Rolf Roland Weber

Aliphatic and Aromatic Hydrocarbons in Sediments of Santos and Cananéia, SP, Brazil

Sediment samples from Santos and Cananéia, São Paulo Brazil were analysed by GC-FID and GC-MS for aliphatic and aromatic hydrocarbons in order to gather information on the degree of contamination by oil and other biogenic contributions. Concentrations of total n-alkanes in Santos varied from 1.05 to 4.29 microg g(-1) and aromatic hydrocarbons from 0.08 to 42.39 microg g(-1). In Cananéia total n-alkanes varied from 4.37 to 157.90 microg g(-1). However, aromatic hydrocarbons were not detected. In Cananéia n-alkanes of terrestrial plants with high molecular weight predominate (n-C25, n-C27, n-C29, n-C31 and n-C33). In Santos, a more uniform distribution of the n-alkanes and aromatic hydrocarbons was found at all the sediment stations. The hydrocarbon data from stations close to the Saboó Wharf, at Alemoa and in the COSIPA Channel revealed alarming levels of acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene and chrysene.

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.

Aromatic hydrocarbons on surface waters of Admiralty Bay, King George Island, Antarctica

Abstract Total aromatic hydrocarbons were measured for surface seawater at 24 points in Admiralty Bay, Antarctica, during the summers of 1989, 1990, 1992 and 1993, using the spectrofluorimetric method. The levels varied between 0.05 and 8.86 μg l −1 , but the majority of the samples presented levels below 1.00 μg l −1 , so there were no alarming oil inputs in the area. In 1992, one point in front of the Antarctica Station Comandante Ferraz was sampled with an automatic pre-concentration unit capable of processing large volumes of seawater for GC-MS analysis. This water sample presented a total aromatic content of 0.080 μg l −1 . Main two-ring aromatic compounds quantified by GC-MS were naphthalene, acenaphthylene, 1-methylnaphthalene, 2-methylnaphthalene and acenaphthene. Of the three-ring polycyclic aromatic hydrocarbons (PAHs), phenanthrene contributes more than anthracene. Of the four-ring members, fluoranthene is more abundant than pyrene. Five-ring or six-ring members were not found. These individual levels and types of PAHs are typical of marine environments with small oil-derived hydrocarbons inputs.

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-

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.

Dissolved/dispersed petroleum aromatic hydrocarbons in the São Sebastião Channel, São Paulo, Brazil

Abstract A monitoring programme at Sao Sebastiao Channel, Sao Paulo, Brazil, was conducted in terms of dissolved/dispersed petroleum aromatic hydrocarbons (DDPAH) in water analysed by flourescence spectroscopy. The study was done in order to establish a baseline data for this area and verify the petroleum hydrocarbon influence from the oil terminal (DTCS) and other human activities over the channel. The DDPAH concentrations on subsurface waters were low and only one station presented a chronic local contribution. An oil spill occurred in May 1994 and it was followed-up to verify its influence in this area. The obtained data were important to verify the influence of the oil spill along the Channel. The oil spilled reached the majority of the sampling stations, and the highest mean concentration found was close to the accident point (49.6 μg l−1). Due to the intense wind driven currents of the Channel area, however, the elevation of the hydrocarbons levels in the surface waters was only temporary.

Determination of polychlorinated biphenyls in Antarctic macroalgae Desmarestia sp.

Selected polychlorinated biphenyl (PCB) congeners were measured in Desmarestia sp., an abundant algae in the Antarctica Peninsula and South Shetlands. Samples were collected from various points of Admiralty Bay, King George Island, Antarctic Peninsula, during the 1993-1994 austral summer. Total PCB concentrations ranged from 0.46 to 3.86 ng g(-1) (dry weight). Predominant PCB congeners were 52, 101, 110, 138 and 153. The low levels of PCBs found on all samples and the predominance of low molecular weight congeners indicate that there are no significant local PCBs sources in the area of study.

Formation of low molecular weight carbonyl compounds by sensitized photochemical decomposition of aliphatic hydrocarbons in seawater

SummaryAnthraquinone has been found to be a compound occuring frequently in seawater. Excited by solar radiation it acts as one of many natural and man-made photosensitizers and can thus be used as a model substance for the study of sensitized photochemical reactions of environmental chemicals. Experimentally it has been shown to mediate the oxidative photochemical decomposition of aliphatic hydrocarbons which, lacking absorption bands in the solar UV range at sea level, are by themselves photochemically inert. Formaldehyde, smaller amounts of acetaldehyde and acetone as well as a still unidentified carbonyl compound are the principal low molecular weight products generated in the anthraquinone-sensitized photooxidation, with natural as well as artificial sunlight, of straight chain saturated hydrocarbons accommodated in high purity water. Qualitatively the same results were obtained in natural seawater as reaction medium from which particles were removed by glass fiber filtration and organic compounds by adsorption on activated charcoal. The concomittant generation of homologous series of methylketones and terminal alkenes suggest a decomposition mechanism involving cyclic electron rearrangement in a 6-membered transition state. Based on HPLC analysis of their 2,4-dinitrophenylhydrazones, the rates of volatile carbonyl generation in the sensitized photo-oxidation of n-tetradecane was determined in the liquid phase. Also determined was the rate of formaldehyde formation in the gas phase from n-tetradecane and from two Brazilian crude oils. The rates of generation of acetaldehyde and acetone could not be determined in the experiments with crude oils because of irregular changes of concentrations with time. The rate of concentration increase of formaldehyde in the vapour phase over the hydrocarbon surface film was similar to that in the water underneath. The artifical light source was a high pressure xenon lamp whose emission spectrum closely resembles that of natural sunlight at sea level. It was calibrated against the intensity of natural sunlight using pnitroacetophenone/pyridine as binary chemical actinometer.

Determination of Geochemically Important Sterols and Triterpenols in Sediments Using Ultrahigh-Performance Liquid Chromatography Tandem Mass Spectrometry (UHPLC–MS/MS)

A fast, sensitive, and selective ultrahigh-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method that is able to quantify geochemical biomarkers in sediment is described. A pool of 10 sterols, which can be used as biomarkers of autochthonous (cholesterol, cholestanol, brassicasterol, ergosterol), allochthonous (stigmasterol, β-sitosterol, campesterol, and stigmastanol) and anthropogenic (coprostanol and epicoprostanol) organic matter (OM), and three triterpenols (lupeol, α-amyrin, and β-amyrin) were chosen as the analytes. The method showed excellent analytical parameters, and, compared with the traditional GC-MS methods that are commonly applied for the analysis of sterols, this method requires no sample cleanup or derivatization and presents improved values for the LOD and LOQ. UHPLC can separate the diastereoisomers (epicoprostanol, coprostanol, and cholestanol) and the isomers (lupeol, α-amyrin, and β-amyrin). The method was successfully applied for the quantification of the biomarkers, and thus, it was applied to assess the OM sources and the impacts of anthropogenic activities in sediments from different environments, such as Antarctica and other Brazilian systems (Continental Shelf, São Sebastião Channel, and Santos Estuary). Unique profiles of the biomarkers were observed for the contrasting environments, and β-amyrin and cholesterol were more predominant in the Santos Estuary and Antarctica samples, respectively. The sterol ratios indicated a higher level of sewage contamination in the Santos Estuary.

Organochlorine pesticides residues and PCBs in benthic organisms of the inner shelf of the São Sebastião Channel, São Paulo, Brazil

Thirty seven benthic samples of the inner shelf area of Sao Sebastiao, Brazil, were collected between April 1994 and August 1998 and analysed for seventeen chlorinated pesticide residues and PCBs congeners. Pesticide residues and PCBs congeners levels were low (ng/g) and predominantly found in the crustacean samples. DDE was the most frequently residue with a maximum of 9,7 ng/g followed by HCHs with maximum of 17,1ng/g. As for the PCBs, the heavier congeners predominate: CB 138,153,170, 180 and 183. Maximum total PCBs was 17,4 ug/g in a crab sample. Higher levels of PCBs are related to feeding habits and local inputs of raw sewage or land runoff. Although EPA and FDA (U.S.A) below the guidelines for human consumption propose these levels, they do show that even in marine areas without intense agricultural or industrial activities these compounds are present at detectable levels.