Rosalinda Carmela Montone

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.

Polycyclic aromatic hydrocarbons (PAHs) in a large South American industrial coastal area (Santos Estuary, Southeastern Brazil): sources and depositional history.

Located in southeastern Brazil, the Santos Estuary has the most important industrial and urban population area of South America. Since the 1950s, increased urbanization and industrialization near the estuary margins has caused the degradation of mangroves and has increased the discharge of sewage and industrial effluents. The main objectives of this work were to determine the concentrations and sources of polycyclic aromatic hydrocarbons (PAHs) in sediment cores in order to investigate the input of these substances in the last 50 years. The PAHs analyses indicated multiple sources of these compounds (oil and pyrolitic origin), basically anthropogenic contributions from biomass, coal and fossil fuels combustion. The distribution of PAHs in the cores was associated with the formation and development of Cubatão industrial complex and the Santos harbour, waste disposal, world oil crisis and the pollution control program, which results in the decrease of organic pollutants input in this area.

Plastic ingestion by Procellariiformes in Southern Brazil

The Procellariiformes are the birds most affected by plastic pollution. Plastic fragments and pellets were the most frequent items found in the digestive tract of eight species of Procellariiformes incidentally caught by longline fisheries as well as beached birds in Southern Brazil. Plastic objects were found in 62% of the petrels and 12% of the albatrosses. The Great shearwater, Manx shearwater, Corys shearwater and Antarctic fulmar were found to have greater quantities and frequencies of occurrence of plastic. There was no significant difference in the number of plastics between the birds from longline fisheries and beached birds. No correlation was found between the number of prey and number of plastics in the digestive tract of the birds analyzed, but this does not discard the hypothesis that, in some cases, the presence of plastic in the digestive tract has a negative effect on the feeding efficiency of these birds.

Natural and anthropogenic sterols inputs in surface sediments of Patos Lagoon, Brazil

The Patos Lagoon, the largest coastal lagoon in the world, has long been receiving considerable anthropogenic input resulting from urban, rural and industrial activities. Thus, sewage contamination possibly originating from the more than 2 million inhabitants living within its drainage basin is examined in this study. Sediment samples collected from various points along the Lagoon were extracted, purified and analysed by GC-MS. Ten different sterols and ketones, including coprostanol and epicoprostanol, were identified and quantified. The highest coprostanol concentration was found near Porto Alegre City (1,423 ng g-1 dry wt.), whilst most sediment levels ranged between < DOL and 91.78 ng g-1. The highest concentrations were found at those three sites located closest to domestic outfalls though levels tended to decrease with distance from the sources. The 5b/(5b+5a) isomeric ratios indicated sewage-contaminated sediments near Porto Alegre City, while the epicoprostanol/coprostanol ratio showed values characteristic of untreated sewage input.

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.

Determination of butyltin compounds in surface sediments from the São Paulo State coast (Brazil) by gas chromatography–pulsed flame photometric detection

Occurrence and the effects of butyltin compounds (BTs) have been studied for some years, mainly in countries of the Northern Hemisphere. Due to widespread use of tributyltin compounds (TBTs) and considering their deleterious effects, it is necessary to conduct studies on its occurrence, especially in the marine environment because of its excessive use in coatings of ship hulls to prevent fouling. Moreover, it was important to extend the evaluation to areas where there is no current information about their occurrence. The present work reports the occurrence of BTs in marine sediments of São Paulo state, Brazil. Commercial and leisure harbor sampling sites were selected because these areas are potentially exposed to BTs from antifouling paints used on ship hulls. Analytical conditions for organotin analysis in marine sediments were optimized for GC with pulsed flame photometric detection. Detection limits ranged from 8A to 66.3 ng g(-1) using a 610-nm filter, and the linearity range was 20-500 ng g(-1). Concentration levels of BTs were highest in Santos harbor (360 ng g(-1) TBT in average) and Guarujá marina (670 ng g(-1) TBT in average), which seems to be related to intensive boat traffic. Lower levels of BTs were observed in Cananéia, where only fishing boats are present (50 ng g(-1) TBT in average).

Arsenic and trace metal contents in sediment profiles from the Admiralty Bay, King George Island, Antarctica

Admiralty Bay (Antarctica) hosts three scientific stations (Ferraz, Arctowski and Macchu Picchu), which require the use of fossil fuel as an energy source. Fossil fuels are also considered the main source of pollution in the area, representing important inputs of major pollutants (organic compounds) and trace metals and metalloids of environmental interest. Accordingly, this work presents the results of As, Cd, Cr, Cu, Ni, Pb and Zn in sediment profiles from Admiralty Bay. The sediment results from Ferraz station were slightly higher than the other sampling sites. The highest contents were observed for Cu and Zn (from 44 to 89 mg kg(-1)). Otherwise, by using enrichment factors and geochronology analysis, the most relevant enrichment was observed for As in the samples collected close to the Ferraz station, indicating that increasing As content may be associated with the activities associated with this site.

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-

An Efficient Ethanol-Based Analytical Protocol to Quantify Faecal Steroids in Marine Sediments

The majority of the analytical methods for steroids in marine sediments are laborious and time consuming and involve the use of large volumes of organic (frequently chlorinated) solvents. A method has been developed utilising ethanol extraction with a rapid alumina-ethanol elution clean up, providing an environmentally friendly and inexpensive alternative. Recoveries of steroids (coprostanol, epicoprostanol, cholesterol, cholestanol, 5a-coprostanone and 5b-coprostanone) ranged from 70 to 93% and compared favourably with more traditional analyses. Analytical performance was tested through analysis of reference material and concentrations recorded for coprostanol, cholesterol and cholestanol were close to the mean certified values and were within acceptable values. Relative standard deviations from triplicate analyses were small (6-12%). These initial tests also indicate that the simplified clean up (without fractionation) is not subject to interference in the quantification of the selected faecal steroids.