# Antifoulant (butyltin and copper) concentrations in sediments from the Great Barrier Reef World Heritage Area, Australia

David Haynes*, Dominica Loong 1

Great Barrier Reef Marine Park Authority, PO Box 1379, Townsville 4810, Australia

Received 31 May 2001; accepted 31 December 2001



### ‘‘Capsule’’: Antifoulant concentrations are generally low in the Great Barrier Reef, although ship grounding sites present a previously unidentified significant source of antifoulant pollutants in the Great Barrier Reef.

Abstract

Antifoulant concentrations were determined in marine sediments collected from commercial harbours, marinas, mooring locations on mid-shelf continental islands, and outer reef sites in four regions within the Great Barrier Reef World Heritage Area in 1999. Highest copper concentrations were present in sediments collected from commercial harbour sampling sites (28–233 mg Cu

g  1 

### dry wt.). In contrast, copper concentrations in sediments collected from boat mooring sites on mid-shelf continental islands and outer reef sites were at background concentrations (i.e. < 20 mg Cu g

 1 

### dry wt.). Butyltin was only detectable in four of the 42 sediments sampled for analysis, and was only present in sediments collected from commercial harbours (18–1275 ng Sn g

 1 

### dry wt.) and from marinas (4–5 ng Sn g

 1 

### dry wt.). The detection of tributyltin at marina sites implies that this antifoulant may continue to be used illegally on the hulls of smaller recreational vessels. Sediment samples were also collected opportunistically from the site of a 22,000 t cargo ship grounding in May 1999 at Heath Reef, in the far northern Great Barrier Reef. Butyltin concentrations were grossly elevated (660–340,000 ng Sn g

 1 

### dry wt.) at the grounding site. The impact of residual antifoulants at large ship grounding sites should be recognised as a significant, long-term environmental problem unless antfoulant clean-up strategies are undertaken. # 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Copper; Great Barrier Reef; Harbours; Ship grounding; TBT



### 1. Introduction

Organotin compounds are potent toxins, and this property has lead to their use in a range of biocidesincluding ship antifouling paints (Stewart and Thompson, 1994). Their use on ocean going ships is extensive, with most of the world’s ocean-going fleet reliant on their use to inhibit fouling growth (Bosselmann, 1996;Hallers-Tjabbes, 1997; Michel and Averty, 1999a). Tributyltin (TBT) based antifoulant paints have been usedin Australia since the early 1970s, although use on vessels smaller than 25m was banned in Eastern AustralianStates in 1989 in response to growing evidence of environmental impacts in semi-enclosed waters subject to intensive shipping or ship-related activity (Batley and Scammell, 1989a,b; Batley et al., 1992; Batley, 1995, 1996; Evans, 1999). Monitoring of various locations around the world (e.g. Dowson et al., 1993; Evans et al.,1995; Chau et al., 1997; Michel and Averty, 1999b; Shim et al., 1999; Tselentis et al., 1999) has indicated
that reductions in TBT concentrations have occurred insome areas frequented by smaller vessels such as marinas, whereas concentrations of TBT present in areas used by larger vessels still exceed those that will result in environmental impacts.

Copper is also a widely used antifoulant. It is used as both an additive in TBT-based paints (usually as copper oxide or copper thiocyanate) to increase the spectrum of biocidal activity in these paints, as well as the main biocide in copper based paints applied to smaller craft (Batley et al., 1992). As a consequence, concentrations of copper in marine sediments in enclosed waters such
as marinas and harbours have also increased to levels of concern (Hall and Anderson, 1999; Olsgard, 1999).

0269-7491/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved. PII: S0269-7491(02)00113-6 Environmental Pollution 120 (2002) 391–396 www.elsevier.com/locate/envpol

* Corresponding author. Tel.: +61-747500700; fax: +61-
747726093.
E-mail address: d.haynes@gbrmpa.gov.au (D. Haynes).

1 Present address: Australian Centre for Tropical Freshwater Research, James Cook University, Townsville 4811, Australia.

### Surveys of antifoulant concentrations in Australian waters are limited (Batley et al., 1989a, 1989b; Batley and Scammell, 1991; Kilby and Batley, 1993), with the most comprehensive survey of Queensland waters being carried out in 1989 (Witney, 1991). This current work presents the first data on concentrations of TBT presentin the Great Barrier Reef World Heritage Area, Australia, as well as presenting contemporary data on concentrations of copper associated with shipping and ship related activity in the region.

2. Materials and methods

2.1. Sediment collection

Marine sediment samples were collected from four regions [Port Douglas, Cairns, Townsville and Airlie Beach (the Whitsundays)] within the Great Barrier ReefWorld Heritage Area which have a variety of commercial, tourist and recreational maritime activity (Fig. 1). Within each region, three or four locations representing commercial harbours (Cairns and Townsville regions only), marinas, boat mooring locations on mid-shelf continental islands, and outer reef sites were sampled for sediment antifoulant concentrations in April andMay 1999 (Table 1). A commercial harbour is not present in the Port Douglas or Whitsunday regions.

Collection of surficial (top 10 cm) sediment was carried out using a van-Veen grab lowered over the side of a boat or jetty at inshore and mid-shelf continentalisland sites; or by divers at outer reef sites. Three replicate sediment samples were collected randomly at each site. Each replicate sample was composited from three ‘‘grabs’’ or successive container scoops of sediment and contained approximately 500 g of sediment. Samples were stored frozen in acid-washed plastic containers.

Sediment samples were also collected opportunistically from the site of a ship grounding in May 1999 at Heath Reef (13 

### 28 0 

### S, 143 

### 400

### E), far-north Queensland (Fig. 1). The 22,000 tonne cargo ship New Reach was grounded on the outer reef for 6 h before being freedfrom the reef under its own power. Two replicate sediment samples were collected in acid-washed plastic containers by scuba divers from three sites at increasing distances from the grounding location, 9 days after the ship was refloated.

2.2. Laboratory analyses

Sediment samples were thawed, sub-sampled andanalysed for antifoulant concentrations. Butyltin determinations were performed at the CSIRO Centre for Analytical Chemistry, Sydney. Sediment subsampleswere thoroughly homogenised by grinding in a porcelain mortar and pestle. One gram of sediment was separated from the homogenised sample for analysis. Butyltins were extracted from each sediment sample matrix using 50% v/v methanol in 10 M HCl in an ultrasonic bath. The supernatant was then extracted with dichloromethane in the presence of tropolone and finally back-extracted into dilute nitric acid. Volatile tinhydrides were formed by the addition of sodium borohydride to the nitric acid solutions and these were trapped onto a packed column at

 190 

### C and thermally desorbed into the light path of an electrically heated quartz furnace atomic absorption spectrometer (AAS).

Sediment copper analyses were carried out at the Advanced Analytical Centre, James Cook University, Cairns. Sediment samples were dried in a Gallenkamp
oven at 60 

### C overnight and then ground to a finepowder in a Rocklabs benchmill and prepared as compressed pellets. The pellets were analysed for copper using X-ray fluorescence spectrometry (Siemens SRS3000). Compton scatter techniques were used for correction of absorption effects in copper determination (Potts, 1996).

2.3. Quality sssurance and satistical analysis

External calibration standards and blank reagents were measured at the same time as antifoulant analyses.

Table 1 Sediment antifoulant sampling locations and port and harbour capacities, central and northern Great Barrier Reef World Heritage Area

Region Harbour type and capacity

Commercial harbours Mainland marinas Mooring sites, mid-shelf island Mooring sites, outer reef

Port Douglas npa Port Douglas Marina Low Isles Agincourt Reef (120 berths) Cairns Cairns Port Yorkey’s Knob Fitzroy Island Michaelmas Reef (1.1 million tonnes per annum) (197 berths) Townsville Townsville Port Breakwater Marina Magnetic Island Kelso Reef (8.9 million tonnes per annum) (243 berths) Whitsundays np Abel Point Marina South Molle Island Bait Reef (235 berths)

a Not present. 392 D. Haynes, D. Loong / Environmental Pollution 120 (2002) 391–396Fig. 1. Antifoulant sampling sites, 1999, Great Barrier Reef World Heritage Area, Australia. D. Haynes, D. Loong / Environmental Pollution 120 (2002) 391–396 393

### TBT and its breakdown products dibutyltin (DBT) andmonobutyltin (MBT), were undetectable in all laboratory reagent blanks and mean recoveries of spiked TBT and DBT samples ranged from 86–104%, and 80–113% respectively. Recoveries of copper certified reference materials (MAG-1 and GSD-3) were 96  0.5 and
87  2% respectively.

Differences in sediment copper concentrations were investigated using a two-factor analysis of variance (ANOVA) with sampling locations (marinas, boat mooring locations on mid-shelf continental islands andouter reef sites) nested in sampling regions (Port Douglas, Cairns, Townsville and the Whitsundays). Commercial harbour sites were excluded from this analysis as they are only present in the Townsville and Cairns regions. All statistical analyses were carried using SYSTAT V7 software (Wilkinson, 1996).

3. Results and discussion

3.1. Butyltin

Butyltin was only detectable in four of the 42 sediments sampled for analysis, and only occurred in
sediments collected from commercial harbours and from inshore marinas (Table 2). Highest tributyltin concentrations (1275 ng Sn g

 1 

### ) were detected in the Cairns Port Authority harbour adjacent to a large shipyard and slipway, and in the Townsville Port Authority swing-basin adjacent to a large shipping berth (Berth 2, 18 ng Sn g

 1 

### ). Low concentrations of TBT were detected in samples collected from both the Townsville and Cairns marinas (4 ng Sn g

 1 

### and 5 ng Sn

g  1 

### respectively). TBT was undetectable ( < 1 ng Sn g

 1 

### ) at all other sites including mid-shelf mooring sites and outer reef sites. This is in agreement with studies of concentrations of TBT in open waters around theworld, which have indicated that these types of environments are generally free of butyltin contamination (Evans, 1999). Low concentations ( < 1–161 ng Sn g

 1 

### ) of DBT and/or MBT were usually detectable wheneverTBT was present in collected sediments (Table 3), implying that TBT deposition had also occurred historically.

The presence of TBT in commercial harbour sediments is typical of mooring locations used by ocean-going vessels greater than 25 m in length, which legally rely on
TBT as an antifoulant. Levels of TBT contamination only exceeded ANZECC (2000) effect range low (ERL) guideline (5 ng S g

 1 

### ) at one sampling site in Cairns and Townsville harbours, and were low in comparison to
levels detected in sediments from harbours elsewhere (Chau et al., 1997; Shim et al., 1999; Tselentis et al., 1999). Concentrations of TBT detected in the Cairns
and Townsville marinas were two to three orders ofmagnitude lower than concentrations detected in sediments adjacent to European and Canadian marinas (e.g. Dowson et al., 1993; Chau et al., 1997; Tselentis et al., 1999), and can be regarded as lightly contaminated (Dowson et al., 1993). However, the detection of TBT and its breakdown products at marina sites, not visitedby large vessels, raises the possibility that this antifoulant is currently being used illegally on the hulls ofsmaller recreational vessels, or that TBT is being dispersed away from harbours through wind and wave
action.

3.2. Copper

The highest sediment copper concentrations were associated with the intensive shipping and industrial activity in Cairns and Townsville commercial harbours, (28–140 mg g  1 

### and 37–233 mg g  1 

### , respectively; Table 4).These concentrations of copper are consistent with contamination arising from hull cleaning and painting practices, and stormwater runoff from large urban centres.

Significant differences in sediment copper concentrations were present between sampling regions (F 3, 29.05, 

### P < 0.001), and sampling locations (F 8, 58.30, 

### P < 0.001), with sediments collected from all marinas except Port Douglas having the highest average concentrations of copper (32–112 mg g  1 

### ; Table 4). Copper concentrations

Table 2 Sediment TBT concentrations, central and northern Great Barrier Reef Region (all concentrations ng Sn g

 1 dry w.t., n =3)

Commercial harbours Mainland marinas Mooring sites, mid-shelf island Mooring sites, outer reefs

Port Douglas np a < 1 < 1 < 1
Cairns < 1–1275 < 1–5.5 < 1 < 1
Townsville < 1–18 < 1–4.2 < 1 < 1 Whitsundays np < 1 < 1 < 1

a Not present. Table 3 Tributyltin degradation species concentrations (all concentrations ng Sn g

 1 dry w.t., n =1)

Sampling location TBT DBT MBT

Cairns harbour 1275 71 161
Cairns marina 5.5 < 1 33
Townsville harbour 18 < 1 47
Townsville marina 4.2 < 1 < 1 394 D. Haynes, D. Loong / Environmental Pollution 120 (2002) 391–396

### in sediments collected from boat mooring sites on midshelf continental islands, outer reef sites and from thePort Douglas marina were at background concentrations (i.e. < 20 mg g  1 

### dry w.t.; Doherty et al., 2000).

Concentrations of copper detected in sediments collected from commercial harbours and a majority of the recreational marina sites in this study were similar, and are likely to reflect its extensive use in antifouling paintswhere it is legally used on boats and ships for antifouling purposes (Brady et al., 1994). Average copper concentrations at both commercial harbour locations and at two of the marina locations exceeded the ANZECC, (2000) effect range low (ERL) guideline (65 mg g  1 

### ), implying that the heavy metal has some potential for environmental impact at these sites.

3.3. Ship grounding antifoulant concentrations

Butyltin concentrations detected in sediments collected from the Heath Reef grounding site, far northern Great Barrier Reef, were grossly elevated (Table 5). Heath Reef was extensively damaged at the time of the ship grounding and elevated concentrations of butyltin were a consequence of antifoulant paint being abraded from the ships hull at the time of grounding and during subsequent refloating. Butyltins are highly toxic to a range of marine reef biota including scleractinian corals (Morse et al., 1988; Allemand et al., 1998; Heyward and Negri, 1999; Negri and Heyward, 2001), octocorals (Sebens, 1983), other cnidarians (Mercier et al., 1996;Leitz, 1997) and molluscs (Labare et al., 1997), bryozoans (Kitamura and Hirayama, 1987) and echinoderms(Johnson and Sutton, 1994). Its mode of action is primarily through disruption of the functioning of cell membranes (Viarengo, 1989; Fent, 1996), and microcosm experiments have demonstrated its effectiveness against organisms that recruit to hard substrata (Henderson, 1988). This present study identifies, for the first time,that the potential long-term impacts of residual antifoulants at such grounding sites need to be recognised as a significant environmental problem. Where possible, clean-up strategies to remove antifoulant contaminantsfrom the sites of large ship groundings should be completed to ensure long-term viability of the affected marine
environment.

Acknowledgements

Graham Batley and Chris Brockbank (CSIRO Centre for Analytical Chemistry, Sydney) supervised butyltinanalyses, and Rob Cirroco, Advanced Analytical Centre, James Cook University, analysed copper samples. Ken Anthony, Barney Bebendorf and Britta Schafelke (Great Barrier Reef Marine Park Authority) andAndrew Griffith, Rob Buck and Mike Short (Queensland Parks and Wildlife Service) are thanked for assistance with sediment collection. Jane Waterhouse (Great Barrier Reef Marine Park Authority) is thanked forassistance with Fig. 1. Andrew Negri (Australian Institute of Marine Science) and John Lewis (DSTO Aeronautics and Maritime Research Laboratory) are thanked for comments on a draft of the manuscript.

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