Graduation Year

2010

Document Type

Dissertation

Degree

Ph.D.

Degree Granting Department

Geology

Major Professor

Thomas Pichler, Ph.D.

Keywords

Florida, Constructed wetland, Wastewater treatment, Clay settling area, Geogenic arsenic, Isotope mass-balance, Reactive transport modeling

Abstract

The efficiency to improve the water quality of industrial and municipal wastewater in a constructed wetland/filter basin treatment system was investigated. The wetland system was constructed in a closed phosphate mine used for clay settling and sand tailings in Polk County, Florida. During 18-months of monitoring the chemical/microbiological composition of treated wetland water remained relatively constant, despite significant seasonal variations in temperature, rainfall and humidity. The following changes in water quality between input and output were observed: substantial decrease of water temperature (up to 10°C), reduction of As, SO4, F, Cl, NO3, NO2, Br, Na, K, Ca, and Mg, change in pH from 9 to 6.5-7, increase of H2S (up to 1060 micrograms/L), and a change from positive to negative ORP.

There were no exceedances of the primary drinking water standards, volatile organic compounds, synthetic organic compounds, and radionuclides, but a number of exceedances for the secondary drinking water standards (Al, F, Fe, Mn, color, odor, total dissolved solids, and foaming agents). The concentration of fecal and total coliform bacteria in the wetland water was high, but subsequently reduced during filtration in the filter basin from 30 - 730 and 1000 - 7000 count/100 mL to < 2 and < 100 count/ 100 mL, respectively. To resolve the complex hydrogeological conditions a combined isotope/chemical mass-balance approach was applied.

The results were the following: (1) the composition of water in the wetland varied throughout the period of the study; (2) a change in isotopic composition along the wetland flow path; (3) the wetland contained mainly wastewater (88 - 100 %) during normal pumping operations; however, hurricanes and inconsistent pumping added low conductivity water directly and triggered enhanced groundwater inflow into the wetland of up to 78 %; (4) the composition of water in monitor wells was mostly groundwater dominated; however periodically seepage from a water body to the north was detected; and (5) seepage from adjacent water bodies into the wetland was not identified during operation, which would indicate a potential water loss from the wetland.

To test if the wetland system could be a prospective pre-treatment option for water used in aquifer storage and recovery (ASR) scenarios, a set of bench-scale leaching experiments was carried out using rocks from the Avon Park Formation, the Suwannee Limestone and the Ocala Limestone. Since As in the Floridan Aquifer was mainly present as an impurity in the mineral pyrite the elevated iron and sulfide concentrations in the wetland water were thought to prevent pyrite dissolution. The experiments which covered a range of redox conditions showed that the amount of As released from the aquifer matrix was not perfectly correlated with the bulk rock As concentration, nor the redox state of the water.

The following important results were obtained: (1) the highest concentration of As was leached from the Avon Park Formation and the lowest - from the Suwannee Limestone, although the Ocala Limestone had the lowest bulk rock As; (2) minor to no As was released using native Floridan groundwater; (3) Tampa tap water, which chemically and physically resembled the ASR injection water, caused the As leaching of up to 27 micrograms/L, which was higher than the As drinking water standard; (4) the wetland and filter basin waters caused the highest release of As (up to 68 micrograms/L), which was unexpected because those water types were less oxygenated than Tampa tap water and thus should be less aggressive; (5) the in-situ filtration of the wetland water through a 0.2 micrometer membrane resulted in a reduction of As from 30 microgram/L to 16 microgram/L; and (5) the UV treatment significantly reduced both fecal and total coliform bacteria, but facilitated the increase of DO in initial waters, a change from negative to positive ORP, and the increase of As concentration in leachates.

The experiments confirmed that perturbations of native aquifer conditions caused the release of As from the Floridan aquifer matrix, although the reaction may not be as simple as the dissolution of pyrite by oxygen, but additionally governed by a complex set of factors including the ORP of the system, SO4²?/S², Fe³?/Fe²?, dissolved organic carbon and microbial activity. In addition, the trend of As leaching could be governed by a set of factors, such as the porosity and permeability of the aquifer matrix influencing the rate and degree of free water saturation, amount of pyrite to be exposed to the preferential water flow paths, limited surface reactivity of pyrite with favored reactions on fractured mineral surfaces, the concentration and the selective leaching of As from individual pyrite crystals.

To characterize and verify the geochemical processes in the column experiments, the Geochemist's Workbench reactive transport models (React and X1t) were developed. Results from the models correlated well to those from the column experiments and confirmed the following: (1) the water-rock reaction between the aquifer matrix and native groundwater was favorable for pyrite stability preventing the release of As into solution; (2) the injection of oxidizing surface water into reducing native groundwater caused a change in redox potential of the system thus promoting the dissolution of pyrite, and (3) 1D reactive transport model of water-rock reaction between the aquifer matrix and surface water indicated a diverse behavior of As along the column, such as the oxidative dissolution of pyrite, mobilization and simultaneous sorption of As onto neo-formed HFO, followed by the reductive dissolution of HFO and secondary release of adsorbed As, and the potential non-oxidative dissolution of pyrite contributing the additional source of As to the solution.

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