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ANALYTICAL , GEOCHEHI CAL AND BIOGEOCHEHICAL

STUDIES OF TUNGSTEN AND MOLYBDENUM

A the si s presented in parti al ful fi lment of

the requirement 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 )

ABSTRACT

Section I : S tudies were carried out which

significantly imr.-roved l:he se!lsitiv:i.ty of the

cal orimetric met hod for the determination of tungsten

in geochemical and pl ant samples with dithiol.

Proton-induced x-ray fluorescence was al s o inve stigated

t o determine it s suitabil ity for the detection of

nanogram quantit ies of tungsten. However al though

it showed considerable potent ial , the sensit ivity

of the method could not be devel oped sufficiently

to compare favourably with col orimetry.

A rapid method for the determination of

tungsten in ore s ill1d c oncentrates by atomic absorption

spectrometry was devel oped which , throu gh the use of

an alkal ine sample solut :i_on, was free of int erference

and instabil ity probl ems .

Fol l owing a ca!'eful study of the parameters

involved in the cal orimetric me thod for the

determination of molyodenum with dithiol 7 a simple

procedure was developed which coulc_ be used for the

analysis of a wide range of materials.

The usP of thP nitric/hvdrofluoric acid mixture for the digestion of soil s and rock s was

investigated. I!:: was found that the t endency for

c alcium and mag-fle sium to precipit ate as their

fluorides could be avoided by the addition of a

small quantity of perchl oric acid .

Section II : Scheelites from several

l ocalities in New Zealand were analysed for their

trace el ement c ontent . They were found t o contain

very l ow a"Tlount s of impurit ies . Their Sr/Ba ratio was found to be useful for distinguishing between

l odes .

( v )

Secti on III : An i nvesti gati on was c arri ed out

to compare the rel ative effi cacy of geochemi cal and

bi o geochemical e�:pl oratiml for �cungsten under a wide range of geol ogical , vegetati onal , climati c and

topo graphi cal condi ti onso It was found that, under

most condi ti ons7 both soil and pl ant sampling could

be used equally succes sfully to pinpoint scheel i te

bearing veins. In areas of high rainfal l and rugged

topography , soil sampling did no-:: always r2veal the

presence of reefs and , in the se cases, trunk-s ampling

of trees could provide addi ti onc.l informati on. It

was found that, for the purposes of biogeochemical

prospecting, all tree speci es coul d be grouped

to gether.

Following thi s i nves ti gati on, a more intensive

s tudy was carri ed out at Barryto"�Jm to test the

sui tabil i ty of trend surfc..ce anc.lysi s of bi o geochemi cal

data for loc ating ri ch pockets of scheelite wi th

veins , wi th promi sing resul ts.

A brief compar,sonof geochemical and

bi o geochemical prospecting for molybdemMn was carri ed

out at C anaan, Nel s on. It was fmmd tL:tt plant sampl ing gave more i nformati on where the l ow soi l

pH prevented movement of molybdenum into the upper

s oi l .

Secti on IV : Foll owing the results of the bi ogeochemical expl orati on in Secti on IV� which showed the exi stence of di fferences in the

di stributi on of tungsten between tree organs from

Barrytown and C anaan , the affect of soi l sodium and

potas sium was investi gated and was found to be

responsible for these di fferences.

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 FIGURE 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 colorimetric method 1 2 ( a ) Introduction 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

in 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 sample 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 21 l a ) Introduction 21 b) 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 ( iii ) Puri fi cati on and concentrat i on

of tungsten using ani on-exchange chromatography 28 Introduct i on 28 Experiment al 28 Resul t s and di scussion 29

c.

( iv ) Puri fi cat i on and concentrati on of tungsten by extrac tion into a solut i on of di thi ol in

( viii )

i soillnyl ace t ate 30 Introduct i on 30 Experimental 30 Re sul ts ill1d di scussi on 3 1 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 concentrates ( a ) Introduction ( b ) Literature survey ( c ) Devel opment

( i ) Di gestion ( ii ) Flillne condi tions

Fl illne s t oi chtometry Positi on of the flillne Air draught s in the l aborat ory Air vel oci ty in the fume exhaust

( iii ) Calibrati on curve ( d ) Experimental

( i ) Equi pment ( ii ) S t andard tungsten soluti ons (iii ) Di gesti on of the sample (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 lity and accuracy

( f ) Interferences ( g ) sensi ti vi ty ( h ) Productivi ty ( i ) Conclusi 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 57 6 1 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 samples

( b ) Determination of molybdenum in geochemical sampl es

( c ) Determinati on of rnolybdenum in steel s

Testing 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 ssolution procedure Treatment of plm1t samples ( 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 reproducibili 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 CHEELITES

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 ties 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

80 80 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 90 90 90 93 9 3 94

(x )

SECTION I I I - GEOCHEl'UCAL AND BI OGEOCHEHICAL EXPLORATI ON FOR TUNGSTEN AND HOLYBDENUI'-1

A.

B .

c .

INTRODUCTION 1 • Tungsten 2. I1olybdenum TUNGSTEN 1 . The detec tion of scheel i te-bearing

ore-bodies by the analysi s of pl ant s and soi l s ( a ) Introduction ( b ) Description of test areas

( i ) Glenorchy , Paradi se , 11acrae's Fl at and Top Valley Descri pti on of minerali sati on

( ii ) Barryt o\\m and canaan Descri ption of minerali sation

( 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 ) Canaan

( f ) Di scussi on ( i ) Glenorchy , Paradi se , Macrae's

Fl at and Top Valley ( ii ) Barrytm1m and Canaan

( 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 ) Results ( e ) Di scussi on and c onclusi on

HOLYBDENUM 1 . Bi ogeochemical explorati on for molybdenum

at canaan , 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 SIUI'1 BY NOTHOFAGUS

1 . Introducti on 2 . 3. 4. 5 .

6 .

Preliminary fi eld work Setting up of pot tri al Analytical �ethods Resul t s and di scussi on Distri buti on of tungsten Day 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 scussi 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 SUBSTRATES 1 ·. Introducti on 2. The s tudy areas 3 . S illnpl ing and analysi s 4 . Resul t s and di scussi 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 3 1 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 64 1 67 1 7 3 1 86

Fi g . 0 . 1 •

Fig . I . 1

rig. 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 Calibrat i on curve for c al orimetri c determinati 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 orimetric determinati on of tungs ten in geochemical sampl 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 ( Ca\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 area of scheeli te minerali sat i on 27 X-ray spectrum of pl ant ash extract dri ed ont o Kapton film 3 1 S t andard curves for tungsten by proton-induced x-ray fluorescence , showing effec t of limi ted or unlimi ted sample depths 32 Absorpti on profiles for tungs ten ( 0.1 % ) in rich and lean ni trous-oxide acetylene flillnes 45 S t andard curve for tungsten ,no scale 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 alorimetric determinati on of 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 8 1

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 in 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 . IV . 6

Pl at e IV . 1

( xi i i )

'l'ransec t dat a for tungsten in soi l s and ve getat i on . ( a ) Barryt own; ( b ) C anaan I1ap of BarrytO\'m study area showing site of Transects Original tungsten-tree dat a for Transects A and B Trend surface analysi s of dat a for Transects A and B (a) i soconcentrati on contours ; ( b ) trend surfaces; ( c ) "residuals11 Hap showing location of molybdenum minerali s ati on, Canaan , Nel son

Growth and ni trogen yield responses 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 stograms 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

Table I . 1 5

Table I . 1 6

Table I.1 7

Table II . 1

Table II . 2

Table I I . 3

( xiv )

LIST 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 Compari 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 replicate determinati on of tungsten in synthetic standards and ore s amples 5 0 Analytical data for determinati on of tungst en in one sampl e on twenty consecutive days 52 Compari son of 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 tric acid 6 8 Analytical dat a for replicate determinat i ons of rnolybdenum 7 0 Nolybdenum recovered from vari ous sample s 7 8 Detai 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 9 1 Average concentrati ons of penali sable and other met allic impuri ties 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 areas 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 III.4 Molybdermm concentrati ons 1n soi l s and dead wood 1 26

Table I I I . 5 1'-iolybdenum concentrati ons in tree sampl es col l ec ted above inferred posi tion 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 IV . 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 concentrati ons of tun gs ten in the organs of two tree speci es conunon to Barryt o\lm and Canaan Average concentrat 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 seedlings, Day 300 Detai l s of nutrient 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 appli ed tungst ate Experimental dat a expre ssed in concentrati ons Analyti c al dat a for s oils and tree l eaves from acidic ( a ) and basic ( b ) areas

1 34

1 36 1 38 1 40

1 42 1 48

1 50

1 5 2

1 59