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 ~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.

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 g BC (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.

Nitryl Chloride (ClNO2) mixing ratios above 1 ppbv have been measured off the coast of Southeast Texas ClNO2 formation the result of heterogeneous N2O5 uptake on chloride-containing aerosols has a significant Impact on oxidant formation for the Houston area This work reports on the modeling of ClNO2 formation and describes the sensitivity of ClNO2 formation to key parameters Model sensitivity analyses found that (1) Chloride availability limits the formation of nitryl chloride at ground level but not aloft (2) When excess particulate chloride was assumed to be present at ground level through sea salt ClNO2 concentrations increased in some locations by a factor of 13 as compared to cases where sea salt chloride was assumed to be limited (3) Inland formation of ClNO2 seems feasible based on chloride availability and could have a large impact on total ClNO2 formed in the region and (4) ClNO2 formation is quite sensitive to the assumed yield of ClNO2 from N2O5 uptake These results demonstrate that there is a need for further field studies to better understand the geographic extent of ClNO2 formation and the atmospheric conditions which control partitioning of chloride into the particle phase In addition this work examined the role of ClNO2 in the cycling of chlorine between chloride and reactive chlorine radicals The modeling indicated that the majority of reactive chlorine in Texas along the Gulf coast is cycled through ClNO2 demonstrating the importance of including ClNO2 into photochemical models for this region Published by Elsevier Ltd

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).

The air quality and climate forcing impacts of atmospheric aerosols in a metropolitan region depend on the amount, composition, and size of the aerosol transported into the region; the input and removal of aerosols and aerosol precursors within the region; and the subsequent chemical processing in the atmosphere. These factors were studied in the Houston‐Galveston‐Gulf of Mexico region, aboard the NOAA R/V Ronald H. Brown during the Texas Air Quality Study and Gulf of Mexico Atmospheric Composition and Climate Study (TexAQS/GoMACCS 2006). The aerosol measured in the Gulf of Mexico during onshore flow (low radon concentrations indicating no contact with land for several days) was highly impacted by Saharan dust and what appear to be ship emissions (acidic sulfate and nitrate). Mean (median) mass concentrations of the total submicrometer and supermicrometer aerosol were 6.5 (4.6) μg m−3 and 17.2 (8.7) μg m−3, respectively. These mass loadings of “background” aerosol are much higher than typically observed in the marine atmosphere and thus have a substantial impact on the radiative energy balance over the Gulf of Mexico and particulate matter (PM) loadings (air quality) in the Houston‐Galveston area. As this background aerosol moved onshore, local urban and industrial sources added an organic rich submicrometer component (66% particulate organic matter (POM), 20% sulfate, 14% elemental carbon) but no significant supermicrometer aerosol. The resulting aerosol had mean (median) mass concentrations of the total submicrometer and supermicrometer aerosol of 10.0 (9.1) μg m−3 and 16.8 (11.2) μg m−3, respectively. These air masses, with minimal processing of urban emissions contained the highest SO2/(SO2 + SO4=) ratios and the highest hydrocarbon‐like organic aerosol to total organic aerosol ratios (HOA/POM). In contrast, during periods of offshore flow, the aerosol was more processed and, therefore, much richer in oxygenated organic aerosol (OOA). Mean (median) mass concentrations of the total submicrometer and supermicrometer aerosol were 20.8 (18.6) μg m−3 and 7.4 (5.0) μg m−3, respectively. Sorting air masses based on their trajectories and time over land provides a means to examine the effects of transport and subsequent chemical processing. Understanding and parameterizing these processes is critical for the chemical transport modeling that forms the basis for air quality forecasts and radiative forcing calculations.

Measurements were made on board the NOAA RV Ronald H. Brown during the second New England Air Quality Study (NEAQS 2004) to determine the source of the aerosol in the region and how sources and aging processes affect submicrometer aerosol chemical composition and optical properties. Using the Lagrangian particle dispersion model FLEXPART in combination with gas phase tracer compounds, local (urban), regional (NE U.S. urban corridor of Washington, D.C.; New York; and Boston), and distant (midwest industries and North American forest fires) sources were identified. Submicrometer aerosol measured near the source region (Boston Harbor) had a molar equivalence ratio near one with respect to NH4+, NO3−, and SO4=, had a large mass fraction of particulate organic matter (POM) relative to SO4=, and had relatively unoxidized POM. As distance from the source region increased, the submicrometer aerosol measured in the marine boundary layer became more acidic and had a lower POM mass fraction, and the POM became more oxidized. The relative humidity dependence of light extinction reflected the change in aerosol composition being lower for the near‐source aerosol and higher for the more processed aerosol. A factor analysis performed on a combined data set of aerosol and gas phase parameters showed that the POM measured during the experiment was predominantly of secondary anthropogenic origin.

Measurements during recent field campaigns downwind of the Indian subcontinent, Asia, and the northeastern United States reveal a substantial decrease in the relative humidity dependence of light scattering, f σsp (RH), with increasing mass fraction of particulate organic matter (POM) for submicrometer aerosol. Using data from INDOEX (INDian Ocean EXperiment), ACE Asia (Aerosol Characterization Experiment – Asia), and ICARTT (International Consortium for Atmospheric Research on Transport and Transformation), we have identified, within measurement limitations, the impact of POM on the f σsp (RH) of accumulation mode sulfate‐POM mixtures. The result is a parameterization that quantifies the POM mass fraction ‐ f σsp (RH) relationship for use in radiative transfer and air quality models either as input or as validation. The parameterization is valid where the aerosol consists of an internally mixed sulfate‐carbonaceous accumulation mode and other externally mixed components (e.g. sea salt, dust) and is applicable on both global and regional scales.