Development of a candidate certified reference material of cypermethrin in green tea.

This paper presents the preparation of a candidate certified reference material (CRM) of cypermethrin in green tea, GLHK-11-01a according to the requirements of ISO Guide 34 and 35. Certification of the material was performed using a newly developed isotope dilution mass spectrometry (IDMS) approach, with gas chromatography high resolution mass spectrometry (GC-HRMS) and gas chromatography-tandem mass spectrometry (GC-MS/MS). Statistical analysis (one-way ANOVA) showed excellent agreement of the analytical data sets generated from the two mass spectrometric detections. The characterization methods have also been satisfactorily applied in an Asia-Pacific Metrology Program (APMP) interlaboratory comparison study. Both the GC-HRIDMS and GC-IDMS/MS methods proved to be sufficiently reliable and accurate for certification purpose. The certified value of cypermethrin in dry mass fraction was 148 µg kg(-1) and the associated expanded uncertainty was 14µg kg(-1). The uncertainty budget was evaluated from sample in homogeneity, long-term and short-term stability and variability in the characterization procedure. GLHK-11-01a is primarily developed to support the local and wider testing community on need basis in quality assurance work and in seeking accreditation.

The first international proficiency test on ketamine and norketamine in hair.

This paper discusses the organization of the first international proficiency test (PT) programme on ketamine (K) and norketamine (NK) in hair samples. The primary objective of the programme was to evaluate the analytical capability of participating laboratories on hair analysis for K and NK via comparison of results. Authentic samples, instead of spiked samples were used in the programme to mimic the analysis of incorporated illicit drugs in real-life situations. Eight of the ten participating medical or forensic laboratories from Australia, France, Hong Kong, Italy, Singapore and the USA returned results to the organizer. Quantification methods from these laboratories were confined to GC-MS and LC-MS/MS. Performance assessment based on z-score indicated that only three laboratories achieved satisfactory results for both the analysis of K and NK. It was concluded that the overall performance of the participating laboratories was fair and there is still room for further improvement. Additional similarly designed PT programmes are recommended to be organized in order to encourage reliable measurements of illicit drugs in hair samples. Taking into account the substantial effect on the consensus values within limited number of data points, a recommendation on the provision of reference values assigned by accurate methods will be of benefit to small size PT programmes in the forensic field.

Development of melamine certified reference material in milk using two different isotope dilution mass spectrometry techniques.

A new certified reference material (CRM) of melamine in milk GLHK-11-02 was developed aiming to address the great demand from the testing community after the melamine crises. The material was prepared by adding an appropriate quantity of melamine into the skimmed milk samples and the final product was in the form of fine lyophilized powder. Characterization of the material relied on two newly developed gravimetric isotope dilution mass spectrometry (IDMS) methods, one using liquid chromatography-tandem mass spectrometry (LC-MS/MS) and another gas chromatography-mass spectrometry (GC-MS). Experimental parameters with crucial effects on the performance of the two IDMS methods were thoroughly investigated. These included purity of standard used, equilibration time of isotopes, efficiency of extraction methods as well as possible interferences from the matrix and melamine analogues. Precision was found to be excellent with a coefficient of variation of 2.5% for the LC-IDMS/MS (n=46) and 1.9% for the GC-IDMS (n=30) respectively. Using one-tail Student's t-test at 95% confidence interval, analytical data sets generated from the two methods were found to exhibit no significant difference. Measurement accuracy of the methods was further verified through an Asia Pacific Metrology Program (APMP) pilot study. Analytical results of the present LC-IDMS/MS for the two milk test samples at the concentration level of about 0.45 and 3.5 mg kg(-1) were proven to be very good. There were excellent overlaps between our results and the assigned reference values, and the absolute deviation was less than 3.2%. Both the LC-IDMS/MS and GC-IDMS methods were shown to be sufficiently reliable and accurate for certification of the melamine CRM. Certified value of melamine in dry mass fraction in GLHK-11-02 was 1.14 mg kg(-1). Expanded uncertainty due to sample inhomogeneity, long term and short term stability and variability in the characterization procedure was at 7.1% or 0.08 mg kg(-1). The CRM is primarily used to provide a complete method validation for and to improve the technical competence of melamine analysis to food and chemical testing laboratories.