Roles of Natural Phenolic Compounds in Polycyclic Aromatic Hydrocarbons Abiotic Attenuation at Soil-Air Interfaces through Oxidative Coupling Reactions.

Little information is available on the roles of natural phenolic compounds in polycyclic aromatic hydrocarbons (PAHs) attenuation at dry soil-air interfaces. The purpose of this study was to determine the roles of model phenolic constituents of soil organic matter (SOM) on the abiotic attenuation of PAHs. The phenolic compounds can significantly change the attenuation rates of PAHs, among which hydroquinone was the most effective in promoting anthracene and benzo[a]anthracene attenuation. Product identification and sequential extraction experiments revealed hydroquinone enhanced the formation of oxidative coupling products and promoted the incorporation of PAHs into humic analogues, thereby reducing potential risks to humans and ecosystems. Electron paramagnetic resonance spectroscopy analyses showed both PAHs and phenolic compounds could donate electrons to Lewis acid sites of soil minerals, resulting in the generation of persistent free radicals (PFRs). PFRs could promote the generation of ·OH to enhance PAH oxidation and could cross-couple with PAHs, resulting in high-molecular-weight oxidative coupling products. This study revealed for the first time the reaction mechanism between PAHs and phenolic components of SOM under relatively dry conditions and provided new insights into promoting PAHs detoxification in soils but also a potential strategy to increase the organic carbon sequestration.

The dangerous link between coal dust exposure and DNA damage: unraveling the role of some of the chemical agents and oxidative stress.

Exposure to coal mining dust poses a substantial health hazard to individuals due to the complex mixture of components released during the extraction process. This study aimed to assess the oxidative potential of residual coal mining dust on human lymphocyte DNA and telomeres and to perform a chemical characterization of coal dust and urine samples. The study included 150 individuals exposed to coal dust for over ten years, along with 120 control individuals. The results revealed significantly higher levels of DNA damage in the exposed group, as indicated by the standard comet assay, and oxidative damage, as determined by the FPG-modified comet assay. Moreover, the exposed individuals exhibited significantly shorter telomeres compared to the control group, and a significant correlation was found between telomere length and oxidative DNA damage. Using the PIXE method on urine samples, significantly higher concentrations of sodium (Na), phosphorus (P), sulfur (S), chlorine (Cl), potassium (K), iron (Fe), zinc (Zn), and bromine (Br) were observed in the exposed group compared to the control group. Furthermore, men showed shorter telomeres, greater DNA damage, and higher concentrations of nickel (Ni), calcium (Ca), and chromium (Cr) compared to exposed women. Additionally, the study characterized the particles released into the environment through GC-MS analysis, identifying several compounds, including polycyclic aromatic hydrocarbons (PAHs) such as fluoranthene, naphthalene, anthracene, 7H-benzo[c]fluorene, phenanthrene, pyrene, benz[a]anthracene, chrysene, and some alkyl derivatives. These findings underscore the significant health risks associated with exposure to coal mining dust, emphasizing the importance of further research and the implementation of regulatory measures to safeguard the health of individuals in affected populations.

Seasonal assessment of the distribution, source apportionment, and risk of water-contaminated polycyclic aromatic hydrocarbons (PAHs).

The research aims to evaluate the seasonal differences in the distribution, source, and risks of water-contaminated PAHs. The PAHs were extracted by the liquid-liquid method and analyzed with GC-MS, and a total of eight PAHs were detected. There was a percentage increase in the average concentration of the PAHs from the wet to the dry season in the range of 20 (Anthracene)-350 (Pyrene)%. Total PAHs (∑PAHs) range from 0.31 to 1.23 mg/l in the wet period and from 0.42 to 1.96 mg/l in the dry period. The distribution of the average PAHs in mg/l showed that Fluoranthene ≤ Pyrene < Acenaphthene < Fluorene < Phenanthrene < Acenaphthylene < Anthracene < Naphthalene in wet period and while Fluoranthene < Acenaphthene < Pyrene < Fluorene < Phenanthrene < Acenaphthylene < Anthracene < Naphthalene in the dry period. The children were exposed to non-carcinogenic risk through non-dietary ingestion due to the accumulative effect (HI) of the PAHs in the dry period. Furthermore, the naphthalene was responsible for ecological and carcinogenic risk in the wet period, while the fluorene, phenanthrene, and anthracene were responsible for ecological and carcinogenic risk in the dry period. However, while adults and children are both susceptible to carcinogenic risk through the oral channel during the dry period, only children are susceptible to non-carcinogenic risk through this pathway. The multivariate statistical analysis revealed the influence of physicochemical parameters on the detected PAHs and also showed the PAHs' sources to be mainly combustion, pyrolysis, and vehicular emission.

The study of three beaches of South-West Cameroon polluted by polycyclic aromatic hydrocarbons.

The US Environmental Protection Agency (US-EPA) published a priority list of 16 polycyclic aromatic hydrocarbons (PAHs), which are compounds that are studied in a variety of matrices due to their wide range of risks. Environmental compartments can be contaminated with PAHs from different sources, such as wastewater from industries and petroleum spills. For the case of Cameroon, there are no recorded data concerning the sources, distributions, and toxicity levels of PAHs in water and sediment from Cameroon beaches which are found in South-West, Littoral, and South Regions. In this work, only three beaches from South-West Region were studied regarding the sources, distributions, and toxicity levels of PAHs in water and sediment. The analyzed samples came from Bobende coastal beach, Down-beach, and Cape-Limboh beach. To achieve the analyses, liquid-liquid extraction and gas chromatography enabled the identification and quantification of PAH compounds from sediments and marine water. Out of the 16 PAHs listed by US-EPA, twelve were identified and quantified among which four of them were light molecular weight PAHs (acenaphthylene, fluorene, phenanthrene, and anthracene). Anthracene in the Cape-Limboh sample presented the highest concentration (477.57 ng/kg weight of dry sediment) of LMW-PAHs. Eight identified and quantified PAHs of high molecular weight as a whole, three absent PAHs (benzo[a]anthracene, dibenzo[a,h]anthracene, and benzo[g,h,i]perylene) in the Cape-Limboh sample, while only one is absent in the Bobende samples (dibenzo[a,h]anthracene) and Down Beach (benzo[g,h,i]perylene). According to the ratios used for the determination of the sources of PAHs, it came out that the source of PAHs from all beaches is pyrolytic. In all samples, BaA is the only high molecular weight PAH presenting serious toxicity and ecological risk.

Hydrophobic microporous extraction on polyurethane sponges for convenient and sensitive analysis of organic molecules in water.

RATIONALE: Various solvent supports have been developed to overcome solvent instability during liquid-phase microextraction. The hydrophobic polyurethane sponge (PS) possesses numerous cross-linked internal microchannels and terminal micropores that can facilitate steady solvent storage capacity, high extraction efficiency, extractant loading, and recycling convenience. METHODS: In this study, an easy, convenient, and efficient PS-supported liquid-phase microextraction (PS-LPME) coupled with gas chromatography-mass spectrometry (GC-MS) method was developed for the trace analysis of different organic compounds in aqueous solutions. Different extraction solvents, PS dosages, stirring speeds, and extraction times were first investigated by extracting eight polycyclic aromatic hydrocarbons (PAHs: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, and pyrene), and then applied for the analysis of triazines, amides, chloroacetamides, and organophosphorus compounds. RESULTS: High enrichment factors (approximately 208-439) were observed for the monitored PAHs. Good linearities, with determination coefficients (r2 ) greater than 0.9992, were achieved in the concentration range of 0.01-50 µg L-1 . Low limits of detection and quantification were found in the ranges of 0.3-3 ng L-1 and 1-10 ng L-1 , respectively. At three spiked concentrations (0.1, 1, and 10 µg L-1 ), good recoveries were obtained in the range of 91.6-118.5% with intra- and inter-day relative standard deviations of less than 6.4% and 11.7%, respectively. CONCLUSIONS: The developed PS-LPME method coupled with GC-MS was successfully applied in the analysis of different organic compounds in aqueous solutions and has shown great convenience and satisfactory enrichment performance in microextraction analysis.

Correlation of soil microbiome with crude oil contamination drives detection of hydrocarbon degrading genes which are independent to quantity and type of contaminants.

The impacts of crude oil contamination on soil microbial populations were explored in seven different polluted areas near oil and gas drilling sites and refineries of Assam, India. Using high-throughput sequencing techniques, the functional genes and metabolic pathways involved in the bioconversion of crude oil contaminants by the indigenous microbial community were explored. Total petroleum hydrocarbon (TPH) concentrations in soil samples ranged from 1109.47 to 75,725.33 mg/kg, while total polyaromatic hydrocarbon (PAH) concentrations ranged from 0.780 to 560.05 mg/kg. Pyrene, benzo[a]anthracene, naphthalene, phenanthrene, and anthracene had greater quantities than the maximum permitted limits, suggesting a greater ecological risk, in comparison to other polyaromatic hydrocarbons. According to the metagenomic data analysis, the bacterial phyla Proteobacteria, Actinobacteria, Acidobacteria, and Bacteroides were the most prevalent among all polluted areas. The most prominent hydrocarbon degraders in the contaminated sites included Burkholderia, Mycobacterium, Polaromonas, and Pseudomonas. However, the kinds of pollutants and their concentrations did not correlate with the abundances of respective degrading genes for all polluted locations, as some of the sites with little to low PAH contamination had significant abundances of corresponding functional genes for degradation. Thus, the findings of this study imply that the microbiome of hydrocarbon-contaminated areas, which are biologically involved in the degradation process, has various genes, operons and catabolic pathways that are independent of the presence of a specific kind of contaminant.

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.

Performances of the barrel kiln used in cottage industry for fish processing and effects on physicochemical characteristics and safety of smoked fish products.

BACKGROUND: In the traditional food sector, the smoking process and smoking-drying process are widely used to increase the shelf-life of seafood products. The smoking process and smoking-drying process are mainly performed using barrel kiln and wood as fuel in many West African countries. The present study evaluated the performances of the barrel kiln and its effects on physicochemical characteristics and safety of smoked fish (SF) and smoked-dried fish (SDF). Twelve follow-ups were conducted with three experimental processors and 24 samples of fish collected at different steps of processing were analyzed in a laboratory using standard methods. RESULTS: The extreme values of combustion temperature recorded during the smoking process (456.4 °C) and smoking-drying process (482.8 °C) were higher than 450 °C, the temperature at which wood pyrolysis generates polycyclic aromatic hydrocarbons (PAHs). Smoked fish were highly contaminated with PAHs, and showed maximal levels of benzo[a]pyrene (52.7 µg kg-1 ) and PAH4 (i.e. sum of benzo[a]pyrene, chrysene, benzo[b]fluoranthene and benz[a]anthracene) (290.9 µg kg-1 ) exceeding the European Union limits by about 25-fold. After smoking of Scomber scombrus and smoking-drying of Cypselurus cyanopterus, no significant differences were recorded for lipid, protein and biogenic amine contents between fresh and processed fish, even if the histamine content of both fish exceeded the limit fixed by the European Union regulation. CONCLUSION: The results obtained in the present study showed that smoked fish and smoked-dried fish produced using barrel kiln and wood fuel are highly contaminated by PAHs. Therefore, there is a need to improve the preservation practices of raw fish and smoking conditions to limit the contamination of end-products by PAHs known to be carcinogenic components for humans and to ensure consumer safety. © 2021 Society of Chemical Industry.

Influence of vehicular emissions on the levels of polycyclic aromatic hydrocarbons (PAHs) in urban and industrial areas of La Plata, Argentina.

Polycyclic aromatic hydrocarbons (PAHs) are considered potentially toxic, even carcinogenic, because of their affection to public health and the environment. It is necessary to know their ambient levels and the origin of these pollutants in order to mitigate them. A concerning scenario is the one in which commercial/administrative, industrial, and residential activities coexist. In this context, Gran La Plata (Argentina) presents such characteristics, in addition to the presence of one of the most important petrochemical complexes in the country and intense vehicular traffic. The source apportionment of PAH emission in the region, associated to 10-µm and 2.5-µm particulate matter fractions, was studied. First, different missing value imputation methods were evaluated for PAH databases. GSimp presented a better performance, with mean concentrations of ∑PAHs of 65.8 ± 40.2 ng m-3 in PM10 and 39.5 ± 18.0 ng m-3 in PM2.5. For both fractions, it was found that the highest contribution was associated with low molecular weight PAHs (3 rings), with higher concentrations of anthracene. Emission sources were identified by using principal component analysis (PCA) together with multiple linear regression (MLR) and diagnostic ratios of PAHs. The results showed that the main emission source is associated with vehicular traffic in both fractions. Classification by discriminant analysis showed that emissions can be identified by region and that fluoranthene, benzo(a)anthracene, and anthracene in PM10 and anthracene and phenanthrene in PM2.5 are a characteristic of emissions from the petrochemical complex.

Aloe gel-base food products: Chemical, toxicological, and regulatory aspects.

Aloe products are increasingly valued as ingredients in food supplements and flavoring agents. In early March 2020, the European Commission drafted a ban on the use of Aloe products that contain hydroxyanthracene derivatives (HADs) in food, following the opinion on concerns about the toxicity of vegetable extracts containing HADs carried out by the European Food Safety Authority (EFSA). Aloe gel preparation is characterized by minimal amounts of HADs, only present as contaminants during extraction, compared to other sold Aloe preparations such as Aloe latex and Aloe whole leaf extract. This review provides a comprehensive account of the toxicological aspects of Aloe gel, and briefly discusses the chemical profile of other Aloe preparations. Unlike these other preparations, pure Aloe gel shows no toxic effects. However, further toxicological studies remain necessary to establish the maximum permissible limit of HAD contaminants in Aloe gel, considering daily doses and maximum duration of treatments. Finally, officially validated analytical methods for determination of HADs are required, in the form of tools for use by Companies and Competent Authorities to ensure the absence of HAD contamination in raw materials or in finished products.

Determination of Absolute Purities of Hygroscopic Substances by Quantitative NMR Analysis for the Standardization of Quantitative Reagents in the Japanese Pharmacopoeia (Part 2).

As a new absolute quantitation method for low-molecular compounds, quantitative NMR (qNMR) has emerged. In the Japanese Pharmacopoeia (JP), 15 compounds evaluated by qNMR are listed as reagents used as the HPLC reference standards in the assay of crude drug section of the JP. In a previous study, we revealed that humidity affects purity values of hygroscopic reagents and that (i) humidity control before and during weighing is important for a reproducible preparation and (ii) indication of the absolute amount (not purity value), which is not affected by water content, is important for hygroscopic products determined by qNMR. In this study, typical and optimal conditions that affect the determination of the purity of ginsenoside Rb1 (GRB1), saikosaponin a (SSA), and barbaloin (BB) (i.e., hygroscopic reagents) by qNMR were examined. First, the effect of humidity before and during weighing on the purity of commercial GRB1, with a purity value determined by qNMR, was examined. The results showed the importance afore-mentioned. The results of SSA, which is relatively unstable in the dissolved state, suggested that the standardization of humidity control before and during weighing for a specific time provides a practical approach for hygroscopic products. In regard to BB, its humidity control for a specific time, only before weighing, is enough for a reproducible purity determination.

Simultaneous and rapid determination of polycyclic aromatic hydrocarbons by facile and green synthesis of silver nanoparticles as effective SERS substrate.

A green synthesis method for nanoscale silver using ß-cyclodextrin as both reducing agent and stabilizer was developed. ß-cyclodextrin was used not only as a reducing agent but also a stabilizing agent for nano-silver, and is also an excellent detection substrate due to its special structure (inner hydrophobic and outer hydrophilic ring structure). Then, the green synthesized silver nanoparticles were used as Surface-enhanced Raman spectroscopy (SERS) enhanced substrates to detect polycyclic aromatic hydrocarbons, such as: anthracene, pyrene, chrysene and triphenylene. The SERS substrate can be used for both quantitative detection of the four polycyclic aromatic hydrocarbons and qualitative identification of mixtures of these hydrocarbons. This synthesis method is simple and convenient, having great potential in simultaneous and rapid detection of environmental organic pollutants.

Coumarins as Powerful Photosensitizers for the Cationic Polymerization of Epoxy-Silicones under Near-UV and Visible Light and Applications for 3D Printing Technology.

In this study, eight coumarins (coumarins 1-8) are proposed as near-UV and blue light sensitive photoinitiators/photosensitizers for the cationic polymerization (CP) of epoxysilicones when combined with 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (IOD). Among these coumarins, four of them (coumarins 1, 2, 6 and 8) have never been reported in the literature, i.e., these structures have been specifically designed to act as photoinitiators for silicones upon near UV and visible irradiation. Good final reactive epoxy function conversions (FCs) and also high rates of polymerization (Rp) were achieved in the presence of the newly proposed coumarin-based systems. The polymers generated from the photopolymerization of epoxysilicones can be considered as attractive candidates for several applications such as: elastomers, coatings, adhesives, and so on. The goal of this study focuses also on the comparison of the new proposed coumarins with well-established photosensitizers i.e., 1-chloro-4-propoxythioxanthone (CPTX), 9,10-dibutoxyanthracene (DBA) or some commercial coumarins (Com. Coum). As example of their high performance, the new proposed coumarins were also used for laser write experiments upon irradiation with a laser diode at 405 nm in order to develop new cationic 3D printing systems.

Hybrids of a 9-anthracenyl moiety and fluorescein as chemodosimeters for the detection of singlet oxygen in live cells.

Singlet oxygen (1O2) plays an important role in human innate immune response, plant physiology and anticancer photodynamic therapy (PDT). Therefore, its monitoring by convenient and sensitive methods (e.g. by detecting a fluorescence signal) by using non-toxic reagents would be advantageous. Known fluorogenic 1O2-chemodosimeters can potentially consume reducing agents in cells leading to the generation of toxic side products that limit their applications. In this paper we report on a series of 9-anthracenyl-fluorescein hybrids, which do not require any reducing agents for their reaction with 1O2. The selected compound 8d at a very low concentration of 100 nM is able to detect 1O2 in live human promyelocytic leukemia HL-60 cells with over 35-fold fluorescence signal enhancement within only 20 min assay time. This chemodosimeter is not toxic to HL-60 cells at concentrations ≤1 µM (higher concentrations were not tested) even at long incubation times ≤48 h.

Accumulation and translocation of phenanthrene, anthracene and pyrene in winter wheat affected by soil water content.

Polycyclic aromatic hydrocarbons (PAHs) are universal organic pollutants in the agro ecosystems in China, therefore, it is important to understand the uptake and accumulation of PAHs in crops growing on PAHs contaminated soils for human health risk assessments. Water management is a common practice to maintain high grain yields during wheat production. However, the effects of soil water content on the accumulation and translocation of PAHs in wheat are still not clear. The main objectives of the present study were to investigate the effects of soil water content on the accumulation of three selected PAHs (Σ3PAHs, phenanthrene, anthracene and pyrene) in wheat during whole plant growth stage and on translocation or remobilization of Σ3PAHs from vegetative tissues to wheat grains. Winter wheat (Triticum aestivum cv. Xiaoyan22) were grown on Σ3PAHs spiked soils maintaining 80%, 60% or 40% water-holding capacity during the whole plant growth stage. Plant samplings were performed at jointing, anthesis or maturity stage, respectively. The present study showed that grain yield and biomass of the crop increased with soil water content increasing. Transpiration rate of wheat leaf under 80% and 60% water-holding capacity treatments was significantly (p < 0.05) higher than that under 40% water-holding capacity treatment at both anthesis and filling stage. Soil water content and plant growth stage had significant (p < 0.0001) effects on concentrations of phenanthrene, anthracene and pyrene in winter wheat. When exposed to 0, 15, 60, and 150 mg kg-1 Σ3PAHs in soils, Σ3PAHs concentrations in the grains under 60% water-holding capacity treatment were 46.6%, 69.9%, 89.5% and 81.7% of those under 80% water-holding capacity treatment, respectively. The highest concentrations of Σ3PAHs in the crop were recorded at anthesis stage. The distribution of PAHs in different tissues of wheat varied among different soil water treatments and plant growth stages. The present study indicated that optimizing soil water content during winter wheat production could apparently reduce concentrations of Σ3PAHs in grains via influence root uptake of Σ3PAHs and translocation of Σ3PAHs from stem or leaf into grain, suggesting the potential of water management to cope with PAHs contamination in crops growing on PAHs contaminated soils.

Ratiometric SERS detection of polycyclic aromatic hydrocarbons assisted by ß-cyclodextrin-modified gold nanoparticles.

A surface-enhanced Raman scattering (SERS) method is described for the determination of trace polycyclic aromatic hydrocarbons (PAHs) in the environment efficiently and economically. Detection sensitivity is improved by modifying gold nanoparticles (AuNPs) with 4-mercaptophenylboronic acid (4-MPBA) conjugated to ß-cyclodextrin (ß-CD) as a new method for ratiometric determination of PAHs in solution. Pyrene (with a Raman band at 580 cm-1) and anthracene (750 cm-1) were used as the model analytes, while 4-MPBA (1570 cm-1) was used as the internal reference to normalize the SERS signals. The intensity ratios of pyrene/4-MPBA increase linearly in the 2 to 10 nM pyrene concentration range, and the intensity ratios of anthracene/4-MPBA increase linearly in the 10 to 100 nM anthracene concentration range. The detection limits are 0.4 nM for pyrene and 4.4 nM for anthracene. This method was applied to the determination of the two analytes in soil sample extracts and the recoveries of pyrene (at levels of 236 ng∙g-1 and 170 ng∙g-1) and anthracene (334 ng∙g-1 and 510 ng∙g-1) agreed well with the results from GC-MS analyses. The good recovery rates (101.8% and 102.5% for pyrene and 106.4% and 101.7% for anthracene) confirmed the reliability of the method. Graphical abstract Schematic illustration of SERS signal enhancement of pyrene, as an example of polycyclic aromatic hydrocarbons, by ß-cyclodextrin modified gold nanoparticles.

Evaluating the mycostimulation potential of select carbon amendments for the degradation of a model PAH by an ascomycete strain enriched from a superfund site.

Although ecological flexibility has been well documented in fungi, it remains unclear how this flexibility can be exploited for pollutant degradation, especially in the Ascomycota phylum. In this work, we assess three mycostimulation amendments for their ability to induce degradation in Trichoderma harzanium, a model fungus previously isolated from a Superfund site contaminated with polycyclic aromatic hydrocarbons. The amendments used in the present study were selected based on the documented ecological roles of ascomycetes. Chitin was selected to simulate the parasitic ecological role while cellulose and wood were selected to mimic bulk soil and wood saprobic conditions, respectively. Each amendment was tested in liquid basal medium in 0.1 and 1% (w/v) suspensions. Both chitin and cellulose amendments were shown to promote anthracene degradation in T. harzanium with the 0.1% chitin amendment resulting in over 90% removal of anthracene. None of the targets monitored for gene expression were found to be upregulated suggesting alternate pathways may be used in T. harzanium. Overall, our data suggest that mycostimulation amendments can be improved by understanding the ecological roles of indigenous fungi. However, further research is needed to better estimate specific amendment requirements for a broader group of target fungi and follow up studies are needed to determine whether the trends observed herein translate to more realistic soil systems.

Novel method for in situ investigation into graphene quantum dots effects on the adsorption of nitrated polycyclic aromatic hydrocarbons by crop leaf surfaces.

Nitrated polycyclic aromatic hydrocarbons (NPAHs) are PAH derivatives with more toxic effects to ecosystem, and the partitioning of NPAHs in crop system constitutes the potential exposure to human health through the dietary pathway. In the present study, a novel method for in situ detection of 9-nitroanthracene (9-NAnt) and 3-nitrofluoranthene (3-NFla) adsorbed onto the leaf surfaces of living soybean and maize seedlings was established based on the fiber-optic fluorimetry combined with graphene quantum dots (GQDs) as a fluorescent probe. The detection limits for the in situ quantification of the two adsorbed NPAHs ranged from 0.8 to 1.6 ng/spot (spot represents determination unit, 0.28 cm2 per spot). Using the novel method, the effects of GQDs on the adsorption of individual 9-NAnt and 3-NFla by the living soybean and maize leaf surfaces were in situ investigated. The presence of GQDs altered the adsorption mechanism from the sole film diffusion to the combination of film diffusion and intra-particle diffusion, and shortened the time required to achieving adsorption equilibrium by 15.8-21.7%. Significant inter-species and inter-chemical variability existed in terms of the equilibrated adsorption capacity (qe) with the sequence of soybean > maize and 3-NFla > 9-NAnt. The occurrence of GQDs enlarged the qe values of 9-NAnt and 3-NFla by 22.8% versus 28.7% for soybean, and 16.2% versus 20.3% for maize, respectively, which was largely attributed to GQDs-induced expansion to the surface area for adsorbing NPHAs and the stronger electrostatic interaction between the -NO2 of NPAH molecules and the functional groups (e.g., -COOH, -OH) of GQDs outer surfaces. And, the varied enhancement degrees in the order of 3-NFla > 9-NAnt might be explained by the steric effects that resulted in the easier accessibility of -NO2 of 3-NFla to the outer surface of GQDs. Summarily, the GQDs increased the retention of NPAHs on crop leaf surfaces, potentially threatening the crop security.

Soils impacted by PAHs: Would the stabilized organic matter be a green tool for the immobilization of these noxious compounds?

The objective of this study was to investigate the role of stabilized organic matter (vermicompost) and tropical soils in the sorption of naphthalene, anthracene and benzo[a]pyrene. The results obtained for the three compounds were extrapolated for the priority polycyclic aromatic hydrocarbons (PAHs) pollutants according to Environmental Protection Agency (US EPA). To evaluate the sorption process, high performance liquid chromatography was employed and the data was fitted by Freundlich isotherms. The results suggest that the sorption effect generally increases with the number of benzene rings of the PAHs, and that the persistence of PAHs in the environment is possibly related to the number of benzene rings in the PAH molecule. In addition, the pH of the vermicompost can strongly affect the adsorption process in this matrix.

The effect of soil pollution with petroleum-derived substances on Porcellio scaber Latr. (Crustacea, Isopoda).

Presented research aimed at investigating the effect of short-term contact with petroleum-derived substances (PDSs) on life parameters of Porcellio scaber Latr. (Isopoda) and accumulation of polycyclic aromatic hydrocarbons (PAHs) in its body. The influence of presence of P. scaber on the total petroleum hydrocarbons (TPH) content in soil was also determined. The following objects were established: control-unpolluted soil; soil polluted with petrol; soil polluted with diesel fuel and soil polluted with used engine oil. Every pollutant was used in the amounts equal to 6000 mg of fuel/kg d.m. of soil 15 months earlier. In the laboratory, survival and body mass change of P. scaber reared in investigated soils were observed. The delivered food was not contaminated with PDSs. P. scaber reveals a considerable resistance in a short (4 weeks) contact with PDSs, evidenced as high survivability (from 68% on the soil polluted with engine oil to 77% on the soil polluted with diesel fuel) and undisturbed increase in body mass (on the level similar to control). It indicates the potential usefulness of this animal as a monitoring organism. No positive correlation was observed between TPH depletion in the soils contaminated with PDSs and P. scaber presence during 4 weeks of the experiment. PAH level in P. scaber bodies was generally very low (with the highest level of anthracene 0.40 µg/g of wet mass-after 4 weeks of rearing on the diesel fuel-contaminated soil), which may confirm the thesis about considerable abilities of isopods for biotransformation of these pollutants and low susceptibility to these xenobiotic penetration through integuments. However, a tendency for accumulation for phenanthrene and anthracene in conditions of soil polluted with diesel fuel was observed respectively 0.07 and 0.21 µg/g of wet mass for phenanthrene and 0.22 and 0.40 µg/g of wet mass for anthracene, observed successively in the 2nd and 4th week of rearing.