Some numerical considerations in the geochemical analysis of distal microtephra

The use of Late Quaternary tephra horizons as isochronous markers for high resolution correlation between records is of growing importance in a number of scientific fields. Particular advancements have been made through the identification of microtephra deposits (very distal deposits of volcanic ash invisible to the naked eye). The successful correlation of ash layers and volcanic eruptions depends on the acquisition of the major element chemistries of a tephra layer, derived from microprobe analyses of individual glass shards. This is particularly important for microtephras where aeolian fractionation has removed much of the mineral phase of the ash deposit, which often aids tephra discrimination. There are, however, difficulties in distinguishing precisely between different eruptions of the same volcano using major element composition and this may not always be resolved by the use of trace elements. Given the potential of tephrochronology as a correlative tool in many disciplines it is important to resolve this difficulty. One way forward is to perform more robust statistical analyses on the geochemical data, as in general, analyses are confined to a series of bi-plots of major elements. Here the authors explore some of the problems associated with dealing with microprobe data generated for individual tephras and pay particular attention to the ‘unit sum problem’. Using a subset of data generated as part of a EURODELTA project on tephra distribution in the Adriatic, the authors demonstrate that this problem is detectable in major element data from tephras and have consequently applied the logratio method before further analyses of the data. It is demonstrated that the use of logratios combined with discriminant functions analysis provides a more robust assessment of likely chemical correlations between tephras, and are superior to the use of bi-plots alone; and obviate the need for any data normalization, a particular point of contention between tephrochronologists.     

Comment on “Hydrolysis of neptunium(V) at variable temperatures (10-85 °C)” by L. Rao, T.G. Srinivasan, A.Yu. Garnov, P. Zanonato, P. Di Bernardo, and A. Bismondo

In a recent study [Rao, L., Srinivasan, T.G., Garnov, A.Yu., Zanonato, P., Di Bernardo, P., Bismondo, A., 2004. Hydrolysis of neptunium(V) at variable temperatures (10-85 °C). Geochim. Cosmochim. Acta68, 4821-4830.] the hydrolysis of Np(V) was investigated at 10-85 °C by absorption spectroscopy, potentiometry, and microcalorimetry along the titration of Np(V) solutions with tetramethylammonium hydroxide up to pH 10. However, there is strong evidence that the precautions to avoid competing reactions with carbonate were not sufficient and that the measured effects are not caused by the formation of Np(V) hydroxide complexes but primarily by the formation of Np(V) carbonate complexes. The reported equilibrium constants, enthalpies, entropies, and heat capacities for the complexes NpO₂OH(aq) and are severely in error and must not be used for the geochemical modeling of neptunium. If the hydrolysis constants reported by Rao et al. [Rao, L., Srinivasan, T.G., Garnov, A.Yu., Zanonato, P., Di Bernardo, P., Bismondo, A., 2004. Hydrolysis of neptunium(V) at variable temperatures (10-85 °C). Geochim. Cosmochim. Acta68, 4821-4830] are used to calculate neptunium solubilities in alkaline solutions relevant for nuclear waste repositories, the Np(V) concentrations are overestimated by orders of magnitude.     

Comment on “A critical evaluation of the boron isotope-pH proxy: The accuracy of ancient ocean pH estimates” by M. Pagani, D. Lemarchand, A. Spivack and J. Gaillardet

Pagani et al. [Pagani M., Lemarchand D., Spivack A., and Gaillardet J. (2005). A critical evaluation of the boron isotope-pH proxy: the accuracy of ancient ocean pH estimates. Geochim. Cosmochim. Acta69(4), 953-961] use data from previous boron isotope studies to suggest that the fractionation between boric acid and borate in seawater as well as the history of δ¹¹B in seawater are poorly understood, thus limiting our ability to capture realistic ocean pH with this proxy. Although we agree with the authors that the long recognized uncertainty in the secular variation of δ¹¹B_seawater imposes a temporal limit on paleo-pH reconstructions, their evaluation of the δ¹¹B/pH relationship in carbonates is flawed. Potential complications from vital, temperature and dissolution effects reported in that paper are based on studies that are experimentally and/or analytically poorly constrained. Using published validation studies we will demonstrate that many of the problems outlined by Pagani et al. have already been addressed, or are based on misinterpretations of previous work. Most importantly, statistical evaluation suggests empirical data are best described by a fractionation of ∼20‰. Recent paleoreconstructions confirm that the boron isotope proxy can be used with confidence, if sample selection and analyses are done carefully.