Release Of Polycyclic Aromatic Hydrocarbons Research Articles

Dermal bioaccessibility and absorption of polycyclic aromatic hydrocarbons (PAHs) in indoor dust and its implication in risk assessment

Numerous studies have focused on assessing the risk of human exposure to polycyclic aromatic hydrocarbons (PAHs) in indoor dust via dermal contact. However, the dermal bioaccessibility and dermal absorption of PAHs in indoor dust have seldom been reported. In the present study, the effects of temperature, sweat ratio, solid-liquid ratio and incubation time on the dermal bioaccessibility of PAHs were examined. Naphthalene, phenanthrene, pyrene and benzo[a]pyrenewere selected for examination in an absorption assay with keratinocyte cells. The results showed the release of PAHs from indoor dust fitted a first-order one-compartment model. Naphthalene had the highest rate of release, which was consistent with the bioaccessibility assay results. In addition, the absorption rate of naphthalene and phenanthrene by keratinocytes was higher than that of pyrene and benzo[a]pyrene, with the latter being of higher molecular weight. These results indicated that low molecular weight PAHs were much more easily absorbed via dermal contact than were high molecular weight PAHs. The dermal bioavailability of PAHs in indoor dust was estimated by multiplying the bioaccessibility of PAHs in indoor dust by the ratio of dermal absorption by skin cells, and ranged from 0.12 to 51.0%. These data will be useful in risk assessments.

A facile cooling-assisted solid-phase microextraction device for solvent-free sampling of polycyclic aromatic hydrocarbons from soil based on matrix solid-phase dispersion technique

Solvent-free analysis of organic pollutants from a complex matrix has attracted significant attention. In this work, we designed and fabricated a facile cooling-assisted solid-phase microextraction device (CA-SPME) that could be used for the solvent-free extraction of volatile and semivolatile compounds from a complex matrix using a commercial SPME probe. Determination of polycyclic aromatic hydrocarbons (PAHs) from soil samples was carried out to evaluate the performance of the designed CA-SPME device. The effects of heating temperature, cooling temperature, extraction time, and moisture content in soil on extraction efficiency were investigated. To enhance the extraction efficiency of the targeted analytes, the matrix solid-phase dispersion technique (MSPD) by grinding soil with silica gels was applied. The results showed that grinding with silica gels promoted the release of PAHs from the soil matrix to the headspace by disrupting the matrix structure, which then facilitated the extraction efficiency. Under optimized conditions, for all of the targeted PAHs, the method exhibited good linearity (40–4000 ng g−1) with regression coefficients (R2) ranging from 0.9586 to 0.9964. The limits of detection and limits of quantification ranged from 4.2 to 8.5 ng g−1 and 14.0–28.5 ng g−1, respectively. Relative standard deviations corresponding to the analysis of spiked soil samples (n = 5) were 8.1–13.4%. The solvent-free analysis of the certified soil sample using the proposed method demonstrated satisfactory results.

Reduction of polycyclic aromatic hydrocarbons (PAHs) emission from household coal combustion using ferroferric oxide as a coal burning additive

Household coal combustion is identified to be the second largest emission source of polycyclic aromatic hydrocarbons (PAHs) in China. In this study, ferroferric oxide (Fe3O4) was used as a coal burning additive to reduce PAHs emission from coal combustion in a household coal stove. The results showed that Fe3O4 participated in the coal combustion process. The addition of Fe3O4 reduced the release of PAHs during the coal combustion process, and could improve the residence capacity of ash residue to these PAHs. Toxic equivalent quantity (TEQ) of PAHs in flue gas from combustion of coal mixed with Fe3O4 was less than that from the raw coal combustion. For a typical combustion temperature of 850 °C, the TEQ of PAHs for the mixture of coal and 2.0 wt% Fe3O4 decreased 21.98% compared to that for the raw coal. The abundant active surface oxygen species originated from the phase transformation of iron oxides probably accelerated the cracking of PAHs, and hence led to the reduction of PAH emissions and their TEQ. The study could help to develop new technology for reduction of PAHs emission from household coal combustion.

Physiological and biochemical responses of Amaranthus cruentus to polycyclic aromatic hydrocarbon pollution caused by thermal power units.

Pollution due to release of polycyclic aromatic hydrocarbons from thermal power plants is a major global issue as the same is highly toxic and carcinogenic. The current research aims to investigate the responses of a dietary plant Amaranthus cruentus towards PAH pollution. For the said purpose, the plant was collected from agricultural land in close vicinity to thermal power units and the effects of PAH pollution on its chlorophyll and various nutraceutical content was evaluated. Oxidative stress biomarkers and antioxidant defense enzymes status and PAH accumulation was quantified as well. Real-time evidence of cell death, depletion of nutraceutical resources, and stomata configuration was generated through various histochemical studies and SEM analysis. Results indicated significant decline of chlorophyll a to the extent of 77% when compared to control. Oxidative stress markers, namely, superoxide radical, H2O2, and hydroxyl radical in pollution exposed plants were 12.7, 2.2, and 2.4 times respectively higher over the control which eventually resulted in 35% more cell death for the pollution exposed group. Total phenolics and flavonoids showed a decline of 57.6% and 41.3% respectively in the group exposed to PAH pollution. Similar decreasing trend was also observed for ascorbic acid, α-tocopherol, β-carotene, total proteins, and carbohydrate contents as well. PAH-induced stress also resulted in complete imbalance in the redox homeostasis of the plant which was evident from increase in super oxide dismutase, catalase, and peroxidase antioxidant enzymes by more than 2-fold when compared to control. PAH accumulation in sample group was 10-20 times more when compared to control. Proteomic analysis also indicated upregulation of some proteins related to stress situation. Results are evident of the fact that severe depletion of nutraceutical resources of dietary plants can take place if subjected to oxidative stress arising from PAH pollution.

Physicochemical properties and sorption capacities of sawdust-based biochars and commercial activated carbons towards ethoxylated alkylphenols and their phenolic metabolites in effluent wastewater from a textile district

Three biochars were produced using sawdust from waste biomass, via a simple pyrolysis thermal conversion at 450, 650, and 850 °C (BC450, BC650, and BC850), without any activation process. These materials, together with vegetal and mineral commercial activated carbons (VAC and MAC), were characterized for their elemental composition, Brunauer–Emmett–Teller surface area, t-plot microporosity and Barrett-Joyner-Halenda mesoporosity. Moreover, iodine, phenol and methylene blue porosity indexes were measured. The materials were also evaluated for their pH of the point of zero charge, as well as near-surface chemical composition and surface functionality by means of X-ray photoelectron and Fourier-transform infrared spectroscopy. Ash content, water-extractable metals and polycyclic aromatic hydrocarbons (PAHs) were also determined. BC650 showed a much higher surface area (319 m2 g−1) compared to BC450 (102 m2 g−1), as well as an increase in aromatization and the residual presence of functional polar groups. BC850 exhibited a loss of polar and aromatic groups, with the dominance of graphitic carbon and the highest value of surface area (419 m2 g−1). Biochars comply with the EN 12915-1/2009 limits for metal and PAH release in water treatment. Biochars and MAC were tested using Langmuir and Freundlich isotherms for the sorption in real effluent wastewater of a mixture of 14 branched ethoxylated 4-t-octyl and 4-nonylphenols, as well as 4-t-octyl and 4-nonylphenol, the latter representing persistent, endocrine disrupting contaminants, widespread in the effluents from wastewater treatment plants and listed as priority/priority hazardous substances in the Directive 2013/39/EU. Biochars showed a lower sorption efficiency compared to MAC. The best performance was found for BC650 towards the alkylphenols (9–13 times less efficient than the MAC). Considering the lower market price of biochar compared to MAC (estimated as at least 16 times less expensive by a small market survey), the former can be considered more competitive than the latter.

The Influence of Soil Mechanical Redesigning on Polycyclic Aromatic Hydrocarbon (PAH) Release: a Column Approach

Intrinsic molecular parameters (solubility, chemical structure, etc.) as well as physico-chemical properties of the medium (lithology, permeability, organic matter content, etc.) and hydrological specificities (rainfall regimes) are usually put forward to characterize the mobility of polycyclic aromatic hydrocarbons (PAHs). Here, we study the role of aggregate mechanical redesigning on the ability of anciently impacted soils to release polycyclic hydrocarbons. Soil columns were collected in a heavily impacted wasteland (Villeneuve la Garenne, France) for this purpose and submitted to continuous and sequential leaching regimes. The soil’s organo-mineral properties were characterized with suited techniques (Rock Eval, FT/IR) prior to the leaching experiments. The release of 18 PAHs (naphthalene, 1 methyl naphthalene, 2 methyl naphthalene, acenaphtylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz(a)anthracene, chrysene, benz(b)fluoranthene, benz(k)fluoranthene; benzo(a)pyrene, indeno[1,2,3-cd]pyrene, dibenz(a,h)anthracene, benzo(g,h,i) perylene) was assayed under non-disturbed configuration of the columns, then under reshuffled (10 mm), and finely sieved (4 mm) states in order to evaluate the impact of grain redistribution on the mobilization of the aromatic molecules. For both sequential and continuous leaching regimes, results showed a substantial increase of released amounts when the systems were disturbed. Significant increases of PAH concentrations were indeed observed when the columns were reshuffled (10 mm). The release was more intense when the mechanical reworking was performed with a smaller threshold (4 mm). Greater accessibility of the molecules drove very likely PAH release during the mechanical reworking operations.

Molecular-Dynamics Simulation Approach to Identifying PAH Release from Asphalt Concrete Pavements due to Mechanical and Environmental Factors

AbstractAsphalt is a primary source of polycyclic aromatic hydrocarbons (PAHs) in urban runoff originating mainly from asphalt concrete (AC) pavements and parking lots. High levels of PAHs have bee...

Leaching of polycyclic aromatic hydrocarbons (PAHs) from sewage sludge-derived biochar

Polycyclic aromatic hydrocarbons (PAHs), a family of persistent organic pollutants with various negative health effects, are inherently formed during biochar pyrolysis. However, the knowledge regarding the leaching potentials and mechanisms of PAHs remains limited for biochar implementation to soil. In this study we evaluated the leaching behaviors of PAHs from sewage sludge-derived biochar pyrolyzed at different temperatures (300–700 °C) using the protocol of Synthetic Precipitation Leaching Procedure (SPLP) with deionized water. Leachate concentrations of sixteen U.S. Environmental Protection Agency PAHs increased with the increasing pyrolysis temperature, exhibiting an opposite pyrolytic temperature dependence with their concentrations in biochar. The total leachate PAH concentration peaked at 700 °C with 11.75 μg/L, corresponding to 15.9% of total PAHs present in biochar. PAH leaching was associated with the release of hydrophobic organic compounds (HOCs) that created a mobile phase to facilitate the mobilization of PAHs into water. The enhanced release of calcium, aluminum, and barium from the biochars with pyrolysis temperature could also favor the leaching of biochar PAHs, due to the destruction of HOCs-(metal ions)-mineral linkages, which improved the release of HOCs and HOCs-bound PAHs; and because the extent of metal cross-linking in biochar is reduced, enabling better diffusion of PAHs through the inner matrix and thus accelerating their desorption.

Turnover and legacy of sediment-associated PAH in a baseflow-dominated river

Polycyclic Aromatic Hydrocarbons (PAH) ubiquitously occur in rivers and threaten the aquatic ecosystem. Understanding their fate and behaviour in rivers can help in improving management strategies. We develop a particle-facilitated transport model considering suspended sediments with sorbed PAH from different origins to investigate the turnover and legacy of sediment-bound PAH in the baseflow-dominated Ammer River in southwest Germany. Our model identifies the contributions of dissolved and particle-bound PAH during wet and dry periods to the annual load. The analysis of in-stream processes enables investigating the average turnover times of sediments and attached PAH for the main stem of the river. The legacy of sediment-bound PAH is studied by running the model assuming a 50% reduction in PAH emissions after the introduction of environmental regulation in the 1970s. Our results show that sediment-bound and dissolved PAH account for 75% and 25% of the annual PAH load, respectively. PAH are mainly emitted from urban areas that contribute over 74% to the total load. In steep reaches, the turnover times of sediments and attached PAH are similar, whereas they differ by 1–2 orders of magnitude in reaches with very mild slopes. Flow rates significantly affect PAH fluxes between the mobile water and the riverbed over the entire river. Total PAH fluxes from the river bed to the mobile water are simulated to occur when the discharge is larger than 5 m3s −1. River segments with large sediment storage show a potential of PAH legacy, which may have caused a PAH release over 10–20 years after the implementation of environmental regulation. This study is useful for assessing environmental impacts of PAH in rivers (e.g., their contribution to the river-water toxicity) and exemplifies that the longitudinal distribution, turnover, and legacy potential of PAH in a river system require a mechanistic understanding of river hydraulics and sediment transport.

Release of polycyclic aromatic hydrocarbons from biochar fine particles in simulated lung fluids: Implications for bioavailability and risks of airborne aromatics

Airborne carbonaceous fine particles, such as soot and biochar, represent a significant fraction of air particulate matter and have received widespread concern due to their health effects. Atmospheric carbonaceous particles can contain high concentration of polycyclic aromatic hydrocarbons (PAHs), and may pose significant health risks when carried into respiratory system from inhalation of particulates. In this study, the bioaccessibility of two PAH compounds, phenanthrene and pyrene, bound to biochar fine particles was assessed by examining their release in two simulated lung fluids: Gamble's solution and artificial lysosomal fluid (ALF). We observed that only 0.47 to 0.75% of biochar-bound PAHs were released in the simulated lung fluids, most likely due to the physical entrapment of PAH molecules in the micropore regimes of biochar, resulting in strong desorption hysteresis, even though apparent desorption equilibrium was reached within 30 min, well within the average clearance time of particulate matter in lung system. The inorganic and organic salts in the simulated lung fluids were found to inhibit the release of PAHs by exerting the pore blockage effect and salting-out effect. Moreover, the low molecular weight organic acids (LMWOAs) in the lung fluids further inhibited PAH release by increasing the micropore volume and surface area of biochar fine particles. When taking into account the inhibited release, the estimated carcinogenic risks of biochar-bound PAHs are typically low, even under extreme conditions wherein both biochar concentrations and PAH loadings on biochar are very high. An important implication is that contaminant bioavailability needs to be taken into account when assessing the risks of the contaminants bound to airborne carbonaceous materials.

Aging as the main factor controlling PAH and polar-PAC (polycyclic aromatic compound) release mechanisms in historically coal-tar-contaminated soils.

In industrial sites, historically contaminated by coal tar (abandoned coking and manufactured gas plants), other families of organic pollutants than the 16 PAHs (polycyclic aromatic hydrocarbons) classified by the US-EPA can occur and induce potential risk for groundwater resources. Polar PACs (polycyclic aromatic compounds), especially oxygenated and nitrogenated PACs (O-PACs and N-PACs), are present in the initial pollution and can also be generated over time (i.e., O-PACs). Their aqueous solubilities are much greater than those of the PAHs. For these reasons, we need to increase our knowledge on polar PACs in order to better predict their behavior and the potential on-site risk. Batch leaching tests were carried out under various conditions of temperature, ionic strength, and availability of pollutants to determine the mechanisms and key parameters controlling their release. The results show a release of low-molecular-weight PAHs and polar PACs mainly by dissolution, while higher molecular weight PAHs are mainly released in association with colloids. Aging mainly controls the former mechanism, and ionic strength mainly controls the latter. Temperature increased both dissolution and colloidal mobilization. The Raoult law predicts the PAC equilibrium concentration for soils presenting high pollutant availability, but this law overestimates PAC concentration in aged soils (low pollutant availability). This is mainly due to limitation of PAC diffusion within coal-tar particles with aging. The most soluble PACs (especially polar PACs) are the most sensitive to aging. For better prediction of the PAC behavior in soils and water resources management, aging needs to be taken into account.

Impact of suspended sediment on the behavior of polycyclic aromatic hydrocarbons in the Yellow River: Spatial distribution, transport and fate

A total of 150 samples were collected from 25 sites in the Yellow River of Henan Province during 2014 to demonstrate the impact of suspended sediment (SS) load on the behavior of semi-volatile organic compounds (SVOCs) in the Yellow River. The average concentrations of SS ranged from <0.01 g/L to 1.7 g/L and the total loading/removal of SS was 108 Mt in the Henan section of the Yellow River. The sixteen polycyclic aromatic hydrocarbons (PAHs) were detected with concentrations of 23-370 ng/L in the dissolved phase and 36–3700 ng/g dw in the particulate phase, respectively. The concentrations of ∑16PAHs (sum of PAHs in the dissolved and particulate phase) along the river flow showed a decreasing trend and then an increasingly varied SS concentration. In the SS-abundant section, PAHs were released from the particle phase to the dissolved phase. Based on the mass balance of water and SS, 43% of the total load of PAHs is ascribed to the scouring processes, indicating that PAHs release from river-bed soil to the Yellow River is significant.

Application of biochar to soils may result in plant contamination and human cancer risk due to exposure of polycyclic aromatic hydrocarbons

Biochars are added to soil to improve agronomic yield. This greenhouse- and field-scale study evaluated polycyclic aromatic hydrocarbon (PAH) contamination in 35 commercial and laboratory-produced biochars, and assessed the effects of biochar amendment of soils on PAH accumulation in vegetables and the risk for cancer. The total and bioavailable PAH concentrations in biochars varied from 638 to 12,347 μg/kg and from below the detection limit (BDL) to 2792 μg/kg, respectively. PAH formation in biochars decreased with increasing production temperature (350–650 °C). Root exudates enhanced PAH release from biochars. The total PAH concentrations in eight edible vegetables growing in biochar-amended soil varied according to biochar and vegetables type from BDL to 565 μg/kg. A health risk assessment framework was integrated with the benzo[a]pyrene toxic equivalency quotient and the incremental lifetime cancer risk (ILCR) to estimate the exposure risk for human beings via ingestion of PAH-contaminated vegetables. The total ILCR for adults was above 10−6, which suggests a risk to human health from direct exposure to PAHs in vegetables grown in biochar-amended soil. These results demonstrate that biochar application may lead to contamination of plants with PAHs, which represents a risk to human health. The PAH levels in biochars produced using different conditions and/or feedstocks need to be evaluated and biochars should be pretreated to remove PAHs before their large-scale agronomic application.

Remobilization and bioavailability of polycyclic aromatic hydrocarbons from estuarine sediments under the effects of Nereis diversicolor bioturbation

The effects of Nereis diversicolor bioturbation on the remobilization and bioavailability of polycyclic aromatic hydrocarbons from estuarine sediment were determined after 60 d in a laboratory experiment. The release fluxes and mass transfer coefficients showed that bioturbation by N. diversicolor can lead to a significant remobilization of polycyclic aromatic hydrocarbons (PAHs) from estuarine sediments. Bioturbation enhanced the release of PAHs from sediment to water by accelerating the transport of sediment particles to the sediment-water interface followed by PAHs desorption to the water. The bioavailability of PAHs was described by SPMD-sediment accumulation factors (SSAF). The SSAF of low molecular weight PAHs with bioturbation was significantly higher than that of PAHs without bioturbation, and there were no significant variations in high-molecular-weight PAHs. Our results revealed that N. diversicolor bioturbation significantly increased PAHs release from sediment to water but only increased the bioavailability of low-molecular-weight PAHs.

Impact of Lebanese practices in industry, agriculture and urbanization on soil toxicity. Evaluation of the Polycyclic Aromatic Hydrocarbons (PAHs) levels in soil

This study was carried out in order to investigate the toxicity on Lebanese soil and to show the impact of the anthropogenic activities, industrialization and urbanization, on the release of Polycyclic Aromatic Hydrocarbons (PAHs) in Lebanese soils. Hundred soil samples of different land use were screened for 17 PAHs using a UAE/GC-MS method. Detection frequency varied between 76 and 100% for most of the PAHs, where the ΣPAHs ranged from 33.5 to 4062.9 ng g−1. Moreover, BaPeq values varied between 0.93 and 332.4 ng g−1. BaPeq values in industrial and urban soils were 777 and 256 times higher than those in rural soil, respectively. None of the soil samples showed concentrations above the safe BaPeq value of 600 ng g−1. Significant decrease in concentration levels of ΣPAHs was obtained in the following order: Industrial, urban, traffic and agricultural. Furthermore, the relative high contribution of Chrysene, Benzo(a)Anthracene and Benzo(k)Fluoranthene in agricultural soils indicates that open burning remains an adopted way in Lebanon for disposal of agricultural residues, while the predominance of Benzo(ghi)Perylene and Benzo(b)Fluoranthene in industrial soils suggests the broad use of diesel powered engines in the Lebanese industrial sector. The ratios of Low Molecular Weight/High Molecular Weight and fluoranthene/fluoranthene+pyrene (Fln/Fln+Pyr) showed that PAHs in soil samples are mainly pyrogenic and created during combustion of petrol, coal, wood and other biomasses.

Skin Surface Film Liquid as New Migration Medium for the Determination of PAHs Released from Rubber Containing Consumer Goods

ABSTRACTExposure of consumers, in particular children, to polycyclic aromatic hydrocarbons (PAHs) via contact with consumer products has been the subject of considerable public attention over the last years. Eight PAHs with a harmonized classification as carcinogen 1B, according to the Regulation EC No 1272/2008 on classification, labeling and packaging of substances and mixtures, have been identified in plastic and rubber contained in some consumer articles, such as toys, bicycle grips or sporting goods. These constitute a potential source for dermal, or even oral, exposure. Concerning the former, it is desirable to develop easy and reliable methods for migration determination using simulated environments that mimic as realistically as possible the hydro-lipidic film on human skin composed of aqueous sweat and sebum.This work proposes a protocol for the determination of PAH release from rubber using a migration simulant that mimics real skin conditions. Various compositions of skin surface film liquid (SSFL), a mixture of aqueous sweat and sebum, were tested for their stability and suitability for the measurements. The results indicated that SSFL containing 0.2% sebum showed good agreement with relative migration rates obtained using 20% ethanol, which in past studies has proved to be a valid migration medium for this purpose. The aqueous SSFL has the advantage that it does not interact with the elastomer sample matrix.The SSFL described in this work may serve as a migration simulant for future product-to-skin migration studies, in which the simulant's properties need to realistically reflect the conditions on human skin.

Adverse pregnancy outcomes in women with changing patterns of exposure to the emissions of a municipal waste incinerator

Municipal solid waste incinerators emissions contain pollutants that, despite their low concentration, might adversely affect reproductive health. In the present study, we examined rates of miscarriage and birth defects among women who resided or were employed in the vicinity of a municipal solid waste incinerator plant from 2003 to 2013. In 2009, a progressive shutdown of the old incineration lines and operation of a new line caused considerably higher atmospheric release of polycyclic aromatic hydrocarbons, particularly of dioxins, due to these irregular operating conditions, technological renovation, and increased capacity. We used dioxin emission levels, based on a dispersion model, to define exposure status of the residing population to air pollutants emitted by the waste incinerator. In women who resided in areas characterized by higher emission exposures compared with a referent area, the relative risk (RR) of miscarriage was 1.04 (95% confidence interval (CI) 0.80–1.32) based on 62 cases overall, with little evidence of a dose-response relation. RRs were similarly null for both 2003–2008 and 2010–2013 periods (RR 1.12 (95% CI 0.80–1.53) and 0.98 (95% CI 0.63–1.48), respectively). Concerning birth defects in the offspring of women residing in the exposed area, no evidence of increased risk emerged, since the prevalence ratio at birth was 0.64 (95% CI 0.29–1.26), with comparable results in the 2003–2008 and 2010–2013 period. Corresponding analyses carried out in municipal residents who worked in the exposed area confirmed these findings. We also did not detect abnormally high rates of miscarriage and birth defects in the exposed cohorts in the single year 2009.Overall, these results do not suggest an effect of exposure to the emissions of the municipal solid waste incinerator we investigated on two indicators of reproductive health. However, the limited statistical stability of the estimates and the absence of individual-based information on some potential confounders suggest caution in the interpretation of study findings.

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.

Mechanisms of biochar reducing the bioaccumulation of PAHs in rice from soil: Degradation stimulation vs immobilization

This study aimed to elucidate the mechanisms by which biochar reduces the bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) in rice under anaerobic conditions. Corn straw- or bamboo-derived biochar pyrolyzed at 300 °C and 700 °C (CB300 or BB700), respectively, was amended into flooded PAH-contaminated soil. After harvest, 2% CB300, 0.5% BB700 or 2% BB700 amendments reduced the bioaccumulation of PAHs in rice root, especially that of high-molecular-weight PAHs (p < .05). Total PAH concentrations were higher, and their bioavailable concentrations were lower in BB700-amended soils than the control. The stimulation of PAH desorption from BB by low-molecular-weight organic acids (LMWOAs) was gentle and did not significantly retard the adsorption of PAHs on BB700, indicating that BB700 reduced PAH bioavailability primarily via immobilization. The total and bioavailable concentrations of PAHs were both lower in the 2% CB300-treated soils than the control. LMWOAs facilitated PAH release from CB300-amended soils, thus increasing the bioavailability of immobilized PAHs. The relative abundances of the bacteria, functional genes, and methanogens involved in PAH anaerobic degradation were significantly higher in the 2% CB300 treatment than other treatments. Fast PAH dissipation in soil amended with 2% CB300 may be attributed to the increased bioavailability of immobilized PAHs and enhanced biodegradation, both of which were induced by LMWOAs and CB. In summary, biochar types and root presence jointly affected the mechanisms by which biochar reduced the bioaccumulation of PAHs in rice under anaerobic conditions.

Comparison of direct benthic flux to ebullition-facilitated flux of polycyclic aromatic hydrocarbons and heavy metals measured in the field

No studies to date have compared directly the ebullition-facilitated organic and metal contaminant fluxes to direct benthic contaminant fluxes measured in the field. To address this knowledge gap, we measured benthic organic and metal contaminant fluxes at the sediment-water interface and compared them to simultaneously measured ebullition-facilitated contaminant fluxes at nine sites in a contaminated waterway in the Chicago River, IL, USA, to determine the relative importance of each transport mechanism to total sediment release. Two benthic flux chambers with integrated gas ebullition samplers were built to measure both gas ebullition and in situ fluxes of polycyclic aromatic hydrocarbons (PAHs), metals, sulfide, ammonia, nitrate, dissolved organic carbon (DOC), total filtered phosphorus (TFP), and dissolved oxygen (DO) across the sediment-water interface over time. Aqueous pH and oxidation-reduction potential (ORP) within the chamber were also monitored. The gas ebullition collection system trapped heavy metals and the 16 United States Environmental Protection Agency (USEPA) priority-pollutant PAHs (Σ16PAH) transported with gas bubbles through sorption and particle entrainment on a pre-combusted glass wool trap as in our previous studies. The results demonstrate that gas ebullition contaminant transport is a significant source of pollution release to the water column, as great as or greater than direct benthic transport. In several sites, release rates of Σ16PAHs and some metals from the sediment by gas ebullition were more than an order of magnitude higher than from direct benthic release. The average total PAH ebullition-facilitated release of all sites is predicted to be nearly 0.5 g m−2 on an annual basis. Gas ebullition is an important pathway for release of PAHs and heavy metal pollutants to the water column and monitoring of this important release pathway should be performed to adequately address the true environmental impacts of polluted sediments.