Evaluation of a New Chemical Mechanism for 2-Amino-2-methyl-1-propanol in a Reactive Environment from CSIRO Smog Chamber Experiments.

Amines are considered as an emerging class of atmospheric pollutants that are of great importance to atmospheric chemistry and new particle formation. As a typical amine, 2-amino-2-methyl-1-propanol (AMP) is one of the proposed solvents for capturing CO2 from flue gas streams in amine-based post-combustion CO2 capture plants, and it is expected to result in AMP emission and secondary product formation in the atmosphere. However, the current knowledge of its atmospheric chemistry and kinetics is poorly understood, particularly in a reactive environment. In this work, we used the CSIRO smog chamber to study the photo-oxidation of AMP in the presence of volatile organic compound (VOC)-NOx surrogate mixtures over a range of initial amine concentrations. O3 formation was significantly inhibited when AMP was added to the surrogate VOC-NOx mixtures, implying that AMP could alter known atmospheric chemical reaction pathways and the prevailing reactivity. Simultaneously, a large amount of AMP-derived secondary aerosol was formed, with a considerably high aerosol mass yield (i.e., ratio of aerosol formed to reacted AMP) of 1.06 ± 0.20. Based on updated knowledge of its kinetics, oxidation pathways, and product yields, we have developed a new mechanism (designated as CSIAMP-19), integrated it into the Carbon Bond 6 (CB6) chemical mechanism, and evaluated it against available smog chamber data. Compared with the existing AMP mechanism (designated as CarterAMP-08), the modified CB6 with CSIAMP-19 mechanism improves prediction against AMP-VOC-NOx experiments across a range of initial AMP concentrations, within ±10% model error for gross ozone production. Our results contribute to scientific understanding of AMP photochemistry and to the development of the chemical mechanism of other amines. Once some potential limitations are considered, the updated AMP reaction scheme can be further embedded into the chemical transport model for regional modeling scenarios where AMP-related emissions are of concern.

Differential injurious effects of ambient and traffic-derived particulate matter on airway epithelial cells.

BACKGROUND AND OBJECTIVE: Exposure to airborne particulate matter (PM) may promote development of childhood asthma and trigger acute exacerbations of existing asthma via injury to airway epithelial cells (AEC). METHODS: We compared the response of AEC to ambient particulates with median aerodynamic diameters of <10 µm or <2.5 µm from the Sydney metropolitan region (Sydney PM10 or PM2.5), to traffic-derived particulates from the exhaust stack of a motorway tunnel or to inert carbon black as a control. RESULTS: Sydney PM10 strongly stimulated messenger RNA expression and secretion of the pro-inflammatory cytokines interleukin 6 (IL-6) and chemokine (C-X-C motif) ligand 1 (CXCL1) by mouse tracheal AEC. In contrast, traffic-derived particulates did not. Similarly, PM10 stimulated expression of IL6, IL8 and IL1B by human AEC. Mass spectrometric analysis showed that PM10 contained much higher levels of elements associated with dusts of geological origin. In contrast, tunnel soot contained much higher levels of various organic compounds, notably including long straight-chain alkanes and diesel-derived polycyclic aromatic hydrocarbons. Sydney PM2.5, as well as PM10 collected during a period including a major dust storm, both of which contained relatively lower levels of iron but similar levels of other crustal elements, did not stimulate expression or secretion of CXCL1 by mouse AEC. CONCLUSIONS: Ambient PM10 is likely to be more important than traffic-derived PM in causing injury to AEC leading to production of pro-inflammatory cytokines. The injurious effects may be related to the presence of iron in the coarse fraction of airborne PM. These findings are likely to be relevant to the pathogenesis of asthma.

Characterization and ecological risk assessment of nanoparticulate CeO2 as a diesel fuel catalyst.

Nanoparticulate cerium dioxide (nano-CeO2 ), when combusted as an additive to diesel fuel, was transformed from 6 nm to 14 nm sizes into particles near 43 nm, with no obvious change in the unit cell dimensions or crystalline form. Cerium sulfate, if formed during combustion, was below detection limits. Ceria nanoparticles were agglomerated within the soot matrix, with a mean aerodynamic diameter near 100 nm. The dissolution of cerium from the dried ceria catalyst in synthetic soft water was extremely small (<0.0006% or <0.2 µg Ce/L), with particles being highly agglomerated (<450 nm). Agglomeration was reduced in the presence of humic acid. In the combusted samples, soot was dominant, and the solubility of cerium in soft water showed an almost 100-fold increase in the <1 nm fraction compared to that before combustion. It appeared that the nano-CeO2 remained agglomerated within the soot matrix and would not be present as dispersed nanoparticles in aquatic or soil environments. Despite the increased dissolution, the solubility was not sufficient for the combusted ceria to represent a risk in aquatic ecosystems. The predicted environmental concentrations were still orders of magnitude below the predicted no effects concentration of near 1 mg/L. In the soil environment, any cerium released from soot materials would interact with natural colloids, decreasing cerium concentrations in soil solutions and further minimizing the potential risk to soil organisms.