THREE-WAY METHODS FOR THE CALIBRATION OF CHROMATOGRAPHIC SYSTEMS:COMPARING PARAFAC AND THREE-WAY PLS

For the calibration of chromatographic systems,different methods can be used.One class of methodsutilizes three-way approaches.The calibration problem is stated in such a way that the decompositionof a three-way array can serve for the prediction of retention on new stationary phases.Two three-way approaches are presented:the Unfold-PCA and PARAFAC models.The theory ofboth methods is presented and the differences are highlighted,the main difference being that PARAFACis a trilinear decomposition whereas Unfold-PCA is not.Both three-way methods are evaluated on asmall data set consisting of retention measurements of eight solutes at six mobile phase compositions onsix stationary phases.The differences in performance of the two models are minor,For calibration purposes,two variants of the methods are discussed:three-way PLS and an extensionof PARAFAC.Again the theory and differences between the two methods are explained.The predictiveperformance of the two methods is compared using the same data set as earlier.The differences inpredictive performance,however,are minor.Both methods are capable of predicting 98% of thevariation in the test sets.Yet,there are other considerations when comparing methods than predictiveperformance,e.g.the quality of the predictions.     

Evaluation of an empirical orthogonal function–based method to downscale soil moisture patterns based on topographical attributes

Soil moisture influences many hydrologic applications including agriculture, land management and flood prediction. Most remote‐sensing methods that estimate soil moisture produce coarse resolution patterns, so methods are required to downscale such patterns to the resolutions required by these applications (e.g. 10‐ to 30‐m grid cells). At such resolutions, topography is known to affect soil moisture patterns. Although methods have been proposed to downscale soil moisture based on topography, they usually require the availability of past high‐resolution soil moisture patterns from the application region. The objective of this article is to determine whether a single topographic‐based downscaling method can be used at multiple locations without relying on detailed local observations. The evaluated downscaling method is developed on the basis of empirical orthogonal function (EOF) analysis of space–time soil moisture data at a reference catchment. The most important EOFs are then estimated from topographic attributes, and the associated expansion coefficients are estimated on the basis of the spatial‐average soil moisture. To test the portability of this EOF‐based method, it is developed separately using four data sets (Tarrawarra, Tarrawarra 2, Cache la Poudre and Satellite Station), and the relationships that are derived from these data sets to estimate the EOFs and expansion coefficients are compared. In addition, each of these downscaling methods is applied not only for the catchment where it was developed but also to the other three catchments. The results suggest that the EOF downscaling method performs well for the location where it is developed, but its performance degrades when applied to other catchments. Copyright © 2011 John Wiley & Sons, Ltd.     

Correction of the ionospheric distortion on the MARSIS surface sounding echoes

Mars Advanced Radar for Subsurface and Ionospheric Sounding (MARSIS) on the Mars Express (MEX) spacecraft has made numerous measurements of the Martian surface and subsurface. However, all of these measurements are distorted by the ionosphere and must be compensated before any analysis. We have developed a technique to compensate for the ionospheric distortions. This technique provides a powerful tool to derive the total electron content (TEC) and other higher-order terms of the limited expansion of the plasma dispersion function that are related to overall shape of the electron column profile. The derived parameters are fitted by using a Chapman model to derive ionospheric parameters like n₀, electron density primary peak (maximum for solar zenith angle (SZA) equal 0), and the neutral height scale H.

Our estimated ionospheric parameters are in good agreement with Mars Global Surveyor (MGS) radio-occultation data. However, since MARSIS does not have the observation geometry limitations of the radio occultation measurements, our derived parameters extend over a large range of SZA for each MEX orbit.

The first results from our technique have been discussed by Safaeinili et al. [2007, Estimation of the total electron content of the Martian ionosphere using radar sounder surface echoes. Geophys. Res. Lett. 34, L23204, doi:10.1029/2007GL032154].     

The nature of the hard state of Cygnus X-3

The X-ray binary Cygnus X-3 (Cyg X-3) is a highly variable X-ray source that displays a wide range of observed spectral states. One of the main states is significantly harder than the others, peaking at ∼20 keV, with only a weak low-energy component. Due to the enigmatic nature of this object, hidden inside the strong stellar wind of its Wolf–Rayet companion, it has remained unclear whether this state represents an intrinsic hard state, with truncation of the inner disc, or whether it is just a result of increased local absorption. We study the X-ray light curves from RXTE /ASM and CGRO /BATSE in terms of distributions and correlations of flux and hardness and find several signs of a bimodal behaviour of the accretion flow that are not likely to be the result of increased absorption in a surrounding medium. Using INTEGRAL observations, we model the broad-band spectrum of Cyg X-3 in its apparent hard state. We find that it can be well described by a model of a hard state with a truncated disc, despite the low cut-off energy, provided the accreted power is supplied to the electrons in the inner flow in the form of acceleration rather than thermal heating, resulting in a hybrid electron distribution and a spectrum with a significant contribution from non-thermal Comptonization, usually observed only in soft states. The high luminosity of this non-thermal hard state implies that either the transition takes place at significantly higher   L / L _E  than in the usual advection models, or the mass of the compact object is  ≳20 M_⊙  , possibly making it the most-massive black hole observed in an X-ray binary in our Galaxy so far. We find that an absorption model as well as a model of almost pure Compton reflection also fit the data well, but both have difficulties explaining other results, in particular the radio/X-ray correlation.     

The formation of small cones in Isidis Planitia,Mars through mobilization of pyroclastic surge deposits

We investigate the distinctive distribution and pattern of subkilometer-sized cones in Isidis Planitia, and their relationship to the material that fills the basin. We observe that: (1) the cones show uniform size, spacing, and morphology across the entire basin; (2) they have large central depressions (relative to cone basal diameters) that are generally filled in and commonly show layering; (3) cone chains form highly organized spatial patterns; cones are also found in isolation and in dense fields; (4) many adjacent chains are parallel, and evenly spaced, creating a pattern that mimics lava flows that have experienced compressional folding; (5) no flows are associated with the cones, even where summit crater rims are breached; (6) the cones are at least temporally related to basin fill; (7) the basin fill material is largely fine-grained, but with locally indurated layers at shallow depth; blocks ejected by small craters from these locally indurated layers are commonly dark in color; and (8) relationships between cones along a chain show no systematic temporal formation sequence along the chain. We conclude that the basin was likely inundated by one or more hot, partially welded pyroclastic flows; devolatilization of these flows remobilized volcaniclastic material to form the cones without associated lava flows. The volume of gas required to account for the observed number of cones is low and does not require the presence of ground water or ice.     

Fresnel modeling of hematite crystal surfaces and application to martian hematite spherules

The gray crystalline hematite at Meridiani Planum first discovered by the Mars Global Surveyor Thermal Emission Spectrometer (MGS-TES) instrument occurs as spherules that have been interpreted as concretions. Analysis of the TES and mini-TES spectra shows that no 390 cm⁻¹ feature is present in the characteristic martian hematite spectrum. Here, we incorporate the mid-IR optical constants of hematite into a simple Fresnel reflectance model to understand the effect of emission angle and crystal morphology on the presence or absence of the 390 cm⁻¹ feature in an IR hematite spectrum. Based on the results we offer two models for the internal structure of the martian hematite spherules.     

Geochemical reconstruction of late Holocene drainage and mixing in Kluane Lake,Yukon Territory

The level of Kluane Lake in southwest Yukon Territory, Canada, has fluctuated tens of metres during the late Holocene. Contributions of sediment from different watersheds in the basin over the past 5,000 years were inferred from the elemental geochemistry of Kluane Lake sediment cores. Elements associated with organic material and oxyhydroxides were used to reconstruct redox fluctuations in the hypolimnion of the lake. The data reveal complex relationships between climate and river discharge during the late Holocene. A period of influx of Duke River sediment coincides with a relatively warm climate around 1,300 years BP. Discharge of Slims River into Kluane Lake occurred when Kaskawulsh Glacier advanced to the present drainage divide separating flow to the Pacific Ocean via Kaskawulsh and Alsek rivers from flow to Bering Sea via tributaries of Yukon River. During periods when neither Duke nor Slims river discharged into Kluane Lake, the level of the lake was low and stable thermal stratification developed, with anoxic and eventually euxinic conditions in the hypolimnion.     

Carbon dioxide segregation in 1:4 and 1:9 CO2:H2O ices

The mid-infrared spectra of mixed vapor deposited ices of CO₂ and H₂O were studied as a function of both deposition temperature and warming from 15 to 100 K. The spectra of ices deposited at 15 K show marked changes on warming beginning at 60 K. These changes are consistent with CO₂ segregating within the ice matrix into pure CO₂ domains. Ices deposited at 60 and 70 K show a greater degree of segregation, as high as 90% for 1:4 CO₂:H₂O ice mixtures deposited at 70 K. As the ice is warmed above 80 K, preferential sublimation of the segregated CO₂ is observed. The kinetics of the segregation process is also examined. The segregation of the CO₂ as the ice is warmed corresponds to temperatures at which the structure of the water ice matrix changes from the high density amorphous phase to the low density amorphous phase. We show how these microstructural changes in the ice have a profound effect on the photochemistry induced by ultraviolet irradiation. These experimental results provide a framework in which observations of CO₂ on the icy bodies of the outer Solar System can be considered.     

Lunar Gravity-Assist Maneuver As a Way of Reducing the Orbit Amplitude in the Spectrum–Röntgen–Gamma Project

Spectrum–Röntgen–Gamma (SRG) is a space observatory designed to observe astrophysical objects in the X-ray range of the electromagnetic spectrum. SRG is planned to be launched in 2019 by a Proton-M launch vehicle with a DM3 upper stage. The spacecraft will be delivered to an orbit around the Sun–Earth collinear libration point L2 located at a distance of ~1.5 million km from the Earth. Although the SRG launch scheme has already been determined at present, in this paper we consider an alternative spacecraft transfer scenario using a lunar gravity-assist maneuver. The proposed scenario allows a oneimpulse transfer from a low Earth orbit to a small-amplitude orbit around the libration point to be performed while fulfilling the technical constraints and the scientific requirements of the mission.