Regions of Interest Multivariate Curve Resolution Liquid Chromatography with Data-Independent Acquisition Tandem Mass Spectrometry.

New data-independent acquisition (DIA) modes coupled to chromatographic separations are opening new perspectives in the processing of massive mass spectrometric (MS) data using chemometric methods. In this work, the application of the regions of interest multivariate curve resolution (ROIMCR) method is shown for the simultaneous analysis of MS1 and MS2 DIA raw data obtained by liquid chromatography coupled to quadrupole-time-of-flight MS analysis. The ROIMCR method proposed in this work relies on the intrinsic bilinear structure of the MS1 and MS2 experimental data which allows us for the fast direct resolution of the elution and spectral profiles of all sample constituents giving measurable MS signals, without needing any further data pretreatment such as peak matching, alignment, or modeling. Compound annotation and identification can be achieved directly by the comparison of the ROIMCR-resolved MS1 and MS2 spectra with those from standards or from mass spectral libraries. ROIMCR elution profiles of the resolved components can be used to build calibration curves for the prediction of their concentrations in complex unknown samples. The application of the proposed procedure is shown for the analysis of mixtures of per- and polyfluoroalkyl substances in standard mixtures, spiked hen eggs, and gull egg samples, where these compounds tend to accumulate.

Effects of Indoor Dust Exposure on Lung Cells: Association of Chemical Composition with Phenotypic and Lipid Changes in a 3D Lung Cancer Cell Model.

Indoor dust is a key contributor to the global human exposome in urban areas since the population develops most of its activities in private and public buildings. To gain insight into the health risks associated with this chronic exposure, it is necessary to characterize the chemical composition of dust and understand its biological impacts using reliable physiological models. The present study investigated the biological effects of chemically characterized indoor dust extracts using three-dimensional (3D) lung cancer cell cultures combining phenotypic and lipidomic analyses. Apart from the assessment of cell viability, reactive oxygen species (ROS) induction, and interleukin-8 release, lipidomics was applied to capture the main lipid changes induced as a cellular response to the extracted dust compounds. The application of chemometric tools enabled the finding of associations between chemical compounds present in dust and lipidic and phenotypic profiles in the cells. This study contributes to a better understanding of the toxicity mechanisms associated with exposure to chemical pollutants present in indoor dust.

Linking MS1 and MS2 signals in positive and negative modes of LC-HRMS in untargeted metabolomics using the ROIMCR approach.

Data-independent acquisition (DIA) mode in liquid chromatography (LC) high-resolution mass spectrometry (HRMS) has emerged as a powerful strategy in untargeted metabolomics for detecting a broad range of metabolites. However, the use of this approach also represents a challenge in the analysis of the large datasets generated. The regions of interest (ROI) multivariate curve resolution (MCR) approach can help in the identification and characterization of unknown metabolites in their mixtures by linking their MS1 and MS2 DIA spectral signals. In this study, it is proposed for the first time the analysis of MS1 and MS2 DIA signals in positive and negative electrospray ionization modes simultaneously to increase the coverage of possible metabolites present in biological systems. In this work, this approach has been tested for the detection and identification of the amino acids present in a standard mixture solution and in fish embryo samples. The ROIMCR analysis allowed for the identification of all amino acids present in the analyzed mixtures in both positive and negative modes. The methodology allowed for the direct linking and correspondence between the MS signals in their different acquisition modes. Overall, this approach confirmed the advantages and possibilities of performing the proposed ROIMCR simultaneous analysis of mass spectrometry signals in their differing acquisition modes in untargeted metabolomics studies.

Human biomonitoring of microplastics and health implications: A review.

BACKGROUND: Microplastics (MPs) are plastic particles (<5 mm) ubiquitous in water, soil, and air, indicating that humans can be exposed to MPs through ingestion of water and food, and inhalation. OBJECTIVE: This review provides an overview of the current human biomonitoring data available to evaluate human exposure and health impact of MPs. METHOD: We compiled 91 relevant studies on MPs in human matrices and MPs toxicological endpoints to provide evidence on MPs distribution in the different tissues and the implications this can have from a health perspective. RESULTS: Human exposure to MPs has been corroborated by the detection of MPs in different human biological samples including blood, urine, stool, lung tissue, breast milk, semen and placenta. Although humans have clearance mechanisms protecting them from potentially harmful substances, health risks associated to MPs exposure include the onset of inflammation, oxidative stress, and DNA damage, potentially leading to cardiovascular and respiratory diseases, as well as cancer, as suggested by in vitro and in vivo studies. CONCLUSION: Based on compiled data, MPs have been recurrently identified in different human tissues and fluids, suggesting that humans are exposed to MPs through inhalation and ingestion. Despite differences in MPs concentrations appear in exposed and non-exposed people, accumulation and distribution pathways and potential human health hazards is still at an infant stage. Human biomonitoring data enables the assessment of human exposure to MPs and associated risks, and this information can contribute to draw management actions and guidelines to minimize MP release to the environment, and thus, reduce human uptake.

Presence of novel and legacy flame retardants and other pollutants in an e-waste site in China and associated risks.

Electrical and Electronic Equipment (EEE) residues and their management have been widely identified as potential sources of plasticizers and flame retardants to the environment, especially in non-formal e-waste facilities. This study evaluates the distribution, partitioning and environmental and human impact of organophosphate esters (OPEs), legacy polychlorinated biphenyls (PCBs), polybromodiphenyl ethers (PBDEs) and organochlorine pesticides (OCPs) in the e-waste recycling area of Baihe Tang village, in the Qingyuan county, Guangdong province, China. A plastic debris lump accumulated in a small pond during years was identified as the main source of pollution with ∑pollutants of 8400 µg/g dw, being OPEs the main contaminants detected, followed by PBDEs. This lump produced the contamination of water, sediments, soils and hen eggs in the surrounding area at high concentrations. Plastic-water and water-sediment partitioning coefficients explained the migration of OPEs to the water body and accumulation in sediments, with a strong dependence according to the KOW. Triphenyl phosphate (TPhP), tricresyl phosphate (TCPs) and high chlorination degree PCBs produced a risk in soils and sediments, considering the lowest predicted no effect concentration, while the presence of PCBs and PBDEs in free range hen eggs exceeded the acceptable daily intake. OCPs were detected at low concentrations in all samples. The presence of organic contaminants in e-waste facilities worldwide is discussed to highlight the need for a strict control of EEE management to minimize environmental and human risks.

Pilot monitoring scheme of water pollutants in Important Bird and Biodiversity Areas.

In this study we have established a monitoring scheme to determine the presence and distribution of widely used pharmaceuticals, pesticides, organophosphate esters (OPEs) and perfluoroalkyl substances (PFAS) in water bodies from Important Bird and Biodiversity Areas (IBAs) from Spain. The monitoring scheme included the georeferenced sampling of rocky mountain, Atlantic forest, riparian forest, Mediterranean forest, agricultural, inland aquatic and coastal aquatic IBAs, with the aim to evaluate the impact of widely used chemicals in those aquatic resources. Water samples were extracted using a generic solid-phase extraction protocol and analyzed by 3 analytical methods based on liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). Quality parameters such as compound recovery, intra and inter-day variation, linearity and limits of detection were calculated in order to validate the methods. In addition, the ionization conditions and the optimization of the most appropriate transitions permitted unequivocal identification. Once the sampling and analytical procedure was set-up, 59 target compounds were monitored in 63 samples. Pharmaceutical, followed by pesticides, OPEs and PFAS were widespread along all IBAs studied at concentrations from 0.5 to 41083 ng/L. Overall, this study highlights the need to monitor the presence of contaminants in areas of high ecological interest to contribute to pollution control and mitigation towards protection of biodiversity.

Long-Term Calculation of Predicted Environmental Concentrations to Assess the Risk of Anticancer Drugs in Environmental Waters.

This study reports the consumption data for 132 anticancer drugs in Catalonia (NE Spain) during the period of 2013-2017 and calculates the predicted environmental concentrations (PECs) in wastewater effluents and rivers. This long-term analysis can determine the evolution of drugs present in the environment according to prescriptions and serve as an adequate tool to determine their presence and impact. Data showed that out of 132 compounds prescribed, 77 reached wastewater effluents, which accounted for the most consumed, those excreted in the highest doses, and the least biodegradable. Once diluted in receiving river waters, only mycophenolic acid and hydroxycarbamide had PEC values higher than 10 ng L-1, which is the value set by the European Medicines Agency (EMA) to carry out further risk assessment. It was also observed that compounds present in river water are those that can pose a high risk, given their persistence and capability to bioaccumulate. Therefore, this study shows that the estimation of PEC, together with physico-chemical properties of detected compounds, is a useful tool to determine the long-term presence and fate of this new class of emerging contaminants.

Migration of Microplastics and Phthalates from Face Masks to Water.

Since the outbreak of COVID-19, face masks have been introduced in the complex strategy of infection prevention and control. Face masks consist of plastic polymers and additives such as phthalates. The aim of this study was to evaluate the migration of microplastics (MP) and phthalates from face masks to water. Four types of masks including FFP2 masks and surgical were studied. Masks were first characterized to determine the different layers and the material used for their fabrication. Then, masks were cut into 20 pieces of 0.5 cm2, including all their layers, placed in water, and the migration of MP and phthalates was evaluated according to the conditions stated in EU Regulation No 10/2011 on plastic materials and articles intended to come into contact with food. For MP, the morphological analysis (shape, dimension, particle count) was performed using a stereomicroscope, while the identification of both masks and MP released was conducted using µ-Fourier-transform infrared spectroscopy (µ-FT-IR). Migration of phthalates was assessed by ultra-high-performance liquid chromatography coupled to triple quadrupole mass spectrometer (UPLC-MS/MS). Face masks analyzed in the present study were made of atactic polypropylene (PP) as stated by the manufacturer. The µ-FT-IR confirmed that PP and polyamide (PA) were released as fragments, while both PP and polyester (PES) were released as fibers. In addition, 4 phthalates were identified at concentrations between 2.34 and 21.0 µg/mask. This study shows that the migration study can be applied to evaluate the potential release of MP and phthalates from face masks to water and could give a hint for the potential impact of their incorrect disposal on the aquatic resources.

Analysis of Dechlorane Plus and related compounds in gull eggs by GC-HRMS using a novel atmospheric pressure photoionization source.

Here, a new gas chromatography-atmospheric pressure photoionization-high-resolution mass spectrometry (GC-APPI-HRMS) method combined with selective pressurized liquid extraction (sPLE) has been developed for the selective determination of Dechlorane Plus (DP) and its related compounds in gull egg samples used as a bioindicator of contamination. To the best of our knowledge, this is the first time these compounds have been analyzed by GC-MS using atmospheric pressure photoionization (APPI). Negative ion dopant-assisted APPI using vapors of diethyl ether and a source temperature of 250 °C provided high ionization efficiencies and mass spectra characterized by intense in-source fragment ions as well as the presence of molecular ion and characteristic cluster ions containing oxygen atoms in their chemical structure. This made it possible to improve the selectivity in the determination of these compounds compared to that obtained with traditional GC-MS ion sources. Under optimized conditions, the sPLE GC-APPI-HRMS (Orbitrap) method provided high recoveries (> 91%), good precisions (RSD% < 12%), and low method limits of detection (0.1-3.5 pg g-1 wet weight). The developed methodology has been applied to the determination of DP and related compounds in eggs of two gull species (L. michahellis and L. audouinii) from several Spanish protected areas. The results obtained showed significant differences in the DP concentration profiles in eggs from different gull breeding locations and between gull species of the same protected area. These results demonstrated the good performance of the GC-APPI-HRMS system to achieve a selective and sensitive determination of DP and related compounds in complex environmental samples.

Analysis of microplastics in drinking water and other clean water samples with micro-Raman and micro-infrared spectroscopy: minimum requirements and best practice guidelines.

Microplastics are a widespread contaminant found not only in various natural habitats but also in drinking waters. With spectroscopic methods, the polymer type, number, size, and size distribution as well as the shape of microplastic particles in waters can be determined, which is of great relevance to toxicological studies. Methods used in studies so far show a huge diversity regarding experimental setups and often a lack of certain quality assurance aspects. To overcome these problems, this critical review and consensus paper of 12 European analytical laboratories and institutions, dealing with microplastic particle identification and quantification with spectroscopic methods, gives guidance toward harmonized microplastic particle analysis in clean waters. The aims of this paper are to (i) improve the reliability of microplastic analysis, (ii) facilitate and improve the planning of sample preparation and microplastic detection, and (iii) provide a better understanding regarding the evaluation of already existing studies. With these aims, we hope to make an important step toward harmonization of microplastic particle analysis in clean water samples and, thus, allow the comparability of results obtained in different studies by using similar or harmonized methods. Clean water samples, for the purpose of this paper, are considered to comprise all water samples with low matrix content, in particular drinking, tap, and bottled water, but also other water types such as clean freshwater.

Pharmaceutical Residues in Senior Residences Wastewaters: High Loads, Emerging Risks.

Senior residences are health-care facilities that are socially-accepted for the assistance of elderly people. Since the elderly account for the foremost pharmaceutical-consuming age-group, senior residences become a hot-spot for pharmaceuticals discharge to the sewage grid. The objectives of the present study were to identify the bioactive pharmaceuticals in sewage waters from senior residences and to propose an on-site monitoring strategy for their control. In this study, we have studied the presence of 43 pharmaceuticals highly consumed by the elderly population in six senior residences located in Spain, France and Portugal. Wastewater was sampled directly from the water-chest in each residence during different times of the day throughout one week. Main compounds detected at the high µg L-1 level were analgesic and antipyretic drugs such as acetylsalicylic acid, paracetamol, ibuprofen; antibiotics such as amoxicillin and sulfamethoxazole; compounds for the treatment of neuropathies as gabapentin, trazodone and valsartan; pharmaceuticals for the treatment of diabetes (vildagliptin) and anticancer drugs. The daily loads discharged were estimated and their fate was evaluated. The final objective of this study is to highlight the need to implement at-source waste water treatment procedures in senior residences, which have been identified as a point source pollution of pharmaceuticals.

Nasal lavages as a tool for monitoring exposure to organic pollutants.

Exposure to air and dust pollutants can cause several adverse effects on human health. This study proposes the use of nasal lavages as a non-invasive sampling technique to determine in a direct way pollutant intake through inhalation. We evaluate the occurrence of compounds widely used in domestic products and construction materials (organophosphorus flame retardants (OPFR), phthalates, alkylphenols and bisphenol A), applied for pest control in cities (pesticides) and emitted through car exhausts (polycyclic aromatic hydrocarbons, PAHs) or smoking (nicotine). Contaminants were liquid-liquid extracted from nasal lavages and analysed using gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). All 29 individuals inhabiting in Barcelona city had phthalates and bisphenol A at concentrations up to 31,300 ng mL-1 for diethylhexyl phthalate (DEHP) and 118 ng mL-1 for BPA. Individual PAHs, OPFR and alkylphenols had median values below their MQLs except for 2-ethylhexyldiphenyl phosphate (EHDPhP) with a median of 1.47 ng mL-1. Nicotine was detected at the highest concentrations in all active smokers (median 2.16 ng mL-1). Contrarily, pesticides were sporadically detected. Nasal lavages revealed to be an appropriate indicator likely to reflect exposure to dust and air contaminants.

Occurrence of flame retardants in landfills: A case study in Brazil.

Huge amounts of waste containing flame retardants reach landfills annually, which can result in environmental contamination if this type of solid residues is not properly managed. This study presents data concerning the occurrence of organophosphorus flame retardants (OPFRs), polybrominated diphenyl ethers (PBDEs) and new brominated flame retardants (NBFRs) in soil, dust, leachate and well water samples from a landfill in Brazil. Samples were collected in different points of the landfill site, including offices, concierge, electronic waste storage area, bulk waste storage area, a place where a recycling cooperative operates, leachate pound and wells. Most of the flame retardants (FRs) were quantified in soil samples (up to 2500 ng g-1). The tris(2-chloroisopropyl) phosphate (TCIPP) and tris(1,3-dichloroisopropyl) phosphate (TDCIPP) were present at the highest levels in the site where bulk waste was disposed in the open air. The most abundant brominated FRs in soil samples were BDE-99, BDE-209, decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), and the highest levels were observed in the samples collected from the electronic waste storage area. Concerning dust samples, the highest levels of brominated FRs were observed in the electronic waste storage area, while the highest levels of OPFRs were observed in the landfill office. TCIPP, TDCIPP and tris(2-choroethyl) phosphate (TCEP) were quantified in the well water sample collected downstream the bulk waste area. Finally, six OPFRs were quantified in leachate at concentrations ranging from 14 to 965 ng L-1. In conclusion, this study demonstrates that an improper management of wastes containing FRs in landfills can potentially contaminate the surrounding environment and groundwater.

Temporal and Spatial Distribution of Mercury in Gulls Eggs from the Iberian Peninsula.

We examined how coastal mercury contamination varied spatially and temporally across the Iberian Peninsula by measuring mercury concentrations in the eggs of the sentinel biomonitor yellow-legged gull (Larus michahellis). Samples were collected from eight colonies that ranged from the Atlantic across the south and northern areas of the Mediterranean. We also measured Hg residues in eggs of the one of the most endangered gull species in the world, the Audouin's gull (Larus audouinii) from the Ebro Delta, where colonies of yellow-legged and Audouin's gull co-occur. Fresh eggs were collected in 2009 and 2016 and samples were pooled from each colony for analysis. Mercury concentrations in yellow-legged gulls ranged between 0.4 and 2.8 mg/kg dry weight (dw); although there were no significant differences in concentrations between sampling periods, significant differences were found between colonies. Higher concentrations were associated with northern Mediterranean colonies (Columbretes and Ebro Delta), likely due to proximity to emission sources, circulatory marine currents and diet composition. Mercury concentrations in yellow-legged gull eggs were lower than those reported to result in impaired hatching. Residues in Audouin's gull eggs from the Ebro Delta were significantly higher (4.0-5.6 mg/kg dw) than those in yellow-legged gull from the same location, probably associated with dietary differences. Mercury levels in Audouin's gull were ten times above the benchmark suggested to reduce nest success by 10%. Overall, these results raise concern for adverse health impacts in this protected seabird species and further investigation in Audouin's gull eggs from the Ebro Delta is recommended.

Chemometrics comparison of gas chromatography with mass spectrometry and comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry Daphnia magna metabolic profiles exposed to salinity.

The performances of gas chromatography with mass spectrometry and of comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry are examined through the comparison of Daphnia magna metabolic profiles. Gas chromatography with mass spectrometry and comprehensive two-dimensional gas chromatography with mass spectrometry were used to compare the concentration changes of metabolites under saline conditions. In this regard, a chemometric strategy based on wavelet compression and multivariate curve resolution-alternating least squares is used to compare the performances of gas chromatography with mass spectrometry and comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry for the untargeted metabolic profiling of Daphnia magna in control and salinity-exposed samples. Examination of the results confirmed the outperformance of comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry over gas chromatography with mass spectrometry for the detection of metabolites in D. magna samples. The peak areas of multivariate curve resolution-alternating least squares resolved elution profiles in every sample analyzed by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry were arranged in a new data matrix that was then modeled by partial least squares discriminant analysis. The control and salt-exposed daphnids samples were discriminated and the most relevant metabolites were estimated using variable importance in projection and selectivity ratio values. Salinity de-regulated 18 metabolites from metabolic pathways involved in protein translation, transmembrane cell transport, carbon metabolism, secondary metabolism, glycolysis, and osmoregulation.

Metabolomic changes induced by nicotine in adult zebrafish skeletal muscle.

Acute exposure to nicotinic agonists induces myotoxicity in zebrafish embryos. The main goal of this work was to evaluate the potential myotoxicity of nicotine acetylcholine receptor agonists on adult zebrafish muscle tissue by using nicotine as a model compound. Liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) datasets were processed with different chemometric tools based on the selection of Regions of Interest (ROI) and Multivariate Curve-Resolution (ROI-MCR procedure) Alternating Least Squares (ALS) for the analysis of different exposure experiments. Analysis of Variance Simultaneous Component Analysis (ASCA) of changes on metabolite peak profile areas showed significant nicotine concentration and exposure time-dependent changes, clearly differentiating between exposed and non-exposed samples and between short (2 h) and long exposure times (6 h or 24 h). Most of the changes observed in the concentrations of different metabolites are probably secondary to the observed hyperlocomotion, as they have been also observed in humans after strenuous muscular exercise. The absence of myotoxicity might be related with the reduced calcium permeability of adult muscle-type nicotinic acetylcholine receptors (nAChRs).

Diet-sourced carbon-based nanoparticles induce lipid alterations in tissues of zebrafish (Danio rerio) with genomic hypermethylation changes in brain.

With rising environmental levels of carbon-based nanoparticles (CBNs), there is an urgent need to develop an understanding of their biological effects in order to generate appropriate risk assessment strategies. Herein, we exposed zebrafish via their diet to one of four different CBNs: C60 fullerene (C60), single-walled carbon nanotubes (SWCNT), short multi-walled carbon nanotubes (MWCNTs) or long MWCNTs. Lipid alterations in male and female zebrafish were explored post-exposure in three target tissues (brain, gonads and gastrointestinal tract) using 'omic' procedures based in liquid chromatography coupled with mass spectrometry (LC-MS) data files. These tissues were chosen as they are often target tissues following environmental exposure. Marked alterations in lipid species are noted in all three tissues. To further explore CBN-induced brain alterations, Raman microspectroscopy analysis of lipid extracts was conducted. Marked lipid alterations are observed with males responding differently to females; in addition, there also appears to be consistent elevations in global genomic methylation. This latter observation is most profound in female zebrafish brain tissues post-exposure to short MWCNTs or SWCNTs (P < 0.05). This study demonstrates that even at low levels, CBNs are capable of inducing significant cellular and genomic modifications in a range of tissues. Such alterations could result in modified susceptibility to other influences such as environmental exposures, pathology and, in the case of brain, developmental alterations.

Perfluoroalkylated Substance Effects in Xenopus laevis A6 Kidney Epithelial Cells Determined by ATR-FTIR Spectroscopy and Chemometric Analysis.

The effects of four perfluoroalkylated substances (PFASs), namely, perfluorobutanesulfonate (PFBS), perfluorooctanoic acid (PFOA), perfluorooctanesulfonate (PFOS), and perfluorononanoic acid (PFNA) were assessed in Xenopus laevis A6 kidney epithelial cells by attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy and chemometric analysis. Principal component analysis-linear discriminant analysis (PCA-LDA) was used to visualize wavenumber-related alterations and ANOVA-simultaneous component analysis (ASCA) allowed data processing considering the underlying experimental design. Both analyses evidenced a higher impact of low-dose PFAS-treatments (10(-9) M) on A6 cells forming monolayers, while there was a larger influence of high-dose PFAS-treatments (10(-5) M) on A6 cells differentiated into dome structures. The observed dose-response PFAS-induced effects were to some extent related to their cytotoxicity: the EC50-values of most influential PFAS-treatments increased (PFOS < PFNA < PFOA ≪ PFBS), and higher-doses of these chemicals induced a larger impact. Major spectral alterations were mainly attributed to DNA/RNA, secondary protein structure, lipids, and fatty acids. Finally, PFOS and PFOA caused a decrease in A6 cell numbers compared to controls, whereas PFBS and PFNA did not significantly change cell population levels. Overall, this work highlights the ability of PFASs to alter A6 cells, whether forming monolayers or differentiated into dome structures, and the potential of PFOS and PFOA to induce cell death.

Occurrence and sources of brominated and organophosphorus flame retardants in dust from different indoor environments in Barcelona, Spain.

In this study, the simultaneous presence of eight polybrominated diphenyl ethers (PBDEs), nine new brominated flame retardants (NBFRs) and ten organophosphorus flame retardants (OPFRs) was investigated in dust samples collected from different indoor environments (homes, schools, theatres, a university and a Research Institute) in Barcelona, Spain. OPFRs were detected at the highest concentrations followed by PBDEs. ∑OPFRs ranged from 2053 to 72,090ngg(-1) and tris(2-chloroisopropyl) phosphate (TCIPP) was the most abundant compound. BDE-209 was the main PBDE congener detected (up to 14,990ngg(-1)), while other PBDEs ranged from 2.6 to 118ngg(-1). Among the studied NBFRs, decabromodiphenyl ethane (DBDPE - up to 4432ngg(-1)) followed by bis(2-ethylhexyl) tetrabromophthalate (BEH-TEBP - up to 508ngg(-1)) were detected at the highest concentration, whereas a lower detection frequency was observed for 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (EH-TBB), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), pentabromotoluene (PBT) and hexabromobenzene (HBB). The levels and profile of flame retardants (FRs) were characteristic of each environment, where theatres followed by homes presented the highest concentrations and schools had the lowest levels. Principal Component Analysis permitted to identify the main sources and distribution of all FRs, according to specific uses in each environment. The simultaneous presence of all FR families in indoor dust points to the need to monitor these compounds to minimize human exposure.

Can activated sludge treatments and advanced oxidation processes remove organophosphorus flame retardants?

This study aims to determine the occurrence of 10 OPFRs (including chlorinated, nonchlorinated alkyl and aryl compounds) in influent, effluent wastewaters and partitioning into sludge of 5 wastewater treatment plants (WWTP) in Catalonia (Spain). All target OPFRs were detected in the WWTPs influents, and the total concentration ranged from 3.67 µg L(-1) to 150 µg L(-1). During activated sludge treatment, most OPFRs were accumulated in the sludge at concentrations from 35.3 to 9980 ng g(-1) dw. Chlorinated compounds tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP) and tris(2,3-dichloropropyl) phosphate (TDCPP) were not removed by the conventional activated sludge treatment and they were released by the effluents at approximately the same inlet concentration. On the contrary, aryl compounds tris(methylphenyl) phosphate (TMPP) and 2-ethylhexyl diphenyl phosphate (EHDP) together with alkyl tris(2-ethylhexyl) phosphate (TEHP) were not detected in any of the effluents. Advanced oxidation processes (UV/H2O2 and O3) were applied to investigate the degradability of recalcitrant OPFRs in WWTP effluents. Those detected in the effluent sample (TCEP, TCIPP, TDCPP, tributyl phosphate (TNBP), tri-iso-butyl phosphate (TIBP) and tris(2-butoxyethyl) phosphate (TBOEP)) had very low direct UV-C photolysis rates. TBOEP, TNBP and TIBP were degraded by UV/H2O2 and O3. Chlorinated compounds TCEP, TDCPP and TCIPP were the most recalcitrant OPFR to the advanced oxidation processes applied. The study provides information on the partitioning and degradability pathways of OPFR within conventional activated sludge WWTPs.