P. Pato

Levels, sources and potential human health risks of organic pollutants in urban soils.

Urban soil quality may be severely affected by PAH and PCB contamination, impairing environmental and human health. A comprehensive study was conducted in two contrasting Portuguese urban areas (Lisbon and Viseu) in order to assess the levels of these contaminants and potential risks to human health, to identify sources and study their behavior in soils. The concentrations of PAHs and PCBs were related to the size of the city. The concentrations found in the larger city (Lisbon) were similar to other urban areas. Differences between profiles of the two urban areas were observed for both groups of contaminants, which could be attributed to differences of sources or climate. Lisbon seems to be affected by nearby sources (traffic, industry and incineration processes) whereas in the smaller city atmospheric transport may be playing an important role. Cluster analysis revealed that PAHs and PCBs were associated with anthropogenic toxic elements (Cu, Pb, Zn and Hg in Lisbon; Pb and Hg in Viseu), therefore reflecting common sources. It was also found that organic carbon was an important factor for PAHs and high chlorinated PCB retention in soils. The incremental probability of developing cancer over lifetime, based on a reasonable maximum exposure to PAHs present in Lisbon residential soils, was 9.0 × 10(-6) and 2.4 × 10(-6) for an occupational exposure, both slightly higher than the target risk of 1 × 10(-6). Similarly, the mutagenic risk of PAHs in Lisbon was 3.3 × 10(-5) for residential soils and 1.8 × 10(-6) in recreational areas.

Mercury pollution in Ria de Aveiro (Portugal): a review of the system assessment

The Ria de Aveiro (Portugal) is a coast al lagoon adjacent to the Atlantic Ocean and it has an inner bay (Laranjo bay) that received a highly contaminated effluent discharged by a mercury cell chlor-alkali plant from the 1950s until 1994. The aim of this study is to review in a holistic way several research studies that have been carried out in the Ria de Aveiro, in order to evaluate the remobilization of the mercury accumulated within the system and the recovery of the lagoon. The spatial distribution of the total mercury in the surrounding terrestrial environment has also been considered. Results indicate that the main mercury contamination problems in the Ria de Aveiro are confined to the Laranjo bay. Mercury export to the coastal waters and its impact on the nearshore compartments (water column, sediment and biota) are low. No direct effects of the mercury from nearby industrial activities were detected in Aveiro’s urban soils, although historical mercury contamination is still affecting soil quality in the immediate vicinity of the chlor-alkali plant, located in Estarreja. Moreover, macrophyte harvesting for human direct or indirect use and the consumption of mussels, crabs and the sea bass from the Laranjo bay may constitute a health risk. Further studies focusing on developing skills for the restoration of the ecosystem are presently underway.

Major inputs and mobility of potentially toxic elements contamination in urban areas

Soil quality in urban areas is affected by anthropogenic activities, posing a risk to human health and ecosystems. Since the pseudo-total concentrations of potentially toxic elements may not reflect their potential risks, the study of element mobility is very important on a risk assessment basis. This study aims at characterising the distribution and major sources of 34 elements in two Portuguese urban areas (Lisbon and Viseu), with different geological characteristics, industrial and urban development processes. Furthermore, the potential availability of As, Co, Cr, Cu, Ni, Pb and Zn was assessed, by measuring the fraction easily mobilised. Lisbon is enriched in elements of geogenic and anthropogenic origin, whereas in the smaller city, the high levels observed are mainly related to a geogenic origin. Background values can be more relevant than the dimension of the city, even when anthropogenic components may be present, and this parameter should be considered when comparing results from different cities. Regarding the potential available fraction, a high variability of results was observed for elements and for sampling sites with an influence of the soil’s general characteristics. Elements showing very high concentrations due to geological reasons presented, in general, a low mobility and it was not dependent on the degree of contamination. For elements with major anthropogenic origin, only Zn was dependent on the pseudo-total content. Yet, the highest available fractions of some elements, both with major geogenic and anthropogenic origin, were observed in specific contaminated samples. Therefore, a site-specific evaluation in urban soils is important due to the high spatial variability and heterogeneity.

Organochlorine accumulation on a highly consumed bivalve (Scrobicularia plana) and its main implications for human health

Contamination by polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) was investigated along a spatial gradient in water, sediments and in commercially important bivalve species Scrobicularia plana, from Ria de Aveiro (Portugal). Organochlorines dissolved in water were below detection limit and concerning suspended particulate matter, only PCBs were quantified, ranging from 3.8 to 5.8 ng∙g(-1) DW (Σ13PCBs). There was a distinct spatial gradient regarding PCB accumulation in sediments. The highest concentrations were found in deeper layers and closest to the pollution source, decreasing gradually along a 3 km area. Contamination in sediments exceeded the Canadian and Norwegian sediment quality guidelines, inducing potential toxic effects in related biota. PCBs tended to bioaccumulate throughout S. plana lifespan but with different annual rates along the spatial gradient. The maximum values were found in older individuals up to 3+ years old, reaching 19.4 ng∙g(-1) DW. HCB concentrations were residual and no bioaccumulation pattern was evident. Congeners 138, 153 and 180 were the most accumulated due to their abundance and long-term persistence in the environment. In the inner area of the Laranjo Bay (0.6 km(2)), the species was able to remove up to 0.4 g of PCBs annually from sediments into their own tissues, which is consequently free for trophic transfer (biomagnification). Concerning human health, and despite the high concentrations found in sediments, PCB levels in bivalves do not exceed the limit established by the European Union for fishery products and are largely below tolerable daily intake. Although PCBs in Scrobicularia plana are present at low levels, their impact to human health after consumption over many years might be harmful and should be monitored in future studies.

Mercury partition in the interface between a contaminated lagoon and the ocean: The role of particulate load and composition

After having estimated the patterns of flow to the ocean and found some seasonal and tidal differences, mainly with regard to the relative importance of dissolved and particulate fractions, mercury partitioning at the interface between a contaminated lagoon and the Atlantic Ocean was investigated during four tidal cycles in contrasting season and tidal regimes. Mercury was found to be located predominantely in the particulate fraction throughout the year, contributing to its retention within the system. Seasonal conditions, variations in marine and fluvial signals and processes affecting bed sediment resuspension influenced the character and concentration of suspended particulate matter in the water column. Variation in the nature, levels and partitioning of organic carbon in the particulate fraction affected levels of particulate mercury as well as mercury partitioning. These results highlight the dominant role of suspended particulate matter in the distribution of anthropogenic mercury and reinforce the importance of competitive behavior related to organic carbon in mercury scavenging.

Inputs from a Mercury-Contaminated Lagoon: Impact on the Nearshore Waters of the Atlantic Ocean

Abstract Ria de Aveiro, a Portuguese coastal lagoon that exchanges water with the Atlantic Ocean, received the effluent from a chloralkali industry for over 50 years; consequently several tons of mercury had been buried in the sediments of an inner basin. To assess the importance (and seasonal variation) of the lagoon waters as carriers of mercury to the nearby coastal area, we measured total mercury levels in several compartments: in surface sediments, in surface and deep waters (including dissolved and particulate matter), and in biota. Dissolved (reactive and total) mercury concentrations both in surface and deep waters were low (<1 to 15 ng L−1). Mean mercury values in suspended particulate matter varied between 0.2 and 0.6 μg g−1 and in sediments between 1 and 9 ng g−1. Aquatic organisms displayed levels below regulatory limits but exhibited some bioaccumulation of mercury, with concentrations ranging from 0.05 to 0.8 μg g−1 [dry weight (dw)]. No seasonal pattern was found in this study for mercury-related determinations. Levels found in the estuary mouth during ebb tide provide evidence for the transport of mercury to the coastal zone. No significant changes in the partition of mercury between dissolved and particulate phases were found in the coastal waters in comparison with the values found in the estuary mouth. In spite of the high levels of mercury found inside some areas of the lagoon, the wide web of islands and channels allows some spreading of contaminants before they reach the coastal waters. Moreover, the low efficiency of local marine sediments in trapping mercury contributes to a dilution of mercury transported in suspended particulate matter over a broader area, reducing the impact in the nearby marine coastal zone.

Sewage contamination of sediments from two Portuguese Atlantic coastal systems, revealed by fecal sterols

Fecal sterols in sediments were used to assess the degree of sewage contamination in Ria de Aveiro lagoon and Mondego River estuary for the first time. Coprostanol, the major fecal sterol, averaged 1.82 ± 4.12 μg g(-1), with maxima of 16.6 μg g(-1). The northwestern sector of the Ria and a marina at Mondego estuary showed the highest level of sewage contamination. This scenario was confirmed by several diagnostic ratios based on fecal sterols and other phytosterols. Our data revealed that in spite of the improvements achieved in the last decades, there is still a need for control the organic inputs into the aquatic environment in the studied regions.

PCB bioaccumulation in three mullet species—A comparison study

Polychlorinated biphenyls (PCBs) are lipophilic contaminants that tend to accumulate in organisms. PCBs were detected in Chelon labrosus, Liza aurata and Liza ramada, along different age groups. L. ramada presented the highest concentration, and it increased with age, whereas C. labrosus and L. aurata concentration remained constant. L. ramada high concentration can be attributed to its ecological niche, since this species is able to accumulate PCBs along its different age groups even in low environmental contamination conditions. PCBs 101, 118, 138, 149, 153, 170 and 180 were the congeners that more contributed to these species contamination, being PCB 138 and 153 the congeners with higher concentration. Mullets are edible in many countries, being important in fisheries and aquaculture. L. ramada is the most common mullet for capture and human consumption. All species presented concentrations below the regulation limit establish by the European Union, and therefore safe for human consumption.

Uptake and depuration of PCB-153 in edible shrimp Palaemonetes varians and human health risk assessment

A medium-term mesocosm exposure study was conducted to elucidate bioaccumulation and depuration of polychlorinated biphenyl congener 153 (PCB-153) in edible shrimp Palaemonetes varians. Over the 15-day exposure period, shrimp under different exposure concentrations exhibited a significant increase in PCB-153 concentration compared with control organisms. Distinct bioaccumulation patterns and uptake rates were observed depending on the exposure concentrations. For low PCB-153 exposure levels (0.25μgL(-1)), accumulation followed a saturation model, reaching an apparent steady state after fifteen days exposure. For intermediate (2.5μgL(-1)) and high PCB-153 levels (25μgL(-1)), accumulation was faster and linear. In addition, the bioaccumulation rate was not proportional to PCB-153 concentration, and the bioaccumulation was higher at intermediate exposure concentrations. Regarding the depuration phase, P. varians lost up to 30% of PCB-153 after 72h and levels continued slowly to decrease until the end of the 30-d experimental period. However, PCB-153 levels in shrimp did not reach background values, and those exposed to moderate and high PCB-153 concentrations presented contamination levels much higher than the regulatory limit for human food consumption (75ngg(-1) ww for Σ6 PCB).

Organochlorine contaminants in different tissues from Platichthys flesus (Pisces, Pleuronectidea)

Polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) are organic contaminants that tend to accumulate in fish. Estuaries are exposed to high anthropogenic activities, therefore tending to accumulate more contaminants than the adjacent coastal waters. Platichthys flesus, a fish with high economic value, was analysed for PCBs and HCB along its different age groups, in liver, gills, gonads and muscle. Younger fishes were caught in the estuary, whereas older fishes were caught in the adjacent coastal waters and acquired at Figueira da Foz Regional Office of Docapesca-Portos e Lotas, SA. Both contaminants concentrations follow the pattern: liver>gills>muscle. Hepatosomatic index had the lowest values in younger fishes and the highest values in older fishes. Condition factor values remain stable with age. Younger fishes had higher PCBs concentrations than the older fishes. In opposition HCB was only detected in fish from 3+ to 5+ and its concentration tended to increase with age. Overall P. flesus is considered safe for human intake.