Mineral Aerosol Particles Research Articles

Atmospheric fate of typical liquid crystal monomers in the tropospheric gas, liquid, and granular phases

Mineral aerosol particles significantly impact environmental risk prediction of liquid crystal monomers (LCMs). In this work, we investigated the reaction mechanisms and kinetics of three typical LCMs (4-cyano-3,5-difluorophenyl 4-ethylbenzoate (CEB-2F), 4-cyano-3-fluorophenyl 4-ethylbenzoate (CEB-F), and 4-cyanophenyl 4-ethylbenzoate (CEB)) with ozone (O3) in the atmospheric gas, liquid, and particle phases employing density functional theory (DFT). Here, O3 is prone to add to the benzene ring without F atom(s) in the selected LCMs. The ozonolysis products are aldehydes, carboxylic acids, epoxides, and unsaturated hydrocarbons containing aromatic rings. Those products undergo secondary ozonolysis to generate small molecular compounds such as glyoxal, which is beneficial for generating secondary organic aerosol (SOA). Titanium dioxide (TiO2), an essential component of mineral aerosol particles, has good adsorption properties for LCMs; however, it slightly reduces the reactivity with O3. At 298 K, the reaction rate constant of the selected LCMs reacting with O3 in the gas and atmospheric liquid phases is (2.74‒5.53) × 10−24 cm3/(mol·sec) and 5.58 × 10−3‒39.1 L/(mol·sec), while CEB-2F reacting with O3 on (TiO2)6 cluster is 1.84 × 10−24 cm3/(mol·sec). The existence of TiO2 clusters increases the persistence and long-distance transportability of LCMs, which enlarges the contaminated area of LCMs.

Cloud history can change water–ice–surface interactions of oxide mineral aerosols: a case study on silica

Abstract. Mineral aerosol particles nucleate ice, and many insights have been obtained on water freezing as a function of mineral surface properties such as charge or morphology. Previous studies have mainly focused on pristine samples despite the fact that aerosol particles age under natural atmospheric conditions. For example, an aerosol-containing cloud droplet can go through freeze–melt or evaporation–condensation cycles that change the surface structure, the ionic strength, and pH. Variations in the surface properties of ice-nucleating particles in the atmosphere have been largely overlooked. Here, we use an environmental cell in conjunction with nonlinear spectroscopy (second-harmonic generation) to study the effect of freeze–melt processes on the aqueous chemistry at silica surfaces at low pH. We found that successive freeze–melt cycles disrupt the dissolution equilibrium, substantially changing the surface properties and giving rise to marked variations in the interfacial water structure and the ice nucleation ability of the surface. The degree of order of water molecules, next to the surface, at any temperature during cooling decreases and then increases again with sample aging. Along the aging process, the water ordering–cooling dependence and ice nucleation ability improve continuously.

Experimental Studies of Aerosols in the Atmosphere of Semiarid Landscapes of Kalmykia: 1. Microphysical Parameters and Mass Concentration of Aerosol Particles

This paper summarizes the results of long-term (2004–2016) comprehensive experimental studies of microphysical parameters and the mass concentration of aerosol particles in the atmospheric surface layer of semiarid regions of Kalmykia arranged by the Obukhov Institute of Atmospheric Physics of the Russian Academy of Sciences. Characteristic values of the mass and number concentrations of aerosol particles in the summer have been determined for different velocities. A significant decrease in the concentration of surface submicron- and micron-sized aerosols in comparison with their values observed in desert areas of Kalmykia in the 1990s has been found. Mass concentration distributions over aerosol particle fractions have been obtained. The diurnal course of the particle number concentration has been studied taking the meteorological conditions (air temperature, velocity, and humidity) and the underlying surface into consideration. The particle-size distribution functions characteristic of atmospheric aerosols in Kalmykia have been determined. The removal of particles has been coupled with the main meteorological parameters in the atmospheric near-surface layer. A large number of submicron-sized particles have been found to persist in the atmospheric surface layer of semiarid landscapes, confirming that they are the main sources of transport of fine mineral aerosol particles, which are most dangerous to human health and actively engaged in biospheric and climate change processes.

Online single particle analysis of ice particle residuals from mountain-top mixed-phase clouds using laboratory derived particle type assignment

Abstract. In situ single particle analysis of ice particle residuals (IPRs) and out-of-cloud aerosol particles was conducted by means of laser ablation mass spectrometry during the intensive INUIT-JFJ/CLACE campaign at the high alpine research station Jungfraujoch (3580 m a.s.l.) in January–February 2013. During the 4-week campaign more than 70 000 out-of-cloud aerosol particles and 595 IPRs were analyzed covering a particle size diameter range from 100 nm to 3 µm. The IPRs were sampled during 273 h while the station was covered by mixed-phase clouds at ambient temperatures between −27 and −6 °C. The identification of particle types is based on laboratory studies of different types of biological, mineral and anthropogenic aerosol particles. The outcome of these laboratory studies was characteristic marker peaks for each investigated particle type. These marker peaks were applied to the field data. In the sampled IPRs we identified a larger number fraction of primary aerosol particles, like soil dust (13 ± 5 %) and minerals (11 ± 5 %), in comparison to out-of-cloud aerosol particles (2.4 ± 0.4 and 0.4 ± 0.1 %, respectively). Additionally, anthropogenic aerosol particles, such as particles from industrial emissions and lead-containing particles, were found to be more abundant in the IPRs than in the out-of-cloud aerosol. In the out-of-cloud aerosol we identified a large fraction of aged particles (31 ± 5 %), including organic material and secondary inorganics, whereas this particle type was much less abundant (2.7 ± 1.3 %) in the IPRs. In a selected subset of the data where a direct comparison between out-of-cloud aerosol particles and IPRs in air masses with similar origin was possible, a pronounced enhancement of biological particles was found in the IPRs.

Effect of Formaldehyde on the Heterogeneous Reaction of Nitrogen Dioxide on γ-Alumina.

Heterogeneous reactions of NO2 on various mineral aerosol particles have been investigated in many previous studies, but a fundamental understanding of how the adsorption of formaldehyde influences the heterogeneous reactions of NO2 remains unclear. In this work, the effect of formaldehyde preadsorption on heterogeneous reaction of NO2 on the surface of γ-Al2O3 at 298 K and ambient pressure was investigated by using diffuse reflectance infrared Fourier transform spectrometry (DRIFTS). It was found that the preadsorption of HCHO on γ-Al2O3 could suppress the formation of nitrate, and the rate of nitrate formation decreased with increasing amount of preadsorbed HCHO, whereas the following heterogeneous uptake of NO2 could suppress the hydration reaction of HCHO and promote the production of HCOO(-) during the reaction. Surface nitrite was formed and identified to be an intermediate product and gradually disappeared as the reaction proceeded. The amount of the formed nitrite decreased when the amount of HCHO increased. Uptake coefficients of heterogeneous reactions were calculated and found to be sensitive to the adsorption of HCHO. A possible mechanism for the influence of HCHO adsorption on the heterogeneous conversion of NO2 on γ-Al2O3 was proposed, and atmospheric implications based on these results were discussed.

Ways of far-distance dust transport onto Caucasian glaciers and chemical composition of snow on the Western plateau of Elbrus

We present and discuss the chronology of dust deposition events documented by the shallow firn and ice cores extracted on the Western Plateau, Mt. Elbrus (5150 m a.s.l.) in 2009, 2012 and 2013. Snow and ice samples were analysed for major ions and minor element concentrations including heavy metals. Dust layers are formed on the surface of the glaciers as a result of atmospheric transport of mineral dust and aerosol particles to the Caucasus region. Satellite imagery (SEVIRI), trajectory models, and meteorological data were used for accurate dating of each the dust layers revealed in the ice cores. Then we tried to determine origins of the dust clouds and to investigate their transport pathways with high resolution (50–100 km). It was found that the desert dust is deposited on Caucasus glaciers 3–7 times in a year and it comes mainly from deserts of the Middle East and more rarely from the Northern Sahara desert. For the first time average annual dust flux (264 µg/cm 2 per a year) and average mass concentration (1.7 mg/kg) over the period 2007–2013 were calculated for this region. The deposition of dust resulted in elevated concentrations consists of mostly ions, especially Ca 2+ , Mg 2+ , K + , and sulphates. Dust originated from various sources in the Middle East, including Mesopotamia, or similar dust clouds passing over the Middle East are characterised by high concentrations of nitrates and ammonia that may be related to atmospheric transport of ammonium from agricultural lands that may explain high concentrations of ammonium in the dust originating from this region. Mean values of crustal enrichment factors (EF) for the measured minor elements including heavy metals were calculated. We believe that high content of Cu, Zn and Cd can be a result of possible contribution from anthropogenic sources. Studies of the Caucasus ice cores may allow obtaining new independent data on the atmosphere circulation and high-altitude environment of this region.

Impact of dust particle non‐sphericity on climate simulations

AbstractAlthough mineral aerosol (dust) particles are irregular in shape, they are treated as homogeneous spheres in climate model radiative transfer calculations. Here, we test the effect of dust particle non‐sphericity in the ECHAM5.5‐HAM2 global aerosol–climate model. The short‐wave optical properties of the two insoluble dust modes in HAM2 are modelled using an ensemble of spheroids that has been optimized to reproduce the optical properties of dust‐like aerosols, thereby providing a significant improvement over spheres. First, the direct radiative effects (DRE) of dust non‐sphericity were evaluated diagnostically, by comparing spheroids with both volume‐equivalent and volume‐to‐area (V/A) equivalent spheres. In the volume‐equivalent case, the short‐wave DRE of insoluble dust at the surface and at the top of the atmosphere (TOA) was slightly smaller (typically by 3–4%) for spheroidal than for spherical dust particles. This rather small difference stems from compensating non‐sphericity effects on the dust optical thickness and asymmetry parameter. In the V/A‐equivalent case, the difference in optical thickness was virtually eliminated and the DRE at the TOA (surface) was ∼20% (∼13%) smaller for spheroids than for spheres, due to a larger asymmetry parameter. Even then, however, the global‐mean DRE of non‐sphericity was only 0.055 W m−2at the TOA and 0.070 W m−2at the surface. Subsequently, the effects of dust non‐sphericity were tested interactively in simulations in which ECHAM5.5‐HAM2 was coupled to a mixed‐layer ocean model. Consistent with the rather small radiative effects noted above, the climatic differences from simulations with spherical dust optics were generally negligible.

Modeling optical properties of mineral aerosol particles by using nonsymmetric hexahedra

We explore the use of nonsymmetric geometries to simulate the single-scattering properties of airborne dust particles with complicated morphologies. Specifically, the shapes of irregular dust particles are assumed to be nonsymmetric hexahedra defined by using the Monte Carlo method. A combination of the discrete dipole approximation method and an improved geometric optics method is employed to compute the single-scattering properties of dust particles for size parameters ranging from 0.5 to 3000. The primary optical effect of eliminating the geometric symmetry of regular hexahedra is to smooth the scattering features in the phase function and to decrease the backscatter. The optical properties of the nonsymmetric hexahedra are used to mimic the laboratory measurements. It is demonstrated that a relatively close agreement can be achieved by using only one shape of nonsymmetric hexahedra. The agreement between the theoretical results and their measurement counterparts can be further improved by using a mixture of nonsymmetric hexahedra. It is also shown that the hexahedron model is much more appropriate than the "equivalent sphere" model for simulating the optical properties of dust particles, particularly, in the case of the elements of the phase matrix that associated with the polarization state of scattered light.

Investigation of the hygroscopic properties of Ca(NO<sub>3</sub>)<sub>2</sub> and internally mixed Ca(NO<sub>3</sub>)<sub>2</sub>/CaCO<sub>3</sub> particles by micro-Raman spectrometry

Abstract. To understand and predict the role of mineral aerosol particles processed by reactive nitrogen species in the atmosphere, the hygroscopic properties of both Ca(NO3)2 and Ca(NO3)2-containing mineral particles must be well understood. Using a micro-Raman system, the hygroscopic behaviors of micro-sized individual Ca(NO3)2 and internally mixed Ca(NO3)2/CaCO3 particles in both dehumidifying and humidifying processes were investigated systematically. In addition to accurate quantification of the dependence of water content on relative humidity (RH), significant new spectroscopic evidence related to chemical structure was also obtained to confirm the occurrence of amorphous solid state and to better understand the phase transition process. The Ca(NO3)2 particles exhibit reversible behavior in the dehumidifying and humidifying processes; they are in the state of solution droplets above 10% RH and amorphous hydrates below 7% RH, and phase transition occurs at 7–10% RH. The hygroscopic behavior of Ca(NO3)2/CaCO3 particles is identical to that of pure Ca(NO3)2 particles, suggesting a negligible effect of the slightly soluble CaCO3 inclusion on the hygroscopic behavior of a(NO3)2/CaCO3 particles.

Atmospheric Fe deposition modes at Bermuda and the adjacent Sargasso Sea

The atmospheric fluxes of Fe and Al were determined from bulk (wet + dry) plus wet only deposition and aerosol samples collected at Bermuda from 1999 to 2001. During the sampling period, dry deposition accounted for majority (>70%) of total Fe deposition estimated by both modeled and measured means. This contrasts the North Pacific, where generally wet dominates dry deposition. This may be caused by the size and proximity of continental dust sources and seasonal patterns of precipitation to the North Atlantic. Comparing time series measurement of wet soluble Fe deposition indicates that the North Atlantic Oscillation (NAO) may impact the deposition mode of Fe in these areas. The dry deposition velocities of Fe‐bearing aerosols (DDVFe) were estimated from paired averages of measured dry deposition (bulk‐wet fluxes) divided by corresponding aerosol concentrations, and a seasonal trend was observed. During the summer months of 1999, the DDVFe ranged from 0.1 to 0.3 cm s−1; yet, during the fall and winter months, the DDVFe ranged from 2.0 to 6.0 cm s−1. It is hypothesized that with increased humidity and wind speeds at Bermuda during fall and winter, mineral aerosol particles could be internally mixed with sea salt and gaseous S and N pollutants to increase effective particle sizes. Such marine particle aggregation is reported elsewhere and could seasonally increase the apparent dry deposition velocity of mineral aerosols.

Mineral particle size as a control on aerosol iron solubility

Aerosol iron solubility is a major uncertainty in the global biogeochemical cycle of iron and, via its impact on ocean productivity, the carbon cycle and their influence on global climate. Previous studies have reported widely different values for this solubility (0.01 – 80%). Here we show that the primary control on aerosol iron solubility is the surface area to volume ratio of mineral aerosol particles, which changes during atmospheric transport as mineral aerosol concentration decreases due to preferential removal of larger particles (assuming particle morphology to be relatively constant with particle size). This important result indicates that aerosol iron solubility is not fixed, but will change predictably as an inverse function of dust concentration on both spatial and temporal (e.g. glacial – interglacial) scales.

Saharan dust events at the Jungfraujoch: detection by wavelength dependence of the single scattering albedo and first climatology analysis

Abstract. Scattering and absorption coefficients have been measured continuously at several wavelengths since March 2001 at the high altitude site Jungfraujoch (3580ma.s.l.). From these data, the wavelength dependences of the Ångström exponent and particularly of the single scattering albedo are determined. While the exponent of the single scattering albedo usually increases with wavelength, it decreases with wavelength during Saharan dust events (SDE) due to the greater size of the mineral aerosol particles and their different chemical composition. This change in the sign of the single scattering exponent turns out to be a sensitive means for detecting Saharan dust events. The occurrence of SDE detected by this new method was confirmed by visual inspection of filter colors and by studying long-range back-trajectories. An examination of SDE over a 22-month period shows that SDE are more frequent during the March-June period as well as during October and November. The trajectory analysis indicated a mean traveling time of 96.5h, with the most important source countries situated in the northern and north-western part of the Saharan desert. Most of the SDE do not lead to a detectable increase of the 48-h total suspended particulate matter (TSP) concentration at the Jungfraujoch. During Saharan dust events, the average contribution of this dust to hourly TSP at the Jungfraujoch is 16µg/m3, which corresponds to an annual mean of 0.8µg/m3 or 24% of TSP.

Dissolution and solubility of trace metals from natural and anthropogenic aerosol particulate matter

An open flow reactor is used to simulate the dissolution process of mineral aerosol particles in atmospheric water droplets. Data on dissolution kinetic and solubility are provided for the major trace metals from two kinds of matrix: alumino-silicated and carbonaceous sample. The results emphasise that the metals contained in the carbonaceous aerosols are easier dissolved than in the alumino-silicated particles. The released concentrations are not related to the total metal composition or the origin of particles, but are directly associated with the type of liaisons whereby the metals are bound in the solid matrix. Thus, the metals coming from carbonaceous particles are adsorbed impurities or salts and hence are very soluble and with a dissolution hardly dependent on pH, whereas the metals dissolved from alumino-silicated particles are less soluble, notably the ones constitutive of the matrix network (Fe, Mn), and with a dissolution highly influenced by pH. Consequently, in the regions with an anthropogenic influence, the dissolved concentrations of metals found in the atmospheric waters are mainly governed by the elemental carbon content. Moreover, it appears that the dissolution kinetic of metals is not constant as a function of time. The dissolution rates are very rapid in the first 20 min of leaching and then they are stabilised to lower values in comparison to initial rates. By consequence, the total dissolved metal content is provided after the first 20 min of the droplet lifetime. For this reason, the effects of trace metals on the atmospheric aqueous chemistry and as atmospheric wet input to the marine biota are maximal for “aged” droplets.

Light reflected by an atmosphere containing irregular mineral dust aerosol

We simulate polarimetric satellite observations of sunlight reflected by a turbid atmosphere over the ocean. We determine the sensitivity of these observations with respect to the optical thickness and the single‐scattering albedo of irregular mineral aerosol. Simulated results indicate that both quantities can be retrieved from simultaneous polarization and intensity measurements. Aerosol scattering is modelled using a true measured scattering matrix of irregularly‐shaped mineral dust aerosol. We study the suitability of various approximations of the particle shape used for the numerical calculation of scattering matrices. Approximations with spheres or spheroids with a distribution of moderate axis ratios can lead to large errors of the simulated light intensities. A spheroidal approximation including extreme axis ratios is found to be the most appropriate one for simulations of light scattering by irregular mineral aerosol particles, if measured scattering matrices are not available.

Mineral aerosol particles collected in Dunhuang, China, and their comparison with chemically modified particles collected over Japan

Continental China has been recognized as one of the most important sources of atmospheric mineral dust particles (called Kosa in Japan, which literally means yellow sand). Many investigators have pointed out the importance of study of the long‐range transport of mineral dust particles and their modifications in this process even during the nondust storm periods. Because of these modifications, particles can change their radiative properties and their ability to be a condensation nucleus. Therefore it is important to examine the composition of individual mineral particles in their source region and compare these particles with those after long‐range transport. A number of investigations have been carried out on the subject; however, the amount of data is still insufficient. Samples of aerosol particles were collected in Dunhuang, China, in different seasons in 2001 and 2002 during the ACE‐Asia campaign. The collected particles were examined using a scanning electron microscope equipped with an energy dispersive X‐ray analyzer. The particles in all the samples were mainly mineral particles. Similar types of mineral particles were found in the free troposphere over Japan. A number of differences were found between the particles collected in China and those collected over Japan, and these differences can be explained by chemical modifications that occurred in the particles during their transport from China to Japan. Approximately 40–45% of mineral particles mixed internally with sulphate during their transport in the troposphere. Also, the particles collected over Japan were found to be different from those obtained in ground‐based measurements in Nagasaki, Nagoya, and Fukuoka, Japan (reported by other research groups). The portion of mineral particles that mixed internally with sea salt and sulphates was considerably smaller than for the samples obtained in Japan near the ground. It is important to take this fact into account while investigating the impact of mineral particles on the biogeochemical cycle and climate.

Experimental determination of scattering matrices of randomly oriented fly ash and clay particles at 442 and 633 nm

We present measurements of the scattering angle distribution of the whole scattering matrix for randomly oriented particles of three mineral samples: fly ash, green clay, and red clay at 442 and 633 nm. Fly ash consists of aggregates of nearly spherical particles while green clay and red clay particles represent irregular compact particles. We compare the measured results for fly ash with an experimentally determined average scattering matrix which is based on measurements for a broad selection of irregular mineral aerosol particles. We find that the scattering matrix of our polydisperse sample of aggregates of nearly spherical particles differs considerably from that of compact particles. In addition, the angular distribution of the elements of the scattering matrix (except F22(θ)/ F11(θ)) for fly ash particles seem to be dominated by the single monomers. The effects of small differences in composition on the scattering behavior have also been studied by comparing our experimental results for green clay particles with those obtained by Volten et al. [2001] for red clay particles at the same wavelengths.

Scattering matrices of mineral aerosol particles at 441.6 nm and 632.8 nm

We present measured scattering matrices as functions of the scattering angle in the range 5°–173° and at wavelengths of 441.6 nm and 632.8 nm for seven distinct irregularly shaped mineral aerosol samples with properties representative of mineral aerosols present in the Earth's atmosphere. The aerosol samples, i.e., feldspar, red clay, quartz, loess, Pinatubo and Lokon volcanic ash, and Sahara sand, represent a wide variety of particle size (typical diameters between 0.1 and 100 μm) and composition (mainly silicates). We investigate the effects of differences in size and complex refractive index on the light‐scattering properties of these irregular particles. In particular, we find that the measured scattering matrix elements when plotted as functions of the scattering angle are confined to rather limited domains. This similarity in scattering behavior justifies the construction of an average aerosol scattering matrix as a function of scattering angle to facilitate, for example, the use of our results for the interpretation of remote sensing data. We show that results of ray‐optics calculations, using Gaussian random shapes, are able to describe the experimental data well when taking into account the high irregularity in shape of the aerosols, even when these aerosols are rather small. Using the results of ray‐optics calculations, we interpret the differences found between the measured aerosol scattering matrices in terms of differences in complex refractive index and particle size relative to the wavelength. The importance of our results for studies of astronomical objects, such as planets, comets, asteroids, and circumstellar dust shells is discussed.

Mineral particles collected in china and japan during the same Asian dust-storm event

Aerosol particles were collected at China and Japan in the same spring Asian dust-storm event of 1991 in order to study the change in composition of mineral aerosol particles during long range transport. It was found on the basis of a microchemical analysis that dust particles containing Mg, Al, Si, K, Ca and Fe were a major fraction of the aerosol particles collected at Hohhot and Beijing, China, and Nagasaki, Japan. A large fraction of the mineral aerosol particles was internally mixed with sea salt in Nagasaki. Present study suggests that the internal mixed particles were mainly produced by cloud processes through droplet coalescence.

Dissolved input of manganese to the ocean: Aerosol source

Aerosol particle samples representative of polluted air, dust‐laden air, and clean marine air were collected in marine regions and used in a series of dissolution studies. These samples were exposed to seawater for varying lengths of time and to deionized (Milli‐Q®) water at various values of pH. The percentage of aerosol Mn dissolved in Milli‐Q® water increased from 55 to 80% between pH 8 and pH 2 for pollution aerosols. Less dissolution occurred with the mineral aerosol particles, for which the dissolved Mn increased from 25 to 50% between pH 8 and pH 2. As similar behavior is found for particles collected in clean marine air, we conclude that the dissolution process for aerosol particles from a remote marine area, where crustal Mn dominates pollution Mn, is controlled by the background mineral content. The kinetics of Mn dissolution in seawater are rapid for all the samples: a concentration plateau is reached after 10 min or less of exposure. Release of dissolved Mn from polluted aerosols in seawater was approximately twice the value obtained with mineral particles (55 and 30%, respectively). Apparently, no additional Mn dissolution beyond that which has clearly taken place in rain occurs when rainwater enters the ocean. A positive relationship evidently exists between the total Mn concentration of the aerosol and the dissolved concentration after exposure in seawater. Extrapolating the relationship from the available data suggests that the dissolved saturation value is approximately 60 nmol L−1. Considering the different behavior found for the different types of particles, at least two cases must be considered when assessing mass balances or calculating atmospheric fluxes of Mn to the ocean. Based on the results of our dissolution studies, the resulting dissolved fluxes of Mn of atmospheric origin during a pulse of Saharan dust range from 0.16 to 0.33 μmol m−2d−1 over the duration of the pulse. The total dissolved Mn flux from anthropogenic sources in western North Europe is estimated to be 0.3 μmol m−2d−1. Fluxes of dissolved Mn of mineral and anthropogenic origin resulting from this calculation in the two examples selected are of the same order of magnitude. The spatial and temporal patterns of these different sources and the dynamics of the upper water column have to be taken into account to estimate quantitatively the impact of atmospheric input on Mn concentrations in the water column.

Rare Earth element composition of precipitation, precipitation particles, and aerosols

We report the rare earth element (REE) composition of aerosols and precipitation (dissolved and particle phases) from Bermuda, Lewes (Delaware), and Woods Hole (Massachusetts). There is large‐scale fractionation of REEs between the continents, atmosphere, and the oceans. The REE compositions of atmospheric samples are highly fractionated relative to (1) each other (e.g., aerosol/precipitation pairs), (2) the upper crust of the Earth, and (3) seawater. Precipitation samples exhibit markedly convex‐up shale‐normalized patterns, large negative Eu anomalies and large and systematic depletions in the heavy REE (Lu > Yb > Er > Dy). Aerosols are strongly depleted in the heavy REE which dissolutions experiments show are attributable to the presence of HREE‐enriched refractory minerals. We argue that in situ selective dissolution of mineral aerosol particles is responsible for the unusual REE composition of precipitation. This has major implications for the interpretation of the biogeochemical cycles of REEs in the oceans, particularly the partitioning between solution and particle phases, residence times, and the composition of seawater.