April L. Pulvirenti

Composition and particle size of superparamagnetic corrosion products in tap water

Chemical analyses, magnetization, Mössbauer spectrum, and x-ray diffraction measurements were made on solids removed from tap water by means of membrane filters. The taps from which this water was obtained had previously been unused for prolonged periods of time. When these taps were reactivated and water was first drawn, it was observed that the quantity of coarse solids in the water gradually decreased with flow, while at the same time the quantity of fine solids gradually increased. The magnetization, Mössbauer spectra, and x-ray diffraction patterns of the solids showed the presence of a significant number of superparamagnetic particles of magnetite. In the temperature range of our measurements (77 K<T<300 K), paramagnetic iron-based species, particularly lepidocrocite, were also present in the solids. Contaminants such as Pb, Cu, and As were observed to be present in significant amounts, and it is shown that these are adsorbed to the magnetic nanoparticles. It was observed that almost all of the solid particles could be removed by means of 5-microm filters. This removal process can be explained by means of a model which assumes that initial deposition of coarse aggregates of corrosion products on the filters forms a coating, rich in extremely fine iron oxides. The coating has a high capacity for sorption of very small individual particles.

Chemical treatment of spent carbon liners used in the electrolytic production of aluminum

Abstract Chemical cleaning methods were developed for the removal of leachable hazardous cyanide and fluoride impurities from spent carbon liners used in aluminum metal production. Cyanide can be destroyed by treatment with NaOCl solutions at near-neutral pH. Fluoride can be removed by treatment with solutions of strong acids, e.g., 0.5 M H 2 SO 4 . This treatment is more effective at elevated temperatures (e.g., 80 °C). The acid used in chemical cleaning can be treated in order to remove extracted fluoride by passing it through an alumina bed.

Acid generation upon thermal concentration of natural water: the critical water content and the effects of ionic composition.

Thermal evaporation of a variety of simulated pore waters from the region of Yucca Mountain, Nevada, produced acidic liquids and gases during the final stages of evaporation. Several simulated pore waters were prepared and then thermally distilled in order to collect and analyze fractions of the evolved vapor. In some cases, distillates collected towards the end of the distillation were highly acidic; in other cases the pH of the distillate remained comparatively unchanged during the course of the distillation. The results suggest that the pH values of the later fractions are determined by the initial composition of the water. Acid production stems from the hydrolysis of magnesium ions, especially at near dryness. Near the end of the distillation, magnesium nitrate and magnesium chloride begin to lose water of hydration, greatly accelerating their thermal decomposition to form acid. Acid formation is promoted further when precipitated calcium carbonate is removed. Specifically, calcium chloride-rich pore waters containing moderate (10-20 ppm) levels of magnesium and nitrate and low levels of bicarbonate produced mixtures of nitric and hydrochloric acid, resulting in a precipitous drop in pH to values of 1 or lower after about 95% of the original volume was distilled. Waters with either low or moderate magnesium content coupled with high levels of bicarbonate produced slightly basic fractions (pH 7-9). If calcium was present in excess of bicarbonate, waters containing moderate levels of magnesium produced acid even in the presence of bicarbonate, due to the precipitation of calcium carbonate. Other salts such as halite and anhydrite promote the segregation of acidic vapors from residual basic solids. The concomitant release of wet acid gas has implications for the integrity of the alloys under consideration for containers at the Yucca Mountain nuclear waste repository. Condensed acid gases at very low pH, especially mixtures of nitric and hydrochloric acid, are capable of corroding even alloys, such as nickel-based Alloy 22, which are considered to be corrosion-resistant under milder conditions.

Removal of superparamagnetic corrosion products and contaminants from drinking water using activated carbon

AbstractParticulate matter separated from tap water using columns of coarse and fine activated carbon was characterized by means of chemical analysis, magnetization measurements, X-ray diffraction (XRD) and scanning electron microscopy (SEM)––energy dispersive X-ray spectrometry (EDS). A large fraction of the solids accumulated on the activated carbon consisted of iron oxides, in particular magnetite nanoparticles, and of iron oxyhydroxides, specifically goethite and lepidocrocite. These species formed as a result of corrosion of iron or carbon steel pipes. The removal of various iron species was measured using a two-column system consisting of a column of coarse activated carbon followed by a column of fine activated carbon. The results indicated that coarse activated carbon was only effective in removing oxyhydroxide particles, while the fine activated carbon was also able to remove nanoparticles of anhydrous iron oxides such as magnetite and maghemite. In addition, it was observed that while a majority...

Effects of Lead, Mercury, and Reduced Sulfur Species on the Corrosion of Alloy 22 in Concentrated Groundwaters as a Function of pH and Temperature

The effect of Pb, Hg, thiosulfate and sulfide on the corrosion of Alloy 22 was studied. In solutions of 1000xJ13 groundwater doped with these contaminants, disks and U-bend specimens exhibited general corrosion and pitting at pH 1, and some dissolution at pH 13. One specimen exposed to the presence of Pb cracked catastrophically. In basic media thiosulfate and sulfide caused both oxide spalling and enhanced general corrosion.

Effects of Fluoride and other Anions on the Corrosion of Alloy 22

Samples of Alloy 22 were tested in solutions containing various anions in order to determine their effect on the corrosion of the alloy. It was found that Alloy 22 is relatively corrosion resistant in HCl and HNO 3 at pH 1 and 160°C (general corrosion rates on the order of 10 μm/year), but more susceptible to phosphoric acid, especially under reducing conditions. The presence of fluoride raised the corrosion rate of Alloy 22 to the order 1 mm/year at pH 1, and fluoride is still active towards Alloy 22 at pH levels as high as 3.5. Samples tested in solutions of 1000xJ13 in which the pH was altered during testing showed an increase in corrosion rate over solutions of constant pH. Preliminary electrochemical tests suggest that nitrate may be an effective corrosion inhibitor in fluoride containing solutions, while sulfate is not.

Effects of Volatilization on Groundwater Chemistry

Both concentrated and dilute simulated solutions of saturated J13 and unsaturated UZ pore water were concentrated through distillation of the solutions under atmospheric pressure. It was observed that condensed vapors from the pH of J13 waters steadily rose during the distillations to a value of 10, while the pH of UZ waters remained steady until 90% of the volume of the solution had been distilled, after which the pH of the condensed vapors dropped precipitously, often below 1. Residual solutions analyzed when most of the solution had been distilled away were also found to be extremely acidic. The temperature of these residual solutions was around 144°C due to their high solute content causing boiling point elevation. All experiments were performed with the condenser open to ambient air at atmospheric pressure. The pH drop during the distillation of UZ water is attributed largely to the presence of large amounts of magnesium. Specimens of Alloy 22 tested in the residual solutions of at their boiling temperature (around 144°C) showed significant rates of general corrosion over a broad range, often approaching 1 mm/year. Similarly high corrosion rates were also observed in tests on Alloy 22 specimens in condensates obtained during the late stages of the distillation. These tests were performed either in situ at 75–80°C using a Soxhlet extractor, or in separate pressure vessels at temperatures between 90 and 130°C.