Complexation of some trivalent lanthanides, scandium(III) and thorium(IV) by benzylidenepyruvates and cinnamylidenepyruvate in aqueous solution

The protonation constants of benzylidenepyruvate, 2-chloro-, 4-chlorobenzylidinepyruvate and cinnamylidenepyruvate as well as the stability constants of their binary 1:1 complexes with Cu(II), La(III), Pr(III), Sm(III), Lu(III), Sc(III) and Th(IV) have been determined spectrophotometrically in an aqueous medium at 25 °C and ionic strength 0.500 M, held with sodium perchlorate. Coordination centres in the aforementioned ligands are suggested. © 1995.

Ce(III) and Ce(IV) (re)distribution and fractionation in a laterite profile from Madagascar: Insights from in situ XANES spectroscopy at the Ce LIII-edge

The distribution of trivalent and tetravalent cerium, Ce(III) and Ce(IV) respectively, in a lateritic profile from Madagascar, has been characterized by X-ray-absorption near-edge structure (XANES) spectroscopy at the Ce LIII-edge on the LUCIA beamline (SOLEIL synchrotron, France). XANES spectra were acquired on bulk-rock samples as well as on specific lateritic minerals or polymineral zones (in-situ measurements) of the tonalite bedrock and the three overlying weathered horizons (C-, B- and A-horizons). Geochemically, the bedrock, and the A- and C-horizons show similar rare earth element content (REE = 363–405 mg/kg). They also display the same positive Ce-anomaly (CeCN/Ce∗ = 1.12–1.45), which is therefore likely to be inherited from the bedrock. In the B-horizon, the higher REE content (REE = 2194 mg/kg) and the larger Ce-anomaly (CeCN/Ce∗ = 4.26) are consistent with an accumulation zone caused by the evaporation of groundwater during the dry season. There is a good agreement between the Ce(III)/Cetotal ratio (XCe(III)) deduced from the positive Ce-anomaly (bulk-rock geochemical data) and that derived from XANES spectroscopy on the same bulk-rock samples (BR-XCe(III)-XANES) in the bedrock, and the C- and B-horizons. In the A-horizon, XANES measurements on bulk rock and minerals revealed a higher BR-XCe(III)-XANES (up to 100%) compared to the XCe(III) deduced from geochemical data (XCe(III) = 79%). The preservation of a positive Ce-anomaly in the A-horizon suggests that the Ce mobilization and redistribution during weathering occurred with no significant Ce fractionation from other trivalent REE. Remarkably, the only investigated sample where cerianite is observed belongs to the B-horizon. Within this horizon, Ce oxidation state varies depending on the microstructural position (porosity, cracks, clay-rich groundmass). The highest Ce(IV) concentrations are measured in cerianite (and aluminophosphates) localized in pores at the vicinity of Mn-rich domains (XCe(III)-XANES = 30–51%). Therefore, Ce fractionation from other REE is attributed to a Ce oxidation and precipitation potentially assisted by oxyhydroxide scavenging. In the C-horizon, Ce(III) and Ce(IV) are mainly distributed in REE-minerals of the rhabdophane group found in pores and cracks. The similarity between the Ce(III) proportion of rhabdophane grains (XCe(III)-XANES = 74–89%) with that of the bedrock (BR-XCe(III)-XANES = 79%) suggests no significant fractionation of Ce(III) and Ce(IV) between solution and mineral during the successive stages of primary REE-mineral alteration, transport in solution and secondary precipitation in the incipient stages of weathering. Overall, our novel spectroscopic approach shows that Ce is not necessarily oxidized nor fractionated from other REE during weathering in lateritic conditions. This implies that like Ce(III), Ce(IV) can be mobilized in aqueous fluids during weathering, possibly thanks to complexation with organic molecules, and can precipitate together with Ce(III) in secondary REE-bearing minerals. The corollary is that (paleo)redox reconstructions in soils and/or sediments based on Ce-anomaly in weathered rocks or minerals must be interpreted with caution.

Freeze and Phase IV

At head of cover title: Economic stabilization program

Louisiana energy conservation plan, in response to title III, part C, Energy policy and conservation act of 1975 (Public Law 94-163) and title IV, part B, Energy conservation and production act of 1976 (Public Law 94-385) /

Cover title: Energy conservation plan for the State of Louisiana, (Public Law 94-163 & 94-385).

Mrs. Fitzherbert and George IV,

"List of authorities": p. 464-466.

Astronomical and geographical essays: containing, I. A ... view, on a new plan, of the general principles of astronomy. II. The use of the celestial and terrestrial globes ... III. The description and use of the most improved planetarium, tellurian, and lunarium. IV. An introduction to practical astronomy.

Tailpiece.

Mrs. Fitzherbert and George IV,

"List of authorities": v.2, p.323-326.

An inventory of the ancient monuments in Wales and Monmouthshire. IV. County of Denbigh.

Mode of access: Internet.

Examination of the overlap between DSM-111-R overanxious disorder and DSM-IV generalized anxiety disorder in childhood

Since DSM-III-R criteria for Overanxious Disorder (OAD) was subsumed under Generalized Anxiety Disorder (GAD) in DSM-IV, three studies have investigated the overlap between the diagnoses. Although two studies have identified children meeting both OAD and GAD criteria (OAD/GAD group), a third study has identified children who met criteria for OAD, but not GAD (OAD group). Based on finding these two groups of children, we examined whether children in the OAD group (n= 30) could be differentiated from children in the OAD/GAD group (n=81) based on self and parent report of anxious symptoms and level of functional impairment. Conditional probability rates were also calculated for each of the DSM anxious symptoms to determine their overall clinicalutility. Findings revealed that the OAD group of children experienced fewer anxious symptoms than children in the OAD/GAD group, though both groups showed some amount of impairment. The implications for research and practice are discussed.

Oxidative DNA damage induced by S(IV) in the presence of Cu(II) and Cu(I) complexes

The DNA damage induced by S(IV) in the presence of some Cu(II) complexes in air saturated solution was investigated. The addition of S(IV) to an air saturated solution containing CuII GGA (GGA = glycylglycyl-L-alanine), CuII G3 (G3 = triglycine) or CuII G4 (G4 = tetraglycine) and Ni(II) traces, causes rapid formation of the respective Cu(III) complex, with simultaneous O2 uptake and S(IV) oxidation. SO3•- and HO• were detected by EPR-spin trapping experiments. The DNA strand breaks were attributed to the oxysulfur radicals formed. In the reduction of Cu(II)/BCA (BCA = 4,4' dicarboxy-2-2'-biquinoline) by S(IV), with CuI BCA complex formation, there is the possible formation of carbon centered radical of BCA or peroxyl radical (ROO•) capable of oxidizing DNA bases. The intensity of DNA damage in the presence of these Cu(II) complexes and S(IV) (10-300 µmol L-1) followed the order: CuII BCA ∼ CuII G4 ∼ Cu(II) (added as Cu(NO3)2) > CuII G3 ∼ CuII GGA. Specifically for CuII BCA the damage occurred even at lower S(IV) concentration (0.1 µmol L-1). For the Cu(II) complexes with glycylglycylhistidine, glycylhistidylglycine, glycylhistidyllysine and glycylglycyltyrosylarginine the Cu(III) formation and the DNA damage was not observed.