See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/316699759

Plant Ash.

Chapter · September 2017

DOI: 10.1002/9781118941065.ch17

CITATIONS READS

21 2,897

2 authors:

Matthew Canti Jacques Elie Brochier

Historic England French National Centre for Scientific Research, Aix-en-Provence, France
58 PUBLICATIONS 2,566 CITATIONS 127 PUBLICATIONS 2,060 CITATIONS

SEE PROFILE SEE PROFILE

All content following this page was uploaded by Matthew Canti on 05 November 2019.

The user has requested enhancement of the downloaded file.


17
Plant Ash
Matthew G. Canti1 and Jacques Élie Brochier2
1
Historic England, Eastney, United Kingdom
2
Aix-Marseille Université (AMU), UMR 7269 LAMPEA, Aix‐en‐Provence, France
17.1 Introduction
Ash is formed when oxidation of plant material in fires
has progressed beyond charring, to the point where the
carbon, hydrogen and oxygen components are largely
vaporized. The previously small quantities of mineral
constituents in the plant then become the major
component left behind as ash.
17.1.1 Ash Composition
The main mineral constituents of plants are silica (sili-
ceous phytoliths) and calcium oxalate (oxalate phytoliths),
which exist in different forms and quantities according
to the plant families.
Silica is widespread in plants but commonest in the
monocotyledons, especially grasses and horsetails, where
it can be a large percentage of the ash composition. It
takes the form of intercellular and intracellular bodies,
either discrete phytoliths (Figure 17.1), multicellular
cuticle structures (Figure 17.2) or silica skeletons
cementing the whole vascular system (Figure 17.3).
Calcium oxalate (as the monoclinic monohydrate
whewellite, CaC2O4.H2O; or the tetragonal dihydrate
weddellite, CaC2O4.2H2O) is ubiquitous in most herbs,
trees and shrubs but very rare in grasses (Metcalfe 1960;
Prychid & Rudall 1999). It occurs in a variety of shapes
(see for examples Scurfield et al. 1973; Franceschi &
Horner 1980); the commonest types are the prismatic
crystals, which are single or twinned individual crystals,
typically 10–20 µm (Figure 17.4) and the druse, which
is a 15–50 µm rosette of radially aligned crystals
(Figure 17.5). They are generally not preserved in archae-
ological sediments, but have occasionally been found
protected in degraded plant tissues (Figure 17.6).
Archaeological Soil and Sediment Micromorphology, First Edition. Edited by Cristiano Nicosia and Georges Stoops.
© 2017 John Wiley & Sons Ltd. Published 2017 by John Wiley & Sons Ltd.
147
17.1.2 Ash Formation
On heating, calcium oxalate transforms directly into
calcium carbonate at around 400–500 °C by loss of CO
(Pobeguin 1943; Dollimore 1987; Frost & Weier 2003,
2004). If fires get hotter, CO2 is driven off leaving CaO,
which, on cooling becomes Ca(OH)2 then recarbonates
with atmospheric CO2 to form CaCO3. Experiments
with plant calcium oxalates show that the transformation
into lime occurs around 600 °C, which is lower than the
conversion temperature measured on synthetic calcium
oxalate (Pobeguin 1943; Brochier 1983). Recent experi-
mentation has, however, measured a higher transforma-
tion temperature (ca. 700 °C) from some plant oxalates
(Shahack‐Gross & Ayalon 2013), suggesting that influ-
ences from other variables are yet to be clarified for this
system. The calcium carbonate in ash can be derived
through either of these transformation (direct or by
recarbonation) routes (Folk 1973; Shahack‐Gross &
Ayalon 2013).
Although some changes occur during heating (notably
the loss of OH groups), silica is mostly unaffected by the
temperatures in normal domestic fires, as long as it does
not enter into a melt with alkaline salts (see section 17.2).
Variable quantities of mainly potassium and sodium salts
are present in fresh ash, and these can play a part in
subsequent taphonomic changes.
17.2 Micromorphology
The transformation of calcium oxalate into calcium
carbonate results in the molecular rearrangement of the
relatively large oxalate crystals into microcrystalline
aggregates of CaCO3, which retain the varied gross
148 Archaeological Soil and Sediment Micromorphology
20 μm
Figure 17.1 Silica phytoliths from garden soil deposits in
Leicester, United Kingdom. PPL.
30 μm
Figure 17.2 Dendriform phytoliths from Graminae. Middle Bronze
Age layers, Cazals cave (Aude). Viewed with interference contrast,
which improves image of isotropic materials.
250 μm
Figure 17.3 Silica skeletons left behind after burning of grasses
(Graminae sp.). PPL.
100 μm
Figure 17.4 Calcium oxalate crystals lining the veins in a leaf of
birch (Betula pendula). PPL.
25 μm
Figure 17.5 Druse, twinned and single prismatic calcium oxalate
crystals from a leaf of downy oak (Quercus pubescens). A few
siliceous tracheids (isotropic) are also visible. Viewed with
interference contrast, which allows birefringent and isotropic
materials to be seen in the same image.
morphologies of the oxalates. Thus, both prismatic and
druse pseudomorphs (Figures 17.7, 17.8 and 17.9) may
be found intact in ash (Brochier 1983; Brochier et al.
1992; Cailleau et al. 2005).
The pseudomorphs are made up of very small calcite
crystals, a few of which can be seen under the highest
magnification, but the remainder are submicron in size.
The smaller the crystals are, the higher is the proportion
of the microscopic view being taken up by the dark crys-
tal outlines. The pseudomorphs are thus darkened
almost to opacity in plane polarized light due to com-
pound relief produced by multiple overlying crystals
(Figure 17.9a). Under crossed polars (Figure 17.9b),
the compound birefringence of the stacked submicron

(a)
(b)
(c)
Figure 17.6 (a) Calcium oxalate crystals preserved in degraded
plant tissue in an ash deposit; note the grey colouration of the
microcrystalline calcium carbonate pseudomorphs produced by
compound relief (C), and the clearer light transmission through
the intact oxalate crystals (O). PPL. (b) Note the weaker compound
interference colours of the microcrystalline calcium carbonate
pseudomorphs (C) and the stronger ordered bands of interference
colours on the intact oxalate crystals (O). XPL. (c) Note the bright
diffused white of the calcium carbonate pseudomorphs (C) and
the duller transmitted light of the intact oxalate crystals (O).
Reflected light. Mesolithic layers, Cuzoul de Gramat rock shelter.
Image courtesy of G. Delfour.
Plant Ash 149
5 μm
Figure 17.7 SEM photograph of a twinned prismatic oxalate
crystal transformed into microcrystalline calcium carbonate.
Figure 17.8 SEM photograph of a twinned prismatic oxalate
crystal transformed into microsparitic calcium carbonate from
Neolithic layers in Santa Maira rock shelter (Alicante). Image
courtesy of C. Verdasco.
crystals produces high‐order interference colours but
the opacifying effect of the compound relief acts to
strongly reduce the overall brightness (Canti 2003). The
submicron crystals are randomly oriented; thus the
pseudomorphs never go into extinction when the stage
is rotated, although very elongated prisms may occa-
sionally show partial extinction. Under reflected light,
they appear as bright white crystalline forms owing to
150 Archaeological Soil and Sediment Micromorphology

(a) (b)

Figure 17.9 (a) Calcium carbonate pseudomorphs of prismatic crystals from modern bonfire ash, PPL. (b) Same as (a), XPL.

(a) (b)

Figure 17.10 (a) Pinus sylvestris L. (b) Tilia platyphyllos Scop. Radial sections showing calcitic pseudomorphs of prismatic oxalate crystals in
the phloem parenchyma cells. Photos: J. É. Brochier and M. Thinon.

light diffusion (see white areas in Figure 17.6c). Some

oxalate pseudomorphs, frequently observed in archaeo-
logical deposits, have slightly larger crystals (micro-
sparite – Figure 17.8). Their shapes are less sharp, and
they are sometimes difficult to recognize. They have
never been produced experimentally and the formation
process is still unclear, although some type of recrystal-
lization seems most likely (Brochier & Thinon 2003).
Although there are numerous forms of calcitic pseu-
domorphs after oxalate (as numerous as the crystal
habits of plant whewellite and weddellite), very few of
them can be attributed to a specific taxon. It is, how-
ever, possible to recognize, on morphometric grounds
(Brochier 1991, 1995), the genus Pinus (very elongated
prisms) and the two species (cordata and platyphyllos)
of the genus Tilia (elongated and short prisms associ-
ated with druses). See Figures 17.10, 17.11 and
Table 17.1.
Figure 17.11 Prismatic pseudomorph from Balma de la
It is often not possible to see the edges of densely Margineda (Andorra, Early Neolithic). The elongation index of
packed siliceous phytoliths in thin sections, but the 3.6 and width of 16 µm indicates the genus Tilia. PPL.
 Plant Ash 151

Table 17.1 Statistical parameters of elongation index, length and width for Tilia cordata, T. platyphyllos, Pinus
halepensis and prismatic calcium carbonate pseudomorphs.

Distribution data Pinus halepensis Pinus sylvestris Tilia cordata Tilia platyphyllos

Elongation index (length/width)

Mean ± standard error 5.33 ± 0.29 6.06 ± 0.42 2.76 ± 0.08 3.88 ± 0.16
Standard deviation 1.01 1.57 0.48 1.03
Median 5.20 5.84 2.67 3.77
Quartile 1 4.38 4.73 2.38 3.22
Quartile 3 6.29 6.93 3.05 4.54
Maximum 7.2 10.0 4.0 6.6
Minimum 4.0 4.0 1.8 2.1

Length (µm)
Mean ± standard error 39.0 ± 2.0 30.5 ± 2.3 43.6 ± 1.3 45.0 ± 1.6
Standard deviation 6.8 8.5 8.1 10.7
Median 40.0 29.3 41.8 45.3
Quartile 1 35.6 23.6 37.5 35.0
Quartile 3 43.8 35.6 48.1 52.0
Maximum 50.0 50.0 62.0 70.0
Minimum 25.0 20.0 29.5 25.0

Width (µm)
Mean ± standard error 7.5 ± 0.5 5.0 ± 0.2 16.2 ± 0.6 11.9 ± 0.4
Standard deviation 1.8 0.6 3.7 2.3
Median 7.3 5.0 15.0 10.5
Quartile 1 6.1 4.9 13.9 10.0
Quartile 3 9.4 5.0 19.3 14.6
Maximum 10.0 7.0 25.0 15.5
Minimum 5.0 4.5 10.0 7.0

negative relief of opaline silica (R.I. typically 1.41–1.46)
is frequently noticeable on the surfaces and sculpturing
of phytoliths in plane polarized light. Under crossed
polars, silica phytoliths are isotropic (Figure 17.12).
Although the gross morphology of opaline silica is
largely unchanged in ash, heating phytoliths does alter
the refractive index by removing the water and hydroxyl
groups (Elbaum et al. 2003). The effect must technically
be visible in thin sections but the range of RI differences
is quite small (ca. 0.05) and measuring it requires delib-
erate sample preparation in refractive oil. Phytoliths can
be darkened by burning but some are naturally dark
without any heating (Parr 2006). These colour differ-
ences are thought to be due to occluded carbon, which
can also provide valuable radiocarbon dates (Wilding
1967; Mulholland & Prior 1992), but see Santos et al.
(2012) for problems with this approach.
Silica can undergo significant morphological altera-
tion by fusion. This happens when the ash contains a
high enough proportion of fluxing agents such as sodium
and potassium, which lower the overall melting point of
the mixture. The resulting material ranges from a lightly
fused cast of the original plant silica skeleton through to
lumps of glassy clinker‐like material, usually vesicular
(Figure 17.13) due to gas bubbles developing in the liquid
melt (Vélain 1878; Folk & Hoops 1982; Thy et al. 1995;
Guélat et al. 1998; Brochier & Claustre 2000; Canti 2007).
Fused silica can form considerable accumulations as, for
example, in the Deccan ash mounds (Allchin 1963) and
burnt kraals in South Africa (Jacobson et al. 2003).
152 Archaeological Soil and Sediment Micromorphology

(a) (b)

Figure 17.12 Silicified plant remains (Si) in mixed ash from the fuel of a corn drying oven at Grateley, United Kingdom. (a) PPL; (b) XPL.

17.3 Ash Taphonomy

Once deposited, ash can undergo a wide range of tapho-
nomic processes, including trampling, mixing, colluvia-
tion and recrystallization (Brochier 1993, 2002; Karkanas &
Goldberg 2010; also see Mallol et al. 2017, this book).
If retained in a dry, undisturbed environment, ash will
preserve indefinitely, but this is not the commonest
taphonomic outcome. Many outdoor archaeological sit-
uations have enough rainfall to dissolve it completely,
sometimes leaving a fine charcoal layer to mark where
the ash used to be. Areas of restricted rainfall, for exam-
ple Middle Eastern open‐air sites, will retain ash to a
considerable extent where burial is rapid (e.g., Shillito
et al. 2011; Friesem et al. 2014; Gur‐Arieh et al. 2014).
Figure 17.13 Silica ash melt from Northampton, United
Kingdom. PPL. The best preservation is generally found in caves and

(a) (b)

Figure 17.14 (a) Ash from Early Neolithic cave deposits in the Upper Ebro valley with slightly browner central area of phosphatic staining,
PPL. (b) Same as (a), with central area of phosphatic staining producing isotropy. XPL. Image courtesy of A. Polo Díaz.

rock shelters. These have often sustained long periods of
occupation, sometimes with repeated burning of animal
bedding and manure, resulting in deep ash accumula-
tions. However, even caves contain moist air, dripping
water and bat colonies, which together produce a range
of effects. The ash itself will sometimes partially dissolve
and recrystallize as neoformed calcite, losing some or all
of its oxalate pseudomorph characteristics. In the pres-
ence of phosphates (from either degrading bat guano or
dissolving bones), the ash calcite will convert to apatite
or other phosphates (Karkanas et al. 2000; Shahack‐
Gross et al. 2004) and therefore loose its birefringence.
References
Allchin, F. R. (1963) Neolithic Cattle Keepers of South
India. A Study of the Deccan Ashmounds. Cambridge
University Press, Cambridge.
Brochier, J. É. (1983) Bergeries et feux néolithiques dans le
Midi de la France, caractérisation et incidence sur le
raisonnement sédimentologique. Quatar 33/34,
181–193.
Brochier, J. É. (1991) Géoarchéologie du monde
agropastoral. In: Guilaine, J. (ed.) Pour une Archéologie
Agraire,. Armand Colin, Paris, pp. 303–322.
Brochier, J. É. (1993) Çayönü Tepesi. Domestication,
rythmes et environnement au PPNB. Paléorient 19/2,
39–49.
Brochier, J. É. (1995) Estudi geoarqueològic dels dipòsits
holocens de la Balma de la Margineda: capes de 1 a la 6.
(Étude géoarchéologique des dépôts holocènes de la
Balma Margineda, Andorre, couches 1 à 6). In: Guilaine, J.
& Martzluff, M. (eds) Les Excavacions a la Balma de la
Margineda (1979–1991), Vol. 1. Edicions del Govern
d’Andorra, Andorra, pp. 56–90.
Brochier, J. É. (2002) Les sédiments anthropiques.
Méthodes d’étude et perspectives. In: Miskovsky, J. C.
(ed.) Géologie de la Préhistoire: Méthodes, Techniques,
Applications. Géopré Éditions, Paris, pp. 453–477.
Brochier, J. É. & Claustre, F. (2000) Le parcage des bovins
et le problème des litières du Néolithique final à l’Âge du
Bronze dans la Grotte de Bélesta. In: Vaquer, J., Guilaine,
J. & Martin, H. (eds) Le Néolithique du Nord‐ouest
Méditerranéen: XXIVe Congrès Préhistorique de France,
Carcassonne, 1994. Actes Société Préhistorique
Française, Paris, pp. 27–36.
Brochier, J. É. & Thinon M. (2003) Calcite Crystals, Starch
Grains Aggregates or … POCC? Comment on ‘Calcite
Crystals inside Archaeological Plant Tissues’. Journal of
Archaeological Science 30, 1211–1214.
Brochier, J. É., Villa, P., Giacomarra, M. et al. (1992)
Shepherds and sediments: Geo‐ethnoarchaeology of
Plant Ash 153
Near‐isotropic areas in ashy deposits often signal this
process (Figure 17.14).
Geogenic calcite in the form of either fragments of
limestone from cave walls / roof or speleothems is some-
times difficult to distinguish from recrystallized calcitic
ash without additional analyses (Shahack‐Gross et al.
2008; Shahack‐Gross & Ayalon 2013). Where detrital
inputs are significant to interpretation, variation in the
abundance of calcitic pseudomorphs dispersed in an
archaeological profile can play a useful role (along with
other anthropic particles) in helping determine sedimen-
tation / dissolution rates (Brochier 1993, 1995).
pastoral sites. Journal of Anthropological Archaeology
11, 47–102.
Cailleau, G., Braissan, O., Dupraz C. et al. (2005)
Biologically induced accumulations of CaCO3 in orthox
soils of Biga, Ivory Coast. Catena 59, 1–17.
Canti, M. G. (2003) Aspects of the chemical and
microscopic characteristics of plant ashes found in
archaeological soils. Catena 54, 339–361.
Canti, M. G. (2007) Geoarchaeological studies at
Flixborough‐North Conesby: understanding the burial
environment, taphonomy and preservation conditions.
In: Loveluck, C. & Atkinson, D. (eds) The Early Medieval
Settlement Remains from Flixborough, Lincolnshire:
The Occupation Sequence, c. AD 600–1000. Oxbow
Books, Oxford, pp. 17–23.
Dollimore, D. (1987) The thermal decomposition of
oxalates. A review. Thermochimica Acta 117, 331–363.
Elbaum, R., Weiner, S., Albert, R. M. et al. (2003) Detection
of burning of plant materials in the archaeological
record by changes in the refractive indices of siliceous
phytoliths. Journal of Archaeological Science 30,
217–226.
Folk, R. L. (1973) The geological framework of Stobi.
Studies in the Antiquities of Stobi, 1, 37–59.
Folk, R. L. & Hoops, G. K. (1982) An early Iron‐Age layer
of glass made from plants at Tel Yin’am, Israel. Journal of
Field Archaeology 9, 455–456.
Franceschi, V. R. & Horner, H. T. (1980) Calcium oxalate
crystals in plants. The Botanical Review 46, 361–427.
Friesem, D. E., Zaidner, Y. & Shahack‐Gross, R. (2014)
Formation processes and combustion features at the
lower layers of the Middle Palaeolithic open‐air site of
Nesher Ramla, Israel. Quaternary International 331,
128–138.
Frost, R. L. & Weier, M. L. (2003) Thermal treatment of
weddellite – a Raman and infrared emission
spectroscopic study. Thermochimica Acta 406, 221–232.
154 Archaeological Soil and Sediment Micromorphology
Frost, R. L. & Weier, M. L. (2004) Thermal treatment of
whewellite – a thermal analysis and Raman
spectroscopic study. Thermochimica Acta 409, 79–85.
Guélat, M., Paccolat, O. & Rentzel, P. (1998) Une étable
gallo‐romaine à Brigue‐Glis VS, Waldmatte. Annuaire
de la Société Suisse de Préhistoire et d’Archéologie 81,
171–182.
Gur‐Arieh, S., Shahack‐Gross, R., Maeir, A. M. et al. (2014)
The taphonomy and preservation of wood and dung
ashes found in archaeological cooking installations: case
studies from Bronze and Iron Age Israel. Journal of
Archaeological Science 46, 50–67.
Jacobson, L., Loock, J. C., van der Westhuizen, W. A. et al.
(2003) The occurrence of vitrified dung from the
Kamdeboo district, southern Karoo, and Den Staat,
Limpopo Valley, South Africa. South African Journal of
Science 99, 26–28.
Karkanas, P., Bar‐Yosef, O., Goldberg, P. et al. (2000)
Diagenesis in prehistoric caves: The use of minerals
that form in situ to assess the completeness of the
archaeological record. Journal of Archaeological
Science 27, 915–929.
Karkanas, P. & Goldberg, P. (2010) Site formation processes
at Pinnacle Point Cave 13B (Mossel Bay, Western Cape
Province, South Africa): resolving stratigraphic and
depositional complexities with micromorphology.
Journal of Human Evolution 59, 256–273.
Mallol, C., Mentzer, S. M. & Miller C. E. (2017)
Combustion features. In: Nicosia, C. & Stoops, G. (eds)
Archaeological Soil and Sediment Micromorphology.
John Wiley & Sons, Ltd, Chichester, pp. 299–330.
Metcalfe, C. R. (1960) Anatomy of the Monocotyledons. I.
Graminae. Clarendon Press, Oxford.
Mulholland, S. C. & Prior, C. (1992) Processing of
phytoliths for radiocarbon dating by AMS. The
Phytolitharien Newsletter 7, 7–9.
Parr, J. F. (2006) Effect of fire on phytolith coloration.
Geoarchaeology 21, 171–185.
View publication stats
Pobeguin, T. (1943) Les oxalates de calcium chez quelques
angiospermes. Annales des Sciences Naturelles,
Botanique et Biologie Vegetale (11th series) 4, 1–95.
Prychid, C. J. & Rudall, P. J. (1999) Calcium oxalate crystals
in Monocotyledons : A review of their structure and
systematics. Annals of Botany 84, 725–739.
Santos, G. M., Alexandre, A., Southon, J. R. et al. (2012)
Possible source of ancient carbon in phytolith
concentrates from harvested grasses. Biogeosciences 9,
1873–1884.
Scurfield, G., Michell, A. J. & Silva, S. R. (1973) Crystals in
woody stems. Botanical Journal of the Linnean Society
66, 277–289.
Shahack‐Gross, R., Ayalon, A, Goldberg, P. et al. (2008)
Formation processes of cemented features in karstic cave
sites revealed using stable oxygen and carbon isotopic
analyses: A case study at Middle Paleolithic Amud Cave,
Israel. Geoarchaeology 23, 43–62.
Shahack‐Gross, R. & Ayalon, A. (2013) Stable carbon and
oxygen isotopic compositions of wood ash:
An experimental study with archaeological implications.
Journal of Archaeological Science 40, 570–578.
Shahack‐Gross, R., Berna, F., Karkanas, P. et al. (2004) Bat
guano and preservation of archaeological remains in cave
sites. Journal of Archaeological Science 31, 1259–1272.
Shillito, L‐M., Bull, I. D., Matthews, W. et al. (2011)
Biomolecular and micromorphological analysis of
suspected faecal deposits at Neolithic Çatalhöyük,
Turkey. Journal of Archaeological Science 38, 1869–1877.
Thy, P., Segobye, A. K. & Ming, D. W. (1995) Implications
of prehistoric glassy biomass slag from East‐Central
Botswana. Journal of Archaeological Science 22,
629–637.
Vélain, C. H. (1878) Étude microscopique des verres
résultant de la fusion des cendres de graminées. Bulletin
de la Société Française de Minéralogie 1, 113–125.
Wilding, L. P. (1967) Radiocarbon dating of biogenic opal.
Science 156, 66–67.