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In situ measurements of isoprene and monoterpenes within a south-east Asian tropical rainforest

Biogenic volatile organic compounds (BVOCs) emitted from tropical rainforests comprise a substantial fraction of global atmospheric VOC emissions, however there are only relatively limited measurements of these species in tropical rainforest regions. We present observations of isoprene, α-pinene, camphene, Δ-3-carene, γ-terpinene and limonene, as well as oxygenated VOCs (OVOCs) of biogenic origin such as methacrolein, in ambient air above a tropical rainforest in Malaysian Borneo during the Oxidant and Particle Photochemical Processes above a south-east Asian tropical rainforest (OP3) project in 2008. Daytime composition was dominated by isoprene, with an average mixing ratio of the order of ~1 ppb. γ-terpinene, limonene and camphene were the most abundant monoterpenes, with average daytime mixing ratios of 102, 71 and 66 ppt respectively, and with an average monoterpene toisoprene ratio of 0.3 during sunlit hours, compared to 2.0 at night. Limonene and camphene abundances were seen to be related to both temperature and light conditions. In contrast, γ-terpinene emission continued into the late afternoon/evening, under relatively low temperature and light conditions. The contributions of isoprene, monoterpenes and other classes of VOC to the volatile carbon budget and OH reactivity have been summarised for this rainforest location. We observe good agreement between surface and aircraft measurements of boundary layer isoprene and methacrolein above the natural rainforest, suggesting that the ground-level observations are broadly representative of isoprene emissions from this region.
Quantification of aerosol chemical composition using continuous single particle measurements

Mass concentrations of sulphate, nitrate, ammonium, organic carbon (OC), elemental carbon (EC) were determined from real time single particle data in the size range 0.1–3.0 μm measured by an Aerosol Time-of-Flight Mass Spectrometer (ATOFMS) at urban and rural sites in Canada. To quantify chemical species within individual particles measured by an ATOFMS, ion peak intensity of m/z −97 for sulphate, −62 for nitrate, +18 for ammonium, +43 for OC, and +36 for EC were scaled using the number and size distribution data by an Aerodynamic Particle Sizer (APS) and a Fast Mobility Particle Sizer (FMPS). Hourly quantified chemical species from ATOFMS single-particle analysis were compared with collocated fine particulate matter (aerodynamic diameter < 2.5 μm, PM2.5) chemical composition measurements by an Aerosol Mass Spectrometer (AMS) at a rural site, a Gas-Particle Ion Chromatograph (GPIC) at an urban site, and a Sunset Lab field OCEC analyzer at both sites. The highest correlation was found for nitrate, with correlation coefficients (Pearson r) of 0.89 (ATOFMS vs. GPIC) and 0.85 (ATOFMS vs. AMS). ATOFMS mass calibration factors, determined for the urban site, were used to calculate mass concentrations of the major PM2.5 chemical components at the rural site near the US border in southern Ontario. Mass reconstruction using the ATOFMS mass calibration factors agreed very well with the PM2.5 mass concentrations measured by a Tapered Element Oscillating Microbalance (TEOM, r = 0.86) at the urban site and a light scattering monitor (DustTrak, r = 0.87) at the rural site. In the urban area nitrate was the largest contributor to PM2.5 mass in the winter, while organics and sulphate contributed ~64 % of the summer PM2.5 in the rural area, suggesting a strong influence of regional/trans-boundary pollution. The mass concentrations of five major species in ten size-resolved particle-types and aerosol acidity of each particle-type were determined for the rural site. On a mass basis sulphate and OC rich particle-types (OC-S and OC-S-N) accounted for up to 59 % of the particles characterized and aerosols were weakly acidic in the rural area. This is the first study to estimate hourly quantitative data of sulphate, nitrate, ammonium, OC and EC in ambient particles from scaled ATOFMS single particle analysis; these were closely comparable with collocated high time resolution data of sulphate, nitrate and ammonium detected by AMS and GPIC.
Impact of continental outflow on chemistry of atmospheric aerosols over tropical Bay of Bengal

The continental outflow from Indo-Gangetic Plain and south-east Asia dominates the widespread dispersal of pollutants over tropical Bay of Bengal (BoB) during the late NE-monsoon (January–March). It is thus pertinent to assess the impact on marine atmospheric boundary layer of BoB. The chemical data, based on analyses of size-segregated (PM2.5 and PM10) aerosols, suggest the dominance of nss-SO42− (range: 1.3 to 28 μg m−3) in PM2.5. Almost all SO42− is of anthropogenic origin and accounts for as much as 65 % of the water-soluble inorganic constituents. The impact of anthropogenic sources is further evident from the widespread depletion of chloride (range: 40 to 100 %) compared to sea-salt composition. The carbonaceous species (EC and OC) contribute nearly 25 % to PM2.5; and significant linear relationship with K+ suggests biomass burning as their dominant source (biofuels and agricultural waste). The enhancement in the fractional solubility of aerosol Fe, as assessed in PM2.5, re-emphasizes the impact of combustion sources (biomass and fossil-fuel) and chemical processing (of dust) during the long-range transport. The high enrichment factors of heavy metals (Pb and Cd) further demonstrate the influence of pollution sources on the chemistry of MABL. The downwind transport of pollutants and exchange across air-sea interface can, thus, have profound impact on the ocean surface biogeochemistry.
Combined retrievals of boreal forest fire aerosol properties with a polarimeter and lidar

Absorbing aerosols play an important, but uncertain, role in the global climate. Much of this uncertainty is due to a lack of adequate aerosol measurements. While great strides have been made in observational capability in the previous years and decades, it has become increasingly apparent that this development must continue. Scanning polarimeters have been designed to help resolve this issue by making accurate, multi-spectral, multi-angle polarized observations. This work involves the use of the Research Scanning Polarimeter (RSP). The RSP was designed as the airborne prototype for the Aerosol Polarimetery Sensor (APS), which was due to be launched as part of the (ultimately failed) NASA Glory mission. Field observations with the RSP, however, have established that simultaneous retrievals of aerosol absorption and vertical distribution over bright land surfaces are quite uncertain. We test a merger of RSP and High Spectral Resolution Lidar (HSRL) data with observations of boreal forest fire smoke, collected during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS). During ARCTAS, the RSP and HSRL instruments were mounted on the same aircraft, and validation data were provided by instruments on an aircraft flying a coordinated flight pattern. We found that the lidar data did indeed improve aerosol retrievals using an optimal estimation method, although not primarily because of the contraints imposed on the aerosol vertical distribution. The more useful piece of information from the HSRL was the total column aerosol optical depth, which was used to select the initial value (optimization starting point) of the aerosol number concentration. When ground based sun photometer network climatologies of number concentration were used as an initial value, we found that roughly half of the retrievals had unrealistic sizes and imaginary indices, even though the retrieved spectral optical depths agreed within uncertainties to independent observations. The convergence to an unrealistic local minimum by the optimal estimator is related to the relatively low sensitivity to particles smaller than 0.1 (μm) at large optical thicknesses. Thus, optimization algorithms used for operational aerosol retrievals of the fine mode size distribution, when the total optical depth is large, will require initial values generated from table look-ups that exclude unrealistic size/complex index mixtures. External constraints from lidar on initial values used in the optimal estimation methods will also be valuable in reducing the likelihood of obtaining spurious retrievals.
Change of the Asian dust source region deduced from the composition of anthropogenic radionuclides in surface soil in Mongolia

Recent climate change, especially during the 2000s, may be the primary reason for the expansion of the Asian dust source region. The change in the dust source region was investigated by examining anthropogenic radionuclides contained in surface soil samples from Mongolia. Surface soil was globally labeled by radioactive fallout from nuclear testing during the late 1950s and early 1960s, but there are no current direct sources for anthropogenic radionuclides in the air (before the Fukushima nuclear power plant accident in 2011). Radionuclides in the atmosphere are therefore carried mainly by wind-blown dust from surface soil, that is, aeolian dust. Asian dust carries traces of 90Sr, 137Cs, and other anthropogenic radionuclides; the heaviest deposition occurs in spring and has been recorded in Japan since the early 1990s. The composition of anthropogenic radionuclides in atmospheric depositions would be affected by a change in the dust source. Previous studies of atmospheric deposition at long-term monitoring sites (e.g. in Tsukuba, Japan) have detected changes in the 137Cs/90Sr ratio and in the specific activity of the radionuclides. These changes in the composition of observed atmospheric depositions are supposed to reflect changes in the climatic conditions of the dust source region. To investigate this dust source change, we conducted a field survey of radionuclides (90Sr and 137Cs) in surface soil samples in September 2007 in the eastern and southern regions of Mongolia, where dust storms have occurred more frequently since 2000. The specific activities of both radionuclides as well as the 137Cs/90Sr ratio in the surface soil were well correlated with annual average precipitation in the Mongolian desert-steppe zone. Higher specific activities and a higher 137Cs/90Sr ratio were found in grassland regions that experienced greater precipitation. These findings suggest that the increased specific activities and the activity ratio detected in atmospheric depositions in Japan during years with frequent Asian dust transport events in the 2000s are a sign of grassland degradation.
Temporal and spatial variability of the stable isotopic composition of atmospheric molecular hydrogen: observations at six EUROHYDROS stations

Despite the potential of isotope measurements to improve our understanding of the global atmospheric molecular hydrogen (H2) cycle, few H2 isotope data have been published so far. Now, within the EUROpean network for atmospheric HYDRogen Observations and Studies project (EUROHYDROS), weekly to monthly air samples from six locations in a global sampling network have been analysed for H2 mixing ratio (m(H2)) and the stable isotopic composition of the H2 (δ(D,H2), hereafter referred to as δD). The time series thus obtained now cover one to five years for all stations. This is the largest set of ground station observations of δD so far. Annual average δD values are higher at the Southern Hemisphere (SH) than at the Northern Hemisphere (NH) stations; the maximum is observed at Neumayer (Antarctica), and the minimum at the non-arctic NH stations. The maximum seasonal differences in δD range from ≈18 &permil; at Neumayer to ≈45 &permil; at Schauinsland (Southern Germany); in general, seasonal variability is largest at the NH stations. The timing of minima and maxima differs per station as well. In Alert (Arctic Canada), the variations in δD and m(H2) can be approximated as simple harmonic functions with a ≈5-month relative phase shift. This out-of-phase seasonal behaviour of δD and m(H2) can also be detected, but delayed and with a ≈6-month relative phase shift, at Mace Head and Cape Verde. However, no seasonal δD cycle could be observed at Schauinsland, which likely reflects the larger influence of local sources and sinks at this continental station. At the two SH stations, no seasonal cycle could be detected in the δD data. If it is assumed that the sink processes are the main drivers of the observed seasonality in m(H2) and δD on the NH, the relative seasonal variations can be used to estimate the relative sink strength of the two major sinks, deposition to soils and atmospheric oxidation by the hydroxyl (OH) radical. For the NH coastal and marine stations this analysis suggests that the relative contribution of soil uptake to the total annual H2 removal increases with latitude.
Global modelling of H2 mixing ratios and isotopic compositions with the TM5 model

The isotopic composition of molecular hydrogen (H2) contains independent information for constraining the global H2 budget. To explore this, we have implemented hydrogen sources and sinks, including their stable isotopic composition and isotope fractionation constants, into the global chemistry transport model TM5. For the first time, a global model now includes a simplified but explicit isotope reaction scheme for the photochemical production of H2. We present a comparison of modelled results for the H2 mixing ratio and isotope composition with available measurements on seasonal to inter annual time scales for the years 2001–2007. The base model results agree well with observations for H2 mixing ratios. For δD[H2], modelled values are slightly lower than measurements. A detailed sensitivity study is performed to identify the most important parameters for modelling the isotopic composition of H2. The results show that on the global scale, the discrepancy between model and measurements can be closed by adjusting the default values of the isotope effects in deposition, photochemistry and the stratosphere-troposphere exchange within the known range of uncertainty. However, the available isotope data do not provide sufficient information to uniquely constrain the global isotope budget. Therefore, additional studies focussing on the isotopic composition near the tropopause and on the isotope effects in the photochemistry and deposition are recommended.
Aerosol nucleation spikes in the planetary boundary layer

Photochemically driven nucleation bursts, which typically occur within a few hours after sunrise, often produce strong aerosol number concentration (ANC) fluctuations. The causes of such ANC spikes were investigated using a detailed aerosol model running in the parcel mode. Two potential mechanisms for the ANC spikes were proposed and simulated. The blocking of actinic flux by scattered clouds can significantly influence new particle production, but this does not cause strong fluctuations in the number of aerosols within sizes greater than the detection limit of our measurements. A more plausible mechanism is the turbulence eddy effect. Strong aerosol nucleation may occur in both updrafts and downdrafts, while the cloud formation at the boundary layer top strongly reduces the number of aerosols. As the number of aerosols is sensitive to turbulence eddy and cloud formation properties, a changing turbulence condition would result in large fluctuations in the evolution of ANC similar to that observed at the surface.
Emissions and photochemistry of oxygenated VOCs in urban plumes in the Northeastern United States

Photochemical processes inside urban plumes in the Northeast of the United States have been studied using a highly detailed chemical model, based upon the Master Chemical Mechanism (MCM). The model results have been compared to measurements of oxygenated VOCs (acetone, methyl ethyl ketone, acetaldehyde, acetic acid and methanol) obtained during several flights of the NOAA WP-3D aircraft, which sampled plumes from the New York City area during the ICARTT campaign in 2004. The agreement between the model and the measurements was within 40–60 % for all species, except acetic acid. The model results have been used to study the formation and photochemical evolution of acetone, methyl ethyl ketone and acetaldehyde. Under the conditions encountered during the ICARTT campaign, acetone is produced from the oxidation of propane (24–28 %) and i-propanol (<15 %) and from a number of products of i-pentane oxidation. Methyl ethyl ketone (MEK) is mostly produced from the oxidation of n-butane (20–30 %) and 3-methylpentane (<40 %). Acetaldehyde is formed from several precursors, mostly small alkenes, >C5 alkanes, propanal and MEK. Ethane and ethanol oxidation account, respectively, for 6–23 % and 5–25 % of acetaldehyde photochemical formation. The results highlight the importance of alkanes for the photochemical production of ketones and the role of hydroperoxides in sustaining their formation far from the emission sources.
Microphysical, macrophysical and radiative signatures of volcanic aerosols in trade wind cumulus observed by the A-Train

Increased aerosol concentrations can raise planetary albedo not only by reflecting sunlight and increasing cloud albedo, but also by changing cloud amount. However, detecting aerosol effect on cloud amount has been elusive to both observations and modeling due to potential buffering mechanisms and convolution of meteorology. Here through a natural experiment provided by long-term degassing of a low-lying volcano and use of A-Train satellite observations, we show modifications of trade cumulus cloud fields including decreased droplet size, decreased precipitation efficiency and increased cloud amount are associated with volcanic aerosols. In addition we find significantly higher cloud tops for polluted clouds. We demonstrate that the observed microphysical and macrophysical changes cannot be explained by synoptic meteorology or the orographic effect of the Hawaiian Islands. The "total shortwave aerosol forcin", resulting from direct and indirect forcings including both cloud albedo and cloud amount, is almost an order of magnitude higher than aerosol direct forcing alone. Furthermore, the precipitation reduction associated with enhanced aerosol leads to large changes in the energetics of air-sea exchange and trade wind boundary layer. Our results represent the first observational evidence of large-scale increase of cloud amount due to aerosols in a trade cumulus regime, which can be used to constrain the representation of aerosol-cloud interactions in climate models. The findings also have implications for volcano-climate interactions and climate mitigation research.