Anabela Cachada

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.

The variability of polychlorinated biphenyls levels in urban soils from five European cities

The concentration of PCBs in topsoils from five European cities was assessed and the highest levels were found in Glasgow (Scotland), followed by Torino (Italy), Aveiro (Portugal), Ljubljana (Slovenia) and Uppsala (Sweden). All cities showed the presence of local sources in addition to diffuse contamination from global atmospheric transport. The association of general soil parameters with PCBs in Glasgow and with heavier congeners in Torino and Ljubljana indicates that retention of these compounds is occurring. The profiles obtained resemble Aroclor 1254 and 1260, which are important local sources. Nevertheless, differences in PCB profiles were observed among cities, due to the combined effects of the age of the contamination (which determines the time available for volatilisation and degradation), different sources of PCBs and differences in climate (which influence volatilisation and deposition).

The prediction of PAHs bioavailability in soils using chemical methods: state of the art and future challenges.

The evaluation of the available fraction of hydrophobic organic contaminants (HOCs) is extremely important for assessing their risk to the environment and human health. This available fraction, which can be solubilized and/or easily extracted, is believed to be the most accessible for bioaccumulation, biosorption and/or transformation by organisms. Based on this, two main types of chemical methods have been developed, closely related to the concepts of bioaccessibility and freely available concentrations: non-exhaustive extractions and biomimetic methods. Since bioavailability is species and compound specific, this work focused only in one of the most widespread group of HOCs in soils: polycyclic aromatic hydrocarbons (PAHs). This study aims at producing a state of the art knowledge base on bioavailability and chemical availability of PAHs in soils, clarifying which chemical methods can provide a better prediction of an organism exposure, and which are the most promising ones. Therefore, a review of the processes involved on PAHs availability to microorganisms, earthworms and plants was performed and the outputs given by the different chemical methods were evaluated. The suitability of chemical methods to predict bioavailability of the 16 US EPA PAHs in dissimilar naturally contaminated soils was not yet demonstrated, being especially difficult for high molecular weight compounds. Even though the potential to predict microbial mineralization using non-exhaustive extractions is promising, it will be very difficult to achieve for earthworms and plants, due to the complexity of accumulation mechanisms which are not taken into account by chemical methods. Yet, the existing models could be improved by determining compound, species and site specific parameters. Moreover, chemical availability can be very useful to understand the bioavailability processes and the behavior of PAHs in soils. The inclusion of chemical methods on risk assessment has been suggested and it is promising, despite some methods overpredict risks.

Optimisation of a microbial bioassay for contaminated soil monitoring: bacterial inoculum standardisation and comparison with Microtox® assay

This work represents the first step to set up a toxicity testing procedure and to evaluate the sensitivity of the test microorganism to several classes of environmental pollutants. First, three different techniques were employed to standardise the microbial inoculum, then two different toxicity assessment protocols have been compared: Microtox and a dehydrogenase (DHase) activity inhibition test. The main goal was the optimisation of a microbial bioassay based on the dehydrogenase activity (DHase) inhibition in Pseudomonas fluorescens bacterial strain ATCC 13525. Triphenyl tetrazolium chloride (TTC) was used as electron acceptor and its reduction produces Triphenyl formazane (TPF). The P. fluorescens DHase inhibition bioassay was investigated for being a reliable and rapid method for assessing toxicity. The optimisation of the operating conditions resulted in a repeatable bioassay. Then, P. fluorescens and Vibrio fischeri sensitivity were firstly compared by testing Zn++, one of the reference compounds for Microtox test. In addition, other compounds (Ni++, Cd++, Cu++, phenol) were also tested with both bioassays. A high statistical significance of data was obtained with the logistic curve. The present work has demonstrated that P. fluorescens is as sensitive as Microtox culture (V. fischeri), for some of the metal ions. With reference to organic compounds, the lower sensitivity of P. fluorescens to phenol makes its use difficult in organic polluted samples.

Validation of avoidance assays for the screening assessment of soils under different anthropogenic disturbances.

A chemical characterization of the soil compartment per se does not supply any information about the synergistic/antagonistic effects of mixtures of chemicals, resulting in an under- or overestimation of the risks. Therefore the existence of rapid and ecologically relevant toxicity assays becomes of paramount importance, allowing the evaluation of invertebrates behavioural parameters with equal consequences in terms of functionality of the edaphic community. The aim of this study was to evaluate the sensitivity of avoidance assays, with the earthworm Eisenia andrei, in discriminating natural soils under different anthropogenic disturbances. Although earthworms were able to discriminate soils with similar contamination, it is nonetheless questionable whether the preference for some soils is determined by the reduced bioavailability of contaminants, the great affinity of the species for organic matter-rich soils, or the inability of chemoreceptors to detect some contaminants from complex environmental mixtures, usually present in natural contaminated soils.

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.

Sources of potentially toxic elements and organic pollutants in an urban area subjected to an industrial impact

Urban and industrial development has caused a major impact on environmental soil quality. This work assesses the extent and severity of contamination in a small urban area subjected to an industrial impact and identifies the major anthropogenic inputs. Twenty-six soil samples were collected from agricultural and urban sites, and concentrations of potentially toxic elements (As, Cd, Cu, Cr, Fe, Mn, Ni, Pb and Zn), PAHs and PCBs, were determined. In spite of the low median concentrations observed, some sites represent a potential hazard for human health and ecosystems. Concentrations of contaminants were higher than those found in a nearby city, indicating that the study area is affected by the surrounding industry. The use of multivariate statistical analyses allowed for the identification of the main factors controlling the variability of potentially toxic elements and organic pollutants in the soils. The presence of Cr, Fe, Mn and Ni was associated with geogenic inputs, and Cu, Pb, Zn, As, PAHs and PCBs were associated with anthropogenic inputs. Industry and traffic were the most important anthropogenic sources. Soil characteristics were identified as important factors controlling the spatial variability of elements, both from recognised natural and anthropogenic origin. Differences between land uses were observed, which may be attributed to both management practices and proximity to sources.

Risk assessment of urban soils contamination: The particular case of polycyclic aromatic hydrocarbons.

The assessment of soil quality and characterization of potential risks to the environment and human health can be a very difficult task due to the heterogeneity and complexity of the matrix, the poor understanding about the fate of contaminants in the soil matrix, scarcity of toxicological/ecotoxicological data and variability of guidelines. In urban soils these difficulties are enhanced by the patchy nature of urban areas and the presence of complex mixtures of organic and inorganic contaminants resulting from diffuse pollution caused by urban activities (e.g. traffic, industrial activity, and burning of carbon sources for heating). Yet, several tools are available which may help to assess the risks of soil contamination in a simpler, cost effective and reliable way. Within these tools, a tiered risk assessment (RA) approach, first based on a chemical screening in combination with geostatistical tools, may be very useful in urban areas. However, there is still much to improve and a long way to go in order to obtain a reliable RA, especially in the case of hydrophobic organic compounds such as polycyclic aromatic hydrocarbons (PAHs). This paper aims at proposing a RA framework to assess the environmental and human health risks of PAHs present in urban soils, based on existing models. In addition, a review on ecotoxicological, toxicological, and exposure assessment data was made, as well as of the existing soil quality guidelines for PAHs that can be used in the RA process.

Structural effects of the bioavailable fraction of pesticides in soil: suitability of elutriate testing.

This study focused the ecotoxicological evaluation of four different pesticides (chlorpyrifos, glyphosate, vinclozolin, endosulfan), sprayed into an agricultural soil, using a standard battery of aquatic bioassays for testing of soil elutriates: Vibrio fischeri -Microtox(®); Pseudokirchneriella subcapitata growth inhibition; Daphnia magna acute and chronic toxicity. Despite relevant pesticide residues were recovered from the soil matrix (concentrations higher than 1000 μg kg(-1)), much lower concentrations could be retrieved from elutriates (highest records for endosulfan of ca. 250 ng L(-1)and 1400 ng L(-1); dissolved and particulate concentration, respectively) and little effects were generally found in the bioassays. Lethal effects (D. magna 48 h-EC50 of 36.8%) could be noticed following exposure to the endosulfan elutriate. Elutriates induced no toxicity on V. fischeri; algal growth was generally inhibited at high elutriate dilutions and stimulated at the lower elutriate dilutions; and no overall impairment of D. magna life-history was noticed. Results revealed that cross-contamination during field application, input of organic matter and nutrients by elutriates in test solutions, and choice of test species and endpoints may constrain the ecotoxicological assessment. Suitability of established aquatic bioassay test batteries for these purposes, and questioning on whether direct assays with soil organisms could be more protective tools is discussed.