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Polycyclic aromatic hydrocarbon (PAH) derivatives are mutagenic, carcinogenic, teratogenic and bioaccumulative pollutants. Investigations on hydroxylated PAHs (OH–PAHs) and Nitrated PAHs (NPAHs) in surface water are not enough. In this study, optimization and validation of an analytical method targeting nine kinds of OH–PAHs and one kind of nitrated PAH in environmental water samples are presented. The method was validated for linearity, limits of detection and quantification and recovery using spiked matrix. The linear range of most target compounds was 0.1–200 ng∙mL−1. However, the linear range of 1–hydroxy pyrene and 3–hydroxy benzo[a]pyrene started at 1 ng∙mL−1 and the linear range of 1–hydroxy phenanthrene and 9–hydroxy benzo[a]pyrene could not reach 200 ng∙mL−1. All the correlation coefficients (r2) were over 0.997. The instrumental limits of detection (LOD) and method detection limits (MDL) ranged from 0.01 to 0.67 ng∙mL−1 and 1.11 to 2.26 ng∙L−1, respectively. With this method, a lake in Hebei province, China, were screened. Three kinds of target compounds were detected. The average concentration was around 2.5 ng∙L−1, while the highest concentration reached 286.54 ng∙L−1.

Apple Replant Disease (ARD) is a significant problem in apple orchards that causes root tissue damage, stunted plant growth, and decline in fruit quality, size, and overall yield. Dysbiosis of apple root-associated microbiome and selective richness of Streptomyces species in the rhizosphere typically concurs root impairment associated with ARD. However, possible roles of Streptomyces secondary metabolites within these observations remain unstudied. Therefore, we employed the One Strain Many Compounds (OSMAC) approach coupled to high-performance liquid chromatography-high-resolution tandem mass spectrometry (HPLC-HRMSn) to evaluate the chemical ecology of an apple root-associated Streptomycesciscaucasicus strain GS2, temporally over 14 days. The chemical OSMAC approach comprised cultivation media alterations using six different media compositions, which led to the biosynthesis of the iron-chelated siderophores, ferrioxamines. The biological OSMAC approach was concomitantly applied by dual-culture cultivation for microorganismal interactions with an endophytic Streptomyces pulveraceus strain ES16 and the pathogen Cylindrocarpon olidum. This led to the modulation of ferrioxamines produced and further triggered biosynthesis of the unchelated siderophores, desferrioxamines. The structures of the compounds were elucidated using HRMSn and by comparison with the literature. We evaluated the dynamics of siderophore production under the combined influence of chemical and biological OSMAC triggers, temporally over 3, 7, and 14 days, to discern the strain’s siderophore-mediated chemical ecology. We discuss our results based on the plausible chemical implications of S. ciscaucasicus strain GS2 in the rhizosphere.

Vesuvius eruption that destroyed Pompeii in AD 79 represents one of the most important events in history. The cataclysm left behind an abundance of archeological evidence representing a fundamental source of the knowledge we have about ancient Roman material culture and technology. A great number of textiles have been preserved, rarely maintaining traces of their original color, since they are mainly in the mineralized and carbonized state. However, one outstanding textile sample displays a brilliant purple color and traces of gold strips. Since the purple was one of the most exclusive dyes in antiquity, its presence in an important commercial site like Pompeii induces us to deepen the knowledge of such artifacts and provide further information on their history. For this reason, the characterization of the purple color was the main scope of this research, and to deepen the knowledge of such artifacts, the SERS (Surface Enhanced Raman Scattering) in solution approach was applied. Then, these data were enriched by HPLC-HRMS analyses, which confirmed SERS-based hypotheses and also allowed to hypothesize the species of the origin mollusk. In this context, a step-by-step integrated approach resulted fundamental to maximize the information content and to provide new data on textile manufacturing and trade in antiquity.

RATIONALE: Anthropogenic organic inputs to freshwaters can exert detrimental effects on aquatic ecosystems, raising growing concern for both environmental conservation and water security. Current regulation by the EU water framework directive (European Union, 2000/60/EC) relates to organic pollution by monitoring selected micropollutants, however, aquatic ecosystem responses requires a comprehensive understanding of dissolved organic matter (DOM) composition. The introduction of high-resolution mass spectrometry (HRMS) is set to greatly increase our understanding of thecomposition of DOM of both natural and anthropogenic origin derived from diffuse and point sources.METHODS: DOM was extracted from riverine and treated sewage effluent using solid phase extraction (SPE) and analysed using dissolved organic carbon (DOC) analysis, direct infusion-high resolution Orbitrap™ mass spectrometry (DI-HRMS) and high-performance liquid chromatography (HPLC/HRMS). The data obtained were analysed using univariate and multivariate statistics to demonstrate differences in background DOM, anthropogenic inputs and in-river mixing. Compound identifications were achieved based on MS2 spectra searched against on-line databases.RESULTS: DI-HRMS spectra showed the highly complex nature of all DOM SPE extracts. Classification and visualisation of extracts containing many thousands of individual compounds were achieved using PCA and hierarchical cluster analysis. Kruskal-Wallis analyses highlighted significant discriminating ions originating from the sewage treatment works for more in-depth investigation by HPLC/HRMS. The generation of MS2 spectra in HPLC/HRMS provided the basis for identification of anthropogenic compounds including; pharmaceuticals, illicit drugs, metabolites and polymers, although many thousands of compounds remain unidentified.CONCLUSIONS: This new approach enables comprehensive analysis of DOM in extracts without any preconceived ideas of the compounds which may be present. This approach has the potential to be used as a high throughput, qualitative, screening method to determine if the composition of point sources differs from that of the receiving water bodies, providing a new approach to the identification of hitherto unrecognised organic contribution to water bodies.

Microalgae have recently become a popular functional food due to their health benefits. Sulfolipids, a class of substances abundant in this matrix, have been reported to have interesting bioactivities, such as anti-carcinogenic activity. However, despite the potential interest in sulfolipids, a dedicated analytical method for their characterization is currently lacking but would significantly increase the coverage of sulfolipids with respect to the direct lipidomic analysis. To achieve this goal, in this work a procedure, based on graphitized carbon black solid phase extraction, was developed for clean-up and enrichment of sulfolipids (sulfoquinovosyldiacylglycerols and sulfoquinovosylmonoacylglycerols) and it was applied to spirulina (Arthrospira platensis) microalgae. A careful study of the solid phase extraction conditions was performed, first to maximize the recovery of reference standards, then to increase the total number of identified sulfolipids from the spirulina lipid extract. All samples were analysed by ultra-high performance liquid chromatography coupled to high resolution mass spectrometry and lipids were tentatively identified by Lipostar, for a reliable lipid structure assignment. The developed method was compared to the direct lipidomic analysis without enrichment, to establish the enrichment efficiency in terms of number of identifications. From the comparison, the enrichment procedure proved better and allowed the tentative identification of 199 sulfolipids, which is the largest number reported so far for the Arthrospira platensis species. The described method was validated in terms of precision, accuracy, recovery, limit of quantitation and detection for two sulfolipids. Finally, a relative lipid quantitation based on peak area was carried out on the microalgae sample, which indicated nine abundant sulfolipids as representing ca. 60% of sulfolipids in spirulina microalgae.

The identification of dyes from ancient textiles represents a challenging issue requiring high proficiency and versatility, that must be guided by the principles of non-destructiveness. The complexity of the dye/textile system influences both the choice of sampling and extraction procedures and the analytical methodology. For instance, in order to preserve both the fibre and the original chromophores on it, the extraction procedures commonly used for natural dyes have evolved in last few decades towards increasingly mild conditions. Along with this approach, the use of solid substrates for sampling has become prominent in several fields of Cultural Heritage diagnostics.With reference to these two aspects, the aim of this work is to combine gel substrates and a mild basic solution for the extraction of anthraquinone dyes (madder and cochineal) from wool textiles, in order to evaluate the versatility of the extraction procedure for different analytical techniques. Because of their wide use in the field of Conservation, agar and nanorestore gel substrates soaked in an ammonia-EDTA solution were tested. The dye-extracting substrates were then analysed with Raman and SERS spectroscopy, whilst the fraction re-extracted from them was examined with HPLC-HRMS. Finally, scanning electron microscopy was used to monitor the integrity of the wool after the extraction treatment with the ammonia-EDTA solution.HPLC-HRMS results show that the basic solution in both gels is effective for the dye extraction, and no alteration of wool fibres was evidenced by SEM-EDS. The Raman spectra give no information about the dyes, but only substrate signals are obtained. Conversely, SERS spectroscopy makes it possible to distinguish the two dyes, especially using the 633 nm laser on the agar substrate.

The analysis of lipid molecules in living organism is an important step in deciphering metabolic pathways. Recently, the zebrafish has been adopted as a valuable animal model system to perform in vivo metabolomics studies, however limited methodologies and protocols are currently available to investigate zebrafish lipidome and even fewer to analyze specific classes of lipids. Here we present an HPLC-HRMS based method to rapidly measure multiple prenol lipid molecules from zebrafish tissues. In particular, we have optimized our method for concurrent detection of ubiquinones (Coenzyme Q6, Coenzyme Q9, Coenzyme Q10), cholesterol, vitamin E (α-tocopherol), vitamin K1 and vitamin K2. The purpose of this study was to compare different ionization modes, mobile phases and stationary phases in order to optimize lipid molecules separation. After HPLC-HRMS parameters selection, several extraction conditions from zebrafish embryos were evaluated. We assessed our methodology by quantitation of analytical recovery on zebrafish extracts from wild-type or zebrafish mutants (barolo) affected by impaired biosynthesis of ubiquinones.

In this paper, an innovative alkaline mild extraction method has been applied to characterize the dyes present in lake-pigment and textile, prepared from American and Armenian cochineal. This extraction methodology, successfully employed for the conservation of glycosyl moieties in anthraquinone dyes from madder ( Rubia tinctorum L.), is applied on cochineal lake and textiles in order to evaluate if its application results in obtaining new information about cochineal dyes composition. Furthermore, in this paper, a slightly modified ammonia-Na 2 EDTA extraction methodology is presented. The modification of the extraction methodology resulted to be necessary to ensure its applicability to this class of natural dyes. Once optimized the protocol, the extracts have been analyzed through HPLC-HRMS, in order to characterize the present compounds. In particular, basing on the MS/MS paths reported in literature, it has been possible to recognize several O -glycosyl compounds, never found before in American cochineal dyed yarns or lake pigments extracts. In particular, for the first time, an O -glycoside of flavokermesic acid, known as pp6, suggested until this moment as a marker of Polish cochineal, has been recognized in both lake-pigment and dyed yarns prepared from American cochineal. In addition, it has been possible to compare the composition of American cochineal dyed yarns ammonia-Na 2 EDTA extracts with those obtained from Armenian cochineal dyed yarn, extracted with the same protocol.

The roots and rhizomes of licorice plants (genus Glycyrrhiza L.) are commercially employed, after processing, in confectionery production or as sweetening and flavouring agents in the food, tobacco and beer industries. G. glabra, G. inflata and G. uralensis are the most significant licorice species, often indistinctly used for different productions. Licorice properties are directly related to its chemical composition, which determines the commercial values and the quality of the derived products. In order to better understand the characteristics and properties of each species, a chemical characterization of three species of licorice (G. glabra, G. inflata, G. uralensis) is proposed, through an untargeted metabolomic approach and using high-resolution mass spectrometry. The statistical analysis reveals new possible markers for the analyzed species, and provides a reliable identification of a high number of metabolites, contributing to the characterization of Glycyrrhiza metabolome.

In this paper, an analytical method has been developed and validated for the analysis of new psychoactive substances (NPS) and metabolites in hair samples. The method was based on pressurized liquid extraction (PLE) followed by solid-phase extraction (SPE) clean-up and high performance liquid chromatography-high resolution mass spectrometry (HPLC-HRMS) analysis. To evaluate extraction efficiency and the applicability of the method, hair samples were fortified by soaking in order to obtain a good surrogate for drug users' hair; the amount of incorporated drugs related to their lipophilicity, similarly to in vivo drug incorporation. To the best of our knowledge, this is the first method that allowed for the analysis of both cathinones (5) and synthetic cannabinoids (7) in hair with a single extraction procedure and chromatographic run. A phenethylamine (2C-T-4), 4- fluorophenylpiperazine and methoxetamine were also included showing that PLE coupled to SPE clean-up was suitable for a multi-class analysis of NPS in hair. In addition, the use of PLE significantly reduced hair analysis time: decontamination, incubation, clean-up, and liquid chromatography-mass spectrometry (LC-MS) analysis were carried out in approximately 45 min. The method was fully validated according to Scientific Working Group for Forensic Toxicology (SWGTOX) and Society of Hair Testing (SoHT) guidelines. Limit of quantification (LOQ) values ranged from 8 to 50 pg mg

Honey is a valuable functional food rich in phenolic compounds with a broad spectrum of biological activities. Analysis of the phenolic compounds in honey is a very promising tool for the quality control, the authentication and characterization of botanical origin, and the nutraceutical research. This work describes a novel approach for the rapid analysis of five phenolic acids and 10 flavonoids in honey. Phenolic compounds were rapidly extracted and concentrated from diluted honey by dispersive liquid-liquid microextraction (DLLME) and then analyzed using high performance liquid chromatography with UV absorbance detection (HPLC-UV). Some important parameters, such as the nature and volume of extraction and dispersive solvents, pH and salt effect were carefully investigated and optimized to achieve the best extraction efficiency. Under the optimal conditions, an exhaustive extraction for twelve of the investigated analytes (recoveries >70%), with a precision (RSD