Availability of polycyclic aromatic hydrocarbons to earthworms in urban soils and its implications for risk assessment.

Polycyclic aromatic hydrocarbons (PAHs) are a global problem, and in urban soils they can be found at potentially hazard levels. Nevertheless, the real risks that these contaminants pose to the environment are not well known, since the bioavailability of PAHs in urban soils has been poorly studied. Therefore, the bioavailability of PAHs in some selected urban soils from Lisbon (Portugal) was evaluated. Moreover, the applicability of a first screening phase based on total contents of PAHs was assessed. Results show that bioavailability of PAHs is reduced (low levels in earthworms, low accumulation percentages, and low biota-to-soil accumulation factors values), especially in more contaminated soils. The aging of these compounds explains this low availability, and confirms the generally accepted assumption that accumulation of PAHs in urban areas is mostly related with a long-term deposition of contaminated particles. The comparison of measured PAHs concentrations in earthworm tissues with the ones predicted based on theoretical models, reinforce that risks based on total levels are overestimated, but it can be a good initial approach for urban soils. This study also highlights the need of more reliable ecotoxicological data.

Lead and PAHs contamination of an old shooting range: A case study with a holistic approach.

Soil pollution at firing ranges is an issue of growing importance, due to the accumulation in soils of contaminants derived from ammunition and clay targets. The concentration of Pb and PAHs was determined in five soils of an abandoned shooting range in Galicia (northwest Spain), and an ecotoxicological characterization was performed in order to obtain an assessment of risks. Therefore, the retention capacity of soils was assessed using test organisms of different trophic levels, and the role of soils as habitat for soil invertebrates was assessed by reproduction tests and bioaccumulation assays with earthworms. The sum of 15 PAHs ranged between 38 and 360mgkg-1, which exceed, together with Pb (160-720mgkg-1), the Galician generic reference value for urban and sporting field soils. Bioaccumulation in E. andrei showed contents up to 104,000µgPbkg-1dw, and up to 645µgPAHskg-1fw. High contents of Pb and PAHs in soil samples and in Eisenia andrei whole body, caused a reduction in the number of juveniles produced, whereas, Vibrio fischeri, Raphidocelis subcapitata and Daphnia magna displayed a slight toxic response to the soil elutriates tested. Therefore, the function of these soils to retain contaminants seemed not compromised, probably due to the high organic matter content and pH values, which are weakly acidic. The habitat function was affected, indicating that soil solution is not the only route of exposure to contaminants to E. andrei. The integration of chemical and ecotoxicological lines of evidence give rise to high risks values, restricting the use of these areas, and pointing for risks to surrounding ecosystems due to possible trophic transferences. The calculation of risks using the chemical and ecotoxicological data, required by Spanish legislation, could be a good approach to communicate with those responsible and/or involved in the management of contaminated sites.

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.

Catalog of total excitation-emission and total synchronous fluorescence maps with synchronous fluorescence spectra of homologated fluorescent pesticides in large use in Morocco: development of a spectrometric low cost and direct analysis as an alert method in case of massive contamination of soils and waters by fluorescent pesticides.

The purpose of this research is to develop a direct spectrometric approach to monitor soils and waters, at a lower cost than the widely used chromatographic techniques; a spectrometric approach that is effective, reliable, fast, easy to implement, and without any use of organic solvents whose utilization is subject to law limitation. It could be suitable at least as an alert method in case of massive contamination. Here, we present for the first time a catalog of excitation-emission and total synchronous fluorescence maps that may be considered as fingerprints of a series of homologated pesticides, in large use in Morocco, aiming at a direct detection of their remains in agricultural soils and neighboring waters. After a large survey among farmers, agricultural workers and product distributors in two important agricultural regions of Morocco (Doukkala-Abda and Sebou basin), 48 commercial pesticides, which are fluorescent, were chosen. A multi-component spectral database of these targeted commercial pesticides was elaborated. For each pesticide, dissolved in water at the lowest concentration giving a no-noise fluorescence spectrum, the total excitation-emission matrix (TEEM), the total synchronous fluorescence matrix (TSFM) in addition to synchronous fluorescence spectra (SFS) at those offsets giving the highest fluorescence intensity were recorded. To test this preliminary multi-component database, two real soil samples, collected at a wheat field and at a vine field in the region of Doukkala, were analyzed. Remains of the commercial Pirimor (Carbamate) and Atlantis (Sulfonylurea) were identified by comparison of the recorded TEEM, TSFM, and SFS to those of the preliminary catalog at one hand, and on the basis of the results of a field pre-survey. The developed approach seems satisfactory, and the fluorimetric fingerprint database is under extension to a higher number of fluorescent pesticides in common use among the Moroccan agricultural regions.

Geochemistry, mineralogy, solid-phase fractionation and oral bioaccessibility of lead in urban soils of Lisbon.

An urban survey of Lisbon, the largest city in Portugal, was carried out to investigate its environmental burden, emphasizing metallic elements and their public health impacts. This paper examines the geochemistry of lead (Pb) and its influence on human health data. A total of 51 soil samples were collected from urban recreational areas used by children to play outdoors. The semi-quantitative analysis of Pb was carried out by inductively coupled plasma mass spectrometry after an acid digestion. X-ray diffraction was used to characterize the soil mineralogy. The solid-phase distribution of Pb in the urban soils was investigated on a subset of 7 soils, out of a total of 51 samples, using a non-specific sequential extraction method coupled with chemometric analysis. Oral bioaccessibility measurements were obtained using the Unified BARGE Method developed by the Bioaccessibility Research Group of Europe. The objectives of the study are as follows: (1) investigation of Pb solid-phase distribution; (2) interpretation of Pb oral bioaccessibility measurements; (3) integration of metal geochemistry with human health data; and (4) understanding the influence of geochemistry and mineralogy on oral bioaccessibility. The results show that the bioaccessible fraction of Pb is lower when major metal fractions are associated with less soluble soil phases such as Fe oxyhydroxides, and more increased when the metal is in the highly soluble carbonate phase. However, there is some evidence that the proportion of carbonates in the soil environment is also a key control over the oral bioaccessibility of Pb, irrespective of its solid-phase fractionation.

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.

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.

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.

Pesticide application to agricultural fields: effects on the reproduction and avoidance behaviour of Folsomia candida and Eisenia andrei.

The objective of this work was to assess the impact of pesticide application to non-target soil organisms simulating what happens following pesticide application in agricultural fields and thus obtaining higher realism on results obtained. For that purpose, three commercial formulations containing the insecticides chlorpyrifos and endosulfan and the herbicide glyphosate were applied to a Mediterranean agricultural field. The soil was collected after spraying and dilution series were prepared with untreated soil to determine the impact of the pesticides on the avoidance behaviour and reproduction of the earthworm Eisenia andrei and the collembolan Folsomia candida. A significant avoidance was observed at the recommended field dose in case of endosulfan by earthworms (60 %) and in case of chlorpyrifos by collembolans (64 %). In addition, both insecticides affected the number of juveniles produced by the earthworms (EC(50) were below the recommended field dose). Glyphosate did not seem to affect either earthworms or collembolans in the recommended field dose. Folsomia candida was more sensitive to pesticide application than Eisenia andrei, what was corroborated by the EC(50) and LC(50) values. In conclusion, insecticides may affect the structure of the soil community by reducing the survival of collembolans and the reproductive capacity of collembolans and earthworms.

Characterization and validation of a Portuguese natural reference soil to be used as substrate for ecotoxicological purposes.

This study describes the first attempt to validate a Portuguese natural soil (PTRS1) to be used as reference soil for ecotoxicological purposes, aimed to both: (i) obtain ecotoxicological data for the derivation of Soil Screening Values (SSVs) with regional relevance, acting as a substrate to be spiked with ranges of concentrations of the chemicals under evaluation and (ii) act as control and as substrate for the dilution of contaminated soils in ecotoxicological assays performed to evaluate the ecotoxicity of contaminated soils, in tier 2 of risk assessment frameworks, applied to contaminated lands. The PTRS1 is a cambisol from a granitic area integrated in the Central Iberian Zone. After chemical characterization of the soil in terms of pseudo-total metals, PAHs, PCBs and pesticide contents, it was possible to perceive that some metals (Ba, Be, Co, Cr and V) surpass the Dutch Target Values (Dtvs) corrected for the percentage of organic matter and clay of the PTRS1. Nevertheless, these metals displayed total concentrations below the background total concentrations described for Portuguese soils in general. The same was observed for aldrin, endosulfan I, endosulfan II, heptachlor epoxide, and heptachlor; however the Dtvs corrected become negligible. The performance of invertebrate and plant species, commonly used in standard ecotoxicological assays, was not compromised by both soil properties and soil metal contents. The results obtained suggest that the PTRS1 can be used as a natural reference soil in ecotoxicological assays carried out under the scope of ecological risk assessment.

Lead availability in soils from Portugal's Centre Region with special reference to bioaccessibility.

Previous environmental biomonitoring studies indicated higher environmental lead (Pb) pollution levels at the districts of Aveiro and Leiria (Portugal). In evaluating the risk for human health, which is associated with contaminated soils after oral uptake, total soil concentrations have generally been held against criteria established from toxicological studies based upon the assumption that the uptake of the contaminant is similar in the toxicological studies and from the soils assessed. This assumption is not always valid, as most toxicological studies are carried out with soluble forms of the contaminants, whereas many soil contaminants are or become embedded in the soil matrix and thus exhibit limited availability. This study intends to estimate the soluble fraction of Pb in the soils from central Portugal, and to assess the bioaccessibility of Pb and, hence, infer exposure and risk for human health. Yet, as the physical-chemical properties of the soil exert some control over the solubility of Pb in the surface environment, the relation between such soil properties and the estimated soluble and/or bioaccessible fractions of Pb is also investigated. Other objective, with a more practical nature, was to give some contribution to find a suitable in vitro mimetic of the gastrointestinal tract environment. The results indicate relatively low total metal concentrations in the soils, even if differences between regions were observed. The Aveiro district has the higher total Pb concentration and the metal is in more soluble forms, that is, geoavailable. Soils with higher concentrations of soluble Pb show higher estimates of bioaccessible Pb. Soil pH seems to influence human bioaccessibility of Pb.

In situ aquatic bioassessment of pesticides applied on rice fields using a microalga and daphnids.

This study assessed the effects of episodic contamination on a drainage canal adjacent to an area of intensive rice production (Coimbra, Portugal). Four monitoring periods were considered [i) before herbicide application (day-14), ii) at the first application day (day 0), iii) 3 or 5 and iv) 6days after]. Each one consisted in three complementary evaluation lines: a) physico-chemical analyses, b) whole effluent toxicity (WET) assays with Pseudokirchneriella subcapitata, c) in situ bioassays to assess microalgae (P. subcapitata) growth, and the feeding rate and survival of Daphnia longispina and Daphnia magna. Study sites were located upstream, in a protected wetland (L1), and downstream, in the vicinity of rice fields (L2). Along with the application of agrochemicals, there was a general decrease of the water quality, especially in L2, due to nutrient and herbicide inputs. Herbicide peaks (on days 0, 5 and 6) in L2 water samples were recorded concomitantly or immediately after their application. Regarding the in situ bioassessment, the algae growth decrease from day 0 onwards in L1, whilst in L2 its inhibition was generally coherent with the decline of the water quality. Apparently, WET tests indicated that the limitation of nutrients could be affecting algae growth in L1, however, conclusions should be cautious. The feeding depression of daphnids occurred on days 0 and 5 for D. longispina and only on day 0 for D. magna, while significant reductions on survival were restricted to day 0 for both species. The impairments occurring on day 0 were linked to a potential increased toxicity driven by the ingestion of particle-bound herbicides and suspended particles. The feeding rate of daphnids provided an earlier indication of toxic impairments, though it is prompted the use of complementary endpoints and trophic levels in order to understand the cumulative effects due to various herbicide pulses.

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).

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.

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 invertebrate's 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.