Impact of Legislation on Brominated Flame Retardant Concentrations in UK Indoor and Outdoor Environments: Evidence for Declining Indoor Emissions of Some Legacy BFRs.

Concentrations of polybrominated diphenyl ethers, hexabromocyclododecane (HBCDD), and novel brominated flame retardants (NBFRs) were measured in indoor dust, indoor air, and outdoor air in Birmingham, UK. Concentrations of ΣBFRs ranged from 490 to 89,000 ng/g, 46-14,000 pg/m3, and 22-11,000 pg/m3, respectively, in UK indoor dust, indoor air, and outdoor air. BDE-209 and decabromodiphenyl ethane (DBDPE) were the main contributors. The maximum concentration of DBDPE (10,000 pg/m3) in outdoor air is the highest reported anywhere to date. In contrast with previous studies of outdoor air in Birmingham, we observed significant correlations between concentrations of tri- to hepta-BDEs and HBCDD and temperature. This may suggest that primary emissions from ongoing use of these BFRs have diminished and that secondary emissions (e.g., evaporation from soil) are now a potentially major source of these BFRs in outdoor air. Conversely, the lack of significant correlations between temperature and concentrations of BDE-209 and DBDPE may indicate that ongoing primary emissions from indoor sources remain important for these BFRs. Further research to clarify the relative importance of primary and secondary sources of BFRs to outdoor air is required. Comparison with earlier studies in Birmingham reveals significant (p < 0.05) declines in concentrations of legacy BFRs, but significant increases for NBFRs over the past decade. While there appear minimal health burdens from BFR exposure for UK adults, dust ingestion of BDE-209 may pose a significant risk for UK toddlers.

Occurrence, source apportionment, and ecological risk assessment of organophosphate esters in surface sediment from the Ogun and Osun Rivers, Southwest Nigeria.

Organophosphate esters (OPEs) are synthetic chemicals widely used as e.g., flame retardants and plasticisers in various consumer products. Due to the toxicity of OPEs in aquatic ecosystems, exposure of fauna and flora to these compounds is of potential concern. In this study, the concentrations, profiles, sources, and ecological risk of eight OPEs were investigated in the sediments from the two major rivers in southwest Nigeria. Concentrations of ∑OPEs in surface sediments were in the range 13.1 - 2110 ng/g dry weight (dw) (median: 378 ng/g dw) in the Ogun River and 24.7-589 ng/g dw (median: 174 ng/g dw) in the Osun River. These concentrations are broadly within the range of those reported in surface sediment in previous studies conducted in other locations around the world. Tris (2-butoxyethyl) phosphate (TBOEP) was the dominant OPE in the sediment samples with a median concentration of 337 and 126 ng/g dw for the Ogun and Osun Rivers respectively, while tri-n-butyl phosphate (TnBP) was not detected in any sample. Excluding TBOEP, the chlorinated organophosphate esters: tris(2-chloroethyl) phosphate (TCEP), tris(2-chloro-propyl) phosphate (TCIPP), and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) were the dominant OPEs in the Osun River, while the aryl-OPEs: triphenyl phosphate (TPHP), 2-ethylhexyl diphenyl phosphate (EHDPP), and tri-m-tolyl phosphate (TMTP) were dominant in the Ogun River. Under a median exposure scenario, moderate ecological risk was predicted from exposure to TCIPP in the Osun River. In contrast, under a high exposure scenario, concentrations of TDCIPP (risk quotient, RQ = 5.33-5.37) constituted a high ecological risk in both rivers, with moderate risks observed for TBOEP (RQ = 0.022-0.18) and TCIPP (RQ = 0.097 - 0.16). Therefore, the risk to aquatic organisms from concomitant exposure to mixtures of OPEs in freshwater ecosystems requires further investigation.

100 years of anthropogenic impact causes changes in freshwater functional biodiversity.

Despite efforts from scientists and regulators, biodiversity is declining at an alarming rate. Unless we find transformative solutions to preserve biodiversity, future generations may not be able to enjoy nature's services. We have developed a conceptual framework that establishes the links between biodiversity dynamics and abiotic change through time and space using artificial intelligence. Here, we apply this framework to a freshwater ecosystem with a known history of human impact and study 100 years of community-level biodiversity, climate change and chemical pollution trends. We apply explainable network models with multimodal learning to community-level functional biodiversity measured with multilocus metabarcoding, to establish correlations with biocides and climate change records. We observed that the freshwater community assemblage and functionality changed over time without returning to its original state, even if the lake partially recovered in recent times. Insecticides and fungicides, combined with extreme temperature events and precipitation, explained up to 90% of the functional biodiversity changes. The community-level biodiversity approach used here reliably explained freshwater ecosystem shifts. These shifts were not observed when using traditional quality indices (e.g. Trophic Diatom Index). Our study advocates the use of high-throughput systemic approaches on long-term trends over species-focused ecological surveys to identify the environmental factors that cause loss of biodiversity and disrupt ecosystem functions.

Over long periods of time, environmental changes ­ such as chemical pollution and climate change ­ affect the diversity of organisms that live in an ecosystem, known as 'biodiversity'. Understanding the impact of these changes is challenging because they can happen slowly, their effect is only measurable after years, and historical records are limited. This can make it difficult to determine when specific changes happened, what might have driven them and what impact they might be having. One way to measure changes in biodiversity over time is by analysing traces of DNA shed by organisms. Plants, animals, and bacteria living in lakes leave behind genetic material that gets trapped and buried in the sediment at the bottom of lakes. Similarly, biocides ­ substances used to kill or control populations of living organisms ­ that run-off into lakes leach into the sediment and can be measured years later. Therefore, this sediment holds a record of life and environmental impacts in the lake over past centuries. Eastwood, Zhou et al. wanted to understand the relationship between environmental changes (such as the use of biocides and climate change) and shifts in lake biodiversity. To do so, the researchers studied a lake community that had experienced major environmental impacts over the last century (including nutrient pollution, chemical pollution and climate change), but which appeared to improve over the last few years of the 20^th century. Using machine learning to find connections over time between biodiversity and non-living environmental changes, Eastwood, Zhou et al. showed that, despite apparent recovery in water quality, the biodiversity of the lake was not restored to its original state. A combination of climate factors (such as rainfall levels and extreme temperatures) and biocide application (particularly insecticides and fungicides) explained up to 90% of the biodiversity changes that occurred in the lake. These changes had not been identified before using traditional techniques. The functional roles microorganisms played in the ecosystem (such as degradation and nitrogen metabolism) were also altered, suggesting that loss of biodiversity may lead to loss of ecosystem functions. The findings described by Eastwood, Zhou et al. can be used by environmental regulators to identify species or ecosystems at risk from environmental change and prioritise them for intervention. The approach can also be used to identify which chemicals pose the greatest threat to biodiversity. Additionally, the use of environmental DNA from sediment can provide rich historical biodiversity data, which can be used to train artificial intelligence-based models to improve predictions of how ecosystems will respond to complex environmental changes.

Persistent Organic Contaminants in Dust from the International Space Station.

Polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), "novel" brominated flame retardants (NBFRs), organophosphate esters (OPEs), polycyclic aromatic hydrocarbons (PAH), perfluoroalkyl substances (PFAS), and polychlorinated biphenyls (PCBs) were measured in a composite sample of dust from the International Space Station (ISS). Notwithstanding the unique environment from which the dust originated, while concentrations of all target compound classes frequently exceeded the median values in terrestrial indoor microenvironments in the US and western Europe, ISS dust concentrations were generally within the terrestrial range. The relative abundance of the three HBCDD diastereomers is dominated by γ-HBCDD (96.6% ΣHBCDD). This matches very closely with the commercial mixture added to materials and contrasts with the diastereomer distribution observed in most terrestrial indoor dust samples (in which γ-HBCDD is typically ∼60-70% ΣHBCDD). This suggests conditions inside the ISS do not favor the previously reported photolytically mediated formation in dust of α-HBCDD. Also of note, the concentration of perfluorooctanoic acid (PFOA) in ISS dust (3300 ng/g) exceeds the maximum reported (1960 ng/g) in a 2008 survey of dust from US child daycare centers and homes. This may reflect the widespread use of waterproofing treatments in the ISS to prevent microbial growth. Our findings can inform future material choices for manned spacecraft such as the ISS.

Dermal bioaccessibility of perfluoroalkyl substances from household dust; influence of topically applied cosmetics.

PFAS are known contaminants of indoor dust. Despite the adherence of such dust to skin, the dermal penetration potential of PFAS is not well understood. By applying in vitro physiologically based extraction tests, the bioaccessibility of 17 PFAS from indoor dust to synthetic human sweat sebum mixtures (SSSM) was assessed. The composition of the SSSM substantially impacted the bioaccessibility of all target compounds. PFAS bioaccessibility in a 1:1 sweat:sebum mixture ranged from 54 to 92% for perfluorocarboxylic acids (PFCAs) and 61-77% for perfluorosulfonic acids (PFSAs). Commonly applied cosmetics (foundation, sunscreen, moisturiser, and deodorant) significantly impacted the dermal bioaccessibility of target PFAS, e.g., the presence of moisturiser significantly decreased the total bioaccessibility of both PFCAs and PFSAs. Preliminary human exposure estimates revealed dermal contact with indoor dust could contribute as much as pathways such as drinking water and dust ingestion to an adult's daily intake of PFAS. While further research is needed to assess the percutaneous penetration of PFAS in humans, the current study highlights the potential substantial contribution of dermal exposure to human body burdens of PFAS and the need for further consideration of this pathway in PFAS risk assessment studies.

Harnessing water fleas for water reclamation: A nature-based tertiary wastewater treatment technology.

Urbanisation, population growth, and climate change have put unprecedented pressure on water resources, leading to a global water crisis and the need for water reuse. However, water reuse is unsafe unless persistent chemical pollutants are removed from reclaimed water. State-of-the-art technologies for the reduction of persistent chemical pollutants in wastewater typically impose high operational and energy costs and potentially generate toxic by-products (e.g., bromate from ozonation). Nature-base solutions are preferred to these technologies for their lower environmental impact. However, so far, bio-based tertiary wastewater treatments have been inefficient for industrial-scale applications. Moreover, they often demand significant financial investment and large infrastructure, undermining sustainability objectives. Here, we present a scalable, low-cost, low-carbon, and retrofittable nature-inspired solution to remove persistent chemical pollutants (pharmaceutical, pesticides and industrial chemicals). We showed Daphnia's removal efficiency of individual chemicals and chemicals from wastewater at laboratory scale ranging between 50 % for PFOS and 90 % for diclofenac. We validated the removal efficiency of diclofenac at prototype scale, showing sustained performance over four weeks in outdoor seminatural conditions. A techno-commercial analysis on the Daphnia-based technology suggested several technical, commercial and sustainability advantages over established and emerging treatments at comparable removal efficiency, benchmarked on available data on individual chemicals. Further testing of the technology is underway in open flow environments holding real wastewater. The technology has the potential to improve the quality of wastewater effluent, meeting requirements to produce water appropriate for reuse in irrigation, industrial application, and household use. By preventing persistent chemicals from entering waterways, this technology has the potential to maximise the shift to clean growth, enabling water reuse, reducing resource depletion and preventing environmental pollution.

Are UK E-waste recycling facilities a source of environmental contamination and occupational exposure to brominated flame retardants?

Investigations into the impacts of regulated electrical and electronic waste (e-waste) recycling activities on urban environments in Europe remain rather scarce. In this study, dust samples taken both inside and outside of five UK e-waste recycling facilities were analysed for concentrations of polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), and hexabromocyclododecane (HBCDD). Average concentrations of ∑BFRs in dust inside and outside UK e-waste recycling facilities were 12,000 ng/g and 180 ng/g, with median concentrations of 7500 ng/g and 85 ng/g, respectively. BDE-209 and decabromodiphenyl ethane (DBDPE) were the most abundant BFRs in both indoor and kerb dust, making a combined contribution to ∑BFRs of ~90 % on average. While four out of the five studied e-waste facilities showed a lack of significant impact on BFR contamination in surrounding environment, one of the studied e-waste recycling facilities was identified as a likely source of BFR contamination to UK urban environments, with industrial activities as another potential source of NBFRs. Occupational exposure of UK e-waste recycling workers to BFRs via dust ingestion was generally lower than that estimated for e-waste recyclers from other countries, but was comparable to BFR exposure via dust ingestion of UK office workers. Our estimates suggested that health burdens posed by dust ingestion of BFRs were minimal for UK e-waste recycling workers.

Novel Insights into the Dermal Bioaccessibility and Human Exposure to Brominated Flame Retardant Additives in Microplastics.

In this study, we optimized and applied an in vitro physiologically based extraction test to investigate the dermal bioaccessibility of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD), incorporated as additives in different types of microplastics (MPs), and assess human dermal exposure to these chemicals. The dermal bioaccessibility of PBDEs in polyethylene (PE) MPs was significantly higher (P < 0.05) than in polypropylene (PP) MPs. Both log Kow and water solubility influenced the dermal bioaccessibility of PBDEs. For HBCDDs in polystyrene MPs, the dermally bioaccessible fractions were 1.8, 2.0, and 1.6% of the applied dose for α-, ß-, and γ-HBCDDs, respectively. MP particle size and the presence of cosmetic formulations (antiperspirant, foundation, moisturizer and sunscreen) influenced the bioaccessibility of PBDEs and HBCDDs in MP matrices at varying degrees of significance. Human exposure to ∑PBDEs and ∑HBCDDs via dermal contact with MPs ranged from 0.02 to 22.2 and 0.01 to 231 ng (kg bw)-1 d-1 and from 0.02 to 6.27 and 0.2 to 65 ng (kg bw)-1 d-1 for adults and toddlers, respectively. Dermal exposure to PBDEs and HBCDDs in MPs is substantial, highlighting for the first time the significance of the dermal pathway as a major route of human exposure to additive chemicals in microplastics.

Temporal trends in concentrations of brominated flame retardants in UK foodstuffs suggest active impacts of global phase-out of PBDEs and HBCDD.

Global restrictions on use of legacy brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) have generated demand for novel BFRs (NBFRs) as substitutes. Our research group has previously reported decreased concentrations of PBDEs and HBCDD and increased concentrations of NBFRs in UK indoor environments, suggesting that restrictions on PBDEs and HBCDD are exerting an impact. In this study, we analysed UK foodstuffs collected in 2020-21 and compared the BFR concentrations found with those found in similar samples collected in 2015 to investigate whether similar trends in BFR concentrations would be observed. Concentrations of PBDEs and HBCDD isomers detected in our samples had declined by 78-92 % and 59-97 % since the 2015 study, respectively. Moreover, concentrations of NBFRs (dominated by 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE or TBE), and bis(2-ethyl hexyl) tetrabromophthalate (BEH-TEBP or TBPH)) in UK foodstuffs increased significantly (28-1400 %) between 2015 and 2020-21. Combined, these findings suggest that restrictions on use of PBDEs and HBCDD have had a discernible impact on concentrations of these legacy BFRs and their NBFR replacements in UK foodstuffs. Interestingly, given recent reports of a significant increase in concentrations of decabromodiphenyl ethane (DBDPE) in UK house dust between 2014 and 2019, a significant decline (70-84 %) in concentrations of DBDPE was observed in UK foodstuffs.

Daphnia as a Sentinel Species for Environmental Health Protection: A Perspective on Biomonitoring and Bioremediation of Chemical Pollution.

Despite available technology and the knowledge that chemical pollution damages human and ecosystem health, chemical pollution remains rampant, ineffectively monitored, rarely prevented, and only occasionally mitigated. We present a framework that helps address current major challenges in the monitoring and assessment of chemical pollution by broadening the use of the sentinel species Daphnia as a diagnostic agent of water pollution. And where prevention has failed, we propose the application of Daphnia as a bioremediation agent to help reduce hazards from chemical mixtures in the environment. By applying "omics" technologies to Daphnia exposed to real-world ambient chemical mixtures, we show improvements at detecting bioactive components of chemical mixtures, determining the potential effects of untested chemicals within mixtures, and identifying targets of toxicity. We also show that using Daphnia strains that naturally adapted to chemical pollution as removal agents of ambient chemical mixtures can sustainably improve environmental health protection. Expanding the use of Daphnia beyond its current applications in regulatory toxicology has the potential to improve both the assessment and the remediation of environmental pollution.

Organophosphate esters in UK diet; exposure and risk assessment.

Food ingestion has been established as an important human exposure route to many environmental contaminants (brominated flame retardants, dioxins, organochlorine pesticides etc). However, information regarding dietary exposure to organophosphate esters (OPEs) in the UK remains limited. This study provides the first comprehensive dataset on OPEs in the UK diet by measuring concentrations of eight OPEs in 393 food samples, divided into 15 food groups, collected from Birmingham, UK. All target OPEs were measured above the limit of quantification in at least one of the food groups analysed. Concentrations were highest (mean ∑8OPEs = 18.4 ng/g wet weight (ww)) in milk and milk products, followed by those in cereal and cereal products (mean ∑8OPEs = 15.9 ng/g ww), with concentrations lowest in chickens' eggs (mean ∑8OPEs = 1.61 ng/g ww). Interestingly, concentrations in animal-derived foods (mean ∑8OPEs = 44.2 ng/g ww) were statistically indistinguishable (p˃0.05) from plant-derived foods (mean ∑8OPEs = 36.8 ng/g ww). Estimated daily dietary intakes (EDIs) of ∑8OPEs under mean and high-end exposure scenarios for the four age groups considered were: toddlers (420 and 1547 ng/kg bw/day) ˃ children (155 and 836) ˃ elderly (74.3 and 377) ˃ adults (62.3 and 278) ng/kg bw/day, respectively. Baby food contributed 39 % of ∑8OPEs exposure for toddlers, with non-alcoholic beverages contributing 27 % of exposure for children, while cereal and cereal products (25 %) and fruits (22 %) were the main contributors for adults and the elderly. The concentrations of OPEs in UK foodstuffs were generally of the same order of magnitude as those reported for other countries and our estimates of dietary exposure were well below the corresponding health-based limit values.

Comparative in vitro metabolism of short chain chlorinated paraffins (SCCPs) by human and chicken liver microsomes: First insight into heptachlorodecanes.

Short chain chlorinated paraffins (SCCPs) are emerging persistent organic pollutants of great concern due to their ubiquitous distribution in the environment. However, little information is available on the biotransformation of SCCPs in organisms. In this study, a chlorinated decane: 1, 2, 5, 5, 6, 9, 10-heptachlorodecanes (HeptaCDs) was subjected to in vitro metabolism by human and chicken liver microsomes at environmentally relevant concentration. Using ultra-performance liquid chromatography-Q-Exactive Orbitrap mass spectrometry, two metabolites: monohydroxylated hexachlorodecane (HO-HexCD) and monohydroxy heptachlorodecane (HO-HeptaCD) were detected in human liver microsomal assays, while only one metabolite (HO-HexCD) was identified in chicken liver microsomal assays. The formation of HO-HexCD was fitted to a Michaelis-Menten model for chicken liver microsomes with a Vmax (maximum metabolic rate) value of 4.52 pmol/mg/min. Metabolic kinetic parameters could not be obtained for human liver microsomes as steady state conditions were not reached under our experimental conditions. Notwithstanding this, the observed average biotransformation rate of HeptaCDs was much faster for human liver microsomes than for chicken liver microsomes. Due to the lack of authentic standards for the identified metabolites, the detailed structure of each metabolite could not be confirmed due to the possibility of conformational isomers. This study provides first insights into the biotransformation of SCCPs, providing potential biomarkers and enhancing understanding of bioaccumulation studies.

Exposure, risk and predictors of hexabromocyclododecane and Tetrabromobisphenol-A in house dust from urban, rural and E-waste dismantling sites in Thailand.

In this study, for the first time, we determined concentrations of hexabromocyclododecane (HBCDD) and tetrabromobisphenol-A (TBBPA) in house dust and estimated human exposure to these substances in houses located in an e-waste dismantling site and in urban and rural residential areas of Thailand. The median HBCDD concentration in urban residential houses (2.10 ng g-1) was similar to that in houses in an e-waste dismantling site (2.05 ng g-1, p > 0.05) and slightly higher than that in rural residential houses (1.11 ng g-1, p > 0.05). In contrast, significantly higher TBBPA concentrations were present in house dust from an e-waste dismantling site (median = 720 ng g-1; range = 44-2300 ng g-1) compared to those in urban (68.6 ng g-1; 3.5-300 ng g-1, p < 0.001) and rural residential areas (17 ng g-1; 2.0-201 ng g-1, p < 0.001). TBBPA concentrations increased with the increasing presence of electronic devices and a decreasing distance to the e-waste dismantling site. These results suggest that e-waste dismantling activities may contribute to TBBPA contamination of house dust. The median estimated daily intake (EDI) of HBCDD and TBBPA through dust ingestion for toddlers exceeded that for children and adults. However, EDI values for HBCDD and TBBPA from all age groups were below the oral reference dose guideline value suggested by the US National Research Council and National Toxicology Program (NTP).

Dermal uptake: An important pathway of human exposure to perfluoroalkyl substances?

Per- and polyfluoroalkyl substances (PFAS) have been produced and used in a broad range of products since the 1950s. This class, comprising of thousands of chemicals, have been used in many different products ranging from firefighting foam to personal care products and clothes. Even at relatively low levels of exposure, PFAS have been linked to various health effects in humans such as lower birth weight, increased serum cholesterol levels, and reduced antibody response to vaccination. Human biomonitoring data demonstrates ubiquitous exposure to PFAS across all age groups. This has been attributed to PFAS-contaminated water and dietary intake, as well as inadvertent ingestion of indoor dust for adults and toddlers. In utero exposure and breast milk have been indicated as important exposure pathways for foetuses and nursing infants. More recently, PFAS have been identified in a wide range of products, many of which come in contact with skin (e.g., cosmetics and fabrics). Despite this, few studies have evaluated dermal uptake as a possible route for human exposure and little is known about the dermal absorption potential of different PFAS. This article critically investigates the current state-of-knowledge on human exposure to PFAS, highlighting the lack of dermal exposure data. Additionally, the different approaches for dermal uptake assessment studies are discussed and the available literature on human dermal absorption of PFAS is critically reviewed and compared to other halogenated contaminants, e.g., brominated flame retardants and its implications for dermal exposure to PFAS. Finally, the urgent need for dermal permeation and uptake studies for a wide range of PFAS and their precursors is highlighted and recommendations for future research to advance the current understanding of human dermal exposure to PFAS are discussed.

Occurrence, human exposure, and risk of microplastics in the indoor environment.

Microplastics (MPs) are a group of emerging contaminants that have attracted increasing scientific and societal attention over the past decade due to their ubiquitous detection in all environmental compartments. So far, most studies on MPs focus on characterizing their occurrence, fate, and impact in the aquatic environment. Therefore, very little is known about the magnitude, patterns, and associated risks of human exposure to MPs, particularly indoors. This is a significant research gap given that people spend most of their time (up to 90%) indoors, which is exacerbated over the past year by COVID-19 lockdown measures. Critical evaluation of the existing literature revealed the presence of MPs at higher concentrations in indoor air and dust (from homes and offices) compared to outdoors. This was attributed to several factors including: indoor MPs sources (e.g. furniture, textiles), increased deposition of atmospheric MPs indoors, and less atmospheric mixing and dilution compared to outdoor air. Current understanding is that indoor human exposure to MPs occurs via a combination of inhalation, ingestion, and dermal contact. Dietary intake was considered the major pathway of human exposure to MPs until recent studies revealed potential high exposure via inhalation. Moreover, exposure via inadvertent dust ingestion and dermal contact cannot be neglected, particularly for young children. This is alarming due to the potential toxic implications of MPs exposure. Early toxicological evidence indicates that small MPs (<20 µm) can cause oxidative stress and inflammation, while particles <5 µm can be engulfed by cells and translocated to accumulate in different organs. Also, there is increasing concern over potential leaching of toxic chemicals used as plastic additives (e.g. plasticizers and flame retardants) upon exposure to MPs due to their large surface area. However, MPs exposure and risk assessment in humans is still in its infancy and more research is necessary to provide the knowledge base required for regulations to protect human health and environment against MPs.

Microplastics in freshwater sediments: Analytical methods, temporal trends, and risk of associated organophosphate esters as exemplar plastics additives.

It has been estimated that over 28 million tonnes of plastics end up in water bodies annually. These plastics degrade into microplastics (MPs), which along with microbeads and MPs from other sources such as wastewater treatment plants continue to threaten the aquatic system. At such small sizes, and corresponding larger surface areas per unit mass/volume, MPs exhibit enhanced capacity for absorbing and desorbing toxic chemicals/additives. Therefore, MPs can serve as vectors through which additives as well as other persistent, bio-accumulative, and toxic chemicals can enter the food chain. Additives are a significant component of most plastic products with some identified as hazardous to health and the environment. One group of additives that has continued to attract interest is organophosphate esters (OPEs), which are used both as flame retardants and plasticizers. Some of these OPEs are suspected carcinogens and endocrine disruptors and have been reported to exert serious toxic effects on freshwater biota. Separate studies on the presence and fate in the freshwater environment of these additives and MPs have emerged recently. However, no studies exist that examine the extent to which plastics additives such as OPEs in sediments are sorbed to MPs as opposed to the sediment itself. This has potentially important implications for the bioavailability of such additives and studies to examine this are recommended. This paper reviews critically the current state-of-knowledge on MPs in freshwater sediments, methods for their analysis, as well as their occurrence, temporal trends, and risks to the freshwater aquatic environment. Moreover, to facilitate the study of additives associated with MPs that have been extracted from sediments, we consider the possible effect of MP isolation methods on the determination of concentrations of associated additives like OPEs.

Formal waste treatment facilities as a source of halogenated flame retardants and organophosphate esters to the environment: A critical review with particular focus on outdoor air and soil.

Extensive use of halogenated flame retardants (HFRs) and organophosphate esters (OPEs) has generated great concern about their adverse effects on environmental and ecological safety and human health. As well as emissions during use of products containing such chemicals, there are mounting concerns over emissions when such products reach the waste stream. Here, we review the available data on contamination with HFRs and OPEs arising from formal waste treatment facilities (including but not limited to e-waste recycling, landfill, and incinerators). Evidence of the transfer of HFRs and OPEs from products to the environment shows that it occurs via mechanisms such as: volatilisation, abrasion, and leaching. Higher contaminant vapour pressure, increased temperature, and elevated concentrations of HFRs and OPEs in products contribute greatly to their emissions to air, with highest emission rates usually observed in the early stages of test chamber experiments. Abrasion of particles and fibres from products is ubiquitous and likely to contribute to elevated FR concentrations in soil. Leaching to aqueous media of brominated FRs (BFRs) is likely to be a second-order process, with elevated dissolved humic matter and temperature of leaching fluids likely to facilitate such emissions. However, leaching characteristics of OPEs are less well-understood and require further investigation. Data on the occurrence of HFRs and OPEs in outdoor air and soil in the vicinity of formal e-waste treatment facilities suggests such facilities exert a considerable impact. Waste dumpsites and landfills constitute a potential source of HFRs and OPEs to soil, and improper management of waste disposal might also contribute to HFR contamination in ambient air. Current evidence suggests minimal impact of waste incineration plants on BFR contamination in outdoor air and soil, but further investigation is required to confirm this.

Atmospheric concentrations of polychlorinated biphenyls, brominated flame retardants, and novel flame retardants in Lagos, Nigeria indicate substantial local sources.

Polychlorinated biphenyls (PCBs), brominated flame retardants (BFRs) like polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), and novel flame retardants (NFRs) like decabromodiphenyl ethane (DBDPE) are ubiquitous environmental pollutants. Despite this, little is known about their concentrations in outdoor air in the African continent. To address this knowledge gap, concentrations of BFRs, NFRs, and PCBs were measured in outdoor air at 8 sites located within the metropolitan area of Lagos, Nigeria. Concentrations of ∑8BDEs, ∑HBCDD, ∑7NFRs and ∑8PCBs were: 21-750 (median = 100) pg/m3, <12-180 (median = < 12) pg/m3, 34-900 (median = 300) pg/m3 and 85-460 (median = 300) pg/m3, respectively. Decabromodiphenyl ether (BDE-209, range: <16-620 pg/m3, median = 71 pg/m3) and DBDPE (range: <37-890 pg/m3, median = 280 pg/m3) were the dominant BFRs detected, while the non-Arochlor PCB 11 (range: 49-220 pg/m3, median = 100 pg/m3) was the dominant PCB. To the authors' knowledge, these are the first data on the non-Arochlor PCB 11 in outdoor air in Africa. In general, concentrations of all target contaminants in this study were within the range reported elsewhere in Africa and worldwide. Likely due to the tropical climate of Lagos, no seasonal variation in concentrations was discernible for any of the target contaminants. While concentrations of PBDEs and some NFRs were correlated with population density, concentrations of PCBs appear more impacted by leaks from electrical transformers and for PCB 11 to proximity to activities like textile factories that produce and use dyes.

A critical review of human exposure to organophosphate esters with a focus on dietary intake.

Organophosphate esters (OPEs) are common additives in a wide range of commercial and industrial products. Elevated and prolonged exposure to OPEs may induce several adverse effects. This is concerning as they are ubiquitous in air, indoor dust, drinking water, and other environmental matrices. However, information on the presence of OPEs in foodstuffs and consequent health risks remains scant. This review critically evaluates available information on levels and sources of OPEs in food, discusses the relative significance of diet as a pathway of human exposure, identifies knowledge gaps, and suggests directions for future research. For toddlers, dermal uptake from dust ingestion appears the predominant pathway of exposure to chlorinated OPEs, as well as ethylhexyl diphenyl phosphate (EHDPP) and triphenyl phosphate (TPHP). In contrast, diet appears the main pathway of exposure to all eight OPEs considered for adults, and for tri n-butyl phosphate (TnBP), tris 2-ethylhexyl phosphate (TEHP), and tris (2-butoxyethyl) phosphate (TBOEP) for toddlers. While summed exposures via all pathways are within reference dose (RfD) values, they do not include high-end exposure estimates, and for highly-exposed individuals, the margin between exposure and RfD values is smaller. Moreover, our exposure estimates are based on a meta-analysis of multiple exposure assessments conducted over a range of points in space and time. There is an urgent need for assessments of human exposure to OPEs that examine all relevant pathways in a spatially and temporally-consistent fashion. Given food is an important exposure pathway to OPEs, regular monitoring of their presence as well as their metabolites (that may have toxicological significance) in foodstuffs is recommended. While dermal uptake from indoor dust appears an important human exposure pathway, no evaluations exist of exposure via dermal uptake from OPE-containing products such as foam-filled furniture. This review also highlights very few data exist on OPEs in drinking water.