Dimethyl sulfide (DMS), emitted from the oceans, is the most abundant biological source of sulfur to the marine atmosphere. Atmospheric DMS is oxidized to condensable products that form secondary ...aerosols that affect Earth’s radiative balance by scattering solar radiation and serving as cloud condensation nuclei. We report the atmospheric discovery of a previously unquantified DMS oxidation product, hydroperoxymethyl thioformate (HPMTF, HOOCH₂SCHO), identified through global-scale airborne observations that demonstrate it to be a major reservoir of marine sulfur. Observationally constrained model results show that more than 30% of oceanic DMS emitted to the atmosphere forms HPMTF. Coincident particle measurements suggest a strong link between HPMTF concentration and new particle formation and growth. Analyses of these observations show that HPMTF chemistry must be included in atmospheric models to improve representation of key linkages between the biogeochemistry of the ocean, marine aerosol formation and growth, and their combined effects on climate.
Nitrogen oxides are essential for the formation of secondary atmospheric aerosols and of atmospheric oxidants such as ozone and the hydroxyl radical, which controls the self-cleansing capacity of the ...atmosphere. Nitric acid, a major oxidation product of nitrogen oxides, has traditionally been considered to be a permanent sink of nitrogen oxides. However, model studies predict higher ratios of nitric acid to nitrogen oxides in the troposphere than are observed. A 'renoxification' process that recycles nitric acid into nitrogen oxides has been proposed to reconcile observations with model studies, but the mechanisms responsible for this process remain uncertain. Here we present data from an aircraft measurement campaign over the North Atlantic Ocean and find evidence for rapid recycling of nitric acid to nitrous acid and nitrogen oxides in the clean marine boundary layer via particulate nitrate photolysis. Laboratory experiments further demonstrate the photolysis of particulate nitrate collected on filters at a rate more than two orders of magnitude greater than that of gaseous nitric acid, with nitrous acid as the main product. Box model calculations based on the Master Chemical Mechanism suggest that particulate nitrate photolysis mainly sustains the observed levels of nitrous acid and nitrogen oxides at midday under typical marine boundary layer conditions. Given that oceans account for more than 70 per cent of Earth's surface, we propose that particulate nitrate photolysis could be a substantial tropospheric nitrogen oxide source. Recycling of nitrogen oxides in remote oceanic regions with minimal direct nitrogen oxide emissions could increase the formation of tropospheric oxidants and secondary atmospheric aerosols on a global scale.
CH
is the most abundant reactive greenhouse gas and a complete understanding of its atmospheric fate is needed to formulate mitigation policies. Current chemistry-climate models tend to underestimate ...the lifetime of CH
, suggesting uncertainties in its sources and sinks. Reactive halogens substantially perturb the budget of tropospheric OH, the main CH
loss. However, such an effect of atmospheric halogens is not considered in existing climate projections of CH
burden and radiative forcing. Here, we demonstrate that reactive halogen chemistry increases the global CH
lifetime by 6-9% during the 21st century. This effect arises from significant halogen-mediated decrease, mainly by iodine and bromine, in OH-driven CH
loss that surpasses the direct Cl-induced CH
sink. This increase in CH
lifetime helps to reduce the gap between models and observations and results in a greater burden and radiative forcing during this century. The increase in CH
burden due to halogens (up to 700 Tg or 8% by 2100) is equivalent to the observed atmospheric CH
growth during the last three to four decades. Notably, the halogen-driven enhancement in CH
radiative forcing is 0.05 W/m
at present and is projected to increase in the future (0.06 W/m
by 2100); such enhancement equals ~10% of present-day CH
radiative forcing and one-third of N
O radiative forcing, the third-largest well-mixed greenhouse gas. Both direct (Cl-driven) and indirect (via OH) impacts of halogens should be included in future CH
projections.
Wildfires are an important source of nitrous acid (HONO), a photolabile radical precursor, yet in situ measurements and quantification of primary HONO emissions from open wildfires have been scarce. ...We present airborne observations of HONO within wildfire plumes sampled during the Western Wildfire Experiment for Cloud chemistry, Aerosol absorption and Nitrogen (WE-CAN) campaign. ΔHONO/ΔCO close to the fire locations ranged from 0.7 to 17 pptv ppbv–1 using a maximum enhancement method, with the median similar to previous observations of temperate forest fire plumes. Measured HONO to NO x enhancement ratios were generally factors of 2, or higher, at early plume ages than previous studies. Enhancement ratios scale with modified combustion efficiency and certain nitrogenous trace gases, which may be useful to estimate HONO release when HONO observations are lacking or plumes have photochemical exposures exceeding an hour as emitted HONO is rapidly photolyzed. We find that HONO photolysis is the dominant contributor to hydrogen oxide radicals (HO x = OH + HO2) in early stage (<3 h) wildfire plume evolution. These results highlight the role of HONO as a major component of reactive nitrogen emissions from wildfires and the main driver of initial photochemical oxidation.
High time resolution measurements of volatile organic compounds (VOCs) were collected using a proton‐transfer‐reaction quadrupole mass spectrometry (PTR‐QMS) instrument at the Platteville Atmospheric ...Observatory (PAO) in Colorado to investigate how oil and natural gas (O&NG) development impacts air quality within the Wattenburg Gas Field (WGF) in the Denver‐Julesburg Basin. The measurements were carried out in July and August 2014 as part of NASA's “Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality” (DISCOVER‐AQ) field campaign. The PTR‐QMS data were supported by pressurized whole air canister samples and airborne vertical and horizontal surveys of VOCs. Unexpectedly high benzene mixing ratios were observed at PAO at ground level (mean benzene = 0.53 ppbv, maximum benzene = 29.3 ppbv), primarily at night (mean nighttime benzene = 0.73 ppbv). These high benzene levels were associated with southwesterly winds. The airborne measurements indicate that benzene originated from within the WGF, and typical source signatures detected in the canister samples implicate emissions from O&NG activities rather than urban vehicular emissions as primary benzene source. This conclusion is backed by a regional toluene‐to‐benzene ratio analysis which associated southerly flow with vehicular emissions from the Denver area. Weak benzene‐to‐CO correlations confirmed that traffic emissions were not responsible for the observed high benzene levels. Previous measurements at the Boulder Atmospheric Observatory (BAO) and our data obtained at PAO allow us to locate the source of benzene enhancements between the two atmospheric observatories. Fugitive emissions of benzene from O&NG operations in the Platteville area are discussed as the most likely causes of enhanced benzene levels at PAO.
Key Points
Unexpectedly high benzene mixing ratios were observed in Colorado's Wattenburg Gas Field in July and August 2014
Oil and natural gas extraction activities are implicated as the primary source for the high benzene observations
Gas field measurements of VOCs put a spatial constraint on the location of the gas field benzene source
The hydroxyl radical (OH) reacts with thousands of chemical species in the atmosphere, initiating their removal and the chemical reaction sequences that produce ozone, secondary aerosols, and ...gas-phase acids. OH reactivity, which is the inverse of OH lifetime,influences the OH abundance and the ability of OH to cleanse the atmosphere. The NASA Atmospheric Tomography (ATom) campaign used instruments on the NASA DC-8 aircraft to measure OH reactivity and more than 100 trace chemical species. ATom presented a unique opportunity to test the completeness of the OH reactivity calculated from the chemical species measurements by comparing it to the measured OH reactivity over two oceans across four seasons. Although, throughout much of the free troposphere, the calculated OH reactivity was below the limit-of-detection for the ATom instrument used to measure OH reactivity, the instrument was able to measure the OH reactivity in and just above the marine boundary layer. The mean measured value of OH reactivity in the marine boundary layer across all latitudes and all ATom deployments was 1.9 s-1, which is 0.5 s-1larger than the mean calculated OH reactivity. The missing OH reactivity, the difference between the measured and calculated OH reactivity, varied between 0 s-1to 3.5 s-1, with the highest values over the Northern Hemisphere Pacific Ocean. Correlations of missing OH reactivity with formaldehyde, dimethyl sulfide, butanal, and sea surface temperature suggest the presence of unmeasured or unknown volatile organic compounds or oxygenated volatile organic compounds associated with ocean emissions.
Formaldehyde (HCHO) is one of the most abundant non-methane volatile organic compounds (VOCs) emitted by fires. HCHO also undergoes chemical
production and loss as a fire plume ages, and it can be an ...important oxidant precursor. In this study, we disentangle the processes controlling HCHO
by examining its evolution in wildfire plumes sampled by the NASA DC-8 during the Fire Influence on Regional to Global Environments and Air Quality experiment (FIREX-AQ) field campaign. In 9 of the 12 analyzed plumes,
dilution-normalized HCHO increases with physical age (range 1–6 h). The balance of HCHO loss (mainly via photolysis) and production (via
OH-initiated VOC oxidation) seems to control the sign and magnitude of this trend. Plume-average OH concentrations, calculated from VOC decays,
range from −0.5 (± 0.5) × 106 to 5.3 (± 0.7) × 106 cm−3. The production and loss rates of
dilution-normalized HCHO seem to decrease with plume age. Plume-to-plume variability in dilution-normalized secondary HCHO production correlates
with OH abundance rather than normalized OH reactivity, suggesting that OH is the main driver of fire-to-fire variability in HCHO secondary
production. Analysis suggests an effective HCHO yield of 0.33 (± 0.05) per VOC molecule oxidized for the 12 wildfire plumes. This finding can
help connect space-based HCHO observations to the oxidizing capacity of the atmosphere and to VOC emissions.
Abstract
External cycling regenerating nitrogen oxides (NO
x
≡ NO + NO
2
) from their oxidative reservoir, NO
z
, is proposed to reshape the temporal–spatial distribution of NO
x
and consequently ...hydroxyl radical (OH), the most important oxidant in the atmosphere. Here we verify the in situ external cycling of NO
x
in various environments with nitrous acid (HONO) as an intermediate based on synthesized field evidence collected onboard aircraft platform at daytime. External cycling helps to reconcile stubborn underestimation on observed ratios of HONO/NO
2
and NO
2
/NO
z
by current chemical model schemes and rationalize atypical diurnal concentration profiles of HONO and NO
2
lacking noontime valleys specially observed in low-NO
x
atmospheres. Perturbation on the budget of HONO and NO
x
by external cycling is also found to increase as NO
x
concentration decreases. Consequently, model underestimation of OH observations by up to 41% in low NO
x
atmospheres is attributed to the omission of external cycling in models.
Formaldehyde (HCHO) has been measured from space for more
than 2 decades. Owing to its short atmospheric lifetime, satellite HCHO
data are used widely as a proxy of volatile organic compounds (VOCs; ...please
refer to Appendix A for abbreviations and acronyms), providing constraints
on underlying emissions and chemistry. However, satellite HCHO products from
different satellite sensors using different algorithms have received little
validation so far. The accuracy and consistency of HCHO retrievals remain
largely unclear. Here we develop a validation platform for satellite HCHO
retrievals using in situ observations from 12 aircraft campaigns with a chemical
transport model (GEOS-Chem) as the intercomparison method. Application to
the NASA operational OMI HCHO product indicates negative biases (−44.5 %
to −21.7 %) under high-HCHO conditions, while it indicates high biases (+66.1 % to
+112.1 %) under low-HCHO conditions. Under both conditions, HCHO a priori
vertical profiles are likely not the main driver of the biases. By providing
quick assessment of systematic biases in satellite products over large
domains, the platform facilitates, in an iterative process, optimization of
retrieval settings and the minimization of retrieval biases. It is also
complementary to localized validation efforts based on ground observations
and aircraft spirals.
Aerosol indirect radiative forcing (IRF), which characterizes how aerosols alter cloud formation and properties, is very sensitive to the preindustrial (PI) aerosol burden. Dimethyl sulfide (DMS), ...emitted from the ocean, is a dominant natural precursor of non-sea-salt sulfate in the PI and pristine present-day (PD) atmospheres. Here we revisit the atmospheric oxidation chemistry of DMS, particularly under pristine conditions, and its impact on aerosol IRF. Based on previous laboratory studies, we expand the simplified DMS oxidation scheme used in the Community Atmospheric Model version 6 with chemistry (CAM6-chem) to capture the OH-addition pathway and the H-abstraction pathway and the associated isomerization branch. These additional oxidation channels of DMS produce several stable intermediate compounds, e.g., methanesulfonic acid (MSA) and hydroperoxymethyl thioformate (HPMTF), delay the formation of sulfate, and,
hence, alter the spatial distribution of sulfate aerosol and radiative
impacts. The expanded scheme improves the agreement between modeled and
observed concentrations of DMS, MSA, HPMTF, and sulfate over most marine
regions, based on the NASA Atmospheric Tomography (ATom), the Aerosol and
Cloud Experiments in the Eastern North Atlantic (ACE-ENA), and the
Variability of the American Monsoon Systems (VAMOS)
Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx)
measurements. We find that the global HPMTF burden and the burden of sulfate produced from DMS oxidation are relatively insensitive to the
assumed isomerization rate, but the burden of HPMTF is very sensitive to a
potential additional cloud loss. We find that global sulfate burden under PI and PD emissions increase to 412 Gg S (+29 %) and 582 Gg S (+8.8 %), respectively, compared to the standard simplified DMS oxidation scheme. The resulting annual mean global PD direct radiative effect of DMS-derived sulfate alone is −0.11 W m−2. The enhanced PI sulfate produced via the gas-phase chemistry updates alone dampens the aerosol IRF as anticipated (−2.2 W m−2 in standard versus −1.7 W m−2, with updated gas-phase chemistry). However, high clouds in the tropics and low clouds in the Southern Ocean appear particularly sensitive to the additional aqueous-phase pathways, counteracting this change (−2.3 W m−2). This study confirms
the sensitivity of aerosol IRF to the PI aerosol loading and the
need to better understand the processes controlling aerosol formation in the PI atmosphere and the cloud response to these changes.
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