UNIVERSITY OF AGRICULTURE, FAISALABAD

DEPARTMENT OF PHYSICS
(Synopsis for M.Phil. Physics)

TITLE: Spectral Diagnosis of Toxic Contaminants in Cosmetic Samples

Using Laser-Induced Breakdown Spectroscopy

Name of the Student: Warisha Akbar

Registration No. : 2019-ag-2392

Abstract
Laser-induced breakdown spectroscopy is a basic investigation technique. The elemental
composition of all types of samples can be determined by this technique. It can detect all types
of elements or materials like metal, non-metal, cosmetic products, soil, etc. This technique does
not require any sample preparation, limited by used laser parameters like wavelength, energy,
time resolution of the spectrometer, and sensitivity of the detector. By using the LIBS technique,
we can determine the toxic elemental composition in cosmetic products like foundation, lipstick,
blusher, eye shadow, mascara, etc. Such types of make-up products will be analyzed under LIBS
by using a Q-switched Nd: YAG laser. Plasma will be created on the surface of the sample. When
the hot plasma cools down after a certain time then its spectral lines will be observed by a
spectrometer. CCD detector will be used to detect the spectral lines. Plasma temperature and
number density will also be determined and Local Thermodynamic Equilibrium (LTE)
conditions will be verified.

1
 UNIVERSITY OF AGRICULTURE, FAISALABAD
DEPARTMENT OF PHYSICS
(Synopsis for M.Phil. Physics)

TITLE: Spectral Diagnosis of Toxic Contaminants in Cosmetic Samples

Using Laser-Induced Breakdown Spectroscopy

Date of Admission : 24-09-2019

Date of initiation : After Approval

Probable Duration : 6 Months

Personal:
Name of Student : Warisha Akbar

Registration Number : 2019-ag-2392

Supervisory Committee:
Dr. Ayesha Younus : (Supervisor)

Dr. Yasir Javed : (Member)

Dr. Raziya Nadeem : (Member)

Introduction:
Laser-induced breakdown spectroscopy (LIBS) is a vital investigative technique. It is used to
examine very low weight to high weight elements in the periodic table. Many kinds of literature
have been available on frequent use of LIBS to find the presence of toxic elements in different
types of materials (Haider et al., 2012). Investigation of contaminated particles in cosmetics or
any kind of material can be investigated through LIBS (Ledesma et al., 2020). In this technique,
plasma is produced by the direct emission of a laser beam on the sample surface. With the help
of a spectrometer, plasma is collected and then phenomena of optical emission take place.
Through the calibration curves, identification of elements and sample composition takes place.
The whole process is done with the help of the resulting signal of LIBS. The plasma which
determines through the spatial and temporal way provides additional advantages over standard
systematic techniques. By the use of multi-elemental investigation at low and high-
temperature, standoff analysis and in situ process are done with the help of LIBS technique.
LIBS has further been used in the field of fiber optics, real-time and fast analysis. It can also

2
be used in the science of materials, the science of forensic, and biological science (Corazza et
al., 2009).

It applies to solid, liquid, and aerosols. Nowadays, powerful computers are used to determine
the outcomes which are more beneficial for the industrial use of LIBS. Most of the applications
of LIBS are based on metals and alloy processing. While further is based on the characterization
of highly radioactive nuclear waste. On an industrial scale, LIBS is used in pharmaceutical,
chemical, and metallurgy fields. LIBS makes a possible online investigation of raw materials
for the analysis of industrial use (Bhatt et al., 2020).

For the enhancement of skin beauty or protection of skin from harmful elements in cosmetics
are broadly used. Particularly, some cosmetic products not only affect the skin but also affect
the human health. Cosmetics are made up of certain types of waxes, surfactants, oils, water,
metallic powders, and polymers. Among these constituents, metallic fine particles like iron and
zinc are most commonly used for blocking the ultraviolet light in cosmetics. On the other hand,
zinc oxide is used as a sun care product that is limited under a maximum certified concentration
associated with the protection. For example, certain metallic powders such as nickel, lead,
chromium, and cadmium are added to beauty products (Sun et al., 2000).

Current research has conveyed that these metallic elements can cause certain kinds of diseases.
Ni can also cause certain skin problems. The use of lead contained eye shadows or cosmetics
are intensely associated with the prominent cause of eye problem, so lead-containing eye
shadow is officially banned due to its toxic nature. Consequently, the number of metals in
beauty products should be determined carefully. As a result, it is essential to improve the
method for determining metal detection. Several methods are used nowadays such as ICP- MS,
ICP-AES, and FAAS have been established to investigate the samples from food, soil, air, and
water (Hernández-García et al., 2017).

Cosmetics implementation on the skin may cause certain problems because they have
composite organic and inorganic materials. Advanced ICP-MS gives the idea as a dominant
mechanism for tracing metal particles in cosmetics. On the other hand, it demands a great cost
and required extraordinary maintenance. Flame atomic absorption spectroscopy is a typical
technique frequently used to achieve elemental determination in certain systematic
laboratories. By increasing the mechanism and exploration methods. Flame atomic absorption
spectroscopy could identify seventy dissimilar brands of metals with an upgraded detection
(Cha et al., 2010).

3
Quantitative and qualitative analyses of toxic elements that are present in the sample of
cosmetics are determined by the most appropriate technique known as LIBS. LIBS is a type of
atomic emission spectroscopy that develops the characteristics of emission of induced plasma.
For the elemental investigation, LIBS has many advantages over other recognized techniques
such as LIBS does not need sample preparation, originality of sample doesn’t change in this
technique, and sample under LIBS technique does not destroy, so call it non-destructive
technique. It requires a very small amount of sample. It can be applied to any kind of material
and can be used to locate the unreachable dangerous location. LIBS is an immediate and fast
technique that has a low limit of detection and high sensitivity. The sample is accelerated with
the help of a highly directional laser pulse that has a great fluency to create a plasma cloud on
the sample, which is an exclusive alignment of electrons and ions. Firstly, the emission of light
gives a spectrum of unimaginative band. After the bombardment of hundreds of nanoseconds,
the heated plasma cools down. In this situation, before the cooling of plasma completely,
plasma configuration consists of truthfully agitated atomic and ionic species. By the use of the
LIBS technique, a major task in the quantification of components is helpful for the absorption
and reabsorption of the radiated photons, that is owing to the electron-photon interaction within
the plasma. When the photo-induced plasma is in its thermo-dynamical equilibrium state then
self-absorption is less. Features of plasma are defined by the collision process such type of
phenomena undergo with the radiation phenomena that can be ignored by a high electron
density in plasma (Rehan et al., 2019).

Aims and Objectives:

The main aim of that kind of research work is:

➢ To study laser-induced breakdown spectroscopy for spectral diagnosis of toxic

contaminants in cosmetic samples.

➢ To compare the obtained data with the NIST database to monitor the presence of toxic
elements in cosmetic samples.

➢ To determine the plasma temperature and electron number density of the produced
plasma.

4
Review of Literature:

Gondal et al (2010) detected the concentration of certain poisonous elements like Pb, Cr, Cd,
and Zn in different types of lipstick products by using LIBS. Such samples were hazardous and
allergic to human health. Generalization of these materials in the human body causes certain
disorders in the nervous system and may cause kidney damage. To verify the LIBS results that
were used in typical technique such as (ICP-AES) was also be applicable. So, that was the best
way of LIBS technique which was applicable for the determination of toxic elements in certain
kinds of lipsticks. The extreme identification in certain lipstick products was much advanced
than the allowed safe restrictions for human routine and could lead to severe health difficulties.
It was costly to bring up the lipstick that was not compact relatively in a liquid state. And it
was not insignificant to investigate such kinds of lipstick by using the LIBS system. For this
determination of lipstick, sections were compulsory to investigate with the LIBS system.
Gondal et al (2013) studied the profound LIBS sensor that was established utilizing Nd: YAG
laser and charge couple detector with spectrograph which was used to determine the toxic
elements in cosmetic hair color and eye shadow. For hair color chromium was identified
through spectral lines of certain values that were determined by the characterization of LIBS
sensor having a few detection limits. For the eye, shadows lead and chromium was identified
using certain atomic transition wavelengths. Pb and Cr were determined by the range of certain
detection limits respectively. Bocca et al (2014) investigated the determination of metals in
surroundings and their natural existence in rocks, soil, and water that gives a reason to them to
be existing in the creation of pigments and other raw materials that are used in the cosmetic
industry. So, people can face these types of toxic metals as a bit pollutant in cosmetic products
which were used on daily basis. Cosmetics may have numerous procedures and have different
types of uses. Metals confined in these beauty products can cause skin native problems but also
general effects appeared after their absorption through the skin. Cosmetics corporations are not
appreciative to crash on that type of contaminations. The concentration of metals in many types
of cosmetic sets that were shifted worldwide. Eight metals for the concern of review were
antimony, arsenic, cadmium, chromium, cobalt, mercury, nickel, and lead. That was the main
reason, they were omitted as calculated components in cosmetics, which had potential
impurities so-called toxics. Augusto et al (2016) explored his work about the LIBS system
which provides models that were focused on the identification of dirtied substances that have
a high concentration of metal particles such as cadmium, cobalt, chromium, nickel, etc. The
analytical procedure was established by merging emission band information that was collected

5
by LIBS and reference concentration values were gathered from (ICP-OES). Many chemo-
matric tools i.e, principal component analysis, soft independent modeling of class analogies,
K- nearest neighbor, and partial least squares for discriminant analysis, all of these were used
to perform exploratory analysis. By this type of study, it was imaginable to find the
concentrations of toxic metals daily using cosmetics or beauty products. Ahmed et al (2019)
studied different kinds of blusher brands that were sold in local markets. The main purpose of
them was to identify its procedure appropriateness by which various Chinese products form the
widely held many kinds of blushers. X-ray fluorescence and LIBS had been functioned to
determine the attentiveness of several elements like Mg, Si, Al, Ba, Zn, and Rb in dissimilar
Chinese blusher products being traded at native Iraqi markets. To verify our LIBS results, a
method like X-ray powder diffraction was useful. The absorption of fundamental impurities
dignified with our LIBS setup was in close agreement with results by X-ray fluorescence and
X-ray powder diffraction. It was established that the element of these blusher constituents such
as Rutile and Talc. Furthermore, it had been bringing into being that some components species
such as Si, Ti, and Mg have much-developed consideration than the safe acceptable boundaries
associated to confirm the food & drug management boundaries for human practice and could
focal to severe health difficulties, which was a problem of crucial anxiety especially local
blusher models. Therefore, it was extremely mentioned for conclusion manufacturers to
monitor up all the yields being traded in market places. Daileg et al (2019) was chosed the way
of work on poisonous constituents that were investigated by mass of Pb and Cr by using LIBS
technique that was set sidewise for harmless tolerable stages of these elements. Before and after
the standardization outcomes were compared with the related and better results that were
achieved when the spectrum was stabilized. An ordinary analytical method, ICP-OES that was
related to the worth of selected models by the LIBS effect. By implying the consistency of
LIBS measurement, both conclusions were confirmed easily.The previous literature was
prominent for the health and study of aloe vera based cosmetics. Imran Rehan et al (2020)
studied the cosmetic products that were based on aloe vera. Determination of Pb and Cr in aloe
vera based cosmetics were done by LIBS. By the use of Q-switched Nd: YAG laser, the
amounts of (Pb & Cr) were defined in original aloe vera founded beauty soaps. Accurate
investigational work was calculated to recover the understanding of the finding system. Liu et
al (2020) analyzed the manufacturing of cosmetic products that exhibits vital effects on human
health. The presence of heavy metals in cosmetics was detected in previous years. For this
purpose, reliable analytical techniques were used. From previous decades, LIBS was used as a
most powerful and reliable technique. That technique was rapidly used to trace the heavy

6
elements in cosmetics. The sensitivity of LIBS quiet needs development to meet the criteria.
For this resolution, the establishment of ultrasound-assisted extraction sample pretreatment
method for LIBS to trace heavy metals like lead and cadmium in low-quality cosmetic
products. A typical additional method was active for elemental quantification by sum up
identified amounts of analysis into the extracted solution and gets the specified curves of Pb
and Cd. LIBS with the UAE method was a profound and accurate method for the determination
of toxic elements in cosmetics. Mesko et al (2020) analyzed the cosmetic products that were
used on daily basis, the customer may cause several health problems after using these chemical
elements that were present in cosmetic products. The desires for appropriate quality
mechanisms and maximum restrictions for poisonous and hypothetically toxic fundamentals in
foundations had fascinated the consideration of scientific civic and approved certain
organizations all over the world. Maximum restrictions for chemical components in some
foundations may have been set. On the other hand, there were dissimilarities between them.

Materials and Method:

In the present research, samples will be obtained of cosmetic products from different brands
available commercially. Using a LIBS technique, a sample will be examined directly. LIBS
technique will give the full summarizing outcomes of the sampled elements. A setup that will
be designed for the LIBS consists of a Q switched Nd: YAG pulse laser, which distributes a
specific pulse of laser energy at a specific wavelength, time, and repetition rate to record the
LIBS sample spectrum (Tiwari et al., 2017). The average laser bands will be used to get the
final LIBS spectrum. Laser-induced plasma will be created on the sample surface when a light
beam constantly falls on the sample's surface by using a distinct focal length. The sample will
be placed on a translational stage to achieve this objective so that each laser blast incident on
the sample’s surface. The light emitted from the resulting plasma will be collected through a
series of lenses that will be mounted on the tip of the optical fiber and the signals fed to that
lenses and then stored into the device. The stored signals will be compared with the NIST
database and plasma temperature and electron no. density will be calculated to verify local
thermodynamic equilibrium conditions (Dubey et al., 2011).

7
Literature Cited
Ahmed, A., M. Salman, M. Alwazzan, and A. Meri. 2019. Blushers component analysis for
unbranded cosmetic brands: Elements’ concentration levels and their effect on the
human body. Journal of Advanced Research in Dynamical and Control Systems, 11(5
Special Issue): 412-419.
Augusto, A. D. S., É. F. Batista and E. R. Pereira-Filho. 2016. Direct chemical inspection of
eye shadow and lipstick solid samples using laser-induced breakdown spectroscopy
(LIBS) and chemometrics: Proposition of classification models. Analytical Methods,
8(29): 5851-5860.
Bhatt, C. R., H. K. Sanghapi, F. Y. Yueh, and J. P. Singh. 2020. LIBS application to powder
samples. Laser-Induced Breakdown Spectroscopy, 2nd ed. Elsevier B.V.
Bocca, B., A. Pino, A. Alimonti, and G. Forte. 2014. Toxic metals contained in cosmetics: A
status report. Regulatory Toxicology and Pharmacology, 68(3): 447-467.
Cha, N. R., J. K. Lee, Y. R. Lee, H. J. Jeong, H. K. Kim, and S. Y. Lee. 2010. Determination
of iron, copper, zinc, lead, nickel, and cadmium in cosmetic matrices by flame atomic
absorption spectroscopy. Analytical Letters, 43(2): 259-268.
Corazza, M., F. Baldo, A. Pagnoni, R. Miscioscia, and A. Virgili. 2009. Measurement of
nickel, cobalt, and chromium in toy make-up by atomic absorption spectroscopy. Acta
Dermato-Venereologica, 89(2): 130-133.
Daileg, J. A., C. J. De Ocampo, C. D. Domingo, and M. I. Guerrero. 2019. Chemical
Analysis of Heavy Metals in Organic, Counterfeit, and Local Brand Lipsticks Using
Hydride Vapor Generation Technique – Atomic Absorption Spectroscopy 3(2): 7-11.
Dubey, A., G. Keyvan, R. Hsia, K. Saranteas, D. Brone, T. Misra, and F. J. Muzzio. 2011.
Analysis of pharmaceutical tablet coating uniformity by laser-induced breakdown
spectroscopy (LIBS). Journal of Pharmaceutical Innovation, 6(2): 77-87.
Gondal, M. A., Y. W. Maganda, M. A. Dastageer, F. F. Al-Adel, A. A. Naqvi, and T. F.
Qahtan. 2013. Development of a laser-induced breakdown sensor for detection of
carcinogenic chemicals in cosmetic products. 2013 High Capacity Optical Networks and
Emerging/Enabling Technologies, HONET-CNS 2013, 84-87.
Gondal, M. A., Z. S. Seddigi, M. M. Nasr, and B. Gondal. 2010. Spectroscopic detection of
health-hazardous contaminants in lipstick using Laser-Induced Breakdown
Spectroscopy. Journal of Hazardous Materials, 175(1–3): 726-732.
Haider, A. F. M. Y., R. S. Lubna, and K. M. Abedin. 2012. Elemental analyses and

8
 determination of lead content in kohl (Stone) by laser-induced breakdown spectroscopy.
Applied Spectroscopy, 66(4): 420-425.
Hernández-García, R., M. E. Villanueva-Tagle, F. Calderón-Piñar, M. D. Durruthy-
Rodríguez, F. W. B. Aquino, E. R. Pereira-Filho and M. S. Pomares-Alfonso. 2017.
Quantitative analysis of Lead Zirconate Titanate (PZT) ceramics by laser-induced
breakdown spectroscopy (LIBS) in combination with multivariate calibration.
Microchemical Journal, 130: 21-26.
Ledesma, R., F. Palmieri, and J. Connell. 2020. Laser-induced breakdown spectroscopy of
polymer matrix composites for real-time analysis of trace surface contaminants: A
review. International Journal of Adhesion and Adhesives, 98(August 2019): 102528.
Liu, Y., Y. Chu, Z. Hu, S. Zhang, S. Ma, M. S. Khan, F. Chen, D. Zhang, L. Guo, and C.
Lau. 2020. High-sensitivity determination of trace lead and cadmium in cosmetics using
laser-induced breakdown spectroscopy with ultrasound-assisted extraction.
Microchemical Journal, 158(June): 105322.
Mesko, M. F., D. L. R. Novo, V. C. Costa, A. S. Henn, and E. M. M. Flores. 2020, February
15. Toxic and potentially toxic elements determination in cosmetics used for make-up:
A critical review. Analytica Chimica Acta.
Rehan, I., M. A. Gondal, K. Rehan, S. Sultana, M. A. Dastageer, and F. F. Al-Adel. 2019.
LIBS for the detection of lead in ready to use henna paste and nutrients in fresh henna
leaves and cultivated soils. Talanta, 199: 203-211.
Rehan, Imran, M. Z. Khan, K. Rehan, S. Sultana, I. Qasim, S. Ud Din, H. Anwar, and Sayyar
Muhammad. 2020. Determination of Lead and Chromium in Aloe Vera Pulp and Aloe
Vera-Based Cosmetics by Laser-Induced Breakdown Spectroscopy (LIBS). Analytical
Letters, 53(16): 2571-2584.
Santos, M. C., and F. M. V. Pereira. 2020. Direct analysis of human hair before and after
cosmetic modification using a recent data fusion method. Journal of the Brazilian
Chemical Society, 31(1): 33-39.
Sperança, M. A., D. F. Andrade, J. P. Castro, and E. R. Pereira-Filho. 2019. Univariate and
multivariate calibration strategies in combination with laser-induced breakdown
spectroscopy (LIBS) to determine Ti on sunscreen: A different sample preparation
procedure. Optics and Laser Technology, 109(September 2018): 648-653.
Sun, Q., M. Tran, B. Smith, and J. D. Winefordner. 2000. In-situ evaluation of barrier-cream
performance on human skin using laser-induced breakdown spectroscopy. Contact
Dermatitis, 43(5): 259-263.

9
Tiwari, P. K., S. Awasthi, B. K. Ghosh, and A. K. Rai. 2016. Empirical investigation and
discrimination of Personal care products using LIBS and Multivariate Analysis
(September): 20-23.

10