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CHEMOMETRIC DISCRIMINATION OF BLEACHED AND DYED HUMAN SCALP HAIR USING ATTENUATED TOTAL REFLECTANCE INFRARED SPECTROCOPY NURUL ASMA SALSABILA BINTI MOHAMAD ALIAS UNIVERSITI TEKNOLOGI MALAYSIA

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Page 1: CHEMOMETRIC DISCRIMINATION OF BLEACHED AND DYED …eprints.utm.my/id/eprint/78880/1/NurulAsmaSalsabilaMFS2017.pdftujuan aplikasi forensik. Enam orang subjek wanita yang memiliki rambut

CHEMOMETRIC DISCRIMINATION OF BLEACHED AND DYED HUMAN

SCALP HAIR USING ATTENUATED TOTAL REFLECTANCE INFRARED

SPECTROCOPY

NURUL ASMA SALSABILA BINTI MOHAMAD ALIAS

UNIVERSITI TEKNOLOGI MALAYSIA

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CHEMOMETRIC DISCRIMINATION OF BLEACHED AND DYED HUMAN

SCALP HAIR USING ATTENUATED TOTAL REFLECTANCE INFRARED

SPECTROCOPY

NURUL ASMA SALSABILA BINTI MOHAMAD ALIAS

A dissertation submitted in partial fulfilment of the

requirements for the award of the degree of

Master of Science

Faculty of Science

Universiti Teknologi Malaysia

SEPTEMBER 2017

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To my late father, Mohamad Alias Mohamad Yunus and my everything, Aziah

Mohd Shah Baki

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ACKNOWLEDGEMENTS

Alhamdulillah, in the name of Allah, the Most Gracious and the Most

Merciful, with His perfect arrangements I was able to complete my dissertation.

First and foremost, heartfelt gratitude to my late father, Mohamad Alias,

my dearest umi, Aziah Mohd Shah Baki, and my family members, Nurul Khairun

Nisaa, Nurul Atiqah, Nurul Amirah, Muhammad Hadi Fathi, Mohamad Aizat

Daniel and Munzir Zulkifli. This dissertation is also dedicated to my friends and

comrades in battles, Nur Najwa Zulkifli, Faridah Aminullah, Siti Fatimah Hussen,

Aida Rasyidah Azman, Yew Wan Hui, Aidil Fahmi Shahdan, Elissa Shafura

Suleman and many more. Thank you for listening to my rants, always reminding

me I am capable of something more and believing in me when others don‟t. No

words can describe their continuous and undivided supports. For your endless

prayers and faith in me, I thank you from the bottom of my heart.

Gratitude to my supervisor and co-supervisors, Dr Hasmerya Maarof, Dr

Naji Arafat Mahat and Supt. Tan Yan Thian for their patient guidance,

constructive criticism, recommendations and encouragements. Special thanks to

Puan Norhaznita Noordin, Grace Duraisingham as well as the volunteers from

Akademi Rambut Mayang Emas for willingly participated in this study. Thank

you to the Faculty of Science and staff for their kind assistance and cooperation.

Finally, indeed this dissertation was made with blood, sweat and tears.

Therefore, utmost appreciation to myself for persevering and making it this far.

Salsabila, you deserved this.

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ABSTRACT

The range of products, different formulation, and variables used in

cosmetic treatments hold out great potential for forensic identification of hair

evidence although in reality little of that potential is realized due to preferences on

DNA testing and lack of analytical chemistry expertise among forensic examiners.

It is therefore of interest to produce a rapid data acquisition technique that can

classify cosmetically treated human hair for forensic application. Six female

donors with natural black hair underwent a series of cosmetic hair treatments

namely bleaching and dyeing. The following hair strands were collected; natural

(control), bleached, day-1 dyed hair/ week 0, week 2, week 4, week 6 and week 8.

Statistical interpretation of the triplicate absorbance readings of 126 hair samples,

determined using ATR-FTIR was used to classify the type of treatments, the two

different brands and weekly intervals of collected hair samples. A wavenumber

region of hair protein variability from 1750 to 800 cm-1

was selected for pattern

recognition analysis, Principal Component Analysis (PCA) and Hierarchal Cluster

Analysis (HCA). PCA provided a satisfying classification based on the types of

cosmetic treatments, brands as well as weekly intervals of hair, and permitted up

to more than 90% amount of variance, indicating the reliability and validity of the

model. Results from HCA complemented the deduction. This present study sheds

light in proposing the use of ATR-FTIR combined with chemometric analysis for

a simple and accurate classification technique of cosmetically treated human scalp

hair which can be incorporated into a forensic hair screening protocol.

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ABSTRAK

Rangkaian produk, formulasi yang berbeza dan pembolehubah dalam

penggunaan rawatan rambut kosmetik mempunyai potensi untuk proses

identifikasi bukti rambut forensik walaupun dalam realiti potensi itu tidak disedari

kerana keutamaan pada ujian DNA dan kekurangan pakar kimia analitikal dalam

kalangan pemeriksa forensik. Justeru itu, kajian ini berminat untuk menghasilkan

suatu kaedah pemerolehan data yang pantas dan berupaya untuk

mengklasifikasikan rambut manusia yang telah melalui rawatan kosmetik bagi

tujuan aplikasi forensik. Enam orang subjek wanita yang memiliki rambut asli

berwarna hitam telah melalui suatu siri rawatan kosmetik rambut iaitu pelunturan

dan pewarnaan. Berikut merupakan rambut yang telah dikumpul ; asli (terkawal),

diluntur, hari-1 diwarna/ minggu 0, minggu 2, minggu 4, minggu 6 dan akhirnya,

minggu 8. Tafsiran statistik bagi tiga ulangan bacaan serapan 126 sampel rambut

telah ditentukan menggunakan ATR-FTIR untuk mengklasifikan jenis rawatan,

dua jenama berbeza dan selangan mingguan sampel rambut yang telah dikumpul.

Nombor gelombang mewakili kepelbagaian protein dalam rambut bermula dari

1750 hingga 800 cm-1

telah dipilih untuk analisis pengenalpastian corak iaitu

Analisis Komponen Utama (PCA) dan Analisis Kelompok Hierarchal (HCA).

PCA telah menghasilkan klasifikasi yang memuaskan berdasarkan jenis rambut

yang telah melalui rawatan kosmetik, jenama produk serta selangan mingguan dan

membenarkan sehingga lebih daripada 90% jumlah varians menunjukkan

kebolehpercayaan dan kesahihan model sementara HCA melengkapi deduksi

tersebut. Kajian ini telah mencadangkan penggunaan ATR-FTIR bersama analisa

„chemometric‟ untuk menghasilkan suatu teknik pengklasifikasian yang ringkas

dan tepat bagi sampel rambut kepala manusia yang telah dirawat dengan kosmetik

sebagai protokol forensik untuk pemeriksaan rambut.

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TABLE OF CONTENT

CHAPTER TITLE PAGE

DECLARATION ii

ACKNOWLEDGEMENT iv

ABSTRACT v

ABSTRAK vi

TABLE OF CONTENT vii

LIST OF TABLES x

LIST OF FIGURES xi

LIST OF ABBREVIATIONS xiv

LIST OF SYMBOL xvi

LIST OF APPENDICES xvii

1 INTRODUCTION

1.1 Research Background

1.2 Problem Statement

1.3 Objective and Hypothesis

1.4 Scope of Study

1.5 Significance of Study

1

3

4

5

5

2 LITERATURE REVIEW

2.1 Physiology of Human Hair

2.1.1 Cuticle

6

8

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2.1.2 Cortex

2.1.3 Medulla

2.2 Cosmetic treatments of human hair

2.2.1 Bleaching

2.2.2 Dyeing

2.2.3 Washing and conditioning

2.2.4 Weathering

2.3 Hair as forensic evidence

2.4 Infrared spectrosocpy

2.5 Chemometric Methods

2.5.1 Principal Component Analysis (PCA)

2.5.2 Hierarchal Cluster Analysis (HCA)

2.6 IR and chemometric analysis of hair

10

10

11

12

13

17

18

18

19

22

22

23

26

3 METHODOLOGY

3.1 Materials

3.2 Methods

3.2.1 Experimental design

3.2.2 Microscopic and ATR-FTIR

Analysis

3.2.3 Chemometric analysis

29

30

30

32

33

4 RESULTS AND DISCUSSION

4.1 Rationale

4.2 Preliminary observation using compound

microscope

4.3 ATR-FTIR analysis

4.3.1 Natural hair

4.3.2 Comparison of natural hair to

chemically treated hair

4.4 PCA and HCA analysis

34

35

40

40

43

46

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4.4.1 Classification of natural, bleached

hair and day-1 dyed hair

4.4.2 Classification of day-1 dyed hair from

two different brands

4.4.3 Classification of hairs dyed by two

different brands exposed to varying

weathering intervals

4.4.3.1 Brand A

4.4.3.2 Brand B

4.4.3.3 Week 8 datasets

4.4.4 Analysis of the entire datasets

4.4.4.1 PCA Scree Plot

4.4.4.2 PCA Loading Plots

4.4.4.3 PCA Score Plots

4.4.4.4 HCA dendogram

4.5 Forensic hair evidence screening procedure

4.6 Limitation

47

54

57

58

62

67

71

71

73

75

77

78

81

5 CONCLUSION AND

RECOMMENDATIONS

5.1 Conclusion

5.2 Recommendations

82

83

REFERENCES 85

Appendices A - C 94 - 101

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LIST OF TABLES

TABLE NO. TITLE PAGE

2.1 Chemical species present in human hair 7

2.2 Characteristics of the different types of hair dyes 15

2.3 Oxidation products of different hair treatments 27

4.1 Comparison of band peaks in accordance with

previous study

45

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LIST OF FIGURES

FIGURE NO. TITLE

PAGE

2.1 Cross section of human skin showing hair

growing out of follicle

7

2.2 Schematic cut away section of a hair fiber

indicating the cuticle, cortex, and medulla

9

2.3 Medulla patterns of human hair 11

2.4 A histograph depicting the relationship between

the frequency in casework with different type of

trace evidence in criminal cases

19

2.5 ATR setup 21

2.6 The procedure of a hierarchal cluster method 24

2.7 Computation for the distance between a data

cluster and a point

25

3.1 The flow chart of the study 31

3.2 (a) Subject‟s hair upon applying the mixture of

bleach powder and stabilizer (b) Subject‟s hair

after rinsing from bleach (c) Subject‟s hair final

color copper

32

4.1 Microscopic image of (a) normal hair (b)

bleached hair (c) day-1 dyed hair brand A (d)

day-1 dyed hair brand B with magnification of

200x

37

4.2 Dyed hair of Brand A, after the following time

interval (a) 2 weeks (b) 4 weeks (c) 6 weeks (d)

8 weeks with magnification of 200x

38

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4.3 Dyed hair of Brand B, after the following time

interval (a) 2 weeks (b) 4 weeks (c) 6 weeks (d)

8 weeks with magnification of 200x

39

4.4 Natural hair spectrums from 6 donors (1) Amide

A and B (2) CH stretch (3) CH stretch (4)

Amide I (5) Amide II (6) C-H deformation

bands (7) Amide III (8) Cysteine Monoxide

41

4.5 Bleached hair spectrums of a) subject 1 b)

subject 2 c) subject 3 d) subject 4 e) subject 5 f)

subject 6

42

4.6 Spectrums of a) natural b) bleached c) day-1

dyed hair

44

4.7

4.8

2D PCA score plots of natural, bleached and

day-1 dyed hair datasets

3D PCA score plots of natural, bleached and

day-1 dyed hair datasets

48

49

4.9 HCA dendogram of natural, bleached and day-1

dyed hair datasets

50

4.10

4.11

2D PCA score plot of natural and bleached hair

3D PCA score plot of natural and bleached hair

51

52

4.12 HCA dendogram of natural and bleached hair

datasets

53

4.13 PCA score plots of day-1 dyed hair of brand A

and B (a) 2D and (b) 3D

55

4.14 HCA dendogram of day-1 dyed hair datasets 56

4.15 PCA score plots of brand A dyed hair based on

0, 2, 4, 6, 8 weeks (a) 2D and (b) 3D

59

4.16 HCA dendogram of brand A week 0, 2, 4, 6 and

8 datasets.

60

4.17 2D PCA score plots of brand A dyed hair based

on 2, 4, 6, 8 weeks datasets

61

4.18 3D PCA score plot of brand A dyed hair based

on 2, 4, 6, 8 weeks datasets

62

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4.19 2D PCA score plot of brand B dyed hair based

on 0, 2, 4, 6, 8 weeks datasets

63

4.20 3D PCA score plot of brand B dyed hair based

on 0, 2, 4, 6, 8 weeks datasets

64

4.21 HCA dendogram of brand B week 0, 2, 4, 6 and

8 datasets

65

4.22 PCA score plots of brand B dyed hair based on

2, 4, 6, 8 weeks datasets (a) 2D and (b) 3D.

66

4.23 PCA score plots of week 8 dyed hairs from two

different brands (a) 2D and (b) 3D

68

4.24 HCA dendogram of week 8 datasets for

different types of brands

69

4.25 PCA scree plot 72

4.26 (a) Loading plot of PC1 versus PC2 (b) loadings

on PC1 (c) loadings on PC2

74

4.27 PCA score plots (a) 2D and (b) 3D 76

4.28 HCA dendogram of all datasets 77

4.29 Procedure for hair sample screening based on

present findings

79

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LIST OF ABBREVIATIONS

.XLS - Microsoft Excel file format

2D - 2 Dimensional

3D - 3 Dimensional

ATR - Attenuated Total Reflectance

ATR-FTIR - Attenuated Total Reflectance - Fourier

Transform Infrared

cm - centimetres

cm-1

- Reciprocal centimetres

DNA - Deoxyribonucleic Acid

E.g. - Exempligratia

etc. - Et cetera

FTIR - Fourier Transform Infrared

HCA - Hierarchal Cluster Analysis

HPLC - High Performance Liquid Chromatography

i.e. - In essence

Inc. - Incorporation

IR - Infrared

PCA - Principal Component Analysis

PCs - Principal Components

PC1 - First principal component

PC2 - Second principal component

PC3 - Third principal component

pH - Potential of hydrogen

R groups - group in which a carbon or hydrogen atom is

attached to the rest of the molecule

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SEM - Scanning Electron Microscope

TLC - Thin Layer Chromatography

USA - United States of America

UV - Ultraviolet

UV-Vis - Ultraviolet-Visible

Vol. - Volume

Viz. - Videlicet

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LIST OF SYMBOLS

C - Carbon

H - Hydrogen

KBr - Potassium Bromide

O - Oxygen

S - Sulphur

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LIST OF APPENDICES

APPENDIX TITLE PAGE

A Research acknowledgement 94

B Research Information Form 95

C1 Consent Form 97

C2 Consent Form 98

C3 Consent Form 99

C4 Consent Form 100

C5 Consent Form 101

C6 Consent Form 102

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CHAPTER 1

INTRODUCTION

1.1 Research Background

The field of forensic science is generally defined as the application of

scientific approach in legal issues (Nordby, 2005), encouraging the advancement of

scientific methods and procedures to facilitate individualization since cases with

diverging circumstances are commonly encountered. Evidence, particularly biological

specimens, retrieved from the crime scene are most likely affected by the

environment (Brandes, 2009). Trace evidence transferred during a crime forms an

integral part of a forensic investigation as it may be the significant evidence

associating or acquitting an individual to a crime (Barton, 2011).

Apart from blood, human hair is one of the most transferable biological

specimens and often found in a large amount (Brandes, 2009). In principle, a person

shed approximately 50 to 100 hair strands per day (Deedrick, 2000), making it a

common evidence recovered at crime scenes. Due to its rigidity, flexibility as well as

durability (Velasco, 2009), hair forms a reasonably good piece of physical evidence.

Generally, the information that could be obtained from a single strand of hair includes

DNA profile, hair pigmentation, toxicity, and characteristics (e.g. hair colorant or

treatments as well as the possible race/ethnicity) (Tobin, 2005). However, the

process of acquiring DNA from hair is always subjected to degradation,

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contamination, extremely costly, and does not always generate successful results,

especially in the absence of follicles (Manheim, 2015). Considering instances

wherein hairs are found without their follicles, rendering difficulties for extracting

DNA, they are classified as the class characteristic evidence (Saferstein, 2011).

Microscopic examination of hair may reveal forensically important

information viz. color, thickness, shape, race, somatic origin, as well as the method of

removal i.e. either forcefully or naturally (Barton, 2011). However, interpretation of

the results relies largely on individual expert interpretation that may vary from one

another (Manheim, 2015), “owing to a lack of a uniform reference for identifying the

specific microscopic characteristic seen in a study hair” (Barton, 2011). In this

context, analyzing the chemical compositions of hair, especially the dyed ones using

non-destructive analytical instruments such as Fourier Transform Infrared (FTIR) for

revealing forensic information has been suggested (Panayiotou and Kokot, 1999).

Considering the current trend that involves a myriad of hair treatments (e.g. coloring,

bleaching, straightening and perming) (Guerra-Tapia and Gonzalez-Guerra, 2014), as

well as the prevailing environmental pollutions (Sporkert et al., 2012) that may

influence chemical decompositions, continuous researches on such chemical

decompositions acquire forensic consideration.

Hair evidence treated with chemical e.g. bleaches or dyes may increase its

individuality by providing unique characteristics for criminalistics assessment

(Brandes, 2009). Robertson (1999) has classified hair dyes into three main categories

namely temporary dyes, semi-permanent and permanent. Ever going development of

products and techniques in hair cosmetic treatments may alter the evidential value of

hair in terms of morphology (Dias, 2015), chemical composition and its ability in

storing the history of the substance of abuse (Cuypers et al., 2014; Crunelle et al.,

2015). In an instance, bleaching (or also known as oxidation treatment) is reported to

alter the structure of cysteine in hair (Kuzuhara et al., 2013). Hence, analyzing hair

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as an evidence may throw light to forensic investigators by providing valuable clues

for narrowing down the search.

Currently, the use of chemometric techniques such as Principle Components

Analysis (PCA) and Hierarchal Cluster Analysis (HCA) for enabling discriminations

of materials has been acquiring popularity (Pilatti et al., 2017; Myron et al., 2017).

In forensic science, such an application has been referred to as forensic provenancing

(Kreitals and Watling, 2014). Such chemometric techniques can be especially useful

when dealing with populations that exhibit limited genetic divergence with

indistinctive boundaries (Alacs et al., 2010). As for hair analysis, the use of

chemometric techniques has also been reported for chemically treated hair (Barton,

2011; Brandes, 2009; Panayiotou and Kokot, 1999). Considering a great deal of

variations in hair treatments, continuous assessments in this aspect may prove useful.

1.2 Problem Statement

Hair remains one of the most important evidence recovered at crime scenes.

Although DNA analysis would provide individualization, the fact that in many

instances the hair strands are recovered without follicles, analyzing them for DNA

profiling may prove problematic (Barton, 2011). Because the use of chemical

treatments such as dyes and bleach has been acquiring considerable popularity in the

population (Guerra-Tapia and Gonzalez-Guerra, 2014), and may denote certain cults

or social groups, characterizing the microscopic traits of hairs such as its morphology

and presence of dyes (Dias, 2015), may be useful for narrowing down the search for

suspects, an important clue for forensic investigators. The fact that many different

types and brands of hair dyes, constituting varying chemical compositions, have been

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continuously introduced into the market, continuous assessment on chemical

characterization of hair in vivo proves necessary. In addition, continuous exposure of

treated hairs towards the environment, as well as the natural human biological

processes may lead to variations in the chemical decomposition of such hairs (Wong,

1972). Hence, this present research that investigated the changes in the composition

of varying functional groups between the natural hairs (control) with that of bleached

and subsequently dyed using two different brands of Copper hair dyes, for enabling

forensic characterization using PCA and HCA, merits specific consideration.

1.3 Objectives and Hypothesis

Using Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR)

coupled with either PCA or HCA, this present research was designed to characterize

and discriminate the in vivo:

(a) Natural and bleached hairs.

(b) Hairs dyed using two different brands of copper dyes.

(c) Hairs dyed by the two different brands exposed to varying weathering

intervals (0, 2, 4, 6 and 8 weeks).

It was hypothesized that utilization of the PCA and/or HCA would provide

adequate separations among the different groups of hairs and dyes, suitable for

criminalistics assessment.

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1.4 Scope of Study

The natural, bleached and dyed human scalp hairs were collected from six

female subjects residing in Kajang, Selangor. The subjects were divided into two

groups i.e. Group A (n=3) and Group B (n=3), each dyeing their hair using the A

and B brands of Copper color dye, respectively. Analysis was then done on hairs

for both groups exposed to four different intervals (0, 2, 4, 6 and 8 weeks). Pre-

discrimination of the hair samples was done using a compound microscope, while

ATR-FTIR with the spectral region ranging between 4000-600 cm-1

was used for

chemical characterization of the collected samples. The data from the IR spectra

were interpreted chemometrically using PCA and HCA.

1.5 Significance of Study

The significance of this present study is to ease the process of discrimination

of hair evidence found at crime scenes. This study is proposing a method that

allows extraction of the utmost forensic information, particularly human hairs that

are subjected to chemical treatments. By analyzing its chemical profiles using the

statistical interpretation of IR analysis, a more specific discrimination may be

feasible, especially when individualization could not be attempted. For real

forensic casework applications, the approach may possibly narrow down the search

for suspects, as well as exonerate the innocents.

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