Employing a magnetic chitosan/molybdenum disulfide nanocomposite for efficiently removing polycyclic aromatic hydrocarbons from milk samples.

This study aimed to develop a highly efficient nanocomposite composed of magnetic chitosan/molybdenum disulfide (CS/MoS2/Fe3O4) for the removal of three polycyclic aromatic hydrocarbons (PAHs)-pyrene, anthracene, and phenanthrene. Novelty was introduced through the innovative synthesis procedure and the utilization of magnetic properties for enhanced adsorption capabilities. Additionally, the greenness of chitosan as a sorbent component was emphasized, highlighting its biodegradability and low environmental impact compared to traditional sorbents. Factors influencing PAH adsorption, such as nanocomposite dosage, initial PAH concentration, pH, and contact time, were systematically investigated and optimized. The results revealed that optimal removal efficiencies were attained at an initial PAH concentration of 150 mg/L, a sorbent dose of 0.045 g, pH 6.0, and a contact time of 150 min. The pseudo-second-order kinetic model exhibited superior fitting to the experimental data, indicating an equilibrium time of approximately 150 min. Moreover, the equilibrium adsorption process followed the Freundlich isotherm model, with kf and n values exceeding 7.91 mg/g and 1.20, respectively. Remarkably, the maximum absorption capacities for phenanthrene, anthracene, and pyrene on the sorbent were determined as 217 mg/g, 204 mg/g, and 222 mg/g, respectively. These findings underscore the significant potential of the CS/MoS2/Fe3O4 nanocomposite for efficiently removing PAHs from milk and other dairy products, thereby contributing to improved food safety and public health.

Polyaromatic Hydrocarbon-Functionalized 2D MXene-Based 3D Porous Antifouling Nanocomposite with Long Shelf Life for High-Performance Electrochemical Immunosensor Applications.

Affinity-based electrochemical (AEC) biosensors have gained more attention in the field of point-of-care management. However, AEC sensing is hampered by biofouling of the electrode surface and degradation of the antifouling material. Therefore, a breakthrough in antifouling nanomaterials is crucial for the fabrication of reliable AEC biosensors. Herein, for the first time, we propose 1-pyrenebutyric acid-functionalized MXene to develop an antifouling nanocomposite to resist biofouling in the immunosensors. The nanocomposite consisted of a 3D porous network of bovine serum albumin cross-linked with glutaraldehyde with functionalized MXene as conductive nanofillers, where the inherited oxidation resistance property of functionalized MXene improved the electrochemical lifetime of the nanocomposite. On the other hand, the size-extruded porous structure of the nanocomposite inhibited the biofouling activity on the electrode surface for up to 90 days in real samples. As a proof of concept, the antifouling nanocomposite was utilized to fabricate a multiplexed immunosensor for the detection of C-reactive protein (CRP) and ferritin biomarkers. The fabricated sensor showed good selectivity over time and an excellent limit of detection for CRP and ferritin of 6.2 and 4.2 pg/mL, respectively. This research successfully demonstrated that functionalized MXene-based antifouling nanocomposites have great potential to develop high-performance and low-cost immunosensors.

Estimating Binding Energies of π-Stacked Aromatic Dimers Using Force Field-Driven Molecular Dynamics.

π-π stacking are omnipresent interactions, crucial in many areas of chemistry, and often studied using quantum chemical methods. Here, we report a simple and computationally efficient method of estimating the binding energies of stacked polycyclic aromatic hydrocarbons based on steered molecular dynamics. This method leverages the force field parameters for accurate calculation. The presented results show good agreement with those obtained through DFT at the ωB97X-D3/cc-pVQZ level of theory. It is demonstrated that this force field-driven SMD method can be applied to other aromatic molecules, allowing insight into the complexity of the stacking interactions and, more importantly, reporting π-π stacking energy values with reasonable precision.

Distinct Photochemistry of Odd-Carbon PAHs from the Even-Carbon Ones During the Photoaging and Analysis of Soot.

Polycyclic aromatic hydrocarbons (PAHs) are the primary organic carbons in soot. In addition to PAHs with even carbon numbers (PAHeven), substantial odd-carbon PAHs (PAHodd) have been widely observed in soot and ambient particles. Analyzing and understanding the photoaging of these compounds are essential for assessing their environmental effects. Here, using laser desorption ionization mass spectrometry (LDI-MS), we reveal the substantially different photoreactivity of PAHodd from PAHeven in the aging process and their MS detection through their distinct behaviors in the presence and absence of elemental carbon (EC) in soot. During direct photooxidation of organic carbon (OC) alone, the PAHeven are oxidized more rapidly than the PAHodd. However, the degradation of PAHodd becomes preponderant over PAHeven in the presence of EC during photoaging of the whole soot. All of these observations are proposed to originate from the more rapid hydrogen abstraction reaction from PAHodd in the EC-photosensitized reaction, owing to its unique structure of a single sp3-hybridized carbon site. Our findings reveal the photoreactivity and reaction mechanism of PAHodd for the first time, providing a comprehensive understanding of the oxidation of PAHs at a molecular level during soot aging and highlight the enhanced effect of EC on PAHodd ionization in LDI-MS analysis.

High temperature and solar radiation in the Red Sea enhance the dissolution of crude oil from surface films.

The Red Sea is a hotspot of biodiversity susceptible to oil pollution. Besides, it is one of the warmest seas on the Earth with highly transparent waters. In this study, we estimated the oil dissolution rates under natural sunlight spectra and temperature conditions using coastal oil slicks collected after the 2019 Sabiti oil spill in the Red Sea. Optical analyses revealed the significant interactive effect of sunlight and temperature in enhancing the dissolution of oil into dissolved organic matter (DOM). The highest oil dissolution rate (38.68 g C m-3 d-1) was observed in full-spectrum sunlight. Oil dissolution significantly enhanced total organic carbon (TOC) and polycyclic aromatic hydrocarbons (PAHs) in seawater. High nucleic acid (HNA) bacteria, likely the oil degraders, proliferated from 30 to 70 - 90% after 4 days. The heavier stable carbon isotopic composition of methane (δ13C-CH4) and lighter stable carbon isotopic composition of carbon dioxide (δ13C-CO2) indicate the putative role of bacterial processes in the natural degradation of crude oil. The results indicated that the combined effect of temperature and solar radiation enhanced the biological and photochemical dissolution of oil on the Red Sea surface.

Structure-based modeling to assess binding and endocrine disrupting potential of polycyclic aromatic hydrocarbons in Daniorerio.

Environmental contaminants, such as polycyclic aromatic hydrocarbons (PAHs), have raised concerns regarding their potential endocrine-disrupting effects on aquatic organisms, including fish. In this study, molecular docking and molecular dynamics techniques were employed to evaluate the endocrine-disrupting potential of PAHs in zebrafish, as a model organism. A virtual screening with 72 PAHs revealed a correlation between the number of PAH aromatic rings and their binding affinity to proteins involved in endocrine regulation. Furthermore, PAHs with the highest binding affinities for each protein were identified: cyclopenta[cd]pyrene for AR (-9.7 kcal/mol), benzo(g)chrysene for ERα (-11.5 kcal/mol), dibenzo(a,e)pyrene for SHBG (-8.7 kcal/mol), dibenz(a,h)anthracene for StAR (-11.2 kcal/mol), and 2,3-benzofluorene for TRα (-9.8 kcal/mol). Molecular dynamics simulations confirmed the stability of the protein-ligand complexes formed by the PAHs with the highest binding affinities throughout the simulations. Additionally, the effectiveness of the protocol used in this study was demonstrated by the receiver operating characteristic curve (ROC) analysis, which effectively distinguished decoys from true ligands. Therefore, this research provides valuable insights into the endocrine-disrupting potential of PAHs in fish, highlighting the importance of assessing their impact on aquatic ecosystems.

A polyfunctionalized carbon framework composite for efficient decontamination of Cr(VI) and polycyclic aromatic nitrides from acidic wastewater.

Developing multifunctional engineered adsorbents is an effective strategy for decontaminating the environment from various pollutants. In this study, a polyfunctionalized carbon-framework composite, MSC-CFM, was synthesized. The composite comprises an aromatic carbon framework enriched with various functional groups, including magnetic nanoparticles, hydroxyl, and amino groups. MSC-CFM was used to decontaminate Cr(VI) and polycyclic aromatic nitrides (p-dimethylaminoazobenzene sulfonate (DAS) and diphenyl-4, 4 '-di [sodium (azo-2 -) -1-amino-naphthalene-4-sulfonate] (DANS)) from acidic wastewater. The adsorption capacities of MSC-CFM for Cr(VI), DAS and DANS, quantified using the Langmuir isotherm model, were 161.28, 310.83, and 1566.09 mg/g, respectively. Cr(VI) and PAHs (DAS and DANS) were monolayer adsorbed controlled by chemisorption. MSC-CFM could maintain good adsorption efficiency after up to 6 adsorption and desorption cycles. The presence of polycyclic aromatic nitrides promoted the adsorption of Cr(VI) in the Cr(VI)-DAS/DANS binary systems. Removal of pollutants by MSC-CFM involved a variety of unreported reaction mechanisms, such as electrostatic attraction, redox reaction, anion exchange, intermolecular hydrogen bonding, complexation reaction, π-π interaction, and anion-π interaction. MSC-CFM, enriched with a variety of functional groups, is a promising new material for environmental protection. It has good potential for practical application in treating polluted wastewater.

Ultrafine CuO/graphene oxide cellulose nanocomposites with complementary framework for polycyclic aromatic hydrocarbon pollutants removal.

Efficient and sustainable methods for eliminating polycyclic aromatic hydrocarbon pollutants (PAHPs) are in highly desired. Proven technologies involve physical and chemical reactions that absorb PAHPs, however they encounter formidable challenges. Here, a bottom-up refining-grain strategy is proposed to rationally design ultrafine CuO/graphene oxide-cellulose nanocomposites (LCelCCu) with a mirror-like for tetracycline (TC) to substantially improve the efficient of the purification process by active integrated-sorption. The LCelCCu captures TC with a higher affinity and lower energy demand, as determined by sorption kinetic, isotherms, thermodynamics, and infrared and X-ray Photoelectron Spectroscopy. The resulting material could achieve ultra-high sorption capacity (2775.23 mg/g), kinetic (1.2499 L g-1 h-1) and high selectivity (up to 99.9 %) for TC, nearly surpassing all recent adsorbents. This study simultaneously unveils the pioneering role of simultaneous multi-site match sorption and subsequent advanced oxidation synergistically, fundamentally enhancing understanding of the structure-activity-selectivity relationship and inspires more sustainable water purification applications and broader material design considerations.

Sphingobium sp. SJ10-10 encodes a not-yet-reported chromate reductase and the classical Rieske dioxygenases to simultaneously degrade PAH and reduce chromate.

Both polycyclic aromatic hydrocarbons (PAHs) and heavy metals persist in the environment and are toxic to organisms. Their co-occurrence makes any of them difficult to remove during bioremediation and poses challenges to environmental management and public health. Microorganisms capable of effectively degrading PAHs and detoxifying heavy metals concurrently are required to improve the bioremediation process. In this study, we isolated a new strain, Sphingobium sp. SJ10-10, from an abandoned coking plant and demonstrated its capability to simultaneously degrade 92.6 % of 75 mg/L phenanthrene and reduce 90 % of 3.5 mg/L hexavalent chromium [Cr(VI)] within 1.5 days. Strain SJ10-10 encodes Rieske non-heme iron ring-hydroxylating oxygenases (RHOs) to initiate PAH degradation. Additionally, a not-yet-reported protein referred to as Sphingobium chromate reductase (SchR), with low sequence identity to known chromate reductases, was identified to reduce Cr(VI). SchR is distributed across different genera and can be classified into two classes: one from Sphingobium members and the other from non-Sphingobium species. The widespread presence of SchR in those RHO-containing Sphingobium members suggests that they are excellent candidates for bioremediation. In summary, our study demonstrates the simultaneous removal of PAHs and Cr(VI) by strain SJ10-10 and provides valuable insights into microbial strategies for managing complex pollutant mixtures.

A combination of microbial electrolysis cells and bioaugmentation can effectively treat synthetic wastewater containing polycyclic aromatic hydrocarbon.

The anaerobic biodegradation of polycyclic aromatic hydrocarbons (PAHs) is challenging due to its toxic effect on the microbes. Microbial electrolysis cells (MECs), with their excellent characteristics of anodic and cathodic biofilms, can be a viable way to enhance the biodegradation of PAHs. This work assessed different cathode materials (carbon brush and nickel foam) combined with bioaugmentation on typical PAHs-naphthalene biodegradation and analyzed the inhibition amendment mechanism of microbial biofilms in MECs. Compared with the control, the degradation efficiency of naphthalene with the nickel foam cathode supplied with bioaugmentation dosage realized a maximum removal rate of 94.5 ± 3.2%. The highest daily recovered methane yield (227 ± 2 mL/gCOD) was also found in the nickel foam cathode supplied with bioaugmentation. Moreover, the microbial analysis demonstrated the significant switch of predominant PAH-degrading microorganisms from Pseudomonas in control to norank_f_Prolixibacteraceae in MECs. Furthermore, hydrogentrophic methanogenesis prevailed in MEC reactors, which is responsible for methane production. This study proved that MEC combined with bioaugmentation could effectively alleviate the inhibition of PAH, with the nickel foam cathode obtaining the fastest recovery rate in terms of methane yield.

Evaluating the Kinetics and Molecular Mechanism for Biomimetic Metabolic Activation of PAHs by Surface-Enhanced Raman Scattering Spectroscopy.

Biomimetic cytochrome P450 for chemical activation of environmental carcinogens is an efficient in vitro model for evaluating their mutagenicity and ultimately acquiring the metabolites that cannot be easily accessed by conventional routes of organic synthesis. Different kinds of mutagen derived from polyaromatic hydrocarbons (PAHs) by metalloporphyrin/oxidant model systems have been reported, but the underlying molecular mechanisms are poorly understood. Herein, we have for the first time demonstrated an effective surface-enhanced Raman scattering (SERS) protocol to study the dynamics and biomimetic metabolic behaviors of pyrene (Pyr) in the presence of various oxygen donors. Quantitative information on the relative concentration of Pyr and its metabolites in the biomimetic system can be extracted from the SERS spectra. On the basis of our results, we conclude that the oxidative metabolism of Pyr is highly influenced by the types and concentrations of oxygen donors, leading to the formation of 1-hydroxypyrene and dioxygenated products. Besides, the addition of an appropriate amount of an organic solvent can promote the formation of secondary oxidation products. These results offer valuable insights into the dynamics of PAHs metabolism and the regulation of their metabolic pathways in biomimetic activation. In comparison to traditional liquid chromatography-mass spectrometry, the present SERS approach is more suitable for high-throughput evaluation of the metabolic process and kinetics of PAHs. We anticipate that this approach will enable a more general and comprehensive tracking of metabolic dynamics and molecular mechanisms involved in the biomimetic activation of other xenobiotics, such as procarcinogens, promutagens, and drugs.

Fine-tuning an aromatic ring-hydroxylating oxygenase to degrade high molecular weight polycyclic aromatic hydrocarbon.

Rieske nonheme iron aromatic ring-hydroxylating oxygenases (RHOs) play pivotal roles in determining the substrate preferences of polycyclic aromatic hydrocarbon (PAH) degraders. However, their potential to degrade high molecular weight PAHs (HMW-PAHs) has been relatively unexplored. NarA2B2 is an RHO derived from a thermophilic Hydrogenibacillus sp. strain N12. In this study, we have identified four "hotspot" residues (V236, Y300, W316, and L375) that may hinder the catalytic capacity of NarA2B2 when it comes to HMW-PAHs. By employing structure-guided rational enzyme engineering, we successfully modified NarA2B2, resulting in NarA2B2 variants capable of catalyzing the degradation of six different types of HMW-PAHs, including pyrene, fluoranthene, chrysene, benzo[a]anthracene, benzo[b]fluoranthene, and benzo[a]pyrene. Three representative variants, NarA2B2W316I, NarA2B2Y300F-W316I, and NarA2B2V236A-W316I-L375F, not only maintain their abilities to degrade low-molecular-weight PAHs (LMW-PAHs) but also exhibited 2 to 4 times higher degradation efficiency for HMW-PAHs in comparison to another isozyme, NarAaAb. Computational analysis of the NarA2B2 variants predicts that these modifications alter the size and hydrophobicity of the active site pocket making it more suitable for HMW-PAHs. These findings provide a comprehensive understanding of the relationship between three-dimensional structure and functionality, thereby opening up possibilities for designing improved RHOs that can be more effectively used in the bioremediation of PAHs.

Biomolecular condensates of Chlorocatechol 1,2-Dioxygenase as prototypes of enzymatic microreactors for the degradation of polycyclic aromatic hydrocarbons.

Polycyclic aromatic hydrocarbons (PAHs) are molecules with two or more fused aromatic rings that occur naturally in the environment due to incomplete combustion of organic substances. However, the increased demand for fossil fuels in recent years has increased anthropogenic activity, contributing to the environmental concentration of PAHs. The enzyme chlorocatechol 1,2-dioxygenase from Pseudomonas putida (Pp 1,2-CCD) is responsible for the breakdown of the aromatic ring of catechol, making it a potential player in bioremediation strategies. Pp 1,2-CCD can tolerate a broader range of substrates, including halogenated compounds, than other dioxygenases. Here, we report the construction of a chimera protein able to form biomolecular condensates with potential application in bioremediation. The chimera protein was built by conjugating Pp 1,2-CCD to low complex domains (LCDs) derived from the DEAD-box protein Dhh1. We showed that the chimera could undergo liquid-liquid phase separation (LLPS), forming a protein-rich liquid droplet under different conditions (variable protein and PEG8000 concentrations and pH values), in which the protein maintained its structure and main biophysical properties. The condensates were active against 4-chlorocatechol, showing that the chimera droplets preserved the enzymatic activity of the native protein. Therefore, it constitutes a prototype of a microreactor with potential use in bioremediation.

Environmental significance of PAH photoproduct formation: TiO2 nanoparticle influence, altered bioavailability, and potential photochemical mechanisms.

Interactions between polycyclic aromatic hydrocarbons (PAHs) and titanium dioxide (TiO2) nanoparticles (NPs) can produce unforeseen photoproducts in the aqueous phase. Both PAHs and TiO2-NPs are well-studied and highly persistent environmental pollutants, but the consequences of PAH-TiO2-NP interactions are rarely explored. We investigated PAH photoproduct formation over time for benzo[a]pyrene (BaP), fluoranthene (FLT), and pyrene (PYR) in the presence of ultraviolet A (UVA) using a combination of analytical and computational methods including, identification of PAH photoproducts, assessment of expression profiles for gene indicators of PAH metabolism, and computational evaluation of the reaction mechanisms through which certain photoproducts might be formed. Chemical analyses identified diverse photoproducts, but all PAHs shared a primary photoproduct, 9,10-phenanthraquinone (9,10-PQ), regardless of TiO2-NP presence. The computed reaction mechanisms revealed the roles photodissociation and singlet oxygen chemistry likely play in PAH mediated photochemical processes that result in the congruent production of 9,10-PQ within this study. Our investigation of PAH photoproduct formation has provided substantial evidence of the many, diverse and congruent, photoproducts formed from physicochemically distinct PAHs and how TiO2-NPs influence bioavailability and time-related formation of PAH photoproducts.

Investigation of the speciation and environmental risk of heavy metals in biochar produced from textile sludge waste by pyrolysis at different temperatures.

The aim of the present study was to find environmentally friendly solutions for the disposal of problematic and toxic textile sludge (TS) by producing textile sludge biochar (TSB) by pyrolysis and evaluating its chemical properties, polycyclic aromatic hydrocarbon (PAH) content, heavy metals (HMs) speciation, environmental risks, and effects on seed germination. Pyrolysis of TS at temperatures ranging from 300 to 700 °C significantly reduced (85-95%) or eliminated certain PAHs in the biochar, enriched heavy metal content within land use limits, and increased bioavailability of HMs in biochar produced at 300 °C and decreased leaching capacity of HMs in biochar produced at 700 °C. The speciation of HMs and their bioavailability during pyrolysis processes was strongly temperature dependent, with lower temperatures increasing the toxic and bioavailable forms of Zn and Ni, while higher temperatures converted the bioavailable Ni to a more stable form, while Cu, Cr, and Pb were transformed from stable to toxic and bioavailable forms. The ecological risk index (RI) values of TSB-300 and TSB-700 are below the threshold value of 150, indicating a low-risk level, and the risk level decreases at temperatures above 500 °C. Further, the extracts of TSB-300 and TSB-700 had the highest percentage of germinating seeds, while the extracts of TS and TSB-500 inhibited seed germination by 20-30% compared to the control. These results indicate that pyrolysis effectively reduces PAHs and binds leachable HMs in biochar, however, the specific pyrolysis temperature influences metal speciation, bioavailability, seed germination, and environmental risk.

Polycyclic aromatic hydrocarbon skin permeation efficiency in vitro is lower through human than pigskin and decreases with lipophilicity.

Polycyclic aromatic hydrocarbons (PAH) are persistent environmental pollutants, which occasionally appear as contaminants in consumer products. Upon dermal contact, transfer of PAH into the stratum corneum (s.c.) and migration through the skin may occur, resulting in this class of highly toxic compounds to become bioavailable. In this study, dermal penetration through human and porcine skin of 24 PAH, comprising broad molar mass (M: 152-302 g/mol) and octanol-water partition coefficient (logP: 3.9-7.3) ranges, was evaluated via Franz diffusion cell in vitro assays. More lipophilic and potentially more toxic PAH had decreased permeation rates through the rather lipophilic s.c. into the more hydrophilic viable (epi-)dermis. Furthermore, human skin was less permeable than pigskin, a commonly used surrogate in skin penetration studies. In particular, the s.c. of human skin retains a greater share of PAH, an effect that is more pronounced for smaller PAH. Additionally, we compared the skin permeation kinetics of different PAH in pigskin. While small PAH (M < 230 g/mol, logP < 6) permeate the skin quickly and are detected in the receptor fluid after 2 h, large PAH (M > 252 g/mol, logP ≥ 6) do not fully permeate the skin up to 48 h. This indicates that highly lipophilic PAH do not become bioavailable as readily as their smaller congeners when transferred to the skin surface. Our data suggest that pigskin could be used as a surrogate for worst case scenario estimates of dermal PAH permeation through human skin.

Remediation of carcinogenic PAHs from landfill leachate by Electro-Fenton process - Optimization and modeling.

PAHs is the group of emerging micro-pollutants present in most environmental matrices that has the tendency to bioaccumulate and cause carcinogenic effects to human health. The present research involved the quantification and treatment of leachate produced from secured landfill, to eliminate the PAHS. Electro-Fenton process, a class of advanced oxidation process, is adopted to degrade the PAHs using titanium electrodes as both anode and cathode. Artificial intelligence based statistical tool "Central Composite Design" a module of JMP -19 software was used to design the experiments and optimize the critical parameters involved in the research. It was observed that the value of P is significant (P < 0.05) for all the independent variables evidencing the significant correlation between experimental values and predicted values of the software. The value of R2 obtained was 0.96 and 0.97 for COD and PAHs respectively. The maximum removal efficiency of COD and PAH was found to be 84.24% and 90.78% respectively. The optimized conditions obtained from the central composite design were: pH = 5; Fe2+ = 0.1 g/L; H2O2 = 2 g/L; reaction time = 60 min; and electric intensity = 0.2 A. Additionally, optimized experimental conditions were used to study the removal efficiencies of individual 16 PAHs and are also reported. From the close proximity of experimental and predicted results of the software it can be proved that central composite design is efficient enough to be used as a statistical tool in design and analysis for treatment of landfill leachate.

Importance of soil ecoenzyme stoichiometry for efficient polycyclic aromatic hydrocarbon biodegradation.

Efficient remediation of soil contaminated by polycyclic aromatic hydrocarbons (PAHs) is challenging. To determine whether soil ecoenzyme stoichiometry influences PAH degradation under biostimulation and bioaugmentation, this study initially characterized soil ecoenzyme stoichiometry via a PAH degradation experiment and subsequently designed a validation experiment to answer this question. The results showed that inoculation of PAH degradation consortia ZY-PHE plus vanillate efficiently degraded phenanthrene with a K value of 0.471 (depending on first-order kinetics), followed by treatment with ZY-PHE and control. Ecoenzyme stoichiometry data revealed that the EEAC:N, vector length and angle increased before day five and decreased during the degradation process. In contrast, EEAN:P decreased and then increased. These results indicated that the rapid PAH degradation period induced more C limitation and organic P mineralization. Correlation analysis indicated that the degradation rate K was negatively correlated with vector length, EEAC:P, and EEAN:P, suggesting that C limitation and relatively less efficient P mineralization could inhibit biodegradation. Therefore, incorporating liable carbon and acid phosphatase or soluble P promoted PAH degradation in soils with ZY-PHE. This study provides novel insights into the relationship between soil ecoenzyme stoichiometry and PAH degradation. It is suggested that soil ecoenzyme stoichiometry be evaluated before designing bioremeiation stragtegies for PAH contanminated soils.

Eco-Friendly Inorganic Binders: A Key Alternative for Reducing Harmful Emissions in Molding and Core-Making Technologies.

Many years of foundry practice and much more accurate analytical methods have shown that sands with organic binders, in addition to their many technological advantages, pose risks associated with the emission of many compounds, including harmful ones (e.g., formaldehyde, phenol, benzene, polycyclic aromatic hydrocarbons, and sulfur), arising during the pouring of liquid casting alloys into molds, their cooling, and knock-out. The aim of this research is to demonstrate the potential benefits of adopting inorganic binders in European iron foundries. This will improve the environmental and working conditions by introducing cleaner and more ecological production methods, while also ranking the tested binders studied in terms of their harmful content. The article pays special attention to the analysis of seven innovative inorganic binders and one organic binder, acting as a reference for emissions of gases from the BTEX (benzene, toluene, ethylbenzene, and xylenes) and PAHs (polycyclic aromatic hydrocarbons) groups and other compounds such as phenol, formaldehyde, and isocyanates (MDI and TDI) generated during the mold pouring process with liquid metals. The knowledge gained will, for the first time, enrich the database needed to update the Reference Document on The Best Available Techniques for the Smitheries and Foundries Industry (SF BREF).

Evaluation of surfactant-aided polycyclic aromatic hydrocarbon biodegradation by molecular docking and molecular dynamic simulation in the marine environment.

Marine oil spills directly cause polycyclic aromatic hydrocarbons (PAHs) pollution and affect marine organisms due to their toxic property. Chemical and bio-based dispersants composed of surfactants and solvents are considered effective oil spill-treating agents. Dispersants enhance oil biodegradation in the marine environment by rapidly increasing their solubility in the water column. However, the effect of dispersants, especially surfactants, on PAHs degradation by enzymes produced by microorganisms has not been studied at the molecular level. The role of the cytochrome P450 (CYP) enzyme in converting contaminants into reactive metabolites during the biodegradation process has been evidenced, but the activity in the presence of surfactants is still ambiguous. Thus, this study focused on the evaluation of the impact of chemical and bio-surfactants (i.e., Tween 80 (TWE) and Surfactin (SUC)) on the biodegradation of naphthalene (NAP), chrysene (CHR), and pyrene (PYR), the representative components of PAHs, with CYP enzyme from microalgae Parachlorella kessleri using molecular docking and molecular dynamics (MD) simulation. The molecular docking analysis revealed that PAHs bound to residues at the CYP active site through hydrophobic interactions for biodegradation. The MD simulation showed that the surfactant addition changed the enzyme conformation in the CYP-PAH complexes to provide more interactions between the enzyme and PAHs. This led to an increase in the enzyme's capability to degrade PAHs. Binding free energy (ΔG||Bind) calculations confirmed that surfactant treatment could enhance PAHs degradation by the enzyme. The SUC gave a better result on NAP and PYR biodegradation based on ΔG||Bind, while TWE facilitated the biodegradation of CHR. The research outputs could greatly facilitate evaluating the behaviors of oil spill-treating agents and oil spill response operations in the marine environment.