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Nitrous acid (HONO) plays an important role in tropospheric oxidation chemistry as it is a precursor to the hydroxyl radical (OH). Measurements of HONO have been difficult historically due to instrument interferences and difficulties in sampling and calibration. The traditional calibration method involves generation of HONO by reacting hydrogen chloride vapor with sodium nitrite followed by quantification by various methods (e.g., conversion of HONO to nitric oxide (NO) followed by chemiluminescence detection). Alternatively, HONO can be generated photolytically in the gas phase by reacting NO with OH radicals generated by H2O photolysis. In this work, we describe and compare two photolytic HONO calibration methods that were used to calibrate an iodide adduct chemical ionization mass spectrometer (CIMS). Both methods are based on the water vapor photolysis method commonly used for OH and HO2 (known collectively as HOx) calibrations. The first method is an adaptation of the common chemical actinometry HOx calibration method, in which HONO is calculated based on quantified values for [O3], [H2O], and [O2] and the absorption cross sections for H2O and O2 at 184.9 nm. In the second, novel method HONO is prepared in mostly N2 ([O2]=0.040 %) and is simply quantified by measuring the NO2 formed by the reaction of NO with HO2 generated by H2O photolysis. Both calibration methods were used to prepare a wide range of HONO mixing ratios between ∼400 and 8000 pptv. The uncertainty of the chemical actinometric calibration is 27 % (2σ) and independent of HONO concentration. The uncertainty of the NO2 proxy calibration is concentration-dependent, limited by the uncertainty of the NO2 measurements. The NO2 proxy calibration uncertainties (2σ) presented here range from 4.5 % to 24.4 % (at [HONO] =8000 pptv and [HONO] =630 pptv, respectively) with a 10 % uncertainty associated with a mixing ratio of ∼1600 pptv, typical of values observed in urban areas at night. We also describe the potential application of the NO2 proxy method to calibrating HOx instruments (e.g., LIF, CIMS) at uncertainties below 15 % (2σ).

Ozone (O3), a potent greenhouse gas that is detrimental to human health, is typically found in elevated concentrations within biomass burning (BB) smoke plumes. The radical species OH, HO2, and RO2 (known collectively as ROx) have central roles in the formation of secondary pollutants including O3 but are poorly characterized for BB plumes. We present measurements of total peroxy radical concentrations ([XO2] ≡ [HO2] + [RO2]) and additional trace-gas and particulate matter measurements from McCall, Idaho, during August 2018. There were five distinct periods in which BB smoke impacted this site. During BB events, O3 concentrations were enhanced, evident by ozone enhancement ratios (ΔO3/ΔCO) that ranged up to 0.06 ppbv ppbv−1. [XO2] was similarly elevated during some BB events. Overall, instantaneous ozone production rates (P(O3)) were minimally impacted by the presence of smoke as [NOx] enhancements were minimal. Measured XO2 concentrations were compared to zero-dimensional box modeling results to evaluate the Master Chemical Mechanism (MCM) and GEOS-Chem mechanisms overall and during periods of BB influence. The models consistently overestimated XO2 with the base MCM and GEOS-Chem XO2 predictions high by an average of 28 % and 20 %, respectively. One period of BB influence had distinct measured enhancements of 15 pptv XO2 that were not reflected in the model output, likely due to the presence of unmeasured HOx sources. To the best of our knowledge, this is the first BB study featuring peroxy radical measurements.

The FORCAsT (FORest Canopy Atmosphere Transfer) model version 1.0 is updated to FORCAsT 2.0 by implementing five major changes, including (1) a change to the operator splitting, separating chemistry from emission and dry deposition, which reduces the run time of the gas-phase chemistry by 70 % and produces a more realistic in-canopy profile for isoprene; (2) a modification of the eddy diffusivity parameterization to produce greater and more realistic vertical mixing in the boundary layer, which ameliorates the unrealistic simulated end-of-day peaks in isoprene under well-mixed conditions and improves daytime air temperature; (3) updates to dry deposition velocities with available measurements; (4) implementation of the Reduced Caltech Isoprene Mechanism (RCIM) to reflect the current knowledge of isoprene oxidation; and (5) extension of the aerosol module to include isoprene-derived secondary organic aerosol (iSOA) formation. Along with the operator splitting, modified vertical mixing, and dry deposition, RCIM improves the estimation of first-generation isoprene oxidation products (methyl vinyl ketone and methacrolein) and some second-generation products (such as isoprene epoxydiols). Inclusion of isoprene in the aerosol module in FORCAsT 2.0 leads to a 7 % mass yield of iSOA. The most important iSOA precursors are IEPOX and tetrafunctionals, which together account for >86 % of total iSOA. The iSOA formed from organic nitrates is more important in the canopy, accounting for 11 % of the total iSOA. The tetrafunctionals compose up to 23 % of the total iSOA formation, highlighting the importance of the fate (i.e., dry deposition and gas-phase chemistry) of later-generation isoprene oxidation products in estimating iSOA formation.

Reactions of the hydroxyl ( OH ) and peroxy ( HO2 and RO2 ) radicals play a central role in the chemistry of the atmosphere. In addition to controlling the lifetimes of many trace gases important to issues of global climate change, OH radical reactions initiate the oxidation of volatile organic compounds (VOCs) which can lead to the production of ozone and secondary organic aerosols in the atmosphere. Previous measurements of these radicals in forest environments characterized by high mixing ratios of isoprene and low mixing ratios of nitrogen oxides ( NOx ) (typically less than 1–2 ppb ) have shown serious discrepancies with modeled concentrations. These results bring into question our understanding of the atmospheric chemistry of isoprene and other biogenic VOCs under low NOx conditions. During the summer of 2015, OH and HO2 radical concentrations, as well as total OH reactivity, were measured using laser-induced fluorescence–fluorescence assay by gas expansion (LIF-FAGE) techniques as part of the Indiana Radical Reactivity and Ozone productioN InterComparison (IRRONIC). This campaign took place in a forested area near Indiana University's Bloomington campus which is characterized by high mixing ratios of isoprene (average daily maximum of approximately 4 ppb at 28 ∘C ) and low mixing ratios of NO (diurnal average of approximately 170 ppt ). Supporting measurements of photolysis rates, VOCs, NOx , and other species were used to constrain a zero-dimensional box model based on the Regional Atmospheric Chemistry Mechanism (RACM2) and the Master Chemical Mechanism (MCM 3.2), including versions of the Leuven isoprene mechanism (LIM1) for HOx regeneration (RACM2-LIM1 and MCM 3.3.1). Using an OH chemical scavenger technique, the study revealed the presence of an interference with the LIF-FAGE measurements of OH that increased with both ambient concentrations of ozone and temperature with an average daytime maximum equivalent OH concentration of approximately 5×106 cm−3 . Subtraction of the interference resulted in measured OH concentrations of approximately 4×106 cm−3 (average daytime maximum) that were in better agreement with model predictions although the models underestimated the measurements in the evening. The addition of versions of the LIM1 mechanism increased the base RACM2 and MCM 3.2 modeled OH concentrations by approximately 20 % and 13 %, respectively, with the RACM2-LIM1 mechanism providing the best agreement with the measured concentrations, predicting maximum daily OH concentrations to within 30 % of the measured concentrations. Measurements of HO2 concentrations during the campaign (approximately a 1×109 cm−3 average daytime maximum) included a fraction of isoprene-based peroxy radicals ( HO 2 * = HO 2 + α RO 2 ) and were found to agree with model predictions to within 10 %–30 %. On average, the measured reactivity was consistent with that calculated from measured OH sinks to within 20 %, with modeled oxidation products accounting for the missing reactivity, however significant missing reactivity (approximately 40 % of the total measured reactivity) was observed on some days.

Oxidation flow reactors (OFRs) are an emerging tool for studying the formation and oxidative aging of organic aerosols and other applications. The majority of OFR studies to date have involved the generation of the hydroxyl radical (OH) to mimic daytime oxidative aging processes. In contrast, the use of the nitrate radical (NO3) in modern OFRs to mimic nighttime oxidative aging processes has been limited due to the complexity of conventional techniques that are used to generate NO3. Here, we present a new method that uses a laminar flow reactor (LFR) to continuously generate dinitrogen pentoxide (N2O5) in the gas phase at room temperature from the NO2 + O3 and NO2 + NO3 reactions. The N2O5 is then injected into a dark Potential Aerosol Mass (PAM) OFR and decomposes to generate NO3; hereafter, this method is referred to as “OFR-iN2O5” (where “i” stands for “injected”). To assess the applicability of the OFR-iN2O5 method towards different chemical systems, we present experimental and model characterization of the integrated NO3 exposure, NO3:O3, NO2:NO3, and NO2:O2 as a function of LFR and OFR conditions. These parameters were used to investigate the fate of representative organic peroxy radicals (RO2) and aromatic alkyl radicals generated from volatile organic compound (VOC) + NO3 reactions, and VOCs that are reactive towards both O3 and NO3. Finally, we demonstrate the OFR-iN2O5 method by generating and characterizing secondary organic aerosol from the β-pinene + NO3 reaction.

Ozone (O3), a potent greenhouse gas that is detrimental to human health, is typically found in elevated concentrations within biomass burning (BB) smoke plumes. The radical species OH, HO2, and RO2 (known collectively as ROx) have central roles in the formation of secondary pollutants including O3 but are poorly characterized for BB plumes. We present measurements of total peroxy radical concentrations ([XO2] ≡ [HO2] + [RO2]) and additional trace-gas and particulate matter measurements from McCall, Idaho during August 2018. There were five distinct periods in which BB smoke impacted this site. During BB events, O3 concentrations were enhanced as evidenced by ozone enhancement ratios (ΔO3/ ΔCO) that ranged up to 0.25 ppbv ppbv−1. [XO2] was similarly elevated during some BB events. Overall, quantified instantaneous ozone production rates (P(O3)) were only slightly impacted by the presence of smoke as NOx enhancements were minimal. Measured XO2 concentrations were compared to zero-dimensional box modeling results to evaluate the effectiveness of the Master Chemical Mechanism (MCM) and GEOS-Chem mechanisms during periods of BB influence and overall agreed within 31 %. One period of BB influence had distinct measured enhancements of 15 pptv XO2 that were not reflected in the model output, likely due to the presence of an unmeasured HOx source, quite likely nitrous acid (HONO). To our knowledge, this is the first BB study featuring peroxy radical measurements.

Observations of total peroxy radical concentrations ([XO2] ≡ [RO2] + [HO2]) made by the Ethane CHemical AMPlifier (ECHAMP) and concomitant observations of additional trace gases made on board the Aerodyne Mobile Laboratory (AML) during May 2017 were used to characterize ozone production at three sites in the San Antonio, Texas, region. Median daytime [O3] was 48 ppbv at the site downwind of central San Antonio. Higher concentrations of NO and XO2 at the downwind site also led to median daytime ozone production rates (P(O3)) of 4.2 ppbv h−1, a factor of 2 higher than at the two upwind sites. The 95th percentile of P(O3) at the upwind site was 15.1 ppbv h−1, significantly lower than values observed in Houston. In situ observations, as well as satellite retrievals of HCHO and NO2, suggest that the region was predominantly NOx-limited. Only approximately 20 % of observations were in the VOC-limited regime, predominantly before 11:00 EST, when ozone production was low. Biogenic volatile organic compounds (VOCs) comprised 55 % of total OH reactivity at the downwind site, with alkanes and non-biogenic alkenes responsible for less than 10 % of total OH reactivity in the afternoon, when ozone production was highest. To control ozone formation rates at the three study sites effectively, policy efforts should be directed at reducing NOx emissions. Observations in the urban center of San Antonio are needed to determine whether this policy is true for the entire region.

Nitrogen oxides (NOX) and methane impact air quality through the promotion of ozone formation, and methane is also a strong greenhouse gas. Despite the importance of these pollutants, emissions in urban areas are poorly quantified. We present measurements of NOX, CH4, CO, and CO2 made at Drexel University in Philadelphia along with NOX and CO observations at two roadside monitors. Because CO2 concentrations in the winter result almost entirely from combustion with negligible influence from photosynthesis and respiration, we are able to infer fleet-averaged fuel-based emission factors (EFs) for NOX and CO, similar in some ways to how EFs are determined from tunnel studies. Comparison of the inferred NOX and CO fuel-based EF to the National Emissions Inventory (NEI) suggests errors in NEI emissions of either NOX, CO, or both. From the measurements of CH4 and CO2, which are not emitted by the same sources, we infer the ratio of CH4 emissions (from leaks in the natural gas infrastructure) to CO2 emissions (from fossil fuel combustion) in Philadelphia. Comparison of the CH4/CO2 emission ratios to emission inventories from the Environmental Protection Agency suggests underestimates in CH4 emissions by almost a factor of 4. These results demonstrate the need for the addition of long-term observations of CH4 and CO2 to existing monitoring networks in urban areas to better constrain emissions and complement existing measurements of NOX and CO.

Peroxy radicals play important roles in the atmospheric oxidation of organic compounds and the formation of ozone and secondary organic aerosol. There are few peroxy radical measurement techniques; the most common, chemical amplification using CO and NO, requires the use of toxic reagents, and its calibration factor is very sensitive to relative humidity. We present a new method for quantifying atmospheric peroxy radicals, ECHAMP (Ethane CHemical AMPlifier). Sampled air is mixed with NO and C2H6 (rather than CO), effecting a series of reactions that ultimately produces 25 molecules of NO2 per sampled peroxy radical under dry conditions. This “amplification” factor decreases to 17 at a relative humidity of 50%, yielding a 1σ precision for 90 s average measurements of 0.8–2.5 ppt depending on the atmospheric variability of ozone. We demonstrated the utility of the new technique with measurements in Bloomington, IN, in July 2015.

Peroxy radicals were measured in a mixed deciduous forest atmosphere in Bloomington, Indiana, USA, during the Indiana Radical, Reactivity and Ozone Production Intercomparison (IRRONIC) during the summer of 2015. Total peroxy radicals ([XO2] ≡ [HO2] + Ʃ[RO2]) were measured by a newly developed technique involving nitric oxide (NO) – ethane (C2H6) chemical amplification followed by NO2 detection by cavity attenuated phase shift spectroscopy (hereinafter referred to as ECHAMP). The sum of hydroperoxy radicals (HO2) and a portion of organic peroxy radicals ([HO2*] = [HO2] + Ʃαi[RiO2], 0 We compared ambient measurements from both instruments and conducted a calibration source comparison. For the calibration comparison, the ECHAMP instrument, which is primarily calibrated with an acetone photolysis method, sampled the output of the LIF-FAGE calibration source which is based on the water vapor photolysis method and, for these comparisons, generated a 50–50 % mixture of HO2 and either butane or isoprene-derived RO2. A bivariate fit of the data yields the relation [XO2]ECHAMP = 0.88 ([HO2] + RO2])IU_cal + 6.6 ppt, with an R2 of 0.99. This level of agreement is within the combined analytical uncertainties for the two instruments' calibration methods. A linear fit of all the 30-minute averaged [XO2] ambient data with the 1-minute averaged [HO2*] data (one point per 30 minutes) yields the relation [XO2] = 0.85 [HO2*] + 3.3 ppt, with an R2 of 0.67. Day to day variability in the [XO2] / [HO2*] ratio was observed. The lowest [XO2] / [HO2*] ratios between 13:00 and 16:00 were 0.8 on 13 and 18 July, whereas the highest ratios of 1.1 to 1.3 were observed on 24 and 25 July – the same two days on which the highest concentrations of isoprene and ozone were observed. Although the exact composition of the peroxy radicals during IRRONIC is not known, 0-dimensional photochemical modeling of the IRRONIC dataset using the RACM2, RACM2-LIM1, MCM 3.2, and MCM 3.3.1 chemical mechanisms predicts afternoon [XO2] / [HO2*] ratios of between 1.1 to 1.5 depending on mechanism. Differences between the observed ambient [XO2] / [HO2*] ratio and that predicted with the 0-D modeling can be attributed to deficiencies in the model, errors in the two measurement techniques, or both. Although these comparison results are encouraging and demonstrate the viability of using the new ECHAMP technique for field measurements of peroxy radicals, further research investigating the overall accuracy of the measurements and possible interferences from both methods is warranted.

Observations of total peroxy radicals (XO2 = RO2 + HO2) made by the Ethane CHemical AMPlifier (ECHAMP) and concomitant observations of additional trace gases made onboard the Aerodyne Mobile Laboratory (AML) during May 2017 were used to characterize ozone production at three sites in the San Antonio, Texas region. Median daytime [O3] was 48 ppbv at the site downwind of central San Antonio. Higher concentrations of NO and XO2 at the downwind site also led to median daytime ozone production rates (P(O3)) of 4.2 ppbv hr−1, a factor of two higher than at the two upwind sites. The 95th percentile of P(O3) at the upwind site was 15.1 ppbv hr−1, significantly lower than values observed in Houston. In situ observations, as well as satellite retrievals of HCHO and NO3, suggest that the region is NOx limited for times after approximately 09:00 local time, before which ozone production is VOC-limited. Biogenic volatile organic compounds (VOC) comprised 55 % of total OH reactivity at the downwind site, with alkanes and non-biogenic alkenes responsible for less than 10 % of total OH reactivity in the afternoon, when ozone production was highest. To control ozone formation rates at the three study sites effectively, policy efforts should be directed at reducing NOx emissions. Observations in the urban center of San Antonio are needed to determine whether this policy is true for the entire region.

The 2010 Comprehensive Flare Study provided the opportunity for the first blind validation of a remote sensing technique for flare combustion efficiency (CE) against extractive analysis techniques. The overall test results show that both remote sensing and extractive sampling accurately determined the flare performance curve. Both remote and extractive sampling techniques are challenged by the fluctuating and inhomogeneous nature of the flare exhaust plume. Accurate measurement of CE values near 100% is of interest to flare manufacturers, users, and regulators, while measurement of low CE flares is of interest in the development of other applications of combustion monitoring, and the 2010 tests provided information on both. In practice, accurate values of CE can be determined through the measurement of a small number of gaseous species, including fuel components and products of combustion. Nominal error bars generated from the fluctuations in these component measurements were adequate to account for most ...

During the 2010 Comprehensive Flare Study a suite of analytical instrumentation was employed to monitor and quantify in real-time the volatile organic compound (VOC) emissions emanating from an industrial chemical process flare burning either propene/natural gas or propane/natural gas. To our knowledge this represents the first time the VOC composition has been directly measured as a function of flare efficiency on an operational full-scale flare. This compositional information was obtained using a suite of proton-transfer-reaction mass spectrometers (PTR-MS) and quantum cascade laser tunable infrared differential absorption spectrometers (QCL-TILDAS) to measure the unburned fuel and associated combustion byproducts. Methane, ethyne, ethene, and formaldehyde were measured using the QC-TILDAS. Propene, acetaldehyde, methanol, benzene, acrolein, and the sum of the C3H6O isomers were measured with the PTR-MS. A second PTR-MS equipped with a gas chromatograph (GC) was operated in parallel and was used to veri...

We report combustion emissions data for several alternatives to petroleum based Jet A jet fuel, including a natural gas–derived Fischer–Tropsch (FT) synthetic fuel; a 50/50 blend of the FT synthetic fuel with Jet A-1; a 20/80 blend of a fatty acid methyl ester (FAME) with jet fuel; and a 40/60 blend of FAME with jet fuel. The chief distinguishing features of the alternative fuels are reduced (for blends) or negligible (for pure fuels) aromatic content and increased oxygen content (for FAME blends). A CFM International CFM56-7 gas turbine engine was the test engine, and we measured NOX, CO, speciated volatile organic compounds (including oxygenates, olefins, and aromatic compounds), and nonvolatile particle size distribution, number, and mass emissions. We developed several new methods that account for fuel energy content and used the new methods to evaluate potential fuel effects on emissions performance. Our results are categorized as follows: (1) regulated pollutant emissions, CO, and NOX; (2) volatile ...

Exhaust emitted from jet engines contains high concentrations of combustion by-products, some of which are damaging to human and ecosystem health. As these pollutants mix with the surrounding air, they undergo chemical reactions that eventually break them down to their water-soluble or inert forms. To date, the reactivity of aircraft exhaust has been largely unexplored, and it is not known whether state-of-the-art models account for chemistry at the plume level, which directly relates to air quality downwind of airports. To a large extent, the concentrations of hydroxyl (OH) and hydroperoxyl (HO2) radicals—collectively called HOx—present in emitted plumes determine the rate at which components of the exhaust are oxidized. In January 2009, the authors quantified emissions of all HOx precursors including nitrous acid (HONO), formaldehyde (HCHO), acetaldehyde (CH3CHO), and ozone (O3) at the Alternative Aviation Fuels Experiment in Palmdale, California. The results indicate that (a) HOx production rate due to direct emission of these precursors is orders of magnitude faster in the exhaust plume than in “normal” urban air; (b) the concentration of pollutants in plumes does not reach typical ambient levels until it has been diluted by a factor of about 6,000; and (c) photolysis of HONO in these plumes is by far the biggest source of HOx during daytime. Analyses of the reactions involving HOx demonstrate that propagation of these radicals is favored over termination, which indicates that chemical reactivity will continue to be enhanced in these plumes even after being diluted to ambient levels.

Mobile emissions represent a significant fraction of the total anthropogenic emissions burden in the Mexico City Metropolitan Area (MCMA) and, therefore, it is crucial to use top-down techniques informed by on-road exhaust measurements to evaluate and improve traditional bottom-up official emissions inventory (EI) for the city. We present the measurements of on-road fleet-average emission factors obtained using the Aerodyne mobile laboratory in the MCMA in March 2006 as part of the MILAGRO/MCMA-2006 field campaign. A comparison of our on-road emission measurements with those obtained in 2003 using essentially the same measurement techniques and analysis methods indicates that, in the three year span, NO emission factors remain within the measured variability ranges whereas emission factors of aldehydes and aromatics species were reduced for all sampled driving conditions. We use a top-down fuel-based approach to evaluate the mobile emissions from the gasoline fleet estimated in the bottom-up official 2006 MCMA mobile sources. Within the range of measurement uncertainties, we found probable slight overpredictions of mean EI estimates on the order of 20-28% for CO and 14-20% for NO. However, we identify a probable EI discrepancy of VOC mobile emissions between 1.4 and 1.9; although estimated benzene and toluene mobile emissions in the inventory seem to be well within the uncertainties of the corresponding emissions estimates. Aldehydes mobile emissions in the inventory, however, seem to be underpredicted by factors of 3 for HCHO and 2 for CH(3)CHO. Our on-road measurement-based estimate of annual emissions of organic mass from PM(1) particles suggests a severe underprediction (larger than a factor of 4) of PM(2.5) mobile emissions in the inventory. Analyses of ambient CO, NO(x) and CO/NO(x) concentration trends in the MCMA indicate that the early morning ambient CO/NO(x) ratio has decreased at a rate of about 1.9 ppm/ppm/year over the last two decades due to reductions in CO levels rather than by NO(x). These trends, together with the analysis of fuel sales and fleet size, suggest that the relative contribution of diesel vehicles to overall NO(x) levels has increased over time in the city. Despite the impressive increase in the size of the vehicle fleet between 2000 and 2006, the early morning ambient concentrations of CO and NO(x) have not increased accordingly, probably due to the reported low removal rates of older vehicles, which do not have emissions control technologies, and partially due to the much lower emissions from newer gasoline vehicles. This indicates that an emission-based air quality improvement strategy targeting large reductions of emissions from mobile sources should be directed towards a significant increase of the removal rate of older, highly-polluting, vehicles. US Department of Energy's Atmospheric Sciences Program DE-FG02-05ER63980, DE-FG02-05ER63982 US National Science Foundation's Atmospheric Chemistry Program ATM-0528170, ATM-528227 Mexico's Comision Ambiental Metropolitana

Observations at a mountain-top site within the Mexico City basin are used to characterize ozone production and destruction, nitrogen oxide speciation and chemistry, and the radical budget, with an emphasis on a stagnant air mass observed on one afternoon. The observations compare well with the results of recent photochemical models. An ozone production rate of ~50 ppbv/h was observed in a stagnant air mass during the afternoon of 12 March 2006, which is among the highest observed anywhere in the world. Approximately half of the ozone destruction was due to the oxidation of NO2. During this time period ozone production was VOC-limited, deduced by a comparison of the radical production rates and the formation rate of NOx oxidation products (NOz). For [NOx]/[NOy] values between 0.2 and 0.8, gas-phase HNO3 typically accounted for less than 10% of NOz and accumulation-mode particulate nitrate (NO3(PM1)−) accounted for 20%–70% of NOz, consistent with high ambient NH3 concentrations. The fraction of NOz accounted for by the sum of HNO3(g) and NO3(PM1)− decreased with photochemical processing. This decrease is apparent even when dry deposition of HNO3 is accounted for, and indicates that HNO3 formation decreased relative to other NOx "sink" processes during the first 12 h of photochemistry and/or a significant fraction of the nitrate was associated with the coarse aerosol size mode. The ozone production efficiency of NOx on 11 and 12 March 2006 was approximately 7 on a time scale of one day. A new metric for ozone production efficiency that relates the dilution-adjusted ozone mixing ratio to cumulative OH exposure is proposed.

Measurements of nitrogen oxides from a variety of commercial aircraft engines as part of the JETS-APEX2 and APEX3 campaigns show that NOx (NOx [triple bond] NO + NO2) is emitted primarily in the form of NO2 at idle thrust and NO at high thrust. A chemical kinetics combustion model reproduces the observed NO2 and NOx trends with engine power and sheds light on the relevant chemical mechanisms. Experimental evidence is presented of rapid conversion of NO to NO2 in the exhaust plume from engines at low thrust. The rapid conversion and the high NO2/NOx emission ratios observed are unrelated to ozone chemistry. NO2 emissions from a CFM56-3B1 engine account for approximately 25% of the NOx emitted below 3000 feet (916 m) and 50% of NOx emitted below 500 feet (153 m) during a standard ICAO (International Civil Aviation Organization) landing-takeoff cycle. Nitrous acid (HONO) accounts for 0.5% to 7% of NOy emissions from aircraft exhaust depending on thrust and engine type. Implications for photochemistry near airports resulting from aircraft emissions are discussed.

We report in situ measurements of N2O5, NO2, and O3 in Contra Costa County, California during January 2004. Mixing ratios of N2O5, an intermediate compound in the atmosphere's nocturnal cleansing process, ranged up to 200pmol/mol at night. The highest N2O5 concentrations were correlated with low O3 and high NO2 concentrations. The calculated steady state lifetime for N2O5 ranged from 5 to 30min. The total HNO3 produced by N2O5 hydrolysis over a 14h night was comparable to ambient NO2 concentrations, and is estimated to be a factor of nine bigger than the HNO3 produced during the day.

Pollutant concentrations in the exhaust plumes of individual diesel trucks were measured at high time resolution in a highway tunnel in Oakland, CA, during July 2010. Emission factors for individual trucks were calculated using a carbon balance method, in which pollutants measured in each exhaust plume were normalized to measured concentrations of carbon dioxide. Pollutants considered here include nitric oxide, nitrogen dioxide (NO(2)), carbon monoxide, formaldehyde, ethene, and black carbon (BC), as well as optical properties of emitted particles. Fleet-average emission factors for oxides of nitrogen (NO(x)) and BC respectively decreased 30 ± 6 and 37 ± 10% relative to levels measured at the same location in 2006, whereas a 34 ± 18% increase in the average NO(2) emission factor was observed. Emissions distributions for all species were skewed with a small fraction of trucks contributing disproportionately to total emissions. For example, the dirtiest 10% of trucks emitted half of total NO(2) and BC emissions. Emission rates for NO(2) were found to be anticorrelated with all other species considered here, likely due to the use of catalyzed diesel particle filters to help control exhaust emissions. Absorption and scattering cross-section emission factors were used to calculate the aerosol single scattering albedo (SSA, at 532 nm) for individual truck exhaust plumes, which averaged 0.14 ± 0.03.

The emissions from a Garrett-AiResearch (now Honeywell) Model GTCP85-98CK auxiliary power unit (APU) were determined as part of the National Aeronautics and Space Administration's (NASA's) Alternative Aviation Fuel Experiment (AAFEX) using both JP-8 and a coal-derived Fischer Tropsch fuel (FT-2). Measurements were conducted by multiple research organizations for sulfur dioxide (SO2, total hydrocarbons (THC), carbon monoxide (CO), carbon dioxide (CO2), nitrogen oxides (NOx), speciated gas-phase emissions, particulate matter (PM) mass and number, black carbon, and speciated PM. In addition, particle size distribution (PSD), number-based geometric mean particle diameter (GMD), and smoke number were also determined from the data collected. The results of the research showed PM mass emission indices (EIs) in the range of 20 to 700 mg/kg fuel and PM number EIs ranging from 0.5 x 10(15) to 5 x 10(15) particles/kg fuel depending on engine load and fuel type. In addition, significant reductions in both the SO2 and PM EIs were observed for the use of the FT fuel. These reductions were on the order of approximately 90% for SO2 and particle mass EIs and approximately 60% for the particle number EI, with similar decreases observed for black carbon. Also, the size of the particles generated by JP-8 combustion are noticeably larger than those emitted by the APU burning the FT fuel with the geometric mean diameters ranging from 20 to 50 nm depending on engine load and fuel type. Finally, both particle-bound sulfate and organics were reduced during FT-2 combustion. The PM sulfate was reduced by nearly 100% due to lack of sulfur in the fuel, with the PM organics reduced by a factor of approximately 5 as compared with JP-8.

Given the predicted growth of aviation and the recent developments of alternative aviation fuels, quantifying methane (CH(4)) and nitrous oxide (N(2)O) emission ratios for various aircraft engines and fuels can help constrain projected impacts of aviation on the Earth's radiative balance. Fuel-based emission indices for CH(4) and N(2)O were quantified from CFM56-2C1 engines aboard the NASA DC-8 aircraft during the first Alternative Aviation Fuel Experiment (AAFEX-I) in 2009. The measurements of JP-8 fuel combustion products indicate that at low thrust engine states (idle and taxi, or 4% and 7% maximum rated thrusts, respectively) the engines emit both CH(4) and N(2)O at a mean ± 1σ rate of 170 ± 160 mg CH(4) (kg Fuel)(-1) and 110 ± 50 mg N(2)O (kg Fuel)(-1), respectively. At higher thrust levels corresponding to greater fuel flow and higher engine temperatures, CH(4) concentrations in engine exhaust were lower than ambient concentrations. Average emission indices for JP-8 fuel combusted at engine thrusts between 30% and 100% of maximum rating were -54 ± 33 mg CH(4) (kg Fuel)(-1) and 32 ± 18 mg N(2)O (kg Fuel)(-1), where the negative sign indicates consumption of atmospheric CH(4) in the engine. Emission factors for the synthetic Fischer-Tropsch fuels were statistically indistinguishable from those for JP-8.

This paper describes the development and testing of a gas sampling probe that quenches chemical reactions by using supersonic expansion and helium dilution. Gas sampling probes are required for accurate measurement of exhaust emissions species, which is critical to determine the performance of an aircraft engine. The probe was designed through rounds of computational modeling and laboratory testing, and was subsequently manufactured and then tested at the University of Tennessee Space Institute (UTSI) behind a General Electric J85 turbojet engine at different power settings: idle, maximum military and afterburning. The experimental test results demonstrated that the Chemical Quick-Quench (CQQ) probe suppressed the oxidation of carbon monoxide (CO) inside the probe system and preserved more CO at afterburning conditions. In addition, the CQQ probe prevented hydrocarbons from being partially-oxidized to form CO at idle powers, and measured higher hydrocarbons and lower CO emission compared to a conventional probe at that low power condition. The CQQ probe also suppressed nitrogen dioxide (NO2 ) to nitric oxide (NO) conversion through all engine power settings. These data strongly support the conclusion that the CQQ probe is able to quench unwanted chemical reactions inside the probe for all engine power levels.Copyright © 2010 by ASME

Aerosol mass spectrometer (AMS) measurements are used to characterize the evolution of exhaust particulate matter (PM) properties near and downwind of vehicle sources. The AMS provides time-resolved chemically speciated mass loadings and mass-weighted size distributions of nonrefractory PM smaller than 1 microm (NRPM1). Source measurements of aircraft PM show that black carbon particles inhibit nucleation by serving as condensation sinks for the volatile and semi-volatile exhaust gases. Real-world source measurements of ground vehicle PM are obtained by deploying an AMS aboard a mobile laboratory. Characteristic features of the exhaust PM chemical composition and size distribution are discussed. PM mass and number concentrations are used with above-background gas-phase carbon dioxide (CO2) concentrations to calculate on-road emission factors for individual vehicles. Highly variable ratios between particle number and mass concentrations are observed for individual vehicles. NRPM1 mass emission factors measured for on-road diesel vehicles are approximately 50% lower than those from dynamometer studies. Factor analysis of AMS data (FA-AMS) is applied for the first time to map variations in exhaust PM mass downwind of a highway. In this study, above-background vehicle PM concentrations are highest close to the highway and decrease by a factor of 2 by 200 m away from the highway. Comparison with the gas-phase CO2 concentrations indicates that these vehicle PM mass gradients are largely driven by dilution. Secondary aerosol species do not show a similar gradient in absolute mass concentrations; thus, their relative contribution to total ambient PM mass concentrations increases as a function of distance from the highway. FA-AMS of single particle and ensemble data at an urban receptor site shows that condensation of these secondary aerosol species onto vehicle exhaust particles results in spatial and temporal evolution of the size and composition of vehicle exhaust PM on urban and regional scales.

The Aircraft Alternative Fuels Emissions experiment (AAFEX) was conducted at National Aeronautic and Space Administration (NASA) Dryden Flight Research Center (DFRC) Aircraft Operations Facility (DAOF) in Palmdale, California, during January and February 2009. The purpose was to systematically investigate the effect of alternative fuels on both gas-phase and particle emissions from a CFM56-2C1 engine on NASA’s DC-8 aircraft parked on the ground as functions of engine power, fuel composition, and exhaust plume age. Emissions parameters were measured at 6 engine power settings, ranging from idle to maximum thrust, in samples collected at 1, 30, and 145 meters (m) downstream of the exhaust plane as the aircraft burned three pure fuels and two fuel blends. The fuels included JP-8, two fuels produced using the Fischer-Tropsch process and 50/50 blends by volume of the F-T fuels with JP-8. The 1 m sampling rakes contained multiple gas and particle inlet probes and could also be traversed in order to measure the spatial variation of emissions across the engine exhaust plane. The #2 inboard engine on the left side always burned JP-8 while the #3 inboard right side engine was fueled with the various fuels and fuel blends. In addition, emissions from the Auxiliary Power Unit (APU) were also evaluated with both JP-8 and one pure F-T fuel. Both gaseous and particulate emissions are presented. Results show that the synthetic fuels reduced pollutant emissions while having relatively little effect on engine operation or performance.Copyright © 2010 by ASME

The potential human health and environmental impacts of aircraft gas turbine engine emissions during normal airport operation are issues of growing concern. During the JETS/Aircraft Particle Emissions eXperiment(APEX)-2 and APEX-3 field campaigns, we performed an extensive series of gas phase and particulate emissions measurements of on-wing gas turbine engines. In all, nine different CFM56 style engines (including both CFM56-3B1 and -7B22 models) and seven additional engines (two RB211-535E4-B engines, three AE3007 engines, one PW4158, and one CJ6108A) were studied to evaluate engine-to-engine variability. Specific gas-phase measurements include NO2, NO, and total NOx, HCHO, C2H4, CO, and a range of volatile organic compounds (e.g., benzene, styrene, toluene, naphthalene). A number of broad conclusions can be made based on the gas-phase data set: (1) field measurements of gas-phase emission indices (EIs) are generally consistent with ICAO certification values; (2) speciation of gas phase NOx between NO and NO2 is reproducible for different engine types and favors NO2 at low power (and low fuel flow rate) and NO at high power (high fuel flow rate); (3) emission indices of gas-phase organic compounds and CO decrease rapidly with increasing fuel flow rate; (4) plotting EI-CO or volatile organic compound EIs against fuel flow rate collapses much of the variability between the different engines, with one exception (AE3007); (5) HCHO, ethylene, acetaldehyde, and propene are the most abundant volatile organic compounds present in the exhaust gases that we can detect, independent of engine technology differences. Empirical correlations accurate to within 30% and based on the publicly available engine parameters are presented for estimating EI-NOx and EI-NO2. Engine-to-engine variability, unavailability of combustor input conditions, changing ambient temperatures, and complex reaction dynamics limit the accuracy of global correlations for CO or volatile organic compound EIs.

Quantification of exposure to traffic-related air pollutants near highways is hampered by incomplete knowledge of the scales of temporal variation of pollutant gradients. The goal of this study was to characterize short-term temporal variation of vehicular pollutant gradients within 200–400 m of a major highway (>150 000 vehicles/d). Monitoring was done near Interstate 93 in Somerville (Massachusetts) from 06:00 to 11:00 on 16 January 2008 using a mobile monitoring platform equipped with instruments that measured ultrafine and fine particles (6–1000 nm, particle number concentration (PNC)); particle-phase (>30 nm) NO3−, SO42−, and organic compounds; volatile organic compounds (VOCs); and CO2, NO, NO2, and O3. We observed rapid changes in pollutant gradients due to variations in highway traffic flow rate, wind speed, and surface boundary layer height. Before sunrise and peak traffic flow rates, downwind concentrations of particles, CO2, NO, and NO2 were highest within 100–250 m of the highway. After sunrise pollutant levels declined sharply (e.g., PNC and NO were more than halved) and the gradients became less pronounced as wind speed increased and the surface boundary layer rose allowing mixing with cleaner air aloft. The levels of aromatic VOCs and NO3−, SO42− and organic aerosols were generally low throughout the morning, and their spatial and temporal variations were less pronounced compared to PNC and NO. O3 levels increased throughout the morning due to mixing with O3-enriched air aloft and were generally lowest near the highway reflecting reaction with NO. There was little if any evolution in the size distribution of 6–225 nm particles with distance from the highway. These results suggest that to improve the accuracy of exposure estimates to near-highway pollutants, short-term (e.g., hourly) temporal variations in pollutant gradients must be measured to reflect changes in traffic patterns and local meteorology.

Many recent models underpredict secondary organic aerosol (SOA) particulate matter (PM) concentrations in polluted regions, indicating serious deficiencies in the models' chemical mechanisms and/or missing SOA precursors. Since tropospheric photochemical ozone production is much better understood, we investigate the correlation of odd-oxygen ([Ox]≡[O3]+[NO2]) [([O subscript x] ≡ [O subscript 3] + [NO subscript 2])] and the oxygenated component of organic aerosol (OOA), which is interpreted as a surrogate for SOA. OOA and Ox [O subscript x] measured in Mexico City in 2006 and Houston in 2000 were well correlated in air masses where both species were formed on similar timescales (less than 8 h) and not well correlated when their formation timescales or location differed greatly. When correlated, the ratio of these two species ranged from 30 μg [mu g] m−3/ppm [m superscript -3 / ppm] (STP) in Houston during time periods affected by large petrochemical plant emissions to as high as 160 μg [mu g] m−3/ppm [m superscript -3 / ppm] in Mexico City, where typical values were near 120 μg [mu g] m−3/ppm [m superscript -3 / ppm]. On several days in Mexico City, the [OOA]/[Ox] [[OOA] / O subscript x]] ratio decreased by a factor of ~2 between 08:00 and 13:00 local time. This decrease is only partially attributable to evaporation of the least oxidized and most volatile components of OOA; differences in the diurnal emission trends and timescales for photochemical processing of SOA precursors compared to ozone precursors also likely contribute to the observed decrease. The extent of OOA oxidation increased with photochemical aging. Calculations of the ratio of the SOA formation rate to the Ox [O subscript x] production rate using ambient VOC measurements and traditional laboratory SOA yields are lower than the observed [OOA]/[Ox] [[OOA] / O subscript x]] ratios by factors of 5 to 15, consistent with several other models' underestimates of SOA. Calculations of this ratio using emission factors for organic compounds from gasoline and diesel exhaust do not reproduce the observed ratio. Although not successful in reproducing the atmospheric observations presented, modeling P(SOA)/P(Ox) [P (SOA) / P (O subscript x)] can serve as a useful test of photochemical models using improved formulation mechanisms for SOA., National Science Foundation (U.S.) (Grant ATM-528227), National Science Foundation (U.S.) (Grant ATM-0528170), National Science Foundation (U.S.) (Grant ATM-0513116), National Science Foundation (U.S.) (Grant ATM-0449815), United States. Dept. of Energy. Office of Biological and Environmental Research. Atmospheric Science Program (Grant DE-FGO2-05ER63982), United States. Dept. of Energy. Office of Biological and Environmental Research. Atmospheric Science Program (Grant DEFGO2- 05ER63980), United States. Dept. of Energy. Office of Biological and Environmental Research. Atmospheric Science Program (Grant DE-FG02-08ER64627), United States. National Oceanic and Atmospheric Administration (Grant NA08OAR4310656)

The goal of this research is to quantify diesel- and gasoline-powered motor vehicle emissions within the Mexico City Metropolitan Area (MCMA) using on-road measurements captured by a mobile laboratory combined with positive matrix factorization (PMF) receptor modeling. During the MCMA-2006 ground-based component of the MILAGRO field campaign, the Aerodyne Mobile Laboratory (AML) measured many gaseous and particulate pollutants, including carbon dioxide, carbon monoxide (CO), nitrogen oxides (NOx) [(NO subscript x)], benzene, toluene, alkylated aromatics, formaldehyde, acetaldehyde, acetone, ammonia, particle number, fine particulate mass (PM2.5) [(PM subscript 2.5)], and black carbon (BC). These serve as inputs to the receptor model, which is able to resolve three factors corresponding to gasoline engine exhaust, diesel engine exhaust, and the urban background. Using the source profiles, we calculate fuel-based emission factors for each type of exhaust. The MCMA's gasoline-powered vehicles are considerably dirtier, on average, than those in the US with respect to CO and aldehydes. Its diesel-powered vehicles have similar emission factors of NOx [NO subscript x] and higher emission factors of aldehydes, particle number, and BC. In the fleet sampled during AML driving, gasoline-powered vehicles are found to be responsible for 97% of total vehicular emissions of CO, 22% of NOx [NO subscript x], 95–97% of each aromatic species, 72–85% of each carbonyl species, 74% of ammonia, negligible amounts of particle number, 26% of PM2.5 [PM subscript 2.5], and 2% of BC; diesel-powered vehicles account for the balance. Because the mobile lab spent 17% of its time waiting at stoplights, the results may overemphasize idling conditions, possibly resulting in an underestimate of NOx [NO subscript x] and overestimate of CO emissions. On the other hand, estimates of the inventory that do not correctly account for emissions during idling are likely to produce bias in the opposite direction.The resulting fuel-based estimates of emissions are lower than in the official inventory for CO and NOx [NO subscript x] and higher for VOCs. For NOx [NO subscript x], the fuel-based estimates are lower for gasoline-powered vehicles but higher for diesel-powered ones compared to the official inventory. While conclusions regarding the inventory should be interpreted with care because of the small sample size, 3.5 h of driving, the discrepancies with the official inventory agree with those reported in other studies., National Science Foundation (U.S.) (Grant ATM-0528170), National Science Foundation (U.S.) (Grant ATM-0528227), United States. Dept. of Energy (Grant DE-FG02-05ER63982), United States. National Aeronautics and Space Administration, Molina Center for Energy and the Environment

The advent of continuous wave quantum cascade lasers operating at near room temperature has greatly expanded the capability of spectroscopic detection of atmospheric trace gases using infrared absorption at wavelengths from 4 to 12 μm. The high optical power, narrow line width, and high degree of single mode purity result in minimal fractional absorptions of 5x10-6 Hz-1/2 detectable in direct absorption with path lengths up to 210 meters. The Allan plot minima correspond to a fractional absorbance of 1x10-6 or a minimum absorption per unit path length 5x10-11 cm-1 in 50s. This allows trace gas mixing ratio detection limits in the low part-per-trillion (1 ppt = 10-12) range for many trace gases of atmospheric interest. We present ambient measurements of NO2 with detection precision of 10 ppt Hz-1/2. The detection precision for the methane isotopologue 13CH4 is 25 ppt Hz-1/2 which allows direct measurements of ambient ratios of 13CH4/12CH4 with a precision of 0.5‰ in 100 s without pre-concentration. Projections are given for detection limits for other gases including COS, HONO and HCHO as CWRT lasers become available at appropriate wavelengths.

Mobile sources produce a significant fraction of the total anthropogenic emissions burden in large cities and have harmful effects on air quality at multiple spatial scales. Mobile emissions are intrinsically difficult to estimate due to the large number of parameters affecting the emissions variability within and across vehicles types. The MCMA-2003 Campaign in Mexico City has showed the utility of using a mobile laboratory to sample and characterize specific classes of motor vehicles to better quantify their emissions characteristics as a function of their driving cycles. The technique clearly identifies "high emitter" vehicles via individual exhaust plumes, and also provides fleet average emission rates. We have applied this technique to Mexicali during the Border Ozone Reduction and Air Quality Improvement Program (BORAQIP) for the Mexicali-Imperial Valley in 2005. We analyze the variability of measured emission ratios for emitted NOx [NO subscript x], CO, specific VOCs, NH3 [NH subscript 3], and some primary fine particle components and properties by deploying a mobile laboratory in roadside stationary sampling, chase and fleet average operational sampling modes. The measurements reflect various driving modes characteristic of the urban fleets. The observed variability for all measured gases and particle emission ratios is greater for the chase and roadside stationary sampling than for fleet average measurements. The fleet average sampling mode captured the effects of traffic conditions on the measured on-road emission ratios, allowing the use of fuel-based emission ratios to assess the validity of traditional "bottom-up" emissions inventories. Using the measured on-road emission ratios, we estimate CO and NOx [NO subscript x] mobile emissions of 175±62 and 10.4±1.3 metric tons/day, respectively, for the gasoline vehicle fleet in Mexicali. Comparisons with similar on-road emissions data from Mexico City indicated that fleet average NO emission ratios were around 20% higher in Mexicali than in Mexico City whereas HCHO and NH3 [NH subscript 3] emission ratios were higher by a factor of 2 in Mexico City than in Mexicali. Acetaldehyde emission ratios did not differ significantly whereas selected aromatics VOCs emissions were similar or smaller in Mexicali. Nitrogen oxides emissions for on-road heavy-duty diesel truck (HDDT) were measured near Austin, Texas, as well as in both Mexican cities, with NOy [NO subscript y] emission ratios in Austin < Mexico City < Mexicali., Mexico. Comisión Ambiental Metropolitana, National Science Foundation (U.S.) (Grant ATM-0528227), Molina Center for Energy and the Environment, University of Texas at Austin, Latin American Scholarship Program of American Universities

We present results obtained from a greatly improved version of a previously reported nitrogen dioxide monitor (Anal Chem. 2005, 77, 724-728) that utilizes cavity attenuated phase shift spectroscopy (CAPS). The sensor, which detects the optical absorption of nitrogen dioxide within a 20 nm bandpass centered at 440 nm, comprises a blue light emitting diode, an enclosed stainless steel measurement cell (26 cm length) incorporating a resonant optical cavity of near-confocal design and a vacuum photodiode detector. An analog heterodyne detection scheme is used to measure the phase shift in the waveform of the modulated light transmitted through the cell induced by the presence of nitrogen dioxide within the cell. The sensor, which operates at atmospheric pressure, fits into a 19 in.-rack-mounted instrumentation box, weighs 10 kg, and utilizes 70 W of electrical power with pump included. The sensor response to nitrogen dioxide (calculated as the cotangent of the phase shift) is demonstrated to be linear (r20.9999) within +/- 1 ppb over a range of 0-320 ppb (by volume). The device exhibits a detection limit (3sigma precision) of less than 60 parts per trillion (0.060 ppb) with 10 s integration, a value derived from measurements at NO2 concentration levels of both 0 and 20 ppb; the detection limit improves as the integration time is increased to several hundred seconds. The observed baseline drift is less than +/- 0.5 ppb overthe course of a month. An intercomparison of measurements of ambient NO2 concentrations over several days using this sensor with a quantum cascade laser-based infrared absorption spectrometer and a standard chemiluminescence-based NOx analyzer is presented. The data from the CAPS sensor are highly correlated (r20.99) with the other two instruments. The absolute agreement between the CAPS and each of the two other instruments is within the expected statistical noise associated with the infrared laser-based absorption spectrometer (+/- 0.3 ppb with 10 s sampling) and chemiluminescence analyzer (+/- 0.4 ppb with 60 s averaging). The major limitation concerning accuracy is a direct spectral interference with phototchemically produced 1,2-dicarbonyl species (e.g., glyoxal, methylglyoxal). However, this interference can be readily removed by shifting the detection band to a slightly longer wavelength and ensuring that the lower edge of the detection band is greater than 455 nm.

[1] Photochemically processed urban emissions were characterized at a mountain top location, free from local sources, within the Mexico City Metropolitan Area. Analysis of the Mexico City emission plume demonstrates a strong correlation between secondary organic aerosol and odd oxygen (O3 + NO2). The measured oxygenated-organic aerosol correlates with odd oxygen measurements with an apparent slope of (104–180) μg m−3 ppmv−1 (STP) and r2 > 0.9. The dependence of the observed proportionality on the gas-phase hydrocarbon profile is discussed. The observationally-based correlation between oxygenated organic aerosol mass and odd oxygen may provide insight into poorly understood secondary organic aerosol production mechanisms by leveraging knowledge of gas-phase ozone production chemistry. These results suggest that global and regional models may be able to use the observed proportionality to estimate SOA as a co-product of modeled O3 production until more complete models of SOA formation become available.

We describe a prototype designed for in situ detection of the nitrate radical (NO3) by laser-induced fluorescence (LIF) and of N2O5 by thermal dissociation followed by LIF detection of NO3. An inexpensive 36 mW continuous wave multi-mode diode laser at 662 nm is used to excite NO3 in the B2E'(0000)-- X2A'2(0000) band. Fluorescence is collected from 700 to 750 nm. The prototype has a sensitivity to NO3 of 76 ppt for a 60 s integration with an accuracy of 8%. Although this sensitivity is adequate for studies of N205 in many environments, it is much less sensitive (about 300 times) than expected based on a comparison of previously measured photophysical properties of NO2 and NO3. This implies much stronger nonradiative coupling of electronic states in NO3 than in NO2.

[1] Observations of total alkyl nitrates (ΣANs) were obtained using thermal dissociation-laser-induced fluorescence at La Porte, Texas, from 15 August to 15 September 2000, along with an extensive suite of other nitrogen oxides, hydrocarbons, and O3. The ΣAN mixing ratios ranged as high as 5.2 ppbv. The median midday mixing ratio was 1.2 ppbv, and the median nighttime mixing ratio was 0.26 ppbv. These are higher mixing ratios than the sum of individual nitrates in virtually every prior study. The diurnal variation of ΣANs was similar to that of HNO3 and of total peroxy nitrates, with a peak near 1300 local time (LT) indicating a photochemical source. Mixing ratios decreased rapidly in the afternoon, suggesting that ΣAN deposition is nearly as fast as HNO3 deposition. The observed correlation between O3 and ΣANs has a slope that increases from 29 (R2 = 0.73) ΔOx/ΔΣANs at 0900–1200 LT to 41 (R2 = 0.74) ΔOx/ΔΣANs at 1400–1800 LT. We present calculations constrained by the observed hydrocarbons showing that both the mixing ratio of ΣANs and the correlation of ΣANs with O3 are to be expected on the basis of the branching ratios for alkyl nitrate formation in the RO2 + NO reaction.

[1] We describe measurements of NO2, total peroxy nitrates (ΣPNs), total alkyl nitrates (ΣANs), and HNO3 using thermal dissociation followed by laser-induced fluorescence detection of NO2 at three continental locations. The ΣAN observations are unique and provide novel constraints on atmospheric photochemistry. At a rural site in California, measurements over a full annual cycle show that ΣANs are routinely 10–20% of NOy. At this rural site, at a suburban site in California and an urban site in Houston, Texas, both the absolute concentration of ΣANs and the fraction of the higher oxides of nitrogen (NOz) represented by ΣANs are greater than or equal to values reported in any prior observations. Although the contrast with prior observations is striking, we show that large abundances of ΣANs are consistent with simple chemical models of tropospheric ozone production and with the few prior comprehensive model studies. We also show that ΣANs are a large part, if not all, of the “missing NOy” reported in many prior experiments and emphasize that the ratios of ΣANs/NOz and of O3/ΣANs are especially useful for evaluating chemical models and comparing observations at different sites.

We review our recent results in development of high-precision laser spectroscopic instrumentation using midinfrared quantum cascade lasers (QCLs). Some of these instruments have been directed at mea- surements of atmospheric trace gases where a fractional precision of 10 −3 or better of ambient concentration may be required. Such high precision is needed in measurements of fluxes of stable atmospheric gases and measurements of isotopic ratios. Instruments that are based on thermoelectrically cooled midinfrared QCLs and thermoelectrically cooled detectors have been demonstrated that meet the requirements of high-precision atmospheric measurements, without the need for cryo- gens. We also describe the design of and results from a new dual QCL instrument with a 200-m path-length absorption cell. This instrument has demonstrated 1-s noise of 32 ppt for formaldehyde (HCHO) and 9 ppt for carbonyl sulfide (OCS). C 2010 Society of Photo-Optical Instrumentation Engineers.