Air pollution creates high Fe solubility in pyrogenic aerosols, raising the flux of biologically essential Fe to the oceans.

This work reports on the current status of the global modeling of iron (Fe) deposition fluxes and atmospheric concentrations and the analyses of the differences between models, as well as between models and observations. A total of four global 3-D chemistry transport (CTMs) and general circulation (GCMs) models participated in this intercomparison, in the framework of the United Nations Joint Group of Experts on the Scientific Aspects of Marine Environmental Protection (GESAMP) Working Group 38, The Atmospheric Input of Chemicals to the Ocean. The global total Fe (TFe) emission strength in the models is equal to ∼ 72 Tg Fe yr⁻¹ (38–134 Tg Fe yr⁻¹) from mineral dust sources and around 2.1 Tg Fe yr⁻¹ (1.8–2.7 Tg Fe yr⁻¹) from combustion processes (the sum of anthropogenic combustion/biomass burning and wildfires). The mean global labile Fe (LFe) source strength in the models, considering both the primary emissions and the atmospheric processing, is calculated to be 0.7 (±0.3) Tg Fe yr⁻¹, accounting for both mineral dust and combustion aerosols. The mean global deposition fluxes into the global ocean are estimated to be in the range of 10–30 and 0.2–0.4 Tg Fe yr⁻¹ for TFe and LFe, respectively, which roughly corresponds to a respective 15 and 0.3 Tg Fe yr⁻¹ for the multi-model ensemble model mean. The model intercomparison analysis indicates that the representation of the atmospheric Fe cycle varies among models, in terms of both the magnitude of natural and combustion Fe emissions as well as the complexity of atmospheric processing parameterizations of Fe-containing aerosols. The model comparison with aerosol Fe observations over oceanic regions indicates that most models overestimate surface level TFe mass concentrations near dust source regions and tend to underestimate the low concentrations observed in remote ocean regions. All models are able to simulate the tendency of higher Fe concentrations near and downwind from the dust source regions, with the mean normalized bias for the Northern Hemisphere ( ∼ 14), larger than that of the Southern Hemisphere ( ∼ 2.4) for the ensemble model mean. This model intercomparison and model–observation comparison study reveals two critical issues in LFe simulations that require further exploration: (1) the Fe-containing aerosol size distribution and (2) the relative contribution of dust and combustion sources of Fe to labile Fe in atmospheric aerosols over the remote oceanic regions.

The fractional solubility of aerosol-derived trace elements deposited to the ocean surface is a key parameter of many marine biogeochemical models. Despite this, it is currently poorly constrained, in part due to the complex interplay between the various processes that govern the solubilisation of aerosol trace elements. In this study, we used a sequential two-stage leach to investigate the regional variability in fractional solubility of a suite of aerosol trace elements (Al, Ti, Fe, Mn, Co, Ni, Cu, Zn, Cd, and Pb) from samples collected during three GEOTRACES cruises to the North Atlantic Ocean (GA01, GA03-2010, and GA03-2011). We present aerosol trace element solubility data from two sequential leaches that provide a solubility window, covering a conservative lower limit to an upper limit, the maximum potentially soluble fraction, and discuss why this upper limit of solubility could be used as a proxy for the bioavailable fraction in some regions. Regardless of the leaching solution used in this study (mild versus strong leach), the most heavily loaded samples generally had the lowest solubility. However, there were exceptions. Manganese fractional solubility was relatively uniform across the full range of atmospheric loading (32 ± 13 and 49 ± 13 % for ultra high-purity water and 25 % acetic acid leaches, respectively). This is consistent with other marine aerosol studies. Zinc and Cd fractional solubility also appeared to be independent of atmospheric loading. Although the average fractional solubilities of Zn and Cd (37 ± 28 and 55 ± 30 % for Zn and 39 ± 23 and 58 ± 26 % for Cd, for ultra high-purity water and 25 % acetic acid leaches, respectively) were similar to Mn, the range was greater, with several samples being 100 % soluble after the second leach. Finally, as the objective of this study was to investigate the regional variability in TE solubility, the samples were grouped according to air mass back trajectories (AMBTs). However, we conclude that AMBTs are not sufficiently discriminating to identify the aerosol sources or the potential effects of atmospheric processing on the physicochemical composition and solubility of the aerosols.

Changing atmospheric acidity alters the delivery of nutrients to the ocean and affects marine productivity and ecology.

The composition and oxidation state of aerosol iron were examined using synchrotron-based iron near-edge X-ray absorption spectroscopy. By combining synchrotron-based techniques with water leachate analysis, impacts of oxidation state and mineralogy on aerosol iron solubility were assessed for samples taken from multiple locations in the Southern and the Atlantic Oceans; and also from Noida (India), Bermuda, and the Eastern Mediterranean (Crete). These sampling locations capture iron-containing aerosols from different source regions with varying marine, mineral dust, and anthropogenic influences. Across all locations, pH had the dominating influence on aerosol iron solubility. When aerosol samples were approximately neutral pH, iron solubility was on average 3.4%; when samples were below pH 4, the iron solubility increased to 35%. This observed aerosol iron solubility profile is consistent with thermodynamic predictions for the solubility of Fe(III) oxides, the major iron containing phase in the aerosol samples. Source regions and transport paths were also important factors affecting iron solubility, as samples originating from or passing over populated regions tended to contain more soluble iron. Although the acidity appears to affect aerosol iron solubility globally, a direct relationship for all samples is confounded by factors such as anthropogenic influence, aerosol buffer capacity, mineralogy and physical processes.