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Speciated atmospheric mercury observations collected over the period from 2008 to 2010 at the Environmental Protection Agency and National Atmospheric Deposition Program Atmospheric Mercury Network sites (AMNet) were analyzed for its spatial, seasonal, and diurnal characteristics across the US. Median values of gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM) and particulate bound mercury (PBM) at 11 different AMNet sites ranged from 148–226 ppqv (1.32–2.02 ng m<sup>−3</sup>), 0.05–1.4 ppqv (0.47–12.4 pg m<sup>−3</sup>) and 0.18–1.5 ppqv (1.61–13.7 pg m<sup>−3</sup>), respectively. Common characteristics of these sites were the similar median levels of GEM as well as its seasonality, with the highest mixing ratios occurring in winter and spring and the lowest in fall. However, discernible differences in monthly average GEM were as large as 30 ppqv, which may be caused by sporadic influence from local emission sources. The largest diurnal variation amplitude of GEM occurred in the summer. Seven rural sites displayed similar GEM summer diurnal patterns, in that the lowest levels appeared in the early morning, and then the GEM mixing ratio increased after sunrise and reached its maxima at noon or in the early afternoon. Unlike GEM, GOM exhibited higher mixing ratios in spring and summer. The largest diurnal variation amplitude of GOM occurred in spring for most AMNet sites. The GOM diurnal minima appeared before sunrise and maxima appeared in the afternoon. The increased GOM mixing ratio in the afternoon indicated a photochemically driven oxidation of GEM resulting in GOM formation. PBM exhibited diurnal fluctuations in summertime. The summertime PBM diurnal pattern displayed daily maxima in the early afternoon and lower mixing ratios at night, implying photochemical production of PBM in summer.
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The volatility of submicron atmospheric aerosol particles was investigated at a boreal forest site in Hyytiälä, Finland from January 2008 to May 2010. These long-term observations allowed for studying the seasonal behavior of aerosol evaporation with a special focus on compounds that remained in the aerosol phase at 280 °C. The temperature-response of evaporation was also studied by heating the aerosol sample step-wise to six temperatures ranging from 80 °C to 280 °C. The mass fraction remaining after heating (MFR) was determined from the measured particle number size distributions before and after heating assuming a constant particle density (1.6 g cm<sup>−3</sup>). On average 19% of the total aerosol mass remained in the particulate phase at 280 °C. The particles evaporated less at low ambient temperatures during winter as compared with the warmer months. Black carbon (BC) fraction of aerosol mass correlated positively with the MFR at 280 °C, but could not explain it completely: most of the time a notable fraction of this non-volatile residual was something other than BC. Using additional information on ambient meteorological conditions and results from an Aerodyne aerosol mass spectrometer (AMS), the chemical composition of MFR at 280 °C and its seasonal behavior was further examined. Correlation analysis with ambient temperature and mass fractions of polycyclic aromatic hydrocarbons (PAHs) indicated that MFR at 280 °C is probably affected by anthropogenic emissions. On the other hand, results from the AMS analysis suggested that there may be very low-volatile organics, possibly organonitrates, in the non-volatile (at 280 °C) fraction of aerosol mass.
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Fires are a global phenomenon that impact climate and biogeochemical cycles, and interact with the biosphere, atmosphere and cryosphere. These impacts occur on a range of temporal and spatial scales and are difficult to quantify globally based solely on observations. Here we assess the role of fires in the climate system using model estimates of radiative forcing (RF) from global fires in pre-industrial, present day, and future time periods. Fire emissions of trace gases and aerosols are derived from Community Land Model simulations and then used in a series of Community Atmosphere Model simulations with representative emissions from the years 1850, 2000, and 2100. Additional simulations are carried out with fire emissions from the Global Fire Emission Database for a present-day comparison. These results are compared against the results of simulations with no fire emissions to compute the contribution from fires. We consider the impacts of fire on greenhouse gas concentrations, aerosol effects (including aerosol effects on biogeochemical cycles), and land and snow surface albedo. Overall, we estimate that pre-industrial fires were responsible for a RF of −1 W m<sup>−2</sup> with respect to a pre-industrial climate without fires. The largest magnitude pre-industrial forcing from fires was the indirect aerosol effect on clouds (−1.6 W m<sup>−2</sup>). This was balanced in part by an increase in carbon dioxide concentrations due to fires (+0.83 W m<sup>−2</sup>). The RF of fires increases by 0.5 W m<sup>−2</sup> from 1850 to 2000 and 0.2 W m<sup>−2</sup> from 1850 to 2100 in the model representation from a combination of changes in fire activity and changes in the background environment in which fires occur, especially increases and decreases in the anthropogenic aerosol burden. Thus, fires play an important role in both the natural equilibrium climate and the climate perturbed by anthropogenic activity and need to be considered in future climate projections.
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Radiocarbon (<sup>14</sup>C) measurements of elemental carbon (EC) and organic carbon (OC) separately (as opposed to only total carbon, TC) allow an unambiguous quantification of their non-fossil and fossil sources and represent an improvement in carbonaceous aerosol source apportionment. Isolation of OC and EC for accurate <sup>14</sup>C determination requires complete removal of interfering fractions with maximum recovery. The optimal strategy for <sup>14</sup>C-based source apportionment of carbonaceous aerosols should follow an approach to subdivide TC into different carbonaceous aerosol fractions for individual <sup>14</sup>C analyses, as these fractions may differ in their origins. To evaluate the extent of positive and negative artefacts during OC and EC separation, we performed sample preparation with a commercial Thermo-Optical OC/EC Analyser (TOA) by monitoring the optical properties of the sample during the thermal treatments. Extensive attention has been devoted to the set-up of TOA conditions, in particular, heating program and choice of carrier gas. Based on different types of carbonaceous aerosols samples, an optimised TOA protocol (Swiss_4S) with four steps is developed to minimise the charring of OC, the premature combustion of EC and thus artefacts of <sup>14</sup>C-based source apportionment of EC. For the isolation of EC for <sup>14</sup>C analysis, the water-extraction treatment on the filter prior to any thermal treatment is an essential prerequisite for subsequent radiocarbon measurements; otherwise the non-fossil contribution may be overestimated due to the positive bias from charring. The Swiss_4S protocol involves the following consecutive four steps (S1, S2, S3 and S4): (1) S1 in pure oxygen (O<sub>2</sub>) at 375 °C for separation of OC for untreated filters and water-insoluble organic carbon (WINSOC) for water-extracted filters; (2) S2 in O<sub>2</sub> at 475 °C followed by (3) S3 in helium (He) at 650 °C, aiming at complete OC removal before EC isolation and leading to better consistency with thermal-optical protocols like EUSAAR_2, compared to pure oxygen methods; and (4) S4 in O<sub>2</sub> at 760 °C for recovery of the remaining EC. <br><br> WINSOC was found to have a significantly higher fossil contribution than the water-soluble OC (WSOC). Moreover, the experimental results demonstrate the lower refractivity of wood-burning EC compared to fossil EC and the difficulty of clearly isolating EC without premature evolution. Hence, simplified techniques of EC isolation for <sup>14</sup>C analysis are prone to a substantial bias and generally tend towards an overestimation of fossil sources. To obtain the comprehensive picture of the sources of carbonaceous aerosols, the Swiss_4S protocol is not only implemented to measure OC and EC fractions, but also WINSOC as well as a continuum of refractory OC and non-refractory EC for <sup>14</sup>C source apportionment. In addition, WSOC can be determined by subtraction of the water-soluble fraction of TC from untreated TC. Last, we recommend that <sup>14</sup>C results of EC should in general be reported together with the EC recovery.
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For a case study of Typhoon Ewiniar performed with a mesoscale model, we compare stratospheric gravity wave (GW) momentum flux determined from temperature variances by applying GW polarization relations and by assuming upward propagating waves, with GW momentum flux calculated from model winds which is considered as a reference. The temperature-based momentum-flux profile exhibits positive biases relative to the reference, which fluctuate significantly with altitude. The vertically-averaged magnitude of the positive biases is about 14% of the reference momentum flux. We found that this deviation from the reference stems from the interference between upward and downward propagating waves. The downward propagating GWs are due mainly to partial reflections of upward propagating waves at altitudes where the background wind and stability change with height. When the upward and downward propagating waves are decomposed and their momentum fluxes are calculated separately from temperature perturbations, the fraction of the momentum flux arising from the downward propagating waves is about 4.5–8.2% of that from the upward propagating waves. The net momentum flux of upward and downward propagating GWs agrees well with the reference from the model wind perturbations. The implications of this study for the GW momentum-flux observations from satellites are discussed.
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Caesium-137 (<sup>137</sup>Cs) and iodine-131 (<sup>131</sup>I) are radionuclides of particular concern during nuclear accidents, because they are emitted in large amounts and are of significant health impact. <sup>137</sup>Cs and <sup>131</sup>I attach to the ambient accumulation-mode (AM) aerosols and share their fate as the aerosols are removed from the atmosphere by scavenging within clouds, precipitation and dry deposition. Here, we estimate their removal times from the atmosphere using a unique high-precision global measurement data set collected over several months after the accident at the Fukushima Dai-ichi nuclear power plant in March 2011. The noble gas xenon-133 (<sup>133</sup>Xe), also released during the accident, served as a passive tracer of air mass transport for determining the removal times of <sup>137</sup>Cs and <sup>131</sup>I via the decrease in the measured ratios <sup>137</sup>Cs/<sup>133</sup>Xe and <sup>131</sup>I/<sup>133</sup>Xe over time. After correction for radioactive decay, the <sup>137</sup>Cs/<sup>133</sup>Xe ratios reflect the removal of aerosols by wet and dry deposition, whereas the <sup>131</sup>I/<sup>133</sup>Xe ratios are also influenced by aerosol production from gaseous <sup>131</sup>I. We find removal times for <sup>137</sup>Cs of 10.0–13.9 days and for <sup>131</sup>I of 17.1–24.2 days during April and May 2011. The removal time of <sup>131</sup>I is longer due to the aerosol production from gaseous <sup>131</sup>I, thus the removal time for <sup>137</sup>Cs serves as a better estimate for aerosol lifetime. The removal time of <sup>131</sup>I is of interest for semi-volatile species. We discuss possible caveats (e.g. late emissions, resuspension) that can affect the results, and compare the <sup>137</sup>Cs removal times with observation-based and modeled aerosol lifetimes. Our <sup>137</sup>Cs removal time of 10.0–13.9 days should be representative of a "background" AM aerosol well mixed in the extratropical Northern Hemisphere troposphere. It is expected that the lifetime of this vertically mixed background aerosol is longer than the lifetime of fresh AM aerosols directly emitted from surface sources. However, the substantial difference to the mean lifetimes of AM aerosols obtained from aerosol models, typically in the range of 3–7 days, warrants further research on the cause of this discrepancy. Too short modeled AM aerosol lifetimes would have serious implications for air quality and climate model predictions.
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Although oxidation of the atmospherically relevant compound α-pinene has been extensively studied, chemical mechanisms leading to the formation of later generation oxidation products remain poorly understood. The present work uses cyclobutyl methyl ketone (CMK) to study the oxidation mechanism of pinonic acid, an α-pinene reaction product, by hydroxyl radicals (·OH). CMK has a similar but simpler chemical structure compared to pinonic acid. Succinic acid, 4-hydroxybutanoic acid and 4-oxobutanoic acid were identified as first generation products of CMK. These observed organic acids were compared to compounds found in secondary organic aerosol formed from the oxidation of α-pinene. Results suggest that 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), terpenylic % corrected name for MBTCA (3-methyl-1,2,3-butanetricarboxylic acid) acid and diaterpenylic acid acetate are first generation products of OH oxidation of pinonic acid. Therefore, there is strong evidence that ·OH oxidation greatly increases the oxygenation of organic compounds (e.g. monocarboxylic acid to tricarboxylic acid) through radical mechanisms, without requiring a stable intermediate. These observations cannot be explained by traditional atmospheric chemistry mechanisms.
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Oceanic emissions of halogenated very short-lived substances (VSLS) are expected to contribute significantly to the stratospheric halogen loading and therefore to ozone depletion. The amount of VSLS transported into the stratosphere is estimated based on in-situ observations around the tropical tropopause layer (TTL) and on modeling studies which mostly use prescribed global emission scenarios to reproduce observed atmospheric concentrations. In addition to upper-air VSLS measurements, direct observations of oceanic VSLS emissions are available along ship cruise tracks. Here we use such in-situ observations of VSLS emissions from the West Pacific and tropical Atlantic together with an atmospheric Lagrangian transport model to estimate the direct contribution of bromoform (CHBr<sub>3</sub>), and dibromomethane (CH<sub>2</sub>Br<sub>2</sub>) to the stratospheric bromine loading as well as their ozone depletion potential. Our emission-based estimates of VSLS profiles are compared to upper-air observations and thus link observed oceanic emissions and in situ TTL measurements. This comparison determines how VSLS emissions and transport in the cruise track regions contribute to global upper-air VSLS estimates. The West Pacific emission-based profiles and the global upper-air observations of CHBr<sub>3</sub> show a relatively good agreement indicating that emissions from the West Pacific provide an average contribution to the global CHBr<sub>3</sub> budget. The tropical Atlantic, although also being a CHBr<sub>3</sub> source region, is of less importance for global upper-air CHBr<sub>3</sub> estimates as revealed by the small emission-based abundances in the TTL. Western Pacific CH<sub>2</sub>Br<sub>2</sub> emission-based estimates are considerably smaller than upper-air observations as a result of the relatively low sea-to-air flux found in the West Pacific. Together, CHBr<sub>3</sub> and CH<sub>2</sub>Br<sub>2</sub> emissions from the West Pacific are projected to contribute to the stratospheric bromine budget with 0.4 pptv Br on average and 2.3 pptv Br for cases of maximum emissions through product and source gas injection. These relatively low estimates reveal that the tropical West Pacific, although characterized by strong convective transport, might overall contribute less VSLS to the stratospheric bromine budget than other regions as a result of only low CH<sub>2</sub>Br<sub>2</sub> and moderate CHBr<sub>3</sub> oceanic emissions.
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The uncertainties associated with the wet removal of aerosols entrained above convective cloud bases are investigated in a global aerosol-climate model (ECHAM5-HAM) under a set of limiting assumptions for the wet removal of the entrained aerosols. The limiting assumptions for the wet removal of entrained aerosols are negligible scavenging and vigorous scavenging (either through activation, with size-dependent impaction scavenging, or with the prescribed fractions of the standard model). To facilitate this process-based study, an explicit representation of cloud-droplet-borne and ice-crystal-borne aerosol mass and number, for the purpose of wet removal, is introduced into the ECHAM5-HAM model. This replaces and is compared with the prescribed cloud-droplet-borne and ice-crystal-borne aerosol fraction scavenging scheme of the standard model. <br><br> A 20% to 35% uncertainty in simulated global, annual mean aerosol mass burdens and optical depth (AOD) is attributed to different assumptions for the wet removal of aerosols entrained above convective cloud bases. Assumptions about the removal of aerosols entrained above convective cloud bases control modeled upper tropospheric aerosol concentrations by as much as one order of magnitude. <br><br> Simulated aerosols entrained above convective cloud bases contribute 20% to 50% of modeled global, annual mean aerosol mass convective wet deposition (about 5% to 10% of the total dry and wet deposition), depending on the aerosol species, when including wet scavenging of those entrained aerosols (either by activation, size-dependent impaction, or with the prescribed fraction scheme). Among the simulations, the prescribed fraction and size-dependent impaction schemes yield the largest global, annual mean aerosol mass convective wet deposition (by about two-fold). However, the prescribed fraction scheme has more vigorous convective mixed-phase wet removal (by two to five-fold relative to the size-dependent impaction scheme) since nearly all entrained accumulation and coarse mode aerosols are assumed to be cloud-droplet borne or ice-crystal borne, and evaporation due to the Bergeron-Findeisen process is neglected. <br><br> The simulated convective wet scavenging of entrained accumulation and coarse mode aerosols has feedbacks on new particle formation and the number of Aitken mode aerosols, which control stratiform and convective cloud droplet number concentrations and yield precipitation changes in the ECHAM5-HAM model. However, the geographic distribution of aerosol annual mean convective wet deposition change in the model is driven by changes to the assumptions regarding the scavenging of aerosols entrained above cloud bases rather than by precipitation changes, except for sea salt deposition in the tropics. Uncertainty in the seasonal, regional cycles of AOD due to assumptions about entrained aerosol wet scavenging is similar in magnitude to the estimated error in the AOD retrievals. <br><br> The uncertainty in aerosol concentrations, burdens, and AOD attributed to different assumptions for the wet scavenging of aerosols entrained above convective cloud bases in a global model motivates the ongoing need to better understand and model the activation and impaction processes that aerosols undergo after entrainment into convective updrafts.
