The studied soil profile under the Main Market Square (MMS) in Krakow was characterised by the influence of medieval metallurgical activity. In the presented soil section lithological discontinuity (LD) was found, which manifests itself in the form of cultural layers (CLs). Moreover, in this paper LD detection methods based on soil texture are presented. For the first time, three different ways to identify the presence of LD in the urban soils are suggested. The presence of LD had an influence on the content and distribution of heavy metals within the soil profile. The content of heavy metals in the CLs under the MMS in Krakow was significantly higher than the content in natural horizons. In addition, there were distinct differences in the content of heavy metals within CLs. Profile variability and differences in the content of heavy metals and phosphorus within the CLs under the MMS were activity indicators of Krakow inhabitants in the past. This paper presents alternative methods for the assessment of the degree of heavy metal contamination in urban soils using selected pollution indices. On the basis of the studied total concentration of heavy metals (Zn, Pb, Cu, Mn, Cr, Cd, Ni, Sn, Ag) and total phosphorus content, the Geoaccumulation Index (Igeo), Enrichment Factor (EF), Sum of Pollution Index (PIsum), Single Pollution Index (PI), Nemerow Pollution Index (PINemerow) and Potential Ecological Risk (RI) were calculated using different local and reference geochemical backgrounds. The use of various geochemical backgrounds is helpful to evaluate the assessment of soil pollution. The individual CLs differed from each other according to the degree of pollution. The different values of pollution indices within the studied soil profile showed that LDS should not be evaluated in terms of contamination as one, homogeneous soil profile but each separate CL should be treated individually.

The studied soil profile under the Main Market Square (MMS) in Krakow was characterised by the influence of medieval metallurgical activity. In the presented soil section lithological discontinuity (LD) was found, which manifests itself in the form of cultural layers (CLs). Moreover, in this paper LD detection methods based on soil texture are presented. For the first time, three different ways to identify the presence of LD in the urban soils are suggested. The presence of LD had an influence on the content and distribution of heavy metals within the soil profile. The content of heavy metals in the CLs under the MMS in Krakow was significantly higher than the content in natural horizons. In addition, there were distinct differences in the content of heavy metals within CLs. Profile variability and differences in the content of heavy metals and phosphorus within the CLs under the MMS were activity indicators of Krakow inhabitants in the past. This paper presents alternative methods for the assessment of the degree of heavy metal contamination in urban soils using selected pollution indices. On the basis of the studied total concentration of heavy metals (Zn, Pb, Cu, Mn, Cr, Cd, Ni, Sn, Ag) and total phosphorus content, the Geoaccumulation Index (Igeo), Enrichment Factor (EF), Sum of Pollution Index (PIsum), Single Pollution Index (PI), Nemerow Pollution Index (PINemerow) and Potential Ecological Risk (RI) were calculated using different local and reference geochemical backgrounds. The use of various geochemical backgrounds is helpful to evaluate the assessment of soil pollution. The individual CLs differed from each other according to the degree of pollution. The different values of pollution indices within the studied soil profile showed that LDS should not be evaluated in terms of contamination as one, homogeneous soil profile but each separate CL should be treated individually. | Medieval industry, Lithological discontinuity, Cultural layers, Pollution indices, Heavy metals, Urban soils | 40 | 1023-1036 | 218

Land use type, physical and chemical stressors, and organic microcontaminants were investigated for their effects on the biological communities (biofilms and invertebrates) in several Mediterranean rivers. The diversity of invertebrates, and the scores of the first principal component of a PCA performed with the diatom communities were the best descriptors of the distribution patterns of the biological communities against the river stressors. These two metrics decreased according to the progressive site impairment (associated to higher area of agricultural and urban-industrial, high water conductivity, higher dissolved organic carbon and dissolved inorganic nitrogen concentrations, and higher concentration of organic microcontaminants, particularly pharmaceutical and industrial compounds). The variance partition analyses (RDAs) attributed the major share (10%) of the biological communities' response to the environmental stressors (nutrients, altered discharge, dissolved organic matter), followed by the land use occupation (6%) and of the organic microcontaminants (2%). However, the variance shared by the three groups of descriptors was very high (41%), indicating that their simultaneous occurrence determined most of the variation in the biological communities.

Land use type, physical and chemical stressors, and organic microcontaminants were investigated for their effects on the biological communities (biofilms and invertebrates) in several Mediterranean rivers. The diversity of invertebrates, and the scores of the first principal component of a PCA performed with the diatom communities were the best descriptors of the distribution patterns of the biological communities against the river stressors. These two metrics decreased according to the progressive site impairment (associated to higher area of agricultural and urban-industrial, high water conductivity, higher dissolved organic carbon and dissolved inorganic nitrogen concentrations, and higher concentration of organic microcontaminants, particularly pharmaceutical and industrial compounds). The variance partition analyses (RDAs) attributed the major share (10%) of the biological communities' response to the environmental stressors (nutrients, altered discharge, dissolved organic matter), followed by the land use occupation (6%) and of the organic microcontaminants (2%). However, the variance shared by the three groups of descriptors was very high (41%), indicating that their simultaneous occurrence determined most of the variation in the biological communities.

Pesticides generate transformation products (TPs) when they are released into the environment. These TPs may be of ecotoxicological importance. Past studies have demonstrated how difficult it is to predict the occurrence of pesticide TPs and their environmental risk. The monitoring approaches mostly used in current regulatory frameworks target only known ecotoxicologically relevant TPs. Here, we present a novel combined approach which identifies and categorizes known and unknown pesticide TPs in soil by combining suspect screening time-of-flight mass spectrometry with in silico molecular typology. We used an empirical and theoretical pesticide TP library for compound identification by both non-target and target time-of-flight (tandem) mass spectrometry, followed by structural proposition through a molecular structure correlation program. In silico molecular typology was then used to group TPs according to common molecular descriptors and to indirectly elucidate their environmental parameters by analogy to known pesticide compounds with similar molecular descriptors. This approach was evaluated via the identification of TPs of the triazole fungicide tebuconazole occurring in soil during a field dissipation study. Overall, 22 empirical and 12 yet unknown TPs were detected, and categorized into three groups with defined environmental properties. This approach combining suspect screening time-of-flight mass spectrometry with molecular typology could be extended to other organic pollutants and used to rationalize the choice of TPs to be investigated towards a more comprehensive environmental risk assessment scheme.

International audience | Once released into the environment, pesticides generate transformation products (TPs) which may be of (eco-)toxicological importance. Past studies have demonstrated the difficulty to predict pesticide TP occurrence and their environmental risk by monitoring-driven approaches mostly used in current regulatory frameworks targeting only known toxicologically relevant TPs. We present a novel combined approach which identifies and categorizes known and unknown pesticide TPs in soil by combining suspect screening time-of-flight mass spectrometry with in silico molecular typology. This approach applies an empirical and theoretical pesticide TP library for compound identification by both non-target and target time-of-flight (tandem) mass spectrometry and structural elucidation through a molecular structure correlation program. In silico molecular typology was then used to group the detected TPs according to common molecular descriptors and to indirectly elucidate their environmental properties by analogy to known pesticide compounds having similar molecular descriptors. This approach was evaluated via the identification of TPs of the triazole fungicide tebuconazole occurring in a field dissipation study. Overall, 22 empirical and 12 yet unknown TPs were detected and categorized into three groups with defined environmental properties. This approach combining suspect screening time-of-flight mass spectrometry with molecular typology could be extended to other organic pollutants and used to rationalize the choice of TPs to be intensively studied towards a more comprehensive environmental risk assessment scheme.

International audience | Once released into the environment, pesticides generate transformation products (TPs) which may be of (eco-)toxicological importance. Past studies have demonstrated the difficulty to predict pesticide TP occurrence and their environmental risk by monitoring-driven approaches mostly used in current regulatory frameworks targeting only known toxicologically relevant TPs. We present a novel combined approach which identifies and categorizes known and unknown pesticide TPs in soil by combining suspect screening time-of-flight mass spectrometry with in silico molecular typology. This approach applies an empirical and theoretical pesticide TP library for compound identification by both non-target and target time-of-flight (tandem) mass spectrometry and structural elucidation through a molecular structure correlation program. In silico molecular typology was then used to group the detected TPs according to common molecular descriptors and to indirectly elucidate their environmental properties by analogy to known pesticide compounds having similar molecular descriptors. This approach was evaluated via the identification of TPs of the triazole fungicide tebuconazole occurring in a field dissipation study. Overall, 22 empirical and 12 yet unknown TPs were detected and categorized into three groups with defined environmental properties. This approach combining suspect screening time-of-flight mass spectrometry with molecular typology could be extended to other organic pollutants and used to rationalize the choice of TPs to be intensively studied towards a more comprehensive environmental risk assessment scheme.

Drospirenone (DRO) is one of the most widely used progestins in contraceptive treatments and hormone replacement therapies. The pharmacokinetics and potential toxicological effects of DRO were investigated in juvenile sea bass (Dicentrarchus labrax) exposed through the diet (0.01–10 μg DRO/g) for up to 31 days. DRO was detected in the blood (4–27 ng/mL) of fish exposed to the highest concentration, with no significant bioaccumulation over time and no alteration of hepatic metabolizing enzymes, namely, CYP1A and CYP3A-catalysed activities and UDP-glucuronyltransferase (UGT). Pregnenolone (P5), progesterone (P4), 17α-hydroxyprogesterone (17P4), 17α-hydroxypregnenolone (17P5), androstenedione (AD) and testosterone (T) were determined in plasma and gene expression of cyp17a1, cyp19a1a and cyp11β analysed by qRT-PCR in gonads. The significant increase in plasmatic levels of 17P5, 17P4 and AD detected after 31 days exposure to 10 ng DRO/g together with the increased expression of cyp17a1 in females evidence the ability of DRO to alter steroid synthesis at low intake concentrations (7 ng DRO/day). However, the potential consequences of this steroid shift for female reproduction remain to be investigated.

8 pages, 4 figures, 3 tables | Drospirenone (DRO) is one of the most widely used progestins in contraceptive treatments and hormone replacement therapies. The pharmacokinetics and potential toxicological effects of DRO were investigated in juvenile sea bass (Dicentrarchus labrax) exposed through the diet (0.01–10 μg DRO/g) for up to 31 days. DRO was detected in the blood (4–27 ng/mL) of fish exposed to the highest concentration, with no significant bioaccumulation over time and no alteration of hepatic metabolizing enzymes, namely, CYP1A and CYP3A-catalysed activities and UDP-glucuronyltransferase (UGT). Pregnenolone (P5), progesterone (P4), 17α-hydroxyprogesterone (17P4), 17α-hydroxypregnenolone (17P5), androstenedione (AD) and testosterone (T) were determined in plasma and gene expression of cyp17a1, cyp19a1a and cyp11β analysed by qRT-PCR in gonads. The significant increase in plasmatic levels of 17P5, 17P4 and AD detected after 31 days exposure to 10 ng DRO/g together with the increased expression of cyp17a1 in females evidence the ability of DRO to alter steroid synthesis at low intake concentrations (7 ng DRO/day). However, the potential consequences of this steroid shift for female reproduction remain to be investigated | Maria Blanco acknowledges a pre-doctoral fellowship (FPI, BES-2012-054438) from the Spanish Government and Paula Medina the pre-doctoral fellowship MECE2, ANT0806. Denise Fernandes acknowledges a post-doctoral fellowship (SFRH/BPD/34289/2006) from the Portuguese Fundação para a Ciência e Tecnologia (FCT) of the Ministry of Science and Technology of Portugal. This study was supported by the Spanish National Plan of Research (Project Ref. CGL2011-24538) | Peer Reviewed

Drospirenone (DRO) is one of the most widely used progestins in contraceptive treatments and hormone replacement therapies. The pharmacokinetics and potential toxicological effects of DRO were investigated in juvenile sea bass (Dicentrarchus labrax) exposed through the diet (0.01-10 mu g DRO/g) for up to 31 days. DRO was detected in the blood (4-27 ng/mL) of fish exposed to the highest concentration, with no significant bioaccumulation over time and no alteration of hepatic metabolizing enzymes, namely, CYP1A and CYP3A-catalysed activities and UDP-glucuronyltransferase (UGT). Pregnenolone (P5), progesterone (P4), 17 alpha-hydroxyprogesterone (17P4), 17 alpha-hydroxypregnenolone (17P5), androstenedione (AD) and testosterone (T) were determined in plasma and gene expression of cyp17a1, cyp19a1a and cyp11 beta analysed by qRT-PCR in gonads. The significant increase in plasmatic levels of 17P5, 17P4 and AD detected after 31 days exposure to 10 ng DRO/g together with the increased expression of cyp17a1 in females evidence the ability of DRO to alter steroid synthesis at low intake concentrations (7 ng DRO/day). However, the potential consequences of this steroid shift for female reproduction remain to be investigated. (C) 2016 Elsevier Ltd. All rights reserved. | Spanish Government and Paula Medina the pre-doctoral fellowship MECE2, ANT0806; Spanish National Plan of Research (Project Ref. CGL2011-24538)

In this study, 50 pesticides were analyzed in the Ebro River basin in 2010 and 2011 to assess their impact in water, sediment and biota. A special emphasis was placed on the potential effects of both, individual pesticides and their mixtures, in three trophic levels (algae, daphnia and fish) using Risk Quotients (RQs) and Toxic Units (TUs) for water and sediments. Chlorpyrifos, diazinon and carbendazim were the most frequent in water (95, 95 and 70% of the samples, respectively). Imazalil (409.73 ng/L) and diuron (150 ng/L) were at the highest concentrations. Sediment and biota were less contaminated. Chlorpyrifos, diazinon and diclofenthion were the most frequent in sediments (82, 45 and 21% of the samples, respectively). The only pesticide detected in biota was chlorpyrifos (up to 840.2 ng g⁻¹). Ecotoxicological risk assessment through RQs showed that organophosphorus and azol presented high risk for algae; organophosphorus, benzimidazoles, carbamates, juvenile hormone mimic and other pesticides for daphnia, and organophosphorus, azol and juvenile hormone mimics for fish. The sum TUsite for water and sediments showed values < 1 for the three bioassays. In both matrices, daphnia and fish were more sensitive to the mixture of pesticide residues present.

In this study, 50 pesticides were analyzed in the Ebro River basin in 2010 and 2011 to assess their impact in water, sediment and biota. A special emphasis was placed on the potential effects of both, individual pesticides and their mixtures, in three trophic levels (algae, daphnia and fish) using Risk Quotients (RQs) and Toxic Units (TUs) for water and sediments. Chlorpyrifos, diazinon and carbendazim were the most frequent in water (95, 95 and 70% of the samples, respectively). Imazalil (409.73 ng/L) and diuron (150 ng/L) were at the highest concentrations. Sediment and biota were less contaminated. Chlorpyrifos, diazinon and diclofenthion were the most frequent in sediments (82, 45 and 21% of the samples, respectively). The only pesticide detected in biota was chlorpyrifos (up to 840.2 ng g−1). Ecotoxicological risk assessment through RQs showed that organophosphorus and azol presented high risk for algae; organophosphorus, benzimidazoles, carbamates, juvenile hormone mimic and other pesticides for daphnia, and organophosphorus, azol and juvenile hormone mimics for fish. The sum TUsite for water and sediments showed values < 1 for the three bioassays. In both matrices, daphnia and fish were more sensitive to the mixture of pesticide residues present. | This work has been supported by the Spanish Ministry of Economy and Competitiveness through the projects NET-SCARCE project (CTM2015-69780-REDC); “Evaluation of Emerging Contaminants in the Turia River Basins: From Basic Research to the Application of Environmental Forensics (EMERFOR)” (GCL2011- 29703-C02-02, http://mefturia.es) and European Communities 7th Framework Programme funding under Grant Agreement No. 603629-ENV-2013-6.2.1-Globaqua. A, Ccanccapa gratefully acknowledges the Conselleria DEducaci o, Cultura y Sport de Valencia for the financial support through “Santiago Grisolía” Scholarship Program. | Peer reviewed

Studying long-term trends of contaminants in Arctic biota is essential to better understand impacts of anthropogenic activities and climate change on the exposure of sensitive species and marine ecosystems. We concurrently measured temporal changes (2006–2014) in mercury (Hg) contamination of little auks (Alle alle; the most abundant Arctic seabird) and in their major zooplankton prey species (Calanoid copepods, Themisto libellula, Gammarus spp.). We found an increasing contamination of the food-chain in East Greenland during summer over the last decade. More specifically, bird contamination (determined by body feather analyses) has increased at a rate of 3.4% per year. Conversely, bird exposure to Hg during winter in the northwest Atlantic (determined by head feather analyses) decreased over the study period (at a rate of 1.5% per year), although winter concentrations remained consistently higher than during summer. By combining mercury levels measured in birds and zooplankton to isotopic analyses, our results demonstrate that inter-annual variations of Hg levels in little auks reflect changes in food-chain contamination, rather than a reorganization of the food web and a modification of seabird trophic ecology. They therefore underline the value of little auks, and Arctic seabirds in general, as bio-indicators of long-term changes in environmental contamination.

International audience | Studying long-term trends of contaminants in Arctic biota is essential to better understand impacts of anthropogenic activities and climate change on the exposure of sensitive species and marine ecosystems. We concurrently measured temporal changes (2006e2014) in mercury (Hg) contamination of little auks (Alle alle; the most abundant Arctic seabird) and in their major zooplankton prey species (Calanoid copepods, Themisto libellula, Gammarus spp.). We found an increasing contamination of the food-chain in East Greenland during summer over the last decade. More specifically, bird contamination (determined by body feather analyses) has increased at a rate of 3.4% per year. Conversely, bird exposure to Hg during winter in the northwest Atlantic (determined by head feather analyses) decreased over the study period (at a rate of 1.5% per year), although winter concentrations remained consistently higher than during summer. By combining mercury levels measured in birds and zooplankton to isotopic analyses, our results demonstrate that inter-annual variations of Hg levels in little auks reflect changes in food-chain contamination, rather than a reorganization of the food web and a modification of seabird trophic ecology. They therefore underline the value of little auks, and Arctic seabirds in general, as bio-indicators of long-term changes in environmental contamination.

International audience | In estuarine ecosystems, metallic and organic contaminants are mainly associated with fine grain sediments which settle on mudflats. Over time, the layers of sediment accumulate and are then transformed by diagenetic processes mainly controlled by microbial activity, recording the history of the estuary's chemical contamination. In an environment of this specific type, we investigated the evolution of the chemical contamination and the structure of both total and active microbial communities, based on PhyloChip analysis of a 4.6-m core corresponding to a 40-year sedimentary record. While the archaeal abundance remained constant along the core, a decrease by one order of magnitude in the bacterial abundance was observed with depth. Both total and active microbial communities were dominated by Proteobacteria, Actinobacteria, and Firmicutes in all sediment samples. Among Proteobacteria, alpha-Proteobacteria dominated both total (from 37 to 60 %) and metabolically active (from 19.7 to 34.6 %) communities, including the Rhizobiales, Rhodobacter, Caulobacterales, and Sphingomonadales orders. Co-inertia analysis revealed a relationship between polycyclic aromatic hydrocarbons, zinc and some polychlorobiphenyls concentrations, and the structure of total and active microbial communities in the oldest and most contaminated sediments (from 1970 to 1975), suggesting that long-term exposure to chemicals shaped the structure of the microbial community.

In estuarine ecosystems, metallic and organic contaminants are mainly associated with fine grain sediments which settle on mudflats. Over time, the layers of sediment accumulate and are then transformed by diagenetic processes mainly controlled by microbial activity, recording the history of the estuary’s chemical contamination. In an environment of this specific type, we investigated the evolution of the chemical contamination and the structure of both total and active microbial communities, based on PhyloChip analysis of a 4.6-m core corresponding to a 40-year sedimentary record. While the archaeal abundance remained constant along the core, a decrease by one order of magnitude in the bacterial abundance was observed with depth. Both total and active microbial communities were dominated by Proteobacteria, Actinobacteria, and Firmicutes in all sediment samples. Among Proteobacteria, alpha-Proteobacteria dominated both total (from 37 to 60 %) and metabolically active (from 19.7 to 34.6 %) communities, including the Rhizobiales, Rhodobacter, Caulobacterales, and Sphingomonadales orders. Co-inertia analysis revealed a relationship between polycyclic aromatic hydrocarbons, zinc and some polychlorobiphenyls concentrations, and the structure of total and active microbial communities in the oldest and most contaminated sediments (from 1970 to 1975), suggesting that long-term exposure to chemicals shaped the structure of the microbial community.