The influence of multivariate analysis methods and target grain size on the accuracy of remote quantitative chemical analysis of rocks using laser induced breakdown spectroscopy     

Ryan B. Anderson  Richard V. Morris 《Icarus》2011,215(2):608-627

Laser-induced breakdown spectroscopy (LIBS) was used to quantitatively analyze 195 rock slab samples with known bulk chemical compositions, 90 pressed-powder samples derived from a subset of those rocks, and 31 pressed-powder geostandards under conditions that simulate the ChemCam instrument on the Mars Science Laboratory Rover (MSL), Curiosity. The low-volatile (<2 wt.%) silicate samples (90 rock slabs, corresponding powders, and 22 geostandards) were split into training, validation, and test sets. The LIBS spectra and chemical compositions of the training set were used with three multivariate methods to predict the chemical compositions of the test set. The methods were partial least squares (PLS), multilayer perceptron artificial neural networks (MLP ANNs) and cascade correlation (CC) ANNs. Both the full LIBS spectrum and the intensity at five pre-selected spectral channels per major element (feature selection) were used as input data for the multivariate calculations. The training spectra were supplied to the algorithms without averaging (i.e. five spectra per target) and with averaging (i.e. all spectra from the same target averaged and treated as one spectrum). In most cases neural networks did not perform better than PLS for our samples. PLS2 without spectral averaging outperformed all other procedures on the basis of lowest quadrature root mean squared error (RMSE) for both the full test set and the igneous rocks test set. The RMSE for PLS2 using the igneous rock slab test set is: 3.07 wt.% SiO₂, 0.87 wt.% TiO₂, 2.36 wt.% Al₂O₃, 2.20 wt.% Fe₂O₃, 0.08 wt.% MnO, 1.74 wt.% MgO, 1.14 wt.% CaO, 0.85 wt.% Na₂O, 0.81 wt.% K₂O. PLS1 with feature selection and averaging had a higher quadrature RMSE than PLS2, but merits further investigation as a method of reducing data volume and computation time and potentially improving prediction accuracy, particularly for samples that differ significantly from the training set. Precision and accuracy were influenced by the ratio of laser beam diameter (∼490 μm) to grain size, with coarse-grained rocks often resulting in lower accuracy and precision than analyses of fine-grained rocks and powders. The number of analysis spots that were normally required to produce a chemical analysis within one standard deviation of the true bulk composition ranged from ∼10 for fine-grained rocks to >20 for some coarse-grained rocks.  相似文献   

Measurement of LNAPL flow using single-well tracer dilution techniques   总被引：1，自引：0，他引：1  

Sale T  Taylor GR  Iltis G  Lyverse M 《Ground water》2007,45(5):569-578

This paper describes the use of single-well tracer dilution techniques to resolve the rate of light nonaqueous phase liquid (LNAPL) flow through wells and the adjacent geologic formation. Laboratory studies are presented in which a fluorescing tracer is added to LNAPL in wells. An in-well mixer keeps the tracer well mixed in the LNAPL. Tracer concentrations in LNAPL are measured through time using a fiber optic cable and a spectrometer. Results indicate that the rate of tracer depletion is proportional to the rate of LNAPL flow through the well and the adjacent formation. Tracer dilution methods are demonstrated for vertically averaged LNAPL Darcy velocities of 0.00048 to 0.11 m/d and LNAPL thicknesses of 9 to 24 cm. Over the range of conditions studied, results agree closely with steady-state LNAPL flow rates imposed by pumping. A key parameter for estimating LNAPL flow rates in the formation is the flow convergence factor alpha. Measured convergence factors for 0.030-inch wire wrap, 0.030-inch-slotted polyvinyl chloride (PVC), and 0.010-inch-slotted PVC are 1.7, 0.91, and 0.79, respectively. In addition, methods for using tracer dilution data to determine formation transmissivity to LNAPL are presented. Results suggest that single-well tracer dilution techniques are a viable approach for measuring in situ LNAPL flow and formation transmissivity to LNAPL.  相似文献   

Phosphorus and iron cycling in deep saprolite,Luquillo Mountains,Puerto Rico     

Heather L. Buss  Ryan Mathur  Arthur F. White  Susan L. Brantley 《Chemical Geology》2010,269(1-2):52-61

Rapid weathering and erosion rates in mountainous tropical watersheds lead to highly variable soil and saprolite thicknesses which in turn impact nutrient fluxes and biological populations. In the Luquillo Mountains of Puerto Rico, a 5-m thick saprolite contains high microorganism densities at the surface and at depth overlying bedrock. We test the hypotheses that the organisms at depth are limited by the availability of two nutrients, P and Fe. Many tropical soils are P-limited, rather than N-limited, and dissolution of apatite is the dominant source of P. We document patterns of apatite weathering and of bioavailable Fe derived from the weathering of primary minerals hornblende and biotite in cores augered to 7.5 m on a ridgetop as compared to spheroidally weathering bedrock sampled in a nearby roadcut.Iron isotopic compositions of 0.5 N HCl extracts of soil and saprolite range from about δ⁵⁶Fe = 0 to ? 0.1‰ throughout the saprolite except at the surface and at 5 m depth where δ⁵⁶Fe = ? 0.26 to ? 0.64‰. The enrichment of light isotopes in HCl-extractable Fe in the soil and at the saprolite–bedrock interface is consistent with active Fe cycling and consistent with the locations of high cell densities and Fe(II)-oxidizing bacteria, identified previously. To evaluate the potential P-limitation of Fe-cycling bacteria in the profile, solid-state concentrations of P were measured as a function of depth in the soil, saprolite, and weathering bedrock. Weathering apatite crystals were examined in thin sections and an apatite dissolution rate of 6.8 × 10^? 14 mol m^? 2 s^? 1 was calculated. While surface communities depend on recycled nutrients and atmospheric inputs, deep communities survive primarily on nutrients released by the weathering bedrock and thus are tightly coupled to processes related to saprolite formation including mineral weathering. While low available P may limit microbial activity within the middle saprolite, fluxes of P from apatite weathering should be sufficient to support robust growth of microorganisms in the deep saprolite.  相似文献   

Solar Proton Rigidity Spectra From 1 to 10 gv of Selected Flare Events Since 1960     

Lockwood  J.A.  Debrunner  H.  Flueckiger  E.O.  Ryan  J.M. 《Solar physics》2002,208(1):113-140

We have deduced the power-law rigidity spectra, J(P)=AP ^–, and the spectral evolution of the solar flare events that occurred in the present solar activity cycle on 6 November 1997, 14 July 2000, and 15 and 18 April 2001. The implications of these results for the acceleration of high-energy protons are discussed. The analysis is based on the ratios of the Mt. Washington to the Durham neutron monitor count-rate increases during the solar flare events. These two neutron monitors are located at different elevations (828 and 1030 g cm^–2, respectively) but at approximately the same geographical latitude and longitude. The proton spectra from 1 to 10 GV determined from the ratios of the count rate increases of the two neutron monitors are found to agree with those deduced from the global neutron monitor network or selected neutron monitors in 10 solar flare events from 1960 to 1990 for which comparative results are available. Thus the ratio method is quick, easy and reliable for deducing the spectral shape of solar flare protons at neutron monitor rigidities and for obtaining the spectral evolution as a function of time.  相似文献   

The role of FAST in pulsar timing arrays     

George Hobbs  Shi Dai  Richard N.Manchester  Ryan M.Shannon  Matthew Kerr  Ke-Jia Lee  Ren-Xin Xu 《天文和天体物理学研究(英文版)》2019,(2)

The Five-hundred-meter Aperture Spherical radio Telescope(FAST) will become one of the world-leading telescopes for pulsar timing array(PTA) research. The primary goals for PTAs are to detect(and subsequently study) ultra-low-frequency gravitational waves, to develop a pulsar-based time standard and to improve solar system planetary ephemerides. FAST will have the sensitivity to observe known pulsars with significantly improved signal-to-noise ratios and will discover a large number of currently unknown pulsars. We describe how FAST will contribute to PTA research and show that jitter-and timing-noise will be the limiting noise processes for FAST data sets. Jitter noise will limit the timing precision achievable over data spans of a few years while timing noise will limit the precision achievable over many years.  相似文献   

Sub-Micrometre Resolution FIB-SEM-based ToF-SIMS Used to Map Geochemical Zoning in Four Zircon Reference Materials     

Ryan North  Lloyd T. White  Mitchell Nancarrow  Anthony Dosseto  Dominique Tanner 《Geostandards and Geoanalytical Research》2023,47(1):125-142

Zircon geochemistry can vary over micrometre scales; therefore, natural reference materials need to be well characterised before being used to calculate trace element mass fractions in unmeasured samples. Moreover, reference material homogeneity needs to be ensured with the accelerating rate of geoanalytical developments to map mineral chemistry at increasingly finer scales. Here, we investigate trace element zoning in four widely used zircon reference materials: 91500, Mud Tank, Temora and Plešovice, as well as zircon crystals from the Mount Dromedary/Gulaga Igneous Complex, Australia. Sub-micrometre resolution focused ion beam scanning electron microscope (FIB-SEM) based time-of-flight secondary ion mass spectrometry (ToF-SIMS) and 5 μm resolution LA-ICP-MS mapping show that trace elements are zoned in all reference materials, though 91500 exhibited the least zonation. We demonstrate that FIB-SEM-based ToF-SIMS can rapidly resolve variations in trace elements (e.g., U, Th, Sc, Y, Gd, Dy, Yb and Li) at sensitivities down to the μg g^-1 level with a spatial resolution of 195 nm for areas 100 × 85 μm to 959 × 828 μm. Zircon 91500 is recommended for future quantitative analyses provided that (1) the spatial distribution of elements is imaged before analysis of unknown samples and (2) it is used in conjunction with a doped glass as the primary reference material.  相似文献