A new automated multi-function core scanning instrument, named ITRAX, has been developed that records optical, radiographic and elemental variations from sediment half cores up to 1.8 m long at a resolution as fine as 200 pm. An intense micro-X-ray beam focused through a flat capillary waveguide is used to irradiate samples to enable both Xradiography and X-ray fluorescence (XRF) analysis. Data are acquired incrementally by advancing a split core, via a programmable stepped motor drive, through the flat, rectangular-section X-ray beam. Traditional XRF determination of element composition in sediments provides high-quality data, but it takes a considerable time and normally consumes gram quantities of material that is often only available in limited quantities. The ITRAX core scanner non-destructively collects optical and X-radiographic images, and provides highresolution elemental profiles that are invaluable for guiding sample selection for further (destructive) detailed sampling. This paper presents a description of the construction, characteristics and capabilities of the ITRAX system. High-resolution ITRAX data obtained from sediment cores are also presented and compared with results from traditional wavelength-dispersive XRF analysis at lower resolution. Finally, some recent technical developments linked to the second-generation ITRAX are presented.

Pb isotopic studies of airborne particulate matter, incinerator ash, and gasoline have been carried out to determine sources of Pb pollution in urban areas from France and the southern United Kingdom. 206 Pb/ 207 Pb ratios in gasoline range from 1.061 to 1.094 (average values are 1.084 for France and 1.067 for the U.K.) while for industrially-derived Pb, 206 -Pb/ 207 Pb ratios vary from 1.143 to 1.155. Natural Pb is more radiogenic and literature values for pre-industrial sediments give 206 Pb/ 207 Pb ratios of 1.19-1.20 in France and 1.17-1.19 in the U.K. The measured Pb isotopic signature of airborne particulate matter reflects the relative importance of each of these sources, and samples taken from urban areas close to traffic in France and the U.K. show 206 Pb/ 207 Pb ratios that vary widely from 1.085 to 1.158. While alkyl-lead additives in gasoline are typically still the dominant source of Pb in urban particulate matter, the relative importance of gasoline-derived Pb has decreased, and as a result other sources (industrial and natural) can be identified using isotopic studies. This is a consequence of recent EU environmental legislation that significantly limits concentrations of Pb in gasoline and the increased market penetration of unleaded gasoline. In addition, at a given location, the Pb isotopic composition of particulate matter can vary considerably due to temporal variations in sources (i.e., variations in traffic density) and with wind direction.

The public reporting burden for this collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data needed, and completing and reviewing the collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information, including suggestions for reducing the burden, to Department of Defense, Washington Headquarters Services, Directorate for Information 14. ABSTRACT The mechanics of uncemented soft sediments during bubble growth are not widely understood and no rheological model has found wide acceptance. We offer definitive evidence on the mode of bubble formation in the form of X-ray computed tomographic images and comparison with theory. Natural and injected bubbles in muddy cohesive sediments are shown to be highly eccentric oblate spheroids (disks) that grow either by fracturing the sediment or by reopening preexisting fractures. In contrast, bubbles in soft sandy sediment tend to be spherical, suggesting that sand acts fluidly or plastically in response to growth stresses. We also present bubble-rise results from gelatin, a mechanically similar but transparent medium, that suggest that initial rise is also accomplished ABSTRACT idization, e.g., gravity flows, during some natThe mechanics of uncemented soft sediments during bubble growth are not widely ural disturbances have suggested that such understood and no rheological model has found wide acceptance. We offer definitive ev-sediments can act fluidly or plastically in reidence on the mode of bubble formation in the form of X-ray computed tomographic sponse to stress. Past mechanical models of images and comparison with theory. Natural and injected bubbles in muddy cohesive bubbles in these sediments have visualized the sediments are shown to be highly eccentric oblate spheroids (disks) that grow either by bubbles as essentially spherical (e.g., Wheeler, fracturing the sediment or by reopening preexisting fractures. In contrast, bubbles in soft 1988; Sills et al., 1991), with the implication, sandy sediment tend to be spherical, suggesting that sand acts fluidly or plastically in intentional or not, that the surrounding mediresponse to growth stresses. We also present bubble-rise results from gelatin, a mechan-um reacts fluidly or plastically to their growth ically similar but transparent medium, that suggest that initial rise is also accomplished and rise. Scientists and engineers have develby fracture. Given that muddy sediments are elastic and yield by fracture, it becomes oped an impressive understanding of bubble much easier to explain physically related phenomena such as seafloor pockmark forma-growth in fluids, and a vast literature covers tion, animal burrowing, and gas buildup during methane hydrate melting.the topic (e.g., Clift et al., 1978; Lohse, 2003). However, we show here that muddy sediment Keywords: bubbles, mud, fracture, methane.does not respond mechanically either a...

No abstract

A multivariate log-ratio calibration (MLC) model for XRF-core-scanning devices is presented, based on a combination of basic XRF-spectrometry theory and principles of compositional data analysis. The performance of the MLC model is evaluated in comparison with other empirical calibration procedures for XRF core scanner data using two data sets acquired with two different XRF core scanners. The quality of calibration models is assessed by calculating the uncertainties associated with predicted concentrations using cross-validation techniques. Results show that (1) the commonly used direct linear calibration (DLC) methods, which are based on the questionable assumption of a unique linear relation between intensities and concentrations and do not acknowledge the compositional nature of the calibration problem, give poor results; (2) the univariate log-ratio calibration (ULC) model, which is consistent with the compositional nature of the calibration problem but does not fully incorporate absorption and enhancement effects on intensities, and permits estimation of "relative" concentrations only, is markedly better, and (3) the MLC algorithm introduced in this contribution, which incorporates measurement uncertainties, accommodates absorption and enhancement effects on intensities, and exploits the covariance between and among intensities and concentrations, is the best by far. The predictive power of the MLC model may be further increased by employing automatic sample selection based on the multivariate geometry of intensity measurements in log-ratio space. The precision attained by MLC in conjunction with automatic sample selection is comparable to that attained by conventional XRF analysis of heterogenous materials under laboratory conditions. A solution to the long-standing problem of XRF core scanner calibration implies that high-resolution records of sediment composition with associated uncertainties can now be routinely established, which should increase the range of quantitative applications of XRF-core-scanning devices and strengthen inferences based on analysis of geochemical proxies.

No abstract

Abstract. Slowly accumulated (<5 cm kyr '1) and rapidly accumulated (5-20 cm kyr -1) sediments have been compared to define the initiation and termnation times of the most recent sapropel (S1) in the eastern Mediterranean Sea. The Ba/A1 ratio has been employed as a more persistent index of productivity than C•g. Accelerator mass spectrometry radiocarbon dating of pelagic foraminifera indicates a maximum duration for increased Ba/A1 levels in S 1 from -9500-6000 (uncorrected radiocarbon convention years B.P.) in the rapidly accumulated sediments and -9500-5300 years B.P. in the slowly accumulated sediments. This difference is ascribed to bioturbation affecting the slower accumulated S1 sediments. In the two most rapidly accumulated S1 units, from the Adriatic and Aegean Seas, there is a "saddle" of lower values centered on 7500 years B.P. in the Corg and Ba/AI profiles, so that the visual S 1 unit appears as a doublet. Geochemical evidence indicates that this intervening period is best interpreted as an episode of increased ventilation and bottom water oxygenation during the period of sapropel accumulation.

XRF core scanners, with their rapid and non-destructive analytical capability, have now been used for two decades in the analysis of marine sediments. Initially they were used to record variations in fundamental parameters such as calcium carbonate stratigraphy and terrigenous sediment delivery, using major element integrals, such as Ca and Fe, to provide detailed insights into oceanographic and climatic processes. In recent years, proxy selection has progressed to routine normalisation and presentation as log-ratios to include 60 elements or ratios to document a wide range of environmental and process changes. We review the development and application of XRF core scanning of marine sediments and discuss the basis of particular proxies, their uses and limitations to assist users in their selection. To date, there has been no systematic overview of elemental proxies and their application in the analysis of marine sediment records.