Journal of Archaeological Science (2003) 30, 217–226

doi:10.1006/jasc.2002.0828

Detection of Burning of Plant Materials in the Archaeological

Record by Changes in the Refractive Indices of Siliceous
Phytoliths
Rivka Elbaum and Steve Weiner*
Department of Structural Biology, Weizmann Institute of Science, Rehovot, 76100 Israel

Rosa M. Albert
Department of Prehistory, Ancient History and Archaeology, Facultat de Geografia i Historia, Universitat de
Barcelona. c/ Baldiri Reixach, s/n, 08028 Barcelona, Spain

Michael Elbaum
Department of Materials and Interfaces, Weizmann Institute of Science, Rehovot, 76100, Israel

(Received 6 December 2001, revised manuscript accepted 4 March 2002)

The most resilient remains of plants in most archaeological sites are the siliceous phytoliths—special cells that are
partially or completely silicified during the plant’s life. These cells have characteristic morphologies, and thus the
phytoliths can often be used to identify the taxonomic affinities of plants brought to an archaeological site. In order to
determine what they were used for, other means of analysis are needed.
We present here a method to distinguish burnt from unburnt phytolith assemblages. The method is based on
measuring the refractive index (RI) of individual phytoliths. The phytoliths even from a single plant have a range of RI
values. Burning a phytolith sample causes a shift to higher RI. Comparing burnt and unburnt samples we demonstrate
that it is possible to differentiate between them based on the fraction of phytoliths with RI higher than 1·440. This serves
as a basis for a simplified mode of measurement that requires only the use of a petrographic light microscope and a
mineral oil of RI 1·440. We apply the simplified method to two Natufian samples from Hayonim cave (Western Galilee,
Israel).  2002 Elsevier Science Ltd. All rights reserved.

Keywords: PHYTOLITH, OPAL, FIRE, REFRACTIVE INDEX, BURNING.

Introduction These minerals thus constitute an invaluable record of

the plant components of an archaeological site.
lants are used by humans for food, fuel, The most common form of silica produced by plants

P housing, and tools such as handles, sieves,

mats, clothing and more. Plant materials thus
potentially constitute an important component of an
archaeological site. They are only rarely preserved as
such, because they are usually degraded rapidly. The
degradation process results in loss of the organic
components and some of the mineral components,
such as the oxalates. What remains for much longer
periods of time are the more insoluble and hence stable
silica minerals produced by many plants (Piperno,
1988; Pearsall, 1989; Mulholland & Rapp, 1992).
*To whom correspondence should be addressed:
steve.weiner@weizmann.ac.il
0305–4403/03/$-see front matter
is an almost pure opal that either impregnates cell
walls, intercellular spaces, or even whole cells. In so
doing the mineral tends to replicate the cell mor-
phology (Blackman, 1969). These so-called opaline or
silica phytoliths are produced in large amounts by the
grasses (in some cases they constitute around 10% by
weight of the dried plant (Epstein, 1994)), and in
smaller amounts by many other plants, including trees
(Amos 1952; Scurfield et al., 1974). In the latter they
are located mainly but not exclusively in the wood,
bark, and leaves (Albert & Weiner, 2001). Trees also
produce a second type of relatively stable mineral
E-mail: phase, the so-called siliceous aggregates. These are soil
minerals cemented together by a matrix of silica which
217
 2002 Elsevier Science Ltd. All rights reserved.
218 R. Elbaum et al.

Table 1. Phytolith samples examined in this study

Sample Plant Part Source Extraction method Remarks

wh1 Bread wheat (Triticum Inflorescence Beit Keshet, Israel Wet ashing 1 (at 100C)
aestivum)
wh1/700 Bread wheat (Triticum Inflorescence Beit Keshet, Israel Wet ashing 1 (at 100C) wh1 heated at
aestivum) 700C for 7 h
wh2 Domesticated Emmer Ripe awns Gilat Experimental Wet ashing 1 (at 100C)
wheat (Triticum dicoccum) Agriculture Station, Israel
wh3/1000 Domesticated Emmer Ripe awns Beit Qama, Israel Wet ashing 1 (at 100C) Heated at 1000C
wheat (Triticum dicoccum) for 1·5 h
p1 Pine (Pinus halepensis) Leaves Bat-Shelomo, Israel Wet ashing 1 (at 100C)
A1 Unknown Mixture of leaves Qumran cave (5000–10,000 ), Wet ashing 1 (at 100C)
the Judean Desert.
wh4 Bread wheat (Triticum Stems and leaves Gilat, Experimental Wet ashing 2 (at 65C)
aestivum) Agriculture Station, Israel
p2/500 Pine (Pinus halepensis) Leaves Bat Shelomo, Israel Dry ashing (at 500C)
A2 Unknown Grotte XVI, Upper Paleolithic, Heavy liquid separation Fractions 5+6
the Dordogne valley,
France
A3 Unknown Hayonim cave, Heavy liquid separation Fractions 5+6
Natufian layer, Israel Hearth sample
A4 Unknown Hayonim cave, Heavy liquid separation Fractions 5+6
Natufian layer, Israel Sedimant sample

also contains many other elements, such as aluminum,
potassium and iron (Schiegel et al., 1995). They do
not have characteristic morphologies, and under the
microscope they are difficult to differentiate from clay
particles.
Phytoliths are present in large amounts in the sedi-
ments of archaeological sites, and due to their specific
morphologies have been widely used to determine the
taxonomic affinities of the plants brought to the site by
its inhabitants (e.g. Piperno 1988). Quantitative analy-
ses of phytoliths per unit weight sediment combined
with information on the more general affinities of the
plant phytoliths (e.g. from wood, bark, leaves, grasses
etc.) is proving to be a powerful tool for reconstructing
aspects of past human behavior (e.g. Albert et al.,
2000, 2001). Phytoliths from fruit or seed shells may be
genus specific, and sometimes even species specific.
This was used to monitor the domestication processes
of squashes and gourds in the American tropics
(Piperno, 2000). The phytolith assemblages can
also provide indications of paleoclimatic conditions
(Piperno, 1988), paleodiet (Fox et al., 1994), irrigation
patterns (Rosen & Weiner, 1994), and site formation
processes (Albert et al., 1999). Burnt phytoliths have
slightly distorted shapes (Kealhofer & Penny, 1998),
and are commonly colored (Piperno, 1988). Here we
present a method for determining whether phytolith
assemblages extracted from archaeological sediments
were burned based on a physical property of the opal.
This information can help differentiate plants used
for fuel, as they will contribute burnt phytolith
assemblages, as compared to plants used for cooking,
bedding, roofing, etc. The latter will have unburnt
phytolith assemblages (unless they were subjected to
catastrophic fires).
The method is based upon the measurement of the
refractive index (RI) of individual phytoliths. The RI
of opal or silica (terms used here synonymously for
the same mineral) is dependent upon the extent of
hydration of the silica (Heinrich, 1965). It is known
that phytoliths extracted by acid treatment (wet ash-
ing) have a RI range of 1·427–1·440 while phytoliths
extracted by ashing at 450–550C have a RI range of
1·438–1·487, and their water contents are substantially
lower. At temperatures above 1000C the RI range is
around 1·48 (Jones & Milne, 1963). Upon heating to
temperatures above 200C water molecules start to
form from the surface hydroxyl groups. The hydroxyl
groups are completely stripped off at 600C (Jones &
Segnit, 1969). These observations suggest to us that
changes in the RI of phytoliths from archaeological
sites might be indicative of burning at high tempera-
tures. Here we confirm that phytolith RI values
increase as a result of burning. We present a simple
method for differentiating between phytolith assem-
blages that were burnt and those that were not
burnt, and show that this method can be used for
archaeological material.
Materials and Methods
Materials
The plant materials used and the phytolith extraction
methods are listed in Table 1. The refractive index
oils were purchased from Cargille (R.P. Cargille
Laboratories, Inc., NJ, U.S.A.).
Methods
Phytolith extraction. Phytoliths were extracted from
the plant matrix by wet or dry ashing, or from
 Detection of Burning of Plant Materials in the Archaeological Record 219
sediment samples by heavy liquid separation. Wet
ashing was performed using a mix of acids heated to
either 100C (method 1) or 65C (method 2).
Wet ashing: method 1 (Piperno, 1988). A sample of
0·2–5 g of dry plant material was washed with about
5% solution of Decon 90 (strong detergent) using
ultrasonic treatment for 1–2 h, followed by a wash with
double distilled water (DDW). An Erlenmeyer flask
containing 10–100 ml Schultz solution (75 ml HNO3,
25 ml water, 2 g KClO3) was heated in boiling water
and the washed sample was added until the plant
matrix was degraded. After 4 h of heating small
amounts of KClO4 were added. The heating and the
addition of KClO4 were stopped when no bubbles
formed when additional KClO4 was added. The
solution was centrifuged at 3500 rpm in 50 ml tubes
and the supernatant was discarded. The pellet was
washed twice with DDW, once with 1 N HCl, twice
with DDW, and then transferred to a 2 ml Eppendorf
microcentrifuge tube. The white powder was washed
twice with acetone and then air dried at room
temperature.
Wet ashing: method 2 (Shahack-Gross et al., 1996).
Leaves and stems of fresh wheat were dried at 60C for
72 h. The dried samples were ground in a mill and 3 g
of the powder was divided into three 50 ml tubes. A
20 ml solution of 1:1 mixture of 70% HNO3 and 70%
HClO4 was added to each tube. The tubes were par-
tially capped and held at 65C for 3 h. DDW was
added to each tube, and the tubes were centrifuged at
4500 rpm for 2 min. The supernatant was removed and
the three sub-samples were combined and washed
again with water. The acid treatment was repeated for
2 h, followed by washing. The samples were further
treated with a 20 ml solution of 4:1 mixture of 70%
HNO3 and 98% H2SO4 for about 17 h, washed five
times with water, and dried at 60C for 24 h.
Dry ashing (Albert et al., 1999). Plant material was
washed with water in a sonic bath for about 10 min
and then dried. The sample was burned at 500C for
4 h in an oven (Lindberg Blue M 848). The sample was
then treated with 10 ml of an equivolume solution of
3 N HCl and 3 N HNO3 heated in boiling water for
30 min and rinsed with DDW three times, and then
burned again at 500C for 90 min. If remnants of
organic material were still observed, the sample was
heated in H2O2 to completely eliminate all organic
material.
Extraction of phytoliths from sediments (based on
Albert et al., 1999). Ten ml 1 N HCl was slowly added
to one gram of sediment and sonicated until the
bubbling stopped. The sample was then washed with
DDW and centrifuged three times (3500 rpm), washed
with acetone, and dried under a heat lamp.
The minerals in the sample were then separated
according to their specific gravity. The sample was
transferred to a 15 ml centrifuge tube and 5 ml sodium
polytungstate solution [Na6(H2W12O40) . H2O] of 2·4
gram/ml density was added (3:1 ratio by weight of
sodium polytungstate to water). The suspension was
vortexed and sonicated until it was well dispersed. It
was then centrifuged at 3500 rpm for 5 min. The super-
natant was transferred to another centrifuge tube, 1 ml
DDW was added, and the tube was vortexed and again
centrifuged as above. This cycle was repeated 4–6 times
until the supernatant was clear. Then the tube was
filled with DDW and centrifuged once more to ensure
that all mineral particles were recovered. After each
centrifuge step the pellet was washed twice with DDW,
transferred to an Eppendorf tube, washed with DDW
and acetone, and dried. Phytoliths were concentrated
in the pellets of fractions 4, 5, 6.
The RI vs temperature calibration curve. A drop of
mineral oil with RI of 1·45755 was placed in a
temperature-regulated refractometer (Bleeker Zeist,
Holland. No. 33885) and its RI was measured. The
apparatus was calibrated to 1·45755 at 25C and
heated slowly to 70C. The RI of the oil was recorded
every 5C.
Slide preparation. A drop of a mineral oil with a known
RI of 1·45755 or 1·440 was placed on a glass micro-
scope slide. A clean sample of phytoliths (approxi-
mately 1 mg) was mixed with the oil to form an even
spread on the slide, which was then covered by a cover
slip.
Measurement of the Refractive Index of a single
phytolith by varying temperature. The measurement
was performed using an optical microscope (Carl Zeiss
Inc. Axiovert25, objective lens 10 and 20) fitted
with a temperature control stage (THMS 600 hot stage
with TMS93 temperature controller. Linkam Scientific
Instruments LTD, England). The microscope was
operated with closed condenser aperture (aperture iris)
in order to increase the contrast. Samples were pre-
pared between two microscope cover slips (as opposed
to a slide and a cover slip) to ensure fast heat transfer
from the hot stage to the sample. The rate of tempera-
ture rise was 10C/min, which is slow enough to
equilibrate with the oil.
The RI of a single phytolith was measured using the
Becke line (Head, 1962), in which the particle is
immersed in a liquid with a known RI. As a result of
reflecting and refracting light, a line of light appears at
the border of the particle when it is in focus. This is the
Becke line. When the sample is moved to underfocus
position (i.e. the objective is moved to a distance
greater than the position at which the sample is in
focus) the Becke line will move into the phase with the
higher RI (Figure 1). When the RI of the particle is
higher than that of the oil, the Becke line will appear in
220 R. Elbaum et al.
Figure 1. Illustration of the use of the Becke line to determine
whether a phytolith has a RI above or below the RI of the liquid.
Wheat hair-phytolith (about 240
m in length) immersed in calibra-
tion oil of RI 1·45755 at 27C, and heated from 27C to 140C. The
left panel shows the sample in the overfocus position (microscope
stage brought close to the lens) and the right panel in the underfocus
position (microscope stage moved away from the lens). At 27C the
RI of the oil is higher than that of the phytolith. Therefore as the
objective is moved from the overfocus position to underfocus, light is
reflected and refracted out of the phytolith and it becomes darker
than the background. At this position (right panel) a line of light can
be seen at the particle-oil border outside the particle. This is the
Becke line (Head, 1962). As the oil is heated, its RI decreases and
becomes similar to that of the phytolith at 90C. The edges of
the phytolith are hardly seen. When the oil is heated further the
phytolith edges reappear. As the objective is moved from the
overfocus position to the underfocus position light refracts and
reflects into the phytolith, and the Becke line is seen inside the
particle. The contrast of the particle is thus reversed with respect to
that at 27C. The RI of this particle, calculated at 90C by the
calibration formula, is 1·434.
the particle and the particle will be lighter than its
background (Figure 1 at 140C). When the situation is
reversed and the RI of the oil is higher, the particle will
look darker than its background in the underfocus
position (Figure 1 at 27C). Thus the RI of the particle
can be compared to that of the liquid, and determined
to be higher or lower than the known RI of the liquid.
When the RI of the particle matches that of the liquid,
it will have no contrast in the medium and the particle
will therefore be invisible (Figure 1 at 90C).
The total number of phytoliths in a field of view was
determined at room temperature, where in underfocus
position the Becke lines of all the phytoliths appears in
the immersion oil, and the phytoliths are dark. The
sample was heated to 30C and the number of particles
with bright contrast was counted. Then the sample was
further heated to 40C and the counting was repeated.
The procedure was repeated until the temperature at
which each phytolith changed its contrast due to the
decrease in the RI of the oil, was noted. The value of
the RI of each phytolith was set to be the RI value of
the oil at the temperature the particle changed its
contrast (with a resolution of 10C, corresponding to
0·004 units of RI).
Measurement of the fraction of phytoliths with RI lower
than 1·440. The measurement was performed using
a Nikon Labophot 2-pol petrographic microscope,
objective lens 40. The microscope was operated with
closed condenser aperture (aperture iris) to increase
contrast. The total number of phytoliths and the
number of phytoliths with light contrast were counted
on a sample prepared on a microscope slide with the
Cargille mineral oil with a RI of 1·440.
Results
We confirmed that burning causes an increase in the RI
of the phytoliths by comparing under the microscope
phytoliths that were burnt at 700C and phytoliths that
were not burnt. In order to further investigate this
phenomenon we wanted to accurately measure the RI
of phytoliths.
The standard approach to measure the RI of a
mineral is to place particles of the unknown mineral in
oils with different RI’s and find the particular oil in
which the particles are invisible. The RI of the particles
is then equivalent to the RI of the index matching oil.
This is not practical for measuring the RI of individual
phytoliths, as the microscopic particle has to be some-
how transferred, until the oil with the appropriate RI is
found, or the oil around each particle has to be
replaced.
We therefore took advantage of the fact that the RI
of a pure mineral oil is almost linearly dependent on
the temperature (Kurtz et al., 1950). By heating the
calibration oil obtained from Cargille and measuring
its RI at different temperatures, we verified that there is
a linear temperature dependence of the RI of this oil
(Figure 2). Extrapolation of the relation was made to
120C and in one case to 150C. (Any deviation from
this calibration curve will be consistent for all the
samples measured.) We then used this curve to measure
the RI of individual phytoliths in an assemblage of
phytoliths. A sample was immersed in the calibration
oil and the total number of phytoliths in the micro-
scope field was counted at room temperature, as all the
opal phytoliths are assumed to have RI values equal to
 Detection of Burning of Plant Materials in the Archaeological Record 221
Figure 2. Calibration graph showing the linear dependence of
refractive index of the index matching oil on temperature. The
linear dependence is characterized by the equation: RI=1·4679–
0·00039 X T(C), R=0·995.
or below 1·46 (Heinrich, 1965). The sample was then
heated and every 10C the number of visible phytoliths
was counted. (Some phytoliths that have RI of 1·46
appear only at elevated temperatures.) The number of
invisible phytoliths was calculated assuming that either
at room temperature or at the maximal temperature of
measurement all the phytoliths were visible. Figure 3
shows the number of invisible particles as a function of
temperature. Clearly, the phytoliths do not all have the
same RI even though they are derived from the same
plant or even the same part of an individual plant. The
distribution of phytolith RI values in the sample is
close to a normal distribution, though the measure-
ments higher than 100C were not made. In the sample
shown in Figure 3 the centre of distribution is close to
80C—the temperature at which most of the particles
disappeared. The RI value calculated at 80C from the
calibration curve is 1·437. The width of the distribution
is 20C (corresponds to 0·008 RI units (Figure 2)).
This reflects both the measurement uncertainty and the
fact that the sample contains phytoliths with different
RI values.
Instead of indirectly counting the phytoliths that are
invisible in the field of view, we decided to follow the
approach used by Jones & Beavers (1963), and count
the visible phytoliths with bright contrast at each
temperature (i.e. each RI value). This represents the
fraction of phytoliths that have RI higher than that of
the oil. In Figure 4 we show the same assemblage of
phytoliths used in Figure 3 in this representation. In
practice this is the fraction of the phytoliths with bright
contrast as compared to the RI of the oil at the time of
measurement. (RI values were inferred from the oil
Figure 3. Distribution of RI values in a single plant. The number of
visible phytoliths in the field was counted at different temperatures. It
is assumed that all the phytoliths in the field are visible either at room
temperature or at the maximal temperature of measurement. The
number of invisible particles was calculated by subtracting the
number of visible particles from the total number of phytoliths in the
field. The bars represent the number of wheat phytoliths that were
not visible (sample wh1), as a function of the sample temperature.
The continuous line is a normal distribution curve with a mean
temperature of 78C (equals RI of 1·438) and a standard deviation of
20C (equivalent to 0·008 RI units). Measurements were made
up to 100C.
temperature, using Figure 2.) The point chosen to
represent the phytolith assemblage is where 50% of the
phytoliths have a higher RI than the oil. In this sample
it is 1·437. The 50% value can then be used to compare
phytolith RI values of different samples.
In Figure 5 we compare the RI values of burned and
unburned phytolith samples. This Figure shows that
unburned and burned samples have different ranges of
refractive indices. The variation does not depend on
the species, as can be seen by comparing the wheat and
pine samples (wh1, wh4 and p1) nor does it depend on
the wet extraction method used (wet ashing method 1
and method 2 (not shown)). Samples that were heated
show a shift to higher values of RI, as demonstrated by
wh1 and wh1/700 and p1 and p1/500. The range of 50%
RI values of burnt samples is between 1·442–1·452,
while the unburnt range is 1·417–1·438. These values
are similar to the RI values measured by Jones & Milne
(1963). The upper limit of the measurements here was
limited to the RI of the calibration oil at room tem-
perature (1·458). There is no overlap between the burnt
and unburnt 50% values, although the difference in
some samples is not large. Figure 5 thus shows that RI
can be used to differentiate between burnt and unburnt
phytolith assemblages. As this mode of measurement is
cumbersome and requires the use of a temperature
controlled stage, we developed a simplified measuring
222 R. Elbaum et al.
Figure 4. Distribution of the RI values of the plant shown in Figure
3, but represented as the fraction of wheat phytoliths (sample wh1)
that have a RI higher than that of the calibration oil. The RI values
on the x-axis were calculated from the sample temperature.
method that can be performed on any petrographic
light microscope.
Simplified method
According to Figure 5, when the 50% RI value is larger
than 1·440, the sample is burnt. This offers the oppor-
tunity to simplify the method and count the fraction of
phytoliths with RI lower than 1·440 in order to decide
whether the sample was burnt or not. To measure this
fraction all that is needed is to prepare the phytolith
sample immersed in a mineral oil of RI=1·440, and
count the fraction of phytoliths with bright contrast. If
more than 50% of the phytoliths in a sample have RI
higher than 1·440, the sample is most probably burnt.
The assumption is well founded if the 50% point is
much above 1·440 (or much below 1·440, for unburnt
samples), but could be ambiguous if it is close to 1·440.
Furthermore, in those cases most of the phytoliths will
hardly be visible and the error of the measurement will
be very high.
In order to determine the minimal number of parti-
cles needed to be counted for a reliable measurement,
samples of 400 particles or more were measured and
the ratio of phytoliths with RI>1·440 was recorded. It
was found that after counting 200 particles the ratio
did not change by much. To verify this observation we
conducted a statistical test for comparing two binomial
proportions. We compared the ratio after counting a
total number of 200 and 300 phytoliths and found that
200 particles are sufficient for 95% confidence. Some of
the samples that were measured by heated oil were
measured again in oil of RI=1·440. The results are
shown in Table 2. We thus conclude that this mode of
measurement can be used to differentiate most cases of
burnt from unburnt phytoliths.
We applied this simplified method to a pair of
samples from the Natufian sediments from Hayonim
Cave (samples A3, A4), and measured the fraction of
phytoliths with RI>1·440. In the sample from a hearth
(A3) 95% of the phytoliths have a RI>1·440, and in the
sample from the surrounding sediments (A4) 98% have
a RI>1·440. Analysis of the phytolith morphologies in
these samples showed that most of the plant material in
the sediment originated from grasses, with minor pro-
portions being derived from wood/bark and leaves
(Albert et al., 2001). The RI analysis thus shows that
both samples were burnt. We do note that one type of
phytolith, a spheroid of 7
m in diameter, consistently
had an RI<1·440, implying that it was not burnt.
Discussion
We present here a new method for identifying burnt
from unburnt phytolith assemblages in archaeological
sites based on the measurement of the RI of individual
phytoliths using a light microscope.
We found that individual phytoliths from a specific
plant have different RI values. The reason for this is
most probably the differences in the proportions of
water molecules that are incorporated into the opal
(Heinrich, 1965). The amount of water can be influ-
enced by the microenvironment in which the phytoliths
form, about which very little is known. This in turn
may also be related to the environmental conditions
during the life of the plant (Rosen, 1999). We also
noted that the 50% value is different for different plants
even of the same species (Figure 5). This too may be
due to differences in phytolith formation conditions or
different plant growth conditions. The variation of RI
within a plant, as shown in Figure 3, requires the
measurement of an assemblage of phytoliths in order
to determine whether or not it was burned.
The effect of burning on the refractive index depends
on the time and temperature of heating. The higher the
temperature, the stronger is the effect, as shown by
comparing the same sample exposed to 700C and
1000C (Figure 5—wh1/700, wh3/1000). Heating for
1·5 h at 700C showed a very weak shift in the refrac-
tive index, and heating to 200C did not affect the
refractive index at all (not shown). The temperature
range of a regular campfire is 600–900C (Livingstone,
2001). The fuel for fires exposed to temperatures higher
than 500C for several hours will therefore be easily
identified as burnt. Cooked food, on the other hand, is
exposed to temperatures around 200C. This level of
heating will not affect the RI of the phytoliths con-
tained in the food, and a RI shift will not be recog-
nized. Note that we did not notice a change in color in
the burnt phytoliths we examined. We did note that
Figure 5. Comparison of the RI distribution values of eight different phytolith samples. The fraction of phytoliths with RI higher than that of the calibration oil is plotted at each point.
Samples that were exposed to high temperatures are marked by the open symbols and thin lines. Samples that were not heated are marked by closed symbols and bold lines. The total number
of particles counted for each sample is marked in parenthesis. Samples details are shown in Table 1.
Detection of Burning of Plant Materials in the Archaeological Record 223
224 R. Elbaum et al.
Table 2. Percent of phytoliths with RI>1·440 measured by heated and
unheated oil
Measured
Measured by with oil of
Sample heated oil* RI=1·440*
wh1 13% (329) 15% (396)
wh2 19% (388) 21% (889)
wh1/700 65% (59) 50% (288)
wh3/1000 90% (65) 96% (216)
p1 35% (107) 29% (343)
A2 75% (46) 71% (208)
*Number in parentheses indicates the total number of phytoliths
counted.
elongated phytoliths exhibited some distortion when
heated to 900C.
Diagenesis of phytoliths is always an issue when
using them for analyses. It is conceivable that with time
at ambient temperatures the degree of hydration and
hence the RI may change. The sample from Grotte
XVI, which is dated to the Middle to Upper Paleolithic
transition, still shows RIs indicative of features of
burnt phytoliths (Figure 5—A2 and Table 2). Indeed
the layer from which the sample was derived shows
many signs of burning and many of the phytoliths were
derived from wood and bark (Karkanas et al., 2001).
From this we conclude that in this case the RI burnt
signal is preserved, and the opal did not rehydrate. The
sample from Qumran, which is dated to 5–10 ky ago,
shows a non-burnt phytolith RI signal (Figure 5—A1).
This is consistent with the fact that the organic matter
of this sample was still preserved and therefore it was
certainly not burned. This observation also supports
the assumption that a change in the RI does not occur
spontaneously with time.
The simplified method does not require a tempera-
ture controlled stage to measure RI values and there-
fore can be easily applied by using a regular light
microscope, even in the field. This increases the error of
the measurement because some fraction of the phyto-
liths may have a RI close to 1·440 and will hardly be
seen. The technique will only be definitive for samples
that have RI values shifted significantly from 1·440. To
be able to apply this method and reduce the error,
more than 200 particles should be measured. The
choice of measuring the 50% value in this study is
arbitrary. The 80% value also differentiates the burnt
from unburnt samples (Figure 5). For that an oil of RI
of 1·435 can be used, and a burnt sample will be a
sample in which more than 80% of the particles have a
bright contrast. Observation of the sample in a second
oil with RI far from 1·440 and identification of the
phytolith types may improve precision and the infor-
mation that can be obtained from this analysis (e.g. the
case study below).
Another source of error may be a mixed sample
of burnt and fresh phytoliths. If there is a way to
separate the two groups by their morphology, then it
may be possible to show that one group was burnt and
the other was not. But in any other case the measure-
ment of the refractive index will give a misleading
Burnt result, according to the proportions of the two groups
in the sample. The RI values of soil phytoliths from
— Illinois silt loam were analyzed previously (Jones &
— Beavers, 1963) and found to cover the whole range
+ of opal refractive indices observed here. About 75%
+ of the phytoliths in this sample have a RI equal or
—
+
higher than 1·440, a value which relates to a burnt
sample. This may be explained by degradation of the
plant material mainly by fire, though a fraction of
the sample may have been degraded by biological
processes.
Hayonim Cave case study
The Hayonim Cave study demonstrates a way to apply
the method developed here to an archaeological site.
Phytoliths from sediment samples of a hearth and the
sediments in which the hearth was buried showed RI
values greater than 1·440. This means that both
samples were burnt. The sample of the hearth consists
of the almost pure remains of the ash (mostly calcite)
(Albert et al., 2001) and is therefore expected to show
burnt features. The associated sediment also contains
large quantities of calcite together with smaller
amounts of clay. The RI analysis indicates that all the
phytoliths were burnt. This need not necessarily have
been the case as there could have been input of
phytoliths from outside the cave (together with the clay
material) or phytoliths could have been derived from
unburnt roofing or bedding materials. A comparison of
the phytolith types showed only minor differences
between the two samples (Albert et al., 2001) and this
is consistent with the fact that both are mainly or
entirely derived from ash.
It is interesting to note that one phytolith type, a
spheroid, consistently has a RI lower than 1·440 in
both samples, implying that it was not burnt. Spheroid
phytoliths are found in the wood and bark of many
trees, and also in their fruits. Comparing the size of
that spheroid to the ones cataloged in the reference
collection prepared from local vegetation (Albert &
Weiner, 2001) two possible sources arise. One is
that the phytoliths were derived from the wood of a
Christ-thorn tree (Ziziphus spina-cristi L.), and the
other is from the fruit of the Carob tree (Ceratonia
siliqua L). Both trees grow in the area of Hayonim
Cave today.
The fact that unburnt phytoliths are found in a
sediment that definitely originated from a hearth is
puzzling. We burned a Carob tree fruit at 800C for 3 h
and identified the spheroid phytoliths. They had a RI
higher than 1·440, as expected. Therefore we conclude
that the phytoliths found in A3 were not burnt, though
we cannot offer a simple explanation.
 Detection of Burning of Plant Materials in the Archaeological Record 225
Implications for archaeological applications
Since the phytolith shapes are often typical of their
source plant, it is possible to use phytolith RI to
identify the types of plants that were used for fuel.
Identifying the plants that were not burnt could indi-
cate use for roofing, food, bedding etc. This method
will help in reconstructing human behaviour at the
site—did people use the local vegetation for food? Did
they prefer certain kinds of wood for fire? Was the
entire site burnt from time to time (in order to clean it
or as a result of catastrophic fires)?
The effect of burning for periods longer than several
hours was not examined here. We observed a shift to
higher values of RI as a function of the exposure time
to heat, when comparing samples that were heated at
700C for 1·5 h and 7 h (not shown), and an even
stronger shift when heated to 1000C for a short time
(1·5 h) (Figure 5—wh3/1000). Jones & Milne (1963)
showed that the RI range decreases when phytoliths
are burnt at 1000C or higher. This may offer the
possibility of recognizing very high temperatures that
were due to catastrophic fires or possibly due to metal
or ceramic production.
Conclusions
We present here a method to differentiate between
phytolith samples that were exposed to high tempera-
tures characteristic of fire, and samples that were not
heated or heated to low temperatures for short times
that are characteristic of food preparation conditions.
The method was simplified such that it requires only a
petrographic microscope and a mineral oil with refrac-
tive index of 1·440. The simplified method cannot be
applied to mixed (burnt/unburnt) samples or to
samples with phytoliths that have refractive indices
close to 1·440.
The RI analysis may contribute to recognition of fire
in the archaeological record, and to understanding the
division of space within a site. It may be used to learn
about the utilization of specific plants, recognized by
their typical phytolith morphologies, for fuel or other
applications such as food, building material, baskets
and more.
Acknowledgements
We thank Arlene Rosen and Ruty Shahack-Gross for
the phytolith samples, and Edna Shechtman for the
help in the statistic analysis. This research was sup-
ported by THE ISRAEL SCIENCE FOUNDATION
(Center of Excellence, grant No. 302/00) to S.W., and
the Kimmel Center for Archaeological Science at the
Weizmann Institute.
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