On least squares estimation of generalized covariance functions

Least squares estimation (LSE) is theoretically related to quadratic unbiased estimation of variance components. It is argued that these methods of estimation of variance components essentially generalize LSE though they are not formally equivalent.     

A Sophisticated Ground Water Analytical Tool

Stiff diagrams arc a multivariate method of analysis used to describe the chemical state of ground water. The use of Stiff diagrams to describe multiconstituent contamination sites, such as landfills, has distinct advantages over single constituent analyses. Problems associated with traditional Stiff diagram analyses, such as diagram attentuation, can be addressed by allowing the scale of the diagram to vary with the ionic strength of the analyzed sample. The use of these sliding scale Stiff diagrams reveals the chemical slate of the ground water over wide ranges of constituent concentrations and thus allows for sensitive and sophisticated depictions of complicated contamination sites in a fashion that is extremely difficult to replicate with single constituent analyses. This approach has possible applications for understanding and tracing the mixing and chemical changes in uncontaminated settings.     

Compositions,sources and depositional environments of organic matter from the Middle Jurassic clays of Poland

The comprehensive biomarker characteristics from previously undescribed Middle Jurassic clays of Poland are presented. The molecular composition of the organic matter (OM) derived from clays of Aalenian to Callovian age has not changed significantly through time. High relative concentrations of many biomarkers typical for terrestrial material suggest a distinct dominance of OM derived from land plants. Increasing concentrations of C₂₉-diaster-13(17)-enes towards the northern part of the basin indicate an increase in terrestrial input. This terrestrial material would have originated from the enhanced transport of organic matter from land situated at the northern bank of the basin, i.e., the Fennoscandian Shield. The organic matter was deposited in an oxic to suboxic environment, as indicated by relatively low concentrations of C₃₃–C₃₅ homohopanes, moderate to high Pr/Ph ratio values, an absence of compounds characteristic for anoxia and water column stratification, such as isorenieratane, aryl isoprenoids and gammacerane, as well as common benthic fauna and burrows. δ¹⁸O measurements from calcitic rostra of belemnites suggest that the mean value of the Middle Jurassic sea-water temperature of the Polish Basin was 13.1 °C. It is suggested that this mirrored the temperature of the lower water column because belemnites are considered here to be necto-benthic. The organic matter from the Middle Jurassic basin of Poland is immature. This is clearly indicated by a large concentration of biomarkers with the biogenic configurations, such as ββ-hopanes, hop-13(18)-enes, hop-17(21)-enes, diasterenes and sterenes. The identification of preserved, unaltered biomolecules like ferruginol, 6,7-dehydroferruginol and sugiol in Protopodocarpoxylon wood samples from these sediments present particularly strong evidence for the presence of immature OM in the Middle Jurassic sediments. Moreover, the occurrence of these polar diterpenoids is important due to the fact that they are definitely the oldest known natural products detected in geological samples.     

Changes in ice-season characteristics of a European Arctic lake from 1964 to 2008

The long-term ice record (from 1964 to 2008) of an Arctic lake in northern Europe (Lake Kilpisj?rvi) reveals the response of lake ice to climate change at local and regional scales. Average freeze-up and ice breakup occurred on 9 November and 19 June, respectively. The freeze-up has been significantly delayed at a rate of 2.3 d per decade from 1964 onward (P?<?0.05). No significant change has taken place in ice breakup. Annual average ice thickness has become smaller since the mid-1980s (P?<?0.05). Air temperature during the early ice season significantly affected the ice thickness. The freeze-up date exhibits the highest correlation with the 2-month average daily minimum air temperature centered at the end of October, while the ice breakup date exhibits the highest correlation with the 2-month average daily maximal air temperature centered in mid May. A 1°C increase in the surface air temperature corresponds to a freeze-up later by 3.4?days and an ice breakup earlier by 3.6?days. Snow cover is a critical factor in lake-ice climatology. For cumulative November to March precipitation of less than 0.13?m, the insulating effect of the snow dominated, while higher rates of precipitation favored thicker ice due to the formation of snow ice. Variations in ice records of Lake Kilpisj?rvi can serve as an indicator of climate variations across the northern Europe. The North Atlantic Oscillation (NAO) does not significantly affect the ice season there, although both the local air temperatures and winter precipitation contain a strong NAO signal.     

A systematic study of variability in a sample of ultraluminous X-ray sources

We present results from a study of short-term variability in 19 archival observations by XMM–Newton of 16 ultraluminous X-ray sources (ULXs). Eight observations (six sources) showed intrinsic variability with power spectra in the form of either a power-law or broken power-law-like continuum and in some cases quasi-periodic oscillations (QPOs). The remaining observations were used to place upper limits on the strength of possible variability hidden within. Seven observations (seven sources) yielded upper limits comparable to, or higher than, the values measured from those observations with detectable variations. These represented the seven faintest sources, all with   f_x < 3 × 10⁻¹² erg cm⁻² s⁻¹  . In contrast, there are four observations (three sources) that gave upper limits significantly lower than both the values measured from the ULX observations with detectable variations, and the values expected by comparison with luminous Galactic black hole X-ray binaries (BHBs) and active galactic nuclei (AGN) in the observed frequency bandpass (10⁻³–1 Hz). This is the case irrespective of whether one assumes characteristic frequencies appropriate for a stellar mass  (10 M_⊙)  or an intermediate mass  (1000 M_⊙)  black hole, and means that in some ULXs the variability is significantly suppressed compared to bright BHBs and AGN. We discuss ways to account for this unusual suppression in terms of both observational and intrinsic effects and whether these solutions are supported by our results.     

Pyroxenite xenoliths from Marsabit (Northern Kenya): evidence for different magmatic events in the lithospheric mantle and interaction between peridotite and pyroxenite

Garnet-bearing and garnet-free pyroxenite xenoliths from Quaternary basanites of Marsabit, northern Kenya, were analysed for microstructures and mineral compositions (major and trace elements) to constrain the thermal and compositional evolution of the lithospheric mantle in this region. Garnet-bearing rocks are amphibole-bearing websterite with ~5–10 vol% orthopyroxene. Clinopyroxene is LREE-depleted and garnet has high HREE contents, in agreement with an origin as cumulates from basaltic mantle melts. Primary orthopyroxene inclusions in garnet suggest that the parental melts were orthopyroxene-saturated. Rock fabrics vary from weakly to strongly deformed. Thermobarometry indicates extensive decompression and cooling (~970–1,100°C at ~2.3–2.6 GPa to ~700–800°C at ~0.5–1.0 GPa) during deformation, best interpreted as pyroxenite intrusion into thick Paleozoic continental lithosphere subsequently followed by continental rifting (i.e., formation of the Mesozoic Anza Graben). During continental rifting, garnet websterites were decompressed (garnet-to-spinel transition) and experienced the same P–T evolution as their host peridotites. Strongly deformed samples show compositional overlaps with cpx-rich, initially garnet-bearing lherzolite, best explained by partial re-equilibration of peridotite and pyroxenite during deformation and mechanical mingling. In contrast, garnet-free pyroxenites include undeformed, cumulate-like samples, indicating that they are younger than the garnet websterites. Major and trace element compositions of clinopyroxene and calculated equilibrium melts suggest crystallisation from alkaline basaltic melt similar to the host basanite, which suggests formation in the context of alkaline magmatism during the development of the Kenya rift. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Submicron scale imaging of soil organic matter dynamics using NanoSIMS - From single particles to intact aggregates

The specific features of the nano-scale secondary ion mass spectrometry (NanoSIMS) technology with the simultaneous analysis of up to seven ion species with high mass and lateral resolution enables us to perform multi-element and stable isotope measurements at the submicron scale. To elucidate the power of this technique, we performed an incubation experiment with soil particles of the fine silt and clay fractions (from an Albic Luvisol), with occluded particulate organic material and intact soil aggregates (from a Haplic Chernozem), using a ¹³C and ¹⁵N labelled amino acid mixture as tracer. Before and during 6-day incubation after the addition of the label, samples were consecutively prepared for NanoSIMS analysis. For this purpose, two different sample preparation techniques were developed: (i) wet deposition and (ii) the sectioning of epoxy resin embedded samples. Single soil particles (fine silt/clay fraction) showed an enrichment of ¹³C and ¹⁵N after label addition that decreased over time. On aggregates of particulate organic matter, re-aggregated during the 6-day incubation experiment, we could show a spatially heterogeneous enrichment of ¹³C and ¹⁵N on the particle surface. The enrichment in ¹⁵N demonstrated the diffusion of dissolved organic matter into intact soil aggregate interiors. The prospects of NanoSIMS for three dimensional studies of stable C and N isotopes in organo-mineral associations is demonstrated by the recorded depth profiles of the organic matter distribution on mineral particles.     

Evolution of anthropogenic and biomass burning emissions of air pollutants at global and regional scales during the 1980�C2010 period

Several different inventories of global and regional anthropogenic and biomass burning emissions are assessed for the 1980?C2010 period. The species considered in this study are carbon monoxide, nitrogen oxides, sulfur dioxide and black carbon. The inventories considered include the ACCMIP historical emissions developed in support of the simulations for the IPCC AR5 assessment. Emissions for 2005 and 2010 from the Representative Concentration Pathways (RCPs) are also included. Large discrepancies between the global and regional emissions are identified, which shows that there is still no consensus on the best estimates for surface emissions of atmospheric compounds. At the global scale, anthropogenic emissions of CO, NO_x and SO₂ show the best agreement for most years, although agreement does not necessarily mean that uncertainty is low. The agreement is low for BC emissions, particularly in the period prior to 2000. The best consensus is for NO_x emissions for all periods and all regions, except for China, where emissions in 1980 and 1990 need to be better defined. Emissions of CO need better quantification in the USA and India for all periods; in Central Europe, the evolution of emissions during the past two decades needs to be better determined. The agreement between the different SO₂ emissions datasets is rather good for the USA, but better quantification is needed elsewhere, particularly for Central Europe, India and China. The comparisons performed in this study show that the use of RCP8.5 for the extension of the ACCMIP inventory beyond 2000 is reasonable, until more global or regional estimates become available. Concerning biomass burning emissions, most inventories agree within 50?C80%, depending on the year and season. The large differences between biomass burning inventories are due to differences in the estimates of burned areas from the different available products, as well as in the amount of biomass burned.