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- All Subjects: Environmental sciences
- Creators: Hartnett, Hilairy E
In two-week natural sunlight photo-oxidation experiments the DOC concentration did not change, while the SUVA254 and TF decreased. In addition, the FI and ‘freshness’ increased and HIX decreased during photo-oxidation. Photo-oxidation can explain the upstream to downstream trends for TF, FI, HIX, and freshness observed in river water. Serial photo-oxidation and biodegradation experiments were performed on water collected from three sites along the Colorado River. Bulk DOC concentration in all samples decreased during the biodegradation portion of the study, but DOC bioavailability was lower in samples that were photo-oxidized prior to the bioavailability study.
The upstream to downstream trends in DOC concentration and composition along the river can be explained by a combination of photo-chemical and microbial degradation. The bulk DOC concentration change is primarily driven by microbial degradation, while the changes in the composition of the fluorescent DOC are driven by photo-oxidation.
In order to better constrain the importance of biomass versus entrained soil as a source of trace metals in burn aerosols, small-scale burn experiments were conducted using soil-free foliage representative of a variety of fire-impacted ecosystems. The resulting burn aerosols were collected in two stages (PM > 2.5 μm and PM < 2.5 μm) on cellulose filters using a high-volume air sampler equipped with an all-Teflon impactor. Unburned foliage and burn aerosols were analyzed for Fe and other trace metals using inductively coupled plasma mass spectrometry (ICP-MS).
Results of this analysis show that less than 2% of Fe in plant biomass is likely mobilized as atmospheric aerosols during biomass burning events. The results of this study and estimates of annual global wildfire area were used to estimate the impact of biomass burning aerosols on total atmospheric Fe flux to the ocean. I estimate that foliage-derived Fe contributes 114 ± 57 Gg annually. Prior studies, which implicitly include both biomass and soil-derived Fe, concluded that biomass burning contributes approximately 690 Gg of Fe. Together, these studies suggest that fire-entrained soil particles contribute 83% (576 Gg) of Fe in biomass burning emissions, while plant derived iron only accounts for at most 17%.
More than half of all accessible freshwater has been appropriated for human use, and a substantial portion of terrestrial ecosystems have been transformed by human action. These impacts are heaviest in urban ecosystems, where impervious surfaces increase runoff, water delivery and stormflows are managed heavily, and there are substantial anthropogenic sources of nitrogen (N). Urbanization also frequently results in creation of intentional novel ecosystems. These "designed" ecosystems are fashioned to fulfill particular needs of the residents, or ecosystem services. In the Phoenix, Arizona area, the augmentation and redistribution of water has resulted in numerous component ecosystems that are atypical for a desert environment. Because these systems combine N loading with the presence of water, they may be hot spots of biogeochemical activity. The research presented here illustrates the types of hydrological modifications typical of desert cities and documents the extent and distribution of common designed aquatic ecosystems in the Phoenix metropolitan area: artificial lakes and stormwater retention basins. While both ecosystems were designed for other purposes (recreation/aesthetics and flood abatement, respectively), they have the potential to provide the added ecosystem service of N removal via denitrification. However, denitrification in urban lakes is likely to be limited by the rate of diffusion of nitrate into the sediment. Retention basins export some nitrate to groundwater, but grassy basins have higher denitrification rates than xeriscaped ones, due to higher soil moisture and organic matter content. An economic valuation of environmental amenities demonstrates the importance of abundant vegetation, proximity to water, and lower summer temperatures throughout the region. These amenities all may be provided by designed, water-intensive ecosystems. Some ecosystems are specifically designed for multiple uses, but maximizing one ecosystem service often entails trade-offs with other services. Further investigation into the distribution, bundling, and tradeoffs among water-related ecosystem services shows that some types of services are constrained by the hydrogeomorphology of the area, while for others human engineering and the creation of designed ecosystems has enabled the delivery of hydrologic ecosystem services independent of natural constraints.
Nitrogen is an essential, often limiting, element for biological growth that can act as a pollutant if present in excess. Nitrogen is primarily transported by water from uplands to streams and eventually to recipient lakes, estuaries, and wetlands, but can be modulated by biological uptake and transformation along these flowpaths. As a result, nitrogen can accumulate in aquatic ecosystems if supply is high or if biological retention is low. Dryland and urban ecosystems offer interesting contrasts in water supply, which limits transport and biological activity in drylands, and nitrogen supply that increases with human activity. In my dissertation, I ask: What is the relative balance among nitrogen retention, removal, and transport processes in dryland watersheds, and what is the fate of exported nitrogen? My dissertation research demonstrates that water is a major control on where and when nitrogen is retained and removed versus exported to downstream ecosystems. I used a mass-balance model based on synoptic surveys to study seasonal and spatial patterns in nitrate loading to a dryland stream network. I found that irrigation diversions transport nitrate from agricultural areas to the stream network year-round, even during dry seasons, and are an important driver of nitrate loading. I further explored how seasonal precipitation influences flood nutrient export in an intermittent desert stream by coupling long-term data of flood-water chemistry with stream discharge and precipitation data. I found that higher precipitation prior to a flood fills water storage sites in the catchment, leading to larger floods. In addition, higher antecedent precipitation stimulates biological nitrogen retention in the uplands, leading to lower nitrogen concentration in floods. Finally, I evaluated the consequences of nitrogen export from watersheds on how urban wetlands attenuate nitrate through denitrification that permanently removes nitrogen, and dissimilatory nitrate reduction to ammonium (DNRA) that retains nitrogen in another biologically reactive form. I found that DNRA becomes proportionally more important with low nitrate concentration, thereby retaining nitrogen as ammonium. Collectively, my dissertation research addresses how dryland and urban ecosystems can be integrated into models of watershed nitrogen cycling.
diverse range of anaerobic microbes, but its sources and sinks are poorly understood. The overarching goal of my dissertation is to explore abiotic N2O formation and microbial N2O consumption across reducing environments of the early and modern Earth. By combining experiments as well as diffusion and atmospheric modeling, I present evidence that N2O production can be catalyzed on iron mineral surfaces that may have been present in shallow waters of the Archean ocean. Using photochemical models, I showed that tropospheric N2O concentrations close to modern ones (ppb range) were possible before O2 accumulated. In peatlands of the Amazon basin (modern Earth), unexpected abiotic activity became apparent under anoxic conditions. However, care has to be taken to adequately disentangle abiotic from biotic reactions. I identified significant sterilant-induced changes in Fe2+ and dissolved organic matter pools (determined by fluorescence spectroscopy). Among all chemical and physical sterilants tested, γ - irradiation showed the least effect on reactant pools. Targeting geochemically diverse peatlands across Central and South America, I present evidence that coupled abiotic and biotic cycling of N2O could be a widespread phenomenon. Using isotopic tracers in the field, I showed that abiotic N2O fluxes rival biotic ones under in-situ conditions. Moreover, once N2O is produced, it is rapidly consumed by N2O-reducing microbes. Using amplicon sequencing and metagenomics, I demonstrated that this surprising N2O sink potential is associated with diverse bacteria, including the recently discovered clade II that is present in high proportions at Amazonian sites based on nosZ quantities. Finally, to evaluate the impact of nitrogen oxides on methane production in peatlands, I characterized soil nitrite (NO2–) and N2O abundances along soil profiles. I complemented field analyses with molecular work by deploying amplicon-based 16S rRNA and mcrA sequencing. The diversity and activity of soil methanogens was affected by the presence of NO2– and N2O, suggesting that methane emissions could be influenced by N2O cycling dynamics. Overall, my work proposes a key role for N2O in Earth systems across time and a central position in tropical microbial ecosystems.