Separation of brown carbon from black carbon for IMPROVE and Chemical Speciation Network PM2.5 samples.

The replacement of the Desert Research Institute (DRI) model 2001 with model 2015 thermal/optical analyzers (TOAs) results in continuity of the long-term organic carbon (OC) and elemental carbon (EC) database, and it adds optical information with no additional carbon analysis effort. The value of multiwavelength light attenuation is that light absorption due to black carbon (BC) can be separated from that of brown carbon (BrC), with subsequent attribution to known sources such as biomass burning and secondary organic aerosols. There is evidence of filter loading effects for the 25% of all samples with the highest EC concentrations based on the ratio of light attenuation to EC. Loading corrections similar to those used for the seven-wavelength aethalometer need to be investigated. On average, nonurban Interagency Monitoring of PROtected Visual Environments (IMPROVE) samples show higher BrC fractions of short-wavelength absorption than urban Chemical Speciation Network (CSN) samples, owing to greater influence from biomass burning and aged aerosols, as well as to higher primary BC contributions from engine exhaust at urban sites. Sequential samples taken during an Everglades National Park wildfire demonstrate the evolution from flaming to smoldering combustion, with the BrC fraction increasing as smoldering begins to dominate the fire event. IMPLICATIONS: The inclusion of seven wavelengths in thermal/optical carbon analysis of speciated PM2.5 (particulate matter with an aerodynamic diameter ≤2.5 µm) samples allows contributions from biomass burning and secondary organic aerosols to be estimated. This separation is useful for evaluating control strategy effectiveness, identifying exceptional events, and determining natural visibility conditions.

Filter light attenuation as a surrogate for elemental carbon.

Light attenuation (b(att)) measured from filter light transmission is compared with elemental carbon (EC) measurements for more than 180,000 collocated PM2.5 (particulate matter [PM] < or = 2.5 microm in aerodynamic diameter) and PM10 (PM < or = 10 microm in aerodynamic diameter) samples from nearly 200 U.S. locations during the past 2 decades. Although there are theoretical reasons for expecting highly variable relationships between b(att) and EC (such as the effects of "brown carbon" and iron oxides in PM2.5), reasonable correlations are found. These correlations are not a strong function of season or location (e.g., rural vs. urban). Median EC concentrations can be predicted from filter transmittance measurements to within +/- 15-30%. Although EC predicted from b(att) shows larger uncertainties (30-60%), especially at concentrations less than 0.3 microg/m3, the consistent mass absorption efficiency (sigm(att)) derived from the regression analysis demonstrates the feasibility of using b(att) as a surrogate for EC. This study demonstrates that a constant factor of 0.1 g/m2 (equivalent to the 10 m2/g sigma(att) used in the Interagency Monitoring of Protected Visual Environments chemical extinction formula) can be used to estimate EC concentrations from b(att) through a Teflon-membrane filter sample. Greater accuracy is achieved with site-specific sigma(att) derived from a period with collocated EC measurements.