Table SI1: Target compounds, molecular formula, and relevant physicochemical properties

Target Compound / CAS Nº / Molecular formula / Mm
(g mol-1) / Water solubility (mg L-1) / pKa / logP / Pv (mmHg) / Ctt. Henry
(atm m3 mol-1)
CAP / Capecitabine / 154361-50-9 / C15H22FN3O6 / 359.3 / 26 / 1.9 / 0.56 / 1.12·10-12 / 2.9·10-19
CHL / Chlorambucil / 305-03-3 / C14H19NO2Cl2 / 304.2 / 1.24·104 / 5.75 / 1.7 / 9.3·10-7 / 2.71E-10
CYC / Cyclophosphamide / 6055-19-2 / C7H15Cl2N2O2P / 261.1 / 40 / - / 0.76 / 1.15·10-4 / -
CYP / Cyproterone / 427-51-0 / C22H27ClO3 / 374.5 / 6.65 / 17.61 / 3.37 / 3.18·10-9 / 2.688·10-9
DAU / Daunorubicin / 23541-50-6 / C27H29NO10 / 527.5 / 39.2 / 11.02 / 0.766 / 6.13·10-25 / 2.1·10-13
DOX / Doxorubicin / 25316-40-9 / C27H29NO11 / 543.5 / 10 / 11.02 / 1.27 / 9.64·10-28 / 2.23·10-23
EPI / Epirubicin / 56390-09-01 / C27H29NO11 / 543.5 / 1.18 / 11.02 / 1.41 / 9.64·10-28 / -
ERL / Erlotinib / 183319-69-9 / C22H23N3O4 / 393.4 / 810 / 3.37 / 2.79 / 2.69·10-12 / 2.61·10-12
FLU / Fludarabine / 21679-14-1 / C10H12FN5O4 / 285.2 / 3530 / 6.26 / -1.18 / 3.7·10-15 / 1.3·10-22
GEM / Gemcitabine / 122111-03-9 / C9H11F2N3O4 / 263.1 / 5.13·104 / 3.6 / -1.4 / 2.41·10-11 / 1.7·10-17
GOS / Goserelin / 145781-92-6 / C59H84N18O14 / 1269.4 / 20 / 6.2 / - / - / -
IFO / Ifosfamide / 3778-73-2 / C7H15Cl2N2O2P / 261.1 / 3780 / 4.75 / 0.86 / 2.98·10-5 / 1.36·10-11
IRI / Irinotecan / 100286-90-6 / C33H38N4O6 / 586.6 / 107 / 3.2 / 1.31·10-32 / -
LEU / Leuprolide / 74381-53-6 / C59H84N16O12 / 1209.4 / - / 9.6 / - / - / -
MEG / Megestrol / 595-33-5 / C22H30O3 / 342.4 / 2 / 17.61 / 4 / 4.37·10-9 / 1.23·10-9
MEL / Melphalan / 148-82-3 / C13H18Cl2N2O2 / 305.2 / 45.7 / -0.432 / -0.52 / 3·10-10 / 4.2·10-13
MPA / Mycophenolic acid / 24280-93-1 / C17H20O6 / 320.3 / 22 / 3.57 / 2.8-4.2 / 1.59·10-10 / 3.04·10-12
PRE / Prednisone / 53-03-2 / C21H26O5 / 358.4 / 312 / 13.9 / 1.46 / 5.09·10-13 / 2.83·10-10
TAM / Tamoxifen / 10540-29-1 / C26H29NO / 371.5 / 0.167 / 5.31 / 6.3 / 3.46·10-8 / 4.49·10-10

SI2. LC-Orbitrap-MS analysis

The gradient started at 95% A and 5% B, increased to 70% B in 30 min, then increased to 100% A in 1 min, and then held for 10 min. Initial conditions were attained in 4 min and the system was stabilized for 5 min. The flow was 200 µL min-1 and 5 µL were injected. Cytostatics were measured under positive electrospray ionization (ESI+). Full scan acquisition was performed over a mass range of 50-900 Da at 50,000 full width at half maximum (FWHM), with the spray voltage at 3.5 kV, capillary voltage at 30 V, skimmer voltage at 28 V, and tube lens voltage at 130 V. All these conditions were chosen on the basis of a previous optimization study (Gómez-Canela et al. 2013).

SI3. Quality parameters LC-Orbitrap-MS

Target compounds / Rt
(min) / Linearity
(ng/µL) / R² / IDL
(ng) / Intra-day
precision
(ng/µL) / Inter-day
precision
(ng/µL) / %R±SD Milli-Q water / %R±SD
river water / MDL
(ng/L)
Gemcitabine / 2.75 / 0,001-0,5 / 0.994 / 0.025 / 13.2 / 9.3 / 60±6 / 29±18 / 8.4
Fludarabine / 6.58 / 0,05-0,5 / 0.995 / 0.025 / 7.4 / 11.1 / 66±8 / 68±6 / 10.6
Goserelin / 14.10 / 0,02-1 / 0.996 / 0.1 / 31.7 / 29.3 / 79±3 / 77±1 / 3.4
Leuprolide / 14.11 / 0,02-1 / 0.995 / 0.1 / 21.1 / 36.4 / 79±1 / 79±1 / 2.4
Irinotecan / 14.42 / 0,001-0.7 / 0.993 / 0.005 / 5.9 / 38.1 / 60±21 / 33±0 / 0.7
Doxorubicin / 15.30 / 0,001-1 / 0.995 / 0.05 / 10.3 / 35.0 / 76±26 / 48±9 / 1.1
Cyclophosphamide / 15.54 / 0,001-1 / 0.999 / 0.005 / 6.4 / 30.1 / 110±4 / 111±7 / 0.7
Epirubicin / 15.79 / 0,001-1 / 0.991 / 0.005 / 17.5 / 33.3 / 68±15 / 75±8 / 2.1
Ifosfamide / 16.26 / 0,001-1 / 0.993 / 0.005 / 3.9 / 31.6 / 99±9 / 65±9 / 0.8
Melphalan / 16.35 / 0,001-1 / 0.996 / 0.005 / 4.9 / 24.1 / 95±2 / 43±4 / 1.9
Daunorubicin / 17.14 / 0,01-1 / 0.995 / 0.1 / 4.1 / 33.5 / 72±12 / 62±8 / 3.4
Erlotinib / 17.16 / 0,001-1 / 0.993 / 0.005 / 1.3 / 24.4 / 56±6 / 81±3 / 0.3
Capecitabine / 17.67 / 0,001-1 / 0.995 / 0.025 / 9.6 / 29.1 / 48±22 / 96±50 / 2.9
Prednisone / 17.84 / 0,001-1 / 0.996 / 0.005 / 3.3 / 26.0 / 62±11 / 73±6 / 1.8
Mycophenolic acid / 23.69 / 0,001-1 / 0.997 / 0.005 / 6.7 / 21.8 / 114±3 / 69±19 / 1.4
Tamoxifen / 25.03 / 0,001-2 / 0.997 / 0.005 / 4.7 / 29.2 / 71±22 / 44±16 / 0.2
Chlorambucil / 29.48 / 0,001-1 / 0.994 / 0.005 / 3.3 / 20.2 / 82±16 / 50±15 / 0.5
Cyproterone / 31.04 / 0,001-1 / 0.997 / 0.025 / 2.5 / 19.3 / 86±3 / 72±22 / 1.8
Megestrol / 31.27 / 0,001-1 / 0.999 / 0.005 / 0.01 / 15.4 / 80±3 / 66±15 / 1.0
IDL, instrumental detection limit; MDL, method detection limit

SI3. . Concentrations (ng L-1) of the 7 cytostatic drugs detected in the Besòs River and its tributaries on May (M) and July (J) 2014. No acc.= no accessible

IFO / CYC / ERL / MPA / TAM / CHL / MEG
M1 / M
J
M2 / M / 16.0
J / lod / lod / 3.9 / 18.1 / 25.1 / 4.1
M3 / M / 8.1
J / lod / 5.0 / 4.8 / 6.0
Co1 / M / lod / lod
J / lod / lod / 8.6 / 14.3 / 2.5 / lod
Co2 / M
J / lod
Co3 / M / lod
J / lod / lod
B1 / M / 0.5
J
T1 / M / 0.9
J
T2 / M
J
B2 / M / 13.1
J / lod / lod / 1.4 / 1.7
Ca1 / M
J
Ca2 / M / 10.0
J / lod / 13.7 / 2.3 / 4.4
B3 / M / 89.5
no acc.
R1 / M
J / lod / 1.4 / 2.0
R2 / M / 8.4 / 15.9
J / 13.9 / 5.5
R3 / M
J / 10.1 / 6.9
B4 / M / 7.8 / 84.0
J / lod / lod / 171.3 / 1.9
B5 / M / 84.9
J / 5.2 / 656.2 / lod
B6 / M / 46.4
J / lod / lod / lod

Gómez-Canela C, Cortés-Francisco N, Ventura F, Caixach J, Lacorte S (2013) Liquid chromatography coupled to tandem mass spectrometry and high resolution mass spectrometry as analytical tools to characterize multi-class cytostatic compounds J Chromatogr A 1276:78-94