Riverine discharge of perfluorinated carboxylates from the European continent.

The discharge of C6-C9 perfluorinated carboxylates (PFCAs) from major European rivers was studied and employed to assess European emissions of these compounds. Water samples were collected close to the mouths of 14 major rivers including the Rhine, Danube, Elbe, Oder, Seine, Loire, and Po. PFCA concentrations were determined using LC-MS/MS and used together with the mean annual water flow to estimate the riverine discharge of the PFCAs. The highest concentration measured was 200 ng/L for perfluorooctanoate (PFOA) in the Po River. The Po accounted for two-thirds of the total PFOA discharge of all the rivers studied, suggesting a major industrial source of PFOA in the Po watershed. All other nonremote rivers showed PFOA concentrations in the lower ng/L range, which indicates that widely distributed sources are also significant contributors to PFOA emissions in Europe. The total discharge of PFOA from the European rivers was estimated to be 14 tonnes/year, which is in reasonable agreement with reported emissions estimates. However, the total riverine discharge of perfluorohexanoate (PFHxA) of 2.8 tonnes/year estimated in this study was three times greater than the reported global emissions estimate, suggesting that there are significant, as yet unidentified sources of this compound.

Short- and medium-chain chlorinated paraffins in biota from the European Arctic -- differences in homologue group patterns.

Congener and homologue group patterns of chlorinated paraffins (CPs) in biota can be influenced by different processes, but these are not well studied yet. Short- (SCCPs) and medium-chain chlorinated paraffins (MCCPs) were quantified in liver from Arctic char and seabirds (little auk and kittiwake) collected at Bear Island (European Arctic) as well as in cod from Iceland and Norway. CP concentrations were between 5 and 88 ng/g wet weight (ww) for SCCPs and between 5 and 55 ng/g ww for MCCPs with one exception of 370 ng/g measured in a liver sample from little auk. The SCCP homologue group patterns were compared with those of technical mixtures and of SCCPs present in cod liver from the Baltic Sea. The latter showed a more common SCCP homologue distribution (sum of C(11) and C(12)>60%) in contrast to cod liver from the Northwest of Europe, which had a high abundance of C(10) and C(12) congeners. Seabirds from Bear Island contained an equally distributed SCCP homologue group pattern. In Arctic char, the SCCP distribution was closer to technical products, but with a high proportion (average of 18.9%) of C(10) congeners. A comparison of C(10)/C(12) ratios confirmed the higher abundance of C(10) congeners in samples from higher latitudes. For the first time, MCCPs could be detected in Arctic samples. The average proportion of C(14) congeners was 65.8%. The C(14)/C(15) abundance ratio was similar to technical mixtures. High-chlorinated CPs (Cl(>7)) were also detectable. The average chlorine content of the SCCPs was 61.9% (59.0-63.3%), and that of the MCCPs 55.8% (54.5-57.4%).

New quantification procedure for the analysis of chlorinated paraffins using electron capture negative ionization mass spectrometry.

An improved quantification procedure for the analysis of chlorinated paraffins (CPs) is presented based on electron capture negative ionization mass spectrometry. It compensates differences in response factors between reference CP mixtures and the CP pattern present in environmental samples. The use of a CP standard with a matching degree of chlorination is no longer necessary. It could be shown that the response factors of C10-, C11-, C12- and C13-CP mixtures of both 50 and 60% chlorine content were only slightly influenced by the carbon chain length. A linear correlation (R2 = 0.965) between the total response factor of a CP mixture and its chlorine content was obtained for seven short chain chlorinated paraffin mixtures (SCCP, C10-C13) with different composition and chlorine content (51-69%). Maximum single deviations were <7% for this reference set. It allowed to determine the correct total response factor of the CP composition present in a sample. The deviations were not more than 7-33% for five independent SCCP control samples compared to up to 373% for the conventional procedure. The procedure was tested by quantifying the SCCP and MCCP levels in 10 fish liver samples. The proposed method allowed to compensate the influence of the degree of chlorination of the applied reference standard on the total response factor.

Evaluation of four mass spectrometric methods for the gas chromatographic analysis of polychlorinated n-alkanes.

The suitability of four mass spectrometric methods for the gas chromatographic analysis of polychlorinated n-alkanes (PCAs, also called chlorinated paraffins) was evaluated and compared using spiked and fish liver samples. Electron ionization tandem mass spectrometry (EI-MS/MS) as well as electron capture negative ionization (ECNI) combined with low and high resolution mass spectrometry and CH4/CH2Cl2-negative ion chemical ionization (NICI) low resolution mass spectrometry were investigated. All methods showed an accuracy of <21% for the analysis of spiked fish samples. However, the analysis of real samples showed deviations of up to 46% between the four mass spectrometric methods. The influence of the selected reference standard on quantification was also evaluated. The use of a quantification standard with a degree of chlorination deviating from that of the sample can result in differences of > 100% for the ECNI methods. EI-MS/MS and CH4/CH2Cl2-NICI led to errors of maximum 17% and 33%, respectively, independent from the degree of chlorination of the used reference standard.

First study of congener group patterns and concentrations of short- and medium-chain chlorinated paraffins in fish from the North and Baltic Sea.

This study presents the first investigation of concentrations and congener group patterns of short- (SCCPs) and medium-chain chlorinated paraffins (MCCPs) in fish from the North and Baltic Sea. North Sea dab, cod and flounder were studied. High resolution gas chromatography (HRGC) coupled to low resolution mass spectrometry (LRMS) in the electron capture negative ionization mode (ECNI) was employed. Good linearity (R2>0.993, 7 measuring points) was achieved between 1 and 100 ng/g of CP mixtures for SCCPs and MCCPs. The limits of detection were 0.5-1 ng/microl of CP mixture for the major congener groups of SCCPs and MCCPs. A clean-up comprising fat extraction, adsorption chromatography on silicagel impregnated with concentrated sulphuric acid and adsorption chromatography on Florisil was employed to avoid interferences from other polychlorinated compounds. Recoveries of CPs in spiked samples ranged between 80% and 100%. Accuracy was controlled with spiked samples and deviated not more than 10% from the expected values. Quantification was performed with standards of an average chlorine content as close as possible to that of the samples (SCCPs: 59-62%, MCCPs: 53-58%). SCCP concentrations ranged between 19 and 286 ng/g liver wet weight (ww), MCCP concentrations were comparable with a range of 25-260 ng/gww. Congener group patterns were also determined and discussed. In samples from the Baltic Sea the SCCP congener pattern was similar to that of commercial SCCP mixtures or C13 congeners were most abundant. In samples from the North Sea a higher relative abundance of C10 congeners was observed.

Determination of total polychlorinated n-alkane concentration in biota by electron ionization-MS/MS.

Electron ionization (EI) tandem mass spectrometry (MS/MS) allowed the fast determination of the total concentration of short- and medium-chained polychlorinated n-alkanes (PCAs) in biota. EI fragment ions common to all PCAs could be identified. Collision-induced dissociations (CIDs) were carried out by ion trap and triple quadrupole EI-MS/MS. CIDs of m/z 91 --> 53 (limit of detection (LOD) 0.15 ng/microL), 102 --> 65 (LOD = 0.2 ng/microL), and 102 --> 67 (LOD = 0.1 ng/microL) were applied for the determination of the total short- and medium-chain PCA concentration in pooled fish liver samples (North Sea dab, cod, flounder) from the North Sea and from the Baltic Sea using both MS technologies. Total PCA concentrations were in the range of 88-607 ng/g. Accuracy was controlled with spiked samples and deviated not more than 15% from expected values.

Limitations of low resolution mass spectrometry in the electron capture negative ionization mode for the analysis of short- and medium-chain chlorinated paraffins.

The analysis of complex mixtures of chlorinated paraffins (CPs) with short (SCCPs, C(10)-C(13)) and medium (MCCPs, C(14)-C(17)) chain lengths can be disturbed by mass overlap, if low resolution mass spectrometry (LRMS) in the electron capture negative ionization mode is employed. This is caused by CP congeners with the same nominal mass, but with five carbon atoms more and two chlorine atoms less; for example C(11)H(17)(37)Cl(35)Cl(6) ( m/ z 395.9) and C(16)H(29)(35)Cl(5) ( m/ z 396.1). This can lead to an overestimation of congener group quantity and/or of total CP concentration. The magnitude of this interference was studied by evaluating the change after mixing a SCCP standard and a MCCP standard 1+1 (S+MCCP mixture) and comparing it to the single standards. A quantification of the less abundant C(16) and C(17) congeners present in the MCCP standard was not possible due to interference from the major C(11) and C(12) congeners in the SCCPs. Also, signals for SCCPs (C(10)-C(12)) with nine and ten chlorine atoms were mimicked by MCCPs (C(15)-C(17)) with seven and eight chlorine atoms (for instance C(10)H(12)Cl(10) by C(15)H(24)Cl(8)). A similar observation was made for signals from C(15)-C(17) CPs with four and five chlorine atoms resulting from SCCPs (C(10)-C(12)) with six and seven chlorine atoms (such as C(15)H(28)Cl(4) by C(10)H(16)Cl(6)) in the S+MCCP mixture. It could be shown that the quantification of the most abundant congeners (C(11)-C(14)) is not affected by any interference. The determination of C(10) and C(15) congeners is partly disturbed, but this can be detected by investigating isotope ratios, retention time ranges and the shapes of the CP signals. Also, lower chlorinated compounds forming [M+Cl](-) as the most abundant ion instead of [M-Cl](-) are especially sensitive to systematic errors caused by superposition of ions of different composition and the same nominal mass.

Dichloromethane-enhanced negative ion chemical ionization for the determination of polychlorinated n-alkanes.

The use of dichloromethane/methane reagent gas mixtures is described as an alternative to conventional electron capture negative ionization for the determination of polychlorinated n-alkanes (PCAs). A nearly exclusive formation of [M + Cl]- adduct ions was observed suppressing the generation of other fragment ions. The resulting enhanced selectivity and sensitivity lowered quantification limits to 3 ng for a technical PCA mixture and 10.5-13.5 pg for single congeners. Response factors for congeners of different degrees of chlorination varied by not more than a factor of 2. Interferences from other polychlorinated compounds present in environmental samples such as toxaphene or chlordanes were suppressed by a factor of 5 or more. The technique was applied for the determination of the composition of technical PCA mixtures as well as for the analysis of PCAs in North Sea dab liver.