<?xml version="1.0" encoding="ISO-8859-1"?><article xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance">
<front>
<journal-meta>
<journal-id>1647-581X</journal-id>
<journal-title><![CDATA[Comunicações Geológicas]]></journal-title>
<abbrev-journal-title><![CDATA[Comunicações Geológicas]]></abbrev-journal-title>
<issn>1647-581X</issn>
<publisher>
<publisher-name><![CDATA[LNEG - Laboratório Nacional de Energia e Geologia]]></publisher-name>
</publisher>
</journal-meta>
<article-meta>
<article-id>S1647-581X2010000100005</article-id>
<title-group>
<article-title xml:lang="en"><![CDATA[Speleothems of Granite Caves]]></article-title>
<article-title xml:lang="pt"><![CDATA[Espeleotemas de Cavernas Graníticas]]></article-title>
</title-group>
<contrib-group>
<contrib contrib-type="author">
<name>
<surname><![CDATA[Vidal Romaní]]></surname>
<given-names><![CDATA[J. R.]]></given-names>
</name>
<xref ref-type="aff" rid="A01"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname><![CDATA[Sanjurjo Sánchez]]></surname>
<given-names><![CDATA[J.]]></given-names>
</name>
<xref ref-type="aff" rid="A01"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname><![CDATA[Vaqueiro]]></surname>
<given-names><![CDATA[M.]]></given-names>
</name>
<xref ref-type="aff" rid="A01"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname><![CDATA[Fernández Mosquera]]></surname>
<given-names><![CDATA[D.]]></given-names>
</name>
<xref ref-type="aff" rid="A01"/>
</contrib>
</contrib-group>
<aff id="A01">
<institution><![CDATA[,Instituto Universitario de Xeoloxía Isidro Parga Pondal  ]]></institution>
<addr-line><![CDATA[Coruña ]]></addr-line>
<country>Spain</country>
</aff>
<pub-date pub-type="pub">
<day>00</day>
<month>00</month>
<year>2010</year>
</pub-date>
<pub-date pub-type="epub">
<day>00</day>
<month>00</month>
<year>2010</year>
</pub-date>
<numero>97</numero>
<fpage>71</fpage>
<lpage>80</lpage>
<copyright-statement/>
<copyright-year/>
<self-uri xlink:href="http://scielo.pt/scielo.php?script=sci_arttext&amp;pid=S1647-581X2010000100005&amp;lng=en&amp;nrm=iso"></self-uri><self-uri xlink:href="http://scielo.pt/scielo.php?script=sci_abstract&amp;pid=S1647-581X2010000100005&amp;lng=en&amp;nrm=iso"></self-uri><self-uri xlink:href="http://scielo.pt/scielo.php?script=sci_pdf&amp;pid=S1647-581X2010000100005&amp;lng=en&amp;nrm=iso"></self-uri><abstract abstract-type="short" xml:lang="en"><p><![CDATA[The run-off infiltration through the discontinuities of the granitic rocky massifs causes the alteration of the rock and the associated formation of deposits which are considered speleothems due to the environment and genetic process where they are formed. Speleothems are formed by minerals (opal-A, pigotite, struvite, evansite-bolivarite, taranakite, goethite, etc.) whose constituent elements come from the rock weathering by the water strengthened by the biological activity that is developed in the fissural system and that modifies the geochemical properties of the water increa­sing its corrosivity. The fabric of these speleothems is highly porous and allows the development of microorganisms either in the voids or on the surface of the speleothem. There have been identified colonies of bacteria, cells, fungi hyphae, spores, algae, diatoms, polychetes, mites, etc., organisms that at least develop part of their vital cycle in the speleothem and that have an active role in the construction of speleothems when acting as deposition nuclei or sedimentary trap of the mobilized materials. The development of speleothems is intermittent and associated with water circulation episodes normally coupled with rain events.]]></p></abstract>
<abstract abstract-type="short" xml:lang="pt"><p><![CDATA[A infiltração do escoamento através das descontinuidades dos maciços rochosos graníticos provoca a alteração das rochas e a formação de depósitos associados que são considerados espeleotemas, devido ao ambiente e ao processo genético, onde são formadas. Espeleotemas são formados por minerais (opala-A, pigotite, estruvita, evansite-bolivarite, taranakite, goethita, etc.), cujos elementos constituintes provêm do intemperismo de rocha pela água reforçada pela atividade biológica que se desenvolve no sistema fissural e que modifica as propriedades geoquímicas da água aumentando a sua agressividade. A fabric destes espeleotemas é altamente porosa e permite o desenvolvimento de microorganismos, quer nos vazios ou na superfície do espeleotemas. Foram identificadas colónias de bactérias, células, hifas de fungos, esporos, algas, diatomáceas, polychetes, ácaros, etc., os organismos que desenvolvem, pelo menos, parte do seu ciclo vital no espeleotemas e que têm um papel activo na construção de espeleotemas quando actuam como núcleos de deposição de sedimentos ou armadilha dos materiais mobilizados. O desenvolvimento dos espeleotemas é intermitente e associada a episódios de circulação de água normalmente associada a períodos de chuva.]]></p></abstract>
<kwd-group>
<kwd lng="en"><![CDATA[Granite cave]]></kwd>
<kwd lng="en"><![CDATA[biospeleothem]]></kwd>
<kwd lng="en"><![CDATA[opal-A]]></kwd>
<kwd lng="en"><![CDATA[pigotite]]></kwd>
<kwd lng="en"><![CDATA[struvite]]></kwd>
<kwd lng="en"><![CDATA[evansite]]></kwd>
<kwd lng="pt"><![CDATA[Cova granítica]]></kwd>
<kwd lng="pt"><![CDATA[bioespeleoteme]]></kwd>
<kwd lng="pt"><![CDATA[opala A]]></kwd>
<kwd lng="pt"><![CDATA[pigotite]]></kwd>
<kwd lng="pt"><![CDATA[struvite]]></kwd>
<kwd lng="pt"><![CDATA[evansite]]></kwd>
</kwd-group>
</article-meta>
</front><body><![CDATA[ <p ><b>Speleothems of Granite Caves</b></p>      <p >&nbsp;</p>      <p >Vidal Roman&iacute;, J. R.*; Sanjurjo S&aacute;nchez, J.*; Vaqueiro, M.*,**    &amp; Fern&aacute;ndez Mosquera, D.*</p>      <p >* Instituto Universitario de Xeolox&iacute;a Isidro Parga Pondal. 15071 A Coru&ntilde;a, Spain.</p>      <p >** CEM. c/ Manuel de Castro 8-3&ordm;D, 36201 Vigo, Spain.</p>      <p >E-mail and Fax of the corresponding author:</p>     <p > <a href="mailto:xemoncho@udc.es">xemoncho@udc.es</a>. Fax (0034) 981167172</p>      <p ><i>All the authors contributed equally to this work</i></p>      <p >&nbsp;</p>      <p ><b >Abstract</b></p>      ]]></body>
<body><![CDATA[<p >The run-off infiltration through the discontinuities of the granitic rocky    massifs causes the alteration of the rock and the associated formation of deposits    which are considered speleothems due to the environment and genetic process    where they are formed. Speleothems are formed by minerals (opal-A, pigotite,    struvite, evansite-bolivarite, taranakite, goethite, etc.) whose constituent    elements come from the rock weathering by the water strengthened by the biological    activity that is developed in the fissural system and that modifies the geochemical    properties of the water increa&shy;sing its corrosivity. The fabric of these    speleothems is highly porous and allows the development of microorganisms either    in the voids or on the surface of the speleothem. There have been identified    colonies of bacteria, cells, fungi hyphae, spores, algae, diatoms, polychetes,    mites, etc., organisms that at least develop part of their vital cycle in the    speleothem and that have an active role in the construction of speleothems when    acting as deposition nuclei or sedimentary trap of the mobilized materials.    The development of speleothems is intermittent and associated with water circulation    episodes normally coupled with rain events. </p>     <p ><b >Keywords</b>: Granite cave, biospeleothem, opal-A, pigotite, struvite, evansite.  </p>      <p >&nbsp;</p>      <p ><b>Espeleotemas de Cavernas Gran&iacute;ticas</b></p>      <p ><b >Resumo</b></p>     <p >A infiltra&ccedil;&atilde;o do escoamento atrav&eacute;s das descontinuidades    dos maci&ccedil;os rochosos gran&iacute;ticos provoca a altera&ccedil;&atilde;o    das rochas e a forma&ccedil;&atilde;o de dep&oacute;sitos associados que s&atilde;o    considerados espeleotemas, devido ao ambiente e ao processo gen&eacute;tico,    onde s&atilde;o formadas. Espeleotemas s&atilde;o formados por minerais (opala-A,    pigotite, estruvita, evansite-bolivarite, taranakite, goethita, etc.), cujos    elementos constituintes prov&ecirc;m do intemperismo de rocha pela &aacute;gua    refor&ccedil;ada pela atividade biol&oacute;gica que se desenvolve no sistema    fissural e que modifica as propriedades geoqu&iacute;micas da &aacute;gua aumentando    a sua agressividade. A fabric destes espeleotemas &eacute; altamente porosa    e permite o desenvolvimento de microorganismos, quer nos vazios ou na superf&iacute;cie    do espeleotemas. Foram identificadas col&oacute;nias de bact&eacute;rias, c&eacute;lulas,    hifas de fungos, esporos, algas, diatom&aacute;ceas, polychetes, &aacute;caros,    etc., os organismos que desenvolvem, pelo menos, parte do seu ciclo vital no    espeleotemas e que t&ecirc;m um papel activo na constru&ccedil;&atilde;o de    espeleotemas quando actuam como n&uacute;cleos de deposi&ccedil;&atilde;o de    sedimentos ou armadilha dos materiais mobilizados. O desenvolvimento dos espeleotemas    &eacute; intermitente e associada a epis&oacute;dios de circula&ccedil;&atilde;o    de &aacute;gua normalmente associada a per&iacute;odos de chuva. </p>      <p ><b >Palavras-chave</b>: Cova gran&iacute;tica, bioespeleoteme, opala A, pigotite,    struvite, evansite. </p>      <p >&nbsp;</p>         <p ><b>1. INTRODUCTION </b></p>      <p >Run-off in continental zones is produced not only subaerially but also through    the system of discontinuities of the rocky massifs. The effects of the water    circulation through the massifs of non-soluble rocks (granite, quartzite) are    relatively well-known, (Urbani, 1996, Wray, 1997a, 1997b, 1997c, Twidale and    Vidal Romani, 2005). The first one is the chemical weathering (oxidation, hydration,    hydrolisation, solubilisation, etc.) of the rock then complementing it with    the mechanical or physical erosion. For the granite the weathering affects the    minerals that form the rock, mainly quartz, feldspar and mica ordered from minor    to greater susceptibility to weathering, in a different way. Water is the main    weathering agent though in granitic fissural environments the biological effect    has to be added as it contributes decisively to remark their effects (influence    on pH and Eh) when increasing the water aggressiveness in weathering processes.    Likewise, the velocity to which water flows through the fissural system has    influence on the weathering processes and also depends on different factors,    ones of general character (position of the base level, geomorphic stress (gravity),    dimensions of the conduits through which water flows) and other more specific    ones such as water movement by capillarity, superficial water tension or water    adherence to the conduit walls. From all the enumerated factors the ones that    influence more on the speleothem development are morphology and dimensions of    the conduit through which water circulates (Figs. 1a and 2a). Small conduits    will imply a slow water circulation, increasing the reactivity time of the water    with the rock and, therefore, the persistence of the chemical and biological    weathering. </p>     ]]></body>
<body><![CDATA[<p >&nbsp;</p>     <p ><img src="/img/revistas/cg/n97/n97a05f1.jpg" width="303" height="342"></p>     
<p >Fig. 1 &#8211; Opal-A speleothems: (a) Gypsum twins formed by planar crystals    on the tip of a speleothem. &Aacute;vila, Central Spain.; (b) Water output on    the ceiling of a granite cave with associated rim of opal-A stalactites; (c)    Opal-A coats the porous texture near the tip of speleothem from Traba Mountains,    Northern Galicia, Spain; (d) Opal-A grass-shaped stalactites on the ceiling    of a granite cave, Cova do Demo, Vigo, Spain; (e) Opal-A antistalactites from    Mina Clavero, C&oacute;rdoba, Argentina; (f) Opal-A stalagmite from Colegio    Lique&ntilde;o, Pampa de Achala, C&oacute;rdoba, Argentina.</p>     <p >&#8211; Espeleotemas de Opala-A: (a) Maclas de gesso formadas por cristais    planares na ponta de uma espeleotema (&Aacute;vila, Espanha Central); (b) Infiltra&ccedil;&atilde;o    de &aacute;gua no tecto de uma caverna gran&iacute;tica com bordos de estalactites    de opala-A associados; (c) A opala-A cobre a textura porosa perto da ponta de    uma espeleotema das Montanhas Traba (Norte da Galiza, Espanha); (d) Estalactites    de opala-A com &#8220;forma de relva&#8221; no tecto de uma caverna gran&iacute;tica    (Caverna do Demo, Vigo, Espanha); (e) Anti-estalactites de opala-A da Mina Clavero    (C&oacute;rdoba, Argentina); (f) Estalagmite de opala-A de Colegio Lique&ntilde;o    (Pampa de Achala, C&oacute;rdoba, Argentina).</p>     <p >&nbsp;</p>     <p ><img src="/img/revistas/cg/n97/n97a05f2.jpg" width="443" height="421"></p>     
<p ><a name="topf2"></a><a href="#f2">Fig. 2</a> &#8211; Different kinds of speleothems.    (a) Granite tafone from Los Gigantes (Sierra Grande de C&oacute;rdoba, Argentina):    the gray and black dots are the water outputs where the speleothems are formed;    (b) Pigotite column, covered by gour dam, 3000 years old from Trapa Cave, Gali&ntilde;eiro,    Galicia Spain; (c) Evansite deposits associated to planar fissure. Monte Costa    Grande, Muros, Coru&ntilde;a Spain; (d) Cross-section of a pigotite speleothem    formed by rhythmic accretion, with dark and light layers from Trapa Cave, Gali&ntilde;eiro,    Galicia Spain.</p>     <p >&#8211; Diferentes tipos de espeleotemas. (a) Tafone de granito de Los Gigantes    (Sierra Grande de C&oacute;rdoba, Argentina): os pontos cinzentos e pretos s&atilde;o    infiltra&ccedil;&otilde;es de &aacute;gua onde as espeleotemas se formam; (b)    Coluna de pigotite coberta por uma micro-barragem com 3000 anos de idade da    Caverna Trapa (Gali&ntilde;eiro, Galiza, Espanha); (c) Dep&oacute;sitos de evansite    associados a fissura planar (Monte Costa Grande, Muros, Corunha, Espanha); (d)    Perfil transversal de uma espeleotema de pigotite formada por acre&ccedil;&atilde;o    r&iacute;tmica com camadas escuras e claras na Caverna Trapa (Gali&ntilde;eiro,    Galiza, Espanha).</p>     <p >&nbsp;</p>     <p >Early reports described the deposits only considering their morphology, being known as coralloids, crusts, speleothems, etc. (Caldcleugh 1829, Swarzlow and Keller, 1937, Finlayson, 1981, Finlayson, 1982, Finlayson and Webb 1985, Finlayson, 1986, Kashima, 1987). In later works, more precise terminology is used; the deposits associated with a punctual output of the water at the roof of the rock cavity are called stalactites; the ones due to the dripping on the ground of the cavity, stalagmites; while the ones formed from a laminar water flow over a place of any inclination from horizontal to vertical are called flowstones (Vidal Roman&iacute; et al., 2003). But in all cases the speleothem growth is controlled by the water contribution that justifies a preferential growth in the sense of the gravity with lineal or planar development when the dropping is either free or related to a surface of slope variable (Fig. 1b). But a reduction in volume or speed (they are related magnitudes) of the water flow channelled towards the speleothem will reduce the influence of the geomorphic stress (gravity) on the water movement, increasing the importance of the other forces that also has influence on the water movement: capillarity, viscosity, superficial tension, water adherence to the surface on which the speleothem develops giving rise to another type of speleothems such as grass-shaped speleothems, antistalactites (Vidal Roman&iacute; and Vaqueiro, 2007).</p>      ]]></body>
<body><![CDATA[<p >&nbsp;</p>     <p ><b>2. SPELEOTHEM MINERALOGY AND GENESIS</b></p>      <p >One of the features of the speleothems of granitic cavities is the chemical    composition that, though very varied, is always monomineral, what indicates    that are formed in only one process of mineralogenesis. The speleothem mineralogy    cited up to now is: evansite-bolivarite, struvite, pigotite, taranakite, allophane,    goethite, hematite, etc. (Webb, 1976, Mac&iacute;as et al., 1980, Hill and Forti,    1995) though the prevailing mineralogy of speleothems in granite rocks are opal-A,    pigotite and evansite-bolivarite. The geographic-climatic environments where    they have been described are also varied: temperate humid (Spain, Portugal,    United Kingdom, Germany, Poland, Czech Republic), tropical (Brazil, Venezuela,    Madagascar, Hawaii), arid (Australia, Argentina, Brazil, Nigeria, New Mexico,    USA) (Willems et al., 1998, 2002, Twidale and Vidal Roman&iacute; 2005). </p>      <p >Following there are described the more frequent mineralogical types found    in speleothems of granitic fissural environments and their relationship with    the biological processes developed inside them. </p>     <p >&nbsp;</p>     <p ><b><i>Opal-A speleothems. SiO<sub>2</sub>.15(H<sub>2</sub>O)</i></b></p>      <p >They are mainly formed by Si and H<sub>2</sub>O and are associated with the    fissural systems of acid rocks: granites, quartzites and quartz veins (Table    1).</p>     <p ><a name="topt1"></a></p>     <p ><b><a href="#t1">TABLE 1</a></b></p>     <p >Summary of elemental composition of speleothems obtained by EDS coupled to    SEM, from samples of diverse provenance.</p>     ]]></body>
<body><![CDATA[<p >S&iacute;ntese da composi&ccedil;&atilde;o elementar das espeleotemas obtida    por EDS acoplado a SEM de amostras de diversas proveni&ecirc;ncias.</p>     <p ><img src="/img/revistas/cg/n97/n97a05t1.jpg" width="807" height="373"></p>     
<p >&nbsp; </p>     <p >In the chemical composition of opal speleothems associated with granites,    Si and H<sub>2</sub>O prevail while, Al, Ca, Fe, Mg, Na, K, Cl and Ti are in    less proportion. Also, there are other elements of biogenic origin like S and    C. The DTA-GTA diagrams of opal-A speleothems show the endothermic peak of low    temperature (145&ordm;C) corresponding to dehydration and the exothermic peak    between 300 and 450&ordm;C (sometimes 500&ordm;C) due to organic matter oxidation    (Vidal Roman&iacute; and Vilaplana, 1984) (Vidal Roman&iacute; et al., 1998).    X-ray diffraction (Mac&iacute;as et al., 1979) shows the diffuse band between    8.8 &Aring; and 10 &Aring; corresponding to amorphous opal. For the development    of the opal-A speleothems the decisive step is the dissolution of Si of the    minerals of the granite, and especially of quartz, a process defined by the    water pH. In natural environments (with pH values between 5-8), the Si dissolution    included in the most stable crystalline structures (quartz) is very low (Welch    and Ullman, 1996). However, after the biogenic weathering by bacteria, fungi,    lichens silicates are dissolved and Si is easily mobilized (Ehrlich, 1996; Barker    et al., 1997; Furukawa and O&#8217;Reilly, 2007). The attack of lichens is very    aggressive both physically and chemically due to the high chelant ability of    the lichenic acids (Barker et al., 1997). Bacteria and fungi, ubiquitous in    superficial environments, also produce similar destructive effects (Ehrlich,    1996) by means of the production of organic acids of low molecular weight (mainly    oxalate) (McMahon and Chapelle, 1991, Barker et al., 1997) which increases the    solubility of quartz in the pH range 2.0-8.5 (Brady and Walter, 1990, Bennett,    1991). Opal-A speleothems are formed by precipitation of the dissolved Si by    oversaturation by evaporation and/or synthesis carried out by some organisms,    (e.g., diatoms). The so formed deposits present two types of textures: open    work (highly porous) (Fig. 1c) and massive non porous. The most frequent one,    especially in young speleothems, is the first and is formed by a porous agglomerate    of angulous clasts of opal-A. On the contrary, in older speleothems or of greater    dimensions, the texture is massive, with few voids as they have been infilled    with re-dissolved opal-A (Fig. 1b). SEM and petrographic microscope analyses    provide more information on shape and internal texture of speleothems. The speleothems    are developed according to the water flow towards the point where the speleothem    grows (Vidal Roman&iacute; and Vilaplana, 1984). A slow flow is the most suitable    for the development of speleothems, whichever type it is (blanket, branched    or cylindrical) (Vidal Roman&iacute; et al., 1998). Either cylindrical speleothems    or flowstones show identical porous texture. This is due to dehydration of silica    gel that produces angulous clasts of opal-A whose accumulation is a sediment    with open work texture (Fig. 1b). This porous fabric allows the circulation    and also the temporal water storage in the speleothem. The process is similar    for the flowstone where the water movement accumulates on the surface of the    rock marking the maximum overspill rim with glassy opal clast accumulations    of sinuous outline that allows damming water producing microgours or rimstone    (Figs. 1c, d and e). From the examination of thin sections (Twidale and Vidal    Roman&iacute;, 2005) of stalactites it may be appreciated the rhythmic texture    formed by layer-by-layer accretion as it occurs in their congeners in limestone    caves (Vidal Roman&iacute; and Vilaplana, 1984). As the preferential water circulation    in opal speleothems is mainly external, the rhythmic structure will be located    on the free ends of the stalactites (Fig. 1b). On the contrary, it has not been    observed in other types of speleothems (stalagmites, mini gour, anti-gravitational    stalactites, grass-shaped stalactites, etc.) (Vidal Roman&iacute; and Vaqueiro,    2007) not related to dripping but laminar flow or with water capillary movement.  </p>      <p >The porous fabric of the speleothems where water stores temporarily is the suitable place for the development of microbiological activity (Fig. 1f). Microorganisms have a role in the Si fixation either stabilizing the clasts themselves or incorporating the Si into their organic structures. It is the case of certain fungi that have molecules in their walls that cause the Si precipitation or in the silaffins of diatoms (Kr&ouml;ger et al., 1999). Additionally, organic acids produced by some organisms act as chelant compounds that have influence on the pH changes (Franklin et al., 1994, Welch and Ullman, 1996). </p>      <p >&nbsp;</p>        <p ><b>2.1. Formation of gypsum crystals</b></p>        <p >Some organisms (bacteria and fungi) decompose the organic material generating    reduced S (H<sub>2</sub>S) that quickly oxidises into SO4<sup>&#8211;2</sup><sup>    </sup>which is combined with the Ca of the plagioclases finally forming gypsum    (SO<sub>4</sub>Ca.2H<sub>2</sub>O), normally a mineral that is always associated    with opal speleothems. These gypsum crystals are idiomorphic and are normally    developed in the free end of the speleothem and correspond to the end of the    growing stage. They form a crest of gypsum whiskers giving rise to the so-called    cauliflower crystals (Vidal Roman&iacute; et al., 1998). Gypsum whiskers are    associated as druses where crystals appear twinned with astonishing idiomorphic    shape. They appear (Twidale and Vidal Roman&iacute;, 2005) as (1) prismatic    twins: monoclinic class 2/m, (2) acicular twins and (3) planar twins, respectively.    The growth of these whisker druses is produced inside of the last drop that    has concentrated on the free end of the speleothem. For drops located inside    the channels, acicular crystal beams are formed. For the ellipsoid drops, elongated,    along the sense of the gravity, the pseudoprismatic crystals will be formed,    while for platy drops (typical of the stalagmites), crystal druses or bevelled    planar twins limited by the upper surface of the drop. </p>      <p >&nbsp;</p>      <p ><b><i>Pigotite speleothems. </i></b></p>     ]]></body>
<body><![CDATA[<p ><i><b>Al<sub>4</sub>C<sub>6</sub>H<sub>5</sub>O<sub>10</sub>.13H<sub>2</sub>O&nbsp;    or&nbsp; 4Al<sub>2</sub> O<sub>3</sub>.C<sub>12</sub> H<sub>10</sub> O<sub>8</sub>.27H<sub>2</sub>O</b></i></p>      <p >This is a salt composed of alumina and organic acids formed on the surface    of the granite and typically found in granitic cavities (Table 1). It forms    incrustations on the walls of granitic fissures and caverns (Fig. 2b). This    mineral was early described by Johnston (1840) in coastal caves from Cornwall    (United Kingdom) and was dedicated to Rev. M. Pigot. Johnston (1840) considered    it as an organic substance derived from the decay of moist moorlands above the    cave what he calls mudesous acid, combined with Al (dominant) and Fe (secondary).    Due to its amorphous character, the information given by the existing bibliography    is not very precise when trying to define the chemical and mineralogical composition.    Pigotite is presented as stalactites, stalagmites, columns and flowstone covering    from horizontal surfaces to very stepped walls, even vertical. Up to now, the    biggest pigotite speleothem has been located by one of us (M. Vaqueiro (Fig.    2b)) in Serra do Gali&ntilde;eiro, Galicia, NW Spain and is formed by the union    of a stalactite and a stalagmite in a column of more than 1 metre long. A cross    or longitudinal section of that sample shows a rhythmic accretion structure    in concentric layers (Fig. 2d) as it occurs in calcite speleothems. The different    layers alternatively show light (Al prevails) (cream) and dark colours (Fe prevails)    (reddish chestnut) that seem to correspond to seasonal stages (winter-summer)    similar to the varves of lake deposits. On surface the aspect of these pigotite    deposits is slightly different presenting a crenulated morphology due to the    development of mini gours with dimensions from millimetres to some micra. For    the speleothems described in Galicia, NW Spain, the radiocarbon dating gave    an age ranging from 1500 years B.P. (O Fol&oacute;n System, Galicia, Spain)    to 3000 years B.P. (Trapa cave system, Gali&ntilde;eiro Sierra, Galicia, Spain)    what confirms a great continuity and quickly growth in the deposition process    even when compared to calcium carbonate speleothems. The quantity of water present    in this mineral is highly variable, but always important in natural conditions.    Once a sample is taken from the cave, the dehydration transforms the mineral    into a powdered mass with very little cohesion in a short time. </p>      <p >&nbsp;</p>      <p ><b><i>Evansite-bolivarite. </i></b></p>     <p ><i><b>Al<sub>3</sub>(PO<sub>4</sub>)(OH)<sub>6</sub>.6(H<sub>2</sub>O)- Al<sub>2</sub>(PO<sub>4</sub>)(OH)<sub>3</sub>.4-5(H<sub>2</sub>O)</b></i></p>      <p >These kinds of speleothems are found in well jointed rocky massifs with development    of sheet structure. All these types of speleothems display a typical structure    in rhythmic layers or layered sequences (flowstone), some centimetres thick    covering surfaces of various square metres (<a name="f2"></a><a href="#topf2">Fig.    2c</a>). The colour of evansite is yellow to yellowish brown to reddish. Evansite    is amorphous and massive with a morphology in botryoidal or reniform coatings;    concentric, colloform structure at times; opaline; stalactitic. They are very    frequent in Galicia, NW Spain, but also in other parts of the World (Mt. Zeleznik,    Gomor, Slovakia). A mineral species related to evansite and also amorphous is    the bolivarite defined for the first time in Campo Lameiro, Pontevedra, Spain    (Navarro and Barea 1921), which is shown to have physical and optical properties    similar to those of evansite. Both minerals are X-ray amorphous. According to    previous literature (Garc&iacute;a-Guinea et al., 1995), DTA spectra of both    minerals show a strong endothermic effect at 120 &ordm;C and a weaker one at    399 &ordm;C. IR spectra show absorption peaks at 3500, 1600 and 100 cm (super    &#8211;1), which are attributed to OH, H<sub>2</sub> O and PO<sub>4</sub>, respectively.    NMR spectra give a P signal centred at &#8211;10.7 ppm, typical of amorphous    phosphates, and an Al signal centred at &#8211;4.2 ppm, which is typical of    Al in octahedral coordination. Chemical analyses give the empirical formula    Al<sub>2</sub> (PO<sub>4</sub>) (sub 0.92) (OH) (sub 3.25) .4.03H<sub>2</sub>O    for bolivarite and Al<sub>3</sub> (PO<sub>4</sub>) (sub 1.09) (OH) (sub 5.73)    .7.77H<sub>2</sub>O for evansite. The results of analyses of specimens of hydrous    aluminium phosphates from Costa Grande (Galicia, Spain) indicate a range of    Al:P atomic ratios varying between 2 and 3.58. Because of the amorphous nature    of these materials, it is difficult to know if these analytical data pertain    to mixtures of hydrous aluminium phosphates or if bolivarite and evansite represent    intermediate members of a wide solid-solution series in which PO<sub>4</sub>    radicals are replaced by 3(OH). Some authors, (Mart&iacute;n Cardoso and Parga    Pondal, 1935; Garc&iacute;a-Guinea et al., 1995), believe that under the name    of evansite-bolivarite there may be represented transition terms between alumina    silicates and alumina phosphates where the phosphorous that appears in them    increases progressively as Si diminishes till substituting it completely. </p>      <p >&nbsp;</p>      <p ><b>3. BIOLOGICAL ACTIVITY IN SPELEOTHEMS</b></p>      <p >In the fissural systems developed in granitic rocks through which water circulates,    different traces of biological activity may be recognized: organisms s.s.; pollen    and spores and products of biological activity (organic S, P and C). All these    organic remains are also distinguished if they come from outside the fissural    system (allochthonous) or from biological activity in the same fissure (autochthonous).  </p>      <p >&nbsp;</p>        ]]></body>
<body><![CDATA[<p ><b>3.1. Allochthonous remains</b></p>      <p >They come from organisms that develop most of their vital cycle outside the    fissural system where the speleothem will be formed or when they correspond    only to reproductive forms (pollen or spores). Up to now, there have been identified:    Polychaetes (Polychaeta) (Fig. 3a), Arthropod Mytes sp. (Acarus) (Fig. 3b),    palynomorphs of Pinaceae, Oleaceae, Mimosaceae, Poaceae, Brassicaeae (Fig. 3c),    Cyperaceae (Fig. 3d), Fagaceae, Anacardiaceae, etc., spores of ferns (Pteridophyta)    (Fig. 4a) and Dinophyceae.</p>      <p >&nbsp;</p>     <p ><img src="/img/revistas/cg/n97/n97a05f3.jpg" width="390" height="293"></p>       
<p >Fig. 3 &#8211; Organisms found in opal-A speleothems (I): (a) Polychete on    the surface of an opal-A speleothem from Eyre Peninsula, South Australia; (b)    Pollen grain of Brassicaceae from Cerros Blancos, Pampa de Achala, C&oacute;rdoba,    Argentina (courtesy of L. de Villar Seoane); (c) Mite trapped in a gour dam    of opal-A from Cerros Blancos, Pampa de Achala, C&oacute;rdoba, Argentina; (d)    Pollen grain of Anacardiaceae from Cerros Blancos, Pampa de Achala, C&oacute;rdoba,    Argentina (courtesy of L. de Villar Seoane).</p>      <p >&#8211; Organismos encontrados nas espeleotemas de opla-A (I): (a) Poliquetas na superf&iacute;cie de uma opala-A da Pen&iacute;nsula Eyre (Sul da Austr&aacute;lia); (b) Gr&atilde;o de p&oacute;len de Brassicaceae de Cerros Blancos (Pampa de Achala, C&oacute;rdoba, Argentina) (cortesia de L. de Villar Seoane); (c) &Aacute;caro preso numa micro-barragem de opala-A de Cerros Blancos (Pampa de Achala, C&oacute;rdoba, Argentina); (d) Gr&atilde;os de p&oacute;len de Anacardiaceae de Cerros Blancos (Pampa de Achala, C&oacute;rdoba, Argentina) (cortesia de L. de Villar Seoane).</p>      <p >&nbsp;</p>     <p ><img src="/img/revistas/cg/n97/n97a03f4.jpg" width="592" height="196"></p>     
<p >Fig. 4 &#8211; Organisms found in opal-A speleothems (II): (a) Spore of Pteridaceae,    Pampa de Achala, Argentina; (b) Algae Oscillatoria sp Pampa de Achala, Argentina;    (c); Cyanobacteria filaments, Cerros Blancos, Argentina. (d) Germinated Ascospores,    Pampa de Achala, Argentina. (e). Diatom frustule of Planothidium sp, Colegio    Lique&ntilde;o, Argentina. (f). Diatom frustules of Stephanodiscus sp, Cerros    Blancos, Argentina. (courtesy of L. de Villar Seoane).</p>     <p >&#8211; Organismos encontrados nas espeleotemas de opla-A (II): (a) Esporo    de Pteridaceae (Pampa de Achala, Argentina); (b) Algae Oscillatoria sp (Pampa    de Achala, Argentina); (c) Filamentos de cianobact&eacute;ria (Cerros Blancos,    Argentina); (d) Ascosporos germinados (Pampa de Achala, Argentina); (e) Fr&uacute;stula    diatom&aacute;cea de Planothidium sp (Colegio Lique&ntilde;o, Argentina); (f)    Fr&uacute;stula diatom&aacute;cea de Stephanodiscus sp (Cerros Blancos, Argentina)    (cortesia de L. de Villar Seoane).</p>     ]]></body>
<body><![CDATA[<p >&nbsp;</p>       <p ><b>3.2. Autochthonous remains </b></p>      <p >The term autochthonous is used here in the sense of organisms that develop naturally in the speleothems though they may be cosmopolitan species. Vegetative forms and forms of resistance are found in the speleothem developed in their vital cycle. Up to now, there have been identified: heterotrophic bacteria and cyanobacteria, filamentous ones (Schizotrix (Figs. 4b and c), Anabaena, Nostoc), unicellular (Xenococcaceae and other unidentified ones), Algae in developed colonies and as resistance forms like cistes and spores. There are observed unicellular individuals and colonies of pennal diatoms (Neidium, Synedra, Sellaphora, Odontidium sp.) and central diatoms (Melosira, Aulacoseira, Stephanodiscus sp.) (Fig. 4e and f), Crysophyceae (Cryptomonas sp.), haptophyta, among other undentified ones, fungi like spores and unicellular and multicellular vegetative forms (hyphae). There are observed hyphae of Basiomicetes, unicellular fungi (Ascomycetes and Mixomycetes) and Protozoa that appear as isolated individuals or rarely grouped.</p>      <p >&nbsp;</p>        <p ><b>3.3. Products of organic activity</b></p>      <p >They are mainly represented by organic C, P and S (<a name="t1"></a><a href="#topt1">Table    1</a>) as proved by the isotopic fractionation of S of some of them though no    trace of the organism is recognized in them. These 3 elements do not appear    individua&shy;lized but combined with other mineral components pertaining to    the rock giving place to minerals like evansite-bolivarite, struvite, pigotite,    taranakite, etc. </p>      <p >The 3 types of organic remains described in the speleothems allow the reconstruction with high accuracy of the ecological conditions of the microenvironment of the speleothem and of the adjoining environment where it is developed. Another aspect to be underlined is that these organic remains have an important role in the development of speleothems when acting as physical trap to fix the opal clasts of the speleothems or even when acting as precipitation nuclei of the different substances that carry water in dissolution. Another important effect is the role that they have, especially the waste of organic activity (C, P and S) when changing the conditions of the pH originating the precipitation or the complexation of Si and Al giving place to speleothems of evansite-boliviarite, opal, pigotite or even to the growth of crystals of calcium sulphate, calcium carbonate, phosphate, etc. </p>      <p >&nbsp;</p>      <p ><b>4.</b> <b>DISCUSSION</b></p>      <p >The weathering of granitic rocky massifs is carried out inside their fissure system when this is partially open and allows the water circulation through it at very slow speed. In the weathering process of the granite the microbiological activity has an important role as it accelerates its decay (Ca&ntilde;averas et al., 2001). The mobilization of the mineral ions coming from the rock depends on the water pH at the same time closely related to the content in organic matter that depends on the microbiological activity (Barker et al., 1997). The chemical elements of the rock minerals are dissolved and will be deposited close to their initial position creating the speleothems. The precipitations of Si, Al and organic matter are produced by oversaturation due to water evaporation.</p>      ]]></body>
<body><![CDATA[<p >When Si, Al and humic acids precipitate, opal-A, evansite-bolivarite and pigotite speleothems are produced respectively. However, the biological influence on the speleothem development does not finish with the first deposition but is renewed after each new episode of rainwater circulation, what explains the varved structure seen in the speleothems, for example the ones described in this paper of evansite-bolivarite, pigotite and opal-A, similar to the ones of the speleothems of carbonated or soluble rocks. </p>      <p >Though the speleothems described herein are associated with systems of discontinuities in partially open granitic rocks and with water circulating through them, the other factor clearly related to the development of speleothems is the interference with the biological activity developed either in the same subterranean environment or outside it. The distinction between allochthonous and autochthonous organic elements clearly shows that the same organisms or their activity products are the ones that influence on the development of the speleothems what allow to reasonably classifying them as biospeleothems for their close relation either in the genesis of the new minerals, in the precipitation mechanisms or in the weathering processes of the rocky substratum. A clear example of this relationship, microorganism and speleothem development, is the diatom colonies associated with opal-A speleothems. Some authors (Kashima 1987; Forti 2001) have supposed that the diatoms are alien to the system presuming that they are introduced from outside by the rainwater infiltrated in the rocky fissure system. Whichever their origin is, external or internal, they have a clear development in the same speleothem (Vidal Roman&iacute; et al., 1998) having direct or indirect influence on the final aspect of the speleothem. These associations may be specially observed in the drop associated with the free end of the cylindrical speleothem (Vidal Roman&iacute; et al., 1998) though they may also appear on their external surface or in any small concavity where water accumulates temporarily. The development of diatom colonies is reduced progressively as water evaporation is transformed into silica gel which finally will totally cover the diatoms incorporating them to the speleothem as fabric elements. Another element of influence of the organic activity in the speleothem development is the sulphates produced by oxidation of organic matter (bacteria, fungi) that are combined with Ca coming from the alteration of the plagioclases giving place to gypsum crystals (whiskers) (Twidale and Vidal Roman&iacute;, 2005). Generally, whiskers are calcium sulphate crystals though in some cases (Vidal Roman&iacute;, 1983) calcium carbonates or phosphates have been found. The formation of whiskers of substances in low concentrations from a base of silica gel is a well-known process in lab experiments (Garc&iacute;a-Ruiz et al., 1981, Garc&iacute;a-Ruiz et al., 1982, L&oacute;pez Azevedo and Garc&iacute;a Ru&iacute;z, 1982) and allows the growth of very pure crystals and with good morphologic development. </p>      <p >&nbsp;</p>      <p ><b>5. CONCLUSIONS</b></p>      <p >The granite weathering in the fissural systems, partially open, are produced    by the interaction water-rock where there are involved not only the chemical    weathering but also microbiological processes either directly (conducted by    the same microorganisms) or indirectly (reactions between the rock and the metabolic    products derived from the organic activity). The microbiological activity enhances    the rock alteration and dissolves elements from rock minerals (Si and Al, preferably    and in less proportion others as Ca, K, Na, Fe) as other organic ones due to    the microbiological activity (S, P and C). The oversaturation by water evaporation    causes the precipitation of the elements and solubilised compounds originating    speleothems of pigotite (fulvic acids), evansite-bolivarite (Al and Si phosphates)    and opal-A (Si and H<sub>2</sub>O) combined with gypsum (S, C, O, H<sub>2</sub>O).    Opal-A is the most frequent and morphologically most diversified kind of speleothem    and the one in which the interaction between microorganisms and speleothem growth    is better shown. The mineralogical chemical composition of the speleothems are    an image of the influence of the chemical processes of the rock weathering and    of the ones related to microbiological activity developed in the rocky fissural    system materialized in the different types of speleothems. The pigotite speleothems    are formed when the biological effects prevail over the chemical ones; the evansite-bolivarite    ones would be an intermediate case, and finally the opal-A ones would be those    where the chemical effects prevail over the biological ones. All of them, however,    are a proof that at micro scale there exists a close relationship between chemical    weathering and biological activity in the rock weathering in the fissural environments    of granitic rocky massifs and of their relationship with the runoff that circulates    through them.</p>      <p >&nbsp;</p>      <p ><b>ACKNOWLEDGEMENTS</b></p>      <p >We thank Ana Martelli for the English translation of the paper in draft form and the help to eliminate many errors and inconsistencies. We gratefully acknowledge Dra. Liliana Villar de Seoane for the identification of biological remains in opal-A speleothems. This paper is a contribution to the Research Project BTE-CGL-2006-08996 of the Ministry of Education and Science of Spain. </p>      <p >&nbsp;</p>      <p ><b>REFERENCES</b></p>      ]]></body>
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<body><![CDATA[<p >Vidal Roman&iacute;, J. R. &amp; Vilaplana, J. M. (1984) &#8211; Datos preliminares para el estudio de espeleotemas en cavidades gran&iacute;ticas. Cadernos do Laboratorio Xeol&oacute;xico de Laxe, 7: 305-324. </p>      <p >Vidal Roman&iacute;, J. R. &amp; Vaqueiro, M. (2007) &#8211; Types of granite cavities and associated speleothems: genesis and evolution. Nature Conservation 63, 41-46. </p>      <p >Vidal Roman&iacute;, J. R., Bourne, J. A., Twidale, C. R. &amp; Campbell, E. M. (2003) &#8211; Siliceous cylindrical speleothems in granitoids in warm semiarid and humid climates. Zeitschrift f&uuml;r Geomorphologie, 47(4): 417-437. </p>      <p >Vidal Roman&iacute;, J. R., Twidale, C. R., Bourne, J. &amp; Campbell, E. M. (1998) &#8211; Espeleotemas y formas constructivas en granitoides. In: Investigaciones recientes en la Geomorfolog&iacute;a espa&ntilde;ola. (Ort&iacute;z, A. G. and Franch, F. S., Eds.) 1.&ordf; edici&oacute;n. Barcelona: Actas Reuni&oacute;n de Geomorfolog&iacute;a (Granada). 777-782. </p>      <p >Webb, W. B. (1976) &#8211; Cave minerals and speleothems. Book In: The science of speleology, Ford, T. D. and Cullingford, C. H. D., eds.). London: Academic Press, 267-328. </p>      <p >Welch, S. A. &amp; Ullman, W. J. (1996) &#8211; Feldspar dissolution in acidic and organic solutions: Compositional and pH dependence of dissolution rate. Geochimica et Cosmochimica Acta, 60(16), 2939-2948. </p>      <!-- ref --><p >Willems, L., Comp&egrave;re, P., Hatert, F., Pouclet, A., Vicat, J. P., Ek, C. &amp; Boulvain, F. (2002) &#8211; Karst in Granitic rocks, South Camerun: cave genesis and silica and taranakite speleothems. Terra Nova, 14: 355-362. &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;[&#160;<a href="javascript:void(0);" onclick="javascript: window.open('/scielo.php?script=sci_nlinks&ref=155088&pid=S1647-581X201000010000500001&lng=','','width=640,height=500,resizable=yes,scrollbars=1,menubar=yes,');">Links</a>&#160;]<!-- end-ref --><p >Willems, L., Compere, P. &amp; Sponholz, B. (1998) &#8211; Study of siliceous karst genesis in eastern Niger: microscopy and X-ray microanalysis of speleothems. Zeitschrift f&uuml;r Geomorphologie, 42(2), 129-142. </p>      <p >Wray, R. A. L. (1997a) &#8211; The formation and significance of coraline silica speleothems in the Sidney Basin, southeastern Australia. Physical Geography, 18(1): 1-17. </p>      <p >Wray, R. A. L. (1997b) &#8211; A global review of solutional weathering forms on quartz sandstones. Earth- Science Reviews. 42(3): 137-160. </p>      ]]></body>
<body><![CDATA[<p >Wray, R. A. L. (1997c) &#8211; The formation and significance of coraline silica speleothems in the Sidney Basin, southeastern Australia. Physical Geography, 18(1): 1-17. </p>        ]]></body><back>
<ref-list>
<ref id="B1">
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<person-group person-group-type="author">
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<surname><![CDATA[Willems]]></surname>
<given-names><![CDATA[L.]]></given-names>
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<given-names><![CDATA[J. P.]]></given-names>
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<article-title xml:lang="en"><![CDATA[Karst in Granitic rocks, South Camerun: cave genesis and silica and taranakite speleothems]]></article-title>
<source><![CDATA[Terra Nova]]></source>
<year>2002</year>
<numero>14</numero>
<issue>14</issue>
<page-range>355-362</page-range></nlm-citation>
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</back>
</article>
