We report the first observations of formaldehyde (HCHO) flux measured via eddy covariance, as well as HCHO concentrations and gradients, as observed by the Madison Fiber Laser-Induced Fluorescence Instrument during the BEACHON-ROCS 2010 campaign in a rural, Ponderosa Pine forest northwest of Colorado Springs, CO. A median noon upward flux of ~80 μg m⁻² h⁻¹ (~24 ppt_v m s⁻¹) was observed with a noon range of 37 to 131 μg m⁻² h⁻¹. Enclosure experiments were performed to determine the HCHO branch (3.5 μg m^-2 h⁻¹) and soil (7.3 μg m⁻² h⁻¹) direct emission rates in the canopy. A zero-dimensional canopy box model, used to determine the apportionment of HCHO source and sink contributions to the flux, underpredicted the observed HCHO flux by a factor of 6. Simulated increases in concentrations of species similar to monoterpenes resulted in poor agreement with measurements, while simulated increases in direct HCHO emissions and/or concentrations of species similar to 2-methyl-3-buten-2-ol best improved model/measurement agreement. Given the typical diurnal variability of these BVOC emissions and direct HCHO emissions, this suggests that the source of the missing flux is a process with both a strong temperature and radiation dependence.

We present simultaneous fast, in-situ measurements of formaldehyde and glyoxal from two rural campaigns, BEARPEX 2009 and BEACHON-ROCS, both located in Pinus Ponderosa forests with emissions dominated by biogenic volatile organic compounds (VOCs). Despite considerable variability in the formaldehyde and glyoxal concentrations, the ratio of glyoxal to formaldehyde, R_GF, displayed a very regular diurnal cycle over nearly 2 weeks of measurements. The only deviations in R_GF were toward higher values and were the result of a biomass burning event during BEARPEX 2009 and very fresh anthropogenic influence during BEACHON-ROCS. Other rapid changes in glyoxal and formaldehyde concentrations have hardly any affect on R_GF and could reflect transitions between low and high NO regimes. The trend of increased R_GF from both anthropogenic reactive VOC mixtures and biomass burning compared to biogenic reactive VOC mixtures is robust due to the short timescales over which the observed changes in R_GF occurred. Satellite retrievals, which suggest higher R_GF for biogenic areas, are in contrast to our observed trends. It remains important to address this discrepancy, especially in view of the importance of satellite retrievals and in situ measurements for model comparison. In addition, we propose that R_GF represents a useful metric for biogenic or anthropogenic reactive VOC mixtures and, in combination with absolute concentrations of glyoxal and formaldehyde, furthermore represents a useful metric for the extent of anthropogenic influence on overall reactive VOC processing via NO_x. In particular, R_GF yields information about not simply the VOCs dominating reactivity in an airmass, but the VOC processing itself that is directly coupled to ozone and secondary organic aerosol production.