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Supplementary Material:

Photolysis of pharmaceuticals and personal care products under simulated sunlight conditions: Irradiation and identification

Aasim M. Ali1, RolandKallenborn 2, Leiv K. Sydnes3, Helene Thorsen Rønning 2, Walied M. Alarif 1, Sultan S. Al‐lihaibi1

1: Department of Marine Chemistry, Faculty of Marine Sciences, King Abdulaziz University, PO. Box 80207, Jeddah 21589, Saudi Arabia

2: Faculty of Chemistry, Biotechnology and Food Sciences (KBM), Norwegian University of Life Sciences (NMBU), Christian M. Falsen veg 1, NO-1432, ÅS, Norway

3: Department of Chemistry, University of Bergen, P.O. Box 7803, N-5020 Bergen, Norway

4: Faculty of Veterinary Medicine, Norwegian University of Life Sciences (NMBU), Christian M. Falsen veg 1, NO-1432, ÅS, Norway

* Corresponding authors:

Sultan S Al‐lihaibi,email: , Tel.: +966 (012) 6952000 Ext. 64554;

Roland Kallenborn, email: . Tel.: +47 67232497

S1: Analysis

The Analytical method is completely described in an earlier study [60]. The seawater sample preparation was performed according to Batt et al [83]. The fish samples were prepared according to Klosterhaus et al. [62].

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The mass spectrometric conditions are described in table S1.

Table.S1. LC-MS/MS parameters in MRM mode, retention times, precursor ions and product ions of the analytes and internal standards

Compound / RT (min)a / Delta RT (min)a / Fragb (V) / Precursor ion (m/z) / Product ion1(m/z) / CE1c / Product ion2(m/z) / CE2c / Product ion3(m/z) / CE3c / Polarity
Ranitidine / 2.4 / 2 / 110 / 315.1 / 170 / 10 / 130 / 20 / Positive
Atrazine / 4.8 / 2 / 135 / 216.0 / 174 / 20 / 104.1 / 30 / Positive
Atenolol / 2.4 / 2 / 135 / 267.2 / 145 / 30 / 190.1 / 20 / Positive
Atenolol-d7 / 2.4 / 2 / 135 / 274 / 145 / 30 / Positive
Amitriptyline / 4.2 / 2 / 135 / 278.2 / 91 / 30 / 105 / 20 / Positive
Acetaminophen / 2.6 / 2 / 90 / 152 / 110 / 20 / 65.1 / 30 / Positive
Acetaminophen-d4 / 2.6 / 2 / 100 / 156 / 114 / 17 / Positive
Ciprofloxacin / 3.0 / 2 / 100 / 332 / 288 / 20 / 245 / 30 / Positive
Ciprofloxacin-d8 / 3.0 / 2 / 100 / 340.2 / 322 / 15 / 296 / 15 / Positive
DEET / 4.9 / 2 / 135 / 192 / 119 / 20 / 91 / 30 / Positive
Carbamazepine / 4.4 / 2 / 135 / 237 / 194 / 15 / 179 / 35 / Positive
Caffeine / 2.9 / 2 / 135 / 195 / 138 / 20 / 110 / 30 / Positive
Compound / RT (min)a / Delta RT (min)a / Fragb (V) / Precursor ion (m/z) / Product ion 1(m/z) / CE1c / Product ion 2(m/z) / CE2c / Product ion 3(m/z) / CE3c / Polarity
Chlorphenamine / 3.4 / 2 / 135 / 275 / 230 / 10 / 167 / 30 / Positive
Sulfamethoxazole / 6.8 / 2 / 135 / 254 / 156 / 10 / 108 / 20 / 92 / 30 / Positive
Trimethoprim / 2.9 / 2 / 135 / 291.5 / 261.1 / 25 / 123.2 / 25 / Positive
Metronidazole / 2.6 / 2 / 135 / 172 / 128 / 10 / 82 / 25 / Positive
Diclofenac / 5.7 / 2 / 60 / 294 / 250 / 10 / 214 / 20 / Negative
Warfarin / 5.4 / 2 / 80 / 307.2 / 161 / 15 / 250.1 / 25 / 117.1 / 30 / Negative
Methylparaben / 4.0 / 2 / 80 / 151 / 136 / 10 / 92 / 25 / Negative
DCF-226b / 4.5 / - / 135 / 226 / 180 / 20 / Positive
DCF-260 b / 2.7 / - / 135 / 260 / 214 / 20 / Positive
CBZ-180 / 1.7 / - / 135 / 180 / 152 / 20 / Positive
CMZ-253 / 3.6 / - / 135 / 253 / 180 / 30 / 236 / 30 / Positive
CBZ-271 / 3.8 / - / 135 / 271 / 253 / 30 / 236 / 30
ACE-152 / 1.0 / - / 135 / 152 / 110 / 20 / 134 / 20 / Positive

a(RT )= retention time (min). bFrag =fragmenter voltage. c (CE ) =collision energy (eV).

The transitions marked in grey are for the photolytic transformation products

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Figure.S.1. (A) Typical HPLC-QTOF chromatogram (relevant m/z range) obtained with positive ESI for DCF. (B) product ion mass spectrum of [M + H]+ for diclofenac (DCF)

Fig.S.2. (A) Typical full scan HPLC/QToF chromatogram (relevant m/z range) obtained in ESI positive-ion mode for the photolytic transformation product D-260. (B) product ion mass spectrum of [M + H]+ for D-260.

Fig.S.3. (A) Typical full scan HPLC/QToF chromatogram (relevant m/z range) obtained in ESI positive-ion mode for the photolytic transformation product D-226. (B) product ion mass spectrum of [M + H]+ for D-226.