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Recent  Devel opment  i n Si mul t aneous  M ul t i . .   El em ent  Det erm i nat i on of  t he Pl at i num   Group El em ent s  and Gol d i n Geol ogi cal  

and Envi ronment al  Samb mpl es木 ●     REN  Ma n(任 曼 )‘  a ’ n d   DENG  Ha i l i n g( 邓海琳 )   1)( I n s t i t u t e   fG o e o c h e mi s t r y,Ch i n e s e   Ac a d e m)o fS c i e n c e s ,Gu a n gz h o u   51 0 6 4 0。C h i n a)   2)(G r a d u a t e   S c ho o l ,Ch i n e s e   Ac a d e r n ?o f  S c i e ce n s,Be in t l g  1 0 0 0 3 9.Ch i n Ⅱ)   Abs tr act:I n r ecent  year s.t he moder n met ho ds  of  mul t i — el ement  anal ysi s  of  pr eci ous  met a l s   have at t r act ed wi de  at t ent i on  i n s ci ent i ic r f es ear ch  and i ndust r y The  appl i cat i on and devel op—   .

ment  i n t he  decomposi t i on of   sampl es,separ at i on and enr i chment and mode rn i ns t r ument al  a.   .

n a l y s i s   o f   t he   p l a t i nu m— g r ou p   e l e me n t s(PGEs )a n d  g o l d   i n   g e o l o g i ca l  a n d  e n v i r o nme nt a l  s a m.   pl es  have  been  r evi ewed.Fi na l l y,t he  t endency of  anal ysi s  of  preci ous  met al s  i s  al s o pr os pec.   t e d.  

Key wor ds:pl at i num - gr oup el ement s;gol d;geol ogi c al   and envi ronm ent al  s am pl es:si m.   ul t aneous  mul t i - el ement  det ermi nati on:renew 

1  Introduct i on  Due  t o  t hei r   gr e at  i mpo r t ance   i n s ci e nt i c  r e se ar c h  and  ec onomi c   dm  el opment de t er mi nat i on  of   ,

t h e   p l a t i n um— g r o u p  e l e me n t s(PGEs)a nd  g o l d  ha s   a r o u s e d   c o n s i de r a b l e  i n t e r e s t  i n  ma ny  f ie l ds.   s uc h as  geoc hemi s t r y, envi r onment al  s ci ence,bi ol ogy  and mat e r i al  s ci ence (Rno  and Re ddi . 

2000).  I n  t hi s  pa per,mor e   at t ent i on  has  been  pai d  t o  t he   anal ys i s  o f   t r ace  pr eci ous  met a l s  i n g e0一   l ogi cal  and e nvi r o nment a l  s ampl es.The  s i gni icance f  i n  de t er mi na t i on o f   t he  PGEs  and  gol d i n  geo-  

l o g i c a l   a n d   e nv i r o n me n t a l   s a mp l e s   c a n   b e   de s c r i b e d  a s   f o l l o ws:(1)t o   g ui d e   g e o c he mi c a l   e x pl o r a —   t i on;(2)t o   be  us ed  as  a  geo chemi c al  t r ace r;(3)t o be  a new i s o t ope  chr o nol o gy  met hod es t a b—   l i s hed o n t he  bas i s  o f   bot h   Re_t 8 7 Os  and ‘ 9 oPt _1 8 8 Os  i s o t 0pe   de cav   s che mes  i n  Ear t h  and  pl ane t ar y  

s c i e n c e s(Mo r g a n   e t   a 1 .,2 0 02);( 4)t o   e x pl o r e   t h e   i mp a c t   o f   e x t r a t e r r e s t r i a l   ma t e r i a l s   i n   t e ms r   0 f   unus uaII eve l s  of   PGEs(Xi e  Li ewe n e t   a1 ..2001).   Howev er,acc ur at e  det e r mi na t i on  of   PGEs  and  gol d i s  ve r y  di m cul t  due  t o  t hei r   ext r eme 1 v   l o w 

c onc ent r at i ons,he t er o genei t y(“nugget  e f f e ct ”),r e f r ac t or y pha s es.and l ar ge  amo unt s  of   c ompl e x   mat ri x el ement s.1n recent  years wi t h  t he   dev el opment   of   modem i ns t r ument al   t e chni ques de t er m i .   ,



nat i on  of  PGEs  and g ol d has  changed  i t s  o r i ent at i o n f r om mono— el ement  aHal ys i s  t 0  si muI t ane 0us   mul t i — el ement   anal ys i s . Thi s   paper   has   r evi e wed   t he   s i gni f i ca nt   r es e ar c h  cont r i but i 0ns   i n  t he   f i el ds   0 f   s ampl e  decompos i t i on,pr econcent r at i o n  and  i ns t r ument al   t echni ques   f or   PGEs   and   gol d  i n   geol o gi cal   and e nvi r onment al  s ampl es .  

I SSN l O 0O- 9426  

Gr ant ed   j oi nt l y  by   t he   Nat i 。na[Key   Bas i c  Re s ear ch  Dev el opment  a nd Pl anni ng  Pr og r am (G1   9 99043205)and  l nn ova t i 。 n l ' r o j ect   Funds   of   t he  Chi nes e   Aca demy   of   Sci en ces(KZXZ一 1 01).  

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2 D ecom posi t i on  Nat ur al   s ampl e s,i n ge ner a l,need  t o be decompos ed be f or e  de t er mi na t i o n,f or  t he  concent r a —   t i o ns  of   pr eci o us  me t al s   ar e   ver y   l ow.Met ho ds   o f   s a mpl e   deco mpos i t i on  i ncl ude  f i r e  as s ay,al ka l i  f u—   s i on  and a ci d di s s ol ut i on.   2.1  Fi re  ass ay  As   a  t r a di t i onal  a nd  cl as s i ca l   t echni que,f i r e   ass a y  ca n  be   us ed  t o  decompos e  s ampl es  and  s epa —   r at e  PGEs  and  gol d  f r om bas e   met al s  and  s i l i ca t es  i n  s ampl es.Ther e  a r e  s eve r al  col l e ct or s,such  as  

Ni S,P b,Bi ,S n,S b,o f   wh i c h   Ni S   i s   t h e   mo s t   i mp o r t a nt(Wu   Ru i l i n   e t   a 1 .,1 99 7).Summa y  r o f   Ni S f ir e  as s ay  i s  pr es ent e d i n  Tabl e  1.  

Tabl e  1. Fi r e as say 

For  Ni S— FA.t he   mi xt ur e   of   sampl e   and  lux f   i S   f us ed  at   a bout   1 000℃ f 0r   1  t o  2  h.The  Ni S  but —   t on  i s  t r eat ed wi t h aci d,and t hen t he  i ns ol ubl e  pr eci ous  met al  s ul ides f  a r e  at t ac ked by  oxi di z i ng   a ci d.   To  obt ai n a  hi gh r e cover y ,t he  key  f a ct or s  of  Ni S  f i r e  a s sa y  ar e  f l ux  i ngr edi ent s,t emper a t ur e,   t i me,and  t r ea t ment  of   t he  f ir e  but t on.As  f 0 r   lux f  i ng r edi ent s.t wo par a met er s  s houl d be e xa mi ned 

s ys t emat i cal l y:E,t he  r at i o   of   t he  combi ne d wei ght s  of   s ampl e+f lux  t o  t he  wei ght  of   t he  col l e ct or,  

a nd   Sc,t he   p e r c e n t a g e   o f   s u l f ur   i n   t he   c o l l e c t o r(Pa uk e r t  a nd   Ru be s ka,1 9 93).McDo na l d   e t   a 1 .   (1 994)r epor t ed  t hat  l ar ger  r ecover y (94% 一98% VS .84% 一92% )was   obt a i ned  by  addi ng  mor e   s i l i ca  a nd bor a x  t o  t he   us ua l   lux f   composi t i ons  f or   Ni — FA.i n  t hei r   s t udy  of   s ome  Sout h Af r i can  ki m—   ber 1   i t es  

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Us ual l y,l os s es   of   pr eci ous   met al s   Occ ur   at  t he  s t a ges  o f   f i r e   as s ay,but t on  cr us hi ng   and di s s o—   l ut i on. Loss es   can  be  av oi de d when  but t ons  ar e  di r ec t l y  di s s o l ved i n  heat ed s cr ewed— cappe d Tef l on  

bo mbs(Sun  Mi n  e t   a1 .,1   993).A  modi f i ed   t echni que.na mel y   a  s emi — o pen   di s s ol ut i on   s ys t em  af t er  

f us i o n.us i ng  r ef l ux  s et up,al l o ws  Os  t o  be  a l mos t  co mpl e t el y  r ecove r e d (GF OS  et   a1 .,2002).   Compar ed  wi t h  al kal i   f us i on  and  aci d  di ges t i on.t he  mai n  adv ant ages   of   Ni — FA  ar e   des cr i bed  as  

f o l l o ws:(a)e a s y   h a n dl i n g   o f   l a r g e   s a mp l e   we i g h t s   t h a t   c a n   o v e r c o me   n u g g e t   e f f e c t s;(b)a s s u r a n c e   of   qua nt i t a t i ve   col l e ct i on  of   a1 I  PGEs   and   gol d:(c)di r ec t   det er mi nat i on   wi t h  Ni S   but t on.The   di s ad—  

vant ag e  of   Ni S— FA  i s  t he  l ar ge  r eag ent   bl ank  t ha t  i s   der i ved  mai nl y   f r om Ni(Ogur i  e t   a1 .,1999).   2.2  Al kal i   f us i on  Al kal i  f us i on  of   s ampl es  i n  s mal l  cr u ci bl es   wi t h Na2   O2   and/or   Li 2   02  or   combi ned  wi t h NaOH ,   pr ovi des  an  i deal  means   of   s ampl e   decompos i t i o n.A  number   of   r epor t s  ar e  s ummar i z ed  i n  Ta bl e   2.   Tabl e   2.Al kal i  f usi on 

Met hods   of   aqua  r egi a   l eachi ng  a nd  s odi um per o xi de   s i nt er i ng  wer e  co mpa r ed;t he  dat a  s howed 

t hat   al kal i  f us i on  i s  bet t er   be caus e  of   t he  s t r ong  abi l i t y  o f   dec ompos i t i o n (Nogui er a   and Fi guei r edo,   1 995).I t  i s  i mpo tant r  t o  s e l ect  a  ki nd o f   s ui t abl e c r uci bl es.Ma ny  e xpe r i me nt s  hav e  de mons t r at e d 

t ha t   c o un r du m  c uc r i b l e   i s   t h e   b e s t   c h o i c e(Qi   Li a ng   a nd   Hu   J i n g.1   9 99).   I t  c an  be  c oncl ude d  t ha t   t he   pos i t i ve   as pect s   of   al kal i   f us i on  a r e:(1)eas i l y  a t t acki ng   r ef r act or y   s a mpl es   s uc h as   chr omi t es  a nd  s i l i cat es:a nd(2)l ow  cos t .On  t he   ot her   ha nd,t he   nega t i ve   as pe ct s  

a r e:( 1)l i mi t a t i o n   i n   ha nd l i ng   l a r g e   we i g ht s   o f   s a mp l e s;( 2)l a r g e   a mo u n t s   o f   s o di u m  s a l t s,wh i c h   r es ul t s  i n  hi gh  di s s o l ved  s al t  co nt e nt  i n  t he  s ol ut i ons(Dai   Xi aoxi ong   et   a1 ..2001).   2. 3 Ac i d  di s s ol ut i on  Aci d  di s s ol ut i o n pr o cedur es  ar e  wi del y  appl i ed  t o  r a pi d  de t er mi na t i on o f   PGEs  a nd  gol d. Mi x   t ur es  of   HC1,HNO3,HF,HC1 04,HBr,H2   O2,e t c.,ar e  us ed  i n  ei t her  open or  c l os ed ves s el s .  

Ther e   ar e   t hr ee   met ho ds   of   aci d  di ges t i on:(1)open  a ci d  di ges t i on,whi ch  i s   not  s ui t a bl e  f or   quant i   t a t i v e   a n a l y s i s(No g ui e r a   a n d   Fi g u e i r e d o,1 9 9 5);( 2)hi g h— p r e s s u r e   d i g e s t i o n(e. g.El y   e t   a 1 .,   1999:Mei s e l   et   a1 .,2001);and(3)aci d  l eachi ng  c ombi ne d wi t h s odi um per oxi de  f us i on  of  t he   i ns ol ubl e  r es i dues(Co edo  et  a1 .,1 997).The   de t ai l s   ar e  l i s t ed i n  Tabl e  3.   Ther e   has   bee n e ver  i ncr eas i ng  i nt er es t  i n  t he  met hods   of   Car i us  t ube   and hi gh— pr es s ur e  di ges .   t i on  whi c h i s  s omet i mes  f ol l owed by a l kal i  f us i on of  r es i dues. Car l us  t ube i s  ai r pr o of.whi ch ac.   count s   f or   t he  quant i t at i ve  dat a   of   PGE  and co mpl e t e  i s ot ope   equi l i br i um .  

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Tabl e  3. Aci d di ges t i on 

Th e   a d va n t a g e s   o f   Ca r i us   t ub e   a n d   h i g h— p r e s s u r e   d i g e s t i o n   a r e:(1)t h e   l o we s t   r e a g e n t   bl a n k;   ( 2)s uf ic i e n t   e q ui l i b r i um  o f   PGEs   i s o t o p e s,e s p e c i a l l y   f o r   Os ;a n d( 3)t o l e r a nc e   t o   r e l a t i v e l y   h i g h   t empe r a t ur e(3 0 0 ̄ C)a n d  hi g h   p r e s s ur e   whi c h  c a n   h a s t e n   s a mp l e   d i s s o l u t i o n.I n   c o n t r a r y,t he   dr a w—   b a c ks   a r e:(1)h i g h   c o s t ;( 2)r e q u i r e me n t   o f   s t a i n l e s s   s t e e l   j a c ke t   f o r   s ec ur i t y;a nd( 3)l i t t l e   s a m-   pi e  wei ght(e.g.Shi r ey  a nd  Wal ker,1 995;Du Anda o  et   a1 .,2001).   3 Preconcentrati on t echni ques  I n  gener a l,pr ec0ncent r a t i on  i s   neces s ar y  pr i or  t o  i ns t r ument a l  det er mi nat i on o f   PGEs  and  gol d  i n  geol ogi ca l   and   envi r onment al   s ampl es .I n  t he   pr ocedur es,PGEs  ar e  c oncent r at ed  rom di f l ut ed  S O—  

l u t i o ns,a nd   s e pa r a t e d   ro f m  ma j o r   ma t r i x   e l e me n t s   a nd   o t h e r   mi n o r   e l e me nt s,whi c h   wo ul d   i nt e r f e r e   wi t h t he  subs equent  ana l ys i s . Copr eci pi t at i on,i on exchange/ads o r pt i on,and s ol vent  ext r act i on ar e  

adopt ed  commo nl y.   3.1  Coprec i pi t at i on  Copr ec i pi t at i on  i s  empl oyed  i n many  a nal yt i c al  pr ocedur es  t o r eco ver  t he pl a t i num— gr oup el e—   ment s  and g ol d,es peci al l y  i n  geol o gi cal   and  envi r onment al   ma t er i al s.Tel l ur i um ,i s   mos t   requent f l y  

empl oyed,combi ned  wi t h  t i n (1 I)chl or i de   as   a  r educt ant .The  key  f ac t or s.gover ni ng  t he  r ec over —   i es  o f   PGEs  and gol d,a r e  t emper at ur e,t i me,and aci di t y. I n gener a1.t he r ec over y of   I r  i S  l o wer   t ha n t ha t   of   ot her   pr eci ous   met al s.Howe ver.wi t h  t he  pr es ence   of   KI  i n s a mpl e  s ol ut i on.t he  r ecov—  

cr y of   I r   wi l l   be   obvi ous l y  enhanced  rom  f 33% (wi t hout  KI)t o  97. 5% (Amoss e,1998).Hi g h r e—   cover i es(>90% )c oul d  be  obt ai ned under   t he  opt i mum o per at i on f ac t or s(Gr os  e t  a 1 ..2002).I t  

ca n   b e   c o n c l ud e d   t h a t   t h e   a d va n t a g e s   o f   Te   c o pr e c i p i t a t i o n   a r e:(1)hi . g h   r e c o ve r i e s( g e ne r a l l y,>  90% )of   al l   PGEs   and gol d.and (2)eas y  ma ni pul a t i o n.   3.2 I on exchange/ads Orpt i On  I on  excha nge  r es i ns  a nd a ds or be nt s  ar e  us ed as  efec t i ve means  of   s epar a t i ng  PGEs  a nd go l d  f r o m ot her   el ement s.The   r ec over i es   of   t he   pr eci ous   met a l s   by   r es i ns   or   ads or bent s  a r e   l i s t ed  i n  Tabl e 

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4.The  pa r amet e r s,gover ni ng  t he  r e co ver i es   of   t he  PGEs,i nc l ude aci di t y  of   me di a,e l ect r ova l enc e  o f   PGEs   compl ex,et c.   A pr oce dur e   has   be en  dev el oped  f or   s ampl es   cont ai ni ng  pr eci ous  met al s  g r ea t er   t han  1   g ・g 

(S hi r e y   a n d   Wa l ke r ,1 9 95).S o me   mo d i ie f d   p r o c e d ur e s   we r e   r e po te r d   t o   g a i n   h i g h e r   r e c o v e r i e s .Fo r   i ns t anc e,t wo  st a ges  ar e i nv ol ved i n t he  r o ut i ne  pr ocedur e:chl or i nat i ng  s ol ut i ons  and dupl i cat i ng  

s o r pt i o n   o n t o   a   s ma l l   a ni o n   e x c ha ng e   c o l u mn( Da i   Xi a o x i o ng   e t   a 1 .,2 0 01).The   r e s i n   r e t a i ni n g   t h e   PGEs   i s   a t t a c ke d   i n   t he   HPA— S   wi t h   c o n c e nt r a t e d   HNO ( e. g.Co e do   et   a 1 .,1 99 7;Me i s e l   e t   a 1 .,   2001).   A  nu mb e r   o f   a ds o r b e nt s   ha v e   be e n   r e po te r d   s u c h   a s   ibe f r( Xu   Li qi a ng   a n d   Ca i   Xi mi n g,1 9 9 4),   s u l ll f y dr y l   c o t t on(Li u   S ha o  ̄n g   et   a 1 .,1 9 9 4),p o l y u r e t h a ne   oa f m (Wi l d ha g e n   a n d   Kr i v a n,2 0 02),   a n d   s i l i c a   g e l( Pu   Qi a o s he ng   e t   a 1 .,1 9 99).   S ome   d i s a dv a nt a g e s   o f   i o n   e x c h a n g e /a ds o r pt i o n  a r e  l i s t e d  a s   ol f l o ws:(1)i o n  e x c ha n g e   r e s i ‘ n   c a n n o t   s e pa r a t e   Rh,du e   t o   i t s  p o o r   a b s o r ba b i l i t y;( 2)i t   i s  d i f f i c u l t   t o   de s o r b   qu a n t i t a t i v e l y   t h e s e   a na l y t e s;( 3)d i g e s t i o n   r e s i ns   o r   a ds o r b e nt s   ne e d  r i g o r o us   c o nd i t i o n s(e. g.hi gh  p r e s s u r e);a n d   ( 4)ha n dl i n g   i s   t i me— c o ns umi n g.   Tabl e  4. Recover i es  of   t he pl at i num ・ gr oup  el ement s and gol d on resi ns or  ads orben ̄ 

3.3 SoI vent   e xt r ac t i on  PGEs  a nd  Au  i n  s o l ut i o ns   can  be   s epa r at e d  f r om  ot her   el ement s   by  means   o t   l i qui d— l i qui d  o r   l i q—  

ui d— s ol i d  ext r act i o ns,a ccor di ng  t o  di f f er ent   di s t r i but i on  co ef f i ci ent s   o f   PGEs   a nd  gol d i n t wo  phas es.  

A  me t ho d   f o r   s e pa r a t i o n   o f   s t a n n o u s   c hl o r i d e   c o mpl e x   a ni o n s   o f   Pt(I I),Pd(I I),Rh(m)a nd   Au(m)wi t h   l i q ui d— l i q ui d   e x t r a c t i o n   o f   t h e   n— p r o py l   a l c o ho l 一 (NH4) 2   S O4 一 wa t e r   s y s t e m,wa s   r ep o r —   t e d( Ga o   Yunt a o   e t   a 1 .,20 0   1).The   e x pe r i me n t a l   r e s ul t s   i nd i c a t e d   t ha t   t h e   met ho d  c o ul d   e x t r a c t   t hes e  pr eci ous  met al s   si muhane ous l y  a nd  t hei r   e xt r act i on r at i os  wer e   98% 一 1 00% . Sever a l  s t udi e s  

we r e   r e p o r t e d   or f   t he   s e p a r a t i o n   o f   Pt(I I),Pd(Ⅱ)a nd   Au(1 l I)wi t h   l i q u i d— s o l i d   e x t r a c t i o n   o f   t h e   p 0l y v i n y l py r r 0 I i d0 n e — s a l t — wa t e r   s y s t e m (Wu   L i s he n g   a nd   Ga o y unt a o,1 9 98),a nd   or f   e n r i c hme nt   0f   Pt   and  Rh   as   2一 mer capt 0benz 0 t hi az 0l e  c ompl exes   by   means   of   mol t en  napht hal e ne   ext r act i on(Xi ao   Hongz han  and Li a ng  Shuquan,1 994).Rel at i vel y,t her e  ar e mor e  r epor ts  about  Re— Os  det e r mi na—  

t i o n   wi t h   s o l v e nt   e x t r a c t i o n(Pe a r s o n   a n d   Wo o d l a n d,2 00 0) .   Sol v ent  ext r act i on,ge ner a l l y, i s  i nf er i or  t o  copr eci pi t at i on and i on exchang e,be ca us e  of   t he 

f o l l o wi n g   t wo   r e a s o n s:(1)l a r g e   a mo un t s   o f   o r g a n i c   s o l v e nt s   wh i c h   a r e   a l wa y s   po i s o n o u s;a n d( 2)   l ow sel ect i vi t y.  

4 I nst rument al  det ermi nat i on of  t he PGEs  and Au  Wi t h t he  r a pi d  de vel opment   o f   i nst r ument al  t echnol ogy,i t  i s  pos s i bl e t o  det e r mi ne  t r ac e PGEs  

a nd  Au s i muhaneousl y   or  s equent i al l y.The  det ect i on  l i mi t s  of   i ns t r ument al  t echni ques   or f   t he  PGEs  

a n d   Au   a r e   d e s c ibe r d   i n   Ta b l e   5(Do n g   S ho u’a n,2 00 0).  

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Tabl e  5. Avai l abl e  techni ques  f or det erm i nat i on  of   the  preci ous metal s   0f   di f f erent l   c0ncent rat i 0ns 

4. 1   I nduc t i ve l y   c o up l e d  p l as ma   ma s s   s pe c t r ome t r y( I CP- MS)   The  I CP- ・ MS  t echni que   has   become   a  popul ar   appr oach  t o   de t er mi nat i on  of   PGEs   and  Au  i n  geo— ・  

l og i c a l   a n d  e nv i r o n me nt a l   s a mpl e s   o wi ng   t o   i t s   f o l l o wi ng   a d v a nt a g e s:(1)s i mp l e  s p e c t r a;(2)e x —   c e l l e n t   d e t e c t i o n   l i mi t s   g e ne r a l l y( 0. 001—0. 1)×1 0一;( 3)wi de   l i ne a r   dy n a mi c   r a n g e( iv f e   t o   s i x   o r d e r s );( 4)c a pa bi l i t y   o f   s i mu l t a ne o us   mul t i — e l e me n t   a na l ys e s   d ue   t o   r a pi d   s c a n ni n g   f a c i l i t y;( 5)   a   f a i r   d e g r e e   o f   t o l e r a n c e   t o   i nt e r f e r e nc e;( 6)a bi l i t y   o f   me a s u r i ng   i s o t o p e   r a t i o s;a n d( 7)p os s i b i l i t y   of   i s ot ope  di l ut i on cal i br at i on s t r at e gi es  t hat  o ver come  t he  i nt e fer r ence  of  l oss es  o f  anal yt es  at  t he  

pr epar a t i on s t ages.The  l ar ge  qua nt i t i es  of  r ef er e nces  on  PGEs  and gol d det er mi nat i on  by  I CP— MS  s ho wed t hat  i t   i s  a  f avor i t e  t echni que.  

On e   l i mi t i n g   f a c t o r   i s   t h e   l o w  t o l e r a n c e   t o   hi gh   di s s o l v e d   s a l t s   i n   s a mp l e   s o l ut i o ns .Fl o w  i n j e c —   t i o n   c o ul d   o v e r c ome   t he   pr o bl e m  t o   s o me   e x t e n t( Ca o   Sh uq i n   e t   a 1 .,2 00 0).La s e r   a b l a t i o n(L A)i s   an  al t er nat i ve   means   of   i nt r oduct i on  f o r   r api d  det er m i nat i o n.The   LA— I CP- MS t e chni que   i s  a ppl i e d t o 

de t e r mi na t i o n   o f   t h e   c o n c e n t r a t i o n s   o f   Pt ,Pd  a n d  Rh  i n   u r b a n   r o a d   s e d i me nt s(Mo t e l i c a — He i no  e t   a 1 .,2 00   1),a nd   o f   Au   a nd   t h e   pl a t i n um— gr o u p   e l e me n t s   i n   ge o l o g i c a l   s i l i c a t e s(Kl e mm  a n d   Bo n— r   bach,200  1).Howe ver,t her e  r emai n s ome  pr obl ems  i n LA— I CP— MS,s uc h as  poor  r epr o duci bi l i t y   and ac cur a cy,t he   l ack  o f   s ui t a bl e   i nt er n al   s t andar d  el ement s   f or   t he   cal i br at i on  of   pea k  dr i f t   and  ma—   t ri x i nt e  rente.  

4. 2  Ne ut r o n  ac t i va t i o n  a na l ys i s(NAA)   NAA i s  al s o  one  o f   t he  pr ef er r ed t e chni ques  f or  pr eci ous  met al  a nal ys i s  i n  geol ogi cal  and envi —   r onme nt al  s ampl es,owni ng t o i t s  hi gh s ensi t i vi t y,f ine  a ccur a cy,a nd f ree dom f rom c ont ami nat i on 

(Li  Xi a ol i n et  a1 ..1996).   Among t he  pr eci ous  met al s,t he  mos t  s ens i t i v e  el ement s  f or  NAA ar e  I r,Rh a nd Au (McDo—  

n a l d   e t   a 1 .。1   9 94).Two   t e c h ni q ue s。n a me l y   1 CP— MS   a n d  NAA。we r e   e mp l o y e d   t o  d e t e mi r ne   t he   PGEs   i n   g e o l o g i c a l  s a mp l e s,a nd   t he   da t a   s ho we d   t he y   a r e   c o mpl i me nt a r y(Li  Ch un s he n g   e t  a 1 .,   20 0   1) .Ho u   Qua nl i n   a n d   Ma   Pe i x u e(1   9 97)co nc l u de d   t ha t   t he   i n t e fe r r e nc e   o f   Au   o n   Pt   wa s   s e r i o us   f 0r  mo st  r ocks.yet  t he  i nt er fer ence  of  U on Ru or  Pd was  ne gl i gi bl e  by NAA f or  mos t  ul t r amaf ic   r ocks   and  s ul ide f   or es.   Due  t o  unhea l t hy  and t i me— cons umi ng  of  i ra di at i on,t he  use  of   NAA t ends  t o  decl i ne  s t ep  by   st ep.  

4. 3   Ne g at i ve   t he r mal   i o ni z a t i on   ma s s   s pe c t r o me t r y(NTI MS)   I s o t o pi c  a na l ys i s   by   ne g a t i v e   t he r ma l   i on   ma s s   s pe c t r o me t y( r NTI MS)ha s   pl a y e d   a   gr e a t   r o l e   i n   d e t e r mi n a t i o n   o f   Re,Os   a n d   Pt   or f   c h r o n o l o g y(e. g .Pe u c k e r — Eh r e n br i nk   a n d   Bl um,1   9 98;S ha r ma   e t   a 1 .,1 9 99;Du   And a o   e t   a 1 .,20 01).Cr e a s e r   e t   a 1 .(1 9 91)e s t a bl i s he d   a   me t h o d   o f   NTI MS   or f   pr e ci s e i s ot opi c  a nal ys i s  of   Os,Re  and l r   and a chi eved  an e xcel l ent   r es ul t .  

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Vo1 .23  

Compa r ed  wi t h I CP— MS,t he  r at i o  o f   i oni z at i on i s  hi gher  t ha n t hat  of  I CP— MS,t her ef or e,t he   s ens i t i vi t y  of   NTI MS i s,i n  gener al ,hi ghe r   t ha n  t hat  o f   I CP— MS.Anot her   advant age  of   NTI MS i s   no  

i s oba r i c  i nt er fer e nce   bet we en Re  and Os.Thus,s epar a t i on o f   Os  and Re  i s   unneces s ar y.   4. 4  Ot her  t ec hni ques  

Fl ame   at omi c  abs or pt i on s pec t r ome t r y f   FAAS)i s  a  us ef ul  t ool  t o det er mi ne  PGEs  and  go l d a t   hi gh l evel s.but  i s   no t   s ui t abl e   f or   t hos e  a t   t he   concent r at i ons   l ower   t ha n ng・g~ .The   us e   of   FAAS 

or f   t he  PGEs  a nal ys i s  has   be en  di s cus s ed  i n  de t ai l(Zhang  Kai  e t   a1 .,1   997).Compar ed  t o  FAAS,  

g r a p h i t e   f l a me   a t o mi c   a bs o r pt i o n  s pe c t r o me t y (GFAAS)ha r s   l o we r   de t e c t i on   l i mi t s(Br z e z i c ka   a nd   Bar a no wska,2001).Osmi um i s ot opes   and s i l ver,as   t r acer s  o f   a nt hr opoge ni c  me t a l s  i n s edi ment s,   wer e  det er mi ned  bv  GFAAS a nd NTI MS,r es pect i vel y(Ravi z z a  and  Bot hne,1   996).The  out s t a nd—   i ng  di s advant ages  of   GFAAS  ar e  i t s  poor   pr oduct i vi t y  and s ever e  i nt e fer r ences .  

I CP— AES   i s   c ha r a c t e r i z e d   by   hi g h  t e mp e r a t u r e(~1   0 00 0  K),r e s u l t i ng  i n  s up e r i o r   de t e c t i o n   l i mi t s.1 ow backgr o und  emi s s i on.f e w chemi caIi nt er f er ences   and a   wi de   l i nea r   r es pons e   r ange (5— 

6   o r d e r s   o f   ma g ni t u de).Ho we v e r ,d ue   t o   t h e   r e q ui r e me n t   o f   a   l a r g e   s a mpl e   we i g h t   t o   v o l u me   r a t i o,   t he  appl i ca t i on o f   t he  t echni que  i s  l i mi t e d.  

5 Concl usi ons  As  t o  s ampl e  deco mpos i t i on,Ni S  f ir e  as s ay  i s   f a vor i t e   or f  s ampl es  co nt ai ni ng   pr e ci ous   met al s   at   ng.g~ l e ve1 .Hi gh— pr es s ur e  di ges t i on  and Car i us   t ube   have   been  co mmonl y  appl i ed  t o  s ampl es   con—  

t a i ni ng  ul t r a— t r ac e  pr e ci ous  me t al s,whi ch c oul d  pr omot e  gr eat l y  chr onol ogi cal  r es ear c h.As   or f   pr e—   concent r at i on,Te— copr eci pi t at i on  i s  pr ef e r abl e.Wi t h  r e gar d  t o  i ns t r ument al   t echni ques,I CP— MS  en—  

j o y s   a   l e a d i ng   r o l e,d ue   t o   h i g h   r e l i a bi l i t y,a nd   NTI MS   i s   a   po we fu r l   t o ol   or f   t he   a n a l y s i s   o f   Re,Os,   and  Pt .  

Ana l yz i ng  t he   de vel opment   and  appl i ca t i o n o f   s i mul t a neo us   o r   s eque nt i al   de t er mi na t i on  of   mul t i —   el ement  PGEs  and Au  i n  t he   wor l d,we   can  ind  f out   a  bas i c   f or m ul a  or f   t he   whol e   de t e r mi nat i on  pr o—   cedur e:a  r api d, pr eci s e  and ac cur at e  i ns t u ment r  det er m i nat i on me t hod combi ne d wi t h compl e t e   s ampl e  de composi t i on and e f f e ct i ve  s epar at i on.  

Ref erence s   Amo s s e,J ,1   998,Det e r mi n at i o n of  pl at i num— gr oup el ement s  and  g ol d i n g eol og i c al  ma t r i c es  b y i nduc t i v el y  c oupl ed pl as ma  ma ss  

s pe e t r o me t  ̄( I CP— MS)a f t e r   s e p a r a t i o n   wi t h   s e l e ni u m  a n d   t e l l i u m  c a r r i e r s[ J ]:Ge o s t a n da rd s   Ne ws l e t t e r ,v . 2 2,n .1 ,P.9 3—   1 O2.  

Br z e zi c ka,M .and  I .Bar anows ka,2001.Met hods  f o r   s e par a t i on   of   t r ac e   amo unt s   of   pl a t i num  and  i nve st i gat i on   of   t he  i nf luence   of   i n—   t er f er i ng  el eme nt s  dur i ng  pl at i num det e r mi nat i on i n  co pper   or e s  and  co pper   conc ent r at es  by  g ra phi t e  f ur nace  a t o mi c  abs or pt i on  

s p e c t r o me t r y[ J ]:S pe c t r o c h i mi c a   Ae t a( Pa r t   B):At e mi c   S pe c t r o s c o p y,v . 56,n. 1 2,P. 2 51 3—2 52 0.   Cao   Shuqi n,Che n Hangf ing,and  Ze ng   Xi a nj i n,200 0,Ma t ix  r e fec t s  i n  low  f i nj e ct i on— i nduc t i ve l y  c oupl ed  pl a s ma  mas s   s pect r omet r y  

J ]:Ch i n e s e   J o u na r l   o f   An a l y t i c a l   Ch e mi s t  ̄,v . 28,n . 1 2,P. 1 4 76—1 48 0( i n   Ch i n e s e   wi t h   Eng l i s h   a bs t r a c t )   Chen  Shug ui ,Zuo   Yanl i n,So ng   Ha owei   et   1.,1 a   996,Si mul t aneo us   det e r mi na t i o n  o f   t r ac e  g ol d,pl a t i num,pa ll a di um  and  r ho di um  i n  

g e o l o g i c a l   s a mp l e s   b y   c a t i o n   e x c h a n g e   r e s i n   s e p m' a t i o n — p a ti r a l   l e a s t   s q u a r e s   s p ee t r o p h o t o me t r y[ J   J.Chi n e s e   J o ur na l   o f   An a l y t i c a l   Che mi s t r y .



v  24,n.9,P.1 056—1058(i n  Chi nes e  wi t h En gl i s h  abs t r a ct).  

Coedo,A.G.,M.T.Dor a do,I .Pa di l l a   et   a 1 .,1 997,Pr e eon( : ent r at i on  and  ma t r i x  s e pa r a t i on   of   pr eci ous   me t al s   i n  g e ol o gi ca l   and  r e—   l at e d ma t e ial r s   us i ng   me t al f i x— c hel ami ne   r es i n  pr io r   t o   i nduc t i v e1 v   cou pl e d  pl a s ma   mas s  s pec t r ome t  ̄ J]:Ana1 .Chi m.Act a,   .

340.P. 31—4O.  

Cr e as er,R.A.,D.A.Papanas t a ss i ou,a nd  G. J.Was s e lmr f g,1 991,Ne gat i ve   t he ma r l  i on  ma s s   s pect r o met l y o f   os mi um,r heni um ,  

and  i idi r um J]:Geoc hi m.Cos mochi m.Ac t a,v 55,P.397—401.   Dai  Xi a oxi o ng,C. Koe be d,and  H. Fr S s ehl,2001,Det er mi na t i on   o f   pl at i num — ro g up  el eme nt s  i n   i mpac t   br e cci as   us i ng   neut r on  a et i —  

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va t i on  anal vs i s  an d ul t r as oni c  ne bul i z a t i on  i nduct i v el y  c oupl e d pl as ma ma s s  s pee t r omet u a f t er  a ni on  ex cha nge  p  e conce nt r at i on  

J]:Ana1 .Chi m.Act a.v.436.P.79—85.  

D0 n g   S h o u a n.2 0 0 0.An a l y s i s   o f   p r e c i o u s   me t a l   ma t e r i a l s: J ]:Ro c k   a n d   Mi n e r a l   An a l y s i s ,v . 1 9,n .1 ,P. 2 0—3   1( i n   Ch i n e s e   wi t h   Eng l i s h  ab st r a ct ).   Du  Anda o.Zha o  Dunmi n,Wang   Shu xi an  e t   a1 .,200   1,Pr eci s e  Re— Os  dat i ng   f or   mol ybdeni t e  by   I D— NTI MS  wi t h  Ca r i us   t ube  s a mpl e 

p r e p a r a t i o n[ J ]:Ro c k   a n d   Mi n e r a l   An ly a s i s ,v  2 0,n. 4,p.2 47—2 52(i n   Ch i n e s e   wi t h   En g l i s h   a b s t r a c t ).   El i s a,K.,Shi buy a,E.S.S.J o r ge   et   a1 .,1 998,De t er mi na t i o n  of   pl at i num— gr o up  el ement s   and   gol d  i n  g eol o gi ca l   mat er ia ls   us i ng   a n 

u l t r a v i o l e t   l a s e r   a Ll a t i o n   h i g h- r e s o l u t i o n   i n d u c t i v e l y   c o u p l e d   p l a s ma   ma s s   s p e c t r o me t r i c   t e c h n i q u e[ J ]:J o u r n a l   o f   An ly a t i c a l   A—     t omi e  Spe ct r omet r y v.13,n.9,P.941—944. .



El y,J.C.,C.R.Ne al,J r.J.A.O’Nei l l  et  a1 .,1 999,Quan t i f yi ng  t he  p l a t i num— g r oup  el ement s(PGEs)and g ol d  i n  ge ol og i ca l  s a mpl es  usi ng   c at i on  e xc hange   pr et r e at ment   and  ul t r a s oni c  nebul i z at i on  i nduc t i v el y   c oupl e d  pl a s ma— ma s s   s pe ct r omet r y (USN- I CP—   "



MS)『J]:Chem.Ge o1 .,v.1 57.P. 21 9—234.   Enz wei l er,J .,P.J.Pot t s,and  K.E.J ar vi s,1 995,Det er mi nat i on  o f   pl at i num,pa ll adi um,r ut heni um  and  i idi r um  i n   ge ol og ic l  a s a m—   pi es  by   i s o t ope   di l ut i o n  i nduct i v el y   co upl e d  pl as ma   mas s   s pe ct r omet  ̄ us i ng   a   s odi um  pe r o xi de  f us i on  an d  t el l ur ium  eo pr eci pi t at i —  

on  J1.Anal ys t ,v.1 20.P.1391—1 396.   Fr i mpong,A,,B. J.Fr y er,H.P. L on ger i c h e t  a 1 .,1 995,Re cov e ̄ of   pr ec i ous  me t al s  us i ng  ni ckel  s ul ide f  f ir e  a s s ay  co l l e ct i on:  

P r o b l e ms   a t   n a n o ra g m  p e r   g r a m  c o n c e n t r a t i o n s[ J ]:An a l y s t ,v . 1 2 0,P. 1 6 7 5—1 6 8 0.   Ga o  Yunt ao,Wu  Li she ng,and  Wang   Wei ,2001,Se par a t i o n  of   pl at i num,pa ll adi um,r hodi um  and  gol d  by  l i qui d- l i qui d  e xt r a ct i on  

s   y s t e m  o f   n — p r o p y l   a l c o h o l 一 ( NH4) 2 s 04 一 wa t e r[ J ]:Ch i n e s e   J o u na r l   o f An a l y t i c l  a Ch e mi s t  ̄,V . 2 9,n  8,P  9 01—9 03( i n   Ch i -   ne s e  wi t h  Eng l i s h  abs t r a ct ).   Gr os,M.,J.P.b r a nd,a nd  A.Lu gue t,2002, Ana ly si s  o f   pl at i num- g r oup  el ement s   and  g ol d  i n  g eol og i cal  ma t e ia r ls   usi ng  Ni S f ir e  

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Ho u   Qu a n l i n   a nd   Ma   P e i x u e,1 9 9 7,l n t e r e l e me n t   i n t e r f e r e n c e s   i n   p l a t i n u m- ro g u p   e l e me n t s   a n a l y s i s   b y   NAA[ J]:Ro c k   nd a   Mi n e r a l   Ana l y si s,v.16,n.1,P.1 8—21(i n  Chi nes e   wi t h  Engl i s h a bs t r ac t).   J a r vi s,1 .,M.M.Tof land,and  K.E.J a r vi s,1 997,As s es s ment  o f   Dowex  1一 X8. ba s ed  ani on. e xcha nge  pr o ce dur e  f o r   t he  s epa rat i on  a nd  det er mi na t i o n  of   ut r heni um,r hodi um,pal l adi um,i idi r um,pl at i num  and  go l d i n  geo l ogi c al   s ampl es  by  i nduct i vel y ,c oupl ed  pl asma mass spect romet ry [ J  :Ana lys t ,v.122,P.1 9—26.   .

J or ge,A.P.S.,J.Enz wei l e r,E.K.Shi buya   e t   a 1 .,1 998,Pl at i num— roup  g e l eme nt s   and   gol d  de t er mi nat i on   i n  Ni S   ir f e   as s ay   but t ons   by  UV  l ser a  a bl at i o n  l CP- MS   J :Geos t an da r ds  News l et t e r,v. 22,n.1,P. 47—55.   J uv onen,R.,E.Ka l l i o,and  T.Lako maa,1994,Det er mi nat i o n o f   pr e ci ous   met a l s  i n  r o cks  by  i nduc t i v el v  co upl e d pl as ma  ma s s  

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t i o n s[ J  :An a 1 .Ch i m.Ae t a,v . 3 3 4,n. 1—2,P. 1 6 7—1 7 5.   Li   Chun she ng,Chai   Zhi Nng,Mao   Xue yi ng  et   a1 .,2 00   1,Det e m i r na t i o n  o f   pl at i num- ro g up  e l ement s   by   neut r on  a ct i v at i on   ana l y s i s   and  

i n d u c t i v e l y   c o up l e d   p l a s ma — ma s s  s p e c t r o s c o p e   c o mb i n e d  wi t h  f i r e  a s s a y  p r e e o n e e n t r a t i o n [J]:Ch i n e s e   J o u r n l o a f   An ly a t i c a l   Chemi s t r y v . 29,n  5,P. 53 4—537(i n  Chi nes e   wi t h  Engl i s h  abs t r a ct ).   .



Li  Xi a ol i n,Ton g  Chunan,Zhu  Ji e pi ng   e t   a1 .,1 996,De t e mi r nat i on   of   pl a t i num— g r oup   el eme nt s  i n   f o ur   ne w  r e f e r enc e  s m pl a e s   o f   ma.   r i ne   s edi ment s   and  nodul e s  by  ne ut r on  ac t i v at i on  ana ly si s  a ft e r   ni ckel s   s ul phi de  ir f e  as s ay  pr eeo neent r at i on f   J  :Geo st an da rds   ,

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292 

CHI NESE  JOURNAL  OF  GEOCHEMI STRY 

Nogui er a,C.A.and M.G. Fi guei r edo,1995,Det er mi na t i o n  of   pl at i num ,pa l l a di um



Vol _23 

i idi r um and  g ol d i n  s el ect e d g eol og i ca l  r ef er .  

e nc e  ma t er ial s   by   r adi ao chemi ca l  neut r on   aet i vat i un  a na1 )s i s:Compar is o n  o f   pr oce dur es   bas e d  on  a qua  r egi a   l e achi ng  a nd  s odi um 

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MS)  J ]:Ch e m.Ge o 1 .,v .1 5 7,P .1 8 9—1 9 7.   Pauke ̄,T. a nd I . Rube s ka, 1 993。Ef f e ct s   of   f us i on  c bar g e  co mpos i t i on  i n  t he  det er mi na t i o n o f  p l at i num - gr o up e l eme nt s   usi ng   co1 .  

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a n d   Re - Os   i s o t o p e s   i n   g e o l o g i c a l   s a mp l e s   b y   i s o t o pe   d i l u t i o n   I CP- MS[ J  :Ch e m.Ge o 1 .,v . 1 6 5,P . 8 7—1 07 .   Pe uc ker - Ehr e nbr ink,B.a nd  J.G.Bl um,1 998,Re- Os  i s ot ope   s ys t ema t i c   and  we at her ing  of   Pr ec ambr ian  c r us t al   r ocks:I mpl i cat i ons  

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Sun Mi n,J .1 ai n,Zhou  Mei f u   et   1.,1 a 993,A  p r oce dur al   modi ica f t i on   f 0 r   e nha nce d  r ec ov er y  of   pr eci o us   met ls(Au.PGE)f a ol l o w.   i ng   ni c kel  s ul phi de   ir f e   a s sa y   and  t el l ur ium  c opr ec i pi t at i on:Appl i ca t i o ns   f or   a na lys i s   o f   ge ol o gi ca l   s ampl es   by  i nduct i v el y   coupl ed  

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Wu   Ru n l i n,L i   Ma o s h u,a n d   Wu   L i s h e n g,1 9 97,De v e l o p me n t   i n   i f r e   a s s a y   o f   p r e c i o u s   me t ls[ a J]:P r e c i o u s   Me t a l s ,v . 1 8,n .1,P.   44 —48(i n  Chi nes e   wi t h  Engl i s h  ab st r a ct ).   Xi ao   Hongz ha n a nd Li ang  Shuqua n,1994,Enr ichment   of   t r ac e   amount s   o f   pl a t i num  and  t hodi um  by   means   of   mo l t ed   napht ha l e ne   e x-  

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i s o t o p e   d i l u t i o n   i n du c t i v e l y   c o u p l e d   p l a s ma   ma s s   s p e c t r o me t r y   i n   g e o l o g i c a l   s a mp l e s[ J ]:An 1.Ch a e m.,v . 6 8,n. 8.P . 1 4 4 4一   l 450  

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