The number fraction of iron-containing particles affects OH, HO₂ and H₂O₂ budgets in the atmospheric aqueous phase

Reactive oxygen species (ROS), such as OH, HO2, H2O2 affect the oxidation capacity of the atmosphere and cause adverse health effects of particulate matter. The role of transition metal ions (TMIs) in impacting the ROS concentrations and conversions in the atmospheric aqueous phase has been recognized for a long time. Model studies usually assume that the total TMI concentration as measured in bulk aerosol or cloud water samples is distributed equally across all particles or droplets. This assumption is contrary to single-particle measurements that have shown that only a small number fraction of particles contain iron and other TMIs (FN,Fe < 100 %) which implies that also not all cloud droplets contain TMIs. In the current study, we apply a box model with an explicit multiphase chemical mechanism to simulate ROS formation and cycling in (i) aqueous aerosol particles and (ii) cloud droplets. Model simulations are performed for the range of 1 % ≤ FN,Fe ≤ 100 % for constant pH values of 3, 4.5 and 6 and constant total iron concentration (10 or 50 . Model results are compared for two sets of simulations with FN,Fe < 100 % (FeN < 100) and 100 % (FeBulk). We find largest differences between model results in OH and HO2/O2− concentrations at pH = 6. Under these conditions, HO2 is subsaturated in the aqueous phase because of its high effective Henry's law constant and the fast chemical loss reactions of the O2− radical anion. As the main reduction of process of Fe(III) is its reaction with HO2/O2−, we show that the HO2 subsaturation leads to predicted Fe(II)/Fe(total) ratios for FN,Fe < 100 % that are lower by a factor of ≤ 2 as compared to bulk model approaches. This trend is largely independent of the total iron concentration, as both chemical source and sink rates of HO2/O2− scale with the iron concentration. The chemical radical (OH, HO2) loss in particles is usually compensated by its uptake from the gas phase. We compare model-derived reactive uptake parameters γ(OH) and γ(HO2) for the full range of FN,Fe. While γ(OH) is not affected by the iron distribution, the calculated γ(HO2) range from 0.0004 to 0.03 for FN,Fe = 1 % and 100 %, respectively. Implications of these findings are discussed for the application of lab-derived γ(HO2) in models to present reactive HO2 uptake on aerosols. As the oxidant budget in aerosol particles and cloud droplets is related to the oxidative potential, we also conclude that the iron distribution FN,Fe should be taken into account to estimate the ROS concentrations and health impacts of particulate matter that might be overestimated by bulk sampling and model approaches. Our study suggests that the number concentration of iron-containing particles may be more important than the total iron mass concentration in determining ROS budgets and uptake rates in cloud and aerosol water.

Effect of Organic Substances on the Efficiency of Fe(Ii) to Fe(Iii) Oxidation and Removal of Iron Compounds from Groundwater in the Sedimentation Process

One of the problems with iron removal from groundwater is organic matter. The article presents the experiments involved groundwater samples with a high concentration of total iron - amounting to 7.20 mgFe/dm3 and an increased amount of organic substances (TOC from 5.50 to 7.50 mgC/dm3). The water samples examined differed in terms of the value of the ratio of the TOC concentration and the concentration of total iron (D). It was concluded that with increase in the coexistence ratio of organic substances and total iron in water (D = [TOC]/[Fetot]), efficiency of Fe(II) to Fe(III) oxidization with dissolved oxygen decreased, while the oxidation time was increasing. This rule was not demonstrated for potassium manganate (VII) when used as an oxidizing agent. The application of potassium manganate (VII) for oxidation of Fe(II) ions produced the better results in terms of total iron concentration reduction in the sedimentation process than the oxidation with dissolved oxygen.

Simulation of Iron Distribution after Crystallization of mc Silicon

Interstitial iron (Fei) and iron-boron pairs influence or even limit the recombination lifetime in industrial block cast multicrystalline (mc) silicon, though the proportions in the total iron concentration are generally small. Most of the iron in mc silicon is precipitated and less recombination active. This work aims for a better understanding of the distribution of iron in its different states (precipitated or dissolved) over the block height, as well as in regions of different crystal quality. In experimental studies several features of iron in mc silicon were observed, which occur due to the high extended defect density. In our 2-dimensional model for mc silicon, trapping of interstitial Fe at extended defects and precipitation at the extended defects are taken into account. The results are compared with NAA-data and spatial resolved measurements of the Fei concentration.

Kinetics of Ferrous Iron Oxidation by Leptospirillum Ferriphilum at Moderate to High Total Iron Concentrations

The effects of temperature, pH and iron concentration on the kinetics of ferrous iron biooxidation by a free suspended culture of Leptospirillum ferriphilum were studied in shake flasks and a circulating bed bioreactor at moderate to high total iron concentration. The kinetic study showed that there are two distinct modes of iron biooxidation: growth associated and non-growth associated, depending on the pH of the medium. There were also distinctive maxima of the effect of temperature and pH on the rate of biooxidation. A kinetic model of the process was proposed, based on an electrochemical-enzymatic model. The proposed model indicates that at moderate to high concentrations (above ~12 g/L), the total iron concentration becomes the single most prominent inhibiting factor.

The Effect of Total Iron Concentration and Iron Speciation on the Rate of Ferrous Iron Oxidation Kinetics of Leptospirillum ferriphilum in Continuous Tank Systems

In this study the results from a systematic study of the oxidation kinetics of Leptospirillum ferriphilum in continuous culture at total iron concentrations ranging from 2 to12 g/L are reported. In all experiments the steady-state concentrations of ferrous iron were small and comparable, and at least 97% of was as ferric. Surprisingly, the specific ferrous iron utilisation rate decreased with increasing total iron concentration, while yield coefficients increased. It was noted that the biomass concentration in the reactor (as measured by both CO2 uptake rate and cell counts) dramatically increased with increasing total iron concentrations, whereas it stayed more or less the same over a wide range of dilution rates at a given total iron concentration. The experimental data was re-analysed in terms of ferrous iron kinetics using Monod kinetics with a ferric inhibition term. The results confirm that the maximum specific iron utilisation rate is itself a function of ferric iron concentration, declining with increasing concentration. It thus appears that high concentrations of ferric iron stimulate microbial growth while at the same time inhibiting the rate of ferrous iron oxidation. It is postulated that these phenomena are related, i.e. that more growth occurs to reduce the load on the individual cell, possibly by sharing some metabolic functions.