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."

Alternativas quimiométricas para a resolução de problemas analíticos clássicos: determinação espectrofotométrica de misturas de zircônio e háfnio

The determination of zirconium-hafnium mixtures is one of the most critical problem of the analytical chemistry, on account of the close similarity of their chemical properties. The spectrophotometric determination proposed by Yagodin et al. show not many practical applications due to the significant spectral interference on the 200-220 nm region. In this work we propound the use of a multivariate calibration method called partial least squares ( PLS ) for colorimetric determination of these mixtures. By using PLS and 16 calibration mixtures we obtained a model which permits determination of zirconium and hafnium with accuracy of about 1-2% and 10-20%, respectively. Using conventional univariate calibration the inaccuracy of the determination is about 10-25% for zirconium and above 57% for hafnium.

Organometallic Hydroxides of Transition Elements

Northern Illinois University DeKalb,Institut fu¨r Anorganische Chemie & Southern Methodist University

Geochemistry of Central American Volcanic Arc basement samples

The Central American Volcanic Arc (CAVA) has been the subject of intensive research over the past few years, leading to a variety of distinct models for the origin of CAVA lavas with various source components. We present a new model for the NW Central American Volcanic Arc based on a comprehensive new geochemical data set (major and trace element and Sr-Nd-Pb-Hf-O isotope ratios) of mafic volcanic front (VF), behind the volcanic front (BVF) and back-arc (BA) lava and tephra samples from NW Nicaragua, Honduras, El Salvador and Guatemala. Additionally we present data on subducting Cocos Plate sediments (from DSDP Leg 67 Sites 495 and 499) and igneous oceanic crust (from DSDP Leg 67 Site 495), and Guatemalan (Chortis Block) granitic and metamorphic continental basement. We observe systematic variations in trace element and isotopic compositions both along and across the arc. The data require at least three different endmembers for the volcanism in NW Central America. (1) The NW Nicaragua VF lavas require an endmember with very high Ba/(La, Th) and U/Th, relatively radiogenic Sr, Nd and Hf but unradiogenic Pb and low d18O, reflecting a largely serpentinite-derived fluid/hydrous melt flux from the subducting slab into a depleted N-MORB type of mantle wedge. (2) The Guatemala VF and BVF mafic lavas require an enriched endmember with low Ba/(La, Th), U/Th, high d18O and radiogenic Sr and Pb but unradiogenic Nd and Hf isotope ratios. Correlations of Hf with both Nd and Pb isotopic compositions are not consistent with this endmember being subducted sediments. Granitic samples from the Chiquimula Plutonic Complex in Guatemala have the appropriate isotopic composition to serve as this endmember, but the large amounts of assimilation required to explain the isotope data are not consistent with the basaltic compositions of the volcanic rocks. In addition, mixing regressions on Nd vs. Hf and the Sr and O isotope plots do not go through the data. Therefore, we propose that this endmember could represent pyroxenites in the lithosphere (mantle and possibly lower crust), derived from parental magmas for the plutonic rocks. (3) The Honduras and Caribbean BA lavas define an isotopically depleted endmember (with unradiogenic Sr but radiogenic Nd, Hf and Pb isotope ratios), having OIB-like major and trace element compositions (e.g. low Ba/(La, Th) and U/Th, high La/Yb). This endmember is possibly derived from melting of young, recycled oceanic crust in the asthenosphere upwelling in the back-arc. Mixing between these three endmember types of magmas can explain the observed systematic geochemical variations along and across the NW Central American Arc.

Geochemistry of DSDP Leg 91 basalts

Basalts recovered from Sites 595 and 596 on Mesozoic crust in the southwest Pacific range from olivine-bearing tholeiites to ferrobasalts. Despite having undergone extensive low-grade alteration, which has raised K and Rb abundances, the basalts have consistent interelement ratios of Ti, Zr, Hf, rare-earth elements, Y, Th, Ik, and Nb. La/Ta (-18), Lan/Ybn (0.6), Ti/Zr (115), Zr/Nb (20), and Th/Hf (0.08) ratios all fall within the range of N-type mid-ocean-ridge basalt. The basalts from Sites 595 and 596 indicate that the Mesozoic Pacific crust was derived from a mantle source by processes similar to those operating at the present-day East Pacific Rise.

Geochemistry of basalts at DSDP Site 89-462

At Site 462 in the Nauru Basin, western Pacific Ocean, 56 lithologic units have been recovered from an extensive flood basalt province. Fossil evidence suggests that the lavas were emplaced during the interval 100-115 Ma, some 30 m.y. after formation of the underlying Jurassic ocean crust. The lithologic units can be broadly divided into three chemical units, the lowermost two of which are chemically monotonous, suggesting rapid eruption of basalt from a compositionally homogeneous magma chamber. All the basalts are hypersthene- (hy-) rich tholeiites, with approximately chondritic La/Sm, La/Yb, Zr/Nb, La/Ta, and Th/Hf ratios. Chemically they resemble, in part, "transitional" mid-ocean ridge basalts (MORB) from areas such as the Reykjanes Ridge, although Rb, Ba, and K contents are very low and similar to those of "normal" MORB. Their 87Sr/86Sr ratios are higher than in N-type MORB (Fujii et al., 1981). The chemistry of the Nauru basalts differs from that of continental flood basalts, which tend to be strongly enriched in large-ion lithophile (LIL) elements, although the extent to which the differences result from sialic contamination or source variability is not clear.

Element concentrations of aluminosilicate components from ODP sites in the Pacific Ocean

We measured major and trace element concentrations in the operationally defined, chemically extracted, residual aluminosilicate component of sediment from Ocean Drilling Program Sites 1215 and 1256 in the central and eastern equatorial Pacific Ocean and found that this residual component contains volcanogenic and authigenic aluminosilicates in addition to inferred eolian material. While the residual component younger than 20 Ma from the central Pacific (ODP Site 1215) is similar compositionally to upper continental crust and suggests an increase in the delivery of Asian dust material since 20 Ma, the residual in sediment older than 20 Ma indicates significant amounts of volcanogenic and authigenic materials. Volcanogenic debris comprises as much as ~ 40% of the residual between 23-40 Ma, which coincides with the mid-Tertiary "ignimbrite flare-up" that occurred in much of western North America. The residual component extracted from the 50 Ma biogenic sediment reflects authigenic signatures (seawater-like negative cerium anomalies and elevated Fe/Si ratios). The previously interpreted increase in an andesitic detrital source in North Pacific locations may instead be authigenic material, presenting significant challenges for many paleoclimate proxies. Additionally, in the eastern Pacific (ODP Site 1256), the residual component contains ~70% of volcanogenic material, most likely originating from Central America, and also includes refractory barite. The ability to separately identify eolian, volcanogenic, and authigenic materials in the aluminosilicate component of pelagic sediment allows resolution, respectively, of the climatic, geologic, and chemical processes contributing to the paleoceanographic archive in this critical oceanic region.

CONTRIBUTION TO THE STUDY OF ZIRCONIUM AND HAFNIUM ALPHA-HYDROXYCARBOXYLATES

A study of both zirconium and hafnium alpha-hydroxycarboxylates for analytical applications is presented, These compounds are studied by infrared spectroscopy, thermal analysis and X-ray diffractometry. dl-Mandelic, dl-p-bromomandelic and dl-2-naphthylglycolic acids are the more adequate reagents for gravimetric determinations of zirconium and hafnium, the ligands dl-2-hydroxyhexanoic and dl-2-hydroxydodecanoic acids were used for the first time and the results showed that they are also adequate reagents for the same purpose.

Zirconium and hafnium, a bibliography,

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