Determination of chlorinated paraffins (CPs): Analytical conundrums and the pressing need for reliable and relevant standards.

The determination of chlorinated paraffins (CPs) has posed an intractable challenge in analytical chemistry for over three decades. The combination of an as yet unspecifiable number (tens - hundreds of thousands) of individual congeners in mass produced commercial CP mixtures and the steric interactions between them, contrive to defy efforts to characterise their residual occurrences in environmental compartments, food and human tissues. However, recent advances in instrumentation (mass spectrometric detectors and nuclear magnetic resonance), combined with interlaboratory studies, have allowed a better insight into the nature of the conundrums. These include the variability of results, even between experienced laboratories when there is insufficient matching between analytical standards and occurrence profiles, the poor (or no) response of some instrumentation to some CP congener configurations (multiple terminal chlorines or < four chlorines) and the occurrence of chlorinated olefins in commercial mixtures. The findings illustrate some limitations in the existing set of commercially available standards. These include cross-contamination of some standards (complex CP mixtures), an insufficient number of single chain standards (existing ones do not fully reflect food/biota occurrences), lack of homologue group standards and unsuitability of some configurationally defined CP congeners/labelled standards (poor instrument response and a smaller likelihood of occurrence in commercial mixtures). They also indicate an underestimation in reported occurrences arising from those CPs that are unresponsive during measurement. A more extensive set of standards is suggested and while this might not be a panacea for accurate CP determination, it would reduce the layers of complexity inherent in the analysis.

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.

Chlorinated paraffins - A historical consideration including remarks on their complexity.

Chlorinated paraffins (CPs) are high production volume chemicals currently produced and used in higher quantities than any other medium-size polyhalogenated compound (class). In addition, the composition of industrial CP mixtures is highly complex and poorly understood. In this article, we searched in the literature for the beginning of the chlorination of alkanes and how this substance class developed from niche applications to unmatched quantities in various industrial applications. Also, an estimation was made on the theoretical variety of chloroparaffins and the possible complexity of industrial CP mixtures. These data may explain why little is known about CPs although the production volume throughout the industrial generation was virtually always higher than the one of PCBs and has continued to increase after the ban of the latter.

Chlorinated Paraffin Levels in Relation to Other Persistent Organic Pollutants Found in Pooled Human Milk Samples from Primiparous Mothers in 53 Countries.

BACKGROUND: The current production and use of chlorinated paraffins (CPs) at >1 million tons/y likely exceeds the lifetime production of polychlorinated biphenyls (PCBs). These persistent organic pollutants (POPs) are a concern to human health. OBJECTIVES: The United Nations Environment Programme conducts global surveys of human milk samples from individual countries as a noninvasive method of investigating levels and trends in human exposures to POPs such as CPs. We measured CP concentrations and assessed their relation to other POPs in pooled samples collected during 2012-2019. METHODS: We analyzed 57 official nationwide pooled milk samples from 53 countries on five continents (Africa, Central/South America, Asia, Europe, and Australia/Oceania). CP concentrations were further characterized by subgroups and compared with concentrations of 19 other POPs, including PCBs and a variety of pesticides. RESULTS: CPs were detected in pooled samples from all 53 countries, with concentrations of 23-700 ng/g lipid. CPs accounted for 18-46% of the total summed POPs in human milk, second only to dichlorodiphenyltrichloroethane (DDT). CP concentrations exceeded PCB concentrations in pooled samples from most countries. DISCUSSION: The presence of CPs in all samples, including samples from isolated locations (e.g., Pacific Island countries), emphasizes the ubiquitous presence of these compounds, whereas differences in subgroup ratios indicate a delay in the shift toward nonregulated medium-chain CPs (MCCPs) for these regions. The predominance of MCCPs in samples from many countries suggests a need for regulation and research on health effects. https://doi.org/10.1289/EHP7696.

Short- and medium-chain chlorinated paraffin exposure in South Germany: A total diet, meal and market basket study.

Short- and medium-chain chlorinated paraffins (SCCPs, MCCPs) are high-production volume industrial chemicals that have been previously reported to occur in food, packaging material and the environment. This study presents an assessment of dietary exposure for consumers in Southern Germany based on three different sampling approaches: (i) a classical market basket study (n = 154), (ii) the analysis of ready-made meals from restaurants (n = 10), and (iii) a total diet approach (n = 21). In 35% of the samples, CPs were below the method limit of quantification. Highest amounts of SCCPs and MCCPs were found especially in extra virgin olive oils (EVOOs) and fish. Homologue patterns indicated the partial removal of CPs during the refining of (other) edible oils. Ready-made meals contained only low amounts of CPs equal to estimations based on market basket samples. Total diet samples from the same hospital were generally comparable with each other regardless of diet, although vegetarian meal plans with high amounts of cheese and other dairy products contained up to an order of magnitude more CPs than other diets. Taking all approaches into account, calculated daily exposures for adults ranged 35-420 ng/kg bw/day for ΣSCCPs and 22-840 ng/kg bw/day for ΣMCCPs, which is between one and two orders of magnitude higher than the current dietary intake of polychlorinated biphenyls (indicator PCBs) in Europe.

Addressing Main Challenges Regarding Short- and Medium-Chain Chlorinated Paraffin Analysis Using GC/ECNI-MS and LC/ESI-MS Methods.

The risk assessment of chlorinated paraffins (CPs), chemicals of widespread industrial use, is struggling without standardized analytical methods to obtain reliable occurrence data. Indeed, scientists face analytical challenges that hinder the comparability of analytical methods, among them uncontrolled ionization efficiency and lack of quantification standards. In this study, our goal was to investigate potential issues faced when comparing data from different mass spectrometry platforms and quantification methods. First, the injection of the same set of single-chain length standards in three different instrumental mass spectrometry set-ups (liquid chromatography-electrospray-Orbitrap (LC/ESI-HRMS), liquid chromatography-electrospray-time-of-flight (LC/ESI-MS), and gas chromatography-electron capture negative ion-Orbitrap (GC/ECNI-HRMS)) revealed a shift of homologue response patterns even in-between LC/ESI-based set-ups, which was more pronounced for CPs of low chlorination degree. This finding emphasizes the need for a comprehensive description of instrument parameters when publishing occurrence data. Second, the quantification of a data set of samples with four quantification methods showed that quantification at the sum SCCP and MCCP levels presented good comparability, while quantification at the homologue level remained unsatisfactory. In light of those results, we suggest that (i) response pattern comparison should only be performed between similar instrumental set-ups, (ii) experimental chlorination degrees should be used when quantifying according to the %Cl (instead of those provided by the suppliers), and (iii) concentration results should be expressed as the sum of SCCPs and MCCPs primarily, with an indication on the match between samples and quantification standards (for example their chlorine content).

Photolytic Transformation Products of Decabromodiphenyl Ethane (DBDPE).

The photolytic transformation of decabromodiphenyl ethane-a current-use brominated flame retardant and major substitute of the structurally related decabromodiphenyl ether-was investigated in different solvents (toluene, dichloromethane, chlorobenzene, and benzyl alcohol). The transformation rate followed pseudo first order kinetics, with increasing half-life ( t1/2) in the order of toluene ( t1/2 = 4.6 min), chlorobenzene ( t1/2 = 14.0 min), dichloromethane ( t1/2 = 27.9 min), and benzyl alcohol ( t1/2 ≈ 60 min). Formation and amount of transformation products varied depending on the solvent used. A detailed study of the hydrodebromination products allowed us to tentatively assign all three possible nonaBDPEs (BDPE 207, 208, and in benzyl alcohol only BDPE 206) and three predominant octaBDPE congeners (BDPE 197, 201, and 202). Next to the reported BDPEs, formation of several oxygen containing transformation products (OxyTPs), dominated by octabrominated OxyTP, was verified by GC-Orbitrap-HRMS analysis. Use of HPLC and Florisil column enabled the separation of OxyTPs and BDPEs, and the polybrominated OxyTPs were most likely tricyclic compounds with almost planar structure.

Chlorinated paraffin analysis by gas chromatography Orbitrap high-resolution mass spectrometry: Method performance, investigation of possible interferences and analysis of fish samples.

For decades, high quantities of short-chain chlorinated paraffins (SCCP) and medium-chain chlorinated paraffins (MCCP) have been widely used, for instance as plasticizers or flame retardants, leading to global pollution due to unintentional emissions from products or waste. Due to the high complexity of chlorinated paraffins with several thousand congeners there is no consensus on an analytical procedure for SCCPs and MCCPs in food samples. Amongst the multitude of methods currently in use, high-resolution mass spectrometry is particularly valuable for in-depth studies of homologue patterns. Here we analyse SCCPs and MCCPs with gas chromatography coupled to high-resolution Orbitrap mass spectrometry (GC-Orbitrap-HRMS) operated in full-scan acquisition in electron capture negative ion (ECNI) mode at 60,000 and 120,000 resolution (FWHM, m/z 200, equals roughly 30,000 and 60,000 at 5% peak height). Linear dynamic range, selectivity and sensitivity tests confirmed an excellent linearity in a concentration range of 25-15,000 pg/µL with very low limits of detection (LODs) in the low pg/µL range. Spiking experiments with high levels of native mono- and di-ortho-polychlorinated biphenyls (PCBs) and mixtures of MCCP and SCCP standards did not have a negative impact on isotope ratios of the examined homologues. Besides the [M-Cl]- fragment ions used for quantification, the mass spectra of homologues also featured [M-HCl]- ions whose abundance increased with decreasing chlorination degree. In addition, [M-HCl-Cl]- ions were detected with a relative abundance of 5-10%. Three salmon (Salmo salar) samples farmed in Norway showed a consistent CP homologue pattern which differed both from the CP pattern in a sample from Scottish aquaculture and a wild salmon sample. These measurements produce evidence that discretely different CP patterns may exist in different areas of origin. Our results demonstrate that GC/ECNI-Orbitrap-HRMS is well-suited for the analysis of CPs by overcoming a range of mass interference problems and due to its thus far unmatched sensitivity.