Brink, N.W., van den

Ruiter-Dijkman, E.M., de

van den Brink, N.W.

de Ruiter-Dijkman, E.M.

NARCIS 

Trans-nonachlor, octachlorstyrene, mirex and photomirex in Antarctic seabirds

Wageningen Yield 

Antarctic Science 9 (4): 4 14-4 17 (1997) 
Trans-nonachlor, octachlorostyrene, mirex and photomirex in 
Antarctic seabirds 
NlCO W. VAN DEN BRINK and ELZE M. DE RUITER-DIJKMAN 
Institute for Forestry and Nature Research (IBN-DLO), PO Box 23, NL-6700 AA Wageningen, The Netherlands 
Abstract: Octachlorostyrene (OCS) and trans-nonachlor (TNC) were detected in cape petrels (Daption 
cupense) of King George Island, which tallies with their presence in samples of gentoo penguins (Pygoscelis 
pupua) of the Falkland Islands. The detection of TNC in a sample of the Antarctic southern fulmar (Fulmarus 
glacialoides) implies that the Antarctic region has been contaminated by this compound. Mirex and 
photomirex were also detected in samples of the cape petrels and southern fulmar, as well as in Addlie penguins 
(Pygoscelis adeliae) from Hop Island. The ratios of the mirex and photomirex concentrations in the truly 
Antarctic species from different locations are similar, which suggests that these compounds are diffusely 
distributed over the continent. The detection of organochlorine pollutants in Antarctic seabirds is an 
indication that these compounds have a global distribution. Screening of subcutaneous fat of Antarctic 
seabirds for organochlorines provides an excellent indication of the occurrence of organochlorine pollutants 
in Antarctica, and as such an 'early warning' for the global dispersion of these compounds. 
Received 10 December 1996, accepted 25July 1997 
Keywords: Antarctic seabirds, early warning, monitoring, organochlorine pollutants 
Introduction 
Following the detection of DDT compounds in a crabeater 
seal (Lobodon carcinophagus) and AdClie penguins 
(Pygoscelis adeliae) by Sladen et al. (1966) there have been 
several reports on the occurrence of organochlorine pollutants 
in Antarctic samples (i.e. Hidaka et al. 1983, Tanabe et al. 
1983, Focardi et al. 1992, Fuoco et ul. 1994, Van den Brink 
1997b). Data on organochlorine pollutants in Antarctic 
samples indicate contamination of this environment and as 
such can act as an 'early warning' for the global distribution 
of these man-made chemicals (Walton & Shears 1994). 
Since concentrations of organochlorines in subcutaneous 
fat have been shown to correlate with concentrations in other 
tissues (Van den Brink 1997a), we initiated this study to 
assess the value of analysis of subcutaneous fat samples of 
Antarctic seabirds as indicators of the occurrence of unknown 
organochlorine pollutants at low levels in the Antarctic 
ecosystem. 
Materials and methods 
The eight AdClie penguins (Pygoscelis udeliae) used in this 
study were found dead in the summer of 1991-92 around 
their breeding colonies at Hop Island and Magnetic Island 
near Davis station (68'33's 77"54'E). Three failed breeding 
pairs of cape petrels (Duption cupense) were collected at 
Demay Point, near Arctowski station at King George Island 
(62*09'S 58*29'W) in January 1991. A southern fulmar 
(Fulmarus glacialoides) was found dead at Ardery Island 
near Casey station (66*17'S 110*32'E). 
The birds were dissectedunder clean lab conditions and the 
subcutaneous fat analysed for organochlorines with GC- 
ECD (cf. Van den Brink 1997b) with confirmation and 
quantification using GC-MS. Compounds were identified on 
the GC-MS using their mass-spectrum and retention time. 
For quantification of the different compounds the masses of 
three ion fragments were summed. The ion fragments with 
following mass-to-charge ratios were used for the different 
compounds: OCS: m/z 341, 343, 345, TNC: m/z 407,409, 
411, mirex: m/z 270, 272, 274, photomirex: m/z 270, 272, 
274. Standards of mirex, TNC and OCS were obtained from 
Ehrenstorfer. A standard of photomirex was quantified as 
the loss of mirex after photo-degradation (UV-light: 254 and 
366 nm) for 16 hours. 
Results and discussion 
Identification of unknown peaks 
In Fig. 1 a GC-ECD chromatogram is presented of a typical 
sample of a cape petrel. In this chromatogram some peaks are 
numbered for reference. In this sample three unknown peaks 
(number 2, 3 & 7) are of interest. Peak 7 also occurs in 
samples of Ad&lie penguins and peak 3 and 7 in the sample 
of the southern fulmar. In Figs 2 4  the mass spectra of the 
three unknown compounds in the subcutaneous fat of a cape 
petrel are presented. 
The mass spectrum of peak 2 (Fig. 2) strongly resembles 
the mass spectrum of OCS and has an identical retention 
time. Hence, peak 2 is considered to be OCS. 
41 4 
ORGANOCHLORINES IN BIRDS 41 5 
2000.0 
1800.0 
1600.0 
1400.0 
1200.0 
1000.0 
800.0 
600.0 
400.0 
3 1 
5 
6 
- 
10.0 15.0 20.0 25.0 30.0 
2 0 0 . 0 L  . 
Minutes 
Fig, 1. ECD-chromatogram of subcutaneous fat of a cape 
petrel. Peaks with the following numbers are identified as: 1: 
hexachlorobenzene; 4: p,p'-DDE; 5:  PCB153; 6: PCB138; 8: 
PCB180; 9: mirex; 15 PCB170; 11: PCB194; 12: 
octachloronaphtalene (internal standard). Peaks 2,3 and 7 are 
unidentified so far and discussed. 
475 
e 
3 
0 a 
388 
388 
I la , , , , , , , , 
368 388 480 120 440 468 480 w r  
Fig. 2. Mass spectrum of peak 2 in subcutaneous of a cape 
petrel . 
The mass spectrum for peak 3 (Fig. 3) corresponds with the 
mass spectrum of TNC. However, in the spectrum of this 
compound the ion fragments with the ratios of m/z 407,409 
and 411 are relatively low compared to the standard for TXC. 
This is probably due to contamination of the spectrum by the 
background signal because of the relatively low concentration 
of TNC. Nevertheless, the retention times of this peak in all 
samples are identical to the TNC standard. So, peak 3 has 
been provisionally identified as TNC, and results quantified 
on this basis. 
The detection of OCS and TNC in samples of the cape 
petrels from King George Island is a confirmation of the 
detection of these compounds in brains, liver and muscles of 
13800 1 
208 220 240 268 288 
407 
Fig. 3. Mass spectrum of peak 3 in subcutaneous of a cape 
petrel. 
3 as 
Fig. 4. Mass spectrum of peak 7 in subcutaneous of a cape 
petrel. 
gentoo penguins (Pygoscelispapua) from the more northerly 
Falkland Islands (De Boer & Wester 1991). 
Peak7 (Fig. 4) shows a mass spectrum characterized by the 
ion fragments with the mass-to-charge ratios of m/z 272 and 
475. The former fragment is typical of the spectrum of mirex, 
but the fragment of mlz 475 is not. The mass spectrum of 
photomirex strongly resembles that of peak 7 in the sample 
of the cape petrel. The retention time of photomirex is equal 
to peak 7, so this compound is considered to be photomirex. 
Quantification 
The results show the possibility of detection of unknown 
organochlorines in subcutaneous fat of Antarctic seabirds. In 
cape petrels the concentrations of TNC are highest of the 
three species (Table I). In the AdClie penguin no TNC could 
be detected and the southern fulmar only contained low 
concentrations of TNC. The latter is remarkable because the 
sample amount collected from the southern fulmar is small. 
The concentrationsofTNCfound inliversof gentoopenguins 
41 6 NlCO W. VAN DEN BRINK & ELZE M. DE RUITER-DIJKMAN 
Table I. The geometric means (range in between brackets) of concentrations of trans-nonachlor, octachlorost yrene, mirex and photomirex. 
TNC ocs mirex photomirex 
ng g-' fat ng g-' fat ng g' fat ng g' fat 
cape petrel ( n  = 6) 1.7*10* 42 2.3'103 5.1' lo2 
(47-1.9' lo3) (22-1.0'102) (1.4*10)-5.2'103) (2.8' 102 -1.4'103) 
Adtlie penguin (n = 8) < 0.5 < 0.5 82 12 
(27-1 S.10') (7-21) 
southern fulmar (n = 1) 51 < 40 3.0 lo4 4.7.10' 
caught near the Falkland Islands (De Boer & Wester 1991) 
are within the range detected in subcutaneous fat of cape 
petrels in the current study. 
OCS was detected in the cape petrels but not in the truly 
Antarctic species. The OCS concentrations in livers of 
gentoo penguins are considerable lower than those in the 
cape petrels (De Boer & Wester 1991). The different tissues 
that were analysed in the two studies, or the different feeding 
ecologies of the species investigated may account for the 
differences in OCS concentrations. 
In contrast to the absolute concentrations of mirex and 
photomirex, the ratio between the concentrations of mirex 
and photomirex are similar between the southern fulmar and 
the Adtlie penguin. These species are both restricted to 
Antarctica, but the samples were collected at different 
locations. Although only one sample of the southern fulmar 
was analysed, the similar ratios of mirex and photomirex 
concentrations suggest a correlated distribution of mirex and 
photomirex in Antarctica. 
The ratio of the concentrations of mirex and photomirex 
found in the cape petrel is lower than in the Antarctic species. 
Thismay be explained by the different geographic distribution 
of the species (Van den Brink 199713). Ratios found in birds 
of the Great Lakes in Canada are lower (Sergeant et al. 1993) 
than in the cape petrels. The distribution ranges of the 
species of the current study are well away from the potential 
(Alley et al. 1973, Sergeant et al. 1993). The fact that the 
concentrations of the degradation product are lower further 
away from the source is in contrast for what is found for 
p,p'-DDT. It seems that photomirex disperses less easily 
through atmospheric transport than mirex. This may be 
related to physical and chemical properties of the compound 
(Van den Brink 1997b). 
Conclusions 
The detection of TNC and OCS in the cape petrels of the 
current study is in agreement with the reported occurrence of 
these compounds in gentoo penguins of the Falkland Islands 
(De Boer & Wester 1991). However, the OCS concentrations 
in the cape petrels in the current study are higher. OCS was 
not detectable in the species confined to the Antarctic region. 
TNC was detected in one sample of a southern fulmar which 
may suggest that this compound has reached the Antarctic 
region. 
Mirex and photomirex, a degradation product of mirex, 
were detected in all species. The similar ratios between 
concentrations of mirex and photomirex in the southern 
fulmar and AdClie penguins from different locations suggest 
a diffuse distribution of the compounds within the Antarctic 
ecosystem. In the cape petrel the ratio is lower, which implies 
an higher relative concentration of photomirex. This may be 
related to the geographical distribution of the species. 
Analysis of samples of subcutaneous fat of Antarctic 
seabirds indicates the occurrence of organochlorine pollutants 
in Antarctic seabirds and therefore the Antarctic environment. 
This information can be used as an 'early warning' for the 
global distribution of these compounds. 
Acknowledgements 
Jacob DeBoerenPeter Wester are thankedfor their suggestions 
on the interpretation of the mass spectra. We are grateful to 
the station leader John Wilson and all other station personnel 
of Davis station in the summer of 1991-92, especially 
Charles Pascoe, Robin Carter and Sue Robertson who helped 
by the collection of the Adtlie penguins. Jan Andries van 
Franeker is greatly appreciated for the collection of the 
southern fulmar and for the dissection of the petrels. Wim 
Wolff and Tom van Spanje are acknowledged for the collection 
of the cape petrels. Wim Wolff and Rob Gast are thanked for 
their comments on a draft of this paper. We also thank 
Drs D. Osborn, A. Sarkar and an annonymous referee for 
their constructive comments. 
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Trans-nonachlor, octachlorstyrene, mirex and photomirex in Antarctic seabirds

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