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The objective of this work was to study the possibility of identifying andquantifying atmospheric carbonate carbon (CC) by thermal-opticalanalysis. Three different temperature protocols, two modifiedNIOSH-like protocols (RT-QUARTZ-840 and RT-QUARTZ-700), and the EUSAAR_2protocol were tested on filter samples containing known amounts of CC withthe semi-continuous Sunset analyzer. Carbonate was quantified by the manualintegration of the sharp peak appeared at the maximum temperature step ofthe inert mode. High recoveries of CC were achieved by all the thermalprotocols. Using the EUSAAR_2 thermal protocol, more than 95% of CCevolved as OC during the maximum temperature step in inert atmosphere for CCamounts up to 56 μg. Using the RT-QUARTZ-840 protocol specificallydeveloped for on-line analyses, CC completely evolves as OC during themaximum temperature step in the inert node, regardless of the CCconcentration. However, the quantification of CC by the RT-QUARTZ-840protocol suitable for the semi-continuous analyzer implies a high level ofuncertainty (manual integration, residual contribution of organic carbon).Therefore, it is advisable to determine CC with an independent method (e.g.by acidic decomposition of CO32- and subsequent detection ofCO2) when other sample aliquots are available. The comparison of thepeak integration method with the direct determination of the CC samplecontent by acidic CO2 release showed that the peak integration methodprovides always higher CC concentrations of about 33%. Nevertheless, thedetermination of CC with the RT-QUARTZ-840 protocol may be considered incases where on line monitoring instruments are used and for areas where CCconcentrations are expected to be significant e.g. Southern Europeancountries. This case study suggests that users of the semi continuous Sunsetanalyzer can manually integrate the sharp peak (if present) at the maximumtemperature step of the He mode (between 128–130 and 160–165 s when using theRT-QUARTZ-840 protocol) and calculate the CC concentration though with arather high error

On the quantification of atmospheric carbonate carbon by thermal/optical analysis protocols