ARTICLE IN PRESS Marine Pollution Bulletin xxx (2010) xxx–xxx Contents lists available at ScienceDirect Marine Pollution Bulletin journal homepage: www.elsevier.com/locate/marpolbul Baseline Changes and variations of polycyclic aromatic hydrocarbon concentrations in fish, barnacles and crabs following an oil spill in a mangrove of Guanabara Bay, Southeast Brazil Abílio Soares-Gomes a, Roberta L. Neves b, Ricardo Aucélio b, Paulo H. Van Der Ven c, Fábio B. Pitombo a, Carla L.T. Mendes a, Roberta L. Ziolli b,* a Laboratório de Ecologia de Sedimento, Departamento de Biologia Marinha, Universidade Federal Fluminense, Caixa Postal 100644, Niterói, RJ 24001-970, Brazil b Laboratório de Estudos Ambientais e Toxicologia (LEATox), Departamento de Química, Pontifícia Universidade Católica do Rio de Janeiro (PUC-Rio), Rua Marquês de São Vicente, 225, Gávea, Rio de Janeiro, RJ 22453-900, Brazil c Vale Moçambique Ltda, Vila Carbomoc Casa 20, Moatize, Tete, Mozambique article info abstract Keywords: On April 26th, 2005, an accident caused a leak of 60,000 L of Diesel Oil Type ‘‘B”, freighted by train wagons Polycyclic aromatic hydrocarbons upstream on a mangrove area within Guanabara Bay, Southeast Brazil. After the accident, samples from Oil spill animals with different biological requirements were collected in order to monitor polycyclic aromatic Crabs hydrocarbons concentrations for the following 12 months. Sessile, mobile, carnivorous, omnivorous, Barnacles organic detritus feeders, planktivorous and suspension feeders were some of the attributes compared. Fish Concentrations of PAHs did not vary in relation to different dietary habits and the best response was from Sentinel À1 Guanabara Bay the sessile suspensivorous barnacles. A background level of <50 lgkg was suggested based on the ref- erence site and on values observed in the following months after the accident. The highest values of PAH concentrations were observed in barnacles in the first month immediately after the spill, decreasing to background levels after few months. Barnacles are suggested as a sentinel species. Ó 2010 Elsevier Ltd. All rights reserved. On April 26th, 2005, an accident took place on the railway oper- mours and cancer (Hoffman, 2003). Relationships between the ated by ‘‘Ferrovia Centro-Atlântica” (FCA), in Itaboraí municipality, occurrence of neoplasia and liver tumours in fish and PAH concen- Rio de Janeiro State. The accident caused the leakage of 60,000 L of trations in sediment where they were collected have shown that diesel oil freighted by train wagons. Part of the oil was retained on- there is a strong causal link between these factors (Malins et al., site and part reached the Aldeia and Caceribú Rivers (Fig. 1). In 1988; Varanasi, 1989; Hoffman, 2003; Ariese et al., 2005). Polycy- spite of the immediate containment work, the oil was spread over clic aromatic hydrocarbons affect humans primarily through food by the river and through the mangrove channels of Caceribu estu- consumption. Once ingested, PAHs can be absorbed by the human ary, within the Guapimirim Environmental Protected Area [‘‘APA body and may cause cancers and decreased fecundity, among other de Guapimirim”], driven by tidal flow. The spill product was clas- health problems (Fleming et al., 2006). Besides ecological conse- sified as Diesel Oil Type ‘‘B”, used as fuel by automotive vehicles. quences, seafood safety is an issue of concern in every oil spill inci- After the accident, FCA contacted scientific institutions and consul- dent. Commercial and recreational fisheries and subsistence tants to begin monitoring the effects of the oil on biota, specially seafood use could potentially be affected as a consequence of the edible organisms. It is in this scope that this present research plays fauna and flora exposure to oil. In order to guarantee public health, its role, being part of the environmental studies developed volun- restrictions or closure of seafood harvesting might be necessary tarily by FCA and under the supervision of the Brazilian Federal (Yender et al., 2002). In Brazil, determining safety concentration Environmental Agency, Instituto Chico Mendes de Conservação levels of PAHs in seafood exposed to oil is usually dealt with in da Diversidade (ICMBIO). workshops developed on the occasion of the spill, with the partic- Polycyclic aromatic hydrocarbons (PAHs) affect organisms ipation of the State staff and federal agencies, and the responsible through toxic actions. A major concern in animals is the ability of party. To date, no agency has adopted clear guidelines for fisheries the reactive metabolites of some PAHs to bind cellular proteins closure or reopening after an incident of oil environmental con- and DNA, leading to mutations, developmental malformations, tu- tamination (Silva et al., 2007). Since the affected areas were within a mangrove environment, * Corresponding author. Tel.: +55 21 3527 1824; fax: +55 21 3527 1637. used by the local fisherman to catch crabs and finfish for selling E-mail address: [email protected] (R.L. Ziolli). at nearby markets, the main concern of this study was to assess 0025-326X/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.marpolbul.2010.05.013 Please cite this article in press as: Soares-Gomes, A., et al. Changes and variations of polycyclic aromatic hydrocarbon concentrations in fish, barnacles and crabs following an oil spill in a mangrove of Guanabara Bay, Southeast Brazil. Mar. Pollut. Bull. (2010), doi:10.1016/j.marpolbul.2010.05.013 ARTICLE IN PRESS 2 A. Soares-Gomes et al. / Marine Pollution Bulletin xxx (2010) xxx–xxx Mage Itaborai Duque de Caxias Sao Goncalo Guanabara Bay Rio de Janeiro Niteroi 5km Atlanctic Ocean 430 2'30''W 430 0'0''W 420 57'30''W 420 55'0''W N railway main road Caceribu River cafoecalPtnedic S''03'2422 Aldeia River 0 Guanabara Bay Mangrove S''0'5422 Sampling site 0 1km Fig. 1. Map showing the site of the accident and the area affected by the oil spill. environmental contamination through biota using species with whereas crabs and barnacles were sampled at six fixed stations distinct ecological niches. This approach allowed an assessment (Fig. 1). Specimens were maintained in ice in an isotherm box until of environmental contamination from different perspectives, tissue extraction in the laboratory. Muscle tissue (10 g) of each col- allowing a better evaluation of the accident and its consequences. lected fish and crab was extracted and approximately 10 barnacles Guanabara Bay is one of the most important embayments of the were pooled per station in order to obtain enough mass for analy- Brazilian coast and various forms of pollution threaten its estuarine sis. Specimens of crabs and fishes from reference areas (Angra dos environment. The bay includes two refineries, 16 oil terminals, Reis and Itaipú) and from a fish market (São Pedro Municipal Mar- 6000 industries and two shipyards, and receives an estimated daily ket, Niterói) were also analysed for comparison. oil input around 9.5 tons, among other pollutants (Francioni et al., PAH extraction was carried out based on the extraction method 2005). The PAH contamination of the bay sediment was docu- employed by Meniconi et al. (2002). Each sample was freeze-dried mented by several studies (Hamacher, 1996; Lima, 1996; Meniconi and approximately 1 g of the homogenate was extracted in Tedia et al., 2002) and a detailed description of the bay has been pre- methylene chloride pesticide grade (50 mL) for 3 min, using a high sented by Kjerfve et al. (1997). In spite of being located in a highly rotation tissuemizer (11,000–16,000 rpm). The residue obtained urbanized area and thus considered heavily polluted (Kjerfve et al., was re-extracted and the extracts were pooled and filtered. The li- 1997), the bay supports important local fisheries (Jablonski et al., pid content was reduced by cleanup on a 2% deactivated Merck 2006) and still retains 90 km2 of fringing mangroves (Pires, 1992) aluminium oxide 90 active neutral (70–230 mesh ASTM) column of which ca. 50% are relatively preserved inside the Guapimirim (20 g), using 100 mL of methylene chloride. The extract obtained Environmental Protection Area (APA de Guapimirim). after cleanup was concentrated on a rotatory evaporator to 5 mL. After the oil spill, monthly samples were taken in the affected Fixed Fluorescence spectroscopy (FF) measurements were per- area. The first sampling was conducted between 6th and 10th days formed on a Perkin-Elmer LS 55 Luminescence Spectrometer. Spec- after the accident on May 2nd to 6th 2005. The second was also tra were recorded in 1 cm quartz cuvettes with both excitation (ex) carried out in May and after that, monthly samplings were per- and emission (em) slit widths set to 4 nm. Pyrene (>97%) pur- formed until March 2006, totalling 12 surveys. Each sampling sur- chased from Sigma (St. Louis, USA) was used as the standard PAH vey was performed within the affected area (i.e. were the oil slick and its optimal wavelength pair for detection was identified as was observed in the first campaign), and in each survey different being 334/383 nm. As other polycyclic aromatic compounds can species of fish, the crab Ucides cordatus and the barnacle Fistulobal- present fluorescent properties in the same wavelength pair used anus citerosum were collected. Fish were randomly collected, for detection, results were indicated as pyrene equivalents. The Please cite this article in press as: Soares-Gomes, A., et al. Changes and variations of polycyclic aromatic hydrocarbon concentrations in fish, barnacles and crabs following an oil spill in a mangrove of Guanabara Bay, Southeast Brazil. Mar. Pollut. Bull. (2010), doi:10.1016/j.marpolbul.2010.05.013 ARTICLE IN PRESS A. Soares-Gomes et al. / Marine Pollution Bulletin xxx (2010) xxx–xxx 3 Table 1 the accident), in levels higher than those of the first sample after List of sampled fish from the oil exposed area.