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.

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.

Compositional and structural analysis of engineered stones and inorganic particles in silicotic nodules of exposed workers.

BACKGROUND: Engineered stone silicosis is an emerging disease in many countries worldwide produced by the inhalation of respirable dust of engineered stone. This silicosis has a high incidence among young workers, with a short latency period and greater aggressiveness than silicosis caused by natural materials. Although the silica content is very high and this is the key factor, it has been postulated that other constituents in engineered stones can influence the aggressiveness of the disease. Different samples of engineered stone countertops (fabricated by workers during the years prior to their diagnoses), as well as seven lung samples from exposed patients, were analyzed by multiple techniques. RESULTS: The different countertops were composed of SiO2 in percentages between 87.9 and 99.6%, with variable relationships of quartz and cristobalite depending on the sample. The most abundant metals were Al, Na, Fe, Ca and Ti. The most frequent volatile organic compounds were styrene, toluene and m-xylene, and among the polycyclic aromatic hydrocarbons, phenanthrene and naphthalene were detected in all samples. Patients were all males, between 26 and 46 years-old (average age: 36) at the moment of the diagnosis. They were exposed to the engineered stone an average time of 14 years. At diagnosis, only one patient had progressive massive fibrosis. After a follow-up period of 8 ± 3 years, four patients presented progressive massive fibrosis. Samples obtained from lung biopsies most frequently showed well or ill-defined nodules, composed of histiocytic cells and fibroblasts without central hyalinization. All tissue samples showed high proportion of Si and Al at the center of the nodules, becoming sparser at the periphery. Al to Si content ratios turned out to be higher than 1 in two of the studied cases. Correlation between Si and Al was very high (r = 0.93). CONCLUSION: Some of the volatile organic compounds, polycyclic aromatic hydrocarbons and metals detected in the studied countertop samples have been described as causative of lung inflammation and respiratory disease. Among inorganic constituents, aluminum has been a relevant component within the silicotic nodule, reaching atomic concentrations even higher than silicon in some cases. Such concentrations, both for silicon and aluminum showed a decreasing tendency from the center of the nodule towards its frontier.

Potential of environmental concentrations of the musks galaxolide and tonalide to induce oxidative stress and genotoxicity in the marine environment.

Polycyclic musk compounds have been identified in environmental matrices (water, sediment and air) and in biological tissues in the last decade, yet only minimal attention has been paid to their chronic toxicity in the marine environment. In the present research, the clams Ruditapes philippinarum were exposed to 0.005, 0.05, 0.5, 5 and 50 µg/L of the fragrances Galaxolide® (HHCB) and Tonalide® (AHTN) for 21 days. A battery of biomarkers related with xenobiotics biotransformation (EROD and GST), oxidative stress (GPx, GR and LPO) and genotoxicity (DNA damage) were measured in digestive gland tissues. HHCB and AHTN significantly (p < 0.05) induced EROD and GST enzymatic activities at environmental concentrations. Both fragrances also induced GPx activity. All concentrations of both compounds induced an increase of LPO and DNA damage on day 21. Although these substances have been reported as not acutely toxic, this study shows that they might induce oxidative stress and genotoxicity in marine organisms.

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.

Stress under the sun: Effects of exposure to low concentrations of UV-filter 4- methylbenzylidene camphor (4-MBC) in a marine bivalve filter feeder, the Manila clam Ruditapes philippinarum.

UV filters are a class of emerging contaminants with an annual estimated production of 10,000 tons worldwide that continuously enter aquatic environments. Among UV filters, 4-methylbenzylidenecamphor (4-MBC) is an organic camphor derivative used in the cosmetic industry for its ability to protect the skin against UV, specifically UV B radiation. Individuals of the Japanese clam, Ruditapes philippinarum, were exposed to 4-MBC at environmentally relevant and slightly higher concentrations (nominal: 0, 1, 10, 100 µg L-1) using a semi-static exposure system over a 7-days period followed by a 3-days depuration period (total 10 days) where no 4-MBC was added to the tanks. Assessed mortality reached up to 100 % at the highest exposure concentration and a LC50 value of 7.71 µg·L-14-MBC was derived. Environmental risk assessment carried out in a site specific environment, the Cadiz bay in the south of Spain, revealed a potential risk produced by the presence of 4-MBC. Digestive glands tissues were analysed for differential expression of genes encoding proteins involved in the stress response (SOD, MT, GST, EIF1, BCL2, TP53, CAT, 18S, GADPH, GPX, GADD45, THIO9) by RT-qPCR for relative quantification. Results showed that the presence of 4-MBC at environmentally relevant concentrations induced the expression of genes that encode for antioxidant enzymes (GST) and for proteins related to the inhibition of apoptosis (BCL2) and cellular stress (GADD), suggesting a physiological stress response.

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.

Risk of triclosan based on avoidance by the shrimp Palaemon varians in a heterogeneous contamination scenario: How sensitive is this approach?

As the exposure of organisms to contaminants can provoke harmful effects, some organisms try to avoid a continuous exposure by using different strategies. The aim of the current study was to assess the ability of the shrimp Palaemon varians to detect a triclosan gradient and escape to less contaminated areas. Two multi-compartmented exposure systems (the linear system and the HeMHAS-Heterogeneous Multi-Habitat Assay System) were used and then results were compared. Finally, it was aimed how sensitive the avoidance response is by comparing it with other endpoints through a sensitivity profile by biological groups and the species sensitive distribution. The distribution of the shrimps along the triclosan gradient was dependent on the concentrations, not exceeding 3% for 54 µg/L in the linear system and 7% for 81 µg/L in the HeMHAS; 25% of organisms preferred the compartment with the lowest concentrations in both systems. Half of the population seems to avoid concentrations around 40-50 µg/L. The triclosan concentration that might start (threshold) to trigger an important avoidance (around 20%) was estimated to be of 18 µg/L. The profile of sensitivity to triclosan showed that avoidance by shrimps was less sensitive than microalgae growth and avoidance by guppy; however, it might occur even at concentrations considered safe for more than 95% of the species. In summary, (i) the HeMHAS proved to be a suitable system to simulate heterogeneous contamination scenarios, (ii) triclosan triggered the avoidance response in P. varians, and (iii) the avoidance was very sensitive compared to other ecotoxicological responses.

Disturbance of ecological habitat distribution driven by a chemical barrier of domestic and agricultural discharges: An experimental approach to test habitat fragmentation.

Contamination is an important factor for determining the pattern of habitat selection by organisms. Since many organisms are able to move from contaminated to more favorable habitats, we aimed to: (i) verify if the contamination along the river Guadalete (Spain) could generate a chemical barrier, restricting the displacement of freshwater shrimps (Atyaephyra desmarestii) and (ii) discriminate the role of the contaminants concerning the preference response by the shrimps. A. desmarestii was experimentally tested in a multi-compartmented, non-forced exposure system, simulating the spatial arrangement of the samples just like their distribution in the environment. Water and sediment samples were chemically characterized by analyses of 98 chemical compounds and 19 inorganic elements. Shrimps selected the less contaminated water and sediment samples, with two marked preference patterns: (i) upstream displacement avoiding the sample located at the point of pollutant discharges and those samples downstream from this point and (ii) fragmentation of the population with spatial isolation of the upstream and downstream populations. The preference was related to the avoidance of artificial sweeteners, flame retardants, fragrances, PAHs, PCBs, pesticides, UV filters and some inorganic elements. The threat of contamination was related to its potential to isolate populations due to the chemical fragmentation of their habitat.

Chemical and microbiological characterization of cruise vessel wastewater discharges under repair conditions.

Cruise ship wastewater discharges are pollution sources towards the marine environment that are poorly characterized. In this study, wastewater samples from cruise ships have been obtained during repair works in a shipyard. Different organic pollutants have been analyzed and their concentrations were similar to those in urban wastewaters for pharmaceuticals and fragrances, but higher for UV filters and PAHs. For the first time, cypermethrin, a pesticide highly toxic towards aquatic species, was found at relevant concentrations (>1 µg L^-1). The faecal microorganisms were for all parameters higher than 10^4 CFU 100 mL^-1, which together with the presence of antibiotic compounds in wastewater (e.g., triclosan), could potentially lead to the generation of antibiotic resistance bacteria (ARB). The historical position of cruise ships, determined from the Automatic Identification System (AIS), were used to define the time ships were underway, at port, or in repair. From ship's passenger and crew load, and from estimates of discharges the total volume of wastewater produced by these ships (371,000 m^3 year^-1) and the average flow (0.15 ±â€¯0.03 m^3crew^-1 day^-1) were calculated.

Effects of extreme rainfall events on the distribution of selected emerging contaminants in surface and groundwater: The Guadalete River basin (SW, Spain).

This study is focused on the Guadalete River basin (SW, Spain), where extreme weather conditions have become common, with and alternation between periods of drought and extreme rainfall events. Combined sewer overflows (CSOs) occur when heavy rainfall events exceed the capacity of the wastewater treatment plants (WWTP), as well as pollution episodes in parts of the basin due to uncontrolled sewage spills and the use of reclaimed water and sludge from the local WWTP. The sampling was carried out along two seasons and three campaigns during dry (March 2007) and extreme rainfall (April and December 2010) in the Guadalete River, alluvial aquifer and Jerez de la Frontera aquifer. Results showed minimum concentrations for synthetic surfactants in groundwater (<37.4µg·L-1) during the first campaign (dry weather conditions), whereas groundwater contaminants increased in December 2010 as the heavy rainfall caused the river to overflow. In surface water, surfactant concentrations showed similar trends to groundwater observations. In addition to surfactants, pharmaceuticals and personal care products (PPCPs) were analyzed in the third campaign, 22 of which were detected in surface waters. Two fragrances (OTNE and galaxolide) and one analgesic/anti-inflammatory (ibuprofen) were the most abundant PPCPs (up to 6540, 2748 and 1747ng·L-1, respectively). Regarding groundwater, most PPCPs were detected in Jerez de la Frontera aquifer, where a synthetic fragrance (OTNE) was predominant (up to 1285ng·L-1).

Occurrence and spatial distribution of legacy and emerging organic pollutants in marine sediments from the Atlantic coast (Andalusia, SW Spain).

Contamination of aquatic systems by no longer used but very persistent compounds (e.g., organochlorine pesticides) and newly detected chemicals, such as personal care products (PCPs), represents a raising concern. In this study, we carried out one of the first comparisons of both types of contaminants, legacy and emerging, in two coastal systems (Cadiz Bay and Huelva Estuary). A wide range of analytes were selected to this end, including hydrocarbons, UV filters, fragrances, and antimicrobials. Analysis of surface sediments revealed the occurrence of 46 out of 97 target analytes, most of them predominantly accumulated in depositional areas with high organic carbon content. Polycyclic aromatic hydrocarbons (PAHs), fragrances (e.g., octahydrotetramethyl acetophenone or "OTNE"), UV filters (e.g., octocrylene), and nonylphenol had the highest concentrations (up to 1098, 133.5, 72 and 575ngg-1, respectively). Several inputs were detected, from atmospheric deposition after combustion to wastewater discharges and recreational activities. However, an environmental risk assessment performed for those chemicals for which ecotoxicological data were available, indicated that legacy compounds still pose the highest potential risk towards benthonic organisms (individual hazard quotients up to 580 for dichlorophenyldichloroethylene or "DDE") compared to PCPs.

Solvent bar micro-extraction (SBME) based determination of PAHs in seawater samples.

Measuring the impact of PAHs in seawater samples is often difficult due to the low concentrations in which they appear and the complexity of the sample matrix. Traditional methods for sample preparation such as liquid-liquid extraction and solid phase extraction require the use of excessive amounts of solvents and reagents, and sample handling. In this work, hollow fiber liquid phase micro-extraction (HFLPME), in the configuration of solvent bar micro-extraction (SBME), was proposed as an environmentally friendly and more effective tool, for the extraction of the 16 priority PAHs from seawater samples. Extraction was conducted using hexane as a solvent. Enrichment factors from 45 to 163 were obtained after 60min at a stirring rate of 500rpm in the sample. Moreover, a negative linear relationship was observed between the enrichment factor and the molecular weight of the PAHs. Under optimized conditions, the limits of detection were in the range from 0.21 to 0.82ngL-1, the method showed a linear response up to 500µgL-1, and the average relative standard deviation for seawater samples spiked with 5ngL-1 was 11.6%. After calibration, the SBME was applied to extract PAHs in seawater samples from the Bay of Cadiz (SW Spain), showing an average recovery of 99%. In conclusion, the SBME is an environmentally friendly, one-step alternative for sample preparation in the determination of PAHs in seawater samples.

Distribution, mass inventories, and ecological risk assessment of legacy and emerging contaminants in sediments from the Pearl River Estuary in China.

This study focused on comparing the occurrences and environmental toxic risks for diverse priority and emerging contaminants (>100 chemicals) in the sediments from the Pearl River Estuary (PRE, China). The most predominant compounds were cationic surfactants, organophosphate flame retardants (e.g., triisobutylphosphate), and polycyclic aromatic hydrocarbons (PAHs), accounting for >75% of the total mass inventory (∼330 metric tons). Wastewater discharges seem to be one of the main sources of pollution in the area, as the highest concentrations (>1000ngg-1 for some chemicals) were reported in the upper part of the PRE (near Guangzhou city) and Macau. Highest levels of ultraviolet (UV) filters, however, were observed in recreational areas, revealing the importance of direct sources (e.g., outdoor activities). An environmental risk assessment showed that PAHs and dichlorodiphenyl dichloroethylene had the highest hazard quotient (HQ) values (up to 233). Nonylphenol, a metabolite from nonionic surfactant, and two UV filters (2-ethyl-hexyl-4-trimethoxycinnamate and 4-methylbenzylidene camphor) also posed a significant threat to benthic species (HQ>1). Further research through the realization of monitoring campaigns and toxicity tests is encouraged, as the exposure of the resident aquatic organisms and human population to these and other emerging chemicals is expected to increase over the years.

Distribution and fate of legacy and emerging contaminants along the Adriatic Sea: A comparative study.

The spatial distributions and fates of selected legacy and emerging compounds were investigated and compared in surface sediments sampled along the Adriatic mud-wedge and in deep-sea regions from the southern Adriatic basin. Results indicated that the concentrations of legacy contaminants (PAHs, PCBs and DDTs) and emerging contaminants (tonalide, galaxolide, EHMC, octocrylene, BP3 and NP) ranged from 0.1 to 572 ng g-1 and from

Determination of silicone rubber and low-density polyethylene diffusion and polymer/water partition coefficients for emerging contaminants.

There is a growing interest in assessing the concentration and distribution of new nonregulated organic compounds (emerging contaminants) in the environment. The measurement of freely dissolved concentrations using conventional approaches is challenging because of the low concentrations that may be encountered and their temporally variable emissions. Absorption-based passive sampling enables the estimation of freely dissolved concentrations of hydrophobic contaminants of emerging concern in water. In the present study, calibration was undertaken for 2 polymers, low-density polyethylene (LDPE) and silicone rubber for 11 fragrances, 5 endocrine-disrupting compounds, 7 ultraviolet (UV) filters, and 8 organophosphate flame retardant compounds. Batch experiments were performed to estimate contaminant diffusion coefficients in the polymers (Dp ), which in general decreased with increasing molecular weight. The values for fragrances, endocrine-disrupting compounds, and UV filters were in ranges similar to those previously reported for polycyclic aromatic hydrocarbons, but were 1 order of magnitude lower for organophosphate flame retardant compounds. Silicone rubber had higher Dp values than LDPE and was therefore selected for further experiments to calculate polymer/water partition coefficients (KPW ). The authors observed a positive correlation between log KPW and log octanol/water partition coefficient values. Field testing of silicone rubber passive samplers was undertaken though exposure in the River Alna (Norway) for an exposure time of 21 d to estimate freely dissolved concentration. Some fragrances and UV filters were predominant over other emerging and regulated contaminants, at levels up to 1600 ng L(-1) for galaxolide and 448 ng L(-1) for octocrylene. Environ Toxicol Chem 2016;35:2162-2172. © 2016 SETAC.

In-cell clean-up pressurized liquid extraction and gas chromatography-tandem mass spectrometry determination of hydrophobic persistent and emerging organic pollutants in coastal sediments.

The main goal of this work was to develop, optimize and validate a multi-residue method for the simultaneous determination of 97 contaminants, including fragrances, UV filters, repellents, endocrine disruptors, biocides, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organophosphorus flame retardants, and several types of pesticides in marine sediment samples. Extraction and cleanup were integrated into the same step using pressurized liquid extraction (PLE) with in-cell clean-up (1g of alumina). The extraction was performed using dichloromethane at 100 °C, 1500 psi and 3 extraction cycles (5 min per cycle). Extracts were derivatized with N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA) to improve the signal and sensitivity of some target compounds (i.e., triclosan, 2-hydroxybenzophenone). Separation, identification and quantification of analytes were carried out by gas chromatography (GC) coupled to tandem mass spectrometry. Under optimal conditions, the optimized protocol showed good recovery percentages (70-100%), linearity (>0.99) and limits of detection below 1 ng g(-1) for all compounds. Finally, the method was applied to the analysis of sediment samples from different coastal areas from Andalusia (Spain), where occurrence and distribution of emerging contaminants in sediments is very scarce. Twenty five compounds out of 98 were detected in all samples, with the endocrine disruptor nonylphenol and the fragrance galaxolide showing the highest concentrations, up to 377.6 ng g(-1) and 237.4 ng g(-1), respectively.