lead levels - Journal of Cosmetic Science Digital Archive

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j, Cosmet.
sci., 59, 399-418 (September/October
2008)
A studyof the chemicalcompositionof traditional
eye cosmetics("kohls")usedin Qatarand Yemen
ANDREW D. HARDY, Centre
for MedicalHistory,School
of
Humanities
and SocialSciences,
University
of Exeter,ExeterEX4 4RJ,
Devon,UK; ALEXANDER J. FARRANT, Department
of Chemistry,
School
of BioSciences,
University
of Exeter,ExeterEX4 4QD,
Devon,UK; GAVYN ROLLINSON, Camborne
School
of Mines,
Universityof Exeterin Cornwall,Tremough
Campus,
PenrynTRIO
9EZ, Cornwall,UK; PETER BARSS,Facultyof Medicine& Health
Sciences,
UnitedArab EmiratesUniversity,PO Box 17666,
A1 Ain, United Arab Emirates;and RAGINI
VAISHNAV,
College
of Medicine,
SultanQaboos
University,
Box35,
A1 Khod123, Sultanateof Oman.
Accepted
for publication
February29, 2008.
Synopsis
This study looksat the chemicalcompositionof traditionaleye cosmeticsCkohls")usedin Qatar and
Yemen.Of especialinterestwashowmanysamplesin eachcountrycontainthe toxicelementlead.In Qatar
19 observably
differentkohlsamples
wereobtained,andin Yementensuchsamples
obtained.The analytical
techniques
of scanningelectronmicroscopy
(SEM)andX-ray powderdiffraction(XRPD) wereusedto study
the samples.For the samplesfromQatar, six of the 19 (32%) containedgalena(leadsulfide,PbS)--all as
the main component.However,for the samplesfrom Yemen,five of the ten (50%) samplescontainedgalena
asthe main component,with anotherthreehavingit presentasa minorcomponent.Overall,the othermain
components
werefoundto be:amorphous
carbon(3), ironoxides(hematite,Fe20•; andgoethite,FeO(OH))
(t), quartz(SiO2)(1), sassolite
(H3BO3)(5), talc (Mg3Si40•o(OH)2)(1), and zincite(ZnO) (7).
INTRODUCTION
As part of continuingstudieson Middle Easterntraditionaleyecosmetics("kohls"),we
have looked at the chemicalcompositionof such cosmeticsavailable in Qatar and
Yemen. Of especialinterestis the determinationof thosecontaininga lead compound
(usuallylead sulfide),and comparisonof the percentages
foundof suchsamplesin these
two
countries.
It is thought that traditionaleyecosmeticsare usedmainly by the older generationsin
both Qatar and Yemen, the youngest(e.g., student)generationbeing more inclinedto
usethe importedWestern-madeeye cosmetics.Also, when the kohls are usedin both
399
400
JOURNAL OF COSMETIC SCIENCE
thesecountries,they can be applied solelyas cosmetics--oftenbeing then designated
"cold"--or as both cosmetics
and eyemedicines--theseoften being designated"hot."
In the more industrializedcapital city of Doha (Qatar) there are more kohl samples
imported from India and Pakistanthan are found in the lessindustrializedcapitalcity
of Saana(Yemen).Both cities,as expectedgiven the geographical
proximity, havekohl
samplesimportedfrom SaudiArabia.
To our current knowledgethis is the first study of the (chemical)compositionof
traditional eyecosmetics
usedin Qatar; and for Yemen, while the detailsof the manufactureand compositionof the traditional black dye/body-paint("hidab")have been
studied(1), this is the first study doneon traditionaleye cosmetics.
In the lastfew years,sinceour lastpublication(2), only a few kohl-relatedstudieshave
appearedin the publishedliterature. Three kohl sampleswere characterizedby the
relativelynew techniqueof confocalRamanmicroscopy
(3); a cause-effect
relationship
has been suggestedbetweenthe use of lead-basedkohls and in the accentuationof
periorbital pigmentationand the developmentof associated
anemia (4); and, most
recently,a rare caseof homicidalpoisoningvia a lead-based
kohl has beenpresented
in the literature (5).
In our previousstudieson the chemicalcompositionof kohls obtainedin Oman (6),
Cairo(7), andthe United Arab Emirates(UAE) (2,8), we foundlead(usuallyasthe lead
sulfide,PbS)to be presentin someof the samples.Thus,presentedhere,aspart of our
ongoingstudyinto the presence
of lead in traditionaleyecosmetics
(kohls)and aspart
of an ongoingeducationon the toxicity--especiallyfor younggrowing children--of
usingsuchmaterials,is a comparative
chemicalcomposition
studyof the kohlsavailable
in Qatar and Yemen.
MATERIALS
AND
METHODS
MATERIALS
A total of 28 kohl sampleswerepurchasedin the souksof Doha, the capitalcity of the
Gulf stateof Qatar. They were regardedas a good "crosssection"of all suchsamples
availablefor purchase
in Doha.Of these28 samplesit wasfoundthat 19 wereobservably
different.The priceper kohl samplevariedbetween1 and 6 Qatari riyals(QR), where
3.65 QR wasequivalentto 1 USS.
In Yemen a total of eight kohl sampleswere purchased:sevenin the two souksof the
capitalcity of Saanaandonein the soukof Saadh,a mountaintown severalhoursdrive
northwestof Saana.An additionaltwo kohl sampleswereobtained,aspersonalgifts, in
Aden. Thus, overall,theseten sampleswereregardedasa "selection"
of thoseavailable,
rather than a comprehensive
surveyof a//those available,in Yemen. The price of the
purchasedsamplesvariedbetween150 and 500 Yemeni riyals(YR), where 175 YR was
equivalentto 1 USS.
As in a previouspublication(2), it hadbeendecidedby usthat if a kohl sample'sname,
origin, and (informationon its) container/enclosed
leaflet(if present)wereall foundto
be identical to that of another sample--either from this study or from one of our
previousstudies--then it would usuallybe assumedthat the two sampleshad identical
CHEMICAL
COMPOSITION
OF "KOHLS"
401
chemicalcompositions.
However,for a varietyof reasons
(to checkon the consistency
of
composition
with locationof purchase,
ascloseinspection
of the information
on some
containers/enclosedleaflets revealed small variations from that seen before, and to ac-
commodate
both samplesarrivingovera periodof time and the moreimmediateneeds
of a student's
project),it wasdecidedto analyze
all (i.e., 38) of theobtainedsamples
by
scanningelectronmicroscopy
(SEM). The samplesobtainedin Doha with the same
name,origin,and informationon their containers/leaflets
gaveidenticalSEM results.
Thusonly the resultsfor the 19 observably
differentkohl samplesfrom Dohaaregiven
(Table I) and discussedlater.
Two of the Yemenisamples
("Hashmi
© Kajal"--seeTableII), purchased
in oneof the
souksof Saana,
appeared
to bealmostidenticalto eachother.However,thesellerinsisted
that one (the moreexpensive,
and the one with an "emblemof authenticity"on its
packaging)wasthe "realversion"and that the other(lessexpensive,
and withoutthe
"emblemof authenticity"
on itspackaging)
wasa "fakeversion."
Thusthesetwo samples
were regardedas being observablydifferentfrom eachother, as were the six other
purchased
samples
with no labels.All ten Yemenisamples
wereanalyzed
by the SEM
technique(Table II).
The secondanalyticaltechnique,X-ray powderdiffraction(XRPD), wasappliedto a
totalof 26 kohl samples,
that is, to 16 of the 19 observably
differentsamples
fromDoha
andall ten of theYemenisamples.
While someof the (overall)29 samples
hadbeenseen
in previous
studies,
it wasfelt (forthereasons
givenpreviously)
thatmost(i.e.,all except
three)shouldbe redoneby this techniquefor this study.Any previousdata (SEM and
XRPD, as well as availabilityof data on contents/medical
effects)are given with our
results in Tables I and II and are also mentioned
SCANNING
ELECTRON
MICROSCOPY
in the later Discussion section.
(SEM)
The initial SEM work, on someof the Dohasamples
andon all of the Yemenisamples,
wasdoneon an Hitachi S3200N variablevacuumscanningelectronmicroscopewith an
attachedEDS (energydispersive
spectrometer).
Later,moredetailed,work, on all the
samples,
wasstartedon a JEOLJSM 5300 LV (low-vacuum)
SEM with an attached
RontecEDX (energydispersive
X-ray) microanalyzer.
However,technicalbreakdown
of
this machine meant that the SEM work was finished on an FEI XL 30 ESEM FEG
machinewith a RontecEDX analyzerattached.For all the SEM work, eachsamplewas
mountedon an (aluminum)stubusingan adhesive
carbontab/disc.Also,eachmachine
was designedso that either a graduatedvacuumwas employedor that the specimen
chamberwasdifferentiallyevacuatedto low vacuum.Thus any electricchargeon the
specimen
wasneutralized,
therebyallowingspecimens
to be studiedwithoutcoating.
Elementslighter than carbon(i.e., Z •< 5) cannotbe detectedusingany of these
machines.Elementaldetectionwas qualitative,and the elementpeaksthat were only
just abovethe background
aregivenin bracketsin TablesI andII.
X-RAY
POWDER
DIFFRACTION
(XRPD)
For XRPD, the kohl samples
were,wherenecessary,
groundto a uniformpowderand
then mountedin an aluminumholderon a glassslide.Diffractiondata were collected
402
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CHEMICAL
COMPOSITION
OF "KOHLS"
403
404
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•
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CHEMICAL COMPOSITION
OF "KOHLS"
405
406
using a SiemensD5000 X-ray diffractometeroperatingwith CuKot radiation.A step
scan,usinga stepsizeof 0.02 degreeanda time of Is/step,wasdoneovera 2-thetarange
of 2-70 degreesfor eachof the samples.Thesedata setswerethen usedto determinethe
majorandminor components
(phases)
presentin the samplesby comparingthe obtained
data to the referencedata in the 2004 JCPDS (Joint Committeefor PowderDiffraction
Standards)database.The major phasewas usuallydefinedto be that phasethat had a
presence
estimatedto be •> 70%; anyvariationfrom thispercentage
is mentionedin the
Resultssectionbelow. The minor phasesgiven in parentheses
(in Tables I and II) are
thoseestimatedto be •< 5% of the sample.Also, eachgroupof minor phaseslistedare
in decreasingorder of their estimatedpercentagepresence.
RESULTS
In TablesI (Qatar) and II (Yemen) the variousresults/dataare given, with the samples
being listed in alphabeticalorderof their names(or translatednames).Where samples
had no name, they are listed as "None" (all samplesin Table II are given a letter ("Y")
and a numberso they can be referredto in the text unambiguously)
and, aspreviously
stated,areregardedasall beingobservably
differentfromoneanother.Also,for the few
occasionswhere the same sample name occurredmore than once, extra descriptive
informationisgivenin parentheses
afterthe listednames.Alsogivenin bothTables,ona
simpleY/N basis,is whetheranywritten informationis given(on the container,pack-
aging, or an enclosedleafiet)--here and/or in one of our previousstudies--on the
(chemical)contentsof the sampleor on the medicinaleffectsof usingthe kohl sample.
For the 19 observably
differentsamplespurchasedin Doha (TableI), it wasfoundthat
sixhadgalena(PbS,leadsulfide)presentasthe majorcomponent
(phase).Threeof these
six (powder) sampleswere matte in texture and three "shiny," and were grey (1),
grey-black(3), or black(2) in color.Threeweremadein Pakistanandoneeachin France,
India, and SaudiArabia. Four of thesesampleshad minor phases(betweenapprox.2%
and 8%) of cerussite(PbCO3) and anglesite(PbSO4),wheretheseare regardedas
oxidation/weatheringproductsof the original galena ore. A further five (powder)
samples
hadsassolite
(H3BO•)asthemajorphase,andall weremadein Pakistan.
Their
colorsvariedfrom light grey to black, the grey-black/blackcolorsbeing causedby the
presenceof varyingamountsof (the minor phases)graphiteor amorphouscarbon.One
sample("ShamsiSurma,"madein the Punjab of Pakistan)had minor phasesof halite
(NaC1, at about 35%), quartz (SiO2, at about 10%), and, at lessthan about 5% each:
calcite(CaCO•),anhydrite(CaSO4)
, andsylvite(KC1).Anotherfour(threebeinggreasy
and onea powder)sampleshad zincire(ZnO) asthe majorphase,and againthe black/
grey-blackcolorderivedfrom the presence
of (the minor phases)
amorphous
carbonor
graphite.Three were made in Pakistanand one in India. The latter samplealsohad
camphor(C•oHt60) presentat about21%. Three(two beinggreasyand onea powder)
moresampleshadamorphous
carbonasthe majorphase,andall wereblackin color.Two
were made in India and one in Pakistan.The powdersample(from India) had talc
(Mg•Si4Olo(OH)2)presentasa minor phase,thoughits approximate
percentage
presenceis uncertain.The final (powder)samplehad talc asits majorphase,with its black
color again being causedby the presenceof (a minor phaseof) amorphouscarbon/
graphite.It hadadditionalminorphases
of calcite(at about41%), andat lessthanabout
5% eachwerequartzand an unknownphase.Its countryof origin wasPakistan.
CHEMICAL
COMPOSITION
OF "KOHLS"
407
For the ten samplesobtainedin Yemen (Table II) it wasfoundthat five had galenaas
the main component,with a further threehavingit presentasa minor component.One
of thesefive samples
wasa "shiny"silver-greylump, onea matteblackpowder,andthree
were"shiny"grey-blackpowders.One sample(100% galena)camefrom the mountains
of either (N.) Yemen or from thoseof nearbySaudiArabia, anothercamefrom Saudi
Arabia(Mecca),two were of uncertainorigin (possiblyYemen),and onewasstatedto
comefrom the mountainsnorth of Saana(i.e., in Yemen). Four of the five sampleshave,
asabove,minorphases(varyingbetweenapprox.2% and 18%) of cerussite
andanglesite,
and again theseare thought to be oxidation/weathering
productsof the original galena
ore.A furtherthreesampleshadzinciteasthe majorphase,all beingblackin color.Two
weregreasy(madein Pakistan)and onea powder(madein India). The latter samplehad
amorphouscarbonpresentasa minor phase,while the two from Pakistanhad galenaas
minor phases(at about 3% in eachsample).The two remaining sampleshad quartz
(SiO2, at about95%) and iron oxides(hematite,Fe203;and goethite,FeO(OH), at a
total of about 82%) as their major phases.The latter samplewas red in colorand had
minor phases(at about7% or lesseach)of quartz,galena,calcite,and talc/analuminosilicate;the former was grey in color and had minor phases(at lessthan 5% each)of
calciteand an unknown phase.A few other minor phases(all at lessthan 5%) were
found:wax in the (2) greasysamplesandsphalerite(ZnS),probablyasan impurity in the
original galena,in anothersample.
As alreadystated,the majorphaseslistedin TablesI and II usuallyhada presence
in the
sampleof •>70%. However, for two of the samplesin Table I ("Nirma Surmi" and
"ShamsiSurma")the majorphaselistedwasin factlessthan 70%, being 51% (talc)and
45% (sassolite),
respectively
(whereboth percentages
are estimates).
The meaning/importance
of the texture(i.e., "shiny"or "matte")of a galena-based
(i.e.,
as the majorphase)sampleis mentionedin the Discussionsectionbelow.Also, where
samples
weregreasy(overall,sevensuchsamples),
thiswascausedby the presence
of wax.
This wax wasassumedto be, with onepossibleexception(the sample"Khojati Mumtaz
Cold Kajal"; seebelowfor details),paraffinwax.
DISCUSSION
TOXICOLOGY
OF LEAD
Leadcompounds
aretoxicby ingestion,inhalation,andskinexposure.
Childrenaremore
susceptible
than adultsto leadintoxication.Adults absorb5-15 % of ingestedleadwhile
children can absorb as much as 41%. The toxic effects of lead form a continuum from
clinical or overt effectsto more subtle ones(9). The critical effectsin infants and children
involvethe nervoussystem.Bloodlead levelsoncethought to be safehavebeenshown
to be associated
with intelligencequotientdeficits,behavioraldisorders,
slowedgrowth,
and impaired hearing(10,11). Blood lead level (BLL) valuesin childrenthat are greater
than 10 pg/dl are now considered
abnormal(12), and recentlyit hasbeenshownthat
significantintellectualimpairmentoccursin youngchildrenwho havebloodlead levels
bdow10 pg/dl (13,14). However,while it wasinitially thoughtthat suchimpairments
werepersistentandirreversible,it is now suggested
that the latter may not be true (15).
Increasinglyit is beingsuggested
that the above-mentioned
limit in children(10 pg/dl)
408
is no longera safethreshold,especiallyfor children'sneurodevelopment,
and it hasvery
recentlybeensuggested
that this thresholdbe reducedto 2 pg/dl (16).
Severeleadpoisoning,resultingin encephalopathy,
canresultwhenbloodleadlevelsare
greaterthan 70 pg/dl. A recentreporthasdemonstratedthat younginfantsexposedto
lower levelsof lead following the use of traditional medicinescan alsopresentwith
encephalopathy
(17). Reportedcasesof acuteencephalopathy
in infantsthat area/irect/y
/i,/•ed to excessive
use of a lead-basedkohl are now fewer than were reportedseveral
decades
ago, but unfortunatelydo still occur(18). Deliberatepoisoningvia lead-based
kohl is extremelyrare, and very recentlya caseof such a homicidal poisoningwas
reportedin Egypt (5). It shouldalsobe statedthat lead poisoning,from traditional
remediesand cosmetics,doesstill occasionally
occurin present-dayEurope(19).
Frequently,mothersapply kohl to infants and children as a traditional measureto
beautifyand to protect the child from the "evil eye"/"theevil one." Lead-containing
kohls can be easilyingestedby theseinfants,who may wipe their eyesand faceand
subsequently
lick their fingers.Earlier (animal) studies(20) haveshownthat transcorneal transportis not a significantcontributorymechanismfor absorptionof leadfrom
lead-based
eye cosmetics.
Recentdermalstudies(21,22) haveindicatedthat inorganic
lead compoundsca, be absorbedthrough skin. However, the BLL values,from such
studies,do not showany significantincrease.Thus more work is requiredon dermal
absorptionof lead, especiallywith respectto the small particle-sized(seebelow) lead
sulfide found in some kohls.
More than 90% of lead in bloodresidesin the red bloodcells.The total bodyburden
of leadcanbe dividedinto two kineticpools,whichhavedifferentratesof turnover.The
largestpool is in the skeleton,which hasa very slowturnover(a half life of morethan
20 years)(12). The otherpool is in the softtissue,whereleadis muchmorelabile.Lead
in trabecular bone is more labile than in cortical bone, and trabecular bone has a
shorterturnovertime. Leadin bonemay contributeup to 50% of blood lead. During
pregnancyandlactation,mobilizationof leadfrom maternalboneis a causefor concern.
Strongcorrelationsbetweenmaternaland umbilical cord bloodlead levelsdemonstrate
that lead is transferredfrom the mother to the fetus (23). Cumulative effectsof low levels
of leadexposure
•, •teroandafterbirth canhavesimilardetrimentaleffects.An increase
in maternal-bloodlead level may contributeto a reductionin the gestationperiodand
low birthweight.The fetal brain may alsobe particularlysensitiveto the toxic effectsof
lead because
of the immaturity of the blood-brainbarrier.
In an adult populationthe mostcriticaladverse
effectof leadis probablyhypertension.
Other toxic effectsof concernareperipheralneuropathy,lead-inducedanemia,and lead
nephropathy.
Also,asmentionedin theIntroduction,therehasrecentlybeena suggested
link madebetweenthe frequencyof lead-based
kohl useand the accentuation
of periorbitalpigmentationand the development
of associated
anemia(4).
BLL valueshave been investigatedfor children of both Yemeni and Qatari families.
However, the Yemeni familiesstudiedlived as immigrantsin the Detroit (Michigan,
USA) metropolitanarea,andtherewasnodetailedstudyof anyunderlyingriskfactors.suchaslead-based
kohl usage.The study(24) focusedprimarily on genderandhealth
issuesduring the outreachprogram.Of the total of 112 blood samplestestedit was
foundthat only seven(i.e., 6.2%) hadBLLsgreaterthan 10 pg/dl (andwith no samples
greaterthan 16 pg/dl). Furtherprojectsare underway and may well includethe study
CHEMICAL
COMPOSITION
OF "KOHLS"
409
of suchrisk factorsas the useof traditionalmedicinesand cosmetics.
In Qatar a study
(25) of the BLLsin 200 samples
collectedfromchildrenunder15 yearsof agefoundthat
only threeof the samplesshowedvaluesexceeding25 pg/dl (the then maximumvalue
for normalbloodlead in Qatar). The highestBLL value foundwas 38 pg/dl, and by
comparingthe resultsto thosedonepreviouslyin Qatar it wassuggestedthat there had
beena significantreductionin suchvalues.As in the Yemeni study,no work wasdone
in this Qatari study to determineif lead-basedkohl usagewas a risk factor. A wider
nationalsurveywasrecommended,
and it wasproposedto introducea new (BLL) action
level of 10 pg/dl for childrenand pregnantwomen.
In a previouspublication(7) we discussed
the particlesizeof galena(leadsulfide,PbS)
with respectto the associated
kohl powderbeing"shiny"or "matte"in textureandwith
respect
to its rateof dissolution
in gastricfluid. It wasfoundby usthat at a meanparticle
sizefor galenaof about •<10 pm, the kohl powder(with galenaas the major phase)
becametotally matte in texture.It had previouslybeenfound (20) that reducingthe
particlesizeof galenaleadsto a significantincreasein its rate of dissolution(in gastric
fluid). So,in a verysimplistictoxicologysense,it canbe said:"shinyis goodandmatte
is bad" (as the latter would be much more easilydissolvedin gastricfluid than the
former, with the former perhapsgoing straight through the body with minimum
absorption
andnegligibletoxicity).Thusin TablesI andII we havestatedif the powder
is "shiny"or "matte"in texturewhen galenais the listed majorphase.Only four such
samplesin this studyaredescribed
as"matte,"and sothesefour samplesaremorelikely
than the othergalena-based
samplesto give riseto lead toxicity.
In viewof all of the abovementionedtoxiceffectsandthe still widespread
useof kohlsin
parts of present-dayNorth Africa/Middle East, it follows that children who have a
lead-based
kohl regularlyappliedto them areat risk of seriousandfatal toxicidesof the
nervoussystemand alsoof more subtle,sub-clinical,long-term effects--suchas the
underdevelopment
of neuralpathways.
EXTRA
INFORMATION
ON
CONTAINER/PACKAGING/FROM
VENDOR
Qatar.Nine of the 19 kohl sampleslistedin Table I havewritten qualitativeor quantitative "contentsdata"available(on the container/packaging
or on an enclosedleaflet).
Table III liststhis data,with our besttranslations/interpretations
and their (mostlikely)
chemical/mineralnames.When there is uncertainty,a "?" has been added. Only one
sample("HashmiKohl Aswad,"madein Pakistan)had a majorphase(galena)that was
not listed in its (qualitative)"contentsdata." Another sample("Hashmi Kajal," blue
stick/pencil)had zinc oxide(first) listed, but no suchphasewasfound by us. For the
other sevensampleswith "contentsdata," the major phasefound by us matchedone
listed--usuallyof high givenpercentage
or at the top of the list whenonly qualitative
data were given.
As regardsdata on the medicinaleffectsof usinga particularkohl sample,it wasfound
that ten of the 19 sampleslistedin Table I had this (written) informationavailable.The
four "LateefSurma"sampleshad essentiallythe sameinformationon all the leafletsthat
camewith the four samples--sometimes
in English(the green/redandgrey/blackboxes)
and sometimesonly in other languages(the yellow and red or yellow and blue boxes).
On any one of theseleafletswere variousstatements,suchas: "Excellentfor blephritis
and red eyes,""Immediaterelief from irritating and watery eyes,"and "Giatericvision
410
•g-•go
o
=
T
CHEMICAL
COMPOSITION
OF "KOHLS"
411
412
is improvedand patientscan seecrystalclear,continuoususe will removeyour spectacles."The mainingredientfor all of thesekohl samples
wassassolite
(i.e., boric/boracic
acid, H3BO3, with minor phasesof a zinc borateand carbon(as either graphiteor
amorphous
carbon).Sassolite
is a weakantisepticanda feeblebacteriostatic
andfungistatic,and hasbeenusedin the past, in weakaqueoussolutions,as eye drops/lotion.
However, toxic effectscan sometimesoccurfrom absorptionif it is usedinternallyor
externallyon brokenareasof skin((26) andreferences
therein).Thus,we wouldquestion
at leastsomeof the medicinalefficacyclaimsmadefor thesefour samples.
Two samplesbasedon amorphouscarbonalsohad informationprovidedon their medicinaleffects.The sample"KhojatiMumtaz ColdKajal"merelystates,"It cools,soothes
and protectseyesfrom dust and harmfuleffectsof bright light." The othersample,
"Hind Ka Noor Eye Liner," stateson an enclosedleaflet (in Arabic), "Protectsyou
permanentlyfrom diseases
of the eye"and "Veryadvantageous
againstthe weakness
of
the eye,or waterin the eye,or dirt, or eyepain,or inflammation."While placinga black
material,suchasthesekohls,aroundthe eyesshouldgive them someprotectionfrom
dust, flies, and the glare of a bright sun, it is unlikely that the materialwould be of
assistance
againstdiseaseof the eyes.Also, the Khojati sampleis the only one(of five
suchsamplesoverallthat list "waxes"in their "contentsdata"--seeTable III) to specificallystatethat the waxis "honeyof wax,"i.e., beeswax.
Only paraffinwaxdiffraction
data is currentlyin the (XRPD)JCPDS database.However,we did manageto obtain
(from a bee-keepingcolleague)some fresh yellow beeswaxand thus its diffraction
pattern.Unfortunatelythis patternwasfoundto be verysimilarto that of paraffinwax,
andsoit provedimpossible
to determineif indeedbeeswax
waspresentin this sample.
The two samples"KhojatiSurmaNo. 13 Black"and "HashmiKajal" (in a B&W tube)
both havelimited and generalmedicinaleffectsinformationgiven on a leaflet or on
packaging.Both havemain phasesof zincire(ZnO), with minor phasesof camphorand
carbonfor the first sampleand of wax and carbonfor the secondsample."Keepseyes
cool,cleanand healthy.Its an ideal tonic for the summerseasons.
For externalusein the
eyesonly"is statedfor the Khojati sampleon an enclosed
leaflet.For the Hashmisample
we havethe generalcomments:"Besideskeepingthe eyescool and refreshing,it also
protectsthem"and"... , presented
in the formof blackpastein tubescanbesafelyused
for all ages."Zinc oxide is a mild antisepticand camphora mild counterirritant;thus
both samples,if usedexternallyand in moderation,would not be expectedto give rise
to toxic effects.
Unfortunatelythis cannotbe saidfor the last two samplesfrom Doha ("Khojati Surma
Sada"and "HashmiKohl Aswad")that havemedicinaleffectsdataprovided.Both have
leadsulfidepresentasthe main phase,and both haveit presentasa matte powder(i.e.,
havingsmallparticlesizeand soan increasedlikelihoodof toxicity when absorbed--see
previoussection).The Khojati samplesays,in English,on onesideof an enclosedleaflet,
"Surmais not to be appliedto childrenbelow 12 yearsof age."However,on its other
sideit states,"This is the purestform of surmascientificallygroundin differentnatural
extracts.As thereis no additionof anyotheringredientsit doesnot makethe eyeswater
and can be used for children below 8 years" (our addition of bold). While it also
states(on the box):"Unani medicine.For externalusein the eyesonly,"therecanbe no
justificationfor the abovestatementfor using sucha powderon youngchildren.The
Hashmi samplehasthe followingstatementson its packaging(in Arabic):"Usefulfor
preserving
sight,""Makesall diseases
of the eyemiserable,"
and"Bothyoungandoldcan
CHEMICAL
COMPOSITION
OF "KOHLS"
413
useit equally."It alsoprohibitsits useif thereis itching or inflammationpresent.This
last statementis to be welcomed,but, asfor the aboveKhojati sample,there can be no
justificationfor the useof sucha powder (pure small-particle-sizedgalena)on
Yeme,.Only three of the ten Yemeni kohl sampleshave (qualitative) "contentsdata"
available,andthesearelistedin Table III. For the two "HashmiKajal" samples,the top
two phaseslisted (zinc oxide and waxes)are found as the major and a minor phases,
respectively.
The third phaselisted (amorphous
carbon)coMdbe present,but at a level
of only a few percent,and henceessentiallyunobservable
by XRPD. Unexpectedly,
galenaasa minor phaseat approximately3%, is foundin both thesesamples.Neither
samplehasit listed on its "contentsdata," and the "realversion"specificallystates(on
its packaging),"Lead (P.B.) at 0.00%." The third samplewith "contentsdata" is
"Hashmi Kohl Aswad"--made in India, not Pakistan,as found for the sampleof the
samenamepurchasedin Doha (seeaboveand Table I). Its listed phasesare zinc oxide
and camphor;the first was found as its major phase,but only amorphouscarbonwas
found as a minor phase.
There is only one kohl samplefrom Yemen that has any medicinaleffectsdata on its
container/packaging/leaflet.
This sampleis the "HashmiKohl Aswad"mentionedabove.
On its cardboardpackagingare statementssuch as (in Arabic): "It is made of raw
materialsof the highestquality. It is good for the health of the eye and can be usedby
adultsand children.Do not usein casesof itching, inflammationor a burning sensation." Some of these statements
are similar
to those found on the other "Hashmi
Kohl
Aswad"(i.e., made in Pakistanand having an "emblemof authenticity"on its packaging); given the actual contentsof this Indian-madesample(zinc oxide and amorphous
carbon)comparedto thoseof the Pakistan-madesample(pure galenaof small-particle
size),useof the former is vastlypreferredto that of the latter.
Vendor and other personal(i.e., verbal)commentswere alsomade,on both contentsand
medicinaleffects,for someof the 29 samplesstudiedhere.For the samplespurchased
in
Doha this informationis given in the last columnof Table I. Eight of the 19 listed
sampleswere said to be "cold"--that is, to be usedsolelyas cosmetics.Two were said
to be "hot"--that is, to be usedas either a cosmeticor as an eye medicine.Five of the
sampleslisted as "saidto be cold"are contradictedby the presenceof medicinaleffects
informationprovidedwith the sample.The two "saidto be hot" samples,which also
havemedicinaleffectsinformationprovidedin writing, havemajor phasesof zincite or
sassolite--bothmild antiseptics.Someof the other informationgiven in this column
matchesthat foundon the sample'spackagingor on an enclosedleaflet--for example,
unfortunately,"for children"for the "Khojati Surma Sada"sample.The phrase"mixed
with Saudistone"occurredfor four samplesand the only commonphaseis sassolite--for
which we can find no publishedreferencereferring to its natural presencein Saudi
Arabia. However, western/southwesternSaudi Arabia doeshave fumaroles(27), around
which sassolitecan form, and so this mineral could in fact be available asa "Saudi stone."
For the ten samplesfrom Yemen therewerea few additionalpersonal/vendor
comments
on only two samples.The red-coloredkohl (labeledby us as "Y9," and said to be called
"Ethmart"by the vendor)wassaidto havemedicinaluses--specifically
againstinfected
(white of the) eyes.Also, one of the two samplesobtainedin Aden ("Y2") wasbelieved
by the donorto havemedicinalproperties(for the eyes)and wassaidby her to contain
(in addition to what was in "YI") "added medicines, fish scalesand herbs."
414
COMPARISON
WITH
OTHER
STUDIES
Qatarand Yemen.
The kohl samplesfromYemenwerefoundto be morelikely to contain
galena(eight of ten; i.e., 80%) than thosefrom Doha (six of 19; i.e., 32%). The Yemeni
sampleswere also more likely to have no written labeling (sevenof ten; i.e., 70%,
comparedto onein 19; i.e., 5%, in Doha)and to be locallymade(probablysix of ten;
i.e., approx.60%, ascomparedto nonefrom Doha).Most (17 of 19; i.e., 90%) of the
samplesfrom Doha originatedin India or Pakistan,comparedto only 30% (i.e., three
of ten) of thosefrom Yemen. One samplefrom eachcountrydefinitelyoriginatedin
Saudi Arabia.
Only in Yemen weredefinite"fake"samplesfound. However,the two "HashmiKajal"
samples(onedescribedas "fake"andoneas "real")werefoundto be almostidenticalin
their chemicalcomposition.On the other hand, the "Hashmi Kohl Aswad" (made in
India) hada chemicalcomposition
totallydifferentfrom that foundfor the sampleof the
samename (but made in Pakistan,and having an "emblemof authenticity"on its
packagingand soassumedto be the "realversion")purchased
in Doha (and alsopreviously in the Emirates(2)).
In generalterms,Yemen is a lessindustrializedcountrythan Qatar. ThusYemen would
perhapsbe expectedto havefewerimportsandto makemoreuseof local/near-local
(i.e.,
southernSaudiArabian)resources.
Suchresources
would includenaturallyoccurring
galena (28).
Previoz/s
stz/dies.
In Table IV are listed 18 publicationsof previouskohl analyses.
They
covera 27-yearperiod(1979-2006) andseveralanalyticaltechniques
(AA, CRM, SEM,
and XRPD). The percentagerangefor the number of samplesfound to containlead
variesbetween22% and 100%, with an "average"of 60%. There is someevidenceto
suggest,fromanalyses
doneseveraltimesin a countryovera periodof time (i.e., Greater
Cairo in 1997 and Cairo in 2004, and SaudiArabia in 1993, 1995 (twice), and 2004),
that this percentagedoesdecrease
overtime. However, further studiesin other countries
whereanalyses
havealreadytaken placeare necessary
beforethis positiveeffectcan be
confirmed.
In Doha it wasfoundthat six (of 19) samples(i.e., 32%) containedlead sulfide.This
percentageis very similar to thosefound previouslyin Oman (32%), Cairo (33%),
Bahrain(33%), and the Emiratesof RasA1-Khaimah(36%) and of Dubai and Sharjah
(38% each).It is alsoconsiderably
lowerthat the "average"(60%) of Table IV. However,
the percentage
foundfor samples
containingleadsulfidein Yemen(80%) is considerably
higher than this "average,"and is similar to the valuesfound in oneof the studiesdone
in Saudi Arabia (75%), Karachi (Pakistan) (80%), and Kuwait (85%).
As regardsthe importationof kohl samples(from India and Pakistan),the percentage
importedto Qatar (90%) is much higher than that to Yemen (30%). The formervalue
is similarto thosefoundby usin Dubai andSharjah(81% each),Ajman (86%), andAbu
Dhabi city (89%), while the latter valueis similar to the valuesfoundby us for Oman
(40%) andCairo(22%). Locallymadekohl samples
werefoundto be nonexistent
in the
souksof Doha, a resultthat is very similar to what wasfoundin the souksof the UAE
(UnitedArab Emirates)--onesuchsamplewasfoundoverall,in Dubai.However,about
60% of the kohl samplesfoundin Yemenwerelocallymade--a findingthat is similar
to what was found in Cairo (61%).
CHEMICAL COMPOSITION
OF "KOHLS"
415
416
Over time therehavebeendifferencesin the chemicalcompositions
found for a few of
the kohl samplesstudiedhere.Thus, in TablesI and II are listedthe variousmajorand
minor phasesfound both here and in someof our prior publicationsfor thesesamples.
The "HashmiKajal" samples(in a B&W tubefor both tables,and asa blue stick/pencil
for Table I) are the only onesto havehad variations--betweenamorphouscarbonand
zincire--in their majorphases.For mostof thesevariouslyanalyzedsamples,the minor
phaseshavenot changedsignificantly.One exceptionis in finding galenain both the
"HashmiKajal" samples
listedin TableII. We currentlybelievethat thisgalenaminor
phaseoccursasan occasional
impurity with zinciteorefrom a particularlocation(galena
oftenoccursasan impurity with the zincoresphalerite(ZnS),but onlyoccasionally
with
the ore zincire).
Also,overtime therehavebeenchangesin the informationprovided,on both "contents
data" and "medicaleffects,"for somekohl samples.In the last two columnsof TablesI
and II arelistedthe varying"Y/N" symbolsfor samplesstudiedhereand in oneor more
of our prior publications.For "contentsdata"therehavebeenchangesfor eight samples
in Table I andfor onesamplein Table II. Most (i.e., six in Table I andonein Table II)
of thesechangesare "positive"--that is, a changefrom providing no informationon
contents to providing at least some qualitative data. Regarding "Data on medical
effects,"sixsamples
(in Table I) havechangedfromgiving no suchinformationto giving
at least somesuchdata. However, it should be stated that someof the information now
given--for both contentsand/ormedicinalusage--isnot alwaysof the highestquality
(see above).
The non-leadelementsor compoundsfoundin our presentstudyare broadlysimilarto
thosefoundin the previousstudiesin TableIV. However,severalauthors(32,36,38,41)
did find antimony(usuallyin small/verysmallamounts)in someof their kohl samples,
whereasin all our previousstudies,aswell as here,we found no antimonywhatsoever.
CONCLUSIONS
In the 29 kohlsamples
analyzed
overallin thisstudy,14 (48%) samples
hadgalena(PbS)
presentto somedegree.By countrystudied,this numberandpercentagechangeto: for
Doha (Qatar), six (32%) out of 19; and eight (80%) of ten for Yemen. The other main
phasesfoundin our sampleswere amorphouscarbon(three),iron oxides(one),quartz
(one), sassolite(five), talc (one) and zincire (seven).
In Yemen a large numberof the samplesfor salehad no labelingwhatsoever(and thus
no written informationon contentsor possiblemedicinalusage)and wereoftenlocally
made,whereasfor Qatar all the samplesfoundin the souksof Doha had beenimported
(mostlyfrom India and Pakistan)and only onehad no written labeling.
This studythusshowsthat traditionaleyecosmetics
("kohls")arereadilyavailablein the
souksof Doha (Qatar)andYemen. If a kohl samplewasboughtin a soukin Doha,there
would be an approximatelyone-in-threeprobabilitythat it would containa leadcompound. For the souksof Saana,there would be a higher probabilityof a kohl sample
bought there containinga lead compound(five of the sevensamples,bought in two
souks,containedgalena,thoughin threesamples0n/•yasa minor phase),and on the few
(three) sampleswhere labeling Jxpresent,there would be n0 informationon lead's
presence.
CHEMICAL
COMPOSITION
OF "KOHLS"
417
Moreover,overall,someof the kohlsnot only containlead,but containit in a form (i.e.,
small-particlesize)that makesit moreeasilyabsorbedinto the humangut. We canonly
reiterate,again, that this elementhas no known biologicalvalue and is an insidious
cumulativepoisonhavingpotentiallydevastating
cognitiveeffectsif appliedregularlyto
young children.
ACKNOWLEDGMENTS
We thank the following people for their help in the courseof this study: Mr. Paul
Auchterlonie(Librarianfor Middle EastStudies,ExeterUniversity,UK) and Dr. Sajjad
Rizvi (Institute for Arab and IslamicStudies,ExeterUniversity,UK) for translationsof
Arabic and Urdu, respectively;
and Prof. TerranceB. Murphy (Weil Cornell Medical
College,Doha, Qatar) for help with samplecollection.Also, we thank the staffof the
Chemicaland MaterialsAnalysisUnit (University of Newcastle,UK) for someof the
experimentalSEM work mentionedin this article.
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