content and species composition (Diatoms) in relation to some

ecological factors. Ph.D. thesis. Department of Systematic Botany,

University of Lund, Sweeden. LUNDS/(NBBS-1006). p. 209.

Thompson, E.A., Laughlim, J.D., Tsukada, D.T., 1987. 1985 Refer-

ence site survey, Southern California Coastal Water Research

Project. Technical Report. Long Beach, California. p. 199.

UNEP, United Nations Environment Program, 1991. Determinations

of petroleum hydrocarbons in sediments. Reference Methods for

Marine Pollution Studies. No. 20. p. 97.

Volkman, J.K., Holdsworth, G.D., Neill, G.P., Bavor Jr., J.H., 1992.

Identification of natural, anthropogenic and petroleum hydrocar-

bons in aquatic sediments. The Science of the Total Environment

12, 203–219.

Wells, P.G., Daborn, G.R., 1997. The R�ııo de la Plata. An environ-

mental overview. An EcoPlata Project Background Report. Dal-

housie University, Halifax, Nova Scotia, Canada, p. 256.

Witt, G., 1995. Polycyclic aromatic hydrocarbons in water and

sediment of the Baltic sea. Marine Pollution Bulletin 31, 237–

248.

Zobell, C.E., 1946. Studies on redox potential of marine sediments.

Bulletin of the American Association of Petrology and Geology 30,

477–513.

0025-326X/02/$ - see front matter � 2002 Elsevier Science Ltd. All rights reserved.

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Antifoulant concentrations at the site of the Bunga TerataiSatu grounding, Great Barrier Reef, Australia

David Haynes *, Caroline Christie, Paul Marshall, Kirstin Dobbs

Great Barrier Reef Marine Park Authority, P.O. Box 1379, Townsville 4810, Australia

Keywords: Antifoulant; Copper; Great Barrier Reef; Ship grounding; Tributyltin; Zinc

Approximately 2500 large vessels (>50 m in length)transit an inshore route between Torres Strait andCairns within the northern area of the Great BarrierReef, Australia, every year (Haynes et al., 2001). Ap-proximately 65% of these movements occur through aninner shipping route which lies between the Australianmainland and the outer Great Barrier Reef (Fig. 1).Bulk carriers comprise the greatest proportion of ship-ping, and carry a range of cargos including bauxite,alumina, manganese iron ore, coal and sugar as well asgeneral container freight and oil. Movements of largeships within the northern Great Barrier Reef innershipping route are directed by professional pilots in thecompulsory pilotage area who are taken aboard inTorres Strait at the northern end of the Marine Park, orat the Port of Cairns (Fig. 1) if the ship is sailing north.Despite this service, 19 major grounding incidents haveoccurred in the Marine Park since 1979 (Raaymakers,1994; Haynes et al., 2001). A majority of these incidentshave occurred in remote areas in the far northern sectionof the Great Barrier Reef. Only one incident (thegrounding of the New Reach at Heath Reef in 1999) hasbeen assessed for chemical contamination arising from agrounding. Sediments at this site were found to contain

grossly elevated concentrations of antifoulant (Haynesand Loong, 2002).

On November 2nd, 2000, the 184 m cargo ship BungaTeratai Satu ran aground on Sudbury Reef (16�57:40S,146�09:410E), within the Great Barrier Reef WorldHeritage Area (Fig. 1). The reef sustained extensivestructural damage from the impact and a large U-shapedscar of compressed calcium carbonate surrounded byshattered coral rubble was created by the collision. Thevessel was refloated 14 days after the grounding usingtugs and its own propeller action. Sediment sampleswere collected from the area after the ship was removedto assess the extent of antifoulant contamination re-sulting from the grounding and ship refloating.

Collection of surficial (top 10 cm) sediment was car-ried out by divers scooping up sediment into preparedcontainers at the ship grounding site. Two replicatesediment samples were collected randomly at sites lo-cated 5, 10, 20, 50, 100, 250 and 1000 m along fourtransects radiating away from the ship grounding scar(Fig. 2). Replicate sediment samples were also collectedat three sites within the grounding scar. Each replicatesample was composited from successive scoops of sedi-ment and contained approximately 500 g of sediment.Samples were stored frozen in acid-washed plastic con-tainers.

Sediment samples were thawed, sub-sampledand analysed for butyltin, copper, lead, nickel and zinc

* Corresponding author. Tel.: +61-747500700; fax: +61-747726093.

E-mail address: d.haynes@gbrmpa.gov.au (D. Haynes).

968 Baseline / Marine Pollution Bulletin 44 (2002) 956–976

concentrations at the CSIRO Centre for AnalyticalChemistry, Sydney. Sediment subsamples were thor-oughly homogenised by grinding in a porcelain mortarand pestle. Sediment (1 g) was separated from the ho-mogenised sample for butyltin analysis. Butyltins wereextracted from each sediment sample matrix using 50% v/v methanol in 10 M HCl in an ultrasonic bath. The su-pernatant was then extracted with dichloromethane in thepresence of tropolone and finally back-extracted intodilute nitric acid. Volatile tin-hydrides were formed bythe addition of sodium borohydride to the nitric acidsolutions and these were trapped onto a packed columnat �190 �C and thermally desorbed into the light patch ofan electrically heated quartz furnace atomic absorptionspectrometer (AAS). One hundred mg of sample was also

digested in aqua regia and analysed for copper, nickel,lead and zinc concentrations using inductively coupledplasma atomic emission spectrometry (ICP-AES).

All analyses were carried out in triplicate, and themean concentration of metal reported. External cali-bration standards and blank reagents were measured atthe same time as antifoulant and metal analyses. Trib-utyltin (TBT) and its breakdown products dibutyltin(DBT) and monobutyltin (MBT), and copper, nickel,lead and zinc were undetectable in all laboratory reagentblanks. Mean recoveries of TBT and DBT calibrationsamples ranged from (91–102%) to (90–104%) respec-tively. Pearson correlations between antifoulant spe-cies were calculated, and variation in concentrations ofantifoulants were analysed using a nested two-factor

Fig. 1. The Sudbury Reef grounding site, Great Barrier Reef, Australia.

Baseline / Marine Pollution Bulletin 44 (2002) 956–976 969

analysis of variance (ANOVA). All statistical calcula-tions were carried out using the SYSTAT softwarepackage (Wilkinson, 1996).

Sediment concentrations of TBT in the vicinity of thegrounding site ranged from <1 to 17,000 ng Sn g�1, withthe highest concentrations of TBT detected in, andwithin, 5 m of the vessel grounding scar (Table 1; Fig. 3).Concentrations of TBT were highly variable with bothdirection ðF3;28 ¼70:664, p<0:001Þ and distance ðF24;28 ¼33:067, p<0:001Þ from the grounding site, with thehighest concentrations occurring along the two samplingtransects (transects 1 and 3) extending from the bow ofthe vessel (Figs. 2 and 3). TBT was not detectable in

sediments collected 1000 m away from the groundingsite. The distribution of TBT around the grounding site

Fig. 3. Average TBT concentrations, Sudbury Reef grounding site, November 2000. (n ¼ 8, error bars ¼ 1 SEM). Background image shows

grounded vessel during a refloating attempt.

Fig. 2. Antifoulant sampling sites at 5, 10, 20, 50, 100, 250 and 1000 m along four transects radiating out from the grounding ‘‘footprint’’, Sudbury

Reef, November 2000.

Table 1

Range of antifoulant concentrations, Sudbury Reef, November 2000

Transect TBT Copper Lead Nickel Zinc

Scar 82–1500 972–21,700 <8–44 <2–4 1170–19,400

One <1–4700 <3–41 <8 <2–2 <12–50

Two <1–460 <3 <8 <2–2 <12

Three <1–2900 <3–36 <8 <2–9 <12–46

Four <1–

17,000

<3–21 <8 <2 <12–29

TBT ng Sn g�1 dry wt, Cu, Pb, Ni and Zn mg kg�1 dry wt.

970 Baseline / Marine Pollution Bulletin 44 (2002) 956–976

was likely to be a consequence of both the abrasion ofantifoulant from the vessel hull as it ran aground, andfrom the subsequent dispersion of sediment and an-tifoulant by the ship’s propeller action during the re-floating operation. The propeller action created a plumeof sediment (and antifoulant) which was dispersed pastthe bow of the vessel for a distance of up to 300 m (Fig.4). TBT concentrations at the Sudbury Reef groundingsite were grossly elevated compared with ANZECC(2000) guidelines (72 ngSng�1) and were similar to con-centrations reported following a ship ground at HeathReef, Far Northern Great Barrier Reef in 1999 (660–340,000 ngSng�1; Haynes and Loong, 2002).

Elevated concentrations of both copper and zinc weredetectable in sediments collected from within the shipgrounding scar (Table 1). Copper oxide and Zineb (zincethylenebis(dithiocarbamate)) are two of the activeconstituents of the antifoulant used on the groundedvessel (Intersmooth 220, International Paints). Concen-trations of copper (972–21,700 mg kg�1) and zinc(1170–192,400 mg kg�1) within the grounding scar sub-stantially exceeded ANZECC (2000) sediment guide-lines. Sediment concentrations of TBT were significantlycorrelated with sediment copper ðr ¼ 0:822Þ and sedi-ment zinc ðr ¼ 0:882Þ concentrations within the ground-ing scar, as well as along the sampling transects (TBT:copper r ¼ 0:608 and TBT:zinc r ¼ 0:618), indicative oftheir common source from abraided antifoulant paint.

There was also evidence of minor elevation of con-centrations of nickel (2–4 mg kg�1) and lead (<8–44mg kg�1) in sediments collected from within the shipgrounding scar (Table 1), although neither of thesemetals is a listed constituent of the antifoulant paintused on the grounded ship’s hull. Concentrations of

both metals did not exceed ANZECC (2000) sedimentguidelines at the grounding site, and were unlikely topresent any significant risk to the local environment.

Impact assessment of ship groundings on coral androcky reefs is usually confined to examination of theimpact of cargo or fuel released from the vessel (Edgaraand Barrett, 2000; Hatcher, 1984; Hawkins et al., 1991);and/or the extent of damage and loss of habitat causedby the physical impact of the grounding vessel (Dennisand Bright, 1988; Hawkins et al., 1991; Zobrist, 1998).Coral recovery has often been reported as ‘‘slow’’ fol-lowing groundings (Hatcher, 1984; Hawkins et al.,1991), although this has generally been attributed to thepresence of spilt cargos such as fertlizers or fuel, and tothe continuing impact of mobile sediment and rubble atthe site. The impact of residual antifoulant on adultcoral colonies and juvenile coral recruitment has notbeen considered in these assessments.

Butyltins are highly toxic to a range of marine reefbiota including scleractinian corals (Allemand et al.,1998; Morse et al., 1988), octocorals (Sebens, 1983), andother cnidarians (Mercier et al., 1996). More recentstudies have also demonstrated the toxicity of butyltin(Negri et al., 2002; Negri and Heyward, 2001) and cop-per to coral juvenile recruitment and adult coral health(Esquivel, 1986; Negri et al., 2002), while both copperand zinc are known to inhibit fertilization of coral ga-metes (Reicheld-Brushett and Harrison, 1999). However,concentrations of both copper and zinc were at back-ground concentrations 10 m beyond the grounding scar.Although only one previous study has examined theextent of antifoulant deposition at a coral reef shipgrounding site (Haynes and Loong, 2002), data nowgathered strongly indicate that the presence of residual

Fig. 4. Sediment (and antifoulant) plume generated during the refloating of the Bunga Teratai Satu, Sudbury Reef, November 2000.

Baseline / Marine Pollution Bulletin 44 (2002) 956–976 971

antifoulants at ship grounding sites may present an on-going impediment to coral reef recovery. This informa-tion was pivotal to the commencement of an extensivecleanup effort aimed at reducing levels of antifoulantcompounds around the Sudbury Reef grounding site(Marshall et al., 2002). An ongoing monitoring programis essential if the rate and extent of recovery of the coralreef community following this grounding and the sub-sequent cleanup program is to be ascertained.

Acknowledgements

Graham Batley and Chris Brockbank (CSIRO Centrefor Analytical Chemistry, Sydney) supervised butyltinand metal analyses. Mike Short (Queensland Parks andWildlife Service) and Emre Turak (Australian Institute ofMarine Science) are thanked for assistance with sedimentcollection. Leon Jackson (Great Barrier Reef MarinePark Authority) is thanked for assistance with Fig. 1.

References

Allemand, D., Tambutt�ee, Girad, J., Jaubert, J., 1998. Organic matrix

synthesis in the scleractinian coral Stylophora pistillata: role in

biomineralization and potential target of the organotin tributyltin.

The Journal of Experimental Biology 201, 2001–2009.

ANZECC., 2000. Australian and New Zealand guidelines for fresh and

marine water quality. Australian and New Zealand Environment

and Conservation Council.

Dennis, G.D., Bright, T.J., The impact of a ship grounding on the reef

fish assemblage at Molasses Reef, Key Largo National Marine

Sanctuary, Florida. In: Proceedings of the 6th International Coral

Reef Symposium, Australia 2, 1988, pp. 213–218.

Edgara, G.J., Barrett, N.S., 2000. Impact of the iron baron oil spill on

subtidal reef assemblages in Tasmania. Marine Pollution Bulletin

40, 36–49.

Esquivel, I., 1986. Short term copper bioassay on the planula of the

reef coral Pocillopora damicornis. In: Jokiel, P.L., Richmond,

R.H., Rodgers, R.A. (Eds.), Coral Reef Population Biology,

Hawaii Institute of Marine Biology Technical Report No. 37, pp.

465–472.

Hatcher, B.G., 1984. A maritime accident provides evidence for

alternate stable states in benthic communities on coral reefs. Coral

Reefs 3, 199–204.

Hawkins, J.P., Roberts, C.M., Adamson, T., 1991. Effects of a phos-

phate ship grounding on a Red Sea coral reef. Marine Pollution

Bulletin 22, 538–542.

Haynes, D., Brodie, J., Christie, C., Devlin, M.Z., Michalek-Wagner,

K., Morris, S., Ramsay, M., Storrie, J., Waterhouse, J., Yorkston,

H., 2001. Great Barrier Reef Water Quality: Current Issues. Great

Barrier Reef Marine Park Authority, Townsville.

Haynes, D., Loong, D., 2002. Antifoulant (butyltin and copper)

concentrations in sediments from the Great Barrier Reef World

Heritage Area, Australia. Environmental Pollution (in press).

Marshall, P.A., Christie, C., Dobbs, K., Green, A., Haynes, D.,

Brodie, J., Michalek-Wagner, K., Short, M., Smith, A., Storrie, J.,

Turak, E., 2002. Grounded ship leaves TBT-based antifoulant on

the Great Barrier Reef: an overview of the environmental response.

Spill Science and Technology Bulletin (in press).

Mercier, A., Pelletier, �EE., Hamel, J., 1996. Toxicological response of

the symbiotic sea anenome Aiptasia pallida to butyltin contamina-

tion. Marine Ecological Progress Series 144, 133–146.

Morse, D.E., Hooker, N., Morse, A.N.C., Jensen, R.A., 1988. Control

of larval metamorphosis and recruitment in sympatric agariciid

corals. Journal of Experimental Marine Biology and Ecology 116,

193–217.

Negri, A., Smith, L., Webster, N., Heyward, A., 2002. Understanding

ship-grounding impacts on a coral reef: potential effects of

antifoulant paint contamination on coral recruitment. Marine

Pollution Bulletin 47, 109–115.

Negri, A.P., Heyward, A.J., 2001. Inhibition of coral fertilization and

larval metamorphosis by tributyltin and copper. Marine Environ-

mental Research 51, 17–27.

Raaymakers, S., 1994. Ship sourced oil pollution in the Great Barrier

Reef: causes, frequency, response and prevention. In: Ottensen, P.

(Ed.), Hulls, Hazards and Hard Questions. Shipping in the Great

Barrier Reef: Reducing the Risk of Spilling Oil and Other

Hazardous Substances, Great Barrier Reef Marine Park Authority,

Townsville. pp. 11–24.

Reicheld-Brushett, A.J., Harrison, P.L., 1999. The effect of copper,

zinc and cadmium on fertilization success of gametes from

scleractinian reef corals. Marine Pollution Bulletin 38, 182–187.

Sebens, K.P., 1983. Settlement and metamorphosis of a temperate soft-

coral larvae (Alcyonium siderium Verril): induction by crustose

algae. Biological Bulletin 165, 286–304.

Wilkinson, L., 1996. Systat 7.0 for Windows: Statistics 1996. Chicago,

Microsoft.

Zobrist, E.K., 1998. Reef restoration and protection from vessel

groundings. Gulf Coast Research Reports 10, 85 (Abstract only).

0025-326X/02/$ - see front matter � 2002 Elsevier Science Ltd. All rights reserved.

PII: S0025-326X(02 )00114 -5

972 Baseline / Marine Pollution Bulletin 44 (2002) 956–976