Graduation Year

2011

Document Type

Dissertation

Degree

Ph.D.

Degree Granting Department

Civil and Environmental Engineering

Major Professor

Jeffrey A. Cunningham

Keywords

Bioremediation, EDCs, SPE, SPME, Water Reuse

Abstract

Soil-aquifer treatment (SAT) has been proposed as a method for reusing treated municipal wastewater. SAT is characterized by alternating cycles of aerobic and anaerobic conditions in the subsurface, in response to alternating cycles of flooding and drainage of a surface impoundment. It is not yet known how these alternating redox conditions affect the removal of potentially harmful endocrine-disrupting compounds (EDCs) from treated effluent.

The overall objective of my doctoral research is to determine the fate of EDCs in alternating aerobic/anoxic/anaerobic conditions under simulated SAT conditions. To assess the fate of EDCs in simulated SAT conditions, I first had to develop appropriate analytical methods. Prior researchers have developed sophisticated analytical methods for measuring low concentrations of EDCs in water. However, it is not inherently clear which of these methods is preferable for analysis of any particular set of environmental samples. Therefore, in order to compare the analytical methods, solid-phase extraction (SPE) and solid-phase micro-extraction (SPME) were compared for the analysis of two EDCs, bisphenol-A (BPA) and 17B-estradiol (E2), in water samples of water. Following extraction by SPE or SPME, the target EDCs were derivatized (silylated) and then analyzed by gas chromatography (GC) with mass spectrometry (MS). Also, the performance of two candidate derivatization agents, N,O-bis-(trimethylsiyl) trifluoroacetamide (BSTFA), N-methyl-N-(trimethylsilyl) trifluoroacetamide (MSTFA), was compared. SPME is more convenient, is less labor-intensive, and allows for analysis of smaller sample volumes, but it is expensive because fibers need frequent replacement, and the range of linearity was limited. SPE has a lower material cost and allows for the analysis of a broader range of concentrations, but it is more labor-intensive and large sample volumes may be required. Therefore, the selection of which method is "best" depends upon the constraints (time, money, sample volume, acceptable detection limit) associated with any particular set of samples. The two derivatization agents performed equally when used in conjunction with SPE, but MSFTA yielded higher peak areas for headspace (on-fiber) derivatization during SPME.

To investigate how alternating redox conditions of SAT may affect the removal of harmful EDCs, a simulated SAT systems were constructed in 4-L reactors with 500 g of sediment (collected from a wetland) and 3 L of treated effluent from a municipal wastewater treatment plant; then BPA and E2 were spiked into reactors, two common EDCs often found in treated wastewater. Redox conditions in the mesocosms were controlled by switching the air between air (to induce aerobic conditions) and nitrogen (to induce anaerobic conditions); the length of the anoxic/anaerobic cycles was varied to determine how this affects biodegradation of the target EDCs. The mesocosm environment was supplemented with either nitrate or sulfate to serve as potential electron acceptors during the anoxic/anaerobic cycles. In addition to monitoring the concentrations of the target EDCs in the mesocosms over time, I also monitored the concentration of dissolved oxygen in the water; the redox potential; the concentrations of nitrate, nitrite, and sulfate; and the concentration of bacteria in the water (estimated via flow cytometry).

BPA was biodegraded only during aerobic cycles, but E2 was biodegraded during both aerobic and anoxic/anaerobic cycles. Whenever the redox conditions in the system were switched, there was a temporary drop in the bacterial population, followed by a recovery of the population. When redox conditions were switched from anoxic/anaerobic to aerobic, biodegradation of the target EDCs commenced after a lag period during which no biodegradation was observed. The lag time for biodegradation in the aerobic cycle was longer when the anaerobic cycles were longer in duration. More biodegradation of E2 was observed under anoxic conditions than under anaerobic conditions.

SPE and SPME methods that included derivatization agent are useful method for detection and quantification of EDCs in water. I concluded that SAT is a viable technology to produce potable water from treated WWTP effluent, but the optimal length of flooding and drying cycles of SAT required removing the targeted contaminants during infiltration through the vadose zone.

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