Cokriging nonstationary data

Universal cokriging is used to obtain predictions when dealing with multivariate random functions. An important type of nonstationarity is defined in terms of multivariate random functions with increments which are stationary of orderk. The covariance between increments of different variables is modeled by means of the pseudo-cross-covariance function. Criteria are formulated to which the parameters of pseudo-cross-covariance functions must comply so as to ensure positive-definiteness. Cokriging equations and the induced cokriging equations are given. The study is illustrated by an example from soil science.     

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.     

Palaeotemperature reconstructions of the European permafrost zone during marine oxygen isotope Stage 3 compared with climate model results

A palaeotemperature reconstruction based on periglacial phenomena in Europe north of approximately 51 °N, is compared with high‐resolution regional climate model simulations of the marine oxygen isotope Stage 3 (Stage 3) palaeoclimate. The experiments represent Stage 3 warm (interstadial), Stage 3 cold (stadial) and Last Glacial Maximum climatic conditions. The palaeotemperature reconstruction deviates considerably for the Stage 3 cold climate experiments, with mismatches up to 11 °C for the mean annual air temperature and up to 15 °C for the winter temperature. However, in this reconstruction various factors linking climate and permafrost have not been taken into account. In particular a relatively thin snow cover and high climatic variability of the glacial climate could have influenced temperature limits for ice‐wedge growth. Based on modelling the 0 °C mean annual ground temperature proves to be an appropriate upper temperature limit. Using this limit, mismatches with the Stage 3 cold climate experiments have been reduced but still remain. We therefore assume that the Stage 3 ice wedges were generated during short (decadal time‐scale) intervals of extreme cold climate, below the mean temperatures indicated by the Stage 3 cold climate model simulations. Copyright © 2003 John Wiley & Sons, Ltd.     

The Preboreal climate reversal and a subsequent solar‐forced climate shift

Accurate chronologies are essential for linking palaeoclimate archives. Carbon‐14 wiggle‐match dating was used to produce an accurate chronology for part of an early Holocene peat sequence from the Borchert (The Netherlands). Following the Younger Dryas–Preboreal transition, two climatic shifts could be inferred. Around 11 400 cal. yr BP the expansion of birch (Betula) forest was interrupted by a dry continental phase with dominantly open grassland vegetation, coeval with the PBO (Preboreal Oscillation), as observed in the GRIP ice core. At 11 250 cal. yr BP a sudden shift to a humid climate occurred. This second change appears to be contemporaneous with: (i) a sharp increase of atmospheric ¹⁴C; (ii) a temporary decline of atmospheric CO₂; and (iii) an increase in the GRIP ¹⁰Be flux. The close correspondence with excursions of cosmogenic nuclides points to a decline in solar activity, which may have forced the changes in climate and vegetation at around 11 250 cal. yr BP. Copyright © 2004 John Wiley & Sons, Ltd.     

Leaching mechanisms of oxyanionic metalloid and metal species in alkaline solid wastes: A review

An overview is presented on possible mechanisms that control the leaching behaviour of the oxyanion forming elements As, Cr, Mo, Sb, Se, V and W in cementituous systems and alkaline solid wastes, such as municipal solid waste incinerator bottom ash, fly ash and air pollution control residues, coal fly ash and metallurgical slags. Although the leachability of these elements generally depends on their redox state, speciation measurements are not common. Therefore, experimental observations available in the literature are combined with a summary of the thermal behaviour of these elements to assess possible redox states in freshly produced alkaline wastes, given their origin at high temperature. Possible redox reactions occurring at room temperature, on the other hand, are reviewed because these may alter the initial redox state in alkaline wastes and their leachates. In many cases, precipitation of oxyanions as a pure metalate cannot provide a satisfactory explanation for their leaching behaviour. It is therefore highly likely that adsorption and solid solution formation with common minerals in alkaline waste and cement reduce the leachate concentration of oxyanions below pure-phase solubility.     

Considerations for conducting incubations to study the mechanisms of As release in reducing groundwater aquifers

Microbial Fe reduction is widely believed to be the primary mechanism of As release from aquifer sands in Bangladesh, but alternative explanations have been proposed. Long-term incubation studies using natural aquifer material are one way to address such divergent views. This study addresses two issues related to this approach: (1) the need for suitable abiotic controls and (2) the spatial variability of the composition of aquifer sands. Four sterilization techniques were examined using orange-colored Pleistocene sediment from Bangladesh and artificial groundwater over 8 months. Acetate (10 mM) was added to sacrificial vials before sterilization using either (1) 25 kGy of gamma irradiation, (2) three 1-h autoclave cycles, (3) a single addition of an antibiotic mixture at 1× or (4) 10× the typical dose, and (5) a 10 mM addition of azide. The effectiveness of sterilization was evaluated using two indicators of microbial Fe reduction, changes in diffuse spectral reflectance and leachable Fe(II)/Fe ratios, as well as changes in P-extractable As concentrations in the solid phase. A low dose of antibiotics was ineffective after 70 days, whereas autoclaving significantly altered groundwater composition. Gamma irradiation, a high dose of antibiotics, and azide were effective for the duration of the experiment.     

An optimized method for automated analysis of algal pigments by HPLC

A recent development in algal pigment analysis by high-performance liquid chromatography (HPLC) is the application of automation. An optimization of a complete sampling and analysis protocol applied specifically in automation has not yet been performed. In this paper we show that automation can only be successful if the various methodological aspects of the sampling and analysis protocol are considered in coherence. We introduce an optimized protocol that involves freeze-drying of the sample, subsequent extraction in 90% acetone and the application of water-packing during analysis. The method was evaluated on both natural plankton populations and a broad spectrum of microalgal cultures: Thalassiosira weisflogii (Bacillariophyceae), Emiliania huxleyi (Prymnesiophyceae), Phaeocystis globosa and Phaeocystis antarctica (Prymnesiophyceae) and Pyramimonas sp. (Prasinophyceae). Whereas pigment extracts were unstable in methanol, with recorded chlorophyll a losses from 10% to 60% per day, pigment degradation rates in acetone were generally less than 1% over 18 h storage in the autosampler (4 °C). In addition, it was found that the extraction efficiency of acetone significantly increased upon freeze-drying prior to extraction. Increases as high as 50–60% were measured in P. antarctica. The application of water-packing of the sample during injection resulted in improved peak shape and peak separation, without diluting the pigment concentrations. Automation is especially beneficial for application in the field, when mixed algal assemblages and low biomass put a high demand on the sensitivity as well as reproducibility of the method.     

Transient biouptake flux and accumulation by microorganisms: The case of two types of sites with Langmuir adsorption

The uptake of a chemical species by an aquatic microorganism is modelled considering two kinds of sites where Langmuirian adsorption is followed by first order internalisation kinetics. Simpler models, such as only one internalisation route (while most of the adsorption takes place on non-internalising sites) or a linear isotherm for adsorption on one or both sites, become limiting cases of this double-Langmuirian model. The model considers the sites located on the spherical (or semi-spherical) surface of the organism, and takes diffusion from the medium into explicit account. The numerical solution for the internalisation flux shows a maximum. We provide an estimate for the time needed to reach a certain proximity to steady state. The transient solution confirms that the analytical expressions for the steady-state flux are usually valid and that the accumulated amounts reflect the impact of the short-time uptake. The Instantaneous Steady-State Approximation (ISSA), where an intercept of the linear regression of accumulated amount as a function of time is interpreted as an adsorbed amount, can be critically assessed with the transient numerical code for two cases: (i) when the total burden of metal on the cell is the input data and (ii) when an extraction procedure provides further information on the adsorbed and internalised amount.