Disinfection By-product Precursors Research Articles

Chlorination of soil-derived dissolved organic matter: Long term nitrogen deposition does not increase terrestrial precursors of toxic disinfection byproducts

Terrestrial dissolved organic matter (DOM) in forested watersheds is a known precursor of disinfection byproducts (DBPs) in drinking water. Although the characteristics of terrestrial DOM may change with increasing nitrogen (N) deposition in forests, how these changes alter formation potential and toxicity of DBPs remains unexplored. We analyzed the speciation and toxicity of DBPs from chlorination of DOM derived from soils (O, A, and B horizons) in an experimental temperate forest with 22 years of N addition. With long-term N addition, the DOM reactivity toward the formation of trihalomethanes (from 27.7–51.8 to 22.8–31.1 µg/mg-dissolved organic carbon (DOC)) and chloral hydrate (from 1.25–1.63 to 1.14–1.36 µg/mg-DOC) decreased, but that toward the formation of haloketones increased (from 0.23–0.26 to 0.26–0.33 µg/mg-DOC). The DOM reactivity toward the formation of haloacetonitriles was increased in the deeper soil but reduced in the surface soil. The DBP formation potential of DOM draining from a certain area of forest soils (in µg-DBP/m2-soil) was estimated to be reduced by 20.3% for trihalomethanes and increased by 37.5% for haloketones and have minor changes for haloacetonitriles and chloral hydrate (both <7%). Furthermore, the DBPs from chlorination of the soil-derived DOM showed lowered microtoxicity with N addition possibly due to reduced brominated DBP formation. Overall, this study highlights that N deposition may not increase drinking water toxicity through altering terrestrial DOM characteristics.

Long-term biochar addition alters the characteristics but not the chlorine reactivity of soil-derived dissolved organic matter

Biochar is widely and increasingly applied to farmlands. However, it remains unclear how long-term biochar addition alters the characteristics and chlorine reactivity of soil-derived dissolved organic matter (DOM), an important terrestrial disinfection byproduct (DBP) precursor in watersheds. Here, we analyzed the spectroscopic and molecular-level characteristics of soil-derived DOM and the formation and toxicity of DBP mixtures from DOM chlorination for two long-term (5 and 11 years) biochar addition experimental farmlands. As indicated by spectroscopic indices and Fourier transform ion cyclotron resonance mass spectrometry analyses, 11 years of biochar addition could increase the humic-like and aromatic and condensed aromatic DOM and decrease the microbial-derived DOM, while 5 years of biochar addition at the other site did not. The response of condensed aromatic dissolved black carbon did not increase with increasing cumulative biochar dose but appeared to be affected by biochar aging time. Despite the possible increase in aromatic DOM, biochar addition neither increased the reactivity of DOM in forming trihalomethanes, haloacetonitriles, chloral hydrates, or haloketones nor significantly increased the microtoxicity or genotoxicity of the DBP mixture. This study indicates that biochar addition in watersheds may not deteriorate the drinking water quality via the export of terrestrial DBP precursors like wildfire events.

The effect of operational conditions on the disinfection by-products formation potential of exopolymeric substances from biofilms in drinking water

Biofilms are ubiquitous in drinking water systems due to their external matrix of exopolymeric substances (EPS) that provide them protection and adaptability. They are even more common in low flow conditions where hydraulics favor their growth. EPS are organic substances (i.e., proteins, carbohydrates and humic substances) that can react with disinfectant, forming disinfection byproducts (DBP), some of which are controlled by water regulation. However, there is little information available on biofilm-disinfectant interaction and the effect of operational conditions such as biofilm age, water velocity, chlorine and pipeline length on the DBP formation potential of EPS (DBPfpEPS). Using experimental setup and studies of two different biofilms: Biofilm 1 (2.6 ± 0.8 mg Cl/L) and Biofilm 2 (0.7 ± 0.2 mg Cl/L), the DBPfpEPS was studied and compared to the DBPfp of filtered water (FW). The DBP studied were trihalomethanes (THM), haloacetic acids (HAA), haloacetonitriles (HAN), chloropropanones (CP) and chloropicrin (CPK). The DBP concentration trend in both EPS and FW was HAA > THM > CP > HAN > CPK. Biofilm age only increased chloroform (CF)fpEPS in Biofilm 1, while other DBPfpEPS decreased. A direct relationship between water velocity and CFfp in Biofilm 1 was found, probably related to higher chlorine diffusion and the production of a more reactive matrix. Chlorine positively affected DBPfpEPS, increasing Cl-HAA, Cl-THM, CPK and Br-HAN. Biofilm 2 produced higher quantities of EPS per meter of pipeline, this constituting a precursor of intermediary DBP 1,1 dichloropropanone (1,1, DCP). The study compared DBP in chlorinated water in contact with biofilm (BCW) and without (CW). Biofilm 1 increased levels of Cl-HAA, Cl-CP and dichloro-acetonitrile, while Biofilm 2 diminished Cl-HAA and Cl-HAN. Biofilm 1 reduced some Br-HAA in BCW, whereas Biofilm 2 promoted Br-HAA and 1,1, DCP in BCW. EPS and biofilms were significant in terms of their effect on DBP formation.

Removal of CX3R-type disinfection by-product precursors from rainwater with conventional drinking water treatment processes

In addition to surface water and groundwater, rainwater is used as an important drinking water source in many parts of the world, especially in areas with serious water pollution or insufficient water resources. Conventional drinking water treatment technologies can remove dissolved organic matter and therefore reduce the formation of disinfection by-products (DBPs) during subsequent disinfection using surface water or groundwater as drinking water sources. However, little information has been known about the effect of conventional water treatment processes on DBP formation when rainwater is used as drinking water source. This study evaluated CX3R-type DBP precursors removal from rainwater by conventional drinking water treatments and the corresponding decrease of CX3R-type DBP (trihalomethanes (THMs), haloaldehydes (HALs), haloacetonitriles (HANs) and haloacetamides (HAMs)) formation and toxicity during the subsequent chlor(am)ination. The result showed that both sand filtration (SF) and activated carbon filtration (GAC) were able to remove DBP precursors and GAC outperformed SF, but no DBP precursors removal was observed during coagulation-sedimentation treatment. Among all treatments, SF + GAC was the most effective for DBP precursors removal, with removal efficiencies of 64.2% DOC, 98% DON and 76.6% UV254. Correspondingly, both SF and GAC decreased the formation of THMs, HALs, HANs and HAMs, and GAC performed better than SF. The combination of SF and GAC, especially SF + GAC, greatly decreased DBP formation, with average reduction of 79.2% and 85% during chlorination and chloramination respectively. After different treatments, the comprehensive toxicity risk of CX3R-type DBPs was all reduced, among which GAC + SF exhibited superior performance. Generally, the main contribution of integrated toxicity was HANs during chlor(am)ination. The formation potential of THMs, HALs, HANs and HAMs and the corresponding integrated toxicity were greater during chlorination than that during chloramination. Therefore, the combination of GAC and chloramination was promising in mitigating the comprehensive toxicity risk of THMs, HALs, HANs and HAMs for rainwater.

Interpreting main features of the differential absorbance spectra of chlorinated natural organic matter: Comparison of the experimental and theoretical spectra of model compounds

This study compared chlorination-induced changes of the properties of natural organic matter (NOM) represented by standard humic substances and NOM present in pristine and anthropogenically-affect reservoirs, rivers, groundwater and seawater. The chlorination-induced changes of NOM properties were quantified using the differential absorbance spectra (DAS) which were processed via numeric deconvolution. Six Gaussian bands were found to comprise the DAS of all examined waters. These bands (denoted as A0, A1, A2, A3, A4 and A5, respectively) have maxima located at ca. 200, 240, 276, 316, 385 and 547 nm. The bands A1-A4 were observed in the DAS of representative model chlorinated compounds. Quantum chemical (QC) calculations were carried out to examine the intrinsic nature of these bands and electronic transitions associated with them. QC data demonstrate that bands A1 and A2 are present in almost all aromatic organic species, A3 is likely to be associated with acetophenone- and/or styrene-like groups. A4 can be attributed to the engagement of m-hydroxyaromatic and flavone-type groups typical for the polyphenolic moiety in NOM and known to be the key precursors of disinfection by-product (DBP) formation. Thus, the intensity of band A4 is predicted to be an especially strong predictor of DBP formation.

Spectral and mass spectrometric characteristics of different molecular weight fractions of dissolved organic matter

Dissolved organic matter (DOM) in water, especially the fluorescent DOM, has high reactivity with chlorine, resulting in toxic disinfection byproducts (DBPs). The effective removal of DOM before disinfection is acriticalelement to control the formation of toxic DBPs, which is closely related to the recognition of molecular structures for DOM, especially the fluorescent DOM. However, the limited information about the molecular features of fluorescent DOM left much room for the determination of DBP precursors. In this study, optical characteristics and molecular features of DOM fractions with varying molecular weight were illuminated by using fluorescence excitation-emission matrix spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Through Spearman’s rank correlation analysis of fluorescent component and FTICR-MS peak relative intensities, 840 of formulae shared by different DOM fractions were associated with corresponding fluorescent components, accounting for 58.64% of FTICR-MS peak intensities of raw water. Most of these 840 molecular features are expected to directly account for the optical properties of aggregates for forming macromolecular fluorescent substances. Given the high chlorine reactivity of fluorescent compounds, these 840 molecular features shed some light on the unknown DBP precursors. Although the formulae associated with fluorescent components were illuminated, possible many isomers for a given formula made it complex to demonstrate the structure of DOM. Thus, further functional group characterization was performed via fourier transform infrared spectroscopy, which allowed a deep insight into the functional group structures of DOM.

Reducing disinfection byproduct precursors and chlorine consuming substances by a special integration of biofiltration and ozonation: A pilot study

Saigon river is the primary water supply source for Ho Chi Minh City, Vietnam. Currently, the formation of harmful disinfectant by-products (DBPs) in the piped water is elevating due to the increase in both organic matter pollution in Saigon river and chloride usage at water treatment plants (WTPs). To provide safe drinking water, the WTPs should upgrade their existing conventional surface water treatment technology to reduce DBP precursors and chlorine consuming substances efficiently. In this study, the long-term performance of a pilot system, including a biofiltration-ozonation unit and a biological activated carbon (BAC) filter in removing these compounds was evaluated. Different from other studies, a tricking filter (TF) was placed before a low-dose ozone contactor for water pretreatment. By partially returning the ozonated water to the TF, the removal of dissolved organic carbon (DOC), which contains DBP precursors, in the TF-ozonation unit was doubled. Over two months operated with highly fluctuated river water quality in the rainy season, the pilot systems stably removed 50 % of DOC, 71 % of trihalomethane formation potential (THMFP), 71 % of Fe2+, and 74 % of N-NH4+. The TF-ozonation unit was effective in removing DOC, THMFP, and NH4+, while the BAC filter was more effective in removing Fe2+. If implemented, this system can replace the pre-chlorination process accounting for 74 % of daily chlorine consumption at Tan Hiep WTP. The obtained results indicate that retrofitting WTPs with the tested processes can provide safe drinking water for Ho Chi Minh City residents in the future.

Activated carbon and organic matter characteristics impact the adsorption of DBP precursors when chlorine is added prior to GAC contactors

Pre-chlorination (i.e. dosing chlorine prior to granular activated carbon (GAC) contactors) was recently introduced as a promising method to reduce the formation of disinfection byproducts (DBPs). However, our understanding on the effect of natural organic matter (NOM) and GAC characteristics on pre-chlorination efficiency is still elusive. Thus, we have designed this systematic study to investigate the effects of GAC characteristics (i.e. surface area, pore size, and surface charge) on the subsequent reduction of DBP formation using five well-characterized adsorbents with three different NOM under three initial Br− concentrations. The results revealed that the adsorption of halogenated DBPs precursors mostly occurs in the mesoporous region (i.e. 2 nm < pore size <50 nm) of the adsorbents. Subsequently, pre-chlorination before treatment with HD3000 (i.e. GAC with the highest mesoporous surface area) decreased the formation of DBPs by 58%. Furthermore, oxidation of GAC increased the surface acidity and negatively impacted the adsorption of halogenated DBP precursors, which suggests basic GACs as promising adsorbents when applying pre-chlorination. In addition, experiments with different NOM showed that pre-chlorination was effective with higher aromatic NOM (i.e. high specific ultraviolet absorbance (SUVA254)). However, pre-chlorination of NOM with low SUVA254 has decreased the adsorption of some DBP precursors which resulted in increased formations of haloacetic acid (HAA) and total organic halogen (TOX). Also, experiments with effluent organic matter (EfOM) showed that pre-chlorination did not increase the adsorption of DBP precursors in low SUVA254 wastewater effluents. Besides, increasing initial Br− concentration increased the formation of brominated DBPs (Br-DBPs) and the adsorbed Br-DBP precursors. This study gives in-depth understanding of the mechanisms, advantages, and limitations of pre-chlorination as a potential method to control DBPs formation.

Precursors of typical nitrogenous disinfection byproducts: Characteristics, removal, and toxicity formation potential

The emergence of nitrogenous disinfection byproducts (N-DBPs) in drinking water has become a widespread concern. In this study, dichloroacetonitrile (DCAN), dicholoacetamide (DCAcAm) and trichloronitromethane (TCNM) were chosen as representatives to clarify the characteristics of N-DBP precursors in the raw waters of Taihu Lake, the Yangtze River, and Gaoyou Lake. Removal of DCAN and DCAcAm precursors must focus on nonpolar and positively charged organics, but more attention should be paid to micromolecular, polar and non-positively charged organics as TCNM precursors. Compared to molecular weight (MW) and hydrophilicity fractionation, polarity and electrical classification have higher selectivity to intercept N-DBP precursors. The properties of N-DBP precursors are relatively fixed and traceable in water systems, which could contribute to their targeted removal. Based on investigation of their characteristics, the removal efficiency and preferences of organic precursors under different processes were studied in three drinking water treatment plants (DWTPs). The TCNM precursors produced in preozonation can be effectively removed during coagulation. The cumulative removal efficiency of conventional processes on N-DBP precursors was approximately 20–30%, but O3/BAC process improved removal by about 40%. The key to improving the removal efficiency of N-DBP precursors by O3/BAC is that it can significantly remove low-MW, nonpolar, positively charged, hydrophilic and transphilic organics. In combined toxicity trials, both cytotoxicity and genotoxicity showed a synergistic effect when DCAN, DCAcAm, and TCNM coexisted, which means that low-level toxicity enhancement in the actual water merits attention. DCAN precursors dominated in the toxicity formation potential (TFP), followed by TCNM precursors. In addition, the removal rate of total N-DBP precursors may be higher than that of TFP, leading to overly optimistic evaluation of precursor removal in water treatment practice. Therefore, the removal effect on TFP must also be considered.

Low water treatability efficiency of wildfire-induced dissolved organic matter and disinfection by-product precursors

Wildfire could alter both the quantity and composition of terrestrial organic matter exported into source water, and water treatability of fire-impacted dissolved organic matter (DOM) could be different from its unburned counterpart. Currently, there is no standard protocol to treat wildfire-impacted source water. To identify the best treatment practices in handling post-fire runoffs, we conducted a systematic controlled study using leachates of unburned white fir (Abies concolor) and Ponderosa pine (Pinus ponderosa) and black and white ashes (collected immediately and one year after the 2013 Rim Fire, California) to evaluate coagulation and oxidation strategies for controlling disinfection byproducts (DBPs) formation. Results showed that the efficiency (%) of alum coagulation in removing dissolved organic carbon and nitrogen followed the order of litter > ash immediately after the fire > ash one year after the fire. Alum coagulation was less effectiveness in removing DOM and DBP precursors in ash leachates, compared to litter leachates. This may be attributed to the loss of side chains and the decrease of DOM molecular weight during the wildfire, thus inducing lower removal efficiency of the DOM and DBP precursors during the alum coagulation. Considering use of brominated flame retardants by firefighters, the addition of bromide (Br−) (100 μg/L) greatly increased the formation of haloacetonitriles by chlorine, and this increase was relatively lower in ash leachates. The influence of reaction time and pH on DOM reactivity was similar among the leachates of litter and ash samples. Our results show that alum coagulation followed by chloramination at alkaline pH is an effective strategy for reducing post-fire DBP formation in drinking water.

High-Resolution Mass Spectrometry Identification of Novel Surfactant-Derived Sulfur-Containing Disinfection Byproducts from Gas Extraction Wastewater.

Introduction of oil and gas extraction wastewaters (OGWs) to surface water leads to elevated halide levels from geogenic bromide and iodide, as well as enhanced formation of brominated and iodinated disinfection byproducts (DBPs) when treated. OGWs contain high levels of chemical additives used to optimize extraction activities, such as surfactants, which have the potential to serve as organic DBP precursors in OGW-impacted water sources. We report the first identification of olefin sulfonate surfactant-derived DBPs from laboratory-disinfected gas extraction wastewater. Over 300 sulfur-containing DBPs, with 43 unique molecular formulas, were found by high-resolution mass spectrometry, following bench-scale chlor(am)ination. DBPs consisted of mostly brominated species, including bromohydrin sulfonates, dihalo-bromosulfonates, and bromosultone sulfonates, with chlorinated/iodinated analogues formed to a lesser extent. Disinfection of a commercial C12-olefin sulfonate surfactant mixture revealed dodecene sulfonate as a likely precursor for most detected DBPs; disulfur-containing DBPs, like bromosultone sulfonate and bromohydrin disulfonate, originated from olefin disulfonate species, present as side-products of olefin sulfonate production. Disinfection of wastewaters increased mammalian cytotoxicity several orders of magnitude, with chloraminated water being more toxic. This finding is important to OGW-impacted source waters because drinking water plants with high-bromide source waters may switch to chloramination to meet DBP regulations.

Has the formation of disinfection by-products been overestimated? Membrane leakage from syringe filter heads serves as unexpected precursors

Syringe filters are widely used for sample pretreatments in laboratories. This study found that, surprisingly, these filters can leak dissolved organic carbon (DOC) that can potentially serve as precursors of disinfection by-products (DBPs). Nine common types of syringe filters were assessed. The results showed that the DOC of ultrapure water increased after syringe filtration. The DOC shed from filter membranes was characterized, whose spectra showed that the main compounds exhibited a low apparent molecular weight. Five classes of DBPs were investigated including trihalomethanes, haloacetaldehydes, haloacetonitriles, haloacetamides and halonitromethanes, among which trichloromethane (TCM), dichloroacetaldehyde (DCAL), trichloroacetaldehyde (TCAL), dichloroacetonitrile (DCAN), and trichloronitromethane (TCNM) were principally detected. The DBP formation was affected by chlorination time and membrane types. In general, the use of the poly vinylidene fluoride membrane resulted in the highest formation of TCM and TCAL, whereas nylon and mixed cellulose esters membranes contributed significantly to the formation of DCAN and TCNM, respectively. The shedding DOC and the formation of TCM, DCAL and TCAL from filter membranes were mitigated effectively by pre-washing; however, the contribution of membrane leakage to DCAN and TCNM formation was still notable, even with a pre-wash volume of 50 mL. When unwashed syringe filters were used for a real water sample, the DBP formation increased by up to 73.2% compared to the pre-washed ones; particularly for TCNM it was always over 15%. Therefore, for better quality control in laboratories, more attention should be paid to the syringe filters during sample pre-treatments, particularly when DBP formation is being investigated.

Dynamics of dissolved organic matter and disinfection byproduct precursors along a low elevation gradient in woody wetlands - an implication of hydrologic impacts of climate change on source water quality

Foliar litter is an important terrestrial source of dissolved organic matter (DOM) and disinfection byproducts (DBPs) in the source water supply. Climate changes could alter precipitation patterns and hydroperiods in woody wetlands, resulting in a hydrologic shift along the low elevation gradient and change the productions of DOC and DBP precursors and their exports to source water. Here, we conducted an 80-week field decomposition study using fresh-fallen leaves along an elevation gradient, representing well-drained, relatively moist, and inundated environments, in Congaree National Park, South Carolina. The dissolved organic carbon (DOC) yield and formation potential (FP) of trihalomethanes (THMs; a dominant category of studied DBPs) were 48.9–79.7 mg-DOC/g-litter and 2.23–6.57 mg/g-litter in the freshly fallen leaf litter, respectively. The level of leachable DOM and its DBP FP decreased with time, and during the first 16 weeks of decomposition, the decomposing litter served as an important source of leachable DOM and DBP precursors. Week 28 was a turning point for DOM optical properties, with fewer tyrosine/tryptophan/soluble microbial byproduct-like compounds and more aromatic, humified, and fulvic/humic acid-like compounds. Litterfall primarily occurred from September to January, while less precipitation occurred from October to January, indicating that large amounts of DOC and DBP precursors could be leached from litterfall in February. In the first 16 weeks of field exposure study, we observed higher residual mass and lower water-extractable DOC and DTN in more inundated environments, demonstrating that the shifts of DOM composition and DBP precursors if climate reduces rainfall in the southeastern US.

Two years of post-wildfire impacts on dissolved organic matter, nitrogen, and precursors of disinfection by-products in California stream waters

We investigated the effects of two California wildfires (Rocky and Wragg Fires, 2015) compared to an unburned reference watershed on water quality, dissolved organic matter (DOM), and precursors of disinfection by-products (DBPs) for two years’ post-fire. The two burned watersheds both experienced wildfires but differed in the proportion of burned watershed areas. Burned watersheds showed rapid water quality degradation from elevated levels of turbidity, color, and suspended solids, with greater degradation in the more extensively burned watershed. During the first year’s initial flushes, concentrations of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), ammonium (NH4+/NH3), and specific ultraviolet absorbance (SUVA254) were significantly higher (67 ± 40%, 418 ± 125%, 192 ± 120%, and 31 ± 17%, respectively) in the more extensively burned watershed compared to the reference watershed. These elevated values gradually declined and finally returned to levels like the reference watershed in the second year. Nitrate concentrations were near detection limits (0.01 mg-N/L) in the first year but showed a large increase in fire-impacted streams during the second rainy season, possibly due to delayed nitrification. Changes in DOM composition, especially during the initial storm events, indicated that fires can attenuate humic-like and soluble microbial by-product-like (SMP) DOM while increasing the proportion of fulvic-like, tryptophan-like, and tyrosine-like compounds. Elevated bromide (Br−) concentrations (up to 8.7 μM]) caused a shift in speciation of trihalomethanes (THMs) and haloacetic acids (HAAs) to brominated species for extended periods (up to 2 years). Wildfire also resulted in elevated concentrations of N-nitrosodimethylamine (NDMA) precursors. Such changes in THM, HAA, and NDMA precursors following wildfires pose a potential treatability challenge for drinking water treatment, but the effects are relatively short-term (≤1 year).

Study on the removal of humic acid by ultraviolet/persulfate advanced oxidation technology.

Humic acid (HA) in water is the main precursor of disinfection by-products in the chlorination process of drinking water. In this study, an ultraviolet/persulfate (UV/PS) process, in a laboratory-scale system, is successful in the degradation of HA. The results showed that HA was significantly degraded (UV254 removal rate of ~ 89%) and partially mineralized (~ 62.5%) by UV/PS treatment at a PS dose of 0.4mM, pH of 7.12, and UV irradiation time of 160min. The trihalomethane formation potential (THMFP) was also significantly reduced (THMFP reduction of ~ 85.4%). A strong linear relationship was observed between UV254 and dissolved organic carbon. The removal rate of HA at low pH was better than that at high pH conditions, and the inhibition by Cl- slowed down after an initial increase, and the inhibition was weaker than HCO3-. By analyzing the fluorescence spectrum of two humic-like substances, the fluorescent compounds C1 and C2 in HA were significantly degraded, and the change in C1 and C2 concentration was correlated with the decrease of THMFP. The degradation of different fractions of natural organic matter in real-world water samples indicated that UV/PS has significant potential to decrease HA in water.

Characteristics of low and high SUVA precursors: Relationships among molecular weight, fluorescence, and chemical composition with DBP formation

Disinfection by-products (DBPs) formed upon water treatment is an emerging issue worldwide. While monitoring of DBP precursors can easily be achieved for high specific UV absorbance (SUVA) organic (>6 L/mg·m), low and extremely low SUVA precursors (<2 L/mg·m) are difficult to monitor or even to predict their DBP formation behaviour. This study investigated the relationships among NOM characteristics, such as molecular weight (MW), fluorescence, and chemical composition, with DBP formation resulting from the chlorination of relatively high and low SUVA precursors. High SUVA precursors were formed by C-rich substances (82–85% of total mass) corresponding with high C/N and C/O (>100 and >5, respectively). Such precursors exhibited the fluorescence of long-wavelength humic-like signal and occurred at a high MW range (>30 kDa). By contrast, low SUVA precursors were either N-rich and/or O-rich substances, associated with much lower carbon content (40–70%). Low SUVA, N-rich precursors particularly also occurred at a high MW region (>100 kDa) and produced a strong protein-like fluorescence signal. When SUVA values of O-rich precursors were extremely low (<1 L/mg·m) they were accompanyied by short-wavelength humic-like fluorescence. During DBP tests, high SUVA produced only high yields of carbonaceous DBPs (e.g trichloromethane, haloacetic acids, haloketones), whereas low SUVA N-rich precursors yielded high levels of both C and NDBPs (e.g. haloacetonenitrile, chloropicrin). By contrast, extremely low SUVA precursors produced significantly low levels of both C and NDBPs (total < 30 μg/mgC). Furthermore, 19 of 20 regression models of DBP formation using log-transformed MW gave R2 = 0.50–0.97. The strong regressions and correlations of NOM characteristics with DBPs in this study provide a better understanding of the influence of precursors characteristics on DBP monitoring, especially for low SUVA NOM.

Adsorption of Pb2+ onto freeze-dried microalgae and environmental risk assessment

Dry microalgae Spirulina platensis shows a high capacity for heavy metal uptake, but there is a concern about dissolved organic carbon (DOC) residue, which is the precursor of disinfection by-products (DBPs). Vsp, a kind of Spirulina platensis powder prepared by vacuum freeze-drying, and Osp, a kind of Spirulina platensis powder prepared by the conventional oven drying-pulverization method, were subjected to assessments of their adsorption potential for Pb2+ and DOC residue. The adsorption mechanism of Pb2+ by the two adsorbents was studied by SEM, FT-IR, EDX and N2-BET. The effects of pH, adsorbent dosage, initial Pb2+ concentration and contact time on the biosorption process were investigated. The results showed that Pb2+ biosorption by Vsp and Osp were fit well by a pseudo-second-order kinetic model and the Langmuir model. The maximum amount of Pb2+ biosorption by Vsp was 253 mg/g, which was 33 mg/g greater than that of Osp. In comparison with Osp, Vsp reached adsorption saturation 8 h earlier and had a remarkable effect on the control of DOC residue in water. When both adsorption capacity and environmental risks were considered, it was determined that the dosage of 0.5 g/L Vsp for 2 h of contact time was the best method, with 85.89 mg/g of Pb2+ removal and 3.45 mg/L of DOC residue. In summary, Vsp is a highly efficient and environmentally friendly biosorbent that can be used for heavy metal removal from water.

Effect of granular activated carbon pore-size distribution on biological activated carbon filter performance

Proper granular activated carbon (GAC) selection could improve the performance of biological activated carbon (BAC) filters through a combination of adsorption and biodegradation, while the GACs used in BAC filters are now mainly selected according to adsorption function, ignoring biodegradation. In this study, sand filter effluent obtained from a drinking water treatment plant was fed into continuous-flow bench-scale BAC columns operated in parallel over 245 days to examine the effects of GAC pore-size distribution on BAC filter performance, in terms of the dissolved organic carbon (DOC) and disinfection byproduct (DBP) precursors. A metagenomic analysis indicated that bacterial community structure played an important role in BAC filter performance. A significant correlation was found between metabolism-related proteins and the volume of micro-level macropores based on metaproteomic analysis. It is suggested that the adsorption saturation was dynamic and that adsorption played a role in the performance of the BAC filters throughout the 245-day operating period. Renewed adsorption capacity, or bioregeneration, was driven by bacterial metabolic activity. Such activity largely depended on the organic matter adsorbed by the GAC, in which micro-level macropores, especially those with diameters of 0.2–10 μm, played an important but previously unrecognized role. The results suggest that more attention should be paid to well-developed pores and pore-size distribution in the production and selection of GAC used for full-scale drinking water biofilters.

PARAFAC model as an innovative tool for monitoring natural organic matter removal in water treatment plants.

The increase of fluorescent natural organic matter (fNOM) fractions during drinking water treatment might lead to an increased coagulant dose and filter clogging, and can be a precursor for disinfection by-products. Consequently, efficient fNOM removal is essential, for which characterisation of fNOM fractions is crucial. This study aims to develop a robust monitoring tool for assessing fNOM fractions across water treatment processes. To achieve this, water samples were collected from six South African water treatment plants (WTPs) during winter and summer, and two plants in Belgium during spring. The removal of fNOM was monitored by assessing fluorescence excitation-emission matrices datasets using parallel factor analysis. The removal of fNOM during summer for South African WTPs was in the range 69-85%, and decreased to 42-64% in winter. In Belgian WTPs, fNOM removal was in the range 74-78%. Principal component analysis revealed a positive correlation between total fluorescence and total organic carbon (TOC). However, TOC had an insignificant contribution to the factors affecting fNOM removal. Overall, the study demonstrated the appearance of fNOM in the final chlorinated water, indicating that fNOM requires a customised monitoring technique.

Enhanced formation of carbonaceous and nitrogenous disinfection byproducts from biofilm extracellular polymeric substances undercatalysis of copper corrosion products

Biofilm formation is ubiquitous on the corroded inner surface of water distribution pipes. Extracellular polymeric substances (EPS) secreted by biofilm microorganisms are nonnegligible precursors of disinfection byproducts (DBPs). The aim was to study the catalysis of copper corrosion products (CCPs, CuO and Cu2+) on the formation of carbonaceous and nitrogenous DBPs (C-DBPs and N-DBPs) with EPS as a precursor. Results indicate that CCPs had a remarkable enhancement on the formation of DBPs, especially N-DBPs. The enhancement by Cu2+ was mainly via homogeneous catalysis initiating from its complexation with EPS, while that by CuO was primarily through heterogeneous catalysis initiating from the polarization of Cl atom in HOCl/OCl−. The enhancement was more evident as pH increased because an alkaline condition favored the electrostatic interactions of CCPs with EPS and HOCl/OCl−. The presence of Br− weakened the enhancement, which may be attributed to that HOBr/OBr− had a much higher reaction rate than HOCl/OCl− towards the low reactive moieties in EPS. Due to more phenolic or unsaturated/conjugated groups, EPS proteins had a higher catalytic formation of DBPs than EPS polysaccharides. Among the major amino acids in EPS proteins for DBPs formation, tyrosine had the highest enhancement on the formation of trihalomethanes, while histidine had the highest catalytic formation of halogenated acetic acids, acetonitriles and acetamides. The study helps to understand the formation of DBPs by the joint actions of EPS and CCPs in drinking water distribution systems.