Lian-Jun Bao

Solid-phase Microextraction (SPME) with Stable Isotope Calibration for Measuring Bioavailability of Hydrophobic Organic Contaminants

Solid-phase microextraction (SPME) is a biomimetic tool ideally suited for measuring bioavailability of hydrophobic organic compounds (HOCs) in sediment and soil matrices. However, conventional SPME sampling requires the attainment of equilibrium between the fiber and sample matrix, which may take weeks or months, greatly limiting its applicability. In this study, we explored the preloading of polydimethylsiloxane fiber with stable isotope labeled analogs (SI-SPME) to circumvent the need for long sampling time, and evaluated the performance of SI-SPME against the conventional equilibrium SPME (Eq-SPME) using a range of sediments and conditions. Desorption of stable isotope-labeled analogs and absorption of PCB-52, PCB-153, bifenthrin and cis-permethrin were isotropic, validating the assumption for SI-SPME. Highly reproducible preloading was achieved using acetone-water (1:4, v/v) as the carrier. Compared to Eq-SPME that required weeks or even months, the fiber concentrations (Cf) under equilibrium could be reliably estimated by SI-SPME in 1 day under agitated conditions or 20 days under static conditions in spiked sediments. The Cf values predicted by SI-SPME were statistically identical to those determined by Eq-SPME. The SI-SPME method was further applied successfully to field sediments contaminated with PCB 52, PCB 153, and bifenthrin. The increasing availability of stable isotope labeled standards and mass spectrometry nowadays makes SI-SPME highly feasible, allowing the use of SPME under nonequilibrium conditions with much shorter or flexible sampling time.

Potential health risk for residents around a typical e-waste recycling zone via inhalation of size-fractionated particle-bound heavy metals.

Health risk of residents dwelling around e-waste recycling zones has been a global concern, but has not been adequately examined. The present study was intended to evaluate the potential health risk of residents through inhalation exposure to size-fractionated particle-bound heavy metals in a typical e-waste recycling zone, South China. Anthropogenic metals (Zn, Se, Pb, Sb, As, and Cd) were predominantly enriched in fine particles (Dp<1.8μm), whereas the crustal elements (Ti, Fe, and Co) tended to accumulate in coarse particles (Dp>1.8μm). Although the daily inhalation intakes of the target metals were significantly lower than those through food consumption and ingestion of house dust, the hazard quotients of total metals for adults (95% CI: 1.0-5.5) and children (95% CI: 3.0-17) were greater than 1. Moreover, the incremental lifetime cancer risks of five carcinogenic metals (Cr, Co, Ni, As, and Cd) for adults and children were 1.3×10(-3) (95% CI: 4.1×10(-4)-3.0×10(-3)) and 3.9×10(-3) (95% CI: 1.3×10(-3)-8.6×10(-3)), respectively, substantially higher than the acceptable cancer risk range of 10(-6)-10(-4). All these findings suggested that health risks were high for local residents dwelling around the e-waste recycling zone through inhalation exposure to particle-bound heavy metals, for both adults and children.

Association of soil polycyclic aromatic hydrocarbon levels and anthropogenic impacts in a rapidly urbanizing region: Spatial distribution, soil–air exchange and ecological risk

The occurrence of polycyclic aromatic hydrocarbons (PAHs) in soil of the Pearl River Delta (PRD) and surrounding areas was examined on a basis of six land-use types and four geographic regions, from which the impacts of anthropogenic events on the terrestrial environment were evaluated. No significant difference in the concentrations of Σ28PAH and Σ15PAH (sums of 28 and 15 PAHs, respectively) was found among the land-use types of industry, landfill and residency. On the other hand, higher soil PAH concentrations occurred in the central PRD characterized by dense population and high urbanization level, compared to other geographic regions. Source diagnostics implicated the combustions of coal and refined petroleum as the major input sources of anthropogenic PAHs. Furthermore, low molecular weight PAHs tended to volatilize from soil to air while the opposite was prevailing for high molecular weight PAHs. The mean annual diffusive flux of Σ15PAH (852 μg m(-2)yr(-1)) from the soil to the atmosphere in the central PRD was greater than those in the PRDs periphery (195 μg m(-2)yr(-1)), West region (322 μg m(-2)yr(-1)) and East region (84.9 μg m(-2)yr(-1)), suggesting that the central PRD may have become a secondary source of PAHs to the surrounding areas. Finally, ecological risk assessment based on the classification from Maliszewska-Kordybach showed that 3.5% of soil within the central PRD was heavily contaminated by PAHs and 5.2 million residents may be subjected to high health risk.

Health Risk Characterization for Resident Inhalation Exposure to Particle-Bound Halogenated Flame Retardants in a Typical E-Waste Recycling Zone

Inhalation of pollutants is an important exposure route for causing human health hazards, and inhalation exposure assessment must take into account particle size distribution because particle-bound pollutants are size-dependent. Such information is scarce, particularly for residents dwelling within e-waste recycling zones where abundant atmospheric halogenated flame retardants (HFRs) commonly used in electronic/electrical devices have been widely reported. Atmospheric size-fractioned particle samples were collected using a 10-stage Micro-Orifice Uniform Deposit Impactor from an e-waste recycling zone in South China. The deposition efficiencies and fluxes of size-fractioned HFRs including polybrominated diphenyl ethers (PBDEs), alternative brominated flame retardants, and Dechlorane Plus in the human respiratory tract were estimated using the International Commission on Radiological Protection deposition model. The majority of HFRs was found to deposit in the head airways, with coarse particles (aerodynamic diameter (Dp) > 1.8 μm) contributing the most (69-91%). Conversely, fine particles (Dp < 1.8 μm) were dominant in the alveolar region (62-80%). The inhalation intake of PBDEs within the e-waste recycling zone was 44 ng/d (95% confidence interval (CI): 30-65 ng/d), close to those through food consumption in non-e-waste recycling regions. The estimated total hazard quotient of particle-bound HFRs was 5.6 × 10(-4) (95% CI: 3.8 × 10(-4)-8.8 × 10(-4)). In addition, incremental lifetime cancer risk induced by BDE-209 was 1.36 × 10(-10) (95% CI: 7.3 × 10(-11)-2.3 × 10(-10)), much lower than the Safe Acceptable Range (1.0 × 10(-6)-1.0 × 10(-4)) established by the United States Environmental Protection Agency. These results indicate that the potential health risk from inhalation exposure to particle-bound HFRs for residents dwelling in the e-waste recycling zone was low.

Sorption of PBDE in low‐density polyethylene film: Implications for bioavailability of BDE‐209

The coefficients of partitioning (K(pew) ) between low-density polyethylene (LDPE) film (50-µm thickness) and water for 23 polybrominated diphenyl ether (PBDE) congeners were determined based on a regression analysis of sorption kinetics over an extended exposure period (up to 365 d). A curvilinear relationship between log K(pew) and log K(OW) (octanol-water partition coefficient) was obtained for the target BDE congeners with the turning point at log K(OW) approximately 8. Previously obtained dietary uptake efficiencies of BDE congeners in common carp (Cyprinus carpio) were also found to relate curvilinearly to log K(OW) . In addition, field-measured relative abundances of BDE-209 compiled from previous investigations conducted in the Pearl River Delta of South China were significantly (p < 0.001) higher in abiotic samples (n = 79 from 11 matrices) than in biotic samples (n = 73 from 12 matrices), suggesting the likelihood for reduced bioavailability of BDE-209 in certain biota. Finally, a molecular-scale analysis indicated that the curvilinear relationship between log K(pew) and log K(OW) can be attributed to the energy barrier that a molecule has to overcome as it attempts to diffuse into the LDPE structure, which can become significant for larger molecules. Similarly, the reduced bioavailability of BDE-209 in many biological species can be regarded as a reflection of the magnitude of molecular interactions between cell membranes and BDE-209.

Assessing bioavailability of DDT and metabolites in marine sediments using solid‐phase microextraction with performance reference compounds

Solid-phase microextraction (SPME) has often been used to estimate the freely dissolved concentration (Cfree ) of organic contaminants in sediments. A significant limitation in the application of SPME for Cfree measurement is the requirement for attaining equilibrium partition, which is often difficult for strongly hydrophobic compounds such as DDT. A method was developed using SPME with stable isotope-labeled analogues as performance reference compounds (PRCs) to measure Cfree of DDT and metabolites (DDTs) in marine sediments. Six (13) C-labeled or deuterated PRCs were impregnated into polydimethylsiloxane (PDMS) fiber before use. Desorption of PRCs from PDMS fibers and absorption of DDTs from sediment were isotropic in a range of sediments evaluated ex situ under well-mixed conditions. When applied to a historically contaminated marine sediment from a Superfund site, the PRC-SPME method yielded Cfree values identical to those found by using a conventional equilibrium SPME approach (Eq-SPME), whereas the time for mixing was reduced from 9 d to only 9 h. The PRC-SPME method was further evaluated against bioaccumulation of DDTs by Neanthes arenaceodentata in the contaminated sediment with or without amendment of activated carbon or sand. Strong correlations were consistently found between the derived equilibrium concentrations on the fiber and lipid-normalized tissue residues for DDTs in the worms. Results from the present study clearly demonstrated the feasibility of coupling PRCs with SPME sampling to greatly shorten sampling time, thus affording much improved flexibility in the use of SPME for bioavailability evaluation.

Size-dependent atmospheric deposition and inhalation exposure of particle-bound organophosphate flame retardants.

Atmospheric size-fractionated particles were collected at different heights in an e-waste recycling zone (QY) and urban Guangzhou (GZ), China and analyzed for organophosphate flame retardants (OPFRs). The total air concentrations of eight OPFRs were 130±130 and 138±127 ng m(-3) in QY and GZ, respectively. Compositional profiles of chlorinated OPFRs were different between QY and GZ, but the size distribution patterns of all OPFRs were not significantly different at different heights. Estimated atmospheric deposition fluxes of OPFRs were 51±67 and 55±13 μg m(-2) d(-1) in QY and GZ, respectively, and the coarse particles (Dp>1.8 μm) dominated both the dry and wet deposition fluxes. Moreover, not all particle-bound OPFRs were inhalable and deposited in the human respiratory tract. The calculated inhalation doses of OPFRs were much lower than the reference doses, suggesting that potential health risk due to inhalation exposure to particle-bound OPFRs in the e-waste recycling zone and urban site was low.

Size-dependent distribution and inhalation cancer risk of particle-bound polycyclic aromatic hydrocarbons at a typical e-waste recycling and an urban site

Atmospheric particle size distribution of polycyclic aromatic hydrocarbons (PAHs) in a typical e-waste recycling zone and an urban site (Guangzhou) in southern China featured a unimodal peak in 0.56-1.8 μm for 4-6 ring PAHs but no obvious peak for 2-3 ring PAHs at both sites. The atmospheric deposition fluxes of PAHs were estimated at 5.4 ± 2.3 μg m(-2) d(-1) in the e-waste recycling zone and 3.1 ± 0.6 μg m(-2) d(-1) in Guangzhou. In addition, dry and wet deposition fluxes of PAHs were dominated by coarse (Dp > 1.8 μm) and fine particles (Dp < 1.8 μm), respectively. Fine particles predominated the deposition of PAHs in the lung. The results estimated by incremental inhalation cancer risk suggested that particle-bound PAHs posed serious threat to human health within the e-waste recycling zone and Guangzhou.

Equilibrium and kinetic solid-phase microextraction determination of the partition coefficients between polychlorinated biphenyl congeners and dissolved humic acid

A conventional solid-phase microextraction (SPME) method combined with liquid-liquid extraction was applied under equilibrium and nonequilibrium conditions to determine the partition coefficients (K(doc)) of 25 polychlorinated biphenyl congeners (PCBs) between Sigma-Aldrich humic acid (HA) and water. The values of log K(doc) determined with equilibrium SPME were linearly correlated with the logarithm of the octanol-water partition coefficients (K(ow)) for PCB congeners at logK(ow)< approximately 7.2, but the trends were disrupted for logK(ow) from approximately 7.2 to 8.18. In addition, short-term (5 min to 4 days) and long-term (5-44 days) uptake profiles of PCBs were established, from which a pseudo-equilibrium for sorption of PCBs was revealed at approximately 4 days of extraction. To understand this phenomenon, the uptake profiles were fitted with two equations (one equation is often used for pure water samples and the other one is applicable for samples containing complex matrices) derived from a first-order kinetics model. Subsequently, K(doc) values obtained through kinetic approaches were compared with those acquired from equilibrium SPME. The comparison of K(doc) values indicated that the pseudo-equilibrium was caused by the slow desorption of PCBs from HA rather than the biphasic desorption mechanism.

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.