Wenhai Chu

Precursors of Dichloroacetamide, an Emerging Nitrogenous DBP Formed during Chlorination or Chloramination

Haloacetamides (HAcAms) are an emerging class of nitrogenous disinfection byproducts (N-DBPs). However, there is a limited understanding about the precursors of HAcAms. In this study, we screened the precursors of dichloroacetamide (DCAcAm), the most commonly identified HAcAm in chlorinated or chloraminated drinking water. DCAcAm formation potential (FP) of raw water samples collected in different months from a reservoir in China was determined during chlorination, and the highest DCAcAm FP typically occurred in the summer samples. Dissolved organic matter (DOM) in a representative summer raw water sample was separated into six fractions by a series of resin elutions. Among them, hydrophilic acid (HiA) DOM showed the maximum DCAcAm FP, followed by hydrophilic bases (HiB) and, to a much lower extent, hydrophobic acids (HoA). Fluorescence excitation-emission matrix (EEM) spectra revealed that a mass of protein-like substances in the HiA fraction, made up of amino acids (AAs), were the likely DCAcAm precursors. Finally, we investigated the DCAcAm yields of 20 AAs during chlorination. Among them, seven AAs (aspartic acid, histidine, tyrosine, tryptophan, glutamine, asparagine, phenylalanine) could form DCAcAm during chlorination, with the corresponding DCAcAm yields of 0.231, 0.189, 0.153, 0.104, 0.078, 0.058, and 0.050 mmol/mol AA.

Formation of halogenated C-, N-DBPs from chlor(am)ination and UV irradiation of tyrosine in drinking water

The formation of regulated and emerging halogenated carbonaceous (C-) and nitrogenous disinfection by-products (N-DBPs) from the chlor(am)ination and UV irradiation of tyrosine (Tyr) was investigated. Increased chlorine contact time and/or Cl(2)/Tyr ratio increased the formation of most C-DBPs, with the exception of 4-chlorophenol, dichloroacetonitrile, and dichloroacetamideChloroform and dichloroacetic acid increased with increasing pH, dichloroacetonitrile first increased and then decreased, and other DBPs had maximum yields at pH 7 or 8. The addition of ammonia significantly reduced the formation of most C-DBPs but increased 4-chlorophenol, dichloroacetonitrile, dichloroacetamide, and trichloroacetonitrile yields for short prechlorination contact times before dosing ammonia. When UV irradiation and chlorination were performed simultaneously, the concentrations of the relatively stable C-DBPs increased, and the concentrations of dichloroacetonitrile, dichloroacetamide, and 4-chlorophenol decreased with increasing UV dose. This information was used to develop a mechanistic model for the formation of intermediate DBPs and end products from the interaction of disinfectants with tyrosine.

Ozone-biological activated carbon integrated treatment for removal of precursors of halogenated nitrogenous disinfection by-products

Pilot-scale tests were performed to reduce the formation of several nitrogenous and carbonaceous disinfection by-products (DBPs) with an integrated ozone and biological activated carbon (O(3)-BAC) treatment process following conventional water treatment processes (coagulation-sedimentation-filtration). Relative to the conventional processes alone, O(3)-BAC significantly improved the removal of turbidity, dissolved organic carbon, UV(254), NH(4)(+) and dissolved organic nitrogen from 98-99%, 58-72%, 31-53%, 16-93% and 35-74%, respectively, and enhanced the removal efficiency of the precursors for the measured DBPs. The conventional process was almost ineffective in removing the precursors of trichloronitromethane (TCNM) and dichloroacetamide (DCAcAm). Ozonation could not substantially reduce the formation of DCAcAm, and actually increased the formation potential of TCNM; it chemically altered the molecular structures of the precursors and increased the biodegradability of N-containing organic compounds. Consequently, the subsequent BAC filtration substantially reduced the formation of the both TCNM and DCAcAm, thus highlighting a synergistic effect of O(3) and BAC. Additionally, O(3)-BAC was effective at controlling the formation of the total organic halogen, which can be considered as an indicator of the formation of unidentified DBPs.

The control of emerging haloacetamide DBP precursors with UV/persulfate treatment.

Haloacetamides (HAcAms), an emerging class of nitrogen-containing disinfection byproducts (N-DBPs) of health concern in drinking water, have been reported to occur in treated drinking waters at low μg/L levels typically. The objective of this study was to examine the potential of an ultraviolet light/persulfate (UV/PS) oxidation technology to reduce the precursors of HAcAms and also minimize the formation of other N-DBPs upon subsequent chlorination. Low-pressure UV photolysis alone and PS pre-oxidation alone did not significantly affect HAcAm formation, however UV/PS pre-oxidation achieved a statistically significant reduction in HAcAm formation and also reduced bromine incorporation into the HAcAms. UV/PS also showed a good performance in removing the precursors of haloacetonitriles and halonitromethanes prior to chlorination. Therefore, UV/PS has the potential to minimize the formation of a range of N-DBPs in organic nitrogen-rich waters where N-DBP precursors are prevalent. However, these benefits should be weighed against the potential drawbacks of increased bromate and sulfate formation, particularly in high-bromide waters.

Trace determination of 13 haloacetamides in drinking water using liquid chromatography triple quadrupole mass spectrometry with atmospheric pressure chemical ionization

The haloacetamides (HAcAms) are disinfection by-products (DBPs) in drinking water which are currently receiving increased scientific attention due to their elevated toxicity relative to regulated disinfection by-products. A simultaneous determination method of 13 HAcAms, combining solid-phase extraction (SPE) enrichment, liquid chromatographic (LC) separation, and triple quadrupole mass spectrometry (tqMS) detection with atmospheric pressure chemical ionization (APCI) using selective reaction monitoring in positive mode, was developed to measure HAcAms, including chlorinated, brominated, and iodinated analogs. Ammonium chloride and Oasis HLB were selected as the dechlorinating reagent and polymeric SPE sorbent of HAcAm samples. The used tqMS apparatus showed higher sensitivity for the studied HAcAms in the APCI mode than electrospray ionization. 13 HAcAms were separated by LC in 9.0 min, and the detection limits ranged from 7.6 to 19.7 ng/L. The SPE-LC/tqMS method was successfully applied to quantify 13 HAcAms in drinking water samples for the first time, and first indentified tribromoacetamide and chloroiodoacetamide as DBPs in drinking water.

Formation and speciation of nine haloacetamides, an emerging class of nitrogenous DBPs, during chlorination or chloramination

Haloacetamides (HAcAms) are an emerging class of nitrogenous disinfection by-products (N-DBPs) of health concern. However, there are very limited data on the formation and speciation of the nine bromine- and chlorine-containing haloacetamides (HAcAm9). In the study, their formation and speciation during chlor(am)ination were investigated for a group of waters with a range of specific ultraviolet absorbance at 254 nm (SUVA₂₅₄), dissolved organic nitrogen (DON), and bromide levels. The waters that were the least impacted by anthropogenic pollution had the lowest DON levels, the highest ratios of dissolved organic carbon (DOC) to DON, and exhibited the least HAcAm9 formation. DON/DOC may act as an indicator of HAcAm yields during chlorination. HAcAm9 exhibited more formation during chloramination in the low-SUVA waters with no bromide, relative to high-SUVA waters with bromide. The selected waters all formed primarily dihalogenated (di-) HAcAms, followed by trihalogenated (tri-) species and, to a much lesser extent, monohalogenated (mono-) HAcAms. Di-HAcAm formation had similar trends as that of HAcAm9; whereas chloramination formed more mono- and less tri-HAcAms than chlorination. Bromine utilization factors and bromine incorporation factor increased with decreasing and increasing bromide during either chlorination or chloramination, and bromine was easier to incorporate into tri-HAcAms during chloramination than chlorination.

Impacts of drinking water pretreatments on the formation of nitrogenous disinfection by-products.

The formation of disinfection by-products (DBPs), including both nitrogenous DBPs (N-DBPs) and carbonaceous DBPs (C-DBPs), was investigated by analyzing chlorinated water samples following the application of three pretreatment processes: (i) powdered activated carbon (PAC) adsorption; (ii) KMnO(4) oxidation and (iii) biological contact oxidation (BCO), coupled with conventional water treatment processes. PAC adsorption can remove effectively the precursors of chloroform (42.7%), dichloroacetonitrile (28.6%), dichloroacetamide (DCAcAm) (27.2%) and trichloronitromethane (35.7%), which were higher than that pretreated by KMnO(4) oxidation and/or BCO process. The removal efficiency of dissolved organic carbon by BCO process (76.5%)--was superior to that by PAC adsorption (69.9%) and KMnO(4) oxidation (61.4%). However, BCO increased the dissolved organic nitrogen (DON) concentration which caused more N-DBPs to be formed during subsequent chlorination. Soluble microbial products including numerous DON compounds were produced in the BCO process and were observed to play an essential role in the formation of DCAcAm in particular.

Impact of UV/H2O2 Pre-Oxidation on the Formation of Haloacetamides and Other Nitrogenous Disinfection Byproducts during Chlorination

Haloacetamides (HAcAms), an emerging class of nitrogen-based disinfection byproducts (N-DBPs) of health concern in drinking water, have been found in drinking waters at μg/L levels. However, there is a limited understanding about the formation, speciation, and control of halogenated HAcAms. Higher ultraviolet (UV) doses and UV advanced oxidation (UV/H2O2) processes (AOPs) are under consideration for the treatment of trace organic pollutants. The objective of this study was to examine the potential of pretreatment with UV irradiation, H2O2 oxidation, and a UV/H2O2 AOP for minimizing the formation of HAcAms, as well as other emerging N-DBPs, during postchlorination. We investigated changes in HAcAm formation and speciation attributed to UV, H2O2 or UV/H2O2 followed by the application of free chlorine to quench any excess hydrogen peroxide and to provide residual disinfection. The results showed that low-pressure UV irradiation alone (19.5-585 mJ/cm(2)) and H2O2 preoxidation alone (2-20 mg/L) did not significantly change total HAcAm formation during subsequent chlorination. However, H2O2 preoxidation alone resulted in diiodoacetamide formation in two iodide-containing waters and increased bromine utilization. Alternatively, UV/H2O2 preoxidation using UV (585 mJ/cm(2)) and H2O2 (10 mg/L) doses typically employed for trace contaminant removal controlled the formation of HAcAms and several other N-DBPs in drinking water.

Comparison of inclined plate sedimentation and dissolved air flotation for the minimisation of subsequent nitrogenous disinfection by-product formation

The formation of disinfection by-products (DBPs), including both nitrogenous disinfection by-products (N-DBPs) and carbonaceous disinfection by-products (C-DBPs), was investigated upon chlorination of water samples following two treatment processes: (i) coagulation-inclined plate sedimentation (IPS)-filtration and (ii) coagulation-dissolved air flotation (DAF)-filtration. The removal of algae, dissolved organic nitrogen (DON), dissolved organic carbon (DOC) and UV(254) by coagulation-DAF-filtration was superior to coagulation-IPS-filtration. On average, 53%, 53% and 31% of DOC, DON and UV(254) were removed by coagulation-DAF-filtration process, which were higher than 47%, 31% and 27% of that by coagulation-IPS-filtration process. Additionally, coagulation-IPS-filtration performed less well at removing the low molecular weight organics than coagulation-DAF-filtration process. The concentrations of chloroform, dichloroacetamide (DCAcAm) and dichloroacetonitrile (DCAN) formed during chlorination after coagulation-DAF-filtration reached their maximum values of 13, 1.5 and 4.7μgL(-1), respectively, and were lower than those after coagulation-IPS-filtration with the maximum detected levels of 17, 2.9 and 6.3μgL(-1). However, the trichloronitromethane (TCNM) concentration after the two processes was similar, suggesting that DON may have less of a contribution to TCNM formation than DCAcAm and DCAN.

Removal of phenol by powdered activated carbon adsorption

In this study, the adsorption performance of powdered activated carbon (PAC) on phenol was investigated in aqueous solutions. Batch adsorption studies were performed to evaluate the effects of various experimental parameters like PAC type, PAC dose, initial solution pH, temperature and pre-oxidation on the adsorption of phenol by PAC and establish the adsorption kinetics, thermodynamics and isothermal models. The results indicated that PAC adsorption is an effective method to remove phenol from water, and the effects of all the five factors on adsorption of phenol were significant. The adsorption rate of phenol by PAC was rapid, and more than 80% phenol could be absorbed by PAC within the initial 10 min. The adsorption process can be well described by pseudo-second-order adsorption kinetic model with rate constant amounted to 0.0313, 0.0305 and 0.0241 mg·μg−1·min−1 with coal, coconut shell and bamboo charcoal. The equilibrium data of phenol absorbed onto PAC were analyzed by Langmuir, Freundlich and Tempkin adsorption isotherms and Freundlich adsorption isotherm model gave the best correlation with the experimental data. Thermodynamic parameters such as the standard Gibbs free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) obtained in this study indicated that the adsorption of phenol by PAC is spontaneous, exothermic and entropy decreasing.