Fluorescent Visualization of Chemical Profiles across the Air-Water Interface.

Chemical transfer across the air-water interface is one of the most important geochemical processes of global significance. Quantifying such a process has remained extremely challenging due to the lack of suitable technologies to measure chemical diffusion across the air-water microlayer. Herein, we present a fluorescence optical system capable of visualizing the formation of the air-water microlayer with a spatial resolution of 10 µm and quantifying air-water diffusion fluxes using pyrene as a target chemical. We show for the first time that the air-water microlayer is composed of the surface microlayer in water (∼290 ± 40 µm) and a diffusion layer in air (∼350 ± 40 µm) with 1 µg L-1 of pyrene. The diffusion flux of pyrene across the air-water interface is derived from its high-resolution concentration profile without any pre-emptive assumption, which is 2 orders of magnitude lower than those from the conventional method. This system can be expanded to visualize diffusion dynamics of other fluorescent chemicals across the air-water interface and provides a powerful tool for furthering our understanding of air-water mass transfer of organic chemicals related to their global cycling.

Transfer of Frictional Contact Derived Phthalates from Pad Surface Enhances Dermal Exposure.

Dermal exposure to chemicals derived from object surface contact is an important contributor to increased health risk. However, chemical transfer induced by mechanical friction between dermal and object surface has yet to be adequately addressed. To fill this knowledge gap, rubbing fabrics were used as surrogate skins to stimulate dermal mechanical friction with pad products with phthalates as target analytes. The results showed that the amounts of phthalates transferred increased linearly with contact burden (50-1000 g), contact duration (1-10 min), and sliding speed (3.0-9.0 cm s-1). The surface texture of surrogate skins dictated the accumulation of phthalates. Net/pocket micro-surface structures of rubbing fabrics induced a higher accumulation of phthalates than U-shape structures of fabrics with a similar surface roughness. Covering of the pad surface by a layer of textile was effective in minimizing the transfer of phthalates induced by mechanical motion. The estimated transfer efficiency of bis(2-ethylhexyl) ester (DEHP) derived from rubbing friction (0.005-0.05%) upon the pad surface over 8 h was greater than those for gas-phase emission (0.00002-0.0005% over 24 h) and sweat transfer (0.008-0.012% over 24 h). These results indicated that dermal frictional contact with the surface of pad products was an important exposure pathway.

Use of glioma to assess the distribution patterns of perfluoroalkyl and polyfluoroalkyl substances in human brain.

Human brain has a complex structure and is able to perform powerful functions. Blood-brain barrier blocks the entry of foreign substances and maintains the homeostasis of the brain. However, some exogenous substances are still able to pass through the blood-brain barrier, with distribution patterns yet to be clarified. Perfluoroalkyl and polyfluoroalkyl substances (PFASs), including perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkyl sulfonic acids (PFSAs), a precursor (perfluorooctane sulfonamide that can be degraded to other substances), and emerging PFASs, were analyzed for the first time in living human brain glioma. The target compounds were detected and quantified in 25 out of 26 glioma samples. The concentration range of ∑PFAS was < RL-51 ng g-1 wet weight (applied to all reported concentrations), with a median of 2.9 ng g-1. The most abundant compound was PFCAs (40%), followed by PFSAs (28%), emerging PFASs (22%), and perfluorooctane sulfonamide (10%). Abundant alternatives PFASs, including short-chain PFCAs, short-chain PFSAs, and emerging PFASs (52% of ∑PFAS), were found in the glioma samples, supporting the notion that low molecular weight exogenous compounds have high permeability to cross the blood-brain barrier and accumulate in brain tissue. Gender difference was not significant (p > 0.05) in the concentrations of PFASs in the glioma samples. Concentrations of PFASs increased with increasing age, from 0.61 ng g-1 (0-14 years old) to 1.6 ng g-1 (>48 years old), with no significant linear correlation with age. The present study suggested that glioma is an effective indicator for monitoring exogenous contaminants in brain tissues.

A Novel Personal Passive Sampler for Collecting Gaseous Phthalates.

Dermal absorption of gaseous chemicals is an important contributor to increased health risk and has yet to be adequately addressed due to the lack of available sampling techniques. In the present study, a novel personal passive sampler consisting of a housing (embracing a polydimethylsiloxane (PDMS) disk as the sorbent phase, a membrane filter, and a stainless-steel mesh) and a watchband (traditional wristband) was constructed and used to characterize gaseous phthalates (PAEs) near the air-skin interface. In a real-life setting, the utility of the passive sampler was validated by comparing the composition profiles of PAEs in the PDMS disks and in active samples and watchbands. The compositions of PAEs were consistent in disks and gaseous constituents from ambient air, with low-molecular-weight (<306 g mol-1) PAEs accounting for 87-100% and approximately 100%, respectively. Appreciable amounts of diisononyl phthalate, diisodecyl phthalate, dinonyl phthalate, and skin lipid (e.g., squalene) were detected in watchbands but not in disks. Apparently, the passive sampler can prevent particles and skin-related chemicals from adhering to the disk and collect gaseous PAEs only. The vast majority of PAEs in watchbands was associated with nongaseous constituents. The present study demonstrated that the sampling strategy is a key factor in exposure assessment.

Low Tar Level Does Not Reduce Human Exposure to Polycyclic Aromatic Hydrocarbons in Environmental Tobacco Smoke.

Environmental tobacco smoke (ETS) is known to pose potential risk to human health, but the effects of tar level remain to be clarified. In the present study, ETS samples from two cigarette types with different tar levels in a 72.5 m3 room were collected for measurement of 16 polycyclic aromatic hydrocarbons (PAHs). Urine samples of volunteers participating in smoking events were collected and analyzed for eight hydroxyl-PAHs. The concentrations, compositions, and particle size distribution patterns of PAHs from higher-tar and lower-tar cigarettes were similar, while the emission factors of PAHs from higher-tar cigarettes were lower than those from lower-tar cigarettes. Furthermore, the change in the concentrations of PAH metabolites in urine samples before and after smoking was not attributed to tar level. Assuming that a single cigarette was smoked in a 100 m3 room, the estimated average inhalation cancer risks for different age groups from exposure to PAHs in ETS were below 1.0 × 10-6, but potential risks should not be overlooked, especially considering that only inhaled particle-bound PAHs in ETS were included in this assessment. Apparently, reduced tar levels would not necessarily lead to lowered risk of exposure to PAHs. Kicking the habit is perhaps the best choice to minimize any potential health risk.

Emissions and Occupational Exposure Risk of Halogenated Flame Retardants from Primitive Recycling of E-Waste.

The production and usage of non-polybrominated diphenyl ether (PBDE) halogenated flame retardants (HFRs) have substantially increased after the ban of several PBDEs. This has resulted in widespread environmental occurrence of non-PBDE HFRs, further amplified by emissions from primitive recycling of obsolete electronics (e-waste). The present study conducted chamber experiments to characterize 15 HFRs (∑15HFR) from thermal treatment and open burning of typical e-waste. Emission factors of ∑15HFR from thermal treatment were 2.6 × 104-3.9 × 105 ng g-1, slightly higher than those from open burning (8.8 × 103-1.0 × 105 ng g-1). Greater output over input mass ratios of ∑15HFR were obtained in thermal treatment than in open burning. Particulate and gaseous HFRs dominated the emissions in thermal treatment and open burning, respectively, largely because of the different temperatures used in the two processes. Particulate HFRs were primarily affiliated with fine particles (Dp < 1.8 µm) peaking at 0.56-1.0 or 0.32-0.56 µm in both thermal treatment and open burning. Occupational exposure to most FRs was relatively low, but several PBDEs may pose potential health risk to workers in e-waste home-workshops. Potentially accruing emissions and health risks of non-PBDE HFRs from primitive recycling of e-waste remain a great concern.

Characteristics of Polybrominated Diphenyl Ethers Released from Thermal Treatment and Open Burning of E-Waste.

Primitive processing of e-waste potentially releases abundant organic contaminants to the environment, but the magnitudes and mechanisms remain to be adequately addressed. We conducted thermal treatment and open burning of typical e-wastes, that is, plastics and printed circuit boards. Emission factors of the sum of 39 polybrominated diphenyl ethers (∑39PBDE) were 817-1.60 × 105 ng g-1 in thermal treatment and nondetected-9.14 × 104 ng g-1, in open burning. Airborne particles (87%) were the main carriers of PBDEs, followed by residual ashes (13%) and gaseous constituents (0.3%), in thermal treatment, while they were 30%, 43% and 27% in open burning. The output-input mass ratios of ∑39PBDE were 0.12-3.76 in thermal treatment and 0-0.16 in open burning. All PBDEs were largely affiliated with fine particles, with geometric mean diameters at 0.61-0.83 µm in thermal degradation and 0.57-1.16 µm in open burning from plastic casings, and 0.44-0.56 and nondetected- 0.55 µm, from printed circuit boards. Evaporation and reabsorption may be the main emission mechanisms for lightly brominated BDEs, but heavily brominated BDEs tend to affiliate with particles from heating or combustion. The different size distributions of particulate PBDEs in emission sources and adjacent air implicated a noteworthy redisposition process during atmospheric dispersal.

Importance of Dermal Absorption of Polycyclic Aromatic Hydrocarbons Derived from Barbecue Fumes.

Despite the ubiquity and carcinogenicity of polycyclic aromatic hydrocarbons (PAHs), their dermal absorption for the general population has not been adequately addressed. Aiming to verify the importance of dermal absorption of PAHs, barbecue (BBQ) in Guangzhou, China was chosen as a case study. Urine samples were collected and analyzed for nine hydroxyl (OH)-PAHs. Air, food, and cotton clothing samples were analyzed for 16 PAHs. Dietary exposure was the dominant exposure route with the greatest amounts of OH-PAH excretion and PAH intake. Dermal intake of low molecular-weight PAHs was greater than inhalation intake from the occurrence of atmospheric PAHs. In addition, the net excreted amounts of OH-naphthalene, OH-fluorene, OH-phenanthrene, and OH-pyrene via dermal absorption were 367, 63, 98, and 28 ng, respectively, upon 2.5-h exposure, comparable to those via combined dermal and inhalation exposure, which were 453, 98, 126, and 38 ng. The ratios of excretion to intake via dermal absorption were 0.11, 0.036, and 0.043 for fluorene, phenanthrene, and pyrene, respectively, lower than the ratios from dietary exposure (0.38, 0.14, and 0.060) but higher than the ratios from inhalation (0.097, 0.016, and 0.025). In the case of BBQ fumes, dermal absorption was a more important pathway for intake of low molecular-weight PAHs than inhalation.

Impact of Polymer Colonization on the Fate of Organic Contaminants in Sediment.

Plastic pellets and microbes are important constitutes in sediment, but the significance of microbes colonizing on plastic pellets to the environmental fate and transport of organic contaminants has not been adequately recognized and assessed. To address this issue, low-density polyethylene (LDPE), polyoxymethylene (POM) and polypropylene (PP) slices were preloaded with dichlorodiphenyltrichloroethanes (DDTs), polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) and incubated in abiotic and biotic sediment microcosms. Images from scanning electron microscope, Lysogeny Broth agar plates and confocal laser scanning microscope indicated that all polymer slices incubated in biotic sediments were colonized by microorganisms, particularly the LDPE slices. The occurrence of biofilms induced higher dissipation rates of DDTs and PAHs from the LDPE slice surfaces incubated in the biotic sediments than in the abiotic sediments. Plastic colonization on LDPE slice surfaces enhanced the biotransformation of DDT and some PAHs in both marine and river sediments, but had little impact on PCBs. By comparison, PP and POM with unique properties were shown to exert different impacts on the physical and microbial activities as compared to LDPE. These results clearly demonstrated that the significance of polymer surface affiliated microbes to the environmental fate and behavior of organic contaminants should be recognized.

Dermal Uptake from Airborne Organics as an Important Route of Human Exposure to E-Waste Combustion Fumes.

Skin absorption of gaseous organic contaminants is an important and relevant mechanism in human exposure to such contaminants, but has not been adequately examined. This article demonstrates that dermal uptake from airborne contaminants could be recognized as a significant exposure route for local residents subjecting to combustion fume from e-waste recycling activities. It is particularly true for organic pollutants which have high dermal penetration rates and large skin-air partition coefficients, such as low molecular weight plasticizers and flame retardants.

Barbecue Fumes: An Overlooked Source of Health Hazards in Outdoor Settings?

Barbecuing or charcoal-grilling has become part of popular outdoor recreational activities nowadays; however, potential human health hazards through outdoor exposure to barbecue fumes have yet to be adequately quantified. To fill this knowledge gap, atmospheric size-fractioned particle and gaseous samples were collected near an outdoor barbecuing vendor stall (along with charcoal-grilled food items) in Xinjiang of Northwest China with a 10-stage micro-orifice uniform deposit impactor and a polyurethane foam (PUF) sampler and were analyzed for particulate matter and polycyclic aromatic hydrocarbons (PAHs). Exposure to PAHs through inhalation and dermal contact by adult consumers who spent 1 h per day near a charcoal-grilling vendor for a normal meal (lunch or dinner) amounted to a BaP equivalent (BaPeq) dosage of 3.0-77 ng day(-1) (inhalation: 2.8-27 ng day(-1) of BaPeq; dermal contact: 0.2-50 ng day(-1) of BaPeq), comparable to those (22-220 ng day(-1) of BaPeq) from consumer exposure through the consumption of charcoal-grilled meat, assumed to be at the upper limit of 50-150 g. In addition, the potential health risk was in the range of 3.1 × 10(-10) to 1.4 × 10(-4) for people of different age groups with inhalation and dermal contact exposure to PAHs once a day, with a 95% confidence interval (7.2 × 10(-9) to 1.2 × 10(-5)) comparable to the lower limit of the potential cancer risk range (1 × 10(-6) to 1 × 10(-4)). Sensitivity analyses indicated that the area of dermal contact with gaseous contaminants is a critical parameter for risk assessment. These results indicated that outdoor exposure to barbecue fumes (particularly dermal contact) may have become a significant but largely neglected source of health hazards to the general population and should be well-recognized.

Use of machine learning to identify key factors regulating volatilization of semi-volatile organic chemicals from soil to air.

Volatilization from soil to air is a key process driving the distribution and fate of semi-volatile organic contaminants. However, quantifying this process and the key environmental governing factors remains difficult. To address this issue, the volatilization fluxes of polybrominated diphenyl ethers (PBDEs) and organophosphate esters (OPEs) from soil were determined in 16 batch experiments orthogonally with six variables (chemical property, soil concentration, air velocity, ambient temperature, soil porosity, and soil moisture) and analyzed with machine learning methods. The results showed that gradient-boosting regression tree models satisfactorily predicted the volatilization fluxes of PBDEs (r2 = 0.82 ± 0.07) and OPEs (r2 = 0.62 ± 0.13). Permutation importance analysis showed that partitioning potential of chemicals between soil and air was the most important factor regulating the volatilization of the target compounds from soil. Temperature and soil porosity played a secondary role in controlling the migration of PBDEs and OPEs, respectively, due to higher volatilization enthalpies of PBDEs than those of OPEs and dominant adsorption of OPEs on mineral surface. The effect of soil moisture was negative and positive for the volatilization fluxes of PBDEs and OPEs, respectively. These results suggested different responses in the soil-air diffusive transport of PBDEs and OPEs to high temperature and rainstorm induced by climate change.

Utility of a modified o-DGT passive sampler for measurement of bisphenol analogues in freshwater and coastal waters.

Bisphenol analogues (BPs) are commonly found in riverine and coastal waters. However, the lack of a reliable and robust passive sampling method has hindered our ability to monitor these compounds in aquatic systems. The study developed a novel organic-diffusive gradients in thin film (o-DGT) sampler based on stainless steel mesh membrane, polyacrylamide diffusive gel, and hydrophilic-lipophilic balance (HLB) binding gel. This innovative design tackled issues of filter membrane sorption in traditional o-DGT devices and potential gel damage in membrane-less o-DGT devices, showing promising application prospects. The mass accumulation of 15 target BPs was linear over 10 days in both freshwater (r2 ≥ 0.92) and seawater (r2 ≥ 0.94), with no saturation observed. The diffusion coefficients (D) through polyacrylamide diffusive gels ranged from 4.04 × 10-6 to 5.77 × 10-6 cm2 s-1 in freshwater and from 1.74 × 10-6 to 4.69 × 10-6 cm2 s-1 in seawater for the target BPs (except for bisphenol PH) at 22 °C. The D values of the target BPs in seawater were lower than those in freshwater due to the high salinity in seawater (35 ‰). The o-DGT samplers demonstrated good integrity in field applications. The total concentrations of the eight detected BPs ranged from 9.2 to 323 ng L-1, which was consistent with the measurements obtained by grab sampling. Among all BPs, bisphenol S, bisphenol F, and bisphenol A were consistently detected at all sites using both sampling methods. The concentrations of some novel BPs in coastal water measured by grab sampling were comparable to those measured in rivers, suggesting the need to strengthen pollution control of BPs in coastal areas. These results indicate that the o-DGT passive sampling method developed in the present study can be effectively used for monitoring BPs in freshwater and coastal environments.

Effects of polymer matrix and temperature on pyrolysis of tetrabromobisphenol A: Product profiles and transformation pathways.

Plastics are crucial constituents in electronic waste (e-waste) and part of the issue in e-waste recycling and environmental protection. However, previous studies have mostly focused on plastic recovery or thermal behavior of flame retardants, but not both simultaneously. The present study simulated the process of e-waste thermal treatment to explore tetrabromobisphenol A (TBBPA) pyrolysis at various temperatures using polystyrene (PS), polyvinyl chloride (PVC), and e-waste plastics as polymer matrices. Pyrolysis of TBBPA produced bromophenol, bromoacetophenone, bromobenzaldehyde, and bromobisphenol A. Co-pyrolysis with the polymer matrices increased emission factors by 1 - 2 orders of magnitude. The pyrolytic products of TBBPA, TBBPA+PS, and TBBPA+PVC were mainly low-brominated bisphenol A, while that of TBBPA in e-waste plastics was consistently bromophenol. Increasing temperature drove up the proportions of gaseous and particulate products, but lowered the relative abundances of inner wall adsorbed and residual products in pyrolysis of pure TBBPA. In co-pyrolysis of TBBPA with polymer matrix, the proportions of products in different phases were no longer governed solely by temperature, but also by polymer matrix. Co-pyrolysis of TBBPA with PS generated various bromophenols, while that with PVC produced chlorophenols and chlorobrominated bisphenol A. Transformation pathways, deduced by ab initio calculations, include hydrogenation-debromination, isopropylphenyl bond cleavage, oxidation, and chlorination.

Uptake of Typical Hydrophobic Organic Contaminants in Vegetables: Evidence From Passive Samplers.

Quantifying the root uptake of hydrophobic organic contaminants (HOCs) by plants remains challenging due to the lack of data on the freely available fractions of HOCs in soil porewater. We therefore hypothesized that a passive sampler could act as a useful tool to evaluate the root uptake potential and pathways of HOCs by plants in soil. We tested this hypothesis by exploring the uptake of polybrominated diphenyl ethers (PBDEs) and organophosphate esters (OPEs) by carrot and lettuce with the codeployment of passive samplers in a contaminated soil system. The results showed that the amounts of PBDEs enriched in carrot and lettuce were positively correlated with those in a passive sampler (r2 = 0.46-0.88). No concentration correlation was observed for OPEs between lettuce and passive samplers, due to possible degradation of OPEs in lettuce. The root-to-porewater ratios of PBDEs and OPEs, respectively, were 6.2 to 11 and 0.05 to 0.88 L g-1 for carrot, and 8.8 to 130 and less than reporting limits to 1.2 L g-1 for lettuce. The ratios were negatively correlated with log KOW values for carrot, but increased with increasing log KOW values over a range of 1.97 to 6.80, and then decreased with log KOW values greater than 6.80 for lettuce. This finding indicated that passive transport and partition were the accumulation pathways of PBDEs and OPEs in carrot and lettuce, respectively. Overall, passive samplers performed adequately in assessing the available fractions of persistent HOCs in plants, and can serve as a viable tool for exploring the pathways for plant root uptake of HOCs. Environ Toxicol Chem 2024;00:1-12. © 2024 SETAC.

Per- and polyfluoroalkyl substances (PFAS) exposure in plasma and their blood-brain barrier transmission efficiency-A pilot study.

Per- and polyfluoroalkyl substances (PFAS) have been shown to penetrate the blood-brain barrier (BBB) and accumulate in human brain. The BBB transmission and accumulation efficiency of PFAS, as well as the potential health risks from human co-exposure to legacy and emerging PFAS due to differences in transport efficiency, need to be further elucidated. In the present pilot study, 23 plasma samples from glioma patients were analyzed for 17 PFAS. The concentrations of PFAS in six paired brain tissue and plasma samples were used to calculate the BBB transmission efficiency of PFAS (RPFAS). This RPFAS analysis was conducted with utmost care and consideration amid the limited availability of valuable paired samples. The results indicated that low molecular weight PFAS, including short-chain and emerging PFAS, may have a greater potential for accumulation in brain tissue than long-chain PFAS. As an alternative to perfluorooctane sulfonic acid (PFOS), 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA) exhibited brain accumulation potential similar to that of PFOS, suggesting it may not be a suitable substitute concerning health risk in brain. The BBB transmission efficiencies of perfluorooctanoic acid, PFOS, and 6:2 Cl-PFESA showed similar trends with age, which may be an important factor influencing the entry of exogenous compounds into the brain. A favorable link between perfluorooctane sulfonamide (FOSA) and the development and/or progression of glioma may be implicated by a strong positive correlation (r2 = 0.94; p < 0.01) between RFOSA and Ki-67 (a molecular marker of glioma). However, a causal relationship between RFOSA and glioma incidence were not established in the present study. The present pilot study conducted the first examination of BBB transmission efficiency of PFAS from plasma to brain tissue and highlighted the importance of reducing and/or controlling exposure to PFAS.

Particle transfer mediates dermal exposure of consumers to plasticizers in eraser and pen accessories.

Dermal exposure to chemicals released from daily consumer products is a rising concern, particularly for children who are susceptible to unintentional hand-to-mouth transfer and related chemical exposure risk. However, chemical transfer induced by tiny particles of intact products has yet to be adequately addressed. The objective of the present study was to determine the potentiality of particles release from intact erasers and pen grips upon dermal contact by measuring the migration rates of the embedded plasticizers (phthalates and its alternatives). The results showed that billions of particles were released from erasers (0.6-1.2 × 109) and pen grips (0.2-1.6 × 108) upon dermal contact at ambient temperature, with sizes mainly smaller than 1 µm. The composition of eraser leachates was identical to that of the corresponding bulk eraser, as confirmed by Fourier-transform infrared spectroscopy and pyrolysis. Migrated hydrophobic plasticizers may be used as indicators of particle release from erasers and pen grips. The potentiality of particle release was negatively correlated with the total plasticizer contents (r = -0.51; p < 0.05) for both erasers and pen grips. These findings indicated that particles directly released from school supplies and accessories could be a non-negligible source of human exposure to plasticizers.

Hydrophobic organic contaminants affiliated with polymer-specific microplastics in urban river tributaries and estuaries.

Exposure to microplastics (MPs) and hydrophobic organic contaminants (HOCs) combined at high concentrations may induce adverse effects to aquatic organisms in laboratory-scale studies. To determine environmentally relevant concentrations of HOCs in MPs, it is essential to understand the occurrence of MP-affiliated HOCs in the aquatic environment. Here we report the occurrences of HOCs affiliated with polymer-specific floating MPs from 12 tributaries and three estuaries in the Pearl River Delta, South China. Target HOCs include nine synthetic musks (SMs), 14 ultraviolet adsorbents (UVAs), 15 polycyclic aromatic hydrocarbons (PAHs), eight polybrominated diphenyl ethers (PBDEs), and 14 polychlorinated biphenyls (PCBs). Average concentrations of MP-affiliated ∑9SM, ∑14UVA, ∑15PAH, ∑8PBDE, and ∑14PCB were 1790, 5550, 1090, 412, and 107 ng g-1, respectively. The average concentrations of HOCs affiliated with MPs of different polymer types were 9790, 7220, 72,500, and 55,800 ng g-1 for polyethylene (PE), polypropylene, polystyrene, and other MPs, respectively. As the concentration of PE was the highest among all MPs at the average concentration of 0.77 mg m-3, the monthly outflow of PE-affiliated HOCs accounted for the largest proportion (46 %) in the outflow of MP-affiliated HOCs (2.8 g) to the coastal ocean via three estuaries. These results suggest that HOCs were highly concentrated in MPs and varied among different chemicals and polymer types. Due to the differences of polymer characteristics and half-life of affiliated chemicals, future toxicology studies concerning exposure to these combined pollutants may need to specify polymer types and their affiliated chemicals.

Insufficient evidence to link human exposure to heavy metals with biomarkers of glioma.

Information on molecular mechanisms has implicated potential association between the concentrations of heavy metals and incidences of glioma, but experimental data on human brain tissue remain sparse. To address this data gap, 13 heavy metals were measured in 137 glioma and 35 non-glioma samples collected from 161 alive patients in Guangdong Province, China in 2019 - 2020. All target heavy metals were detected, suggesting they could cross the blood-brain barrier. Concentrations of Mn, Cu, and Zn were higher in glioma than in non-glioma samples, while those of Ni and Se were higher in non-glioma samples, probably suggesting that these five heavy metals are more prone to be altered by changing pathological conditions. In addition, Cu/Zn, Cr/Mn, Cr/Se, Ni/Se, Pb/Mn, and Pb/Se were statistically different between glioma and non-glioma samples by a difference test and a multiple logistic regression model. These concentration ratios may serve as chemical markers to assist pathological analysis for differentiating between tumor and healthy tissues. However, no direct link between heavy metal concentrations or concentration ratios and biomarkers of glioma (i.e., tumor grade, P53, and Ki-67) was observed. No sufficient evidence was obtained to implicate the role of heavy metals in inducing glioma, largely caused by the limited number of samples. Different concentrations and concentration ratios of heavy metals may be the consequence rather than the cause of pathological changes in brain tumors.

Size-resolved gas-particle partitioning characteristics of typical semi-volatile organic compounds in urban atmosphere.

Understanding particle size distribution and size-resolved gas-particle partitioning of semi-volatile organic compounds (SVOCs) is important for characterizing their fate in atmosphere. However, the size-resolved gas-particle partitioning characteristics of SVOCs has not been adequately considered. To address this issue, the present study collected gaseous and size-fractioned particulate samples both in and outside of schools, offices, and residences in three districts of different urbanization levels in a megacity, Guangzhou, South China during two seasons. Typical SVOCs, including 15 polycyclic aromatic hydrocarbons (PAHs), six organophosphate esters and seven phthalic acid esters were measured. Emission sources, physicochemical properties, and environmental conditions at the sampling sites considerably impacted the spatiotemporal distribution patterns and particle size distribution of target SVOCs. Not all observed gas-particle partition coefficients (Kp) of target SVOCs were negatively correlated with subcooled liquid-vapor pressures (PL0), probably because certain factors, such as the non-exchangeable part of the particle-bound SVOCs, were not considered in traditional gas-particle partition theories. Particle size was an important factor affecting gas-particle partitioning. Adsorption was the dominant mechanism for PAHs with high molecular weight in different particle modes. A new model was established to predict size-resolved Kp of PAHs with high molecular weight based on PL0 and particle size.