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Turbulent exchange and segregation of HOx radicals and volatile organic compounds above a deciduous forest

The eddy covariance method was applied for the first time to estimate fluxes of OH and HO2 together with fluxes of isoprene, the sum of methyl vinyl ketone (MVK) and methacrolein (MACR) and the sum of monoterpenes above a mixed deciduous forest. Highly sensitive measurements of OH and HO2 were performed by laser induced fluorescence (LIF), and biogenic volatile organic compounds (BVOCs) were measured by Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) at a time resolution of 5 s, each. Wind speed was measured by a sonic anemometer at 10 Hz. The one-day feasibility study was conducted at a total height of 37 m, about 7 m above forest canopy, during the ECHO (Emission and CHemical transformation of biogenic volatile Organic compounds) intensive field study in July 2003. The daytime measurements yielded statistically significant OH fluxes directed downward into the direction of the canopy and HO2 fluxes mainly upward out of the canopy. This hints towards a significant local chemical sink of OH by reactions with BVOCs, other organic and inorganic compounds and conversion of OH to HO2 above the canopy. For OH the measured flux is locally balanced by chemical sources and sinks and direct transport of OH plays no important role for the local chemical OH budget at the measurement height, as expected from the short OH lifetime (<1 s). For HO2 the chemical lifetime (20 s) is in the range of the turbulent transport time for transfer between the top of the canopy and the measuring point. In this case, the radical balance is significantly influenced by both chemistry and transport processes. In addition, the highly time-resolved trace gas measurements were used to calculate the intensity of segregation of OH and BVOCs, demonstrating that the effective reaction rate of isoprene and OH was slowed down as much as 15% due to inhomogeneous mixing of the reactants. The paper describes the results, the applied methods and provides a detailed analysis of possible systematic errors of the covariance products.
Measured and modeled humidification factors of fresh smoke particles from biomass burning: role of inorganic constituents

During the 2006 FLAME study (Fire Laboratory at Missoula Experiment), laboratory burns of biomass fuels were performed to investigate the physico-chemical, optical, and hygroscopic properties of fresh biomass smoke. As part of the experiment, two nephelometers simultaneously measured dry and humidified light scattering coefficients (bsp(dry) and bsp(RH), respectively) in order to explore the role of relative humidity (RH) on the optical properties of biomass smoke aerosols. Results from burns of several biomass fuels from the west and southeast United States showed large variability in the humidification factor (f(RH)=bsp(RH)/bsp(dry)). Values of f(RH) at RH=80–85% ranged from 0.99 to 1.81 depending on fuel type. We incorporated measured chemical composition and size distribution data to model the smoke hygroscopic growth to investigate the role of inorganic compounds on water uptake for these aerosols. By assuming only inorganic constituents were hygroscopic, we were able to model the water uptake within experimental uncertainty, suggesting that inorganic species were responsible for most of the hygroscopic growth. In addition, humidification factors at 80–85% RH increased for smoke with increasing inorganic salt to carbon ratios. Particle morphology as observed from scanning electron microscopy revealed that samples of hygroscopic particles contained soot chains either internally or externally mixed with inorganic potassium salts, while samples of weak to non-hygroscopic particles were dominated by soot and organic constituents. This study provides further understanding of the compounds responsible for water uptake by young biomass smoke, and is important for accurately assessing the role of smoke in climate change studies and visibility regulatory efforts.
Suppression of warm rain by aerosols in rain-shadow areas of India

Aircraft observations of clouds and aerosols were conducted during the Cloud Aerosol Interaction and Precipitation Enhancement Experiment (CAIPEEX) executed by the Indian Institute of Tropical Meteorology over the Indian subcontinent during the period of May–September 2009. Existence of aerosol layer with large concentrations of cloud drop condensation nuclei extended up to heights of 4 to 5 km was observed over the rain shadow areas to the east of the Western Ghats over central India. The thick aerosol layers were observed to suppress the formation of warm rain in convective clouds up to heights of about 7 km, where mixed phase precipitation formed. This prevented clouds that did not exceed this height from precipitating significantly. This might invigorate the very deep clouds on expense of the smaller clouds. The aerosol radiative effects are suspected to decrease the surface heating and hence the available energy for propelling the convection. The net effect of the aerosols on the rainfall amounts is unknown due to the complexity of the effect, but it is suspected to be detrimental in an area where the rainfall is critical to the livelihood of the inhabitants. This requires continuation of this research.
Technical Note: Vapor pressure estimation methods applied to secondary organic aerosol constituents from α-pinene oxidation: an intercomparison study

We applied and compared seven vapor pressure estimation methods to the condensable compounds generated in the oxidation of α-pinene, as described by the state-of-the-art mechanism of the BOREAM model Capouet et al., 2008. Several of these methods had to be extended in order to treat functional groups such as hydroperoxides and peroxy acyl nitrates. Large differences in the estimated vapor pressures are reported, which will inevitably lead to large differences in aerosol formation simulations. Cautioning remarks are given for some vapor pressure estimation methods.
Microphysical variability in southeast Pacific Stratocumulus clouds: synoptic conditions and radiative response

Synoptic and satellite-derived cloud property variations for the southeast Pacific stratocumulus region associated with changes in coastal satellite-derived cloud droplet number concentrations (Nd) are explored. MAX and MIN Nd composites are defined by the top and bottom terciles of daily area-mean Nd values over the Arica Bight, the region with the largest mean oceanic Nd, for the five October months of 2001, 2005, 2006, 2007 and 2008. The ability of the satellite retrievals to capture composite differences is assessed with ship-based data. Nd and ship-based accumulation mode aerosol concentrations (Na) correlate well (r = 0.65), with a best-fit aerosol activation value dln Nddln Na of 0.56 for pixels with Nd>50 cm−3. The adiabatically-derived MODIS cloud depths also correlate well with the ship-based cloud depths (r=0.7), though are consistently higher (mean bias of almost 60 m). The MAX-Nd composite is characterized by a weaker subtropical anticyclone and weaker winds both at the surface and the lower free troposphere than the MIN-Nd composite. The MAX-Nd composite clouds over the Arica Bight are thinner than the MIN-Nd composite clouds, have lower cloud tops, lower near-coastal cloud albedos, and occur below warmer and drier free tropospheres (as deduced from radiosondes and NCEP Reanalysis). CloudSat radar reflectivities indicate little near-coastal precipitation. The co-occurrence of more boundary-layer aerosol/higher Nd within a more stable atmosphere suggests a boundary layer source for the aerosol, rather than the free troposphere. The MAX-Nd composite cloud thinning extends offshore to 80° W, with lower cloud top heights out to 95° W. At 85° W, the top-of-atmosphere shortwave fluxes are significantly higher (~50%) for the MAX-Nd composite, with thicker, lower clouds and higher cloud fractions than for the MIN-Nd composite. The change in Nd at this location is small (though positive), suggesting that the MAX-MIN Nd composite differences in radiative properties primarily reflects synoptic changes. Circulation anomalies and a one-point spatial correlation map reveal a weakening of the 850 hPa southerly winds decreases the free tropospheric cold temperature advection. The resulting increase in the static stability along 85° W is highly correlated to the increased cloud fraction, despite accompanying weaker free tropospheric subsidence.
Measurement of atmospheric nitrous acid at Bodgett Forest during BEARPEX2007

Nitrous acid (HONO) is an important precursor of the hydroxyl radical (OH) in the lower troposphere. Understanding HONO chemistry, particularly its sources and contribution to HOx (=OH+HO2) production, is very important for understanding atmospheric oxidation processes. A highly sensitive instrument for detecting atmospheric HONO based on wet chemistry followed by liquid waveguide long path absorption photometry was deployed in the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) at Blodgett Forest, California in late summer 2007. The median diurnal variation shows minimum HONO levels of about 20–30 pptv during the day and maximum levels of about 60–70 pptv at night, a diurnal pattern quite different from the results at various other forested sites. Measured HONO/NO2 ratios for a 24-h period ranged from 0.05 to 0.13 with a mean ratio of 0.07. Speciation of reactive nitrogen compounds (NOy) indicates that HONO accounted for only ~3% of total NOy. However, due to the fast HONO loss through photolysis, a strong HONO source (1.59 ppbv day−1) existed in this environment in order to sustain the observed HONO levels, indicating the significant role of HONO in NOy cycling. The wet chemistry HONO measurements were compared to the HONO measurements made with a Chemical Ionization Mass Spectrometer (CIMS) over a three-day period. Good agreement was obtained between the measurements from the two different techniques. Using the expansive suite of photochemical and meteorological measurements, the contribution of HONO photolysis to HOx budget was calculated to be relatively small (6%) compared to results from other forested sites. The lower HONO mixing ratio and thus its smaller contribution to HOx production are attributed to the unique meteorological conditions and low acid precipitation at Blodgett Forest. Further studies of HONO in this kind of environment are needed to test this hypothesis and to improve our understanding of atmospheric oxidation and nitrogen budget.
Modelling microphysical and meteorological controls on precipitation and cloud cellular structures in Southeast Pacific stratocumulus

Microphysical and meteorological controls on the formation of open and closed cellular structures in the Southeast Pacific are explored using model simulations based on aircraft observations during the VAMOS Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx). The effectiveness of factors such as boundary-layer moisture and temperature perturbations, surface heat and moisture fluxes, large-scale vertical motion and solar heating in promoting drizzle and open cell formation for prescribed aerosol number concentrations is explored. For the case considered, drizzle and subsequent open cell formation over a broad region are more sensitive to the observed boundary-layer moisture and temperature perturbations (+0.9 g kg−1; −1 K) than to a five-fold decrease in aerosol number concentration (150 vs. 30 mg−1). When embedding the perturbations in closed cells, local drizzle and pockets of open cell (POC) formation respond faster to the aerosol reduction than to the moisture increase, but the latter generates stronger and more persistent drizzle. A local negative perturbation in temperature drives a mesoscale circulation that prevents local drizzle formation but promotes it in a remote area where lower-level horizontal transport of moisture is blocked and converges to enhance liquid water path. This represents a potential mechanism for POC formation in the Southeast Pacific stratocumulus region whereby the circulation is triggered by strong precipitation in adjacent broad regions of open cells. A simulation that attempts to mimic the influence of a coastally induced upsidence wave results in an increase in cloud water but this alone is insufficient to initiate drizzle. An increase of surface sensible heat flux is also effective in triggering local drizzle and POC formation. Both open and closed cells simulated with observed initial conditions exhibit distinct diurnal variations in cloud properties. A stratocumulus deck that breaks up due solely to solar heating can recover at night. Precipitation in the open-cell cases depletes the aerosol to the extent that cloud formation is significantly suppressed within one diurnal cycle. A replenishment rate of cloud condensation nuclei of order 1 mg−1 h−1 is sufficient to maintain clouds and prevent the boundary layer from collapsing the following day, suggesting that some local and/or remote aerosol sources is necessary for POCs to be able to last for days.
Aerosol spectral absorption in the Mexico City area: results from airborne measurements during MILAGRO/INTEX B

This paper presents estimates of the spectral solar absorption due to atmospheric aerosols during the 2006 MILAGRO/INTEX-B (Megacity Initiative-Local And Global Research Observations/Phase B of the Intercontinental Chemical Transport Experiment) field campaign. The aerosol absorption was derived from measurements of the spectral solar radiation and the spectral aerosol optical depth made on the J31 aircraft flying over the Gulf of Mexico and over Mexico City. We present the spectral single scattering albedo (SSA) and aerosol absorption optical depth (AAOD) for two flights over the Gulf of Mexico and three flights over Mexico City for wavelengths from 350 to approximately 1650 nm. The spectral aerosol optical properties of each case are different and illustrate the variability of the aerosol optical properties in the Mexico City area. The results can be described in terms of three different wavelength regions: The 350–500 nm region where the aerosol absorption often falls off sharply presumably due to organic carbonaceous particles and windblown dust; the 500–1000 nm region where the decrease with wavelength is slower presumably due to black carbon; and the near infrared spectral region (1000 nm to 1650 nm) where it is difficult to obtain reliable results since the aerosol absorption is relatively small and the gas absorption dominates. However, there is an indication of a small and somewhat wavelength independent absorption in the region beyond 1000 nm. For one of the flights over the Gulf of Mexico near the coastline it appears that a cloud/fog formation and evaporation led to an increase of absorption possibly due to a water shell remaining on the particles after the cloud/fog had dissipated. For two of the Mexico City cases, the single scattering albedo is roughly constant between 350–500 nm consistent with other Mexico City results. In three of the cases a single absorption Angstrom exponent (AAE) fits the aerosol absorption optical depth over the entire wavelength range of 350 to 1650 nm relatively well (r2> 0.86).
Corrigendum to "Tropospheric ozone from IASI: comparison of different inversion algorithms and validation with ozone sondes in the northern middle latitudes" published in Atmos. Chem. Phys., 9, 9329–9347, doi:10.5194/acp-9-9329-2009, 2009
Cluster analysis of midlatitude oceanic cloud regimes: mean properties and temperature sensitivity

Clouds play an important role in the climate system by reducing the amount of shortwave radiation reaching the surface and the amount of longwave radiation escaping to space. Accurate simulation of clouds in computer models remains elusive, however, pointing to a lack of understanding of the connection between large-scale dynamics and cloud properties. This study uses a k-means clustering algorithm to group 21 years of satellite cloud data over midlatitude oceans into seven clusters, and demonstrates that the cloud clusters are associated with distinct large-scale dynamical conditions. Three clusters correspond to low-level cloud regimes with different cloud fraction and cumuliform or stratiform characteristics, but all occur under large-scale descent and a relatively dry free troposphere. Three clusters correspond to vertically extensive cloud regimes with tops in the middle or upper troposphere, and they differ according to the strength of large-scale ascent and enhancement of tropospheric temperature and humidity. The final cluster is associated with a lower troposphere that is dry and an upper troposphere that is moist and experiencing weak ascent and horizontal moist advection. Since the present balance of reflection of shortwave and absorption of longwave radiation by clouds could change as the atmosphere warms from increasing anthropogenic greenhouse gases, we must also better understand how increasing temperature modifies cloud and radiative properties. We therefore undertake an observational analysis of how midlatitude oceanic clouds change with temperature when dynamical processes are held constant (i.e., partial derivative with respect to temperature). For each of the seven cloud regimes, we examine the difference in cloud and radiative properties between warm and cold subsets. To avoid misinterpreting a cloud response to large-scale dynamical forcing as a cloud response to temperature, we require horizontal and vertical temperature advection in the warm and cold subsets to have near-median values in three layers of the troposphere. Across all of the seven clusters, we find that cloud fraction is smaller and cloud optical thickness is mostly larger for the warm subset. Cloud-top pressure is higher for the three low-level cloud regimes and lower for the cirrus regime. The net upwelling radiation flux at the top of the atmosphere is larger for the warm subset in every cluster except cirrus, and larger when averaged over all clusters. This implies that the direct response of midlatitude oceanic clouds to increasing temperature acts as a negative feedback on the climate system. Note that the cloud response to atmospheric dynamical changes produced by global warming, which we do not consider in this study, may differ, and the total cloud feedback may be positive.