Assessment of metal and organic pollutants in combination with stable isotope analysis in tunas from the Gulf of Cadiz (east Atlantic).

Bioaccumulation patterns of heavy metals (Pb, Cd, Cr, Ni, Fe and Cu) and organic (priority and emerging) pollutants, in combination with stable isotope analysis (SIA), were assessed in muscle and liver of three tuna species from the Gulf of Cadiz (Atlantic bluefin tuna, Thunnus thynnus; Atlantic bonito, Sarda sarda, and skipjack tuna, Katsuwonus pelamis). SIA and contaminant (heavy metal and organic) profiles separately discriminated between species. There was no significant overlap between the trophic niches estimated from isotopic data, suggesting that there are diet differences which may determine differential bioaccumulation patterns. The levels of heavy metals and persistent organic pollutants in muscle of all the individuals analyzed were below the allowable limits established by the current legislation. Concentrations of most contaminants were higher in liver than in muscle, underlining the powerful detoxifying capacity of the liver in tunas. In addition to diet, other factors such as size and age (exposure time to environmental chemicals) explain differences in pollutant accumulation patterns in tissues between species, each with varying degrees of involvement depending on the pollutant class. Our results show that combining contaminant profile data with trophic features based on SIA may help understand pollutant bioaccumulation patterns in upper levels of marine food webs.

Personal care products: an emerging threat to the marine bivalve Ruditapes philippinarum.

In the last few decades, there has been a growing interest in understanding the behavior of personal care products (PCPs) in the aquatic environment. In this regard, the aim of this study is to estimate the accumulation and effects of four PCPs within the clam Ruditapes philippinarum. The PCPs selected were triclosan, OTNE, benzophenone-3, and octocrylene. A progressive uptake was observed and maximum concentrations in tissues were reached at the end of the exposure phase, up to levels of 0.68 µg g-1, 24 µg g-1, 0.81 µg g-1, and 1.52 µg g-1 for OTNE, BP-3, OC, and TCS, respectively. After the PCP post-exposure period, the removal percentages were higher than 65%. The estimated logarithm bioconcentration factor ranged from 3.34 to 2.93, in concordance with the lipophobicity of each substance. No lethal effects were found although significant changes were observed for ethoxyresorufin O-demethylase activity, glutathione S-transferase activity, lipid peroxidation, and DNA damage.

Vertical distribution and risk assessment of pharmaceuticals and other micropollutants in southern North Sea coastal waters.

Pharmaceutical compounds are micropollutants of emerging concern, as well as other classes of chemicals such as UV filters and artificial sweeteners. They enter marine environments via wastewater treatment plants, aquaculture runoff, hospital effluents, and shipping activities. While many studies have investigated the presence and distribution of these pollutants in numerous coastal areas, our study is the first to focus on their occurrence, spatial distribution, and vertical distribution in the sea surface microlayer (SML) and the near-surface layer of marine environments. We analyzed 62 pharmaceutical compounds, one UV filter, and six artificial sweeteners from the SML to the corresponding underlying water (0 cm, 20 cm, 50 cm, 100 cm, and 150 cm) at four stations in the southern North Sea. One station is the enclosed Jade Bay, one is the Weser estuary at Bremerhaven, and the other two stations (NS_7 and NS_8) are in the open German Bight. Jade Bay receives pollutants from surrounding wastewater treatment plants, while the Weser estuary receives pollutants from cities like Bremerhaven, which has dense populations and industrial activities. Concentrations of pharmaceutical compounds were higher in the upper water layers (from the SML to 20 cm). Eleven pharmaceutical compounds (caffeine, carbamazepine, gemfibrozil, ibuprofen, metoprolol, salicylic acid, clarithromycin, novobiocin, clindamycin, trimethoprim, and tylosin) were detected in >95 % of our samples. One UV filter (benzophenone-4) was found in 83 % and three artificial sweeteners (acesulfame, saccharin, and sucralose) in 100 % of all our samples. All artificial sweeteners posed high risks to the freshwater invertebrate Daphnia magna. Understanding the spatial and vertical distribution of pharmaceuticals and other micropollutants in marine environments may be essential in assessing their dispersal and detection in other aquatic environments.

Bioconcentration, biotransformation, and transcriptomic impact of the UV-filter 4-MBC in the manila clam Ruditapes philippinarum.

Ultraviolet filters (UV-filters) are compounds extensively used in personal care products. These compounds are produced at increasing rates and discharged into marine ecosystems in unknown quantities and with no regulation, making them emerging contaminants. Among those, the UV-filter 4-Methylbenzylidene camphor (4-MBC) is used in a variety of personal care products such as sunscreens, soaps, or lipsticks. This high consumption has resulted in its presence in various environmental matrices at in concentrations ranging from ng to µg L-1. Very little is known, however, about the possible adverse effects in exposed non-target organisms. Our study presents novel data on the bioconcentration, toxicokinetics, and molecular effects of 4-MBC in a marine bivalve species of commercial interest, Ruditapes philippinarum (Manila clam). Organisms were exposed at two different concentrations (1.34 and 10.79 µg L-1) of 4-MBC for 7 days, followed by a 3-day depuration period (clean sea waters). Bioconcentration factors (BCF) were 3562 and 2229 L kg-1 for the low and high exposure concentrations, respectively, making this pollutant bioaccumulative according to REACH criteria. Up to six 4-MBC biotransformation products (BTPs)were identified, 2 of them for the first time. Transcriptomic analysis revealed between 658 and 1310 differently expressed genes (DEGs) after 4-MBC exposure. Functional and enrichment analysis of the DEGs showed the activation of the detoxification pathway to metabolize and excrete the bioconcentrated 4-MBC, which also involved energy depletion and caused an impact on the metabolism of carbohydrates and lipids and in the oxidative phosphorylation pathways. Oxidative stress and immune response were also evidenced through the activation of cathepsins and the complement system. Such elucidation of the mode of action of a ubiquitous pollutant such as 4-MBC at the molecular level is valuable both from an environmental point of view and for the sustainable production of Manila clam, one of the most cultivated mollusk species worldwide.

Occurrence, sources and environmental risk assessment of organic micropollutants in coastal sediments from the Atacama Region (Chile).

Nowadays, there is still a scientific knowledge gap regarding occurrence and distribution of organic contaminants in remote areas. In this study, we have monitored for the first time the presence of a wide range of persistent and emerging organic pollutants in the Atacama Desert coastal region (Chile), a key area in the Humboldt Current System. Nonylphenols (NPs), polycyclic aromatic hydrocarbons (PAHs), pesticides, UV filters, synthetic fragrances, and organophosphate flame retardants (OPFRs) were determined in sediments along the >500 km length Atacama coastline. NPs, well-known endocrine disruptors, were the predominant pollutants in the area (up to 333.5 ng g-1 dw). We identified inputs of different classes of contaminants from anthropogenic activities such as mining, agriculture, direct effluent discharges, harbors, energy plants, recreational activities, and tourism occurring along the coastline. Environmental risk assessment through calculation of hazard quotients (HQs) showed a high ecological risk level for NPs in the three provinces of Atacama (HQ >1). In the case of PAHs, (pyrene, benz(a)anthracene, chrysene, acenaphthene, naphthalene and benzo(a)pyrene) HQ >1 was showed in Copiapó province. Furthermore, estradiol equivalent concentrations (EEQ) were determined to estimate estrogenicity of the environmental sediment samples. The maximum EEQ value was for NPs in H1 (Carrizal Bajo wetland), province of Huasco, where the highest concentration of NPs was found. The sampling point H1 is a particular location because it is the exit of a wetland and a tourist point used as a beach. The potential risks of anthropogenic chemical substances impacting remote regions such as the one studied here highlight the need of expand monitoring efforts worldwide for a better assessment of the global pollution status.

High resolution mass spectrometry (HRMS) determination of drugs in wastewater and wastewater based epidemiology in Cadiz Bay (Spain).

Multi-residue methods for the determination of the myriad of compounds of emerging concern (CECs) entering in the environment are key elements for further assessment on their distribution and fate. Here, we have developed an analytical protocol for the simultaneous analysis of 195 prescription, over-the-counter, and illicit drugs by using a combination of solid phase extraction (SPE) and determination by liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS). The method was applied to the analysis of influent sewage samples from 3 wastewater treatment plants (WWTPs) from Cadiz Bay (SW Spain), enabling the quantification of more than 100 pharmaceuticals, 19 of them at average concentrations higher than 1 µg L-1, including caffeine (92 µg L-1), paracetamol (72 µg L-1), and ibuprofen (56 µg L-1), as well as several illicit drugs (e.g., cocaine). Wastewater based epidemiology (WBE) was applied for 27 of the detected compounds to establish their consumption in the sampling area, which has been never attempted before. Caffeine, naproxen, and salicylic acid stood out because of their high consumption (638, 51, and 20 g d-1·1000pop-1, respectively). Regarding illicit drugs, cocaine showed the highest frequency of detection and we estimated an average consumption of 3683 mg d-1·1000pop-1 in Cadiz Bay. The combination of new HRMS methods, capable of discriminating thousands of chemicals, and WBE will allow for a more comprehensive characterization of chemical substances and their consumption in urban environments in the near future.

Transcriptomic and metabolomic integration to assess the response of gilthead sea bream (Sparus aurata) exposed to the most used insect repellent: DEET.

DEET is one of the most frequently detected insect repellents in the environment reaching concentrations of several µg L-1 in surface water. There is scarce information available regarding its mode of action in non-target organisms. Here, we have used an integrated metabolomic and transcriptomic approach to elucidate the possible adverse effects of DEET exposure in the marine fish gilthead sea bream (Sparus aurata). Individuals were exposed at an environmentally relevant concentration of DEET (10 µg L-1) for 22 days in a continuous flow-through system. Transcriptomic analysis revealed 250 differentially expressed genes in liver, while metabolomic analysis identified 190 differentially modulated features in liver and 98 in plasma. Multi-omic data integration and visualization allowed elucidation of the modes of action of DEET exposure, including: energy depletion through the disruption of carbohydrate and amino acids metabolisms, oxidative stress leading to DNA damage, lipid peroxidation, and damage to cell membrane and apoptosis. Activation of xenobiotic pathway as well as the inmune-inflammatory reaction was evidenced in the present work.

The antibacterials ciprofloxacin, trimethoprim and sulfadiazine modulate gene expression, biomarkers and metabolites associated with stress and growth in gilthead sea bream (Sparus aurata).

The high consumption and subsequent input of antibacterial compounds in marine ecosystems has become a worldwide problem. Their continuous presence in these ecosystems allows a direct interaction with aquatic organisms and can cause negative effects over time. The objective of the present study was to evaluate the effects of exposure to three antibacterial compounds of high consumption and presence in marine ecosystems (Ciprofloxacin CIP, Sulfadiazine SULF and Trimethoprim TRIM) on the physiology of the gilthead sea bream, Sparus aurata. Plasma parameters, enzymatic biomarkers of oxidative stress and damage and expression of genes related to stress and growth were assessed in exposed S. aurata specimens. For this purpose, sea bream specimens were exposed to individual compounds at concentrations of 5.2 ± 2.1 µg L-1 for CIP, 3.8 ± 2.7 µg L-1 for SULF and 25.7 ± 10.8 µg L-1 for TRIM during 21 days. Exposure to CIP up-regulated transcription of genes associated with the hypothalamic-pituitary-thyroid (HPT) (thyrotropin-releasing hormone, trh) and hypothalamic-pituitary-interrenal (HPI) axes (corticotropin-releasing hormone-binding protein, crhbp) in the brain, as well as altering several hepatic stress biomarkers (catalase, CAT; glutathione reductase, GR; and lipid peroxidation, LPO). Similar alterations at the hepatic level were observed after exposure to TRIM. Overall, our study indicates that S. aurata is vulnerable to environmentally relevant concentrations of CIP and TRIM and that their exposure could lead to a stress situation, altering the activity of antioxidant defense mechanisms as well as the activity of HPT and HPI axes.

Assessment of the aerobic and anaerobic biodegradation of contaminants of emerging concern in sludge using batch reactors.

This work explores the degradation of xenobiotic compounds in aerobic and anaerobic batch reactors. Different inoculums were spiked with nine emerging contaminants at nominal concentrations ranging between 1 to 2 mg/L (ibuprofen, diclofenac, naproxen, acesulfame, sucralose, aspartame, cyclamate, linear alkylbenzene sulfonates, and secondary alkyl sulfonates). Ethanol was used as co-substrate in the anaerobic reactors. We found that the kinetic decay was faster in the aerobic reactors inoculated with a Spanish (Spn) inoculum compared to a Brazilian (Brz) inoculum, resulting in rection rates for LAS and SAS of 2.67 ± 3.6 h-1 and 5.09 ± 6 h-1 for the Brz reactors, and 1.3 ± 0.1 h-1 and 1.5 ± 0.2 h-1 for the Spn reactors, respectively. There was no evidence of LAS and SAS degradation under anaerobic conditions within 72 days; nonetheless, under aerobic conditions, these surfactants were removed by both the Brz and Spn inoculums (up to 86.2 ± 9.4% and 74.3 ± 0.7%, respectively) within 10 days. The artificial sweeteners were not removed under aerobic conditions, whereas we could observe a steady decrease in the anaerobic reactors containing the Spn inoculum. Ethanol aided in the degradation of surfactants in anaerobic environments. Proteiniphilum, Paraclostridium, Arcobacter, Proteiniclasticum, Acinetobacter, Roseomonas, Aquamicrobium, Moheibacter, Leucobacter, Synergistes, Cyanobacteria, Serratia, and Desulfobulbus were the main microorganisms identified in this study.

Persistent organic pollutants and contaminants of emerging concern in spinner dolphins (Stenella longirostris) from the Western Atlantic Ocean.

The presence and distribution of persistent organic pollutants (POPs) and contaminants of emerging concern (CECs) were evaluated in spinner dolphins (Stenella longirostris) from the Fernando de Noronha Archipelago (Western Atlantic Ocean). Blubber samples (n = 37) were Soxhlet extracted and analyzed using gas chromatography tandem mass spectrometry. The levels of POPs reported in this study are far below those previously reported in spinner dolphins from the Indian and Pacific Oceans. Despite relatively low levels of contaminants, the presence of chemicals represents an additional stressor to these marine mammals, which are subject to increasing anthropogenic pressures, especially regarding tourism activities, in Fernando de Noronha.

Synthetic surfactants in Swiss sewage sludges: Analytical challenges, concentrations and per capita loads.

Surfactants are high-production-volume chemicals that are among the most abundant organic pollutants in municipal wastewater. In this study, sewage sludge samples of 36 Swiss wastewater treatment plants (WWTPs), serving 32% of the country's population, were analyzed for major surfactant classes by liquid chromatography mass spectrometry (LC-MS). The analyses required a variety of complementary approaches due to different analytical challenges, including matrix effects (which can affect adduct ion formation) and the lack of reference standards. The most abundant contaminants were linear alkylbenzene sulfonates (LAS; weighted mean [WM] concentration of 3700 µg g-1 dry weight), followed by secondary alkane sulfonates (SAS; 190 µg g-1). Alcohol polyethoxylates (AEO; 8.3 µg g-1), nonylphenol polyethoxylates (NPEO; 16 µg g-1), nonylphenol (NP; 3.1 µg g-1), nonylphenol ethoxy carboxylates (NPEC; 0.35 µg g-1) and tert-octylphenol (tert-OP, 1.8 µg g-1) were present at much lower concentrations. This concentration pattern agrees with the production volumes of the surfactants and their fates in WWTPs. Branched AEO homologues dominated over linear homologues, probably due to higher persistence. Sludge concentrations of LAS, SAS, and NP were positively correlated with the residence time in the anaerobic digester. Derivation of the per capita loads successfully revealed potential industrial/commercial emission sources. Comparison of recent versus historic data showed a decrease in NPEO and NP levels by one or two orders of magnitude since their ban in the 1980s. By contrast, LAS still exhibit similar concentrations compared to 30 years ago.

Multi-omic approach to evaluate the response of gilt-head sea bream (Sparus aurata) exposed to the UV filter sulisobenzone.

Sulisobenzone (BP-4) is one of the benzophenone type UV filters most frequently detected in aquatic ecosystems. As a suspected endocrine disrupting compound, scarce information is available yet about other molecular effects and its mechanism of action. Here, we used an integrated transcriptomic and metabolomic approach to improve the current understanding on the toxicity of BP-4 towards aquatic species. Gilt-head sea bream individuals were exposed at environmentally relevant concentrations (10 µg L-1) for 22 days. Transcriptomic analysis revealed 371 differentially expressed genes in liver while metabolomic analysis identified 123 differentially modulated features in plasma and 118 in liver. Integration of transcriptomic and metabolomic data showed disruption of the energy metabolism (>10 pathways related to the metabolism of amino acids and carbohydrates were impacted) and lipid metabolism (5 glycerophospholipids and the expression of 3 enzymes were affected), suggesting oxidative stress. We also observed, for the first time in vivo and at environmental relevant concentrations, the disruption of several enzymes involved in the steroid and thyroid hormones biosynthesis. DNA and RNA synthesis was also impacted by changes in the purine and pyrimidine metabolisms. Overall, the multiomic workflow presented here increases the evidence on suspected effects of BP-4 exposure and identifies additional modes of action of the compounds that could have been overlooked by using single omic approaches.

Emerging contaminants and priority substances in marine sediments from Cartagena Bay and the Grand Marsh of Santa Marta (Ramsar site), Colombia.

Emerging pollutants and priority substances are of growing concern due to their toxicity potential to aquatic organisms and human health. However, few reports on this issue in marine ecosystems in general and, more specifically, on the Colombian Caribbean coast are available. The aim of this study was to detect these compounds in sediments from Cartagena Bay (CB) and in the Grand Marsh of Santa Marta, GMSM (Ramsar site), in order to determine how they related to in vitro cytotoxicity assays on HepG2 cells of sediment extracts. A total of thirty compounds were detected using GC-MS/MS in fifteen stations during both the rainy and the dry seasons. Sediments from CB had a wide range of different toxicants, with polycyclic aromatic hydrocarbons (PAHs) being the most prevalent (12 PAHs, 5.5-881.6 ng/g). Total PCBs ranged from < LOD to 18.6 ng/g, with PCB 138 being the most common detected congener. Residues of p,p'-DDE, Chlorpyrifos and two organophosphate flame retardants, TEHP and ToTP, were found in most sampling locations. The UV filters 4MBC and homosalate were recurrently found in sediments, and the fragrance galaxolide appeared in all cases, with the greatest concentrations found on a touristic beach. In GMSM, with the exception of deltamethrin, all chemicals evaluated had lower average values than in CB. According to sediment quality guidelines, some sites in CB presented values of PAHs higher than the threshold effects level, while in the marsh, none of the stations exceeded it. HepG2 cells exposed to 1% sediment extracts presented reduced cell viability up to 26%. Cytotoxicity displayed a negative correlation with chlorpyrifos concentration. In short, these data suggest the bay and the marsh have specific contamination fingerprints related to anthropogenic interventions. This research highlights the need to further investigate the ecotoxicological implications of detected chemical stressors in these ecosystems.

Mobility of contaminants of emerging concern in soil column experiments.

In this study, laboratory column experiments under water saturated conditions were conducted for over 35 days to investigate the transport of nine pharmaceuticals (nadolol, sulfamethizole, sulfamethoxazole, sulfamethoxypyridazine, carbamazepine, ibuprofen, diclofenac, hydrochlorothiazide, and gemfibrozil) and four artificial sweeteners (acesulfame, saccharin, cyclamate, and sucralose) in two soils (S and C) with similar organic carbon content (between 0.8 and 1.1%) and pH (7.90 and 7.25) but different texture (58.3 and 85.5% of silt+clay, respectively). Ibuprofen and artificial sweeteners reached maximum concentrations at the outlet of the columns and showed a homogenous vertical profile in the aqueous phase, with the same concentration in all sampling ports under flow percolation conditions. Regarding carbamazepine and hydrochlorothiazide, apparent retardation was observed for both and was attributed to sorption. Nadolol, a positively charged beta-blocker, did not show any apparent breakthrough. After 35 days, the columns were washed using tap water for over one week. Soils were then analyzed at different depths and vertical concentration profiles were plotted. Overall, highest concentrations were measured in the top most layers for contaminants in the soil column with higher clay content (C), whereas vertical profiles were more uniform in that with lower clay content (S).

Target and suspect screening analysis reveals persistent emerging organic contaminants in soils and sediments.

An approach to identifying persistent organic contaminants in the environment was developed and executed for Switzerland as an example of an industrialized country. First, samples were screened with an in-house list using liquid chromatography high-resolution mass spectrometry (LC-HRMS/MS) and gas chromatography tandem mass spectrometry (GC-MS/MS) in 13 samples from the Swiss National Soil Monitoring Network and three sediment cores of an urban and agricultural contaminated lake. To capture a broader range of organic contaminants, the analysis was extended with a suspect screening analysis by LC-HRMS/MS of >500 halogenated compounds obtained from a Swiss database that includes industrial and household chemicals identified, by means of fugacity modeling, as persistent substances in the selected matrices. In total, the confirmation of 96 compounds with an overlap of 34 in soil and sediment was achieved. The identified compounds consist generally of esters, tertiary amines, trifluoromethyls, organophosphates, azoles and aromatic azines, with azoles and triazines being the most common groups. Newly identified compounds include transformation products, pharmaceuticals such as the flukicide niclofolan, the antimicrobial cloflucarban, and the fungicide mandipropamid. The results indicate that agricultural and urban soils as well as sediments impacted by agriculture and wastewater treatment plants (WWTPs) are the most contaminated sites. The plausibility of this outcome confirms the combination of chemical inventory, modeling of partitioning and persistence, and HRMS-based screening as a successful approach to shed light on less frequently or not yet investigated environmental contaminants and emphasizes the need for more soil and sediment monitoring in the future.

Passive Samplers vs Sentinel Organisms: One-Year Monitoring of Priority and Emerging Contaminants in Coastal Waters.

Temporal monitoring of pollutants in aquatic systems impacted by human activities is mandatory for a correct assessment on their environmental impact and later management. The aim of this work was to study the suitability of using silicone rubber passive samplers and caged organisms (Ruditapes philippinarum), simultaneously, to examine the spatial and temporal variability of priority and emerging contaminants in a coastal environment (Cadiz Bay, SW Spain) over the course of an entire year. Seasonal trends were observed for some classes of compounds, such as UV filters and fragrances, and attributed to fluctuations in their sources and changes in the hydrodynamic conditions, respectively. Up to 42 out of 48 (in seawater) and 27 out of 37 (in biota) target analytes were detected, the highest concentrations being observed for synthetic fragrances and UV filters in both biota (136.9-159 ng g-1) and the dissolved phase (3322.2-265.7 ng L-1). Conversely, spatiotemporal differences in the concentrations of target contaminants in clam tissues were minimal. Higher field bioaccumulation factors (log BAF > 5) were found for priority substances. Overall, silicone rubber passive samplers proved to be more sensitive than sentinel organisms for monitoring spatiotemporal changes in the dissolved aqueous concentrations of contaminants, whereas the latter allowed for a more realistic evaluation of the potential uptake and bioaccumulation of each compound.

Tracing Urban Wastewater Contaminants into the Atlantic Ocean by Nontarget Screening.

Oceans are the ultimate sink for many of the over 100 million man-made substances. Until now, monitoring was limited to a reduced number of targeted persistent organic pollutants, reaching open waters mainly via atmospheric deposition. However, the composition and fate of the thousands of pollutants reaching the marine environment though wastewater discharges from coastal sources remain largely unexplored. By combining a newly developed nontarget screening (NTS) workflow and high-resolution mass spectrometry (HRMS), we have identified over 500 sewage-derived contaminants occurring in the ocean. Samples from the NE Atlantic contained this anthropogenic imprint at distances over 50 km from the coastline and >500 m depth, beyond the continental margin. The range of identified compounds spans from pharmaceuticals and personal care products to food additives and industrial chemicals, including several that have never been reported in the environment, as they escaped conventional targeted analytical methods. Predicting the effects of the continuous input of this chemical "cocktail" on marine ecosystems is a formidable challenge, since 40% of the detected compounds lack information regarding their use and ecotoxicity.

Historical sedimentary deposition and flux of PAHs, PCBs and DDTs in sediment cores from the western Adriatic Sea.

The sources and depositional history of polycyclic aromatic hydrocarbons (PAHs) and organochlorine compounds (OCs) over the last century were investigated in sediment cores from the North Adriatic Sea (Po River prodelta) and the South-Western Adriatic Margin (SWAM). Contaminant concentrations were higher in the Po River prodelta. ∑16PAHs ranged from 193 to 533 ng g-1, ∑5PCBs ranged from 0.9 to 5.2 ng g-1 and ∑DDTs (p,p'-DDD + p,p'-DDE) ranged from 0.1 to 2.5 ng g-1. In the SWAM, ∑PAHs ranged from 11 to 74 ng g-1 while ∑PCB and ∑DDT concentrations were close to the MQL. Accordingly, contaminant fluxes were much higher in the northern (mean values of 152 ±â€¯31 ng cm2 y-1 and 0.70 ±â€¯0.35 ng cm2 y-1 for PAHs and OCs, respectively) than in the southern Adriatic (2.62 ±â€¯0.9 ng cm2 y-1 and 0.03 ±â€¯0.02 ng cm2 y-1 for PAHs and OCs, respectively). The historical deposition of PAHs seemed to be influenced by the historical socioeconomic development and by changes in the composition of fossil fuel consumption (from petroleum derivatives to natural gas) in Italy from the end of the 19th century to the present. Similarly, vertical variations in DDT concentrations matched its historical use and consumption in Italy, which started around in the mid-late 1940s to fight typhus during the II World War. Contaminant concentrations detected in sediments does not seem to pose ecotoxicological risk for marine organisms in the Adriatic Sea.

Occurrence of 40 pharmaceutically active compounds in hospital and urban wastewaters and their contribution to Mahdia coastal seawater contamination.

In the present study, the occurrence of 40 pharmaceuticals belonging to several therapeutic groups was investigated for the first time in hospital effluent, wastewater treatment plant influent and effluent, and seawater in Mahdia, Tunisia. Forty-six samples were collected within a 6-month sampling period. Pharmaceuticals were analyzed using solid-phase extraction followed by ultra-performance liquid chromatography-triple quadrupole mass spectrometry. Thirty-three out of the forty target compounds were detected over a wide concentration of ranges, from nanograms per liter to micrograms per liter, depending on the type of sample. Maximum values were detected for caffeine at 902 µgL-1 in hospital wastewater. This compound, as well as salicylic acid, sulfadiazine, and sulfamethizole, were detected in all samples. The average concentration of total pharmaceuticals in hospital wastewater (340 µgL-1) was higher than those detected in influent and effluent wastewater and seawater (275.11 and 0.2 µgL-1, respectively). Risk quotients (RQs) were also estimated to provide a preliminary environmental risk assessment and results revealed that sulfadiazine, sulfamethoxazole, and fluoxetine could pose medium/high risk to the tested aquatic organisms for maximum measured concentrations in wastewater (including hospital and WWTP samples). Although the measured environmental concentrations (MECs) detected in seawater samples might not pose a toxic effect to the aquatic organisms (except for salicylic acid, sulfamethoxazole and fluoxetine), further researches are needed due to the continuous release of wastewater in the environment and the limited efficiency of wastewater treatment processes.

Suspect Screening of Hydrocarbon Surfactants in AFFFs and AFFF-Contaminated Groundwater by High-Resolution Mass Spectrometry.

Aqueous film-forming foams (AFFFs) are proprietary mixtures containing hydrocarbon surfactants and per- and polyfluoroalkyl substances (PFASs) that are used to extinguish hydrocarbon-based fuel fires. There is limited information on hydrocarbon surfactants in AFFFs and AFFF-contaminated groundwater even though hydrocarbon surfactants are more abundant (5-10% w/w) than PFASs (0.9-1.5% w/w) in AFFFs. Eight commercial AFFFs manufactured between 1988 and 2012 and 10 AFFF-contaminated groundwaters collected from near source zones of fire-fighter training areas were analyzed for suspect hydrocarbon surfactants by liquid chromatography quadrupole time-of-flight mass spectrometry. A suspect list and a homologous series detection computational tool, enviMass, were combined to screen for hydrocarbon surfactants. Nine classes of hydrocarbon surfactants were detected in AFFFs including octylphenol polyethoxylates, linear alcohol ethoxylates, ethoxylated cocoamines, alkyl ether sulfates, alkyl amido dipropionates, linear alkyl benzenesulfonates, alkyl sulfates, and polyethylene glycols. Of those, six were also found in groundwater along with diethanolamines and alkyl amido betaines, which were not found in the eight archived AFFFs. This indicates that although aerobically biodegradable, hydrocarbon surfactants likely persist in groundwater due to anaerobic aquifer conditions. To the best of our knowledge, this is the first screening for hydrocarbon surfactants in AFFFs and in AFFF-contaminated groundwater.