Wontae Lee

Correlations between organic matter properties and DBP formation during chloramination.

Characteristics, including fluorescence intensity and specific UV absorbance (SUVA), of 16 organic matter (OM) fractions isolated from four OM samples plus a standard were analyzed and correlated with their specific disinfection by-product (DBP) and total organic halogen (TOX) formation after chloramination. These isolates were obtained from various water sources by using XAD-8/4 resins. Chloramination was achieved by adding 20mg/L monochloramine to a solution containing one OM isolate at 5mg/L DOC and buffered at pH 7.5 for 7 days. The fluorescence regional integration (FRI) method was used to analyze the fluorescence intensity data obtained from excitation-emission matrix (EEM) fluorescence spectroscopy, in which the EEM figure was divided into five regions and a normalized fluorescence volume was calculated. The cumulative normalized EEM volumes at regions II and IV (Phi(II+IV,)(n)) showed linear relationships with the yields of dichloroacetic acid (DCAA) (R(2)=0.60), chloroform (R(2)=0.42), dichloroacetonitrile (DCAN) (R(2)=0.53), and TOX (R(2)=0.63). The SUVA values were found to have linear relationships with the yields of DCAA (R(2)=0.82), chloroform (R(2)=0.73), DCAN (R(2)=0.88) and TOX (R(2)=0.80), but not with the yields of cyanogen chloride (CNCl) and chloropicrin (CP). A modified model is proposed to simplify the reactions involving chloramination of OM fractions. FTIR spectra of OM before and after chloramination partially confirmed that ketone groups were reactive with monochloramine.

Solar photolysis kinetics of disinfection byproducts.

Disinfection byproducts (DBPs) discharged from wastewater treatment plants may impair aquatic ecosystems and downstream drinking-water quality. Sunlight photolysis, as one process by which DBPs may dissipate in the receiving surface water, was investigated. Outdoor natural sunlight experiments were conducted in water for a series of carbonaceous DBPs (trihalomethanes, haloacetic acids, halopropanones, and haloacetaldehydes) and nitrogenous DBPs (nitrosamines, halonitromethanes, and haloacetonitriles). Their pseudo-first-order rate constants for photolytic degradation were then used to calibrate quantitative structure-activity relationship (QSAR) parameters, which, in return, predicted the photolysis potentials of other DBPs or related compounds. Nitrogenous DBPs were found to be more susceptible to solar irradiation than carbonaceous DBPs, with general rankings for the functional groups as follows: N-nitroso (N-NO)>nitro (NO(2))>nitrile (CN)>carbonyl (CO)>carboxyl (COOH). Compounds containing a high degree of halogenation (e.g., three halogens) were usually less stable than less halogenated species (e.g., those with two halogens). Bromine- or iodine-substituted species were more photosensitive than chlorinated analogs. While most bromine- and chlorine-containing trihalomethanes and haloacetic acids persisted over the 6-h test, nearly complete removal (>99%) of nitrosamines occurred within 1 h of sunlight exposure. Indoor laboratory experiments using simulated sunlight demonstrated that the degradation of nitrosamines was approximately 50% slower when organic matter was present, and approximately 11% slower in non-filtered water than in filtered water.

Formation of organic chloramines during water disinfection – chlorination versus chloramination

Many of the available studies on formation of organic chloramines during chlorination or chloramination have involved model organic nitrogen compounds (e.g., amino acids), but not naturally occurring organic nitrogen in water. This study assessed organic chloramine formation during chlorination and chloramination of 16 natural organic matter (NOM) solutions and 16 surface waters which contained dissolved organic nitrogen (DON). Chlorination rapidly formed organic chloramines within 10 min, whereas chloramination formed organic chloramination much more slowly, reaching the maximum concentration between 2 and 120 h after the addition of monochloramine into the solutions containing DON. The average organic chloramine formation upon addition of free chlorine and monochloramine into the NOM solutions were 0.78 mg-Cl(2)/mg-DON at 10 min and 0.16 mg-Cl(2)/mg-DON at 24h, respectively. Organic chloramine formation upon chlorination and chloramination increased as the dissolved organic carbon/dissolved organic nitrogen (DOC/DON) ratio decreased (i.e., DON contents increased). Chlorination of molecular weight (10,000 Da) fractionated water showed that molecular weight of DON would not impact the amount of organic chloramines produced. Comparison of three different disinfection schemes at water treatment plants (free chlorine, preformed monochloramine, and chlorine/ammonia additions) indicated organic chloramine formation could lead to a possible overestimation of disinfection capacity in many chloraminated water systems that add chlorine followed by an ammonia addition to form monochloramine.

Formation of disinfection byproducts upon chlorine dioxide preoxidation followed by chlorination or chloramination of natural organic matter

Chlorine dioxide (ClO2) is often used as an oxidant to remove taste, odor and color during water treatment. Due to the concerns of the chlorite formation, chlorination or chloramination is often applied after ClO2 preoxidation. We investigated the formation of regulated and emerging disinfection byproducts (DBPs) in sequential ClO2-chlorination and ClO2-chloramination processes. To clarify the relationship between the formation of DBPs and the characteristics of natural organic matter (NOM), changes in the properties of NOM before and after ClO2 oxidation were characterized by fluorescence, Fourier transform infrared spectroscopy (FTIR), and size and resin fractionation techniques. ClO2 preoxidation destroyed the aromatic and conjugated structures of NOM and transformed large aromatic and long aliphatic chain organics to small and hydrophilic organics. Treatment with ClO2 alone did not produce significant amount of trihalomethanes (THMs) and haloacetic acids (HAAs), but produced chlorite. ClO2 preoxidation reduced THMs, HAAs, haloacetonitriles (HANs) and chloral hydrate (CH) during subsequent chlorination, but no reduction of THMs was observed during chloramination. Increasing ClO2 doses enhanced the reduction of most DBPs except halonitromethanes (HNMs) and haloketones (HKs). The presence of bromide increased the formation of total amount of DBPs and also shifted DBPs to more brominated ones. Bromine incorporation was higher in ClO2 treated samples. The results indicated that ClO2 preoxidation prior to chlorination is applicable for control of THM, HAA and HAN in both pristine and polluted waters, but chlorite formation is a concern and HNMs and HKs are not effectively controlled by ClO2 preoxidation.

Adsorption Studies for the Removal of Nitrate Using Modified Lignite Granular Activated Carbon

The removal of nitrate on ZnCl2 modified lignite granular activated carbon (LGAC) was investigated. The LGAC was modified with varying chemical impregnation ratios (ZnCl2: LGAC) and activation temperatures. Modified LGAC (LGAC5), with a 2:1 chemical impregnation ratio and a 500°C activation temperature had the optimum adsorption capacity for , at a 200 mg/L initial concentration. The initial pH of the testing solutions significantly influenced the adsorption capacity of LGAC5. The contact time studies showed the effectiveness of LGAC5, up to 50 mg/L initial concentration with 30 min of equilibration time. Isotherm studies revealed the highest values of the Langmuir constant (b), confirming strong affinity of LGAC5 for ions. Thermodynamics studies verified the endothermic nature of the adsorption process with randomness at the solid/solution interface. Competitive ion testing demonstrated that interfering anions, such as Cl−, , significantly reduced adsorption on LGAC5.

Effect of hydraulic retention time on lactic acid production and granulation in an up-flow anaerobic sludge blanket reactor

In the present work, lactic acid (LA) production performance with granulation was investigated at various hydraulic retention times (HRTs), 8-0.5h. Glucose was used as a feedstock, and anaerobic mixed cultures were inoculated in an up-flow anaerobic sludge blanket reactor. As HRT decreased, the average diameter and hydrophobicity of the granules increased from 0.31 to 3.4mm and from 17.5% to 38.3%, respectively, suggesting the successful formation of granules. With decreasing HRT, LA productivity increased up to 16.7gLA/L-fermenter/h at HRT 0.5h. The existence of rod-shaped organisms with pores and internal channels at granule surface was observed by scanning electron microscope. Next generation sequencing revealed that Lactobacillus was the dominant microorganism, accounting for 96.7% of total sequences, comprising LA-producing granules.

Chlortetracycline degradation by photocatalytic ozonation in the aqueous phase: mineralization and the effects on biodegradability

Chlortetracycline (CTC) is a hazardous material in aquatic environments. This study was focused on optimization of photocatalytic ozonation processes for removal of CTC from wastewater at pH 2.2 and 7.0. In this study, the tested processes for CTC removal were arranged from the least efficient to the most efficient as: UV, UV/TiO2, O3, O3/UV and O3/UV/TiO2. Ozonation efficiency was due to ozone affinity for electron-rich sites on the CTC molecule. In the O3/UV and O3/UV/TiO2 processes, efficiency was increased by the photolysis of CTC and generation of •OH. At pH 7.0, all the processes were more efficient for CTC degradation than at pH 2.2 due to CTC speciation, ozone decay to •OH and the attractions between ionized CTC and TiO2 particles. UV/O3 at pH 7.0 showed an additive effect while other combination processes showed a synergistic effect that resulted in higher rates of reactions than the sums of individual reaction rates. The TOC removal ranged from 8% to 41% after one hour of reaction, with the above-mentioned order of efficiency. The biodegradability increased rapidly during the early minutes of the reaction. A reaction time of 10–15 min was sufficient for near maximum biodegradability, making these processes good pretreatments for the biological processes.

In situ soft XAS study on nickel-based layered cathode material at elevated temperatures: A novel approach to study thermal stability

Tracking thermally induced reactions has always been challenging for electrode materials of electrochemical battery systems. Traditionally, a variety of calorimetric techniques and in situ XRD at elevated temperatures has been used to evaluate the thermal stability of electrode materials. These techniques are capable of providing variations in heat capacity, mass and average bulk composition of materials only. Herein, we report investigation of thermal characteristics of Li0.33Ni0.8Co0.15Al0.05O2 by using in situ soft XAS measurements in combination with XRD. Fluorescence yield and partial electron yield measurements are used simultaneously to obtain element selective surface and bulk information. Fluorescence yield measurements reveal no energy change of the absorption peak and thus no valence state change in the bulk. However, electron yield measurements indicate that NiO-type rock salt structure is formed at the surface at temperatures above 200°C while no evidence for a surface reaction near Co sites in investigated temperature range is found. These results clearly show that in situ soft XAS can give a unique understanding of the role of each element in the structural transformation under thermal abuse offering a useful guidance in developing new battery system with improved safety performance.

Effects of transmembrane pressure and ozonation on the reduction of ceramic membrane fouling during water reclamation

AbstractThe effects of transmembrane pressure (TMP) and ozonation on the reduction of ceramic membrane fouling were investigated to reclaim and reuse secondary treated wastewater. A tubular ZnO3/TiO2 ceramic membrane with a molecular weight cutoff of 300 kD was used for filtration tests at different TMPs of 1, 2, and 3 bar. Pre-ozonation at 3, 6, and 9 mg/L O3 followed by membrane filtration at 1 bar were also conducted to assess the effect of ozonation on the reduction of membrane fouling and the improvements of water qualities. Ceramic membrane filtration removed large size of molecules, which were mostly aromatic and hydrophobic compounds. However, hydrophobic fractions of organics caused the irreversible fouling of the ceramic membrane; the irreversible fouling increased as TMP increased. Molecular weight distribution and fluorescence excitation emission matrix verified the results. Ozonation improved water quality and membrane permeability, regardless of the doses, but it could not decrease the relat...

Fatty acids fouling on forward osmosis membrane: impact of pH

AbstractThe fouling propensity of the fatty acids is investigated during the operation of the osmotically driven membrane process. Experiments were performed at various pH values ranged from 4.0 to 9.0 in the presence of the octanoic acid as the model fatty acids. Results demonstrated that the fatty acid fouling was significantly dependent on the changes of pH. In all tested pH values, permeate flux was sharply decreased during the initial coverage of fatty acids on the membrane surface, then slowly decreased as the fatty acid layer became developed. At pH 9.0, fouling propensity was less than those of pH values around 4.9 (pKa of octanoic acid) due to the protonation of the carboxylic group of octanoic acid molecules, which resulted in electrostatic repulsion between octanoic acid molecules and membrane surfaces. The measurement of contact angle and FTIR spectra also supports that more octanoic acid molecules are adsorbed on FO membrane surfaces at the low pH than at the high pH.