Transition-State Spectroscopy of Cyclooctatetraene

The 351-nanometer photoelectron spectrum of the planar cyclooctatetraene radical anion (COT·-) shows transitions to two electronic states of cyclooctatetraene (COT). These states correspond to the D4h 1A1g state, which is the transition state for COT ring inversion, and the D8h 3A2u state. The electron binding energy of the 1A1g transition state is 1.099 ± 0.010 electron volts, which is lower by 12.1 ± 0.3 kilocalories per mole than that of the 3A2u state. The photoelectron spectrum shows that the singlet lies well below the triplet in D8h COT and confirms ab initio predictions that the molecule violates Hund's rule. Vibrational structure is observed for both features and is readily assigned by use of a simple potential energy surface.     

Denitrification potential in a grassland subsoil: effect of carbon substrates

We examined the potential of a subsoil to denitrify nitrate under optimal anaerobic conditions in a laboratory-based incubation when supplied with a range of C substrates of increasing recalcitrance. Both topsoil and its associated subsoil were supplied with nitrate and either glucose, starch or cellulose. Microbial respiration and the evolution of N₂O and N₂ were measured. The subsoil supported low amounts of microbial activity and responded only to the glucose treatment; with less than one-fifth of the N₂O production measured in the top soil. Overall, our findings demonstrated that the denitrification potential of this particular subsoil is relatively low and that only simple carbohydrates could be utilised readily by the resident microorganisms.     

Measurements and modeling of tracer transport in a sandy soil

A physically-based dual-porosity model of water and solute transport under transient field conditions was used to simulate³H transport in seven undisturbed monoliths of a coarse-textured sand under bare soil conditions over a period of 15 months. A double-tracer application of³H and³⁶Cl was performed to test whether sidewall flow occurred in this experimental set-up. The objectives of this study were: to identify any impacts of preferential flow in this type of soil, to quantify³H losses from the soil due to evaporation, and to assess the suitability and relative behavior of³H and³⁶Cl as tracers of water. The model input parameter values were obtained by a combination of direct measurements and model calibration. One domain flow simulations of water flow and tracer concentrations in seepage agreed fairly well with those observed, indicating convective-dispersive behavior in this sandy soil. From the observed tracer and water balance for the entire observation period, the recovery of³H and³⁶Cl in seepage was 33 and 91% respectively, with 67% of the applied H lost by evaporation. Both³H and³⁶Cl broke through in seepage simultaneously, showing that³⁶Cl is equally suitable as a tracer of water as³H. The double-tracer test showed that sidewall flow did not occur.     

The textural analysis of cooked potato. 2. Swelling pressure of starch during gelatinisation

Summary It has been disputed whether, when potato starch gelatinises and absorbs water, it generates an osmotic or matric pressure that makes the potato cells become round and separate from one another. Starch suspensions heated at 100°C in dialysis bags absorbed water, suggesting that starch swelling pressure does exist. It was quantified by heating starch suspensions at 85°C in a chamber which absorbed water through a membrane and contained an argon bubble whose volume was measured. This gave starch swelling pressures around 100 kPa, increasing non-linearly with starch concentration. A comparable estimate (a few hundred kPa) of starch swelling pressure within cooked potato tissue was obtained from the fact that it largely prevented the tissue contraction expected due to loss of turgor pressure in the first 1.5 min of boiling. A slight expansion thereafter was attributed to the combined effect of starch swelling pressure and cell wall and middle lamella degradation.     

The relationship between temperature and sprout growth in stored seed potatoes

Summary Sprout growth in a range of European cultivars was studied over two seasons at constant temperatures from 2 to 25°C, with an additional 33 (day)/22°C (night) treatment in the second season. There were only minor differences in the response of the cultivars and the optimum for sprout growth was at 15–18°C in all cases, when measured over an extended period, but initially sprout growth was more rapid at 23–25°C. Sprout growth at 23–25°C was frequently arrested by sub-apical necrosis, and at these temperatures the sprouts remained short enough for the tubers to be planted by hand without desprouting.     

Recalibrated Mariner 10 Color Mosaics: Implications for Mercurian Volcanism

Recalibration of Mariner 10 color image data allows the identification of distinct color units on the mercurian surface. We analyze these data in terms of opaque mineral abundance, iron content, and soil maturity and find color units consistent with the presence of volcanic deposits on Mercury's surface. Additionally, materials associated with some impact craters have been excavated from a layer interpreted to be deficient in opaque minerals within the crust, possibly analogous to the lunar anorthosite crust. These observations suggest that Mercury has undergone complex differentiation like the other terrestrial planets and the Earth's moon.     

Effects of elevated carbon dioxide concentration on growth and nitrogen fixation in Alnus glutinosa in a long-term field experiment

Nitrogen-fixing plant species may respond more positively to elevated atmospheric carbon dioxide concentrations ([CO2]) than other species because of their ability to maintain a high internal nutrient supply. A key factor in the growth response of trees to elevated [CO2] is the availability of nitrogen, although how elevated [CO2] influences the rate of N2-fixation of nodulated trees growing under field conditions is unclear. To elucidate this relationship, we measured total biomass, relative growth rate, net assimilation rate (NAR), leaf area and net photosynthetic rate of N2-fixing Alnus glutinosa (L.) Gaertn. (common alder) trees grown for 3 years in open-top chambers in the presence of either ambient or elevated atmospheric [CO2] and two soil N regimes: full nutrient solution or no fertilizer. Nitrogen fixation by Frankia spp. in the root nodules of unfertilized trees was assessed by the acetylene reduction method. We hypothesized that unfertilized trees would show similar positive growth and physiological responses to elevated [CO2] as the fertilized trees. Growth in elevated [CO2] stimulated (relative) net photosynthesis and (absolute) total biomass accumulation. Relative total biomass increased, and leaf nitrogen remained stable, only during the first year of the experiment. Toward the end of the experiment, signs of photosynthetic acclimation occurred, i.e., down-regulation of the photosynthetic apparatus. Relative growth rate was not significantly affected by elevated [CO2] because although NAR was increased, the effect on relative growth rate was negated by a reduction in leaf area ratio. Neither leaf area nor leaf P concentration was affected by growth in elevated [CO2]. Nodule mass increased on roots of unfertilized trees exposed to elevated [CO2] compared with fertilized trees exposed to ambient [CO2]. There was also a biologically significant, although not statistically significant, stimulation of nitrogenase activity in nodules exposed to elevated [CO2]. Root nodules of trees exposed to elevated [CO2] were smaller and more evenly spaced than root nodules of trees exposed to ambient [CO2]. The lack of an interaction between nutrient and [CO2] effects on growth, biomass and photosynthesis indicates that the unfertilized trees maintained similar CO2-induced growth and photosynthetic enhancements as the fertilized trees. This implies that alder trees growing in natural conditions, which are often limited by soil N availability, should nevertheless benefit from increasing atmospheric [CO2].     

Measuring and modeling conductances of black spruce at three organizational scales: shoot,branch and canopy

To investigate the extent to which the energy balance of a globally important ecosystem is controlled by biological and environmental processes, measurements of water vapor flux were made on individual black spruce (Picea mariana [Mill.] B.S.P.) shoots, branches, and a whole canopy at the BOREAS Southern Study Area Old Black Spruce (SSA OBS) site. These measurements were used to estimate stomatal, branch boundary layer and canopy boundary layer conductances to water vapor. On a projected needle area basis, stomatal conductances varied between 14 and 92 mmol m(-2) s(-1), and total branch conductance varied seasonally between zero and about 35 mmol m(-2) s(-1). On a ground area basis, total canopy conductance varied between 24 and 105 mmol m(-2) s(-1). Total canopy conductance was partitioned into aerodynamic and physiological components by using shoot-scale measurements scaled by leaf area index. Good agreement was found with an independent estimate of aerodynamic conductance measured when the canopy was wet. Compared with most coniferous forests, the canopy was relatively uncoupled from the atmosphere, and at the ecosystem scale, the control of water vapor flux was approximately equally divided between physiological and abiotic conductances. Two widely used steady-state models of stomatal conductance were parameterized from the shoot and branch measurements. Parameters varied considerably throughout the growing season. A time-constant term was added to these static models to construct dynamic models of stomatal conductance under naturally varying environmental conditions. The dynamic versions of the models outperformed the static versions in explaining stomatal response to rapidly changing environmental conditions. The length of the time-constant term, derived using the dynamic models, suggested that stomata were slow to respond to changing environmental conditions, and that the speed of the response was strongly temperature-dependent.     

Long-term photosynthetic acclimation to increased atmospheric CO(2) concentration in young birch (Betula pendula) trees

To study the long-term response of photosynthesis to elevated atmospheric CO(2) concentration in silver birch (Betula pendula Roth.), 18 trees were grown in the field in open-top chambers supplied with 350 or 700 &mgr;mol mol(-1) CO(2) for four consecutive growing seasons. Maximum photosynthetic rates, stomatal conductance and CO(2) response curves were measured over the fourth growing season with a portable photosynthesis system. The photosynthesis model developed by Farquhar et al. (1980) was fitted to the CO(2) response curves. Chlorophyll, soluble proteins, total nonstructural carbohydrates, nitrogen and Rubisco activity were determined monthly. Elevated CO(2) concentration stimulated photosynthesis by 33% on average over the fourth growing season. However, comparison of maximum photosynthetic rates at the same CO(2) concentration (350 or 700 &mgr;mol mol(-1)) revealed that the photosynthetic capacity of trees grown in an elevated CO(2) concentration was reduced. Analysis of the response curves showed that acclimation to elevated CO(2) concentration involved decreases in carboxylation efficiency and RuBP regeneration capacity. No clear evidence for a redistribution of nitrogen within the leaf was observed. Down-regulation of photosynthesis increased as the growing season progressed and appeared to be related to the source-sink balance of the trees. Analysis of the main leaf components revealed that the reduction in photosynthetic capacity was accompanied by an accumulation of starch in leaves (100%), which was probably responsible for the reduction in Rubisco activity (27%) and to a lesser extent for reductions in other photosynthetic components: chlorophyll (10%), soluble protein (9%), and N concentrations (12%) expressed on an area basis. Despite a 21% reduction in stomatal conductance in response to the elevated CO(2) treatment, stomatal limitation was significantly less in the elevated, than in the ambient, CO(2) treatment. Thus, after four growing seasons exposed to an elevated CO(2) concentration in the field, the trees maintained increased photosynthetic rates, although their photosynthetic capacity was reduced compared with trees grown in ambient CO(2).     

A dynamic model for studying flow of water in single trees

Flow of water in a single tree was modeled in terms of the Darcy equation using a catena of four compartments: root, stem (further divided into discs), branches and leaves. Within each compartment or disc, water content was related to both water potential and conductivity of the xylem tissue using power or logarithmic functions, thus introducing both capacitance and variable resistance to flow in the model. Transpiration from the leaves to the atmosphere was used as the upper boundary to the model, and the soil-root interface as the lower boundary. Parameters for the water content, water potential and conductivity functions, together with physical dimensions were obtained by direct measurement or from the literature. A sensitivity analysis showed that the largest changes in simulated water potential and flow were associated with changes in the parameters directly controlling conductivity. Simulation of both smoothed diurnal changes and stepwise changes showed a phase lag down the tree, with flow tending to approach a steady state, but with changes in the gradients of water potential, water content and conductivity. A preliminary test of the model was made against field data using the Penman-Monteith equation to estimate the transpiration rate in a well-watered Pinus contorta Dougl. stand. Stem flow, water potential and water content were measured directly on a representative tree, which was subsequently harvested to provide dimensions and laboratory estimations of the parameters in the functions by direct measurement.