The kinetics of the formation of the titanium-peroxide [TiO 2+ 2 ] complex from the reaction of Ti(IV)OSO 4 with hydrogen peroxide and the hydrolysis of hydroxymethyl hydroperoxide (HMHP) were examined to determine whether Ti(IV)OSO 4 could be used to distinguish between hydrogen peroxide and HMHP in mixed solutions. Stopped-flow analysis coupled to UV-vis spectroscopy was used to examine the reaction kinetics at various temperatures. The molar absorptivity (ε) of the [TiO 2+ 2 ] complex was found to be 679.5 ± 20.8 L mol −1 cm −1 at 405 nm. The reaction between hydrogen peroxide and Ti(IV)OSO 4 was first order with respect to both Ti(IV)OSO 4 and H 2 O 2 with a rate constant of 5.70 ± 0.18 × 10 4 M −1 s −1 at 25 • C, and an activation energy, E a = 40.5 ± 1.9 kJ mol −1 . The rate constant for the hydrolysis of HMHP was 4.3 × 10 −3 s −1 at pH 8.5. Since the rate of complex formation between Ti(IV)OSO 4 and hydrogen peroxide is much faster than the rate of hydrolysis of HMHP, the Ti(IV)OSO 4 reaction coupled to time-dependent UV-vis spectroscopic measurements can be used to distinguish between hydrogen peroxide and HMHP in solution.

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The combined effects of intensive management and planting of improved seedlings have led to large increases in productivity on intensively managed pine forests in the southeastern United States. To best match clones to particular site conditions, an understanding of how specific clones respond to changes in nutrition in terms of biomass partitioning, leaf physiology and biochemistry will be necessary. This study measured the response of biomass partitioning, light-saturated net photosynthesis (A(Sat)) and photosynthetic capacity to a range in soil fertility and fertilization between two contrasting Pinus taeda L. clone ideotypes: a 'narrow crown' clone (NC) that allocates more resources to stem growth and a 'broad crown' clone (BC) that allocates more resources to leaf area (LA). Under field conditions, we found consistent clone by environment (i.e., varying nutrient regimes) interactions in biomass as well as leaf physiology. Nutrient limitations induced by logging residue incorporation resulted in a 25% loss in stem growth in BC, while NC showed no response. We postulated that the decrease in BC was due to the differences in canopy architecture leading to a reduced canopy CO(2) assimilation, as well as to increased belowground maintenance costs associated with fine-root production. In contrast, N and P additions resulted in a 21% greater increase in stem volume in NC relative to BC. Fertilization increased A(Sat) temporarily in both clones, but A(Sat) eventually decreased below control levels by the end of the study. Although we found a clone by fertilization interaction in leaf physiology, the greatest genotype by environment interaction was found in the LA that appeared to have a greater influence than A(Sat) on growth. This research demonstrates the potential importance of selecting appropriate clonal material and silvicultural prescription when implementing site-specific silviculture to maximize productivity in intensively managed southern pine forests.

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