Hongliang Jia

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.

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.

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.

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.

Historical contamination and ecological risk of organochlorine pesticides in sediment core in northeastern Chinese river.

Twenty-eight surface sediment samples and one sediment core were analyzed for 21 organochlorine pesticides (OCPs), in order to provide extensive information of distribution, sources, pollution history and ecological risk of these OCP compounds in Daling River area, China. The results showed that hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethanes (DDTs) were the most frequently detected contaminants in the surface sediment samples with concentrations (in ngg(-1) dry weight (dw)) from 1.1 to 30 and from 2.2 to 45, respectively. Analysis of variance showed significant (P<0.05) differences between HCHs and DDTs residues in surface sediment sampled from the various locations. Residues of HCHs and DDTs in sediment core (in ngg(-1)dw) ranged from 2.1 to 18 and 9.1 to 53, respectively. The temporal trends of HCHs and DDTs concentrations in the sediment core were affected by application history, emission and soil residues. Compositional analysis of HCHs and DDTs indicated that new sources were lindane and dicofol mainly due to agricultural activities. Additionally, based on the available sediment quality guidelines, slight potential health risks of DDTs may exist to benthic organisms in Daling River and Bohai Sea.

Polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs in the coastal seawater, surface sediment and oyster from Dalian, Northeast China

A total of 46 polycyclic aromatic hydrocarbons (PAHs, 21 parent and 25 alkylated) were determined in seawater, surface sediment and oyster from coastal area of Dalian, North China. The concentration of Σ46PAHs in seawater, sediment, and oyster were 136-621 ng/L, 172-4700 ng/g dry weight (dw) and 60.0-129 ng/g wet weight (ww) in winter, and 65.0-1130 ng/L, 71.1-1090 ng/g dw and 72.8-216 ng/g ww in summer, respectively. High PAH levels were found in industrial area both in winter and summer. Selected PAH levels in sediments were compared with Sediments Quality Guidelines (ERM-ERL, TEL-PEL indexes) for evaluation probable toxic effects on marine organism and the results indicate that surface sediment from all sampling sites have a low to medium ecotoxicological risk. Daily intake of PAHs via oyster as seafood by humans were estimated and the results indicated that oyster intake would not pose a health risk to humans even 30 days after a oil spill accident near by. Water-sediment exchange analysis showed that, both in winter and summer, the fluxes for most high molecular weight PAHs were from seawater to sediment, while for low molecular weight PAHs, an equilibrium was reached between seawater and sediment.

Distribution, Fate, Inhalation Exposure and Lung Cancer Risk of Atmospheric Polycyclic Aromatic Hydrocarbons in Some Asian Countries

A large-scale monitoring program, the Asia Soil and Air Monitoring Program (Asia-SAMP), was conducted in five Asian countries, including China, Japan, South Korea, Vietnam, and India. Air samples were collected using passive air samplers with polyurethane foam disks over four consecutive 3-month periods from September 2012 to August 2013 to measure the seasonal concentrations of 47 polycyclic aromatic hydrocarbons (PAHs), including 21 parent and 26 alkylated PAHs, at 176 sites (11 background, 83 rural, and 82 urban). The annual concentrations of total 47 PAHs (∑47PAHs) at all sites ranged from 6.29 to 688 ng/m(3) with median of 82.2 ng/m(3). Air concentrations of PAHs in China, Vietnam, and India were greater than those in Japan and South Korea. As expected, the air concentrations (ng/m(3)) were highest at urban sites (143 ± 117) followed by rural (126 ± 147) and background sites (22.4 ± 11.4). Significant positive correlations were found between PAH concentrations and atmosphere aerosol optical depth. The average benzo(a)pyrene equivalent concentration (BaPeq) was 5.61 ng/m(3). It was estimated that the annual BaPeq concentrations at 78.8% of the sampling sites exceeded the WHO guideline level. The mean population attributable fraction (PAF) for lung cancer due to inhalation exposure to outdoor PAHs was on the order 8.8‰ (0.056-52‰) for China, 0.38‰ (0.007-3.2‰) for Japan, 0.85‰ (0.042-4.5‰) for South Korea, 7.5‰ (0.26-27‰) for Vietnam, and 3.2‰ (0.047-20‰) for India. We estimated a number of lifetime excess lung cancer cases caused by exposure to PAHs, which the concentrations ranging from 27.8 to 2200, 1.36 to 108, 2.45 to 194, 21.8 to 1730, and 9.10 to 720 per million people for China, Japan, South Korea, Vietnam, and India, respectively. Overall, the lung cancer risk in China and Vietnam were higher than that in Japan, South Korea, and India.

Characterization of polycyclic aromatic hydrocarbons in concurrently monitored surface seawater and sediment along Dalian coast after oil spill

Polycyclic aromatic hydrocarbons (PAHs) were measured in concurrently sampled surface seawater and sediment collected at 20 sites around Dalian, China 50 days after an oil spill accident. The concentrations of total PAHs ranged from 15 to 160 ng L(-1) in seawater, and from 64 to 2100 ng g(-1) dry weight in surface sediment. The spatial trends of PAHs in seawater, but not in sediment, showed a significant negative correlation with the distance from the oil spill site, indicating a strong source of PAHs from oil spill place to the surrounding seawater. The similar profiles for PAH composition in both crude oil and seawater could indicate that oil spill caused PAHs concentration in seawater, but not in sediment. Analysis of water-sediment exchange of PAHs showed that the direction of the net flux of PAHs was from sediment to seawater for most priority PAHs, and from water to sediment for a few HWM-PAHs.

Dechloranes in a river in northeastern China: Spatial trends in multi-matrices and bioaccumulation in fish (Enchelyopus elongatus)

Dechloranes (Decs), including Dechlorane Plus (DP) and Dechlorane (Dec) 602, 603, 604, are used as flame retardants. Fifty four samples were collected in a river in northeastern China and analyzed for Decs by gas chromatography/mass spectrometry. The average concentrations of total DP (syn- and anti-) in water, sediment, air, reed (Phragmites australis), and fish (E. elongatus) were 0.30±0.24 (mean±SD) ng L(-1), 1.3±0.69 ng g(-1) dry weight (dw), 0.25±0.18 ng m(-3), 0.63±0.18 ng g(-1) wet weight (ww), and 29±20 ng g(-1) lipid weight (lw), respectively. While Dec 602 and Dec 603 were detected in most of sediment and fish samples, no Dec 604 was found in any of the investigated environmental matrices. The mean ratio of syn-DP to total DP (fsyn) in water, sediment, reed, and fish were 0.28, 0.25, 0.27 and 0.47, suggesting depletion in abiota and enrichment in biota for syn-DP. It was found that biota-sediment accumulation factor (BSAF) was 4.7 for Dec 602, 0.88 for syn-DP, and 0.33 for anti-DP.