ELECTRONIC SUPPLEMENTARY MATERIAL
SOILS, SEC 4 • ECOTOXICOLOGY • RESEARCH ARTICLE
Dechlorinating transformation of propachlor through nucleophilic substitution by dithionite on the
surface of alumina
Chengshuai Liu • Kaimin Shih • Yuanxue Gao • Fangbai Li • Lan Wei
Received: 7 January 2012 / Accepted: 14 March 2012
Springer-Verlag 2012
Responsible editor: Jay Gan
C. S. Liu • Y. X. Gao • F. B. Li () • L. Wei
Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of
Eco-Environmental and Soil Sciences, Guangzhou 510650, P. R. China
e-mail: cefbli@soil.gd.cn
C. S. Liu • K. Shih ()
Department of Civil Engineering, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China
e-mail: kshih@hku.hk
() Corresponding authors:
Fangbai Li
e-mail: cefbli@soil.gd.cn
and
Kaimin Shih
Tel. +852-2859-1973
Fax. +852-2559-5337
e-mail: kshih@hku.hk
Online Resource 1
The X-ray Diffraction (XRD) patterns (Fig. S1) of the three alumina materials were collected using a Bruker D8
diffractometer (Bruker Co., Ltd.) equipped with Cu X-ray tube operated at 40 kV and 40 mA. Scans were
collected from 10° to 90° 2θ-angle, with a step size of 0.02° and a counting time of 1 s/step. Phase identification
was executed by matching XRD patterns with powder diffraction files (PDF) in the database published by
Relative Intensities (arb.unit)
International Centre for Diffraction Data (ICDD).
o
1500 C, 3h
o
650 C, 3h
PURAL SB powder
10
20
30
40
50
60
70
80
90
100
110
120
130
2Theta (degree)
Fig. S1 The XRD patterns of Pural SB powder (γ-AlOOH, boehmite; PDF#74-1895); Boemite powder heated at
650°C for 3 h (γ-Al2O3; Reference #17); and the boehmite powder further heated at 1500°C for 6 h (αAl2O3, corundum; PDF#10-0173)
2
Online Resource 2
Fig. S2 FTIR spectra of the alumina samples in wavenumber from 1500 to 1100 cm-1: (a) γ-AlOOH, (b) γ-Al2O3,
and (c) α-Al2O3. The curves in each figure include the FTIR spectra of alumina samples: before any
potential reactions (a1, b1, and c1), after contacting with propachlor for 10 h (a2, b2, and c2), and after
participating in the reaction of propachlor and dithionite for 10 h (a3, b3, and c3)
3
Online Resource 3
Propachlor transformation products were analyzed by liquid chromatography/mass spectrometry (LC/MS) using
a Shimadazu HPLC system with a Kromasil C18 column (250 mm × 4.6 mm I.D.), SIL-HT autosampler, LC-10
AT vacuum pump, and API 3000 mass analyzer as reported in a previous study (Liu et al. 2011). HPLC
separation was performed at 0.5 mL/min with a mobile phase of 85:15 water/acetonitrile ratio for 1.0 min, a
50:50 ratio for 2 min, with a linear change to the 10:90 ratio over 10 min and then held for 6 min, followed by reequilibration at the initial condition (85:15 water/acetonitrile ratio) for 8.5 min. An electrospray interface (ESI)
was used for the MS measurements in positive MS scan mode and full scan acquisition between m/z 50 and 550.
The other parameters were set as follows: the ESI was 4.0 kV, source block temperature was 80C, and the
desolvation temperature was 400C. The flow rate of the desolvation gas (N2) was set at 400 L/h, and argon was
used as a cone gas at 50 L/h.
Fig. S3 Total ion chromatograms in positive mode and the product spectra of propachlor (10 mg/L)
dechlorination by 5 mM dithionite and 2.0 g/L γ-Al2O3 for 10 h at pH 7.0 and 25°C
4
Online Resource 4
8.30
100
Scan ES+
TIC
7.45e6
CHCH 3CH 3
Propachlor
N
C
CH2 SO 3 H
O
%
C H CH 3C H 3
CH CH 3CH 3
N
C
10.42
C H2 OH
N
8.19
C H 2 SSO 4 H
O
9.63
O
C
0
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
12.00
13.00
14.00
time
209
208
100
CHCH 3CH 3
%
N
C
319
CH2 OH
O
377
318
Positive ion spectra for
reaction product at 8.19 min
0
50
100
150
200
250
300
350
400
450
500
m/z
550
257
100
H
CHCH 3CH 3
N
%
C
258
CH2 SO3 H
O
155
183
Positive ion spectra for
reaction product at 9.63 min
291305
m/z
0
50
100
150
200
250
300
350
400
450
500
550
305
100
142
283
CHCH 3CH 3
%
N
C
306
CH2SSO4H
O
Positive ion spectra for
reaction product at 10.42 min
304
m/z
0
50
100
150
200
250
300
350
400
450
500
550
Fig. S4 Total ion chromatograms in positive mode and product spectra of propachlor (100 µM) transformation
initiated by 10 mM dithionite for 10 h at pH 7.0 and T = 303 K. (Liu et al. 2011)
References
Liu CS, Shih K, Wei L, Wang F, Li FB (2011) Kinetics and mechanism of propachlor reductive transformation
through nucleophilic substitution by dithionite. Chemosphere 85:1438-1443
5