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.

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.

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.

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.

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.

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.

Effects of organic carbon/elemental carbon and particle size on inhalation bioaccessibility of particle-bound PAHs.

Bioaccessible fractions of particle-bound hydrophobic organic compounds (HOCs) are critical to evaluating human inhalation exposure risk. However, the key factors for controlling the release of HOCs into the lung fluid are not adequately examined. To address this issue, eight particle size fractions (0.056-18 µm) from different particle emission sources (barbecue and smoking) were collected and incubated with an in vitro method for determining inhalation bioaccessibilities of polycyclic aromatic hydrocarbons (PAHs). The bioaccessible fractions of particle-bound PAHs were 35-65% for smoke-type charcoal, 24-62% for smokeless-type charcoal, and 44-96% for cigarette. The size distributions of bioaccessible fractions of 3-4 ring PAHs were symmetric with the patterns of their masses, characterized as a unimodal distribution with both the trough and peak at 0.56-1.0 µm. Analysis from machine learning showed that chemical hydrophobicity appeared to be the most significant factor affecting inhalation bioaccessibility of PAHs, followed by organic carbon and elemental carbon contents. Particle size seemed to have little effect on the bioaccessibility of PAHs. A compositional analysis of human inhalation exposure risk from total concentration, deposition concentration, and bioaccessible deposition concentration in alveolar region showed a shift in the key particle size from 0.56-1.0 µm to 1.0-1.8 µm and an increasing in the contributions of 2-3 ring PAHs to risk for cigarette due to the high bioaccessible fractions. These results suggested the significance of particle deposition efficiency and bioaccessible fractions of HOCs in risk assessment.

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.

Glioma is associated with exposure to legacy and alternative per- and polyfluoroalkyl substances.

Data on the occurrences of legacy and alternative per- and polyfluoroalkyl substances (PFASs) in glioma are scarce. It remains unclear if PFASs exposure is related to the prevalence of glioma. A total of 137 glioma and 40 non-glioma brain tissue samples from patients recruited from the Nanfang Hospital, South China were analyzed for 17 PFAS compounds. Perfluorohexanoic acid, perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS), perfluorooctane sulfonamide (FOSA), and 6:2 chlorinated polyfluorinated ether sulfonate were frequently detected (> 60 %) in glioma. The total concentrations (range; median) of 17 PFASs in glioma (0.20-140; 3.1 ng g-1) were slightly higher than those in non-glioma (0.35-32; 2.2 ng g-1), but without statistical significance. The PFAS concentrations in males were statistically higher (p < 0.05) than those in females. Elevated glioma grades were associated with higher concentrations of PFOA, PFOS, and FOSA. Positive correlations were observed between PFAS concentrations (especially for PFOA) and Ki-67 or P53 expression, pathological molecular markers of glioma. Our findings suggested that exposure to PFASs might increase the probability to develop glioma. This is the first case study demonstrating associations between PFASs exposure and brain cancer. More evidences and potential pathogenic mechanisms warranted further investigations.

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.

Distribution profiles of bisphenols in school supplies and implications for human exposure.

Bisphenol compounds (BPs) are usually applied in the production of school supplies, however, little is known on the occurrence of BPs in school supplies. In this study, 15 BPs were detected in 121 samples of school supplies collected from commercial market. Among all compounds studied, BPA, BPF, and BPS were the dominant compounds in school supplies with the detection frequency of 93.15 %, 85.62 % and 82.53 %, respectively, and at median concentrations of 161, 23.64 and 14.11 ng g-1 dw. The total concentrations of BPs varied among types of school supplies in the following order: paper (median: 1347 ng g-1 dw) > fabric (521.4 ng g-1 dw) > plastic (472.7 ng g-1 dw) > rubber (352.4 ng g-1 dw). Risk assessment of BPs in school supplies was evaluated by the estimated daily intake (EDI) via dermal absorption, and the median EDIs of ∑15 BPs were 156.78 ng d-1 (11.27-37,042.37 ng d-1) and 432.75 ng d-1 (32.44-91,624.22 ng d-1) for general and occupational people, respectively.

Utility of benzothiazoles as markers of tire-derived inputs to estuarine waters assessed by polyethylene sheets.

Tire-derived particles and polyethylene (PE) debris co-exist in estuaries and potentially deteriorate water quality. Chemicals can be emitted from tire-derived particles and resorb to PE debris. However, there was lack of information about the interaction (e.g., sorption and desorption) between tire-derived chemicals and PE debris. By combining batch sorption and desorption experiments along with in situ field deployment of PE sheets, we examined the utility of benzothiazoles (BTZs) sorbed in PE as suitable markers of tire-derived inputs. The sorptive characteristics and PE-water partition coefficients (often designated as Kpew) of selected tire-derived marker candidates, i.e., polycyclic aromatic hydrocarbons (PAHs), benzothiophenes (BTPs) and BTZs, were measured. Moderately polar BTPs and BTZs (except for 2-(4-morpholinyl) benzothiazole) reached equilibrium within 2-8 days, compared to 20 days for nonpolar PAHs. The measure Kpew values and octanol-water partition coefficients of PAHs and BTZs were linearly correlated with each other (r2 > 0.80; p < 0.05). The desorption potentiality of PAHs and BTZs from tire particles is consistent with the hydrophilic properties of the target chemicals, while desorption ratios of BTZs and PAHs are 25-87% and <20%, respectively. Samplers with PE sheets as the sorbent phase were deployed in Hailing Bay, an urbanized estuary in South China, to measure concentrations of PAHs, BTPs and BTZs. Benzothiazoles sorbed in PE samples were associated with the massive utilization of automobile tires, while PAHs were linked to the boat maintenance facilities and BTPs were not detected in any tire particle and field PE samples. Therefore sorbed BTZs in PE can potentially serve as chemical markers of tire-derived inputs to estuaries.

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.

Development of an in vitro model to simulate migration of organic contaminants from pad products to human sweat and enhance dermal exposure risk assessment.

Dermal sorption is an important route for human exposure to organic chemicals embedded in consumer products, but the related chemical migration from consumer products to sweats was often overlooked in assessing skin exposure risk. To address this issue, the present study selected polycyclic aromatic hydrocarbons (PAHs), phthalic acid esters (PAEs), and benzothiazoles (BTs) as the target compounds and developed an in vitro simulation model with two artificial sweats (i.e., acidic and alkaline), a sorbent, and a PVC standard material. An appropriate biological inhibitor (ampicillin) and incubation time of 20 d for assessing the maximum migration efficiency of chemicals were selected. The mass balance of the target compounds during the in vitro incubation was verified. The established in vitro simulation model was used to determine the migration ratios of PAEs and BTs in three types of mouse pads. The maximum migration ratios of DBP, DIBP, DEHP, and BT from leather pad to both sweats were less than those for silicone and rubber pads. Key controlling parameters in migration ratios should be examined in subsequent investigations. Risk assessment showed that the daily exposure doses of PAEs and BTs in mouse pads were higher than the literature data. The hazard index of PAEs in leather pad exceed 1, indicating that PAEs could induce non-carcinogenic effects to human health through hand contact. Overall, the established in vitro simulation model provides a feasible alternative for assessing the potential risk for dermal exposure to consumer products.

Determination of low-density polyethylene-water partition coefficients for novel halogenated flame retardants with the large volume model and co-solvent model.

The partition coefficient (Kpew) of an analyte between low-density polyethylene (LDPE) film and water is a critical parameter for measuring freely dissolved concentrations of the analyte with PE passive sampling devices. Measuring log Kpew for super hydrophobic organic chemicals (HOCs) have been proven extremely difficult. The present study developed a large volume model for measuring log Kpew of super HOCs, i.e., novel halogenated flame retardants (NHFRs). Results showed that the measured log Kpew values of selected PAHs and PCBs obtained by the large volume model were in line with those from the co-solvent model and the literature data within less 0.3 log units of difference, while those of NHFRs (6.27-7.34) except for hexachlorocyclopentadienyldibromocyclooctane (HCDBCO) and Decabromodiphenyl ethane (DBDPE) were significantly lower than those (6.51-8.89) from the co-solvent model. A curvilinear relationship was observed between log Kpew and log Kow of all target compounds, with the turning point at log Kow = âˆ¼8.0 in the large volume model, but that was not found for the co-solvent model. These can be attributed to the large molecular volumes (> 450 Å3) for NHFRs, which require high Gibbs free energy to penetrate into the inside structures of LDPE in the large volume model. However, the solvent swelling effects in the co-solvent model needs to be investigated. Therefore, the large volume model is robust to determine the Kpew values of super HOCs for facilitating the application of aquatic passive sampling techniques.

Effects of cooking on oral bioaccessibility of PBDEs, MeO-PBDEs, and OH-PBDEs in fish (tilapia) and chicken egg.

Human health concerns are rising with polybrominated diphenyl ethers' (PBDEs) analogues, methoxylated and hydroxylated PBDEs (MeO-PBDEs and OH-PBDEs), due to their occurrences in foods and greater potential toxicological effects than PBDEs. While the oral bioaccessibilities (BA%) of PBDEs in foods are available, such information on MeO-PBDEs and OH-PBDEs, and the effects of cooking on them have not been adequately addressed. The present study was conducted with fish and chicken egg as typical foods to assess the bioaccessibility (BA%) of PBDEs, MeO-PBDEs, and OH-PBDEs using the colon extended physiologically based extraction test and examine the effects of cooking processes (boiling, frying, and steaming) on them. The results showed that thermal degradation or transformation of the target compounds did not occur during boiling and frying of fish. The BA% of individual PBDEs, MeO-PBDEs, and OH-PBDEs were 20-51% for boiled fish, 11-20% for pan-fried fish, 15-77% for steamed egg, and 42-68% for pan-fried egg. Cooking decreased the BA% of all target compounds in fish due to protein denaturation. However, the BA% of OH-PBDEs in pan-fried egg were greater than those in steamed egg. In addition, the substituent groups of CH3O- and OH- did not pose any effects on the BA% of BDE-47 in fish, but OH-group decreased its BA% in egg. These findings suggested that MeO-PBDEs and OH-PBDEs exhibited the similar oral BA% in fish to PBDEs, but the underlying mechanism for the effects of cooking on BA% of OH-PBDEs in egg needs to be further investigated.

Impact of passive sampler protection apparatus on sediment porewater profiles of hydrophobic organic compounds.

Passive sampling techniques have been widely used to determine the dissolved concentration profiles of hydrophobic organic compounds (HOCs) in sediment porewater. However, the effects of having a protection for the passive sampler on profiling HOCs concentrations in sediment porewater, especially in deep sediment, have remained unclear. To address this issue, low density polyethylene passive samplers with and without protectors, which consisted of glass fiber filter and porous stainless steel shield, were simultaneously deployed in sediment of the Dongjiang River, South China. The results showed that the protectors retarded the dissipation of performance reference compounds (PRCs) from the sampler by a factor of 2-9. The protectors seemed to exert a negligible effect on the measured concentrations of PAHs, BDE-47, and BDE-99 in surficial sediment porewater (0-14 cm depth) from both samplers. However, the sediment porewater concentration profiles of PAHs and BDE-47 from the sampler with protectors were in agreement with those normalized by dry weight in deep sediment (16-34 cm depth), indicating that a diffusion layer established by the protectors may minimize the probability of local depletion of the target analytes in deep sediment. In addition, the log Koc values of PAHs, BDE-47, and BDE-99 exhibited a slight increasing trend with sediment depth. This finding suggested that in situ passive sampling techniques could be a feasible tool in determining the site-specific log Koc values of HOCs at different sediment depths.