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Volatile organic compounds (VOCs) are those chemical species having sufficiently high vapor pressures to exist largely or entirely in the gaseous phase, whereas reactive organic carbon (ROC) encompasses all organics except methane. ROC can be emitted biogenically and anthropogenically, usually in a pure hydrocarbon form that is susceptible to reaction with common atmospheric oxidants such as hydroxyl and ozone in the initial steps to the formation of particulate matter, the criteria pollutant most strongly implicated in human mortality. The diversity of both the emitted VOCs and their possible atmospheric reactions yields countless different compounds existing in the atmosphere with a correspondingly wide range of volatility, solubility, reactivity, etc.. Moreover, the temporal and spatial variability of a given analyte is often large. Real-time chemical characterization of gaseous and particulate organic compounds can be achieved by instrumentation utilizing chromatographic and/or mass spectrometric techniques, but these methods are expensive, often logistically challenging, and require high levels of skills for both operation and data analysis. Conversely, filter-based measurements for organic particulates are inexpensive and straightforward, but do not give real-time data and analytes may be lost or transformed before analysis. There is a niche for robust, low-maintenance, moderate-cost instrumentation that offers chemical information on atmospheric carbon. Presented here are two projects that develop and validate instrumentation for measuring ROC. The first combines flame ionization detection (FID) with a CO2 detector to estimate the O/C ratios of sampled gases and particulates. O/C ratios are a particularly valuable piece of chemical information as higher ratios give lower volatility and higher solubility, meaning increased propensity to partition into the condensed phase. The second project utilizes portable VOC samplers with sorbent tubes that trap and protect analytes for detailed analysis. The samplers' portability and programmable microcontrollers offers the investigator great flexibility, both spatially and temporally. A third project analyzed the chemical composition of commercially available fragrance mixtures and modeled their emissions' impact on oxidant reactivity. It was observed that terpenes, despite their low mole fractions in the mixtures, represent the vast majority of emitted reactivity and are quantitatively evolved from the mixtures in a matter of hours. / Doctor of Philosophy / Organic (i.e., carbon-containing) compounds are emitted into the atmosphere from a variety of natural and anthropogenic sources. Respective examples would include the agreeable aroma of a pine forest (from terpene compounds) or the pungent smell of gasoline (from additives such as toluene). These emitted compounds are often pure hydrocarbons (molecules formed of carbon and hydrogen atoms), and the category VOCs (volatile organic compound) encompasses hydrocarbons and the products of their chemical reactions with atmospheric oxidants like the hydroxyl radical and ozone. In the presence of pollutant nitrogen oxides, oxidants modify these VOCs; adding oxygen lowers the VOCs' vapor pressure and increases aqueous solubility, resulting in higher likelihood of condensation from the gaseous phase into particulates (liquid or solid phases). "Smog" is a colloquial term for the entire suite of noxious chemical compounds produced in the air from reactions of largely anthropogenic organic precursors. Particulates, a.k.a. aerosols, are the most concerning atmospheric pollutant due to deleterious effects on respiratory and cardiovascular health and has shown strong correlations with increased mortality in exposed groups such city dwellers. Determining the chemical identities of the VOCs is useful for pollution forecasting and possibly identifying and quantifying VOC sources. Current methods for chemical identification are cumbersome, expensive, complex, and wholly unsuitable for many investigators. In this work, we introduce two new approaches to gathering chemical information about organic gases and particulates. The first instrument has been demonstrated to give accurate estimates of oxygen/carbon (O/C) ratios; higher O/C ratios represent higher propensities to condense into particulate forms. The second instrument developed is a portable VOC sampler, which traps (and prevents reaction of) a broad range of organics on a sorbent (such as activated charcoal) in a small metal tube. After sampling in remote locales, the tubes can be analyzed in the lab and the VOCs identified and quantified. The third study investigated the chemical composition of fragrance mixtures (present in perfumes, cleaning agents, etc.) and modeled (i.e., estimated) VOC emissions based on the fragrance components as well as the effects on atmospheric oxidant levels. Fragrance mixtures represent a significant source of atmospheric carbon, so a more thorough understanding of the fragrances' impacts on oxidant levels gives further insight into atmospheric processes and aerosol formation.

Rivers are a significant source of particulate and dissolved organic carbon (POC, DOC) into inland waters and coastal systems and provide a fundamental linkage between the terrestrial, oceanic, and atmospheric carbon reservoirs. Recent studies have examined the relationship between the quantity and form (POC vs. DOC) of carbon delivered to the aquatic system; however, little is known about the age of POC and DOC exported and how the radiocarbon age may vary with latitude, topographic gradient, vegetation, and land use. I provide the first global synthesis of published radiocarbon values of POC and DOC (∆14C). Inclusion of DOC and POC parameters (µM, δ13C, ∆14C) reveal significant driving forces of DOC (µM), latitude, and elevation (m) as capable of explaining 25% of the variability in DO14C in rivers and POC (µM) and latitude accounting for 15% of the variability in PO14C. When δ13C of DOC and POC and latitude were incorporated with ∆14C of DOC observations, 61% of the variability in DOC age was explained revealing the necessity to include dissolved and particulate fractions of organic carbon to yield the most robust predictive models. This study found a global trend of increasing age of DOC and increasing δ13C of DOC and POC with increasing latitude. My study suggests future research should incorporate both particulate and dissolved OC parameters along with elevation, vegetation, land cover, and climate zones to increase understanding of what drives the age of carbon exported in riverine systems.

Because of high intense population is in Taiwan, households water use requires a considerable amount. It is substantially reduce daily water use to share primary water resources, if we can reclaim domestic wastewater properly and make it support. Currently, reclaiming water is an emerging requirement for management and application. If we can adequately monitor and treat reclaimed water, reducing environmental contaminants, costs, and environmental feedback is possible. The study treated domestic wastewater of Feng-Shan river using GAC trickling filter with two column in a series and the removal efficiency of organic carbon was observed. The experimental results indicated that removal efficiency of organic carbon concentration was decreased as the empty-bed contact time (EBCT) increased. The best average removal efficiency of TOC and DOC was about 72% and 78%. According to the TOC removal rates using GAC at different temperatures, the TOC removal rates at room temperature and 4¢Jwere respectively 95% and 90% in the first column of the experiment and 85% and 80% in the second column. The removal rates of dissolved organic carbon (DOC) using GAC folter system at room temperature and 4¢J were respectively 95% and 90% in the first column of the experiment and 90% and 87% in the second column. Obviously,the TOC removal rate treated using GAC filter system at room temperature was superior to that treated at 4¢J In comparing treated water and recycled water,most of the water quality parameters (temperature¡BSuspended solids¡BBOD¡BCOD¡BpH) were to meet recycled water quality standards.However, the system due to use GAC trickling filter system treatment that easily decrease dissolved oxygen in treated water but conductivity in treated water without changes. These two water parameters were failed to meet the recycled water standards. By the way, we found trained GAC through SEM irradiation the biofilm area of trained GAC surface at 25¢Jwas superior to that treated at 4¢J. It corresponds to the removal efficiency of organic carbon, the removal efficiency of 25¢J was higher than result of 4¢J. Therefore, a certain relationship between the biofilm area and removal efficiency of organic carbon is existed in this work.

The Bryan/College Station (B/CS) region has been reported to have elevated concentrations of dissolved organic carbon (DOC) in surface water. Increased DOC concentrations are worrisome as DOC has been shown to be an energy source for the recovery and regrowth of E. coli and many watersheds are impaired by high bacteria levels. To examine the sources and fates of DOC in rural and urban regions to better understand DOC movement though the environment, seven watersheds were studied. To investigate source, streams were analyzed using diffuse reflectance near infrared spectroscopy (DR-NIR) and carbon isotopes. Fate of DOC was determined through monthly streams samples, gathered between March 2011 and February 2012, which were incubated for biodegradable DOC (BDOC). Soil in the region was sampled based on land use categories. Soil was analyzed for DOC and BDOC as well as DOC adsorption, the other major fate of DOC. Above ground vegetation was sampled in conjunction with soil and analyzed for BDOC. Data indicated that fecal matter from cliff swallows provided considerable organic material to streams in the B/CS region as shown through DR-NIR. Carbon isotope values in streams ranged from -23.5 +/- 0.7% to -26.8 +/- 0.5%. Stream spectra may be able to predict carbon isotope values in streams (Adj. R2 = 0.88). Mean annual stream DOC concentrations ranged from 11 +/- 3 mg/L to 31 +/- 12 mg/L, which represents a significant decrease in DOC between 2007 and 2011. Concurrent increases in pH and conductivity were also recorded. The decrease in DOC and the increases in pH and conductivity may be due to impacts of high sodium irrigation tap water. Biodegradable DOC was low in streams, which is likely due to DOC being present in streams in refractory forms that are resistant to microbial breakdown. Soil chemistry, including soil adsorption, was greatly influenced by sodium. The elevated adsorption coefficients and release values seen in highly developed and urban open areas can be attributed to frequent exposure to high sodium irrigation water. The results indicate that sodium is a major driver of DOC in the system. Sound management decisions concerning irrigation water chemistry and urban development might eventually emerge to protect water quality as a result of this research.

Reductive dechlorination is a significant natural attenuation process in chloroethene-contaminated aquifers where organic carbon combined with reducing redox conditions support active dechlorinating microorganisms. At sites where natural organic carbon (NOC) associated with the aquifer matrix provides fermentable organics, the ability to measure the NOC is needed to assess the potential for the long-term sustainability of reductive dechlorination. This study focused on developing a method to measure the potentially bioavailable organic carbon (PBOC) associated with aquifer sediment. To measure NOC and evaluate its biodegradability, liquid extraction techniques on aquifer sediment were investigated. Single extractions with different extracting solutions showed that extractable organic carbon associated with the sediment ranged from 1-38% of the total organic carbon content (TOCs). Bioassay experiments demonstrated that 30-60% of the extractable organic carbon can be utilized by a microbial consortium. Alternating between 0.1% pyrophosphate and base solutions over multiple extractions increased the rate of removal efficiency and targeted two organic carbon pools. The result of the investigation was a laboratory method to quantify organic carbon from the aquifer matrix in terms of the PBOC. In the second part, the extractable PBOC was shown to biodegrade under anaerobic conditions, to produce H2 at levels necessary to maintain reductive dechlorination, and to support reductive dechlorination in enrichment cultures. For the third part of the research, the difference in extractable organic carbon inside and outside of a chloroethene-contaminated plume was examined through the combination of PBOC laboratory data and field parameters. Supported by ground-water constituent data, the PBOC extraction and bioassay studies showed that less extractable organic carbon was present inside than outside of the chloroethene plume. The final part of the research investigated the distribution of PBOC extractions across six contaminated sites. PBOC extractions were directly correlated to the TOCs, soft carbon content, and level of reductive dechlorination activity at the sites. Based on these correlations, a range for organic carbon potentially available to subsurface microorganisms was proposed where the upper bound consisted of the soft carbon and the lower bound consisted of the PBOC. / Ph. D.

Groundwater remediation strategies have advanced toward more effective and economical remedial technologies. Monitored natural attenuation (MNA) has become accepted by federal regulatory agencies as a viable remediation strategy for contaminants under site-specific conditions. At chloroethene contaminated sites where MNA is used as a remediation strategy, microbially-mediated reductive dechlorination is typically the dominant pathway for natural attenuation. The efficacy of reductive dechlorination at sites with no anthropogenic carbon sources is often influenced by the availability of readily-biodegradable natural organic carbon along with favorable geochemical conditions for supporting microbial dehalogenation. Recent research studies have suggested that the pool of labile natural organic carbon, operationally defined as potentially bioavailable organic carbon (PBOC), may be a critical component related to sustaining reductive dechlorination at MNA sites. The objective of this study was to evaluate PBOC as a quantitative measure of the labile organic carbon fraction of aquifer sediments in relation to microbial reductive dechlorination of chlorinated solvents. In the first phase of this study, the variability of PBOC in aquifer sediments was examined among 15 chloroethene contaminated sites. Results showed that PBOC displayed considerable variability among the study sites, ranging over four orders of magnitude. Regression results demonstrated that a positive correlation existed between PBOC, solid phase total organic carbon (TOCs), and reductive dechlorination activity at the sites. Results supported that greater levels of PBOC and TOCs corresponded to higher reductive dechlorination activity at the sites. Composition results showed that 6-86% of PBOC consisted of proteins and amino acids. Results also suggested a positive relationship existed between PBOC, concentrations of potentially bioavailable organic compounds present in the aquifer system, expressed as hydrolyzable amino acids (HAA), and the natural attenuation capacity (NAC) at the sites. Higher PBOC levels were consistently observed at sites with greater NAC and levels of HAA. The results of this study suggested that the variability of PBOC in the aquifer sediments exhibited a reasonable correlation with TOCs, hydrolyzable amino acids, and chloroethene transformation among the selected sites. In the second phase of this study, the relationship between PBOC in aquifer sediments and site specific performance data was evaluated among 12 chloroethene contaminated sites. Results demonstrated that PBOC in aquifer sediments was directly correlated to independent field metrics associated with reductive dechlorination. Levels of PBOC demonstrated direct relationships with hydrogen (H2) and dissolved oxygen (DO) concentrations within the groundwater system at the selected study sites. Results also indicated that PBOC demonstrated positive relationships with reductive dechlorination activity and the natural attenuation capacity of the sites. The findings of this study suggested that the level of PBOC in aquifer sediments may be a key factor in sustaining conditions favorable for microbial reductive dechlorination. In the third phase of this study, the distribution of PBOC was investigated at a chloroethene contaminated site. PBOC was measured in surficial aquifer sediment samples collected at varying depths in the vicinity of a chloroethene plume. Results demonstrated that levels of PBOC were consistently higher in aquifer sediments with minimal chloroethene exposure relative to samples collected in the PCE-contaminated source zone. Regression results demonstrated that a statistically significant inverse correlation existed between PBOC levels and chloroethene concentrations for selected temporary wells in the contaminated source zone at the study site. Consistent with these findings, results also indicated a similar trend of increased PBOC in aquifer sediments outside the chloroethene plume relative to aquifer sediments inside the plume. Results from this study further suggested that differences in extracted carbon levels at the site for surficial aquifer sediment samples in the PCE-contaminated source zone could impact the extent of reductive dechlorination within the hydrographic unit. / Ph. D.

Northern peatlands represent a significant carbon reservoir, containing approximately a third of the terrestrial carbon pool. The stability of these carbon stores is poorly understood, and processes of accumulation and degradation appear to be finely balanced. Over the last decade, it has become increasingly clear that losses of dissolved organic carbon (DOC) from peatlands can be of considerable size and this flux appears to have increased substantially over the last 20 years. Despite its significance, the chemical composition of peatland-derived DOC remains poorly understood. This study aimed to characterise dissolved organic matter (DOM) at the molecular level using a novel combination of techniques. The study site (Cors Fochno, Wales, UK) is an ombrotrophic bog on which a number of studies into carbon cycling and hydrology have been carried out, providing a useful context for this project. The size and compositions of the DOC pool was monitored over 18 months, from three banks of piezometers, sampling from depths of 15 cm to 6 m. DOM which is representative of bog runoff was also monitored. DOC concentrations varied considerably between locations, spanning an order of magnitude (11.4 to 114 mgC l-1). Several relationships between DOC concentration and environmental and physical factors were established: DOC levels near the surface of the peatland varied with temperature, those in the runoff were most affected by recent rainfall events and the apparent DOC concentration at depth was related to the hydraulic conductivity of peat at that depth. The annual flux of DOC from the site was estimated at 113 tonnes, or 17.4 gC m-2. Only a small portion of the DOC pool could be characterised by analysis of dissolved combined amino acids (DCAA) and dissolved carbohydrates (as neutral sugars). Non-protein amino acids were most abundant in runoff samples, suggesting microbial reworking of DOM on entering drainage systems. DCAA yields decreased with depth, and the DCAA pool in deeper peat layers was characterised by more hydrophobic compounds. Interpretation of semi-quantitative results from TMAH thermochemolysis GC-MS analysis suggested oxidative degradation of organic matter near the surface of the peatland and photochemical degradation where DOM entered drainage networks, and this was supported by novel interpretation of results from ultrahigh resolution mass spectrometry analysis. The deepest porewaters were dominated by nalkanes, with notable contributions from fatty acids, suggesting a plant wax source for this DOM. The highest DOC concentrations were found at intermediate depth from a site midway between the centre of the bog and the southern boundary where hydraulic conductivities were low, and DOM from these piezometers were characterised by high contributions from a suite of phenolic compounds (with mainly para-hydroxyphenyl structures). These compounds have been linked to Sphagnum species, and are known to be functionally important to the development and maintenance of the unusual chemical environment in peatlands which slows decay rates, reduces microbial activity, and allows the sequestration of the large carbon reservoir. The findings of this study highlight the dynamic nature of peatland derived DOM, both in the size of the carbon pool and its composition which change dramatically with both season and depth.

The effects of predicted future climate change was investigated with special emphasis on the association of organic contaminants with dissolved organic carbon (DOC) in the Baltic Sea. An automated method was developed for the measurements of DOC - water distribution constants at realistic DOC concentrations in brackish water. The method proved to be valid for 30 organic contaminants with different structural elements in the 5 – 100 mg car bon/L DOC concentration range. There were limitations of this method. Firstly, its applicability is limited towards contaminants with lower affinity to DOC. Secondly, at higher (>100 mg carbon/L) DOC concentrations the sorption of contaminants was underest imated. Afterwards, water samples were collected from 15 points within the Baltic Sea in a north - south gradient t o examine the spatial differences in DOC characteristics and sorption properties . The DOC samples were analyzed using proton nuclear magnetic resonance and ultraviolet spectroscopy. Results from both techniques indicated that the aromatic nature of the DOC pool increased towards the northern Baltic Sea. This was expected as the freshwater inflow has high significance in controlling the hydrograp hic conditions in the Bothnian Bay. Sorption of organic contaminants was subsequently measured in the same samples. The results showed decreased sorption from north to south for hydrophobic contaminants such as chlorinated benzenes but for contaminants lik e tributyl - phosphate no spatial tendencies were observed. The data generated was used to determine molecular descriptors of DOC using linear free energy relationships. The results indicated a higher significance of hy drogen bond donor/acceptor functional g roups of the DOC in the south. Changes in contaminant distribution were simulated in model pelagic ecosystems at possible endpoints predicted by future climate change scenarios. Separate and combined effects of temperature a nd DOC were studied in mesocosms. The results indicated interesting tendencies. Increased temperature resulted in increased losses in the amounts of organic contaminants. Increased DOC levels promoted sedimentation and sorption of contaminants to particulate matter and biota. Hi gher amounts of contaminants were retained. The combined effects of the two factors led to and overall decrease in dissolved amounts. Higher losses or increased sedimentation and sorption to particles were also observed depending on contaminant properties. / EcoChange

Paleosols contain information about the rates of soil organic carbon turnover when the soil was actively forming. However, this temporal information is often difficult to interpret without tight stratigraphic control on the age of the paleosol. Here we apply ramped pyrolysis/oxidation (Ramped PyrOx) C-14 analyses to evaluate age spectra of transgressive early Holocene paleosols from the Mississippi Delta in southeastern Louisiana, USA. We find C-14 age spectra from soil organic matter (SOM) in both paleosols and overlying basal peats that represent variability in age that is close to, or only slightly greater than, analytical uncertainty of C-14 measurements, despite different sources of carbon with likely disparate ages. Such age spectra have not previously been observed in the sedimentary record. Here they indicate vigorous soil carbon turnover prior to burial, which homogenized C-14 ages within SOM across the entire thermochemical spectrum. The weighted bulk C-14 ages from Ramped PyrOx of paleosols and overlying peats are identical within analytical and process-associated uncertainty, and corroborate C-14 ages from charcoal fragments and plant macrofossils from the overlying peat. The youngest ages from Ramped PyrOx age spectra may also potentially be applied as chronometers for stratigraphic burial ages. Our results suggest rapid turnover (<<300 years) of carbon in these soils relative to input of allochthonous carbon, indicating that the C-14 age of different soil components is decoupled from thermochemical stability and instead reflects vigorous turnover processes. The concurrence of paleosol and peat C-14 ages also suggests that pedogenic processes were linked with the development of coastal marshes, and that the priming effect potentially masked the signal of allochthonous carbon inputs during sea level rise.