Wet deposition is the dominant mechanism for removing black carbon (BC) from the atmosphere and is key in determining its atmospheric lifetime, vertical gradient and global transport. Despite the ...importance of BC in the climate system, especially in terms of its ability to modulate the radiative energy budget, there are few quantitative case studies of wet removal in ambient environments. We present a case study of BC wet removal by examining aerosol size distributions and BC coating properties sampled in three Canadian boreal biomass burning plumes, one of which passed through a precipitating cloud. This depleted the majority of the plume's BC mass, and the largest and most coated BC-containing particles were found to be preferentially removed, suggesting that nucleation scavenging was likely the dominant mechanism. Calculated single-scattering albedo (SSA) showed little variation, as a large number of non-BC particles were also present in the precipitation-affected plume. The remaining BC cores were smaller than those observed in previous studies of BC in post-precipitation outflow over Asia, possibly due to the thick coating by hydrophilic compounds associated with the Canadian biomass burning particles. This study provides measurements of BC size, mixing state and removal efficiency to constrain model parameterisations of BC wet removal in biomass burning regions, which will help to reduce uncertainty in radiative forcing calculations.
Aircraft and satellite observations indicate the presence of ppt (ppt ≡ pmol/mol) levels of BrO in the free troposphere with important implications for the tropospheric budgets of ozone, OH, and ...mercury. We can reproduce these observations with the GEOS‐Chem global tropospheric chemistry model by including a broader consideration of multiphase halogen (Br‐Cl) chemistry than has been done in the past. Important reactions for regenerating BrO from its nonradical reservoirs include HOBr + Br−/Cl− in both aerosols and clouds, and oxidation of Br− by ClNO3 and ozone. Most tropospheric BrO in the model is in the free troposphere, consistent with observations and originates mainly from the photolysis and oxidation of ocean‐emitted CHBr3. Stratospheric input is also important in the upper troposphere. Including production of gas phase inorganic bromine from debromination of acidified sea salt aerosol increases free tropospheric Bry by about 30%. We find HOBr to be the dominant gas‐phase reservoir of inorganic bromine. Halogen (Br‐Cl) radical chemistry as implemented here in GEOS‐Chem drives 14% and 11% decreases in the global burdens of tropospheric ozone and OH, respectively, a 16% increase in the atmospheric lifetime of methane, and an atmospheric lifetime of 6 months for elemental mercury. The dominant mechanism for the Br‐Cl driven tropospheric ozone decrease is oxidation of NOx by formation and hydrolysis of BrNO3 and ClNO3.
Key Points
Recent BrO observations are interpreted using a new GEOS‐Chem coupled Br‐Cl simulation
Multiphase oxidation of Br‐ by ozone is critical for maintaining the high observed levels of BrO
Br and Cl lower the global burden of O3 by 14% by increasing NOx loss and shortening the O3 lifetime
Atmospheric concentrations of dichloromethane, CH2Cl2, a regulated toxic air pollutant and minor contributor to stratospheric ozone depletion, were reported to have peaked around 1990 and to be ...declining in the early part of the 21st century. Recent observations suggest this trend has reversed and that CH2Cl2 is once again increasing in the atmosphere. Despite the importance of ongoing monitoring and reporting of atmospheric CH2Cl2, no time series has been discussed in detail since 2006. The CARIBIC project (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) has analysed the halocarbon content of whole-air samples collected at altitudes of between ~ 10-12 km via a custom-built container installed on commercial passenger aircraft since 1998, providing a long-term record of CH2Cl2 observations. In this paper we present this unique CH2Cl2 time series, discussing key flight routes which have been used at various times over the past 15 years. Between 1998 and 2012 increases were seen in all northern hemispheric regions and at different altitudes, ranging from ~ 7-10 ppt in background air to ~ 13-15 ppt in regions with stronger emissions (equating to a 38-69% increase). Of particular interest is the rising importance of India as a source of atmospheric CH2Cl2: based on CARIBIC data we provide regional emission estimates for the Indian subcontinent and show that regional emissions have increased from 3-14 Gg yr-1 (1998-2000) to 16-25 Gg yr-1 (2008). Potential causes of the increasing atmospheric burden of CH2Cl2 are discussed. One possible source is the increased use of CH2Cl2 as a feedstock for the production of HFC-32, a chemical used predominantly as a replacement for ozone-depleting substances in a variety of applications including air conditioners and refrigeration.
Exoelectrogenic bacteria are defined by their ability to respire on extracellular and insoluble electron acceptors and have applications in bioremediation and microbial electrochemical systems ...(MESs), while playing important roles in biogeochemical cycling.
MR-1, which has become a model organism for the study of extracellular respiration, is known to display taxis toward insoluble electron acceptors, including electrodes. Multiple mechanisms have been proposed for MR-1's tactic behavior, and, here, we report on the role of electrochemical potential by video microscopy cell tracking experiments in three-electrode electrochemical cells. MR-1 trajectories were determined using a particle tracking algorithm and validated with Shannon's entropy method. Tactic response by MR-1 in the electrochemical cell was observed to depend on the applied potential, as indicated by the average velocity and density of motile (>4 µm/s) MR-1 close to the electrode (<50 µm). Tactic behavior was observed at oxidative potentials, with a strong switch between the potentials -0.15 to -0.25 V versus the standard hydrogen electrode (SHE), which coincides with the reduction potential of flavins. The average velocity and density of motile MR-1 close to the electrode increased when riboflavin was added (2 µM), but were completely absent in a Δ
/Δ
mutant of MR-1. Besides flavin's function as an electron mediator to support anaerobic respiration on insoluble electron acceptors, we propose that riboflavin is excreted by MR-1 to sense redox gradients in its environment, aiding taxis toward insoluble electron acceptors, including electrodes in MESs.
Previous hypotheses of tactic behavior of exoelectrogenic bacteria are based on techniques that do not accurately control the electrochemical potential, such as chemical-in-plug assays or microscopy tracking experiments in two-electrode cells. Here, we have revisited previous experiments and, for the first time, performed microscopy cell-tracking experiments in three-electrode electrochemical cells, with defined electrode potentials. Based on these experiments, taxis toward electrodes is observed to switch at about -0.2 V versus standard hydrogen electrode (SHE), coinciding with the reduction potential of flavins.
We report the first data set of atmospheric abundances for the following four perfluoroalkanes: n-decafluorobutane (n-C4F10), n-dodecafluoropentane (n-C5F12), n-tetradecafluorohexane (n-C6F14) and ...n-hexadecafluoroheptane (n-C7F16). All four compounds could be detected and quantified in air samples from remote locations in the Southern Hemisphere (at Cape Grim, Tasmania, archived samples dating back to 1978) and the upper troposphere (a passenger aircraft flying from Germany to South Africa). Further observations originate from air samples extracted from deep firn in Greenland and allow trends of atmospheric abundances in the earlier 20th century to be inferred. All four compounds were not present in the atmosphere prior to the 1960s. n-C4F10 and n-C5F12 were also measured in samples collected in the stratosphere with the data indicating that they have no significant sinks in this region. Emissions were inferred from these observations and found to be comparable with emissions from the EDGAR database for n-C6F14. However, emissions of n-C4F10, n-C5F12 and n-C7F16 were found to differ by up to five orders of magnitude between our approach and the database. Although the abundances of the four perfluorocarbons reported here are currently small (less than 0.3 parts per trillion) they have strong Global Warming Potentials several thousand times higher than carbon dioxide (on a 100-yr time horizon) and continue to increase in the atmosphere. We estimate that the sum of their cumulative emissions reached 325 million metric tonnes CO2 equivalent at the end of 2009.
We describe the design and execution of the BORTAS (Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites) experiment, which has the ...overarching objective of understanding the chemical aging of air masses that contain the emission products from seasonal boreal wildfires and how these air masses subsequently impact downwind atmospheric composition. The central focus of the experiment was a two-week deployment of the UK BAe-146-301 Atmospheric Research Aircraft (ARA) over eastern Canada, based out of Halifax, Nova Scotia. Atmospheric ground-based and sonde measurements over Canada and the Azores associated with the planned July 2010 deployment of the ARA, which was postponed by 12 months due to UK-based flights related to the dispersal of material emitted by the Eyjafjallajökull volcano, went ahead and constituted phase A of the experiment. Phase B of BORTAS in July 2011 involved the same atmospheric measurements, but included the ARA, special satellite observations and a more comprehensive ground-based measurement suite. The high-frequency aircraft data provided a comprehensive chemical snapshot of pyrogenic plumes from wildfires, corresponding to photochemical (and physical) ages ranging from < 1 day to ~
The atmospheric records of four halons, H-1211 (CBrClF2), H-1301 (CBrF3), H-2402 (CBrF2CBrF2) and H-1202 (CBr2F2), measured from air collected at Cape Grim, Tasmania, between 1978 and 2011, are ...reported. Mixing ratios of H-1211, H-2402 and H-1202 began to decline in the early to mid-2000s, but those of H-1301 continue to increase up to mid-2011. These trends are compared to those reported by NOAA (National Oceanic and Atmospheric Administration) and AGAGE (Advanced Global Atmospheric Experiment). The observations suggest that the contribution of the halons to total tropospheric bromine at Cape Grim has begun to decline from a peak in 2008 of about 8.1 ppt. An extrapolation of halon mixing ratios to 2060, based on reported banks and predicted release factors, shows this decline becoming more rapid in the coming decades, with a contribution to total tropospheric bromine of about 3 ppt in 2060. Top-down global annual emissions of the halons were derived using a two-dimensional atmospheric model. The emissions of all four have decreased since peaking in the late 1980s–mid-1990s, but this decline has slowed recently, particularly for H-1301 and H-2402 which have shown no decrease in emissions over the past five years. The UEA (University of East Anglia) top-down model-derived emissions are compared to those reported using a top-down approach by NOAA and AGAGE and the bottom-up estimates of HTOC (Halons Technical Options Committee). The implications of an alternative set of steady-state atmospheric lifetimes are discussed. Using a lifetime of 14 yr or less for H-1211 to calculate top-down emissions estimates would lead to small, or even negative, estimated banks given reported production data. Finally emissions of H-1202, a product of over-bromination during the production process of H-1211, have continued despite reported production of H-1211 ceasing in 2010. This raises questions as to the source of these H-1202 emissions.
Air samples collected at Cape Grim, Tasmania between 1978 and 2008 and during a series of more recent aircraft sampling programmes have been analysed to determine the atmospheric abundance and trend ...of octafluorocyclobutane (c-C4F8 or PFC-318). c-C4F8 has an atmospheric lifetime in excess of 3000 yr and a global warming potential (GWP) of 10 300 (100 yr time horizon), making it one of the most potent greenhouse gases detected in the atmosphere to date. The abundance of c-C4F8 in the Southern Hemisphere has risen from 0.35 ppt in 1978 to 1.2 ppt in 2010, and is currently increasing at a rate of around 0.03 ppt yr−1. It is the third most abundant perfluorocarbon (PFC) in the present day atmosphere, behind CF4 (~75 ppt) and C2F6 (~4 ppt). Although a number of potential sources of c-C4F8 have been reported, including the electronics and semi-conductor industries, there remains a large discrepancy in the atmospheric budget. Using a 2-D global model to derive top-down global emissions based on the Cape Grim measurements yields a recent (2007) emission rate of around 1.1 Gg yr−1 and a cumulative emission up to and including 2007 of 38.1 Gg. Emissions reported on the EDGAR emissions database for the period 1986–2005 represent less than 1% of the top-down emissions for the same period, which suggests there is a large unaccounted for source of this compound. It is also apparent that the magnitude of this source has varied considerably over the past 30 yr, declining sharply in the late 1980s before increasing again in the mid-1990s.
A chemical ionisation mass spectrometer (CIMS) was developed for measuring hydrogen cyanide (HCN) from biomass burning events in Canada using I− reagent ions on board the FAAM BAe-146 research ...aircraft during the BORTAS campaign in 2011. The ionisation scheme enabled highly sensitive measurements at 1 Hz frequency through biomass burning plumes in the troposphere. A strong correlation between the HCN, carbon monoxide (CO) and acetonitrile (CH3CN) was observed, indicating the potential of HCN as a biomass burning (BB) marker. A plume was defined as being 6 standard deviations above background for the flights. This method was compared with a number of alternative plume-defining techniques employing CO and CH3CN measurements. The 6-sigma technique produced the highest R2 values for correlations with CO. A normalised excess mixing ratio (NEMR) of 3.68 ± 0.149 pptv ppbv−1 was calculated, which is within the range quoted in previous research (Hornbrook et al., 2011). The global tropospheric model STOCHEM-CRI incorporated both the observed ratio and extreme ratios derived from other studies to generate global emission totals of HCN via biomass burning. Using the ratio derived from this work, the emission total for HCN from BB was 0.92 Tg (N) yr−1.
Short-lived organic brominated compounds make up a significant part of the organic bromine budget in the atmosphere. Emissions of these compounds are highly variable and there are limited ...measurements, particularly in the extra-tropical upper troposphere/lower stratosphere and tropical troposphere. Measurements of five very short-lived bromomethanes (VSLB) were made in air samples collected on the CARIBIC project aircraft over three flight routes; Germany to Venezuela/Columbia during 2009–2011, Germany to South Africa during 2010 and 2011 and Germany to Thailand/Kuala Lumpur, Malaysia during 2012 and 2013. In the tropical troposphere, as the most important entrance region to the stratosphere, we observe a total mean organic bromine derived from these compounds across all flights at 10–12 km altitude of 3.4 ± 1.5 ppt. Individual mean tropical tropospheric mixing ratios across all flights were 0.43, 0.74, 0.14, 0.23 and 0.11 ppt for CHBr3, CH2Br2, CHBr2Cl, CHBrCl2 and CH2BrCl respectively. The highest levels of VSLB-derived bromine (4.20 ± 0.56 ppt) were observed in flights between Bangkok and Kuala Lumpur indicating that the South China Sea is an important source region for these compounds. Across all routes, CHBr3 and CH2Br2 accounted for 34% (4.7–71) and 48% (14–73) respectively of total bromine derived from the analysed VSLB in the tropical mid-upper troposphere totalling 82% (54–89). In samples collected between Germany and Venezuela/Columbia, we find decreasing mean mixing ratios with increasing potential temperature in the extra-tropics. Tropical mean mixing ratios are higher than extra-tropical values between 340–350 K indicating that rapid uplift is important in determining mixing ratios in the lower tropical tropopause layer in the West Atlantic tropics. O3 was used as a tracer for stratospherically influenced air and we detect rapidly decreasing mixing ratios for all VSLB above ∼100 ppb O3 corresponding to the extra-tropical tropopause layer.
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