Determination of chlorinated paraffins by GC-MS

Junk, S.; Meisch, Hans-Ulrich

doi:10.1007/bf00323821

Cited by 20 publications

(12 citation statements)

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“…Junk and Meisch [55] developed a low resolution method for PCA analyses based on GC/electron ionization (EI)-MS in the SIM mode. By introducing a commercial formulation directly into the ion source of the MS via a direct insertion probe, and under full scan conditions, they selected the C 5 H 10 35 Cl + (m/z 105) ion to be the characteristic ion, i.e., the quantitation ion, of the standard.…”

Section: Quantitation By Gas Chromatography Mass Spectrometrymentioning

confidence: 99%

“…Because of the difficulty of separating PCAs even on high resolution GC columns, Parlar et al [58] recommended the use of direct introduction into the mass spectrometer via a short uncoated column. Other authors Chlorinated Paraffins 215 have recommended similar approaches to address the difficulty of resolving PCA components [55].The methods outlined above all rely on low resolution MS and inherently lack selectivity [14]. In addition, methods relying on full scan mode or EI mode also lack the sensitivity required to measure trace amounts of PCAs [23,24,55] although they may be suitable for analysis of effluents or commercial products.…”

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confidence: 98%

“…Other authors Chlorinated Paraffins 215 have recommended similar approaches to address the difficulty of resolving PCA components [55].…”

mentioning

confidence: 99%

“…In addition, methods relying on full scan mode or EI mode also lack the sensitivity required to measure trace amounts of PCAs [23,24,55] although they may be suitable for analysis of effluents or commercial products.…”

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confidence: 99%

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Chlorinated Paraffins

Muir

Stern

Tomy

2000

Volume 3 Anthropogenic Compounds Part K

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Chlorinated paraffins or polychlorinated n-alkanes (PCAs) consist of C 10 to C 30 n-alkanes with chlorine content from 30 to 70% by mass. PCAs are used as high temperature lubricants, plasticizers, flame retardants, and additives in adhesives, paints, rubber, and sealants. This chapter reviews the existing data on the production, uses, reactions, methods of quantitative analysis, and levels of PCAs, and includes an assessment of environmental distribution using a steady state non-equilibrium fugacity-based chemical fate models. Short chain PCAs (C 10 to C 13 with 60-70% chlorine) have similar molecular weight and physical properties (octanolwater partition coefficient, water solubility, vapor pressure) to many persistent organochlorines such as PCBs and toxaphene. Medium chain (C 14 to C 17 ) and long chain (C 18 to C 30 ) PCAs are extremely hydrophobic and nonvolatile and likely to be associated with particles in aquatic systems. The limited biodegradation data suggests that PCAs are less persistent in water, sediments, or biota than other organochlorines. To date there is limited information on the distribution and fate of PCAs in the environment. There have been recent advances in the analysis of C 10 to C 13 PCAs using high resolution negative ion mass spectrometry. Interlab comparisons have shown that both high resolution and low resolution negative ion mass spectrometry can be employed to determine PCAs in environmental samples, although agreement between laboratories is poor compared with the determination quantitation of PCBs and organochlorine pesticides. There are indications that PCAs are widespread environmental contaminants at ng/l levels in surface waters and ng/g (wet weight) levels in biota. However, environmental measurements of PCAs are very limited at the present time in the USA and Canada and are only slightly more detailed in western Europe. Application of the Equilibrium Criterion Model, Level III (steady state, nonequilibrium) to representative short (C 12 H 20 Cl 6 ) and medium chain PCAs, (C 16 H 24 Cl 10 ) using the best available physical-chemical property data and estimated degradation rates, showed that that medium chain compound C 16 H 24 Cl 10 would achieve higher concentrations in sediment and soil than the short chain C 12 H 20 Cl 6 because of slower degradation rates and lower water solubility. Volatilization from water to air of both compounds was predicted by the model suggesting the possibility of long range transport via atmosphere and oceans. The environmental residence time of C 16 H 24 Cl 10 is estimated to be 350 days compared to 170 days for C 12 H 20 Cl 6 . Future studies will require better analytical methods and reference materials certified for PCA content. Additional data is needed to evaluate exposure to PCAs in the environment, particularly in light of their continued production and usage around the globe. Keywords. Chlorinated paraffins, Polychlorinated n-alkanes, IntroductionAs their name implies, chlorinated paraffins are chlorinated derivatives of paraffinic...

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Section: Quantitation By Gas Chromatography Mass Spectrometrymentioning

confidence: 99%

mentioning

confidence: 98%

“…Other authors Chlorinated Paraffins 215 have recommended similar approaches to address the difficulty of resolving PCA components [55].…”

mentioning

confidence: 99%

mentioning

confidence: 99%

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Chlorinated Paraffins

Muir

Stern

Tomy

2000

Volume 3 Anthropogenic Compounds Part K

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“…Technical sPCA mixtures consist of several thousand components, and due to the large number of isomers, complete chromatographic separation seems impossible at this point. This analytical challenge has resulted in different analytical approaches to analysis of sPCA [1,2,3,5,8,9,10,17,18].…”

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Polychlorinated Alkanes in Fish from Norwegian Freshwater

Borgen

Schlabach

Kallenborn

et al. 2002

The Scientific World JOURNAL

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Short-chain polychlorinated alkanes (sPCAs) have been measured in freshwater fish samples from different lakes all over Norway and from the Norwegian Arctic. The analyses were performed with high-resolution GC coupled to high-resolution MS in electron capture negative ion mode. The species investigated were trout, Arctic char, and burbot (Lota lota). Muscle tissue in the lake trout and Arctic char, and liver in burbot, were selected for analyses because of their high lipid content. Σ Σ Σ ΣsPCA concentration ranged from 108 to 3700 ng/g fat. The highest value was found in the south of Norway near an industrial area.KEY WORDS: chlorinated paraffins, ECNI, freshwater fish, HRGC/HRMS DOMAINS: environmental chemistry, persistent organic pollutants INTRODUCTIONPolychlorinated alkanes (PCA), or chlorinated paraffins, are straight-chain alkanes with varying degrees of chlorination. They have been produced since the 1930s to an extent of approximately 300 kilotons estimated for the western world [1]. PCA are mainly produced by direct chlorination of a petroleum fraction with molecular chlorine in the presence of UV light [2]. PCA have been used as additives in high temperature and pressure lubricants as well as secondary plasticisers and flame retardants in plastics and paints [1,4].PCA are divided into three main categories -short-(C10-C13), medium-(C14-C17), and long-chain (C18-C30) -and further by their degree of chlorination -low (<50%) and high (>50%) [4]. Because of their relatively high assimilation and accumulation potential, the short-chain, highly chlorinated PCAs have been most widely studied. Although PCA generally have shown low toxicity to mammals, short-chain PCA (sPCA) have a carcinogenic potential in rats and mice [5]. In addition, recent dose-response studies have shown that oral intake of sPCA by mice results in an increase in liver weight, which is considerable compared to reference materials [12]. They have also been shown to be toxic towards certain species in the aquatic environment [4,6,7], although at concentration levels several orders of magnitude higher than for TCDD [7]. Norwegian Freshwater TheScientificWorldJOURNAL (2002) 2, 136-140 Borgen: PCAs in Fish from 137The complexity of sPCA mixtures make it difficult to provide an analytical method for their precise and specific quantitative determination. Technical sPCA mixtures consist of several thousand components, and due to the large number of isomers, complete chromatographic separation seems impossible at this point. This analytical challenge has resulted in different analytical approaches to analysis of sPCA [1,2,3,5,8,9,10,17,18].In this study, sPCA have been measured in lake trout, burbot, and Arctic char from different locations in Norway, and in the Norwegian Arctic. EXPERIMENTALThe fish samples were homogenised with sodium sulphate and 13C-labelled PCB 118 was added as an internal standard. The samples were then extracted with a mixture of ethyl acetate and cyclohexane (1:1). Separation of the PCAs from the fat was done on a GP...

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Evaluation of three ionisation modes for the analysis of chlorinated paraffins by gas chromatography/ion‐trap mass spectrometry

Castells

Santos

Galcerán

2004

Rapid Comm Mass Spectrometry

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The applicability of three ionisation modes to the analysis of short-chain chlorinated paraffins (SCCPs) using gas chromatography coupled with mass spectrometry (GC/MS) was evaluated. MS conditions for electron ionisation (EI), positive chemical ionisation (PCI) and electron-capture negative ionisation (ECNI) were optimised using commercially available individual tetra-, penta- and hexachlorodecanes. In addition, mass spectra were studied and fragmentation pathways were proposed for each individual congener. Different fragment ions were evaluated for quantification, and ECNI-MS using [HCl2](-) and [Cl2](-*) ions was selected for the determination of SCCPs. Quality parameters (repeatability, limits of detection and calibration range) were established for the proposed method, which was then applied to the analysis of SCCPs in river sediments.

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Determination of chlorinated paraffins by GC-MS

Cited by 20 publications

References 9 publications

Chlorinated Paraffins

Chlorinated Paraffins

Polychlorinated Alkanes in Fish from Norwegian Freshwater

Evaluation of three ionisation modes for the analysis of chlorinated paraffins by gas chromatography/ion‐trap mass spectrometry

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