Journal of Paleolimnology (2006) 35:661667 DOI 10.

1007/s10933-005-3604-9

Springer 2006

-1

The morphological and optical properties of volcanic glass: a tool to assess density-induced vertical migration of tephra in sediment cores
Mihaela D. Enache* and Brian F. Cumming
Paleoecological Environmental Assessment and Research Lab (PEARL), Queens University, Kingston, ON, K7L 3N6, Canada; *Author for correspondence (e-mail: enachem@biology.queensu.ca)
Received 14 March 2005; accepted in revised form 15 September 2005

Key words: Mazama, Morphology, Optical properties, Sediment cores, Tephra, Vertical migration, Volcanic glass

Abstract Volcanic ash layers in sediment cores are valuable geochronological markers in paleolimnological research. The composition of volcanic glass is related to identiable, chronologically distinctive volcanic eruptions. Consequently, tephra layers provide time horizons allowing regional-scale correlations for lake sediments. Volcanic glass is often present in samples routinely prepared by paleolimnologists such as diatom slides and thin sections. Knowledge of the morphological and optical properties of volcanic glass allows for its identication. This is essential for the identication of ash layers that are not macroscopically visible or to track their vertical migration in soft organic sediments. The purposes of this note are to: (1) describe how the morphological (i.e., shape, vesicularity) and optical (i.e., refractive index and birefringence) properties can be used to identify volcanic glass in preparations from lake sediments; and (2) show how the quantication of volcanic glass from diatom slides is used to quantify the density-induced displacement of a 4.5 cm-thick Mazama ash-layer through organic sediments and to approximate its timing of initial deposition.

Introduction Solid fragments resulting from volcanic eruptions are known as pyroclastic material and the resulting unconsolidated pyroclastic deposit is also known as tephra (Vincent 2000). The term ash is reserved for pyroclastic material that is less than 2 mm in size, and includes vitric material along with rock and mineral fragments (Heiken and Wohletz 1985). Identication of such glassy fragments from sedimentary sequences is useful as they can provide chronological information on core stratigraphy (e.g., Westgate and Gorton 1981; Leonard 1995; Turney and Lowe 2001) and have multiple

applications in paleolimnological research (e.g., Barker et al. 2003; Colman et al. 2004; Davies et al. 2004; Haberyan and Horn 2005). The vitreous fragments ejected from volcanic vents are deposited via the atmosphere over the surrounding region and often form layers in lake sediments (Vincent 2000). Lacustrine ash layers contain glass shards with a chemical composition that is volcano specic and also related to a particular eruption (Turney and Lowe 2001). Consequently, tephra can provide time-lines or marker horizons, which constitute a precise and condent tool for multiple core and/or regional-scale correlations of sedimentary sequences (Hall and Pilcher 2002).

662 However, in some circumstances ash layers have been reported to vertically migrate in low-density stratigraphic sequences (Beierle and Bond 2002). Paleolimnologists often prepare sediment samples using strong acids to remove organic and carbonate material (Wilson et al. 1996), which leaves silica-rich material such as diatoms, silicate minerals and volcanic glass fragments. This note will rst describe how optical properties can be used to distinguish volcanic glass from silicate minerals by shape, refractive index (i.e., measure of how much the light is bent when entering a new transparent material, Nesse 2000) and by lack of interference colors (i.e., colors seen between crossed polarizers on a petrographic microscope, as a consequence of the light being split into two rays when passing through a mineral, Nesse 2000). Second, we apply this technique to identify volcanic glass in a 14C-dated core from Prosser Lake (494505 N; 1203730 W; British Columbia, Canada). A 4.5 cm-thick tephra layer was identied as the Mazama climactic eruption (Hallett et al. 1997) through electron microprobe analysis. According to our AMS 14C dates, the tephra layer is positioned in the sedimentary sequence at a much older age than previously recorded. We assessed changes in the abundance of the glass shards from diatom slides, above the macroscopically visible tephra layer to identify the initial deposition of this tephra prior to its downward migration in the core. Diatom slides were prepared above the macroscopically visible tephra layer at 2-cm intervals, following procedures described by Wilson et al. (1996). Three size-categories of glass fragments (< 50; 50100; and >100 lm) were counted over the whole surface of the coverslip, calculated as number of fragments/g wet sediment, and then plotted against depth in the core. Volcanic glass was enumerated above the tephra layer until the number of glass fragments decreased to $0 glass shards/g wet sediment. The intervals were compared for glass shards abundances and we considered that a signicant change occurred when the mean of consecutive intervals was higher than the mean + 2SD of the previous or following intervals. ANOVA and t-test analyses, performed with JMP 5.01 (SAS Institute Inc.), were used to assess the statistical signicance of these changes. Identication of volcanic glass fragments Glass particles of volcanic ash appear under the microscope as angular, highly vesicular fragments, with size ranging between a few microns to 2 mm. Vesicles are empty cavities or lled by gas and their shapes can be elongated or stretched by the ow before the volcanic melt is cooled to a glass (Figure 1). Along with their characteristic morphology (i.e., angular vesicular shape), glass fragments can be distinguished from mineral fragments based on their optical properties i.e., the refractive index (Becke line method), and observation in cross-polarized light (Nesse 2000).

Sample preparation and methods A 6.25 m core representing the complete sedimentary record of Prosser Lake was recovered from a depth of 26 m from Prosser Lake, using a 2 Livingstone piston corer, in July 2000. A $4.5 cm-thick tephra layer situated at 472.5 cm depth in the core was identied by microprobe analysis by Dr. P. Roeder at Queens University, as belonging to the climactic eruption of Mazama (Hallett et al. 1997; Zdanowicz et al. 1999). However, 14C AMS dates on pollen at 443 and 500.5 cm, supplied an interpolated age of 7440 cal years BC at the top of the macroscopic tephra layer, which is approximately 2000 years older than ages previously provided (54705620 cal BC, Hallett et al. 1997).

Volcanic glass morphology The main morphological features of volcanic glass are the geometrical shape and size of the grains, surface characteristics, vesicle form and density, and the thickness of walls separating vesicles. Volcanic glass morphologies can vary from spherical or tear-shaped droplets to highly vesicular fragments, sometimes with more than 98% vesicles and thin walls. Glass fragments may also be blocky or angular, with open-vesicle networks or no vesicles (Heiken and Wohletz 1985;

663

Figure 1. Volcanic glass identied in sediments from Prosser Lake, British Columbia. (a, b) Electron Microprobe pictures: volcanic glass identied in Mazama tephra layer (473473.5 cm interval); (c, d) Diatom slides (472472.5 cm interval): (c) volcanic glass from Mazama; (d) diatom fragment; (e, g) Epoxy-embedded thin sections (471.5472.5 cm interval): (e) pumiceous fragment at sediment tephra interface; (f, g) glass fragments and feldspar from Mazama tephra; (g) shows crossed nicols image with dark isotropic glassy material and mineral fragments showing interference colors; (hm) Observations under petrographic microscope (473473.5 cm interval): (h) mineral fragment with Becke line at grain boundary; (i) Becke line moves inside the grain when lowering the microscope stage; (j) Same mineral fragment showing interference colors under crossed polarizers; (k) glass fragment with crystal inclusions showing Becke line at grain boundaries; (l) Becke line moves towards immersion oil around the glass fragment and inside crystal grains when lowering the microscope stage; (m) same picture showing the crystals exhibiting interference colors whereas the volcanic glass appears dark under crossed polarizers. In all pictures, black arrows are pointing volcanic glass and white arrows are pointing minerals.

664 Bardintze 2000). Smaller particles, which are fragments of vesicle walls, are Y-shaped, curved plates, or needle-like (Heiken and Wohletz 1985). Figure 1ac, shows glass fragments with irregular, highly angular-curved shape and high vesicularity, with circular to subovoidal vesicles separated by thin walls from the Mazama ash layer in Prosser Lake. The direction of vesicle elongation indicates the direction of ow. Abundant Y-shaped, platelike, curved, and angular shards (remnant from vesicle wall breakage) are typical of this tephra layer (Figure 1b). Contrasting volcanic glass morphology, a diatom fragment is shown in Figure 1d. Identication of volcanic glass in cross-polarized light The main dierence between volcanic glass and most crystalline minerals (with the exception of isometric crystals) is that most minerals show interference colors under crossed polarizers whereas volcanic glass does not. Volcanic glass is optically isotropic (i.e., the velocity of the light is the same in all directions) whereas most silicate minerals are anisotropic (i.e., the velocity of light varies with direction of transmission). The petrographic microscope is equipped with two polarizers (also called Nicols) placed below and above the microscope stage. The vibration directions of the two polarizers are set at right angles, so that light passing through the lower polarizer is completely absorbed by the upper polarizer. Because volcanic glass is optically isotropic, it does not aect the vibration plane of light coming from the lower polarizer and the upper polarizer will absorb the light. Consequently, under cross polarizers, volcanic glass appears dark in the microscopic eld (Figure 1g, m). In contrast, anisotropic silicate minerals rotate the plane of polarization and thus will show interference colors as the microscope stage is rotated (Figure 1j, m).

The Becke line method The Becke line method involves observation of the volcanic fragments mixed with immersion oil (or mounted in Naphrax or epoxy) on a glass slide using a petrographic microscope with an intermediate power objective (e.g., 10). At this magnication, a rim of light, called the Becke line, can be seen inside or outside of the grain boundary. If the distance between the sample and the objective is increased by lowering the microscope stage (focus is raised), the Becke line moves into the material with the higher index of refraction (Nesse 2000). Most volcanic glass fragments have a refractive index of %1.5, lower than the immersion oil or epoxy (1.531.55), and Naphrax (1.7). Consequently, the Becke line moves towards the immersion oil when the microscope stage is lowered (Figure 1k, l). Crystal fragments usually have a higher refractive index than immersion oil, and the Becke line will move towards the center of the crystal fragment when lowering the microscope stage (Figure 1h, i, k, and l). Thus, it is possible to distinguish volcanic glass from minerals using this technique.

Identication of volcanic glass fragments in diatom slides and thin sections Volcanic glass fragments have similar properties to diatom frustules, are resistant to strong acids and thus survive the overall process of sample preparation for diatoms. The glass shards can be rst identied by their angular, vesicular shape and the Becke line method in order to verify if their refractive index is lower than the 1.7 refractive index of Naphrax. Because many silicate miner-

Table 1. AMS Radiocarbon ages on pollen samples from intervals above and below the Mazama tephra layer. Depth in core (cm) 443444 500.5501 Lab no Age (14C year BP) 6066 44 10,145 51 Age range at 2r (cal year BC) 48055195 941010,350

AA 584871472A AA 580661473A

665 als have a refractive index lower than 1.7, it is also necessary to observe the glass fragments using a petrographic microscope with crossed polarizers as described above. Epoxy-thin sections are used by some paleolimnologists in charcoal quantication (Clark 1988), varve chronology and holistic paleoenvironmental reconstructions (Kemp et al. 2001; Lamoureux 2001). Since the refractive index of epoxy is $1.55, the methods described above can be applied to identify glass fragments. In comparison to the amorphous organic matter, volcanic glass appears as clear, transparent fragments (Figure 1e) and, in contrast to minerals, does not display interference colors (Figure 1g) as discussed above. If glass shards are identied in embedded polished thin sections, microprobe analyses can be undertaken on the same slide. source material used in dating (pollen, this study, vs. charcoal, Hallett et al. (1997)). The 462 cm increase in glass shard abundance may represent a decrease in the settling rate of the tephra bed through the sedimentary sequence. The climactic eruption of Mazama was estimated to result in a voluminous fallout, which lasted up to 23 years after eruption (Zdanowicz et al. 1999). Experimental (Kuenen 1965) and eld observations (Sims 1975; Anderson et al. 1985) show that rapid deposition of ash-layers of thicknesses >3 cm can result in penetration of the underlying sediment column by density-induced displacement and movement of sediment. White and Osborn (1992) and Beierle and Bond (2002) recorded similar downward movement of Mazama ash-layer of more than 3000 years, through low-density organic sediments in Copper Lake, Alberta. In agreement with Beierle and Bond (2002), we infer that the thickness and weight of this volcanic layer resulted in its vertically-induced displacement through the softorganic sediments of Prosser Lake. According to Anderson et al. (1985) and Beierle and Bond (2002), the downward movement of a tephra bed is usually stopped by a change in sedimentary facies to more dense, less organic sediments, with the tephra layer possibly transporting a small portion of the overlying sediment. Observation of the structure of the sediments above the tephra layer also supports the idea of a density-induced displacement of the tephra. At about 11 cm above the macroscopic tephra a gradual change between two sequences contrasting in colour, texture, and bedding takes place. The highly organic, sub-millimetric laminae are replaced, between $450 and 465 cm depth in the core, by sub-cm to cm-thick, light and dark brown laminae, occasionally rich in bivalves, which can be related to a higher mineral content and a dierent sedimentation regime. This change roughly corresponds to a drastic increase in volcanic glass abundance, at ca. 462 cm (6540 cal BC, according to 14C analyses), likely related to decreasing settling of volcanic fragments due to changes in sediment density (Figure 2). Another possible explanation of abundant volcanic glass up to 30.5 cm above the tephra layer might be provided by the hypotheses of resuspension of volcanic fragments in the water column or the secondary deposition of tephra from the lake watershed. However, these hypotheses are not supported by the following evidence: (1) Prosser

Assessment of the amplitude of vertical displacement of Mazama tephra-layer by quantication of volcanic glass from diatom slides Radiocarbon dating based on pollen samples from above and below the tephra bed supplied an interpolated age of 74407700 cal BC (Table 1) for the Mazama tephra, which is ca. 2000 years older than the ages supplied by Hallett et al. (1997) (54705620 cal BC or 74707620 cal BP). Quantication of volcanic glass from diatom slides was undertaken as a tool to identify the extent of downward migration of the Mazama tephra bed. The plots of volcanic-glass fragments above the Mazama tephra-layers show that volcanic glass occurs $30.5 cm above the macroscopical ash layer (442 cm core depth) and is represented by abundant glass shards >50 lm. Downward the core, the volcanic glass displays a quasi-monotonic distribution followed by a signicant (p < 0.5) increase in the abundances of glass shards at the depth of 462 cm, 10.5 cm above the macroscopically observed layer (Figure 2). We suggest that the rst occurrence of abundant glass shards at 442 cm represents the initial timing of Mazama sedimentation in Prosser Lake. Based on 14C analyses, this level provided an age of 4925 cal BC, 445 years younger than the minimum calibrated age previously provided by Hallett et al. (1997). This dierence might be explained by errors associated to 14C dating or by the type of

666

Figure 2. (a) Sediment core between 444 and 477.5 cm; the black arrow points Mazama tephra. (b) Quantication of volcanic glass fragments between 440 and 470.5 cm in the sedimentary column of Prosser Lake.

Lakes sedimentary column displays laminated sediments, with dark-light laminae couplets, suggesting thermal stratication and undisturbed sedimentation regime above the tephra bed; (2) the watershed of Prosser Lake is small (2 ha) and the monotonic distribution of glass shards does not display any peak ow event, which usually is related to secondary deposition (Riedel et al. 2001); and (3) the unmodied structure of individual glass shards retains a jagged, highly angular and fresh appearance like those from the macroscopic ash-layer up to 442 cm above the tephra layer. All these ndings support the idea that a density-induced vertical migration of Mazama tephra through low-density organic sediments took place in Prosser Lake to a level about 2000 years older than the Mazama eruption. This vertical migration of the tephra bed was tracked by quantication of glass shards from diatom slides in order to approximate the initial timing of tephra deposition. We infer that besides quantication of tephra

vertical migration, this approach can also be used to identify tephras which are not macroscopically visible, and thus contribute to increase the number of tephras recorded and determine their regional distribution in lake sediments.

Conclusions The observation of morphological and optical properties of volcanic glass under petrographic microscope constitutes an accurate and rapid way in the identication of volcanic ash in samples currently used by paleolimnologists, such as the diatom slides and epoxy-embedded thin sections. Volcanic glass identied up to 30.5 cm above the Mazama ash-layer supports the idea of a densityinduced settling of the tephra bed through the organic sediments of Prosser Lake. Quantication of volcanic glass from diatom slides helped track the approximate timing of its initial sedimentation

667 in Prosser Lake sedimentary sequence. The careful investigation of such samples by paleolimnologists can help identify the extent of vertical migration of ash-layers in soft organic sediments.
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Acknowledgements We thank Dr. Peter Roeder for constant help and advice concerning volcanic ash identication. We would like to thank Dr John Smol for his comments and useful suggestions. Many thanks to Dr John Westgate who provided constructive comments on a former manuscript. Funding was provided by Ontario Graduate Scholarships (OGS) to MDE, and Natural Sciences and Engineering Research Council of Canada (NSERC) Discovery Grant to BFC.

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