Identification and morphological characterization of different types of plastic microparticles.

The knowledge of the polymeric composition of microplastics (MPs) is interesting because offers useful information on the resistance, durability, and degradability of these materials, also allowing progress in the control of this contamination. However, there is currently a lack of reliable standardized methods for the identification, and characterization of the plastic microparticles. This work uses different techniques in a complementary manner for the identification, and characterization of MPs that more frequently are found in the environment. A total of 10 types of plastics were collected (polystyrene (PS), polyethylene terephthalate (PETE), polyethylene (PE), high- and low-density polyethylene (HDPE and LDPE, respectively), polyvinyl chloride (PVC), polypropylene (PP), polytetrafluoroethylene (PTFE), Polyamide (PA, Nylon 6,6) and poly-carbonate (PC)) and their chemical identification were analyzed by reflectance-attenuated infrared (FTIR-ATR). Furthermore, the samples were observed using light microscopy, and scan-ning electron microscopy (SEM). Also, staining with 12 different dyes was performed to improve the identification of microplastics. The results of this study revealed that PETE, PE, HDPE and LDPE, whose SEM images exhibited smoothness and flat uniformity of their surface, were not (or less) susceptible to adsorb staining solutions while PP, PA, PVC, and PTFE, were capable of adsorbing the dye solutions.

High Amounts of Halogenated Natural Products in Sperm Whales (Physeter macrocephalus) from Two Italian Regions in the Mediterranean Sea.

Halogenated natural products (HNPs) are considered to be emerging contaminants whose environmental distribution and fate are only incompletely known. Therefore, several persistent and bioaccumulative HNP groups, together with man-made polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), were quantified in the blubber of nine sperm whales (Physeter macrocephalus) stranded on the coast of the Mediterranean Sea in Italy. The naturally occurring polybrominated hexahydroxanthene derivatives (PBHDs; sum of TetraBHD and TriBHD) were the most prominent substance class with up to 77,000 ng/g blubber. The mean PBHD content (35,800 ng/g blubber) even exceeded the one of PCBs (28,400 ng/g blubber), although the region is known to be highly contaminated with man-made contaminants. Based on mean values, Q1 ∼ PBDEs > MeO-BDEs ∼ 2,2'-diMeO-BB 80 and several other HNPs followed with decreasing amounts. All blubber samples contained an abundant compound whose molecular formula (C16H19Br3O2) was verified using high-resolution mass spectrometry. The only plausible matching isomer was (2S,4'S,9R,9'S)-2,7-dibromo-4'-bromomethyl-1,1-dimethyl-2,3,4,4',9,9'-9,9'-hexahydro-1H-xanthen-9-ol (OH-TriBHD), a hydroxylated secondary metabolite previously detected together with TriBHD and TetraBHD in a sponge known to be a natural producer of PBHDs. The estimated mean amount of the presumed OH-TriBHD was 3000 ng/g blubber, which is unexpectedly high for hydroxylated compounds in the lipids of marine mammals.

Characterization of PCDD/F and dl-PCB levels in air in Gipuzkoa (Basque Country, Spain).

This research examines the levels and trends of pollutants, specifically 17 congeners of PCDD/Fs and 12 dl-PCBs, in the air measured in the province of Gipuzkoa (Basque Country, Spain). The study used PCDD/Fs, dl-PCB, and the sum of dioxin-like compounds as separate response variables. A total of 113 air samples were collected and analyzed using the method described in the European Standard (EN-1948:2006) from two industrial areas. The results were analyzed using non-parametric test to assess the variability of these pollutants based on different factors (year, season and day of the week) and General Linear Models to assess the weight of each factor. The study found that the toxic equivalents (TEQs) for PCDD/Fs were 12.29 fg TEQm-3 and for dl-PCBs were 1.63 fg TEQm-3, which were in a similar range or lower than those observed in other national and international studies in industrial areas. The results showed temporal variations, with higher levels of PCDD/Fs in autumn-winter than in spring-summer and higher levels of PCDD/Fs and dl-PCBs during weekdays than on weekends. The industrial area where the energy recovery plant (ERP) will be located had higher levels of air pollutants due to the presence of two PCDD/Fs emitting industries nearby, as indicated by the Spanish Registry of Polluting Emission Sources. Both industrial areas showed similar profiles of PCDD/Fs and dl-PCBs, with the PCDD/F profiles dominated by OCDD, 1,2,3,4,6,7,8-HpCDD, and 1,2,3,4,6,7,8-HpCDF in terms of concentrations and 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF, and 2,3,7,8-TCDD in terms of TEQs. The dl-PCB profiles were dominated by PCB 118, PCB 105, and PCB 77 in terms of concentrations and PCB 126 in terms of TEQs. The findings of this study can serve as an indicator of the potential impact of ERP on the health of the resident population and the environment.

Evidence of contamination-associated damage in blue sharks (Prionace glauca) from the Northeast Atlantic.

Top predators such as most shark species are extremely vulnerable to amassing high concentrations of contaminants, but not much is known about the effects that the contaminant body burden imparts on these animals. Species like the blue shark (Prionace glauca) are very relevant in this regard, as they have high ecological and socioeconomic value, and have the potential to act as bioindicators of pollution. This work aimed to assess if differences in contaminant body burden found in blue sharks from the Northeast Atlantic would translate into differences in stress responses. Biochemical responses related to detoxification and oxidative stress, and histological alterations were assessed in the liver and gills of 60 blue sharks previously found to have zone-related contamination differences. Similar zone-related differences were found in biomarker responses, with the sharks from the most contaminated zone exhibiting more pronounced responses. Additionally, strong positive correlations were found between contaminants (i.e., As, PCBs, and PBDEs) and relevant biomarkers (e.g., damaged DNA and protective histological alterations). The present results are indicative of the potential that this species and these tools have to be used to monitor pollution in different areas of the Atlantic.

Assessment of contaminants in blue sharks from the Northeast Atlantic: Profiles, accumulation dynamics, and risks for human consumers.

Chemical pollution is a major threat to marine ecosystems, and top predators such as most shark species are extremely vulnerable to being exposed and accumulating contaminants such as metals and persistent organic pollutants (POPs). This work aimed to study the degree, composition, and the sources of contamination in the blue shark (Prionace glauca) inhabiting the Northeast Atlantic, as well as the potential risk faced by human consumers. A total of 60 sharks were sampled in situ aboard fishing vessels, and the concentrations of a set of metals and POPs were analysed in various tissues and complemented with stable isotope analyses. High levels of contaminants were found in most sharks sampled. The concentrations of most metals were higher in the muscle when compared with the liver. Regarding the dangers to consumers posed by the concentrations of arsenic (As), mercury (Hg), and lead (Pb), over 75% of the sharks presented muscle concentrations of at least one contaminant above the legal limits for human consumption, and a risk assessment determined that consumption of meat of these sharks exceeding 0.07 Kg per week could potentially expose human consumers to dangerous amounts of methylmercury (MeHg). Additionally, the assessment of single contaminants may lead to an underestimation of the risk for the human health. Finally, the overall accumulation of contaminants seems to be mostly influenced by the sharks' geographical distribution, rather than sex, size, or trophic level of their prey.

Occurrence and distribution of persistent organic pollutants in the liver and muscle of Atlantic blue sharks: Relevance and health risks.

Blue shark score among the most abundant, widely distributed and worldwide consumed elasmobranchs. In this work contents of PCBs, PCDD/Fs and PBDEs were studied by means of GC-HRMS in muscle and liver of sixty blue sharks from the North East Atlantic sampled in 2019. Concentrations relatively similar were found for PCBs and PCDD/Fs in comparison with those in Atlantic specimens from the same area sampled in 2015. In contrast, PBDE loads doubled, likely mirroring the increased environmental presence of these pollutants. This, together with the different congener profiles reported for the same species in other geographical areas, highlighted the blue shark's potential as bioindicator of the degree and fingerprints of regional pollution by POPs. Interesting dissimilarities between muscle and liver concentrations were detected, most likely ascribed to distinct toxicokinetics involved for the different pollutants. Whereas most POPs preferentially accumulated in liver, some did the opposite in muscle. BDE-209 was the most prominent example, being almost negligible its presence in liver (0.3%) while accounting for ca. 14% of the total PBDE content in muscle. Different findings in this regard described for other shark species call for focused research to ascertain the role of the species in this apparent favored metabolization of BDE-209 in the liver. From a consumption perspective, the concentrations found in muscle -the most relevant part in the human diet-for PCBs and dioxin-like POPs were below the EU maximum allowed levels in foodstuff. Conversely, in liver about 58% and 78% of samples overpassed the European levels for tolerable intake of i-PCBs and dioxin POPs, respectively. Concentrations of PBDEs exceeded EQS (0.0085 ng/g w.w.) established by the European Water Framework Directive in 100% and 92% of liver and muscle samples, respectively, which adds to the open debate of such as a reduce value for this current EQS.

Global PBDE contamination in cetaceans. A critical review.

This review summarizes the most relevant information on PBDEs' occurrence and their impacts in cetaceans at global scale, with special attention on the species with the highest reported levels and therefore the most potentially impacted by the current and continuous release of these substances. This review also emphasizes the anthropogenic and environmental factors that could increase concentrations and associated risks for these species in the next future. High PBDE concentrations above the toxicity threshold and stationary trends have been related to continuous import of PBDE-containing products in cetaceans of Brazil and Australia, where PBDEs have never been produced. Non-decreasing levels documented in cetaceans from the Northwest Pacific Ocean might be linked to the increased e-waste import and ongoing production and use of deca-BDE that is still allowed in China. Moreover, high levels of PBDEs in some endangered species such as beluga whales (Delphinapterus leucas) in St. Lawrence Estuary and Southern Resident killer whales (Orcinus Orca) are influenced by the discharge of contaminated waters deriving from wastewater treatment plants. Climate change related processes such as enhanced long-range transport, re-emissions from secondary sources and shifts in migration habits could lead to greater exposure and accumulation of PBDEs in cetaceans, above all in those species living in the Arctic. In addition, increased rainfall could carry greater amount of contaminants to the marine environment, thereby, enhancing the exposure and accumulation especially for coastal species. Synergic effects of all these factors and ongoing emissions of PBDEs, expected to continue at least until 2050, could increase the degree of exposure and menace for cetacean populations. In this regard, it is necessary to improve current regulations on PBDEs and broader the knowledge about their toxicological effects, in order to assess health risks and support regulatory protection for cetacean species.

Evaluation of PCDD/Fs, PCBs and PBDEs in two penguin species from Antarctica.

Persistent Organic Pollutants (POPs) are a global threat, but impacts of these chemicals upon remote areas such as Antarctica remain unclear. Penguins can be useful species to assess the occurrence of POPs in Antarctic food webs. This work's aim was the evaluation of polychlorodibenzo-p-dioxins and furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in eggs of two penguin species, chinstrap (Pygoscelis antarticus) and gentoo penguins (Pygoscelis papua), breeding in the South Shetland Islands. Results showed a common pattern in POP levels regardless of the species, characterized by a major abundance of PCBs (98 %), followed by PBDEs (1-2%) and PCDD/Fs (<1 %). Concentrations of POPs in chinstrap and gentoo penguin eggs were 482 and 3250 pg/g l.w., respectively. PCBs, PBDEs and PCDD/Fs were found at higher concentrations in chinstrap penguin eggs, being these differences significant for PBDEs. Interspecies differences in POP levels agree well with potential trophic position differences among species due to changes in prey composition and foraging areas. POP profiles were dominated by congeners with a low degree of halogenation. Our results therefore suggest similar sources of POPs in the food webs exploited by both species and in both cases attributable to the long-range transportation rather than to the presence of local sources of POPs. TEQs were found between 1.38 and 7.33 pg/g l.w. and followed the pattern non-ortho dl-PCBs > PCDFs > PCDDs > mono-ortho dl-PCBs. TEQ values were lower than the threshold level for harmful effects in birds of 210 pg/g WHO-TEQ/g l.w.

Levels and trends of perfluoroalkyl acids (PFAAs) in water (2013-2020) and fish from selected riverine basins in Spain.

The aim of the present study was to assess the presence of perfluoroalkyl acids (PFAAs), namely perfluoroalkane sulfonates and perfluoroalkyl carboxylic acids, in Spanish river basins in order to: identify potential spatiotemporal variations; evaluate the effectiveness of the measures implemented for the reduction/elimination of these pollutants; verify the fulfillment of the Environmental Quality Standards (EQSs) in the European Union. PFOS and PFOA were determined in 116 water samples from four sites in the Duero basin, the largest in the Iberian Peninsula, collected seasonally from 2013 to 2020. In addition, 30 fish sample composites from the sample banks of Duero, Tagus, Ebro, Eastern Cantabrian and Catalonian basins were analyzed for 15 PFAAs. Median PFOS and PFOA concentrations were 0.72 and 0.42 ng/L, ranging from values below the limit of quantification (LOQ) to 81 and 22 ng/L, respectively. During the studied period, 51% of water samples were above the EQS of 0.65 ng/L for PFOS. In the case of fish, the PFOS range was

Global intercomparison of polyurethane foam passive air samplers evaluating sources of variability in SVOC measurements.

Polyurethane foam passive air samplers (PUF-PAS) are the most common type of passive air sampler used for a range of semi-volatile organic compounds (SVOCs), including regulated persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs), and emerging contaminants (e.g., novel flame retardants, phthalates, current-use pesticides). Data from PUF-PAS are key indicators of effectiveness of global regulatory actions on SVOCs, such as the Global Monitoring Plan of the Stockholm Convention on Persistent Organic Pollutants. While most PUF-PAS use similar double-dome metal shielding, there is no standardized dome size, shape, or deployment configuration, with many different PUF-PAS designs used in regional and global monitoring. Yet, no information is available on the comparability of data from studies using different PUF-PAS designs. We brought together 12 types of PUF-PAS used by different research groups around the world and deployed them in a multi-part intercomparison to evaluate the variability in reported concentrations introduced by different elements of PAS monitoring. PUF-PAS were deployed for 3 months in outdoor air in Kjeller, Norway in 2015-2016 in three phases to capture (1) the influence of sampler design on data comparability, (2) the influence of analytical variability when samplers are analyzed at different laboratories, and (3) the overall variability in global monitoring data introduced by differences in sampler configurations and analytical methods. Results indicate that while differences in sampler design (in particular, the spacing between the upper and lower sampler bowls) account for up to 50 % differences in masses collected by samplers, the variability introduced by analysis in different laboratories far exceeds this amount, resulting in differences spanning orders of magnitude for POPs and PAHs. The high level of variability due to analysis in different laboratories indicates that current SVOC air sampling data (i.e., not just for PUF-PAS but likely also for active air sampling) are not directly comparable between laboratories/monitoring programs. To support on-going efforts to mobilize more SVOC data to contribute to effectiveness evaluation, intercalibration exercises to account for uncertainties in air sampling, repeated at regular intervals, must be established to ensure analytical comparability and avoid biases in global-scale assessments of SVOCs in air caused by differences in laboratory performance.

Soil concentrations, compositional profiles, sources and bioavailability of polychlorinated dibenzo dioxins/furans, polychlorinated biphenyls and polycyclic aromatic hydrocarbons in open municipal dumpsites of Chennai city, India.

Several studies have reported the release of halogenated persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs) associated with open burning of municipal solid waste. Considering soil as a sink for such organic contaminants, we conducted an in-depth study on the surface soil concentrations of polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and sixteen USEPA enlisted PAHs collected from thirteen zones of the two major municipal dumpsites, Kodungaiyur dumpsite (KDS) and Perungudi dumpsite (PDS) of Chennai city. Indigenous microbes from dumpsite soil samples were isolated and identified based on 16S rRNA sequencing and phylogenetic analysis. Using indigenous microbes, we have elucidated the bioavailability of the targeted organic pollutants for each site.Range of Σ17PCDD/Fs, Σ25PCBs and ∑16PAHs varied between 3.96-612 pg/g (96.0 pg/g; median), ND-182 ng/g (6.35 ng/g; median) and 0.62-3649 ng/g (64.3 ng/g; median), respectively. All the dumpsite samples showed bioavailability for POPs and PAHs. Toxicity equivalent values (TEQs) associated with dioxin-like PCBs and PCDD/Fs from the zones where dumped municipal solid wastes were collected from electronic-waste/IT-corridor/port areas and toxic PAHs from the zone receiving wastes from the industrial corridor of the city were higher than the soil permissible limit prescribed by the World Health Organization.

Persistent Organic Pollutants Burden, Trophic Magnification and Risk in a Pelagic Food Web from Coastal NW Mediterranean Sea.

The storage capacity, trophic magnification and risk of sixty-two POPs have been evaluated in a well-characterized pelagic food web (including phytoplankton, zooplankton, six fish, and two cephalopods species) from an impacted area in NW Mediterranean Sea. Our results show the high capacity of the planktonic compartment for the storage of polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), consistent with their estimated low trophic magnification factors (TMF) of 0.2-2.0 (PBDEs) and of 0.3-1.1 (PCDD/Fs). ∑PBDEs dominated in the zooplankton size-class 200-1000 µm (∼330 ng g-1 lw, median), whereas ∑PCDD/Fs accumulated preferentially in phytoplankton size-class 0.7-200 µm (875 pg g-1 lw, median). In contrast, polychlorinated biphenyls (PCBs) were preferentially bioaccumulated in the higher trophic levels (six fish species and two cephalopods) with TMFs = 0.8-3.9, reaching median concentrations of 4270 and 3140 ng g-1 lw (∑PCBs) in Atlantic bonito (Sarda sarda) and chub mackerel (Scomber colias), respectively. For these edible species, the estimated weekly intakes of dioxin-like POPs for humans based on national consumption standards overpassed the EU tolerable weekly intake. Moreover, the concentrations of nondioxin-like PCBs in S. sarda were above the EU maximum levels in foodstuffs, pointing to a risk. No risk evidence was found due to consumption of all other edible species studied, neither for PBDEs. The integrated burden of POPs in the food web reached ∼18 µg g-1 lw, representing a dynamic stock of toxic organic chemicals in the study area. We show that the characterized food web could be a useful and comprehensive "bioindicator" of the chemical pollution status of the study area, opening new perspectives for the monitoring of toxic chemicals in Mediterranean coastal waters.

First assessment of POPs and cytochrome P450 expression in Cuvier's beaked whales (Ziphius cavirostris) skin biopsies from the Mediterranean Sea.

The Cuvier's beaked whale (Ziphius cavirostris) is one of the least known cetacean species worldwide. The decreasing population trend and associated threats has led to the IUCN categorising the Mediterranean subpopulation as Vulnerable on the Red List of Threatened Species. This study aimed to investigate for the first time the ecotoxicological status of Cuvier's beaked whale in the NW Mediterranean Sea. The study sampled around the 20% of the individuals belonging to the Ligurian subpopulation, collecting skin biopsies from free-ranging specimens. The levels of polychlorinated biphenyl (PCBs), polybrominated diphenyl ethers (PBDEs) and induction of cytochrome's P450 (CYP1A1 and CYP2B isoforms) were evaluated. Results highlighted that the pattern of concentration for the target contaminants was PCBs > PBDEs and the accumulation values were linked to age and sex, with adult males showing significantly higher levels than juvenile. Concerns raised by the fact that 80% of the individuals had PCB levels above the toxicity threshold for negative physiological effects in marine mammals. Therefore, these findings shed light on this silent and serious threat never assessed in the Mediterranean Cuvier's beaked whale population, indicating that anthropogenic pressures, including chemical pollution, may represent menaces for the conservation of this species in the Mediterranean Sea.

Assessment of PCDD/Fs, dioxin-like PCBs and PBDEs in Mediterranean striped dolphins.

Bio-accumulation of high levels of persistent organic pollutants represent a serious conservation concern for Mediterranean marine odontocetes. In this study, blubber samples from 10 striped dolphins (Stenella coeruleoalba) stranded along the Italian coasts during 2015-2016 were analyzed. All specimens showed dl-PCBs > PBDEs ≫ PCDD/Fs. Median concentrations were 1820 ng/g l.w., 456 ng/g l.w. and 23.9 pg/g l.w., respectively. dl-PCBs accounted for 93.3% of total TEQs. PBDE concentrations suggest that the Mediterranean basin may be considered a hotspot for organobromine compounds. OCDD did not represent the greatest contributor to PCDD/Fs profile, most likely due to a change in dioxin environmental sources in the last two-three decades. Despite international regulations, the present study emphasized that POP exposure levels in Mediterranean striped dolphins have not declined significantly in recent years. Toxicological and risk assessment studies on this sentinel species may provide an early indication of potential adverse health effects on Mediterranean ecosystems.

Plasticizers and bisphenol A in Adyar and Cooum riverine sediments, India: occurrences, sources and risk assessment.

Adyar and Cooum, the two rivers intersecting Chennai city, are exposed to serious pollution due to the release of large quantities of dumped waste, untreated wastewater and sewage. Sediments can act as repository for emerging organic contaminants. Hence, we have monitored the occurrence and risk associated with plasticizers [six phthalic acid esters (PAEs), bis(2-ethyl hexyl adipate) (DEHA)] and bisphenol A (BPA) in surface riverine sediments of Adyar and Cooum rivers from residential/commercial, industrial and electronic waste recycling sites. Σ7plasticizers (PAEs + DEHA) in the Adyar riverine sediment (ARS) and Cooum riverine sediment (CRS) varied between 51.82-1796 and 28.13-856 ng/g, respectively. More than three-fourth of Σ7plasticizers came from bis(2-ethylhexyl) phthalate (DEHP), in accordance with the high production and usage of this compound. BPA varied between 10.70-2026 and 7.58-1398 ng/g in ARS and CRS, respectively. Average concentrations of plasticizers and BPA were four times higher in electronic waste (e-waste) recycling sites when compared with industrial and residential/commercial sites. BPA and DEHP showed a strong and significant correlation (R2 = 0.7; p < 0.01) in the e-waste sites thereby indicating common source types. Sites present at close proximity to raw sewage pumping stations contributed to 70% of the total BPA observed in this study. For the derived pore water concentration of plasticizers and BPA, the ecotoxicological risk has been found to be higher in ARS over CRS. However, sediment concentrations in all the sites of ARS and CRS were much below the recommended serious risk concentration for human (SRChuman) and serious risk concentration for ecotoxicological (SRCeco).

Assessment of POPs in air from Spain using passive sampling from 2008 to 2015. Part II: Spatial and temporal observations of PCDD/Fs and dl-PCBs.

Time series (2008-2015) of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in ambient air from the Spanish Monitoring Program were analyzed. A total of 321 samples were collected seasonally each year in 5 urban and 7 background sites by means of passive air sampling. Air concentrations were higher at urban than background sites (urban vs. background concentration ranges): PCDD/Fs (26.9-1010 vs. 20.0-357 fg/m3), non-ortho PCBs (0.113-3.14 vs. 0.042-2.00 pg/m3) and mono-ortho PCBs (0.644-41.3 vs. 0.500-32.8 pg/m3). Results showed significant decreases from 2009 for non-ortho PCBs and PCDD/Fs as well as for WHO2006-TEQs. These declines were sharper, and sometimes only significant, in urban places resulting in converging levels at urban and background sites for these pollutants at the end of the study period. In contrast, mono-ortho PCBs did not show any significant variation but a steady flat temporal behavior in their concentrations, suggesting the existence of different sources between mono-ortho and non-ortho PCBs. Seasonality was observed for air burdens of all these POPs. PCDD/Fs were mostly measured at higher concentrations in colder than in hot seasons, and the opposite was true for dl-PCBs. Seasonal variations for PCDD/Fs appeared to be related to changes in their sources (e.g. domestic heating, open burning) rather than to temperature per se. In contrast, environmental temperature dependent factors (e.g. increased partitioning into the gas phase) drove seasonal variations in dl-PCBs instead of seasonal changes in their sources. Regarding spatial patterns, significant greater levels of PCDD/Fs and dl-PCBs were generally found in cities compared to background areas, pointing out the role of densely populated areas as sources for these pollutants in Spain. As proven by our results, long-term monitoring activities are essential to assess and understand temporal behaviors for these POPs, as well as to evaluate the achievement of Stockholm Convention objectives.

Assessment of POPs in air from Spain using passive sampling from 2008 to 2015. Part I: Spatial and temporal observations of PBDEs.

The Stockholm Convention (SC) on Persistent Organic Pollutants (POPs) calls for the Parties' effectiveness evaluation of those measures taken to meet the reduction and eventual elimination of POPs from the environment. With that goal, air concentrations of different POP families have been measured uninterruptedly since 2008 under the Spanish Monitoring Program (SMP) by means of passive air sampling. This work focuses on data for polybrominated diphenyl ethers (PBDEs) determined in a total of 321 samples collected seasonally each year in 5 urban and 7 background sites. Neither significant temporal trends nor significant seasonal variations for total PBDE air burdens were detected. In contrast, significant variations were found among PBDE congeners. Those related to the octa-PBDE formulation significantly decreased in the study period. However, PBDEs related to the penta-formulation showed steady concentrations while PBDE-209, the congener found at the greatest levels, showed increasing or steady levels in most sampling sites. Seasonal variations were also markedly different among congeners. Concentrations of the lightest PBDEs (tri- to penta-substituted) were highly influenced by ambient temperature (T), showing maximum values in summer probably due to higher volatilization rates compared to those of heavier PBDEs. Contrarily, no clear seasonal trends were found for hexa- to deca-PBDEs, which were negatively related to precipitation; thereby, indicating an efficient atmospheric wash out by wet deposition episodes. Regarding spatial patterns, overall significant greater PBDE levels were found in cities compared to background areas, pointing out the role of highly populated areas as sources for these pollutants in Spain. Yet and especially in the case of PBDE-209, our results suggested the presence of significant unknown sources of PBDEs in some background sites. Further monitoring efforts are needed to assess potential unknown sources in the sampling network as well as to ensure temporal trends of these pollutants in Spain.

Occurrence, Loading, and Exposure of Atmospheric Particle-Bound POPs at the African and European Edges of the Western Mediterranean Sea.

A comparative study for 62 toxic chemicals based on the simultaneous monthly collection of aerosol samples during 2015-2016 in two coastal cities at both the African (Bizerte, Tunisia) and European (Marseille, France) edges of the Western Mediterranean basin is presented. Legacy polychlorinated biphenyls (∑18PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (∑17PCDD/Fs) show generally higher median levels at the African edge (2.1 and 0.2 pg m-3, respectively) compared to the European coastal site (1.0 and 0.08 pg m-3, respectively). Contrarily, the "emerging" polybrominated diphenyl ethers' (∑27PBDEs) median concentrations were higher in Marseille (∼9.0 pg m-3) compared to Bizerte (∼6.0 pg m-3). Different past usages and current emission patterns were found at both edges of the Western Mediterranean, most probably linked to the respective different regulatory frameworks for toxic chemicals. Our results indicate that the total organic carbon (TOC) and/or the elemental carbon (EC) contents in the atmospheric aerosol may have a stronger effect than the total suspended particle (TSP) content as a whole on the spatial-temporal variability and the long-range atmospheric transport potential of the studied POPs. A "jumping" of the PBDE local atmospheric stocks from the Northwestern European Mediterranean edge to the Northwestern African coast seems to be possible under favorable conditions at present. While a higher PBDE median loading is estimated for the Marseille area (∼550 ng m-2 y-1) compared to Bizerte (∼400 ng m-2 y-1), the median PCB and PCDD/F dry deposition fluxes were higher at the African site, resulting in a 3-fold higher toxic equivalent (TEQ) loading of dioxin-like pollutants (400 pg TEQ m-2 y-1) compared to Marseille (∼140 pg TEQ m-2 y-1), with potential implications for aquatic organisms. However, the inhalation exposure assessment points to a minimum risk for human health at both sites.

Are whale sharks exposed to persistent organic pollutants and plastic pollution in the Gulf of California (Mexico)? First ecotoxicological investigation using skin biopsies.

The whale shark (Rhincodon typus) is an endangered species that may be exposed to micro- and macro-plastic ingestion as a result of their filter-feeding activity, particularly on the sea surface. In this pilot project we perform the first ecotoxicological investigation on whale sharks sampled in the Gulf of California exploring the potential interaction of this species with plastic debris (macro-, micro-plastics and related sorbed contaminants). Due to the difficulty in obtaining stranded specimens of this endangered species, an indirect approach, by skin biopsies was used for the evaluation of the whale shark ecotoxicological status. The levels of organochlorine compounds (PCBs, DDTs), polybrominated diphenyl ethers (PBDEs) plastic additives, and related biomarkers responses (CYP1A) were investigated for the first time in the whale shark. Twelve whale shark skin biopsy samples were collected in January 2014 in La Paz Bay (BCS, Mexico) and a preliminary investigation on microplastic concentration and polymer composition was also carried out in seawater samples from the same area. The average abundance pattern for the target contaminants was PCBs>DDTs>PBDEs>HCB. Mean concentration values of 8.42ng/g w.w. were found for PCBs, 1.31ng/g w.w. for DDTs, 0.29ng/g w.w. for PBDEs and 0.19ng/g w.w. for HCB. CYP1A-like protein was detected, for the first time, in whale shark skin samples. First data on the average density of microplastics in the superficial zooplankton/microplastic samples showed values ranging from 0.00items/m3 to 0.14items/m3. A focused PCA analysis was performed to evaluate a possible correlation among the size of the whale sharks, contaminants and CYP1A reponses. Further ecotoxicological investigation on whale shark skin biopsies will be carried out for a worldwide ecotoxicological risk assessment of this endangerd species.

Towards the implementation of the Stockholm Convention in Spain: Five-year monitoring (2008-2013) of POPs in air based on passive sampling.

Within the framework of the Spanish monitoring program, this study reports on air concentration of DDTs, HCB, HCHs, NDL-PCBs, DL-PCBs, PCDD/Fs and PBDEs measured during the five-year sampling period 2008-2013. Spanish coastal remote and urban locations were studied using PUF disk passive air samplers which were deployed and collected every three months. Despite the wide range of concentrations measured for most contaminants, a common pattern of relative abundance (median values): NDL-PCBs (36.6 pg/m(3)) > HCB (24.8 pg/m(3)) ≈ HCHs (17.9 pg/m(3)) ≈ DDTs (16.6 pg/m(3)) > PBDEs (3.65 pg/m(3)) > DL-PCBs (2.99 pg/m(3)) >> PCDD/Fs (0.060 pg/m(3)) was found fairly consistent across most seasons and locations. Nevertheless, important variations in yearly concentrations were measured for different POPs. In general, higher levels of DDTs, HCHs, NDL-PCBs, DL-PCBs and PCDD/Fs were found in urban sites highlighting important differences between remote and urban sampling locations for most target contaminants. Greater concentrations of the banned organochlorine pesticides in urban locations suggested the existence of unexpected pointed sources that need to be further investigated and characterized. The limited dataset collected thus far rendered no clear temporal trends for most study target compounds, which emphasizes the necessity of the Spanish monitoring program future maintenance in time.