Effects of Chain Length, Chlorination Degree, and Structure on the Octanol−Water Partition Coefficients of Polychlorinated n-Alkanes

Hilger, Bettina; Fromme, Hermann; Völkel, Wolfgang; Coelhan, Mehmet

doi:10.1021/es103098b

Cited by 125 publications

(42 citation statements)

References 34 publications

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“… 52 However, caution should be used in interpreting these predicted data as they are based on only C 14 and C 15 CPs, while the chain length range of CPs can be from C 10 to C 30 and even wider. Meanwhile, CPs with 50–55% Cl showed the minimum experimental log K OW value among mixtures of the same chain length, 46 which is consistent with our prediction ( Table S3 ). Quantitatively, the experimental log K OW of C 15 50.4% Cl was 6.65, 46 while our prediction was 6.77 (C 15 50.00% Cl), which is 1 order of magnitude closer than a prediction of 7.78 based on assumed isomer compositions 45 ( Table S4 ).…”

Section: Resultssupporting

confidence: 90%

“…The structures of CP isomers are crucial in predicting and elucidating physicochemical properties, 45 , 46 environmental behaviors, 47 , 48 and decomposition mechanisms 49 − 51 of complex CP mixtures comprised of these isomers. In the work presented here, the predicted physicochemical and toxicity parameters of the top 100 isomers are summarized in the Supporting Information for each CP mixture.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Chlorines Are Not Evenly Substituted in Chlorinated Paraffins: A Predicted NMR Pattern Matching Framework for Isomeric Discrimination in Complex Contaminant Mixtures

Yuan

Lysak

Soong

et al. 2020

Environ. Sci. Technol. Lett.

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Chlorinated paraffins (CPs) can be mixtures of nearly a half-million possible isomers. Despite the extensive use of CPs, their isomer composition and effects on the environment remain poorly understood. Here, we reveal the isomeric distributions of nine CP mixtures with single-chain lengths (C 14/15 ) and varying degrees of chlorination. The molar distribution of C n H 2 n+ 2 –m Cl m in each mixture was determined using high-resolution mass spectrometry (MS). Next, the mixtures were analyzed by applying both one-dimensional 1 H, 13 C and two-dimensional nuclear magnetic resonance (NMR) spectroscopy. Due to substantially overlapping signals in the experimental NMR spectra, direct assignment of individual isomers was not possible. As such, a new NMR spectral matching approach that used massive NMR databases predicted by a neural network algorithm to provide the top 100 most likely structural matches was developed. The top 100 isomers appear to be an adequate representation of the overall mixture. Their modeled physicochemical and toxicity parameters agree with previous experimental results. Chlorines are not evenly distributed in any of the CP mixtures and show a general preference at the third carbon. The approach described here can play a key role in understanding of complex isomeric mixtures such as CPs that cannot be resolved by MS alone.

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Section: Resultssupporting

confidence: 90%

Section: Resultsmentioning

confidence: 99%

Chlorines Are Not Evenly Substituted in Chlorinated Paraffins: A Predicted NMR Pattern Matching Framework for Isomeric Discrimination in Complex Contaminant Mixtures

Yuan

Lysak

Soong

et al. 2020

Environ. Sci. Technol. Lett.

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“…In the same way, if 5b-hydroCLD is more water soluble that CLD, then it also has necessarily a lower Kow (octanol water partition coefficient) since Kow and solubility are inversely correlated (Kow is a measure of the hydrophobicity of a compound). Remembering that 5b-hydroCLD has one Cl less than CLD, the previous deduction is fully supported by the literature where it is now established that the Kow of haloorganic compounds decreases concurrently with the decrease of the number of halogen atoms bound to the carbon skeleton (Kuramochi et al 2004a;van Noort 2009;Gewurtz et al 2009;Bettina et al 2011). The propensity of a non-ionic organic compound to partition between an aqueous solution and soil is commonly described by the soil water distribution coefficient normalized to the soil organic content, Koc.…”

Section: Different Physical Behaviour Of 5b-hydrocld and Cld Resultinmentioning

confidence: 79%

Natural transformation of chlordecone into 5b-hydrochlordecone in French West Indies soils: statistical evidence for investigating long-term persistence of organic pollutants

Devault

Laplanche

Pascaline³

et al. 2015

Environ Sci Pollut Res

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OATAO is an open access repository that collects the work of Toulouse researchers and makes it freely available over the web where possible. This is an author-deposited version published in : http://oatao.univ-toulouse.fr/ Eprints ID : 15973 Abstract Chlordecone (CLD) was an organochlorine insecticide whose previous use resulted in an extensive pollution of the environment with severe health effects and social consequences. A closely related compound, 5b-hydrochlordecone (5b-hydroCLD), has been searched for and often detected in environmental matrices from the geographical area where CLD was applied. The current consensus considered that its presence was not the result of a biotic or abiotic dechlorination of CLD in these matrices but rather the consequence of its presence as impurity (synthesis by-product) in the CLD released into the environment. The aim of the present study was to determine if and to what extent degradation of CLD into 5b-hydroCLD occurred in the field. To test this hypothesis, the ratios of 5b-hydroCLD and CLD concentrations in a dataset of 810 soils collected between 2006 and 2012 in Martinique were compared to the ratios measured in 3 samples of the CLD dust commercial formulations applied in the banana fields of French West Indies (FWI) and 1 sample of the technical-grade CLD corresponding to the active ingredient used in such formulations. Soil data were processed with a hierarchical Bayesian model to account for random measurement errors and data censoring. Any pathway of CLD transformation into 5b-hydroCLD occurring over the long term in FWI soils would indeed change the ratio of 5b-hydroCLD/ CLD compared to what it was in the initially applied formulations. Results showed a significant increase of the 5b-hydroCLD/CLD ratio in the soils-25 times greater in soil than in commercial formulations-which suggested that natural CLD transformation into 5b-hydroCLD over the long term occurred in these soils. Results from this study may impact future decisions for the remediation of the polluted areas.

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“…Among them, the short‐chain CPs (C 10 –C 13 ) (SCCPs) are the most extensively used . Their physicochemical properties such as low solubility in water (hydrophobic behavior) and high octanol/water partition coefficients (log K ow from 3.82 to 7.75), suggest that these compounds would be mainly adsorbed on the particulate matter, sediments and sewage sludge . Nevertheless, as SCCPs are considered persistent compounds and showed high toxicity toward aquatic organisms, they have been included in the list of priority substances in the field of water policy, amending the European Water Framework Directive (WFD) 2000/60/EC .…”

Section: Introductionmentioning

confidence: 99%

Routine Method for the Analysis of Short‐Chain Chlorinated Paraffins in Surface Water and Wastewater

Rubirola¹,

Santos

Boleda³

et al. 2018

CLEAN Soil Air Water

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Short‐chain chlorinated paraffins (SCCPs) are persistent compounds that are included in the list of priority substances in the field of water policy of the European Union in 2001. In this paper, a method based on liquid–liquid extraction and gas chromatography with electron capture detection (GC‐ECD) is evaluated to be proposed for the routine analysis of SCCPs in environmental water. Limits of quantification (LOQ) at ng L−1 levels that allow compliance with the maximum admissible level established in the Directive 2013/39/EU, good precision (lower than 11%) and expanded measurement uncertainties (ISO 11352) (lower than 20%) for surface and wastewater samples are obtained. The good agreement between the results found using GC‐ECD and gas chromatography coupled with negative ion chemical ionization mass spectrometry (GC‐NICI‐MS), with relative errors lower than 13%, showed that GC‐ECD is a reliable method to control the presence of SCCPs in environmental water. The method is applied to river and wastewater samples collected in the Metropolitan Area of Barcelona (Spain). SCCPs are found in all the influents of wastewater treatment plants at concentrations ranging from <0.01 (MLOQ) to 3.20 μg L−1, while in the effluents they are detected in 54% of samples at levels below 0.13 μg L−1. SCCPs are not detected at the intake of a drinking water treatment plant that supply water to Barcelona city and only sporadically in the Llobregat River.

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Effects of Chain Length, Chlorination Degree, and Structure on the Octanol−Water Partition Coefficients of Polychlorinated n-Alkanes

Cited by 125 publications

References 34 publications

Chlorines Are Not Evenly Substituted in Chlorinated Paraffins: A Predicted NMR Pattern Matching Framework for Isomeric Discrimination in Complex Contaminant Mixtures

Chlorines Are Not Evenly Substituted in Chlorinated Paraffins: A Predicted NMR Pattern Matching Framework for Isomeric Discrimination in Complex Contaminant Mixtures

Natural transformation of chlordecone into 5b-hydrochlordecone in French West Indies soils: statistical evidence for investigating long-term persistence of organic pollutants

Routine Method for the Analysis of Short‐Chain Chlorinated Paraffins in Surface Water and Wastewater

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