Browsing by Subject "Environmental science"
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Item Open Access Alterations of Endophytic Microbial Community Function in Spartina alterniflora as a Result of Crude Oil Exposure(2021) Addis, SamanthaThe 2010 Deepwater Horizon disaster remains one of the largest oil spills in history. This event caused significant damage to coastal ecosystems, the full extent of which has yet to be fully determined. Crude oil contains both toxic substances that are detrimental to microbes and compounds that may be used as food and energy resources by some microbial species. As a result, oil spills have the potential to cause significant shifts in microbial communities. In this study, we assessed the impact of oil contamination on the function of endophytic microbial communities associated with saltmarsh cordgrass (Spartina alterniflora). Soil samples were collected from two locations in coastal Louisiana, USA: one severely affected by contamination from the Deepwater Horizon oil spill and one relatively unaffected location. Spartina alterniflora seedlings were grown in both soil samples under greenhouse conditions, and GeoChip 5.0 was used to evaluate the endophytic microbial metatranscriptome shifts in response to host oil exposure. Microbial functional shifts were detected in functional categories related to metal homeostasis, organic remediation, and phosphorus utilization. These findings show that host oil exposure elicits multiple changes in metabolic response from their endophytic microbial communities, producing effects that may have the potential to impact host plant fitness.
Item Open Access An Ecosystem Approach to Dead Plant Carbon over 50 years of Old-Field Forest Development(2011) Mobley, Megan LeighThis study seeks to investigate the dynamics of dead plant carbon over fifty years of old-field forest development at the Calhoun Long Term Soil-Ecosystem Experiment (LTSE) in South Carolina, USA. Emphasis is on the transition phase of the forest, which is less well studied than the establishment and early thinning phase or the steady state phase. At the Calhoun LTSE, the biogeochemical and ecosystem changes associated with old field forest development have been documented through repeated tree measurements and deep soil sampling, and archiving of those soils, which now allow us to examine changes that have occurred over the course of forest development to date.
In this dissertation, I first quantify the accumulation of woody detritus on the surface of the soil as well as in the soil profile over fifty years, and estimate the mean residence times of that detrital carbon storage. Knowing that large accumulations of C-rich organic matter have piled onto the soil surface, the latter chapters of my dissertation investigate how that forest-derived organic carbon has been incorporated into mineral soils. I do this first by examining concentrations of dissolved organic carbon and other constituents in soil solutions throughout the ecosystem profile and then by quantifying changes in solid state soil carbon quantity and quality, both in bulk soils and in soil fractions that are thought to have different C sources, stabilities, and residence times. To conclude this dissertation, I present the 50-year C budget of the Calhoun LTSE, including live and dead plant carbon pools, to quantify the increasing importance of detrital C to the ecosystem over time.
This exceptional long term soil ecosystem study shows that 50 years of pine forest development on a former cotton field have not increased mineral soil carbon storage. Tree biomass accumulated rapidly from the time seedlings were planted through the establishment phase, followed by accumulations of leaf litter and woody detritus. Large quantities of dissolved organic carbon leached from the O-horizons into mineral soils. The response of mineral soil C stocks to this flood of C inputs varied by depth. The most surficial soil (0-7.5cm), saw a large, but lagged, increase in soil organic carbon (SOC) concentration over time, an accumulation almost entirely due to an increase of light fraction, particulate organic matter. Yet in the deepest soils sampled, soil carbon content declined over time, and in fact the loss of SOC in deep soils was sufficient to negate all of the C gains in shallower soils. This deep soil organic matter was apparently lost from a poorly understood, exchangeable pool of SOM. This loss of deep SOC, and lack of change in total SOC, flies in the face of the general understanding of field to forest conversions resulting in net increases in soil carbon. These long term observations provide evidence that the loss of soil carbon was due to priming of SOM decomposition by enhanced transpiration, C inputs, and N demand by the growing trees. These results suggest that large accumulations of carbon aboveground do not guarantee similar changes below.
Item Open Access Bayesian Statistical Analysis in Coastal Eutrophication Models: Challenges and Solutions(2014) Nojavan Asghari, FarnazEstuaries interfacing with the land, atmosphere and open oceans can be influenced in a variety of ways by anthropogenic activities. Centuries of overexploitation, habitat transformation, and pollution have degraded estuarine ecological health. Key concerns of public and environmental managers of estuaries include water quality, particularly the enrichment of nutrients, increased chlorophyll a concentrations, increased hypoxia/anoxia, and increased Harmful Algal Blooms (HABs). One reason for the increased nitrogen loading over the past two decades is the proliferation of concentrated animal feeding operations (CAFOs) in coastal areas. This dissertation documents a study of estuarine eutrophication modeling, including modeling of major source of nitrogen in the watershed, the use of the Bayesian Networks (BNs) for modeling eutrophication dynamics in an estuary, a documentation of potential problems of using BNs, and a continuous BN model for addressing these problems.
Environmental models have emerged as great tools to transform data into useful information for managers and policy makers. Environmental models contain uncertainty due to natural ecosystems variability, current knowledge of environmental processes, modeling structure, computational restrictions, and problems with data/observations due to measurement error or missingness. Many methodologies capable of quantifying uncertainty have been developed in the scientic literature. Examples of such methods are BNs, which utilize conditional probability tables to describe the relationships among variables. This doctoral dissertation demonstrates how BNs, as probabilistic models, can be used to model eutrophication in estuarine ecosystems and to explore the effects of plausible future climatic and nutrient pollution management scenarios on water quality indicators. The results show interaction among various predictors and their impact on ecosystem health. The synergistic eftects between nutrient concentrations and climate variability caution future management actions.
BNs have several distinct strengths such as the ability to update knowledge based on Bayes' theorem, modularity, accommodation of various knowledge sources and data types, suitability to both data-rich and data-poor systems, and incorporation of uncertainty. Further, BNs' graphical representation facilitates communicating models and results with environmental managers and decision-makers. However, BNs have certain drawbacks as well. For example, they can only handle continuous variables under severe restrictions (1- Each continuous variable be assigned a (linear) conditional Normal distribution; 2- No discrete variable have continuous parents). The solution, thus far, to address this constraint has been discretizing variables. I designed an experiment to evaluate and compare the impact of common discretization methods on BNs. The results indicate that the choice of discretization method severely impacts the model results; however, I was unable to provide any criteria to select an optimal discretization method.
Finally, I propose a continuous variable Bayesian Network methodology and demonstrate its application for water quality modeling in estuarine ecosystems. The proposed method retains advantageous characteristics of BNs, while it avoids the drawbacks of discretization by specifying the relationships among the nodes using statistical and conditional probability models. The Bayesian nature of the proposed model enables prompt investigation of observed patterns, as new conditions unfold. The network structure presents the underlying ecological ecosystem processes and provides a basis for science communication. I demonstrate model development and temporal updating using the New River Estuary, NC data set and spatial updating using the Neuse River Estuary, NC data set.
Item Open Access Biogeochemical Transformations of Trace Element Pollutants During Coal Combustion Product Disposal(2015) Schwartz, Grace EllenCoal fired power plants generate approximately 45% of the electricity produced in the United States every year, and each year, over 100 million tons of coal ash are produced as a by-product of electricity generation. Coal ash is a solid waste made up principally of bottom ash, fly ash, and flue gas desulfurization materials. The chemical composition of coal ash varies depending on the feed coal source, combustion parameters, and the presence and type of air pollution control devices that remove contaminants from the flue gas into the solid waste stream. Although a significant portion of coal ash waste is recycled, the majority of coal ash is disposed in landfills and holding ponds. Coal ash impoundments have a long history of environmental degradation, which includes: contaminant leaching into groundwater, the discharge of contaminant-laden effluent into surface waters, and catastrophic impoundment failures and ash spills. Despite these known problems, coal ash is not considered a hazardous waste, and thus is not subject to stringent disposal requirements. The current coal ash management system is based on risk assessments of coal ash that do not include environmental parameters that have a profound impact on coal ash contaminant mobility, particularly for the toxic elements such as mercury, arsenic, and selenium. This dissertation research focused on the biogeochemical transformations of mercury, arsenic, and selenium associated with coal ash materials in an effort to: (1) define the key environmental parameters controlling mercury, arsenic, and selenium fate during disposal and ash spills; and (2) delineate the relationship between coal ash characteristics, environmental parameters, and leaching potential.
The impact of coal ash on mercury transformations in anaerobic systems was assessed using anaerobic sediment-ash microcosms to mimic an ash spill into a benthic aquatic system. Anaerobic sediments are the primary zones for the microbial conversion of inorganic mercury to methyl mercury (MeHg), a process that is mediated by anaerobic bacteria, particularly sulfate reducing bacteria (SRB). MeHg is a potent neurotoxin that biomagnifies up the aquatic food chain, presenting a human health risk-- especially to children and pregnant women. The results of the sediment-ash microcosm experiments indicated negligible net production of MeHg in microcosms with no ash and in microcosms amended with the low-sulfate/low-Hg ash. In contrast, microcosms amended with sulfate and mercury-rich ash showed increases in MeHg concentrations that were two to three times greater than control microcosms without ash. The enhancement MeHg production in the microcosms was likely due to large quantities of leachable sulfate that stimulated the activity of methylating bacteria. Overall, these results highlight the importance of considering both the geochemical conditions of the receiving environment and the chemical composition of the coal ash in assessing the MeHg potential of coal ash.
The hypothesis that sulfate-rich coal ash can change sediment microbial communities, enhancing MeHg production, was tested by analyzing coal ash impacts on the SRB community in the sediment-ash microcosms using Terminal Restriction Fragment Length Polymorphism (T-RFLP), Quantitative Polymerase Chain Reaction (q-PCR), and Reverse Transcription-qPCR (RT-qPCR). Coal ash did not appear to cause significant changes to the structure of the overall bacterial community, though results showed that it may have caused a decrease in the evenness for species distribution for both SRB and the overall microbial community. During the five-day incubation experiment, the coal ash had a temporary significant effect on SRB abundance during the first one to two days of the experiment and a more sustained effect on SRB activity. This stimulation of SRB population growth and activity also corresponded with increasing net MeHg production. Overall, results indicate that coal ash amendments do not cause large shifts in the overall microbial community or the SRB community, but results indicate that there are connections between SRB abundance/activity and MeHg production. More research is needed to determine how coal ash directly impacts Hg methylating microorganisms, which include diverse array of microorganisms outside of SRB.
The effect of aerobic and anaerobic conditions on arsenic and selenium leaching from coal ash in an ash spill scenario was also assessed using sediment-ash microcosms. The fate of arsenic and selenium associated with coal ash is of particular concern due to the leachability of these elements at neutral pH and their tendency to bioaccumulate in aquatic organisms. Both the redox speciation of arsenic and selenium, and the pH of the aquatic system, are known to influence leaching into the environment, yet current environmental risk assessments of coal ash focus on pH alone as the primary driving force for arsenic and selenium leaching from coal ash and do not take into account the effects of anaerobic conditions and microbial activity. In this research, total dissolved concentrations of arsenic and selenium, dissolved speciation of arsenic, and solid phase speciation of selenium were monitored to determine the biogeochemical transformations and leaching of arsenic and selenium under differing redox conditions. The results from the sediment-ash microcosm studies showed that redox potential was the major determinant of arsenic and selenium mobility in the microcosm systems with greater arsenic leaching occurring in anaerobic microcosms and greater selenium leaching occurring in aerobic microcosms. Furthermore, the experiments provided clues to how coal ash influences the geochemistry of the benthic environment and how these influences affect the speciation and longer term solubility of arsenic and selenium.
Finally, experiments were conducted to determine how differing CaO, SO3, and Fe2O3 concentrations in coal ash affect the release of arsenic and selenium from sediment-ash mixtures in a simulated ash spill environment. Aerobic and anaerobic sediment-ash microcosms were constructed to mimic an ash spill into a benthic aquatic system, and a variety of coal ash materials were tested as amendments, including seven fly ashes, one lime-treated fly ash sample, and two FGD samples. Results showed that, in most cases, the sediment in the microcosm buffered the system at neutral, which counteracted leaching impacts of differing CaO and SO3 concentrations in the microcosms. Regardless of ash material, leaching of selenium was greater under aerobic conditions and was correlated with the total selenium content of the microcosm. Maximum leaching of arsenic occurred in anaerobic microcosms for some ash materials and in aerobic microcosms for other materials, suggesting that ash material chemistry played a significant role in controlling arsenic mobility. In both aerobic and anaerobic microcosms, dissolved arsenic concentration was correlated with total arsenic content of the ash material and in anaerobic microcosms, dissolved arsenic concentrations also correlated with the total iron content of the ash material. Overall, the results of these experiments showed that arsenic and selenium release under environmentally relevant conditions cannot be predicted by the CaO and SO3 content of the ash material. Rather, the total arsenic, total selenium content, and total iron content of the ash material are good predictors of the worst case environmental leaching scenario.
These investigations illuminated two major conclusions: (1) microbial activity and differing redox conditions are key in determining the impact of coal ash on the environment and in determining the mobility of coal ash contaminants, and (2) coal ash characteristics, such as sulfate and iron content, can change the redox chemistry and microbial activity of the surrounding environment, further influencing the fate of ash contaminants. This work will be useful in designing a framework that accurately predicts the leaching potential of ash contaminants under environmentally relevant conditions. The results will also be helpful in developing treatment technologies for ash impoundment effluent, guiding decisions on ash pond closure and remediation, and in designing long-term monitoring plans and remediation strategies for ash-impacted sites.
Item Open Access Biogeomorphodynamics of Coastal Ecosystems under Conditions of Climate Change and Nutrient Enrichment(2013) Margida, Michaela GabrielleAt a given time, tidal landforms inhabit one of three alternate elevation-determined stable states: salt marsh, sub-tidal platform, or tidal flat. The balance between soil production and sea level rise controls transitions between states. Due to increasing anthropogenic inputs to the carbon and nitrogen cycles, CO2 and nutrient enrichment rates are rising. What effect will this have on the evolution of the tidal landform? The present thesis recognizes that (1) soil production depends on halophyte biomass, (2) nutrient enrichment promotes a shift in biomass production from below- to aboveground thus increasing potential for sediment trapping, and (3) elevated CO2 causes an increase in total biomass production. Through use of point- and one-dimensional models, the present thesis finds that under constant suspended sediment levels equal to 20 kg/m3, (1) nutrient enrichment decreases accretion and increases suspended sediment requirements necessary to maintain accessibility of the salt marsh state, (2) elevated CO2 increases accretion decreases suspended sediment requirements necessary to maintain accessibility of the salt marsh state, and (3) the increase in accretion affected by CO2 addition is greater in magnitude than the decrease affected by nutrient enrichment. Thus we can infer that in a future scenario including increasing CO2, nutrient enrichment, and decreasing suspended sediment concentration, the enhancement effect of CO2 will dominate and a net increase in accretion will occur.
Item Open Access Bridging the Scale Gap from Leaf to Canopy in Biosphere-Atmosphere Gas and Particle Exchanges(2016) Huang, ChengWeiTerrestrial 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.
Item Open Access Causes and consequences of microbial symbioses; insights from comparative genomics of plant associated bacterial-fungal interactions(2017) Uehling, Jessie UehlingSymbioses have shaped our modern world, providing for the air we breathe; for the plant and animal diversity we celebrate; and for the functioning of ecosystems from the tops of mountains to the ocean floor. Here I study symbiosis using fungal bacterial interactions as a model for understanding symbiotic dynamics. In this dissertation I present interpretations of experimental data about fungal bacterial interactions that lend insight into dynamics of symbiotic establishment and consequences of long-term endosymbiosis. More specifically, I examine the interactions of a plant-associated zygomycete, Mortierella elongata, and its interactions with several Betaproteobacteria in the Burkholderiales. I used genome sequencing, comparative genomics, physiological assays, and time-lapse microfluidic videography to ask the following questions; How are bacterial fungal symbioses initiated? How do bacteria and fungi communicate? What resources do these microbes share? Are long-term symbioses essential for one or both partners? What are the impacts of removing long-term endosymbionts for fungal host physiology? What are the effects long-term fungal endosymbiosis on bacterial genome content?
In chapter 1 I present lessons learned from genome sequencing of fungus Mortierella elongata and its primary resident endosymbiont, Mycoavidus cysteinexigens. I tested the hypothesis that genome reduction is a commonality of eukaryotic endosymbionts, and that characteristic genes and pathways are impacted by gene loss and inactivation in endosymbionts. I found that compared to its free-living relatives, M. cysteinexigens has a highly reduced genome and has lost genes coding for the biosynthesis of amino acids and intermediates of glycolysis, among other metabolic pathways. I describe a method for clearing fungi of endosymbionts using antibiotics. I report comparative physiological data for the cleared and uncleared strains and draw conclusions about the nature of their interactions based on the behavior of the fungal host lacking the endosymbiont. I tested the hypothesis that sharing of fungal fatty acids underpins this symbiosis, as suggested by the genome sequences of both microbes. I found that when cleared of endosymbionts, M. elongata grows more rapidly and accumulates fatty acids that are likely used by M. cysteinexigens when present.
In chapter 2 I investigate the transcriptional control of fungal-endosymbiont phenotypes. I continued working with the cleared and uncleared strains developed in chapter 1 and quantified transcript abundance in each isolate. I assigned functions to differentially expressed genes by identifying homologues in the fungal genetic model organism Saccharomyces cerevisiae. I layered on transcriptional data to the patterns that emerged from comparative analyses in chapter 1to better understand fungal response to endosymbiosis. I showed that differential expression of conserved genes underpin the increases in growth and altered metabolism in M. elongata when cleared of M. cysteinexigens. I found that endosymbiont presence is associated with toggling of metabolic programs that result in resources more or less bioavailable to M. cysteinexigens based on metabolic capability predicted by genome annotation. I found that genes with homologues in mating pheromone perception pathways are differentially regulated in cleared isolates of M. elongata, and that this aspect of clearing is shared by other isolates of M. elongata when cleared of their bacterial endosymbionts.
In chapter 3 I examine dynamics of pre-symbiotic signaling events between fungi and bacteria using Mortierella elongata and a free-living bacterium, Burkholderia BT03. Using microbial growth assays and a suite of conditioned medias I showed that growth stimulation is mutual for fungi and bacteria, and that signaling leading up to symbiotic phenotypes involves multiple bi-directional signal exchanges. I designed and used a microfluidic platform along with plate based and liquid culture systems to compare fungal growth rates in response to conditioned medias. By extrapolating rates from microbial growth assays including M. elongata, Burkholderia BT03 and related microbes, I inferred directionality, order, conditionality, specificity, and nature of signal exchange leading to microbial growth stimulation in this system.
As a whole this thesis explores how comparative microbial genomics and phenotypic assays can provide mechanistic insight into symbiotic establishment and the effects of long-term symbioses. The results presented here provide novel insights into biotic and abiotic factors dictating symbiotic establishment. Second, they suggest long-term endosymbionts of eukaryotic cells experience convergent gene loss. Lastly they emphasize that long-term endosymbionts strongly impact host metabolism, and that host-microbe metabolic intertwining is a commonality of many symbioses. The use of a systems biology approach to generate comparative genomics data on multiple levels that enable insight into the consequences of fungal bacterial symbioses is a novel contribution for the field.
Item Open Access Characterizing Environmental Per- and Polyfluoroalkyl Substance (PFAS) Exposure and Effects in North Carolina Communities(2022) Hall, Samantha MariePer- and polyfluoroalkyl substances (PFAS) are synthetic chemicals used in a wide array of products and applications (e.g., nonstick cookware, waterproof and water-repellent textiles, firefighting foam). Following their decades of use, PFAS have garnered concern as “forever chemicals” due to their extreme persistence in the environment and in humans. PFAS have further elicited concern because they have been linked to adverse health effects in humans, and their huge number (over 12,000 different chemicals) and complex chemistry make them very challenging to analyze and study for exposure and toxicology. Two particular PFAS chemicals, perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS), are drinking water contaminants that can be found in the blood of the vast majority of people. PFOA and PFOS are also linked to toxic effects like kidney and testicular cancer, increased blood cholesterol, and reproductive outcomes. These two chemicals are being phased out of use and federal drinking water standards are likely upcoming. However, the replacements for these two chemicals are much less well-characterized, and many of these newer, replacement PFAS chemicals can be found in the environment of North Carolina due (at least in part) to industrial pollution.
The overarching goal of this dissertation was to characterize the potential exposure and health effects of PFAS in North Carolina communities. The surface water and drinking water in some areas of North Carolina have been found to be contaminated with PFAS; however, there are additional routes of PFAS exposure beyond drinking water, such as ingestion of house dust or placental transfer during pregnancy. This dissertation explores various routes of PFAS exposure and better characterizes the specific PFAS analytes that can be found in North Carolina and the concentrations in which they are present. Additionally, this dissertation evaluates this exposure and potential associations with some adverse health outcomes in a few North Carolina communities.
In Chapter 2, the relationships between PFAS exposure during pregnancy and birth outcomes are explored. This chapter includes data on PFAS concentrations in placenta samples from 120 participants in Durham, North Carolina and evaluates the subsequent associations between placental PFAS exposure and birth outcomes (e.g., infant birth weight, gestational age). A total of 11 PFAS were measured in placental tissues collected in 2010-2011, and the compounds PFOS, PFOA, PFNA, and PFDA were detected in all placenta samples. A few placental PFAS were associated with birth outcomes. The most striking result was that placental PFOS was associated with changes in birth weight, but the direction of change depended on the sex of the infant. For male infants, placental PFOS was associated with lower birthweight, and in female infants, placental PFOS was associated with higher birthweight.
In Chapter 3, the exposure to PFAS through drinking water is evaluated in a community with known PFAS water contamination. This chapter includes data on PFAS concentrations in blood serum and drinking water samples from 49 participants in Pittsboro, North Carolina. The community receives its drinking water from the Haw River, a part of the Cape Fear River watershed. Blood and water samples were collected at two different timepoints to explore temporal variability in contamination. This community was found to have blood levels of PFAS about two to four times higher than the U.S. average. This chapter also includes results on the associations between PFAS blood level and clinical chemistry measurements, such as serum lipids, as indicators of health. Negative associations were found between serum PFOS and PFHxA with decreased electrolytes and decreased liver enzymes. Positive associations were found between serum PFOA and PFHxS with increased total cholesterol and increased non-HDL cholesterol.
In Chapter 4, the effects and toxicokinetics of PFAS in a pregnant rabbit model are evaluated. This chapter includes data from an animal study of 21 pregnant rabbits provided with drinking water that is representative of the PFAS exposure observed in Pittsboro, North Carolina. Rabbits were exposed to this environmentally-relevant mixture of ten different PFAS during and before pregnancy. After exposure, the wastes and tissues were evaluated to measure the PFAS concentration that accumulated. This provided information on where PFAS are distributed in the body after exposure. The liver of the pregnant rabbit was also evaluated to determine if there was an increase in lipids in the liver, or any changes in liver lipid metabolism. For this study, few differences were noted between treated animals and control animals, indicating that the environmentally-relevant dose had little effect on pregnant rabbits. However, due to the lack of PFAS accumulation in blood, tissue, or in wastes, it is likely that the dose of PFAS given through drinking water was too low.
In Chapter 5, the levels of PFAS in indoor house dust were evaluated. This chapter includes data on PFAS concentrations in indoor dust from 184 homes in Durham, North Carolina, as well as 49 fire stations across the U.S. and Canada. House dust and fire station dust PFAS concentrations were then evaluated for associations with characteristics of the building (e.g., square footage, amount of carpeting, age of building construction). Levels of precursor PFAS, such as fluorotelomer alcohols, were typically higher in dust than the perfluoroalkyl acids. This study, along with previous literature, shows that the legacy PFAS in dust has been decreasing, but the precursor PFAS has been increasing in U.S. house dust. Few associations were found between building characteristics and dust PFAS. However, one notable result was that higher 8:2 FTOH was found in dust from buildings with more carpeting, indicating that carpets may be an important source of exposure to fluorotelomer alcohols (possibly from stain-proofing treatment).
Collectively, this dissertation provides important information on the potential exposure and health effects of PFAS in North Carolina communities.
Item Open Access Characterizing the Binding Potential, Activity, and Bioaccessibility of Peroxisome Proliferator Activated Receptor Gamma (PPARγ) Ligands in Indoor Dust(2015) FANG, MINGLIANGAccumulating evidence is suggesting that exposure to some environmental contaminants may alter adipogenesis, resulting in accumulation of adipocytes, and often significant weight gain. Thus these types of contaminants are often referred to as obesogens. Many of these contaminants act via the activation (i.e. agonism) of the peroxisome proliferator activated receptor γ (PPARγ) nuclear receptor. To date, very few chemicals have been identified as possible PPAR ligands. In the thesis, our goal was to determine the PPARγ ligand binding potency and activation of several groups of major semi-volatile organic compounds (SVOCs) that are ubiquitously detected in indoor environments, including flame retardants such as polybrominated diphenyl ethers (PBDEs) and Firemaster 550 (FM550), and other SVOCs such as phthalates, organotins, halogenated phenols and bisphenols. Additional attention was also given to the potential activity of the major metabolites of several of these compounds. Since the primary sink for many of these SVOCs is dust, and dust ingestion has been confirmed as an important pathway for SVOCs accumulation in humans, the potential PPAR binding and activation in extracts from environmentally relevant dust samples was also investigated.
Previous studies have also shown that SVOCs sorbed to organic matrices (e.g., soil and sediment), were only partially bioaccessible (bioavailable), but it was unclear how bioaccessible these compounds are from indoor dust matrices. In addition, bioactivation of SVOCs (via metabolism) could exacerbate their PPAR potency. Therefore, to adequately assess the potential risk of PPARγ activation from exposure to SVOC mixtures in house dust, it is essential that one also investigates the bioaccessibility and bioactivation of these chemicals following ingestion.
In the first research aim of this thesis, the bioaccessibility and bioactivation of several important SVOCs in house dust was investigated. To accomplish this, Tenax beads (TA) encapsulated within a stainless steel insert were used as an infinite adsorption sink to estimate the dynamic absorption of a suite of flame retardants (FRs) commonly detected in indoor dust samples, and from a few polyurethane foam samples for comparison. Experimental results demonstrate that the bioaccessibility and stability of FRs following ingestion varies both by chemical and by matrix. Organophosphate flame retardants (OPFRs) had the highest estimated bioaccessibility (~80%) compared to brominated compounds (e.g. PBDEs), and values generally decreased with increasing Log Kow, with <30% bioaccessibility measured for the most hydrophobic compound tested, BDE209. In addition, the stability of the more labile SVOCs that contained ester groups (e.g. OPFRs and 2-ethylhexyl-tetrabromo-benzoate (TBB)) were examined in a simulated digestive fluid matrix. No significant changes in the OPFR concentrations were observed in this fluid; however, TBB was found to readily hydrolyze to tetrabromobenzoic acid (TBBA) in the intestinal fluid in the presence of lipases.
In research aims 2 and 3, two commercially available high-throughput bioassays, a fluorescence polarization PPAR ligand binding assay (PolarScreenTM PPARγ-competitor assay kit, Invitrogen, Aim 2) and a PPAR reporter gene assay (GeneBLAzer PPARγ non-DA Assay, Invitrogen, Aim 3) were used to investigate the binding potency and activation of several groups of SVOCs and dust extracts with human PPARγ LBD; respectively. In the PPAR binding assay (Aim 2), most of the tested compounds exhibited dose-dependent binding to PPARγ. Mono(2-ethylhexyl) tetrabromophthalate (TB-MEHP), halogenated bisphenol/phenols, triphenyl phosphate and hydroxylated PBDEs were found to be potent or moderate PPARγ ligands, based on the measured ligand binding dissociation constant (Kd). The most potent compound was 3-OH-BDE47, with an IC50 of 0.24 μM. The extent of halogenation and the position of the hydroxyl group strongly affected binding. Of the dust samples tested, 21 of 24 samples showed significant PPAR binding potency at a concentration of 3 mg dust equivalents (DEQ)/mL. In the PPAR reporter assay (Aim 3), many SVOCs or their metabolites were either confirmed (based on previous reports) or for the first time were found to be potential PPARγ agonists with various potency and efficacy. We also observed that 15 of 25 dust extracts examined showed an activation percentage more than 8% (calculated activation threshold) of the maximal activation induced by rosiglitazone (positive control). In some cases, activation was as high as 50% of the rosiglitazone activation for the dust extracts with the highest efficacy. Furthermore, the correlation between the reporter assay and the ligand binding assay among the house dust extracts was significant and positive (r = 0.7, p < 0.003), suggesting the binding potency was predicting activation. In research aim 2, the effect of bioactivation on the PPARγ binding potency was also investigated. In vitro bioactivation of house dust extracts incubated with rat and human hepatic S9 fractions was used to investigate the role of in vivo biotransformation on PPAR gamma activity. The result showed that metabolism may lead to an increased binding affinity, as a 3-16% increase in PPARγ binding activity was observed following bioactivation of the dust extracts.
In research aim 4, an effect-directed analysis (EDA) was used to identify compounds likely contributing to the observed PPAR activity among the dust extract. Three dust extracts which showed significant PPAR activity with approximately 25, 30, and 50% of the maximal response induced by rosiglitazone at the highest efficacy were fractionated using normal phase high-performance liquid chromatography (NP-HPLC) and each fraction was individually tested for PPAR activity. Active fractions were then analyzed using gas-chromatography mass spectrometry (GC-MS) and possible compounds identified. Three dust extracts showed a similar PPAR activity distribution among the NP-HPLC fractions. In the most active fractions, fatty acids (FAs) were identified as the most active chemicals. The concentrations of four FAs were measured in the house dust extracts, and the concentrations were found to be highly correlated with the observed PPAR activity. These four FAs were also tested for PPAR activity and found to be partial PPAR agonists, particularly oleic and myristic acid. To tentatively identify sources of FAs, FAs in human/animal hair, dead skin cells, and two brands of cooking oil were analyzed. We found the same FAs in those samples and there concentrations were relatively abundant, ranging from 186 to 14,868 µg/g. Therefore, these results suggest that FAs are likely responsible for the observed PPAR activity in indoor dust. Also, this is the first study reporting on the level of FAs in dust samples. The source of these FAs in dust may be either from the cooking or accumulation of human/animal cells in indoor dust.
In conclusion, this research demonstrates that many SVOCs ubiqutiously detected in house dust, and/or their metabolites, can be weak or moderate PPAR ligands. In addition, chemical mixtures in house dust can effectively bind to and activate PPAR. However, our results suggest FAs are probably responsible for these observations, and likely outcompeting the synthetic environmental contaminants present in the dust extract. Furthermore, bioactivation of contaminants present in house dust can potentially increase their affinity for PPAR. And lastly, the bioaccessibility and stability of SVOCs in house dust after ingestion are likely to modulate the PPAR activity in the environmental mixtures and should be considered in future risk assessments.
Item Open Access Chemical Exploration of Global Shipping: Characterization of Organic Pollutants and Disinfection Byproducts Associated with Ship Ballast Water(2018) DeStefano, NoelleCommercial shipping activities place significant strain on one of our most important natural resources as demand for affordable global trade demands ever increasing marine traffic. It has long been recognized as one of the greatest threats to the health of the world’s oceans due to the translocation of invasive species by way of ballasting operations. However, the industry’s role in the global movement of anthropogenic compounds has not been previously investigated. Upcoming regulatory change will further add to the environmental burden as ships will be required to treat ballast water using disinfecting techniques, potentially generating toxic disinfection byproducts. This dissertation was thus focused on revealing current and future potential environmental impacts on the marine environment by using a combination of high resolution mass spectrometry instruments.
Ship ballast water and port water samples were analyzed using both targeted and non-targeted analyses to characterize the organic pollutant burden contained within tanks. This revealed the presence of contaminants derived from both land sources, such as agricultural runoff, as well as compounds associated with shipboard maintenance protocols. Several of these compounds are likely to serve as precursors for disinfection byproduct formation as the shipping industry begins to incorporate ballast water treatment systems. The role of natural organic matter in disinfection byproduct formation was then investigated by chlorinating natural and synthetic seawater. Using a combination of high resolution gas and liquid chromatography paired with accurate mass spectrometry, comprehensive disinfection byproduct profiles were generated to better understand environmental conditions responsible for their formation. A large amount of novel brominated compounds were tentatively identified and should be addressed further prior to global release during ballasting operations. Finally, the ability for continued disinfection byproduct formation to occur beyond quenching disinfection reactions was investigated. This is important to understand further potential risk to sensitive coastal ecosystems beyond the release of treated ballast water.
This dissertation used non-targeted workflows to supplement standard targeted analyses in order to discover compounds that may be of environmental concern relating to the shipping industry. As such, informed recommendations can be made as to the proper environmental conditions in which seawater chlorination should and should not be used. In addition, this allowed for discovery of additional novel disinfection byproducts which can be further investigated for toxicity potential.
Item Open Access Climate Variability and Ecohydrology of Seasonally Dry Ecosystems(2015) Feng, XueSeasonally dry ecosystems cover large areas over the world, have high potential for carbon sequestration, and harbor high levels of biodiversity. They are characterized by high rainfall variability at timescales ranging from the daily to the seasonal to the interannual, and water availability and timing play key roles in primary productivity, biogeochemical cycles, phenology of growth and reproduction, and agricultural production. In addition, a growing demand for food and other natural resources in these regions renders seasonally dry ecosystems increasingly vulnerable to human interventions. Compounded with changes in rainfall regimes due to climate change, there is a need to better understand the role of climate variabilities in these regions to pave the way for better management of existing infrastructure and investment into future adaptations.
In this dissertation, the ecohydrological responses of seasonally dry ecosystem to climate variabilities are investigated under a comprehensive framework. This is achieved by first developing diagnostic tools to quantify the degree of rainfall seasonality across different types of seasonal climates, including tropical dry, Mediterranean, and monsoon climates. This global measure of seasonality borrows from information theory and captures the essential contributions from both the magnitude and concentration of the rainy season. By decomposing the rainfall signal from seasonality hotspots, increase in the interannual variability of rainfall seasonality is found, accompanied by concurrent changes in the magnitude, timing, and durations of seasonal rainfall, suggesting that increase in the uncertainty of seasonal rainfall may well extend into the next century. Next, changes in the hydrological partitioning, and the temporal responses of vegetation resulting from these climate variabilities, are analyzed using a set of stochastic models that accounts for the unpredictability rainfall as well as its seasonal trajectories. Soil water storage is found to play a pivotal role in regulating seasonal soil water hysteresis, and the balance between seasonal soil water availability and growth duration is found to induce maximum plant growth for a given amount of annual rainfall. Finally, these methods are applied in the context of biodiversity and the interplay of irrigation and soil salinity, which are prevailing management issues in seasonally dry ecosystems.
Item Open Access Coal Combustion Residuals in Receiving Lake Ecosystems: Trophic Transfer, Toxicity, and Tracers(2018) Brandt, JessicaModern ecotoxicology draws considerable criticism for its lack of ecological relevance despite its history of interdisciplinary research overlap with the fields of conservation biology and ecology. The overarching aim of this dissertation was to unite the goals of these fields in the context of freshwater pollution by coal-fired power plant (CFPP) effluents, which contribute to the largest point source of environmental pollution in the United States and comprise a substantial threat to receiving ecosystems. CFPPs discharge the by-products of coal combustion, collectively referred to as coal combustion residuals (CCRs), into freshwater rivers and lakes through permitted discharges overseen by the National Pollutant Discharge Elimination System. CCRs are characterized by high concentrations of numerous inorganic elements, many of which are toxic to aquatic organisms. For decades, research on this waste stream has focused on selenium (Se) as an especially toxic trace element for oviparous vertebrates, historically causing severe deformities and species extirpations from which affected ecosystems took decades to recover.
The majority of work described here began with a 2015 field survey of three CFPP-associated lakes in North Carolina from which surface waters, sediments, sediment pore waters, biofilm, zooplankton, and resident fish species were collected and analyzed for their trace element profiles by inductively coupled plasma mass spectrometry (ICP-MS). Initial analyses focusing on Se alone revealed significantly higher tissue liver, muscle, and gonad tissue concentrations in fish from lakes receiving CCR inputs than those from reference systems. At two sites, Mayo Lake and Sutton Lake, water samples and fish tissue concentrations additionally exceeded the US Environmental Protection Agency’s recently revised aquatic life criteria. These analyses were subsequently expanded to consider a more comprehensive suite of ten CCR-associated elements. The results of paired univariate and multivariate analyses of abiotic and biotic compartments for each of the three pairs of lakes showed that CCR-receiving lake sediment pore waters are consistently enriched in manganese, arsenic, selenium, strontium, cadmium, and nickel. From this abiotic compartment, preferential uptake by biological compartments differed among species and among lakes such that only Se was consistently enriched in fish across the three systems. Across all lake pairs, the three fish species differed in their aggregate CCR tissue burdens, with bluegill having the highest burden and largemouth bass having the lowest. A lab-based trophic transfer study of field-collected biofilm and zooplankton to the model fish species, fathead minnow (Pimephalas promelas), supported the hypothesis that diet and trophic position are important mediators of fish tissue trace element composition. CCR loading history, lake size, and water residence time influence the magnitude of trace element accumulation in these systems, with important implications for the legacy of this waste stream as CFPPs are retired and their effluent streams to adjacent water bodies are terminated.
An additional lab-based dietary study of organic selenomethionine exposure sought to describe the bioenergetic consequences of low-level Se exposure to adult zebrafish (Danio rerio) and their offspring. Sex-specific metabolic effects were observed in whole organisms and individual tissue types and metabolic partitioning using the Seahorse Extracellular Flux Analyzer indicated that mitochondrial dysfunction could underlie altered metabolic rates, with implications for the ecological fitness of Se-impacted fish communities. This study also explored maternal and paternal exposure routes of Se exposure to F1 generation embryos and found that both routes of exposure resulted in reduced reserve respiratory capacity relative to control fish.
Inorganic trace elements are incorporated into the lattice of metabolically-stable fish otoliths, providing unique records of fishes’ lifetime exposure history. Two distinct otolith applications are explored here. First, time series otolith concentrations of a subset of CCRs were compared to overlapping time series of CFPP loading data to determine whether changes in system inputs were reflected in otolith uptake. Significant time lags, intra-species variation, and differences among species for Se suggested that otolith chemistry could be reflecting Se input legacies and complex biogeochemical cycling through the food webs from which fish are exposed. In contrast, fish otolith 87Sr/86Sr isotopic ratios did distinguish fish from a CCR-receiving lake in agreement with ratios measured in surface and pore water samples. If this initial proof-of-principle result holds for fish collected from larger reservoirs in which water chemistry is less uniform, otoliths could be powerful biological tracers of freshwater CCR impacts.
In tandem with the decreasing reliance on coal in the US, CFPPs are retiring, excavating their coal ash ponds, and otherwise terminating their CCR effluent streams. As these processes unfold, actively-receiving freshwater ecosystems are undergoing a transition to legacy status. An especially important avenue for future research is how CCR stoichiometry will change over time to reflect the relative transformation, sequestration, and transport of individual elements within and through these recovering systems. The ecotoxicological implications of the legacy CCR waste stream will likely evolve as exposure mixtures change.
Item Open Access Comparisons of Carbon and Water Fluxes of Pine Forests in Boreal and Temperate Climatic Zones(2015) Torngern, PantanaQuantifying carbon fluxes and pools of forest ecosystems is an active research area in global climate study, particularly in the currently and projected increasing atmospheric carbon dioxide concentration environment. Forest carbon dynamics are closely linked to the water cycle through plant stomata which are regulated by environmental conditions associated with atmospheric and soil humidity, air temperature and light. Thus, it is imperative to study both carbon and water fluxes of a forest ecosystem to be able to assess the impact of environmental changes, including those resulting from climate change, on global carbon and hydrologic cycles. However, challenges hampering such global study lie in the spatial heterogeneity of and the temporal variability of fluxes in forests around the globe. Moreover, continuous, long-term monitoring and measurements of fluxes are not feasible at global forest scale. Therefore, the need to quantify carbon and water fluxes and to identify key variables controlling them at multiple stands and time scales is growing. Such analyses will benefit the upscaling of stand-level observations to large- or global-scale modelling approaches.
I performed a series of studies investigating carbon and water fluxes in pine forests of various site characteristics, conditions and latitudinal locations. The common techniques used in these studies largely involved sap flux sensors to measure tree-level water flow which is scaled up to stand-level transpiration and a process-based model which calculates canopy light absorption and carbon assimilation constrained by the sap-flux beased canopy stomatal conductance (called Canopy Conductance Constrained Carbon Assimilation or 4C-A model). I collected and analyzed sap flux data from pine forests of two major species: Pinus taeda in temperate (36 °N) and Pinus sylvestris in boreal (64 °N) climatic zones. These forests were of different stage-related canopy leaf area and some were under treatments for elevated atmospheric CO2 concentration or fertilization.
I found that (Chapter 2) the 17-year long free-air CO2 enrichment (FACE) had little effect on canopy transpiration of a mixed forest with the dominant P. taeda and other broadleaved species as the understory in North Carolina, USA (Duke FACE). The result was due to the compensation of elevated [CO2]-induced increase of canopy leaf area for the reduction of mean canopy stomatal conductance. My next theoretical study (Chapter 3), comparing P. taeda (native at 36 °N in North Carolina), P. sylvestris (native at 64 °N in norther Sweden) and Pinus contorta (native at 58 °N in British Columbia, Canada) canopies, revealed that the interaction between crown architecture and solar elevation associated with site latitude of pine canopies affected the distribution and total amount of canopy light absorption and potentially photosynthesis such that the latitudinally prescribed needle organization of a pine canopy is optimal for light interception and survival in its native location. Then, I quantified and analyzed water fluxes in four pine forests: one composed of P. taeda in North Carolina and three containing P. sylvestris in northern Sweden (Chapter 4). The latter forests consisted of various stage-related canopy leaf area and nutrient status. Combining my estimates with other published results from forests of various types and latitudinal locations, I derived an approach to estimate daily canopy transpiration during the growing season based on a few environmental variables including atmospheric and soil humidity and canopy leaf area. Moreover, based on a water budget analysis, I discovered that the intra-annual variation of precipitation in a forest has a small effect on evapotranspiration and primarily affecting outflow; however, variation of precipitation across latitudes proportionally influences anuual evapotranspiration and outflow. Furthermore, the hydrologic analyses implied the `disequilibrium' of forest water cycling during the growing season when forests may use less and more water in dry and wet regions, respectively, than the incoming precipitation. Nevertherless, at annual timescale, most forests became in `equilibrium' by using similar proportion of incoming precipitation. Finally, (Chapter 5) I estimated and analyzed the temporal and spatial variabilities of carbon fluxes of the same four forests measured in Chapter 4 using the 4C-A computational approach and analyzed their resource-use efficiencies. I concluded that, based on my results and others as available, despite the differences in species clumping and latitudes which influence growing season length and solar elevation, the gross primary productivity can be conservatively linearly related to the canopy light absorption. However, based on previous findings from a global study, different allocation of the acquired carbon to the above- and belowground is regulated by soil nutrient status.
Overall, the findings in this dissertation offer new insights into the impacts of environmental changes on carbon and water dynamics in forests across multiple sites and temporal scales which will be useful for larger-scale analyses such as those pertaining to global climate projection.
Item Open Access Contaminant Interactions and Biological Effects of Single-walled Carbon Nanotubes in a Benthic Estuarine System(2013) Parks, AshleySingle-walled carbon nanotubes (SWNT) are highly ordered filamentous nanocarbon structures. As their commercial and industrial use becomes more widespread, it is anticipated that SWNT will enter the environment through waste streams and product degradation. Because of their highly hydrophobic nature, SWNT aggregate and settle out of aqueous environments, especially in saline environments such as estuaries. Therefore, sediments are a likely environmental sink for SWNT once released. It is important to understand how these materials will impact benthic estuarine systems since they are the probable target area for SWNT exposure in addition to containing many lower trophic level organisms whose survvial and contaminant body burdens can have a large impact on the overall ecosystem. Disruptions in lower trophic level organism survival can have negative consequences for higher trophic levels, impacting the overall health of the ecosystem. It is also important to consider contaminant bioaccumulation, trophic transfer and biomagnification. If SWNT are taken up by benthic invertebrates, there is the possibility for trophic transfer, increasing the exposure of SWNT to higher trophic level organisms that otherwise would not have been exposed. If this type of transfer occurs in environmentally important species, the potential for human exposure may increase. My research aims to determine the magnitude of the toxicity and bioaccumulation of SWNT in benthic estuarine systems, as well as determine how they interact with other contaminants in the environment. This research will contribute to the knowledge base necessary for performing environmental risk assessments by providing information on the effects of SWNT to benthic estuarine systems.
Before investigating the environmental effects of SWNT, it is imperative that a measurement method is established to detect and quantify SWNT once they enter the environment. This research utilized pristine, semiconducting SWNT to develop extraction and measurement methods to detect and quantify these specific materials in environmental media using near infrared fluorescence (NIRF) spectroscopy. Semiconducting SWNT fluoresce in the near infrared (NIR) spectrum when excited with visible&ndashNIR light. This unique optical property can be used to selectively measure SWNT in complex media.
The fate, bioavailability, bioaccumulation and toxicity of SWNT have not been extensively studied to date. Pristine SWNT are highly hydrophobic and have been shown to strongly associate with natural particulate matter in aquatic environments. In light of this, I have focused my research to examine the influence of sediment and food exposure routes on bioavailability, bioaccumulation, and toxicity of structurally diverse SWNT in several ecologically-important marine invertebrate species. No significant mortality was observed in any organism at concentrations up to 1000 mg/kg. Evidence of biouptake after ingestion was observed for pristine semiconducting SWNT using NIRF spectroscopy and for oxidized 14C&ndashSWNT using liquid scintillation counting. After a 24 hour depuration period, the pristine semiconducting SWNT were eliminated from organisms to below the method detection limit (5 &mug/mL), and the 14C&ndashSWNT body burden was decreased by an order of magnitude to a bioaccumulation factor (BAF) of <0.01. Neither pristine SWNT nor oxidized 14C&ndashSWNT caused environmentally relevant toxicity or bioaccumulation in benthic invertebrates. Overall, the SWNT were not bioavailable and appear to associate with the sediment.
In addition to investigating the toxicity and bioaccumulation of SWNT as an independent toxicant, it is important to consider how they will interact with other contaminants in the environment (i.e., increase or decrease toxicity and bioaccumulation of co&ndashcontaminants, alter the environmental transport of co&ndashcontaminants, induce degradation of co&ndashcontaminants, etc.). I wanted to investigate the effects of SWNT on a complex mixture of contaminants already present in a natural system. New Bedford Harbor (NBH) sediment, which is contaminated with polychlorinated biphenyls (PCBs), was amended with pristine SWNT to determine if the presence of SWNT would mitigate the toxicity and bioaccumulation of the PCBs in deposit-feeding invertebrates. A dilution series of the NBH sediment was created using uncontaminated Long Island Sound (LIS) sediment to test 25% NBH sediment, 50% NBH sediment, 75% NBH sediment, and 100% NBH sediment. The results of this work showed increased organism survival and decreased bioaccumulation of PCBs in treatments amended with SWNT, with the greatest reduction observed in the 25% NBH sediment treatment group amended with 10 mg SWNT/g dry sediment. Polyethylene (PE) passive samplers indicated a reduction of interstitial water (ITW) PCB concentration of greater than 90% in the 25% NBH sediment + 10 mg SWNT/g dry sediment amendment. The ITW concentration was reduced because PCBs were not desorbing from the SWNT. Lower bioavailability leads to reduced potential for toxic effects, supporting the observation of increased survival and decreased bioaccumulation. Once in the sediment, not only are SWNT not bioavailable, they act as a highly sorptive phase, such as black carbon (BC), into which hydrophobic organic contaminants (HOCs), such as PCBS and polycyclic aromatic hydrocarbons (PAHs), can partition, thereby reducing the toxicity and bioavailability of co-occurring HOCs.
To more fully understand the impact of SWNT in this environment, their biodegradability also needs to be investigated. Biodegradation of SWNT could lead to release and/or transformation of sorbed HOCs as well as a change in the inherent transport, toxicity, and bioaccumulation of SWNT in the estuarine environment. Because the persistence of SWNT will be a primary determinant of the fate of these materials in the environment, I conducted experiments to determine if the fungus Trametes versicolor, the natural bacterial communities present in NBH sediment, and municipal wastewater treatment plant sludge could degrade or mineralize oxidized 14C&ndashSWNT. Over a six month time period, no significant degradation or mineralization was observed. In all treatments, approximately 99% of the 14C-SWNT remained associated with the solid phase, with only approximately 0.8% of added 14C present as dissolved species and only 0.1% present as 14CO2. These small pools of non-SWNT 14C were likely due to trace impurities, as no differences in production were observed between treatments and abiotic (killed) controls.
Item Open Access Controls on Carbon Uptake and Storage in Southeastern Forests(2012) Oishi, Andrew ChristopherUptake and storage of carbon by forest ecosystems continues to be a major research topic needed for the quantification of global budgets in an increasing atmospheric carbon dioxide environment. However, there are considerable challenges in quantifying carbon budgets of forest across a wide range of spatial and temporal scales. Although general trends in the components of carbon budgets emerge when analyzed over large spatial or temporal scales, these relationships tend to weaken, or even reverse, at smaller spatial (e.g. stand level) and temporal scales. On the other hand, continuous measuring and monitoring is not a feasible or sensible approach for the range of global forests. There is growing need to identify the key variables that drive variability in these localized budgets at multiple time scales. These results will assist in upscaling stand-level observations into large-scale modeling approaches.
Forest carbon dynamics are closely-coupled with the hydrologic cycle, so an approach that attempts to bridge these dynamics must incorporate water availability and use. Water is necessary for trees to transport nutrients, maintain cellular function, and regulate stomatal conductance; however, water is also related to other biological processes, including microbial decomposition of soil carbon, and physiologically-important abiotic factors, such as atmospheric vapor pressure deficit. Thus, much of the key to understanding the variability in forest carbon cycles is identifying the sensitivity of the processes of the carbon cycle to water availability.
Therefore, my research takes the following approach: I begin by using sap flux sensors to measure tree-level transpiration over a four-year period and combine these values with other estimates of stand-level evaporation to generate an accurate estimate of total evapotranspiration, partitioned by component and tree species (Chapter 2). To assess the sensitivity of the water fluxes in the forest, I next establish a complete hydrologic budget for the forest stand over four years, including one severe and one mild drought (Chapter 3). I then focus on the flux of carbon from the soil and its variability over space and time. Using automated, high-frequency measurements of soil CO2 flux over a 10-year period and including 3 forest stands, I assess inter- and intra-stand variability as well as inter- and intra-annual variability in soil flux in relation to climatic factors and stand characteristics representing productivity (Chapter 4). In order to assess how soil CO2 flux may change over longer periods of time within the context of global change, I analyze how enrichment of [CO2] independent of and combined with soil nitrogen availability alter the balance of carbon in a stand (Chapter 5). Finally, building off these previous chapters, I examine the relationship between carbon uptake, allocation, and turnover in a mixed-species forest experiencing interannual variability in water availability (Chapter 6).
I conclude that (Chapter 2) sap flux sensors can successfully be used to estimate tree- to stand-level transpiration if one accounts for both nocturnal water movement through the tree stem and spatial variability of species composition and demography within a stand. (Chapter 3) Despite reductions in transpiration by some species during water-limited (i.e. drought) periods, the magnitude and duration of these reductions results in annual water use that is similar to a non-drought year. The consequence of this invariability in transpiration and evapotranspiration for the hydrologic cycle is that changes in annual precipitation translate directly to changes in water supplied to rivers and streams. (Chapter 4) Diurnal to seasonal variability in soil CO2 flux is driven by temperature, whereas interannual variability is most-strongly influenced by soil moisture. Furthermore, spatial variability of soil CO2 flux is directly related to forest productivity, and by proxy, leaf production, across biomes and, to a lesser extent, across stands within a region. However, within-stand variability may be inversely related to leaf production as a result of differential allocation of carbon between aboveground and belowground uses based on local resource availability. (Chapter 5) Although elevated atmospheric [CO2] enhances productivity, it may only result in a small increase in the flux of CO2 from soils. Instead, nitrogen availability explains much of the variability within a forest stand, regardless of [CO2], with increasing nitrogen availability resulting in lower allocation of carbon belowground and greater aboveground productivity. (Chapter 6) Interannual variability in water availability can affect gross primary productivity in mature forests but these effects may primarily affect the following growing season. The proportionate changes in gross primary productivity appears to show greater reductions with previous year's soil moisture than net primary productivity, leading to increased carbon use efficiency following drought. Variability in leaf biomass in this relatively stable, mature stand appears to drive the interannual variability in photosynthesis as well as the demand for carbon used for biomass production and metabolic activity.
Item Open Access Convexity, Concavity, and Human Agency in Large-scale Coastline Evolution(2014) Ells, Kenneth DanielCoherent, large-scale shapes and patterns are evident in many landscapes, and evolve according to climate and hydrological forces. For large-scale, sandy coastlines, these shapes depend on wave climate forcing. The wave climate is influenced by storm patterns, which are expected to change with the warming climate, and the associated changes in coastline shape are likely to increase rates of shoreline change in many places. Humans have historically responded to coastline change by manipulating various coastal processes, consequently affecting long-term, large-scale coastline shape change. Especially in the context of changing climate forcing and increasing human presence on the coast, the interaction of the human and climate-driven components of large-scale coastline evolution are becoming increasingly intertwined.
This dissertation explores how climate shapes coastlines, and how the effects of humans altering the landscape interact with the effects of a changing climate. Because the coastline is a spatially extended, nonlinear system, I use a simple numerical modeling approach to gain a basic theoretical understanding of its dynamics, incorporating simplified representations of the human components of coastline change in a previously developed model for the physical system.
Chapter 1 addresses how local shoreline stabilization affects the large scale morphology of a cuspate-cape type of coastline, and associated large-scale patterns of shoreline change, in the context of changing wave climate, comparing two fundamentally different approaches to shoreline stabilization: beach nourishment (in which sediment is added to a coastline at a long-term rate that counteracts the background erosion), and hard structures (including seawalls and groynes). The results show that although both approaches have surprisingly long-range effects with spatially heterogeneous distributions, the pattern of shoreline changes attributable to a single local stabilization effort contrast greatly, with nourishment producing less erosion when the stabilization-related shoreline change is summed alongshore.
Chapter 2 presents new basic understanding of the dynamics that produce a contrasting coastline type: convex headland-spit systems. Results show that the coastline shapes and spatially-uniform erosion rates emerge from two way influences between the headland and spit components, and how these interactions are mediated by wave climate, and the alongshore scale of the system. Chapter 2 also shows that one type of wave-climate change (altering the proportion of `high-angle' waves) leads to changes in coastline shape, while another type (altering wave-climate asymmetry) tends to reorient a coastline while preserving its shape.
Chapter 3 builds on chapter 2, by adding the effects of human shoreline stabilization along such a convex coastline. Results show that in the context of increasing costs for stabilization, abandonment of shoreline stabilization at one location triggers a cascade of abandonments and associated coastline-shape changes, and that both the qualitative spatial patterns and alongshore speed of the propagating cascades depends on the relationship between patterns of economic heterogeneity and the asymmetry of the wave-climate change--although alterations to the proportion of high-angle waves in the climate only affects the time scales for coupled morphologic/economic cascades.
Item Open Access Data to Decision in a Dynamic Ocean: Robust Species Distribution Models and Spatial Decision Frameworks(2016) Best, Benjamin DaleHuman use of the oceans is increasingly in conflict with conservation of endangered species. Methods for managing the spatial and temporal placement of industries such as military, fishing, transportation and offshore energy, have historically been post hoc; i.e. the time and place of human activity is often already determined before assessment of environmental impacts. In this dissertation, I build robust species distribution models in two case study areas, US Atlantic (Best et al. 2012) and British Columbia (Best et al. 2015), predicting presence and abundance respectively, from scientific surveys. These models are then applied to novel decision frameworks for preemptively suggesting optimal placement of human activities in space and time to minimize ecological impacts: siting for offshore wind energy development, and routing ships to minimize risk of striking whales. Both decision frameworks relate the tradeoff between conservation risk and industry profit with synchronized variable and map views as online spatial decision support systems.
For siting offshore wind energy development (OWED) in the U.S. Atlantic (chapter 4), bird density maps are combined across species with weights of OWED sensitivity to collision and displacement and 10 km2 sites are compared against OWED profitability based on average annual wind speed at 90m hub heights and distance to transmission grid. A spatial decision support system enables toggling between the map and tradeoff plot views by site. A selected site can be inspected for sensitivity to a cetaceans throughout the year, so as to capture months of the year which minimize episodic impacts of pre-operational activities such as seismic airgun surveying and pile driving.
Routing ships to avoid whale strikes (chapter 5) can be similarly viewed as a tradeoff, but is a different problem spatially. A cumulative cost surface is generated from density surface maps and conservation status of cetaceans, before applying as a resistance surface to calculate least-cost routes between start and end locations, i.e. ports and entrance locations to study areas. Varying a multiplier to the cost surface enables calculation of multiple routes with different costs to conservation of cetaceans versus cost to transportation industry, measured as distance. Similar to the siting chapter, a spatial decisions support system enables toggling between the map and tradeoff plot view of proposed routes. The user can also input arbitrary start and end locations to calculate the tradeoff on the fly.
Essential to the input of these decision frameworks are distributions of the species. The two preceding chapters comprise species distribution models from two case study areas, U.S. Atlantic (chapter 2) and British Columbia (chapter 3), predicting presence and density, respectively. Although density is preferred to estimate potential biological removal, per Marine Mammal Protection Act requirements in the U.S., all the necessary parameters, especially distance and angle of observation, are less readily available across publicly mined datasets.
In the case of predicting cetacean presence in the U.S. Atlantic (chapter 2), I extracted datasets from the online OBIS-SEAMAP geo-database, and integrated scientific surveys conducted by ship (n=36) and aircraft (n=16), weighting a Generalized Additive Model by minutes surveyed within space-time grid cells to harmonize effort between the two survey platforms. For each of 16 cetacean species guilds, I predicted the probability of occurrence from static environmental variables (water depth, distance to shore, distance to continental shelf break) and time-varying conditions (monthly sea-surface temperature). To generate maps of presence vs. absence, Receiver Operator Characteristic (ROC) curves were used to define the optimal threshold that minimizes false positive and false negative error rates. I integrated model outputs, including tables (species in guilds, input surveys) and plots (fit of environmental variables, ROC curve), into an online spatial decision support system, allowing for easy navigation of models by taxon, region, season, and data provider.
For predicting cetacean density within the inner waters of British Columbia (chapter 3), I calculated density from systematic, line-transect marine mammal surveys over multiple years and seasons (summer 2004, 2005, 2008, and spring/autumn 2007) conducted by Raincoast Conservation Foundation. Abundance estimates were calculated using two different methods: Conventional Distance Sampling (CDS) and Density Surface Modelling (DSM). CDS generates a single density estimate for each stratum, whereas DSM explicitly models spatial variation and offers potential for greater precision by incorporating environmental predictors. Although DSM yields a more relevant product for the purposes of marine spatial planning, CDS has proven to be useful in cases where there are fewer observations available for seasonal and inter-annual comparison, particularly for the scarcely observed elephant seal. Abundance estimates are provided on a stratum-specific basis. Steller sea lions and harbour seals are further differentiated by ‘hauled out’ and ‘in water’. This analysis updates previous estimates (Williams & Thomas 2007) by including additional years of effort, providing greater spatial precision with the DSM method over CDS, novel reporting for spring and autumn seasons (rather than summer alone), and providing new abundance estimates for Steller sea lion and northern elephant seal. In addition to providing a baseline of marine mammal abundance and distribution, against which future changes can be compared, this information offers the opportunity to assess the risks posed to marine mammals by existing and emerging threats, such as fisheries bycatch, ship strikes, and increased oil spill and ocean noise issues associated with increases of container ship and oil tanker traffic in British Columbia’s continental shelf waters.
Starting with marine animal observations at specific coordinates and times, I combine these data with environmental data, often satellite derived, to produce seascape predictions generalizable in space and time. These habitat-based models enable prediction of encounter rates and, in the case of density surface models, abundance that can then be applied to management scenarios. Specific human activities, OWED and shipping, are then compared within a tradeoff decision support framework, enabling interchangeable map and tradeoff plot views. These products make complex processes transparent for gaming conservation, industry and stakeholders towards optimal marine spatial management, fundamental to the tenets of marine spatial planning, ecosystem-based management and dynamic ocean management.
Item Open Access Detection and Quantification of Single-walled Carbon Nanotubes in Environmental and Biological Samples for Evaluation of Fate, Transport and Bioaccumulation(2017) Liu, XuehongSingle-walled carbon nanotubes (SWCNT) are unique, anthropogenic allotropes of nanoparticulate black carbon. As numerous industrial and commercial uses of SWCNT result the heavy expansion of production of this material, the release of SWCNT is likely to occur, increasing their level in air, water and soil. SWCNTs have been shown to cause adverse impact in organisms from direct exposure through ingestion or inhalation. In addition to direct exposure, SWCNT can also induce toxicity to organisms by indirect exposure such as adsorption of hydrophobic contaminants (HOCs). One unique property of SWCNT is the quantized nature of their electronic structure, which is dependent on the chiral wrapping angle of the sp2 hybridized graphene sheet that comprises the wall of each SWNT species. Using probe HOCs – one planar polycyclic aromatic hydrocarbon (PAH)14 C-naphthalene and one halogenated aromatic 14 C-hexachlorobenzene and purified conductive and semiconductive SWCNT species, my first study aimed at assessing the role of SWCNT electronic structure on HOC sorption. Despite their differences in electronic structures, the results indicated that overall the electronic structure does not influence the adsorption of HOCs. However, due to the large specific surface area, SWCNT have a general high affinity for HOCs. Upon release of SWCNT into aquatic environment, SWCNT have the potential to affect the distribution of organic contaminants by acting as strong sorbent.
A significant barrier to studying toxicity of SWCNT to animal models is the lack of in vivo techniques to track and quantify SWCNT for assessing their distribution, transport and bioaccumulation. The fluorescence resulting from the unique band gap of each species of semiconductive SWCNT allows the detection and quantification of a bulky SWCNT sample using near infrared fluorescence spectroscopy (NIRF). NIRF is highly sensitive to detect SWCNT in biological tissues due to the low fluorescence in the near infrared region from biological samples. Two exposure routes were investigated using NIRF: ingestion from dietary track using fathead minnow (FHM) fish model in an aquatic environment and inhalation through lung using mouse model. The SWCNT extraction conditions were optimized and validated using spike recovery experiments. SWCNT were extracted from fish tissues, intestine, and liver using ultrasonic extraction in 2% sodium deoxycholate1extraction. Proteinase K digestion was needed for dissolving mouse lung prior to SDC extraction. The quantification results showed that while SWCNT readily passed through fish dietary track with minimal partition into the lumen tissue and caused no acute toxicity; SWCNT was less mobile in respiratory system and was responsible for the lung-term pulmonary disease induced.
The fate, transport and bioaccumulation of SWCNT are essential information for risk assessment and making environmental regulations for nanomaterials. Currently the lack of standardized sensitive characterization and quantitative analytical methods for SWCNT determination at the current levels in the environment is one major barrier for evaluation of their real impact to the environment. NIRF is sensitive for environmental samples. However, this technique is not sensitive to all types of SWCNT. Metal catalysts are widely used in synthetic production of SWCNTs, leading to total metal content ranging from 5 - 30%. The metal: metal ratios and metal: carbon ratios of SWCNT are very distinctive from many geological materials. A metal fingerprinting approach was developed by monitoring the metal type and metal: metal ratios, along with elemental carbon content. SWCNT can be principally quantified using inductive coupled plasma mass spectrometry (ICP-MS). Metal content, metal: metal ratios, elemental carbon and metal: carbon ratios were analyzed for two aerosol matrices, the urban dust NIST SRM 1649b and aerosol collected at Duke University using three types of SWCNT: SG65 SWCNT, SG65i SWCNT and P2 SWCNT. Results demonstrated that the metal finger approach worked well with all aerosol matrices with detection limits near ng m-3. It worked best with elements that were less abundant in the background such as Co and Y. This method offers a robust and economic approach for application to occupational spaces for monitoring possible SWCNT release.
Applying a similar approach in sediment presents a significant challenge as background metals present in sediment complicates such analyses. To overcome these challenges, we have applied density gradient ultracentrifuge (DGU) to isolate and separate SWCNT in sediment extracts prior to both NIRF and ICP-MS analysis. Several types of SWCNTs (arc discharge, CoMoCat, and HiPCO) were spiked and subsequently extracted from estuarine sediments. SWCNTs were separated into different bands after DGU, primarily into two distinct horizons (one showed near infrared fluorescence, while the other did not). Two techniques,near-infrared spectroscopy (NIRF) and ICP-MS, were applied for quantitation of SWCNTs in these bands. Results indicate excellent separation of SWCNT from interferences in sediments. We have also discovered an apparent disconnect between the metal catalyst particles and SWCNT during density gradient ultracentrifuge separation. It is clear that the SWCNT (within the NIRF band) is not physically associated with metal catalyst. This result was further confirmed using single-particle ICP-MS. Although DGU separation seems to be an outstanding method for isolating SWCNT from aquatic sediment for analysis, our current findings indicate that metal fingerprints derived from residual catalyst may not be a good tracer for SWCNT occurrence and fate in marine sediments, as the associated metal catalyst particles in SWCNT preparations might be transported in different ways relative to the SWCNT.
Overall, my research explored several analytical techniques to detect and quantify SWCNTs at their relevant concentration in various environmental matrices. These techniques will provide essential information for evaluating the environmental impact based on SWCNTs fate, transport and bioaccumulation in the environment.
Item Open Access Distribution, Transport, and Control of Mercury Released from Artisanal and Small-Scale Gold Mining (ASGM) in Madre de Dios, Peru(2016) Diringer, Sarah Elisa AxelrothMercury (Hg) is a globally circulating heavy metal released through both natural and anthropogenic sources. The largest anthropogenic source of mercury to the global atmosphere is artisanal and small-scale gold mining (ASGM). During the ASGM process, miners add elemental mercury to large quantities of sediment or soil in order to create gold-mercury amalgams that separate alluvial gold from the remaining geological host material. Miners then heat the amalgam using a blowtorch or similar device to separate the mercury and gold, exposing themselves to mercury vapor and releasing mercury to the environment. Following amalgam heating, mercury can deposit into aquatic ecosystems. There, anaerobic microorganisms can convert mercury to methylmercury (MeHg), a potent neurotoxin that rapidly accumulates in aquatic food webs. A high concentration of MeHg in fish poses serious human health risks, especially to pregnant women and children.
In Peru’s Region of Madre de Dios (MDD), mercury use for ASGM is widespread due to increasing global demand for gold. This region in the tropical Amazon is one of the world’s most biodiverse ecosystems and home to more than 150,000 Indigenous and non-Indigenous people, 40% of whom live below the poverty level. Recently, people living in the region have become more aware of negative impacts of Hg pollution through popular press. However, there is lack of controlled scientific studies to examine the environmental impacts of Hg from ASGM and subsequent exposures to surrounding communities.
This dissertation addresses four questions in order to better understand how mercury from ASGM impacts environmental health in Madre de Dios: (1) How is mercury distributed along the Madre de Dios River in areas of active ASGM activity, and what is the risk for mercury exposure to downstream communities? (2) How does land use change associated with ASGM activity affect soil-mediated mercury transport in the Colorado River, Madre de Dios, Peru? (3) Can sulfurized carbon be manufactured in a feasible way for developing countries and used to capture mercury during ASGM amalgam burning? (4) What is the mercury methylation potential of easy-to-manufacture spent, sulfurized carbon sorbents?
Despite significant information on the direct health impacts of mercury to ASGM miners, the impact of mercury contamination on downstream communities has not been well characterized, particularly in Madre de Dios. In this area, ASGM has increased significantly since 2000 and has led to substantial political and social controversy. The second chapter of this dissertation examines the spatial distribution and transport of mercury through the Madre de Dios River with distance from ASGM activity. It also characterizes risks for dietary mercury exposure to local residents who depend on fish from the river. River sediment, suspended solids from the water column, and fish samples were collected in 2013 at 62 sites near 17 communities over a 560 km stretch of the Madre de Dios River and its major tributaries. In areas downstream of know ASGM activity, mercury concentrations in sediment, suspended solids and fish within the Madre de Dios River were elevated relative to locations upstream of mining. Fish tissue mercury concentrations were observed at levels representing a public health threat, with greater than one-third of carnivorous fish exceeding the international health standard of 0.5 mg/kg. This research demonstrates that communities located hundreds of kilometers downstream of ASGM activity, including children and indigenous populations who may not be involved in mining, are at risk of dietary mercury exposure that exceed acceptable body burdens.
This research involved extensive field sampling in an active mining region and indicated suspended particulate transport may be an important source of mercury from mining areas to downstream communities. Chapter three of this research focused on understanding how land use changes can influence soil and sediment transport from mining regions. Within the MDD, a large portion of mining in concentrated within the Colorado River watershed. In the Colorado River watershed, mining and deforestation have increased dramatically since the 1980s, largely concentrated in the Puquiri subwatershed. Field sampling in Feb 2015 identified a strong correlation between Hg and suspended solids concentrations, with especially high suspended solids concentrations downstream of ASGM activity. This supported the hypothesis that Mercury transport in this region is facilitated by soil mobilization and runoff. In order to understand how ASGM activity in the Puquiri affects sediment mobilization from the watershed over time, we employed a watershed-scale soil mobilization model using satellite imagery from 1986 to 2014. The model estimated that soil mobilization in the Colorado River watershed increased by 2.5 times during the time period, and increased by six times in the Puquiri subwatershed, leading to between 10 and 60 kg of mercury mobilized in 2014. If deforestation continues at its current exponential rate through 2030, soil and heavy metal mobilization may increase by five times. This research shows that deforestation associated with ASGM in the Colorado River watershed can exacerbate soil mobilization and mercury contamination. While the impacts of mercury and deforestation are often considered separately, here we studied how deforestation associated with ASGM in the Madre de Dios region can significantly increase soil mobilization and mercury transport to downstream communities.
With a substantial portion of mercury releases coming from a non-industrialized process in developing countries, low-cost and low-tech mercury capture is becoming increasingly necessary. While impregnated activated carbon sorbents are well studied for mercury-capture in developed countries and large industrialized settings, there exist few suitable low-cost alternatives for mercury capture from artisanal and small-scale gold mining (ASGM) in developing countries. Chapter four sought to develop an easy-to-manufacture carbon sorbent using elemental sulfur and activated carbon or hardwood-based biochar for potential use during ASGM gold-amalgam heating. Consumer-grade sulfur powder was melted on granular activated carbon or hardwood biochar in a process feasible for a cook stove setting. Activated carbon and biochar were successfully sulfurized to more than 5% sulfur by weight using powdered, elemental sulfur. The sorbent products were tested for elemental mercury sorption from an air gas stream at room temperature. The sulfurized activated carbon achieved higher elemental mercury adsorption capacity in air stream (500 μg Hg m-3, 2 L min-2) relative to unsulfurized activated carbon and sulfurized biochar. Sorption isotherms were used to examine the sorption mechanism, and indicated that likely a pseudo first order reaction was occurring. This research provides a possible option for mercury control by modifying established mercury capture technologies to be easy to manufacture, locally available, and less hazardous to produce.
In Chapter 5 of this research, the sulfurized sorbents were examined further to understand methylation potential in sediment slurries. Anaerobic sediment slurries were constructed to examine methylmercury (MeHg) production of spent sorbents. Five sorbent types with approximately 10 mg/kg Hg each were added to slurries at 5 % by mass. Dissolved mercury was used as a control to simulate atmospheric deposition or highly reactive mercury. After a 5 d incubation at room temperature, MeHg production was ten times greater with low-technology sulfurized sorbents as compared to activated carbon or biochar alone. Sulfurized sorbents leached significantly more mercury than their non-sulfurized counterparts during desorption experiments and led to greater dissolved mercury concentrations. This research shows that low-cost mercury-contaminated sorbents can have unintended consequences with increased MeHg production and potential for more harm to local communities than atmospheric release.
Mercury releases from ASGM are expected to grow, leading to higher concentrations of mercury in the atmosphere that may affect ecosystems throughout the globe. Understanding the importance of mercury from ASGM to toxicity and accumulation requires in depth research on mercury transformations and MeHg production associated with ASGM. This research examines mercury distribution and transport from ASGM active regions. It identifies that deforestation, erosion, and particulate transport play important roles in overall mercury transport, leading to hazardous mercury concentrations downstream of ASGM activity. Effective point-of-use mercury capture technologies would dramatically decrease the mass of mercury released to the environment. The final chapters of this research serve as a proof of concept for using sulfurized activated carbon for mercury capture in developing countries.
Our research team has built strong relationships with several governmental and non-governmental organizations in Peru who will aid in distributing information. This research will provide invaluable environmental health information to residents, inform political intervention, and reveal a new potential avenue for low-cost mercury control.
Item Open Access Duke University and the Nicholas School: Encouraging today's youth through environmental education(2013-04-23) Greene, ChaquettaEnvironmental education programs and curriculum have been a crucial part of earth and science education since the mid-1970s. With the increasing scope of environmental issues in the US and worldwide, it is important to prepare our youth to solve pressing environmental problems. This study documents K-12 environmental education initiatives in Durham county public schools sponsored by the Duke University community, including and earth science departments and the Nicholas School of the Environment. The scope, pedagogical approach, and process of development of these initiatives are noted. Moreover, this study offers recommendations for both Duke and the Nicholas School of the Environment based on current academic literature and similar outreach programs at other universities such as the inclusion of training and enhanced professional development for in-service teachers and increased emphasis on service-learning and nature based instructional approaches.