198

Techmcal notes
errors xn o u r procedures is faclhtated b y regular checks of results m o u r secondary s t a n d a r d instruments.

t h e m . T h i s effect is mmxmtsed ff vmls are centrifuged i m m e d i a t e l y after s h a k m g or after accxdental moistenm g of t h e b u n g ( T a b l e 2). F o r most y a n d h a r d fl emttters t h e acuvlty lost to the b u n g ~s m e a s u r e d m a c a h b r a t e d 7 spectrometer. F o r emitters of soft r a d m t i o n s only, the loss ~s estxmated, e g by using results f r o m solutmns w~th mmflar phymco-chemxcal properties b u t c o n t a m m g eamly m e a s u r e a b l e 7 emitters T r a c e c o n t a m m a t m n of b u n g s occurs even with stable solutmns a n d m the absence of d~rect contact because solute dtffuses u p w a r d s t h r o u g h the t h i n layer of motsture condensed o n the wall of the vial F o r example, stoppers o n vmls c o n t a i n i n g soluuons of SCo a n d aSTCs h a d a c c u m u l a t e d a b o u t 0 1 p e r cent of these acttwtxes after I0 m o n t h s of storage Wxth few exceptaons the c o n t a m m a u o n o n b u n g s ~s so small t h a t ~t ~s unnecessary to d e t e r m i n e ~t to m u c h b e t t e r t h a n 4-20 p e r cent Since solutmns r e q u i r e d for acuvxty standardxzatmns are c o m m o n l y h~ghly dilute ( ~ 1 0 0 #g m1-1 total sohds), t h e r e xs t h e posmbfllty of loss of actxve runs to the p y r e x glass c4) Th~s loss is readily checked a n d ~t xs rare, m o u r experxence, t h a t a d s o r p t m n onto the glass accounts for as m u c h as 0 05 p e r cent of the acuvxty p r o v i d e d the correct solvent m used 3~ O u r usual p r o c e d u r e is as follows Before a vml is filled we m e a s u r e xts t a r e weight (wxth the b u n g m p o s m o n ) a n d also the wexght of the b u n g , b o t h corrected to selected values of a t m o s p h e r i c t e m p e r a t u r e a n d pressure Solution is weighed into t h e vial and w h e n all welghmgs h a v e b e e n m a d e the vial is press-sealed, shaken for 10-90 sec 5~ a n d l m m e d t a t e l y centrfl'uged W h e n , a t a later stage, solution is to b e r e m o v e d the w a l is first centrifuged, the a l u m m x u m c a p ts r e m o v e d a n d all wexghts are r e d e t e r m m e d E v a p o r a t m n of solvent whilst the w a l is o p e n d u r i n g t h e weighing of the b u n g a n d the extraction of solution xs generally below 0 05 m g a n d ~s corrected for ff necessary. All results are preserved m a record system w h i c h permits us to trace the hxstory of each solutmn m every detail T h e effects of storage o n the results of standard~sattons increase wxth time a n d d e p e n d also on the phymcal a n d c h e m i c a l characterxsttcs of the soluUons Typtcally, after 6 m o n t h s storage the increase m r a d m a c t l v e c o n c e n t r a t t o n d u e to loss of moisture ~s b e t w e e n 0 2 a n d 0 6 p e r cent while the loss of activity to the b u n g ~s a r o u n d 0 1 p e r cent T h u s there xs a n e t increase m rad~oacUve c o n c e n t r a t t o n by u p to 0 5 p e r cent As a rule we accept results corrected for storage effects u n t t l the u n c e r t a i n t y m the correcuons reaches a b o u t 90 p e r cent of the nncert m n t y m t h e orxgmal c a h b r a U o n T h e d e t e c u o n of

E
G

P.

JOHNSON

C LOWENTHAL

Austrahan Atomze Energy Gomm~sswn Research Estabhshment Lucas Haghts, N.S.W. 2232, Austraha

References
l. MERRITT J . S a n d TAYLOR J G. V. A.E C L R e p o r t C R G P - 1 2 5 6 (1967) 2 LOWENTHAL G C Int J appl. Ra&at Isotopes 20, 559 (1969). 3 The Rad~oehem~cal Manual (2nd E d n ) T h e R a d m chemxcal Centre, A m e r s h a m (1966); see also Y LE GALLIC et al S T I / P U B ] 1 3 9 , SM-79/52 (1967) 4 BAERG A P Metrologza 2, 23 (1966) (See also User's Grade for Radzoactzwty Standards. Subc o m m i t t e e o n the Use of Radloact~wty S t a n d a r d s N A S -N R C , W a s h i n g t o n , D C ( 1 9 6 7 ) ) 5. RYTZ A , COLAS C a n d VEYRADIER C Some

experxments on the dflutxon of radxoacttve solutmns Unpubhshed report ~ssued by the Internatxonal
B u r e a u of Wexghts a n d Measures, Paris (1969)

Intematxonal Journal of Apphed Radlatlon and Isotopes, 1972, Vol 23, pp 198-201 Pergamon P ~ Printed in ~ortJaern Ireland

Rapid Non-Destructive Analysis o f Ancient Bronzes

(Recewed 16 September 1971)
THE PROBLEM concerning t h e d e t e r m l n a t l o n of m e t a l contents m bronzes is of g r e a t interest m the field of works of a r t I n fact one m i g h t hypothemze t h a t each age or ClVdlzatlon IS charactenzable b y a p a r t l c u l a r composltlon of bronzes U n f o r t u n a t e l y very h t t l e c a n be said a b o u t this a r g u m e n t because of a q m t e complete lack of available analyses for example less t h a n 25 quantxtatwe analyses of greek a n d r o m a n s t a t u a r y bronzes h a v e b e e n p u b h s h e d since 1970 (a) Thls lack is p r o b a b l y due to the destructxve c h a r a c t e r of typical chemlcal analyses M o r e o v e r each analyms, m a d e o n single samples t a k e n from some p a r t of the bronze, do not h a v e to represent the average composltton of the b r o n z e itself satisfactorily W e p e r f o r m e d m e a s u r e m e n t s b y means of X - r a y fluorescence analysls ( X R F m the following) which, as xt is well known, is a non-destructive m e t h o d characterized by short m e a s u r i n g tlmcs, w l t h the a r r a n g e m e n t we used, m e a s u r i n g tlmes of a b o u t 100 sec were r e q m r e d

Techn=al notes

199

15000

./ca

1000G

J
~]Sn

Pb counts uttlJzed m content evaluation counts utd~zed Jn content evaluation

5000

50

I00
Channel No

150

Fro. 1. Typical X R F spectrum of a bronze. Content evaluations have been performed by n o r m a h z m g at 105 counts the spectrum area between No. 1 and No. 199 channels.
xJO3counts 12-II-

Pb %
20 o CohbratJon point
Experlrr ental point (seeTable II )

I0~5 9 87-

IOq

5--

4~
3-

o
5

~ 5o

,o

,s

I0

2o--S~%o
2[5 x |O3counts

15

2~)

)erLmental poL~ts concermng the bronzes of Table 2. Fxo 2 Cahbrataon graph and the expc
2. E x p e r i m e n t a l The X R F experimental set-up has been described elsewhere (2.a) Briefly, m the present work we employed a 147pm-A1 source (45 mC1, brehmsstrahlung spectrum), a Xe-filled gas proportional counter (Be w i n d o w thickness 0 5 m m ) and a standard electronic equipment mcludang a 400-channel pulseheight analyser, the whole ,s easily transportable The m e a s u n n g head (source-counter assembly) dehmlts and analyses an area & a b o u t 5-10 cm 2 The analysis revolves a layer with a thackness of about 100 Fro, therefore the examined area must be as clean as possible, l.e without patina and corrosmn products.

200

Technwal notes
TABLE 1 X R F evaluation of s t a n d a r d bronzes' composxtlon (an per cent) Lead 134-02 034-02 014-02 0 2 5 4- 0 2 184-02 4554-025 774-03 684-03 X R F Values Tin 0 4-02 294-02 5354-025 7 3 5 4- 0 2 5 9 0 4- 0 2 5 544-025 934-025 024-02 Copper 9 8 7 :k 0 3 9684-03 94554-03 9244- 03 8 9 2 4- 0 3 9005+035 83004 9304-035 Lead 12 0 0 0 20 47 79 69 Standard data Tm 0 28 52 765 90 50 90 0 Copper 988 972 948 92 35 890 903 831 931

I n Fag 1, t h e X R F s p e c t r u m of a b r o n z e as s h o w n a n d the e l a b o r a t i o n of the results as Indicated. Several samples, p r e p a r e d by weighing a n d mixing dafferent q u a n t m e s of p o w d e r e d copper, lead a n d tan, h a v e b e e n analysed b y X R F spectrometry with the m m of o b t a m m g a cahbrataon m e t h o d for bronzes I n Fig 2, the c a l i b r a t m n g r a p h concerning lead a n d tin contents m c o p p e r m a t r i x as r e p o r t e d , the g r a p h has b e e n o b t a i n e d e x a m i n i n g p o w d e r e d samples Due to t h e b u l k a b s o r p t m n an the sample, t h e aso-concentratmn lanes are n o t parallel to the g r a p h axes T h e relatave c o p p e r c o n t e n t c a n samply be calcul a t e d s u b t r a c t i n g from 100 the d e t e r m i n e d p e r c e n t ages of lead a n d tan I n order to test t h e a p p h c a b i h t y field of the g r a p h we h a v e c o m p a r e d the c o n t e n t of eight s t a n d a r d bronzes wath the corresponding values o b t a i n e d from XRF measurements T h e results are r e p o r t e d an T a b I e I, the a g r e e m e n t with the s t a n d a r d values as excellent. I n the cases of bronzes c o n t a i n i n g zinc as fourth m a r e c o m p o n e n t we h a v e e m p l o y e d different cahb r a t m n curves (4) W e h a v e n o t t a k e n into a c c o u n t the i m p u r m e s generally present an bronzes This a p p r o x a m a t m n gives rise to a copper overestimate very seldom exceeding I p e r cent (5)

3. R e s u l t s a n d D i s c u s s i o n
Analyses h a v e b e e n p e r f o r m e d on a large n u m b e r of ancxent b r o n z e statues, a m p h o r a e , plates, etc gaven In c h a r g e to the Istltnto C e n t r a l e del Restauro, F o r each piece, different areas h a v e been carefully chosen a n d analysed m order to give a sagmficant average v a l u e T h e results so o b t a i n e d from five a n c m n t b r o n z e objects are r e p o r t e d an T a b l e 2 T h e m e a s u r e m e n t s are m progress (4) Concluding, we c a n say t h a t the X R F m e t h o d as very c o n v e n i e n t for collecting a large n u m b e r of reformations, because of the rapadlty of the measurements, of the non-destructive c h a r a c t e r of the m e t h o d a n d of the t r a n s p o r t a b l h t y of the a p p a r a t u s Thls latter aspect wall b e f u r t h e r e n h a n c e d b y using a p o r t a b l e X R F versxon w h i c h employs a modified single-channel analyser I n this way xt will b e possible to c a r r y out easily m sztu m e a s u r e m e n t s o n b r o n z e ' s collectmns, b r o n z e gates a n d statues R F C S CESAREO V F AZ L R ZOI MANCIN! SGIUTI

Istztuto dz Flswa della Facolth d~ Ingegnena Roma, Italy

M MARABELLI

Istztuto Centrale del Restauro Roma, Italy

TABLE 2 P r e l i m i n a r y results concerning the composition of some ancient bronzes (in p e r cent) Object M e d u s a dl N e m x - - M u s e o delle T e r m e R o m a - - I C e n t u r y A D Bronze p a n e l of the C a t h e d r a l g a t e s ~ B e n e v e n t o - - X I I I C e n t u r y A D E t r u s c a n chariot from P o p u l o m a - - M u s e o archeologlco dl Firenze VII Century B C C i n e r a r y etruscan u r n from D o l c l a n o - - M u s e o dl C h l e t i - - V I I I C e n t u r y BC Efebo d a S e h n u n t e (Greek s t a t u a r y bronze) Gastelvetrano V C e n t u r y B C. Gu 85 6 90 8 90 0 88 6 88 3 Pb 14 4 0 0 2 17 17 Sn 13 0 52 9 8 9 7 10 0

Techmcal notes
References

201

] CALEYE R. Chermcal compos:tmn of Greek and Roman Statuary Bronzes, m Symposzum on Classwal Bronzes, The Fogg Art Museum The M.I.T. Press, Cambrxdge (1970) 2. CESAR~O R , FRAZZOLI F V , MANClNI C. and ScItrri S. Not*z~ar,o delG.NE N Anno 16 (n. 11), 57 (1970)

3 C~SAREO R , FRAZZOLI F. V., MANCmI C., MARABELLI M , MORA P , ROTONDI P., Scltrrx S. and URBA~I G To be published m Archaeometry (1972) 4 CESAR~OR and M ~ L L I M Work m progress. 5 CAL~'ZE R AnalyszsofAnczentMetals, pp 112-121. Pergamon Press, London and New York (1964).