ABSTRACT
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.
ABSTRACT
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.
Subject(s)
Hydrocarbons, Chlorinated , Paraffin , China , Environmental Monitoring/methods , Flame Ionization , Gas Chromatography-Mass Spectrometry/methods , Hydrocarbons, Chlorinated/analysis , Paraffin/analysisABSTRACT
Dependence of the response of a corona-charged aerosol detector (corona CAD) on the concentration and densities of brominated flame retardants and some related substrates was studied. The calibration curves of the substrates did not show linearity and the substrate with a lower density exhibited the stronger response. Regardless of the solvents (chloroform or toluene), and the injected volume of the substrate solution, the signal intensity of the substrate observed by a corona CAD was substantially proportional to 2/3 power law of concentration and proportional to (-2/3) power law of the density of the substrates. These results suggest that the responses should be proportional to the surface area of the particles generated through the drying process in corona CAD. Contrary to the former reports that the detector response of a corona CAD was independent of chemical species, it was proved that the response varies with the density of a substrate.
ABSTRACT
The dasD gene is located just downstream of the dasABC gene cluster, encoding components of an ABC transporter for uptake of a chitin-degradation product N,N'-diacetylchitobiose [(GlcNAc)(2) ] in Streptomyces coelicolor A3(2). To clarify the roles of the DasD protein in the degradation and assimilation of chitin, we obtained and characterized a recombinant DasD protein and a dasD-null mutant of S. coelicolor A3(2). The recombinant DasD protein produced in Escherichia coli showed N-acetyl-ß-d-glucosaminidase (GlcNAcase) activity and its optimum temperature and pH were 40 °C and 7, respectively. dasD transcription was strongly induced in the presence of chitin, weakly by chitosan, but not by cellulose or xylan in S. coelicolor A3(2). Immuno-blot analysis demonstrated that DasD is a cytoplasmic protein. The dasD-null mutant exhibited cellular GlcNAcase activity which was comparable with that of the parent strain M145. DasD, thus, did not seem to be a major GlcNAcase. Induced extracellular chitinase activity in the dasD-null mutant was, interestingly, higher than M145, in the presence of colloidal chitin or (GlcNAc)(2) . In contrast to M145, (GlcNAc)(2) temporally accumulated in the culture supernatant of the dasD-null mutant in the presence of colloidal chitin.