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Zeolite occurrences in the Central Metasedimentary Belt of the Grenville Province, Ontario, Quebec and New York State.

The Grenville Geological Province of southeastern Canada and upstate New York has long been known as a source for fine specimens of medium-grade to high-grade metamorphic and skarn minerals, but not zeolites. Recent re-examination of many well-known older localities as well as several new localities has resulted in the discovery of 21 species of zeolites, a number of which occur in collector-quality specimens.

INTRODUCTION

In spite of a long history of mining and mineral specimen production, there are relatively few reports of zeolites in Grenvillian rocks. Willimott (1884) reported chabazite and natrolite from the Haldane Mine and stilbite from the Moore (Seybold) Mine, Gatineau Co., Quebec. Spence (1920) noted the presence of stilbite and heulandite in fluorapatite-phlogopite skarn deposits, and Hoffman (1901) reported faujasite from the Daisy mine, Papineau Co., Quebec. Moyd (1949) mentioned zeolites associated with a band of nepheline-bearing rocks in the Bancroft, Ontario area, and Corriveau (1985) noted thomsonite in an alkalic syenite from Lac Rouge, Labelle Co., Quebec.

The present study was prompted by a serendipitous discovery of well-formed crystals of gismondine, chabazite-Ca and mesolite in a road cut near Laurel, Quebec, by Canadian Museum of Nature staff in 1983. Over the next decade, approximately 1000 road cuts, mines and test pits in the Central Metasedimentary Belt (CMB) and Central Metasedimentary Belt Boundary Zone (CMBBZ) of the Grenville across southern Quebec, southeastern Ontario and northwestern New York State were examined. In all, 101 occurrences containing zeolite mineralization were discovered, and 21 zeolite species were identified (Tables 1 and 2), including the third world occurrence of brewsterite-Ba and the rare species heulandite-Sr. The geochemically associated non-zeolite minerals prehnite, datolite and the apophyllite series were also noted at a number of localities.

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A band of Fluorapatite-Phlogopite Skarn (FPS) deposits and related metasedimentary rocks located in the approximate geographical center of the CMB, and north of the Ottawa-Bonnechere Graben (OBG), hosts the majority of occurrences. However, we have also found zeolites in various granitic pegmatites, nepheline syenitic pegmatites, fractured diabase dikes, calc-silicate gneisses and fenites in the same area, and in agpaitic rocks and calc-silicate skarns in the CMBBZ. Interestingly, no zeolites have been found in any of the above-mentioned lithologies located south of the OBG.

The zeolite nomenclature used in this paper corresponds to that recommended by the International Mineralogical Association (IMA) (Coombs et al., 1997).

GEOLOGIC SETTING

A comprehensive overview of Grenville geology and mineralogy is well beyond the scope of this study, and is best gained from a large number of other sources (e.g., Shaw et al., 1963; Wynne-Edwards, 1972; Davidson et al., 1979; Davidson et al., 1990; Moore et al., 1986; Robinson and Chamberlain, 1982; Windley, 1988; Rivers et al., 1989; Sabina, 1986). The majority of zeolite occurrences described here are in rocks within or adjacent to the Central Metasedimentary Belt (CMB) of the Grenville Province, probably an ancient island arc, composed largely of Precambrian marbles, gneisses, amphibolites, granites, syenites, etc., formed by tectonic and plutonic mountain-building events (Grenville orogeny) at ~950-1080 Ma, during which amphibolite-to-granulite facies conditions were attained. The Central Metasedimentary Belt Boundary Zone (CMBBZ) separates the CMB from the Central Gneiss Belt (CGB) to the west; its eastern border is defined by the Carthage-Colton mylonite zone and Labelle shear zone. The CMBBZ is characterized by brecciated carbonate metasediments, and is host to intrusions of nepheline syenite along its length. Other igneous intrusions paralleling the CMBBZ and north of the Ottawa-Bonnechere Graben (Kumarapeli and Saull, 1966) include the Cawood nepheline syenite complex (Currie, 1976), the St. Veronique and Lac Rouge K-rich to shoshonitic plutons (Corriveau, 1984, 1985), nepheline syenite intrusions near the Cabonga Reservoir (Brunet and Martignole, 1994), and the Wakefield batholith (Hogarth, 1970).

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During the Paleozoic, much of the southern portion of the study area was covered by sediments (sandstones, sandy dolostones, shales and limestones) to a depth of 2-3 km (Sanford, 1993). Minor igneous activity is recorded by the Onslow Syenite and Buckingham Latite (575 Ma) and the Buckingham peridotite (275 Ma). Hydrothermal mineralization along reactivated faults and fractures at 186.6 Ma resulted in a number of Rossie-type galena-calcite and related gash vein deposits (Robinson et al., 2001). The passage of a "hot spot" during Cretaceous time resulted in the alkaline Monteregian intrusives to the east, and may have thermally affected areas in the Gatineau terrain. The Blackburn carbonatite within the field area is similar in age to the Oka carbonatite complex, 110 km to the east (Hogarth et al., 1988).

Younger rocks are unknown in the region; if they were once present they were probably eroded by Pleistocene glaciation, the last remnants of which receded approximately 12,000 years ago. Current isostatic rebound in the area is estimated to be at a rate of about 3 mm per annum (Andrews, 1970), with seismic activity evident, particularly in the Ottawa area.

MINERALOGY

X-ray diffraction and electron microprobe analyses were used to identify all minerals. Chemical analyses were obtained from a JEOL 733 electron microprobe in wavelength-dispersion (WDS) mode using Tracor Northern 5500 and 5600 automation. Operating conditions were 15 kV accelerating voltage, 20 nanoampere beam current and a 30 micron beam diameter to minimize volatilization and decomposition during analysis. A conventional ZAF routine in the Tracor Northern TASK series of programs was used to correct raw data for absorption, fluorescence and atomic number effects, and water was calculated by stoichiometry. Results for selected samples are presented in Table 3.

X-ray powder diffraction patterns were obtained using a 114.6 mm diameter Debye-Sherrer camera with Ni-filtered [Cu.sub.K][alpha] radiation on a Phillips 811801 X-ray generator operated at 44 kV and 22 mA. Refined unit cell dimensions were derived utilizing the computer program CELREF (Appleman and Evans, 1973). Results for selected samples are presented in Table 4.

Analcime Na[Al[Si.sub.2][O.sub.6]] x [H.sub.2]O

Analcime has been found in calc-silicate skarn at FPS and other contact skarn deposits, as well as in granitic pegmatite and nepheline ([+ or -] corundum) syenite. At locality 5 (FPS deposit) it occurs as 0.5-mm colorless, translucent to transparent trapezohedral crystals and shells in cavities in heavily etched meionite. While morphologically cubic, lower symmetry is apparent optically in these crystals, with sector zoning and weak anisotropy evident. The paragenetic sequence of the zeolite mineralization at this locality is calcite(I) [right arrow] chabazite [right arrow] thomsonite [right arrow] mesolite [right arrow] analcime [right arrow] calcite(II) [right arrow] illite.

At locality 44, pseudomorphs of albite after trapezohedral analcime crystals up to 1 cm were found in fine-grained, massive laumontite associated with meionite, titanite, fluorapatite and rare zircon. At locality 68, analcime forms translucent, white, trapezohedral crystals to 0.5 mm associated with an apophyllite series mineral in a microcline-albite-quartz-calcite pegmatite, and at locality 86 it occurs as a white, powdery, surface alteration on nepheline.

Brewsterite-Ba (Ba,Sr)[.sub.2][[Al.sub.4][Si.sub.12][O.sub.32]] x 10[H.sub.2]O

Barium-dominant brewsterite occurs in cavities in prehnite at locality 97, where it forms pale yellow to colorless pinacoidal crystals and aggregates to 1 mm associated with prehnite, quartz, diopside, calcite, wollastonite and microcline. For a complete description, see Robinson and Grice (1993) and Chamberlain et al. (1999). Other than harmotome, brewsterite-Ba is the only barium-dominant zeolite known from the Grenville Province. This occurrence is the third known in the world for the mineral.

Chabazite-Ca ([Ca.sub.0.5], K,Na)[.sub.4][[Al.sub.4][Si.sub.8][O.sub.24]] x 12[H.sub.2]O

Chabazite-Ca is clearly the predominant chabazite species found in the Grenville. At most localities it forms transparent to translucent, colorless to white rhombohedral crystals with or without modifying {021} faces. Crystals rarely exceed 5 mm, though a few exceptional crystals measuring 1 to 1.5 cm are known from localities 47 and 48. Occasionally, pale yellow (locality 35) to deep orange (locality 27) crystals are encountered. Simple penetration twins are common, and yellow to orange "phacolite-habit" twins occur at localities 7 and 90. Microprobe analyses of chabazite samples from thirty-seven localities show that most (thirty-two analyses) contain Ca>K>Sr>Ba, but some (eleven analyses) show Ca>Sr>K>Ba. While Ba and Na are low in all the analyses, the Na content of chabazites from pegmatites is higher than from other modes of occurrence. Otherwise, specific chemical correlations for specimens from the different modes of occurrence are not evident, suggesting that lithology may have played only a limited role in the formation of chabazite-Ca.

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One analysis (locality 6, an FPS deposit) yielded a composition with virtually equal Ca and K contents, suggesting the possible occurrence of chabazite-K in the CMB. This sample, which is physically indistinguishable from other chabazite-Ca specimens, consists of colorless, 1 to 2-mm rhombohedral crystals associated with heulandite-Ca and meionite. The sample also has the highest Mg content of all samples analyzed (0.34 apfu).

Cowlesite Ca[[Al.sub.2][Si.sub.3][O.sub.10]] x 5.3[H.sub.2]O

Cowlesite has been identified from a single occurrence (locality 48), where it forms lustrous white, silky, radiating crystal aggregates to 0.3 mm on a thin overgrowth of albite on a meionite crystal. Associated species include altered pyrite, allanite-(Ce) and intergrowths of levyne and erionite. The meionite crystal hosting the cowlesite was found loose in soil filling the bottom of a 2 X 1.5 X 1-meter solution cavity in brecciated calc-silicate skarn. Interestingly, identical meionite crystals attached to the cavity walls or enclosed in calcite were frequently covered with mesolite, but only crystals found in the soil contained the cowlesite-erionite-levyne assemblage.

Compared to other cowlesite, that from locality 48 contains more Sr and Ba, but has a similar Si:Al ratio (Nawas, 1984; Gottardi et al., 1985; Wise and Tschernich, 1975; Tschernich, 1992; Vezzalini et al., 1992).

Erionite Series (K,Na,[Ca.sub.0.5])[.sub.10][[Al.sub.10][Si.sub.26][O.sub.72]] x ~30[H.sub.2]O

Levyne Series ([Ca.sub.0.5],Na,K)[.sub.6][[Al.sub.6][Si.sub.12][O.sub.36]] x ~17[H.sub.2]O

An erionite-series mineral intimately intergrown with levyne forms lustrous white to gray, silky, asbestiform, radial crystal aggregates to 0.3 mm on meionite at locality 48 (see cowlesite description above). Both species were identified by X-ray diffraction. Because of the paucity of sample, no other determinative techniques were applied. The occurrence of these minerals on meionite in soil may represent a new genetic mode, as they have previously been reported only from basalt and tuffaceous rhyolite beds (Gottardi et al., 1985).

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Faujasite-Na (Na,[Ca.sub.0.5][Mg.sub.0.5]K)[.sub.3-4][[Al.sub.3-4][Si.sub.9-8][O.sub.24]] x 16[H.sub.2]O

Milky white octahedral crystals of faujasite-Na have been described from locality 75 (Hoffman, 1901), but its occurrence there remains unconfirmed. Associated species reported include fluorite, datolite, quartz, barite, chabazite, calcite, pyroxene, phlogopite, pyrite and pyrrhotite. Hoffman (1901) gives the analysis Si[O.sub.2] 48.7, [Al.sub.2][O.sub.3] 17.0, CaO 4.6, [Na.sub.2]O 3.2, [H.sub.2]O 26.0, sum 99.5 weight %, which yields a reasonably good empirical formula for faujasite-Na (based on 40 anions): ([Na.sub.1.11][Ca.sub.0.88])[S.sub.1.99][[Al.sub.3.56][Si.sub.8.69][O.sub.24.22]] x 15.78[H.sub.2]O. In the National Mineral Collection of Canada there are three specimens labeled "faujasite" from this locality matching the description given by Hoffman (1901). Each was analyzed by X-ray diffraction and microprobe and found to be a mixture of fluorite and datolite. Such a mixture could not have yielded the analysis found by Hoffman, and while we have no reason to doubt his identification of faujasite-Na from locality 75, neither can we confirm it.

Garronite Na[Ca.sub.2.5][[Al.sub.6][Si.sub.10]][O.sub.32] x 14[H.sub.2]O

Garronite has been identified by X-ray powder diffraction from locality 86, where it forms a white powder on nepheline crystals.

Gismondine Ca[[Al.sub.2][Si.sub.2][O.sub.8]] x 4.5[H.sub.2]O

Gismondine occurs with chabazite-Ca and prehnite in solution cavities developed in skarn at locality 48. The mineral occurs both as euhedral, pseudotetragonal, bipyramidal, colorless to white, opaque crystals up to 5 mm, and as elongated anhedral growths replacing meionite fibers parallel to the c axis of the meionite.

Harmotome ([Ba.sub.0.5],[Ca.sub.0.5],K,Na)[.sub.5][[Al.sub.5][Si.sub.11][O.sub.32]] x 12[H.sub.2]O

At locality 65 harmotome occurs as equant to long-prismatic, colorless to white, twinned euhedral crystals and divergent aggregates to 2 mm associated with fibrous white spherules of allanite-(Ce), fluorite, calcite, pyrite and montmorillonite in voids in brecciated feldspar. The feldspar is noticeably etched, and slicken-sided surfaces are evident on some specimens. Morvenite. Perier and cruciform twins are common; predominant forms include {100}, {010}, {001} and {110}. A source for the barium required to form harmotome is not evident. Microprobe analyses of both the feldspar and the muscovite from this locality found no detectable Ba, nor were any barite or other Ba-bearing minerals observed. Nine different barite veins cutting carbonate or siliceous meta-sediments within a 130-km distance were examined, but none was found to contain harmotome or any other zeolite mineral.

Heulandite Series ([Ca.sub.0.5],[Sr.sub.0.5],[Ba.sub.0.5],[Mg.sub.0.5],Na,K)[.sub.9][[Al.sub.9][Si.sub.27][O.sub.72]] x ~24[H.sub.2]O

Clinoptilolite Series (Na,K,[Ca.sub.0.5],[Sr.sub.0.5],[Ba.sub.0.5],[Mg.sub.0.5])[.sub.6][[Al.sub.6][Si.sub.30][O.sub.72]] x ~20[H.sub.2]O

Heulandite-Ca, heulandite-Sr and clinoptilolite-Ca have been identified from the study area. Of these, heulandite-Ca is by far the most abundant, and heulandite-Sr the rarest, occurring only at locality 46. Heulandite-Ca forms pearly, transparent to translucent, colorless, yellow, orange or white single crystals and spherical aggregates to 1 cm at a number of localities (Table 2). Observed crystal forms include {100}, {010}, {101} and {011}. Microprobe analyses of heulandite-Ca samples from the CMB show that they typically contain more Sr and Ba and less Na and Fe than does heulandite-Ca from volcanic or sedimentary occurrences, and at locality 46, Sr is the dominant cation in zones of some crystals.

Heulandite-Sr is a rare mineral, and this occurrence may represent its third reported locality. The mineral occurs as white to colorless, 0.5-mm crystals in a fractured 30 cm-wide granitic pegmatite vein that vertically crosscuts calc-silicate gneiss. The crystals are visually indistinguishable from heulandite-Ca, and show the forms {100}, {010}, {101} and {011}. Chabazite-Ca and stilbite-Ca are associated. A microprobe analysis of one Sr-dominant zone is given in Table 3, and unit cell dimensions refined from X-ray powder data for this sample are given in Table 4. The Ba content in this heulandite is also unusually high in comparison to those from other Grenville occurrences.

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Clinoptilolite-Ca has been identified from three localities (30, 48 and 56) in contact zones in calc-silicate skarn or gneiss. At locality 30 this mineral was found as translucent white crystals up to 1 mm on altered meionite, microcline and other minerals in a 50 X 20 X 15-cm pocket in a sheared pegmatitic rock in contact with a diopside-carbonate metasediment.

Laumontite [Ca.sub.4][[Al.sub.8][Si.sub.16][O.sub.48]] x 18[H.sub.2]O

At locality 44 laumontite has been identified as a compact, massive white vein-filling with albite pseudomorphs after analcime in carbonate metasediments. At locality 30 it occurs in an altered calc-silicate band in garnet-sillimanite gneiss as simple, white to red, prismatic crystals to 2 mm displaying forms {110} and {201}; as pseudomorphs after anhedral feldspar (?) crystals; and as tightly packed, radiating, pinkish white crystal aggregates with chabazite-Ca and clay minerals filling voids at the contact between the two rock types.

Mesolite [Na.sub.16][Ca.sub.16][[Al.sub.48][Si.sub.72][O.sub.240]] x 64[H.sub.2]O

Mesolite is a relatively common zeolite in the CMB, often observed in voids in calc-silicate skarn deposits where it forms lustrous white, divergent tufts of acicular crystals. Common associates are chabazite-Ca, stilbite-series species, stellerite and heulandite-Ca. The mesolite may form early or late in the paragenetic sequence. At locality 26, fibrous mesolite forms overgrowths on chabazite-Ca in cavities in diopside-meionite-phlogopite gneiss; at locality 47 it occurs as bundles of fibers associated with pumpellyite, chabazite-Ca, prehnite and thomsonite in voids in calcite and calc-silicate rock. At locality 52 it occurs as fibrous inclusions in phlogopite; at locality 21 it forms inclusions in heulandite-Ca; at locality 5 it appears as inclusions in chabazite-Ca; and at numerous localities it appears as overgrowths on and in cavities in meionite. Mesolite was identified by X-ray diffraction only, as its fibrous nature precluded its analysis by microprobe techniques.

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Natrolite [Na.sub.2][[Al.sub.2][Si.sub.3][O.sub.10]] x 2[H.sub.2]O

Scolecite Ca[[Al.sub.2][Si.sub.3][O.sub.10]] x 3[H.sub.2]O

Natrolite is frequently encountered in the nepheline-bearing metasediments, pegmatitic segregations in nepheline gneiss and nepheline syenite deposits that parallel the CMBBZ. Much of the altered nepheline from these deposits that was formerly called "hydronephelite" is in fact natrolite (Edgar, 1965; Moyd, 1990). Well-formed pseudotetragonal prismatic crystals to 2 cm or longer occur at localities 86 and 97. Those from locality 86 display forms {010}, {110}, {120}, {111} and {331} and are often flattened on {010}, while those from locality 97 are typically simpler, showing only {110} and {111} faces. Microprobe analyses of samples from each locality are given in Table 3. Scolecite has been identified by petrographic means from locality 19 (Donald Hogarth, personal communication, 1993).

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Stilbite-Ca ([Ca.sub.0.5],Na,K)[.sub.9][[Al.sub.9][Si.sub.27][O.sub.72]] x 28[H.sub.2]O

Stellerite Ca[[Al.sub.2][Si.sub.7][O.sub.18]] x 7[H.sub.2]O

Both stilbite-Ca and stellerite are found in the study area, though the former is far more abundant than the latter, occurring at nearly fifty localities. While stellerite has been confirmed from only five localities (6, 22, 26, 30 and 100), it may be more abundant than recognized, since not every stilbite-stellerite series mineral found was chemically analyzed. Furthermore, both species occur at localities 26 and 30, suggesting that some unanalyzed "stilbite" from those localities hosting stilbite-Ca may actually be stellerite. Visually, both minerals display similar colors and pseudo-orthorhombic crystal morphologies, making sight identification unreliable. Crystals are commonly translucent white, pale to deep orange, or pale yellow; they display (monoclinic) forms {100}, {010}, {001} and {111}, and are typically flattened on {010}.

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Microprobe analyses of these minerals show no distinguishing compositional differences between samples from different host rocks.

Thomsonite [Ca.sub.2]Na[[Al.sub.5][Si.sub.5][O.sub.20]] x 6[H.sub.2]O

Thomsonite occurs at localities 47 and 48 as bright white radiating tufts to 2 mm, porcelain-like growths on meionite exposed in cavities by the dissolution of calcite, or translucent tan spherical growths to 5 mm. Associated zeolites include gismondine, chabazite-Ca and mesolite. At locality 5, thomsonite is found as transparent to translucent, colorless to gray, elongated rectangular blades flattened on {001}, as cruciform twins, and as divergent crystal aggregates on altered meionite, diopside and fluorapatite crystals exposed in voids in FPS skarn. Observed forms include {100}, {010}, {001}, and {110}.

DISCUSSION

Much has been written on the paragenesis of zeolites, but little on their occurrence in high-grade metamorphic terrains. In his summary of the genetic modes of occurrence of zeolites, Gottardi (1989) notes that zeolites form during diagenesis or very low grade metamorphism in soils and lakes, in hydrologically open and closed systems, in geo-autoclaves and in marine sediments. A hydrothermal origin is invoked for zeolites in geothermal fields, hydrothermal ore deposits, pegmatites and feldspathic rocks, but there is little information concerning rock-forming zeolites in veins and vugs in "massive rocks." Numerous studies address the role of glass in zeolite genesis in silicic volcanic rocks (e.g., Barth-Wirsching and Holler, 1989; Hawkins, 1981), or hydrothermal zeolite mineralization in basic volcanics (e.g., Kristmannsdottir and Tomasson, 1978). Interestingly, Zen (1961) suggested that "the marginal parts of some ancient fold-belts may have zeolitic assemblages preserved despite the ravages of erosion, but simply have not been discovered." Additional reviews of the formational conditions and geological settings for zeolites are given by Coombs et al. (1959) and Pecover (1987).

Zeolites are known to form at near-atmospheric conditions, often below 70[degrees]C (Barrer, 1982). Because zeolites are indicative of relatively low-temperature environments, their widespread occurrence in the high-grade metamorphic terrain of the Grenville may appear suiprising, though thomsonite has been reported elsewhere from altered aplitic dykes, pegmatites and fractures in gneiss (Gottardi et al., 1985; Tschernich, 1992), and in calc-silicate rocks (Cross and Shannon, 1927; Hogarth and Griffin, 1980).

While most silicates are slow to dissolve in aqueous solutions at atmospheric conditions, alkali elements may be preferentially leached from some silicates under these conditions (Casey and Bunker, 1990). In the Grenville, dissolution of calcite, Na- and K-feldspars, meionite, nepheline and other rock-forming minerals probably contributed to the development of zeolites. Of these, meionite is perhaps most significant, playing a role somewhat analogous to that of glass in zeolite genesis in volcanic rocks and sediments. At the New York pegmatite (locality 65), muscovite is altered to clays, and feldspars are noticeably etched. Here, harmotome crystals occur on brecciated, etched feldspar with calcite, fluorite, cerian epidote/allanite-(Ce), chlorite and pyrite. Nepheline in a mesocratic syenite at Lac Rouge, Quebec (locality 76) is replaced by cancrinite and sodalite, which are subsequently altered to natrolite and thomsonite (Corriveau, 1984). Likewise, altered feldspathoids in the nepheline syenites in the Bancroft, Ontario area (formerly called "hydronephelite" or "giesekite") are mixtures of natrolite and muscovite, [+ or -] analcime and other minor constituents.

In FPS and other skarn deposits, zeolites occur in cavities in coarse-grained calcite, in joints and fractures in calc-silicate skarn and syenitic xenoliths, or as free-standing crystals on earlier-formed crystals of meionite, diopside, feldspars, titanite, fluorapatite, and other minerals that occur in cavities resulting from the dissolution of calcite once in contact with the skarn minerals. At locality 47 one such void contained meionite partially replaced by albite, titanite partially altered to anatase, and the zeolite paragenesis mesolite [right arrow] stilbite-Ca [right arrow] heulandite-Ca [right arrow] chabazite-Ca [right arrow] thomsonite. At the same locality, crystals of chabazite-Ca to 1 cm were found growing on a bridge of etched calcite spanning the walls of a solution cavity hosting large crystals of meionite and diopside-hedenbergite, proving that the pocket, like many in the area, was once tilled with calcite, and that the chabazite-Ca formed after its dissolution (probably by groundwater). Similar geological environments and mineralization were also observed at localities 21-27 and 48.

While the source of the water(s) responsible for calcite dissolution and zeolite mineralization is unknown, most was probably meteoric. The lack of fluid inclusions in the samples and difficulties associated with obtaining reliable stable isotope data from zeolites in general preclude securing definite information on the nature of the solution(s) responsible for zeolite mineralization. Likewise, the timing of zeolite mineralization remains unknown, though it clearly postdates the fracturing of the host rocks and the dissolution of calcite. There is no evidence in the geological record of hydrothermal activity in the area from 110 mA to present, unless the presence of these zeolites marks such an event. Earlier geological events that may have contributed to the mineralization include 1) a mantle plume such as that associated with the Monteregian Hills, 2) carbonatite emplacement in the Gatineau area (Hogarth et al., 1988), 3) Rossie-type vein mineralization (Robinson et al., 2001), 4) a thermal event associated with intrusions of Mesozoic dykes in southeastern Ontario (Barrett et al., 1984), and perhaps others.

It is also interesting to speculate that at least some of the observed mineralization may be Recent, due to uplift and weathering after the retreat of Pleistocene glaciers. At locality 48, thomsonite, cowlesite, levyne, mesolite and prehnite were found on meionite crystals that had dissolved from calcite in a soil-filled solution cavity in skarn within a meter of the present-day surface. Also here, and at other localities, sharp, unabraded chabazite-Ca crystals are present on rock surfaces that were almost certainly exposed to glaciation, and it is difficult to envision how they could have survived erosion by ice and ground moraine. The idea of low-temperature environments for zeolite formation is not new. Nashar and Davies (1960) suggest chabazite may form by slow crystallization from meteoric water at only 5[degrees]C, and Capdecomme (1952) reported laumontite formed by the reaction between plagioclase and water from melting snow. Zeolites are also known to form at low temperatures (45-75[degrees]C) in springs and geothermal wells (Kristmannsdottir and Tomasson, 1978), and heulandite has been observed on colemanite in borax deposits thought to have formed at less than 60[degrees]C (Tschernich, 1992).

SUMMARY

Source materials, geochemical signatures, and the ages of their host rocks differentiate zeolites found in the Grenville from those in most other geological settings. Many zeolites from the CMB have relatively high Sr contents. Despite their diverse host lithologies, most of the zeolites in the CMB probably share a common, low-temperature hydrothermal origin that involves leaching and subsequent precipitation of Ca, Na, Al, Si and other elements from their host rocks by solutions migrating along faults, fractures, shear zones, vugs or other open spaces that behaved as both conduits and repositories. While most are probably meteoric, both the source and age of these solutions remain unknown. Further exploration in the area will almost certainly reveal additional occurrences.

ACKNOWLEDGMENTS

We thank Scott Ercit and Donald Hogarth for their many helpful discussions, and Michel Picard for his assistance in the field. Steven Chamberlain provided locality information for some of the occurrences in the New York segment, and Court Saunders provided several specimens for analysis. We are grateful to Ralph Rowe for creating the map of the Grenville Province shown in Figure 1.

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Jerry Van Velthuizen* and Robert A. Gault

Canadian Museum of Nature, Research Division

P.O. Box 3443, Station D

Ottawa, Ontario, Canada K1P 6P4

George W. Robinson**

A. E. Seaman Mineral Museum

Michigan Technological University

1400 Townsend Drive

Houghton, Michigan 49931

Jeffrey Scovil

P.O. Box 7773

Phoenix, Arizona 85011

* deceased

** Research Associate, New York State Museum, Albany, NY
Table 1. Modes of occurrence of zeolites in the Central Metasedimentary
Belt.

Species                Mode of Occurrence*

 1) Analcime           1, 2, 4, 5
 2) Brewsterite-Ba     8
 3) Chabazite series   1, 2, 3, 9, 10
 4) Clinoptilolite-Ca  1
 5) Cowlesite          2
 6) Erionite series    2
 7) Faujasite-Na       1
 8) Garronite          5
 9) Gismondine         2
10) Gonnardite         5
11) Harmotome          4
12) Heulandite-Ca      1, 2, 3
13) Heulandite-Sr      4
14) Laumontite         2, 3
15) Levyne             2
16) Mesolite           1, 2, 3
17) Natrolite          5
18) Scolecite          6
19) Stellerite         1, 2, 3, 4, 7
20) Stilbite-Ca        1, 2, 3
21) Thomsonite         1, 2

* Modes of Occurrence: 1) fluorapatite-phlogopite skarn deposit, 2)
calc-silicate skarn or gneiss, 3) syenitic-to-gabbroic pegmatitic
segregations in skarn or gneiss, 4) granitic pegmatite, 5) nepheline
syenite, 6) fenite, 7) fracture filling in diabase, 8) prehnite veins in
wollastonite skarn, 9) calcite-prehnite vein in amphibolite gneiss, 10)
fracture filling in granitic gneiss.

Table 2. Zeolite localities in the central metasedimentary belt*.

Locality  Name           Host**  UTM(N)           UTM(E)

Quebec Segment
  1       Haldane         1      5300             3440
  2       Comet           1      5393             3615
  3       road cut        2      5540             3535
  4       road cut        4      4670             3603
  5       Horseshoe       1      5230             3360
  6       prospect        1      5540             3230
  7       Nellie Blanch   1      4195             3880
  8       Featherstone    1      4235             3850
  9       Dacey           1      4980             3688
 10       Thom            1      4950             3775
 11       Blackburn       1      4480             3815
 12       Dibbley         7      3295             3975
 13       outcrop         2      5075             3055
 14       road cut        2      4840             3457
 15       road cut        2      4653             3265
 16       road cut        3      4235             3695
 17       road cut        2      4110             3952
 18       prospect        1      4685             3455
 19       Haycock         6      4360             4210
 20       road cut        3
 21       road cut        3
 22       road cut        2      Series of road cuts on
 23       road cut        2      Highway 819 in
 24       road cut        2      vicinity of UTM 4550N
 25       road cut        2      and 0870-1030E
 26       road cut        2
 27       road cut        2
 28       road cut        7      8570             0280
 29       road cut        2      9190             2760
 30       road cut        2, 7   8820             2545
 31       prospect        1      4515             2440
 32       road cut        2      5275             2250
 33       Chaibee         1      9878             2125
 34       road cut        2      3275             2460
 35       road cut        2      3920             2450
 36       road cut        2      7175             2100
 37       road cut        2      5120             3952
 38       road cut        2      7250             2025
 39       Bain            2      6510             1150
 40       road cut        2      5530             2690
 41       Yates           2      9100             8045
 42       Giroux          2      7680             8130
 43       road cut        2      6895             8040
 44       road cut        2      6895             8150
 45       road cut        3      6970             8140
 46       road cut        4      3790             0330
 47       road cut        2      8427             3125
 48       road cut        2      7780             4250
 49       Seybold         1      5533             3755
 50       Gemmil          1      5920             4030
 51       road cut        2      6430             4415
 52       Breckin         1      5645             4530
 53       Jackson Rae     1      5130             5295
 54       Post            1      5240             5325
 55       Murphy          1      5125             5130
 56       King Edward     1      5810             5455
 57       road cut        2      4813             4763
 58       Laurin          1      5510             4625
 59       Millar          1      5320             5100
 60       Briggs          1      5830             4670
 61       Washington      1      6130             6285
 62       Emerald         1      5985             6180
 63       Aetna           1      5975             6185
 64       Penaud          4      6020             6442
 65       New York        4      5494             5799
 66       Terror Lake     1      6405             4970
 67       Crown Hill      1      7350             4950
 68       High Rock       1, 4   7045             5110
 69       High Rock       1, 4   7110             5095
 70       Allan           1      6565             4870
 71       Cameron         1      7200             5815
 72       France          1      6530             6145
 73       Watts Rapids    1      5970             6140
 74       road cut        3      6915             7880
 75       Daisy           1      6250             6410
 76       Lac Rouge       5      4200             7000

Ontario Segment
 77       road cut        2      1735             3795
 78       road cut        2      1750             3810
 79       road cut        2      1960             4040
 80       Hunt            2      1865             5070
 81       Klondike        5      1840             9520
 82       road cut        2      3100             0680
 83       Gutz Farm       5      2580             0690
 84       Wolfe           5      2300             1760
 85       Princess        5      9485             7916
 86       Davis Hill      5      9408             7915
 87       Egan Chute      5      9465             8470
 88       Golding-Keene   5      9408             8477
 89       Vardy           5      9510             7935
 90       Faraday         3, 4   8910             6965
 91       Burgess         5      1550             8850
 92       Monteagle       5      0265             8637
 93       prospect        1      0320             7520
 94       road cut        2      0020             7460
 95       Gill            5      7563             1040
 96       Fraser          5      7487             0884
 97       Blue Mountain   5      5100             6620

New York Segment
 98       Valentine       8      N44[degrees]07'  W75[degrees]22'
 99       road cut        9      N44[degrees]26'  W75[degrees]11'
100       Scott Farm      3      N44[degrees]13'  W75[degrees]05'
101       Benson Mines   10      N44[degrees]10'  W75[degrees]00'

Locality  Name           Map             Township          County

Quebec Segment
  1       Haldane        31G12           Lapeche           Gatineau
  2       Comet          --              --                --
  3       road cut       --              --                --
  4       road cut       --              --                --
  5       Horseshoe      --              --                --
  6       prospect       --              --                --
  7       Nellie Blanch  --              Hull              --
  8       Featherstone   --              --                --
  9       Dacey          --              --                --
 10       Thom           --              --                --
 11       Blackburn      --              --                --
 12       Dibbley        31G5            --                --
 13       outcrop        31G12           --                --
 14       road cut       --              --                --
 15       road cut       --              --                --
 16       road cut       --              --                --
 17       road cut       --              --                --
 18       prospect       --              --                --
 19       Haycock        --              --                --
 20       road cut       31K8            D'Angoumos        --
 21       road cut       --              --                --
 22       road cut       --              --                --
 23       road cut       --              --                --
 24       road cut       --              --                --
 25       road cut       --              --                --
 26       road cut       --              --                --
 27       road cut       --              --                --
 28       road cut       31F16           Clapham           --
 29       road cut       --              Hincks            --
 30       road cut       --              --                --
 31       prospect       --              Egan              --
 32       road cut       --              --                --
 33       Chaibee        --              Wright            --
 34       road cut       --              Maniwaki          --
 35       road cut       --              --                --
 36       road cut       --              Lytton            --
 37       road cut       31K9            --                --
 38       road cut       --              --                --
 39       Bain           31F9            Masham            --
 40       road cut       31G12           --                --
 41       Yates          31F15           Huddersfield      Pontiac
 42       Giroux         --              Litchfield        --
 43       road cut       --              --                --
 44       road cut       --              --                --
 45       road cut       --              Thorne            --
 46       road cut       31N05           --                --
 47       road cut       31G15           Harrington        Argentieul
 48       road cut       31G16           Wentworth         --
 49       Seybold        31G12           Val des Mont      Papineau
 50       Gemmil         --              --                --
 51       road cut       --              --                --
 52       Breckin        --              --                --
 53       Jackson Rae    --              Templeton         --
 54       Post           --              --                --
 55       Murphy         --              --                --
 56       King Edward    --              --                --
 57       road cut       --              --                --
 58       Laurin         --              --                --
 59       Millar         --              --                --
 60       Briggs         --              Templeton (Gore)  --
 61       Washington     31G11           --                --
 62       Emerald        --              --                --
 63       Aetna          --              --                --
 64       Penaud         --              --                --
 65       New York       --              --                --
 66       Terror Lake    31G12           Portland West     --
 67       Crown Hill     31G13           --                --
 68       High Rock      --              --                --
 69       High Rock      --              --                --
 70       Allan          --              --                --
 71       Cameron        --              Portland East     --
 72       France         --              --                --
 73       Watts Rapids   --              --                --
 74       road cut       31G14           Mulgrave          --
 75       Daisy          31G11           Derry             --
 76       Lac Rouge      31JGW           Kiamika           Labelle

Ontario Segment
 77       road cut       31F6            Griffith          Renfrew
 78       road cut       --              --                --
 79       road cut       --              Brougham          --
 80       Hunt           31F7            --                --
 81       Klondike       31F5            Raglan            --
 82       road cut       31F6            Brudenell         --
 83       Gutz Farm      --              --                --
 84       Wolfe          --              Lyndoch           --
 85       Princess       31F4            Dungannon         Hastings
 86       Davis Hill     --              --                --
 87       Egan Chute     --              --                --
 88       Golding-Keene  --              --                --
 89       Vardy          --              --                --
 90       Faraday        --              --                --
 91       Burgess        --              Carlow            --
 92       Monteagle      --              Monteagle         --
 93       prospect       --              --                --
 94       road cut       --              --                --
 95       Gill           31D16           Glamorgan         Haliburton
 96       Fraser         --              --                --
 97       Blue Mountain  --              Methuen           Peterborough

New York Segment
 98       Valentine      Lake Bonaparte  Diana             Lewis
 99       road cut       Russell         Russell           St. Lawrence
100       Scott Farm     Oswegatchie     Fine              --
101       Benson Mines   Oswegatchie     Clifton           --

Locality  Name           Species**

Quebec Segment
  1       Haldane        16
  2       Comet           3, 12
  3       road cut        3, 12, 16
  4       road cut        3, 12
  5       Horseshoe       1, 3, 12, 20, 21
  6       prospect        3, 12, 19, 20
  7       Nellie Blanch   3, 12, 16, 20
  8       Featherstone    3
  9       Dacey           3, 12, 16
 10       Thom            3
 11       Blackburn       3
 12       Dibbley         3, 12, 20
 13       outcrop         3, 12, 16
 14       road cut        3, 12, 16
 15       road cut        3, 12, 16, 20
 16       road cut        3, 12, 16, 20
 17       road cut        3, 12
 18       prospect        3
 19       Haycock        18
 20       road cut       20
 21       road cut        3, 12, 20
 22       road cut        3, 12, 20
 23       road cut        3, 12, 20
 24       road cut        3, 12, 20
 25       road cut        3, 12, 20
 26       road cut        3, 16, 19, 20
 27       road cut        3, 20
 28       road cut       20
 29       road cut        3, 14
 30       road cut        3, 4, 12, 14, 19, 20
 31       prospect        3, 12
 32       road cut        3, 12, 20
 33       Chaibee         3, 12, 16, 20
 34       road cut        3, 12, 16, 20
 35       road cut        3, 12, 16, 20
 36       road cut        3, 12, 16, 20
 37       road cut        3, 12, 16, 20
 38       road cut        3, 12, 16, 20
 39       Bain            3
 40       road cut        3, 12, 16
 41       Yates           3, 12, 20
 42       Giroux          3, 12, 20
 43       road cut        3, 12
 44       road cut        1, 14
 45       road cut        3, 12
 46       road cut        3, 12, 13, 20
 47       road cut        3, 12, 16, 21
 48       road cut        3, 4, 5, 6, 9, 12, 15, 16, 21
 49       Seybold         3, 12, 20
 50       Gemmil          3, 12, 20
 51       road cut       22
 52       Breckin         3, 12, 16, 20
 53       Jackson Rae     3, 12, 16, 20
 54       Post            3, 12, 20
 55       Murphy          3, 12, 20
 56       King Edward     3, 4, 12, 16, 20
 57       road cut        3, 12
 58       Laurin          3, 12, 20
 59       Millar          3, 12, 16
 60       Briggs          3, 12, 16, 20
 61       Washington      3, 12
 62       Emerald         3, 12, 16, 20
 63       Aetna           3, 12, 16, 20
 64       Penaud          3
 65       New York       11
 66       Terror Lake    18
 67       Crown Hill      3, 16, 20
 68       High Rock       1, 3, 12, 16, 20
 69       High Rock       3, 20
 70       Allan           3
 71       Cameron         3, 12
 72       France          3, 12, 20
 73       Watts Rapids    3, 12, 16, 20
 74       road cut        3, 20
 75       Daisy           3, 7
 76       Lac Rouge      17, 21

Ontario Segment
 77       road cut        3, 12, 20
 78       road cut        3, 12, 20
 79       road cut        3, 12, 20
 80       Hunt            3
 81       Klondike        3
 82       road cut        3, 12, 20
 83       Gutz Farm       1, 8, 10
 84       Wolfe           1, 12
 85       Princess        1, 17
 86       Davis Hill      1, 8, 17
 87       Egan Chute      1
 88       Golding-Keene  17
 89       Vardy           1
 90       Faraday         3
 91       Burgess         1, 17
 92       Monteagle      17
 93       prospect        3, 17
 94       road cut        3, 12
 95       Gill            1, 17
 96       Fraser          1
 97       Blue Mountain   1, 17

New York Segment
 98       Valentine       2
 99       road cut        3
100       Scott Farm      3, 12, 19, 20
101       Benson Mines    3

*The data in this table were accumulated by the senior author (deceased)
and have not been verified. They are presented here as a starting point
for the benefit of those wishing to visit some of these occurrences.
**As given in Table 1.

Table 3. Electron microprobe analyses for selected samples.

                     1      2      3        4       5       6

Si[O.sub.2]          55.29  47.80   41.79    54.20   54.03  63.93
Ti[O.sub.2]                                   0.08
[P.sub.2][O.sub.5]           0.10    0.14
[Al.sub.2][O.sub.3]  21.75  19.51   29.43    15.60   16.68  12.79
CaO                          8.59   15.56             3.06   4.54
SrO                          0.35    0.20             6.20   0.54
BaO                          0.21            22.80    4.42   0.13
MgO                                                          1.15
FeO
[Na.sub.2]O          13.93           0.78     0.09    0.05
[K.sub.2]O            0.30   0.32    0.05     0.08    1.51   0.88
[H.sub.2]O            0.30  20.99   25.88    16.32   14.71  13.15
Sum                  99.40  97.87  113.83*  109.17  100.66  97.12
[Si.sup.4+]           2.04   3.41    4.36    11.95   26.43  29.14
[Ti.sup.4+]                                   0.01
[P.sup.5+]                   0.01    0.01
[Al.sup.3+]           0.95   1.64    3.62     4.05    9.62   6.87
[Ca.sup.2+]                  0.66    1.74             1.60   2.22
[Sr.sup.2+]                  0.01    0.01             1.76   0.14
[Ba.sup.2+]                  0.01             1.97    0.85   0.02
[Mg.sup.2+]                                                  0.78
[Fe.sup.2+]
[Na.sup.1+]           0.99           0.16     0.04    0.05
[K.sup.1+]            0.01   0.03    0.01     0.02    0.94   0.51
N([H.sub.2]O)         1.00   5.00    9.00    12.00   24.00  20.00
# [O.sup.2-]          7.00  15.00   25.00    44.00   92.00  92.00

                     7       8      9       10       11     12     13

Si[O.sub.2]           50.93  45.61  45.66    59.55   35.78  35.59  36.78
Ti[O.sub.2]
[P.sub.2][O.sub.5]     0.07                           0.08   0.06   0.08
[Al.sub.2][O.sub.3]   21.71  26.12  25.94    18.19   30.25  30.11  29.32
CaO                   11.61          0.05     8.63   12.92  11.30  11.62
SrO                                                   1.05   3.01   2.08
BaO
MgO                    0.21
FeO                    0.40
[Na.sub.2]O                  16.29  16.41     0.94    3.73   3.75   4.15
[K.sub.2]O             0.31                   0.51
[H.sub.2]O            17.28   9.19   9.18    18.86   12.89  12.77  12.86
Sum                  102.52  97.21  97.24   106.68*  96.70  96.59  96.91
[Si.sup.4+]           15.91   2.98   2.98    26.51    5.00   5.01   5.14
[Ti.sup.4+]
[P.sup.5+]             0.02                           0.01   0.01   0.01
[Al.sup.3+]            7.99   2.01   2.00     9.54    4.98   5.00   4.83
[Ca.sup.2+]            3.89          0.003    4.12    1.93   1.71   1.74
[Sr.sup.2+]                                           0.09   0.25   0.17
[Ba.sup.2+]
[Mg.sup.2+]            0.10
[Fe.sup.2+]            0.10
[Na.sup.1+]                   2.06   2.08     0.81    1.01   1.02   1.12
[K.sup.1+]             0.12                   0.29
N([H.sub.2]O)         18.00   2.00   2.00    28.00    6.00   6.00   6.00
# [O.sup.2-]          66.00  12.00  12.00   100.00   26.00  26.00  26.00

* high sum probably due to decomposition during analysis
1: analcime, locality #5; 2: cowlesite, locality # 48; 3: gismondine,
locality 48; 4: harmotome, locality # 65; 5: heulandite-Sr, locality 46;
6: clinoptilolite-Ca, locality 30; 7: laumontite, locality 30; 8:
natrolite, locality 86; 9: natrolite, locality 97; 10: stilbite-Ca,
locality 42: 11: thomsonite, locality 5; 12: thomsonite, locality 47;
13: thomsonite, locality 48.

Table 4. X-ray data for selected samples.

Locality  Species        Cell Parameters (in [Angstrom]) and References

 5        analcime       a = 13.710(2) (cubic cell)
48        cowlesite      a 11.653(2), b 15.509(1), c 12.538(2) based on
                           orthorhombic cell of Wise and Tschernich
                           (1975)
48        gismondine     a 10.024(2), b 10.614(2), c 9.48(2), [beta]
                           92.28[degrees]
65        harmotome      a 9.806(2), b 14.191(3), c 8.697(2), [beta]
                           124.39[degrees] based on monoclinic cell of
                           Sahama and Lehtinen (1967)
46        heulandite-Sr  a 17.733(3), b 17.744(2), c 7.415(3), [beta]
                           116.20[degrees] based on JCPDS 24-469 (Cerny
                           and Povondra, 1969)
30        laumontite     a 14.935(3), b 13.047, c 7.510(2), [beta]
                           111.58[degrees]
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Author:Van Velthuizen, Jerry; Gault, Robert A.; Robinson, George W.; Scovil, Jeffrey
Publication:The Mineralogical Record
Geographic Code:1U2NY
Date:Jul 1, 2006
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