First determination of high levels of organophosphorus flame retardants and plasticizers in dolphins from Southern European waters.

This study evaluates for the first time organophosphorus flame retardant (OPFR) occurrence in the Alboran Sea delphinids (Spain). OPFRs were detected in all the individuals with concentration levels up to 24.7 µg/g lw. Twelve out of sixteen tested analytes were detected, being TBOEP which presented the highest detection frequency, and IDPP which presented the highest levels of concentration. OPFR distribution in different tissues (blubber, brain, kidney, muscle and liver) was evaluated. The pattern distribution showed the highest contribution for blubber (mean value of 68%) and the lowest contribution for liver (mean value of 2%). Seven OPFRs were detected in brain samples showing their capacity to surpass the blood-brain barrier and reach the brain. Moreover, high affinity for the brain tissue was observed. This is extremely important due to the neurotoxic effects of several compounds such as TCEP and TNBP. OPFR levels were compared with previously published PBDE concentrations, and no significant differences were observed. Taking into account the lower use and lower bioaccumulation and biomagnification capacities of OPFRs, this could indicate an additional OPFR source of pollution in addition to their use as FRs.

Halogenated Natural Products in Dolphins: Brain-Blubber Distribution and Comparison with Halogenated Flame Retardants.

Halogenated natural products (MHC-1, TriBHD, TetraBHD, MeO-PBDEs, Q1, and related PMBPs) and halogenated flame retardants (PBDEs, HBB, Dec 602, Dec 603, and DP) in blubber and brain are reported from five Alboran Sea delphinids (Spain). Both HNPs and HFRs were detected in brain, implying that they are able to surpass the blood-brain barrier and reach the brain, which represents a new finding for some compounds, such as Q1 and PMBPs, MHC-1, TriBHD, TetraBHD, or Dec 603. Moreover, some compounds (TetraBHD, BDE-153, or HBB) presented higher levels in brain than in blubber. This study evidence the high concentrations of HNPs in the marine environment, especially in top predators. It shows the importance of further monitoring these natural compounds and evaluating their potential toxicity, when most studies focus on anthropogenic compounds only. While no bioaccumulation was found for ∑HNPs, ∑HFRs increased significantly with body size for both common and striped dolphins. Studies evaluating BBB permeation mechanisms of these compounds together with their potential neurotoxic effects in dolphins are recommended.

Gas chromatography/tandem mass spectrometry method for the simultaneous analysis of 19 brominated compounds in environmental and biological samples.

A methodology for the simultaneous analysis of eight polybrominated diphenyl ethers (PBDEs); eight methoxylated PBDEs (MeO-PBDEs); and three emerging flame retardants, hexabromobenzene (HBB), pentabromoethyl benzene (PBEB), and decabromodiphenyl ethane (DBDPE) by gas chromatography coupled to tandem mass spectrometry (GC-MS-MS) was developed for two environmental matrices (sediment and sludge) and three biological matrices (fish, dolphin blubber, and bird eggs). The use of selective reaction monitoring (SRM) allows a high selectivity, which is critical in the analysis of complex samples like blubber. Analytical parameters such as linearity, reproducibility, or accuracy were evaluated. Method limits of detection and quantification were evaluated and compared with GC-EI-MS and GC-NCI-MS. Method detection limits were valid for the environmental analysis in all cases, with values between 0.01 and 1.65 ng/g dw for sediment, 0.05 and 2.78 ng/g dw for sludge, 0.04 and 10.6 ng/g lw for fish, 0.01 and 1.11 ng/g lw for dolphin blubber, and 0.03 and 3.20 ng/g lw for bird eggs. The developed method was applied to five samples of each matrix. PBDEs were detected in all samples, while MeO-PBDEs were only detected in dolphin blubber. DBDPE was detected in sediment and sludge.

Comprehensive risk assessment of the inhalation of plasticizers from the use of face masks.

Disposable masks, formed mainly from polymers, often incorporate various chemical additives to enhance their performance. These additives, which include plasticizers, may be released during mask usage, presenting a novel source of human exposure to these compounds. In this study, the presence of 16 organophosphate esters (OPEs), 11 phthalates, and four alternative plasticizers, in four various types of face masks, were studied, as well as their release during simulated mask use (artificial laboratory conditions). Total plasticizer concentrations exhibited minimal variation across different mask types, with mean values of 7.27 µg/face mask for surgical, 8.61 µg/face mask for reusable, 11.0 µg/face mask for KN-95, and 13.9 µg/face mask for FFP2 masks. To explore plasticizer release behavior, inhalation experiments were conducted under different conditions. The findings revealed a significant temperature-dependent enhancement in plasticizer release from masks, subsequently increasing human inhalation exposure. The inhalation experiments showed variation in the release percentages, ranging from 0.1 to 95 %, depending on the specific compound and mask type. Notably, OPEs exhibited a mean release percentage of 1.0 %, similar to phthalates, which showed a 1.2 % release. Although alternative plasticizers were less frequently released, they still presented a notable percentage of release of 4.1 %. Daily intake estimations via inhalation ranged from 0.01 to 9.04 ng/kg body weight (bw)/day for these additives. Using these estimations, carcinogenic and non-carcinogenic risks associated with this exposure to these compounds were evaluated. All calculated values for the specific compounds studied in this paper remained below the established threshold limits. However, they do represent an additional exposure pathway that, when considered alongside other more predominant routes such as indoor/outdoor inhalation, dermal absorption, and dietary intake, makes the total exposure worthy of consideration.

Pesticides in water and sediments from natural protected areas of Spain and their associated ecological risk.

In the last years, issues related to intensive agriculture have been found in protected areas potentially harming wildlife. This study aimed to analyze a wide range of pesticides in water and sediments of two protected areas namely Doñana Natural Park (DNP) and Tablas de Daimiel National Park (TDNP) performing an environmental risk assessment in order to highlight potential risks to living organisms derived from pesticide burden. Higher pesticide load was found in DNP than TDNP with similar distribution profiles, with pyrethroid insecticides (PYRs) the main detected class. Particularly problematic are two PYRs, cyhalothrin and fenvalerate, which were detected at high concentrations that can pose a high risk to aquatic organisms. In addition, despite being detected at lower concentrations, the presence of chlorpyrifos, cypermethrin, and permethrin in water, and of chlorpyrifos, dicofol, and diflufenican in sediments, must be taken into account due to their potential risks for aquatic organisms. Moreover, some banned pesticides such as dimethoate, terbutryn, diazinon, and tricyclazol were detected in water at levels which deserve further investigation to assess their potential sources, including potential illegal practices.

Pesticide contamination of bird species from Doñana National Park (southwestern Spain): Temporal trends (1999-2021) and reproductive impacts.

Doñana National Park (DNP) is a protected area renowned for hosting a wide variety of birds. However, the agricultural practices in its surroundings might cause pesticide contamination of the park biota. This work aimed to assess temporal trends of a wide variety of pesticides, including organochlorine (OCPs), organophosphate (OPPs) and pyrethroid (PYRs) pesticides, in bird eggs collected for more than twenty years (1999-2021) in DNP. Twenty-six pesticides were detected, being 4,4'-DDE the most frequently detected and also the one with the highest concentrations (up to 2.55 µg g-1 ww), exceeding in some cases the values usually reported to cause detrimental health and reproductive effects in avian species. An overall decreasing trend of OCPs was observed. In contrast, an apparent increase in PYRs was detected from 2013 onwards, especially for fenvalerate, whose median concentration was 3-5 orders of magnitude higher in the most recent samples. Moreover, other pesticides such as oxadiazon, oxyfluorfen and fenitrothion were first detected in 2021 samples. Finally, two variables estimating the cumulative impact of pesticides significantly decreased the breeding performance of a top predator such as the booted eagle. Therefore, it is essential to control the use of pesticides in the agricultural practices surrounding DNP and to study their potential negative impact on the bird populations breeding in this protected area.

Dechlorane-related compounds in franciscana dolphin (Pontoporia blainvillei) from southeastern and southern coast of Brazil.

Concentrations of Dechlorane (Dec) 603 (0.75 ng/g lipid weight (lw); mean) and Dec 602 (0.38 ng/g lw; mean) were quantified in more than 95% of the franciscana (Pontoporia blainvillei) dolphin samples, whereas the frequency of detection decreased to 75% for Dechlorane Plus (DP) (1.53 ng/g lw, mean). The presence of Chlordene Plus (CP) was also observed (0.13 ng/g lw, mean) in half of the samples. On the contrary, Dec 604, decachloropentacyclooctadecadiene (aCl(10)DP), and undecachloropentacyclooctadecadiene (aCl(11)DP) concentrations were below the limit of quantifications in all cases. To the best of our knowledge, this is the first article reporting the presence of Dec 603, Dec 602, and CP in mammals. For comparative purposes, levels of Mirex, polybrominated diphenyl ethers (PBDEs), and decabromodiphenylethane (DBDPE) are also reported. Considering geographic distribution evaluation together with the strong positive correlations found between DP and PBDEs (r(s) = 0.63; p < 0.01), highly anthropogenic areas were identified as potential sources of these chemicals in this dolphin species. However, local sources for Dec 602, 603, Mirex, CP, and DBDPE were not found indicating that in this case historical use and/or atmospheric transport and deposition may play an important role in their fate.

Dechlorane Plus and related compounds in aquatic and terrestrial biota: a review.

Dechlorane Plus, dechlorane 602, dechlorane 603 and dechlorane 604 are flame retardants that have been used for a long time as a substitute for mirex, but they have not been noticed as environmental contaminants until recently (2006). Regardless of their large molecular size and very high lipophilicity (log K(OW) > 9), Dechlorane Plus and related compounds have been detected in different aquatic and terrestrial species, supporting their bioaccumulation and biomagnification. Moreover, some studies showed different behaviour of the syn-Dechlorane Plus and anti-Dechlorane Plus isomers in the environment and different biomagnification factors in biota. This review describes the different analytical approaches applied to the determination of Dechlorane Plus and related compounds. Moreover, a summary of their levels in aquatic and terrestrial biota, as well as in humans, is presented, showing also current research results on their bioaccumulation and biomagnification potential. Finally, isomer-specific bioaccumulation of Dechlorane Plus is also discussed.

Pesticides in sediments of the Ebro River Delta cultivated area (NE Spain): Occurrence and risk assessment for aquatic organisms.

Intense agricultural activities are performed in the Ebro River Delta (NE Spain) with extensive use of pesticides. Medium to highly polar pesticides have not been studied intensively in sediments despite its larger use in the recent years. This work aimed at assessing the occurrence of 69 pesticides, including medium to highly polar compounds, in sediments collected from drainage and irrigation channels of the Ebro River Delta during the main rice growing season. In addition, an environmental risk assessment was performed to evaluate the potential adverse effects to sediment-dwelling organisms with the risk quotient approach. A total of 24 pesticides were detected in sediments with bentazone and cypermethrin exhibiting high detection frequencies (79%) as well as high mean concentration levels (61.9 and 81.8 ng g-1 dw, respectively). Overall, the Alfacs bay, in the South of the delta, presented higher pesticide contamination than the Fangar bay, in the North. A similar pesticide distribution profile was observed in both bays, with oxadiazoles, organochlorines, pyrethroids, benzothiazinones and organophosphates as major, predominant classes. The presence of oxadiazon, pendimethalin and thifensulfuron methyl in the sediments may pose a moderate risk to sediment-dwelling organisms while bentazone, chlorpyrifos, and cypermethrin exhibited a potential high risk. Thus, the importance of the inclusion of medium to highly polar pesticides in the analysis of sediments is emphasized since some polar pesticides such as bentazone, imidacloprid, and thifensulfuron-methyl have been detected at concentrations that may pose a risk to aquatic organisms. Moreover, the co-occurrence of pesticides may potentially pose a high risk to sediment-dwelling organisms in 13 out of the 14 investigated locations. Finally, it could be concluded that the risk derived from the presence of pesticides in sediments must be assessed since some pesticides not detected at concerning levels in water, may pose a moderate/high risk in the sediments.

Exposure of e-waste dismantlers from a formal recycling facility in Spain to inhalable organophosphate and halogenated flame retardants.

Concentration levels of 16 organophosphate esters (OPEs) and 18 halogenated flame retardants (HFRs) were measured in airborne fine particulate matter (PM2.5) from an e-waste dismantling facility in Catalonia (Spain) to assess their occurrence, profiles and potential health risks. Three different areas from the facility were studied, including an area for cathodic ray-tube (CRT) TV dismantling, a grinding area, and the outdoor background. OPEs and HFRs were detected in all samples, with concentrations between 10.4 and 110 ng/m3 for OPEs and from 0.72 to 2213 ng/m3 for HFRs. The compounds with highest concentrations in both working areas were triphenyl phosphate (TPHP) and tris(2-chloroisopropyl) phosphate (TCIPP) for OPEs and decabromodiphenyl ether (BDE-209) for HFRs. Higher concentration levels were found in the CRT area compared to the grinding one, probably due to the lower ventilation and different types of e-waste being processed. OPEs were also detected in the solid e-waste from the facility, highlighting the need to evaluate pollutant levels in e-waste before proceeding to its re-use. Estimated daily intakes via inhalation during workday were calculated, as well as carcinogenic and non-carcinogenic health risks, these being 25 and 50 times lower than threshold risk values in the worst cases, respectively. However, this calculated risk only considers the workday exposure via inhalation, while other routes of exposure (e.g., ingestion, dermal) could bring these values closer to threshold values.

E-waste dismantling as a source of personal exposure and environmental release of fine and ultrafine particles.

Electronic waste (WEEE; from TV screens to electric toothbrushes) is one of the fastest growing waste streams in the world. Prior to recycling, e-waste components (metals, wood, glass, etc.) are processed by shredding, grinding and chainsaw cutting. These activities generate fine and ultrafine particle emissions, containing metals as well as organics (e.g., flame retardants), which have high potential for human health impacts as well as for environmental release. In this work, release of fine and ultrafine particles, and their exposure impacts, was assessed in an e-waste recycling facility under real-world operating conditions. Parameters monitored were black carbon, particle mass concentrations, ultrafine particles, and aerosol morphology and chemical composition. Potential health impacts were assessed in terms of cytotoxicity (cell viability) and oxidative stress (ROS) on <2 µm particles collected in liquid suspension. Environmental release of WEEE aerosols was evidenced by the higher particle concentrations monitored outside the facility when compared to the urban background (43 vs.11 µgPM2.5/m3, respectively, or 2.4 vs. 0.2 µgCa/m3). Inside the facility, concentrations were higher in the top than on the ground floor (PM2.5 = 147 vs. 78 µg/m3, N = 15.4 ∗ 104 vs. 8.7 ∗ 104/cm3, BC = 12.4 vs. 7.2 µg/m3). Ventilation was a key driver of human exposure, in combination with particle emissions. Key chemical tracers were Ca (from plastic fillers) and Fe (from wiring and other metal components). Y, Zr, Cd, Pb, P and Bi were markers of cathode TV recycling, and Li and Cr of grinding activities. While aerosols did not evidence cytotoxic effects, ROS generation was detected in 4 out of the 12 samples collected, associated to the ultrafine fraction. We conclude on the need for studies on aerosol emissions from WEEE facilities, especially in Europe, due to their demonstrable environmental and human health impacts and the rapidly growing generation of this type of waste.

Performance of gas chromatography/tandem mass spectrometry in the analysis of pyrethroid insecticides in environmental and food samples.

The performance of gas chromatography coupled with tandem mass spectrometry (GC/MS/MS) was tested for the simultaneous determination of twelve pyrethroid insecticides. First, a comparison of two different ionization modes, electron ionization (EI) and negative chemical ionization (NCI), was carried out using MS and MS/MS. NCI-MS/MS provided the best results in terms of selectivity and sensitivity giving very low detection limits of 0.11 to 450 fg injected. The reliability of the method was confirmed through the evaluation of quality parameters such as accuracy (70-100%), and repeatability and reproducibility, with coefficients of variation below 15% and 10%, respectively. The applicability of the GC/MS/MS method to real samples and influence of matrix effects were evaluated through the analysis of spiked water, sediment and milk at 0.25 ng L(-1) , 5 ng g(-1) dry weight (dw) and 25 ng g(-1) (dw), respectively, of each pyrethroid insecticide considered. Using GC/NCI-MS/MS, matrix spectral interferences were minimized providing method limits of detection (MLODs) of 0.05-2.59 ng L(-1) , 0.10-87.7 pg g(-1) dw, 2.29-1071 pg g(-1) lipid weight (lw) for water, sediment and milk, respectively. To the best of our knowledge, the MLOD values found in our study were better than those reported in previous studies; in particular for sediment and food samples, they were one order of magnitude lower.

COVID-19 face masks: A new source of human and environmental exposure to organophosphate esters.

For the first time, organophosphate ester (OPE) content was studied in different types of surgical, self-filtering (KN95, FFP2, and FFP3) and reusable face masks used for COVID-19 prevention. OPEs were detected in all mask samples, although in highly variable amounts which ranged from 0.02 to a maximum of 27.7 µg/mask, with the highest mean concentrations obtained for KN95 masks (11.6 µg/mask) and the lowest for surgical masks (0.24 µg/mask). Twelve out of 16 tested analytes were detected, with TEP, TPHP, TNBP, TEHP and TClPP being the most common OPEs as well as present at the highest concentrations. The non-carcinogenic and carcinogenic risks of OPE inhalation were calculated as being always several orders of magnitude lower than threshold levels, indicating that the use of face masks is safe with regard to OPE contamination. However, given the wide range of OPEs observed in different masks, it can be concluded that some masks (e.g. reusable) are less OPE-contaminated than others (e.g. KN95). With regard to environmental pollution, the disposal of billions of face masks is adding to the already substantial levels of microplastics and associated toxic additives worldwide, an impact that is lessened by use of reusable masks, which also have the lowest economic cost per user. However, in situations of relatively high risk of viral inhalation, such as poorly ventilated indoor public spaces, we recommend the use of FFP2 masks.

Organophosphate esters in airborne particles from subway stations.

For the first time, the concentrations of 19 organophosphate esters (OPEs) were measured in airborne fine particulate matter (PM2.5) from subway stations in Barcelona (Spain) to investigate their occurrence, contamination profiles and associated health risks. OPEs were detected in all PM2.5 samples with levels ranging between 1.59 and 202 ng/m3 (mean value of 39.9 ng/m3). Seventeen out of 19 tested analytes were detected, with TDClPP, TClPP and TCEP being those presenting the highest concentrations. OPE concentrations are not driven by the same factors that determine the ambient PM2.5 concentrations of other constituents in the subway. Newer stations presented higher OPE levels, probably due to the materials used in the design of the platforms, with greater use of modern plastic materials versus older stations with tiles and stones. Estimated daily intakes via airborne particles inhalation during the time expended in subway stations were calculated, as well as the carcinogenic and non-carcinogenic health risks (CR and non-CR), all being much lower than the threshold risk values. Thus, subway inhalation exposure when standing on the platform to OPE's per se is not considered to be dangerous for commuters.

Particle-phase concentrations and sources of legacy and novel flame retardants in outdoor and indoor environments across Spain.

Levels of particle-phase legacy polybrominated diphenyl ethers (PBDEs), and novel brominated and chlorinated flame retardants, such as decabromodiphenyl ethane (DBDPE) and Dechlorane Plus (DP), were measured in ambient outdoor air, indoor workplace air and indoor dust, in different locations across Spain. PBDE concentrations were generally higher in outdoor ambient air samples than in indoor air, ranging between 1.18 and 28.6 pg m-3, while DP was the main flame retardant (FR) in indoor air (2.90-42.6 pg m-3). A different behavior of legacy versus novel FRs was observed in all the environments and matrices considered, which seemed to indicate a progressive replacement of the former. Although the emission sources could not be fully identified, certain evidences suggested that high outdoor PBDE concentrations could be associated with old goods in landfills and recycling centers, while high indoor DP concentrations were linked to the presence of new electronic devices. A direct impact of land use on outdoor atmospheric DP concentrations was observed, with DP concentrations correlating with high density of buildings within a city. In addition, DP concentrations outdoors correlated with inorganic species with FR properties (e.g., Cr, Cu). Significant differences in the fraction of anti-DP to the total DP (Fanti ratio) were observed between indoor air (PM2.5) and dust (PM10), which could be related with: a) a dependence on particle size, suggesting a higher relative abundance of the anti-isomer in PM10 than in PM2.5, while similar concentrations were recorded for the syn-isomer; b) a higher deposition rate of the anti-isomer compared to the syn-isomer; and/or c) a more accentuated preferential degradation of the anti-isomer linked to artificial light or other agents coexisting in the air. The detectable presence of all the FR families analyzed in indoor air and dust points to the importance of monitoring these compounds in order to minimize human exposure.

Decreasing but still high levels of halogenated flame retardants in wetland birds in central Spain.

The occurrence of classical and emerging halogenated flame retardants in bird samples collected between 2010-17 from the Castrejón reservoir (central Spain) was studied. Different wetland bird samples were analysed, including unhatched bird eggs and liver of dead nestlings. Polybrominated diphenylethers (PBDEs) were detected in all the samples at high concentration values, with levels up to 5167 ng/g lw. Dechloranes were found in 78% of analysed samples, but at lower concentration levels, between not detected (nd) and 2153 ng/g lw. The time trend evaluation over the sampling period showed an approximately 50% decline in mean concentrations of PBDEs. However, the most recent data for PBDEs (2016-17) still indicate that, in some cases, and based on reported LOECs, wetland birds were exposed to PBDE concentrations that are associated with possible ecological hazards.

Contaminants of emerging concern in freshwater fish from four Spanish Rivers.

This study investigated the occurrence of 135 contaminants of emerging concern (CECs) - pharmaceuticals, pesticides, a set of endocrine disrupting compounds (EDCs) (parabens, bisphenols, hormones, triazoles, organophosphorus flame retardants and triclosan), UV-filters, perfluoroalkyl substances (PFASs) and halogenated flame retardants (HFRs) - in 59 fish samples, collected in 2010 in 4 Spanish Rivers (Guadalquivir, Júcar, Ebro and Llobregat). Of the 135 CECs, 76 including 8 pharmaceuticals, 25 pesticides, 10 EDCs, 5 UV-filters, 15 PFASs and 13 HFRs were detected. Pharmaceuticals were the less frequently found and at lower concentrations. Pesticides, EDCs, UV-filters, PFASs and HFRs were detected more frequently (>50% of the samples). The maximum concentrations were 15 ng/g dry weight (dw) for pharmaceuticals (diclofenac), 840 ng/g dw for pesticides (chlorpyrifos), 224 ng/g dw for EDCs (bisphenol A), 242 ng/g dw for UV-filters (EHMC), 1738 ng/g dw for PFASs (PFHxA) and 64 ng/g dw for HFRs (Dec 602). The contaminants detected in fish are commonly detected also in sediments. In light of current knowledge, the risk assessment revealed that there was no risk for humans related to the exposure to CECs via freshwater fish consumption. However, results provide detailed information on the mixtures of CECs accumulated that would be very useful to identify their effects on aquatic biota.

Development of a pressurized liquid extraction-solid-phase extraction followed by liquid chromatography-electrospray ionization tandem mass spectrometry method for the quantitative determination of benzoxazolinones and their degradation products in agricultural soil.

A new analytical method for the quantitative determination of benzoxazolinones and their degradation products in agricultural soils based on the use of pressurized liquid extraction (PLE) followed by solid-phase extraction (SPE) and then instrumental determination using liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS-MS) is described. Using this method, the characterization, separation and quantitative detection of a mixture of two benzoxazolinones, benzoxazolin-2-one (BOA) and 6-methoxybenzoxazolin-2-one (MBOA) and their degradation products, 2-aminophenol (APH), N-(2-hydroxyphenyl)malonamic acid (HMPMA), 2-amino-3-H-phenoxazin-3-one (APO), 9-methoxy-2-amino-3-H-phenoxazin-3-one (AMPO), 2-acetylamino-3-H-phenoxazin-3-one (AAPO) and 2-acetylamino-9-methoxy-2-amino-3-H-phenoxazin-3-one (AAMPO) was achieved. The complete LC-ESI-MS-MS precursor-product ion fragmentation pathways for the degradation products of benzoxazolinones are described for the first time. Quantitative analysis was done in the multiple reaction mode using two specific combinations of precursor-product ion transitions for each compound. The optimized method was quality assessed by the measure of parameter as recovery, linearity, sensitivity, repeatability and reproducibility. Recoveries of the analytes ranged from 53 to 123%. The developed method offered improvements to the sensitivity as compared with our previously LC-MS method, with detection limits down to 2.4-21 ng/g of dry weight. This achievement allows us to identify and quantify for the first time degradation products of benzoxazolinones in real agricultural soil samples. Analytes were found in the range of 20.6-149 ng/g dry weight.

Characterization of organic aromatic compounds in soils affected by an uncontrolled tire landfill fire through the use of comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry.

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

Halogenated flame retardants in stranded sperm whales (Physeter macrocephalus) from the Mediterranean Sea.

In recent years, decline of marine mammals' populations and increased frequency of strandings have arised the interest on the role that pollution may have in these events. The present work aimed at quantifying levels of brominated flame retardants (BFRs) and dechloranes (DECs) in tissues of 3 adult females and one foetus of sperm whales stranded in the Southern Adriatic Sea coasts (Italy). Results proved the presence of different flame retardants (FRs) in tissues of sperm whales, including various polybrominated diphenyl ethers (PBDE) congeners (47, 99, 100, 154, entering the composition of PentaBDE mixture), hexabromocyclodecanes (HBCDs), Dec 602 and methoxylated polibrominated diphenyl ethers (MeO-BDEs). In blubber, a target tissue for contaminant accumulation, ΣPBDEs reached values of 160, 158 and 183 ng/g lw, α-HBCD of 5.75 ng/g lw, Dec 602 of 1632 ng/g lw and MeO-BDEs of 563 ng/g lw. The availability of foetal tissues allowed evaluating the potential maternal transfer on many of these compounds, and to discuss the potential adverse effects on foetal health. To the best of our knowledge, obtained data are the first reporting placental transfer of FRs in sperm whales. PBDE levels detected in foetus suggested a potentially long-term exposure to BFRs, which could cause severe damages to the developing organism, likely at the cerebral, endocrine and immunologic levels. Dec 602, which was detected at the highest concentrations among all FRs considered, could potentially cause dysfunctional effects on the immune system of adult females.