Nitryl chloride (ClNO2) is produced at night by reactions of dinitrogen pentoxide (N2O5) on chloride containing surfaces. ClNO2 is photolyzed during the morning hours after sunrise to liberate highly reactive chlorine atoms (Cl center dot). This chemistry takes place primarily in polluted environments where the concentrations of N2O5 precursors (nitrogen oxide radicals and ozone) are high, though it likely occurs in remote regions at lower intensities. Recent field measurements have illustrated the potential importance of ClNO2 as a daytime Cl center dot source and a nighttime NOx reservoir. However, the fate of the Cl center dot and the overall impact of ClNO2 on regional photochemistry remain poorly constrained by measurements and models. To this end, we have incorporated ClNO2 production, photolysis, and subsequent Cl center dot reactions into an existing master chemical mechanism (MCM version 3.2) box model framework using observational constraints from the CalNex 2010 field study. Cl center dot reactions with a set of alkenes and alcohols, and the simplified multiphase chemistry of N2O5, ClNO2, HOCl, ClONO2, and Cl-2, none of which are currently part of the MCM, have been added to the mechanism. The presence of ClNO2 produces significant changes to oxidants, ozone, and nitrogen oxide partitioning, relative to model runs excluding ClNO2 formation. From a nighttime maximum of 1.5 ppbv ClNO2, the daytime maximum Cl center dot concentration reaches 1x10(5) atoms cm(-3) at 07:00 model time, reacting mostly with a large suite of volatile organic compounds (VOC) to produce 2.2 times more organic peroxy radicals in the morning than in the absence of ClNO2. In the presence of several ppbv of nitrogen oxide radicals (NOx = NO+NO2), these perturbations lead to similar enhancements in hydrogen oxide radicals (HOx = OH+HO2). Neglecting contributions from HONO, the total integrated daytime radical source is 17% larger when including ClNO2, which leads to a similar enhancement in integrated ozone production of 15 %. Detectable levels (tens of pptv) of chlorine containing organic compounds are predicted to form as a result of Cl center dot addition to alkenes, which may be useful in identifying times of active Cl center dot chemistry.

Atmospheric black carbon (BC) absorbs solar radiation, and exacerbates global warming through exerting positive radiative forcing (RF). However, the contribution of BC to ongoing changes in global climate is under debate. Anthropogenic BC emissions, and the resulting distribution of BC concentration, are highly uncertain. In particular, long-range transport and processes affecting BC atmospheric lifetime are poorly understood. Here we discuss whether recent assessments may have overestimated present-day BC radiative forcing in remote regions. We compare vertical profiles of BC concentration from four recent aircraft measurement campaigns to simulations by 13 aerosol models participating in the AeroCom Phase II intercomparison. An atmospheric lifetime of BC of less than 5 days is shown to be essential for reproducing observations in remote ocean regions, in line with other recent studies. Adjusting model results to measurements in remote regions, and at high altitudes, leads to a 25% reduction in AeroCom Phase II median direct BC forcing, from fossil fuel and biofuel burning, over the industrial era. The sensitivity of modelled forcing to BC vertical profile and lifetime highlights an urgent need for further flight campaigns, close to sources and in remote regions, to provide improved quantification of BC effects for use in climate policy.

Black carbon (BC) mass emission factors (EFBC; g BC (kg fuel)(-1)) from a variety of ocean-going vessels have been determined from measurements of BC and carbon dioxide (CO2) concentrations in ship plumes intercepted by the R/V Atlantis during the 2010 California Nexus (CalNex) campaign. The ships encountered were all operating within 24 nautical miles of the California coast and were utilizing relatively low sulphur fuels (average fuel sulphur content of 0.4%, 0.09% and 0.03% for vessels operating slow-speed, medium-speed and high-speed diesel engines, respectively). Black carbon concentrations within the plumes, from which EFBC values are determined, were measured using four independent instruments: a photoacoustic spectrometer and a particle soot absorption photometer, which measure light absorption, and a single particle soot photometer and soot particle aerosol mass spectrometer, which measure the mass concentration of refractory BC directly. These measurements have been used to assess the level of agreement between these different techniques for the determination of BC emission factors from ship plumes. Also, these measurements greatly expand upon the number of individual ships for which BC emission factors have been determined during real-world operation. The measured EFBC's have been divided into vessel type categories and engine type categories, from which averages have been determined. The geometric average EFBC (excluding outliers) determined from over 71 vessels and 135 plumes encountered was 0.31 +/- 0.31 gBC (kg fuel)(-1), where the standard deviation represents the variability between individual vessels. The most frequent engine type encountered was the slow-speed diesel (SSD), and the most frequent SSD vessel type was the cargo ship sub-category. Average and median EFBC values from the SSD category are compared with previous observations from the Texas Air Quality Study (TexAQS) in 2006, during which the ships encountered were predominately operating on high-sulphur fuels (average fuel sulphur content of 1.6 %). There is a statistically significant difference between the EFBC values from CalNex and TexAQS for SSD vessels and for the cargo and tanker ship types within this engine category. The CalNex EFBC values are lower than those from TexAQS, suggesting that operation on lower sulphur fuels is associated with smaller EFBC values.

Emissions factors (EFs) for gas and sub-micron particle-phase species were measured in intercepted plumes as a function of vessel speed from an underway research vessel, the NOAA ship Miller Freeman, operating a medium-speed diesel engine on low-sulfur marine gas oil (fuel sulfur content similar to 0.1% by weight). The low-sulfur fuel in use conforms to the MARPOL fuel sulfur limit within emission control areas set to take effect in 2015 and to California-specific limits set to take effect in 2014. For many of the particle-phase species, EFs were determined using multiple measurement methodologies, allowing for an assessment of how well EFs from different techniques agree. The total sub-micron PM (PM1) was dominated by particulate black carbon (BC) and particulate organic matter (POM), with an average POM/BC ratio of 1.3. Consideration of the POM/BC ratios observed here with literature studies suggests that laboratory and in-stack measurement methods may overestimate primary POM EFs relative to those observed in emitted plumes. Comparison of four different methods for black carbon measurement indicates that careful attention must be paid to instrument limitations and biases when assessing EFBC. Particulate sulfate (SO42-) EFs were extremely small and the particles emitted by Miller Freeman were inefficient as cloud condensation nuclei (CCN), even at high super saturations, consistent with the use of very low-sulfur fuel and the overall small emitted particle sizes. All measurement methodologies consistently demonstrate that the measured EFs (fuel mass basis) for PM1 mass, BC and POM decreased as the ship slowed. Particle number EFs were approximately constant across the speed change, with a shift towards smaller particles being emitted at slower speeds. Emissions factors for gas-phase CO and formaldehyde (HCHO) both increased as the vessel slowed, while EFs for NOx decreased and SO2 EFs were approximately constant.

Natural gas production is associated with emissions of several trace gases, some of them classified as air toxics. While volatile organic compounds (VOCs) have received much attention, hydrogen sulfide (H2S) can also be of concern due to the known health impacts of exposure to this hazardous air pollutant. Here, we present quantitative, fast time-response measurements of H2S using protontransfer-reaction mass-spectrometry (PTR-MS) instruments. An ultra-light-weight PTR-MS (ULW-PTR-MS) in a mobile laboratory was operated for measurements of VOCs and H2S in a gas and oil field during the Uintah Basin Winter Ozone Study (UBWOS) 2012 campaign. Measurements of VOCs and H2S by a PTR-MS were also made at the Horse Pool ground site in the Uintah Basin during UBWOS 2013. The H2S measurement by PTR-MS is strongly humidity dependent because the proton affinity of H2S is only slightly higher than that of water. The H2S sensitivity of PTR-MS ranged between 0.6-1.4 ncps ppbv-1 during UBWOS 2013. We compare the humidity dependence determined in the laboratory with in-field calibrations and determine the H2S mixing ratios for the mobile and ground measurements. The PTR-MS measurements at Horse Pool are evaluated by comparison with simultaneous H2S measurements using a PTR time-of-flight MS (PTR-ToF-MS) and a Picarro cavity ring down spectroscopy (CRDS) instrument for H2S/CH4. On average 0.6 +/- 0.3 ppbv H2S was present at Horse Pool during UBWOS 2013. The correlation between H2S and methane enhancements suggests that the source of H2S is associated with oil and gas extraction in the basin. Significant H2S mixing ratios of up to 9 ppmv downwind of storage tanks were observed during the mobile measurements. This study suggests that H2S emissions associated with oil and gas production can lead to short-term high levels close to point sources, and elevated background levels away from those sources. In addition, our work has demonstrated that PTR-MS can make reliable measurements of H2S at levels below 1 ppbv.

A particle-phase relative rates technique is used to investigate the heterogeneous reaction between OH radicals and tris-2-butoxyethyl phosphate (TBEP) at 298 K by combining aerosol time-of-flight mass spectrometry (C-ToF-MS) data and positive matrix factor (PMF) analysis. The derived second-order rate constants (k(2)) for the heterogeneous loss of TBEP is (4.44 +/- 0.45) x 10(-12) cm(3) molecule(-1) s(-1), from which an approximate particle-phase lifetime was estimated to be 2.6 (2.3-2.9) days. However, large differences in the rate constants for TBEP relative to a reference compound were observed when comparing internally and externally mixed TBEP/organic particles, and upon changes in the RH. The heterogeneous degradation of TBEP was found to be depressed or enhanced depending upon the particle mixing state and phase, highlighting the complexity of heterogeneous oxidation in the atmosphere. The effect of gas-particle partitioning on the estimated overall lifetime (gas C particle) for several organophosphate esters (OPEs) was also examined through the explicit modeling of this process. The overall atmospheric lifetimes of TBEP, tris-2-ethylhexyl phosphate (TEHP) and tris-1,3-dichloro-2-propyl phosphate (TDCPP) were estimated to be 1.9, 1.9 and 2.4 days respectively, and are highly dependent upon particle size. These results demonstrate that modeling the atmospheric fate of particle-phase toxic compounds for the purpose of risk assessment must include the gas-particle partitioning process, and in the future include the effect of other particulate components on the evaporation kinetics and/or the heterogeneous loss rates.

Understanding of the atmosphere/forest canopy exchange of volatile organic compounds (VOCs) requires insight into the deposition, emission, and chemical reactions of VOCs below the canopy. Between 18 July and 9 August 2009, VOCs were measured with proton-transfer-reaction mass spectrometry (PTR-MS) at six heights between 1 and 6 m beneath a 23 m high mixed-forest canopy. Measured VOCs included methanol, isoprene, acetone, methacrolein and methyl vinyl ketone (MACR + MVK), monoterpenes, and sesquiterpenes. There are pronounced differences in the behaviour of isoprene and its by-products and that of the terpenes. Non-terpene mixing ratios increase with height, suggesting predominantly downward fluxes. In contrast, the terpene mixing ratios decrease with height, suggesting upward fluxes. A 1-D canopy model was used to compare results to measurements with and without surface deposition of isoprene and MACR + MVK and emissions of monoterpenes and sesquiterpenes. Results suggest deposition velocities of 2.7 mm s(-1) for isoprene and 1.2 mm s(-1) for MACR + MVK and daytime surface emission rates of 63 mu g m(-2) h(-1) for monoterpenes. The modelled isoprene surface deposition is approximately 2% of the canopy-top isoprene emissions and the modelled emissions of monoterpenes comprise approximately 15 to 27% of the canopy-top monoterpene emissions to the atmosphere. These results suggest that surface monoterpene emissions are significant for forest canopy/atmosphere exchange for this mixed-forest location and surface uptake is relatively small for all the species measured in this study.

In the atmosphere, volatile organic compounds such as glyoxal can partition into aqueous droplets containing significant levels of inorganic salts. Upon droplet evaporation, both the organics and inorganic ions become highly concentrated, accelerating reactions between them. To demonstrate this process, we investigated the formation of organo-nitrogen and light absorbing materials in evaporating droplets containing glyoxal and different ammonium salts including (NH4)(2)SO4, NH4NO3, and NH4Cl. Our results demonstrate that evaporating glyoxal-(NH4)(2)SO4 droplets produce light absorbing species on a time scale of seconds, which is orders of magnitude faster than observed in bulk solutions. Using aerosol mass spectrometry, we show that particle-phase organics with high N:C ratios were formed when ammonium salts were used, and that the presence of sulfate ions promoted this chemistry. Since sulfate can also significantly enhance the Henry's law partitioning of glyoxal, our results highlight the atmospheric importance of such inorganic organic interactions in aqueous phase aerosol chemistry.

Gas-phase acids in light duty diesel (LDD) vehicle exhaust were measured using chemical ionization mass spectrometry (CIMS). Fuel based emission factors (EF) and NOx ratios for these species were determined under differing steady state engine operating conditions. The derived HONO and HNO3 EFs agree well with literature values, with HONO being the single most important acidic emission. Of particular importance is the quantification of the EF for the toxic species, isocyanic acid (HNCO). The emission factors for HNCO ranged from 0.69 to 3.96 mg kg(fuel)(-1), and were significantly higher than previous biomass burning emission estimates. Further ambient urban measurements of HNCO demonstrated a clear relationship with the known traffic markers of benzene and toluene, demonstrating for the first time that urban commuter traffic is a source of HNCO. Estimates based upon the HNCO-benzene relationship indicate that upward of 23 tonnes of HNCO are released annually from commuter traffic in the Greater Toronto Area, far exceeding the amount possible from LDD alone. Nationally, 250 to 770 tonnes of HNCO may be emitted annually from on-road vehicles, likely representing the dominant source of exposure in urban areas, and with emissions comparable to that of biomass burning.

Jacobson argues that our statement that ``many climate models may overestimate warming by BC'' has not been demonstrated. Jacobson challenges our results on the basis that we have misinterpreted some model results, omitted optical focusing under high relative humidity conditions and by involatile components, and because our measurements consist of only two locations over short atmospheric time periods. We address each of these arguments, acknowledging important issues and clarifying some misconceptions, and stand by our observations. We acknowledge that Jacobson identified one detail in our experimental technique that places an additional constraint on the interpretation of our observations and reduces somewhat the potential consequences of the stated implications.

Gaseous elemental mercury (GEM) in the atmosphere was measured during an oceanographic cruise in coastal waters between San Diego and San Francisco, California during the CalNex 2010 campaign. The goal of the measurements was to quantify GEM in the various environments that the ship encountered, from urban outflow, the Port of Long Beach and associated shipping lanes, coastal waters affected by upwelling, the San Francisco Bay, and the Sacramento ship channel. Mean GEM for the whole cruise was 1.41 +/- 0.20 ng m(-3), indicating that background concentrations were predominantly observed. The ship's position was most often in waters off the coast of Los Angeles (74% of time with latitude <34.3 degrees N) and mean GEM for this section was not significantly (P > 0.05) higher than the whole cruise mean. South of 34.3 degrees N, GEM was observed to vary diurnally and as a function of wind direction, displaying significantly higher concentrations at night and in the morning associated with general transport from the land to the sea. GEM and CO concentrations were positively correlated with a slope of 0.0011 ng m(-3) ppbv(-1) (1.23 x 10(-7) mol mol(-1)) during periods identified as ``Los Angeles urban outflow'', which given the inventoried CO emissions for the region, suggests a larger source of GEM than is accounted for by the inventory. The timing of the diel maximum in GEM (9:00 local time) was intermediate between the maxima of CO and NO2 (6:00) and that of NO and SO2 (10:00-12:00), suggesting that a mixture of urban and industrial sources were contributing to GEM. There was no observable postsunrise dip in GEM concentrations due to reaction with atomic chlorine in the polluted coastal atmosphere. On three occasions, significantly higher GEM concentrations were observed while in the Port of Long Beach (similar to 7 ng m(-3)), and analyses of wind directions, ratios of GEM with other copollutants, and the composition of single particles, suggest that these plumes originated from the local waste incinerator in the Port area. A plume encounter from a large cargo ship allowed for the estimation of a mass-based emission factor for GEM (0.05 +/- 0.01 mg kg(-1) fuel burned). GEM enhancements observed in the Carquinez Straits, were lower than expected based on the observed NOx/SO2 ratios in the plumes and emissions inventories of the nearest oil refineries. In a region north of Monterey Bay known for upwelling, GEM in the air was positively correlated with dimethyl sulfide (DMS) in seawater and in the air. Using the observed GEM/DMS(g) relationship and the calculated mean DMS ocean-atmosphere flux for the cruise, an ocean-atmosphere flux of GEM of 0.017 +/- 0.009 mu mol m(-2) d(-1) was estimated. This flux was on the upper end of previously reported GEM ocean-atmosphere fluxes and should be verified with further measurements of Hg species in seawater and air. Citation: Weiss-Penzias, P. S., E. J. Williams, B. M. Lerner, T. S. Bates, C. Gaston, K. Prather, A. Vlasenko, and S. M. Li (2013), Shipboard measurements of gaseous elemental mercury along the coast of Central and Southern California. J. Geophys. Res. Atmos., 118, 208-219, doi: 10.1029/2012JD018463.

The redox activity of diesel exhaust particles (DEP) collected from a light-duty diesel passenger car engine was examined using the dithiothreitol (DTT) assay. DEP was highly redox-active, causing DTT to decay at a rate of 23-61 pmol min(-1) mu g(-1) of particle used in the assay, which was an order of magnitude higher than ambient coarse and fine particulate matter (PM) collected from downtown Toronto. Only 2-11% of the redox activity was in the water-soluble portion, while the remainder occurred at the black carbon surface. This is in contrast to redox-active secondary organic aerosol constituents, in which upward of 90% of the activity occurs in the water-soluble fraction. The redox activity of DEP is not extractable by moderately polar (methanol) and nonpolar (dichloromethane) organic solvents, and is hypothesized to arise from redox-active moieties contiguous with the black carbon portion of the particles. These measurements illustrate that ``Filterable Redox Cycling Activity'' may therefore be useful to distinguish black carbon-based oxidative capacity from water-soluble organic-based activity. The difference in chemical environment leading to redox activity highlights the need to further examine the relationship between activity in the DTT assay and toxicology measurements across particles of different origins and composition.

A large oxygenated organic uptake to aerosols was observed when exposing ambient urban air to inorganic acidic and non-acidic sulfate seed aerosol. For non-acidic seed aerosol the uptake was attributed to the direct dissolution of primary vehicle exhaust gases into the aqueous aerosol fraction, and was correlated to the initial seed sulphate mass. The uptake of primary oxygenated organic gases to aerosols in this study represents a significant amount of organic aerosol (OA) that may be considered primary when compared to that reported for primary organic aerosol (POA), but is considerably more oxygenated (O : C similar to 0.3) than traditional POA. Consequently, a fraction of measured ambient oxygenated OA, which correlates with secondary sulphate, may in fact be of a primary, rather than secondary source. These results represent a new source of oxygenated OA on neutral aerosol and imply that the uptake of primary organic gases will occur in the ambient atmosphere, under dilute conditions, and in the presence of pre-existing SO4 aerosols which contain water. Conversely, under acidic seed aerosol conditions, oligomer formation was observed with the uptake of organics being enhanced by a factor of three or more compared to neutral aerosols, and in less than 2 min, representing an additional source of SOA to the atmosphere. This resulted in a trajectory in Van Krevelen space towards higher O : C (slope similar to -1.5), despite a lack of continual gas-phase oxidation in this closed system. The results demonstrate that high molecular weight species will form on acidic aerosols at the ambient level and mixture of organic gases, but are otherwise unaffected by subsequent aerosol neutralization, and that aerosol acidity will affect the organic O : C via aerosolphase reactions. These two processes, forming oxygenated POA under neutral conditions and SOA under acidic conditions can contribute to the total ambient OA mass and the evolution of ambient aerosol O : C ratios. This may be important for properly representing organic aerosol O: C ratios in air quality and climate models.

Although black carbon (BC) is one of the key atmospheric particulate components driving climate change and air quality, there is no agreement on the terminology that considers all aspects of specific properties, definitions, measurement methods, and related uncertainties. As a result, there is much ambiguity in the scientific literature of measurements and numerical models that refer to BC with different names and based on different properties of the particles, with no clear definition of the terms. The authors present here a recommended terminology to clarify the terms used for BC in atmospheric research, with the goal of establishing unambiguous links between terms, targeted material properties and associated measurement techniques.

Atmospheric gaseous and size-segregated particle samples were collected from urban Guangzhou at the heights of 100 and 150 m above the ground in daytime and at night in August and December 2010, and were analyzed for polycyclic aromatic hydrocarbons (PAHs). Particulate PAHs were more abundant at night than in daytime, and significantly higher in winter than in summer. The observed vertical, diurnal, and seasonal variability in the occurrences of PAH were attributed to varying meteorological conditions and atmospheric boundary layers. More than 60% of the particulate PAHs were contained in particles in the accumulation mode with an aerodynamic diameter (D-p) in the range of 0.1-1.8 mu m. Different mass transfer velocities by volatilization and condensation are considered the main causes for the different particle size distributions among individual PAHs, while combustion at different temperatures and atmospheric transport were probable causes of the observed seasonal variation in the size distribution of PAHs. Based on the modeled size-dependent dry deposition velocities, daily mean dry deposition fluxes of particulate PAHs ranged from 604 to 1190 ng m(-2) d(-1), with PAHs in coarse particles (D-p > 1.8 mu m) accounting for 55-95% of the total fluxes. In addition, gaseous PAHs were estimated to contribute 0.6-3.1% to the total dry deposition fluxes if a conservative dry deposition velocity for gaseous species (2 x 10(-4) m s(-1)) were used. Finally, disequilibrium phase partitioning, meteorological conditions and atmospheric transport were regarded as the main reasons for the variances in dry deposition velocities of individual PAHs. (C) 2012 Elsevier Ltd. All rights reserved.

This paper presents a study of the evolution of particles and gases downwind of a highway, with a focus on the diurnal variation of pollutant gradients and its controlling variables. A mobile laboratory was used to measure the concentration gradients of ultra-fine particles (UFP), black carbon (BC), CO2, NO, and NO2 at varying distances up to 850 m from a major highway. The horizontal distributions of pollutants show a strong diurnal pattern. Results suggest that the horizontal gradients are predominantly influenced by traffic levels, friction velocity, and atmospheric stability. The results were compared to a dispersion model, which showed good agreement with the measurements and was able to qualitatively capture the observed diurnal cycles. Emission rates [g km(-1)] calculated from the model fits are within 10% of the Mobile 6.2C inventory for CO2 and demonstrate good agreement for NOx, but are higher than the inventory by a factor between 2.0 and 5.9 for black carbon. Hourly NOx emission rates correlate with the fraction of heavy-duty vehicles in the total fleet and agree with inventory values based on maximum vehicle emission rates. Crown Copyright (C) 2012 Published by Elsevier Ltd. All rights reserved.

In August and September of 2010, measurements of turbulent fluxes and turbulent kinetic energy were made on highways in the Toronto area (Ontario, Canada). In situ turbulence measurements were made with a mobile laboratory while driving on the highway with traffic. Results demonstrate that the turbulent kinetic energy (TKE) spectrum is significantly enhanced on and near the highway by traffic for frequencies above 0.015 Hz. The decay of TKE with distance behind vehicles is well approximated by power-law curves. The strongest increase in TKE is seen while following heavy-duty trucks, primarily for frequencies above 0.7 Hz. From these results, a parameterization of on-road TKE enhancement is developed that is based on vehicle type and traffic-flow rate. TKE with distance downwind of the highway also decays following a power law. The enhancement of roadside TKE is shown to be strongly dependent on traffic flow. The effect of vehicle-induced turbulence on vertical mixing was studied by comparing parameterized TKE enhancement with the typical TKE predictions from the Global Environmental Multiscale weather forecast to predict the potential increase in vertical diffusion that results from highway traffic. It is demonstrated that this increase in TKE by traffic may be locally significant, especially in the early morning.

The magnitude and sources of chlorine atoms in marine air remain highly uncertain but have potentially important consequences for air quality in polluted coastal regions. We made continuous measurements of ambient ClNO2 and Cl-2 concentrations from May 15 to June 8 aboard the Research Vessel Atlantis during the CalNex 2010 field study. In the Los Angeles region, ClNO2 was more ubiquitous than Cl-2 during most nights of the study period. ClNO2 and Cl-2 ranged from detection limits at midday to campaign maximum values at night reaching 2100 and 200 pptv, respectively. The maxima were observed in Santa Monica Bay when sampling the Los Angeles urban plume. Cl-2 at times appeared well correlated with ClNO2, but at other times, there was little to no correlation implying distinct and varying sources. Well-confined Cl-2 plumes were observed, largely independent of ClNO2, providing support for localized industrial emissions of reactive chlorine. Observations of ClNO2, Cl-2, and HCl are used to constrain a simple box model that predicts their relative importance as chlorine atom sources in the polluted marine boundary layer. In contrast to the emphasis in previous studies, ClNO2 and HCl are dominant primary chlorine atom sources for the Los Angeles basin.

The sea breeze/land breeze diurnal circulation within the Los Angeles Basin and adjacent waters transports marine air into the basin during the day and urban air to Santa Monica Bay during the night. Nitryl chloride, ClNO2 is a nocturnal trace gas formed from the heterogeneous reaction of dinitrogen pentaoxide (N2O5) with chloride containing aerosol. Its photolysis after sunrise produces atomic chlorine radicals and regenerates NO2, both of which may increase ozone production. Mixing of the chloride source from marine sea salt with the urban NOx source in Los Angeles provides conditions ideal for the production of ClNO2. This paper presents an analysis using a wind profiler on the coast and measurements of ClNO2 and its precursors made from both ship and aircraft to assess the prevailing meteorological conditions important for ClNO2 production in this region, with a particular focus on the production over water within the land breeze phase of the circulation. A box model is used to calculate an upper limit to the amount of ClNO2 capable of being produced strictly over Santa Monica Bay during the land breeze. On three out of the four nights of ClNO2 measurements in Santa Monica Bay, the ClNO2 exceeds the upper limit calculated using the box model and shows that the majority of the ClNO2 is produced over the city and transported to Santa Monica Bay by the land breeze. This ClNO2 transport suggests the sea breeze more efficiently transports aerosol chloride inland than land breeze transports NOx offshore.

Measurements of black carbon (BC) with a high-sensitivity laser-induced incandescence (HS-LII) instrument and a single particle soot photometer (SP2) were conducted upwind, downwind, and while driving on a highway dominated by gasoline vehicles. The results are used with concurrent CO2 measurements to derive fuel-based BC emission factors for real-world average fleet and heavy-duty diesel vehicles separately. The derived emission factors from both instruments are compared, and a low SP2 bias (relative to the HS-LII) is found to be caused by a BC mass mode diameter less than 75 nm, that is most prominent with the gasoline fleet but is not present in the heavy-duty diesel vehicle exhaust on the highway. Results from both the LII and the SP2 demonstrate that the BC emission factors from gasoline vehicles are at least a factor of 2 higher than previous North American measurements, and a factor of 9 higher than currently used emission inventories in Canada, derived with the MOBILE 6.2C model. Conversely, the measured BC emission factor for heavy-duty diesel vehicles is in reasonable agreement with previous measurements. The results suggest that greater attention must be paid to black carbon from gasoline engines to obtain a full understanding of the impact of black carbon on air quality and climate and to devise appropriate mitigation strategies.