Direct flame-photometric determination of calcium in soil and plant extracts,water and serum with special reference to sodium,potassium and phosphate interference

An investigation of the possibilities for the direct determination of calcium with a single-cell filter flame photometer, without preliminary separation as oxalate, led to the following conclusions:Calibration curves for 100 p.p.m. of calcium are rectilinear.Sodium causes an appreciable positive error.The error due to potassium interference is relatively much smaller than that due to sodium. Up to a certain concentration it is positive and increases with the concentration, then the emission seems to be gradually depressed and the error finally becomes negative.Phosphates cause a very significant negative error, which tends to be asymptotic. The “radiation buffer” method of correction is not practical here because the max. error is too high (—92.5%).Except for extreme cases, calcium can be determined by direct spraying, without preliminary separation as oxalate: (a) in drinking and irrigation water, correction being necessary only for sodium interference, (b) in soil extracts, correcting only for phosphate effects, (c) in normal blood sera, without clinically significant corrections at 1+3 dilution.Owing to the large variations in the contents of Na, K and PO₄^-3 in plants, calcium cannot be determined in plant-ash extracts without preliminary separation as oxalate. This applies also to abnormal sera, although there the variations in Na and PO₄^-3 content are not so large.     

Sampling and determination of hydrogen cyanide in cigarette smoke

A method for sampling and determination of hydrogen cyanide in cigarette smoke is described. Cigarette smoke is filtered through a glass fiber filter paper, and only gaseous compounds, such as hydrogen cyanide, are collected in a dilute sodium hydroxide solution. The cyanide is determined spectrophotometrically at 550 nm by the isonicotinic acid–pyrazolone method. Maximum absorbance is achieved within 10 min at room temperature, and remains constant for about 20 min. Beer’s law is obeyed in the range 0.04∼0.80 μg mL^–1 cyanide, with a molar absorptivity of 3.48 × 10⁴ L mol^–1 cm^–1. Received: 30 November 1998 / Revised: 21 April 1999 / Accepted: 30 April 1999     

Sampling and determination of hydrogen cyanide in cigarette smoke

A method for sampling and determination of hydrogen cyanide in cigarette smoke is described. Cigarette smoke is filtered through a glass fiber filter paper, and only gaseous compounds, such as hydrogen cyanide, are collected in a dilute sodium hydroxide solution. The cyanide is determined spectrophotometrically at 550 nm by the isonicotinic acid–pyrazolone method. Maximum absorbance is achieved within 10 min at room temperature, and remains constant for about 20 min. Beer’s law is obeyed in the range 0.04∼0.80 μg mL^–1 cyanide, with a molar absorptivity of 3.48 × 10⁴ L mol^–1 cm^–1. Received: 30 November 1998 / Revised: 21 April 1999 / Accepted: 30 April 1999     

A review of interference effects and their correction in chemical analysis with special reference to uncertainty

This paper reviews matrix effects and interference in chemical analysis and the methods by which analytical chemists reduce their effects to either negligible or minimal magnitude. The aim is to provide a framework for estimating the contribution to uncertainty due to these effects in analysis, with or without the application of procedures for correcting them. The general characteristics of matrix effects and interference are discussed, and general principles for the estimation of uncertainty associated with matrix effects are introduced. The principal techniques available to minimise matrix effects are described, together with methods of uncertainty estimation where appropriate.The Analytical Methods Committee of the Royal Society of Chemistry has received and approved for publication the following report from its Matrix Effects Working Group. The constitution of the working group was Dr. S. Ellison (Chairman), Prof. M. Thompson, Dr. D. Bullock, Dr. J. Dean, Prof. T. Fearn, W. Hardcastle, Dr. T. Lynch, Dr. N. Reid, Dr. S. Scott, Dr. Thompson.

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The titrimetric determination of carbon dioxide with special reference to the determination of carbon in organic compounds

The titrimetric barium carbonate method for the determination of. carbon in organic compounds has been examined and the various sources of error are discussed. The carbon dioxide from the combustion of the sample is absorbed in excess baryta containing 20% (w/v) barium chloride and the excess is back-titrated with hydrochloric acid in the presence of o-cresolphthalein indicator.The value of this method in conjunction with the previously described determination of water with succinyl chloride, for the simultaneous determination of carbon and hydrogen is assessed     

The automatic determination of silicate-silicon in natural waters with special reference to sea water

An automatic method using a Technicon AutoAnalyzer is described for the determination of silicate in natural waters in the range 0–4 mg Si/l. It is based on the conversion of silicate to β-silicomolybdic acid which is reduced by means of a metolsulphite reagent to molybdenum blue. Interference of phosphate is prevented by oxalic acid. The relationship between silicate concentration and optical density is linear in both fresh waters and sea water. With sea water the salt error of the method is ca. 5% at a salinity of 35‰ A coefficient of variation of 0.8% was found at a silicate concentration of 1 mg Si/l with both fresh and sea waters.     

The colorimetric determination of silicate with special reference to sea and natural waters

The optimum conditions for the determination of silicate in natural waters by a molybdenum blue method have been investigated p-Methylaminophenol sulphate has a number of advantages over other reducing agents for the reduction of silicomolybdic acid to molybdenum blue. Beer's law is obeyed up to concentrations of at least 3 mg/l.The interference of several inorganic ions has been investigated; none of those encountered in natural waters is likely to cause error. The method has been applied to the analysis of sea-water and the “salt error” correction evaluated.     

Liquid membrane electrodes for the selective determination of nicotine in cigarette smoke

Five liquid membrane electrode systems responsive to the nicotinium cation are described. These electrodes are based on the use of the ion-association complexes of the nicotinium cation with tetraphenylborate, 5-nitrobarbiturate, flavianate, reineckate and picrolonate counter anions in nitrobenzene solvent as ion-exchange sites. The performance characteristics of these electrodes, evaluated according to IUPAC recommendations, reveal fast, stable and near-Nernstian responses for 10(-2)-10(-5) M nicotine over the pH range 3.5-7. Many inorganic and organic cations do not interfere. The direct potentiometric determination of 3 micrograms ml-1-1.6 mg ml-1 of nicotine in aqueous solutions showed an an average recovery of 99.5% and a mean standard deviation of 1.2%. The electrodes were also used for monitoring the titration of nicotine with sodium tetraphenylborate, measuring the pK of nicotine and determining nicotine in the smoke from different cigarettes. The results compare favourably with those obtained by the standard gas chromatographic method.     

Platinum determination by instrumental neutron activation analysis with special reference to the spectral interference of Sc-47 on the platinum indicator nuclide Au-199

A method of instrumental neutron activation analysis (INAA) is developed for the determination of platinum by the ¹⁹⁹Au daughter of ¹⁹⁹Pt in the presence of the spectral interference from the ⁴⁷Sc daughter of ⁴⁷Ca. The contributions of the Pt and Ca signals to the integral 157–161 keV peak were separated by calculating the number of disintegrations due to the ⁴⁷Sc from the signal of her parent ⁴⁷Ca at 1297.1 keV γ-ray. The method was used to calculate the trace concentrations of Pt in air samples, collected on filters.     

Direct determination of hydrogen cyanide in cigarette mainstream smoke by ion chromatography with pulsed amperometric detection

The determination of hydrogen cyanide in cigarette mainstream smoke has been achieved by ion chromatography (IC) with pulsed amperometric detection (PAD). The proposed method of totally trapping whole cigarette mainstream smoke by Cambridge filters, which are treated with sodium hydroxide/ethanol solution, possesses the advantage of fast analysis time over the widespread used solution absorption method. The possible co-existing interferents are evaluated under the optimized detection conditions and excellent recoveries of cyanide are obtained. The cyanide content of absorption solution can be directly determined by the optimized IC-PAD method without any pretreatments. The linear range is 0.0147-2.45 μg/mL with R2 value of 0.9997. The limit of the detection is 3 μg/L for a 25 μL injection loop. The overall relative standard deviation of the method is less than 5.20% and the recovery range from 94.3% to 101.0%. The results obtained from the developed method are in good agreement with that of continuous flow analyzer (CFA) method.     

Ultraviolet action spectra in perspective: with special reference to mutation

Abstract— Problems of determining action spectra are considered as well as various types of action spectra for U.V. action upon cell activities. U.V. is an effective mutagenic agent producing point mutations and chromosomal changes. U.V. is readily absorbed by superficial layers of cells in tissues; therefore, special experimental procedures are necessary for induction of mutations in animals or plants. U.V. is, however, suitable for mutagenesis in microorganisms because their cells are small, permitting the radiation to reach the nuclei. Action spectrum studies reveal that u.v. mutagenesis results from absorption of the radiation by nucleic acid. The most prominent alteration in DNA following absorption of u.v. is dimerization of pyrimidines, chiefly thymine. Such a change not only retards DNA replication but results in errors (mutations). U.V. mutagenesis therefore depends upon the conditions before, during and after irradiation. Thus immediate post-treatment with visible and long u.v. light splits pyrimidine dimers, thereby reversing impending u.v. mutagenesis. For cells kept in the dark, conditions which prevent DNA replication by interfering with the metabolism of the cell provide time for dark repair of the DNA lesion and so for reversal of the impending mutation.     

A novel protocol for ultra-trace detection of pesticides: Combined electrochemical reduction of Ellman's reagent with acetylcholinesterase inhibition

This paper proposed a novel method for ultra-trace detection of pesticides combining electrochemical reduction of Ellman's reagent with acetylcholinesterase (AChE) inhibition. The amperometric biosensor, fabricated by immobilizing AChE on multi-walled carbon nanotubes-chitosan (MWCNTs-Chi) nanocomposites modified glassy carbon electrode, enjoyed high sensitivity owing to the excellent conductivity and favourable biocompatibility of MWCNTs-Chi nanocomposites. Meanwhile, the sensitivity of the biosensor was further enhanced using the electrochemical reduction signal of DTNB for determination. Under optimum conditions, methyl parathion was detected based on its inhibition effect on AChE activity and the subsequent change in electrochemical reduction response of DTNB. Good relationship was obtained between the reduction current and pesticide concentration in the ranges of 5.0 × 10⁻⁷ to 1.0 × 10⁻¹² M with a detection limit of 7.5 × 10⁻¹³ M (S/N = 3). Moreover, the proposed protocol was successfully employed for the determination of methyl parathion in water and soil samples.     

Simultaneous determination of amino-alpha-carbolines and amino-gamma-carbolines in cigarette smoke condensate by high-performance liquid chromatography

A method for the simultaneous detection of amino-alpha-carbolines (2-amino-alpha-carboline and 2-amino-3-methyl-alpha-carboline) and amino-gamma-carbolines (3-amino-1,4-dimethyl-5H-pyrido [4,3-b]indole and 3-amino-1-methyl-5H-pyrido [4,3-b]indole) by high-performance liquid chromatography has been developed. It consists of a three-step purification using three different columns with fluorometric detection. With this method, we have demonstrated that both amino-alpha-carbolines and amino-gamma-carbolines are present in cigarette smoke condensate. The method may be useful for detecting these carcinogens in various materials.     

Isotope dilution gas chromatography-mass spectrometry in the determination of benzene, toluene, styrene and acrylonitrile in mainstream cigarette smoke

A cryogenic trapping method with isotope dilution gas chromatography-mass spectrometry analysis has been developed for the determination of benzene, toluene, styrene and acrylonitrile in mainstream vapor phase cigarette smoke. The method is simple, direct, and quantitative. Vapor phase samples are collected cryogenically in a series of four traps following removal of the particulate phase with a Cambridge filter pad. For all four analytes, 75-85% of the total amounts recovered were found in the initial trap and less than 1% in the final trap. Assessment of instrumental precision by multiple injections of a sample gave relative standard deviations of less than 2%. Linear calibration for all analytes over the analysis range gave an r2 value greater than 0.99 with average relative standard deviations at the mean ranging from 1.4 to 8.2%. The cigarettes analyzed include a reference cigarette (Kentucky 1R4F), a commercial ultra-low "tar" mentholated cigarette, and two cigarettes that heat but do not burn tobacco. The values determined for the four analytes in the 1R4F samples are comparable to reported values of similar cigarettes. The cigarettes which heat rather than burn tobacco yield less of all four analytes compared to the other cigarettes in the study.     

Quantitative determination of selected compounds in a Kentucky 1R4F reference cigarette smoke by multidimensional gas chromatography and selected ion monitoring-mass spectrometry

Eight compounds from a Kentucky 1R4F reference cigarette smoke condensate have been determined by selected ion monitoring-mass spectrometry (SIM-MS) to confirm the validity of multidimensional gas chromatography (MDGC) as a quantitative tool in complex mixture analyses. Four electrostatically precipitated smoke condensate samples of 100 cigarettes each are dissolved individually in 25 mL of 2-propanol. The 2-propanol contains two methyl esters (C8 and C14) and seven deuterium-labeled compounds used as internal standards (IS). Analysis of the compounds of interest, pyridine; acetamide; acrylamide; phenol; o-, m-, and p-cresol; and quinoline, is accomplished by using two heartcuts. Heartcut times of the MDGC analysis are selected such that at least one IS is transferred with each group of compounds being analyzed. This study shows that the MDGC technique previously developed and described can be used for quantitative analyses. A comparison is made between the two types of internal standards. The results obtained for both types of internal standards agree within 20% of each other, on the average, with higher standard deviations for approximately 60% of the compounds where methyl esters are used as internal standards.     

Platinum determination in nutrient plants by inductively coupled plasma mass spectrometry with special respect to the hafnium oxide interference

Platinum, emitted from automobile exhaust catalysts, is mainly oxidised in a humic soil, as described previously [1]. An experiment with nutrient plants was carried out to elucidate the bioavailability and accumulation of these platinum containing species. The plants [Allium cepa L. (Weiß, Frühling), Rephanus sativus L. (Riesenbutter), Vicia faba L. (Hedin, Herzfreya), Zea mays L. (Delis) and Solanum tuberosum L. (Selma)] were grown under natural conditions. For mass balances all ways of platinum transport into and out of the system were monitored during the growing period. Plants growing in untreated soil took up less than 1% of the platinum naturally present in the soil [0.15±0.11?μg?kg^-1 (78%)]. Plants growing in soil treated with a platinum containing tunnel dust took up slightly more platinum. The comparison of ICPquadrupole-MS results with those obtained by a double focusing magnetic sector ICP-MS showed a strong dependence of the platinum concentration on the Hf-content in the sample. An evaluation method for the correction of the Hf-influence for ICP-quadrupole-MS is presented.