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Research Paper |
1 Department of Geology, Colgate University, Hamilton, New York 13346, and 2 Department of Civil and Environmental Engineering, Syracuse University, Syracuse, New York 13244, USA
* E-mail: rapril{at}mail.colgate.edu
(Received 30 July 2003; revised 7 November 2003)
| ABSTRACT |
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KEYWORDS: Adirondacks, Podzols, smectite, soils, Spodosols, vermiculite, weathering
Smectite is common in soils that are poorly drained, influenced by or formed from volcanics, and in which the mineral is inherited directly from the parent material (Borchardt, 1989). Also now widely recognized is the occurrence of smectite as a weathering product in well drained soils, in particular, Spodosols (Podzolic soils), which formed under temperate climates from parent material of granitic composition (Brown & Jackson, 1958; Gjems, 1960, 1962; Franzmeier & Whiteside, 1963; Ross & Mortland, 1966; Kodama & Brydon, 1968; Melkerud, 1983, 1985; Hluchy, 1984; Keller, 1988; Allen & Hajek, 1989; Feldman et al., 1991; Carnicelli et al., 1997; Righi et al., 1999; Gillot et al., 2000). Most often the smectite is restricted to the albic (E) horizon and appears to form from the progressive weathering of phyllosilicates, primarily muscovite, biotite and chlorite, present in the underlying parent material. Ross (1980), in reviewing the mineralogy of Spodosols, suggested that the dominance of smectite or vermiculite, or both, in the E horizon is characteristic of the clay mineralogy of this soil type.
Previous studies of the mineralogy of soil and glacial deposits from forested sites across the Adirondack Mountains of New York State reported on the up-profile mineral weathering sequence of mica
mixed-layered mica-vermiculite
vermiculite
low-charge vermiculite (April & Newton, 1983; April et al., 1986). Although this weathering sequence in soils is well documented, it can vary according to the specific mica mineral involved and the prevailing climatic, biotic and soil conditions (e.g. Jackson, 1963; Lagaly, 1982; Borchardt, 1989; Douglas, 1989; Fanning et al., 1989; Feldman et al., 1991; Wilson, 1999). Intermediate products in this weathering sequence, such as mixed-layered and hydroxy-interlayered clays, as well as other end products such as kaolinite have been noted (e.g. Sawhney & Voigt, 1969; Gilkes & Suddhiprakarn, 1979; Banfield & Eggleton, 1988). However, in any given solum all intermediate and final products may not be present (see, e.g. Ahn & Peacor, 1987). In the Adirondack Mountains, Johnson & McBride (1989) identified a hydroxy-interlayered smectite and found that the mineral was concentrated in E horizons.
In the present paper we report on clay minerals identified in the upper horizons of Adirondack soil profiles, including the Bhs, the albic E and the organic-rich A and O horizons. We show that the previously described up-profile mineral weathering sequence of mica
mixed-layered mica-vermiculite
vermiculite
low-charge vermiculite progresses further to smectite, and that smectite is a common clay mineral in the uppermost soil horizons.
| MATERIALS AND METHODS |
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The mineralogy of surficial sediments at any given locality is strongly influenced by and closely reflects the mineralogy of the regional bedrock. Till and outwash sands typically contain abundant feldspar (both K-feldspar and plagioclase) and quartz, and minor amounts of hornblende, ilmenite, magnetite and garnet (April & Newton, 1983). Phyllosilicates, including muscovite, biotite and chlorite, may be present or absent depending on location. The last remnants of glacial ice disappeared from the region 12,000 to 14,000 years ago and soils, which today are dominated by acidic Spodosols, developed on the glacial sediments.
Sampling and analytical techniques
For this investigation we focused our soil sampling in Huntington Forest, a 6000 ha preserve near the geographic centre of the Adirondack Park, located in the Town of Newcomb, western Essex County and in the Town of Long Lake, eastern Hamilton County, New York (latitude 44°00' N; longitude 74°13' W). Additional samples were collected from the Big Moose Lake area in the west-central portion of the Adirondacks (latitude 43°50' N; longitude 74°51' W); and from the Whiteface Mountain area of the high peaks region (latitude 44°22' N; longitude 73°54' W) (Fig. 1
). The Spodosols sampled comprise well to moderately drained Typic Haplorthods and Fragiorthods (Becket-Mundell series sandy loams coarse-loamy, mixed, frigid typic Haplorthods) developed on till. Profile depths generally average ~75 cm or less and may terminate on bedrock or grade into the underlying parent material. Soil samples were collected using trowels and straight edged tools from horizons exposed on the sides of excavated pits ~1 m square. In all, 20 composite Oa and A horizon samples (referred to hereafter as O+A composites), some individual Oa and A horizons, and 30 E, B and C horizon samples were analysed for bulk mineralogy and clay mineralogy.
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radiation, a 1° beam slit, medium resolution soller slit and a 0.1° receiving slit. X-ray fluorescence (XRF) analyses of the bulk soil and selected clay fractions, fused into glass discs with lithium tetraborate, were made using a Diano XRF-8560 vacuum-path X-ray spectrometer equipped with a dual target Cr/W tube. Calibration curves for major elements were prepared by multiple linear regression and matrix correction techniques using 40 rock, mineral and synthetic glass standards. In addition, the <1 µm clay fractions of selected samples were mounted on carbon stubs and analysed chemically with a Tracor Northern energy dispersive X-ray analysis system (EDS), mounted to a Cambridge Stereoscan 200 SEM, using a 200 s count time, 15 kV acceleration potential, and a 50 µm spot diameter. Grain size was determined on 1015 g aliquots of soil by wet sieving following the procedures of Jackson (1974). Samples were rinsed with dilute ammonium hydroxide through standard sieves and separated into sand and silt + clay. The sand fractions were oven dried and weighed. The silt + clay mixtures were poured into 1000 ml settling tubes for grain-size analysis using the pipette method (Jackson, 1974).
Mineral abundances in the fine-sand fraction of both light (sp.gr. <2.95) and heavy (sp.gr. >2.95) mineral separates were determined by point counts of ~300 grains per slide using a petrographic microscope (Galehouse, 1969, 1971). Grain mounts were also inspected in the scanning electron microscope (SEM) and the identity of grains was checked using the semi-quantitative elemental spectrum obtained by the EDS system. Chemical analyses of biotite grains were acquired using both the EDS system and a JEOL 8900M Superprobe electron microprobe (Binghamton University).
| RESULTS |
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Clay mineralogy
Results from the XRD analysis of the <2 µm clay fractions showed that smectite is a common constituent in the upper soil horizons of Spodosols collected at all sites included in this study. In general, the presence of smectite in the clay fraction was indicated by a 14 Å reflection in the air-dried, Mg-saturated state that shifts to an 18 Å reflection following glycerol solvation. (There is some disagreement in the literature as to how to distinguish smectite from high- and low-charge vermiculite in XRD patterns [Moore & Reynolds, 1997; Douglas, 1989, pp. 652657]. We use the conventional operational definition here for distinguishing between vermiculite and smectite, as discussed in Moore & Reynolds, 1997, p. 160.) Using peak height as a rough indicator of relative abundance, smectite ranged from being the dominant mineral in the clay fraction of several O+A horizons collected from the Big Moose area to being a minor constituent (Fig. 2
). Variable amounts of vermiculite and small to trace amounts of kaolinite and a 10 Å mica were also present in some samples.
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| DISCUSSION |
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Clay mineral stabilities in the soil profile are reflected by the depth-dependent conversions of hydroxy-interlayered vermiculite to vermiculite to low-charge vermiculite to smectite, up profile. Humic, fulvic and other organic acids have been shown to be aggressive weathering agents in soils, especially with respect to the dissolution of clay minerals (Huang & Keller, 1971; Antweiler & Drever, 1983; Sposito, 1989; Ugolini et al., 1991). Chemical conditions, therefore, are most extreme in the O and A horizons where, as observed for the sites sampled in this study, only low-charge aluminous vermiculite and aluminous smectite (e.g. beidellite however, the Greene-Kelly test gave us variable and inconclusive results; Lim & Jackson, 1986) co-exist as the end-products of weathering. Kaolinite is also present in these horizons, but its origin has yet to be determined.
An intermediate product in the conversion vermiculite to smectite is the low layer charge variety of vermiculite, which could form chelation in the upper soil horizons progressively removes Al from the interlayer and structural sites of vermiculite. The latter process would result in gradual decrease of net layer charge on the clay (as Si substitutes for Al in tetrahedral sites) towards the top of the soil profile and the eventual formation smectite. The chemistry of soil solutions collected from lysimeters installed in Huntington Forest and Big Moose Lake area soils is consistent with these mineralogical transformations (Fig. 6
). In all soil solutions studied, concentrations of organic complexes of Al (and Si) were significant in Oa horizon leachates, suggestive of Al cheluviation (see Cronan & Schofield, 1990; Walker et al. 1990). The data suggest that the Al released by the weathering of phyllosilicates and other aluminosi licates is transported downwards in the soil profile, largely as organically complexed Al, to the spodic (B) horizon where it eventually precipitates as amorphous to poorly crystalline hydroxide and oxyhydroxide grain coatings or cement, is (re-?)incorporated into the interlayer sites of vermiculite to produce Al hydroxy-interlayered vermiculite, or forms para- or non-crystalline aluminosilicates (Johnson & McBride, 1989). As stated, although kaolinite was found (by XRD analysis) to be present in most samples, we have no evidence to indicate whether the mineral formed from the continued alteration of smectite, or whether it was simply inherited from previously weathered material (e.g. Stevens et al., 1987).
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Although most of the E and composite O+A horizons examined in this study contained the clay mineral assemblage described above, XRD patterns of upper horizon soil from the Whiteface Mountain site, in the High Peaks region (Fig. 1
), displayed weak reflections that only hinted at the presence of low-charge vermiculite or smectite in the clay fraction of the upper soil horizons. Peak definition in these XRD patterns was generally poor, probably due to a lack of clay-sized material. One reason for the lack of clay development may be the low mica content of parent till in the High Peaks region. Anorthosite, the dominant bedrock type in the area, contains almost no micas or chlorite. In one of the few earlier studies of Adirondack Spodosols, Coen & Arnold (1972) suggested that smectite in soils of the Whiteface Mountain area may have been derived largely from aeolian inputs, or from the subsequent weathering of minerals, such as mica and chlorite, that are added to the soil as dust. Whereas our findings do not rule out the possibility that aeolian-derived material adds to the amount of smectite in Adirondack soils, especially those containing little to no pre-existing phyllosilicates, our data suggest that when phyllosilicates are present in the parent material, podzolization leads to the formation of smectite in upper soil horizons.
In summary, the results from this study lend support to the growing and convincing body of evidence that smectite forms through transformation of micas in the upper horizons of Spodosols (for a recent summary of this literature see Wilson, 1999). Futhermore, as suggested by Feldman et al. (1991), and others, as long as mica is present as a primary aluminosilicate, the weathering sequence of mica
mixed-layered mica-vermiculite
vermiculite
smectite, and the presence of these minerals in Podzols, will be controlled more by biotic and climatic factors than by any differences in initial parent-material composition.
| ACKNOWLEDGMENTS |
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