Kentucky’s Upper Green River Basin has received significant attention due to the area’s high biodiversity and spectacular karst development. While carbonate bedrock is present throughout the watershed, it is more extensive and homogenous along the river between Greensburg and Munfordville than upstream from Greensburg where the geology is more heterogeneous. This research quantitatively evaluated how lithological differences between the two catchment areas impact hydrochemistry and inorganic carbon cycling. This first required correcting catchment boundaries on previous US Geological Survey Hydrologic Unit Maps to account for areas where the boundaries cross sinkhole plains. Basin boundaries using existing Kentucky Division of Water dye trace data differed from the earlier versions by as much as three kilometers. The river at the downstream site is more strongly influenced by carbonate mineral dissolution, reflected in higher specific conductance (SpC) and pH. The SpC at Munfordville ranges from 0.9 to 4.8 times that at Greensburg, averaging 2.0 times higher. Although rainfall is impacted by sulfuric acid from coal burning, river pH is buffered at both sites. The pH is higher at Munfordville 91% of the time, by an average of 0.28 units. Diurnal, photosynthetic pH variations are damped out downstream suggesting interactions between geologic and biological influences on river chemistry. River temperature differences between the two sites are at least 4oC higher at Greensburg under warm season conditions, but there is a clear trend of temperature differences diminishing as the river cools through the fall and winter. This results from a relatively stable temperature at Munfordville, impacted by large spring inputs of groundwater within the karst region downstream. Although weak statistical relationships between SpC and HCO3 - create uncertainties in high resolution carbon flux calculations, measurement of these fluxes is more highly impacted by discharge variations than concentration variations, which resulted in average daily atmospheric flux estimates within 34% between the two basins using weekly concentration data (3.3x108 vs. 2.2x108 gkm-2 d-1, where km2 is the outcrop area of carbonate rocks), and within only 12% using 15-minute concentration data from regressions (2.6x108 vs. 2.3x108 gkm-2 d-1) for Greensburg and Munfordville, respectively.

Nitrification, a key step in biological nitrogen removal processes, is the oxidation of ammonia into nitrate performed by ammonia oxidizing bacteria (AOB) and nitrite oxidizing bacteria (NOB) under aerobic condition. Researchers have focused on factors affecting the performance of nitrification for decades, but the inorganic carbon limitation on nitrification had been neglected. However, the increase in nitrogen in wastewater has increased the need to evaluate and improve our understanding of this limitation. In a previous research, the hypothesis that different inorganic carbon concentrations would enrich different AOB populations has been examined. In this study, the focus was on the effect of inorganic carbon concentration on NOB, which has a close relationship with AOB. Two 5L lab–scale continuous–flow stirred tank reactors (CSTR) were operated to evaluate the nitrification performance and microbial ecology of nitrifier populations acclimated under inorganic carbon sufficient (high–IC) and limited (low–IC) conditions for approximately 700 days. During the operation period, both bioreactors were able to maintain satisfactory nitrification efficiency higher than 95% at an influent ammonium concentration of 250 mg–N/L. Nitrate was the major end product and no significant nitrite accumulation was observed. To evaluate the effects of inorganic carbon on NOB community structures, cloning/sequencing and real–time PCR were applied to target and quantify the two common NOB genera, Nitrospira and Nitrobacter, as no molecular probe targeting all known NOB is available presently. The results showed that these two genera were both found in the two reactors. Nitrospira was the dominant NOB population in the high–IC bioreactor, while Nitrobacter was dominant in the low–IC one after one year acclimation. Kinetic analysis revealed that NOB enriched in the two reactors have different kinetic performances. However, IC concentration did not show a significant impact on the nitrite oxidizing kinetics of NOB in the batch tests.

abstract: Photosynthesis converts sunlight to biomass at a global scale. Among the photosynthetic organisms, cyanobacteria provide an excellent model to study how photosynthesis can become a practical platform of large-scale biotechnology. One novel approach involves metabolically engineering the cyanobacterium Synechocystis sp. PCC 6803 to excrete laurate, which is harvested directly. This work begins by defining a working window of light intensity (LI). Wild-type and laurate-excreting Synechocystis required an LI of at least 5 µE/m2-s to sustain themselves, but are photo-inhibited by LI of 346 to 598 µE/m2-s. Fixing electrons into valuable organic products, e.g., biomass and excreted laurate, is critical to success. Wild-type Synechocystis channeled 75% to 84% of its fixed electrons to biomass; laurate-excreting Synechocystis fixed 64 to 69% as biomass and 6.6% to 10% as laurate. This means that 16 to 30% of the electrons were diverted to non-valuable soluble products, and the trend was accentuated with higher LI. How the Ci concentration depended on the pH and the nitrogen source was quantified by the proton condition and experimentally validated. Nitrate increased, ammonium decreased, but ammonium nitrate stabilized alkalinity and Ci. This finding provides a mechanistically sound tool to manage Ci and pH independently. Independent evaluation pH and Ci on the growth kinetics of Synechocystis showed that pH 8.5 supported the fastest maximum specific growth rate (µmax): 2.4/day and 1.7/day, respectively, for the wild type and modified strains with LI of 202 µE/m2-s. Half-maximum-rate concentrations (KCi) were less than 0.1 mM, meaning that Synechocystis should attain its µmax with a modest Ci concentration (≥1.0 mM). Biomass grown with day-night cycles had a night endogenous decay rate of 0.05-1.0/day, with decay being faster with higher LI and the beginning of dark periods. Supplying light at a fraction of daylight reduced dark decay rate and improved overall biomass productivity. This dissertation systematically evaluates and synthesizes fundamental growth factors of cyanobacteria: light, inorganic carbon (Ci), and pH. LI remains the most critical growth condition to promote biomass productivity and desired forms of biomass, while Ci and pH now can be managed to support optimal productivity. / Dissertation/Thesis / Doctoral Dissertation Civil and Environmental Engineering 2015

Submitted by Mario BC (mario@bc.ufrpe.br) on 2016-08-09T14:23:59Z No. of bitstreams: 1 Mauro Cesar Palmeira Vilar.pdf: 814000 bytes, checksum: 898ef4b9e5f74ce240a9e2939d558d3d (MD5) / Made available in DSpace on 2016-08-09T14:23:59Z (GMT). No. of bitstreams: 1 Mauro Cesar Palmeira Vilar.pdf: 814000 bytes, checksum: 898ef4b9e5f74ce240a9e2939d558d3d (MD5) Previous issue date: 2015-07-31 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Cylindrospermopsis raciborskii (Wolozynska) Seenayya & Subba Raju is a cosmopolitan diazotrophic and potentially toxic specie considered as invasive in different latitudes. Its capacity of occupying several niches is a feature which is linked to its physiological traits, which allow it to have wide ecological amplitude to several environmental parameters. However, in laboratory conditions that specie might show some growth limitations related to pH, temperature and nutrients. In this scenario, this work aimed to investigate the effect of pH and source of inorganic carbon in growth-related parameters of C. raciborskii. The strain ITEP-A1 (saxitoxin-producing) was cultured in ASM-1 medium and maintained under controlled conditions. Experiments were worked out in 2L erlenmeyers filled with 1.5 L culture medium in different pH ranges and inorganic carbon availability, with/without CO2 enriched-air bubbling. Cyanobacterial growth, morphological traces, biomass acquisition, temperature, pH, conductivity, alkalinity and total inorganic carbon dissolved were analyzed. Results were compared using repeated-measures ANOVA and ANOVA one way with Tukey’s test post hoc (p<0.05). Graphics and statistical analysis were performed in Statistica 7.0 and R i386 3.1.2, respectively. C. raciborskii ITEP-A1 showed better growth rate and biomass under alkaline pH (> 8.0) (P<0,05) in both aeration conditions. pH, alkalinity and inorganic carbon showed an increasing trend throughout the experiment under pH free. At the pH condition > 8.0 with aeration the bicarbonate ion (HCO3-) was the main source of inorganic carbon available to the photosynthetic process, which favored C. raciborskii growth. These results can be extrapolated to a global scale, and suggested as factors that have favored the distribution and expansion of this cyanobacterium to other latitudes. / Cylindrospermopsis raciborskii (Wolozynska) Seenayya & Subba Raju é uma espécie diazotrófica cosmopolita, potencialmente tóxica e considerada invasora em diferentes latitudes. A capacidade de ocupar diferentes nichos é uma característica que está ligada às suas peculiaridades fisiológicas, as quais permitem que possua uma elevada amplitude ecológica para diferentes variáveis ambientais. No entanto, em condições de cultivo, essa espécie pode apresentar limitações para o crescimento relacionadas ao pH, temperatura e nutrientes. Neste cenário, o presente trabalho objetivou investigar o efeito do pH e fonte de carbono inorgânico em parâmetros relacionados ao crescimento de C. raciborskii. A cepa ITEP-A1 (produtora de saxitoxinas) foi cultivada em meio de cultura ASM-1 e mantida sob condições controladas. O delineamento experimental consistiu do cultivo da linhagem ITEP-A1 em diferentes faixas de pH e disponibilidade de carbono inorgânico, com e sem aeração. Os experimentos foram realizados em erlenmeyers de 2 L com 1,5 L de meio de cultura e foram analisadas curvas e taxas de crescimento, traços morfológicos, aquisição de biomassa, temperatura, pH, condutividade, alcalinidade e carbono inorgânico total dissolvido. Os resultados foram comparados usando ANOVA fatorial com medidas repetidas e ANOVA unifatorial com Teste de Tukey a posteriori, sendo as análises estatísticas e gráficos realizados no programa Statistica 7.0 e R i386 3.1.2, respectivamente. C. raciborskii ITEP-A1 apresentou melhor taxa de crescimento e biomassa sob pH alcalino (>8,0), em ambas condições de aeração. Na condição de pH > 8,0 e com aeração, o íon bicarbonato (HCO3-) foi a principal fonte de carbono inorgânico disponível ao processo fotossintético, o que favoreceu o crescimento de C. raciborskii. Tais resultados podem ser extrapolados para uma escala global, e sugeridos como fatores que têm favorecido a distribuição, bem como expansão dessa cianobactéria para outras latitudes.

It has been estimated that approximately half of all anthropogenic fossil fuel carbon dioxide (CO2) emissions have been absorbed by the oceans. Air-sea gas exchange of CO2 and the buffering capacity of seawater allows the oceans to store significant amounts of dissolved inorganic carbon (DIC; ~38,000 GtC). The Arctic Ocean is currently warming at double the rate of the rest of the planet, yet the effect of climate change on the Arctic marine carbon cycle remains unconstrained. Recent work suggests that Arctic marine environments are a carbon sink for the majority of the year, and plays a key role in storing anthropogenic carbon below the mixed layer. Baffin Bay is a semi-enclosed, Arctic basin that supplies cold surface water to the Labrador Sea; a critical region for North Atlantic deep-water formation. While the physical oceanography of surface Baffin Bay is well characterized, less is known about deep water formation mechanisms and its ventilation age. The few residence times for Baffin Bay Deep Water (BBDW) range widely from 20-1450 years. Improved residence time estimates are essential for understanding the role Baffin Bay plays in the Arctic carbon cycle and how this region will respond to climate change. Radiocarbon (D14C) and stable carbon (δ13C) measurements of DIC are powerful tools for parameterizing water mass sources, aging and residence times. However, very few DIC Δ14C and d13C data have been reported in the Arctic Ocean, comprising only a handful of stations in the Eurasian Basin, Canadian Basin, and Beaufort Sea. With this goal in mind, we conducted a study in which DIC samples were collected aboard the CCGS Amundsen in 2019 for δ13C and Δ14C analysis. DIC δ13C and D14C values ranged from 0.68‰ to +1.90‰ and -90.0‰ to +29.8‰, respectively. Surface DIC δ13C values were +0.69‰ to +1.90‰, while deep (>100m) d13C values ranged -0.01 to -0.68‰. Significant linear correlations were found for δ13C and potential density, suggesting DIC δ13C is an effective water mass and carbon source tracer in Baffin Bay. Surface DIC Δ14C values ranged -5.4‰ to +22.9‰, while deep DIC (>1400m) DIC Δ14C averaged -82.2 8.5‰ (n = 9). Much larger surface to deep gradients in DIC Δ14C are observed in Baffin Bay vs. that of the North Atlantic Ocean, suggesting significant aging of BBDW. Next, we used the potential alkalinity method (Palk) and the ΔC* method to quantify the amount of “bomb” 14C and anthropogenic C (DICanth) to model “natural” DIC Δ14C profiles. Both Palk and ΔC* proxies had high errors in cold, low salinity surface water. In particular, surface (<400m) Δ14Cbomb was overestimated at all stations. However, both proxies did not indicate Δ14Cbomb or DICanth contributions below 1000m. Two 14C residence times were estimated based on two proposed mechanisms of BBDW formation. A residence time of 690 +/- 35 years was estimated assuming surface brine rejection in Nares Strait is the main source of BBDW. Another plausible source of BBDW is the entrainment of dense north Atlantic Water over Davis Strait mixed with brine enriched surface water. A comparison of DICanth and Δ14Cbomb corrected deep DIC Δ14C values from the North Atlantic (GO SHIP A16N) to BBDW, resulted in a residence time of 360 +/- 35 years. These residence times (360-690 years) provide new constraints on the ventilation age of deep Baffin Bay and suggest this basin has the potential to store carbon for centuries.

Investigations were conducted at a salt/premix storage facility lying on top of a glacial drumlin near the coastline in eastern Massachusetts, to characterize salt contaminated groundwater. Groundwater hydrogeochemical variations at different depths were determined based on ten years of monthly or quarterly water quality data from 54 monitoring wells. Groundwater was grouped in three water categories – shallow, middle and deep. Hydrogeochemical characterization indicates that the dominant water types are Na-Cl, Na-Ca-Cl and Ca-HCO3 from the shallow to deep water group. Rock weathering is the dominant hydrogeochemical process for deep water group, whereas salt water percolation and cation exchange control chemical compositions of the shallow and middle water groups. Groundwater is classified as post-cation exchange, under-cation exchange and non-cation exchange groups. Gaseous CO2 and total dissolved inorganic carbon (TDIC) transport in unsaturated and saturated zones of the glacial drumlin was also investigated. A measurement system with non-dispersive infrared gas sensors was used to monitor the recovery of CO2 concentration in the headspace of purged monitoring wells. The transient, radial diffusion of CO2 from surrounding soil to the monitoring well is analogous to an existing slug test theory when the headspace is fully mixed. A nested Fibonacci search was performed to calibrate equilibrium soil CO2 concentration and soil gas porosity near the water table. The results demonstrate that water table wells with partially submerged screens can facilitate the equilibrium between the gaseous and dissolved phase of CO2. In the saturated zone, a new model was developed to describe the vertical transport of TDIC in the groundwater. The vertical transport was considered to be a balance of uniform vertical advection and vertical dispersion, subject to a first order source term with two boundary conditions at depth and at the water table. Fifteen years of monthly or quarterly data from 28 monitoring wells in the southern part of the site were used to calibrate a vertical dispersivity α of 5.9 cm and a first order source constant λ of 8.2 x10-9 s-1. These values suggest minimal degassing of groundwater CO2 across the water table and till deposition during Late Wisconsinan deglaciation of the region.

No description available.

The flux of CO2 between the ocean and the atmosphere is an important measure in determining local, global, and regional, as well as short term and long term carbon budgets. In this study, air-sea CO2 fluxes measured using a floating chamber were used to examine the spatial and temporal variability of CO2 fluxes in Florida Bay. Measurements of dissolved inorganic carbon and total alkalinity obtained concurrently with chamber measurements of CO2 flux allowed calculation of ΔpCO2 from flux measurements obtained at zero wind velocity. Floating chamber measurements of ΔpCO2 were subsequently coupled with wind speed data to provide a simple yet reliable means of predicting absolute flux values. Florida Bay is a marine-dominated, sub-tropical estuary located at the southern tip of the Florida peninsula. Spatial variability within the bay reveals four distinct regions that appear to be affected by a variety of physical, chemical and biological processes. In the eastern part of the bay, the waters tend to be oversaturated with respect to CO2, likely due to the input of freshwater from Taylor Slough. The central portion of the bay is characterized by a number of extremely shallow semi-isolated basins with limited exchange with the rest of the bay. This area is typically undersaturated with respect to CO2 and provides a sink for atmospheric CO2. Both the northern and southern regions were highly variable both spatially and temporally.

To establish the structural and lithological controls on gas hydrate distribution and to assess the potential energy resource and environmental hazards in the Indian Ocean, non-pressurized and pressurized cores were recovered from the Krishna-Godavari (K-G) and Mahanadi Basins offshore east India, and from an Andaman Sea site. The pore fluids were analyzed for: salinity, Cl-, sulfate, sulfide, carbonate alkalinity, Ca2+, Mg2+, Sr2+, K+, Na+, Ba2+, and Li+ concentrations, δ13C-DIC, δ18O, D/H, and 87Sr/86Sr ratios; together with infra-red imaging they provided important constraints on the presence and distribution of gas hydrates, thus on the subsurface hydrology. Evidence for methane hydrate was obtained at each of the sites. Only in the K-G Basin, between the sulfate-methane transition zone (SMT) depth and ~80 mbsf, higher than seawater chloride concentrations are observed; below this zone to the depth of the base of the gas hydrate zone (BGHSZ), chloride concentrations and salinity are lower than seawater value. In the Andaman Sea and Mahanadi Basin, only lower than seawater chloride concentrations are observed, and the shallowest gas hydrates occur at 100-200 m below the sulfate-methane transition zone (SMT) and extend to the depth of the BGHSZ. In the K-G Basin, the highest methane hydrate concentrations are associated with fracture zones in clay-rich sediments and/or in some coarser grained horizons. In the Andaman Sea, however, they are primarily associated with volcanic ash horizons. Assuming dilution by water released from dissociated methane hydrate, chloride and salinity anomalies suggest pore volume occupancies on the order of <1% to a maximum of ~61% at two sites (10, 21) in the K-G Basin and <1% to a maximum of ~76% at the Andaman Sea site. Overall, the percent pore volume occupancies based on pressure core methane concentrations and the chloride concentrations in conventional cores are similar. Variations in sulfate gradients were observed with the steepest gradient having the SMT at 8 mbsf in the K-G Basin and the deepest SMT at ~25 mbsf at the Andaman Sea site. The extreme negative δ13C values of the dissolved inorganic carbon (DIC), ranging from -38‰ to -47‰ at the SMT at some of the sites, indicate that anaerobic oxidation of methane (AOM) is an important reaction responsible for sulfate reduction at these sites. At several sites in the K-G Basin, however, the δ13C-DIC values indicate that organic matter oxidation is the dominant reaction.

No description available.