Electron Capture Negative Ionization Mass Research Articles

A simple laboratory method for the generation of mixed brominated-chlorinated paraffin single chain mixtures

Brominated-chlorinated paraffins (Br-CPs) are a comparably new compound class that features both Cl and Br atoms on one or several alkane backbones. Due to legal restrictions in the use of conventional chlorinated paraffins (CPs), Br-CPs have the potential to become emerging contaminants. Currently, their determination is hampered by the lack of suitable reference standards. Here, we present a simple synthesis procedure with single chain alkanes that leads to Br-CPs with ∼4–8 chlorine and 1 to 4 bromine substituents according to gas chromatography with electron capture negative ion mass spectrometry (GC/ECNI-MS). The single-chain Br-CP mixtures were obtained by the shared chlorination and bromination of eight single-chain alkanes (C10 to C17) at two reaction times, respectively. The carbon content of the 16 single-chain Br-CP products, determined by elemental analysis (EA), ranged from 30.8 to 43.8 %. The typical hump peak known from CPs was detected with GC with flame ionization detection (GC/FID), electron capture detection (GC/ECD) and GC/ECNI-MS. The complexity indicated that low-resolution mass spectrometry is not sufficient for an adequate analysis of Br-CPs. A mathematical formula was developed which allows to calculate all possible combinations of Br and Cl that are in line with the carbon content. The proton magnetic resonance spectroscopy (1H NMR) spectra showed similarities to the ones of CPs with one chemical shift range for protons on nonhalogenated carbons and one for protons with one halogen on the same carbon.

Short- and medium-chain chlorinated paraffins in sediment from the Haihe River Basin: Sources, distributions, and ecological risk assessment

Chlorinated paraffins (CPs) can accumulate in sediment and pose risks to ecological systems and human health. The Haihe River Basin is one of the seven main river basins in China and is mainly in the Beijing–Tianjin–Hebei region, which is densely populated and very urbanized. There is therefore a high probability of CP pollution in the Haihe River Basin. However, CP pollution and the environmental risks posed by CPs in the Haihe River are not well understood. In this study, the concentrations of short-chain CPs (SCCPs) and medium-chain CPs (MCCPs) in sediment from six rivers in the Haihe River Basin system were determined using two-dimensional gas chromatography electron-capture negative ionization mass spectrometry. The total SCCP and MCCP concentrations in the sediment samples ranged from 131.83 to 1767.71 and from 89.72 to 1442.82 ng/g dry weight, respectively. The total organic carbon content did not significantly correlate with the CP concentrations. The dominant SCCP congener groups were C10Cl6–7 and the dominant MCCP congener groups were C14Cl7–8. Significant relationships (R = 0.700, p < 0.05) were found between the SCCP and MCCP concentrations, indicating that SCCPs and MCCPs may have similar sources. Hierarchical cluster analysis and principal component analysis indicated that sediment in the study area was contaminated with CPs through the use of the CP-42 and CP-52 commercial products in industrial processes and human activities. The ecological risks posed by CPs were assessed and SCCPs were found to pose high risks in the Yongding New River but moderate risks in the other rivers. MCCPs were found to pose minimal risks to the aquatic environment at most of the sampling points.

Chlorinated paraffins in nut-nougat and chocolate spreads from the German market

Chlorinated paraffins (CPs) are amongst the most discussed polyhalogenated pollutants in recent years. Their ubiquitous occurrence in the environment and especially foodstuff has given rise to concerns about CP uptake levels. Especially animal products and oils, i.e. foodstuff with high fat contents showed comparably high CP contaminations. In this study, nut-nougat and chocolate spread samples (n = 30) from the German market were analyzed on the occurrence of short-chain CPs (SCCPs) and medium-chain CPs (MCCPs) via gas chromatography coupled with electron capture negative ion mass spectrometry (GC/ECNI-MS). Fifteen (= 50%) of the samples contained CPs, with MCCPs being much higher abundant (17–270 ng/g fresh weight (fw)) in most samples than SCCPs (7.5–50 ng/g fw). No statistical correlation could be established between SCCP or MCCP occurrence on one hand and manufacturer or ingredients, such as palm oil on the other hand. A preliminary risk assessment of the detected levels gave margins of exposure (MOE) to CPs from consumption of chocolate and nut-nougat spreads ranging from approx. 16,000 to 48,000. Since health concerns are expected at an MOE of <1,000, this indicated no risk from CP intake for the consumer by consumption of these products, based on current knowledge. • CPs were analyzed in 30 nut-nougat and chocolate spreads from the German market. • Short-chain CPs (SCCPs) and medium-chain CPs (MCCPs) were separately quantified. • Fifteen samples (50%) contained CPs between 7.5 and 270 ng/g fat. • MCCPs were higher abundant than SCCPs in most samples. • A preliminary risk assessment indicated no risk from CP intake for consumers.

Occurrence of legacy organochlorine pesticides in small mammals from two mountainous National Parks in southeastern Brazil

In southeastern Brazil, particular altitudinal grassland ecosystems, known as campos de altitude, occur at mountainous summits that host an outstanding level of biodiversity and endemism. However, despite being environmentally protected areas, several studies have shown their susceptibility to the impacts of climate change and airborne pollution. Previous studies highlighted that organochlorine pesticides (OCPs), present higher atmospheric concentrations along altitudinal gradients and can be locally deposited. On top of that, formerly used OCPs are still detected in the atmosphere on those mountaintops, long after their phase-out. Nevertheless, the potential bioaccumulation of OCPs by endemic species has not yet been assessed. Thus, we aimed to investigate the occurrence of OCPs in terrestrial subalpine wildlife and to establish a baseline for further in-depth studies on OCPs, or similar hazardous chemicals, in these endangered environments. In summary, 28 OCP congeners were investigated in 49 liver samples of ten small mammal species collected in 2013 and in 2016. Chemical analyses were based on gas chromatography coupled with electron capture negative ionization mass spectrometry (GC/ECNI-MS). Additional stable isotope analyses (δ 15 N and δ 13C) were performed to elucidate the role of trophic position on OCP bioaccumulation. Mirex, heptachlor, hexachlorobenzene, chlordane, and hexachlorocyclohexane congeners were the most frequently detected OCPs (59–97% of all samples). Regarding OCP contents in liver tissues, Mirex was also dominant. The atmospheric transport from secondary sources was assumed to be the origin of OCPs in the studied environment and their occurrence and difference between the two sampling sites are in good agreement with previous atmospheric monitoring. Further studies are needed to evaluate the exposure of campos de altitude endemic organisms to other airborne hazardous chemicals and to assess the potential toxicity posed by contaminant mixtures.

Short and medium-chain chlorinated paraffins in indoor dust from a multistory residential building in Beijing, China: Vertical distribution and potential health risks

In this study, we conducted a preliminary investigation of the vertical distribution and potential health risks of short and medium-chain chlorinated paraffins (SCCPs and MCCPs) in indoor dust from a multistory residential building in Beijing, China. Forty-eight SCCP and MCCP congener groups in dust from different floors of the multistory residential building were determined by two-dimensional gas chromatography coupled with electron capture negative ionization mass spectrometry. The concentration ranges for SCCPs and MCCPs in the dust samples were 0.0239–207 μg/g and 0.135–2903 μg/g, respectively. MCCPs were the dominant group, on average accounting for 76.8 % of ∑CPs. Generally, the concentrations of both SCCPs and MCCPs greatly decreased as the floor level increased, which indicated that the CP contamination was attributed to exogenous atmospheric transport and deposition. C13Cl7–8 and C14Cl7–8 were the dominant SCCP and MCCP congener groups, possibly indicating the use of industrial CP-52 products was the main source of CPs. In the worst-case scenario using the maximum concentrations of CPs, the daily intake of SCCPs for toddlers was of the same order of magnitude as the reference dose. It should be noted that CPs exposure may be more serious when indoor decorations, furniture, and various plastic products are taken into consideration. Overall, more attention should be paid to CPs exposure and control measures in high-rise buildings.

A fast gas chromatography coupled with electron capture negative ion mass spectrometry in selected ion monitoring mode screening method for short-chain and medium-chain chlorinated paraffins.

Chlorinated paraffins (CPs) are a group of anthropogenic pollutants that consist of complex mixtures of polychlorinated n-alkanes of different chain lengths (~C10 to C30 ). Persistence, bioaccumulation, toxicity, and long-range transport of short-chain chlorinated paraffins (SCCPs, C10 - to C13 -CPs) have prompted their classification as persistent organic pollutants (POPs) by the Stockholm Convention in 2017. Due to the varying chain lengths and chlorination degrees, quantification of SCCPs and medium-chain chlorinated paraffins (MCCPs, C14 - to C17 ) using gas chromatography coupled with electron capture negative ion mass spectrometry in selected ion monitoring mode (GC/ECNI-MS-SIM) is not only challenging but also very time consuming. In particular, up to eight GC runs per sample are required for the comprehensive GC/ECNI-MS-SIM quantification of SCCPs and MCCPs. These efforts are high especially if the samples do not contain CPs above the limit of detection (LOD), subsequently. We developed a semi-quantitative and sensitive method for the examination of SCCPs and MCCPs in one GC run. This GC/ECNI-MS-SIM screening method was based on the recording of Cl- (m/z 35 and 37), Cl2 - (m/z 70 and 72), and HCl2 - (m/z 71 and 73) isotope ions and evaluation of the ratios between them. Correctness of the results of the screening method was verified by analysis of edible oils with and without CPs, CP standards, as well as a technical CP mixture. Polychlorinated biphenyls (PCBs) and other polyhalogenated aromatic compounds, as well as brominated flame retardants, do not form all of the fragment ions analyzed by the screening method. After the screening, only CP-positive samples may need to be measured in detail. Measurement time will already be gained in the case of ~10% samples without CPs.

Air–soil exchange of and risks posed by short- and medium-chain chlorinated paraffins: Case study in a contaminated area in China

Short-chain (SC) and medium-chain (MC) chlorinated paraffins (CPs) are found widely in the environment. Little research into air–soil exchange of SCCPs and MCCPs has been performed. In this study, CP concentrations, congener group profiles, and air–soil exchange in a typical contaminated area were investigated. A total of 10 soil samples and 10 air samples were collected from Zhoushan, an island in China. The samples were analyzed by two-dimensional gas chromatography electron capture negative ionization mass spectrometry. The SCCP and MCCP concentrations in the soil samples were 72–3842 and 117–8819 ng/g, respectively, and the SCCP and MCCP concentrations in the air samples were 57–208 and 1.8–25 ng/m3, respectively. The highest CP concentrations in both soil and air were found in samples from near shipyards, possibly because of CPs being emitted from metal cutting fluids and marine paints used at the shipyards. C14–15Cl7-9 were the dominant CP congener groups in the soil samples. C10Cl6–7 were the dominant CP congener groups in the air samples. Chlorinated decane and undecane and penta-, hexa-, and hepta-chlorinated CPs were enriched in the air relative to the soil. These congeners may have been released from the commercial CP-42 and CP-52. The fugacity fractions (ffs) of 48 homologs decreased as Koa increased. The ffs indicated that SCCPs and MCCPs dominated deposition. The net air–soil exchange fluxes of CPs were 201–769 ng/(m2·h). A preliminary risk assessment indicated that CPs pose low ecological risk except at sampling site S7 and do not pose significant health risks.

Concentrations, homolog profiles, and risk assessment of short- and medium-chain chlorinated paraffins in soil around factories in a non-ferrous metal recycling park

Chlorinated paraffins (CPs) are used as additives in metal processing in the metal smelting industry. Data on CPs in the environment near metal smelting plants are limited. The objectives of this study were to investigate the concentrations and congener profiles of CPs in soil around factories in a non-ferrous metal recycling park located in Hebei, China, and to investigate human exposure to CPs in the soil. The concentrations of short-chain CPs (SCCPs) and medium-chain CPs (MCCPs) were determined by two-dimensional gas chromatography with electron capture negative ionization mass spectrometry. The SCCP and MCCP concentrations in the soil samples were 121–5159 ng/g and 47–6079 ng/g, respectively. Generally, the CP concentrations in soils around the factories were relatively high compared with those near other contaminated sites and in rural and urban areas. There were significant correlations between the MCCP concentrations, some SCCP carbon homologs, and the total organic carbon content (p < 0.05). The major SCCP and MCCP congener groups were C10Cl6–7 and C15–16Cl5, respectively. Hierarchical cluster analysis and principal component analysis indicated that SCCPs and MCCPs in the soil might originate from extreme pressure additives containing CP-42 and CP-52 and CP-containing waste material from the factories. The concentrations in two samples collected near a metal recycling factory posed a moderate risk according to a risk assessment conducted using risk quotients. Further risk assessment showed that the CPs concentrations in soil did not pose significant health risks to either children or adults.

A new synthesis approach for the generation of single chain CP mixtures composed of a few major compounds

Chlorinated paraffins (CPs) are complex mixtures, which consist of thousands of individual compounds with no dominant representative. Consequently, knowledge on structure and environmental relevance of individual CP congeners is poor. Similarly to the synthesis of individual CPs, the generation of less complex CP mixtures that can be thoroughly analyzed may be used to overcome some drawbacks of the highly complex technical CP mixtures. Here, we present a new synthesis approach to generate such simple CP mixtures by decarboxylation of polyunsaturated fatty acids followed by saturation of the double bonds by chlorination. Specifically, α-linolenic acid (18:3Δ9,12,15) was decarboxylated to heptadecatriene. The resulting raw product was chlorinated with SO2Cl2. Purification by column chromatography led to a main fraction consisting of four major peaks originating from hexachloroheptadecane (C17H30Cl6) isomers (∼80% of the total peak area) along with ∼20 low abundant by-products, according to gas chromatography with electron capture negative ion mass spectrometry. In the same way, decarboxylation and subsequent chlorination of other polyunsaturated fatty acids may lead to further simple CP mixtures with other chain lengths. Although these simple CP mixtures cannot fully reflect the various structural features present in technical mixtures they could be beneficial for transformation studies because changes in the CP pattern can easily be noted which is in contrast to technical CP mixtures. Such simple CP mixtures could also be used in toxicity tests which are difficult to perform with technical CP mixtures because of their high complexity.

Naturally occurring organobromine compounds (OBCs) including polybrominated dibenzo-p-dioxins in the marine sponge Hyrtios proteus from The Bahamas

Halogenated natural products (HNPs) were identified from organic extracts of the marine sponge Hyrtios proteus from The Bahamas using gas chromatography with electron capture negative ion mass spectrometry and non-targeted gas chromatography with electron ionization mass spectrometry. The HNPs found have similar properties to anthropogenic persistent organic pollutants (POPs). Two ortho-methoxy brominated diphenyl ethers (MeO-BDEs) 2′-MeO-BDE 68 and 6-MeO-BDE 47 were the most abundant compounds. Fourteen other MeO-BDEs were detected along with several polybrominated dibenzo-p-dioxins (PBDDs) (1,3,7-triBDD, 1,3,6,8-tetraBDD and 1,3,7,9-tetraBDD) and MeO-PBDDs. Further analysis of a higher trophic level octopus (Octopus maya) from the same FAO fishing area showed that the major HNPs detected in Hyrtios proteus were also predominant. Moreover, HNPs were more than 30-fold higher in abundance than the major POPs in the octopus, i.e., polychlorinated biphenyls. Hence, Caribbean marine organisms, including those potentially used for food, harbor relatively high concentrations of HNPs.

Occurrence of pyrethroids in the atmosphere of urban areas of Southeastern Brazil: Inhalation exposure and health risk assessment

The occurrence of organochlorine pesticides (OCPs) used decades ago for vector control in urban areas is still reported as a threat to human health. Pyrethroids emerged as a replacement for OCPs in sanitary campaigns and are currently the main insecticides used for vector control worldwide, with prominent use as agricultural and household insecticides, for veterinary and gardening purposes, and as wood preservative. This study aimed to assess the occurrence, seasonal variation, and potential sources of pyrethroids in ambient air of two urban regions of Southeastern Brazil, along with the potential health risks to local populations via inhalation exposure. Pyrethroids were sampled by polyurethane foam passive air samplers and their concentrations were determined by gas chromatography coupled with electron capture negative ionization mass spectrometry (GC/ECNI-MS). Atmospheric pyrethroid concentrations (hereinafter reported in pg m−3) were considerably higher than those reported by previous studies worldwide. Cypermethrin (median: 2446; range: 461–15 125) and permethrin (655; 19–10 328) accounted for 95% of the total measured pyrethroids in ambient air. The remaining fraction comprised smaller amounts of bifenthrin (46; <limit of detection (LOD)–5171), deltamethrin (58; <LOD–564), phenothrin (7; <LOD–22) and fenvalerate (0.3; <LOD–3). Bifenthrin, deltamethrin and permethrin were linked to local sources, while cypermethrin, fenvalerate and phenothrin had more prominent regional contributions. In broad terms, most pyrethroids showed no clear seasonal trend. The concentrations and hazard quotients (HQs) showed the following order of occurrence and magnitude: urban > urban-industrial > background areas. HQs increased with decreasing age group, but deterministic and probabilistic estimates did not identify direct health risks for any group. Nevertheless, since only inhalation exposure was considered in this work, other pathways should be investigated to provide a more comprehensive risk assessment of the human exposure to pyrethroids.

High levels of halogenated natural products in large pelagic fish from the Western Indian Ocean

Concentrations, profiles and muscle-liver distribution of halogenated natural products (HNPs) and anthropogenic persistent organic pollutants (POPs) were investigated in five large pelagic fish species and one smaller planktivore fish species from the Western Indian Ocean. Analysis of swordfish muscle from the Seychelles revealed the predominance of HNPs, with the highest concentrations found for 2′-methoxy-2,3′,4,5′- tetraBDE (2′-MeO-BDE 68 or BC-2), 6-methoxy-2,2′,4,4′- tetraBDE (6-MeO-BDE 47 or BC-3) and 2,3,3′,4,4′,5,5′-heptachloro-1′-methyl-1,2′-bipyrrole (Q1), along with varied contributions of further HNPs. The mean concentration of ∑HNPs (330 ng/g lw) was one or two orders of magnitude higher than ∑DDTs (60 ng/g lw) and ∑PCBs (6.8 ng/g lw). HNPs (BC-2, BC-3 and Q1) were also predominant in individual samples of three tropical tuna species from the Seychelles and from other regions of the Western Indian Ocean (Mozambique Channel, off Somalia and Chagos Archipelago). Non-targeted gas chromatography coupled with electron capture negative ion mass spectrometry operated in the selected ion monitoring mode (GC/ECNI-MS-SIM) analysis of one swordfish sample indicated low abundance of rarely reported HNPs (three hexachloro-1′-methyl-1,2′-bipyrrole (Cl6-MBP) isomers and pentabromo-1,1′-dimethyl-2,2′-bipyrroles (Br5-DBP)) but no further abundant unscreened polyhalogenated compounds.

Resonant electron capture negative ion mass spectrometry: the state of the art and the potential for solving analytical problems

Resonant electron capture negative ion mass spectrometry: the state of the art and the potential for solving analytical problems

Highly elevated levels, infant dietary exposure and health risks of medium-chain chlorinated paraffins in breast milk from China: Comparison with short-chain chlorinated paraffins.

Short-chain chlorinated paraffins (SCCPs) are persistent organic pollutants which are toxic to human. Median-chain chlorinated paraffins (MCCPs) have similar toxicity to SCCPs. The productions of chlorinated paraffins (CPs) in China were 1 million tons in 2013 and remained high after that, which may lead to high risks for human exposure to CPs. To investigate temporal trends and health risks of SCCPs and MCCPs in breast milk in China, samples (n=2020) were collected from urban and rural areas of 11 Chinese provinces in 2017 and mixed into 42 pooled samples. SCCPs and MCCPs were analyzed by two-dimensional gas chromatography with electron-capture negative-ionization mass spectrometry (GC×GC-ECNI-MS). The MCCP concentrations (median (range)) were 472 (94-1714) and 567 (211-1089) ng g-1 lipid in urban and rural areas, respectively, which showed continuously rapidly increasing during 2007-2017. The SCCP concentrations (median (range)) were 393 (131-808) and 525 (139-1543) ng g-1 lipid in urban and rural areas, respectively. The results showed SCCP levels decreased in urban areas between 2007 and 2017. Significant increases in MCCP/SCCP ratios might arise from extensive manufacturing and use of MCCPs. The median estimated dietary intake via breast milk in urban and rural samples were 1230 and 2510ngkg-1d-1, respectively, for SCCPs and 2150 and 1890ngkg-1d-1, respectively, for MCCPs. Preliminarily risk assessment showed that SCCPs posed a significant health risk to infants via breastfeeding. The high MCCP levels should also be of concern because of continuous growth and negative effect on infants. Correspondence analysis indicated congeners with higher carbon and chlorine numbers in dietary tend to accumulate in breast milk.

Evidence for cometabolic transformation of weathered toxaphene under aerobic conditions using camphor as a co-substrate.

Toxaphene is a persistent organic pollutant, composed of approximately 1000 highly chlorinated bicyclic terpenes. The purpose of this study was to evaluate if camphor, a structural analogue of toxaphene, could stimulate aerobic biotransformation of weathered toxaphene. Two enrichment cultures that degrade camphor as the sole carbon source were established from contaminated soil and biosolids. These cultures were used to evaluate aerobic transformation of weathered toxaphene. Only the biosolids culture could transform compounds of technical toxaphene (CTTs) in the presence of camphor, while no transformation was observed in the presence of glucose or with toxaphene as a sole carbon source. The transformed toxaphene had lower concentration of CTTs with longer retention times, and higher concentration of compounds with lower retention times. Gas chromatography with electron capture negative ion mass spectrometry (GC/ECNI-MS) showed that aerobic biotransformation mainly occurred with Cl8 - and Cl9 -CTTs compounds. The patterns of Cl6 - and Cl7 -CTTs were also simplified albeit to a much lesser extent. Seven camphor-degrading bacteria were isolated from the enrichment culture but none of them could degrade toxaphene. Camphor degrading culture can aerobically transform CCTs via reductive pathway probably by co-metabolism using camphor as a co-substrate. Since camphor is naturally produced by different plants, this study suggests that stimulation of aerobic transformation of toxaphene may occur in nature. Moreover plants, which produce camphor or similar compounds, might be used in bioremediation of contaminated soils.

Spatial distributions, source apportionment and ecological risks of C9-C17 chlorinated paraffins in mangrove sediments from Dongzhai Harbor, Hainan Island.

The spatial distributions, possible sources of C9-C17 chlorinated paraffins (CPs), and the ecological risks posed in mangrove sediment in Dongzhai Harbor (Hainan Island, China) were investigated. Comprehensive two-dimensional gas chromatography combined with electron capture negative ionization mass spectrometry was used to determine 50 C9-C17 CP congener groups. The concentrations of C9-CPs, short-chain CPs (SCCPs), and medium-chain CPs (MCCPs) in the mangrove sediment samples were 8.28-79.7, 89.2-931, and 58.8-834ngg-1 dry weight, respectively. The CPs concentrations in the mangrove sediment samples were moderate compared with those found in other regions worldwide. The spatial distributions and congener patterns of the CPs indicated that the CP concentrations were mainly controlled by local emissions and that wastewater discharged from livestock and shrimp breeding facilities and domestic sewage were the main sources of CPs in mangrove sediment in Dongzhai Harbor. C10Cl6-7 and C14Cl7-8 were the dominant SCCP and MCCP congener groups, respectively. The MCCP concentrations and total organic carbon contents significantly correlated (R2=0.607, P<0.05). Hierarchical cluster analysis and principal component analysis indicated that the SCCP and MCCP congeners were from different commercial CP formulations and sources. Risk assessments suggested that SCCPs and MCCPs in mangrove sediment in Dongzhai Harbor do not currently pose marked risks to sediment-dwelling organisms.

Polycyclic aromatic hydrocarbons (PAHs) and oxy- and nitro-PAHs in ambient air of the Arctic town Longyearbyen, Svalbard

Abstract. Polycyclic aromatic hydrocarbons (PAHs) are not declining in Arctic air despite reductions in their global emissions. In Svalbard, the Longyearbyen coal-fired power plant is considered to be one of the major local sources of PAHs. Power plant stack emissions and ambient air samples, collected simultaneously at 1 km (UNIS) and 6 km (Adventdalen) transect distance, were analysed (gaseous and particulate phases separately) for 22 nitro-PAHs, 8 oxy-PAHs, and 16 parent PAHs by gas chromatography in combination with single quadrupole electron capture negative ionization mass spectrometry (GC-ECNI-MS) and gas chromatography in combination with triple quadrupole electron ionization mass spectrometry (GC-EI-MS/MS). Results confirm low levels of PAH emissions (∑16 PAHs =1.5 µg kg−1 coal) from the power plant. Phenanthrene, 9,10-anthraquinone, 9-fluorenone, fluorene, fluoranthene, and pyrene accounted for 85 % of the plant emission (not including naphthalene). A dilution effect was observed for the transect ambient air samples: 1.26±0.16 and 0.63±0.14 ng m−3 were the sum of all 47 PAH derivatives for UNIS and Adventdalen, respectively. The PAH profile was homogeneous for these recipient stations with phenanthrene and 9-fluorenone being most abundant. Multivariate statistical analysis confirmed coal combustion and vehicle and marine traffic as the predominant sources of PAHs. Secondary atmospheric formation of 9-nitroanthracene and 2+3-nitrofluoranthene was evaluated and concluded. PAHs partitioning between gaseous and particulate phases showed a strong dependence on ambient temperatures and humidity. The present study contributes important data which can be utilized to eliminate uncertainties in model predictions that aim to assess the extent and impacts of Arctic atmospheric contaminants.

NMR and GC/MS analysis of industrial chloroparaffin mixtures

Chlorinated paraffins (CPs) are high-volume chemicals used worldwide in various industries as plasticizers, lubricants, and flame retardants. CPs are produced by chlorination of alkane mixtures which leads to complex products of thousands of homologs and congeners. Classic mass spectrometric analyses of CPs allow determining carbon chain lengths and degrees of chlorination while information on the substitution patterns cannot be derived. Therefore, we performed different one- and two-dimensional nuclear magnetic resonance spectroscopy (NMR) experiments, elemental analysis (EA), and gas chromatography coupled with electron capture negative ion mass spectrometry (GC/ECNI-MS) for the analysis of ten technical CP products with 42%, 52%, and 70% chlorine content from four producers. Slight differences in chlorine content but varying chain length compositions were observed for similarly labeled products from different manufacturers. Two-dimensional heteronuclear spectral quantum coherence (HSQC) measurements helped to evaluate ten structural elements in the products and confirmed the presence of geminal chlorine atoms in primary and secondary carbons in products with 70% chlorine. The variation of signal groups increased with increasing chlorine content of the products. Two-dimensional heteronuclear multiple bond coherence (HMBC) analysis of one sample and GC/ECNI-MS measurements indicated the presence of impurities (e.g., C9-CPs, iso-alkanes) in different technical CP products. These methods could in future allow for better distinction of CP mixtures, and an improved trace-back of environmental CPs to the source, based on specific structural features. Additionally, further structural characterization could help in the development of more accurate analysis processes.Graphical

Screening of halogenated phenolic compounds in plasma and serum from marine wildlife

The growing knowledge of the impact of halogenated phenolic compounds on hormonal and metabolic systems has led to an increased interest in the exposure and potential effects of these compounds in wildlife. In the present study, a screening procedure was developed to detect and quantify halogenated phenolic compounds in serum and plasma from marine wildlife. A mass spectral library containing selective ion monitoring data was created using gas chromatography electron capture negative ionization mass spectrometry. The selective ion monitoring data in the library were accompanied with retention indices to increase the specificity of each entry in the library. The library together with the developed extraction procedure and optimized instrumental settings can be used for the detection of 52 different halogenated phenolic compounds of environmental concern, including 23 hydroxylated polychlorinated biphenyls and 24 hydroxylated polybrominated diphenyl ethers. The instrument limit of detection for the compounds included in the library ranged from 30 to 320 fg/injection, with a median detection limit of 90 fg/injection. The average recovery of 11 different halogenated phenolic compounds, from four species of marine wildlife, was 66 ± 14%. A full-scan mass spectral library was also created containing an additional seven compounds. Gray seals, long-tailed ducks, and two species of fish from the Baltic Sea were screened for halogenated phenolic compounds using the developed procedure. A total of 33 compounds included in the library were detected and quantified.

Gaining of analytical information about a compound for structural group analysis using mass spectra of negative ions

Successful functioning of expert systems designed for determination of the molecular structure of organic compounds by spectral characteristics requires the availability of most complete initial analytical information. Successful functioning of expert systems designed for determination of the molecular structure of organic compounds by spectral characteristics requires the availability of most complete initial analytical information which necessitates summarizing and using data gained in different analytical methods. We consider prospects of gaining new information about test compounds by the method of resonant electron capture negative ion mass spectrometry using a serial quadrupole mass-spectrometer. A number of phosphorus-containing organic compounds are used to demonstrate a possibility of recording mass spectrum peaks of deprotonated molecules, which is rather important for determination of the molecular mass and, hence, correct identification of the compound. Examples of successful detection of the fragments with positive electron affinity present in the structure of compounds under study are listed. The obtained results substantially differ from that obtained by the “classical” method of electron ionization positive ion mass spectrometry and can be considered as a complementary data about the structure of compounds for the purposes of structural group analysis., We also present the results of experiments in which mass spectra of negative ions were obtained using the advanced cathode power supply device via multiple change in the energy of ionizing electrons during the analysis. The possibility of implementing both analytical methods on the same device is an additional advantage of this approach.