Rebecca A. Trenholm

Prediction of Micropollutant Elimination during Ozonation of Municipal Wastewater Effluents: Use of Kinetic and Water Specific Information

Ozonation is effective in improving the quality of municipal wastewater effluents by eliminating organic micropollutants. Nevertheless, ozone process design is still limited by (i) the large number of structurally diverse micropollutants and (ii) the varying quality of wastewater matrices (especially dissolved organic matter). These issues were addressed by grouping 16 micropollutants according to their ozone and hydroxyl radical ((•)OH) rate constants and normalizing the applied ozone dose to the dissolved organic carbon concentration (i.e., g O3/g DOC). Consistent elimination of micropollutants was observed in 10 secondary municipal wastewater effluents spiked with 16 micropollutants (∼2 μg/L) in the absence of ozone demand exerted by nitrite. The elimination of ozone-refractory micropollutants was well predicted by measuring the (•)OH exposure by the decrease of the probe compound p-chlorobenzoic acid. The average molar (•)OH yields (moles of (•)OH produced per mole of ozone consumed) were 21 ± 3% for g O3/g DOC = 1.0, and the average rate constant for the reaction of (•)OH with effluent organic matter was (2.1 ± 0.6) × 10(4) (mg C/L)(-1) s(-1). On the basis of these results, a DOC-normalized ozone dose, together with the rate constants for the reaction of the selected micropollutants with ozone and (•)OH, and the measurement of the (•)OH exposure are proposed as key parameters for the prediction of the elimination efficiency of micropollutants during ozonation of municipal wastewater effluents with varying water quality.

Pilot-scale evaluation of ozone and biological activated carbon for trace organic contaminant mitigation and disinfection.

In an effort to validate the use of ozone for contaminant oxidation and disinfection in water reclamation, extensive pilot testing was performed with ozone/H(2)O(2) and biological activated carbon (BAC) at the Reno-Stead Water Reclamation Facility in Reno, Nevada. Three sets of samples were collected over a five-month period of continuous operation, and these samples were analyzed for a suite of trace organic contaminants (TOrCs), total estrogenicity, and several microbial surrogates, including the bacteriophage MS2, total and fecal coliforms, and Bacillus spores. Based on the high degree of microbial inactivation and contaminant destruction, this treatment train appears to be a viable alternative to the standard indirect potable reuse (IPR) configuration (i.e., membrane filtration, reverse osmosis, UV/H(2)O(2), and aquifer injection), particularly for inland applications where brine disposal is an issue. Several issues, including regrowth of coliform bacteria in the BAC process, must be addressed prior to full-scale implementation.

Development of surrogate correlation models to predict trace organic contaminant oxidation and microbial inactivation during ozonation.

The performance of ozonation in wastewater depends on water quality and the ability to form hydroxyl radicals (·OH) to meet disinfection or contaminant transformation objectives. Since there are no on-line methods to assess ozone and ·OH exposure in wastewater, many agencies are now embracing indicator frameworks and surrogate monitoring for regulatory compliance. Two of the most promising surrogate parameters for ozone-based treatment of secondary and tertiary wastewater effluents are differential UV(254) absorbance (ΔUV(254)) and total fluorescence (ΔTF). In the current study, empirical correlations for ΔUV(254) and ΔTF were developed for the oxidation of 18 trace organic contaminants (TOrCs), including 1,4-dioxane, atenolol, atrazine, bisphenol A, carbamazepine, diclofenac, gemfibrozil, ibuprofen, meprobamate, naproxen, N,N-diethyl-meta-toluamide (DEET), para-chlorobenzoic acid (pCBA), phenytoin, primidone, sulfamethoxazole, triclosan, trimethoprim, and tris-(2-chloroethyl)-phosphate (TCEP) (R(2) = 0.50-0.83) and the inactivation of three microbial surrogates, including Escherichia coli, MS2, and Bacillus subtilis spores (R(2) = 0.46-0.78). Nine wastewaters were tested in laboratory systems, and eight wastewaters were evaluated at pilot- and full-scale. A predictive model for OH exposure based on ΔUV(254) or ΔTF was also proposed.

Contaminants of emerging concern in municipal wastewater effluents and marine receiving water

The occurrence and concentrations of contaminants of emerging concern (CECs) were investigated in municipal effluents and in marine receiving water. Final effluent from four large publicly owned treatment works (POTWs) and seawater collected near the respective POTW outfall discharges and a reference station were collected quarterly over one year and analyzed for 56 CECs. Several CECs were detected in effluents; naproxen, gemfibrozil, atenolol, and tris(1-chloro-2-propyl)phosphate were the compounds most frequently found and with the highest concentrations (>1 µg/L). Gemfibrozil and naproxen had the highest seawater concentrations (0.0009 and 0.0007 µg/L) and also were among the most frequently detected compounds. Effluent dilution factors ranged from >400 to approximately 1,000. Fewer CECs were detected and at lower concentrations in seawater collected from the reference station than at the outfall sites. Effluent concentrations for some CECs (e.g., pharmaceuticals) were inversely related to the degree of wastewater treatment. This trend was not found in seawater samples. Few temporal differences were observed in effluent or seawater samples. Effluent CEC concentrations were lower than those currently known for chronic toxicity thresholds. Nevertheless, the evaluation of potential chronic effects for CECs is uncertain because aquatic life toxicity thresholds have been developed for only a few CECs, and the effluent and seawater samples had compounds, such as nonylphenol, known to bioaccumulate in local fish. Additional data are needed to better understand the significance of CEC presence and concentrations in marine environments.

An evaluation of a pilot-scale nonthermal plasma advanced oxidation process for trace organic compound degradation

This study evaluated a pilot-scale nonthermal plasma (NTP) advanced oxidation process (AOP) for the degradation of trace organic compounds such as pharmaceuticals and potential endocrine disrupting compounds (EDCs). The degradation of seven indicator compounds was monitored in tertiary-treated wastewater and spiked surface water to evaluate the effects of differing water qualities on process efficiency. The tests were also conducted in batch and single-pass modes to examine contaminant degradation rates and the remediation capabilities of the technology, respectively. Values for electrical energy per order (EEO) of magnitude degradation ranged from <0.3 kWh/m(3)-log for easily degraded compounds (e.g., carbamazepine) in surface water to 14 kWh/m(3)-log for more recalcitrant compounds (e.g., meprobamate) in wastewater. Changes in the bulk organic matter based on UV(254) absorbance and excitation-emission matrices (EEM) were also monitored and correlated to contaminant degradation. These results indicate that NTP may be a viable alternative to more common AOPs due to its comparable energy requirements for contaminant degradation and its ability to operate without any additional feed chemicals.

Determination of household chemicals using gas chromatography and liquid chromatography with tandem mass spectrometry

A method has been developed for the determination of 24 household high production volume (HPV) chemicals in municipal wastewater systems using solid-phase extraction (SPE) and analyses using both gas chromatography and liquid chromatography, each with tandem mass spectrometry (GC-MS/MS and LC-MS/MS). Target compounds include pesticides, antioxidants, fragrances, plasticizers, preservatives and personal care products. Method reporting limits ranged from 0.1 to 100 ng/L in water and recoveries for most compounds were between 54 and 112%. Household HPVs were consistently detected in raw sewage entering three full-scale wastewater treatment plants. Compounds such as vanillin, DEET, benzophenone, 3-indolebutyric acid, bisphenol A, triclosan and triclocarban were detected in all wastewater influent and effluent samples, but were significantly lower in the effluent. Many of the remaining compounds were detected in the influent, but below detection in effluent samples. Menthol and phenoxyethanol had the highest observed concentrations in influent samples ranging from 1.5 to 13 microg/L for menthol, and 8.8 to 22 microg/L for phenoxyethanol. MGK-11, methylresorcinol, trifluralin, hexabromododecane, acriflavin and atrazine were not detected in any samples. The method described here detects a broad range of HPV chemicals with great sensitivity and selectivity.

Organic Contaminant Abatement in Reclaimed Water by UV/H2O2 and a Combined Process Consisting of O3/H2O2 Followed by UV/H2O2: Prediction of Abatement Efficiency, Energy Consumption, and Byproduct Formation

UV/H2O2 processes can be applied to improve the quality of effluents from municipal wastewater treatment plants by attenuating trace organic contaminants (micropollutants). This study presents a kinetic model based on UV photolysis parameters, including UV absorption rate and quantum yield, and hydroxyl radical (·OH) oxidation parameters, including second-order rate constants for ·OH reactions and steady-state ·OH concentrations, that can be used to predict micropollutant abatement in wastewater. The UV/H2O2 kinetic model successfully predicted the abatement efficiencies of 16 target micropollutants in bench-scale UV and UV/H2O2 experiments in 10 secondary wastewater effluents. The model was then used to calculate the electric energies required to achieve specific levels of micropollutant abatement in several advanced wastewater treatment scenarios using various combinations of ozone, UV, and H2O2. UV/H2O2 is more energy-intensive than ozonation for abatement of most micropollutants. Nevertheless, UV/H2O2 is not limited by the formation of N-nitrosodimethylamine (NDMA) and bromate whereas ozonation may produce significant concentrations of these oxidation byproducts, as observed in some of the tested wastewater effluents. The combined process of O3/H2O2 followed by UV/H2O2, which may be warranted in some potable reuse applications, can achieve superior micropollutant abatement with reduced energy consumption compared to UV/H2O2 and reduced oxidation byproduct formation (i.e., NDMA and/or bromate) compared to conventional ozonation.

Photochemical degradation of atenolol, carbamazepine, meprobamate, phenytoin and primidone in wastewater effluents.

The photochemical degradation of five pharmaceuticals was examined in two secondary wastewater effluents. The compounds, which included atenolol, carbamazepine, meprobamate, phenytoin and primidone, were evaluated for both direct and sensitized photolysis. In the two wastewaters, direct photolysis did not lead to significant compound degradation; however, sensitized photolysis was an important removal pathway for the five pharmaceuticals. Upon solar irradiation, hydroxyl radical (HO) was quantified using the hydroxylation of benzene and singlet oxygen ((1)O2) formation was monitored following the degradation of furfuryl alcohol. Degradation via sensitized photolysis was observed following five-day exposures for atenolol (69-91%), carbamazepine (67-98%), meprobamate (16-52%), phenytoin (44-85%), and primidone (34-88%). Varying removal is likely a result of the differences in reactivity with transient oxidants. Averaged steady state HO concentrations ranged from 1.2 to 4.0×10(-16)M, whereas the concentrations of (1)O2 were 6.0-7.6×10(-14)M. Partial removal due to presence of HO indicates it was not the major sink for most compounds examined. Other transient oxidants, such as (1)O2 and triplet state effluent organic matter, are likely to play important roles in fates of these compounds.

Analysis of formaldehyde formation in wastewater using on-fiber derivatization–solid-phase microextraction–gas chromatography–mass spectrometry

A method has been developed for the quantification of the formation of formaldehyde during the advanced oxidation treatment (AOT) of wastewater destined for reuse. This method uses solid-phase microextraction (SPME) with on-fiber derivatization followed by gas chromatography-mass spectrometry (GC-MS) analysis. Based on calculated method detection limits (MDL) and ambient background levels, the method reporting (MRL) limit for formaldehyde was set at 10 microg/L. Precision for formaldehyde using this technique resulted in 23% relative standard deviation (RSD), while the internal standard, acetone-d(6), was only 6%. This method was used to evaluate the formation of formaldehyde in bench scale UV-AOT experiments using natural organic matter (NOM) fortified reagent water and tertiary treated wastewater effluent. Results suggest that the formation of formaldehyde increases in both the reagent water and wastewater matrices with increasing UV exposure and hydrogen peroxide concentrations, with overall higher concentrations of formaldehyde in the wastewater samples. No appreciable amount of formaldehyde formation was observed when UV was applied in the absence of hydrogen peroxide in both matrices tested.

The Effects of Solids Retention Time in Full-Scale Activated Sludge Basins on Trace Organic Contaminant Concentrations

Although pharmaceuticals and personal care products (PPCPs) and endocrine disrupting compounds (EDCs) are largely unregulated, water resource recovery facilities are increasingly using advanced chemical/physical treatment technologies (e.g., advanced oxidation and reverse osmosis) to remove or destroy these trace organic contaminants (TOrCs). This can both reduce potential adverse human health effects in reuse applications and mitigate environmental effects on aquatic ecosystems. Unfortunately, advanced treatment technologies are typically energy intensive and costly to implement, operate, and maintain. The goal of this study was to determine whether optimization of solids retention time (SRT) provided sufficient benefits to warrant such operational strategies for TOrC mitigation. Specifically, SRTs of 5.5, 6, and 15 days were evaluated to determine the effects on several standard wastewater parameters (e.g., nitrite, nitrate, and ammonia concentrations) and the degradation of TOrCs. The experimental SRTs were operated simultaneously in parallel, full-scale activated sludge basins. The results indicate that it can be beneficial to implement biological process optimization strategies using existing infrastructure while reducing reliance on advanced treatment technologies. This study also identified potential operational issues that might arise in activated sludge systems operating at extended SRTs.