strzyszcz (industrial emissions)

12
THE INFLUENCE OF INDUSTRIAL IMMISSIONS ON THE MAGNETIC SUSCEPTIBILITY OF SOILS IN UPPER SILESIA ZYGMUNTSTRZYSZCZA NDTADEUSZ MAGIERA Institute of Environmental Engineering, Polish Academy of Sciences, Zabrze, Poland 1 FRIEDRICHHELLER lnstitut fiir Geophysik, Zarich, Switzerland 2 S u m m a r y : Samples of metallurgical dusts and fly ashes from coal power plants and iron works in Upper Silesia as well as soil profiles in the close vicinity of these plants and in Ojcow National Park (ca. 25 km east o f the industrial area) have been studied magnetically and mineralogically. The metallurgical dusts and fly ashes are highly enriched in ferromagnetic minerals. The topsoils from profiles collected near the plants have very high values o f magnetic susceptibility while susceptibility in the fermentation and humic subhorizons in soil profiles from Ojcow National Park is considerably increased The magnetic properties of the metallurgical dusts and fly ashes such as frequency dependence of susceptibility, saturation remanence or coercivity are similar to those observed in the top horizons of the soils. They are mostly related to the occurrence of large (multidomain) grains o f non-stoichiometric magnetite ranging from I to 20 I.tm. The similarity of the magnetic particles in the soils is taken as evidence of an anthropogenic origin. They are responsible for the high soil susceptibilities in Upper Silesia and in adjacent areas. Some of the magnetic particles carry substantial quantitities o f trace elements such as Pb, Ni, Zn and Cu. Field and laboratory susceptibility measurements can therefore be used as a simple and costeffective method f detecting the presence of heavy metals in the soi& o f this area. K eyw ords: anthropogenic ferrimagnetics, metallurgical dust, fly ashes, trace elements 1. INTRODUCTION Upper Silesia (Katowice voivodeship) is the most industrialised and most polluted region of Poland. Many heavy industry plants are concentrated in this small area covering ca. 6650 km 2. Environmental hazards are mostly linked to the old metallurgical plants, cokery plants and power plants which combust large amounts of hard coal and emit many types of gaseous and dusty pollutants. Dependent on character and size, the pollutants can be transported over variable distances as solid phase particles or in aerosols. After landing on the soil surface, the dust particles penetrate into the soil profile and accumulate mostly in the fermentation (Of) and humic (Oh) subhorizons. The industrial dust falls contain also a certain proportion of magnetic particles, which cause an increase of magnetic susceptibility in the topsoil. According to records at many monitoring stations in the voivodeship since 1981 the dust fall in the study area varied from 200 to 450 gm-2year 1 (Strzyszcz, 1994) and the iron flux in dustfall varied from 10 to 200 gm-2year 1 (Fig. 1). Earlier investigations of metallurgical dusts and fly ashes from power plants (Strzyszcz et aL, 1988," Strzyszcz, 1989a; Strzyszcz and Magiera, 1993) demonstrated very high magnetic susceptibility 1 Address: Institute of Environmental Engineering, Polish Academy of Sciences, ul. M. Sklodowskiei 34, PL-41-800 Zabrze, Poland (Fax: +48-32-t 7174 70) 2 Address: Institut ftir Geophysik, ETH Honggerberg, CH-8093 Ztirich, Switzerland 27 6 Studia geoph, et geod. 40 (1996), 276-286 © 1996 StudiaGeo s.r.o., Prague

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Page 1: Strzyszcz (Industrial Emissions)

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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

© 1996 StudiaGeo s.r.o., Prague

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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

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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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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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Z S t r zy s zc z e t aL

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)

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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.~..

2O

R u d a S la s k a

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

(c )

1 0 ¸

2 0 .

¢ ~ 3 0 .

4 0 .

6o~

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\\~ *

15

20

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

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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)

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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

References

Beckwith P.R . , El lis J .B . , Re vi t t D .M . and Oldfield F. , 198 6: Heavy m eta l and magnet icrelationships for urban source sediments. Phys. Earth Planet. Inter. 42, 67-75.

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.

Studia geoph, et geod. 40 (1996) 285

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