1
2
3
Marina G. Pintado-Herrera
†
, Pablo A. Lara-Martín
† , Eduardo González-Mazo †
, Ian J.
Allan‡ *
4
5
6
†
Physical Chemistry Department, Faculty of Marine and Environmental Sciences,
University of Cadiz. Campus de Excelencia Internacional del Mar (CEI-MAR). Cadiz,
Spain, 11510
7
8
‡ Norwegian Institute for Water Research (NIVA), Gaustadalléen 21, NO-0349 Oslo,
Norway
9 *Corresponding author: ian.allan@niva.no
10 Summary of the Supplementary Information
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14
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27
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30
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24
25
26
S1. Information on chemicals
S2. Diffusion experiments: theory
S3. Additional information on polymer-water partition coefficient measurements
S4. Chemical analysis
S5. Methodology for the estimation of freely dissolved concentrations in the Alna River.
Supplementary Table S1. Recovery percentages for the target compounds from liquidliquid extraction.
Supplementary Table S2. LogK pw
values obtained using the co-solvent method (intercept of the linear regression of logK pw
with the fraction or the mole fraction of methanol in water, LL and MF model).
Supplementary Figure S1.1. Examples of concentration profiles across polymer sheets: measured and predicted concentration profiles for galaxolide and benzophenone 3 (BP-3) in silicone rubber.
Supplementary Figure S1.2. Correlation between logD p
and logK ow
(left) and molecular weight (MW) (right) in A) silicone rubber and B) LDPE for fragrances and PAHs (data previously reported by Rusina et al. 2010, ref. 10).
Supplementary Figure S2. Logarithm of polymer mixture water-methanol (logK pm
) as a function of the volume fraction of co-solvent (methanol). Different percentages of
1
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55
56
57
58
59
60
61
48
49
50
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52
53
44
45
46
47
40
41
42
43
36
37
38
39
31
32
33
34
35
62
63 methanol were tested (10%, 20%, 30% and 50%). Results are presented for A) nitro musks,
B) polycyclic musks, and C) some organophosphate flame compounds.
Supplementary Figure S3. Retention fraction for performance reference compounds
(PRCs) for 21 day of exposure time. The solid line represents the best model fit using the unweighted non-linear least square method (NLS) from Booij and Smedes (34).
S1. Information on chemicals
Galaxolide (HHCB) as well as triclosan d
3
(TCS-d
3
), musk xylene d
15
(MX- d
15
), methyltriclosan
13
C
12
(MTCS-
13
C
12
) were purchased from Dr Ehrenstorfer GmbH (Augsburg,
Germany). Oxybenzone (BP-3), octocrylene (OC), nonylphenol technical mixture (NP), musk xylene (MX), musk ketone (MK), triclosan (TCS), methyl triclosan (MTCS), octylphenol (OP), 2-hydroxybenzophenone (2-OHBP), homosalate (HMS), 2-ethylhexyl salicylate (EHS), 2-ethylhexyl-4-methoxycinnamate (EHMC), 4-methylbenzylidene camphor (4-MBC), and benzophenone d
10
(d
10
-BP) were purchased from Sigma-Aldrich
(Madrid, Spain). Celestolide (ADBI), tonalide (AHTN), traseolide (ATII), phantolide
(AHMI), musk tibetene (MT), musk ambrette (MA), cashmeran and irgarol were purchased from LGC Standards (Barcelona, Spain). OTNE fragrance was from Bordas Chinchurreta
Destilations (Seville, Spain). Tris-isobutylphosphate (TIBP), tris-n-butylphosphate (TBP),
2-ethylhexyldiphenylphosphate (EHDPP), triphenylphosphate (TPP), tris-2ethylhexylphosphate (TEHP), tris-o-tolylphosphate (ToTP), tris-m-tolylphosphate
(TmTP), tris-p-tolylphosphate (TpTP), tris-n-butylphosphate-d
27
(TBP-d
27
) and triphenylphosphate d
15
(TPP-d
15
) were purchased from Chiron (Trondheim, Norway).
Analytical standards for polycyclic aromatic hydrocarbons deuterated were purchased from
Chiron AS (Trondheim, Norway) and purities were >99.5 % for deuterated PAHs. Stock solutions of these analytes were prepared in acetone and stored at -20 ºC in tightly closed amber vials.
S2. Diffusion experiments: Theory
The mathematical theory of diffusion of isotropic substances is based on the hypothesis that the rate of transfer of diffusing substance through unit area is proportional to the
2
64
65
66 concentration gradient measured (Fick´s first law). According to Fick´s second law, where changes in concentration with time is taken into account:
𝜕𝐶
= D p
𝜕𝑡
𝜕
2
𝐶
𝜕𝑥 2
67
68
69
D p
is the diffusion coefficient through the polymer, C is the concentration of the compound to study, x is the distance (in our case, from the central point) and t is the time. We solved this equation using a complementary error function, erfc as described in Crank (1975).
70 𝐶(𝑥, 𝑡) =
1
2
𝐶
0 erfc 𝑥
2√𝐷𝑡
71
72
73
74
75 where C
0
is the initial contaminant concentration in the spiked polymer sheet (calculated as the sum of concentrations measured in the five sheets at the end of the experiment). At time t = 0, chemicals were however homogenously distributed in a polymer sheet of defined thickness (2h) with C = C
0
for –h < x < +h (x 0,0 is the centre of the spiked sheet).
Accordingly, the equation above can be changed to:
76 𝐶(𝑥, 𝑡) =
1
2
𝐶
0
{erf ℎ − 𝑥
2√𝐷𝑡
+ erf ℎ + 𝑥
2√𝐷𝑡
}
80
81
82
77
78
79 where erf is the Gauss error function. Since there is a no flux condition for the outer edge of the two polymer sheets on either sides of the stack (when x = L, distance between the centre of the stack and the outer edge), in such a finite system (x =
L
and ∂C/∂x = 0, a boundary condition), and the curve is reflected (Supporting Information, Fig. S1.1). A solution of this equation can be obtained by Laplace transform (Crank, 1975, section 2.2.4, equation 2.17. Ref 27):
83 𝐶 =
1
2
𝐶
0 𝑛=∞
∑ [erf ℎ + 2𝑛𝐿 − 𝑥
2√𝐷𝑡 𝑛=−∞
+ erf ℎ − 2𝑛𝐿 + 𝑥
]
2√𝐷𝑡
84
85
86
87
88
89
The time parameter t was set according to the two experimental durations of 4 or 12 hours.
In this model, LDPE and silicone rubber layers were divided into different layers with thicknesses of 0.5 and 5 µm, respectively. Because of the film stack’s impermeable boundaries, the successive terms in the equation above (with n varying from -∞ to +∞) are to account for successive reflection of the curve at the outer edges. For practical purposes, we used n = 100. The resulting profiles of concentrations C(x) across each polymer sheets
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102
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104
105
98
99
100
101
106
95
96
97
90
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92
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94 were averaged to enable comparison of the modelled profile outputs with experimentally measured concentrations. In the model system, each polymer sheet was divided into 10 model slices (50 and 9 µm for silicone rubber and LDPE, respectively) and the mean of concentrations in these 10 slices were calculated for comparison with measured concentrations. LogD p
was estimated by selecting the minimum in the sum-squared residual differences (RMSD) between measured and estimated concentrations.
S3. Additional information on polymer-water partition coefficient measurements
The spiked sheets were transferred to new bottles with an initial fraction of methanol of 50
%. The percentages of methanol tested with the co-solvent method [17] were 50 %, 30 %,
20 %, 10 % and 0 %. For the experiments with methanol volumes lower than 50 %, water was added until the appropriate volume fraction was reached. For the 100/0 (v/v) experiments (no methanol), water was added until a volume ratio of 95/5. Following this, the solvent was discarded and only ultrapure water was added to this same flask. The polymer masses, the percentage of methanol and the volume of the aqueous phase used for the polymer-water partition coefficient measurements are given below.
% methanol mass sampler (g) vol. aqueous phase (ml)
S4. Chemical analysis
50
2
80
30
0.5
80
20
0.5
80
10
0.2
800
0
0.2
1800
A derivatising agent (10 µL of N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide) was added to the final extract before analysis to enhance the MS signal and/or improve peak shape of some target compounds (i.e. triclosan).
The gas chromatography and mass spectrometry conditions were as follows: the column temperature ramp was as follows: 70 ºC for 1 min, increased at a rate of 35 ºC min
ºC, then at a rate of 4.50 ºC min -1
-1
to 180
to 290 ºC, and held for 8 min. The electron impact source, transfer line and quadrupole analyser temperatures were 250, 300 and 150 ºC, respectively.
The mass detector acquired in selected-ion-monitoring (SIM), using 70 eV as electron impact ionization (EI) energy, for the analysis of samples from laboratory experiments.
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125
126
127
128
129
130
131
118
119
120
121
Identification of target compounds and the PRCs ( d
10
-acenaphthene, d
10
-phenanthrene, d
10
fluoranthene, d
12
-chrysene, and d
12
-benzo[a]pyrene) was based on comparing retention times and two different ions one for quantification and one for confirmation with those for commercially available pure standards.
On the other hand, the analysis of field samplers were carried out by using the same ramp temperature but the mass detector operated in multiple reaction monitoring (MRM) mode.
The collision gas was argon with a pressure of 2 mTorr. MS/MS transitions and collision energies were optimized for each target compound. Their identification and quantification were based on comparing retention times and at least two transitions for each analyte (one for quantification and one for confirmation) to those for commercially available pure standards. The ion ratio between both transitions was also considered. Retention time, Q1
(precursor ion) and Q3 (product ion), collision energy and instrumental detection limits
(iLODs) are given below.
Compound Name traseolide (ATII) tonalide (AHTN) phantolide (AHMI) celestolide (ADBI)
Compound Name galaxolide (HHCB) musk tibetene (MT) musk xylene (MX) musk ketone (MK) musk ambrette (MA) cashmeran (DPMI)
Retention time
(min)
Q1 First
Mass
12.25
12.35
11.51
11.1
215
215
215
243
243
229
229
229
229
229
229
Retention time
(min)
Q1 First
Mass
12.31
13.08
12.35
13.40
12.14
9.60
243
243
266
251
251
282
282
279
279
279
253
253
191
Q3 First
Mass
213
171
251
130
159
128
118
191
203
118
106
120
119
Q3 First
Mass
173
157
131
187
159
187
145
171
173
131
57
Collision
Energy
(V)
10
20
20
10
20
10
20
20
10
20
10
Collision
Energy
(V)
15
20
30
15
20
20
20
20
10
10
40
20
40 iLOD
(μg L -1 )
0.93
0.14
0.93
0.06 iLOD
(μg L -1 )
0.094
1.5
1.2
0.46
0.04
0.5
5
OTNE irgarol methyl triclosan (MTCS) triclosan (TCS) octylphenol (OP) nonylphenol mix (NP)
2-hydroxybenzophenone(2OHBP) homosalate (HMS) octocrylene (OC)
4-methylbenzylidene camphor
(4-MBC) benzophenone-3(BP-3)
2-ethylhexyl salicylate (EHS)
10.79
14.13
14.62
16.56
13.91
13.40
14.10
15.59
18.82
14.06
16.12
14.87
2-ethylhexyl-4-methoxycinnamate
(EHMC) tris-n-butyl phosphate
(TNBP) tris (2-ethylhexyl) phosphate
(TEHP)
16.06
10.38
17.14 99
Compound Name triisobutylphosphate
(TIBP) tris-o-tolyl phosphate
(ToTP) tris-m-tolyl phosphate
(TmTP) tris-p-tolyl phosphate
(TpTP)
2 ethyl hexyl diphenyl phosphate
(EHDPP) triphenylphosphate
(TPP)
Retention time
(min)
Q1 First
Mass
9.46
18.28
18.68
19.36
16.97
16.83
99
211
165
368
368
368
368
368
368
251
251
326
325
191
191
254
254
254
285
285
285
195
195
178
178
195
195
195
248
232
254
182
253
182
302
302
200
345
345
263
263
263
235
197
197
211
155
81
Q3 First
Mass
81
99
115
181
165
242
196
154
165
77
152
168
169
109
121
239
211
105
242
241
212
159
115
132
161
177
159
115
165
176
155
109
196
125
252
188.9
170
199.9
184.8
165
91
221
121
152
150
99
81
0.34
0.04
0.02
0.004
0.03
0.57
0.37
0.02
0.06
1
0.005
0.03
0.05
0.13
0.03
Collision
Energy
(V)
30
30
40
20
30
30
40
30
30
30
30
40
20 iLOD
(μg L -1 )
0.01
0.15
0.05
0.57
0.31
0.08
20
30
40
20
30
30
20
40
10
30
20
40
30
20
30
10
10
10
20
20
30
40
30
40
40
30
40
40
30
40
20
20
10
40
30
6
145
146
147
148
141
142
143
144
149
150
136
137
138
139
140
132
133
134
135
151
152
153
154
155
156
157
158
159
325
326
231
214.9
15
30
S5. Methodology for the estimation of freely dissolved concentrations in the Alna
River.
The unweighted non-linear least square method by Booij and Smedes [34] was used to estimate sampling rates, R s
, for compounds of interest from the PRC dissipation data assuming boundary layer controlled exchange between sampler and water. This procedure allows the optimisation of a deployment-specific parameter (adjustable parameter β sil
), essentially related to the thickness of the diffusive boundary layer for that specific deployment:
𝑅 𝑠
= 𝛽 𝑠𝑖𝑙
𝐾 −0.08
𝑝𝑤
Values of logβ sil
for the replicate samplers were 0.909 and 0.939, respectively. The β sil parameter has the same units as R s
, L d
-1
and is similar to an exposure adjustment factor that corrects R s
for specific deployment conditions. Estimated sampling rates were 3.2 and
3.5 L d
-1
based on these β sil
values for substances with log K pw
of 5. Under these conditions, we can assume that all emerging contaminants of interest are sampled under boundarylayer controlled uptake. The general uptake equation below was then used to estimate freely dissolved water concentrations:
𝑤
𝑎𝑐𝑐
𝑝𝑤
𝑝
𝐾 𝑝𝑤 𝑠
𝑚 𝑝
where C w
is the time-weighted water concentration (ng L
-1
), m p
is the sampler mass (kg) and t is the exposure time (d), N acc
is the contaminant mass accumulated in the sampler
(ng), with the remaining parameters described previously. No corrections of K pw
for differences in the temperature between the laboratory experiment and the river water were applied.
Table S1. Recovery percentages for the target compounds from liquid-liquid extraction.
Compounds
Musk ketone
Fragrances
7
Recovery (%)
82
(MK)
Musk xylene
(MX)
Musk tibetene
(MT)
Musk ambrette
(MA)
Galaxolide
(HHCB)
Tonalide
(AHTN)
Celestolide
(ADBI)
Traseolide
(ATII)
70
84
72
82
77
82
81
Phantolide
(AHMI)
Cashmeran
(DPMI)
90
73
OTNE
Methyl triclosan
(MTCS)
60
Endocrine disrupting compounds
Triclosan
71
(TCS)
76
75 Irgarol
Nonylphenol
(NP)
Octylphenol
(OP)
UV-filters
2-ethylhexyl methoxycinnamate
(EHMC)
4-methylbenzylidene camphor
(4-MBC)
2-ethylhexyl salicylate
(EHS)
Homosalate
(HMS)
70
73
80
78
75
60
Benzophenone-3
(BP-3)
2-hydroxybenzophenone
(2-OHBP)
90
65
Octocrylene
(OC)
86
Organophosphate flame retardants
Tris-isobutylphosphate
70
(TIBP)
8
164
165
166
167
160
161
162
163
168
169
170
171
172
Tris-n-butylphosphate
(TBP)
2-ethylhexyldiphenylphosphate
(EHDPP)
Triphenylphosphate
(TPP)
Tris-2-ethylhexylphosphate
(TEHP)
Tris-o-tolylphosphate
(ToTP)
Tris-m-tolylphosphate
(TmTP)
Tris-p-tolylphosphate
(TpTP)
80
65
99
70
65
70
74
Table S2. Log K pw values (L kg -1 ) obtained using the co-solvent method (intercept of the linear regression of log K pw
with the volume fraction and the mole fraction of methanol in water, LL and MF model, respectively).
Compounds
Musk ketone (MK)
Musk xylene (MX)
Musk tibetene (MT)
Musk ambrette (MA)
Galaxolide(HHCB)
Tonalide (AHTN)
Celestolide (ADBI)
Traseolide (ATII)
Phantolide (AHMI)
Cashmeran (DPMI)
OTNE
Methyl triclosan (MTCS)
Triclosan (TCS)
Irgarol log K pw estimated
LL
3.16
3.47
4.16
3.92
4.12
4.05
4.06
4.43
3.89
3.56
3.76
3.81
2.98
3.72 log K pw estimated
MF
3.11
3.45
4.26
3.94
4.08
4
4.01
4.38
3.85
3.49
3.72
3.79
2.85
3.61
Compounds
TIBP
TBP
EHDP
TPP
TEHP
ToTP
TmTP
TpTP log K pw estimated
LL
4.7
5.08
5.48
4.97
5.7
5.53
5.7
5.8 log K pw estimated
MF
4.61
5.01
5.37
4.88
5.68
5.4
5.62
5.7
9
179
Nonylphenol (NP)
Octylphenol (OP)
EHMC
4-MBC
EHS
HMS
Benzophenone-3(BP-3)
2-OHBP
Octocrylene (OC)
3.68
3.24
4.75
3.57
4.83
4.74
3.01
2.97
4.96
3.65
3.2
4.9
3.53
4.78
4.7
2.96
2.9
5.15
173
174
175
176
177
178
191
192
193
187
188
189
190
180
181
182
183
184
185
186
Figure S1.1. Examples of concentration profiles across polymer sheets: measured and predicted concentration profiles for galaxolide and benzophenone-3 (BP-3) in silicone rubber.
10
194
195
196
197
198
199
200
201
Figure S1.2. Correlation between logD p
and logK ow
(left) and molecular weight (MW)
(right) in A) silicone rubber and B) LDPE for fragrances and PAHs (data previously reported by Rusina et al. 2010, ref. 11).
11
202
203
204
205
206
207
208
Figure S2. Logarithm of polymer mixture water-methanol partition coefficient
(logK pm
) as a function of the volume fraction of co-solvent (methanol). Different percentages of methanol were tested (0%, 10%, 20%, 30% and 50%). Results are presented for A) nitro musks, B) polycyclic musks, and C) some organophosphate flame compounds.
12
209
210
211
212
213
Figure S3. Retention fraction for performance reference compounds (PRCs) for 21 day exposure time. The solid line represents the best model fit using the unweighted non-linear least square method (NLS) from Booij and Smedes (34).
214
215
216
217
218
13