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The observed iron mobilization rate from size-fractionated coal fly ash is consistent with the model predictions for a limiting case of mass transfer where the dominant resistance is diffusion through a layer of depleted solid between the surface of spherical particles and a shrinking core of unreacted material. The rate of mobilization of iron from coal fly ash under physiologically relevant conditions in vitro was previously shown to depend on the size of the ash particles and on the source of the coal, and these in vitro measurements have been shown to correlate with indirect measurements of excess iron in cultured cells. Existing iron mobilization data were compared to mathematical models for mass transfer and chemical reaction in solid-liquid heterogeneous systems. Liquid-phase diffusion resistance can be ruled out as the rate-limiting mechanism for iron mobilization as the model predictions for this case are clearly inconsistent with the measurements. Other plausible hypotheses, such as a rate limited by a heterogeneous surface reaction, cannot be conclusively ruled out by the available data. These mathematical analysis methods are applicable to the design of future experiments to determine the rate-limiting mechanism for the mobilization of iron and of other transition metals from both ambient air samples and surrogates for major sources of particulate air pollution.

Iron speciation by Mössbauer spectroscopy indicates that ferric iron in an aluminosilicate glass phase is the source of the bioavailable iron in coal fly ash and that this iron species is associated with combustion particles, but not with crustal dust derived from soil minerals. Urban particulate has been shown to be a source of bioavailable iron and has been shown to be able to induce the formation of reactive species in cell culture experiments. Crustal dust and laboratory-generated coal fly ash have been studied as surrogates for two sources of metal-bearing particles in ambient air. As much as a 60-fold difference in the amount of iron mobilized by the chelator citrate was observed between fly ash and crustal dust samples with similar total iron contents. The extent of iron mobilization by citrate in vitro has been shown to correlate with indirect measures of excess iron in cultured cells and with assays for reactive oxygen species generation in vitro. Mössbauer spectroscopy of coal fly ash, before and after treatment with the chelator desferrioxamine B, showed that the iron in an aluminosilicate glass phase was preferentially removed. The removal of the glass-phase iron greatly reduced the amount of iron that could be mobilized by citrate and prevented the particles from inducing interleukin-8 in cultured human lung epithelial (A549) cells. Ferric iron in aluminosilicate glass is associated with particles formed at high temperatures followed by rapid cooling. The observation that ferric iron in aluminosilicate glass is the source of bioavailable iron in coal fly ash suggests that particles from ambient sources and other specific combustion sources should be examined for the presence of this potential source of bioavailable iron.

Particulate air pollution contains iron, and some of the pathological effects after inhalation may be due to radical species produced by iron-catalyzed reactions. We tested the hypothesis that iron present in coal fly ash (CFA) could induce the expression and synthesis of the inflammatory cytokine interleukin-8 (IL-8). CFA, containing as much as 14% iron, was used as a model combustion source particle. Three coal types were used to generate three size fractions enriched in particles [submicron (<1 micrometer), fine (<2.5 micrometer), or coarse (2.5-10 micrometer]), as well as the fraction of >10 micrometer. Treatment of human lung epithelial (A549) cells for 4 h with CFA from Utah enriched in <1 micrometer particles (20 microgram/cm(2)) resulted in a 2.6-fold increase in mRNA levels for IL-8. IL-8 levels were increased in the medium by as much as 8-fold when cells were treated with the fraction enriched in the smallest size Utah CFA for 24 h. IL-8 production was completely inhibited when the CFA was pretreated with the metal chelator desferrioxamine B, suggesting that a transition metal was responsible for the induction, probably iron. Treatment with a soluble form of iron, ferric ammonium citrate (FAC), mimicked the IL-8 level increase observed with CFA. There was a direct relationship, above a threshold level of bioavailable iron, between the levels of IL-8 and bioavailable iron in A549 cells treated with CFA or FAC. Further, the relationship between IL-8 and bioavailable iron for CFA was indistinguishable from that for FAC. These results strongly suggest that iron can induce IL-8 in A549 cells and that iron was the likely component of CFA that induced IL-8. CFA-induced IL-8 production was inhibited by tetramethylthiourea or dimethyl sulfoxide, suggesting that radical species were involved in the induction. These results demonstrate that iron present in CFA may be responsible for production and release of inflammatory mediators by the lung epithelium through generation of radical species and suggest that iron may contribute to the exacerbation of respiratory problems by particulate air pollution.

Particulate air pollution, including coal fly ash, contains iron, and some of the pathological effects after inhalation may be due to reactive oxygen species produced by iron-catalyzed reactions. The objective of this study was to determine whether iron, present in coal fly ash, was mobilized, leading to ferritin induction in human airway epithelial cells, and whether the size of the particles affected the amount of iron mobilized. Three types of coal were used to generate the three size fractions of fly ash collected. The Utah coal fly ash was generated from a bituminous b coal, the Illinois coal fly ash from a bituminous c coal, and the North Dakota coal fly ash from a lignite a coal. Three size fractions were studied to compare the amount of iron mobilized in human airway epithelial (A549) cells and by citrate in cell-free suspensions. The size fractions selected were fine (<2.5 microm) and coarse (2.5-10 microm) components of PM10, airborne particulate matter <10 microm in diameter, and the fraction greater than 10 microm. Coal fly ash samples were incubated with 1 mM citrate to determine if iron associated with coal fly ash could be mobilized. Iron was mobilized by citrate from all three size fractions of all three coal types to levels as high as 56.7 nmol of Fe/mg of coal fly ash after 24 h. With all three coal types, more iron was mobilized by citrate from the <2.5 microm fraction than from the >2.5 microm fractions. Further, the mobilized iron was in the Fe(III) form. To determine if iron associated with the coal fly ash could be mobilized by A549 cells, cells were treated with coal fly ash, and the amount of the iron storage protein ferritin was determined after 24 h. Ferritin levels were increased by as much as 11.9-fold in cells treated with coal fly ash. With two of the three types of coal studied, more ferritin was induced in cells treated with the <2.5 microm fraction than with the >2.5 microm fractions. Further, inhibition of the endocytosis of the coal fly ash by the cells resulted in ferritin levels that were near that of the untreated cells, suggesting that iron was mobilized intracellularly, not in the culture medium. The results of this study suggest that differences in particle size and speciation of iron may affect the release of iron in human airway epithelial cells.