Chromium (VI) is a pervasive groundwater contaminant that poses a considerable threat to human health. Remediation techniques have focused on the reduction of the highly mobile Cr(VI) to the sparingly soluble, and less toxic, Cr(III) species. Traditionally, remediation performance has been evaluated through the measurement of Cr(VI) concentrations; however, this method is both costly and time-consuming, and provides little information regarding the mechanism of Cr(VI) removal. More recently, Cr isotope analysis has been proposed as a tool for tracking Cr(VI) migration in groundwater. Redox processes have been shown to produce significant Cr isotope fractionation, where enrichment in the ⁵³Cr/⁵²Cr ratio in the remaining Cr(VI) pool is indicative of a mass-transfer process. This thesis describes laboratory batch and column experiments that evaluate the Cr isotope fractionation associated with the reduction of Cr(VI) by various materials and under various conditions. Laboratory batch experiments were conducted to characterize the isotope fractionation during Cr(VI) reduction by granular zero-valent iron (ZVI) and organic carbon (OC). A decrease in Cr(VI) concentrations was accompanied by an increase in δ⁵³Cr values for the ZVI experiments. Data were fitted to a Rayleigh-type curve, which produced a fractionation factor α = 0.9994, suggesting a sorption-dominated removal mechanism. Scanning electron microscopy (SEM), X-ray absorption near-edge structure (XANES) spectroscopy, and X-ray photoelectron spectroscopy (XPS) indicated the presence of Cr(III) on the solid material, suggesting that reduction of Cr(VI) occurred. A series of batch experiments determined that reaction rate, experimental design, and pre-treatment of the ZVI had little to no effect on the Cr isotope fractionation. The interpretation of isotope results for the organic carbon experiments was complicated by the presence of both Cr(VI) and Cr(III) co-existing in solution, suggesting that further testing is required. A laboratory column experiment was conducted to evaluate isotopic fractionation of Cr during Cr(VI) reduction by OC under saturated flow conditions. Although decreasing dissolved Cr(VI) concentrations also were accompanied by an increase in δ⁵³Cr values, the isotope ratio values did not fit a Rayleigh-type fractionation curve. Instead, the data followed a linear regression equation yielding α = 0.9979. Solid-phase analysis indicated the presence of Cr(III) on the surface of the OC. Both the results of the solid-phase Cr and isotope analyses suggest a combination of Cr(VI) reduction mechanisms, including reduction in solution, and sorption prior to reduction. The linear characteristic of the δ⁵³Cr data may reflect the contribution of transport on Cr isotope fractionation.

I analyzed the 21 year dynamics of dissolved organic carbon (DOC) in 55 lakes in five sites across Eastern Canada in relation to regional and global variables. Regional variables included total solar radiation (TSR), precipitation (PPTN), air temperature (T) and sulfate deposition (SO4). Global variables included the Southern Oscillation Index (SOI), North Atlantic Oscillation (NAO) and Pacific Decadal Oscillation (PDO). A synchronous pattern in DOC was found among lakes within each region; however, a synchronous pattern in DOC was not found between sites, except for Kejimkujik and Yarmouth which were only 80 km apart from each other. This suggested that the variation of the long-term DOC pattern was in response to the temporal pattern of regional variables, and it supports the recent understanding that regional factors have a strong influence on many lake properties. Significant long-term trends in DOC were not evident except at the Experimental Lakes Area (ELA), where an increase in DOC was observed together with a decrease in summer TSR and an increase in summer precipitation. Annual mean air temperature has increased at the Nova Scotia and Turkey lakes sites over the study period. The relationship between the long-term pattern in DOC with the regional and global variables was analyzed for each study site to determine the key variables that could best explain the variation in the long-term pattern in DOC. TSR and PPTN were important independent variables across all sites, except for the Turkey Lakes Watershed site (TLW). Summer TSR (annual TSR for Kejimkujik and Yarmouth) had a negative relationship, while summer precipitation had a positive relationship with the long-term DOC pattern for all sites except TLW. TSR and PPTN explained 78%, 49% and 84% of the variation in the long-term DOC pattern at Dorset, ELA, and Nova Scotia (NS) sites, respectively. In contrast, the long-term pattern in DOC at TLW only had a weak relationship with the regional and global variables considered. A General model was developed to compare the strength of the response of DOC to the regional variables among sites. Therefore, only the variables which had a significant linear correlation with DOC across sites were selected. If a site had no variables in common with other sites, it was excluded from the general model. This resulted in TLW being excluded from the general model because the long-term DOC pattern at TLW was not significantly correlated with any regional variables. The best general model included TSR from Dorset, ELA and NS sites and precipitation from only the NS site. The strengths of the response of DOC to precipitation were weak at Dorset and ELA compared to NS, therefore, they were excluded. The general model explained 91% of the site-to-site variation of DOC among sites. Among them, TSR was an important negative variable which contributed 56% of the explanation to the general model. Precipitation at NS was an important positive variable for the general model. It contributed 34% of the explanation to the model. As the response of the long-term DOC pattern to the changes of environmental variables (TSR and PPTN) was very strong at NS, the NS site dominated the general model, and its temporal (year-to-year) variation in the long-term DOC pattern explained 60% of the site-to-site variation of DOC in Eastern Canada. The other two sites, Dorset and ELA, had weak contributions (20% and 11%, respectively) to the general model.

Soil organic N (SON) comprises 90% of all N in surface soils, yet as much as half remains in forms which are chemically unknown or, at best, poorly understood. Analytical methods such has pyrolysis field-ionization mass spectrometry (Py-FIMS) and 15N cross polarization magic-angle spinning nuclear magnetic resonance (CPMAS-NMR) spectroscopy are widely used for the characterization of SON; however, these methods have limitations which contribute to the gaps in our understanding of SON chemistry. For example, Py-FIMS may produce heat-induced secondary compounds, and 15N-NMR may lack sensitivity and resolution for experiments at natural 15N abundance. X-ray absorption near edge structure (XANES) spectroscopy probes the bonding environment of individual elements. The application of this technique to complex environmental samples such as soil is still in its infancy, but early studies suggest that this technique may help resolve SON molecular structure. This dissertation sought to develop and apply synchrotron-based N and C K-edge XANES spectroscopy to the study of soil and soil extracts to determine the structures in which SON is bound. In these studies, Py-FIMS was coupled with XANES as a corroboratory technique.<p> Initial methodological development resulted in a calibration method whereby N2 gas generated in ammonium-containing salts was used to calibrate a soft X-ray beamline at the N K-edge. Although XANES can produce secondary compound artifacts, contrary to early assertions that it is a non-destructive technique, it was shown in a second study that beam-induced decomposition can be minimized by moving the beam to a fresh spot between scans.<p> Three applied studies exploring SON composition were conducted. These studies followed a spatial gradient ranging from the landscape scale, through a rhizosphere study, and ended with a study of glomalin-related soil protein (GRSP). Glomalin-related soil protein is a persistent soil glycoprotein of arbuscular mycorrhizal origin (AMF) implicated in aggregation and long-term C and N storage. Nitrogen and C K-edge XANES and Py-FIMS were used in all studies, and GRSP was further characterized using proteomics techniques.<p> Soil organic N composition was largely controlled by topographic position, and to a lesser degree, by cultivation. Divergent (i.e., water shedding) positions were enriched in carbohydrates and low molecular weight lignins, whereas convergent, depressional and level positions showed enrichment in lipid-type compounds. These differences were attributed to tillage-induced redistribution of soil, and water movement from upper to lower slope positions. Nitrogen XANES revealed a unique form of organic N, identified as N-bonded aromatics, particularly in the divergent positions.<p> Rhizosphere soil was enriched in higher molecular weight lipid-type materials and depleted in low molecular weight polar compounds. This was attributed to increased input of fresh plant material and higher microbial turnover in the rhizosphere. Nitrogen-bonded aromatics also were detected in the rhizosphere.<p> The GRSP extracts were characterized as mostly proteinaceous, but also contained many co-extracted, non-protein compounds. Despite being previously described as a glycoprotein, only weak carbohydrate signals were observed. Proteomics-based assessment of GRSP showed no homology to any proteins of AMF origin, instead showing homology with thioredoxin and with heat-stable soil proteins. This may be because protein databases do not yet contain glomalin-related sequences, or that glomalin is homologous to non-AMF soil proteins.<p> This dissertation demonstrated that N XANES is a sensitive and novel method for characterizing SON, and can be used complementarily with other analytical techniques such as Py-FIMS and proteomics. The continued development of XANES will provide a useful tool for SOM research into the future.

Taiwan Water Supply Cooperation (TWSC) has upgraded traditional purification processes into advanced treatment systems in south Taiwan for many years. The removal efficiency of assimilable organic carbon (AOC) by ultrafiltration (UF) with reverse osmosis (RO) systems was 47% was lower than that of 62% by ozone with biological activated carbon system (BAC). In this work, we investigate the removal of AOC and disinfection by products formation potential (DBPFP) of raw water took from a water treatment plant by using BAC and membrane treatment units. BAC system of granular activated carbon(GAC) and powder activated carbon (PAC) showed two kind carbons have certain efficiency for AOC removal. Results we found could reach above 50% (from 44.28¡Ó9.84£gg acetate-C/L reduce to 20.93¡Ó4.25£gg acetate-C/L for GAC and from 45.92¡Ó17.75£gg acetate-C/L reduce to 21.23¡Ó4.25£gg acetate-C/L for PAC), when hydraulic retention time (HRT) in BAC reactor was at 1 hour. When HRT raised to 6 hours the concentration of AOC in effluent of BAC systems were reduced under 15 £gg/L, and removal efficiency could reach above 70%. The suggested limit level of AOC is 50 £gg/L of drinking water. In removal of DBPFP, BAC of two carbons has showed certain efficiency on trihalomethanes formation potential (THMFP) and haloacetic acids formation potential (HAA5FP). The results were done in removal of THMFP (from 20.54¡Ó6.48£gg/L reduce to 14.21¡Ó4.47£gg/L for GAC and from 24.64¡Ó6.74£gg/L reduce to 14.75¡Ó4.04£gg/L for PAC) and HAA5FP (from 39.64¡Ó10.38£gg/L reduce to 17.35£gg/L for GAC and from 17.86¡Ó5.13£gg/L reduce to 11.76¡Ó3.76£gg/L for PAC) in BAC reactors. They were all lower than national standard of drinking water (THMs 80£gg/L, HAAs 60£gg/L). It is believed that two kind carbons in BAC system could all reduce effectively on AOC and DBPFP to obtain high quality of drinking water with biological stability at HRT of 6 hours.

Carters Creek in Brazos County, Texas, like many surface water reaches in the Texas Gulf Coast region, has been identified for bacteria and nutrient impairment on the Texas Commission on Environmental Quality (TCEQ) 303(d) List. Carters Creek drains a rapidly urbanizing watershed and has been found to carry high concentrations of dissolved organic carbon (DOC), nitrate, phosphate and sodium. These constituents have a severe impact on the creek?s capacity for healthy aquatic life and increase the potential for eutrophication downstream. The creek has also had chronic high Escherichia coli counts, making the creek unsuitable for contact recreation according to the accepted standard for surface water quality, which is a geometric mean of 126 CFU per 100 ml. In this study, grab samples were taken twice monthly from fifteen sites on Carters Creek and its subcatchments from July 2007 to June 2008. The samples were analyzed for E. coli, DOC, total N, NO3-N, NH4-N, Na+, K+, Mg2+, Ca2+, F-, Cl-, Br-, NO2-, SO42- and PO4-3. Mean annual DOC concentrations varied from 24.8 mg/L in Carter at Boonville Road to 55.5 mg/L in Wolfpen Creek; sodium varied from 33 mg/L in Carter at Old Reliance Road to 200 mg/L, also in Wolfpen Creek. Burton 4, the subcatchment with the highest geometric mean for E. coli with 2547 CFU/100 mL, was also sampled with greater geographical intensity for E. coli and optical brightener fluorescence at 445 nm to identify any leaking sewer pipes, but no evidence of defective pipes was found. During both the spring season and annual high flow (storm events), E. coli counts were positively correlated with total urban land use, probably caused by storm runoff carrying residues from impervious surfaces into the stream. High flow E. coli also had a negative relationship with potassium and a positive relationship with calcium, possibly suggesting a bioflocculation effect. Sites downstream of wastewater treatment plants (WWTPs) showed higher nitrate, phosphate, sodium, potassium, chloride and fluoride than other urban subcatchments. Creeks with golf courses carried more phosphate, sodium and fluoride than subcatchments without golf courses or WWTPs.

Abstract In order to understand the source, transport pathway and sink of settling particulates off northeast Taiwan, time-series sediment traps (PPS-3/3) were deployed on the north slope of Ilan ridge (T18) and in the Okinawa trough (T15 and T16) to collect settling particulates. The trapped particulate samples were determined for apparent mass flux (T18), particle size distribution, and contents of lithogenic portion, metals (Al, Mg, Ca, Fe, Mn, Cu), opal, OC (organic carbon) and IC (inorganic carbon). The results show that mass flux in winter is higher than in summer except for typhoon or rainstorm in summer which may cause high particulate flux. At mooring T11 and T17, only 2 cups had collected particulates but with rapid decrease, and the remaining cups were empty. It is not clear whether Kuroshio plays a role and further investigation is needed. The trapped particulates were mainly clay and silt in the north slope of Ilan ridge and south Okinawa trough, and were sand and silt in the Mien-Hwa canyon. The portion of coarse silt and larger particles (>31 mm) decreases with an increase of distance from the land (from T11 to T18). The grain size distribution of particulate at T18 is similar to that at T15 and T16, but the mass flux in the north slope of Ilan ridge is an order of magnitude higher than in the south Okinawa trough. The size distribution pattern below 600m water depth is very similar at both T15 and T16, but the coarse fraction (> 31 mm) is more at the upper than lower traps, presumably due to lateral transport. The Mn content of the trapped particulates in the south Okinawa trough is twice as hign as that in the north slope of Ilan ridge. High Mn/Al ratio in the trough suggests that Mn is supplied by hydrothermal activities. Lithogenic portions occupy about 84~88.5% at T18, T16 and T15. Relative to other marginal seas biogenic contributions are clearly lower.

It is well documented that increases in soil organic matter (SOM) improve soil physical properties and increase the overall fertility and sustainability of the soil. Research in SOM storage has recently amplified following the proposal that agricultural soils may provide a significant carbon (C) sink that may aid in the mitigation of increasing atmospheric carbon dioxide. Observed differences in lint yield and nitrogen response from a cotton performance study at the Texas A&M University Experimental Farm near College Station, TX prompted us to examine the effects of tillage and rotation on soil organic C (SOC), soil microbial biomass C (SMBC), 38-day cumulative C mineralization (38-day CMIN), hot-water extractable organic C (hot-WEOC), carbohydrate C, and total glomalin. The treatments examined included conventional-till continuous cotton (CT), reduced-till continuous cotton (RT), and conventional-till cotton after corn rotation (CC) treatments. In pre-plant soil samples, SOC, SMBC, and 38-day CMIN in the top 5 cm were 33, 58, and 79 % greater in RT and 29, 32, and 36 % greater in CC vs. CT. Comparable differences were observed for hot-WEOC and carbohydrate C. Little seasonal variation was observed for labile-C pools throughout the growing season, suggesting minimal C input from cotton roots. Water-stable aggregation was not significantly affected by management, and did not correlate with labile-C pools or total glomalin. Labile-C pools were generally more responsive to management vs. SOC and were strongly correlated with one another. Carbohydrate C of hot-water extracts exhibited the strongest relationships with SMBC and 38-day CMIN, even though it comprised only 3 and 5 % of these pools, respectively. Our data suggest that increasing SOC in Texas cotton-cropping systems through conservation management is possible. Long-term data are still needed to fully address SOC storage potentials in Texas, but increases in labile-C pools resulting from conservation management are attainable and have the potential to positively impact soil fertility.

Diffuse reflectance spectroscopy (DRS) is a rapid proximal-sensing method that is being used more and more in laboratory settings to measure soil properties. Diffuse reflectance spectroscopy research that has been completed in laboratories shows promising results, but very little has been reported on how DRS will work in a field setting on soils scanned in situ. Seventy-two soil cores were obtained from six fields in Erath and Comanche County, Texas. Each soil core was scanned with a visible near-infrared (VNIR) spectrometer with a spectral range of 350-2500 nm in four different combinations of moisture content and pre-treatment: field-moist in situ, air-dried in situ, field-moist smeared in situ, and air-dried ground. Water potential was measured for the field-moist in situ scans. The VNIR spectra were used to predict total and fine clay content, water potential, organic C, and inorganic C of the soil using partial least squares (PLS) regression. The PLS model was validated with data 30% of the original soil cores that were randomly selected and not used in the calibration model. The root mean squared deviation (RMSD) of the air-dry ground samples were within the in situ RMSD and comparable to literature values for each soil property. The validation data set had a total clay content root mean squared deviation (RMSD) of 61 g kg-1 and 41 g kg-1 for the field-moist and air-dried in situ cores, respectively. The organic C validation data set had a RMSD of 5.8 g kg-1 and 4.6 g kg-1 for the field-moist and air-dried in situ cores, respectively. The RMSD values for inorganic C were 10.1 g kg-1 and 8.3 g kg-1 for the field moist and air-dried in situ scans, respectively. Smearing the samples increased the uncertainty of the predictions for clay content, organic C, and inorganic C. Water potential did not improve model predictions, nor did it correlate with the VNIR spectra; r2-values were below 0.31. These results show that DRS is an acceptable technique to measure selected soil properties in-situ at varying water contents and from different parent materials.

Growth of bacteria in drinking water distribution and storage systems can lead to the deterioration of water quality, violation of water standards, and increased operating costs. Growth or Regrowth results from viable bacteria surviving the disinfection process and utilizing nutrient in the water and biofilm to sustain growth. Factors other than nutrients that influence regrowth include temperature, residence time in mains and storage units, and the efficacy of disinfection. Tests to determine the potential for bacterial regrowth focus on the concentration of nutrients. Not all organic compounds are equally susceptible to microbial decomposition; the fraction that provides energy and carbon for bacterial growth has been called labile dissolved organic carbon, biodegradable organic carbon (BDOC), or Assimilable Organic Carbon (AOC). Easily measured chemical surrogates for AOC are not available now. As alternative to chemical methods, bioassays have been proposed. Assimilable Organic Carbon (AOC) is that portion of the biodegradable organic carbon that can be converted to cell mass and expressed as a carbon concentration by means of a conversion factor. In this study, two organisms, namely Psuedomonas fluorescens strain P17 and Spirillum species NOX were selected for the AOC determination. The growth of the bacteria was determined by periodic colony counts with spread plate technique on LLA (Lab-Lemco nutrient agar) cultivation medium until the growth reached maximum (maximum colony count, Nmax). Results showed that AOC follows a trend based on the climatic and seasonal changes (local climate) with peaks in summer and low during winter season and vice versa in term of AOC removing capability. In addition to confirm AOC removal rate in biofiltration bed was evaluated with a test column containing the same filling materials, Granular Activated Carbon (GAC). Long term test showed that GAC would last for forty weeks without any special treatment. Other result showed that biofiltration bed has a better removal efficiency rate 72% (average based on four year), than the test column 49% since it experience frequent back-washing, thus maintaining a healthy removal rate. In the test column change in total organic carbon was quite abnormal. AOC yearly distribution was also studied and differentiated into four stages. AOC removal of each stage was 48%, 70%, 83% and 77%. Total organic carbon concentration was much higher in the effluent 384 than influent 334 £gg C/L; later methionine was found in water sample (effluent) which strongly suggests that the indigenous microbes had been reducing organic material such as cystein to methionine thus increasing the organic carbon content of the effluent. The microbial growths inside the GAC test column is entirely based on the long term feed of water at the treatment plant. Several other parameters such as Scanning Electron Microscope (SEM), Excitation Emissions Fluorescence Matrix (EEFM), Molecular Weight and Amino acids detection were selected and coupled with the AOC to shed light on the working mechanisms of both GAC as filtration material and characteristics of indigenous microbes towards the removal of organic contaminants and changes they can bring about to the quality of clear water.

To improve water quality of drinking water, the Taiwan Water Supply Corp (TWSC) upgraded three water treatment plants (WTP), changing traditional treatment processes into two advanced membrane processes and one advanced ozonation processes in recent years. Membrane water treatment units of the water treatment plant comprise ultrafiltration (UF) and reverse osmosis (RO). And the advanced ozonation water treatment units comprise pellet softening, post-ozonation and biological activated carbon (BAC) adsorption. This study investigated the formation of disinfection byproducts (DBPs), dissolved organic carbon (DOC) and assimilable organic carbon (AOC) at two advanced water treatment plants (ATP) in Kaohsiung City, Taiwan, by implementing a sampling program. The purposes of this study include¡G(1) The evaluation of treatment efficiency of advanced water treatment plants. (2) Application of powdered activated carbon and membrane bioreactor in removing organic compounds in drinking water. TCM was by far the predominant species in the finished water, the average concentration of DPBs in this study at both plants were 13.97¡Ó4.18£gg/L and 21.49¡Ó10.59£gg/L of THMs for plant A and plant B, respectively. However, levels for DPBs compound are low in both plants and lower than the current national drinking water quality standards 80 £gg / L. But for anther typical DPBs (HAAs compounds), the average concentrations were 17.67¡Ó14.50£gg/L and 33.03¡Ó16.24£gg/L of HAA5 for plant A and plant B, respectively. DCAA and TCAA were the two major species of HAAs found in the two water samples under study. The sums of the two species represented in finished water were about 67% and 83% of HAA5 in A and plant B, respectively. The results showed that HAA5 concentration of all samples could meet current USEPA standards for drinking water quality. Importantly, our work show the advanced treatment processes have good removal on DPBs of treated water. In organic compounds removal, there is high efficiency by using post-ozonation combined with BAC, but low efficiency for membrane process due to the inhibition of electrical charge happened on surface of membrane. This inhibition is caused probably by high hardness and high ion strength in water. We found by combining BAC with membrane filtration process will effectively remove the organic compounds and lower the concentration of AOC for passing the limit value suggested in related researches of the world.