This research addressed the question whether a constructed wetland system with phytoremediation could successfully uptake 1,4-Dioxane in groundwater and secondary effluent. It further addressed whether open pond storage could successfully treat wetland discharge. The project was located at the University of Arizona's Constructed Ecosystems Research Facility (CERF) in Tucson, Arizona. This two-year field study was motivated by previous laboratory studies which demonstrated the capability of plants to remediate the recalcitrant contaminant 1,4-Dioxane.The study was conducted in two open steel tanks configured to simulate constructed wetlands. The efficacy of 1,4-Dioxane uptake by cottonwood trees was tested in a side-by-side comparison utilizing planted and unplanted tanks. The sub-surface hydraulic conditions were fully characterized by bromide tracer studies. Six experiments were conducted, in which tapwater or secondary effluent was spiked with 5.2 mg/L 1,4-Dioxane and fed to the planted and unplanted (control) tank. The tank discharges were retained in separate open ponds to test if open pond storage would reduce 1,4-Dioxane content. Additional side experiments were conducted to examine the role of volatilization and UV degradation. Comparison of 1,4-Dioxane mass discharge from the planted and the control tank demonstrated an 18-48 percent uptake by the cottonwood trees. Mass balance assessments showed 1,4-Dioxane uptake efficiency was positively correlated to cottonwood transpiration rates in the planted tank. The open pond 1,4-Dioxane measurements demonstrated a 64-85 percent reduction in 1,4-Dioxane concentration due to volatilization during the initial 120 hours pond lapse time. Elimination of 1,4-Dioxane from the ponds followed first order kinetics. Field and laboratory side experiments demonstrated the potential for UV photo degradation of 1-4-Dioxane.

Air pollution became a major concern in South Africa in the late 1980’s and regulatory requirements for the chemical process industries to reduce hazardous emissions have increased ever since. Volatile organic compounds (VOCs) contribute significantly to the formation of ozone and photochemical oxidants and their associated impact on human health has become a major issue worldwide. Volatilisation is a significant process in determining the fate of organic compounds in the environment. In this study, volatilisation rate of VOCs (specifically benzene, toluene, ethylbenzene, and xylene) from a wastewater collection basin, also called the oily sewer basin (OSB) was measured using a flux chamber method and the VOCs were characterised. Theoretical models that can be used to estimate volatilisation rate were also studied. Meteorological data was collected to evaluate the effect of temperature, humidity and wind speed on volatilisation rate. This study showed that toluene and ethylbenzene have the highest volatilisation rate compared to benzene and o-xylene. It was found that system conditions and physicochemical properties of a compound have a significant effect on volatilisation. It was also identified that the measured concentrations of VOCs escaping from the OSB do comply with Occupational Health and Safety Act and Regulations 85 of 1993 standards. It was recommended that surfactants be used to inhibit volatilisation of VOCs

No description available.

No description available.

<p> An apparatus was designed and built to enable the study of volatilization reactions using a novel variant of thermogravimetry called thermoradiometry. The usefulness of the apparatus was demonstrated by investigating the volatilization of iron from solid samples with the fluorinated ligands 1,1,1-trifluoro-2,4-pentanedione and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione.</p> / Thesis / Master of Science (MSc)

In 1990, creosote contamination was discovered at a railroad tie yard in Oneida, Tennessee. A phytoremediation system that included over 1,200 hybrid poplar trees was installed between 1997 and 1998 for hydraulic control of the groundwater and enhancement of the natural biodegradation processes in the subsurface. Since then, Virginia Polytechnic Institute and State University has monitored eight polycyclic aromatic hydrocarbons (PAHs) in the soil and groundwater. They have found that concentrations of smaller and more volatile PAHs have decreased over the years as the DNAPL contamination has become more enriched with the larger PAHs. This thesis focuses on the movement of naphthalene through the subsurface because it comprises the majority of the creosote and evidence for its remediation exists. Of the many mechanisms within the phytoremediation system that serve to remediate contaminated groundwater and soil, the most important are rhizosphere bioremediation and plant uptake. However, another mechanism, direct volatilization through the soil, was thought to have significant remediation capabilities at this site. Because naphthalene is a highly volatile PAH, it was hypothesized that naphthalene is volatilizing directly through the soil to the atmosphere and that the rate of volatilization may be enhanced by the presence of the phytoremediation system. The goals of this research are to measure the amount of naphthalene that volatilizes from the subsurface and determine the factors that significantly influence this direct volatilization. A flux chamber was designed and constructed to measure naphthalene fluxes from the soil. Factors that influence direct volatilization include the groundwater level, soil moisture, precipitation, pressure changes, temperature and humidity, the most important of which we found to be the groundwater level through its influence on naphthalene concentrations in the groundwater. We found that the presence of the trees significantly affects groundwater levels. As trees transpire and lower the groundwater table, concentrations in the uppermost portion of the groundwater increase, and under dry conditions, naphthalene fluxes from the soil are maximized. To complement the field measurements of direct volatilization, we also investigated rates of volatilization and biodegradation in the laboratory. Column experiments were conducted to determine the importance of direct volatilization on biodegradation in the vadose zone. We hypothesize that the combined mechanisms of contaminant transfer to the vadose zone, followed by rapid biodegradation, speeds up remediation in contrast to biodegradation that occurs only in the saturated zone under high groundwater conditions. Several columns using contaminated and uncontaminated soil from the site were constructed with a naphthalene source. Vertical naphthalene vapor concentration profiles were measured, and first-order biodegradation rates were determined. We found that biodegradation rates in the bacterially active columns were small initially, but that the biodegradation rates of the contaminated soil dramatically increased at day 60, while the biodegradation rates of the uncontaminated soil did not begin to increase until day 150. By the end of the experiment, both soil types had approximately the same biodegradation rate, signifying that soil that had previously been exposed to naphthalene degrades naphthalene more efficiently in the early stages than soil that has not been exposed, but that over time the non-exposed soil degrades naphthalene as efficiently as the pre-exposed soil. We determined that the combined mechanisms of diffusion and biodegradation in the unsaturated zone have significant remediation capabilities. Because long-term exposure risks are associated with inhaling indoor contaminant vapors, the Johnson and Ettinger vapor intrusion model was applied to the creosote-contaminated site, as outlined in Appendix C. This model takes into account soil, chemical, and building foundation characteristics to determine a dimensionless attenuation ratio, which is the ratio of contaminant vapor concentration in an enclosed space (i.e. basement) to the vapor concentration directly above the source. For a conservative case, the Johnson and Ettinger model without biodegradation was used. We found that if the land were developed, naphthalene vapor intrusion would not pose any health risks based on regulatory standards and levels at which health effects have been recorded. / Master of Science

O objetivo foi avaliar a influência de fertilizantes nitrogenados e do fornecimento de enxofre sobre a composição químico-bromatológica e algumas características agronômicas da cultura da cana-de-açúcar, bem como as perdas de N no sistema solo x Planta. O estudo foi conduzido no município de Araras/SP, numa área do Grupo Usina São João, durante dois anos de avaliação. A variedade utilizada foi a SP80-1816. As avaliações iniciaram-se após o primeiro e segundo cortes, sem queima prévia, e mecanicamente. O delineamento experimental foi em blocos inteiramente casualizados, com dez tratamentos (T1: Testemunha+Gesso (-N+S); T2: Testemunha absoluta (-N-S); T3: Uréia 45%N; T4: Uréia+Gesso; T5: Uréia+Sulfato de Amônio (SA) - 21%N/24%S - (33:00:00+12%S); T6: Nitrato de Amônio (NA) - 30%N; T7: Nitrato de Amônio (NA) - 30%N + Gesso; T8: NA + Sulfato de Amônio - 21%N/24%S - (27,8:00:00+6%S); T9: SA; T10: FASN (SA e NA - 26%N/14%S)) e quatro repetições, formando 40 parcelas experimentais, para o fornecimento de 100 kg N/ha. Cada parcela experimental constou de sete linhas de cana-de-açúcar espaçadas de 1,4 metro e 13 metros de comprimento, perfazendo área total de 127,4 m2, considerando-se como úteis as cinco linhas centrais, descontando-se as duas linhas laterais e 1,5 metro de cada extremidade da parcela, como bordadura. As avaliações das perdas de N-NH3 por volatilização foram efetuadas após a colheita, no momento da adubação de cobertura. As maiores perdas acumuladas de N-NH3 provieram da aplicação de Uréia seguida pelos tratamentos Uréia+Gesso e Uréia+SA em ambas as socas da cana-de-açúcar. Ocorreram, na segunda soca aumento nas perdas, que foram maiores logo após a aplicação sendo os níveis mínimos aos 9 e 11 dias para 1ª e 2ª soca respectivamente. As fontes nitrogenadas aumentaram os teores de N foliar na cana-de-açúcar. As fontes de enxofre beneficiaram os teores do elemento no solo, considerando-se a camada de 0-20 cm. As fontes de nitrogênio e enxofre propiciaram redução da porcentagem de fibras de acordo com os resultados da composição químico-bromatológica da cana-de-açúcar. Para a produtividade da cana-de-açúcar acumulada em duas safras consecutivas, o FASN foi a fonte que proporcionou melhor resposta, seguido do SA e NA. / The present studys objective was to evaluate the nitrogen fertilizing efficiency and the sulphur supplying over the chemical bromatological composition of some sugar cane agronomical characteristics as well as the nitrogen losses in the soil x plant system. The study was performed in Araras/SP county, in the Sao Joao Usine Group area, in a two year evaluation period. The used variety was the SP80-1816. The evaluation started after the first and second harvest, without previous burning, and mechanically. The experimental design was based on the random blocks standard, with ten treatments (T1: Control+Gypsum (-N+S); T2: Control (-N-S); T3: Urea 45%N; T4: Urea+Gypsum; T5: Urea+Ammonium Sulphate (SA) - 21%N/24%S - (33:00:00+12%S); T6: Ammonium Nitrate (NA) - 30%N; T7: Ammonium Nitrate (NA) - 30%N + Gypsum; T8: NA + Ammonium Sulphate - 21%N/24%S - (27,8:00:00+6%S); T9: SA; T10: FASN (SA e NA - 26%N/14%S)) and four repetitions, totalizing 40 experimental parcels, for 100Kg N/ha. Each experimental parcel was composed by 7 sugar cane lines spaced in 1,4m and 13 m long, distributed in a 127,4 m2 area, considering the five central line as useful, discounting two lateral lines and 1,5 m from each parcels extremity, as border segment. The N-NH3 volatization loss evaluation was effectuated after harvest, during cover fertilization. The highest accumulated N-NH3 losses were generated from Urea application followed by Urea+Gypsum and Urea+SA in both sugar canes ratoons. It was observed, in the second ratoon, a loss increasing, that was higher after the application, where the minimum rate were in the 9th and 11th days for the 1st and 2nd ratoon, respectively. The nitrogen sources increased the N leaf rate in sugar cane. The sulfur sources beneficiated this specific element rate in the soil, considering the 0-20 cm stage. The nitrogen and sulfur sources generated fiber percentage reduction, according to the chemical bromatological composition results. For accumulated sugar cane productivity in two consecutive crops, the FASN was the source that generated the best response, followed by SA and NA.

O objetivo foi avaliar a influência de fertilizantes nitrogenados e do fornecimento de enxofre sobre a composição químico-bromatológica e algumas características agronômicas da cultura da cana-de-açúcar, bem como as perdas de N no sistema solo x Planta. O estudo foi conduzido no município de Araras/SP, numa área do Grupo Usina São João, durante dois anos de avaliação. A variedade utilizada foi a SP80-1816. As avaliações iniciaram-se após o primeiro e segundo cortes, sem queima prévia, e mecanicamente. O delineamento experimental foi em blocos inteiramente casualizados, com dez tratamentos (T1: Testemunha+Gesso (-N+S); T2: Testemunha absoluta (-N-S); T3: Uréia 45%N; T4: Uréia+Gesso; T5: Uréia+Sulfato de Amônio (SA) - 21%N/24%S - (33:00:00+12%S); T6: Nitrato de Amônio (NA) - 30%N; T7: Nitrato de Amônio (NA) - 30%N + Gesso; T8: NA + Sulfato de Amônio - 21%N/24%S - (27,8:00:00+6%S); T9: SA; T10: FASN (SA e NA - 26%N/14%S)) e quatro repetições, formando 40 parcelas experimentais, para o fornecimento de 100 kg N/ha. Cada parcela experimental constou de sete linhas de cana-de-açúcar espaçadas de 1,4 metro e 13 metros de comprimento, perfazendo área total de 127,4 m2, considerando-se como úteis as cinco linhas centrais, descontando-se as duas linhas laterais e 1,5 metro de cada extremidade da parcela, como bordadura. As avaliações das perdas de N-NH3 por volatilização foram efetuadas após a colheita, no momento da adubação de cobertura. As maiores perdas acumuladas de N-NH3 provieram da aplicação de Uréia seguida pelos tratamentos Uréia+Gesso e Uréia+SA em ambas as socas da cana-de-açúcar. Ocorreram, na segunda soca aumento nas perdas, que foram maiores logo após a aplicação sendo os níveis mínimos aos 9 e 11 dias para 1ª e 2ª soca respectivamente. As fontes nitrogenadas aumentaram os teores de N foliar na cana-de-açúcar. As fontes de enxofre beneficiaram os teores do elemento no solo, considerando-se a camada de 0-20 cm. As fontes de nitrogênio e enxofre propiciaram redução da porcentagem de fibras de acordo com os resultados da composição químico-bromatológica da cana-de-açúcar. Para a produtividade da cana-de-açúcar acumulada em duas safras consecutivas, o FASN foi a fonte que proporcionou melhor resposta, seguido do SA e NA. / The present studys objective was to evaluate the nitrogen fertilizing efficiency and the sulphur supplying over the chemical bromatological composition of some sugar cane agronomical characteristics as well as the nitrogen losses in the soil x plant system. The study was performed in Araras/SP county, in the Sao Joao Usine Group area, in a two year evaluation period. The used variety was the SP80-1816. The evaluation started after the first and second harvest, without previous burning, and mechanically. The experimental design was based on the random blocks standard, with ten treatments (T1: Control+Gypsum (-N+S); T2: Control (-N-S); T3: Urea 45%N; T4: Urea+Gypsum; T5: Urea+Ammonium Sulphate (SA) - 21%N/24%S - (33:00:00+12%S); T6: Ammonium Nitrate (NA) - 30%N; T7: Ammonium Nitrate (NA) - 30%N + Gypsum; T8: NA + Ammonium Sulphate - 21%N/24%S - (27,8:00:00+6%S); T9: SA; T10: FASN (SA e NA - 26%N/14%S)) and four repetitions, totalizing 40 experimental parcels, for 100Kg N/ha. Each experimental parcel was composed by 7 sugar cane lines spaced in 1,4m and 13 m long, distributed in a 127,4 m2 area, considering the five central line as useful, discounting two lateral lines and 1,5 m from each parcels extremity, as border segment. The N-NH3 volatization loss evaluation was effectuated after harvest, during cover fertilization. The highest accumulated N-NH3 losses were generated from Urea application followed by Urea+Gypsum and Urea+SA in both sugar canes ratoons. It was observed, in the second ratoon, a loss increasing, that was higher after the application, where the minimum rate were in the 9th and 11th days for the 1st and 2nd ratoon, respectively. The nitrogen sources increased the N leaf rate in sugar cane. The sulfur sources beneficiated this specific element rate in the soil, considering the 0-20 cm stage. The nitrogen and sulfur sources generated fiber percentage reduction, according to the chemical bromatological composition results. For accumulated sugar cane productivity in two consecutive crops, the FASN was the source that generated the best response, followed by SA and NA.

Trichloroethylene (TCE) is a carcinogenic, chlorinated volatile organic compound that was commonly used as a degreasing solvent for aircraft maintenance at many US Air Force bases. Past improper disposal of TCE has resulted in contaminated groundwater at many of these facilities. Phytoremediation, defined as the use of plants and their associated microorganisms to stabilize or remove contamination, has been implemented as part of a TCE groundwater cleanup at Travis Air Force base near Sacramento, CA and is being considered as a remediation option at other bases. Volatilization of TCE from leaves and the surface of the soil near the trees were shown to be the most important removal mechanisms at the Travis site. Past studies conducted on indigenous trees growing above TCE contaminated groundwater at several Hill Air Force Base (HAFB) locations have also shown that TCE is taken up and volatilized by the trees. However, phytoremediation has not been implemented, in part because of the difficulty in predicting the potential effectiveness of TCE removal over time. Flow through or recirculating chambers were used to quantify the amount of TCE removed by volatilization through leaf, trunk, and soil surfaces. Tenax™ sorbent tubes, used to collect TCE from the chambers, were analyzed by thermal desorption gas chromatography/mass spectrometry. Tree cores were collected using an incremental borer and analyzed by headspace GC/MS to quantify the TCE mass contained in the trees. Field measured transpiration stream concentrations (TSC) and groundwater data were used to calculate transpiration stream concentration factors (TSCF) for TCE. Comparing current and historical data, it was found that trees reach a steady state TSCF value of 0.26 after about 15 years. Using this information, it was predicted that a phytoremediation plot containing 40 poplar trees located in a seep area within HAFB OU2 would remove 4.82 kg of TCE annually. A larger plot covering the entire hillside above this seep (160 trees) could remove up to 19.28 kg of TCE annually, once trees reach a steady state TSCF.

Overapplication of manure in sensitive watersheds is an issue of increasing environmental concern due to increased nutrient loading and antibiotic release into aquatic environments. Manure is typically surface applied, leaving nutrients and antibiotics vulnerable to loss at the soil surface. Elevated nutrient and antibiotic loading into water bodies can increase the rate of eutrophication and occurrence of antibiotic resistance genes in areas of high animal agriculture production, such as the Chesapeake Bay watershed. Manure injection is a new technology that incorporates manure into the soil with minimal disturbance, and management strategies that reduce manure loss from agricultural fields could prevent the transport of nutrients and antibiotics to sensitive waterways. However, little is known about the efficacy of dry litter injection to decrease nitrogen (N) loss when compared to surface application. Also, there are no studies that determine the effects of injection on antibiotic transport and transformation after manure application. Therefore, this project focused on changes in N cycling, orchardgrass hay yield and quality, and transport and transformation of pirlimycin and cephapirin, two common antibiotics in dairy production, when manure is injected. Subsurface injection eliminated ammonia volatilization and N loss in runoff and increased soil inorganic N when compared to surface application after volatilization, incubation, and rainfall simulation studies. Although these benefits did not translate to higher yields in orchardgrass hay, protein increased when poultry litter was injected, indicating greater N uptake. Injection of dairy manure decreased losses of pirlimycin to levels of the control when compared to surface application. Although, pirlimycin had a slower degradation rate within the injection slit compared to surface application, potentially increasing the amount of time soil microbes are exposed to antibiotics. In an incubation study, pirlimycin concentrations decreased after 7 days, but concentrations increased sharply after 14 days. This indicates that conjugates formed in the liver or digestive tract of dairy cows may revert back to the parent compound after manure application. With increased retention of nutrients and antibiotics, injection could be a best management practice used to reduce the loss of these compounds to the environment while increasing the quality of crops produced. / Ph. D.