César C. Martins

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.

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.

Anthropogenic organic matter inputs indicated by sedimentary fecal steroids in a large South American tropical estuary (Paranaguá estuarine system, Brazil).

Urban sewage is considered one of the most important sources of marine pollution in South America, because most coastal cities do not have proper facilities to treat and dispose of sewage. The Paranaguá estuarine system is an important estuarine environment of the South American coast where fishing, urban and tourist activities, industries and the main Brazilian grain shipping port are potential sources of pollution in this area. The anthropogenic input of sedimentary organic matter, represented by sewage contribution, was evaluated by fecal steroid concentrations. The coprostanol levels were comparatively low (<0.10 μg g(-1)), except at the sites close to Paranaguá city, where the coprostanol concentration reached 2.22 μg g(-1) showing strong sewage contamination. Fecal steroid levels were comparable to the lower to midrange concentrations reported for coastal sediments worldwide. The results of this work demonstrated that sewage pollution can be considered a problem for a small part of the Paranaguá estuary.

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.

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.

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.

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.

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.