Performance of correlation functionals in ab initio chemisorption cluster-model calculations: Alkali metals on Si(111)

The performance of different correlation functionals has been tested for alkali metals, Li to Cs, interacting with cluster models simulating different active sites of the Si(111) surface. In all cases, the ab initio Hartree-Fock density has been obtained and used as a starting point. The electronic correlation energy is then introduced as an a posteriori correction to the Hartree-Fock energy using different correlation functionals. By making use of the ionic nature of the interaction and of different dissociation limits we have been able to prove that all functionals tested introduce the right correlation energy, although to a different extent. Hence, correlation functionals appear as an effective and easy way to introduce electronic correlation in the ab initio Hartree-Fock description of the chemisorption bond in complex systems where conventional configuration interaction techniques cannot be used. However, the calculated energies may differ by some tens of eV. Therefore, these methods can be employed to get a qualitative idea of how important correlation effects are, but they have some limitations if accurate binding energies are to be obtained.

Trace element partitioning in HP-LT metamorphic assemblages during subduction-related metamorphism, Ile de Groix, France: a detailed LA-ICPMS study

Devolatilization reactions and subsequent transfer of fluid from subducted oceanic crust into the overlying mantle wedge are important processes, which are responsible for the specific geochemical characteristics of subduction-related metamorphic rocks, as well as those of arc magmatism. To better understand the geochemical fingerprint induced by fluid mobilization during dehydration and rehydration processes related to subduction zone metamorphism, the trace element and rare earth element (REE) distribution patterns in HP-LT metamorphic assemblages in eclogite-, blueschist- and greenschist-facies rocks of the Ile de Groix were obtained by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) analysis. This study focuses on 10 massive basic rocks representing former hydrothermally altered mid-ocean ridge basalts (MORB), four banded basic rocks of volcano-sedimentary origin and one micaschist. The main hosts for incompatible trace elements are epidote (REE, Th, U, Pb, Sr), garnet [Y, heavy REE (HREE)], phengite (Cs, Rb, Ba, B), titanite [Ti, Nb, Ta, REE; HREE > LREE (light REE)], rutile (Ti, Nb, Ta) and apatite (REE, Sr). The trace element contents of omphacite, amphibole, albite and chlorite are low. The incompatible trace element contents of minerals are controlled by the stable metamorphic mineral assemblage and directly related to the appearance, disappearance and reappearance of minerals, especially epidote, garnet, titanite, rutile and phengite, during subduction zone metamorphism. Epidote is a key mineral in the trace element exchange process because of its large stability field, ranging from lower greenschist- to blueschist- and eclogite-facies conditions. Different generations of epidote are generally observed and related to the coexisting phases at different stages of the metamorphic cycle (e.g. lawsonite, garnet, titanite). Epidote thus controls most of the REE budget during the changing P-T conditions along the prograde and retrograde path. Phengite also plays an important role in determining the large ion lithophile element (LILE) budget, as it is stable to high P-T conditions. The breakdown of phengite causes the release of LILE during retrogression. A comparison of trace element abundances in whole-rocks and minerals shows that the HP-LT metamorphic rocks largely retain the geochemical characteristics of their basic, volcano-sedimentary and pelitic protoliths, including a hydrothermal alteration overprint before the subduction process. A large part of the incompatible trace elements remained trapped in the rocks and was recycled within the various metamorphic assemblages stable under changing metamorphic conditions during the subduction process, indicating that devolatilization reactions in massive basic rocks do not necessarily imply significant simultaneous trace element and REE release.

Trace element supplementation modulates pulmonary infection rates after major burns: a double-blind, placebo-controlled trial.

Infections remain the leading cause of death after major burns. Trace elements are involved in immunity and burn patients suffer acute trace element depletion after injury. In a previous nonrandomized study, trace element supplementation was associated with increased leukocyte counts and shortened hospital stays. This randomized, placebo-controlled trial studied clinical and immune effects of trace element supplements. Twenty patients, aged 40 +/- 16 y (mean +/- SD), burned on 48 +/- 17% of their body surfaces, were studied for 30 d after injury. They consumed either standard trace element intakes plus supplements (40.4 micromol Cu, 2.9 micromol Se, and 406 micromol Zn; group TE) or standard trace element intakes plus placebo (20 micromol Cu, 0.4 micromol Se, and 100 micromol Zn; group C) for 8 d. Demographic data were similar for both groups. Mean plasma copper and zinc concentrations were below normal until days 20 and 15, respectively (NS). Plasma selenium remained normal for group TE but decreased for group C (P < 0.05 on days 1 and 5). Total leukocyte counts tended to be higher in group TE because of higher neutrophil counts. Proliferation to mitogens was depressed compared with healthy control subjects (NS). The number of infections per patient was significantly (P < 0.05) lower in group TE (1.9 +/- 0.9) than in group C (3.1 +/- 1.1) because of fewer pulmonary infections. Early trace element supplementation appears beneficial after major burns; it was associated with a significant decrease in the number of bronchopneumonia infections and with a shorter hospital stay when data were normalized for burn size.

Control of Concrete Deterioration Due to Trace Compounds in Deicers, HR-299, 1992

This report describes the research completed under the research contract entitled "Development of a Conductometric Test for Frost Resistance of Concrete" undertaken for the Iowa Highway Research Board. The objective of the project was to develop a test method which can be reasonably and rapidly performed in the laboratory and in the field to predict, with a high degree of certainty, the behavior of concrete subjected to the action of alternate freezing and thawing. The significance of the results obtained, and recommendations for use and the continued development of conductometric testing are presented in this final report. In this project the conductometric evaluation of concrete durability was explored with three different test methods. The test methods and procedures for each type of test as well as presentation of the results obtained and their significance are included in the body of the report. The three test methods were: (1) Conductometric evaluation of the resistance of concrete to rapid freezing and thawing, (2) Conductometric evaluation of the resistance of concrete to natural freezing and thawing, and (3) Conductometric evaluation of the pore size distribution of concrete and its correlation to concrete durability. The report also includes recommendations for the continued development of these test methods.

Effects of Deicing Salt Trace Compounds on Deterioration of Portland Cement Concrete, HR-271, 1987

A study was made of the detrimental effects of trace amounts of calcium sulfate (occurring naturally in halite deposits used for deicing) on portland cement concrete pavements. It was found that sulfate introduced as gypsum with sodium chloride in deicing brines can have detrimental effects on portland cement mortar. Concentrations of sulfate as low as 0.5% of the solute rendered the brine destructive. Conditions of brine application were critical to specimen durability. The mechanisms of deterioration were found to be due to pore filling resulting from compound formation and deposition. A field evaluation of deteriorating joints suggests that the sulfate phenomena demonstrated in the laboratory also operates in the field. A preliminary evaluation was made of remedies: limits on sulfates, fly ash admixtures, treatment of existing pavement, and salt treatments. This report gives details of the research objectives, experimental design, field testing, and possible solutions. Recommendations for further study are presented.

Control of Concrete Deterioration Due to Trace Compounds in Deicers, HR-299 Phase I, 1988

This report presents the results of research on the influence of trace compounds from rock salt deicers on portland cement mortar and concrete. An evaluation of the deicers in stock throughout the state showed that about ninety-five percent contained enough sulfate to cause accelerated deterioration of concrete. Of the impurities found in rock salts, sulfate compounds of calcium and magnesium were found to be equally deleterious. Magnesium chloride was found to be innocuous. Introduction of fly ash eliminated the damage to portland cement mortar caused by sulfates. When used with frost resistant Alden aggregate in fly ash concrete and exposed to a variety of deicer brine compositions, the concrete did not deteriorate after exposure. With the exception of a high calcium brine, the behavior of the frost-prone Garrison aggregate was independent of deicer treatment; the high calcium brine reduced frost damage with this aggregate. Two approaches to reducing sulfate deterioration from deicers are suggested as (1) limiting the amount of sulfate to about 0.28 percent, and (2) making concrete sulfate-resistant by using fly ash. Techniques for making existing concrete deicer-sulfate-resistant are essential to a practical solution.

Control of Concrete Deterioration Due to Trace Compounds in Deicers, Phase II, HR-299, 1989

This report presents results of research on ways to reduce the detrimental effects of sulfate-tainted rock salt deicers on portland cement concrete used for highway pavements. Repetitious experiments on the influence of fly ash on the mortar phase of concrete showed significant improvement in resistance to deicing brines is possible. Fifteen to twenty percent by weight of fly ash replacement for portland cement was found to provide optimum improvement. Fly ashes from five sources were evaluated and all were found to be equally beneficial. Preliminary results indicate the type of coarse aggregate also plays an important role in terms of concrete resistance to freeze-thaw in deicing brines. This was particularly true for a porous ferroan dolomite thought to be capable of reaction with the brine. In this case fly ash improved the concrete, but not enough for satisfactory performance. An intermediate response was with a porous limestone where undesirable results were observed without fly ash and adequate performance was realized when 15% fly ash was added. The best combination for making deicer-resistant concrete was found to be with a non-porous limestone. Performance in brines was found to be adequate without fly ash, but better when fly ash was included. Consideration was given to treating existing hardened concrete made with poor aggregate and no fly ash to extend pavement life in the presence of deicers, particularly at joints. Sodium silicate was found to improve freeze-thaw resistance of mortar and is a good candidate for field usage because of its low cost and ease of handling.

Atmospheric deposition and migration of artificial radionuclides in Alpine soils (Val Piora, Switzerland) compared to the distribution of selected major and trace elements.

Artificial radionuclides ((137)Cs, (90)Sr, Pu, and (241)Am) are present in soils because of Nuclear Weapon Tests and accidents in nuclear facilities. Their distribution in soil depth varies according to soil characteristics, their own chemical properties, and their deposition history. For this project, we studied the atmospheric deposition of (137)Cs, (90)Sr, Pu, (241)Am, (210)Pb, and stable Pb. We compared the distribution of these elements in soil profiles from different soil types from an alpine Valley (Val Piora, Switzerland) with the distribution of selected major and trace elements in the same soils. Our goals were to explain the distribution of the radioisotopes as a function of soil parameters and to identify stable elements with analogous behaviors. We found that Pu and (241)Am are relatively immobile and accumulate in the topsoil. In all soils, (90)Sr is more mobile and shows some accumulations at depth into Fe-Al rich horizons. This behavior is also observed for Cu and Zn, indicating that these elements may be used as chemical analogues for the migration of (90)Sr into the soil.