Sorption Of Polycyclic Aromatic Hydrocarbons Research Articles

Sorption Behavior of Organic Pollutants on Biodegradable and Nondegradable Microplastics: pH Effects

Microplastics (MPs), chlorinated phenols (CPs), polycyclic aromatic hydrocarbons (PAHs) and halogenated benzenes (HBs) are pollutants that are widely present in freshwater systems. As alternatives to conventional plastics, bioplastics are receiving a lot of attention, but there are limited data on their impact on pollutant behavior. This work therefore investigated the impact of pH on the sorption of CPs, PAHs and HBs, as some of the toxic and highly persistent pollutants, on seven different plastics using kinetic and isotherm studies. The pH of the water matrix impacted the adsorption behavior of CPs on all selected MPs, with the highest degree of adsorption occurring at pH 7 for the majority of the selected CPs. The highest adsorption affinity of CPs on the MPs, at pH 7, was obtained for 4-chlorophenol and 2,4-dichlorophenol on powdered polyethylene standard (qt = 221 μg/g), while the lowest was obtained for the adsorption of pentachlorophenol on polyethylene terephthalate (qt = 25 μg/g). On the other hand, the pH value of the water matrix did not affect the adsorption of halogenated benzenes and PAHs on MPs. The pseudo-second-order rate model fit the adsorption kinetics data of all experiments. The results obtained for the adsorption of CPs on MPs indicated a lower sorption affinity of CPs with MPs at pH 4 and pH 10 compared to pH 7. The Langmuir isotherm, at pH 7, implied that 4-chlorophenol’s adsorption affinity was not significantly influenced by the type of MPs. On the other hand, at pH 7, the adsorption of 2,4-dichlorophenol, 2,4,6-trichlorophenol and pentachlorophenol varied greatly, with powdered MP types showing the highest affinity for CP adsorption. Furthermore, the obtained adsorption isotherm results imply that electrostatic attraction, hydrogen bonds, π-π interactions and van der Waals interactions, are an integral part of adsorption mechanisms of the CPs on the MPs.

Unravelling mixed sources of polycyclic aromatic hydrocarbons (PAH) in urban soils by visual characterization of anthropogenic substrates and coal particles, 71 PAH and alkylated PAH patterns

The identification of polycyclic aromatic hydrocarbon (PAH) sources in heterogeneous urban soils containing pyrogenic and/or petrogenic anthropogenic substrates is a common task for risk assessment. Here, for the first time, the results of source identification using analysis of 71 PAH, alkylated PAH patterns and PAH Alkylation Index were related to visually identified and quantified anthropogenic substrates in 50 soil samples. Only the combination of chemical methods with visual characterization enabled the deeper understanding of varying alkylated PAH patterns used for source apportionment and their superimposition if multiple sources occur. Pyrogenic substrates show homogenic slope-shape PAH patterns despite large visual variety. Petrogenic substrates (bituminous coals), show prevailingly bell-shape patterns but pyrogenic patterns also occur, probably due to residues from industrial processes and/or sorption of other pyrogenic PAH. Superimposition of both PAH patterns within a sample results in intermediate patterns, which are determined by the abundance of substrates and their individual PAH contents. A discrepancy between the share of petrogenic substrates and petrogenic PAH was observed due to low-medium PAH contents from coals/tailings. This may lead to misinterpretations if only chemical source identification methods are applied. With increasing proportion of petrogenic PAH in the mixture, the intermediate V-shape pattern (later bell-shape) appears in lower molecular weight PAH and moves progressively to higher molecular weight PAH. ∑71 PAH contents vary from 1.77 to 326.5 mg/kg (median 26.5 mg/kg). Non-EPA PAH measured include highly toxic ∑4 dibenzopyrene isomers (0.045–6.23 mg/kg, median 0.79 mg/kg) and 7H-benzo[c]fluorene (0.008–1.57 mg/kg, median 0.12 mg/kg). Most common anthropogenic substrates are bottom ashes, slags, bituminous coals/tailings and coke/coke ash. The PAH Alkylation Index identifies reliably samples dominated by either petrogenic (<0.4) or pyrogenic (>0.9) PAH, independently of the PAH content. Mixed or primarily pyrogenic PAH sources (0.4–0.9) need further investigations, like the presented combination of methods, which enables a reliable source apportionment.

Exploring sorption of pesticides and PAHs in microplastics derived from plastic mulch films used in modern agriculture

The sorption and vector effect of microplastics on the transfer of pesticides and polycyclic aromatic hydrocarbons (PAHs), as well as its impact on agriculture remain largely unexplored. This comparative study is first to investigate the sorption behavior of different pesticides and PAHs at environmentally realistic concentrations by model microplastics and microplastics derived from polyethylene mulch films. Sorption was found to be up to 90% higher in the case of microplastics derived from mulch films as opposed to pure polyethylene microspheres. For microplastics from mulch films, the sorption percentages for pesticides in media containing CaCl2 were reported to be: pyridate (75.68% and 52.44%), fenazaquin (48.54% and 32.02%), pyridaben (45.04% and 56.70%), bifenthrin (74.27% and 25.88%), etofenprox (82.16% and 54.16%) and pyridalyl (97.00% and 29.74%) at 5 μg/L and 200 μg/L pesticide concentration levels respectively. For PAHs, the sorption amounts were: naphthalene (22.03% and 48.00%), fluorene (38.99% and 39.00%), anthracene (64.62% and 68.02%) and pyrene (75.65% and 86.38%) at 5 μg/L and 200 μg/L PAH concentration levels respectively. Sorption was influenced by the octanol-water partition coefficient (log Kow) and ionic strength. Kinetics of the process in the case of sorption of pesticides were best explained by pseudo-first order kinetic model (R2 between 0.90 and 0.98) while the best fitting isotherm model was Dubinin-Radushkevich (R2 between 0.92 and 0.99). Results suggest the presence of surface level physi-sorption through a micropore volume filling mechanism and the role of hydrophobic and electrostatic forces. Pesticide desorption data in polyethylene mulch films indicate that pesticides with high log Kow were almost completely retained in mulch films, while those with lower log Kow were desorbed rapidly into the surrounding media. Our study highlights the role of microplastics from plastic mulch films as vectors for pesticide and PAH transport at environmentally realistic concentrations and the factors that influence it.

Benchmarking biochar with activated carbon for immobilizing leachable PAH and heterocyclic PAH in contaminated soils

Remediation of residually contaminated soils remains a widespread problem. Biochar can immobilize polycyclic aromatic hydrocarbons (PAH). However, studies on its ability to immobilize PAH and N, S, and O substituted PAH (hetero-PAH) in real soils, and benchmarking with commercial activated carbon are missing. Here, we compared the ability of pristine biochar (BC), steam-activated biochar (SABC), and commercial activated carbon (AC) to immobilize PAH and hetero-PAH. The three carbons were tested on soils from four different contaminated sites in Austria. Different amendment rates (w/w) of the carbons were investigated (BC: 1.0, 2.5, and 5%; SABC: 0.5, 1.0, and 2.0%; AC: 1%) in batch experiments to cover meaningful ranges in relation to their performance. SABC performed better than AC, removing at least 80% PAH with the lowest application rate of 0.5%, and achieving a complete removal at an application rate of 1.0%. BC performed slightly worse but still acceptable in residually contaminated soils (40 and 100% removal at 1 and 5% amendment, respectively). The ability of BC and SABC to immobilize PAH decreased as the PAH-molar volume increased. PAH with three or more rings were preferentially removed by AC compared to SABC or BC. This can be explained by the difference in pore size distribution of the carbons which could limit the accessibility of PAH and hetero-PAH to reach sorption sites for π- π electron donor-acceptor interactions, which drive PAH and hetero-PAH sorption to carbons. Column percolation tests confirmed the results obtained in batch tests, indicating, that decisions for soil remediation can be derived from simpler batch experiments. In soil samples with 1% BC, a reduction of over 90% in the total concentration of PAH in the leached water was observed. Overall, BC and SABC were demonstrated to be valid substitutes for AC for stabilizing residually contaminated soils.

Impact of biochar on sorption of polycyclic aromatic hydrocarbons in water

Impact of biochar on sorption of polycyclic aromatic hydrocarbons in water

Monitoring microplastic-contaminant sorption processes in real-time using membrane introduction mass spectrometry.

Microplastics are environmentally ubiquitous and their role in the fate and distribution of trace contaminants is of emerging concern. We report the first use of membrane introduction mass spectrometry to directly monitor the rate and extent of microplastic-contaminant sorption. Target contaminant (naphthalene, anthracene, pyrene, and nonylphenol) sorption behaviours were examined at nanomolar concentrations with four plastic types: low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), and polystyrene (PS). Under the conditions employed here, short-term sorption kinetics were assessed using on-line mass spectrometry for up to one hour. Subsequent sorption was followed by periodically measuring contaminant concentrations for up to three weeks. Short-term sorption followed first order kinetics with rate constants that scaled with hydrophobicity for the homologous series of polycyclic aromatic hydrocarbons (PAHs). Sorption rate constants on LDPE for equimolar solutions of naphthalene, anthracene, and pyrene were 0.5, 2.0, and 2.2 h-1, respectively, while nonylphenol did not sorb to pristine plastics over this time period. Similar trends among contaminants were observed for other pristine plastics with 4- to 10-fold faster sorption rates associated with LDPE when compared to PS and PP. Sorption was largely complete after three weeks, with the percent analyte sorbed ranging from 40-100% across various microplastic-contaminant combinations. Photo-oxidative ageing of LDPE had little effect on PAH sorption. However, a marked increase in nonylphenol sorption was consistent with increased hydrogen-bonding interactions. This work provides kinetic insights into surface interactions and describes a powerful experimental platform to directly observe contaminant sorption behaviours in complex samples under a variety of environmentally relevant conditions.

Effect of sorption properties on the content, ecotoxicity, and bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) in bottom sediments.

Polycyclic aromatic hydrocarbons (PAHs) tend to accumulate in the sediment due to their high hydrophobicity. Despite PAHs have been the subject of several reviews, PAH sorption processes in bottom sediments has not been comprehensively discucorrelation coefficients between sorption parameters and contessed. Understanding the dependencies governing PAH sorption processes will allow to predict, monitor, and mitigate the ecological effects of PAH contamination and the associated risks to humans or wildlife. The objectives of the study were to assess the relationship between the sorption properties and the content of PAHs in bottom sediments and mussels. The PAH profile was dominated by higher-molecular hydrocarbons, which accounted for 73% of the total concentration of PAHs. Potentiometric studies revealed the steric-based PAH sorption mechanism that strongly depended on the presence of negatively dissociating structures such as carboxylic or phenolic functional groups. Based on the changes in Q8 values, the size-exclusion effect was more likely for 5- and 6-ring compounds. Pores <5µm, which had the largest share in the specific surface area, were the preferred sites for PAH sequestration and stabilization in bottom sediments. The availability of PAHs was reduced in sediments with high organic matter content. The PAH bioaccumulation factor significantly decreased with increasing TOC content in sediments. Higher mortality and growth inhibition of H. incongruens were observed in samples with high and medium TOC contents than in those with low TOC content.

Comparative analysis of fluorescent methods selectivity for ecotoxicants environmental monitoring

A comparative analysis of classical and synchronous fluorescent methods selectivity for ecotoxicants determination of polycyclic aromatic hydrocarbons (PAHs) was carried out. PAHs sorption preconcentration from aqueous cetyltrimethylammonium bromide micellar solutions and spectra recording on a viscose matrix were used. In the case of complex environmental samples, the scope of fluorimetric analysis can be expanded by registering synchronous fluorescence spectra obtained by simultaneously scanning the excitation and emission wavelengths with a constant shift: λem - λex = Δλ = const. The composition of PAHs mixture (phenanthrene, anthracene, fluorene, pyrene) was experimentally evaluated by classical fluorescence with selective excitation and synchronous fluorescence. It was concluded that the use of synchronous spectra makes it possible to improve the selectivity of the PAHs fluorescence analysis in a mixture. These methods can be successfully applied to identify individual PAHs in monitoring of environment water bodies.

A comparative investigation of the sorption of polycyclic aromatic hydrocarbons to various polydisperse micro- and nanoplastics using a novel third-phase partition method

Evidence for direct adverse effects of micro- and nanoplastic particles (MNPs) on human health is scarce, but it has been hypothesized that MNPs act as carriers for environmental pollutants such as polycyclic aromatic hydrocarbons (PAHs). Many studies have already investigated the sorption of PAHs to microplastics, typically using the batch-equilibrium method. Here we established a novel third-phase partition (TPP) method utilizing thermo-extractable polydimethylsiloxane-coated stir-bars as re-usable passive samplers to compare the sorption of PAHs to 17 different MNPs. This method facilitates the quantification of MNP-sorbed pollutants, including those with poor water-solubility without requiring laborious filtration and solvent-extraction steps. Using benzo[a]pyrene (B[a]P) as a representative PAH, sorption kinetics and isotherms for MNPs were evaluated. B[a]P sorption was generally strong but differed by over two-orders of magnitude, clustering according to polymer types in the order of polyamides > polyethylenes ≫ Tire Rubber > polyurethanes > polymethyl methacrylate. B[a]P sorption was diminished for photo-aged MNPs. Within given polymer types, properties including particle size, polarity/hydrophobicity and chain mobility notably influenced B[a]P sorption. When comparing different PAHs, their sorption to selected MNPs increased over five-orders of magnitude with hydrophobicity: anthracene < B[a]P < dibenzo[a,l]pyrene. Our data is an important contribution to the understanding of the sorption behaviors of MNPs. The novel TPP-method represents a universally-applicable approach for the reliable evaluation of sorption characteristics of contaminants and MNPs, and can be easily adapted to desorption studies.Graphical

Sorption of benzo(a)pyrene and of a complex mixture of petrogenic polycyclic aromatic hydrocarbons onto polystyrene microplastics

Microplastics (MPs) largely occur in aquatic ecosystems due to degradation of larger plastics or release from MP-containing products. Due to the hydrophobic nature and large specific surface of MPs, other contaminants, such as polycyclic aromatic hydrocarbons (PAHs), can potentially sorb onto MPs. Several studies have addressed the potential impact of MPs as vectors of PAHs for aquatic organisms. Therefore the role of MPs as sorbents of these compounds should be carefully investigated. The present study aimed to determine the sorption capacity of benzo(a)pyrene (B(a)P), as a model pyrolytic PAH, to polystyrene (PS) MPs of different sizes (4.5 and 0.5 μm). In addition, the sorption of PAHs present in the water accommodated fraction (WAF) of a naphthenic North Sea crude oil to 4.5 μm MPs was also studied as a model of a complex mixture of petrogenic PAHs that could appear in oil-polluted environments. The results indicated that 0.5 μm MPs showed higher maximum sorption capacity (Qmax) for B(a)P (145–242.89 μg/g) than 4.5 μm MPs (30.50–67.65 μg/g). From the WAF mixture, naphthalene was sorbed at a higher extent than the other PAHs to 4.5 μm MPs but with weak binding interactions (Kf = 69.25 L/g; 1/n = 0.46) according to the analysis of the aqueous phase, whereas phenanthrene showed stronger binding interactions (Kf = 0.24 L/g; 1/n = 0.98) based on the analysis of the solid phase. Sorption of PAHs of the complex WAF mixture to 4.5 μm MPs was relatively limited and driven by the hydrophobicity and initial concentration of each PAH. Overall, the results indicate that sorption estimations based solely on the analysis of the aqueous phase could overestimate the capacity of MPs to carry PAHs. Therefore, controlled laboratory assays assessing the “Trojan Horse effect” of MPs for aquatic organisms should consider these findings in order to design accurate and relevant experimental procedures.

Integration of soil washing and cork permeable reactive barriers for the remediation of soil contaminated with polycyclic aromatic hydrocarbons

AbstractBACKGROUNDSoil washing is a well‐known technology for the remediation of soils polluted by organic contaminants, including polycyclic aromatic hydrocarbons (PAHs). This study aimed to go further by integrating soil washing and permeable reactive barriers (PRBs) made of cork granules to remove PAHs from the soil. While PAHs may be transferred from the soil to the washing solution in the soil washing step, the cork PRB may provide the removal of PAHs from the washing solution, ultimately leading to the reuse of this solution.RESULTSThe integrated approach was tested by means of packed bed column experiments in the absence and presence of cork PRBs. Two PAHs were under focus: fluorene (FLU) and phenanthrene (PHE). In soil with 0.5 mmol L−1 kgsoil−1 of FLU and PHE, the soil washing technique employing thermally treated cork granules and a solution of 70%/30% water/acetonitrile (v/v) flowing at 2.2 mL min−1 promoted the transfer of ~58% of PAHs from the soil to the washing solution, while the cork PRB retained ~98% of the PAHs from the washing solution. The acetonitrile content of the water/acetonitrile washing solutions contributed to the soil washing since it was responsible for PAH desorption and elution, however it was unfavorable for PAH sorption onto the cork as acetonitrile competed with PAHs for cork sorption sites.CONCLUSIONCork PRBs were able to retain PAHs from soil washing solutions and provide final solutions free of PAHs, demonstrating the viability of integrating solvent‐aided soil washing with cork PRBs. © 2022 Society of Chemical Industry (SCI).

Contributions of partition and adsorption to polycyclic aromatic hydrocarbons sorption by fractionated soil at different particle sizes.

Partition and adsorption of polycyclic aromatic hydrocarbons (PAHs) are critical mechanisms determining their fate at the solid-liquid interface. The complexity of soil composition makes it difficult to distinguish between partition and adsorption, and bates the accuracy of the research results. This study found that the composition and structure of the soil particles (SAs) of varying particle sizes were significantly different. Partition contributed significantly to phenanthrene (Phe) sorption in SAs over 0.002mm. However, PAHs had the highest sorption coefficient (Kd) in SA less than 0.002mm (SA-3), and the lower aqueous phase equilibrium concentration of Phe, the greater the adsorption effect. According to morphology and structural analysis, Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS), interactions of micropores, soil organic matter (SOM) and minerals enhanced the sorption of PAHs. Additionally, thermogravimetry and mass spectrometry (TG-MS) results proved that SOM could inhibit the release of PAHs adsorbed in SAs during heating process. We observed that the Log Koc of PAHs was the most important factor in determining the Kd in SAs applying principal component analyses (PCA), and they have significant linear relationships (R2=0.79-0.93). These findings provide new understandings on interface reactivity of PAHs sorption to soils and the development of interface model.

Polycyclic aromatic hydrocarbons in sediment–porewater system from the East China Sea: Occurrence, partitioning, and diffusion

The distribution, partitioning behavior, and diffusion of polycyclic aromatic hydrocarbons (PAHs) within sediment–porewater system were determined in two cores obtained from the Min-Zhe coastal mud of the East China Sea (ECS). Depth profiles of apparently dissolved PAH levels exhibited greater variabilities, with their elevated levels at depth and a high abundance of two-to three-ring PAHs observed. These distribution and composition patterns were inconsistent with the corresponding sediment PAHs, indicating differences in controlling factors for PAHs present in the system. In addition to compound's hydrophobicity, low detection of heavier PAHs in porewater was possibly correlated with the sediment transport process, as indicated by a relatively high weathering ratio in southern Min-Zhe coastal mud. PAH sorption affinity to the collected core sediments exhibited a generally decreasing trend downcore, as expressed by sediment–porewater partition coefficients. This was consistent with the higher content of porewater PAHs in deep core sediment. The established sediment total organic carbon (TOC)–porewater partitioning profiles in cores were predicted with amorphous organic carbon (AOC)-, coal tar-, and TOC-based distribution models, suggesting a dominant nonlinear sorption of PAHs to AOC. Through activity determinations, PAH diffusion within porewater was elucidated, with significant upward and downward mass transfer for PAHs occurring in both cores. The upward diffusion in the core collected from northern Min-Zhe coastal mud was in significant association with sediment TOC. This suggests that sediment TOC (especially AOC)-desorption of lighter PAHs into porewater, and therefore the possibility of their participation in environmental cycling. Baseline toxicity potential and toxic unit calculations indicated a relatively low exposure risk for benthic organisms to porewater PAHs.

A comparative study of the sorption of O-PAHs and PAHs onto soils to understand their transport in soils and groundwater

Polycyclic aromatic hydrocarbons (PAHs) and their oxygenated derivates (O-PAHs) are identified in soils and groundwater of industrialized sites and contribute to the risk for Humans and the Environment. Nevertheless, data are scarce in literature concerning their retention and transfer in soils and no soil - water partition coefficients are available for these compounds. Sorption of two PAHs, fluorene and acenaphthene and two O-PAHs, 9H-fluorenone and dibenzofuran onto two soils with different organic carbon contents was evaluated and compared by determining their sorption isotherms. Effect of ionic strength and liquid to solid ratio, on fluorene and fluorenone sorption was also evaluated. Sorption equilibrium is achieved within less than 24 hr of mixing and linear sorption models best fit the isotherm data. Acenaphthene and dibenzofuran are similarly sorbed onto the soil. KD of fluorene is higher than the one of fluorenone, showing a smaller affinity of fluorenone towards the solid phase. This means that O-PAH could form larger contamination plumes in groundwater than PAHs. Decreasing the L/S ratio from 100 to 50 and 30, increases the sorption of fluorenone onto the soil by 56% and 67% respectively, while the sorption of fluorene is slightly increased. Increasing the ionic strength of the aqueous phase also modifies the sorption of fluorenone, contrary to the sorption of fluorene which is slightly affected.

Differential accumulation of polycyclic aromatic hydrocarbons (PAHs) in three earthworm ecotypes: Implications for exposure assessment on historically contaminated soils

This study compared accumulation of the 16 US-EPA priority polycyclic aromatic hydrocarbons (PAHs) in three different earthworm ecotypes, Amynthas sp., Eisenia fetida, and Lumbricus terrestris, in four historically (> 50 years) contaminated manufactured gas plant (MGP) soils using bioassays. Epi-endogeic deep burrowing and soil ingesting Amynthas sp. accumulated significantly more ∑16 PAHs than any other species (upto 8.7 times more), and epigeic surface dwelling E. fetida showed the lowest ∑16 PAH accumulation. Results indicated the importance of earthworm habit and physiology on PAH partitioning into earthworm lipids. Exposure to soil borne PAHs via the gut, as compared with passive diffusion from pore water, was important in species tested, being most evident in burrowing species Amynthas sp. and L. terrestris and for the desorption-resistant higher molecular weight (HMW) PAHs. Biota-soil accumulation factors (BSAF) were low, as influenced by aging, sequestration and strong PAH sorption to secondary sorptive phases in the historically contaminated soils. Bioconcentration factors (BCFs) calculated from freely dissolved pore water PAH concentrations derived from polyoxymethylene solid-phase extractions (POM) were species specific, indicating stronger relationships with octanol-water partition coefficient (KOW) for Amynthas sp. and L. terrestris than for E. fetida. Modelling demonstrated that KOW values were not a reliable proxy for BCF in equilibrium partitioning theory (EqPT) to predict bioavailability for the range of earthworms tested, being less accurate for E. fetida compared to the burrowing species. The study showed that including burrowing and soil feeding earthworm species, such as Amynthas sp. and L. terrestris, in standard testing would benefit regulatory decisions for more accurate quantification of PAH bioavailability in ecological risk assessment on historically contaminated soils.

Removal of polycyclic aromatic hydrocarbons (PAHs) from water through degradable polycaprolactone electrospun membrane.

Polycyclic aromatic hydrocarbons (PAHs) are common and persistent environmental pollutants produced during the incomplete combustion of fuels. They are known for their carcinogenic and mutagenic properties. Thus, their removal from water bodies is highly crucial and has become a critical issue globally. As a solution, here an electrospun polycaprolactone (PCL) membrane with a mean fiber diameter of 2.74 ± 1.3 μm was produced by electrospinning. Water contact angle (WCA) analysis confirmed the hydrophobic nature of the PCL membrane with a WCA of 124°, which remained stable over time. Differential scanning calorimetry analysis (DSC) revealed the semicrystalline nature of the membrane with the respective melting temperature (Tm) of 61.5 °C and crystallization temperature (Tc) of 29.6 °C. X-ray diffraction (XRD) analysis demonstrated that the crystalline structure of the PCL membrane could be preserved after electrospinning. Scanning electron microscopy analysis revealed that the membrane could be stretched without any rupture. The PCL membrane was used to scavenge PAHs (i.e. phenanthrene and anthracene) from water; the membrane could reach equilibrium capacity in a few hours, demonstrating the rapid removal of PAHs from water. The adsorption capacities for anthracene and phenanthrene were found to be 173 ± 17 and 560 ± 51 μg/g, respectively. The adsorption data fitted well with the pseudo-first-order kinetics model for both PAH molecules. The sorption could be attributed to hydrophobic adsorption, which allowed using the PCL membrane repeatedly with ethanol exposure to get rid of the adsorbed PAHs from the membrane's surface. The partial degradation of the fibrous membrane in water was observed due to their hydrolysis-induced bulk erosion. However, the degradation was slow for the membrane kept in the air for 3 months. Overall, the PCL membrane with inherent biocompatibility, biodegradability, and good PAH sorption performance is a promising material for water depollution from toxic PAH compounds.

Polycyclic Aromatic Hydrocarbon Sorption by Functionalized Humic Acids Immobilized in Micro- and Nano-Zeolites

Polycyclic aromatic hydrocarbons (PAHs) are hazardous compounds originating from anthropogenic activity. Due to their carcinogenic properties for humans, several technologies have been developed for PAH removal. Sorption with natural and organic materials is currently one of the most studied due to its low cost and its environmentally friendly nature. In this work, a hybrid sorbent involving functionalized humic acids (HAs) and nano-zeolite is proposed to entrap PAHs. The use of functionalized HAs immobilized in a porous support is designed to address the instability of HAs in solution, which has been already reported. HA functionalization was carried out to increase the non-polarity of HAs and aliphatic group formation. The HAs were functionalized by esterification/etherification with alkyl halides, and their chemical changes were verified by FTIR and NMR. The sorption isotherms of the functionalized HAs in micro- and nano-zeolites were used to assess the performance of the nano-zeolites in adsorbing these HAs. The hybrid support allowed the removal of anthracene and pyrene at percentages higher than 90%; fluoranthene, of angular molecular structure, was adsorbed at 85%. PAHs are ubiquitous in the environment, and a stable sorption of them in solid matrices will allow their removal from the environment through effective and environmentally friendly methods.

PAHs sorption to biochar colloids changes their mobility over time

Biochar is an efficient sorbent for polycyclic aromatic hydrocarbons (PAHs). However, little is known about PAHs sorption kinetics and the effect on the mobility of biochar colloids in saturated porous media. In this study, naphthalene (NAP) and phenanthrene (PHE) were chosen as typical PAHs. In different stages, different sorption sites of PAHs on biochar played a distinct role in affecting the transport of biochar colloids in saturated porous media. The biochar colloids showed less negative surface charge as the contact time between biochar colloids and PAHs increased from 0.017 h to 96 h, which led to the mobility of biochar colloids decreasing over time. But after 168 h contact time, the surface charge of biochar colloids became more negative again, and the inhibition effect of PAHs on biochar colloid transport was weakened. This was related to the sorption kinetics of PAHs on biochar colloids: (1) PAHs sorption onto outer biochar surface; and (2) adsorbed PAHs diffusion into internal biochar pores. PAHs sorption onto the outer biochar surface shielded the negative surface charge and then decreased the mobility of biochar colloids, and then the adsorbed PAHs diffusion into internal biochar pores increased their mobility again. Our results suggested that porous colloids-facilitated PAHs transport in porous media might be highly related to interaction time between PAHs and porous colloids.

Soil texture as a key driver of polycyclic aromatic hydrocarbons (PAHs) distribution in forest topsoils

Due to the dynamic development of civilization and the increasing demand for energy, pollution by harmful chemicals, including polycyclic aromatic hydrocarbons (PAHs) compounds, is a serious threat to forest soils. The aim of the study was to determine the role of texture in the distribution of polycyclic aromatic hydrocarbons (PAHs) and trace elements in forest soils. The areas with different texture ranging from sand through sandy loam to silt loam were selected for the study. The study was carried out in the Chrzanów Forest District in southern Poland (50° 7′ 18 N; 19° 31′ 29 E), which in one of the most intensive industrial emission zones in Europe. The soil samples for properties determination were collected from locations distributed on a regular grid 100 × 100 m (20 points). The samples were collected from the humus horizon (0–10 cm) after removing organic horizon. Basic chemical properties, heavy metal content, polycyclic aromatic hydrocarbons (PAHs) content and magnetic susceptibility values were determined in soil samples. Additionally, enzymatic activity and microbiological biomass was determined in the samples. Our study confirmed the importance of texture in PAHs distribution. A strong correlation between PAHs content and silt content in the soils studied was noted. The regression tree analysis confirmed the importance of the silt content, followed by soil organic carbon in PAHs distribution. Organic carbon content and nitrogen content played a predominant role in controlling the microbial activity. In our study, we did not note a relationship between enzymatic activity, microbiological soil biomass and the amount of PAHs. This may be due to the effective sorption and immobilization of PAHs by particles of fine fractions, especially silt. Obtained results confirmed the usefulness of magnetic susceptibility in the assessment of heavy metals contamination of forest soils. We noted high correlation between magnetic susceptibility value and heavy metals content. Moreover, the relationship between magnetic susceptibility and soil texture of the topsoil was also observed.

Effect of forest and agricultural land use on the accumulation of polycyclic aromatic hydrocarbons in relation to soil properties and possible pollution sources

This study investigated the effects of forest and agricultural land use on the accumulation of polycyclic aromatic hydrocarbons (PAHs) in relation to the chemical and biochemical properties of soil. The heavy metal content in soil samples was also determined; PAH diagnostic ratios were used to identify pollution emission sources. Soils from the Rybnik Forest District of Poland, which has suffered some of the most intense impacts from industrial PAH emissions in Europe, were investigated. Six 200-m-long transects were designated for the experiment, with samples taken every 50 m. These transects were located across forest, agricultural land, and ecotone zones. The organic C and total N contents, pH, hydrolytic acidity and base cation content of the soil samples were determined, as well as the microbial biomass of C, N and P, the enzymatic activity, and the PAH and heavy metal content. A significant impact of land management on the PAH content of the soil due to the supply of organic matter was confirmed. The forest soils were more contaminated with PAHs than the agricultural soils, with an average PAH content in the forest soils of 565.18 µg·kg−1, almost six times higher than in agricultural soils (91.42 µg·kg−1). In addition, soil biological activity, expressed by enzymatic activity, depended on the amount and quality of the soil organic matter and, to a lesser extent, on the PAHs and heavy metals accumulated in the soils. This study confirmed that organic matter has a significant impact on PAH accumulation and is the main soil component involved in the sorption and ageing of PAHs.