Satie Taniguchi

Historical record of polycyclic aromatic hydrocarbons (PAHs) and spheroidal carbonaceous particles (SCPs) in marine sediment cores from Admiralty Bay, King George Island, Antarctica

This paper describes the first results of polycyclic aromatic hydrocarbons (PAHs) and spheroidal carbonaceous particles (SCPs) in sediment cores of Admiralty Bay, Antarctica. These markers were used to assess the local input of anthropogenic materials (particulate and organic compounds) as a result of the influence of human occupation in a sub-Antarctic region and a possible long-range atmospheric transport of combustion products from sources in South America. The highest SCPs and PAHs concentrations were observed during the last 30 years, when three research stations were built in the area and industrial activities in South America increased. The concentrations of SCPs and PAHs were much lower than those of other regions in the northern hemisphere and other reported data for the southern hemisphere. The PAH isomer ratios showed that the major sources of PAHs are fossil fuels/petroleum, biomass combustion and sewage contribution generally close to the Brazilian scientific station.

Aliphatic and polycyclic aromatic hydrocarbons in surface sediments in Admiralty Bay, King George Island, Antarctica

Aliphatic (AHs) and polycyclic aromatic hydrocarbons (PAHs) concentrations were measured in marine surface sediments around the Brazilian station in Admiralty Bay, during the summers of 1997/98 and 1999/2000 using GC-FID and GC-MS. Total aliphatic hydrocarbons ranged from 0.15 to 13.28 μg·g−1 (dry weight) while n-alkanes varied between 0.10 and 9.63 μg·g−1. The highest concentrations were obtained at the sewage outfall, with decreasing levels away from the outfall. The distribution of n-alkanes showed significant quantities of long chain n-alkanes (n-C22 to n-C34) at sites near the Brazilian station that may be attributed to the station activities. A short chain n-alkanes sequence (n-C12 to n-C21) associated with diesel fuel arctic (DFA) was present in all the samples. Total PAHs varied from 9.45 to 270.5 ng·g−1. The higher PAHs level and the presence of an unresolved complex mixture only in sediment from the sewage outfall is an indication of oil contamination at this location. A slight increase in PAHs near the Brazilian station since 1993 may be attributed to an increase in the number of staff over recent years. In general, the concentration of AHs and PAHs was similar to that found in other Antarctic areas.

Results from a 15-year study on hydrocarbon concentrations in water and sediment from Admiralty Bay, King George Island, Antarctica

Abstract Admiralty Bay on the King George Island hosts the Brazilian, Polish and Peruvian research stations as well as the American and Ecuadorian field stations. Human activities in this region require the use of fossil fuels as an energy source, thereby placing the region at risk of hydrocarbon contamination. Hydrocarbon monitoring was conducted on water and sediment samples from the bay over 15 years. Fluorescence spectroscopy was used for the analysis of total polycyclic aromatic hydrocarbons (PAHs) in seawater samples and gas chromatography with flame ionization and/or mass spectrometric detection was used to analyse individual n-alkanes and PAHs in sediment samples. The results revealed that most sites contaminated by these compounds are around the Brazilian and Polish research stations due to the intense human activities, mainly during the summer. Moreover, the sediments revealed the presence of hydrocarbons from different sources, suggesting a mixture of the direct input of oil or derivatives and derived from hydrocarbon combustion. A decrease in PAH concentrations occurred following improvement of the sewage treatment facilities at the Brazilian research station, indicating that the contribution from human waste may be significant.

Evaluation of tropical water sources and mollusks in southern Brazil using microbiological, biochemical, and chemical parameters

Florianópolis, a city located in the Santa Catarina State in southern Brazil, is the national leading producer of bivalve mollusks. The quality of bivalve mollusks is closely related to the sanitary conditions of surrounding waters where they are cultivated. Presently, cultivation areas receive large amounts of effluents derived mainly from treated and non-treated domestic, rural, and urban sewage. This contributes to the contamination of mollusks with trace metals, pesticides, other organic compounds, and human pathogens such as viruses, bacteria, and protozoan. The aim of this study was to perform a thorough diagnosis of the shellfish growing areas in Florianópolis, on the coast of Santa Catarina. The contamination levels of seawater, sediments, and oysters were evaluated for their microbiological, biochemical, and chemical parameters at five sea sites in Florianópolis, namely three regular oyster cultivation areas (Sites 1, 2, and oyster supplier), a polluted site (Site 3), and a heavily polluted site (Site 4). Samples were evaluated at day zero and after 14 days. Seawater and sediment samples were collected just once, at the end of the experiment. Antioxidant defenses, which may occur in contaminated environments in response to the increased production of reactive oxygen species (ROS) by organisms, were analyzed in oysters, as well as organic compounds (in oysters and sediment samples) and microbiological contamination (in oysters and seawater samples). The results showed the presence of the following contaminants: fecal coliforms in seawater samples (four sites), human adenovirus (all sites), human noroviruses GI and GII (two sites), Hepatitis A viruses (one site), JC Polyomavirus in an oyster sample from the oyster supplier, Giardia duodenalis cysts, and Cryptosporidium sp oocysts (one site). Among organochlorine pesticides, only DDT (dichlorodiphenyltrichloroethane) and HCH (hexachlorocyclohexane) were detected in some sediment and oysters samples in very low levels; site 4 had the highest concentrations of total aliphatic hydrocarbons, PAHs, and linear alkylbenzenes (LABs) found either in oysters or in sediment samples. The major concentration of fecal sterol coprostanol was found at site 4, followed by site 3. After 14 days of allocation in the four selected sites, there was a significant difference in the enzymes analyzed at the monitored spots. The detection of different contaminants in oysters, seawater, and sediment samples in the present study shows the impact untreated or inadequately treated effluents have on coastal areas. These results highlight the need for public investment in adequate wastewater treatment and adequate treatment of oysters, ensuring safe areas for shellfish production as well as healthier bivalve mollusks for consumption.

Biochemical biomarkers and hydrocarbons concentrations in the mangrove oyster Crassostrea brasiliana following exposure to diesel fuel water-accommodated fraction.

Understanding the toxic mechanisms by which organisms cope to environmental stressful conditions is a fundamental question for ecotoxicology. In this study, we evaluated biochemical responses and hydrocarbons bioaccumulation of the mangrove oyster Crassostrea brasiliana exposed for 96 h to four sublethal concentrations of diesel fuel water-accommodated fraction (WAF). For that purpose, enzymatic activities (SOD, CAT, GPx, GR, G6PDH, GST and GGT), HSP60 and HSP90 immunocontent and lipid peroxidation (LPO) levels were determined in the gill and digestive gland of oysters and related to the hydrocarbons accumulated in the whole soft tissues. The results of this study revealed clear biochemical responses to diesel fuel WAF exposure in both tissues of the oyster. The capacity of C. brasiliana to bioaccumulate aliphatic and aromatic hydrocarbons in a dose-dependent manner is a strong indication of its suitability as a model in biomonitoring programs along the Brazilian coast, which was also validated by the response of the antioxidant defenses, phase II biotransformation and chaperones. HSP60 levels and GGT activity were the most promising biomarkers in the gill, while GST and GR activities stood out as suitable biomarkers for the detection of diesel toxicity in the digestive gland. The decrease of SOD activity and HSP90 levels may also reflect a negative effect of diesel exposure regardless the tissue. The present results provide a sound preliminary report on the biochemical responses of C. brasiliana challenged with a petroleum by-product and should be carefully considered for use in the monitoring of oil and gas activities in Brazil.

Polycyclic aromatic hydrocarbons (PAHs) in plastic pellets: Variability in the concentration and composition at different sediment depths in a sandy beach

Plastic pellets have the ability to adsorb organic pollutants such as PAHs. This study analyzed the variability in the concentration and composition of PAHs on plastic pellets sampled up to 1m deep in the sediment of a sandy beach. The toxic potential of PAHs was analyzed, and the possible sources of contamination are discussed. The total PAHs varied, with the highest concentrations in the surface layer; the priority PAHs showed a different pattern. PAHs at greater depths did not reach toxicity levels above the PEL. The composition of PAHs differed between pellets from the shallower and from deeper sediment layers, and was suggested a mixture of sources. These results provided the first information on the depth distribution of PAHs in sandy beaches, associated with plastic pellets; and evidenced the potential environmental risk. Similarly to the abundance of pellets, the toxic potential is underestimated in surface samples.

Chlorinated pesticides, polychlorinated biphenyls and polycyclic aromatic hydrocarbons in the fat tissue of seabirds from King George Island, Antarctica.

Persistent organic pollutants (POPs), such as chlorinated pesticides, polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs), have been detected worldwide, including in the Antarctic region. The Antarctic continent can no longer be considered pristine, as there has been a localized but considerable human impact on the region (UNEP, 2002). Local pollution caused by research stations, tourism and long-range transport account for the presence of these compounds in the biota (Risebrough and Carmignani, 1972; Lukowski,1983a,b; Montone et al., 2001b; Corsolini et al., 2002), atmosphere (Bidleman et al., 1993; Montone et al., 2005), water (Gupta et al., 1996; Bicego et al., 1996; Bicego et al., 2002) and sediment (Montone et al., 2001a; Martins et al., 2004; Curtosi et al., 2007) in Antarctica. Several organisms may be used to investigate local pollution. Birds have a number of advantages in this respect. The ecology and behavior of birds are particularly well understood and the background knowledge of their biology enhances their usefulness as biomonitors (Furness and Greenwood, 1993). Antarctica has over 40 species of nesting birds. Many are natives to this remote region of Earth (e.g., Adelie penguin, Antarctic petrel, Snow petrel) and others come to the Antarctic continent and sub Antarctic islands to breed and then migrate to lower latitudes the rest of the year (e.g., Southern fulmar, Cape petrel, South Polar skua). As long-range migratory and top predators, skuas can accumulate high concentrations of anthropogenic contaminants as they forage over large areas. In contrast, penguins show greater fidelity to the Antarctic and sub Antarctic region. This baseline report presents the concentration of selected chlorinated pesticides, polychlorinated biphenyls and polycyclic aromatic hydrocarbons (PAHs) measured in archived fat samples from Brown skuas (Catharacta antarctica, n = 6) and three species of penguins [Adelie (Pygoscelis adeliae; n = 2), Chinstrap (Pygoscelis antarctica; n = 2) and Gentoo (Pygoscelis papua; n = 3)] captured in the vicinity of a Brazilian and a Polish Antarctic Station on King George Island. Opportunistic samples of Antarctic tern (Sterna vittata; n = 2), Snowy sheathbill (Chionis alba; n = 1) and Blue-eyed shag (Phalacrocorax atriceps; n = 1) were also analyzed. Subcutaneous fat samples from these birds were collected near the Comandante Ferraz (62 050S–58 230W; Brazil) andH. Arctowski (62 090S–58 280W; Poland) Antarctic Stations, located in Admiralty Bay during the summer of 1997–1998 (Fig. 1), wrapped in aluminium foil and immediately frozen at 15 C. The analytical procedure followed that described by MacLeod et al. (1985). Briefly, after the addition of anhydrous Na2SO4, approximately 0.5 g of wet tissue was extracted withmethylene chloride using a tissumizer. Prior to extraction, 4,40-dibromooctafluorbiphenyl (DBOFB), 2,20,4,50,6-pentachlorobiphenyl (PCB 103); 2,20,3,30,4, 5,50,6-octachlorobiphenyl (PCB 198); d8-naphthalene, d10-acenaphthene, d10-phenanthrene, d12-chrysene and d12-perylene were added to samples, blanks and reference material (SRM 1945 from the National Institute of Standards and Technology) as surrogates for chlorinated pesticides, PCBs and PAHs, respectively. Extracts were initially cleaned by using partially deactivated silica:alumina column chromatography eluted with a 1:1 mixture of pentane and methylene chloride. The fraction was further purified by high-performance liquid chromatography (HPLC) to remove excess lipids and finally concentrated to a volume of 0.5 mL in hexane. Internal standards (2,4,5,6-tetrachlorometaxylene (TCMX) for chlorinated pesticides and PCBs; and d10-fluorene and d10-benzo[a]pyrene) for PAHs) were added prior to gas chromatographic analysis. Chlorinated pesticides and PCBs were analyzed through gas chromatography using an electron capture detector (ECD). PAHs were quantitatively analyzed through a gas chromatograph coupled to a mass spectrometer (GC–MS) in a selected ion mode (SIM). Table 1 displays mean concentrations (±standard deviation) on a lipid weight (lw) basis for HCHs, HCB, DDTs, chlordanes, dieldrin, mirex, total PCBs and total PAHs in the seabirds studied. Except for HCHs and HCB, the concentrations of most chlorinated pesticides were significantly higher in skuas than in the other species of birds (Fig. 2). In contrast, no significant differences in the concentrations of these compounds were found among the three species of penguins studied (Fig. 3). Lukowski (1983a) found a similar profile of DDTs in adipose tissue of the same three species of penguins collected in the proximity of the Arctowski Station in Admiralty Bay, but at significantly lower concentrations (0.548 ± 0.314, 0.340 ± 0.238, 0364 ± 0.155 ng g 1 w for P. adeliae, P. antarctica and P. papua, respectively). Average concentrations of oxychlordane, dieldrin, mirex and p,p0-DDE in skuas (408 ± 169, 254 ± 158, 2210 ± 1590 and 5840 ± 4020 ng g 1 lw, respectively) were approximately 15, 10, 25 and 30 times higher than in penguins. Lukowski (1983b) also found DDT contents approximately 15 times higher in skua than in penguins. This difference demon-

INTEGRATED ASSESSMENT OF MULTILEVEL BIOMARKER RESPONSES AND CHEMICAL ANALYSIS IN MUSSELS FROM SAO SEBASTIAO, SAO PAULO, BRAZIL

The aim of the present study was to investigate the presence of contaminants in the mussel Perna perna from São Sebastião Channel, São Paulo, Brazil, and to evaluate the effects of these contaminants on these organisms at biochemical (catalase [CAT], glutathione-S-transferase [GST], and cholinesterase [ChE]), cellular (neutral red retention time [NRRT] assay), and physiological (cardiac monitoring) levels. Two sampling surveys were performed (winter of 2001 and summer of 2002) at six stations along the channel: Cigarras, station 1; Iate Clube de Ilhabela, station 2; Oil Terminal, station 3; Toque Toque, station 4; Ponta da Sela, station 5 (reference station); and Taubaté, station 6. Differences in CAT activity were observed between mussels from stations 3 and 5 during the winter, but no differences were detected in the summer. No differences in GST activity were found among stations during the winter, although animals from station 3 showed higher activity during the summer. The ChE activity was significantly higher in the mussels from stations 1 and 2 during the winter and from stations 1 and 3 during the summer. Organisms from stations 1 through 4 showed statistically lower NRRT in both seasons. Similar heart rates were observed in the mussels from all stations. Hydrocarbons were detected in organisms from all the stations in both seasons. During the winter, higher polycyclic aromatic hydrocarbon (PAH) levels were observed in organisms from station 3, whereas during the summer, higher levels of metals were found in organisms from stations 1, 3, and 4. The multivariate analyses showed a strong influence of PAHs on the winter biological results, but metals showed higher influence on these responses in the summer, indicating multiple contaminant sources.

Distribution of sewage input in marine sediments around a maritime Antarctic research station indicated by molecular geochemical indicators

Sediments from Admiralty Bay, Antarctica were collected during the austral summers of 2002/2003 and 2003/2004 in order to assess the distribution and concentration of sewage indicators originating from Comandante Ferraz Brazilian Antarctic Station. Fecal sterols (coprostanol+epicoprostanol) and linear alkylbenzenes (LABs) ranged from <0.01 to 0.95 microg g(-1) and <1.0 to 23 ng g(-1) dry weight, respectively. In general, the higher concentrations were found only locally in the vicinity of Ferraz station at Martel Inlet. Baseline values for fecal sterols and coprostanone were calculated as 0.19 and 0.40 microg g(-1), respectively. According to fecal sterols concentrations, sewage contribution to Martel Inlet has increased more than twice since 1997, as result of the increase in the number of researchers at the station especially during the last decade. A low correlation was found between total LABs and fecal steroids, which could be attributed to the contribution of the natural sources of steroids.

Occurrence of organochlorine compounds in Euphausia superba and unhatched eggs of Pygoscelis genus penguins from Admiralty Bay (King George Island, Antarctica) and estimation of biomagnification factors.

Polychlorinated biphenyls (PCBs) and organochlorine pesticides are compounds that do not occur naturally in the environment and are not easily degraded by chemical or microbiological action. In the present work, those compounds were analysed in unhatched penguin eggs and whole krill collected in Admiralty Bay, King George Island, Antarctica in the austral summers of 2004-2005 and 2005-2006. The compounds found in higher levels (in a wet weight basis) were, in most of the egg samples, the PCBs (2.53-78.7 ng g(-1)), DDTs (2.07-38.0 ng g(-1)) and HCB (4.99-39.1 ng g(-1)) and after Kruskal-Wallis ANOVA, the occurrence seemed to be species-specific for the Pygoscelis genus. In all of the cases, the levels found were not higher than the ones in Arctic birds in a similar trophic level. The krill samples analysis allowed estimating the biomagnification factors (which resulted in up to 363 for HCB, one order of magnitude higher than DDTs and chlordanes and two orders of magnitude higher than the other groups) of the compounds found in eggs, whose only source of contamination is the female-offspring transfer.