There are indications that the widespread use of organotin compounds (TBT and TPT) as antifoulings, as stabilizers in plastic and as pesticides, has severely affected several species of marine organisms. The most striking effect of TBT and TPT as hormonal disruptors is the development of male organs in females of gastropods, currently denominated imposex. This syndrome can lead to the sterilization and death of affected organisms. The present work gives an overview of the present state of knowledge on imposex occurrence and reports results of a survey conducted in Guanabara Bay, Rio de Janeiro and in several sites along the coast of Fortaleza, Ceará State. Different stages of imposex development were verified in this survey, however, the most prominent levels appeared associated to known spot sources of TBT and TPT.
Organotin compounds (OTs) were used in antifouling paints for more than four decades. However, due to their widespread intensive use and high toxicity, undesirable effects in non-target marine organisms have been detected since the early 1980s. Consequently, the International Maritime Organization banned new maritime applications of these products on January 1, 2003 and their presence on ship hulls from January 1, 2008. Although extensively studied in Europe, North America, Oceania, and Asia, environmental levels and effects of organotin contamination are still poorly known for South America. Thus, the current review aimed to present the actual status of this problem in South America by summarizing and comparing the available data in the literature. An overview of the OTs concentrations in sediment and biota and their effects, mainly imposex in marine gastropods, are presented. This work showed that in Atlantic coastal areas of South America there are "hot spots" of OTs contamination, similar to that observed in industrialized countries of Northern Hemisphere. On the other hand, the number of accomplished studies in the Pacific coast is extremely low. Despite the limitation on studies about OTs environmental levels and their related effects, the available data pointed out for a widespread TBT contamination along the South American coastal areas. Therefore, the establishment of baselines of organotin contamination in the Pacific coast and the implementation of temporal trend studies in the South American coastal areas is crucial to verify the effectiveness of local regulations and OTs global ban, and to map the most sensitive areas related to present and future antifouling impacts.
The first appraisal of butyltins (BT) contamination linked with imposex incidence in the Pacific coast of South America was performed in the current study. Imposex occurrence was analyzed in three muricid species (Thais biserialis, T. brevidentata, and T. kiosquiformis) distributed along 14 sites from the coastal areas of Ecuador. All studied muricids species showed imposex, which was observed in 11 out of 14 sites. The highest imposex levels were observed in T. kiosquiformis collected inside the Gulf of Guayaquil [relative penis length index (RPLI) 9.0-40.7], whereas RPLI values for T. biserialis and T. brevidentata ranged from 4.0 to 26.1 and 0.0 to 1.9, respectively. Additionally, BT compounds [tributyltin (TBT), dibutylin (DBT), and monobutylin (MBT)] were determined in surface sediments collected in 6 of the sites (main harbor areas), and values ranged between 12.7 and 99.5 ng Sn g(-1) (dry weight) for TBT, 1.8 and 54.4 ng Sn g(-1) for DBT, and 44 and 340 ng Sn g(-1) for MBT. Although BT degradation indexes suggested an aged input of TBT, the high imposex levels detected in the current study suggest that international restrictions on TBT based antifouling paints were still not effective in Ecuador. Considering that the southern coast, especially nearby harbors inside the Gulf of Guayaquil, have shown to be contaminated by BTs, a combination of T. kiosquiformis and T. biserialis (the most sensitive species) can be used for future biomonitoring of Ecuador coastal areas.
The first appraisal of butyltin (BT) contamination linked with imposex incidence in Peruvian coastal areas was performed in the present study. Imposex occurrence and BT levels in female bodies were analyzed in the rock snail Thais chocolata distributed along 10 sites in areas under the influence of Callao and Chimbote Harbors. Imposex levels associated to high tributyltin (TBT) concentrations were observed in six of 10 studied sites, and the highest imposex levels were seen in gastropods collected near the harbor terminals. Tributyltin concentrations were the highest reported for gastropod mollusks (up to 662 ng Sn g(-1)) in recent studies. Although TBT-based antifouling paints have been banned globally (International Maritime Organization, 2008), the combination of high imposex and TBTs level with butyltin degradation index values indicated fresh TBT inputs in these Peruvian coastal areas. Thus, the need to implement local regulatory strategies related to the use of TBT-free antifouling paints is urgent, as is a thorough assessment of the effectiveness of the TBT global ban. Moreover, the wide distribution of T. chocolata combined with its capability to elicit imposex and bioaccumulate BTs renders this a good sentinel species for TBT contamination along the western South American coast.
Recebido em 7/6/10; aceito em 11/1/11; publicado na web em 1/4/11 THIRD GENERATION ANTIFOULING PAINTS: NEW BIOCIDES IN THE AQUATIC ENVIRONMENT. Antifouling agents have been used on vessels and boats since ancient civilizations. Thus, a brief history on the three generations of antifouling paints was provided in the present review. Additionally, information about physic-chemical properties, environmental levels, toxicology and analytical methods was discussed for the 16 "new" booster biocides used as third-generation antifouling paints. The main problems, limitations and future trends related to this subject were also presented. Finally, actions were suggested in order to appraise the current status of the environmental impact caused by these compounds in South America.Keywords: antifouling; paint; booster biocides. INTRODUÇÃODentre os diversos grupos de contaminantes orgânicos potencialmente danosos a ecossistemas aquáticos, despontaram nos últimos anos os biocidas utilizados como princípio ativo de tintas antiincrustantes. Essas tintas são aplicadas como sistemas de proteção, com a finalidade de combater a formação e o estabelecimento de comunidades bioincrustantes (fouling) sobre superfícies expostas à água. Usualmente, tintas anti-incrustantes são aplicadas em embarcações comerciais e de passeio, plataformas petrolíferas, tubulações submarinas, comportas de represas, tanques destinados à aquicultura, dentre outras estruturas. 1Dentre as aplicações mencionadas para as referidas tintas, a utilização como revestimento protetor em embarcações tem sido apontada por muitos autores como a mais impactante para o ambiente, devido ao seu caráter altamente difundido em zonas costeiras.2 Segundo Kotrikla, 3 o emprego de sistemas anti-incrustantes em embarcações é justificado pelos seguintes motivos: o aumento da fricção entre o casco e a água, demanda uma maior potência dos motores e, consequentemente, gera um aumento no consumo de combustível; aumento da frequência de docagens, gerando um incremento de custos e de resíduos gerados; aumento das taxas de corrosão e, introdução não intencional de espécies exóticas em ambientes aquáticos.O primeiro registro de uso de sistemas anti-incrustantes data de 2 mil anos atrás, quando os cascos de madeira eram revestidos com chumbo e "untados" com misturas de óleo de baleia, enxofre e arsênio. Em 1625, uma receita letal combinando arsênio, cobre e goma em pó foi patenteada como agente anti-incrustante por Wilian Beale, na Inglaterra. A utilização de sistemas anti-incrustantes incorporados às tintas passou a ser comum, e cada vez mais frequente, na medida em que os cascos de madeira das embarcações foram substituídos por cascos metálicos, fato ocorrido em meados do século XVIII. A partir de então, a navegação comercial e o uso de embarcações de lazer se tornaram cada vez mais populares, aportando aos ambientes aquáticos quantidades cada vez maiores de biocidas utilizados em tintas anti-incrustantes. 1Em meados do século XX, os óxidos de cobre e de zinco foram os primeiros biocidas ut...
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