Canadian Minzralogist Vol. 14, pp.47-57 (1976)

ECOLOGIGALCONSEOUENCE OF ACIDIG AND HEAW-METAL DISCHARGESFROM THE SUDBURVSMELTERS

L. M. WHITBY, P. M. STOKES, T. C. HUTCHINSON eNo G. MYSLIK Institute for Environmental Studies and. Department of Botany, University of Toronto, Toron:to, Ontarto.

ABSTRACT trds vastes r6gions forestibres, par facidification du sol et les 6rosions terrestres majeures subs6quetrtes. Studies have been made of the effects on temes- De plus, les m6taux lourds fondus se sont accumu- trial and aquatic ecosysiemg of heavy-oetal emis- l6s jusqu'i de trds fortes concentrations sur une sions, sulfur dioxide, and acidic rain-induced grando 6tendue, et surtout dans les sols superficiels. problems, caused by smelting activities in the Sud- Ces niveaux 6taient toxiques, meme en fabsence de bury region. The effects have been profound. Phyto- dioxyde sulfurique, i une grande vari6t6 d'espdces plankton populations have been reduced from 2,000 solutions i 'negligible' 6tudi6es dans des extraits ou dans des cells,/ml to in many of the lakes close m6tal unique. 13s am6liorations du sol avec la to the Coniston smelter, alrd around both Falcon- chaux ont eu des effets dramatiques sur 1a crois- bridge and Copper Cliff. Levels of nickel (up to sance et la survie des plantes. La proportion de m6' 6.5 ppm) and colper (up to 0.2 ppm) occur in these tal s'est trouv6e r6duite, par la meme occasion, i lakes, and these, combinetl with increased acidity, comparer i etle des sols notr-amaiores. are major obstacles to survival of primary produc- Cfraduit Par le journal) ers. The whole food chain has suffered parallel and often even greater extinctions in these lakes and especially in those to the northwest. INmooucrroN For terrestrial systems, emissions of sulfur diox- ide have directly damaged very extensive areas of Aquatic and terestrial studies of possible forest, witl soil acidificatiron and subsequent major heary-metal effects were commenced around soil erosion. In addition to this, the smelted heavy Sudbury in 1968 to determine whether parti- metals have accumulated to very high concentra- culate emissions had caused changes in the tion$ over a wide area, especially in zurface soils. physical properties of the aquatic These levels were, even in the absence of sulfur chemical and and to dioxide, toxic to a wide range of species tested in and terrestrial ecosystems in the region, oxtracts or in single-metal solutions. Lime amend- determine possible long-term consequencesof ments to soil had dramatic effects on grofih and such emissions compared with sulfur dioxide. survival of plants. Metal uptake was found to be The very high accumulation of Ni and Cu correspondingly reduced compared with uptake on especially in soils and theil patterns of distribu- unamended so,ils. tion relative to soil depth and distance from the smelter have already been reported (e.g. & Rfsur,4€ Costescu & Hutchinsot 1972; Hutchinson Whitby 1,974;Whitby & Hutchinsot 1974). T\e Des 6tudes ont 6t6 effectu6es sur les effets des toxicity of soils over an area of many square €missions de m6tal lourd, de dioryde sulfurique et miles has been emphasized and the long-term problbmes des d'acides provoqu6s par la pluie et problems described. Studies have focused on caus6s par des activit6s de fusion dans la r6gion de the Coniston smelter, which was Sudbury, sur 6cosystBmes transects from des terrestres et aquati- previously continu- ques. ks etfets ont 6t6 importants. Les populations closed in 1972 but had run de phytoplancton ont 6t6 r6duite.s de 2,000 cellules/ ously since 1913. ml i des proportions n6gligeables dans plusieurs The water bodies in the Sudbury area are lacs pGs de la fonderie Coniston, et autour de Fal- mainly small Shield lakes and mine streams. conbridge et de Copper Cliff. Des niveaux de nickel In their natural state tlese lakes are typically (usqu'ir 6.5 ppm) et de cuiwe (jusqu'i 0.2 ppm) oligotrophic, soft-water, shallow and generally apparaissent dans ces lacs et ceux-ci combin6s avec with a low conductivrly, a low organic content uno acidit6 accrue, sont des obstacl.es majeurs i and with a poor buffering oapacity. The altera' la survie des producteurs premiers. Toute la chalne tion in the chemical status of the lakes close to do nourriture a connu des extinctions parallbles et smelting astivities m6me souvent plus grandes dans ces lacs et parti- Sudbury due to mining and culidrement dans ceux du nord-ouest. can be estimatedby selectinga range of lakes at Quant aux systdmes terrestres, les 6missions de different distances from a point source such as dioxyde sulfurique ont endommag6 directement de a single smelter and determining correlations 47 48 THE CANADIAN MINERALOGIST

between distance and chemical parameters. were collected in June L969 and 1970 at sites Similarly, the biological changes *^nicl might at least 100 m from ro-adways.A1l sites were be occurring can be deter,minedbv field studies on hill tops, where the plumes from smelter (e.g. primary productivity, standing crop, algal stacks impinge most often. cell numberso species diversity) and by labora- In 1,969, natarul vegetation was collected tory bioassay of lake waters with standard test twice (June and August), at nine of the sites. organisms. In many instances,a speciespresent at one site Such data have been acquired over the past was absent at several others, especially at sites six years. The lakes selected range from 1.6 close to the smelter where plant cover and km to 12.0 km from the Coniston smelter. speciescomposition were poor.

MarsRrAr,s AND METHoDs Analytical methods Methods for the analysis and determination Choice of tenestrial sampling areas of pH, conductivity, loss on ignition, total The Coniston smelter was selected as the heavy-metalconcentrations, water-soluble metals, focus for the terrestrial studies (Fig. 1). Conis- water-soluble sulfate etc. have been described ton is off the main ore bodies, and away from previously (Hutchinson & Costescu L972; Hut- dykes; no tailings are nearby, and only a small chinson & Whitby 7974, 1.975;Whltby 1974). area around it is covered by slag heaps. Samples of natural vegetation were washed Sites were chosen at distances from 0.g to to remove all surface contamination, rinsed in 50 km from the Coniston smelter. selected to 5 changesof deionized water, then dried for 48 traverse Dreisinger's 1970 isopleths @reisinger hours at 6O"C. O.2g plant material was predi- 1970). Soil samples from lOcmdepth profiles gested for 16 hours in 3 ml concentrated nitric-

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/ / I L--j---J--J-1-J milss L==+_=J km

Ftc.- l.-Sketch map of the Sudbury region, with sites marked for soil and vegetation samples and lakes in which.bioassays were carried out. The lines marked 20, l0 anC 5 join points indicating number of damaging fumigations noted in l97l (after Dreisinger 1970). ECOLOGICAL CONSEQUENCES OF DISCIIARGES FROM SUDBURY SMELTERS 49 perchloric acid (ratio 1:1), then heated to 75"C germinated before planting. After 28 days, the in a sandbath for 5 hours. Each sample was plants were harvested and treated in a similar diluted to 10 rnl with deionized water without manner to the field-experiment plants. filtering. Rainfall-dustfall samples were collected Aquatic studies throughout the sampling region during 1970 Most of the methods used in the algal bio- and l97I (Ilutchinson & Whitby 1975). assays of lake waters from the Sudbury region All samples were analyzed for Ni, Cu, Co, have been described in detail (Ilutchinson & N, Zt, Mn, and Fe by atomic-absorption spec- Stokes 1975). I-ake waters were collected from trophotometry. a ftmgo of water bodies arranged along a tran- sect south of the Coniston smelter (Fig. 1). Algal growth Bioassayslor seeding using root counts were expressedas cells per ml of original elongation as nt index lake-water sample. Algal cells were preserved The radicle elongation of germinated seedlings in the field using Lugol's iodine. was used as a method for assayingthe toxicity Water for laboratory bioassays was filtered of Sudbury soils, with root growth acting as an immediately after collection, to remove major index of soil response. A soil-water extract was debris. Four laboratory test organisms were obtained from each of the sites at three depths, used for the study of the potential ability of by shaking 33.3 g soil in 10O ml deionized wa- lake waters to support algal growth. The effect ter for 4 hours. of pH adustment and addition of nutrients on A series of bioassays was also performed to these lake-water sampleswas also tested by in- determine the effects of single-metal salts in creasing the pH of the acidic lake waters to nutrient solution (Whitby & Hutchinson 1974; 6.8 and by addition of a one-tenth strength so' whitby 1974). lution of Bolds Basal Medium (BBM), an in- organic algal nutrient solution. Field and greenhouse experiments Chemical methods were standard atomic- Field experiments were conducted during the absorption spectrophotometry for heavy metals summers of. 1,969-L971.Experiments were con- and a modified barium-chloride turbimetric ducted at nine sites - L.5, 1.7, I.9, 3.8, 7.4, method for sulfate. 1A.4,13.5, 19.3 and 49.8 km from the Coniston smelter. Four lm-square plots were set out at Rnsurts each site. One plot was left untreated, one plot fertilized with 100 g So-Green 7-7-7 ferllJtzer, Terrestrial studies one plpt was limed to pH 7, and the fourth The physical and chemical properties of the plot both limed to pH 7 and fertilized with 1O0g soils have been extensively reported (Ilutchin- So-Green 7-7-7 fertrlizer. son & Costescu 1972; Htttchinson & Whitby Seeds of a variety of naturally-occurring and 1974, 1975) and therefore are briefly sum- horticultural species were planted in the plots marized. in June and harvested after 75 days. All plants The pH of the soils is naturally acidic, rang- were carefully removed from the soil to pre- ing from 3.8 to 4.8 in areas unaffected by serve root systems.The plants were washed to smelting operations. The lowest pH values oc- remove soil particles, rinsed five times in de- curred in surface soils close to the smelter. ionized water and dried at 60"C for 48 hours. Surface pH values were below 3.0 to a distance Dry weights for each plant were obtained after of.7.4 ki from the smelter.pH values increased the roots were removed, since complete root through the soil profile. systemscould not be preserved.The plants were The conductivity values were high in soils digested and analyzed for heavy-metal contents close to the smelter (552 pmhos at 1'6 km) and as described previously. decreased to normal levels as distance from Tests were run on soils collected from the Coniston increased(58 g.mhos at 49.8 km). The field under controlled greenhouse conditions highest conductivity was in the surface soils and during 1969-7I. The soil samples from each decreased through the soil profile. site were divided into 1 kg sections- one was Concentrations of Cu and Ni, the major left untreated, a second was treated with 14 g metals smelted in the region, were also highest So-Green 7-7-7 f.ertiluer. a third limed to pH 7, in surface soils closest to the smelter. Ni and a fourth limed to pH 7 and fertilized with showed the highest concentrations, e.g. 5104 14 g So-Green 7-7-7 fertilizer. The soil from ppm at 1.1 km, 282 PPm at lO.4 km and 35 each treatment was then placed in 20 X 7.5cm ppm at 49.8 km. Both Ni and Cu occurred at plastic pots. Four test species were used and concentrations greater than 1,000 ppm in all 50 THE cANADIAN MINERALOGIST

soils within 7.4 km of tle Coniston smelter. The Mn in Vaccinium angustifolium and Acer ru- patterns for the other elementssmelted at Conis- bram are given in Table I. In all speciestested, ton, such as Co, Fe and Ag were similar, with Ni, Cu, Co, and Fe were elevated in foliage the highest concentrations close to the smelter, collected close to the smelter. pot gaamFle, and a decreasing concentration $/ith increasing Vaccinium angustilolium contained 92 ppm Ni, distance from the smelter. Metals not smelted 75 ppm Cu, 10 ppm Co, and 618 ppm Fe at at Coniston showed no patterns related to dis- 1.6 km which decreasedto 14 ppm Ni, 14 ppm tance from the smelter or depth in the soil pro- Cu, 5 ppm Co and 88 ppm Fe at 49.8 km. Al, file. which was not smelted at Coniston. rtras also Two species, the blueberry, Vaccinium an- elevated in vegetation growing close to the gustifolium and the red maple, Acer rubrum, smelter and decreasedrsith increasing distance. were collected at eight sites. Four species \rere Foliage of V. angustifolium contained 100 ppm collected in at least six sites _- trembling aspen N at 1.6 km and 35 ppm at 49.8 km. Populus tremuloides, sweet fern Comptonia pe- There was no consistent pattern of metal regrina, paper birch Betula papyrifera" and wavy elevation in foliage when samples collected in hair grass Deschampsia flexuosa. August were compared with tlose from June. Concentrations of Ni, Cu, Co, Al, Fe, and For elamFle, Vaccinium angustifoliunx had higher concentrations of Ni in August than rn June, whereas Acer rubrurn had higher con- TABLEI. I.IETALCONTENT IN FOLIAOEOF NATUMLLY-OCCURRINGPLAI,IT centrations of Ni in June than SPECIESALONG A TRANSECTFROM THE COI{ISION sI'IELTER. in Auzust.

Distance l{eanppn of trc homgenizedsamples Soil-water extracts Species ( kn) Nt cu Al te lln co The water-soluble concentrations of heavy v@cinl@ t.6 92 75 100 618 223 metals from three soil depths a14wt1:f,oLi.w 2.1 55 30 60 383 455 at different dis- (LotrSweet 7.4 45 35 240 245 133 tances from Coniston and soil pH values are Blueberry) 13.5 37 22 120 223 lt20 to ? 36 19 70 |35 1260 given in Table 2. For all soils, except that ob- 28.9 '1416 l9 t00 123 ll30 tained from 49.8 km 49.8 14 35 88 465 from the smelternthe pH w.as lowest at the zurface and increased with Acet tubw 1.6 98 37 125 698 197 n (Red ltaple) 2.1 88 26 depth through the profile. 170 455 ',t80135 soil In addition, pH 7,4 4s 3l t 25 173 I increased 33 20 20 170 690 with distance from the smelter. lo 1 57 28 80 208 220 In the water extracts, Ni concentrations were ,ao 14 16 22 275 t055 generally higher than Al and Cu. The highest sampleswere collected ln,June 1969. metal concenftations again occurred in tle sur- face soils and decreased through the profile. TABLE2. COI{CENIMTIONS,IN SUDBURYSOILS, OF HEAVYMETALS Also, the highest concentrations generally oc- EXTRACTEDBY DISTILTED!.IATER curred closestto the smelter. Beyond a distance Distance Deoth of 13.5 km, the concentrations of most of niles km (cin) pH -rf__l!!!#l4l{+#!+P1!t+ the metals were below the limits of detection of 0.5 0.8 0 3.08 381.0 126.0 13.8 t5t.8 2.9 the technique and were recorded as nonde, 3.36 42.8 22.8 0.6 20.7 0,2 tectable. t0 4.48 31.8 18.3 nd 17.4 0.1 0.95 1.5 0 3.40 321.9 178.5 10.2 231.3 2.1 It must be emphasized that all metal con- 5 3.59 168.0 59.7 4.5 155.4 1.6 centrations recorded l0 3.69 57.6 29.7 1.2 69.0 0.4 were for water extracts 1.9 0 3.25 426.0 | 78.5 and are therefore probably an underestimateof q 13.2 296.7 4.1 3.48 108.9 ,o7 3.0 a! 1 t n the concentrations plants 10 3.86 50.I 18.0 actually available to 0.6 4r.4 0.2 for growth. 3.8 0 3.59 43.2 0.6 31.2 0.6 5 3.57 36.9 19.2 0.3 3t.2 0.5 l0 3.67 4l.l 21.6 0.3 31.2 0.5 Root elongation bioassays 4.6 7.4 0 3.41 't2.625.t3 9.0 nd 19.5 0.3 3.54 4.5 nd 19.5 0.2 A soil-water extract of 1:3 t0 3.65 6.3 2.4 no was used for bio- 13.2 0.2 assays. germinated 10.4 0 3.86 19.5 0.9 no 45.9 1.2 When seeds were in these 5 4. n 3.9 nd no i6.5 0.1 extracls, at all sites closer than 3.8 km from t0 4.22 3.6 nd nd 16.5 0.1 the smelter there was almost complete inhibition 4.4 t3.5 0 3.93 3.0 0.6 no 6.6 nd 4.32 nd nq no nd nd of radicle elongation. At distances greater than l0 4.69 nd nq nd nd nd 3.8 km, the relative inhibition of root elongation l?.0 19.3 0 4.Jv nd nd nd nd nd 5 4.46 nd nd nd nd nd as compared with controls, related to distance 10 4.70 nd nd no nd nd from the smelter. In addition, the surface soiis 3l.0 49.8 0 4.79 0.3 no nd 1.5 nd 5 4.69 nd nd nd i.5 nd were generally most toxic, except at distances t0 4.44 nd nd nd 1.5 nd greater than 13.5 km. nd = belor]lnits of detectionby thls technlque. Investigations using single-salt metal solu- ECOLOGICAI. CONSEQUENCES OF DISCHARGES FROM SUDBURY SMELTERS 51 tions of Cu, Ni, Co or Al confirmed that the TABLE3. NUMBEROF SURVIVOR5AND IIEAN I,IEI6HT (M9) OF THEABOVE. concentrations of these metals in the soil-water GROUNDPOR1I0NS 0F ragopgw aaggtttqtw (BUCKI',IHEAT)GRol',{N IN THE extracts were inhibitory to root elongation FIELDDURING I970.

(Whitby & Hutchinson t974; Whitby 1974). Site m None Fertillzqr' Lire Lime & Although we attempted to establish vegeta- Fertil i zer tion on the Coniston soils in the field for three successiveyears (1969-71), only the results for f survl vors 8 l0 ..; 1B8 443 l97O are reported. Seedlingsof several species, rean weight (ng) 149 such as sugar maple Acer saccharum and red 1.7 f survivors rean treight (mg) 74 I 78 442 maple Acer rubrum, did not emerge at any site 7.4 # survivors ; 48 27 l0 although the seeds were pre-treated and found meanweight (ng) l3 92 r55 3r0 '10.4 to germinate well in the laboratory. Most seed- # survivoE I l8 30 25 lings which grew, especially those close to the man weight (ng) 21 174 227 257 smelten, showed marked sulfur-dioxide damage 10 1 # sufvlvors 3 2 3l meanweight (mg) 33 B5 343 273 symptoms. 'i 49.8 # survivors 3 I --- Germination at the field sites was very poor. '134 (mg) The number of survivors and the mean weight man weight 2l 27 (above ground growth) of seedlings of buck- At 1.9,3.8 and 13.5 km,no seedlingsemerged. *o"ig. wheat Fagopyrunx sagittatum are given in Ta- f ot seeds50 per treatrent. ble 3. The metal concentrationsin the roots and leaves of F. sagittatum grown in the field ex- SH00TIIEIGHT 0F Rqhow eaf,tu@ 6R0l'lNUNDER GREEN- periments given in Figure 2. TABLE4. MEAN are HOU5ECONDIIIOI1S ON THE SOITSCOLLECTED AT VARIOUSDISTAI1CES FROM Fertilizer additions increased the above- THECOIIISTON SMELTER.T ground biomass over that obtained with no Distance treatment. This increasedbiomass became more (km) Fertllizer Line Llre & significant as distance from the smelter in- (mg./seedling) Fertllizer creased. increased when Growth dramatically 7.4 5.6i1.8 4,6:1.8 41.7!27.0 23.0114.0 'I lime was added (with or without fertilizer), For 10.4 6.5:4.4 43.0135.9 60.811i .8 123. 1 138.6 example, at 7.4 km F. sagittatum grown in un- 15.7:5,8 78.5155.8 42.8!13.2 87.0r?5.9 amended soil had a mean weight of 13 mg, in 19.3 8.71l.t 7.813.3 59.5115.3 121.0146.3 fertilizer-treated soil 92 mg, in lime-treated soil 49.8 67.8!17.9 76.4139.3 101.8128.1 62.9!34,3 155 mg and in fertilizer and limed soils 310 Eachwelght is the rean of l0 seedlings that survlved the one-- mnth growlngperiod. SeedlJngsgrcm on solls-collectedwlthin mg. Thus, raising the soil pH to 7.0 very mar- 7.4 kmof Conistondid not survJvethe one-rcnthgrcB1ng perrod. kedly increased plant growth. Plants that sur- vived in untreated or fertilizer-only additions failed to produce flowers. Plants grown in lime soils, ppm Ni and 209 or lime and fertilizer produced flowers and in fertilizer-treated 213 ppm gtown sofu, and 88 abundant fruits. Cu when in $ned ppm Ni and 158 ppm Cu when grown in limed After the plants divided into harvest, were and fertilized soils" roots, stems, leayes, flowers seeds, for and Metal concentration in the plants decreased metal most the highest analysis. In instances, with increasing distance from the Coniston of metals found in the concentrations were smelter. For example, Fagopyrum sagittatum roots. levels were found in the stems, The lowest roots in limed and fertilized soils at 19.3 kd followed by flowers seeds. Leaves gave and contained 226 ppm Ni and 27I ppm Cu, com- higher stems. For metal concentrations than did pared with 335 ppm Ni and 478 ppm Cu in Fagopyrum grown in example, sagittaturn fer- limed and fertilized soils from 1.5 km. tilized soils 1.6 km from Coniston, contained at Species differed in the quantities of metals 594 ppm Ni 9O9 ppm Cu in the roots, but and they accumulated ,(Whitby 1974). The cerealso only ppm ppm shoots 299 Ni and 175 Cu in the oats and barley, and the grass Deschampsia (Fie. 2). flexuosa contained higher concentrations than The highest metal uptale occurred on un- did other species such as buckwheat and fack amended soils and those treated only with fertil- pine. izer. The application of lime decreasedthe con- centration of metals found in the leaves and roots. For example, at 7.4 km, the roots o[ Gre4nhouseexperiments Fagopyrum sagittatum contained 882 ppm Ni Dry weights for Raphanus sativus grown un- and 1098 ppm Cu when grown in unamended der greenhouse conditions on treated and un- soils, 292 ppm Ni and 183 ppm Cu when grown treated soils are given in Table 4. Seedlings 52 THE CANADIAN MINERALOGIST grown oo soils collected within 7.4 km of the weight of Raphanus sativus was 15.7 mg in un- smelter died within the 28day period. amended soils, 78.5 mg in fertilized soil, 42.8 On the soil collected at 7.4 km ftom Coniston mg in limed soil and 87.0 in limed and f.efiiJizrd, all species survived, but growth was extremely soil. poor on the unamended soil. Fertilizer treat- The concentations of Ni, Cq Fe, and Mn ments alone did not insrease growth. plants in roots and shoots from greenhouse experimmts grew best on the limed soils. Lime plus fertiliz- are given fot Raphanus salivus in Table 5. er treatments increased plant growth compared Plants grown in unamended soils contained with controls (Iable 4). Similarly on soil col- the highest concentration of metals. These con- lected from 10.4 km and beyond, the growth centrations were lower in fertilizer applications. was poorest in unamended soils. With the excep- Concentrations were lowest in the lime plus tion of the 19.3 km site, however, there was a fertilizer treatment. marked reElonse to fertilizer. Indeed, in some Metal concentrations were higher in the roots cases, the reqponse was as high or higher than than in the shoots for Ni, Cu, and Fe. Mn dis- that to lime. For examplg at 13.5 km the mean tributions between shoot and root did not follow

UNAMENDED +FERTTLIZERZ | +LtM€ LIITIE + FERT.

30 4001o |(m FROttt coNtsToN ECOLOGICAL CONSEQUENCBS OF DISCIIARGES FROM SUDBURY SMELTERS 53 this pattern. The highest Mn concentrations green algae, whereas diatoms were present as were often found in the shoots rather than in dominants in DiU, and also present in Richard. the roots. Mn in the seedlings also increased Blue-green algae and Chrysophyceae\rere pre- with distance from the smelter. sent in Daisy Lake. This increase in diversity and apparent sensitivity of certain groups is pa- Aquaic studies ralleled in the higher plants at terrestrial sites The location of the test lakes are shown in along transects from the Sudbury smelters. Figure 1. The standing crop of phytoplankton Fish populations are now absent from Alice in the lakes was measured in 1969 and 1970 and Baby Lakes and invertebrates very rare. and data for five of the lakes are given in Elevated Cu and,/or Ni levels occur in Alice, Table 6. Lakes close to the smelter had marked- Baby and Daisy Lakes. Algal bioassaysof some ly'reduced algal populations, with only a very lake waters (Fig. 3) are shown for the unicel- few individual cells. A count of the order of lular gteen alga Chlamydomonas eugaftTetos, 2,@0 cells per ml is considered normal for both for unaltered lake waters and for additions the oligotrophic Shield lakes. Dill Lake (11.6 of nutrients (BBM) or pH adjustrnent to 6.8. km from the smelter) alone had such values. Long Lake had low Ni and Cu, whereasKelley Species diversity (not shown in Table 6) in- showed good growth despite elevated Ni and creased with distance from the smelter, i.e. 3 Cu levels. Boucher and Norway lakes are also speciesin Baby Lake and more than 50 species high in Ni and Cu. They are located near Fal- in Dill Lake. The Baby Lake species were conbridge (Fig. 1), whereas Lady Macdonald metal-tolerant (Stokes et aI. 1973). The algal Lake is approximately 1 km west of Copper groups in the polluted lakes were unicellular Cliff. Long L,ake, the furthest of those shown

+ FERTILIZER LIM€ + FERT.

- - - toott -shoofr R fl fl Ir f\

q gl rl ;l .t ;r ir I I I I t T

ro20to400 fo?o3()400 10 20 5() 40 fo 20 30 4() xm FROr CON|STO|I Fro. 2. Metal concentrations in leaves and roots of Fagopyrum sagittatam (buckwheat), grown in field experiments, 1970: (a) Fe and Mn; (b) Ni and Cu. 54 THE CANADIAN MINERALOGIST

TASLE5. CoI{CENIRATIoNS0F !'IETALS tN R@t@w @rrru GROHNtN in Figure 2, is approximately GREENHoUSE,0N SoILS CoLLECTED Iit C0NISTONAREA. 15 km SSW of Co- niston and 7 km SW of Copper Cliff. Dlstance Treat- Plant ill Cu Fe liln frcn Conlston mnt Part The stippled histograms for unamended wa- smlter ters clearly indicate the deleterious nature of 7.4 kn N Shoot 433 305 347 81 the lake waters to algal growth. Lakes such as Root I,150 926 4,920 76 Norway, Boucher, Alice, Baby and Lady M,ac- F Shoot 94 74 2U 43 Root 669 5t3 3,790 39 donald are quite toxic to this organism. Growth L Shoot 51 25 226 26 in Long Lake was tle best in unamended wa- Root 534 406 |,472 32 ters. The acidic nature of lakes such as Baby L&F Shoot l0l 49 102 37 Root 300 420 1,800 20 and Lady Macdonald (pH 3.7) was probably a 14.3 kn N contributory factor in this poor response. The Shoot 220 24 'I1,296 164 Root 429 136 ,857 29 adjustment of all pH's to 6.8 the .F and addition Shoot 288 ]43 39 of (added Root 206 126 853 52 nutrients since this may be a limiting L Shoot 16 12 il5 38 factor in oligotrophic and/or acidic Lakes) R@t 192 153 552 34 evoked marked re$ponses in some instances. L&F Shoot 76 183 22 Root 83 97 ],187 47 Norway Lake became a better medi lm for al- gal growth and large 49.8 km N Shoot 144 84 358 responses occurred in R0ot 67 46 700 947 Kelley, Ramsey and Long Lake flasks. How- F Shoot 43 ever, the inhibitory factor(s) in Alice, Rooi 20 32 574 495 Baby and Shoot at Lady Macdonald Lakes were hardly touched by 58 ',Is',r50 Root 20 60 883 these adjustments. L&F Shoot '163100 26 2,005 283 Root 138 2,875 213 Sulfate levels declined with distance with ex- cessivelevels in those lakes close to the stacks Ir9a!ren!-- N. no mndEnt, F = fertlllzer added,L llre added, (Iable 7). Bioassays on single-salt solutions of L & F. llm plus " fertiliser. sulfate (up to 250 ppm), of Ni (up ro 1.5 ppm), and of Cu (to 1.0 ppm) indicated a non-toxic effect of sulfate even at very high levels, a IABLE6. PHYTOPLANKTONSTANDING IN SOMESUDBURY TAKES high toxicify of Cu even at O.l-0.2 ppm, (CELLSpER and nl) lesser toxicity of N| with death of cells at 0.5- Lake Distancefrom Date 1.O ppm (Stokes & Hutchinson 1975). Conistonsmelter JUty Aus-Cy July km 1969 | 970 The very high Ni levels of Alice I-ake (6.4 ppm) and Cu levels in Baby Lake support the A1ice 2.0 negligible contention that metals were the main source of Baby 2.4 negllgible 'll toxicity to algae. Lady Macdonald was found Daisy 4.0 I95 t9l 523 I44 to have 1.5 ppm Cu and up to 7.0 ppm Ni Rlchard 6.4 I 040 1496 427 l3ll 740 in '| 1971. Dil1 ll.6 2121 504 1503 3288 I I 54 Boucher Lake in l97O had a pH of.7.5, Cu levels of 0.10 ppm but Ni of 2.5 ppm. Alice: deep glacial ti'll on one side, blackened ercded rocks on the other three, largely devoid of veqetation. Irrtu on glacial ti l I at lake edge. Babv: DrscussroN ileep, ercdJng mcky sides and slopes, lacking vegeta- Elon. oalsyr sparse vegetation, a few deciduous A number of studies 'in Sor-resistant trees have emphasized the protected areas, no ground vegetation. deleterious ecological consequencesof sulfur- Richard: declduous trees, good grcund cover. glacial tlll over bedrock, conplete grcund cover. dioxide emissionsfrom the Sudbury-area smelt- jack 0lll: pine in with decjduous trees, complete grcund cover ers on the forests of the area (Linzon 1958; Gorham & Gordon 1960; Dreisinger L970), and on the quality of lake waters (Gordon & Gor- ham 1963, Gorham & Gordon 1960b). Leblanc IA8LE 7. HEAyYllETruS (ppE) AtD pH tAtUlS FORSOtt! !.A(ES Iil THE CON!S]O{ARIA OF SIJOUJRY,SEPIINBER I97O & Rao (L966) correlated the decline of lichens Dlstlnce (lor, and mossesin the Sudbury area with their sensi- Lah f@ n€amst pH C. Cu ill A9 Cd Fe sulflb tivity to sulfur-dioxide fumigation.

All@ 2.0 kn 6.3 n.2 0.06 6.4 0.001 0.005 0.23 In the present studies emphasis has been Eaby 2,4 4.1 3.6 0.52 2.7 0.003 0.003 0.28 72 placed on heavy-metal emissions and their ac- odlsy 4.0 6.1 5.8 0.20 0.40 nd 0.002 0.10 48 cumulation in soils as potential toxic factors in Rlchard 6.4 6.4 12.8 0.005 0.15 nd 0.002 0.25 40 0il1 ll.6 6.7 8.2 0.003 nd nd nd 0.30 25 seedling establishment of the forest species Long 7.0 7.1 5.0 0.03 0.12 0.@3 nd 0.30 (Hutchinson & Whitby 1974; Whitby & Hut- lclley 3.2 6.5 60.8 0.16 0.95 0.008 0.008 0.73 chinson 1974). Widespread contamination Lldy 3.0 5.0 ld.6 0.49 3.02 0.03 0.006 0.37 of the ihcd@ald soils of the area has been shown for the smelted nd. bel@ det4ilon l.lnlts of @tj|od. metals nickel, copper and iron. Co, which is ECOLOGICAL CONSEQUENCES OF DISCIIARGES FROM SI'DBURY SMBLTERS 55 produced in lesser quantities, has also accumu- believed to be a contributing factor in increas- ing heavy-metal uptake, and in converting these lated in surface soils around the Coniston 'available') smelter. Ni and Cu especially are currently metals to soluble (and therefore present to levels of 100O ppm and more for a forms. drstance of. 7.4 km from the Coniston stack. In the field experiments a lalge numbel of Concentrations decline with distance from the species were sown as seed at sites on transects smelters and with depth through the soil profile. out from Coniston. Most speciesfailed to germi Elevated levels of Ni, Cu, and Fe occur in the nate and/or survive for even a single growing foliage of natural vegetation. For example, season. Buckwheat (Fagopyrum saggitatum) Bowen (1966) quotes onormal' levels for land gave the best over-all performance. Many seed- plants as 3 ppm for Ni, and 14 ppm for Cu. lings of several suwiving species showed sul- Stone (1968) found, for Acer rubrum, that fur-fumes {amage to their foliage. An'alysis of foliar Cu levels in a non-polluted area were 3.6 field-grown plants disclosed very high levels of to 9.0 ppm. In the present study, Acer rubrum Ni and Cu within the foliage of the seedlings Ni levels were in excessof 30 ppm to 20 km (Fig. 2). These levels were markedly reduced by from Coniston, and Cu in excessof 2O ppm also a soil amendment of lime, which also increased to 20 km (Iable 1). Al and Fe concentrations the size of the plants and their survival (Iable showed simil4l palterns of elevation. The in- 3). creased acidity of soils close to the smelters is Rather similar results were obtained when

SUDBURYLAKE WATERS-CHLAMYoOM0NASougomotos

ZA +aeut PHADuusrED To 6.8 D +aBM,Nor AD,rusrED ffl -BBM, " '!r

J o E F z 3Go

|l o

\o-40 i F 3 3zo c,

C ONTROL SOUCHER NORWAY ALlCE EABY LADY KELLEY LONG MA@ONALD Frc. 3. Growth, expressedas cell counts after 10 days in cultures, of cells of Chlamydomonaa,eugametos rn controlled laboratory conditions when gtown in lake waters from the Sudbury region, with or with- out pH adjustment and nutrient (BBM) additions. 56 TFIE CANADIAN MINERALOCIST

soils were removed from the field and seedlings to Coniston was revealed. Both standing crops grown on them under controlled greenhouse and species diversity were found to be markedlv conditions. These conditions excluded the com_ reduced Cfable 6). The chemical analvses re- plicating field factors of sulfur-dioxide fumisa_ vealed several lakes to have pH as low as 4.0 tions, droughts and micro-meteorological Jff- and Cu and Ni concentrations to L and 6 ppm ferences between sites. None of the seedlingsof respectively. The presence of a very few surviv_ the species tested survived the 2g-day ing cells in some of the lakes strongly polluted mntal period on soils ""i"ri- obtained within 7.4 km with heavy metals is perhaps surprising in view from the Coniston smelter (Iable 4). Clearly of the high toxicity of Cu to a^lgaeat levels these sofu were toxic to the seedlings and the as low as 0.1 ppm and Ni at levels as low as similar responsesin the laboratorv and at the 0.5 ppm (Ilutchinson 1973). However" havins field-sites are strongly suggestive that heavy- found some cells still surviving, it is ihen nd metal accumulations have exceeded seedling surprising to find them to be both nickel- and tolerancesover a wide area. Forest regeneration, copper-tolerant (Stokes et al. L973). An addi- without soil amendmenl is thus seriouslv in tional factor is that for many algae, Ni and Cu doubt., Indeed, the greenhouse-grown piants rnutually enhance tle foxicify of each otler, showed symptoms in typical of heavy-metaitoxi- an example of heavy-metal synergism (Hutchin_ city. Lime and lime plus fertilizer amendments son 1973; Stokes 1974). were again successful in a) improving growtb Although pH and survival and b) decreasing6"avy-met adjustments and nutrient addi- t up- tions take to the tops (Iable 5). had marked effects in ameliorating the toxicity of some waters, for the worst_J Water extracts of the field-collected soils ta_ minated lakes even this was not enough to confirmed the highly soluble nature of a signi- allow algal grofih, e.g. Alice Lake. The casi of Kelley ficant percentage of the Ni, Cq and Al in ;ils Lake is.a special perhaps suggesting within 10 km of the smelter. Water_extractable -thanan approach to acid lake restoration oiher Ni at concentrations to 20 ppm (and as high simple ant-acid additions via lime. Kelley Lake as 42O ppm) was found in surface soils. A si- should u poor phytoplankton popilutioo milar pattern was found for Cu and for Al !?u," and be highly toxic to algae if its heavy_metal (Iable 2). All three of these metals have been content alone is considered. However. found to reduce root growth of a number of the presence of a high organic content via sewage test speciesby as much as 5O7o at solution son- annear-s-.to play a major role in centrations of 2 ppm or less (Whitby & Hutchin- fnu1.s reducing the "expected" toxicity. Organic ligands son 1974). The potential toxicity to vegetation com_ plexing potentially-toxic heavy metals=seem of these soils in the field is clear. The sitr.ration to be part of the answer, although the is not nnique however, as Buchauer (1973) increaseddiva_ re- lent-cation levels, especially ported similar vegetational penn- of calcium, mav be effects near a contributing factors. sylvania smelter. Tli. asp"ct is currently The scale is much greater at being studied Sudbury. at the University of Toronto (e.g. Stokes & Hutchinson l97S\. The loss of the forest cover and the conse- The possibility of quent erosional loss of the soil has also been a the high sulfate levels be_ ing controlling factor in comtamination of the many lakes toxic factors was largely ruled in out_by the area. Soluble and insoluble heaw metals lio_assaysusing sulfate gradienis as high as 25G3OO ppm have been entering water bodies for the past sulfate. These high Ievels d'id not inhibit algal growth 4O-50years, and the metal loss of the waters has been accentuated by the acidifying nature of Since the acidity of lakes over a wide area the precipitation, which yields sulfur-laden acid around Sqdbury, and especially to the south- rains over an extensive area. west has increased over the past 15 years, one anticipate The phytoplankton studies have indicated "an a continuing irosion of tiie io the affected lakes. pro-bl-emsregarding both increased lake acidity Heavy-metal and aciditv in_ Gractions are likely and increased Ni, Cu, and sulfate contents of to lead to reduction uod t*, of the primary producers. lakes close to the smelters (Stokes et al. 1973: This is paralleled and often_preceded by loss Hutchinson & Stokes 1975). The decline in fish of zooplankton and fish populations. Control populations which correlate with increasedacidi- of sulfur-dioxide emis_ sions-appearsto fication has already been referred to in be an essentialfirst step. H;;;_ the metal controls literature @eamish & Harvey 1972). on emissionsalso need t; be inJi_ tuteq although so much is now available from Algal standing crops were sle:lsuted in 1969- soil run-off that it is apparent that vervJ lonp----o 7l and. the depauperate nature of lakes close term damageis already-done. 57 ECOLOGICAL CONSEQT'BNCES OF DISCIIARGES FROM SUDBURY SMELTERS

(1974): HeavY metal ACKNOWLEDGEMENTS & Wnrrsr, L. M. pollution in the Sudbury mining and smelting The work was partly supported by National iegion of Canada. 1. Soil and vegetation col- Research Council operating gtants to two of tamination by nickel, copper' and other metals' the authors (P. M. Stokes and T. C. Hutchin- Environmental Conservatia.n t, 123-132. son). & - (I975)z The effects of acid rainfall and heavy metal particulates on a boreal near the Sudbury smelting re- RETERET.{CBS forest ecosystem gion. Presenied at Flrst Internat. Symposium on BEAMIsH, R. J. & Herwv, H, H. (1972): Acidifi- Actd Precipitation and the Forest Ecosystem. Ontario cation'of tle La Cloche Mountain lakes, LEBLANc, F. & Reo, D. N. (1966): R6actions de and resulting fish mortalities. J. Fish. Res. Bd, quelques lichens et mousses 6prphytiques a Canad.a 29, lL3L-Lt43, l;anhvdride sulfureux dans la r6gion de Sudbury' BowEN, H. J. M. (1966): Trace Elements in Bio' Ontario. Bryologist 69, 338-346. p' chemistry. Academic Press, New Yotk 241 Lnrzo\ S. N. (1958): The influence of smelter BucHArtER, M. J. (1973): Contamination of soil fumes on the growth of White Pine in the Sud' and vegetation 1s41 I zing smelter by zinc,-cad' bury region. Ontario Dept. Lands Forests and mium, copper and lead. Environ. Sci, Tech' 7' Ontario Dept. Mines. 45 PP. 131-135. Srorrs, P. M. (1974): Uptake and accumulatioa CosrEscu, L. M. & HutcttnvsoN, T. C. (1972): of copper and nickel by metal tolerant strains The ecological consequencos of soil pollution by of Scenedesmus. Proc, XIX Congress Internat. metallic dust from t.he Sudbury smelters. Proc' Assoc. Limnnlog!. lSth Ann. Mtg. Inst. Envlrontnental ,Sci., New & HurcnrNsoN, T. C. (1975): Copper York, 540-545. toxicity to phytoplankton, as affected by organic DREIsINcBR,,B. R. (1970): SOz levels and vegeta' ligands, other cations and inherent tolerance of tatiou injury in the Sudbury area during the 1969 algae to copper. Symp. Internat. Joint Commis- season. Dept. Enetgy Res. Management, Prov' sion Toxicity ol Biota to Metal Forms in Na- ince of Ontario, Canoda, publ. April L97O' 45 pp. tulal Waters. Duluth Oct- 1975 (in press). Gonneu, E. & Gonoory A. G. (1960a): Some ef- & KRAUTER,K, (1973): Heavy fects of smelter pollution northeast of Falcon- metal tolerance in algae isolated from contamin- bridge, Ontario. Can. l. Bot. 38, 307-3t2' ated lakes near Sudbury, Ontario. Can. J. Botany 5L, 2L55-2168, & - (1960b): The influence of smelter fumes upon the chemical composition of SToxE, E. L. (1968): Microelement nutrition of lakes waters near Sudbury, Ontario and upon forest trees; a review. In Forest Fertilization: the surrounding vegetation. Can. I. Bot.38' 477' Theory and practice. Tennessee Valley Authority 487. USA. 306 pp. & _- (1963): Some effects of Wrursy, L. M. & Hurcril.IsoN, T. C. (1974): smelter pollution upon tho aquatio ve-getation Heavy metal pollution io the Sudbury mining and near Sudbury, Ontario. Can, J. Bot. 4L' 371:378' smelting region of Canada II Soil toxicity tests. Environ nental Cowervation l, l9l2$o. HrrTcHnlsoN, T. C. (1973): Comparative studies of tle phytotoxicity of heavy metals to phyto' Wnrrav, Leslie (Costescu) (1974): The Ecologlcal plankton and tleir synergistic interactions. 7[a' Consequences of Airborne MetuAic Contaminants ter Poltattan Res. Can., Proc. 8th Can. Symp' lrom the Sudbdry Srnalters. Ph.D. thesis, Univ. (in press). Toronto, Dept. Eotany. & SrorBs, P. M. (1975): HeaW metal toxicity and algal bioassays. ln Watet Quolty iiioofutrrt. Amlr. Soc.Testing Mat. Spec. Tech. Manuscript receivedtuly 1975, emendedNovember Pub. 678, PhiladelPhia. 1975'