Improvement of the quantitativeness of the thermal desorption-GC/MS method and development of polystyrene certified reference material for the quantification of decabromodiphenyl ether (BDE 209) by using isotope dilution mass spectrometry.

A polystyrene (PS) certified reference material (CRM) for the analysis of decabromodiphenyl ether (BDE 209) was issued. PS disk was prepared by injection molding of the mixture of versine PS and BDE 209. The certification of the PS CRM was conducted by two analytical methods with different sample preparation methods using isotope dilution mass spectrometry (IDMS). The certified value, wCRM, was 978 mg/kg, and this value coincided with the regulation value of BDE 209 in the Restriction of Hazardous Substances directive (1000 mg/kg). The uncertainties related to certification, uwmean, inhomogeneity, uhom, and long- and short-term instability, usts and ults, respectively, were evaluated based on the mass fraction of BDE 209. The uwmean, uhom, usts, and ults were 0.0265, 0.0046, 0.0061, and 0.0099 (relative), respectively, and the expanded uncertainty for this CRM was determined as 57 mg/kg (coverage factor is 2). Additionally, the quantitative capability of the thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was evaluated. In TD-GC/MS, the analytical values of the developed CRM obtained by the external and internal standard methods with matrix-free calibrants were out of the range of the wCRM (almost 10% larger or smaller), whereas those with matrix-matched calibrants agreed with the wCRM. In contrast to these results, the analytical values obtained by TD-GC/MS using IDMS were consistent with the wCRM no matter if matrix-free or matrix-matched calibrants were used. These results indicated that, for quantification of BDE 209 in PS, the trueness and precision of TD-GC/MS can be enhanced by applying IDMS without matrix-matched calibrants.

A simple reliable quantification of glyphosate in human urine using MonoSpin TiO extraction and isotope dilution mass spectrometry.

A method of quantifying glyphosate (Gly) in human urine by means of MonoSpin TiO extraction and 9-fluorenylmethoxycarbonyl chloride (FMOC-Cl) derivatization with isotope dilution mass spectrometry (IDMS) was investigated and optimized. The method's quantification limit under optimized conditions was 0.3 µg/kg for FMOC-Gly, which was comparable to or lower than those described in previous studies. When a spike test using human urine samples was carried out with optimized analytical conditions, the trueness for FMOC-Gly was as follows: 101.6-104.9% for a spike level of 0.5 µg/kg and 99.2-101.0% for a spike level of 30 µg/kg. The intra-day repeatability and inter-day reproducibility were <6.5%. The spike test results for validation between the "with" and "without" derivatization methods were comparable at 1 µg/kg. Our results indicate that using MonoSpin TiO extraction and FMOC-Cl derivatization with IDMS is an accurate method for analyzing Gly in human urine.

Interlaboratory trial of short-chain chlorinated paraffin: comparison of mass fractions and homolog profiles in a simulation environmental sample.

Short-chain chlorinated paraffins (SCCPs) are listed in the Stockholm Convention. Therefore, selecting suitable methods for their accurate quantification is essential. Nowadays, the quality of commercial reagents employed as quantification standards is not guaranteed. As a solution, we adopted an SCCP formulation reference material with known homolog composition ratios as the quantification standard to evaluate the appropriateness of the methods. By mixing the SCCP formulation and interferences, an analytical sample was independently prepared and used as the simulation environmental sample. The homolog compositional profiles of the SCCPs resembled those of the quantification standard and the analytical sample. The mass fractions and the homolog profiles, including the carbon chain length and chlorine homolog profiles, of the SCCPs were reported by 14 different laboratories. For the mass fraction, the results reported by participants were consistent, except for the participants that employed low-resolution gas chromatography (GC). The results generated from liquid chromatography (LC) and GC were slightly different, despite of the similar homolog composition ratios between the quantification standard and the analytical sample. Although there were discreet discrepancies in the overall chlorine homolog profiles, the carbon chain length profiles acquired from GC and LC were similar. The differences depended on the method employed. Additionally, compared with the low-resolution data, the high-resolution data displayed less fluctuation since the effect of the interferences on the analytical sample was reduced because of the mass accuracy of high-resolution instruments. Accordingly, the interlaboratory trial employing the similar homolog compositional profiles of the quantification standard and the analytical sample proved valuable in elucidating the differences among methods, considering equipment, resolution specification, and ionization.

Differences in the internal energies of ions in electrospray ionization mass spectrometers equipped with capillary-skimmer and capillary-RF lens interfaces.

Small metabolites are commonly analyzed using electrospray ionization mass spectrometry (ESI-MS). Although the protonated form of a compound of interest is typically the target ion in ESI-MS, the protonated forms of small metabolites occasionally undergo fragmentation during ion transmission from ambient conditions to vacuum conditions, hindering the unambiguous identification of analyte molecules. To estimate the fragmentation efficiency during ESI processes, the internal energy distribution of the ions (P(E)) must be evaluated. The common approach for the P(E) evaluation is the survival yield method, which uses thermometer ions. In this study, the P(E) of ions produced by an ESI source in a commercial triple quadrupole mass spectrometer equipped with a capillary-skimmer and capillary-RF lens interfaces was evaluated using benzyl ammonium thermometer ions. Furthermore, this study proposes the use of 3-(aminomethyl)indole and related compounds, which have the lowest Eapp values among the reported thermometer ions, to obtain P(E) values of the ions more accurately. Results showed that P(E) strongly depends on whether a capillary-skimmer interface or capillary-RF lens interface was used for ion transport to the vacuum. ESI-MS with a capillary-skimmer interface provided a considerably lower and narrower P(E) of ions than that with a capillary-RF lens interface, thereby producing intact protonated molecules without significant fragmentation of most small metabolites. However, ESI-MS equipped with capillary-RF lens interfaces provided a higher efficiency of ion transmission than ESI-MS equipped with a capillary-skimmer interface, allowing for highly sensitive analysis of metabolites.

Quantitative Determination of Organophosphorus, Pyrethroid, and Dithiolane Pesticide Residues in Brown Rice Using Supercritical Fluid Extraction and Liquid Chromatography-Tandem Mass Spectrometry.

BACKGROUND: Supercritical fluid extraction (SFE) is a fast, versatile, and solvent-efficient automatic extraction method. Despite its advantages, the results of our proficiency tests imply that the applicability assessments of SFE for pesticide residues were insufficient. OBJECTIVE: In this study, as analytical method using SFE was optimized and validated by testing the incurred and fortified brown rice samples with organophosphorus (OP), pyrethroid (PYR), and dithiolane (DIT) pesticides. METHOD: A validation study using the incurred sample with etofenprox, fenitrothion, and isoprothiolane was performed by comparing the analytical results obtained using the SFE and solid-liquid extraction with homogenization (SLE), which is a well-validated official multi-residue extraction method. The tests on the fortified samples were also performed for seven pesticide residues, chlorpyrifos, diazinon, O-ethyl O-4-nitrophenyl phenylphosphonothioate (EPN), etofenprox, fenitrothion, isoxathion, and isoprothiolane, at three fortification levels, 0.001, 0.01, and 0.1 mg/kg. RESULTS: In the test on the incurred samples, optimized SFE-to-SLE analytical values (CSFE/CSLE) were 99.2-100.1%, with RSD lower than 3%. In contrast, the analytical-to-spiked concentrations in the tests on the fortified samples were 96.4-105.0%, with RSD lower than 8.8%. CONCLUSIONS: These results indicate that the proposed SFE method, which is well validated with the incurred brown rice sample, is useful for determining OP, PYR, and DIT pesticide residues in brown rice. HIGHLIGHTS: The proposed SFE method satisfies EU and Japanese maximum residue limits (MRLs). The consumption of solvent can be reduced to one-fourth of that of SLE using the proposed SFE method.

Nationwide distribution of per- and polyfluoroalkyl substances (PFAS) in road dust from India.

In India, information on the occurrence and distribution of legacy and emerging per- and polyfluoroalkyl substances (PFAS) is deficient. In the present study, nationwide 79 road dust samples were collected from 12 states and 1 union territory for the analysis of 34 PFAS. Overall, total concentrations of 21 quantified PFAS (∑21PFAS) ranged 23-861 pg/g (median: 116 pg/g), with perfluorooctane sulfonic acid (PFOS) being predominant (median: 19.9 pg/g). Short to long chain perfluoroalkyl carboxylic acids (PFCAs; C4 - C18) were detected, where the concentrations of PFAS decreased with the increase in PFAS carbon chain length. ∑21PFAS was highest in road dust from urban area (n = 27; median: 230 pg/g), followed by suburban (n = 21; median: 126 pg/g) and rural areas (n = 31; median: 76 pg/g), suggesting environmental impacts of industriallization and urbanization on PFAS distribution. PFAS composition in rural road dust was significantly different from those in suburban and urban samples (p < 0.01). Regarding 4 geographical regions of India, PFAS in road dust showed spatial difference where higher concentrations were found in South India compared to other regions. ∑21PFAS were positively associated with city-wise population of India (rs = 0.40, p < 0.01). Strong to moderate positive correlation was observed between ∑21PFAS, fluorotelomer sulfonic acids, and PFCAs (rs = 0.23, 0.30, and 0.28, respectively; p < 0.05) and the total state-wise vehicles in India, suggesting that vehicles exhaust or non-exhaust (e.g., vehicle tire debris and polishing material) might contribute to the PFAS occurrence in Indian road dust. Toddlers (2-5 years) had the highest estimated daily intake of ∑PFAS via road dust ingestion under average-case and worst-case scenarios (0.55 and 1.16 pg/kg bw/day, respectively). This is the first time to evaluate PFAS in Indian road dust nationwide, aiding to provide first-hand data for human exposure to PFAS in India.

Residue Distribution and Daily Exposure of Per- and Polyfluoroalkyl Substances in Indica and Japonica Rice.

Per- and polyfluoroalkyl substances (PFAS) have excellent chemical stability but have adverse environmental impacts of concern. Furthermore, bioaccumulation of PFAS in rice varieties─which is the essential staple food crop in Asia─has not been verified. Therefore, we cultivated Indica (Kasalath) and Japonica rice (Koshihikari) in the same Andosol (volcanic ash soil) paddy field and analyzed the air, rainwater, irrigated water, soil, and rice plants for 32 PFAS residues, throughout the cultivation to human consumption. During the rice cultivation period, the cultivation environment in atmospheric particulate matter (PM) constituted perfluoroalkyl carboxylic acids (PFCAs), with minimal perfluorinated sulfonic acids (PFSAs). Furthermore, perfluorooctanesulfonic acid (PFOS) migrates at a PM > 10 to drop in a cultivation field and was conducive to leakage and accumulation of PFCAs in air particles in the field environment. Moreover, precipitation was a sources of irrigation water contamination, and cultivated soil with a high carbon content could capture PFSAs and PFCAs (over C10). There were no major differences in residual PFAS trends in the rice varieties, but the distribution of PFAS in the growing soil, air, and rainwater differed. The edible white rice part was mainly affected by irrigation water in both varieties. Monte Carlo simulations of daily exposure assessments of PFOS, PFOA, and perfluorononanic acid showed similar results for Indians consuming Indica rice and Japanese consuming Japonica rice. The results indicate that the ultratrace PFAS residue concentrations and their daily exposure were not cultivar-specific.

Reliable estimation of Raman shifts for peaks of L-cystine (NMIJ CRM 6025-a) in the low-frequency region.

Raman scattered light is generated by the interaction of irradiated light with molecular vibrations, and it provides molecular information. Although Raman shifts of peaks in the low-frequency region (< 200 cm-1) provide useful information related to molecular structures, there are no reliable materials available for calibrating Raman spectrometers in this region. In this study, we chose high-purity L-cystine (NMIJ CRM 6025-a) and used it to reliably evaluate Raman shifts of peaks with uncertainty by a combination of HeNe laser and Ne emission lines. To evaluate their uncertainty, we considered the uncertainty originating from wavenumbers of Ne emission lines and HeNe laser, evaluation of wavenumber for peak-tops and changes in temperature. The obtained Raman shifts of eight peaks from 9 to 160 cm-1 and their uncertainty were 0.3 cm-1 or 0.4 cm-1 and these values were validated with the results using a 532 nm laser.

A reference material (NMIJ RM 4076-a) for the determination of short-chain chlorinated paraffins.

Chlorinated paraffins are primary industrial chemical products used for metalworking fluids and flame retardants. However, short-chain chlorinated paraffins (SCCPs) are registered in Annex A of the Stockholm Convention on Persistent Organic Pollutants. Therefore, since an accurate quantitative determination of SCCPs is crucial to monitor the level of pollution, analysis quality assurance with reference materials is needed. In this study, a reference material (RM), NMIJ RM 4076-a, was developed by the National Metrology Institute of Japan at the National Institute of Advanced Industrial Science and Technology (NMIJ/AIST) for the quantification of SCCPs. We determined the mass fraction of SCCPs by subtracting the impurities quantified using the mass-balance method, a combination of gas chromatography-flame ionization detection, Karl Fischer titrations, headspace-gas chromatography-mass spectrometry, and thermal gravimetric analysis. The mass fraction value of NMIJ RM 4076-a was concluded to be 0.9996 kg/kg. The standard uncertainty of this mass fraction was evaluated on the basis of the mass-balance method, the sample homogeneity, and stability obtained using the above analytical techniques. Accordingly, the expanded uncertainty estimated using a coverage factor of k = 2 was found to be 0.0013 kg/kg. The mass fraction of chlorine and the homologue compositional ratios are also given for this RM as supplementary technical information. This RM is expected to be applicable for use in the calibration of instruments, or for checking the validity of analytical methods or instruments for estimating the comparability of SCCP analyses.

Comparison of short-chain chlorinated paraffin concentrations and homolog profiles by interlaboratory trial using a candidate reference material.

Chlorinated paraffins (CPs) are industrial chemicals that have been primarily used in applications involving metalworking fluids. Among CPs, short-chain chlorinated paraffins (SCCPs) are a well-known environmental pollutant and are listed under Annex A of the Stockholm Convention on Persistent Organic Pollutants. CPs are alkanes substituted with chlorine atoms, and SCCPs are comprised of 10-13 carbon atoms. Reliable quantification of SCCPs is a critical issue because of the large number of SCCP isomers that are in use across multiple industries. Some interlaboratory comparisons of SCCP analyses have been conducted, and the reliability of these results was overwhelmingly determined as inferior to that of comparable PCB and dioxin analyses because of variations in the quality of commercial reagents that were employed as quantification standards. In order to address such inconsistencies, this study endeavored to prepare and evaluate a novel SCCP formulation as a candidate reference material for use as a reliable quantification standard. A subject trial study was hence performed to evaluate methods such as gas- and liquid-chromatography mass spectrometry (GC/MS and LC/MS) on sample matrices (without a clean-up process), and to subsequently elucidate the interpreted specifications for their candidacy as a reliable quantification standard. Results ultimately showed that the SCCP concentrations obtained from GC and LC were comparable. When the homologs reported by a subset of 14 separate laboratories were unified (excluding all results for Cl4 homologs), the carbon chain length profiles obtained from GC and LC were found to be similar; however, the overall chlorine homolog profiles did exhibit slight differences. Moreover, the results from high-resolution MS showed less variation than those from low-resolution MS. Thus, it was overarchingly determined that the deployment of this candidate reference material would serve as an effective mechanism for estimating the comparability of SCCP quantifications/evaluations of standard materials.

Evaluation of flame retardancy and flexural property on prepared plastic disks containing known concentrations of flame retardants through simulated weathering tests.

The standardized acrylonitrile-butadiene-styrene (ABS) or polycarbonate (PC) resin disk with added flame retardants (FRs) has a potential to be a suitable tool for predictions of both aging of the plastic materials and release rate of a flame retardants exposed under different outdoor and indoor conditions. The experiments examined the dynamics and kinetics of the release of dechlorane plus, tetrabromobisphenol A, triphenyl phosphate and antimony trioxide as FRs from a standardized plastic disk before and after exposure to artificial sunlight. Assessments were carried out independently to measure changes in the content of flame retardants and monitor the flame retardancy and flexural properties after exposure (60 W/m2) over a period of 200 h and 500 h, which are reasonable to predict a short-time tendency and to receive any advice for a safe re-use. The releases of three organic flame retardants and four elements (Cl, Br, P and Sb) from weathered ABS and PC disks were very limited, except for surface delamination and resin microparticles. Triphenyl phosphate was stable without hydrolysis, while the degradation of tetrabromobisphenol A was observed (approximately 20% decrease for ABS disk and approximately 50% decrease for PC disk). During the study, no significant differences in the flame retardancy and flexural properties of the disks could be detected. In practice, the results obtained from disks of acrylonitrile-butadiene-styrene or polycarbonate resin with selected flame retardants used in specific conditions may provide technical expertise regarding weathering processes.

Development of a Polystyrene Reference Material for Raman Spectrometer (NMIJ RM 8158-a).

The Raman shift is one of the most important parameters in Raman spectroscopy, and is calculated from the difference in the wavenumbers for excitation and for Raman scattering. Because the observed shifts are strongly dependent on the spectrometer and the measurement conditions, physically and chemically stable reference materials for Raman-shift validation are required. We reliably estimated the Raman shift and evaluated its uncertainty for peaks of a 4-mm-thick, 25-mm-diameter polystyrene disc by using a HeNe laser and Raman-scattered light calibrated with Ne/Ar emission lines. We considered uncertainties originating from the fitting, repeatability, and reproducibility of both the Ne/Ar emission lines and the Rayleigh/Raman-scattered lights, as well as the wavenumber of the unstabilised HeNe laser, and pixel and spectral resolutions. We also considered uncertainty originating from inhomogeneity among and within discs, as well as their long-term stability. The obtained Raman shifts of 11 peaks (reference values) were comparable to those described in ASTM E1840 with expanded uncertainty at 1.1 or 1.2 cm-1 (k = 2, coverage factor).

Development of Artificial Urine Certified Reference Material for Quantification of Neonicotinoid Insecticides.

BACKGROUND: Neonicotinoid insecticides (neonicotinoids) are widely used, however, they can negatively affect human health. Thus, neonicotinoids and their metabolites in human urine are analyzed globally to assess exposure levels and health risks. To properly assess the exposure levels and health risks, accurate analytical results are a necessity. OBJECTIVE: This study aims to develop urine certified reference material (CRM), NMIJ CRM 7408-a, for the quantification of neonicotinoids. METHOD: To develop NMIJ CRM 7408-a, commercially available artificial urine was used as the raw material to which the target neonicotinoids were added. Analyses of neonicotinoids in NMIJ CRM 7408-a were carried out by isotope dilution mass spectrometry (IDMS). RESULTS: Sample homogeneity was assessed, with the results showing that acetamiprid, clothianidin, thiacloprid, and thiamethoxam exhibited sufficiently homogeneous distributions in the material. The relative uncertainties due to inhomogeneity were 1.2-7.0%. The results obtained from long-term stability assessment indicated that the target neonicotinoids were stable. The relative uncertainties due to instability were 9.4-17.2% (for an expiry date of 21 months). The characterization for providing concentration values was carried out using one (clothianidin and thiacloprid) or two (acetamiprid and thiamethoxam) analytical methods. The certified values of the target neonicotinoids (acetamiprid, clothianidin, thiacloprid, and thiamethoxam) were 0.19-1.38 µg/kg. CONCLUSIONS: This is the first frozen artificial urine CRM in which neonicotinoids were quantified by IDMS and will be useful for evaluating the accuracy of analysis and validation of analytical methods for the determination of neonicotinoids in urine. HIGHLIGHTS: NMIJ CRM 7408-a, which has been certified for four neonicotinoids, was developed by NMIJ.

Evaluation of supercritical fluid extraction for the determination of neonicotinoid pesticides in green onion.

A supercritical fluid extraction (SFE) method was presented for the determination of neonicotinoid pesticides in green onion. We optimized the SFE parameters, namely the pressure, temperature, type and concentration of the modifier solvent, and extraction time, by testing on the incurred green onion applied with four commercial neonicotinoid formulations at the harvesting stage. The analytical values of the four neonicotinoids, obtained by 5 min dynamic SFE with a 25% (v/v) methanol/supercritical carbon dioxide mixture at 80 °C and 25 MPa, were in good agreement with those obtained by solid-liquid extraction using a homogenizer. This latter homogenization method is employed as a Japanese official method for the analysis of pesticide residues in food. The SFE-to-homogenization analytical value ratios were in the range 98.8-100.0%. Spike-and-recovery testing with spiked green onion was also performed by optimized SFE. The ratios of the analytical-to-spiked concentrations for six neonicotinoids obtained by the SFE method were 96.1-102.1% for 0.4 mg/kg and 93.9-104.1% for 4.0 mg/kg spiking levels. These values satisfied the Japanese validation guidelines for the testing method of pesticides in food. These results indicate that SFE is applicable for the analysis of neonicotinoids in green onion and enables automatic extraction with a small amount of solvent.

Mixture Touch: A Web Platform for the Evaluation of Complex Chemical Mixtures.

Risk assessment of chemical mixtures isRisk assessment of chemical mixtures is challenging because information about the chemical structure, concentration, properties, and toxicity, down to the individual compounds, is generally not readily accessible. To cope with this challenge, we think Mixture Touch- a web platform that offers a one-window solution, for free, for the risk assessment of complex mixtures that are analyzed with comprehensive two-dimensional gas chromatography (GC × GC). GC × GC is a powerful analytical technique for target and nontarget analysis of complex mixtures. Our web platform allows users to visualize the GC × GC data, conduct spectral identification, estimate properties, and analyze potential risks based on established methods. For illustration purpose, we show how to assess the aquatic bioaccumulation potential of short-chain chlorinated paraffin (SCCP), which is an industrially manufactured mixture. The platform readily demonstrated that most of the SCCP congeners did not have the tendency to accumulate in aquatic organisms but in humans. The platform can bridge the gap between the GC × GC experts, GC × GC users, analytical experts, and risk assessors. It could enhance the level of risk assessments of mixtures utilizing the high performance of the state-of-the-art analytical instruments.

Reliable Evaluation of the Lateral Resolution of a Confocal Raman Microscope by Using the Tungsten-dot Array Certified Reference Material.

Confocal Raman microscopes are widely used in various applications because they provide physical and chemical information at a submicron scale. A high lateral resolution in the confocal Raman microscope is essential for obtaining high-quality images. We used an array of tungsten dots at a 600 nm pitch on a Si substrate of the certified reference material (NMIJ CRM 5207-a) to reliably evaluate the lateral resolution of a confocal Raman microscope at various pinhole sizes. The precision of the mapping scale in the x- and y-pitches was confirmed from Si signal profiles, and the lateral resolution was evaluated by a straight-edge method using scale indicators in the reference material. Because these procedures are applicable to other confocal Raman microscopes with popular specifications (532 nm laser, 100× objective lens, numerical aperture 0.9, step size 0.1 µm), they are suitable for both a reliable evaluation of the lateral resolution of a confocal Raman microscope and for daily checks on the precision of its mapping scale.

Proficiency testing by the National Metrology Institute of Japan for quantification of pesticide residues in grain samples from 2012 to 2018.

From 2012 to 2018, proficiency testings (PTs) were carried out to support the analytical skill development of participants. Grains were sprayed with various target pesticides and used as material samples for PTs. It was found that 27-56% and 10-43% of participants used the Japanese official multiresidue method and a solid-phase extraction technique with the Quick, Easy, Cheap, Effective, Rugged, and Safe (modified QuEChERS, known as "STQ" in Japan) method, respectively. Reported results were evaluated using two types of z-scores: one was based on consensus values calculated from the analytical results reported by the participants, and the other was based on values obtained by the National Metrology Institute of Japan (NMIJ). Acceptable z-scores based on the consensus values and NMIJ reference values were achieved by 78-95% and 67-94% of the participants, respectively. Many laboratories improved their z-scores by continuing participation in our PT.

Evaluation of pressurized liquid extraction for the determination of neonicotinoid pesticides in green onion.

A pressurized liquid extraction (PLE) method was presented for the determination of six neonicotinoid pesticides, acetamiprid, clothianidin, dinotefuran, imidacloprid, thiacloprid, and thiamethoxam in green onion. The critical parameters of PLE, e.g. extraction solvent, temperature, pressure, number of cycles, and static extraction time, were optimized by test on the spiked green onion with six neonicotinoids and the incurred green onion applied with four commercial neonicotinoid insecticide formulations (acetamiprid, dinotefuran, imidacloprid, and thiamethoxam). As a result, the recoveries of six neonicotinoids obtained by one cycle PLE with acetonitrile at 140 °C and 50 bar for 10 min were 94.7-99.5%. These results were acceptable according to the validation guideline for testing method of agricultural chemicals in food by Ministry of Health, Labour, and Welfare in Japan. PLE was also validated by the test on the incurred green onion. The analytical values of four neonicotinoids obtained by PLE were good agreement with those obtained by solid-liquid extraction with homogenizer, which is employed for Japanese official method for the analysis of pesticide residues in food (the ratios of analytical values obtained by PLE to those obtained by solid-liquid extraction were 99.7-101.2%). These results indicate that PLE is applicable for the determination of neonicotinoids in green onion.

Evaluation of the impact of matrix effects in LC/MS measurement on the accurate quantification of neonicotinoid pesticides in food by isotope-dilution mass spectrometry.

The use of isotope-labeled internal standards is the most widely accepted approach to overcome the matrix effects on quantification of pesticides in food by LC/MS. We evaluated the impact of the matrix effects on quantification of six neonicotinoid pesticides, acetamiprid, clothianidin, dinotefuran, imidacloprid, thiacloprid, and thiamethoxam, in food by using deuterated internal standards. The calibration curves for each pesticide were obtained by using matrix-free and matrix-matched calibration solutions with blank brown rice, carrot, and green onion extracts. For brown rice and carrot, the matrix effects were not observed. In contrast, the slopes of calibration curves for each pesticide were influenced by presence of green onion extracts in calibration solutions (variability of the slopes was 4-9%), because the ratios of peak area for native pesticide to those for internal standards were influenced by matrix. The spike-and-recovery test with green onion was also performed. The analytical values obtained by using matrix-free calibration solution were biased from the spiked concentration, whereas those obtained by using matrix-matched calibration solution were comparable to the spiked concentration. These results indicate that matrix-matched calibration solution should be used for accurate quantification of neonicotinoid pesticides in food by LC/MS using deuterated internal standards.

Effect of Long-time Heating for Elements from Flame Retardants in Acrylonitrile Butadiene Styrene and Polycarbonate Resin Disks.

The effect of long-time heating for elements from flame retardants (FRs) such as dechlorane plus (DP), tetrabromobisphenol A (TBBPA), triphenyl phosphate (TPhP) and antimony trioxide (Sb2O3) in both acrylonitrile-butadiene-styrene (ABS) and polycarbonate (PC) resin disks was examined in the present study. The heating temperature by a drying oven was 80°C, which was expected to be a harder environment than that of usual dump site to discard electric and electronic equipment, and the long-time heating was carried out for up to 722 days. As a result, the increases for both ether (C-O-C) and ketone (C=O) groups and the decrease of C=C double bond as well as methylene group (=CH2) were found for an ABS resin disk by fourier transform infrared (FTIR) spectrometry, which was expected to result in an increase of mass of the disk up to ca. 4% due to oxidation during the long-time heating. The changes in concentrations for bromine (Br), chlorine (Cl), phosphorous (P) and Sb, which were originated elements from FRs contained, were also evaluated by energy dispersive X-ray fluorescence (ED-XRF) spectrometry and the decreases in concentrations of ca. 5% in ABS resin disk were observed which could be almost explained by increasing ca. 4% mass of the disk. On the contrary, the mass and chemical form of a PC resin disk as well as the concentrations of elements contained did not change during the long-time heating. From these results, it could be considered that most of the elements from DP, TBBPA, TPhP and Sb2O3 contained as FRs in the ABS and PC resin disks examined in the present study were not lost during the long-time heating, even though the color, shape, mass and chemical form of ABS resin disk were changed.