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572-574. (57) Eadie, B. J.; Landrum, P. F.; Faust, W. R. In Polynuclear Aromatic Hydrocarbons: Tenth International Symposium on a Decade of Progress; Cooke, M. W., Dennis, A. J., Eds.; Battelle Press: Columbus, OH, 1985, pp 195-209.
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Eadie, B. J.; Morehead, N. R.; Landrum, P. F. Chemosphere 1990, 20, 161-178. Connolly, J. P.; Pedersen, C. J. Enuiron. Sci. Technol. 1988, 22, 99-103. Alldredge, A. L. Limnol. Oceanogr. 1979,24, 855-866. Elder, D. L.; Fowler, S. W. Science 1977, 197, 459-461. Beasley, T. M.; Heyraud, M.; Higgo, J. J. W.; Cherry, R. D.; Fowler, S. W. Mar. Biol. 1978, 44, 325-328. Schrader, H. J. Science 1971, 174, 55-57.
Received for review July 18, 1990. Revised manuscript received October 12,1990. Accepted October 15, 1990. This work is the result of research sponsored by the Minnesota Sea Grant College Program supported by the N O A A Office of Sea Grant, Department of Commerce, under Grant NA-85-AA-D-SG136, Journal Reprint No. 256. T h e U.S. Government is authorized to reproduce and distribute reprints for government purposes, not withstanding any copyright notation that may appear hereon.
Grounding of the Bahia Paraiso at Arthur Harbor, Antarctica. 1. Distribution and Fate of Oil Spill Related Hydrocarbons Mahlon C. Kennicutt 1 1 , " ~Stephen ~ 1.Sweet,+ William R. Fraser,s William L. Stockton,§ and Mary Culvert
Geochemical and Environmental Research Group, College of Geosciences, Texas A&M University, 833 Graham Road, College Station, Texas 77845, Pt. Reyes Bird Observatory, 4990 Shoreline Highway, Stinson Beach, California 94970, and Institute of Marine Studies, University of California, Santa Cruz, California 95064 In January to March 1989 water, organisms, and sediments within a 2-mile radius of Arthur Harbor were contaminated with an estimated 600000 L of petroleum spilled by the Bahia Paraiso. All components of the ecosystem were contaminated to varying degrees during the spill, including birds, limpets, macroalgae, clams, bottom-feeding fish, and sediments. The high-energy environment, the relatively small volume of material released, and the volatility of the released product all contributed to limiting toxic effects in time and space. The most effective removal processes were evaporation, dilution, winds, and currents. Sedimentation, biological uptake, microbial oxidation, and photooxidation accounted for removal of only a minor portion of the spill. One year after the spill several areas still exhibited contamination. Subtidal sediments and the more distant intertidal locations were devoid of detectable PAH contaminants whereas sediments near the docking facility at Palmer Station continued to reflect localized nonspill-related activities in the area. Arthur Harbor and adjacent areas continue to be chronically exposed to low-level petroleum contamination emanating from the Bahia Paraiso. Introduction
Petroleum derived from tanker accidents is believed to account for 10-15% of the oil released to the environment each year ( I ) . The majority of oil spill studies in the past have generally been restricted to temperate climates (2-9). However, the continued development of polar energy reserves, increased ship and tourist activities, and recent catastrophic releases of petroleum in polar regions have focused concern on high latitudes (10-14). Extensive investigations of the fate and effects of petroleum in the 'Texas A&M University. Pt. Reyes Bird Observatory. 5 University of California. 0013-936X/91/0925-0509$02.50/0
Arctic were undertaken in response to the development of oil reserves in northern Alaska and the subsequent construction of a trans-Alaska pipeline (1,15-18). On the other hand, little knowledge is available on the effects of oil on southern polar ecosystems and extrapolation from findings in the Arctic may be inappropriate (1, 19, 20). Increasingly, man's activities in the southern oceans have raised concerns about human impacts on what is seen as one of the last pristine areas on earth. Highlighting these concerns was the public response to the accidental release of refined petroleum products near Anvers Island on the Antarctic Peninsula in 1989 (21). Enroute to resupply an Argentine Antarctic base the Bahia Paraiso ran aground on 28 January 1989. The vessel contained a cargo of diesel fuel arctic (DFA), jet fuel (JP-1),gasoline, and compressed gas cylinders totaling more than one million L. An estimated 600000 L of DFA was released during the main phase of the spill. Palmer Station personnel and scientists instituted a comprehensive sampling effort within 1 day of the spill, including collections of water, intertidal organisms, sediment from beaches, and oil slicks. Samples were routinely collected at regular intervals at established sites to provide information on the location, fate, and effects of the spill. A research team consisting of benthic ecologists, algal physiologists, avian biologists, microbiologists, and hydrocarbon chemists was dispatched to the area in early March 1989 to continue and expand the initial activities (21). A resampling 1 year after the spill was undertaken in March 1990. The hydrocarbon chemistry program reported here focused on documenting the distribution and fate of the petroleum release.
Methods A variety of samples were collected and analyzed by methods commensurate with their use in the study (Table I; Figure 1). Samples from the intertidal and subtidal (sediments, macroalgae, and limpets) were collected by
0 1991 American Chemical Society
Environ. Sci. Technol., Vol. 25, No. 3, 1991 509
LOUDWATER Norse1 Pt.
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+ 1
Intertidal Sites Diver Assisted Intertidal / Subtidal Sites + Grab Samples
Old Palmer Station
64'46' S
Janus Is.
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Flgure 1. Sampling sites occupied during the Bahia Paraiso spill study. Two dive transects not shown were located near Dream Island, 9 miles northwest of Arthur Harbor.
hand by divers or from the shore. Sediments were collected in syringes and stoppered by the diver or scooped up with clean spatulas into sample containers. Sediment samples in deeper portions of the bays were sampled by a Smith-MacIntyre grab sampler from the R / V Polar Duke. Water column samples were collected by opening combusted glass-stoppered bottles immersed to the appropriate depth in the water column or by use of 30-L Go-Flo Niskin bottles. Slicks were collected by skimming the water surface into a glass bottle or by using a screen mesh. Refined products were collected from the Bahia Paraiso, R/V Polar Duke, Palmer Station, and Old Palmer Station including JP-1, DFA, lube oil, heating fuel, and hydraulic fluid. For preliminary screening, macroalgae were freeze-dried, sonicated in CH2C12,purified with alumina, and analyzed by total scanning fluorescence (22). Fluorescence intensity and spectra were used to detect the presence of petroleum hydrocarbons (22). If petroleum-related fluorescence was present, extracts were analyzed in greater detail by highresolution, fused-silica, capillary column gas chromatography with flame ionization ( G C I F I D ) and/or mass spectrometric (GC/MS) detection. The analytical procedures have been described in detail elsewhere and provide accurate, precise, and reproducible results (23, 2 4 ) . Water samples (500-1000 mL) were acidified to a p H of 2 with concentrated HC1 and liquid-liquid extracted three times with methylene chloride. The extracts were combined, concentrated, and dried with NaS04. Sediment samples (25-30 g) were freeze-dried, ground, and Soxhlet 510
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Table I. Summary of Bahia Paraiso Samples Analyzed
sample type water column sediments
analytical methodology solvent extraction, screening by GC/FID and fluorescence" solvent extraction, purification, quantitative GC/FID and GC/MS
tissues limpets
solvent extraction, quantitative PAHs by GC/MS solvent extraction, screening by macroalgae fluorescence" solvent extraction, screening by bird feathers fluorescence" solvent extraction, quantitative plankton tows GC/FID and GC/MS miscellaneous organisms solvent extraction, quantitative PAHs by GC/MS screening by GC/FID and GC/MS slicks fuels Samples showing significant fluorescence responses were analyzed further by GC/FID and GC/MS.
extracted for 12 h with 200 mL of methylene chloride. The extract was concentrated and exchanged into 2 mL of hexane. A 5-15-g sample of tissue (wet weight) was dried with Na2S04and macerated in 100 mL of CH2Cl2three times with a Tissuemizer for 3 min or digested in 6 N KOH at 35 "C for 18 h. For cold solvent extraction the extract was concentrated to 2 mL of hexane. For digestion the solution was serially extracted with ethyl ether and then concentrated.
Table 11. Concentration of Selected Aromatic and Aliphatics Compounds in Various Hydrocarbon Fluids Collected in the Vicinity of Arthur Harbor
benzene,
PPI g
DFA in a drum Polar Duke Palmer Station JP-1 lube oil a slick collected on 1/29
toluene,
ethylbenzene,
m- + p-xylene,
o-xylene,
n-C9,
n-CI4,
PPIP
PPIP
PPIP
PPlP
PPIP
PPIP
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