1. Figure S-3. RRT, RIA, FID examples
Figure S-3. RRT, RIA, FID examples. (a) Example of RRT calculation (α, relative retention time) and RRT difference with a reference analytical run with pure standard(s). (b) Relative Isotopic Abundance (RIA, in %; squares, grey line) and RIA error tolerance (diamonds, black curve) for Rm/z = 1x106, against [C] number in the molecule. The depicted RIA error tolerance corresponds to the maximum RIA error to establish the number of carbon, N, with a deviation of ±1. RIA error tolerance for Cn±1 is depending on [C] number and Rm/z. RIA spectra and [(M+1)/M] ratios are depicted for 2 molecules (*; boxes) at 3 different Rm/z and show that the resolution of 33S, 15N and 13C at isotope M+1 is an advantage in formulae identification. (c) Fine Isotopic Distributiuon (FID) of sulfamethoxazole ([C10H11N3O3S+H]+) at M+1 and M+2 isotopes and for 3 different Rm/z. High and especially ultra-high resolution can resolve 33S, 15N and 13C isotopes in M+1 as well as 34S, 13C15N, 18O and 13C2 isotopes and facilitate the determination of chemical compositions of unknown compounds. In the right-hand side box, atom isotopes and their abundance are depicted. Graph (d) shows measured and theoretical spectra of triclosan-sulfate, C12H7Cl3O5S, as well as the extracted ion chromatogram of triclosan-sulfate isotopic ions (M+1 to M+7) found in a plasma extract. RIA and FID have been calculated with Xcalibur® software (Thermo, USA).

2. Relative Retention Time deviation (%)
Figure S-3
IS: 31.0
Met: 24.0
RRTref = 31/24 = 1.292
Reference Sample
RRT = - 20% : [( )/1.29)]
Sample with an
unknown compound
Unk: 30.0
IS: 11.05
Unk: 10.7
RRTmeas = 11.05/10.7 = 1.033
RRTref = 31/36 = 0.861
IS: 11.07
RRTmeas = 11.07/10.7= 1.033
Met: 36.0
RRT = + 20% : [( )/0.861]
Met: RT of a known metabolite in the reference run (literature or database)
Unk: RT of an unknown metabolite
IS: RT of an internal standard for RT alignement/RRT calculation
RRTmeas : relative retention time measured with the unkown metabolite
RRTref : relative retention time of a known metabolite in the reference run
Relative Retention Time deviation (%)
RRT deviation = [RRTmeas - RRTref] / RRTref) x100
RRT = (t2-t0)/(t1-t0)
RRT = t’2/ t’1 t0 t1 t2
Time [min]
RT alignement I.
II.
(a)

3. Figure S-3 (b) RIA error tolerance for number of [C] +/- 1 at R = 10670
(b)
66.7
y = 200/x
C8H10N4O2 + H+
195
196
197 60
RIA error tol.*: < 25%
RIA : (M+1)/M
8.7% : R = 240,000
8.9% : R = 100,000
10.3% : R = 40,000
y = 1.082x
54.1 50
RIA error tolerance for number of [C] +/- 1 at R = 106
RIA according to number of [C] at R = 106
40.0
43.3 40
C29H31N7O + H+
494
495
496 30
31.4
RIA error tol.* : < 6.9%
RIA : (M+1)/M
31.8% : R = 240,000
34.4% : R = 100,000
34.4% : R = 40,000 25
20.0 20
21.6
15.4
14.1 10
10.8
8.7
10.0
5.4
6.9
5.0
3.2
4.0 10 20 30 40 50
Number of [C] in the molecule

4. Figure S-3 (c) M+1 Sulfamethoxazole Mmonoisotopic [C10H11N3O3S+H]+
254.0
255.0
256.0
m/z 50
100
Relative Abundance
Figure S-3
Sulfamethoxazole
(c)
Mmonoisotopic
[C10H11N3O3S+H]+
M+1 isotope(s)
M+2 isotope(s)
M+1
M+2
100
Rm/z =
220,000
50,000
140,000
13C
100
34S
Relative Abundance 50
Relative Abundance 50
13C15N
18O
15N
13C2
33S 2H
m/z
m/z

5. Figure S-3 (d) C12H7Cl3O5S triclosan-sulfate M M + 2
m/z
366
367
368
369
370
371
372
373
374
100
Relative Abundance
theoretical RIA and m/z
measured RIA and m/z M
M + 7
M + 1
M + 2
M + 3
M + 4
M + 5
M + 6
(d) 5 6 7 8 9 10
Time [min]
100
RT: 7.75
peak height: 3,118 x103
peak height: 385 x103
peak height: 3,037 x103
peak height: 390 x103
peak height: 1,019 x103
peak height: 132 x103
peak height: 122 x103
peak height: 14 x103
Relative Abundance
triclosan-sulfate M
M+1
M+2
M+3
M+4
M+5
M+6
M+7
C12H7Cl3O5S