Sorption of Polycyclic Aromatic Sulfur Heterocycles (PASH) on Nylon Microplastics at Environmentally Relevant Concentrations.

Microplastics have garnered an infamous reputation as a sorbate for many concerning environmental pollutants and as a delivery vehicle for the aquatic food chain through the ingestion of these contaminated small particulates. While sorption mechanisms have been extensively studied for polycyclic aromatic hydrocarbons, polycyclic aromatic sulfur heterocycles (PASHs) have not been investigated, partly due to their low concentrations in aquatic ecosystems. Herein, an analytical methodology is presented for the analysis of dibenzothiophene, benzo[b]naphtho[1,2-b]thiophene, benzo[b]naphtho[2,1-b]thiophene, benzo[b]naphtho[2,3-b]thiophene, chryseno[4,5-bcd]thiophene and dinaphtho[1,2-b:1',2'-d]thiophene at relevant environmental concentrations based on solid phase extraction and high-performance liquid chromatography. The sorption uptake behavior and the sorption kinetics of the three benzo[b]napthothiophene isomers were then investigated on nylon microplastics to provide original information on their environmental fate and avoid human contamination through the food chain. The obtained information might also prove relevant to the development of successful remediation approaches for aquatic ecosystems.

Polycyclic aromatic hydrocarbons (PAHs): Updated aspects of their determination, kinetics in the human body, and toxicity.

Polycyclic aromatic hydrocarbons (PAHs) are legacy pollutants of considerable public health concern. Polycyclic aromatic hydrocarbons arise from natural and anthropogenic sources and are ubiquitously present in the environment. Several PAHs are highly toxic to humans with associated carcinogenic and mutagenic properties. Further, more severe harmful effects on human- and environmental health have been attributed to the presence of high molecular weight (HMW) PAHs, that is PAHs with molecular mass greater than 300 Da. However, more research has been conducted using low molecular weight (LMW) PAHs). In addition, no HMW PAHs are on the priority pollutants list of the United States Environmental Protection Agency (US EPA), which is limited to only 16 PAHs. However, limited analytical methodologies for separating and determining HMW PAHs and their potential isomers and lack of readily available commercial standards make research with these compounds challenging. Since most of the PAH kinetic data originate from animal studies, our understanding of the effects of PAHs on humans is still minimal. In addition, current knowledge of toxic effects after exposure to PAHs may be underrepresented since most investigations focused on exposure to a single PAH. Currently, information on PAH mixtures is limited. Thus, this review aims to critically assess the current knowledge of PAH chemical properties, their kinetic disposition, and toxicity to humans. Further, future research needs to improve and provide the missing information and minimize PAH exposure to humans.

Investigation of the Effects of Dioctyl Sulfosuccinate on the Photodegradation of Benzo[a]Pyrene in Aqueous Solutions under Various Wavelength Regimes.

Due to the relatively high concentrations of polycyclic aromatic hydrocarbons (PAHs) in oil samples, oil spills in aquatic ecosystems release significant amounts of PAHs. Although remediation efforts often take place during or immediately after an oil spill incident, a portion of the released PAHs remains in the body of water. A natural phenomenon resulting from the direct exposure of PAHs to sunlight is photodegradation. This article investigates the effect of dioctyl sulfosuccinate (DOSS) on the photodegradation of benzo[a]pyrene (BaP), the most toxic PAH in the priority pollutants list of the US Environmental Protection Agency (EPA). DOSS is a surfactant typically used in the remediation of oil spills. Three lamps with maximum emission wavelengths at 350 nm, 419 nm, and 575 nm were individually and simultaneously used to irradiate aqueous solutions of BaP in the absence and the presence of DOSS. When irradiated with the 419 nm lamp or the 575 lamp, BaP showed no photodegradation. Upon irradiation with the 350 nm lamp and with the simultaneous use of the three lamps, the photodegradation of BaP followed first-order kinetics. Independent of the irradiation wavelength, the presence of DOSS increased the half-life of BaP in the aqueous solution. In the case of the 350 nm lamp, the rate constant of photodegradation in the absence and the presence of DOSS varied from (3.79 ± 0.97) × 10-3 min-1 to (1.10 ± 0.13) × 10-3 min-1, respectively. Under simultaneous irradiation with the lamps, the rate constant of photodegradation varied from (1.12 ± 0.35) × 10-3 min (no DOSS) to (3.30 ± 0.87) × 10-4 (with DOSS). Since the largest rate constants of photodegradation were observed in the absence of DOSS, the longer half-lives of BaP in the presence of surfactant were attributed to the incorporation of PAH molecules into the DOSS micelles.

Nondestructive Forensic Comparison of Nylon Trace Evidence Using Room-Temperature Fluorescence Spectroscopy.

The increasing accessibility of 3D printers makes their use for criminal activity more likely. Current forensic analysis of trace evidence left by 3D-printed materials focuses on identifying the general type of plastic, which includes acrylonitrile butadiene styrene, polylactic acid, nylon, polycarbonate, polyethylene terephthalate, and chlorinated polyethylene. Herein, we present a nondestructive approach capable of differentiating among different types of nylons. The new approach is based on room-temperature fluorescence spectroscopy. Excitation-emission matrices, excitation and emission spectra, and synchronous fluorescence spectra are directly recorded from single microplastics with the aid of a fiber-optic probe coupled to a commercial spectrofluorometer. The comparison of spectral features demonstrates the capability to differentiate microparticles originating from Nylon 11, Nylon 12, Nylon 6/6, and Nylon 6/12. The observed differences are attributed to the presence of fluorescent impurities embedded in the polymer during its fabrication. The outstanding matching of excitation-emission matrices, excitation and emission spectra, and synchronous fluorescence spectra demonstrates the potential of this approach to link trace evidence to a specific source beyond its general plastic type.

Solid State Multicolor Emission in Substitutional Solid Solutions of Metal-Organic Frameworks.

Preparing crystalline materials that produce tunable organic-based multicolor emission is a challenge due to the inherent inability to control the packing of organic molecules in the solid state. Utilizing multivariate, high-symmetry metal-organic frameworks, MOFs, as matrices for organic-based substitutional solid solutions allows for the incorporation of multiple fluorophores with different emission profiles into a single material. By combining nonfluorescent links with dilute mixtures of red, green, and blue fluorescent links, we prepared zirconia-type MOFs and found that the bulk materials exhibit features of solution-like fluorescence. Our study found that MOFs with a fluorophore link concentration of around 1 mol % exhibit fluorescence with decreased inner filtering, demonstrated by changes in spectral profiles, increased quantum yields, and lifetime dynamics expected for excited-state proton-transfer emitters. Our findings enabled us to prepare organic-based substitutional solid solutions with tunable chromaticity regulated only by the initial amounts of fluorophores. These materials emit multicolor and white light with high quantum yields (∼2-14%), high color-rendering indices (>93), long shelf life, and superb hydrolytic stability at ambient conditions.

Modular Design of Fluorescent Dibenzo- and Naphtho-Fluoranthenes: Structural Rearrangements and Electronic Properties.

A library of 12 dibenzo- and naphtho-fluoranthene polycyclic aromatic hydrocarbons (PAHs) with MW = 302 (C24H14) was synthesized via a Pd-catalyzed fluoranthene ring-closing reaction. By understanding the various modes by which the palladium migrates during the transformation, structural rearrangements were bypassed, obtaining pure PAHs in high yields. Spectroscopic and electrochemical characterization demonstrated the profound diversity in the electronic structures between isomers. Highlighting the significant differences in emission of visible light, this library of PAHs will enable their standardization for toxicological assessment and potential use as optoelectronic materials.

Normal-phase liquid chromatography retention behavior of polycyclic aromatic sulfur heterocycles and alkyl-substituted polycyclic aromatic sulfur heterocycle isomers on an aminopropyl stationary phase.

Retention indices for 67 polycyclic aromatic sulfur heterocycles (PASHs) and 80 alkyl-substituted PASHs were determined using normal-phase liquid chromatography (NPLC) on an aminopropyl (NH2) stationary phase. The retention behavior of PASH on the NH2 phase is correlated with the number of aromatic carbon atoms and two structural characteristics have a significant influence on their retention: non-planarity (thickness, T) and the position of the sulfur atom in the bay-region of the structure. Correlations between solute retention on the NH2 phase and T of PASHs were investigated for three cata-condensed (cata-) PASH isomer groups: (a) 13 four-ring molecular mass (MM) 234 Da cata-PASHs, (b) 20 five-ring MM 284 Da cata-PASHs, and (c) 12 six-ring MM 334 Da cata-PASHs. Correlation coefficients ranged from r = -0.49 (MM 234 Da) to r = -0.65 (MM 334 Da), which were significantly lower than structurally similar PAH isomer groups (r = -0.70 to r = -0.99). The NPLC retention behavior of the PASHs are compared to similar results for PAHs.

Qualitative characterization of three combustion-related standard reference materials for polycyclic aromatic sulfur heterocycles and their alkyl-substituted derivatives via normal-phase liquid chromatography and gas chromatography/mass spectrometry.

The research described here provides the most comprehensive qualitative characterization of three combustion-related standard reference materials (SRMs) for polycyclic aromatic sulfur heterocycles (PASHs) and some alkyl-substituted (alkyl-) derivatives to date: SRM 1597a (coal tar), SRM 1991 (coal tar/petroleum extract), and SRM 1975 (diesel particulate extract). An analytical approach based on gas chromatography/mass spectrometry (GC/MS) is presented for the determination of three-, four-, and five-ring PASH isomers and three- and four-ring alkyl-PASHs in the three SRM samples. The benefit of using a normal-phase liquid chromatography (NPLC) fractionation procedure prior to GC/MS analysis was demonstrated for multiple isomeric PASH groups. Using a semi-preparative aminopropyl (NH2) LC column, the three combustion-related samples were fractionated based on the number of aromatic carbon atoms. The NPLC-GC/MS method presented here allowed for the following identification breakdown: SRM 1597a - 35 PASHs and 59 alkyl-PASHs; SRM 1991-31 PASHs and 58 alkyl-PASHs; and SRM 1975-13 PASHs and 25 alkyl-PASHs. These identifications were based on NPLC retention data, the GC retention times of reference standards, and the predominant molecular ion peak in the mass spectrum. Prior to this study, only 11, 1, and 0 PASHs/alkyl-PASHs had been identified in SRM 1597a, SRM 1991, and SRM 1975, respectively. Graphical abstract NPLC-GC/MS analysis for the three- and four-ring parent PASH isomers in SRM 1597a.

Qualitative characterization of SRM 1597a coal tar for polycyclic aromatic hydrocarbons and methyl-substituted derivatives via normal-phase liquid chromatography and gas chromatography/mass spectrometry.

A normal-phase liquid chromatography (NPLC) fractionation procedure was developed for the characterization of a complex mixture of polycyclic aromatic hydrocarbons (PAHs) from a coal tar sample (Standard Reference Material (SRM) 1597a). Using a semi-preparative aminopropyl (NH2) LC column, the coal tar sample was separated using NPLC based on the number of aromatic carbons; a total of 14 NPLC fractions were collected. SRM 1597a was analyzed before and after NPLC fractionation by using gas chromatography/mass spectrometry (GC/MS) with a 50% phenyl stationary phase. The NPLC-GC/MS method presented in this study allowed for the identification of 72 PAHs and 56 MePAHs. These identifications were based on the NPLC retention times for authentic reference standards, GC retention times for authentic reference standards, and the predominant molecular ion peak in the mass spectrum. Most noteworthy was the determination of dibenzo[a,l]pyrene, which could not be measured directly by GC/MS because of low concentration and co-elution with dibenzo[j,l]fluoranthene. The NPLC-GC/MS procedure also allowed for the tentative identification of 74 PAHs and 117 MePAHs based on the molecular ion peak only. This study represents the most comprehensive qualitative characterization of SRM 1597a to date. Graphical abstract NPLC-GC/MS analysis for the six-ring MM 302 Da PAH isomers in SRM 1597a.

Normal-phase liquid chromatography retention behavior of polycyclic aromatic hydrocarbon and their methyl-substituted derivatives on an aminopropyl stationary phase.

Retention indices for 124 polycyclic aromatic hydrocarbons (PAHs) and 62 methyl-substituted (Me-) PAHs were determined using normal-phase liquid chromatography (NPLC) on a aminopropyl (NH2) stationary phase. PAH retention behavior on the NH2 phase is correlated to the total number of aromatic carbons in the PAH structure. Within an isomer group, non-planar isomers generally elute earlier than planar isomers. MePAHs generally elute slightly later but in the same region as the parent PAHs. Correlations between PAH retention behavior on the NH2 phase and PAH thickness (T) values were investigated to determine the influence of non-planarity for isomeric PAHs with four to seven aromatic rings. Correlation coefficients ranged from r = 0.19 (five-ring peri-condensed molecular mass (MM) 252 Da) to r = -0.99 (five-ring cata-condensed MM 278 Da). In the case of the smaller PAHs (MM ≤ 252 Da), most of the PAHs had a planar structure and provided a low correlation. In the case of larger PAHs (MM ≥ 278 Da), nonplanarity had a significant influence on the retention behavior and good correlation between retention and T was obtained for the MM 278 Da, MM 302 Da, MM 328 Da, and MM 378 Da isomer sets. Graphical abstract NPLC separation of the three-, four-, five-, and six-ring PAH isomers with different number of aromatic carbon atoms and degrees of non-planarity (Thickness, T). The inserted figure plots the number of aromatic carbon atoms vs. the log I value for the 124 parent PAHs.

Nondestructive Total Excitation-Emission Fluorescence Microscopy Combined with Multi-Way Chemometric Analysis for Visually Indistinguishable Single Fiber Discrimination.

The potential of total excitation-emission fluorescence microscopy combined with multiway chemometric analysis was investigated for the nondestructive forensic analysis of textile fibers. The four pairs of visually indistinguishable fibers consisted of nylon 361 dyed with acid yellow 17 and acid yellow 23, acetate satin 105B dyed with disperse blue 3 and disperse blue 14, polyester 777 dyed with disperse red 1 and disperse red 19, and acrylic 864 dyed with basic green 1 and basic green 4. Excitation emission matrices were recorded with the aid of an inverted microscope and a commercial spectrofluorimeter. The full information content of excitation-emission matrices was processed with the aid of unsupervised parallel factor analysis (PARAFAC), PARAFAC supervised by linear discriminant analysis (LDA), and discriminant unfolded partial least-squares (DU-PLS). The ability of the latter algorithm to classify the four pairs of fibers demonstrates the advantage of using the multidimensionality of fluorescence data formats for the nondestructive analysis of forensic fiber evidence.

Identification of detergents for forensic fiber analysis.

Trace fibers are an important form of trace evidence, and identification of exogenous substances on textile fibers provides valuable information about the origin of the fiber. Laundering textiles can provide a unique fluorescent spectral signature of the whitening agent in the detergent that adsorbs to the fiber. Using fluorescence microscopy, the spectral characteristics of seven detergents adsorbed to single fibers drawn from laundered textiles were investigated, and principal component analysis of clusters was used to characterize the type of detergent on the fiber. On dyed nylon fibers, spectra from eight different detergent pairs could be resolved and washed validation fibers correctly classified. On dyed acrylic fibers, five different detergent pairs could be resolved and identified. Identification of the detergent type may prove useful in matching a trace fiber to its bulk specimen of origin.

Parallel Factor Analysis of 4.2 K Excitation-Emission Matrices for the Direct Determination of Dibenzopyrene Isomers in Coal-Tar Samples with a Cryogenic Fiber-Optic Probe Coupled to a Commercial Spectrofluorimeter.

Several studies have shown high concentrations of polycyclic aromatic hydrocarbons (PAHs) in living spaces and soil adjacent to parking lots sealed with coal-tar-based products. Recent attention has been paid to the presence of seven PAHs in coal-tar samples, namely, benz[a]anthracene, benzo[k]-fluoranthene, benzo[b]fluoranthene, benzo[a]pyrene, chrysene, dibenz[a,h]anthracene, and indeno[1,2,3-cd]pyrene, and their association to significant increases in estimated excess lifetime cancer risk for nearby residents. Herein, we present an analytical approach to screen the presence of five highly toxic, high-molecular weight PAHs (HMW-PAHs) in coal-tar samples. These include dibenzo[a,l]pyrene, dibenzo[a,i]pyrene, dibenzo[a,e]pyrene, dibenzo[a,h]pyrene, and naphtho[2,3-a]pyrene. Their direct analysis, without chromatographic separation, in a reference coal-tar sample is made possible with the combination of excitation-emission matrices (EEMs) and parallel factor analysis (PARAFAC). EEMs are recorded at 4.2 K with the aid of a cryogenic fiber-optic probe and a commercial spectrofluorimeter. The simplicity of the experimental procedure and the excellent analytical figures of merit demonstrate the screening potential of this environmentally friendly approach for the routine analysis of numerous coal-tar samples.

Single fiber identification with nondestructive excitation-emission spectral cluster analysis.

Identification methods for single textile fibers are in demand for forensic applications, and nondestructive methods with minimal pretreatment have the greatest potential for utility. Excitation-emission luminescence data provide a three-dimensional matrix for comparison of single-fiber dyes, and these data are enhanced by principal component analysis and comparison of fibers using a statistical figure of merit. No dye extraction methods are required to sample the spectra from a single fiber. This approach has been applied to the analysis of single fibers to compare closely matched dye pairs, acid blue (AB) 25 and 41 and direct blue (DB) 1 and 53. In all cases, the accuracy of fiber identification was high and no false positive identifications were made.

Screening method for the analysis of Rhodamine B in chili powder.

Rhodamine B is a synthetic dye known to enhance the visual appearance of chili powder. Due to its toxicity and carcinogenicity, chromatographic methods have been developed to monitor its presence in adulterated chili powder, but their assays are laborious, time consuming and expensive for screening purposes. The present studies propose an alternative for screening Rhodamine B in chili powder samples. The method combines thin layer chromatography (TLC) to solid surface room-temperature fluorescence spectroscopy. The scrape-dissolution procedure common to the instrumental analysis of TLC procedures was replaced with a fiber optic probe coupled to a commercial spectrofluorometer. The determination of Rhodamine B on the chromatographic plate is based on its retardation factor and maximum excitation and emission wavelengths. The limit of detection (1.9 ng.mL-1) and the limit of quantitation (5.2 ng.mL-1) are well below the usual contamination of Rhodamine B in adulterated foods.

Differentiating Nylon Samples with Visually Indistinguishable Fluorescence Using Principal Component Analysis and Common Dimension Partial Least Squares Linear Discriminant Analysis with Synchronous Fluorescence Spectroscopy.

Fluorescence spectroscopy is an attractive candidate for analyzing samples of nylon. Impurities within the polymers formed during the synthesis and processing of nylons give rise to the observed fluorescence, allowing for nylons to be analyzed based on their impurities. Nylons from the same source are expected to display similar fluorescence profiles, and nylons with different fluorescence are expected to be from different sources. This paper investigates an important case where different nylons displayed similar fluorescence, preventing easy discrimination. Samples of Nylon 6 and Nylon 6/12 had visually indistinguishable excitation-emission matrices (EEM), excitation spectra, fluorescence spectra, and synchronous fluorescence spectra at larger Δλ. By collecting synchronous fluorescence spectra at smaller Δλ, additional features in the fluorescence profiles were identified that allowed for some discrimination between the two nylons. Combining the EEM and synchronous fluorescence data with chemometric algorithms provided a clearer differentiation between the two nylons. parallel factor analysis, principal component analysis, and common dimension partial least squares (ComDim-PLS) showed two distinct clusters in the data, with ComDim-PLS providing the greatest distinction between the clusters. The loadings revealed the variables of interest to the ComDim-PLS were the 400 nm and 335 nm bands for all synchronous fluorescence spectra, the 460 nm and 310 nm bands for the Δλ = 20 nm and Δλ = 30 nm synchronous fluorescence spectra, and the 440 nm band for the Δλ = 20 nm synchronous fluorescence spectra. The linear discriminant analysis performed with the PLS data yielded a classification accuracy of 95% with the EEM data and 100% with the synchronous fluorescence data, displaying the power of this technique to differentiate two different nylons with visually indistinguishable fluorescence spectra.

Total synchronous fluorescence spectroscopic data modeled with first- and second-order algorithms for the determination of doxorubicin in human plasma.

In this work, we present the development of a method for the determination of doxorubicin in plasma samples in the presence of an unexpected component (riboflavin) by using total synchronous fluorescence spectroscopic data matrices. To the best of our knowledge, this is the first time that the second-order advantage is obtained with this kind of data. Two strategies including unfolding the data and: (a) processing with multivariate curve resolution coupled to alternating least-squares as first-order data or (b) processing with unfolded partial least-squares and exploiting the second-order advantage by the residual bilinearization procedure were considered. The calibration set was built with human plasma samples spiked with doxorubicin, while the validation set was prepared with human plasma samples spiked with both doxorubicin and riboflavin, a drug whose spectrum highly overlaps with the one corresponding to doxorubicin. Both methodologies reached good indicators of accuracy: recoveries of ca. 100 ± 8% and REP of ca. 5%; and precision: coefficient of variations between 7 and 9%.

Determination of polycyclic aromatic hydrocarbon metabolites in milk by a quick, easy, cheap, effective, rugged and safe extraction and capillary electrophoresis.

We describe the first application of a quick, easy, cheap, effective, rugged and safe extraction technique to the CZE analysis of monohydroxylated metabolites of polycyclic aromatic hydrocarbons in milk. Complete resolution of 2-hydroxyfluorenene, 1-hydroxynaphthalene, 2-hydroxynaphthalene, 3-hydroxyphenanthrene, and 9-hydroxyphenanthrene was accomplished in 4 min of electrophoretic run. Limits of detection at the parts-per-billion were obtained with a single solvent (acetonitrile) for metabolite extraction and sample stacking. The small sample volume (1.2 mL) and the conservative usage of chemicals provided a simple and rapid procedure for the simultaneous extraction of numerous samples. Adding 4 min of electrophoretic run per sample, it should be possible to screen ten samples in approximately 1 h of analysis time. The nanoliter extract volume required for sample injection allows for further chromatographic usage and confirmation of positive samples. The unique electrophoretic pattern of the studied metabolites demonstrates the potential for the unambiguous determination of positional isomers with very similar chromatographic behaviors and undistinguishable mass fragmentation patterns.

On the co-elution of benzo[a]pyrene and dibenzo[a,l]pyrene in chromatographic fractions and their unambiguous determination in tobacco extracts via laser-excited time resolved Shpol'skii spectroscopy.

High performance liquid chromatography is widely used for the analysis of polycyclic aromatic hydrocarbons in a wide variety of samples. Of particular concern are benzo[a]pyrene and dibenzo[a,l]pyrene, two of the most toxic polycyclic aromatic hydrocarbons ever tested. Under EPA method 610, these two compounds co-elute with almost identical retention times. Our studies demonstrate the feasibility of directly determining them in a chromatographic fraction without further separation. Their unambiguous determination is based on spectral and lifetime information with a two-step experimental procedure consisting of the evaporation of the chromatographic fraction followed by the dissolution of the residue with microliters of n-octane. With the aid of a 77 K fiber optic probe, limits of detection at the parts-per-billion concentration level (ng mL-1) are obtained from the microliter sample via laser excited time resolved Shpol'skii spectroscopy. This approach is then applied to the analysis of benzo[a]pyrene and dibenzo[a,l]pyrene in tobacco extracts.