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ANALYTICAL , GEOCHEHI CAL AND BI OGEOCHEHI CAL S TUDIES OF TUNGSTEN AND MOLYBDENUM
A the si s presented in parti al ful fi lment of the requi rement s for the de gree of
Doc tor of Phi l sophy at
Mas sey Universi ty
BERTRAH FRANCI S QUI N 1 974
To Lyn
ACKNOWLEDGEMENTS
I would like to thank my supervisor Dr. R.R. Brooks, for his enthusiastic encouragement and assistance during the course of the work described in this thesis. I also thank my eo-supervisor, Professor J . K . Syers, for his guidance during the absence of Dr. Brooks.
Particular thanks are due to the Mineral Resources Sub-Committee of the University Grants Committee for funds to support this project.
Thanks to Mr. J.H. Hogland of the Grasslands Division, D.S.I.R. for his assistance with the clover pot trials.
Mr. P. Nes kindly carried out the nitrogen analyses.
To Dr. N.E. Whitehead of the Nuclear Sciences Institute, D.S.I.R. for his assistance during the investigation into the use of proton-induced X-ray fluorescence.
To Dr. C.R. Boswell of the Computer Science Department, Massey University, for carrying out the trend surface
analysis of biogeochemical data.
To Dr. M.H. Timperley of Chemistry Division, D.S.I.R.
for the use of his soil and plant data.
I am indebted to Carpentaria Exploration Ltd. for
logistic support during the investigations at Barrytown, and in particular I would like to thank l'1lr. J .A. C. Painter of this company for his assistance. Alex Harvey Industries k indly provided accommodation at Glenorchy. I am very grateful to Mr. E.J. Sixtus of Motueka for his assistance during the investigations at Canaan.
Finally, I would lil{e to thank the Ministry of
Agriculture and Fisheries for permission to complete this thesis after my appointment.
(iv)
ABS TRACT
S e c t ion I : S tudie s were carried out which significant ly imr.-roved l:he s e!lsitiv:i.ty of the
cal orimetric met hod for the determinat ion of tungsten in geochemic al and pl ant samples with dit hio l .
Pro t on-induced x-ray fluorescence was al s o inve st igat e d t o determine it s s uit ab il ity for the det e c t ion o f
nano gram quantit ie s of tungs t en. However al though it showed c onsiderab l e pot ent ial , the sensit ivity of the method coul d not be devel oped sufficient ly to c ompare favourably with c ol orimet ry.
A rapid method for the determinat ion of
t ungsten in ore s ill1d c oncent rates by at omic absorpt ion spect romet ry was devel oped which , throu gh t he use of an alkal ine sampl e s olut :i_on, was free of int erference and ins t abil ity probl ems .
Fol l owing a ca!'eful study of t he paramet ers involved in the cal orimet ric me thod for the
det ermination of molyodenum with dithiol 7 a simple procedure was developed which coul c_ be used for the analysis of a wide range of mat erials .
The usP of thP nitric/hvdrofluoric ac id mixture for the dige s t ion of s oil s and rock s was inve st igat ed. I!:: was found that the t endency for c alcium and mag-fle sium to precipit ate as their
fluoride s c ould be avoided by the addit ion of a small quantity of perchl oric acid .
Section II : S chee l it e s from several l ocalit ies in New Zealand were analysed for their trace el ement c ontent . They were found t o c ontain very l ow a"Tlount s of impurit ie s . Their S r/B a rat io was found t o be u seful for dis t inguishin g between l ode s .
(v)
S ecti on III : An i nvesti gati on was c arri ed out to compare the rel ative effi c acy of geochemi c al and bi o geochemi cal e�:pl oratiml for �cungs ten under a wi de range of geol ogi c al , vegetati onal , climati c and
topo graphi c al condi ti onso It was found that, under most condi ti ons7 both soil and pl ant samp l i n g c ould be used equally s ucces s fully to pinpoint s cheel i te beari n g veins. In are a s of hi gh rai nfal l and rugged topography , soi l s amp l i n g did no-:: always r2veal the pres enc e of reefs and , i n the s e c as e s , trunk-s ampl i n g o f tre e s coul d provi de addi ti onc.l i nformati on. It was found that, for the purposes of biogeochemi c al
prospecting, all tree s peci es coul d be grouped to gether.
F ollowin g thi s i nve s ti gati on, a more inten sive s tudy was carri ed out at Barryto"�Jm to tes t the
sui tabil i ty of trend surfc..ce anc.lysi s of bi o geochemi cal d ata for loc ati ng ri ch pockets of scheelite wi th
vein s , wi th promi sing resul ts .
A bri e f compar,sonof geochemi cal and
bi o geochemi cal prospecting for molybdemMn was c arri ed out at C anaan, Nel s on. It was fmmd tL:tt plant
s ampl i n g gave more i nf ormati on where the l ow s oi l pH prevented movement of molybdenum into the upper s oi l .
Secti on IV : Fol l owing the results of the bi o geochemi c al expl orati on i n Secti on IV� whi ch showed the exi s tenc e of di fference s in the
di s tri buti on of tun g sten between tree organs from Barrytown and C anaan , the affect of s oi l s odium and potas sium was i nves ti gated and was found to be
responsible for the s e di fference s .
As considerable areas containing scheelite mineralisation support pasture 1 c..n inves �i gation \If as carried out to study the effects of applied tungsten on clover growth. Tunssten: applied as tungstate, was found to sli gf1·l:ly decrease growth where fixation was the sole :1.i·trogen so"v:rce. I n the presence of
combined. r..i trogci1; huwever, i11.creases were
recorded.
A cor:1p2rlson of the elemental composition of
native tree spE.cies was carried out to iYlvestigatE::
the effects of Sl.:'.ostr2,te cornr:osi tion. It was found that; wnereas vegetation a:r1alysis can :i_n general be used to indicat� th2 presence of mineralisation within a :�oclc type? it is not a reliable indicator of the composition of different rock types.
(vi)
(vii)
TABLE OF CONTENTS ACKNOULEDGEHENTS
ABSTRACT
TABLE OF CONTENTS L I ST OF F I GURE S
page (i i i) (iv) (vi i) L I ST OF TABLE S
GENERAL INTRODUCTI ON
(xi i) (xiv)
1 SECTION I - DEVELOPl·iENT OF ANALYTICAL HETHODS 8
A . INTRODUCTION 9
B . TUNGSTEN 1 2
1 . Further development of c ol orimetri c
method 1 2
(a) Introduct i on 1 2
(b) Descri pt i on of exi sting procedures 1 3
(i) Equirment 1 3
(ii) Soluti ons 1 3
(iii) Determinat i on of tungsten
in soi l s and rocks 1 4
(iv) Determinat i on of tungsten
i n pl ant sampl es 1 5
(c) Further devel opment s investi gated 1 5 (i) Improvement of sensi tivi ty 1 5 U se of small er s ample volume 1 5 Use of l arger sample si ze 1 6 (ii) Improvement of productivi ty 1 7
Soi l s 1 7
Pl ant s ampl es 1 9
(d) Conclusions 1 9
2 . Investi gati on into the use of proton
induced x-ray fluorescence for the determinati on of nanogr�n quanti ties
of tungsten
l
a) Introduct i on 21 21b) Equi pment 2 3
c) Devel opment work 26
(i) Introduct i on 26
(i i) Analysi s of pl ant ash and
s oi l s ample s 27
(i i i) Puri fi cati on and c oncentrat i on of tungsten using ani on-
exchange chromatography 28
Introduct i on 28
Experiment al 28
Re sul t s and di scussion 29
c.
(iv) Puri fi cat i on and concentrati on of tungsten by extrac t i on into a solut i on of di thi ol in
( vi i i )
i soillnyl ace t ate 30
Introduct i on 30
Experimental 30
Re sul ts ill1d di scussi on 31
Sensi tivi ty 32
Conclusi ons 3 3
3 . Development of an at omic absorption spectrophot ometri c method for the analysi s of tungsten in ores and c oncentrates
( a ) Introduct i on
(b) Literature survey (c) Devel opment
(i) Di ge s t i on
( ii ) Flillne condi t i ons Fl illne s t oi chtometry Positi on of the flillne
Air drau ght s in the l aborat ory Air vel oci ty in the fume exhau s t (i i i)C alibrati on curve
( d ) Experimental (i) Equi pment
(ii) S t andard tungsten soluti ons (iii)Digesti on of the s ample
(iv) Atomic abs orption determinat i on of tungsten
( e ) Reproducibi l i ty and recovery tes t s (i) Recovery of tungsten
( ii ) Reproducibi l i ty and accuracy ( f ) Interferences
( g ) sen si ti vi ty ( h ) Productivi ty ( i ) C onclusi on MOL YBDZNU11
1 . Li terature survey
2 . Survey of exi sting di thi ol procedure s 3 . Development of the method
( a ) Preliminary t reatment of s illnpl es (i) Ashing of botani cal sillnpl es ( ii ) Fusi on of geochemic al sillnpl es ( ii i ) Di ssoluti on of steel sample s ( b ) Parameters affecting the formati on
and extracti on of the c omplex ( i ) The nature of the di thi ol
s olvent
( ii ) Acidi ty of the sample soluti on (c) Interferences from other el ement s
(i) Tungsten ( ii ) I ron (ii i ) C opper (iv ) Tin
3 5 3 5 36 40 40 41 42 42 45 45 46 47 47 47 47 48 48 48 48 48 5 3 5 3 5 3 5 5 5 5 6 1 57 6 1 6 1 6 1 6 2 6 5 6 5 6 6 67 67 6 9 7 2 74
c.
4 . 5 .
6 .
Experimental ( a) Equi pment ( b ) Reagent s Procedures
( a) Determinati on of molybdenum in botani cal m1d bi ol ogical
s amples
( b ) Determination of molybdenum in geochemical sampl es
( c ) Determinati on of rnolybdenum in steel s
Te sting of method
(a) Reproducibi l i ty and recovery tes t s (b) Sensi tivi ty
( c ) Productivity Conclusions
OTHER ELE11ENTS 1 •
2 . 3.
4.
5 . 6 . 7 .
Introducti on
Treatment of geochemic al samples ( a ) Prelim�nary treatment
( b ) Di ssolut i on procedure Treatment of plm1t s amples ( a ) Preliminary treatment ( b ) Ashing techniques Interferences
( a ) Chemi cal interferences ( b ) S cat terins; and non-at omic
absorpti on
C ondi ti ons used in atomic absorpti on determinat i ons
Accuracy and reproducibi li ty of the di s soluti on and analyti cal methods D . S . I . R . analyses
SECTION II - THE TRACE ELEIIENT COHPOSITION OF NEU ZEALAND S CHEELITE S
A . B .
c.
INTRODUCTI ON
ANALYS I S OF SCHEELITE 1 . Puri ficat i on
2 . Chemical analysi s RE SULTS AND DI SCUS S I ON
1 . Level s of impuri t i e s in scheelites 2 . Correl ati on between l odes
( a) Introduct i on
( b ) Re sult s and di scussi on
(ix)
7 4 7 4 7 5 7 5
7 5 7 6 7 7 7 7 7 7 7 9 7 9 7 9 8 0 8 0 8 0 8 0 8 0 8 2 8 2 8 2 8 4 84 84 8 5 8 5 8 5 8 8 8 9 9 0 90 9 0 9 0 90 93 9 3 94
(x )
SECTI ON I I I - GEOCHEl'UCAL AND BI OGEOCHEHICAL EXPLORATI ON FOR TUNGS TEN AND HOLYBDENUI'-1
A.
B .
c .
INTRODUCTION 1 • Tungsten 2. I1olybdenum TUNGS TEN
1 . The detec tion of scheel i te-bearing ore-bodies by the analysi s of
pl ant s and soi l s ( a ) I ntroduct i on
( b ) Descri ption of test areas
( i ) Glenorchy , Paradise, 11acrae's Fl at and Top Valley
Descri pti on of minerali sati on ( ii ) Barryt o\\m and canaan
Descri ption of minerali sat i on ( c ) Fi eld work
( d ) Chemi cal analysi s ( e ) Resul ts
( i ) Glenorchy ( ii ) Paradi se
( ii i ) Hacrae's Fl at ( iv ) Top Valley (v) Barryt o�m (vi ) C anaan ( f ) Di scu s si on
( i ) Glenorchy, Paradise, Macrae's Fl at and Top Valley
( ii ) Barrytm1m and C anaan ( g ) Conclusions
2 . Trend-surface analysi s of tungsten concentrati ons in tree truruc s at Barrytown
(a ) Introducti on
(b ) Trend-surface analysis (c ) Field work
(d ) Re su l t s
( e ) Di scussi on and c onclusi on HOLYBDENUM
1 . Bi o geochemical explorati on for molybdenum at c anaan , Nelson
( a) Introduct i on ( b ) Field work
( c ) Chemical analysi s
( d ) Resul t s and di scussion ( e ) C onclusi ons
97 93 98
1 00 1 02 1 02 1 02 1 02 1 02 1 04 1 06 1 07 1 08 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 11 2 1 1 3 1 1 3 1 1 3 1 1 5 1 1 6
1 1 7 1 1 7 1 1 8 1 20 1 20 1 2 3 1 2 3 1 2 3 1 23 1 24 1 25 1 25 1 27
SECTION IV - BIOGEOCHEIHCAL STUDIES A . INTRODUCTI ON
B .
c .
D .
THE EFFECT OF S OI L SODIUM ON THE UPTAKE OF TUNGS TEN FUSCA
AND POTAS S IUI'1 BY NOTHOFAGU S 1 . Introducti on
2 . 4. 3.
5 . 6.
Preliminary fi eld work Setting up of pot tri al Analyt i c al �ethods
Resul t s and di scussi on Distri buti on of tungsten D ay 300
Conclusi ons
i n pl ant s ,
THE EFFECTS OF TUNGSTATE AND NI TROGEN S OURCE ON THE DRY HEI GHT AND NITROGEN YIELDS , AND NOCYBDENUl1 AND TUNGSTEN CONTENT , OF l:lHITE CLOVER ( TRIFOLIUI'1 REPENS )
1 . Introducti on 2 . l1ethods
3. Re sul t s
( a) Dry ·wei ght and ni trogen yields ( b ) Holybdenum content s
( c ) Tungst en content s
4· Di scu s si on
A COl'1PARI S ON OF l'1ETAL CONCENTRATI ONS IN THE LEAVE S OF FIVE NEU ZEALAND NATIVE TREE
SPECI E S GROHING ON ACIDIC AND BAS IC SUBSTRATE S
1·. Introducti on 2. The s tudy are as
3 . S illnpl ing and analysi s 4 . Resul t s and di scu s si on
( a ) Potas sium ( b ) C alcium ( c) Hagnesi um ( d) I ron
( e ) Hanganese ( f ) Zinc
( g) C opper (h) C abal t ( i ) Chrorni um ( j ) Nickel 5 . Conclusi ons
SU111'1ARY AND GENERAL CONCLU S I ONS REFERENCES
PUBLICATIONS ARI S ING FROl'JI THI S THE S I S
( xi )
1 31 1 3 2
1 3 3 1 3 3 1 3 5 1 3 5
1 3 9 1 3 9 1 41 1 43
1 44 1 44 1 46 1 47 1 47 1 48 1 5 1 1 5 1
1 5 6 1 5 6 1 5 6 1 5 3 1 5 8 1 5 8 1 6 0 1 60 1 6 1 1 6 1 1 6 2 1 6 2 1 6 2 1 6 3 1 6 3 1 6 4 1 67 1 7 3 1 86
Fi g . 0 . 1 • Fig . I . 1
ri g. I . 2
Fi g. I . 3 Fig. I . 4 Fig. I . 5 Fig. I . 6 a Fi g . I . 6b Fi g . I . 7 Fi g . I . 8
FiCJ. I . 9 Fi g . I . 1 Oa Fig. 1 . 1 Ob Fi g. I . 1 1
Fi g. 1 . 1 2 Fi g. I . 1 3 Fig. I . 1 4
Fi g. I I I . 1
Fi g. I I I . 2
L I ST OF FIGURE S ( xi i )
After page no .
Hap of S outh Isl and, New Zeal and, showing schi sts of geosyncl ine and l oc at i on of s tudy areas
Cal i brat i on curve for c al orimetri c de terminat i on of tungsten in
geochemi cal sampl es and pl ant ash ,
using l arge cel l s 1 5
Cal ibrat i on curve for the cal orimetri c determinati on o f tungs ten i n
geochemical s ampl es and pl ant ash ,
using micro cel l s 1 7
Prot on-induced x-ray fluorescence 24 Computer-assi sted analysi s of
x-ray spectra 24
X-ray spectrum of scheeli te
( C a\10 ) 26
X-ray4spectrum of pl ant ash from
area of scheel i te minerali sat i on 27 X-ray spectrum of s oil from are a of scheeli te minerali s at i on 27 X-ray spectrum of pl ant ash extract dri ed ont o Kapton fil m 3 1
S t andard curves for tungsten by proton-induced x-ray fluorescence , showing effec t of limi ted or
unlimi ted s ample depths 32
Absorpti on profi les for tungs ten ( 0.1 % ) in rich and lean ni trous-
oxide acetylene flillnes 45
S t andard curve for tungsten ,no
s c ale expansi on 46
S t andard curve for tungsten , 40%
s c ale expansion 46
Effect of emi ssion l ine broadening and sel f-absorpti on on fl illne
absorpti on 46
Rate of extracti on of molybdenum
into vari ous solvent s 6 5
S t andard curve for c al orime t ri c
de terminati on o f molybdenum 7 9 F l ow sheet for di s s olut i on and
analysi s of geochemical and pl ant
s ampl es 81
Det ai l ed maps of tungsten explorati on s tudy areas . ( a) Gl enorchy ; ( b ) Paradi se; ( c ) Macrae ' s Fl at ; ( d ) Top Val ley ;
6
( e ) B arrytovm; ( f ) Canaan 1 02 Transect dat a for tungsten i n soi l s and vegetation. ( a ) Glenorchy ;
(b ) Paradi se; ( c ) Macrae ' s Fl at ;
(d) Hai rau Valley 1 1 1
Fi g. I I I . 3
Fi g. I I I . 4 Fi g. Ill . 5 Fi g. I I I . 6
Fi g. I I I . 7 Fi gs . IV . 1
and 2
Fi gs. IV. 3 and 4
Fi g . IV. 5
Fi g . I V . 6
Pl at e IV . 1
( xi i i )
'l'ransec t dat a for tungsten in soi l s and ve get at i on . ( a ) Barryt own; ( b ) C anaan
I1ap of BarrytO\'m study area showing site of Transects
Original tungs ten-tree dat a for Transects A and B
Trend surface analysi s of dat a for Transec t s A and B
(a) i soconcentrati on contours ; (b ) trend surfaces;
(c ) "residuals11
Hap showing location of molybdenum mineral i s ati on, C anaan , Nel son
Growth and ni trogen yield re sponses of whi te cl over to tungst ate when
growing on di fferent ni trogen sources . (a) fixati on; ( b ) ni trate ;
(c ) ammonium
l'·Iolybdenum and tungsten re sponses of whi te c l over t o tungst ate when
growing on di fferent ni trogen sources . ( a ) fixati on ; ( b ) ni trate; ( c )
ammonium
Hap of New Zeal and showing sites chosen for ve get ati on composi tion compari s on
Hi s t o grams of el ement al
concentrati ons in soi l s and pl ant s fron1 acidic ( a ) and basi c ( b ) areas Leaves from the trees sampled
1 1 2 1 20 1 20
1 2 2 1 24
1 49
1 49
1 5 6 1 5 8 1 5 7
Table 0 . 1
Table I . 1 Table I . 2 Table I.3 Table I . 4
Table I . 5
Table I . 6 Table I . 7 Table I . 8
Table I . 9 Table I . 1 0 Table I . 1 1 Table I . 1 2 Table I . 1 3
Table I . 1 4 T able I . 1 5 Table I . 1 6 Table I.1 7 Table II . 1 Table II . 2 Table I I . 3
(xiv)
L I S T OF TABLES page
Physic al and chemic al properties of
tungs ten and molybdenum 3
Analysi s of soi l s for tungst en using
fusi on and igni tion tecru1iques 1 8 Analysis of tungsten in ve ge t at i on
ui th and wi thout pri or ashing 20
X-ray pealcs of tungsten 25
C ompari s on of analysi s of pl ant ash for tungsten by col orimetry and
proton-induced x-ray fluorescence 34 Effect of time on extracti on of
tungsten from acid decomposi t i on
residue wi th potas sium hydro::idQ 43 Effect of N2ojc2H2 rat i o on tungsten
absorbance 44
Recovery of uo3 added to low-grade
ore-sillnple 49
Analyti c al dat a for repli cate
determinati on of tungsten i n synthetic standards and ore s amples 5 0 Analytical data for determinati on of
tungst en in one sampl e on twenty
consecutive days 5 2
Compari son o f at omic absorpt i on and
cal orimetri c analysi s of tungsten ores 5 4 Compari s on o f dry and wet ashing of
pl ant materi al 6 3
Compari son of KHSO fusion and HF/HNO':l, di gestion �f geochemic al
sampl e � 64
Effect of final acid concentrat i on on complexing of tungsten wi th ci tri c
acid 6 8
Analyt i c al dat a for repl i c ate
de terminat i ons of rnolybdenum 7 0 Nolybdenum recovered from vari ous
sample s 7 8
De t ai l s o f condi t i ons for at omic
absorpti on spectrometry 86
Analysi s of standard di ab ase \·7-1 87 Typic al J apanese tungsten ore
speci fi cati on 91
Average c oncentrat i ons of penal i sable and other met al l i c impuri t i e s in
scheel i tes 92
Strontium and barium content s of
New Zeal and scheeli te s 96
( xv )
Table I I I . 1 Rainfal l and soil pH dat a for t he
test are as 1 05
Table II I . 2 Tungsten BAC values for trees from
Barryt m1m and Canaan 1 1 0
Tabl e II I . 3 Summary of dat a for concentrati ons
of tungsten in s oi l s and plrult ash from transect s acros s minerali sed reefs 1 1 4 Table I I I .4 Molybdermm concentrati ons 1n soi l s
and dead wood 1 26
Table I I I . 5 1'-iolybdenum c oncentrati ons in tree sampl es col l ec ted above inferred
posi t i on of reef , 5 0m from out crop 1 28 Table I I I . 6 Holybdenum concentrati ons in t rees
Tabl e IV .1
Table I V . 2 Table I V . 3 Table IV . 4 Table I V . 5 Table IV . 6 Table IV . 7
Table IV . 8 Table IV . 9
and soi l s at an area of transported
molybdenum 1 29
Average c oncentrati ons of tun gs ten in the organs of two tree speci es conunon to Barryt o\lm and Canaan
Average c oncentrat i ons of sodium and potas sium in two tree species from Barryto\1m and Canaan
S oi l dat a for pot tri al Pl ant dat a for pot tri al Di stributi on of tungsten in
seedl ings, D ay 300
Detai l s of nutri ent s oluti ons
Percentage change from \"/0 t reatment, in shoot dry wei ght and ni t ro gen yields , wi th vari ati on in appl i ed
tungst ate
Experimental dat a expre ssed i n concentrati ons
Analyti c al d at a for s oi l s and tree l eaves from acidi c ( a) and basic
( b ) area s
1 34 1 36 1 38 1 40 1 42 1 48
1 50 1 5 2
1 59
