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In the field of conservation of cultural heritage, one must always consider the environmental conditions in which the works of art are located and the level of atmospheric pollution to which they are exposed, especially in the case of monuments stored outdoors. The present study is focused on the detection and the quantification of polycyclic aromatic hydrocarbons (PAHs) in black crust samples from the Monumental Cemetery of Milan (Italy), and the assessment of their sources through the analysis of the distributions of the different compounds in the samples, together with the use of diagnostic ratios. Six black crust samples taken from funerary monuments were analyzed. Fourteen polycyclic aromatic hydrocarbons were identified (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benzo[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene) by high-performance liquid chromatography with a diode-array detector (HPLC-DAD), with a total concentration from 0.72 to 3.81 μg/g (mean of 1.87 μg/g). The known carcinogenic benzo[a]pyrene accounted for 5-10% of the total polycyclic aromatic hydrocarbons in the samples analyzed, with concentrations up to 0.20 μg/g. Moreover, the study of the distribution and diagnostic ratios allowed us to confirm that anthropogenic sources such as traffic and the proximity of the train station are the major causes of the degradation of the monuments contained in this Cemetery., (© 2024. The Author(s).)

The study of anaerobic high molecular weight polycyclic aromatic hydrocarbons (HMW-PAHs) biodegradation under sulfate-reducing conditions by microorganisms, including microbial species responsible for biodegradation and relative metabolic processes, remains in its infancy. Here, we found that a new sulfate-reducer, designated as Desulforamulus aquiferis strain DSA, could biodegrade pyrene and benzo[a]pyrene (two kinds of HMW-PAHs) coupled with the reduction of sulfate to sulfide. Interestingly, strain DSA could simultaneously biodegrade pyrene and benzo[a]pyrene when they co-existed in culture. Additionally, the metabolic processes for anaerobic pyrene and benzo[a]pyrene biodegradation by strain DSA were newly proposed in this study based on the detection of intermediates, quantum chemical calculations and analyses of the genome and RTqPCR. The initial activation step for anaerobic pyrene and benzo[a]pyrene biodegradation by strain DSA was identified as the formation of pyrene-2-carboxylic acid and benzo[a]pyrene-11-carboxylic acid by carboxylation Thereafter, CoA ligase, ring reduction through hydrogenation, and ring cracking occurred, and short-chain fatty acids and carbon dioxide were identified as the final products. Additionally, DSA could also utilize benzene, naphthalene, anthracene, phenanthrene, and benz[a]anthracene as carbon sources. Our study can provide new guidance for the anaerobic HMW-PAHs biodegradation under sulfate-reducing conditions., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

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., (© 2023. The Author(s).)

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.

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

Petroleum refineries generate oily sludge that contains hazardous polycyclic aromatic hydrocarbons (PAH), and hence, its proper disposal is of foremost concern. Analysis of the physicochemical properties and functions of indigenous microbes of the contaminated sites are essential in deciding the strategy for bioremediation. This study analyses both parameters at two geographically distant sites, with different crude oil sources, and compares the metabolic capability of soil bacteria with reference to different contamination sources and the age of the contaminated site. The results indicate that organic carbon and total nitrogen derived from petroleum hydrocarbon negatively affect microbial diversity. Contamination levels vary widely on site, with levels of PAHs ranging from 5.04 to 1.66 × 10 3  μg kg -1 and 6.20 to 5.64 × 10 3  μg kg -1 in Assam and Gujarat sites respectively, covering a higher proportion of low molecular weight (LMW) PAHs (fluorene, phenanthrene, pyrene, and anthracene). Functional diversity values were observed to be positively correlated (p < 0.05) with acenaphthylene, fluorene, anthracene, and phenanthrene. Microbial diversity was the highest in fresh oily sludge which decreased upon storage, indicating that immediate bioremediation, soon after its generation, would be beneficial. Improvement in the bio-accessibility of hydrocarbon compounds by the treatment of biosurfactant produced by a (soil isolate/isolate) was demonstrated., with respect to substrate utilization., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Dr. Atya Kapley reports financial support was provided by India Ministry of Science & Technology Department of Biotechnology., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The aim of this study was to evaluate the concentration of 5-hydroxymethylfurfural (HMF), furfural, polycyclic aromatic hydrocarbons (PAHs), and pesticide residues, as well as assessment of cancer risk of the Polish-origin bee products. The bee product samples were prepared using a modified QuEChERS method, then PAHs and pesticides were analysed by gas chromatography-mass spectrometry (GC-MS), neonicotinoids by high-performance liquid chromatography with a diode array detector (HPLC-DAD), and HMF and furfural by spectrophotometry (HPLC-UV/Vis). The results showed that the highest furfural content was found in bee bread from the northeast part of Poland; moreover, samples obtained from the same region were also characterized with a higher level of HMF. The total sum of PAHs ranged from 324.0 to 866.4 μg/kg; the highest content of PAH4 (the sum of benzo[a]anthracene, chrysene, benzo[b]fluoranthene and benzo[a]pyrene) was 21.0 μg/kg, but only benzo[a]anthracene and chrysene were detected in the samples. Imidacloprid and acetamiprid were found only in bee bread from the northeast part of Poland, while clothianidin was detected in honey samples. The acceptable cancer risk has been calculated for PAHs due to ingestion of honey, while increasing the risk of cancer was calculated for bee bread and bee pollen. Due to the high concentration of PAHs and excessively high recommended consumption dose, regular consumption of bee bread and pollen may pose a severe threat to human health and should be strictly limited., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Anthracene biodegradation potential has been studied in liquid culture and soil microcosm environment by employing green synthesized TiO 2 nanoparticles (NPs) and Alcaligenes faecalis HP8. The bacterium was isolated from crude oil contaminated soil, while TiO 2 nanoparticles were synthesized using Paenibacillus sp. HD1PAH and Cyperus brevifolius which have PAHs remediation abilities. The dual application of TiO 2 nanoparticles and Alcaligenes faecalis HP8 decreases anthracene concentration up to 21.3% in liquid at the end of 7 days and 37.9% in the soil treatments after completion of 30 days. Besides, the GC-MS analysis revealed production of five metabolites including 1,2-anthracenedihydrodiol; 6,7-benzocoumarin; 3-hydroxy-2-naphthoic acid; salicylic acid and 9,10-anthraquinone at different time interval of the treatments. Anthracene degradation pathway confirms the breakdown of three ring anthracene to one ring salicylic acid. Additionally, soil dehydrogenase, urease, alkaline phosphatase, catalase and amylase activities increased up to 4.09 folds, 8.6 folds, 4.4 folds, 3.6 folds and 2.1 folds respectively after the combined treatments of TiO 2 nanoparticles and Alcaligenes faecalis HP8. The bacterial biomass and residual anthracene concentration were found to be negatively correlated. Finally, the study brings into light a novel anthracene biodegradation pathway and provides a new dimension in nano assisted bacterial remediation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

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., (© 2023. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Volatile organic compounds (VOCs) are a group of organic compounds that have a molecular structure containing carbon and their chemical properties allow them to be easily converted to steam and gas and remain for a long period of time and have diverse effects on the environment. The purpose of this study is determination of the concentration of VOCs such as alachlor, anthracene, benzene, bromoform, chloroform, heptachlor, isophorone, tetrachloroethylene, γ -chlordane, toluene, etc. in water matrices. The results showed that among studies conducted on VOCs, the concentration of tetrachloroethylene, m,p-xylene, and toluene were at the top in water matrices, and the lowest average concentrations were found in chloroform, anthracene, and butyl benzyl phthalate. In terms of VOC concentrations in water matrices, China was the most polluted country. Moreover, the data analysis indicated that China was the only country with carcinogenic risk. A Monte-Carlo simulation showed that although the averages obtained were comparable to the acceptable limits, for heptachlor, the maximum carcinogenic risk is achieved at a level that is slightly over the limit, only 25% from the population being exposed., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

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 (r 2 ) 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., (© 2022 John Wiley & Sons Ltd.)

Polycyclic aromatic hydrocarbons (PAHs) are among the most harmful persistent organic pollutants that possess high carcinogenicity and teratogenicity; hence, establishing a highly sensitive analytical method for monitoring PAHs in environmental samples is an urgent need. However, due to the low PAHs content in environmental samples and the complex matrix of the samples, it is difficult to directly determine the amount of PAHs using the existing analytical instruments. Therefore, an essential pretreatment of environmental samples should be carried out before instrumental analysis. In most pretreatment techniques, the extraction efficiency depends on the characteristics of the extraction materials. Currently, metal-organic framework materials (MOFs), which are porous materials self-assembled by metal ions and organic ligands, are used as solid-phase microextraction (SPME) coating materials for the extraction of PAHs. However, the following problems limit the application of MOFs in the SPME field: (1) MOF coating materials often require a long equilibration time for extraction because the it is difficult for the target to reach the deep adsorption sites; (2) In addition, most MOFs are formed by the coordination of single metal ions with organic monomers. The single type of open metal active sites is not conducive for realizing high extraction performance. In this study, a hollow bimetal-organic framework (H-BiMOF) was synthesized by the solvothermal method and characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), nitrogen adsorption-desorption analysis, thermogravimetric analysis, etc. The TEM images and XRD patterns demonstrated the successful synthesis of H-BiMOF with a hollow structure, which was formed through the competitive coordination between benzoic acid and water. The H-BiMOF material showed type-Ⅳ isotherms with a surface area of 1437 m 2 /g and excellent thermal stability. Subsequently, a H-BiMOF-coated SPME fiber was prepared by the physical adhesion method and used to extract trace PAHs from environmental samples. Due to the hollow structure of H-BiMOF, the prepared fibers offer the advantages of high utilization of specific surface area as well as short mass transfer distance, so that the extraction process quickly reaches equilibrium. At the same time, the introduction of bimetals provides a variety of metal active sites, which improves the extraction efficiency of the fiber against electron-rich cloud targets such as PAHs. The prepared fiber also had good service life, with at least 150 cycles. Combined with gas chromatography-tandem mass spectrometry (GC-MS/MS), a new method for the determination of PAHs in environmental water samples was established. Single factor experiments were performed to investigate the effects of the SPME conditions on the analytical performance. Under the optimal conditions, the established method showed low limits of detection (0.01-0.08 ng/L), wide linear range (0.03-500.0 ng/L), good linearity (correlation coefficients≥0.9986), and acceptable reproducibility (relative standard deviations≤9.8%, n =5). Finally, typical water samples were analyzed by the established method. Four environmental water samples were collected from Dianchi Lake, Poyang Lake, Taihu Lake, and Xihu Lake in China. No benzo( a )anthracene (BaA) and chrysene (CHR) were detected in any of the water samples. However, 17.9 ng/L of fluorene (FLU) and 5.3 ng/L of phenanthrene (PHE) were found in the Poyang Lake sample; 11.3 ng/L of fluoranthene (FLA) and 24.2 ng/L of pyrene (PYR) were found in the Taihu Lake sample; 50.0 ng/L of FLU, 19.5 ng/L of PHE, 14.9 ng/L of anthracene (ANT), 34.2 ng/L of FLA, and 44.5 ng/L of PYR were found in the Xihu Lake sample. The contents of the PAHs detected in all the lake water samples were lower than the Chinese National Standard GB 5749-2006 (2000.0 ng/L). The results of this study indicate that the developed method is suitable for the sensitive detection of trace levels of PAHs in real environmental water samples.

Developing functional fiber coating for selective solid phase microextraction (SPME) of trace pollutants is critical in environmental analysis. Herein, the novel covalent organic frameworks (COFs) with three-dimensional (3D) frameworks and multiple interactions were designed and presented for the selective SPME of polychlorinated biphenyls (PCBs). Using tetra (p-aminophenyl) methane (TAM) and 1,3,5-triformylphloroglucinol (Tp) as the monomers, the 3D TpTAM-COF was synthesized and possessed a large specific surface area, high thermal stability, and spatial selectivity toward PCBs. Characterizations such as morphology, XPS, XRD, thermal stability, and enhancement factors (EFs) were studied. Multiple interactions including π-π conjugation, hydrophobic interaction, and selectivity toward non-planar structure were adopted, which resulted in a superior adsorption affinity toward PCBs on TpTAM-COF. Under the optimal conditions, the spatial selectivity toward PCBs, organic analogs (o-dichlorobenzene, biphenyl) and polycyclic aromatic hydrocarbons (naphthalene, pyrene, and anthracene)) was achieved. Efficient and selective adsorption of fifteen PCBs was fulfilled with the highest EF up to 10305. Using the HS-SPME-GC-MS method, the recoveries of PCBs in the river water and soil samples were determined to be 84.8 ± 7.8% ∼ 117.2 ± 8.5% (n = 3) and 84.4 ± 8.6% ∼ 114.7 ± 7.6% (n = 3), respectively. Compared with most commercial SPME fibers and other COFs-based fibers, the resultant TpTAM-COF-coated fibers possessed higher selectivity and EFs of PCBs. It proposed a promising approach for selective SPME of trace PCBs by multiple interactions in the steric structure of 3D COFs., Competing Interests: Declaration of Competing Interest The authors declare no conflict of interest. We declare that we have no financial and personal relationships with other people or organizations that can inappropriately influence our work, there is no professional or other personal interest of any nature or kind in any product, service and/or company that could be construed as influencing the position presented in, or the review of, the manuscript entitled “Efficient and selective solid-phase microextraction of polychlorinated biphenyls by using a three-dimensional covalent organic framework as functional coating”., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Many solid-phase microextraction (SPME) sorbents have been developed from aerogels because of their low densities, large surface areas, and high porosities. Melamine-formaldehyde (MF) aerogel, made from melamine and formaldehyde by a sol-gel reaction, is one of the typical organic aerogels. MF aerogel has better mechanical strength, chemical stability and extraction performance than inorganic aerogels. The performance of the aerogel is limited in some fields, while composite aerogels can meet different requirements such as good mechanical strength and strong adsorption performance. Graphene oxide (GO) is a two-dimensional nanomaterial composed of a single layer of carbon atoms and provides π-π interaction by a large π-electron. In addition, the oxygen-containing groups at the edge of the lamellar structure improve the hydrophilicity of the material and can interact with various compounds. To improve the extraction performance of MF aerogel for polycyclic aromatic hydrocarbons (PAHs), GO/MF aerogels were prepared by functionalizing MF aerogel with GO. In this study, 1.2612 g of melamine and 80 mg of sodium carbonate were dissolved in 30 mL of water, and the mixture was heated to 80 ℃ under stirring. Then, 2.8 mL formaldehyde solution (37%) was slowly added, and a clear solution was obtained gradually. Next, 50 mg of GO powder was ultrasonically dispersed in 10.0 mL of water and evenly mixed with the above solution. After adjusting the pH to 1.5, the sol-gel process was performed for 48 h, then the gel was aged at room temperature for 24 h. The gel was then soaked in ethanol, acetone, and cyclohexane in turn to replace the solvent. Finally, the GO/MF aerogel was obtained by freeze-drying for 24 h. The GO/MF aerogel was characterized by scanning electron microscopy (SEM) and X-ray photoelectric spectroscopy (XPS), confirming that GO was successfully introduced into MF aerogel, while retaining its three-dimensional network and porous structure. GO/MF aerogel was coated onto the surface of a stainless steel wire to be used as sorbent. Four such wires were placed into a polyetheretherketone (PEEK) tube (0.75 mm i. d., 30 cm length) for in-tube (IT) SPME. The tube was combined with a high-performance liquid chromatography (HPLC) unit to construct an IT-SPME-HPLC online system. When the six-way valve was in the Load state, sample solution achieved online enrichment with analytes while it flowed through the extraction tube. After extraction, the valve was turned to the Inject state, and the analytes were eluted into the chromatographic column by the mobile phase at a flow rate of 1.0 mL/min for separation and detection with the detector. Under the same extraction conditions (sampling volume=30 mL, sampling rate=1.00 mL/min, and concentration of polycyclic aromatic hydrocarbons (PAHs, viz. naphthalene (Nap), acenaphthylene (Acy), acenaphthene (Ace), fluorine (Flu), phenanthrene (Phe), anthracene (Ant), fluoranthene (Fla) and pyrene (Pyr))=5.00 μg/L), GO/MF aerogel-based tube was compared with that of MF aerogel-based tube. GO enhanced the enrichment efficiency of MF aerogel towards PAHs from 1.1 to 2.5 times, due to the increased number of adsorption sites and enhanced π-π interaction with PAHs. IT-SPME was affected by the sampling volume, sampling rate, concentration of organic solvent in sample, desorption solvent, desorption rate, and desorption time. To obtain accurate results, the main extraction and desorption conditions (sampling volume, sampling rate, organic solvent concentration, desorption time) were investigated carefully. As the sampling volume in the extraction tube was increased, the extraction efficiency was found to increase gradually until saturation. In this study, the extraction efficiency was investigated for sampling volumes ranging from 30 to 80 mL, and 70 mL was selected as a suitable sampling volume to achieve satisfactory extraction efficiency. The sampling rate affects not only the extraction efficiency, but also the extraction time. When the sample flows through the extraction tube at a low rate, it requires a long test time. Although the increase in sampling rate reduces the extraction time, it often decreases extraction efficiency. In addition, large sampling rate leads to high pressure in the tube, which in turn reduces the service life of the tube. Therefore, the effect of sampling rate (1.25-2.50 mL/min) on extraction efficiency was investigated, and good extraction efficiency and short test time were achieved when the sampling rate was 2 mL/min. High hydrophobic PAHs have poor solubility in water. An appropriate amount of organic solvent in the sample solution can improve the solubility of PAHs to obtain accurate analytical results. However, the extraction efficiency was affected by the added organic solvent. Thus, the effect of volume fraction of methanol (0, 0.5%, 1%, 2%, 3%, and 5%, v/v) on the extraction efficiency was investigated. The sample solution without methanol afforded better extraction efficiency and satisfactory repeatability. After online extraction, the desorption directly affects the desorption efficiency. The peak areas of the eight PAHs were investigated with different desorption times (0.2, 0.4, 0.6, 0.8, 1.0, and 2.0 min), and a desorption time of 2.0 min was required to fully desorb all analytes and reduce their residuals. The IT-SPME-HPLC-DAD method was established under the optimized conditions, and the limits of detection (LODs), linear equations, linear ranges, and correlation coefficients were obtained. The LODs of the eight PAHs were in the range of 0.001-0.005 μg/L, the quantitative ranges of the analytes were 0.003-15.0 μg/L for Fla and Pyr, 0.010-20.0 μg/L for Phe and Ant, and 0.017-20.0 μg/L for Nap, Acy, Ace and Flu, the enrichment factors were in the range of 2029-2875, and the analytical precision was satisfactory (intra-day RSD%≤4.8%, and inter-day RSD≤8.6%). Compared with some reported methods, the method reported herein provided higher sensitivity, wider linear range, and shorter test time. This method was applied to the detection of PAHs in common drinking water, including bottled mineral water and water from drinking fountain. The satisfactory recovery (76.3%-132.8%) obtained proves that the method is suitable for the determination of trace PAHs in real water samples, with high sensitivity, rapid testing, online detection, and good accuracy. The extraction tube also exhibited satisfactory durability and chemical stability.

In this paper, a new aqueous two-phase extraction system(ATPES) consisting of UCON (poly(ethylene glycol-ran-propylene glycol) monobutyl ether)-NaH 2 PO 4 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 NaH 2 PO 4 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 R 2 was 96.20-98.53%, proving that the model is robust and reliable.

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., (© 2022. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

Exposure to electronic and electrical waste (e-waste) has been related to a few adverse health effects. In this study, sediment samples from an e-waste recycling town in China were collected, and aryl hydrocarbon receptor (AhR) agonists in the samples were identified using an effect-directed analysis (EDA) strategy. The CBG2.8D cell line reporter gene bioassay was used as a toxicity test, while suspect screening against chemical databases was performed for potential AhR agonist identification where both gas chromatography- and liquid chromatography-high resolution mass spectrometry analyses were run. When the original sample extract showed high AhR-mediated activity, sample fractionation was performed, and fractions exhibiting high bioactivity were chemically analyzed again to reveal the corresponding AhR agonists. In total, 23 AhR agonists were identified, including 14 commonly known ones and 9 new ones. Benzo [k]fluoranthene and 6-nitrochrysene were the dominant AhR agonists, covering 16-71% and 2.7-12%, respectively, of the AhR activation effects measured in the parent extracts. The newly identified AhR-active chemicals combined explained 0.13-0.20% of the parent extracts' effects, with 7,12-dimethylbenz [a]anthracene and 8,9,11-trimethylbenz [a]anthracene being the major contributors. A diagnostic isomer ratio analysis of polycyclic aromatic hydrocarbons suggested that the major source of AhR agonists identified in these e-waste related sediment samples were probably petroleum product combustion and biomass combustion. In the future, for a more comprehensive AhR agonist investigation, in-house chemical synthesis and purification, and, when necessary, a secondary sample fractionation, would be beneficial., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Novel aryl hydrocarbon receptor (AhR) agonists were identified in coastal sediments in the Yellow and Bohai Seas by use of a combination of effect-directed analysis (EDA) and in silico prediction. A total of 125 sediments were screened for AhR-mediated potencies using H4IIE-luc bioassay. Great potencies were observed in organic extracts, mid-polar fraction (F2), and subfractions of F2 (F2.6-F2.9) of sediments collected from Nantong, Qinhuangdao, and Yancheng. Less than 15% AhR potencies could be explained by detected dioxin-like PAHs. Full-scan screening analysis was conducted for the more potent fractions using GC-QTOFMS to investigate the presence of unmonitored AhR agonists. A five-step prioritization strategy was applied; 92 candidate compounds satisfied all criteria. Among these chemicals, thirteen were evaluated for AhR efficacy. Six compounds; benz[b]anthracene, 6-methylchrysene, 2-methylbenz[a]anthracene, 1-methylbenz[a]anthracene, 1,12-dimethylbenzo[c]phenanthrene, and indeno[1,2,3-cd]fluoranthene, exhibited significant AhR-mediated efficacies. 1,12-dimethylbenzo[c]phenanthrene and indeno[1,2,3-cd]fluoranthene were identified as novel AhR agonists. Potency balance analysis showed that the six newly identified AhR agonists explained 0.4-100% of the total AhR-mediated potencies determined. Overall, combining EDA and in silico prediction applied in this study demonstrated the benefits of assessing the potential toxic effects of previously unidentified AhR agonists in sediments from the coasts of China and Korea., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Herein, magnetic porous pinecone-derived hydrochar (MPHC MW ) co-activated by KHCO 3 and K 2 FeO 4 through one-step microwave-assisted pyrolysis was innovatively synthesized for hexavalent chromium (Cr(VI)) and anthracene (ANT) removal from water. The analyses of characterization consequences and co-activation mechanisms not merely proved the high specific surface area (703.97 m 2 /g) and remarkable microporous structures of MPHC MW caused by the synergistic chemical activation of KHCO 3 and K 2 FeO 4 , but also testified successful loading of Fe 0 and Fe 3 O 4 on MPHC MW by the process of carbothermal reduction between K 2 FeO 4 and carbon matrix of hydrochar. The resultant MPHC MW possessed pH-dependence for Cr(VI), while adsorption for ANT was hardly impacted by the pH of solution. Moreover, the adsorption processes of MPHC MW could attain equilibrium within 60 min for Cr(VI) and 30 min for ANT with multiple kinetics, and the corresponding adsorption capacity for Cr(VI) and ANT was 128.15 and 60.70 mg/g, respectively. Additionally, the adsorption percentages of MPBC MW for Cr(VI)/ANT was maintained at 87.87/82.64% after three times of adsorption-desorption cycles. Furthermore, pore filling, complexation, electrostatic interaction, reduction and ion exchange were testified to enhance the removal of Cr(VI), while the ANT removal was achieved via π-π stacking, complexation, pore filling and hydrogen bonding force., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

More than 5.8 million tonnes of oil have been spilled into the oceans. Some oil disasters marked history, causing multiple social and economic consequences in addition to catastrophic environmental impacts. Recently, Brazil and Mauritius faced oil disasters that have severely impacted seafood sanitary credibility. One of the components of the oil composition are the polycyclic aromatic hydrocarbons (PAH), which are the main contamination markers of petrogenic origin. There is enough evidence to correlate the intake of food contaminated with PAH with increased risks of developing cancer. The set PAH4, composed of benzo[a]anthracene, benzo[a]pyrene, benzo[b]fluoranthene, and chrysene, and the set PAH8, composed of benzo[a]anthracene, benzo[a]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[ghi]perylene, chrysene, dibenzo[a,h]anthracene, and indeno[1,2,3-cd]pyrene are recognized as markers of food chemical contamination. After oil disasters in the oceans, the risk to the health of seafood consumers tends to be of special concern, Countries like the European Union set maximum levels for benzo[a]pyrene (5 µg kg -1 ) and PAH4 (30 µg kg -1 ) in bivalve mollusks. Levels of concern established by countries that have faced oil disasters are given special attention in this review. Laboratory analysis of PAH in food samples is very challenging because it deals with quite different kinds of matrices. Furthermore, analytical results are usually related to the closure or reopening of cultivated areas and fishing points. Therefore, the progress of the analytical methods for PAH in seafood is covered in detail. Chemical laboratory measurements provide essential data to assess the potential risks to human health due to consumption of seafood contaminated with PAH. The main human health risk assessment approaches in a seafood contamination scenario with PAH are reviewed and discussed, providing an insightful and guiding tool to each step of the risk assessment framework., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Polycyclic aromatic hydrocarbons (PAHs) are hazardous and ubiquitous pollutants in the aquatic environment, and understanding the pollution characteristics and risk levels of PAHs is of great significance to the sustainable development of drinking water sources and drinking water safety. Hence, PAHs residues were measured qualitatively and quantitatively with solid-phase extraction-gas chromatography-mass spectrometry (SPE-GC-MS) in 33 water samples (including 22 groundwater and 11 surface water samples) of the drinking water sources in the Manzhouli and Xinyouqi areas of northeast Inner Mongolia, and assessments of the pollution level of PAHs and the health and ecological risks were carried out. The results showed that PAHs were detected in all 33 sampling points of Manzhouli drinking water sources, except for benzo[k] fluoranthene, benzo[a] pyrene, and dibenzo[a,h] anthracene, with detection rates ranging from 36.36% to 95.45%; the detection rates of the other 13 PAHs monomers were 100%. The detection range of ρ （ΣPAHs） was 42.76-164.50 ng·L -1 , and the mean value was 90.82 ng·L -1 . The detection ranges of ρ （ΣPAHs） in surface water and groundwater were 66.39-164.50 ng·L -1 and 42.76-147.70 ng·L -1 , respectively. The concentration of the detected naphthalene was the highest, with a mean value of 36.91 ng·L -1 , and the concentration of anthracene was the lowest, with a mean value of 0.81 ng·L -1 ; there were no significant differences among the concentrations of all the PAHs monomers of the surface and groundwater ( P >0.05). The pollution of PAHs was at a median level in China and abroad, mainly in the middle and low loops (3-4 loops). The analysis of the sources of PAHs in groundwater and surface water in Manzhouli using the ratio feature method and principal component analysis showed that the PAHs in the drinking water source water bodies in the Manzhouli area were mainly affected by the combustion of coal and biomass and oil, and some surface water sources were affected by the oil source. The human health and ecological risk assessment results showed that the water body of drinking water would not cause health risks to the human body, and the ecological risk was at a medium level; however, the high risk of benzo[b] fluoranthene (BbF) monomer production should be continuous cause for concern. From the perspective of the sustainable development of drinking water sources and drinking water safety, the necessary supervision and protection measures should be considered to prevent further pollution. The results of this research provide a scientific basis for the pollution control and prevention and control of PAHs in drinking water sources.

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., (© 2021 Society of Chemical Industry.)

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., (Copyright © 2020 Elsevier Inc. All rights reserved.)

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 Rb 1 (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.

A green synthesis method for nanoscale silver using β-cyclodextrin as both reducing agent and stabilizer was developed. β-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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

This study developed a new method for analysing 6-ClBaP and 7-ClBaA in six oil samples using liquid-liquid extraction and solid-phase extraction followed by GC-QQQ-MS. The recoveries of 6-ClBaP and 7-ClBaA were 44.26 ± 2.81% and 92.61 ± 4.09%, respectively. Both the instrument and method LODs were lower than 0.2 μg kg -1 , while the intra-day and inter-day RSD were less than 5%. Five waste frying oils and one peanut oil were tested with the validated determination method. The concentrations of 6-ClBaP and 7-ClBaA in the tested samples ranged from no detection to 0.29 μg kg -1 and no detection to 0.20 μg kg -1 , respectively. The data of 6-ClBaP and 7-ClBaA detected in this study suggest that a large scale of investigation on Cl-PAHs in foods is necessary., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The traditional smoking procedure, which is the use of open fire, can lead to the formation of PAHs in sausages. The aim of this paper was to assess the types and concentrations of 16 PAHs in 30 samples of Slavonska kobasica , a traditional smoked sausage. In general, some samples showed high values of anthracene and acenaphthylene. In one sample, acenaphthylene reached the value of 1050 µg/kg and in another 1491 µg/kg anthracene was measured. Cancerogenic benzo( a )pyrene content was little above the maximum limit of 5 µg/kg in four samples, but mainly remained below the limit of quantification. PAH4 (i.c. benzo( a )anthracene, chrysene, benzo( b )fluoranthene and benzo( a )pyrene) were above the maximum limit of 30 µg/kg in three samples. Generally, it can be noted from the results that samples with high PAH4 and benzo( a )pyrene concentrations also have high PAH16 concentrations.

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.

Light-matter interactions have always been a fundamentally significant topic that has attracted much attention. It is important to reveal a fluorophore-plasmon interaction on the nanoscale. However, as a powerful investigative tool, fluorescence spectroscopy still suffers from a limited spectral resolution and the susceptibility to interfering substances. In this work, excitation-emission synchronization-mediated surface-plasmon-coupled emission (EES-SPCE) is proposed to break the bottleneck. By actively screening the energy transitions for observation, an improved spectral resolution has been achieved, which is advantageous to the investigation of the fluorophore-plasmon interactions under different coupling modes. The spectral information related to the plasmonic interactions through tuning vibrational energy levels is clearly distinguished at directional emission angles. EES-SPCE is demonstrated to selectively and efficiently extract the coupled emission from the vibrational resolution, which would open up the opportunity to improve the capability of spectral feature identification and signal collection for practical applications of plasmonic fluorescence spectroscopy.

Enriching and locating target analytes into specific "hot spots" are vital for ultrasensitive molecular identification and detection using plasmonic-based techniques. Inspired by mass transportation in lamp wicks, we develop an effective enrichment strategy for highly diluted analytes in which analytes and Au nanoparticles are transported via a solution microflow under the capillarity driving force of glass fiber papers to a heated region. After evaporation, a large volume of a solution containing analytes and Au nanoparticles is condensed into a very limited area, and thus, analyte molecules are effectively enriched and located into surface-enhanced Raman scattering (SERS) hot spots. Using this enrichment strategy, the sensitivity and detection limits of SERS are remarkably improved. Detection levels of crystal violet and anthracene are down to 10 -16 and 10 -10 M, respectively. This enrichment strategy is very robust and easy to implement, and it can potentially be exploited in various plasmonic-based molecular detection and identification techniques.

Roasting is an important process in cocoa production which may lead to formation of non-desirable compounds such as polycyclic aromatic hydrocarbons (PAHs). Therefore, PAH4 (sum of four different polycyclic aromatic hydrocarbons; benz[a]anthracene, chrysene, benzo[b]fluoranthene, and benzo[a]pyrene) in roasted cocoa beans was determined using a modified method (combination of QuEChERS and DLLME), and quantified by HPLC-FLD. The modified method was validated and met the performance criteria required by the EU Regulation (No. 836/2011). Results show a significant (p < 0.05) increase of PAH4 (0.19-7.73 ng/g) with an increase in temperatures (110-190 °C) and duration (10-50 min). The PAHs content in whole cocoa bean roasting was detected even at the lowest temperature (110 °C) compared to nib roasting detected at 150 °C which indicates that PAHs was transferred from dried shells to roasted cocoa beans during the roasting process. The data obtained may help to control and minimize PAH4 formation during cocoa processing., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Numerous studies have demonstrated that dozens of polycyclic aromatic hydrocarbons (PAHs) are mutagenic, genotoxic and strongly carcinogenic. PAHs are found to be widely present in foods contaminated through multiple paths. Due to their lipophilic nature, these compounds easily accumulate in edible oils and fatty foods where they can range from no detection to over 2000μg/kg. Compared to precursor PAHs, researchers have seldom studied the presence of PAH derivatives, especially in food matrices. This chapter includes the physical and chemical characteristics of PAHs and their types, occurrence, sample pretreatment and instrumental determination methods, and their formation, change and control in edible oils and fatty foods. The occurrence and formation of PAH derivatives in foods are much less investigated compared to those of their precursor PAHs. Although the removal of matrix effects and accuracy remain difficult for current rapid determination methods, a prospective research direction of PAH analysis for large-scale screening is in demand. To date, physical absorption, chemical oxidation and biodegradation have been widely used in PAH removal techniques. Specific types of bacteria, fungi, and algae have also been used to degrade PAHs into harmless compounds. However, most of them can only degrade a range of LPAHs, such as naphthalene, anthracene and phenanthrene. Their ability to degrade HPAHs requires further study. Moreover, it is still a great challenge to maintain food nutrition and flavor during the PAH removal process using these methods., (© 2020 Elsevier Inc. All rights reserved.)

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.

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 (Σ 3 PAHs, phenanthrene, anthracene and pyrene) in wheat during whole plant growth stage and on translocation or remobilization of Σ 3 PAHs from vegetative tissues to wheat grains. Winter wheat (Triticum aestivum cv. Xiaoyan22) were grown on Σ 3 PAHs 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 Σ 3 PAHs in soils, Σ 3 PAHs 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 Σ 3 PAHs 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 Σ 3 PAHs in grains via influence root uptake of Σ 3 PAHs and translocation of Σ 3 PAHs from stem or leaf into grain, suggesting the potential of water management to cope with PAHs contamination in crops growing on PAHs contaminated soils., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Polycyclic aromatic hydrocarbons (PAHs) are primarily produced during the incomplete combustion of organic matter. PAHs are suspected endocrine disruptors and possible carcinogenic materials. The major sources of human exposure to PAHs are inhaled fumes and food. The aim of this study was to provide an alternative drying method to mitigate PAH formation in dried red peppers. We prepared dried red pepper samples using air-drying and heat pump-assisted drying methods, and measured the concentrations of four PAHs (PAH4), benzo[a] anthracene (B[a]A), chrysene (CHR), benzo[b]fluoranthene (B[b]F), and benzo[a]pyrene (B[a]P), in the resulting pepper samples. The PAH concentrations ranged from 3.61 to 18.0 µg/kg and from 2.22 to 8.35 µg/kg in the air-dried and heat pump-dried pepper samples, respectively. Overall, the results have shown that dried peppers contain PAH4, that the drying conditions for these contaminants should be optimized for mitigating the PAH formation in dried red peppers., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Knipholone (1) and knipholone anthrone (2), isolated from the Ethiopian medicinal plant Kniphofia foliosa Hochst. are two phenyl anthraquinone derivatives, a compound class known for biological activity. In the present study, we describe the activity of both 1 and 2 in several biological assays including cytotoxicity against four human cell lines (Jurkat, HEK293, SH-SY5Y and HT-29), antiplasmodial activity against Plasmodium falciparum 3D7 strain, anthelmintic activity against the model organism Caenorhabditis elegans, antibacterial activity against Aliivibrio fischeri and Mycobacterium tuberculosis and anti-HIV-1 activity in peripheral blood mononuclear cells (PBMCs) infected with HIV-1 c . In parallel, we investigated the stability of knipholone (2) in solution and in culture media. Compound 1 displays strong cytotoxicity against Jurkat, HEK293 and SH-SY5Y cells with growth inhibition ranging from approximately 62-95% when added to cells at 50 μM, whereas KA (2) exhibits weak to strong activity with 26, 48 and 70% inhibition of cell growth, respectively. Both 1 and 2 possess significant antiplasmodial activity against Plasmodium falciparum 3D7 strain with IC 50 values of 1.9 and 0.7 μM, respectively. These results complement previously reported data on the cytotoxicity and antiplasmodial activity of 1 and 2. Furthermore, compound 2 showed HIV-1 c replication inhibition (growth inhibition higher than 60% at tested concentrations 0.5, 5, 15 and 50 μg/ml and an EC 50 value of 4.3 μM) associated with cytotoxicity against uninfected PBMCs. The stability study based on preincubation, HPLC and APCI-MS (atmospheric-pressure chemical ionization mass spectrometry) analysis indicates that compound 2 is unstable in culture media and readily oxidizes to form compound 1. Therefore, the biological activity attributed to 2 might be influenced by its degradation products in media including 1 and other possible dimers. Hence, bioactivity results previously reported from this compound should be taken with caution and checked if they differ from those of its degradation products. To the best of our knowledge, this is the first report on the anti-HIV activity and stability analysis of compound 2., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Passive air sampling was conducted in Toronto and the Greater Toronto Area from 2016 to 2017 for 6 periods, in order to investigate ambient levels of polycyclic aromatic compounds (PACs) associated with different source types. The selected sampling sites (n = 8) cover geographical areas with varying source emissions including background, traffic, urban, industrial and residential sites. Passive air samples were analyzed for PACs which include PAHs, alkylated PAHs (alk-PAHs), dibenzothiophene and alkylated dibenzothiophenes (DBTs) and results for PAHs were used to calculate inhalation cancer risks using different approaches. The samples were also characterized for PAH derivatives including nitrated PAHs (NPAHs) and oxygenated PAHs (OPAHs). Concentrations of Σalk-PAHs and DBTs, which are known to be enriched in fossil fuels, as well as ΣNPAHs, were highest at a traffic site (MECP) located adjacent to the 18-lane Highway 401 that runs across Toronto. Except for an industrial site (HH/BU), PAC compositions were similar across the sampling sites with Σalk-PAHs being the most abundant class of PACs suggesting traffic emission was a major contributor to PACs in the atmosphere of Toronto. The industrial site exhibited a distinct chemical composition with ΣPAHs dominating over Σalk-PAHs and with elevated levels of fluoranthene, 9-nitroanthracene, and 9,10-anthraquinone, which likely reflects emissions from nearby industrial sources. MECP and HH/BU exhibited higher lifetime excess inhalation cancer risks indicating an association with traffic and industrial sources. The importance of the traffic sector as a source of PACs to ambient air is further supported by strong correlations of the ΣPAHs, Σalk-PAHs, DBTs, and ΣOPAHs with NO x . This study highlights the importance of traffic as an emission source of PACs to urban air and the relevance of PAC classes other than just unsubstituted PAHs that are important but currently not included in air quality guidelines or for assessing inhalation cancer risks., (Crown Copyright © 2019. Published by Elsevier Ltd. All rights reserved.)

Dianthrone derivatives are minor constituents of Polygonum multiflorum Thunb. (PM). These derivatives are potential hepatotoxic components in PM. Fraction D 6 contains many dianthrone derivatives and was successfully enriched using an efficient three-step approach. An effective and reliable high-performance liquid chromatography (HPLC) technique coupled with ultraviolet detection (UV) and a linear ion trap FT-ICR hybrid mass spectrometry (HPLC-UV/LTQ-FT-ICR-MS) method were successfully developed to separate and identify the dianthrones of the fraction D 6 . The characteristic diagnostic fragment ions and characteristic fragmentation pathway of the seven dianthrone standards, namely, Polygonumnolide B1 (S1), Polygonumnolide C3 (S2), Polygonumnolide C2 (S3), Polygonumnolide E (S4), Polygonumnolide A1 (S5), Polygonumnolide A2 (S6) and cis-emodin dianthrones (S7), were compared with unknown compounds in fraction D 6 , and 45 dianthrone derivatives were characterized or tentatively identified. Of these derivatives, 32 new dianthrone derivatives were tentatively characterized in PM. Therefore, LTQ-FT-ICR-MS combined with a selective enrichment method provided a powerful means for analyzing dianthrone derivatives. This study provides a meaningful basis for correcting some mistakes in previous studies, as well as further quality control and pharmacological and toxicological research., (Copyright © 2019 Elsevier B.V. All rights reserved.)

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 β-cyclodextrin (β-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 β-cyclodextrin modified gold nanoparticles.

Brassica rapa is a plant species that can germinate and grow in mixed contaminated soil with PAH and metals (Cr, Pb and Cd). This plant was selected among 14 plant species for electro-phytoremediation tests because its fast germination and growth in contaminated soil. The influence of type of the electric field (AC, DC) and mode of application (continuous, periodic and polarity inversion) was studied in the electro-phytoremediation tests. The application of 1 ACV/cm potential gradient around B. rapa resulted in the effective elimination of anthracene and phenanthrene, but only minor metal removal. The results of this work suggest that alternating current (AC) may be the most suitable electric field for large scale applications. The spatial configuration of electrodes affects the distribution of the electric field in the soil. Various spatial distribution of electrodes have been tested and it has been identified that parallel anodes and cathodes on the soil surface are the most appropriate configuration for field scale applications. Other configurations can be used to concentrate the contaminant around the growing pant or to transport the contaminants from deep soil layers to the rhizosphere., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Halogenated polycyclic aromatic hydrocarbons (HPAHs) were identified in biological samples from the Alberta Oil-Sands Region (AOSR) using gas chromatography coupled with high-resolution time-of-flight mass spectrometry (GC-HRTOF-MS) at a resolving power of 25,000. Knowledge of the electron ionization (EI) fragmentation behavior of individual HPAH isomers, achieved by injecting authentic standards in full-scan MS mode, was paramount in identifying a suite of HPAHs in samples from the AOSR. Confirmation of compounds in biological samples was based on the measured mass accuracy (±3 ppm) of 2 characteristic ions prominent in the EI mass spectra of each compound. Numerous compounds were detected in the high resolution total ion chromatogram in liver extracts of 4 biological species from the AOSR: river otter (Lontra Canadensis), northern pike (Esox lucius), lake whitefish (Coregonus clupeaformis) and snails (Gastropod sp.) many of which remain unidentified. Careful examination of the high-resolution accurate mass data suggests that dichloro-anthracene/phenanthrene, bromo-anthracene/phenanthrene and dibromo-fluorene were present in the biological samples. Lipid corrected concentrations of dichloro-PAHs were estimated to be 16.3 ± 11.4 (n = 4) and 5.5 (n = 1) ng/g in lake whitefish and river otter, respectively. Concentrations of mono-bromo-PAHs were an order of magnitude greater in snails (170.5 ng/g) than in northern pike (12.5 ng/g) while concentrations of dibromo-PAHs were 4 times greater in snails than in northern pike. The detection of these compounds in biota implies that these compounds are bioaccumulative. The liver-based biomagnification factor of the dichloro-PAH congener in the river otter/lake whitefish feeding relationship is much smaller than 1 implying that this compound does not biomagnify., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

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.

This study provides contamination levels, distributions and source apportionment of PAHs in surface sediments in the mid-Adriatic and along the Croatian coast. Median summed concentrations of parent and alkyl-PAHs are circa 10 times lower in the off-shore transect stations of the mid-Adriatic (22.3 and 18.2 μg.kg -1 d.w.) than the ranges determined at the coastal stations, including those of Kaštela bay (227-331 and 11.7-197 μg.kg -1 d.w., respectively). The highest levels, circa 20 times higher, were found in Šibenik bay (median 6603 and 3051 μg.kg -1 ). The overall range of PAH concentrations spans more than 2000 times between the lowest and the highest contamination level. The geographical distributions reflect the presence of strong gradients at local and regional scales. A major factor influencing sedimentary PAH distributions at local scale appears to be the distance from their known continental and coastal upstream emission sites (urban, industrial, harbour …), whereas at regional scale, this distribution depends more on the routes of entry of PAHs into the study area. Two combustion and one petroleum model source profiles of PAHs were determined by alternative least square analysis. Benzo[b+j]fluoranthenes and fluoranthene/pyrene are compounds characterizing two pyrogenic sources respectively, while signatures of alkyl-substituted homologues (phenanthrenes/anthracenes, fluranthenes/pyrenes, chrysenes and dibenzothiophenes) delineate a petrogenic source profile. The quantitative apportionment of source contributions shows significant geographical differences, with a dominant petrogenic source found along the mid-Adriatic transect (approximately 74%) and in Kaštela bay (61%). In the coastal sediments about a fifty-fifty contamination mix is assigned to a petrogenic/pyrogenic source of PAHs (47% and 53% respectively), whereas in Šibenik bay a strong predominance is apportioned to the combustion compounds (81%)., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

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 cm 2 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 (q e ) with the sequence of soybean > maize and 3-NFla > 9-NAnt. The occurrence of GQDs enlarged the q e 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 -NO 2 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 -NO 2 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., (Copyright © 2018 Elsevier Inc. All rights reserved.)

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.

Forest vegetation burning is an important source of atmospheric particulates. In this study, 22 kinds of typical tropical trees in Southeast Asia, which can be divided into evergreen trees, deciduous trees, and shrubs, were selected for experimentation. The emission characteristics of dehydrated sugar, acephenanthrylene, aceanthrylene, and retene were analyzed. The trend of the average emission factor for total sugar was evergreen trees (1.56 g·kg -1 ±1.01 g·kg -1 ) < shrubs (1.99 g·kg -1 ±0.64 g·kg -1 ) < deciduous trees (5.38 g·kg -1 ±7.18 g·kg -1 ). Furthermore, the trend of the average emission factor of acephenanthrylene was evergreen trees (2.63 mg·kg -1 ±2.44 mg·kg -1 ) ≈ shrubs (2.46 mg·kg -1 g±2.14 mg·kg -1 ) < deciduous trees (6.07 mg·kg -1 ±8.50 mg·kg -1 ). For ratios of organic biomarkers, the average ratios of Lev/Man for trees and shrubs were 20.6±11.90 and 23.2±9.20, respectively. The range of Lev/Man was 5.8-51.5 in this study. The average ratios of AP/AC for trees and shrubs were 7.13±5.18 and 5.53±1.51, respectively. Compared with the dehydrated sugar, which was affected by more conditions, the analysis methods of aromatic hydrocarbons were simple. Furthermore, although the ratio of AP/AC was less stable than that of FL/PY in this manuscript, AP/AC was less affected by other sources of pollution and had higher specificity. In conclusion, the advantages and disadvantages of each organic biomarker can be synthetically considered in terms of biomass source analysis in order to improve accuracy, and acephenanthrylene was a better choice than other biomarkers.

Six kinds of provenance of Rheum tanguticum collected from Qinghai province as the test materials, which were transplanted under 3 different environments by using complete randomized block design with three replicates. The contents of the chemical components was determined by HPLC. This study aimed at analyzing the effect of genotype, environment and their interactions on the 4 kinds of functional components (phenolic acids, bianthrone, free anthraquinones and combined anthraquinones) in 14 kinds of active components of Rh. tanguticum, in order to provide a theoretical basis for the selection of cultivated Rh. tanguticum in high quality producing area and excellent provenance. The provenance trial showed that the genotype and environment influence on the effect of all kinds of functional components in Rh. tanguticum were significant ( P <0.05). The content of phenolic acids was mainly influenced by environment, and the other three kinds of functional components were affected by environment and their interactions. The proportion of environment was larger. The cultivation quality of Rh. tanguticum should give priority to environment, then choose a provenance. Sichuan may be beneficial in accumulation of combined anthraquinones in Rh. tanguticum, Gansu may facilitate the binding of free anthraquinone, phenolic acids and bianthrone content. Preliminary inference based on the content and proportion of efficacy components, T4 could be potential special medicinal germplasm that have function of heat-clearing and detoxifying drugs and activate blood circulation to dissipate blood stasis; T3 and T6 could all be potential specialmedicinal germplasms that exist diarrhea attack characters. The results of this study have certain guiding significance for the production of rhubarb precision medicinal materials., Competing Interests: The authors of this article and the planning committee members and staff have no relevant financial relationships with commercial interests to disclose., (Copyright© by the Chinese Pharmaceutical Association.)

Eight kinds of provenance of Rheum palmatum collected from 4 provinces Sichuan, Ningxia, Gansu, Shannxi as test materials, which were transplanted under 3 different environments by using complete randomized block design with three replicates. The contents of the chemical components was determined by HPLC. This study aimed at analyzing the effect of genotype, environment and their interactions on the 4 kinds of functional components (phenolic acids, bianthrone, free anthraquinones and combined anthraquinones) in 14 kinds of active components of R. palmatum, in order to provide a theoretical basis for the selection of cultivated R. palmatum in high quality producing area and excellent provenance. The functional components of R. palmatum were influenced by genotype and environment. The content of phenolic acids was mainly influenced by environment, and the other three kinds of functional components were affected by environment and their interactions. The proportion of environment was larger. The cultivation quality of R. palmatum should give priority to environment, then choose a provenance. Sichuan may be beneficial in accumulation of free anthraquinones in R. palmatum, Gansu may facilitate the binding of combined anthraquinone, phenolic acids and bianthrone content. Preliminary inference based on the content and proportion of efficacy components, P2 could be potential special medicinal germplasm that have function of heat-clearing and detoxifying drugs. P6 could be potential special medicinal germplasm that activate blood circulation to dissipate blood stasis. P7 and P1 could all be potential specialmedicinal germplasms that exist diarrhea attack characters. The results of this study have important guiding significance for the production of rhubarb precision medicinal materials., Competing Interests: The authors of this article and the planning committee members and staff have no relevant financial relationships with commercial interests to disclose., (Copyright© by the Chinese Pharmaceutical Association.)