Analysis of PAHs in Water and Fruit Juice Samples by DLLME Combined with LC-Fluorescence Detection

A simple, rapid and efficient method termed dispersive liquid–liquid microextraction combined with liquid chromatography-fluorescence detection, has been developed for the extraction and determination of polycyclic aromatic hydrocarbons (PAHs) in water and fruit juice samples. Parameters such as the kind and volume of extraction solvent and dispersive solvent, extraction time and salt effect were optimized. Under optimum conditions, the enrichment factors ranged from 296 to 462. The linear range was 0.01–100 μg L^?1 and limits of detection were 0.001–0.01 μg L^?1. The relative standard deviations (RSDs, for 5 μg L^?1 of PAHs) varied from 1.0 to 11.5% (n = 3). The relative recoveries of PAHs from tap, river, well and sea water samples at spiking level of 5 μg L^?1 were 82.6–117.1, 74.9–113.9, 77.0–122.4 and 86.1–119.3%, respectively. The relative recoveries of PAHs from grape and apple juice samples at spiking levels of 2.5 and 5 μg L^?1 were 80.8–114.7 and 88.9–123.0%, respectively. It is concluded that the proposed method can be successfully applied for determination of PAHs in water and fruit juice samples.     

Electrochemical DNA biosensor for polycyclic aromatic hydrocarbon detection

Four DNA electrochemical biosensors using four types of DNA (calf thymus ssDNA, calf thymus dsDNA, salmon testis ssDNA and salmon testis dsDNA) were constructed using graphite screen printed electrodes. These biosensors were exploited as analytical tool to detect polycyclic aromatic hydrocarbons-DNA interactions using benzo(a)anthracene and phenantrene as model analytes, the guanine oxidation peak variation being the signal revealing the interaction between PAHs and immobilized DNA. The salmon testis ssDNA biosensor resulted as the most promising device and was further evaluated for benzo(a)anthracene, fluorene, indeno(1,2,3-cd)pyrene, anthracene, and phenanthrene in 5–40 ng mL^?1 solutions, and for benzo(a)pyrene (5–50 ng mL^?1). A concentration dependent variation of the DNA guanine oxidation peak was observed for all compounds. The effect of benzo(a)pyrene ultraviolet (UV) activation on the benzo(a)pyrene (BaP)-DNA interaction was evaluated at concentration levels of 20 and 50 ng mL^?1, and a 3.5- and 2.7-fold increases of the guanine oxidation peak was measured respectively. The salmon testis ssDNA biosensor was examined with PAHs contaminated samples of Mytilus galloprovincialis. Upon UV irradiation of three sample extracts exceeding the BaP maximum level, a positive variation of the DNA guanine oxidation was obtained. An average 2.4-fold increase of the guanine oxidation peak was detected demonstrating that the sensor can be used to detect toxic degradation products of PAHs.     

Simple Determination of 4-Methylimidazole in Soft Drinks by Headspace SPME GC–MS

A simple method to detect 4-methylimidazole in soft drinks is described. This method is based on headspace solid-phase micro-extraction and gas chromatography–mass spectrometry (HS-SPME GC–MS). The HS-SPME parameters (selection of fiber, extraction temperature, heating time, and pH) were optimized and selected. Under the established condition, the detection and the quantification limit were 1.9 and 6.0 μg L^?1 using 4 mL of the liquid sample, respectively. The relative standard deviation for five independent determinations at 100.0 and 500.0 μg L^?1 was less than 8 %. The calibration curve was y = 0.6027x–0.0033 with a linearity of r ² = 0.997. Using the proposed method, the levels of 4-MEI were detected in a range from 94.0 to 324.8 μg L^?1. The comparison of liquid chromatography tandem mass spectrometry (LC–MS/MS) with the proposed method was performed and the agreement with LC–MS/MS for all samples was acceptable.     

An automated headspace solid-phase microextraction followed by gas chromatography–mass spectrometry method to determine macrocyclic musk fragrances in wastewater samples

A fully automated method has been developed for determining eight macrocyclic musk fragrances in wastewater samples. The method is based on headspace solid-phase microextraction (HS-SPME) followed by gas chromatography–mass spectrometry (GC-MS). Five different fibres (PDMS 7 μm, PDMS 30 μm, PDMS 100 μm, PDMS/DVB 65 μm and PA 85 μm) were tested. The best conditions were achieved when a PDMS/DVB 65 μm fibre was exposed for 45 min in the headspace of 10 mL water samples at 100 °C. Method detection limits were found in the low ng L^?1 range between 0.75 and 5 ng L^?1 depending on the target analytes. Moreover, under optimized conditions, the method gave good levels of intra-day and inter-day repeatabilities in wastewater samples with relative standard deviations (n?=?5, 1,000 ng L^?1) less than 9 and 14 %, respectively. The applicability of the method was tested with influent and effluent urban wastewater samples from different wastewater treatment plants (WWTPs). The analysis of influent urban wastewater revealed the presence of most of the target macrocyclic musks with, most notably, the maximum concentration of ambrettolide being obtained in WWTP A (4.36 μg L^?1) and WWTP B (12.29 μg L^?1), respectively. The analysis of effluent urban wastewater showed a decrease in target analyte concentrations, with exaltone and ambrettolide being the most abundant compounds with concentrations varying between below method quantification limit (<MQL) and 2.46 μg L^?1.

Custom-Made C18 Column for Simultaneous Determination of Endocrine Disrupting Substances in Water by Diode-Array and Fluorescence Detectors

A C₁₈ stationary phase was synthesized for a custom-made HPLC column. When compared to a commercial C₁₈ column, better chromatographic performances were obtained. This column was successfully applied for simultaneous determination of p,p′-DDT, o,p′-DDT, benzo(a)anthracene, benzo(b)fluoranthene, and benzo(a)pyrene in waters by high performance liquid chromatography coupled with dual detectors (diode array and fluorescence detectors) combined with solid phase extraction. Low method detection limits were obtained, i.e., p,p′-DDT: 0.5 µg L^?1, o,p′-DDT: 1 µg L^?1, benzo(a)anthracene: 2.5 ng L^?1, benzo(b)fluoranthene: 5 ng L^?1, and benzo(a)pyrene: 2.5 ng L^?1. High recoveries that ranged from 82 to 94% were obtained for all compounds.     

A Screening Method for Polycyclic Aromatic Hydrocarbons Determination in Sediments by Headspace SPME with GC–FID

A screening method for polycyclic aromatic hydrocarbons (PAHs) determination in sediment using headspace solid phase microextraction (HS-SPME) with gas chromatography–flame ionization detection was developed. In order to obtain the convenient experimental conditions for HS-SPME extraction an experimental design with two steps was done. 0.2 g of sediment and 85 µm polyacrylate fibre, 80 °C and 120 min were the chosen extractions conditions. The limit of detection (LOD) was from 0.8 ng g⁻¹ (fluoranthene) to 8 ng g⁻¹ (chrysene). The relative standard deviation (RSD) was less than 7.0%. Determination of PAHs in NRC–CNRC–HS–3B reference marine sediment showed good agreement with the certified values. The method was applied in the analysis of ten river and estuary surface sediments from Gipuzkoa (North Spain). PAHs total concentration ranged from 400 to 5,500 ng g⁻¹.

     

Determination of N-methylcarbamate pesticides using flow injection with photoinduced chemiluminescence detection

A sensitive, economic, rapid and simple method for the determination of four N-methylcarbamate pesticides: methomyl (2.0–80 μg L^?1), aldicarb (5.0–50 μg L^?1), butocarboxim (2.0–60 μg L^?1) and oxamyl (2.0–60 μg L^?1); is reported. It relies on the coupling of photoinduced chemiluminescence (PICL) detection with flow injection (FI) methodology. The automation of FI together with the use of light as a reagent decreased the environmental impact of the analysis. The proposed method was based on the oxidation of these pesticides, previously irradiated on-line with UV light, with cerium(IV), using quinine as a sensitiser. Limits of detection below the legal limits (100 ng L^?1) established by the European Union for drinking waters were obtained without the need of preconcentration steps. A good inter-day reproducibility (1.6–6.4%, n = 5), repeatability (rsd = 2.7 %, n = 25) and high throughput (123 h^?1) were achieved. The method was successfully applied to the determination of methomyl in natural waters with mean recoveries ranging from 90% to 98%.     

Preparation of a Robust and Sensitive Gold-Coated Fiber for Solid-Phase Microextraction of Polycyclic Aromatic Hydrocarbons in Environmental Waters

A robust gold-coated solid-phase microextraction fiber was rapidly prepared on an etched stainless-steel wire based on chemical deposition. Gold(III) was reduced to produce a mechanically robust fiber with a stable coating. Subsequently, it was applied for solid-phase microextraction of five polycyclic aromatic hydrocarbons in water samples coupled to high performance liquid chromatography with an ultraviolet-visible detector. The preconcentration conditions were optimized, including extraction and desorption time, temperature, stirring rate, and ionic strength. Under the optimized conditions, the calibration graphs were linear in the range from 1 to 500 µg · L^?1 for naphthalene and 0.20–500 µg · L^?1 for phenanthrene, anthracene, fluoranthene, and pyrene. Limits of detection were between 0.016 and 0.22 µg · L^?1 (signal-to-noise ratio = 3). The analysis of water samples showed that the recoveries ranged from 86.0% to 112.9% with relative standard deviations between 2.03% and 11.7%. The fiber coating was sensitive and suitable for the preconcentration and determination of polycyclic aromatic hydrocarbons in environmental waters. Compared with previously reported solid-phase microextraction methods, this device offered easy preparation, low cost, resistance to organic solvents, good stability, and high durability.     

Voltammetric procedure for trace metal analysis in polluted natural waters using homemade bare gold-disk microelectrodes

Voltammetric procedures for trace metals analysis in polluted natural waters using homemade bare gold-disk microelectrodes of 25- and 125-μm diameters have been determined. In filtered seawater samples, square wave anodic stripping voltammetry (SWASV) with a frequency of 25 Hz is applied for analysis, whereas in unfiltered contaminated river samples, differential pulse anodic stripping voltammetry (DPASV) gave more reliable results. The peak potentials of the determined trace metals are shifted to more positive values compared to mercury drop or mercury-coated electrodes, with Zn always displaying 2 peaks, and Pb and Cd inversing their positions. For a deposition step of 120 s at ?1.1 V, without stirring, the 25-μm gold-disk microelectrode has a linear response for Cd, Cu, Mn, Pb and Zn from 0.2 μg L^?1 (1 μg L^?1 for Mn) to 20 μg L^?1 (30 μg L^?1 for Zn, Pb and 80 μg L^?1 for Mn). Under the same analytical conditions, the 125-μm gold-disk microelectrode shows linear behaviour for Cd, Cu, Pb and Zn from 1 μg L^?1 (5 μg L^?1 for Cd) to 100 μg L^?1 (200 μg L^?1 for Pb). The sensitivity of the 25-μm electrode varied for different analytes from 0.23 (±0.5%, Mn) to 4.83 (±0.9%, Pb) nA L μmol^?1, and sensitivity of the 125-μm electrode varied from 1.48 (±0.7%, Zn) to 58.53 (±1.1%, Pb  nA L μmol^?1. These microelectrodes have been validated for natural sample analysis by use in an on-site system to monitor Cu, Pb and Zn labile concentrations in the Deûle River (France), polluted by industrial activities. First results obtained on sediment core issued from the same location have shown the ability of this type of microelectrode for in situ measurements of Pb and Mn concentrations in anoxic sediments.      

Ultrasound-Assisted Dispersive Liquid�CLiquid Microextraction Combined with Low Solvent Consumption for Determination of Polycyclic Aromatic Hydrocarbons in Seawater by GC�CMS

Ultrasound-assisted dispersive liquid?Cliquid microextraction (USA-DLLME) with low solvent consumption was demonstrated for gas chromatography-mass spectrometry (GC?CMS) determination of 16 typical polycyclic aromatic hydrocarbons (PAHs) in seawater samples. Factors affecting the extraction process, such as extraction and dispersive solvent, phase ratio, temperature, extraction and centrifugation time, were investigated thoroughly and optimized. The linear range was 20?C2,000 ng L^?1 except for acenaphthylene (Acy) at 10?C2,000 ng L^?1 and phenanthrene (Phe), fluoranthene (Flu) and pyrene (Py) all at 5?C2,000 ng L^?1. Enrichment factors (EFs) ranging from 722 to 8,133 were obtained, achieving limits of detection at 1.0?C10.0 ng L^?1. The method attained good precision (relative standard deviation, RSD) from 3.4 to 14.2% for spiked 50 ng L^?1 individual PAHs standards. Method recoveries were in the range 87?C124% and 70?C127% for spiked samples from simulated seawater and beach seawater, respectively. The proposed USA-DLLME helped to obtain about 1.1?C10 times higher EFs in a minimum amount of solvent and in less time than traditional DLLME.     

Porous carbon derived from aluminum-based metal organic framework as a fiber coating for the solid-phase microextraction of polycyclic aromatic hydrocarbons from water and soil

A nanoporous carbon derived from an aluminum-based metal-organic framework was deposited on stainless steel wires in a sol–gel matrix. The resulting fibers were applied to the solid-phase microextraction of the polycyclic aromatic hydrocarbons (PAHs) naphthalene, acenaphthene, fluorene, phenanthrene and anthracene from water and soil samples. The fiber was then directly inserted into the GC injector and the PAHs were quantified by GC-MS. The effects of salt addition, extraction temperature, extraction time, sample volume and desorption conditions on the extraction efficiency were optimized. A linear response to the analytes was observed in the 0.1 to 12 μg∙L⁻¹ range for water samples, and in the 0.6 to 30 μg∙kg⁻¹ for soil samples, with the correlation coefficients ranging from 0.9934 to 0.9985. The limits of detection ranged from 5.0 to 20 ng∙L⁻¹ for water samples, and from 30 to 90 ng∙kg⁻¹ for soil samples. The recoveries of spiked samples were between 72.4 and 108.0 %, and the precision, expressed as the relative standard deviations, is <12.8 %.

A MOF derived nanoporous carbon coated fiber for use in solid-phase microextraction was prepared via sol–gel technology. The coated fiber has a porous, rough and wrinkled structure, and shows a high thermal stability, good extraction repeatability and long lifetime. The established HS-SPME-GC-MS method is suitable for the determination of the PAHs from water and soil samples.

     

Analysis of eight pyrethroids in water samples by liquid–liquid microextraction based on solidification of floating organic droplet combined with gas chromatography

A novel method was developed for the determination of eight pyrethroids in water samples by liquid–liquid microextraction based on solidification of floating organic droplets followed by gas chromatography with electron capture detection. The type and volume of the extraction solvents, extraction time, sample solution temperature, stirring rate and ionic strength were studied and optimized. Under the optimum conditions, enrichment factors ranged from 824 to 1,432, and the limit of detection range from 2.0 to 50 ng?L^?1. The calibration graph is linear from 0.15 to 80 μg?L^?1 for cyfluthrin, fenvalerate, fluvalinate and deltamethrin, 0.09 to 80 μg?L^?1 for fenpropathrin, 0.006 to 80 μg?L^?1 for lambda-cyhalothrin, 0.026 to 80 μg?L^?1 for permethrin, 0.01 to 80 μg?L^?1 for cypermethrin. The correlation coefficients (r) varied from 0.9961 to 0.9988. The method was successfully applied to the determination of pyrethroid pesticide residues in tap water, well water, reservoir water, and river water. Recoveries ranged from 79.0% to 113.6%, and relative standard deviations are between 4.1% and 8.7%.     

Optimization of parameters for the alcoholic-assisted dispersive liquid–liquid microextraction of estrogens in water

Extraction and determination of estrogens in water samples were performed using alcoholic-assisted dispersive liquid–liquid microextraction (AA-DLLME) and high-performance liquid chromatography (UV/Vis detection). A Plackett–Burman design and a central composite design were applied to evaluate the AA-DLLME procedure. The effect of six parameters on extraction efficiency was investigated. The factors studied were volume of extraction and dispersive solvents, extraction time, pH, amount of salt and agitation rate. According to Plackett–Burman design results, the effective parameters were volume of extraction solvent and pH. Next, a central composite design was applied to obtain optimal condition. The optimized conditions were obtained at 220 μL 1-octanol as extraction solvent, 700 μL ethanol as dispersive solvent, pH 6 and 200 μL sample volume. Linearity was observed in the range of 1–500 μg L^?1 for E2 and 0.1–100 μg L^?1 for E1. Limits of detection were 0.1 μg L^?1 for E2 and 0.01 μg L^?1 for E1. The enrichment factors and extraction recoveries were 42.2, 46.4 and 80.4, 86.7, respectively. The relative standard deviations for determination of estrogens in water were in the range of 3.9–7.2 % (n = 3). The developed method was successfully applied for the determination of estrogens in environmental water samples.     

238U and 222Rn activity concentrations and total radioactivity levels in lake waters

The concentrations and distributions of natural radioactivity, uranium and radon in lake waters from around Van, Turkey were investigated with an aim of evaluating the environmental radioactivity. Fourteen lake waters were collected from different six lakes around Van (Turkey) to determine ²³⁸U, ²²²Rn and total alpha and total beta distributions in 2009. The total α and total β activities were counted by using α/β counter of the multi-detector low background system (PIC-MPC-9604) and the ²³⁸U concentrations were determined by inductively coupled plasma-mass spectrometry (Thermo Scientific Element 2) and radon concentrations were measured with the solid state nuclear track detector technique. The activity concentrations ranging from ND to 0.039 Bq L^?1 and from 0.026 to 3.728 Bq L^?1 for total alpha and beta, respectively, and uranium concentrations ranging from 0.083 to 3.078 μg L^?1, and radon concentrations varying between 47.80 and 354.86 Bq m^?3 were observed in the lake waters.     

Determination of heavy polycyclic aromatic hydrocarbons of concern in edible oils via excitation–emission fluorescence spectroscopy on nylon membranes coupled to unfolded partial least-squares/residual bilinearization

Seven heavy polycyclic aromatic hydrocarbons (PAHs) of concern on the US Environmental Protection Agency priority pollutant list (benzo[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3-c,d]-pyrene) were simultaneously analyzed in extra virgin olive oil. The analysis is based on the measurement of excitation–emission matrices on nylon membrane and processing of data using unfolded partial least-squares regression with residual bilinearization (U-PLS/RBL). The conditions needed to retain the PAHs present in the oil matrix on the nylon membrane were evaluated. The limit of detection for the proposed method ranged from 0.29 to 1.0 μg kg^?1, with recoveries between 64 and 78 %. The predicted U-PLS/RBL concentrations compared favorably with those measured using high-performance liquid chromatography with fluorescence detection. The proposed method was applied to ten samples of edible oil, two of which presented PAHs ranging from 0.35 to 0.63 μg kg^?1. The principal advantages of the proposed analytical method are that it provides a significant reduction in time and solvent consumption with a similar limit of detection as compared with chromatography.

Pressurized fluid extraction of polycyclic aromatic hydrocarbons using silanized extraction vessels

We have investigated the extraction efficiency of a pressurized fluid extraction system using an Ottawa sand matrix, soils and a certified reference material (HS-6) spiked with the 16 polycyclic aromatic hydrocarbon (PAHs) associated with method EPA 8100. Acceptable recoveries were achieved for all PAHs using a nominal sand concentration of 2.0 μg.g^-1. However, similar experiments that were conducted at a concentration of 0.20 μg.g^-1 afforded poor recoveries and poor reproducibility for the six-ring PAHs indeno(1,2,3-cd)pyrene, dibenz(a)anthracene, and benzo(ghi)perylene. These were not adequately addressed by the use of indeno(1,2,3-cd)pyrene-d12 and benzo(g,h,i)perylene-d12 surrogates. Silanization of vessels using dichlorodimethylsilane adequately passivates the system but is only required for the high surface area retention frits. Replicate analyses at concentrations of 200 and 20 ng.g^-1 demonstrated that detection limits in the low ppb range (ng.g^-1) are achieved for Ottawa sand, dry soil and soil with moisture contents up to a mass fraction of 30 %. Such performance is consistent with the analytical requirements of the Canadian Sediment Quality Guidelines. Improved analyte recoveries were also observed for the certified reference material HS-6 which were further improved by increasing extraction temperatures from 100 to 150 °C.

Use of a Headspace Solid-Phase Microextraction-Based Methodology Followed by Gas Chromatography–Tandem Mass Spectrometry for Pesticide Multiresidue Determination in Teas

This study reports on the development of a fast and efficient method based on headspace solid-phase microextraction (HS-SPME) coupled to gas chromatography–tandem mass spectrometry (GC–MS/MS) for simultaneous analysis of 128 volatile or semi-volatile pesticide residues belonging to nine classes of pesticides. The important factors related to HS-SPME performance were optimized; these factors include fiber types, water volume, ion strength, extraction temperature, and extraction time. The best extraction conditions include a PDMS/DVB fiber, and analytes were extracted at 90 °C for 60 min from 1 g of tea added to 5 mL of 0.2 g mL^?1 NaCl solution. The methodology was validated using tea samples spiked with pesticides at three concentration levels (10, 50, and 100 μg kg^?1). In green tea, oolong tea, black tea, and puer tea, 82.8, 88.3, 79.7, and 84.3% of the targeted pesticides meet recoveries ranging from 70 to 120% with a relative standard deviation of?≤?20%, respectively, when spiked at a level of 10 μg kg^?1. Limits of quantification in this method for most of the pesticides were 1 or 5 μg kg^?1, which are far below their maximum residue limits prescribed by EU. The optimized method was employed to analyze 30 commercial samples obtained from local markets; 17 pesticide residues were detected at concentrations of 2–452 μg kg^?1. Chlorpyrifos was the most detected pesticide in 80% of the samples, and the highest concentration of dicofol (452 μg kg^?1) was found in a puer tea. This is the first time to find that the optimized extraction temperature for pesticide residues is 90 °C, which is much higher than other reported HS-SPME extraction conditions in tea samples. This developed method could be used to screen over one hundred volatile or semi-volatile pesticide residues which belong to multiple classes in tea samples, and it is an accurate and reliable technique.     

Optimized solid phase extraction based on diethyldithiocarbamate-coated Fe3O4 magnetic nanoparticles followed by ICP-OES for determination of Cd(II) and Ni(II) in rice and water samples

In the present study, application of Fe₃O₄ magnetic nanoparticles (MNPs) coated with diethyldithiocarbamate as a solid-phase sorbent for extraction of trace amounts of cadmium (Cd²⁺) and nickel (Ni²⁺) ions by the aid of ultrasound was investigated. The analytes were determined by inductively coupled plasma-optical emission spectroscopy. Fe₃O₄ MNPs were prepared by solvothermal method and characterized with dynamic light scattering, scanning electron microscope and X-ray diffraction. Response surface methodology was used for optimization of the extraction process and modeling the data. The optimal conditions obtained were as follows: chelating agent, 1.2 g L^?1; pH, 6.13; sonication time, 13 min and Fe₃O₄ MNPs, 10.3 mg. The calibration curves were linear over the concentration range of 1–1,000 μg L^?1 for Cd²⁺ and 2.5–1,000 for Ni²⁺ with the determination coefficients (R ²) of 0.9997 and 0.9995, respectively. The limits of detection were 0.27 μg L^?1 for Cd²⁺ and 0.76 μg L^?1 for Ni²⁺. The relative standard deviations (n = 7, C = 200 μg L^?1) for determination of Cd²⁺ and Ni²⁺ were 2.0 and 2.7 %, respectively. The relative recoveries of the analytes from tap, river and lagoon waters and rice samples at the spiking level of 10 μg L^?1 were obtained in the range of 95–105 %.     

QuEChERS and solid phase extraction methods for the determination of energy crop pesticides in soil,plant and runoff water matrices

QuEChERS and solid phase extraction (SPE) methods were applied for determining four herbicides (metazachlor, oxyfluorfen, quizalofop-p-ethyl, quinmerac) and one insecticide (α(±)-cypermethrin) in runoff water, soil, sunflower and oilseed rape plant matrices. Determination was performed using gas chromatography mass spectrometry (GC-MS), whereas high-pressure liquid chromatography mass spectrometry (HPLC-MS) was used for quinmerac. In all substrates linearity was evaluated using matrix-matched calibration samples at five concentration levels (50–1000 ng L^?1 for water, 5–500 μg kg^?1 for soil and 2.5–500 μg kg^?1 for sunflower or oilseed rape plant). Correlation coefficient was higher than 0.992 for all pesticides in all substrates. Acceptable mean recovery values were obtained for all pesticides in water (65.4–108.8%), soil (70.0–110.0%) and plant (66.1–118.6%), with intra- and inter-day RSD% below 20%. LODs were in the range of 0.250–26.6 ng L^?1 for water, 0.10–1.8 μg kg^?1 for soil and 0.15–2.0 μg kg^?1 for plants. The methods can be efficiently applied for field dissipation studies of the pesticides in energy crop cultivations.     

Application of Self-Assembled Monolayers in the Preparation of Solid-Phase Microextraction Coatings

Self-assembled monolayers (SAMs) of polyaminithiophenol (PATP) were used as a covalent bonded coating for solid-phase microextraction (SPME). Thiolated aniline-analog monomers (mixture of 2- and 3-aminothiophenols, 2/3-ATP) were anchored on the gold surface and then electropolymerized. Due to the strong S?CAu bond, thiol-terminated coating on the gold surface was very stable. The proposed covalent bonded coating showed higher mechanical (re-usability up to 100 times) and thermal stability (up to 320???C) than non-covalent bonded polyaniline coating (re-usability up to 20 times and thermal stability up to 250???C). The extraction capability of the proposed fiber for the extraction of five polycyclic aromatic hydrocarbons (PAHs), including phenanthrene, anthracene, pyrene, 9,10-dimethylanthracene and benzo[??]anthracene was examined. The effects of different parameters influencing the extraction efficiency of analytes including extraction temperature, extraction time, ionic strength, stirring rate and sample volume were examined and optimized. Linear ranges of 1?C250???g?L^?1 for phenanthrene and anthracene, and 1?C100???g L^?1 for the other compounds were obtained. Detection limits were in the range of 0.1?C0.32???g?L^?1. Single fiber repeatability and fiber to fiber reproducibility were less than 8.9 and 15.8%, respectively. Seawater sample was analyzed as real sample and good recoveries (81?C108%) were obtained for target analytes.