Determination of methylcyclopentadienylmanganese tricarbonyl (MMT) in gasoline and environmental samples by gas chromatography with helium microwave plasma atomic emission detection

A highly sensitive and specific method is described for the determination of methylcyclopentadienylmanganese tricarbonyl (MMT) in gasoline and environmental samples by gas chromatography–plasma atomic emission detection (GC–AED). The procedure is simple, rapid and free from interferences. The absolute limit of detection is 0.5 fg of MMT (0.5×10⁻¹⁵ g) expressed as Mn. The precision for replicate injections ( n =5) of an MMT solution (10 pg Mn) was 2.8% relative standard deviation (RSD ). Applications of the method to analysis of gasoline (petrol), and preliminary results of the analyses of environmental samples such as air and roadside dirt, are given. © 1997 by John Wiley & Sons, Ltd.     

5-Aryl-1,3,4-oxadiazoline-2(3H)-thiones in reactions with alkyl haloacetates

The reaction of 5-aryl-1,3,4-oxadiazoline-2(3H)-thiones with alkyl haloacetates has been studied. It was shown that the reaction proceeds to give S-substituted products. The effect of the nature of the substituents in the molecules of both the thiones and the haloacetates on the reaction route and yields has been examined.     

Development of a highly sensitive method for determining atmospheric carbonyl compounds by passive sampling and application of the method to a survey of indoor air

A simple, highly sensitive analytical method for measuring many kinds of carbonyls in air using a passive sampler containing a sorbent (silica gel) coated with 2,4-dinitrophenylhydrazine has been developed. The carbonyls collected by the sampler were extracted with a solvent, and the extracts were subjected to high-performance liquid chromatography (HPLC; UV detection) without first being concentrated. In this method, the volume injection is examined, and is found to have a sensitivity at least 20 times that of ordinary HPLC methods. The air concentrations of nine carbonyls collected by passive sampling over a period of 24?h were estimated by means of conversion equations derived from the results of active sampling;c?=?^{10[log ( y} )^{??? b ] a} , where c is the carbonyl concentration in air (µg/m³); y is the amount of carbonyl collected by the passive sampler (µg); and a and b are constants for each carbonyl compound. The calculated air concentrations were consistent with the concentrations measured by active sampling. This method may be useful in determining personal exposure to ambient carbonyls.     

Chitosan Based Diamond Paste Stochastic Microsensors Modified with Gold Nanoparticles Detect Hepatitis C Virus Core Antigen

Three types of chitosan (chitosan I (n=371–744), chitosan II (n=682–930), and chitosan III (n=868–1365)) as well as gold nanoparticles (10 nm diameter) were used to modify diamond paste for the design of new stochastic microsensors. Hepatitis C virus core antigen was used as model analyte to prove the stochastic behavior of the proposed microsensors. The microsensors cover a linear range of concentration between 40 fg/mL and 4 ng/mL. The highest sensitivity (1.38×10⁵ s^?1/mg/mL) and the lower limit of determination (40 fg/mL) were obtained for chitosan III based microsensor. The hepatitis C virus core antigen was assayed from whole blood samples with recoveries higher than 98.00 %.     

N-Alkanes in Air Particulates of the Eastern Province of Saudi Arabia

Abstract

Oil hydrocarbons represent a great proportion of organic compounds in the atmosphere. Information about these compounds in the atmosphere of the Eastern Province of Saudi Arabia is lacking. In this study, n-alkanes and polynuclear aromatic hydrocarbons in air particulates were determined. The highest median concentration levels of n-alkanes in three urban areas and three areas near oil production centers were 121 ng/m³ and 42.9 ng/m³, respectively. Polynuclear aromatic hydrocarbons were also detected, although they are present in too low concentration for reliable quantitative measurement by GC and GC/MS techniques. A positive correlation was found between the concentration levels of n-alkanes in air particulates and the total suspended particulates measured at most locations. The carbon preference index (CPI) and the presence of the unresolved complex envelope suggested an anthropogenic origin for the n-alkanes.     

Application of passive sampling technique in monitoring research on quality of atmospheric air in the area of Tczew,Poland

This paper presents the results of atmospheric air quality research in Tczew (adjacent to the Vistula River) on the content of BTEX compounds. procedure applied during the sampling of the analytes from the air used the passive sampling technique (diffusive passive sampler, Radiello^®). For determination of BTEX compounds in atmospheric air, two-stage thermal desorption technique combined with gas chromatography (TD-GC-FID) was applied.

Research was conducted from March to December 2011. The annual average concentration of benzene, toluene, ethylbenzene and total xylenes determined in atmospheric air for the monitoring period were: 0.87 μg m^–3, 2.9 μg m^–3, 1.3 μg m^–3 and 5.9 μg m^–3, respectively. In order to pre-identify potential sources of emissions of BTEX compounds, statistical analysis was carried out. This determined interactions between specified concentration levels of BTEX compounds in atmospheric air for the monitored area.     

Quantification of transformation products of rocket fuel unsymmetrical dimethylhydrazine in air using solid-phase microextraction

Quantification of unsymmetrical dimethylhydrazine transformation products in ambient air is important for assessing the environmental impact of heavy rocket launches. There are very little data of such analyses, which is mainly caused by the low number of analytes covered by the available analytical methods and their complexity. A simple and cost-efficient method for accurate simultaneous determination of seven unsymmetrical dimethylhydrazine transformation products in air using solid-phase microextraction followed by gas chromatography-mass spectrometry was developed. The method was optimized for air sampling and solid-phase microextraction from 20-mL vials, which allows full automation of analysis. The extraction for 5 min by Carboxen/polydimethylsiloxane fiber from amber vials and desorption for 3 min provided the greatest analytes' responses, lowest relative standard deviations, linear calibration (R² ≥ 0.99), and limits of detection from 0.12 to 0.5 μg/m³. Samples with concentrations 500 μg/m³ can be stored at 21 ± 1°C without substantial losses (1–11%) for up to 24 h, while air samples with concentrations 10 and 50 μg/m³ stored for up to 24 h can be used for accurate quantification of only two and four out of seven analytes, respectively. The developed method was successfully tested for the analysis of air above real soil samples contaminated with unsymmetrical dimethylhydrazine rocket fuel.     

Determination of femtogram quantities of 239Pu and 240Pu in bioassay samples by thermal ionization mass spectrometry

Summary A thermal ionization mass spectrometry (TIMS) method is described for the determination of ultra-trace levels of plutonium isotopes in human urine samples. The method has been validated through the analysis of artificial urine samples spiked with known amounts of ²³⁹Pu ranging from 2.5 fg to 50 fg (6-115mBq). A slight positive bias of 1.7%-2.7% was determined, with a relative precision of 2.2% at 50 fg, increasing to 2.7% for 5-25 fg ²³⁹Pu. The detection limit of the method was 0.53 fg (1.2mBq) ²³⁹Pu, and the instrumental detection limit was at least 0.1 fg. The determination of the isotopic signature of the sample with ²³⁹Pu, ²⁴⁰Pu, and ²⁴¹Pu amounts of several femtograms is possible, and was demonstrated with the determination of the 240 to 239 ratio in an inter-laboratory sample comparison. The method is relatively free from interferences, 95% of sample preparations were acceptable both in terms of chemical recovery and lack of isobaric interference. The isotopic abundance of the ²⁴²Pu SRM 4334E of the National Institute of Standards and Technology (NIST) was also determined by TIMS and was found to be 99.99967 atom% ²⁴²Pu.     

ESR study of weak exchange interactions in binuclear copper(ii) complexes with acyldihydrazones of fluorinated β-diketones

A series of binuclear copper(ii) complexes with acyldihydrazones of aliphatic dicarboxylic acids (from malonic to adipic) and fluorinated -diketones (trifluoro- and hexafluoroacetylacetone) of composition Cu₂L·2Py (H₄L is acyldihydrazone) were studied by ESR spectroscopy. The ESR spectra of solutions of complexes with trifluoroacetylacetone acyldihydrazones have an isotropic signal with a seven-line hyperfine structure from two equivalent copper nuclei (g = 2.112, a _Cu = (39—40)·10^–4 cm^–1), which is indicative of weak exchange interactions between the paramagnetic centers due to spin density delocalization through a chain of the -bonds of the polymethylene bridge. On going to hexafluoroacetylacetone derivatives, the coupling is suppressed and the ESR spectra of solutions of such complexes show a signal with a four-line hyperfine structure (g = 2.121—2.131, a _Cu = (55—63)·10^–4 cm^–1) typical of mononuclear copper complexes.     

A novel, ultra sensible biosensor built by layer-by-layer covalent attachment of a receptor for diagnosis of tumor growth

In the presented research, a novel, ultra sensitive biosensor for the impedimetric detection of vascular endothelial growth factor (VEGF) is introduced. The human vascular endothelial growth factor receptor 1 (VEGF-R1, Flt-1) was used as a biorecognition element for the first time. The immobilization of VEGF-R1 on glassy carbon electrodes was carried out using layer-by-layer covalent attachment of VEGF-R1. The electrochemical properties of the layers constructed on the electrodes were characterized by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The differences in electron transfer resistance (R_et) between the working solution and the biosensor surface, recorded by the redox probe K₃[Fe(CN)₆]/K₄[Fe(CN)₆], confirmed the binding of VEGF to VEGF-R1. The new biosensor allowed a detection limit of 100 fg mL⁻¹ with a linear range of 100–600 fg mL⁻¹ to be obtained. The biosensor also exhibited good repeatability (with a correlation coefficient of 1.95%), and reproducibility.     

Development of diffusive solid phase microextraction method for sampling of epichlorohydrin in air

Epichlorohydrin is used frequently in many industrial processes. Exposure to this pollutant could induce harmful effects. The present work developed a novel solid phase microextraction (SPME) method for time weighted average determination of epichlorohydrin in the air by GC/MS. CAR/PDMS in 0.5?cm retracted mode was selected and the effect of environmental parameters on sampling properties of SPME was examined. Experimental sampling rate for epichlorohydrin (8.89?×?10^?3?cm³/min) was slightly less than theoretical value (9.059?×?10^?3?cm³/min). There was no significant difference among sampling rates at different temperature and velocities but relative humidity had a significant effect on the sampling rate. Limit of detection for SPME method was 0.8?ng per sample, which is good enough in comparison with the NIOSH 1010 method. Comparison of the results between the developed SPME and the NIOSH 1010 method on standard test atmosphere and field showed satisfactory agreement (y?=?1.162x?+?1.8 r ²?=?0.992 and y?=?1.009x+0.76 r ²?=?0.98 respectively).     

Spectra and structure of organophosphorus compounds: XLIX. Microwave,infrared, and Raman spectra,electric dipole moment,molecular structure,and ab initio calculations of dimethylphosphonothioic fluoride

The microwave spectra of (CH₃)₂PSF, (CH₃)(CD₃)PSF, (CD₃)₂PSF, and (CH₃)₂P³⁴SF have been investigated from 20.0 to 40.0 GHz. Botha-type R branch andc-type Q branch transitions have been measured in the ground states of each isotopic species. From a least-square adjustment to fit 12 rotational constants, the following structural parameters were obtained:r(P–F)=1.582 ± 0.003 Å;r(P=S)=1.902 ± 0.001 Å;r(P-C)=1.800 ± 0.001 Å;r(C-H)=1.088 ± 0.002 Å; HCP=109.28 ± 0.12°; SPF=114.50 ± 0.13°; and SPC=116.33 ± 0.06°. From Stark effect measurements, the dipole moment components have been determined to be ¦ _a ¦ =3.556 ± 0.005; ¦ _c ¦=2.026 ± 0.009; and ¦ _t ¦=4.093 ± 0.009 (D). The Raman spectra (3200 to 100 cm^–1) of each isotopic species have been measured for the solid, and liquid and qualitative depolarization values obtained. Additionally, the mid-infrared spectra (3200 to 500 cm^–1) of the solids have been recorded. Proposed assignments of the normal modes have been made on the basis of Raman depolarization values and group frequencies which are supported by normal coordinate analysis utilizing an ab initio force field. Optimized structural parameters have been obtained with both the 3-21G^* and 6-31G^* basis sets. These results are compared to the corresponding quantities for several similar molecules.For part XLVIII, seeJ. Raman Spectrosc.1922,23, 107.     

Atmospheric levels of polycyclic aromatic hydrocarbons in gas and particulate phases from Tarragona Region (NE Spain)

The atmospheric levels of polycyclic aromatic hydrocarbons (PAHs) in atmospheric samples taken at two urban sites and two sites near industrial areas of the Tarragona region (Catalonia, Spain), where one of the most important petrochemical complexes in the south of Europe is located, were determined. Gas and particulate phase of air were separately sampled and analysed. Concentrations of 16 PAHs studied ranged from 4.2 to 22.5 ng m^?3, with predominant levels of PAHs appearing in gas phase (～90% of total PAHs). In all samples, the most abundant compounds were phenanthrene, with a contribution to total PAHs between 32 and 44%, followed by naphthalene, fluorene and fluoranthene (contribution range: 10–22%). The levels of total PAHs, expressed as benzo[a]pyrene toxic equivalent factors (BaP_TEF), were lower than 0.06 ng m^?3.     

The infrared carbonyl band of ethyl haloacetates and rotational isomerism

The integrated intensities of the carbonyl band components of the following ethyl haloacetates, R-COOFt (R = CH₂Cl, CH₂Br, CHCl₂ and CHBr₂), have been measured at different temperatures. From these intensities, values of ΔH° for the equilibrium between the $\text{cis}$ and $\text{gauche}$ rotamers have been estimated. Ethyl haloacetates have been studied in both CCl₄ solution and in gas phase. The absolute values of ΔH° in solution are lower than in gas phase. Results obtained in gas phase indicate that the stability of the $\text{gauche}$ rotamer increases with the size of the halogen atom.     

Passive sampling of airborne furan indoors by solid-phase microextraction

Furan may be formed in food under heat treatment and is highly suspected to appear in indoor air. The possible exposure to indoor furan raises concerns because it has been found to cause carcinogenicity and cytotoxicity in animals. To determine airborne furan, solid-phase microextraction (SPME) technique was utilised as a diffusive sampler. The Carboxen/Polydimethylsiloxane (CAR/PDMS, 75 μm) fibre was used, and the SPME fibre assembly was inserted into a polytetrafluoroethene tubing. Furan of known concentrations was generated in Tedlar gas bags for the evaluation of SPME diffusive samplers. After sampling, the sampler was inserted into the injection port of a gas chromatograph coupled with a mass spectrometer (GC/MS) for thermal desorption and analysis. Validation of the SPME device with active sampling by charcoal tube was performed side by side as well. The charcoal tube was desorbed by acetone before analysis with GC/MS. The experimental sampling constant of the sampler was found equal to (9.93 ± 1.28) × 10^?3 (cm³ min^?1) at 25°C. Furthermore, side-by-side validations between SPME device and charcoal tube showed linear relationship with r = 0.9927. The designed passive sampling device for furan has the advantages of both passive sampling and SPME technique and looks suitable for assessing indoor air quality.     

Urban air pollutants and their micro effects on medieval stained glass windows

Levels of urban gaseous and particulate pollutants were investigated in the Cathedral of Cologne, Germany in the framework of the EU-project “VIDRIO”. The purpose of this study was to evaluate the influence of a protective double glazing system on the preservation of ancient stained glass windows by sampling at protected and unprotected windows (indoors, in the interspace and outdoor of the Cathedral). The interspace between the ancient stained glass window and the protective glazing is flushed in the Cathedral by indoor air, hence isolating the historic glass from the outdoor air and exposing it to indoor air on both sides of the glass panels. Concentrations of aggressive gaseous pollutants such as NO₂, SO₂, O₃ and CO₂ as well as elemental concentrations of bulk particles and relative abundances of single particles were surveyed at all sampling locations. Elemental concentrations in bulk particulate matter were found to be significantly lower inside the Cathedral in comparison to the outdoor air. This result is advantageous for the stained glass windows. Single particle analysis of the samples from Cologne showed also soil dust and organic particles as well as sulphates and nitrates, from which the latter two compounds are dangerous for the stained glass windows. On the base of the obtained results, it can be concluded that the protective glazing system in the Cathedral of Cologne can be considered as predominantly advantageous from both the gases' point of view (except for NO₂-candles burning) and from the particles' point of view.     

Low level detection of <Superscript>135</Superscript>Cs and <Superscript>137</Superscript>Cs in environmental samples by ICP-MS

The measurement of fission product cesium isotopes ¹³⁵Cs and ¹³⁷Cs at low femtogram (fg) 10⁻¹⁵ levels in ground water by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) is reported. To eliminate the natural barium isobaric interference on the cesium isotopes, in-line chromatographic separation of the cesium from barium was performed followed by high sensitivity ICP-MS analysis. A high efficiency desolvating nebulizer system was employed to maximize ICP-MS sensitivity ~10 cps/fg. The three sigma detection limit for ¹³⁵Cs was 2 fg/mL (0.1 μBq/mL) and for ¹³⁷Cs 0.9 fg/mL (0.0027 Bq/mL) measured from the standard with analysis time of less than 30 min/sample. Cesium detection and 135/137 isotope ratio measurement at very low femtogram levels using this method in a spiked ground water matrix is also demonstrated.     

Rapid screening technique for tetrachlorodibenzo-p-dioxins in complex environmental matrices by gas chromatography/tandem mass spectrometry with an ion-trap detector

A capillary column gas chromatographic/ion-trap tandem mass spectrometric (GC/MS/MS) technique was applied to the determination of tetrachlorodibenzo-p-dioxins (TCDDs) in complex environmental matrices. A detection limit of 500 fg μl^-1 injected, with a signal-to-noise ratio of 6:1, was obtained when MS/MS was combined with broadband ion ejection of matrix ions and selected ion isolation. Calibration graphs were constructed from extracted fragment ion mass chromatograms and were found to be linear over the range 0.5-200 pg. Concentrations of total TCDDs and of 2,3,7,8-TCDD were determined for extracts from fish, air and soil; in most cases, the results found by GC/MS/MS were comparable to those obtained by high-resolution MS and triple quadrupole MS.     

Diorganotin halide carboxylates,thiocarboxylates and halide haloacetates

Twenty-eight diorganotin halide acetates, thioacetates, haloacetates and carboxylates, eighteen not previously reported, have been synthesized by the reaction between the diorganotin oxides and acid halides, and by transacyloxylation reactions between diorganotin halide acetates and carboxylic acids. Infrared in the 2000—200 cm^-1 range, proton and carbon-13 NMR and tin-119m Mössbauer data are interpreted in terms of acetoxy-bridged, trigonal bipyramidal tin in the solid phase with depolymerization occurring in solution where a dynamic equilibrium between diorganotin dihalide and dicarboxylate species is rapidly established. A new infrared absorption also appears at 100–125 cm^-1 to higher frequency of the v_asym(CO₂) which disappears on heating. A dimeric structure based upon four-membered Sn₂O₂ or Sn₂OX rings in which carboxylate group oxygen atoms bridge tin atoms of a second molecule leaving the CO group free is proposed. The halide thioacetates are associated in the solid state but are monomeric in solution.     

A sensitive and efficient method for trace analysis of some phenolic compounds using simultaneous derivatization and air‐assisted liquid–liquid microextraction from human urine and plasma samples followed by gas chromatography–nitrogen phosphorous detection

In present study, a simultaneous derivatization and air‐assisted liquid–liquid microextraction method combined with gas chromatography–nitrogen phosphorous detection has been developed for the determination of some phenolic compounds in biological samples. The analytes are derivatized and extracted simultaneously by a fast reaction with 1‐flouro‐2,4‐dinitrobenzene under mild conditions. Under optimal conditions low limits of detection in the range of 0.05–0.34 ng mL^?1 are achievable. The obtained extraction recoveries are between 84 and 97% and the relative standard deviations are less than 7.2% for intraday (n = 6) and interday (n = 4) precisions. The proposed method was demonstrated to be a simple and efficient method for the analysis of phenols in biological samples. Copyright © 2015 John Wiley & Sons, Ltd.