Analytical Quality Assurance Procedures Developed for the IAEA's Reference Asian Man Project (Phase 2)

Analytical quality assurance procedures adopted for use in the IAEA Co-ordinated Research Project on Ingestion and Organ Content of Trace Elements of Importance in Radiological Protection are designed to ensure comparability of the analytical results for Cs, I, Sr, Th, U and other elements in human tissues and diets collected and analysed in nine participating countries. The main analytical techniques are NAA and ICP-MS. For sample preparation, all participants are using identical food blenders which have been centrally supplied after testing for contamination. For quality control of the analyses, six NIST SRMs covering a range of matrices with certified and reference values for the elements of interest have been distributed. A new Japanese reference diet material has also been developed. These quality assurance procedures are summarized here and new data are presented for Cs, I, Sr, Th and U in the NIST SRMs.     

Quality assurance and quality control for thermal/optical analysis of aerosol samples for organic and elemental carbon

Accurate, precise, and valid organic and elemental carbon (OC and EC, respectively) measurements require more effort than the routine analysis of ambient aerosol and source samples. This paper documents the quality assurance (QA) and quality control (QC) procedures that should be implemented to ensure consistency of OC and EC measurements. Prior to field sampling, the appropriate filter substrate must be selected and tested for sampling effectiveness. Unexposed filters are pre-fired to remove contaminants and acceptance tested. After sampling, filters must be stored in the laboratory in clean, labeled containers under refrigeration (<4 °C) to minimize loss of semi-volatile OC. QA activities include participation in laboratory accreditation programs, external system audits, and interlaboratory comparisons. For thermal/optical carbon analyses, periodic QC tests include calibration of the flame ionization detector with different types of carbon standards, thermogram inspection, replicate analyses, quantification of trace oxygen concentrations (<100 ppmv) in the helium atmosphere, and calibration of the sample temperature sensor. These established QA/QC procedures are applicable to aerosol sampling and analysis for carbon and other chemical components.     

Synthesis and analytical application of a novel tetradentate N(2)O(2) Schiff base as a chromogenic reagent for determination of nickel in some natural food samples

A novel sensitive chromogenic reagent, N,N′-bis(3-methylsalicylidene)-ortho-phenylene diamine (MSOPD), has been synthesized and used in the spectrophotometric determination of nickel. At pH 8, MSOPD can react with nickel ion at room temperature to form a 1:1 complex. The apparent molar absorptivity is 9.5 × 10⁴ l mol⁻¹ cm⁻¹ at 430 nm. Beer's low is obeyed over the range 0-1.0 × 10⁻⁵ M of nickel with a detection limit of 1.36 × 10⁻⁸ M. The relative standard deviation for measurement of 3.41 × 10⁻⁶ M nickel is 1.3% (n = 10). The method has successfully been applied to determination of trace amounts of nickel in some natural food samples.     

Spectrophotometric method for the determination of sorbic acid in various food samples with iron(III) and 2-thiobarbituric acid as reagents

A simple, rapid and accurate spectrophotometric method has been developed for the determination of sorbic acid in various food samples based on the oxidation of sorbic acid by iron(III) at 100 degrees C to malonaldehyde, which then reacts with 2-thiobarbituric acid to form a reddish brown product. The optimum experimental conditions for colour development have been assessed. Absorbance measurements were made at 529 nm in the presence of 0.4% m/V citric acid. The calibration graph was linear for 0-6 micrograms ml-1 of sorbic acid with a slope of 0.131 A micrograms-1 ml. The recoveries of sorbic acid at concentrations of 164-557 micrograms ml-1 ranged from 96 to 103%. The relative standard deviations of ten replicate determinations of sorbic acid in a synthetic cream soda sample spiked with 573 micrograms ml-1 of sorbic acid and in an onion juice sample containing 82 micrograms ml-1 of sorbic acid were 1.6 and 1.9%, respectively. Interferences from several common food additives can be minimised by extracting sorbic acid with diethyl ether and then back-extracting the acid with sodium hydrogen carbonate. The method has been applied successfully to the determination of sorbic acid in a wide range of food samples including beverages, cake, cake mate, garlic bread sprinkle, onion juice, oyster flavoured sauce and grenadine syrup.     

Quality control and quality assurance aspects of the routine use of capillary electrophoresis for serum and urine proteins in clinical laboratories

Using capillary electrophoresis (CE) for serum protein electrophoresis, the quality of results begins with monitoring a well-functioning instrument, using scrupulously clean capillaries, well-calibrated methods as well as regular use of an internal quality control material. Quality assurance programs are available in countries such as Australia, United Kingdom, United States, and European countries such as Sweden and Germany. The present commercial control material that is available gives percentages of albumin, alpha 1, alpha 2, beta- and gamma-globulins, the gamma-component being of normal distribution, and not containing any monoclonal protein component. We feel that a quantitative commercial control material containing a monoclonal protein at decision level for treating myeloma patients would be beneficial to all laboratories as a serum protein electrophoresis control, whether the analysis is by CE or agarose gels. The same applies for control material for urinary protein electrophoresis.     

Quality assurance of iodine-124 produced via the nuclear reaction124Te (d, 2n)124I

For more than a year,¹²⁴I (T=4.15 d) has been produced routinely with a compact cyclotron by irradiation of¹²⁴TeO₂ with 14 MeV deuterons, followed by dry distillation of the iodine radioisotopes formed from irradiated target materials. The following by-products have been measured and compiled in each charge: 13.2-d¹²³I, 60-d¹²⁵I, 13.0-d¹²⁶I, 12.4-h¹³⁰I and 8.02-d¹³¹I. The data show that after 45 h decay time, the sum of the activities of these nuclides is less than 5% of the¹²⁴I activity. Observation of this limit has been required by the Swiss Regulatory Agencies for a PET study of cell proliferation in human brain tumors using [¹²⁴I] IUdR.     

Novel thionin-functionalised core shell magnetic nanoparticles for dispersive solid-phase extraction of Hg(II) in food and water samples

To develop an accurate and precise method for separation and pre-concentration of Hg(II), a novel thionin functionalised core shell structure magnetic material has been prepared and characterised. The extraction ability of the material was evaluated by magnetic solid-phase extraction coupled with inductively coupled plasma mass spectrometry determination of Hg(II) in food and water samples. Combining the advantages of magnetic separation with selective extraction of thionin towards Hg(II), the material exhibits enhanced enrich selectivity and efficiency for Hg(II). The experimental parameters influencing Hg(II) extraction efficiency, including pH of the aqueous solution, the dosage of the adsorbent, extraction time and sample volume, were systematically investigated. Under the optimised conditions, concentration of Hg(II) at 1.0 μg L^?1 can be successfully enriched by the material without the interference of the common co-existing ions. The enrichment factor and adsorption capacity were 250 and 75.2 mg g^?1, and precise of the method was confirmed by analysing the spiked food, water samples and standard water reference samples with the recoveries of 92.5–101.8%.     

Results of the second inventory on quality assurance/quality control (QA/QC) and good laboratory practice (GLP) for European Union National Reference Laboratories for residue analyses.

In February 1996 the "Second inventory on QA/QC and GLP for EU-NRLs" was submitted to all European Union National Reference Laboratories (EU-NRLs) for residue analyses. This second inventory was a follow up on the "Inventory on QA/QC" (1993) which was used for the organisation of the first workshop on "GLP for EC-NRLs". In February 1997 a response on the second inventory of 100% was achieved. From the completed inventories it became evident that almost all EU-NRLs for residue analyses now have a described quality program based on an international standard. However only 33% of the EU-NRLs are officially accredited, certified or in compliance with good laboratory practice (GLP) principles. Most of the accredited EU-NRLs have a quality program based on the European Standard EN45001. Seven of the EU-NRLs still do not have a described quality program or have not appointed a quality officer and for 12 of the EU-NRLs the independence of the QA officer is not formally arranged. Only about 50% of the EU-NRLs have a standard operating protocol (SOP) to handle complaints. Almost all of the EU-NRLs have SOPs available and a system to control them. In comparison with the results of the first inventory it is evident that most of the EU-NRLs have made considerable progress in the implementation of quality systems. However it is also evident that a substantial number of EU-NRLs still lack some critical QA facilities. The new deadline for the full implementation of all relevant QA facilities is January 2002.     

6-Oxy-(N-succinimidyl acetate)-9-(2'-methoxycarbonyl)fluorescein as a new fluorescent labeling reagent for aliphatic amines in environmental and food samples using high-performance liquid chromatography

6-Oxy-(N-succinimidyl acetate)-9-(2'-methoxycarbonyl)fluorescein (SAMF), a new fluorescein-based amine-reactive fluorescent probe was well designed, synthesized and used as a pre-column derivatizing reagent for the determination of aliphatic amines in HPLC. It exhibited relatively pH-independent fluorescence (pH 4-9) and excellent photostability. The derivatization was performed at room temperature in 6min. On a C18 column, the derivatives of SAMF with eight aliphatic amines were baseline separated in 28 min with a mobile phase of methanol-water (57:43, v/v) containing 10 mmol l(-1) pH 5.0, H3Cit3-NaOH buffer. With fluorescent detection at lambda(ex)/lambda(em) = 484/516 nm, the detection limit could reach 2-320 fmol (signal-to-noise = 3), which was equivalent to or better than the detection limits obtained from other analytical methods of aliphatic amines. The proposed method has been applied to the determination of the aliphatic amines in environmental and food samples such as lake water, red wine, white wine, and cheese with satisfying recoveries varying from 95 to 106%.     

Preconcentration of Cd(II) and Cu(II) ions by coprecipitation without any carrier element in some food and water samples

A simple, rapid, sensitive and environmentally friendly separation and preconcentration procedure, based on the carrier element free coprecipitation (CEFC) of Cu(II) and Cd(II) ions by using an organic coprecipitant, 2-{[4-(4-fluorophenyl)-5-sulphanyl-4H-1,2,4-triazol-3-yl]methyl}-4-{[(4-fluorophenyl) methylene]amino}-5-(4-methylphenyl)-2,4-dihydro-3H-1,2,4-triazol-3-one (MEFMAT) was developed. The analyte ions were determined by flame atomic absorption spectrometric (FAAS) determinations. The optimum conditions for the coprecipitation process were investigated on several commonly tested experimental parameters such as pH of the solution, amount of MEFMAT, sample volume, standing time, centrifugation rate and time. The influences of some anions, cations and transition metals on the recoveries of analyte ions were also investigated, and no considerable interference was observed. The preconcentration factor was found to be 50. The detection limits for Cu(II) and Cd(II) ions based on the three times the standard deviation of the blanks (N:10) were found to be 1.49 and 0.45 μg L^{− 1}, respectively. The relative standard deviations were found to be lower than 3.5% for both analyte ions. The method was validated by analyzing two certified reference materials (CRM-TMDW-500 Drinking Water and CRM-SA-C Sandy Soil C) and spike tests. The procedure was successfully applied to sea water and stream water as liquid samples and tobacco, hazelnut and black tea as solid samples.     

Binary Phase Behavior of 1,3-Distearoyl-2-oleoyl-sn-glycerol (SOS) and Trilaurin (LLL)

This paper reports the precise analysis of the eutectic mixing behavior of 1,3-distearoyl-2-oleoyl-sn-glycerol (SOS) and trilaurin (LLL), as a typical model case of the mixture of cocoa butter (CB) and cocoa butter substitute (CBS). SOS was mixed with LLL at several mass fractions of LLL (w_LLL); the mixtures obtained were analyzed for polymorphic phase behavior using differential scanning calorimetry (DSC) and synchrotron radiation X-ray diffractometry (SR-XRD). In melt crystallization with constant-rate cooling, SOS and LLL formed eutectics in their metastable polymorphs, allowing the occurrence of a compatible solid solution at w_LLL ≥ 0.925. With subsequent heating, the resultant crystals transformed toward more stable polymorphs, then melted in a eutectic manner. For mixtures aged at 25 °C after melt crystallization, eutectics were found in the extended w_LLL region, even at w_LLL = 0.975. These results indicate that phase separation between SOS and LLL progressed in their solid solution under stabilization. The crystal growth of the separated SOS fraction may cause fat-bloom formation in compound chocolate containing CB and CBS. To solve this problem, the development of retardation techniques against phase separation is expected.     

Quartz crystal microbalance (QCM) in high-pressure carbon dioxide (CO2): experimental aspects of QCM theory and CO2 adsorption

The quartz crystal microbalance (QCM) technique has been developed into a powerful tool for the study of solid-fluid interfaces. This study focuses on the applications of QCM in high-pressure carbon dioxide (CO2) systems. Frequency responses of six QCM crystals with different electrode materials (silver or gold) and roughness values were determined in helium, nitrogen, and carbon dioxide at 35-40 degrees C and at elevated pressures up to 3200 psi. The goal is to experimentally examine the applicability of the traditional QCM theory in high-pressure systems and determine the adsorption of CO2 on the metal surfaces. A new QCM calculation approach was formulated to consider the surface roughness contribution to the frequency shift. It was found that the frequency-roughness correlation factor, Cr, in the new model was critical to the accurate calculation of mass changes on the crystal surface. Experiments and calculations demonstrated that the adsorption (or condensation) of gaseous and supercritical CO2 onto the silver and gold surfaces was as high as 3.6 microg cm(-2) at 40 degrees C when the CO2 densities are lower than 0.85 g cm(-3). The utilization of QCM crystals with different roughness in determining the adsorption of CO2 is also discussed.     

Phase Analysis of the Binary System of Cryolite (Na3AlF6) and Sodium Metasilicate (Na2SiO3)

The phase analysis of cryolite (Na₃AlF₆) and sodium metasilicate (Na₂SiO₃) was performed by thermal analysis. The eutectic system with a region of two immiscible substances at a concentration of Na₂SiO₃ between 42.8 and 46.3 mol‐% was identified and the eutectic temperature determined to (886±2) °C. Based on the results of mass‐loss measurements, it was assumed that the introduced Na₂SiO₃ reacts with Na₃AlF₆ due to the formation of some nonvolatile stable compounds. The stable reaction products were identified by X‐ray diffraction analysis and IR spectroscopy of the spontaneously cooled samples, which established the formation of NaF and stable amorphous aluminosilicate compounds.     

Solid phase extraction of heavy metals on chemically modified silica-gel with 2-(3-silylpropylimino) methyl)-5-bromophenol in food samples

Trace amounts of Fe³⁺, Pb²⁺, Cu²⁺, Ni²⁺, Co²⁺ and Zn²⁺ ions were efficiently enriched following complexation with silica-gel chemically functionalized with 2-((3-silylpropylimino)methyl)-5-bromophenol. The enriched metal ions efficiently eluted with 6?mL of 4.0?mol?L^?1 nitric acid and their metal contents were determined by flame atomic absorption spectrometry (FAAS). The influences of the analytical parameters and experimental variables on the recoveries of the metal ions under study were investigated and optimized. The method has high sorption preconcentration efficiency even in the presence of various interfering ions. At optimum values of all variables the method is applicable for analysis of real samples with recoveries in the range of 95 to 105% with RSD lower than 4.2% and detection limits between 1.4 and 2.8?µg?L^?1.     

Validation and application of an HPLC method for determination of di (2-ethylhexyl) phthalate and mono (2-ethylhexyl) phthalate in liver samples

A reversed-phase gradient elution, UV detection method is developed for the simultaneous determination of mono (2-ethylhexyl) phthalate [MEHP] and di (2-ethylhexyl) phthalate [DEHP] in tissue samples. The method is validated with respect to extraction recovery, inter and intra-day precision, linearity of response, detect ability, and specificity. The validated method has been successfully applied to the study of DEHP and MEHP in liver, kidney, testis, brain, and plasma samples from rat.