A L IN A K A B A T A -P E N D IA S , EDW ARD BO LIBRZU CH , PIO TR TA R ŁO W SK I
IMPACT OF A COPPER SMELTER ON AGRICULTURAL ENVIRONMENTS
PART I. CONTAMINATION OF SOILS
In stitu te of S oil S cien ce and C u ltiv a tio n of P la n ts at P u ła w y
IN TR O D U C TIO N
High concentrations of heavy m etals in soils and plants of industrial areas have been reported by several authors. An impact of m etallic sm elters on agricultural quality should be of a special environm ental concern.
The m ain objective of the studies conducted on chemical changes in n atu ra l vegetation surrounding the copper sm elter was an evaluation of a degree of plant contam ination and a delineation of an area affected by the sm elter emissions. The studies obtained two the most common crops of the ru ral area around the copper sm elter. A contam ination of eatable parts of plants by heavy m etals was also investigated to provide some inform ation on a health hazard.
Legnica-Głogów Copper Belt located in northern-east p art of Lower Silesia is a m ajor producer of copper in Poland. The copper mines operate on the new discovered (1957) ore copper deposits of sedim entary origin. Copper and other nonferrous m etals are associated w ith the schists and carbonates rocks. Copper occurs m ainly as bornite, chalcopyrite and chalcocite [6]. Głogów Sm elter built as the second plant in this area began the copper production in 1969-1970 years.
The copper production from sedim entary ores is known to be one of more contam inating industry due to a large am ount of ore wastes (up to 98 per cent) and due to an emission of sulfur and polym etallic com pounds [1]. The emission from five stacks of Głogów Sm elter is calcu lated for 300-500 tons per year [4, 10].
The sm elter is located w ithin the ru ra l area of subhum id climate w ith m ean annual precipitation about 500 mm (with the highest rainfall in A pril to September) and mean annual tem perature 8.4°C (winter
0.9°C, sum m er 17.8°C). The predom inant wind direction is from SW and W (about 40 per cent) w ith the speed 2-5 m/sec (about 50 per cent). The topography of this lands is typical for a fluvioglacial low territo ry eleva tion 70-100 m a.s.l.
Basing on the results of the prelim inary investigations conducted in the sum m er 1973, the proxim ity along downwind direction from the Głogów Sm elter was established for the fu rth er studies carried out during 1974-1978 period.
M A TE R IA L S A N D M ETH ODS
The locations of sampling of plants and soils are shown on Fig 1.
The detailed description of soil and plant samples is given in the earlier publication [7].
F ig. 1. L ocation of sa m p lin g a lon g th e d o w n w in d n o rth ea st tra n sect from th e copper sm elter. B lack spots sh ow lo ca tio n ta k e n fo r th e stu d y on h ea v y m eta ls in soils and p la n ts of v a rio u s zones. O pen and n u m b ered spots in d ica te th e location of sam p lig of w h o le soil p ro files. T ra in g le sp ots sh o w lo ca tio n s of e x p erim en ta l
p lo ts
Chemical composition of soils was determ ined after a fusion w ith
Na2C 03 or after a digestion w ith a m ixture of acids (H2F2, H C IO4, HC1).
P lan t m aterial was decomposed w ith a m ixture of acids after an ignition in a m uffle a t 450°C.
Extractable heavy m etal concentrations were determ ined by agitating 10 g of air dried soil samples w ith 100 m l 0.1 N HC1 for 1 hr. W ater
soluble elements were m easured in the n atu ral soil solution obtained from the soil samples by centrifugation.
The concentrations of the elements were determ ined by the atomic absorption flam e spectrom etry. Content of S was determ ined by the X -ray fluorescence, content of N and P — by spectrophotom etry.
Mean relative recovery of the addition of known am ounts of the metals to samples produced results w ith following agreem ents (in per cen t): F e ± 9.27, M n±1.73, C u±4.21, C d ±3.10, Z n ±13.2, P b ±15.5.
All data for chemical composition are given in air dry w eight for soli samples and in oven dry (70°C) w eight for vegetation samples. Units used are : p p m = mg/kg for solid samples and p p m = jxg/1 for liquid samples.
R E SU L T S A N D D IS C U S S IO N
Soils surrounding the copper sm elter represent a great variety of pseudopodzols, brow nearths and blackearths derived from fluovioglacial or alluvial deposits. The predom inant kind of soils was silty light loam. The samples from the whole soil profiles were collected in 1974 and 1975 years. The reference samples for thic collection was soil located at the site 27 at 18 km distance. The surface soil samples were collected during 1975-1977 period. The samples from the V zone at 22-27 km distance were background for this collection (Fig. 1).
The distribution of heavy m etals in the soil profiles was typical for brown soils. There was an accum ulation of Cu, Pb and Cd at the upper
A horizon, while Mn and Fe were p a rtly concentrated at the lower (B)
horizon (Table 1).
The range of concentration of these elements a t the upper horizons was following (in ppm) : Cu 6-125, Pb 17-63, Cd 0.1-2, Zn 20-108, Mn 120-280, Ni 8-14. These concentrations correspond to data given by S z e r s z e ń et al. [13] for the time of beginning of the sm elter operation, b u t a higher values exceed the background established for th a t kind of soils [8].
Total sulfur content of soil reported by some other authors has not been changed during six years, of the sm elter operation and ranged from 50 to 680 ppm [5, 12]. However, there was observed a slight decrease of soil pH, especially at the nearest proxim ity to the sm elter.
It has been already w ell known th a t m etallic pollutants are likely to be accum ulated in the thin surface layer of soils. Observations of the contam inated soils indicated th a t this phenom ena is also due to a sim ultaneous emission of hydrocarbons increasing to a g reat extent the sorption of m etals [7, 9].
Topsoil samples (0-3 cm depth) were collected for each zones at the distances indicated on Fig. 1. Cu and Pb total concentration and 0.1 N
T a b l e 1 D ia t r i b u t i o n с Г heavy гаеt a l s w i t h i n th e s o i l p r o f i l e s sam pled
i n 1974 and 1975 y e a r я /ppm / L o c a l i t y , d i r e c t i o n and d i s t a n c e t'roni a m e lte r Km
Kind and type o f y o i l th o f •■jamplir.s era pi! in 1 '• .‘X I Cu ?b Cd Zn Mn Ni i n Fe % 1 :< .3 - & 5 6 7 В ...9 .. 10 11 ? S i l t y aar.d, 5-25 5 .5 125.0 4 2 .5 0 .2 5 35 290 8 0 .5 8 1.1 S orewn ty?;- 40-60 6 .5 6 .7 12 .5 0* 18 10 470 8 0 .5 6 о 0 1 с 6 .3 4 .8 8 .7 0 .1 3 10 92 9 0 .5 3 3 o i 'i t y aan d , 5-15 6.1 7 2 .5 3 1 .3 0 .2 5 20 2C0 6 0 .5 3 1 .5 В brown ty p e 30-40 5 .9 5 .5 1 1 .3 0 .1 3 15 360 4 0 .5 3 100-120 6 .;. 5 .0 8 .3 С.Об 5 93 6 0 .4 5 1.'0-140 6.1 9 .0 1 > 0 .0 6 20 103 8 0 .6 8 13 S i l t y 3ur.d, 5-15 6 .0 10 1 .0 4 6 . } 2 .0 21 119 - 0 .4 2 2 .6 £ b la c k v i r t h 25-05 4 .9 4 .5 1 0 .0 1 .0 9 101 - 0 .3 7 ty p e 70-80 4 .6 4 .5 1 1 .3 1 .0 9 115 - 0 .4 0 1A .J.iïty car.d, 5 - 15 6 .0 3 4 .0 2 2 .5 1 .0 29 315 - 0 .9 0 5 .2 b la c k e a r t h ■G-SO 6 .1 8 .0 1 3 .7 1 .0 15 185 - 0 .7 7 7C-S0 7 .4 5 .5 1 0 .0 1 .0 15 120 - 0 .6 0 12 S i l t y l i g h t 5-15 6 .8 2 8 .0 3 2 .5 2 .0 85 330 - 1 .3 9 1 1 .7 2 loam , .35-45 7 .5 1 3 .0 1 7 .5 0 .5 25 120 - 0 .6 3 brown type 6 0-00 7 .5 6 .0 1 5 .0 0 .5 25 130 - 0 .5 0 ■ Il G i l t y l i g h t 5-20 6 .1 1 4 .0 6 2 .5 1 .0 103 240 - 0 .7 3 ia .O л loam , 40-50 5 .9 1 0 .0 2 2 .5 1 .0 38 350 - 1.31 brown typo 70 6 .2 1 3 .0 2 5 .0 1 .0 65 260 - 2 .0 0 л S i l t y san d , 5-15 6 .4 2 9 .0 1 7 .5 1 .3 0 30 145 6 0 .6 3 1 . , g re y ty p e 30-40 4 .2 1 1 .0 13 .8 0 .6 0 45 325 14 1 .2 0 90-110 4 .9 1 0 .0 2 2 .5 0 .6 0 40 410 26 2 .2 3 130 5 .5 5 .0 1 1 .3 0 .1 3 25 130 12 1 .0 0 3 A l l u v i a l 5-15 4 .5 34 .0 3 2 .5 0 .1 0 45 500 14 1 .1 5 2 .5 NE l i g h t loam , 40-50 5 .2 10 .5 2 7 .5 0.C8 30 920 24 1.4 5
brown type GO-70 5 .6 1 8 .0 3 5 .0 0 .1 2 40 770 34 2 .7 5
90-100 6 .0 3 .0 2 3 .5 0 .1 8 10 57 6 0 .3 5 7 A l l u v i a l 5-15 6 .7 2 0 .0 3 1 .3 0 .1 7 50 660 12 2 .0 5 4 .3 ira l i g h t loam , 30-40 5 .6 1 5 .0 2 7 .5 0 .0 8 40 920 22 2 .8 5 brown ty p e 5 0-60 5 .4 18 .5 2 5 .0 0 .1 3 60 770 36 4 .0 0 8 0 -9 0 5 .8 1 0 .0 2 1 .5 0 .0 3 35 730 18 2 .5 0 120-130 5 .7 3 .0 1 7 .5 0 .0 3 10 45 4 0 .4 3 6 A l l u v i a l 5-15 7 .3 1 2 .5 j 3 1 .3 0 .2 5 40 380 8 0 .8 3 4 .8 NE l i g h t loam , 40-50 4 .9 5 .0 1 3 .8 0 .0 6 60 150 14 1.5 8 brown ty p e 6 0 -7 0 5 .4 4 .0 1 1 .8 о . о з 10 127 6 0 .8 5 9 0 -100 5 .6 3 .0 1 8 .8 0 .0 3 5 35 2 0 .3 0 5 S i l t y l i g h t 5 -20 5 .1 5 .5 4 1 .3 0 .2 5 20 120 8 0 .4 0 8 .0 NE loam , 6 0-70 5 .5 1 .0 1 6 .3 0 .0 6 10 35 6 0 .1 5 brown ty p e 120-130 6 .7 1 .0 1 2 .5 0 .0 6 5 30 2 0 .1 3
HCl soluble forms seem to be a function of the distance from the sm elter (Fig. 2 and in P a rt II Fig. 1). This is not the case however for other
Fig. 2. C o n cen tration s of Cu and Pb in so ils as a fu n c tio n of d o w n w in d d istan ce from th e copper sm elter a lon g th e n orth east tra n sect
1 — to ta l c o n te n t, 2 — 0.1 N HC1 so lu b le c o n te n t
heavy metals. A higher concentration of total Cu and Pb (830 and 325 ppm) in topsoil samples collected in 1976 as compared to the values obtained for 1975 and 1977 is reflected a higher emission from the sm elter and indicated also th a t process of additive accum ulation of m etallic pol lutants is not observed yet in these soils.
D istribution p atterns of Cu nad Pb in soils along the northeast transect of the prevalent wind direction show the typical function of the distance from the sm elter stacks (Fig. 2 and in P a rt II Fig. 1). The con centration of Cu in topsoils from the F irst Zone varied during three years of the experim ent from 440-825 ppm and exceed in average about 84 times the value for soils from the F ifth Zone (Fig. 1). The same figures for Pb are respectively : 90-388 ppm exceeding 10 times the background content. Sim ilar proportion in increasing Cu and Pb content
in soils around copper sm elters has been reported by other authors [2,
3, 11, 13].
A high m obility of heavy m etal pollutants is of a great environm ental corcern. Concentration of Cu in the n atu ra l solution of the contam inated soils is extrem ely high. An increase of Zn concentration in the soil solution was also noticed above its norm al range [9]. The relative solubility of heavy m etals in w ater phase was variable and depending much on a soil kind. Contam inated sandy soils released into the w ater phase 15-22% of total Zn, 5-10% of total Cd and 2-6% of total Cu, while this value for loamy soils were respectively, 0.3, 0.1 and 0.3 (Table 2).
The solubility of m etallic pollutants in the surface layer of soils was m uch smaller. The concentrations found in the n atu ral soil solution
of those samples correspond in average to 2.5% of total Cu, 1% of total
T a b l e 2 o o l u b i l i t y o f heavy m e ta ls in th e n a t u r a l a o i l s o l u t i o n and in th e w a te r e x t r a c t s / i n p e rc e n t o f t o t a l c o n t e n t / S o i l and l o c a l i t y W aterphase Cu Pb Cd Zn : l i l t y 3 a n d MS 1.7 0 .1 10 1‘> P-K pH 5.2 WE 3 .0 0 .6 7 4 J i l t y sand N3 6 .3 0 .4 5 22 P-2 pH 4 .5 WE 10.0 0 .7 5 10 L ig h t loam NS 0 .3 0 .0 2 0 .1 0 .3 P-8 pH 5 .8 WE 6 .3 1 .4 0 .5 1.5 NS - n a t u r a l a o i l s o l u t i o n WE - w a te r e x t r a c t s P r e p a r a tio n o f w a te r p h a se s i s d e s c r i p t e d in o th e r p u b l i c a t i o n [ j j
Contamination of soils by Cu and Pb was adversely correlated w ith the distance from the stacks w ithin 14 km downwind the northeast transect. The contam inated soils show the highest contents of m etals in very th in top layer. Copper and lead accum ulated in topsoils were easily soluble, w hat was p artly affected by a high soil acidity due to a heavy sulfur fallout.
A high content of Cu and Pb and increased level of Cd and Zn in topsoils of the close proxim ity to the copper sm elter have a serious im pact on chemical balance of environm ents.
The authors appreciate very m uch the partial support of this study by the USDA under the PL-480 Program.
Advices and rem arks of Dr. A. W. Taylor are gratefully acknowled ged. Thanks are also extended to Ing. M. W ierzbicki and the staff of the Environmental Protection Division of the Copper Sm elter for their
kind cooperation.
R EFEREN CES
[1] B e c k m a n L .: R ön n sk är sm elter — o c cu p ia tio n a l and en v iro n em n ta l e ffe c ts in and around a p o llu tin g in d u stry in N orth ern S w ed en . A m b io 7, 1979, 226-231.
[2] C r e c e l i u s E. A., J o h n s o n C. J., H o f e r G. C. : C ontam ination of soils n ea r a copper sm elter by arsen ic, a n tim o n y and lead. W ater, A ir, S o il P oll. 3, 1974, 337-342.
[3] C z u l d z i j a n H. : In d u stria l co n ta m in a tio n b y copper in Z la tiszk a K o tlo - w in a (G old V a ley ) (in B u lgarian ). P o czw o w . A groch im . 6, 1976, 41-52. [4] D u d a S. : S om e a sp ects o f in d u stria l im p act on fo r e st in L eg n ica — G łogów
C opper B e lt (in P o lish ). S y lw a n 10, 1977, 39-45.
[5] G a j e w s k i K. , G r e i n e r t H. , L e n a r t o w s k i M. : E ffects of atm osp h eric p o llu tio n b y h e a v y m e ta ls and su lfu r on so ils and p la n ts in a v ic in ity of a copper sm elter (in P olish ). Proc. C onf. E ffe c ts of T race E lem en t P o ll, on A gric. E nvir. Q u ality, IU N G , P u ła w y , 1, 1978, 163-170.
[6] J a s i ń s k i A. : F orm ation of ore m in erals of copper deposit in the P resu - d etia n M onocline (in P olish ). A rch. M in. 35, 1979, 29-40.
[7] K a b a t a - P e n d i a s A. : T he im p act of copper m in in g and in d u stria l a c iv ity of L o w er S ile sia on th e ch em ica l co m p o sitio n of p lan ts. IU N G , P u ła w y , 1978, pp. 172.
{8] K a b a t a - P e n d i a s A. : H eavy m etal concentrations in arable soils of P olan d (in P olish ). Pam . puł. 74, 1981, 101-111.
[9] K a b a t a - P e n d i a s A. , G o n d e k В. : B io a v a ila b ility of h ea v y m eta ls in th e v ic in ity of a copper sm elter. T race Sub st. E nvir. H ea lth 12, 1978, 523-531. [10] K o w a l k o w s k i A. : F o rest in th e in d u stria l areas (in P olish ). S y lw a n 10,
1977, 59-66.
[11] P a c y n a J., Z w o ź d z i a k J., Z w o ź d z i a k A. : In flu en ce of a ir-b o rn e p o llu ta n ts on h e a v y m eta l c o n ta m in a tio n of w a ters, so ils and p la n ts in th e C opper B e lt A rea (in P o lish ). Proc. C onf. E ffe c ts of T race E lem en t P oll, on A gric. E nvir. Q u ality, IU N G P u ła w y , 1 , 1980, 129-138.
[12] R o s z y k E., R o s z y k S. : In flu e n c e o f th e copper m eta llu rg y on som e p rop erties of so ils and ch em ica l com p osition of crops (in P olish ). Rocz. G lebozn. 27, 1976, 4, 57-68.
[13] S z e r s z e ń L., L a s k o w s k i S., R o s z y k E. : D y n a m ics of Cu, P b and Zn in so ils of th e b u ffer zone o f a copper sm elter (in P olish ). P roc. C onf. E ffects of T race E lem en t P oll, on A gric. E n vir. Q u ality, IU N G P u ła w y , 1, 1978, 53-60.
A. K A B A T A -PE N D IA S, E. BOLIBRZUCH, P . TARŁOW SKI
O D D ZIA Ł Y W A N IE H U T Y M IEDZI N A PRZY R O D N IC ZE W A R U N K I R O LNICTW A
CZĘŚĆ I. ZA N IEC ZY SZC ZEN IE G LE B In sty tu t U p raw y, N a w o żen ia i G leb o zn a w stw a
w P u ła w a ch S t r e s z c z e n i e
L ok a liza cja p rzem y słu h u tn iczeg o w rejon ach ro ln iczy ch stw arza za grożen ie dla ró w n o w a g i ch em iczn ej ła ń cu ch a pokarm ow ego. B ad an ia p o d ejm o w a n e w tak ich o k ręgach m ają na celu o k reślen ie k ieru n k ó w zm ian zach od zących w środ ow isk u p rzyrod n iczym pod w p ły w e m e m isji h u tn iczy ch oraz u sta le n ie p o d sta w do w y z n a czen ia zasięgu stref ochrony san itarn ej w o k ó ł za k ła d ó w p rzem y sło w y ch .
B a d an ia zm ian sk ład u ch em iczn eg o g leb i ro ślin w rejo n ie ob jętym w p ły w e m em isji H u ty M ied zi G łogów b y ły p row ad zon e w la ta ch 1974-1978. A n a lizo w a n o skład ch em iczn y , a przed e w sz y stk im zaw artość Cu, P b, Zn i Cd w ca ły ch p ro
fila c h g leb o w y ch oraz w p o w ierzch n io w y ch p oziom ach gleb. B ad an ia sk on cen tro w a n o w w y zn a czo n ej str e fie d om in u ją cy ch w ia tr ó w (NS) o zasięgu do 27 km od źródła em isji.
Z m iany w za w a rto ści m eta li cięż k ich w g leb a ch w sk a zu ją , że Cu i P b są g łó w n y m i m e ta la m i zan iecz y szcza ją cy m i, Cd i Zn (także siark a e m ito w a n a w d u ży ch ilościach) p od legają zn aczn ie słab szej a k u m u la cji w gleb ach . N a jw ięk sze stężen ia Cu i Pb w y stę p u ją w p ły tk im poziom ie p o w ierzch n io w y m (0-3 cm) o sią gając k olejn o w a rto ści 830 i 325 ppm . N a procesy siln ej a k u m u la cji ty ch m eta li w p ły w a w d u żym stop n iu jed n oczesn a im isja su b sta n cji b itu m iczn y ch w y s tę p u ją cy ch w p y ła ch h u tn iczych . R ozp u szczaln ość w fa zie w od n ej Cu i P b sk o n cen tro w a n y ch w p o w ierzch n io w y ch p oziom ach gleb jest duża i dlatego są one ła tw o p ob ieran e przez roślin y.
W zw ią zk u ze zn aczn ym zan iecz y szczen iem m eta la m i cięż k im i (głów n ie Cu i Pb) g leb w bezp ośred n im są sied ztw ie h u ty m ied zi k on ieczn e jest w y zn a czen ie k ieru n k u ich racjon aln ego zagosp od arow an ia.
P ro f. d r A lin a K a b a t a - P e n d i a s
I n s t y t u t U p r a w y , N a w o ż e n i a i G l e b o z n a w s t w a w P u ła w a c h
