Search

Intermediate-volatility and semi-volatile organic compounds (I/SVOCs) are key precursors of secondary organic aerosol (SOA). However, the comprehensive characterization of I/SVOCs has long been an analytical challenge. Here, we develop a novel method of speciating and quantifying I/SVOCs using two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-ToF-MS) by constructing class-screening programs based on their characteristic fragments and mass spectrum patterns. Using this new approach, we then present a comprehensive analysis of gaseous I/SVOC emissions from heavy-duty diesel vehicles (HDDVs). Over three-thousand compounds are identified and classified into twenty-one categories. The dominant compound groups of I/SVCOs emitted by HDDVs are alkanes (including normal and branched alkanes, 37-66%), benzylic alcohols (7-20%), alkenes (3-11%), cycloalkanes (3-9%), and benzylic ketones (1-4%). Oxygenated I/SVOCs (O-I/SVOCs, e.g., benzylic alcohols and ketones) are first quantified and account for20% of the total I/SVOC mass. Advanced aftertreatment devices largely reduce the total I/SVOC emissions but increase the proportion of O-I/SVOCs. With the speciation data, we successfully map the I/SVOCs into the two-dimensional volatility basis set space, which facilitates a better estimation of SOA. As aging time goes by, approximate 45% difference between the two scenarios after seven-day aging is observed, which confirms the significant impact of speciated I/SVOC emission data on SOA prediction.

Comprehensive characterization of diesel vehicle emitted polycyclic aromatic hydrocarbon (PAH) emissions is yet to achieve due to the limitation of analytical methods. Therefore, we herein developed a two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-ToF-MS) method and quantified the total PAHs from diesel vehicles based on their characteristic fragments and mass spectral patterns. Overall, the emission factors (EFs) of total PAHs (gas + particle) are observed to range from 4.1 ± 2.5 mg km

Emissions of major reactive nitrogen compounds, including nitric oxide (NO), nitrogen dioxide (NO2) and ammonia (NH3), from heavy-duty diesel vehicles (HDDVs) place substantial pressure on air quality for many large cities in China. To control nitrogen oxide (NOX) emissions from HDDVs, selective catalytic reduction (SCR) systems have been widely used since the China IV standards. To investigate the impacts of aftertreatment technologies and driving conditions on real-world emissions of reactive nitrogen compounds, a portable emissions measurement system was employed to test eighteen heavy-duty diesel trucks in China. The results showed that the China IV and China V HDDVs with appropriate SCR functionality could reduce NOX emissions by 36% and 53%, respectively, compared to the China III results, although their real-world emissions were still higher than the corresponding emission limits for regulatory engine tests. For these HDDVs, five samples were tested with NH3 emissions, ranging from 1.67 ppm to 51.49 ppm. The NH3 emission rates tended to significantly increase under high-speed driving conditions. The results indicate that the current SCR technology may have certain risks in exceeding the future China VI NH3 limit. However, five China IV/V HDDVs were found to have SCR temperature sensors that were intentionally tampered with, resulting in comparable or even higher NOX emissions and zero NH3 emissions. Increased NO2 emissions due to the adoption of diesel oxidation catalysts and diesel particulate filters were also found from our experiments. This study highlights the importance of enhancing in-use compliance requirements and eliminating aftertreatment tampering for China IV and China V HDDVs.