- Email: [email protected]
Aliphatic and aromatic hydrocarbons in benthic invertebrates from two sites in Antarctica
Marine Pollution Bulletin
constructive note on which to end. Oil spill impact assessment in previously unsurveyed areas presents considerable problems in selection of reference or 'control' sites and interpretation of data. For some types of investigation, field experiments provide an alternative approach which is particularly useful in the tropics as choice of experimental sites for convenience can eliminate the transport and accommodation problems of surveys in remote areas. The experimental applications of oils and dispersants now being planned in both Nigeria and Indonesia are feasible in any tropical country and provide an opportunity for properly controlled, quantitative biological work of academic, applied and educational value.
Cairns, J., Heath, A. G. & Parker, B. C. (1975). Temperature influence on chemical toxicity to aquatic organisms. War. Pollut. ControlFed., 47, 267-280. Earl, G. W. (1837). TheEastern Seas. W. H. Allen, London. LEMIGAS (Lembaga Minyak dan Gas Bumi) and Smithsonian Institution Office of International and Environmental Program). (1974). Coastal zone pollution in Indonesia with emphasis on oil. LEMIGAS, Jakarta. Macnae, W. (1968). A general account of the fauna and flora of mangrove swamps and forests in the Indo-West Pacific region. Adv. Mar. Biol. 6, 73-270. Odum, E. P. (1971). Fundamentals o f Ecology. W. B. Saunders, Philadelphia-London-Toronto. Rao, G. N. S. (1965). Use of seaweeds directly as food. Indo-Pacific Fisheries Council, Bangkok (Reg. Stud. Indo-Pacif. Fish. Coun. No. 2). Sanders, H. L. (1968). Marine benthic d i v e r s i t y - a comparative study. A m . Natur., 102. (925), 243-282. Schuster, W. H. (1952). Fish culture in brackish water ponds of Java. Diocesan Press, Madras (Indo-Pacif. Fish. Coun. Spec. PuN. No. 1).
MarinePollutionBulletin, Vol. 12, pp. 10-14 PergamonPressLtd. 1981.Printedin Great Britain.
0025-326X/81/01014)010$02.00/0
Aliphatic and Aromatic Hydrocarbons in Benthic Invertebrates from Two Sites in Antarctica* ANDREW CLARKE 1- and ROBIN LAW ¢
¢ British Antarct& Survey, NERC, Madingley Road, Cambridge CB50ET, UK ¢ MAFF." Directorate of Fisheries Research, Fisheries Laboratory, Remembrance A venue, Burnham-on-Crouch, Essex CMO 8HA, UK
Samples of marine benthic invertebrates collected from two sites in the Antarctic have been analysed for both aliphatic and aromatic hydrocarbons in order to establish baseline concentrations for some classes of hydrocarbons. Samples from Signy Island, a pristine site, contained low concentrations of the hydrocarbons determined, whereas those from King Edward Cove, South Georgia, contained significantly higher concentrations. King Edward Cove has a known history of pollution from whaling operations. Platt & Mackie (1979) have suggested that the hydrocarbons in sediments from King Edward Cove are a result of the world-wide dissemination of the pyrolysis products of fossil fuels. Our work suggests, in contrast, that the hydrocarbons in the benthos are derived from local sources. Antarctica is one area of the globe which remains relatively unpolluted by man's activity; the volume of shipping is small and permanent human settlements are few. These factors and the prevailing pattern of water currents suggest *© Crown Copyright.
10
that hydrocarbon concentrations in Antarctic benthos should represent background or baseline concentrations, i.e., marine invertebrates sampled from pristine areas in Antarctica should contain only biogenic hydrocarbons. Unfortunately, parts of Antarctica do not measure up to this high quality, and in this paper we present data for the hydrocarbon content of marine invertebrates from two sites in Antarctica, one with a known history of severe pollution from a whaling station; the other is believed to be a pristine site. The intention of this work was to establish baseline concentrations for some classes of hydrocarbons (which could be used in future pollution investigations); and to compare with concentrations present in invertebrates from an area subject at an earlier date to industrial pollution.
Materials and M e t h o d s Samples were collected from King Edward Cove, South Georgia, and from Normanna Strait, Signy Island. The positions of these two islands are shown in Fig. 1. King Edward Cove, South Georgia (54 ° 17' S, 36 ° 30' W) is a small, shallow cove with a bottom comprised largely of
Volume 12/Number l/January 1981
I
FALKLAND
~
ISLANDS
I
!
50 °
40*
',~AMERICA f
/
/ /
~SSoS
/
80 °
J
30"~ f
J
S O U T H GEORGIA
J /
/
f
550S, ¢~,6'
SIGNY /
,
ISLAND
"
?
~65*S
20
D"
WEDDELL
""*~(_':.:F'
90°W
. . . . . . . . . . . . ~5 "'~""
SEA
....
65"S
lOg
o__.
~,,
75°S
,.,,i '- ",,'.. ,, ....... ,,
100 ° 100 °
90°W
~0 o
/ i
"
.~..~. (,," 70 °
6o . . . . , 5o °
':~, 40 ° ',"
30°w,
20 °`
75°s, ,'1°°
,~,
0°/
Fig. 1 Map of Antarctica showing location of sampling areas.
uncompacted mud at the centre, grading to fine sand in shallower water. From 1904 until 1965 this cove was the site of an active whaling station, and considerable quantities of fossil fuels and biological material were discharged into its waters. Descriptions of this environment are to be found in Platt (1979a,b) and an analysis of the benthic community following the cessation of whale processing is to be found in Platt (1978). Mackie et aL (1978) have presented analyses of the n-alkanes in representative marine and terrestrial organisms from this area. Normanna Strait, Signy Island (60 ° 43' S, 45 ° 38' W) has been little affected by human presence with the exception of the occasional passage of ships. The area is extensively covered by fast-ice in winter, and as there is no evidence of petroleum seeps in the area, it is believed to be a pristine environment. As far as was possible comparable organisms were taken from each site, and details of these are given in Table 1. Benthos was collected by SCUBA diving and Euphausia superba by midwater trawl. Both were immediately frozen to - 40°C. Storage and transport also took place at - 40°C under nitrogen. Care was taken to avoid contamination from sampling apparatus or as a result of poor technique,
particularly by avoiding the use of plastics, oil and grease. Both procedural blanks and a deliberately contaminated 'blank' were analysed at the same time as the samples. Lipids were extracted from the samples with methanolchloroform (Clarke, 1979), and hydrocarbons were purified from these extracts by chromatography on silica gel (7% deactivated with water). The hydrocarbon fractions were then analysed on a 25 m glass capillary column coated with OV-1 in a Carlo Erba 2151 gas chromatograph (n-alkanes), and by mass fragmentography using a Finnigan 3200-6110 computerized capillary GC-MS system (aromatics) (see Law, 1978a,b). GC-MS quantitation was by internal standardization; known weights of the fully deuterated analogues of naphthalene (naphthalene-d8) and phenanthrene (phenanthrene-dl0) (Merck, Sharp and Dohme, Hoddesdon, Hertfordshire) being added before sample extraction.
Results Results of the analyses are given in Tables 2 and 3. Consistent and striking differences were apparent in the chromatograms of samples from the two areas, as shown by 11
Marine Pollution Bulletin
TABLE
1
Antarctic marine invertebrates analysed for hydrocarbons. South Georgia
Signy Island
Class
Species
No. in sample
Species
No. in sample
Echinodermata
Odontaster validus
6 immature
Odontaster validus
1
Mollusca
Chlanidota densesculpta
3
Neobuccinum eatoni
1
1 1
Crustacea
Serolis pagenstecheri
1
1; 1;
Serolis cornuta
1 1 1 1 5 immature
1; 1: 4immature
Euphausia superba
6 gravid .
TABLE 2
Aliphatic hydrocarbon content of Antarctic marine invertebrates (ng g - ] wet weight).
Species
Site
No. of samples
~ 15 Z.., 33
Odontaster validus
SG SI
1 1
525.5 24.3
Pristane
Phytane
47 18
23 0.7
Chlanidota densesculpta
SG
3
nd- 124.3
34-100
nd- 13
Neobuccinum eatoni
SI
2
nd-21.8
nd-3.5
nd-l.2
Serolis pagenstecheri
SG
5
36.6-859.9
2.4-16
2.1-6.0
Serolis cornuta
SI
6
56.7-96.5
4.7-25
3.5-14
Euphausia superba
SG
1
110.4
630
1.5
SG : South Georgia SI : Signy Island nd : not detected
15 33 : Total n-alkanes (C15-C33)
TABLE 3
Aromatic hydrocarbon contents of Antarctic marine invertebrates (ng g I wet weight). No. of Site samples
Species
Total
N
CI-N
C2-N
C3-N
P
CI-P
C2-P
CI-D
C2-D
NPD
Odontaster validus
SG SI
1 1
330 2.3
1.0 nd
2.1 0.5
8.5 2.8
430 2.0
12 0.5
10 nd
8.0 nd
14 nd
815.6 10.9
Chlanidotadensesculpta
SG
3
41-63
nd-l.8
nd-2.4
4.0-9.1
2.6-4.8
nd-3.4
nd-3.0
nd-3.2
nd-2.6
59.2-85.5
Neobuccinum eatoni
SI
1
2.6
nd
nd
nd
3.1
1.1
0.3
1.9
1. !
10.1
Serolispagenstecheri
SG
5
nd-74
nd-1.2
nd-2.3
nd-5.8
4.1-44
nd-3.5
nd-4.7
nd-6.1
nd-7.1
40-118
Seroliscornuta
S1
6
nd-3.7
nd-0.3
nd-0.7
nd-5.1
nd-8.8
nd-4.1
nd-3.4
nd-4.0
nd-3.2
14.2-22.8
Euphausia superba
SG
I
8.5
18
140
98
1()
2.4
nd
5.2
nd
282.1
SG SI nd N P
: : : : :
South Georgia Signy Island not detected naphthalene phenanthrene
the two traces from whole tissues of Serolis (Figs 2a,b). Chromatograms of animals from King Edward Cove exhibited a wide range of n-alkane peaks, superimposed on a prominent unresolved complex mixture (UCM). This type of chromatogram is usually considered to indicate the presence of pollutant petroleum hydrocarbons (Farrington & Meyer, 1975). In contrast, chromatograms of samples from Signy Island contained fewer peaks and no UCM. However, most of these Signy Island samples showed a very prominent triplet of peaks which were absent from South Georgia samples (with the exception of one of the five samples of Serolis pagenstecheri). 12
D C 1C2-
: : : NPD :
dibenzothiophene methyl derivative dimethyl or ethyl derivative naphthalene, phenanthrene, dihenzothiophene and those derivatives determined in this study.
In all cases the envelope of n-alkane peaks was smooth, with no indication of any odd-carbon predominance; the peak of the envelope was at about C24-26. Although the alkane distributions of invertebrates from South Georgia and Signy Island were similar, the total concentrations differed greatly, particularly between the Serolis species. Serolis cornuta at Signy Island contained between 56.7 and 96.5 ng g ~ wet weight total n-alkanes (C15-33), whereas Serolis pagenstecheri from South Georgia contained extremely variable concentrations, with the maximum nearly an order of magnitude greater (between 36.6 and 859.9 ng g ~; Table 2). The concentrations from the
Volume 12/Number l / J a n u a r y 1981
(a)
o
Z
c~
UCM
(b)
¥ a.
Fig. 2 (a) Capillary GC trace of hydrocarbons from Serolis pagenstecheri, King Edward Cove, South Georgia. 1 o', fresh weight 2.45 g, 25 m W C O T O V - 1. (b) Capillary GC trace of hydrocarbons from Serolis cornuta, Signy Island. 19, wet weight 3.70 g. 25 m W C O T OV-1.
13
Marine Pollution Bulletin
predatory whelk Chlanidota densesculpta at South Georgia were also very varied, one whelk containing 124.3 ng g-J total n-alkanes (C15-33), whereas another sample contained no detectable n-alkanes. Mackie et al. (1979) reported concentrations of total n-alkanes (C15-33) for several benthic invertebrates from King Edward Cove, South Georgia. Their data were also very variable, ranging from 38 ng g- ~in a pooled sample of the starfish Diplasterias meridionalis to 2736 ng g-~ in the burrowing tectibranch mollusc Philine gibba. A single pooled sample of Chlanidota densesculpta contained 121 ng g ~, very similar to our own value of 124.3 ng g-1. Pristane concentrations were similar to those reported here, with the exception of their Chlanidota densesculpta (1264 ng g-~) and Philine gibba(194 ng g ~). Aromatic hydrocarbons concentrations are given in Table 3. In general these repeat the trends shown by the n-alkane data; e.g. South Georgia invertebrates contained more variable and usually much greater amounts than those from Signy Island. The single starfish Odontaster validus from Signy Island contained only 10.9 ng g- ] wet weight of the aromatics determined (Table 3), whereas those from South Georgia contained 815.6 ng g-~. The ranges of the results emphasize this difference: 10.1-22.8 ng g ~(Signy Island); 85.5-815.6 ng g-l (South Georgia). South Georgia samples generally contained slightly more of the alkylated aromatics measured in this study, but also contained large quantities of the unsubstituted compounds naphthalene and phenanthrene. Pyrolysis reactions during the combustion of fossil fuels lead to a predominance of unsubstituted aromatics over alkylated derivatives, whereas the opposite is usually the case in unburnt petroleum oils. Contamination from this former source could explain the observed composition at South Georgia. The triplet of peaks found in most Signy Islands samples, and one from South Georgia, are aliphatic materials probably of natural origin, although their source is unknown. Similar peaks have also been found recently in samples of intertidal mud from the estuary of the River Crouch, on the south-east coast of England (Law, unpublished data).
Discussion From their analyses of King Edward Cove sediments, Platt & Mackie (1979) suggested that the aromatic components of the samples resulted from a world-wide dissemination of combustion products. However, this cannot be the reason for the high concentrations of unsubstituted aromatics in benthos from South Georgia, as neither benthos from Signy Island nor an offshore sample of krill, Euphausia superba, from South Georgia contained these high concentrations, even though the krill had a high total aromatic content. This suggests that the naphthalene and phenanthrene found in King Edward Cove samples are derived from a local source. The authors would like to thank Tim Flood, Steven Jones and Richard Luxmore for help in the collection of samples; and Stan Evans of Finnigan Instruments for help in the library searching of unknown mass spectra. Disclaimer: The reference to proprietary products in this paper should not be construed as an official endorsement of these products, nor is any criticism implied of similar products which have not been mentioned.
Clarke, A. (1979). Lipid content and composition of the pink shrimp, Pandalus montagui (Leach) (Crustacea: Decapoda). J. exp. mar. Biol. Ecol., 38, 1-17. Farrington, J. W. & Meyer, P. A. (1975). Hydrocarbons in the marine environment. In Environmental Chemistry, Vol. 1, pp. 109-136, G. Eglinton (ed.). The Chemical Society, London. Law, R. J. (1978a). Petroleum hydrocarbon analyses conducted following the wreck of the supertanker Amoco Cadiz. Mar. Pollut Bull., 9, 293 -296. Law, R. J. (1978b). Determination of petroleum hydrocarbons in water, fish and sediments following the Ekofisk blow-out. Mar. Pollut. Bull., 9, 321-324. Mackie, P. R., Platt, H. M. & Hardy, R. (1978). Hydrocarbons in the marine environment. II. Distribution of n-alkanes in the fauna and environment of the sub-Antarctic lsland of South Georgia. Estuar. Coastal Mar. Sci., 6, 301-313. Platt, H. M. (1978). Assessment of the macrobenthos in an Antarctic environment following recent pollution abatement. Mar. Pollut. Bull., 9, 149-153. Platt, H. M. (1979a). Sedimentation and the distribution of organic matter in a sub-Antarctic marine bay. Estuar. Coastal Mar. Sci., 9, 51-63. Platt, H. M. (1979b). Ecology of King Edward Cove, South Georgia: macro-benthos and the benthic environment. Bull. Br. Antarct. Surv., 49, 231-238. Platt, H. M. & Mackie, P. R. (1979). Analysis of aliphatic and aromatic hydrocarbons in Antarctic marine sediment layers. Nature, Lond., 280, 576-578.
Marine Pollution Bulletin, Vol. 12, pp. 14-19
0025-326X/81/0101 0014$02.00"0
©Pergamon PressLtd. 1981.Printedin Great Britain.
Effects of Surface and Sunken Crude Oil on the Behaviour of a Sea Urchin V. AXIAK and L. J. SALIBA
Department of Mathematics and Science, University of Malta, Tal-Qroqq, Malta Studies have been made of the effects of exposure to various forms of crude oil on the righting behaviour of Paracentrotus lividus and its reactions towards the presence of oil. Prolongation of the righting response was recorded in animals exposed to contact with surface or sunken fresh crude oil or to their water soluble fractions. No such effect
14
was recorded on exposure to weathered oils and results indicate that the more volatile components of crude oil were responsible for this effect. Paracentrotus showed no avoidance reaction to the presence of sunken oil in its vicinity. The likely ecological significance of these results is discussed.
constructive note on which to end. Oil spill impact assessment in previously unsurveyed areas presents considerable problems in selection of reference or 'control' sites and interpretation of data. For some types of investigation, field experiments provide an alternative approach which is particularly useful in the tropics as choice of experimental sites for convenience can eliminate the transport and accommodation problems of surveys in remote areas. The experimental applications of oils and dispersants now being planned in both Nigeria and Indonesia are feasible in any tropical country and provide an opportunity for properly controlled, quantitative biological work of academic, applied and educational value.
Cairns, J., Heath, A. G. & Parker, B. C. (1975). Temperature influence on chemical toxicity to aquatic organisms. War. Pollut. ControlFed., 47, 267-280. Earl, G. W. (1837). TheEastern Seas. W. H. Allen, London. LEMIGAS (Lembaga Minyak dan Gas Bumi) and Smithsonian Institution Office of International and Environmental Program). (1974). Coastal zone pollution in Indonesia with emphasis on oil. LEMIGAS, Jakarta. Macnae, W. (1968). A general account of the fauna and flora of mangrove swamps and forests in the Indo-West Pacific region. Adv. Mar. Biol. 6, 73-270. Odum, E. P. (1971). Fundamentals o f Ecology. W. B. Saunders, Philadelphia-London-Toronto. Rao, G. N. S. (1965). Use of seaweeds directly as food. Indo-Pacific Fisheries Council, Bangkok (Reg. Stud. Indo-Pacif. Fish. Coun. No. 2). Sanders, H. L. (1968). Marine benthic d i v e r s i t y - a comparative study. A m . Natur., 102. (925), 243-282. Schuster, W. H. (1952). Fish culture in brackish water ponds of Java. Diocesan Press, Madras (Indo-Pacif. Fish. Coun. Spec. PuN. No. 1).
MarinePollutionBulletin, Vol. 12, pp. 10-14 PergamonPressLtd. 1981.Printedin Great Britain.
0025-326X/81/01014)010$02.00/0
Aliphatic and Aromatic Hydrocarbons in Benthic Invertebrates from Two Sites in Antarctica* ANDREW CLARKE 1- and ROBIN LAW ¢
¢ British Antarct& Survey, NERC, Madingley Road, Cambridge CB50ET, UK ¢ MAFF." Directorate of Fisheries Research, Fisheries Laboratory, Remembrance A venue, Burnham-on-Crouch, Essex CMO 8HA, UK
Samples of marine benthic invertebrates collected from two sites in the Antarctic have been analysed for both aliphatic and aromatic hydrocarbons in order to establish baseline concentrations for some classes of hydrocarbons. Samples from Signy Island, a pristine site, contained low concentrations of the hydrocarbons determined, whereas those from King Edward Cove, South Georgia, contained significantly higher concentrations. King Edward Cove has a known history of pollution from whaling operations. Platt & Mackie (1979) have suggested that the hydrocarbons in sediments from King Edward Cove are a result of the world-wide dissemination of the pyrolysis products of fossil fuels. Our work suggests, in contrast, that the hydrocarbons in the benthos are derived from local sources. Antarctica is one area of the globe which remains relatively unpolluted by man's activity; the volume of shipping is small and permanent human settlements are few. These factors and the prevailing pattern of water currents suggest *© Crown Copyright.
10
that hydrocarbon concentrations in Antarctic benthos should represent background or baseline concentrations, i.e., marine invertebrates sampled from pristine areas in Antarctica should contain only biogenic hydrocarbons. Unfortunately, parts of Antarctica do not measure up to this high quality, and in this paper we present data for the hydrocarbon content of marine invertebrates from two sites in Antarctica, one with a known history of severe pollution from a whaling station; the other is believed to be a pristine site. The intention of this work was to establish baseline concentrations for some classes of hydrocarbons (which could be used in future pollution investigations); and to compare with concentrations present in invertebrates from an area subject at an earlier date to industrial pollution.
Materials and M e t h o d s Samples were collected from King Edward Cove, South Georgia, and from Normanna Strait, Signy Island. The positions of these two islands are shown in Fig. 1. King Edward Cove, South Georgia (54 ° 17' S, 36 ° 30' W) is a small, shallow cove with a bottom comprised largely of
Volume 12/Number l/January 1981
I
FALKLAND
~
ISLANDS
I
!
50 °
40*
',~AMERICA f
/
/ /
~SSoS
/
80 °
J
30"~ f
J
S O U T H GEORGIA
J /
/
f
550S, ¢~,6'
SIGNY /
,
ISLAND
"
?
~65*S
20
D"
WEDDELL
""*~(_':.:F'
90°W
. . . . . . . . . . . . ~5 "'~""
SEA
....
65"S
lOg
o__.
~,,
75°S
,.,,i '- ",,'.. ,, ....... ,,
100 ° 100 °
90°W
~0 o
/ i
"
.~..~. (,," 70 °
6o . . . . , 5o °
':~, 40 ° ',"
30°w,
20 °`
75°s, ,'1°°
,~,
0°/
Fig. 1 Map of Antarctica showing location of sampling areas.
uncompacted mud at the centre, grading to fine sand in shallower water. From 1904 until 1965 this cove was the site of an active whaling station, and considerable quantities of fossil fuels and biological material were discharged into its waters. Descriptions of this environment are to be found in Platt (1979a,b) and an analysis of the benthic community following the cessation of whale processing is to be found in Platt (1978). Mackie et aL (1978) have presented analyses of the n-alkanes in representative marine and terrestrial organisms from this area. Normanna Strait, Signy Island (60 ° 43' S, 45 ° 38' W) has been little affected by human presence with the exception of the occasional passage of ships. The area is extensively covered by fast-ice in winter, and as there is no evidence of petroleum seeps in the area, it is believed to be a pristine environment. As far as was possible comparable organisms were taken from each site, and details of these are given in Table 1. Benthos was collected by SCUBA diving and Euphausia superba by midwater trawl. Both were immediately frozen to - 40°C. Storage and transport also took place at - 40°C under nitrogen. Care was taken to avoid contamination from sampling apparatus or as a result of poor technique,
particularly by avoiding the use of plastics, oil and grease. Both procedural blanks and a deliberately contaminated 'blank' were analysed at the same time as the samples. Lipids were extracted from the samples with methanolchloroform (Clarke, 1979), and hydrocarbons were purified from these extracts by chromatography on silica gel (7% deactivated with water). The hydrocarbon fractions were then analysed on a 25 m glass capillary column coated with OV-1 in a Carlo Erba 2151 gas chromatograph (n-alkanes), and by mass fragmentography using a Finnigan 3200-6110 computerized capillary GC-MS system (aromatics) (see Law, 1978a,b). GC-MS quantitation was by internal standardization; known weights of the fully deuterated analogues of naphthalene (naphthalene-d8) and phenanthrene (phenanthrene-dl0) (Merck, Sharp and Dohme, Hoddesdon, Hertfordshire) being added before sample extraction.
Results Results of the analyses are given in Tables 2 and 3. Consistent and striking differences were apparent in the chromatograms of samples from the two areas, as shown by 11
Marine Pollution Bulletin
TABLE
1
Antarctic marine invertebrates analysed for hydrocarbons. South Georgia
Signy Island
Class
Species
No. in sample
Species
No. in sample
Echinodermata
Odontaster validus
6 immature
Odontaster validus
1
Mollusca
Chlanidota densesculpta
3
Neobuccinum eatoni
1
1 1
Crustacea
Serolis pagenstecheri
1
1; 1;
Serolis cornuta
1 1 1 1 5 immature
1; 1: 4immature
Euphausia superba
6 gravid .
TABLE 2
Aliphatic hydrocarbon content of Antarctic marine invertebrates (ng g - ] wet weight).
Species
Site
No. of samples
~ 15 Z.., 33
Odontaster validus
SG SI
1 1
525.5 24.3
Pristane
Phytane
47 18
23 0.7
Chlanidota densesculpta
SG
3
nd- 124.3
34-100
nd- 13
Neobuccinum eatoni
SI
2
nd-21.8
nd-3.5
nd-l.2
Serolis pagenstecheri
SG
5
36.6-859.9
2.4-16
2.1-6.0
Serolis cornuta
SI
6
56.7-96.5
4.7-25
3.5-14
Euphausia superba
SG
1
110.4
630
1.5
SG : South Georgia SI : Signy Island nd : not detected
15 33 : Total n-alkanes (C15-C33)
TABLE 3
Aromatic hydrocarbon contents of Antarctic marine invertebrates (ng g I wet weight). No. of Site samples
Species
Total
N
CI-N
C2-N
C3-N
P
CI-P
C2-P
CI-D
C2-D
NPD
Odontaster validus
SG SI
1 1
330 2.3
1.0 nd
2.1 0.5
8.5 2.8
430 2.0
12 0.5
10 nd
8.0 nd
14 nd
815.6 10.9
Chlanidotadensesculpta
SG
3
41-63
nd-l.8
nd-2.4
4.0-9.1
2.6-4.8
nd-3.4
nd-3.0
nd-3.2
nd-2.6
59.2-85.5
Neobuccinum eatoni
SI
1
2.6
nd
nd
nd
3.1
1.1
0.3
1.9
1. !
10.1
Serolispagenstecheri
SG
5
nd-74
nd-1.2
nd-2.3
nd-5.8
4.1-44
nd-3.5
nd-4.7
nd-6.1
nd-7.1
40-118
Seroliscornuta
S1
6
nd-3.7
nd-0.3
nd-0.7
nd-5.1
nd-8.8
nd-4.1
nd-3.4
nd-4.0
nd-3.2
14.2-22.8
Euphausia superba
SG
I
8.5
18
140
98
1()
2.4
nd
5.2
nd
282.1
SG SI nd N P
: : : : :
South Georgia Signy Island not detected naphthalene phenanthrene
the two traces from whole tissues of Serolis (Figs 2a,b). Chromatograms of animals from King Edward Cove exhibited a wide range of n-alkane peaks, superimposed on a prominent unresolved complex mixture (UCM). This type of chromatogram is usually considered to indicate the presence of pollutant petroleum hydrocarbons (Farrington & Meyer, 1975). In contrast, chromatograms of samples from Signy Island contained fewer peaks and no UCM. However, most of these Signy Island samples showed a very prominent triplet of peaks which were absent from South Georgia samples (with the exception of one of the five samples of Serolis pagenstecheri). 12
D C 1C2-
: : : NPD :
dibenzothiophene methyl derivative dimethyl or ethyl derivative naphthalene, phenanthrene, dihenzothiophene and those derivatives determined in this study.
In all cases the envelope of n-alkane peaks was smooth, with no indication of any odd-carbon predominance; the peak of the envelope was at about C24-26. Although the alkane distributions of invertebrates from South Georgia and Signy Island were similar, the total concentrations differed greatly, particularly between the Serolis species. Serolis cornuta at Signy Island contained between 56.7 and 96.5 ng g ~ wet weight total n-alkanes (C15-33), whereas Serolis pagenstecheri from South Georgia contained extremely variable concentrations, with the maximum nearly an order of magnitude greater (between 36.6 and 859.9 ng g ~; Table 2). The concentrations from the
Volume 12/Number l / J a n u a r y 1981
(a)
o
Z
c~
UCM
(b)
¥ a.
Fig. 2 (a) Capillary GC trace of hydrocarbons from Serolis pagenstecheri, King Edward Cove, South Georgia. 1 o', fresh weight 2.45 g, 25 m W C O T O V - 1. (b) Capillary GC trace of hydrocarbons from Serolis cornuta, Signy Island. 19, wet weight 3.70 g. 25 m W C O T OV-1.
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Marine Pollution Bulletin
predatory whelk Chlanidota densesculpta at South Georgia were also very varied, one whelk containing 124.3 ng g-J total n-alkanes (C15-33), whereas another sample contained no detectable n-alkanes. Mackie et al. (1979) reported concentrations of total n-alkanes (C15-33) for several benthic invertebrates from King Edward Cove, South Georgia. Their data were also very variable, ranging from 38 ng g- ~in a pooled sample of the starfish Diplasterias meridionalis to 2736 ng g-~ in the burrowing tectibranch mollusc Philine gibba. A single pooled sample of Chlanidota densesculpta contained 121 ng g ~, very similar to our own value of 124.3 ng g-1. Pristane concentrations were similar to those reported here, with the exception of their Chlanidota densesculpta (1264 ng g-~) and Philine gibba(194 ng g ~). Aromatic hydrocarbons concentrations are given in Table 3. In general these repeat the trends shown by the n-alkane data; e.g. South Georgia invertebrates contained more variable and usually much greater amounts than those from Signy Island. The single starfish Odontaster validus from Signy Island contained only 10.9 ng g- ] wet weight of the aromatics determined (Table 3), whereas those from South Georgia contained 815.6 ng g-~. The ranges of the results emphasize this difference: 10.1-22.8 ng g ~(Signy Island); 85.5-815.6 ng g-l (South Georgia). South Georgia samples generally contained slightly more of the alkylated aromatics measured in this study, but also contained large quantities of the unsubstituted compounds naphthalene and phenanthrene. Pyrolysis reactions during the combustion of fossil fuels lead to a predominance of unsubstituted aromatics over alkylated derivatives, whereas the opposite is usually the case in unburnt petroleum oils. Contamination from this former source could explain the observed composition at South Georgia. The triplet of peaks found in most Signy Islands samples, and one from South Georgia, are aliphatic materials probably of natural origin, although their source is unknown. Similar peaks have also been found recently in samples of intertidal mud from the estuary of the River Crouch, on the south-east coast of England (Law, unpublished data).
Discussion From their analyses of King Edward Cove sediments, Platt & Mackie (1979) suggested that the aromatic components of the samples resulted from a world-wide dissemination of combustion products. However, this cannot be the reason for the high concentrations of unsubstituted aromatics in benthos from South Georgia, as neither benthos from Signy Island nor an offshore sample of krill, Euphausia superba, from South Georgia contained these high concentrations, even though the krill had a high total aromatic content. This suggests that the naphthalene and phenanthrene found in King Edward Cove samples are derived from a local source. The authors would like to thank Tim Flood, Steven Jones and Richard Luxmore for help in the collection of samples; and Stan Evans of Finnigan Instruments for help in the library searching of unknown mass spectra. Disclaimer: The reference to proprietary products in this paper should not be construed as an official endorsement of these products, nor is any criticism implied of similar products which have not been mentioned.
Clarke, A. (1979). Lipid content and composition of the pink shrimp, Pandalus montagui (Leach) (Crustacea: Decapoda). J. exp. mar. Biol. Ecol., 38, 1-17. Farrington, J. W. & Meyer, P. A. (1975). Hydrocarbons in the marine environment. In Environmental Chemistry, Vol. 1, pp. 109-136, G. Eglinton (ed.). The Chemical Society, London. Law, R. J. (1978a). Petroleum hydrocarbon analyses conducted following the wreck of the supertanker Amoco Cadiz. Mar. Pollut Bull., 9, 293 -296. Law, R. J. (1978b). Determination of petroleum hydrocarbons in water, fish and sediments following the Ekofisk blow-out. Mar. Pollut. Bull., 9, 321-324. Mackie, P. R., Platt, H. M. & Hardy, R. (1978). Hydrocarbons in the marine environment. II. Distribution of n-alkanes in the fauna and environment of the sub-Antarctic lsland of South Georgia. Estuar. Coastal Mar. Sci., 6, 301-313. Platt, H. M. (1978). Assessment of the macrobenthos in an Antarctic environment following recent pollution abatement. Mar. Pollut. Bull., 9, 149-153. Platt, H. M. (1979a). Sedimentation and the distribution of organic matter in a sub-Antarctic marine bay. Estuar. Coastal Mar. Sci., 9, 51-63. Platt, H. M. (1979b). Ecology of King Edward Cove, South Georgia: macro-benthos and the benthic environment. Bull. Br. Antarct. Surv., 49, 231-238. Platt, H. M. & Mackie, P. R. (1979). Analysis of aliphatic and aromatic hydrocarbons in Antarctic marine sediment layers. Nature, Lond., 280, 576-578.
Marine Pollution Bulletin, Vol. 12, pp. 14-19
0025-326X/81/0101 0014$02.00"0
©Pergamon PressLtd. 1981.Printedin Great Britain.
Effects of Surface and Sunken Crude Oil on the Behaviour of a Sea Urchin V. AXIAK and L. J. SALIBA
Department of Mathematics and Science, University of Malta, Tal-Qroqq, Malta Studies have been made of the effects of exposure to various forms of crude oil on the righting behaviour of Paracentrotus lividus and its reactions towards the presence of oil. Prolongation of the righting response was recorded in animals exposed to contact with surface or sunken fresh crude oil or to their water soluble fractions. No such effect
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was recorded on exposure to weathered oils and results indicate that the more volatile components of crude oil were responsible for this effect. Paracentrotus showed no avoidance reaction to the presence of sunken oil in its vicinity. The likely ecological significance of these results is discussed.