Márcia C. Bícego

Assessment of contamination by heavy metals and petroleum hydrocarbons in sediments of Montevideo Harbour (Uruguay)

As part of the first environmental assessment within Montevideo Harbour, in summer and winter of 1998, sediments samples were collected at eight locations to determine the spatial distribution of anthropogenic pollutants. Muddy sediments with high organic matter content dominate the study area. Heavy metal levels indicated that sediments were highly polluted with Zn (overall mean: 312+/-102 microg g(-1) dry sediment), Pb (85+/-31), Cu (89+/-25), Cr (162+/-62), and Hg (0.63+/-0.3) and moderately with Ni (30+/-2) and Ag (1.2+/-0.4). Depending on location and season, aliphatic hydrocarbons reached from 21 to 120 microg g(-1), while the unresolved complex mixture represented up to 76% of the total aliphatic fraction. Total PAH concentrations ranged from 1.56 to 90.44 microg g(-1); except at one location, petroleum derivatives were identified as main local source. The results pointed out that almost all the harbour area presented some substances that can cause adverse biological effects, especially in the inner region where all metals are above PEL levels. Principal components analysis confirmed that the inner harbour region is most severely affected by the pollutants and it was possible to differentiate three regions according to their environmental quality.

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.

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.

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.

Sunlight-induced compositional alterations in the seawater-soluble fraction of a crude oil

Abstract Oil released into the sea undergoes immediate compositional changes as a result of processes of volatilization, dissolution, particle adsorption, and microbial and photochemical decomposition. Based on our observation of the molecular composition of oil residues dissolved in subtropical ocean waters, we hypothesized photo-oxidation of alkyl-substituted polycyclic aromatic hydrocarbons (PAH) and heterocyclic aromatics in preference to their unsubstituted parent compounds. As the ratios of alkyl to parent PAH are used to assign sources to contaminant residues in environmental samples, we tested the hypothesis in a controlled experiment: membrane-filtered seawater collected near the island of Bermuda was saturated with a Nigerian crude oil and exposed to natural sunlight in a quartz flask. Comparison with a dark control under otherwise identical conditions served to differentiate between sunlight-induced and microbially mediated decreases in concentration and changes in composition. We conclude on the basis of UV fluorescence, GC-MS, and microbiological data that sunlight-induced oxidation is responsible for the rapid loss of the UV fluorescence signal for total aromatic hydrocarbons and for the preferential depletion of the alkyl-substituted PAH and heterocyclic aromatics. Structure-dependent selectivity in the photo-oxidation of dissolved oil residues may thus result in residual hydrocarbon blends which could be mistaken as originating from incomplete combustion processes.

Sedimentary biomarkers along a contamination gradient in a human-impacted sub-estuary in Southern Brazil: A multi-parameter approach based on spatial and seasonal variability

The composition and seasonal variations of sedimentary organic matter were investigated along the Cotinga sub-estuary, located in Paranaguá Bay, a large South American estuary where urban activities and the primary Brazilian grain shipping port are sources of pollution. Steroids and hydrocarbons were analyzed in surface sediments collected during the austral winter (2008) and summer (2009) in three distinct sectors, along this sub-estuary in a presumed gradient of fecal contamination. Concentrations ranged from 0.28 to 7.33 μgg (-1) (in dry sample weight thereafter), <DL (below detection limit) to 57.2 ng g(-1) and <DL to 1.69 μg g(-1) for aliphatic hydrocarbons (ΣAHs), polycyclic aromatic hydrocarbons (ΣPAHs) and coprostanol, respectively. Petrogenic inputs may be considered as source of AHs due to the presence of unresolved complex mixture in the majority of sites; however the levels observed do not indicate oil contamination. The highest ΣPAHs concentrations were found during the summer in the middle sector of the sub-estuary but were below the threshold effect levels (TEL), suggesting the absence of contamination by PAHs. Selected PAH isomer ratios indicated pyrolytic sources, whereas fecal sterols indicated decreasing sewage contamination from sub-estuary to the open ocean. The absence of correlation between organic markers and grain-size parameters suggested no preferential deposition sites of organic matter in the study area. The Principal Components Analysis suggested spatial variation in the distribution of sterols and AHs; however, temporal variations were only evident in the distribution of PAHs.

Modern sedimentation in the Cabo Frio upwelling system, Southeastern Brazilian shelf

The analyses of U k � 37 paleotemperatures and sedimentological parameters in box cores from the Cabo Frio upwelling zone, southeastern Brazil, were used to understand the modern sedimentation as well as to evaluate the role played by the upwelling process in the sedimentary patterns. Three box-cores located closer to the upwelling area show a general trend of cooling waters taking place in the last 700 years. Since the present upwelling is dependent on local and remote wind regime, a phase of dominating NE winds favors a more effective upward transport of the cold thermocline level South Atlantic Central Water towards the coast. The intensification in the upwelling regime for the last ca. 700 years can be associated with the strengthening of the NE winds off the area and a possible increase of the Brazil Current mesoscale activity. Nevertheless, the lack of significant correlation of the paleotemperatures and most of sedimentological parameters indicate that upwelling is not the only sedimentation mechanism in the area. Also, the comparison of sedimentological parameters reveals that eventual temporal changes are superimposed by the geographical variability. Sedimentation rates vary from 0.26 mm.yr –1 to 0.66 mm.yr –1 .

Multi-molecular markers and metals as tracers of organic matter inputs and contamination status from an Environmental Protection Area in the SW Atlantic (Laranjeiras Bay, Brazil).

The sources and concentrations of aliphatic hydrocarbons (AHs) and polycyclic aromatic hydrocarbons (PAHs), faecal and biogenic sterols, and trace metals at 10 sampling sites located in Laranjeiras Bay, a large Environmental Protection Area in the southern Atlantic region of Brazil, were determined to assess the sources of organic matter and the contamination status of estuarine sediments. Organic compounds were determined by GC-FID and GC-MS, and ICP-OES was used to evaluate trace metals. The total AHs concentration ranged from 0.28 to 8.19 μg g(-1), and n-C(29) and n-C(31) alkanes were predominant, indicating significant inputs from higher terrestrial plants. Unresolved complex mixtures (UCM) were not detected at any site, suggesting that the study area was not significantly contaminated by fossil fuels. The total PAH concentration varied from 3.85 to 89.2 ng g(-1). The ratio between selected PAH isomers showed that combustion of biomass, coal, and petroleum is the main source of PAHs in the study area. The concentrations of the faecal sterols coprostanol and epicoprostanol were below the detection limits, suggesting that sewage was not a significant contributor to sedimentary organic matter. The concentrations of the trace metals (As, Cr, Cu, Ni, Pb and Zn) were low, except near sites located at the mouths of rivers that discharge into the study area and near urbanised regions (Paranaguá city and the adjoining harbour). In general, the concentrations of PAHs were below the threshold effect concentrations (TEL) levels. Although the As, Cr and Ni concentrations were above the TEL levels, the study area can be considered as preserved from human activities.

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.