Assessment of Daily Exposure to Organophosphate Esters through PM2.5 Inhalation, Dust Ingestion, and Dermal Contact.

Inhalation of airborne fine particulate matter (PM2.5), dust ingestion, and dermal contact with dust are important pathways for human exposure to different contaminants, such as organophosphate esters (OPE), compounds that are widely used as flame retardants and plasticizers. There are limited studies assessing the extent of the contamination of OPE in indoor airborne PM2.5. This study offers a novel approach by examining various indoor environments, such as homes, workplaces, and means of transport, where people typically spend their daily lives. The goal is to provide a comprehensive assessment of daily exposure to these pollutants. Both PM2.5 and dust samples were collected in order to determine the concentration levels of 17 different OPEs. Fifteen OPEs in PM2.5 and 16 in dust samples were detected. Concentration levels in indoor air ranged from 4.37 to 185 ng/m3 (median 24.4 ng/m3) and from 3.02 to 36.9 µg/g for the dust samples (median 10.2 µg/g). Estimated daily intakes (EDIs) of OPEs were calculated for adults, yielding median values of 3.97 ng/(kg bw × day) for EDIInhalation, 5.89 ng/(kg bw × day) for EDIDermal, and 1.75 ng/(kg bw × day) for EDIIngestion. Such levels lie below human health threshold risk limits, although in some cases they could be only 2 times below the threshold for carcinogenic risk, with a main contribution from tris(2-chloroethyl) phosphate (TCEP). Given this threshold proximity, additional exposure to these chemicals from other pathways, such as food ingestion, gas phase exposure, and/or inhalation of coarser particles (PM10-2.5), could therefore lead to health limit exceedances.

A new look at rubber recycling and recreational surfaces: The inorganic and OPE chemistry of vulcanised elastomers used in playgrounds and sports facilities.

We revisit current understanding of the chemical complexity of different kinds of particulate vulcanised elastomers widely used in playgrounds and sports fields, adding new data on trace element and organophosphate ester contents of used tyre and EDPM crumb rubber. Enrichments in elements such as Zn, S, Co, Bi and Nd relate to the vulcanised mixtures created during manufacture. Zinc concentrations vary across an order of magnitude, being highest in our used tyre particulate samples (up to 2.4 %). In contrast, other trace element variations are due to coloured pigments causing increases in Cu and Zr (blue), Cr (green), and Fe and Sn (red and yellow) concentrations. The use of pale fillers such as CaCO3 and clay minerals (rather than carbon black) strongly influences Ca and Al concentrations, which are much higher in the coloured EPDM than in black used tyre crumb rubber. Representatives from all three of the main organophosphate ester (OPE) groups, namely chlorinated (e.g. TCEP, TCIPP, TDCPP), alkyl (e.g. TEHP, TEP, TNBP, TBOEP) and aryl (e.g. TPHP, EHDPP, TCP) were identified, confirming how these chemicals are commonly used in modern rubber compounding as flame retardants and plasticisers. Elevated concentrations of TEHP (up to 117 µg/g) in coloured-coated used tyre turf infill crumb rubbers were traced to the coating rather than the crumb rubber itself. The presence and weathering behaviour of OPEs in recreational crumb rubber materials deserve closer investigation. The ecological "onehealth" impact of potentially toxic substances present in recreational crumb rubbers will depend on if and how they are released during play and sports activities, maintenance procedures, and natural weathering. We argue that detailed chemical data on these materials should be available to buyers, as manufacturers strive to reduce ecotoxin content as part of the quest towards sustainable use and recycling of vulcanised elastomers.

Size-resolved chemical composition and toxicity of particles released from refit operations in shipyards.

Ship refit and repair operations in shipyards generate aerosol emissions with high potential for environmental impacts. Metal-bearing nano-, fine and coarse particles are incidentally formed and can be released to indoor and ambient air and the aquatic environment. This work aimed to further the understanding of these impacts by characterising particle size-resolved chemical composition (15 nm - 10 µm), organophosphate esters (OPEs) content (e.g., plasticisers) and cytotoxic and genotoxic potential. Results showed that nanoparticle emissions (20-110 nm) took place in bursts, coinciding with the use of mechanical abraders and spray-painting guns. Tracers of these activities were Sc, V, Cr, Co, Ni, Cu, Rb, Nb, and Cs. Key components were V and Cu, probably sourcing from nanoadditives in the coatings. Abrasion of coatings also emitted OPEs, especially from old paints. Toxicity assessments consistently evidenced hazardous potential for the different endpoints assessed, for a number of samples. Exposures to spray-painting aerosols were linked with reduced cell viability (cytotoxicity), significant generation of reactive oxygen species (ROS), and increases in micronuclei frequency (genotoxicity). Even though spray-painting did not contribute significantly to aerosol mass or number concentrations, it was a major driver of potential health effects. Results suggest that aerosol chemical composition (e.g., content in nano-sized Cu or V) may have a larger impact on toxicity than aerosol concentration. While direct human exposures may be prevented using personal and collective protective equipment and environmental release can be minimised by enclosures and filtration systems, impacts on ambient air and the aquatic environment cannot be fully prevented. The continued use of good practices (exhaust, dilution, general ventilation systems, PPE, already in place) is encouraged to reduce inhalation exposures inside the tents. Understanding the size-resolved chemical and toxicological properties of aerosols is key to reducing human health and environmental impacts of ship refit operations in shipyards.

First study on the presence of plastic additives in loggerhead sea turtles (Caretta caretta) from the Mediterranean Sea.

Loggerhead turtles (Caretta caretta) voluntarily ingest floating plastic debris and hence are chronically exposed to plastic additives, but very little is known about the levels of these compounds in their tissues. This work studied the presence of organophosphate esters (OPEs) on sea turtles collected from two different areas in the western Mediterranean, some of their prey and some floating plastic debris. OPEs were detected in all the samples analysed and ∑OPEs ranged from 12.5 to 384 ng/g wet weight (ww) in the turtles from the Catalan coasts, with a mean value of 21.6 ng/g ww, and from 6.08 to 100 ng/g ww in the turtles the Balearic Islands, with a mean value of 37.9 ng/g ww. Differences in ∑OPEs were statistically significant, but turtles from the two regions did not differ in their OPE profiles. As per turtle's prey, ∑OPEs ranged from 4.55 to 90.5 ng/g ww. Finally, marine plastic litter showed ∑OPEs concentrations between 10.9 and 868 ng/g. Although most compounds were present in both potential sources of contamination, prey and plastic debris, the OPE profiles in loggerhead turtles and these sources were different. Some OPEs, such as tris(2-isopropylphenyl) phosphate (T2IPPP), tripropyl phosphate (TPP) and tris(2-butoxyethyl) phosphate (TBOEP), were detected in plastic debris and turtle muscle but not in their prey, thus suggesting that ingestion of plastic debris was their main source. Contrarily, the levels of triethyl phosphate (TEP), diphenyl cresyl phosphate (DCP), 2-isopropylphenyl diphenyl phosphate (2IPPDPP) and 4-isopropylphenyl diphenyl phosphate (4IPPDPP) in turtle muscle were much higher than in jellyfish, their main prey, thus indicating a biomagnification potential. Regular ingestion of plastic debris and contamination from their prey may explain why ∑OPEs in loggerhead turtles is much higher than the values reported previously for teleost fishes and marine mammals from the western Mediterranean.