Combining High-Resolution Gas Chromatographic Continuous Fraction Collection with Nuclear Magnetic Resonance Spectroscopy: Possibilities of Analyzing a Whole GC Chromatogram.

This study presents, for the first time, the successful application of analyzing a whole gas chromatography (GC) chromatogram by nuclear magnetic resonance (NMR) spectroscopy using a continuous repeatable and stable (n = 280) high-resolution (HR) GC fractionation platform with a 96-well plate. Typically with GC- or liquid chromatography-mass spectrometry analysis, (isomer) standards and/or additional NMR analysis are needed to confirm the identification and/or structure of the analyte of interest. In the case of complex substances (e.g., UVCBs), isomer standards are often unavailable and NMR spectra too complex to achieve this. This proof of concept study shows that a HR GC fractionation collection platform was successfully applied to separate, purify, and enrich isomers in complex substances from a whole GC chromatogram, which would facilitate NMR analysis. As a model substance, a chlorinated paraffin (CP) mixture (>8,000 isomers) was chosen. NMR spectra were obtained from all 96 collected fractions, which provides important information for unravelling their full structure. As a proof of concept, a spectral interpretation of a few NMR spectra was made to assign sub-structures. More research is ongoing for the full characterization of CP isomers using multivariate statistical analysis. For the first time, up to only a few CP isomers per fraction were isolated from a highly complex mixture. These may be further purified and certified as standards, which are urgently needed, and can also be used for persistency, bioaccumulation, or toxicity studies.

Optimization of a low flow sampler for improved assessment of gas and particle bound exposure to chlorinated paraffins.

An optimized low volume sampler was developed to determine both gas- and particle bound concentrations of short and medium-chain chlorinated paraffins (S/MCCPs). Background contamination was limited by the sampler design, providing method quantification limits (MQLs) at least two orders of magnitude lower than other studies within the gas (MQL: 500 pg (ΣSCCPs), 1.86 ng (ΣMCCPs)) and particle (MQL: 500 pg (ΣSCCPs), 1.72 ng (ΣMCCPs) phases. Good repeatability was observed between parallel indoor measurements (RSD ≤ 9.3% (gas), RSD ≤ 14% (particle)) with no breakthrough/saturation observed after a week of continuous sampling. For indoor air sampling, SCCPs were dominant within the gas phase (17 ± 4.9 ng/m3) compared to MCCPs (2.7 ± 0.8 ng/m3) while the opposite was observed in the particle bound fraction (0.28 ± 0.11 ng/m3 (ΣSCCPs) vs. 2.7 ± 1.0 ng/m3 (ΣMCCPs)). Only SCCPs in the gas phase could be detected reliably during outdoor sampling and were considerably lower compared to indoor concentrations (0.27 ± 0.10 ng/m3). Separation of the gas and particle bound phase was found to be crucial in applying the appropriate response factors for quantification based on the deconvoluted S/MCCP sample profile, thus avoiding over- (gas phase) or underestimation (particle phase) of reported concentrations. Very short chain chlorinated paraffins (vSCCPs, C5-C9) were also detected at equal or higher abundance compared to SCCP congener groups (C10-C13) congener groups, indicating an additional human indoor inhalation risk.

Spatial variation of short- and medium-chain chlorinated paraffins in ambient air across Australia.

Atmospheric levels of chlorinated paraffins (CPs) at five remote, six rural and four urban sites in Australia were measured using XAD-2 passive air samplers (XAD-PAS). While long-chain CP (LCCP, C>17) levels were below method detection limits (MDLs), short-chain CPs (SCCPs, C10-13) and, for the first time, medium-chain CPs (MCCPs, C14-17) and CPs with a carbon chain length of nine (CP-C9) were found at many sites (88%, 81% and 88%, respectively) across the Australian continent, representing a range of environmental conditions. Applying preliminary sampling rates of the XAD-PAS for CPs, gaseous CP levels in Australian air were

Evaluating age and temporal trends of chlorinated paraffins in pooled serum collected from males in Australia between 2004 and 2015.

Chlorinated paraffins (CPs) are high production volume chemicals of which some show resistance to environmental degradation, long-rang transport, bioaccumulation and toxicity potential. Information regarding their presence in humans is limited, including their human bioaccumulation potential. The present study aimed to evaluate CP levels in human serum from Australia in order to better understand their exposure and current pollution status as well as trends associated with age and time between 2004 and 2015. For this, we selected a male sub-group of the Australian population under 60 years old (n = 16 pools, total 1600 serum samples). While long-chain CP (C18-20) and most short-chain CP (C10-13, SCCPs) levels were below method detection limits (MDL), medium-chain CPs (C14-17, MCCPs) were found in most serum samples (detection frequency 94%) as well as CPs with a carbon chain length of nine (detection frequency 76%). The levels of ΣSCCPs and ΣMCCPs ranged from

First detection of short-chain chlorinated paraffins (SCCPs) in humpback whales (Megaptera novaeangliae) foraging in Antarctic waters.

Short-chain chlorinated paraffins (SCCPs) are particularly prone to environmental dispersal through long range atmospheric transport. Consequently, they have been detected in biota and environmental matrices at both the North Pole and South Pole. This study shows the first detection of SCCPs in southern hemisphere humpback whales feeding in Antarctic waters. Blubber of specimens stranded along the Australian coastline was analysed and SCCPs were detected in 7 out of 9 individuals. Levels of SCCPs detected in this study were generally low with concentrations up to only 46 ng/g lw. These results were significantly lower than those detected in Northern Hemisphere odontocetes from previous studies, although no reported burdens in northern hemisphere baleen whales are available for comparison. Both the highest level and lowest ( C13. Further investigation is needed in order to evaluate the presence and distribution of SCCPs in the remote Antarctica ecosystem, and delineate longer term environmental consequences of recent inclusion of SCCPs under Annex A of the Stockholm Convention, securing their phase out in ratifying nations.

Chlorinated paraffins in indoor dust from Australia: Levels, congener patterns and preliminary assessment of human exposure.

Chlorinated paraffins (CPs) are a group of polychlorinated n-alkanes with high production volumes. Until now, there are only limited data on the levels of CPs in the environment, especially in the indoor environment. In this study, dust samples were collected from 44 indoor environments, including 27 private houses, 10 offices, and 7 vehicles. Short-, medium-, and long-chain CPs were detected in all dust samples. The median concentration of ∑CPs (C10-C21) was 57, 160 and 290 µg/g, in houses, offices, and vehicles, respectively. Medium-chain CPs were the dominant group, on average accounting for 86% of ∑CPs. Cl6 and Cl8 groups had the highest contributions to ∑CPs across all the different microenvironments, while C13 and C14 were the predominant groups of SCCPs and MCCPs. Median exposure to ∑CPs via indoor dust were estimated at 80 ng/kg/day and 620 µg/kg/day for Australian adults and toddlers respectively. The daily intake of CPs via dust, in the worse scenario, was still 2-3 orders of magnitudes lower than the reference doses based on neoplastic effects.

Chlorinated paraffins in the environment: A review on their production, fate, levels and trends between 2010 and 2015.

This review provides an update on information regarding the production volumes, regulations, as well as the environmental levels, trends, fate and human exposure to chlorinated paraffin mixtures (CPs). CPs encompas thousands congeners with varying properties and environmental fate. Based on their carbon chain lengths, CPs are divided into short- (SCCPs; C10-13), medium- (MCCPs; C14-17) and long- (LCCPs; C ≥ 18) chained groups. They are high production volume and persistent chemicals, and their cumulative global production already surpasses that of other persistent anthropogenic chemicals (e.g. PCBs). However, international regulations are still curbed by insufficient information on their levels and fate, including bioaccumulation and toxicity potential. An increasing number of studies since 2010 demonstrate that CPs are detected in almost every compartment in the environment, including remote areas. Consensus on the long range transport and high bioaccumulation potential (BCF > 5000 & TMF > 1) has recently been reached for SCCPs, fulfilling criteria under the Stockholm Convention for designation as a persistent organic pollutant; information on their levels is, however, still sparse for many countries. M/LCCPs have received comparatively little attention in the past, but as replacement chemicals for SCCPs, MCCPs are now considered in an increasing number of studies. The limited data to date suggests MCCPs are widely used. Although data on their bioaccumulation and toxicity are still inconclusive, MCCPs and LCCPs with C<20 may also have a bioaccumulation potential. Considering this and their high production volumes, use, and ubiquitous occurrence in the environment, a better understanding on the levels and fate of all CPs is needed.

Recent developments in capabilities for analysing chlorinated paraffins in environmental matrices: A review.

Concerns about the high production volumes, persistency, bioaccumulation potential and toxicity of chlorinated paraffin (CP) mixtures, especially short-chain CPs (SCCPs), are rising. However, information on their levels and fate in the environment is still insufficient, impeding international classifications and regulations. This knowledge gap is mainly due to the difficulties that arise with CP analysis, in particular the chromatographic separation within CPs and between CPs and other compounds. No fully validated routine analytical method is available yet and only semi-quantitative analysis is possible, although the number of studies reporting new and improved methods have rapidly increased since 2010. Better cleanup procedures that remove interfering compounds, and new instrumental techniques, which distinguish between medium-chain CPs (MCCPs) and SCCPs, have been developed. While gas chromatography coupled to an electron capture negative ionisation mass spectrometry (GC/ECNI-MS) remains the most commonly applied technique, novel and promising use of high resolution time of flight MS (TOF-MS) has also been reported. We expect that recent developments in high resolution TOF-MS and Orbitrap technologies will further improve the detection of CPs, including long-chain CPs (LCCPs), and the group separation and quantification of CP homologues. Also, new CP quantification methods have emerged, including the use of mathematical algorithms, multiple linear regression and principal component analysis. These quantification advancements are also reflected in considerably improved interlaboratory agreements since 2010. Analysis of lower chlorinated paraffins (