Assessment of rainwater volatile organic carbon in southeastern North Carolina,USA

Extensive production of ethanol and vehicular use of this biofuel have recently been suggested as possible sources of elevated volatile organic carbon (VOC) in rain in Brazil (Campos, M.L.A.M., Nogueira, R.F.P., Dametto, P.R., Francisco, J.G., Coelho, C.H., 2007. Dissolved organic carbon in rainwater: glassware decontamination and sample preservation and volatile organic carbon. Atmos. Environ. 41, 8924–8931; Coelho, C.H., Francisco, J.G., Nogueira, R.F.P., Campos, M.L.A.M., 2008. Dissolved organic carbon in rainwater from areas heavily impacted by sugar cane burning. Atmos. Environ. 42, 7115–7121). Furthermore, these studies suggested that the global flux of rainwater dissolved organic carbon (DOC) may be underestimated since most DOC analytical methods do not measure VOC. The current study examined rain VOC in Wilmington, North Carolina USA in order to assess the importance of rain VOC in a location that does not have the unique conditions of ethanol production and usage found in Brazil. VOC was observed in one of six whole rain events analyzed in the current study. This event had an air mass back trajectory that originated over the Midwestern USA, the primary region where ethanol is produced and used as fuel. The other five storms which had no influence from the central US prior to arrival at the rain collection site had non-detectable VOC suggesting that air mass back trajectory has a dramatic impact on the VOC content of rainwater. VOC was also observed in the initial 1 mm of rain from two of these events but was not detectable in the whole event samples suggesting VOC is efficiently washed out of the atmosphere and is not rapidly resupplied in rainwater at this location. Considering the results of the previous Brazilian studies and the current study, and the likelihood of increased global production and consumption of ethanol based biofuels, it is imperative that future measurements of rainwater DOC include measurement of VOC. Monitoring changes in the VOC contribution to rain DOC will provide an assessment of the impact of increased ethanol biofuel usage on rainwater composition and allow for future refinements of global rainwater DOC flux estimates.     

Chemical characteristics of chromophoric dissolved organic matter in rainwater

Proton nuclear magnetic resonance (¹H-NMR), UV absorbance and excitation-emission matrix (EEM) fluorescence spectroscopy were used to define the chemical characteristics of chromophoric dissolved organic matter (CDOM) in whole and C₁₈ extracted rainwater. The average total recovery of fluorescence determined from the sum of extract and filtrate fractions relative to the whole was 86% suggesting that 14% of fluorescent CDOM in rainwater is comprised of very hydrophobic material that cannot be eluted from the column. Half the fluorescence of rainwater was recovered in the filtrate fraction which is important because it suggests that 50% of the chromophoric material present in precipitation is relatively hydrophilic. The average spectral slope coefficient was smaller in extracted samples (16.3 ± 9.0 μm^?1) relative to whole samples (18.9 ± 2.8 μm^?1) suggesting that the extracted material contains larger molecular weight material. Approximately one-third of the total dissolved organic carbon (DOC) in rainwater exists in the extract fraction suggesting that a large percentage of the uncharacterized DOC in rainwater can be accounted for by these hydrophobic macromolecular species. The fluorescence of extracted samples is strongly correlated with total NMR integration and is most sensitive to aromatic protons suggesting that molecules in this region are the most important in controlling the optical properties of rainwater. The lower removal efficiency of CDOM in rainwater relative to surface waters or the water-soluble fraction of aerosols during solid phase extraction (SPE) suggests that rainwater contains significantly more hydrophilic chromophoric compounds which are compositionally different than found in these other aquatic matrices.     

Seasonal variability of formaldehyde production from photolysis of rainwater dissolved organic carbon

Photochemical production of formaldehyde (HCHO) was measured in rainwater from 13 precipitation events in Wilmington, North Carolina, USA under conditions of simulated sunlight. HCHO concentrations increased in all samples irradiated with no changes observed in dark controls. HCHO photoproduction rates were strongly correlated with dissolved organic carbon (DOC) suggesting HCHO was derived from direct or indirect photolysis of rainwater DOC. The higher photoproduction rates (0.03–2.9 μM h^?1) relative to those reported for surface waters suggests that rainwater DOC is more photolabile in terms of HCHO production than surface waters. HCHO photoproduction rates were higher in growing season (1.0 ± 1.0 μM h^?1) compared to non-growing season (0.08 ± 0.05 μM h^?1) even when rates were normalized for DOC (6.8 ± 3.6 μM h^?1 mM C^?1 versus 1.8 ± 1.0 μM h^?1 mM C^?1). The higher growing season rate may be related to seasonal differences in the composition of DOC as evidenced by differences in fluorescence per unit carbon of rainwater samples. Irradiation of C18 extracts of rainwater also produced HCHO, but at lower rates compared to corresponding whole rain samples, suggesting that hydrophyllic components of rainwater play a role in HCHO photoproduction. Our results indicate that photolysis of rainwater DOC produces significant amounts of HCHO, and possibly other low molecular weight organic compounds, likely increasing its reactivity and bioavailability.