A systematic assessment of research trends on polycyclic aromatic hydrocarbons in different environmental compartments using bibliometric parameters.

Polycyclic aromatic hydrocarbons (PAHs) are a large group of diverse hazardous organic compounds that are relatively stable and widely distributed throughout the world's ecosystems due to various anthropogenic activities. They are generally less soluble in water and have a low vapour pressure, but dissolve easily in adipose tissues; and they bioaccumulate into high concentrations in aquatic animals, thereby exerting a variety of hazardous and lethal effects. Despite the plethora of research studies on these pollutants, only few bibliometric reviews on the subject have been documented in the literature. As a result, the present study aimed to assess the research growth on PAHs-related studies across different ecosystems. Science Citation Index-Expanded of Web of Science was explored to obtain the research studies that were conducted between 1991 and 2020, and RStudio was utilized for the data analysis. Annual productivity increased arithmetically over the years, with a 9.2% annual growth rate and a collaboration index of 2.52. Foremost among the trend topics in this field of study include soil, sediments, biodegradation, bioremediation, bioavailability, and source apportionment. China, USA, Spain, France and Germany were the five top-ranked countries in terms of publications and citations over the three decades investigated; however, Korea, Japan, United Kingdom, Germany, and Canada were ranked as the five leading countries in terms of collaboration per published article (MCP ratio). Therefore, efforts to strengthen international collaboration in this field of study especially among the less participating countries and continents are thus encouraged. The findings of this study are expected to provide future direction for the upcoming researchers in identifying the hot spots in this field of study as well as research leaders whom to seek collaboration in their future research plan.

Application of an agitation-assisted dispersed solvent microextraction for analysis of naphthalene and its derivatives from aqueous matrices.

Agitation-assisted dispersive liquid-liquid extraction without a dispersing solvent is lately receiving considerable attention owing to the low to no solvent loss relative to its predecessor, which suffers severe extracting solvent loss. Herein, we report the application of a simple agitation-assisted dispersive liquid-liquid microextraction method, without a disperser solvent, for the extraction of naphthalene and its derivatives from aqueous solutions. Under the optimised conditions, namely, 25 µL 3:1 mixture of dichloroethane and ethylacetate with 20 s agitation, in 2-mL aqueous solutions containing 10% NaCl, the method demonstrated acceptable figures of merit: linearity-R2 ≥ 0.9914 in the concentration range 0.5-50 ng/mL, repeatability (%RSD ≤ 12.9 for n = 15) and limits of detection (0.034-0.081 ng/mL). The recoveries obtained from the spiked dam water sample were also satisfactory (94-103%). These parameters are comparable with those reported in literature, especially for dispersive liquid-liquid microextraction techniques albeit for different analytes. Despite only naphthol being detected in one of the three sampled sites, the method shows considerable promise for routine monitoring of river and dam water quality subject to accuracy validation using certified reference materials.

Comparison of Soxhlet and reflux techniques for extraction and characterisation of potential endocrine-disrupting compounds from solid waste dumpsite soil.

Landfill leachate contains a myriad of hazardous chemicals; as such, they should always be planned and constructed following approved guidelines. A sample of soil collected from the old quarry designated as the official solid waste disposal site in Maseru, the capital city of Lesotho, was exposed to two extraction techniques, namely Soxhlet and reflux extractions, for characterisation of the potential endocrine-disrupting chemicals in the leachate. Principal component analysis was used to compare the extractability of these chemicals between the two methods, and it revealed that phthalates extract better in Soxhlet than in reflux extraction. Other compounds do not show as much difference. Qualitative analysis of the extracts revealed several compounds of environmental health interest, namely anthracene, bis-di-ethylhexyl-phthalates and di-tert-butylphenol. A review of the literature on some of the annotated compounds was explored for the likely sources thereof. It was discovered that most of the compounds that were identified have plastic origins and are listed as potential endocrine disruptors. The identified compounds were similar to those reported elsewhere in the literature.

Solvent-assisted headspace sampling using solid phase microextraction for the analysis of phenols in water.

Headspace analysis is used widely and relies on volatilization of analytes into the headspace above the matrix. We detail the dramatic influence that added solvent can have on headspace analysis of phenols, without the requirement for specialized headspace vials. The use of water-immiscible solvents is key and leads to a 1-3 orders of magnitude enhancement in the volatilization of these analytes and shorter fiber exposure times than are otherwise required.

Bioprospecting of Essential Oil-Bearing Plants: Rapid Screening of Volatile Organic Compounds Using Headspace Bubble-in-Drop Single-Drop Microextraction for Gas Chromatography Analysis.

Essential oils are vital constituents of oil-bearing plants. However, their screening still demands harvesting of the plant for laboratory analysis. We report herein a simple, rapid and robust headspace bubble-in-drop microextraction screening technique (BID-SPME) requiring only small amounts of plant material. The optimised method uses 0.5 g of the crushed plant leaves sample obtained in a 2 mL capped chromatography vial, heated to 55 °C and sampled with 2 µL heptadecane in a Hamilton gastight syringe equilibrated for 15 min exposed to the headspace volume. The method was applied to three plants, Pinus radiata, Tagetes minuta and Artemisia afra, which are known for their essential oil content. The method was able to extract at least 80% of the oil constituents in such abundance that they could be easily annotated using the gas chromatography-mass spectrometry (GC-MS) mass spectral libraries. The major volatile organic compounds (VOCs) detected included tagetone, terpinen-4-ol, ocimenone, caryophyllene, dihydrotagetone, terpinolene and artemisia ketone, just to mention a few, at different concentrations in different plants. Importantly, these annotated VOCs were also reported in other studies in the same and even different plants, extracted using normal steam distillation and importantly those reported in the literature for different extraction techniques.

Bubbles in solvent microextraction: the influence of intentionally introduced bubbles on extraction efficiency.

Significant improvements to microdrop extractions of triazine pesticides are realized by the intentional incorporation of an air bubble into the solvent microdroplet used in this microextraction technique. The increase is attributed partly to greater droplet surface area resulting from the air bubble being incorporated into the solvent droplet as opposed to it sitting thereon and partly to thin film phenomena. The method is useful at nanogram/liter levels (LOD 0.002-0.012 µg/L, LOQ 0.007-0.039 µg/L), is precise (7-12% at 10 µg/L concentration level), and is validated against certified reference materials containing 0.5 and 5.0 µg/L analyte. It tolerates water and fruit juice as matrixes without serious matrix effects. This new development brings a simple, inexpensive, and efficient preconcentration technique to bear which rivals solid phase microextraction methods.

Rapid Screening of Volatile Organic Compounds from Aframomum danielli Seeds Using Headspace Solid Phase Microextraction Coupled to Gas Chromatography Mass Spectrometry.

Volatile organic compounds (VOCs) derived from plants have been used in the fragrance industry since time immemorial. Herein we report on the rapid screening of VOCs from seeds of ripe Aframomum danielli (family, Zingiberaceae) using a polydimethylsiloxane fibre headspace solid phase microextraction coupled to a gas chromatography mass spectrometry (SPME-GC/MS) instrument. Portions of 0.25, 0.35, and 0.50 g of ground sample were weighed and extraction of volatile organic compounds (VOCs) was achieved using a 100 µm polydimethylsiloxane solid phase microextraction (PDMS SPME) fibre, with the equilibrium time of 40 minutes and extraction temperature of 50°C; the following compounds with their respective relative abundances were obtained as the top ten most abundant and annotated ones using NIST, Wiley, and Fragrances Libraries: eucalyptol (58%); ß-pinene (22%); α-pinene (7.5%); α-terpineol (4%), α-terpinyl acetate (2%); α-bergamotene (1%); pinocarveol (0.39%); α-copaene (0.35%); caryophyllene (0.34); and ß-bisabolene (0.31%). These compounds have been reported elsewhere in the literature and listed in the Fragrances Library, incorporated into the Saturn QP2020 GCMS Solution® software used for their analysis.

Hollow-Fibre-Supported Dispersive Liquid-Liquid Microextraction for Determination of Atrazine and Triclosan in Aqueous Samples.

We report the application of the dispersive liquid-liquid microextraction coupled to hollow-fibre membrane-assisted liquid-phase microextraction and its application for extraction of atrazine and triclosan. Under optimum conditions, namely, 25 µL of a 1 : 4 chlorobenzene : ethyl acetate mixture dispersed in 1 mL of aqueous sample, 10% (m/v) NaCl, a magnetic stirrer speed at 600 rpm, and 10 minutes' extraction time with toluene-filled fibre as the acceptor phase, the method demonstrates sufficient figures of merit. These include linearity (R2 ≥ 0.9975), intravial precision (%RSD ≤ 7.6), enrichment factors (127 and 142), limits of detection (0.0081 and 0.0169 µg/mL), and recovery from river water and sewerage (96-101%). The relatively high detection limits are attributed to the flame ionization detector which is less preferred than a mass spectrometer in trace analyses. This is the first report of a homogenous mixture of the dispersed organic solvent in aqueous solutions and its employment in extraction of organic compounds from aqueous solutions. It therefore adds yet another candidate in the pool of miniaturised solvent microextraction techniques.

Highlighting mass spectrometric fragmentation differences and similarities between hydroxycinnamoyl-quinic acids and hydroxycinnamoyl-isocitric acids.

BACKGROUND: Plants contain a myriad of metabolites which exhibit diverse biological activities. However, in-depth analyses of these natural products with current analytical platforms remains an undisputed challenge due to the multidimensional chemo-diversity of these molecules, amplified by both isomerization and conjugation. In this study, we looked at molecules such as hydroxyl-cinnamic acids (HCAs), which are known to exist as positional and geometrical isomers conjugated to different organic acids namely quinic- and isocitric acid. OBJECTIVE: The study aimed at providing a more defined distinction between HCA conjugates from Amaranthus viridis and Moringa oleifera, using mass spectrometry (MS) approaches. METHODS: Here, we used a UHPLC-MS/MS targeted approach to analyze isobaric HCA conjugates extracted from the aforementioned plants. RESULTS: Mass spectrometry results showed similar precursor ions and fragmentation pattern; however, distinct differences were seen with ions at m/z 155 and m/z 111 which are associated with isocitric acid conjugates. CONCLUSION: Our results highlight subtle differences between these two classes of compounds based on the MS fingerprints, enabling confidence differentiation of the compounds. Thus, these findings provide a template reference for accurate and confident annotation of such compounds in other plants.

Picogram-level quantification of some growth hormones in bovine urine using mixed-solvent bubble-in-drop single drop micro-extraction.

Growth hormones are important biologically active compounds. However, they can cause deleterious effects if not used with care and their use in farmed animals is banned in the European Union. This study presents the development and application of a mixed-solvent "bubble-in-drop single drop micro-extraction" (BID-SDME) method for enrichment of stilbene hormones in bovine urine samples. The hormones are quantified using GC-MS showing good linearity with the coefficient of determination (R(2)) of 0.999 and 0.999 for hexestrol and diethylstilbestrol, respectively, in the concentration range 0.05-10 ng mL(-1). Excellent precision (RSD<10%) and accuracy (using a bovine urine certified reference material) were obtained. The observed detection capability (CCα, or LOD) values were 0.01 ng mL(-1) (hexestrol), 0.03 ng mL(-1) (cis-diethylstilbestrol) and 0.02 ng mL(-1) (trans-diethylstilbestrol), respectively, while the decision limit (CCß, or LOQ) values were 0.03 ng mL(-1), 0.08 ng mL(-1) and 0.07 ng mL(-1), which are comparable to or better than those reported in literature. Importantly, sample handling is significantly simplified by our method and enrichment values are greatly enhanced. The results show that a 3:1 chloroform/toluene mixture gave the highest extraction efficiency with a drop-bubble ratio of 2:1. We highlight the importance of solvent density on the success of the BID-SDME method.

Rapid detection of atrazine and metolachlor in farm soils: gas chromatography-mass spectrometry-based analysis using the bubble-in-drop single drop microextraction enrichment method.

Tracking of metolachlor and atrazine herbicides in agricultural soils, from spraying through to harvest, was conducted using our recently reported "bubble-in-drop single-drop microextraction" method. The method showed good linearity (R(2) = 0.999 and 0.999) in the concentration range of 0.01-1.0 ng/mL with LOD values of 0.01 and 0.02 ng/mL for atrazine and metolachlor, respectively. Sonication methods were poor at releasing these herbicides from the soil matrixes, while hot water extraction readily liberated them, providing an efficient accessible alternative to sonication techniques. Good recoveries of 97% and 105% were shown for atrazine and metolachlor, respectively, from the soil. The spiking protocol was also investigated, resulting in a traceless spiking method. We demonstrate a very sensitive technique by which to assess, for example, the length of residence of pesticides in given soils and thus risk of exposure.