Supporting Information for:
Uptake of perfluoroalkyl acids in the leaves of coniferous
and deciduous broad-leaved trees
HUANHUAN ZHANG, WEI LIU, * XIN HE, YU WANG, QIAN
ZHANG
Key Laboratory of Industrial Ecology and Environmental Engineering, MOE, School of
Environmental Science and Technology, Dalian University of Technology, Dalian, China
Contents:
Sampling and pretreatment of air and soil samples
Table S1: Target analytes and optimized parameters for PFAAs analysis using
LC/MS/MS.
Table S2: Limits of detection (LOD) and limits of quantification (LOQ) for the
optimized analytical method of PFAAs in leaves.
Table S3: Recoveries of leaf PFAAs using acid and alkaline digestion methods.
Table S4: Recoveries of leaf PFAAs using different extraction solvents.
Table S5: Comparison of PFAAs concentrations in leaves in different seasons.
Table S6: Site-specific leaf soil bioaccumulation factors (LSAF) of PFAAs
Figure S1: PFSAs profile in various leaves collected on May 5th, 2013, at Dalian.
Figure S2: Relationship between LSAF and chain-length of PFCAs.
1
Experimental Section:
Sampling and pretreatment of air and soil samples
Air sampling was performed using a high-volume sampling device (HV-1000V, Sibata,
Japan) with a glass fiber filter (Advantec QR-100, 8*10 IN., Japan). Sampling times
of approximately 24 h resulted in air volumes of about 1300 m3. Soil was sampled in
campus (randomly selected six sites) using shovel digging holes vertically, and stored
and transported in polyethylene plastic bags
Samples were extracted using the following method. Briefly, 5 g of soil (for air
samples, half of glass fiber film) was weighed into a 50 mL PP tube, and vortexed
with 2 mL of cleaned PFCs-free water. Two millilitre of 0.25 M Na2CO3 and one litre
of 0.5 M TBAHS solutions were then added and vortex mixed before duplicate
extraction with MTBE. The combined MTBE extracts were brought to dryness under
a gentle stream of high purity nitrogen, and reconstituted in a 2 mL 40% methanol
aqueous.
2
Table S1 Target analytes and optimized parameters for PFAAs analysis using
LC/MS/MS
Quantitation
Qualification
Delta
Collision
Transition(m/z)
Transition(m/z)
EMV(-)
Energy a
Analyte
a
MPFOA
417>372
417>172
600
4(16)
MPFOS
503>99
503>80
600
48(72)
PFBA
213>169
213>93
600
3(15)
PFPeA
263>219
263>113
600
5(15)
PFHxA
313>269
313>119
600
3(15)
PFHpA
363>319
363>169
600
5(10)
PFOA
413>369
413>168.9
600
4(16)
PFNA
463>419
463>219
600
5(10)
PFDA
513>469
513>269
600
5(15)
PFUdA
563>519
563>269
600
5(20)
PFDoA
613>569
613>169
600
4(24)
PFTrDA
663>619
663>169
600
5(25)
PFBS
299>99
299>80
600
30(40)
PFHxS
399>99
399>80
600
40(48)
PFOS
499>99
499>80
600
48(72)
PFDS
599>99
599>80
600
60(80)
Collision Energy are for Quantitation Transition (Qualification Transition)
3
Table S2. Limits of detection (LOD) and limits of quantification (LOQ) for the optimized analytical method of PFAAs in leaves (ng/g dw, n=7)
S4
S6
S8
S10
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
PFBS
PFHxS
PFOS
PFDS
PFBA
PFPeA
PFHxA
PFHpA
PFOA
PFNA
PFDA
PFUdA
PFDoA
PFTrDA
LOD
0.43
1.43
0.5
0.61
0.5
0.58
0.64
0.36
0.67
0.04
0.03
0.04
0.02
0.05
LOQ
1.28
4.29
1.5
1.84
1.44
1.75
1.94
1.09
2.00
0.13
0.08
0.12
0.07
0.16
LOD and LOQ were determined by calculating 3×, 10× the standard deviation of the method blanks concentration.
4
Table S3 Recoveries of leaf PFAAs using acid and alkaline digestion methods (%,
n=3)
Pine needle
Plane-tree
Analytes
HCl (1 M)
NaOH (0.5 M)
HCl (1 M)
NaOH (0.5 M)
MPFOA
90±7
108±7
110±9
92±5
MPFOS
120±9
115±9
116±5
109±7
PFBS
70±9
75±5
60±8
66±8
PFHxS
75±10
55±8
59±10
63±5
PFOS
103±1
69±1
110±6
90±7
PFDS
150±7
87±10
120±8
110±8
PFBA
26±7
54±5
59±10
54±5
PFPeA
77±7
79±6
69±7
75±3
PFHxA
60±8
65±6
56±4
79±7
PFHpA
61±10
69±10
78±10
70±6
PFOA
140±10
80±10
45±11
55±8
PFNA
60±11
73±5
55±10
77±7
PFDA
72±8
73±8
125±8
75±8
PFUdA
96±8
101±7
140±6
106±5
PFDoA
140±10
95±10
119±8
125±9
PFTrDA
154±15
115±7
120±10
110±5
Recovery was determined by extraction from quality control leaf samples spiked with 8 ng/g
standards.
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Table S4 Recoveries of leaf PFAAs using different extraction solvents (%, n=3)a
MeOH
MeOH/Acetone
(v:v=1:1)
Acetonitrile
MTBE
ion-pairing
MPFOA
108±7(92±5)b
115±10(105±7)
120±9(110±3)
90±12(80±4)
MPFOS
115±9(109±7)
88±9(70±3)
115±11(89±5)
88±10(95±5)
PFBS
75±5(66±8)
131±3(115±6)
127±15(125±10)
180±5(130±9)
PFHxS
55±8(63±5)
54±7(70±9)
52±5(55±8)
60±5(63±9)
PFOS
69±1(90±7)
110±10(103±8)
200±13(126±5)
188±13(136±5)
PFDS
87±10(110±8)
160±3(140±9)
162±6(145±5)
160±2(139±6)
PFBA
54±5(54±5)
37±8(49±10)
200±8(168±5)
26±8(64±7)
PFPeA
79±6(75±3)
66±9(69±7)
100±9(79±2)
55±10(86±1)
PFHxA
65±6(79±7)
150±8(125±2)
72±10(88±4)
140±11(126±5)
PFHpA
69±10(70±6)
89±12(92±3)
24±4(35±7)
117±10(130±8)
PFOA
80±10(55±8)
103±11(82±3)
160±10(136±5)
158±9(126±5)
PFNA
73±5(77±7)
97±5(105±9)
196±18(153±6)
160±4(150±7)
PFDA
73±8(75±8)
136±4(120±7)
180±9(137±2)
160±2(157±2)
PFUdA
101±7(106±5)
120±3(108±1)
180±13(160±6)
170±2(136±5)
PFDoA
95±10(125±9)
169±2(153±3)
150±7(136±5)
200±2(138±3)
PFTrDA
115±7(110±5)
196±3(149±7)
200±13(162±5)
180±2(150±7)
a
Recovery was determined by extraction from quality control leaf samples spiked with 8 ng/g
standards.
b
Pine needles and plane-tree were analyzed, respectively, and the results for plane-tree were in
parentheses.
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Table S5 Comparison of PFAAs concentrations in leaves in different seasons.
pine
Chi-Square 5.600
df
2
Asymp. Sig. 0.061
cypress
poplar
sophora
willow
plane
7.261
2
0.027
5.535
2
0.063
4.904
2
0.086
5.804
2
0.055
6.252
2
0.044
a Kruskal Wallis Test
b Grouping Variable: seasons
Table S6 Site-specific leaf soil bioaccumulation factors (LSAF) of PFAAs
C4
C5
C6
C8
C9
C12
C13
S4
S8
needles
12a
16
4.5
0.9
2
2
0.13
17
14
Cypress
0.53
0.53
0.64
0.9
0.8
0.75
11
0.59
1.4
Ginkgo
0.34
0.21
1.3
0.62
2
2
26
0.12
0.35
Poplar
0.31
0.28
0.29
0.89
0.075
0.06
16
0.038
0.13
Willow
0.31
0.34
1.3
1
0.15
0.1
0.5
0.038
0.11
Sophora
0.24
0.21
0.67
1
0.15
0.15
1
0.038
0.054
Plane-tree
0.2
0.21
0.71
1
0.3
0.1
0.75
0.038
0.053
a
b
LSAF = PFAAs in leaves (ng/g) / PFAAs in soil (ng/g).
The leaf and soil samples were collected on May 5th, 2013, at Dalian.
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PFSAs Concentrations (ng/g dw)
40
PFDS(S10)
35
PFOS(S8)
30
PFHxS(S6)
25
PFBS(S4)
20
15
10
5
0
Figure S1. PFSAs profile in various leaves collected on May 5th, 2013, at Dalian.
8
60
LSAF
50
GSAF(Yoo, 2011)
LSAF(Shan, 2014)
AF
40
30
20
10
0
2
3
4
5
6
7
8
9
10
11
12
13
Carbon chain length
Figure S2. Relationship between LSAF and chain-length of PFCAs in pine needles.
AF= accumulation factors
LSAF= Leaf/Soil - accumulation factors using pine needles
LSAF(Shan)= Leaf/Soil - accumulation factors by Shan et al using camphor.
GASF= Grass/Soil - accumulation factors by Yoo et al.
References:
Shan GQ, Wei MC, Zhu LY et al. 2014. Concentration profiles and spatial of perfluroalkyl substances
in an industrial center with condensed fluorochemical facilities. Sci Total Environ 490: 351-359.
Yoo H, Washington J W, Thomas M et al. 2011. Quantitative determination of perfluorochemicals and
fluorotelomer alcohols in plants from biosolid-amended fields using LC/MS/MS and GC/MS. Environ
Sci Technol 45: 7985-7990.
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