First-principles theory for the H + CH4 --> H2 + CH3 reaction

A full-dimensional quantum dynamics simulation of a hydrogen atom reacting with methane on an accurate ab initio potential energy surface is reported. Based on first-principles theory, thermal rate constants are predicted with an accuracy comparable to (or even exceeding) experimental precision. The theoretical prediction is within the range of the significantly varied experimental rate constants reported by different groups. This level of accuracy has previously been achieved only for smaller, three-or four-atom reactive systems. Comparison with classical transition state theory confirms the importance of quantum mechanical tunneling for the rate constant below 400 kelvin.     

Enhanced modern heat transfer to the Arctic by warm Atlantic Water

The Arctic is responding more rapidly to global warming than most other areas on our planet. Northward-flowing Atlantic Water is the major means of heat advection toward the Arctic and strongly affects the sea ice distribution. Records of its natural variability are critical for the understanding of feedback mechanisms and the future of the Arctic climate system, but continuous historical records reach back only ~150 years. Here, we present a multidecadal-scale record of ocean temperature variations during the past 2000 years, derived from marine sediments off Western Svalbard (79°N). We find that early-21st-century temperatures of Atlantic Water entering the Arctic Ocean are unprecedented over the past 2000 years and are presumably linked to the Arctic amplification of global warming.     

Self-organization of sorted patterned ground

Striking circular, labyrinthine, polygonal, and striped patterns of stones and soil self-organize in many polar and high alpine environments. These forms emerge because freeze-thaw cycles drive an interplay between two feedback mechanisms. First, formation of ice lenses in freezing soil sorts stones and soil by displacing soil toward soil-rich domains and stones toward stone-rich domains. Second, stones are transported along the axis of elongate stone domains, which are squeezed and confined as freezing soil domains expand. In a numerical model implementing these feedbacks, circles, labyrinths, and islands form when sorting dominates; polygonal networks form when stone domain squeezing and confinement dominate; and stripes form as hillslope gradient is increased.     

Challenges of modeling ocean basin ecosystems

With increasing pressure for a more ecological approach to marine fisheries and environmental management, there is a growing need to understand and predict changes in marine ecosystems. Biogeochemical and physical oceanographic models are well developed, but extending these further up the food web to include zooplankton and fish is a major challenge. The difficulty arises because organisms at higher trophic levels are longer lived, with important variability in abundance and distribution at basin and decadal scales. Those organisms at higher trophic levels also have complex life histories compared to microbes, further complicating their coupling to lower trophic levels and the physical system. We discuss a strategy that builds on recent advances in modeling and observations and suggest a way forward that includes approaches to coupling across trophic levels and the inclusion of uncertainty.     

Effect of summer throughfall exclusion, summer drought, and winter snow cover on methane fluxes in a temperate forest soil

Soil moisture strongly controls the uptake of atmospheric methane by limiting the diffusion of methane into the soil, resulting in a negative correlation between soil moisture and methane uptake rates under most non-drought conditions. However, little is known about the effect of water stress on methane uptake in temperate forests during severe droughts. We simulated extreme summer droughts by exclusion of 168 mm (2001) and 344 mm (2002) throughfall using three translucent roofs in a mixed deciduous forest at the Harvard Forest, Massachusetts, USA. The treatment significantly increased CH₄ uptake during the first weeks of throughfall exclusion in 2001 and during most of the 2002 treatment period. Low summertime CH₄ uptake rates were found only briefly in both control and exclusion plots during a natural late summer drought, when water contents below 0.15 g cm⁻³ may have caused water stress of methanotrophs in the A horizon. Because these soils are well drained, the exclusion treatment had little effect on A horizon water content between wetting events, and the effect of water stress was smaller and more brief than was the overall treatment effect on methane diffusion. Methane consumption rates were highest in the A horizon and showed a parabolic relationship between gravimetric water content and CH₄ consumption, with maximum rate at 0.23 g H₂O g⁻¹ soil. On average, about 74% of atmospheric CH₄ was consumed in the top 4-5 cm of the mineral soil. By contrast, little or no CH₄ consumption occurred in the O horizon. Snow cover significantly reduced the uptake rate from December to March. Removal of snow enhanced CH₄ uptake by about 700-1000%, resulting in uptake rates similar to those measured during the growing season. Soil temperatures had little effect on CH₄ uptake as long as the mineral soil was not frozen, indicating strong substrate limitation of methanotrophs throughout the year. Our results suggest that the extension of snow periods may affect the annual rate of CH₄ oxidation and that summer droughts may increase the soil CH₄ sink of temperate forest soils.     

Influence of Soil Type on the Effects of Elevated Atmospheric CO2 and N Deposition on the Water Balance and Growth of a Young Spruce and Beech Forest

Sixteen open-top chambers, each equipped with two non-weighablegravity-drained lysimeter compartments, were used to investigate the impacts of elevated atmospheric carbon dioxide (CO₂) concentration and nitrogen (N) deposition on the water relations and growth of young model forest ecosystems on two different types of soils. The same vegetation of a mixed spruce and beech overstorey and various herbs in the understorey was planted in all treatments on both soils. The soils were repacked on top of a drainage layer. Four combinations of treatments were applied in four replicates each: ambient (370 cm³ m^-3) CO₂ + low (7 kg N ha^-1 a^-1) N deposition, ambient CO₂ + high(70 kg N ha^-1 a^-1) N deposition, elevated (590 cm³ m^-3) CO₂ + low N deposition, and elevated CO₂ + high N deposition. After canopy closure, treatment effects on evapotranspiration and growth during the third year of study were very different for the two soils.On the acidic sandy loam, elevated CO₂ enhanced growth(leaf biomass +21%, roots +27%) at reduced evapotranspiration (–9%). High N deposition increased aboveground growth even more strongly (+50%), but also increased evapotranspiration (+16%). Together, elevated CO₂ and high N had a more than additive fertilizer effect on growth, while their effects on evapotranspirationcompensated. On the calcareous loamy sand, elevated CO₂not only tended to enhance growth (leaf biomass +17%, roots +20%), but also increased evapotranspiration (+5%).On this soil, aboveground growth was stimulated by N only incombination with elevated CO₂, but less than on the acidic soil, while evapotranspiration (–6.5%) and root growth into the subsoil (–54%) were decreased by increased N deposition at both CO₂ concentrations, in contrast to the N treatments on the acidic sandy loam. The influence of the soil on the observed ecosystem responses canbe interpreted in terms of the concept of optimal resource allocation.     

Effects of root exudates and humic substances on weathering kinetics

The effect of complex natural organic ligands on the weathering kinetics of aluminum oxide was investigated in laboratory experiments. A peat-derived humic substance and root exudates obtained from ectomycorrhizal (Picea abies — Hebeloma crustuliniforme) and non-mycorrhizal Norway Spruce trees; and γ-Al₂O₃ were used as a model system. The experimental weathering rates are in accordance with a surface-controlled dissolution mechanism. The effect of the humic material on dissolution rates appears to depend on the degree of protonation of the humic (macro)molecules: we observed dissolution-enhancement or -inhibition at pH 3 and 4, respectively. Ectomycorrhizal exudates proved to be effective weathering agents at pH 4, as opposed to humic material and non-mycorrhizal exudates. Our results suggest that (i) the role of humic materials in mineral weathering and podzolization is different from what is commonly thought, and (ii) mineral weathering rates in the rhizosphere may be higher than in the bulk soil.     

Einfluß von Cd,Cu, Ni und Zn auf die Synthese metallothioneinähnlicher Substanzen in Scenedesmus subspicatus

Influence of Cd, Cu, Ni and Zn on the synthesis of metalloproteins by Scenedesmus subspicatus In short term experiments under controlled growth conditions the effect of increasing Cd-, Cu-, Ni-, and Zn-concentrations in the nutrient solution on the amount of biomass, the accumulation of heavy metals and the synthesis of metalloproteins by the unicellular greenalga Scenedesmus subspicatus was studied. Among the 4 elements Cd was taken up at the highest rate. Cu revealed to be the most toxic element according to the biomass production. In the Cd trials a protein fraction could be established, which was not detected in the control and in the Cu-, Ni-, and Zn-trials. The further characterization of the isolated fraction indicates the existence of a Cd-metallothionein in the algae.     

Soil‐ and plant‐based nitrogen‐fertilizer recommendations in arable farming

Under‐ as well as overfertilization with nitrogen (N) will result in economic loss for the farmer due to reduced yields and quality of the products. Also from an ecological perspective, it is important that the grower makes the correct decision on how much and when to apply N for a certain crop to minimize impacts on the environment. To aggravate the situation, N is a substance that is present in many compartments in different forms (nitrate, ammonium, organic N, etc.) in the soil‐plant environment and takes part in various processes (e.g., mineralization, immobilization, leaching, denitrification, etc.). Today, many N‐recommendation systems are mainly based on yield expectation. However, yields are not stable from year to year for a given field. Also the processes that determine the N supply from other sources than fertilizer are not predictable at the start of the growing season. Different methodological approaches are reviewed that have been introduced to improve N‐fertilizer recommendations for arable crops. Many soil‐based methods have been developed to measure soil mineral N (SMN) that is available for plants at a given sampling date. Soil sampling at the start of the growing period and analyzing for the amount of NO ‐N (and NH ‐N) is a widespread approach in Europe and North America. Based on data from field calibrations, the SMN pool is filled up with fertilizer N to a recommended amount. Depending on pre‐crop, use of organic manure, or soil characteristics, the recommendation might be modified (±10–50 kg N ha^–1). Another set of soil methods has been established to estimate the amount of N that is mineralized from soil organic matter, plant residues, and/or organic manure. From the huge range of methods proposed so far, simple mild extraction procedures have gained most interest, but introduction into practical recommendation schemes has been rather limited. Plant‐analytical procedures cover the whole range from quantitative laboratory analysis to semiquantitative “quick” tests carried out in the field. The main idea is that the plant itself is the best indicator for the N supply from any source within the growth period. In‐field methods like the nitrate plant sap/petiole test and chlorophyll measurements with hand‐held devices or via remote sensing are regarded as most promising, because with these methods an adequate adjustment of the N‐fertilizer application strategy within the season is feasible. Prerequisite is a fertilization strategy that is based on several N applications and not on a one‐go approach.