Air Pollution and Aspects of Stone Degradation “Umayyed Liwân -... Citadel as a Case Study” Elgohary, M.A,

Journal of Applied Sciences Research, 4(6): 669-682, 2008
© 2008, INSInet Publication
Air Pollution and Aspects of Stone Degradation “Umayyed Liwân - Amman
Citadel as a Case Study”
Elgohary, M.A,
Conservation dept. Faculty of Arts, Sohag University, Egypt.
Abstract: Many natural stone monuments have suffered from serious damages that due to natural
weathering, pollution and other factors of deterioration and using insufficient maintenance of susceptible
materials or inappropriate conservation. Considerable attention has been paid in recent years to the decay
of carbonate building stones [Limestone and Marble] especially in aggressive polluted environments,
moreover, color changes, patina, blacking of rock's surfaces in monuments and associated phenomena
practically always have been related to other environmental factors of deterioration. The aim of this
research is to study and investigate the different deterioration factors affecting Amman citadel either
chemically physically or biologically resulted from the different effects of air pollution using some
scientific techniques and using methods to achieve this aim such as XRD, Stereo microscope, ICP-OES
techniques and some other electronic instruments”. All investigation and specific measurements proved
that our case study suffered and still suffering from many deterioration aspects resulting from several
deterioration factors and mechanisms either physical or chemical such as Crustation, Crystallization, dirties
accumulations and other deterioration forms, that essentially due to many sources of air pollution either
stationary, mobile or anthropogenic sources. Finally, we can define the effective methods, materials and
preservation measurements for restoring and maintaining the monument under study, which require cooperation of monuments owners, archaeologists, scientists and restorers.
Key words: Air pollution - Deterioration - pollutants - Decomposition - Aspects - TSP - Stereo M -XRD
– ICP-OES.
especially with the presences of other synergetic
deterioration factors such as air temperature, relative
humidity and wind erosion.
INTRODUCTION
Air pollution as a general term means, that there
are unexpectedly of some particles pollutants with high
concentration, it occurs almost everywhere and has a
long history[1 ]. Also, it is well known that natural
stones are considered as the most durable building
materials through ages [2 ].
Thus, weathering and deterioration of stone
monuments became natural process particularly
near
urban
and
industrial areas owing to air
pollution, which if we can't stop, we have to slow
it down, otherwise we will not have any cultural
heritage to preserve in the future [3 ,4 ,5 ]. Recently, we
can see that rapid and increasing deterioration of
stone façades and monumental buildings have
been
reported
in
several
countries,
this
phenomenon mostly occurs in different regions and
different ages with varied external deterioration
aspects [6 ].
The aim of this study is to explain the threat of air
pollution on our cultural heritage and to focus on the
acceleration of weathering processes affecting stone
monuments through it and its resulted aspects
Archaeological Features of Umayyad Liwân: Amman
"the capital of Jordanian kingdom", contains many
archaeological sites such as desert palaces, ancient
mosques and Islamic citadels, it is considered one of
the oldest and most famous capitals in the middle East
and located in the Northern side of about 88 km
Southern Eastern of Jerusalem [7 ]. The citadel "the most
famous archaeological site" in Amman has complicated
buildings which extended along several eras beginning
from 2 n d Iron Age to Islamic period, fig. (1). It has a
plain shape from Northern W estern to Southern Eastern
surrounded by many valleys from all directions except
Northern direction which faces Al-Hussein M ountain [8 ].
In addition, this citadel includes many archaeological,
sites that characterized by many artistic features such
as Open Historical Lake, Umayyed Houses and
Umayyed Liwân “the topic of our study” [9 ]. This Liwân
is one of the most famous archaeological buildings not
only in Amman citadel but also in all the kingdom,
which, is situated in the outcrop of Roman ruined
Corresponding Author: Elgohary, M.A, Conservation dept. Faculty of Arts, Sohag University, Egypt.
E-mail: [email protected]
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J. Appl. Sci. Res., 4(6): 669-682, 2008
Fig. 1: Showing satellite view of Amman citadel
Fig. 2: Showing General picture of the Liwan
from 4 th centaury and it was built by Abdel-Malek
Ibn Mrwan (65-68 Hegra) to be as a reception [1 0 ,1 1 ],
where he could meet his expeditions and army leaders
fig. (2).
society depend on many different qualities and
meanings that they ascribe [1 4 ,1 5 ].
Here, some of these values relate directly to our
site that makes it an important site with a special
cultural significance, where we notice that its historical
value is equally important if not the most important
that characterize the study area, which has been
inhabited since Neolithic period, but the more
inhabitation in this area was during Islamic period [1 6 ,1 7 ].
Also, our monument has a great identity, wonder,
spiritual, social and symbolic values that essentially due
to its important location and its different artistic
Related Values the Study Area: The great importance
of any archaeological sites is reflected by many
effective values of cultural heritage; those that are
deemed significant will provide justification for its
p rotectio n, preservatio n, co nservatio n and
maintenance [1 2 ,1 3 ]. W here different values perceived in
the archaeological heritage by various segments of
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J. Appl. Sci. Res., 4(6): 669-682, 2008
features. Thus, we decide without any doubt that all of
these values represent lot of things for Jordanian
people and make our site an undeniable source of
nationality and real identity.
suspended particulate matters (Dust, fumes, M ists and
Smokes), gaseous (Gases and Vapors) or Odors, where,
clean air comprises O (21%), N (78 % ), a number of
rare gases as Argon and CO 2 at a low percentage
concentration (0.03 %) [2 3 ]. Also, the clean air contains
approximately 0.03ppm of SO 2 0.053ppm of NO 2 and
0.08ppm of O 3 varied with meteorological condition. In
addition to chlorine compounds and other kinds of
pollutants which produced by industrial activities [24],
and vehicular traffic [2 5 ,2 6 ]. From this environmental point
of view, complete measurements of the most dominated
pollutants in the study area made by Jordanian royal
s c ie ntific so cie ty 1 9 8 6 - 1 9 9 0 a n d J o r d a n ia n
environmental
healthy
department 1997-2003
according to W HO and Jordanian standards by
using different analytical instruments such as HiVol Sampler, Pulsed UV Fluorescence and NonDispersive Infrared. Through analyzing all these data
we notice that air quality in this area characterized by
the presences of some aggressive pollutants that
affect monumental buildings and we can conclude it
in the next points:
Pollution and Pollutants in the Study Area: In this
part, we studied the different components and chemical
characteristics of ambient air in Amman city according
to national and International standards through realizing
the next topics:
Sources of Air Pollution in the Study Area: Through
several statistical and analytical studies of all industrial
activities in Jordan, one can say that the different
values of air pollution were increased as a direct result
of great development and wide using of energy which
lead to presences of negative effects on air quality.
From environmental point of view, we can classify the
different sources of air pollution dominated in Amman
city which affected the study area into two main
sources" stationary and mobile" [1 8 ].
Stationary sources: There are many stationary sources
of air pollution distributed along the kingdom,
that are significantly affective ambient concentrations
of
air
contaminates
regulated
as criteria or
hazardous pollutants either through direct or indirect
roles. These sources such as Zarga petroleum refinery,
Al Hussein calorific station northern east Zarga,
Cement factories, in addition to domestic waste water
stations, and quarries. All of these sources lead to
produce some aggressive pollutants such as TSP,
Fuels, Dusts, Oxides, Organic matters, Hydrocarbons
and some effective gases "CO, CO 2 , SO 2 , NO x , H 2 S,
NH 4 , CH 4 " [1 9 ].
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M obile Sources: These sources result essentially from
the effects of transportation means such as cars, buses
and planes in different station and civil or military
airports with noticing the direct effects of Marka
airport "about 4-5 km from the study area", which lead
to exhaust emissions inside and around study area [2 0 ].
Most of these pollutants were increased through the
last 20 years especially as direct results of wide using
of diesel fuel which is considered a complex mixture
of normal branched and cyclic alkanes "60 to > 90%"
by volume [2 1 ]. All of these means lead to the emission
of some harmful pollutants and different Gaseous such
as: TSP, CO, CO 2 , and SO 2 in particular NO 2 . They
play an important role in oxidation processes [2 2 ], then,
lead to many deterioration effects, mechanisms
"chemical and/or physical" and forms.
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Air Quality in the Study Area: It is well known that
air pollutants are usually classified either into
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TSP, SO 2 , CO, No x and Pb are the major
dominated oxides in air composition affecting the
study area, all of these pollutants are decreased in
weekends because of low movement of means of
transport and they exceed the W HO standards.
There is a trust relation between the pollutant
levels and meteorological parameters especially
W ind speed, RH and Air temperature that are
usually elevated in winter.
The main sources of TSP due to both frequent
traffic congestions, domestic and commercial space
heating.
There is a strong variation between SO 2 levels
recorded in different seasons according to fuel
consumption, domestic and commercial heating, in
addition to poor maintenance of motor engines and
lake of any natural regulations, regarding vehicles
emission. In contrast to SO 2 that have been
observed during the 1 st part of the day, we can see
that CO levels were observed during the 2 nd and 3 rd
parts of the day, also, we can notice that CO
levels were highest during cold periods of the year
and the lowest were recorded in hot periods.
Pb is considered one of the secondary pollutants
dominated in air composition in the study area;
it is due to several industrial activities resulted
from liquid battery factories and lead's vapors in
Marka zone.
Finally, we confirm that all obtained data showed
that ambient No levels were generally low and No 2
levels were incomplete so we can't evaluate their
levels correctly.
J. Appl. Sci. Res., 4(6): 669-682, 2008
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Relation Between Air Quality and Rain W ater in
the Study Area: Through several scientific studies that
have been done on the relation between air pollutants
and chemical nature of precipitation we can say that
there are some aggressive changes in its chemistry
particularly for over 2 decades, these changes defined
as acidification of precipitation and it was called quite
naturally acid deposition or acid rain [2 7 ]. Initially the
term "Acid Rain" refers to both wet and dry acid
deposition, although acid deposition is a more correct
term, acid rain is more commonly term used [2 8 ], this
deposition of gaseous and pollutant particles
characterized by anomalously low pH values, that
became a key to environmental issue from the
beginning of the 1980 [2 9 ]. From the environmental point
of view, acid rain was increased as a primarily result
due to the increasing emission of SO 2 and NO x that
have accompanied by the great increasing of economic
activities. Therefore, these oxides are oxidized over
several hours to several days to compose or create two
of the most serous acids "H 2 SO 4 " "H NO 3 ", that are
generally captured by raindrops and returned to stone
surfaces acid precipitation [3 0 ], as shown in fig (3-a, b).
Then, these precipitations lead to many deterioration
mechanisms that affect materials and stone structures
especially carbonated rocks, in particular with presence
of other synergetic deterioration factors such as air
temperature [3 1 ].
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Internal Parts:
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General Aspects of Deterioration Dominate in Study
Area: Through a complete survey of the Liwan
"exterior and interior parts" which carried out by using
field observation, digital photography and a close visual
inspection, we decide that there are complicated
processes of destruction and distress that varied in its
materials, factors and environmental forces, which lead
to typical structural changes, different types of
deterioration aspects, weathering forms and stone
damages that were occurred on 2 parts of the Liwan
"External and Internal" classified as fallow:
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Cracking and loosing of some surface details
because of aggressive effects of internal pressures
and micro strains resulted from the growing of
some salt crystals types especially inside the pore
structures, fig. (5-a)
Efflorescence or Sub-efflorescence aspects affecting
our monument that lead to leaching of different
material from inside to outside as calcium
carbonate salt, fig. (5-b)
Presences of some layers of un-noble patina and
colored surface crusts, often due to direct
synergetic effects between rain water and soiling
by particles, fig. (5-c)
Presence of some weathering aspects dominate in
the urban environments such as exfoliation and
scaling that mostly due to the action of freezing
thaw with presence of acidic pollutants, fig. (5-d)
Detachment of mortar layers and some stone
fragments because of the effects of salinity water,
some external actions and vibrations, fig. (5-e)
Formation of some salty hard-crusts on stone
surfaces and within stone pores that create some
aggressive internal pressures, which finally lead to
bleeding of stone aspects, fig. (5-f)
Samples' Criteria and Instrumental Analysis: In
order to distinguish the different environmental
parameters and quantitative description of stone's
deterioration, some samples should be taken and
investigated to get a proper understanding of the
harmful effect of air pollution. From the analytical
point of view, abroad range of surface and microanalytical techniques are invoked in recent deterioration
studies of the different archaeological materials to
define its different characteristics [3 2 ]. In our study some
of theses techniques have been used for studying and
analyzing both natural stones, its deteriorated surfaces
and weathering products.
External Parts:
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Presence of some colored hard crusts resulted from
the acid rain effects, heavy metals dominate in air
composition and fly ashes "Ferrous oxides", fig.
(4-d)
Disappearance of some parts of stone surfaces as
a direct result of salt crystal growth due to
alternative processes between wet and dry cycles
either daily, seasonally or annually, fig. (4-e)
Black and dark aspects resulted directly from air
pollution effects and its different components as
soot and organic black matters, fig. (4-f)
Severe etching and loosing of calcite grains on
stone surface, because of dissolution processes
resulted directly from acid rains' effects, fig. (4-a)
Discoloring of some zones on the stone surfaces
essentially due to soot, dirties, impurities of
polluted oxides and erosion signs, fig. (4-b)
Eroded of the exposed stone surfaces to direct
effects of botanical and microbiological actions,
that lead to many surface details as carving and
relief which will be lost through time pasting
depending on other microenvironment actions
dominated, especially accumulated pollutants,
fig. (4-c).
Ocular Examination: The evaluation of our stone
surface, different appearances and changes in thickness
due to air pollution effects which have been defined
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Fig. 3- a, b: Showing cycle of acid rain and its effects on weathering processes
Fig. 4: Showing deterioration aspects in External parts of the citadel
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J. Appl. Sci. Res., 4(6): 669-682, 2008
Fig. 5: Showing deterioration aspects in internal parts of the citadel.
and documented through visual observation, by critical
eye, digital camera and digital-clipper, different results
of investigation were listed in table (1)
From the previous examination, we decide that
there
are
non affected areas as represented in
(sample-1) and affected area which totally transformed
into salty hard crusts as represented in (samples-2, 3),
generally, the different aspects of deterioration affecting
the monuments under study by air pollution are divided
into 3 categories according to deterioration range as
fallow:
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results showed
follows:
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different
deterioration
aspects
as
Accumulations of some black hard crusts, fig. (6-a)
Presences of some features of salt efflorescence
and sub-efflorescence covering both stone surfaces
and mortar layers, fig. (6-b)
Dissolution and erosion of stone surfaces, fig. (6-c)
Presences of some colored spots and strange
grains, fig. (6-d)
X-Ray Powder Diffraction Analysis: Randomly
oriented powder were prepared from 10 samples
obtained by surface scraping from different parts of the
Liwân and were analyzed by this technique, the
resulting data were divided according to its
deterioration state into 2 essential groups.
The 1 st group, represents all samples collected from
sheltered or non deteriorated parts, which contains
[Calcite CaCO 3 ] with some trace and low detectable
minerals such as [Kaolinite Al2 Si 2 O 5 (OH)4 ] , [Halite
Na Cl] and [Gypsum CaSO 4 . 2H 2 O].
The 2 n d group, represents all samples collected
from affected or deteriorated parts, that contains some
major compounds such as [Calcite CaCO 3 ], [Gypsum
CaSO 4 . 2H 2 O], [Hydrocerocite Pb (CO 3 ) (OH)2 ],
[Halite Na Cl], [Kaolinite Al2 Si2 O 5 (OH)4 ], [Goethite
FeO (OH)] and [Dolomite Ca Mg (C0 3 ) 2 ] as manor
and traces surfaces accumulations, all of these results
are shown in fig. (7-a, b)
Light polluted surfaces physically affected
(samples-4, 5, 6)
Moderate polluted surfaces chemically affected
samples (samples-7, 8)
Heavy polluted surfaces chemically and physically
affected samples (samples-9, 10)
Stereo M icroscope Observation: The capture of
colored pictures through using scientific stereo
photograph is considered one of the developed
techniques that used for studying and documenting
different surface features of stone and evaluation of
future deterioration speeds and processes [3 3 ], where; it
makes possible to analysis the stone topographical
features by means of visual stereo-interpretation of the
photographs.
Stereo microscope model Wild Heerbrugg, with
camera Wild MPS 51 and Wild MPS 45 photo-automat
unit used with different magnification to investigate
different deteriorated surface of the samples collected
during field's observation after preparing them, different
Inductively Coupled Plasma: Inductively Coupled
Plasma [3 4 ]. Optical Emission Spectrometry [ICP-OES] is
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J. Appl. Sci. Res., 4(6): 669-682, 2008
Showing description and different characteristics of the collected sam ples
Sam ples details and visual observations
Sam ples
------------------------------------------------------------------------------------------------------------------------------------------------------------------Kind
D irection
Altitude
Thickness
Sam ples description
1
Lim estone
SW
170 cm
W hite Rosy non affected sam ple
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------2
H alite
SW
170 cm
Pure white salty hard crust
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------3
Gypsum
E
250 cm
Pale white salty soft crust
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------4
Surface crust
W
210 cm
0.15 m m
D ark yellow stained by grey soiling
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------5
Surface crust
W
260 cm
0.35 m m
Light brown crust
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------6
Surface crust
SW
160 cm
0.48 m m
Light brown stained by grey soiling
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------7
Surface crust
N
300 cm
0.82 m m
H igh coarse dark grey crust
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------8
Surface crust
E
60 cm
0.88 m m
M ilky surface crust
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------9
Surface crust
NW
100 cm
1.02 m m
Coarse flaking crust grey to brown
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------10
Surface crust
NW
280 cm
1.29 m m
H igh coarse m ilky to light grey
Table 1:
Fig. 6: Showing Surfaces appearances of investigated samples by Stereo microscope.
pH meter" and "digital conductivity meter" to analyze
4 samples of rain water and determine its elemental
ratios and different characteristics, all results are listed
in the table (2)
Through analyzing the previous data, we decide
that there are some aggressive families of salts
formed
according to chemical simple reactions
between Cations and Anions such as [Calcium
Bicarbonate 19.64 %], [Gypsum 7.92 %], [Calcium
chloride, 22.03 %], [Magnesium chloride 17.32 %],
[Halite 24.44 %], [Sylvite 1.86 %] and [Niter 6.79 %],
in addition to some other undetectable elements not
dissolved completely such as Al, Mn, Fe and Pb as
shown in fig. (8)
widespread technique, used to the analysis waste water
and soil, levels of trace, minor and major elements can
be determined simultaneously, thus ensuring low
analysis costs [3 5 ]. It was used since the 1970 to detect
the different trace elements in several environmental
samples after dissolution. And it can be used as
quantitative and elemental isotopic analysis for over
70 elements because of its low detection limits[3 6 ].
Also, other techniques were used for defining other
analytical parameters such as pH meter to measure pH
value and conductivity meter for measuring electrical
conductivity of different samples[3 7 ]. From this point of
view, all measurements were performed using "Varian
Vista Series ICP-OES Spectrometers", "glass electrode
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Analytical results and effective characteristics of rain water in the study area
Analytical results
Cations
Anions
--------------------------------------------------------------------------------------------------------------------------------------------------------------------Elem ents
m g/l
%
Elem ents
m g/l
%
N a+
277.0
1133.3
24.44
H Co 3 70.0
356.43
19.64
M g++
196.03
17.32
Cl234.0
65.65
Al+
0.13
undetectable
So 4 -28.23
7.92
K+
98.0
8.65
N o324.20
6.79
Ca + +
562.0
49.59
O ther effective characteristics
----------------------------------------------------------------------------------------M n++
0.003
undetectable
PH Value
5.38l
Fe + +
0.09
undetectable
EC
483 µs
Pb + +
0.04
undetectable
TD S
163.0 M g / l
Table 2:
Fig. 7-a, b: showing XRD patterns of stone and surfaces crusts
Discussion: Through different results of this research,
we can reveal that air pollution can significantly affect
the corrosion and deterioration of archaeological
materials all over the world as discussed before by
Van Grieken, et al. [3 8 ]. Also as explained before by ElGohary [3 9 ], who decide that both outdoor and indoor air
pollutants cause several chemical and physical damages
that affected monumental stones and frescoes by
deposition of particulate material or absorption of
present gases leading to many deterioration aspects
showed before, which we can conclude in the next
paragraphs.
Ocular Examination shows that the deterioration
aspects' rates affecting our building materials due to air
pollution is a complex multi-parameter function, as
proved before by Haber [4 0 ] in similar cases. W here, the
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J. Appl. Sci. Res., 4(6): 669-682, 2008
Fig. 8: Show analytical results of rain water in the study area
stone surface shows various degrees of damages resulted by severe effects of air pollution that due to many
deterioration mechanisms, these aspects are divided into 3 essential categories as fallow:
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Light polluted surfaces, this category mostly dues to physical mechanisms that result essentially by different
dry deposits as reported before by Hicks [4 1 ]. Some of these aggressive materials "SO 2 , SO 3 , CO 2 , NH 3 , dark
impurities, dusts, soot and H ydrocarbon" lead to many physical aspects and characterize by light to little dark
colours and low thickness "0.15-0.48mm" as shown in (samples-4, 5, 6), these results completely agree what
is reported by Elfving [4 2 ].
Moderate polluted surfaces, this category mostly dues to corrosive chemical mechanisms that result by air
pollution with other synergetic effects as rain water or different sources of moisture, for example, we can
notice that the sulphate that was found in some stone surfaces is formed by chemical reactions of SO 2 with
CaCO 3 , as reported by many researches as Fassina [4 3 ] and Russ, et al.[4 4 ]. This mechanism leads to the
formation of some aggressive salty hard crusts on stone surfaces as Gypsum "CaSO 4 . 2H 2 O" the most
ubiquitous salt found as a result of dissolution processes of Calcite "CaCO 3 " through the main process that
may be outlined in the next formulas:
Here, we see that the rate of chemical reaction between stone surface and acid rain depends mainly on several
catalytic effective metal ions as discussed before by Penkett, et al.[4 5 ] and Flatt, et al.[4 6 ]. Finally this salt will
penetrate into stone pore spaces and will crystallize there and leads to crystallization processes over years, then
breaking the stone surfaces, as pointed before by Lewin [4 7 ], also this phenomenon depends essentially on the amount
of salt presence, its nature and number of dry-wet cycles, Binda, and B aronio [4 8 ]. Also, we see that the presence
of calcite as salty crusts due essentially to the chemical reaction between CO 2 "normal constituents of air
composition or this results by the combustion of organic materials" and rainwater forming CO 2 . H 2 O in the first
instance, then HCO 3 that react with CaCO 3 forming firstly Ca [HCO 3 ] 2 and finally CaCO 3 salty crust according
the next formulas:
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J. Appl. Sci. Res., 4(6): 669-682, 2008
From specialized point of view, we decide that the
final crust of CaCO 3 reprecipitates near the surface
forming a hard crust that hides a weakened matrix of
sto ne as argued previously by Cussler and
Featherston [4 9 ]. It characterizes by large crystals and
high porosity index, where CaCO 3 as an essential
m in e ra l o f L i m e s to n e is c h a ra c te riz e d b y
microcrystalline structure and very low porosity index,
as represented before by Winkler [50], Amoroso and
Fassina [5 1 ]. Also, we notice that this category
characterizes by changing of colours that varied
between light and dark, in addition to moderate
thickness "0.82-0.88mm" as shown in (samples-7, 8).
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surfaces and mortar layers due to the crystallization
and re-crystallization cycles of salts coming from acid
rains especially after drying cycles either by air
temperature or by air currents. In addition to presences
of some deterioration features as dissolution and
erosion of stone surfaces because of some chemical
effects resulting from acidity spots composed as direct
results of interaction between air gaseous and rain
water "Acid rains".
XRD Analysis Results confirmed that all results of
sheltered investigated samples pointed that Calcite
essentially due to Limestone that was used as a
building material in construction field along times.
Also, we notice that the presence of some trace
compounds that composed of some minerals such as,
Kaolinite due to different physical effects of air
pollution and air born particles affected stone surface
mainly resulted from the effects of industrial activities
that owe to the transported pollutants through urban
meteorological elements dominated in the area. In
addition to Dolomite that is found in limestone
composition, it is similar to that calcite and composed
of calcium carbonate with magnesium carbonate
belonged to Iso structural carbonate but with Ca and
Mg layers alternating along the C axis as referenced
before by Klein [5 8 ].
It is occur in our case study as a direct result of
chemical reaction between Mg ions dominated in acid
rains and different components of building materials. In
addition to some salt crusts such as Halite that
originates from different sources as "Rocks, Soils or
resulted through different chemical effects and drying
cycles", Abdel Hady [5 9 ]. In our case this salt dues to
the effect of Cl ion dominated in and between ambient
air resulted from industrial emission and Na ion
dominated as a major constituent in the ground or
through salinity groundwater as discussed before by
El-Gohary[6 0 ] in a similar case. On the other hand, we
can say that the presence of Calcium salty crust in
unsheltered investigated samples due to the chemical
reaction between Limestone and Carbonic acid
dominated in acid rain after some wetting and drying
cycles. Also, we notice that all deteriorated crusts
composed of some salty minerals such as Gypsum and
Halite resulted essentially as a direct result of chemical
weathering through chemical reactions between some
polluted gaseous as SO 2 No x and dominated ions in
soils with building materials. Also, we decide that the
presence of Hydrocerocite as a thin black or dark Gray
layer resulted essentially by chemical reaction between
Pb and stone surface with presence of atmospheric CO 2
under normal conditions as reported previously by
Carradice and Campbell[6 1 ] . W here, it acts as a
reservoir for moisture and harmful chemicals, and then
Heavy polluted surfaces, this category mostly
affected through both severe chemical and physical
mechanisms, that resulted from synergetic effects
of deterioration dominated in the area and lead to
many weathering aspects explained above but with
severe characterizations; as high dark color index
and big thickness"1.22-1.29mm" as shown in
(samples-9,10), mostly composed from Gypsum
and Anhydrite crusts that considered common
features of carbonated rocks in polluted area
especially after water evaporation as reported
before by Lal Gauri and Yerrapragada [5 2 ] and
Lindqvist, et al. [5 3 ]. Also, lead to the presence of
some crystals of Halite, which is considered one of
the most aggressive salt that affect limestone
surfaces particularly with continuous alternative
cycles of wetting and drying, as discussed by
Löfvendahl [5 4 ] and Mirwald, et al. [5 5 ].
Stereo Microscope Observations proved that all
facades display some dark spots, strange grains and
colored hard crusts "black, reddish and yellowish" both
on the stone surfaces and within the stone pores which
essentially due to accumulation of some dusts, heavy
metals, car exhaust and air pollutant particles resulted
from different sources of air pollution "stationary and
mobile" or that due to anthropogenic activities as
referenced by Elgohary [3 9 ]. On the other hand, we see
that these colored stains may due to oxidation of
Iron-bearing carbonates and lead to a penetrative
Yellowish or Reddish brown stating. Also, we agree
completely with B egonha [5 6 ] in his scientific explanation
about the presence of black crusts that was formed as
a direct result of gypsum crystallization with fly ashes
and soot originated from air pollution. Or they may be
formed through chemical reaction between pure calcite
with metals-bearing acidic water to produce colored
alteration products, as explained before by Gribble and
Hall[5 7 ]. In addition, there are several aspects of salt
efflorescence and sub-efflorescence covering both stone
678
J. Appl. Sci. Res., 4(6): 669-682, 2008
can accelerate the decay process. In addition to other
secondary minerals that are found in stone surfaces as
a colour impurities and surface accumulation such as
Goethite, it is an iron bearing oxide mineral found in
soil and other low temperature environments and it
often forms through the weathering of other iron-rich
minerals, and thus is a common component of
soils, may also be precipitated by groundwater or in
other sedimentary conditions, Catling and Moore [6 2 ].
In general, goethite formation is favored in alkaline
solution at moderate temperature, in our case; it
resulted as final product of ferrous oxidation in solution
depending on environmental conditions dominated in
the study area.
ICP-OES Analytical Results, indicate without any
doubt that analyzed samples classified as slightly acid
water according to the standard scale of pH value, and
it contain some aggressive salty minerals such as
Calcium Bicarbonate, Gypsum, Calcium chloride,
Magnesium chloride, Halite, Sylvite and Niter, in
addition there are some other undetectable minerals as
Mn Cl2 , Fe Cl 2 . All of these salts resulted by chemical
reaction of rain water and different air pollutants
dominated in the study area, where, they play an
important role in deterioration processes either as a
primary role by Gypsum, Halite, Sylvite and N iter or
through secondary role by other wake salt materials as
a dissolution media of accumulating pollutants on these
surfaces, W inkler [6 3 ]. On the other hand, they play
partial role as a direct media of dissolution processes
by acid rain itself because of neutralizing actions'
resulted by carbonatic dusts dominated in TSP in
surround ambient air, where, the injury values of
Sulpher ion depend essentially on the level of Calcium
ion, Guderain [6 4 ].
From this point of view, we can say that the
damage produced by acid rain on calcareous stone can
obviously be seen on the carved surfaces with
only some mm depth that can be lost very fast
depending
on pH value, rain quantity, impurities
quality
and
wind
direction as reported by
Charola, [6 5 ].
This
phenomenon leads to increase
stone's porosity, and then water will penetrate and
react with internal cement materials and Calcite
grains. It also, increases the ratio of damage and
loses
the
cohesive
index
of
structure and
eventually falling out structure after producing socalled sugaring appearance, Rands, et al.[6 6 ], or at least
leads to leach some chemical components of stone
surfaces as Ca and Al. Also, we can say that the
transition metals such as Iron "Fe" and Manganese
"M n" which commonly found in the atmosphere as
suspended particulates catalyze the oxidation of SO 2 to
SO 3 according to the following equation:
These catalysts play a synergistic role in
deterioration mechanisms, where its activity increase by
the increasing of pH value essentially pH of the
droplets and facilitate H 2 SO 4 to absorb within the
stone pores leading to some internal strains as observed
by Barrie and Georgii,[6 7 ], Penkett, et al.,[6 8 ]. Also, we
see that the presence of other Cations as Al and Pb
due to micro effects of industrial activities and some
species of microorganisms dominated in the soil.
Finally, we decide that air pollution is considered one
of the most aggressive and severe factors that lead to
many deterioration aspects especially with presence and
combination between other factors in surrounded
environment such as rain water, air temperature and
wind currents.
Conclusion: It is pertinent to device some scientific
methods and interventions to reduce all factors of air
pollution and removing its harmful concentration from
historic and archaeological sites through traffic
management and taking account the effects of air
pollution phenomena during town planning studies.
From this point of view, a successful working schedule
should be taken in consideration; it should include
many scientific tools to prevent the harmful effects of
air pollution such as:
C
C
C
C
Scientific diagnosis through using several methods
and analytical techniques.
Consequences methods of cleaning according to
deterioration status.
Consolidation materials should be applied by using
some consolidant materials and water repellents
through suitable scientific techniques to reinforce
and restorative affected stone surfaces to make
them apart from severe effects of air pollution.
Maintenance procedures should be taken in
consideration for minimizing all interventions in
the future through some important processes such
as protection against all sources of moisture
especially salinity groundwater and acidity
rainwater and protection against dirties, particles
and all surface accumulations through a complete
p ro je c t th a t in c lud e d iffe re n t s c ie n t i f i c
interventions, "Immediate or urgent interventions,
N ece ssa ry in te rv en tio n s and P e rm a n e n t
interventions"
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