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T H E I N F L U E N C E O F I N D U S T R I A L I M M I S S I O N S O N T H E M A G N E T I C

S U S C E P T I B I L I T Y O F S O I L S I N U P P E R S I L E S I A

ZYGMUNT STRZYSZCZ AND TADEUSZ MAGIERA

Ins t i tu te o f Env ironm e nta l Eng ine e r ing , Po l i sh Ac ad e my o f Sc ie nc e s , Zabrze , Po lan d 1

FRIEDRICH HELLER

lns t i tu t f i i r Ge ophy s ik , Zar ic h , Sw i t z e r land 2

S u m m a r y : S a m p l e s o f m e t a l l u rg i c a l d u s t s a n d f l y a s h e s f r o m c o a l p o w e r p l a n t s a n d i r o n

wo rk s in U ppe r S i le s ia as w e l l as so i l pro f i l e s in the c lose v ic in i ty o f the se p lan ts an d in O jc owNat io na l Pa rk ( ca . 25 k m e as t o f the indus t r ia l are a) hav e be e n s tud ie d mag ne t ic a l ly and

mine ra log ic a l ly . The me ta l lurg ic a l dus t s and f l y ashe s are h igh ly e n r ic he d in f e r rom agn e t ic

mine ra ls . The topso i l s f ro m pro f i l e s c o l le c te d ne ar the p lan ts hav e v e ry h igh v a lue s o f mag ne t ic

susc e p t ib i l i t y wh i le susc e p t ib i l i t y in the f e rm e nta t io n a nd hum ic subhor i zons in so i l pro f i l e s f ro m

O j c o w N a t i o n a l P a r k i s co n s i d e ra b l y i n c r e a s e d T h e m a g n e t i c p r o p e r ti e s o f th e m e t a ll u r g ic a l d u s t s

a n d f l y a s h e s s u c h a s f r e q u e n c y d e p e n de n c e o f s u s ce p t ib i li ty , s a t u r a t i o n r e m a n e n c e o r c o e r c i v i tyare s imi lar to those ob se rv e d in the top hor i zons o f the so i l s. The y are m os t ly r e la te d to the

oc c urre nc e o f large (mul t idomain) gra ins o f non-s to ic h iome tr ic magn e t i t e rang ing f ro m I to 2 0 I .tm .

The s imi lar i t y o f the magne t ic par t ic le s in the so i l s i s tak e n as e v ide nc e o f an a n thropoge n ic or ig in .

The y are r e spons ib le fo r the h igh so i l susc e p t ib i li t i es in Uppe r S i le s ia and in ad jac e n t are as . Som e

o f the magne t ic par t ic le s c ar ry subs tan t ia l quan t i t i t ie s o f t rac e e le me nts suc h a s Pb , Ni , Z n and Cu .

F ie ld and labora tory susc e p t ib i l i t y me asure me nts c an the re fore be use d as a s imple andc os te f f e c tiv e me thod o f de te c t ing the pre se n c e o f he av y me ta l s in the so i& o f th i s area .

K e y w o r d s : anthropo genic ferr imagnetics, metallurgical dus t, f ly ashes , trace elements

1. IN T R O D U C T I O N

Up per Si les ia (Katow ice voivodeship) i s the m ost indus tr ia l ised and m ost pol luted region o fPoland. M any h eavy indust ry plants are concen trated in this smal l area cover ing ca. 6650 km 2.Environm ental hazards are most ly l inked to the old metal lurgical p lants, cok ery plants and p ow er

p lan ts w hich com bus t l arge am ount s o f hard coa l and emit m any types o f gas eous and dus typollutants . De pen den t on chara cter and size, the pollutants can be transported o ve r variab le

distances as solid phase particles or in aerosols . After landing on the soil surface, the dust particles

penetrate into the soil profile an d accum ulate mostly in the fermentation (Of) and hu m ic (Oh)subhor izons .

The indus tr ia l dus t falls contain also a certain propor t ion o f mag net ic part ic les , wh ich cause a n

increase o f ma gnet ic susceptibil ity in the topsoil . Ac cord ing to records at man y mo ni tor ing s tat ionsin the vo ivodes h ip s ince 1981 the dus t f al l i n the s tudy a rea vari ed f rom 200 to 450 gm-2 year 1(Strzyszcz , 1994) and the i ron f lux in dust fal l var ied f rom 10 to 20 0 gm -2y ear 1 (Fig. 1) . Ear l ier

inves tigat ions o f metallurgical dus ts and f ly ashes f rom pow er plants (Strzyszcz e t aL, 1988,"

S t r zy s zc z , 1989a; S t r zy s zc z an d Magie ra , 1993) demonstrated ve ry high m agn etic susceptibil ity

1 Ad dress : Inst itu te of Environmental Engineering, Pol ish Ac ade m y o f Sciences , u l . M.Sklodowskiei 34, PL-41-80 0 Zabrze, Poland (Fax: +4 8-32 - t 7174 70)

2 Ad dress : Ins t i tu t f ti r Geo phys ik, ET H Ho ngge rberg, CH -8093 Zt ir ich, Switzerland

276 Studia geoph, et geod. 40 (1996), 276-286

The I n f lue nc e o f I ndus t r ia l I m m iss ions on t he Mag ne t i c Susc e p t ib i l i t y . . .

3 0 k m , . ~ . - . . . . . _ ~ " . ~. j. ,. ,- -~ - -~ -- ~

. f • - ~ , ~ . . . . . . - '~ ~ K ~ w | c _ e ~ 7 ¢ Nat iona l Park

'~'~ ~ :.,.~ " ~ . , Cz~owk~ ! >~u

Fig. l . Iron fall (Fe203) in Katowice District (Up per Silesia) in 1987, in gm -2 a 1.

values: max. > 18000 x 10-8m3kg -1 for metallurgical dusts and 2 500 x 10-8m3kg 1 for f ly ashes.

Th ese values point at a considerable am ount o f ferrimagnetic iron ox ides in the industrial dusts. Themagnetic low field susceptibil ity in 1 50 0 soil samples from U ppe r Silesia increases distinctly in the

topsoils (mostly subhorizons O f and Oh ). This effect has been observed especially nea r the gre atindustrial plants (Strzyszcz e t aL, 1994) . There is also evidence o f a close direct co rrelation betweenmagnetic susceptibil ity o f soils and concentration o f som e heav y metals.

Th e purpose o f present work is to investigate the m agnetic particles in the industrial d usts andashes and in the topsoils of industrial areas, where these particles cause an artificial increase ofmagnetic susceptibil i ty. The former field observations by S t r zy s zc z ( 1988 ,1989a , 1989b ,1991 ) ,S t r z y s z c z a n d M a g i e r a ( 1 9 9 3 ) and S t r zy s zc z e t aL ( 1994) will be supplemented by laboratorycharacterization o f the ferromagn etic mineralogy.

2 . MATERIALS AN D METHODS

Tw o l a r ge indus t r ia l p l an t s in U p pe r S i l e s ia have be en s e l ec t ed f o r t h i s s t udy : Th e

" P o k o j " i r o n w o r k s in R u d a S l a s k a a n d t h e h u g e p o w e r p la n t J a w o r z n o I I I ( u n d e r l in e d

l oca l i ti e s i n F i g . 1 ). M e t a l lu r g i ca l dus t s f r om t w o b l a s t - f u r naces o f t he " Po ko j " i r on w or ks

a n d a s h e s f r o m t h e e l e c tr o - fi lt e r o f t h e J a w o r z n o I I I p o w e r p l a n t h a v e b e e n s a m p l e d . O v e r

6 0 s o i l s a m p l e s h a v e b e e n c o l l e c te d d u r i n g a n e a r l ie r s t u d y f r o m t h e a r e a n e a r t h e s e p l a n t s

b e t w e e n 1 9 8 8 a n d 1 9 9 2 ( s e e r e f e r e n c e s a b o v e ) . T w o s o i l p r o f i l e s c o l l e c t e d i n t h e

p r e v a i l i n g w i n d d i r e c ti o n 1 .2 a n d 2 . 4 k m N E f r o m " P o k o j " i r o n w o r k s a n d s a m p l e s f r o m

t h e to p o f a p e a t s o il n e a r th e J a w o r z n o I I I p o w e r p l a n t h a v e b e e n c h o s e n f o r th e p r e s e n t

l a b o r a t o r y s tu d y . T h e t h ir d a r e a s e l e c t e d f o r t h e p r e s e n t s tu d y is O j c o w N a t i o n a l P a r k

( O N P) , w h i ch i s s i t ua t ed 25 km ea s t o f t he U pp er S i l e s i a i ndus t r ia l d i s t r ic t i n a r eg i on

w i t h o u t l a r g e s o u r c e s o f p o ll u ti o n . A c c o r d i n g t o G r o d z i e n s k a ( 1 9 9 2 ) , t h e h e a v y m e t a l

c o n c e n t r a t i o n i n m o s s e s f r o m O j c o w N a t i o n a l P a r k i n d i c a t e s t h e m o s t s t r o n g l y p o l l u t e dn a t i o n a l p a r k i n P o l a n d . S o i l p o l l u t i o n a n d m a g n e t i c s u s c e p t i b i l i t y h a v e b e e n s t u d i e d i n

Studia geoph , et geo d. 40 (1996) 277

Z Strzyszcz et al.

th i s a rea in 20 soi l prof i les by S t r z ys z c z a n d M a g i e r a ( 1 9 9 3 ). T w o o f th e m , w h i c h h a v e t h e

highes t magnet ic suscept ib i l i ty va lues , have been se lec ted for the present inves t iga t ion.

So i l s ampl es f rom O N P and a round t he J aw orzno I I I pow er p l an t have been co l l ec t ed in

fores t s , where the topsoi l i s not d i s turbed by agr icul tura l ac t iv i ty and pol lu t ion inc ludingmagne t i c pa r t i c l e s con t i nued ove r a l ong t i me . The so i l s a round t he "Poko j " i r on w orks

have been co l l ec ted f rom de fo res t ed a reas w h i ch w ere no t cu l t i va ted and p l oug hed du r i ng

the las t 30 years .D ur i ng t he f i r st s tage o f th i s s t udy t he fo l l ow i ng magne t i c pa r am e t e r s have been

measured :Z - t he spec i f ic magne t i c bu l k suscep t ib i li t y measu red us i ng a l ow - f r equency , l ow

f ie ld suscept ib i l i ty br idge K LY -2;

Zfd - t he f r equency dependence o f magn e t ic l ow f i e l d suscep t ib i l it y measu red a t t w o

f r equenc i e s ( d if f e r ence be t w een ZI f a t 0 . 47 k H z and Zhf a t 4 -7 kH z , expres sed a s

pe rcen t age o f Z) us i ng a B ar t i ng ton suscep t ib i l it y b r idge ;

S I R M - t he s a t u r a t i on i so t he rma l r emanen t magne t i za t i on w hi ch w as acqu i r ed a t r oomt empera t u r e i n f i e l ds up t o 1 T measured on D i g i co f l uxga t e sp i nne r

magne t omet e r ;I R M - i so the rma l r emanen t magn e t i s a ti on measured a s a f unc t i on o f t he app l i ed f i e l d i n

o rde r t o d e t e rr a ine t he IR M / SIR M ra ti os i n va r i ab le f ie l ds ;

(B0)cr - the co erc iv i ty of sa tura t ion reman ent m agne t iza t ion;

M s ( T ) - t he t empera t u r e dependence o f s a t u r a ti on magne t i za t ion measured us i ng a C ur ie

ba l ance w hereby t he s ampl es w ere sub j ec t ed t o a h ea t i ng and coo l i ng cyc le i n a i r ,

i n a s t eady magne t i c fi e l d o f0 -1 T ;

Magne t i c concen t r a t e s ( us i ng a hand magne t ) w ere ob t a i ned f rom four s ampl es fo r

fur ther minera logica l s tudies . This mater ia l has been subjec ted to the chemical and

mi ne ra l og i ca l ana lys i s u si ng a C am eca SX 50 e l ec t ron m i c roprobe .

3. RESU LTS AND DISCUSSION

3 .1 M e t a l l u r g i c a l d u s t s

The me t a l l u rg i ca l dus t s ampl es f rom t he "Poko j " i r on w orks have h i gh magne t i c

suscept ib i l i ti es ranging f rom 5900 to 6400 x 10-Sm3kg 1 . The se sam ples rea ch o r are

c lose ly to m agnet ic sa tura t ion in a f i e ld o f 300 mT . F igure 2a presents the ba ckf ie ld

dem agne t iza t ion for the meta l lurgica l dus t sample HP 2 (blas t - furnace dus t ) . The coerc iv i ty

(B0)cr am oun ts to 25 m T an d the S- ra t io which i s def ined as the ra t io o f i so therm al

r eman ence a t a backf ie l d o f 0 .1 T ve r sus S IR M (S t obe r and Thom pson , 1979), equ a l s-0 . 7 2 . C oerc i v i t y va l ues be t w een 20 and 40 mT a r e cha rac t e ri s ti c o f r e l a ti ve l y coa r sem agne t i t e gra ins (Scoul los e t a l. , 1979). T he S-value sugges t s tha t m agn et i t e is the

p redom i nan t magne t i c mi ne ra l in t he s ampl e and t he p r e sence o f h i gh coe rc i v i ty

ant i fer rom agne t ic m inera l s i s ma rginal .

L ow .Zfd values be tw een 1-07 and 1-44% are a l so charac ter is t i c . Th e sm al l f requ encydepend ence is cha rac te r is t ic f o r s i ng l e - t o m ul t idom ai n g r a ins o f magne t i t e - m os t l y g r ai ns

ove r 1 gm (Ki t t e l , 1949; Ban er je e e t a l ., 1 981) . Very smal l gra ins be low the s ingle-

domai n / supe rpa ramagne t i c t h r e sho l d w ou l d show grea t e r changes o f magne t i c

suscept ib i l i ty a t var iable f ie ld f requen cy.

278 Stud ia geoph, et geo d. 40 (1996)

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S = 0.62 .

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(Soiom Ojcow NatonalPark Profe 2)

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(B.°,= 36 roT.

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zooameaucd

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Z S t r zy s zc z e t a l.

Thermomagne t i c ana l yses show t ha t t he C ur i e po i n t s o f me t a l l u rg i ca l dus t s r ange

be t w een 600 and 610 °C (F i g . 3a ). These va l ues a re be t w een t he C ur i e t empera t u r e fo r

pure mag ne t i t e ( 585°C ) and t ha t o f pu re haema t i te (675°C ) . T he t he rmom agne t i c cu rves

a r e non- r eve rs i b le . A t t e r hea t ing and co o l i ng to 650°C , t he room t empera t u r emag ne t i za t ion va l ue rep resen ts o n l y abou t 80% of t he i n i ti a l va l ue . Som e p ropor t ions o f

t he f e r romagne t i c i r on mi ne ra l s mus t have been t r ans fo rmed i n t o mi ne ra l s o f l ow er

spon t aneous m agne t i za t ion dur i ng hea ti ng . Th i s behav i our i s t yp i ca l f o r magh emi t e and is

connec t ed w i t h g r adua l t rans fo rma t i on o f maghem i t e t o hem at i te i n t he t empera t u r e r ange

3 0 0 - 5 0 0 ° C T h e o f t e n o b s e r v e d n e g l i g i b l e m a g n e t i z a t i o n l o s s d u r i n g h e a t i n g a t

t empera t u r es be l ow 400 °C comb i ned w i t h a d i s ti nc t k i nk o f t he magne t i za t i on cu rve

sugges t s the presence of a t l eas t two fer r imagnet ic minera l s in the meta l lurgica l dus t s

w hi ch acco rd i ng to t he above magne t i c r e su l ts m us t be cha rac t e r ized by l ow coe rc i v i t y andhigh S values .

The compo s i ti on o f the m os t l y sphe ri ca l magne t i c g r a ins i n the me t a l l u rg i ca l dus t s has

been de termin ed by microprobe analys i s . Var iable resul t s of the s to ichiom et r icquan t i ta t ive chem i ca l ana l ys is o f the p e r cen t age com pos i t ion a r e ob t a i ned fo r d i f f e r en t

par t ic les . The to ta l analys i s c loses be tween 89.90 to 94.39% (Table 1) very near to the

t heore t ica l va lues o f pu re magne t i t e a t 93 -06% and o f pu re m aghem i t e a t 90 . 41%. E i t he r

o f t he t w o p hases m ay cons t i tu t e t he mag ne t i c g ra i ns. Som e pa r t ic l e s , how ever , a r e m ade

up o f a mi x t u r e o f bo t h phases .

3 . 2 F l y a s h e s

The magn e t i c suscep t ib i l it y o f the f l y a shes f rom Jaw o rzno I l l pow er s t a t ion r ange

a round 2500 x 10-Sm3kg-I . This va lue i s reduced a t h igher f requency only l i t t l e by 1 .6 -

- 1 .7% (Zfd) . (B0)cr and S (Fig . 2b) are s im i lar to the cor respo nding values m easured forme ta l lurgica l dus t s . The y sugg es t tha t s imi lar magnet ic par t ic les occu r in the f ly ashes .

The t he rmom agne t i c ana l ysi s fo r f l y a sh f rom Jaw orzno I I I sugges t s t ha t magne t i t e is

the pred om inant fer romag net ic minera l in the sample (Fig . 3c) . Th e C ur ie point i s s l ight ly

below 600°C, and the magn et iza t ion curve i s a lmo st revers ib le upon cool ing.

G ranu l om et r i c ana l ys is o f the m agne t ic f r ac t ion f rom f l y a sh f rom Jaw orzno I l l show s

t ha t 75% of f e r romagne t i c g r a ins a r e con t a i ned i n t he r ange 2 - 50 ~m w hereas t he

f rac t ion < 2 k tm am ounts on ly to 6% (Table 2) .

3 .3 S o i l s a r o u n d " P o k o j " i r o n w o r k s

Sand y c l ays and sands cons t i tu t e t he subs t ra t e i n the a r ea o f "P ok o j " i r on w orks . T he i r

spec i f ic magne t i c suscep t ib i li ti e s va ry be t w een 15 and 30 x 10 -8m 3k g- / T he se va l ues a re

i nadequa t e t o accoun t f o r t he magne t i c suscep t i b i l i t y va l ues obse rved i n t he uppe rmos t

20 cm o f the soi l prof i les (Fig . 4a , b) .In prof i le 1 , the suscept ib i l i ty va lues are h igh across the u pperm ost 20 cm o f the soi l

wi th the m axim um be tween 15 - 20 em . In prof i le 2 , cons iderable suscep t ib i li ty increase i s

observed only in the topm ost 5 cm of the soi l. T he high bulk su scept ib i l i ty Z i s

accom pan i ed by ve ry l ow suscep t ib i l it y f requency-depend ence (Zfd ), w h i ch va r i e s be t w een1.10 and 1 .78% in prof i le 1 . In prof i le 2 , Zfd seems to b e inverse ly propor t ional to the Z.

Zfd has a m ax i mu m (4 . 04 % ) in t he ho r izon w h ere t he bu l k suscep t i b i li t y is m i n i ma l .

280 Studia geoph, et geod. 40 (1996)

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Ta ble I . Stochiometric analysis o f f ive different magnetic particles ( in % ) from metallurgical dust.

1 2 3 4 5

SiO 2 0,00 0.02 1.93 0-19 0.24

TiO 2 0.00 0.05 0-04 0.06 0,12

AI203 0.10 0.44 0.52 0.11 0.87

FeO 89.76 93.73 88.34 90.05 88.79

M nO 0.00 0.02 0-01 0.08 0-03

Mg O 0-00 0.05 0-00 0-00 0-01

CaO 0-01 0.06 0.53 0-03 0.03

N a2 0 0.02 0.02 0.00 0.00 0,04

K 20 0.01 0.00 0.00 0.02 0,00

Total 89.90 94.39 91.36 90.54 90.13

T h e v a l u e s o f t h e S p a r a m e t e r a n d c o e r c i v i ty o f r e m a n e n c e (B 0 )c r (F i g . 2 c ) a r e h i g h e r

t han i n t he m e t a l l u r g i ca l dus t , bu t t hey a r e s t il l i n a r ange ch a r ac t e r i s t i c o f r e l a t i ve l y coa r s e

g r a i n e d m a g n e t i te ( S c o u l l o s e t a l ., 1 9 7 9 ) . Th e va l ue o f ( B0)c r ( 45 m T) i n p r o f i le 1 and t he

pos i t i on o f t he ho r i zon w i t h m ax i m um s u s cep t ob i l i t y in the s o i l p r o f i l e ( 15 - 20 cm ) cou l d

s ugge s t tha t po s s i b l y a l s o f ine r f e r r im a gne t i c s o f pedog en i c o r i g i n ex i st . The ve r y l ow Zf a,

h o w e v e r , s h o w s t h a t t h e s e m a g n e t i c m i n e ra l s a r e n o t i n th e r a n g e o f s u p e r p a r a m g n e t i c

g r a i n s . Th e r e f o r e a pedo gen i c o r i g i n i s exc l uded . I n p r o f i l e 2 , Xfd ( 2 . 6 9% ) i s a l it tl e b i t

h i ghe r , bu t i s s ti ll too l ow t o g i ve de f i n i te ev i d enc e f o r t he occu r r ence o f f i ne - g r a i ned

p e d o g e n i c m a g n e t i c m i n e r a ls .

T h e r m o m a g n e t i c a n a l y s i s ( F ig . 3 d ) s h o w s t h a t th e C u r ie p o i n t is j u s t a b o v e 6 0 0 ° C l ik ei n t he m e t a l l u r g i ca l dus t . Th i s s ugges t s t ha t t he p r edom i nan t m agne t i c m i ne r a l i s non -

s t o i ch i om e t r i c m agne t i t e . The t he r m om agne t i c cu r ve i s i r r eve r s i b l e and a f t e r coo l i ng t o t he

r oom t em per a t u r e , t he m agne t i s a t i on i nc r eas es by 40% i n r e l a t i on t o t he i n i t i a l va l ue . Th i s

i n c r ea s e h a s p r o b a b l y re s u l te d f r o m t h e c o n v e r s i o n o f p a r a m a g n e t i c m a t e r ia l a t h ig h

t e m p e r a t u r e t o f e r r i m a g n e t i c m i n e r a l s . S c a n n i n g e l e c t r o n m i c r o s c o p e o b s e r v a t i o n s h a v e

s h o w n t h e p r e s e n c e o f sp h e r ic a l m a g n e t i c p a r ti c l e s w h i c h h a v e d i a m e t e r s b e t w e e n 1 a n d

20 ~tm.3 . 4 S o i l s a r o u n d J a w o r z n o I I I p o w e r s t a t i o n

P e a t s o il s w h i c h d e v e l o p e d o n s a n d s , p r e d o m i n a t e a r o u n d t h e J a w o r z n o 1 II p o w e r p l an t .

Th ey a r e ve r y good co l l ec to r s o f i ndus tr ia l po l l u ti on . T he o r ga n i c ho r i zo n i n s o i ls f r om

J a w o r z n o s h o w s v e r y h i g h s u s c e p ti b il it ie s b e t w e e n 1 3 0 0 - 1 5 0 0 × 1 0 -S m 3 k g 1 . T h e

Ta ble 2. Granulometric com position o f the magn etic fraction of f ly ash from Jaworzno III power

plant.

Analys is Percen tofgra ins i ze ~act ion( in ~ m )

1000-500 500-250 250-100 100-50 50-20 20 -6 6 - 2 < 2

I 0 1 14 5 20 31 23 6

2 0 1 14 5 19 32 23 6

3 0 1 14 5 20 31 23 6

282 Studia geoph, et geod. 40 (1996)

T h e I n fl u e n c e o f l n d u s t r i a t l mm i ss i o n s o n t h e M a g n e t i c S u sc e p t i b i l i t y ...

suscep t ib i l it y dec reases ab rup t l y be l ow t he o rgan i c ho r i zon t o a va l ue 2 5 0 - 280 ×× 10-8m3kg - I. A f t e r r emova l o f o rgan i c ma t t e r and concen t r a t i on o f t he ma gne t i c pa r t i c le s

us i ng a hand m agne t , so il s ampl es f rom t he o rgan i c ho r i zon sh ow a l mos t i den t i ca l va l ues

of magn et ic param eters l ike the soi l samp les col lec ted near the i ron work s (Figs . 2d , 3d) .The coe rc i v i t y (B 0)cr i s 45 mT and t he S pa r ame t e r equa l s - 0 . 64 . I t sugges t s tha t aga i n a

h i gh concen t r a t ion o f an th ropogen i c m agne t i c pa r ti c le s i s r e spons i b l e f o r t he abnorm a l l y

h i gh m agne t i c suscep ti b il it y . B es ides o f the ac t i v i ty o f the pow er p l an t and t he spec i f ic so i l

t ype , the g eograph i c pos i ti on o f J aw orzno i n the eas te rn pa r t o f U pper S i l e s ian Indus t r i a l

D i s t r ic t p l ays an add i t iona l r o l e f o r t he h i ghe r con cen t r a t ion o f f e r r i magne t i c s i n t h i s a r ea .

Since wes ter ly wind s predom inate in th i s a rea , th i s par t of Upp er Si les ia i s espec ia l ly

exposed t o an i n f l ux o f po l l u t ion f rom t he cen t r a l pa r t o f U p per S i l es i a , w h ere m any b i g

emi t ters are located .

3 .5 S o i l s f r o m O j c o w N a t i o n a l P a r k

So i l p ro f il e s have been t aken i n O j cow N a t i ona l Pa rk , w h i ch i s s it ua t ed 25 km f rom t he

eas t border o f the Up per S i lesian Indus t r ia l Dis t r ic t . The y show a s ign i f icant susce pt ib i l i ty

i nc r ease i n t he uppe rmos t f ew cen t i me t e r s o f t he f e rmen t a t i on (O f ) and humi c (O h)subho r izons (Fig . 4c ,d) . The su scept ib i l i ty in these sub hor izon s i s severa l t im es h igh er

t han i n t he o t he r p ro f i l e pa r t s w h i ch deve l oped on ex t r eme l y w eak l y magne t i c Ju r as s i c

l imes tones . Th e suscept ib i l i ty o f these b edrock s i s about 7 × 10-Sm3kg - I . Th e Zfd value in

s u b h o r iz o n s w i t h m a x i m u m s u s c e p t ib i li ty is v e r y l o w ( 1 . 5 - 2 % ) . T h e m a x i m u m Z f d

occur s be l ow 10 cm, mo s t l y i n t he B -hor izon , w here t he suscep t i b il i ty i s l ow and p robab l ydue t o t he ex i s t ence o f na tu r a l, f i ne -g ra ined an t i fe r romagne t i c and p a r amag ne t i c g r a i ns .

( a ) S u s c e p t i b i l i t y ( x l O " m : k g "~ x ( % )

~ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ ~ ~ ' ~~ ~x.x.x.x.x.x.x.~x.x.x.x.xx.x.~..

R u d a S la s k a

Profile t (1.2 km N E from ron-works)

1 0 ¸

¢ ~ 3 0 .

S u = c e p t t b l t t t y ( x l O ' = m ~ k g " * } X r n( % )

0 2 0 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0 1 6 0 0 1 0

Ojcow Nat iona l ParkPro file I

( b ) S u l c e p t l b l l i t y ( x l f f * m ] k g "~ X le (% )0 2 0 0 4 0 0 6 0 0 8 0 0 1 0 0 0 1 2 0 0 1 0 )

~\K~\\<,\\\\\\\\~\\\\\\\\\~\K\\\\\\\K\\~ *

Ruda Slaska

Pro file 2 (2.4 km NE from ron-world)

( d ) S u s c e p t i b i l i t y ( x t O " m a k g "1 1 X f = (% )

0 S 0 1 0 0 1 5 0 2 0 0 0 1 0

~ ~ .~.~~~ ~~~ 5 ~~~~~ " ....

2o 1 ~ O l c o wNa t iona l Pa rk

3o Pro f i le 2

Fig. 4. Bulk and frequency dependent magnetic susceptibility in soil profiles near an ironwork (a,b)and in the Ojcow National Park (c,d).

Studia geoph, et geod. 40 (1996) 283

Z. Strzyszcz et al.

T h e c o e r c i v i ty o f r e m a n e n c e ( ca . 3 5 m T ) in th e l a y e rs o f m a x i m u m s u s c e p ti b il it y

p r o v e s t h a t m a g n e t i t e m u l t i d o m a i n g r a i n s a r e p r e d o m i n a n t l i k e i n t h e s o i l s a r o u n d t h e

" P o k o j " ir o n w o r k s a n d J a w o r z n o I I I p o w e r pl an t . T h e S - v a l u e s at - 0 . 6 3 a n d - 0 - 7 0

( F i g . 2 e , f ) w i t n e s s t o th e p r e p o n d e r a n c e o f f e r ri m a g n e t i c o v e r a n t i f e r r o m a g n e t i c i r o no x i d es . T h e t h e r m o m a g n e t i c c u r v e i s a l s o s im i la r t o t h o s e p r e s e n te d b e f o r e . T h e s a m e

f e r r i m a g n e t i c s o f a n t h r o p o g e n i c o r i g i n a r e r e s p o n s i b l e f o r th e s u s c e p t i b i l i ty i n c r e a s e o f t h e

t o p s o i l s f r o m O j c o w N a t i o n a l P a rk .

4 . M A G N E T I C PA R T I C L E S A N D H E A V Y M E T A L S

M a n y a u t h o r s h a v e e m p h a s i z e d t h e c o n n e c t i o n b e t w e e n t h e in c r e a s e o f m a g n e t i c

s u s c e p t i b i l it y a n d t h e c o n c e n t r a t i o n o f c e r t a in h e a v y m e t a l s i n v a r i o u s e n v i r o n m e n t s .

Beckwi th e t a l . ( 1986) s h o w a l in e a r r e l a ti o n s h i p b e t w e e n t h e c o n c e n t r a t i o n o f

f e r r i m a g n e t i c s a n d t h e C u , F e , P b a n d Z n c o n t e n t i n s e d i m e n t s c o l l e c t e d i n a n u r b a n a r e a

a s w e l l a s n e a r a n h i g h w a y . A s i m i l a r r e l a t i o n s h i p b e t w e e n S I R M a n d s u s c e p t i b i l i t y o n t h eo n e h a n d a n d P b , C u , Z n , a n d C d i n a t m o s p h e r i c p a r t i c u l a t e s o n t h e o t h e r h a s b e e n

o b s e r v e d b y Hunt e t a l . (1984) . T h e r e la t io n b e t w e e n t h e p r e s e n c e o f m a g n e t i c m i n e r al s

a n d t h e c o n c e n t r a ti o n o f h e a v y m e t a ls in th e m a r in e e n v i r o n m e n t h a s b e e n c o n f i r m e d b y

Sco ul lo s e t aL ( '1979). A l in e a r re l a ti o n s h ip b e t w e e n s o m e m a g n e t i c p a r a m e t e r s a n d t h e P b

a n d C u c o n c e n t r a t io n i n m o d e m l a cu s tr in e d e p o s i t s h a s b e e n p o i n t e d o u t b y Old f i e ld e t a l .

(1984) . S t r zy s zcz and M ag iera (1993) h a v e o b s e r v e d a p o s i t i v e c o r r e l a t i o n b e t w e e n

s u s c e p t i b i l it y a n d t h e c o n c e n t r a t i o n o f m e t a l s s u c h a s Z n , P b a n d C d i n t h e t o p s o i l s o f

O j c o w N a t i o n a l P a r k. Hu l t e t e t aL (1980) o b s e r v e d t h a t t h e f i r s t r o w t r a n s i t i o n e l e m e n t s -

V , C r , M n , C o , N i , Z n a n d C u - p r e s e n t in fl y a s h e s f r o m A m e r i c a n p o w e r p l a n t s a r e

m o s t l y c o n n e c t e d w i t h m a g n e t i c m i n e r a l p h a s e s , a n d o c c u r u s u a l l y i n t h e f o r m o f

s u b s t i t u t e d s p i n e ls F e 3 . x M x O 4 .

T h e r e f o r e s o m e p a r ti c le s f r o m a m a g n e t i c c o n c e n t r a t e o f f ly a sh f r o m J a w o r z n o I I I

p o w e r p l a n t w e r e a n a l y z e d m i c r o c h e m i c a l l y . E l e v e n p a r t i c l e s w h i c h a c c o r d i n g t o

s t o i c h i o m e t r i c c h e m i c a l a n a l y s i s a n d m a g n e t i c in v e s t i g a t i o n s a r e m a d e o f n o n -

s t o i c h i o m e t r i c m a g n e t i t e o r / a n d m a g n e t i t e - m a g h e m i t e t r a n s i t i o n m i n e r a l s , h a v e b e e n

s e l ec t e d f o r tr a c e e l e m e n t m i c r o p r o b e a n a l y s is . T h e s i z e s o f t h e s e p a r t ic l e s a r e 1 0 -

- 4 0 I .t m . S e v e n m o s t c o m m o n h e a v y m e t a l s (C r , M n , N i , C u , Z n , C d , P b ) h a v e b e e n

Table 3 . He avy metals in ma gnet ioc par tic les o f f ly ash f rom Jaw orzno I I I pow er plant (in ppm).

C r M n N i C u Z n C d P b

I < 100 < 100 < 100 < 00 < 100 < 100 340

2 < 100 < 100 < 00 < 100 330 < 100 260

3 < 100 < 100 110 250 < I00 < 100 < 100

4 < 100 < 100 < 100 < 00 < 100 < 100 130

5 < 100 < 100 < 100 < 00 < 100 < 100 320

6 < 100 < 100 100 < 100 350 < I00 220

7 < 100 < 100 < 100 < 00 < 100 < 100 < 100

8 < 100 < 100 640 170 120 < 100 730

9 < I00 < 100 < 100 < 100 < 100 < 100 320

10 < 100 < 100 100 < 100 < 100 < 100 500

11 < 100 < 100 880 < 100 < 100 < 100 < 100

284 Studia geoph, et ge od. 40 (1996)

The Inf luence o f lndus tr ial Imm iss ions on the Mag net ic Suscept ibi l i ty . ..

determined (Table 3) . I t was found tha t l ead , n ickel , z inc and copper occur in subs tant ia l

quan t i ti e s in some o f t he 11 pa r ti c le s . C oncen t r a t ions o f > 100 ppm o f l ead w ere m easured

in e ight par t ic les , those o f n ickel in f ive , those o f z inc in three , an d cop per in two. T he

o t he r i nves t iga t ed me t a l s w ere be l ow r e so l u t ion o f the m i c roprobe used . I n mag ne t i cpa r t ic l e s ove r 300 / .t m i n d iame t e r , manganese o ccur s i n quan t i t ie s even u p t o 2 -3%. In t he

met a l l u rg i ca l dus t s, t he magne t i c pa r ti c le s con t a i n up t o 0 . 08% of man ganese (Tab l e 2 ).

5. CONCL USIONS

1. A ccum ul a t i on o f an th ropogen i c f e r ri magne t i c s due t o i mm i ss ion o f i ndus t r ia l dus t s ove r

l ong t i me pe r i ods causes cons i de r ab l e i nc r ease o f magne t i c suscep t i b i l i t y i n so i l s ,

especia l ly in the fermenta t ion (Of) and humic (Oh) subhor izons of so i l l i t t e r . The

suscept ib i l i ty o f so i l s in indus t r ia l i zed regions ca n be tak en as a me asure o f the

i ndus t ri a l imm i ss ions ove r a l a rge a rea and a w i de r ange o f emi s s ions . Th e so i ls o f the

O j cow N a t i ona l Pa rk , a l though p l aced a l r eady some 25 km eas t f rom t he m a i n sourceso f emiss ion in Up per Si les ia , indica te ra ther extens ive pol lu t ion .

2 . M i ne ra log i ca l and chemi ca l s t ud ie s o f magn e t i c pa r t ic l e s , w h i ch a r e r e spons i b l e f o r t he

cons iderab le increase of suscept ib i li ty in top sub hor izon s o f the soi l s in Up per Si les ia

show c l ea r l y t ha t t hese a r e mos t l y r e l a t i ve l y l a rge (mul t i domai n ) magne t i t e g r a i ns

rang ing f rom 1 to 20 ~tm in s ize . The ma gnet i t e genera l ly is non-s to ich iom et r ic , be ing

an i n t e rmed i a t e phase be t w een Fe304 and 7Fe203 . Magne t i c pa r t i c l e s w i t h t he s amemagnet ic charac ter i s t i cs and chemical composi t ion are present in meta l lurgica l dus t s

w hi ch a r e em i t t ed from iron w orks , i n f l y a shes o r i g i na t ing f rom ha rd -coa l co mb us t i on

in powe r p lants and a l so in the soi l s o f the ind us t r ia l a reas . The s imi lar i ty of mag net ic

pa r t i c l e s i s t aken a s ev i dence fo r an an t h ropogen i c o r i g i n o f pa r t i c l e s w h i ch a r e

r e spons ib l e f o r t he h i gh magne t i c suscep t ib i li ty o f so i l s i n U pper S i l e si a and i n ad j acen t

areas.3 . The s t udy o f add i t i ona l magne t i c pa r ame t e r s such a s X fd , S I R M , 1 R M and (B0)cr and

t he rmom agne t i c ana lys i s is ab l e t o cha rac t er i ze t he t ype o f t he ma gne t i c pa r t ic l e s , t he i r

dom ain s ta tus , and the i r anthropogenic or na tura l or ig in .4 . C ons i de r ab l e amo un t s o f heavy me t a l s w h i ch can b e a po t en t i a l haza rd fo r t he

env i ronment , a r e bound t o t he magne t i c pa r t i c l e s . The f a s t and r e l a t i ve l y cheap

measuremen t s o f t he magne t i c l ow f i e l d suscep ti b il it y can be used a s a p r e l i mi na ry

met ho d o f s t udy i ng po ll u t ion e f f ec t s i n so i ls be fo re s t a r t ing t i me-con sum i ng and

expens i ve chemi ca l me t hods . The an t h ropogen i c f e r r i magne t i c s can be t r ea t ed a s a

t r ace r f o r the p r e sence o f heavy me t a ls .

Man uscr ip t r ece ived: 12 Nove mb er 1995; Rev i s ed: 10 Februa ry 1996

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Banerjee S.K ., King J. and M arv in J. , 1981: A rap id method for magn etic granulometry withapplications to environmental studies. Geophys. Res. Lett. 8, 333-336.

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Z S t r zy s zc z e t a l, : The In f l ue nc e o f Indus t r i a l Imm i s s i ons on t he M agne t i c Susc e p t i b i l i ty ...

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part iculates ofa nth rop og en ic or igin . Sci. Total Environ. 33 , 129-139 .

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Scou l los M. , Oldf ield F. and Thom pson R. , 1979: M agnet ic m oni tor ing o f mar ine par t iculatepollu tion in the Elefsis G ulf , Greece. Mar. Pot tut . Bul l , 10 , 287-2 91 .

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far den Nach weis von fer romagnetischen Eisen in der Umwelt . Arch. Ochr, Srod. 3 - 4 ,137-143 ( in German) .

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Strz ysz cz Z., 1993: M agn etic susceptibili ty o f soils in the area influenced by industrial emissions.In : Soi l M oni t ori ng , M onte Verita, Birkh~tuser Verlag, Basel, pp. 255 -2 69 .

S t r zys zcz Z. and Magie ra T . , 1993 : Fer romagne tycznos c g leb w Parkach N arodo wy ch i j e j

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286 Studia geoph, et ge od. 40 (1996)

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