scholarly journals Predicting Partition Coefficients of Short-Chain Chlorinated Paraffin Congeners by Combining COSMO-RS and Fragment Contribution Model Approaches

Author(s):  
Satoshi Endo ◽  
Jort Hammer

Chlorinated paraffins (CPs) are highly complex mixtures of polychlorinated <i>n</i>-alkanes with differing chain lengths and chlorination patterns. Knowledge on physicochemical properties of individual congeners is limited but needed to understand their environmental fate and potential risks. This work combines a sophisticated but time-demanding quantum chemically based method COSMO-RS and a fast-running fragment contribution approach to establish models to predict partition coefficients of a large number of short-chain chlorinated paraffin (SCCP) congeners. Molecular fragments of a length of up to C<sub>4</sub> in CP molecules were counted and used as explanatory variables to develop linear regression models for predicting COSMO-RS-calculated values. The resulting models can quickly provide COSMO-RS predictions for octanol–water (<i>K</i><sub>ow</sub>), air–water (<i>K</i><sub>aw</sub>), and octanol–air (<i>K</i><sub>oa</sub>) partition coefficients of SCCP congeners with an accuracy of 0.1–0.3 log units root mean squared errors (RMSE). The model predictions for <i>K</i><sub>ow</sub> agree with experimental values for individual constitutional isomers within 1 log unit. The ranges of partition coefficients for each SCCP congener group were computed, which successfully reproduced experimental log <i>K</i><sub>ow</sub> ranges of industrial CP mixtures. As an application of the developed approach, the predicted <i>K</i><sub>aw</sub> and <i>K</i><sub>oa</sub> were plotted to evaluate the bioaccumulation potential of each SCCP congener group.

2020 ◽  
Author(s):  
Satoshi Endo ◽  
Jort Hammer

Chlorinated paraffins (CPs) are highly complex mixtures of polychlorinated <i>n</i>-alkanes with differing chain lengths and chlorination patterns. Knowledge on physicochemical properties of individual congeners is limited but needed to understand their environmental fate and potential risks. This work combines a sophisticated but time-demanding quantum chemically based method COSMO-RS and a fast-running fragment contribution approach to establish models to predict partition coefficients of a large number of short-chain chlorinated paraffin (SCCP) congeners. Molecular fragments of a length of up to C<sub>4</sub> in CP molecules were counted and used as explanatory variables to develop linear regression models for predicting COSMO-RS-calculated values. The resulting models can quickly provide COSMO-RS predictions for octanol–water (<i>K</i><sub>ow</sub>), air–water (<i>K</i><sub>aw</sub>), and octanol–air (<i>K</i><sub>oa</sub>) partition coefficients of SCCP congeners with an accuracy of 0.1–0.3 log units root mean squared errors (RMSE). The model predictions for <i>K</i><sub>ow</sub> agree with experimental values for individual constitutional isomers within 1 log unit. The ranges of partition coefficients for each SCCP congener group were computed, which successfully reproduced experimental log <i>K</i><sub>ow</sub> ranges of industrial CP mixtures. As an application of the developed approach, the predicted <i>K</i><sub>aw</sub> and <i>K</i><sub>oa</sub> were plotted to evaluate the bioaccumulation potential of each SCCP congener group.


2020 ◽  
Author(s):  
Satoshi Endo ◽  
Jort Hammer

Chlorinated paraffins (CPs) are highly complex mixtures of polychlorinated <i>n</i>-alkanes with differing chain lengths and chlorination patterns. Knowledge on physicochemical properties of individual congeners is limited but needed to understand their environmental fate and potential risks. This work uses a sophisticated but time-demanding quantum chemically based method COSMO-RS and a fast-running fragment contribution approach to enable prediction of partition coefficients for a large number of short-chain chlorinated paraffin (SCCP) congeners. Fragment contribution models (FCMs) were developed using molecular fragments with a length of up to C<sub>4</sub> in CP molecules as explanatory variables and COSMO-RS-calculated partition coefficients as training data. The resulting FCMs can quickly provide COSMO-RS predictions for octanol–water (<i>K</i><sub>ow</sub>), air–water (<i>K</i><sub>aw</sub>), and octanol–air (<i>K</i><sub>oa</sub>) partition coefficients of SCCP congeners with an accuracy of 0.1–0.3 log units root mean squared errors. The FCM predictions for <i>K</i><sub>ow</sub> agree with experimental values for individual constitutional isomers within 1 log unit. The distribution of partition coefficients for each SCCP congener group was computed, which successfully reproduced experimental log <i>K</i><sub>ow</sub> ranges of industrial CP mixtures. As an application of the developed FCMs, the predicted <i>K</i><sub>aw</sub> and <i>K</i><sub>oa</sub> were plotted to evaluate the bioaccumulation potential of each SCCP congener group.<br>


2020 ◽  
Author(s):  
Satoshi Endo ◽  
Jort Hammer

Chlorinated paraffins (CPs) are highly complex mixtures of polychlorinated <i>n</i>-alkanes with differing chain lengths and chlorination patterns. Knowledge on physicochemical properties of individual congeners is limited but needed to understand their environmental fate and potential risks. This work uses a sophisticated but time-demanding quantum chemically based method COSMO-RS and a fast-running fragment contribution approach to enable prediction of partition coefficients for a large number of short-chain chlorinated paraffin (SCCP) congeners. Fragment contribution models (FCMs) were developed using molecular fragments with a length of up to C<sub>4</sub> in CP molecules as explanatory variables and COSMO-RS-calculated partition coefficients as training data. The resulting FCMs can quickly provide COSMO-RS predictions for octanol–water (<i>K</i><sub>ow</sub>), air–water (<i>K</i><sub>aw</sub>), and octanol–air (<i>K</i><sub>oa</sub>) partition coefficients of SCCP congeners with an accuracy of 0.1–0.3 log units root mean squared errors. The FCM predictions for <i>K</i><sub>ow</sub> agree with experimental values for individual constitutional isomers within 1 log unit. The distribution of partition coefficients for each SCCP congener group was computed, which successfully reproduced experimental log <i>K</i><sub>ow</sub> ranges of industrial CP mixtures. As an application of the developed FCMs, the predicted <i>K</i><sub>aw</sub> and <i>K</i><sub>oa</sub> were plotted to evaluate the bioaccumulation potential of each SCCP congener group.<br>


1977 ◽  
Vol 55 (12) ◽  
pp. 2404-2410 ◽  
Author(s):  
Douglas M. Chen ◽  
Fred Y. Fujiwara ◽  
Leonard W. Reeves

The degree of order of solubilized molecules and ions in oriented lyomesophases has been determined at specifically deuterated C—D bond axes from the quadrupole splitting of the deuterium magnetic resonance. Mixtures at low concentration of specifically deuterated alkanes, alcohols, carboxylic acids, and carboxylates of different chain length have been observed in host cationic and anionic lyomesophases. The degree of order of a given C—D position in alcohols increases strongly with chain length up to a length comparable with the host detergent. A broad series of carboxylic acids and carboxylate ions from C2 to C16 have been deuterated in the α position. The α-C—D bond axis in the solubilisate increases in order with chain length, the anion having lower order than the parent acid. An accurately linear increase in the degree of order of the α position is observed for intermediate chain lengths. At chain lengths approximately equal to the host chain lengths the α position reaches a limiting value in the degree of order and further segments do not influence the order. At short chain lengths the degree of order is less than that predicted from extrapolation of order in the linear region. This has been interpreted in terms of distribution into the aqueous compartment by the solubilisates of short chain length. Acetic acid and the acetate, propionate, butanoate, and pentanoate ions spend an appreciable amount of time in the aqueous region. An estimate has been made of these distributions based on reasonable assumptions.


Author(s):  
Paolo Giudici

Several classes of computational and statistical methods for data mining are available. Each class can be parameterised so that models within the class differ in terms of such parameters (see, for instance, Giudici, 2003; Hastie et al., 2001; Han & Kamber, 2000; Hand et al., 2001; Witten & Frank, 1999): for example, the class of linear regression models, which differ in the number of explanatory variables; the class of Bayesian networks, which differ in the number of conditional dependencies (links in the graph); the class of tree models, which differ in the number of leaves; and the class multi-layer perceptrons, which differ in terms of the number of hidden strata and nodes. Once a class of models has been established the problem is to choose the “best” model from it.


Author(s):  
Jennifer L. Perret ◽  
Colleen O. Best ◽  
Jason B. Coe ◽  
Amy L. Greer ◽  
Deep K. Khosa ◽  
...  

A relatively high risk of poor mental health has been described among Canadian veterinarians, but no published studies have explored the impact that veterinarian mental health may have on veterinary clients and patients. In order to investigate the association between veterinarian mental health and veterinary client satisfaction, veterinarians were randomly sampled and recruited throughout southwestern Ontario, Canada, from November, 2017, through January, 2019. Sixty participating veterinarians completed an enrollment survey that included psychometric scales measuring resilience, perceived stress, anxiety, depression, emotional distress, emotional exhaustion, depersonalization, personal accomplishment, burnout, secondary traumatic stress, and compassion satisfaction. Nine hundred and ninety-five companion animal clients of these veterinarians were recruited in-clinic over 2–3 days and completed a post-appointment survey including the Client Satisfaction Questionnaire. The associations between clients' satisfaction scores (as the outcome variable) and each of the veterinarians' mental health measures (as the explanatory variables) were assessed using separate, multilevel, multivariable linear regression models. The associations between client satisfaction and veterinarian mental health measures were non-linear and complex; in several of the models, relatively higher client satisfaction was unexpectedly associated with poor veterinarian mental health states, while lower client satisfaction was associated with mental health scores suggesting wellness. Given that client satisfaction may impact client adherence to medical recommendations, client loyalty, and business income, the association with veterinarian mental health may have broad implications and warrants further investigation.


2019 ◽  
Vol 60 (4) ◽  
pp. 755-790 ◽  
Author(s):  
Christopher J Grose ◽  
Juan C Afonso

Abstract We examine REE (Rare-Earth Element) and isotopic (Sr–Hf–Nd–Pb) signatures in OIB (Ocean Island Basalts) as a function of lithospheric thickness and show that the data can be divided into thin- (&lt;12 Ma) and thick-plate (&gt;12 Ma) sub-sets. Comparison to geophysically constrained thermal plate models indicates that the demarcation age (∼12 Ma) corresponds to a lithospheric thickness of about 50 km. Thick-plate OIB show incompatible element and isotopic enrichments, whereas thin-plate lavas show MORB-like or slightly enriched values. We argue that enriched signatures in thick-plate OIB originate from low-degree melting at depths below the dry solidus, while depleted signatures in MORB and thin-plate OIB are indicative of higher-degree melting. We tested quantitative explanations of REE systematics using melting models for homogeneous fertile peridotite. Using experimental partition coefficients for major upper mantle minerals, our equilibrium melting models are not able to explain the data. However, using a new grain-scale disequilibrium melting model for the same homogeneous lithology the data can be explained. Disequilibrium models are able to explain the data by reducing the amount of incompatible element partitioning into low degree melts. To explore new levels of detail in disequilibrium phenomena, we employ the Monte-Carlo Potts model to characterize the textural evolution of a microstructure undergoing coarsening and phase transformation processes simultaneous with the diffusive partitioning of trace elements among solid phases and melt in decompressing mantle. We further employ inverse methods to study the thermochemical properties required for models to explain the OIB data. Both data and theory show that OIB erupted on spreading ridges contain signatures close to MORB values, although E-MORB provides the best fit. This indicates that MORB and OIB are produced by compositionally indistinguishable sources, although the isotopic data indicate that the source is heterogeneous. Also, a posteriori distributions are found for the temperature of the thermomechanical lithosphere-asthenosphere boundary (TLAB), the temperature in the source of OIB (Tp, oib) and the extent of equilibrium during melting (i.e. grain size). TLAB has been constrained to 1200–1300°C and Tp, oib is constrained to be &lt;1400°C. However, we consider the constraints on Tp, oib as a description of all OIB to be provisional, because it is a statistical inference from the global dataset. Exceptional islands or island groups may exist, such as the classical ‘hotspots’ (Hawaii, Reunion, etc) and these islands may originate from hot sources. On the other hand, by the same statistical arguments their origins may be anomalously hydrated or enriched instead. Mean grain size in the source of OIB is about 1–5 mm, although this is also provisional due to a strong dependence on knowledge of partition coefficients, ascent rate and the melting function. We also perform an inversion in which partition coefficients were allowed to vary from their experimental values. In these inversions TLAB and Tp, oib are unchanged, but realizations close to equilibrium can be found when partition coefficients differ substantially from their experimental values. We also investigated bulk compositions in the source of OIB constrained by our inverse models. Corrections for crystallization effects provided ambiguous confirmations of previously proposed mantle compositions, with depleted mantle providing the poorest fits. We did not include isotopes in our models, but we briefly evaluate the lithospheric thickness effect on isotopes. Although REE data do not require a lithologically heterogeneous source, isotopes indicate that a minor enriched component disproportionately contributes to thick-plate OIB, but is diluted by high-degree melting in the generation of thin-plate OIB and MORB.


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