Interactions between Crown Ethers and Water,Methanol, Acetone,and Acetonitrile in Halogenated Solvents

The interactions between crown ethers and water, methanol, acetone, and acetonitrile molecules in halogenated solvents are studied by means of calorimetric measurements. The results reveal the formation of 1:1 complexes between crown ethers and water in chloroform. The hydrogen bonding and ion–dipole interactions are responsible for the complex formation between the water molecules and crown ethers. For a better understanding of the influence of chloroform upon the complexation between crown ethers and water, chloroform is replaced by dichloromethane, 1,2-dichloroethane, and carbon tetrachloride. Since the hydrogen bonds are responsible for the complex formation between crown ethers and water in the halogenated solvents, further investigations are performed with methanol, acetone and acetonitrile. The interactions, the ligand nature, the concentrations of polar solvents, and the nature of nonpolar solvents involved in complexation are analyzed and discussed.     

Determination of Tetrachloroethylene and Other Volatile Halogenated Organic Compounds in Oil Wastes by Headspace SPME GC–MS

Oil wastes and slops are complex mixtures of hydrocarbons, which may contain a variety of contaminants including tetrachloroethylene (perchloroethylene, PCE) and other volatile halogenated organic compounds (VHOCs). The analytical determination of PCE at trace levels in petroleum-derived matrices is difficult to carry out in the presence of large amounts of hydrocarbon matrix components. In the following study, we demonstrate that headspace solid-phase microextraction (HS-SPME) combined with GC–MS analysis can be applied for the rapid measurement of PCE concentration in oil samples. The HS-SPME method was developed using liquid paraffin as matrix matching reference material for external and internal calibration and optimisation of experimental parameters. The limit of quantitation was 0.05 mg kg⁻¹, and linearity was established up to 25 mg kg⁻¹. The HS-SPME method was extended to several VHOCs, including trichloroethylene (TCE) in different matrices and was applied to the quantitative analysis of PCE and TCE in real samples.     

Interlaboratory comparison study for the determination of halogenated hydrocarbons in water

Sixty laboratories of five different countries participated in a large-scale interlaboratory comparison test for the determination of halogenated hydrocarbons in water. Participants used their in-house method with 44 laboratories applying head space GC ECD analysis and 5 using liquid/liquid extraction. A set of two artificially produced samples was prepared; the halogenated hydrocarbons investigated were trichloroethylene, tetrachloroethylene, 1,1,1-trichloroethane, trichloromethane, tetrachloromethane, 1,1-dichloroethylene, dichloromethane, dibromochloromethane, bromodichloromethane, 1,2-dichloroethane and tribromomethane. The procedure of sample preparation, storage and distribution was monitored by an extensive quality assurance system including homogeneity tests, stability tests, and trend analysis of the submitted data. The analytical results submitted by the participants exhibited RSD values of up to 35% and outlier rates of up to 19%. The percentage of false positive and false negative results was at the highest 12% for selected substances. Recovery rates varying from 86% to 106% proved the correctness of the analytical results submitted by the participants and showed that the procedure developed in this study for sample preparation and distribution is well suited for the performance of large-scale interlaboratory comparison tests of halogenated hydrocarbons in water.     

Interlaboratory comparison study for the determination of halogenated hydrocarbons in water

Sixty laboratories of five different countries participated in a large-scale interlaboratory comparison test for the determination of halogenated hydrocarbons in water. Participants used their in-house method with 44 laboratories applying head space GC ECD analysis and 5 using liquid/liquid extraction. A set of two artificially produced samples was prepared; the halogenated hydrocarbons investigated were trichloroethylene, tetrachloroethylene, 1,1,1-trichloroethane, trichloromethane, tetrachloromethane, 1,1-dichloroethylene, dichloromethane, dibromochloromethane, bromodichloromethane, 1,2-dichloroethane and tribromomethane. The procedure of sample preparation, storage and distribution was monitored by an extensive quality assurance system including homogeneity tests, stability tests, and trend analysis of the submitted data. The analytical results submitted by the participants exhibited RSD values of up to 35% and outlier rates of up to 19%. The percentage of false positive and false negative results was at the highest 12% for selected substances. Recovery rates varying from 86% to 106% proved the correctness of the analytical results submitted by the participants and showed that the procedure developed in this study for sample preparation and distribution is well suited for the performance of large-scale interlaboratory comparison tests of halogenated hydrocarbons in water. Received: 7 December 1998 / Revised: 23 March 1999 / Accepted: 24 March 1999     

Partition of Neutral Molecules and Ions from Water to <Emphasis Type="Italic">o</Emphasis>-Nitrophenyl Octyl Ether and of Neutral Molecules from the Gas Phase to <Emphasis Type="Italic">o</Emphasis>-Nitrophenyl Octyl Ether

We have set out an equation for partition of 87 neutral molecules from water to o-nitrophenyl octyl ether, NPOE, an equation for partition of the 87 neutral molecules and 21 ionic species from water to NPOE, and an equation for partition of 87 neutral molecules from the gas phase to NPOE. Comparison with equations for partition into other solvents shows that, as regards partition of neutral (nonelectrolyte) compounds, NPOE would be a good model for 1,2-dichloroethane and for nitrobenzene. In terms of partition of ions and ionic species, NPOE is quite similar to 1,2-dichloroethane and not far away from other aprotic solvents such as nitrobenzene.     

Analysis of class 1 residual solvents in pharmaceuticals using headspace-programmed temperature vaporization-fast gas chromatography-mass spectrometry

A sensitive method is presented for the fast screening and determination of residual class 1 solvents (1,1-dichloroethene, 1,2-dichloroethane, 1,1,1-trichloroethane, carbon tetrachloride and benzene) in pharmaceutical products. The applicability of a headspace (HS) autosampler in combination with GC equipped with a programmed temperature vaporizer (PTV) and a MS detector is explored. Different injection techniques were compared. The benefits of using solvent vent injection instead of split or splitless-hot injection for the measurement of volatile compounds are shown: better peak shapes, better signal-to-noise ratios, and hence better detection limits. The proposed method is extremely sensitive. The limits of detection ranged from 4.9 ppt (benzene) to 7.9 ppt (1,2-dichloroethane) and precision (measured as the relative standard deviation) was equal to or lower than 12% in all cases. The method was applied to the determination of residual solvents in nine different pharmaceutical products. The analytical performance of the method shows that it is appropriate for the determination of residual class 1 solvents and has much lower detection limits than the concentration limits proposed by the International Conference on Harmonization (ICH) of Technical Requirements for the Registration of Pharmaceuticals for Human Use. The proposed method achieves a clear improvement in sensitivity with respect to conventional headspace methods due to the use of the PTV.     

Extraction—spectrophotometric determination of benzethonium and benzalkonium salts with bomocresol green and quinine

A method is described for the determination of benzethonium and benzalkonium compounds (1–5 × 10^?6 M) based on the formation of ion-associates with bromocresol green (BCG) and quinine in 1,2-dichloroethane. Benzethonium and benzalkonium are extracted quantitatively after the formation of a new type of ion-associate with BCG and quinine in an aqueous solution at pH 8.2. The ion-associate shows an absorption maximum at 630 nm. Many other quaternary ammonium species and amines do not interfere. The method is applied to a range of pharmaceutical products.     

A radioreagent method of analysis of boron in sub-microgram range

A radioreagent method for the determination of boron in submicrogram range is described. This method is based on the reaction of boric acid with hydrofluoric acid labeled with¹⁸F and the measurement of the activity of the product, HBF ₄ ^* , which is isolated by complexation with methylene blue and extraction with 1,2-dichloroethane. The 0.51 Mev gamma ray activity resulting from¹⁸F of an aliquot of the extract is found to be proportional to the amount of boron in the sample. It was found that at least 0.1 μg of boron can be measured by this method with an accuracy of about 5% error. The short-lived nature of¹⁸F makes it necessary that the analysis be performed as soon as the isotope is available. The sample to be analyzed should be freed from hydrofluoric acid as well as other species which form precipitate or complexes with Hf. The method was applied successfully to the analysis of one of the Netional Bureau of Standards reference samples.     

Response surface optimisation applied to a headspace-solid phase microextraction-gas chromatography-mass spectrometry method for the analysis of volatile organic compounds in water matrices

A new method for the simultaneous determination of 12 volatile organic compounds (trans-1,2-dichloroethene, 1,1,1-trichloroethane, benzene, 1,2-dichloroethane, trichloroethene, toluene, 1,1,2-trichloroethane, tetrachloroethene, ethylbenzene, m-, p-, o-xylene) in water samples by headspace solid phase microextraction (HS–SPME)–gas chromatography mass spectrometry (GC–MS) was described, using a 100?µm PDMS (polydimethylsiloxane) coated fibre. The response surface methodology was used to optimise the effect of the extraction time and temperature, as well as the influence of the salt addition in the extraction process. Optimal conditions were extraction time and temperature of 30?min and ?20°C, respectively, and NaCl concentration of 4?mol?L^?1. The detection limits were in the range of 1.1?×?10^?3–2.3?µg?L^?1 for the 12 volatile organic compounds (VOCs). Global uncertainties were in the range of 4–68%, when concentrations decrease from 250?µg?L^?1 down to the limits of quantification. The method proved adequate to detect VOCs in six river samples.     

Electrophilicity of α-oxo gold carbene intermediates: halogen abstractions from halogenated solvents leading to the formation of chloro/bromomethyl ketones

α-Oxo gold carbenes generated via intermolecular oxidation of terminal alkynes are shown to be highly electrophilic and can effectively abstract halogen from halogenated solvents such as 1,2-dichloroethane or 1,2-dibromoethane. Chloro/bromomethyl ketones are prepared in moderate efficiencies in one step using Ph(3)PAuNTf(2) as the catalyst and 8-methylquinoline N-oxide as the oxidant.     

Determination of tarce water in non-polar organic solvents with a flow-injection system and tin tetrachloride or antimony pentachloride

Low levels of water (limit of detection 2-5 mg kg^1?)can be determined in a non-polar organic solvents such as benzene, 1,2-dichloroethane (DCE) and n-hexane by utilizing the reaction of water with SnCl₄ or SbCl₅. The reaction results of hydrolysis in halide and is accompanied by a decrease in optical absorption. With SnSl₄, the reaction is monitored near 300 nm and with SbCl₅ it is monitored at lower wavelengths (350-420). Niether reactons proceeds well in media containing only DCE and n-hexane. For this reason, the arrangemens involves a halide reagent dissolved in benzene which is merged with a benzene/n-hexane/DCE carrier stream into which samlpe is injected. A configuration in which only 2μl of a concentrated halide reagent solution is injected into the flowing sample stream is also shown to be viable for the determination of water in benzene. A membrane-permeation-based calibration method for preparing trace water standards is described.     

Development of a procedure for the gas-chromatographic determination of vinyl chloride and 1,2-dichloroethane in blood with the use of headspace analysis

A procedure for the determination of the weight concentrations of vinyl chloride and 1,2-dichloroethane in blood over the range of 0.1–2.0 μg/cm³ was developed. The procedure is based on a static version of gas-chromatographic headspace analysis. The determination was performed on a column packed with a Chromaton N-AW-DMCS sorbent with 15 wt % Apiezon L using flame-ionization detection. The relative error of the procedure was no higher than 20%.     

Direct acetylation followed by solid-phase disk extraction and GC-ITDMS for the determination of trace phenols in water

Summary A rapid, accurate and sensitive method is described for the analysis of phenolic compounds, including phenol, alkylphenols, halogenated phenols and nitrophenols in tap, ground and river water samples. The method consists in direct acetylation of the aqueous phenols with acetic anhydride, extraction of the phenol acetates with a C₁₈ disk and analysis by gas chromatography with an ion-trap detector mass spectrometer. Using this method, the sample preparation time was approximately 1.5 h for six 1-L water samples, and recoveries for most of the phenolic compounds studied were more than 80% at concentration levels of 0.1 and 1.0g L^–1. The detection limits were in the range 2 to 15 ng L^–1 for phenol, alkylphenols and halogenated phenols, and 25 to 50 ng L^–1 for nitrophenols.     

The effect of additives of strong inorganic acids on IR-spectroscopic determination of water in organic solutions

The possibility of the quantitative determination of water in organic solvents containing strong acids by IR spectrophotometry at 3500–3700 cm^?1 was studied. The molar absorption coefficients at the maximum of the most intense absorption bands of water in acetonitrile, chloroform, and 1,2-dichloroethane were 115, 43, and 88 M^?1 cm^?1, respectively. The study of the effect of acid additions to acetonitrile showed that hydrochloric and nitric acids had little on the shape and intensity of the IR spectra of water. The presence of perchloric acid reduces the intensity (for 0.027 M HClO₄, by 40% at 3618 cm^?1), which was due to the state of acids in the solvents. Conductometric measurements showed that, under these conditions, HCl and HNO₃ were unionized, while HClO₄ dissociated almost completely.     

Microwave induced plasma atomic emission spectrometry: a suitable detection system for the determination of volatile halocarbons

Microwave induced plasma atomic emission spectrometry (MIP-AES), a highly sensitive detection system for organometal compounds, was coupled to an automated purge and trap gas chromatographic system for the determination of volatile halogenated hydrocarbons in environmental water samples. Optimisation of the parameters affecting the injection and detection system led to relative detection limits from 1 to 14 ng · L^–1 for chlorine- and bromine-compounds and from 10 to 75 ng · L^–1 for iodine-compounds, on basis of a 10 mL sample volume. A comparison of the analytical characteristics between atomic emission detection (AED) and electron capture detection (ECD) showed a lower sensitivity of the atomic emission detector for halocarbons, but the detection thresholds are low enough to use the method for the determination of volatile halocarbons in trace level concentrations. The ability of the atomic emission detector provides increased selectivity for monitoring individual halogenated compounds under simplified and rapid chromatographic conditions, within a total analysis time of only 30 min. The method was applied with gas chromatographic separation for the analysis of sea water samples. Concentrations for the different elements between 0.05 and 15.28 μg · L^–1 were determined.     

A new approach to determine method detection limits for compound-specific isotope analysis of volatile organic compounds

Compound-specific isotope analysis (CSIA) has been established as a useful tool in the field of environmental science, in particular in the assessment of contaminated sites. What limits the use of gas chromatography/isotope ratio mass spectrometry (GC/IRMS) is the low sensitivity of the method compared with GC/MS analysis; however, the development of suitable extraction and enrichment techniques for important groundwater contaminants will extend the fields of application for GC/IRMS. So far, purge and trap (P&T) is the most effective, known preconcentration technique for on-line CSIA with the lowest reported method detection limits (MDLs in the low microg/L range). With the goal of improving the sensitivity of a fully automated GC/IRMS analysis method, a commercially available P&T system was modified. The method was evaluated for ten monoaromatic compounds (benzene, toluene, para-xylene, ethylbenzene, propylbenzene, isopropylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, fluorobenzene) and ten halogenated volatile organic compounds (VOCs) (dichloromethane, cis-1,2-dichloroethene, trans-1,2-dichloroethene, carbon tetrachloride, chloroform, 1,2-dichloroethane, trichloroethene, tetrachlorethene, 1,2-dibromoethane, bromoform). The influence of method parameters, including purge gas flow rates and purge times, on delta13C values of target compounds was evaluated. The P&T method showed good reproducibility, high linearity and small isotopic fractionation. MDLs were determined by consecutive calculation of the delta13C mean values. The last concentration for which the delta13C value was within this iterative interval and for which the standard deviation was lower than +/-0.5 per thousand for triplicate measurements was defined as the MDL. MDLs for monoaromatic compounds between 0.07 and 0.35 microg/L are the lowest values reported so far for continuous-flow isotope ratio measurements using an automated system. MDLs for halogenated hydrocarbons were between 0.76 and 27 microg/L. The environmental applicability of the P&T-GC/IRMS method in the low-microg/L range was demonstrated in a case study on groundwater samples from a former military air field contaminated with VOCs.     

GC determination of halogenated olefins by photoionization and hall electrolytic conductivity detectors in series in matrices of hydrofluorocarbons and hydrochlorofluorocarbons

Summary Gas chromatography (GC) with photoionization (PI) and Hall electrolytic conductivity (E1C) detectors connected in series, has been used for the determination of chlorofluorinated olefins. The separation of different standard solutions containing eight chlorofluorinated ethenes in nitrogen and in halogenated matrices has been performed in wide bore capillaries, 0.53 mm i.d., and normal capillaries, 0.32 mm i.d. The quality of separation is obviously influenced by their limited load capacity and by the response time of the Hall detector. At concentrations 1–150 μL L⁻¹ halogenated olefins, both PI and ElC detectors have linear response and can detect minimum levels of 0.2–0.5 ng and 0.4–1.2 ng, respectively. The PID is particularly selective toward halogenated olefins and is extremely useful for the determination of traces of unsaturated halogenated hydrocarbons in a matrix of saturated homologues. The results of this work are of great interest for the detection of chorofluorinated olefins, highly toxic compounds usually formed as by-products in the industrial production of hydrofluorocarbons and hydrochloro-flurocarbons.     

Optimisation of stir bar sorptive extraction and in-tube derivatisation-thermal desorption-gas chromatography-mass spectrometry for the determination of several endocrine disruptor compounds in environmental water samples

The analysis of organic pollutants in environmental water samples requires a pre-concentration step. Pre-concentration techniques such as stir bar sorptive extraction (SBSE) have gained popularity since they minimise the use of toxic organic solvents and can be considered as green analytical techniques. Similar to other pre-concentration techniques, one of the problems when SBSE is used is the matrix effect, which often occurs during the analysis of environmental water samples such as estuarine or wastewater samples. The present work studied the matrix effect during SBSE coupled to in-tube derivatisation–thermal desorption (TD)–gas chromatography–mass spectrometry for the determination of several endocrine disruptor compounds, such as alkylphenols, bisphenol A, estrogens and sterols, in environmental water samples, after optimisation of the major variables affecting the determination. Variables such as the addition of methanol or an inert salt to the donor phase, the extraction temperature, the volume of the donor phase, the stirring rate and the extraction time were studied during the SBSE optimisation. In the case of the in-tube derivatisation and TD step, the volume of the derivatisation reagent (N,O-bis(trimethylsilyl)triufloroacetamide with 1% of trimethylchlorosilane (BSTFA + 1% TMCS)) and the cryo-focusing temperature were fixed (2 μL and −50 °C, respectively) according to a consensus between maximum signal and optimal operation conditions. Good apparent recovery values (78–124%) were obtained for most of the analytes in Milli-Q water, except for 4-tert-octylphenol (4-tOP), which showed apparent recovery values exceeding 100%. Precision (n = 4) was in the 2–27%, and method detection limits were in the low nanogrammes per litre level for most of the analytes studied. The matrix effect was studied using two different approaches. On the one hand, Milli-Q water samples were spiked with humic acids, and apparent recovery values were studied with and without correction with the corresponding deuterated analogue. On the other hand, estuarine water and wastewater samples were spiked with known concentrations of target analytes, and apparent recoveries were studied as explained above. In general, the matrix effect could be corrected with the use of deuterated analogues, except for 4-tOP and nonylphenols for which [²H₄]-n-nonylphenol did not provide good corrections.     

Determination of a wide range of volatile and semivolatile organic compounds in snow by use of solid-phase micro-extraction (SPME)

Quantification and transformation of organic compounds are pivotal in understanding atmospheric processes, because such compounds contribute to the oxidative capacity of the atmosphere and drive climate change. It has recently been recognized that chemical reactions in snow play a role in the production or destruction of photolabile volatile organic compounds (VOC). We present an environmentally friendly method for determination of VOC and semi-VOC in snow collected at three sites—remote, urban, and (sub-)arctic. A solid-phase micro-extraction (SPME) procedure was developed and (semi-)VOC were identified by gas chromatography with mass spectrometric detection (GC–MS). A broad spectrum of (semi-)VOC was found in snow samples, including aldehydes, and aromatic and halogenated compounds. Quantification was performed for 12 aromatic and/or oxygenated compounds frequently observed in snow by use of neat standard solutions. The concentrations detected were between 0.12 (styrene and ethylbenzene) and 316 μg L⁻¹ (toluene) and limits of detection varied between 0.11 (styrene) and 1.93 μg L⁻¹ (benzaldehyde). These results indicate that the SPME technique presented is a broad but selective, versatile, solvent-free, ecological, economical, and facile method of analysis for (semi-)VOC in natural snow samples.