Nanoparticles are being used in broad range of applications; therefore, these materials probably will enter the environment during their life cycle. The objective of the present study is to identify changes in properties of nanoparticles released into the environment with a case study on aluminum nanoparticles. Aluminum nanoparticles commonly are used in energetic formulations and may be released into the environment during their handling and use. To evaluate the transport of aluminum nanoparticles, it is necessary not only to understand the properties of the aluminum in its initial state but also to determine how the nanoparticle properties will change when exposed to relevant environmental conditions. Transport measurements were conducted with a soil-column system that delivers a constant upflow of a suspension of nanoparticles to a soil column and monitors the concentration, size, agglomeration state, and charge of the particles in the eluent. The type of solution and surface functionalization had a marked effect on the charge, stability, and agglomeration state of the nanoparticles, which in turn impacted transport through the receiving matrix. Transport also is dependent on the size of the nanoparticles, although it is the agglomerate size, not the primary size, that is correlated with transportability. Electrostatically induced binding events of positively charged aluminum nanoparticles to the soil matrix were greater than those for negatively charged aluminum nanoparticles. Many factors influence the transport of nanoparticles in the environment, but size, charge, and agglomeration rate of nanoparticles in the transport medium are predictive of nanoparticle mobility in soil.
Historically, obtaining quantitative chemical information using laser desorption ionization mass spectrometry for analyzing individual aerosol particles has been quite challenging. This is due in large part to fluctuations in the absolute ion signals resulting from inhomogeneities in the laser beam profile, as well as chemical matrix effects. Progress has been made in quantifying atomic species using high laser powers, but very few studies have been performed quantifying molecular species. In this study, promising results are obtained using a new approach to measure the fraction of organic carbon (OC) associated with elemental carbon (EC) in aerosol particles using single particle laser desorption ionization. A tandem differential mobility analyzer (TDMA) is used to generate OC/EC particles by size selecting EC particles of a given mobility diameter and then coating them with known thicknesses of OC measured using a second DMA. The mass spectra of the OC/EC particles exiting the second DMA are measured using an ultrafine aerosol timeof-flight mass spectrometer (UF-ATOFMS). A calibration curve is produced with a linear correlation (R 2 = 0.98) over the range of OC/EC ion intensity ratios observed in source and ambient studies. Importantly, the OC/EC values measured in ambient field tests with the UF-ATOFMS show a linear correlation (R 2 = 0.69) with OC/EC mass ratios obtained using semi-continuous filter based thermo-optical measurements. The calibration procedure established herein represents a significant step toward quantification of OC and EC in sub-micron ambient particles using laser desorption ionization mass spectrometry.
Simultaneous measurements of the effective density and chemical composition of individual ambient particles were made in Riverside, California by coupling a differential mobility analyzer (DMA) with an ultrafine aerosol time-of-flight mass spectrometer (UF-ATOFMS). In the summer, chemically diverse particle types (i.e., aged-OC, vanadium-OC-sulfate-nitrate, biomass) all had similar effective densities when measured during the same time period. This result suggests that during the summer study the majority of particle mass for the different particle types was dominated by secondary species (OC, sulfates, nitrates) of the same density, while only a small fraction of the total particle mass is accounted for by the primary particle cores. Also shown herein, the effective density is a dynamic characteristic of the Riverside, CA ambient aerosol, changing by as much as 40% within 16 h. During the summer measurement period, changes in the ambient atmospheric water content correlated with changes in the measured effective densities which ranged from approximately 1.0 to 1.5 g x cm(-3). This correlation is potentially due to evaporation of water from particles in the aerodynamic lens. In contrast, in the fall during a Santa Ana meteorological event, ambient particles with a mobility diameter of 450 nm showed three distinct effective densities, each related to a chemically unique particle class. Particles with effective densities of approximately 0.27 g x cm(-3), 0.87 g x cm(-3), and 0.93 g x cm(-3) were composed mostly of elemental carbon, lubricating oil, and aged organic carbon, respectively. It is interesting to contrast the seasonal differences where in the summer, particle density and mass were determined by high amounts of secondary species, whereas in the fall, relatively clean and dry Santa Ana conditions resulted in freshly emitted particles which retained their distinct source chemistries and densities.
[1] An aerosol time-of-flight mass spectrometer (ATOFMS) was used to measure the sizeresolved mixing state of particles over the northern Indian Ocean in October and November 2004. This period was chosen to observe the impact of the monsoonal transition on the size, chemistry, sources, and radiative properties of atmospheric aerosols in the region. Overall, elemental carbon with sulfate (EC-sulfate), biomass/biofuel burning, fresh sea salt (SS), aged sea salt, fly ash, and EC mixed with sea salt were the dominant supermicron particle types, whereas EC-sulfate, biomass/biofuel burning, and fly ash were the dominant submicron particle types. Interestingly, particles composed mostly of aged organic carbon and nitrate were virtually absent during the campaign. This is possibly from low ozone formation in the region or selective scavenging during transport. Notably, during long-range transport periods when an aethalometer measured the highest black carbon concentrations, 77% of submicron particles between 0.5 and 2.5 mm and 71% of EC/soot particles contained an intense 39 K + ion (a known tracer for biomass/biofuel combustion). These observations suggest when the air mass originated from India, biofuel combustion represented a significant source of the regional atmospheric brown cloud. The majority ($80%) of EC and biomass/biofuel burning particles were mixed with significant amounts of sulfate due to extensive secondary processing of these particles during transport. EC mixed with sea salt was also observed suggesting the particles had undergone cloud processing and become internally mixed during transport. These measurements support the use of an internal mixture of sulfate with EC/soot and biomass/biofuel burning in models to accurately calculate radiative forcing by aerosols in this region.
Gold nanoparticles (GNPs) are used as the matrix for visible-wavelength matrix-assisted laser desorption/ionization (VIS-MALDI) of individual aerosol particles containing ∼50 attomole of a small peptide. A dual polarity time-of-flight mass spectrometer was used to obtain both positive and negative ion mass spectra simultaneously from individual particles using a tunable wavelength desorption/ionization laser. The wavelength of the laser was changed from λ = 440 to 680 nm to observe the wavelength dependence of analyte ion formation. Detection of the positive sodiated molecular ions and negative deprotonated molecular ion of a small peptide was only possible using 5-nm GNPs and not with larger sized (19- and 44-nm) GNPs. While the masses of gold within the sample particles were similar, surface areas were about 10 times more in the 5-nm GNPs, suggesting the total surface area of GNPs within the sample particles may play a role in the formation of molecular ions. At wavelengths near the peak plasmon resonance of the GNPs (λ = 500−540 nm), negative molecular ion signals from a small peptide was higher than with desorption/ionization at λ = 440 nm, with increased fragmentation observed at λ = 440 nm. At wavelengths longer than the peak plasmon absorption, the ability to generate a detectable ion signal decreased rapidly, which is consistent with the steep decrease in the absorbance of GNPs by surface plasmon resonance at these wavelengths. Silver nanoparticles, which also exhibit a surface plasmon resonance, were tested and under our conditions did not appear to work as well. The presented results demonstrate that noble metal nanoparticle matrices can be used for on-line VIS-MALDI analysis of small molecular weight species such as peptides or sugars.
Individual particles produced from atomized rainwater samples collected in California and the Indian Ocean were analyzed with an aerosol time‐of‐flight mass spectrometer (ATOFMS) to investigate the chemical composition of the individual rain residue particles. Insoluble residue particle types were determined on the basis of a comparison of the rainwater particle mass spectra with ambient particle spectra. Major particle types found in rainwater include dust, organic carbon with sodium, aromatic organic carbon, vegetative detritus, and an internally mixed sea salt and elemental carbon class. A unique internally mixed sea salt–elemental carbon particle type was detected in both the ambient and rainwater samples, suggesting this particle type was most likely formed by cloud processing occurring during long‐range transport. The presence of this particle type in remote marine locations has important climate ramifications as it is anticipated it will be strongly absorbing on the basis of the combination of an absorbing particle (elemental carbon) mixed with a high refractive index material (sea salt). Most of the particle types detected in rainwater were detected in the ambient particles with the exception of a unique aromatic particle type detected in rainwater samples from both locations. The presence of the aromatic type coupled with the absence of biomass particles in the rainwater samples leads to the hypothesis the aromatic components were originally associated with atmospheric biomass burning particles. The ubiquitous presence of this aromatic type in rainwater samples highlights the potential importance of biomass burning and/or humic‐like substances (HULIS) compounds in cloud formation and rain processes.
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