- Email: [email protected]
Distribution of selected metals in sediment cores of puck bay, Baltic Sea
V o l u m e 3 0 / N u m b e r 9 / S e p t e m b e r 1995
Edited by D. J. H. Phillips The objective of BASELINE is to publish short communications on different aspects of pollution of the marine environment. Only those papers which clearly identify the quality of the data will be considered for publication. Contributors to Baseline should refer to 'Baseline--The New Format and Content' (Mar. Pollut. Bull. 24, 124). Marine Pollution Bulletin, Vol. 30, No. 9, pp. 615-618, 1995
-~ ° e r " a m o n
Copyright © 1995 Elsevier Science Ltd Printed in Great Britain. All rights reserved 0025-326X/95 $9.50+0.00
0025-326X(95)00079-8
Distribution of Selected Metals in Sediment Cores of Puck Bay, Baltic Sea P. SZEFER*, A. KUSAK*, K. SZEFER*, H. JANKOWSKAt, M. WOLOWlCZ~: and ANIS AHMED ALl§ *Department of Analytical Chemistry, Medical University of Gdahsk, al. Gen. J. Hallera 107, PL 80-416 Gdafisk, Poland t Department of Chemical Geology, Institute of Oceanography, Gdahsk University, aL Marsz. J. Pitsudskiego 46, PL 81-378 Gdynia, Poland 5;Laboratory of Estuarine Ecology, Institute of Oceanography, Gdahsk University, al. Marsz. J. Pitsudskiego 46, PL 81-378 Gdynia, Poland § University of Aden, Faculty of Science, Arts and Education, P O. Box 6014, Khormaksar, Aden, Yemen
Sediments from coastal regions near industrial and urban areas are commonly contaminated with heavy metals and the concentrations found in newer (surface) sediments may be significantly higher compared to those from 50-100 years ago (Erlenkeuser et al., 1974). Marine sediments serve as an ultimate sink for heavy metals discharged into the aquatic environment (Luoma & Bryan, 1981). Sub-sections of sediment cores reflect the geochemical history of a given region, including any anthropogenic impact. Hence, sediments act as useful indicators of long- and medium-term metal flux. As the concentrations of elements depend on the particle size distribution in sediments, a standardized procedure with regard to particle size is required for comparative analysis. However, many different grain sizes have been used, based on the following fractions: 60-200 ~tm (Sager et al., 1990), < 100 ~tm (Luoma & Bryan, 1981), < 63 ~m (Horowitz et al., 1990; Pena & Picot, 1991), < 2 0 ~tm (Glasby etal., 1988) and < 2 ~tm (Szefer et al., 1993). In this study, three granulometric fractions i.e. < 2, 2-63 and 63-200 Ixm, were separated
and analysed in order to understand the distribution of metallic pollutants in sediment cores of Puck Bay. Two core samples were taken during the cruise of the R.V. Oceanograf H in 1991. The locations of the sampling stations are shown in Fig. 1. Subsamples of the wet sediments were washed through polyethylene mesh and the excess water was evaporated on a water bath at 80°C, to obtain a thick slurry. The material was dried at ll0°C and weighed, prior to digestion with concentrated HNO 3 (65%), HF (40%) and HCIO 4 (70%) in volume ratios of 7 : 7 : 1 (Szefer et al., 1995). The dry residue was converted to chlorides by evaporation with concentrated HC1 (36%), and was dissolved in 1 M HC1. The concentrations of selected elements were measured by AAS using deuterium-background correction. The accuracy and precision of the method employed were satisfactory as estimated using intercomparison data for a reference material from the IAEA in Monaco (sediment sample code SD-N-1/2); see Szefer et al. (1995, in press). Figures 2 and 3 show the vertical distributions of Ag, Cd, Cr, Cu, Pb and Zn in the sediment cores from Puck Bay. The concentration of Cr did not vary significantly with sediment depth in core No. 8. By contrast, concentrations of Ag (core 8), Cu, Pb, Zn and especially Cd decreased gradually with depth of the successive sediment segments. Irregular variations of Ag concentrations in the 2-63 ~tm fraction of sediment core 25 (with maximum levels in the surface and the deepest segments) were unexpected and remain difficult to explain at the present stage of the investigations.
54ON
I I
I
POLAND
1 I
1
#'
/
17OE
-54040 ,
-54o30"
o
Fig. 1 L o c a t i o n of the s a m p l i n g stations.
615
Marine Pollution
4 3.5 3 2.5 2 8
1.5 1 0.5
_
o-5
5-10
10-15
. 15-20
0
. 20-25
cm
60 0' 40
O-5
S-10
lo-15
15-20
20-25
cm
cm 35c
7
3oc 250 200 if
150 100 50 0,
O-5
5-10
IO-15
15-20
5-10
20-25
cm
cm
STATION 8
Fig. 2 The vertical distributions of selected metals in sediments station 8 in Puck Bay. All data as yg g-l dry wt.
616
lo-15
from
‘15-20
20-25
Bulletin
Volume 30/Number 9/September 1995
25-
20-
15.
<
10
5-
6-
7, /
5'
/ / / / / / / / /, / / /
4"
;v :1/
7
/ ,¢ / /
3"
:L/ it/ :t/
"o
(J
2" /
il/
/
~1/ L
1,
" :Ltg
L 5-10
0-5
10-15
5-20
0
20-25
/ / / / I / / / I / I / / / / /
0-5
,ik 5-10
10-15
cm
250-
200
150-
100-
50,
5-20
20-25
cm
90~ / / / / / / / / / / / / / ¢, /
0-5
80'
70"
i
60"
i
50"
40-
|
Li 5-I0
i
,
L
'
i
30-
/
10-15
15-20
0
20-25
250
600 ..........
200
500"
i
0-5
5-t~
10-15 cm
400"
I I / I / / / /
N 200'
50.
1000
10-15 crn
15-20
20-25
20-25
i !
7,
300-
loo
15-20
i
150-
5-10
=[=I
I0.
crn
0-5
J
t
20'
/ 0-5
5-11
!
L 10-15
15-20
20-25
cm
STATION
25
Fig. 3 T h e vertical d i s t r i b u t i o n s o f s e l e c t e d m e t a l s in s e d i m e n t s f r o m s t a t i o n 2 5 in Puck Bay. All data as Ixg g-~ dry wt,
617
Marine Pollution Bulletin TABLE 1
~Smthropogenic factors' calculated for selected metals in fine grained fractions of sediment cores from Puck Bay. Granulometric fraction (~m)
Ag
Cd
Cr
Cu
Pb
Zn
Station No. 8
<2 2-63
2.9 >6.8*
> 18.4" 18.0
1.3 1.4
2.7 3.1
8.0 3.6
5.5 5.1
1.4 0.7
>27.8* > 13.0"
2.1 2.6
1.9 1.6
t 2.4
2.3 3.0
Station No. 25
<2 2-63
*AF value was calculated by dividing the metal concentration in top layer of sediment by < 0.1 Ixg g-l, i.e. the limit of detection obtained for this metal in the deepest segment. tPb was not analysed in this fraction.
To quantify presumed anthropogenically-derived changes in the study area, an 'anthropogenic factor' (AF) was calculated according to the formula AF = M~/ Md, where Ms is the mean concentration of metal in the top layer of sediment (fractions < 2 and 2-63 ~tm); and Ma is the mean concentration of the metal in the deepest layer of the sediment (fractions of < 2 and 2-63 ~tm). AF values are listed in Table 1. In some instances, only moderate enrichment of metals was observed in the surface sediments, AF values being < 3 (Ag in most cases; Cr, Cu and some values for Pb and Zn). However, greater enrichment was noted for Ag, Pb and Zn in fractions of core 8 in particular, and Cd exhibited very high AF values in all cases. As expected, significant variations of metal concentrations in relation to sediment particle size were identified (Figs 2 and 3). The greatest concentrations were generally found in the fine-grained (sub-colloidal) fraction, while the 63-200 ~tm fraction commonly exhibited the lowest levels of the metals analysed. Chemical analysis of the sediment cores from Gdafisk Bay has confirmed an anthropogenic enrich-
618
ment of the metals studied, especially Ag and Cd. This is in agreement with previous reports (Szefer & Skwarzec, 1988; Szefer & Kaliszan, 1993; Szefer et al., 1993, 1995, in press), and indicates that anthropogenic sources are responsible for much of the input of Ag, Cd, Cu, Pb and Zn in near-shore regions in the Gulf of Gdafisk. This research was supported by grant No. 6 P202 034 06 (to ES.) from the National Committee of Scientific Research, Warsaw (Komitet Badafi Naukowych, Warszawa), as part of the LOICZ Programme. Erlenkeuser, H., Suess, E. & Willkomm, H. (1974). Industrialization affects heavy metal and carbon isotope concentrations in recent Baltic Sea sediments. Geochim. Cosmochim. Acta 38,823-842. Glasby, G. P., Stoffers, P., Walter, P., Davies, K. R. & Renner, R. M. (1988). Heavy-metal pollution in Manukau and Waitemata Harbours, New Zealand. N Z J. Mar. Freshwater Res. 22,595-611. Horowitz, A. J., Rinella, E A., Lamothe, P., Miller, T. L., Edwards, T. K., Roche, R. L. & Rickert, D. A. (1990). Variations in suspended sediment and associated trace element concentrations in selected riverine cross sections. Environ. Sci. Technol. 24, 1313-1320. Luoma, S. N. & Bryan, G. W. (1981). A statistical assessment of the form of trace metals in oxidized estuarine sediments employing chemical extractants. Sci. TotalEnviron. 17, 165-196. Pena, G. & Picot, B. (1991). MEtaux traces dans les s6diments d'une lagune m~diterran6enne: l'6tang de Thau. Oceanologica Acta 14, 459-472. Sager, M., Pucsko, R. & Belocky, R. (1990). Evaluation of the speciation of inorganic constituents in sediments of Reservoir at Attenworth of the River Danube. Arch. Hydrobiol. Suppl. 84, 37-72. Szefer, P. & Skwarzec, B. (1988). Distribution and possible sources of some elements in the sediment cores of the southern Baltic. Mar. Chem. 23,109-129. Szefer, P. & Kaliszan, R. (1993). Inter-elemental relationships in sediment cores from southern Baltic. Special Symposium of Emerging Industrial and Engineering Chemistry Division, American Chemical Society, Atlanta, GA, 27-29 September 1993. Szefer, P., Jankowska, H., Wot'owicz, M., Kusak, A. & Pempkowiak, J. (1993). Vertical and horizontal distribution of heavy metals in bottom sediments from Gdafisk Bay, Baltic Sea. Special Symposium of Emerging Industrial and Engineering Chemistry Division, American Chemical Society, Atlanta, GA, 27-29 September 1993. Szefer, P., Glasby, G. R, Pepkowiak, J. & Kaliszan, R. (1995). Extraction studies of heavy metal pollutants in surficial sediments from the southern Baltic Sea off Poland. Chem. Geol. 120, 111-126. Szefer, P., Glasby, G. R, Szefer, K., Pempkowiak, J. & Kaliszan, R. (In press). Heavy-metal pollution in surficial sediments from the southern Baltic Sea off Poland. J. Environ. Sci. Health.
Edited by D. J. H. Phillips The objective of BASELINE is to publish short communications on different aspects of pollution of the marine environment. Only those papers which clearly identify the quality of the data will be considered for publication. Contributors to Baseline should refer to 'Baseline--The New Format and Content' (Mar. Pollut. Bull. 24, 124). Marine Pollution Bulletin, Vol. 30, No. 9, pp. 615-618, 1995
-~ ° e r " a m o n
Copyright © 1995 Elsevier Science Ltd Printed in Great Britain. All rights reserved 0025-326X/95 $9.50+0.00
0025-326X(95)00079-8
Distribution of Selected Metals in Sediment Cores of Puck Bay, Baltic Sea P. SZEFER*, A. KUSAK*, K. SZEFER*, H. JANKOWSKAt, M. WOLOWlCZ~: and ANIS AHMED ALl§ *Department of Analytical Chemistry, Medical University of Gdahsk, al. Gen. J. Hallera 107, PL 80-416 Gdafisk, Poland t Department of Chemical Geology, Institute of Oceanography, Gdahsk University, aL Marsz. J. Pitsudskiego 46, PL 81-378 Gdynia, Poland 5;Laboratory of Estuarine Ecology, Institute of Oceanography, Gdahsk University, al. Marsz. J. Pitsudskiego 46, PL 81-378 Gdynia, Poland § University of Aden, Faculty of Science, Arts and Education, P O. Box 6014, Khormaksar, Aden, Yemen
Sediments from coastal regions near industrial and urban areas are commonly contaminated with heavy metals and the concentrations found in newer (surface) sediments may be significantly higher compared to those from 50-100 years ago (Erlenkeuser et al., 1974). Marine sediments serve as an ultimate sink for heavy metals discharged into the aquatic environment (Luoma & Bryan, 1981). Sub-sections of sediment cores reflect the geochemical history of a given region, including any anthropogenic impact. Hence, sediments act as useful indicators of long- and medium-term metal flux. As the concentrations of elements depend on the particle size distribution in sediments, a standardized procedure with regard to particle size is required for comparative analysis. However, many different grain sizes have been used, based on the following fractions: 60-200 ~tm (Sager et al., 1990), < 100 ~tm (Luoma & Bryan, 1981), < 63 ~m (Horowitz et al., 1990; Pena & Picot, 1991), < 2 0 ~tm (Glasby etal., 1988) and < 2 ~tm (Szefer et al., 1993). In this study, three granulometric fractions i.e. < 2, 2-63 and 63-200 Ixm, were separated
and analysed in order to understand the distribution of metallic pollutants in sediment cores of Puck Bay. Two core samples were taken during the cruise of the R.V. Oceanograf H in 1991. The locations of the sampling stations are shown in Fig. 1. Subsamples of the wet sediments were washed through polyethylene mesh and the excess water was evaporated on a water bath at 80°C, to obtain a thick slurry. The material was dried at ll0°C and weighed, prior to digestion with concentrated HNO 3 (65%), HF (40%) and HCIO 4 (70%) in volume ratios of 7 : 7 : 1 (Szefer et al., 1995). The dry residue was converted to chlorides by evaporation with concentrated HC1 (36%), and was dissolved in 1 M HC1. The concentrations of selected elements were measured by AAS using deuterium-background correction. The accuracy and precision of the method employed were satisfactory as estimated using intercomparison data for a reference material from the IAEA in Monaco (sediment sample code SD-N-1/2); see Szefer et al. (1995, in press). Figures 2 and 3 show the vertical distributions of Ag, Cd, Cr, Cu, Pb and Zn in the sediment cores from Puck Bay. The concentration of Cr did not vary significantly with sediment depth in core No. 8. By contrast, concentrations of Ag (core 8), Cu, Pb, Zn and especially Cd decreased gradually with depth of the successive sediment segments. Irregular variations of Ag concentrations in the 2-63 ~tm fraction of sediment core 25 (with maximum levels in the surface and the deepest segments) were unexpected and remain difficult to explain at the present stage of the investigations.
54ON
I I
I
POLAND
1 I
1
#'
/
17OE
-54040 ,
-54o30"
o
Fig. 1 L o c a t i o n of the s a m p l i n g stations.
615
Marine Pollution
4 3.5 3 2.5 2 8
1.5 1 0.5
_
o-5
5-10
10-15
. 15-20
0
. 20-25
cm
60 0' 40
O-5
S-10
lo-15
15-20
20-25
cm
cm 35c
7
3oc 250 200 if
150 100 50 0,
O-5
5-10
IO-15
15-20
5-10
20-25
cm
cm
STATION 8
Fig. 2 The vertical distributions of selected metals in sediments station 8 in Puck Bay. All data as yg g-l dry wt.
616
lo-15
from
‘15-20
20-25
Bulletin
Volume 30/Number 9/September 1995
25-
20-
15.
<
10
5-
6-
7, /
5'
/ / / / / / / / /, / / /
4"
;v :1/
7
/ ,¢ / /
3"
:L/ it/ :t/
"o
(J
2" /
il/
/
~1/ L
1,
" :Ltg
L 5-10
0-5
10-15
5-20
0
20-25
/ / / / I / / / I / I / / / / /
0-5
,ik 5-10
10-15
cm
250-
200
150-
100-
50,
5-20
20-25
cm
90~ / / / / / / / / / / / / / ¢, /
0-5
80'
70"
i
60"
i
50"
40-
|
Li 5-I0
i
,
L
'
i
30-
/
10-15
15-20
0
20-25
250
600 ..........
200
500"
i
0-5
5-t~
10-15 cm
400"
I I / I / / / /
N 200'
50.
1000
10-15 crn
15-20
20-25
20-25
i !
7,
300-
loo
15-20
i
150-
5-10
=[=I
I0.
crn
0-5
J
t
20'
/ 0-5
5-11
!
L 10-15
15-20
20-25
cm
STATION
25
Fig. 3 T h e vertical d i s t r i b u t i o n s o f s e l e c t e d m e t a l s in s e d i m e n t s f r o m s t a t i o n 2 5 in Puck Bay. All data as Ixg g-~ dry wt,
617
Marine Pollution Bulletin TABLE 1
~Smthropogenic factors' calculated for selected metals in fine grained fractions of sediment cores from Puck Bay. Granulometric fraction (~m)
Ag
Cd
Cr
Cu
Pb
Zn
Station No. 8
<2 2-63
2.9 >6.8*
> 18.4" 18.0
1.3 1.4
2.7 3.1
8.0 3.6
5.5 5.1
1.4 0.7
>27.8* > 13.0"
2.1 2.6
1.9 1.6
t 2.4
2.3 3.0
Station No. 25
<2 2-63
*AF value was calculated by dividing the metal concentration in top layer of sediment by < 0.1 Ixg g-l, i.e. the limit of detection obtained for this metal in the deepest segment. tPb was not analysed in this fraction.
To quantify presumed anthropogenically-derived changes in the study area, an 'anthropogenic factor' (AF) was calculated according to the formula AF = M~/ Md, where Ms is the mean concentration of metal in the top layer of sediment (fractions < 2 and 2-63 ~tm); and Ma is the mean concentration of the metal in the deepest layer of the sediment (fractions of < 2 and 2-63 ~tm). AF values are listed in Table 1. In some instances, only moderate enrichment of metals was observed in the surface sediments, AF values being < 3 (Ag in most cases; Cr, Cu and some values for Pb and Zn). However, greater enrichment was noted for Ag, Pb and Zn in fractions of core 8 in particular, and Cd exhibited very high AF values in all cases. As expected, significant variations of metal concentrations in relation to sediment particle size were identified (Figs 2 and 3). The greatest concentrations were generally found in the fine-grained (sub-colloidal) fraction, while the 63-200 ~tm fraction commonly exhibited the lowest levels of the metals analysed. Chemical analysis of the sediment cores from Gdafisk Bay has confirmed an anthropogenic enrich-
618
ment of the metals studied, especially Ag and Cd. This is in agreement with previous reports (Szefer & Skwarzec, 1988; Szefer & Kaliszan, 1993; Szefer et al., 1993, 1995, in press), and indicates that anthropogenic sources are responsible for much of the input of Ag, Cd, Cu, Pb and Zn in near-shore regions in the Gulf of Gdafisk. This research was supported by grant No. 6 P202 034 06 (to ES.) from the National Committee of Scientific Research, Warsaw (Komitet Badafi Naukowych, Warszawa), as part of the LOICZ Programme. Erlenkeuser, H., Suess, E. & Willkomm, H. (1974). Industrialization affects heavy metal and carbon isotope concentrations in recent Baltic Sea sediments. Geochim. Cosmochim. Acta 38,823-842. Glasby, G. P., Stoffers, P., Walter, P., Davies, K. R. & Renner, R. M. (1988). Heavy-metal pollution in Manukau and Waitemata Harbours, New Zealand. N Z J. Mar. Freshwater Res. 22,595-611. Horowitz, A. J., Rinella, E A., Lamothe, P., Miller, T. L., Edwards, T. K., Roche, R. L. & Rickert, D. A. (1990). Variations in suspended sediment and associated trace element concentrations in selected riverine cross sections. Environ. Sci. Technol. 24, 1313-1320. Luoma, S. N. & Bryan, G. W. (1981). A statistical assessment of the form of trace metals in oxidized estuarine sediments employing chemical extractants. Sci. TotalEnviron. 17, 165-196. Pena, G. & Picot, B. (1991). MEtaux traces dans les s6diments d'une lagune m~diterran6enne: l'6tang de Thau. Oceanologica Acta 14, 459-472. Sager, M., Pucsko, R. & Belocky, R. (1990). Evaluation of the speciation of inorganic constituents in sediments of Reservoir at Attenworth of the River Danube. Arch. Hydrobiol. Suppl. 84, 37-72. Szefer, P. & Skwarzec, B. (1988). Distribution and possible sources of some elements in the sediment cores of the southern Baltic. Mar. Chem. 23,109-129. Szefer, P. & Kaliszan, R. (1993). Inter-elemental relationships in sediment cores from southern Baltic. Special Symposium of Emerging Industrial and Engineering Chemistry Division, American Chemical Society, Atlanta, GA, 27-29 September 1993. Szefer, P., Jankowska, H., Wot'owicz, M., Kusak, A. & Pempkowiak, J. (1993). Vertical and horizontal distribution of heavy metals in bottom sediments from Gdafisk Bay, Baltic Sea. Special Symposium of Emerging Industrial and Engineering Chemistry Division, American Chemical Society, Atlanta, GA, 27-29 September 1993. Szefer, P., Glasby, G. R, Pepkowiak, J. & Kaliszan, R. (1995). Extraction studies of heavy metal pollutants in surficial sediments from the southern Baltic Sea off Poland. Chem. Geol. 120, 111-126. Szefer, P., Glasby, G. R, Szefer, K., Pempkowiak, J. & Kaliszan, R. (In press). Heavy-metal pollution in surficial sediments from the southern Baltic Sea off Poland. J. Environ. Sci. Health.