Biomass burning and urban air pollution over the Central Mexican Plateau

Observations during the 2006 dry season of highly elevated concentrations of cyanides in the atmosphere above Mexico City (MC) and the surrounding plains demonstrate that biomass burning (BB) significantly impacted air quality in the region. We find that during the period of our measurements, fires contribute more than half of the organic aerosol mass and submicron aerosol scattering, and one third of the enhancement in benzene, reactive nitrogen, and carbon monoxide in the outflow from the plateau. The combination of biomass burning and anthropogenic emissions will affect ozone chemistry in the MC outflow

Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE): Emissions of particulate matter from wood-and dung-fueled cooking fires, garbage and crop residue burning, brick kilns, and other sources

The Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE) characterized widespread and under-sampled combustion sources common to South Asia, including brick kilns, garbage burning, diesel and gasoline generators, diesel groundwater pumps, idling motorcycles, traditional and modern cooking stoves and fires, crop residue burning, and heating fire. Fuel-based emission factors (EFs; with units of pollutant mass emitted per kilogram of fuel combusted) were determined for fine particulate matter (PM2.5), organic carbon (OC), elemental carbon (EC), inorganic ions, trace metals, and organic species. For the forced-draft zigzag brick kiln, EFPM2.5 ranged from 12 to 19gkg-1 with major contributions from OC (7%), sulfate expected to be in the form of sulfuric acid (31.9%), and other chemicals not measured (e.g., particle-bound water). For the clamp kiln, EFPM2.5 ranged from 8 to 13gkg-1, with major contributions from OC (63.2%), sulfate (23.4%), and ammonium (16%). Our brick kiln EFPM2.5 values may exceed those previously reported, partly because we sampled emissions at ambient temperature after emission from the stack or kiln allowing some particle-phase OC and sulfate to form from gaseous precursors. The combustion of mixed household garbage under dry conditions had an EFPM2.5 of 7.4±1.2gkg-1, whereas damp conditions generated the highest EFPM2.5 of all combustion sources in this study, reaching up to 125±23gkg-1. Garbage burning emissions contained triphenylbenzene and relatively high concentrations of heavy metals (Cu, Pb, Sb), making these useful markers of this source. A variety of cooking stoves and fires fueled with dung, hardwood, twigs, and/or other biofuels were studied. The use of dung for cooking and heating produced higher EFPM2.5 than other biofuel sources and consistently emitted more PM2.5 and OC than burning hardwood and/or twigs; this trend was consistent across traditional mud stoves, chimney stoves, and three-stone cooking fires. The comparisons of different cooking stoves and cooking fires revealed the highest PM emissions from three-stone cooking fires (7.6-73gkg-1), followed by traditional mud stoves (5.3-19.7gkg-1), mud stoves with a chimney for exhaust (3.0-6.8gkg-1), rocket stoves (1.5-7.2gkg-1), induced-draft stoves (1.2-5.7gkg-1), and the bhuse chulo stove (3.2gkg-1), while biogas had no detectable PM emissions. Idling motorcycle emissions were evaluated before and after routine servicing at a local shop, which decreased EFPM2.5 from 8.8±1.3 to 0.71±0.45gkg-1 when averaged across five motorcycles. Organic species analysis indicated that this reduction in PM2.5 was largely due to a decrease in emission of motor oil, probably from the crankcase. The EF and chemical emissions profiles developed in this study may be used for source apportionment and to update regional emission inventories

Investigations of primary and secondary particulate matter of different wood combustion appliances with a high-resolution time-of-flight aerosol mass spectrometer

A series of photo-oxidation smog chamber experiments were performed to investigate the primary emissions and secondary aerosol formation from two different log wood burners and a residential pellet burner under different burning conditions: starting and flaming phase. Emissions were sampled from the chimney and injected into the smog chamber leading to primary organic aerosol (POA) concentrations comparable to ambient levels. The composition of the aerosol was measured by an Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) and black carbon (BC) instrumentation. The primary emissions were then exposed to xenon light to initiate photo-chemistry and subsequent secondary organic aerosol (SOA) production. After correcting for wall losses, the average increase in organic matter (OM) concentrations by SOA formation for the starting and flaming phase experiments with the two log wood burners was found to be a factor of 4.1±1.4 after five hours of aging. No SOA formation was observed for the stable burning phase of the pellet burner. The startup emissions of the pellet burner showed an increase in OM concentration by a factor of 3.3. Including the measured SOA formation potential, average emission factors of BC+POA+SOA, calculated from CO<sub>2</sub> emission, were found to be in the range of 0.04 to 3.9 g/kg wood for the stable burning pellet burner and an old log wood burner during startup respectively. SOA contributed significantly to the ion C<sub>2</sub>H<sub>4</sub>O<sub>2</sub><sup>+</sup> at mass to charge ratio <i>m/z</i> 60, a commonly used marker for primary emissions of wood burning. This contribution at <i>m/z</i> 60 can overcompensate for the degradation of levoglucosan leading to an overestimation of the contribution of wood burning or biomass burning to the total OM. The primary organic emissions from the three different burners showed a wide range in O:C atomic ratio (0.19−0.60) for the starting and flaming conditions, which also increased during aging. Primary wood burning emissions have a rather low relative contribution at <i>m/z</i> 43 (<i>f</i> 43) to the total organic mass spectrum. The non-oxidized fragment C<sub>3</sub>H<sub>7</sub><sup>+</sup> has a considerable contribution at <i>m/z</i> 43 for the fresh OA with an increasing contribution of the oxygenated ion C<sub>2</sub>H<sub>3</sub>O<sup>+</sup> during aging. After five hours of aging, the OA has a rather low C<sub>2</sub>H<sub>3</sub>O<sup>+</sup> signal for a given CO<sub>2</sub><sup>+</sup> fraction, possibly indicating a higher ratio of acid to non-acid oxygenated compounds in wood burning OA compared to other oxygenated organic aerosol (OOA)

Community production modulates coral reef pH and the sensitivity of ecosystem calcification to ocean acidification

Author Posting. © American Geophysical Union, 2017. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Oceans 122 (2017): 745–761, doi:10.1002/2016JC012326.Coral reefs are built of calcium carbonate (CaCO3) produced biogenically by a diversity of calcifying plants, animals, and microbes. As the ocean warms and acidifies, there is mounting concern that declining calcification rates could shift coral reef CaCO3 budgets from net accretion to net dissolution. We quantified net ecosystem calcification (NEC) and production (NEP) on Dongsha Atoll, northern South China Sea, over a 2 week period that included a transient bleaching event. Peak daytime pH on the wide, shallow reef flat during the nonbleaching period was ∼8.5, significantly elevated above that of the surrounding open ocean (∼8.0–8.1) as a consequence of daytime NEP (up to 112 mmol C m−2 h−1). Diurnal-averaged NEC was 390 ± 90 mmol CaCO3 m−2 d−1, higher than any other coral reef studied to date despite comparable calcifier cover (25%) and relatively high fleshy algal cover (19%). Coral bleaching linked to elevated temperatures significantly reduced daytime NEP by 29 mmol C m−2 h−1. pH on the reef flat declined by 0.2 units, causing a 40% reduction in NEC in the absence of pH changes in the surrounding open ocean. Our findings highlight the interactive relationship between carbonate chemistry of coral reef ecosystems and ecosystem production and calcification rates, which are in turn impacted by ocean warming. As open-ocean waters bathing coral reefs warm and acidify over the 21st century, the health and composition of reef benthic communities will play a major role in determining on-reef conditions that will in turn dictate the ecosystem response to climate change.NSF Grant Number: 12205292017-07-3

Impact of aftertreatment devices on primary emissions and secondary organic aerosol formation potential from in-use diesel vehicles: results from smog chamber experiments

Diesel particulate matter (DPM) is a significant source of aerosol in urban areas and has been linked to adverse health effects. Although newer European directives have introduced increasingly stringent standards for primary PM emissions, gaseous organics emitted from diesel cars can still lead to large amounts of secondary organic aerosol (SOA) in the atmosphere. Here we present results from smog chamber investigations characterizing the primary organic aerosol (POA) and the corresponding SOA formation at atmospherically relevant concentrations for three in-use diesel vehicles with different exhaust aftertreatment systems. One vehicle lacked exhaust aftertreatment devices, one vehicle was equipped with a diesel oxidation catalyst (DOC) and the third vehicle used both a DOC and diesel particulate filter (DPF). The experiments presented here were obtained from the vehicles at conditions representative of idle mode, and for one car in addition at a speed of 60 km/h. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was used to measure the organic aerosol (OA) concentration and to obtain information on the chemical composition. For the conditions explored in this paper, primary aerosols from vehicles without a particulate filter consisted mainly of black carbon (BC) with a low fraction of organic matter (OM, OM/BC < 0.5), while the subsequent aging by photooxidation resulted in a consistent production of SOA only for the vehicles without a DOC and with a deactivated DOC. After 5 h of aging ~80% of the total organic aerosol was on average secondary and the estimated "emission factor" for SOA was 0.23–0.56 g/kg fuel burned. In presence of both a DOC and a DPF, only 0.01 g SOA per kg fuel burned was produced within 5 h after lights on. The mass spectra indicate that POA was mostly a non-oxidized OA with an oxygen to carbon atomic ratio (O/C) ranging from 0.10 to 0.19. Five hours of oxidation led to a more oxidized OA with an O/C range of 0.21 to 0.37

Volatility and hygroscopicity of aging secondary organic aerosol in a smog chamber

Peer reviewe

Emissions from biomass burning in the Yucatan

In March 2006 two instrumented aircraft made the first detailed field measurements of biomass burning (BB) emissions in the Northern Hemisphere tropics as part of the MILAGRO project. The aircraft were the National Center for Atmospheric Research C-130 and a University of Montana/US Forest Service Twin Otter. The initial emissions of up to 49 trace gas or particle species were measured from 20 deforestation and crop residue fires on the Yucatan peninsula. This included two trace gases useful as indicators of BB (HCN and acetonitrile) and several rarely, or never before, measured species: OH, peroxyacetic acid, propanoic acid, hydrogen peroxide, methane sulfonic acid, and sulfuric acid. Crop residue fires emitted more organic acids and ammonia than deforestation fires, but the emissions from the main fire types were otherwise fairly similar. The Yucatan fires emitted unusually high amounts of SO2 and particle chloride, likely due to a strong marine influence on this peninsula. As smoke from one fire aged, the ratio ΔO3/ΔCO increased to ~15% in 1×10^7 molecules/cm^3) that were likely caused in part by high initial HONO (~10% of NO_y). Thus, more research is needed to understand critical post emission processes for the second-largest trace gas source on Earth. It is estimated that ~44 Tg of biomass burned in the Yucatan in the spring of 2006. Mexican BB (including Yucatan BB) and urban emissions from the Mexico City area can both influence the March-May air quality in much of Mexico and the US

Total Observed Organic Carbon (TOOC): A synthesis of North American observations

Measurements of organic carbon compounds in both the gas and particle phases measured upwind, over and downwind of North America are synthesized to examine the total observed organic carbon (TOOC) over this region. These include measurements made aboard the NOAA WP-3 and BAe-146 aircraft, the NOAA research vessel Ronald H. Brown, and at the Thompson Farm and Chebogue Point surface sites during the summer 2004 ICARTT campaign. Both winter and summer 2002 measurements during the Pittsburgh Air Quality Study are also included. Lastly, the spring 2002 observations at Trinidad Head, CA, surface measurements made in March 2006 in Mexico City and coincidentally aboard the C-130 aircraft during the MILAGRO campaign and later during the IMPEX campaign off the northwestern United States are incorporated. Concentrations of TOOC in these datasets span more than two orders of magnitude. The daytime mean TOOC ranges from 4.0 to 456 μgC m^−3 from the cleanest site (Trinidad Head) to the most polluted (Mexico City). Organic aerosol makes up 3–17% of this mean TOOC, with highest fractions reported over the northeastern United States, where organic aerosol can comprise up to 50% of TOOC. Carbon monoxide concentrations explain 46 to 86% of the variability in TOOC, with highest TOOC/CO slopes in regions with fresh anthropogenic influence, where we also expect the highest degree of mass closure for TOOC. Correlation with isoprene, formaldehyde, methyl vinyl ketene and methacrolein also indicates that biogenic activity contributes substantially to the variability of TOOC, yet these tracers of biogenic oxidation sources do not explain the variability in organic aerosol observed over North America. We highlight the critical need to develop measurement techniques to routinely detect total gas phase VOCs, and to deploy comprehensive suites of TOOC instruments in diverse environments to quantify the ambient evolution of organic carbon from source to sink

Investigation of the correlation between odd oxygen and secondary organic aerosol in Mexico City and Houston

Many recent models underpredict secondary organic aerosol (SOA) particulate matter (PM) concentrations in polluted regions, indicating serious deficiencies in the models' chemical mechanisms and/or missing SOA precursors. Since tropospheric photochemical ozone production is much better understood, we investigate the correlation of odd-oxygen ([Ox]≡[O3]+[NO2]) [([O subscript x] ≡ [O subscript 3] + [NO subscript 2])] and the oxygenated component of organic aerosol (OOA), which is interpreted as a surrogate for SOA. OOA and Ox [O subscript x] measured in Mexico City in 2006 and Houston in 2000 were well correlated in air masses where both species were formed on similar timescales (less than 8 h) and not well correlated when their formation timescales or location differed greatly. When correlated, the ratio of these two species ranged from 30 μg [mu g] m−3/ppm [m superscript -3 / ppm] (STP) in Houston during time periods affected by large petrochemical plant emissions to as high as 160 μg [mu g] m−3/ppm [m superscript -3 / ppm] in Mexico City, where typical values were near 120 μg [mu g] m−3/ppm [m superscript -3 / ppm]. On several days in Mexico City, the [OOA]/[Ox] [[OOA] / O subscript x]] ratio decreased by a factor of ~2 between 08:00 and 13:00 local time. This decrease is only partially attributable to evaporation of the least oxidized and most volatile components of OOA; differences in the diurnal emission trends and timescales for photochemical processing of SOA precursors compared to ozone precursors also likely contribute to the observed decrease. The extent of OOA oxidation increased with photochemical aging. Calculations of the ratio of the SOA formation rate to the Ox [O subscript x] production rate using ambient VOC measurements and traditional laboratory SOA yields are lower than the observed [OOA]/[Ox] [[OOA] / O subscript x]] ratios by factors of 5 to 15, consistent with several other models' underestimates of SOA. Calculations of this ratio using emission factors for organic compounds from gasoline and diesel exhaust do not reproduce the observed ratio. Although not successful in reproducing the atmospheric observations presented, modeling P(SOA)/P(Ox) [P (SOA) / P (O subscript x)] can serve as a useful test of photochemical models using improved formulation mechanisms for SOA.National Science Foundation (U.S.) (Grant ATM-528227)National Science Foundation (U.S.) (Grant ATM-0528170)National Science Foundation (U.S.) (Grant ATM-0513116)National Science Foundation (U.S.) (Grant ATM-0449815)United States. Dept. of Energy. Office of Biological and Environmental Research. Atmospheric Science Program (Grant DE-FGO2-05ER63982)United States. Dept. of Energy. Office of Biological and Environmental Research. Atmospheric Science Program (Grant DEFGO2- 05ER63980)United States. Dept. of Energy. Office of Biological and Environmental Research. Atmospheric Science Program (Grant DE-FG02-08ER64627)United States. National Oceanic and Atmospheric Administration (Grant NA08OAR4310656