Biogeochemical studies of nickel and copper in New Zealand : a thesis presented in partial fulfilment of the requirements for the degree of Doctor of Philosophy at Massey University

Copyright is owned by the Author of the thesis. Permission is given for

a copy to be downloaded by an individual for the purpose of research and

private study only. The thesis may not be reproduced elsewhere without

the permission of the Author.

BIOGEOCliE:UCAL STUDIES OF

NICKEL iu'ID ^COPPER IN

1'>. thesis prescnte<l in pm·tial fulfiluent of ^the require:-.JGnts f•lr the degree

of

fioctor

of 21ilosoJhy at

Massey University

Michael Hornce ^Tiuperley

'1 9 71

j_j_

growing on the: Ri•·1ak:a Basic Conpl•;x, !iorth-·:;G:::>t Nelson, No'.:v l82:.land,

were investigated by the applicc.tion oi' st::ctistical techniqw's to biogeochemical data. Particular referen^ce was given to nickel aau copper to evaluate the usefulnes�; of plant analysis as a prospeccing

too^l.

Prelininary investit;ations sho·.-.red that serious errors cuuld result frou the filethods of sanpling p^lant^{s and} soil3 ,;^, iY� 3<:i<.lpling

procedures were ado^pted to ninini^se these ^errors. In addition, errors aris^ing froB atonic absorption analysis nere found to be significant for some metals.

and

Q

^.acu

1;;_i

folia as well as their ,;.:· sociotc·d

manganese ^and potas siwJ. �i'he l)l<m c:.; �·,·sr0 also an::tlys2'l for ^iron.

These results sho;-;ed that each species ::tccw.mlated diffc;rcn�, but related, amounts of various ueta.l::> and that they distributed these metals in different ways between their leaves and tnigs^.

N.truncata ^and N.fusca which are closely related genetically, accumulated metals to similar detjrees, while N:.men^zi^esii which is not closely related to the ^oth^er Hothofagus species accLu-Julated metals to differing degrees.

iii

ancl in the soils '.·:ere <JY<'lu-tl.)rl �;;·.- compucin:; correLtti·.:11 coc.,f�icients.

The best correlations for niclwl nere obt':tined for the

H�-��ll_f�

genus although the other 0recics nl�3o showed hit;hly significant cor relations. The -�---- �- 1_:: N othof.:-· ^;-us ;_,;e nus 2..lso shc;•1ecl th•.c ^best correlation for copper.

In vie,, of the r..:.bove results, a nore extensive stuci:;,r of tlw Nothofa__gus genus ;vas carriecl out. n. sucond ::;urvcy '.'12..:._, C.ll'J.: .. �·i:; · e11 in

the

s aee area in which le3.f &C:.!aples of this genus as ilolJ. ^u.; :;heir associated soils �ere collected. �hile the metal concentrations in the soils col^lec^ted in this ^survey compared well to those collected previously' the oetal conc.:.:ntr8. cions ir: th8 plan l; s' in �;enc;.cal' did not sho� good agreeoent.

concentrations of the:sc ::ct;::.l.:; :Lt th8 ^soils. It ·_·;:..5 sl1..:;· ^{.. -:-l} �)y

co^r:1parison of the trend ;.;urf-?..cOJ --nJ. residual3 th2t. the.: :·ccctl!.:ule.tion of nickel was rleteroined prir.1urily by the concentration of nickel ⁱⁿ

the soil, whereas for copper the accunulation by the plant ·.:as a

f

u

n

ct

ion

p

rimarily of the specific requirement of the ^plant for ^this

Lletal.

Multiple r egression analysis was used to inprove the pr

e

dic

t

ion

of

the copper a

nd nickel concen trations in the soil frol�1 the ^concen-

trations of these metals

in

the leaves

of the Nothofagus s^pe

c

i

e

s,

by

making quantitative allowance for the processes influencing

the

·'

iv

acclliilulation

of these metals by

^the

plants. I

n^provene

nt

s of

bot··.'leen

25% and 35% were obtclined

ut the

9o%

^co

n

^fi

d

^e

n

^ce

level.

Inter-netal

ratios in the leaves

were c

^ons

id

^er

e

^d as possible indicators of ni ckel

and

^copper concentrations

in

^the

soil l)ut

^the

results

Ylere di scouraging.

Stu

di

^{es were made of}

the locations and chemical

^forms

of nickel, copper, zinc and

iron in both

freeze-dried and

^{fresh l}

e

^aves

from some trees

^{growing on the C} onplex. i. toi :ic n.bs^orpt

i

on spectrophcto; ;ctry

was used to

me

asu

^{re the} cC!1ccn:�r ·; �· ')!1S of thL:se Jo^!etal

s

in

'uutL

^plant

extracts and on

^the electropl1c-:rcc;:i:-o i'nrl chronatop·"·t·,;�.:l i'E'.:J·;rs used

to

se

p

arate t;113 I!letal cor:1plexos

in

the ex\;racts. :1:::s;Jli:s incl.ic-·ted

that

the major

^part

of

^th.;

nic:�c;l

�;:C8SCo!1t in the L::� '!t�: ^·, :· �) aoc contained

in

^cell orgn.nellos nor "··, s it '.:,ouncl to cull n. i_L;, !m·c

existed as a

posi tivcly

^charc;od conplex

in

ci ^thor the cyco�Jl.:csn

and / or

^{the vacuo}

le

^. Copper, zinc 2.nd

iron

were distributed differ.mtly with varying fractions, depending on tho uetal, existing predci.l:Ln­

ately as anionic coi!!plexes.

It was concluded

^the.t

the research

^{embodied i n}

this

thesis

had illustrated the application of statistical

techniques to biocc0chowical

studies, sho;:red that biogcochenical

prospecting for

nic.:'.L:l in New

Zealand was feasible and that uethods of total analysis for metals

could be applied to the stu� of microgram amounts of metals in

biological systems.

V ACKNOWLEDGEMENTS

���. -�·-

The author would like to thank his supervisors Dr.�.�.Brooks and nr. P.J.Peter son for their valuable advice and assistance during the course of t his project.

To the staff 01' tho eo : mcf;r unit, tLe autlw1· -�:x c011cts ills thanks

for the oany helpful suggr;sti^c;ls ,J,_;rin - the· ^wri ti11:�� of ::.�,: c • ::.uter progrru:1nes.

He also nishes t. ^· thank ^Mr;; D�-m I·Iansfox·d.

r·or·

^{tYl•in,_ ·c]L thesis}

and his v1if8, H8l en, for assistancu with th8 diagr!lllls.

The author is oast crateful to t he Mineral R_esources Su;J-

Com.r.,ittee of t he New Zealand Gr:1nts Coicmittee for finance to SUHJOr^t t:t·D.s project and also to the fornar ^Mcintyre ].;ines

(?\f.Z.)

^{Ltd. i'or}

assistance ·.vith transpc�rt anJ accJ.i.Iilodation in the field.

TABLB OF CONTENTS

--� ... ^{-.,.._,...,_�·}"' ...,.,_...., ______ _

:..BSTRJ�CT ii

.:..CKNCY;iLEDGEMENT S ^V

Tf.BLE OF CONTENTS

LIST OF FIGURES xi

LI3T OF Tf.BLES SECTION I SECTION II

i:....

B.

c.

D.

E.

xiii

Ins trULJents and Che;;ucals.

Sensitivities and Linits of Measurement.

Treatment of Plant Sanples,

i6

21

1. PruliElinary treatoent 21

2. :�shing techni<;lue 21

3.

^{Loss of rteb .. ls} during dry ashing 22 4. Dissolutic:t alld analytical technique

adoptud 1.�or plant sanples

25

Treatment of Soil Saoples.

1 ^• 2.

Prelininary tre:;atnent Dissolution procedure

Chenucal and Spectral Interfe rencGs.

26 2(.

F. The J�ccuracy ,,_nd Precision of the Dissolub_on and ;.nalytical Methods for Pla:1ts ''L:�l Soils and the Effec ts of these

G.

?araoeters on Statistical Techniques. 29

1

^•

3. 2.

Introducti·::·n PrecisiOl'­

J�ccuracy

IAeasurenent o£' ) ·il pH.

_)1 ji

3)

H . Statistical Proccclnrus. ��0

SECTION III - PRELHITN1-.RY BIOG:;:::o _,=r;;, Ic:�L SURVEY 41

:^{. •} The Snnpling Grid. h2

B. i�tine ralisation �!i thin the Sanpling Grid. 1:-3

C.

Vegetation Cover. 44

1

^•

2.

3.

Introduction

i�e rial l' hotogra phy Ground nurvey

lf-4

4-4 47

vi

vii

P ^(·� ^.. �·o.

D. Evo.lUc'l.tion of PL.1, ·, c-.n -, )oil ^{Sa; ;�)lint;}

Procedures.

1 . Int:codu.c ci m

2.

Leav>.:;s, t·.:i:'!,0 ::md -�runk woods; ,1_;,-;_

! (_I

·:-.J

fr' ),:: di f:t\, n� i'lt ho i bht s .JU

3.

So.i tples fro: ·_ different depths in

the ^soil 50

E.

F.

SECTION IV

s.

VccriA.ti(ln:J of the r.1etal concuntrat­

ions in plants and soils over s�all distances

Discussion and conclusions Sta tisticr^{.l Treatment} of the Data.

1 •

2. Correlation coefficients The r.ed�wed m:ajor axis and craphinc_; techniq

u

_es

Prelininary Sarapling Survey.

1. ^Metal concentrations in the leav0s

and. tni..:;s of the sp^(;:cies sanpled The relationships between the �etal

concentrations in the plants and

2.

the ^soil

The

three ?.c;,t_hC2_f�gus

spec

i

es

��u.JOR BIOGEOCHE1;ICJ.L SURVEY

Introduction.

B. ^The Precisi<m 01 �.;--cll.:::,j_co.l s.nd Biogeoch':-':-:ic:::cl -3o.. ^:: •lit;.:;.

1 ^•

2. 3.

Introductirm

Results

Discussion

C. _Further Cum,'L�nts ^· '' the three i•!otilOf:.t ··: .s

D.

... -.� --- --. .... -..') ^{____ .}

S^pecies.

1

^•

2.

3.

lnt:co<lucU.on

Results Discussion

The Relationships between the Metal Concentrations in the leaves of _the Nothofagus Species and the Metal Concentrations in the soil.

1 •

2. 3.

Introduction

Preparation of soil fractions Differences between the metal

concentrations i n the plants and

53 55

57 57 58

69 75

81

!2

•"'; \

..J • f"t') U.•

,.,,, t.J!.I

97 97 97

in the various soil fractions 104 Correlation coefficients 1;_etween

the metal concentrat ions in the plants a nd in _the various soil

fractions 107

E. The Use of Trend i .. nalysis to Compare and ^Interpret Uiogeochenical and Geooheuical Data.

1 •

3. 2.

Introduction

Data distributions

The application ^of trend analysis

to the present study

F. _The II:lp^roved Prediction of ^Metal Concen­

t^ration^{s in} the Soil fror1. the 11'1eta^l

G.

Concentrations in the Leaf J,sh.

1 ^•

3. 2.

5-6.

7. 8.

Introduction

i'.ul tiplc rcp·2. :si on :::na.lysi3

The indepec.llcn l:. vr-criro bles seh)ct.:;d for regression analysis

D i stri ":·utionG '.r t:-t-: indop•:ndont variablc;o;

Procedu!'e Results Discussi�n

Conclu��j r•rcs

The E,'fect.·3 o:f.'

Ji)l

Concentra: j,()nS oi'

Nickel and Co}per in the 3oil on the Metal Concentrations in the Leaves of

th� No�hc!�� ^3pecies.

1. Introd�lction

2.

Inter-netal relationships within the leaves

3.

'l'ho influences of high nickel and

copper concentrations in the soil on thu motEtl c^oncentrations in

the

leaves

Thc: influences of high nickel and

copper concentrations in the ^soi^l on the ratio<J of the Jletal con­

centrations in the leaves

Ratios of the I:letal concentrations in the leaves as in^dicators of soils contaiⁿing high c once^ntrations of

viii

1 1 0 .; iO i i ; J•i 6

125 125 1 ·�:s

1?7

'') . I . ^{- �J}

13:)

13�

139

142

i�-5

copper

150

H.

Essential and Non-essen tial Trace Metals and how their n_atur^e affects Biogeo­

chemica l Prospecting Result s.

1

^•

2. 3.

4.

Introduction

The use of dc<ta distributions The coefficioacs of variation

The relative nccuDulation of a l·lecal as a function nf ^the total concen­

t ration of the ,Jet:-cl in the S 'lil

154 '154 15G

155

1 G1

SECTION

V

11

.•

B.

TR.LCE MET;.L COJ'.IPLEXES IN LE...VES

Introduction.

Experimental.

1 •

2.

^Saupl� oollection

Che!Jlicals and. Jli.' ssware

ix

. f

., '·' '

.· -··1

I I ^•

•!71 171 C. Differential Centrifugation of Fresh

Leaves. 17h-

17�­'17-1�

1 ..

2.

3.

4.

s.

i'Iethod Proceclurc

.i;nalytic

^{'i .} •o�;bod

Results Discuss inn

1 7:J i75 ne

D. Solvent Extracti<;!l of J•JicJcel fre>u Frecz.8-

dried

Leaf

_{Tissue. ·J} ,;o

.

, ,0 L;u 1 81

I �}3 E.

F.

G.

1 •

....

') . Extractioll prC'��)c�dL<ro

"l.nalytic<< ^. .l Lit;thod

Results Discussion

High-vol tacc: Electrophoresis of ^tho

soA

l.queous Ethanol Extracts from ?reczo­

dried Leaves.

1

^{• Procedure}

2.

L l1.ill

yt

ⁱcal ''ethvd

3.

Results 4. Discusr.;ion

Invcstiga tions of thu Soluble ?1letal Cowplexes in tlw �''resh Leaves of

&_�.

186

1G6 186 187 180

1. Introduction ·J 9G

2.

Electrophoresis of the extract 1)0

3.

Couparisons with chelates of citric

acid and oxalic acid

193

4.

Chrouatography

of

the

coppe r, zinc

and iron complexes 1 94

s;

Partial purification of the extract

by Gel filtration 197

6. High-vol tag() electropho resis of the

partially purified extract 200 7. _{Paper chrn,} Htot;r.cophy of the par-l:ially

purified extract 203

C�Dnclusions. 206

SECTION

_VI

BIBLIOGRJ..PHY

J.PPENDICES

I

Plant species raccr�od

II

Frc;quc;ncy '.lic>-�-::-·:l.1.·e<l:iociS of v·:;.rL . le:s

X

20;)

2.28

used ^{in ;} ·ul-:;ipl:· ^1_', ._;r>J�Gi· ^·!1

:c..n::Llysis 2)1 Ill

IV

V

VI VII

Correlation cooffici-.:mt progra:-;.: .c

Des

criptio;1 or' the �)rogra;,u·.ce

B. Progro.ilL�c ^listing

8top�1i se regression analysis prot;ri.l:.une

B.

c.

Description of the programne

Sw.�::ar:_,r of the essential procedures involved in each r::ain prograr.Y:e Prograrm:rc listinG

Prograr�ne to ^conput(; the ^proba0ili ^ty of site overlap

� l •

B.

Descripti::m of the proc;ra,� _e Progr2.1:111e listing

Data listing

Publications arisin:; froLl thⁱs ^thesis

'J ·zrJ / _ _) '-·

') 7 I I • .Jo..f-

2�o

^)U

238 24-1 24-4

251,-

289

r}gu

^{re No.}

I ^- 1

I ^-

2 I

^-

3 I

_{- 4-}

II

^-

1 II

^- ₂

III -

1

III -

2

III _{- 3}

III ^-

4 III

- 5

III -

6

Dl ^-

1

IV -

2

IV

_-

3

Dl- 4

Path;mys of cnvirnr:.···.0ntal :::ovo:.:ent of trace elc,•ents.

The Geochm1icnl ^Cycl2.

The Bio�:c:;ocl: _., :ic' .. l ::.:,role.

Gee -logic<:-:.1 ::;k:::tcL . ,a�J of ^th0 ca �;tc�rn

2

iO

part of North-··:lcst :ielson.

13

Flo>.rchart for plant

and

soil analysis. 25

.icpp

a

r

e

nt concentrat ions due.; t o lⁱgh

t

scatter by the folloHing netals: calciw::l, iron, r ^•. -.::ncsiu,:, alu^·::in

i

um^{, p}otass

i

um and sucli u:.. ^{• •}

The sarapling

gri(l.

Soil profiles.

Variations of the netal concentrations

35

42

50 xi

in plants and soils over srr1all distances. j�.

Metal c oncentrations in the plants san:pled.

Iso-concentration contours of nickel in b oth the plants and soils.

Iso-cencentration contours of copper in both the 1'� t�t_;!:':-::C�i]'US S!'�P• an·l the soil.

Relationships bcb:oen the data coll�ctod in the March, 1 _<;69

and

the Nover:.bcr,

61

73

73

1969

sanpling prot:;r.'.: ^:.;.:es. .�6

Concentrations Ol' ;.:etals ^extracted fro;..1 soils by c old I M r;cl

as a

function or'

tine . Ca

lci

um

, 1.;ag

n

cs

i

tiD, nickel and

copper. 102

Concentrations of metals ext

^rac

ted

frora soils by cold 1 M HC l as a function of tine . Potas s ium, chromium and zinc. 102 Trend s urface s and i so-concentration

contours of both the observed data and the pos it ive autocorrelated re s idual s

for nickel in t he plant s and s oi l s .

117

EJ._g_u

r

e

_No.

IV _-

5

IV - 6

IV _{- 7}

IV ^- 8

V - V ^-

2

V ^- 3

V - 4

V _-

5

V -

6

V ^- 7

V -

8

V _- 9

Plate I

Plate II

Trend surfaces Dnd i[,l,-c··mccn1:;r3.ti,_.n

contours of bot'1 c:h.: olJ su'vGd cl., ta and

tho

pos:L �ivc3 ··_u·�·.;correl:·i;;,_:d re

s

idua^l::; for COJY·<'r in thu

rlants

and soils.

Concentrations L1 the i'!o

tll.o�

^spp.

l

_eaf

ash

and predⁱ

c

_ted concentrations in the-; soil

( 0.10

^{levGl of}

significance)

plotterl ag2.inst the obser

v

ed concen­

trations in the soil for nick

e

l and

xii

copper. 1 33

Trend surfaces

(0.05

level of s

i

_gnif­

ic^ance^{) of}

the

observed and predicted

data.

133

Relati

v e

_a

c

c

w!lu

^l.'ltion versus t

o

tal

soil concentration. ·iGj

Differontial centrifugation

scheme. 171:

Solvent extractior, scher.te for freeze­

dried leaf tissue.

Patterns of

nickel

after ele

c

trop

h

^oresis

at pH 5. 3

of the 8q;� ^aq UEcl, ut:. ethanol

leaf extract.:;.

Patterns of S8J:lc i'i'-'cals 'lftcr

electr0-

phoresis at pH 5. 3 of ^-Lhc) a��ucous

180

extract

of fresl: :·.c.cutif,;lia le' ve;,.

1

_{� i}

�-'1....-... --... . .... ,__..-

Chromatogra1)hy il:

,,,�'c2nol/3.cctic aciLl/

water 12:3:5 01' _,-ct"ll ^c;; -� loxcs isol0.t.::cl by prepara _·(;i VG-Bee" l) ulectr':.,t;hc)re.:,ls. ·i:S

Gel filtrat

io

ⁿ of the a.quoous ex^tra

c

_t

of ^f

r

_es

h

.:bacutifolia leaves.

·190

Patterns of nickel after electrophoresis at pH

5.3

of both t he partially purified aqueous extract of fresh g.acutifolia

leaves and nickel cation standards. 201 Chromatography of the partially purified aqueous extract from g.acutifolia leaves.

Patterns of nickel.

204

Chromatography in ethanol/water 8: 2 of

the �acutifolia lea.f ^extract.

201:.

Aerial photograph showing the topography and vegetation cover in the vicinity

of the sampling grid.

42

Leaves frow the trees sampled.

80

Table No.

---

II

_{- 1}

II

_{- 2}

II ...

³

III-i

III

_-

2

III

_{- 3}

I II

_{- 4}

III

_{- 5}

III

_-

6

III

_{- 7}

III

_-

8

III

_{- 9}

IV -

1

IV ^- 2

xj_ii

LIJ:r

_{OF T .. J5LiS}

... --- . - ... ·- � .._ . .. . . ... ...

Pr _{. .·--·} ·�.; ... i�0.

Details of th(e analytical cavtbiliti<:;:::

of the method:> ^uscrl.

Percentage recnverios of 1

0�

^G each of n_(a icke

)

₄₅₀ l

,

⁰ C cr;>:.}'er ^J. and ^.

(b 500

and zin

)

^{0 C for c} after ashing 12 hours ^at in

the pros8nco of filt^er pqper.

24

i.nalysi:> _of the st.,�.nd.ard diab.:1s^{e ·,; -}

1

³²

i'·I8tal concontratic>ns in ash of lc;aves, t'Nigs and trunJ: ·.;0od taken fron differcmt

heights up t·.;,' spr,.,cir.lens of

Q_

otl��R[lUS

fusca. ji

Total metal concentrations at differ,;nt

depths in t^he soil.

Mean metal concentrations in the leaves and twigs of tha p^lan^ts sar.1p^led.

!,iean relativu accu..r:ulations ^{of the} netals in ^{the le�vos} �n� t·1i�s 8f the plants

saapled.

Mean coⁿcent^ra �J.;m:; ^r:n·l cOl1centnxt:i.on

ranges of calciu ^·, ;:,gne:::i.u n.nd

potass illlli in :�111::. clry lcnvos of 1lif'i'·;r :n :.

trees.

Correlc:tj_c:;-; coe;�·;_'ici�.:1�s b;.;t·.;,Jcn tb=:

;:1etal concG!1tratio·,,;j i:·: the pl;-hlrl.s ··.n·l

62

in ^{the soils.} 71

Gean Betal concentrations in the leaves of the three l'loth<2f'�s species.

f.-lean relative accuuulations for the f.Lletals in tho leaves of the three i'!othofagus

s^pecies

..

⁷⁷

Mean relative accunulations for N

.

^truacata

and N.menziesii expressed relative to the

val

ue'"sfo

r

p. ris�.

⁷⁹

Mean i>1etal concentrations in the plants and soils collected in March, 19 69 and

Novenber, 19 69. Bit-

Correlation coefficients between sauples collected in March, 1969 and November,

1969. 85

Table No.

IV -

³

IV

-

⁴

IV

-

⁵

IV

-

⁶

IV

- 7

IV -

⁸

IV

- 9

IV -10

IV -11

IV -1 2 IV -

1 3

IV

-1 4

Mean concentrations of SOLle .1etals in the lee.ve s of the three iJ otho

l'��

species collected in Hoveuber, 1969.

Mean relc1ti ve accUt-:Iulations of some r::etals in tl1o leaves of the three i'lothofa[QJ-� 3pecies collected in March,

xiv

1969, ^and Nove:1ber, 1969. 90

r/,ean metal concenl;r��tions in the dry leaves -1

the

^{th1.'0C :}

l(}_t::;'l

^o

l�-

r:us s·)ech�s collected in /.:-"L'C!l,

·

^{19 G9}

,

i'!.nd. iio re;_ ·ber,

1969.

Vetlues of Stucllont.:; '1t<� fnr th ^_, (li.Lferc nee

in the precent·:[:;C:

.,

^-:.h

;:eit_;hts

^{and tltc}

dry leaf concen:�r ·<;:i_<.'.''s of zi:1c --:>nd iro,l, )2

botw-"en ths three; :·'�!;_�:_

?f

^{·,r:-us species.}

93 L�af

^length in rcL:· c:i.on tl> the r1can

relative ac:cuLtulu.tions of pota�;.:,iun anu manganese in the dr:,r leaves.

,�nalyses of ^a soil fraction at each

stage o.l' four successive passings through 95

a

400

uesh i.Jrass sieve. 99

Mean netal co ncentra tions in the leaf ash of th<-- _I·

�

c-�t

)

l

�91-'�u

s 0pecies and in the

various soil fractions. 105

Correlation coefficic.mts between the

;:etal ^conccmtra

tions

^{in the leaves and}

the metal concentrations in the various soil fractions.

Trend equations derived a t the 0.05 level of significance.

Results of regression analysis.

Correlation coef.Licients for nickel and copper bet··:re::cn the observed con­

centrations in tlw soil and both the predicted concontr1�ions in the soil

118 130

and the concontratio.ms in the leaf ash.

·

^{j 3�-}

Significant

(�o.w 1)

correlation coeff icients

(

^r

)

^{beh1ucn the ;:�Gtal}

concentrations in the ^leaves of the

three Nothofar.:;us SfJ;:cies. 'i40

Table No.

IV ^-15

IV ..

1,

IV

_-17

IV ^-18

IV

_-19

IV -20

V

_{- 1}

V

-

2

V

-

3

Corre lation coefficic�ts ^betueen the metal conccntr&t�ons in the lenf ash and the nickel ;•;ll eo; ·-�·er concentrations

XV

iu ^{the soil}

(

^{-2CJ :}

:- -;h).

^111--:;

Correlation coei'f:i.c:iunts licbz :en the inter-metal r&ti8s in thG loqf �3h of the three

_0_ot\�-2�<::22.E\.

:.Jpecie:::> and the nickel an<1 c�l:::,·or c^:

,

^nccmtra tions

in _the :::>�·il

(

^-1�J

.esh).

The evi.llu.a tion ')£' inter-;,:etal ro. Cios in the l eaf a:::>h for indicating

anomalous concentrations of copper in the soil.

Ratios of the geor,etric and arithmetric

!:leans ^{to the} r.10dians for various ^uetals in different pla nt species.

152

157

Coefficients of v�riation for some I:letal concentrations in tLe leaf as h of various p^la^nt species ^and their associated soils. 159

Correlation coe fficient^s between the relative accunulations ancl the total

metal concentrations ^{in the} S(lil.

162

Details _of the lec:..f samples used ⁱⁿ the study of ^the netal complexes in

leaves. 172

Percentage distrDJutions of some netals in the ^fractions c,lJtained by diff.:::rcntial

centrifugation. 177

Percentage ^distri '.:n_,_tions oi' nickel ⁱⁿ

the freeze-dri<Jd l,�·"Vt;S a, ;on,u; the varicus

solvent extract3. I �2