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Chemical Weathering of Lime Mortars from the Jahangir Tomb, Lahore-


Pakistan

Article · November 2014


DOI: 10.12983/ijsrce-2014-p0106-0114

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International Journal of Scientific Research in Chemical Engineering, 1(7), pp. 106-114, 2014
Available online at http://www.ijsrpub.com/ijsrce
ISSN: 2345-6787; ©2014; Author(s) retain the copyright of this article
http://dx.doi.org/10.12983/ijsrce-2014-p0106-0114

Full Length Research Paper

Chemical Weathering of Lime Mortars from the Jahangir Tomb, Lahore-Pakistan


Saima Gulzar1, 2*, Muhammad Nawaz Chaudhry1, Jean-Pierre Burg2, Sohail Anwer Saeed3
1
College of Earth and Environmental Sciences, University of the Punjab, Lahore, Pakistan
2
Geological Institute, Swiss Federal Institute of Technology Zurich, Switzerland
3
Sohail Saeed &Associates, Lahore, Pakistan
*Corresponding Author: Email: saimagulzar@yahoo.com, saima.gulzar@erdw.ethz.ch

Received 30 September 2014; Accepted 20 November 2014

Abstract. The effects of environmental pollution on cultural heritage have been widely studied in different parts of the world
over the last few decades but not with the reference to Pakistan, although cultural heritage in this part of the world is
deteriorating at an alarming rate. Determination of the deterioration processes and causes are the fundamental parameters for
the preservation on scientific grounds of these cultural assets. This study investigates the effect of environmental pollution on
the façades of the 17th century historic monuments of Jahangir Tomb in Lahore (Pakistan). For this purpose, samples were
collected from weathered as well as from sound interior surfaces. The samples were characterized by XRF, XRD, SEM-EDS
and stereomicroscopy/wet chemistry to understand the weathering mechanisms and products. Those are mainly comprised of
sulphates, chlorides and nitrates along with high contents of soil particulates and biological colonization. Results show that
chemical weathering is occurring at the mortar-atmosphere interface of the historic fabric, conjoining the petrographic
characteristics of the mortars and enveloping atmospheric composition. This interaction is responsible for the current
deterioration of the historic lime mortars.

Key words: chemical; weathering; XRF; XRD; SEM-EDS; mortars; Pakistan

1. INTRODUCTION al., 2010). The main damage occurring to mortars


exposed to urban atmosphere is the transformation of
Environmental pollution is now one of the major calcium carbonates into calcium sulphates due to the
factors contributing to the degradation of historical deposition of airborne sulphur compounds, dissolution
buildings especially in the emerging countries like by rainfall and SO2, blackening by soot deposition,
Pakistan (Sarkar et al., 1992; Arif, 2003; Gulzar et al., thermal damage, degradation by soluble salts and
2004). The exponential growth of vehicles and rapid biological colonization (Brimblecombe, 2004; Hall et
industrial developments over the last decades al., 2011). Pollution-triggered deterioration was
generated highly polluted atmospheric conditions, especially intense from 1700s in Europe. In the late
which are aggressive to the historic garden city of 19th and early 20th centuries the dominant impact of
Lahore (capital of Mughal Empire). This resulted into environmental pollution was the sulphation of
enhanced chemical weathering of historic monuments surfaces. The parallel deposition of soot caused the
(Gulzar et al., 2013). blackening of surfaces and the formation of black
The determination of environmental impacts is not crusts (Sabbioni et al., 2010).
straight-forward because of their complex and The Jahangir Tomb, a landmark of Mughal
variable nature (Viles, 2011). They may be natural or architecture and funeral landscape in Pakistan, is
anthropogenic. It is presently hybrid because of the subjected to the adverse impacts of visibly identifiable
influx of pollutants from both natural and natural and anthropogenic deterioration processes
anthropogenic sources, which together accelerate (Awan, 2009). The current deterioration of these
deterioration of historic structures (Inkpen, 2004; remarkable buildings were incentive to the presented
World Heritage Report No. 22, 2007). All gases and research on the causes of material degradation,
particles emitted into the atmosphere deposited back especially the lime mortars, in order to formulate
to the Earth’s surface directly or through wet suitable solutions to restore this cultural asset and
accumulation, which involves scavenging by transmit it to future generations.
precipitation (Searle and Mitchell, 2006; Sternberg et
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Gulzar et al.
Chemical Weathering of Lime Mortars from the Jahangir Tomb, Lahore-Pakistan

Site inspection revealed that the historic façades 2. MATERIALS AND METHODS
suffered from several types of deterioration
phenomena (Fig 1 and 2) and are presently reaching 2.1. Sample
critical conditions due to negligence, lack of necessary
maintenance and poorly adopted conservation The samples were collected keeping in view the
strategies. Mortars were observed importantly significance of this cultural asset and the needs for
cracked, blistered and leached from the masonry multidisciplinary scientific examination (Delalieux et
joints, leaving cavities at multiple locations (Fig 2). al., 2001; Binda et al., 2007). Mortar samples were
Close visual inspection of the damaged mortars also taken from different places of the main tomb building
revealed discoloration and the formation of black and to incorporate all types of weathered mortar surfaces.
green patinas. The interior surfaces (-of mortars-) Sample MS1 was obtained from the exterior façade
exhibited characteristic symptoms of localized directly exposed to polluted atmosphere, driving rain
efflorescence –whitish patches and deposition of and sunshine. Sample MS2 was extracted from the
pollutants corresponding to black surfaces, which is leached joint of stone masonry whereas MS3 was
even more evident from exfoliated surfaces. taken from the washed off exterior façade. The severe
The main objective of this study is to understand deterioration on exterior of the historic buildings is
the deterioration factors, identify the deterioration also one of basic and dramatic contributor to further
products and characterize the deterioration decay of the interior façades. MS4 was sampled from
mechanisms affecting the heritage structures of the internal façades indirectly exposed to driving rain,
Jahangir tomb. The results obtained in this study will rain run-off and direct sunshine; MS5 was extracted
help formulating a conservation plan and specifying from cored mortars for determination of original
suitable materials for future restoration on the site. constituents/compositions.

Table 1: Mineralogical composition of mortars by XRD


Sample Description Location Calcite Quartz Clay/ Feldspar Gypsum Thenardite Anhydrite Hematite Halite Calcium
Illite oxalate

MS1 Exterior Exposed ++ +++ + + ++ + - + ? t/?


layer Surface
MS2 Jointing Leached +++ ++ + + + + t + + +
mortar surface
MS3 Exterior Washed off ++ +++ +/t t ++ ++/+ +/t +/ t +/ t -
layer surface
MS4 Interior layer Inner layer +++ ++/+ + +/t ++/+ ++ ? ++/+ t -
MS5 Intermediate Directly on +++ ++ + t t/ ? ? - + - -
layer masonry
+++Abundant, ++ present, + small amount, t traces,? doubts in presence,-undetected

2.2. Laboratory determinations mortar and core mortar samples were studied with a
petrographic polarizing microscope to confirm the
The chemical compositions were determined with X- mortar matrix constituent’s alteration identified by
ray fluorescence spectrometer (WD-XRF, Axios, XRD in addition to the conventional standard
PANalytical) to compare element concentration in chemical analysis. The elemental composition and
sound and decayed mortar samples, and understand texture of the mortars along with the composition and
the involved alteration (Binda et al. 2007). The morphology of the salts were studied with SEM-EDS
mineralogy of powdered sample was determined with (JEOL-JSM 6390-EDS-Oxford-1 NCA) as detailed
X-ray diffraction (XRD) using a Bruker, AXS D8 compositional investigation of individual particles
Advance powder diffractometer with CuKα radiation. require this analytical combination.
The petrographic characteristics of the deteriorated

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International Journal of Scientific Research in Chemical Engineering, 1(7), pp. 106-114, 2014

Table 2: Chemical composition of mortars determined by SEM-EDS averaged in wt%.


Sample MS1 MS2 MS3 MS4 MS5
Oxides-wt%
Na2O 1.97 1.00 1.52 1.37 1.50
MgO 3.67 2.71 2.62 2.61 5.50
Al2O3 8.98 6.59 7.14 8.78 9.13
SiO2 32.04 25.49 31.17 28.42 23.03
P2O5 0.17 0.10 0.09 0.16 0.10
SO3 1.30 0.92 1.49 3.63 0.13
Cl 0.12 0.49 0.73 0.82 0.04
K2O 1.35 1.90 2.56 2.88 1.43
CaO 46.06 57.44 50.74 47.60 54.83
TiO2 0.10 0.28 0.17 0.17 0.00
Cr2O3 0.13 0.29 0.02 0.30 0.14
FeO 3.31 2.18 1.75 3.18 3.98
NiO 0.37 0.61 0.00 0.01 0.28
Total 99.57 99.71 100 99.99 100

3. RESULTS AND DISCUSSIONS land use and unchecked urban sprawl created now the
highly polluted micro-environment of the site, which
The studied Jahangir tomb is located close to the large is playing a significant role in damaging the historic
industrial area of Shahdara and Grand Trunk road structure (Gulzar, 2004). The Environment Protection
which transformed from lush green gardens to densely Department of Lahore measured an abruptly increased
populated industrial area with heavy vehicular traffic level of oxides sulphur and nitrogen along with the
over the last 300 years, particularly since 1958 when amount of soot and dust. These severe changes
rapid industrialization and urbanization started (Awan, resulted in the identified degradation pattern of the
1994a, 2009b; Gulzar et al., 2013). The change of historic lime mortars.

Fig. 1: Deteriorated historic surfaces; a) exterior façade mortar leaching from stone masonry joints and b) formation of black
and white crusts in the Jahangir Tomb, Shahdara (Lahore)

3.1. XRD analysis location. The other deterioration products are


thenardite, traces of anhydrite, halite, calcium oxalate
The XRD analysis (Table 1) indicates that core and excess clay.
sample MS5 (collected for determination of original Petrographic observations showed that the mortar
constituents) is mainly composed of calcite-high is composed of small calcite and quartz grains bonded
peaks and moderate peaks for quartz in addition to with a fine calcareous material, containing a range of
few low peaks for clay-illite and accessory minerals pores (MS5), often found filled with gypsum crystals
(feldspar, hematite, etc.). Gypsum is present in all the (MS1, MS2, MS3, and MS4) in the weathered
other samples and its abundance is related to sample samples.

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Gulzar et al.
Chemical Weathering of Lime Mortars from the Jahangir Tomb, Lahore-Pakistan

Fig. 2: Visually identified and megascopically studied sites; a) eroded exterior façade mortar b) deposition of black and white
particles c) washed off mortar surfaces d) rusting and staining of mortar e) biological colonization growth on exterior surfaces
around the rainwater disposal junction and f) dissolution of inner mortar surfaces from the Jahangir Tomb, Shahdara-Lahore

3.2. Chemical analysis weathering/alteration which was further


complemented by increased amounts of other
The X-ray fluorescence analysis (Fig 3) and the SEM- contents.
EDS area measurements (Table 2) show significant The amount of SiO2, Al2O3 and Fe2O3 in weathered
differences between samples, depending upon their MS1 (34.718, 8.106 and 3.507%, respectively) are
exposure and interaction with the surrounding higher than in the core MS5 sample (20.984, 5.262
environment. Sample MS1 from the external façade and 2.285%, respectively). The relative enrichment of
directly exposed to the environmental attack has the Si, Al and Fe is derived from the deposition of
following characteristics compared with the core atmospheric particles (Qin et al., 2005) since the
sample (MS5): Jahangir tomb site (once built away from the busy
The calcite content (CaO+LOI) of intact Mughal urban area) is presently surrounded by a busy road
mortar is 65% while MS1 has less than 50% calcite with increased traffic flows over the past few years.
content (Fig 3); the difference is due to
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International Journal of Scientific Research in Chemical Engineering, 1(7), pp. 106-114, 2014

The amount of SO3 in MS1 is 1.30% which is observable lichen colonization and the blackish color
much higher than that in MS5 (0.13%) measured by of the sampled mortar surface.
SEM-EDS. SO3 is due to SO2 emitted by The SiO2 and CaO contents of 37.92 and 23.50,
anthropogenic sources like combustion of fossil fuels, respectively, with LOI 22.45% (XRF analysis) and
automobile emissions, small foundries and smelters in high amounts of SO3 and Cl (EDS-measurements) in
the vicinity. sample MS3 is attributed to its direct exposure to
The increased amount of Cl (0.12%) in MS1 atmospheric pollutants and rainwater. The relatively
(compared to 0.04% in MS5) is attributed to reaction high amount of moisture favours absorption of
of the mortar substrate with water-transported chloride sulphur dioxide in rainwater and the development of
salts that leads to crystallization and whitish crust moist film on mortar surfaces, where mortar is
formations on exposed surfaces. oxidized to form a sulphuric acid; this acid dissolves
The amount of TiO2 and MnO are 0.44% in MS1 in turn the calcium carbonate by gypsum formation
against 0.08% in MS5. The high content in Ti-Mn (Gauri and Holdern, 1981; Rampazzi, 2004; Qin et al.,
witnesses industrial and urban emissions. The content 2005).
of transition metal oxides contributes to the catalytic Sample MS4 taken from the severely deteriorated
oxidation of atmospheric SO2 and to the sulphation of internal façades shows highest SO3 and Cl contents of
calcium carbonate, which is one of the ongoing 3.63 and 0.82% (Table 2), respectively, compared to
chemical weathering phenomena, as further discussed all other samples. Chloride favours dissolution of
in this contribution. sulphate minerals, creating a process of solubility and
The XRF and EDS measurements performed on precipitation in the high humidity level of 70%
sample MS2 show SiO2 and CaO contents of 19.49 characteristic of the monsoon climatic pattern at
and 33.80, respectively, with LOI 34.55%. This data Lahore (Arif, 2003; Awan and Kazmi, 2009). This
clearly indicates that sample MS2 is rich in organic further allows deposition of the atmospheric pollutants
material, confirmed by traces of calcium oxalate in that are clearly identified from the blackish spotty
XRD, which is ascribable to macroscopically surface of sample MS4.

Fig. 3: X-ray fluorescence analysis of sampled mortars

3.3. Chemical weathering mechanisms time of interaction with pollutants. The resulting
chemical weathering is discussed in the following.
The heavily polluted atmosphere surrounding the
heritage site of Jahangir tomb in addition to the 3.3.1. SOx-rich environment chemical weathering
unfavorable climatic patterns (high humidity,
temperature, moisture etc.) is responsible for the Deposition of sulphur containing particulates results
weathering of historic fabric especially the lime in the following chemical reactions that involve the
mortars. The deposition mechanism of pollutants is constituents of the mortar surface.
complex and depends on several factors. The most (a) The gaseous deposition of SO2 on the mortar
critical factors are the location and exposure of the surfaces initiates the reactions:
historic fabric surface along with its condition at the SO2+CaCO3 → CaSO3+CO2
CaSO3+1/2O2 → CaSO4
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Gulzar et al.
Chemical Weathering of Lime Mortars from the Jahangir Tomb, Lahore-Pakistan

the generation of lichens on the mortar surfaces as


In presence of moisture/water, the wet deposition observed in MS2.
reaction is as follows: 2CaCO3+ (NH4)2SO4+4O2→ Ca (NO3)2+
(b) CaSO4+H2SO4→ CaSO4+H2O+CO2 CaSO4+2CO2+4H2O
The formation of anhydrous CaSO4 in both cases mortar+ microorganisms+ oxygen→ Ca (NO3)2+
is followed by the formation of gypsum: CaSO4+2CO2+4H2O
CaSO4+2H2O→ CaSO4.2H2O Deposition of nitrate on mortars is not a simple
(c) With the formation of gypsum come two function of NOx concentration and is under further
possibilities related to situation: investigation to elucidate this deterioration
-In rain-exposed areas such as those where samples mechanism (Gulker et al., 2004, Arzu at al., 2009).
MS1 and MS3 were taken, CaSO4 or gypsum will be
dissolved (Norvaisiene, 2003; Siegesmund et al., 3.3.3. CL--rich environment chemical weathering
2008).
CaSO4 → Ca++ + SO4-2 The presence of Cl- in the weathered mortar samples
CaSO4.2H2O→ Ca++ + SO4-2+2H2O is indicative of the following weathering mechanisms
-In rain-protected areas the formation of gypsum Stefanis, 2001):
gives rise to surface incrustation that attracts more (a) Salt crystallization-NaCl inducing mechanical
atmospheric pollutants, as observed in MS4. stresses within the mortar constituents and with
interacting surfaces, thus developing into mechanical
3.3.2. NOx-rich environment chemical weathering disintegration.
(b) Playing a significant role in the swelling of clay
Nitrogen oxides (nitrous oxide, nitric oxide and fractions in mortars, which commonly results in
nitrogen dioxide) were found in small concentrations material loss.
but play an important role in weathering of lime (c) An additional phenomenon under investigation
mortars: is the reaction of chloride salt with nitric acid:
(a) NOx besides attacking the historic fabric in NaCl + HNO3 → NaNO3+ HCl
gaseous form is capable of conversion to nitrous and
nitric acids, which are strongly corrosive and 4. CONCLUSION
oxidizing agents reacting with mortar constituents by
converting the carbonates into: Environmental pollution, with (i) emission of S and
NO2+O3→ NO3+O2 N-rich particles into the atmosphere by traffic and
NO2+NO3→ N2O5 industry and (ii) water-transported Cl into mortars are,
NO2+H2O→2HNO3 together with unfavorable climatic patterns,
NO2+H2O→2HNO3 responsible for the chemical weathering of the lime
CaCO3+2HNO3→ Ca (NO3)2+ H2O+CO2 mortars in the Jahangir tomb. Different combinations
The so-formed calcium nitrate is very soluble in of these factors due to variable exposure in different
rain water, leaving cavities in the historic fabric where locations have created incompatibilities between
more pollutants can accumulate. This is one of the mortar constituents and generated deformation.
reasons for detected low concentrations in nitrates in Sulphates (together with associated products) that
the weathered samples (Vazquez-Calvo, 2007). severely affect the lime mortars are a typical result of
(b) Nitrate also contributes to weathering of lime increased vehicular pollution and industry, in addition
mortars by converting SO2 into sulphuric acid that to their natural production. Moreover, the high
chemically weathers the lime mortar surface (Bonazza generation (as secondary pollutants) and
et al., 2009): transportation (one of the major environmental issue
S+O2 → SO2 of polluted cities) of nitrates and chlorides are
2SO2+O2→ 2SO3 disintegrating the mortar constituents and facilitate the
2SO3+ H2O→ H2SO4 formation of various weathering products. Chemical
(c) Another chemical reaction is the catalytic alteration due to above discussed pollutants further
oxidation of sulphur dioxide into sulphuric acid in the enhances the deposition of foreign particles (aerosols,
presence of metals elements such as Ti, Mn, Cu etc. in particulate matter, carbon black soot, biogenic
combination with NOx products etc.) on the weathered surfaces. This initiates
catalyst secondary weathering phenomena, mainly biological
SO2+ H2O+ 1/2O2 → H2SO4 colonization.
(d) The combined corrosive act of SOx and NOx is Dissolution and crystallization of mortar
the biochemical weathering of mortars by promoting constituents in the polluted atmosphere are the main
causes of tensions created within the mortars. Tensile
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International Journal of Scientific Research in Chemical Engineering, 1(7), pp. 106-114, 2014

stresses lead to mechanical disintegration and erosion by microscopic speckle pattern interferometry.
of historic fabric as observed in the Jahangir Tomb In Proceedings of the 10th International
historic façades. Congress on Deterioration and Conservation of
Stone, Stockholm, June 27–July 2, 2004, ed: D.
ACKNOWLEDGEMENTS Kwiatkowski and R. Lofvendahl, vol. 2,
Stockholm: ICOMOS Sweden, 619–626.
The authors would like to acknowledge the Gulzar S (2004). Environmental effects on cultural
Department of Archaeology and Museums and all heritage: Shahdara Complex-Lahore. M.Sc
contributors. We would like to thank Department of Thesis, University of the Punjab, Lahore.
Earth Sciences ETH-Zurich, for their assistance in Gulzar S, Chaudhry MN, Burg JP (2013). Chemical
XRF and SEM-EDS analysis, respectively. and mineralogical characterization of old
mortars from Jahangir tomb, Lahore-Pakistan.
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Dr. Saima Gulzar is an architect working in the field of architectural heritage conservation and
restoration. She has done her Ph.D in Earth and Environmental Sciences focusing on Environmental
Conservation of Architectural Heritage in Pakistan in 2013 and carried out analytical work on
heritage materials in ETH-Zurich during 2009-2011. Presently, she is an academic guest in
Geological Institute for carrying out her postdoctoral research on Ornamental Techniques of 17th
century Mughal architecture in Pakistan. She has published 6 research publications in international
peer reviewed journals along with several posters and conference publications.
Tel + (41) 44 632 85 79; Fax + (41) 44 632 10 30; Email: saima.gulzar@erdw.ethz.ch

Dr. M.N. Chaudhry is a Professor in College of Earth and Enviornmental Sciences from 12 December
2005 to date and Fellow of Pakistan Academy of Sciences. He has earned his Ph.D in Mineralogy
from London University in 1967 and did his postdoc from ETH Zurich, Switzerland in 1996. He has
been the Director of Intitute of Geology from 1997-2001, Director for Postgraduate Center for Earth
Sciences from 2001-2002 ans Director for Intgegrated Mountain Researcg from 1999-2000. He was
also serving as Distinguished Professor of HEC in Punjab University from 2003-2005. He has
published more than 215 national and international publications, 117 papers and posters presented at
national and international seminars. Prof. Chaudhry has been editor (1974-77&1985-1997) and chief
editor (1997-2000) of Geological Bulletin of Punjab University. He is been ranked No.1 in 2005 in
the Directory of Productive Scientist of Pakistan by PCST and ranked No. 2 after change of criteria.
He was also awarded Gold Medals for his outstanding research by Punjab Geological Society,
Pakistan Academy for Geological Sciences and Pakistan Academy of Sciences.
Tel +92 (345) 4005008; Fax +92 (42) 3595 31 00; Email: muhammadnawazchaudhry@yahoo.com

Jean-Pierre Burg has been full Professor (ETH/University of Zurich) at the Institute of Geology of the
ETH Zurich since September 1, 1993. Prof. Burg was born on April 25, 1953 in Meknès, Morocco
and is of French nationality. He received a scholarship from the British Council enabling him to study
as a graduate student at the Imperial College in London from October 1975 to July 1976. From 1979
to 1983 he did scientific research at the French CNRS. His dissertation was honored with great
distinction by the USTL Montpellier in May 1983. In November 1983 he assumed a post as research
fellow at Melbourne University. In March 1986 he was appointed Research Director at the CNRS
Center for Geology and Geophysics in Montpellier, a post he held until he was called to the ETH.
Prof. Burg has many editorial responsibilities. He has been chief editor of "Geodinamica Acta" and
"Géologie de la France" and is now one of the Chief Editors of "TECTONOPHYSICS". His
dedication merited the Australian Society of Educational Technology Award in 1986. He was
awarded the Prix Henri Becquerel from the Academy of Sciences in Paris on 26 November 1990. On the decision of the Sofia
University Council, Prof. Burg received the title Doctor honoris causa on 22 May 1995; at that time he was also given the "The
Blue Ribbon" from Sofia University.
Tel + (41) 44 632 60 27; Fax + (41) 44 632 10 30; Email: jean-pierre.burg@erdw.ethz.ch

Architect Sohail Anwer Saeed is an Associate Professor for Architecture Design at the Superior
University in Lahore and has his own architectural practice in Lahore-Pakistan. He earned his Master
of Science in Architecture-Advance Architectural Studies (Spatial Design: Architecture and Cities)
from Bartlett School of Architecture and Planning, UCL, UK in 1992. He has more than 30 years
experience in architectural design and urban planning projects in Pakistan and Middel East. He has
won many architectural design competitions at national level and senior member of professional
forums. He is an active researcher in the field of architecture, urban spatial planning, conservation
and disaster risk reduction. He has many national and international publications.
Tel + 92(300) 9475408; Fax + 92(42) 3583 18 66; Email: architectsohailsaeed@gmail.com

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