Combustion-generated nanoparticulates in the El Paso, TX, USA / Juarez, Mexico Metroplex: their comparative characterization and potential for adverse health effects.

In this paper we report on the collection of fine (PM1) and ultrafine (PM0.1), or nanoparticulate, carbonaceous materials using thermophoretic precipitation onto silicon monoxide/formvar-coated 3 mm grids which were examined in the transmission electron microscope (TEM). We characterize and compare diesel particulate matter (DPM), tire particulate matter (TPM), wood burning particulate matter, and other soot (or black carbons (BC)) along with carbon nanotube and related fullerene nanoparticle aggregates in the outdoor air, as well as carbon nanotube aggregates in the indoor air; and with reference to specific gas combustion sources. These TEM investigations include detailed microstructural and microdiffraction observations and comparisons as they relate to the aggregate morphologies as well as their component (primary) nanoparticles. We have also conducted both clinical surveys regarding asthma incidence and the use of gas cooking stoves as well as random surveys by zip code throughout the city of El Paso. In addition, we report on short term (2 day) and longer term (2 week) in vitro assays for black carbon and a commercial multiwall carbon nanotube aggregate sample using a murine macrophage cell line, which demonstrate significant cytotoxicity; comparable to a chrysotile asbestos nanoparticulate reference. The multi-wall carbon nanotube aggregate material is identical to those collected in the indoor and outdoor air, and may serve as a surrogate. Taken together with the plethora of toxic responses reported for DPM, these findings prompt concerns for airborne carbonaceous nanoparticulates in general. The implications of these preliminary findings and their potential health effects, as well as directions for related studies addressing these complex issues, will also be examined.

Carbon nanotubes and other fullerene nanocrystals in domestic propane and natural gas combustion streams.

Carbon nanotubes and other aggregated fullerene-related multi-layer shell structures have been collected in propane and natural gas flame emissions from domestic cooking stoves and observed by transmission electron microscopy. Some aggregated nanoparticles collected on 3 mm electron microscope grids by thermal precipitation were mostly multi-walled nanotubes; many tangled and distorted, and aggregated with other closed-concentric, multi-shell forms. Such clean-burning regimes may be major contributors to complex particulate matter in indoor and outdoor air.

Chemistry and nanoparticulate compositions of a 10,000 year-old ice core melt water.

Particulates extracted from a single section of a 10,000 year-old ice core melt sample exhibited characteristics of contemporary, airborne fine particulates: a majority were microcrystalline particulates and aggregated microcrystals, including some mixtures of microcrystals and carbonaceous matter. Particularly significant were the presence of carbon nanotubes and fullerene nanocrystals composing aggregated particulates reflecting global combustion products similar to contemporary, airborne carbon nanocrystal aggregates. ICP elemental analysis of the melt water showed significant concentrations of Ca, K and especially Na (corresponding to K, NaCl), S, Si, Se, and Zn. Overall, the elemental analysis of the melt water is similar to local tap water. However, lead was absent in the local tap water and only half the concentration of selenium was present in the tap water in contrast to the ice core water. While these observations cannot be generalized, the methodology illustrates the potential to characterize and compare airborne particulate regimes and water chemistries in antiquity.

Characterization of nanostructure phenomena in airborne particulate aggregates and their potential for respiratory health effects.

Airborne aggregates of nanoparticulates were collected on carbon/form-coated, 100-mesh Ni TEM grids in a thermal precipitator and observed in an analytical TEM utilizing a BF-SAED-DF-EDS characterization protocol to identify the nanocrystalline or nanoparticulate components, especially their degree of crystallinity, size, structural/morphologic features, and chemistries. Reference aggregates of TiO2 rutile and anatase as well as Si3N4 nanoparticles were used to establish these characterization protocols, which were applied to several hundred individual particulates: homogeneous aggregates of carbonaceous/diesel particulate matter, complex mixtures of carbonaceous matter, including carbon nanocrystals, and inorganic nanocrystals; and heterogeneous, nanocrystal/nanoparticulate aggregates. Most airborne particulates were aggregates ranging in aerodynamic diameters from a few nanometers to a few microns; containing as few as 2 nanocrystals to several thousand nanocrystals or nanoparticulates such as carbonaceous spherules arranged in complex branched homogeneous aggregates composing diesel exhaust, with spherule diameters ranging from 10 to 30 nm. The potential for ultrafine airborne aggregates to fragment into hundreds or thousands of nanoparticulate components in human airways and act as toxic agents in deep lung tissue is demonstrated.