Qian-Yuan Wu

Dichloroacetonitrile and Dichloroacetamide Can Form Independently during Chlorination and Chloramination of Drinking Waters, Model Organic Matters, and Wastewater Effluents

The increasing usage of organic nitrogen-rich wastewater- or algal-impacted waters, and chloramines for secondary disinfection, raises concerns regarding the formation of haloacetonitriles, haloacetamides and other nitrogenous disinfection byproducts (N-DBPs). Previous research obtained contradictory results regarding the relative importance of chlorination or chloramination for promoting these byproducts, but applied chlorine and chloramines at different doses and exposure periods. Additionally, mechanistic work, mostly using model precursors, suggested that haloacetonitrile and haloacetamide formation should be correlated because hydrolysis of haloacetonitriles forms haloacetamides. In this work, the formation of dichloroacetonitrile (DCAN) and dichloroacetamide (DCAcAm) were compared across a range of chlorine and chloramine exposures for drinking waters, wastewater effluents, algal extracellular polymeric substances (EPS), NOM isolates and model precursors. While chlorination favored formation of DCAN over DCAcAm, chloramination nearly always formed more DCAcAm than DCAN, suggesting the existence of haloacetamide formation pathways that are independent of the hydrolysis of haloacetonitriles. Experiments with asparagine as a model precursor also suggested DCAcAm formation without a DCAN intermediate. Application of (15)N-labeled monochloramine indicated initial rapid formation of both DCAN and DCAcAm by pathways where the nitrogen originated from organic nitrogen precursors. However, slower formation occurred by pathways involving chloramine incorporation into organic precursors. While wastewater effluents and algal EPS tended to be more potent precursors for DCAN during chlorination, humic materials were more potent precursors for DCAcAm during chlorination and for both DCAN and DCAcAm during chloramination. These results suggest that, rather than considering haloacetamides as haloacetonitrile hydrolysis products, they should be treated as a separate N-DBP class associated with chloramination. While use of impaired waters may promote DCAN formation during chlorination, use of chloramines may promote haloacetamide formation for a wider array of waters.

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.

Effects of chlorination on the properties of dissolved organic matter and its genotoxicity in secondary sewage effluent under two different ammonium concentrations

Recently, NH(4)(+) has been reported to induce potential risks during wastewater chlorination. Thus, the effects of chlorination on genotoxicity and fluorescence spectra of secondary sewage effluents, were investigated in this study before and after adding a high NH(4)(+) quantity. Chlorination decreased the genotoxicity of secondary sewage effluent, while the presence of a high level of NH(4)(+) inhibited this decrease. By further ultrafiltration following XAD-8 resin fractionation, it was found that, with a high NH(4)(+) concentration, the genotoxicity in the fraction of hydrophobic acids (HOA) increased after chlorination and a sub-fraction of HOA with molecular weight less than 1 kDa was the key fraction resulting in this increase. Similar to genotoxicity changes, NH(4)(+) was also found to influence the changes in fluorescence spectra during chlorination. After chlorination, the fluorescence intensity of the dissolved organic matter (DOM) notably decreased, and the emission band of DOM fluorescence spectra shifted to a lower wavelength. However, the presence of NH(4)(+) inhibited both the decrease in intensity and shift. The changes in fluorescence spectra suggested that the fluorescent structure of secondary effluent may decompose during chlorination, but NH(4)(+) could inhibit this decomposition.

Differences in dissolved organic matter between reclaimed water source and drinking water source

Dissolved organic matter (DOM) significantly affects the quality of reclaimed water and drinking water. Reclaimed water potable reuse is an effective way to augment drinking water source and de facto reuse exists worldwide. Hence, when reclaimed water source (namely secondary effluent) is blended with drinking water source, understanding the difference in DOM between drinking water source (dDOM) and reclaimed water source (rDOM) is essential. In this study, composition, transformation, and potential risk of dDOM from drinking water source and rDOM from secondary effluent were compared. Generally, the DOC concentration of rDOM and dissolved organic nitrogen (DON) content in reclaimed water source were higher but rDOM exhibited a lower aromaticity. Besides, rDOM comprises a higher proportion of hydrophilic fractions and more low-molecular weight compounds, which are difficult to be removed during coagulation. Although dDOM exhibited higher specific disinfection byproducts formation potential (SDBPFP), rDOM formed more total disinfection byproducts (DBPs) during chlorination including halomethanes (THMs) and haloacetic acids (HAAs) due to high DOC concentration. Likewise, in consideration of DOC basis, rDOM contained more absolute assimilable organic carbon (AOC) despite showing a lower specific AOC (normalized AOC per unit of DOC). Besides, rDOM exhibited higher biotoxicity including genotoxicity and endocrine disruption. Therefore, rDOM presents a greater potential risk than dDOM does. Reclaimed water source needs to be treated carefully when it is blended with drinking water source.

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.

Monitoring and evaluation of removal of pathogens at municipal wastewater treatment plants

The concentrations and removal of Cryptosporidium, Giardia, and microbial indicators, including somatic coliphages and fecal coliforms were investigated through the wastewater treatment processes at three municipal wastewater treatment plants in Beijing, China. The experimental results showed that the concentrations of Cryptosporidium in untreated wastewater, primary treatment effluent, secondary treatment effluent, tertiary treatment effluent were 33-600, 67-333, 0-9 and 0-0.4 oocysts L(-1), and that of Giardia were 130-3,600, 533-2,033, 0-32 and 0-2.1 cysts L(-1), respectively. The reduction ratios of Cryptosporidium and Giardia by the primary treatment process were 0.12 log and 0.18 log, respectively. Oxidation ditch process had higher reduction efficiency to Cryptosporidium and Giardia than anaerobic-anoxic-oxic process and conventional activated sludge process, probably because of longer retention time and higher sludge concentration. Membrane ultrafiltration had a notably better efficiency to reduce microorganisms, especially Cryptosporidium and Giardia, than conventional flocculation sedimentation and sand filtration process, as the tertiary treatment. Comparing with total coliforms, fecal coliforms and heterotrophic bacteria, concentration of somatic coliphages was correlated better with that of Cryptosporidium and Giardia in untreated wastewater and secondary treatment effluent.

Removal of genotoxicity in chlorinated secondary effluent of a domestic wastewater treatment plant during dechlorination

PurposeDechlorination with tetravalent sulfur is widely used in wastewater treatment processes after chlorination. Dechlorination can remove certain genotoxic disinfection by-products (DBPs). However, the reactions occurring during dechlorination of chlorinated secondary effluent and their genotoxic chemicals are still very complex, and the related genotoxicity changes remain unknown. Therefore, the effects of dechlorination on genotoxicity in secondary effluent and its fractions and typical genotoxic chemical after chlorination were evaluated.MethodsThe dissolved organic matter in the secondary effluent sample was separated into four fractions with XAD-8 resin. Genotoxicity of secondary effluent and its fractions was evaluated by SOS/umu test, an ISO standard method. The concentration of typical genotoxic chemical named ofloxacin was determined by liquid chromatography with a mass spectrometer and a fluorescence detector.ResultsDechlorination with the addition of Na2SO3 notably decreased the genotoxicity in the chlorinated secondary effluent, especially in the presence of high ammonia nitrogen concentration in the sample before chlorination. The Na2SO3 addition significantly decreased the genotoxicity of the secondary effluent and its genotoxic ofloxacin prior to chlorination. The genotoxicity in the fractions containing hydrophobic acids (HOA) increased after chlorination, while addition of Na2SO3 decreased the genotoxicity induced by chlorination. Tryptophan found in HOA exhibited genotoxicity after chlorination, while dechlorination decreased the genotoxicity in chlorinated tryptophan induced by DBPs.ConclusionsDechlorination was found to decrease the genotoxicity of chlorinated secondary effluent. The decrease was associated with the reduction of genotoxicity in genotoxic chemicals in secondary effluent prior to chlorination and DBPs.

Formation of haloacetonitriles and haloacetamides during chlorination of pure culture bacteria

The increasing reuse of organic nitrogen-rich wastewater raises concerns regarding the formation of nitrogenous disinfection by-products (N-DBPs), such as haloacetonitriles and haloacetamides. Previous research mainly focused on N-DBPs formation from dissolved organic matter in wastewater. In this study, dichloroacetonitrile (DCAN) and dichloroacetamide (DCAcAm) formation from particles in the secondary effluents of a domestic wastewater treatment plant during chlorination was assessed to account for 26-46% of the total formation. As part of particles in wastewater, bacterial cells enriched in organic nitrogen are considered a potential source for the formation of N-DBPs during chlorination. The formation of DCAN, DCAcAm and trichloroacetamide (TCAcAm) during the chlorination of a Gram-negative bacterium of Escherichia coli (E. coli) and a Gram-positive bacterium of Enterococcus faecalis (E. faecalis) were then evaluated. Compared with dissolved organic matter in the secondary effluent, bacterial cells formed more DCAN, DCAcAm and TCAcAm during chlorination. E. faecalis formed more DCAN, but less DCAcAm and TCAcAm than E. coli did under most chlorination conditions. Moreover, the effects of contact time, chlorine dose, pH value and ammonia nitrogen concentration on the N-DBPs formation from the two bacterial suspensions were investigated. Under the chlorination conditions in this study, DCAN formation from the bacterial suspensions initially increased and then decreased, while TCAcAm formation increased with increasing contact time and chlorine dose. DCAcAm formation from the bacterial suspensions increased with the prolonged contact time, and increased and then decreased with increasing chlorine dose. DCAN, DCAcAm and TCAcAm formation was favored under neutral pH condition, but was reduced with the addition of ammonia during the chlorination of the two bacterial suspensions.

Transformation of anti-estrogenic-activity related dissolved organic matter in secondary effluents during ozonation

Anti-estrogenic activity of dissolved organic matter (DOM) in reclaimed water is gaining increasing attention. In this study, anti-estrogenic activity removal efficiency by ozonation in the tertiary treatment process of domestic wastewater was investigated. The anti-estrogenic activity in the secondary effluents used in this study ranged between 0.95 and 2.00 mg-TAM L(-1) and decreased significantly after ozonation. The removal efficiency of anti-estrogenic activity at a dose of 10 mg-O3 L(-1) was 65-87%. The removal of the anti-estrogenic activity was highly correlated with the removal of UV254, suggesting that UV254 can be used as a surrogate for anti-estrogenic activity during ozonation. The results of size exclusion chromatography of the wastewater samples during ozonation showed that the UV254 absorbance of the DOM fraction with large apparent molecular weight (MW) around 7.6 k Da dropped significantly, and the DOM fraction was suspected to be humic substances which have been previously identified as anti-estrogenic constituents in secondary effluents. The excitation emission matrix fluorescence spectra of the wastewater samples proved that humic substances existed in the DOM and indeed reacted with the ozone. With the help of two-dimensional correlation of Fourier transform infrared, it was confirmed that the aromatic structures in the DOM were largely destroyed by ozonation. Therefore, it was suggested that the destruction of the aromatic structures in the DOM was related to the removal of the anti-estrogenic activity.

Removal potential of anti-estrogenic activity in secondary effluents by coagulation

Anti-estrogenic activity in wastewater is gaining increased attention because of its endocrine-disrupting function. In this study, the level and removal efficiency by coagulation of anti-estrogenic activity in secondary effluents of domestic wastewater treatment plants were studied. Anti-estrogenic activity was detected in secondary effluent samples at a tamoxifen (TAM) equivalent concentration level of 0.38-0.94 mg-TAML(-1). Dissolved organic matters (DOM) with the molecular weight (MW) less than 3000 Da in hydrophobic acids (HOA) and hydrophobic neutrals (HON) fractions of the secondary effluent were the key fractions related to anti-estrogenic activity. Coagulation with FeCl(3) and polyaluminium chloride (PAC) can remove the anti-estrogenic activity of the secondary effluents, but the removal efficiency was limited. The removal efficiency using FeCl(3) coagulant was higher than that induced by PAC. Dissolved organic carbon was continuously removed with increased coagulant dose (0-120 mg L(-1) FeCl(3) or 0-60 mg L(-1) PAC). However, the removal of anti-estrogenic activity was not enhanced further when the coagulant concentration was beyond a critical value (30 mg L(-1) FeCl(3) or 10 mg L(-1) PAC). The highest removal of anti-estrogenic activity was about 36% by FeCl(3) and 20% by PAC. Size exclusion chromatography results indicated difficulty in removing DOM with MW less than 3000 Da in the secondary effluent during coagulation even at a high coagulant concentration, which led to low removal efficiency of anti-estrogenic activity.