Robert E. Stickel

Eddy covariance fluxes of peroxyacetyl nitrates (PANs) and NOy to a coniferous forest

up to approximately � 14 ng N m � 2 s � 1 . The average daytime flux peaked at � 6.0 ng N m � 2 s � 1 and accounted for � 20% of the daytime NOy flux. Calculations suggest minimum daytime surface resistances for PAN in the range of 70–130 s m � 1 .I t was estimated that approximately half of daytime uptake was through plant stomates. Average PAN deposition velocities, Vd(PAN), showed a daytime maximum of � 10.0 mm s � 1 ; however, deposition did not cease during nighttime periods. Vd(PAN) was highly variable at night and increased when canopy elements were wet from either precipitation or dew formation. Diel patterns of deposition velocity of MPAN and PPN were similar to that of PAN. These results suggest that deposition of PAN, at least to coniferous forest canopies, is much faster than predicted with current deposition algorithms. Although deposition of PAN is unlikely to compete with thermal dissociation during warm summer periods, it will likely play an important role in removing PAN from the atmosphere in colder regions or during winter. The fate of PAN at the surface and within the plants remains unknown, but may present a previously ignored source of nitrogen to ecosystems.

Evidence of Reactive Aromatics As a Major Source of Peroxy Acetyl Nitrate over China

We analyze the observations of near-surface peroxy acetyl nitrate (PAN) and its precursors in Beijing, China in August of 2007. The levels of PAN are remarkably high (up to 14 ppbv), surpassing those measured over other urban regions in recent years. Analyses employing a 1-D version of a chemical transport model (Regional chEmical and trAnsport Model, REAM) indicate that aromatic non-methane hydrocarbons (NMHCs) are the dominant (55-75%) PAN source. The major oxidation product of aromatics that produces acetyl peroxy radicals is methylglyoxal (MGLY). PAN and O(3) in the observations are correlated at daytime; aromatic NMHCs appear to play an important role in O(3) photochemistry. Previous NMHC measurements indicate the presence of reactive aromatics at high levels over broad polluted regions of China. Aromatics are often ignored in global and (to a lesser degree) regional 3D photochemical transport models; their emissions over China as well as photochemistry are quite uncertain. Our findings suggest that critical assessments of aromatics emissions and chemistry (such as the yields of MGLY) are necessary to understand and assess ozone photochemistry and regional pollution export in China.

Atmospheric ammonia measurement using a VUV/photo-fragmentation laser-induced fluorescence technique

Vacuum ultraviolet/photofragmentation laser-induced fluorescence has been demonstrated to be a highly specific and sensitive method for the quantitative measurement of atmospheric ammonia (NH(3)). The fluorescence detected in this approach results from the two 193-nm photon photofragmentation step NH(3)?NH(2)? NH(b(1)Sigma(+)) followed by the excitation of the NH(b(1)Sigma(+)) NH(c(1)Pi) transition via a 450-nm photon with final emission being observed from the NH(c(1) Pi) NH(a(1)Delta) transition at 325 nm. Limits of detection for the instrumentpresented here are < 10 pptv and < 4 pptv for 1- and 5-min integration periods, respectively, in ambient sampling conditions. The technique is free from interferences and system performance does not significantly degrade in adverse sampling conditions (i.e., rain, fog, clouds, haze, etc.). Spectroscopic selectivity in the NH(b(1)Sigma(+))?NH(c(1)Pi) transition is sufficient to resolve (15)NH(3) and (14)NH(3) contributions for use in atmospheric tracer studies. Average ammonia measurements at Stone Mountain, GA, ranged from approximately 110 pptv for air temperatures <5 degrees C to approximately 240 pptv for air temperatures >/=<5 degrees C over the period from Dec. 1987 to the end of Apr. 1988.

Evidence of Aerosols as a Media for Rapid Daytime HONO Production over China

Current knowledge of daytime HONO sources remains incomplete. A large missing daytime HONO source has been found in many places around the world, including polluted regions in China. Conventional understanding and recent studies attributed this missing source mainly to ground surface processes or gas-phase chemistry, while assuming aerosols to be an insignificant media for HONO production. We analyze in situ observations of HONO and its precursors at an urban site in Beijing, China, and report an apparent dependence of the missing HONO source strength on aerosol surface area and solar ultraviolet radiation. Based on extensive correlation analysis and process-modeling, we propose that the rapid daytime HONO production in Beijing can be explained by enhanced hydrolytic disproportionation of NO2 on aqueous aerosol surfaces due to catalysis by dicarboxylic acid anions. The combination of high abundance of NO2, aromatic hydrocarbons, and aerosols over broad regions in China likely leads to elevated HONO levels, rapid OH production, and enhanced oxidizing capacity on a regional basis. Our findings call for attention to aerosols as a media for daytime heterogeneous HONO production in polluted regions like Beijing. This study also highlights the complex and uncertain heterogeneous chemistry in China, which merits future efforts of reconciling regional modeling and laboratory experiments, in order to understand and mitigate the regional particulate and O3 pollutions over China.

Influence of Ohio River valley emissions on fine particle sulfate measured from aircraft over large regions of the eastern United States and Canada during INTEX-NA

Aircraft measurements of fine inorganic aerosol composition were made with a particle-into-liquid sampler coupled to dual ion chromatographs (PILS-IC) as part of the NASA INTEX-NA study. The sampling campaign, which lasted from 1 July to 14 August 2004, centered over the eastern United States and Canada and showed that sulfate was the dominant inorganic species measured. The highest sulfate concentrations were observed at altitudes below 2 km, and back trajectory analyses showed a distinct difference between air masses that had or had not intercepted the Ohio River valley (ORV) region. Air masses encountered below 2 km with a history over the ORV had sulfate concentrations that were higher by a factor of 3.2 and total sulfur (S) concentrations higher by 2.5. The studys highest sulfate concentrations were found in these air masses. The sulfur of the ORV air masses was also more processed with a mean sulfate to total sulfur molar ratio of 0.5 compared to 0.3 in non-ORV measurements. Results from a second, independent trajectory model agreed well with those from the primary analysis. These ORV-influenced air masses were encountered on multiple days and were widely spread across the eastern United States and western Atlantic region.

Mechanistic and kinetic study of formaldehyde production in the atmospheric oxidation of dimethyl sulfide

Tunable diode laser spectroscopic detection of formaldehyde (H 2 CO) and HCl coupled with laser flash photolysis of Cl 2 CO–CH 3 SCH 3 –O 2 –N 2 mixtures, in both the presence and absence of NO, has been utilized to conduct a mechanistic and kinetic investigation of the atmospheric oxidation of the CH 3 SCH 2 radical, a product of dimethyl sulfide (DMS, CH 3 SCH 3 ) reactions with OH and NO 3 in the atmosphere. The temperature dependence of the CH 3 SCH 2 O 2 + NO rate coefficient (k 2 ) and the 298 K rate coefficient for the CH 3 SCH 2 O 2 self reaction (k 4 ) have been measured. The Arrhenius expression k 2 = 4.9 × 10 −12 exp(263/T) cm 3 molecule −1 s −1 adequately summarizes our CH 3 SCH 2 O 2 + NO kinetic data over the temperature range 261–400 K. Contributions from side reactions, which are not completely quantifiable, limit the accuracy of the k 4 (298 K) determination; our results indicate that the true value for this rate coefficient is within the range (1.2 ± 0.5) × 10 −11 cm 3 molecule −1 s −1 . In both reactions CH 3 SCH 2 O 2 is converted to H 2 CO with unit yield (at T = 298 K). Our results demonstrate that the lifetime of CH 3 SCH 2 O, a proposed precursor to H 2 CO, is less than 30 µs at 261 K and 10 Torr total pressure.

Quantum yield for carbon monoxide production in the 248 nm photodissociation of carbonyl sulfide (OCS)

Tunable diode laser absorption spectroscopy has been coupled with excimer laser flash photolysis to measure the quantum yield for CO production from 248 nm photodissociation of carbonyl sulfide (OCS) relative to the well known quantum yield for CO production from 248 nm photolysis of phosgene (Cl{sub 2}CO). The temporal resolution of the experiments was sufficient to distinguish CO formed directly by photodissociation from that formed by subsequent S({sup 3}P{sub j}) reaction with OCS. Under the experimental conditions employed, CO formation via the fast S({sup 1}D{sub 2})+OCS reaction was minimal. Measurements at 297K and total pressures from 4 to 100 Torr N{sub 2}+N{sub 2}O show the CO yield to be greater than 0.95 and most likely unity. This result suggests that the contribution of OCS as a precursor to the lower stratospheric sulfate aerosol layer is somewhat larger than previously thought. 25 refs., 1 fig., 2 tabs.

Narrow-linewidth, tunable ultraviolet, Ti:sapphire laser for environmental sensing

We describe a compact, narrow-linewidth, etalon-tuned titanium:sapphire laser cavity that is designed for field environmental sensing and is pumped by the second harmonic of a kilohertz Nd:YAG laser. The fundamental tunable range is from 690 to 1100 nm, depending on mirror reflectivities and the optics kit used. The conversion efficiency is at least 25% for the fundamental and 2-3% for intracavity frequency doubling from 3.5 to 4 W 532 nm pump power. The linewidth is <0.1 cm(-1), and the pulse width is 18 ns. Applications of this cavity include the measurement of trace gas species by laser-induced fluorescence, cavity ringdown spectroscopy, and micropulse lidar in the UV-visible regions.

Laboratory studies of atmospheric sulfur chemistry using tunable diode laser probes

Tunable lead-salt diode laser absorption spectroscopy (TDLAS) provides a sensitive and versatile probe for the study of the kinetics and mechanisms of atmospheric reactions. In our laboratory, the combination of laser flash photolysis with TDLAS detection of reactant and/or product species has proven useful in several studies of the gas phase oxidation of the atmospheric sulfur compound dimethylsulfide, a process which may play an important role in global climate modification/regulation. Typically a radical species is produced by UV laser photolysis of a stable precursor in a slowly flowing mixture of reactant and buffer gases. The concentration of this radical or a selected reaction product is then followed by TDLAS on a time scale of microseconds to milliseconds. This method allows direct determination of reaction rates and product branching ratios over a range of temperature, pressure and reactant concentrations in complete isolation from reactor surfaces.