Nominally hydrous magmatism on the Moon.

For the past 40 years, the Moon has been described as nearly devoid of indigenous water; however, evidence for water both on the lunar surface and within the lunar interior have recently emerged, calling into question this long-standing lunar dogma. In the present study, hydroxyl (as well as fluoride and chloride) was analyzed by secondary ion mass spectrometry in apatite [Ca(5)(PO(4))(3)(F,Cl,OH)] from three different lunar samples in order to obtain quantitative constraints on the abundance of water in the lunar interior. This work confirms that hundreds to thousands of ppm water (of the structural form hydroxyl) is present in apatite from the Moon. Moreover, two of the studied samples likely had water preserved from magmatic processes, which would qualify the water as being indigenous to the Moon. The presence of hydroxyl in apatite from a number of different types of lunar rocks indicates that water may be ubiquitous within the lunar interior, potentially as early as the time of lunar formation. The water contents analyzed for the lunar apatite indicate minimum water contents of their lunar source region to range from 64 ppb to 5 ppm H(2)O. This lower limit range of water contents is at least two orders of magnitude greater than the previously reported value for the bulk Moon, and the actual source region water contents could be significantly higher.

Explaining the effects of T-O-T bond angles on NMR chemical shifts in aluminosilicates: A natural bonding orbital (NBO) and natural chemical shielding (NCS) analysis.

It has long been recognized that the 29Si and 27Al NMR chemical shifts for aluminosilicate crystals and glasses correlate to some extent with the T-O-T bond angle (where T is the tetrahedral atom Si or Al). With increasing T-O-T bond angle, the 29Si and 27Al NMR shieldings increase and the shifts thus become more negative. This result has been demonstrated both experimentally and through quantum computations. However, no simple qualitative explanation has ever been given for what appears to be a simple qualitative trend. We here provide such an explanation based upon quantum calculations. We have used high level ab initio NMR shielding calculations, natural bonding orbital (NBO) analysis, and natural chemical shielding (NCS) analysis, performed on model clusters with different T-O-T angles, to obtain an explanation for this trend from an electronic structure point of view. On the basis of both NBO populations and the NCS analysis, the following factors account for the correlation of shift with T-O-T angle: (1) a slight increase in population of the Al-O and Si-O bond orbital electrons and a dramatic change in bond orbital shapes and hybridization (with more s character and less bond bending as the T-O-T angle increases), (2) a movement of one of the lone pairs on O toward the vicinity of the Si or Al as the T-O-T angle increases, and (3) a change in the shielding contribution from the core 2p electrons of Al or Si. The changes in the 17O NMR shift with T-O-T angle are more complex, and the shifts are also more strongly influenced by distant atoms, but some systematic changes in O lone pair contributions can be identified.