We argue that
zeolites should have also formed in the rims of the giant
geodes if these cavities were present in the rock during H1.
Giant geodes mostly lack injected sand, which is
present in some smaller geodes; only in a few occurrences
is sand present in larger (20 cm) geodes, for example, Salto
do Jacuí, an indication that H2 also opened some cavities.
Hence, the giant protogeodes were not present in the rock
during sand injection. The sand was injected during H2 in
processes similar to those described by Hurst et al. (2003),
Fernandes et al. (2007), Shoulders and Cartwright (2007),
and Cartwright (2010), and made available to the basalts
a very large volume of silica for dissolution and repre-
cipitation in the giant geodes. Some silica may, however,
have come from the altered host rock. Event H3 was also
responsible for the opening of the giant protogeodes and
their filling with the valuable silica minerals, calcite, and
gypsite.
Geological evidence indicates that the hydrothermal
processes occurred shortly after lava extrusion, because
aeolian sand (now the Botucatu Formation) can only be
fluidized by water as loose grains. Although geologically
poorly defined, other sediments intercalated in the Serra
Geral Group lavas may have contributed to the injected
sand budget. After diagenesis and lithification, this now
lithified sand remained in situ and was not injected upwards
into the lavas. Hot water probably continues to percolate
in the basalts on a smaller scale to this day; for example,
there are approximately 100 hot springs within the volcanic
region. Dating of celadonite from basalts (Vasconcellos
1998) indicates the beginning of hydrothermal processes
close to the age of volcanism (135 Ma; Innocent et al.
1997; Wildner et al. 2006) and protracted alteration with
a peak at 60 Ma.
The systematic presence of a similar sequence of open-
ing and filling of cavities over a large area (500 × 500 km)
indicates that all three steps were needed to form the
 12 L.A. Hartmann et al.
amethyst-filled cavities – filling of the vesicles (H1), injec-
tion of sand (H2), and complete alteration of the basalt by
hot water. First, anomalous heating of the mantle under the
lithosphere caused the generation of the basaltic rocks that
are suitable hosts for the geodes and caused heating of the
huge aquifer and its ascent as hot water and its hot vapour.
This hydrothermal process caused the intense alteration
of the lavas and the sealing of their initial high poros-
ity by the deposition of zeolites in vesicles and fractures.
After this point in time, there was an explosive intrusion
of fluidized sand into the lavas. After the sealing of this
newly formed porosity, this hot fluid caused the formation
of the giant protogeodes and their filling with the spectacu-
lar crystals of quartz, amethyst, calcite, and gypsite. As so
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often in ore deposits, only the completion of all the phases
of hydrothermal interaction of channelized fluid with the
host rock leads to an ore deposit.
We have thus solved the two main questions posed
by Commin-Fischer et al. (2010): (1) Silica minerals did
not deposit in the vesicles (now amygdales) because these
were already filled by zeolites during H1 and no space
remained for additional deposition of minerals; also, per-
meability was reduced so the amygdales were not reached
by the silica-oversaturated fluid; silica was only available
to form silicates during H1, not silica minerals; (2) Silica
mineral zoning is only observed at the geode scale because
fluid ascended nearly vertically; no zoning in silica miner-
als occurred along the mineralized basalt flow because the
hydrothermal fluid only percolated horizontally at the mine
scale but not along the flow for long distances.
Later events were unrelated to the formation of cav-
ities and their filling, because the large faults of the F
event do not contain hydrothermal minerals. Weathering
formed both soil over the entire volcanic sequence and
particularly gossan over amethyst and agate deposits and
copper occurrences, a classical prospecting guide for new
deposits.
Conclusions
Based on extensive field and some key laboratory inves-
tigations, we elucidated the structural and mineralogical
evolution of cavities in the Serra Geral Group of the Paraná
volcanic province of southern Brazil and northwestern
Uruguay. This evolution resulted in the formation of world-
class deposits of amethyst geodes in Brazil and in Uruguay,
which are hosted in lavas from one of the largest volcanic
provinces in the world.
The opening and filling of the giant cavities (geodes)
with silica minerals was the third hydrothermal event
(H3) that altered the basaltic rocks of the Paraná volcanic
province in the Cretaceous. A sequence of three hydrother-
mal events was required to form and fill the large cavities
with amethyst. The first event (H1) filled the late-magmatic
(event M) vesicles present in the upper and lower crusts
of the lavas mostly with zeolites, which are absent from
the geodes, and sealed existing fractures. The second event
(H2) caused the injection and effusion of fluidized sand.
Two sealing events occurred intercalated in the hydrother-
mal events after H1 and H2, respectively. The sequence of
hydrothermal events affected most of the Paraná volcanic
province because of heating and ascent of hot water and
vapour from the underlying Guarani aquifer.
Acknowledgements
Conselho Nacional do Desenvolvimento Científico e Tecnológico
(Brazilian Government) offered systematic support for the inves-
tigations (Edital Universal), including field and laboratory work
and scholarships to several authors. Fundação de Amparo à
Pesquisa do Estado do Rio Grande do Sul and CNPq granted
support through a project of excellence on: ‘Strategic miner-
als from southern Brazil’, coordinated by LAH. The Institüt für
Mineralogie und Kristallchemie (Universität Stuttgart, Germany)
and the University of Western Australia offered scientific exper-
tise and significant support in their laboratories. Paul E. Potter and
Matthew Brown are thanked for the English revision.
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