Determination of analytical limits in solid sampling ETAAS: a new approach towards the characterization of analytical quality in rapid methods

In the present study the lower analytical limits of solid sampling electrothermal atomization atomic absorption spectrometry (SS-ETAAS) were characterized by means of blank measurements and – for the first time – by means of the calibration curve method, where a calibration near the range of these limits (limit of decision, detection and quantification) was performed. The limit of decision as derived from blank measurements was calculated according to the 3σ-criterion to be 0.003 and 0.019 ng for Cd and Pb, respectively. For Pb and Cd a roughly threefold increase of these limits was observed when the calibration method according to DIN 32 645 was applied. When solid reference material was used, only a slight increase could be observed. The analytical limits were 2 to 20 times lower than reported for sample decomposition methods. The blank measurement and conventional calibration curve method, however, do not account for factors relating to solid sampling such as sample mass and matrix. Therefore, the calibration curve model was applied to data derived from comparisons between direct solid sampling ETAAS and a compound reference method (ETAAS following sample homogenization and digestion). The observed analytical limits were not found to be substantially increased if enough samples with low element contents were available for calibration. Coupling of the calibration curve model with the comparison of methods included real test samples and thus the relevant maximum sample mass and analyte content in the range of the lower analytical limits. As validation procedures frequently include comparisons of methods, the present approach might prove to be of some general interest for the characterization of analytical quality in rapid methods.     

Determination of element concentrations in biological reference materials by solid sampling and other analytical methods

Summary Using solid sampling with graphite furnace atomic absorption spectrometry (GFAAS), values for cadmium, copper, lead and zinc in six biological reference materials were obtained from up to four laboratories participating in three collaborative studies. These results are compared with those obtained with other methods used in routine analysis from laboratories of official food control. Under certain conditions solid sampling with GFAAS seems to be suitable for routine analysis as well as conventional methods.     

A rapid solid sampling method for determination of nickel and copper along human hair by ETAAS

A procedure for copper and nickel determination in scalp hair by solid sampling electrothermal atomic absorption spectrometric method was described. The hair samples (0.02 to 0.4 mg) were inserted directly on the platforms of solid sampling autosampler. The effects of pyrolysis temperature, atomization temperature, the amount of sample as well as addition of a modifier (Pd/Mg) and/or auxiliary digesting agents (hydrogen peroxide and nitric acid) and/or a surfactant (Triton X-100) on the determination of copper and nickel by solid sampling atomic absorption spectrometry were investigated. After optimization of parameters, the average recoveries of copper in two different certified reference hair samples were 105.7 and 97.6%. The recoveries of nickel in the both certified reference hair samples were in 95.2 and 96.4%. The limits of detection (3σ, N = 10) for copper and nickel were 22 ng/g and 35 ng/g, respectively. Heterogenous distribution of analyte in microscale for segmental analysis could be determined which is important to know that analyte quantity and time of poisoning of a person was exposed. For this purpose, 0.5 cm of pieces were cut along one or a few close strands and analyzed by solid sampling. This process could not be performed by wet-digestion method because 50 mg of sample is needed each time. Finally, the method was applied for the determination of copper and nickel concentrations in the hairs of different persons.     

A new and consistent parameter for measuring the quality of multivariate analytical methods: Generalized analytical sensitivity

Generalized analytical sensitivity (γ) is proposed as a new figure of merit, which can be estimated from a multivariate calibration data set. It can be confidently applied to compare different calibration methodologies, and helps to solve literature inconsistencies on the relationship between classical sensitivity and prediction error. In contrast to the classical plain sensitivity, γ incorporates the noise properties in its definition, and its inverse is well correlated with root mean square errors of prediction in the presence of general noise structures. The proposal is supported by studying simulated and experimental first-order multivariate calibration systems with various models, namely multiple linear regression, principal component regression (PCR) and maximum likelihood PCR (MLPCR). The simulations included instrumental noise of different types: independently and identically distributed (iid), correlated (pink) and proportional noise, while the experimental data carried noise which is clearly non-iid.     

The analytical characterization of municipal solid waste incinerator fly ash: methods and preliminary results

ICP/OES, AES, ETAAS, TXRF, IC, XRPD, XPS, SEM/EDX, FT-IR, Raman, M?ssbauer and ESR have been used to characterize inorganic components in a fly ash sample. It has been possible to determine silicates and aluminium silicates (gehlenite, gismondine and cabasite) in addition to many inorganic compounds (halite, sylvite, anhydrite, bassanite, gypsum, syngenite, ettringite, haematite, calcite and rutile). Received: 17 March 1999 / Revised: 14 June 1999 / Accepted: 21 June 1999     

The analytical characterization of municipal solid waste incinerator fly ash: methods and preliminary results

ICP/OES, AES, ETAAS, TXRF, IC, XRPD, XPS, SEM/EDX, FT-IR, Raman, Mössbauer and ESR have been used to characterize inorganic components in a fly ash sample. It has been possible to determine silicates and aluminium silicates (gehlenite, gismondine and cabasite) in addition to many inorganic compounds (halite, sylvite, anhydrite, bassanite, gypsum, syngenite, ettringite, haematite, calcite and rutile).     

A new approach for the determination of sulphur in airborne particles by HR-CS ETAAS

In this work, water and nitric acid extractable sulphur concentrations in PM2.5 fraction of urban aerosols were determined by high-resolution continuum source electrothermal molecular absorption spectrometry using most suitable CS molecular absorption band at 258.056 nm. For this purpose, the PM2.5 airborne particulates were collected on quartz filters using a high-volume sampler (500 L/min) in Istanbul (Turkey) during six months (January–June) of two consecutive years. The instrumental and experimental parameters (pyrolysis temperature, molecule formation temperature and leaching reagents) were optimised. The validity of the method for the sulphur was tested using standard reference material and the results were found to be in the uncertainty limits of the certified value.     

Determination of trace elements in lithium niobate crystals by solid sampling and solution-based spectrometry methods

Solid sampling (SS) graphite furnace atomic absorption spectrometry (GFAAS) and solution-based (SB) methods of GFAAS, flame atomic absorption spectrometry (FAAS), inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS) were elaborated and/or optimized for the determination of Cr, Fe and Mn trace elements used as dopants in lithium niobate optical crystals.     

Determination of arsenic in mussels by slurry sampling and electrothermal atomic absorption spectrometry (ETAAS)

A method for the determination of arsenic in slurries of mussel tissue using palladium-magnesium nitrate as modifier was optimized. The slurry was stabilized by a 0.015% (v/v) of Triton X-100. To achieve complete mineralization the slurries were ashed at 480 °C for 10s in an air flow (50 ml/min) and at 1200 °C for 15s in an argon flow (300 ml/min) in the presence of Pd—Mg(NO₃)₂ as modifier. The optimum atomization temperature was 2200 °C. The precision and accuracy of the method were studied using the Reference Material BCR n ° 278 Mussel Tissue (Mytilus edulis). The detection limit (LOD) of the final slurry solution was 1 g/l of arsenic corresponding to an arsenic level in the mussel of 1.3 g/g, for a 0.5% (m/v) slurry. Results of calibration using aqueous standards and the standard additions method were compared. The method was applied to the determination of arsenic in mussels from the Galician coast. The levels found lie between 2 and 9.3 g/g of arsenic.     

Comparison of analytical methods for the quality control of a new formulation containing soy extract and melatonin

Three analytical methods have been developed and compared for the quality control of a new formulation (Soymen GN(R) capsules) containing soy extract and melatonin for the treatment of menopausal symptoms. The first method is based on MEKC with diode-array detection, using a mixture of basic carbonate buffer (95%) and methanol (5%), containing 55 mM SDS, as the BGE. The second method is an HPLC method with UV detection at 260 nm. The third method is an HPLC method coupled to amperometric detection which is carried out at an oxidation potential of +0.8 V. In both HPLC systems, the chromatographic separation is obtained on an RP C18 column using a mixture of ACN and an acidic phosphate buffer (25:75 v/v) as the mobile phase. A feasible pretreatment procedure with a methanol/water mixture has been implemented to achieve the quantitative extraction of the main soy isoflavones and of melatonin from the capsules. The results obtained with the three methods are in good agreement with each other and satisfactory in terms of linearity (r(2) >0.9996), precision (RSD <5.4%) and accuracy (recovery >97%). Thus, each of the three analytical methods seems to be suitable for the simultaneous analysis of the main soy isoflavones and melatonin in the new commercial formulation.     

Distribution of low-density lipoprotein-bound low-molecular-weight thiols: a new analytical approach

We have recently demonstrated that low-density lipoprotein (LDL) apoprotein is able to bind the most concentrated plasma thiols such as cysteine, cysteinylglycine, and homocysteine by disulfide linkage. However, the LIF CE assay employed to measure linked thiols was not sensitive enough to verify whether low concentrated plasma thiols as glutathione and glutamylcysteine are also linked to apoprotein. By modifying sample treatment and electrophoretic parameters we set up a new method with an LOQ of about 1.5 nmol/L, by which we demonstrate that LDL apoprotein binds all physiological plasma thiols. The increased sensitivity was obtained by drying released apoB thiols after reduction treatment, dissolving them directly in a low volume of derivatization buffer and decreasing the dilution factor of derivatized sample before CE injection. Moreover, by increasing the concentration of the electrolyte buffer, we improved the selectivity of peaks, in particular between glutathione (GSH) and the impurity peak derived from unreacted 5-iodoacetamidofluorescein, which in the previous electrophoretic conditions were overlapped. The method optimization, reached by searching the best combination between sample matrix and CE run buffer, is fully described. Given the potential pathologic significance of protein thiolation, the proposed method may be useful to understand the mechanisms and the balances that regulate the interaction between thiols and -SH free groups of proteins.     

Validation of analytical methods involved in dissolution assays: Acceptance limits and decision methodologies

Dissolution tests are key elements to ensure continuing product quality and performance. The ultimate goal of these tests is to assure consistent product quality within a defined set of specification criteria. Validation of an analytical method aimed at assessing the dissolution profile of products or at verifying pharmacopoeias compliance should demonstrate that this analytical method is able to correctly declare two dissolution profiles as similar or drug products as compliant with respect to their specifications. It is essential to ensure that these analytical methods are fit for their purpose. Method validation is aimed at providing this guarantee. However, even in the ICHQ2 guideline there is no information explaining how to decide whether the method under validation is valid for its final purpose or not. Are the entire validation criterion needed to ensure that a Quality Control (QC) analytical method for dissolution test is valid? What acceptance limits should be set on these criteria? How to decide about method's validity? These are the questions that this work aims at answering. Focus is made to comply with the current implementation of the Quality by Design (QbD) principles in the pharmaceutical industry in order to allow to correctly defining the Analytical Target Profile (ATP) of analytical methods involved in dissolution tests. Analytical method validation is then the natural demonstration that the developed methods are fit for their intended purpose and is not any more the inconsiderate checklist validation approach still generally performed to complete the filing required to obtain product marketing authorization.     

A new analytical approach for the comprehensive characterization of polar xenobiotic organic compounds downgradient of old municipal solid waste (MSW) landfills

Groundwater samples collected downgradient from a former municipal solid waste landfill near Berlin, Germany, were analyzed by GC-MS, HPLC-MS, and HPLC-NMR hyphenated techniques to comprehensively characterize the xenobiotic organic compounds (XOCs). The focus thereby was on the detection and identification of the polar XOCs which were analyzed in the extract obtained after separation of the unpolar components by pre-extraction. HPLC-NMR and HPLC-MS runs were used to identify polar XOCs on-line or to obtain preliminary structure information on the other XOCs. These compounds were then isolated by HPLC fractionation and their structures elucidated by off-line NMR and MS investigations. A variety of polar XOCs, products of the dye industry, degradation products of polyethylene glycol, and some heterocyclic compounds could be identified. Furthermore, a semi-quantitative estimation of the identified polar compounds is given.     

Nuclear analytical methods in quality control of microanalysis

Quantitative calibration and quality control have been a major bottleneck in microanalysis due to the lack of natural-matrix CRMs certified at sample sizes compatible with those of unknown samples. In this paper, a solution is described to characterize sampling behavior for individual elements, so as to identify elements homogeneous enough at stated sample size levels in given CRMs/RMs. By using a combination of several nuclear analytical techniques, INAA-EDXRF-μPIXE, sampling behavior for individual elements can be characterized at sample size levels from grams down to pg. Natural-matrix CRMs specifically for QC of microanalysis may thus be created. Additional information in certificates of these new generation CRMs is imagined. This revised version was published online in July 2006 with corrections to the Cover Date.     

Absolute assessment of adsorption-based porous solid characterization methods: comparison methods

The design and use of microporous solids depends on having access to characteristics such as the pore volume and surface area. Comparison methods such as the alpha(s) method are one of the most widely used means of determining these parameters. An assessment of this group of methods was undertaken by comparing estimates obtained from them using adsorption isotherms generated by grand canonical Monte Carlo simulation on a selection of model nanoporous solids with exactly known surface areas and pore volumes. Conclusions are drawn from this absolute assessment in regard to the validity of the alpha(s) method for determining the micropore volume, the mesopore surface area, and the separation of pore groups based on the concept of primary and cooperative filling, the subtracting pore effect (SPE) method, and the required character of the reference surface.     

A new solid phase approach for rapid syntheses of oligonucleotides bearing a 3′-terminal phosphate group

Synthesis of pentanucleotide ApTpCpTpTp containing a 3′-terminal phosphomonoester group was accomplished with the help of the new phosphate-solid phase link 2-(4-carboxyphenyl-mercapto)ethanol; a similar molecule, 2-benzylsulfonylethanol, revealed interesting features as a temporary 3′-phosphate protecting group.     

Passive sampling as a tool for obtaining reliable analytical information in environmental quality monitoring

Passive sampling technology has been developing very quickly for the past 20 years, and is widely used for monitoring pollutants in different environments, for example air, water, and soil. It has many significant advantages, including simplicity, low cost, no need for expensive and complicated equipment, no power requirements, unattended operation, and the ability to produce accurate results. The present generation of passive samplers enables detection and analysis of bioavailable pollutants at low and very low concentrations and investigation of the environmental concentration of organic and inorganic pollutants not only on the local scale but also on continental and global scales. This review describes the current application of passive sampling techniques in environmental analysis and monitoring, under both equilibrium and non-equilibrium conditions.