j. Soc.Cosmet.

Chem.,35, 379-390 (December1984)

Analysisof hair by electronspectroscopy

for chemicalanalysis
C. R. ROBBINS and M. K. BAHL, ColgatePalmolive
Co.,
Research
Center,909 RiverRoad,Piscataway,
NJ 08854.
ReceivdJuly26, 1984.
Synopsis

An exploratory
studyis presented
evaluating
electronspectroscopy
for chemical
analysis
(ESCA)asa tool
for studyinghumanhair. ESCAprovides
valuableinformation
aboutthe hairsurface
to a depthof 20 to
30 angsttoms,
andESCAis especially
usefulfor studyingthe oxidationof disulfidesulfurin hair. ESCA
canalsobe usedto studythe removalof lipid fromhair and/orthe adsorption
of ingredients
to hair such
assulfate-containing
surfactants.

A primaryreactionin theweathering
of humanhairinvolves
degradation
of disulfidesulfur,andultraviolet
radiationis a principalcauseof this degradation.
This reactionoccurs
primarilyat or nearthe hairsurface
andappears
to involvedegradation
of cystineresidues
via the C-Sfissionmechanism.
Chemicalbleaching
of disulfidein hair by alkalinehydrogenperoxideis differentand appearsto proceedthroughthe S-S
fission route.

INTRODUCTION

Chemicalanalysisof humanhair, modifiedby weatheringeffectsanddifferentcosmetic

treatments,has beenthe objectof severalscientificinvestigations(1-5). Suchstudies
often involve analysisof whole fiber (1-5), which disregardsthe fact that both the
chemicalstructureand chemicalmodificationsto hair generallyare not uniform along
the fiber crosssection.Prior to sophisticated
spectroscopic
techniques,chemical(6) or
physical(7) separationof the fiber was essentialto analyzethe chemistryof the hair
fiber surface.

Electronspectroscopy
for chemicalanalysis
(ESCA)involvesirradiationof a samplewith
X-raysof knownenergywhichcauses
coreelectrons
to beejectedfromthesample.The
"binding energy"of theseejectedelectronsprovidesinformationabout the chemical
composition
of the samplesurface(8). Zhao, Liu, andWang (9) haveshownthat ESCA
canbe usedto studyoxidativechangesto cystineresiduesin hair. The presentinvestigationdemonstrates
that ESCAis a sensitiveand usefulmethodfor studyingabsorption or chemicalchangesat or near the hair fiber surface,to a depth of 20 to 30
angstroms.

EXPERIMENTAL
STANDARD

COMPOUNDS

Sodiumlauryl sulfate(SLS)waspurchased
from EastmanOrganicChemicalsandcystine
379

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JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

from PierceChemicalCompany.The sodium3-hydroxyhexadecylsulfonatewasa high

purity sampleobtainedfrom Ethyl Corporation.
HAIR

Unaltered
hair. Samplesof chemicallyunalteredhair werepurchased
from females,ages
5 to 30, purportedto have neverbleached,dyed, or permanentwavedtheir hair three
yearsprior to cutting. Thesehair sampleswere shampooed
and then cut at the scalp.
A triethanolammonium
lauryl sulfate,cocamideDEA shampoowasused.Dark brown
Oriental hair, purchasedfrom DeMeo Brothers,New York, wasalsousedin this study.
This

hair was used intact

and not washed unless indicated

and also bleached with

alkalinehydrogenperoxide.

Bleached
hair. Fivegramsof 10-inchOrientalhairwasbleached
for 30 minutesat 25C
with 6% hydrogenperoxide(200 ml) adjustedto pH 10 with ammoniumhydroxide.
Ultravioletexposure.
Hair sampleswereexposed
to two ultravioletlampsof modelXX
15 C from Ultra-Violet Products, Inc. of California. These lamps emit ultraviolet
radiationat a maximumwavelengthof 360 nm. The distancebetweenultravioletlamps
and hair wasapproximately25 cm, the temperature70F, and the relativehumidity
between50 to 70 percent.
Sodium/aury/surfate
treatment.
One gram tresses
from Oriental hair were immersedin
1% SLSfor 5 minutesand then rinsedundera deionizedwater tap for 2 minutesand
allowedto dry overnightat room temperature.
ESCAmeasurements.
ESCAmeasurements
wereperformedin a Perkin-Elmer560 ESCA/
SAM analysissystem.This systemis equippedwith a dual anodeMg/AI X-ray tube,
differentialpumpedion gun, and a SIMS II system.The hair samplesweremounted
on indium foil. Samplesizewasapproximately1 cm x 1 cm. All ESCAspectrawere
takenwith a PHI model25-270 AR doublepasscylindricalmirror analyzeroperating
in the large aperture mode and at a passenergyof 100 eV for surveyscans.High
resolutionspectrawere taken at passenergiesof 25 and/or 50 eV. For argon ion
sputteringof the hair samples,a differentialpumpedion gun using a 5 kV-25 mA
argonion beamwasused.The vacuumin the main chamberof the spectrometer
during

accumulation
of spectra
wastypicallyof theorderof 5 x 10-8 torr.
The percentconcentration
of eachelementis relatedto thepeakareaandto a sensitivity
factorfor eachelement. Sensitivityfactorsand the softwareto calculateatomicconcentration wereprovidedby Perkin-Elmer.

RESULTS
SURVEY

AND

ANALYSIS

DISCUSSION
AND

WEATHERING

OF HAIR

In an initial experiment,an ESCA surveyscanof a humanhair samplewasmadefrom

0 to 1,000 eV, to determinewhich elementsare presentin the hair surface(Figure 1).
From this surveyscanwe decidedto evaluatecarbon,oxygen,nitrogen,and sulfurat
higher resolution,using passenergiesof 25 and 50 eV scans.

Averageresultsfrom thesehigh resolutionscansfor both root and tip portionsof 8

different hair samples,purportedto be cosmeticallyundamaged,are summarizedin

HAIR

ANALYSIS

BY ESCA

381

C AUGER

12

io

oAUGER

0 Is

NIs

cis

s 2s s2p

2 , "' i x4

-I000

-900

-800

-700

-600

-500

-400

-300

-200

-I00

BINDING
ENERGY,
Figure 1. ESCAsurveyspectrum
of hair. N(E) = numberof countsat kineticenergyE of thoseelectrons
at the specificbinding energy(eV) in electronvolts.

Table i. Thesedata showthree significantroot-to-tip differences.The tip endsof hair

containlesscarbonand more oxygen,suggestingthat oxidationof hair hasoccurredin
the tip ends.Prior studiessuggestthat one oxidativereactioninvolvedin weathering
of hair occursat sulfur (3,9). The sulfur 2p scansproducedtwo peaks,with binding

energies
of approximately
168.0 and 163.3 eV (deltaeV = 4.7) (Figure2). Comparison
of thesebindingenergieswith the literature(8) (Table iI) and with thoseof standard
compounds
(cystineand sodium3-hydroxyhexadecylsulfonate)suggests
that the lower

binding
energy
corresponds
to disulfide
sulfur,referred
toasSn, andthehigherbinding
Table

ElementalCompositionChangesBetweenRoot and Tip Endsof the Hair Surfaces

Root

Tip

% Carbon

80

72*

% Oxygen
% Nitrogen

14
3

21'
4

% Sulfur

sW/sn

0.63

2.2'

$ N = 8; hair 10 to 18" long.

* Differencein valuesbetweenroot and tips arestatisticallysignificantby Wilcoxonmatchedpairssigned
ranks test.

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JOURNAL

OF THE SOCIETY OF COSMETIC CHEMISTS

0 [

-176

-174

-172

I , I
-170

-168

I
-166

I,
~164 -162

-160

-158

BNDINGENERGY(eV)
Figure 2. S 2P spectraof root and tip endsof hair. N(E) = numberof countsat kineticenergyE of
thoseelectrons
at the specificbindingenergy(eV) in electronvolts.

energy,whichroutinelyoccursat a separation
distanceof 4.5 - 0.5 eV fromdisulfide,

corresponds
primarilyto sulfonate
andis referred
to asSw.
Binding energyvaluesare assignedrelativeto the carbon1 S peakat 284.6 eV. This
assumesthat this binding energyis not affectedby chemicalenvironmentand is the
samein hair asaromaticor alkyl carbonis in purecompounds.
For assignment
of peaks
that are a few electronvolts or lessapart, it is morereliableto considerbindingenergy
differencesrather than absolutevalues.Therefore,throughoutthis report we referto
sulfur binding energydifferencesrel,ativeto disulfide. Table II summarizesbinding
energydifferencesbetweenseveralspeciesof oxidizedsulfurand disulfide,from data
by Siegbahneta/. (8), on pure organicsulfur compounds.

Theincrease
in theratioof STM
to SI in tip endsvsrootends(Figure2) isin agreement
with infrared and other studies(4, 10, 11) and confirmsthat oxidation of sulfur is an
important reactionin the weatheringof human hair.

HAIR

ANALYSIS

Table

BY ESCA

383

II

Binding Energiesof Different Sulfur Structures*

BindingEnergy
Sulfur Structure
R-S-S-R

Disulfide

eV
162.7

Binding Energy
-

R-S-SO-R
162.3 -0.4
Diulfide Monoxide

R-S-SO-R

164.8

2.1

R-S-SO2-R

162.8

0.1

DiJulfide
Dioxide
R-S-SO2-R

167.1

4.4

R-SO-

167.2

4.5

167.8

5.1

162.8

0.1

Sulfonate

I R-S-SO

S-Sui-fonate
(Bunte's
Salt)
R-S-SO
3-

* From data by Siegbahnetal. (6).

: A represents
the differencein binding energybetweenthe designatedsulfur atom (underlined)and
disulfide sulfur.

The total oxygenincreaseduring weathering(Table I) is greaterthan can be accounted

for by sulfur oxidationalone. This is consistentwith oxidationby ultraviolet light
where no mechanicaldamageoccurred(seebelow). These data suggestthat another
oxidationreactionoccursat carbonduring weatheringof hair. We intend to studythis
reactionin greaterdetail, and to report on it in a subsequent
publication.
What is called root ends here actually representshair cut near the scalp. The actual
portion of the analyzedsampleswas approximately1 to 2 cm from the scalp, representativeof approximatelyone to two monthsweathering.ESCA indicatesthat these

eight samplesof hair (s'eeExperimental

sectionunderUnalteredHair) nearthe scalp

containan average
of 39% STM(% of totalsulfur)anda rangeof 15 to 56%. This
amount seems unusually high. However, ESCA representsonly the top 20 to 30

angsttomsof the hair fiber surface,which is the regionmostsusceptible

to weathering
actions.The largevariationin the relativeamountsof oxidizedto unoxidizedsulfurin
the hair surfaceof thesesamplesis probablyfrom variation in the exposureof the
samplesto different environmentalconditionsas well as to differencesin the susceptibilities of thesesamplesto oxidation.
Oxidationstatesof sulfur in eachof the 8 hair samplesare summarizedin Table III.
In 7 of the 8 samples,there is a greateramountof oxidizedsulfurin tip endsthan in
root ends. Evaluationof thesedata by the Wilcoxon matchedpairs signedrankstest

shows
a significantly
greater
ratioof Sw to SI in tip endsthanin rootends,consistent
with weatheringoxidation.

Sample#4 is an exception.This hair was the shortestsampleexamined,and came

from a 21-year-old female. Discussionswith the seller did not provide any clues to

384

JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

Table

III

Weathering
of Hair Shown
by Difference
in sVi/s
riFromRootandTip Ends
Ratio sVI/sII

SampleNo.

Lengthof Hairs
(In. from Scalp)

Root

Tip

1
2
3

12
12
14

O.33
0.67
0.46

0.56
1.71
1.16

10

1.29

0.5

16

0.75

1.18

17

0.27

3.1

7
8

13
18

0.17
1.1
0.63

2.6
6.78
2.2

Differencein valuesbetweenroot and tip endsare significantly

differentvia Wilcoxonmatchedpairs
signedranks test at ot = 0.05 level.

S Hair purchased
from femaleCaucasions
aged5 to 30 and cut next to scalp,exceptsample#8 cut
approximately
6" from scalp.

explain this anomaly.All subsequentsamplesobtainedwere from femalesaged 5 to

12 to minimize the possibilityof on-headtreatmentvariations.
To exploreand to help explain the effectsof sulfur oxidationduring weatheringexposure,we examinedsample#7 at approximately7.6-cm intervalsalong the fiber
axis. The resultsof this studyare summarizedin Table IV. Thesedata showincreasing
amountsof sulfur oxidationwith increasingdistancefrom the scalp,consistentwith
weatheringaction over time.
ACTION

OF ULTRAVIOLET

LIGHT

ON

HAIR

Veldsman(12) concludesthat ultraviolet radiation is the most important single factor

in the weatheringof wool fiber. Thereforeultravioletradiationmust be important in
weatheringof human hair. To test the hypothesisthat oxidativedegradationof hair is

inducedby ultravioletlight, we exposedonehair sampleto ultravioletradiation(360

nM) for 13 days, and analyzedit by ESCA. Table V summarizesthe resultsof this
experimentand showssimilar trends to the tip end effects,i.e. decreases
in carbon

Table

IV

Axial Distribution of Oxidized Sulfur in One Hair Sample*

Distance

0 to

% STM

From

Scalp(cm)
2.54
7.6
15.2
22.9
33.0

RatiosVl/s
TM

in Sample

0.17
0.32

15
24

0.58
1.51

37
60
72

2.60

* Sampleno. 7 (seeTable III), 13" long from scalp.

HAIR

ANALYSIS

Table

BY ESCA

385

Effectsof UV Light on Hair

Average
Root End

Atom

Average
Tip Ends

13 Days.q:
UV Lamp

% Carbon

80

72

69

% Oxygen
% Nitrogen

14
3

21
4

27
3

% Sulfur

sV/sI

0.27

3.1

7.3

Sample#6, rootendsexposed
to UV radiation.

content,
andincreases
in oxygen
content
andanincrease
in theSTMtOSII ratiorelative
to root ends.

TableVI summarizes
datafrom anotherexperimentin whichhair sample#6 had been
exposedto ultraviolet radiationfor increasingtimes. Thesedata showincreasingcon-

version
ofdisulfide
toSvI withincreasing
exposure
toultraviolet
radiation.
These
results
are consistentwith the hypothesisthat ultravioletlight is primarily responsible
for the
oxidationof sulfur in weatheringof human hair.

The ultravioletradiationusedin this experimentis in the UV-A (320 to 400 mu)

portion of the spectrum.In anotherexperimentwe demonstratedthat UV-B (290 to
320 mu) radiationis alsocapableof oxidizingsulfurin hair.

Only two samplesof hair were exposedto UV-B (310 mu) radiationand the resultant
binding energieswere the sameas obtainedfrom UV-A exposedhair. No direct comparisonon the samehair sourcewasmadebetweenthesetwo wavelengthregions,and
thereforewe cannotassess
the relative hair damagingeffects.
SURFACTANT

INTERACTION

WITH

HAIR

ESCAcanalsobeusedto provideusefulinformationaboutthe adsorption

of ingredients
to the hair surface.Hair was washedwith 1% SLSas describedin the Experimental
section,and examinedby ESCA relative to a control washedwith deionizedwater.
Table VII summarizesthe resultsof this studyand showsa decrease
in percentcarbon,

anincrease
in sodium
andnitrogen
percentage,
andanincrease
in theSTMtOSII ratio.
Table

VI

Effect of UV Light on Sulfur in Hair*

Ratio

# DaysExposed

sVI/s

% sVI.J:

0.27

21

3
6
9

O.65
1.29
2.48

39
56
71

13

7.33

88

* Sample#6 (seeTable III), root endsexposedto UV radiation.

.'1:
% STMto total sulfur.

386

JOURNAL OF THE SOCIETYOF COSMETICCHEMISTS

Table
SLS Reaction With

VII
the Hair Surface

UnwashedHair*

SLSWashed Hair:

% Carbon

67

64

% Oxygen
% Nitrogen

23
5.9

23
7.3

% Sulfur
% Sodium

3.4
0.9

3.4
1.6

sW/stt

0.31

0.45

* Oriental hair from DeMeo Bros., New York, NY, rinsed with deionizedwater.

: SeeExperimentalsection.

The decreasein percentcarboncontentand increasein percentnitrogencontentare

consistentwith the removalof a lipid type soil from the surfaceof a proteinaceous

substrate.
Theincrease
in theSTMto Sn ratiois consistent
with theadsorption
of lauryl
sulfateto the hairsurface.
The SvI bindingenergyoccurred
at 168.8eV or 5.3 eV
from the disulfidepeak at 163.5 eV. This peakwasresolvedinto two peaks,one at
4.2 eV and the otherat 6.1 eV from the disulfidepeak.We assignthe formerpeak
to sulfonateand the latter to sulfate, basedon Siegbahn'sbinding energydifferences
betweendisulfideand sulfonateof approximately4.5 eV and approximately6.0 eV
between disulfide and sulfate (8).

Only one replica for eachsamplewas analyzed,and thereforestatisticscannotbe ap-

plied.However,the indication
of a newshoulder
shiftingthe STMbindingenergyto a
higher level suggeststhe adsorptionof lauryl sulfateto the hair surface.
SURFACE

VS BULK

ANALYSIS

ESCA is a method for analysisof approximatelythe top 20 angstromsof a solid.

ThereforeESCA can provide a meansto comparesurface-vs-bulk
reactionsby either
comparingESCAdatawith data from othermethods,or by usingspecialseparation
or
blendingtechniquesin combinationwith ESCA.

Table

VIII

Bulk Analysisof Sulfur vs ESCA

SV/srI
ESCA

Ground

Control

Sample#8
Tip End
Sample# 12

Hair*

Calculated from

Amino Acid Analysis

0.02

6.78

Root End

0.27

0.16

Tip End

0.69

0.32

* Groundby handwith mortarand pestlein li%uidnitrogen.

HAIR ANALYSIS BY ESCA

387

Table VIII showsresultsof ESCA data from the tip endsof one hair sample(#8),

comparing
the STMto S ratio,with aminoacidanalysis
of thesamehairsample.The
ESCAresultsreflectonly the outersurfaceof the first cuticlelayer,andadsorbed
matter.
The aminoacidanalysisprovidesan averageresultacrossthe entirecross-section
of the

hair. Furthermore,
the Sv fromthe ESCAresultreflects
all species
of oxidizedsulfur
(predominatelysulfonate)(9), while the amino acid analysisconsidersonly sulfonate
(cysteicacid) as oxidizedsulfur.

The unusuallylarge differencesby thesetwo methodssuggestthat the weathering

actionof hair occursprimarily at or nearthe fiber surfaceand decreases
rapidlytoward
the fiber interior. This conclusion
wassupportedby analyzingrootandtip endportions
of the samesample,both intact and after hand grinding the hair with a mortar and
pestlein liquid nitrogen. ESCA resultsfrom the groundhair (Table VIII) providea

lowerratioof STMto S thanfromtheintacthairasexpected.

Morethorough
grinding
of thehairto providemoreeffective
blending
shouldlowerthe STMto S ratioeven
further,andtheoretically
theSv to S ratioshould
approach
equivalence
for rootand
tip samplesin the vicinity of the valuecalculatedfrom the aminoaciddata. The fact
that thesevaluesare so far from that calculatedvaluesuggeststhat this handgrinding
is a very inefficientmeansfor blendinghair.
Sputteringis a techniquein which the sampleis exposedto an argonion beamthat
removes(sputters)the outer surfacelayersof the solid. In our systeman argon ion
beamof 4 KeV wasusedwhich hasan approximatesputteringrate of 20 angstroms/
minute. Our objectivewasto determineif sputteringmight be usefulfor studyingthe
depth of penetrationand/oractionof chemicalsin hair. Our exploratoryresultssuggest
that sputteringis not usefulfor analysisof eithersulfuror nitrogenin hair because
it

is a reductive
process
whichconverts
STMto S andprotonated
amineto freeamine.
Thesereactionsdiminish the usefulness
of sputteringas a techniquefor hair analysis.
CEMC^

VS WE^'P,SG

OXD^'OS

OF SUFUP,

IS

^P,

Hair sampleswhich had been bleachedwith alkaline hydrogenperoxide(seeExperimental section)were analyzedby ESCA. The data are summarizedin Table IX and

showan increasing
ratioof STMto S with increasing
chemical
bleaching.
Thedecrease
in percentoxygenremainsunexplained.Note the large increasein percentnitrogen,
whichis consistent
with the removalof a lipid (soil)fromthe surfaceof a proteinaceous
substrate.

The STMpeakfor this chemically

oxidizedhair appears
at 4.0 eV fromthe disulfide

Table

IX

Effectof ChemicalBleachingon the ElementalCompositionof the Hair Surface

Control

Bleached(1 X )

Bleached(5 X )

% Carbon

67.3

68

67

% Oxygen
% Nitrogen

23
5.9

20
8.7

20
9.9

% Sulfur

3.5

3.7

3.7

sV/sn

0.31

0.69

1.19

388

JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

bindingenergy,and closeto the valueof 4.1 eV reportedby Zhao,Liu, andWang

(9). This is a slightly smallerenergydifferencethan expectedfor sulfonateat 4.5 eV
in pure organiccompounds(8) (Table II).
The chemicaloxidationof cystineis believedto proceedvia the S-Sfissionroutethrough
severalintermediateoxidationproductssuchas disulfidemonoxideand dioxide(Table
II, Figure 3). Low concentrations
of theseintermediatesin the presenceof sulfonate
and disulfideshoulddecrease
the binding energydifferencebetweenthesetwo species.
A higher resolutionESCA spectrometer
is requiredto resolvethe binding energiesof
these speciesto determine to what extent they exist as end productsin chemically
bleachedhair. However, we concludewith others that sulfonateis the major end
productof the oxidationof the disulfidebondin hair with alkalinehydrogenperoxide
(9-11).

Table X summarizesbinding energiesfor weatheredhair, hair exposedto ultraviolet

light, and chemicallybleachedhair. The binding energiesfor the weatheredhair and
the hair exposedto ultravioletlight aresimilar. However,the binding energydifference

for the STMpeakvs disulfide

of chemically
bleached
hairappears
to be lower.Similar
binding energiessuggestsimilar mechanismsof sulfur oxidation, and differencesin
binding energiessuggestdifferentmechanisms
of action.As indicatedabove,the mechanismfor peroxideoxidationof disulfideis believedto be throughthe S-Sfissionroute

(13,14), whilefor irradiationof cystinethe C-Sfissionrouteis preferred(14) (seeFigure

3). For the formerreactionthe main end productis sulfonicacid (13,14), but for the
latter reaction, the main productsare the -S-sulfonicand sulfonicacids(14).

Foronesampleof weathered
hairin bothrootandtip endstheSTMpeakwasresolved
into two peaks,one at a binding energydifferenceof 5.4 eV and the otherat 4.3 eV
from the disulfidepeak(Figure4). The dataof TableII showsthat the formerpeakis
closeto the expectedbinding energydifferencefor -S-sulfonate
and that the latter peak
is closeto the expectedvalue for sulfonate.In the root end region the relative amount
of sulfur corresponding
to sulfonatewasapproximatelytwo times that of-S-sulfonate,
and in the tip end region approximatelyfour times. This is consistentwith the fact
that prolongedirradiationof cystineproduces
cysteicacidasthe main product(14).

Hair exposed
to ultraviolet
lightprovided
a bindingenergy
forSv of 4.7 eV fromthe
binding energyfor disulfide. This is closeto the expectedvalue of 4.5 for sulfonate

(8). TheSv peakwasresolved

intotwopeaks
corresponding
to bindingenergy
differS-S

FISSION

RS-S-R--R-SO-S-R
R-S02-SR[-S02-SO-R]..-S(-S2R-SO)H
c-s

R-S-S-RR

FISSION

-S-S-OH

R-S-SOiH
R-S -SO)H
R-SO)H
+ H2SO

R-OH

Figure 3. Mechanisticschemesfor oxidationof the disulfidebond.

HAIR ANALYSIS BY ESCA

Table

389

Sulfur Binding Energiesin VariousHair Samples

Binding Energies(eV)

Hair Samples

SII

SIV

Weathered Hair

163.5 -+ 0.2

168.3 _+ 0.3

4.8

Exposedto
Ultraviolet Lamp
(Root Ends)

163.6 + 0.1

168.3 + 0.1

4.7

163.5 --+ 0.1

167.5 --+ 0.1

4.0

Chemical

AEV

Bleached

(8202)

ences vs disulfide of 4.5 and 5.8 eV. The former we attribute

to sulfonate and the

latter to -S-sulfonate.We attribute the shift to a higher binding energyto the presence
of sulfateion formedby breakdownof S-sulfonate(Figure 3). Siegbahn(6) indicatesa

binding energydifferencebetweendisulfideand inorganicsulfateof 5.0 to 6.0 e

dependingon the accompanying
counterion. Evidencefor this conclusion
(presence
of
inorganicsulfate)is the fact that water rinsing of hair exposedto ultravioletradiation

for 13daysreduces
thebindingenergy
difference
between
S andSTM.We believe
this
is due to rinsing the water-solublesulfateion from the hair.

150

//-R-S-S-R
100

R-S-SO

5O

-178

-176

-174

-172

-17o

-168

-166

-164

-162

-16o

BINDING
ENERGY,
(eV)
Figure 4. Resolutionof S 2P binding energiesin weatheredhair. N(E) = numberof countsat kinetic
energyE of thoseelectronsat the specificbinding energy(eV) in electronvolts.

390

JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

SUMMARY

AND

CONCLUSIONS

ESCA is a usefultechniqueto studyweatheringreactionsof humanhair, surfactant

interactions,and chemicalbleachingof hair. Ultraviolet radiationis primarily responsible for weathering degradationof hair, with the primary action occurringnear the
fiber surface.Data is presentedwhich supportsthe S-Sfissionmechanism
for peroxide
degradationof sulfur in hair and the C-S fissionroute for weatheringdegradation.
Sputteringis a reductiveprocessand thereforeof limited valuefor ESCA studiesof
sulfur or nitrogen in hair.
REFERENCES

(1) R. Clay, K. Cook, andJ. Routh, Studiesin the compositionof humanhair, J. Amer.Chem.Soc.,
62, 2709-2710

(1940).

(2) J. Lang and C. Lucas, Analysisof hair keratin. I. Application of microbiologicaltechniquesto

hydrolyzatesof human hair, Biochem.
J., 52, 84-87 (1952).
(3) C. Robbins,Weatheringin humanhair, Text. Res.J., 37, 337 (1967).
(4) C. R. Robbinsand C. H. Kelly, Amino acidcomposition
of humanhair, TextileRes.J., 40, 891896 (1970).
(5) C. Robbinsand C. Kelly, Amino acid analysisof cosmeticallyaltered hair, J. Soc.Cosmet.
Chem.,
20, 555-564 (1969).
(6) J. H. BradburyandJ. D. Leeder,Keratin fibers.IV. Structureof cuticle,Amt. J. Biol. Sci., 23,
843 (1970).
(7) J. A. Swift and B. Bews, The chemistryof human hair cuticle-I: A new method for the physical
isolationof cuticle,J. Soc.Cosmet.
Chem.,25, 13-22 (1974).
(8) K. Siegbahn,C. Nordling, A. Fahlman,et al., Electronspectroscopy
for chemicalanalysis,Tech
ReportAFML-TR-68-189, Wright PattersonAir ForceBase,Ohio, National TechnicalInformation
Service(1968).

(9) L. Zhao, S. Liu, and T. Wang, A study of the mechanismof the oxidationof hair keratin by
photoelectronspectroscopy,
Acta Biochimica
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