Abstract. Submicron aerosol was analyzed during the MILAGRO field campaign in March 2006 at the T0 urban supersite in Mexico City with a High-Resolution Aerosol Mass Spectrometer (AMS) and complementary instrumentation. Positive Matrix Factorization (PMF) of high resolution AMS spectra identified a biomass burning organic aerosol (BBOA) component, which includes several large plumes that appear to be from forest fires within the region. Here, we show that the AMS BBOA concentration at T0 correlates with fire counts in the vicinity of Mexico City and that most of the BBOA variability is captured when the FLEXPART model is used for the dispersion of fire emissions as estimated from satellite fire counts. The resulting FLEXPART fire impact factor (FIF) correlates well with the observed BBOA, acetonitrile (CH3CN), levoglucosan, and potassium, indicating that wildfires in the region surrounding Mexico City are the dominant source of BBOA at T0 during MILAGRO. The impact of distant BB sources such as the Yucatan is small during this period. All fire tracers are correlated, with BBOA and levoglucosan showing little background, acetonitrile having a well-known tropospheric background of ~100–150 pptv, and PM2.5 potassium having a background of ~160 ng m−3 (two-thirds of its average concentration), which does not appear to be related to BB sources. We define two high fire periods based on satellite fire counts and FLEXPART-predicted FIFs. We then compare these periods with a low fire period when the impact of regional fires is about a factor of 5 smaller. Fire tracers are very elevated in the high fire periods whereas tracers of urban pollution do not change between these periods. Dust is also elevated during the high BB period but this appears to be coincidental due to the drier conditions and not driven by direct dust emission from the fires. The AMS oxygenated organic aerosol (OA) factor (OOA, mostly secondary OA or SOA) does not show an increase during the fire periods or a correlation with fire counts, FLEXPART-predicted FIFs or fire tracers, indicating that it is dominated by urban and/or regional sources and not by the fires near the MCMA. A new 14C aerosol dataset is presented. Both this new and a previously published dataset of 14C analysis suggest a similar BBOA contribution as the AMS and chemical mass balance (CMB), resulting in 13% higher non-fossil carbon during the high vs. low regional fire periods. The new dataset has ~15% more fossil carbon on average than the previously published one, and possible reasons for this discrepancy are discussed. During the low regional fire period, 38% of organic carbon (OC) and 28% total carbon (TC) are from non-fossil sources, suggesting the importance of urban and regional non-fossil carbon sources other than the fires, such as food cooking and regional biogenic SOA. The ambient BBOA/ΔCH3CN ratio is much higher in the afternoon when the wildfires are most intense than during the rest of the day. Also, there are large differences in the contributions of the different OA components to the surface concentrations vs. the integrated column amounts. Both facts may explain some apparent disagreements between BB impacts estimated from afternoon aircraft flights vs. those from 24-h ground measurements. We show that by properly accounting for the non-BB sources of K, all of the BB PM estimates from MILAGRO can be reconciled. Overall, the fires from the region near the MCMA are estimated to contribute 15–23% of the OA and 7–9% of the fine PM at T0 during MILAGRO, and 2–3% of the fine PM as an annual average. The 2006 MCMA emissions inventory contains a substantially lower impact of the forest fire emissions, although a fraction of these emissions occur just outside of the MCMA inventory area.

The OH-radical initiated oxidation of a series of monocyclic aromatic hydrocarbons (benzene, toluene, o-, m-, and p-xylene) in the presence of oxygen and NO(x) was investigated in a flowtube coupled with a chemical ionization mass spectrometer (CIMS). OH-radical addition to the aromatic ring--the major reaction pathway--has previously been shown to have a particular sensitivity to experimental conditions. This is the first flowtube study that demonstrates the atmospheric relevance of product yields from the OH-addition channel on the millisecond time scale (35-75 ms); the phenol yield from benzene and cresol yields from toluene are found to be 51.0 +/- 4.3% and 17.7 +/- 2.1%, in excellent agreement with previous studies under close to atmospheric conditions. We further report unambiguous experimental evidence that dealkylation is a novel and significant pathway for toluene and o-, m-, and p-xylene oxidation. At 150 Torr of O2 partial pressure, toluene is found to dealkylate with a yield of 5.4 +/- 1.2% phenol; similarly, m-, o-, and p-xylene dealkylate with yields of 11.2 +/- 3.8%, 4.5 +/- 3.2%, and 4.3 +/- 3.1% cresol, respectively. A dealkylation mechanism via OH-addition in the ipso position is feasible (DeltaH = -9 kcal/mol for phenol formation from toluene) but does not lend itself easily to explain the significant isomer effect observed among xylenes; instead an alternative mechanism is presented that can explain this isomer effect and forms phenol and likely epoxide type products with identical m/z (indistinguishable in our CIMS analysis) via a carbene-type intermediate. Dealkylation adds to the atmospheric production of phenol- and likely epoxide-type products, with aldehydes as expected co-products, and helps improve the carbon balance in the initial stages of aromatic oxidation.

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Rate coefficients for the gas-phase reaction between nitrate radicals and the unsaturated alcohols 2-buten-1-ol (crotyl alcohol, a mixture of cis and trans), 3-methyl-2-buten-1-ol (MBO321), and 3-methyl-3-buten-1-ol (MBO331) and the alkenes 2-methyl-1-butene and 3-methyl-1-butene have been determined. The values that are found are (4.1 ( 0.4) × 10 -13 , (1.0 ( 0.1) × 10 -12 , (2.7 ( 0.2) × 10 -13 , (5 ( 1) × 10 -13 , and (1.4 ( 0.2) × 10 -14 cm 3 molecule -1 s -1 , respectively. In addition, the rate coefficients for 2-propen-1-ol (allyl alcohol), 3-buten-2-ol, 2-methyl-3-buten-2-ol (MBO232), and 2-methyl-2-butene were redetermined. The experiments were performed using the relative rate technique. One set of experiments was carried out using a glass reactor and long-path FTIR spectroscopy. A second set of experiments was carried out with a collapsible sampling bag as the reaction chamber, employing solid-phase micro extraction (SPME) for sampling and gas chromatography/flame ionization detection for analysis of the reaction mixtures. The results from the two experimental methods showed good correspondence. All experiments were carried out at 297 ( 2 K and 1020 ( 10 mbar and using both synthetic air and nitrogen as the bath gas. The energy of the highest occupied molecular orbital (E HOMO ) of the investigated organic compounds was calculated using the PM3 semiempirical approach, and a relation to ln(k) was observed. A similar relation, available from the literature developed for alkenes, would underestimate the unsaturated alcohol rate coefficients slightly. The measured values of the rate coefficients for the unsaturated alcohols are in reasonable agreement with those predicted by a structureactivity relationship (SAR) available in the literature. However, the SAR slightly overestimates the rate coefficients. The presence of the OH group in the examined alcohols does not affect the NO 3 rate coefficient compared to that of the parent alkene, except in the case of MBO321 and MBO331 where steric effects may be responsible for lowering the reactivity.

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The aim of this study was to evaluate the reliability of direct determination of trace and major element concentrations in plasma samples from wild (six hawksbill, nine green, and nine loggerhead) and captive sea turtles (25 howksbill, five green, and three loggerhead) in Okinawa, Japan. The particle induced X-ray emission method allowed detection of 23 trace and major elements (Al, As, Br, Ca, Cl, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Ni, P, Pb, S, Se, Si, Sr, Ti, Y, and Zn). The wild sea turtles were found to have high concentrations of As and Pb in plasma compared with captive, but there were no significant changes in the Al and Hg concentrations. Loggerhead sea turtles were found to have significantly higher accumulation of As and Pb in plasma in comparison to other species. These findings may be useful when adjusting environmental and species-related factors in severely polluted marine ecosystems. Our results indicate that measuring the plasma As and Pb concentrations in wild sea turtles might be of help to assess the level of pollution in marine ecosystems, keeping in mind that loggerhead sea turtles had been shown to have higher levels of As and Pb in plasma.

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