Spectrophotometric reaction-rate method for the determination of nitrite in waters with pyridine-2-aldehyde 2-pyridylhydrazone

A method for the kinetic determination of submicrogram amounts of nitrite has been developed, based on its acceleration of the rate of bromate oxidation of pyridine-2-aldehyde 2-pyridylhydrazone in acidic medium. The reaction is monitored spectrophotometrically at 372 nm. A comparative study with hydrochloric acid and perchloric acid media shows that the analytical parameters are affected by the type of acid used. Within-day precision, based on ten replicate determinations, was better than 0.011 μ/ml, which corresponds to 2.2-1.5% relative standard deviation at the concentrations examined. Application of this method in the determination of nitrite in water has been discussed. The recovery of nitrite from drinking waters ranges from 90 to 117% and the average relative standard deviation for nitrite determinations in polluted river water is 3.2%. Large amounts of nitrate and ammonium ions do not interfere. However, there is interference by Cu²⁺, Pd²⁺ and electroactive substances. Major advantages for the method are simplicity, absence of a reagent blank, and the wide determination range.     

Calculation of the best estimates for measurements of radioactive substances when the presence of the analyte is not assured

The best estimate and its standard deviation are calculated for the case when the a priori probability that the analyte is absent from the test sample is not zero. In the calculation, a generalization of the Bayesian prior that is used in the ISO 11929 standard is applied. The posterior probability density distribution of the true values, given the observed value and its uncertainty, is a linear combination of the Dirac delta function and the normalized, truncated, normal probability density distribution defined by the observed value and its uncertainty. The coefficients of this linear combination depend on the observed value and its uncertainty, as well as on the a priori probability. It is shown that for a priori probabilities larger than zero the lower level of the uncertainty interval of the best estimate reaches the unfeasible range (i.e., negative activities). However, for a priori probabilities in excess of 0.26 it reaches the unfeasible range even for positive observed values. The upper limit of the confidence interval covering a predefined fraction of the posterior is derived.     

Sensitive Kinetic-Spectrophotometric Determination of Trace Amounts of Periodate Ion

A simple, precise, sensitive and accurate method was developed for rapid determination of trace quantities of periodate. The method is based on the accelerating effect of periodate on the reaction of bromate and hydrochloric acid in the presence of hydrazine. The decolorization of methyl orange with the reaction products was used to monitor the reaction spectrophotometrically at 525 nm. Periodate could be determined in the concentration ranges of 0.02–1.5 g/mL. The relative standard deviation for ten replicate determinations of 0.3 g/mL of periodate was 1.12%. The method was applied to the determination of periodate in water samples and indirect determination of ethylene glycol in gasoline and glycerol in vegetable oil via Malaprade reaction with satisfactory results.     

An automated procedure for the simultaneous determination of specific conductance and pH in natural water samples

An automated, continuous-flow system is utilized to determine specific conductance and pH simultaneously in natural waters. A direct electrometric procedure is used to determine values in the range pH 4–9. The specific conductance measurements are made with an electronically modified, commercially available conductivity meter interfaced to a separate module containing the readout control devices and printer. The system is designed to switch ranges automatically to accommodate optimum analysis of widely varying conductances ranging from a few μmhos cm^-1 to 15,000 μmho cm^-1. Thirty samples per hour can be analyzed. Comparison of manual and automated procedures for 40 samples showed that the average differences were 1.3% for specific conductance and 0.07 units for pH. The relative standard deviation for 25 replicate values for each of five samples was significantly less than 1% for the specific conductance determination; the standard deviation for the pH determination was ? 0.06 pH units.     

Sensitive kinetic-spectrophotometric determination of iodate in iodized table salt based on its accelerating effect on the reaction of bromate with chloride ion in the presence of hydrazine.

A simple, precise, sensitive and accurate method was developed for rapid determination of trace quantities of iodate. The method is based on the accelerating effect of iodate on the reaction of bromate and chloride acid in the presence of hydrazine in acidic media. The decolorization of Methyl Orange with the reaction products was used to monitor the reaction spectrophotometrically at 525 nm. Iodate could be determined in the concentration ranges of 0.03 - 1.2 microg ml(-1). The relative standard deviation for ten replicate determinations of 0.3 microg ml(-1) of iodate was 1.65%. The proposed method was applied to the determination of iodate in table salts with satisfactory results.     

Evaluation of measurement uncertainty for analytical procedures using a linear calibration function

In the EURACHEM/CITAC draft ”Quantifying uncertainty in analytical measurement” estimations of measurement uncertainty in analytical results for linear calibration are given. In this work these estimations are compared, i.e. the uncertainty deduced from repeated observations of the sample vs. the uncertainty deduced from the standard residual deviation of the regression. As a result of this study it is shown that an uncertainty estimation based on repeated observations can give more realistic values if the condition of variance homogeneity is not correctly fulfilled in the calibration range. The complete calculation of measurement uncertainty including assessment of trueness is represented by an example concerning the determination of zinc in sediment samples using ICP-atomic emission spectrometry. Received: 9 February 2002 Accepted: 17 April 2002     

Estimation of limits of detection and determination in X-ray fluorescence analysis by the dependence of the relative standard deviation on analyte concentration

An experimental dependence of the relative standard deviation on analyte concentration of hyperbolic type, characterizing the precision of quantitative chemical analysis, was used to estimate the limits of detection and determination in the X-ray fluorescence analysis. A method is proposed for the determination of their values using the approximation of the experimental dependence of the relative standard deviation on the analyte concentration by a power function. The choice of the values of the relative standard deviation, being criteria for the estimation of these limits, is substantiated. A concept of the limits of detection and determination of an analytical procedure is formulated, according to which the limit of detection of an analytical procedure is an objective value depending only on the precision of determinations, and the limit of determination of an analytical procedure is a subjective value depending not only on the precision of determinations but also on the requirements to their limiting (admissible) accuracy. The limits of detection and determinations of an analytical procedure found by this approach completely characterize the possibilities of an analytical procedure in determining low concentrations of analytes. The proposed approach can be used for the estimation of the limits of detection and determination of analytical procedures and in other methods of chemical analysis with the hyperbolic dependence of the relative standard deviation on the analyte concentration.     

溴酸钾-二甲酚橙体系-顺序注射-催化光度法测定痕量钒

在酸性介质条件下,钒(Ⅳ)能显著催化溴酸钾对二甲酚橙的氧化褪色反应。据此建立了测定痕量钒(Ⅳ)的顺序注射催化光度法。方法的线性范围为0.5~50ng/mL、检出限为0.4ng/mL。对10ng/mL的钒(Ⅳ)连续11次测定的相对标准偏差为1.1%。用于环境水样中痕量钒(Ⅳ)的测定,加标回收率为91%~108%。     

溴酸钾二甲酚橙体系-顺序注射-催化光度法测定痕量钒

在酸性介质条件下,钒(Ⅳ)能显著催化溴酸钾对二甲酚橙的氧化褪色反应。据此建立了测定痕量钒(Ⅳ)的顺序注射催化光度法。方法的线性范围为0.5⁵0ng/mL、检出限为0.4ng/mL。对10ng/mL的钒(Ⅳ)连续11次测定的相对标准偏差为1.1%。用于环境水样中痕量钒(Ⅳ)的测定,加标回收率为91%50ng/mL、检出限为0.4ng/mL。对10ng/mL的钒(Ⅳ)连续11次测定的相对标准偏差为1.1%。用于环境水样中痕量钒(Ⅳ)的测定,加标回收率为91%¹08%。     

Atomic Absorption Spectrophotometric Determination of Copper (I) after Adsorption of its 4′-(p-Methoxyphenyl)-2, 2′:6′, 2″-Terpyridine Tetraphenylborate Ion-Associated Complex on Microcrystalline Naphthalene

A new atomic absorption spectrophotometric method has been developed for the trace determination of copper after adsorption of its 4′-(p-methoxyphenyl)-2, 2′:6′,2″-terpyridine tetraphenylborate ion-associated complex on microcrystalline naphthalene. This complex is adsorbed on microcrystalline naphthalene in the pH range 0.5-11.0 by shaking for a few seconds. The solid mass so formed is separated by filtration, dissolved in dimethylformamide and the absorbance is measured at 324.7 nm. Beer's law is obeyed in the concentration range 5.0-60.0 μg of copper in 10 ml of the final dimethylformamide solution. The replicate determinations of a sample containing 30 μg of copper gave a mean absorbance of 0.171 with a standard deviation of 0.0019 and a relative standard deviation of 1.11%. The method has been applied to the determination of copper in certain standard reference materials.     

Assessment of limits of detection and quantitation using calculation of uncertainty in a new method for water determination

 An approach to the assessment of the limit of detection and the limit of quantitation using uncertainty calculation is discussed. The approach is based on the known evaluation of the limits of detection and quantitation as concentrations of the analyte equal to three and ten standard deviations of the blank response, respectively. It is shown that these values can be calculated as the analyte concentrations, for which relative expanded uncertainty achieves 66% and 20% of possible results of the analyte determination, correspondingly. For example, the calculation is performed for the validation of a new method for water determination in the presence of ene-diols or thiols, developed for analysis of chemical products, drugs or other materials which are unsuitable for direct Karl Fischer titration. A good conformity between calculated values and experimental validation data is observed. Received: 27 July 1998 · Accepted: 29 November 1998     

Accurate mass measurement at enhanced mass-resolution on a triple quadrupole mass-spectrometer for the identification of a reaction impurity and collisionally-induced fragment ions of cabergoline

In this study, accurate mass measurements were made by electrospray ionization (ESI) on a triple quadrupole mass spectrometer operating in enhanced mass-resolution mode (peak width = 0.1 u FWMH), to give qualitative information relating to the pharmaceutical, cabergoline. Accurate mass determinations by ESI-MS were performed on a protonated impurity formed during cabergoline storage. The accurate mass measurement resulted in only one proposed elemental composition for the impurity, using reasonable elemental limits and mass tolerance for the calculation. This information was sufficient to propose a structure for the impurity where ESI-MS/MS proved consistent. The difference between the accurate mass measurement and the exact mass calculated for the proposed structure was 0.8 mmu, with a standard deviation of 0.7 mmu for replicate accurate mass determinations. Accurate mass determinations in ESI-MS/MS provided information on cabergoline fragment ions formed through collisionally-induced dissociation. Since the potential formation of isobaric ions exists for two major cabergoline fragment ions, accurate mass measurement allowed for the determination of the most probable fragment ion structures. The differences between the accurate mass measurements and exact masses calculated for the proposed fragment ions were 1.9 and 2.1 mmu, with standard deviations of 0.4 and 0.8 mmu, respectively, for replicate determinations.     

Estimation of measurement uncertainty in food microbiology: The ISO approach

Given the current interest in measurement uncertainty (MU) in food microbiology, in particular for laboratory accreditation purposes, and the need to have harmonized reference documents specifically in that area at the international level, ISO is conducting works to meet this need. An ISO Technical Specification (ISO/TS 19036) is being prepared on MU estimation for quantitative determinations. A global approach has been chosen, based on the reproducibility standard deviation of the final result of the measurement process. Three possibilities are envisaged for the estimation of the reproducibility standard deviation, in a decreasing order of preference: The intra-laboratory standard deviation, the inter-laboratory standard deviation derived from method validation, and the inter-laboratory standard deviation derived from proficiency testing.The uncertainty of qualitative determinations is still under investigation, and will be covered by a separate ISO publication. Presented at AOAC Europe/Eurachem Symposium March 2005, Brussels, Belgium     

Determination of lead in rocks by radiometric isotope dilution and substoichiometric extraction

A rapid procedure is described for the determination of lead in rocks by an isotope-dilution substoichiometric method. After the sample has been digested with acid in the presence of ²¹⁰Pb tracer, the lead is separated by dithizone extractions. After the lead has been back-extracted into aqueous solution, it is reacted with a substoichiometric amount of EDTA. Excess of unreacted lead is removed by extraction with dithizone in carbon tetrachloride, and the specific activity of the aqueous complex is determined by counting ²¹⁰Pb. The standard deviation of the method is less than 10 % for replicate determinations of lead in several U.S. Geological Survey standard rocks. The agreement with literature values indicates that the method is accurate.     

The determination of chromium in low-alloy irons and steels by atomic absorption spectrophotometry

An atomic absorption spectrophotometric procedure for the determination of 0.001–0.50% chromium in low-alloy iron and steel is described. The sample is dissolved in phosphoric-sulphuric acid before atomisation. The method is rapid, preliminary separations are not required and the accuracy obtained with standard samples is well within the permissible range for routine determinations.     

微波消解-原子吸收法测定氧化铝为载体的钯催化剂中钯

报道了微波消解-AAS法测定氧化铝为载体的钯催化剂中钯的新方法,试验了微波消解溶样条件（溶解试剂、压力、时间和功率等）,研究了测定介质的影响,通过在样品测定液中加入铝基体至铝浓度为4 mg/mL,消除了铝对钯测定的干扰.该法测定结果与光度法的结果一致,相对标准偏差小于1.5%（n=5）.     

Determination of Some Catecholamines Based on Their Reaction with Periodate

An indirect kinetic-spectrophotometric method is proposed for the determination of trace amounts of levodopa, methyldopa, dopamine, and adrenaline based on their reaction with periodate in acidic media. The excess periodate that is related to the amount of catecholamines is determined by its reaction with iodide in the presence of methylene blue. The reaction is monitored spectrophotometrically by measuring the decrease in the absorbance of the solution at 665 nm with a fixed time method of 3.0 min. The relative standard deviation for seven replicate determinations of 0.5 gmL^–1 of L-dopa, methyldopa, dopamine and adrenaline was 1.80, 1.20, 0.92 and 1.35%, respectively. The method was successfully applied to the determination of catecholamines in pure form and in pharmaceutical preparations.     

Determination of the fungicide ferbam in wheat grains after adsorption onto microcrystalline naphthalene

A procedure was developed for the determination of iron(III) dimethyldithiocarbamate by converting it into iron(II)-bathophenanthroline-tetraphenylborate complex, which was then adsorbed onto microcrystalline naphthalene. The absorbance was measured at 534 nm against a reagent blank. Beer's Law was obeyed over the concentration range of 0.4-20 microg mL in final solution. Ten replicate determinations on 70 microg ferbam solutions gave a mean absorbance of 0.36, with a relative standard deviation of 0.91%. The method is sensitive and highly selective. It was applied for the determination of ferbam in a commercial sample and in mixtures with various dithiocarbamates (ziram, zineb, maneb) and wheat grains.     

A novel chemiluminescence flow-through sensor for the determination of analgin

A novel chemiluminescence (CL) flow-through sensor for the determination of analgin with flow-injection analysis (FIA) based on the auto-oxidation of analgin in the presence of Tween 80 sensitized by Rhodamine 6G immobilized on a cation-exchange column is described. This sensor responds linearly to the analgin concentration in the range of 0.4 ∼ 10 mg/L, with a detection limit (3σ) of 0.15 mg/L. A complete analysis, including sampling and washing, takes 1 min with a relative standard deviation of < 5%. The sensor is stable for over 200 determinations and has successfully been applied to the determination of analgin in pharmaceutical preparations. Received: 1 October 1998 / Revised: 19 April 1999 / Accepted: 6 May 1999     

Flow-injection chemiluminescence determination of tryptophan using galangin-potassium permanganate–polyphosphoric acid system

A high sensitive flow-injection chemiluminescence （FI-CL） method for the determination of tryptophan has been developed. The method is based on the chemiluminescence reaction of galangin-potassium permanganate-tryptophan in polyphosphoric acid （PPA） media. Under the optimized conditions, tryptophan was determined in the range 0.05-10 μg/mL with the detection limit （3tr） of 5.0 × 10^-3 μg/mL. The relative standard deviation （RSD） was 1.0% for 11 replicate determinations of 1.0 μg/mL tryptophan. Three synthetic samples were determined selectively with recoveries in the range from 99.6% to 102.0% in the presence of other amino acids.