Cadmium Pollution of Belledune Harbour, . New Brunswick, Canada
J. F. Uthe and V. Zitko (Editors)
Biological Station St. Andrews, N.B., EOG 2XO
October 1980
·- ... ~'.:. Canadian Technical Report of Fisheries and Aquatic Sciences No. 963 ·
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Canadian Technical Report of tz_zs Fisheries and Aqua tic Sciences W>.1 . A~41'? lA-c. ~k,
October 1980
CADMIUM POLLUTION OF BELLEDUNE HARBOUR, NE\~ BRUNSWICK, CANADA
J. F. Uthel and V. Zitko [Editors)
Fisheries and Environmental Sciences Department of Fisheries and Oceans Biological Station St. Andrews, New Brunswick EOG 2XO
!Fisheries and Environmental Sciences ARLlS Department of Fisheries and Oceans Alaska Resources llalifax Laboratory Library & Information Serv1ces Halifax, N.S. B3J 2S7 Anchorage, Alaska
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This is the one hundred and twenty-:eighth Technical R por4:Lft.~fu:A DEPT. OF FISH 8: r t· \A[ the Biological Station, St. Andrews, N.B. 333 Raspberry f' :' Anchorage, Alaska S, _ i i PREFACE
The presPnCt' of the New Brunswick ~1lning and Smelting Corporiltion Ltd, (Smelling Division) operation in Belledunt>, New Brunswick, has, since its construction, n'prest>ntcd a potential source of heavy metals to the Baie de Chaleur. Biological monitoring studies, both hy the compilny and hy the fedc>ral llep The Brunswick Smelting report documenting the 1979 biological monitoring activities in the Belledune area was made available to the Department of Fisheries and Oceans April 18, 1980. This report indicated that the concentrations of heavy metals, in particular cadmium, have been increasing at an accelerated rate i.n several marine resources. The area affected, as delineated by concentrations of cadmium in mussels "upstream" and below Belledune Harbour, was expanding. Most significantly, the levels of cadmium in lobsters in Belledune Harbour were becoming dangerous from a public health standpoint. With the lobster s'"'son destined to open May 1st, rApid action was required. The Director General, Fisheries Mnnagement 1>1arLtimes Region, declared that emergency procedures he instituted to investigate the situCJtion and to develop recommendatIons regarding the exploitiltion of the lobster resource from the llelledune area. The Bedford Institute of Oce.1nography offered its assistance in the investigations. The Fisheries and Environmental Sciences Division of the Maritimes Resource Branch was identified as the lead organization to carry out the required scientific investigations on behalf of the Department. The Immediate research objectives were (1) to determine the geographic extent of cadmium contamination of lobster stocks in Bc,lledune Harbour and adjacent vicinity and to delineate where elevated cadmium levels in lobster return to "baseline"; (2) to develop scient! fie evidence necessary to establish a "safe" level for cadmium in lobster; (3) to determine the extent to lvhich the sediments were contaminated with cadmium and the effect of local currents and oceanic circulation on the distribution of cadmium in the area; (4) to evaluate the effect of cadmium on the other marine resources in the area. Tn addition to the above investigations, there remained the operational requirements to meet with fishermen's groups, to establish a controlled fishing zone where all lobstf>rs would have to be specially processed, to encourage implementation of the planned improvements to the effluent control facilities at the smelter, and to develop, with Health and Welfare Canada, appropriate "tolerance" limits for cadmium in lobster. This report represents the scientific data base that was developed in response to this emergency. It represents an ~nportant benchmark on the presence and distribution of cadmium in the ~lledune area (against which future pollution control actions can he measured) and provides a better understanding of the fate and biological effects of cadmium on the lobster. The use of the information provided by this report and the continuing research efforts by Noranda Research on behalf of Brunswick Smelting and the effluent treatment facilities should ultimately lead to an Improved marine habitat in the Belledune area. Strategies for the mana~ement of the Belledune lobster fishery in 1981 are already being planned; with sufficient lead time, there should be no undue disruption in the 1981 lobster fishery in the Belledune area. It is important to take this opportunity to acknowledge the cooperation and assistance received from Brunsw_ick SnH.-'1 Ling and the Norancia Research Centre~ The cooperation received from the Environmenta1 Protvction S<,rvice of the Department of the Environment and the Nc" llruiH>Wick Department of Environment is also The Editors and I wish to acknowledge the• assistance of Ms. Ruth Garnett for technical editing and Mrs. Brenda McCullough for typing and assembling the report. R. H. Cook, Chief Fisheries and Environmental Sciences Department of Fisheries and Oceans Biological Station St. Andrews, N.B. EOC 2XO @ Minister of Supply and Services Canada 1980 Cat. No. Fs 97-6/963 ISSN 0706-6457 Corrt•ct citation for this publication: lltlw, J. F., and V. /,itko [Editors]. 19110. Cadmium 1mllutlon of !lelledune Harbour, New Brunswick, Canada. C:ln. Tt•ch. RPp. Fish. Aquat. Sci. 96·), v + l07 p. iii TABLE OF CONTENTS Pre· face Abstract iv Fisheries concerns associated with the cadmium problem at Belledune - D. C. Riley Industrial discharges of cadmium at Belledune D. B. Sergeant and G. F. Westlake 3 Distribution of cadmium in marine biota in the vicinity of Belledune - S. Ray, D. W. McLeese, C. D. Metcalfe, L. E. Burridge and Jl. A. Haiwood • • • • • • • • • • • • 11 A preliminary survey of circulation and heavy metal contamination in Belledune Harbour and adjacent areas - D. H. Loring, J. M. Hewers, G. Seibert and K. Kranck • 35 The lPach.ing of cadmium from three llelledune smelter materials - D. ll. Sergeant and S. Ray 49 UptnkP and excretion of cadmium by mari.ne organisms from sea water >~ith cadmium at lo>~ concen- tration: a revie>~ D. W. McLeese ••••••••••• 55 Cadmium ln American lobster (Homarus americanus) from the area of Belledune Harbour - J. F. Uthe, C. L. Chou and D. Ro-binso_n__ •••••••••• 65 Crtdmium i_n hepatopancreas of American lobster (Homarus americanus) from eastern Canada ,]. F. Uthe and H. C. Freeman • • • • • • • • • • • • • • • • • • • • 73 Studies on the forced depuration of cadmium from the American lobster (Homarus americanus) - J. F. Uthe • • • • • • • • • • • • • • • • • • • • • • • • 77 The uptake of cadmium by rats from a diet based on canned American lobster (Homaru~ americanus) lwpatopancrpas preparation - C. L. Chou and J. F. Uthe • • • • • • • • • • • 81 Aden vi 1\ l"···liminary ,_;tudy of the histology of the ill'palop;l!ll'rcas, gill and gn•c•n gland tissues of American lobsters (llomarus amerlcanus) collected from till' Belledune ar,•;~ of the Bay of Chaleur- P. Od en sc -;;-,-;·d-C-,:-A;;-;;-,;-;~~-=--. • • • • • • • • • • . • • • • • • • • • • • • • 93 ( v ABSTRACT Uthe, J. F., and V. Zitko [Editors]. 1980. Cadmium pollution of Belledune Harbour, Ne1v Brunswick, Canada. C<1n. Tech. Rep. Fish. Aquat. Sci. 963, v + 107 p. Hesults of invcstig<1tion of cadmium (Cd) pollution in Belledune Harbour, New Brunswick, CanadA, in April- June 1980 are described. 11w investigAtion WAS carried out by the DepArtment of Fisheries And OceAns in response' to studies by Brunswick ~lining and Smelting Corporation Limited (Sme1ting Division) that indicated an increase• of C:d concc>ntration in blue mussel (~J'!_i_:l_ll_s_ ~~is) and the American lobster (Homax:_LL_s_ amcric<_l_nus) hPtWPCn !977 and 1979. Brunswick SmPI t ing lead (Ph) smelter at Belledune is the source of Cd in Belledune Harbour and in the immediate vicinity, 111e smelter processes Pb concentrat<> and Pb/Cd dust into refined Pb by tr3ditional smelting and refining techniques. Sources of Cd are emissions, surface runoff, slag pond discharge, and leaching of slag and Cd baghouse dust, containing C:d at about TIH• exchange of ~<•ater between Belledune Harbour and coastal flow in the Bay of Chaleur to the southeast appc.·ars to be' limited to diffusion, but this may be changed hy easterly or northeasterly winds. The concrntration of Cd in 1vater within lll'lledlliH' Harbour (tlvo se~mples) was 125 pg/L near the smelter oul Llil, located at the eost end, ond 2'1.5 pg/1. in till' C<'nter of the' harbour, nnd decren.se>d to O.l-2.0 pg/L out>:ide tlu• harbour. The concentration of Cd in sedimpnt was 9-()J ~g/g dry weight with the highest values ln the W<'Ster The concentration of Cd in hiota had a similar patt0rr1. Outside the harbour Laminar~ digit~t:_i_l_, Fucus vesir::_l]105.'1_8__, and ~scc>_phyl_l_l~ nodosum contained 0.4-1.8, 1.3-30, and 0.3-18 ~g Cd/g wet weight, respectively. C:cl content of _l'!y_ti.lus _e_dul.is, Nodiolus modiolus, Cancer irroratus gill, coxal muscle, cheliped muscle, hPpatopancrc'as, Littorina littorea, and Buccinum undatum was 7.9-112, 15.2-55.6, 1.7-53.5, 0.2-29.2, 0.1-8.1, 2. '3-394, J. J-1;4,~and OklJB ~g/g -dry weight, respectively. The concentration of Cd in polychactes, flatfish viscera and muscle was 0.2-3.6, 0.3-2.0, and 0.02-0.4 ~g/g dry weight, respectively. Lobsters within the harho11r wpre highly contaminated. CJ11e geometric meon concentration of C.d in the hepatopancreas was 176 (N=2Y), 62 (N=2il) and 24 pg/g wet weight (N=30) in lobsters from thP western and eastern parts and just outside tlw harbour, respectively. At approximott•ly 17 km from the mouth of the harbour to the southeast the concentration was 11.6 pg/g wet weight (N=3l). Gl'ometric means of C.d concentration in lobster hepatopancreas frnm v:1rious lncnlitiPs in eaBtern Cnnada range from ~R to 17D2ug/gwct weight~ Sturl it.'.c.; or ::1dcnylate enprgy chnrgl', ATPnsc .:1ctivit_y, and histology do not indicate any ;HlversP effects of Ccl 011 lobstt•rs from Be l.ll'dunp Harbour. A revLL'VJ of tht' literature indicates that marine fauna rtccumuJates Cd from seawater even if concentration of C:d is ns low as 0.5 J.tg/L, and the c•xcn:tion rate of Cd appears exceedi.ngly lo1v. Excretion of Ccl from lobstcrs could not be achieved by feeding or injecting chelati.ng agents. 11~e availability of CAl to rats from t'ont:unlnated hepatop<:1ncrc;:ls was only Rbout SO% of thAt from a Cd-contaminrtterl, casein-based diet .. K('Y \-Vords: cadmilm1, 1eacl, :;:inc, heavy metals, trace elements) mining, smelting, American lobster, bivalve molluscs, crabs, Belledune v Utlw, J. F., and V. Zitko [Editors]. 1980. CHdmium pollution of Belledune HHrhour, New Brunswick, CnnHda. Can. Tech. Rep. Fish. Aquat. Sci. 963, v + 107 p. Les auteurs presentent les resultats d'une etude realisee en mai et ]Uln 1980 par ]e ministere des Peches et: Oceans, portant sur la pollution par le cadmium du port de Belledune et hasee sur ]'information transmise par Brunswick Mining and Smelting Corporation Limited (Smelting Division) indiquant une augmentation de la concentration du cadmitun chez la moulc bleuc, MyJJ:lus edulis, et le homard, Homarus americanus, entre 1977 et 1979. Brunswick Sm(~l ting exploitf' une jnnderiP cle plomh ;] Bf?lledunP en bordurl' du 11ort. La fonderil' transforme un concentrC de plomb el une poussiC.rt> enrichie de plomh-cadmiurn Les echanges d' eau entre le port et le courant c6tier de la Ba ie Des Chaleurs, lequel est oriente vers le sud-est, semblent se limiter a une diffusion. Cependant, il est possible que des p€riodes de vents d'est ou du nord-est, modifie ce mod~le. Lef; concentrations de cadmium dans l'eau de mer (d'apres l'analysL~ de deux echantillons) etaient de 125 ~g/L pres de 1 'effluent dP Ia fondt'rie sJ tueC' dans la partie est du port et de 25,5 ~g/L au centre de port hors dugut'l etles baissait~nt 8_ 0,2-2}0 l-lg/L~ Dans les s6diments, l(:'S concentrations variaient entre 9 et 61 pg/t~ dans lt• port, les maxLma 6tant observes dans 1a partie ouest pour di.minuer entre 0)4 et 1,0 Jlg/g 8 l'esL6rieur du port .. Une hande cte sEdiments contarnini§s, ori.entCc vers le sud-est, s'i§tend sur 12 km a partir de 1'entrCe du port. Les c->3UX et les sediments du port E>taient E>galement fort contrtmines par le zinc. Pour ce qui est des conct~ntrations de cadmium dans le biotope marin, on remarquait la meme tendance. A I 'exlerieur du porl, des echantillons de _l:_amin~riil ~it L'Ptucle la charge energ2tiquc des ad§ny.lates, de lractivite ATP-asique et des coupes histologirJues d'hGpaLopancr6as indiqul' que 1e cadmium, aux concentrations observ§es, ne semble pas avoir d'effets nocifs chez 1~ homard dt1 pt)rt de Belledt•ne~ D 1 apr2s unC' &tude bihliographique, la jaune marine concentre du cadmium meme lorsque ce dernier est prC~.;t'nt dans 1 'eau rlt> mer R des nivt:-aux aussi bas que 0,0':> pg/L, et semhle ne 1'excri?ter que tr€s lentementc Ainsl des l.'Xpt?riPnces d' ingestion et rl' injection d'agents chl>l.R.teurs chPz le homard n'ont pas reussi a pr\)Voq\H'r UIH' excrCtion du cadmfnrn~ De p1us, des expt?riences ont df.montr& flUE' des rats nourris avec des h6p;lLnpancr6ns t:ontamin6s n 1 assimilent qu'environ 1n moiliP du cadmium qu'ils assfmilPnt d'un r6gime ca s6iniq111:> (•nrit·hl de cadmi11m~ -1- FISHERIES CONCERNS ASSOCIATED \-JTTfl THE CADHTUf! PROllLEf1 AT BELLEDUNE by D. C. Riley Fisheries and Environmental Sciences Department of Fisheries and Oceans Hal ifax l;;boratory Halifax, Nova Scotia B3J 2S7 -2- The discovery of high cadmium ( Cd) levels in assessed after implementation hut there is good lobsters taken from the Belledune Harbour area this reason to believe a significant improvement can be year poses a significant resource management problem expected. A potential hazard exists with respect to as well as environmental protection ramifications. existing high levels of cadmium in marine sediments While the most urgent problem that had to be and its availability to marine organisms. A addressed when the cadmium contamination became solution to this continuing hazard is necessary known was to document the extent and nature of the although the options available to the company are contamination, in vi.ew of the imminent opening of rather limited. the lobster fishing season, the biological and ecological implications remain a continuing major concern to this department. Physiological and behavioral effects on lobsters and other marine species from high cadmium exposure will require further research and investigation before the extent of resource implications can be established. The more immediate and obvious effects, such as loss of income to fishermen due to area closures and poten tial impact on local and foreign markets, can be addressed in an operational fashion but long-term biological impact on marine organisms remains and is a much more complex and difficult problem to address. The Belledune cadmium incident, being a localized point source problem, facilitated the application of stringent control measures to be applied within a limited area. Although a control zone extending outside the harbour was ultimately established, lobster fishing within this control zone was permitted and all catches within this area were subjected to special processing procedures under the supervision of departmental personnel. The department 1vas seriously handicapped in determining what level of cadmium was permissible from a human health aspect because no specific levels have been stipulated. Only after extensive consultation with Federal Health and Welfare personnel were permissible levels in lobster tomalley and muscle determined. These levels were based on extensive pre-analyses of lobsters taken from inside and outside Belledune Harbour and previously established background levels for the area. Based on this information a final control zone was establ"lshed but not Llllt:i 1 the Lobster ishlng season was well under way. If permissible levels of cadmium, based on human heal.th require ments, had been established earlier, the delay and f rust rat ion would have been minimized. The lag period encountered for transmission of scientific data on the Belledune cadmium problem from industry to regulatory agencies and from regu latory agencies to the department resulted in a short lead time in which the department was able to react before the fishing season opened. This created serious Internal administrative difficulties and remains a major concern to the department. Improved procedures for more timely exchange of environmental data having fisheries implications, and corrective measures to be adopted to prevent a similar situation from occurring in the future, are matters that require serious discussion with regu latory agencies and industry officials. A much more timely transfer of new information relative to possible fisheries implications is warranted. The Brunswick Smelting plant situated adjacent to Belledune Harbour has been identified as the prime contributor of the elevated cadmium levels within and immediately outside the harbour. Recently, additional measures have been implemented by the owners to reduce cadmium and other heavy metals being released into Belledune Harbour. The success of these corrective measures can only be -3- INDUSTRIAL DISCHARGES OF CADMIUr1 AT BELLE DUNE by D. B. Sergeant Fisheries and Enviro11mental Sciences Departrnt:•nt of Fishprit>s .:1nd Ocr>ans !Hological Station St. Andrews, NPw llrunswi c k EOG 2XO and G. F. Westlake Water Pollution Control Division Environmental Protection Service Department (Jf Enviro11ment Atlantic Region ') ll)l Ceorge Street llnl il"ilx, Nov;l Scotia BJJ IH', fNTRODlH :T fON Brunswick Mining prod•>ec's n lead-zinc-copper sliver ore of which BO% is sulfides and 20% is quartz, calcite and silicate. Brunswick Mining Since 1966 Brunswick Kining and Smelting concentrator produces Cu, Zn and Ph concentrates by Corporation Limited, Smelting Division (Brunswick a differential flotation process (Neumann and Smelting) has operated a lead/zinc smelting and Schnarr 1971). Brunswick Smelting currently reflning plant at Belledune. In 1971 the refining receives 225,000 MT of Ph concentrate from this of zinc was terminated, but the lead smelting source, plus minor amounts of purchased high-grade continued. 'l"ne plant produces some 60,000 metric concetrtrate. The pas-t~-and present analyses of mine tons (MT) of lead, 3,600 Wf of copper matte, lesser concenlrate are shown in Table 1. amounts of silver and lead-antimony alloys and 175,000 MT of sulfuric acid per year. This paper Since 1976 approximately 4500 NT per annum of describes the operation of the smelting and refining Cottrell dust (approximately l-2% Cd) from Noranda and of the fertilizer plant at the same location, Horne mine in northern Quebec has been brought in by and their discharges to the Bay of Chaleur. r·ai.l, unloaded by a rotary car dump and stockpiled on the Belledune site in a covered building. The Horne dust and the above concentrate are used in the THE LEAD SMELTING AND REFINING PROCESS charge preparation. AT THE BELLE DUNE SMELTER CHARGE PREPARATION The plant at Belledune originally produced both At this stage of the process, Pb concentrates lend (Ph) and zinc (Zn) by the Imperial Smelting nre mixed with fluxes (sand and lime), sinter fines, Proc<'SS (ISP) but, in 1972, the llellDdune smeltet· dusts, drosses, sludges, etc. (which contain Pb and was modified to produce only refined Pb and otlwr metr ls TilE Pb CONCENTRATE vo1ati lized and carried off with the so.) and dust. At Brunswick Smelting, so 2 from the sinter In ores, cadmium (Cd) is clos<2ly associated machine is drawn through an electrostatic precipi with Zn and small 2mour1ts of Zn are present in Pb tator to remove most (98%) of the Pb dust prior to concc'nLrates (Lymbnrner 1974) from the mining gas c 1 ean ing in the Acid Plant. The prec i pita ted flotation processes. The boiling point of Cd i.s Cd-bearing dust is returned to the process at the 767°C (Consi.dine 1971,) in contrast to the boiling rate of 1~-2 MT per hour to recover Pb. point of Pb which is l740°C (Considine 1974). Above these temperatures the metals will be present as The hot sinter corning off the end of the vapors or "fumes .. " machine is broken by a claw breaker into pieces Table i. Composition of Pb concentrates. Brunswick Mining No. 12 Pb concentrate Pb concentrate (Brunswick Smelting data) Component (Neumann & Schnan 1971) Jan-Mar l 97 9 1980 Pb 38 32 Jl) Zli !0 7 7 s 27 13 34 Fe 14 2 3 23 Crl 0.02 O.Oli• 0.014 -5- approximately 10.2 em diameter and fed into the melt. The Cu crust is skimmed off the top, resul- blast furnace. The fines are removed and returned ing in reduction of the Cu content of the hullion to the sintering process charge preparation stage. from several percent to less than 0. 5%. The liquid lead is then transferred to a second kettle where BLAST-FURNACE SMELTING nuother Cu drossing occurs lowering the Cu content of the Ph to less than 0.0!%. The Cu drosses are The sinter is mixed with coke and fed to the then processed further to form Cu matte. hlasL furnace. Table 2 shows the typical Brunswick Smelting sinter analysis. Next the Ph is softened to remove Sb, As and tin (Sn), This is accomplished by a process known A series of complex chemical reactions occur in as oxygen softening (previously oxidative slagging the blast furnace, yielding the following products: with sodium hydroxide and sodium nitrate was used in this softening process). An air-oxygen mixture is l) Pb bullion, which still contains the injected iuto the molten Pb and the As, Shand Sn impurities) Cu~ arsenic (As), antimony ( Sb), are oxidized and form a crust which is skimmed off. bismuth (Bi) and some lver (Ag). This Ag and Au are then removed by treatment of the bullion must be re lned further to produce a mol ten Pb with Zn metal, Zn combines with Ag and Au higher puri Pb final product. to form alloys that are insoluble in Ph and forms a crust that is skimmed off and treated to produce Ag. 2) S I , which is composed of the silicates of The tr«cc> amounts of l:n remaining in the mol ten Pb ir()!l, ca]citlrn) magnesium and almost all of are reJn(Jved Hnd recovered by a vacuum distilliltion~ the Z.n, present or lginally tn t-lw concen- Bi is then removed in a two-step process wl tli rate .. At Brunswick Smelting no attempt is add it ions of calcium and magnesium and a lowering of made to recover the Zn~ Thjs lag is then the mol ten Pb temperature. The crust of inter granuLated by Impacting a stream of molten metallic compounds is skimmed off and the Bi slag with a jet of fresh water and recovered. tra.nr->ported with a stream of seawater to the slun·y pumps. "l11e granulated slag formed TI10 molten Pb is now of high purity and is cast I bLack, glassy and consists of sand-like into pigs (25.4 or 45.4 kg) and jumbos (0.91 MT). particles or larger lumps. The granulated The refining operations at different Pb smelters can slag Hnd water are then pumped to the slag vary in the type of processes used (due to the pile v1here the water part of the slurry runs variation in the concentrations of the impurities 0 fl. and which byproducts are desired). These operations re complex, with various cl1emicals being nrlcit'd in 3) 1\aghollsP du:ot, v;hich is recvclcd to the combination with heating, cooling and transferring cont~:~nt inter pl_nnt., How('Vt!f 1 when tbe Cd betw00n kettles of the molten Ph. apprucwlll• 10%, a portion ·is stockpiled for future salt' .. FERTILII:ER PLANT OPERATION 1<1\F INC: OPERA T TONS The impure Ph bull ion i refined by a series of To use the and so3 byproducts released drosslng (fioatLng on the surface) operations .. The in smelting, Brunswick Smelting operates a sulfuric ilritnc ohjP<'tive of drossi11g is to remove metal] ic acid plant. Sulfuric acid is conducted by a short i mpur l ties~ Dross i ng occurs in J arge, stee], hem i pipe] ne to the Belledune phosphate fertilizer sph<-"'f i 1 kettles up to '). (,() m in d lametPr and p1<~nt. In the plant a Florida phosphate rock c;1pcthl e oJ llol_d ing up to 20q /V1T of mol ten nwte ia 1 ~ (127,000 HT in 1970) is ground in H hall mill and ket l]PS ,'lfl' h~._'rl t'Xlt.-'1Tl Tab1 c 2~ Composition o sinter$ Belledune sinter (Brunswick Smelting data) Compont'll t Cu 0.6 1.0 Ph 32 lO Fe 20 22 s 1.0 1.0 Zn il.O 7.0 Cd 0.38 0.30 -6- RELEASE OF Cd TO THE ENVIRONMENT and by Gale and Wixson (1979). Elevated Cd concen trations were found in forest litter and the decom posed litter along stream beds, with appreciable The significant discharges or emissions of Cd contributions of dissolved Cd to watershed runoff. to the environment are to the air, by surface runoff Cd emissions were discussed by Dugdale and Hummel due to precipitation events, by cooling water ( 1977). Losses to the atmosphere were estimated to discharges, from slag pond discharges, from the be 3,391 kg Cd/yr from baghouses and scrubbers. fertilizer plant discharges, and from the leaching Figure l shows the distribution pattern of several of solids (dusts, slags) by salt, fresh or heavy metals in surface soil samples in the area of rainwater. the smelter complex along with some indication of wind direction. If one considers the background Cd AIR EMISSIONS concentration in soils to be between 1 and 2 ~g/g, then the effects due to the smelter appear to be Since 1968, dust from the blast furnace, sinter localized within the first few kilometers. This plant and lead refinery has been collected in same pattern of localization appears to hold for baghouses and recycled to the sinter plant. The heavy metal concentrations in vegetation. total baghouse capacities have been increased from Undoubtedly, there is a similar pattern of depo 150,000 a.c.f.m. in 1968 to 1,000,000 a.c.f.m. in sition on the surface of the estuary. Quantifying 1976 with the construction of two larger baghouses this deposition is difficult but for Pb it has in 1973 and 1976. It should be noted that used been estimated at 9 kg/ha x month (Dugdale and baghouse dust tubes are also recycled back to the Hummel 1977) and may be in the order of 0.2 kg/ha x blast furnace. Because of the recycle of dust, the month for Cd at the smelter complex, dec rea sing Cd concentration in all dusts (particularly that rapidly within the first few kilometers from the from the blast furnace) gradually increases. When site. Although the air pollution controls are the the Cd concentration in the blast-furnace dust best available for this type of industry, heavy reaches about 10% (has been known to exceed 20% in metals reaching the surface of the water from the past), it is bled off and sealed in containers, fugitive baghouse and scrubber dusts may be in a for sale and refining elsewhere or is piled in the readily bioavailable form. These air emissions may yard (about 180 MT at present). This Cd-laden dust be a significant source of Cd. Smaller amounts of is the major output source of Cd (of about 545 MT Cd-containing dust may be released to the atmosphere produced last year, the company sold approximately from the rotary car dump facility where the concen 363 MT). trate from Brunswick No. 12 and the Horne dust are unloaded from rail cars. Cd in forest ecosystems around lead smelters in Missouri has been documented by Wixson et al. (1977) ,------~ I Average Heavy Metal Concentration In First Six Inches of Soil Near Lead Smelter in Belledune, N. B. 1975 Charlo ...--/~ [ifl,_['b, "Cd]- .ug I 9 . Relative Wind // Belledune lake Fig. 1. Average concentrations of Zn, Pb and Cd in ~g/g in the first 6 in. of soil near the lead smelter in Belledune, N.B., 1975. -7- SURFACE WATER RUNOFF of 1980 the cooling water will no longer combine with the process water. A study of the drainage patterns near the smelter was made for Brunswick Mining and Smelting PROCESS \~ATERS AND SLAG POND DISCHARGE HATERS in 1979 by Montreal Engineering Company Limited. Drainage from approximately 809 ha passes around and Figure 2 is a simplified water balance diagram through the smelter property. East and west ditches for the smelter. Fresh water from the various pro divert runoff from all but 28 ha of the smelter cesses in the plant, as well as the salt water used proper. TI1e latest change (made this year) was to to transport the slag to the slag pile, combine in divert the runoff from 10 ha south of Highway 11 to the slag pond, which in turn discharges into the the west diversion ditch. main cooling vJater channel. Heavy metal concen trations in process water range from 1. 5-4.2 mg/L In the past years the smelter runoff drained for Pb, 3.2-16.4 mg/L for Zn, and 0.6-38.0 mg/L for into the bay at several points along the property, Cd at the discharge of the slag pond ( 1979 data, but primarily through the slag pond and a contami Brunswick Smelting). After combining with the nated ditch on the east side. In 1980 modifications cooli.ng water, the concentrations range from 0. 4-2.3 were made that have diverted this drainage to mg/L for Pb, 0.3-9.2 mg/L for Zn, and 0.3-3.0 mg/L northeast corner of the site, where a new treatment for Cd. Based on the volume of water used in the facility has been constructed. process this is also a significant source of Cd to the environment. Treatment of these process waters Heavy metal concentrations in runoff can be to remove heavy metals is now planned. estimated for the contaminated ditch on the east side of the smelter. 'The concentrations of Pb, Zn, Figure 3 is a schematic diagram showing the and Cd are 0.8, 5.3 and 0.1, and 6.6, 35.2, and 1.6 sulfuric aci.d plant. The acid stream washer water mg/L during dry weather and heavy precipitation, is diluted sulfuric acid and is added to the repro respectively (1979 data, Brunsv1ick Smelting). cess water pond. As acid will solubilize Cd and as Accordingly, surface runoff can contribute signifi·· there is probably an overflow in this pond, it cant amounts of Cd to the Bay of Chaleur. stands to reason that more Cd will be added back into the process by recycling this water (then COOLING WATER subject to loss of high Cd water) or to ditches via overflow .. Typi.cally, 45, 460-54, 550 L/min of salt water are used for cooling. This water i.s passed through LEACHING OF SLAG AND DUSTS the plant by means of two channels on the northwest side of the property. Since it does not contact the Leonard et al. (1977) reported the concentra process waters within the plant, it contributes very tion of Cd at various steps in the refining process. little to the heavy metal loading of the harbour. Some of their findings are shown in Table 3. However, the saltwater inlet is very close to the process water outlet and there is some entrainment Also in this reference was a leaching study of the final effluent in the cooling water intake. performed with secondary blast-furnace slag, furnace Before entering Belledune Harbour, the cooling water dust and scrubber sludge. Only one test \vas per- combines with the slag pond discharge. By the end formed for each, the pH was not specified and higher Sal Water 1500 l 000 SLAG TRANSPORT SLAG GRANULATION 1818 I~ISCELLANEOUS FRESHWATER 1""--'-'77-"5--l<'ro.'=""""""" ------1 USES FRESHWATER 390 * NOTE - the diagram is an enrwnnrne exactly balance in part due to losses Fig. 2. Water balance diagram for Brunswick Smelting operation at Belledune. -8- Emission Control Flow Sheet STACK ( .3fo S0 2) FURNACE SINTER CONCENTRATE FEED + CaO Si02 .014% Cd DUST DUST SLURRIED RETURN FINE DRY! NG TOWER 93% SULPHURIC Blast ACID Furnace Sinter Machine / SLAG GRANULATED / / 0.008% Cd UNDER FLOW BACK TO COOLING AND MIXING LEAD BULLION / / WATER REUSED IN SCRUBBERS, ETC. Fig. 3. Emission control schematic diagram showing dust recycling and so 2 removal processes in the smelter complex. or lower pH's T<1blt· 1. C~1dmium (Cd) concentrations at various stages in U.S. Ph industries ;md Cd sol ubi I ity in watc•r expoS<'cl to process materials (Leonard et aL 1977). Haterial analyzed Cd concentration (ppm) Plant A Fresh blast-furnace slag 10 Old blast-furnace slag 88 nter scrubber sludge 900 Lagoon dredg ings 700 Baghouse dust 14000 Plant B Fresh blast-l"urnacr sl II 'ill Old bl Scrubber sLudge \·h1stewaLer treatment sludg<' Filt Blast-furnace slag (). 03 Lc>ad fuming slag o. 01 Hl~tst-furnace dtlSt 8.0 Sinter scrubber sludge 9. 1 Lagoon dredgings 11.0 Primary lead Slag I 66 SmC'lting <1nd refining Sludge 6900 POU.UTION CONTROL NF:ASURES d iscouragPd (in particular, storagp of 10% Cd dust in the open) 38 this will only be wind-blown. By laL(' 1980 the following pollution control mensures will be in place: ACKNOWLEDGMENTS 1 ~ AlL clean watec drainage will have been cfiverted around the plant~ We thank Dr. V. Zitko for providing us with many of the references, Dr. J. Uthe for his comments 2~ Conventional treatment for sewage wastes on an earlier draft, and Brunswick Smelting for the will be• opf'raLionrll. release of their data. l~ All contaminated surfacr: water drainage from the site will be collected in ont::~ place for REFERENCES t reri tmen t .. All contaminated Welters \.Jl 11 be trc•atcd hy Considinr, D. ~1. (Ed.). 1971,. Chemical .-md Process pll adjustment, congul;1tinn and settling~ Teclmology Encycloped in. NcGraw-Hi 11 llook Comp<1ny, N,Y .. '>. llnderflnw (slurry of sludge) from this trc• Once tl1ese pollution abatement meast1res are in Leonard, R. P., R. C. Ziegler, H. R. Brown, J. Y. plAce, the Cd dischargc>d into the Pnvironm<•nt should Yang, and H. C:. Rei f. 1977. Assessment of drop significantly. However, the storing of dust industrial hazardous waste practices in the mnterials in the open ilt Lhe site should also he metal smelting and refining industry. ll.S. -10- Dept. Commerce, National Tech. Info. Serv. PB-276 169, PB-276 170, PB-276 171, and PB-276 I 72. Lymburner, D. B. 1974. Environmental contaminants inventory study No. 2. The production, use and distribution of cadmium in Canada. Environ. Can • Re p • Se r • No • 3 9. Neumann, G. \~., and J. R. Schnarr. 1971. "The Brunswick Story" concentration operation at Brunswick Mining and Smelting Corporation's No. 12 mine. The Canadian Mining and Metallurgical (CIM) Bull. for Sept. 1971, p. 51-61. Nilsson, R. 1980. Swedten's ban on cadmium under fire from European industry. Amhio IX(2), 107. \~ixson, B. C., N. L. Gale, and K. Downey. 1977. Control of environm('ntal contaminati.on by cadmium, lead and zinc near a new lead belt smPlter~ Trace substances in environmental health- XL D.D. Hemphill (ed.). Proceedings of Univ. Nissouri's lith Ann. Conf. on Trace Substances in Environmental Health, Univ. Missouri-Colrnnbia. -11- DISTRIBUTION OF CADMIUM IN MARINE BIOTA IN THE VICINITY OF BELLEDUNE by S. Ray, D. \v. t".cLeesc, C. D. Netcal fe, L. E. flurri.dge and B. A. Haiwood ~isheries and Environmental Sciences Department of Fisheries and Oceans Biological Station St. Andrews, !'klv Brunswick EOC 2XO -12- INTRODUCTION scallop drag, and D stations (29-34 m) were sampled by ponar grab. A 14-m vessel owned by C. Doucette \>Jas used for sample collections. The occurrence of high cadmium (Cd) levels in the tissues of lobsters and mussels taken from the Scallops, mussel , crabs, barnacles, and macro vicinity of the Brunswick Smelting lead smelter at phytic algae were the taxa collected most exten Belledune, N.B., was brought to our attention in sively. Biota with limited distribution were not late April 1980. The lobster fishing season was due analyzed (Table 1). Immediately upon collection, to open on May l and a study was initiated all individual samples were immediately to determine the extent of \~ contami frozen nation in lobsters in the area (Uthe et al., this report). SAMPLE PREPARATION We conducted a survey during May 5-16, 1980, to Biota samples were thawed and washed with determine the extent of Cd contamination in marine deionized water to remove grit and salt before biota other than lobsters. TI1e survey included sampling stations in the area bounded by Beresford were and Little Belledune, N.B. Included in the biota , gill, gonad, hepatopancreas, sampled were several commercially important plant, adductor muscle, and mantle. bivalve, crustacean and fish species. Also, sedi flatfish ment samples were collected at each sampling site. The main fisheries in the Belledune area irroratus include lobster trapping at depths of 3-ll m within and Hyas araneus crabs were hepato- L 5 km of shore, scallop dragging at 12-18 m in pancreas, gill, cheliped (pincer) muscle, and coxal areas offshore of Beresford, N.B., and Belledune, (shoulder) Whole sp, crabs and and herring fishing with gill nets or seines. There barnacles were prepared, For are no extensive beds of clams, oysters, quahogs or all other tissues were used, Irish moss. Crabs and shrimp are not fished -::"-"---'--""='== ---'----'--"- algae were commercially in the area. Polychaetes, periwinkles, barnacles, scallop SAMPLING AND ANALYSIS adductor muscle, and C. irroratus and H. araneus crab tissues were freeze-dried only. Flatfish muscle, macrophytic algae, Mytilus edulis and COLLECTION _::_~~'--'- -.;-'-:---"'~=- mussels, cockles, Aporrhais crabs, and scallop mantles Samples of plants, animals, and sediments were milled to a powder. Scallop collected at 11 shore and 22 offshore stations (Fig. and flatfish viscera, quahogs and whelks were 1). The A stations v1ere sampled from shore at low homogenized with deionized water by using a Sorval tide and B stations (8-11 m) were sampled by SCUBA homogenizer and then freeze-dried. Sediment samples divers. TI1e C stations (ll-20 m) were sampled by were thawed, dried at 60°C, and sieved through 250-)Jm and 63-)Jm stainless-steel s1eves, Biota samples (0, 2-0.5 g) were ashed for 12 h at L,S0°C and taken up in 1 mL nitric acid for Cd analysis. Sediment samples were digested with 1 mL nitric:hydrochloric acid (3:1 v/v), filtered and made to volume for analysis, 1he acids used were of Aristar quality (B.D.H. Chemkals Ltd., Poole, U.K.), Cd was measured by using a Perkin-Elmer Model 503 atomic absorption spectrometer and Model 500 graphite furnace, Accuracy and precision were checked using N.B.S, reference materials (#1643a - water, 566 - oyster tissue), The results are expressed on a dry weight basis, except where stated otherwise. Animal sizes and either the wet weights and dry weights or wet weight-dry weight relation ships for biota samples are tabulated in Appendix I. RESULTS AND DISCUSSION The general distribution of bottom sediments in the survey area, as determined by SCUBA observation and subjective examination of bottom grabs, is illustrated in Fig. 2. The distribution of the biota in the survey area appears to be related to the bottom type. For instance, scallops are generally located in the areas with gravel and clay sediment and cockles were collected in muddy areas. Except for fish and crabs, few species were seen by Fig. 1. Locations of sampling transects and stations divers in the silt zone surrounding the lead in the survey area adjacent to the Brunswick Mines smelter, smelter. -13- Table !. Species collected in the survey area. Numbers of specimens collected are in brackets and P denotes a pooled sample. Species marked with asterisk were not analyzed. Spec 0 2 3 4 5 6 7 8 9 10 Molluscs l ) C(3) C(l) B(l) C(3) C(3) C(3) C(3) 2) C(2) C(2) 3) A(2) A(7 P) A(SP) A(SP) A(4P) A(SP) A( SF) A(4P) A( lOP) A(SP) B(3) B(3) C(2) 4) 5(2) C( 1) C(2) 5) 0(2) D(2) 0(2) D(2) (,) B(2) 7 ) A(7P) A(6P) A(7P) A( 6P) A(2P) fl) C(l) C(l) D(l) C(l) C(l) D(l) 9) C(2) C( 4) C(l) 10) ll( I ) l l ) B(J) C(2) l 2) D(2) D(L•) D(2) Crustaceans l 3) Cancer irroratus B(2) B(l) C(l) C(l) B(l) C(l) B(3) A(l) ----~ --~---- C(l) C(l) B(l) C(l) ]1,) !'agurus l"::'J:>_escen£;_ C(2) B(l) B(l) B(l) C( 1) 14) Pagur~~ ~cadianus C(l) C( 1) 1 5) ll_xas ':'_raneus_ C(l) D(3) 16) Balanus balanoides A(l2P) A(S) A(lSP) A(l6P) A(l7P) A(l4P) ~-~------''Amphipod A( 4) '~i'1ys ld A(4) ------Polycha -- --··------~- fviac rnphyl t~- H 1 g,JP ( Sl'i\W('Pds) 11) l__:_(~~~i!~.0_~_f_~L -~-£lii-~·at_~_ II A A /\ A A A B l\ B ll lE~) l~ttcus vesictJlosus A A A A A A A A B A A A A A C(2) C( 1) C(2) B(2) C(l) B(l) B(l) ,\(10) St;u- fish 2 6 ) --==,~-:::.:c_c__ C( 1) C(l) D(l) 27 ll(3) ll(l) D(2) 1 )Scallop; 2)1ce>land scallop; 3)Hussel; 4)Horse mussel; S)Iceland cockle; 6)Bar clam; ?)Periwinkle; S)American pelican's foot; 9)Dog whE'lk; !O)Soft shelled clam; ll )Waved Astarte>; l2)Tusk shell; 13)Rock crab; l4)Hermit crah; 15)Spider crab; 16)Barnacle; l7)Kelp; l8)Bladder wrack; 19)Knotted wrack; 20)Yellowtail flounder; 2l)American plaice; 22)Hinter flounder; 23)Skate; 24)Sculpin; 25)Stickleback; 26)Sun star; 27)BrHtle star. -14- Placopecten magellanicus (C Stations-18m) '[ 20 250 :1 .2 8 (f) 200~ 3 -g 0 150 ~ ::;: Transects Smelter Fig. 3. Mean cadmium (Cd) concentrations in meat, mantle, viscera, and whole animals of P. magellanicus sampled at C stations (18-m), Fig. 2. General distribution of bottom sediment types in the survey area. I (' I l SCALLOPS " \ collected from seven r~ s from two stations. The I mean muscle, mantle and I viscera of the scallops from each station is illustrated in Fig. 3-6. The means (ranges) of Cd levels (N=17) in P. from the survey area were 3. 7 (0. 5= *8.43 .2-18.0) and 183.4 (87.6-493.2) ~g/g for \ muscle, mantle and viscera, tively. For \ " \ comparison, of approximately I the same size range, from Passamaquoddy I Bay, N.B., had lower mean Cd concentrations of 0.8, ,.I L3 and 47.7 11 g/g in jlluscle, mantle and viscera (Ray et al., unpubl Pesch et al. (1977) reported Scallop Meats Cd concentrations of 20.9 Jlg/g for whole, Mean Cd Concentration -~~~~~~~~~ __ collected near ocean 1. s 7- Placapeclen m0\181!o;n "''' S. Atlantic coast. For (1.92)- Chlomys islandicus comparison, the mean and range of concentrations in whole scallops in the Belledune area of 50.25 Jlg/g ·-Commercial Scallop (23.1-115.6) were estimated from the sum of the Cd burdens in the various tissues. Zook et al. (1976) found 0.1 (.04-0.2) 11g Cd/g wet weight in adductor muscle from~· magellanicus collected off the U.S. Atlantic coast, The mean and range of Cd concentrations on a wet weight basis for P. muscle in the Belledune area-were 0.8 Cd levels in the three tissues of magellanicus taken at C stations (Fig. indicate that concentrations are elevated at transects 0, 3, Fig. 4. Mean cadmium (Cd) concentrations in meat 5 and possibly 7. Estimates of the whole-body of ~· magellanicus and C. islandicus samples from concentration follow this general trend, although the survey area. -15- variations in the proportion of viscera in the ('' scallops cause the Cd maximum to shift to transect \ 5. The data for C. islandicus were limited to two {1.25)'- _11.71) sampling stations. However, adductor muscle from both scallop species from the same sites contained •8.08 approximately equal levels of Cd, while Cd concen ' \ • 11.77\ I trations in the mantles and viscera of C. islandicus \ were considerably lower than for P. magellanicus. MUSSELS '"12.57 \ \ were collected from 13 stations \ from four stations within the 1 \ some stations, several M. \ were pooled for analysis but, 120' of variations in the Cd content of subsamples from the pooled tissues, the remaining mussels were so' analyzed individually. All M. were So' \ Scallop Mantle analyzed individually. (~g Mean Cd Concentration /g l "8,66 in the soft parts of M. edulis and each station are illustrated in Fig. s.ss- Placopecten mogellanicus ' \ {I 25)- Chlamys islandicus The soft tissues of M. and contained a mean and range (2. and 32.1 (15.2-55.9) ~g/g of Cd, respectively. These concentrations are considerably higher than the Cd levels reported in the literature (Table 2) for mussels from unpolluted and moderately polluted marine areas. In M. edulis from shore (A) stations (Fig. 7), the mean-Cd concentration decreases with distance to the north or south of transects 6 and 7. M. modiolus at stations 10C, 8C and 5C contained Fig. 5. Mean cadmium (Cd) concentrations in mantles relatively uniform concentrations of Cd (Fig. 8). of £• magellanicus and C. islandicus sampled from the survey area. r------~-~------, '-- {5915) ~) 1111168.71 I 120 e 167.09 I 100 --...en \ 0' 223.07 \.._,_ "'- 1 ( 80 \ \ \ \ ." \ 120' c: 60 I \ ,. c: \ 0 Scallop Viscera \ ~ Mean Cd Concentration ( ug/g l ,_ c 40 Fig. 6. Mean cadmium (Cd) concentrations in the Fig. 7. Mean cadmium (Cd) concentrations in soft viscera of P. magellanicus and C. islandicus sampled parts of M. edulis sampled at A stations (shore). from the survey area. -16- CRABS I I I ' The mean concentrations of Cd in hepatopan creas, gill, coxal muscle and cheliped muscle of ----=---- and and in whole e (28.30)-... Fig. 9-14. -- .....--·\ \ I Samples of H. Pagurus sp. crabs \ were too infrequent to the distribution of I Cd within the survey area. \ 12.0' pancreas tissue is elevated at stations 5B and SB, and moderately elevated at station 7C (Fig. 9). The oo· distributions of Cd concentrations in the other Whole Mussels I tissues (Fig. 10-13) also reflect this general Mean Cd Concenlral10n so' pattern. 4.40 ~ Mytilus edu!is (46.69}- Modiolus modiolus The mean and range of Cd levels in C. irroratus tissues from the survey area were 87.1 (2.3-394.3), 17.4 (1.7-53.5), 5.3 (0.2-29.2) and 1.3 (0.1-8.1) ~g/g dry weight for hepatopancreas, gill, coxal muscle and cheliped muscle, respectively. The calculated mean and range of concentrations on a wet weight basis in hepatopancreas and coxal muscle were 7.1 (0.2-35.1) and 0.65 (0.03-3.8) ~g/g. C. l_rroratus (N=4) of approximately the same size range from Passamaquoddy Bay, N.B., and from ocean dump sites off the U.S. Atlantic coast (Table 3) had Fig. 8. Mean cadmium (Cd) concentrations in soft lower levels in their tissues. Concentrations in C. parts of M. edulis and M. modiolus sampled from the ~~~7 from two British sites (Topping 1973; survey area. and Reynolds 1971) were approximately the Table 2. Cadmium (Cd) concentrations reported for whole soft tissue of mussels. Cd concentration - mean or range Species (ppm) Location Reference 5. 1(dry wt)' Irish Sea Segar et al. (1971) 5. S(dry wt) Mytilus edulis 2. 5(dry M:) Southampton, U.K. Leatherland & Burton (1974) Mytilus edulis wt) New Zealand Nielsen & Nathan (1975) MOdiOIUs~landicus Mytilus edulis O.l-0.9(wet wt) Scotland Topping (1973) Mytilus edulis 0. 2-18. 2(wet wt) Victoria, Australia Phillips (1976) Nytilus galloprovincialis 0.4-5.9(dry wt) N.H. Mediterranean Fm.;rler & Oregioni (1976) Mytilus edulis 1. 4-4. 2(dry wt) St. Croix est., Me. Fink et al. (1976) Mytilus edulis 0. 9-1. S(dry wt) Maine Goldberg et al. ( 1978) 1. 7 (dry wt) Narrangansett Bay Mytilus edulis 2.9-112.2(dry wt) Belledune area This study Modiolus modiolus 15.2-55,6(dry wt) -15- variations in the proportion of viscera in the I'' scallops cause the Cd maximum to shift to transect \ 5. The data for C. islandicus were limited to two sampling stations. However, adductor muscle from both scallop species from the same sites contained ' \ approximately equal levels of Cd, while Cd concen ' \ "'11. 77\ I trations in the mantles and viscera of \ were considerably lower than for P. MUSSELS ~ 12.57 \ \ were collected from 13 stations from four stations within the and ::c.:c:::_::c:::.::c:::.::: :::c-:=== some stations, several M. were pooled for analysis but, 120' of variations in the Cd content of subsamples from the pooled tissues, the remaining mussels were 90' analyzed individually. All M. were Scallop Mantle analyzed individually. Mean Cd Concentration '"8.66 in the soft parts of M. edulis and " each station are illustrated in Fig. s.ss- Plocopecten magellanlcus ' (I 25}- Chlamys islondicus ' ' The soft tissues of M. edulis and M. contained a mean and range of 30. r (2. 9=1 and 32.1 (15.2-55.9) ~g/g of Cd, respectively. These concentrations are considerably higher than the Cd levels reported in the literature (Table 2) for mussels from unpolluted and moderately polluted marine areas. In from shore (A) stations (Fig. 7), the mean concentration decreases with distance to the north or south of transects 6 and 7. M. at stations lOC, 8C and SC contained Fig. 5. Mean cadmium (Cd) concentrations in mantles uniform concentrations of Cd (Fig. 8). of f· magellanicus and C. islandicus sampled from the survey area. \ "·--.(59 15) ~' * 168.71 I 120 111167.09 I 100 0' \ ' 223.07 '-.. I I 80 \ \ \ I 120' c 60 I \ ,. c: \ \ .2 ~ c: 40 Fig. 6. Mean cadmium (Cd) concentrations in the Fig. 7. Mean cadmium ( Cd) concentrations in soft viscera of p. magellanicus and C. islandicus sampled parts of M. edulis sampled at A stations (shore). from the su~vey area. -16- CRABS I I \ The mean concentrations of Cd in hepatopan creas, g Hl, coxal muscle and cheliped muscle of and Hyas araneus, and in whole ('I ~~~~~are illustrated in Fig. 9-14. (:II {28.30)" -"---- .___ --·\ \ I Samples of~· araneus and Pagurus sp. crabs .(34.871' \ were too infrequent to indicate the distribution of \ i Cd within the survey area. Whole Pagurus sp. I contained an average of 1.2 ~g Cd/g and H. araneus contained Cd concentrations of 4.2, 9.7,-0.6 and 0.8 Pte 48.55 ,, Verte ~g/g in hepatopancreas, gill, coxal muscle and cheliped muscle, respectl.vely. \ \ I The more extensive data for C. irroratus indi-· ·- cate that the mean concentration ~f Cd in hepato 120' pancreas tissue is elevated at stations SB and 8B, I and moderately elevated at station 7C (Fig. 9). The oo' distributions of Cd concentrations in the other Whole Mussels \ Mean Cd Concentration tissues (Fig. 10-13) also reflect this general pattern. 4.40 - Myti!us edulis (46.69)- Modiolus modiolus The mean and range of Cd levels in C. irroratus tissues from the survey area were 87.1 (2.3-394.3), 17.4 (1. 7-53. 5), 5.3 (0. 2-29. 2) and 1.3 (0.1-8.1) ~g/ g dry 0 10 9 8 7 6 5 4 3 2 0 t Transects Smelter Fig. 9. Mean cadmium (Cd) concentrations in the Fig. 11. Mean cadmium (Cd) concentrations in the hepatopancreas of C. irroratus sampled at B (9 m) coxal muscle of C. irroratus and H. araneus sampled and C (18m) stati~ns. from the survey area. ; ; I I ' • {0 54) ' • {3 651 ' \ ~- --- 0 34.85 --..._ $ 25.07 ....._ 3.11. I I ' ' ·' "26.30 \ I ' \ 'I \ I 90' 90' I Cheliped Muscle of Crabs Hepatopancreas of Crabe Mean Cd Concenlrotlon (~9 /g) Mean Cd Concentration .. 2.31 0.14- Cancer irrorotus 3.11~ Cancer irrorafus "'47.43 (0.14)-Hyas araneus {3.65)- Hyas aroneus Fig. 10. Mean cadmium (Cd) concentrations in the Fig. 12. Mean cadmium (Cd) concentrations in the hepatopancreas of ~· irroratus and H. araneus sampled cheliped muscle of C. irroratus and H. araneus from the survey area. sampled from the survey area. -18- I same as found in C. irroratus from the survey area. I ( r ' Gill tissue from ~. irroratus in the present study contained proportionally higher concentrations of Cd in relation to hepatopancreas tissue than did C. • I 10.611 pagurus analyzed by Over nell and Trewhella ( 1979). I PERIHINKLES I i ' Littorina sp. lvere collected at several shore ' \ (A) stations within the survey area. The mean Cd I concentrations in soft tissue (Fig. 15) are higher I at transects 5 and 6 than at transects 1, 9 and 10. \ o\ \ The mean and range of Cd concentrations in ' periwinkles from the entire survey area were 17.8 \ (1.1-44.0) ~g/g. This is higher than Cd levels reported for species from other marine 120'' areas (Table the exception of L. littoralis collected from the polluted Severn estu;ry so' (Leatherland and Burton 1974) and Bristol Channel Gllls of Crabs (Nickless and Stenner 1972) in the U.K. Mean Cd Concentrollon (llQ /g) ~ 9.36 3.61- Cancer irrorofus {10.61)- Hyos araneus LiUorina sp. ""'~ 0 <= ..... Fig. 13. Mean cadmium (Cd) concentrations in the 0 gills of C. irroratus and H. araneus sampled from - _J the survey area. c:: c 0 "§ c "'u c: 0 u 10 "0 u c;; 0 ::::;:"' '.. 1.38 I 10 9 8 7 6 5 4 3 2 0 t Transecls Smeller Whole Pagurue Crabill Fig. 15. Mean cadmium (Cd) concentrations in soft parts of Littorina sp. sampled at A stations Mean Cd Concenlrollon lll9 /Q) Q 1.16 (shore). o.s1- Pogurus pubescens (0.80)- Pogurus acodianus BARNAClES The highest mean Cd concentrations in Balanus balanoides collected at shore (A) stations were from animals collected at transect 3 (Fig. 16). However, mean concentrations decreased at transect 5 and rose to a second maximum at transect 7. The mean and range of Cd concentration in B. Fig. 14. Mean cadmium (Cd) concentrations in whole balanoides from the survey area were 1.5 (0.2-3~9) pubescens and P. acadianus sampled from the R· llg/g. There is little published information on Cd survey area. -19·- Table J. Cadmium (Cd) conc<•ntr;tt_lon,; •·eporlt•d for tissues of crab species. Cd concentration - mean or range Species ( ~ g/ g) Location Reference ------ 0. 4 (He t <-It ) Northumberland, UK Wright ( 1976) C • .E.':'l2.'_,.rus muscle 3. 6-5. 2(Het wt) Scotland Topping (1973) C. 5,/+(Wet \>Jt) Dt:von ~ UK Reyno Ids & Reynolds ( I 97 1 ) patop;wcreas 'JO.O(wet wt) C • .E.':'12.llCUS- gJ]] O.Fl-l.O(wet wt) OrknPy b., Scot. OvPrnell & Trewhl'11n (1979) - muscle 0. 1;-() • 9 ( w<: t wl ) he pa to pane reas 2. 0-17. S(wet wt) C. i rroratus - gill 0. 7-2. 7(wct wt) American Atlantic Greig et i-ll. (l977a) - muf-;cle 0.1-l.O(wet wt) - dumpsites he pe! to pane reils 1. 1-4. Fl(t.Jet wt) c. irroratus - gill 4. 2-21,, !(dry wt) Passamaquoddy Hay, Ray et al. (unpubl.) - coxal muscle 0. 5-6. 6( dry wt) N. B. - chel ired muscle 0. 02--0. 2(dry wt) - he pa to pancreas 8.8-ll'i.O(dry wt) c. irroratus - gill l.7-53.S(dry wt) flelledune area This study - coxal muscle 0.2-29.2(dry wt) - chel ired muscle 0. 1-8.1(dry '"t) - hepatopancreas 2. 3-391.. J(dry wt) !!. araneus - gill l. 3-19. 4(clry wt) Belledune area This study - coxal muscle 0. 4-1. 4(dry wt) cheliped muscle 0. 2-0. 9(dry wt) - he pa to pancreas 2. r,-s. 9(clry wt) (). 3-2.4(dry wt) lle 1 I eel nne :~reil 0. •,_ l • 1 ( cl r y wt ) 'lids stuclv -----·------·--·------·-· ------·-·------···------ Taole 4. Cadmi Cd concentration - mean or rf::l.nge Spec ic• s ( ~ g/ g) Location Re fe ren\ e L. (). 9(dry Littorea (). 03-0. 'l( wet wt) Scotland Topping (1973) L • .----- littorea 2. ()(dry wt) English Channel, UK Bryan (1976) L • ------ L • littorea !. J-2.1(dry wt) St. Croix est. Me. Fink et al. (1976) littorea ND-210.0(dry wt) Bristol Channel,UK Nickless Stenner (1972) L. ----- & L. l ittorea 0. 9-7 • 3 (we t wt ) UK, several areas Howard & Nickless (I 97 8) I~ • littorea J.J-41,,0(dry wt) ReJ ledune area 111i s study -----· -20- Balanus balanoides (A Stations-shore) c> Ciinocardium ciliatum Stations-31m) ~ "' "" ""':::l "" E CD"' 2 "" 2 ~ :: 0 0 <.:> -"" 0 3: c "' c:: .!::' 0 -~ 0"" <= -~ "'u <= 0 <.:> u ""c 0 -.::> u u -.::> c::; u 0 ..J 0 t::: 0 ::::;:"' 10 9 8 7 6 5 4 3 0 10 9 8 7 6 5 4 3 2 0 Transecls ::::;:"' Transecis Sm I r Fig. 16. Mean cadmium (Cd) concentrations in whole Fig. 17. Mean cadmium (Cd) concentrations in soft B. balanol.des sampled at A stations (shore). parts of C. sampled at D stations (31m). levels in barnacles from other marine habitats, but area. The fronds of F. vesiculosus and A. nodosum, Stenner and Nickless (1975) reported concentrations which are zones of rapid growth, were separated from of 4.5-12.1 llg/g dry weight for v1hole Balanus the stem, since the uptake of heavy metals by sea and from the polluted Rio Heeds appears related to groHth (Bryan 1969). It is balanoides con- not certain Hhether samples of digitata from each centrated Cd by a factor approximately 1200 station Here always taken from same portion of during 30 d exposure to seawater solutions of Cd the kelp blade. (Rainbow et al. 1980). The mean concentration of Cd in L. COCKLES the survey area is 0.8 (0.4-1.8) ]Jg/g~ data have been found for Cd levels L. -==.:;--;:::;:::-~"'= ~=== were collected at four D from other areas, but (1969) mean Cd levels in cockles from concentrations of 1.6 in transects 3 and 5 appear greater than levels in Seaton area of Britain. Since copper have a samples from transects 1 and 7 (Fig. 17) •, The mean similar affinity for alginate extracts of L. and range of Cd concentration for all samples were digitata (Haug 1961), it appears that conc;ntrations 1.2 (0.5-2.1) llg/g. This is higher than of Cd in the kelp from the vicinity of the smelter the mean Cd concentration of 0. 8 dry weight may not be excessive. The distribution of Cd con- reported for collected from Solway centrations in (Fig. 18) does not Firth, U.K. Burton 1974). conform to a pattern, possibly as a result of non-uniformity in the sampling of the kelp MISCELLANEOUS FAUNAL SPECIES blade. Polychaetes, flatfish The mean and range of Cd concentrations in samples from the survey area Here 8. =_;;;_;;==='-', edible whelk 77 pelican's foot ~~~~,~~g/g and 10.2 (1.3-30.3) ]Jg/g for stems were not collected at a and fronds, respectively. Similarly, mean and range to indicate the distribution of Cd within the of concentrations in A. nodosum stems and fronds survey area. A comparison between the mean Cd con were 6.2 (0.3-13.7) and 5.5 (0.6-18.0) ~g/g. These centrations in these biota (Table 5) and related concentrations fall Hithin the upper range of Cd species from other marine areas (Table 6) indicates levels in F. vesiculosus and nodosum from other that the polychaetes and flatfish are not exces marine environments (Table 7 • The Cd concentra sively contaminated Hith Cd, whereas IJ:• mercenaria tions at each station for these species are from station 5B and the tHo large gastropod species illustrated in Fig. 19-21. With the exception of 4 appear to contain elevated levels of Cd. out of 14 samples, concentrations were higher in fronds than in stems. Cd levels in F. vesiculosus MACROPHYTIC ALGAE from shore stations (Fig. 19a) were at a maximum at transect 7. Cd concentrations in A. nodosum are The brown algae, Fucus ~====~ less variable, but they follow the same general nodosum and Laminaria digitata, Here pattern (Fig. 19b). collected from shore (A) stations in the survey -21- Table 5. Mean cadmium (Cd) concentrations in flatfish, polychaetes and some mollusc species from the vicinity of the Brunswick Mines smelter, N.H. Mean Cd concentration (~g/g) Species by dry wt by wet wt Stations sampled Molluscs 9.8(6. 7-12. 9) 0.6(0.3-0.8) SB 39.6(0.1;-137.8) 4. 3(0.1-16. 3) OC, OD 14.3(0.2-98.3) 3.2(0.03-22.2) 1C, 3D, 7C, 7D, 8C, 10C Po lye haetes Arahellid 1.9(1.1-2.6) oc, 8D Nephtyid l. l ( 0 • 8-!. 6) 3C, 3D ]. 2 ( 0. 6-l. 8) 1D, 10D 0,1; 3D 2.9(2.2-3.6) lD, 10D !.1(0.2-2.0) 3C Flat· I ish (viscera) 0.9(0.3-2.0) oc, lC, 8B 0.6(0.4-0.9) oc, 1C, 10C american us 2.0 3C (muscle) 0.10(0.02-().L,O) 0.012( .004-.03) OC, 1C, 8B 0.07(0.05-0.10) 0.005(0.002-0.01) OC, 1C, 10C 0.05 0.005 3C T;ll'1" b. C;uimlum (Cd) concentrations reported lor flatfish, polychaetes and some mollusc spt~c-Les~ Cd concentration - mean or range Species ( ~g/ g) Location Reference Holt uses 2. 1 (dry >It) Irish Sea Segar et al. ( 1 97 l ) 0 • l -() • 2 ( we t wt) u.s. At 1. coast Zook et RL ( 1976) 2. :1 (d ry wt) Irish Sea St-~ gn r et ,l\ • ( I 97 l) 0 • I -ll • 2 ( Wp ' wt) ll. s. At J. CO(lSt C:rt>ig et a1. (I 977) Po tychiH' tes 1.0-2.0(dry wt) 0 • 2-4 • 3 (dry •1t ) St. Croix est., Fink et al. ( 19i6) 0. 7-2.2(dry wt) ~le. !. 9(dry wt) N. virens 0. 3-0. S(dry wt) Passamaquoddy Bay, Ray et al. (in press) N.B. N. diversicolor 0. 1-3. 6(dry wt) S.W. England Bryan & Hummerstone (1973) Flatfish (muscle) Limanda ferruginea Nl1-0.06(wet wt) Ceo rges Ilan k Zook et al. (1976) ND-0.2l(dry wt) German Bight Westernhagen et al. ( !980) ND-0.16(dry wt) German !light £._., platessa <. 002-. Ol (wet lvt) Lowes toft, UK Pentreath (1977) -22- Table 7. Cadmium (Cd) concentrations reported for rnacrophytic algae. Cd concentration range Species ( llg/ g dry wt) Location Reference Fucus vesiculosus (frond) 3.8-25.6 Bristol Channel,UK Fuge and James (1974) l:':_· vesiculosus (whole) 7.0-13.0 Norway Mel huus et al. ( 197 8) Ascophyllurn nodosurn 0.4-14.3 Norway Haug et al. (1974) (whole) F. vesiculosus (whole) 1.8-2.1 Near Liverpool, UK Foster (1976) A. nodosum (whole) 1. 5-1. 8 F. vesiculosus (frond) 1.1-1.4 UK, several areas Preston et al. ( 1972) F. vesiculosus (whole) l. 3-2.2 St. Croix est., Me. Fink et al. (1976) A. nodosurn (whole) o. 8-1.2 Larninaria digitata o. 4-1.8 Belledune area This study F. ------vesiculosus- stems 1.3-18.2 Belledune area This study - fronds 1.3-30.3 A. nodosurn - sterns 0.3-13.7 Belledune area This study - fronds 0.6-18.0 I I I I I Fucus vesiculosus (A Stations-shore) 0 ~ \ (..) \ 0 I :::;;:: I 1~0' 0 \ c: 90' Ascophyl!um nodosum \ <= Lamlnarls dlgltata 0 0 c: Q) (..) c:: 0 0 -.:::> 0 c: 0 0 Fig. 18. Mean cadmium (Cd) concentrations in L. Fig. 19. Mean cadmium (Cd) concentrations in£· digitata sampled from the survey area. vesiculosus and A. nodosurn sampled at A stations (shore). -23- SEDIMENTS I I Each sediment sample was separated into three particle size fractions silt-clay (<63 ' ~m), fine sand (63-250 ' gravel ( >2 50 ~m) • Shore fine and coarse sand, and sediments from B, C and D stations contained varying proportions of all three fractions (Table 8). Silt-clay fractions from C, D and some B stations analyzed for Cd. The fine sand fractions from A stations and selected B and C s ta tiona were also analyzed. At B and C stations, Cd concentrations in silt clay fractions (Table 8) reach a maximum at tran sects 8 and 5, respectively. The same trend is I obvious in fine sand fractions from these stations. I Similarly, Cd in silt-clay from D stations is I 90' slightly elevated at transects 3 and 5. Fucus vesiculosus In samples from shore (A) sta tiona, Cd levels Mean Cd Concentration (ug /g l in fine sand (Table 8) are variable, possibly as a 1.31 ~Stems result of erosi.on and deposition processes on the I 1 31 I -Fronds shore. However, there is a trend to higher Cd concentrations at transects 4 through 7. A comparison of the range of Cd concentrations in sediments from this study (0.1-7 .1 JJg/g) and from other marine sediments (Table 9) indicates that the sediments in the survey area are moderately contami.nated, but not as grossly contaminated as those reported for other areas by Bloom and Ayling (1977) and Bower et aL (1978). This may be partly because there are no fine fluvial sediments in the Fig. 20. Mean cadmium (Cd) concentrations in F. Belledune area. vesiculosus sampled from the survey area. The data of Loring et al. (this report) approximate the Cd levels found in sediments from this survey. The slightly lower concentrations in this study may be attributed to the smaller silt-clay fraction (<53 pm) analyzed by Loring. CONCLUSIONS ' \ The data for Cd concentrations in the silt-clay fraction of the sediments (Fig. 22) indicate B band of contaminated sediment extends diagonally from Belledune Harbour to the southeast across the \ sampling area. The data further show a decline in I the Cd concentration with depth of the water column. \ Table 10 shows that minimum concentrations of \ \ Cd were~ generally found in animals at the extremes of the survey area (transects 0, 1 and 10) and !20' maximum concentrations found in animals from I the center of·the area (transects 3-8). Results of t-tests show that the differences between minimum Ascophyllum nodosum and maximum mean Cd concentrations were significant Mean Cd Concentration (ug /g l (P < 0.05) for P •. ~~~~~~~ meats and mantles, i· M. sp. and~· balanoides 0.21- Siems (1.79) -Fronds viscera, irroratus muscle were because of high variability between samples and small sample size. Data for biota in which only one sample was taken per station could not be tested. The diagonal pattern of contamination, as noted for sediment, also seems to apply to Cd concentra tions in biota. As discussed throughout the text, Cd in the non-motile Fig. 21. Mean cadmium (Cd) concentrations in A. nodosum sampled from the survey area. -24- Table 8. Percent fraction of the whole sediment and cadmium (Cd) concen tration in the silt-clay and fine sand fractions. Silt-clay Fine sand Fraction Cd Fraction \Al Station (%) (~g/g) (%) ( p g/ g) 0/\ 96.4 0.8 JA 2A 48.8 0. 6 3/\ 1. 7 0. 2 4!1 0.3 2. 2 SA 4. 1 l. 'i 6A 2.6 0.9 71\ 1.1 1. 1 SA 9A s. 7 0. 3 lOA 1.2 0. 2 Oll 5.2 1.9 8.4 lll 2 7. 5 ]. 0 JB SB 1.5 83. 7 0.4 8ll 7. 1 67.3 5. 7 JOB 0.2 1.0 89.8 oc 0.9 0.9 63.9 o. 1 1C 14. 5 0.4 50.1; 0.2 3C 6.8 ]. I, 3 7. 5 2. 8 sc 7.2 '). 6 40. 1 6. 3 7C 1.8 ].8 14. 9 (). 3 8C 1.3 1.7 I;!.() 1 oc 2. 7 1.1 1 '). 2 0.4 OD 2. 5 o. 5 12. g 10 9.3 ().I; 22. 1 31l 2 ') 0.8 38.6 Sll Lt ~ 7 O.il 39.1l 7ll g.,q 0. 4 3b. 1 flD C\.9 (1.1, 20.1l ]()I) l ') .. s 0. '] 23.R Silt-cLty Table 9. Cadmium (Cd) concentrations reported for marine sediments. Cd concentration Sediment - mean or range fraction ( ~ g/ g cl r y wt ) Location Reference To till 0.6-0. 7 Southampton, IlK To tnl 3. l Severn est., liK LC'ntlwrLmrl illld Burton (1974) To ta 1 4.2 MersL'V c'st., UK <204 ~lin ND-4.0 Solway Firth, UK Perkins et al. (1973) Total 0.8-L 3 Solway Firth, UK Taylor (1976) Total <0.2-4.2 S.W. England Bryan and Hummers tone ( !973) Total ND-4.2 Long Ts. Sound, N.Y. Greig et al. (1977b) Tota 1 <1.0-15.0 Rcnit;cm Bay, N.J. Greig and McGrath ( 1977) <16 wm 0.6-20.0 Rhine-Neuse est., Salomons and ~look (1977) North Sen Total <0.'5-1400 Derw,,nt est., Au.st. Bloom and Ayling (1977) - Zn smelter To ta 1 l-908 Hudson R. est., N.Y. Bower et al. (1978) - battery factory To tal o. 2-850 Bryan (1976) Table• !(). Ratios and L-tests of minimum ;md maximum 111-ean cadmium ( Cd) concentrations in selected biota and sediments from the survQy area& Min .. mean Cd Station Nax .. mean Cd Station P-atio t-test Species cone., ( )l g/ g) II cone., (ll g/ g) !! max/min result P. Jl1agell;micus - me.:1t !.0 sc 8.4 3C 8.4 Significant - m patopancreas 2. 3 oc 394. 3 SB 171.4 coxal muscle 0.2 oc jl,, 6 81l 73.0 Not signi fie ant - cheliped muse., 0.1 3C 8. l 8C 81.0 ·- gills 1.7 lOB 53. 5 1+/1 31. 5 p. 0.3 !D 2.4 JB 8.0 B. 0.4 lA 2. 8 3A 7.0 Significant c. o. 7 7D 1.6 JD 2.3 Significant L. 0.4 OA 1.8 8A 4. 5 F. l.'l lOA "lO. 3 he\ 21. 3 - stems 1.1 lOA 18.2 bA ] 4. () A. nodosum -· ------fronds (1, l lOA IR.O ')i\ 6.0 - stems !.() 4A 13.7 )i\ n. 7 Sediment - silt/day o. 3 lOD 7. 1 Hll 23. 7 - fine sand (1.! oc 6.3 sc 63.0 -26- REFERENCES Sediment - Silt I Fraction Bloom, H., and G. M. Ayling. 1977. Heavy metals in the Derwent estuary. Environ. Geol. 2: 3-22. .____= Bower, P.M., J, H. Simpson, S.C. Williams, and Y. H. Li. 1978. Heavy metals in the sediments "":::l. of Foundry Cove, Cold Spring, New York. >- Environ. Sci. TechnoL 12: 683-687. 0 u .____ I \ C Sins Bryan, G. W. 1969. The absorption of zinc and ·- I \ other metals by the brown seaweed U) \ J, Mar. Biol. Assoc. u. c: I I <::: 0 l 1976. Heavy metal contamination in the I sea, p. 185-302. In Marine Pollution, R. ~ Johnston (ed.). Academic Press, N.Y. <::: 3 '-' ""'c: Bryan, G. H., and L. G. Hurnmerstone. 1973. Adapta- 0 u tion of the polychaete diversicolor to ""0 2 estuarine sediments high concen- u 0 trations of zinc and cadmium. J. Mar. Biol. c: Assoc. U.K. 53: 839-857. Cl ~ Fink, L. K., D. M, Pope, A, B. Harris, and L. L. Schick. 1976. Heavy metal levels in suspended particulates, biota and sediments of the St. 0 Croix estuary in Maine. OWRT Project No. B-010-ME, ICDC Ref. 76-22, Land Water Res. Inst., Univ. Maine at Orono, 60 p. Transects Foster, P. 1976. Concentrations and concentration factors of heavy metals in brown algae, Environ. Pollut. 10: 45-53. Fig. 22. Mean cadmium (Cd) concentrations in the silt/clay fraction of sediments sampled at B (9 m), Fowler, S. W., and B. Oregioni. 1976. Trace metals C (18m) and D (31m) stations. in mussels from the N.H. Mediterranean. Har. Pollut. Bull. 7: 26-29. Fuge, R., and K. H. James. 1974. Trace metal con stations were elevated at transects 5 through 8. centrations in Fucus from the Bristol Channel. For crabs (_£. irroratus) taken offshore at 9 and 18 Har. Pollut. Buil.S: 9-12. m, maximum Cd concentrations were found at transects 5, 7 and 8. Scallops P at 18m had Goldberg, E. D., V. T. Bowen, J. H. Farrington, G. maximum Cd concentrations at transect Further Harvey, J. H. Martin, P. L. Parker, R. H. offshore, at 31 m, C. ciliatum from transects 3 and Risebrough, W. Robertson, E. Schneider, and E. 5 contained maximum --Cd concentrations. Gamble. 1978. The mussel watch. Environ. Conserv. 5: 101-125. In comparison to data reported for biota from other marine areas, in this survey the filter- Greig, R. A., and R. A. HcGrath. 1977. Trace feeding bivalves M. edulis, M. metals in sediments of Raritan Bay. Har. modiolus, ciliatum, .contained high Pollut. BulL 8: 188-192. levels of ---As may expec , predators upon bivalves (~. undatum, A. occidentalis) also Greig, R. A., D. R. Wenzloff, A. Adams, B. Nelson, containe.d very high Cd-concentrations. In addition, and C. Shelpuk. 1977a. Trace metals in the herbivorous gastropod, Littorina sp., the organisms from ocean disposal sites of the filter-feeding crustacean B. balanoides, and the middle eastern United States. Arch. Environ. carnivore/scavenger C. irr;ratus contained high Contam. Toxicol. 6: 395-409. levels of Cd. Of th; biota analyzed, only macro phytic algae, polychaetes and flatfish species Greig, R. A., R. N. Reids, and D. R. Henzloff. contained Cd levels near reported "baseline" 1977b. Trace metal concentrations in sediments concentrations. Low concentrations in the latter from Long Island Sound. Mar. Pollut. Bull. 8: taxa may be related to their mobility, and low Cd in 183-188. algae may indicate low levels of dissolved Cd in water in inshore areas. -27- Haug, A. 1961. The affinity of some divalent Ray, S., D. W. NcLeese, and M. R. Peterson. !9HO. metals to different types of al.ginates. Acta Accumulation of copper, zinc, cadmium and lead Chom. Scand. 15: 1794-1795. from two contaminated sediments by thr<>e marine invertebrates - a laboratory study. Estuar. Ha ug, A. , S. He l som, and S. Oinang. 197 4. Coast. ~1ar. Sci. (in press). Estimation of heavy metal pollution in two Norwegian fjord areas by analysis of the brown Reynolds, C. V. , and E. B. Reynolds. 197 l. Cadmium nodosum. Envi.ron. Pollut. 7: in crabs and crabmeat. J. Assoc. Publ. AnaL 9: 112-llS. Howard, A. c:., and G. Nickless. 197 8. Heavy metal Salomons, , and H. G. Hook. !977. Trace metal complex;;tion in polluted molluscs. III. concentrations in estuarine sediments: mobilization, mixing or precipitation. Neth. J. Sea Res • 11 : 11 9-l 2 9. Segar, D. A., .J. D. Collins, and .J. P. Riley. 1971. 'TI1e distribution of the major and some minor Leather land, t1., and J. D. Burton. 1974. 11w elements in marine animals. Part IL Molluscs. occtlrreilCe of sorne trac met~tls in coastal J. Har. Biol. Assoc. U.K. 51: 131-136. organisms with particular reference to the SoJent region. J, Mar. llioL Assoc. U.K. 54: Stenner, R. D., and G. Nickless. 197'i. He;lVv 4'>7-1•68. metals i.n organisms nf the Atlantic coast nf S.\V. Spain Nickless, C., cmd R. Stenner. 1972. DJ stribution Topping, G. 1973. Heavy metals in shell fish from o cadmimn, lead and zinc in the Bristol Scottish waters. Aquaculture 1: 379-384. Channel. r1ar. Pollut. Bull. 3: 188-190. Westernhagen, H. Von, V. Dethlefsen, and H. Nielsen, S. A., and 1\. NBt:han. 1975. Heavy metal Rosenthal. 1980. Correlation between cadmium leve-ls ill Ne" Zealand molluscs. N.Z. J. Mar. concentration in the water and ti.ssue residue Freshwater Res. 9: 467-l!fll. levels In dab, Limanda limanda L., and plaice, platesso L. and the thornback ray, Overnvll, J., and 1•:. Trewhella. 1979. Evidence ror L. J, Har. lliol. Assoc. U.K. 6(1: the natltrrt1 occurrence of (cadm1urn, copper) mc•L1llothione!.n in tl1e crab ~gurus. C:nmp. Biochem. Physiol. 64C: Wright, D. A. 1976. Heavy metals in anim;lls from the northeast coast. flar. Pollut. Bull. 7: Pentreath, }(. J. 1977. The accumu1atlon of cadmium 36-38. h y the plaice , _:_:::.:c=::-=c=. .-:c:= J..=:=:::-_:c=::: and the tlwrnback ray, • Mar. Zook, E. C., J, J. Powell, B. N. Hackley, .J. A. BioL EcoL 30: Emerson, .J. R. Brooker, and C. M. Knobl, Jr. 1976. National :'Iarine Fisheries Service Perkins, E. J., J. R. Gilchrist, 0. Abbott, preliminary survey of selected seafoods for and ll. Ha lcrow. 1973. Trace metals i.n Solway mercury~ lead, cadmium, chromium and arsenic Firth sediments. Har. Pollut. llull. 4: 59--G!. content. J. Agric. Food Chem. 24: 47-53. PP~ch, C-., B~ Reynolds, and P~ Rogerson~ 1977~ Tl-:-lCl' metals in scnl!nps from within ,Jnd .1round two ocL~ Phi 11 ips, il. J. ll. 1976. The common mussel.~~·--- is as an ind~ator of pollution by urn, lead and coppPr. II. RPlationship of rnetal_s in tl1e mttssel to tl1ose disc~harged by industry. Mar. lli.ol. 38: 71--80. Preston, A., [). F. Jefferies, J. W. R. Dutton, B. R. Harvey, and :\. K. Steele. 1972. llrHish Isles coast S~, ~~~ Rn inbow, P .. /-\, C., Scull, /\, \"i?,gins 1 ;md 1(, \1 • .i !lpp<'IHI ix T nnd is 1 n1ullcus Sc" I I ops - P. ~~~!_5~~~ c. -----·-··--- Dry weight-wet wr•l gilt relnt i Dry wt (g) Cd (~g/ g dry wt) Station Valve length (em) Meat Viscera Mantle Meat Viscera Mantle P. magellanicus OC-l 18.0 3.6 !.2 1.1 7. 9 192.0 9. l OC-2 14.0 6. 7 0.9 2.8 6.6 191.3 11.3 OC-3 8.5 0.9 1.6 0.6 1.5 92.6 5.7 3C 13.0 4.2 2. 3 2.3 8.4 223.1 12.6 5B 13. 5 5. l l. 2 1.9 7. 7 493.2 18.0 5C--l 7.5 1,,() !. 8 1.1 5. 6 185.5 5. 8 5C-2 8.3 2.2 2. 5 0.3 4.4 223.9 17.6 5C-3 11.0 0.9 0.9 0.5 2.0 121.0 11.9 7C-1 7.5 0.9 0.9 0.3 3. 0 111.6 8.1 7C-2 9.0 2.4 1.6 0.8 3.5 156.2 6. 7 lC-3 12.0 5.2 1.0 1.3 1,, 2 233. 5 9.4 SC-I 7.0 0.9 o. 7 0.3 1.1 II 7. 1 4.9 8C-2 11.0 J. 9 0.9 1.1 !. 7 1.19. 8 3. 3 8C-1 7.0 !.9 1. l o. 3 13. 3 24.9 1.1 8C-2 8.5 i.9 1.3 0.0 1.0 93.4 2. 3 lOC-I 6 .. 5 5.2 o. 7 0. l 3. t, 21.4 l.l lOC-2 7.0 l.l !. 0 0.4 0.5 29.8 l. 4 -29- Appendix I (coat'd) Musscels M. edulis and N. modiolus Dry weight-wet weight relationship: Het wt 12.6 + 3.9 (dry wt) Station Valve length (em) Dry wt (g) Cd (~g/g dry wt) M. edulis OA-1 s. 8 o. 7 13. 9 OA-2 6.3 J. 5 12.2 !A 7P (4.3-6.2)8 1.9 19.0 2A SP ( 6. 1-6. 7) 2.6 33. 7 JA SP (5.8-7.8) 2.6 30.0 3B-1 7.4 2. 5 26.9 3B-2 6.4 1.7 25. 5 JB-3 6.9 J. 5 26.2 I, A 4P ('i.J-6.6) 2. 1 48.6 SA SF (5. 7-6. 4) 2.9 53.4 6A SP ( 4. 9-6. ')) 2.0 112. 2 ?A 4P (I,. 7-7. 4) 2.6 102.9 9A lOP (3. 9-8. 2) 2.0 20.3 lOA SP (6.3-8.0) 2.0 14.9 lOB-1 6.6 1. 9 6.6 1 OB-2 6.0 1.2 7.0 lOfl-3 8.2 2. 3 9.0 lOC-1 6.7 1.4 5.9 1 OC-2 s. 8 o. 5 2.9 M. modiolus 1B-l 9. 5 2.9 24. 1 1B-2 7. 7 1.6 15.2 sc 53.4 5.4 34.9 8C-1 29.0 3.9 24.4 8C-2 63. 8 4. 1 32.2 lOC-1 111. 1 15.6 55.9 1 OC-2 108.8 15. 3 37.8 8 xP (n1-n2) refers to the range of valve lengths [or a pooled SE!tnple of x number of animals. -30- Appendix I (cont'd) Crabs - c. irroratus and H. araneus Dry weight-wet weight relationships: He pa to pancreas - Wet wt 2. 1 + 3.2 (dry wt) Gills - Wet wt 1. 6 + 9.6 (dry wl) Coxal muscle - Wet wt 1.5 + 4. 7 (dry wt) Cheliped muscle- Wet wt 0.8 + 4.5 (dry wt) Carapace Dry wt (g) Cd (~g/g dry wt) Stat ion length (em) Hepato. Gills Cheliped Coxal He pa to. Gills Cheliped Coxal c. irroratus OB-1 8.2 0.8 0.4 ]. I, 0.3 ill. 4 2[.4 0.2 0.6 OB-2 7.6 0.6 0.4 1.2 0.2 !3.5 19.4 0. I 0.4 oc 4.8 0.1 o. 1 0. I 0. I 2. 3 9.4 0.2 (1. 2 lll 6.9 0.7 0.2 0.4 o. 2 5.4 10. 2 !.2 o.s 3C 7.6 o. 7 (),1, 0.9 (),] 26.3 7.4 0.1 (). 8 5!3 5.0 0.1 0. I 0.2 0.2 394.3 19.8 2.0 10. 7 7C s. 3 o. 5 0.2 0.6 0.2 85.8 24.6 0.9 2. 7 8B-1 5.6 0.3 o. 1 0.4 0.2 280. 3 23.2 o. 7 29.2 SB-2 7.5 1.1 0.3 1.4 0.4 56. I 12.0 0Lo4 ' 9.9 8B-3 7.4 0.3 0.1 o. 3 0.2 124.4 53.5 0.8 4. 6 8C s. 5 o. 5 0.2 o. 5 0.2 25. 1 20. 1 8. 1 6. 3 lOB 4.9 0.6 0.1 (). 7 (1.1 3. 1 1. 7 0.2 0.4 lOC 6.8 0. 7 o. 2 0.3 0.1 34.9 3.6 0. I 2.4 ll. araneus 1C 7.5 0.6 0. 1 0. 3 o. 2 5.9 6.9 0.6 1.4 7D-1 10.8 1.2 o. 7 1.6 1.6 5.3 19.4 0.9 o. 7 7D-2 9 ~ ) 3. 7 0.2 2. 5 1.5 3.1 1.3 0.2 0.4 7D-3 9.9 1.1 o. l !. 6 o. 3 2.6 ll.l o. 5 0.6 Polych;1cetes St0tion Spec ie s \-Vet wt (g) Dry Wl (g) Cd (~ g/ g dry wt) oc Ar abelli.d 0.2 O.l ].I lD sp. 1.6 0.2 1.8 lD sp. 4. 4 !.I 2.2 3C: 1.0 0.2 1.6 3C: 56. 7 8.0 2.0 3C 1.2 O.J 0.8 'lC: 50.4 5.4 0.2 31l 1.'3 0.2 1.0 3D J=. .. squamatus 0 .. ~~ 0. I 0.4 8D i\r nlw l 1 ld o. 3 0. I o. 1 ]()[) ~r.J: l od OC_<:_ sp. ],1, (). l 0.6 lOll An1hell icl (1,1, tl.l 2.h JOD Clymenel1a sp. 7.0 J.l 1.6 ------·--- -31 Appendix I (cont 'd) Flatfish Dry weight-wet weight relationships: Muscle -Wet wt 2.8 + 8.1 (dry wt) Viscera -Wet wt = 5.1 + 4.2 (dry wt) Sample Whol.e Cd(11g/g dry wt) Station Sppc Jes Length (em) '"et wt (kg) Huscle Viscera oc L. 29.0 ().2) (), 1 4. 6 o.os 0.44 oc !!. J JL; • 0 0.36 J. 0 'J.O 0.03 0.26 oc -2 22.0 0.18 l.O 1.8 o. 12 I. 31 1C L. 1 23.0 o. 14 0.6 0.8 0.05 o. 93 1C 28. 5 0.21 1.0 2.6 o. 11 o. 60 IC H. 31. 0 (). 22 1.2 2. 2 (). 02 o. 77 IC 27.0 o. J il 0. 7 1.7 0.06 o. 36 3C P. americanus 31.0 0 • L;O 3. 2 3. 4 0.05 !. 97 8B H. platessoides 30.0 0. I 9 0.0 I. 2 0.41 l. 95 lOC ferruginea 29.0 0.28 0.6 4.8 0.07 o. 55 Whelk B. undaturn Station Wet wt - soft part: s ( g) Dry wt (g) Cd G g/g dry wt) 7C-l 16.9 2.7 0.4 7C-2 43. 5 L,, 8 3.8 SC-I 10. '5 1.4 2.0 SC-2 16.8 2.9 6.3 SC-3 23.4 [.9 137.8 SC-4 21. 3 3.2 108.5 lOC 17.8 3. 3 18.2 American Pelican's Foot - A~ occiclentalis Station Het wt - soft parts (g) Dry wt (g) Cd C11g/g dry wt) oc 2.6 (2 animals) 0. L; 0.2 OD 1.1 0.2 o. 3 JC 2.9 o. '5 0.4 3D 2.4 0.4 0.2 7C: 1.2 0.3 98. 3 7D 2. 1 O.J 0.2 sc: 6.4 (5 an ima1s) 1.0 0.6 -32- Appendix I (cont'd) Quahog - M. mercenaria Station Valve length (em) 'Ae t wt: - so f t parts (g) Dry wt (g) Cd (\1 g/ g dry wt) SB-1 10.4 196.9 12.8 12. 9 SB-2 3.8 6. 5 0.4 6. 7 Crabs P. l'_ll_i1escens Hnd P. acad i_anus - ~~-~--~ Station Species \1e t wt (g) Dry wt (g) Cd ()lg/ g dry wt) oc P. Jl.lclhescens 2. 1 () .., ().9 oc h. 5 1.7 1.5 lD 17.4 I.,() 0.3 Jll !.3 0.3 2.4 3C 8.3 2 ~ () 1. 4 SB 3.6(4 anim) 1.1 1.4 sc P. acadianus 1o. 9 3. 2 1.6 lOB P. oubescens 2. 2(2 anim) 0.6 o. 5 IOC P. acadia nus 3.8 1.1 0.8 -~--- Cockles - c. ciliatum Station Valve length (em) Wet wt - soft parts (g) Dry wt (g) Cd ( \lg/ g dry lo.'t) l D-1 4.8 22. 1 2. 2 0.8 1 D-2 4.7 13. 5 ], 3 1.1 30-1 I,, 7 !'l. 2 1. 4 1.1 'lll-2 1,, R l 3. 3 !.4 2. I SD-1 1+. 5 9. 3 0.9 1.5 Sll-2 4.4 10.8 ].0 1.2 7D-l 4. 5 l 1. I, 1.5 o. 5 7D-2 4.9 12. 7 1.3 0.9 -33- Appendix I (cont'd) Barnacles (_I?_. balanoides) and periwinkles (Littorina sp.) Data for dry weight-wet weight relationships not available. Barnacles Periwinkles Station Dry wt (g)a Cd (pg/g dry wt) Station Dry wt (g)a Cd (pg/g dry wt) lA 2. 5(4) 0.5 lA 3.1(4) 6.5 lA 2.3(1,) 0.1, lA 3.3(3) 7.7 lA 2. 1 ( 4) 0.3 SA 0.6(2) 8.0 3A 0.4(!) 2.9 SA 0.1,(1) 14. 2 3A 1.4(2) !.7 SA o. 4(1) 19.2 3A 1. 7(2) 3.9 SA o. S(l) 26.3 SA 0.4(1) 1.1 SA O. S(l) 31. 1 SA 1.2(4) 1.2 6A 0.2(2) 18.0 SA 1. 3( 5) !.4 6A 0.3(2) 44.0 SA 1. 5(5) 1.5 6A 1.4(5) 1.1 6A 0. L,(3) 43.0 6A 1.5(5) 2.9 9A 0.3(3) 2.0 6A 1. 3(5) 1.7 9A 0.3(3) 10.9 6A 1. 7(S) 1.5 lOA 0.1(2) 1.1 7A 0. 7 (1) 2. 1 7A 1.1(6) 1.8 7A ().9(5) 2.2 () ') 9A 1.1(6) o L 9A 0.6(4) 0.7 9A 1.9(5) 0.6 ~~~----··---~-~~--~------~-- "Data in parentheses refer to numbers of animals used in a pooled sample. Appendix I (cont'd) Macrophytic algae Data for dry weight-wet weight relationships not available. L. digitata F. vesiculosus - frond Station Dry wt (g) Cd (~g/g dry wt) Station Dry wt (g) Cd (l!g/ g dry wt) OA 0.7 0.4 OA 3.9 6.3 lA 5.0 1.2 lA 3.0 5.8 lil 0.8 1.2 Ill 7.0 2. 5 2A 3. 5 0.8 2A 3.9 2.9 JA 3.8 0.8 3A 8. I 13.3 3ll 2.2 0.8 6/\ 3. I 18.9 4/\ 2.4 0.7 7A 4.0 30.3 SA 3. 5 0.6 9A n. 7 1.3 Sil 1.6 1.3 6A 3. l 0.4 A. nodosum - stem 8A 1.7 !.8 9A 1.2 o. 7 lOA 1.5 0.4 3A 1.4 13.7 lOll 2.6 0.7 4A 5. I 1.5 SA 0.3 13.7 F. vcsiculostJS - stem 8A J. 5 7.2 -· ~-~---- 9A ].() 0.6 ------·---~----~~------lOA I. 3 0.3 ()A 0.9 2. 7 l/\ 0.2 8. 'j A. nodosum - frond J H l.l !].() --~~------2A 0.4 1.7 3A n. s 9.8 3A 7.4 0.6 6A 0.1 18.2 4A 3. I 1.0 7A 0.9 8.2 SA 3.9 18.0 8A 12. 9 10.9 911 7. 7 0.8 lOA ll. 4 1.8 -35- A PRELIMINARY SURVEY OF CIRCULATION AND HEAVY METAL CONTAMINATION IN BELLE DUNE HARBOUR AND ADJACENT AREAS by D. H. Loring, J. M. lleHers, G. Seibert, and K. Kranck Ocean and Aquatic Sciences Department of Fisheries and Oceans Bedford Institute of Oceanography Dartmouth, Nova Scotia B2Y 4A2 -36- INTRODUCTION This document is a preliminary report of the circulation studies, sediment and suspended matter results, size analyses of sediment particles and Following a request from the Fisheries Manage water analyses, respectively. ment of the Department of Fisheries and Oceans, units of Ocean and Aquatic Sciences, Atlantic, conducted a preliminary survey of the circulation PHYSICAL OCEANOGRAPHY and heavy metal contamination of sediments, water and suspended matter in the marine environment surrounding Belledune Harbour, N.B. The field work This note summarized the physical oceanographic was conducted using the vessel NAVICULA between May data obtained by the Bedford Institute in 1964 6 and May 8, 1980. 1wenty-two grab samples and six (Canadian Hydrographic Service 1965) and 1980. For water samples were collected at selected sites in the dispersal and movement of water-borne contami Belledune Harbour (Fig. la) and a further 13 grab nants, the following processes are thought to be and 12 water samples were obtained from coastal zone important (no relative scale): transects both to the west and east of Belledune Harbour (Fig. lb). At each location from which (1) Nature and strength of the coastal water samples were collected, a sample of suspended eire ulation; particulate matter (SPH) was also obtained. A vertical profiling current meter was used to obtain (2) Response of the harbour to external hydrographic information. events; b')"(K) - ----~------(3) Circulation within the harbour, source points of contaminants, and exchange with the coastal zone ( 5 km) • NATURE AND STRENGTH OF THE COASTAL CIRCULATION There are several current systems in the near shore zone which dominate the water movements. We will confine ourselves to discussing two: (a) long shore currents produced by an oblique wave approach to the shoreline; (b) coastal currents due to freshwater runoff. (a) Longshore currents due to waves - this type of current is significant in that it is responsible for the net transport of sand or other beach material along the shore. Belledune Point is subjected to wave action from a sector ranging from NW through north to southeast; however, only the eastern fetch has considerable length. The wave Fig. la, Station locations in Belledune Harbour. characteristics for this sector range from 2,1 m@ 5 s to 5.8 m@ 9 s, The longshore current for waves coming from the east is shown in Fig. 2. Note the convergence zone on the east side of the Point. It should be no ted that the wave action on the eastern side of Belledune Point is usually heavier than on the western side, giving rise to a net littoral drift which is oil predominantly west,vard, However, other •18 •19 current systems may modify this pattern, >lli3 •14 <:1;5 (b) Coastal currents due to freshwater runoff fresh ~Jater by the Restigouche River (600 smaller coastal tributaries set up a flow along the southern coast. Current measurements in 1964 and spot measurements at some of the locations shown in Fig. 1 show that typical rates in the surface (0-10 m) layer are of the order 10-20 cm/s, directed to the east, and following the coastline, Large varia tions in those speeds could however occur, achieving maximum values of 1.6 knots. Figure 3a shows a qualitative picture of the coastal flow determined from parachute drogues released at regular intervals during August 1964. In general, the flow offshore tends to be aligned with the shoreline; some flow separation may occur due to the projection of the breakwater Fig. lb. Station locations on coastal zone into the stream. If we assume that this transects. -37- flow is decoupled from those waters below 10 m, an estimate of the width of this current can be made. Measurements in May 1980 show a typical density contrast of 2 x l0-4 A.ssuming a rate of 15 cm/s and ' \ thickness of 10 m, the width of this A current will be about 2 km. \ \ RESPONSE OF THE HARBOUR TO EXTERNAL EVENTS During May 1980, a sub-surface pressure gauge was installed at the inner end of the wharf. This gauge measured total pressure (atmospheric + / pressure due to fl uc tua tions in mass above the instrument) every 30 s over a time span of 2 d • "'"' / ' .... \ Figure 4 gives the variation of equivalent water / height for the duration. Note that the only \ significant variations are due to tides. Seiching, which could contribute to the flushing of the \ harbour, is either absent or insignificant during \ the sampling period. N \ 0 200 400 METRES t Fig. 2. Direction of longshore current. A - for waves from NE; B -for waves from east. 50' 40 48' 00' BAlE DES CHALEURS --===-~~ TlmP 55' Fig. 4. Water level time history - Belledune ""-~"'~ ~\' Harbour. 0 .. . v,;} ·•\.""' \ 'O'v" ' ··:·."':i•\ CIRCULATION WITHIN THE HARBOUR .... ·. 50' 50' The coastal flow due to freshwater discharge is 50' 40' of sufficiently large scale that it does not "see" the opening of the harbour. However, a flow past Fig. 3a. Coastal currents due to freshwater runoff its mouth could introduce a circulation pattern as in the vicinity of Belledune Point. shown in Fig. 3b. If this picture is correct, it tends to indicate that the exchange between harbour and coastal flow is limited to diffusive effect only; for all practical purposes the harbour is a 50' closed system. However, this pattern could be altered when easterly or northeasterly winds disturb the coastal flow. BOTTOM SEDIMENTS After removal of material >2 mm, a representa tive part of each sediment sample was oven-dried for chemical analysis. From another portion of the sample, the sand particles (2.0-0.053 mm diam.) and mud size particles ( <0. 053 mm diam.) were separated by wet sieving, and the fraction <0.053 mm or 53 um was retained for chemical analysis. The amounts (by weight) of the sand and mud size material in each sample (Table 1) were also used to classify the textural characteristics of the sediments according to the nomenclature of Loring and Rantala (1977) and to estimate the partition of cadmium (Cd) in the Fig. 3b. Circulation pattern in Belledune Harbour. sediments (Table l). -38- Table 1. (',admi um (Cd) in llelleclune Harbour and coastal sediments. Sus pend ed particulate Station Sediment Mud ~{, mud (<53 pm) matter no .. (ppm Cd) (ppm Cd) (in sediments) (ppm Cd) Lagoon 12.6 13.0 61+. 8 Slag 53.6 I lla rbour not analyzed sand 6.6 srtnd 2 Harbour 9.2 7.9 58.6 3 Harbour 9.2 15.6 42.8 s. 7 4 Harbour 9.5 13.8 33.4 5 Harbuur 13.3 19.6 56. I 15.2 6 Coastal 1.8 4.4 33.8 2.6 7 .I .4 36.8 6.2 8 Coastal • 2 .6 43.6 3. 1 9 Coastal • 5 1.2 48.6 10 Coastal not analyzed 1.1 gravelty sand 2.8 gravelly sand J 1 Coasta t . 2 ,f) 24.8 2. I 12 Coastal • 2 1.6 9.3 3. 5 I 3 Coastal not analyzed rocks 4.0 (rocks) 14 Coast at • 2 J. J 13.4 4.6 15 Coastr-11 l.il 8. ') 30.3 2.4 16 Coastal 2.8 6.6 1,2. 7 5.0 17 Coastal • 2 .4 52. 1 2.9 18 Coastal • 2 • G 32.1 2.9 l 9 CoastaL • 3 .a 37.5 3.4 20 Harbour 16.9 27.8 26.9 96.0 21 Harbour 30.0 40.2 so. 8 23.6 22 Harbour 60.8 54.8 83.4 23 Harbour 49./; 61.5 so. 2 24 Harbour 60.8 63.5 05.2 2'i Harbour 39.G 41,, 6 41,. 9 2() Harbour 54.2 74.0 54. 1 27 Harbour 1;6. f) 38.4 8'3. s 2il Ha rhour JL•• 0 34.4 i\6.3 l!J llarhour 21.0 28. 3 3il.6 30 Hct rbour 2 I. 'l 28.0 'iS. 11 31 ttarbour II(,. 6 4').4 69.6 32 Harbour /+].() 37.2 84. s 31 Harbottr 32. 2 34.11 79.9 ]I; thrbour 10.6 17.6 II]. 2 35 Harbour ]!,. 6 l 9. 2 47.7 36 Harbour 16.0 23.3 50. 2 37 Harbour 16.4 21.8 4 7. l -39- t;4•so The harbour sediments contain <5-86% by weight ------~:0~ ------,---- mud and 14->95% sand. Texturally they vary from sand (>95% by weight sand particles) through very sandy (>30% sand) muds, to the sandy (5-30% sand) muds (Stations 21, 22, 27, 28) found just off the lagoon and wharf breakwater. ., CADMIUM IN SEDIMENTS AND SUSPENDED PARTICULATE MATTER Total Cd and zinc (Zn) concentrattons were determined by using flameless (Cd) and flame (Zn) A. A. techniques in a dried portion ( 10-500 mg) of the total sample, in a portion of the 0. 053 mm fraction from each sample, and in the SPM. Total Cd varies from 9-61 ppm in the harbour BEL.LEDUNE WHfiRF sediments (Fig. 5). The highest concentration (30-61 ppm) occurs in that part of the harbour west of a line drawn between Chapel Pte and the end of the breakwater. Seaward, Cd concentrattons drop to 9-17 ppm off and to the east of the Brunswick Mining Fig. 6. Cadmium (Cd) in <53 ~m fraction of sedi and Smelting Limited outfall. Since the highest ments (ppm) in Belledune Harbour. concentrations occur along the edge of the lagoon breakwater and around to the wharf, the Cd pattern 64"50 suggests an input of Cd-rich material in this area. ------~----- The enrichment factor for these sediments is about 100-200 times above a background level of about 0.3 ppm found in the adjacent coastal sediments. e 1.8 oil • I) • 10 ., ., FlELLEDUNE WHARF ____ _!_'f-l Fig. 7. Cadmium (Cd) in >53 pm fraction of sedi BCLl_EDUNE WHARF ments (ppm) in Belledune Harbour. pattern as the Cd in the total sample and <0. 053 mm Fig. 5, Cadmium ( Cd) in sediments (ppm) in Belledune fraction. The enrichment factor for the Cd-rich Harbour. sand material is about 150 times above a calculation background level of about 0. 05 ppm Cd in the offshore sand fraction and is the same as the enrichment factor found in the mud-size material. In the mud fraction (<0.053 mm), Cd concen trations vary from 8-74 ppm (Fig. 6) and have a Further calculations of the contributions of Cd comparable distribution pattern to those found for in the sand and mud size fractions to the total Cd the whole sediment. High Cd concentrations (28-74 concentrations show that 13-56% of the total Cd in ppm) occupy the western part of the harbour and the harbour sediments occur in the sand size decrease seaward (8-28 ppm). TI1e enrichment factor fraction and the remainder (44-87%) of the Cd is for Cd-rich material is about 50-150 times above a contributed by the mud size fraction. Regionally, background level of about 0-5 ppm we found in the the highest percentage (30-56% of the total) of Cd offshore mud fraction. contributed by the sand size fraction occurs in the western part of the harbour and the lowest percen Calculation of absolute concentrations of Cd in tages occur seawards. TI1e sand size particles the sand size fraction (Fig. 7) (2.0-0.53 mm) from contribute 3.0-19.6 ppm Cd to the total Cd concen the total and <0.053 mm Cd data indicates this total tration of the samples and the mud size particles Cd in the sand fraction varies from 4-91 ppm. The contribute ,.,7. 5-48.7 ppm. The highest concentra highest concentrations (88-91 ppm) of Cd occur just tions of Cd-rich sand contributions (.-v20 ppm Cd) off the wharf and form part of a Cd-rich sand area occur just off the lagoon breakwater and thus (52-91 ppm) in the northwestern section of the decrease gradually seaward with concentrations harbour. Seaward over a distance of L 5 km the Cd falling to 5 ppm at the mouth of the harbour. High concentrations decrease sharply towards the harbour Cd concentrations in the mud fraction (--'30-45 ppm) mouth (52-5 ppm) and follow the same dispersal also occur in the western part of the harbour. -40- Seaward Cd contribution in the mud decreases sharply from 30 ppm off Chapel Pte to <5 ppm at the mouth of the harbour. This partition pattern and the absolute Cd concentration in the sand and mud fractions (Fig. 6, 7 respectively) imply that Cd-rich particles are bimodal and represent the input of both relatively coarse and fine Cd-rich material to the harbour, They also indicate that the Cd-rich coarse- and fine-grained material is also mostly trapped at the head of the harbour adjacent to the breakwater with little Cd-rich material being transported more than 1. 5 km seaward, Although the exact source has not yet been identified, the coarse particles may reflect spillage of Cd-rich materials (see Sergeant and Ray, this report) and the deposition of the fine-grained particulate Cd, perhaps from the out fall, as suggested by the high Cd concentration (~96 ppm) of the SPM at the outfall at the southeastern corner of the harbour. Offshore, most of the Cd (70-99%) is located in the mud size fraction and the sand fraction does not contain any significant amounts of Cd-rich sand size particles. Fig. 9. Cadmium (Cd) in sediments (ppm) on coastal zone transects. Five spot samples from the harbour contained approximately 6-96 ppm Cd with the highest concen tration (96 ppm) occurring at the Brunswick Mining and Smelting Limited outfall (Fig. 8). Other high The distribution of Cd in the <0.053 mm values (24 ppm) occurred in the center of the fraction also shows the extent of the seaward harbour and at the seaward end (15 ppm) of the migration of Cd (Fig. 10). In this fraction Cd breakwater. At the mouth of the harbour on its concentration varies from 0.4-8.5 ppm Cd. The southward side, Cd levels are reduced to 6-7 ppm. highest concentration (8.5 ppm) also occurs at station 15. About 2 km seaward of station 15, Cd concentrations decline rapidly to -1 ppm at station 14, a level which is also found in the fine fraction about 2-3 km off Pte Verte and Rochette and Trap a 2.6 Pte. Beyond these stations Cd levels decline to background levels of 0. 4-0.6 ppm in the fine fraction. 15.2 "' o. ~ •0.6 OIJ.3 •l.i t!8.5 4j),i BELLEDUNE WHARF <10.6 <11.6 ,~}) !M!Hl:O Fig. 8. Cadmium (Cd) in suspended matter (ppm) in Belledune Harbour. In the three coastal transects to the east of the harbour (Fig. 9), total Cd varies from 0.1-1.8 ppm in the sediments. Except for sediments at station 15 about 3 km seaward of Belledune Pte and Station 16 adjacent to the west side of the break water that contain 1.8 ppm and 2.8 ppm Cd (Fig. 8), all the other sediments on this transect and those to the east contain low concentrations of Cd Fig. 10. Cadmium (Cd) in <53 ~m fraction of sedi (0.1-0.5 ppm). To the west of the harbour the ments (ppm) on coastal zone transects. sediments along the control transect at Tr~p Pte are also low in Cd as they contain 0. 20-0.30 ppm Cd. These concentrations are considered to be at or near background values. -41- Preliminary analysis of SPM from the coastal 64"::.0 waters shows that they contain 2.1-6.2 ppm Cd (Fig. ·------,---- 11). Although these values are much higher than in ,. .,.,. most coastal sediments, they do not seem to be " greatly enriched in Cd when their fine-grained nature is considered. Thus, there is little indi cation that the sediments, their fine fractions, and the SPM are contaminated with Cd more than 3 km seaward of the harbour mouth or eastward along the coast to Pte Rochette. ~"- BELLEDUNE WHARF ?Jl '>IJ{) 750 M[ff!fS Fig. 12. Zinc ( Zn) in sediment (ppm) in Belledune Harbour. •l/' •,:, • 300 e500 ·o·""Ei'-'"'1l'''~ccc>~R'o • 900 • 850 egoo 0 700 Fig. 11. Cadmium (Cd) in suspended matter (ppm) on coastal zone transects. ZINC TN SEDIMENTS AND SUSPENDED PARTICULATE MATTER BELLEDUNE WHARF The tentative results to date show that total ·1/" Zn concentrations are also very high in the harbour :.~ sediments and their fine (<0.053 mm) fractions. Total Zn concentrations (Fig. 12) vary from 925-3800 ppm, with the highest concentrations being found, Fig. 13. Zinc (Zn) in <53 pm fraction of sediment! like those of Cd, in the sediments next to the (ppm) in Belledune Harbour. breakwater in the northwest corner. The lowest Zn concentration occurs close to the Brunswick Mining and Smelting Corporation Limited outfall (Fig. 12). •1/" ,. The fine fractions are also enriched in total Zn " with concentrations varying from 700 ppm at the " sea\vard end of the harbour to 2350-5250 ppm at the landward (western) end (Fig. 13). This pattern is thus comparable to the Cd distribution (Fig. 6). The SPM samples contain 380-2115 ppm Zn with the highest concentration (2115 ppm), like Cd, being found at the station adjacent to the Brunswick Mining and Smelting Corporation Limited outfall (Fig. 14). Another high value is found in the center of the harbour (961 ppm) but lower concen trations (380 ppm) occur in the SPM adjacent to Belledune Pte. Thus, there is some indication that Cd-Zn rich material i.s being injected as particulate BELLEDUNI: WHARF matter into the harbour at the Brunswick Mining and Smelting Corporation Limited outfall but becomes quickly diluted by relatively Cd-Zn poor material at the seaward end of the harbour. Offshore, Zn contamination in the total sedi-· Fig. 14. Zinc (Zn) in suspended matter (ppm) in men t has not been determined at the present, but the Belledune Harbour. Zn values in the fine (< 0. 053 mm) fractions (Fig. 15) vary from 117-500 ppm. The highest Zn -42- SIZE FRACTIONATION OF CADMIUM-RICH SEDIMENT FROM BELLEDUNE HARBOUR For the purpose of determining the Cd concen ~ 113 • 1~0 tration associated with the fine-grained, most mobile, size fractions, a bottom sample from Belledune Harbour was fractionated, by settling, 0:86 0127 into different modal sizes and the grain size of eZ15 each compared with the Cd content. The experimental procedure consisted of suspending similar amounts of the sediment in super-Q water and from each 3 L suspension withdrawing a pipette fraction from a constant depth after exponentially increasing time intervals. Figure 17 shows the grain-size composition of each sample corrected to a constant initial concentration. In Table 2 is listed the sediment and Cd concentration of each withdrawal sample. From the difference between consecutive samples the nature of individual graded fractions was calculated (Table 3). Size analyses of ore concentrate samples were performed for comparison (Fig. 18). Fig. 15. Zinc (Zn) in <53 ~m fraction of sediments on coastal zone transects. concentrations (420 and 500 ppm), like those of Cd, are found at station 15 about 3 km seaward of Belledune Pte and at station 16 adjacent to the western side of the breakwater. Beyond station. 15 and to the east along the coast, Zn concentrations 0 z c fall quickly to ~120-180 ppm which can be considered w to be near background when compared to levels of ::J w0 113-156 ppm found in the fine fractions along the 0~ control transect off Trap Pte. lL In the offshore SPM samples (Fig. 16) total Zn varies from 230-503 ppm without a clearcut distri button pattern. Since SPH samples from the Bay of Fundy normally contain 400-900 ppm Zn, the Zn values ,, __ !__ recorded here appear to be close to expected back -01 ,_, ground concentrations for SPM. 10 100 DIAMETER, )Jm Fig. 17. Size fractionation of Cd-rich sediment. For definition of individual samples and fractions see Tables 1 and 2. Z3G Results indicate that during the first five .. 316 draw-offs, concentration, grain size and Cd content eZ9? decreased in a regular, consistent manner; 94.33% of g}60 the Cd present in the first draw-off had settled out by the third draw-off, indicating that most of the Cd was associated with particles of 12-20 ~m modal diameter. The fraction corresponding to modal sizes ~m • 5'J3 of 8 and 5 contained only 2.4 and 2.3% Cd, respectively. In the last two draw-off samples the Cd values were higher than found in the last sample and consequently no Cd values could be calculated for the 3.0 and 1.5 ~m fractions. This increase is most likely due to flocculation or absorption of colloidal or dissolved Cd onto larger particles. The loss of Cd in this form to the super-Q water is shown by a dissolved Cd content of 0.45 ppb measured in the filtered water of the last draH-off. The one order of magnitude variation in the Cd to surface area ratio is evidence that the Cd does not occur as a coating on larger sediment grains but as discrete Fig. 16. Zinc (Zn) in suspended matter (ppm) on Cd-rich particles. coastal zone transects. -43- Table 2. Size fractionation of Cd-rich sediment from Relledune Harbour. Settling Total Sur face rate Correction cone,. Cd are(i Cd Fractiona (em/ s) factor (mg/L) ppm ( wt) (~m2/L) (mg/L) >I,. 45E-2 l. 45 70.79 70 2.80El0 I. 04E-2 2 >I.IlE-2 ].] 61.Ril 54 l. 9/+E lO i+.OSE-3 3 >6.94E-3 2. I l ). 43 38 L 'i5El0 5.il6E-4 4 >1. 74E-4 2. l 7. 7l 43 7. lOE9 3.3IE-4 5 >B.68E-5 1.8 !;, 94 39 4.24E9 1. RflE-1, 6 >4.21E-5 I.6 4.80 91 2.f>7E9 1;, 36E-4 7 >2.10E-5 1.0 4.30 58 1. 62E9 3. SSE-I; a sec Fig. !. T11hle l. Size fractionation of Cd-rich sediment from Relledune Hat·bour. ------·------Surface area Cd surface Fracttona Mode size Cd mg/L a/a total ~m2/L mg/cm2 A 1. l1E-2 - 20 6. 35E-3 61.0() O.il6El0 7.33E-1 I• ,1•5E-2 B 6. 9/;E-4 - 12 3.46E-3 33.27 0.39El0 8.87E-l l. llE-2 c 1. 711E-4 8 2. 54E-1, 2.44 0.84E9 3.02E-1 6. 94E-4 j) 8.68E-5 - 5 I. 43E-4 ]. 38 2.85E9 5.0JE-2 l. 74E-4 E 4.2JE-5 - 3 I. 56E9 8.68E-5 F 2. JOE-5 - J.) I. 05E9 I;. 20E·-5 98. 15 .g Sef) Fig. ]. -44- Table 4. Inside the harbour, Cd and Zn concentra tions were too high for the preconcentration/ 12 8 extraction procedures chosen for this study. As a result, very low extraction efficiencies led to low 0 0 6~ results for the analysis of samples 803320 and " 803321 by atomic absorption. Anodic stripping voltametric analysis gave the much higher results 32 - A g for these two samples that are quoted in Table 4. p Otherwise, the ASB and AAS methods yielded n CDo 0 "")- - 0 u IG comparable results. z 33% w :::J 0 ·8 - w (l~ RESULTS lL 4 - The concentrations of Cu, Zn, and Cd in water are shown in Fig. 19-24. 1hese concentrations are best appreciated in the context of the ranges of . l ___l each metal in typical lmcontaminated coastal sea 15 32 64 125 250 500 water. These are as follows: DIAMETEH, JJm Cu 0.3-0.5 ]Jg/L (Yeats et al. 1978); Fig. 18. Grain size analysis of ore concentrate Zn 0.8-2.0 )lg/L (Bewers 1979); samples from Belledune area. Samples marked: 1. Cd o. 05-0.10 vg/L (Bewers and Yeats 1979). High Cd dust from stock pile; 2. Lead concentrate from Church (RMS); 3. Blast-furnace slag from stock pile. Also shown are relative concentrations of Cd in individual size fractions of fractionated bottom sample. $ 0. 3(, The ore concentrate samples are dominated by grains larger than 5-8 vm. Two out of three of the samples also contain finer particles. Optical examination showed that the sample labeled "high Cd-rich dust from stock pile" was rich in very fine opaque material similar in appearance to grains seen in the Belledune samples. In conclusion, Cd in the Belledune sediment samples is present mainly in 5-8 vm and larger grains but fine, partly sub-micron material causes high relative concentrations in the finer fractions which '"ould dominate the suspended matter. Cadmium in the latter may be expected to shift between the dissolved and particulate fraction during normal Fig. 19. Copper (Cu) in water ()lg/L) in Belledune resuspension and settling action of the sediment. Harbour. HATER SAMPLING AND ANALYSIS ~-·- Water samples were collected at a depth of 7 m •' at selected stations by using a General Oceanics 12-L GO-FLO sampling device. Subsamples of the '"ater were collected for salinity and trace metal determinations. The trace metal samples were fil tered through preweighed 0. 4 v m pore-size Nuclepore filters to remove and collect suspended particulate matter. The filtrate was then acidified with HCl to pH ::2 and stored in 2-L conventional polyethylene bottles (Bewers et aL 1976). In the laboratory, filters were washed, dried and reweighed to determine the concentration of suspended particulate matter (SPM) per unit volume of water. Aliquots of the filtered water samples were analyzed for Cd, Cu, and Zn by graphite furnace-atomic absorption spectrophotometry following preconcentration by chelation and solvent extraction (Bewers et al. 1976). Separate aliquots of these samples ivere also analyzed by anodic stripping voltametry. The concentrations of SPM, Cu, Zn, and Cd at each station are presented in Fig. 20. Copper (Cu) in water (vg/L) in coastal zone transects. -45- Table 4. Concentration of copper (Cu), zinc (Zn), and cadmium (Cd) in seawater. Data in parentheses are based upon anodic stripping voltametry. All other analyses were conducted by atomic absorption spectrometry following chelation/solvent extraction procedures. Suspended particulate Station Salinity matter Cu cone. Zn cone. Cd cone. no. o/oo mg/L ~g/L (SD) ~g/L (SD) llg/L (SD) 8033 01 21.61 l. 34 0.472(0.007) 6.29(1.08) 2.26 (0.19) 03 23.48 1. 49 0.481(0.032) 2.79(0.32) o. 506(0. 021) 05 23.69 1. 95 0.433(0.062) 1.68(0.15) 0.173(0.006) 06 23.70 l. 14 0. 4 71 ( 0. 06 6) 5. 40(0. 53) 2. 50 (0. 25) 07 27.34 1. 42 0.540(0.024) 2.41(0.22) 0.125(0.016) 08 24.24 l. 66 0.384(0.031) l. 91 ( 0. 34) 0.196(0.016) 09 24.33 0.751(0.053) 1.93(0.18) 0.198(0. 018) 10 27.61 l. 38 0. 460 ( 0. Oll) 2. 37(0.15) 0.176(0.020) 11 27.08 l. 67 0.387(0.010) 2.10(0.09) 0.161(0.006) 12 25.89 1.44 0.460(0.010) 2.65(0.26) 0.190(0.006) 13 27.66 l. 32 0.356(0.018) 2. 62(0. 07) 0.185(0. 027) 14 27.68 1. 93 0.464(0.024) 1.92(0.05) 0.108(0.004) 15 27.02 2.45 o. 384(0. 023) 2.26(0.18) 0.182(0.008) 16 29.98 l. 51 o. 363(0. 017) 3.19(0.12) 0.458(0.032) 17 27.93 1. 87 0.553(0.018) 0.168(0.012) 18 28.20 l. 24 0.393(0.013) 2.68(0.02) 0.235(0.018) 19 28.05 2.00 0.426(0.005) 2.58(0.10) 0.230(0.010) 20 24.29 7.84 0.907(0.019) 260 125(23) 21 25.10 0.531(0.005) 34.3(2. 7) 25.5(2.1) 9 3.19 $ 1.68 BELLEDUI'JE WHARF ------'- -- Gs·oo bq:~- -- Fig. 21. Zinc (Zn) in water (~g/L) in Belledune Fig. 22. Zinc (Zn) in seawater (!lg/L) in coastal Harbour. zone transects. -46- breakwater. All Zn concentrations on the four near shore transects in the Bay of Chaleur were close to expected coastal water values. Thus, it appears • ? .:,o that the major Zn contamination of the water is confined to Belledune Harbour with somewhat elevated levels also evident in the area adjacent to the HII ~- A K\'1 I t f\ harbour breakHater. The Cd distribution is very similar to that of Zn. Levels in the general area are somewhat higher than typical coastal water samples but this may be the consequence of mineralization of the local land area. Higher values are confined to the vicinity of Belledune Harbour where concentrations can be 100 times ambient. As in the case of Zn, the samples obtained just outside the northern break~>Jater are elevated in Cd, but not to the extent found inside Gt_L _EDlmE WI-I/\11F Belledune Harbour. CONCLUSIONS Fig. 23. Cadmium (Cd) in seawater (~g/L) in Belledune Harbour. Preliminary conclusions that may be drawn from the data contained in this paper are that: 1) Belledune Harbour is heavily contaminated Hith Cd and Zn in both aqueous and sedimentary phases, and 2) contamination levels decrease rapidly SHay from the harbour such that none of the coastal zone transects further than 3 km from Belledune Harbour can be regarded as yielding abnormal metal distri butions. Within the harbour, Cd-rich particles are found to have a bimodal distribution which suggests that both fine and coarse particles are important agents of Cd transport. Host of these Cd-·rich particles remain trapped at the Hestern end of the harbour, close to the breakHater, and little material seems to be transported more than 1.5 km seaward. It is possible that any exported metals have been transported predominantly into the deeper regions of Chaleur Bay to the northeast. Never theless, it is our conviction that, under normal atmospheric conditions, residual coastal circulation would be the most prominent mechanism of particle and aqueous transport. It is likely that storm events could produce considerable redistribution of the contaminated sediments and this aspect of transport Hould be worthy of further investigation. Fig. 24. Cadmium (Cd) in seawater (vg/L) in coastal ACKNO\vLE DGMENTS zone transects. We In contrast, both Zn (Fig. 21-22) and Cd (Fig. 23-24) show considerably increased levels in the REFERENCES vicinity of Belledune Harbour. The Zn concentration of the sample collected adjacent to the outfall (260 vg/L) was .-v150 times the normal levels i.n coastal BeHers, J. M. 1979. Trace metals in Haters within waters but the concentrations rapidly decrease to the jurisdictional area of the International L 7-6.3 vg/L in the section across the harbour Commission for the Northwest Atlantic mouth. Outside the harbour high concentrations were Fisheries. Bedford Institute of Oceanography found only at stations 6 and 16 along the outside of Report BI-R--79-2. the breakwater. These elevated concentrations may have arisen from releases from the outfall of the fertilizer plant or transport of water from Belledune Harbour through or around the end of the llewers, J. M., ll. Sundby, and P. A. Yeats. 1976. The distribution of trace metals in the western North Atlantic off Nova Scotia. Geochirnica et Cosrnochirnica Acta 40: 687-696. Bewccrs, J. M., and P. A. Yeats. 1979. The behaviour of trace metals in estuaries of the St. Lawrence Basin. Naturaliste canadien 106: 14 9-161. Canadian Hydrographic Service. 1965. Data compilation; Helledune Point current survey, 1964 season. Bedford Institute of Oceanography Data Series Report 6S-I. Loring, n. H., and R. T. T. Rantala. 1977. Geochemical analyses of marine sediments and sw;pended particulate materiaL Fish. Mar. Serv. Tech. Rep. 700, 58 p. Rantala, R. T. T., and D. H. Loring. 1980. Direct determination of cadmium in si li.cates from a f]uoboric - boric acid matrix by graphite furnace atomic absorption spectrometry. Atomic Spectroscopy (In press). Yeats, 1'. A., J. M. Hewers, and A. \-laJ ton. 1978. Sensitivity of coastal waters to anthropogenic trace metal emissions. Mar. Poll. Bull. 9: 2 64-268. -49- Till·: LEACHING OF CADMIUM FRm1 THREE BELLE DUNE S"1ELTF.R MATER lALS hv ll. !1. Sergc;l!ll and S. Rav Fisheries and Environmental Sciences Department of Fisheries and Oceans Biological Station St. Andrews, New Brunswick EnG 2XO -50- INTRODUCTION Emissions of cadmium (Cd) associated with Brunswick Smelting's operation at Belledune were 0 described by Sergeant and Westlake (this report). 140 Slog The levels of Cd found in water, sediment and biota from this area may be related to the leaching of Cd 120 from various materials used in, or produced by, the en smelting process. Of particular concern with :;; 100 a respect to leaching are: the slag because of its Q_ -o quantity (at present, 1.4 million metric tons (MT) 0 .c"' 80 '-' 0 in the slag pile); the baghouse dust which is 0 removed from the when the Cd concentration 0 -'"' 60 --- o .... reaches about 10% MT last year), because of its 0 "0 0 high concentration of Cd and the Cottrell dust 0 0 ~o~ received from Nor and a Horne mine, because of its 0> 40 =>. / volume and 1% Cd content (4542 MT for each of 1978 / 0 and 1979). These materials were subjected to leaching tests to determine their relative leaching potential in a rapid preliminary study covering a 0 short time period and using arbitrary, non-standard 2 00 400 600 techniques. Leaching criteria in relation to Time (Hours) smelting and refining s are discussed, for example, by Leonard et al. 1977). Fig. 1. Graph of )lg Cd leached/g slag in different media. METHODOLOGY 0 Slag in acidified distilled water b. Slag in normal seawater Polyethylene bottles ( 1 L, soaked overnight with 50% nitric acid and then washed three times D Slag in acidified seaHater with deionized distilled water) were filled with: a) distilled water at pH 1; b) normal seawater; c) seawater at pH 1 (pH was adjusted by addition of nitric aci.d, BDH Aristar grade), The initial volume in each bottle was 900 mL. Approximately 0. 9 g (wet - _u_.....,.!? weight) of each sample was added, 60 000 ,.,. ' ' The bottles were thoroughly shaken periodically ' 'o and the contents were allowed to settle for 16 h prior to sampling. No haziness was observed at the :;; I ' \ Q_ 0 time of sampling. A 20-mL Hater sample Has Hith- -!:! -o 40 000 I drawn by pipette Hithout from each bottle I ' .c"' '-' I Baghouse Dust at 0, 17, 41, 94, 166, 304, 376, and 523 h. The 0 unacidified seaHater samples Here acidified Hith tHo _J"' /o drops of Aristar nitric acid at the time of samp -o 0 ling. Cd concentrations in the unfiltered Hater u en 20 000 samples Here determined by graphite furnace atomic =>. /). 6 ·-,c,·-.6.- absorption spectroscopy. Accuracy and precision of -·-·-6·- Cd analyses were checked NBS standard .,.,-----· -·-· reference material 1643a Hater), The results (llg Cd leached/g material) of the OL-~~-L~---'--L--~-L~--'L-~ 2 00 400 600 leaching tests are presented in Fig. 1-3. Plotted Time (Hours) lines Here fitted to the data by least square regressions. Analytical (interference) problems encountered Hith the baghouse dust in distilled Fig. 2. Graph of )lg Cd leached/g baghouse dust in water for the 17-h sample led to sampling and different media. analysis of Hater samples from this bottle being terminated after that time. b. Baghouse dust in normal seaHater D Baghouse dust in acidified seaHater Samples of slag, baghouse dust and Cottrell dust Here analyzed by the NeH BrunsHick Research and Productivity Council (RPC) (Fredericton, N.B.). Baghouse dust Has also analyzed by the National Research Council (NRC) laboratories (OttaHa, Ont.) (Table 1, 2). -51- Table 1. Analysis of baghouse dust (NRC, Ottawa). ------Wet weight Wet weight Element % Element % Fe (iron) 20 Sn (tin) 0.1 Pb (lead) 10 In (indium) 0.1 Zn (zinc) 10 Bi (bismuth) o. 1 Ca (calcium) 10 Sb (antimony) 0.06 As (arsenic) 5 Ag (silver) 0.03 Si (silicon) 3 Ti (titanium) 0.03 Al (aluminum) 0.3 Mn (manganese) 0.03 Cu (copper) 0.3 B (boron) 0.01 Mg (magnesium) 0.1 cda(cadmiwn) 7.5 aFlame atomic absorption. Table 2. Analyses of slag, baghouse dust and Cottrell dust (RPC, Frederic ton). Wet weight Wet weight in Wet weight in slag baghouse dust in Cottrell dust Element % % % Fe (iron) 30.6 7.6 19.2 Zn (zinc) 12.8 5.3 4.6 Cu (copper) 0.30 o. 61 0.33 Pb (lead) 4.06 32.6 30.3 Cd (cadmium) 0.01 9. 7 o.o1a Bi (bismuth) 0.01 0.11 0.04 Sb (antimony) 0.03 0.06 0.08 Ca (calcium) 10.4 2.32 0.06 As (arsenic) 0.12 1.6 0.32 Ag (silver) 34 ppm 219 ppm 467 ppm aproblems with precipitation of material during dissolution process. 100 Cottrell Dust o-.. RESULTS AND DISCUSSION 80 0' :;; a. a LEACHING STUDY / -o 60 p~ "' .c:"' Slag, baghouse dust and Cottrell dust are '-' 0 / 0 0 0 _.. "' potentially subject to leaching of Cd by contact _J"' 0 ,.. / with water. Of particular concern is the baghouse 40 "" dust which contains high levels of Cd (approximately "'0 ,. / "" /' 10%). Rozovsky ( 1974) reported that the Cd in the = / ::< 0 .... 0 dust from the electrostatic precipitator on the 20 ,o .... sintering machine was in the oxide form, and thus b /:>. -·-·- presumably readily leachable. Q 0 /:>.-·-·-· I:!. -·-· !::,. /:>. I -·/."}.-·-·-• Acidified distilled and seawater were chosen as 0 200 400 600 leaching solvents to give an estimate of the maximum Time (Hours) leaching potential of each material, compared to the leaching potential in seawater. Fig. 3. Graph of ~g Cd leached/g Cottrell dust in Physical characteristics different media. The slag sample was a slightly wet, black, 0 Cottrell dust in acidified distilled water coarse, sand-like, glassy material; the baghouse dust from the stockpile was wet, greyish-green and ~Cottrell dust in normal seawater very fine with some agglomerations; the Cottrell 0 Cottrell dust in acidified seawater dust was a dry, very fine, dark-grey powder and -52- agacn had some agglomerations. These characteris Cottrel 1. dust tics explain why fine matArial from the baghouse dust and Cottrell dust was observed floating on the Leaching in acidified distilled water proceeded surface in the acidified distilled water bottles. slowly with equilibrium being reached after about Few0r floating particles were observed in the 4'i0 h (Fig. 3a). The amocmt leached was about the seawater tests with tl1ese materials. In both same as from the slag. For normal seawater acidified and normal seawater the baghouse dust leaching, a constant leaching rate was observed br'came a silvery color. (Fig. 3b). In comparison with the acidified dis-· tilled water, less than one quarter of the amount of Although sett1 i11g rates werP nor determined, Cd was leached in normal seawater. Tbe scatter of the tendency to s To see if our samples (Table 2) were repre sentative of typical materials, we obtained some ({<-!pid lr.~<1chJng by acidified seawater followed Brunswick Smelting data on the typical composition ov equi I ibrium was observed (Fig. 2). The dust in of such materials at the Relledune smelter. Except nnrrnn l [.;eawater leAched rapidly at· fi.rst, then for the Cd analysis on the Cottrell dust, there was grHdunl1y through the remainder of the experiment. good agreement in composition. ln_ Oc)t-h !ll(~diA the qu~Hlti_ti_cs of Cd 1_pached were 10-~ t:ilnPs tl1e lev~ls observed for slag. Acidified dlst i llt'rl water ]p;qched nbout the snn1l' amount of Cd CONCLllS IllNS as ac i_di fieri st•awat-Pr at 17 h wh('n this tPst was t<'nnindt-ed. The prohlem encount(~red wHs that of a .split peak on t-lH' recorder and failure of the pE~n !:1) ThP leaching potential decreases in the order r~·tlJftl t<) baseline indicating a probahle inter- baghouse dust>>> slag =>Cottrell dust. The fen-•nce phenomenon. SincP the dust was determined baghouse dust is the most hazardous material from t '' cont in 8. 6% viPt weight Cd (average of Cd values leaching and environmental points of view. The in nblPs l and 2) on a wet wPight basis, then slag, despite its low Cd content and relatively normal seawater had leached about 21% of the total limited leachability, may also be a source of Cd Cd from the rlust and the acidified seawater about because of its quantity. 6 7%. The quantity of dust produced and its hand! ing ACKNOWLEDGMENTS and storage are ther(~fore of concer·n dtte to its h1p,h Cd Cr)ntcnt. Tf this dust i_s conVf'yr-d by wind ~)J- Leonard, R. P., R. C. Ziegler, W. 1\. Brown, J. Y. Yang, and H. C. Re if. 1977. Assessment of industrial hazardous wastE• prac·tices in the metal smelting and refining industry. U.S. Dept. Commerce, National Tech. Info. Centre PB-276 169, PB-276 170, PB-276 171, and PB-276 172. Rozovsky, H. 1974. Lead and the environment at the Smelting Division of Brunswick Mining and Smelting Corporation, Bathurst, N.B. Can. Inst. Mining and Metallurgy BulL. 67: 50-60. -5')- UPTAKE AND EXCRETION OF C!lll~1Tlif1 BY ~li\R TNE ORGANTS~1S FROM SEA HATF<:R WTTH Ci\DM1U~1 i\T LO\v CONCENTR!ITWN: A REVH:H by D. IV. McLeese Fisheries and Environmental Sciences Department of Fisheries and Oceans Biological Station St. Andrews, New Brunswick EOG 2XO -56- INTRODUCTION Crustaceans Lobsters (Homarus americanus) exposed to sea The objectives of this review are: water with 0, 3--;;r&ppb (added) Cd for 30 d showed no change in Cd concentration ln hepatopancreas, (A) to assess cadmitun (Cd) accumulation by marine 20.3-23.5 ppm wet wt, or in muscle tissue (< 0.12 ppm organisms when they are exposed to sea \vater with Cd wet wt, cletec tion limit). An elevated Cd concen at low concentration (ppb range), tration occurred in the gill tissue with exposure to 6 ppb Cd but not to 3 ppb Cd (Thurberg et al. 1977) (B) to assess the potential for Cd excretion by (Table 3). marine organisms. Lobsters exposed to !O ppb Cd for 10 d showed A. ACCUMULATION OF CADMIUM no change i.n Cd concentration in viscera (pre sumably, hepa topanc reas and gonad tissues) or muse le Summan; tissue but \,d concentrations in gills and shell were elevated (Eisler et al. !972) (Table 4). The From the data for sea weeds, crustaceans, differences in concentration between control and polychaete worms and molluscs, there is evidence test animals yield CF's of 33 and 38 for shell and that Cd accumulates in the tissues of these gills, respectively. organisms from water containing Cd at very low C(Jncentrations, from trace amounts to less than 0.5 Brown shrimp ( Crangon crangon) exposed to 1. 5 pph Cd in water. For animals exposed to 0. 5 ppb Cd pph Ccl in we~ter for 20 d showed no uptake of C,d, the or less, uptake rates are low, ranging From 0.05 to tissue concentration remaining constant at 0. 5~ ppm 15.3 ppb Cd/h (dry \vt). Cd ctrv wt. Exposure to 2. ~ ppb Cd resulted in " higher concentration, 1.1 ppm Cd, in tile tissues Sea weed (Dethlefsen 1977 /78) (Table 5). The difference ( 1. 1-0. 55) yields a CF of 2211. Fucus vesiculosus te~ken from water with 0. 3 ppb Cd had tissue concentration of IS ppm Cd dry wt, and Crangon septemspinosa showed no ace umulat ion of from water with 0. 5 ppb Cd had tissue concentration Cd when exposed for 30 d to a trace amount (< 0.01 of 30 ppm Ccl (Butterworth et al. 1974) (Table 1), ppb) of Cd (Ray et al. 1980b). yielding concentration factors (CF's) of 50,000 and 60,000, respectively. Polychaete.s F. vesiculosus taken from water with mean Nereis virens exposed for 30 d to a trace annual Cd concentration of 0. 27 ppb had tissue con amoun~Ol ppb) of Cd showed an increase in Cd centration of 3. 8 ppm Cd dry wt, and from lvater with concentration from 0. 37 to 0. 58 ppm Cd dry wt (Ray 0. 59 ppb Cd, the tissue concentration was ll. 3 ppm et aL 1980b). Cd (Harris and Bale 1975) (Table 2), yielding CF's o up to 25,500 and up to 51,400, respectively, Nereis diversicolor from two estuaries with close to the valuPs reported above. differenthackground levels of Cd in the sediment Table !. From Butterworth et al. (1974) - Fucus and molluscs from nature. Cd in water Cd in tissues of various species (ppm dry wt) ppb Fucus CF Littorina CF ----Patella CF Thais CF 5.8 220 38'a 550 95 I 3.8 200 53 7 210 55 1 220 58' 2.0 50 25' 140 70' 200 !00' 425 212' 1.3 25 !9' 30 23' ll () 85' 330 254' !.0 20 20' 25 25' 50 50 I 270 270' 1 1. 2 44 37' 40 33 70 58 I 120 !00 1 0.5 30 60 1 16 32' 30 60 I 65 !30' o. 3 15 50' 15 50' 30 100' 62 207 I 0. l (open sea) a38' 38,000, etc. -57- Table 2. From Morris and Bale (1975) -Focus from nature. Annual average Cone. Cd in Cd in water Range of Fucus Average ppb Cd in water ppm dry ,.,t CF l. 34 0.91-2.02 19. 5 l4.5 1 a !. 07 0.65-1.50 15.8 14.8 1 o. 75 0.45-1.28 19.2 25.6 1 o. 59 0.29-1.20 9.3 15.8 1 o. 59 0.22-1.77 11.3 19.2 1 0.27 0.15-0.38 3.8 11+. 2 1 u,, 500, etc. Table 'l. From Thurberg et al. (1977) - lobsters <'Xposed to 0, 3 and 6 ppb Cd for 30 d. Cd in water Cd in various tissues (ppm wet wt) CF ppb Hepa to pane reas Gills Muscle Gills 0 20.3 1.5 <0.12 3 22.5 1.8 <0. 12 100 6 23. 5 3.4 <0. 12 465 Table 4. From Eisler et al. (1972)- lobsters exposed to 10 ppb Cd for 10 d. Control Test Tissue Cd ppm 1vet wt Cd ppm wet wt CF Whole lobster o. 51 o.n 21 Muscle 0.20 0.21 'i She 11 o. ')9 0. SH 33 Gil 1 0.49 ().P,7 38 Viscerd ] • 21 I. 21 0 Table 'i. From Dethlefsen (1977/78)- Brown shrimp (Crangon crangon). Cd in water Cd in shrimp Cd in shrimp ppb ppm dry wt CF ppm dry wt CF static tests (30 d) (30 d) (40 d) (40 d) 5 3.P, 760 10 I, 500 20 7. 3 365 50 8. 'l 165 14.7 295 100 16. 1 160 22.0 220 Flow Lhrough tests 1. 5 constant level at 0.')5 ppm during 30 d 2. 'i I • I ppm 11 t 10 d - C F 2 211 -58- were exposed to l ppb Cd in water for 38 d (Bryan Littorina and Patella accumulated Cd from water and Hummerstone 1973) (Table 6). Worms from the with 1 ppb Cd, Thais from water with 0. 5 ppb Cd. Avon area, with the lower background level, For all three species it is possible that there was accumuiated Cd to 208 ppm (CF about 208,000) and accumulation from 0.3 ppb Cd (Butterworth et al. those from Restronguet Creek accumulated 140 ppm Cd 1974) (Table 1). The CF's from exposure to 0.3 ppb dry wt (CF about 140,000). Cadmium was absorbed at a Cd are about 50,000, 100,000 and 207,000 for slower rate by the worms from the area with the Littorina, and Thais, respectively. higher background level of C,d. Hacoma controls had 0. 24 ppm Cd dry wt; those Molluscs expos~a trace (<0.01 ppb) amount of Cd for 30 d had 0. 6 ppm Cd (Ray et al. 1980b). Macoma exposed in water with <0. 5 ppb Cd showed for 15 d to sea water with I ppb Cd showed an nn .--;--~_, level in tissues from 0. 3 increase tn CF from <190, initially, to about 370 at (control) to 10 ppm dry wt (CF of 20,000). TI1ose end of exposure (He Leese et al., unpubl.). exposed to L,, 6 ppb Cd showed an increase to 70 ppm (CF of 15,200) (Westernhagen et nl. 1978). Calculated and extrapolated uptake rates for Cd Oysters (Crassostrea virginica) accumulated Cd Some of the reviewed data were for organisms from vJater with 0.1 (CF about 1,000,000) and 0.2 ppb t~kPn in nature, presumably at long-term equilib Cd (CF about 500,000) (Shuster and Pringle l%9) rium, ;mel uptake rates could not be calculated. For (Table 7). the remaining data, organisms h.:1d bet~n exposed to water with 6 ppb Cd or less and uptake rntes were f· virginica from water with 0. l to 0.2 ppb Cd calculated (Table 9) according to the following had tissue level of 2.7 ppm Cd wet wt (l 1.8 ppm Cd formula: dry wt). Exposure to 5.0 ppb Cd for 40 wk resulted in elevated Cd concentrations in the tissues, 13.6 Rate of uptake ppm wet ( 105 ppm Cd dry, CF of 18, 600) (Zaroogian Exposure time in h and Cheer 1976) (Table 8). Table 6. From Bryan and Hummer stone ( 1973) - Nereis diversicolor from two areas exposed to Cd in lvater for up to 816 h (35 d). Worms from Worms from Cd in water Avon Rest. Creek pph ppm Cd dry wt CF ppm Cd dry wt CF 1.0 208 208 .a 140 140 1 2. 5 471 188 1 225 90 I 1 10 1860 186 I 629 63 1 25 1970 79 1630 65 I 100 4010 40' 1300 13 1 a20H' 208,000, etc. Table 7. From Shuster and Pringl<' (1969)- oysters exposed to Cd for 16 and 20 wk. Cd in water Cd in oysters ppb ppm wet wt CF Control I. 17 and 2, 6L1 0.1 (16 wk) 122. 5 and 105. 7 l,225'aand I, 060' 0.2 (13 wk) 94.5 and 125.8 I; 73 I and 02 9 I a1,225' ~ 1,225,000, etc. -59- Table 8. From Zaroogian and Cheer (1976) - oysters exposed to 0.1-0.2 (controls) and 0.5 Cd for 40 wk. Cd in water ppb wt wet o. 1-o. 2 2. 72 11.83 5.0 13. 57 104. 95 2.2'a 18.6' 2,200, etc. Table 9. Calculated uptake rates of cadmium (Cd) for marine invertebrates exposed to Cd in 1vater at concentrations of 6 ppb or less. Exposure Calculated time cone$ uptake rate Anima 1 Rt:~ ference (d) (ppb) (ppb/h) Polychae tes Nereis virens Ray et aL. ( 1980b) 30 trace 0. 3 (dry) Crustaceans ~--~~ ~~~mspin?sa Ray et aL. (1980b) 30 trace No uptake de tee ted ~~~~ £rangon Dethlefsen (1977/78) 30 !.5 No uptake de tee ted 30 2. 5 0. 76 (dry) Homarus americanus Thurberg et al. (1977 )30 '3 0. 4 (gill, wet) 30 6 2. 6 (gill, wet) Holluscs Ray et al. ( 1 980b) 30 trace 0. ') (dry) Westernhagen (1978) 163-300 0. 'i !. 3- 2. 5 (dry) 4. ') 9. 7-17.8 (dry) Crassostren virginic~ Zaroog"lan and 287 ).0 13.5 (dry) Cheer (l 97(,) 1. 6 (wet) where CdA concent ion in animals after exposure agreement except for oysters, where the calculated rate ls 6 times greater than the extrapolated rate. CclAC conC'(~ntrati.on in control animals For 0. 5 ppb Cd exposure, the polychaete Data for animals cxpused to water with higher .'-L-""'-'-'==~-"-c.c_:._ has an uptake about 18 times concEntralions of Cd (10 ppb or more) were no rate t:ha t for Nereis (Table 10). The discussed previously. From these additional data, rates for oystErs and mussels are equal Hptake ratc~s were calculrtted as above and the rates greater than the rates for quahogs, and were plotted against exposure concentration 011 log 40 times greater than the rate for surf clams. The log paper. '!1w line rt'presenti.ng thE relationship data for shrimp indicate no Cd uptake from water bet\veen upL1ke rate and exposure concentration was with trace to 1.5 ppb Cd, so the extrapolated rate Pxlrapolatpd to provide estimates of uptake rates from water with 0.5 ppb Cd may not applv. f,,r <'Xposures to 0.')-2.0 pph Ccl (Table lfl). Tiw cotl\'entrations of CAl accumulated in l yr Uptake rates, where given in the literature, from water with 0. 5 ppb Cd have been calculated for remil ined constant throughout the exposure periods; shrimp and mussels (Table 12), using calcu- consequently, for calculating the rates (above), and extrapolated uptake rates. This provides constant rates \vere assumed. Kleckner (1979) a rough idea of the magnitude of the effects to be rEportecl an exception. Polychaete worms were ex pee ted from long exposure to low concentrations of exposed to 10-1000 ppb Cd for 64 d and the Cd wherE uptake rates are low. concentration of Cd in those exposed to 1000 ppb Cd ( l 708 ppm Ccl dry wt) was approaching an asymptote at B. EXCRETION OF CADMIU~1 61, d. If so, the rate of uptake would not be constant, at least during the latter part of the expusure.v From the Oatn For crustaceans, pol ychacte worms Cenerally the uptake rates, wlwt:her calculated and molluscs, therE is little evidence to ind icctt<' or extr<~polated, rtre low when animals ;1re exposed to tlwt l'xcretion of Cd. occurs .. hllH:"re there is an 0. r, ppb Cd or less. Comparison of thP rates indication, the process llf excretion ls slov1. For obtained by tlw two nwt:hods Is possible for some of fish, LhPrt• [s evidence of Cd excretion if Cd is t:ht' dat:1 (Table' II), 'l1 Table 10. Extrapolated uptake rates of cadmium (Cd) at 0.5 to 2.0 ppb Cd for animals exposed to Cd at high concentrations. Exposure Extrapolated uptake rates at time cone. 0.5 ppb, 1.0 ppb and 2.0 ppb Cd Animal Reference (d) (ppb) (rate in ppb/h) Po lye haetes Nereis virens Ray et al. ( 1 980a) --- -~~--- 1-2 g 14 30-8200 O.'i 1.0 1.8 (dry) 5-7 g 14 30-8600 0.3 0.6 1.0 (dry) KHickner (l 97 6) 64 10-1000 9.0 13.0 19.0 (dry) Crustaceansa Crangon crangon Dethlefsen (1977/78)20 5-20 30-1,0 10-JOO (I. 7 1. 1 1.8 (dry) Pandalus montagui Ray et al. ( 1980c) 14 37-40 t aData for crustaceans (shrimp) show a reasonable fit by a single line. Table 11. Comparison of rates of uptake of cadmium ( Cd) obtained by calculation and by extrapolation. Calculation Extrapolation exposure uptake rate exposure uptake rate Ratio An _imaJ ppb Cd ppb/h ppb Cd ppb/h C/E Nereis trace 0.3 o.s 0.3-0.5 I Shrimp 2. 5 0.7(i 2.0 1.8 0.4 Mussels 0.5 ]. 3-2. 5 0.5 0.2 (wet) o. s-o. 96 2. 6 (dry) Oystet- o. 5 1.2 (wet) (1. 5 o. 2 (wet) 6 15.3 (dry) 2.6 (dry) 5.9 administer-ed in thr,; diet, but not if administered in the losses from exoskeleton and gills being most the water .. important (Wright 1977) (Table 13). Cru.staceans For Pandalus montagui exposed to 37 ppb Cd followed by 57 d in uncontaminated water, the Cd In Crangon crangon, there was no loss in Cd content of tail muscle, carcass, eggs and whole during 12 d depuration from animals previously animal may have decreased slightly but there was a exposed to 5 and 10 ppb Cd in water (whole body continual increase in Cd levels in the hepato concentrations of 2.25 and 2.60 ppm Cd dry wt pancreas (Ray et al. 1980c). res pee tively). For those exposed to 20 pph Cd, there was a loss in Cd (from 5. S-4. 3 ppm Cd) during Polychaetes the first 3 cl of depuration (Dethelefsen 1977/78). Hlue crabs (Callinectes sapidus) Pxposed to 10 SeverHl groups of small and large Nereis virens ppm Cd for 8 d showed no loss of Cd from carapace, w:! th concentrations of Cd from 4-21 ppm dry wt ___ gills or hepatopancreas duriflg 96 h post-exposure showed Little or no excretion of Cd during periods (Hutcheson 1974). up to 75 d (Ray et al. 1980a). Ueda et ill. ( 1976) reported similar results for polychaetes during 19 d Green crabs (Carcinus maenas) exposed to 20 ppb depuration. Cd in water for 37 d showed losses in Cd from shell, gills, he pa topanc reas and whole body during ll d depuration. About one half the Cd '"as lost in 11 d, -61- Te!hle 12. E:stimates uf cadmium (Cd) accumuLHed in 1 yr from exposurt• to cadmium in seawater at 0 .. 5 pph .. Concentr:1t ion of Cd Rate of uptake accumulated in 1 yr Animal ppb/h ppm dry wt Nereis o. 3-0.5 (Tables 9, 10) 2.6-4.4 Shrimp 0.7 (Table 10) 6. 1 Mussel ].3-2.5 (Table 9) 11-22 2.6 (Table 10) 23 Table 13. llat:1 on vxcrc~tion of cadmi From Wright~ ( 197 7) - Shore crab exposed to 20 ppb Cd for 37 d- excr,•tion during 11 d. Days for ~------~ Cd in tissues (p mole g-1 excretion Slwll Cills l!epatopancreas \olhole body () • If 55 .266 .261 .170 7 .388 .090 • 168 .147 11 .206 .132 • 21 9 .087 (Losses from shell and giLls important) Avf'rage excretion rate (as pmole/kg/h) -1 -(). 75 -0. 16 -0.35 MolL uses Fish Oys t ,, rs exposed to R;1inhow trout were exposed to Cd in water and 1'ipphCclin by a 16-wk to Cd in the l'ood supply. 1he concentration of Cd in dppurntion period. CndJHium conc(~ntration i.n the the fish dec1ined during 10 \•lk pnst-exposures oysl t' did not chang~._, during this excretion period (dilution through growth). However, the total Cd (/,a roog i:m 1979). loAd (~g Cd/fish) remained unchanged during 10 wk post-exposure for Lhe fish exposed to Cd in water. Burrowing trans- On the other hand, for fish exposed to Cd in food, i ~~,rr~-'d bPt.ween two c'S not atta the Cd load decreased markedly during 4 wk post- equality of Cd concentration between the transferred exposure when fed non-contaminated food. ThP and nature animals even after 1 yr (Bryan and authors concluded that the route of uptake of CAl, llurnrnc>rstone 197 8). from water or from food, may influence the retention or lack of excretion of Cd (Kumada et al. l 980). Marjori and Petronio (1973) provided datil for uptake ;1!1d excretion of Cd by mussels ll 1lwmusselswere to50 4 or H d. For excrtetion, the nHI~Si'ls \vere maintained in clean water for 5 or 27 d afLer t'xposure .. 11u.? results are summarized in Table 14. The cxcretlon rates (2.6-11 pph/h) are 9-33% of the uptakc r·atPS (2 7. 7-33.7 ppb/h). i'l_ Table 14. Uptake and excretion data for cadmium (Cd) and mussels (from Majori and Petronio 1973). Exposure Uptake Final Excretion Excretion Final Total t i_me rate cone .. time rate cone~ loss (d) ppb/h ppm (wet) (d) ppb/h ppm (wet) ppm (wet) Control 0.2 8 21.6 4. 144 8 18.2 3. 504 I, 33. 7 3.240 5 -11 1. 920 (-1. 320) I, 32.5 3.224 5 - 4. 2 2. 720 ( -0. 50 5) I, 27.7 2.660 27 2.6 o. 959 ( -1. 701) REFERENCES Phillips, D. J. II. 1976. The common mussel ~tilus edulis as an indicator of pollution by zinc, cadmium, lead and copper. I. Effects of Bryan, C. W., and L. C. Hummerstone. 1973. environmental variables on uptake of metals. Adaptations of the polychaete Ne_!:.eis Mar. lliol. 38: 59-69. diversicolor to estuarine sediments containing high concentrations of zinc and cadmium. J. Ray, S., D. W. McLeese, and D. Pezzack. 1980a. Mar. lliol. Ass. U.K., 53, 839-857. Accumulation of cadmium by Nereis virens. Arch. Environ. Contam. Toxicol. 9:~ 1978. Heavy metals in the burrowing bivalve SorobicularLpuration '39-63. Fish Mar. Serv. Trans]. Ser. No. 3143. of cadmium and copper by lire American oyster, Crassostrea virginica. Bull. Environ. \.-0ntam. Morris, A. W., and A. J. lla!e. l97r)~ The accumu- Toxl.col. 23: 117-!22.· lation of cadmium, copper, manganese -65- CADNIUM IN Al1ER ICAN LOBSTER (!:!OMARU~ AMERICANUS) FROM THE AREA OF BELLEDUNE HARBOUR by J. F. Uthe, C. L. Chou, and D. Robinson! Fisheries and Environmental Sciences Department of Fisheries and Oceans Halifax Laboratory Halifax, Nova Scotia B3J 2S7 llnvertt'hrates and f-'larlne Plants Department of f'isheries and Oceans Halifax, Nova Scotia RJJ 2S7 -66- INTRODUCTION ~6~~~oo~·----~M~----~w~·-----·~'-·----~~··~o ____ ~M~·--, 48oo· ... 00 Following an initial assessment of information documenting ecological studies carried out by the BAlE Noranda Research Centre on behalf of Brunswick Mining and Smelting Corporation Limited on Belledune Harbour, N.B. (Environmental Protection Service, confidential communication), the Department of Fisheries and Oceans immediately initiated investi gations to determine the magnitude and geographical extent of cadmium (Cd) contamination in lobsters from the Belledune Harbour area. The information received from Noranda's studies indicated that between 1977 and 1979 Cd levels in muscle tissue (claws and tail) from lobsters captured within Belledune Harbour during the summer had risen substantially. Noranda supplied infor mation from a 1980 sample taken in early April which indicated that Cd levels in muscle tissue were lower than in 1979 but still were significantly elevated over pre-1977 levels. It was recognized that the observed changes could reflect a shift induced by sampling period changes rather than an absolute Fig. 2. Lobster sample sites surrounding Belledune decrease. No rand a agreed to supply the Department Harbour. with the hepatopancreas from the 1980 sampling to allow a more comprehensive 1979/1980 comparison in levels to be made. Following analyses of this material, it was judged that no significant decrease Tail muscle samples were obtained by dissecting an in levels of Cd had occurred. The Department of appropriately sized cube from the dorsal mid-section Fisheries and Oceans therefore proceeded to carry of the right lobe. Claw samples were obtained from out a detailed survey of Cd levels in lobsters from the dorsal mid-section of the large muscle of the the area. claw. Care was taken to avoid thawing of muscles during dissection to avoid drip. Hepatopancreas samples ( 1. 0-2. 0 g) were digested in 50 mL Fol in-Hu MATERIALS AND METHODS tubes with 5 mL cone. HN03 (BDH boiling chips) while muscle samples (1.0-1.5 g) were similarly digested with 1.5 mL cone. H2S04 and 2.5 mL HN03. Lobster capture sites are shown in Fig. 1 and Initially the tubes were heated gently until 2. Animals were captured by conventional trapping frothing had ceased and then more vigorously for methods and transported live to the laboratory approximately 30 min. After cooling, each digest was (Shediac, N. B., or Halifax, N. S.), individually made up to 25 mL in the calibrated Folin-Hu tube. bagged in polyethylene. Following determination of Digests of hepatopancreas were assayed for Cd by sex, total weight and carapace length, the hepato flame atomic absorption spectrophotometry, taking pancreas was removed and weighed. The tail muscle care to ensure that the aspirator tube did not was also removed from the shell. These tissues and contact the coagulated fat at the surface of the both clmvs were bagged separately in polyethylene digest. Flame atomic absorption conditions were: and deep-frozen. Prior to analytical sampling, the wavelength 228.3 run, slit width 1 mm with an air/ hepatopancreas was homogenized by hand-kneading. acetylene flame utilizing a deuterium arc backround corrector. External standard curves were checked by the method of standard additions. In muscle analysis, where the level of Cd was below the limits 'fl" of detection of flame atomic absorption, a graphite 55' furnace (Perkin-Elmer HGA2100) system was utilized (drying 100°C/30 sec, ashing 350°C/40 sec, and atomization 1700°C/6 sec). In both cases a Perkin OBOD BREAKWATER LOBE Elmer model 403 atomic absorption spectrophotometer HARBOUR EAST was used. Recoveries of added Cd by these methods averaged 99.4 ± 3. 05%. The laboratory has partici pated in the intercalibration exercises coordinated by the International Council for the Exploration of the Sea during the past number of years. Arithmetic and geometric mean Cd levels were calculated for each sample. Relative standard deviations were calculated from the log-transformed data. BELLEDUNE HARBOUR 47° 54' 64"50' Fig. 1. Lobster sample sites within and around Belledune Harbour. -67- RESULTS i\ND DISCUSSION mean for Harbour West is 175.8 11g Cd/g wet weight with a relative standard deviation of ll. 7%. The geometric mean of the Harbour East snmplL's ls 62.3 Tn the 1979 study of lobsters captured during 11g Cd/g wet weight with a relatlve standard devia the summer from within Ilelledune Harbour and tion of 21%, a mean significantly diffL'rcnt (t = analyzed by Noranda Research the arithmetic 5.17, P < • 01) from the lb rbour \Vest mean. 11w (standard deviation) and geometric mean (relative data for Harbour West and Harbour East suggest that standard deviation) levels of Cd in hepatopancreas there are two distinct populations characterized by were 88.34 (84. 3) and C,6. 87 (28%) ~g/g wet weight a minor degree of interpopulation migration. (28 animals). Arithmetic and geometric mean levels of Cd in hepatopancreas from lobsters captured by Two samples were taken from the seaward side of Noranda Research in mid-April 1980, as in the breakwater at Belledune Harbour. These samples our laboratory, were 151.2 (141.7) and 91.2 had geometric means of 21,.1 llg Cd/g wet weight ~g/g wet weight (58 animals), respectively. (24.0%) for the site opposite the dock (OllOD) and Re sampling of the harbour was carried out by the 24.1 11g Cd/g wet weight (23. 7%) for the site on the Department of Fisheries and Oceans at the end of seaward side of the distal end of the breakwater April 1980, and arithmetic and geometric means of (LOHE). This suggests that lobsters dwelling on the 150.7 (104. 5) and 105.9 (19. 4%) (55 animals), semvard side of the breakwater are a single popu respectively, were obtained. This suggests that li!tlon as Far as Cd is concerned and that few highly levels of Cd in lobster hepatopancreas from contnminated animals from within the harbour migrate Be lleclunc !!arbour had inc rea sed between the summer to the seaward side of the breakwater (both sites of 1979 and the spring of 1980. No significant had a combined total of 44 animals, one of which had d i.fference in total weight mean exists between the " hepaU1pancreas concentration of C'.d of 209 ~g/g; two 1980 samples (arithmetic mean weights of 453 ± the next highest level observed was 68.3 Jlg/ g). One 23 5. 2 g for the mid-Apri.l sample and 4 'i6 ± 239 g for sample of only six animals was obtained from the late April sample) hut the 1979 mean weight of approximately 1 km seaward from the mouth of 5fl8 ± 2 SJ g was 'wmewha t larger than the 1980 means. Relledune Harbour. One of these animals had a l}l ThP LinPar relationship between total weight :md Cd Level ln its hc>pat:opancrcas of 399 11 g Cd/g while the level in the hepatopancreas, while not al1vays slx hilli a g<'ometric mean of 23.1 (49. 7%). 1l1e wide significant (see he1ow), was always positlve so the variatl.on was caused by the presence of thl s one difference in Cd levels between 1979 and 1980 is animal" probably greater st ll than that calculated without taking the cffec t of weight of the animals into Levels of Cd in hepatopancreas from lobsters account .. captured at greater distances from Ilelledune Harbour are shown in Table 3. Cd levels decrease in both 1l1e late April lobster sample was taken from east and west directions from Be1ledune harbour. two areas: one along the harbour side of the 111e decrease is greater over the same distance conveyor causeway, designated hereafter as Harbour towards the west than towards the east. The major \Vest; the second along the harbour side of the' current floH along this coast is from west t Table L Cadmium (Cd) levels (llg/g wet weight) in lobster hepatopancreas from the area of Rellcdun<' Harbour. Relative standard Geometric deviation Arithmetic Sample site mean (%) mean (SD) N ------·------· Harbour Hest 175.8 ll • 7 47.6-372 203. 7 (9b. 'i) 29 lla rho<1r East 62. 3 21.2 11. 7-263 88. 8 (7 8. 9) 28 Outside harbour) opposite dock (OllOD) 24.1 24.0 1,,70-68.3 30.4 (19. 9) 15 Outside harbour at end of breakwater (LOBE) 24.1 23.7 4.65-209 32. 8 (36. 8) 30 0.8 km off end of breakwater (LOll E),) 23.1 1,9. 0 ~. 97-399 80. 3(156. 6) 6 ---~------~------~------68- Table 2. Frequency of cadmium ( Cd) levels in hepatopancreas of lobsters from nine areas (Fig. 1, 2). Cadmium concentration Harbour Harbour Point ~g/g wet 1-1eight West East P.E. I. L1W LOBE LIE L3E L4E L5E 0-10 5 15 3 3 1 2 10-20 3 14 11 7 11 8 4 8 20-30 1 4 3 10 7 10 8 5 30-40 8 2 1 2 3 6 7 t,o-so 2 3 5 3 3 50-100 2 4 2 6 2 100-150 6 2 l 150-200 3 3 200-250 7 3 250-300 5 1 300-350 3 350-400 1 29 28 26 31 30 31 30 25 17 Table 3. Cadmium ( Cd) levels ( ~g/ g wet weight) in lobster he pa to pane reas from areas around Belledune Harbour. ·------ Relative standard Geometric deviation Arithmetic Sample site mean (%) l~nge mean (SD) N Heron Is land, N.B. 3.85 22.0 2.19-8.26 4.03 ( L 31) 10 !.6 km west 3 (LHI) 11.8 2il. 5 4.13-119 16.3(20.0) 29 Be 11 edune Ha rhot1r ( Chapel Point) - Zero point 1.6 km C'ilS t (Ll E) 28.9 18.2 10.2-110 34.9(23.7) 31 4. 8 km eRst (L3E) 22.8 24. 5 t,, 55-246 32. 5(43. 5) 30 6 ,I, km east ( L4E) LB.O 12.5 7.13-53.9 30.15(10.8) 26 9.6 km east (L6E) l7. 3 22.2 6.1-50.9 20.5 (9.6) 19 Petit Roc her, N.B. 11.6 12. 3 6.26-22.1 21.2 (3. 9) 31 Nigadoo, N.B. 12.1 21.1 5.00-77.3 14.4(12. 6) 33 Stoneha ven, N.B. 7. 2 20.9 3.90-16.2 7.8 (3. 3) 35 Beach Point, P.E.I. ( 1973) 17.2 1.7. 7 6.07-52.0 19.4(10.3) 26 aHighway distances (on highway opposite Chapel Point) were: LlE - 3.1 km; L3E- 5.(, km; L4E- 7.il km; L61C- 10.0 km; Petit Rocher- 17.4 km, and Nigadoo- 21.0 km. -69- lobsters from Beach Point, P.E.I. are included for do\vnstream where it has been incorporated into the comparative purposes. This area, which has no known lobsters' food web (e.g. mussels) and accounts for anthropogenic inputs of Cd, had the highest levels the elevation over the 1973-1980 period. The of Cd of any of the areas sampled within eastern individuals containing high levels of Cd in their Canada (Uthe and Freeman, this report). hepatopancreas probably reflect movement of animals from Harbour West following incorporation of Cd into The Harbour West site is characterized by a their bodies. large number of highly contaminated lobsters, i 25 of the 29 (86%) individuals had hepatopancreas In a few of the sampl.ings a large enough size levels of greater than 100 ~g and none of the range VIas obtained to justify investigating the animals had a level below 40 In the relationship between the animal Height and Cd level Harbour East sample, highly contaminated animals in the hepatopancreas. The results are shoVJn in were still present but at a substantially decreased Table 4. A relatively small but significant frequency, i.e. only 9 o 27 (33%) individuals had positive relationship between total animal Height hepatopancreas Cd levels greater than 100 ~g/g while and Cd level in the hepatopancreas was found for the IS (55%) of animals had hepatopancreas Cd levels Harbour West and L6E sample sites (coefficients of less than 50 ~g Cd/g. determination of 0.24 and 0.33 respectively) but such a relationship is not precise enough to hav<' The frequency o highly contaminated lobsters any meaningful predictive value for calculation of fell sharply within the samplces obtained outside of the Cd level in hepatopancreas from total weight of Belledune Harbour. Considering the LlW, LOBE, animals. The very loVJ coefficients of determlnation LlE, L3E, L4E and L6E sites as a group, only 4 (2%) found with the Harbour East and Heron Island (New out of lh4 animals had a Cd level greater than 100 Mills) sampling probably reflect mixing of animals ~g/g while 148 (90%) had levels of less than SO Pg from within and external to the harbour in the first Cd/g. These data suggest that an acute Cd contami case and the narrow weight range present in the nat ion situation exists within Bel Ledune Harbour and second inst"ance., a mor0 cllrc>Ilic one in areas surroLtnding the hurbour~ Time has allowed only limited studies on Cd Animals within the western part of !lelledune levels in lobster muscle tissue. The results of Harbour are grossly contaminated (86% >100 ~g Cd/g) this study are shown in Table 5. It is obvious that but the frequency decreases VIith increasing cl istance the hepatopancreas Is a major Cd storage site since from this site. All the geometric means of the mean levels of Cd tn hepatopancreas corres-- Petit Rocl•er, Nigadoo and Stonehaven samples were ponding muscle means by from 96 to 2560 times. below that found in the sample from Beach Point Levels of Cd in tail muscle are considerably loVJer (Table ')) and may be considered as background or ( 3-lOx) than correspond .ing crusher claVI muse le normal levels. However, these levels should be levels. TI1e relationships between Cd levels in the compared with (l) the geometric mean of 3.85 ~g Cd/g three tissues analyzed are also shown (Table 6) and in the Heron IRland sample, and (2) the geometric again, while some significant linear relationships mean of 4.'30 pg/g in a sample from Petit Rocher were found between tissue pairs, only in the case of obtained in 1973 (Uthe and Freeman, this report). the LlE tail and crusher claw CA:I Levels is the These values may be a more realistic evaluaticln of relationship tight enough to be used in a predictive the levels to be expected wi.thin this area harl no manner. '111e lack of such a tight agreement in the ma_jor anthrrlpogenic sources c>f Cd been present. L4E and LbE samples is probablv due to the verv low Th_is suggPsts that a generalized area of Cd 1Pvel of Cd in il muscle from these site~ in whL:h pollution in lobster ists betv1een at least the Ll.\~ crtSt' Lhe analytical variClnce he1.._·omes a signifi~._·ant i te and do~,om ream heyond Stonebaven~ Tt ~..-·ont: ibutor to the variance within the system* impossible to detennine hov.J nnh·h of th-fs contami nation originates from Belledune Harhour a.nd how Tl1ere was no signi icatlt di.fferenl·e hetwec11 the much from other sources such as the city of Pklthurst geo1netric means for male and female lohsters from Uttd various river in thi l1ighly mineralized area. five sites (Table 7). TI1e wide range in Cd levels, Although the geon~tric mean of the Nigadoo sample is the smaller, non-normalized weigl1t and length larger tl1a11 tl1e corresponding mean of the Petlt ranges, would mask small sexual-related differences l.Zoche_r s Table 4. Hepatopancreas cadmium (Cd) levels/total weight relationships in Belledune area lobsters. Carapace Geometric length mean Regression equation Sample site (mm) N (~g Cd/g wet wt) ( coe ff ic ien t of determination) Harbour West >80 20 223.1 63-80 7 100.6 ( Cd) 90.47 + 0.21 (total wt) (0,24)a <63 2 114.5 Harbour East >80 8 85.8 63-80 15 56.3 ( Cd) 60.97 + 0.07 (to ta 1 wt) (0.04)C <63 3 54.4 L6E >80 2 36.69 63-80 9 16.53 ( Cd) 4.87 + 0.056 (total wt) (0.33)b <63 2 14.95 Ne'" Mills >80 2 5.66 63-80 28 3.75 ( Cd) 2.82 + 0.0035 (total wt) (0,()2)C <63 0 astgnificant at p < 0.01 bsignificant at 0.01 < p < 0.05 CNot significant; p > 0.05 Table 5. Comparison of cadmium (Cd) levels (geometric means) in hepatopancreas, tail muscle, and crusher claw muscle (relati.ve standard deviation) in lobsters from the Belledune area. Crusher claw Hepatopancreas Tail muscle muscle (~g Cd/g wet wt) (~g Cd/g wet wt) (~g Cd/g wet wt) Sample site N (%) (%) (%) LlF. 10 21+. 7 ( 16) 0.02 (14) 0.26 (11) L4E 12 2il.2 (7) 0.01 ( 11) 0.04 ( 1 0) L6F. 12 20.8 (17) 0.01 (20) 0.04 (14) -71- Table 6. Relationships between cadmium (Cd) content (~g Ccl/g wet wt) of hepatopancreas (]lg Cd/kg \vet wt), tail muscle, and cla1v muscle for lobsters from three sample sites. Coeffi.c ient Sample site Regression equation of determination LlE ( Cd) crusher 3.645 + 0.069 (Cd) tail o. 94" ( Cd) tan 12.38 + O. 36 (Cd) hepatopancreas 0.4lb L4E ( Cd) crusher 14.62 + 1.99 (Cd) taU 0. 29C ( Ccl) tail 6. 03 + 0.19 (Cd) hepatopancreas o. nc L6E ( Cd) crusher 15.41 + 2.61 (Cd) tail ( Cd) tan 4.16 + 0.31 (Cd) hepatopancreas asignificant at p < 0.01 bsignlficant at 0.05 > p ., 0.01 CNot significant; p > 0.05 Table 7. Cadmium (Cd) levels (~g/g wet weight) in male and female lobster hepatopancreas; number sampled in parentheses. Male Female Statistical Sample site Geometric Geometric significance mean (N) mean (N) Heron Island 3.66 (14) 4. 10 (16) NSa Harbour West 170. l ( 2 l) 191. 8 ( 8) NS Hi1 rbour East 58.79 (18) 69.93 (9) NS LIE 27.05 (16) 2G .. SLt (15) Petit Roc her 12.23 (15) II. 08 ( J 6) NS a p > .l (] -73- CADHTUH TN HEPATOPANCREAS OF AHER [CAN LOBSTER (llONARUS ANERTCANUS) FRON EASTI~RN CANADA by J. F. Lithe and H. C. Freeman Fisheries and Environmental Sciences Department of Fisheries and Oceans Halifax Laboratory Halifax, Nova Scotia BJJ 2S7 -74- INTRODUCTION cantly lower average wei.ght than the other samples. The effect of weight on Cd is small, as judged from the following observations: Tiw selection of the This study was initiated in 1973 when the larger animals from Petit Rocher (mean weight 'il6 ± 1nspection Service of the Canadian Department of 40 g) and Shippegan (mean weight 'i03.2 ± 37.2) gave Environment became concerned about the levels of geometric means of Cd for hepatopancreas of 5.13 and cadmium (Cd) in commercially canned lobster paste. 4. 37 ~ g/g (\vet wt) respectively, compancd with the Lobster paste is a popular food product prepared, in means of 4. 30 and 3. 79 ~ g/ g (wet wt) res pee ti vely large part, from lobster hepatopancreas. Therefore, for the complete samples. a study of Cd Levels in the hepatopancreas of lobsters from different e1reas of eastern Canada was The narro\V range of sample weights from ench carried out. site makes it impossible to assess accurately the relationship between Cd levels in hepatopancreas and total weights. \>le therefore sampled as wide a total ~1ATERIALS AND HETHODS weight range (market size) of lobsters as possible (N=41) in one area (Lismore). TI1e relationship bet\veen the total weight in grams and the hepatop 1~irteen live lobsters of each sex weighing ancreas's Ccl level in ~g/g (wet wt) was (Ccl HP) = between 400 and 700 g \vere obtained from each site 3.233 + 0.013 (total vrt, g) with a coefficient of by field personnel of the Department of Environment. determinatl.on of 0.30! where (Ccl HP) ~g Cd/g (wet Each sample area \vas not over 15 km in diameter and wt) hepatopancreas. The log transformation of the each sample was purchased during a single day of Cd values gave lop, 1o (CAl HP) = 0. 763 + 0.000381 fishing. (total wt) with a coefficient of determination of 0.346. Before sampling the lobsters, the sex, carapace length, and total weight were recorded. TI1e hepato In a similar manner the relationship between pancreas was removed intact, placed in a polyethy carapace lengths and Cd level in hepatopancreas from lene hag, and frozen for transportation to our the' Lismore sample was calculated to he log (Cd HP) laboratory. TI1ere, each hepatopancreas was weighed, = 0.247 + 0.084 (carapace length, em). The thawed, and thor-oughly mixed by kneading within the coefficient of determination ~Vas 0. 3!4. Tiw total bag. The Cd concentrations were determined in weight and length ranges used in the Lismore study duplicate acid digests (5 mL HzS04/HN03; 4: I, v/v) were 425-1731 g and 7.7-13.6 em respectively. of 0.2-0.5 g portions by atomic absorption spectro photometry (Perkin-Elmer Hodel 403 fitted with Some caution should still be used in inter deuterium arc background correction). Either a preting differences in levels among the various flame or graphite furnace was employed as well as areas sampled (Table I) since mean weights of the method of standard additions as required. sampled lobsters differ. The geometric mean concentration of Cd WilS It is of interest to consider temporal changes calculated for each site since probit Analysis in Cd levels in hepatopancreas. Five areas were indicated that the log-transformed concentrations sampled I yr later (Table 2). In this case, animals were more normally distributed than the non- were selected from within the same weight range. transformed data. Relative standard deviation of The geometric means of the C:d levels at !leach Point ench geometric mean was also calculated& and Neat Cove were significantly different from those found at the same sites the previous year (p < 0.01 and p < 0.05 respectively). We believe that RESULTS AND DISCUSS TON the difference at Neat Cove could be caused by the last sample being caught at somewhat different locations hut in the same general areas. TI1e marked The atomic ahsnrpt ion method used in this study difference in means for the Beach Point s~l1nples is fur cletE•rtninj_ng Cd was previottsly validated hy t1sing probably a result of sampling completely different a common standard atomic absorption method wh{_'re sites In the 2 yr. Support for this hypothesis Is chclated (APDC) Cd was extracted into an organic apparent in the llelledune study where signlfiC'Rnt solvent (HIHK) followed by atomic absorption spec changes in Cd levels i.n lobster hepatopancreas trophotometry .. \.Vhen our laboratory participated in occurred over distances less than 15 km. TI1ese five the Tnternation<1l Council for Exploration of the resamplcd areas are not in the vicinity of intensive Sea 1 _Lnterca1ibration studies, our results for Cd humnn habitation or industrial activity and it is fell in the mid-range of the values submitted by the unlikely that the changes observed In two of them other participants (Topping and Holden 1978). were due to changes in C'Ai loading of the environ ment. The distances between the designated ''ites on The results are shown in Table ]. 111e geo the north side of Prince Edward Island were not metric mecms vary from a 1 ow of 2. 82 wg of Ccl/g (wet large; therefore, changes in climate between the 2 wl) of hc>patopancre.:ls for 1ohstprs fr(lm Comfort f:ove yr is an unlikely cause of the differenL'e oDt;lincd toil high of 17.22 )1?,/g (\Vet wt) for tho,;c' from in llw ne;Jch Point me;1ns for, if this were true, the Br•aclt Point .. The nritllnH•tic nwan of ;~ll geometrLc otlH.'l- ln spit-e of the 1og trnnsfurmntion td- t·lH' dat.-1, REF I·:R I·:NCI·:s lht' LltiV!-' ~tnndard dt'VLlt:ions or t' Table t. Cadmium (Cd) In hepatopancreas of American lobster (Homarus americanus) from sites in eastern Canada in 1973. To ta 1 weight Weight of Cd in lobster of lobsters hepatopancreas hepatopancreas (g) (g) vg/g wet weight Arithmetic Arithmetic Geometric No. of mean mean mean Location animals (SD)a (SD) ( RSD Range NEWFOUNDLAND Arnold's Cove 50 532(96) 32.!(9.7) 8.82(31) 2.45-48.9 Comfort Cove 21 S31l(JJ5) 2R.I(6.3) 2. 82(311) 1.72-6.43 Lark Harbour 25 521l(75) 28.5(73) 10.89(21) 3.78-33.6 Britannia 20 639(200) 33.1(!00) 12.63(19) 4.il2-30.3 Bay 1' Argent 26 559(97) 32.9(8.0) 10. 83(16) 4.59-20.2 Port aux Basques 26 476(91) 29.5(5.!) 10.70(23) 4.25-45.0 NOVA SCOTIA Arichat 25 536(70) 26.0(4.()) 7.87(27) 3.22-19.6 Cape John 25 1,6il( 54) 22.9(3.8) 9.34(20) 3.06-18.0 Cheticamp 23 613(119) 34.4(7.9) 9. 14(36) 2.13-36.3 Dingwall 26 573( 139) 33.9(8.6) 13.30(20) 5.14-27.4 Frambois 25 499(61) 23.3(5.5) 12. 51(22) 4.05-52.9 Gulliver's Cove 25 466(52) 24.3(3.1) 11.84(16) 4. 70-lil.O Judique 25 442(73) 23.3(5.6) 8. 78(18) 4.54-25.8 La Have 26 557(83) 28.0(5.1) 8.15(18) 2.94-15.4 Larry's River 26 511!(91+) 27.4(4.3) il. 27(22) 3. 92-25. 1 Lismore 17 542(72) 25.3(3.7) 8.64(22) 3. 82-24.5 Liverpool 26 547(80) 21. 5(5. 3) 5.19(34) 1.33-1().7 Lockeport 23 506(83) 26.9(5.3) 7.38(28) 2.130-22.4 Main-a-Dieu 26 552(98) 30.8(4.8) 12. 58(22) 4.89-47.2 Meat Cove 26 547(124) 29.6(5.8) 6.32(23) 1.85-12.1 Parrsboro 26 612(104) 32.4(8.4) 9.13(31) 1.02-59.0 Pictou 26 481(59) 23.1(3. 3) 14. 36(27) 3.77-79.1 Pubnico 24 480(65) 24. 5(4. 8) l0.42(4) 5, 18-21. I, Sambro 25 679(79) 30. 1 ( 5. 6) il.03(23) 2.0 -18.0 Tangier 26 495(58) 24.5(3.7) 6.15(35) 2.4 -20.0 Victoria Beach 26 1,95(58) 22. 3(2. 9) 6.47(38) 1. 60-22.8 Whale Cove (Digby) 24 457(52) 23.6(4. 7) 7.05(29) 3. 77-20.7 PRINCE lm\·1 ARD [SLAND Beach Point 26 526(89) 24. 7(5. 2) 17.22(18) 6.07-52.0 French River zr, 491(94) 24. 5(5. 5) 11.95(31) 2.29-48.3 North Lake 24 599(135) 31.4(7.!) 16.73(20) 7.18-53.1, Tignish 2.) 531l(l19) 27.3(7.0) 14.03(19) 5.52-37.8 NEI~ BRLINSIVI CK Back Ray 26 471(82) 21+.6(4.4) 5.31(30) !.76-!4.'i Cape Torment i ue 2S 561(1!2) 27.11(6.3) to. 90(18) 1,. 13-22.4 Caraquet ] 7 380(52) 22.2(3.2) 3.47(33) 1.37-8.46 Grand Hanan 26 530(52) 26.8(4.11) 6.93(35) 2.60-31.5 Maces Bay 25 5fl0(99) 29. 7(5. 7) 9.65(31) 2. 93-40. 7 ~1iscou River 26 1,89(88) 25.4(6.9) 1,, 38(31) 1.65-10.6 Nequac 26 350(61) 21.3(5.7) 4. 72(24) 2.38- 9. 7 Petit Roc her 26 1,36(74) 25.0(5.2) 4.30(32) J.ll9-10.7 Richibucto 26 460(70) 22. 2(3. 3) 6.26(23) 3. 51,-]1,. 4 Shippegan 26 478(89) 25. 6(1,, 6) 3.79(39) 1.35-11.3 QUEBEC St e-Therese-de- Gaspe 26 56!(!24) 27.3(5.5) 10. 53(33) 3. 82-47.4 Arithmet lc overall mean a - Standard deviati Table 2. Cadmium (Cd) content in hepatopancreas of lobsters from five areas in 1974 and 1975; total weight range of lobsters 452-581 g. Cd in hepatopancreas, )Jg/g wet weight Geometric Geometric mean mean Area 1974 197 5 N Significance Tignish, P. E. I. 14.48(ll)a 15. 54(19) 0.23 28 NSb french River, P.E. I. 1!.88(6) 12.06(20) 0.04 24 Nsb Beach Point, P. E. T. 17.05(7) 8.44(19) 4.30 24 HSc North Lake, P. E. I. 14.65(14) 14.34(13) l. 02 25 Nsb Meat Cove, N.S. 6.32(17) 10. 77(8) 2.475 23 sd a Number of animals bNot significant CHighly significant (p < 0.01) dsignificant (p < 0.05) -77- STUDIES ON THE FORCED DEPURATION OF CADMIUM FROM THE AMERICAN LOBSTER (Hm1ARU~ AMERICANUS) by J. F. Uthe Fisheries and Environmental Sciences Department of Fisheries and Oceans Halifax Laboratory Halifax, Nova Scotia BJJ 2S7 -78- INTRODUCTION mortalities; pectate group- 6 mortalities). Analysis of sections of tissuP from a single hepatopancreas demonstrated that insignificant Cadmium (Cd) levels in lobster hepatopancreas ( <10%) differences in Cd levels exist among various are very high (l-50 JJg Cd/g wet weight) even in sections of the gland. Cd analyses were carried out lobsters obtained from areas with minimal human as described by Uthe and Freeman (this rt>port). impact (Uthe and Freeman, this report). High levels of Cd could be expected to affect sales of lobster Since long-term fet>d ing t>xperiments are not since Cd is known to accumulate in the kidney of man practical from an industrial point of view, the throughout Life and believed to begin inducing feasibility of removing Cd by injection of a common irreversible kidney damage nt kidney cortex levels chelator was investigated. Disodium calcium of approximately 200 JJg Cd/g (Friberg et al. 1971). ethylenedlamitH'tetracetate (NazCa EDTA), ns well The availability of a simple operation by which a as the divalent cations calcium or zinc or calcium frontal lobe of one side of the hepatopancreas could gluconate were tried. All solutions were made up in be removed enabled timed, forced depuration studies 3% NaCl to approximate isotonicity with lobster to be carried out by using measurements over time of blood. an individual animal's hepatopancreas level of Cd. Animals were to bt> injected every 2 d from 9 d postoppratively. The injt>ctions were administered MATERIAL AND METHODS into the ventral sinus, using disposable tuberculin syringes fitted with 25G needles. The following solutions were administered: Lobsters weighing between 450 and 600 g were held in individual plastic tanks, each with running 1. 10 mg calcium/mL as Na2Ca •EDTA; sea water (""l0°C at 100-200 mL/min) which was aerated prior to individual delivery to each tank. 2. Solution No. l containing 7.5 mg Cct Tht> frontal lobe of the hepatopancreas was removed g luconate/mL; by scribing a circular groove w:lth a dental drill ( 112 round burr) about 1-1~ em in diameter into the 3. Solution No. 1 containing 0.3 mg Na2Zn· carapacP, just enclosing the white tt>ndon mark EDTA/mL. (behind and below the eye) at about 10 o'clock and cutting tht> rest of the way through tht> shell with a All animals rt>ct>ivt>d 5 mg NazCa EDTA/kg per dose. scalpel at an angle describing a cone with its apex Gaffkemia infection was found in the lobstc'rs after insl.de the lobster. This sloping cut will allow five injections (12 d). The experiment was termi pasy reattachment of the shell piece. Tht> shell and nated immediately and the remaining frontal lobe of its underlying structurP are cut far enough around the hepatopancreas removed. to allow lifting of the incised area. The frontal lobe of the hepatopancreas is carefully grasped and tl1e isthmus joining the two lobes severed with a RESULTS AND DISCUSS ION sharp scalpt>l. The shelL and underlying parts were replaced and the shell piece glued to the main body of the shell with a thin layer of N-histoacryl-Blau, The results of the modified sodium alginate or a commercially avai lahle surgical cyanoacrylate pee tate feeding Pxperiments are shown in Table l. glue (Dr. D. E. Aikt>n, St. Andrews Biological The mean values for the individual groups at the Station). Cd Levt>ls were determined in each lobe start of the feeding period, the 70-d point and tht> after homogenization and digestion (200 mg tissue/5 158-d termination are also shown. In all cases mL HN03) by atomic absorption spectrophotometry. means were calculated only for those animals sampled Lobsters did not appear to he adversely affected by at two relt>vant periods. Differences were calcu this surgery. They resumed eating about 10 d post latt>d on tht> basis of individual data obtained for operatively and could successfully molt at a minimum each animal and significance levels were determined of 40 d postoperatively. by paired t-tpsts. Positive difference values indi cate' decre;sing levels of Cd over the test pt>riod. Partially degradt>d sodium alginate and sodium Only animals which consumed more than 5 g food per pectate we're prepared by Dr. Y. Tanaka (McGill feeding period were includt>d in these calculations. University). Tht> efficiency of thesP materials in preventing intestinal absorption of administered Cd It i.s obvious from the data that dietary has been described (Skoryna et al. 1972). administration of insoluble, indigestible, Cd binding agpnts is unablt> to bring about a large Dit>ts wert> composed of 20% cellulose' (replaced decrease in the level of Cd in the hepatopancreas. by either 5% alginate or pectate as requirt>d) and Of course, it is possihlt> that lobsters could digest 75% clams cast in 5% gelatin (J. Castell, pt>rsonal these degraded carbohydrate's hut, from the copious communication). All animals wt>re fed the control quantities of feces present in the tanks, it is diet (20% cellulose) for l wk, 14 d postopt>ratively doubtful. Attempts were made to collect and weigh prior to initiation of the expt>riment. Lobsters feces but variability in feeding and losses through were fed 10 g diet (as one pit>ce) three times a week overflow prevpnted accurate determination of daily over the course of the expt>riment. After 10 wk the fecal mass. In the control group it appears that Cd remaining frontal lobe was removed. Feeding was levels might increase somewhat over the course of rec;,.mecl 2 wk postoperat1veJy for an additional 88 d. the experiment. If this is so, then the alginate Consumption by each animal was determined by and pcctate feeding effect may be greater than the removing, weighing and discarding remaining food small decreases in Cd levels found hut the effects just prior to the next feeding. Each of the three are stlll of little significance to any practical feeding groups, containing 28 animals (mixed sexes) usage. at the start of the experimt>nt, suffered some mortalities during the coursP of the experiment The large relative standard deviation in (control group - 14 mortalities; alginate group- 9 hepatopancrt>as Cd levels (ranges from 35-80%) makes -79- sturlies of this sort extremely difficult unless yield lO ~gCd/g of hepatopancreas would be at least techniques like the surgical removal of hepato 100,000. pancreas portions are used to utilize each animal as its o¥m control. 'The operation is fast, simple and The very high concentration of Cd present in apparently does not harm the animal since feeding, hepatopancreas makes it tempting to postulate a growth and molting are readily resumed. Gross biochemical role for Cd in the lobster. 11lis would autopsy of animals which had been held post not be novel since a hl.ologl.cal requirement for Cd operatively for l yr or more in our aquaria showed in optimum growth in rats has been described that the frontal lobe does not regenerate. However, (Schwarz and Spallholz 1978) but the high level may adhesions between the hepatopancreas and other soft simply reflect a phenomenon similar to man in which tissues at the severing site were noted. Cd is stored in the kidney, the level increasing with age (Friberg et aL 1971). Cd in lobster Injection of divalent ions and chelators at increases with increasing weight (Uthe and Freeman, relatively high levels did not induce removal of Cd this report) so it is likely that the hepatopancreas from the hepatopancreas (Table 2). The log of the simply acts as a reservoir for Cd in lobster. binding constant of Cd EDTA is 16. 5. This suggests that, if any appreciable Cd equilibrium exists between haemolymph and hepatopancreas cells and a REFERENCES reasonable level of Cd is present in the haemolymph, EDTA should effect rapid removal of Cd from the hepatopancreas. This did not happen, suggesting Friberg, L., M. PiscRtor and G. Nordberg. llJ71. that either the concentration of free \.d in the C.:1dmium in the environment .. CRC Pres~;~ blood is too low to form appreciable• amounts of FWTA Cif'vc>Lll1d. lh6 p. complex or the animal is unable to to•xcret:c' the complex. lt is doubtful that the latter suggt•sl ion Schwarz, K., :mel J.E. Spallholz. 1978. Crowtil holds since EDTA is rapidly excreted by mammal ian effects of small cadmium supplements in rats kidney anrl not reabsorbed. It was also hoped that maintained under trace element-controlled the fortification of the injection solution with conditions. In Cadmium 1977. Edited cC!lcium gluconate or zinc could increase the Proceedings: First International Cadmium availability of Cd in the haemolymph by competitive Conference, San Franc is co. Metal Bullet in Lt., action of these divalent cations for Cd binding London. p. 105-109. sites. No such effect was found within the relatively short time period of this experiment. Skoryna, S.C., Y. Tanaka, H. Moore jr., and J.F. Stara. 1972. Prevention of gastrointestinal All of these results suggest that Cd in lobster absorption of excessive trace elements intake. hepatopancreas is extremely tightly bound and _!_r1_ Trace Substances in Environmental Jlp;J] th, dynamic<1Lly llllilVnilahlc to either the haemolymph or VT. Proceedings of University of Missouri's the gut lumen~ 11lis is not unexpected since, if OlH' 6th Annunl Conference nn Trace Suhstance..-; in considers a background lt~Vl'l of Cd in \Vater Lo be Environnwntalllealth. Ed._D.D. lk>mphill. around 0 .. l JJg/L or less, Llw concentrat fon factor lo University of ~1issr>uri-Columhia, ~!o. p. 1-ll. Table J. Ef feet of feeding degraded sodium alginate or sodium pee tate upon cadmium ( Ccl) levels in lobster he pa topanc reas - means and differences ( ~ g Cd/ g wet wt), N Differenced Control group 7. RR + 2.91 ().93 + 2. 70 22 0. 75 + 2.46b 6.83 + 3.20 9. 27 + 1,. 09 12 -2. 52 + 2. 59 7.68 + 3.36 9. 27 + 4.09 12 -1.59 + 2. 71, 10.61 + 6.40 9.50 + 4. 22 1.10 + 4. 64 9.28 + 4. 72 7.98 + 4. 22 16 1. 37 + 3. 78 10.1•2 + 7.15 7. 98 + 4. 22 16 2.45 + 4. 82c Sodium pee tate group 12.41 + 9.7() 10.59 + 7.12 26 l. Sl + 4.15 10.78 + 7.26 LO. 87 + 7. 79 20 -0.09 + 2.07 12.40 + 9.07 10.87 + 7.79 20 1.53 + 2. 50 "A positi.ve value indicAtes a drop in Cd levels over the ti.me period. bMean + standard deviation for individual animal rlifferences. cNot significant at the 5% level; all other differences are not significant. -80- Table 2. Effectiveness of intrasi.nal injections upon cadmium (Cd) levels in hepatopancreas. Treatment Mean + Std. Dev. N Differencea CaNa 2 EDTA Start 12.13 + 3. 43 7 End 11.71 + 5.28 7 o. t.l + 1.6ob CaNa 2 EDTA + Start 11.25 + 3. 33 7 ZnNa 2 EDTA End 10.78 + 2.12 7 0.49 + l. 58 CaNa 2 EDTA + Start 13.88 + 8.15 7 Ca Gluconate End 13.78 + 9.33 7 0.27 + 2. 30 aMean + standard deviation for individual animal dHferences. bAll differences are not significant. -81- THE UPTAKE OF CADNilJM BY RATS FROM A DIET BASED ON CANNED AMERICAN lDBSTER ( HOMARUS ANERICANlJS) HE PATOPANCREAS PREPARATION by C.L. Chou and J.F. lithe Fisheries and Environmental Sciences Department of Fisheries and Oceans Halifax Laboratory Halifax, Nova Scotia B3J 2S7 -82- INTRODUCTION RESULTS AND DISCUSSION This paper is a summary of a publication (Uthe The animals in the various groups did not eat and Chou 1980) on the uptake of cadmium (Cd) by rats significantly different quantities of food, nor show from a diet based on canned lobster hepatopancreas, significantly different weight gain. and from a generally used experimental diet based on casein. lloth casein- and hepatopancreas-based diets Average Cd levels for kidney, 1 iver, spleen and contained equivalent amounts of the Pssential bral.n from each dietary group are shown in Table l. nutrients for rats. C'.anned lobster hc'patopancreas Cd Levels in kidney, liver and splec>n of rats on the was selected as on<> of the diets lwcausL' hepato I,,f>ster hepatopancreas diet we're significantly lower pancreas is the major ingredient of canned lobster than those of rats on the casein-based diets spiked paste, a commercial product retailed in Canada. with 0:1 chloride. Cd uptake in kidneys and livers of rats on the first diet was only 55 and 68% respectively of the amounts taken up by these MATER IA LS AND METHODS tissues in rats on the second diet (Table 2). The amount of "free" (polarographically active) Diets were prepared based upon either casein Cd in the canned lobster hepatopancreas was 45% of (10 or 20% protein) or canned lobster paste (10% total Cd. protein). Diets were .isocaloric (332 cal/ g), con tained Cd at 20.9 11g/g wet weight and for all prac These results indicate that "free" rather than tical purposes had the same coefficients of digesti "total" Cd of a diet determines the extent of Cd bility. Cd chloride was used to fort! fy both casein uptake. Hepatopancreas, when assayed after rPmoval diets. Levels of calcitun, selenium, and zinc in from frc>shly killed animals, had no det,~ctablc deficient diets were fortified to the highest diet amount of free Cd. If the uptake l.s dependent upon level with calcitun chloride, sodium selenite and the presence of free Cd, then Cd in hepatopancreas zinc sulfate. Groups of 18 young female Sprague from a boiled lobster may be much less available Dawley rats were individually fed ad libitum for than Cd from canned lobster hepatopancreas, since 90 d. Body weights were determinedtwice weekly and boiling is a much less vigorous treatment than the food ingest ion was determined dally. At the end of canning process. the feeding experiment, following decapitation, the brain, 1 iver, kidneys and spleen were removed from each animal, blotted, freed of extraneous tissue and REFERENCES weighed. After homogenization with water, the samples were frozen for storage until analyzed for Cd by atomic absorption spec tropho tome try. Due to Uthe, J. F., and C. L. Chou. 1980. Cadmium levels in analytical difficulties encountered by the con selected organs of rats fed three dietary forms tractor, we reanalyzed as many of the original of cadmium. J, Environ. Sci. Health !SA: homogenates as possible (Uthe et al., this report). 101-119. Table 1. CadmiLm1 ( Cd) (~g/ g wet weight) in tissues from rats fed various diets. Diet Casein Lobster heEatoEancreas 10% !.'rote in 20% Erotein 10% Erotein Mean SD N Mean SD N Mean SD N Kidney 12.32 2.41 15 11. 2 3.0 16 5.06 l. 41 11 Liver 5.29 o. 97 16 5. 80 1. 36 12 2. 72 1. 56 10 Spleen o. 79 0.28 18 0.23 0.117 18 Brain 0.019 o. 014 1 5 0.034 o. 015 16 o. 017 o. 013 18 -83- Table 2. Total uptake of cadmium (Cd) (~g), mean and (SD), in tissues from rats fed various diets. Diets Casein Lobster he~:ato~:ancreas fo% 2rotein 20% protein 10% ~:rote in Total Cd ingested 20300 ( 2 800) 27200 (2300) 2.5700 (2000) Total Cd kidney 20.6 ( 5. 1) 20. 1 ( .5. 5) 10.5 (2.0) % ingested 0.072 0.074 0.040 (55%)a Total Cd liver 35.4 (6700) 39.0 (l 0800) 22600 (3000) % ingested 0.118 O.L40 0.088 (68%)a a % ingested relative to casein diets -85- ADENYLATE ENERGY CHARGE AND ATPASE ACTIVITY IN AMERICAN LOBSTER (HOMARUS AMERICANUS) FRON BELLEDUNE HARBOUR by K. Haya, C. E. Johnston 1 , and B. A. Ivai wood Fisheries and Environmental Sciences Department of Fisheries and Oceans Biological Station St. Andrews, New Brunswick EOG 2XO ll'resent address: Biology Department, University of Prince Edward Island, Charlottetown, P.E.I. CIA 4P3 INTRODUCTION Approxinwtely 1 g or :lCC\11"iltP1y welr•,lll'd, pulverized gil_l or hepatopctncreas tissue was homogenized, at ice bath temperatures, in 2 mL of 6% It has become evident that acute toxicity tests HCl04 The effect of anoxia or salinity stress on the Cd ANALYSIS adenine nucLeotides and AEC of aquatic animals has been variable. Exposure of edulis to air l'nere was a wide variation in Cd Levels between (Wijsman 1976) and exposure estuarine individuals, especially in those from Belledune molluscs to reduced sali.nity (Rainer et al. 1979) Harbour area (large range values, Tables 1-3). Two caused a decrease in AEC but the total adenlyate d ist inc t populations were found in the Belledune pool remained constant. Both the AEC and to tal lobsters (N=24): those having significantly elevated adenylates dec rea sed during hypoxia in the muscles Cd levels (N=l7, p < .001) compared to the of gold fish, auratus (van den Thillart et Stoneha ven lobsters ( N=l2), and those showing no al. 1980). anoxia caused a decrease significant difference (N=7). There was no corre hottler 1978). Tile AEC may lation between size of Belledune lobsters and their also remain stable when ATP decreases, by reduction Cd content. of the total adenylate pool (Chapman and Atkinson !973). '11w results from our lobster studies All data were classified, according to the Cd resemble the latter case. Although the AEC of gills content of lobsters, into the following: Belledune from Bll and RC lobsters ls significantly lower than Harbour lobsters having elevated Cd levels ( BC), SH controls, the difference is small. Addlliomllly, llelledune Harbour lobsters with control levels of C,d the AEC is no too different from the sl.abil i?.ed (llU) and St:onehaveu (SH) controls. 11w llU lobsters idc.ll value of 0. 85 (Chapman et • l 97 1) and well probably recently migrated into the Cd-contamtnated within the range (0.8-0.9, Ivanovici 1979) expected area, and were caught before significant Cd uptake for viable cells. occurred. TI1e causative agent for lower AEC and adenine 'll1e Cd concentration of a11 lobsters varied nucleotides of llU and HC lobsters compared to SH among the hep8topancreas, gill and muscle (483.2 ± controls is unknown. Cd is probably not responsible 153. l, 69. 79 ± 27, 22, 2, 18 ± 1. 28 ppm dry wt, since the values for BU lobsters 1vere identical to res pee tively, Tables 1·-3). 11w hepatopancreas Cd BC lobsters. No correlation between Cd levels and concentration was 5-8 times greater than the Cd any of the biochemical parameters was observed concentration of gill, and gill Cd concentration was (Tables 1-3). High Cd levels were observed in the 30 times greater than the Cd concentration of BC, but apparently have not reached toxic levels as muscle. Induction of metallothioneins may be others have remained healthy since their capture. involved in the preferential deposition of Cd in the The differences observed between Bell.edune Harbour hepatopancreas. Tne occurrence of metallothioneins area and Stonehaven lobst"rs may be due to has been found i.n several marine invertebrates geographically related reasons or to the presence of (Olafson et al. 1979; Talbot and Hagee 1978). sublethal concentrations of other pollutants. ANALYSIS OF ADENINE NUCLEOTIDES ATPASE ACTIVITY The size of the total adenylate pool per gram No significant differences were found in the of tissue in the lobsters increased in the order Na,K ATPase or residual ATPase (ouabain-insensitive) hepatopancreas < gills< muscle (Tables 1-3). 11H• activity among BU, BC or SH Lobster gills (Table 1). major cHUSl.:. of this dlsparity tn distribution of tlH.' Previous stud il"s wi lh Homarus nmPricanus dPmon adenylntes is the ATP comron('nt., ThP ('Olll't"'!ltJ~atlons strnt:t~d '' ?'i% incrt·Hst•_ln_r-,:->'l Table 1. Cadmium (Cd) levels and biochemical analysis results for muscle tissues of Cd-contaminated lobsters from Belledune Harbour. Mean ± 95% Parameter confidence Correlati.ona analyzed N interval Rrtnge coefficient Cd ppm Controlb 12 o. 10 :1: o. 06 0.01- 0.35 dry wt BelleduneC 17 2.18 ± l. 28**d 0.41-11.15 ATP Control 12 20.77 ± 1.10 17.11-23.59 -0.291 p mole/ g Belledune 17 20.49±2.20 6.61-26.17 -0. 187 ADP Control 12 3.32±0.16 2. 71 3.88 -0.599* lJ mole/ g Belledune 17 3.45±0.36 1. 95- 4. 10 -0. 192 AMP Control 12 0.52±0.04 0.41 0.61 -0.594* lJ mole/ g Belledune 17 0.53 ±0.07 0.38- 0.94 -0.102 Total adenylates Control 12 24. 98 ± o. 96 22.95-28.08 o. 174 lJ mole/ g Belledune 17 24.1+9 ±2. 45 8.96-30.50 -0. 190 AEC Control 12 o. 911± o. 003 0.902-0.920 0.437 Belledune 17 0.905±0.009 0.845-0.921 -0.038 acd concentration vs parameter analyzed, * p <.05. bcontrol animals: 6 males, 6 females; mean wt = 473 ± 71 g. CBelledune Harbour Cd-contaminated animals: 14 males, 3 females; mean wt = 601 ± 77 g. dLevel of significance in t-test - ** p < .01. Table 2. Cadmium (Cd) levels and biochemical analysis results for hepatopancreas tissues of Cd-contaminated lobsters from Belledune Harbour. Mean ± 95% Parameter confidence Correlationa analyzed N interval Range coefficient Cd ppm Controlb 12 30.88 ± 9.68 9.48 - 70. 11 dry wt Belledunec l7 483.2 ±l53.1***d 10h.30 -1103.00 ATP Control 12 2.62 ± o.] 9 2.23 - 3.25 o. 180 jJmOll'/ g Helledune 17 2.49 ± o. 16 I. 85 3.03 -0.087 ADP Control 12 0.69 ± o. 11 il. 33 - I. 03 0.366 pmole/g Belledune 17 0.67 ± 0.07 0.40 - 0.91 0.366 AMP Control 12 0.25 ± 0.03 o. 18 - 0.35 0.338 ~mole/ g Belledune 17 0.24 ± 0.03 o. 11 - 0.41 0.236 Total adenylates Control 12 3. 56 ± 0.29 2.89 - 4.63 0. 292 jJmOle/g Belledune 17 3.37 ± 0.19 2.36 - 4. 13 o. 125 AEC Control 12 0.836± 0.014 0.808- 0.869 -0.055 Belledune 17 o. 83!± 0.013 0.781- 0.876 -0.326 -----· acd concentration vs parameter analyzed .. bcontrol animals: 6 males, 6 females; mean wt 473 ± 71 g. CBelledune Harbour Cd-contaminated animals: 14 males, 3 females; mean wt = 601 ± 77 g. dLevel of significance in t-test - *** p <.001. -89- Table 3. Cadmium (Cd) levels and biochemicaL analysis results for gill tissues of Cd-contaminated lobsters from Belledune Harbour. Mean ± 95% Parameter confidence Correlation" analyzed N interval Range coefficient Cd ppm Controlb 12 3.68 ± o. 76 1.91 7.19 dry wt Belledunec 17 69.79 ±27.22***d 24.40 -267.30 ATP Control 12 5.27 ± 3.69 4.24-6.78 0.268 pmole/g Belledune 17 3.99 ± 0.27*** 3. 10 - 5. 22 0.051 ADP Control 12 o. 63 ± o. 07 0.43 - o. 85 -0.033 Jlmole/g Belledune 17 0.65 ± 0.07 o. 32 - o. 85 o. 007 AMP Control 12 o. 55 ± o. 44 o. 43 - 0.68 -0.019 pmole/g Belledune 17 0.48 ± 0.05* o. 32 - o. 64 0.082 Total adenylates Control 12 6.45 ± 0.44 5.10- 8.24 0.217 pmole/ g Belledune 17 5. 12 ± o. 34*** 4.02 6. 62 0.054 AEC Control 12 o. 866± o. 006 o. 843- 0.882 0.333 Belledune 17 o. 841;± o. 008**'' 0.820- o. 872 -0.030 Na, K ATPase Control 12 4. 93 ± o. 73 3.1!5- 7.29 -0.330 pmole Pi/mg Belledune 16 5.07 ± I. 24 0.83-10.93 -0.050 pro te in/h Residual ATPase Control 12 14.88 2. 61 9.65- 23.28 0.221 pmole Pi/mg Belledune 16 14. 70 ± 2.69 2. 65 20.88 o. 084 pro te in/h acd concentration vs parameter analyzed. bcontrol animals: 6 males, 6 females; mean wt = 47'3 ± 71 g. c Belledune Harbour Cd-contaminated animals: 14 males, 3 females; wt 601 ± 77 g. dLevel of significance in t-test - * r <.05, *** p <.001. -90- Table 4. Cadmium ( Cd) levels, adenine nucleo tides and adenylate energy charge of Cd-uncontaminated lobsters (N=7) from Belledune Harbour. Mean ± 95% Correlation Parameter confidence coefficient t-test - a Tissue analyzed interval Range compared to [Cd) results Gills Cd 5.58 ± 1. 74 2.42 - 9.31 NS SH ppm dry wt p <.001 BC ATP 4. 13 ± o. 60 2.65 - 4.95 0.289 p <.001 SH ~mole/g NS BC ADP 0.69 ± o. 13 o. 51 - 0.92 0.243 NS SH ~mole/g NS BC AMP 0.58 ± 0.09 o. 32 - o. 72 -0.325 NS SH ~mole/g NS llC To tal adenine nucleotides 5.39 ± o. 74 3.48 - 6. 33 0.2lll p <.05 SH ~mole/ g NS BC AEC 0.830± O.O!L1 o. 792-0.84 5 0.755 p <.001 SH NS BC Tail muscle Cd o. 18 ± 0.2 0.04 - 0.45 NS SH ppm dry wt p <.01 BC He pa topanc reas Cd 2 7. 17 ±14.46 7.53 -65. 46 NS SH ppm dry wt p <.001 BC asll = Stonehnven control LolH;ters, N=12. BC = llcUedune Harbour Cd-contaminnted lobslt'rs, N=l7. llelledune Harbour uncontaminated lobstet·s: 4 males, 3 ft'males; mean wt .'>03 ± 100 g. activity is transitory and, under the more chronic These criteria may still be useful to :indicate exposure to Cd of BC lobsters, the stimulatory sublethal effects in lobsters under stressful effect of Cd on residual ATPase activity is lost conditions of Cd; however, the Belledune Harbour through some adaptive mechanism. There are large area lobsters are unaffected by present levels of individual variations in Na, K ATPase and residual Cd. ATPase (see range Table 3) and a larger sample size may have demonstrated some differences. ACKNOWLEDGMENTS CONCLUSION hie thank Dr. B. Dredzic for helpful suggestions for the development of adenine nucleotide assays, L. Lobsters residing in the Cd-polluted waters of E. Burridge for assistance in Cd assays, A. Belledune Harbour have remained healthy. The high Sreedharan for assistance in statistical analyses, leve] s of Cd accumulated by Belledune lobsters have Drs. V. Zitko and J. F. Uthe for reviewing the not resulted in deleterious changes in ion transport manuscript. in the gills, or the metaboLic energy state of the animal because: REFERENCES 1. 111e AEC was within the range expected for healthy individuals; Atkinson, D. E. 1977. Cellular Energy Metabolism 2. Lack of correlation of Cd levels to changes and its Regulation. Academic Press, New York, in AEC and adenine nucleotide pool; p. 85-107. 3. No significant differences of ATPase Bakke, T., and H. R. SkjoldaL 1979. Effects of activity between Cd-contaminated and toluene on the survival, respiration and non-contaminated lobsters; adenylate system of a marine isopod. Mar. Pollut. BulL 10: 111-llS. 4. Lack of differences in adenine nucleotides and AEC between Belledune Harbour lobsters \vith high Cd levels and those with Cd levels similar to Stonehaven controls. -91- Be is, I., and E. A. Newsholme. 1975. The contents Talbot, V., and R. J. Magee. 1978. Naturally of adenine nucleotides, phosphagens and some occurring heavy metal binding proteins in glycolytic intermediates in resting muscles invertebrates. Arch. Environ. Contam. Toxicol. from vertebrates and invertebrates. Biochem. 7: 73-81. J. 152: 23-32. Thurberg, F. P., A. Calabrese, E. Gould, R. A. Chapman, A. C., and D. E. Atkinson. 1973. Stabili Greig, M. H. Dawson, and R. K. Tucker. 1977. zation of adenylate energy charge by the Response of the lobster, Homarus americanus, to adenylate deaminase reaction. J. Biol. Chern. sublethal levels of cadmium and mercury~ 248: 8309-8312. 185-197. In Physiological Responses of Marine Biota to Pollutants, Vernberg, F. J., A. Chapman, A. G., L Fall, and D. Calabrese, F. P. Thurberg, and v. B. Vernberg Adenylate energy charge in ( eds.). Academic Press, New York. during growth and starvation. 1072-1086. Tucker, R. K. 1979. Effects of vivo cadmium exposure on ATPases in gill the lobster, Hartree, E. F. 1972. Determination of protein: A Bull. Environ. Contam. modification of the Lowry method that gives a linear photometric response. AnaL Biochem. l;8: 422-427. Van den Thillart, G., F. Kesbeke, and A. van Haarde. 1980. Anaerobic energy-metabolism in gold fish, Hess, B., and K. Brand. 1974. Methods for animal Carassius (L.). Influence of hypoxia tissues and micro-organisms, p. 400. In and anoxia compounds and Methods of Enzymatic Analysis, H. U. glycogen. J, Comp. Physiol. B 136: 45-52. (ed.), Academic Press, Inc., New York. Watson, T. A., and F. W. H. Beamish. 1980. Effects Ivanovici, A. M. 1979. Adenylate energy charge: of zinc on branchial ATPase activity in vivo in potential value as a tool for rapid deter rainbow trout, Salmo Comp-;-Bioc hem. mination of toxicity effects. Proceedings of Physiol. 66C: ll-82. the Fifth Annual Aquatic Toxicity Workshop, November 7-9, 1978, Hamilton, Ontario. Wong, Wijsman, T. C. M. 1976. Adenosine phosphates and P. T. S., P. V. Hodson, A. J. Niimi, V. W. energy charge in different tissues of _Hytilus Cairns, and U. Borgmann (eds.). Fish. Mar. edulis L. under aerobic and anaerobic Serv. Tech. Rep. 862, p. 241·-255. conditions. J, Comp. Physiol. B 107: 129-140. Jaworek, D., W. Gruber, and H. U. Bergmeyer. 197L,, Zs-Nagy, and M. Ermini. 1972. ATP production in Adenosine-5'-diphosphate and adenosine-5' the tissues of the bivalve Mytilus monophosphate, p. 2127-2131. In Methods of galloprovincialis (pelecypoda) under normal and Enzymatic Analysis, H. U. Bergmeyer (ed.). anoxic conditions. Comp. Biochem. Physiol. Academic Press Inc., New York. 438: 593-600. Lamprecht, W., and I. Trautschold. 1974. Adenosine-5'-triphosphate, determination with hexokinase and glucosc-6-phosphate dehydro genase, P• 2101-21!0. In Methods of Enzymatic Analysis, H. U. 8ergmeyer (ed.). Academic Press Inc~, New York~ Neufeld, C. J., C. W. Holliday, and J. ll. Pritchard. 1980. Salinity adaptlon of gill Na,K ATPase in the blue crab, sapidus. J. Exptl. Zool. 211: 21 Neufeld, G. L, and J, B. Pritchard. 1979. Osmoregulation and gill Na, K ATPase in the rock crab, : response to DDT., Comp., lliochem. : 165-172. Olafson, R. W., A. Kearns, and R. G. Sim. 1979. Heavy metal induction of metallothionein synthesis in the hepatopancreas of the crab Comp. Biochem. Physiol. 628: Rainer, S. F., A. M. Ivanovici, and H. A. \~adley. 1979. Effect of reduced salinity on adenylatc energy charge in three estuarine molluscs. Mar. Biol. 54: 91-99. Schottler, U. 1978. The influence of anaerobiosis on the levels of adenosine nucleotides and some glycolytic metabolites in sp. (Annelida, Oligochaeta). Physiol. 61B: 29-32. -93- A PRELIMINARY STUDY OF THE HISTOLOGY OF TilE HEPATOPANCREAS, GILL AND GREEN GLAND TISSUES OF AHERICAN LOBSTERS (HOMARUS AMERICANUS) COLLECTED FROH THE BELLEDUNE AREA OF THE BAY OF CHALEUR by P. Odense and C. Annand Fisheries and Environmental Sciences Department of Fisheries and Oceans Halifax Laboratory Halifax, Nova Scotia B3J 2S7 -94- INTRODUCTION (Panulirus argus Latreille) and the crayfish (Astacus fluviatilis), respectively. Travis was concerned with cellular changes during the course of High levels of cadmium ( Cd) had been found in the molt cycle while Davis and Burnett used auto the hepatopancreas tissues of lobsters caught in the radiography to demonstrate the growth and cell Belledune Harbour area (Uthe et al., this report). differentiation, or ontogeny, as these authors pre In addition to the concern that the levels were fer, of the cells of the hepatopancreas during the potentially dangerous to human health, it was also intermol t period. Of these studies, the work by considered possible that the Ccl could be harmful to Davis and Burnett is the most definitive and, the lobster itself. For this reason, sampling of although the study was done on tlw crayfish, our lobster tissues for histopathological examination results indicate that the work may be extrapolated was carried out in con june tion with the sampling for to 8pply to the American lobster. Cd analysis. Tn essence, the hepatopancreas consists of a 111e he pa to pane reas was se lee ted for histo vast number of tubules which open into a clue t logical study both because of its sometimes high Cd system. The tubules are blind sacs and, at the levels (Uthe and Freeman, this report) and because apex, embryonic cells are found which divide and of its active role in the storage and metabolism of move proximally down the tubule to become in order divalent metals - iron, copper and calcium - during an absorptive cell, a secretory cell, a fibrillar the molt cycle (Davis and Burnett 1964; Travis cell and finally an atrophying cell at the entrance 1955a). Cd affects cell membranes and for this into the hepatopancreas ducts. The absorptive cell reason the gill tissues with their thin epithelial has a basal or a centra] nucleus, small granules cell cov"ring and the epithelial cells of the and, during the premol t or early postmol t stages, tuhul es of the green gloncls wert> contddert:'d as has many small vacuoles at the' periph<>ry fi ll"cl with potentially susceptible tissues whic·h wnuld he' cnlcospher[tes or calcium phosphate spherul('S~ In target organs of Cd toxicity. thP spcretory stage th<> nuc!pus 1s has;ll and large vacuoles appear in the cytoplasm and are som('tirnes Also, in a study on factors affecting thc' seen dischacging their contents into the lumen of toxicity of Cd to the fiddler crab, Uca pugilator, the tubule. Secretory cells become fibrillar cells O'Hara (1973) reported finding the highest concen and these are seen only in small numbers among the tration of Cd in the green gland, followed by gill, other cells. They contain iron and show striations hepatopancreas and muscle. running from the base to the lumen, and have a basally located nucleus with a large nucleolus. Finally, at the proximal end of the tubule, MATERIALS AND METHODS atrophying cells are found which are small, have pycnotic nuclei and, in some instances, the nuclei havp undergone karyorrhexis .. During the lll'riod April 28-May 5, 1980, 'l72 lobst,,.s wen' snmplecl for chemical analysis. During Jn the examination of the Belledune lobster this time v;c t:ook t:issue samples from 118 lobsters hepatopilncreas sections, ,qll these types of cells for histological study. In all cases, carapace were observed.. Sections may be cut through one length, weight of hepatopancreas, total hocly cveight, tubule at the level of the absorptive cells, another sex, rlat:e and location of capture of each animal tubule at the level of the secretory cells, or a cvere recorded and the lobster sample numbers used longitudinal or oblique section may demonstrate the for chemical and histological examinati.on presence of all these cell types in one tubule. corresponded. Whenever possible, the molt cycle Most of the ·lobsters were staged by the method of stage was determined. Drach (1939) and were found to be in the intermolt or early premolt stage. Travis has observed that The sarnpl ing r-ecord is summarized in Table L the cellular composition of the tubule varies during The lobsters which vJere sampled, the Li ssues sampled the molt cycle. She also notes that the animal's and the fi.xatives used are listed together with El. size anrl water temperature may affect the rate of key to the area where the lobster was captur.~ed and, change of cellular composition of the tubules during if available, its stage in the molt cycle. An "a" the molt cycle, while Ogura (1959) notes that the in the table indicates lohsters which were selected properties of the epithelial cells of the gland vary by Dr. J. Uthe for a blind study in which the to a certain extent according to the individual histology and the pathology (if any) of the lobsters animal studied. It is thus in the light of this were compared without a prior knowledge of the Cd information about cell types and individual varia levels found in the tissues of these animals. After ti.on that the sections of the hepatopancreas must be fixation, all the tissues were embedded in paraffin, considered. Our conclusion is that no histopatho sectioned at S11 and stained with haematoxylin and logical changes are to be seen in the sections which eosin. The sLides were examined and photomicro \.Jere examined and hence' the elevated Cd levels in graphs taken, using a Zeiss Photomicroscope III. the hepatopancreas have been without detectable effect on this tissue. The cell types and varintions observed wert> all within the normal RESULTS AND DTSCUSS TllN limits of' variation. However, 1t should also be norl'd t:h;tt other workt-"rs have rt>porled t-hat crw;tilCPtlns ;~rp mort> suS('t)pt!hl(• to tilt' c•fft>cts of toxic SllbSiilllCt'S during moltln)'. or ,.,·dysls (Silrogll;, '""' Sc;H In the Crustacea, the paired green or antennal gLmds produce a secretion or "urine" and are The hepatopancreas, gill and green gland involved in ionic and osmotic regulation. Travis tissues of 118 lobsters from various areas at or ( 1955b) suggests that in the spiny lobster this near Belledune Harbour in the Bay of Chaleur have organ is instrumental in conserving calcium for been examined histologically. No histopathological hardening the skeleton following the molt, and this changes were observed regardless of the \AI level is accomplished by reclucing the amount of calcium found in the hepatopancreas of the animals being excreted In the urine. In the lobster the pair of examined. While this is an encouraging result, any glands are found at the base of the antennae just in enthusiasm should be modified by the following front of the stomach sac and consist of an end sac, considerations: First, the lobsters examined were an excretory tubule or labyrinth, and a bladder all in their intermolt or early premolt stage. As which opens to the outside by a shor duct. The noted earlier, crustaceans are more susceptible to tubules in the labyrinth are lined by single cell toxic substances during the ecdysis or molt period. layers of cuboidal eplthel ial cells wlth cent t-al Secondly, the hepatopa.ncrens was examined because of nuclei. Figure 5 shows a portion of the labyrinth. the high level of Cd found in this tissue, and the The cells are Ln the secretory stage and large gills ;lnd green glands for reasons give11 above. vacuoles appear to he dischargl.ng into the lumen. A Ho\·lever, Cd also i.s known to be toxic to gonad brush border l.s present on the proximal or lumen tissues, aud a more complete study should include surface of the cells. The nuclei are large with consideration of the reproductive tissues of the scattered chromatin. Blood cells are present lobster. Thirdly, the tissues examined were studied between the layers of tubular epi.thel ium. The gland by light microscopy, using haemotoxylin and eosin is normal in appearance and corresponds in descrip stained material. Closer examination, staining for tion lo the secretory stage of the green gland of specific cellular constituents, or ultrastructural crayfish Astacus astacus described by von studies might reveal deleterious changes induced by Ruddenbrock ( 1954~0nce again there is no evidence the high C'.d levels. Thus this report indicates no of histopathological change in the green gland of effect of Cd upon the lobster tissues examined but lobsters containing elevated levels of Cd in thelr should be considered as a preliminary study. hepatopancreas tissue. This is also shown by Gonadal and other tissues were also fixed and can he 6, a phot:nmicrograph of the tubules of lobster 'i, studied further. with a Ccl level of 304 ppm in its hepatopancreas. Cellular detaU is normal. AC KNOWLE DGNENTS GfLLS The lobster has 20 pairs of gills, found in The authors are indebted to Dr. M. Gilgan for narrow branchial chambers on each side of the body determining the molt stage of the lobsters by the and covered by the overlapping carapace. The method of Drach. anatomy of the gi Us has he('n describc>d briefLy by Herrick ( 1911) while the histology and ultra- s true ture of two closely related REFERF.NCES a spiny lobster, aud .-=-c:.:::c:_:::======, have heen Smith ( 1970) and by Burggren respec- Burggren, \v. W., B. R. ~icMahon, and .J. \.], \.0sterton. tively. In the lohster the gills are "feathery" 1971,. llranchial water- and blood-r!ow [liltterns structures with many fine lateral filaments <1nd the structur•' of the gill of the crayfish ex lending out from a main ax-Is,. Tho filaments are clarkiL Can. J. Zool. 52: covered with a thin chitinous layer below which is a layer of epithel.iaL cells. Blood flov1s through an afferent vessel to the tip of the filament and Davis, L. E., and A. L. Burnett. 1964. A study of returns to the base of the filament through a growth and cell differentiation in the para] lel efferent vessel. The vessels are separated hepatopancreas of the crayfish. Develop. lliol. from each other by a connective tissue septum 10: 122-153. similar to the pillar cell arrangement in fish gills. Holes in rhe septum near the outer edge of Drach, P. 1939. Mue et cycle d'intermue chez les the filament allow some blood to cut across from the rustaces decapods. Ann. Inst. C'x:eanogr. 19: afferent vessel to the parallel efferent vessel 103-391. without flowing out to the tip of the gill filament. Herrick, F. H. 1911. Natural history of the American lobster. Hull. U. S. Ru r • F l s h . 2 'J: In this study the sections of gill examined u. 9-1;08. showed the integrity of the epithelial cell layers was preserved and no differences were detectable Ogura, K. 1959. Midgut gland cells accumulating between the gills of lobsters containing either high iron or copper in the crayfish, Procamharus or low levels of Cd in their hepatopancreas (Fig. clarkii. Annotationes Zool. Japon. 32, No. 3. 7). Certainly it might be expected that the epi thel i.al cells would be the first to show evidence of O'Hara, J. 1973. Tioe influence of temperature and the toxic effects of Cd. These cells are in direct sall.nity on the toxicity of cadmium to the contact wi rh the seawater and would be constantly fiddler crab, Uca pugHator. Fish. Hull. exposed t~o any toxic substance in the environnH-:~nt .. 71(!): 149-153. -96- Saroglia, M. G., and G. Scarano. 1979. Influence of molting on the sensitivity to taxies of the crustacean Penaeus kerathurus (Forskal). Ecotoxicol. Environ. Safety 3: 310-320. Strangways-Dixon, J., and D. S. Smith. 1970. The fine structure of gill "podocytes" in Panulirus argus (Crustacea). Tissue & Cell 2: 611-624. Travis, D. F. 1955a. The molting cycle of the spiny lobster, Panulirus argus Latreille. II. Pre-ecdysial histological and hislochemical changes in the he pat o pane rpas and l n tegumental tissues. Biol. Bull. 108: 88--Ll2. l955b. The molting cycle of the spiny lobster, Panulirus argus Latreille. III. Physiological changes which occur in the blood and urine during the normal molting cycle. Biol. Bull. 109(3): 484-503. 1957. The molting cycle of the spiny lobster, Panulirus argus Latreille. IV. Post-ecdysial histological and histochemical changes in the he pa to pane reas and integumental tissues. Biol. Bull. 113: 451-479. von Buddenbrock, 1-1. 1951,. Physiologic der Decnpoden. Tn: Bronn's Tierreich. lld. '• Abt. l, Rch. 7, Lfg. 9, 1157-1175. Akademlsche Verlagsges., Leipzig. -97- Table l. Lobsters used in the histopathological survey. Cd i.n he pa to Lobster patopancreas pane reas (~ g/ g Number area Stage H FC H FC H FC wet weight) 2 OBOD X X X J X X X 4 X X X 5 X X X fi X X X 16 LlE X X X lR X X X 19 X X X 21 X X X 22 X X X 23 X X X 24 X X X 25 X X X 26 X X X 27 X X X 28 X X X 29 X X X 30 X X X Jl HW X X X 32 X X X 33 X X X 34 X X X 35 X X X 16 X X X 7') HE X X X 81 X X X RJ X X X 85 X X X 87 X X X B8 X X X 89 X X X 90 X X X 91 X X X 92 X X X 93 X X X 94 X X X 9Sa C-Do X X X X X X 304 96 X X X X X 97 X X X X 98a c X X X X X X 243 99 X X X X X lOOa Do X X X X X X 304 101<1 c X X X X X X 129 102<1 C-Do X X X X X X 54 103 i1 c X X X X X X ]QI, 104a Do X X X X X X 136 105 X X X X X 106 a LlW c X X X X X X 7. 50 107 X X X X X 108a c X X X X X X 9.93 109 X X X X X 110 X X X X X lll X X X X X 112 X X X X X ll·l" c X X X X X X ]]l,a x(?) X X X X X 115 L1E c X 116 X 117 C-Do X 118 c X 119 X -98- Tab! e 1. (cont 'd) ------Tissue Cd in he pa to- Lobster He pa to pane reas Gill Green gland pane reas (~ g/ g Num her area Stage H FC H FC H FC wet weight) 120 X 121 X 122 X 123 C-Do X 124a HH c X 333 12 )a Co X 222 126 X 127 X 128 X 129 X 110 X 131 X 132a C-Do X 47.6 133 X 134 L1H X 135a X 7. 88 136 X 137 X 118 X Ll9 X 140 X 141 X JL,z X 11+3 LiE X 144 X 14 sa C-Do X 1 1() 146 X 147 X 3 148 X 10. 2 11+9 X 150 X 151 X 3 152 X 25.8 3 153 X 43.9 3 156 X 154 223 L6E X X X X 224 X X () X 3 226 C-Do X X X X X so. 9 227 X X X X 3 228 c X X X X X 6. 12 229 X X () )( 3 230 c X )( X X X 16. 3 231a c X X X X X 21.9 232" C-Do X X X X X 231 X X X X 26.4 242 LlH X X X X 243 X X X X -99- Table l. (cont'd) Cd in hepato- Lobster pancreas ( llg/ g Number area Stage H FC H FC H FC I>Jet weight) 250a NIGADO Do-C X X X X X X 12.2 25la C-Do X X X X X X 5.66 252a c X X X X X X 14.6 253a c X X X X X X 8.57 254a c X X X X X X 8.46 255a C-Do X X X X X X !8.3 256a C-Do X X X X X X 17. I 257a C-Do X X X X X X 10.3 258a C-Do X X X X X X 10.2 2 59a C-Do X X X X X X 12. 3 x - Tissues fixed and processed H - Helly's fixative CF - formal calcium fixative Areas: LlW 1 mi west of Belledune Harbour L3E - 3 mi east of Belleclune Harbour HW - harbour west, inside harbour LIE - 1 mi east of Belledune Harbour OBOD outside harbour, opposite dock HE - harbour east, inside harbour L6E - 6 mi east of Belledune Harbour NICAllO- Nigadoo, N.B. "Samples which were compared in a blind study to attempt Lo discover if there was a correlation between Cd levels in Llw hl•patopancreas and any histopathological findings in these animals. -100- Fig. 1. A photomicrograph of a transverse section of several tubules of the hepatopancreas of lobster #103, fixed in Helly's fluid, sectioned at 5~ and stained with haematoxylin and eosin. The tubules are shown sectioned at different levels. Some consist mostly of absorptive cells (A), tall columnar cells with a basal nucleus and a striated border facing the lumen. Others are mostly secretory cells (S), also with basal nuclei, hut large secretory vacuoles. Some tubules were sectioned in the transition zone and both secretory and absorptive cells are present. The Cd level in this lobster was 104 ppm. 1bere is no evidence of tissue damage; magnification l60x. Fig. 2. A photomicrograph of the heparopancTeas of Johster 11232, in the early prcmolt stagc>. A tubule is seen sectioned transversely through the absorptive cell region and many small vacuoles nre evident containing calcospherites (Arrows). Tlw calcospherites are also evident i.n an adjacent oblique section of a tubule. Loose connective tissue is present between the tubules (C). The Cd level in the hepatopancreas of this lobster was 26.4 ppm (Helly's fixative, H and E stain; magnification 250x). -101- 102- Fig. ]. A photomicrograph of transversP sections of tubules of the hepato pancreas of lobster 11251 (Cd level 5.6 ppm). Tubules are sectioned at proximal end near he pa topanc reas duet. Cells are atrophying and nuclei are pycnotic (N). Lumen is filled with granular material; magnification 160x. Fig. 4. A photomicrograph of the hepatopancreas tubules of lobster 11230, Cd level 16.3 ppm. Tubules are cut obliquely and transition from embryonic cells (E) to absorptive cells (A) to secretory cells ( S) is seen. Lobster is in intermolt C stage and no calcospherites are visible (Helly's fixative, Hand E stain; magnification l60x). !03- ][]!,- Fig. 5. Photomicrograph of green gland labyrinth of lobster 1/230. The epll:helial cells (E) of the tubules are short columnar to cuboidal, with large central nuclei (N). Vacuoles (V) are present at apex of cells, discharging their contents into the ltnnen of the tubule. Chromatin granules in nuclei are dispersed. Blood cells (H) are present between epithelial cell Layers. Cd le.vei of hepatopancreas of this lobster was 16.3 ppm (Belly's fixative, Hand E stain; magnification 6I10x). Fig. 6. Photomicrograph of green gland labyrinth of lobster 1195, Cd level in hepatopancreils 301+ ppm. Blood cells (H) are seen between epithelial cell (E) layers of tubules. Normal central nuclei are seen In epithelial cells; some celLs are S(~creting vacuolar contents into lumen .. There is no evident membrane or other cellular damage apparent which might have been produced by Cd; magulfication 160x. -106- Fig. 7. Transverse section of lobster gil.!. The gill filament is covered with a thin lctyer of chJtin (CH). Below this layer lie t\vO blood vessels, afferent vessel (A) and efferent vessel (B) enclosed by an epithelial layer of cells (E) and separated hy a connective tissue septum (CT). This lobster is 11250 and contained 12.2 ppm Cd in its hepatopancreas; magnification 160x. -107-rie Pt p1us particuliCrement dt>s (>missions, du ruissPllement rh1 surface, dt>s df.versements du bassin cie r6_tention dl'S SCOriPS et finalement de ln lixiviation des SCOriE'S et deS flOUSSi£>res de L1 chamhre d<'S flltn~s. Ces scorh's et ces poussicres ont une Lenuer respr>ctive en cadmium de <0,01 et de 9:1:. Les poussieres de la chambre des filtres sont cnsuite recyclees jusqu'a ce que la teneur en cadmium tittl•igne JO%; elles en sont alors retirees puis exp§di§es 8 d'autres raffineries. Des experiences ant d6montre que le cadmium est lixiviable des scories et de la poussiere au contact de l'eau de mer.