V. Sinha

OH reactivity measurements within a boreal forest: evidence for unknown reactive emissions.

Boreal forests emit large amounts of volatile organic compounds (VOCs) which react with the hydroxyl radical (OH) to influence regional ozone levels and form secondary organic aerosol. Using OH reactivity measurements within a boreal forest in Finland, we investigated the budget of reactive VOCs. OH reactivity was measured using the comparative reactivity method, whereas 30 individual VOCs were measured using proton transfer reaction mass spectrometry, thermal-desorption gas chromatography mass spectrometry, and liquid chromatography mass spectrometry, in August 2008. The measured OH reactivity ranged from below detection limit (3.5 s(-1)), to approximately 60 s(-1) in a single pollution event. The average OH reactivity was approximately 9 s(-1) and no diel variation was observed in the profiles. The measured OH sinks (approximately 30 species) accounted for only 50% of the total measured OH reactivity, implying unknown reactive VOCs within the forest. The five highest measured OH sinks were: monoterpenes (1 s(-1)), CO (0.7 s(-1)), isoprene (0.5 s(-1)), propanal and acetone (0.3 s(-1)), and methane (0.3 s(-1)). We suggest that models be constrained by direct OH reactivity measurements to accurately assess the impact of boreal forest emissions on regional atmospheric chemistry and climate.

Total OH reactivity measurements in Paris during the 2010 MEGAPOLI winter campaign

Hydroxyl radicals play a central role in the troposphere as they control the lifetime of many trace gases. Measurement of OH reactivity (OH loss rate) is important to better constrain the OH budget and also to evaluate the completeness of measured VOC budget. Total atmospheric OH reactivity was measured for the first time in an European Megacity: Paris and its surrounding areas with 12 million inhabitants, during the MEGAPOLI winter campaign 2010. The method deployed was the Comparative Reactivity Method (CRM). The measured dataset contains both measured and calculated OH reactivity from CO, NOx and VOCs measured via PTR-MS, GC-FID and GC-MS instruments. The reactivities observed in Paris covered a range from 10s to 130s, indicating a large loading of chemical reactants. The present study showed that, when clean marine air masses influenced Paris, the purely local OH reactivity (20s) is well explained by the measured species. Nevertheless, when there is a continental import of air masses, high levels of OH reactivity were obtained (120 – 130 s) and the missing OH reactivity measured in this case jumped to 75%. Using covariations of the missing OH reactivity to secondary inorganic species in fine aerosols, we suggest that the missing OH reactants were most likely highly oxidized compounds issued from photochemically processed air masses of anthropogenic origin. Chapitre 4 : Mesure de la réactivité OH à Paris pendant MEGAPOLI hiver 2010 146 Mesure de la réactivité atmosphérique totale avec les radicaux OH : Développement et applications en Ile-de-France

Atmospheric benzenoid emissions from plants rival those from fossil fuels

Despite the known biochemical production of a range of aromatic compounds by plants and the presence of benzenoids in floral scents, the emissions of only a few benzenoid compounds have been reported from the biosphere to the atmosphere. Here, using evidence from measurements at aircraft, ecosystem, tree, branch and leaf scales, with complementary isotopic labeling experiments, we show that vegetation (leaves, flowers, and phytoplankton) emits a wide variety of benzenoid compounds to the atmosphere at substantial rates. Controlled environment experiments show that plants are able to alter their metabolism to produce and release many benzenoids under stress conditions. The functions of these compounds remain unclear but may be related to chemical communication and protection against stress. We estimate the total global secondary organic aerosol potential from biogenic benzenoids to be similar to that from anthropogenic benzenoids (~10 Tg y−1), pointing to the importance of these natural emissions in atmospheric physics and chemistry.

Limitation of the Use of the Absorption Angstrom Exponent for Source Apportionment of Equivalent Black Carbon: a Case Study from the North West Indo-Gangetic Plain

Angstrom exponent measurements of equivalent black carbon (BCeq) have recently been introduced as a novel tool to apportion the contribution of biomass burning sources to the BCeq mass. The BCeq is the mass of ideal BC with defined optical properties that, upon deposition on the aethalometer filter tape, would cause equal optical attenuation of light to the actual PM2.5 aerosol deposited. The BCeq mass hence is identical to the mass of the total light-absorbing carbon deposited on the filter tape. Here, we use simultaneously collected data from a seven-wavelength aethalometer and a high-sensitivity proton-transfer reaction mass spectrometer installed at a suburban site in Mohali (Punjab), India, to identify a number of biomass combustion plumes. The identified types of biomass combustion include paddy- and wheat-residue burning, leaf litter, and garbage burning. Traffic plumes were selected for comparison. We find that the combustion efficiency, rather than the fuel used, determines αabs, and consequently, the αabs can be ∼1 for flaming biomass combustion and >1 for older vehicles that operate with poorly optimized engines. Thus, the absorption angstrom exponent is not representative of the fuel used and, therefore, cannot be used as a generic tracer to constrain source contributions.

Contribution of post-harvest agricultural paddy residue fires in the N.W. Indo-Gangetic Plain to ambient carcinogenic benzenoids, toxic isocyanic acid and carbon monoxide

In the north west Indo-Gangetic Plain (N.W.IGP), large scale post-harvest paddy residue fires occur every year during the months of October-November. This anthropogenic perturbation causes contamination of the atmospheric environment with adverse impacts on regional air quality posing health risks for the population exposed to high concentrations of carcinogens such as benzene and toxic VOCs such as isocyanic acid. These gases and carbon monoxide are known to be emitted from biomass fires along with acetonitrile. Yet no long-term in-situ measurements quantifying the impact of this activity have been carried out in the N.W. IGP. Using high quality continuous online in-situ measurements of these gases at a strategic downwind site over a three year period from 2012 to 2014, we demonstrate the strong impact of this anthropogenic emission activity on ambient concentrations of these gases. In contrast to the pre-paddy harvest period, excellent correlation of benzenoids, isocyanic acid and CO with acetonitrile (a biomass burning chemical tracer); (r≥0.82) and distinct VOC/acetonitrile emission ratios were observed for the post-paddy harvest period which was also characterized by high ambient concentrations of these species. The average concentrations of acetonitrile (1.62±0.18ppb), benzene (2.51±0.28ppb), toluene (3.72±0.41ppb), C8-aromatics (2.88±0.30ppb), C9-aromatics (1.55±0.19ppb) and CO (552±113ppb) in the post-paddy harvest periods were about 1.5 times higher than the annual average concentrations. For isocyanic acid, a compound with both primary and secondary sources, the concentration in the post-paddy harvest period was 0.97±0.17ppb. The annual average concentrations of benzene, a class A carcinogen, exceeded the annual exposure limit of 1.6ppb at NTP mandated by the National Ambient Air Quality Standard of India (NAAQS). We show that mitigating the post-harvest paddy residue fires can lower the annual average concentration of benzene and ensure compliance with the NAAQS. Calculations of excessive lifetime cancer risk due to benzene amount to 25 and 10 per million inhabitants for children and adults, respectively, exceeding the USEPA threshold of 1 per million inhabitants. Annual exposure to isocyanic acid was close to 1ppb, the concentration considered to be sufficient to enhance risks for cardiovascular diseases and cataracts. This study makes a case for urgent mitigation of post-harvest paddy residue fires as the unknown synergistic effect of multi-pollutant exposure due to emissions from this anthropogenic source may be posing grave health risks to the population of the N.W. IGP.

Large unexplained suite of chemically reactive compounds present in ambient air due to biomass fires

Biomass fires impact global atmospheric chemistry. The reactive compounds emitted and formed due to biomass fires drive ozone and organic aerosol formation, affecting both air quality and climate. Direct hydroxyl (OH) Reactivity measurements quantify total gaseous reactive pollutant loadings and comparison with measured compounds yields the fraction of unmeasured compounds. Here, we quantified the magnitude and composition of total OH reactivity in the north-west Indo-Gangetic Plain. More than 120% increase occurred in total OH reactivity (28 s−1 to 64 s−1) and from no missing OH reactivity in the normal summertime air, the missing OH reactivity fraction increased to ~40 % in the post-harvest summertime period influenced by large scale biomass fires highlighting presence of unmeasured compounds. Increased missing OH reactivity between the two summertime periods was associated with increased concentrations of compounds with strong photochemical source such as acetaldehyde, acetone, hydroxyacetone, nitromethane, amides, isocyanic acid and primary emissions of acetonitrile and aromatic compounds. Currently even the most detailed state-of-the art atmospheric chemistry models exclude formamide, acetamide, nitromethane and isocyanic acid and their highly reactive precursor alkylamines (e.g. methylamine, ethylamine, dimethylamine, trimethylamine). For improved understanding of atmospheric chemistry-air quality-climate feedbacks in biomass-fire impacted atmospheric environments, future studies should include these compounds.