Exchange Of Polycyclic Aromatic Hydrocarbons Research Articles

Dissolved PAHs in the Beibu Gulf and adjacent waters of the South China Sea: Physical and biochemical processes-driven distributional variations

Polycyclic aromatic hydrocarbons (PAHs) in semi-enclosed gulfs are influenced by physical and biochemical processes, which haven’t been well understood. This study aims to investigate the spatial distribution and vertical profiles of dissolved PAHs in the Beibu Gulf and adjacent waters of the South China Sea, along with hydrological, meteorological, and biochemical variables. Particularly relevant are the effects of atmospheric pressure, salinity, ammonium, chlorophyll-a, as well as riverine inputs (RI), sea currents, and upwelling. In surface seawater, the total concentrations of eight dissolved PAHs (∑8PAHs) were 7.76 ± 2.16ng/L, with a distribution pattern of western Guangdong waters (WGWs) > BG > Qiongzhou Strait (QS). ∑8PAHs in the northern BG (9.10 ± 2.00ng/L) was significantly higher than that in the southern BG (6.65 ± 1.54ng/L) (p < 0.01), suggesting that local anthropogenic activities and unique environmental characteristics significantly influenced PAHs distribution. In water column, PAHs in BG displayed enrichment in surface and bottom but decreased in medium water, while those in WGWs and QS decreased with increasing depth. Source apportionment concluded that PAHs in QS and WGWs were primarily from petroleum sources, and PAHs in BG were mainly from coal combustion. RI, combined with circulation, coastal current, and intrusion of SCS water influenced the surface PAHs distribution in BG, with eddy impacts observed. Specifically, regarding the surface PAHs distribution, differences in atmospheric pressure may influence the air-sea exchange of PAHs, especially positively affecting 4-ring PAHs. Salinity factors further corroborated the contribution of RI to 3-ring PAHs, followed by the regulation of PAHs through biological pumps (ammonia and chlorophyll-a). Moreover, upwelling-induced biodegradation and resuspension affected the vertical distribution of PAHs. While most PAHs posed a negligible risk, coking-generated fluorene posed a moderate risk to ecosystems due to changes in the energy structure, warranting further investigation into its toxicological impacts.

Air-sea exchange of PAHs in the Taiwan Strait: Seasonal dynamics and regulation mechanisms revealed by machine learning approach

In this study, to understand the seasonal dynamics of air-sea exchange and its regulation mechanisms, we investigated polycyclic aromatic hydrocarbons (PAHs) at the air-sea interface in the western Taiwan Strait in combination with measurements and machine learning (ML) predictions. For 3-ring PAHs and most of 4- to 6-ring, volatilization and deposition fluxes were observed, respectively. Seasonal variations in air-sea exchange flux suggest the influence of monsoon transitions. Results of interpretable ML approach (XGBoost) indicated that volatilization of 3-ring PAHs was significantly controlled by dissolved PAH concentrations (contributed 24.0 %), and the gaseous deposition of 4- to 6-ring PAHs was related to more contaminated air masses originating from North China during the northeast monsoon. Henry’s law constant emerged as a secondary factor, influencing the intensity of air-sea exchange, particularly for low molecular weight PAHs. Among environmental parameters, notably high wind speed emerges as the primary factor and biological pump’s depletion of PAHs in surface seawater amplifies the gaseous deposition process. The distinct dynamics of exchanges at the air-water interface for PAHs in the western TWS can be attributed to variations in primary emission intensities, biological activity, and the inconsistent pathways of long-range atmospheric transport, particularly within the context of the monsoon transition.

Air–plant interaction and air–soil exchange of polycyclic aromatic hydrocarbons in a large human-influenced reservoir in southwest China

The Three Gorges Reservoir (TGR) is totally manmade, strongly influenced by anthropogenic activity, and lies on the upper reaches of Yangtze River. The periodic storage and discharge of water from the Three Gorges Dam could have altered the original air-plant/soil interactions of contaminants in TGR. Herein, paired atmospheric gas–particle, air–plant, and air–soil samples were collected to investigate the air–plant interaction and air–soil exchange of 16 USEPA priority polycyclic aromatic hydrocarbons (PAHs). The air–plant interaction based on McLachlan's framework to our datasets suggests that PAHs were absorbed via gaseous deposition that was restricted by the plant–gas dynamic equilibrium. The equilibrium indicates a dynamic balance between the gaseous phase and plant surface in PAH absorption. The main limiting factor influencing the PAH uptake was the plant species rather than the atmospheric PAH concentration. The air–soil exchange of PAHs exhibited a net volatilization flux of 16.71 ng/m2/d from the soil to the air based on annual average. There was more volatilization and less deposition in summer and more deposition and less volatilization in autumn and winter. The soil serves as a secondary source of atmospheric PAHs. As the first attempt on probing the multi-interface geochemical process of PAHs, this study highlights the influence of manual water level manipulation from the TGD and environmental factors (such as temperature, humidity, and soil properties) on the regional fate of PAHs in the TGR.

Gas-particle partitioning and air-water exchange of polycyclic aromatic hydrocarbons in the Three Gorges Reservoir, southwest China

A 30 m vertical drawdown water level fluctuation zone (WLFZ) was formed annually due to seasonal water impoundment in the Three Gorges Reservoir (TGR) in Southwest China. In this study, a super site in downstream of WLFZ, ∼200 km off the Three Gorges Dam, was used to investigate the seasonally gas-particle partitioning and air-water exchange of USEPA 16 polycyclic aromatic hydrocarbons (16 PAHs). The average concentrations of 16 PAHs in the particle phase were 66.63 ± 9.15 ng/m3 in winter and 8.43 ± 2.95 ng/m3 in summer. In the gas phase, they were 28.47 ± 4.79 ng/m3 in winter and 10.57 ± 1.51 ng/m3 in summer. In the dissolved phase of surface water, they were 38.65 ± 6.37 ng/L in winter and 56.53 ± 8.86 ng/L in summer. The logarithmic gas-particle partitioning coefficient (lgKp) was negatively correlated with the logarithmic subcooled liquid vapor pressure (lgPL0). While the lgKp was positively correlated with logarithmic octanol-air distribution coefficient (lgKOA). These two regressions both indicated un-equilibrium of gas-particle partitioning of PAHs in the atmosphere. Applying “Whitman two-film resistance model” to our datasets shows that 3-ring PAHs had a net volatilization from water to air (2.74–6.43 ng/m2/d), and 4 ∼ 5-ring PAHs favored deposition from air to water (−0.614 to −0.413 ng/m2/d). The water as a potential ‘source’ for 3-ring and a ‘sink’ for 4 ∼ 5-ring PAHs was thereby revealed. The results of this study are crucial for understanding atmospheric gas-particle partitioning of PAHs and for revealing the factors and mechanisms governing their geochemical cycling at air and water interfaces.

Profiling and assessing soil-air exchange of polycyclic aromatic hydrocarbons (PAHs) in playground dust and soil using ex situ equilibrium passive sampling

Cancer risk can be associated with exposure to polycyclic aromatic hydrocarbons (PAHs) in playground dust and soil. This study investigated the profiles and sources of PAHs from poured rubber-surfaced playground dust and uncovered playground surface soil, by applying an ex-situ equilibrium passive sampling technique. Surface dust and soil samples were collected from 15 different playgrounds in Seoul, Republic of Korea. The total 16 EPA PAHs concentrations in surface dust and soil varied from 198 to 919 μg kg−1 dw and 68–169 μg kg−1 dw, respectively. 4- to 6-ring PAHs were dominant, accounting for approximately 53.8%–94.5% of the total PAHs in surface dust and soil. The diagnostic ratios and principal component analysis suggested that a mixed coal combustion and vehicular emission was likely the main source of PAHs in the surface dust and soil. The higher total organic carbon content can explain the higher PAH accumulation and lower fugacities of PAHs. The fugacity comparison of phenanthrene and pyrene in dust, soil, air, and playground surface material indicated that atmospheric deposition is the main source of PAHs in the dust and soil on rubber-surfaced and uncovered surfaced playgrounds. This study contributes to the understanding of PAHs sources in dust and soil samples in children's playground and helps policymaker determine the right contamination sources for risk management.

Exploring the influence of water exchange on the distribution of polycyclic aromatic hydrocarbons in marine sediments by numerical calculation model

Polycyclic aromatic hydrocarbons (PAHs) are one of the most important pollution factors in the marine environment. It is significant to expound their distribution in the complex marine environment for pollution prevention and control. In our previous research, we found that water exchange of PAHs has an important influence on their concentration distribution in sediments. With the help of Delft3D technology, a multi-process coupled dynamic model of PAHs was constructed, being based on the survey data of Liaodong Bay from May to June 2015. The water exchange rate of PAHs was calculated and studied by using mathematical statistics and numerical simulation. The results showed that the half water exchange time of PAHs in Liaodong Bay is about 57–580 days. The water exchange rate of PAHs has a significant influence on their concentration distribution of PAHs in sediments. Where there is a high water exchange rate, there the concentration of PAHs in sediment was relatively low. The closer areas are to bay-head, the lower the water exchange rate, and the easier leading to the formation of high concentration areas of PAHs in the sediments.

Riverine transport and water-sediment exchange of polycyclic aromatic hydrocarbons (PAHs) along the middle-lower Yangtze River, China

We examined the riverine transport of polycyclic aromatic hydrocarbons (PAHs) based on their spatial-temporal distributions in water and sediments from the mainstream along the middle and lower Yangtze River. According to the fugacity fraction (ff) estimation, sediments performed as a secondary emission source of two-, three-, and four-ringed PAHs and as a sink for five- and six-ringed congeners, leading to higher ecological and human health risks especially towards the lower reaches. The higher PAH levels observed in the more developed delta and megacities were highly linked to economic parameters. This was further supported by the source apportionment performed using the principal component analysis-multiple linear regression (PCA–MLR) model, which showed major contributions of coal and coke combustions along with vehicle emissions. The spatial-temporal distribution revealed that water runoff was the major contribution to PAHs transport along the middle-lower Yangtze River, whereas a sharp decrease in sediment discharge due to the dam impoundment along the upper reaches would lead to an increase in the catchment retention effect of PAHs. Hence, the biogeochemical processes of PAHs and their impacts on the fragile ecosystems as a consequence of the further modification of the sedimentary system in rivers need to be fully explored.

Sources and diffusive air–water exchange of polycyclic aromatic hydrocarbons in an oligotrophic North–Patagonian lake

Polycyclic aromatic hydrocarbons (PAHs) are semivolatile organic compounds of environmental concern. This study aims to investigate the influence of local sources of anthropogenic PAHs and their air–water exchange fluxes in an oligotrophic North–Patagonian lake in Chile. The monitoring was carried out in Panguipulli Lake during a six-month period during the autumn and winter seasons (March to August 2017) using a high–volume air sampler and a pump system for water samples. We detected and quantified fifteen PAHs in the gas phase (mean ∑15PAHs = 11.6 ng m−3) and dissolved water phase (mean ∑15PAHs = 961.8 pg L−1). Methylphenanthrenes and pyrene dominated the concentrations of PAHs in the studied phases. To determine sources of PAHs we used the PAH ratios of Light Molecular Weight/Heavy Molecular Weight (∑LMW/∑HMW) and Phenanthrene/Anthracene (Phe/Ant). The PAH ratio results revealed a pyrogenic source. We estimated the air–water diffusive exchange fluxes and fugacity ratios for the studied compounds. In general, air–water diffusive exchanges of PAHs showed a net volatilization for the less hydrophobic (log KOW < 4) and lighter PAHs (MW ≤ 170 g mol−1), and a net deposition trend for the more hydrophobic (log KOW 4–7) and higher molecular weight PAHs (MW ≥ 178 g mol−1). We found a significant correlation between log water/air fugacity ratios and log KOW of PAHs. Therefore, it is suggested that this oligotrophic lake acts as a sink by accumulating hydrophobic and mid-high molecular weight PAHs derived mainly from pyrogenic sources. This study is the first attempt to understand the sources and behavior of PAHs in oligotrophic lakes in the Southern Chile where information is scarce regarding the occurrence of PAHs.

Distribution, sources, and behavior of PAHs in estuarine water systems exemplified by Salt River, Taiwan

Water, suspended particulate matter (SPM), and sediment samples were collected from Salt River in Taiwan and analyzed the concentrations of 16 types of polycyclic aromatic hydrocarbons (PAHs). The analysis results were used to examine the distribution, source, partition behavior, and potential ecological risks of PAHs in the estuarine water systems. The mean concentration of total PAHs in water, SPM, and sediment samples was 0.485–10.2 μg/L, 26.7–169 mg/kg dw, and 0.343–29.4 mg/kg dw, respectively. The highest concentration was found at the river mouth and decreased toward the river and sea with the tide. The distribution of the diagnostic ratios of PAHs showed that the combustion of coal and petroleum products are the main sources of PAHs in Salt River. The in site organic carbon normalized partition coefficients for SPM-water (K'oc(SPMW)) and sediment-water (K'oc(SedW)) were 2.8–4.5 and 4.6–6.0 (log units), respectively, increasing with the number of rings in PAHs. The values log K'oc(SedW) and log K'oc(SPM-W) showed a significant linear correlation with their octanol-water partition coefficients (p < 0.01), and their slopes were 0.427 and 0.316, respectively. The fugacity fraction was used to evaluate the exchange of PAHs in water-SPM-sediment systems. Results showed that in SPM, 2–4-ring PAHs tend to be released into water, whereas 5–6-ring PAHs in water tend to be adsorbed onto SPM. The exchange of PAHs between water and sediment occurs in the direction of adsorption onto sediment from water. The assessment of the mean risk quotient, total toxicity equivalence, and mean effect range-median quotient of PAHs showed that the PAHs in the water and SPM of Salt River may have moderate to high ecological risk. In sediment, PAHs in the lower reaches and estuary may pose moderate to high ecological risk, whereas PAHs in the middle and upper reaches show low to moderate ecological risk.

Soil concentrations and soil-air exchange of polycyclic aromatic hydrocarbons in five Asian countries

The Asia Soil and Air Monitoring Program (Asia-SAMP) is a large-scale monitoring program spanning China, Japan, South Korea, Vietnam and India. 47 polycyclic aromatic hydrocarbons (PAHs) were analyzed in 169 concurrently collected surface soil samples across the five study regions. Total PAH concentrations (∑47PAHs) ranged from 13.1 to 7310 ng/g dry weight, with a median value of 272 ng/g dry weight. Higher concentrations of ΣPAHs were recorded in soils from urban areas, followed by soils from rural areas and background soils. Low correlation coefficients were found between PAHs concentrations with population density, surface air temperature and soil organic content. A trend of depleting high molecular weight PAHs and enrichment of low molecular weight PAHs occurred from east to west in Chinese soils. Based on atmospheric PAHs detected in almost the same sampling sites, the equilibrium status of PAHs in the atmosphere and on the ground was investigated. Sample sites with a soil-air equilibrium status for different PAH congeners recorded differences, and differences were recorded between seasons. 2-ring PAHs were mainly volatilized, and 5- & 6-ring PAHs were mainly deposited in all seasons and across all study regions. 3- & 4-ring PAHs were more affected by soil-air transfer, showing a tendency to accumulate in soils in cold regions/seasons and to be re-volatilized into the atmosphere in warm regions/seasons. Partitioning and exchange of PAHs among soil and air were significantly affected by the air temperature.

Atmospheric Concentrations and Air-Soil Exchange of Polycyclic Aromatic Hydrocarbons (PAHs) in Typical Urban-Rural Fringe of Wuhan-Ezhou Region, Central China.

During the summer of 2015, polycyclic aromatic hydrocarbons (PAHs) in the atmosphere were collected by passive air samplers in typical urban-rural fringe of Wuhan-Ezhou region, Central China. The results showed that 16 kinds of PAHs were ubiquitouswith the concentrations of ∑16PAHs from 14.69 to 136.30ng·m-3 and the mean concentration of 43.03ng·m-3. Phenanthrene (Phe), fluoranthene (Fla) and pyrene (Pyr) were major components, which accounted for 81% of ∑16PAHs. PAHs atmospheric concentrations presented obvious spatial variation, being significantly related to geographical environment and influenced by anthropogenic activity. Air-soil exchange status of PAHs was discussed according to the fugacity fraction (ff). The results showed that HMW-PAHs behaved as net deposition, while LMW-PAHs were more likely to establish dynamic equilibrium between atmosphere and soil than MMW-PAHs and HMW-PAHs. For some PAHs, such as acenaphthylene (Acy) and anthracene (Ant), the soil acted as second sources of them.

Tidal variability of polycyclic aromatic hydrocarbons and organophosphate esters in the coastal seawater of Dalian, China

We investigated the tidal variability of polycyclic aromatic hydrocarbons (PAHs) and organophosphate esters (OPEs) in water dissolved phase from a coastal area of Dalian, China, as well as their air-water exchange trends. The concentrations of PAHs and OPEs in water were in the range of 50.5–74.7 ng/L and 21.6–61.5 ng/L, respectively. Phenanthrene (PHE) was the dominant congener followed by fluorene (FLU) for PAHs, while tris(2-chloroisopropyl) phosphate (TCIPP) and tris(2-chloroethyl) phosphate (TCEP) dominated for OPEs. PAHs in coastal water showed a tidal variability, but not for OPEs, which may due to the influence of occasional wastewater discharges of OPEs. The source apportionments using principle component analysis and positive matrix factorization suggested that PAHs in the coastal water mainly came from oil spill from ships, coal combustion, and petroleum combustion, while OPEs were derived from diverse sources. The fugacity fractions (ff) suggested that ACY, ACE, FLU, PHE, TCEP, and TPHP volatilized from water into air, while TNBP, TCIPP, and TDCIPP deposited from air into water, and FLA, PYR, BaA, CHR, and EHDPP reached equilibrium. The ff values varied slightly with tidal circle, but the variations were not enough to alter the air-water exchange directions of those compounds. Although the influences of tide on the air-water exchange of PAHs and OPEs were limited, tide still played an important role on the transports and diffusions of those chemicals in the coastal water, which requires further studies.

Air-soil diffusive exchange of PAHs in an urban park of Shanghai based on polyethylene passive sampling: Vertical distribution, vegetation influence and diffusive flux

Compared with dry and wet deposition rates, air-soil exchange fluxes cannot be directly measured experimentally. Polyethylene passive sampling was applied to assess transport directions and to measure concentration gradients in order to calculate diffusive fluxes of polycyclic aromatic hydrocarbons (PAHs) across the air-soil interface in an urban park of Shanghai, China. Seven campaigns with high spatial resolution sampling at 18 heights between 0 and 200 cm above the ground were conducted in 2017–2018. Air-to-soil deposition was observed, e.g. for phenanthrene, and soil-to-air volatilization for high molecular weight compounds, such as benzo[b]fluoranthene. Significant linear correlations between gaseous PAH concentration and log-transformed height were observed. Influence of vegetation on vertical concentration gradients of gaseous PAHs was insignificant in most cases except during the growing season. Local micrometeorological conditions resulted in a directional eddy diffusion in air and then influenced vertical diffusion of gaseous PAHs. Furthermore, the vertical eddy diffusivity was estimated as a function of distance to the air-soil surface. Air-soil exchange fluxes based on the Mackay's fugacity approach were calculated and confirmed by diffusive fluxes within air layer based on vertical concentration gradient of PAHs and eddy/molecular diffusion. Polyethylene passive sampling technology provides a useful tool to investigate air-soil exchange process.

Polycyclic aromatic hydrocarbons in two polluted lagoons, eastern coast of the Red Sea: Levels, probable sources, dry deposition fluxes and air-water exchange

The air-water exchange of polycyclic aromatic hydrocarbons (PAHs) is an important process in determining the fate, transport and chemical loadings of these contaminants in the atmosphere and water bodies. Concentration levels of PAHs in air (gaseous and particulate) and surface water were investigated in the environments of two polluted lagoons along the eastern coast of the Red Sea to study air water exchange and dry deposition fluxes. Nine priority parent PAHs and nine methylated PAHs were identified and quantified by GC-MS. The range of total PAHs in surface water was from 120.29 ng L−1 to 524.45 ng L−1 (average: 308.7 ng L−1, n = 19). The PAHs levels in air recorded significant rise form the previous study. The probable sources of dissolved PAHs in water were found predominantly to be of petrogenic origin in one lagoon and of pyrogenic origin in the other lagoon. The dry deposition fluxes for individual congeners ranged between 0.01 ng m−2d−1 to 2.82 μg m−2d−1. After Henry's law constant corrections for temperature and salinity; the air-water exchange fluxes were found in the range of −9.7 × 104 to 8.6 × 106 ngm−2d−1 with an average of 6.8 × 105 ngm−2d−1. Beside the other sources of PAHs in the studied lagoons, high temperature and wastewater dumping might affect the magnitude and direction of air-water exchange fluxes.

Seasonal atmospheric deposition and air–sea gas exchange of polycyclic aromatic hydrocarbons over the Yangtze River Estuary, East China Sea: Implications for source–sink processes

In this work, air samples and surface seawater samples covering four seasons from March 2014 to January 2015 were collected from a background receptor site in the YRE to explore the seasonal fluxes of air–sea gas exchange and dry and wet deposition of 15 polycyclic aromatic hydrocarbons (PAHs) and their source–sink processes at the air–sea interface. The average dry and wet deposition fluxes of 15 PAHs were estimated as 879 ± 1393 ng m−2 d−1 and 755 ± 545 ng m−2 d−1, respectively. Gaseous PAH release from seawater to the atmosphere averaged 3114 ± 1999 ng m−2 d−1 in a year round. The air–sea gas exchange of PAHs was the dominant process at the air–sea interface in the YRE as the magnitude of volatilization flux of PAHs exceeded that of total dry and wet deposition. The gas PAH exchange flux was dominated by three-ring PAHs, with the highest value in summer and lowest in winter, indicating a marked seasonal variation owing to differences in Henry's law constants associated with temperature, as well as wind speed and gaseous-dissolved gradient among seasons. Based on the simplified mass balance estimation, a net 11 tons y−1 of PAHs (mainly three-ring PAHs) were volatilized from seawater to the atmosphere in a ∼20,000 km2 area in the YRE. Other than the year-round Yangtze River input and ocean ship emissions, the selective release of low-molecular-weight PAHs from bottom sediments in winter due to resuspension triggered by the East Asian winter monsoon is another potential source of PAHs. This work suggests that the source–sink processes of PAHs at the air–sea interface in the YRE play a crucial role in regional cycling of PAHs.

Spatial variation of PAHs and PCBs in coastal air, seawater, and sediments in a heavily industrialized region

Concurrent coastal seawater (n=22), sediment (n=22), and atmospheric samples (n=10) were collected in the Aliaga industrial region, Turkey, to explore the spatial variation, sources, and air-seawater exchange of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). Seawater Σ16PAH concentrations (particle+dissolved) ranged between 5107 and 294,624pgL-1, while Σ41PCB concentrations were in the range of 880-50,829pgL-1. Levels in sediments were highly variable ranging between 35.5-49,682 and 2.7-2450μgkg-1 in dry weight for Σ16PAHs and Σ41PCBs, respectively. Atmospheric concentrations varied between 1791-274,974 and 104-20,083pgm-3 for Σ16PAHs and Σ41PCBs, respectively. Sediment organic matter (OM) content and levels of Σ16PAHs and Σ41PCBs correlated weakly (r 2=0.19-0.23, p<0.05) suggesting that the spatial variations of PAHs and PCBs were mainly affected by local sources rather than their sorption to OM. The geographical distribution of PAH and PCB concentrations in air, seawater, and sediment and factor analysis on the sediment levels pointed out that the major sources in the region are steel plants, petroleum refinery, petrochemical complex, ship breaking, loading/unloading activities at the ports, vehicular emissions, and fossil fuel combustion emissions. The direction of the air-seawater exchange was also explored by estimating seawater fugacity fractions of PAHs and PCBs. For PAHs, the number of cases implying deposition (43.0%) and volatilization (39.5%) was similar, while for PCBs, the number of cases implying volatilization (60.4%) was much higher compared to deposition (21.6%). Fugacity fractions were generally <0.36 (deposition) at the sites close to industrial and ship breaking activities where the highest seawater and sediment levels were measured, implying that atmospheric deposition is an important mechanism affecting seawater and sediment PAH and PCB levels.

Air-water exchange of PAHs and OPAHs at a superfund mega-site

Chemical fate is a concern at environmentally contaminated sites, but characterizing that fate can be difficult. Identifying and quantifying the movement of chemicals at the air-water interface are important steps in characterizing chemical fate. Superfund sites are often suspected sources of air pollution due to legacy sediment and water contamination. A quantitative assessment of polycyclic aromatic hydrocarbons (PAHs) and oxygenated PAH (OPAHs) diffusive flux in a river system that contains a Superfund Mega-site, and passes through residential, urban and agricultural land, has not been reported before. Here, passive sampling devices (PSDs) were used to measure 60 polycyclic aromatic hydrocarbons (PAHs) and 22 oxygenated PAH (OPAHs) in air and water. From these concentrations the magnitude and direction of contaminant flux between these two compartments was calculated. The magnitude of PAH flux was greater at sites near or within the Superfund Mega-site than outside of the Superfund Mega-site. The largest net individual PAH deposition at a single site was naphthalene at a rate of −14,200 (±5780) (ng/m2)/day. The estimated one-year total flux of phenanthrene was −7.9×105 (ng/m2)/year. Human health risk associated with inhalation of vapor phase PAHs and dermal exposure to PAHs in water were assessed by calculating benzo[a]pyrene equivalent concentrations. Excess lifetime cancer risk estimates show potential increased risk associated with exposure to PAHs at sites within and in close proximity to the Superfund Mega-site. Specifically, estimated excess lifetime cancer risk associated with dermal exposure and inhalation of PAHs was above 1 in 1 million within the Superfund Mega-site. The predominant depositional flux profile observed in this study suggests that the river water in this Superfund site is largely a sink for airborne PAHs, rather than a source.

Sediment-Water Exchange, Spatial Variations, and Ecological Risk Assessment of Polycyclic Aromatic Hydrocarbons (PAHs) in the Songhua River, China

The sediment-water exchange, spatial variations, and ecological risk of polycyclic aromatic hydrocarbons (PAHs) in the water and sediment of the Songhua River, China, were investigated and assessed in this paper. The fugacity fraction (ff) was used to evaluate the sediment–water exchange of PAHs between the water and sediment. The results suggest that the values of ff decreased with an increasing number of PAH rings. The sediment acts as a secondary emission source for three- and four-ring PAHs, whereas five-ring PAHs were deposited in the sediment from the water. The high ff values of PAHs found in autumn suggest large releases of PAHs after abundant deposition in summer, and the lowest ff values of PAHs occurred in summer. The values were especially low for five- and six-ring PAHs, which exhibited considerable deposition from the water to the sediment. PAHs with low molecular weights showed strong variations, which were potentially caused by their active physical-chemical properties. Additionally, high molecular weight BaP displayed weak variations, increasing the potential risk in the sediment. The simplified qualitative method of Cwater/Csediment is useful for assessing variations in the sediment–water exchange. The relationships between Cwater/Csediment and ff were investigated by determining the Pearson correlation coefficients (R). The results exhibited a significant negative correlation, with R = −1.000 and P = 0.000 for Flu, R = −0.993 and P = 0.007 for Phe, R = −0.998 and P = 0.002 for FlA, and R = −0.971 and P = 0.029 for BaP. The coefficients of variation indicated that five-ring PAHs were more sensitive than three- and four-ring PAHs. Thus, these low-ring PAHs can be easily exchanged between the sediment and the water. Additionally, the ecological risk of PAHs to aquatic organisms in the Songhua River is relatively low.

Exchange of polycyclic aromatic hydrocarbons across the air-water interface in the Bohai and Yellow Seas

In this study, air and surface seawater samples collected from the Bohai (BS) and Yellow Seas (YS) in May 2012 were determined exchange of PAHs, especially of low-molecular-weight (LMW) PAHs (three- and four-ring PAHs) at the air-water interface. Net volatilization fluxes of LMW PAHs were 266–1454 ng/m2/d and decreased with distance from the coast, indicating that these PAHs transported from coastal runoff were potential contributors to the atmosphere in the BS and YS. Moreover, LMW PAHs were enriched in the dissolved phase compared with those in the particulate phase in the water column, possibly suggesting that the volatilized LMW PAHs were directly derived from wastewater discharge or petroleum pollution rather than released from contaminated sediments. The air–sea exchange fluxes of the three-ring PAHs were 2- to 20-fold higher than their atmospheric deposition fluxes in the BS and YS. The input to and output from the water reached equilibrium for four-ring PAHs. Differently, five- and six-ring PAHs were introduced into the marine environment primarily through dry and wet deposition, indicating that the water column was still a sink of these PAHs from the surrounding atmosphere.

Seasonal variation in diffusive exchange of polycyclic aromatic hydrocarbons across the air–seawater interface in coastal urban area

Concentrations of 15 polycyclic aromatic hydrocarbons (PAHs) in air–seawater interface were measured over 1year in the coastal region of Incheon, South Korea. Most individual PAHs and total PAHs in air displayed statistically significant negative correlations with temperature, but not significant in seawater. Less hydrophobic compounds with three rings were at or near equilibrium in summer, while PAHs with four to six rings were in disequilibrium in all seasons, with higher fugacity gradients in colder seasons and for more hydrophobic compounds. Differently from fugacity gradients, the highest net fluxes occurred for some three- and four-ring PAHs showing the highest atmospheric concentrations. Net gaseous exchange, which was higher in winter, occurred from air to seawater with an annual cumulative flux of 2075μg/m2/year (for Σ15PAHs), indicating that atmospheric PAHs in this region, originating from coal/biomass combustion, can deteriorate the quality of seawater and sediment.