Polluted Marine Boundary Layer Research Articles

Microphysical, macrophysical, and radiative responses of subtropical marine clouds to aerosol injections

Abstract. Ship tracks in subtropical marine low clouds are simulated and investigated using large-eddy simulations. Five variants of a shallow subtropical stratocumulus-topped marine boundary layer (MBL) are chosen to span a range of background aerosol concentrations and variations in free-tropospheric moisture. Idealized time-invariant meteorological forcings and approximately steady-state aerosol concentrations constitute the background conditions. We investigate processes controlling cloud microphysical, macrophysical, and radiative responses to aerosol injections. For the analysis, we use novel methods to decompose the liquid water path (LWP) adjustment into changes in cloud and boundary-layer properties and to decompose the cloud radiative effect (CRE) into contributions from cloud macro- and microphysics. The key results are that (a) the cloud-top entrainment rate increases in all cases, with stronger increases for thicker than thinner clouds; (b) the drying and warming induced by increased entrainment is offset to differing degrees by corresponding responses in surface fluxes, precipitation, and radiation; (c) MBL turbulence responds to changes caused by the aerosol perturbation, and this significantly affects cloud macrophysics; (d) across 2 d of simulation, clouds were brightened in all cases. In a pristine MBL, significant drizzle suppression by aerosol injections results not only in greater water retention but also in turbulence intensification, leading to a significant increase in cloud amount. In this case, Twomey brightening is strongly augmented by an increase in cloud thickness and cover. In addition, a reduction in the loss of aerosol through coalescence scavenging more than offsets the entrainment dilution. This interplay precludes estimation of the lifetime of the aerosol perturbation. The combined responses of cloud macro- and microphysics lead to 10–100 times more effective cloud brightening in these cases relative to those in the non-precipitating MBL cases. In moderate and polluted MBLs, entrainment enhancement makes the boundary layer drier, warmer, and more stratified, leading to a decrease in cloud thickness. This LWP response offsets the greatest fraction of the Twomey brightening in a moderately moist free troposphere. This finding differs from previous studies that found larger offsets in a drier free troposphere, and it results from a greater entrainment enhancement of initially thicker clouds, so the offsetting effects are weaker. The injected aerosol lifetime in cases with polluted MBLs is estimated to be 2–3 d, which is much longer than estimates of typical ship track lifetimes from satellite images.

Quantification of Non-refractory Aerosol Nitrate in Ambient Air by Thermal Dissociation Cavity Ring-Down Spectroscopy.

A thermal dissociation cavity ring-down spectrometer (TD-CRDS) for real-time quantification of non-refractory aerosol nitrate in ambient air is described. The instrument uses four parallel detection channels and heated quartz inlets to convert particulate organic nitrate (pON) (at 350 °C) and ammonium nitrate (NH4NO3) aerosol (at 540 °C) to nitrogen dioxide (NO2), whose mixing ratio is monitored via its absorption at 405 nm. Concentrations of aerosol nitrate are determined by difference relative to a parallel TD-CRDS channel in which aerosol is removed by in-line filtering. The method was validated by sampling gas streams containing laboratory-generated NH4NO3 aerosol in parallel to a scanning mobility particle sizer (SMPS). Scatter plots of TD-CRDS and SMPS data correlated (r2 > 0.9) with slopes near unity, confirming quantitative TD-CRDS response to NH4NO3 aerosol. In contrast, no response was observed when sampling (NH4)2SO4 aerosol. Instrument limits of detection (LOD; 2σ, 10 s) were 120 parts per trillion by volume (10-12, pptv) for NO2 and 148 pptv for ammonium nitrate. Partial and unsustained conversion of refractory sodium nitrate (NaNO3) was observed at the inlet temperature used for complete dissociation of HNO3 and NH4NO3, suggesting that this channel may not constitute a robust measurement of total odd nitrogen (NOy) in environments where NaNO3 particles may be present (e.g., the polluted marine boundary layer). A potential application of the TD-CRDS is the calibration of particle counters, for which convenient methods are not currently available. Sample ambient air measurements of pON and total aerosol nitrate in Calgary are presented.

Observational Constraints on the Formation of Cl2 From the Reactive Uptake of ClNO2 on Aerosols in the Polluted Marine Boundary Layer

AbstractWe use observations from the 2015 Wintertime Investigation of Transport, Emissions, and Reactivity (WINTER) aircraft campaign to constrain the proposed mechanism of Cl2 production from ClNO2 reaction in acidic particles. To reproduce Cl2 concentrations observed during WINTER with a chemical box model that includes ClNO2 reactive uptake to form Cl2, the model required the ClNO2 reaction probability, γ (ClNO2), to range from 6 × 10−6 to 7 × 10−5, with a mean value of 2.3 × 10−5 (±1.8 × 10−5). These field‐determined γ (ClNO2) are more than an order of magnitude lower than those determined in previous laboratory experiments on acidic surfaces, even when calculated particle pH is ≤2. We hypothesize this is because thick salt films in the laboratory enhanced the reactive uptake ClNO2 compared to that which would occur in submicron aerosol particles. Using the reacto‐diffusive length‐scale framework, we show that the field and laboratory observations can be reconciled if the net aqueous‐phase reaction rate constant for ClNO2 (aq) + Cl‐(aq) in acidic particles is on the order of 104 s−1. We show that wet particle diameter and particulate chloride mass together explain 90% of the observed variance in the box model‐derived γ (ClNO2), implying that the availability of chloride and particle volume limit the efficiency of the reaction. Despite a much lower conversion of ClNO2 into Cl2, this mechanism can still be responsible for the nocturnal formation of 10–20 pptv of Cl2 in polluted regions, yielding an atmospherically relevant concentration of Cl atoms the following morning.

Observations of gas phase hydrochloric acid in the polluted marine boundary layer

AbstractShip‐based measurements of gas phase hydrochloric acid (HCl), particulate chloride (pCl−), and reactive nitrogen oxides (NOy) were made in the polluted marine boundary layer along the California coastline during spring 2010. These observations are used to assess both the rate of Cl atom production from HCl and the role of direct HCl emissions and subsequent partitioning as a source for pCl−. Observations of HCl made in coastal Southern California are broadly correlated with NOz (NOz ≡ NOy – NOx), peaking at 11 A.M. The observed median HCl mixing ratio in Southern California is 1.3 ppb (interquartile range: 0.53–2.7 ppb), as compared to 0.19 ppb (interquartile range: 0.10–0.38 ppb) measured along the Sacramento River between San Francisco and Sacramento. Concurrent measurements of aerosol ion chemistry indicate that aerosol particles sampled in Northern California are heavily depleted in Cl−, corresponding to a mean pCl− deficit of 0.05 ± 0.03 (1σ) ppb for sub‐10 µm aerosol particles. In comparison, aerosols measured in Southern California indicate that over 25% of particles showed an addition of Cl− to the particle population. Observations presented here suggest that primary sources of HCl, or gas phase chlorine precursors to HCl, are likely underestimated in the California Air Resource Board emissions inventory. These results highlight the need for future field observations designed to better constrain direct reactive halogen emissions.

Presence of high nitryl chloride in Asian coastal environment and its impact on atmospheric photochemistry

Nitryl chloride (ClNO2) is a product of nocturnal halogen activation of nitrogen oxides and has potential to impact atmospheric photochemistry. Here we report the first observation result of ClNO2 in an Asian environment. The measurements were made with a thermal decomposition chemical ionization mass spectrometer at a coastal site in southern China during late summer of 2012. A clear diurnal pattern of ClNO2 was observed with nighttime 1-min average mixing ratio up to 1997 pptv, which is among the highest values ever reported in the world. The elevated ClNO2 mixing ratios were observed in plumes from Hong Kong and the Pearl River Delta region compared to the lower levels in maritime air. Calculations suggest that the production of chlorine atom from photolysis of ClNO2 in the early morning exceeds the production of hydroxyl radical via ozone photolysis by several factors. Therefore, ClNO2 plays an important role in jump-starting the atmospheric photochemistry in polluted marine boundary layer of southern China.

Nitryl Chloride and Molecular Chlorine in the Coastal Marine Boundary Layer

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 ClNO(2) 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, ClNO(2) was more ubiquitous than Cl(2) during most nights of the study period. ClNO(2) 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 ClNO(2), 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 ClNO(2), providing support for localized industrial emissions of reactive chlorine. Observations of ClNO(2), 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, ClNO(2) and HCl are dominant primary chlorine atom sources for the Los Angeles basin.

NO<sub>3</sub> radical measurements in a polluted marine environment: links to ozone formation

Abstract. Nighttime chemistry in polluted regions is dominated by the nitrate radical (NO3) including its direct reaction with natural and anthropogenic hydrocarbons, its reaction with NO2 to form N2O5, and subsequent reactions of N2O5 to form HNO3 and chlorine containing photolabile species. We report nighttime measurements of NO3, NO2, and O3, in the polluted marine boundary layer southwest of Vancouver, BC during a three week study in the summer of 2005. The concentration of N2O5 was calculated using the well known equilibrium, NO3+NO2↔N2O5. Median overnight mixing ratios of NO3, N2O5 and NO2 were 10.3 ppt, 122 ppt and 8.3 ppb with median N2O5/NO3 molar ratios of 13.1 and median nocturnal partitioning of 4.9%. Due to the high levels of NO2 that can inhibit approach to steady-state, we use a method for calculating NO3 lifetimes that does not assume the steady-state approximation. Median and average lifetimes of NO3 in the NO3-N2O5 nighttime reservoir were 1.1–2.3 min. We have determined nocturnal profiles of the pseudo first order loss coefficient of NO3 and the first order loss coefficients of N2O5 by regression of the NO3 inverse lifetimes with the [N2O5]/[NO3] ratio. Direct losses of NO3 are highest early in the night, tapering off as the night proceeds. The magnitude of the first order loss coefficient of N2O5 is consistent with, but not verification of, recommended homogeneous rate coefficients for reaction of N2O5 with water vapor early in the night, but increases significantly in the latter part of the night when relative humidity increases beyond 75%, consistent with heterogeneous reactions of N2O5 with aerosols with a rate constant khet=(1.2±0.4)×10−3 s−1−(1.6±0.4)×10−3 s−1. Analysis indicates that a correlation exists between overnight integrated N2O5 concentrations in the marine boundary layer, a surrogate for the accumulation of chlorine containing photolabile species, and maximum 1-h average O3 at stations in the Lower Fraser Valley the next day when there is clear evidence of a sea breeze transporting marine air into the valley. The range of maximum 1-h average O3 increase attributable to the correlation is ΔO3=+1.1 to +8.3 ppb throughout the study for the average of 20 stations, although higher increases are seen for stations far downwind of the coastal urban area. The correlation is still statistically significant on the second day after a nighttime accumulation, but with a different spatial pattern favouring increased O3 at the coastal urban stations, consistent with transport of polluted air back to the coast.

Discovery and measurement of an isotopically distinct source of sulfate in Earth's atmosphere

Sulfate (SO(4)) and its precursors are significant components of the atmosphere, with both natural and anthropogenic sources. Recently, our triple-isotope ((16)O, (17)O, (18)O) measurements of atmospheric sulfate have provided specific insights into the oxidation pathways leading to sulfate, with important implications for models of the sulfur cycle and global climate change. Using similar isotopic measurements of aerosol sulfate in a polluted marine boundary layer (MBL) and primary sulfate (p-SO(4)) sampled directly from a ship stack, we quantify the amount of p-SO(4) found in the atmosphere from ships. We find that ships contribute between 10% and 44% of the non-sea-salt sulfate found in fine [diameter (D) < 1.5 microm) particulate matter in coastal Southern California. These fractions are surprising, given that p-SO(4) constitutes approximately 2-7% of total sulfur emissions from combustion sources [Seinfed JH, Pandis SN (2006) Atmospheric Chemistry and Physics (Wiley-Interscience, New York)]. Our findings also suggest that the interaction of SO(2) from ship emissions with coarse hydrated sea salt particles may lead to the rapid removal of SO(2) in the MBL. When combined with the longer residence time of p-SO(4) emissions in the MBL, these findings suggest that the importance of p-SO(4) emissions in marine environments may be underappreciated in global chemical models. Given the expected increase of international shipping in the years to come, these findings have clear implications for public health, air quality, international maritime law, and atmospheric chemistry.

Influence of aerosols on the shortwave cloud radiative forcing from North Pacific oceanic clouds: Results from the Cloud Indirect Forcing Experiment (CIFEX)

Aerosols over the Northeastern Pacific Ocean enhance the cloud drop number concentration and reduce the drop size for marine stratocumulus and cumulus clouds. These microphysical effects result in brighter clouds, as evidenced by a combination of aircraft and satellite observations. In‐situ measurements from the Cloud Indirect Forcing Experiment (CIFEX) indicate that the mean cloud drop number concentration in low clouds over the polluted marine boundary layer is greater by 53 cm−3 compared to clean clouds, and the mean cloud drop effective radius is smaller by 4 μm. We link these in‐situ measurements of cloud modification by aerosols, for the first time, with collocated satellite broadband radiative flux observations from the Clouds and the Earth's Radiant Energy System to show that these microphysical effects of aerosols enhance the top‐of‐atmosphere cooling by −9.9 ± 4.3 W m−2 for overcast conditions.

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.

Optical properties of the Indo‐Asian haze layer over the tropical Indian Ocean

Multiwavelength backscatter and extinction profiling was performed with a unique aerosol Raman lidar at Hulhule (4°N, 73°E), Maldives, as part of the Indian Ocean Experiment (INDOEX) between February 1999 and March 2000. The Raman lidar allowed a direct determination of the volume extinction coefficient of the particles at 355 and 532 nm at ambient conditions. Heavily polluted air masses from the Asian continent passed over the Maldives during the northeast monsoon seasons. The mean 532‐nm particle optical depth was about 0.3; maximum values of 0.7 were measured. Above the polluted marine boundary layer, lofted plumes were found up to 4000‐m height. On average, the free‐tropospheric aerosol layers contributed 30–60% to the particle optical depth. The volume extinction coefficient at 532 nm typically ranged from 25 to 175 Mm−1 in the elevated layers. The pollution plumes are characterized separately for the air masses from Southeast Asia, North India, and South India. The analysis includes backward trajectories and emission inventory data for India. The extinction‐to‐backscatter ratio (lidar ratio) at 532 nm was mostly between 30 and 100 sr, and accumulated at 50–80 sr for highly absorbing particles from northern India. The shift of the lidar‐ratio distribution for northern Indian aerosols by about 20 sr toward larger values compared to European values is consistent with an aerosol black‐carbon content of up to 20%. The Ångström exponent (for short wavelengths 355/400/532 nm) ranged mostly from 1 to 1.6 for Southeast Asian particles, from 0.8 to 1.4 for North Indian pollution, and from 0.6 to 1 for South Indian air masses. The comparably low Indian Ångström exponents (indicating a comparably large mean particle radius) are possibly caused by the high contribution of biomass combustion to the aerosol formation in India. Results of a correlation analysis based on the lidar ratio, extinction coefficient, Ångström exponents, and relative humidity are presented. In most cases only a weak relationship or no relationship was found between the different parameters.

The influence of cloud chemistry on HO&amp;lt;sub&amp;gt;x&amp;lt;/sub&amp;gt; and NO&amp;lt;sub&amp;gt;x&amp;lt;/sub&amp;gt; in the moderately polluted marine boundary layer: a 1-D modelling study

Abstract. A 1-D marine stratocumulus cloud model has been supplemented with a comprehensive and up-to-date aqueous phase chemical mechanism for the purpose of assessing the impact that the presence of clouds has on gas phaseHOx, NOx and O3 budgets in the marine boundary layer. The simulations presented here indicate that cloud may act as a heterogeneous source of HONOg. The conversion of HNO4(g) at moderate pH (~ 4.5) is responsible for this, and, to a lesser extent, the photolysis of nitrate (NO3-). The effect of introducing deliquescent aerosol on the simulated increase of HONOg is negligible. The most important consequences of this elevation in HONOg are that, in the presence of cloud, gas phase concentrations of NOx species increase by a factor of 2, which minimises the simulated decrease in O3(g), and results in a regeneration of OHg. This partly compensates for the removal of OHg by direct phase transfer into the cloud and may have important implications regarding the oxidising capacity of the marine boundary layer.

A Case Study of Ship Track Formation in a Polluted Marine Boundary Layer

A case study of the effects of ship emissions on the microphysical, radiative, and chemical properties of polluted marine boundary layer clouds is presented. Two ship tracks are discussed in detail. In situ measurements of cloud drop size distributions, liquid water content, and cloud radiative properties, as well as aerosol size distributions (outside-cloud, interstitial, and cloud droplet residual particles) and aerosol chemistry, are presented. These are related to remotely sensed measurements of cloud radiative properties. The authors examine the processes behind ship track formation in a polluted marine boundary layer as an example of the effects of anthropogenic particulate pollution on the albedo of marine stratiform clouds.

A Case Study of Ships Forming and Not Forming Tracks in Moderately Polluted Clouds

The effects of anthropogenic particulate emissions from ships on the radiative, microphysical, and chemical properties of moderately polluted marine stratiform clouds are examined. A case study of two ships in the same air mass is presented where one of the vessels caused a discernible ship track while the other did not. In situ measurements of cloud droplet size distributions, liquid water content, and cloud radiative properties, as well as aerosol size distributions (outside cloud, interstitial, and cloud droplet residual particles) and aerosol chemistry, are presented. These are related to measurements of cloud radiative properties. The differences between the aerosol in the two ship plumes are discussed;these indicate that combustion-derived particles in the size range of about 0.03–0.3-μm radius were those that caused the microphysical changes in the clouds that were responsible for the ship track. The authors examine the processes behind ship track formation in a moderately polluted marine boundary layer as an example of the effects that anthropogenic particulate pollution can have in the albedo of marine stratiform clouds.

A simple non-linear analytical relationship between aerosol accumulation number and sub-micron volume, explaining their observed ratio in the clean and polluted marine boundary layer

A simple non-linear analytical relationship between aerosol accumulation number and sub-micron volume, explaining their observed ratio in the clean and polluted marine boundary layer

Vertical profiling of the Indian aerosol plume with six‐wavelength lidar during INDOEX: A first case study

During the Intensive Field Phase (IFP) of the Indian Ocean Experiment (INDOEX) lasting from 15 February to 26 March 1999, a large number of pollution outbreaks from India and southeast Asia were observed with a unique six‐wavelength aerosol lidar at Maldives International Airport, Hulule (4.1°N, 73.3°E). An example is presented here. Above the polluted marine boundary layer a 3‐km deep aerosol layer was advected from the Indian subcontinent. The aerosol optical depths of the marine boundary layer and the free‐troposphere layer were approximately 0.2 and 0.4 at 532 nm, respectively. Inversions using spectrally resolved particle backscatter and extinction data indicate an effective particle radius of 0.17 µm, volume and surface concentrations around 13 µm³ cm−3 and 600 µm² cm−3, respectively, and considerable absorption by the free‐tropospheric particles.

A simple non-linear analytical relationship between aerosol accumulation number and sub-micron volume, explaining their observed ratio in the clean and polluted marine boundary layer

We propose an analytical expression for the relation between aerosol accumulation number and sub-micron volume over the marine boundary layer (MBL), based on a simple balance equation. By providing appropriate source and sink terms which account for entrainment, coagulation, in-cloud scavenging and condensational growth, the model is able to reproduce the observed ratio between MBL particles larger than 80 nm diameter (as a proxy for accumulation mode number) and submicron aerosol volume, from freshly polluted to background conditions. Entrainment and coagulation are essential in predicting the observed ratio. Budget and lifetime calculations show that, due to relatively low source rates of oceanic non-sea-salt-sulfate and sea-salt, the anthropogenic signature in aerosol volume remains significant even after 8 days of MBL transport.

New particle occurrence in the polluted marine boundary layer during the ACE-2 experiment

New particle occurrence in the polluted marine boundary layer during the ACE-2 experiment

Processes relating aerosol number, aerosol volume and non-seasalt sulfate concentrations in the clean and polluted marine boundary layer

Processes relating aerosol number, aerosol volume and non-seasalt sulfate concentrations in the clean and polluted marine boundary layer

Interaction between nitrogen and sulfur cycles in the polluted marine boundary layer

Simultaneous measurements are reported of the nitrate radical (NO3), nitrogen dioxide (NO2), ozone (O3), and dimethylsulfide (DMS) in the nighttime marine boundary layer over Biscayne Bay in South Florida. These field observations are analyzed and used to initialize a boundary layer box model which examines the relative importance of the various sinks for NOx in the marine boundary layer. The results show that the observed lifetime of NO3 (≤6 min.) is probably controlled both by the loss of nitrogen pentoxide (N2O5) to reaction with water vapor and aerosols and by the reaction between NO3 and DMS. The model is then extended to investigate the loss of nitrogen oxides from an air parcel that remains in the boundary layer with a constant sea‐to‐air DMS flux for several days. The principal conclusions are (1) that DMS is a much more important sink for NO3 at lower NO2 levels and (2) that the reaction between NO3 and DMS is an important sink for DMS in the marine boundary layer and could exceed that of the daytime removal by OH.