Bioaccessibility Of Polycyclic Aromatic Hydrocarbons Research Articles

A method for measuring the bioaccessibility of polycyclic aromatic hydrocarbons in cell culture media

Airborne polycyclic aromatic hydrocarbons (PAHs) and their derivatives are of particular concern for population health due to their abundance and toxicity via inhalation. Lung toxicity testing includes exposing lung epithelial cell lines to PAHs in a culture medium containing inorganic species, lipids, proteins, and other biochemicals where the cell response is influenced among others by the toxic chemical accessibility in the medium. While inhalation bioaccessibility of PAHs and other toxicants was previously studied in surrogate lung fluids, studies measuring bioaccessibility in cell culture media are rare. In this work, a method was developed to characterize PAH bioaccessibility in a culture medium used for mouse lung epithelial (FE1) cells. Further, the optimised method was tested using commercially available standard reference material of urban particulate matter (PM) as well as polyurethane foam passive air samplers (PUF-PAS). The method provided a high precision and recovery of analytes, indicating no losses during sample processing and analysis. PAHs had non-linear concentration-responses, with the culture medium approaching saturation with PM concentration of 500 μg mL−1. The results showed that phenanthrene, a 3-ring PAH, was significantly more bioaccessible than ≥4-ring congeners in the culture medium (up to ∼2.5 folds; p < 0.05). Finally, using pre-deployed PUF-PAS from a residential and an industrial site, five PAHs were found in the culture medium, including naphthalene, phenanthrene, anthracene, fluoranthene, and pyrene. This work provides a proof of concept to enable future studies to assess the inhalation bioaccessibility of polycyclic aromatic compounds and other airborne pollutants collected using PUF-PAS.

Inhalation bioaccessibility and risk assessment for PM-bound organic components: Co-effects of component physicochemical properties, PM properties, and sources

Inhalation bioaccessibility and deposition in respiratory tracts of organic components in atmospheric particulate matter (PM) are key factors for accurately estimating health risks and understanding human exposures. This study evaluated the in-vitro inhalation bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) and PAH derivatives, phthalic acid esters (PAEs), polychlorinated biphenyls (PCBs), and organophosphate flame retardants (OPFRs) in size-resolved PM from a Chinese megacity. The bioaccessibility ranged from 0.2% to 77.8% in the heating period (HP), and from 0.7% to 94.2% in the non-heating period (NHP). Result suggests that less hydrophobic organics might be more bioaccessible. Bioaccessibility of medium logKow organics in sizes > 0.65 µm was significantly inhibited by high carbon fractions, indicating the co-effects. Then, this is the first study to explore effects of sources on inhalation bioaccessibility of organics. Coal and biomass combustion in HP and traffic emission in NHP negatively correlated with bioaccessibility. Secondary particles also negatively correlated with bioaccessibility of medium logKow organics. Incremental lifetime cancer risk (ILCR) and non-cancer risk (HQ) for all measured components in PM10 were estimated after considering the bioaccessibility and deposition efficiencies and the HQ and ILCR were within the acceptable range. BaP and DEHP were strong contributors to HQ and ILCR, respectively.

Oral Bioaccessibility of Polycyclic Aromatic Hydrocarbons in Fly Ash Derived from Incineration of Petroleum Products and Waste Motor Tyres

Aim: The aim of this study is to generate and investigate oral bioaccessibility based on the health risk of polycyclic aromatic hydrocarbon (PAHs) in fly ash from waste tyres and petroleum products in Rivers State, Nigeria.&#x0D; Study Design: Crude oil, crude oil asphalt, artisanal diesel, refined diesel, waste engine oil and waste tyres samples were collected and incinerated. The different fly ash samples were analyzed with GC-MS.&#x0D; Place and Duration of Study: Rivers State is a state that is rich in oil in the Niger Delta area of Nigeria. The State has been experiencing the release of soot into the environment for more than five (5) years now. This soot is noticeable to all residents of Port Harcourt and its environment with soot covering both indoor and outdoor objects such as clothes, cars, houses, floors, soil, water body, etc. The five (5) petroleum products and waste tyres samples were collected and incinerated for six (6) weeks (22nd of June to 7th of August 2021).&#x0D; Methodology: The petroleum products and waste tyres samples were collected and incinerated. The different fly ash samples were collected after combustion daily. The total and oral bioaccessible PAH concentrations were determined using GC-MS. The oral bioaccessibility of PAHs in the fly ash was evaluated using the physiologically-based extraction test method (PBET) to determine the bioaccessible concentrations of 16 priority US Environmental Protection Agency (USEPA) PAHs in fly ash samples. The results obtained for PAHs were used for health risk assessment.&#x0D; Results: A wider range of total PAH concentrations were observed in the six (6) fly ash samples from 49.71 to 926.62 mg/kg. The PAHs concentrations were significantly higher in higher molecular weight PAHs (with benzene of 4-5-6 rings) than lower molecular weight PAHs (benzene of 2-3 rings). Naphthalene, acenaphthylene, acenaphthene, and fluorene with 2-3 ring structures had the highest bioaccessible concentrations in both gastric and gastrointestinal phases of all the six fly ash samples studied. Flourene had the maximum percentage bioaccessibility of 91.30 % in the gastric phase from locally refined diesel fly ash whilst acenaphthene had a maximum percentage bioaccessibility of 98.75% in the gastrointestinal phase from crude oil asphalt fly ash.&#x0D; Conclusion: Data obtained from this study indicated that crude oil fly ash is a potential point source of toxic polycyclic aromatic hydrocarbons with significant levels of health risk to humans.

Effects of organic carbon/elemental carbon and particle size on inhalation bioaccessibility of particle-bound PAHs

Bioaccessible fractions of particle-bound hydrophobic organic compounds (HOCs) are critical to evaluating human inhalation exposure risk. However, the key factors for controlling the release of HOCs into the lung fluid are not adequately examined. To address this issue, eight particle size fractions (0.056–18 μm) from different particle emission sources (barbecue and smoking) were collected and incubated with an in vitro method for determining inhalation bioaccessibilities of polycyclic aromatic hydrocarbons (PAHs). The bioaccessible fractions of particle-bound PAHs were 35–65% for smoke-type charcoal, 24–62% for smokeless-type charcoal, and 44–96% for cigarette. The size distributions of bioaccessible fractions of 3–4 ring PAHs were symmetric with the patterns of their masses, characterized as a unimodal distribution with both the trough and peak at 0.56–1.0 μm. Analysis from machine learning showed that chemical hydrophobicity appeared to be the most significant factor affecting inhalation bioaccessibility of PAHs, followed by organic carbon and elemental carbon contents. Particle size seemed to have little effect on the bioaccessibility of PAHs. A compositional analysis of human inhalation exposure risk from total concentration, deposition concentration, and bioaccessible deposition concentration in alveolar region showed a shift in the key particle size from 0.56−1.0 μm to 1.0–1.8 μm and an increasing in the contributions of 2–3 ring PAHs to risk for cigarette due to the high bioaccessible fractions. These results suggested the significance of particle deposition efficiency and bioaccessible fractions of HOCs in risk assessment.

Nanoplastics Weathering and Polycyclic Aromatic Hydrocarbon Mobilization.

Despite increasing efforts to recycle plastic materials, large quantities of plastics waste continue to accumulate in the oceans. Persistent mechanical and photochemical degradation of plastics in the oceans yields micro- and nanoscale plastic particles, which represent potential vectors for mobilizing hydrophobic carcinogens in an aqueous milieu. Yet, the fate and potential threats associated with plastics remain largely unexplored. Herein, we apply an accelerated weathering protocol to consumer plastics to characterize the effect of photochemical weathering on the size, morphology, and chemical composition of nanoplastics under defined conditions and validate that the photochemical degradation is consistent with plastics harvested from the Pacific Ocean. Machine learning algorithms trained with accelerated weathering data successfully classify weathered plastics from nature. We demonstrate that photodegradation of poly(ethylene terephthalate) (PET)-containing plastics produces enough CO2 to induce a mineralization process that results in the deposition of CaCO3 on nanoplastics. Finally, we determine that despite UV-radiation induced photochemical degradation and mineral deposition, nanoplastics retain their ability to sorb, mobilize, and increase bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) in water and under simulated physiological gastric and intestinal conditions.

Assessment of the bioaccessibility of PAHs and other hazardous compounds present in recycled tire rubber employed in synthetic football fields.

Recycled tire crumb rubber (RTCR) surfaces contain harmful and carcinogenic substances, which can be ingested by the users of these facilities, mainly athletes and children. In this work, the potential in-vitro oral bioaccessibility of eighteen polycyclic aromatic hydrocarbons (PAHs) from RTCR employed as infill in synthetic football fields was studied in human synthetic body fluids (saliva, gastric, duodenal and bile), prepared according the Unified Bioaccessibility Method. Solid-phase extraction (SPE) using commercial sorbents and a new green material based on cork (cork industry by-product) were used to isolate the bioaccessible PAHs before gas chromatography-tandem mass spectrometry analysis. The method was optimized and validated attending the analytical figures of merit. The feasibility of cork biosorbent for the extraction of the compounds was demonstrated, as well as the suitability of the UBM method to perform the digestion with good precision. The application to real samples collected from football fields demonstrated the presence of 17 of the 18 target PAHs in the biofluids. Most volatile PAHs such as NAP, ACY, ACE, FLU, PHN and ANC, achieved the highest bioaccessibility percentage levels. The carcinogenic B[a]P was detected in 75 % of the samples at concentrations up to 2.5 ng g-1 (bioaccessible fraction). Children exposure assessment was carried out to identify potential risk. Other hazardous and environmentally problematic compounds such as N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone (6PPD-quinone), recently related with the dead of coho salmon, and hexamethoxymethylmelamine (HMMM), among others, were also detected. This is the first study in which the bioaccesibility from real crumb rubber samples of 15 out of the 16 PAHs considered as priority pollutants by the United States Environmental Protection Agency (EPA) and the presence of 6PPD-quinone and HMMM in the bioaccessible fractions is reported.

Bioaccessibility and Toxicity Assessment of Polycyclic Aromatic Hydrocarbons in Two Contaminated Sites.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous soil contaminants, and their bioaccessibility determines their environmental risks in contaminated land. In the present study, the residual concentrations of PAHs in the soils of two industrial sites were determined, and their bioaccessibility was estimated by the hydroxypropyl-β-cyclodextrin extraction (HPCD) extraction method. The results showed heavy PAH contamination at both site S1 (0.38-3342.5mgkg-1) and site S2 (0.2-138.18mgkg-1), of which high molecular weight (HMW) PAHs (4-, 5-, and 6-ring compounds) accounted for approximately 80%. The average bioaccessibility of PAHs at sites S1 and S2 was 52.02% and 29.28%, respectively. The bioaccessibility of certain PAH compounds decreased with increasing ring number of the molecule. Lower PAH bioaccessibility was detected in loamy and silty soil textures than in sandy soil. Moreover, among the soil properties, the dissolved organic matter, total organic carbon, total potassium, and total manganese concentrations had significant effects on the bioaccessibility of PAHs. The toxicity analysis showed that the composition and bioaccessibility of PAHs could affect their potential toxicity in soil. We suggest that bioaccessibility should be taken into consideration when assessing the toxicity of PAHs in soil, and more attention should be given to low-ring PAHs with high bioaccessibility.

Evaluating the inhalation bioaccessibility of traffic-impacted particulate matter-bound PAHs in a road tunnel by simulated lung fluids

Polycyclic aromatic hydrocarbons (PAHs) are the most highly concerned pollutants bound on traffic-impacted particulate matter (TIPM). The inhaled TIPM-bound PAHs risk has attracted much attention, whereas the inhalation bioaccessibility, a method to refine the exposure risk assessment, has not yet been extensively introduced in the exposure risk assessment. Thus, in vitro assays using artificial lung fluids including artificial lysosomal fluid (ALF), Gamble's solution (GS), and modified GS (MGS) were conducted to assess the inhalation bioaccessibility of USEPA 16 PAHs in TIPM collected from an expressway tunnel, the influence factors of PAHs' inhalation bioaccessibility were explored, and the exposure risk of TIPM-bound PAHs was estimated based on inhalation bioaccessibility. Results showed that the average PAHs concentrations were 30.5 ± 12.9 ng/m3, 36.2 ± 5.19 ng/m3, and 39.9 ± 4.31 ng/m3 in the tunnel inlet PM2.5, TSP, and tunnel center PM2.5, respectively. Phe, Flt, Pyr, Nap, Chr, BbF, and BkF were found as the dominant species in TSP and PM2.5, indicating a dominant contribution of PAHs from diesel-fueled vehicular emissions. The bioaccessible fractions measured for different PAH species in tunnel PM2.5 and TSP were highly variable, which can be attributed to PAHs' physicochemical properties, size, and carbonaceous materials of TIPM. The addition of Tenax into SLF as an “adsorption sink” can greatly increase PAHs' inhalation bioaccessibility, but DPPC has a limited effect on tunnel PM-bound PAHs' bioaccessibility. The incremental lifetime carcinogenic risk (ILCR) of tunnel inlet PM2.5-bound PAHs evaluated according to their total mass concentration exceeded the threshold (1.0 × 10−6) set by the USEPA, whereas the ILCRs estimated based on the inhalation bioaccessibility were far below the threshold. Hence, it is vitally important to take into consideration of pollutant's bioaccessibility to refine health risk assessment.

Inhalation Bioaccessibility of Polycyclic Aromatic Hydrocarbons in PM2.5 under Various Lung Environments: Implications for Air Pollution Control during Coronavirus Disease-19 Outbreak.

Global spread of coronavirus disease-19 (COVID-19) is placing an unprecedented pressure on the environment and health. In this study, a new perspective is proposed to assess the inhalation bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) in PM2.5 for people with various lung health conditions. In vitro bioaccessibility (IVBA) was measured using modified epithelial lung fluids simulating the extracellular environment of patients with severe and mild lung inflammation. The average PAH IVBA in PM2.5 of 24.5 ± 4.52% under healthy conditions increased (p = 0.06) to 28.6 ± 3.17% and significantly (p < 0.05) to 32.3 ± 5.32% under mild and severe lung inflammation conditions. A mechanistic study showed that lung inflammation decreased the critical micelle concentrations of main pulmonary surfactants (i.e., from 67.8 (for dipalmitoyl phosphatidylcholine) and 53.3 mg/L (for bovine serum albumin) to 44.5 mg/L) and promoted the formation of micelles, which enhanced the solubilization and competitive desorption of PAHs from PM2.5 in the lung fluids. In addition, risk assessment considering different IVBA values suggested that PAH contamination levels in PM2.5, which were safe for healthy people, may not be acceptable for patients with lung inflammation. Because of the large number of COVID-19 infections, and the fact that some survivors of COVID-19 were observed to still show symptoms of interstitial lung inflammation, the finding here can provide important implications for both the scientific community and policy makers in addressing health risk and air pollution control during the COVID-19 outbreak.

Bioaccessibility-based monitoring and risk assessment of indoor dust-bound PAHs collected from housing and public buildings: Effect of influencing factors.

Polycyclic aromatic hydrocarbons (PAHs) bounded in indoor dust have significant effects in residents' health. Although various researches has evaluated exposure to PAHs in some indoor areas around the world, no work has been conducted on bioaccessibility of indoor PAHs in the buildings of Bushehr city. Therefore, dust samples were collected from various indoor microenvironments including residential buildings (RB), office buildings (OB), commercial buildings (CB), industrial buildings (IB), school classroom (SC), laboratory (LR), drugstores (DS), beauty salons (BS), smoking cafés (SC) and restaurants (Res) - 10 from each microenvironment. In order to determine the levels of polycyclic aromatic hydrocarbons (PAHs), bioaccessible PAHs, and sink sorption PAHS were analyzed in them. The results showed that the highest level of these contaminants was detected in SC and the lowest in Lab. The median concentration of dust-bound ΣPAHs, bioaccessible ΣPAHs, and sink sorption ΣPAHs in the SC samples were 10,890.00, 1157.92, and 297.28ng/g, and they were 1160.00, 19.69, and 0.75ng/g in Lab samples. The results also indicated that the ΣPAHs concentration had a negative and significant association with the ventilation rate (pvalue <0.05 in most cases), as well as a positive and significant relationship with smoking inside buildings (pvalue <0.05). The estimated daily intake (EDI) values calculated for residential buildings (RB) were higher compared to most of the other studied microenvironments. These observations can be due to the fact that people spend much more time in residential buildings (50% of the entire day) compared to occupational settings (22%). Thus, they intake more dust within a longer time, and are hence exposed to larger amounts of pollutants bound with these particles.

Size-dependent in vitro inhalation bioaccessibility of PAHs and O/N PAHs - Implications to inhalation risk assessment

Size segregated samples (<0.49, 0.49–0.95, 0.95–1.5, 1.5–3.0, 3.0–7.2 and > 7.2 μm) of atmospheric particulate matter (APM) were collected at a traffic site in the urban agglomeration of Thessaloniki, northern Greece, during the cold and the warm period of 2020. The solvent-extractable organic matter was analyzed for selected organic contaminants including polycyclic aromatic hydrocarbons (PAHs), and their nitro- and oxy-derivarives (NPAHs and OPAHs, respectively). Mean concentrations of ∑16PAHs, ∑6NPAHs and ∑10OPAHs associated to total suspended particles (TSP) were 18 ng m−3, 0.2 ng m−3 and 0.9 ng m−3, respectively, in the cold period exhibiting significant decrease (6.4, 0.2 and 0.09 ng m−3, respectively) in the warm period. The major amount of all compounds was found to be associated with the alveolar particle size fraction <0.49 μm. The inhalation bioaccessibility of PAHs and O/N PAHs was measured in vitro using two simulated lung fluids (SLFs), the Gamble's solution (GS) and the artificial lysosomal fluid (ALF). With both SLFs, the derived bioaccessible fractions (BAFs) followed the order PAHs > OPAHs > NPAHs. Although no clear dependence of bioaccessibility on particle size was obtained, increased bioaccessibility of PAHs and PAH derivatives in coarse particles (>7.2 μm) was evident. Bioaccessibility was found to be strongly related to the logKOW and the water solubility of individual compounds hindering limited mobilization of the most hydrophobic and less water-soluble compounds from APM to SLFs. The lifetime cancer risk due to inhalation exposure to bioaccessible PAHs, NPAHs and OPAHs was estimated and compared to those calculated from the particulate concentrations of organic contaminants.

Bioaccessibility of Polycyclic Aromatic Hydrocarbons (PAHs) in Grilled Meat: The Effects of Meat Doneness and Fat Content.

Exposure to polycyclic aromatic hydrocarbons (PAHs) through diet is gaining concern due to the risk it poses to human health. This study evaluated the bioaccessibility of PAHs contained in charcoal-grilled beef and chicken in different segments of the gastrointestinal tract (GIT) with regard to the degree of doneness and fat content of the meats. The levels of 15 PAHs in the grilled meat samples and bioaccessible fractions were determined using high-performance liquid chromatography (HPLC) equipped with PAH column, and UV and fluorescence detectors. Total PAHs were found in beef (30.73 ng/g) and chicken (70.93 ng/g) before its digestion, and different PAHs’ bioaccessibility were observed in the different segments of GIT, with the highest in the stomach followed by the small intestine, despite the relatively higher bioaccessibility of individual PAHs in grilled beef as compared to those in grilled chicken. Additionally, the PAHs’ bioaccessibility increased with the increase in the degree of doneness. Positive linear correlation was observed for the PAHs’ bioaccessibility and the fat contents of grilled meat. Overall, this study highlights the influence of meat doneness (cooking time) and fat contents on the bioaccessibility and bioaccumulation of PAHs.

Magnetic poly(β-cyclodextrin) combined with solubilizing agents for the rapid bioaccessibility measurement of polycyclic aromatic hydrocarbons in soils

The rapid determination of the bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) in soils is challenging due to their slow desorption rates and the insufficient extraction efficiency of the available methods. Herein, magnetic poly(β-cyclodextrin) microparticles (Fe3O4@PCD) were combined with hydroxypropyl-β-cyclodextrin (HPCD) or methanol (MeOH) as solubilizing agents to develop a rapid and effective method for the bioaccessibility measurement of PAHs. Fe3O4@PCD was first validated for the rapid and quantitative adsorption of PAHs from MeOH and HPCD solutions. The solubilizing agents were then coupled with Fe3O4@PCD to extract PAHs from soil-water slurries, affording higher extractable fractions than the corresponding solution extraction and comparable to or higher than single Fe3O4@PCD or Tenax extraction. The desorption rates of labile PAHs could be markedly accelerated in this process, which were 1.3–12.0 times faster than those of single Fe3O4@PCD extraction. Moreover, a low HPCD concentration was sufficient to achieve a strong acceleration of the desorption rate without excessive extraction of the slow desorption fraction. Finally, a comparison with a bioaccumulation assay revealed that the combination of Fe3O4@PCD with HPCD could accurately predict the PAH concentration accumulated in earthworms in three field soil samples, indicating that the method is a time-saving and efficient procedure to measure the bioaccessibility of PAHs.

Inhalation bioaccessibility, health risk assessment, and source appointment of ambient PM2.5-bound polycyclic aromatic hydrocarbons (PAHs) in Caofeidian, China.

The inhalation bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) is significant for accurately assessing the health risks posed by PM2.5-bound PAHs. In this study, 96 PM2.5 samples from Caofeidian, China, were investigated for PM2.5-bound PAH source appointment and bioaccessibility assessment during four seasons. PAH18 potential sources were identified by positive matrix factorization. The inhalation bioaccessibility of PAH18 was investigated by simulated epithelial lung fluid extraction. The incremental lifetime cancer risk (ILCR) model was subsequently used to evaluate the carcinogenic risk posed by PM2.5-bound PAHs in children, teenagers, and adults. Four potential sources of PM2.5-bound PAH18 were identified: industry emissions (44%), petroleum volatilization (30%), vehicle emissions (15%), and coal combustion (11%). The average inhalation bioaccessibility of PAHs ranged from 17.8% (dibenzo [a,h] anthracene) to 67.9% (fluorene). The ILCR values for children and teenagers were lower than the acceptable levels (10-6) in the four seasons considering inhalation bioaccessibility. However, the ILCR value of adults was higher than the threshold in winter (1.26 × 10-6). Source identification suggested that reducing industrial pollution was the primary measure for controlling PM2.5-bound PAHs in Caofeidian. Additionally, the inhalation bioaccessibility of PM2.5-bound PAHs was evaluated to precisely estimate the health risks caused by PAHs.

Inhalation bioacessibility and absorption of polycyclic aromatic hydrocarbons (PAHs) in indoor PM2.5 and its implication in risk assessment

Inhalation bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) in PM2.5 was assessed in numerous studies, however, the lung cell uptake and penetration of PAHs was seldom taken into account in risk assessment. In the present study, eighteen indoor PM2.5 samples collected from Guangzhou, China were analyzed for the inhalation bioavailability of PAHs combining the inhalation bioaccessibility and cell absorption of PAHs. Two simulated epithelial lung fluid mimicking the healthy condition (as represented by gamble's solution (GMB), pH = 7.4) and the inflammatory condition (as represented by artificial lysosomal fluid (ALF), pH = 4.5) were employed to evaluate the inhalation bioaccessibility. The results indicated that the bioaccessibility of PAHs under the inflammatory condition (1.28%–87.7%) was higher than that under healthy condition (0.88%–87.6%). Naphthalene, phenanthrene, pyrene and benzo[a]pyrene were selected for absorption assay of lung epithelial cells (A549). The absorption rate of PAHs ranged from 64.7 to 90.7% and it was inversely proportional to the number of aromatic rings. Taken together, the inhalation bioavailability based on the bioaccessibility of PAHs and the lung cell absorption ratio ranged from 9.9 to 56.9% under the healthy state, from 12.7 to 65.6% under inflammatory condition. The correction parameter (Fc) was thus established and can be used to improve the risk assessment of human exposure to PAHs via PM2.5 inhalation in future work.

Distribution and bioaccessibility of polycyclic aromatic hydrocarbons in industrially contaminated site soils as affected by thermal treatment

Thermal treatment can not only efficiently remove volatile pollutants but also distinctly alter the speciation of organic carbon (C) and the behaviors of residual pollutants in contaminated soils. Here we examined the distribution and bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) in industrially contaminated site soils affected by thermal treatment (temperature ranging of 105–650 ℃) using synchrotron-based infrared microspectroscopy and n-butanol extraction (a mild solvent extractant). In the pristine soils, the sequestration and distribution of PAHs were simultaneously controlled by aromatic C, aliphatic C and clay minerals. Desorption efficiency of PAHs was substantially increased with increasing temperature, whereas the residual PAHs were strongly immobilized within their binding sites evidenced by their dramatically decreased bioaccessibility. Aliphatic and carboxylic C were gradually decomposed and/or carbonized with increasing temperature. In contrast, aromatic C remained relatively recalcitrant during the thermal treatment and was the key controlling factor for the desorption of residual PAHs in the soils with either thermal treatment or n-butanol extraction. This study is the first to visualize the changes in the binding sites and bioaccessibility of PAHs induced by thermal treatment, which have important implications for understanding the sequestration mechanisms of organic pollutants in soil and optimizing the remediation technique.

Inhalation bioaccessibility estimation of polycyclic aromatic hydrocarbons from atmospheric particulate matter (PM10): Influence of PM10 composition and health risk assessment

Polycyclic aromatic hydrocarbons (PAHs) inhalation bioaccessibility was assessed in 65 atmospheric particulate matter samples (PM10) collected at an Atlantic coastal European urban site. The proposed method consists on a physiologically based extraction (PBET) by using Gamble’s solution followed by a vortex assisted liquid-liquid micro-extraction (VALLME) and quantification by high performance liquid chromatography with fluorescence detection (HPLC-FLD). The use of a micro-extraction technique combined with FLD detection, provides a simple, fast, sensitive, accurate and low-cost methodology to PAHs quantification in bioaccessible fractions. Accuracy of the bioaccessibility study was assessed by means of a mass balance approaches using a PM10 filter and a certified reference material (ERM-CZ100). High-moderate inhalation bioaccessibilities were found for phenanthrene (Phe), fluoranthene (Ft) and pyrene (Pyr) (average ratios in the 52–65% range); while dibenz (a,h)anthracene (DBahA), indeno (1,2,3-cd)pyrene (IP) and benzo (g,h,i)perylene (BghiP) were observed to be less bioaccessibles (average ratios in the 11–14% range). Relationship between PM10 composition (major ions, trace metals, equivalent black carbon (eBC) and UV-absorbing particulate matter (UVPM)) and PAHs bioaccessibility ratios was also assessed. Principal Component Analysis (PCA) showed that PAHs bioaccessibility percentage is dependent on anthropogenic (eBC, UVPM and Sb concentrations) and marine sources of PM10. Predicted PAHs bioaccessibilities after applying a multiple linear regression model based on marine and anthropogenic source of PM10 could also be established. Health risk assessment of target PM10-associated PAHs via inhalation was assessed considering bioaccessibility concentrations by using hazard index (HI) and BaP equivalent concentration (BaPeq) approaches, suggesting no carcinogenic risk in the area during the sampling campaign.

Effect of sediment particle size on polycyclic aromatic hydrocarbon bioaccessibility and degradation by ultrasound

The effect of particle size on sonochemical desorption, degradation and change in bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) on contaminated sediments was investigated. Batch experiments were performed with the whole sediment (WS < 850 μm), a large size range fraction (150 μm < LSR < 850 μm), and a small size range fraction (SSR < 150 μm) of the whole sediment. PAH degradation followed pseudo first-order kinetics; PAHs on LSR sediments underwent more rapid degradation than on SSR and WS sediments (νPAH,LSR > νPAH,WS > νPAH,SSR). In addition, a higher sediment slurry concentration resulted in slower degradation of PAHs. Results are consistent with the more rapid particle size reduction of the LSR. More rapid particle size reduction and faster PAH degradation for the LSR fraction combined with analysis of particle velocities in both size ranges indicates that microjets as opposed to particle–particle collisions due to shockwaves are effective in rapid particle size reduction and PAH degradation. Moreover, the bioaccessible fraction (FPAH,fast,t) of sorbed PAHs in both particle size fractions was found to increase with sonication time but was more rapid with the LSR. Likewise, the more tightly bound PAHs, those in the slow desorbing fraction (FPAH,slow,t) of PAHs, decreased faster with sonication of LSR particles compared to SSR particles, consistent with the trend of particle size reduction. Results of this study suggest that ultrasonic treatment is more effective for larger size particle sediments, although sonication is also viable for small sediment sizes.

Temporal Evolution of PAHs Bioaccessibility in an Aged-Contaminated Soil during the Growth of Two Fabaceae.

Polycyclic aromatic hydrocarbons (PAHs) are health-concerning organic compounds that accumulate in the environment. Bioremediation and phytoremediation are studied to develop eco-friendly remediation techniques. In this study, the effects of two plants (Medicago sativa L. and Trifolium pratense L.) on the PAHs’ bioaccessibility in an aged-contaminated soil throughout a long-term rhizoremediation trial was investigated. A bioaccessibility measurement protocol, using Tenax® beads, was adapted to the studied soil. The aged-contaminated soil was cultured with each plant type and compared to unplanted soil. The bioaccessible and residual PAH contents were quantified after 3, 6 and 12 months. The PAHs’ desorption kinetics were established for 15 PAHs and described by a site distribution model. A common Tenax® extraction time (24 h) was established as a comparison basis for PAHs bioaccessibility. The rhizoremediation results show that M. sativa developed better than T. pratense on the contaminated soil. When plants were absent (control) or small (T. pratense), the global PAHs’ residual contents dissipated from the rhizosphere to 8% and 10% of the total initial content, respectively. However, in the presence of M. sativa, dissipation after 12 months was only 50% of the total initial content. Finally, the PAHs’ bioaccessible content increased more significantly in the absence of plants. This one-year trial brought no evidence that the presence of M. sativa or T. pratense on this tested aged-contaminated soil was beneficial in the PAH remediation process, compared to unplanted soil.

Influence of dietary patterns on contaminants bioaccessibility and intestinal transport by in vitro assays

Food contaminants are usually studied as isolated molecules, not considering the overall meal components. Notwithstanding, contaminants are not ingested individually, therefore their risks should be assessed in the context of the overall diet. In the present study the influence of three well known dietary patterns, Western (W), Mediterranean (M) and vegetarian (V), on the bioaccessibility and intestinal transport of polycyclic aromatic hydrocarbons (PAHs) (benzo[a]pyrene (BaP) and benzo[b]fluoranthene (BbF)), heterocyclic aromatic amines (HAAs) (2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) and 2-Amino-9H-pyrido[2,3-b]indole (AAC)) and mycotoxins (MY) (aflatoxin B2 (AB2) and ochratoxin A (OTA)) was evaluated. Whole meals representative of W, M and V patterns were spiked with 100 µg kg−1 of each contaminant and subjected to the Infogest in vitro digestion method. Intestinal transport was performed using Caco-2 cells in apical/basolateral inserts. Contaminants were quantified by QuEChERS/HPLC/Fluorescence analysis.The dietary pattern itself influenced significantly the bioaccessibility of some contaminants, since higher bioaccessibility of HAAs (PhIP and AAC) was observed for V diet, while higher bioaccessibility of PAHs (BBF and BAP) and the MY (OTA) was observed for W diet. Concerning intestinal transport, the effect of the diet matrices was less noticed. Notwithstanding, AAC transport increased with W diet, while AB2s transport increased with the V diet. Regarding PAHs the three patterns either blocked (BbF) or reduced (BaP) the transport. Besides the well known nutritional, protective or deleterious effects of the different dietary patterns, the increased bioaccessibility or intestinal transport of some food contaminants, can have an additional influence on the global health impact.