Magnetite (Fe3O4) is a key economically valuable component in iron ore and is extracted by dissolution processes, but among the Fe (oxyhydr)oxides its solubility behavior is one of the least understood. The objective of this study was to improve understanding of magnetite dissolution mechanisms leading to thermodynamic equilibrium by comparing the dissolution of two solid samples, one synthetic and one industrial, using oxalic, sulfuric, and nitric acids at varying concentrations and temperatures. Of the three solid-liquid systems investigated, only the system consisting of magnetite and oxalic acid reached an equilibrium state within the duration of an individual experiment (6 h). In this system, increasing the acid concentration resulted in a significant increase in the equilibrium concentration of dissolved Fe. When dissolving synthetic and industrial magnetite, increasing the temperature not only increased the rate of reaction but also affected the concentration of dissolved Fe. Significant effects were observed when increasing the temperature from 15 to 35°C, but only slight differences were seen on further increases in temperature. Observations regarding the equilibrium state of the sulfuric and nitric acid systems could not be made because equilibrium was not reached. The most important individual observation regarding the equilibrium state of the nitric- and sulfuric-acid systems seems to be that in future studies a much longer reaction time is necessary, due to slow kinetics of the dissolution mechanism. A proton-based mechanism has been hypothesized as the one governing the dissolution of magnetite by these two acids, but only the dissolution of the industrial sample yielded results that were similar for these two acids and consistent with that hypothesis.

The dissolution kinetics of sepiolite in hydrochloric acid and nitric acid were studied in a batch reactor. The effects of reaction temperature, acid concentration, particle size and solid-to-liquid ratio on the dissolution process were investigated. Experimental studies were carried out in the ranges of 25–75°C for reaction temperature, 0.25–1.00 mol/L for acid concentration, 0.00755–0.05020 cm for average particle size and 2.5 to 12.5 g of solid/100 mL of acid for solid-to-liquid ratio. It was determined that the dissolution process is controlled by resistance of the diffusion through the product layer. The activation energies of the process were determined to be 40.8 and 38.3 kJ/mol for hydrochloric and nitric acid, respectively. The apparent rate constants were expressed as a function of reaction temperature, acid concentration, particle radius and solid-to-liquid ratio: kαe−4910(1/T)Cr−0.6 (s/l)−1 and kαe−4606(1/T)Cr−0.5 (s/1)−1 for hydrochloric and nitric acid, respectively; k is the apparent rate constant in min−1; T, the reaction temperature (K); C, the acid concentration (mol/L); r, the initial particle radius (cm); s/l, the solid-to-liquid ratio (g of solid/100 mL of acid).

It is well established that the reaction of HO2 with NO plays a central role in atmospheric chemistry, by way of OH/HO2 recycling and reduction of ozone depletion by HOx cycles in the stratosphere and through ozone production in the troposphere. Utilizing a photochemical box model, we investigate the impact of the recently observed HNO3 production channel (HO2+NO → HNO3) on NOx (NO + NO2), HOx (OH + HO2), HNO3, and O3 concentrations in the boundary layer at the South Pole, Antarctica. Our simulations exemplify decreases in peak O3, NO, NO2, and OH and an increase in HNO3. Also, mean OH is in better agreement with observations, while worsening the agreement with O3, HO2, and HNO3 concentrations observed at the South Pole. The reduced concentrations of NOx are consistent with expected decreases in atmospheric NOx lifetime as a result of increased sequestration of NOx into HNO3. Although we show that the inclusion of the novel HNO3 production channel brings better agreement of OH with field measurements, the modelled ozone and HNO3 are worsened, and the changes in NOx lifetime imply that snowpack NOx emissions and snowpack nitrate recycling must be re-evaluated.

Les aciers inoxydables austénitiques non sensibilisés peuvent subir dans l’acide nitrique un type de corrosion intergranulaire (CIG) particulier. Un modèle d’estimation de la durée de vie de ces matériaux dans ces milieux est proposé. Il reproduit de manière fiable les cinétiques de corrosion obtenues expérimentalement.

Dedicated nitric oxide equipped ventilators are now available commercially but are not yet common in clinical practice. With other ventilators, there is no standardized procedure for the administration or monitoring of nitric oxide. Wedescribe the use of nitric oxide in conjunction with a simple time–cycled, pressure regulated, flow generating ventilator attached to a model infant–sized lung. The measured nitric oxide concentrations were always less than calculated. Infusion site, minute ventilation and sampling port all affected nitric oxide concentration (P<0.05). Increasing minute ventilation lowered measured nitric oxide concentration exponentially. Mixing of gases improved when nitric oxide was infused closer to the ventilator. Acid contamination was found in water samples from humidifier, water trap and ventilator gas outlet. Acidification was reduced, without change in measured nitric oxide delivery, when infused prehumidifier. We recommend, when used as therapy, nitric oxide levels in inspired gases should always be measured.

Ammonia was necessary for the origin of life. However, NH3 would not have been a significant component of the neutral or mildly reducing (N2, CO2, H2O) atmosphere which characterized the Hadean earth (>3·8 Gyr ago), especially in view of the u.v. lability of NH3, the greater u.v. output of the young sun than pertains today, and the absence of an atmospheric u.v. screen. Heterogeneous phase reactions, following atmospheric chemistry, have been proposed as a prebiotic NH3 source. Lightning, or bolides (meteorites and comets), generated NOx., and Fe2+ in the sea could have reduced NO2− resulting from the NOx. to NH4+; this disequilibrium NH4+ level could have supported the production of the nitrogenous organic building blocks of life. NOx. and NHy thus could both have had important roles in the origin and evolution of life. Burgeoning biota could soon have depleted abiotically generated NH4+, and biological N2 fixation could have evolved in its present Fe-demanding, O2-sensitive forms in the Archaean O2-free, Fe2+-rich environment. Organic matter could have driven biological denitrification reactions based on NO2− and NO3− generated abiologically using some redox components which evolved in earlier chemolithotrophs and photolithotrophs, regenerating atmospheric NOx. and producing N2O. Any atmospheric NH3 leaking from oceanic biology would have been subject to u.v. breakdown and rain-out. Although O2-evolving photosynthesis probably began in the Archean some 3·5 Gyr ago, any O2 accumulation was local until 2·0 Gyr ago (Proterozoic) due to consumption by oxidation of Fe2+ and S2−. However, localized O2 accumulation before 2·0 Gyr ago could account for the observed early evolution of cytochrome oxidase and the possibility of O2-consuming chemolithotrophic and chemoorganotrophic nitrification, with further possibilities of NOx. production. Oxygen accumulation globally from 2·0 Gyr onwards coincided approximately with the evolution of eukaryotes, which contributed phagotrophy to the reactions of the N cycle as well as the nutrification-like aerobic production of NO. by nitric oxide synthetase, while lightning and bolides could now generate NO. from N2 and O2.

Evidence for terrestrial ecosystems is found from 1·0 Gyr onwards; NOx. and NH3 generated by terrestrial biota stands a greater chance of escaping to the atmosphere than do these compounds generated in the sea where recycling within the water body is likely. As CO2 levels fell and O2 levels rose, NH3 cycling in the photorespiratory carbon oxidation cycle might have been evident as early as 1 Gyr ago, although this does not seem to be a major contributor to atmospheric NH3 today. Embryophyte evolution on land 450 Myr ago, together with symbionts and biophages, increased primary productivity and N cycling on land, with greater quantitative possibilities for NOx. and NH3 escape to the atmosphere. The evolution of lignin (and related phenylpropanoids) at least 400 Myr ago, with associated NH3 recycling in vascular land plant, does not seem (on present evidence) to increase NH3 loss to the atmosphere significantly. Biomass burning occurred at least 350 Myr ago with lightning as the likely ignition source; such burning yielded NO., NH3, N2O and N2 from organic N. As in earlier times, the existence of terrestrial embryophyte vegetation has been punctuated by major bolide impacts, with the Cretaceous-Tertiary boundary impact generating perhaps 104 as much NO. as a year's thunderstorms do today, although the toxicity of NOx.per se to vegetation might not have been the major effect of the NOx. on biota. Terrestrial plants suffered fewer extinctions at this time than did many other major taxa. Despite such very significant generators of atmospheric combined N as major bolide impacts, the mean levels of NHy, NOx. and N2O (and O3) in the atmosphere during the 450 Myr existence of embryophyte vegetation was lower than the current, globally averaged, anthropogenically influenced values. Current globally averaged levels of atmospheric combined N are thus not without precedent in the history of life, globally for NOx., and locally for NHy, so vegetation has had evolutionary experience of high atmospheric combined N. However, this should not make us complacent about the impact of current wide-spread and continuing anthropogenic inputs of combined N, in view of the rate and extent of the inputs, and their combination with other aspects of local anthropogenic influence (e.g. SO2 from burning of high-S coal), stratospheric O3 depletion, and global environmental change (increasing CO2, temperature and sea-level).