-f M. Cetin GOLOVALI

TR(J -f

TRACE ELEMENTS IN TURKISH TOBACCO

DETERMINED BY INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS

A MASTER THESIS

SUBMITTED TO THE DEPARTMENT OF CHEMICAL ENGINEERING

AND THE COMMITTEE ON THE FACULTY OF ENGINEERING

OF MIDDLE EAST TECHNICAL UNIVERSITY

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS

FOR THE DEGREE OF

MASTER OF SCIENCE

By

M. Cetin G O L O V A L I

April 1977

TBAC3 ELEMENTS IS TURKISH TOBACCO

DETERMINED BY INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS

A MASTER THESIS

SUBMITTED TO THE.DEPARTMENT OF CHEMICAL ENGINEERING

AND THB COMMITTEE ON THE FACULTY OP ENGINEERING

OF MIDDLE EAST TECHNICAL UNIVERSITY

IN PARTIAL FULFILLMENT OF THB RBC&0IFEMSN2S

FOR THE DECREE OF

MASTER OF SCIENCE

By

M, Qstin Ctilovali

April 1977

"' I

I certify that I hava ;:o"-d this thesis and that in my

opinion it is fully adoqup-te, in scope and quality, as

a theBis for the degreo of Master of Science,

Supervisor

I certify that this thes:.3 3.i*isfiPs pl l -Mis recj.\zirGments

as a thesis for the dogroe of Master of 3oi.-mf j»

Chairman of the Department

Examining Comittee in Chs-rge:

Comittee Chairman

ABSTRACT

TRACE ELEMENTS IN TURKISH TOBACCO

DETERMINED BY IITST7?V:777AL ITPJTrOTT ACTIVATION ANALYSIS

.GiJLOVALI, MP Cat i n

. -.•••M,,S-, i n Chemical E n g i n e e r i n g

, S^^p9^viaor< 'Dr, Gungb'r Gundiiz

19T7, (57) pages

This s tudy "ms •arJw.'. ' i-vcn •',-•<:• '.c fcermino Mir; c o n c e n t r a t i o n

of t r a c e e lements i n n:..m '; L/fo/or-j r*;>.rid3 of j?v.:-k';.t;h oiga.rfitte

t o b a c c o , p ipe tobacco and fc;hr-vj:.c •>^}.,

Instrumental noutron p.ctivr.t.lor. analysis T>.S employed,

and a g°mmp.-ray spectrometer consisting of 40 cm Gc(Li) dotoctor

coupled to 1024 and 4096-ohp.ras.nl an°lyzfrs warn used. Samples were

13 -2 -1irradiated at ft thermal neutron flux of about 10 cm sec .

Concentrations of ]7a, K, Sc, Cr, Fe, Co, Zn, As, Se, Br,

Rt>, Sb, Cs, Ba, La., Ce, Eu, Ef, Hg and Th WVTI dot^rminsd in tobacco

and ash; percent transforonco of these olomonts into ash wera

calculated.

It was found • out that tr«co ^loments in cigarette

tobacco «r? loft in the ash but only a small percentage is

transforr«d into tho smoko.

Kny Wordst Tobacco, Trace Elements, Activation Analysis.

iii

ALETLi aOTROii WxJ.M YOFTSMIYLS

TURK TtMNLPlRINDE ESER ELfiiOTTLERIN TAYI

GOLOVALI,

Yiiksck Ll3-nn, Kiroy* Mtihondiallgi

• Yor r t i c i ; Dr. Gungor Gtindiiz

1977, (57) sP,yfa

Bu gali§mada dokuz dsj;i§ik Tiirk si.'-rrrv i:it:i:!ii, pipo tu-buni

ve tiitiin kuHi-^s osei- «lDi.i'iitl<5rin ic r ig in i l t r i . +• ,:L..i s^-Maiigtir.

A le t l i r citron uy"ri ycrJ---.;:" ve 40 en' S(=(Li) d»dektoru,

1024 ve 4O96-k?-n?>l?Li f;:-1*.-". 7or-Is-- ",&n JIU?/.'.:! .-?•:--I^-IIII spektromotrerai

"" * -2 •-]§ t i r . Hiimunftl ^ 10'^ cm sn " 11> t»rr-n.l natron akismda

Tutun ve kulde II?, K, So, Crs PB, CO, Zn, As, Se, 3r , RTD, Sb,

Cs, 3n., La, Co, Eu, Hf, Hg v^ Th drri§iE.l ^ri '-syi:! e d i l i p , bu e l e -

mentitr i i i Llilo Jrev"i§ yu-."el-i'i

Sonug olf-rpk, sigara ttiturnindeki eaer eloranntlRrin biiyiik

b i r Vasmimn kiilde kf ld i^ i ancsk kugiik b i r miktnranin dumana geg-

t i g i g8zlenmi§tir .

Anahtei" Sozouklers Tiitiin, Kser BT.e:..?ntler, Notron Uvara Y6nt°iai

i v

The author wishes to <?xpross his deep grotitudi? to

'V. r-"ns'-':"- Gund^z for his guidance, supervision and advico e

throughout thn course of this r^

It 'TO".ld to almost impossible to eomploto this work

without th.i hair °f +<h •- followir.-.JS

My îfo find pfrn;its 'vho in so inn;,1 '?•• •» = ?yp7.ort";d «md

so much possiblo^

Dr» ilha.ii Oxmc- .. for his support, guidance and

constructivo critif-isii-.

Stftff of Ank-.vp. Huolop-r Bosep.TCh ".id Training Center

Nuclonr Chemistry Group-

Reactor n-nd Isotope Production groups of Qnl^mecQ Nuclear

EosRarch *nd Training Contor for carrying out ^xtonsive irradiations

Msmhers of th'j Nucl.n .r Division of EosG.'-'i'ch and

Development Ifhoratcri .s of Army (AEGE) pf>rmiting mo tc uss their

facilities,

TABLE OF CONTENTS

Pago

ABSTRACT »...a.......a..............«•••>.. iii

ACKNOWLEDGEMENTS ••••• v

LIST OF TABLES , riii

LIST OF FIGURES ......... ix

CHAPTER

I, INTRODUCTION . 1

II, LITERATURE^SURVEY .....•• 3

2*1 Tobace* ,, 3

2«2 Tra.ee Elements .................... 6

III.ACTIVATION ANALYSIS $

3,1 General Theory of Activation Analysis 9

3*2 G*.iniBa»Ray Spaetrometry 1'6

IV. EXPERIMENTAL PROCEDURE ... ., , 2J

4.1 Sample and Standard Preparation ..» 23

4.2 Irradiation «**•••»t.i»»tk»..»».... 24

4*3 Counting technique 24

4,4 Percent Transference Calculation .. 27

V. RESULTS 28

VI i DISCUSSION AND CONCLUSION 57

A. DISCUSSION 37

6»1 Concentration of Elements in Tobacco 37

6,2 Percent Transference of Elements into

Tobacco Ash ...» 40

B. CONCLUSION 41

Page

REFERENCES .„*,...„........,..,„..., 42

'.FPKNDIX A: Biological Effects and Major Sources

of Several Toxic Trace El^m^nts in the

t • t i » 9 > l . * « « » i > » « » » « i i « AC

APPENDIX E? D-, b'-,ctio>,-t limits for Activation

i!::-•'ysis ,«..,e n»,,r .^.».•» 50

APPENDIX 0s Elemental Concentrations in the

Nn.tionP-1 'Barr.p.v. of Standards'

Envircam'-.nt.'j.l Coal Standard

APPENDIX Dt Concontrntion of TrftC5 Sleuon'js in

C i g . - I ' S J 1 !-. J1.-.V .".COS u « r e « J « i o o . 57

vii

LIST OF T/iBLSS

Table Page

l 0 I r r a d i a t i o n and Counting Timos for the El^ra^nts

Obsdrvcd in Tobacr," . » , . <,, .„, , ? . , . » « . 25

2, Production p;id Prop.-.rt:!..<>£ of Radionuclei Observed 2 ^

3» Cononntrfi-tions of b^7ors».l S.Lemonts Observed in

Different Brands of Turkish Cig^ratte T'obA cose -> 2c1

4* Concentrations cf Sevural Elemonts Obser .-ad :".n

Cigars t t s Tobacco /sh t . , . . n . . » » c « »«,<..-<,« 31

5. P^rcsnt Trr.i?sfe7-!-cs cf Slomonts into TOIDP.CCO I sh 3^

Appendix

B - l , Compr.rison of Dnbaction Lin i t s By Nauti-OM

Activation Analysis »nd Spectroch^r-ical Mothods 54

0 . ?]..-. jj'-^tp.l Concentrp-tions in tho Fat.:: ;,]•. 1 lu;-oau

of Standprds1 Environmental Coal -•.i<-\.-iiart

Reference M°-to.ri."2 .. r•«..-• <.coa»e«».......aoo<..f 56

D- Concoiitrr-'.tion ff TrP-06 Eletmn^s in Cigaret te

T o b a c c o s i M , i < > ' < M ^ t < M > < ' j < i » < , » . . , c ^ c ^ „ 5 7

viii

LIST OP FIC-UEES

"F5.sn.iro Page

1 > Gonovp.l B lock 'i)L*'gwni r-f H Gamma-Ray

C o u n t i n g Sys t em o . r * « . . . * « . IS

2 . P u l s o - " l i g h t A:-^lj-£'i.d Dat i r>s H His ' r =;..-P.S. ?1

3» Granm"--: ~.y £p^'.-lrum of Tobacco Follovin0-

4-hr I r r a -d i ? t i on with Th ?.rn<L w ' t i trons p.nd.

5 Dfys Cooling . , . . , , , 32

4« G-tt-3-jsft"ray SpocJuruia cf Tobacco F o i l c r i ^ 5

4^-hr I r r a d i a t i o n Ti'itn Thsraial IT ;rJj.cci o ^nd

30 Days Cooling Cor»>e..<,><..- .« »«•-<• 23

5. i3i.mm?--ray Spectrum of Tobacco AsL

Following 4-hr I r r ' -diw-ion T i f i T' -j-m-J

Neutrons and.7.Days Cooling c» «. 34

6 . Gamrae--ray Sp^-ctrixm of Tob^.cco Ash Following

4~nr I r r a d i a t i o n ^ i t h Thermal Fotttrons and

30 Days Cooling « „ . . 35

ix

INTRODUCTION

Tobacco is cultivated throughout the wovld for conturie

•- . 1 cigarette smoking hes 110001110 very commori in our culture.,

Objectives of Laboratory studies have bên tc. .31 tormina whether

various tobacco nrid tobacco smok.? products might proves to bra

carcinogen! 1.., Current interest in the production of tobacco and tho

physiological offsets of h'cauii consumption of tobacco, mp»ko it

desirable tr study the trr en olomonta in tobacco products 0

Trace olemonta fulfill important functions in biological

systems. Mod^^-n nj.tr:lt:.on rasearoh^s h-T-ve £fi.ven the m'v~ basic

knowledge about trace elements ossential to animals p-nd man. The

essential ^lrcmenbs ?r« indisnrnsabl'-j for mrmnl function, w«ll bîng

and survival. On tho other handj fh»ir ±c?Aorl''.<-'- -:•?,! effects, play

a major rol*? in disease mechanism if th'.-rn is ti>o little or too

much, and if there aro disturbpnees in thoii- utilization and

m?tplolismo Aside from thoir con::'i:.iption î A ~?-"o6., tr^ce olemonts

arp also inhalod from air, *? t> result of n<- ••yp>*.l And man-mn-de

pollution, and cigarotto smoking is ono of tho important sources.

Eotormin."-tion and Eoasurom^nt of traoG oloments roquiro

sensitive and accurate techniques. The selection of activation

analysis as the appropriate technique based on its sensitivity,

sper.d. ability to analyze samples for n wide spectrum of elements

?vb the same time.. On the other hand, Instrumental Neutron

Activation Analysis rrqnlns no radiochomical sepprationsj and the

samples an"lyzod without any contamination <^r loss. For many f the

problems in bioinorganic cbsmistry, clinical and environmental

research, "-.ctivatir-/. analysis ».ppe*.r to bo the optimal

In recent y>\rs, several studios report mop-suromants nf

tr«oo dloiwnt conoGnti-'ti^ns in cigarottR tobacco (69 FJ.» 70 N2P

73 Al) r In vie^ of ths physiological i^portpr»oo, tho i'.icroasing

number of cigarette smokors, tho variations in tho traoo .3lenient

concentration of soil °.nd pl'-nts in different rogiens : a.T'3 tho

differences in manufacturing proc^sc3es? i t va,s aegir'3.'b"'.e to make

this study <">n ci.?pr~tta tobaccos of Turkry,

In tb-5 j.r"&oni study? cniiiontrntinns "f twonty trace

elements wra detGrmin^d in nine different trar.cLa of Turkish

cigarotto and a branft of pipe tobaccos. AlthciftY- the conenntration

of trace r-lempnts in t«bpcoo gi'.ro on idcA ».J.•••;+, thn plant i tself

and the offset of smoking, i t was necessary •• . nal^se the tobacco

acih, and interpret the results in terms of the percent transference

of these t.r?ce f;lement^ into the tobacco ash.

,, SUHVEY

" ] Tobacco

In the Nocotiana genus there are moro than sixty gnnetic

specios, hvA only two :..r them, Nicotiana. tabacum and Niootiana

rusticftj e.x.i cu''.tivat,--.'j. for use as tobacco,, Th» former is gro^-i in

appreciable ^.mounts throvg.iout tho world in noarly *.?!'-• hundred

countries &nd constitubr>£ the commnrciai tobôco.

Tobacco is cultivf.tod widely througlioufc th^ •orlA,

indicating "ihat ib is ada.ptc3. to a •••ido ringe of ndaphic (soil)

and motsorologic (climatic) conditions,. Th.T odaphic factors includs

the character 01 parent. roo>s from ^hich tho soils aro derived,

soil toxturo, .and contsnt of olemonts of Hiin.ir.1-1 nutrition, organic

mattor, microbes, Tator, and of gases.. The clia-'tic factors include

the amount and distribution of rainfall, pi"-"'.':'ling tomprraturos,

and duration and intenaity of li,:?ht.. Both ••....p.'.Ic .•••id climatic factors

vary in OP ch tobacco-growing locality, tut *:noy ieo vary appreciably

in any givnn locality from ysar to yoar. Bach ono and its components

aro capablo of modifying the, physical and chomical proptortios of

the loaf producodo

Each green leaf on any given plant differs froan the others

in age, size, color, proportion of length to Tidth, thiclknoss, and

amounts ?nd distribution of chemical constituents,. Consequently,

ths cured IS'IVRS, which is not just a di-i d loaf of tobacco,

differ markedly in physical and chemicl features.

The mature grc.;:) hj-'S tobacco a:( •:•:• ,.• oein<< harvested is

subjected to appropriate humidity and tempers :;urs for curingo

There are essentially four kinds of curing procossc-s, namely?

flLI;-curing (heat-curing), air curing (natural curing), fire-

jarir.g, r.nd sun-curing- In fact, each process requires ".ir,

noni? is anaerobic. Virginia tobacco is fluo-cur:.d, "nd Burley,

Maryland • -3 cig .r v-.riati'js are nir-curods Turkish n.nc. other

oriental tobaccos ar*1 cun-orred (67 W l ) .

Two processes, ono of which is dehydration, or w»ter

loss, and tho other f 'SGrir-s of cnGjnica.l a •-.-,--3.J c'.iT^cterize

curing:, it the ind of curing, the 'Tator c onto rib hf-'-s boon reduced

by 80-90 fc of green le -i weights 0 jlor changes, primarily the

destruction of cVlnôpIiyll, .°.cc. j-. ny drying. During the early

stages of curing, respiration <:;v_ other lir^ ;...-oc sses occur but

they cease- when the loss of water rench^s '•• rtr-in point.

Thereafter, numerous enzymes continue to °.C-J, but at reduced

rates, f\or. during sJ.:-.vr.go and subscj'.iontiy uvjir.7 fermentation.

Tarkish tobaccos arc- harvested by the priming msthod,

which means removal of leaves at successive intervals, as they

mature. The loaves are placed on strings that are attached to

sticks and are cured by exposure to sunshine,, The cured leaves

aro then bulked until ambient humidity permits thorn to be graded

and b«lod. In this condition, they aro mr.rketo', graded, and

tilfid in very tightly compacted bales, after which they are

o'i. in storage*

iurkish tobacco^ a-; tr--.ted ".-mprioally luring storage

to promote fermentation. During fermentation thr- bal.-s a m turned

• v •• systematically so that they - :.• on the differ'*:.t sides smi

,-cTs.- Sui'.rjr temperatures of approxlmf'tely 20V0, p::-opnr ventilation,-

and aontrollod humidity of 65-75 i° are mîntPlnor: in the storage

rooms.- If the l- .vos v. too moist ^hon balod, they bocomf? darl:.

and a .y moL/.,, pnu tho .3-?onntic substancos will voltv/bilivoo If -bha

l-?.v.o •••.rr3 too ''Ify, thny do not f-ii'm nt or will foiiront only to a

slight °xtont. The proper moisture? content df 12-16 ^, Usually

two y--ars ftp'; roquirsd for ic

0;:.- o.:' en- impcrtr.nt cha.rp.ctoristics of Turkish tobacco

is its aromr, and all t'cir finli cult"..ro is '.im^d <=.t maximum

production of n--jf-G3Sp.r"' oiit', with »•• Jiu-ing mot hod designed for

their preservation by drying as quickly ao possalilo without oxcissive

heat. The greatest production of aromatic oil3 jomns from tho slow

growth of small-leaved plants undor xerophyt' .• conditions- Soils

with lo"f iB.-.'tility, either because they af. /' •;; ;. -.llc'T or of

coarse texture, will give the best rosiilts- Also Turkish tobaccos

have low nicotine content, this is due to the close spacing of

plants- in the field and to shallow soils. As it is well known,

nearly all of the nocotine is first accumulated in tobacco roots

and is then transported to the leaves. It follows, therefore, that

ft small production of nicotine is correlated directly with a

smill i-cot sy3trsm (67 W l ) .

Tobacco contains more than a hundred known chemical

compounds, including nicotiner Some of the substances found in

tobacco rrmain in the ashes of a, burnod cign.rottn; others are

greatly changed durin.',- tho turning process. More than 270 chemical

compounds have boon io.- ntif :nd in cignr"ttc- smoko. Those included

IT .jotine «.nd at loasfc 15 chomicals kno^M as oarcis :-gnns, '^hich arc-

"..!•- •.nAt rirf.Is causing

C*: thr oth"i liH.r.d, tobacco itsolf and its sraohr-: o

j- .a-p.co c7.CTr.onts som cf ^'hich " T O ssintial p.nd others b«5ing

Op to dato many o-g?.r.:lc substpneê h^vo b<?on onn-lyzod in

tobacco. Pi-.:s'-.nt intoi-su i.3 tho tr cra nlcnowt a on <-/ r.trr lions in

tobacco, and th-- rol'-.tod physiological wffoct? .

2.2 Traco Elnnicnts

Trp.co .'.-iGm-nta arc those that arc prfsont in minuto

amounts within °. givon matriy, Th^r-by tho oiu-.H-.ion of ?:hat

constitutes f. trace; amount is cloarly a îattor cf convention and

usage c

olsmonts hnv<5 «. doopor moaning in "biological systems

since thoy -'ithin living m^tricos =--ro not present as coincidental

contaminants but fulfill important functions. On the oth-^r hand,

their fcoxicological effects, play a major role in disease mechanism

if there is too little or too much, and if there are disturbances

in Itc-iv utilization and metabolism.

The bulk of living matter is constituted by the eleven

elements of lovr atomic weight out of the naturally occuring

nint.y two obtunts lis-icd in t]i~ classical p .•:iodio tabli and

are among th™ smallest; tônty ?l.->Er.ntsr,

ilodern nutri oj.on r:a:jarchos h">vo given thr> ,::ov basic

knowledge about trace ^l^m^nts essential to animals and mano

Almost a century took fhn scientists to identify th3 amino acida

and vitamin; "Ttiinh arR &'• .• 'B.nn oiânio irutri-;?r';s , '•.« TU.S th<?n

i/'i...'. to clarify the iv-ind rnd th.' toxicity of th: i:io::ga:iio

3 r;lamentsc Iron h?-s b^^n r^cog.aizsd as an

cr? th" ssv^r.bsienth cîrlury, "but :?•,guirRin'r-"1

discovorrsd la te r in iCJO • TJ".cil 1957, the nuirD r of ;"•!•.merits

r^cognizod P-5 osaf.Tibi&l ra-P s^v^n: iron- io-5.:r>o, copper, manganese,

zinc, cobalt, and molyT3.1'-.r.u-ii» In the last t ^ n t y years, six new

essential el'smrni.'.b havr> bo;n addeds seler.rlua, chromium, t in ,

vanadium, fluorine, and silicon (72 S l ) ,

Th'-. essential elements »-vr, indil.i -y.i. j . bl i for normal

function, ".o?-l b'-'ing and survival, Th^so w forna vo bo linkrd to

organic compounds through coordination or cov^lent ^nnds. The

physiochftmical conditions in •which trscr elements fu l f i l l their

specialized catalytic fv.notic.u3 ar^ not only dcap-nd^nt on the

concentration but also on the ch-mical form and val^nc1 stato of

thr? s

As with almost a l l good things in l i f ••, tr .ie elements

acre related to disease if th-=rr; is too l i t t l e or too auch. The

organisir. has son? officiant mechanisms to prevent i t se l f from

undesirable element, on?-: of th- .i is -the nembj-ene tr;..r.sport« If

the michanisr! of ut i l izat ion or stor.ê is die turbid, R, disease

n>«ohf".ii3sm rn^-y stprte In particular, sota-° correlations have beenI

sccabliâed between the nonnzr.-.',,~atioi]tf -of various mr-tsllic

'. ..-. '-J i:-. nhs body and the incidfsnes of disease (65 LI, 69 Ll),

nn elements, aaido fron th«ir consumption with food,

are also inh^"1.°d from si.,:. ?«3 f. result of npturaii and man-made

polluticio Ci:^rT-;t? srnokjiig n fl br?en tl-n DIP.in ? • ".c rrj of -icn^nti

for the liicotinf-! content of tobacco* Recently several gtudins

report imasur-.m-Tnts of i / r c ; eloment concenJ;ri=tions in r.l^p.j ette

tobacco (69 Nl, 70 N2, 1) Al),

Appendix A .suF.;j?ri7if:.a biolr&icpX ^fi-;ots and major sources

of several toxic irr--.' is • v...">o"ite j

ACTIVATION

3.1 GensrT-l Theory of ijÂvation Analysis

Thr> scientist "x=>s RI'ATS s -prchod fox* s- motaod of

b .Tir'ral o.nQ.lysir which is accurate, precise, spocif J.c,

nor.d«s\rucvivo, fast , economical, nnd universally applicable.

Active t.: on 'V.alysis is >••••. analytical tio.hniq.uf? ijiat cortss

CIOSG to sa-t fjfyir./j tho,c. :i cr-i-braria.- T'ho t'->jnni<y.zo is particularly

suitod ior th^ srnsitivs and a.ccuratrs dBtfsrnsination or :•'. vide

variety of elononts which ?.r° not conveniently d^t^rîn'-id ty

st^.ndart mnthoda of tr?""-: ij.nalysis. In conire,ft '•"> c >.v~ntdonal

chemical analysis, ths ^r !.:;ciplc? limitations ::" Lho t--clinig.uo

firiso from the ru."." •;.-:•? rôr'rtifis of .n olcin--r.t end not from

i t s chemistry.

Aft"r th? discovery of -.nducsdj or a r t i f i c i a l

radioactivity bv Curi1^ and Juliot in 1955 > i- + c- appl ic t ion to

the solution of analytical problems was rowdily rc-cognized5

The discovery ths.t neutrons WRro prodi3cfd toy irixr'ng radium and

•boryllii'm oy Ch-"dTick (32 C 1 ) w&s soon followid by the f i r s t

applications of neutron activation analysis by Hcvosy and L<~vi

in 1936 (36 H i ) . Thn incr«f,sing ''••police tion of r.°.d:.oriviGliAos and

nucloar chemistry to analytical problems lod to p. rapid growth

of activation analysis as an ost^blished laboratory technique.

In tha past docades, p. wid" rpn^ of methodological principles of

activation analysis has b"-3n d.'jvtioped. On tha r, '^sis and n.s a

result of rapid tochnic"! advances the nothod om now be used

routjmly for solving m~ny rwly t ic - i problems in science

p.nd technology, Thore "-.v r . ;y.p,t r/inlor of ->°p=rs -published

".D.d several symposip. organized on v/->is :;u!.,/•;.it ("JO HI, 71 Nl,

72 Hi, 76 I I , 76 Ml).

Thri sol-ction of a otivat ..:•.:; analysis ~s the ;\ppropriatr-.

technique in thn studina of the origin and ths behaviour of

trp.ee ..lcm^nts is b^sod on i ts sensitivity, spend, abi l i ty to

nnalvzo s-",r.v Iss for •". wido spoctrum of înmfints "-.t ths s"r"5 timR,

On the oth^r h'"nd instrument'-1 nuclear methods of pn^.lysis h^ve

sevir^l f\dvR.ntagc?s ovor th(5 othGr instrumental analysis, First ,

contamination cr loss of tr.ioe elements -".rn •'•-/oidsd 'iinco fnro

is no nc-fid to ch-°.ngp tho physical form of tho sample in §c-:nor l»

Second, sixicfi tho incoming nuclear projectiles f.nd outgoing

rp-dif.tions of the rp.dio^ctivo products h=we long ranges, there

t>.r<?. Intt loj if f'V-j, m -. rix offoctn. Third, since tho tRchniq.ue

is nond^structi^-s, *s scon P.S the induced wlio^ct ivi ty hp-s

docyod to s«.fs levels, tho samples c~n be ."-iiPlysKd by other

methods. Fourth, for mf-ny of the ralaments observable, the

technique io moi-. ssnsitivo, sel'Ttivo pnd r --curate thP.n other

motbods such as atomic absorption sôctroan-ry5 colorimutry

(Appendix B, Tn.ble l ) ,

Th" tpchniq.ue of ".otiv.ntion ".n*1-lysis is "b'sed on the

formp.tion of rp,diop.ctivfi nuclidps P.S ", not result of r^p-ctions

br.tv-on nuclrp.r particles nnd the isotopes of tho trfl.ee nlnur.°nts

of intorrst- Th s-? isotopes p.ro transformed into different

isotopes of either the srme or different ^lsrnntso Tho particles

r-TP. "vpilpble in sufficient intr.-nsity for gr:nor-<L use

10

are neutrons, protons, dnv/c- y -as, •' itens, flpha p-.fticlos, "nd

photons produced by ru-<itors, cyc\ >trons P.I</* Iruionr ^ccelor''tors.

In the neutron -".ctivation method, noutrons used

w i l y ci0 \;«ro kia.is, .vmraly; therii -l (0,025 '^0 r-rd f^st (in

i .-. .-v.ng-i of 14 H G V ) . Of th- noutron sources, the largest,

highest intnnsity, most widily used typn is the

/hich usuf.lj.y h^s noui,..-on flux in tho TP-nge -o.f 10 mutrons cm"

a^c ~e Irr- '. >t . i ra by th.Trn°l noutrons producon rndiof ciivo

isotopes by (ricV) r^''!ction, for this rn.ison intr-rf'-.>^:-iof.a due

to tbo other nucl^-^r rnr.ctions such as (n, p) ^nd (n,OC) flr-=

minimized,

Th": m.'sb corrO"i c itrvntion r^P.ction is neutron Cf-ptur9

in which a lovr-energy (OcO25 eV) neutron is absorbed by a

nucleus with th ^ prompt emission ^f ? ?.r.ma T"ny. The reaction

can bfi illustrP.t'-d for instpno^ "by th° n«ti+;.•<•••:_ ^p.pture of iron

such as :

58Pe + Xn * 59Fe (3.1-1)26 # 26

ThR neutron capture rosults in an isotope of the san','5 clement,

having incros.sed the mass number from A to A+l, Th^ neutron to

proton r^tio thus increases from N/Z to (U+l)/Z And for most

stablrs target nuclidss this increase is sufficient to result

in a product isotope which is unstable with respect to /& decay*

26Th9 isotope of cgFe is unstable snd has a half life of 45 days,

~- ?7.-r niodf? if Q and Lh.c dr.ught~-r isotope rqô j •-" stable.

11

Tho isotope- t,o^c- -nuca ? siag'i.-- gp.rmi;- with different

gamrna energy (keV) r«l-"tivn intensity

142.450 800

192..23C 25OO

334.810 300

1099.270 56000

44000

Thra emitt-.d g^mma-r^ys orn then ho d~ tooted, identified

countrd; th?.- t-.-chniquo is called th--

The O-.CCTJS D.f th-'. instrum^nta.1 -octiv"'Ion /=.n«>-lysis is

primarily duo to tbo -P.V-.U dGvsloptr.nnt of tho following:

1« Stof5.dy-opGr"ting rc-fctorg -"nd .^cooler"tors.

2. AutO3H!'tic methods to tmnsfor snmplos to irradiation

sources *nd rp.di^tion dot°ctor systems.

3 . Efficient scint i l lat ion -".nd si--nif;-:>ductor r^di-tion

detectors coup?.sd to high-resolution r-^.i^tion-'-ncrsy. .s

4. High-spiod computational fac i l i t ies f>.nd methods to

rosolv? q,ufntitf t ivsly the complex doony curvos p-nd tho complex

spoctr-" of mixture of rndi ftions into thoir component, rp-dionuclides.

Rigorous trontmont of tho gonr-rp.l r^ta ^qu^tions governing

the nuclear transformations ^nd th1? docA.y of the "ctiTrntion

products has Tjsen ptfesentci TyBubinson (49 H 1) CTnti hy Lewis

L l ) . Thfi b«».sis of «>.ll such calculations is thp.t r"dio.".ctive

12

i s r. vu-?ly p

jt- tistic r>lny» Thus th-j r<vc<-, of dscp.y of a l^rge number of

•tors, F, ia proportional to N.

•».'.oj.w \ is the diaint v^ra^xon constant of the r^d

srsej^s eoncr.rnoci» I t e n p.^sily bo 3ho'7n th^t

\-'j£ (3,1-3)

i/2

whoro t , /_is thro 'h^-lf-iifn' of th<3 species, th^t i s s tho time

t^ken for t?io •lumbor o' °tora to b" roduocd to hrlf of i t s

originp-l v . l ue . Int^prc.+i on of th- d^cp.y ^qu^cion giv«a;

U = Fo T ^ * (3.1-4)

whoro H is th" nuraVr o" ^toirs i'!ra»J.niny "i time t B.nd No is

the i n i t i a l numo-r, AoT"'.vifci a e n br; substituted for numbnr of

A = Aoo"-^" (3*1-5)

which st^'C's tha woll-'uiown f'".ct thr-.t P- rf?.~. '•-•ci'\<--j source

decays ^xponenti'';,lly.

Whoa P. rp.dio".ctivo spf.c-'-:•.•• is produced by i r radia t ion

in '-. oonst-'iit flux of p^r t iolos . the roaotioa r--te H (in

events p^r second) inn,y b-." ^-xprcssod AS tho numbor of product

nuclei 15 cr-f.t^d p .-r second by

E - — - n (X $ (3,i .6)dt

13

n = number of t'<.rg"'-c "i.oms •••_ >a,.nt

n = &£ x 6,o2 x 102?

M

W = V-V-ifyht of thrj dosircd element

f = fractional -'• c'otr/ic ".-.• dftneo of givr:i V-.'gr-.t nuclido

M - "tomic woi&u"!, of tbi ~l';r.mnt

$ = 1.rr.''.(?;. tioi flux, nûtrons/cm -sec

2- c r o o * • ? a c t i o n , 3ui

r^-t"1 of c i- ngc of product nuclei during tho irradiat ion i s

gi.vnn "h,~ J;h' diff'^-nco tntwnon thn production r-°x,^ R ••'nd

the- deday r".to AK, or

^ = •:; . :-,ir 1-7) - - = nOjzJ - ? a 0 .1 - s )dt dt

The solution of Jr,h.r. r.bovs diffsrr-nti-'l .-PuP.tion e n bo obtained

by integrating for tho i r r a d i a t i o n time t.,

N = ••—-•^ (l - e" i ) (3.1-9)A

fnd tho induced -"ctivitv is .jhmn bys

A = 'AN(3.1-10) 4= J I C ^ - . ' I - Q " " * ? ) ( ? W - 1 1 )

Tho tf.irn (l-o~ i ) is sonntim^s called tho s"+uY-'.tion frctor ,

S, As thG irr^dintion timo ( t . ) ^ o i c s l«rgc- oompr.ro 1 to the

h^.lf l i fe of the product ("t-i/p)' ^ ^ sp-tur^tion f.i.otor "ppro^chos

unity. Thonfom <•• t tho sp-t'j.r™tion time

A = nCT^ (3.1-12)

At t;o'. - nd of p. cooling timr (t ) , the fin<"l "oiiivity of r.

givon r.uclido CP.II b^ r>xpressc-d by ths

.ft - aCTjrf (!-«" t : 1) o" *<» (3-1-13)

14

Usin$T this pqus.tj.or, :'t Is possible to make sr. analysis

for a given '-'lp.in^nt. This •w.il'l r~r: 'r~ th^t the values of QT ,

<f>, t j , and t, /„ bo know <wid the vr.lue of A 'he determined

•jjcperimontallye This type of absolute determination is complicated

:' . nr-ny w /&, such as 5 (l) tho cross sections of most nuolides

are probably known to i .i better then botwjn 5 to 13$ accuracy,

(2) th > flux can v^ry durin.? 'the irradiation poriod, or fliix

grfidionts o. .1 e r . i t in vho Rumple> or th'-) flux is sinply not

accur?taly !.:IOTUJ and (3) i t is difficult or time consuming to

make absolute activity pi a.anr'vmon+s on th? samples or the

efficiency f?coor for tho detoctor is not p-ocvr^tcly lnovnu

V/hfln th:s trvchr/iu--- is usnd i t is difficult to got an

accuracy of bratt-ir th jn <-2O9» without extror.e wrs *»nd effort in

detormin^tions v.?f:! most s T p b s (6$ W l ) .

Tin majority of Hct::.v>tit..i ".nn lys-s 3or tod'.y ut i l ize

comprr-viiva tochnici.uo. In this method, " ' • " s .f.plo (of

wnight) contr.ininR1 the nlpm'.nt to bo .i j^rm:.nwl tho unknown

-s r.ri :rro.di----tpd simult-^n.-'ously for the BT,? Miac at ths

flux. The specific act ivi t ies (disintegration rato/unit

weight of element) of both st-nd^rd "nd unknown pre th« sp.me0

Therefore on's c-n count th'? unknown *»nd tho standard undor

ideiii,ioal conditions (counting efficiencies 'boing oqii.-.l in both

c°ses) "nd us" the relations

As

or, sin~-o V.s: count rat^s »m proportional to tho disintegration

15

i

V Vx' (3.1-15)

R /$a' s

whoro:

W - ifoignt of --.nnnt x in unknown

•= v'-'ii."ht of ' 1.?moru- x in ss

A = disintogr^tion r°.ti of unknown

A = dr'.înt-'gr-iîon r -tc- of as

£ = counting offic:rnoy of unknown

countinfr of:. ioirvnc;.r of s

.Tc."! countin,- c o n d i t i o n s , t and t , T O r-.qup.l,

therofore*W E

>-^-£ (3.1-18)

This comp-''.r.''tivci tochniq.tiR oliEiinM,:^ n -ny of tho

•urxcortri.-i.iit.ies in the

3,2 Cammi-R^y Spootrom^try

G-arnins.-ray spectrom^try by the F.ethod of

analysis m",kes possible the direct determination of individual

radionuclidos in a gamma-emitting sample. Such •^terminations

are possibl-; bôs-uso tho method provides a bng-i.s fcr ths

i&Giitifieation of specific nuclear transitions, and those, in

turn. <va jliarftctrristio of specific mdionuclides. ThG method

has provfin to be naay to use, highly sensitivo and fast, and

16

has bpon applied routinely, with gooi success, to r-nalytical

problems ir. radiochemir-cry-.. ;'.us, sM.r.ipl' s c.-r.rtv in ing complex

mixtures of rpdionuclides,. v-ith act ivi t ies ranging from the

nano-curie to the picocurie l~vel, p.rs rraadily m^rsurod non-

iost/'uctivoly, in prari-xls of timo ;:e.nglng frcm a feP SGcond3

re- nr.vflpjj ] houi-s.,

1 is p. simplified block diagram of the

instrument •• '- . syotom mo:." ccrcronly usod in this application. In

principlfi, &s.mni?--Tt&yB eratt^d by tho radioactive ss.raplp, intsra-ct

with tho dodr-ctor, and ^lictrics.l impulses whose amplitudes .re

approximately linearly -proportional to "ths -i.Ti-gy of ganin?-rays,

aro obtained. The pulsss are shaped, amplified, .'vid then

elr>ctronico.l.'.y s..>rti.r according to their amplitudes so that a

pulso-hîght distributior. (or puls^-hoight spectrum) is obts.incd.

1!h.r. pul so-height spectrum w'-y b« dispâynd or recorded on

vn.riou.s davicGS,

Thfj electronic instruments rog,uirGd for a;3.?".m?.-rn..y

sp^ctrornvtry incliide the following! (l) high TO It.'fen siippliesj

(2) pulso pro-amplifiers; (3) pulso prnplifiprsj (4) pulsa-

hoight ans-lyzGrs; (5) stabil izers; ?nd (6) output devices

(R.g., printor, plotter, p~per-t''po punch, cfr<i punch,

.p? reoordGr)»

Tho pulso hslght spoctrum is P. plot on which pulse-

hoight increments per unit timo .".rfi plottod P,S a fi:nction of

tinzvgy ±ncT:m'-:ntz Aistributrid into channels of ths •"•

17

Preamplifier

Amplifier

Analog-to-Digital

Converter ADC

IOUTPUT

- Magnetic Tape- Teletype- X-Y Plotter- Parallel Printer

Figure 1. A General Block Diagram ofa Gamma-Ray Counting System

18

This -plot if* n continuum fozrrrd by " s^ri^s of approximately

gaussian-saapud ponks. '.,'hc- p:. Ics •••?;', tlv: co-< :Lnuum arf* the

display of fan various interaction processes which have: t-"ke.n

• .ace '.'it'oin thn drat'TC o

If a l l of thrs f:;i>Tffy of a tfamms-ray photon,

=pr-iET>.it=!tivo of P. specific nuclear trnnsitio/i within the

' ; WG'-" divyiooitod "'"'.thin th1?: dot^ctor, a ' ful l cnar?y

yulsc' './oulo. br. n'baTV•"-•''..« lh-s'» full onor.^y pulses ' ould appear

in the pulso-hoiffht smctrun Ji.stribution about a ' ful l or.zrgy

psak' t ths ccv?t..'"r of T'uich wou'.d bra displacod from zero on the

pulsr,-height seal':- =>. distance proportional to tho photon ^

The intoractioa of tre nma-Tf-y photons result in the

ionization, ^xcit"-i.ioa ^nd po3sibl.: dissociation of the

molecules of tha dotoci;•...,:• ia.l.f-,-1 ial» The soi.doon'juotor detoctor?

which is mostly usod in gar-'ra-ray sp^ctroTn'-tryj •"'"•nctions as

a solid-st"to ionizp-tion 'jPiamb r, and has characteristics Thich

makf:- possible Fn improvTr. dGtoctiiTi •'ffici:>rit.7 for gamma-rays

and a superior rasoluti* n ca;:abj I'.r,y. Ii-:sclutici.., •--- the term

is applied to the g*nnn!"-my pulso-h^.ight spcctruTi, is a measure

of fh~. minimum -.n'jrgy difference fh?" must oxi&t brtwra^n two

g'.mma-rays for thîr corresponding ûll-on.Tgy prjaks to be

distinguishable. '7ho convention for a detector, has bo&n to

d(5fine resolution as the PWHM (full width at h«lf maximum) of

thf? full energy peak oxpressod »s an «q.uivplc;nt amount gam.ina-

ray -.uorgy. TV. 1.53 MsV gajnna-ray of Co has frequently been

19

used as r. s•;;<•.YidT1! fo r oomp" "'iôn pu rposes , 'nd r e s o l u t i o n

f i g u r s s ».r'. visual ly quo;. "1 vi-oh r&foT-i-.-n to - h i s g«v;ii:o-rs

R e s o l u t i o n from 2 t o 4 ksV p.r<3 tj ' -picrl f o r c u r r e n t l y

r.. ^ L i ) &<} t'" • c t or a «

Nhchods t o r n s o l v e mixod gamTn^-r^y sp~ctrp. h.°.v3 bôn

Anvelo-:od vrhich f.rr b"sod on f n c i y t i o n j or isrraphio«l p roenduros ,

clftct?' .inic r";n-ns in m u l t i c h a n n e l "-vv.lyzors, ^nd nunc?ricpl

by

Anilysf.s of gf.rr-nn.-rpy spoctr^ in diglt"! forn: "rr-s asscribsd

by Covoll (59 C l ) e In this method th° respon..- • cf -;-Y.a pu'.se-

height '"n?.lyzGr is r-^pnaontf-.d graphically ns rnct^r.gl-.s vhose

areas f-rra proportion*-1 to to., nunb'-rs of counts in the channels*

Figure 2 shows •• -fiiV.L- ?-.i..rgy i?>.!r plotted in histogram form.

r e sponses ".ro d - j i rn=t . ;a a^.,s.2 , p , _ : . . . . « , ?. .

Summation of the responses from a, to r. gives P. value

that roprGsonbs th" total counts contain' d in tb.c- ch^nnelsj

shown graphically ?g th'; fv.p P in "Fig- 2, If tl:s ."".rea P is

dividod by '•>. lin^ connooting ths ordinata values a nnd ». , the

PI-TOP abovn th" line, given by 3\T in Fig. 2, is r?l«tod to ths

peak >*nd thus to th'? gar-^r-r-ay intensity. Thn r.•-•->. Q is related

to tho "background1, «nd is subtracted from thfi xroa P, £>.nd is

estimated as the area below the base line extrapolated between

the vS'll'-ys - dj c'-iit to the pe"!;«

20

tJ I

J i an

/

/ Van-i

\

Figure 2. Pulse-Height Analysis Data as

a Histogram

21

From Figure 2 i t is notsd t:."-'-

nP - II a i (3.3-1)

Q = "n

US = P - Q (3.2-3)

l t (3,2-4)

The ditfils pnd th>- applications of the technique î.v&n in

the roforences 66 I 1, 71 K 1, ?.r.& 75 C 1,

22

EXPi-.'RIV Y:.iL PROCEDURE

4,,1 Sample and Standard Preparat ion

r ••:•' d i f fe ren t brands of c i g a r e t t e s wero purchased from

l o c a l frrocsry s t o r e s . Thas^ ciârett .ns woro opaned and tho

wrapping papers w-sro r o j - c t ^ d , only th^ combined tobacco of

o i g a i v t t o s -wi u t i l i z " a s All tobacco samples wevj mixed

thoroti?hlj-0 Tho tobacco3 êxe dr ied a t 30^ humidity ".nd 2.C)OC

tempsrature for 48 hours . Repl icate samples of thss.^ toc-^coos

were -pressed in to po l l :td of 1-cm in diamTto.^- --.id c'--.r'r-°l mm.

thick.

Thr^R d i f fe r nt tr->nds of cigarottr? tobaccos wcr^

t ?00 C w jfnout "ch- "'repping p-^rars. Tho ash samples

woighod in r?nclrf>.nr*& polyethylene tubss and h^pt sealed^

The measur^msnt of conoontrations o? t:?-"CG "leip-^nts by

comparative m^tho'i of a c t i v a t i o n ana lys i s i-0CLuir.?s r e l i a b l e

standards cont° in ing same Rl^m^nts of int^r-.-st in comparable

p-inounts. U?3tionr.l Burp"u of Standprds' environmental coal

standard rnforence mf'tori ' ' i WPS usod "s str-.nd"rd, and p- . l le ts of

1-cm in 'liamfiter wsro pressed for i r r a d i a t i o n (Appendix C),

The p c l l e t i z s d tobacco samples and coal st^nd^rd were

wfii^bci and stacVod up in ths sane polyefhyltr.^ •oi':* --.nd then

4.2 Irradiation

The pelletized tobacco samples, ash saipplss and coal

stfmc^rd" w "."* i rrrdiatî f c four hours at Qekmfice Nuclear

""• 3"inrch '.id Training <J<jntfir (Istanbul) reseproh reactor TB-1

r.t v MU:-. -.-a fluji. of P. .out 10 cm""sec »

4 , ? J c - uat i :.(=• T^ chniq.u .•

Ths a-c i iv i t i f i s oi' samples f-nd stand":•:•.••; worn counted

with a Ge(LiN dstp.ctor >f 40 cm act ive volume coupled to 1024

and 4096-chan:: i l puls:? height p-np-lyzors. Ths . •.solving pjwer

of FffEM was 2.2 keV Pt n 33 fe"V of Co Line. Th<? detnetor was

housod in -•• l-~p .. sh^c.1'. to suppress V*.cVground.

Counting .'..i.i oo.ilin , tiro'ss mm arr^-nôd According1

to the nucT.'V.r prop"-rtic-s of radioisotopss. Short livod species

were counted for 1000 seconds aft^r 3-days cf cooling. A decay

period of ono month W A S allo'"od for lon,<- \-j ••.• ... s •n- oios ?-nd the

sP.irpl s rr-.vi count d for 3 to 6 hours for ins dwt rrain?tion of

these radionuclid's. T:i<3 irradiation Q.nd the counting timss for

~l.;3i.:r.ts observed in tobacco is srivon in Tnblf; 1,

The r>n" lyzor was op-librat^d with scsvor" ' s

sources e«ch time when r set of reading was t^ken. Table- 2

lists tho ensrgiss of th« gamma rays of rndionuclidos used in

the so :l'jtarain-"tiona«

Irrfldi.--i.-l;ion5" and Cov.ntin.7 Ti

For t!Vi,. ];i?i-:'--.ts OV,s^rvo'l in Tobacco

t. t ,. t ,. Elements Observedirr cooling counting

4 hr 7; d&ya 1000 second Na, Kt .is, Br, La

4 hr 30 d-?yt 3 - 6 hours ^c, Cr, Fe, Co, ii;n,

S.-i, HTs, STD, C S , B a ,

C - , 7!-a, H f , E g , T h .

a 13 -9 -1Samples v-?,-e irrs-distî a\, a thprpa.1 nfri;t.-_-o flux of ] 0 cm '"sec ,

25

Production n.nd Proportias of Raclionuclsi Observed

i'r- -;et Prcduc* Bsst&'-ray usedUticl.-n.r Reaction's Abu^nc--,". H^j.f-iiy"e for determination,keV

?3IT.?(n,^)24Tira 100 15.05 h 1360

K "'1K(;n,^)/!?K 6.88 12.49 h 1524

Sc Sc(:i,,y) Sc 100 84 »0 d 889jll?0

Cr 5OCrv.:rX)5iCr 4.31 27.7 •! 320

FG ^8Ffi(...!^)^'Pe 0.33 44.6 t 1009, i?5i

Co !59Co(n,^)60Co 100 5,27 y 1173, 1332

Zn 4Zn(n:.!i) ^Zn 48.89 244 cl 1115

As 7Âs(n,d) As 100 26.4 "i 559,^57

Se 74Se(n,.>)75S<3 0.87 120 J. ?C^

Br 81Br(n,&)o2Bv 49.46 35»3 h 554, 776

Rb ^Rb(njS') ^b 72.15 18.7 d IO76

Sb 125Sb(n5c<) l24Sb 42,Y5 60.0 d 1691

Cs 153Cs{n,L<)134Cs 100 748 d 569, 796

La 139L?'(n,^)14OLp. 99.91 40,2 a 487, 1396

C« Ce(n,o) Ce 88.48 53 d 145

Eu 1 5 1Eu(n,^)1 5 2Eu 47,32 12.5 y 344,964,1403

Hf 18OHf(n,^)181Hf 35,24 45,0 5 482

Hg Hg(n,cf) 3Hg 29. SO 46.6 o 279

Th ?753|fh(n,K):235Th 100

1 27.4 d 300,312

26

Thr3 n.TOPS u n d o r t h e r." ->tcp.---.is v.-v-. c••:.'•-,?•?•

subtrf.ctrad b^sû on tho ir t^rpolnt j on of points on

both sidos of the p-i^Jc. We-coss^ry corrections for fl^cny times

"cooTding1 to th<5 hi="i.f-livss c-i' rP-lilTlaoôpns ~.nd oo^nting times

•x, '.hf.J. • ••rrind out,

The* "mount of <*. giv^n fjlem«3nt in n sample WP-S computed

x'rom t""i r>-.••"'o of th?. i'-s- k irsn.s in tho sample to the .°râ.s of

+hn oor^fisp •-xli;\i- ro°.kf3 in i-": \ st"n«i»Td. The comparative tf?chnio-ae

h'.s -"l-crdy b*sn '-.xplîn'd in Chrptor I I I .

71;I t i--s :i?coss^v>y to s t r ip out tho COIP.-.O.I.;.- t ,-i' .jt

from tho 279 koY photopor.k of ^Hg prior to cr-Taul^tin.j the

ccncc-ntr?.tiG.i-. of mr i c\i:.-y. ^11 othor phctop.?-".kf.; onployod in the

analysis ^^rc found to c j.r-^c of spôtr"'! ii-'iTrf-

A.A Vsi'op.nt Transference!

Tho p~rc:mt trr>risforr:?act> of tr^.co ".. . x':s from tobacco

into the tobacco "-sh is dofin^d °-ss

C

x P x 100 (4-4-1)

i- T ! ^ Tr»nsf(?rnnco into the tobp.cco ••'•sh

Cn , t p.buncip.ncG of th? element in tobacco p.sh, in ppm.

Ctob * "^mrlr-no° o f thn ^l";niont in tobp-cco, in ppm3

F s woight of th. f.sh obta,inf5d pfjr grp-m "f tobacco".shed, which ia in th is cp.se 0.15 g '°-sh por gtobacco.

then, c

fu T = >£S& x 0,15x100 (4.4-2)

c"ion

27

^s 3 -ni 4 give tho results of .nm,lys<is for 20

sjl5nifsats in the I'urkisii pipe '-nd îg^r .tte *ir>b'-cooaj

'he?; roapoctivoly*

Piguroa 5> 4» I? flnd 6 shov: the S|X*ctr!i. of irradifi.t3a

PI ^shas aft-r difforont decay ani counting ti:r:s.

Table 5 gives tho 'prrv-.ni twnsf r-z. vnr.. vni'ins of

Rlomr>nts in to th<3 tobacco ".sh.

Thn 'irinfT3 quo"^.d ar."; tho deviat ions cfroru oh*

of tho observr-d VP.IU.'.S Ft. clotain^ci by •=.-/ ;? ;••'••• g "Lhe values

from sovoral mr^-surfunor t-iu

tobaccoss

B.---JL 1 s Tutiin

B s Bfifra

C : Bi r inc i

D : Kulup

E : Hsrmf.n

F : S i l a h l i Kuwetlor ( f i l t e r )

G : Sfoltepe ( " )

H : Sfmsun ( " )

I s Export S?.msun ( " ) 0

28

n/>BLE "

Ooncentrr-tiorr-i of S'sv?rp-X 31<=1-i'v.its Observed.

in Different Brands of Turkish Cigar-; J;tG Tobacco

(concfiiitra •';•". :.i;i! yy'r uti.'

Elomenh Pip*-.

708+3'

1' (fj 1.3+v-

Sc

Cr

Fe

Co

Zn

As

Se

Br

Bb

Sb

Cs

Ba

La

Ce

Eu

Hf

Hg

Th

O.35+*

Tobacco

'-

.',02

13.5+2

(#)0.17+-

1.0+0.

49+5

1.0+0.

0.15+0.

30+3

14+ 1

0.12+0,

0.28+0,

52+2

0.80+0.

1.6+0

0.041+0

0.27 +0

N.O.

0.,38+Oe'

,1

,1

.05

01

04

08

.15

.003

.05

03

0

0

j

0

0

0,

0 ,

1

OoC

0.

0 .

AT94+10

•\4V' • M

0,38+0,02

7,5+0

. 11+0

.85+0

-,2 +4

o „,'-.-.).

.]4+0,

67+2

2«--a

.08+0.

,22+0,

57+3

,99+0.

..85+C

)33+O.

,13+0.

0.02

31+0.

.5

. 0 1

.05

. 1

,02

,02

,04

01

>.15

003

01

02

Cigarette

B

406+20

2,5+0.1

0.3 7+0 ..01

6 0 3+0 ,,2

0.10+0.01

0.80+0.04

54+4

1.-.1+0,1

0.20+0.08

53+2

Vj+l

0.11+0.02

0.31+0 .,03

63+3

1.070.2

1.8+0.1

0.035+0.003

0.17+0.01

JT.O.

0.34+0.03

Brands

C

420+20

2.3+0.1

0.34+0.01

6.0+0.4

0.10+0X1

0.75+0*04

38+4

1.3+0.1

0.20+0.05

62+3

18+1

.-,"i:+0X2

0O7-O.04

46+4

1.0 +0d

1.7+0.1

0.035+O0O05 1

0.15+0.01

u.o.

0.29+0,03

I)

4^:J-15

^ 9 + 0 ,

0.35+0

7.3+0,

0,10+0

O.76+O

35+3

1.1+0

0.17+0

61+3

15+2

0.11+0.

0.25+0,

57+3

1.2+O.J

2.3+0,

1

8 01

5

. 0 1

. 0 2

. 1

,01

.02

.03

>

,3

0,038+0,004

0.21+0.03

ir.o.

0.33+0.02

29

(Table 3 continued)

Na

1?

Or

r-,

Zn

As

Se

Br

Eb

Sb

Ca

Ba

La

Ce

Eu

Hf

Hg

Th

it

41O-

;; ..+0

10.3+0

o.i:, ^

o,7r. ).

22'r2

1.5+0,

0.25+0

64+r

19-1

0.07+0,

0.19+0.

ea.o~o;

1.-S+0.

0^3+0 .

0.11+0.

0,05+

0,54+Or

3

. 2

. 0 1

,5

. 0 1

, 0 *

,1

•04

,01

.01

2

1

004

01

04

F

/125+20

2,5+0.1

0./.1 ;+O,v'r

7 "5+0,5*

O. .L2+C,O1

0 ..JO-O.CS

18+1

O.'--T-O/L

O.lfi-''-O.O2

5^3

'.3-1

o.ov:.o,i-2

0.2f+0.i '2

59+4

1.2^0.2

1.8+0.1

0.0^6+0,003

0.18+0. )2

0.07

0.36+0.02

... Br^r.ls

G

345+10

2-^+0.1

o.3y-TCcO2

l>< 2+0,1

0.12+0.01

0,Qr)+0,05

25+3

0., .v T-o . 1

0.20+0.05

52+3

18+1

0,17+0^03

C. 2 2+0 .-01

82+5

Oo0+0.1

1.9+0,1

0.03 3+0 ,.004

0,18+0,0?.

0,08

0.36+0.03

H

565+10

") \^ .1 At f / ~ W ,

o,35-"O

S7+0

0.10^0

O.'7j4..,

l : l 3

*i ; !_*!,'- -i • * ^ C (

0- . "."O

17-5+1,

O.Ofa+O,

0..20+0,

88+5

I.GTJ.

1.-+0,

0.0- 0+,

0,15-To.

0,03

0.30+0.

e 2

,02

-5

, 01

-;-5

=1;

. I !

.5

.n2

<01

.1

1

03

01

02

T

559+5

2,4+0

0.27-70

^.4+0

o,c*fo

O..6Ô

21+r

0.18X0

0,i5~o

l?4+4

15+1

0.0^-vo

0.14+0

61+4

1.2+0

1.9+0

0.032+0.

0,13+0,

0.C7

0,27+0,

O

.02

el

• -'a.

. 02

.:•

.02

. 0 1

, 1

, i

,004

,02

.02

N»O.J Net observed

30

•&BI/3 A

icontr^ti'-on oi' ;>-:verrl Tiilf-i

Cif:?.rott. Tot)?, ceo Ash

(cîoooni.: • .'.ion ,;i#/g unless f* indicate3

is.sa of CD.PJ-I • ottf-.

K (?'') 1./.20 14.8 1;C3

So 2, .50 2,24 20?0

Cr 56.6 52,5 52c4

Fe- (^) 0 G?. 0,62 0.60

Cc \? 4,4 4.6

Zn 8L-«4 88 ,,1 82,4

As 5.1 3o8 5,2

Se 0.6 0.8 0,75

Br 295 274 295

Bt 76.4 73.8 72,4

C s 1.1 1.3 1.3

Ba 356 572 400

I"1- 6<i4 5.6 6^3

Co 11 10 10

Ett 0.19 O.17 0.I8

Hf 0.89 0.80 0.-92

Hg 0.06 0.05 0.03

Th 1.8 1.7 1 > 7

31

r~

2-

i

o

LJ

CJ

42K

313• • *

82Br .

554

511 keV

i\; \

VbAs

.559! ' • • • • • • ' •

82Rr619

fJi

//

698

82Bi

// I

// 776

]

\\

\

\\

827

I 1• . . . / •. 1

CO

LJ O,Q.

LO

o 1-(J

500

2500

700 900 1100 1300 1500 1700 1900

82Br

1044

1 1 1 1

24Na

1368

•

T 1 1 1

\

T

42K

1524jlli!|

Br I •1475 / [

i i i

Brand F

140La

1596

1 1 1

2700 2900 3100 3300 3500 3700 3900Channel Number

Figure. 3. Gamma-ray Spectrum of Tobacco Following 4 - h r I r rad ia t ion

with Thermal Neut rons and 3 Days Cooling.

233Pa

75 233_311 C r

S e 300 I

ioo. CeIJJ1146 ^ 131 134 124 134

181 Ba cs 5b+Cs,H82 , A 9 6 511 keV 5 6 9

• • • • • • • • ^ • • i i

134152 Cs

Eu 796779

J-.A I).• • • • • • ' . . . . • •

2500 2700 2900 3100 3300 3500 3700 3900Channel Number

Figure 4. Gamma-ray Spectrum of Tobacco Following 4-hr Irradiationwith Thermal Neutrons and 30 Days Cooling.

12DC

l / )8

§4.

600

300

700 800

400

82Br

1044

. . , . . . .„,,,••., .

24Na

1368

82Br

1317

II,..,

42K

1524

82Br1475

« I

x2>

140La

1596

A

0/ f Brand HNa1734(DE)

ii

900 Channel Number

Figure 5. Gamma-ray Spectrum of Tobacco Ash Following 4-hr Irradiation

with Thermal Neutrons and 3 Days Cooling-

M

C

ooCD

CN1 00 CD CSI OJ o oo CD »<r

( _OLX) 13NNVH0 *J3d SINHOO£ 35

^

CD

CD

o-o

00

o• of -

o.o

CD

low

inFo

l

S-

<fouund

X IO

1

"ua

t f\\J i

$i

05

E

cRo

ays

Q

oro

"UC

O

z

Ei—

(—

\—

.c

Tr^nsferovios of ElGiafcn-s ir-to Vobacco Ash

•,r.ont

K

l o

r r

Co

Zn

As

Se

Br

RTD

Cs

Bn

l>r.

Ce

Eu

Hf

Hg

T i i

Brand I'

91.2

97-•

87

93.0

88,,1

22 o9

42,3

45,0

05.5

60.'

53.2

84.8

96.0

91.6

81,4

78.5

79,4

Ii-^nsf '*:•".. .co

I'-r- nd G

89.4

86.2

R5.6

75.0

73.3

52,9

63.3

60.0

79 oO

61:3

88.6

68.0

90.0

fS.8

77.3

66.6

9.3

70.0

/b.'s.nu. H

79.1

94,3

'O.3

90,0

93.2

82.4

69.6

70.0

85.1

62.0

97.5

68C2

87,0

wf.; 2

90.0

92e0

15,0

85.0

3,6-

DISCUSSION AND CONCLUSION

A. DISCUSSION

6.1 Concentration of Elements in Tobacco

Tobacco, lilra other plant tissues, contains minerals

and other inorganic constituents deriving from soil, fertilizers,

or agricultural sprays. Upon combustion, the metals remain

largely in the ash, unless ^hey become vaporized or transferred

into the stnok* stream entrained in microfragmenta of ask*

In view of the wide variations in trace element

concentrations in soil in different regions, nine different

•brands of cigarettes and a br -nd of pipe tobacco were analyzed.

In Table 3 trace element concentrations of pipe and

cigarette tobaccos are given. First striking point is that*

some of the elements in pipe tobacco have quite different

concentrations* The observed concentration values of pipe

tobacco for K and Br are one-half e"<l for flf nTe tîca the

corresponding value* for cigarette tobaccos. Fa is also found

to be present in higher amounts in pipe tobacco. Cr end Zn

are the other two elements with concentrations about twice as

much ths values obtained for cigarette tobaccos.

The factors responsible for these differences are due

to genetic difference* within each type as Tell as to

differences in soil tjrpe, stalk position of the leaves and

more than all of these to saucing material added to pipe

tobacco*

57

i c pipe tobacco i s ?.lso sun-cured c.nd fermented as

the cigo.vstta tobaccos. iV-. • :.ly diff^rorion is the "raucing"

material, or casings contaijdnsc licorie"., sT'=r>toni;ig agonts,

"'vr?.~s, and other flavoring -iiatorials added to improve the

*'iiyn;<( aremdf and Prnok:-. t<?i"i.< P? ,t G tobsccos nay coi.hp.in as

mr.wh • H 50?,.. soucx;^- fltid i^s.jng ma-;, .r ial .

J.nv '.. '"Lgp - - on '•. 'eh'! VI-RCG olom^nt conctt.Jitrctions

cigars .:a t.-.iv.eeCJ slio"-. t'TPt ''.Imost PI.1 of tb/; olpmsnts

present at shout the sans p.romnts. At th.-> v-ry f i r s t s i^ht , the

high Br content of tho . j-.'ind I ciga-rrjtt^ "ohscco js ftr"OBr'--nt,

and about twice ths concentrations in ^th's- b v n u i , i"bo 'brand

I ciga- gtto 3* ir.n.nu.-f -so-iu^d rbroad v.'ith Turkish tob?.cc;s, Vat

with ? quit^ di'.'f-rro^t prosos3. Tho diffcr^rco in Br content

may b'. due i;o tnc uso f ai'ithyl bromido as prTs«rvf.tivo during

the 3torajc (•"id transporJ>ft c:?. pori.'d, as w.il1. flq to alcohol-

solu'Erle flaTrors and froOT-ati? substanir.s add "id ••"urirg ns.nuâcturing

e.s iro.<3t 01 tin foreign oi/?ai"!t-,cs aro processed,

'.''ho f i r s t four brands o c'.r\.i etto t-.bûnos, ..? B, C

D ar^ Ic.iown -to be "'strong" and tôir Zn ooneon~r".tioi;n are

h.i.s'hrsr ths-n t'ls ochr.r four brand?!. Tho brand i tobp.cco i s

gpTjially prepared for hand trapping ani togo.th.or with the brand

B hn.v; .;!•.-, ;..ijliQst Zn amount, about. twic«s as much the las t four

The rrosGncr. of Eg is noticeable, but th^ vary lo-i

urations founi are very far to bs alarming, and in fact

B# -!T«s not dR-tooted, in four br-nds under those irradiation and

counting cmvlitions.

38

r"-T! concent r n t i u i o n* '••-•• ' "'•'-JT^L ;P ..• .AT •• -icr-.n "nd

Trs.na"-:; c i g a r e t t e tot'->.c ,os '/. ..yJ.vwn . n Appor.-- 7. T) H'l^r.g w i th

tho fi-voragc oovicont::-"•!;! '•:".* J-'OV Turkish tobaccos .

U?ht; u i f fc- 1 n-iâ or s ••'.. ol'-rnnnts fti"? q.a.'te hif?he Ti-.

oo->.CGi:"!;i'-'1tifa of ?-• i r X.:-''ui>'--.. or.p irrat t" tobn.ccf; i s p.ppreo:.

^h^r then i r T-*:-lw.sh br^nr ts . v'his ?s du'; t o th.* uco of

-'-a -.J-f •'•:.vc r r i r ^ p-fco:.-»'.frj p.5y>iod 73 .4 •:.),

bv.m.- l.s ; i , '• 5 • r-r.icp cigp-rattrs or - .^ . r -d b "

Univ^yvJity of Krar4jncy Tobacco •"i,nd Heal th Hesonrch I n s u i t u t " ,

h^.s iu".v - h^.i. • ^r p.nd ' n r.onton'. th«".n rh'? oLh- ~' -,Trr'.c-n ".nd

Turkish b r a n d s .

-hr- •;onc.'-Vitr"J.ions o K Cs7 ?r|.P L- and TJ. a r e

n.pprc-ci~bly h i^h^ r i i Tv^k" sh îf- \'."cxi t o b ' o o "'•'hs>n in o t h s r

"hr-^nds. K rnA p.°- .",r". ^bout •-•- t imos acre in '.!': - ;ri£h "or^rda

th"n i n

A?sariic conoentr^.tior. in Turkish cigp.rotb;, -job cc--) is

much loss thnn in American brands me. i t lo report.":.1, th".* Aa is

not dotuctod in Ir'-ni^n brands, pnd this is pr--jum^blj- 'becûao

-".t present p-rs'.iic insect" cides =?•••. not usi?d V" Irf.ni.~.n tobacco

( 7 3 A l ) .

Sslsnium concentration is ".prsr^cir-.'bly lowor in Turkish

oigarott'? tobp.coo then in both Apisrican «nd I--n.n:.-'-i ?-^nds, »:id

Sb is lot»er thîi in Am':ricari brands„

S i l v r , gold ."nd zirconium frn net <io.-.ctod in Turkish

t to tol-^ccos. Th. differ..-'ices f-nd the pvosonce if silvor

is ^ttributfid to handling of tobacco by "••orknrs whoss Ivnds may

1 .-. '. -.n v-. contact with silvor coins could lor.d to Ag

cf.-.t-Vuir^ti on Pit .'f'riou..-; poin-1- in thn m"nufr-cti.irin£ run(70 N l ) .

This is not I'^r- CPS* for Turkish oig-TOtt'j tobn.cr;r s i n e silvor

coins • ••* on1:- of cu--r«noy in Turkey.

6.-2 POJC .. »nt Xi•".ri...r'.i"-;nc- ..± 1"" ni-.iii.- into Tob':•;••) ish

Althoagh th". df?I.Grmii.]/>tion of tr^co ol vjnt roii3nntr-"tions

in cig"retto toVcoos ffi''"•-- p'"' id^n .'•'bout th'? pl-"nt i t se l f f.nd

the eff-cts of "; oK'TTifj, i t i:r-"-.s necossprjr to p.iv.lyze the tobr-cco

"•sh for tr^.co olcin9vit=!, Th-••-foi'"» r-itn--1 th .n discussing traco

<5lpmont conenntr-tions -'n "sh, i t is bpliwv-?'! to be more

snlightcning tc 3ntf?:<-pret thf- resul ts in tf.riris cf the pflrcont

transference of these trace elsments into the tobfcco p-sh»

Ths- p - . r c 3 n . t t r a n c ^ - - . e n r " - : va.l\xms :~x-x 4±\-:->.n -r^ T a b l e 5»

As i t 5s s*-.?n from Table 5> ths percent transference

velu'-s for ths Hlîu^nts incr^ppft in tho following sequences Hg,

Zn, As, S->, Rb, Bs., Th, Hf, Cs, Br, Eu, Co, Cr, !>•<}, K, Ce, La

«md Sc. Volatile pl^m^nts like Hg, Zn, As, and Sn h^vo the

lowast vftluTa as ^xp'.ctod, in oth~>r Trords, they ev noro easi ly

trfnsfsrrrd into tb-; smok3. I t i s interesting to note the.-; the

tos;ic eler-snts in th--> cigar-, tt'? tobacco hav- low

in th." ash <*.;S. -.m. i.';h?d jn tLo smoko.

40

The percent transference values for the each brand of

cigarette tobacco differ but follow the above sequence in general,

The differences in the sequence of the elements have no correlation

i»ith the concentrations of the elements in the tobacco.

The levels of trace elements in the cigarette smoke

condensate have been determined by Nadkarni and Ehmann (70 N l ) ,

and the percent transference of these trace elements from tobacco

has been calculated. The percent transference values for the

elements into the smoke condensate decrease in the following

sequence: As, Se, Brt Zn, Cr, Se, Cs, Co, La, and Fe. Even the

volatile elements like As, Se, Br and Zn have only 6.29, *»54»

2*41 and 2.JO peyoent transference into sacke condensate, and

all the other elements b»low 2 percent. This is a good agreement

tettwaen the two investigations.

It i^,af»*%. ta TMt* that a large portion of trace eleasats.

in the cigarette tobawo. <t% f«ft in the ash an4 •nly *. «•»&

fraction is tr?n.sf.3,r*eG An.t» the smeke.

B. CONCLUSION

The results of Uiia work show that about twenty elements

can be dotftrminad In Turkish cigarette tobaccos by instrumental

neutrm activation analysis. Some of the elements present in

for«ign tobaeeos suck as Zr, Ag and Au were not detected. The

differences in the number and concentrations of elements may

depend on the chemical compositions of soil, fertilizers and

inseetieides used* The effects of these must also be

investigated.

The contamination of tobacco from surroundings during

storage and processing nuat also be investigated.

41

1

;2 0 1 ChMwick, Z,, Proo»Roy,Soc.A0 12£, 692, 1932.

36 H 1 Hovosy, G«. Lovd, H.5 Kgl, ]>nsko Vidonsk^b,

xilsV'b, M'-th.-F^cModd,, 1.4.. "No* 5, 1936

49 5 1 Rubins on, W,JS, 0 -.ChGmcPhys.12,542, 1S49--

51 L 1 Lewis, WBBOf llucloonics, 12, Ho. l0 o , 30, 1954

59 C 1 Ccvell , D.:••.-. Anftl.Chem,,- 31, p d .""-:-:79O,/ 1959 =

64 Wl Lvon. J r o ? WjSc, Gfuido to ictivf>.ticn ir.- ' .lysis, DB

Tan Noti-cr^nd Company, I n c . , TTiw York, 1964_

65 L 1 Lnnr'bx., JJleA*, Thoi:'-. 021, S,J , (Sds.)» Activation

Analysis, Pr inciples ».nd Applirs^.tf ons, Acf.dr-mic

Press , London, 1965*

66 D 1 Dc^.rnF.loy, G-,, n.nd Forthrop, B:C3 Somi conduct or

Counters for Wuclop-r R^di^tions, 2 nd od t E n.nd

F.K. Spon Limited, London, 1966,

67 W 1 Wynde: , EOLC, Hoffmann, D., Tobacco and Tobacco

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69 H 1 Hannerz, L, f and J^rnslov, A., ITature, 223«

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69 1 1 Lenihan, J<.M<.AO, Collected Papersi Volo3. Activat ion

Analysis5 HfistoTn Regional Hospital Board, (Jlaskow,

1969.

42

59 ".T 1 W-' lkarci , E ,A, e Ihmp-sn, W.D., T n ^ . r - u - ^ n ^ l A o t i v e i i o n

Analys is of T O > O J O P r o d u c t s . Jlc".. - ra T-=v:.is i n

^ctrv^. t io- ' .4"i9.1y<3-'.f!), NBS, Sp-sc.Pu'jl .Nc. 312, V o l . 1 ,

p .191-196 , 1969.

69 >T >? w.?.:.icn , M,,. loan !>„, -Tick, H . , Shap i ro , S . , and

L'isrds, G.P... n?^ T,on c 9 t» 2,, "> 329, 1

70 IT 1 Fucl'S'-.r T? iiV-.iiq.ufis i n Fnviro^r.-rj.b^.l Po i l r .o ion , TAEi

S-g.lzû-g, 1 9 7 0 K

K="-7iog:>o"L, T. >:-sr3c ,4, IT, 'p.325-3i»v > 1970,

71 K 1 Kni,7«si*, P.. . P-irc?.;-l - s of A c t i v a t i o n A n a l y s i s ,

i71 IT 1 Hucleo.r Msttoods in E:iviroiim-nr-I .. -.-'-rch, AITS

Trpic.-.l Mating, Univ. of Mis?ou.'.;. Crlunbi?, 1971.

72 Ji 2 ITuclep.r Activ-tio:! Tc;chnic|.Tie 3 in the Ldfq Sciences,

3"d:.-igs of s. Sym., Bled, 10, 1972.

72 E 1 Rhodes, J.E., Pre.dzynski, A.HC5 and Sieb i-g, B.B.,

ISA Transactions: 11, 337, 1972.

72 S 1 Scwarz, K., Nuclear Ac+^vation Tschniq.uss in ths

Life S-.irr>ot.3, r;;jc3-djngs of s. Syn.. 331 •?«?., 10, 1972,

43

73 A 1 A b s d i n z a d e h , 25., !'• j a a , B»

•Jlioin. 1 4 , p : 1 3 9 - - - 4 5 , 197 3

75 0 1 Coombor, D e l - ; Radioohi=im:loal M^-thorLa i n A n a l y s i s ,

I ;u-:-r. F r a s s ; ITSJT Y o r k , 1 9 7 5 .

75 0 i Ondov, J . M . , Z o l l o r , ?',.H., Olmoz, I , , AI-AS , N.K. ,

Gordon, G*E-.. T</-Micit,3l] l , L.A... i'-r.:' K.'.{., P i l b y s 1 ,H. ,

Shah, K e B, , :.:id l U ^ a i n i , R , C , An.-': '-.••-i-, 4J.- 1102,

1975.

75 I 1 I n t o r n a t i •>n£.l ojnnposiun c.a tho Div-ilopF.^nt of Nuclear

Basftc. .nr ch.ii:j.v s, f o r tha Ti"'-a.sur-(?'n^nt, Dotfiotion and

Contro l of Plnviicnu'-ncal P?ilu;.^2..ts, Vienna . 1976*

76 M 1 Modern 'ihr.^nds i n A c t i v a t i o n Ane lyors , I n t o r n a t i o n a l

^nce , Miinchou,

44

APPBiTOIX A

Biological Si'foots trr./l Major Sourcof of Several

Toxic Tri*-"^ Elîm-ints :>n fas Environment

Arson!o (As"); This i s a v o l a t i l e el'smont of high

t o x i c i t y o: . i... «•-! ijn; .^rity, or ever, a:: add i t i ve , in 'both

meta l lurgica l an-5 minor^l tr< atment processsse- Con.1, poti-oloum,

de tergents , smelbers processing a rsen ica l oros, i n s r c t i c i d 3 s ,

horbicidras and p.T:sticii^s aro the mrin sources .

Symptoms: Vprif:ty of g a s t r o i n t e s t i n a l d i s o r i o r s ; skin

d isorders , prota^ly csrc:.nog{?nic. S ' l p i n s wnvy le.vgo dos^s for

toxic o f f s e t s . Modcr^.tn ^.Founts protect P.gninst solenium t o x i c i t y ,

Loth?,l c!oso ov^r 24-hrc period i s ?V;n.t 4';> mg por kg of

body weight in ma

Barium (Ba^; Barium is not general ly s igni f icant

sincn i t i s probably net pssfditip.l to m«.n and i s hardly t o x i c .

BoryIlium (Bo);_ Goal burning, rockot fuel; new uses

proposed in nuol3Bi powor industry, ar-> thr; m".in sources„

Symptoms: Dogon^r^tive lung disease call9d "• >eryllosisl%

lung cancer, acu'L? and chronic system poison.

Threshold limit for Bo is 0.002 mg p'-sr cubic motor of

air, and breathing air at this concentration level, lsads to

accumulation of Be in lungs,

45

Ca&crl.'am (Co); •' -: '-•.•. i s g&n-i-r-lly toxic and a

cumulitivn poison in man and. ;.r.i^p.?.t-- Si'.;i+,;•;.?.>> tin;.' industry, COP.1,

I.TI'J mirn.r;.,, phor-jphat'. f-rtiij.z^r'.; i r? t.ha nr-i'.'i sources.

oyaptomst Hjp.srtonsion r-.rid ctVvr cr-.rdiovf.sculpr diso*-sos;

in v':cy Mr;h dos-53 ct us-:S "ouch-ouch" ciis-^Fo, painful ^ff]ic-';ion

of bOii.-s r . joints 1 ,. o'tiibl. cnr

lngns wlon of 10 mg or moro OV-^T fr>7F -Ip-ys mi«!" OOUSG

severs prolDlGRis ^

t (Co); CobB.lt i s nnta.TDoile^-.ly significp.nt.

I t i s an sss ,>ntiPl ol-::r:nt ".nd included i::i tlii :iJ"-°>Tr:Ln B 12 EIOIGCUICS,

"but i s p-lso rcgf.i-d-.il by cc."/ iav'ssîgôcrs as ;n.i-cinogenic. I t i s

toxic to plants

ChrOEium fCr) • Cox j •• _r:P.ting; -;•• 1 -.-t^rfiing pigc-nto,

and chrom-'".lloy industr ies arc th° sources .

Ohromium is p.n important QloE"-nt sine? ii i s ossnntial

to mP-n for the mr?tn"boli!3otirn of gluco?-- s On the ctnor h- .nd i t i s

also toxic and c-usos psrfor-^ticn cf n^sal septum, chronic cp.tp-rrh,

p.mphysr>m?.j ^ni c r c i n o gonosis.

Threshold l imit for Cr i s 0.1 mg per cubic m^tcr of a i r

RS chromic ncid and chrom"-tes.

Mercury (Hg) s As in 'roll knows, nnrcurj- i s n

poison in man f-nd the CRUSG of s<?-/3r<°.l dinnsters in

in recor,t y-».rs. Chloro-Rlk«i-li process for manufacturing sodium

rand chlorine; papr?r ar.d pulp induetrissj plas t ics , paint and

L-V.VTiPO iTbivjfll industr ies | herbicides, sli;):icider-. And fungicides

..n • "=. f a?2i of so~.d d"'-.3sir.;. . arc ^he m'.in sources of mercury.

u-y is tlis rncr-t h.~.a<vH.ov.y for;:- of m'-i-cury,

and oonorv^fcrat-.s in ay/patio o;.-g?.;':'sras such °.s fish, crab, shrinp,

Iol3c,t..r, •. .., ,t:;oai ^-A ;z>.au ~ij low r.onennbrp.tions in watnr.

Mr-tbyL^-roury li-.s the pbili t j ' ••:•<: •••incjtr t fi Dod-br'.in-b".rrier

(69 H 1 ) .

Symptoms; J)<-n\r'.gG to brcvin and n~rv'- .'s eystRin, may occur

when daily intake exeseis 0,5 Jig leading to c< ppm in b-?".:ln,

Ni.ckel_(]£±);.. "he •'ioxic iirûr^ of this elGm^nt and

i t s common industrial us; maires i t imp'vta-.-.v in environmental

studies. St?el a-nd niotel-sl loy industry, nicknl pitting1, afabastos?

coal, fu^l o i l , tobacco smoke arn the sourcos of nickol. Kickel

cflrbonyl, Ni (CO), is a known cfrciiiogan,.

Symptoms: Uickol causes lung •.•Tic r i?.i - p.o form of

carbonyl; dermatitis, respiratory disorder.

Threshold limit is 1,0 rv; as Ni or Ni in i t s s a l t s , but

0.007 mg r.s nickel carbonyl per oubic motor of a i r ,

Load (Pb); This toxic clement has probably roceived

morfj popu!i?r attc-ntion than any other a i r pollut-ar.--. -Automobile

exhaust, conl, soil and rock dust, volcanic and marine aerosols,

metal smcltors, battery and pigment production plants are the main

sources.

47

"! 'D-'.rv.g.- -'JO brs-xri nn<?. ncvous system; b^h

•i cor-icrs. convu ls ion ; p.t I n 7;-v\s c u s ^ i iv.usiv'. '-nd i r r i t a t i o n .

Threshold 1- xi'c '"(.••J. Pb is 0»? ma j , •• ruMc motor of ?.ir»

Proh? .us ,-•>. y °.ris\- ".'h-. i t oxor^ds 0.8 p-j;: i r TDl

_(^>..„-. '-n-tor'. .3 ;-. in "'-'lis ;.l.om'.:it ^-ri-jos from i t s

toxi'- ••"'•tu:,'-- >T.O. i t s pc"3-j.ibi< p.ssociP.tion with sulphv.i- ~'.:i tho

"ijnosphsrc,. I t r l s o happens to ~b& r.n osrr!nti<'"- el^msnt. Cor'b'ustion

of p.ny high P' iphur fi'.-5!; ro t a t ing of sulf i^ • > r :p *•:•:> tlirj m«i.in

souress ,

Sol<siiium nay cp.af3f. dont-".l cnv i t i s s , ' b l ind staggers" in

animals, ».nd is circi^. •>-,•.-ii .c in r"'.Js,

n.! doso over 24--hr p- riod is p.hcv.l 0»0O4 mg per kg

of body weight in Tns.mipr.ls.

Tp.na.dium (V) t Tp-n''>aiiin is D&L- . -.-.-;. tr- gosio orgP-nism

though not to mar., pnd i s mo^-or^tr.ly t cx io , I» i s Introduced in to

the -tmQsphc-r.o from the burning of o i l ^nd OOP.1 r.t povr^r s ta t ions

p.nd industrip-l r r c a s g". i o ra l ly -

oausos cp.rdiovascular disi5"S3, f»nd i s a.

c '.rcinogenio.

.d l imit for vanadium i s 0.5 mg 'pO;- dust or

O.I TP« T20c fumo per cubic mater of a i r .

Zinc (Zn)i Zinc is a. suprisingly comron olemont

throughout tho atmospheric snvSrenmsnt bece.use of its relatively

48

volatile pi-operty, ..ir-?. -.;-.^- Mid rftfiî"^, c '. nino cpiv^.niîug are

1 "• - s'm.r'"?3 of poll i.:'" ".on«

'.rinc causes dermatit is, hypertension, a.no erteriosclsrot.i •

R nf • ^.: ar t disease c

Threshold limit f<--r air.c i.-j ^.,0 n:,z ZnO fume ?«=r J I M ?

mratpr of . _'e

49

4PPENDIX B

Detection limits for «cf:'vAticn

Sbutron activation analysis is quite capable of

determining many elemants at nanogram levels provided that

indiv.'dua" • diiomif!3i'.''. 3 &x-. formtd and can he at least so

from .;f?.ch othor?

Tha offoctivenoss and th? detection limit cf bha technique

depend on several factors including nucloar yro^si-tios of elements

and counting procoduros, nnd thos^; can hn summarized as follows:

1, Crcssr .Scj.rcioui ^ho v bo of nucioT reactions in a

given irradiation ays torn is determined not only \>j the numtor of

incident «nd target nuclei pvailnblo for interactions but also by

th© probability th^t an incident particle: v\\i ",-aot with a target

nuolaus. This probability, oxprr;ssed in tor. s :f an area per

incident particle, is called the cross section of tho particular

reaction and is somewhat analogous to the rato constant k used

in choaiicnl kinetics*

Tho cross saction has the dimensions of an area, n.nd is

expressed in the units of the barn, where

0 A 91 barn = 10" cm •

The induced activity is dinctly proportional to the

«ro3s section and pp.rent nuclidfis with large cross sections are

more easily flet^ct-d.

50

In gr-nrair.l, thorm'.l neutron activation cross sections

aro much higher than that of fast neutrons, protons and photons.

T

2a Isotopic •i~.'bud:--'i):.iSi of the, .parent roiolidBi The inducsd

r cîvitj' '•' proportional to th-t amount of a particular element :in

tho R-'.niplc , hut not «\11 of tho stable isotopes of s> givsn elemsnt

will Vcoi" active during irradiation.. For example, all stable

: 07golc1 3 in the form ci ' .= ,;. U^.trpe and wilj , therefore, "be

subject to activation to Au by (n.<3 ) reric :.o~<- TTowevsr,

naturally occuring ii-on is found in four st*.!' isotcpic form?-,

hesn .re 54Pe (5»82#): 56Ps(91.66/0, 5 7 5 8

Only Fe p.nd Fa wi? 1 undergo (n,?^) reaction to give active

products* Usup.lly Fc(n,f/ ) F-3 reaction is utilized for the

deterrain?.tior. ;f :-or in th3 saaple.

5g_Activg.tjon. flux; Tho irradiation flux .-.xprsss s th&

arsa-tima density of the bombprding particl-s in units such p.s

tnutro;:S ;-;r sq.uars coritim = tTr por second, ,".-j >i'gher the flux,

the greater is the indued activity fox- •:*. giv.ru

irradiation

Sinco noutron •'••.ctivatioa analyses "rn in most cases

cp.rriod out by irradiating also the comparet.! 3 st^.ndrrds

simultinoously with unknowi samples, tho constancy of neutron

fluxes is r-il^tivoly unimportant,

4. Irradiation timo; T7hon a radioactivs spscios is

produced. \>y irradiation in *>• constant flux oi* particles, the

51

induced activity ie given

A = Nrf0 (1-e" Ati)

J'hc tors, M-G'***) is c/OAcd tho "c^tuwtion f-.ctor".

As t?n irradiation tiim (t^) bocoiiMS largo compared to the half-

life ,;f tho product (in /p)j the saturation factor approaches unity,

and t'-.fii ma- jium •\c+-iv3'ty is obtained. Iriadi-^tion for tvro hnlf-

livsd produces 75 ' of fcho m xru-uin: "ctivity, P,VI;1 th^ liicro-.so in

radioactivity roach.'.-s the* "economic law cf '-'.'rji Aiicinishing returns"

and, no significant i.-'\-rea,3s in activity is <fbj. in d '•vith

irradiation timo muoh longer than two cr thr3c; nnlf-livvs • When

izradiation "kijt -f i« costly, i t is unoconoarical and impractical to

try to roach too saturation iinlsss tho nuclidi has a half-life in

the ordsr of aeoonis ox r-.% meet mi:iuto3<.

5-- Cooling tii.ic-t In the thermal noutron activation

analysis, tho main activities produced aro iv.i to short-lived

species, for example, in tobacco IS a >-,nd ' Tv (li---If-livGS of

\5*5 hr and 12.4 hr, rospeotively} do cay quickly, »n>l aftor a few

days of croling i t is possible to obs-Tvs the •well-defined

photopraaks of 14°La(1.675 d)» 82Br(l»479d) and 76As(l.l04d). Those

and the other short-lived activibins decay to insignificant levels

after a period of 30-45 days, and most of tho Inng-livod nuclidos

can bo measured at this stage.

Docay time correction is necessary in both "direct" and

"comparative" methods of activation analysis, in ordor to obtain

the activity of nuclidea at a definite time prior to counting.

52

6e Counting time; Counting tiire, like coding time, must

•-Q ad -iST. -.u according '.-o i>,; "•>-:> If-livos of radionnclides. Counting

.:. -. ây -.:.:?y from 10 to 15 njinutos for r.i.?rL -livaJ nuclidss to a

few h'-.urs or more for long-livsd rnolid-g. For lon,j cooling tim^s

Ions counting time is necessary tr: obtain a p^sk above t\c backgroundt

?•: T.-jfoo (|pf. ds\. oto' i. Potootlori l ic i ' oi'

analysis depends largely on tho gs-mma-ray sp^ctror:. try, in which

the f i r s t s-:.:p is the ''J.Gt.-:ction of r«?-di.?.+"i.on.. Jn 2o^:r-:i i.-r^ctic^,

detectors ojnploysd srn ljs.se-d on ionizp,tion of g', <,s ( - , 5 , , proportional

and G-M dot- ci;ar.-s) 5 "rcvi:-' biofi of crystals ^hioh rosu.lts in

luminsscrsnco (- .g , , scr.ntillsi.tion dotec+^rs^, or i^niz^tion of solids

( e g , , somioonu.T'cto."" d ts-3+crs)c The G-M tube- is n."t useful as a

detector for pulso-hcight analysis in dstnct-'on nnd identification

of individual radionuclidos = The sc-miccnductor iotoctors have soveral

ad-/antag-.s r ^ r the gas-fill ad dotccto-c, ••..-c r^r'or enns boing the

number of ^lectron-hole pp-irs prrdU'.- :'•'. :>.?. :.-3 solid compared

the -.iectron-ion pp.irs produced in uho gas .T.": - ha higher

density of solid, Both p.dv.°nt<'.gos rosult in potentially higher

resolution in th.j measurement c :..;• incident particle onergyo

High volume G-j(Li) sclid-stat". dotô1 yzs ars most commonly

used for multi-element analyses without any chemical treatment

•b»r»s.u?se of the high resolution pow?r for a number of nuclides T7

comparable gamma -ra./ eno

53

•f " T XiF !••!

Elonon-

Na

Mg

Al

S i

Gl

K

So

Ti

Cr

Mn

Fe

Co

Ni

Cu

Zn

As

So

Br

Rb

3 r

Z r

Comparison of D':

Acx--vfi-tio:

:

b IFAA

0, '0035

0,03

0.00005

0.0015

O.OfV,

0.0001

0.01

O.OOOOji

O.A^

0,001

0.0C5

0.00035

0.083

0.0001

0,005

0.00015

0.0015

0.03

0 .015

a An- .iysi r.

uimiv of T"

0-005

0 / 1

0,o

n.005

C.I

0.0^5

C.0.J5

0.01

0.1.07

0.01

0.00J

0.07

0.5

0 . ?

0.005

0.0:1

5.0

toctj on Limits

.:id Sp . otrochom

.1. - , J . ^ • -i . a - . ,

PP

0*0002

1 , 0

20

0.01

2 0

1 , 0

0 . 1

2 . 0

10,0

0 . 1

?000

0 . 1

0 . 1

by Krutron

ica l I>I~ "Lhoi?.?

Colorinotry

0,0<

0..002

0-1

0 04

0.03

0,02

0-001

0,05

- 5

0-0/.,

0,03

0,016'

0 . 1

0.13

54

B-l continued)

31 c nont

Mo

Ag

STD

Cs

Ba

La

0 ,

Eu

Hf

Au

Hg

INAA

0.005

0,0055

'VOOO?

0,0015

0.0025

r.oooi

0.005

0.001

0s000i5

0.0065

L-UIV'J of !0

AAS

O.i

0,01

0.-2

0,0.5

0,1

80

0 2

15

0 1

0-2

-tnotiV/

YP

50

0.5

3

5

20

200

100

Colorimotry

0.-1

0,1

0.03

Oe25

0 . 1

0 = 08

, (VI K l )

IEAA : Instrumontal Ktj.utron Activation Analysis

AAS ; Atomic Abaorpticn 2i^

FP j Pl.-ac T^Lotomotry

55

X C

Elsi&ontal Cono'iitrations i:i the ITatiotip-! Bureau of

ônn-i-'^l Coal St^nd^T/:. P.ofor~ncQ

?,L?~r r i a l (75 0 l )

(concentrations ug/g

Jjp-.55ient_

U?.

Me (9?)

01

Sc

Ti

V

Cr

Mn

Co

N i

Zn

As

So

Br

K"b

414+20

0,20 +0,05

i»S5 +0.13

890+125

0*2:8 ?•«), .••'

0 * 4 3 '?0,0 r^

3-7+0,3

1040+110

36+3

19.7+0.9

43+4

0.84+0,04

18,4+4

30+10

6.5+1.4

3.4+0.2

19e3+1.9

21+2

Eljôjnt

Gr

In

Sb

Cg

Ba

La

Cn

Sn

Yb

Lu

Ef

Ta

W

Th

U

C on aQntT^tion

161+16'

c.ofi+o.c;.

0, 20-1-0,12

3.9+1.3

1.4+0.1

352+30

10.7+1.2

19.5 J1

1.7+0.2

0,33+0-04

0,.. 23+0.05

0.7+0.1

0.14+0c01

0.96+0.05

o«?4+o.O4

3.2+0.2

\.41+0.07

56

APPENDIX D

Comparison of Elements! Conc^ntrat5.ons in Ciffa

Tobaccos of Turkoy, USA and I r a n

( c o n c e n t r a t i o n : jig/g unlns^ $ indic^-t ••d)

ill <••;,: . m i

*(*)Sc

Cr

Fe(#)

Co

Zn

As

So

Br

Hb

Zr

Ag

Sb

Cs

Ba

La

CG

Eu

n-rAu

Hg

Th

"•ftark-:."-.i

2.6

0.10

0..7"7

351.0

0.1C

59.2

17.7WcO.

N.Oc

0.10

0*20

64.61,0

1.870.0340,15N.O.0.080.32

/.amrirbrani G

•'••O9

' ..3

0-42

i u

7-3

<jr.3

36

7.1

2-5

14.1

0,51

'•i (69 Nl'Ui'P.rd ].'

0.560-24

0.7925

1,5

58

16.3OC64

7=4

0,33

, 70 HI) j'r«.iiiirn (73 Al)brr.nd 1A1 Zarrr'n

0,11

- <>9

0.0?

1,06

69

3,57U2?

123

0*20

0,1?

0.07

1.96

0.08

0.18

0 , 2 4

0 . 1 ^ 2

>.-

0.-06

0=349

51

N.D,

1,23

108

21.8

0,20

CO63

c 14

5-.-0

0.394

0*98

0.019

0.124

0,024

I1. .19

'.", 183

Oshnoo

0.270,311Oc21

0.100.60

55.8HYD.

0.90206

16,7

0.050.1170.18

4 = 7O0670

1,540.0360.1460.0210.90Od94

57

-f M. Cetin GOLOVALI

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