Early diagenesis of plant-derived dissolved organic matter along a wetland, mangrove, estuary ecotone

We studied the role of photochemical and microbial processes in contributing to the transformation of dissolved organic matter (DOM) derived from various plants that dominate the Florida Everglades. Plant-derived DOM leachate samples were exposed to photochemical and microbial degradation and the optical, chemical, and molecular weight characteristics measured over time. Optical parameters such as the synchronous fluorescence intensity between 270 and 290 nm (Fnpeak I), a strong indicator of protein and/or polyphenol content, decreased exponentially in all plant leachate samples, with microbial decay constants ranging from 21.0 d21 for seagrass to 20.11 d21 for mangrove (half-life [t1/2] 5 0.7–6.3 d). Similar decreases in polyphenol content and dissolved organic carbon (DOC) concentration also occurred but were generally an order of magnitude lower or did not change significantly over time. The initial molecular weight composition was reflected in the rate of Fnpeak I decay and suggests that plantderived DOM with a large proportion of high molecular weight structures, such as seagrass derived DOM, contain high concentrations of easily microbially degradable proteinaceous components. For samples exposed to extended simulated solar radiation, polyphenol and Fnpeak I photochemical decay constants were on average 20.7 d21 (t1/2 1.0 d). Our data suggest that polyphenol structures of plant-derived DOM are particularly sensitive to photolysis, whereas high molecular weight protein-like structures are degraded primarily through physical–chemical and microbial processes. Furthermore, microbial and physical processes initiated the formation of recalcitrant, highly colored high molecular weight polymeric structures in mangrove-derived DOM. Thus, partial, biogeochemical transformation of plant-derived DOM from coastal areas is rapid and is likely to influence carbon and nutrient cycling, especially in areas dominated by seagrass and mangrove forests.

Periodic polymer photonic bandgap structures for on-chip optical cavities

Integrated on-chip optical platforms enable high performance in applications of high-speed all-optical or electro-optical switching, wide-range multi-wavelength on-chip lasing for communication, and lab-on-chip optical sensing. Integrated optical resonators with high quality factor are a fundamental component in these applications. Periodic photonic structures (photonic crystals) exhibit a photonic band gap, which can be used to manipulate photons in a way similar to the control of electrons in semiconductor circuits. This makes it possible to create structures with radically improved optical properties. Compared to silicon, polymers offer a potentially inexpensive material platform with ease of fabrication at low temperatures and a wide range of material properties when doped with nanocrystals and other molecules. In this research work, several polymer periodic photonic structures are proposed and investigated to improve optical confinement and optical sensing. We developed a fast numerical method for calculating the quality factor of a photonic crystal slab (PhCS) cavity. The calculation is implemented via a 2D-FDTD method followed by a post-process for cavity surface energy radiation loss. Computational time is saved and good accuracy is demonstrated compared to other published methods. Also, we proposed a novel concept of slot-PhCS which enhanced the energy density 20 times compared to traditional PhCS. It combines both advantages of the slot waveguide and photonic crystal to localize the high energy density in the low index material. This property could increase the interaction between light and material embedded with nanoparticles like quantum dots for active device development. We also demonstrated a wide range bandgap based on a one dimensional waveguide distributed Bragg reflector with high coupling to optical waveguides enabling it to be easily integrated with other optical components on the chip. A flexible polymer (SU8) grating waveguide is proposed as a force sensor. The proposed sensor can monitor nN range forces through its spectral shift. Finally, quantum dot - doped SU8 polymer structures are demonstrated by optimizing spin coating and UV exposure. Clear patterns with high emission spectra proved the compatibility of the fabrication process for applications in optical amplification and lasing.

Composition of a protein-like fluorophore of dissolved organic matter in coastal wetland and estuarine ecosystems

This study demonstrates the compositional heterogeneity of a protein-like fluorescence emission signal (T-peak; excitation/emission maximum at 280/325 nm) of dissolved organic matter (DOM) samples collected from subtropical river and estuarine environments. Natural water samples were collected from the Florida Coastal Everglades ecosystem. The samples were ultrafiltered and excitation–emission fluorescence matrices were obtained. The T-peak intensity correlated positively with N concentration of the ultrafiltered DOM solution (UDON), although, the low correlation coefficient (r2=0.140, p<0.05) suggested the coexistence of proteins with other classes of compounds in the T-peak. As such, the T-peak was unbundled on size exclusion chromatography. The elution curves showed that the T-peak was composed of two compounds with distinct molecular weights (MW) with nominal MWs of about >5×104 (T1) and ∼7.6×103 (T2) and with varying relative abundance among samples. The T1-peak intensity correlated strongly with [UDON] (r2=0.516, p<0.001), while T2-peak did not, which suggested that the T-peak is composed of a mixture of compounds with different chemical structures and ecological roles, namely proteinaceous materials and presumably phenolic moieties in humic-like substances. Natural source of the latter may include polyphenols leached from senescent plant materials, which are important precursors of humic substances. This idea is supported by the fact that polyphenols, such as gallic acid, an important constituent of hydrolysable tannins, and condensed tannins extracted from red mangrove (Rhizophora mangle) leaves exhibited the fluorescence peak in the close vicinity of the T-peak (260/346 and 275/313 nm, respectively). Based on this study the application of the T-peak as a proxy for [DON] in natural waters may have limitations in coastal zones with significant terrestrial DOM input.