Journal of Soils and Sediments

, Volume 17, Issue 1, pp 35–46 | Cite as

Theoretical investigation of congener-specific soil sorption of polychlorinated biphenyls by DFT computation and potent QSAR analyses

  • Mengrong Zhu
  • Chenggang Gu
  • Yinwen Cheng
  • Xuehai Ju
  • Yongrong Bian
  • Xinglun Yang
  • Yang Song
  • Mao Ye
  • Fang Wang
  • Xin Jiang
Soils, Sec 1 • Soil Organic Matter Dynamics and Nutrient Cycling • Research Article



Few studies have been conducted to understand well the underlying soil sorptive mechanism due to the limited experimental determination for the enormous number of polychlorinated biphenyl (PCB) congeners. The objective of this paper was to obtain further insights into the soil sorption behavior of PCBs with exploration of the sorptive mechanism at the molecular level for sorption affinity, which could be anticipated to help explore the migration fates and assess the bioavailability of PCBs in soil.

Materials and methods

Soil sorption coefficients of 52 kinds of PCB congeners were collected in this paper. The geometries of PCBs were fully optimized within Gaussian 03 suite of programs, and 27 molecular descriptors which describe the electronic and thermodynamic properties were finally determined with optimized structures after optimization. The quantitative structure–activity relationships (QSARs) for predicting the soil sorption of PCBs were developed by the combination of density functional theory (DFT) computation and partial least squares analyses, which maximized the correlation between the DFT-calculated properties and soil sorption of PCBs. The QSAR was critically validated with better performance in sensitivity, robustness, interpretation and prediction, and specific description of the applicability domain.

Results and discussion

For the successfully developed QSAR, R y,cum(adj) 2 and Q cum 2 were respectively recorded as 0.922 and 0.896, and R EXT 2 and Q EXT 2 were respectively recorded as 0.905 and 0.914, which demonstrated the stability and predictability of the model. The molecular electronegativity of PCBs by DFT was significantly indicative of a positive correlation with sorption potency, while polarizability had a negative correlation with it. QSAR analyses also revealed the favorable structural requirement of more chlorination at meta/para sites for soil sorption. It was implied that the soil sorption should be largely ascribed to the electrostatic interaction between PCBs and soil organic matter. Nevertheless, the thermodynamic stability and hydrophobicity related to the molecular entropy increment of PCBs were also beneficial to enhancing soil sorption.


QSAR analyses particularly indicated the strong dependence of variation of soil sorption on molecular electronic properties, such as electronegativity and polarizability, which suggested the predominance of electrostatic interaction with soil organic matter. Meta/para chlorination was illustrated as a preferable structural requirement for soil sorption. In addition, the thermodynamic stability and hydrophobicity driven by entropy increment were also effective for soil sorption. These results contributed to predict the migration and fate of PCBs in soil system.


Congener specificity DFT PCBs QSARs Soil sorption 



Applicability domain


Density functional theory


Highest occupied molecular orbital


Soil organic carbon-normalized sorption coefficient


Lowest unoccupied molecular orbital


Organization for Economic Cooperation and Development


Polychlorinated biphenyls


Partial least squares


Quantitative structure–activity relationship


Variable importance in projection



This work was financially supported by the National Natural Science Foundation of China (21377138), National Basic Research Program (973) of China (2014CB441105), Frontier Program of “135” Plans and Knowledge Innovation Engineering Field of CAS (ISSASIP1618), and National Natural Science Foundation of China (41271464 and 41271327).

Compliance with ethical standards

Conflicts of interest

The authors declare no conflict of interests.

Supplementary material

11368_2016_1487_MOESM1_ESM.docx (68 kb)
ESM 1 (DOCX 68 kb)


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Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  • Mengrong Zhu
    • 1
    • 2
  • Chenggang Gu
    • 1
  • Yinwen Cheng
    • 1
    • 2
  • Xuehai Ju
    • 3
  • Yongrong Bian
    • 1
  • Xinglun Yang
    • 1
  • Yang Song
    • 1
  • Mao Ye
    • 1
  • Fang Wang
    • 1
  • Xin Jiang
    • 1
  1. 1.Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil ScienceChinese Academy of SciencesNanjingPeople’s Republic of China
  2. 2.University of the Chinese Academy of SciencesBeijingPeople’s Republic of China
  3. 3.Department of ChemistryNanjing University of Science and TechnologyNanjingPeople’s Republic of China

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