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The work presented here represents a number of independent studies that investigated various components of the CH4 budget, namely the sources and sinks. We used a chemical-tracer model and created unique long-term time series of atmospheric CH4, carbon monoxide (CO), molecular hydrogen (H2), and methylchloroform (CH3CCl3) measurements at marine background air to derive histories of atmospheric hydroxyl radical (OH) - the main chemical oxidant of CH4, biomass burning - an important source of CH4 in the tropics, and emissions of CH4 from rice paddies - one of the largest anthropogenic sources of CH4, over decadal scales. Globally gridded inventories of CH4 emissions from rice paddies and terrestrial vegetation were created by synthesizing greenhouse and field CH4 fluxes, satellite-derived biophysical data, and terrestrial geospatial information.

The effect of global warming on methane (CH₄) and nitrous oxide (N₂O) emissions from agriculture was investigated and simulated from a soil warming experiment. Experiments were designed and installed in a temperature controlled greenhouse. The relationships between elevated temperatures and CH₄ and N₂O emissions were determined and calculated as the Q₁₀s of production, emission and oxidation. A study of the populations of methanogens and methanotrophs at a range of soil temperatures was performed based on soil molecular DNA analysis. This study showed that global warming would increase CH₄ emissions from rice agriculture and that the resultant emissions will be potentially large enough to cause changes in the present atmospheric concentrations. This research also showed that this increase was most evident for soil temperatures below 30⁰C, above which emissions decreased with increasing temperature. The seasonal average Q₁₀s of CH₄ emission, production, oxidation, methanogen and methanotroph populations were found to be 1.7, 2.6 and 2.2, 2.6 and 3.8, respectively, over a temperature of 20-32⁰C. Considering that the processes of CH₄ production and emission are similar to those in natural wetlands, which is the largest source of atmospheric CH₄, the contribution of this feedback is likely to cause a significant increase to the present CH₄ atmospheric budget if the current global warming trend persists over the next century. The Q₁₀s of N₂O emissions and production were 0.5-3.3 and 0.4-2.9, respectively. The low Q₁₀ values found for N₂O suggest that although global warming will have a direct impact on the production and emission rates. Nevertheless, the magnitude of the impact of global on both CH₄ and N₂O emissions from agriculture is likely to vary from one region to another due to the spatial variations in agricultural soil temperatures and the likely changes in the global regional distribution of water resources (water tables, rainfall patterns), water management practices and the responses of terrestrial CH₄ and N₂O sources such as natural wetlands and plants.

Methane (CH4) is one of the most important greenhouse gases after water vapor and carbon dioxide due to its high concentration and global warming potential 25 times than that of CO2 (based on a 100 year time horizon). Its atmospheric concentration has more than doubled from the preindustrial era due to anthropogenic activities such as rice cultivation, biomass burning, and fossil fuel production. However, the rate of increase of atmospheric CH4 (or the growth rate) slowed from 1980 until present. The main reason for this trend is a slowdown in the trend of CH4 sources. Measuring stable isotopes of atmospheric CH4 can constrain changes of CH4 sources. The main goal of this work is to interpret the CH4 trend from 1978-2010 in terms of its sources using measurements of CH4 mixing ratio and its isotopes. The current work presents the measurements and analysis of CH4 and its isotopes (δ13C and δD) of four air archive sample sets collected by the Oregon Graduate Institute (OGI). CH4 isotope ratios (δ13C and δD) were measured by a continuous flow isotope ratio mass spectrometer technique developed at PSU. The first set is for Cape Meares, Oregon which is the oldest and longest set and spans 1977-1999. The integrity of this sample set was evaluated by comparing between our measured CH4 mixing ratio values with those measured values by OGI and was found to be stable. Resulting CH4 seasonal cycle was evaluated from the Cape Meares data. The CH4 seasonal cycle shows a broad maximum during October-April and a minimum between July and August. The seasonal cycles of δ13C and δD have maximum values in May for δ13C and in July for δD and minimum values between September-October for δ13C and in October for δD. These results indicate a CH4 source that is more enriched January-May (e.g. biomass burning) and a source that is more depleted August-October (e.g. microbial). In addition to Cape Meares, air archive sets were analyzed from: South Pole (SPO), Samoa (SMO), Mauna Loa (MLO) 1992-1996. The presented δD measurements are unique measured values during these time periods at these stations. To obtain the long-term in isotopic CH4 from 1978-2010, other datasets of Northern Hemisphere mid-latitude sites are included with Cape Meares. These sites are Olympic Peninsula, Washington; Montaña de Oro, California; and Niwot Ridge, Colorado. The seasonal cycles of CH4 and its isotopes from the composite dataset have the same phase and amplitudes as the Cape Meares site. CH4 growth rate shows a decrease over time 1978-2010 with three main spikes in 1992, 1998, and 2003 consistent with the literature from the global trend. CH4 lifetime is estimated to 9.7 yrs. The δ13C trend in the composite data shows a slow increase from 1978-1987, a more rapid rate of change 1987-2005, and a gradual depletion during 2005-2010. The δD trend in the composite data shows a gradual increase during 1978-2001 and decrease from 2001-2005. From these results, the global CH4 emissions are estimated and show a leveling off sources 1982-2010 with two large peak anomalies in 1998 and 2003. The global average δ13C and δD of CH4 sources are estimated from measured values. The results of these calculations indicate that there is more than one source which controls the decrease in the global CH4 trend. From 1982-2001, δ13C and δD of CH4 sources becomes more depleted due to a decrease in fossil and/or biomass burning sources relative to microbial sources. From 2005-2010, δ13C of CH4 sources returns to its 1981 value. There are two significant peaks in δ13C and δD of CH4 sources in 1998 and 2003 due to the wildfire emissions in boreal areas and in Europe.

The overall goal of this work was to investigate microbial activity leading to the anaerobic degradation of polycyclic aromatic hydrocarbons and an organophilic clay sediment cap used at a creosote-contaminated Superfund site. To determine whether or not PAHs were being degraded under anaerobic conditions in situ, groundwater and sediment porewater samples were analyzed for metabolic biomarkers, or metabolites, formed in the anaerobic degradation of naphthalene (a low-molecular weight PAH). In addition, a groundwater push-pull method was developed to evaluate whether the transformation of deuterated naphthalene to a deuterated metabolite could be monitored in situ and if conservative rates of transformation can be defined using this method. Metabolites of anaerobic naphthalene degradation were detected in all samples that also contained significant levels of naphthalene. Anaerobic degradation of naphthalene appears to be widespread in the upland contaminated aquifer, as well as within the adjacent river sediments. A zero-order rate of transformation of naphthalene-D₈ to naphthoic acid-D₇was calculated as 31 nM·d-¹. This study is the first reported use of deuterated naphthalene to provide both conclusive evidence of the in situ production of breakdown metabolites and an in situ rate of transformation. Methane ebullition was observed in areas of the sediment cap footprint associated with organophilic clay that was used a reactive capping material to sequester mobile non-aqueous phase liquid (NAPL) at the site. Anaerobic slurry incubations were constructed using sediment core samples to quantify the contribution of the native sediment and the different layers of capping material (sand and organophilic clay) to the overall methane production. Substrate addition experiments using fresh, unused organophilic clay, as well as measured changes in total carbon in organophilic clay over time supported the hypothesis that microbes can use organophilic clay as a carbon source. Quantitative PCR (qPCR) directed at the mcrA gene enumerated methanogens in field samples and incubations of native sediment and capping materials. Denaturing gradient gel electrophoresis (DGGE) was also performed on DNA extracted from these samples to identify some of the predominant microorganisms within the sediment cap footprint. The organophilic clay incubations produced up to 1500 times more methane than the native sediment and sand cap incubations. The organophilic clay field sample contained the greatest number of methanogens and the native sediment contained the least. However, the native sediment incubations had greater numbers of methanogens compared to their respective field sample and comparable numbers to the organophilic clay incubation. An increase in methane production was observed with the addition of fresh, unused organophilic clay to the already active organophilic clay incubations indicating that organophilic clay stimulates methanogenesis. In addition, organophilic clay retrieved from the field lost about 10% of its total carbon over a 300-day incubation period suggesting that some component of organophilic clay may be converted to methane. DGGE results revealed that some of the predominant groups within the native sediment and sediment cap were Bacteriodetes, Firmicutes, Chloroflexi, and Deltaproteobacteria. An organism 98% similar to Syntrophus sp. was identified in the organophilic clay suggesting this organism may be working in concert with methanogens to convert the organic component of organophilic clay ultimately to methane. The capacity of organophilic clay to sequester organic contaminants will likely change over time as the organic component is removed from the clay. This, in turn, affects the use of this material as a long-term remedial strategy in reduced, contaminated environments.

Although the dynamics of methane (CH4) emission from croplands and wetlands have been fairly well investigated, the contribution of trees to global methane emission and the mechanisms of tree transport are relatively unknown. Methane emissions from the common wetland tree species Populus trichocarpa (black cottonwood) native to the Pacific Northwest were measured under hydroponic conditions in order to separate plant transport mechanisms from the influence of soil processes. Roots were exposed to methane enriched water and canopy emissions of methane were measured using a canopy enclosure. Methane accumulation in the canopy was generally linear and the average canopy methane flux was 3.0 ± 2.6 μg CH4 min-1. Flux magnitudes from stem experiments scaled to the area of the main tree stem are comparable to whole-canopy flux values, indicating that the majority of methane emitted from the tree leaves through the stem. Samples for stable carbon isotope composition were taken during the canopy experiments. Compared to the isotopic composition of root water methane, canopy methane was depleted in 13C on average by 8.6 ± 3.3 permil; this indicates that methane moving through the tree is not following a purely bulk flow pathway (where no depletion would occur), but is instead subject to at least one fractionating mechanism. When temperature was varied, the flux at the coolest temperature was significantly different from the higher flux at the warmest temperature (p-value less than 0.02). The calculated Q10 for methane flux was 2.4, which indicates a positive feedback with temperature increase. Analysis of δ13C values of emitted CH4 in the temperature experiments shows increasing depletion with cooler temperatures and lower flux. This indicates that not only does the magnitude of flux vary with temperature, but the actual dominant transport mechanism changes as well.

M.Sc.(Eng.), Faculty of Engineering and the Built Environment, University of the Witwatersrand, 2011

This dissertation consists of three essays in the field of environmental economics. The first chapter provides the first causal evidence that hostile activities online lead to physical violence. Given the recently documented relationship between pollution and social media, I exploit exogenous variation in local air quality as the first step to instrument for online aggression. In an event study setting, I find volatile organic compounds (VOCs) increase by 7% when refineries experience unexpected production outages. Together with higher air pollution, I find more aggressive behaviors both online and offline, as well as worse health outcomes near refineries. A one standard deviation increase in surrounding VOCs leads to 0.16 more hate crimes against Black people and 0.23 more hospital visits per thousand people each day. Second, I consider how emotional contagion spreads through social networks. On days with pollution spikes, surrounding areas see 30% more offensive and racist tweets and 12% more crimes; those geographically distant but socially networked regions also see offensive and racist tweets increase by 3% and more crimes by 4.5%. Nationally, overlooking spillovers would underestimate crime effects of pollution by 24%. My findings highlight the consequences of social media hostility and contribute to the public debate on cyberspace regulation. The second chapter, which is coauthored with Andrew Wilson, analyzes the relationship between weather and railway accidents. Rail thermal expansion and contraction are key considerations in rail design and construction; rail operators and rolling stock may likewise exhibit vulnerability to temperature changes. We quantify the sizes of these effects by leveraging a comprehensive dataset of railway malfunctions in the United States spanning 1997-2019. We find that both heat and cold cause elevated rates of railway malfunctions, with relatively larger increases in the number of incidents leading to a casualty as well as the number of injuries and deaths resulting from these incidents. We find that exposure to daily temperatures averaging over 30°C (86°F) leads to a 16% increase in the number of rail malfunctions, a 13% increase in the number of incidents leading to a casualty, and 18% and 36% increases injuries and deaths-effects net of any operational adjustments made to mitigate these effects. Further, while we also find that warmer locations exhibit a weaker relationship between heat and railway malfunctions, we find no evidence that companies are learning, year-over-year, how to reduce accidents. Finally, we note that effects of heat are strongest for derailments (versus other types of malfunctions) and freight trains (versus passenger trains). Our findings highlight the vulnerability of the railway system to the climate. The number of injuries and deaths associated with weather exposure-especially in comparison to operators' reported private costs of equipment failure-suggests a role for enhanced rail safety regulations and adaptation funding to protect critical heat-exposed infrastructure. The third chapter, which is a joint work with Douglas Almond and Muye Ru, explores the impact of federal policy rollback on methane leakage. Improvements in satellite measurement enable independent assessment of regulatory and climate policy. In August 2020, the Trump Administration lifted Obama-era requirements that oil and gas firms detect and repair methane leaks. We merge geo-identified data from the European TROPOMI (satellite instrument) to the specific locations of the US oil and gas infrastructure. Using a difference-in-differences design, we find a prompt increase in US methane emissions following the summer 2020 rollback. The number of high-methane emission events from the oil and gas sector more than doubled after the rollback relative to the coal sector, which did not experience the same regulatory rollback. While the oil and gas industry claims it faces a persistent, profit-making incentive to stem natural gas leaks and emissions, we find a large and nimble response by industry to changes in federal policy. Public policies that reduce methane externalities are critical given that global methane concentrations are rising at an increasing rate.