Unclassified U.S. Atomic Energy Commission reports on the metallurgy of zirconium and hafnium /

"TID-3508 Metallurgy and Ceramics."

Distillation separation of zirconium and hafnium : summary report for February 14, 1949 to March 31, 1950 /

"Contract No. AT(30-1)-534."

The first spectrum of hafnium (Hf I) /

Mode of access: Internet.

Hafnium cross sections and their temperature dependence,

"Contract W-7 405-Eng. 36 with the U. S. Atomic Energy Commission."

Zirconium and hafnium, a bibliography,

"Work performed under Contract no. AT-(30-1)-534."

(Table 1) Dissolved Hafnium and Neodymium in the South Atlantic measured on water bottle samples during POLARSTERN cruise ANT-XXIV/3

We present the first combined dissolved hafnium (Hf) and neodymium (Nd) concentrations and isotope compositions of deep water masses from the Atlantic sector of the Southern Ocean. Eight full depth profiles were analyzed for Hf and twelve for Nd. Hafnium concentrations are generally depleted in the upper few hundred meters ranging between 0.2 pmol/kg and 0.4 pmol/kg and increase to relatively constant values of around 0.6 pmol/kg in the deeper water column. At the stations north of the Polar Front (PF), Nd concentrations increase linearly from about 10 pmol/kg at depths of ~ 200 m to up to 31 pmol/kg close to the bottom indicating particle scavenging and release. Within the Weddell Gyre (WG), however, Nd concentrations are essentially constant at 25 pmol/kg at depths greater than ~ 1000 m. The distributions of both elements show a positive correlation with dissolved silicon implying a close linkage to diatom biogeochemistry. Hafnium essentially shows invariant isotope compositions with values averaging at epsilon-Hf = +4.6, whereas Nd isotopes mark distinct differences between water masses, such as modified North Atlantic Deep Water (NADW, epsilon-Nd = -11 to -10) and Antarctic Bottom Water (AABW, epsilon-Nd = -8.6 to -9.6), but also waters locally advected via the Agulhas Current can be identified by their unradiogenic Nd isotope compositions. Mixing calculations suggest that a small fraction of Nd is removed by particle scavenging during mixing of water masses north of the PF. Nevertheless, the Nd isotope composition has apparently not been significantly affected by uptake and release of Nd from particles, as indicated by mixing calculations. A mixing envelope of an approximated North Pacific and a North Atlantic end-member shows that Nd isotope and concentration patterns in the Lower Circumpolar Deep Water (LCDW) can be fully explained by ~ 30:70 percentage contributions of these respective end-members.

Hafnium and neodymium in surface waters of the Atlantic sector of the Southern Ocean

Radiogenic isotopes of hafnium (Hf) and neodymium (Nd) are powerful tracers for water mass transport and trace metal cycling in the present and past oceans. However, due to the scarcity of available data the processes governing their distribution are not well understood. Here we present the first combined dissolved Hf and Nd isotope and concentration data from surface waters of the Atlantic sector of the Southern Ocean. The samples were collected along the Zero Meridian, in the Weddell Sea and in the Drake Passage during RV Polarstern expeditions ANT-XXIV/3 and ANT-XXIII/3 in the frame of the International Polar Year (IPY) and the GEOTRACES program. The general distribution of Hf and Nd concentrations in the region is similar. However, at the northernmost station located 200 km southwest of Cape Town a pronounced increase of the Nd concentration is observed, whereas the Hf concentration is minimal, suggesting much less Hf than Nd is released by the weathering of the South African Archean cratonic rocks. From the southern part of the Subtropical Front (STF) to the Polar Front (PF) Hf and Nd show the lowest concentrations (<0.12 pmol/kg and 10 pmol/kg, respectively), most probably due to the low terrigenous flux in this area and efficient scavenging of Hf and Nd by biogenic opal. In the vicinity of landmasses the dissolved Hf and Nd isotope compositions are clearly labelled by terrigenous inputs. Near South Africa Nd isotope values as low as epsilon-Nd = -18.9 indicate unradiogenic inputs supplied via the Agulhas Current. Further south the isotopic data show significant increases to epsilon-Hf = 6.1 and epsilon-Nd = -4.0 documenting exchange of seawater Nd and Hf with the Antarctic Peninsula. In the open Southern Ocean the Nd isotope compositions are relatively homogeneous (epsilon-Nd ~ -8 to -8.5) towards the STF, within the Antarctic Circumpolar Current, in the Weddell Gyre, and the Drake Pasage. The Hf isotope compositions in the entire study area only show a small range between epsilon-Hf = +6.1 and +2.8 support Hf to be more readily released from young mafic rocks compared to old continental ones. The Nd isotope composition ranges from epsilon-Nd = -18.9 to -4.0 showing Nd isotopes to be a sensitive tracer for the provenance of weathering inputs into surface waters of the Southern Ocean.

Amorphous HfO(2) and Hf(1-x)Si(x)O via a melt-and-quench scheme using ab initio molecular dynamics

We have performed ab initio molecular dynamics simulations to generate an atomic structure model of amorphous hafnium oxide (a-HfO(2)) via a melt-and-quench scheme. This structure is analyzed via bond-angle and partial pair distribution functions. These results give a Hf-O average nearest-neighbor distance of 2.2 angstrom, which should be compared to the bulk value, which ranges from 1.96 to 2.54 angstrom. We have also investigated the neutral O vacancy and a substitutional Si impurity for various sites, as well as the amorphous phase of Hf(1-x)Si(x)O(2) for x=0.25, 0375, and 0.5.

Protective effect of different tetrafluorides on erosion of pellicle-free and pellicle-covered enamel and dentine

The aim was to analyze the protective effects of titanium, zirconium and hafnium tetrafluorides on erosion of pellicle-free and pellicle-covered enamel and dentine in vitro. Eight groups of 20 specimens each of bovine enamel and bovine dentine were prepared. Half the specimens in each group were immersed in human saliva for 2 h for pellicle formation. Specimens were then left untreated (controls) or were treated for 120 s with TiF(4), ZrF(4) or HfF(4) solutions (0.4 or 1%) or 1.25% AmF/NaF gel. All specimens were eroded by exposure to hydrochloric acid, pH 2.6, for 25 min. Cumulative calcium release into the acid was monitored in consecutive 30-second intervals for 5 min, then at 2-min intervals up to a total erosion time of 25 min using the Arsenazo III procedure. Data were analyzed by ANOVA. 1% TiF(4) solution offered the best protective effect, especially in dentine (reduction of calcium loss about 50% at 25 min). 1% ZrF 4, 1% HfF 4 and 0.4% TiF(4) also reduced calcium loss, but to a lesser extent. Long-term effects were limited to dentine, while reduction of enamel erosion (about 25%) was restricted to 1-min erosion. The fluoride gel had a protective effect only in dentine. The efficacy of the tetrafluorides was influenced by the presence of the pellicle layer, in that the protection against dentine erosion by TiF(4) and ZrF(4) was greater on pellicle-covered specimens. Tetrafluoride solutions, especially 1% TiF(4), could decrease dental erosion, but were more effective on dentine than on enamel. Copyright (C) 2008 S. Karger AG, Basel.

Combined chemical separation of Lu, Hf, Sm, Nd, and REEs from a single rock digest: Precise and accurate isotope Determinations of Lu-Hf and Sm-Nd using multicollector-ICPMS

A combined procedure for separating Lu, Hf, Sm, Nd, and rare earth elements (REEs) from a single sample digest is presented. The procedure consists of the following five steps: (1) sample dissolution via sodium peroxide sintering; (2) separation of the high field strength elements from the REEs and other matrix elements by a HF-free anion-exchange column procedure; (3) purification of Hf on a cation-exchange resin; (4) separation of REEs from other matrix elements by cation exchange; (5) Lu, Sm, and Nd separation from the other REEs by reversed-phase ion chromatography. Analytical reproducibilities of Sm-Nd and Lu-Hf isotope systematics are demonstrated for standard solutions and international rock reference materials. Results show overall good reproducibilities for Sm-Nd systematics independent of the rock type analyzed. For the Lu-Hf systematics, the reproducibility of the parent/daughter ratio is much better for JB-1 (basalt) than for two analyzed felsic crustal rocks (DR-N and an Archaean granitoid). It is demonstrated that this poorer reproducibility of the Lu/Hf ratio is truly caused by sample heterogeneity; thus, results are geologically reasonable.