The Science of the Total Environment 308 (2003) 111–119

Micromorphology, composition and origin of the orange patina on

the marble surfaces of Propylaea (Acropolis, Athens)
Kyriaki Polikreti*, Yannis Maniatis
Laboratory of Archaeometry, NCSR ‘Demokritos’, Aghia Paraskevi, Attikis 153 10, Greece

Received 10 June 2002; accepted 6 November 2002

Abstract

This paper is an attempt to contribute to the discussion started in the 1980s and continuing until today, on the
origin of orange–brown patinas observed on marble surfaces. SEM and XRD were used in the study of the orange–
brown patina growing at the east stoa of Propylaea, at the Acropolis of Athens. The patina consists of an extremely
compact, homogenous, 500-mm-thick layer, mainly of hydroxyapatite. The outer part (50 mm) of the layer presents
an orange colour attributed to iron in clay particles, which were deposited on the surface of the patina and have
gradually been diffused in the bulk. The interface between the phosphatic layer and the marble is very uneven and
full of cavities colonised by microorganisms. The phosphatic layer penetrates into the grain boundaries and fills the
empty space between the grains. The presence of biological attack at the interface causes progressive erosion and
detachment of both the patina and the marble. The minimum presence of oxalates, the absence of microorganisms or
remnants of them in the phosphatic layer, the homogeneity and compactness of the patina, give evidence against the
theory of biogenic origin. It is suggested that the layer originates from an artificial coating deliberately applied onto
the marble surface for protective or aesthetic reasons, when the marble had already been weathered. Possible manmade
pastes are suggested.
䊚 2002 Elsevier Science B.V. All rights reserved.

Keywords: Marble; Phosphatic patina; Crust; Orange patina; Acropolis

1. Introduction of a few millimetres, well adhered to the marble

This work attempts to contribute to the contro-
versy, which started in the 1980s and continues to
this day, on the origin of orange–brown patinas
observed on marble surfaces. These patinas have
been detected on several Mediterranean monu-
ments and consist of a compact, usually hard layer
*Corresponding author. Tel.: q30-10-6503326; fax: q30-
10-6519430.
E-mail address:
kpolikreti@ims.demokritos.gr (K. Polikreti).
surface with colours varying from dark brown to
light pink. This ‘ochrish tint’ has been reported by
scholars, painters and travellers of the 19th century
(on the Parthenon columns), it is visible on pho-
tographs of the beginning of this century, but has
almost disappeared today.
Its main constituents are oxalates and phos-
phates while high concentrations in Si and Fe have
also been reported (Del Monte et al., 1987; Kouz-
eli et al., 1988; Lazzarini and Salvatori, 1989;
Fassina, 1995). Oxalates are not always present

0048-9697/03/$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 4 8 - 9 6 9 7 Ž 0 2 . 0 0 6 1 3 - 7
112 K. Polikreti, Y. Maniatis / The Science of the Total Environment 308 (2003) 111–119
(Kouzeli et al., 1996) and the concentration of
silicon varies, depending on the natural or anthro-
pogenic factors involved wpast treatment with Kes-
slers’ method for example causes increase in Si
(Fassina, 1995)x.
Two theories have been suggested for its
formation:
(a) The ‘artificial coating’ theory. A group of
researchers believe that the oxalates and phos-
phates have been produced by the bio-degradation
of complex proteins, which were used as protective
materials. Such materials could be the white of
egg, milk, calcium caseinate, animal glue, linseed
oil, etc.
Kouzeli et al. (1988) report the presence of an
orange patina on a Parthenon column, which con-
sists of two layers: (a) a superficial one (thickness
of 100 mm) consisting of aluminosilicates, calcium
carbonate and phosphate and occasionally gypsum;
and (b) a soft, white inner layer (1 mm), consist-
ing of calcium carbonate and oxalates. The unifor-
mity of the patina and the presence of phosphorus
support the hypothesis of a treatment with a
substance such as casein, egg white or animal
glue. The patina covers the broken surfaces of
sculpture, which are dated approximately 379–385
AD, a fact that dates the treatment during the
transformation of the Parthenon into a church
(527–565 AD).
Lazzarini and Salvatori (1989) report the pres-
ence of this patina, called ‘scialbatura’ in several
Roman monuments. They detect brushstrokes on
the patina, and suggest a protective coating made
of calcium caseinate (a well-known glue), proba-
bly with a small amount of yellow–brown ochre.
The proteolytic activity of some heterotrophic
bacteria, streptomycetes or hyphomycetes is
responsible for the hydrolysis of casein. They also
report the existence of patinas without oxalates but
with high amounts of phosphorus (20%), silicon
(25%), iron (5%) and aluminium (7%).
Jenkins and Middleton (1988) report the pres-
ence of oxalates on the surface of the Parthenon
sculpture and architectural pieces from the Elgin
collection (British Museum) and attribute them to
the use of some vegetable or animal substances
for producing paint.
Fassina et al. (1993) report the presence of a
yellow–brown film on two pillars, brought to
Venice in 1258 AD. The presence of oxalates and
phosphates is accompanied by high concentration
of silicon. The presence of silicon is attributed to
the transformation of fluorosilicates, which accord-
ing to the archives, were applied onto the pillars
in 1892. The treatment with fluorosilicates, in three
successive applications, was done according to
Kessler’s method (1883, Fassina et al., 1993). For
the presence of phosphorus, they refer to Ran-
some’s method (1856, Fassina et al., 1993), which
consisted of three application steps: (a) calcium
phosphate; (b) barite solution; and (c) alkaline
silicate.
Papakonstantinou (1994) detects amines, hydro-
carbonates and carbonylic groups on orange–
brown patinas of the West Zoforos of Parthenon.
Casoli et al. (1997) detected amino acids and fatty
acids in orange patinas from the Baptistery of
Parma, indicating the presence of egg proteins,
animal glue or linseed oil.
(b) The ‘biogenic origin’ theory, explains the
presence of oxalates by the action of oxalic acid
secreted by microorganisms, which colonise the
monuments (Del Monte and Sabbioni, 1987; Del
Monte et al., 1987). The interface between the
oxalate layer and the marble is very irregular, with
marble crystals rarely isolated in the oxalate crust,
an observation indicating that it is not a layer
deposited on the stone but rather a transformation
layer within the stone. The transformation is done
by a metasomatic process, which can form up to
20 successive layers. As for the colour, varying
from honey–yellow to orange–brown, it is pro-
duced mainly by carotene-carotenoids or fungal
melanins (especially by the black fungi of the
Dematiacea group) (Krumbein, 1992; Urzi et al.,
1993; Sterflinger and Krumbein, 1997).
More recently, Garcia-Valles et al. (1997, 1998)
report that these patinas show an up to 95% content
of micritic to microsparitic calcite, which is formed
by the mineralisation and successive diagenetic
processes of epilithic colonies of microorganisms.
The orange–brown colour is produced by the
organic matter (melanines, carotenoids or keroge-
ne), trapped between the crystals of the biominer-
als. This process is repeated giving the patina a
 K. Polikreti, Y. Maniatis / The Science of the Total Environment 308 (2003) 111–119
stratified structure. Due to the climatic shift to
dryer and hotter conditions, the microorganisms
avoid the surface due to the lack of water and
intense UV irradiation. They penetrate the patina,
creating a fissure-net along the interface, where
they live. There, they erode the stone causing
detachment of the patina.
Since we do not know if this patina is artificial
or natural, the problem of cleaning or consolidating
it remains unsolved. Besides, these patinas are
reported to keep the relief details and protect the
surface from further weathering (Kouzeli et al.,
1988). However, they are destroyed by acid rain,
since they were reported to exist on Parthenon
surfaces by scholars of the 19th century but have
almost disappeared today (Jenkins and Middleton,
1988).
2. Material studied and experimental techniques
Two types of surface samples were taken with
a surgical blade, from two different locations on
the south wall of the east stoa of Propylaea,
Acropolis (Athens). The first type includes patina
samples with yellow–orange patches on a pale
white base while the second type includes grey–
black surface samples, full of cavities with black
biogenic material.
The samples were analysed with optical micro-
scopy, X-ray diffraction (XRD) analysis and ana-
lytical scanning electron microscopy (SEM) with
EDX microanalysis system using a detector with
removable window for detecting low elements,
down to atomic numbers5 (boron). The semi-
quantitative elemental analysis was ‘standardless’
(accuracy of 1–2%) and obtained with EDAX
software.
3. Results
Under the stereoscope, the outer surface of the
patina sample shows an orange–red colour on a
whitish, non-crystalline layer. Black colonies or
remnants of microorganisms are visible at the
lower parts of the whitish layer and in the marble
crystals. In places where the patina has been
removed, the marble grains under the coating are
corroded, showing large cavities.
113
Fig. 1. Cross-section of the orange–brown patina (polarised
light). The outer coloured layer varies between 40 and 70 mm.
Optical microscopy shows a compact, homoge-
neous, non-crystalline, 500-mm-thick layer, which
covers the marble surface on all samples (Fig. 1).
The outer part of this layer (50–70 mm) shows a
yellow–orange colour and an extremely homoge-
neous texture. Below the outer coloured part, the
layer is whitish and shows a number of cavities,
which are multiplied as we approach the marble
grains. The total distance from the top of the
patina to the healthy marble bulk is approximately
1 mm.
X-Ray diffraction detects calcite (CaCO3),
ankerite wCa(Mg,Fe)(CO3 )x, hydroxyapatite
wCa5(PO4)3(OH)x and quartz (SiO2 ), in all sam-
ples. No calcium oxalates were detected.
3.1. Scanning electron microscopy
3.1.1. Outer surface
The outer surface is relatively smooth and flat.
The microanalysis gives mainly calcium, alumini-
um, silicon, phosphorus, and in lower quantities
magnesium, sulfur and iron (Fig. 2). Calcium and
phosphorus represent the hydroxyapatite of the
phosphatic layer. Sulfur is attributed to gypsum
crystal aggregates, occasionally seen on the sur-
face. EDX microanalysis gives elemental propor-
tions on Fig. 2 (aluminiumysiliconycalcium),
which indicate clay minerals. The presence of iron
in the clay gives the outer surface a red or yellow
colour (orange appearance), depending on the clay
density. Red coloured areas appear to have higher
114 K. Polikreti, Y. Maniatis / The Science of the Total Environment 308 (2003) 111–119

Fig. 2. Typical EDX spectrum of the outer surface.

concentrations of clay minerals, compared with Fig. 3. Colonies of microorganisms appearing from cracks on
the yellow ones. the outer smooth surface of the phosphatic layer.
The low intensity of the carbon peak indicates
the small contribution of biogenic factors in the apatite wCa5(PO4)3(OH)x. The proportion of CayP
formation of the outer surface. Only rarely, the is almost 2 (Fig. 5), which ensures that the
continuity of the outer surface is interrupted by presence of calcite in the layer is not critical. In
small cracks, which reveal colonies of microorgan- addition, the low intensity of the carbon peak
isms (their micromorphology indicates black fungi, together with the XRD results, indicate the possible
Fig. 3). These colonies appear usually as chains presence of oxalates is also not important for the
or spherical aggregates of spherical formations, formation of the layer (the average intensity of the
which penetrate deep in the interface between the carbon peak due to carbon coating was taken into
phosphatic layer and the marble. account).
3.1.2. Phosphatic layer Magnesium, aluminium, silicon, potassium and
The phosphatic layer is extended to a thickness iron are also present in the phosphatic layer. Their
of approximately 500 mm. Its amorphous nature,
homogeneity and absence of any obvious crystal-
line structure are its main characteristics (Figs. 4
and 5), especially at the outer 70–100 mm. Cavi-
ties (diameters ;50 mm) are observed in it,
together with fissures continuing the cracks appear-
ing on the outer surface. As we approach the
marble surface the diameter of the cavities increas-
es and in contact with the surface, are inhabited
by microorganisms.
Table 1 shows a semi-quantitative chemical
analysis of this layer (EDX). Calcium and phos-
phorus are the two main constituents. Several point
analyses at different locations give very similar
results proving that phosphorus is very homoge-
neously distributed. These observations in combi-
nation with the XRD results, lead to the conclusion Fig. 4. Compact phosphatic layer at the right top and cavities
that the main constituent of the layer is hydroxy- with microcolonies at the interface ‘phosphatic layer-marble’.
 K. Polikreti, Y. Maniatis / The Science of the Total Environment 308 (2003) 111–119 115

Fig. 5. Compact and homogenous phosphatic layer and corresponding EDX spectrum.

relative concentration, however, indicates that and analysis grain-by-grain of the interface leads
these elements are associated with clay minerals. to the firm conclusion that the original ‘undis-
The clay minerals are clearly abundant in the first turbed’ thickness of the phosphatic layer is approx-
5 mm from the outer surface but decreases pro- imately 200 mm. However, the phosphatic layer
gressively with depth and becomes negligible after usually fills the cavities and penetrates between
the first 50–70 mm. This gradual decrease indi- the marble grains (Figs. 6 and 7) to a depth of
cates that the clay minerals originate from environ- 500 mm. In many cases, the presence of cavities
mental depositions, which are subsequently can be associated with crystals that have been
absorbed in the phosphatic layer. removed (noted with asterisks in Fig. 6) and in
other cases, the phosphatic layer has penetrated
3.1.3. ‘Phosphatic layer–marble’ interface
The interface between the phosphatic layer and
the marble is by no means even or smooth, but
shows numerous cavities with a diameter of 30–
300 mm. The grain boundaries are corroded and
the marble crystals are loose, down to a depth of
approximately 400 mm inside the underlying mar-
ble. Isolated marble crystals were not observed
inside the phosphatic layer. Detailed examination

Table 1
Semi-quantitative EDX analysis of the phosphatic layer

Element Oxide
Al 0.09 0.17
Si 1.29 2.76
P 19.3 44.3
S 0.88 2.19
Cl 0.10 0.12 Fig. 6. General view of the patina under the SEM (the asterisks
Ca 36.0 50.4 indicate cavities most probably corresponding to missing mar-
ble crystals).
116 K. Polikreti, Y. Maniatis / The Science of the Total Environment 308 (2003) 111–119

patina. We are going to discuss these questions

separately although the arguments and speculations
sometimes overlap.

4.1. The origin of the patina is natural or

manmade?

The morphology, thickness and homogeneity of

the phosphatic layer, as well as the unexpected
smoothness of its outer surface are indications of
an artificial coating, deliberately laid on the marble
surface. No biogenic remnants or peculiar shapes
indicating bio-mineralisation of microorganisms
were found in the mass of hydroxyapatite. The
layer does not show any stratified structure or
differences in crystal dimensions from the top to
Fig. 7. Magnification =10, showing the interface between the inner parts. Living microorganisms were not
marble crystals and hydroxyapatite (Msmarble, Has
Hydroxy-apatite). found in it, except in the cracks and at the
interface. The hypothesis thus of a metasomatic
between marble crystals (Fig. 7) that were obvi- process or bio-mineralisation (Del Monte et al.,
ously loose and opened up prior to the occurrence 1987; Garcia-Valles et al., 1998) cannot be sup-
of the layer. The missing crystals must have been ported. Besides, the presence of oxalates (if any)
dilutedydestroyed by the biological action of the is negligible and calcite is not in abundant to
microorganisms or removed during the polishing indicate calcification processes. Furthermore, this
treatment. simultaneous absence of oxalates and calcite (in
These cavities are usually full of colonies in the high amounts) does not support the hypothesis
form of spherical aggregates similar to those proposed by some researchers that the oxalates
observed on the outer surface (Figs. 3 and 8). On have been gradually transformed to calcite by UV
the cavity walls, pyramid-shaped crystals, the irradiation (Kouzeli et al., 1996).
micro-analysis of which gives only Ca, are usually
present. This is a form of calcite, ‘spiky calcite’
as it is usually referred (Garcia-Valles et al., 1997,
1998). It is observed only at the interface between
crusts and marble and is attributed to the chemical
action of fungi on the marble crystals.
When the outer part of the phosphatic layer has
been removed, the surface is full of cavities with
depositions and colonies of microorganisms. The
composition of the depositions is mainly silicon,
aluminium, potassium, iron, which indicate clay
particles and small amounts of sulfur, indicating
gypsum. The microorganisms have the same shape
and morphology as those found in the cavities and
cracks of the orange patina and interface.
4. Discussion
Fig. 8. Cavities in the marble matrix, colonised by microor-
A lot of critical questions arise concerning both ganisms, at the interface between the phosphatic layer and the
the formation and the evolution of the phosphatic marble.
 K. Polikreti, Y. Maniatis / The Science of the Total Environment 308 (2003) 111–119
4.2. What is the origin of the orange–brown
colour?
The colour of the patina originates from the
presence of clay minerals (bearing iron oxides) in
the superficial layers. The progressive decrease of
the clay content with depth indicates environmen-
tal origin, i.e. atmospheric depositions, which have
been absorbed in the phosphatic layer. The various
shades of orange correspond to different clay
mineral concentrations. The environmental origin
of the colour leads us to the conclusion that the
original colour of the patina and consequently the
manmade coating was white or whitish, as the
colour of the inner parts of the phosphatic layer.
We have to note here, that analysis of the samples
with electron paramagnetic resonance spectroscopy
in order to detect fungal melanins (Saiz-Jimenez
and Shafizadeh, 1985) did not detect any traces of
organic radicals related to melanins.
4.3. When was the protectiveyaesthetic coating
applied?
In an attempt to answer this question, a few
deductions can be done based on the study of the
interface between the phosphatic layer and the
marble. A first invaluable observation is that the
marble surface is very irregular and the grains
have lost their cohesion not only due to the action
of microorganisms. The phosphatic layer usually
penetrates between the marble grains and in the
grain boundaries, indicating that when it was
applied, the marble had already been weathered.
If the coating had been applied on a healthy marble
surface, and the corrosion of the marble came
afterwards due to microorganisms, the cavities on
the marble surface would be either empty or full
of microorganisms alive or dead. This hypothesis
means that the application dating lies far from the
ancient times and it was done for conservation and
protection purposes.
Reference to the Acropolis conservation
archives cannot illustrate the situation. Although
N. Balanos, who restored Acropolis in the begin-
ning of the century, reports that he used a water-
proofing substance without naming it and A.
Shabonnier (a colleague of Balanos) refers to the
117
use of fluorosilicates on Acropolis monuments, it
is not reported that such procedures were per-
formed (Papakonstantinou, 1994).
4.4. What was the original composition of the
coating?
Several recipes have been proposed by the
researchers of orange–brown patinas, always
according to ancient bibliography or the archives
containing the studied monument’s conservation
history. Most probable components are casein
(milk), egg white or animal glue (Kouzeli et al.,
1988; Lazzarini and Salvatori, 1989; Melucco
Vaccaro, 1996).
Pliny (Natural History, XXXVI, 55, 177) refers
to the use of plaster worked with milk (calcium
caseinate) and saffron. Calcium caseinate is a
strong glue, widely used until a few decades ago
in the field of restoration (Lazzarini and Salvatori,
1989), but according to Kouzeli et al. (1996)
treatment of marble surfaces with sodium silicate
solutions containing casein or calcium phosphate
did not result in films similar to the well-known
orange–brown layers.
We think that pulverised animal bones diluted
in an appropriate solvent is the most possible
recipe in agreement with other researchers (Martin-
Gil et al., 1999). Collagen contained in the bones
could also act as an adhesive. Archives of the 11th
century report the treatment of the stone surface
with an animal glue before the application of paint
(Melucco Vaccaro, 1996).
Ransome’s method (1856) includes a first appli-
cation step with calcium phosphate, but the next
two steps (barite solution and an alkaline silicate)
are expected to have left detectable remnants (high
concentration of Ba and Si). More extended
research is thus needed to confirm the original
content of the treatment material.
4.5. Why the patina gradually disappears (at least
since 1950)?
The disappearing of the patina seems to result
from the corrosive action of two factors: microor-
ganisms and acid rain. We have to emphasise here,
that the phosphatic layer does not seem to be a
118 K. Polikreti, Y. Maniatis / The Science of the Total Environment 308 (2003) 111–119
favourable substrate for microbial growth. Neither
on the top of the patina nor in its bulk were
biological factors detected. The microorganisms
(most probably black fungi) live only at the
interface between hydroxyapatite and marble.
There, they destroy not only the marble cohesion
but also the adhesion of the patina on the marble
surface. It is nowadays accepted that biological
attack is mainly mechanical (stresses caused by
the penetration hyphae) and not chemical (secre-
tion of acid and dissolution) (Diakumaku et al.,
1995; Sterflinger and Krumbein, 1997). The
increase in the microorganism biomass causes local
pressure, which loosens the crystals and results in
chipping and detachment. The process is acceler-
ated by acid rain, which dissolves hydroxyapatite
(Kouzeli et al., 1996). Finally, the marble surface,
full of cavities and fungal colonies is exposed to
all types of weathering factors.
5. Conclusion
The overall consideration of the analysis, which
was done on the surface samples from the South-
east wall of the Propylaea, leads us to the following
interpretation for the structure and origin of these
layers:
The marble is covered by a very compact and
homogenous layer consisting of hydroxyapatite,
which has most probably been applied on the
surface for aesthetic and protective purposes. The
orange–brown colour is attributed to iron oxides
together with clay minerals, which have been
deposited on the surface and gradually absorbed
by the phosphatic layer.
The surface under the patina is full of cavities
and the patina usually penetrates between the
marble grains and in the grain boundaries, indicat-
ing that when it was applied, the marble had
already been weathered. This observation indicates
that the application was not done in antiquity but
later on, mainly for conservation and protection
purposes. Milk, egg white or pulverised animal
bones are possible constituents of the original
patina recipe.
At the interface between the patina and the
marble, microcolonies of microorganisms are
growing and as they penetrate in the marble, they
progressively destroy both the patina-marble and
the marble crystal cohesion. All results lead to the
conclusion that the microorganisms are always
growing under the phosphatic layer and never in
or above it. Whenever the biological factors are
observed in the phosphatic layer, it is in cracks,
which could have been formed by penetrating
hyphae as the microorganisms try to avoid the dry
conditions of the surface and intense ultraviolet
irradiation. It is obvious that the phosphatic patina
is not a favourable living substrate for
microorganisms.
The phosphatic layer is being destroyed and
detached due to the biological action at the inter-
face between the patina and the marble, with the
contribution of acid rain. The exposed surface
presents a great number of cavities and holes with
silicate depositions and microorganisms. This
whole procedure indicates a biologically-induced
corrosive process, which is responsible for the
decay and removal of the protective coating.
Acknowledgments
This work was funded by the National Institute
for Scholarships of Greece. We are indebted to K.
Babanika, conservator of the archaeological site of
Acropolis, Athens who introduced us to the prob-
lem of orange patinas and gave us the permission
for sampling the Southeast wall of the Propylaea.
We also thank G. Doganis and A. Galanos, for the
invaluable information they gave us, on the historic
and conservation aspects of the issue.
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