Hong Qi

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.

An Asia-Specific Source of Dechlorane Plus: Concentration, Isomer Profiles, and Other Related Compounds

The distribution of dechloranes, a group of chlorinated flame retardants, were investigated in air, soil, and sediment around a newly discovered Dechlorane Plus (DP) production facility in China (Anpon). To date, the only known DP manufacturing plant is located in Niagara Falls, NY (OxyChem). Dechloranes including DP, Dechlorane (Mirex), and the recently discovered Dechlorane 602 (Dec 602) were detected in air, soil, and sediment, while Dechlorane 603 and Dechlorane 604 were below detection limit in all matrices. DP air concentrations near the facility ranged from 7737 to 26 734 pg m(-3), the greatest reported thus far. Soil concentrations in the same area for DP, Dechlorane, and Dec 602 were 1490+/-3580 ng g(-1), 81.6+/-96.5 ng g(-1), and 7.24+/-13.2 ng g(-1) dry weight, respectively. Interestingly, lower concentrations of DP (4.93+/-4.34 ng g(-1)), Dechlorane (30.2+/-19.9 ng g(-1)), and Dec 602 (2.14+/-2.23 ng g(-1)) were found in sediment from a nearby canal. Spatial trends of Dechlorane and Dec 602 in soil were similar to DP, implying that the DP manufacturing plant may also be a source of these other flame retardants. DP soil concentrations surrounding the facility decreased by an order of magnitude within 7.5 km. The syn-DP fractional abundance (fsyn) value (0.40) for the commercial DP product manufactured at Anpon was slightly higher than that (0.20-0.36) produced by OxyChem. The fsyn value in most air samples was largely similar to the Chinese commercial DP mixture, while most soil and sediment abundances were lower, suggesting a stereoselective depletion of syn-DP.

Concentration and bioaccumulation of dechlorane compounds in coastal environment of northern China.

Dechloranes, including Dechlorane Plus (DP), Mirex (Dechlorane), Dechlorane 602 (Dec 602), Dechlorane 603 (Dec 603), and Dechlorane 604 (Dec 604), were determined using GC-MSD for water, sediment and oyster samples collected at 15 sampling sites near the Bohai and Huanghai Sea shore area of northern China in 2008. DP and Mirex were detected in most water, sediment, and oyster samples, which indicated widespread distribution of these two compounds. The mean concentrations in water, sediment and oyster samples, respectively, were 1.8 ng/L, 2.9 ng/g dry weight (dw) and 4.1 ng/g wet weight (ww) for total DP, and 0.29 ng/L, 0.90 ng/g dw, and 2.0 ng/g ww for Mirex. Dec 602 and Dec 603 were not detected in water but in small portions of the sediment and oyster samples, showing a low level of contamination by these two chemicals in the region. Strong and significant correlations were found between total DP and Mirex concentrations in water, sediment and oyster samples, probably suggesting similar local sources of these two chemicals. Dec 604 was not found in any samples. The biota-sediment accumulation factor (BSAF) of DP, Mirex, and Dec 602 declined along with the increase of their logarithm of octanol-water partition coefficients (log Kow), possibly indicating that compounds with lower log Kow (like Mirex and Dec 602) accumulated more readily in biota. The mean fractional abundance of syn-DP (fsyn) was 0.34 in water samples, a value lower than that in Chinese commercial mixture (0.41), while the mean fsyn for surface sediment (0.44) and oyster (0.45) samples were higher than technical values. Enrichment of syn-DP in oyster was in agreement with previously reported findings in Great Lakes fish. Enrichment of syn-DP in marine surface sediments, however, is contrary to data reported for fresh water sediments. To our knowledge this is the first report of Dec 602, Dec 603, and Dec 604 in a marine environment and also the first report of Dechloranes in marine biota.

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.

Survey of Cyclic and Linear Siloxanes in Sediment from the Songhua River and in Sewage Sludge from Wastewater Treatment Plants, Northeastern China

Siloxanes are used in a wide range of industrial applications, such as fuel additives, automotive polishes and waxes, and antifoaming agents, as well as in personal care products and biomedical devices. Despite the potential for environmental occurrence, few studies have reported sources and pathways of siloxanes in the environment. In this study, we determined concentrations of four cyclic siloxanes, namely, octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and tetradecamethylcycloheptasiloxane (D7) as well as 13 linear siloxanes (L4 to L16), in sediments sampled from the Songhua River and in sewage sludge sampled from treatment plants that discharge wastewater into the Songhua River in northeastern China. Siloxanes were found in all of the sediment samples at total concentrations (sum of all cyclic and linear siloxanes) as high as 2050xa0ng/g dry weight (dw). The respective total concentration ranges for cyclic (D4, D5, D6, and D7) and linear (L4 to L16) siloxanes in sewage sludge were 602 to 2360 and 98 to 3310xa0ng/g dw. Cyclic siloxanes were found at greater concentrations than linear siloxanes in sediment samples. However, the summed concentrations of linear siloxanes were higher than the summed concentrations of cyclic siloxanes in sludge samples. Among cyclic siloxanes, D7 and D5 were the dominant compounds in both sediment and sludge. Among linear siloxanes, L10 and L11 together accounted for 55% of the total concentrations in sludge samples, and L6 accounted for 30% of the total concentration in sediment samples. To our knowledge, this is the first report to document concentrations and compositions of organosiloxanes in sediments and sewage sludge from China.

Polycyclic Aromatic Hydrocarbons and Polychlorinated Biphenyls in Topsoils of Harbin, China

Levels of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in 17 topsoil samples collected in and around the city of Harbin, an industrial center in Northeast China for decades, are presented. Total concentrations (ng/g dry weight [dw]) ranged from 17 to 3,260 (mean: 508) for PAHs and 0.30 to 6.17 (mean: 1.63) for PCBs. As expected, large differences of the concentration levels of PAHs and PCBs in topsoil were found among the samples from urban, suburban, and background/rural sites. Total PCB and PAH concentrations were higher in industrialized areas than those at the other sites, with a ratio of up to one order of magnitude, possibly indicating the urban source of these chemicals. The PAH profiles were similar among samples, with high percentages of high molecular weight (HMW) PAHs and domination of four-ring PAHs. Compositions of PCB homologues showed that tri-CBs and tetra-CBs were abundant in all soil samples. There was also a higher abundance of low molecular weight (LMW) PCBs and lower abundance of HMW PCBs at background sites than other areas, indicating the urban fractionation phenomenon. Pyrogenic origins were the dominant PAH sources in surface soil at most urban sites, whereas petrogenic origins were the major PAH sources in surface soil at all the rural and background sites. The TEQ concentrations (pg/g dw) of all four dioxin-like PCBs (CBs 77, 81, 105, and 118) were 0.009 for humans and mammals, 0.005 for fish, and 1.42 for birds. Strong correlations were found between PAH and PCB concentrations and soil organic matter and, also, between PAH and PCB concentrations.

Urinary Concentrations of Parabens in Chinese Young Adults: Implications for Human Exposure

Parabens are widely used as preservatives in foods, cosmetics, and pharmaceuticals. However, recent studies have indicated that high and systemic exposure to parabens can be harmful to human health. Although a few studies have reported urinary paraben levels in western countries, studies on paraben exposure in the Chinese population are limited. China is currently a major producer of parabens in the world. In this study, 109 urine samples collected from Chinese young adults (approximately 20xa0years old) were analyzed for five parabens (methyl-, ethyl-, propyl-, butyl-, and benzyl-parabens) by high-performance liquid chromatography–tandem mass spectrometry. Methyl-, propyl-, and ethyl-parabens were the three major paraben analogues found in all (100xa0%) samples. The concentration of the sum of the five parabens ranged from 0.82 to 728xa0ng/mL with a geometric mean value of 17.4xa0ng/mL. Urinary concentration of parabens was 2-fold greater in females than in males. Based on the measured urinary concentrations, daily intake of parabens by the Chinese young adults was estimated and compared with those reported for United States adults. The estimated daily intakes (EDIurine) of parabens were 18.4 and 40.8xa0μg/kg bw/day for Chinese males and females, respectively, values that were lower than those reported for United States adults (74.7xa0μg/kg bw/day). Based on the reported concentrations of parabens in foods from China and the United States, the contribution of dietary intake to EDIurine was estimated to be 5.5, 2.6, and 0.42xa0% for Chinese males, Chinese females, and United States adults, respectively, which indicates the significance of nondietary sources of parabens to human exposures.