The Amazon Basin plays key role in atmospheric chemistry, biodiversity and climate change. In this study we applied nanoelectrospray (nanoESI) ultra-high-resolution mass spectrometry (UHRMS) for the analysis of the organic fraction of PM_2.5 aerosol samples collected during dry and wet seasons at a site in central Amazonia receiving background air masses, biomass burning and urban pollution. Comprehensive mass spectral data evaluation methods (e.g. Kendrick mass defect, Van Krevelen diagrams, carbon oxidation state and aromaticity equivalent) were used to identify compound classes and mass distributions of the detected species. Nitrogen- and/or sulfur-containing organic species contributed up to 60 % of the total identified number of formulae. A large number of molecular formulae in organic aerosol (OA) were attributed to later-generation nitrogen- and sulfur-containing oxidation products, suggesting that OA composition is affected by biomass burning and other, potentially anthropogenic, sources. Isoprene-derived organosulfate (IEPOX-OS) was found to be the most dominant ion in most of the analysed samples and strongly followed the concentration trends of the gas-phase anthropogenic tracers confirming its mixed anthropogenic–biogenic origin. The presence of oxidised aromatic and nitro-aromatic compounds in the samples suggested a strong influence from biomass burning especially during the dry period. Aerosol samples from the dry period and under enhanced biomass burning conditions contained a large number of molecules with high carbon oxidation state and an increased number of aromatic compounds compared to that from the wet period. The results of this work demonstrate that the studied site is influenced not only by biogenic emissions from the forest but also by biomass burning and potentially other anthropogenic emissions from the neighbouring urban environments.

We present OH observations from Nitrogen, Aerosol Composition, and Halogens on a Tall Tower 2011 (NACHTT‐11) held at the Boulder Atmospheric Observatory in Weld County, Colorado. Average OH levels at noon were ~ 2.7 × 10⁶ molecules cm⁻³ at 2 m above ground level. Nitrous acid (HONO) photolysis was the dominant OH source (80.4%) during this campaign, while alkene ozonolysis (4.9%) and ozone photolysis (14.7%) were smaller contributions to OH production. To evaluate recycling sources of OH from HO₂ and RO₂, an observationally constrained University of Washington Chemical Mechanism (UWCM) box model (version 2.1) was employed to simulate ambient OH levels over several scenarios. For the base run, not constrained by observed HONO, the model significantly underestimated OH by a factor of 5.3 in the morning (9:00–11:00) and by a factor of 3.2 in the afternoon (13:00–15:00). The results suggest that known chemistry cannot constrain HONO and, subsequently, OH during the observational period. When HONO is constrained in the model by observations (< 50 m), the discrepancy between observation and model simulation improves to a factor of 1.3 in the morning and a factor 1.1 in the afternoon, within the 35% estimated instrumental uncertainty. However, the model produces both a morning and afternoon maximum in OH, in contrast to the observations, which show strong evidence for morning OH production but no distinct morning maximum. Two additional OH sources were also considered, although they do not improve the differences in modeled and measured temporal OH profiles. First, the impact of daytime HONO gradients near the ground surface (< 20 m) was evaluated. Strong HONO gradients were observed between 06:00 and 09:00 MST (mountain standard time), especially within 20 m of the surface. When constrained to HONO observed below 20 m (rather than 50 m), the model produced an even larger morning OH maximum, in contrast to the observations. Second, Cl atoms from ClNO₂ photolysis producing RO₂ from reaction with alkanes, while significant, produced steady state Cl atom levels (~ 10³ atoms cm⁻³) that were too low to significantly perturb measured OH through reactions of organic peroxy radicals produced from Cl reactions with volatile organic compounds.

The San Joaquin Valley (SJV) in California experiences persistent air-quality problems associated with elevated particulate matter (PM) concentrations due to anthropogenic emissions, topography, and meteorological conditions. Thus it is important to unravel the various sources and processes that affect the physicochemical properties of PM in order to better inform pollution abatement strategies and improve parameterizations in air-quality models. During January and February 2013, a ground supersite was installed at the Fresno–Garland California Air Resources Board (CARB) monitoring station, where comprehensive, real-time measurements of PM and trace gases were performed using instruments including an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and an Ionicon proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) as part of the NASA Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) campaign. The average submicron aerosol (PM₁) concentration was 31.0 µg m⁻³ and the total mass was dominated by organic aerosols (OA, 55 %), followed by ammonium nitrate (35 %). High PM pollution events were commonly associated with elevated OA concentrations, mostly from primary sources. Organic aerosols had average atomic oxygen-to-carbon (O / C), hydrogen-to-carbon (H / C), and nitrogen-to-carbon (N / C) ratios of 0.42, 1.70, and 0.017, respectively. Six distinct sources of organic aerosol were identified from positive matrix factorization (PMF) analysis of the AMS data: hydrocarbon-like OA (HOA; 9 % of total OA, O / C = 0.09) associated with local traffic, cooking OA (COA; 18 % of total OA, O / C = 0.19) associated with food cooking activities, two biomass burning OA (BBOA1: 13 % of total OA, O / C = 0.33; BBOA2: 20 % of total OA, O / C = 0.60) most likely associated with residential space heating from wood combustion, and semivolatile oxygenated OA (SV-OOA; 16 % of total OA, O / C = 0.63) and low-volatility oxygenated OA (LV-OOA; 24 % of total OA, O / C = 0.90) formed via chemical reactions in the atmosphere. Large differences in aerosol chemistry at Fresno were observed between the current campaign (winter 2013) and a previous campaign in winter 2010, most notably that PM₁ concentrations were nearly 3 times higher in 2013 than in 2010. These variations were attributed to differences in the meteorological conditions, which influenced primary emissions and secondary aerosol formation. In particular, COA and BBOA concentrations were greater in 2013 than 2010, where colder temperatures in 2013 likely resulted in increased biomass burning activities. The influence from a nighttime formed residual layer that mixed down in the morning was found to be much more intense in 2013 than 2010, leading to sharp increases in ground-level concentrations of secondary aerosol species including nitrate, sulfate, and OOA, in the morning between 08:00 and 12:00 PST. This is an indication that nighttime chemical reactions may have played a more important role in 2013. As solar radiation was stronger in 2013 the higher nitrate and OOA concentrations in 2013 could also be partly due to greater photochemical production of secondary aerosol species. The greater solar radiation and larger range in temperature in 2013 also likely led to both SV-OOA and LV-OOA being observed in 2013 whereas only a single OOA factor was identified in 2010.

Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16–36 % of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigated with an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding ∼ 100 µg m⁻³ of pure H₂SO₄ to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical (k_OH) was estimated as 4.0 ± 2.0 × 10⁻¹³ cm³ molec⁻¹ s⁻¹, which is equivalent to more than a 2-week lifetime. A similar k_OH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (> 1 × 10¹² molec cm⁻³ s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients (γ_OH = 0.59 ± 0.33 in SE US and γ_OH = 0.68 ± 0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of k_OH and γ_OH was observed, consistent with surface-area-limited OH uptake. No decrease of k_OH was observed as OH concentrations increased. These observations of physicochemical properties of IEPOX-SOA can help to constrain OA impact on air quality and climate.

Secondary organic aerosol (SOA) formation from ambient air was studied using an oxidation flow reactor (OFR) coupled to an aerosol mass spectrometer (AMS) during both the wet and dry seasons at the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) field campaign. Measurements were made at two sites downwind of the city of Manaus, Brazil. Ambient air was oxidized in the OFR using variable concentrations of either OH or O₃, over ranges from hours to days (O₃) or weeks (OH) of equivalent atmospheric aging. The amount of SOA formed in the OFR ranged from 0 to as much as 10 µg m⁻³, depending on the amount of SOA precursor gases in ambient air. Typically, more SOA was formed during nighttime than daytime, and more from OH than from O₃ oxidation. SOA yields of individual organic precursors under OFR conditions were measured by standard addition into ambient air and were confirmed to be consistent with published environmental chamber-derived SOA yields. Positive matrix factorization of organic aerosol (OA) after OH oxidation showed formation of typical oxidized OA factors and a loss of primary OA factors as OH aging increased. After OH oxidation in the OFR, the hygroscopicity of the OA increased with increasing elemental O : C up to O : C ∼ 1.0, and then decreased as O : C increased further. Possible reasons for this decrease are discussed. The measured SOA formation was compared to the amount predicted from the concentrations of measured ambient SOA precursors and their SOA yields. While measured ambient precursors were sufficient to explain the amount of SOA formed from O₃, they could only explain 10–50 % of the SOA formed from OH. This is consistent with previous OFR studies, which showed that typically unmeasured semivolatile and intermediate volatility gases (that tend to lack C = C bonds) are present in ambient air and can explain such additional SOA formation. To investigate the sources of the unmeasured SOA-forming gases during this campaign, multilinear regression analysis was performed between measured SOA formation and the concentration of gas-phase tracers representing different precursor sources. The majority of SOA-forming gases present during both seasons were of biogenic origin. Urban sources also contributed substantially in both seasons, while biomass burning sources were more important during the dry season. This study enables a better understanding of SOA formation in environments with diverse emission sources.

The Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H₂O, Organics & Nitrogen (BEACHON) project seeks to understand the feedbacks and inter-relationships between hydrology, biogenic emissions, carbon assimilation, aerosol properties, clouds and associated feedbacks within water-limited ecosystems. The Manitou Experimental Forest Observatory (MEFO) was established in 2008 by the National Center for Atmospheric Research to address many of the BEACHON research objectives, and it now provides a fixed field site with significant infrastructure. MEFO is a mountainous, semi-arid ponderosa pine-dominated forest site that is normally dominated by clean continental air but is periodically influenced by anthropogenic sources from Colorado Front Range cities. This article summarizes the past and ongoing research activities at the site, and highlights some of the significant findings that have resulted from these measurements. These activities include - soil property measurements; - hydrological studies; - measurements of high-frequency turbulence parameters; - eddy covariance flux measurements of water, energy, aerosols and carbon dioxide through the canopy; - determination of biogenic and anthropogenic volatile organic compound emissions and their influence on regional atmospheric chemistry; - aerosol number and mass distributions; - chemical speciation of aerosol particles; - characterization of ice and cloud condensation nuclei; - trace gas measurements; and - model simulations using coupled chemistry and meteorology. In addition to various long-term continuous measurements, three focused measurement campaigns with state-of-the-art instrumentation have taken place since the site was established, and two of these studies are the subjects of this special issue: BEACHON-ROCS (Rocky Mountain Organic Carbon Study, 2010) and BEACHON-RoMBAS (Rocky Mountain Biogenic Aerosol Study, 2011).