Performance evaluation of polycyclic aromatic hydrocarbons analysis in sediment from proficiency testing with metrological reference values.

This paper describes a metrological approach to evaluate the measurement capability of laboratories participating in two proficiency testing (PT) programmes involving the analysis of five polycyclic aromatic hydrocarbons (PAHs) in sediment samples. Reference values of PAHs in the programmes for performance assessment were obtained from an accurate isotope dilution gas chromatography mass spectrometry (ID-GCMS) method which was thoroughly validated and verified. Isotope dilution mass spectrometry (IDMS) technique usually has a well-defined measurement uncertainty budget and a traceability link to an International System of Units. Provision of the metrological reference values in PT enables the establishment of a technical platform to assess the actual competence of the participating laboratories in sediment PAHs analysis. Results of the PT programmes showed that about 80 % of the laboratories employed gas chromatography in their analyses and the remaining used liquid chromatography. Irrespective of the techniques being used, however, the majority of the participating laboratories were observed to underestimate values in which the mean values of the five reported PAHs were less than those of the ID-GCMS-derived reference values by 13-20 %. Only 41-44 % of the participating laboratories were able to achieve satisfactory z-scores. The present study revealed that the reinforcement of the capability for accurate measurement of PAHs in sediment samples in laboratories worldwide should be addressed.

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.

Genetic differentiation between fake abalone and genuine Haliotis species using the forensically informative nucleotide sequencing (FINS) method.

Abalones ( Haliotis species) are a popular delicacy and commonly preserved in dried form either whole or in slices or small pieces for consumption in Asian countries. Driven by the huge profit from trading abalones, dishonest traders may substitute other molluscan species for processed abalone, of which the morphological characteristics are frequently lost in the processed form. For protection of consumer rights and law enforcement against fraud, there is a need for an effective methodology to differentiate between fake and genuine abalone. This paper describes a method (validated according to the international forensic guidelines provided by SWGDAM) for the identification of fake abalone species using forensically informative nucleotide sequence (FINS) analysis. A study of the local market revealed that many claimed "abalone slice" samples on sale are not genuine. The fake abalone samples were found to be either volutids of the genus Cymbium (93%) or the muricid Concholepas concholepas (7%). This is the first report of Cymbium species being used for the preparation and sale as "abalone" in dried sliced form in Hong Kong.

Application of isotope dilution gas chromatography-mass spectrometry in analysis of organochlorine pesticide residues in ginseng root.

A highly accurate and precise method based on isotope dilution gas chromatography-mass spectrometry was developed for the determination of five matrix-bound organochlorine pesticides, namely, hexachlorobenzene and hexachlorocyclohexanes (alpha-, beta-, delta-, and gamma- isomers), in a reference sample of Panax gingseng. Identification of the analytes was confirmed under selective ion monitoring mode by the presence of two dominant ion fragments within the specific time windows (+/-1% of the relative retention time with respect to the calibration standards) and matching of relative ion intensities of the concerned ions in samples and calibration standards (within +/-5%). Quantification was based on the measurement of concentration ratios of the natural and isotopic analogues in the sample and calibration blends. To circumvent the tedious iterative process of exact isotope matching that is often used in isotope dilution mass spectrometry analysis, a single-point calibration procedure was adopted with the isotopic amount ratios in the sample and calibration blends close to unity (0.9-1.1). Under the described approach, intraday and interday repeatability of replicate analyses of organochlorine pesticides in the ginseng root sample were below 1.4%. The expanded relative uncertainty ranging from 4.0 to 6.5% at a coverage factor of 2 was significantly lower than those of conventional gas chromatographic methods using other calibration techniques (internal or external standards). A deviation of less than 2.0% from the certified values was achieved when applying the developed method to determine hexachlorobenzene, alpha-, and beta-hexachlorocyclohexane in a certified reference material (CRM), BCR-CRM 115. Because of the unavailability of relevant CRMs of herbal origins, the concerned ginseng root sample, after verification of the "true values" of the concerned organochlorine pesticides by the valid primary method, is suitable for serving as an in-house reference material for quality assurance and method validation purposes.

Analysis of gamma-irradiated melon, pumpkin, and sunflower seeds by electron paramagnetic resonance spectroscopy and gas chromatography-mass spectrometry.

Seeds of melon (Citrullus lanatus var. sp.), pumpkin (Cucurbita moschata), and sunflower (Heliantus annus) were gamma-irradiated at 1, 3, 5, and 10 kGy and analyzed by electron paramagnetic resonance (EPR) and gas chromatography-mass spectrometry (GC-MS) according to EN1787:2000 and EN1785:2003, respectively. Distinguishable triplet signals due to the presence of induced cellulose radicals were found at 2.0010-2.0047 g in the EPR spectra. The gamma-irradiated radiolytic markers of 2-dodecylcyclobutanone (2-DCB) and 2-tetradecylcyclobutanone (2-TCB) were identified in all irradiated seed samples. Both the free radicals and the alkylcyclobutanones were found to increase with irradiation dose. In general, linear relationships between the amount of radicals and irradiation dosage could be established. Studies at an ambient temperature (20-25 degrees C) in a humidity-controlled environment showed a complete disappearance of the cellulosic peaks for irradiated samples upon 60 days of storage. Such instability behavior was considered to render the usefulness of using EPR alone in the determination of irradiated seed samples. On the other hand, 2-DCB and 2-TCB were also found to decompose rapidly (>85% loss after 120 days of storage), but the radiolytic markers remained quantifiable after 120 days of postirradiation storage. These results suggest that GC-MS is a versatile and complimentary technique for the confirmation of irradiation treatment to seeds.

Seasonal and spatial variation of solvent extractable organic compounds in fine suspended particulate matter in Hong Kong.

The results of a 12-month study of more than 100 solvent extractable organic compounds (SEOC) in particulate matter (PM) less than or equal to 2.5 microm (PM2.5) collected at three air monitoring stations located at roadside, urban, and rural sites in Hong Kong are reported. The total yield of SEOC that accounts for approximately 8-18% of organic carbon (OC) determined by a thermal optical transmittance method was 125-2060 ng/m3, which included 14.6-128 ng/m3 resolved aliphatic hydrocarbons, 39.4-1380 ng/m3 unresolved complex mixtures, 0.6-17.2 ng/m3 polycyclic aromatic hydrocarbons, 41.6-520 ng/m3 fatty acids, and < 0.1-12.1 ng/m3 alkanols. Distinct seasonal variations (summer/winter differences) were observed with higher concentrations of the total and each class of SEOC in the winter and lower concentrations in the summer. Spatial variations are also obvious, with the roadside samples having the highest concentrations of SEOC and the rural samples having the lowest concentrations in all seasons. Characteristic ratios of petroleum hydrocarbons, such as carbon preference index, unresolved to resolved components, and carbon number with maximum concentration, suggest that PM2.5 carbon in Hong Kong originates from both biogenic and anthropogenic sources. The proportion of SEOC in PM2.5 from anthropogenic sources is estimated.

PM2.5 chemical composition in Hong Kong: urban and regional variations.

Chemically speciated PM2.5 measurements were made at roadside, urban, and rural background sites in Hong Kong for 1 year during 2000/2001 to determine the spatial and temporal variations of PM2.5 mass and chemical composition in this highly populated region. Annual average PM2.5 concentrations at the urban and rural sites were 34.1 and 23.7 microg m(-3), respectively, approximately 50-100% higher than the United States' annual average National Ambient Air Quality Standard (NAAQS) of 15 microg m(-3). Daily PM2.5 concentrations exceeded the U.S. 24-h NAAQS of 65 microg m(-3) on 19 days, reaching 131+/-8 microg m(-3) at the roadside site on 02/28/2001. Carbonaceous aerosol is the largest contributor to PM2.5 mass (explaining 52-75% of PM2.5 mass at the two urban sites and 32% at the background site), followed by ammonium sulfate (ranging from 23% to 37% at the two urban sites and 51% at the background site). Ammonium sulfate and crustal concentrations showed more uniform spatial distributions, while the largest urban-rural contrasts found in carbonaceous aerosol (likely due to emissions from on-road gasoline and diesel vehicles). Marine influences accounted for 7% of the mass at the background site (more than twice as much as at the two urban sites). Ternary diagrams are utilized to illustrate the different spatial patterns.

Determination and on-line clean-up of (fluoro)quinolones in bovine milk using column-switching liquid chromatography fluorescence detection.

A simple, cost-effective, and high throughput method using on-line column-switching liquid chromatography fluorescence detection was developed and validated for analysing five (fluoro)quinolones (FQs)--enrofloxacin (ENRO), ciprofloxacin (CIPR), sarafloxacin (SARA), oxolinic acid (OXOL), and flumequine (FLUM) in bovine milk. Norfloxacin (NORF) and nalixidic acid (NALI) were used as internal standards. After simple deproteination of milk sample with 5% (w/v) metaphosphoric acid, the supernatant was subject to on-line column clean-up and direct analysis by LC-FLD. The extraction cartridge was prepared in-house by slurry packing with hydrophilic-lipophilic polymer sorbent. The accuracy of measurement for each (fluoro)quinolone at different maximum residue limits (MRL) was 101-103% (ENRO), 92.8-97.4% (CIPR), 89.8-92.8% (SARA), 116-121% (OXOL), and 81.3-85.5% (FLUM), whilst the precision was 2.9-6.1% (ENRO), 2.5-5.1% (CIPR), 2.3-5.0% (SARA), 3.1-5.9% (OXOL), and 5.6-6.5% (FLUM). The decision limits, detection capabilities, specificity and analytes stability during storage were also investigated.

Distribution of polycyclic aromatic hydrocarbons in the atmosphere of Hong Kong.

This paper reports the monitoring results of eleven polycyclic aromatic hydrocarbons (PAHs), four to six-ring, at two urban sites-Central & Western (CW) and Tsuen Wan (TW) in Hong Kong from January to December 2000; and the findings of a study conducted in 2001 of the partitioning of the gaseous and particulate phases of PAHs. The sum of the eleven PAHs under study (sigmaPAHs) was found to range from 6.46 to 38.8 ng m(-3). The annual mean levels at 12.2 ng m(-3) and 15.8 ng m(-3) for CW and TW respectively are comparable to those recorded for the previous two years and are also within the reported ranges for other metropolitan cities in the Asia Pacific region. Amongst the selected eleven PAHs, fluoranthene and pyrene were the two most abundant found in the urban atmosphere of Hong Kong during the study period accounting for approximately 80%, of the total PAHs. The ratios of benzo(a)pyrene to benzo(g,h,i)perylene (BaP/BghiP) and indeno(1,2,3-cd)pyrene to benzo(g,h,i)perylene (IDP/BghiP) indicate that diesel and gasoline vehicular exhausts were the predominant local emission sources of PAHs. Seasonal variations with high winter to summer ratios for each of the individual PAHs (CW: 1.6-16.7 and TW: 0.82-8.2) and for sigmaPAHs (CW: 1.9 and TW: 1.8) and a spatial variation of BaP amongst the air monitoring stations are noted. Results of correlation studies illustrate that local meteorological conditions such as ambient temperature, solar radiation, wind speed and wind direction have significant impact on the concentrations of atmospheric PAHs accounting for the observed seasonal variations. A snapshot comparison of the concentrations of PAHs at four sites including a roadside site, a rural site and the two regular urban sites CW and TW was also performed using the profiles of PAHs recorded on two particulate episode days in March 2000.