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Identification of novel polyfluoroalkyl substances in surface water runoff from a chemical stockpile fire Full text
2022
Rana, Sahil | Marchiandi, Jaye | Partington, Jordan M. | Szabo, Drew | Heffernan, Amy L. | Symons, Robert K. | Xie, Shay | Clarke, Bradley O.
In 2018, over 30,000 L of fluorine-free firefighting foam was used to extinguish an industrial warehouse fire of uncharacterized chemical and industrial waste. Contaminated firewater and runoff were discharged to an adjacent freshwater creek in Melbourne, Australia. In this study, we applied nontarget analysis using liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QToF-MS) to 15 surface water samples to investigate the presence of legacy, novel and emerging per-and polyfluoroalkyl substances (PFAS). We identified six novel and emerging fluorotelomer-based fluorosurfactants in the Australian environment for the first time, including: fluorotelomer sulfonamido betaines (FTABs or FTSA-PrB), fluorotelomer thioether amido sulfonic acids (FTSASs), and fluorotelomer sulfonyl amido sulfonic acids (FTSAS-So). Legacy PFAS including C₆–C₈ perfluoroalkyl sulfonic acids, C₄–C₁₀ perfluoroalkyl carboxylic acids, and perfluoro-4-ethylcyclohexanesulfonate were also detected in surface water. Of note, we report the first environmental detection of ethyl 2-ethenyl-2-fluoro-1-(trifluoromethyl) cyclopropane-1-carboxylate. Analysis of several Class B certified fluorine-free foam formulations allowed for use in Australia revealed that there was no detectable PFAS. Patterns in the homologue profiles of fluorotelomers detected in surface water are consistent with environments impacted by fluorinated aqueous film-forming foams. These results provide strong evidence that firewater runoff of stockpiled fluorinated firefighting foam was the dominant source of detectable PFAS to the surrounding environment.
Show more [+] Less [-]Microplastics in composting of rural domestic waste: abundance, characteristics, and release from the surface of macroplastics Full text
2021
Gui, Jiaxi | Sun, Yue | Wang, Jingli | Chen, Xu | Zhang, Shuchi | Wu, Donglei
The rural domestic waste (RDW) compost has been widely used in agriculture and horticulture, but little is known about microplastics (MPs) in RDW composting. The current work deals with the abundance and characteristics of MPs in RDW composting, and the effects of composting processes on the composition of MPs. Compost samples from two RDW treatment stations were investigated, and a lab-scale experiment was carried out to verify the possible release of MPs from macroplastics (>25 mm) contained in the RDW during composting. MPs were identified using stereo-microscope and μ-FTIR. The average abundance of MPs (0.05–5 mm) in the RDW compost products was 2400 ± 358 items/kg (dry weight), and the main MPs shapes were fibers and films. Polyester, polypropylene (PP) and polyethylene (PE) were the most common polymer types. MPs having a size <1 mm accounted for more than 50% of the total quantity. With the progress of composting, the proportion of MPs having size <1 mm increased, and more foam MPs were observed in the late stage of composting. Under the influence of mechanical force, oxidation and biodegradation, a piece of expanded polystyrene (EPS), PP and PE macroplastic could release 4–63 MPs particles during the composting. Thus, the RDW compost was a significant source of MPs in soils, and the MPs in compost products were closely related to the quantity and type of plastic waste present in RDW, which helped to suggest better MPs control strategies.
Show more [+] Less [-]The current state of microplastic pollution in the world's largest gulf and its future directions Full text
2021
Shruti, V.C. | Pérez-Guevara, Fermín | Kutralam-Muniasamy, Gurusamy
Microplastics can have several negative consequences on a variety of organisms, and their prevalence in marine ecosystems has become a major concern. Researchers have recently focused their attention on the world's largest gulf, the Gulf of Mexico (GoM), to determine and assess the impact of microplastic pollution on various environmental compartments (i.e., water, sediment, and biota). This paper critically reviews the analytical methodologies as well as summarizes the distribution, accumulation, sources, and composition of microplastics in a handful of studies (n = 14) conducted in the Gulf of Mexico (GoM) covering countries like the USA (n = 10) and Mexico (n = 4). Current quality control measures with respect to sampling and microplastic extraction are summarized. Of 14 studies reviewed, 47% primarily focused on examining sediments for microplastics, with biota and water comprising 35% and 18%, respectively. The abundance ranged from 31.7 to 1392 items m⁻² and 60–1940 items kg⁻¹ in sediment, 12–381 particles L⁻¹ in water, and 1.31–4.7 particles per fish in biota. Irregular shaped fragments were the most abundant, followed by fiber, film, foam, hard, and beads etc. Different polymer types of microplastics have been found, including polyethylene, polypropylene, polystyrene, polyamide, nylon, and rayon etc. According to published research, 46 out of 100 fish thriving in this region are susceptible to microplastic ingestion. Although microplastic concentration in the GoM is among the highest found worldwide, the determination of microplastic contamination is still a growing field of research and methodological discrepancies largely limit the realization of establishing a baseline information on the microplastic abundance of the GoM. In this respect, considerable efforts must be dedicated towards evaluating their distribution and exposure levels; thereby, major challenges and future research directions are briefly discussed.
Show more [+] Less [-]Occurrence and fate of legacy and novel per- and polyfluoroalkyl substances (PFASs) in freshwater after an industrial fire of unknown chemical stockpiles Full text
2021
Marchiandi, Jaye | Szabo, Drew | Dagnino, Sonia | Green, Mark P. | Clarke, Bradley O.
An industrial warehouse illegally storing a large quantity of unknown chemical and industrial waste ignited in an urban area in Melbourne, Australia. The multiday fire required firefighters to use large amounts of fluorine-free foam that carried contaminated firewater runoff into an adjacent freshwater creek. In this study, the occurrence and fate of 42 per- and polyfluoroalkyl substances (PFASs) was determined from triplicate surface water samples (n = 45) from five locations (upstream, point-source, downstream; 8 km) over three sampling campaigns from 2018 to 2020. Out of the 42 target PFASs, perfluorocarboxylates (PFCAs: C4–C14), perfluoroalkane sulfonates (PFSAs: C4–C10), and perfluoroalkyl acid precursors (e.g. 6:2 fluorotelomer sulfonate (6:2 FTSA)) were ubiquitously detected in surface waters (concentration ranges: <0.7–3000 ng/L). A significant difference in ΣPFAS concentration was observed at the point-source (mean 5500 ng/L; 95% CI: 4800, 6300) relative to upstream sites (mean 100 ng/L; 95% CI: 90, 110; p ≤ 0.001). The point-source ΣPFAS concentration decreased from 5500 ± 1200 ng/L to 960 ± 42 ng/L (−83%) after two months and to 430 ± 15 ng/L (−98%) two years later. 6:2 FTSA and perfluorooctanesulfonate (PFOS) dominated in surface water, representing on average 31% and 20% of the ΣPFAS, respectively. Emerging PFASs including a cyclic perfluoroalkanesulfonate (PFECHS) and a C4 perfluoroalkane sulfonamide (FBSA) were repeatedly present in surface water (concentration ranges <0.3–77 ng/L). According to the updated Australian PFAS guidelines for ecological conservation, the water samples collected at the time of monitoring may have posed a short-term risk to aquatic organisms in regard to PFOS levels. These results illustrate that acute high dose exposure to PFASs can result from industrial fires at sites storing or stockpiling PFAS-based waste products. Continued monitoring will be crucial to evaluate potential long-term risk to wildlife in the region.
Show more [+] Less [-]Side-chain fluorotelomer-based polymers in children car seats Full text
2021
Wu, Yan | Miller, Gillian Z. | Gearhart, Jeff | Peaslee, Graham | Venier, Marta
Fabric and foam samples from popular children car seats marketed in the United States during 2018 were tested for fluorine content by particle-included gamma ray emission spectroscopy (PIGE, n = 93) and X-ray photoelectron spectroscopy (XPS, n = 36), as well as for per- and polyfluoroalkyl substances (PFAS) by liquid and gas chromatography mass spectrometry (LC/MS and GC/MS, n = 36). PFAS were detected in 97% of the car seat samples analyzed with MS, with total concentrations of 43 PFAS (∑PFAS) up to 268 ng/g. Fabric samples generally had greater ∑PFAS levels than foam and laminated composites of foam and fabric. The three fabric samples with the highest total fluorine content as represented by the highest PIGE signal were also subjected to ultraviolet (UV) irradiation and the total oxidizable precursor (TOP) assay. Results from these treatments, as well as the much higher organofluorine levels measured by PIGE compared to LC/MS and GC/MS, suggested the presence of side-chain fluorotelomer-based polymers (FTPs), which have the potential to readily degrade into perfluoroalkyl acids (PFAAs) under UV light. Furthermore, fluorotelomer (meth)acrylates were found to be indicators for the presence of (meth)acrylate-linked FTPs in consumer products, and thus confirmed that at least half of the tested car seats had FTP-treated fabrics. Finally, extraction of selected samples with synthetic sweat showed that ionic PFAS, particularly those with fluorinated carbons ≤8, can migrate from fabric to sweat, suggesting a potential dermal route of exposure.
Show more [+] Less [-]Behavior and distribution of polystyrene foams on the shore of Tuul River in Mongolia Full text
2020
Battulga, Batdulam | Kawahigashi, Masayuki | Oyuntsetseg, Bolormaa
Foamed plastic debris in aquatic systems has become one of the emerging global contaminants. In this study, the behavior of polystyrene foam (PSF) and microplastics (MPs) adhered on the PSFs were investigated on the Tuul River shore in Ulaanbaatar, the capital city of Mongolia. The micro-sized (<5 mm) PSF, which was the dominant PSF over 600 pieces in 100 m², have accumulated along the shoreline of Tuul River. Carbonyl index (CI) was calculated to evaluate the surface oxidation of macro-sized (20–100 mm), meso-sized (5–20 mm), and micro-sized PSFs and confirm the relative aging depending on photodegradation. CI ranged from 0.00 to 1.09 in the sampled PSFs, whereby the degraded PSFs with high CI were distributed on the shore of downstream of sewer drainage. Micro-sized PSFs showed a wide range of CI and a relatively high average value of CI as compared to those of meso- and macro-sized PSFs. Most of PSFs aggregated with MPs and the adhered MPs have been ubiquitously detected from the surface of PSFs. Adhered micro-sized plastics explored from the surface of PSFs with various sizes, except for mega-sized (>100 mm) PSF, ranged from 5 to 141 items per piece of PSF fragment. The aggregates of PSFs and MPs were common status of PSFs during their transportation. The present findings, which indicated a high concentration of adhered MPs, raise an environmental concern about the widespread aquatic plastic pollution.
Show more [+] Less [-]Iced block method: An efficient method for preparation of micro-sized expanded polystyrene foams Full text
2020
Kwak, Jin Il | An, Youn-Joo
Recently, numerous studies concerning dye-labeled microplastic beads have reported on the end-of-life, environmental effects of microplastics because of their ubiquitous commercial usage. Less is understood about the toxicity and bioaccumulation of plastics other than microplastic beads, which can also harm the environment (e.g., fragments, fibers, foams, and films). Expanded polystyrene (EPS) is widespread in the environment owing to its many uses, however, limited research has been conducted on EPS foams. This study focuses on developing an efficient method for the preparation of micro-sized EPS foams for research purposes and compares it with previous microplastics preparation methods reported in 68 previous studies. It was demonstrated that the iced EPS block method (iced EPS block + water) generated larger quantities of smaller-sized EPS foams (20–200 and 200–500 μm) compared to the EPS + ice + water and EPS + water methods. The optimal protocol includes 1) iced EPS block preparation, 2) grinding and sieving, and 3) collecting. Additionally, it was confirmed that the iced EPS block method requires less money, labor, and time compared to previously reported methods in the literature. The method proposed in this research can assist future investigations into the environmental effects of EPS foams.
Show more [+] Less [-]Comparison of receptor models for source identification of organophosphate esters in major inflow rivers to the Bohai Sea, China Full text
2020
Qi, Yanjie | Liu, Xing | Wang, Zhen | Yao, Ziwei | Yao, Wenjun | Shangguan, Kuixing | Li, Minghao | Ming, Hongxia | Ma, Xindong
A better understanding of the sources of organophosphate esters (OPEs) is a prerequisite for OPE control and the establishment of related environmental policies. Sources of OPEs in 35 major inflow rivers to the Bohai Sea of China were quantitatively analyzed using three effective receptor models (principal component analysis-multiple linear regression (PCA-MLR), positive matrix factorization (PMF), and Unmix) in this paper. The similarities and differences in results from PCA-MLR, PMF, and Unmix were discussed in depth. All three models well predicted the spatial variability of the total concentrations of nine OPEs (triethyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, tri (2-ethylhexyl) phosphate, tri (2-chloroethyl) phosphate, tris(1-chloro-2-propyl) phosphate, tris(1,3-dichloro-2-propyl) phosphate, triphenyl phosphate, and triphenylphosphine oxide) (∑₉OPEs) (r² = 0.90–0.96, p = 0.000) and explained 98.4%–101.2% of the observed ∑₉OPEs. The predicted ∑₉OPEs values from each pairwise model were significantly correlated (r² = 0.88–0.91, p = 0.000). Three OPE sources were extracted by all three models: rigid and flexible polyurethane foam/coating, cellulosic/acrylic/vinyl polymer/unsaturated polyester, and polyvinyl chloride, contributing 49.9%, 29.7%, and 20.5% by PCA-MLR, 57.9%, 28.6%, and 13.5% by PMF, and 47.9%, 30.8%, and 22.4% by Unmix to the ∑₉OPEs, respectively. PMF was recommended as the preferred receptor model for analyzing OPE sources in water during the monitoring period because of its optimal performance.
Show more [+] Less [-]Personal exposure to polycyclic aromatic hydrocarbons in Appalachian mining communities Full text
2020
Hendryx, Michael | Wang, Shaorui | Romanak, Kevin A. | Salamova, Amina | Venier, Marta
Coal mining activities may increase residential exposure to polycyclic aromatic hydrocarbons (PAHs), but personal PAH exposures have not been studied in mining areas. We used silicone wristbands as passive personal samplers to estimate PAH exposures in coal mining communities in Central Appalachia in the United States. Adults (N = 101) wore wristbands for one week; 51 resided in communities within approximately three miles of surface mining sites, and 50 resided 10 or more miles from mining sites. Passive indoor polyurethane foam (PUF) sampling was conducted in residents’ homes, and a sample of 16 outdoor PUF samples were also collected. Nine PAH congeners were commonly detected in wristbands (mean ± standard deviation), including phenanthrene (50.2 ± 68.7 ng/g), benz[a]anthracene (20.2 ± 58.2 ng/g), fluoranthene (19.4 ± 24.1 ng/g) and pyrene (15.2 ± 18.2 ng/g). Controlling for participant characteristics and season, participants living closer to mining sites had significantly higher levels of phenanthrene, fluorene, fluoranthene, pyrene and ∑PAHs in wristbands compared to participants living farther from mining. Indoor air showed no significant group differences except for pyrene, but outdoor air showed significant or marginally significant differences for phenanthrene, fluorene, pyrene and ∑PAHs. The results suggest that mining community residents face exposure to outdoor mining-related pollutants, and demonstrate that personal silicone wristbands can be deployed as effective passive sampling devices.
Show more [+] Less [-]Semi-volatile organic compounds in infant homes: Levels, influence factors, partitioning, and implications for human exposure Full text
2019
Li, Hai-Ling | Liu, Li-Yan | Zhang, Zi-Feng | Ma, Wanli | Sverko, Ed | Zhang, Zhi | Song, Wei-Wei | Sun, Yu | Li, Yi-Fan
While infants are developing, they are easily affected by toxic chemicals existing in their environments, such as semi-volatile organic compounds (SVOCs): phthalates, polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs), and organophosphate esters (OPEs). However, the specific living environment of infants, including increased plastic products and foam floor mats, may increase the presence of these chemicals. In this study, 68 air, dust, and window film samples were collected from homes, with 3- to 6-month-old infant occupants, to analyze phthalates, PAHs, PBDEs, and OPEs. High detection rates and concentrations suggest that these SVOCs are widespread in infant environments and are associated with cooking methods, smoking habits, the period of time after decoration, and room floors. The partitioning behavior of SVOCs indicates that the logarithms of the dust/gas-phase air partition coefficient (logKD) and the window film/gas-phase air partition coefficient (logKF) in homes are not at an equilibrium state when the logarithm of the octanol/air partition coefficient (logKOA) is less than 8 or greater than 11. Considering the 3 exposure routes, ingestion and dermal absorption have become the main routes of infant exposure to phthalates and OPEs, and ingestion and inhalation have become the dominant routes of exposure to PAHs and PBDEs. The total carcinogenic risk of SVOCs, which have carcinogenic toxicities, via ingestion and dermal absorption for infants in homes exceeds the acceptable value, suggesting that the current levels of these SVOCs in homes might pose a risk to infant health.
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