Pablo Gago-Ferrero

First Determination of UV Filters in Marine Mammals. Octocrylene Levels in Franciscana Dolphins

Most current bioexposure assessments for UV filters focus on contaminants concentrations in fish from river and lake. To date there is not information available on the occurrence of UV filters in marine mammals. This is the first study to investigate the presence of sunscreen agents in tissue liver of Franciscana dolphin (Pontoporia blainvillei), a species under special measures for conservation. Fifty six liver tissue samples were taken from dead individuals accidentally caught or found stranded along the Brazilian coastal area (six states). The extensively used octocrylene (2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate, OCT) was frequently found in the samples investigated (21 out of 56) at concentrations in the range 89-782 ng·g(-1) lipid weight. São Paulo was found to be the most polluted area (70% frequency of detection). Nevertheless, the highest concentration was observed in the dolphins from Rio Grande do Sul (42% frequency of detection within that area). These findings constitute the first data reported on the occurrence of UV filters in marine mammals worldwide.

Fully automated determination of nine ultraviolet filters and transformation products in natural waters and wastewaters by on-line solid phase extraction–liquid chromatography–tandem mass spectrometry

This paper describes the development and validation of the first fully automated method, based on on-line solid phase extraction-liquid chromatography-tandem mass spectrometry (on line-SPE-LC-MS/MS), for the determination of UV filters (UV F) and transformation products, with a wide range of physicochemical properties. The developed method was validated and applied to the analysis of the selected compounds in river water (RW), groundwater (GW), influent and effluent wastewater (IWW and EWW). Comparing with the off-line methodologies published so far the presented method provides several advantages including a shorter extraction time, lower sample volume and minimum manipulation. Low limits of detection were achieved for all the studied matrices, <3ng/L (GW), <3.5ng/L (RW), <4ng/L (EWW) and <10ng/L (IWW), allowing a reliable and accurate quantification of the analytes at trace level. SPE optimization and critical aspects associated with the trace level determination of the target compounds (e.g. matrix effects) have been also considered and discussed. The method was successfully applied to the analysis of the UV F in five real water samples of each considered matrix, being the first time that these compounds were determined in GW.

Extended Suspect and Non-Target Strategies to Characterize Emerging Polar Organic Contaminants in Raw Wastewater with LC-HRMS/MS.

An integrated workflow based on liquid chromatography coupled to a quadrupole-time-of-flight mass spectrometer (LC-QTOF-MS) was developed and applied to detect and identify suspect and unknown contaminants in Greek wastewater. Tentative identifications were initially based on mass accuracy, isotopic pattern, plausibility of the chromatographic retention time and MS/MS spectral interpretation (comparison with spectral libraries, in silico fragmentation). Moreover, new specific strategies for the identification of metabolites were applied to obtain extra confidence including the comparison of diurnal and/or weekly concentration trends of the metabolite and parent compounds and the complementary use of HILIC. Thirteen of 284 predicted and literature metabolites of selected pharmaceuticals and nicotine were tentatively identified in influent samples from Athens and seven were finally confirmed with reference standards. Thirty four nontarget compounds were tentatively identified, four were also confirmed. The sulfonated surfactant diglycol ether sulfate was identified along with others in the homologous series (SO4C2H4(OC2H4)xOH), which have not been previously reported in wastewater. As many surfactants were originally found as nontargets, these compounds were studied in detail through retrospective analysis.

Evaluation of fungal- and photo-degradation as potential treatments for the removal of sunscreens BP3 and BP1.

Photodecomposition might be regarded as one of the most important abiotic factors affecting the fate of UV absorbing compounds in the environment and photocatalysis has been suggested as an effective method to degrade organic pollutants. However, UV filters transformation appears to be a complex process, barely addressed to date. The white rot fungus Trametes versicolor is considered as a promising alternative to conventional aerobic bacterial degradation, as it is able to metabolise a wide range of xenobiotics. This study focused on both degradation processes of two widely used UV filters, benzophenone-3 (BP3) and benzophenone-1 (BP1). Fungal treatment resulted in the degradation of more than 99% for both sunscreens in less than 24 h, whereas photodegradation was very inefficient, especially for BP3, which remained unaltered upon 24 h of simulated sunlight irradiation. Analysis of metabolic compounds generated showed BP1 as a minor by-product of BP3 degradation by T. versicolor while the main intermediate metabolites were glycoconjugate derivatives. BP1 and BP3 showed a weak, but significant estrogenic activity (EC50 values of 0.058 mg/L and 12.5 mg/L, respectively) when tested by recombinant yeast assay (RYA), being BP1 200-folds more estrogenic than BP3. Estrogenic activity was eliminated during T. versicolor degradation of both compounds, showing that none of the resulting metabolites possessed significant estrogenic activity at the concentrations produced. These results demonstrate the suitability of this method to degrade both sunscreen agents and to eliminate estrogenic activity.

Urban groundwater contamination by residues of UV filters

The occurrence and fate of UV filters (UV F) in an urban aquifer in correlation with (1) the spatial distribution of UV F in Barcelonas groundwater, (2) the depth of the groundwater sample, (3) the physicochemical properties of the target compounds, (4) the recharge sources, and (5) the redox conditions of the Barcelona aquifers, were studied for the first time. The highest groundwater concentrations and the largest number of detected UV F were observed in an aquifer recharged by a polluted river (around 55 ng/L in SAP-4). In contrast, the urbanized areas had lower concentrations (around 20 ng/L in MPSP-1). Two pathways can be identified for UV F to enter the aquifers: (1) leakage of row sewage from the sewage network in urbanized areas and (2) wastewater treatment plant (WWTP) effluents discharged into the river. Measured concentrations of UV F were significantly much lower than those estimated from the waste water proportion in groundwater samples suggesting that UV F might undergo transformation processes in both reducing and oxidizing conditions.

Occurrence and spatial distribution of 158 pharmaceuticals, drugs of abuse and related metabolites in offshore seawater

The occurrence and spatial distribution of 158 pharmaceuticals and drugs of abuse were studied in seawater of the Eastern Mediterranean Sea (Saronikos Gulf and Elefsis Bay in central Aegean Sea). This area is affected by various anthropogenic pressures as it receives the treated wastewater of the greatest Athens area and off-shore input fluxes. This study constitutes the largest one in terms of number of analytes in this environmental compartment. It provides the first evidence on the occurrence of several pharmaceuticals in marine environment including amoxicillin, lidocaine, citalopram or tramadol, among others. 22 samples were collected at three different depths in 9 sampling stations in order to assess the presence and the spatial distribution of the target compounds. A multi-residue method based on solid phase extraction and liquid chromatography coupled to tandem mass spectrometry was developed for the determination of the 158 target substances and validated for seawater sample analysis. 38 out of the 158 target compounds were detected, 15 of them with frequencies of detection equal to or higher than 50%. The highest detected values corresponded to amoxicillin, caffeine and salicylic acid, with concentrations in the range of < 5.0-127.8 ng L(-1); 5.2-78.2 ng L(-1) and < 0.4-53.3 ng L(-1), respectively. Inputs from the wastewater treatment plant (WWTP) of Athens revealed to be the main source of pollution in the Inner Saronikos Gulf, whereas, other anthropogenic pressures such as contamination from shipping activity, industrial effluents, dredging and/or inputs from land proved to be also relevant. Τhe concentrations of some compounds varied significantly with depth suggesting that currents play an important role in the dilution of the target compounds.

Occurrence of hydrophobic organic pollutants (BFRs and UV-filters) in sediments from South America

In the present study the occurrence of emerging hydrophobic organic pollutants in sediment samples from South America (Chile and Colombia) was investigated for the first time. Nineteen Chilean and thirteen Colombian sediment samples were analyzed in order to determine their content of brominated flame retardants (BFRs) (including PBDEs and emerging BFRs) as well as UV filters (UV-F). Samples were collected from neighboring aquatic ecosystems highly urbanized and industrialized in Colombia (Magdalena River area) and Chile (Biobio region). Different analytical procedures were applied depending on the selected analytes, based on chromatographic and mass spectrometric methodologies (GC-MS and LC-MS-MS). In general, concentration levels of both BFRs (up to 2.43 and 143ngg(-1) dw of PBDEs in Chile and Colombia, respectively) and UV-F (nd-2.96 and nd-54.4ngg(-1) dw in Chile and Colombia, respectively) were in the low range of published data, and the contribution of BFRs was higher than that of UV-F for almost all the sampled sediments.

Multi-residue method for trace level determination of UV filters in fish based on pressurized liquid extraction and liquid chromatography-quadrupole-linear ion trap-mass spectrometry.

So far, the very few studies addressing the occurrence of UV filters (UV F) in biota showed important limitations in the analysis of the so complex biological matrices. In order to improve the knowledge on the bioaccumulation of UV F by fish, a simple and highly sensitive method was successfully developed and validated for the simultaneous determination of eight extensively used UV F and transformation products with a wide range of physicochemical properties. The present study demonstrated that liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) using a QqLIT mass analyser was applicable to the simultaneous analysis of UV F in fish. Pressurized liquid extraction (PLE) was chosen for the sample pretreatment due to the good extraction efficiency provided. An additional SPE clean-up step was added in order to minimize matrix effects and to improve the sensitivity. The method allowed recovery efficiencies in the range 70-112% for most compounds at the three spike levels. The low limits of detection (MLOD) achieved (0.1-6.0 ng/g dw) allowed the reliable quantification of UV F residues in fish samples. The developed methodology was applied to assess the occurrence of UV F in different fish species from the Guadalquivir river basin (Spain). Results confirmed the bioaccumulation of benzophenone-3 (BP3), ethylhexyl methoxycinnamate (EHMC) and octocrylene (OC) in the fish samples. The maximum concentration of 240 ng/g dw corresponded to EHMC, which was also the most ubiquitous compound. The reported concentrations constitute the first occurrence data of UV F residues in fish from Iberian rivers.

UV filters bioaccumulation in fish from Iberian river basins

The occurrence of eight organic UV filters (UV-Fs) was assessed in fish from four Iberian river basins. This group of compounds is extensively used in cosmetic products and other industrial goods to avoid the damaging effects of UV radiation, and has been found to be ubiquitous contaminants in the aquatic ecosystem. In particular, fish are considered by the scientific community to be the most feasible organism for contamination monitoring in aquatic ecosystems. Despite that, studies on the bioaccumulation of UV-F are scarce. In this study fish samples from four Iberian river basins under high anthropogenic pressure were analysed by liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Benzophenone-3 (BP3), ethylhexyl methoxycinnamate (EHMC), 4-methylbenzylidene camphor (4MBC) and octocrylene (OC) were the predominant pollutants in the fish samples, with concentrations in the range of ng/g dry weight (d.w.). The results indicated that most polluted area corresponded to Guadalquivir River basin, where maximum concentrations were found for EHMC (241.7 ng/gd.w.). Sediments from this river basin were also analysed. Lower values were observed in relation to fish for OC and EHMC, ranging from below the limits of detection to 23 ng/gd.w. Accumulation levels of UV-F in the fish were used to calculate biota-sediment accumulation factors (BSAFs). These values were always below 1, in the range of 0.04-0.3, indicating that the target UV-Fs are excreted by fish only to some extent. The fact that the highest concentrations were determined in predators suggests that biomagnification of UV-F may take place along the freshwater food web.

Removal of pharmaceuticals, polybrominated flame retardants and UV-filters from sludge by the fungus Trametes versicolor in bioslurry reactor

Conventional wastewater treatments are inefficient in the removal of many organic pollutants. The presence of these contaminants in the final sludge represents a source of environmental pollution due to the increasing use of biosolids in land application. A biotechnological approach which employed the fungus Trametes versicolor in a sludge-bioslurry reactor was assessed in order to remove several groups of emerging pollutants. Biological fungal activity was monitored by means of ergosterol and laccase determinations. Fifteen out of 24 detected pharmaceuticals were removed at efficiencies over 50% after the treatment, including eight completely degraded. Removal ranged between 16-53% and 22-100% for the brominated flame retardants and the UV-filters, respectively. Only two of all the detected compounds remained unchanged after the treatment. Although elimination results are promising, the toxicity of the final sludge increased after the treatment. This finding is contrary to the toxicity results obtained in similar treatments of sludge with T. versicolor in solid-phase.