Supplemental Information

Mass Accuracy and Isotopic Abundance Measurements for HR-MS instrumentation: Capabilities for Non-Targeted Analyses

Running title: HR-MS Mass Accuracy and Isotopic Abundance

Ann M. Knolhoff, John H. Callahan, Timothy R. Croley

U.S. Food and Drug Administration, Center for Food Safety and Applied Nutrition, HFS-707, 5100 Paint Branch Pkwy, College Park, MD 20740

Table S1. List of compounds in the standard mixture; compounds cover a mass range of m/z 127-1128, wide retention time, are composed of a variety of elements, and are from different compound classes.

Analyte / Formula / RT (min) / m/z
amoxicillin / C16H19N3O5S / 1.1 / 366.1118
ampicillin / C16H19N3O4S / 4.4 / 350.1169
androstenedione / C19H26O2 / 22.9 / 287.2006
Brodifacoum / C31H23BrO3 / 38.5 / 523.0903
Brodifacoum B / C31H23BrO3 / 39.0 / 523.0903
cephapirin / C17H17N3O6S2 / 2.1 / 424.0632
codeine / C18H21NO3 / 1.9 / 300.1594
codeine (labeled) / C18H18D3NO3 / 1.9 / 303.1783
colchicine / C22H25NO6 / 16.0 / 400.1755
dexamethasone / C22H29FO5 / 18.7 / 393.2072
Difenacoum / C31H24O3 / 36.0 / 445.1798
Difenacoum B / C31H24O3 / 36.5 / 445.1798
emetine / C29H40N2O4 / 9.4 / 481.3061
enrofloxacin / C19H22FN3O3 / 9.7 / 360.1718
ephedrine / C10H15NO / 1.5 / 166.1226
estrone / C18H22O2 / 22.4 / 271.1693
ethylparaben / C9H10O3 / 13.8 / 167.0703
Furathiocarb / C18H26N2O5S / 33.6 / 383.1635
hydrocodone / C18H21NO3 / 3.0 / 300.1594
hydrocodone (labeled) / C18H18D3NO3 / 3.0 / 303.1783
hydrocortisone / C21H30O5 / 16.5 / 363.2166
Indoxacarb / C22H17ClF3N3O7 / 33.0 / 528.0780
melamine / C3H6N6 / 0.6 / 127.0727
methylparaben / C8H8O3 / 9.1 / 153.0546
methylprednisolone / C22H30O5 / 18.4 / 375.2166
methylpseudoephedrine / C11H17NO / 1.7 / 180.1383
norephedrine / C9H13NO / 1.1 / 152.1070
norpseudoephedrine / C9H13NO / 1.2 / 152.1070
oxycodone / C18H21NO4 / 2.5 / 316.1543
oxycodone (labeled) / C18H18D3NO4 / 2.5 / 319.1732
penicillin / C16H18N2O4S / 7.1 / 335.1060
prednisolone / C21H28O5 / 16.3 / 361.2010
prednisone / C21H26O5 / 16.2 / 359.1853
progesterone / C21H30O2 / 27.9 / 315.2319
propylparaben / C10H12O3 / 17.9 / 181.0859
pseudoephedrine / C10H15NO / 1.6 / 166.1226
Pyridaben / C19H25ClN2OS / 37.7 / 365.1449
Pyridalyl / C18H14Cl4F3NO3 / 43.1 / 489.9753
ricinine / C8H8N2O2 / 1.8 / 165.0659
ricinine (labeled) / C2(13C)6H8N2O2 / 1.8 / 171.0860
sildenafil / C22H30N6O4S / 17.2 / 475.2122
solanine / C45H73NO15 / 17.2 / 868.5053
Spinetoram B / C43H69NO10 / 30.3 / 760.4994
Spinosyn A / C41H65NO10 / 27.3 / 732.4681
strychnine / C21H22N2O2 / 5.2 / 335.1754
tadalafil / C22H19N3O4 / 20.0 / 390.1448
testosterone / C19H28O2 / 22.4 / 289.2162
valinomycin (M+NH4+) / C54H90N6O18 / 49.1 / 1128.6650
vardenafil / C23H32N6O4S / 15.4 / 489.2279
yohimbine / C21H26N2O3 / 11.1 / 355.2016

Table S2. Calculated RIA error (%). The value listed is the average + standard deviation of the absolute value of the RIA error (%).

A+1
pg on column / Standards / Apple Juice / Baby Food / Yogurt / Formula
Q-Exactive, Overall: 10.46+18.05
10 / 16.47+27.58 / 23.10+40.57 / 22.09+26.89 / 19.34+23.84 / 17.10+19.69
100 / 10.38+14.48 / 13.24+20.34 / 14.18+27.24 / 12.4+16.29 / 13.39+18.82
500 / 6.24+7.71 / 7.21+8.42 / 6.84+7.19 / 7.87+9.49 / 7.25+8.61
2000 / 4.28+4.92 / 5.52+6.46 / 5.89+9.49 / 5.31+8.63 / 4.99+6.19
MaXis, Overall: 27.24+71.29
10 / 42.37+29.94 / 55.53+36.06 / 62.95+46.58 / 51.94+33.06 / 57.37+105.52
100 / 24.31+30.05 / 46.40+150.54 / 41.75+129.15 / 52.15+171.27 / 28.72+41.51
500 / 19.12+55.19 / 28.89+55.10 / 19.57+33.98 / 22.93+54.20 / 19.15+30.91
2000 / 9.99+15.71 / 15.23+32.94 / 11.84+18.49 / 10.57+14.26 / 10.82+14.80

Figure S1: Mass analyzer temperature monitored at the start time of acquisition for each data file. Room temperature (not shown) scales proportionally with mass analyzer temperature.

Figure S2: Orbitrap and Q-TOF mass accuracy measurements of the lock mass ion (without lock mass calibration applied).

Figure S3: The absolute value of the experimental mass accuracy versus monoisotopic peak intensity. Each individual data point corresponds to the calculated mass accuracy for an individual detected compound.

Figure S4: Comparison of original instrument calibration and applied lock mass calibration post-data acquisition for the yogurt sample set (Orbitrap). Each individual data point corresponds to the calculated mass accuracy for an individual detected compound. The color of the individual data points represent the amount loaded on column.

Figure S5: RIA error (%) versus monoisotopic peak intensity.