New England Air Quality Study Research Articles

The POWER Experiment: Impact of Assimilation of a Network of Coastal Wind Profiling Radars on Simulating Offshore Winds in and above the Wind Turbine Layer

AbstractDuring the summer of 2004 a network of 11 wind profiling radars (WPRs) was deployed in New England as part of the New England Air Quality Study (NEAQS). Observations from this dataset are used to determine their impact on numerical weather prediction (NWP) model skill at simulating coastal and offshore winds through data-denial experiments. This study is a part of the Position of Offshore Wind Energy Resources (POWER) experiment, a Department of Energy (DOE) sponsored project that uses National Oceanic and Atmospheric Administration (NOAA) models for two 1-week periods to measure the impact of the assimilation of observations from 11 inland WPRs. Model simulations with and without assimilation of the WPR data are compared at the locations of the inland WPRs, as well as against observations from an additional WPR and a high-resolution Doppler lidar (HRDL) located on board the Research Vessel Ronald H. Brown (RHB), which cruised the Gulf of Maine during the NEAQS experiment. Model evaluation in the lowest 2 km above the ground shows a positive impact of the WPR data assimilation from the initialization time through the next five to six forecast hours at the WPR locations for 12 of 15 days analyzed, when offshore winds prevailed. A smaller positive impact at the RHB ship track was also confirmed. For the remaining three days, during which time there was a cyclone event with strong onshore wind flow, the assimilation of additional observations had a negative impact on model skill. Explanations for the negative impact are offered.

Radicals in the marine boundary layer during NEAQS 2004: a model study of day-time and night-time sources and sinks

Abstract. This paper describes a modelling study of several HOx and NOx species (OH, HO2, organic peroxy radicals, NO3 and N2O5) in the marine boundary layer. A model based upon the Master Chemical Mechanism (MCM) was constrained to observations of chemical and physical parameters made onboard the NOAA ship R/V Brown as part of the New England Air Quality Study (NEAQS) in the summer of 2004. The model was used to calculate [OH] and to determine the composition of the peroxy radical pool. Modelled [NO3] and [N2O5] were compared to in-situ measurements by Cavity Ring-Down Spectroscopy. The comparison showed that the model generally overestimated the measurements by 30–50%, on average. The model results were analyzed with respect to several chemical and physical parameters, including uptake of NO3 and N2O5 on fog droplets and on aerosol, dry deposition of NO3 and N2O5, gas-phase hydrolysis of N2O5 and reactions of NO3 with NMHCs and peroxy radicals. The results suggest that fog, when present, is an important sink for N2O5 via rapid heterogeneous uptake. The comparison between the model and the measurements were consistent with values of the heterogeneous uptake coefficient of N2O5 (γN2O5)>1×10−2, independent of aerosol composition in this marine environment. The analysis of the different loss processes of the nitrate radical showed the important role of the organic peroxy radicals, which accounted for a significant fraction (median: 15%) of NO3 gas-phase removal, particularly in the presence of high concentrations of dimethyl sulphide (DMS).

Fine aerosol bulk composition measured on WP-3D research aircraft in vicinity of the Northeastern United States – results from NEAQS

Abstract. During the New England Air Quality Study (NEAQS) in the summer of 2004, airborne measurements were made of the major inorganic ions and the water-soluble organic carbon (WSOC) of the submicron (PM1.0) aerosol. These and ancillary data are used to describe the overall aerosol chemical characteristics encountered during the study. Fine particle mass was estimated from particle volume and a calculated density based on measured particle composition. Fine particle organic matter (OM) was estimated from WSOC and a mass balance analysis. The aerosol over the northeastern United States (U.S.) and Canada was predominantly sulfate and associated ammonium, and organic components, although in unique plumes additional ionic components were also periodically above detection limits. In power generation regions, and especially in the Ohio River Valley region, the aerosol tended to be predominantly sulfate (~60% μg μg−1) and apparently acidic, based on an excess of measured anions compared to cations. In all other regions where sulfate concentrations were lower and a smaller fraction of overall mass, the cations and anions were balanced suggesting a more neutral aerosol. In contrast, the WSOC and estimated OM were more spatially uniform and the fraction of OM relative to PM mass was largely influenced by sources of sulfate. The study median OM mass fraction was 40%. Throughout the study region, sulfate and organic aerosol mass were highest near the surface and decreased rapidly with increasing altitude. The relative fraction of organic mass to sulfate was similar throughout all altitudes within the boundary layer (altitude less than 2.5 km), but was significantly higher at altitude layers in the free troposphere (above 2.5 km). A number of distinct biomass burning plumes from fires in Alaska and the Yukon were periodically intercepted, mostly at altitudes between 3 and 4 km. These plumes were associated with highest aerosol concentrations of the study and were largely comprised of organic aerosol components (~60%).

Intercontinental Chemical Transport Experiment Ozonesonde Network Study (IONS) 2004: 2. Tropospheric ozone budgets and variability over northeastern North America

Daily ozone soundings taken from the R/V Ronald H. Brown from 7 July through 11 August 2004 as part of the Intercontinental Chemical Transport Experiment (INTEX) Ozonesonde Network Study (IONS) are used to investigate the vertical structure of ozone over the Gulf of Maine and to characterize variability in sources of tropospheric ozone: stratosphere, regional convection and lightning, advection, and local boundary layer pollution. These soundings were part of a network of twelve IONS (http://croc.gsfc.nasa.gov/intex/ions.html) stations that launched ozonesonde‐radiosonde packages over the United States and maritime Canada during the INTEX/International Consortium for Atmospheric Research on Transport and Transformation (ICARTT)/New England Air Quality Study (NEAQS) project from 1 July to 15 August 2004. Four of the IONS stations were in mid‐Atlantic and northeast United States; four were in southeastern Canada. Although the INTEX/ICARTT goal was to examine pollution influences under stable high‐pressure systems, northeastern North America (NENA) during IONS was dominated by weak frontal systems that mixed aged pollution and stratospheric ozone with ozone from more recent pollution and lightning. These sources are quantified to give tropospheric ozone budgets for individual soundings that are consistent with tracers and meteorological analyses. On average, for NENA stations in July‐August 2004, tropospheric ozone was composed of the following: 10–15% each local boundary layer and regional sources (the latter including that due to lightning‐derived NO) and 20–25% stratospheric ozone, with the balance (∼50%) a mixture of recently advected ozone and aged air of indeterminate origin.

Shipboard multisensor merged wind profiles from the New England Air Quality Study 2004

The New England Air Quality Study (NEAQS) was a regional portion of the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) planned by groups in North America and Europe to develop a better understanding of the factors that shape air quality in their respective regions and the remote North Atlantic. The NOAA research vessel Ronald H. Brown was only one of a number of platforms given the task of monitoring the emissions of aerosol and ozone precursors and the atmosphere in which they reside. Two remote and one in situ sensor were used to measure wind profiles. A radar wind profiler (RWP) permanently deployed on the ship and corrected in real time for ship motion provided continuous hourly profiles at 60‐ and 100‐m vertical resolutions. A high‐resolution Doppler lidar (HRDL) was also operated during the experiment and provided continuous low‐level wind profiles. Rawinsondes were launched 4–6 times daily and provided a detailed profile of winds. Initial results show that the RWP, HRDL, and rawinsonde data compare very well. The ability of HRDL to monitor low‐level winds below the minimum range gate of the RWP, while the RWP wind data extend to a much greater height than can be reached by HRDL, make the two systems complementary. Single merged profiles were generated using the RWP and HRDL data, which in turn were used to calculate trajectories to help better understand the transport of pollutants within the Gulf of Maine.

Evaluation of several PM2.5 forecast models using data collected during the ICARTT/NEAQS 2004 field study

Real‐time forecasts of PM2.5 aerosol mass from seven air quality forecast models (AQFMs) are statistically evaluated against observations collected in the northeastern United States and southeastern Canada from two surface networks and aircraft data during the summer of 2004 International Consortium for Atmospheric Research on Transport and Transformation (ICARTT)/New England Air Quality Study (NEAQS) field campaign. The AIRNOW surface network is used to evaluate PM2.5 aerosol mass, the U.S. EPA STN network is used for PM2.5 aerosol composition comparisons, and aerosol size distribution and composition measured from the NOAA P‐3 aircraft are also compared. Statistics based on midday 8‐hour averages, as well as 24‐hour averages are evaluated against the AIRNOW surface network. When the 8‐hour average PM2.5 statistics are compared against equivalent ozone statistics for each model, the analysis shows that PM2.5 forecasts possess nearly equivalent correlation, less bias, and better skill relative to the corresponding ozone forecasts. An analysis of the diurnal variability shows that most models do not reproduce the observed diurnal cycle at urban and suburban monitor locations, particularly during the nighttime to early morning transition. While observations show median rural PM2.5 levels similar to urban and suburban values, the models display noticeably smaller rural/urban PM2.5 ratios. The ensemble PM2.5 forecast, created by combining six separate forecasts with equal weighting, is also evaluated and shown to yield the best possible forecast in terms of the statistical measures considered. The comparisons of PM2.5 composition with NOAA P‐3 aircraft data reveals two important features: (1) The organic component of PM2.5 is significantly underpredicted by all the AQFMs and (2) those models that include aqueous phase oxidation of SO2 to sulfate in clouds overpredict sulfate levels while those AQFMs that do not include this transformation mechanism underpredict sulfate. Errors in PM2.5 ammonium levels tend to correlate directly with errors in sulfate. Comparisons of PM2.5 composition with the U.S. EPA STN network for three of the AQFMs show that sulfate biases are consistently lower at the surface than aloft. Recommendations for further research and analysis to help improve PM2.5 forecasts are also provided.

Airborne measurements of HCHO and HCOOH during the New England Air Quality Study 2004 using a pulsed quantum cascade laser spectrometer

Atmospheric mixing ratios of formaldehyde and formic acid have been measured from the NOAA WP‐3 aircraft during the New England Air Quality Study (NEAQS) of July and August 2004 using a newly developed quantum cascade laser (QCL) spectrometer operating at a wavelength of 5.6 μm. The laser operates in pulsed mode with thermoelectric cooling. The detection is based on direct absorption in a compact 76‐m multiple pass absorption cell. The laser is swept over a 0.5 cm−1 spectral region containing multiple lines of both HCHO and HCOOH. Absolute concentrations are retrieved by simultaneous spectral fitting routines with a detection limit (2σ) for HCHO of 0.3 parts in 109 (ppbv) with an averaging time of 60 s under stable flight conditions. HCHO mixing ratios in the range from 0.3 to 5 ppb were encountered during flight conditions. Some of the highest mixing ratios of HCHO were observed over heavily vegetated areas of Florida during the test flights where the ratios of HCHO to methacrolein and methyl vinyl ketone, measured by proton transfer mass spectroscopy, are consistent with formaldehyde production by isoprene oxidation. The highest mixing ratios of HCOOH, up to 10 ppbv, were observed in an aged forest fire plume encountered over northern Canada, in which ratios of HCOOH/CO are greater than previous observations, while the ratios of HCHO/CO are less than previous reports from forest fire plumes. Observations of HCHO/CO and HCOOH/CO in urban plumes are indicative of a mixture of sources from direct emissions and secondary oxidation of anthropogenic and biogenic hydrocarbons. The ability to measure both HCHO and HCOOH simultaneously is of value in assessing the oxidation mechanisms of atmospheric hydrocarbons and secondary organic aerosol formation and oxidation.

Reactivity and loss mechanisms of NO3 and N2O5 in a polluted marine environment: Results from in situ measurements during New England Air Quality Study 2002

Concentrations of NO3 and N2O5 were measured using an in situ instrument aboard the NOAA research vessel Ronald H. Brown in the marine boundary layer along the United States east coast as part of the New England Air Quality Study (NEAQS) in the summer of 2002. We analyze the results in terms of the loss partitioning and sink budgets for both of these compounds. Analysis of the data on nights with large N2O5 losses allowed for a determination of its heterogeneous uptake coefficient and gave γ(N2O5) = 0.03 ± 0.02. Reactions of NO3 with terrestrially emitted biogenic volatile organic compounds (isoprene and monoterpenes), advected into the marine boundary layer, and with DMS emitted from the ocean surface were also important. In general, loss of NO3 and N2O5 was rapid, and the partitioning between NO3 and N2O5 losses was roughly equal. Because rapid N2O5 loss consumes NOx at twice the rate of the reaction of NO2 with O3, whereas rapid NO3 loss leads to NOx removal at the same rate, the equal partitioning of losses indicates a nocturnal NOx loss rate of approximately 1.5 times the rate of NO2 + O3. Activation of halogens from the uptake of NO3 and N2O5 on sea salt was calculated to have produced substantial amounts of active Cl on some mornings through the nocturnal formation and sunrise photolysis of ClNO2 if the process proceeded at the rate determined by laboratory studies. However, there was no direct observational evidence to test the magnitude of the predicted source.

Analysis of the isoprene chemistry observed during the New England Air Quality Study (NEAQS) 2002 intensive experiment

Isoprene and its first and second generation photochemical products, methyl vinyl ketone (MVK), methacrolein (MACR), and peroxymethacrylic nitric anhydride (MPAN), were measured off the coast of New England during the 2002 New England Air Quality Study (NEAQS) on board the NOAA Research Vessel Ronald H. Brown. The results of these measurements were analyzed using a simple sequential reaction model that has been used previously to examine regional oxidant chemistry. The highest isoprene impact was observed in air masses that had passed over an area of high isoprene emission WSW of Boston. The relative concentrations of isoprene and its first generation products show that the photochemistry is consistently “older” than the isoprene photochemistry observed at continental sites. The sequential reaction model was also applied to the aldehyde‐PANs (Peroxycarboxylic nitric anhydride) system, and the resulting PPN (peroxypropionic nitric anhydride)/propanal and PAN (peroxyacetic nitric anhydride)/acetaldehyde relationships were consistent with additional sources of PAN in this environment, e.g., isoprene photochemistry. This isoprene source was estimated to result in approximately 1.6 to 4 times more PAN in this environment relative to that produced from anthropogenic VOCs (volatile organic compounds) alone.

Performance and Diagnostic Evaluation of Ozone Predictions by the Eta-Community Multiscale Air Quality Forecast System during the 2002 New England Air Quality Study

A real-time air quality forecasting system (Eta-Community Multiscale Air Quality [CMAQ] model suite) has been developed by linking the National Centers for Environmental Estimation Eta model to the U.S. Environmental Protection Agency (EPA) CMAQ model. This work presents results from the application of the Eta-CMAQ modeling system for forecasting ozone (O3) over the Northeastern United States during the 2002 New England Air Quality Study (NEAQS). Spatial and temporal performance of the Eta-CMAQ model for O3 was evaluated by comparison with observations from the EPA Air Quality System (AQS) network. This study also examines the ability of the model to simulate the processes governing the distributions of tropospheric O3 on the basis of the intensive datasets obtained at the four Atmospheric Investigation, Regional Modeling, Analysis, and Estimation (AIRMAP) and Harvard Forest (HF) surface sites. The episode analysis reveals that the model captured the buildup of O3 concentrations over the northeastern domain from August 11 and reproduced the spatial distributions of observed O3 very well for the daytime (8:00 p.m.) of both August 8 and 12 with most of normalized mean bias (NMB) within [H11006]20%. The model reproduced 53.3% of the observed hourly O3 within a factor of 1.5 with NMB of 29.7% and normalized mean error of 46.9% at the 342 AQS sites.The comparison of modeled and observed lidar O3 vertical profiles shows that whereas the model reproduced the observed vertical structure, it tended to overestimate at higher altitude. The model reproduced 64 –77% of observed NO2 photolysis rate values within a factor of 1.5 at the AIRMAP sites. At the HF site, comparison of modeled and observed O3/nitrogen oxide (NOx) ratios suggests that the site is mainly under strongly NOx-sensitive conditions (>53%). It was found that the modeled lower limits of the O3 production efficiency values (inferred from O3-CO correlation) are close to the observations.

Dominance of organic aerosols in the marine boundary layer over the Gulf of Maine during NEAQS 2002 and their role in aerosol light scattering

Aerosol chemical, physical, and optical measurements were made aboard the NOAA R/V Ronald H. Brown off the coast of New England from July 12 through August 10, 2002, as part of the New England Air Quality Study (NEAQS). Measurements (generally 20 to 100 km from the coast) were made downwind of urban centers (New York City, Boston) and rural areas, and in air masses that had not been in contact with land for several days. On average during NEAQS, 75 ± 8% of the sub‐10 μm aerodynamic diameter dry aerosol mass sampled 18 m above the sea surface was in the sub‐1 μm fraction (size cut at 55% RH). The major submicrometer aerosol components were ammonium sulfate and particulate organic matter (POM, defined here as 1.6 times the mass concentration of organic carbon) comprising more than 92 ± 4% of the total mass. Under northwesterly flow with an average submicrometer total mass concentrations of 11 ± 4.5 μg m−3, POM was the dominant component (68 ± 8%) followed by (NH4)xHySO4 (23 ± 8%), inorganic oxidized material (IOM) (6 ± 4%), and EC (3 ± 1%). Under southwesterly flow with an average submicrometer total mass concentrations of 30 ± 11 μg m−3, (NH4)xHySO4 was the dominant component (54 ± 9%) followed by POM (41 ± 9%), IOM (3 ± 2%), and EC (2 ± 1%). Mie calculations using submicrometer nonrefractory (NR) POM and NR (NH4)xHySO4 + H2O size distributions to calculate submicrometer light scattering (σsp) at a wavelength of 550 nm suggest that POM was a dominant chemical component contributing to aerosol light scattering (haze) during NEAQS 2002, and contributed 60 ± 6 % and 57 ± 11 % to σsp at 55% RH during two pollution episodes off the New England Coast. These results are similar to those from the mid‐Atlantic states during TARFOX but contrary to the long‐term monitoring measurements over the continental northeast United States that show the New England haze is primarily a result of sulfate aerosol.

Regional aerosol properties: Comparisons of boundary layer measurements from ACE 1, ACE 2, Aerosols99, INDOEX, ACE Asia, TARFOX, and NEAQS

Means and variability of aerosol chemical composition and optical properties are compared for the first and second Aerosol Characterization Experiments (ACE 1 and ACE 2), a cruise across the Atlantic (Aerosols99), the Indian Ocean Experiment (INDOEX), the Asian Aerosol Characterization Experiment (ACE Asia), the Tropospheric Aerosol Radiative Forcing Observational Experiment (TARFOX), and the New England Air Quality Study (NEAQS). These experiments were focused either on the remote marine atmosphere (ACE 1) or areas downwind of continental aerosol source regions including western Europe, North America, Africa, India, and Asia. Presented here are size‐segregated concentrations of aerosol mass, sea salt, non‐sea‐salt (nss) SO4=, NH4+, NO3−, dust, organic carbon (OC), elemental carbon (EC), and nss K+, as well as mass ratios that are commonly used to identify aerosol sources and to assess aerosol processing (Cl− to Na+, OC to nss SO4=, EC to total carbon (TC), EC to nss SO4=, nss K+ to EC, Fe to Al, and Si to Al). Optical properties that are compared include size‐segregated scattering, backscattering, and absorption coefficients, and single‐scattering albedo at 550 nm. Size‐segregated mass scattering and mass absorption efficiencies for the total aerosol and mass extinction efficiencies for the dominant chemical components also are compared. In addition, we present the contribution to light extinction by the dominant chemical components for each region. All data are based on shipboard measurements performed at a relative humidity of 55 ± 5%. Scattering coefficients and single‐scattering albedos also are reported at ambient relative humidity (RH) using published values of f(RH). Finally, aerosol optical depths from each region are compared. Identical sampling protocols were used in all experiments in order to eliminate sampling biases and to make the data directly comparable. Major findings include (1) nss SO4= makes up only 16 to 46% of the submicron aerosol mass, which means there is a large and variable fraction of the aerosol that is not sulfate, (2) particulate organic matter (POM) makes up 1 to 51% of the submicron mass, with highest POM mass fractions observed downwind of the NE United States, (3) highest submicron mass fractions of EC and lowest single‐scattering albedos were observed in biomass‐burning plumes from Africa and downwind of the Indian subcontinent, (4) NO3− was found predominantly in the supermicron size range due to the interaction of gas phase oxidized nitrogen species with sea salt aerosol, and (5) mass extinction efficiencies for the individual chemical components were consistent between regions. All data presented are available as auxiliary material.

The Accuracy of Solar Irradiance Calculations Used in Mesoscale Numerical Weather Prediction

In this paper, solar irradiance forecasts made by mesoscale numerical weather prediction models are compared with observations taken during three air-quality experiments in various parts of the United States. The authors evaluated the fifth-generation Pennsylvania State University–National Center for Atmospheric Research (PSU–NCAR) Mesoscale Model (MM5) and the National Centers for Environmental Prediction (NCEP) Eta Model. The observations were taken during the 2000 Texas Air Quality Experiment (TexAQS), the 2000 Central California Ozone Study (CCOS), and the New England Air Quality Study (NEAQS) 2002. The accuracy of the model forecast irradiances show a strong dependence on the aerosol optical depth. Model errors on the order of 100 W m−2 are possible when the aerosol optical depth exceeds 0.1. For smaller aerosol optical depths, the climatological attenuation used in the models yields solar irradiance estimates that are in good agreement with the observations.

Modification, Calibration and a Field Test of an Instrument for Measuring Light Absorption by Particles

A filter-based single-wavelength photometer (Particle Soot Absorption Photometer, PSAP) for measuring light absorption by aerosols was modified to measure at three wavelengths, 467 nm, 530 nm, and 660 nm. The modified and an unmodified photometer were calibrated during the Reno Aerosol Optics Study (RAOS) 2002 against two absorption standards: a photoacoustic instrument and the difference between the extinction and scattering coefficient. This filter-based absorption method has to be corrected for scattering aerosol and transmission changes. A simple function for this was derived from the calibration experiment as a function of transmission and single-scattering albedo. For an unmodified PSAP at typical atmospheric absorption coefficients the algorithm yields about 5–7% lower absorption coefficients than does the usually used method. The three-wavelength PSAP was used for atmospheric measurements both during RAOS and during the New England Air Quality Study (NEAQS).

Quantification of ozone formation metrics at Thompson Farm during the New England Air Quality Study (NEAQS) 2002

Several metrics have been estimated to investigate preliminarily ozone (O3) formation dynamics at the University of New Hampshire Atmospheric Observing Station at Thompson Farm, which is associated with the Atmospheric Investigation, Regional Modeling, Analysis, and Prediction program. This paper focuses on the August time frame of the New England Air Quality Study 2002. These metrics include instantaneous and net O3 production rate (P(O3)), instantaneous and average O3 production efficiency (OPE), and hydrocarbon and carbon monoxide (CO) reactivity. In general, the seacoast region of New Hampshire experiences low P(O3) values compared to other continental locations. Use of a photochemical model yields a range of instantaneous values of 0.2 to 8.5 ppbv h−1 and a range of net values of 0.2 to 8.3 ppbv h−1. Corresponding calculations for instantaneous OPE range from 0.2 to 2.4, with regression techniques yielding average OPE values of 7.7 and 9.7. These high regression values, the mixing ratios of NOy, and the concentration ratios of O3 to NOz indicate a NOx‐limited atmosphere. Total hydrocarbon and CO reactivity ranges from 0.9 to 20.2 s−1. In conjunction with back trajectory analysis the metric values calculated for this location indicate that strong peaks in O3 during this period are most likely a result of mixing of processed, O3‐rich air masses rather than direct in situ chemical formation.

Ship‐based nitric acid measurements in the Gulf of Maine during New England Air Quality Study 2002

Gas phase nitric acid (HNO3) was measured at 5‐min resolution on board the National Oceanographic and Atmospheric Administration (NOAA) research vessel Ronald H. Brown during the second leg (29 July to 10 August) of the New England Air Quality Study (NEAQS) 2002 cruise. A primary objective of the cruise was to improve understanding of the oxidation of NOx in, and removal of the oxidation products from, the polluted marine boundary layer east of northeastern North America. For the first 9 days of this leg the ship remained north of Cape Cod, and the cruise track did not extend much farther north than the New Hampshire‐Maine border. During this period, HNO3 averaged 1.1 ppb and accounted for 19% of total reactive nitrogen oxides (measured NOy). On all days, peak HNO3 mixing ratios were observed in the early afternoon (average 2.3 ppb), at levels twofold to fourfold higher than the minima around sunrise and sunset. In these daytime peaks, HNO3/NOy averaged 28%. There were secondary nighttime peaks of HNO3 (0.9 ppb average), when HNO3 accounted for 16% of total reactive nitrogen oxides. This pronounced diurnal pattern confirms that production, and subsequent deposition, of HNO3 in the polluted marine boundary layer downwind of New England removes a significant fraction of the NOx exported to the atmosphere over the Gulf of Maine. Nitric acid was correlated with O3, particularly during the early afternoon interval when both molecules reached maximum mixing ratios (R2 = 0.66). The ozone production efficiency (OPE) inferred from the slope (10 ppb O3/ppb HNO3) was similar to the OPE of 9 estimated at the Atmospheric Investigation, Regional Modeling, Analysis and Prediction (AIRMAP) Thompson Farm station in coastal New Hampshire during the study period.

Nighttime removal of NOx in the summer marine boundary layer

The nitrate radical, NO3, and dinitrogen pentoxide, N2O5, are two important components of nitrogen oxides that occur predominantly at night in the lower troposphere. Because a large fraction of NO2 reacts to form NO3 and N2O5 during the course of a night, their fate is an important determining factor to the overall fate of NOx (=NO and NO2). As a comprehensive test of nocturnal nitrogen oxide chemistry, concentrations of O3, NO, NO2, NO3, N2O5, HNO3 and a host of other relevant compounds, aerosol abundance and composition, and meteorological conditions were measured in the marine boundary layer from the NOAA research vessel Ronald H. Brown off the East Coast of the United States as part of the New England Air Quality Study (NEAQS) during the summer of 2002. The results confirm the prominent role of NO3 and N2O5 in converting NOx to HNO3 at night with an efficiency on par with daytime photochemical conversion. The findings demonstrate the large role of nighttime chemistry in determining the NOx budget and consequent production of ozone.

Validation of proton transfer reaction‐mass spectrometry (PTR‐MS) measurements of gas‐phase organic compounds in the atmosphere during the New England Air Quality Study (NEAQS) in 2002

Organic compounds were measured by proton transfer reaction‐mass spectrometry (PTR‐MS) on board the National Oceanic and Atmospheric Administration's research ship Ronald H. Brown during the New England Air Quality Study (NEAQS) in July and August of 2002. PTR‐MS has the potential to measure many important organic species with a fast time response, but its validity has not been proven sufficiently. The results obtained by PTR‐MS during NEAQS were compared with those from (oxygenated) hydrocarbon measurements by gas chromatography/mass spectrometry (GC‐MS), peroxyacyl nitrate measurements by gas chromatography/electron capture detection, and carboxylic acid measurements by mist chamber/ion chromatography. The PTR‐MS and GC‐MS data for methanol, acetonitrile, acetone, isoprene, benzene, and toluene agreed within the measurement uncertainties. The comparison for C8 aromatics and acetaldehyde was less quantitative due to calibration inaccuracies. In addition, PTR‐MS measured the sum of methyl vinyl ketone and methacrolein at 71 amu, the sum of C9 aromatics at 121 amu, and the sum of monoterpenes at 81 and 137 amu. The PTR‐MS signal at 61 amu was found to correlate well with data for acetic acid. The signal at 73 amu correlated reasonably well with methyl ethyl ketone data, but the quantitative disagreement suggested interference from other species, possibly methyl glyoxal. The signal at 77 amu correlated well with data for peroxyacetyl nitrate, and the sensitivity inferred from the field data agreed within 30% with the results from laboratory calibrations. Finally, the signal at 105 amu was attributed to styrene and peroxy isobutyryl nitrate. These results prove that many important organic species can be measured accurately and with a fast response time by PTR‐MS.