Modeling Responses of Diatom Productivity and Biogenic Silica Export to Iron Enrichment in the Equatorial Pacific Ocean

Using a three-dimensional physical-biogeochemical model, we have investigated the modeled responses of diatom productivity and biogenic silica export to iron enrichment in the equatorial Pacific, and compared the model simulation with in situ (IronEx II) iron fertilization results. In the eastern equatorial Pacific, an area of 540,000 km(2) was enhanced with iron by changing the photosynthetic efficiency and silicate and nitrogen uptake kinetics of phytoplankton in the model for a period of 20 days. The vertically integrated Chl a and primary production increased by about threefold 5 days after the start of the experiment, similar to that observed in the IronEx II experiment. Diatoms contribute to the initial increase of the total phytoplankton biomass, but decrease sharply after 10 days because of mesozooplankton grazing. The modeled surface nutrients (silicate and nitrate) and TCO(2) anomaly fields, obtained from the difference between the "iron addition'' and "ambient'' (without iron) concentrations, also agreed well with the IronEx II observations. The enriched patch is tracked with an inert tracer similar to the SF6 used in the IronEx II. The modeled depth-time distribution of sinking biogenic silica (BSi) indicates that it would take more than 30 days after iron injection to detect any significant BSi export out of the euphotic zone. Sensitivity studies were performed to establish the importance of fertilized patch size, duration of fertilization, and the role of mesozooplankton grazing. A larger size of the iron patch tends to produce a broader extent and longer-lasting phytoplankton blooms. Longer duration prolongs phytoplankton growth, but higher zooplankton grazing pressure prevents significant phytoplankton biomass accumulation. With the same treatment of iron fertilization in the model, lowering mesozooplankton grazing rate generates much stronger diatom bloom, but it is terminated by Si(OH)(4) limitation after the initial rapid increase. Increasing mesozooplankton grazing rate, the diatom increase due to iron addition stays at minimum level, but small phytoplankton tend to increase. The numerical model experiments demonstrate the value of ecosystem modeling for evaluating the detailed interaction between biogeochemical cycle and iron fertilization in the equatorial Pacific.

The Chemical Mechanism of a Brown-Rot Decay Mimtic System and its Application in Paper Recycling Processes

This work is aimed at improving our current knowledge of the non-enzymatic inecl~anisins involved in brown-rot decay, as well as the exploration of potential applications of a brown-rot mimetic model system in paper recycling processes. The study was divided into two parts. The first part focussed on the chemical mechanisms involved in chelation and reduction of iron by a low molecular weight chelator (isolated from the brown-rot fungus Gloeophyllz~m tmbeum) and its model compound 2,3- dihydroxybenzoic acid (2,3-DHBA). Chelation as well as free radical generation mediated by this system were studied by ESR measurement. The results indicate that the effects of the chelator/iron ratio, the pH, and other reaction parameters on hydroxyl radical generation by a Fenton type system could be determined using ESR spin-trapping techniques. The results also support the hypothesis that superoxide radicals are involved in the chelator-mediated Fenton process. In the second part of the study, the effect of a chelator-mediated Fenton system for the improvement of deinking efficiency and the n~odification of fiber and paper properties was studied. For the deinking study, copy paper was laser printed with an identical standard pattern. Then repulping and flotation operations were performed to remove ink particles. Under properly controlled deinking conditions, the chelator mediated treatment (CMT) resulted in a reduction in dirt count over that of conventional deinking procedures with no significant loss of pulp strength. To study the effect of the chelator system treatment on the quality of pulp with different fines content, a fully bleached hardwood kraft pulp was beaten to different freeness levels and treated with the chelator-mediated free radical system. The result shows that virgin fiber and heavily beaten fiber respond differently to the free radical treatment. Unbeaten fibers become more flexible and easier to collapse after free radical treatment, while beaten fibers show a reduction in fines and small materials after mild free radical treatment.