electronic supplementary material: aerosol and air quality ... · electronic supplementary...

Electronic Supplementary Material: Aerosol and Air Quality Research Uncertainty Associated with the Analysis of Secondary Organic Aerosol Compounds Formed in Smog Chambers by Gas Chromatography-Mass Spectrometry

Oscar Pindado Jiménez, Rosa Mª Pérez Pastor

1. Equations to calculate uncertainty components. Figure 1: Scheme of equations employed to calculate uncertainty.

2. Uncertainty derived from analyte concentration. 2.1. Uncertainty derived from calibration.

Table 1: Uncertainty from calibration by a linear squares regression.

2.2. Uncertainty from preparation of standard solutions. 2.2.1. Uncertainty from stock solution.

Table 2: Uncertainty of stock solution: influence of purity.

Table 3: Uncertainty of stock solution: influence of mass.

Table 4: Uncertainty of stock solution: Influence of volume (contribution of temperature).

Table 5: Uncertainty of stock solution: Influence of volume (contribution of tolerance of flask).

Table 6: Uncertainty of stock solution: Influence of volume (contribution of repeatability).

2.2.2. Uncertainty from calibration solutions.

Table 7: Uncertainty of calibration solution: Influence of dilution factor (Uncertainty of syringe).

Table 8: Uncertainty of calibration solution: Influence of dilution factor.

Table 9: Uncertainty of each calibration solution I.

Table 10: Uncertainty of each calibration solution II.

Table 11: Uncertainty of each calibration solution III.

2.3. Uncertainty derived from repeatability. Table 12: Uncertainty derived from repeatability.

3. Uncertainty derived from recovery. Table 13: Uncertainty derived from recovery.

U

1

Uncertainty Assoc

. Equations to

ciated with the An

o calculate

nalysis of Seconda

Figure 1

Electrary Organic Aeros

: Scheme of equ

ronic Supplemsol Compounds F

uations employed

mentary Matormed in Smog C

d to calculate un

erial: AerosoChambers by Gas C

Oscar Pin

certainty.

ol and Air QuChromatography-

ndado Jiménez, Ro

uality Researc-Mass Spectromet

osa Mª Pérez Past

ch try

tor



2. Uncertainty derived from analyte concentration. 2.1 Uncertainty derived from calibration.

Table 1: Uncertainty from calibration by a linear squares regression.

Compounds Conc (mg L-1) Slope Intercept s sxx p n u(conc) u(conc)r (u(conc)r)2

Adipic acid 8.678 0.358 -0.501 0.601 383.4 1 5 1.841 0.1841 3.389 x 10-2

Benzoic acid 7.392 0.166 -0.093 0.191 278.3 1 5 1.275 0.1275 1.626 x 10-2

2,3-butanedione 6.498 0.114 -0.047 0.120 214.9 1 5 1.181 0.1181 1.394 x 10-2

4-etoxyphenol 7.018 0.137 -0.144 0.172 250.7 1 5 1.394 0.1394 1.943 x 10-2

Hidroxyacetone 12.619 0.691 -1.752 1.604 507.1 1 5 2.556 0.2556 6.535 x 10-2

Glycoaldheyde 7.220 0.394 -0.419 0.533 265.4 1 5 1.625 0.1625 2.639 x 10-2

Glyoxal 7.942 0.762 -0.136 0.268 321.1 1 5 0.388 0.0388 1.503 x 10-3

Glyoxilic acid 7.798 1.973 -1.281 2.595 309.5 1 5 1.450 0.1455 2.103 x 10-2

Norpinonic acid 7.740 0.187 -0.209 0.256 304.9 1 5 1.504 0.1504 2.262 x 10-2

Malonic acid 6.845 0.078 -0.040 0.109 238.5 1 5 1.549 0.1549 2.398 x 10-2

Methyl benzoquinone 9.306 0.307 -0.049 0.712 216.0 1 5 2.591 0.2591 6.711 x 10-2

Methyl glyoxal 8.650 1.904 0.817 0.971 380.9 1 5 0.560 0.0560 3.135 x 10-3

Pinic acid 7.042 0.101 -0.062 0.077 263.7 1 5 0.851 0.0851 7.237 x 10-3

Pinonic acid 7.104 0.126 -0.079 0.110 257.0 1 5 0.975 0.0975 9.514 x 10-3

Pyruvic acid 9.036 1.088 -0.278 1.326 577.2 1 5 1.337 0.1337 1.787 x 10-2

Succinic acid 8.130 0.609 -0.780 1.010 336.5 1 5 1.825 0.1825 3.329 x 10-2



2.2. Uncertainty from preparation of standard solutions.

2.2.1. Uncertainty from stock solutions.

Table 2: Uncertainty of stock solution: influence of purity. Influence of purity

Compounds Purity u(purity) (u(purity)r)2

Adipic acid 0.995 0.005 2.525 x 10-5 Benzoic acid 0.995 0.005 2.525 x 10-5

2,3-butanedione 0.994 0.006 3.644 x 10-5

4-etoxyphenol 0.99 0.01 1.020 x 10-4

Hidroxyacetone 0.9 0.009 1.000 x 10-4

Glycoaldheyde 0.98 0.02 4.165 x 10-4

Glyoxal 0.4 0.004 1.000 x 10-4

Glyoxilic acid 0.98 0.02 4.165 x 10-4

Norpinonic acid 0.98 0.02 4.165 x 10-4

Malonic acid 0.99 0.01 1.020 x 10-4

Methyl benzoquinone 0.98 0.02 4.165 x 10-4

Methyl glyoxal 0.4 0.004 1.000 x 10-4

Pinic acid 0.98 0.02 4.165 x 10-4

Pinonic acid 0.98 0.02 4.165 x 10-4

Pyruvic acid 0.98 0.02 4.165 x 10-4

Succinic acid 0.995 0.005 2.525 x 10-5



Table 3: Uncertainty of stock solution: influence of mass. Influence of mass

Compounds Mass (mg) u(mass) (u(mass)r)2

Adipic acid 5.62 0.007 1.551 x 10-6 Benzoic acid 5.97 0.007 1.375 x 10-6

2,3-butanedione 5.26 0.007 1.771 x 10-6

4-etoxyphenol 5.78 0.007 1.467 x 10-6

Hidroxyacetone 5.16 0.007 1.840 x 10-6

Glycoaldheyde 5.95 0.007 1.384 x 10-6

Glyoxal 6.82 0.007 1.053 x 10-6

Glyoxilic acid 5.86 0.007 1.427 x 10-6

Norpinonic acid 3.37 0.007 4.315 x 10-6

Malonic acid 5.53 0.007 1.602 x 10-6

Methyl benzoquinone 5.23 0.007 1.791 x 10-6

Methyl glyoxal 5.15 0.007 1.847 x 10-6

Pinic acid 5.11 0.007 1.877 x 10-6

Pinonic acid 6.45 0.007 1.178 x 10-6

Pyruvic acid 5.43 0.007 1.662 x 10-6

Succinic acid 7.78 0.007 8.098 x 10-7



Table 4: Uncertainty of stock solution: Influence of volume (contribution of temperature). Influence of temperature

Compounds Volume (mL)

T (ºC)

∆T (ºC)

Cexp (ºC-1) (u(VT)r)2

Adipic acid 10 20 5 0.00021 2.756 x 10-7

Benzoic acid 10 20 5 0.00025 3.906 x 10-7

2,3-butanedione 10 20 5 0.00021 2.756 x 10-7

4-etoxyphenol 10 20 5 0.00140 1.225 x 10-5

Hidroxyacetone 10 20 5 0.00021 2.756 x 10-7

Glycoaldheyde 10 20 5 0.00021 2.756 x 10-7

Glyoxal 10 20 5 0.00021 2.756 x 10-7

Glyoxilic acid 10 20 5 0.00021 2.756 x 10-7

Norpinonic acid 10 20 5 0.00137 1.173 x 10-5

Malonic acid 10 20 5 0.00021 2.756 x 10-7

Methyl benzoquinone 10 20 5 0.00021 2.756 x 10-7

Methyl glyoxal 10 20 5 0.00021 2.756 x 10-7

Pinic acid 10 20 5 0.00137 1.173 x 10-5

Pinonic acid 10 20 5 0.00137 1.173 x 10-5

Pyruvic acid 10 20 5 0.00021 2.756 x 10-7

Succinic acid 10 20 5 0.00021 2.756 x 10-7



Table 5: Uncertainty of stock solution: Influence of volume (contribution of tolerance of flask). Influence of tolerance of flask


Division (mL) (u(Vflask)r)2

Adipic acid 10 0.02 1.333 x 10-6

Benzoic acid 10 0.02 1.333 x 10-6

2,3-butanedione 10 0.02 1.333 x 10-6

4-etoxyphenol 10 0.02 1.333 x 10-6

Hidroxyacetone 10 0.02 1.333 x 10-6

Glycoaldheyde 10 0.02 1.333 x 10-6

Glyoxal 10 0.02 1.333 x 10-6

Glyoxilic acid 10 0.02 1.333 x 10-6

Norpinonic acid 10 0.02 1.333 x 10-6

Malonic acid 10 0.02 1.333 x 10-6

Methyl benzoquinone 10 0.02 1.333 x 10-6

Methyl glyoxal 10 0.02 1.333 x 10-6

Pinic acid 10 0.02 1.333 x 10-6

Pinonic acid 10 0.02 1.333 x 10-6

Pyruvic acid 10 0.02 1.333 x 10-6

Succinic acid 10 0.02 1.333 x 10-6



Table 6: Uncertainty of stock solution: Influence of volume (contribution of repeatability). Influence of repeatability


m (g) s (u(Vrep)r)2

Adipic acid 10 7.918 0.0013 1.69

Benzoic acid 10 10.009 0.0018 3.24 x 10-8

2,3-butanedione 10 13.302 0.0019 3.61 x 10-8

4-etoxyphenol 10 10.009 0.0018 3.24 x 10-8

Hidroxyacetone 10 10.009 0.0018 3.24 x 10-8

Glycoaldheyde 10 10.009 0.0018 3.24 x 10-8

Glyoxal 10 10.009 0.0018 3.24 x 10-8

Glyoxilic acid 10 7.865 0.0023 5.29 x 10-8

Norpinonic acid 10 10.009 0.0018 3.24 x 10-8

Malonic acid 10 10.009 0.0018 3.24 x 10-8

Methyl benzoquinone 10 10.009 0.0018 3.24 x 10-8

Methyl glyoxal 10 7.865 0.0023 5.29 x 10-8

Pinic acid 10 7.865 0.0023 5.29 x 10-8

Pinonic acid 10 10.009 0.0018 3.24 x 10-8

Pyruvic acid 10 10.009 0.0018 3.24 x 10-8

Succinic acid 10 7.918 0.0013 1.69 x 10-8



2.2.2. Uncertainty from calibration solutions.

Table 7: Uncertainty of calibration solution: Influence of dilution factor (Uncertainty of syringe). Volume

(mL) Tolerance

(mL) u(Vtol)r srep

(mL) u(Vrep)r (u(V)r)2

1 0.01 4.08 x 10-3 4.60 x 10-4 4.60 x 10-4 1.73 x 10-5

0.5 0.005 4.08 x 10-3 1.70 x 10-4 3.40 x 10-4 1.72 x 10-5 0.25 0.0025 4.08 x 10-3 2.90 x 10-4 1.16 x 10-3 1.84 x 10-5 0.1 0.001 4.08 x 10-3 3.10 x 10-4 3.10 x 10-3 2.67 x 10-5 0.05 0.0005 4.08 x 10-3 7.00 x 10-5 1.40 x 10-3 1.90 x 10-5 0.01 0.0001 4.08 x 10-3 4.00 x 10-5 4.00 x 10-3 3.31 x 10-5

Table 8: Uncertainty of calibration solution: Influence of dilution factor. Solution (mg L-1)

Stock (mg L-1)

V0 (µL)

Vf (µL) F (u(Vf)/Vf)2 (u(V0)/V0)2 (u(F)/F)2

30 500 60 1000 0.0625 4.333 x10-5 3.394 x10-5 7.727 x10-5 20 500 40 1000 0.04 3.568 x10-5 3.394 x10-5 6.962 x10-5

10 20 500 1000 0.5 3.384 x10-5 3.394 x10-5 6.778 x10-5

5 20 250 1000 0.25 3.507 x10-5 3.394 x10-5 6.901 x10-5

1 10 100 1000 0.1 4.333 x10-5 3.394 x10-5 7.727 x10-5

0.1 10 10 1000 0.01 4.972 x10-5 3.394 x10-5 8.366 x10-5



Table 9: Uncertainty of each calibration solution I. Dissolution 30 (mg L-1) Dissolution 20 (mg L-1)

Compounds (u(stock)r)2 (u(F)r)2 (u(Ccal)r)2 (u(stock)r)2 (u(F)r)2 (u(Ccal)r)2

Adipic acid 2.842 x 10-5 7.727 x 10-5 1.057 x 10-4 2.842 x 10-5 6.962 x 10-5 9.804 x 10-5

Benzoic acid 2.836 x 10-5 7.727 x 10-5 1.056 x 10-4 2.836 x 10-5 6.962 x 10-5 9.798 x 10-5

2,3-butanedione 3.983 x 10-5 7.727 x 10-5 1.171 x 10-4 3.983 x 10-5 6.962 x 10-5 1.094 x 10-4

4-etoxyphenol 1.171 x 10-5 7.727 x 10-5 1.944 x 10-4 1.171 x 10-4 6.962 x 10-5 1.867 x 10-4

Hidroxyacetone 1.035 x 10-5 7.727 x 10-5 1.807 x 10-4 1.035 x 10-4 6.962 x 10-5 1.731 x 10-4

Glycoaldheyde 4.195 x 10-5 7.727 x 10-5 4.968 x 10-4 4.195 x 10-4 6.962 x 10-5 4.891 x 10-4

Glyoxal 1.027 x 10-5 7.727 x 10-5 1.799 x 10-4 1.027 x 10-4 6.962 x 10-5 1.723 x 10-4

Glyoxilic acid 4.195 x 10-5 7.727 x 10-5 4.968 x 10-4 4.195 x 10-4 6.962 x 10-5 4.892 x 10-4

Norpinonic acid 4.339 x 10-5 7.727 x 10-5 5.112 x 10-4 4.339 x 10-4 6.962 x 10-5 5.035 x 10-4

Malonic acid 1.053 x 10-5 7.727 x 10-5 1.825 x 10-4 1.053 x 10-4 6.962 x 10-5 1.749 x 10-4

Methyl benzoquinone 4.199 x 10-5 7.727 x 10-5 4.972 x 10-4 4.199 x 10-4 6.962 x 10-5 4.895 x 10-4

Methyl glyoxal 1.035 x 10-5 7.727 x 10-5 1.807 x 10-4 1.035 x 10-4 6.962 x 10-5 1.731 x 10-4

Pinic acid 4.314 x 10-5 7.727 x 10-5 5.087 x 10-4 4.314 x 10-4 6.962 x 10-5 5.011 x 10-4

Pinonic acid 4.307 x 10-5 7.727 x 10-5 5.080 x 10-4 4.307 x 10-4 6.962 x 10-5 5.004 x 10-4

Pyruvic acid 4.198 x 10-5 7.727 x 10-5 4.970 x 10-4 4.198 x 10-4 6.962 x 10-5 4.894 x 10-4

Succinic acid 2.768 x 10-5 7.727 x 10-5 1.049 x 10-4 2.768 x 10-5 6.962 x 10-5 9.730 x 10-5



Table 10: Uncertainty of each calibration solution II. Dissolution 10 (mg L-1) Dissolution 5 (mg L-1)








Glyoxal 1.723 x 10-4 6.778 x 10-5 2.401 x 10-4 1.723 x 10-4 6.901 x 10-5 2.413 x 10-4


Norpinonic acid 5.035 x 10-4 6.778 x 10-5 5.713 x 10-4 5.035 x 10-4 6.901 x 10-5 5.725 x 10-4










Table 11: Uncertainty of each calibration solution III. Dissolution 1 (mg L-1) Dissolution 0.1 (mg L-1)








Glyoxal 2.401 x 10-4 3.568 x 10-5 2.758 x 10-4 2.401 x 10-4 4.972 x 10-5 2.898 x 10-4


Norpinonic acid 5.713 x 10-4 3.568 x 10-5 6070 x 10-4 5.713 x 10-4 4.972 x 10-5 6.210 x 10-4










Table 12: Uncertainty derived from repeatability. Peak area

Compounds (A) (B) (C) (D) (E) (F) (G) (H) Average n s u(rep)r

Adipic acid 4.373 3.876 3.150 2.731 2.805 2.824 2.764 2.613 3.142 8 0.639 7.193 x 10-2

Benzoic acid 6.096 5.459 6.609 5.688 5.687 5.655 5.535 5.334 5.758 8 0.410 2.519 x 10-2

2,3-butanedione 2.352 2.044 2.454 2.161 2.181 2.143 2.112 2.099 2.193 8 0.139 2.236 x 10-2

4-etoxyphenol 3.437 2.928 3.689 3.062 3.101 3.089 3.053 2.956 3.164 8 0.262 2.930 x 10-2

Hidroxyacetone 12.887 12.661 12.960 11.980 13.226 11.976 13.096 11.661 12.556 8 0.597 1.681 x 10-2

Glycoaldheyde 14.353 13.913 14.558 12.892 14.557 12.968 14.446 12.403 13.761 8 0.873 2.244 x 10-2

Glyoxal 20.589 18.346 21.579 19.787 19.589 19.459 19.393 19.589 19.791 8 0.947 1.691 x 10-2

Glyoxilic acid 45.883 45.876 42.731 37.754 42.071 38.146 42.039 36.498 41.375 8 3.599 3.075 x 10-2

Norpinonic acid 1.098 0.953 0.891 0.796 0.806 0.819 0.782 0.782 0.866 8 0.111 4.548 x 10-2

Malonic acid 17.194 15.586 16.322 14.667 15.172 15.005 14.780 14.115 15.355 8 0.991 2.281 x 10-2

Methyl benzoquinone 31.102 27.863 32.439 32.751 30.205 29.814 29.722 29.666 30.445 8 1.603 1.861 x 10-2

Methyl glyoxal 4.946 4.411 5.028 4.580 4.517 4.535 40460 4.504 4.623 8 0.231 1.770 x 10-2

Pinic acid - - 0.757 0.652 0.680 0.696 0.652 0.632 0.678 6 0.045 2.336 x 10-2

Pinonic acid 4.946 4.411 5.028 4.580 4.517 4.535 4.460 4.504 4.623 8 0.231 1.770 x 10-2

Pyruvic acid 16.529 14.809 14.825 13.296 13.177 13.168 13.447 13.155 14.051 8 1.230 3.096 x 10-2

Succinic acid 27.526 23.291 27.783 23.574 23.987 23.924 23.531 22.553 24.521 8 1.982 2.862 x 10-2



Table 13: Uncertainty derived from recovery. Recovery (%)

Compounds (A) (B) (C) (D) (E) (F) (G) (H) Average n s u(rep)r

Adipic acid 69 104 79 108 65 84 83 78 84 8 15 6.432 x 10-2

Benzoic acid 63 79 59 53 53 58 39 42 56 8 13 7.961 x 10-2

2,3-butanedione 98 82 97 84 71 83 92 83 86 8 9 3.684 x 10-2

4-etoxyphenol 55 68 52 43 48 52 38 33 49 8 11 7.809 x 10-2

Hidroxyacetone 41 61 47 34 37 43 36 38 42 8 9 7.465 x 10-2

Glycoaldheyde 56 75 59 47 56 57 46 45 55 8 10 6.357 x 10-2

Glyoxal 8 8 10 13 10 12 11 11 10 8 2 5.822 x 10-2

Glyoxilic acid 91 82 93 90 92 94 84 75 88 8 7 2.664 x 10-2

Norpinonic acid 103 74 104 77 107 85 88 76 89 8 14 5.403 x 10-2

Malonic acid 58 46 55 47 51 42 29 43 46 8 9 6.921 x 10-2

Methyl benzoquinone 42 75 56 45 35 70 53 38 52 8 15 1.004 x 10-1

Methyl glyoxal 61 104 44 70 53 103 95 72 75 8 23 1.084 x 10-1

Pinic acid 148 108 150 110 104 133 130 115 125 8 18 5.136 x 10-2

Pinonic acid 108 95 104 120 94 128 141 110 112 8 16 5.152 x 10-2

Pyruvic acid 88 82 93 93 95 86 76 69 85 8 9 3.729 x 10-2

Succinic acid 102 109 92 68 94 84 71 67 86 8 16 6.588 x 10-2

electronic supplementary material: aerosol and air quality ... · electronic supplementary...

Documents