A s s a y i n g o f g o l d je we l le ry –

C h oi c e of t e c h ni q ue
DR CHRISTOPHER W. CORTI
W or ld Gol d Co u nc il , Lon don , E ngl an d

Introduction A ssa yi n g o f gol d je we lle ry

coin, w hen melt ed, resu lts in the gold
A ncient m an firs t learnt the craft of
plat ing alloying w it h t he u nderlying W h y as s ay?
m et alw ork ing s ev eral thousand years W hy do w e need t o as s ay gold
bas e m etal w it h a consequ ent colou r
ago, mak ing jew ellery and ot her
change. jew ellery in m odern t im es ? W hy? –
decorative artefacts from nat iv e gold
How ev er, as w ell as t hes e rou gh Becau se gold jew ellery is sold on t he
and copper, w ell before t he Bronze bas is of its gold content . We desc ribe
and ready m et hods of t est ing
and I ron A ges . This nat iv e gold jew ellery in t erms of its F inenes s, in
preciou s m etals , t he ancient G reeks
contained s ilv er and ot her m et als as
k new of 3 qu ant itat iv e met hods for parts per t housand gold, or Carat age,
impu rities , but it did not tak e long for
ass aying gold and s ilver and all 3 are w here 2 4 carat represent s pure gold.
m an t o deliberat ely alloy gold w it h I n many cou nt ries , t here are law s t hat
still in use t oday: the touchst one, fire
copper t o im prov e properties du ring gov ern t he act ual caratages of
ass ay and dens ity m et hods. W e w ill
t he s econd m illennium BC. A ll t his
ex am ine each of these t echniq u es jew ellery that can be sold and t he
natu rally led to the early us e of gold
lat er in t erm s of t heir relev ance in allow able t olerances on t he gold
and s ilv er as coinage around t he 7t h content. I n m any count ries, t he law
t oday’s w orld.
Cent u ry BC. ins ist s t hat each piece of jew ellery is
Defi n it i on of ‘as s ayin g’ test ed – or assayed – and m ark ed w it h
F or g er y o f coin age t he gold cont ent . This is com monly
I t w as not long, how ev er, before the A t t his point , it is appropriat e t o k now n as Hallm ark ing w hen done by
appearance of debas ed or plat ed define t he term ‘As saying’. Ass aying an independent ass ay laborat ory.
coins . A ndrew O ddy ( 1) not es t hat is t he t echnical t erm u s ed for t he
q u ant it at iv e chem ical analys is of a Rushforth (4) has dis cussed this as pect
coin forgery w as comm onplace in the in som e det ail. S ince the p rice you pay
ancient w orld, a fact w hich is m at erial, or object , for one specific is prim arily gov erned by the gold
dem ons t rat ed by t he num ber of m et al or chem ical elem ent of cont ent , u ndercarat ing, w hether by
s u rv iv ing cou nt erfeits made of part icu lar int eres t . I t is oft en
ass ociated w it h t he analys is of ores accident or by int ent ion, is tantamou nt
s ilv er-or gold-plat ed bas e m etal. t o frau d, particu larly w here there is
F orgeries ex ist for v irtu ally all t he and met als ; in t he cont ex t of gold hallm ark ing legis lat ion giv ing
precious m et al coinages s t ru ck in jew ellery, as s aying m eans t he consu m er prot ect ion. A s has been
ant iqu it y. G ilding of s ilv er and bas e determ ination of t he gold cont ent of
t he it em . rem ark ed prev iou s ly (5),
m etal ( i.e. coat ing the object w it h a
gold-rich su rface layer) w as a
t echniqu e w ell k now n t o ancient
m an (1 -3) . I t is not s u rpris ing,
t herefore, t hat gov ernm ent s of
ant iqu ity w ere v ery concerned t hat
t heir coinage w as not debas ed or
cou nt erfeit ed and m any enacted law s
to protect it, w it h sev ere p enalt ies
for those conv ict ed of forgery.
To det ect forgery, coins needed to
be test ed. There w as litt le indicat ion
in t hese early law s of how test ing of
coins w as to be car ried out . Cu tting of
coins w as one met hod u s ed and
many ex amples of coins w ith cuts are
know n, m ade to ensu re that the coins
w ere not plat ed. Acou st ic ‘ringing’ of
coins by dropping t hem ont o a hard
s u rface w as also pract is ed, as w as
m elt ing of t he coin and its
s u bs equ ent s olidificat ion. A plat ed F i g u r e 1 - Undercarating of gold jewellery in the USA (AJM Magazine, 1997)

20
u ndercarat ing is a m ajor problem in cos t and accu racy, fact ors s u ch as I n s ev eral of t he t echniq u es , t he
s om e cou nt ries . Ev en t he US A is not s peed of m easu rem ent , cons is t ency accu racy of the m et hod depends on
ex em pt from t he problem, F i gu r e 11 of m easu rem ent , w het her it is t he use of reference alloy st andards ,
The im port ant point is t hat dest ru ct iv e or non-des tructiv e, size of eit her t o calibrat e t he equ ipment or
k now ledge of t he gold as s ay is s am ple, et c also play a part in run against the test sample. O pt imum
es s ent ial to t he jew ellery s elect ing t he appropriat e t echniqu e. accuracy in som e techniques requ ires
m anu factu rer, t he ret ailer and t he The need for an accu rat e, q u ick a large num ber of reference alloy
cu s t om er. That jew ellery is not t echniq u e, us ing cheap eq u ipm ent s t andards .
u ndercarat ed or debased can only be and a low s k ill bas e t o operat e is a F or hallm ark ing pu rpos es , w e
det erm ined by t es t ing – by ass aying cont inu ing req u irem ent in t he s hou ld als o not e t hat t he
t he it em . Ass aying ens u res t hat t he indu s try. allow able t echniq u es and proce-
gold cont ent m eet s legis lat iv e Today, t here are a num ber of du res are defined in various IS O
requ irements , prot ecting the consum er m odern ins t rum ent al analys is S t andards
and allow ing m anu fact u rers and t echniq u es available as w ell as t he 3
retailers to operat e t heir bus iness on a ancient t echniq u es m ent ioned
lev el playing field. F or m anufactu rers , earlier. A re t hes e old t echniqu es s t ill
t here is als o a need t o ass ay jew ellery, relev ant in t oday ’s w orld?
w ork -in-progres s and recycled s crap Unfortu nat ely, for mos t jew ellers, it is
during manu factu re for quality control difficu lt t o m ak e an inform ed
pu rpos es . S om et im es , t here is a need com paris on of t echniqu es . W hils t
s im ply t o dis t ingu is h different t here are articles in t he literatu re on
carat ages of com ponent parts . F or s om e t echniqu es , t here hav e been
bu yers of s crap jew ellery, t here is a few at t empt s t o prov ide an ov erall
need t o det erm ine its carat age t o rev iew . The Ass aying and Refining
enable a fair price t o be paid w it hou t booklet (8) pu blis hed by World Gold
ex cess iv e risk . Council w as a recent att em pt and this
rev iew s eek s t o u pdat e t hat
A ccu r a cy o f a s s a yin g pu blicat ion in a w ay us efu l for
Thu s, t here are sev eral reasons w hy jew ellers s o t hat t hey can m ak e an
det erm inat ion of gold cont ent is inform ed choice.
im port ant . The accu racy of
m easu rem ent req u ired, how ev er, Th e te chn i que s o f a ssa yi n g
v aries according t o need. F or Table 1 lis t s t he m ore comm on
Hallm ark ing pu rpos es , gold cont ent t echniqu es av ailable for as saying of
is defined in parts per thous and , s o gold jew ellery, each of w hich w e
t he m easu rem ent t echniqu e u s ed s hall dis cuss in t u rn. I n s om e of the
m u st be capable of m easu ring t o 1 m odern inst rum ental t echniqu es , not
part per t hous and or less, i.e. in part s only can t he gold cont ent be
per t en t housand. On t he ot her hand, m easu red, bu t t he ot her alloying
t o dist ingu is h betw een, s ay, 14 carat m et als and im pu rit ies can als o be
and 18 carat com ponents in a m as s analysed s imu lt aneous ly. This is of
m anufactu ring line req u ires a low er s om e im portance in a m anu fact u ring
accu racy, s ay only 1 -2 w t . %. s it u at ion and is an addit ional
At this point, it is w ort h not ing that adv antage.
t he accu racy of t he as say is not only
det erm ined by t he accu racy of t he
ass aying t echniq u e, but als o by t he
Table 1. Assaying te chniques for gold je welle ry
representat iv eness of t he s am ple on
w hich t he m easu rement is t ak en. The Technique Destructive Comment
only t ru ly accu rat e as say v alu e of a Anc ie n t Fire Assay Yes – sample ta ken Weighing
piece of jew ellery is obt ained by Touchsto ne Yes, rubbing ta ken Colo ur comparison
t es t ing the w hole piece des t ru ct iv ely.
Density No Archimedes method
This is obv iou s ly not a pract ical
propos it ion and so s om e Parting Yes – sample ta ken Weighing
com prom is e has t o be m ade. The Moder n Electronic Go ld Pen No – surface only Capacitance decay
s am ple s ize req u ired t o as su re X-ray Fluorescence
No – surface only Measures emitted X-ray s
representat iv it y is almost a science in Spectrometry (XRF)
it s elf ( 6 ,7 ) . Atomic Absorp tion Yes – sample in solution Atomic absorption
Spectroscopy (AAS) or as solid cath ode lines measured
Cho ic e o f tec hniq ue
The m et hods of ass aying are als o of Inductively Coupled Atomic emission lines
interes t for other reas ons . A part from Plasma Spectrometry (ICP) Yes – sample in solution measured

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1 . Fi r e A s s a y (C up e l l a t i o n )
This ancient t echniq u e is firs t
referenced by t he E gypt ians in a
Cu neiform t ablet dat ing back t o
arou nd 13 60 BC, F igu re 2 , and is
bas ed on a gold refining t echniqu e. I n
it s pres ent form , it rem ains t he m os t
accu rat e t echniq u e for gold as s ay and
s erv es as t he s t andard techniqu e
against w hich all ot hers are com pared.
I t is cov ered by I S O s t andard I SO
11 426 :19 93 and is t he reference
t echniqu e u s ed by all t he A ss ay
O ffices w orldw ide.
The t echniqu e d epends u pon tw o
w eighings, s o analyt ical accu racy is
related t o the abilit y t o w eigh to high
accu racies , i.e. the precis ion of t he
analyt ical balance.
The principle is bas ed on t he
rem ov al of all bas e m etals from a
s m all w eighed s ample by ox idat ion in
t he cu pellat ion s tage t o leav e a pu re
gold-s ilv er alloy, follow ed by removal
of the silv er by dissolut ion in nit ric acid
– t he part ing s t age – t o leav e a residu e
of pu re gold w hich is then w eighed t o
allow calcu lat ion of t he gold cont ent .

Figure 3 - Fire Assay

(a) Sampling a gold ring by scraping
(b) Weighing sample on an analytical
balance
(c) Wrapping gold sample and silver
addition in lead foil
(d) Samples in refractory cupel placed in
furnace
(e) Cupels a ft e r removal from furnace
showing gold-silver beads
(f) Rolling the flattened gold-silver bead
(g) Dissolution of the silver from the
‘ co r n et’ in nitric acid

I n pract ice, a s am ple of t he

Figure 2 - Cuneiform tablet of King
Burraburiash of Babylon (1385-1361 BC),
recording assaying of a consignment of gold
from Egypt (from re ference 1).
leav e a sm all gold-s ilv er alloy bead,
jew ellery is t ak en, u s u ally by
Figu re 3e, w hich w ill als o cont ain any
s craping, F igu re 3 a, and w eighed,
plat inum group m et als pres ent in the
F igu re 3 b. S om e addit ional s ilv er is
s ample. A reference gold sam ple of
added before w rapping it in a pu re
k now n gold cont ent is normally ru n
lead foil, Figure 3 c, and placing it in a
in parallel w it h t he s ample t o
s pecial porous cru cible called a
elim inat e ex perim ent al errors .
cu pel. This is placed into a fu rnace at
On cooling, this bead is hammered
arou nd 1 100 ° C ( 201 2°F ) , F igu re 3d.
flat and rolled t o a t hin s t rip t o
The silv er is added to dilu te t he gold
increas e its s u rface area, F igure 3 f. It
cont ent to 25 % or les s ( k now n as
is coiled loos ely int o a ‘cornet ’ and
I nq u art at ion) . The lead m elts and
t he s ilv er dis solv ed out in 2 s tages in
alloys w it h t he s am ple and added
nit ric acid, F igu re 3 g. This is w hy
s ilv er and t hen all bas e m et als are
ox idis ed t o form a liqu id s lag. This silver is added to t he original sample.
F or su ccessfu l parting of the silv er, it
s lag is abs orbed int o t he cu pel t o
is necessary for the gold content t o be

22
Table 2. Fineness of gold in gold je welle ry alloys obtaine d by t ouchs tones w as q u it e w ides pread in
cupellation (ISO 11426) prehis t oric t im es .
I t is arguable t hat t his ancient
A llo y Cupellation Ita ly Cupellation Germa ny m et hod is es s ent ially non-
Test A lloy Ty pe U [ ‰] (s )(a ) A [ ‰] (s )(a ) dest ru ctive. It is based on rubbing t he
jew ellery article on t he s u rface of a
333/932 CG 333. 05 ± 0 .16 (8) 332. 96 ± 0 .15 ( 5)
smoot h, s light ly abras ive hard s tone –
376/904 CG 375. 86 ± 0 .13 (8) 375. 77 ± 0 .10 ( 5)
or t ou chs t one – t o leav e a m etallic
585. 1403 CG 585. 32 ± 0 .13 (7) 585. 27 ± 0 .10 ( 5)
s t reak of t he it em on t he st one.
585/143 0 CG 584. 88 ± 0 .21 (8) 585. 00 ± 0 .35 ( 5)
Ru bbings of k now n s t and ard
585/145 1 CG 587. 74 ± 0 .12 (8) 588. 19 ± 0 .23 ( 5)
reference alloys (t ouch needles) are
751/180 2 CG 750. 98 ± 0 .07 (7) 750. 70 ± 0 .16 ( 5)
placed bes ide it , F igu re 5 a; all are
751/181 0 CG 750. 08 ± 0 .36 (7) 749. 68 ± 0 .32 ( 5)
t hen t reat ed w it h s om e drops of
755/188 5 CG 753. 27 ± 0 .12 (8) 753. 43 ± 0 .12 ( 5)
s pecial t ouch acids , w hich are bas ed
750/185 1 CG 751. 90 ± 0 .14 (8) 751. 90 ± 0 .15 ( 3)
on nit ric acid, F igu re 5 b. This reacts
750/185 3 CG 747. 00 ± 0 .08 (8) 747. 44 ± 0 .07 ( 5)
585 Pd WG WG 584. 88 ± 0 .08 (8) 585. 00 ± 0 .00 ( 2) w it h the bas e met als and s ilv er t o
590 N i WG WG 590. 30 ± 0 .14 (7) 590. 60 ± 0 .35 ( 2) leav e a colou red mark w hich, aft er
750 Pd WG WG 750. 92 ± 0 .13 (8) 750. 50 ± 0 .00 ( 2) drying, is com pared t o t he colou r of
760 N i WG WG 759. 83 ± 0 .12 (8) 758. 90 ± 0 .14 ( 2) t he reference alloy ru bbings , F igu re
22/G old G CG 917. 18 ± 0 .11 (7) 917. 30 ± 0 .57 ( 2) 5 c. A dark er colou r m eans m ore
Au99 /T11 CG 988. 57 ± 0 .14 (8) 988. 60 ± 0 .00 ( 2) chem ical at t ack t hat , in t u rn, means
Stan dard de viatio n of les s gold. I t is a s u bject iv e t es t , in
all sin gle d e t e r mi n a - s (12 3) = 0,13 4 s (48) = 0.21 5 w hich t he colour of the s ample after
t i o n s of Au (‰ ) at t ack is com pared t o that of t he
reference alloy ru bbing.
a m ax im um of 25 %. O t herw is e t he res pect iv ely. S am ple s ize is t ypically
gold atoms w ill su rrou nd some of the abou t 2 50 m g, alt hou gh
s ilv er atoms and prev ent acces s by m icrocu pellat ion t echniqu es allow
t he nit ric acid. I n pract ice t he gold for mu ch s maller s am ples of abou t
cont ent can be higher than 25 %, u p 1 0m g w it h cons eq u ent s hort er
t o 3 4 % ( 9) . The rem aining gold process ing t im e (1 0) . A t s u ch sm all
cornet is pu re and can be w as hed, s am ple s izes , ensu ring t hat it is
dried and w eighed. repres ent at iv e of t he bu lk alloy
If insoluble plat inum group m et als becom es m ore difficu lt .
s u ch as iridiu m and ru t henium are Typically, F ire A ss ay can achiev e
pres ent in t he jew ellery, t hes e remain an accu racy of about 2 parts per t en
in t he gold and s o w ill lead t o high t hou sand, as dem ons trated from the
v alu es of gold being recorded u nless s tandard dev iat ion v alu es in Table 2 ,
fu rt her s t eps are t ak en t o rem ov e w hich is t ak en from Brill’s det ailed
t hem . Their pres ence can oft en be rev iew (1 0 ) . Brill not es t hat t he
obs erv ed on t he gold-s ilv er bead efficiency of fire ass ay can be
aft er cu pellat ion (8 ) . N ick el and des cribed as ex cellent and its
s olu ble plat inum m et als s u ch as perform ance enables it t o be
palladiu m are more difficu lt t o em ployed rou t inely in ass ay offices
rem ov e and m odified procedu res t o for hallm ark ing w here u p t o 10 00
ens u re t heir rem ov al m us t be t ak en s am ples per day are analys ed. He
( 8) . Thus , if t his m et hod is not done als o rem ark s t hat , at su ch ou t pu ts ,
properly, t here w ill be a t endency t o fire as s ay ( cu pellat ion) has no
overst at e t he gold cont ent. It helps t o compet itors w ith regard t o cost . N ot
k now t he approx im at e gold cont ent bad for an ancient t echniq u e!
of t he s am ple so t hat t he correct
am ou nt of s ilv er can be added. This 2. T o u c h s t o n e
can be det erm ined rou ghly and This t echniq ue is know n to dat e back
q u ick ly by t ou chs t one or X -ray t o t he Greeks in the 6t h cent ury BC,
flu ores cence , as w e s hall s ee lat er. alt hou gh there is s om e belief that it
A t ypical F ire Ass ay t ak es abou t 2 originat ed in E gypt in t he 12 t h
hou rs bu t m any samples (u p to 100 at cent u ry BC ( 1 ) . A n ancient
a t im e) can be ass ayed t ou chst one fou nd in F rance is s how n
s im u ltaneous ly. W here nick el or in Figu re 4 . I t dates back t o t he lat e Fig ure 4 - Touc hstone from Ch oisy -au-
palladiu m are pres ent , proces s ing Bronze A ge, abou t 8 -7t h centu ry BC Bac, France (from reference 11)
t im e is ext ended by 30 and 5 0 m in. ( 1 1) , s how ing t hat t he u se of

23

Figure 5 - Touchstone testing (from re ference 12)
(a) Rubbings from test piece (left) and touch needle
(b) Applying touch acids to rubbings
(c) Visual observation of rubbings
(d) Rubbings of alloys containing (from le ft) 700, 720 and 750 parts per thousand gold
Figure 6 - Equipment for touchstone
testing (from re ference 12)
24
The accu racy of t he m et hod
depends , in part , on k now ing t he
s ilv er : copper rat io. O ddy claims an
accu racy of 1 -2 w t % at bes t from
hist orical reports . This accords w ell
w it h t he m odern es t im at es of
dis t ingu ishing betw een alloys of
s light ly different gold cont ents , if
done by s k illed hands , F igu re 5 d.
Clearly, it is not nearly accu rat e
enou gh for det erm inat ion of a
definitive ass ay v alue for hallmark ing
pu rpos es bu t it is a q u ick t es t and
u s efu l as a s ort ing t es t and as a
preliminary t est prior to fire ass ay. It
is st ill us ed in Ass ay O ffices for t his
latt er pu rpos e. I t is not so good for
t he s oft high carat golds and t he
w hit e golds (1 2 ) .
The eq uipm ent is s im ple and
cheap, as s een in F igure 6 . Fu ll details
of test ing by t his m et hod, including
details of t he tou ch acids, are given in
the paper by W alchli & V uilleum ier in
G o l d T e c h n o l og y no. 3 (12) .
3 . D e ns i t y M et h o d
G old is one of t he heav ies t m et als
w ith a density of 19 .32 g/cm 3 , w hilst
the alloying met als in carat golds are
m uch lighter. S ilver has a dens ity of
only 10 .5 g/ c m 3 and copper is
ev en lighter at 8 .9 g/cm 3 .
Therefore, as caratage is low ered,
t he alloy dens ity – or s pecific grav ity
– redu ces . Thu s
ancient m an realis ed t hat
m easu rem ent of dens it y cou ld be
u s ed as an indicat ion of debas em ent
of the gold.
The philos opher, A rchim edes ,
w ho liv ed about 28 7 – 2 12 BC,
dis cov ered t he principle k now n by
all s choolboys t hat w hen a s olid is
im m ers ed in a liq u id, it s m as s is
redu ced by an am ou nt equ al t o the
m ass of liq u id dis placed. This allow s
calcu lat ion of dens it y by w eighing
t he s olid in air and t hen again w hen
im m ers ed in a liq u id. It is reported
( 1) t hat A rchim edes hims elf used t he
t echniq u e to check w het her t he
craft s m an w ho m ade a crow n for
Kin g Hi e r o h a d a d d e d a n y
b a s e m et als t o t he gold.
How ev er, t he u s e of t he dens it y
m et hod as a qu ant it at iv e ass aying
t echniq ue is not recorded u nt il mu ch
later in t he 6t h cent u ry AD , follow ed
by s ev eral lat er m anu s cripts dat ing
from 10 t h - 1 3t h centu ry A D , one of
w hich refers to ass aying of gold-silv er
alloys . F igu re 7 s how s its us e in
L ondon in t he 17 t h cent ury.
Wit h m odern analyt ical balances, it
is pos s ible t o w eigh very accu rat ely
s o, in t heory, det erm inat ion of
dens it y can be m ade t o a high
accu racy. The t echniq u e m eas u res
t he w hole piece of jew ellery and is
non-des t ru ct iv e. There are no
s am pling errors in t his m et hod!
I n pract ice, how ev er, there are a
nu m ber of problem s in us ing t his
m et hod. F irst ly, how do w e relate the
Figure 7 - Density measurement
(foreground) in London, 17th century.
Fire assay can be seen behind (from
reference 1)

Figure 8 - Alloy densities in gold-silver-
copper alloy system (fro m re ference 13)
m easu red dens ity t o gold cont ent?
F or binary alloys s u ch as gold-s ilv er
or gold-copper, t his is
s t raightforw ard. Real jew ellery alloys
are rarely s imple binary alloys but
contain 3 or ev en more m et als –
gold -s ilv er-copper w it h, perhaps ,
addit ions of zinc, nick el, palladium ,
grain refiners and deox idis ers . Thus ,
for a giv en gold content , t he act ual
dens ity of t he alloy w ill depend on
t he relat iv e am ounts of the alloying
m etals . F or 18 carat golds , t ypical
dens it ies range from 15 .15 for red
golds t o 16 .1 for w hite golds . It
m us t be rem ark ed t hat a dens it y
figu re for one alloy m ay be ident ical
t o t hat of anot her w ith a differing
gold cont ent . This is clearly show n
for t ernary gold-silver-copper alloys
in F igu re 8 , t ak en from t he w ork of
Krau t and S tern (13 ) .
The s econd pract ical problem is
t hat of meas u ring dens ity accu rat ely.
I f t he jew ellery contains poros ity or
inclu s ions , t he measu red apparent
dens it y w ill be low ered. I t is als o
difficu lt t o ens ure that no air bubbles
are t rapped w hen w eighing t he it em
in a liq u id. Las t ly, a piece of real
jew ellery w ill als o cont ain s olders of
different com pos it ions (and hence
dens it ies ) w hich w ill complicat e
t hings fu rt her. Thus , t he dens it y
m ethod is a s imple, cheap and qu ick
non-des t ru ct ive m et hod bu t it cannot
give an accu rat e ass ay. At best , it can
only giv e a s em i-q u ant it at iv e
indication of caratage, u nless the it em
is a k now n binary alloy w it hou t any
s olders . Hence its cont inu ed us e in
ex am ining old coins . A fu ll
des cript ion of t he m et hod and s om e
of its lim itations is given by N ordt et only t o t he neares t 1 -2 carat s (4 -8
al (14). w t .%) . I t is not cons is t ent and
now here near accu rat e ( 15 ) and s o
4 . P a r t i n g ( F a l s e Fi r e A s s a y ) s hou ld only be u s ed as a qu ick
I include t his ass aying t echniq u e t o s orting t est to different iate caratages .
illu st rat e s om e of t he ignorance st ill
fou nd t oday in t he indu st ry arou nd
t he w orld. N ot infreq uent ly, I hav e
fou nd m anu fact u rers and so-called
as s ayers claim ing t o do fire as s ay
w hen all t hat t hey do is t o place the
s am ple of the gold alloy in nit ric acid
– t he part ing s t age of t he fire as say
procedu re. The as s um pt ion is t hat
nit ric acid w ill diss olve all bas e
m et als and s ilv er and leav e pu re gold
u nt ou ched. This is not t ru e. F or a
s t art , not all t he s ilv er w ill be
dis s olv ed aw ay as som e w ill be
m ask ed by t he gold, unless t he gold
content is 25 % or less . There is also
no gu arant ee t hat all ot her bas e
m et als w ill be rem ov ed com plet ely.
Cert ainly, any non-m et allic
inclu s ions , ox ides, et c are unlik ely to
be rem ov ed. Thus , this m ethod w ill
alw ays giv e false high res u lts , s o that
a gold it em t hat is actu ally
u ndercarat ed can appear t o be ov er
t he m inimu m gold cont ent and
w ithin carat age. A m et hod not t o be
recom m ended!
5 . E l e c t r o n i c G o l d ‘ Pe n ’
I t is poss ible to bu y cheap port able
elect ronic inst rum ents for m eas u ring
gold cont ent , F igu re 9 . A probe or
‘pen’ is placed on t he su rface of the
jew ellery in cont act w it h a
conduct iv e gel and t he gold cont ent
read off a m et er at t ached t o it . This
t ype of ins t ru m ent us u ally w orks on
t he capacit ance decay principle of
t he s u rface and relat ing it t o gold
cont ent . W hils t qu ick and non-
des t ru ct iv e, it is dependent on
s u rface com pos it ion. I t m eas u res
Figure 9 - Electronic P en
25
 6. X - r a y F l u o r es c e n c e
S p e c t r o s co p y ( ‘ X R F ’ )
Commonly know n as ‘X RF’, t his is an
increas ingly popu lar t echniq u e,
finding s erv ice in bot h jew ellery
m anu factu ring and in as s aying
laborat ories . I n t his t echniqu e, t he
s u rface of t he jew ellery is bom barded
w ith radiat ion, us ually from an X -ray
t u be s ou rce. This radiat ion im pact s
t he at oms and cau s es elect rons t o
m ove lev els ( orbit al s hells ) w it h t he
Figure 10 - X-ray Fluorescence: the photoelectric e ffe c t (from re ference 16)
Figure 11 - X-ray spectrum from a 14 carat yellow gold (from re ference 16)
26
em iss ion of X-rays , F igu re 10 , hence
t he t erm ‘flu or es cenc e’. Thes e are
collect ed and m eas u red in a
s pect rometer. The important point is
t hat t he X -rays ex cit ed and em it t ed
from t he su rface w ill hav e a defined
energy w it h a w avelengt h
characterist ic of the at om from w hich
it is generated. Thus , different m et als
em it X -rays of different w avelengt hs.
The am ou nt of energy em it t ed w ill
depend on t he relat iv e num ber of
at oms of t hat m et al pres ent . I f w e
cou nt t hat energy, w e can det erm ine
t he am ount of t hat m et al pres ent .
F igu re 11 s how s a typical s pect rum
from a 14 carat gold.
This techniq u e is non-des t ru ct iv e
but it only measu res a small sam ple at
t he su rface of the jew ellery, t ypically
a layer of 1 0 – 5 0 m icrons t hick ,
depending on alloy com pos it ion and
t he m etal being m eas u red. Thus ,
ensu ring t he s am ple is t ypical of t he
bu lk alloy is critical. Elect roplat ing or
chem ical t reatm ents , su ch as
bom bing and acid pick ling w hich
change the s u rface com pos it ion, w ill
dis tort the analys is . Measu rem ents
can be m ade on a s ingle s pot , on an
average of s ev eral s pots or line or an
area by ras t ering t he beam ov er the
s u rface. I n t he latt er m ode, an
elem ent al dis t ribu t ion m ap can be
produ ced.
F or opt im u m m eas u rem ent , t he
s u rface s hou ld be clean, flat and
polis hed and at least 3mm diamet er.
Cu rv ed s u rfaces redu ce accu racy as
t he em it t ed X -rays are s catt ered.
Typically, m eas u rem ents take about
2 – 3 m in. w it h t he inst ru m ent
comput ing t he res u lt s au tomat ically.
A ccu racy im prov es w ith increas ing
m easu ring t im e.
The physics of the technique are
complex and it is not appropriate to go
into much detail here, as Kloos has
recently review ed this topic (16). Suffice
to say that there are matrix interaction
effects betw een metals and so the raw
data collected must be corrected to yield
an accurate analysis. As you w ill note in
Figure 11, there can be overlap of
adjacent w avelengths and these must be
mathematically deconvoluted to separate
the individual metals. Cheaper
instruments may not be able to
qu ant it at ive ly separate metals w ith
ov erlappin g cu rv es du e t o t heir
poorer resolut ion. Z inc is a t ypical
ex am ple of t his problem in gold
a llo y s
The accu racy of t he t echniqu e
depends , t herefore, on the correct ion
m odels u sed in the s oftw are as w ell
as the phys ical condit ions of
m eas u rem ent. Therefore, t he
ins t ru m ent needs t o know w hat
m et als are pres ent and t o m eas u re
t hem all, if accu rat e v alues for gold
are t o be obt ained. The s pect rom et er
comm only us ed is t he energy
dis pers iv e type, w hich collects and
m eas u res t he w hole spect ru m of X -
radiat ion s im u lt aneous ly, w hich
allow s all m et als pres ent t o be
analys ed. A more accu rate t ype is the
w av elengt h dispers iv e s pect rom et er,
w hich m easu res only one met al at a
t im e bu t it is m ore ex pens iv e.
A ccu racy is significantly im proved
by calibrat ing t he X RF us ing standard
alloys of k now n com pos it ion and
clos e to t hat of the u nknow n s am ple.
In som e inst rum ents, s uch calibrat ion
is done by the X RF manufactu rer and
stored in t he inst rument , so that it can
be used w it hout the need for fu rther
calibrat ion du ring us e. A ccording t o
Brill (1 0) , XRF can m eas ure gold t o
0.75‰ ( parts per t hous and) under
opt imu m condit ions but for
m icroX RF , typical of m any gold
ass aying ins t rum ent s, an accu racy of
0 .2 – 0 .3 % can be achiev ed w ith a
m eas u rem ent t im e of 3 m in.
Marru cco and St ank iew icz ( 1 7 )
demons t rat ed an accu racy of 0 .12 %
w as at tainable in t heir research
s t udies of t he t echniqu e.
Thu s, X RF is not qu it e accu rat e
enou gh for Hallm ark ing pu rpos es ,
bu t is close and im prov ing ev ery
year. It finds cons iderable applicat ion
in Ass aying O ffices as an alt ernat iv e
t o t ouchs tone for prelim inary t est ing
of jew ellery. I t can be us ed t o
ex am ine jew ellery by scanning
Figure 12 - XRF analysis of ball links in a
coloured gold chain (from re ference 10)
Figure 13 - Typical XRF instruments (a) Spectro Analytical Inc (b) X-Tester installed in retail
shop in India
different areas t o det erm ine if s am ples or s am ples in s olu tion. The
u ndercarated s olders or components s olid s am ple is s pu t t ered as t he
have been us ed, for ex am ple, F igu re cat hode and t he resu lt ing v apou r
12 , or if the item has been gold m easu red by t he atom ic abs orpt ion
plated or t he solders contain t echniqu e. Solu t ion A AS , us ing
cadm iu m. This can help t o s elect s amples diss olv ed in aq u a regia, is
w hich areas of jew ellery are s am pled anot her approach but s olu t ions of
for fire ass ay. It is a qu ick and v ery gold st andards are not s t able,
flex ible t echniqu e and can analys e according t o Brill (10) w ho conclu des
for all metals pres ent in t he that AAS is not as econom ical as ICP
jew ellery. s pect rom et ry.
I t also finds increas ing applicat ion MicroA AS u s es only a 1 0 m g
in jew ellery m anu fact u ring as a sample but Brill claims t hat t he resu lts
quality cont rol tool, not only for gold are not as good as I CP spect rom et ry.
cont ent but for complet e analys is of O n t his bas is , A AS w ill not be
jew ellery alloys and scraps . I n I ndia, dis cu ss ed fu rther here. A ccu racy of
one m ajor u pm ark et jew ellery chain t he techniqu e is abou t 0.1 % at best ,
has installed XRF m achines in each of making it u nsu itable as a rou tine t est
it s s hops , F igu re 13 b, s o that for finenes s m eas u rem ent for
cu st om ers can check that t heir new hallm ark ing.
jew ellery is on carat age. A certificat e
is print ed ou t as a gu arantee w it hin 3
m inut es .
There are many manu fact u rers of
XRF instruments on the market , many
w ith m odels t ailored for assaying of
gold alloys and jew ellery. Tw o
ex am ples are s how n in F igu re 13 .
The price and performance of thes e
v aries . For example, cheaper models
m ay be fit t ed w it h a proport ional
count er w hich only has a res olu tion
of 0 .5 %, w hereas m ore ex pens iv e
m odels are fit t ed w it h solid s tat e
counters w ith a higher res olu tion of
50 ppm . How ev er, thes e latter cos t a
fact or of around 6 t im es m ore. A
typical cos t of su itable inst rum ents is
US $20 ,0 00 – $35 ,0 00 , depending on
perform ance and addit ional featu res
fitted.
Figure 14 - Atomic Absorption
7. A t o m i c A b s o r p t i o n Spectrometer (fro m re ference 10)
Sp ect r o met r y
A t om ic abs orpt ion s pect ros copy
( A AS ) us ing a m u lt i-element
s pect rom et er, Figu re 1 4, is anot her
poss ible t echniq u e for as saying of
gold jew ellery, us ing eit her s olid
27
8. In d u ct iv el y Co u pl ed Plas ma
S p e ctr os cop y ( ‘ IC P’ )
I ndu ct iv ely cou pled plas ma s olu tion
s pect rom et ry (I CP) is a s eriou s
contender t o fire assay for ass aying of
carat golds and it is finding
cons iderable us e in many preciou s
m et al analyt ical laborat ories . F or
w hit e golds containing nick el or
pallad iu m, I CP has an adv ant age du e
t o its great er element s elect iv ity ( 10) .
The t echniq u e allow s for a fu ll
analysis of t he gold s am ple, w hich is
an added advantage ov er fire as say.
The use of I CP for gold determinat ion
in jew ellery has been dis cuss ed by
Brill (18 ) in som e det ail.
I n t his t echniqu e, a w eighed
buffered aqu eous s olut ion of the gold
s am ple is nebu lis ed and inject ed int o
a plasm a flam e, F igu re 15 , and t he
s pect ral em iss ion analys ed in mu lt i-
elem ent s pect rom et ers, w it h
s imu lt aneous m easu rement of
Y tt riu m as an int ernal s t andard. The
intens ity of the emission is relat ed t o
t he am ou nt of m et al present .
Calibrat ion against s olu t ions of alloy
s t andards is req u ired. Micro-I CP
allow s us e of samples of abou t 10 –
2 0 m g. Accu racy is 1 part per
t hous and for gold.
Figure 15 - P lasma fla me in ICP
Spectrometry (from re ference 10)
28
Figure 16 - Inductively Coupled P lasma
Spectroscopy machine (from re ference 18)
I CP has a nu m ber of adv antages
ov er fire as s ay:
• S peed of ass aying is s im ilar t o
fire as s a y
• S peed is fas t er t han fire ass ay for
nick el- and palladium -w hit e golds
• S m aller s am ple w eights are
req u ired
• There is no int erference du e to
plat inum , rhodium and iridiu m
• A ll alloying addit ions analys ed
s imu lt aneous ly, inclu ding t race
elem ent s
• There are no em iss ions of t ox ic
lead fum es as in fire as say
• The process can be aut omat ed
( 19 ) The m ajor dis advantage of I CP
is its cost , t ypically abou t $1 50 ,00 0.
Thus , it finds us e only in t he
laboratories of t he m ajor As s ay
O ffices and large precious m etal
and jew ellery com panies , F igu re 16 .
C ompa ri son o f te chni que s
A s s tat ed earlier, F ire As s ay
( Cu pellat ion) is t he s tandard
reference t echniq ue against w hich all
ot her t echniq u es m ay be com pared.
D es pit e its age, it rem ains the m ost
accu rate t echniq u e. I n his rev iew ,
Brill ( 10 ) giv es mu ch dat a on s u ch
comparis ons in the assaying of gold
in jew ellery alloys . This clearly
demons t rat es t he s uperiorit y of fire
ass ay ov er all ot hers .
The qu est ion of w hich techniq ue is
s elect ed for ass aying of gold
jew ellery tu rns on the s pecific
needs :
1. F in en ess det er min at i on fo r
H al lm arkin g pur pos es.
F ire ass ay has the bes t accu racy. I CP
S pect rom et ry is clos e and has a
nu mber of advantages , inclu ding an
ability t o prov ide a com plete analys is.
Its major dis advantage is its cos t. XRF
is not q u it e good enou gh, alt hou gh
im proving, in accu racy t erms but has
an adv ant age in being non-
dest ruct iv e. It s m ajor short com ing is
t hat it m eas u res only a t hin s u rface
layer t hat may not be t ypical of t he
bu lk alloy compos it ion.
F or a rou gh prelim inary
ass ess ment, t ou chs tone or X RF may
be us ed. XRF has adv antages in being
able t o q u ick ly s can it ems t o
det erm ine any pot ent ial problem
areas and to ass ist in s elect ing w here
s amples are t ak en.
2 . Qu ali t y con t rol i n pr odu cti on
F ire ass ay rem ains a preferred
t echniq u e for accu rat e gold ass aying,
bu t X RF is finding increas ed
application, w it h a sufficient accuracy
for m ost pu rpos es . A fas t t echniqu e
that allow s a com plete analys is of the
alloying m et als.
3. A s a qui ck s ort in g t es t t o
d e t e r mi n e a p p r o x i ma t e
car at age
Tou chs t one rem ains u s efu l for t his
pu rpos e; it is q u ick and cheap and
port able. X RF is ju st as q u ick and
m ore accu rat e, bu t m ore cost ly. Bot h
are non-des tru ct ible. The E lect ronic
pen is als o applicable t o this s ect or
bu t it does not give cons is t ent
res u lt s .
Su mmary
A summa ry of the techniq ues is given
in Table 3. The equ ipm ent cost s are
only indicat iv e. The cost of fire assay
w ill depend on t he num ber of
s am ples t es t ed per day. W here this is
low , capit al costs w ill be low er t han
t hose q u ot ed. Brill als o giv es an
indicat ion of annu al operat ing cos ts
in his rev iew (1 0) , bas ed on carrying
ou t hundreds of as says per day.
Fu tu re devel op me nts
A s w e hav e s een, t he m os t ancient
t echniqu e of fire as say cont inu es t o
dom inat e t oday. I t has a nu mber of
adv ant ages including accu racy,
alt hou gh it can only m eas u re gold
cont ent . The cont inu ing
im provement s t o t he X RF t echniqu e
hav e already been ment ioned and it is
reas onable to cons ider that it may yet
becom e a techniqu e accu rat e enou gh
for finenes s det erm ination. This w ill
depend on improv ed det ectors and
s oftw are. P rogres s in s olid s t at e
det ectors is being m ade s t eadily.
Wider use of I CP spect rom et ry remains
u nlikely unless t he capit al cos t of the
inst rum ents is redu ced su bs tant ially.
 Chem ical Compos it ion”, Go l d
T a b l e 3 . C o m p a r i s o n o f A ss a yi n g T e c h n i q u e s
Bu l let i n , 3 3 (2 ) , 2000 , 52- 55.
Technique Versatility Sa mple size Accuracy Limitat ions
Equipment 1 4 N ordt , P .N., Hill, W .C. & Rohr,
Cost K.L ., “P ract ical A pplicat ions of
Fire Assay Only gold ~ 250 mg 0.02%
M od i fic a t ions Moderate S pecific G rav it y D et erm inat ion
for Ni and Pd $50,000 to P lat inu m Jew elry
ICP
Complete
~ 20 mg 0.1% –
High Manu factu ring – The Us es and
analy sis $150,00 0
L im it at ions of A rchim edes
XRF
Complete Non- 0 .1 – 0 .5%
Surface lay er, Moderate P rinciple”, in Pl at in u m
analy sis destructive flat samples $25,000+
Man u fac tu rin g Pro c e s s V o l. II I ,
Unsuitable for
Touc hsto ne Only gold Almost no n- 1-2% high carat and Low 1 99 7, 38 -47 , P u bl. P GI , US A .
destructive white go lds $100 1 5 Johns ton, P .V .A., P r o c . 1 6 t h
In t e rn at io n al Pr e c io u s Me t a ls
Electronic Pe n Only gold Non- 4-8% Not cons isten t Low $200 C o n f e r e n c e , 1 992 , 205 , pu bl
destructive
I P MI , US A .
1 6 Kloos , D ., “ED XRF A nalys is of
Non- Only for binary Low
Density Only gold
destructive
Poor
alloy s $500 G old Karat A lloys us ing
P roport ional Cou nt er bas ed
Te ch n o lo g y N o 26 , Ju ly 1999 , Micro-ED X RF ”, P ro c . 2 4 t h
The us e of las ers t o put hallm arks 1 6 -23 . In t e rn at io n al Pr e c io u s Me t a ls
on jew elle ry is a recent dev elopment 4 Rushforth, R.W.E., “International C o n f e r e n c e , Ju ne 2 00 0, publ.
(20, 21). It is poss ible to env isage t hat Hallmarking – Pipedream or I P MI , US A .
the m et al v apou r generated from t he P oss ibilit y”, Pro c . S an t a F e 1 7 Marucco, A ., & St ank iew icz, W.,
laser engraving cou ld be fed into an Sy m po siu m , 1999, 461-485, publ. “D ev elopm ent of an X RF
at om ic em iss ion s pect rom et er for Met -Chem Res earch I nc.; als o S pectrom et ry A nalyt ical Method
direct analys is , as Brill has su ggest ed G o ld Tech n o lo g y , N o 27 , for G old D et erm inat ion in G old
( 1 0 ) in his rev iew . I f t his s hou ld N ov ember 19 99, 21 -29 . Jew elle ry A lloys ”, G old
m at erialis e, t hen it is pos s ible t o 5 Corti, C.W ., “Qualit y in Jew ellery Tech n o lo g y , N o 24 , S ept em ber
conceive that t he ancient met hods for Manu fact u re – Beyond 200 0 ”, 1 99 8, 14 -22 .
gold ass aying w ill finally be replaced P r o c . S an t a F e S y m po s iu m , 1 8 Brill, M. and W iedemann, K-H.,
w it h the modern ones . 1998, 1-31 , Met -Chem Research “Determ ination of G old in G old
I nc. S ee als o ‘E dit or’s Jew elle ry A lloys by I CP
C onclu si on s Comments’, Go ld Tech n o lo g y , S pectrom et ry”, Go ld B u l l et i n ,
This review has s how n that w hilst t he N o 29 , Su mm er 200 0 , 3 0 -31 . 2 5(1 ) , 19 92 , 13 -2 6.
m odern ins t rum ental t echniqu es for 6 Shepherd, O.C. and D iet rich, 1 9 Brill, M., “Robot is ed I CP -
assaying gold jew ellery hav e much to W .F ., “F ire Ass aying”, 1 940 , L aborat ory for t he Analys is of
offer, t he ancient t echniq ues of F ire reprint ed by Met -Chem Res earch Precious Metals ”, Go ld Bu llet i n ,
A ss ay and Touchs t one cont inue to I nc, US A , 198 9. 28 (2) , 19 95 , 38 -53 .
play a m ajor role becaus e of t heir 7 S m it h, E.A ., “The S am pling and 2 0 A non, “Breakt hrou gh in L as er
advant ageous charact erist ics , w ith Assaying of the Precious Metals”, Mark ing for P reciou s Metals ”,
accu racy and cost being of 2 nd ed., 1947 , reprint ed Met - G o ld Tech n o lo g y , N o 2 4,
significance in t he cas e of fire as say. Chem Res earch I nc, USA , 19 87. S ept em ber 1 998 , 11 -12 .
How ever, XRF continu es to progress 8 “A ss aying and Refining of G old 2 1 “Relief-Las ering m ak es a F ine
and is finding increasing application. Jew ellery”, pu bl. 1997 , World Im press ion”, Th e An ch o r
The ass aying t echniq u e s elected G old Council, L ondon. ( N ew slet t er of the Birm ingham
w ill depend on t he part icu lar need 9 I . Bayley, Birm ingham A ss ay A ss ay O ffice) , S pring 2 000 ,
and cost of the eq u ipm ent . F or the O ffice, P rivat e commu nicat ion, page 1 .
latt er reas on, I CP S pect rom et ry w ill 2001
only find lim it ed applicat ion. 1 0 Brill, M., “A nalys is of Carat
Gold”, G o ld Tech n o lo gy , No 22,
R e fe renc e s Ju ly 1997 , 1 0-2 5.
1 O ddy, A ., “A ss aying in Antiquity”, 1 1 E lu ere, C., “A P rehis t oric
Go ld Bu l let i n , 16(2), 1 983 , 5 2- Tou chs tone from France”, Go l d
59 . Bu l let i n , 1 9 (2 ) , 1986 , 58 -61 .
2 Jacobson, D .M., “Corint hian 1 2 Walchi, W . & V u illeum ier, P .,
Bronze and t he G old of the “Tou chstone Test ing of Precious
A lchem ist s ”, Go l d B u l le t in , Metals”, G o ld Tech no lo gy , No 3,
3 3( 2) , 20 00 , 60 -66 . Janu ary 19 91 , 9 -18 .
3 G rimw ade, M.F ., “The S u rface 13 Krau t, J.C. and St ern, W .B., “The
Enrichm ent of Carat G old alloys D ens it y of G old-S ilv er-Copper
– D eplet ion Gilding”, G o l d A lloys and its Calcu lat ion from

29
 A ck n o w led g em en t s
This rev iew is adapt ed from a paper
present ed at the Sant a Fe Symposium
on jew elry m anu factu ring t echno-
logy, held in A lbu q u erq u e, N .M.,
US A in May 2 00 1 .
My thanks and appreciation to the
m any people and com panies w ho
hav e prov ided adv ice and
inform at ion. Thes e inclu de D on
Kloos , CMI I nt ernat ional, and
Michael Has chk e, Röt genana lyt ik
Messt echnik GmbH for their help and
inform at ion on XRF , Mark G rimw ade
and Pet er Raw for t heir WG C s em inar
m at erials , w hich hav e s erv ed as a
bas is for t his pres ent at ion and Ian
Bayley of t he Birm ingham A ss ay
O ffice. I hav e draw n heav ily on the
papers of A ndrew O ddy, Brit is h
Mu s eum , and D r Manfrid Brill
( form erly W .C.Heraeu s Gm bH) .
Many of t he figu res hav e been taken
from t he referenced pu blicat ions .
F igu re 9 is cou rt es y of Rio G rande,
US A and F igu re 13 is cou rt es y of
S pect ro and Titan Indus t ries , I ndia.

“
MABOR”
Magnesia Refractory Cu pels & Bu l l i on Blocks
(Serving t he G old Indust ry for more than 100 Years )

U s ed by F ire As s ay ing est ablishments , P recious M et al Refiners , J ew ellery

M anufact urers and H all M arking Laborat ories in more than 50 Count ries .

Cont act :

30
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