Environmental persistent free radicals in diesel engine exhaust particles at different altitudes and engine speeds

The occurrence of environmental persistent free radicals (EPFRs) in the environment has attracted a great deal of research attention. Although the major sources of EPFRs in the environment is diesel engine exhaust, the study on the emission characteristics of EPFRs at different working conditions is still very limited. An integrated engine system was adopted to simulate different working conditions of various altitudes and engine speeds, and to examine the emission process of a diesel engine. The results suggested that low engine speed and high altitude are generally associated with high PM₁₀ emission with more stable and ordered structures. Based on the analysis of PAHs on solid and gas phases, PM₁₀ generated from diesel engine at altitude higher than 2000 m may contain substantial amounts of PAHs embedded inside particles, but not adsorbed on the surface. EPFRs signal up to 1.66 × 10²⁰ spins/g were detected in PM₁₀ of the diesel exhaust. Higher engine speed and lower altitude were associated with stronger EPR signals on PM₁₀. However, the accumulated EPR signal intensities after consuming 1 L of diesel were higher at lower engine speed and higher altitude, suggesting higher overall risks. A positive correlation between R value (signal strength ratio of D and G peaks on the Raman spectra) and EPFRs intensity indicated that the EPR signals were associated with the defects of carbon structure. EPFRs intensity in particles showed no significant change in dark, and over 70% of the EPR signals survived under UV light in a one-month aging simulation. The strong persistence of these EPFRs suggested their potential long lasting and widespread risks, which should be investigated extensively.