Ying-Xue Sun

Effects of operating conditions on THMs and HAAs formation during wastewater chlorination

Disinfection is the last barrier of wastewater reclamation process to protect ecosystem safety and human health. However, the chlorination process results in the formation of mutagenic/carcinogenic disinfection by-products (DBPs) deriving from the reaction of the chlorine with organic compounds in wastewater. The effects of operating conditions (chlorine dose, contact time, reaction temperature and pH value) of chlorination on the formation of trihalomethanes (THMs) and haloacetic acids (HAAs) in biologically treated wastewater samples were investigated in this study. The results indicated that the total THMs (TTHM) and total HAAs (THAA) increased exponentially with increasing chlorine dose, but there are discrepancies between the formation rates of TTHM and THAA. The THAA reached a peak at contact time of 2h and thereafter decreased with extended time. The formation time of THMs depends on the wastewater content of quick or slow formers. The yields of bromated HAAs (as MBAA, BCAA, and BDCAA) would decrease markedly after the contact time over 2h during wastewater chlorination, and were favored in low pH values of 4 and high pH values of 9 under certain contact time. In addition, the formation of MBAA, BCAA, BDCAA decreased gradually as reaction temperature increased from 4 to 30 degrees C in the chlorination of wastewater containing a certain concentration of bromide. The effects of operating conditions on THMs and HAAs formation during wastewater chlorination were completely different from those of surface water disinfection.

Reduced effect of bromide on the genotoxicity in secondary effluent of a municipal wastewater treatment plant during chlorination.

Chlorination of wastewater can form genotoxic, mutagenic, and/or carcinogenic disinfection byproduct (DBPs). In this study, the effect of bromide on genotoxicity in secondary effluent of a municipal wastewater treatment plant during chlorination was evaluated by the SOS/umu test. The presence of bromide notably decreased the genotoxicity in secondary effluent during chlorination, especially under conditions of high ammonia concentration. Bromide significantly decreased the concentration of ofloxacin, a genotoxic chemical in secondary effluent, during chlorination with high concentration of ammonia, while genotoxic DBPs formation of humic acid and aromatic amino acids associated with bromide limitedly contributed to the changes of genotoxicity in secondary effluent under the conditions of this study. By fractionating dissolved organic matter (DOM) in the secondary effluent into different fractions, the fractions containing hydrophilic substances (HIS) and hydrophobic acids (HOA) contributed to the decrease in genotoxicity induced by bromide. Chlorination of HOA without bromide increased genotoxicity, while the addition of bromide decreased genotoxicity.

Characterization and biotoxicity assessment of dissolved organic matter in RO concentrate from a municipal wastewater reclamation reverse osmosis system

Reverse osmosis (RO) concentrate from municipal wastewater reclamation reverse osmosis (mWRRO) system containing organic compounds may associate with toxic risk, and its discharge might pose an environmental risk. To identify a basis for the selection of feasible technology in treating RO concentrates, the characteristics and biotoxicity of different fractions of dissolved organic matter (DOM) in RO concentrates from an mWRRO system were investigated. The results indicated that the hydrophilic neutrals (HIN), hydrophobic acids (HOA) and hydrophobic bases (HOB) accounted for 96% of the dissolved organic carbon (DOC) of the total DOM in the RO concentrate. According to the SEC chromatograph detected at 254 nm wavelength of UV, the DOM with molecular weight (MW) 1-3 kDa accounted for the majority of the basic and neutral fractions. The fluorescence spectra of the excitation emission matrix (EEM) indicated that most aromatic proteins, humic/fulvic acid-like and soluble microbial by-product-like substances existed in the fractions HOA and hydrophobic neutrals (HON). The genotoxicity and anti-estrogenic activity of the RO concentrate were 1795.6 ± 57.2 μg 4-NQOL(-1) and 2.19 ± 0.05 mg TAM L(-1), respectively. The HIN, HOA, and HOB contributed to the genotoxicity of the RO concentrate, and the HIN was with the highest genotoxic level of 1007.9 ± 94.8 μg 4-NQOL(-1). The HOA, HON, and HIN lead to the total anti-estrogenic activity of the RO concentrate, and HOA occupied approximately 60% of the total, which was 1.3 ± 0.17 mg TAM L(-1).

Effects of chemical agent injections on genotoxicity of wastewater in a microfiltration-reverse osmosis membrane process for wastewater reuse

With combined microfiltration (MF)/ultrafiltration (UF) and reverse osmosis (RO) process being widely used in municipal wastewater reclamation, RO concentrate with high level genotoxicity is becoming a potential risk to water environment. In this study, wastewater genotoxicity in a MF-RO process for municipal wastewater reclamation and also the effects of chemical agent injections were evaluated by SOS/umu genotoxicity test. The genotoxicity of RO concentrate ranged 500-559 μg 4-NQO (4-nitroquinoline-1-oxide)/L and 12-22 μg 4-NQO/mg DOC, was much higher than that of RO influent. Further research suggested that Kathon biocide was a key chemical agent associated with the genotoxicity increase. Kathon biocide used in RO system was highly genotoxic in vitro and Kathon biocide retained in RO system could contribute to a higher genotoxicity of RO concentrate. Hence, treatments for biocides before discharging are necessary. Chlorination of secondary effluent could significantly decrease the genotoxicity and increasing chlorine dosage could be an efficacious method to decrease the genotoxicity of RO concentrate. According to the result of the experiment, the dosage of chlorine in dual-membrane process could be set to about 2.5 mg Cl₂/L. The effect of antiscalant (2-phosphomobutane-1,2,4-tricarboxylic acid) was also investigated; it turned out to have no effect on genotoxicity.

Changes in the components and biotoxicity of dissolved organic matter in a municipal wastewater reclamation reverse osmosis system

ABSTRACT The characteristics of dissolved organic matter (DOM) and the biotoxicity of these components were investigated in a municipal wastewater reclamation reverse osmosis (mWRRO) system with a microfiltration (MF) pretreatment unit. The MF pretreatment step had little effect on the levels of dissolved organic carbon (DOC) in the secondary effluent, but the addition of chlorine before MF promoted the formation of organics with anti-estrogenic activity. The distribution of excitation emission matrix (EEM) fluorescence constituents exhibited obvious discrepancies between the secondary effluent and the reverse osmosis (RO) concentrate. Using size exclusion chromatography, DOM with low molecular weights of approximately 1.2 and 0.98 kDa was newly formed during the mWRRO. The normalized genotoxicity and anti-estrogenic activity of the RO concentrate were 32.1 ± 10.2 μg4-NQO/mgDOC and 0.36 ± 0.08 mgTAM/mgDOC, respectively, and these values were clearly higher than those of the secondary effluent and MF permeate. The florescence volume of Regions I and II in the EEM spectrum could be suggested as a surrogate for assessing the genotoxicity and anti-estrogenic activity of the RO concentrate.

Characterization of trihalomethane, haloacetic acid, and haloacetonitrile precursors in a seawater reverse osmosis system

Seawater reverse osmosis (SWRO) has been extensively applied to replenish the limited freshwater resources. One concern of such technology is the formation of disinfection by-products (DBPs) during the pre-chlorination process. For the SWRO tested in this study, the concentrations of trihalomethanes (THMs), haloacetic acids (HAAs), and haloacetonitriles (HANs) increased by 35.1, 23.7 and 4.9μg/L, respectively, after a seawater sample (with UV254/DOC of 3.7L/mg·m and Br- of 50.9mg/L) was pre-chlorinated (1-2mg-Cl2/L). The dissolved organic matter (DOM) with molecular weight (MW) <1kDa dominated the formation of total THMs, HAAs and HANs. To further investigate DBPs precursors in the seawater, the DOM with MW<1kDa was fractionated to hydrophobic acids (HOA), hydrophobic bases (HOB), hydrophobic neutrals (HON), and hydrophilic substances (HIS). The excitation emission matrix fluorescence spectra analysis showed that most aromatic protein and fulvic acid of the DOM with MW<1kDa were present in the HON and HIS fractions. The HON fraction was the dominant precursor to form THMs and HAAs, while HIS controlled the formation of HANs. Furthermore, bromo - DBPs dominated the total DBPs yields after the chlorination of HIS fraction.