ELECTRONIC SUPPLEMENTARY MATERIAL
SOILS, SEC 3 • REMEDIATION AND MANAGEMENT OF CONTAMINATED OR DEGRADED
LANDS • RESEARCH ARTICLE
Sorption of polycyclic aromatic hydrocarbons to soils enhanced by heavy metals: perspective of
molecular interactions
Xiao Liang1, 2 • Lizhong Zhu1, 2 • Shulin Zhuang1
Received: 12 October 2015 / Accepted: 14 December 2015
© Springer-Verlag Berlin Heidelberg 2015
Responsible editor: Jan Schwarzbauer
1
Department of Environmental Science, Zhejiang University, Hangzhou, Zhejiang 310058, China
2
Zhejiang Provincial Key Laboratory of Organic Pollution Process and Control, Hangzhou, Zhejiang
310058, China
 Lizhong Zhu
zlz@zju.edu.cn
Table S1 Potential interactions in aromatic π-systems
Interaction
Energy (kJ mol-1)
References
Van der Waals forces
<4
(Halgren 1996)
N-π EDA
25-40
(Haderlein and Schwarzenbach 1993)
Self-stacking
4-30
(Boyd et al. 2001; Meyer et al. 2003)
(Emsley 1980; Feyereisen et al. 1996;
H bonding
5-50
Jeffrey 1997)
Electrostatic
11-90
(Gorb et al. 2000; Li et al. 2004)
(Hong et al. 2003; Meyer et al. 2003;
π-π EDA
17-111
Orabi and Lamoureux 2012)
Table S2
Bond length (r) and interaction energy (G) between PAHs and heavy metal cations at the
B3LYP/def2svp level
PAH
Metal
r (Å)a
G ( kcal mol-1)
Naphthalene
Cu(II)
2.17
-14.69
Pb(II)
2.80
-84.52
Cr(III)
3.78
-139.3
Cu(II)
2.12
-15.54
Pb(II)
2.85
-90.89
Cr(III)
3.76
-141.2
Cu(II)
2.12
-11.69
Pb(II)
2.80
-93.77
Cr(III)
3.80
-150.5
Phenanthrene
Pyrene
12000
(a) Naphthalene
Amount of Sorption, qe (mg kg-1)
Amount of Sorption, qe (mg kg-1)
6000
4500
3000
Soil 1
Soil 2
1500
(b) Phenanthrene
9000
6000
Soil 1
Soil 2
3000
0
Cu(II)
Amount of Sorption, qe (mg kg-1)
32000
Pb(II)
Cr(III)
Pb(II)
Cr(III)
0
Cu(II)
Pb(II)
Cr(III)
(c) Pyrene
24000
16000
8000
Soil 1
Soil 2
0
Cu(II)
Fig. S1
-1
Sorption of 1.0 mmol L heavy metal cations to soil 1 and soil 2, the solid-to-liquid ratio
(w/v): (a) 0.8 g/8 mL; (b) 0.4 g/20 mL; (c) 0.05 g/20 mL
(a)
(b)
Cu2+
Nap
(d)
Pb2+
Nap
(g)
Nap
Fig. S2
Pyr
(f)
Pb2+
Phe
(h)
Cr3+
Cu2+
Phe
(e)
Pb2+
(c)
Cu2+
Pyr
(i)
Cr3+
Cr3+
Phe
Pyr
The binding conformations of PAH molecules with heavy metal cations in the aqueous
solution: (a) Cu(II)-Nap, (b) Cu(II)-Phe, (c) Cu(II)-Pyr, (d) Pb(II)-Nap, (e) Pb(II)-Phe, (f) Pb(II)-Pyr, (g)
Cr(III)-Nap, (h) Cr(III)-Phe, (i) Cr(III)-Pyr. Nap, Phe and Pyr were the abbreviations of naphthalene,
phenanthrene and pyrene
References
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nitrobenzenes by smectite clays. Environ Sci Technol 35:4227-4234
Emsley J (1980) Very strong hydrogen bonding. Chem Soc Rev 9:91-124
Feyereisen MW, Feller D, Dixon DA (1996) Hydrogen bond energy of the water dimer. J Phys Chem
100:2993-2997
Gorb L, Gu J, Leszczynska D, Leszczynski J (2000) The interaction of nitrobenzene with the hydrate
basal surface of montmorillonite: an ab initio study. Phys Chem Chem Phys 2:5007-5012
Haderlein SB, Schwarzenbach RP (1993) Adsorption of substituted nitrobenzenes and nitrophenols to
mineral surfaces. Environ Sci Technol 27:316-326
Halgren TA (1996) Merck molecular force field. II. MMFF94 van der Waals and electrostatic
parameters for intermolecular interactions. J Comput Chem 17:520-552
Hong L, Ghosh U, Mahajan T, Zare RN, Luthy RG (2003) PAH sorption mechanism and partitioning
behavior in lampblack-impacted soils from former oil-gas plant sites. Environ Sci Technol
37:3625-3634
Jeffrey GA (1997) An introduction to hydrogen bonding, 12. Oxford university press New York
Li H, Teppen BJ, Johnston CT, Boyd SA (2004) Thermodynamics of nitroaromatic compound
adsorption from water by smectite clay. Environ Sci Technol 38:5433-5442
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biological recognition. Angew Chem Int Edit 42:1210-1250
Orabi EA, Lamoureux G (2012) Cation-π and π-π Interactions in aqueous solution studied using
polarizable potential models. J Chem Theory Comput 8:182-193