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Pollutants’ dynamics in rivers flowing through industrial areas is linked to the entrainment and transport of contaminants attached to solid particles. The transport of sediment is mainly associated to high discharges and flood episodes, and these events constitute one of the main factors causing fluxes of buried pollutants in rivers. We performed a field study in the lower River Cinca (Ebro basin, Northeast Spain) to quantify the mobilization and transfer of several contaminants present in the river bed sediments. We focused on contaminants previously identified (PCBs, DDXs, PBDEs, HBCDs and PFRs) to occur in the river. River bed sediment samples were collected during low flows and a subsequent sampling campaign was used to capture sediment borne contaminants during a flood event. Water samples were taken at the same locations as the static sediment samples and used to determine the suspended sediment concentrations and the contaminants content (i.e. mass of contaminant per sediment mass unit) during the event. We estimated mass fluxes for both sediment and pollutants, and determined that sediment transport followed a clockwise hysteresis. This is typically observed in high flow events after dry summer periods. With sediments there was a large mobilization of PFRs (36 kg in 48 h in one of the main tributaries) and PCBs not previously observed in the static sediment. Observed contaminant load ranges during the two-day sampling campaign were: PCB (34–152 g), DDT (12–213 g), PBDE (50–1740 g), HBCD (0–2.2 g) and PFR (2410–35,895 g). An environmental risk assessment was carried out by comparing the pollutant concentrations found in the sediments with the Canadian quality guidelines (ISQC), showing a significant noncompliance for PCBs in dynamic sediments. Our results point out to the need of a regular assessment of the downstream transfer of the sediment-borne pollutants in drainage basins historically affected by intense industrial activities and associated contaminati

Determining the exposure and magnitude at which various pollutants are differentially assimilated at the breeding and non-breeding grounds of migratory wildlife is challenging. Here, the possibility of applying the migratory connectivity framework to understanding contamination in birds is illustrated by considering flame retardants in inviable eggs of a migratory raptor, the black kite (Milvus migrans). The occurrence and concentration of legacy and emerging compounds in eggs from the southeastern peri-urban area of Madrid city, central Spain, were compared with those from Doñana National Park in southern Spain. A much higher occurrence and concentration of multiple polybrominated diphenyl ethers and Dechlorane 602 were found in Madrid than Doñana, but the opposite patterns were found for Dechlorane Plus. Individuals from these and other breeding areas in western Europe showed a strong intermixing pattern over widespread wintering areas in Africa, as assessed by ringing recoveries and movements tracked by satellite devices. This diffuse migratory connectivity reveals breeding areas as the main contamination grounds. High contamination burdens sequestered in eggs point to rapid assimilation of these compounds before laying, associated with important emission sources in Madrid, especially landfills of partially incinerated urban refuse, and other anthropogenic operations. Diet composition regarding aquatic vs. terrestrial prey, and bioaccumulation and biomagnification processes are suggested to explain differential assimilation of some compounds, especially Dechlorane Plus in Doñana, although a local emission source polluting this area cannot be ruled out. Insight from the migratory connectivity framework can help to disentangle large-scale patterns of contaminant uptake and refocus attention on key regions and potential causes of chemical hazards in declining migratory species and human populations.

Discarded vehicle tires have become an increasing concern worldwide due to the enormous amount of wastes generated and the increasing evidence of health problems associated to their disposal and accidental combustion. Previous studies conducted involving either simulated or open uncontrolled tire fires have identified aromatics belonging to two main classes, volatile organic compounds and polycyclic aromatic compounds (PAHs), as the most relevant chemicals generated in these burning processes. As a consequence, and due to their recognized toxicity, most studies reported up to now have mainly focused on these two categories of compounds being information concerning the possible occurrence of other aromatic classes rather limited. In this study, the enhanced separation power and structural confirmation capabilities provided by comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry (GC × GC – ToF MS) has been used, for the first time, for the non-targeted analysis of soils impacted by a tire fire and an ash collected at the scene of the fire. In total, 118 volatile and semi-volatile aromatic compounds have been differentiated. Among them, 104 compounds have been either positively or tentatively identified. PAHs with 3–5 rings and their alkyl-derivatives were the most numerous and relevant classes in the investigated samples. A significant number of sulfur, oxygen- and nitrogen-containing PAHs were also detected in the samples. The application of a script function to the raw GC × GC – ToF MS data allowed the fast filtering and automatic recognition of compounds containing halogens in their structure. This part of the study evidenced that only a limited number of regulated persistent organic pollutants were present in the investigated samples. However, it also revealed the presence of emerging organophosphorous flame retardants, whose levels in tire fire impacted soils are reported for the first time.

This study evaluates the current situation regarding PBDE and HBCD levels in different river fish species. We collected published data in the last five years in different countries around the world. These levels of pollution were compared with Environmental Quality Standards (EQS) for biota established by the European Directive in the field of water policy. Although HBCD situation is not critical, with only some values exceeding the limit about 5 times, the PBDE levels clearly exceeded the established EQS, with 25% of fish samples exceeding up to ten thousand times. Although it is expected that levels of pollution by PBDEs will decrease over the next years due to the ban in their use, it is not expected that this decrease will reach the EQS values by the end of 2021, as demanded by the European Directive. Hence, it is necessary to implement new strategies in order to minimize the impact of PBDEs on the environment. © 2017 The Authors

PBDEs (congeners 28, 47, 99, 100, 153, 154, 183, 209), HBCD (?, ?, ?), emerging brominated flame retardants (PBEB, HBB and DBDPE), dechloranes (Dec 602, 603, 604, syn- and anti-DP), TBBPA, 2,4,6-TBP and MeO-PBDEs (8 congeners) were analysed in commercial seafood samples from European countries. Levels were similar to literature and above the environmental quality standards (EQS) limit of the Directive 2013/39/EU for PBDEs. Contaminants were found in 90.5% of the seafood samples at n.?d.-356 ng/g lw (n.?d.-41.1 ng/g ww). DBDPE was not detected and 2,4,6-TBP was detected only in mussels, but at levels comparable to those of PBDEs. Mussel and seabream were the most contaminated species and the Mediterranean Sea (FAO Fishing Area 37) was the most contaminated location. The risk assessment revealed that there was no health risk related to the exposure to brominated flame retardants via seafood consumption. However, a refined risk assessment for BDE-99 is of interest in the future. Moreover, the cooking process concentrated PBDEs and HBB.Copyright © 2016 Elsevier Ltd. All rights reserved.

Pyrethroid pesticides were analysed in liver of striped dolphin (Stenella coeruleoalba) from the Alboran Sea (south of Spain, Mediterranean Sea). The occurrence and bioaccumulation of pyrethroid insecticides in marine mammal tissues from the northern hemisphere had never been determined before. Pyrethroids were detected in 87% of the specimens with a mean total concentration of 300 ng g lw ± 932 (range 2.7–5200 ng g lw). Permethrin and tetramethrin were the main contributors to the pyrethroid profiles, with enantiospecific accumulation for the first and isomer specific accumulation for the latter. Bioaccumulation of pyrethroids was unlike that of persistent organic pollutants (POPs), as pyrethroid concentrations were not correlated to the maturity stage of the specimens. Concentrations slightly increased from calves to juveniles, whereas juveniles presented similar concentrations to adults. Metabolization of pyrethroids after achieving sexual maturity might account for this pattern.

The present study uses bird eggs of seven wild species as a biomonitoring tool for sunscreens occurrence. Seven UV filters (UV-Fs), including 3 hydroxy-metabolites of oxybenzone (benzophenone 3, BP3) were characterized in unhatched eggs from Donana Natural Space (Spain). High frequency of detection was observed for all UV-Fs, ranging from 95% to 100%. The oxybenzone metabolite 4-hydroxybenzophenone (4HB) was ubiquitous at concentrations in the range 12.0-3348 ng g dry weight (dw). The parent compound, oxybenzone, was also present in all samples at lower concentrations (16.9-49.3 ng g dw). Due to the three BP3′s metabolites, benzophenone 1 (BP1), 4HB, and 4,4′-dihydroxybenzophenone (4DHB) presence in unhatched eggs, it can be inferred that parent compounds are absorbed into the bird through the upper gut and the OH-derivatives formed are transferred by the mother to the egg before the lying. White stork (Ciconia ciconia) and western marsh harrier (Circus aeruginosus) were the most contaminated species, with mean total UV-Fs concentrations of 834 and 985 ng g dw, respectively. Results evidenced that biomagnification process across the bird species studied cannot be ruled out.

The Tablas de Daimiel National Park (TDNP) is a unique floodplain ecosystem in central Spain, serving as permanent resting and breeding areas for many waterbird species. In the last decades, this biodiversity hotspot has been severely endangered by poorly treated wastewater discharges from upstream urban communities arriving through its two major contributors, the Cigüela and Guadiana rivers. In this work, we analysed the potential risk of this constant input of micropollutants (estrogens, dioxin-like compounds and other endocrine disruptors) for the resident wildlife. We sampled 12 locations in TDNP and in the nearby Navaseca Pond during 2013, and performed a series of in-vivo and in-vitro bioassays, including Daphnia magna post-exposure feeding inhibition and recombinant yeast-based assays for dioxin-like and estrogenic activities. These results were then compared with the chemical composition of the samples, analysed by GC–MS/MS and LC-MS/MS, and evaluated according to their toxic potential as toxic equivalents or TEQ. The Navaseca Pond, heavily impacted by wastewater from the town of Daimiel, showed the highest levels of toxic compounds, estrogenic activity, and Daphnia toxicity. Conversely, the less impacted TDNP sites showed low residue levels of contaminants, low estrogenicity and dioxin-like activity and negligible toxicity. The results indicates that the current good chemical status of TDNP is menaced by both the inflow of wastewater treatment plants effluents from Guadiana and Cigüela rivers into TDNP tributaries and, as it occurs in the Navaseca Pond, by direct sewage discharges.

Classic (polybromodiphenyl ethers, PBDEs) and emerging halogenated flame retardants (HFRs) such as decabromodiphenyl ethane (DBDPE) and halogenated norbornenes, as well as organophosphate flame retardants (OPFRs) were analysed in 52 sediments and 27 fish samples from three European river basins, namely the Evrotas (Greece), the Adige (Italy) and the Sava (Slovenia, Croatia, Bosnia and Herzegovina and Serbia). This is the first time that FR levels have been reported in these three European river basins. The highest contamination was found in the Adige and Sava rivers, whereas lower values were obtained for the Evrotas. The levels in sediment samples ranged between 0.25 and 34.0 ng/g dw, and between 0.31 and 549 ng/g dw, for HFRs and OPFRs respectively. As regards levels in fish, concentrations ranged between 9.32 and 461 ng/g lw and between 14.4 and 650 ng/g lw, for HFRs and OPFRs, respectively. Thus, whereas OPFR values were higher in sediments, similar concentrations (in the Evrotas) and even lower concentrations than HFRs (Sava) were found for OPFRs in the fish samples, indicating the lower bioaccumulation potential of OPFRs. Biota to sediment accumulation factors (BSAFs) were calculated and higher values were obtained for HFRs compared to those assessed for OPFRs. © 2017 The Author(s)

Classic (polybromodiphenyl ethers, PBDEs) and emerging halogenated flame retardants (HFRs) such as decabromodiphenyl ethane (DBDPE) and halogenated norbornenes, as well as organophosphate flame retardants (OPFRs) were analysed in 52 sediments and 27 fish samples from three European river basins, namely the Evrotas (Greece), the Adige (Italy) and the Sava (Slovenia, Croatia, Bosnia and Herzegovina and Serbia). This is the first time that FR levels have been reported in these three European river basins. The highest contamination was found in the Adige and Sava rivers, whereas lower values were obtained for the Evrotas. The levels in sediment samples ranged between 0.25 and 34.0 ng/g dw, and between 0.31 and 549 ng/g dw, for HFRs and OPFRs respectively. As regards levels in fish, concentrations ranged between 9.32 and 461 ng/g lw and between 14.4 and 650 ng/g lw, for HFRs and OPFRs, respectively. Thus, whereas OPFR values were higher in sediments, similar concentrations (in the Evrotas) and even lower concentrations than HFRs (Sava) were found for OPFRs in the fish samples, indicating the lower bioaccumulation potential of OPFRs. Biota to sediment accumulation factors (BSAFs) were calculated and higher values were obtained for HFRs compared to those assessed for OPFRs.

Pyrethroids are the most popular drug against sea lice in salmon farming. Although they are more toxic to insects, they have toxic effects in mammals. Pyrethroids were detected in 100% of farmed salmon with a mean concentration of 1.31 ± 1.39 ng g−1 ww and in 50% of wild salmon with a mean of 0.02 ± 0.03 ng g−1 ww. Cypermethrin and deltamethrin, the active ingredients of anti-sea lice formulations, represented 77 ± 27% of the total contamination of farmed salmon. Although farmed salmon had higher concentrations than wild salmon, the daily intake of pyrethroids through salmon consumption was several orders of magnitude below the accepted daily intake (ADI). Thus, the pyrethroids treatment on salmon does not pose a threat on the health of the consumers. © 2017 Elsevier Ltd

© 2014 Elsevier Ltd. For the first time, this work described pyrethroid bioaccumulation in edible river fish samples. We analyzed 42 whole fish samples collected in 4 different Iberian rivers. All samples were positive to these insecticides. Levels of concentration ranged from 12 to 4938ngg-1 lipid weight (lw). Moreover, isomeric characterization was carried out. Our results remarked a general preference of cis isomers in bioaccumulation. Finally, the enantiomeric evaluation showed that there was an enantioselective bioaccumulation of some pyrethroids, depending on the studied species. Pyrethroid concentrations were compared with levels obtained for other common pollutants, such as flame retardants, personal care products, hormones and pharmaceuticals. The highest values corresponded to pyrethroid insecticides, even though, pyrethroid levels are safe for human consumption taken into account the current regulations.