Supplementary Information

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1

Supplementary Information

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

19

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21

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27

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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

54

55

56

57

58

59

60

61

48

49

50

51

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

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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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117

102

103

104

105

98

99

100

101

106

95

96

97

90

91

92

93

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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123

124

125

126

127

128

129

130

131

118

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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:

𝐶

𝑤

=

𝑁

𝑎𝑐𝑐

𝐾

𝑝𝑤

𝑚

𝑝

(1 − 𝑒

−𝑅

𝐾 𝑝𝑤 𝑠

𝑡

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

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