Simultaneous analysis of atmospheric halocarbons and non-methane hydrocarbons using two-dimensional gas chromatography

A gas chromatographic system was constructed to simultaneously measure ambient non-methane hydrocarbons (NMHCs) and halocarbons, which play significant roles in tropospheric ozone formation and stratospheric ozone loss, respectively. A heart-cut device based on a Deans switch was connected to two capillary columns to cover the full range of NMHCs and halocarbons. Analytes more volatile than C₆ NMHCs and the halocarbon CFC-113 were separated with a PLOT column, while the remaining less volatile compounds were separated with a DB-1 column. Merge-and-split of the flows at the end of the two columns allowed the NMHCs and halocarbons to be observed simultaneously by electron capture detection (ECD) and flame ionization detection (FID). To avoid peak-overlap from the two columns while merging, programmed pressures were incorporated to control the Deans switch. In addition to the advantage of measuring two important classes of compounds in the atmosphere at the same time, this method has the additional benefit of using the homogeneity of atmospheric CFC-113 as an “intrinsic” internal reference. Thus, better data continuity, less consumption of gas standards, and real-time quality control can all be achieved.     

Isotope analysis of hydrocarbons: trapping, recovering and archiving hydrocarbons and halocarbons separated from ambient air

It is argued that isotope analysis of atmospheric non-methane hydrocarbons (NMHCs) and, in particular, the analysis of the deuterium/hydrogen (D/H) ratio is valuable because the dominant self-cleansing property of the troposphere is based on the OH radical which removes, e.g., CH4 and other alkanes by H-atom abstraction, which induces large kinetic isotope effects. The major obstacle in applying D/H isotope analysis to atmospheric NMHCs is not only the low abundance of D itself but, in particular, the low concentrations of NMHCs in the parts per trillion range. We show how a selection of NMHCs can be quantitatively separated from 300 L air samples together with CO2 as carrier gas matrix, by using high efficiency cryogenic traps. After diluting the extracted NMHC mixtures with hydrocarbon free air, and determining the mixing ratios, good agreement with original whole air sample analysis exists for alkanes and several halocarbons. For unsaturated hydrocarbons and some other halocarbons the extraction and recovery yield under the given conditions fell considerably, as a function of boiling point. Furthermore, the mixture of NMHCs in the CO2 matrix is proven to remain unchanged over several years when conveniently stored in glass ampoules. The 'extracts' or 'concentrates' of condensables extracted from larger air samples will enable the D/H isotope analysis of ultra trace gases in the atmosphere.     

Determination of polycyclic aromatic hydrocarbons in Athens atmosphere

Concentrations of total suspended particulates (TSP), benzene soluble fraction (BSF) and polycyclic aromatic hydrocarbons (PAH) have been determined in ambient air from four different sites in Athens, situated in urban, semi-industrial and industrial areas. GLC analysis has been applied for the determination of PAH, while the CGC/MS technique was used in order to confirm the obtained results. The same PAH pattern was observed for all stations. The identified PAH have been fluoranthene (FLA), pyrene (PYR), benzo(a)anthracene (BaA), chrysene (CHR), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), benzo(e)pyrene (BeP) and benzo(ghi)perylene (B(ghi)P). The concentrations of individual PAH ranged from traces to 33 ng m-3 (e.g. same or lower comparing to other large cities). The higher values of PAH were found during adverse meteorological conditions.     

High-volume sampling of polycyclic aromatic hydrocarbons in the workplace atmosphere

During the determination of the exposure of workers to polycyclic aromatic hydrocarbons (PAH), two sampling systems have been compared at a workplace in the refractory industry: a stationary high-volume dust sampling system equipped with a glass fibre filter and a stationary sampling device consisting of a glass wool filter and serially connected impingers. Repeated parallel sampling operations over several hours showed that the amounts of PAH collected by the dust collection system have been generally smaller.Dedicated to Professor Dr. Dr. h.c. mult. J. F. K. Huber on the occasion of his 70th birthday     

Detection and measurement of volatile hydrocarbons at ambient concentrations in the atmosphere

Modern techniques for the sampling and analysis of volatile hydrocarbons present at ppm-ppM levels in air are reviewed. Emphasis is placed on methods designed to detect and determine individual hydrocarbons of particular interest. Advances in instrumentation and automation are discussed with particular reference to systems combining gas chromatography, mass spectrometry and computerized data-analysis.     

Gas chromatography negative ion chemical ionization mass spectrometry: application to the detection of alkyl nitrates and halocarbons in the atmosphere

Alkyl nitrates and very short-lived halocarbon species are important atmospheric trace gas species that are present in the low to sub parts per trillion concentration range. This presents an analytical challenge for their detection and quantification that requires instrumentation with high sensitivity and selectivity. In this paper, we present a new in situ gas chromatograph negative ion chemical ionization mass spectrometer (GC/NICI-MS) coupled to a non-cryogen sample pre-concentration system. This instrument, with detection limits of <0.01 ppt, is capable of detecting and quantifying a large suite of alkyl nitrate and halocarbon species with high sensitivity and precision. The effects of ion source temperature and reagent gas pressure on the ionization efficiency of the NICI mode are investigated and the results are used to optimize the sensitivity. The NICI mode is compared to the more frequently used electron impact (EI) ionization and the enhancements in sensitivity are presented for all the calibrated compounds.     

Trace analysis of halocarbons in water; Direct aqueous injection with electron capture detection

Interest in monitoring halogenated organics in drinking water and natural surface and ground water in the low ppb range continues to grow. There is a tendency to include still more volatile halocarbons, the trace determination of which is known to be rather demanding. This prompted us to re-examine the feasibility of large-volume direct aqueous injection onto capillary columns, coupled with ECD. A primary problem was to avoid simultaneous elution of water with halocarbons, since water suppresses the ground current of the ECD. The following measures contributed to the solution of this problem. Apolar, extremely inert, columns are required to elute water completely, and even before very light halocarbons. Their coatings have to be far thicker (≈? 5 mUm) than commonly employed thick films since they must permit isothermal analysis at a column temperature around 100°C in order to ensure rapid and complete elution of water. Finally, it is essential that sampling be carried out on-column for two reasons: diffusion of water vapor in the injector, resulting in delayed elution, is then eliminated, and peak distortion during splitless injection is avoided. Although we now know that persilylated columns with immobilized coatings withstand routine water injections, more longterm experience is needed to provide detailed recommendations for the handling of these columns.     

"Cold" solid-phase microextraction method for the determination of volatile halocarbons present in the atmosphere at ultra-trace levels

Anthropogenic volatile halocarbons are compounds of great enviromnental concern because of their involvement in global change phenomena. They are present in the atmosphere at concentration levels in the order of parts per trillion by volume. The chosen analytical method for their determination is capillary gas chromatography coupled to mass spectrometry, preceded by an enrichment step on suitable adsorbent resins. The method here presented makes use of the solid-phase microextraction as a pre-analytical technique, using sub-ambient temperature in order to enhance the retention capability of the fiber coating. The proposed method was evaluated in terms of extraction efficiency, linearity, reproducibility, andlimits of detection. Results obtained showed that trace atmospheric halocarbons are detectable even when enriching very small air sample volumes. A good chromatographic resolution is obtained as a consequence of the extremely low injection volume. Finally a standard GC-MS instrumentation equipped with a simple split-splitless injector was employed, thus avoiding the use of expensive dedicated apparatus. The method was also applied to the analysis of actual samples collected both in remote, and in semi-remote sites.     

Formation of disilanes in the reaction of stable silylenes with halocarbons

Reactions of stable silylenes 1 and 2 with a variety of halogenated organic compounds have been studied. Depending on the nature of the halocarbon, the products can be disilanes, LSiX-LSiR, or monosilanes, LSiXR, or a mixture of both types of products. Hexachloroethane reacts with the silylenes to give mainly the dichlorodisilane, LSiX-LSiX. The experimental results are rationalized in terms of several related free-radical chain mechanisms.     

Reactions of a stable silylene with halocarbons

An unusual product formation is observed for the insertion reaction of the thermally stable silylene Si[(NCH(2)Bu(t))(2)C(6)H(4)-1,2][abbrev. as Si(NN)] into the carbon-halogen bond of alkyl or aryl halides RHal (Hal=Cl, Br). In general, depending on the halogen, the reaction either results in a disilane of type (NN)Si(Hal)-(R)Si(NN) for Hal=Cl or a mixture of disilane and the monosilane (NN)Si(R)(Hal) for Hal=Br. The results are put into context to previously suggested mechanisms. The disilane (NN)Si(Hal)-(R)Si(NN)(Hal=Cl or Br) is thermally labile and mild thermolysis yields the corresponding monosilane (NN)Si(R)(Hal) and silylene 1. Additionally, strong evidence is presented for a radical pathway for the reaction of 1 and RHal.     

The vertical distribution of halocarbons in the stratosphere

Summary By means of cryogenic sampling and subsequent gas-chromatographic analysis vertical profiles of CCl₄, CCl₃F, CCl₂F₂, CClF₃, CF₄, C₂Cl₃F₃, C₂Cl₂F₄, C₂ClF₅, C₂F₆, CH₃Cl and CH₃CCl₃ were derived for stratospheric heights up to 35 km. Vertical profiles of halocarbons computed by means of one-dimensional and two-dimensional models fall off less rapidly in the stratosphere than the measured profiles, this systematic discrepancy being due to deficiencies in the radiation and transport schemes of present models. It is shown that measured profiles of fully halogenated hydrocarbons provide a tool for systematically studying these deficiencies and thus improving the models. Sources and sinks of halocarbons are discussed, and an assessment of past and future sources of organically bound chlorine in the atmosphere is made.

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Die vertikale Verteilung halogenierter Kohlenwasserstoffe in der stratosphäre

Zusammenfassung Die vertikalen Profile von CCl₄, CCl₃F, CCl₂F₂, CClF₃, CF₄, C₂Cl₃F₃, C₂Cl₂F₄, C₂ClF₅, C₂F₆, CH₃Cl und CH₃CCl₃ wurden für stratosphärische Höhen bis zu 35 km mit Hilfe kryogener Probenahme und anschließender gas-chromatographischer Analyse bestimmt. Die mit Hilfe von ein- und zweidimensionalen Modellen berechneten Profile fallen in der Stratosphäre weniger schnell ab als die gemessenen. Dieser systematische Unterschied ist auf Mängel in den Strahlungs- und Transportmechanismen der gegenwärtigen Modelle zurückzuführen. Es wird gezeigt, daß die gemessenen Profile der vollhalogenisierten Kohlenwasserstoffe dazu dienen können, diese Mängel zu untersuchen und die Modelle zu verbessern. Ursprung und Verbleib der halogenierten Kohlenwasserstoffe werden beschrieben und vergangene und zukünftige Quellen organisch gebundenen Chlors in der Atmosphäre diskutiert.

     

Remarks on the sampling procedures for polycyclic aromatic hydrocarbons from the atmosphere

Summary Despite all efforts to optimize the sampling procedure for polycyclic aromatic hydrocarbons (PAH) a part of the PAH is lost during the sampling period. The amount of loss depends on the vapour pressure, the air flow rate, the oxidants in the suspended matter and on the sampling time. The sampling time in return is determined by the PAH concentration in the atmosphere and cannot be shortened infinitely, at least not at the expense of the air flow rate. When the concentration of the PAH is extremely low, a repeated change of the filters is advisable. Losses of PAH even occur when filters are stored in the dark. An evaluation of these losses is difficult for many reasons. There is no relationship between the amount of loss and time unit; the decrease of each PAH is different and seems to depend on the composition of the particulate matter collected on the filter. The disappearance of the PAH from the filter is a continual process, therefore a rapid performance of the analysis is inevitable.

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Bemerkungen zur Probenahme von polycyclischen aromatischen Kohlenwasserstoffen aus Luft

Zusammenfassung Trotz aller Bemühungen um die Optimierung der Probenahme von Polycyclen sind Verluste nicht zu vermeiden. Die Höhe solcher Verluste ist abhängig vom Dampfdruck, von der Strömungsgeschwindigkeit der Luft, vom Vorhandensein von Oxidationsmitteln und von der Dauer der Probenahme. Letztere hängt wiederum von der Konzentration der Polycyclen in der Luft ab und kann nicht beliebig vermindert werden, zumindest nicht auf Kosten der Strömungsgeschwindigkeit. Bei extrem niedrigen Konzentrationen ist ein wiederholter Filterwechsel ratsam. Verluste treten auch dann auf, wenn die Filter im Dunkeln gelagert werden. Eine Erklärung dieser Verluste ist aus verschiedenen Gründen schwierig. Die Höhe des Verlusts steht in keiner Beziehung zur Zeit. Die Abnahme der verschiedenen Polycyclen ist unterschiedlich und scheint von der Zusammensetzung der auf dem Filter gesammelten Teilchen abzuhängen. Das Verschwinden der Polycyclen vom Filter erfolgt kontinuierlich, so daß eine schnelle Durchführung der Analyse notwendig ist.

     

Thermal electron capture in the mixtures of halocarbons and atmospheric gases

The electron capture processes in the mixtures containing halocarbon (CH₂F₂ or CHF₃) and nitrogen as well as halocarbon, oxygen and carbon dioxide have been investigated. The mechanism has been revealed and the corresponding rate constants have been determined.     

Optimization of the gas-chromatographic determination of airborne halocarbons

Summary Airborne C₁- and C₂-halocarbons can be determined by cartridge sampling, gas chromatography and electron capture detection. High accuracy is achieved in the concentration range typical for rural and forest air, when the following components of the analytical train are meticulously optimized: enrichment on adsorption cartridges, thermodesorption, cryofocussing, capillary gas chromatography and electron capture detection. The parameters associated with sample collection, i.e. type and properties of adsorbent, dimensions and design of the cartridge, temperatures, and gas flows must be judiciously balanced under consideration of the prevalent air concentrations and the dynamic range of the ECD, in order to achieve standard deviations of 10% or less for replicate analyses.

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Optimierung der gas-chromatographischen Bestimmung von Halogenkohlenwasserstoffen in Luft

     

Identification of halocarbons in the Tiber and Marta rivers by static headspace and liquid–liquid extraction analysis

Volatile organochlorine compounds in the Tiber and Marta rivers have been analyzed by liquid–liquid extraction and headspace gas chromatography. Several different halogenated compounds were identified, in particular chloroform, bromoform, trichloroethane, trichloroethene, and tetrachloroethene. The concentrations of the halocarbons varied between 0.05 and 4.5 μg L^–1 with a relative standard deviation ≤4.0%. The highest concentrations were observed for chloroform, bromoform, and tetrachloroethene in the Marta and Tiber rivers. The results obtained by use of the two analytical methods were similar.     

TG-MS与Py-GC相结合法研究惰性气氛下含硫模型化合物热解过程中硫的脱除及释放行为研究

采用热重-质谱法( TG-MS)和热解-气相色谱法( Py-MS)相结合的方法对模型化合物(十四硫醇、二丁基硫醚、苯硫醚、二甲基噻吩、苯并噻吩和二苯并噻吩等)在惰性气氛下硫的脱除及释放行为进行研究。惰性气氛下硫的脱除顺序为：十四硫醇>二丁基硫醚>二甲基噻吩>苯并噻吩>苯硫醚>二苯并噻吩,苯硫醚除外,该顺序与含硫官能团的热分解顺序一致。在热解过程中,所有模型化合物在质谱和气相色谱仪上均被检测到SO2;除苯硫醚和二苯并噻吩外,其他模型化合物中均检测到了COS;而只在十四硫醇、二丁基硫醚和二甲基噻吩中检测到了H2 S。且热解气中SO2含量要显著高于H2 S和COS。这是由于活性炭作载体时,惰性气氛下内部氢的含量显著小于内部氧的含量,所以大多数的含硫自由基易与内部氧结合以SO2的形式逸出。对于苯硫醚、苯并噻吩和二苯并噻吩中没有检测到H2 S,是由于内部氢的不足,使得含硫自由基不能与内部氢结合,所以没有检测到H2 S逸出。     

Proteomic maps-toxicity relationship of halocarbons studied with similarity index and genetic algorithm

In this work we analyzed proteomic maps obtained from hepatocytes, which were treated with 14 halocarbons. A similarity index was introduced as a robust measure of similarity between two maps or between two selections of spots within the maps. A searching algorithm was used to identify the spots that may play an important role in toxicity mechanism. The highest correlation coefficients obtained between the similarity index and biological parameter were larger than 0.9.     

Problems of the control of volatile halogenated hydrocarbons in tap and waste waters

The concentration of volatile halogenated hydrocarbons in chlorinated tap water does not stay constant but increases during its passage through water supply systems, which indicates a certain incompleteness and the continuation of the transformation of humic substances upon the chlorination of water. The known official (certified) procedures, including the State Standard ones, seven in number, which are based on headspace gas chromatography, do not take into account such a peculiarity of tap water and deal with the quantification of free halogenated derivatives of hydrocarbons only. The comparative evaluation of official procedures is performed, and the sources of errors exceeding the acceptable level are inventoried; methods of optimization of all analytical steps are proposed to elaborate procedures ensuring the minimal error and reliable information on the concentration of volatile halogenated hydrocarbons in tap and waste waters.