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31 
Figure 3: Comparison of a high-resolution EI-TOF MS with that from the ToF-ACSM. Note that the ToF-ACSM tungsten 
peaks are much stronger relative to the background than is observed in the EI-TOF. The multiple ions visible in the EI-TOF 
are measured as only single, broad, peaks in the ToF-ACSM. 
Figure 4: Left, example ToF-ACSM mass spectra for clean and recently-vented (ie, dirty) vacuum chambers, showing the 
tungsten isotope ion pattern superimposed on background peaks of different relative magnitudes. Right, width of the isobaric 
peaks as a function of mass-to-charge for the same MS. The solid circles denote the isobars containing the tungsten isotope 
peaks. These lie under the general trend in the clean case, but follow the trend in the recently-vented case. Owing to instrument 
tuning, the peaks are generally broader in the recently-vented case. 
10 
Atmos.Meas.Tech.Discuss.,doi:10.5194/amt-2016-13,2016
ManuscriptunderreviewforjournalAtmos.Meas.Tech.
Published:2March2016
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Author(s)2016.CC-BY3.0License.
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32 
Figure 5: Compensating for the mass positions of calibrant peaks by assuming interferences are present of equal magnitude 
and mass excess to the surrounding isobaric peaks. 
Figure 6: Estimated relative compensation that would need to be applied to the W
+
exact mass owing to an influencing, 
overlapping, background peak separated by 0.095 Th and of relative signal strength indicated by the x-axis. 
10 
Atmos.Meas.Tech.Discuss.,doi:10.5194/amt-2016-13,2016
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Atmos.Meas.Tech.Discuss.,doi:10.5194/amt-2016-13,2016
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Figure 10: The isobaric peaks from NO
+
(m/Q = 29.997 Th) and CH
2
O
+
(m/Q = 30.010 Th) at 30 Th have a peak separation 
of 0.34 half-widths for resolving power m/dm = 400.  
Atmos.Meas.Tech.Discuss.,doi:10.5194/amt-2016-13,2016
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shading around the black line indicates the expected precision predicted by the parameterisation of Cubison and Jimenez 
(2015). 
Atmos.Meas.Tech.Discuss.,doi:10.5194/amt-2016-13,2016
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Atmos.Meas.Tech.Discuss.,doi:10.5194/amt-2016-13,2016
Atmos.Meas.Tech.Discuss.,doi:10.5194/amt-2016-13,2016
Figure 15: Timeseries of MSA fragments CHS
+
(44.98 Th), CH
3
S
+
(47.00 Th), HSO
2
+
(64.97 Th), CH
2
SO
2
+
(77.98 Th), 
CH
3
SO
2
+
(78,99 Th) and CH
4
SO
3
+
(95.99 Th) during episode 2. 
10 
Atmos.Meas.Tech.Discuss.,doi:10.5194/amt-2016-13,2016
represents the sum of the signals from the peaks C
4
H
6
O
6
+
and C
10
H
14
O
+
Atmos.Meas.Tech.Discuss.,doi:10.5194/amt-2016-13,2016
Bottom right: Time-series of the fitted As
2
+
intensities, with the perturbed mass calibration cases shown in red and blue. The 
shading around the black line indicates the expected precision predicted by the parameterisation of Cubison and Jimenez 
(2015). 
Figure 19: Time-series (left) and regression (right) of the average mass excess and OOA fractions. Shown also the time-series 
10 
of the estimated carbon oxidation state from mass excess analysis. 
Atmos.Meas.Tech.Discuss.,doi:10.5194/amt-2016-13,2016
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