Bao-Zhong Zhang

Occurrence of Polybrominated Diphenyl Ethers in Air and Precipitation of the Pearl River Delta, South China: Annual Washout Ratios and Depositional Rates

On the basis of a one-year (from October 2006 to September 2007) sampling campaign, 34 air samples and 23 bulk precipitation samples were collected in the Pearl River Delta (PRD) in southern China and analyzed for polybrominated diphenyl ethers (PBDEs). Fifteen tri- to deca-BDE congeners (sum of which is defined as Sigma15PBDE) were detected in more than 70% of the samples. In three urban-rural regions, Sigma15PBDE concentrations ranged from 77 to 372 pg/m3 in air (particulate + vapor) and 1.98 to 15.5 ng/L in rain (particle+dissolved) from Dongguan, from 195 to 1450 pg/m3 in air and 4.71 to 17.2 ng/L in rain from Shunde, and from 23.7 to 148 ng/L in rain from Guangzhou. Among the BDE congeners, BDE-209 was the predominant component. Linear correlations between the gas-particle partition coefficients (Kp) and the subcooled vapor pressures (P(O/L)) of individual BDE congeners were observed for both the wet and dry seasons, but the slopes (-0.572 to -0.525) of the fitted equations all substantially deviated from equilibrium condition (slope = -1). The total washout ratio by bulk rainfalls was determined to be 2 x 103 for tri-BDEs and 6 x 104 for BDE-209. The estimated annual dry and wet depositional rates were 6720 and 2460 kg/yr, respectively, for BDE-209, and 7270 and 2940 kg/yr for Sigma15PBDE in the PRD, indicating a dominant pathway for PBDEs input into the PRD soil and aquatic environments.

Size-Dependent Dry Deposition of Airborne Polybrominated Diphenyl Ethers in Urban Guangzhou, China

Gaseous and size-segregated particulate PBDEs (specifically BDE-47, -99, -183, -207, and -209) in the air were measured in urban Guangzhou at 100 and 150 m above the ground in daytime and at night in August and December 2010, to assess dry deposition of these contaminants accurately with regards to influences of meteorological factors but without confounding surface effects. Particulate PBDEs were more abundant at night than in daytime, and slightly higher in winter than in summer, likely from varying meteorological conditions and atmospheric boundary layers. More than 60% of particulate-phase PBDEs was contained in particles with an aerodynamic diameter (D(p)) below 1.8 μm, indicating long-range transport potential. The average daily particle dry deposition fluxes of PBDEs in August ranged from 2.6 (BDE-47) to 88.6 (BDE-209) ng m(-2) d(-1), while those in winter ranged from 2.0 (BDE-47) to 122 (BDE-209) ng m(-2) d(-1). Deposition fluxes of all PBDE congeners were significantly higher in daytime than at night for both months, due to the effect of diurnal variability of meteorological factors. In addition, mean overall particle deposition velocities of individual BDE congeners ranged from 0.11 to 0.28 cm s(-1). These values were within a factor of 2 of assumed values previously used in southern China and the Laurentian Great Lakes, suggesting that such assumptions were reasonable for sites with similar particulate size distributions and PBDE sources. Dry deposition velocities of PBDEs were lower at night than those in the daytime, probably reflecting higher mechanical and thermal turbulence during daytime. Dry deposition of particulate-bound PBDEs is influenced by short-term temporal variability from meteorological factors, and also by particulate size fractions.

Calculated respiratory exposure to indoor size-fractioned polycyclic aromatic hydrocarbons in an urban environment

Polycyclic aromatic hydrocarbons (PAHs) associated with inhalable particles are harmful to human health, especially to people in urban indoor environments. To evaluate human respiratory exposure to indoor PAHs properly, respiratory deposition fluxes of size-fractioned PAHs were estimated based on size-segregated distribution of PAHs in indoor air of an urban community of Guangzhou, China. The concentrations of ∑(16)PAH (sum of the 16 priority PAHs designated by the United States Environmental Protection Agency) were 28.9±10.0 ng/m(3), with the mean benzo(a)pyrene equivalent (BaPE) concentration at 4.1±1.6 ng/m(3). Particle size distributions of both ∑(16)PAH and BaPE concentrations peaked in the 1.0-1.8 μm fraction. The mean respiratory deposition flux of ∑(16)PAH was 5.9 ng/h, and accumulation mode particles contributed 20.5-83.8% of the respiratory deposition fluxes for individual PAHs. In addition, 8.6-10.2% of inhaled ∑(16)PAH were calculated to be deposited in the alveoli region, with accumulation particles as the largest contributor. In particular, ultrafine particles contributed 0.4-21.7% of individual PAHs deposited in the alveoli region, more than twice the fraction of the PAHs in the ultrafine particles (0.2-8.5%). Finally, lifetime cancer risk via inhalation of indoor particulate PAHs may be greater than the cancer risk guideline value (10(-6)), depending on specific assumptions used in this risk assessment.

Occurrence, bioaccumulation and potential sources of polybrominated diphenyl ethers in typical freshwater cultured fish ponds of South China

To determine the potential input sources of polybrominated diphenyl ethers (PBDEs) to fish farming environments in South China, samples of seven various environmental matrices were collected from October 2006-September 2007. Tri- to deca-BDEs were detected in all samples analyzed, with mean concentrations (+ or - standard deviations) at 5.7 + or - 3.6 ng/L in pond water, 15 + or - 11 ng/g dry wt. in pond sediment, 12 + or - 3.8 ng/g dry wt. in bank soil, 21 + or - 20 ng/g lipid wt. in fish, and 93 + or - 62 ng/g lipid wt. in fish feeds. In addition, BDE-209 was the major constituent in all samples except fish and BDE-47 was predominant in fish samples. Relatively high abundances of BDE-49 were detected in all the samples compared to those in the penta-BDE technical products. Several bioaccumulation factors were evaluated. Finally, statistical analyses suggested that fish feed, as well as pond water at a lesser degree, may have been the major source of PBDEs in freshwater farmed fish.

Bioaccumulation kinetics of polybrominated diphenyl ethers and decabromodiphenyl ethane from field-collected sediment in the oligochaete, lumbriculus variegatus

The extensive use of polybrominated diphenyl ethers (PBDEs) and decabromodiphenyl ethane (DBDPE) has made them widespread contaminants in abiotic environments, but data regarding their bioavailability to benthic organisms are sparse. The bioaccumulation potential of PBDEs and DBDPE from field-collected sediment was evaluated in the oligochaete Lumbriculus variegatus using a 49-d exposure, including a 28-d uptake and a 21-d elimination phase. All PBDEs and DBDPE were bioavailable to the worms with biota-sediment accumulation factors (BSAFs) ranging from 0.0210 g organic carbon/g lipid to 4.09 g organic carbon/g lipid. However, the bioavailability of highly brominated compounds (BDE-209 and DBDPE) was poor compared with that of other PBDEs, and this was confirmed by their relatively low freely dissolved concentrations (C(free)) measured by solid-phase microextraction. The inverse correlation between BSAFs and hydrophobicity was explained by their uptake (k(s)) and elimination (k(e)) rate constants. While ke changed little for PBDEs, ks decreased significantly when chemical hydrophobicity increased. The difference in bioaccumulation kinetics of brominated flame retardants in fish and the worms was explained by their physiological difference and the presence of multiple elimination routes. The appropriateness of 28-d bioaccumulation testing for BSAF estimation was validated for PBDEs and DBDPE. In addition, C(free) was shown to be a good indicator of bioavailability.

Bioaccumulation of Highly Hydrophobic Organohalogen Flame Retardants from Sediments: Application of Toxicokinetics and Passive Sampling Techniques

Highly hydrophobic organohalogen flame retardants (HHOFRs) are found ubiquitously in the environment; therefore, a better understanding of their bioavailability is needed. In the current study, bioaccumulation testing using the oligochaete, Lumbriculus variegatus, and passive sampling (solid-phase microextraction (SPME)) were performed to study the bioaccumulation potential of HHOFRs, including decabromodiphenyl ether (deca-BDE), decabromodiphenyl ethane (DBDPE), and dechlorane plus (DP), in laboratory-spiked and field-collected sediments. The HHOFRs were bioavailable to L. variegatus even though their biota-sediment accumulation factors were low (0.016 ± 0.002 to 0.48 ± 0.082 g organic carbon/g lipid, syn-DP > anti-DP > deca-BDE > DBDPE). Hydrophobicity and stereoisomerism affected HHOFR bioavailability. Meanwhile, HHOFR concentrations on the SPME fibers (Cf) correlated with those in biota (Cb), suggesting the potential application of SPME in bioavailability prediction for those compounds. The log Cf to log Cb correlation for deca-BDE and DP had a greater intercept than that for polychlorinated biphenyls (data obtained from the literature) although the slopes were similar, while data for DBDPE fell on the regression line for PCBs, implying some uncertainty in application of SPMEs across chemical classes. The increasing sorptive ability of proteins for HHOFRs in comparison to the less-brominated BDEs suggested that protein-binding should be considered when estimating bioaccumulation potential of HHOFRs in benthic invertebrates.