Biochar nanosphere-functionalized carbon fibers for in-tube solid-phase microextraction of polycyclic aromatic hydrocarbons in environmental water followed by liquid chromatography and diode array detection.

In order to improve the extraction ability of carbon fibers (CFs) for microextraction of polycyclic aromatic hydrocarbons (PAHs), biochar nanospheres derived from glucose were in-situ grown onto the surface of CFs via hydrothermal synthesis. The surface morphology and elemental composition of biochar nanospheres-CFs were investigated by scanning electron microscopy and X-ray photoelectron spectroscopy. Thereafter, the biochar nanosphere-CFs were pulled into the polyetheretherketone tube for solid-phase microextraction, and the tube was combined with high-performance liquid chromatography-diode array detector to online detect PAHs. With the help of π-stacking, hydrophobic, and hydrophilic effect of biochar nanospheres, the extraction efficiency of CFs was greatly enhanced (enrichment factor increased by 293% compared with  the original). The conditions affecting the analytical performance (sampling volume, sampling rate, methanol content, and desorption time) were investigated. Under the optimal conditions, an online analytical method for microextraction and determination of several PAHs was developed, and satisfactory results were achieved. The limits of detection were 0.003-0.010 ng mL-1 owing to high enrichment effect (2973-3600), linearity ranged from  0.010-15.0 ng mL-1, and relative standard deviations were 0.4%-1.6% (intra-day) and 2.4%-4.4% (inter-day), respectively. The method was applied to analyze environmental water samples (rain water, snow water, and river water), and spiked recoveries within 80.0%-119% were obtained.

[Recent advance of new sample preparation materials in the analysis and detection of environmental pollutants].

To successfully analyze complex samples and detect trace targets, sample pretreatment is essential. Efficient sample pretreatment techniques can remove or reduce interference from the sample matrix. It can also enrich analytes, thereby improving analytical accuracy and sensitivity. In recent years, various sample preparation techniques, including SPE, magnetic dispersion SPE, pipette tip SPE, stir bar extraction, fiber SPME, and in-tube SPME, have received increasing attention in environmental analysis and monitoring. The extraction efficiency mainly depends on the type of adsorbent material. Therefore, the development of efficient adsorbents is a crucial step toward sample preparation. This review summarizes and discusses the research advances in extraction materials over recent years. These extraction materials contain inorganic adsorbents, organic adsorbents, and inorganic-organic hybrid materials such as graphene, graphene oxide, carbon nanotubes, inorganic aerogels, organic aerogels, triazinyl-functionalized materials, triazine-based polymers, molecularly imprinted polymers, covalent organic frameworks, metal-organic frameworks, and their derivatives. These materials have been applied to extract different types of pollutants, including metal ions, polycyclic aromatic hydrocarbons, plasticizers, alkanes, phenols, chlorophenols, chlorobenzenes, polybrominated diphenyl ethers, perfluorosulfonic acids, perfluorocarboxylic acids, estrogens, drug residues, and pesticide residues, from environmental samples (such as water and soil samples). These sample preparation materials possess high surface areas, numerous adsorption sites, and allow extraction via various mechanisms, such as π-π, electrostatic, hydrophobic, and hydrophilic interactions, as well as hydrogen and halogen bond formation. Various sample pretreatment techniques based on these extraction materials have been combined with various detection methods, including chromatography, mass spectrometry, atomic absorption spectroscopy, fluorescence spectroscopy, and ion mobility spectroscopy, and have been extensively used for the determination of environmental pollutants. The existing challenges associated with the development of sample preparation techniques are proposed, and prospects for such extraction materials in environmental analysis and monitoring are discussed. Major trends in the field, including the development of efficient extraction materials with high enrichment ability, good selectivity, excellent thermal stability, and chemical stability, are discussed. Green sample pretreatment materials, environmentally friendly synthesis methods, and green sample pretreatment methods are also explored. Rapid sample pretreatment methods that can be conducted within minutes or seconds are of significant interest. Further, online sample pretreatment and automatic analysis methods have attracted increasing attention. Besides, real-time analysis and in situ detection have been important development directions, and are expected to be widely applicable in environmental analysis, biological detection, and other fields. Modern synthesis technology should be introduced to synthesize specific extraction materials. Controllable preparation methods for extraction materials, such as the in situ growth or in situ preparation of extraction coatings, will acquire importance in coming years. It will also be important to adopt high-performance materials from other fields for sample pretreatment. Organic-inorganic hybrid extraction materials can combine the advantages both organic materials and inorganic materials, and mutually compensate for any disadvantages. Extraction materials doped with nanomaterials are also promising. Although existing sample pretreatment techniques are relatively efficient, it is still imperative to develop novel sample preparation methods.

Dendritic mesoporous silica nanospheres@porous carbon for in-tube solid-phase microextraction to detect polycyclic aromatic hydrocarbons in tea beverages.

It is pretty necessary to detect effectively polycyclic aromatic hydrocarbons (PAHs, including naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, and pyrene) in foods due to their widespread distribution, trace concentration, and harmful risk to humans beings. Herein, dendritic mesoporous silica nanospheres@porous carbon was developed for solid-phase microextraction of PAHs. Firstly, three-dimensional dendritic mesoporous silica nanospheres (DMSNs) with high surface area and large pore volume were synthesized via an oil-water biphase stratification approach, then porous carbon was further prepared by utilizing DMSNs and asphalt as the template and carbon source, respectively. A core-shell DMSNs@porous carbon material was successfully developed and characterized by Raman spectroscopy, elemental analysis, Brunauer-Emmett-Teller test, scanning electron microscopy, and transmission electron microscopy. DMSNs@porous carbon was proved to be a potential extraction material based on large surface area (442 m2 g-1), suitable pore sizes (about 45 nm), and high carbon content (17.36%). Subsequently, it was developed as an extraction coating and applied to online in-tube solid-phase microextraction of PAHs from tea beverages. Through coupling with high-performance liquid chromatography, an analytical method was established under optimal extraction conditions and desorption, low limits of detection (0.010-0.070 µg L-1), wide linear ranges in 0.033-10 µg L-1, and excellent correlation coefficients (most of the r reach 0.999) were received. The relative standard deviations (RSDs, n = 3) of intra-day test and inter-day test were obtained corresponding to the ranges of 0.1-2.5% and 1.0-4.1%. Finally, the method was used for detecting trace PAHs in different tea beverages from the market.

Recent Advances of Triazine-Based Materials for Adsorbent Based Extraction Techniques.

This review mainly focused on the synthesis and properties of triazine-based materials as well as the state-of-the-art development of these materials in adsorption-based extraction techniques in the past 5 years, such as solid-phase extraction, magnetic solid-phase extraction, solid-phase microextraction and stir bar sorptive extraction, and the detection of various pollutants, including metal ions, drugs, estrogens, nitroaromatics, pesticides, phenols, polycyclic aromatic hydrocarbons and parabens. In the triazine-functionalized composites, triazine-based polymers and covalent triazine frameworks have been developed as the adsorbents with potential for environmental pollutants, mainly relying on the large surface area and the affinity of triazinyl groups with the targets. Triazine-based adsorbents have satisfactory sensitivity and selectivity towards different types of analytes, attributed from various mechanisms including π-π, electrostatics, hydrogen bonds, and hydrophobic and hydrophilic effects. The prospects of the materials for adsorption-based extraction were also presented, which can offer an outlook for the further development and applications.

Recent advances in micro- and nanomaterial-based adsorbents for pipette-tip solid-phase extraction.

There are a lot of review papers of sample pretreatment, but the comprehensive review on pipette-tip solid-phase extraction (PT-SPE) is lacking. This review (133 references) is mainly devoted to the development of different types of micro- and nanosorbent-based PT-SPE, including silica materials, carbon materials, organic polymers, molecularly imprinted polymers, and metal-organic frameworks. Each section mainly introduces and discusses the preparation methods, advantages and limitations of adsorbents, and their applications to environmental, biological, and food samples. This review also demonstrates the advantages of PT-SPE like convenience, speed, less organic solvent, and low cost. Finally, the future application and development trend of PT-SPE are prospected.

Polyaniline/titanium dioxide nanorods functionalized carbon fibers for in-tube solid-phase microextraction of phthalate esters prior to high performance liquid chromatography-diode array detection.

To improve extraction performance of carbon fibers (CFs) towards phthalate esters (PAEs), titanium dioxide (TiO2) nanorods array was in-situ grown on the surface of CFs, then polyaniline (PANI) was used to modify it. PANI/TiO2 nanorods-CFs were placed into a polyetheretherketone tube for solid-phase microextraction (SPME). Combining the tube to high performance liquid chromatography (HPLC), it was evaluated and displayed good extraction performance for several PAEs. Compared with bare CFs, TiO2 nanorods and PANI, PANI/TiO2 nanorods presented best performance, attributed to the unique advantages between high surface area of TiO2 nanorods and multiple adsorption interactions (like π-π stacking, hydrogen bond) of PANI. After the optimization of the important factors (sampling volume, sampling rate, sample pH, concentrations of organic solvent and salt in sample, and desorption time), the online in-tube SPME-HPLC method was established. It provided low limits of detection (0.01-0.05 µg L-1) and wide linear ranges (0.03-30, 0.10-30, 0.17-30 µg L-1) with correlation coefficients larger than 0.9991. The relative standard deviations (n=6) between intra-day and inter-day tests were in the ranges of 3.5-10.3% and 4.7-13.9%, respectively. The method was successfully used to determine seven PAEs in real water samples. Besides of satisfactory durability, the material also exhibited superior extraction performance than some materials.

Poly(ionic liquid)-hybridized silica aerogel for solid-phase microextraction of polycyclic aromatic hydrocarbons prior to gas chromatography-flame ionization detection.

Using poly(ionic liquid) (PIL) and tetraethyl orthosilicate (TEOS) as the co-precursors, PIL-hybridized silica aerogel was prepared via sol-gel method for solid-phase microextraction (SPME). The ratio between PIL and TEOS was regulated to achieve the best extraction effect. The aerogel was coated onto the surface of stainless steel wire to get SPME fiber. Coupled to gas chromatography-flame ionization detector (GC-FID), the fiber was separately evaluated by the determination of alkanes, polycyclic aromatic hydrocarbons (PAHs), as well as BTEX (benzene, toluene, ethylbenzene, and xylenes) in immersion mode. The extraction performance of PAHs was attributed to π stacking and hydrophobic effect. After optimization of main extraction and desorption conditions, the SPME-GC-FID method was established towards eight PAHs, and it provided low detection limits (0.005 µg L-1, 0.010 µg L-1) and wide linear ranges (0.016-20.00 µg L-1, 0.033-20.00 µg L-1) with good linear coefficients (0.9991-0.9998). The method was applied to detect trace PAHs in real water samples, with relative recoveries of 86.2-119.2%. Furthermore, PIL-hybridized silica aerogel exhibits some superiorities like higher sensitivity, shorter extraction time, and better repeatability over other extraction coatings. The present work not only extends the range of aerogel materials but also promoted their further applications in sample preparation. Graphical abstract.

Triazine-based covalent porous organic polymer for the online in-tube solid-phase microextraction of polycyclic aromatic hydrocarbons prior to high-performance liquid chromatography-diode array detection.

A triazine-based covalent organic porous polymer (COP) was synthesized from the monomers 1,3,5-triphenylbenzene and tricyanogen chloride via the Friedel-Crafts reaction and characterized in detail using Brunauer-Emmett-Teller analysis, X-ray photoelectron spectroscopy, elemental analysis, and scanning electron microscopy, which confirmed that the COP had a rough surface and suitable extraction site. It was then employed in in-tube solid-phase microextraction combined with a high-performance liquid chromatography-diode array detector. The COP adsorbent was evaluated with different types of analyte, including estrogens, polycyclic aromatic hydrocarbons (PAHs), and plasticizers. The COP produced its best performance with PAHs. In order to obtain the highest extraction efficiency for PAHs, the main influential factors were optimized. Furthermore, a sensitive analytical method was established with the limits of detection of 0.004-0.010 µg L-1, high enrichment factor of 1110-2763, and wide linear ranges (0.013-20.0 µg L-1, 0.016-20.0 µg L-1 and 0.033-20.0 µg L-1). The relative standard deviation in intra-day and inter-day tests was also controlled to be within 0.3-3.1%. The proposed method was employed in the online detection of trace PAHs in real water samples, with satisfactory results obtained.

Application of biocharcoal aerogel sorbent for solid-phase microextraction of polycyclic aromatic hydrocarbons in water samples.

A facile method was introduced for preparing a biocharcoal aerogel, which was derived from pomelo peel as the only raw material. The inner spongy layer of pomelo peel was freeze-dried for maintaining three-dimensional structure and then carbonized under high temperature and oxygen-limited conditions. The morphological structure and graphitization degree of biocharcoal aerogel were characterized using a scanning electron microscope and Raman spectrum. After sifting and grinding, the biocharcoal aerogel as an adsorbent was coated onto the surface of stainless steel wires. Through placing the wires into a polyetheretherketone tube, the in-tube solid-phase microextraction device was obtained. Coupled with high-performance liquid chromatography, it exhibited good extraction performance for polycyclic aromatic hydrocarbons, then an online analytical method was established with low limits of detection (0.005-0.050 ng/mL), wide linear ranges (0.017-15 ng/mL) with superior correlation coefficients higher than 0.9990, high enrichment factors (1128-3425), and acceptable intra- and inter-day repeatabilities (relative standard deviations ≤ 6.7%, n = 3). The method was applied to detect polycyclic aromatic hydrocarbons in bottled water samples, environmental water samples, and soft drinks with satisfactory recoveries (83.3-120.9%). This research not only developed a new carbon aerogel but also evaluated its adsorption performance in sample preparation.

Carbon nanotubes functionalized mesoporous silica for in-tube solid-phase microextraction of polycyclic aromatic hydrocarbons.

A mesoporous silica was functionalized by carbon nanotubes to enhance the extraction performance. The mesoporous material was coated on stainless steel wires, and three wires were inserted inside of a polyetheretherketone tube for in-tube solid-phase microextraction. The tube was coupled to high-performance liquid chromatography with diode array detection to obtain online analytical system, then its extraction performance was evaluated using eight polycyclic aromatic hydrocarbons as the targets. In order to good sensitivity and accuracy, four conditions were optimized such as sampling volume, sampling rate, methanol content in the sample, and desorption time. Under the optimum conditions, an online analytical method was established and exhibited low limits of detection from 0.005 to 0.050 µg/L, wide linear range of 0.016-20.00 µg/L with acceptable correlation coefficients in 0.9921-0.9999, as well as large enrichment factors in the range of 311-2412. The method was successfully applied to determine trace polycyclic aromatic hydrocarbons in some real water samples including, two kinds of bottled water, tap water, and river water, a few polycyclic aromatic hydrocarbons were detected but none quantified in these samples.

Triazine-based organic polymers@SiO2 nanospheres for sensitive solid-phase microextraction of polycyclic aromatic hydrocarbons.

Triazine-based organic polymers@SiO2 nanospheres were prepared and applied as an extraction coating onto stainless steel wires and the wires were filled into polyetheretherketone tube for in-tube solid-phase microextraction. Taking polycyclic aromatic hydrocarbons as targets, main factors affecting extraction performance of the tube were investigated through coupling to high performance liquid chromatography. Under the optimum conditions, an online analytical method for polycyclic aromatic hydrocarbons was established with large linear ranges (0.010-20 µg/L), low limits of detection (0.003-0.010 µg/L), high enrichment factors (533-2954), and good repeatability (relative standard deviations <1.7% for intraday test, <5.0% for interday test). The analysis method was successfully applied to the detection of trace targets in real water samples and the relative recoveries ranged from 82.9 to 119.9%, which demonstrated the applicability of extraction tube in sample preparation.

An ionic-liquid-modified melamine-formaldehyde aerogel for in-tube solid-phase microextraction of estrogens followed by high performance liquid chromatography with diode array detection.

A combination between an ionic liquid and melamine-formaldehyde aerogel on the carbon fibers was developed for in-tube solid-phase microextraction of estrogens with high efficiency. The sorbent has a high enrichment capability for several estrogens. Scanning electron microscopy showed that the aerogel on the carbon fibers has a porous three-dimensional network structure. Several important parameters such as sampling volume, sampling rate, the concentration of organic solvent in sample, pH value of sample as well as desorption time were optimized towards estrogen targets. Comparing with melamine-formaldehyde aerogel coating, the coating gave higher extraction efficiency. Comparing with melamine-formaldehyde aerogel coating, the new coating displays higher extraction efficiency. An online analytical method of estrogens was established, by the combination between in-tube solid-phase microextraction and high performance liquid chromatography with diode array detector. Analytical figures of merit include low limits of detection (<0.20 µg L-1), wide linearity (0.15-20 µg L-1), high enrichment factors (1028-1256), good extraction repeatability (RSDs<2.5%) and satisfactory preparation repeatability (RSDs<10.5%). The method was applied to the determination of trace estrogen targets in plastic bottle, tap water and surface water. Graphical abstractSchematic representation of online combination between in-tube solid-phase microextraction and high performance liquid chromatography, based on an ionic liquid (IL)-modified melamine-formaldehyde (MF) aerogel coating on carbon fibers (CFs) in a polyether-etherketone (PEEK) tube.

Carbonized silk fibers for in-tube solid-phase microextraction to detect polycyclic aromatic hydrocarbons in water samples.

Silk fibers were carbonized to develop a biomass carbon material as an adsorbent for solid-phase microextraction. The surface structure of the carbonized silk fibers was characterized by scanning electron microscopy, and the graphitization degree was determined by Raman spectrometry. After carbonization under high temperature, the orderliness and structural regularity of carbon atoms on silk fibers were promoted. Extraction tube packed with carbonized silk fibers was prepared for in-tube solid-phase microextraction. Coupled with high performance liquid chromatography, it exhibited good extraction performance for hydrophobic polycyclic aromatic hydrocarbons. Main parameters including sampling volume, sampling rate, methanol content in sample, and desorption time were systematically investigated. Under the optimum conditions, the analysis method was established and it exhibited wide linear range (0.016-20 µg/L) with good linearity (correlation coefficient ≥ 0.9947), low limits of detection (0.005-0.050 µg/L), and high enrichment factors (1189-2775). Relative standard deviations (n = 3) for intraday (≤3.3%) and interday (≤9.6%) tests indicated that the extraction material had satisfactory repeatability. Finally, the analytical method was successfully applied to detect trace polycyclic aromatic hydrocarbons in real water samples, demonstrating its satisfactory practicability.

Nano-MoO3 for highly selective enrichment of polycyclic aromatic hydrocarbons in in-tube solid-phase microextraction.

Nano-molybdenum trioxide was prepared from nano-molybdenum disulfide by simple firing in muffle furnace. Nano-molybdenum trioxide was used as the extraction coating on the stainless steel wire. Four wires were filled in a polyetheretherketone tube to get an extraction tube. The tube was connected to the six-port valve of a high performance liquid chromatograph, and the online analysis system was constructed. Extraction selectivity of the tube for different types of compounds, including polycyclic aromatic hydrocarbons, plasticizers, estrogens, anilines and neonicotinoids, was studied. Good enrichment ability for polycyclic aromatic hydrocarbons, but the extraction efficiency of others was not satisfactory. Using eight polycyclic aromatic hydrocarbons as the targets, an analytical method was established after optimizing main factors such as sampling volume, sampling rate, methanol content, and desorption time. The established method exhibited wide linear range to 0.016-20.00 µg/L and low limits of detection to 0.005 µg/L, and the enrichment factors can be up to 2443. The method was applied to the detection of trace polycyclic aromatic hydrocarbons in tap water and river water, and a good recovery was obtained. The tube showed good durability and chemical stability, and it still remained good extraction effect after more than 140 run.

Bare polyprolylene hollow fiber as extractive phase for in-tube solid-phase microextraction to determine estrogens in water samples.

Polypropylene hollow fibers as the adsorbent were directly filled into a polyetheretherketone tube for in-tube solid-phase microextraction. The surface properties of hollow fibers were characterized by a scanning electron microscope. Combined with high performance liquid chromatography, the extraction tube showed good extraction performance for five environmental estrogen hormones. To achieve high analytical sensitivity, four important factors containing sampling volume, sampling rate, content of organic solvent in sample, and desorption time were investigated. Under the optimum conditions, an online analysis method was established with wide linear range (0.03-20 µg/L), good correlation coefficients (≥0.9998), low limits of detection (0.01-0.05 µg/L), low limits of quantitation (0.03-0.16 µg/L), and high enrichment factors (1087-2738). Relative standard deviations (n = 3) for intraday (≤3.6%) and interday (≤5.1%) tests proved the stable extraction performance of the material. Durability and chemical stability of the extraction tube were also investigated, relative standard deviations of all analytes were less than 5.8% (n = 3), demonstrating the satisfactory stability. Finally, the method was successfully applied to detect estrogens in real samples.

Carbonized cotton fibers via a facile method for highly sensitive solid-phase microextraction of polycyclic aromatic hydrocarbons.

Cotton fiber is an environmentally friendly and natural material with a certain extraction capacity, while its enrichment ability is poor. In order to improve the extraction efficiency of cotton fibers, it was carbonized to form a layer of amorphous carbon as the sorbent by a simple carbonization method. Carbonized cotton fibers were filled into a polyetheretherketone tube for in-tube solid-phase microextraction. The carbonization time was investigated to obtain high extraction efficiency. Coupled to high-performance liquid chromatography, the extraction tube was evaluated with polycyclic aromatic hydrocarbons, estrogens and phthalates, and it exhibited best extraction efficiency for polycyclic aromatic hydrocarbons. Under the optimum conditions, an online analysis method for several polycyclic aromatic hydrocarbons was established with large linear ranges (0.016-0.20 µg/L), low limits of detection (0.005-0.020 µg/L), and high enrichment factors (948-2874). Analysis method was successfully applied to the detection of targets in the real samples and shown satisfactory durability and chemical stability. Moreover, the relative recoveries ranged from 82 to 119.2%, which demonstrated the applicability of carbonized cotton fibers in sample preparation. Compared with other reported methods, the proposed method provided shorter extraction time, higher enrichment factors, comparable limits of detection, and recoveries.

Polydopamine-coated cotton fibers as the adsorbent for in-tube solid-phase microextraction.

Polydopamine was coated onto cotton fibers as the adsorbent to improve the extraction efficiency. Polydopamine-coated cotton fibers were placed into a polyetheretherketone tube for in-tube solid-phase microextraction. To develop an online analysis system, the extraction tube was connected with high-performance liquid chromatography. The tube was evaluated with five estrogenic analytes, and the extraction and desorption conditions were optimized to get high extraction efficiency. Under the optimum conditions, the enrichment factors of five analytes were 143-1745. An online analysis method was established, it had large linear ranges (0.10-40 and 0.16-40 µg/L), low limits of detection (0.03, 0.05 µg/L) and satisfactory repeatability (≤3.2%). The analysis method was applied to detect targets in the real samples like as hot water in new plastic cup and tap water. The relative recoveries spiked at 1 and 5 µg/L in these samples were investigated and the results were in the range of 83.7-109%.

Melamine-formaldehyde aerogel functionalized with polydopamine as in-tube solid-phase microextraction coating for the determination of phthalate esters.

To improve the extraction performance and stability of the melamine-formaldehyde (MF) aerogel, a melamine-formaldehyde aerogel functionalized with polydopamine (PDA/MF) has been prepared on the carbon fibers (CFs), and it was used as a solid-phase microextraction (SPME) material via packing into a polyetheretherketone (PEEK). The morphological structure of this SPME material was characterized by scanning electron microscope, and its performance was evaluated via coupled it with a high performance liquid chromatography (HPLC). The material exhibited good extraction performance for seven phthalate esters (PAEs). Compared with CFs and MF aerogel coated-CFs, PDA/MF aerogel coated-CFs have the best extraction efficiency for PAEs. Several influence factors were investigated in detail, including extraction volume, sampling flow rate, methanol content in sample and desorption time. Under the optimal conditions, an online in-tube SPME-HPLC analytical method was established with low limits of detection (LODs) (0.02-0.05 µg L-1) and limits of quantification (LOQs) (0.07-0.16 µg L-1), wide linear ranges (0.07-30 µg L-1) and superior correlation coefficients (0.9954-0.9986). The relative standard deviations (RSDs, n = 3) of the method were in the ranges of 1.0-4.9% (intra-day) and 1.6-7.3% (inter-day), respectively. RSDs of preparation repeatability among three tubes ranged from 6.6% to 12.1%. The analysis method was applied to the detection of seven PAEs from three real samples. The proposed extraction material had good durability and chemical stability, and it also exhibited a superior extraction performance than other SPME materials, including lower LODs, higher enrichment factors and shorter extraction time.

A green extraction material - natural cotton fiber for in-tube solid-phase microextraction.

Natural cotton fiber was applied as a green extraction material for in-tube solid-phase microextraction. Cotton fibers were characterized by scanning electron microscope. A bundle of cotton fibers (685 mg, 20 cm) was directly packed into a polyetheretherketone tube (i.d. 0.75 mm) to get the extraction device. It was connected into high performance liquid chromatography, building an online extraction and dectection system. Through the online analysis system, several polycyclic aromatic hydrocarbons were used as the targets to evaluate the extraction performace of the device. In order to get high extraction efficiency and sensitivity, the extraction and desorption conditions were optimized. Under the optimum conditions, the sensitive analysis method was established, and provided low limits of detection of 0.02 and 0.05 µg/L, good linearity ranges of 0.06-15 and 0.16-15 µg/L, as well as high enrichment factors of 176-1868. The method was applied to the online determination of trace polycyclic aromatic hydrocarbons in snow water and river water, and the relative recoveries corresponding to 2 and 5 µg/L were in the range of 80-116%. The repeatability of extraction and preparation of the device was investigated and the relative standard deviations (n = 3) were less than 3.6 and 5.2%.

Diamond nanoparticles coating for in-tube solid-phase microextraction to detect polycyclic aromatic hydrocarbons.

Diamond nanoparticles were coated onto stainless steel wires as a extraction material, then it was filled into a poly(ether ether ketone) tube for in-tube solid-phase microextraction. Coupled with high-performance liquid chromatography, the extraction tube was evaluated with different types of analytes including polycyclic aromatic hydrocarbons, estrogens and plasticizers. As the coating, diamond nanoparticles exhibited greater extraction capacity for hydrophobic analytes. Several polycyclic aromatic hydrocarbons were used as model analytes, four main extraction and desorption factors were optimized, including sampling volume, sampling rate, methanol content in sample and desorption time. A sensitive analysis method was established with wide linear range (0.016-20 µg/L), good correlation coefficients (0.9991-0.9997), low limits of detection (0.005-0.020 µg/L), low limits of quantitation (0.016-0.070 µg/L) and high enrichment factors (305-2396). Relative standard deviations for intra- and interday were less than 2.4% (n = 3) and 8.4% (n = 3), respectively. Durability and chemical stability were satisfactory with relative standard deviations less than 7.9% (n = 3). Finally, the method has been successfully applied to the detection of polycyclic aromatic hydrocarbons in real samples.