Biologically formed nanoparticles of the strongly magnetic mineral, magnetite, were first detected in the human brain over 20 y ago [Kirschvink JL, Kobayashi-Kirschvink A, Woodford BJ (1992) Proc Natl Acad Sci USA 89(16):7683-7687]. Magnetite can have potentially large impacts on the brain due to its unique combination of redox activity, surface charge, and strongly magnetic behavior. We used magnetic analyses and electron microscopy to identify the abundant presence in the brain of magnetite nanoparticles that are consistent with high-temperature formation, suggesting, therefore, an external, not internal, source. Comprising a separate nanoparticle population from the euhedral particles ascribed to endogenous sources, these brain magnetites are often found with other transition metal nanoparticles, and they display rounded crystal morphologies and fused surface textures, reflecting crystallization upon cooling from an initially heated, iron-bearing source material. Such high-temperature magnetite nanospheres are ubiquitous and abundant in airborne particulate matter pollution. They arise as combustion-derived, iron-rich particles, often associated with other transition metal particles, which condense and/ or oxidize upon airborne release. Those magnetite pollutant particles which are <∼200 nm in diameter can enter the brain directly via the olfactory bulb. Their presence proves that externally sourced iron-bearing nanoparticles, rather than their soluble compounds, can be transported directly into the brain, where they may pose hazard to human health.brain magnetite | magnetite pollution particles | Alzheimer's disease | combustion-derived nanoparticles | airborne particulate matter

Funding: In part by SEP-CONACYT 255956. Funding source had no involvement in study design; collection, analysis and interpretation of data; in the writing of the report; and in the decision to submit the article for publication.

The rover has documented lacustrine sediments at Gale Crater, but how liquid water became physically stable on the early Martian surface is a matter of significant debate. To constrain the composition of the early Martian atmosphere during sediment deposition, we experimentally investigated the nucleation and growth kinetics of authigenic Fe-minerals in Gale Crater mudstones. Experiments show that pH variations within anoxic basaltic waters trigger a series of mineral transformations that rapidly generate magnetite and H(). Magnetite continues to form through this mechanism despite high P and supersaturation with respect to Fe-carbonate minerals. Reactive transport simulations that incorporate these experimental data show that groundwater infiltration into a lake equilibrated with a CO-rich atmosphere can trigger the production of both magnetite and H() in the mudstones. H(), generated at concentrations that would readily exsolve from solution, is capable of increasing annual mean surface temperatures above freezing in CO-dominated atmospheres. We therefore suggest that magnetite authigenesis could have provided a short-term feedback for stabilizing liquid water, as well as a principal feedstock for biologically relevant chemical reactions, at the early Martian surface.

In the world-famous sediments of the Chinese Loess Plateau, fossil soils alternate with windblown dust layers to record monsoonal variations over the last ∼3 My. The less-weathered, weakly magnetic dust layers reflect drier, colder glaciations. The fossil soils (paleosols) contain variable concentrations of nanoscale, strongly magnetic iron oxides, formed in situ during the wetter, warmer interglaciations. Mineralogical identification of the magnetic soil oxides is essential for deciphering these key paleoclimatic records. Formation of magnetite, a mixed Fe/Fe ferrimagnet, has been linked to soil redox oscillations, and thence to paleorainfall. An opposite hypothesis states that magnetite can only form if the soil is water saturated for significant periods in order for Fe to be reduced to Fe, and suggests instead the temperature-dependent formation of maghemite, an Fe-oxide, much of which ages subsequently into hematite, typically aluminum substituted. This latter, oxidizing pathway would have been temperature, but not rainfall dependent. Here, through structural fingerprinting and scanning transmission electron microscopy and electron energy loss spectroscopy analysis, we prove that magnetite is the dominant soil-formed ferrite. Maghemite is present in lower concentrations, and shows no evidence of aluminum substitution, negating its proposed precursor role for the aluminum-substituted hematite prevalent in the paleosols. Magnetite dominance demonstrates that magnetite formation occurs in well-drained, generally oxidizing soils, and that soil wetting/drying oscillations drive the degree of soil magnetic enhancement. The magnetic variations of the Chinese Loess Plateau paleosols thus record changes in monsoonal rainfall, over timescales of millions of years.

Exposure to airborne particulate pollution is associated with premature mortality and a range of inflammatory illnesses, linked to toxic components within the particulate matter (PM) assemblage. The effectiveness of trees in reducing urban PM10 concentrations is intensely debated. Modeling studies indicate PM10 reductions from as low as 1% to as high as ~60%. Empirical data, especially at the local scale, are rare. Here, we use conventional PM10 monitoring along with novel, inexpensive magnetic measurements of television screen swabs to measure changes in PM10 concentrations inside a row of roadside houses, after temporarily installing a curbside line of young birch trees. Independently, the two approaches identify >50% reductions in measured PM levels inside those houses screened by the temporary tree line. Electron microscopy analyses show that leaf-captured PM is concentrated in agglomerations around leaf hairs and within the leaf microtopography. Iron-rich, ultrafine, spherical particles, probably combustion-derived, are abundant, form a particular hazard to health, and likely contribute much of the measured magnetic remanences. Leaf magnetic measurements show that PM capture occurs on both the road-proximal and -distal sides of the trees. The efficacy of roadside trees for mitigation of PM health hazard might be seriously underestimated in some current atmospheric models.

The mechanism of green rust sulfate (GR-SO(4)) formation was determined using a novel in situ approach combining time-resolved synchrotron-based wide-angle X-ray scattering (WAXS) with highly controlled chemical synthesis and electrochemical (i.e., Eh and pH) monitoring of the reaction. Using this approach,GR-SO(4) was synthesized under strictly anaerobic conditions by coprecipitation from solutions with known Fe(II)/Fe(III) ratios (i.e., 1.28 and 2) via the controlled increase of pH. The reaction in both systems proceeded via a three-stage precipitation and transformation reaction. During the first stage,schwertmannite (Fe(8)O(8)(OH)(4.5)(SO(4))(1.75)) precipitated directly from solution at pH 2.8-4.5. With increasing pH (>5), Fe(2+) ions adsorb to the surface of schwertmannite and catalyze its transformation to goethite (alpha-FeOOH) during the second stage of the reaction. In the third stage, the hydrolysis of the adsorbed Fe(2+) ions on goethite initiates its transformation to GR-SO(4) at pH >7. The GR-SO(4) then continues to crystallize up to pH approximately 8.5. These results suggest that with an Fe(II)/Fe(III) ratio of < or = 2 in the initial solution the structural Fe(II)/Fe(III) of the GR-SO(4) will be close to that of the starting composition.

In this study, direct evidence for the formation of magnetite via a green rust intermediate is reported. The Fe(II) induced transformation of ferrihydrite, was quantified in situ and under O 2 -free conditions using synchrotron-based time-resolved energy dispersive X-ray diffraction. At pH 9 and Fe(II)/Fe(III) ratios of 0.5 and 1, rapid growth (6 min) of sulphate green rust and its subsequent transformation to magnetite was observed. Electron microscopy confirmed these results, showing the initial rapid formation of hexagonal sulphate green rust particles, followed by the corrosion of the green rust as magnetite growth occurred, indicating that the reaction proceeds via a dissolution-reprecipitation mechanism. At pH 7 and Fe(II)/Fe(III) ratio of 0.5, sulphate green rust was the stable phase, with no transformation to magnetite.

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