Bridging the Scale Gap from Leaf to Canopy in Biosphere-Atmosphere Gas and Particle Exchanges

Terrestrial ecosystems, occupying more than 25% of the Earth's surface, can serve as

`biological valves' in regulating the anthropogenic emissions of atmospheric aerosol

particles and greenhouse gases (GHGs) as responses to their surrounding environments.

While the signicance of quantifying the exchange rates of GHGs and atmospheric

aerosol particles between the terrestrial biosphere and the atmosphere is

hardly questioned in many scientic elds, the progress in improving model predictability,

data interpretation or the combination of the two remains impeded by

the lack of precise framework elucidating their dynamic transport processes over a

wide range of spatiotemporal scales. The diculty in developing prognostic modeling

tools to quantify the source or sink strength of these atmospheric substances

can be further magnied by the fact that the climate system is also sensitive to the

feedback from terrestrial ecosystems forming the so-called `feedback cycle'. Hence,

the emergent need is to reduce uncertainties when assessing this complex and dynamic

feedback cycle that is necessary to support the decisions of mitigation and

adaptation policies associated with human activities (e.g., anthropogenic emission

controls and land use managements) under current and future climate regimes.

With the goal to improve the predictions for the biosphere-atmosphere exchange

of biologically active gases and atmospheric aerosol particles, the main focus of this

dissertation is on revising and up-scaling the biotic and abiotic transport processes

from leaf to canopy scales. The validity of previous modeling studies in determining

iv

the exchange rate of gases and particles is evaluated with detailed descriptions of their

limitations. Mechanistic-based modeling approaches along with empirical studies

across dierent scales are employed to rene the mathematical descriptions of surface

conductance responsible for gas and particle exchanges as commonly adopted by all

operational models. Specically, how variation in horizontal leaf area density within

the vegetated medium, leaf size and leaf microroughness impact the aerodynamic attributes

and thereby the ultrane particle collection eciency at the leaf/branch scale

is explored using wind tunnel experiments with interpretations by a porous media

model and a scaling analysis. A multi-layered and size-resolved second-order closure

model combined with particle

uxes and concentration measurements within and

above a forest is used to explore the particle transport processes within the canopy

sub-layer and the partitioning of particle deposition onto canopy medium and forest

oor. For gases, a modeling framework accounting for the leaf-level boundary layer

eects on the stomatal pathway for gas exchange is proposed and combined with sap

ux measurements in a wind tunnel to assess how leaf-level transpiration varies with

increasing wind speed. How exogenous environmental conditions and endogenous

soil-root-stem-leaf hydraulic and eco-physiological properties impact the above- and

below-ground water dynamics in the soil-plant system and shape plant responses

to droughts is assessed by a porous media model that accommodates the transient

water

ow within the plant vascular system and is coupled with the aforementioned

leaf-level gas exchange model and soil-root interaction model. It should be noted

that tackling all aspects of potential issues causing uncertainties in forecasting the

feedback cycle between terrestrial ecosystem and the climate is unrealistic in a single

dissertation but further research questions and opportunities based on the foundation

derived from this dissertation are also brie

y discussed.

Rapid ratiometric determination of hemoglobin concentration using UV-VIS diffuse reflectance at isosbestic wavelengths.

We developed a ratiometric method capable of estimating total hemoglobin concentration from optically measured diffuse reflectance spectra. The three isosbestic wavelength ratio pairs that best correlated to total hemoglobin concentration independent of saturation and scattering were 545/390, 452/390, and 529/390 nm. These wavelength pairs were selected using forward Monte Carlo simulations which were used to extract hemoglobin concentration from experimental phantom measurements. Linear regression coefficients from the simulated data were directly applied to the phantom data, by calibrating for instrument throughput using a single phantom. Phantoms with variable scattering and hemoglobin saturation were tested with two different instruments, and the average percent errors between the expected and ratiometrically-extracted hemoglobin concentration were as low as 6.3%. A correlation of r = 0.88 between hemoglobin concentration extracted using the 529/390 nm isosbestic ratio and a scalable inverse Monte Carlo model was achieved for in vivo dysplastic cervical measurements (hemoglobin concentrations have been shown to be diagnostic for the detection of cervical pre-cancer by our group). These results indicate that use of such a simple ratiometric method has the potential to be used in clinical applications where tissue hemoglobin concentrations need to be rapidly quantified in vivo.

In situ concentration of semi-volatile aerosol using water-condensation technology

The effect of concentrating semi-volatile aerosols using a water-condensation technology was investigated using the Versatile Aerosol Concentration Enrichment System (VACES) and the Aerodyne Aerosol Mass Spectrometer (AMS) during measurements of ambient aerosol in Pittsburgh, PA. It was found that the shape of the sulfate mass-weighed size distribution was approximately preserved during passage through the concentrator for all the experiments performed, with a mass enhancement factor of about 10-20 depending on the experiment. The size distributions of organics, ammonium and nitrate were preserved on a relatively clean day (sulfate concentration around 7μg/m3), while during more polluted conditions the concentration of these compounds, especially nitrate, was increased at small sizes after passage through the concentrator. The amount of the extra material, however, is rather small in these experiments: between 2.4% and 7.5% of the final concentrated PM mass is due to "artifact" condensation. An analysis of thermodynamic processes in the concentrator indicates that the extra particle material detected can be explained by redistribution of gas-phase material to the aerosol phase in the concentrator. The analysis shows that the condensation of extra material is expected to be larger for water-soluble semi-volatile material, such as nitrate, which agrees with the observations. The analysis also shows that artifact formation of nitrate will be more pronounced in ammonia-limited conditions and virtually undetectable in ammonia-rich conditions. © 2004 Elsevier Ltd. All rights reserved.

Direct and Indirect Effects of Dissolved Organic Matter Source and Concentration on Denitrification in Northern Florida Rivers

Using a natural gradient of dissolved organic carbon (DOC) source and concentration in rivers of northern Florida, we investigated how terrestrially-derived DOC affects denitrification rates in river sediments. Specifically, we examined if the higher concentrations of DOC in blackwater rivers stimulate denitrification, or whether such terrestrially-derived DOC supports lower denitrification rates because (1) it is less labile than DOC from aquatic primary production; whether (2) terrestrial DOC directly inhibits denitrification via biochemical mechanisms; and/or whether (3) terrestrial DOC indirectly inhibits denitrification via reduced light availability to-and thus DOC exudation by-aquatic primary producers. We differentiated among these mechanisms using laboratory denitrification assays that subjected river sediments to factorial amendments of NO3- and dextrose, humic acid dosing, and cross-incubations of sediments and water from different river sources. DOC from terrestrial sources neither depressed nor stimulated denitrification rates, indicating low lability of this DOC but no direct inhibition; humic acid additions similarly did not affect denitrification rates. However, responses to addition of labile C increased with long-term average DOC concentration, which supports the hypothesis that terrestrial DOC indirectly inhibits denitrification via decreased autochthonous production. Observed and future changes in DOC concentration may therefore reduce the ability of inland waterways to remove reactive nitrogen. © 2013 Springer Science+Business Media New York.