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There are few whole-canopy or ecosystem scale assessments of the interplay between canopy temperature and photosynthesis across both spatial and temporal scales. The stable oxygen isotope ratio (δ18O) of plant cellulose can be used to resolve a photosynthesis-weighted estimate of canopy temperature, but the method requires independent confirmation. We compare isotope-resolved canopy temperatures derived from multi-year homogenization of tree cellulose δ18O to canopy-air temperatures weighted by gross primary productivity (GPP) at multiple sites, ranging from warm temperate to boreal and subalpine forests. We also perform a sensitivity analysis for isotope-resolved canopy temperatures that showed errors in plant source water δ18O lead to the largest errors in canopy temperature estimation. The relationship between isotope-resolved canopy temperatures and GPP-weighted air temperatures was highly significant across sites (p

Nitrous acid (HONO) is important as a significant source of hydroxyl radical (OH) in the troposphere and as a potent indoor air pollutant. It is thought to be generated in both environments via heterogeneous reactions involving nitrogen dioxide (NO2). In order to enable fast-response HONO detection suitable for eddy-covariance flux measurements and to provide a direct method that avoids interferences associated with derivatization, we have developed a 2-channel tunable infrared laser differential absorption spectrometer (TILDAS) capable of simultaneous high-frequency measurements of HONO and NO2. Beams from two mid-infrared continuous-wave mode quantum cascade lasers (cw-QCLs) traverse separate 210 m paths through a multi-pass astigmatic sampling cell at reduced pressure for the direct detection of HONO (1660 cm−1) and NO2 (1604 cm−1). The resulting one-second detection limits (S/N=3) are 300 and 30 ppt (pmol/mol) for HONO and NO2, respectively. Our HONO quantification is based on revised line-strengths and peak positions for cis-HONO in the 6-micron spectral region that were derived from laboratory measurements. An essential component of ambient HONO measurements is the inlet system and we demonstrate that heated surfaces and reduced pressure minimize sampling artifacts.

In situ measurements of stratospheric sulphate aerosol, reactive nitrogen and chlorine concentrations at middle latitudes confirm the importance of aerosol surface reactions that convert active nitrogen to a less active, reservoir form. This makes mid-latitude stratospheric ozone less vulnerable to active nitrogen and more vulnerable to chlorine species. The effect of aerosol reactions on active nitrogen depends on gas phase reaction rates, so that increases in aerosol concentration following volcanic eruptions will have only a limited effect on ozone depletion at these latitudes.

The N2O content of waters in the Potomac and Merrimack Rivers was measured on a number of occasions over the period April to July 1977. The concentrations of dissolved N2O exceeded those which would apply in equilibrium with air by factors ranging from about 46 in the Potomac to 1.2 in the Merrimack. Highest concentrations of dissolved N2O were associated with sewage discharges from the vicinity of Washington, D. C., and analysis indicates a relatively high yield, 1.3 to 11%, for prompt conversion of waste nitrogen to N2O. Measurements of dissolved N2O in fresh water ponds near Boston demonstrated that aquatic systems provide both strong sources and sinks for atmospheric N2O.

Rapid loss of ozone over Antarctica in spring requires that the abundance of gaseous nitric acid be very low. Precipitation of particulate nitric acid has been assumed to occur in association with large ice crystals, requiring significant removal of H2O and temperatures well below the frost point. However, stratospheric clouds exhibit a bimodal size distribution in the Antarctic atmosphere, with most of the nitrate concentrated in particles with radii of 1 micron or greater. It is argued here that the bimodal size distribution sets the stage for efficient denitrification, with nitrate particles either falling on their own or serving as nuclei for the condensation of ice. Denitrification can therefore occur without significant dehydration, and it is unnecessary for temperatures to drop significantly below the frost point.