Refinement and extension of COSMO-RS-trained fragment contribution models for predicting the partition properties of C<sub>10–20</sub> chlorinated paraffin congeners

Endo, Satoshi

doi:10.1039/d1em00123j

Cited by 12 publications

(29 citation statements)

References 18 publications

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“…However, as might be expected, the log K OW values predicted from EPISuite for all possible isomers are similar, ranging between 5.8 and 7.5, with a mean value of 6.4. Sophisticated quantum mechanical calculations by Endo and Hammer and Endo also showed that there is a similarly narrow range of log K OW values for short-chain PCA isomers. These values reflect the uncertainty that is introduced when a single randomly selected isomer is used to represent the behavior of the entire elemental composition group.…”

Section: Results and Discussionmentioning

confidence: 89%

“…EPISuite employs a QSPR model that produces the same logK AW value regardless of isomeric structure. However, the results of Endo and Hammer 35 and Endo 36 suggest that the distribution of logK AW values of isomers is also quite narrow, with standard deviations of ∼0.4 for all short-chain PCAs considered in their study. All computed parameters, ranges, means, and standard deviations (errors) of all the possible structures of C 10 H 18 C1 4 are summarized in Table S1.…”

Section: Experimental Methodsmentioning

confidence: 85%

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Which of the (Mixed) Halogenated n-Alkanes Are Likely To Be Persistent Organic Pollutants?

Chevez

Silva

et al. 2021

Environ. Sci. Technol.

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Short-chain polychlorinated n-alkanes are ubiquitous industrial chemicals widely recognized as persistent organic pollutants. They represent only a small fraction of the 184,600 elemental compositions (C10–25) and the myriad isomers of all possible (mixed) halogenated n-alkanes (PXAs). This study prioritizes the PXAs on the basis of their potential to persist, bioaccumulate, and undergo long-range transport guided by quantitative structure–property relationships (QSPRs), density functional theory (DFT), chemical fate models, and partitioning space. The QSPR results narrow the list to 966 elemental compositions, of which 352 (23 Br, 83 Cl/F, 119 Br/Cl, and 127 Br/F) are likely constituents of substances used as lubricants, plasticizers, and flame retardants. Complementary DFT calculations suggest that an additional 1367 elemental compositions characterized by a greater number of carbon and fluorine atoms but fewer chlorine and bromine atoms may also pose a risk. The results of this study underline the urgent need to identify and monitor these suspected pollutants, most appropriately using mass spectrometry. We estimate that the resolving power required to distinguish ∼74% of the prioritized elemental compositions from the most likely interferents, i.e., chlorinated alkanes, is approximately 60,000 (full width at half-maximum). This indicates that accurate identification of the PXAs is achievable using most high-resolution mass spectrometers.

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Section: Results and Discussionmentioning

confidence: 89%

Section: Experimental Methodsmentioning

confidence: 85%

Which of the (Mixed) Halogenated n-Alkanes Are Likely To Be Persistent Organic Pollutants?

Chevez

Silva

et al. 2021

Environ. Sci. Technol.

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“…Physicochemical properties (including equilibrium phase partition ratios and atmospheric and biodegradation half-lives) of C 10 –C 30 CP homologues were predicted with quantitative structure–property relationships (Text S1.7). Activation energies for degradation in air, water, and solid were assumed to be 10, 30, and 30 kJ/mol following Krogseth et al, and heats of phase transfer for C 10–20 CP congeners were taken from Endo . For each homologue, the CiP-CAFE modeling was done based on the physicochemical properties of the most abundant congener in the homologue in technical mixtures or environmental samples.…”

Section: Methodsmentioning

confidence: 99%

Global Historical Production, Use, In-Use Stocks, and Emissions of Short-, Medium-, and Long-Chain Chlorinated Paraffins

Wania

Jian-guo

2022

Environ. Sci. Technol.

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The last few decades have seen ubiquitous and increasing contamination of chlorinated paraffins (CPs) worldwide. Here, we develop the first global inventories of production, use, in-use stocks, and emissions of total CPs, including the short-, medium- and long-chain components (SCCPs, MCCPs, and LCCPs) during 1930–2020 using a dynamic substance flow analysis model named Chemical in Products Comprehensive Anthroposhpheric Fate Estimation. The model estimates that a total of ∼33 million metric tons of CPs have been produced and used globally, ∼40% of which still resided in in-use products by 2020 and is available for long-term emissions in the next decades. Global cumulative emissions of CPs have increased to ∼5.2 million metric tons by 2020, with SCCPs, MCCPs, and LCCPs accounting for ∼30, 40, and 30%, respectively. While the production, use, and emissions of CPs started declining in regions such as Western Europe, they remain high in China. The model also suggests that homologues with 10, 14, and 22–23 carbons were predominant in the cumulatively produced and emitted SCCPs, MCCPs, and LCCPs, respectively. The emission estimates were evaluated by generating environmental concentrations that are comparable to literature-reported environmental monitoring data. Our estimates provide opportunities to link the environmental fate and occurrence of CPs to emission sources and lay the basis for future risk-reduction strategies of CPs around the world.

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“…Can LCCPs be global pollutants? Almost all LCCP homologues possess log octanol–air partition coefficients (log K OA ) in excess of 11 . This suggests that they will be primarily associated with particles in the atmosphere and less subject to long-range atmospheric transport.…”

Section: Introductionmentioning

confidence: 95%

“…Almost all LCCP homologues possess log octanol−air partition coefficients (log K OA ) in excess of 11. 20 This suggests that they will be primarily associated with particles in the atmosphere and less subject to long-range atmospheric transport. Model predictions of long-range atmospheric transport indicate that SCCPs belong to the persistent organic chemicals that are most likely to accumulate in the Arctic, while LCCPs with log K OA > 11 will accumulate to a much lesser extent.…”

Section: ■ Introductionmentioning

confidence: 99%

Long-Chain Chlorinated Paraffins Have Reached the Arctic

Yuan

McLachlan

Roos

et al. 2021

Environ. Sci. Technol. Lett.

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Chlorinated paraffins (CPs) were analyzed in marine wildlife from Greenland, Iceland, and the Swedish west coast. CPs up to C29 were detected in the samples from the Arctic, indicating long-range transport of an industrial chemical group with a 2-million-ton annual production volume. CP concentrations were generally higher in biota from the Swedish west coast. The Sweden/Arctic concentration ratios for very-short-chain (vSCCPs, C<10), short-chain (SCCPs, C10–13), medium-chain (MCCPs, C14–17), and long-chain CPs (LCCPs, C>17) in cetacean and bivalve species were in the range of 3.6–150, 5–29, 3–11, and 11–450, respectively. For the first time, fetal accumulation of four CP classes was found, whereby concentrations were 3.4 to 4.5 times lower in the fetus relative to the pregnant female minke whale. Cetacean blubber contained a higher proportion of higher chlorinated CPs compared to muscle tissue, while muscle contained higher lipid-normalized concentrations of longer chain CPs than blubber tissue. LCCPs predominated (52% of total CPs) in the muscle of a killer whale from Swedish waters, which is the first report where concentrations of LCCPs surpassed those of other CPs in marine mammals. This study shows that, like other CP classes, LCCPs are Arctic contaminants that may adversely affect biota in this remote region.

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Refinement and extension of COSMO-RS-trained fragment contribution models for predicting the partition properties of C_10–20 chlorinated paraffin congeners

Abstract: New COSMO-RS-trained fragment contribution models provided quantum chemically based predictions for a range of chlorinated paraffin congener groups and mixtures regarding partition properties and their temperature dependence.

Cited by 12 publications

References 18 publications

Which of the (Mixed) Halogenated n-Alkanes Are Likely To Be Persistent Organic Pollutants?

Which of the (Mixed) Halogenated n-Alkanes Are Likely To Be Persistent Organic Pollutants?

Global Historical Production, Use, In-Use Stocks, and Emissions of Short-, Medium-, and Long-Chain Chlorinated Paraffins

Long-Chain Chlorinated Paraffins Have Reached the Arctic

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Refinement and extension of COSMO-RS-trained fragment contribution models for predicting the partition properties of C10–20 chlorinated paraffin congeners

Abstract: New COSMO-RS-trained fragment contribution models provided quantum chemically based predictions for a range of chlorinated paraffin congener groups and mixtures regarding partition properties and their temperature dependence.

Cited by 12 publications

References 18 publications

Which of the (Mixed) Halogenated n-Alkanes Are Likely To Be Persistent Organic Pollutants?

Which of the (Mixed) Halogenated n-Alkanes Are Likely To Be Persistent Organic Pollutants?

Global Historical Production, Use, In-Use Stocks, and Emissions of Short-, Medium-, and Long-Chain Chlorinated Paraffins

Long-Chain Chlorinated Paraffins Have Reached the Arctic

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Refinement and extension of COSMO-RS-trained fragment contribution models for predicting the partition properties of C_10–20 chlorinated paraffin congeners