Are metals of antifouling paints transferred to marine biota?

Paradas, Wladimir C.; Amado Filho, Gilberto M.

Abstracts

Because of its high toxicity, TBT (trybutiltin) was banned since 2003, which resulted in a greater re-use of Cu as based-biocide in antifouling paints (AFP). The aim of this work is to determine if metals form of AFP are transferred to benthic organisms from Guanabara Bay (GB) (Rio de Janeiro, Brazil). Metal concentrations were measured in two main fouling algae species Ulva flexuosa and U. fasciata and one isopod species, Sphaeroma serratum, in two GB marinas areas from sites with artificial substrate covered by AFP and natural substrate.In addition, control samples were collected in an adjacent open ocean area. Concentrations of Cd, Cr, Cu, Pb and Zn were determined by Atomic Absortion Spectrophotometry. Higher concentrations of Cu, Pb and Zn were detected in both algal species from GB in relation to control areas. Among samples of algae and isopod species from GB, populations collected over artificial surfaces covered by AFP presented significantly higher metal concentration than population of rocky natural substrate. Our data showed that the leaching of metals by antifouling paints present on decks and boats are being taken up by algae and isopods. These results indicate that antifouling coatings are the main source of heavy metal to biota of GB marina area.

antifouling paints; Cu; metal accumulation; benthic organisms; Guanabara Bay

Devido sua alta toxicidade, o TBT está banido desde 2003, o que resultou na re-utilização de tintas a base de cobre. O objetivo deste trabalho é determinar se os metais provenientes das tintas anti-incrustantes (AFP) são transferidos para organismos bentônicos da Baía de Guanabara (BG) (Rio de janeiro, Brasil). Concentrações de metais foram analisadas em duas espécies de algas Ulva flexuosa e U. fasciata e no isópoda, Sphaeroma serratum, em duas áreas de marinas em locais de substrato artificial coberto com tintas AFP e em locais de substrato natural. Também foram coletadas amostras em uma área oceânica (controle). Concentrações de Cd, Cr, Cu, Pb e Zn foram determinadas por Espectrofotometria de Absorção Atômica. Concentrações mais elevadas de Cu, Pb e Zn foram detectadas na BG em ambas espécies de algas em relação a área controle. Dentre as espécies de algas e do isópoda da BG, as populações coletadas sobre as superfícies cobertas com AFP apresentaram concentrações significativamente mais elevadas do que as populações do substrato natural. Os resultados obtidos demonstram que a liberação de metais presentes nas AFP dos decks e embarcações, estão sendo acumulados pelas algas e isópodas. Esses resultados indicam que o revestimento com AFP é a principal fonte de metais para a biota de marinas em áreas da BG.

tintas anti-incrustantes; cobre; acumulação; organismos bentônicos; baía de Guanabara

Amado Filho, G. M.; Andrade, L. R.; Karez, C. S.; Farina, M. & Pfeiffer, W. C. 1999. Brown algae species as biomonitors of Zn and Cd at Sepetiba Bay, Rio de Janeiro, Brazil. Mar. Environ. Res., 48:213-224.
Andrade, L. R.; Farina, M. & Amado Filho, G. M. 2004. Effects of copper on Ulva flexuosa (Chlorophyta) in vitro. Ecotoxicol. Environ. Saf., 58:117-125.
Boxall, A. B. A.; Comber, S. D.; Conrad, A. U.; Howcroft, J. & Zaman, N. 2000. Inputs, monitoring and fate modeling of antifouling biocides in UK Estuaries. Mar. Pollut. Bull., 40(11):898-905.
Callow, M. E. & Callow, J. A. 2002. Marine biofouling: a sticky problem. Biologist 49(1):1-5.
Claise, D. & Alsieu, C. L. 1993. Copper contaminations as a result of antifouling paints regulation? Mar. Pollut. Bull., 26(7):395-397.
Carvalho, C. E. & Lacerda, L. D. 1992. Heavy metals in the Guanabara Bay biota: why such low concentrations? Ci. Cult. J. Ass. Bras. Adv. Sci., 44:184-186.
Correa, J. A.; Gonzáles, P.; Sánchez, P.; Munõz, J. & Orellana, M. C. 1996. Copper-algae interactions inheritance or adaptation? Environ. Monit. Assessment., 40:41-54.
Donadey, C. & Besse, G. 1972. Etude histologique, ultrastructurale et experimentale dês caecums digestifs de Porcellio dilatatus et Ligia oceânica (Crustaceae, isopoda). Tethys, 4:145-62.
Gledhill, M.; Nimno, M.; Hill, S. J. & Brown, T. M. 1997. The toxicity of copper (II) species to marine algae, with particular reference to macroalgae. J.Phycol., 33: 2-11.
Guerra-García, J. M. & García-Gómez, J. C. 2005. Assessing pollution levels in sediments of a harbor with two opposing entrances. Environmental implications. J. Environ. Mgnt., 77:1-11.
Haritonidis, S. & Malea, P. 1999. Bioaccumulation of metals by the green alga Ulva rigida from Thermaikos Gulf, Greece. Environ. Pollut., 104:365-372.
Ho, Y. 1987. Metals in 19 intertidal macroalgae in Hong Kong waters. Mar. Pollut. Bull.,18:564-566.
Hopkin, S. P. & Martin, M. H. 1982. The distribution of zinc, cadmium, lead and copper within woodlouse Oniscus asellus (Crustaceae, Isopoda). Oecologia., 54: 227-32.
IMO - International Maritime Organization. 2001. International Conference on the control of Harmful Anti-fouling Systems on Ships. London: IMO Headquartes.
Karez, C. S.; Amado Filho, G. M.; Moll, D. M. & Pfeiffer, W. C. 1994. Concentrações de metais em algas marinhas bentônicas de três regiões do Estado do Rio de Janeiro. An. Acad. bras. Ci., 66 (2):205-211.
Levent, B. A. T.; Ayse, G.; Murat, S.; Mehmet, Ç.; Gamze, G. & Mehmet, A. 1999. Acute toxicity of zinc, copper and lead to three species of marine organisms from the Sinop Peninsula, Black sea. Turkish. J. Biol., 23:537-544.
Löschau, M. & Krätke, R. 2005. Efficacy and toxicity of self-polishing biocide-free antifouling paints. Environ. Pollut., 138(2):260-267.
Moore, J. V. & Ramamurti, S. 1987. Heavy Metals in near-bottom water. Moscow. 285p.
Reed, R. H. & Moffat, L. 1983. Copper toxicity and copper tolerance in Ulva compressa (L.) Grev. J. expl. mar. Biol. Ecol., 69: 85-103.
Riquelme, C.; Rojas, A.; Flores, V. & Correa, J. A. 1997. Epiphytic bacteria in a copper-enriched environment in Northern Chile. Mar. Pollut. Bull., 34:816-820.
Ruppert, E. E.; Fox, R. S. & Barnes, R. D. 2005. Zoologia dos vertebrados: uma abordagem funcional evolutiva. 7. ed. São Paulo. Rocca, 1.145p.
Schiff, K.; Diehl, D. & Valkirs, A. O. 2004. Copper emissions from antifouling paint on recreational vessels. Mar. Pollut. Bull., 48: 371-377.
Turner, S. J.; Cummings, V. J.; Hewitt, J. E.; Wilkinson, M. R.; Williamson, R. B. & Lee, D. J. Changes in epifaunal assemblages in response to marina operations and boating activities. Mar. environ. Res., 43:181-199.
Thouvenin, M.; Peron, J. J.; Charrateurm, C.; Guerin, P.; Langlois, J. Y. & Vallee-Rehel, K. 2002. A study of the biocide release from antifouling paints. Progr. Org. Coat., 44:75-83.
Valkirs, A. O.; Seligman, P. F.; Haslbeck, E. & Caso, J. S. 2003. Measurement of copper release rates from antifouling paint under laboratory and in situ conditions: implications for loading estimation to marine water bodies. Mar. Pollut. Bull., 46:763-779.
Warken, J.; Dunn, R. J. K. & Teasdale, P. R. 2004. Investigation of recreational boats as a source of copper at anchorage sites using time-integrated diffusive gradients in thin film and sediments measurements. Mar. Pollut. Bull., 49:833-843.
Waterman, B. T.; Daehne, B.; Sievers, S.; Dannenberg, R.; Overbeke, J. C.; Klijnstra, J. W. & Heemken, O. 2005. Bioassays and selected chemical analysis of biocide-free antifouling coatings. Chem., 60:1530-1541.
Wieser, W. 1967. Conquering terra firma: The copper problem from the isopod's point of view. Helgoländer. Wiss. Meeresunter., 15:282-93.
Yenehara, Y.; Yamashita, H.; Kawakamura, C. & Itoh, K. 2001. A new antifouling paint base don a zinc acrylate copolymerer. Prog. Org. Coat., 42:150-158.

Publication Dates

Publication in this collection
26 Oct 2007
Date of issue
Mar 2007

History

Received
09 June 2005
Reviewed
06 Oct 2006
Accepted
18 Oct 2006

This work is licensed under a Creative Commons Attribution 4.0 International License.

[1] Amado Filho, G. M.; Andrade, L. R.; Karez, C. S.; Farina, M. & Pfeiffer, W. C. 1999. Brown algae species as biomonitors of Zn and Cd at Sepetiba Bay, Rio de Janeiro, Brazil. Mar. Environ. Res., 48:213-224.

[2] Andrade, L. R.; Farina, M. & Amado Filho, G. M. 2004. Effects of copper on Ulva flexuosa (Chlorophyta) in vitro. Ecotoxicol. Environ. Saf., 58:117-125.

[3] Boxall, A. B. A.; Comber, S. D.; Conrad, A. U.; Howcroft, J. & Zaman, N. 2000. Inputs, monitoring and fate modeling of antifouling biocides in UK Estuaries. Mar. Pollut. Bull., 40(11):898-905.

[4] Callow, M. E. & Callow, J. A. 2002. Marine biofouling: a sticky problem. Biologist 49(1):1-5.

[5] Claise, D. & Alsieu, C. L. 1993. Copper contaminations as a result of antifouling paints regulation? Mar. Pollut. Bull., 26(7):395-397.

[6] Carvalho, C. E. & Lacerda, L. D. 1992. Heavy metals in the Guanabara Bay biota: why such low concentrations? Ci. Cult. J. Ass. Bras. Adv. Sci., 44:184-186.

[7] Correa, J. A.; Gonzáles, P.; Sánchez, P.; Munõz, J. & Orellana, M. C. 1996. Copper-algae interactions inheritance or adaptation? Environ. Monit. Assessment., 40:41-54.

[8] Donadey, C. & Besse, G. 1972. Etude histologique, ultrastructurale et experimentale dês caecums digestifs de Porcellio dilatatus et Ligia oceânica (Crustaceae, isopoda). Tethys, 4:145-62.

[9] Gledhill, M.; Nimno, M.; Hill, S. J. & Brown, T. M. 1997. The toxicity of copper (II) species to marine algae, with particular reference to macroalgae. J.Phycol., 33: 2-11.

[10] Guerra-García, J. M. & García-Gómez, J. C. 2005. Assessing pollution levels in sediments of a harbor with two opposing entrances. Environmental implications. J. Environ. Mgnt., 77:1-11.

[11] Haritonidis, S. & Malea, P. 1999. Bioaccumulation of metals by the green alga Ulva rigida from Thermaikos Gulf, Greece. Environ. Pollut., 104:365-372.

[12] Ho, Y. 1987. Metals in 19 intertidal macroalgae in Hong Kong waters. Mar. Pollut. Bull.,18:564-566.

[13] Hopkin, S. P. & Martin, M. H. 1982. The distribution of zinc, cadmium, lead and copper within woodlouse Oniscus asellus (Crustaceae, Isopoda). Oecologia., 54: 227-32.

[14] IMO - International Maritime Organization. 2001. International Conference on the control of Harmful Anti-fouling Systems on Ships. London: IMO Headquartes.

[15] Karez, C. S.; Amado Filho, G. M.; Moll, D. M. & Pfeiffer, W. C. 1994. Concentrações de metais em algas marinhas bentônicas de três regiões do Estado do Rio de Janeiro. An. Acad. bras. Ci., 66 (2):205-211.

[16] Levent, B. A. T.; Ayse, G.; Murat, S.; Mehmet, Ç.; Gamze, G. & Mehmet, A. 1999. Acute toxicity of zinc, copper and lead to three species of marine organisms from the Sinop Peninsula, Black sea. Turkish. J. Biol., 23:537-544.

[17] Löschau, M. & Krätke, R. 2005. Efficacy and toxicity of self-polishing biocide-free antifouling paints. Environ. Pollut., 138(2):260-267.

[18] Moore, J. V. & Ramamurti, S. 1987. Heavy Metals in near-bottom water. Moscow. 285p.

[19] Reed, R. H. & Moffat, L. 1983. Copper toxicity and copper tolerance in Ulva compressa (L.) Grev. J. expl. mar. Biol. Ecol., 69: 85-103.

[20] Riquelme, C.; Rojas, A.; Flores, V. & Correa, J. A. 1997. Epiphytic bacteria in a copper-enriched environment in Northern Chile. Mar. Pollut. Bull., 34:816-820.

[21] Ruppert, E. E.; Fox, R. S. & Barnes, R. D. 2005. Zoologia dos vertebrados: uma abordagem funcional evolutiva. 7. ed. São Paulo. Rocca, 1.145p.

[22] Schiff, K.; Diehl, D. & Valkirs, A. O. 2004. Copper emissions from antifouling paint on recreational vessels. Mar. Pollut. Bull., 48: 371-377.

[23] Turner, S. J.; Cummings, V. J.; Hewitt, J. E.; Wilkinson, M. R.; Williamson, R. B. & Lee, D. J. Changes in epifaunal assemblages in response to marina operations and boating activities. Mar. environ. Res., 43:181-199.

[24] Thouvenin, M.; Peron, J. J.; Charrateurm, C.; Guerin, P.; Langlois, J. Y. & Vallee-Rehel, K. 2002. A study of the biocide release from antifouling paints. Progr. Org. Coat., 44:75-83.

[25] Valkirs, A. O.; Seligman, P. F.; Haslbeck, E. & Caso, J. S. 2003. Measurement of copper release rates from antifouling paint under laboratory and in situ conditions: implications for loading estimation to marine water bodies. Mar. Pollut. Bull., 46:763-779.

[26] Warken, J.; Dunn, R. J. K. & Teasdale, P. R. 2004. Investigation of recreational boats as a source of copper at anchorage sites using time-integrated diffusive gradients in thin film and sediments measurements. Mar. Pollut. Bull., 49:833-843.

[27] Waterman, B. T.; Daehne, B.; Sievers, S.; Dannenberg, R.; Overbeke, J. C.; Klijnstra, J. W. & Heemken, O. 2005. Bioassays and selected chemical analysis of biocide-free antifouling coatings. Chem., 60:1530-1541.

[28] Wieser, W. 1967. Conquering terra firma: The copper problem from the isopod's point of view. Helgoländer. Wiss. Meeresunter., 15:282-93.

[29] Yenehara, Y.; Yamashita, H.; Kawakamura, C. & Itoh, K. 2001. A new antifouling paint base don a zinc acrylate copolymerer. Prog. Org. Coat., 42:150-158.