Changes in Dissolved Organic Matter Composition and Disinfection Byproduct Precursors in Advanced Drinking Water Treatment Processes.

Molecular changes in dissolved organic matter (DOM) from treatment processes at two drinking water treatment plants in Japan were investigated using unknown screening analysis by Orbitrap mass spectrometry. DOM formulas with carbon, hydrogen and oxygen (CHO-DOM) were the most abundant class in water samples, and over half of them were commonly found at both plants. Among the treatment processes, ozonation induced the most drastic changes to DOM. Mass peak intensities of less saturated CHO-DOM (positive (oxygen subtracted double bond equivalent per carbon (DBE-O)/C)) decreased by ozonation, while more saturated oxidation byproducts (negative (DBE-O)/C) increased and new oxidation byproducts (OBPs) were detected. By Kendrick mass analysis, ozone reactions preferred less saturated CHO-DOM in the same alkylation families and produced more saturated alkylation families of OBPs. Following ozonation, biological activated carbon filtration effectively removed <300 Da CHO-DOM, including OBPs. Following chlorination, over 50 chlorinated formulas of disinfection byproducts (DBPs) were found in chlorinated water samples where at least half were unknown. Putative precursors of these DBPs were determined based on electrophilic substitutions and addition reactions. Ozonation demonstrated better decomposition of addition reaction-type precursors than electrophilic substitution-type precursors; over half of both precursor types decreased during biological activated carbon filtration.

Comparative investigation of known and unknown disinfection by-product precursor removal and microbial community from biological biochar and activated carbon filters.

Biological activated carbon filter (BAC) is one of the most effective technologies for removing disinfection by-product (DBP) precursors from water. Biochar is a lower-cost medium that has the potential to replace granular activated carbon in BAC applications, thus leading to the development of biological biochar filter (BCF). This study compared BCF with BAC for the removal of DBP precursors using column experiments. Both BCF and BAC achieved the removal of DBP precursors, resulting in concentrations of all DBP formation potential below the World Health Organization guideline values for drinking water. Bromodichloromethane and unknown DBP precursor removal by BCF was comparable to that by BAC. However, BAC removed more chloroform and dichloroacetontrile precursors than BCF. For microbial community analysis, cell numbers in a bottom layer (inlet) of BCF and BAC columns were higher than those in the top layer. The abundances of Nordella and a microbial genus from Burkholderiaceae at the bottom layer showed a strong correlation to the number of DBP precursors removed and were comparable in BCF and BAC. This finding likely contributes to the similarities between DBPs species removed and the removal performances of some known and unknown DBP precursors by BCF and BAC. Overall results from this study revealed that biochar can be served as a low-cost and sustainable replacement of activated carbon in water filter for DBP precursor removal.

Changes in molecular dissolved organic matter and disinfection by-product formation during granular activated carbon filtration by unknown screening analysis with Orbitrap mass spectrometry.

The minimization of disinfection by-product (DBP) formation by the removal of its precursors before water disinfection is a highly effective approach. Granular activated carbon (GAC) filtration is widely used for water treatment, but our understanding of molecular dissolved organic matter (DOM) remains insufficient. This research investigates the removal of DOM and the minimization of DBP formation by pilot-scale coal- and coconut-based granular activated carbon filtrations (coAC and ccAC, respectively) using unknown screening analysis with Orbitrap mass spectrometry. DOM adsorption rates by both GACs were fitted with pseudo-second order models with initial adsorption rates of 0.005 mg g-1 min-1 and 0.022 mg g-1 min-1 for ccAC and coAC, respectively. Based on observations, ccAC was more effective in the removal of dissolved organic carbon and prolonged adsorption longer than coAC, as the breakthrough of coAC was found on Day 10. ccAC removed compounds with carbon, hydrogen, and oxygen (CHO features) with a wide range of oxidation states, as indicated by the carbon oxidation state (Cos), and a wide range of unsaturation, as indicated by oxygen subtracted double bond equivalent per carbon ([DBE-O]/C), while coAC selectively removed only those CHO features with less oxidized characters. Less oxidized compounds (low Cos) were preferentially removed with less contact time, while more oxidized compounds needed more contact time to adsorb on the GACs. A biofilm was developed on Day 60, and many CHO features were found to have increased after GAC treatment on Day 60, indicating the formation of microbial products. Chlorination resulted in a decrease in many CHO and CHO with Cl atom (CHOCl) features and the formation of CHOCl DBPs more than CHO DBP features. ccAC was effective in the minimization of trihalomethane (THM) and CHOCl DBP feature formations on Day 10 and Day 60, while coAC was found to be much less effective.

Characterization of molecular dissolved organic matter removed by modified eucalyptus-based biochar and disinfection by-product formation potential using Orbitrap mass spectrometric analysis.

Biochar is an alternative adsorbent, with similar characteristics to activated carbon, that can be applied to water treatment to remove dissolved organic matter (DOM) as disinfection by-product (DBP) precursors with comparable efficiency and better cost-effectiveness and sustainability relative to commercial alternatives. We applied non-targeted analysis with Orbitrap mass spectrometry to investigate changes in molecular DOM and DBP formation after treating DOM-containing water with biochar. Two surface water sources, Phong River (PR) in Khon Kaen, Thailand and Suwannee river (SR), USA, were tested using three types of eucalyptus-derived biochar (i.e., KOH-modified, calcined, and both) were selected as adsorbents and compared to commercial coconut-based activated carbon (ccAC). The results showed that calcination increased the surface area, pore volume, and functional groups of biochar responsible for adsorption. The calcined biochar achieved higher DOC removal efficiencies for both rivers than other adsorbents. PR contains more adsorbable DOM as over 800 molecules with carbon, hydrogen, and oxygen (CHO) features that were decreased or totally removed by all adsorbents. In contrast, for SR treatment, KOH-modified and calcined biochar was found to decrease over 800 CHO features, compared to around 500 and 400 CHO features for calcined biochar and ccAC, respectively. However, numerous background CHO features with reduced character (i.e., low degree of oxidation) were found after water treatment by calcined biochar, resulting in higher DBP formation after chlorination compared to the other adsorbents. The results of this study have important implications for future preparation of biochar for water treatment.

Characterization of DBP precursor removal by magnetic ion exchange resin using spectroscopy and high-resolution mass spectrometry.

The characteristics of dissolved organic matter (DOM) play an important role in the formation and speciation of carcinogenic disinfection byproducts. This study investigated changes in the characteristics and reactivity of DOM caused by the magnetic ion exchange resins, MIEX® DOC and MIEX® GOLD, using fluorescence excitation-emission matrix (EEM) with parallel factor (PARAFAC) analysis and Orbitrap mass spectrometry (Orbitrap MS) with unknown screening analysis. A five-component PARAFAC model was developed and validated from 208 EEMs of raw and MIEX®-treated water samples. The two resins exhibited preferential removal of the humic-like components (67-87% removal) and successfully removed protein-like components to a lesser extent (5-61% removal). Unknown screening analysis indicated removal of most condensed aromatic structures and lignin-like features that had high O/C values and refractory characteristics of lipid-like features by MIEX® treatments. MIEX® preferentially removed DOM molecules with more oxidized and shorter CH2 chains. The two resins had similar performance in trihalomethanes formation potential removal, but MIEX® GOLD achieved greater haloacetonitriles formation potential removal owing to its larger pore opening. Over 100 CHOCl DBP features were commonly found in all the samples while tens of CHOCl DBPs were uniquely formed in the samples with and without pre-treatments by MIEX®. Treatments by MIEX® before chlorination resulted in more intermediate CHOCl DBPs formed after chlorination compared to chlorinated raw waters. By optical spectroscopic analysis together with Orbitrap MS molecular characterization, we were able to confirm both quantitative and qualitative changes in DOM properties by MIEX® treatment related to DBP formation.

Characterization of dissolved organic carbon and disinfection by-products in biochar filter leachate using orbitrap mass spectrometry.

Biochar is a low-cost adsorbent with considerable potential for utilization as a water filtration medium; however, organic matter leaching from biochar can lead to the formation of disinfection by-products (DBPs). This study investigated the leaching of dissolved organic carbon (DOC) from eucalyptus-derived biochar and the formation of DBPs generated by chlorination and chloramination. Column experiments with empty bed contact times (EBCTs) of 10 and 30 min were conducted for 200 bed volumes (BVs). The highest DOC concentration (3.5 µg-C/g-biochar) was detected with an EBCT of 30 min. Chloroform (49 µg/L) and dichloroacetonitrile (7 µg/L) because of chlorination were found during the first five BVs, but were reduced thereafter. During the first 10 BVs, unknown chlorinated DBPs generated (CHOCl) by chlorination and chloramination (193 and 152 formulae, respectively) were tentatively identified via an unknown screening analysis. The release of DBP precursors from biochar tentatively identified in this study will impact water filtration applications.

Changes in dissolved organic matter during water treatment by sequential solid-phase extraction and unknown screening analysis.

Isolation of complex dissolved organic matter (DOM) from environmental water is a major challenge for unknown screening analysis by high-resolution mass spectrometry. In this study, DOM in process water during advanced drinking water treatment was fractionated sequentially by three solid-phase extraction (SPE) cartridges based on the polarity and charge of DOM molecules. By sequential SPE with unknown screening analysis, over 3000 DOM features were found in raw water, whereas around 2000 were obtained by a single SPE. The hydrophobic neutral (HPON) fraction contained CHO features with highest averaged molecular weight followed by hydrophobic acid (HPOA) and then hydrophilic acid (HPIA). The average degree of carbon double bond equivalents and carbon oxidation states indicated that the HPON fraction contained molecules that were more unsaturated and less oxidized than those of the HPOA and HPIA fractions. Ozone selectively decomposed (1) more unsaturated and less oxidized HPON features, (2) more unsaturated HPOA compounds, and (3) less oxidized HPIA molecules. Oxidation by-products were mostly HPON and HPIA compounds that were more oxidized than the decomposed molecules. During biological activated carbon (BAC) filtration, less oxidized HPON were preferentially removed, whereas HPOA were removed without selectivity. HPON and HPIA molecules with more oxidized character were found to be refractory to BAC treatment. HPON with more unsaturated and HPIA with more oxidized characters were decomposed by chlorine. Many types of HPIA decomposed during chlorination were the oxidation by-products of ozonation that were refractory to BAC treatment. Sequential SPE with unknown screening analysis provided previously unknown details of the molecular characteristics of DOM and its changes during advanced water treatment.

Orbitrap mass spectrometry for the molecular characterization of water resource recovery from polluted surface water using membrane bioreactor.

The increasing organic contamination of surface water hinders the conventional tap water treatment process. Membrane bioreactors (MBRs) are a promising alternative technology for recovering water from polluted surface water. In this study, the composition changes of dissolved organic matters (DOMs) in MBR and ultraviolet/ozone (UV/O3)-MBR systems for polluted surface water treatment were investigated using Orbitrap mass spectrometry analysis with unknown screening. The intense DOM ions within a mass-to-charge ratio range of 100-500 was detected, and 2340 molecular formulae from 5743 peaks were assigned to the two systems. The most abundant components were formulae with C, H, O, N, and CHO only classes. The highest formulae decrease including CHO, CHON, CHOS, and CHONS were attributed to the bio-carrier used in both systems. Results showed that bioprocess was the main contributor in the DOM reduction, and the integration of UV/O3 into the MBR improved the DOM composition changes. Biodegradable components with low O/C ratio in the CHO and CHON classes remarkably increased in the UV/O3-MBR system. The integration of UV/O3 as a polishing step in the recirculation stream of MBR system was effective in improve the DOM removal.

Characterization of lower Phong river dissolved organic matters and formations of unknown chlorine dioxide and chlorine disinfection by-products by Orbitrap mass spectrometry.

Dissolved organic matter (DOM) have been reported as precursors of disinfection byproducts (DBPs) and its molecular characteristics are rarely investigated due to its complexity. In this study, changes in the characteristics of DOM were investigated in the lower Phong River in Thailand in dry season and after the first rain in rainy season, using a non-targeted analysis with Orbitrap mass spectrometry. The river was rich with CHO features dominated by lignin-like molecules, while lipid-like molecules increase after domestic wastewater discharges. Wastewater discharge released DOM with higher molecular weight (MW) that was less oxygenated (low O/C) and less oxidized (low carbon oxidation state [Cos]). A lake affected by anthropogenic activities contributed more oxidized DOM into the river, while surface runoff carried DOM that is more oxygenated (high O/C), less hydrogenated (low H/C), and more oxidized (high Cos) to the stream. Water treatment further modified DOM to be lower MW. Approximately three hundred Cl-containing features (CHOCl) detected upstream were also found downstream. Disinfection by chlorine (Cl2) or chlorine dioxide (ClO2) formed both CHO and CHOCl DBPs. Low chlorine dosage applied to upstream and downstream samples resulted in many common unknown DBPs while increasing chlorine dosage resulted in more unique DBPs. At the same dosage, Cl2 reacted with DOM more than ClO2, including more oxidized molecules that are refractory to ClO2. Both Cl2 and ClO2 produced chlorinated and non-chlorinated DBPs, and some DBPs were commonly found by both disinfections. Cl2-produced DBPs were more unsaturated (higher [DBE-O]/C) and oxidized (higher Cos) than ClO2-DBPs.

Molecular dissolved organic matter removal by cotton-based adsorbents and characterization using high-resolution mass spectrometry.

This research investigates the characteristics of dissolved organic matter (DOM) removal by synthesized cotton-fiber adsorbents using unknown screening analysis with high resolution and accurate mass spectrometry. Molecular characteristics of DOM removed by adsorbents were investigated semiquantitatively and unknown disinfection byproduct (DBP) formation potentials were also investigated. Adsorbents were modified using ferric nitrate to increase the magnetic property. The XRD pattern showed Fe-containing crystalline structures in the modified adsorbent (M-CF). The M-CF possessed higher mesopore volume, which enhanced the dissolved organic carbon (DOC) removal efficiency to 74.50% (compared to 32.12% in the unmodified CF adsorbent). The kinetics experiment showed that both adsorbents were better fitted to pseudo-second orders than pseudo-first orders. The initial rate constant was higher in M-CF (1.40 mg/g min) than in CF (0.02 mg/g min) treatments due to the higher mesopore volume in M-CF. M-CF removed almost 700 carbon­hydrogen­oxygen based DOMs (CHO features), 300 more CHO features than CF. CF selectively adsorbed only higher-molecular-weight (MW) CHO features (more CH2 groups), while the mesopores in M-CF removed DOM with lower MW (fewer CH2 groups) that were refractory to CF. The low MW DOM removed only by M-CF mesopore exhibited more oxidized (positive carbon oxidation state, Cos) and saturated characters (negative oxygen-subtracted double bond equivalent per carbon, (DBE-O)/C). After chlorination, over 50 unknown DBPs were detected, 33 of which were commonly found in all samples. M-CF decreased unknown formation potential more than CF. However, adsorption of M-CF and CF before chlorination resulted in different remaining precursors to water chlorination and formed unique DBPs from those precursors.

Non-target screening of dissolved organic matter in raw water, coagulated water, and chlorinated water by Orbitrap mass spectrometry.

This study aimed to classify the possible molecular formulas of precursors for disinfection by-products (DBPs) in raw, coagulated, and chlorinated water samples from the U-Tapao Canal, Songkhla, Thailand. The molecular formulas of DBPs in chlorinated water were investigated. Polyaluminum chloride (PACl) was employed as a coagulant. Orbitrap Fourier transform-mass spectrometry was able to estimate the composition of dissolved organic matter (DOM) with the carbon (C), hydrogen (H), oxygen (O), nitrogen (N), and sulfur (S) elements contained and DBPs at the molecular level. The molecular formulas of the DOM in the raw water primarily consisted of CHO and CHON when extracted by lichrolut EN. The CHO and CHON species were rich in lignin-, tannin-, and condensed aromatic-like substances. The DOM with high-molecular-weight from 300 to 500 Da were preferentially removed by coagulation. The PACl coagulation decreased the abundances of lignin-, tannin-, and condensed aromatic-like substances in the CHO formulas, while lignin- and condensed aromatic-like substances in the CHON formulas remained. The remaining precursors corresponded to CHON molecules in the coagulated water, which may result in the formation of some chlorine (Cl)-containing molecules. Several DBPs among the CHOCl and CHONCl species were produced in the chlorinated water through the addition reaction of chlorine. New chlorinated N-DBPs of 21 formulas were detected.

Molecular characteristics of dissolved organic matter transformed by O3 and O3/H2O2 treatments and the effects on formation of unknown disinfection by-products.

We investigated semiquantitative changes in almost 1000 dissolved organic matter (DOM) features during oxidation with 1 mg of O3 per liter (mg O3/L), 4 mg O3/L, or 4 mg O3/L + 2.5 mg of H2O2 per liter (advanced oxidation process, AOP) by unknown screening analysis with Orbitrap mass spectrometry. The consequential effects on formation of unknown disinfection by-products (DBPs) by chlorination were evaluated in laboratory-scale experiments. Several hundred unsaturated DOM features with positive oxygen-subtracted double bond equivalents per carbon ((DBE-O)/C) were decomposed by the ozone-only treatment and AOP. The AOP decomposed some saturated (negative (DBE-O)/C)) and reduced molecules, which had negative carbon oxidation states (Cos). Several hundred saturated oxidation by-products were detected after ozonation and the AOP. After chlorination, the samples pre-treated with ozone alone resulted in higher formation of unknown DBPs than the AOP pre-treated sample or the sample without oxidation. Over half of the DBP precursors, estimated by electrophilic substitution, were not totally decomposed by any oxidation process, but they were increased after the ozone-only process and AOP. DBP precursors produced by the ozone-only process or AOP formed unique unknown DBPs. Therefore, post-treatment processes after oxidation and before chlorination are important to minimize formation of unknown DBPs.

Molecular characterization of low molecular weight dissolved organic matter in water reclamation processes using Orbitrap mass spectrometry.

Reclaimed water has recently become an important water source for urban use, but the composition of dissolved organic matter (DOM) in reclaimed water has rarely been characterized at the compound level because of its complexity. In this study, the transformation and changes in composition of low molecular weight DOM in water reclamation processes, where secondary effluent of the municipal wastewater treatment plant was further treated by biofiltration, ozonation and chlorination, were investigated by "unknown" screening analysis using Orbitrap mass spectrometry (Orbitrap MS). The intense ions were detected over an m/z range from 100 to 450. In total, 2412 formulae with various heteroatoms were assigned, and formulae with carbon (C), hydrogen (H) and oxygen (O) only and C, H, O and sulfur (S) were the most abundant species. During biofiltration, CHO-only compounds with relatively high hydrogen to carbon (H/C) ratio or with saturated structure were preferentially removed, while CHOS compounds were mostly removed. Ozonation induced the greatest changes in DOM composition. CHOS compounds were mostly decreased after ozonation while ozone selectively removed CHO compounds with relatively unsaturated structure and produced compounds that were more saturated and with a higher degree of oxidation. After chlorination, 168 chlorine-containing formulae, chlorinated disinfection by-products (DBPs), were additionally detected. Candidate DBP precursors were determined by tracking chlorinated DBPs formed via electrophilic substitution, half of which were generated during the ozonation.