Dissolved copper, zinc and cadmium in the Southern Bight of the North Sea

Volume 13/Number 3/March 1982 Gadd, P. E., Lavelle, J. W. & Swift, D. J. P. (1978). Estimates of sand transport on the New York continental shelf using near-bottom current meter observations. J. sedhn. PetroL, 48,239-252. GESAMP (1977). Joint Group of Experts on the Scientific Aspects of Marine Pollution, Impact of Oil on the Marine Environment, Report and Studies No. 6, Food and Agriculture Organisation, Rome. Goldberg, E. D. (1979). Scientific Problems Relating to Ocean Pollution, US Dept. of Commerce, National Oceanographic and Atmospheric Administration, Environmental Research Laboratories, Boulder. Jay, D. A. (1974). The hydrography and circulation of the New York Harbour and western Long Island Sound: Implications for water quality. Master of Science Thesis, Marine Science Research Center, State University of New York at Stony Brook. Koons, C. B. & Thomas, J. P. (1979). C15 + hydrocarbons in the sediments of the New York Bight. In Proceedings--1979 Oil Spill Co~Tference, pp. 625-628. American Petroleum Institute, Washington. McGrath, R. A. (1974). Benthic macrofaunal census of Raritan Bay. In Hudson River Ecology, 3rd Sympsium. Hudson River Environment Society, New York. McLeod, W. D., Scott Ramos, L., Friedman, A. J., Burrows, D. G., Prohaska, P. G., Fisher, D. L. & Brown, D. W. (1981). Analysis of residual chlorinated hydrocarbons, aromatic hydrocarbons and related compounds in selected sources, sinks and biota of New York Bight, NOAA National Analytical Facility, Seattle (unpublished report). Michael, A. D. (in press). The potential contribution of petroleum hydrocarbons to changes in benthic communities in the New York Bight. In Ecological Stress and the New York Bight: Science and Management. University of South Carolina, Columbia. Mueller, J. A. & Anderson, A. R. (1978). Industrial Wastes. MESA New York Bight Atlas Monograph 30. New York Sea Grant Institute, Albany. Mueller, J. A., Anderson, A. R. & Jeris, J. S. (1976). Contaminants entering the New York Bight: Sources, mass loads, significance. Am. Soc. LimnoL Oceanogr. spec. Symp., 2, 162-170.

NAS (1975). Petroleum in the marine environment. Report from the Workshop on Inputs, Fates and Effects of Petroleum in the Marine Environment. National Academy of Sciences, Washington DC. NOAA (1978). Annual Report for the Fiscal Year 1977, MESA New York Bight Project, Boulder, Colorado, p. 73. Olsen, C. R., Simpson, H. J., Bopp, R. F., Williams, S. C., Peng, T. H. & Deck, B. L. (1978). A geochemical analysis of the sediment and sedimentation in the Hudson estuary. J. sedim. PetroL, 48,401 --418. Searl, T. D., Thomas, J. P. & Huffman, H. L. (1977). Extractable organics and nonvolatile hydrocarbons in New York Harbour waters, In Proceedings of the 5th Conference on the Prevention, Behaviour, Control and Clean-up o f Oil Pollution, pp. 583-588. American Petroleum Institute, New Orleans. Slainken, D. & Frank, U. (1979). Analysis of Raritan Bay bottom waters for polynuclear aromatic hydrocarbons, Bull Envir. Contain. Toxic., 22,480--487. Tanacredi, J. T. (1977). Petroleum hydrocarbons from effluents: detection in the marine environment. J. Wat. Pollut. ControlFed., 49, 216-226. United States Coast Guard (1980). Personal communication. Van Fleet, E. S. & Quinn, J. G. (1977). Input and fate of petroleum hydrocarbons entering the Providence River and Upper Narragansett Bay from wastewater effluents. Envir. Sci. TechnoL, 11, 1086-1092. Van Fleet, E. S. & Quinn, J. G. (1978). Contribution of chronic petroleum inputs to Narragansett Bay and Rhode Island Sound sediments. J. Fish. Res. Bd Can., 35,536-543. Whipple, W., Hunter, J. V. & Yu, S. 1. (1976). Hydrocarbons in sewage and urban run-off - Delaware estuary. In Sources, Effects and Sinks of of Hydrocarbons in the Aquatic Environment, pp. 54-65. American Institute for Biological Sciences symposium, Washington DC.

MarinePollutionBulletin.Vol. 13, No. 3, lap.93-96, 1982. Printedin Great Britain.

0025-326X/82/030093-04 $03.00/0 © 1982PergamonPressLtd.

Dissolved Copper Zinc and Cadmium in the Southern Bight of the North Sea •

9

J. C. DUINKER and R. F. NOLTING

Netherlands Institute for Sea Research, Texel, The Netherlands Concentrations of dissolved copper, zinc and cadmium have been measured in the Dutch and Belgian coastal and offshore regions of the Southern Bight (North Sea), with the aim to compare levels in the central, most saline part of the Bight with those in the coastal region that is under the influence of the rivers Rhine and Scheldt, as well as with those in open ocean surface waters. Large problems are associated with the accurate analytical determination of certain trace elements at the extremely low levels at which they occur in offshore waters. These concentrations have to be known before the effects of human activities and natural processes on the composition of seawater can be evaluated. Additionally, a reliable comparison of data reported by different authors is hampered by the fact that practically all laboratories have used different pretreatment and analytical procedures. This was stressed in a recent review on trace metals in seawater of the OSLO Commission and ICNAF areas (Topping et al., 1979). In the course of our attempts to improve the analysis of seawater solution, we have, like several others, experienced lower detection limits, higher precision and

generally lower concentration levels for offshore and open ocean waters. Recent data suggest that the actual concentrations of e.g. copper, zinc, cadmium and lead are considerably lower than previously accepted values (Patterson & Settle, 1976; Bruland & Franks, 1981). This results from application of improved sampling and analytical equipment and from extreme precautions to avoid contamination during all steps. Available data for open ocean waters are scarce and patchy (Topping et al., 1979). The North Sea is a well studied basin. Still, only a few trace metal studies with a reasonable spatial coverage are available (Dutton et al., 1973; Duinker & Nolting, 1977; Duinker & Kramer, 1977; Gillain et al., 1980). The present results refer to samples obtained in 1975. At that time, reliable data could only be obtained for surface samples, taken with very simple devices. The reliability of our data, obtained by using a (polypropylene) bucket, has been checked by later comparisons with data obtained by using more sophisticated samplers that have become available such as teflonized Go-flo ® bottles (General 93

Marine Pollution Bulletin

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Fig. 1 Sampling stations in the Southern Bight 20-29 October 1975. Numbers indicate sequence of sampling. I0"

Oceanics) and by participation in internationally conducted intercalibration exercises (ICES, I O C / W M O / U N E P ) .

Sampling Scheme and Methods Surface samples for the determination of trace elements in solution and suspension were taken in transects off the Dutch and Belgian coasts in the period 20-29 October 1975 (128 stations, Fig. 1). The estuaries of the Scheldt and Rhine as well as stations within and through the salinity maximum in the Bight were included in the scheme. Surface samples were taken with a polypropylene bucket from the bow of the slowly moving vessel (R.V. Aurelia). 1- to 5-1itre subsamples (volume adjusted as to obtain sufficient particulate matter from the bucket for analysis) were filtered in an all-teflon filtration unit (Duinker & Nolting, 1977), with the necessary precautions to prevent settling of particles in the sampler before subsampling (Duinker et al., 1979). Filtrates (0.45 Wn pore size Millipore) were kept deep frozen. 'Dissolved' concentrations of copper, zinc and cadmium were measured by graphite furnace AAS in APDC-MIBK extracts (Duinker & Nolting, 1977). Data on the particulates will be published separately. Data are also included for samples from the British Channel and the Northern North Sea, taken with teflonized Go-flo bottles (Fig. 2).

Results and Discussion The distribution of salinity and dissolved copper, zinc and cadmium is given in contour representations (Fig. 3). The concentrations along one of the transects are depicted in Fig. 4. In all transects, concentrations decrease in an offshore direction. Minimum values occur in the maximum salinity water in the central part of the Bight. The occurrence of the minimum values for zinc is restricted to the very southern part of the area covered. Although the concentration gradients in the transects are similar (but opposite) to the salinity gradient, they 94

5*

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t0°

Fig. 2 Areas of sampling by the present authors (area C, January 1980), Kramer & Duinker (area D, March 1977), and Jones (areas A and B).

differ quantitatively off the Belgian coast where a tongue of increased concentrations for all three elements occurs. Possible sources are local inputs (dumping or contributions from bottom sediments), variations in the composition of the mixing end members or atmospheric input. Particles derived from the Scheldt containing increased levels of organic matter and certain trace metals have been found to accumulate in bottom sediments and in suspension in the area off the Belgian coast as a result of the convergence of the residual tidal current system (Gullentops et al., 1976). The good correlation between trace metals and organic matter in the sediment column in this area (Wollast, 1976) may indicate that metals are mobilized from the sediments after diagenetic transformation of organic matter. This may lead to an increase of trace elements in the water column. This is supported by budget calculations (Elskens, 1976). The relative importance may differ between elements and the effects may be time-dependent. Gillain et al. (1980) have reported concentrations off the Belgian coast in a rectangular array in an area bordered roughly by the present stations 42 and 51 (Fig. 1). Their values do not show a smooth dependence on the distance of the sampling site from the coast. Several of their offshore data values are higher than near the coast. However, the area covered does not include the maximum salinity region of the Bight and it is also too small to allow conclusions on whether these variations might support our conclusions. The minimum concentrations near the axis of maximum salinity are, in lag.l-J, 0.2-0.3 (Cu), 0.3-0.4 (Zn) and 0.020.03 (Cd). These are comparable to those measured in offshore surface waters of the British Channel by Kramer and Duinker (unpublished results) and by Jones (data given in Topping et al., 1979). The results are summarized in Table 1. Recent, and probably the best presently available values

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for surface offshore shelf waters of the western North Atlantic are (in lag.l- ~): 0.26 (Cu), 0.16 (Zn) and 0.023 (Cd) (Bruland & Franks, 1981)• Our and Jones' values compare favourably with the latter ones. The zinc data are higher than Bruland's data.

Higher concentrations than in the central part of the Bight have been observed in adjacent regions of the Northern North Sea (Fig. 2) by ourselves and Jones (Table 1). Although the average and the range of values in the two sets of data are not identical, they are higher than in the British

TABLE 1 Average and range o f dissolved concentrations o f Cu, Zn and Cd in seawater o f the central part of the Southern Bight, British Channel, Northern North Sea and in shelfwaters of the Western Atlantic. Data in ~ g . l - t and in n m o l e . k g - I. References: (I) present work; (2) Dutton et al., 1973; (3) Kramer & Duinker, unpublished work, area D. (fig. 2); (4) Jones, in Topping et al., 1979 (area B, Fig. 2); (5) Duinker & Nolting, in prep. (area C, Fig. 2); (6) Jones (same as ref. 4, area A, Fig. 2); (7) Bruland & Franks, 1981. Cu

Ref.

/ag.l - I

Minimum values in Southern Bight British Channel

(1) 0.2-0.3 (2) 0.5-1.0 (3) 0.34 ( ± 0.27) (4) 0.22 (0.10-0.40)

Northern North Sea

(5)

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(6)

0.26 (0.1-0.9)

(7)

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Western Atlantic shelf waters

Cd

Zn

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0.02-0.03 0.1-0.3 0.041 (--+0.019) O.Oi (0.01-0.02) 0.03 (0.02-0.03) 0.07 (0.01-0.17)

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95

Marine Pollution Bulletin ,,ttg.L" (Cu, Zn) I0 -I (Cd) 80"

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Fig. 4 Dissolved concentrations of Cu, Zn and Cd in samples along the transect from Rotterdam (Rhine) through the maximum salinity region toward the British coast. Sampling stations as in Fig. 1.

Bruland, K. W. & Franks, R. P. (1981). Mn, Ni, Cu, Zn and Cd in the Western North Atlantic. Nato Advanced Research Institute Conference "Trace metals in Sea water". Erice, Italy, March-April 1981. Duinker, J. C. & Kramer, C. J. M. (1977). An experimental study on the speciation of dissolved zinc, cadmium, lead and copper in river Rhine and North Sea water, by differential pulsed anodic stripping voltammetry. Mar. Chem., 5, 207-228. Duinker, J. C. & Nolting, R. F. (1977). Dissolved and particulate trace metals in the Rhine estuary and the Southern Bight. Mar. Pollut. Bull., 8, 65-71. Duinker, J. C., Nolting, R. F. & van der Sloot, H. A. (1979). The determination of suspended metals in coastal waters by different sampling and processing techniques (filtration, centrifugation). Neth. J. Sea Res., 13, 282-297. Dutton, J. W. R., Jefferies, D. F., Folkard, A. R. & Jones, P. G. W. (1973). Trace metals in the North Sea. Mar. Pollut. Bull., 4, 135-138. Elskens, I. (1976). Le transport de certains m6taux lourds ~_l'int6rieur de l'6cosyst~me marin de la pattie Sud du Southern Bight. In

Programme National de Recherche et D6veloppement-Eau, Projet Met, Rapport final, Volume 9: Contamination des Produits de la Mer (J. C. J. Nihoul & A. Dist6che, eds.), pp. 283-295. Gillain, G., Duyckaerts, C. & Dist~che, A. (1980). Trace metals (Zn, Cd, Pb, Cu, Sb and Bi) levels (ionic forms and dissolved organic complexes) in the Southern Bight (Belgian coast). Int. Counc. Expl. Sea, C.M. 1980/E: 38, 19pp. Gullentops, F., Moens, M., Ringel, A. & Sengier, R. (1976). Geologische kenmerken van de suspensie en de sedimenten. In Programme

National de Recherche et D6veloppement-Eau, Projet Mer, Rapport final, Volume 4: Sedimentologie (J. C. J. Nihoul & F. Gullentops, C h a n n e l . T h i s m a y reflect p i c k - u p o f metals d u r i n g the m a i n circulation p a t t e r n , i n v o l v i n g i n p u t t h r o u g h the Straits o f D o v e r a n d o u t p u t b e t w e e n the U K a n d N o r w a y . T h e d i s t r i b u t i o n p a t t e r n o f the increased c o n c e n t r a t i o n s in the coastal a r e a suggests t h a t higher values o c c u r in waters u n d e r the i n f l u e n c e o f the rivers R h i n e a n d Scheldt. T h e levels in the coastal a r e a are increased o v e r the m i n i m u m values in the central p a r t o f the Bight with factors o f a b o u t 6 (Cu), 25 (Zn) a n d 3 (Cd). E n h a n c e d levels are n o t necessarily d e t e c t e d in areas w i t h c o n s i d e r a b l e a n t h r o p o g e n i c inputs. F o r instance, e n h a n c e d levels o f trace metals in waters o f the G u l f o f St. L a w r e n c e , receiving waste m a t e r i a l f r o m o n e o f the m o s t heavily p o p u l a t e d a n d industrialized areas o f N. A m e r i c a , h a v e n o t b e e n d e t e c t e d (Yeats etal., 1978).

Marine Pollution Bulletin, Vol. 13, No. 3, pp. 96-98, 1982. Printed in Great Britain.

eds.), pp. 1-121. Patterson, C. C. & Settle, D. M. (1976). The reduction of orders of magnitude errors in lead analyses of biological materials and natural waters by evaluating and controlling the extent and sources of industrial lead contamination introduced during sample collecting and analysis. In Accuracy in Trace Analysis: Sampling, Sample Handling, Analysis, Vol. 1 (P. D. LaF[eur, ed.). NBS Spec. Publ. 422, pp. 321-351. Topping, G., Bewers, J. M. & Jones, P. G. W. (1979). A review of the past and present measurements of selected trace metals in sea water in the Oslo Commission and ICNAF areas (mimeo). Prepared for ICES Working Group on Pollution and Monitoring Studies in the North Atlantic. Wollast, R. (1976). Propri6t6s physico-chimiques des sediments et des suspensions de la met du Nord. I n Programme National de Recherche

et D6veloppement-Eau, Projet Mer, Rapport final, VoL 4: Sedimentologie (J. C. J. Nihoul & F. Gullentops, eds.), pp. 123-143. Yeats, P. A., Bewers, J. M. & Walton, A. (1978). Sensitivity of coastal waters to anthropogenic trace metal emissions. Mar. Pollut. Bull., 9, 264-268.

0025-326X/82/030096-03$03.00/0 © 1982 Pergamon Press Ltd.

Effect of an Oil Spill in Spitzbergen in 1978 B J O R N G U L L I K S E N * a n d J E N S P E T T E R T A A S E N t-

*Department o f Marine Biology, Troms¢ M u s e u m , University o f Troms¢, P. O. B o x 255 O, N-9001 Troms¢, Norway. -I-Institute o f Biology and Geology, University o f Troms¢, P. O. B o x 790, N-9001 Troms¢, Norway.

The oil content in the sediment and the marine life along the arctic shores of Van Mijenfjord, Spitzbergen, were investigated about two years after a spill from diesel storage tanks. High values of oil were recorded in the sediment along the shore near the tanks. The shore fauna is generally poor in these areas and the only biological effect detected was the disappearance of the amphipod G a m m a r u s setosus from the surface layers. 96