Supplementary Information
Occurrence and dissipation of benzotriazoles and ultraviolet filters in
biosolid-amended soils
Hua-Jie Lai a, Guang-Guo Ying a *, Yi-Bing Ma b, Zhi-Feng Chen a, Feng Chen a,
You-Sheng Liu a
a
State Key Laboratory of Organic Geochemistry, CAS Centre for Pearl River Delta
Environmental Pollution and Control Research, Guangzhou Institute of Geochemistry,
Chinese Academy of Sciences, Guangzhou 510640, China
b
Ministry of Agriculture Key Laboratory of Plant Nutrition and Nutrient Cycling,
Institute of Agricultural Resources and Regional Planning, Chinese Academy of
Agricultural Sciences, Beijing, 100081, China.
* Corresponding author. Phone/fax: +86 20 85290200.
Email address: guangguo.ying@gmail.com; guang-guo.ying@gig.ac.cn.
Content:
Figure Captions:
Figure S1 GC-MS extracted ion chromatograms (EIC) of the quantitative ions for target
compounds in 200 μg/L standard solution including
2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole (UV-326),
2-(2'-Hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole (UV-327),
2-(2-Hydroxy-3,5-dipenryl-phenyl) benzotriazole (UV-328), 2-(2'-Hydroxy-5'-octylphenyl)
benzotriazole (UV-329) and (2'-Hydroxy-5mg-methylphenyl) benzotriazole (UV-P).
Figure S2 LC-MS/MS extracted ion chromatograms (EIC) of the quantitative ions for target
compounds in 200 μg/L standard solution including benzotriazole (BT),
5-methyl-1H-benzotriazole (5-TT), 5,6-dimethyl-1H-benzotriazole (XT) and
5-chloro-1H-benzotriazole (CBT).
Table Captions:
Table S1. Physicochemical properties of BTs and UV filters in this study.
Table S2. Characteristic ions and retention times for target compounds in GC-MS.
Table S3. Mass transitions and retention times for target compounds in LC-MS/MS.
Table S4. Recoveries (%) and method precision (RSD % for n = 3), limits of detection (LOD) and
quantitation (LOQ) for target compounds.
Table S5. Concentrations of BTs and BUVSs in the soils collected from the three trial sites in
October 2010.
Table S6. Concentrations of BTs and BUVSs in the biosolid-amended soils of treatment 1 (T1) in
Shandong for one year monitoring.
Table S7. Concentrations of BTs and BUVSs in the biosolid-amended soils of treatment 2 (T2) in
Shandong for one year monitoring.
Figure S1 GC-MS extracted ion chromatograms (EIC) of the quantitative ions for target
compounds in 200 μg/L standard solution including
2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole (UV-326),
2-(2'-Hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole (UV-327),
2-(2-Hydroxy-3,5-dipenryl-phenyl) benzotriazole (UV-328), 2-(2'-Hydroxy-5'-octylphenyl)
benzotriazole (UV-329) and (2'-Hydroxy-5mg-methylphenyl) benzotriazole (UV-P).
Figure S2 LC-MS/MS extracted ion chromatograms (EIC) of the quantitative ions for target
compounds in 200 μg/L standard solution including benzotriazole (BT),
5-methyl-1H-benzotriazole (5-TT), 5,6-dimethyl-1H-benzotriazole (XT) and
5-chloro-1H-benzotriazole (CBT).
Table S1. Physicochemical properties of BTs and UV filters in this study.
Properties a
Class
Compound
CAS number
Molecular
formula
MW b
Kocc
(L/kg)
pKa
pKow
Structure
Benzotriazoles
benzotriazole
(BT)
N
95-14-7
C6H5N3
119.13
62.3
8.37
1.44
N
N
5-methyl-1Hbenzotriazole
N
136-85-6
C7H7N3
133.15
87.9
8.66
1.71
N
(5-TT)
N
5-chloro-1Hbenzotriazole
94-97-3
C6H4ClN3
153.57
99.8
(CBT)
7.5/
7.7
2.17
N
N
N
N
5,6-dimethyl-1Hbenzotriazole
Cl
4184-79-6
C8H9N3
147.18
177
7.6
2.26
N
N
(XT)
Benzotriazole
ultraviolet
2-(3-t-butyl-2-hydroxy-5-methylp
stabilizers
henyl)-5-chlorobenzotriazole
(UV-326)
OH
3896-11-5
C17H18ClN3O
315.5
3.9E+04
9.5
6.58
N
N
N
Cl
HO
2-(2'-Hydroxy-3',5'-di-tert-butylp
henyl)-5-chlorobenzotriazole
N
3864-99-1
C20H24ClN3O
357.89
9.7E+04
NA
6.91
N
N
Cl
(UV-327)
2-(2-Hydroxy-3,5-dipenryl-pheny
l) benzotriazole
25973-55-1
C22H29N3O
351.5
1.5E+05
NA
7.25
N
N
N
(UV-328)
HO
OH
2-(2'-Hydroxy-5'-octylphenyl)-be
nzotriazole
3147-75-9
C20H25N3O
323
1.1E+05
NA
6.21
2440-22-4
C13H11N3O
225.25
3539
NA
4.31
N
N
(UV-329)
(2'-Hydroxy-5mg-methylphenyl)
benzotriazole
N
(UV-P)
a Source:
b MW,
http://www.syrres.com/what-we-do//databaseforms.aspx?id=386; EPI suite, US EPA.
molecular weight. c estimated by using EPIWEB 4.0 (KOCWIN), US EPA. d NA, not available.
N
N
HO
N
Table S2. Characteristic ions and retention times for target compounds in GC-MS.
Compound
M.W.
R.T.
Ions a
Chrysene-d12 (IS)
UV-P
Benzyl cinnamate (SS)
UV-326
UV-329
UV-328
UV-327
240
225
238
315
323
351
358
12.510
9.768
9.893
12.958
13.173
13.779
13.837
240
225
131
300
252
322
342
a
Quantification ions.
236
226
192
315
253
323
344
241
224
193
302
323
351
343
Table S3. Mass transitions and retention times for target compounds in LC-MS/MS.
Compound
Fragmentor
(eV)
Precursor ions
(m/z)
Collision Energy
(eV)
Product ions a
(m/z)
Retention time
(min)
Corresponding I.S.
BT
135
120.1
Thiabendozole NH D6
120
134.1
4.446
Thiabendozole NH D6
CBT
140
154
4.883
Thiabendozole NH D6
XT
130
148.1
5.070
Thiabendozole NH D6
Thiabendozole
NH D6
205
208.1
65
39
77
51
98.9
72.9
77
51
179.9
136
3.425
5-TT
44
20
28
48
24
40
28
56
24
32
a
Quantification ions.
3.696
Table S4. Recoveries (%) and method precision (RSD % for n = 3), limits of detection (LOD) and quantitation (LOQ) for target compounds.
Soil
Sludge
Compound
Recoveries
%±RSD
Matrix
%±RSD
LOD
(ng/g)
LOQ
(ng/g)
Recoveries
%±RSD
Matrix %
±RSD
LOD
(ng/g)
LOQ
(ng/g)
BT
5-TT
CBT
TT
UV-326
UV-327
UV-328
UV-329
UV-P
98.1±5.5
85.8±6.6
86.1±6.9
74.7±5.1
81.7±1.5
80.1±0.1
80.4±1.1
117±1.1
99.5±4.5
110±1.7
92.3±0.7
90.7±2.8
77.0±3.8
105±0.1
102±0.3
100±1.0
153±0.7
136±5.6
0.07
0.03
0.07
0.08
0.2
0.23
0.27
0.25
0.47
0.24
0.10
0.23
0.28
0.67
0.77
0.91
0.84
1.57
106±2.1
108±2.8
109±4.6
108±3.6
80.5±4.1
78.9±3.3
70.9±4.6
112±15.2
112±6.1
95.9±1.3
101±2.7
103±3.2
105±1.4
94.7±6.1
84.1±4.0
86.7±6.0
105±21.8
136±4.0
1.15
0.74
1.97
0.90
2.16
2.77
1.13
1.36
3.49
3.84
2.45
6.55
3.01
7.18
9.23
3.76
4.54
11.6
Table S5. Concentrations of BTs and BUVSs in the soils collected from the three trial sites in October 2010.
Treatment
CK c
T1
T2
a
Site
BT
5-TT
a
b
CBT
XT
UV-326
UV-327
UV-328
UV-329
UV-P
HN
ZJ
SD
HN
ZJ
SD
HN
1.2±0.1
1.8±1.3
< LOQ
6.8±0.6a d
2.8±1.7b
4.0±1.3b
15.5±3.2a
< LOD
0.4±0.3
< LOQ
9.2±0.8a
3.9±2.8b
5.6±2.2b
22.6±5.0a
< LOD
< LOD
< LOD
< LOQ
< LOQ
< LOQ
< LOQ
< LOD
< LOD
< LOD
< LOQ
< LOQ
< LOD
0.4±0.1
< LOD
< LOD
< LOD
1.0±0.1b
1.2±0.5b
2.3±0.8a
4.3±0.5ab
0.9±0.1
< LOD
< LOD
1.8±0.2b
1.4±0.6b
3.0±0.8a
6.8±1.1a
< LOD
< LOD
< LOD
3.4±0.4a
3.5±2.3a
5.3±0.6a
23.4±3.0a
< LOD
< LOD
< LOD
5.8±0.8b
5.0±2.5b
10.3±3.1a
30.6±4.7a
< LOD
< LOD
< LOD
2.5±0.4b
3.0±0.8b
4.2±0.5a
8.0±1.1a
ZJ
11.5±7.2ab
19.3±12.1ab
0.7±0.5
0.8±0.8
3.3±0.9b
3.5±0.9b
11.3±5.0b
19.3±2.5b
6.7±2.3a
SD
6.1±0.8b
7.0±1.7b
< LOQ
< LOQ
4.4±0.3a
5.9±0.4a
14.6±2.0b
33.3±7.3a
8.7±1.7a
Mean (ng/g) ± standard deviation (%) (n = 4, replicate samples at the same time).
< LOQ: below the limit of quantification; < LOD: below the limit of detection.
c CK, T1 and T2 represent control, Treatment 1 with one biosolid application, and Treatment 2 with biosolid application every year.
d Letters (a and b) indicate the significant difference of concentration data by Duncan’s multiple range test, p < 0.05.
b
Table S6. Concentrations of BTs and BUVSs in the biosolid-amended soils of treatment 1 (T1) in Shandong.
Time
Oct 2010
Nov 2010
Dec 2010
Mar 2011
Apr 2011
May 2011
Jun 2011
Jul 2011
Aug 2011
Sep 2011
Oct 2011
a
b
BT
4.0±1.3
3.7±1.0
4.9±1.1
5.0±1.2
4.8±1.2
5.5±1.4
3.8±0.8
6.1±1.2
3.3±0.6
3.6±1.8
3.1±0.4
5-TT
a
5.6±2.2
5.8±1.6
7.9±1.3
7.8±1.6
6.1±1.3
6.8±1.7
3.9±0.8
8.2±2.1
4.8±0.8
4.8±2.3
4.0±0.4
CBT
< LOQ
< LOQ
< LOQ
< LOQ
< LOQ
< LOQ
< LOQ
< LOQ
< LOQ
< LOQ
< LOQ
b
XT
UV-326
UV-327
UV-328
UV-329
UV-P
< LOD
< LOQ
< LOQ
< LOQ
< LOQ
< LOQ
< LOQ
< LOQ
< LOQ
< LOQ
< LOQ
2.3±0.8
1.4±0.1
2.3±0.1
2.6±0.2
2.6±0.2
1.5±0.1
1.3±0.1
1.1±0.3
0.7±0.03
1.0±0.1
1.0±0.1
3.0±0.8
2.1±0.3
3.3±0.3
3.4±0.3
3.3±0.3
2.4±0.2
1.5±0.3
2.0±0.5
1.4±0.1
1.7±0.1
1.7±0.03
5.3±0.6
5.3±0.4
6.8±1.0
6.8±1.1
5.9±0.6
5.2±0.6
3.0±0.9
5.1±1.7
3.2±0.4
3.7±0.7
3.5±0.1
10.3±3.1
13.7±0.1
26.4±8.3
19.0±4.4
25.5±11.7
36.4±32.5
15.1±5.4
16.0±3.4
7.7±0.9
7.1±1.6
6.3±1.6
4.2±0.5
3.5±0.3
6.0±0.8
7.0±0.8
25.8±8.5
5.1±1.0
5.1±0.9
4.8±0.6
4.5±0.5
1.8±0.1
2.4±0.7
Mean (ng/g) ± standard deviation (%) (n = 4, replicate samples at the same time).
< LOQ: below the limit of quantification; < LOD: below the limit of detection.
Table S7. Concentrations of BTs and BUVSs in the biosolid-amended soils of treatment 2 (T2) in Shandong.
Time
BT
5-TT
CBT
XT
UV-326 UV-327 UV-328
UV-329
UV-P
a
b
Oct 2010 6.1±0.8
7.0±1.7
< LOQ
< LOQ 4.4±0.3 5.9±0.4 14.6±2.0
33.3±7.3
8.7±1.7
Nov 2010 6.2±1.4
6.5±1.5
< LOQ
< LOQ 5.6±0.9 7.4±0.9 27.8±4.4
71.6±11.8 13.2±2.3
Dec 2010 11.0±1.6 13.4±2.8 < LOQ
< LOQ 6.6±0.7 8.8±0.9 27.5±3.1
140±28.7 21.1±2.8
Mar 2011 9.7±2.3
13.7±2.7 < LOQ
< LOQ 8.7±0.9 9.5±0.8 30.5±2.8
162±42.8 53.4±39.5
Apr 2011 9.8±1.1
10.7±1.1 < LOQ
< LOQ 8.5±0.9 9.8±1.0 29.1±3.0
308±77.0 55.4±13.0
May 2011 10.4±1.1 13.1±2.5 < LOQ
< LOQ 6.9±1.1 7.8±0.9 27.0±3.3
126±17.6 17.9±3.2
Jun 2011 8.7±2.5
8.9±2.4
< LOQ
< LOQ 5.5±1.3 7.8±1.2 26.8±4.2
120±26.5 17.8±4.0
Jul 2011
9.7±2.4
11.0±3.0 < LOQ
< LOQ 7.1±2.5 8.1±1.6 28.1±6.3
106±37.9 16.5±5.0
Aug 2011 6.1±1.1
7.8±1.8
< LOQ
< LOQ 3.7±1.1 5.0±1.1 16.8±10.4 46.2±10.4 10.1±1.8
Sep 2011 6.2±1.5
7.7±2.3
< LOQ
< LOQ 4.2±1.2 5.3±1.0 18.4±4.3
38.7±11.6 7.3±2.3
Oct 2011 5.7±3.7
6.2±4.3
< LOQ
< LOQ 3.0±1.6 4.2±2.1 13.5±8.5
26.4±16.7 5.8±2.7
a Mean (ng/g) ± standard deviation (%) (n = 4, replicate samples at the same time).
b < LOQ: below the limit of quantification; < LOD: below the limit of detection.