Environmental condition-dependent effects of aquatic humic substances on the distribution of phenanthrene in microplastic-contaminated aquatic systems.

Numerous studies have focused on the interaction between microplastics (MPs) and phenanthrene (PHE) in aquatic environments. However, the intricate roles of aquatic humic substances (HS), which vary with environmental conditions, in influencing PHE-MP interactions are not yet fully understood. This study investigates the variable and environmentally sensitive roles of HS in modifying the interactions between PHE and polyethylene (PE) MPs under laboratory-simulated aquatic conditions with varying solution chemistry, including pH, HS types, HS concentrations, and ionic strength. Our findings show that the presence of HS significantly reduces the adsorption of PHE onto both pristine and aged PE MPs, with a more pronounced reduction observed in aged PEs. This effect is highlighted by a notable decrease in the partitioning coefficient (Kd) of PHE, which falls from 2.60 × 104 to 1.30 × 104 L/kg on MPs in the presence of HS. The study also demonstrates that alterations in the net charge of HS solutions are crucial in modifying PHE distribution onto PEs. An initial decrease in Kd values at higher pH levels is reversed when HS is introduced. Furthermore, an increase in HS concentrations is associated with lower Kd values. In conditions of higher ionic strength, the retention of PHE by HS is intensified, likely due to an enhanced salting-out effect. This research highlights the significant role of aquatic HS in modulating the distribution of PHE in MP-polluted waters, which is highly influenced by various solution chemistry factors. The findings are vital for understanding the fate of PHE in MP-contaminated aquatic environments and can contribute to refining predictive models that consider diverse solution chemistry scenarios.

Space-specific flux estimation of atmospheric chemicals from point sources to soil.

Predicting chemical flux to soil from industrial point sources accurately at a regional scale has been a significant challenge due to high uncertainty in spatial heterogeneity and quantification. To address this challenge, we developed an innovative approach by combining California Air Resources Board Puff (CALPUFF) and mass balance models, leveraging their complementary strengths in quantitative accuracy and spatial precision. Specifically, CALPUFF was used to predict the polycyclic aromatic hydrocarbons (PAHs) flux to soil due to industrial sources. Additionally, the spatial distribution coefficient of PAHs flux (e.g., si for spatial unit i) was calculated by neural network and combined with the mass balance model to obtain the results of total PAHs fluxes, which were then combined with the results predicted by CALPUFF to effectively estimate the contribution of industrial sources to soil PAHs flux. Taking a petrochemical industry region located in Zhejiang province, China as a case study, results showed the input Phenanthrene (Phe) and Benzo(a)pyrene (BaP) fluxes predicted by CALPUFF were generally lower than those by the mass balance model, with slightly different distribution patterns. CALPUFF results, based on 36 industrial sources, partially represent those of the mass balance model, which includes all sources and pathways. It was suggested that industrial sources contributed 49%-89% and 65%-100% of soil Phe and BaP, respectively across the study area. The average Phe flux from point sources by deposition averaged 2.68 mg m-2∙a-1 in 2021, accounting for approximately 60% of the total Phe flux to soil. The average BaP flux from point sources by deposition averaged 0.0755 mg m-2∙a-1, accounting for only 0.1%-3.65% of the total BaP flux to soil. Thereby, our approach fills up a gap between the relevance to point sources and the accuracy of deposition quantification in estimating chemical flux from specific point sources to soil at a regional scale.

Aromatase (CYP19) gene as a biomarker for detection of naphthalene and phenanthrene in Colombo to Mirissa coastal water in Sri Lanka.

Naphthalene (NAP) and phenanthrene (PHE) are prevalent Polycyclic Aromatic Hydrocarbons (PAHs) in the environment. High-Performance Liquid Chromatography (HPLC) analysis was performed on marine water samples (n = 57) collected from 19 locations. Molecular screening of the aromatase (CYP19) gene expression was examined using quantitative Reverse Transcriptase PCR (qRT-PCR). The findings of the study showed a significant range of naphthalene concentrations along the coastline, spanning from 1.70 to 15.05 mg/L, where phenanthrene concentrations varied from undetectable to a maximum of 5.36 mg/L. The relative expression of the CYP19 gene ranged from 0.5 to 13.9 in the sampling sites. The ANOVA analysis showed a significant positive correlation (p < 0.05) between the concentrations of PAHs and CYP19 gene expression. The study concluded that the CYP19 gene could be useful in detecting contaminants such as naphthalene and phenanthrene in water. This study may help develop effective strategies to detect and mitigate PAH pollution in coastal areas.

A multi-omics approach to unravelling the coupling mechanism of nitrogen metabolism and phenanthrene biodegradation in soil amended with biochar.

The presence of polycyclic aromatic hydrocarbons (PAHs) in soil negatively affects the environment and the degradation of these contaminants is influenced by nitrogen metabolism. However, the mechanisms underlying the interrelationships between the functional genes involved in nitrogen metabolism and phenanthrene (PHE) biodegradation, as well as the effects of biochar on these mechanisms, require further study. Therefore, this study utilised metabolomic and metagenomic analysis to investigate primary nitrogen processes, associated functional soil enzymes and functional genes, and differential soil metabolites in PHE-contaminated soil with and without biochar amendment over a 45-day incubation period. Results showed that dissimilatory nitrate reduction to ammonium (DNRA) and denitrification were the dominant nitrogen metabolism processes in PHE-contaminated soil. The addition of biochar enhanced nitrogen modules, exhibiting discernible temporal fluctuations in denitrification and DNRA proportions. Co-occurrence networks and correlation heatmap analysis revealed potential interactions among functional genes and enzymes responsible for PHE biodegradation and nitrogen metabolism. Notably, enzymes associated with denitrification and DNRA displayed significant positive correlation with enzymes involved in downstream phenanthrene degradation. Of particular interest was stronger correlation observed with the addition of biochar. However, biochar amendment inhibited the 9-phenanthrol degradation pathway, resulting in elevated levels of glutathione (GSH) in response to environmental stress. These findings provide new insights into the interactions between nitrogen metabolism and PHE biodegradation in soil and highlight the dual effects of biochar on these processes.

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.

[Effect of Microplastics and Phenanthrene on Soil Chemical Properties, Enzymatic Activities, and Microbial Communities].

Microplastic and polycyclic aromatic hydrocarbon (PAHs) pollution have received increasing attention due to their ubiquitous distribution and potential risks in soils. However, the effects of microplastics-PAHs combined pollution on soil ecosystems remain unclear. Polyethylene (PE)/polypropylene (PP) and phenanthrene (PHE) were selected as the representatives of microplastics and PAHs, respectively. A 300-day soil microcosm experiment was conducted to study the single and combined effects of PE/PP and PHE on soil chemical properties, enzymatic activities, and bacterial communities (i.e., quantity, composition, and function), using the soil agricultural chemical analysis method and 16S amplicon sequencing technology. The interactions of soil properties, enzyme activities, and flora in the presence of PE/PP and PHE were analyzed. The results showed that the addition of PE/PP and PHE slightly changed the pH, available phosphorus (AP), and microbial quantity (i.e., bacteria, actinomycetes, and mold) but considerably increased the fluorescein diacetate hydrolase (FDAse) activity. There was a significant enhancement of soil organic matter (SOM) and urease activity in PE, PP, PHE-PE, and PHE-PP amended systems. PHE, PHE-PE, and PHE-PP obviously increased the dehydrogenase/neutral phosphatase activities and available nitrogen (AN) content. PHE had little effect on the microbial community. The PE, PP, PHE-PE, and PHE-PP addition influenced the microbial community to some extent. PE/PP and PHE showed positive effects on the energy production, growth, and reproduction of soil microorganisms and then accelerated the metabolism/degradation of pollutants and membrane transport. The changes in AN and SOM induced by PE/PP and PHE were the key factors affecting soil enzyme activities. Alterations in AN, AP, and pH were mainly responsible for the increase in microbial population. The changes in the microbial community were related to soil chemical properties and enzyme activities, and SOM had a significant effect on the microbial community. The presence of different carbon sources (PE/PP and PHE) in the soil and the microbial interaction also affected the microbiota. In conclusion, the addition of single or combined pollutants of PE/PP and PHE influenced the soil chemical properties, enzymatic activities, bacterial communities, and their interaction processes, thus facilitating the adaptation of the microbial community to pollutant stress.

Transport proteins and their differential roles in the accumulation of phenanthrene in wheat.

The study focuses on the uptake, accumulation, and translocation of polycyclic aromatic hydrocarbons (PAHs) in cereals, specifically exploring the role of peroxidase (UniProt accession: A0A3B5XXD0, abbreviation: PX1) and unidentified protein (UniProt accession: A0A3B6LUC6, abbreviation: UP1) in phenanthrene solubilization within wheat xylem sap. This research aims to clarify the interactions between these proteins and phenanthrene. Employing both in vitro and in vivo analyses, we evaluated the solubilization capabilities of recombinant transport proteins for phenanthrene and examined the relationship between protein expression and phenanthrene concentration. UP1 displayed greater transport efficiency, while PX1 excelled at lower concentrations. Elevated PX1 levels contributed to phenanthrene degradation, marginally diminishing its transport. Spectral analyses and molecular dynamics simulations validated the formation of stable protein-phenanthrene complexes. The study offers crucial insights into PAH-related health risks in crops by elucidating the mechanisms of PAH accumulation facilitated by transport proteins.

Laccase as a useful assistant for maize to accelerate the phenanthrene degradation in soil.

Polycyclic aromatic hydrocarbon (PAH) pollution has attracted much attention due to their wide distribution in soil environment and serious harm to human health. In order to establish an efficient and eco-friendly technology for remediation of PAH-contaminated soil, phytoremediation utilizing maize assisted with enzyme remediation was explored in this study. The results showed that the participation of laccase could promote the degradation of phenanthrene (PHE) from soil and significantly reduce the accumulation of PHE in maize. The degradation efficiency of PHE in soil could reach 77.19% under laccase-assisted maize remediation treatment, while the accumulation of PHE in maize roots and leaves decreased by 41.23% and 74.63%, respectively, compared to that without laccase treatment, after 24 days of maize cultivation. Moreover, it was found that laccase addition shifted the soil microbial community structure and promoted the relative abundance of some PAH degrading bacteria, such as Pseudomonas and Sphingomonas. In addition, the activities of some enzymes that were involved in PAH degradation process and soil nutrient cycle increased with the treatment of laccase enzyme. Above all, the addition of laccase could not only improve the removal efficiency of PHE in soil, but also alter the soil environment and reduce the accumulation of PHE in maize. This study provided new perspective for exploring the efficiency of the laccase-assisted maize in the remediation of contaminated soil, evaluating the way for reducing the risk of secondary pollution of plants in the phytoremediation process.

[Benchmark dose estimation of polycyclic aromatic hydrocarbons exposure base on Bayesian kernel machine regression].

Objective: To explore benchmark dose (BMD) estimations of polycyclic aromatic hydrocarbons (PAHs) based on Bayesian kernel machine regression (BKMR) . Methods: A total of 155 adult residents of a coking plant in Shanxi Province who were surveyed in summer (June to August) from 2014 to 2019 were selected as the research objects. Fasting elbow vein blood of the subjects was collected in the morning for automatic analysis and detection of blood routine. Morning urine samples were collected for automatic analysis and detection of urine routine and urine creatinine detection. BKMR model combined with BMD method was used to calculate the acceptable doses of PAHs exposure on red blood cell damage in non-occupational population. Results: The concentration of hydroxylpolycyclic aromatic hydrocarbons (OH-PAHs) in the red blood cells abnormal group (n=117) was significantly higher than that in the normal group (n=38) (P<0.01). In the combined effect of OH-PAHs, 2-hydrol-naphthalene contributed the most, and the posterior inclusion probability (PIP) value was 0.9354. When OH-PAHs ≥P(55) concentration, the joint effect on the risk of red blood cell abnormalities increased as the concentration of the OH-PAHs mixture increased. When OH-PAHs were at P(65) and P(75) concentrations, respectively, the risk of red blood cell abnormalities in adults were 3.09 and 4.98 times that of OH-PAHs at P(50) concentrations, respectively. Compared with high concentration, low concentration of OH-PAHs exposure was more sensitive to red blood cell darmage. The acceptable doses of 8 kinds of OH-PAHs were 1.010 µmol/mol Cr (2-hydrol-naphthalene), 0.743 µmol/mol Cr (1-hydrol-naphthalene), 0.901 µmol/mol Cr (2-hydroxy-fluorene) and 0.775 µmol/mol Cr (1-hydroxy-phenanthrene), 0.737 µmol/mol Cr (1-hydroxy-pyrene), 0.607 µmol/mol Cr (9-hydroxy-fluorene), 0.713 µmol/mol Cr (2-hydroxy-phenanthrene) and 0.628 µmol/mol Cr (3-hydroxybenzo[a] pyrene), respectively. Conclusion: OH-PAHs mixture has positive combined effect on red blood cell damage in non-occupational population, and low concentration of OH-PAHs exposure is more sensitive to red blood cell damage. It is recommended that the exposure dose of PAHs should be controlled within 1 µmol/mol Cr.

Integument colour change: Tracking delayed growth of Oppia nitens as a sub-lethal indicator of soil toxicity.

Growth is an important toxicity end-point in ecotoxicology but is rarely used in soil ecotoxicological studies. Here, we assessed the growth change of Oppia nitens when exposed to reference and heavy metal toxicants. To assess mite growth, we developed an image analysis methodology to measure colour spectrum changes of the mite integument at the final developmental stage, as a proxy for growth change. We linked the values of red, green, blue, key-black, and light colour of mites to different growth stages. Based on this concept, we assessed the growth change of mites exposed to cadmium, copper, zinc, lead, boric acid, or phenanthrene at sublethal concentrations in LUFA 2.2 soil for 14 days. Sublethal effects were detected after 7 days of exposure. The growth of O. nitens was more sensitive than survival and reproduction when exposed to copper (EC50growth = 1360 mg/kg compared to EC50reproduction = 2896 mg/kg). Mite growth sensitivity was within the same order of magnitude to mite reproduction when exposed to zinc (EC50growth = 1785; EC50reproduction = 1562 mg/kg). At least 25% of sublethal effects of boric acid and phenanthrene were detected in the mites but growth was not impacted when O. nitens were exposed to lead. Consistent with previous studies, cadmium was the most toxic metal to O. nitens. The mite growth pattern was comparable to mite survival and reproduction from previous studies. Mite growth is a sensitive toxicity endpoint, ecologically relevant, fast, easy to detect, and can be assessed in a non-invasive fashion, thereby complimenting existing O. nitens testing protocols.

Microbe combined with Fe2+-heat activated persulfate to decompose phenanthrene in red soil: comparison of acid-resistant degrading microflora and indigenous bacteria.

This work is designed to counteract the deficiency of targeted research on the PAHs polluted specific soil, especially when the chemicals extremely denatured it. Phenanthrene-contaminated red soil was treated through two-stage process: persulfate oxidation (on dosages of 3.48%, 5.21%, and 6.94%, combined with Fe2+ and ß-cyclodextrin, then heated) followed by biodegradation (indigenous bacteria vs. acid-resistant PAHs-degrading microflora (named ADM)) for 90 days. The dosage of oxidant greatly affected the removal efficiencies, which ranged from 46.78 to 85.34% under different treatment. After undergoing oxidation, the soil pH dropped below 3.0 synchronously and retained relatively strong oxidation state. The indigenous bacteria in red soil showed considerable degradation potential that will not vanish upon the sudden change of soil properties, whose average combined removal reached 95.43%, even higher than subgroups of bioaugmentation, but the population structure showed extremely simplex (Proteobacteria as superior occupied proportion of 91.77% after 90-day rehabilitation). The ADM screened from the coking wastewater was dominated by Klebsiella (75.4%) and Pseudomonas (23.6%), whose cooperation with 6.94% persulfate made the residual PHE reduced to less than 50 mg·kg-1 in about 28 days. High-throughput sequencing analysis showed that the microbial community composition of the ADM applied-group was more abundant in the later stage of remediation. ADM inoculation has the advantages of shortening the restoration period and having a positive impact on the soil micro-ecology.

Disturbance of OH-PAH metabolites in urine induced by single PAH lab exposure.

Due to the high exposure toxicity and individual variability of polycyclic aromatic hydrocarbons (PAHs), it is difficult to accurately characterize the actual exposure of exposed individuals through external exposure detection. In this study, the monohydroxyl metabolites of naphthalene, phenanthrene, pyrene, and 9-fluorenone were identified in the urine of low-dose PAH-exposed individuals based on ultra-performance liquid chromatography-high-resolution mass spectrometry (UPLC-HRMS), and their concentrations were monitored for 15 consecutive days after exposure. The results showed that the metabolite concentrations of naphthalene, phenanthrene, and pyrene were basically the same, and all of them reached the maximum value at day 8. In contrast, the metabolite of 9-fluorenone reached its maximum value on day 2. This study showed that the four metabolites were strongly correlated with their parent PAH exposure, with a wide detection window, and their assays were specific, sensitive, and reliable, while the sampling difficulty was low, so the four hydroxylated PAHs may be potential low-dose biomarkers of PAH internal exposure. This study will provide methodological and data support for further health risk studies involving internal exposure to organic pollutants such as PAHs.

Investigation of the spatial distribution of airborne polycyclic aromatic hydrocarbons using Rhytidiadelphus squarrosus in Tórshavn, Faroe Islands.

Due to adverse effects of Polycyclic Aromatic Hydrocarbons (PAHs) on human health, it is important to understand how airborne PAHs, are spatially distributed within urban areas. Moss has been shown to be a suitable material for biomonitoring of airborne PAH pollution. In this study, the moss Rhytidiadelphus squarrosus was sampled throughout Tórshavn, Faroe Islands. 53 Rhytidiadelphus squarrosus samples were extracted using a matrix solid-phase dispersive extraction method and analysed for 19 parent PAHs and six groups of alkylated PAHs using gas chromatography mass-spectrometry. All PAHs were quantified in at least one Rhytidiadelphus squarrosus sample, and the sum of the EPA 16 PAHs (Æ©PAHEPA16) ranged from 0.90 to 344 µg kg-1 dry weight. Higher concentrations were found close to the harbour and the main roads. The spatial correlation was investigated for the Æ©PAHEPA16, pyrene, fluoranthene, chrysene, benzo(e)pyrene, benzo(g,h,i)perylene, C1-phenanthrenes/C1-anthracenes, and C2-phenanthrenes/C2-anthracenes using variograms. The effective range of the spatial correlation was between 500 to 700 m of all PAHs. The evaluation of diagnostic ratios of fluoranthene to pyrene, and benzo(a)anthracene to chrysene suggest that different pollution sources affect urban areas of different types. To the best of our knowledge, this is the first time airborne PAH pollution patterns were mapped in an Arctic town, and the first time, Rhytidiadelphus squarrosus was used for tracing PAH pollution sources. Rhytidiadelphus squarrosus is suitable for biomonitoring and mapping PAH pollution within urban areas since it is widespread, and suitable for mapping PAHs.

Whole-genome sequence analysis reveals phenanthrene and pyrene degradation pathways in newly isolated bacteria Klebsiella michiganensis EF4 and Klebsiella oxytoca ETN19.

Polycyclic aromatic hydrocarbons (PAHs) are diverse pollutants of significant environmental concerns, requiring effective biodegradation. This study used different bioinformatics tools to conduct whole-genome sequencing of two novel bacterial strains, Klebsiella michiganensis EF4 and K. oxytoca ETN19, to improve our understanding of their many genomic functions and degradation pathways of phenanthrene and pyrene. After 28 days of cultivation, strain EF4 degraded approximately 80% and 60% of phenanthrene and pyrene, respectively. However, their combinations (EF4 +ETN19) showed tremendous phenanthrene degradation efficiency, supposed to be at the first-level kinetic model with a t1/2 value of approximately 6 days. In addition, the two bacterial genomes contained carbohydrate-active enzymes and secondary metabolites biosynthetic gene clusters associated with PAHs degradation. The two genomes contained the bZIP superfamily of transcription factors, primarily the cAMP-response element-binding protein (CREB), which could regulate the expression of several PAHs degradation genes and enzymes. Interestingly, the two genomes were found to uniquely degrade phenanthrene through a putative pathway that catabolizes 2-carboxybenzalpyruvate into the TCA cycle. An operon containing multicomponent proteins, including a novel gene (JYK05_14550) that could initiate the beginning step of phenanthrene and pyrene degradation, was found in the EF4 genome. However, the degradation pathway of ETN19 showed that the yhfP gene encoding putative quinone oxidoreductase was associated with phenanthrene and pyrene catabolic processes. Furthermore, the significant expression of catechol 1,2-dioxygenase and quinone oxidoreductase genes in EF4 +ETN19 and ETN19 following the quantitative reverse transcription polymerase chain reaction (qRT-PCR) analysis confirmed the ability of the bacteria combination to degrade pyrene and phenanthrene effectively. These findings present new insight into the possible co-metabolism of the two bacterial species in the rapid biodegradation of phenanthrene and pyrene in soil environments.

The role of multi-low molecular weight organic acids on phenanthrene biodegradation: Insight from cellular characteristics and proteomics.

Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic and ubiquitous pollutants that need to be solved. The low-molecular-weight organic acid (LMWOA) holds the promise to accelerate the capacity of microbes to degrade PAHs. However, the degradation mechanism(s) with multi-LMWOAs has not been understood yet, which is closer to the complex environmental biodegradation in nature. Here, we demonstrated a comprehensive cellular and proteomic response pattern by investigating the relationship between a model PAH degrading strain, B. subtilis ZL09-26, and the mixture LMWOAs (citric acid, glutaric acid, and oxalic acid). As a result, multi-LMWOAs introduced a highly enhanced phenanthrene (PHE) degradation efficiency with up to 3.1-fold improvement at 72 h, which is accompanied by the enhancement of strain growth and activity, but the releasement of membrane damages and oxidative stresses. Moreover, a detailed proteomic analysis revealed that the synergistic perturbation of various metabolic pathways jointly governed the change of cellular behaviors and improved PHE degradation in a network manner. The obtained knowledge provides a foundation for designing the artificial LMWOAs mixtures and guides the rational remediation of contaminated soils using bio-stimulation techniques.

Adsorption of 2-hydroxynaphthalene, naphthalene, phenanthrene, and pyrene by polyvinyl chloride microplastics in water and their bioaccessibility under in vitro human gastrointestinal system.

The interaction of microplastics (MPs) and organic pollutants has recently become a focus of investigation. To understand how microplastic residues affect the migration of organic pollutants, it is necessary to examine the adsorption and desorption behavior of organic pollutants on MPs. In this study, integrated adsorption/desorption experiments and theoretical calculations were used to clarify the adsorption mechanism of 2-hydroxynaphthalene (2-OHN), naphthalene (NAP), phenanthrene (PHE), and pyrene (PYR) by polyvinyl chloride microplastics (PVC-MPs). Based on the phenomenological mathematical models, the rate-limiting step for analyte adsorption onto PVC-MPs was adsorption onto active sites (R2 = 0.865-0.995). Except for PHE, analyte adsorption isotherms were well described by the Freundlich model (R2 = 0.992-0.998), and adsorption thermodynamics showed that analyte adsorption on PVC-MPs was a spontaneous exothermic process (ΔH0 < 0; ΔG0 < 0). Based on the order of adsorption efficiency of 2-OHN < NAP < PHE < PYR, which is identical to the competitive adsorption experiment, polycyclic aromatic hydrocarbon (PAH) adsorption on PVC-MPs increased as the aromatic ring number increased and the hydroxyl content decreased. The release of 2-OHN (49 %-52 %) from PVC-MPs into the simulated gastrointestinal environment was greater than that of NAP (5.5 %-5.7 %). Theoretical calculations and adsorption tests indicated that hydrophobic interaction was the primary influence on the adsorption of PAHs and their hydroxylated derivatives by PVC-MPs. These findings improve our understanding of MPs' behavior and dangers as pollutant carriers in the aquatic environment and help us develop recommendations for the pollution control of MPs.

Fluorescent spectroscopy paired with parallel factor analysis for quantitative monitoring of phenanthrene biodegradation and metabolite formation.

Polycyclic aromatic hydrocarbons (PAHs) are a class of environmental contaminants released into the environment from both natural and anthropogenic sources that are associated with carcinogenic, mutagenic, and teratogenic health effects. Many remediation strategies for the treatment of PAH contaminated material, including bioremediation, can lead to the formation of toxic transformation products. Analytical techniques for PAHs and PAH transformation products often require extensive sample preparation including solvent extraction and concentration, chromatographic separation, and mass spectrometry to identify and quantify compounds of interest. Excitation-emission matrix (EEM) fluorescent spectroscopy paired with parallel factor analysis (PARAFAC) is an approach for analyzing PAHs that eliminates the need for extensive sample preparation and separation techniques before analysis. However, this technique has rarely been applied to monitoring PAH biotransformation and formation of PAH metabolites. The objectives of this research were to compare an established targeted analytical method to two-dimensional fluorescent spectroscopy and combined EEM-PARAFAC methods to monitor phenanthrene degradation by a bacterial pure culture, Mycobacterium Strain ELW1, identify and quantify phenanthrene transformation products, and derive kinetic constants for phenanthrene degradation and metabolite formation. Both phenanthrene and its primary transformation product, trans-9,10-dihydroxy-9,10-dihydrophenanthrene, were identified and quantified with the EEM-PARAFAC method. The value of the EEM-PARAFAC method was demonstrated in the superiority of sensitivity and accuracy of quantification to two-dimensional fluorescent spectroscopy. Quantification of targets and derivation of kinetic constants using the EEM-PARAFAC method were validated with an established gas chromatography-mass spectrometry (GC-MS) method. To the authors' knowledge, this is the first study to use an EEM-PARAFAC method to monitor, identify, and quantify both PAH biodegradation and PAH metabolite formation by a bacterial pure culture.

Toxicokinetic analyses of naphthalene, fluorene, phenanthrene, and pyrene in humans after single oral administration.

Polycyclic aromatic hydrocarbons (PAHs) are generated by incomplete combustion of organic matter. They have health effects in multiple organs and can cause lung, skin, and bladder cancers in humans. Although data regarding their toxicity is available, information on the absorption, distribution, metabolism, and excretion of PAHs in humans is very limited. In the present study, deuterium-labeled naphthalene (Nap), fluorene (Flu), phenanthrene (Phe), and pyrene (Pyr) were orally administered as a single dose (0.02-0.04 mg/kg) to eight healthy adults. Both serum and urine samples were monitored for 72 h after the exposure. Parent compounds and PAH metabolites (monohydroxy-PAHs; OH-PAHs) were measured by headspace-solid phase microextraction coupled with gas chromatography-mass spectrometry and high-performance liquid chromatography-tandem mass spectrometry, respectively. Based on the time-concentration profiles in serum and urine, non-compartmental analysis was performed, and two-compartment models were constructed and validated for each PAH. Subsequently, all of the parent compounds were rapidly absorbed (Tmax: 0.25 to 1.50 h) after oral administration and excreted in urine with a biological half-life (T1/2) of 1.01 to 2.99 h. The fractional urinary excretion (Fue) of OH-PAHs ranged from 0.07 % to 11.3 %; their T1/2 values ranged from 3.4 to 11.0 h. The two-compartment models successfully described the toxicokinetic characteristics of each PAH and its metabolites. Fue and the two-compartment models could be useful tools for exposure simulation or dose-reconstruction of PAHs. The results of this study will provide useful information for interpreting biomonitoring data of PAHs.

Constructing model-averaging species sensitivity distributions of Phenanthrene based on reproductive fitness: Implications for assessing ecological risk in urban watershed.

The challenge in optimizing the method of constructing species sensitivity distribution (SSD) remains. In this study, a model-averaging SSD was created to evaluate the ecological risk of Phenanthrene (PHE) in urban watershed based on reproductive fitness. Specifically, concentrations of PHE were measured in surface water samples collected from various watersheds of Wuhan, including five lake watersheds and the Wuhan reach of the Yangtze River and Han River. The reproductive endpoint of aquatic species was calculated to be most sensitive to PHE exposure, with the value of predict no-effect concentration (PNEC) at 0.19 µg/L. The results of probabilistic assessment methods, including joint probability curve (JPC), overall risk probability (ORP), and distribution-based quotient (DBQ), indicated that the ecological risks of PHE in large lakes have dropped significantly with distance from the downtown area of Wuhan, and the long-term effects of industrial activities may increase the risks in the lake watersheds. Basically, the ecological risks in Yangtze River are negligible; however, there is a relatively high risk of PHE in the Han River and some lake watersheds. The cos Î¸ similarity analysis indicated the Yangtze River is strongly connected to the low-risk lake watersheds, and that in part reflects the risk in the Yangtze River being controlled by its surrounding these lake watersheds.

Simultaneous Prediction, Determination, and Extraction of Four Polycyclic Aromatic Hydrocarbons in the Environment Using a UCON-NaH2PO4 Aqueous Two-Phase Extraction System Combined with High-Performance Liquid Chromatography-Ultraviolet Detection.

In this paper, a new aqueous two-phase extraction system(ATPES) consisting of UCON (poly(ethylene glycol-ran-propylene glycol) monobutyl ether)-NaH2PO4 was established, and four trace polycyclic aromatic hydrocarbons (PAHs: fluorene, anthracene, pyrene and phenanthrene) in water and soil were analyzed by high-performance liquid chromatography (HPLC)-ultraviolet detection. In the multi-factor experiment, the central composite design (CCD) was used to determine the optimum technological conditions. The final optimal conditions were as follows: the concentration of UCON was 0.45 g·mL-1, the concentration of NaH2PO4 was 3.5 mol·L-1, and the temperature was 30 °C. The recovery of the four targets was 98.91-99.84% with a relative standard deviation of 0.3-2.1%. Then UCON recycling and cyclic tests were designed in the experiment, and the results showed that the recovery of PAHs gradually increased in the three extractions because of the remaining PAHs in the salt phase of last extraction. The recovery of PAHs in the UCON recycling test was less than that in the extraction test due to the wastage of UCON. In addition, a two-phase aqueous extraction model was established based on the random forest (RF) model. The results obtained were compared with the experimental data, and the root mean square error (RMSE) was 0.0371-0.0514 and the correlation coefficient R2 was 96.20-98.53%, proving that the model is robust and reliable.