Li-Yan Liu

Polychlorinated Biphenyls in Global Air and Surface Soil: Distributions, Air−Soil Exchange, and Fractionation Effect†

Polychlorinated biphenyl (PCB) concentrations in air and soil, measured by various research groups from around the world, were compiled and analyzed. Data for air were available from most regions, particularly in Europe and Asia. The average air concentrations (pg/m(3)) for SigmaPCB at background sites were 70 (5.1-170) for Europe, 79 (49-120) for North America, 66 (18-110) for South America, 270 (9-670) for Central America, 59 (17-150) for Asia, and 15 (13-17) for Australia. Data for soils exhibited better global coverage compared to air and were available from most regions. The average soil concentrations (pg/g dry weight) for SigmaPCB at background sites were 7500 (47-97 000) for Europe, 4300 (110-25 000) for North America, 1400 (61-9 500) for South America, 580 (120-2 900) for Asia, 390 (94-620) for Africa, and 280 (140-540) for Australia. Based on available studies where coupled measurements of PCBs in air and soil were made, the equilibrium status of PCBs in the air-soil system was investigated for China, West Midlands of the UK, central and southern Europe, and along a latitudinal transect from the south of the UK to the north of Norway. Differences were observed in plots of the soil-air equilibrium status (expressed as the soil-air fugacity fraction, ff) for different PCB homologues. This was explained by varying contributions from primary and secondary emissions-spatially and temporally. The net effect after several decades of PCB emissions to air, preferential transport of lower molecular weight PCBs through primary and secondary emission, and reductions in emissions to air in recent decades is that the lower molecular weight PCBs have achieved (and in some cases exceeded) soil-air equilibrium in many parts of the world. The exception is remote and background sites that are still dominated by primary sources.

Seasonal variations of sources of polycyclic aromatic hydrocarbons (PAHs) to a northeastern urban city, China

Understanding the seasonal variations of sources of polycyclic aromatic hydrocarbons (PAHs) in air in urban region is important to the effective control of air pollution in the region. Based on a year round dataset (from August 2008 to July 2009), the sources of atmospheric PAHs in Harbin, a typical Chinese northeastern urban city, were analyzed by principal component analysis (PCA) and positive matrix factorization (PMF). The average total (gas plus particulate) PAH concentration varied from 6.3 ng m(-3) to 340 ng m(-3) with a mean of 100+/-94 ng m(-3), with higher concentrations in heating season than those in non-heating season. PCA and PMF identified similar source factors to atmospheric PAHs with obvious seasonal variation. The results obtained by PMF method indicated that the main sources were coal-fired boiler (39%), diesel engine (34%) and coal average (22%) in heating season and traffic emissions (59%), ground evaporation (18%) and coal average (17%) in non-heating season. Excellent correlation coefficients between predicted and measured concentrations of PAHs indicated that PMF was a useful model for source apportionment of PAHs in atmosphere.

Occurrence and Profiles of Phthalates in Foodstuffs from China and Their Implications for Human Exposure

Phthalate esters are used in a wide variety of consumer products, and human exposure to this class of compounds is widespread. Nevertheless, studies on dietary exposure of humans to phthalates are limited. In this study, nine phthalate esters were analyzed in eight categories of foodstuffs (n = 78) collected from Harbin and Shanghai, China, in 2011. Dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), benzyl butyl phthalate (BzBP), and diethylhexyl phthalate (DEHP) were frequently detected in food samples. DEHP was the major compound found in most of the food samples, with concentrations that ranged from below the limit of quantification (LOQ) to 762 ng/g wet weight (wt). The concentrations of phthalates in food samples from China were comparable to concentrations reported for several other countries, but the profiles were different; DMP was found more frequently in Chinese foods than in foods from other countries. The estimated daily dietary intake of phthalates (EDIdiet) was calculated based on the concentrations measured and the daily ingestion rates of food items. The EDIdiet values for DMP, DEP, DIBP, DBP, BzBP, and DEHP (based on mean concentrations) were 0.092, 0.051, 0.505, 0.703, 0.022, and 1.60 μg/kg-bw/d, respectively, for Chinese adults. The EDIdiet values calculated for phthalates were below the reference doses suggested by the United States Environmental Protection Agency (EPA). Comparison of total daily intakes, reported previously based on a biomonitoring study, with the current dietary intake estimates suggests that diet is the main source of DEHP exposure in China. Nevertheless, diet accounted for only <10% of the total exposure to DMP, DEP, DBP, and DIBP, which suggested the existence of other sources of exposure to these phthalates.

Atmospheric concentrations, sources and gas-particle partitioning of PAHs in Beijing after the 29th Olympic Games.

A comprehensive sampling campaign was carried out to study atmospheric concentration of polycyclic aromatic hydrocarbons (PAHs) in Beijing and to evaluate the effectiveness of source control strategies in reducing PAHs pollution after the 29th Olympic Games. The sub-cooled liquid vapor pressure (logP(L)(o))-based model and octanol-air partition coefficient (K(oa))-based model were applied based on each seasonal dateset. Regression analysis among log K(P), logP(L)(o) and log K(oa) exhibited high significant correlations for four seasons. Source factors were identified by principle component analysis and contributions were further estimated by multiple linear regression. Pyrogenic sources and coke oven emission were identified as major sources for both the non-heating and heating seasons. As compared with literatures, the mean PAH concentrations before and after the 29th Olympic Games were reduced by more than 60%, indicating that the source control measures were effective for reducing PAHs pollution in Beijing.

Dechlorane Plus in Surficial Water and Sediment in a Northeastern Chinese River

Surface water and sediment samples concurrently collected in Songhua River in northeastern China from May to October 2006 were analyzed for Dechlorane Plus (DP), a chlorinated flame retardant. Samples were obtained from three main areas: SHR-Rul (rural area of Songhua River), SHR-Hrb (the section of the river within the city of Harbin), and Hrb (urban waters of Harbin). The majority of SHR-Rul water samples (85%) and SHR-Hrb water samples (73%) and 33% of urban water samples (Hrb) were below the detection limit. The mean water DP concentration in Hrb (0.55 +/- 0.81 ng L(-1)) was approximately 3 times greater than the levels measured in SHR-Hrb (0.17 +/- 0.38 ng L(-1)) and more than 15 times greater than the levels measured in SHR-Rul (0.03 +/- 0.07 ng L(-1)). DP detection rates in sediment samples were 50% (Hrb), 100% (SHR-Hrb), and 78% (SHR-Rul). The mean sediment DP concentration in SHR-Hrb (0.11 +/- 0.05 ng g(-1)) was approximately three times greater than that in SHR-Rul (0.04 +/- 0.05 ng g(-1)). These DP concentrations are likely attributable to local sources in urban areas rather than distant sources via long-range transport. The mean fractional abundance of the syn isomer of DP (f(syn)) was 0.34 +/- 0.10 in all water samples, a value indistinguishable from that of a commercial mixture (f(syn) = 0.35), indicating the source was local. The mean f(syn) value of 0.23 +/- 0.06 in all sediment samples suggested a stereoselective depletion of syn-DP relative to the anti-DP isomer in sediments. To our knowledge, this paper represents the first report of DP concentrations in Chinese water and sediments.

Polybrominated Diphenyl Ethers in Air across China: Levels, Compositions, and Gas-Particle Partitioning

Air samples were concurrently collected using high volume air samplers for 24 h every week from September 2008 to August 2009 at 15 sites (11 urban, 1 suburban, and 3 background/rural) across China. Twelve polybrominated diphenyl ether (PBDE) congeners (BDE-17, -28, -47, -66, -85, -99, -100, -138, -153, -154, -183, and -209) were measured. Total PBDE concentrations (∑12PBDEs) in air (gas + particle phases) were in the range of 11.0-838 pg m(-3) with a mean of 232 ± 72 (mean ± SE) pg m(-3). The site with the highest concentration was Guangzhou (838 ± 126 pg m(-3)), followed by Beijing (781 ± 107 pg m(-3)). Significant positive correlations were found between PBDEs levels and urban population (R = 0.69, P < 0.05) and gross industrial output values (R = 0.87, P < 0.001) as well. BDE-209 was the dominating congener with the contribution of 64 ± 23% to ∑12PBDEs, followed by BDE-47(8 ± 8%) and -99(6 ± 5%) at all urban and suburban sites. At background/rural sites, however, BDE-47 was the dominating congener, followed by BDE-99, together accounting for 52 ± 21% of ∑12PBDEs, while BDE-209 was only 11 ± 2%. It was found that PBDEs at the 15 sites showed a primary distribution and fractionation pattern. This study produced more than 700 pairs of air samples in gaseous and particulate phases with a wide temperature range of ∼60 °C, providing a good opportunity to investigate gas-particle partitioning for individual PBDE congeners. The results of gas-particle partitioning analysis for PBDEs using both subcooled-liquid-vapor pressure (PL)-based and octanol-air partition coefficient (KOA)-based models indicated that PBDEs in air at all sampling sites had not reached equilibrium because the slope values (mO) in the KOA-based equation and the opposite slope values (mP) in the PL-based equation at all 15 sampling sites were less than 1. It also found that both mO and -mP were significantly and positively correlated with the annual average temperatures of sampling sites and also significantly and negatively correlated with the mole masses of PBDE congeners, indicating a general trend that the higher the temperature at the sampling site and the lower the mole mass of the PBDE congeners are, the closer to the equilibrium the congeners approach and vice versa. To our knowledge, this is the first study to report the correlations of the slope values for both the KOA-based and PL-based equations with temperatures at sampling sites and mole masses for individual PBDE congeners.

Dechlorane plus in multimedia in northeastern Chinese urban region

Dechlorane plus (DP) was quantified by gas chromatography/mass spectrometry (GC/MS) in soil and ambient air (collected from Harbin City, a typical northeastern Chinese urban region), water and sediment samples (collected in the segment within Harbin of Songhua River, located in northeast of China). The average concentrations of DP in sediment and soil samples were 123.6 pg g⁻¹ dry weight (dw), and 11.3 pg g⁻¹ dw, respectively. However, the concentration of DP in water was below the method detection limit (MDL). The inter-media comparison between water and sediment suggested that the sediment may be a receptor for DP. For air samples, two methods were used for collecting air in order to compare, active air sampling (AAS) and passive air sampling (PAS). The average concentrations of DP were 0.4 pg m⁻³ and 6.9 pg m⁻³ for AAS and PAS samples, respectively. Discrepancies of deployment period and different calculated method for DP concentration may help to explain the remarkable difference between PAS and AAS. Overall, DP in all matrices in Harbin City showed lower concentrations than that in the Great Lakes region. The anti-DP isomer was consistently greater than that of the syn-DP isomer in all matrices. The average fractional abundance of the syn-DP isomer (f(syn)) was smaller than the technical DP composition (f(syn)=0.35) according to other studies in the Great Lakes region. As we know, this study is the first attempt to comprehensively study DP concentrations in four different matrices (water, ambient air, sediment and soil) in China.

Monitoring and modeling endosulfan in Chinese surface soil.

Endosulfan is a currently used organochlorine pesticide in China, with annual usage of 2300 t between 1994 and 2004. Concentrations of endosulfan (including α- and β-isomers and their metabolite endosulfan sulfate) were reported for surface soil collected in 2005 at 141 sites (6 background, 95 rural, and 40 urban) across China. The concentrations of total endosulfan (sum of α-endosulfan, β-endosulfan, and endosulfan sulfate) at all sites ranged from BDL (below detection limit) to 19000 pg/g dry weight (dw), with geometric mean (GM) 120 pg/g dw. Rural soils had the highest total endosulfan concentrations, with GM 160 pg/g dw, followed by urban soils (GM = 83 pg/g dw) and background soils (GM = 38 pg/g dw). The observed soil concentrations of α-endosulfan (GM = 6.5 pg/g dw) were much lower than those of β-endosulfan (GM = 49 pg/g dw) and endosulfan sulfate (GM = 47 pg/g dw). The fractional abundance of α-endosulfan F(α-endo) [α-endosulfan/(α-endosulfan + β-endosulfan)] for all soils ranged from 0.00040 to 0.91, with GM 0.10, much lower than those in technical products (ranged from 0.67 to 0.7), which most likely reflects that α-endosulfan is more volatile and degrades faster than β-endosulfan in soil. Consequently, half-life of β-endosulfan in soil is expected longer than α-endosulfan. Significant correlation between endosulfan sulfate and its parent isomers suggested that the presence of endosulfan sulfate originated from its parent isomers. Based on multiple linear regression model, inventories of endosulfan sulfate in Chinese agricultural soil in 2004 with a 1/4° longitude × 1/6° latitude resolution are established. Comparison between field measurements and modeling results showed significant correlations between the modeled and measured endosulfan concentrations, and 89%, 83%, and 70% of monitoring data fell between the lowest and the highest modeled concentrations for α- and β-endosulfan and endosulfan sulfate, respectively. The good agreement lends credibility to modeled soil concentrations of endosulfan. To our knowledge, this is the first soil concentration inventory for endosulfan sulfate, which paves the way for further study on its environmental behavior.

Polybrominated diphenyl ethers (PBDEs) in the indoor dust in China: Levels, spatial distribution and human exposure

Indoor environment is an important source of human exposure to several toxicants, such as brominated flame retardants. Indoor dust samples were collected in winter season in 2010, which covered 23 provinces across China, for the analysis of polybrominated diphenyl ethers (PBDEs). Concentrations of PBDEs (Σ14PBDEs) ranged from 8.92 to 37,500 ng/g, with the mean of 3520 ng/g. BDE-209 was the most dominate congener, followed by BDE-183, BDE-47 and BDE-99. PBDE concentrations and the longitude were significantly correlated (p<0.05), which was consistent with the status of social-economic development and human activities. The results of exposure to PBDEs through dust ingestion and dermal absorption indicated that the toddlers had the highest exposure dose, with the median value of 6.0 ng/kg-bw/day. According to the hazard quotients, health risk of PBDEs via dust ingestion in China is currently acceptable. Monte Carlo simulation was implemented to quantify the uncertainty and sensitivity of exposure models for determining the most influential variables. The results suggested that more specific and accurate parameters should be used for dust ingestion and dermal absorption exposure models in future.

Concentrations and sources of polycyclic aromatic hydrocarbons in indoor dust in China.

Indoor dust samples were collected across China in the winter of 2010 from 45 private domiciles and 36 public buildings. 16 polycyclic aromatic hydrocarbons (PAHs) were determined by GC-MS. Total concentrations of PAHs ranged from 1.00 μg/g to 470 μg/g with a mean value of 30.9 μg/g. High-molecular weight (HMW) PAHs (4 to 6 rings) are the predominant PAHs found in indoor dust, accounting for 68% of the total PAH concentration in private domiciles, and 84.6% in public buildings. Traffic conditions and cooking methods were the two key factors controlling PAH levels, especially for coal combustion and vehicular traffic emission sources. A significant positive correlation was observed between PAH concentrations in indoor dust and based on location (latitude and longitude). The latitudinal distribution indicated a higher usage of coal for heating in Northern China than in Southern China. The longitudinal distribution indicated that the usage of oil and mineral fuels as well as economic development and population density increased from West China to East China. In addition, diagnostic ratios and principal component analysis (PCA) were used to explore source apportion, as indicated in both the pyrogenic and petrogenic sources of PAHs in indoor dust in China. Furthermore, the BaP equivalent was applied to assess the carcinogenic risk of PAHs, which also indicated that traffic emissions and coal combustion were the two major contributions to carcinogenic risk of PAHs in indoor dust in China.