Introduction

Shedding light on of the history of mankind is being conducted by archeologists through their study of ancient artifacts, remnants, manuscripts, and old handicrafts. The ancient Egyptian civilization attracts the attention of many researchers to dig into the secrets of Egyptian fascinating early technology. From the great pyramids to temples, paintings, and mummies, most of them are considered puzzling boundless world that needs to be uncovered. One approach of revealing such mysteries is the use of advanced modern science and technology for analyzing some of their archeological works. The obtained analytical results provide information about the materials used back then and the possible techniques followed to produce such eternal marvels and additionally assist in choosing the proper restoration and conservation methods. Several researchers have investigated the pigments of ancient Egyptian artifacts (Kunjappu 2001; Affifi 2011; Mazzochin et al. 2003). For instance, their conclusion for the formation of black pigments was basically by mixing soot, bee wax, and vegetable gum which was frequently used as a homogeneous painting layer or mixing it with other pigments for darker tones. However, for producing different colors, soot was replaced by other types of materials; for example, ocher was used to make red pigment.

Some conventional spectroscopic techniques such as X-ray fluorescence (XRF) and X-ray diffraction (XRD) methods have been used for the analysis of ancient Egyptian pigments to provide their elemental and molecular composition (Calza et al. 2008; Pradell et al. 2010). Furthermore, particle-induced X-ray emission (PIXE) implemented with an external microprobe has shown great ability to infer the elemental composition of ink as well as papyrus and parchment (Mendes et al. 2008; Hahn et al. 2004). When applying such techniques on unique archeological samples, the analysis might be performed without visible damage, but the mostly required sample pretreatment may jeopardize such precious objects. Moreover, some would provide higher detection limits when compared with plasma-based techniques, matrix dependency, and some relegation to elements of heavy masses. Consequently, sample-friendly techniques are considered safe, practical, and more reliable analytical methodologies.

Laser-induced breakdown spectroscopy (LIBS) has proved its high potential for immediate and multi-elemental qualitative and quantitative analyses for wide-ranging types of samples. Additionally, LIBS worth-noting advantage of producing minimal destruction of the investigated sample as a result of minimum ablated material (~micro-g in a typical LIBS experiment) has recently extended its role to invade the field of archeology and heritage exploration using mobile LIBS systems (Brai et al. 2009; Guirado et al. 2012, 2015). The characterization and differentiation of the different elemental compositions constituting the sample are logically the first stages of proper conservation, restoration, and/or evaluation of historical objects (Abdel-Kareem and Harith 2008). Thus, LIBS has successfully been applied to a variety of objects such as painted artworks, pottery, sculptures, metal, glass, and artifacts (Anabitarte et al. 2012; Ahmed and Nassef 2013, Nassef et al. 2016; Pagnotta et al., 2017). As an example, for the authentication of inks on artistic prints, Oujja et al. (2005) have studied and identified the order in which different ink layers are on a paper substrate using LIBS. They determined the chemical composition and structural distribution of the constituent materials of model prints made by applying one or two layers of several blue and black inks on an Arches paper substrate. By using suitable laser excitation conditions, their analysis of successive spectra on the same spot allowed the identification of the inks and the order in which the inks were applied to the paper. Their results showed the advantages of LIBS for the chemical and structural characterization of art prints. Moreover, Pouzar et al. (2009) developed a method for the analysis of chromium in wool fabric samples dyed by two types of metal complex dyes (C.I. Acid Orange 173 and C.I. Acid Black 60). Their method involved the use of double-pulse laser-induced breakdown spectroscopy (LIBS) for the wool fabric samples. They applied a commercially available LIBS spectrometer which they calibrated with the aid of authentic wool fabric samples previously analyzed by F-AAS after microwave digestion. Their suggested LIBS method provided limits of detection for chromium (from 5 to 10 mg/kg) which were comparable with their measurements using XRF (from 4 to 5 mg/kg).

The aim of the present work is to apply LIBS as a spectrochemical analytical technique for the qualitative analysis of a unique ancient Egyptian textile sample to provide information about the elemental composition of the colors present on the surface of the sample under investigation. Such analyses would avoid the requirement of matrix-matched standards that are associated with quantitative LIBS. To support LIBS results, analyses through SEM-EDX and X-ray diffraction (XRD) techniques are provided.

Samples

In 1922, the unique tomb of King Tutankhamun, which remained sealed for more than 3200 years, has been discovered by the British archeologist Howard Carter in the Valley of the Kings, Luxor, Egypt. The archeological piece of textile under investigation is part of his historical textile collection having the registration no. 16017 in the Egyptian Museum in Cairo. The monumental excavation collection contains a vast accumulation of artifacts and treasures that were believed to accompany the king into the afterlife. The discovered marvelous collection depicts an incredible image of ancient Egypt royal life by more than 740 garments, shrouds, statues, and loincloth. In addition, textiles such as tunics, quivers, and sails of model boats were also found. The objects which have been found in the king’s wardrobe objects were decorated by different colored ornamental units, and the colorful textile objects were distinctively woven by a tapestry type of weave. Ten years after the discovery, most items including textiles were in a relatively modest condition as the majority had been kept in boxes when they were transported to be housed in the Egyptian Museum in Cairo in 1933.

The unbeatable fame of King Tut overall Egyptian pharaohs may originate from the ambiguity of his early death and the probability of being assassinated as a victim of palace power struggles and political intrigues. More importantly, King Tut’s extraordinary valuable tomb and associated artifacts including textile objects are among the best preserved, the most intact ever found, and the most exhibited as well. Fragments that represent very small debris and cannot be re-integrated into the historical objects (including the painted textile sample under investigation) are supportively exploited for auxiliary analyses for unearthing any possible hidden secrets of such archeological remains. Figure 1a shows the layout of the excavated tombs in the Valley of the Kings and the excavated tombs of the pharaohs from the 18th dynasty to Ramesside kings in the 20th dynasty (Earth Observation Science and information Geographic systems (n.d.), http://www.eosgis.com/). Based on the visible distinct colored regions of the drawing of the eye of Horus appearing on the surface of the sample, we focused on each color to study the elemental distribution by the application of both LIBS and SEM-EDX. Figure 1b depicts an image of the Egyptian textile sample showing an overall sample view, besides five investigated selected regions which are labeled and listed in Table 1. Part of Horus eye can be clearly pictured drawn on the textile which was believed as a symbol of protection and divine provision. It may also represent part of the ancient kings’ elaborate titulary which was commonly made up of names, titles, and epithets.

Fig. 1
figure 1

a The layout of the Valley of the Kings and excavated tombs from the pharaohs of the 18th dynasty to the Ramesside kings of the 20th dynasty. b An image of the Egyptian textile sample showing the selected regions analyzed by LIBS

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Table 1 The regions on the textile sample which were subject to the analysis via LIBS
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These five mentioned regions were subject to the investigation via LIBS and SEM-EDX analyses while only pigmented ones in addition to the falling debris were examined by XRD technique.

Experiment and methodology

The details of the used LIBS experimental setup and methodology have been described in previous works (Ahmed and Nassef 2013; Nassef et al. 2016). In summary, a Q-switched Nd:YAG pulsed laser (BRIO, Quantel, France) operating at the fundamental wavelengths 1064 nm and pulse duration of 5 ns (FWHM) was used as the excitation source. The laser beam is focused onto the surface of the sample using a plano-convex fused silica lens with 10-cm focal length to a spot of a diameter of ~ 86 μm. In the present experiment, the pulse energy was set at 25 mJ and 50 mJ which provide laser fluence of ~ 430 J/cm2 and 860 J/cm2, respectively, at a repetition rate of 1 Hz. A 150-cm optical fiber (600 μm diameter) is used to transfer the emitted light from the laser-induced plasma to the detection system of an echelle spectrometer (Mechelle 7500, Multichannel instruments, Sweden) provided with an ICCD camera (DiCAM-PRO, PCO computer optics, Germany). The obtained atomic emission spectra are displayed on a PC where data analysis and processing are carried out using the commercial 2D- and 3D-Gram/32 software programs (National Instruments, USA). Additionally, a comparison between the experimentally measured center wavelengths and those of each element listed in a large emission spectrum database provided by the National Institute of Standards and Technology (NIST) (https://physics.nist.gov/PhysRefData/ASD/lines_form.html) is performed using LIBS++ software for elements’ identification.

The samples were mounted on an X-Y translational stage for controlling the movement of the irradiated position and allow sampling from a fresh location that improves the reproducibility of mass ablation. The laser pulse energy was monitored and recorded before and after running the experiment, using a Joulemeter (SCIENTECH, model AC5001, USA energy meter). Furthermore, to avoid electronic interference and jitters, the control of the detection system was performed using special multi-channel software and the CCD intensifier high voltage was triggered optically at a typical optimized delay time of 1500 ns and gate width 2000 ns. Such acquisition conditions let the initial intense continuum background be avoided, and the optimum signal/background (S/B) results are attained. The resultant overall signal is an accumulation of five single pulse spectra measured under the specified same experimental conditions from several fresh points on the sample surface. This method accounts for possible surface inhomogeneity and also enhances the S/B ratio leading to improving the accuracy of the LIBS analytical results.

For comparison and validation, the investigated archeological samples were examined, imaged, and analyzed via a scanning electron microscope (SEM) (Quanta 250 with Field Emission Gun, FEI Company, Netherlands) attached with energy-dispersive X-ray (EDX) unit, with an accelerating voltage of 30 kV and magnification of 14 up to 106 and resolution of 1 nm. SEM-EDX analyses provide the samples’ surface morphology, samples’ elemental composition, and samples’ concentration.

As a well-known analytical technique for the analysis of minerals and pigments, the composition of the investigated pigmented regions was analyzed by an X-ray diffractometer (Empyrean-PANalytical, Holland) equipped with a variety of different sample holders. The X-ray source is comprised of a Cu radiation tube of wavelength 1.54 Ǻ at 40 kV, 40 mA, 0.004° s−1 with a beta filter nickel. Measurements were performed using a PIXcel 3D detector, in the range 5 < 2θ < 119 with a step of 0.013. The fragments of the sample were positioned on a flat plate sample to characterize the existing compounds by comparing their obtained diffraction data to a typical reference database using PANalytical XRD analysis software (HighScore Plus).

Results and discussion

Plasma characterization

The validity of LIBS measurements and its analytical figures of merit are highly dependent on the physical state of laser-induced plasma (LIP) which can be described in terms of electron density and temperature. LIP is required to be in a local thermodynamic equilibrium (LTE) such that the temperature represents a unique value independent of the thermometric species and in accordance with the electron density. Considering the fast dynamics of LIP and its interaction with the background environment, spatial and temporal gradients of temperature and number densities of both electrons and heavy species occur. For example, plasma peripheral zones are mostly affected by the confinement of the laser-induced shock waves and recombination processes between ions and electrons of the plasma and species from the ambient surrounding. Thus, differences may arise between plasma parameters in external zones and those in plasma core. As LIP homogeneity is a complex issue to establish for the analytical purposes, therefore, the portion coming from the plasma core is here detected where the homogeneity assumption holds (Gaudiuso et al. 2010; Anabitarte et al. 2012).

Additionally, based on the above reasoning, several measures were adopted: (1) careful choice of experimental approaches such as temporal and spatial regions suitable for spectrum detection that ensures the validity of the LTE condition (Kennedy et al. 1997). This has been considered and clarified as already mentioned in the experimental setup and methodology; (2) systematic spectroscopic calculations of both plasma excitation temperature and electron density were performed. For investigating the first parameter, we followed a reported methodology to choose suitable spectral lines for accurate results (Rai et al. 2003). The special conditions required for thermometric purposes should consider the following: lines should be in close spectral proximity so that they could be observed simultaneously and radiance calibration could be considered identical for all lines. Also, the lines should be reasonably intense to provide reasonable S/B ratio in order to minimize background noise degrading the precision of the measured line signals, the transition probability values of the lines should be available, and the difference in upper energy levels from which the emission lines originate should be as large as possible to provide better precision in the temperature measurement.

Adopting one of the spectroscopic methods listed by Griem 1997, the plasma temperature was deduced for each region of the archeological samples. The Boltzmann plot method was applied using selected calcium spectral lines whose corresponding spectroscopic data were obtained from the National Institute of Standards and Technology (https://physics.nist.gov/PhysRefData /ASD/lines_form.html). Calculations resulted in plasma excitation temperature values of ~ 5055 K, 8305 K, 7267 K, 7751 K, and 6119 K for all five regions, respectively, when laser fluence of ~ 860 mJ/cm2 is applied.

The electron density has been calculated from the Hα line at 656.72 nm using the LIBS++ software. The lower limit of the Hα is 1.7 × 1017 cm−3, which verifies the LTE criterion. Hydrogen emission is always present in the LIBS spectra taken in ambient air because of water vapor of the natural humidity of the air. The use of the Hα line for the measurement of the electron density has the definite advantage of providing a result which is not affected by self-absorption unless the sample itself would contain high levels of hydrogen. Moreover, the linear Stark effect acting on hydrogen lines results in a large broadening which reduces the relative uncertainty of the measurement compared with the case of lines emitted by other elements. The deduced electron density in LIP ranged from 0.13 to 0.94 × 1017 (cm−3) for laser fluence of ~ 430 mJ/cm2 and from 0.61 to 1.27 × 1017 (cm−3) when higher laser fluence of ~ 860 mJ/cm2 was applied. In conclusion, calculations of plasma excitation temperature and electron density, which are in agreement with typical values resulting from LIBS experiments, satisfied the criterion (Bekefi 1976) for LTE under the adopted experimental conditions. Thus, LTE can be safely undertaken as a valid assumption for the produced plasma during the adopted observation window which results in reliable outputs.

LIBS elemental analysis

The LIBS measurements’ precision and its sensitivity for elements are highly dependent on the conditions of LIP such as the laser pulse energy and laser wavelength as well as on environmental conditions (surrounding gases or vacuum). In the present work, we conducted the experiment using IR laser which was previously reported to have less damage and shallow craters than that formed by shorter wavelength when applying the same experimental conditions (Ahmed and Nassef 2013). Although working under vacuum enhances LIBS results in terms of S/B ratio, we have conducted LIBS experiments in the air to allow the simulation of portable or mobile LIBS systems that may be used for in situ applications, at museums or excavation sites. To avoid the pulse-to-pulse signal fluctuations, the laser pulse energy was adjusted at a value that exceeds the breakdown threshold and produces clear, visible bright plasma (Camacho et al. 2011). This condition also ensures the production of reproducible plasma and consequently the attainment of better measurements’ precision and sensitivity. Under the adopted LIBS experimental conditions, when a nanosecond pulsed laser beam (5 ns) with long wavelength (1064 nm) is focused on the investigated archeological samples in air, the formation mechanism of the resultant LIP is expectedly dominated by collisional excitation and ionization (Bulajic et al. 2002). The breakdown scenario usually starts with the absorption of the laser energy followed by melting and vaporizing the target material. As the vapor absorbs more energy, high-temperature plasma near the sample surface is formed and expands while transferring its energy to the ambient air. Highly ionized emission lines are presumably found close to the target surface whereas the emission of single ionized and neutral species is likely to appear further away from the surface. The emitted spectral lines of such transient LIP (~ 10 μs in air) are commonly representative of the elements comprising the sample surface under the condition of stoichiometric ablation. Moreover, for analytical signal correction and characterization improvement, LIBS spectral emission signals were normalized to Ca (315.8 nm) as suggested by many researchers (Zorov et al. 2011). Figure 2 provides the LIBS elemental analysis as laser pulse energy (of ~ 50 mJ is focused by the 10-cm focal length lens providing a laser fluence of ~ 860 J/cm2) is applied on the five investigated regions. The normalized LIBS signal for C, Na, Mg, Si, Ca, Al, Ti, Fe, Cu, Sr, Mn, P, and O spectral emission lines indicates their distribution over the sample surface of the investigated regions with different concentrations that are ideally proportional to the intensity of the lines.

Fig. 2
figure 2

LIBS spectral results for some of the detected elements and their corresponding normalized intensity when high laser fluence of ~ 860 J/cm2 is applied on the five investigated regions of the archeological sample

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At high values of laser pulse energy, denser and hotter plasma is formed at the onset of the leading part of the laser pulse; then, the plasma becomes opaque to the laser pulse tail (Harilal et al. 2005). In other words, the descending ending part of the laser pulse would interact with such a plasma surface leading to its absorption and/or reflection without reaching the sample (plasma shielding effect). This situation eventually causes a reduction of the ablation rate, a decrease in the intensity of spectral emission, and a probable increase in the continuum emission. Trying to avoid the occurrence of such effect of plasma shielding, the laser pulse energy was set at a lower value of ~ 25 mJ, providing laser fluence of ~ 430 J/cm2. The possible elements detected by LIBS when such lower laser fluence is applied on the five investigated regions were similar to those obtained when high fluence is used but of lower intensity. A comparison of these two values of laser fluence on region (R1) is shown in Fig. 3.

Fig. 3
figure 3

LIBS emission spectra for region (R1) at the two considered values of laser pulse energy

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It is clear that the application of double-pulse laser fluence resulted in an increase of the intensity of the spectral emission lines indicating an increase in the amount of ablated material which improves LIBS analysis. Enhancement of the emission of some spectral lines such as Mg, Si, and Fe and the detection of some other elements such as Sr, Ti, V, Cu, and Al are obtained when high laser fluence is applied. This also indicates that the applied values of laser pulse energy are away from producing the avoidable plasma shielding effect. Thus, the laser-sample absorption mechanism is attributed to laser-supported radiation wave at both adopted experimental values of laser pulse energy in which plasma temperature becomes very high resulting in plasma transparent for the laser beam, which starts emitting Bremsstrahlung emission due to its high temperature (Aragon et al. 1999; Harilal et al. 2015). The plasma shielding effect is then reduced and the ablation of the target material is enhanced. In this context, it has to be mentioned that the experimental work freely dealt with the investigated archeological sample without an extreme or intense caution as it was directed for scientific research (“Samples”).

Pigmentation analysis

By obtaining the LIBS data, we may infer the ancient used materials and techniques. For region 1 (R1; black pigment), the existence of carbon spectral lines indicates that carbon blacks, the most common ancient black pigments, have been used in the investigated archeological sample. These pigments were easily derived from a partial burning or carbonization of oil, wood, or other organic materials. Also, it is a resultant of any carbon produced in the gas phase arising from the incomplete combustion of hydrocarbon precursors.

For region 2 (R2; yellow pigment), the LIBS elemental analysis shows the existence of several emission lines for Fe and O which support the formation of yellow pigment by iron oxides. The spectral lines of Ti constitute a minor element that could arise from elements of soil. In ancient Egypt, yellow ocher was widely used as a yellow pigment from pre-Dynastic times. It was found in the western desert oases. Examination of Egyptian ocher in ancient paintings was reported to be mostly clay minerals with other varying amounts of iron oxides such as goethite (α-FeO.OH), limonite (FeO.nH2O), and ilmenite (FeTiO2) (Müller et al. 2015).

Different elements such as Cu, Si, Ca, and O that were detected by LIBS for region 3 (R3; grayish green pigment) are closely related to the Egyptian green frit. Researchers have reported that Egyptian green comes from a heterogeneous material ([Ca, Cu]3Si3O9). Its green color is due to silica-rich copper glass, not the copper ions which exist as an impurity. The early technology makes it started with mixing silica, lime, and copper compounds with a ratio of 5:2:2:1 with the addition of flux (Bianchetti et al. 2000; Grifa et al. 2016, Hatton et al. 2008). Several researchers stated that the mixture should contain less copper than calcium, and the added flux should be between 5.7 and 10%.

As previously reported (Lucas 1962; Accorsi et al. 2009; Pagès-Camagna et al. 2010; Johnson-McDaniel et al. 2013) in ancient Egypt, blue pigment was obtained naturally from a bright blue hydrated copper carbonate mineral called azurite whose composition is 2CuCO3.Cu (OH)2. Afterward, during the third millennium BC, the first synthetic blue pigment was prepared as mixture compound presently known as calcium-copper tetrasilicate (CaCuSi4O10). This synthesized pigment was used until the end of the Greco-Roman period (332 BC–395 AD). In the present study, the existence of Cu, Si, and Ca for region 4 (Blue Pigment) leads to a concluding remark that the ancient Egyptian blue pigment contains such synthetic blue.

Region 5 (R5; linen) showed a clear content of C, Ca, Mg, and Na which is a typical elemental representation of linen analysis.

SEM-EDX analysis

The scanning electron microscope (SEM) micrographs provide a characteristic surface morphology and are useful for judging the surface structure of the investigated sample (Nicola 1993; Nord and Tronner 2000). A combination of SEM attached with EDX unit was used to reveal both morphological diagnostic features for an investigated region and the corresponding qualitative and quantitative elemental analysis.

Figure 4 displays SEM micrographs of the Egyptian archeological sample providing a front view of the sample at different positions. The images showed that the surface is extremely roughened, damaged, and cracked with small holes and slits. It is also shown that the textile structure includes a specific type of weaving in which yarns are twisted in circular turns. The EDX spectra providing the elemental composition for the five investigated regions are shown in Fig. 5.

Fig. 4
figure 4

Micrographs of different positions on the surface of the investigated sample with × 600 magnification (left-hand side) and × 160 magnification (right-hand side)

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Fig. 5
figure 5

EDX spectra which represent the main elemental peaks for the five investigated regions

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The elemental EDX output referring to elements’ concentration of the sample surface for each of the five investigated regions is listed in Table 2. An overview of all regions demonstrated that high concentration of carbon (C) exists as a major element which might be the constituent of the linen layer. Presence of Si, Mg, Cl, P, and Ca has also been found throughout the sample which may arise from any source of pollution in the storage or burial environment in the tomb. Appearance of oxygen suggests that most elements are present as oxides. Alumina was known to be added as a stiffening agent and to prevent pigmentation from running off the surface. Evidence of Fe existing in R2 may be an indication for the use of Egyptian ocher used in ancient yellow paintings. For R3, the detected elements such as Cu, Si, Ca, and O are closely related to the Egyptian green frit. One also can infer from the SEM-EDX results for R4 that Cu, Ca, Si, and O may be the components of the blue pigment that consist of a mixture of Egyptian blue (CaCuSi4O10) crystals and partially reacted quartz particles together with varying amounts of the glass phase.

Table 2 The output results of the energy-dispersive X-ray (EDX) analytical technique for the elements’ concentration for the five investigated regions on the surface of the Egyptian archeological sample
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XRD analysis

A supporting high-tech qualitative analytical technique, XRD, is applied in the present work that may provide a clearer picture of the investigated sample’s compounds forming the different pigment contents. Based on the dual-wave/particle nature of X-rays that can conclude information about the structure of crystalline materials, the technique depends on the scattering of the incident X-rays with sample particles which results in the formation of a diffraction pattern. A worth-mentioning problem of such technique in terms of archeological purposes is that the sample should be processed and prepared in the form of powder before being exposed to X-ray. Therefore, for the sake of keeping the sample for any further examinations, the introduction of the sample for XRD analysis was performed in the following manner. By referring to the sample’s image (Fig. 1b), the surface of the fragment comprising R1, R2, and R3 was first placed in the sample’s holder which results in XRD data, shown in Fig. 6a. This was followed by introducing another fragment including R4 along with minute debris of the sample whose data is illustrated in Fig. 6b. An overall qualitative identification of the XRD output spectral data (Fig. 6) indicates the existence of carbon, iron oxide (FeO2), and cuprorivaite (Ca-Cu-Si4-O10) corresponding to the most probable compounds constituting the sample. This could aid validating LIBS elemental analysis and the concluding results for each pigmented region.

Fig. 6
figure 6

XRD spectral data which represents the main constituents for the investigated regions R1, R2, and R3 (a) and for R4 and minute debris of the sample (b)

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Conclusion

In the present study, samples of ancient Egyptian textile from the archeological collections of King Tutankhamun (18th Dynasty), discovered about one century ago, were analyzed via spectrochemical analyses. Applying laser-induced breakdown spectroscopy (LIBS), the physical state of the laser-induced plasma was initially examined for ensuring local thermodynamic equilibrium (LTE) under the adopted experimental conditions. LTE criterion has been checked via calculating plasma parameters: excitation temperature and electron density resulting in safe LTE assumption. The application of laser pulses on fresh spots enabled us to instantaneously detect the spectral plasma emission from discrete points on sample’s surface followed by the analysis of the locally produced spectra for the five investigated regions. The results revealed a visualization of the five distinct investigated regions concluding the existence of some elements such as C, Na, Mg, Si, Ca, Al, Ti, Fe, Cu, Sr, Mn, P, and O. Both values of the applied laser fluence, i.e., 860 mJ/cm2 and 430 mJ/cm2, produced laser-induced plasmas that are found to be optically thin to most investigated emission lines providing better S/B ratio for the higher laser fluence. In summary, quick and informative overview of the elemental analysis of sample’s surface constituents along with minimal destruction has been offered using LIBS. Supporting techniques, i.e., SEM-EDX and XRD, were applied which assist validating LIBS elemental analysis for the investigated archeological sample.