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.     

Rapid invasion of Crassostrea gigas into the German Wadden Sea dominated by larval supply

Invasions of non-indigenous species into coastal habitats have been a frequent phenomenon in the last decades, sometimes with significant impact on the receiving ecosystem. However, the understanding of the entire process and especially the relative importance of larval supply and local recruitment remains unclear. In this study, we simulate the invasion of a benthic invertebrate into a previously uncolonised habitat over several years and validate the results with field data. Therefore, we present field data from a monitoring programme revealing the rapid invasion of the oyster Crassostrea gigas into the East Frisian Wadden Sea, North Sea, between 2003 and 2005. The applied model combines a simple, spatially-explicit population dynamics model for the adult stage with a particle tracking model for the larval stage of the life cycle. Simulation results are able to reproduce the large-scale pattern of the field data and indicate a domination of larval supply on the population dynamics in the early stage of the invasion. Though monitoring and simulations suggest a single larval source outside the study area in the west, the population dynamics in the eastern part is only explainable with an additional source within the study area attributed to an unintentional input of juveniles by mussel fishery. High sensitivities to uncertain parameters result in distinct deviations between monitoring and simulations at particular sites. Especially the impact of site-specific variations of the post-settlement mortality underlines the variability of local recruitment conditions and indicates the need for spatially resolved information for exact predictions.     

Resolving physically and biologically driven suspended particulate matter dynamics in a tidal basin with a distribution-based model

Understanding suspended particulate matter (SPM) dynamics in coastal waters is crucial to assess changes in coastal sediment budgets and biogeochemical fluxes. SPM dynamics are subject to various physical and biological factors and processes such as, e.g. tidal currents and aggregation which can be enhanced by extracellular polymeric substances (EPS) that are produced by algae and bacteria. It is still unclear how the different factors and processes interact and together determine SPM dynamics. To unravel the interacting processes and factors, we propose a new distribution-based modeling approach. Based on the derivation of explicit equations for size distribution characteristics of SPM such as the average radius, we derived a model of reduced complexity characterized by low initialization and parameterization effort as well as low computational cost. The proposed 0D model includes the processes of aggregation and fragmentation due to shear, aggregation due to differential settling, deposition, resuspension and tidal exchange, and describes the evolution of the SPM concentration in the water column linked by the settling velocity to the change of the mass average radius of the aggregate distribution. A systematic parameter variation for critical bottom shear stress of erosion, the size of resuspended aggregates, the fractal dimension, the collision efficiency, and the aggregate strength has been performed and compared to observations in the back-barrier basin of Spiekeroog Island in the German Wadden Sea. This analysis confirms the hypothesis that in winter biological influences on SPM dynamics are smaller compared to summer. This is mainly reflected by a significant shift in the various parameters. We hence conclude that biological control mechanisms have a much more quantitative relevance for SPM dynamics than currently represented by state-of-the-art SPM transport models.     

Gas phase reactions of alkyl nitrates with hydroxyl radicals under tropospheric conditions in comparison with photolysis

Rate constants for the reaction of OH radicals with some branched alkyl nitrates have been measured applying a competitive technique. Methyl nitrite photolysis in synthetic air was used as OH radical source at 295±2 K and 1000 mbar total pressure. Using a rate constant of 2.53×10^-12 cm³ s^-1 for the reaction of OH radicals with n-butane as reference, the following rate constants were obtained (units: 10^-12 cm³ s^-1): isopropyl nitrate, 0.59±0.22; isobutyl nitrate, 1.63±0.20; 3-methyl-2-butyl nitrate, 1.95±0.15; 2-methyl-1-butyl nitrate, 2.50±0.15; 3-methyl-1-butyl nitrate, 2.55±0.35. These values have been combined with the literature data to recalculate the substituent factors F(X) for the different nitrate groups which can be used to predict OH rate constants for organic nitrates for which experimental data are not available.Preliminary measurements of the photolysis frequency of isopropyl nitrate have shown that for this nitrate as a model substance, OH reactions and direct photolysis are of equal importance under tropospheric conditions.     

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.     

Managing coastal area resources by stated choice experiments

In many coastal regions, oil spills can be considered as one of the most important and certainly the most noticeable forms of marine pollution. Efficient contingency management responding to oil spills on waters, which aims at minimizing pollution effects on coastal resources, turns out to be critically important. Such a decision making highly depends on the importance attributed to different coastal economic and ecological resources. Economic uses can, in principal, be addressed by standard measures such as value added. However, there is a missing of market in the real world for natural goods. Coastal resources such as waters and beach cannot be directly measured in money terms, which increases the risk of being neglected in a decision making process. This paper evaluates these natural goods of coastal environment in a hypothetical market by employing stated choice experiments. Oil spill management practice in German North Sea is used as an example. Results from a pilot survey show that during a combat process, beach and eider ducks are of key concerns for households. An environmental friendly combat option has to be a minor cost for households. Moreover, households with less children, higher monthly income and a membership of environmental organization are more likely to state that they are willing to pay for combat option to prevent coastal resources from an oil pollution. Despite that choice experiments require knowledge of designing questionnaire and statistical skills to deal with discrete choices and conducting a survey is time consumed, the results have important implications for oil spill contingency management. Overall, such a stated preference method can offer useful information for decision makers to consider coastal resources into a decision making process and can further contribute to finding a cost-effective oil preventive measure, also has a wide application potential in the field of Integrated Coastal Zone Management (ICZM).     

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.     

Assessment of agri-spillways as a soil erosion protection measure in Mediterranean sloping vineyards

Suitable vineyard soils enhance soil stability and biodiversity which in turn protects roots against erosion and nutrient losses. There is a lack of information related to inexpensive and suitable methods and tools to protect the soil in Mediterranean sloping vineyards(25° of slope inclination). In the vineyards of the Montes de Málaga(southern Spain), a sustainable land management practice that controls soil erosion is actually achieved by tilling rills in the down-slope direction to canalize water and sediments. Because of their design and use, we call them agri-spillways. In this research, we assessed two agri-spillways(between 10 m and 15 m length, and slopes between 25.8° and 35°) by performing runoff experiments under extreme conditions(a motor driven pump that discharged water flows up to 1.33 l s~(-1) for 12 to 15 minutes: ≈1000 l). The final results showed: i) a great capacity by these rills to canalize large amounts of water and sediments; and, ii) higher water flow speeds(between 0.16 m s-1 and 0.28 m s~(-1)) and sediment concentrationrates(up to 1538.6 g l~(-1)) than typically found in other Mediterranean areas and land uses(such as badlands, rangelands or extensive crops of olives and almonds). The speed of water flow and the sediment concentration were much higher in the shorter and steeper rill. We concluded that agri-spillways, given correct planning and maintenance, can be a potential solution as an inexpensive method to protect the soil in sloping Mediterranean vineyards.     

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.