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The ubiquity of microplastics (MPs) in the various environment is of increasing concern. Although micro Fourier Transform Infrared Spectroscopy (μ-FTIR) represents an ideal method for the detection of MPs, this technique lacks a standardized mode to be followed for MPs in diverse environmental matrices. The study focused on the optimization, application, and validation of μ-FTIR techniques for the identification of smaller-sized MPs (20 μm-1 mm). In order to assess the validity of the various detection modes in μ-FTIR (reflection and transmission), a confirmatory test with known standard polymers, viz., polyethylene (PE), polypropylene (PP), polystyrene (PS), polyamide (PA), and polyvinyl chloride (PVC) were executed. Subsequently, for the validation and accuracy of the method, the polymer spectra of standard polymers acquired in μ-FTIR (smaller-sized) were compared with spectra of larger-sized particles (same standards) in FTIR-ATR (Attenuated Total Reflectance). The spectra were comparable and highlighted the similar pattern of the polymeric composition. The spectral quality and matching score (>60 %) with the reference library was taken into account to accentuate the authenticity of the different methods. This study highlighted the reflection mode (particularly diffuse reflection) as more effective for the quantification of smaller-sized MPs in complex environmental samples. The same method was successfully applied to a representative environmental sample (sand), supplied by the EURO-QCHARM for inter-laboratory study. Two polymers (PE and PET) were correctly identified out of three spiked polymers (PE, PET, and PS) in the given sample. Similarly, in terms of matching algorithms, the results for diffuse reflection (PE-71.7 % and PET-89.1 %) were found satisfactory as compared to micro-ATR (PE-67 % and PET-63.2 %) reflection mode. Overall, this study illustrates an extensive perspective of different μ-FTIR techniques, recommending the most reliable, easy, and non-destructive method to unambiguously characterize diverse types of polymers of smaller MPs in complex environmental matrices.

In two series of ambient air measurement campaigns to support the implementation of the global monitoring plan (GMP) component of the Stockholm Convention on Persistent Organic Pollutants (POPs), passive air samplers (PAS) using polyurethane foams were implemented by the United Nations Environment Programme (UNEP). With the same laboratories responsible for the chemical analyses of the different groups of POPs, a total of 423 PUFs were analyzed for organochlorine pesticides (OCPs) including hexachlorobenzene (HCB) and polychlorinated biphenyls (PCB); 242 for dioxin-like POPs. For trend analysis, to compare amounts of POPs in the PUFs during the first phase in 2010/2011 and the second phase from 2017 to 2019, only results were assessed that were generated in the same country and for the same POP in both campaigns. Finally, there were 194 PUFs available for OCPs (GMP1 = 67 and GMP2 = 127), 297 for PCB (GMP1 = 103, GMP2 = 194), 158 for polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDD, PCDF) (GMP1 = 39, GMP2 = 119), and 153 for dl-PCB (GMP1 = 34, GMP2 = 119). Indicator PCB and dioxin-like POPs were quantified in all countries at all times; decreases of about 30% based on median values were determined. A 50% increase was found for HCB. By scale, DDT remained with the highest values, although more than 60% decrease was found; mainly due to smaller values in the Pacific Islands region. Our assessment showed that on relative scale – per PUF – trend analysis was achieved and that such approach should be undertaken at regular intervals, not necessarily on an annual basis.

In support of the United Nations Environment Programme (UNEP) global monitoring plan under the Stockholm Convention contributing laboratories were offered to take part in a series of interlaboratory assessments on persistent organic pollutants (POPs). The results of two rounds of these assessments are reported. The target compounds were polychlorinated biphenyls, organochlorine pesticides, polybrominated diphenylethers, one polybrominated biphenyl and hexabromocyclododecane diastereomers. The matrices distributed were a test solution, fish, sediment, human milk, and air extracts. The number of participants in each round was well over 100, showing the interest of laboratories worldwide. The results showed that many laboratories still struggle to obtain acceptable standard deviations of around 25% for their determinations. In particular for organochlorine pesticides serious improvement in quality is required. Acceptable results were obtained for the air extracts and for the determination of polybrominated diphenylethers in various matrices.

The comparability of laboratories for the analysis of per- and polyfluoroalkyl substances (PFAS) was assessed in the fourth round (2018/2019) of a series of interlaboratory assessments coordinated by the United Nations Environment Programme (UNEP) in support of the Stockholm Convention quality assurance activities as to persistent organic pollutants (POPs) laboratories reporting data under this Convention. The participating laboratories were asked to analyse PFAS concentrations in a test solution of the target compounds, in the four core matrices of the global monitoring plan (GMP), human milk, human plasma, an air extract, and water, and in a sediment and a fish matrix. 39 participating laboratories submitted PFAS data for one or more test materials. The majority of the participating laboratories originated from the Asia-Pacific region, and from the 'Western European and other groups' (WEOG). Only one laboratory from the group 'Latin America and Caribbean' (GRULAC), and two from the Central and Eastern Europe (CEE) region submitted results. None of the African laboratories submitted data. The coefficients of variation (CVs) varied from 7% to 24% (mean 14%) for the test solution. Mean CVs for all matrices, except for the human plasma test material (18%), were above the satisfactory limit of 25%. The highest mean CV was found for human milk (61%). In total 1457 z-scores were assigned of which 64% were satisfactory (|z, Funding agencies:UN Environment, Economy Division, Chemicals and Waste BranchGlobal Environment Facility (GEF)

BackgroundAlthough artificial turf fields are utilized widely around the world, sufficient research has not yet been conducted to assess the potential human and environmental health risks posed by the chemicals contained in the fields’ fibers, backing, and often-used crumb rubber infill. Consequently, there is wide variation in governmental policies.ObjectiveReview the notable policies concerning artificial turf and crumb rubber infill in the European Union, United Kingdom, United States of America, Canada, China, Qatar, and the Global Stockholm Convention of the United Nations.MethodsInformation was collected that included published papers, technical and policy reports, and grey literature. These were then analyzed by a collaborative group familiar with the environmental policies in their respective countries to extract the pertinent legislative or regulatory information. The group members were primarily identified through their involvement in publications pertinent to artificial turf and crumb rubber infill health research and included environmental health professors, active researchers, and governmental agency officials. Most information on direct policies was taken directly from reports provided to the public by various governmental agencies responsible for their countries’ regulations, often available within the respective agency's online archives.ResultsThere are significant differences in the regulatory approaches adopted by the investigated countries with regards to artificial turf and its crumb rubber infill. Some regions, such as the European Union, have taken substantial steps to limit the fields’ chemical components to which the public and environment are exposed. Other regions and countries have done far less to address the issue. Most policies relate directly to (i) the fields themselves, (ii) the microplastic components of crumb rubber infill, or (iii) the concentrations of harmful polycyclic aromatic hydrocarbons (PAHs), perfluoroalkyl and polyfluoroalkyl substances (PFAS), and heavy metals.ConclusionWhile nearly every country acknowledges the potential health risks posed by heavy metals, microplastics, PAHs, and PFAS chemicals, very few have actually implemented artificial turf and crumb rubber infill regulations and/or established adequate surveillance measures to protect those regularly exposed to the fields.

In this study, pesticide practices and related environmental and health effects were investigated in the Central Rift Valley (CRV) of Ethiopia through a farmers’ survey. Questionnaires were distributed to 422 local farmers in the Arsi-Negele, Meki and Ziway areas. Multiple linear regression analyses were used to evaluate the results of the questionnaire and to identify risk factors associated with environmental and health effects after spraying. The majority of the farmers (44.4–55.0%) stored their pesticides in the kitchen or anywhere in the house, while only 6.5–32.0% of the farmers stored them in a separate place outside the house. A large majority of the farmers (63%) did not use personal protective equipment during pesticide spraying and handling, which was negatively associated with understanding pesticide instructions of the pesticide labels, OR: 0.9; (95% CI:0.82–0.98) in the supervised stepwise backwards selection model. Reading the instructions of the pesticide labels was positively associated with understanding instructions OR: 1.59 (95% CI: 1.0–2.54). The risk for water pollution was higher in the Meki region OR: 1.26 (95% CI: 1.14–1.4) compared to Ziway and Arsi-Negele. Most farmers (66%) experienced discomfort after pesticide spraying and Illnesses from pesticide spraying were more frequently reported by educated farmers. Therefore, proper training in pesticide use in this region could strongly reduce the health risk associated with pesticide exposure.

In support of the United Nations Environment Programme (UNEP) global monitoring plan under the Stockholm Convention concentrations of persistent organic pollutants (POPs) were determined during two years in air from 42 countries in Asia, Africa, Latin America, and the Pacific by using polyurethane foams installed in passive samplers. The compounds included were polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenylethers (PBDEs), one polybrominated biphenyl and hexabromocyclododecane (HBCD) diastereomers. Total-DDT and PCBs were the highest in concentrations in about 50% of the samples, which shows their high persistency. Total DDT in air from the Solomon Islands ranged from 200 to 600 ng/polyurethane foam disk (PUF). However, at most locations, a decreasing trend is observed for PCBs, DDT and most other OCPs. Patterns varied per country with e.g. elevated dieldrin in air from Barbados and chlordane in air from the Philippines. A number of OCPs, such as heptachlor and its epoxides, some other chlordanes, mirex and toxaphene have decreased down to almost undetectable levels. PBB153 was hardly found and penta and octa--mix related PBDEs were also relatively low at most locations. HBCD and the decabromodiphenylether were more prominent at many locations and may even still increase. To draw more holistic conclusions more colder climate countries should be included in this program., Funds for this study have been provided by the Global Environment Facility (GEF) through four regional projects: “(Continuing) Support for the implementation of the Global Monitoring Plan under the Stockholm Convention in the African/Asian/GRULAC/Pacific Islands Region”. We are grateful to the RECETOX staff for cleaning and distribution of the PUFs, and local laboratory staff in all countries involved, who installed and exchanged the polyurethane foam filters during this project. We thank Dr. Heidelore Fiedler for her assistance in the preparation of the graphs.

Nowadays concern exists about the safety for both football players and the environment of recycled tire rubber used as infill in synthetic turf football pitches. In this study 40 target compounds, including polycyclic aromatic hydrocarbons (PAHs), plasticizers, antioxidants and vulcanization agents were determined in 50 synthetic football pitches of diverse characteristics to estimate environmental risks. This is the first study of crumb rubber sport facilities in Portugal. Analyses were performed by ultrasound-assisted extraction followed by gas chromatography-tandem mass spectrometry (UAE-GC-MS/MS). To evaluate the transfer of the target chemicals from the crumb rubber to the runoff water, water leachates collected from several football pitches were analyzed by solid-phase microextraction (SPME-GC-MS/MS). In addition, lab-scale runoff simulation experiments were performed to assess whether a persistent inflow of the target compounds from the football pitches into the runoff water wcould exist. Results revealed the presence of most of the target PAHs in crumb rubber at total concentrations up to 57 μg g−1, next to a high number of plasticizers and vulcanization agents. Runoff water collected from the football pitches contained up to 13 PAHs as well as other chemicals of environmental concern. In addition, continuous leaching of chemicals from the crumb rubber to the surrounding water was demonstrated. The transfer of target chemicals into the runoff water poses a potential risk for the aquatic environment.

Crumb rubber obtained from scrap tires is greatly employed for the construction of different facilities for sport, recreational and other uses. However, in recent years the concern about their safety and the related adult and children exposure to these surfaces is growing. This study aims a thorough chemical characterization encompassing 42 hazardous compounds, including polycyclic aromatic hydrocarbons (PAHs), phthalates, adipates, antioxidants and vulcanization agents in a wide range of crumb rubber from different surfaces. For the extraction of the target compounds, a method based on ultrasound-assisted extraction followed by gas chromatography-tandem mass spectrometry (UAE-GC–MS/MS) has been validated. Forty crumb rubber samples coming from synthetic turf football pitches, outdoor and indoor playgrounds, urban pavements, commercial tiles and granulates, and scrap tires, were analyzed. In addition, green alternative materials, such as sand and artificial turf based on cork granulate infill were included to compare the levels of the target compounds with those of crumb rubber. Most of the analyzed recycled surfaces meet the recent limits proposed by the European Commission for rubber granulates and mulches, although they exceed in several cases the maximum levels allowed for rubber consumer products. Besides, most of the other target compounds, including several of them considered as endocrine disruptors, were detected in the analyzed samples, reaching parts per million concentrations.

To make outdoor clothing water- or dirt-repellent, durable water-repellent (DWR) coatings based on side-chain fluorinated polymers (SFPs) are used. During use of outdoor clothing, per- and polyfluoroalkyl substances (PFASs) can be emitted from the DWR to the environment. In this study, the effects of aging, washing, and tumble drying on the concentration of extractable PFASs in the DWR of perfluorohexane-based short-chain SFPs (FC-6 chemistry) and of perfluorooctane-based long-chain SFPs (FC-8 chemistry) were assessed. For this purpose, polyamide (PA) and polyester (PES) fabrics were coated with FC-6- and FC-8-based DWRs. Results show that aging of the coated fabrics causes an increase in concentration and formation of perfluoroalkyl acids (PFAAs). The effect of aging on the volatile PFASs depends on the type of fabric. Washing causes a decrease in PFAA concentrations, and in general, volatile PFASs are partly washed out of the textiles. However, washing can also increase the extractable concentration of volatile PFASs in the fabrics. This effect becomes stronger by a combination of aging and washing. Tumble drying does not affect the PFAS concentrations in textiles. In conclusion, aging and washing of fabrics coated with the DWR based on SFPs release PFASs to the environment.

Social and environmental concern about the use of crumb rubber from end-of-life car tires in the construction of different sport and recreational facilities is increasing due to the presence of hazardous compounds. The aim of this research was the assessment of 42 organic chemicals, including polycyclic aromatic hydrocarbons (PAHs), phthalates, adipates, antioxidants and vulcanisation agents in a large number of infill samples (91) from synthetic turf football pitches of diverse characteristics and geographical origin. Samples were taken worldwide, in 17 countries on 4 continents, to show the global dimension of this problem. Ultrasound assisted extraction was employed to extract the target compounds, followed by gas chromatography coupled to tandem-mass spectrometry (UAE-GC–MS/MS). Seventy-eight crumb rubber samples as well as thirteen samples of alternatives materials, such as cork granulates, thermoplastic elastomers and coconut fibre, were analyzed. The results highlight the presence of all target PAH in most rubber samples at concentrations up to μg g−1, including the eight ECHA (European Chemicals Agency) PAHs considered as carcinogenic, and anthracene (ANC), pyrene (PYR) and benzo[ghi]perylene (B[ghi]P), catalogued as substances of very high concern (SVHC). Endocrine disruptors such as some plasticizers (mainly phthalates), and other compounds like benzothiazole (BTZ) and 2-mercaptobenzothiazole (MBTZ) were found reaching the mg g−1 level. This confirms the presence of the hazardous substances in the recycled crumb rubber samples collected all around the world. Three crumb rubber samples exceeded the limit of 20 μg g−1 for the sum of the eight ECHA PAHs. Regarding the chemical composition of other infill alternatives, cork appears to be adequate, while the thermoplastic elastomers contained high levels of some plasticizers. In addition, the plastic infill as well as the crumb rubber both are microplastics. Microplastics are considered contaminants of emerging concern since they do not biodegrade and remain in the environment for a long time This research was supported by projects RETOS PID2019-104336RB-I00 (Ministry of Science and Innovation, Spain) and UNST10-1E-491 (Infrastructure Program, Ministry of Science and Innovation, Spain). The authors belong to RED2018-102522-T (Ministry of Science, Innovation and Universities, Spain) and to the Galician Competitive Research Groups IN607B 2019/13 and ED431 2020/06 (Xunta de Galicia). This study is based upon work from COST Action CA16215 and from the Sample Preparation Study Group and Network, supported by the Division of Analytical Chemistry of the European Chemical Society. All these programs are co-funded by FEDER (EU). This work was also financially supported by: (i) Base Funding UIDB/00511 2020 of the Laboratory for Process Engineering, Environment, Biotechnology and Energy (LEPABE), by national funds through the FCT/ MCTES (PIDDAC); (ii) Project SAFEGOAL (Ref. PTDC/EQU-EQU/28101/2017; POCI-01-0145-FEDER-028101), funded by FEDER funds through COMPETE2020 – Programa Operacional Competitividade e Internacionalização (POCI) and by national funds (PIDDAC) through FCT/ MCTES. N.R. thanks the Portuguese Foundation for Science and Technology (FCT) for the financial support of his work contract through the Scientific Employment Stimulus - Institutional Call - [CEECINST/00049/2018] SI

In the two rounds of the UNEP-coordinated ‘Biennial interlaboratory assessments of POPs laboratories, which were implemented in 2016/2017 and 2018/2019, 56 and 46 laboratories submitted results for dioxin-like persistent organic pollutants (dl-POPs). Test matrices consisted of solutions of analytical standards and naturally contaminated sediment, air extract, fish and human milk. Performance assessment using z-scores so that satisfactory performance corresponded to 2 z = ±25%, which is recommended for laboratories submitting data to the global monitoring plan of the Stockholm Convention on POPs. Participation has shown that analytical capacity for analyzing dl-POPs exist in all UN regions; however, in Africa and Central and Eastern European countries capacities are (very) limited; in Latin America capacity is increasing. The presence of dioxin laboratories is not limited to industrialized or OECD countries but also present in developing countries such as China, Brazil, Egypt, Thailand, or Vietnam. Laboratories using established methods based on gas chromatographs coupled to high-resolution mass spectrometers (sector field instruments only) by far had the best results. Among the test samples, human milk and especially fish in the last round posed severe problems to all laboratories so that performance must improve, especially in foodstuffs at (very) low concentrations.

Atmospheric levels of chlorinated paraffins (CPs) at five remote, six rural and four urban sites in Australia were measured using XAD-2 passive air samplers (XAD-PAS). While long-chain CP (LCCP, C>17) levels were below method detection limits (MDLs), short-chain CPs (SCCPs, C10-13) and, for the first time, medium-chain CPs (MCCPs, C14-17) and CPs with a carbon chain length of nine (CP–C9) were found at many sites (88%, 81% and 88%, respectively) across the Australian continent, representing a range of environmental conditions. Applying preliminary sampling rates of the XAD-PAS for CPs, gaseous CP levels in Australian air were 3 for ΣSCCPs and ΣMCCPs, respectively, with a significant decreasing trend from more densely to less densely populated areas. Atmospheric median levels in this study (0.37 and 0.47 ng/m3 for SCCPs and MCCPs, respectively) were at the lower end of the median range (0.32–10 and 3.0–4.2 ng/m3 for SCCPs and MCCPs, respectively) reported for CPs at predominantly urban or industrial sites elsewhere (apart from China and extremely remote sites such as Antarctica). Principal component analysis matched the SCCP and MCCP congener group patterns in samples with those found in commercial mixtures, indicating a prevalence of less chlorinated congener groups in the Australian atmosphere. Information about the Australian production, use and disposal of CPs as well as their levels in other environmental matrices, including humans, is needed for assessing their emissions, behaviour, fate and potential exposure.

Effect-directed analysis (EDA) has shown its added value for the detection and identification of compounds with varying toxicological properties in water quality research. However, for routine toxicity assessment of multiple toxicological endpoints, current EDA is considered labor intensive and time consuming. To achieve faster EDA and identification, a high-throughput (HT) EDA platform, coupling a downscaled luminescent Ames and cell-based reporter gene assays with a high-resolution fraction collector and UPLC-QTOF MS, was developed. The applicability of the HT-EDA platform in the analysis of aquatic samples was demonstrated by analysis of extracts from WWTP influent, effluent and surface water. Downscaled assays allowed detection of mutagenicity and androgen, estrogen and glucocorticoid agonism following high-resolution fractionation in 228 fractions. From 8 masses tentatively identified through non-target analysis, 2 masses were further investigated and chemically and biologically confirmed as the mutagen 1,2,3-benzotriazole and the androgen androstenedione. The compatibility of the high-throughput EDA platform with analysis of water samples and the incorporation of mutagenic and endocrine disruption endpoints allow for future application in routine monitoring in drinking water quality control and improved identification of (emerging) mutagens and endocrine disruptors.

Since 2005, the United Nations Environment Programme (UNEP) has supported developing countries with capacity building, including on-site training courses and provision on laboratory materials and consumables, and analysis of samples from Africa, Asia-Pacific and Latin America and the Caribbean (GRULAC) in designated expert laboratories. In order to check the performance of laboratories analyzing persistent organic pollutants (POPs) and giving trust into chemical analytical results, four rounds of interlaboratory assessments (ILs) were organized between 2010 and 2019. These were open to all POPs laboratories. In total, 41 575 z-scores, as indicators of performance, were generated in these four ILs; of these, 8 912 were from laboratories in countries supported by UNEP projects and 3 923 were from expert laboratories; these together constitute 31% of the total. 69% of all z-scores came from laboratories not participating in the UNEP projects, especially from China, who recognized the importance of such exercises for quality control at an early stage. The results showed that POPs analytical capacity has increased over the years, but some gaps could not be closed especially not when LC-MS/MS equipment is essential such as for PFAS and congener-specific HBCD. Use of mass spectrometers provides better results than ECD instruments due to the broad spectrum of organochlorine pesticides to be analyzed under the Stockholm Convention. The main conclusion for all laboratories is that interlaboratory assessments provide important and objective snapshots of performance for the laboratories themselves and for external clients. The methods used in any interlaboratory testing should be the same as during routine analysis between such tests.

The environmental monitoring of plastics is positioned high on the agenda of countries and international organisations worldwide. Large scale national and regional monitoring programs are however hampered by the lack of urgently needed harmonised analytical methods and reference materials for QA/QC of these methods. Data on the presence of plastics in the environment varies largely regarding quality and comparability. Robust and validated harmonised methods and QA/QC tools still missing. Interlaboratory studies are an efficient way to achieve this and both gather information on the state of the art, can be used to validate the methods in terms of uncertainty and to select candidate reference materials. Here we will present the result of two ILS studies of which one is currently on-going and the approach of the new EU project EUROqCHARM which will focus on the harmonisation of analytical methods for nano-, micro- and macro plastic in environmental samples and the production of reference material.

Chlorinated paraffins (CPs) are used in various products to improve their physicochemical characteristics. Due to recycling, CPs may end up in "new" recycled products. In this study we investigated CPs present in end-of-life car tires that are recycled to rubber granulates used on artificial soccer fields, and playground tiles. The -CP(C 10-C 30) concentrations ranged from 1.5 to 67 μg/g in car tires, 13-67 μg/g in rubber granulates, and 16-74 μg/g in playground tiles. MCCPs were the dominant CP group with an average contribution of 72%. LCCPs up to C 30, were detected for the first time in car tires, rubber granulates, and playground tiles. The CPs application in tires is unclear, the low CP concentrations found in this study (

This review reports on how Ghanaian scientists analyse insecticide residues in various matrices in their laboratories as well as the levels of insecticides found in Ghana. It covers different sample preparation methods such as solid-liquid and liquid-liquid extraction. The main technique used for this analysis was gas chromatography (GC) with various detectors such as electron capture, flame photometric, nitrogen phosphorus, and mass spectrometric detection. Liquid chromatography (LC) with mass spectrometric detection was sometimes used to determine the levels of very polar insecticide residues. From the articles reviewed 74% of the insecticides detected were organochlorines with DDTs, lindanes, and endosulfans as most abundant ones. Levels of the insecticides of interest analysed, varied from below the detection limits to clearly above the safety limits. The lowest detected concentration of insecticide residues reported in fruits and vegetables was δ-lindane in pawpaw (0.06 mg/kg) while the highest was fenvalerate (25.6 mg/kg). Insecticide residues reported in sediment were predominantly organochlorines with concentrations ranging from 9.68 ng/kg to 10.98 µg/kg. Endosulfan and its metabolites were the main insecticides found in water bodies with concentrations ranging from 0.036 µg/L to 62.3 µg/L. DDT and its metabolites were the dominant insecticides found in human fluids.

In this study, we investigated chemical additives present in new and used spray polyurethane foams (SPFs) and assessed the dermal transfer through direct contact. This first study shows that cured do-it-yourself spray one-component SPFs (OCFs) often contain chlorinated paraffins (C14-C37), and tris (1-chloro-2-propyl) phosphate (TCIPP), ranging 0.2–50%, and 0.9–30% w/w, respectively. Six OCFs contained CP levels ranging 22–50% w/w, whereas nine OCFs used for similar applications only contained CP levels ranging 2–17% w/w. It is unclear if the combination CPs/TCIPP is meant to improve the flame retardancy of products, and could suggest an unnecessary use of high CPs/TCIPP concentrations in OCFs. The two-component SPFs (TCFs) contained only TCIPP with levels ranging from 7.0% to 9.0%. The CPs and TCIPP were easily transferred from cured OCFs to the hands. Levels up to 590 µg per hand for CPs and up to 2.7 µg per hand for TCIPP were found. After end-of-life, it is challenging to recycle used SPFs. They may, therefore, end up at landfills where the TCIPP/CPs may leach into the environment. Therefore, further investigation is needed to assess potential exposure risks associated with general and occupational use, and the impact of landfill leaching on the environment.

Concern on relatively high levels and the potential bioaccumulation of decabromodiphenylether (BDE209) has led to a European 8-year monitoring program on trends in BDE209 concentrations in birds, sewage sludge and sediments from seven countries. BDE209 was analysed in four environmental matrices: sparrowhawk eggs (UK), glaucous gull eggs (Bear Island, Norway), sewage sludge (UK, Ireland and the Netherlands) and sediment (France, Germany, the Netherlands, UK and Ireland). BDE209 was detected in most of the glaucous gull and sparrow hawk eggs but neither increasing nor decreasing trends in these BDE209 levels were observed. An indication for debromination of BDE209 in sparrowhawk eggs was found. BDE209 concentrations in sediments ranged from very low ng/g (88 ng/g on an organic carbon (OC) basis) concentrations, in the rivers Elbe, Ems, Seine and the Outer Humber, to high μg/g (120 μg/g OC), in the Western Scheldt, Liverpool Bay and River Mersey. Apart from decreasing values in the Western Scheldt sediment no further decreases in BDE209 concentrations were observed over time, neither in sediment nor in sewage sludge showing that the voluntary emissions control program of the bromine industry only had a local effect. In contrast to the sewage sludge samples from the Netherlands (mean 355 ng/g dry weight (dw) or 1026 ng/g OC), the BDE209 concentrations in the UK increased at all sites from 2006 to 2011 (8092 ng/g dw or 22,367 ng/g OC). The BDE209 levels in several UK sediments and sewage sludge were still very high at the end of the program in 2012, most likely caused by frequent use of BDE209 in the textile industry. This may be indicative of the persistence of BDE209 and the limited degradation into lower brominated congeners in sediment, although it cannot be excluded that ongoing BDE209 emissions have played a role as well.

Seven pesticides, profenofos, metalaxyl, λ-cyhalothrin, 4,4′-DDT, 4,4′-DDE, and α- and β-endosulfan, were determined in vegetables (tomato, onion) from 20 locations and surface waters from 12 locations in the Central Rift Valley (CRV) of Ethiopia. Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) and solid phase extraction (SPE) methods were used for the vegetables and water, respectively. In 2.5% of the tomato samples, profenofos was detected above European maximum residue limits (MRLs), in 12.5% of the samples metalaxyl, and in 2.5% α- and β-endosulfan. In 5% of the onion samples, profenofos was detected above European MRLs, in 7.5% of the onion samples metalaxyl, and in 5% λ-cyhalothrin. In surface water, profenofos was detected at the highest concentration of 2300 μg/L in the Bulbula River, 890 μg/L near the agricultural land north of Lake Ziway (ANLZ-1), 1700 μg/L in the floriculture effluent (FE-1), and 900 μg/L in tap water at the Batu Drinking Water (BDW) supply. These results show that the levels of pesticides are in several cases substantially elevated, and emphasize the need of regular pesticide monitoring programs for surface waters and vegetables in the Ethiopian CRV.

To assess the effects of weathering on per- and polyfluoroalkyl substances (PFASs) from durable water repellent (DWR) clothing, thirteen commercial textile samples were exposed to elevated ultra violet (UV) radiation, humidity, and temperature in an aging device for 300 h, which mimics the lifespan of outdoor clothing. Before and after aging, the textile samples were extracted and analysed for the ionic PFASs (perfluoroalkyl acids (PFAAs), perfluorooctane sulfonamide (FOSA)) and volatile PFASs (fluorotelomer alcohols (FTOHs), acrylates (FTACs) and methacrylates (FTMACs)). Results showed that weathering can have an effect on PFASs used in DWR of outdoor clothing, both on the PFAS profile and on the measured concentrations. In most weathered samples the PFAA concentrations increased by 5- to more than 100-fold, while PFAAs not detected in the original textiles were detected in the weathered samples. DWR chemistries are based on side-chain fluorinated polymers. A possible explanation for the increase in concentration of the PFAAs is hydrolysis of the fluorotelomer based polymers (FTPs), or degradation of the FTOHs, which are used in the manufacturing of the FTPs. The concentrations of volatile PFASs also increased, by a factor up to 20. Suggested explanations are the degradation of the DWR polymers, making non-extractable fluorines extractable, or the transformation or degradation of unknown precursors. Further research is needed to unravel the details of these processes and to determine the transformation routes. This study shows that setting maximum tolerance limits only for a few individual PFASs is not sufficient to control these harmful substances in outdoor clothing.

A quantitative assessment of pollutants of emerging concern in the Hartbeespoort Dam catchment area was conducted using liquid chromatography-tandem mass spectrometry (LC-MS/MS) to establish the occurrence, source and distribution of 15 environmental pollutants, including 10 pharmaceuticals, 1 pesticide and 4 steroid hormones. Seasonal sampling was conducted in the Hartbeespoort Lake using sub-surface grab sampling to determine the lake's ecological status and obtain data for establishment of progressive operational monitoring. The Jukskei River, which lies upstream of the Hartbeespoort Dam, was sampled in the winter season. Five year old carp (Cyprinus carpio) and catfish (Clarias gariepinus) were also sampled from the Hartbeespoort Dam to study bioaccumulation in biota as well as to estimate risk associated with fish consumption. In the Jukskei River, the main source of 11 emerging pollutants (EPs) was identified as raw sewage overflow, with the highest ∑11 EP concentration of 593 ng L−1 being recorded at the Midrand point and the lowest ∑11 EP concentration of 164 ng L−1 at the N14 site located 1 km downstream of a large wastewater treatment plant. The Jukskei River was found to be the largest contributor of the emerging contaminants detected in the Hartbeespoort Dam. In the Hartbeespoort Dam EP concentrations were generally in the order efavirenz > nevirapine > carbamazepine > methocarbamol > bromacil > venlafaxine. Water and sediment were sampled from the uMngeni River estuary within 24 h after large volumes of an assortment of pharmaceutical waste had been discovered to be washed into the river estuary after flash rainfall on 18 May 2016. Analytical results revealed high levels of some emerging pollutants in sediment samples, up to 81 ng g−1 for nevirapine and 4 ng g−1 for etilefrine HCL. This study shows that efavirenz, nevirapine, carbamazepine, methocarbamol, bromacil and venlafaxine are contaminants that require operational monitoring in South African urban waters.

Effect-directed analysis (EDA) is a commonly used approach for effect-based identification of endocrine disruptive chemicals in complex (environmental) mixtures. However, for routine toxicity assessment of, for example, water samples, current EDA approaches are considered time-consuming and laborious. We achieved faster EDA and identification by downscaling of sensitive cell-based hormone reporter gene assays and increasing fractionation resolution to allow testing of smaller fractions with reduced complexity. The high-resolution EDA approach is demonstrated by analysis of four environmental passive sampler extracts. Downscaling of the assays to a 384-well format allowed analysis of 64 fractions in triplicate (or 192 fractions without technical replicates) without affecting sensitivity compared to the standard 96-well format. Through a parallel exposure method, agonistic and antagonistic androgen and estrogen receptor activity could be measured in a single experiment following a single fractionation. From 16 selected candidate compounds, identified through nontargeted analysis, 13 could be confirmed chemically and 10 were found to be biologically active, of which the most potent nonsteroidal estrogens were identified as oxybenzone and piperine. The increased fractionation resolution and the higher throughput that downscaling provides allow for future application in routine high-resolution screening of large numbers of samples in order to accelerate identification of (emerging) endocrine disruptors.

Phosphate flame retardants (PFRs) are ubiquitous chemicals in the indoor environment. Diphenyl phosphate (DPHP) is a major metabolite and a common biomarker of aryl-PFRs. Since it is used as a chemical additive and it is a common impurity of aryl-PFRs as well as a degradation product, its presence in indoor dust as an additional source of exposure should not be easily ruled out. In this study, DPHP (and TPHP) are measured in indoor dust in samples collected in Spain and in the Netherlands (n=80). Additionally, the presence of other emerging aryl-PFRs was monitored by target screening. TPHP and DPHP were present in all samples in the ranges 169–142,459ng/g and 106–79,661ng/g, respectively. DPHP concentrations were strongly correlated to the TPHP levels (r=0.90, p

The coupling of comprehensive two-dimensional gas chromatography with high-resolution time-of-flight mass spectrometry offers the best separation efficiency combined with accurate mass measurements over a wide mass range. The tremendous power of this screening tool is illustrated by trace qualitative screening analysis of organohalogenated compounds (OHCs) in pet cat hair. Tentative identification was supported by mass spectral database searches and elemental formula prediction from the experimentally determined accurate mass data. This screening approach resulted in the first tentative identification of pentabromoethylbenzene, decabromodiphenyl ethane, hexabromocyclododecane, trisbromoneopentyl alcohol, tris(2-chloroethyl) phosphate and tris(2-chloroisopropyl)phosphate in the South African indoor environment. A total of seventy-two OHCs were identified in the samples and include known flame retardants, such as polybrominated diphenyl ethers, and legacy contaminants such as polychlorinated biphenyls and organochlorine, organophosphorous and pyrethroid pesticides. The results obtained from cat hair indicate that these pets are exposed to complex mixtures of OHCs and the detection of these compounds suggests that non-invasive cat hair samples can be used to model indoor exposure with reference to external deposition of OHCs present in the air and dust surrounding people. Toddlers share the same environment as pet cats and therefore also the same health risks.

The Salmonella reversion based Ames test is the most widely used method for mutagenicity testing. For rapid toxicity assessment of e.g. water samples and for effect-directed analysis, however, the Ames test suffers from lack of throughput and is regarded as a laborious, time consuming method. To achieve faster analysis, with increased throughput, a (downscaled) luminescent derivative of the Ames Salmonella/microsome fluctuation test has been developed through expression of the Photorhabdus luminescens luciferase in the Salmonella TA98 and TA100 strains. The applicability of this test is demonstrated by analysis of environmentally relevant compounds, a suspended particulate matter extract and an industrial effluent sample. Use of the luminescent reporter reduced the required detection time from 48 to 28 h with a specificity of 84% for responses reported in the literature to a set of 14 mutagens as compared to 72% in the unmodified fluctuation test. Testing of the same compounds in a downscaled luminescent format resulted in an 88% similarity with the response found in the regular luminescent format. The increase in throughput, faster analysis and potential for real-time bacterial quantification that luminescence provides, allows future application in the high-throughput screening of large numbers of samples or sample fractions, as required in effect-directed analysis in order to accelerate the identification of (novel) mutagens.

Recycled crumb rubber (CR) is rich in compounds with unrecognized toxic potency; this study aims at the development of an analytical method that would allow identification and quantification of a very wide range of organic compounds extractable from the complex rubber matrix. The analytical set-up includes target analysis of polycyclic aromatic hydrocarbons (PAHs) and methyl-PAHs and suspect screening of raw extracts to tentatively identify primary organic compounds present, but not included in the standard target analysis of recycled rubber, followed by analytical method development and target analysis of identified compounds. Analyzed samples included weathered and new CR originating from football turf granulates, rubber mats, and end-of-life car tires (ELTs). The developed analytical method involves sonication extraction, followed by solid phase extraction (SPE) fractionation that enables simple and efficient separation of analytes with broad polarity scale. The application of SPE fractionation resolves coelution problems and simplifies the chromatograms. This analytical approach allowed to identify and quantify 46 sample specific compounds, including several heterocyclic PAHs like 2-methylthiobenzothiazole, benzonapthothiophenes, benzonaphthofuranes and aromatic amines like diphenylamine and N-phenyl-2-naphthylamine, which to our knowledge were not determined before. The PAHs concentrations determined in CR tiles purchased in Dutch and Spanish shops exceed the EU limits for articles marketed for use by the public. Furthermore, sets of methylated PAHs, dibenzothiazoles and aromatic amines were identified and quantified, and several other compounds were tentatively identified. The obtained results stress the need for expanding the list of target compounds analyzed in CR and the need for longitudinal studies on weathering processes taking place in CR SI

A study of the distribution of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) utilising 16 priority PAHs, benzo(e)pyrene, perylene, 19 alkylated PAHs and 31 ortho substituted PCBs in South Africa is presented. It was aimed to (a) deduce characteristic contamination patterns for both PCBs and PAHs and (b) provide the first comprehensive dataset for establishment of source characterisation of PCBs and PAHs. This is in line with new South African legislation on mandatory monitoring of PCB and PAH emissions. Bar charts, principal component analysis (PCA) and biplots were utilised to identify signature contamination patterns and distribution of PCBs and PAHs within the Jukskei and Klip Rivers. Sediments from the Jukskei and Klip River catchments both showed distinct contamination signatures for hexa to nonachlorinated PCBs, characteristic of contamination by Aroclor 1254 and 1260 technical mixtures. PCB signature patterns in order of abundance were 138 > 180 > 206 > 153 > 187 > 149 and 138 > 153 > 180 > 149 > 187 > 110 > 170 for the Jukskei and Klip River sediments, respectively. The upstream Alberton point had the highest Σ31 PCB and Σ (parent+alkyl) PAH concentrations in the Klip River of 61 and 6000 μg kg−1 dry weight (dw), respectively. In the Jukskei River, the upstream Marlboro point had the highest Σ31 PCB concentration of 19 μg kg−1 dw and the N14 site recorded the highest Σ (parent+alkyl) PAH concentration of 2750 μg kg−1 dw. PAH concentrations in both the Jukskei and Klip Rivers were significantly higher than the PCB concentrations. Fluoranthene, phenanthrene and pyrene were found in the highest concentrations in both the Jukskei and Klip River sediments. Both the Jukskei and Klip River sediments showed trends of a mixed pyrogenic-petrogenic PAH source contamination.

Thermal paper contains potentially toxic compounds such as bisphenol A (BPA), which is used as a color developer. BPA has been reported in thermal paper in concentrations up to 42,600 μg g−1. The exposure to BPA via dermal transfer has been recently discussed as a significant contribution to the overall human exposure and the estimated daily intake (EDI) has been reported up to 218 μg d−1. BPA has been also detected in recycled paper with concentrations up to 46 μg g−1. Due to the fact that BPA is a known endocrine disruptor and migrates from materials, regulatory restrictions have been established to prevent risks for the human health. As a consequence, structural analogues, such as bisphenol S (BPS) have been introduced into the market. Little is known about the presence and toxicity of these emerging replacements, and concern has risen about them. The present review gives an overview of the occurrence and levels of BPA and replacements in thermal paper. BPA is still the most common color developer found in thermal paper, followed by BPS. The analytical methods used for quantification of BPA and BPA replacements in paper products are also reviewed. BPA is transferred from thermal paper products to the finger pads upon handling it. Paper-skin transfer followed by penetration of BPA depends on conditions (e.g. greasiness of fingers and use of hand cream). It is, however, still debated whether thermal paper as a source for human exposure contributes significantly to the overall internal BPA exposure.

To simultaneously quantify and profile the complex mixture of short-, median-, and long-chain CPs (SCCPs, MCCPs, and LCCPs) in Australian sewage sludge, we applied and further validated a recently developed novel instrumental technique, using quadrupole time-of-flight high resolution mass spectrometry running in the negative atmospheric pressure chemical ionization mode (APCI-qTOF-HRMS). Without using an analytical column the cleaned extracts were directly injected into the qTOF-HRMS followed by quantification of the CPs by a mathematical algorithm. The recoveries of the four SCCP, MCCP and LCCP-spiked sewage sludge samples ranged from 86 to 123%. This APCI-qTOF-HRMS method is a fast and promising technique for routinely measuring SCCPs, MCCPs, and LCCPs in sewage sludge. Australian sewage sludge was dominated by MCCPs with concentrations ranging from 542 to 3645 ng/g dry weight (dw). Lower SCCPs concentrations (

Polychlorinated n-alkanes or chlorinated paraffins (CPs) contain a magnitude of structural isomers and are categorized as short-chain (SCCPs), medium-chain (MCCPs), and long-chain (LCCPs) CPs, according to the carbon chain lengths. In this study the ƩSCCPs, ƩMCCPs, and ƩLCCP concentrations are reported for South African indoor dust and pet cat hair. The median concentrations of the ƩCPs (C9-C37) ranged from 33 to 663 μg/g for freshly collected dust (FD), 36-488 μg/g for dust collected from household vacuum cleaner bags (VD), and 1.2-15 μg/g for cat hair (CH) samples. MCCPs were the dominant CP group, followed by SCCPs and LCCPs. The ƩMCCP concentration ranged from 13 to 498 μg/g in dust and 0.6-6.5 μg/g in cat hair. SCCPs with shorter carbon chains and lower chlorine substitution were observed in cat hair. LCCPs with carbon chains > C20 were detected in dust and hair samples, possibly indicating the use of wax grade LCCP formulations. Non-traditional Kendrick mass defect plots were used to obtain information on the magnitude of CPs and provide evidence of possible interfering compounds. This is the first report on the occurrence of SCCPs, MCCPs, and LCCPs in the South African indoor environment.

Use of halogenated flame retardants continues despite health and environmental concerns

Flame retardants (FRs), such as brominated flame retardants (BFRs) and organophosphorus flame retardants (OPFRs), are diverse groups of compounds used in various products related to the indoor environment. In this study concentrations of eight polybrominated diphenyl ethers (PBDEs), two alternative BFRs and ten OPFRs were determined in indoor dust (n = 20) and pet cat hair (n = 11) from South Africa. The OPFRs were the major FRs, contributing to more than 97% of the total FR concentration. The median Ʃ10OPFRs concentrations were 44,800 ng/g in freshly collected dust (F-dust), 19,800 ng/g in the dust collected from vacuum cleaner bags (V-dust), and 865 ng/g in cat hair (C-hair). Tris(1-chloro-2-propyl) phosphate (TCIPP) was the dominant OPFR in the dust samples with median concentrations of 7,010 ng/g in F-dust and 3,590 ng/g in V-dust. Tris(2-butoxyethyl) phosphate (TBOEP) was the dominant OPFR in C-hair, with a median concentration of 387 ng/g. The concentrations of Ʃ8PBDEs were higher in F-dust than in V-dust. BDE209 was the dominant BFR in all three matrices. Bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (BEH-TEBP) and 2-ethylhexyl-2,3,4,5- tetrabromobenzoate (EH-TBB) showed notable contributions to the BFR profile in cat hair. A worst-case dust exposure estimation was performed for all analytes. The estimated TCIPP daily intake through dust ingestion was up to 1,240 ng/kg bw for toddlers. The results indicate that OPFRs are ubiquitous in South African indoor environment. Indoor dust is a major source of human exposure to environmental contaminants. This can for example occur through hand-to-mouth contact of toddlers, and is an important route of exposure to currently used FRs accumulated on dust particles. The presence of FRs, in particular high concentrations of OPFRs, suggests that children and indoor pet cats may have greater exposure to FRs than adults.

The gas chromatographic retention behaviour of 16 polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs on a new ionic liquid stationary phase, 1,12-di(tripropylphosphonium) dodecane bis(trifluoromethanesulfonyl)imide (SLB&reg, ILPAH) intended for the separation of PAH mixtures, was compared with the elution pattern on more traditional stationary phases: a non-polar phenyl arylene (DB-5ms) and a semi-polar 50% phenyl dimethyl siloxane (SLB PAHms) column. All columns were tested by injections of working solutions containing 20 parental PAHs from molecular weight of 128 to 278 g/mol and 48 alkylated PAHs from molecular weight of 142 to 280 g/mol on a one dimensional gas chromatography-mass spectrometry (GC-MS) system. The SLB PAHms column allowed separation of most isomers. The SLB&reg, ILPAH column showed a rather different retention pattern compared to the other two columns and, therefore, provided a potential for use in comprehensive two-dimensional GC (GC&times, GC). The ionic liquid column and the 50% phenyl column showed good thermal stability with a low bleed profile, even lower than that of the phenyl arylene &ldquo, low bleed&rdquo, column.

This review provides an update on information regarding the production volumes, regulations, as well as the environmental levels, trends, fate and human exposure to chlorinated paraffin mixtures (CPs). CPs encompas thousands congeners with varying properties and environmental fate. Based on their carbon chain lengths, CPs are divided into short- (SCCPs; C10-13), medium- (MCCPs; C14-17) and long- (LCCPs; C ≥ 18) chained groups. They are high production volume and persistent chemicals, and their cumulative global production already surpasses that of other persistent anthropogenic chemicals (e.g. PCBs). However, international regulations are still curbed by insufficient information on their levels and fate, including bioaccumulation and toxicity potential. An increasing number of studies since 2010 demonstrate that CPs are detected in almost every compartment in the environment, including remote areas. Consensus on the long range transport and high bioaccumulation potential (BCF > 5000 & TMF > 1) has recently been reached for SCCPs, fulfilling criteria under the Stockholm Convention for designation as a persistent organic pollutant; information on their levels is, however, still sparse for many countries. M/LCCPs have received comparatively little attention in the past, but as replacement chemicals for SCCPs, MCCPs are now considered in an increasing number of studies. The limited data to date suggests MCCPs are widely used. Although data on their bioaccumulation and toxicity are still inconclusive, MCCPs and LCCPs with C

The Central Himalayas are not only a natural boundary between China and Nepal but also a natural barrier for transport of air masses from South Asia. In this study, 99 samples of surface soil were collected from five regions of Nepal on the southern side of the Central Himalayas, and 65 samples of surface soil were obtained from the northern side on the edge of the Tibetan Plateau, China (TPC). Concentrations of polycyclic aromatic hydrocarbons (PAHs) in soils were measured to determine their distribution, potential for accumulation, and sources, as well as risks to humans and the environment. Mean concentrations of Σ 16 PAHs were 2.4 × 10 2 and 3.3 × 10 2 ng/g dry mass (dm) in soils collected from the TPC and Nepal, respectively. Significant correlations between concentrations of lower molecular weight PAHs (LMW-PAHs) in soils and altitude were found. Total organic carbon (TOC) in soil was positively but weakly correlated with concentrations of PAHs in the study area, which suggested little role of TOC in adsorption of PAHs. The cities of Kathmandu and Pokhara in Nepal and Nyemo (especially Zhangmu Port), Shigatse, and Lhasa on the TPC, were areas with relatively great concentrations of PAHs in soils. The main sources of PAHs identified by positive matrix factorization were emissions from motor vehicles and combustion of coal and biomass in the Central Himalayas. Calculated total benzo[ a ]pyrene potency equivalents of 0.23–44 ng/g dm and index of additive cancer risk of 3.8 × 10 − 3 –9.2 × 10 − 1 indicated that PAHs in almost all soils investigated posed de minimis risk of additional cancer to residents via direct contact and had no significant risk of additional cancers through consumption of potable water. Mean risk quotient values indicated that 39% of soils had a slight risk to wildlife and the ambient environment of the Central Himalayas.

High levels of polycyclic aromatic hydrocarbons (PAHs) in soil are regularly reported worldwide, particularly in industrialized areas. Through traffic and industrial production PAH generation will further increase. Although better insights in bioavailability of PAHs have led to more balanced decisions on intervention, at many locations PAH concentrations will exceed intervention values and remediation of soil will be necessary, e.g. for allowing a sustainable agriculture. This review summarizes recent practical options for remediation of PAH-contaminated soil, with their advantages and disadvantages. If time is available, phytoremediation, in combination with supporting techniques emerges as an environment-friendly and cost-effective technique that can be efficient at the same time, dependent of the degree and type of PAH pollution.

Resorcinol bis(diphenylphosphate) (RDP) is an organophosphorus flame retardant widely used in electric and electronic equipment. It has been detected in house dust of several European countries according to recent literature. Similar to other flame retardants, RDP formulations and products treated with RDP, such as plastics, can contain RDP impurities, byproducts and breakdown products. In this study, we use screening methods based on wide scope solvent extraction and high resolution time-of-flight mass spectrometry for the identification of RDP related compounds in products and in dust. We analyzed both plastics from electrical/electronic equipment that contained RDP and indoor dust collected on and around surfaces of this equipment. A variety of compounds, namely TPHP, hydroxylated TPHP and RDP (meta-HO-TPHP and meta-HO-RDP), dihydroxylated TPHP, RDP with the loss of a phenyl group (RDP-[Phe]) and RDP oligomers were detected in plastics containing high levels of RDP. Regarding dust samples collected on electronics, TPHP meta-HO-TPHP, meta-HO-RDP, RDP-[Phe] and RDP oligomers were detected. High concentrations of meta-HO-TPHP (20-14 227 ng/g), TPHP (222-50 728 ng/g) and RDP (23-29 118 ng/g) were found in many of the dust samples, so that these compounds seem to easily migrate into the environment. These RDP impurities, byproducts and breakdown products are for the first time reported in indoor dust. Meta-HO-TPHP could be relevant for future biomonitoring studies concerning flame retardants.

The evaluation of the oral uptake of engineered nanoparticles (ENPs) contained in personal care products like mouthwashes is of great relevance to estimate the potential hazards and the toxicity of engineered nanomaterials (ENMs). Various experiments were carried out while two commercially available mouthwash products (named M1 and M2) were selected as samples of interest. Asymmetric flow field-flow fractionation (AF4) was chosen and optimized as the particle separation technique and two detectors were on-line coupled while dynamic light scattering (DLS) was used for evaluation and signals obtained by ultraviolet–visible (UV–vis) detection at 254 nm were used to gather additional information about the fate of the ENPs.

In textiles, like outdoor clothing, per- and polyfluoroalkyl substances (PFASs) are often used for durable water repellency (DWR) of the final products. The analytical performance to determine the concentration of these chemicals available for exposure to humans and to the environment need to be established. Here a method for the extraction and analysis of one class of PFASs, namely perfluoroalkyl acids (PFAAs), in outdoor clothing was developed and validated. The PFAAs which were validated, included perfluoroalkyl carboxylic acids (PFCAs) (C4-C14), and perfluoroalkane sulfonic acids (PFSAs) (C4, C6, C7, C8). In addition, perfluorooctane sulfonamide (FOSA) was included in this study. The method was based on an organic solvent extraction and analysis by high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS). No further cleaning was needed. Two commonly used organic solvent compositions were evaluated for the optimal extraction, i.e. methanol and acetone/acetonitrile (80:20, v/v), and the number and duration of the sequential extractions were optimized. Results showed that two sequential extractions with 5 mL methanol and an extraction time of 30 min gave an optimal performance with an extraction efficiency of >90%. The influence of matrix on the quantification of PFAAs was studied. This indicated ion suppression due to different matrix effects or sorption behavior to specific textile samples. Validation of the entire method showed overall recoveries of>80% and relative standard deviations (RSDs) of

Plastics are complex mixtures consisting of a polymer and additives with different physico-chemical properties. We developed a broad screening method to elucidate the nature of compounds present in plastics used in electrical/electronic equipment commonly found at homes (e.g., electrical adaptors, computer casings, heaters). The analysis was done by (a) solvent extraction followed by liquid chromatography coupled to high accuracy/resolution time-of-flight mass spectrometry (TOFMS) with different ionization sources or (b) direct analysis of the solid by ambient mass spectrometry high accuracy/resolution TOFMS. The different ionization methods showed different selectivity and sensitivity for the different compound classes and were complementary. A variety of antioxidants, phthalates, UV filters, and flame retardants were found in most samples. Furthermore, some recently reported impurities or degradation products derived from flame retardants were identified, such as hydroxylated triphenyl phosphate and tetrabromobisphenol A monoglycidyl ether. Graphical abstract Wide screening of plastic additives by direct probe injection (DIP)-APCI, LC-APCI and LC-ion booster ESI Electronic supplementary material The online version of this article (doi:10.1007/s00216-015-9238-5) contains supplementary material, which is available to authorized users.

Chlorinated paraffins (CPs) are high production volume chemicals of which some show resistance to environmental degradation, long-rang transport, bioaccumulation and toxicity potential. Information regarding their presence in humans is limited, including their human bioaccumulation potential. The present study aimed to evaluate CP levels in human serum from Australia in order to better understand their exposure and current pollution status as well as trends associated with age and time between 2004 and 2015. For this, we selected a male sub-group of the Australian population under 60 years old (n = 16 pools, total 1600 serum samples). While long-chain CP (C18-20) and most short-chain CP (C10-13, SCCPs) levels were below method detection limits (MDL), medium-chain CPs (C14-17, MCCPs) were found in most serum samples (detection frequency 94%) as well as CPs with a carbon chain length of nine (detection frequency 76%). The levels of ΣSCCPs and ΣMCCPs ranged from