Redox Dynamics of Mixed Metal (Mn, Cr, and Fe) Ultrafine Particles

The impact of particle composition on metal oxidation state, and on changes in oxidation state with simulated atmospheric aging, are investigated experimentally in flame-generated nanoparticles containing Mn, Cr, and Fe. The results demonstrate that the initial fraction of Cr(VI) within the particles decreases with increasing total metal concentration in the flame. In contrast, the initial Mn oxidation state was only partly controlled by metal loading, suggesting the importance of other factors. Two reaction pathways, one reductive and one oxidative, were found to be operating simultaneously during simulated atmospheric aging. The oxidative pathway depended upon the presence of simulated sunlight and O{sub 3}, whereas the reductive pathway occurred in the presence of simulated sunlight alone. The reductive pathway appears to be rapid but transient, allowing the oxidative pathway to dominate with longer aging times, i.e. greater than {approx}8 hours. The presence of Mn within the particles enhanced the importance of the oxidative pathway, leading to more net Cr oxidation during aging implying that Mn can mediate oxidation by removal of electrons from other particulate metals

The specific surface area and chemical composition of diamond dust near Barrow, Alaska

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/95687/1/jgrd17349.pd

Direct visualization of solute locations in laboratory ice samples, links to videos

Many important chemical reactions occur in polar snow, where solutes may be present in several reservoirs, including at the air-ice interface and in liquid-like regions within the ice matrix. Some recent laboratory studies suggest chemical reaction rates may differ in these two reservoirs. While investigations have examined where solutes are found in natural snow and ice, similar research has not identified solute locations in laboratory samples, nor the possible factors controlling solute segregation. To address this, we examined solute locations in ice samples prepared from either aqueous cesium chloride (CsCl) or Rose Bengal solutions that were frozen using several different methods. Samples frozen in a laboratory freezer had the largest liquid-like inclusions and air bubbles, while samples frozen in a custom freeze chamber had somewhat smaller air bubbles and inclusions; in contrast, samples frozen in liquid nitrogen showed much smaller concentrated inclusions and air bubbles, only slightly larger than the resolution limit of our images (~2 µm). Freezing solutions in plastic versus glass vials had significant impacts on the sample structure, perhaps because the poor heat conductivity of plastic vials changes how heat is removed from the sample as it cools. Similarly, the choice of solute had a significant impact on sample structure, with Rose Bengal solutions yielding smaller inclusions and air bubbles compared to CsCl solutions frozen using the same method. Additional experiments using higher-resolution imaging of an ice sample show that CsCl moves in a thermal gradient, supporting the idea that the solutes in ice are present in liquid-like regions. Our work shows that the structure of laboratory ice samples, including the location of solutes, is sensitive to freezing method, sample container, and solute characteristics, requiring careful experimental design and interpretation of results

Degradation of organic pollutants in/on snow and ice by singlet molecular oxygen (¹O₂*) and an organic triplet excited state.

Singlet molecular oxygen (¹O₂*) can be a significant sink for a variety of electron-rich pollutants in surface waters and atmospheric drops. We recently found that ¹O₂* concentrations are enhanced by up to a factor of 10(4) on illuminated ice compared to in the equivalent liquid solution, suggesting that ¹O₂* could be an important oxidant for pollutants in snow. To examine this, here we study the degradation of three model organic pollutants: furfuryl alcohol (to represent furans), tryptophan (for aromatic amino acids), and bisphenol A (for phenols). Each compound was studied in illuminated aqueous solution and ice containing Rose Bengal (RB, a sensitizer for ¹O₂*) and sodium chloride (to adjust the concentration of total solutes). The RB-mediated loss of each organic compound is enhanced on illuminated ice compared to in solution, by factors of 6400 for furfuryl alcohol, 8300 for tryptophan, and 50 for bisphenol A for ice containing 0.065 mM total solutes. Rates of loss of furfuryl alcohol and tryptophan decrease at a higher total solute concentration, in qualitative agreement with predictions from freezing-point depression. In contrast, the loss of bisphenol A on ice is independent of total solute concentration. Relative to liquid tests, the enhanced loss of tryptophan on ice during control experiments made with deoxygenated solutions and solutions in D₂O show that the triplet excited state of Rose Bengal may also contribute to loss of pollutants on ice

Using singlet molecular oxygen to probe the solute and temperature dependence of liquid-like regions in/on ice.

Liquid-like regions (LLRs) are found at the surfaces and grain boundaries of ice and as inclusions within ice. These regions contain most of the solutes in ice and can be (photo)chemically active hotspots in natural snow and ice systems. If we assume all solutes partition into LLRs as a solution freezes, freezing-point depression predicts that the concentration of a solute in LLRs is higher than its concentration in the prefrozen (or melted) solution by the freeze-concentration factor (F). Here we use singlet molecular oxygen production to explore the effects of total solute concentration ([TS]) and temperature on experimentally determined values of F. For ice above its eutectic temperature, measured values of F agree well with freezing-point depression when [TS] is above ∼1 mmol/kg; at lower [TS] values, measurements of F are lower than predicted from freezing-point depression. For ice below its eutectic temperature, the influence of freezing-point depression on F is damped; the extreme case is with Na2SO4 as the solute, where F shows essentially no agreement with freezing-point depression. In contrast, for ice containing 3 mmol/kg NaCl, measured values of F agree well with freezing-point depression over a range of temperatures, including below the eutectic. Our experiments also reveal that the photon flux in LLRs increases in the presence of salts, which has implications for ice photochemistry in the lab and, perhaps, in the environment