Mechanisms and kinetics study on the trihalomethanes formation with carbon nanoparticle precursors.

With lots of carbon nanoparticles (CNPs) applied in the industry, the possibilities of their environmental release have received much attention. As the CNPs may enter drinking water systems, and persist in water and wastewater treatment systems, their possible reaction with disinfectants should be studied. In this study, the formation of trihalomethanes (THMs) with 5 types of carbon nanotubes (CNTs), graphene oxide (GO) and reduced graphene oxide (rGO) was investigated. All CNPs could act as precursors of THMs in aqueous phase. Total concentrations of THMs formed with CNPs varied from 0.24 to 0.95 µM, much lower than that formed from chlorinated Suwannee River Natural Organic Matter (SRNOM) (approximately 9 µM). The kinetics of THMs formation with GO was 0.0814 M(-1) s(-1), which is higher than most of the chlorinated humic acid obtained from different natural waters. The study indicates that during chlorination, C-Cl bond could be formed on the surface of CNPs. However, carbon atoms at the middle of two meta-positioned OH groups on the benzene ring are more active and may prefer to form THMs with chlorine oxidation. The influences of pH and reactant doses on the formation of THMs were also discussed.

Influence of Water Table Depth on Pore Water Chemistry and Trihalomethane Formation Potential in Peatlands.

Drained peatland catchments are reported to produce more colored, dissolved organic carbon (DOC)-rich water, presenting problems for potable water treatment. The blocking of peatland drainage ditches to restore the water table is increasingly being considered as a strategy to address this deterioration in water quality. However, the effect of ditch blocking on the potential of DOC to form trihalomethanes (THMs) has not been assessed. In this study, the effect of peat rewetting on pore water DOC concentration and characteristics (including THM formation potential [THMFP]) was assessed over 12 months using peat cores collected from two drained peatland sites. The data show little evidence of differences in DOC concentration or characteristics between the different treatments. The absence of any difference in the THMFP of pore water between treatments suggests that, in the short term at least, ditch blocking may not have an effect on the THMFP of waters draining peatland catchments.

Enhanced formation of disinfection byproducts in shale gas wastewater-impacted drinking water supplies.

The disposal and leaks of hydraulic fracturing wastewater (HFW) to the environment pose human health risks. Since HFW is typically characterized by elevated salinity, concerns have been raised whether the high bromide and iodide in HFW may promote the formation of disinfection byproducts (DBPs) and alter their speciation to more toxic brominated and iodinated analogues. This study evaluated the minimum volume percentage of two Marcellus Shale and one Fayetteville Shale HFWs diluted by fresh water collected from the Ohio and Allegheny Rivers that would generate and/or alter the formation and speciation of DBPs following chlorination, chloramination, and ozonation treatments of the blended solutions. During chlorination, dilutions as low as 0.01% HFW altered the speciation toward formation of brominated and iodinated trihalomethanes (THMs) and brominated haloacetonitriles (HANs), and dilutions as low as 0.03% increased the overall formation of both compound classes. The increase in bromide concentration associated with 0.01-0.03% contribution of Marcellus HFW (a range of 70-200 µg/L for HFW with bromide = 600 mg/L) mimics the increased bromide levels observed in western Pennsylvanian surface waters following the Marcellus Shale gas production boom. Chloramination reduced HAN and regulated THM formation; however, iodinated trihalomethane formation was observed at lower pH. For municipal wastewater-impacted river water, the presence of 0.1% HFW increased the formation of N-nitrosodimethylamine (NDMA) during chloramination, particularly for the high iodide (54 ppm) Fayetteville Shale HFW. Finally, ozonation of 0.01-0.03% HFW-impacted river water resulted in significant increases in bromate formation. The results suggest that total elimination of HFW discharge and/or installation of halide-specific removal techniques in centralized brine treatment facilities may be a better strategy to mitigate impacts on downstream drinking water treatment plants than altering disinfection strategies. The potential formation of multiple DBPs in drinking water utilities in areas of shale gas development requires comprehensive monitoring plans beyond the common regulated DBPs.

Reduction of DOM fractions and their trihalomethane formation potential in surface river water by in-line coagulation with ceramic membrane filtration.

This research was aimed at investigating the reduction of DOM fractions and their trihalomethane formation potential (THMFP) by in-line coagulation with 0.1 µm ceramic membrane filtration. The combination of ceramic membrane filtration with a coagulation process is an alternative technology which can be applied to enhance conventional coagulation processes in the field of water treatment and drinking water production. The Ping River water (high turbidity water) was selected as the raw surface water because it is currently the main raw water source for water supply production in the urban and rural areas of Chiang Mai Province. From the investigation, the results showed that the highest percent reductions of DOC, UV-254, and THMFP (47.6%, 71.0%, and 67.4%, respectively) were achieved from in-line coagulation with ceramic membrane filtration at polyaluminum chloride dosage 40 mg/L. Resin adsorption techniques were employed to characterize the DOM in raw surface water and filtered water. The results showed that the use of a ceramic membrane with in-line coagulation was able to most efficiently reduce the hydrophobic fraction (HPOA) (68.5%), which was then followed by the hydrophilic fraction (HPIA) (49.3%). The greater mass DOC reduction of these two fractions provided the highest THMFP reductions (55.1% and 37.2%, respectively). Furthermore, the in-line coagulation with ceramic membrane filtration was able to reduce the hydrophobic (HPOB) fraction which is characterized by high reactivity toward THM formation. The percent reduction of mass DOC and THMFP of HPOB by in-line coagulation with ceramic membrane filtration was 45.9% and 48.0%, respectively.

Effects of dissolved organic matter size fractions on trihalomethanes formation in MBR effluents during chlorine disinfection.

In this study, effects of dissolved organic matter (DOM) size fractions on trihalomethanes (THMs) formation in MBR effluents during chlorination were investigated by fractionating DOM into >100, 30-100, 10-30, 5-10 and <5 kDa fractions using ultrafiltration (UF) membranes based on molecular weight (MW). Fractions of MW>30 kDa constituted 87% of DOM and were the main THMs precursors, which exhibited higher specific ultraviolet absorbance (SUVA) and THMs formation potential (THMFP) and should be reduced to control THMs formation. For these fractions, THMs formation was mostly attributed to slow chlorine decay, and THMs yield coefficients were low because halogenated intermediates derived from the macromolecular DOM were difficult to decompose to produce THMs. Moreover, there was a strong linear correlation between dissolved organic carbon (DOC) concentration and THMFP (R(2)=0.981), as well as between the SUVA and specific THMFP (R(2)=0.993) in all fractions.

Modelling trihalomethanes formation in water supply systems.

Chlorination is the most widely used method for disinfection of drinking water, but there are concerns about the formation of by-products, such as trihalomethanes (THMs), since the chronic exposure to them may pose risks to human health. For these reasons regulations fix maximum acceptable THMs levels throughout distribution networks, so it is very important to be able to correctly reproduce their formation. In the literature many models for predicting THMs formation have been developed, both based on empirical relationships and on kinetics involved during chlorine reactions. In this work the use of some of these models and their reliability in real situations is investigated through the application to the Aurunci-Valcanneto Water Supply System in Southern Lazio (Italy). The comparison of the performances of 18 selected literature empirical models furnishes interesting observations, indicating that the formula, developed using field data, results in being more suitable for reproducing THMs formation for the presented case study. Other considerations are also offered from the comparison with the results obtained using a simple first order kinetic model, calibrated using measured data.

Sustainable and effective control of trihalomethanes in the breakpoint chlorination of wastewater effluents.

The control of trihalomethanes (THMs) in waters subjected to chlorination is essential for protecting public health. However, the necessary means are not always available, especially in developing countries and regions. Under circumstances of scarce resources, one can utilize various means available for the control of THMs: a simple and affordable analytical method for testing of THMs, the study of the parameters tested routinely that could be used as indicators and the dose of chlorine used for the chlorination process. The objective of this work was to study the potential formation of THMs in wastewater effluents using a simple method of detection and various doses of chlorine in relation to the breakpoint and to validate some commonly determined parameters as indicators of THM formation. THM concentrations were measured using a simple spectrophotometric method based on the Fujiwara reaction. To determine the chlorine demand, a super-chlorination was performed and free and residual chlorine was measured; the mean value of chlorine demand was 166.6 mgCl2/L. The chlorination with concentrations well below the chlorine demand produces a significant reduction in microbial content. With regard to the formation of THMs the higher the dose of chlorine added, the higher the concentration of THMs. In relation to commonly determined parameters our data only provide a logarithmic linear regression between THMs and ammonium. According to our results, the breakpoint must be determined for the chlorination of sewage and their effluents, and chlorination should be performed with concentrations of chlorine at approximately 1/3 of the demand.

Study of pH effects on the evolution of properties of brown-water natural organic matter as revealed by size-exclusion chromatography during photocatalytic degradation.

This study shows the effect of pH on the photocatalytic degradation of natural organic matter (NOM). The experiments were carried out in batch reactor (a solar UV-light simulator) with Degussa P-25 titanium dioxide (TiO2). The NOM degradation was followed by size-exclusion chromatography for dissolved organic carbon (DOC), ultraviolet absorption and fluorescence-detection (SEC-DOC, SEC-UV254 and SEC-Fl254/450). Changes in pH values affected the adsorption of NOM onto TiO2, but did not affect the photodegradation sequence of NOM. For high or low pH values, the degradation of the NOM preferentially removed the larger molecular size fraction in comparison to the middle and small molecular size fractions, resulting in the relative increase of these smaller fractions. This sequence of NOM degradation leads to the evolution of the formation potential for disinfection by-products (DBPs). Specifically, the trihalomethanes and halogenated organic compounds formation potential (THMF and AOXFP) decreased steadily.

Formation and speciation characteristics of brominated trihalomethanes in seawater chlorination.

Formation character of brominated-trihalomethanes (Br-THMs) in chlorinated seawater and its dependence on applied chlorine dose, reaction time, and temperature were investigated in the laboratory. Seawater was collected from the east coast of India and a chlorine dose of 1, 3, 5, and 10 ppm was each applied at a temperature of 20, 30, and 40 degrees C to investigate the yield and kinetics of Br-THMs formation. Qualitative and quantitative estimation of THM formation at various intervals of time ranging from 5 min to 168 h was determined by a gas chromatograph equipped with an electron capture detector (GC-ECD). Chlorine dose, chlorine contact time, and reaction temperature positively affected the load of THMs. The ratio of chlorine dose to halogen incorporation decreased from 12% to 5% with increasing applied chlorine dose from 1 to 10 ppm. Significant levels of THMs were found to be formed within 0.5 h of reaction, followed by a very slow rate of formation. Elevated temperature favored both increased rate of formation and overall THM yield. The formation order of different trihalomethane species at all studied temperatures was observed to be bromodichloromethane (CHCl2Br) < dibromochloromethane (CHClBr2) < bromoform (CHBr3). Formation of chloroform was not observed, and bromoform was the dominant (96% to 98%) among the three THM species formed.

I-THM formation and speciation: preformed monochloramine versus prechlorination followed by ammonia addition.

An increasing number of utilities in the United States have been switching from chlorination to chloramination practices to comply with the more stringent trihalomethane (THM) and haloacetic acid (HAA) regulations. This has important implications for disinfection byproduct (DBP) formation because the reactions of chlorine and monochloramine (NH(2)Cl) with natural organic matter (NOM) are not the same. In this study, iodinated trihalomethane (I-THM) formation from preformed NH(2)Cl and prechlorination (at two chlorine doses and contact times) followed by ammonia addition was compared. A representative bromide/iodide ratio of 10:1 was selected and four bromide/iodide levels (ambient, 50/5 or 100/10, 200/20, and 800/80 [µg/L/µg/L]) were evaluated. The results showed that I-THM formation was generally lower for prechlorination as compared to preformed NH(2)Cl due to the oxidation of iodide to iodate by chlorine. However, while prechlorination minimized iodoform (CHI(3)) formation, prechlorination sometimes formed more I-THMs as compared to preformed NH(2)Cl due to a large increase in the formation of brominated I-THM species, which were formed at much smaller amounts from preformed NH(2)Cl. I-THM concentrations and speciation for the two chloramination scenarios (i.e., preformed NH(2)Cl vs prechlorination followed by ammonia) depended on chlorine dose, contact time, bromide/iodide concentration, and NOM characteristics of the source water (SUVA(254)).

Effects of UV irradiation on humic acid removal by ozonation, Fenton and Fe°/air treatment: THMFP and biotoxicity evaluation.

Effects of UV irradiation on humic acid (HA) removal by Fe(0)/air, ozonation and Fenton oxidation were investigated. The trihalomethane forming potential (THMFP) and toxicity of treated solutions were also evaluated. The experimental conditions were ozone of 21 mg min(-1), H(2)O(2) of 8 × 10(-4)M, Fe(0) of 20 g L(-1), air flow of 5 L min(-1), and UVC of 9 W. Results indicated that Fe(0)/air rapidly removed HA color (>99%) and COD (90%) within 9 min. 51-81% of color and 43-50% of COD were removed by ozonation and Fenton oxidation after 60 min. Both UV enhanced ozone and Fenton oxidation removed HA, but the Fe(0)/air process did not. Spectrum results showed all processes effectively diminished UV-vis spectra, except for ozonation. The THMFP of Fe(0)/air-treated solution (114 µg L(-1)) was much lower than those of Fenton- (226 µg L(-1)) and ozonation-treated solutions (499 µg L(-1)). Fe(0)/air with UV irradiation obviously increased the THMFP of treated solution (502 µg L(-1)). The toxicity results obtained from Vibrio fischeri light inhibition test indicated that the toxicity of Fe(0)/air-treated solution (5%) was much lower than that of ozonation- (33%) and Fenton-treated solutions (31%). Chlorination increased the solution toxicity. The correlation between biotoxicity and chloroform in the chlorinated solution was insignificant.

Formation of disinfection by-products in indoor swimming pool water: the contribution from filling water natural organic matter and swimmer body fluids.

The contribution and role of different precursors in the formation of three class of disinfection by-products (DBPs) [trihalomethanes (THMs), haloacetic acids (HAAs), and halonitromethanes (HNMs)] in swimming pool waters were examined using filling waters obtained from five drinking water treatment plant (WTP) effluents and three body fluid analogs (BFAs). BFAs exerted higher chlorine demands as compared to natural organic matter (NOM) in filling waters. BFAs exhibited higher HAA formation potentials than THM formation potentials, while the opposite was observed for the filling water NOM. There was no appreciable difference in the HNM formation potentials of BFAs and filling water NOM. Different components in the BFAs tested exhibited different degree and type of DBP formation. Citric acid had significantly higher THM and HAA yields than other BFA components. The effect of temperature was greater on THM formation, whereas the effect of contact time had more impact on HAA formation. Experiments with filling waters collected from WTP effluents at three different times showed more variability in HAA than THM formation at the WTPs studied.

Photocatalytic oxidation of natural organic matter surrogates and the impact on trihalomethane formation potential.

Natural organic matter (NOM) consists of a complex mixture of organics and acts as precursors for a range of disinfection by-products (DBPs) including trihalomethanes (THMs). The characteristics of these precursors are still not well identified and here we have used a range of NOM surrogates that allows us to investigate how the characteristics of NOM relate to treatability with photocatalytical oxidation. Nine surrogates of NOM (five amino acids, two carbohydrates, two phenolic compounds) were evaluated and the impact of retention time on dissolved organic carbon (DOC) and trihalomethane formation potential (THMFP) measured. Adsorption of the compounds onto TiO(2) was evaluated and electrostatic forces played a significant role in their removal although photocatalytic oxidation was found to be unselective. DOC and THMFP decreased significantly with retention time except for l-leucine where the by-products formed during photocatalytic oxidation were significantly more reactive with chlorine than the parent compound.

The effect of mixed oxidants and powdered activated carbon on the removal of natural organic matter.

Present paper studies the influence of electrochemically generated mixed oxidants on the physicochemical properties of natural organic matter, and especially from the disinfection by-products formation point of view. The study was carried out in a full scale water treatment plant. Results indicate that mixed oxidants favor humic to non-humic conversion of natural organic matter. Primary treatment preferentially removes the more hydrophobic fraction. This converted the non-humic fraction in an important source of disinfection by-products with a 20% contribution to the final trihalomethane formation potential (THMFP(F)) of the finished water. Enhanced coagulation at 40 mg l(-1) of polyaluminium chloride with a moderate mixing intensity (80 rpm) and pH of 6.0 units doubled the removal efficiency of THMFP(F) achieved at full scale plant. However, gel permeation chromatography data revealed that low molecular weight fractions were still hardly removed. Addition of small amounts of powdered activated carbon, 50 mg l(-1), allowed reduction of coagulant dose by 50% whereas removal of THMFP(F) was maintained or even increased. In systems where mixed oxidants are used addition of powdered activated carbon allows complementary benefits by a further reduction in the THMFP(F) compared to the conventional only coagulation-flocculation-settling process.

Litter contributions to dissolved organic matter and disinfection byproduct precursors in California oak woodland watersheds.

Export of dissolved organic matter (DOM) from California oak woodland ecosystems is of a great concern because DOM is a precursor for carcinogenic disinfection byproducts (DBPs) formed during drinking water treatment. Fresh litter and decomposed duff materials for the four dominant vegetation components of California oak woodlands: blue oak (Quercus douglassi H. & A.), live oak (Quercus wislizenii A. DC.), foothill pine (Pinus sabiniana Dougl.), and annual grasses, were exposed in natural condition for an entire rainy season (December to May) to evaluate their contributions of particulate (POC) and dissolved (DOC) organic carbon, particulate (PON) and dissolved (DON) organic nitrogen, inorganic nitrogen (NH4+ and NO3-), and trihalomethane (THM) and haloacetonitrile (HAN) formation potentials, to surface waters. Litter and duff materials can be significant sources of DOC (litter=29-126 mg DOC g(-1) C; duff=6.5-37 mg DOC g(-1) C) and THMs and HANs (up to 4600 mg-THMs g-C(-1) and 137 microg-HANs g-C(-1)). Blue oak litter had the highest yield of DOC, THM, and HAN precursors. When scaled to the entire watershed, leachate production yielded 445 kg-DOC ha(-1), as compared to DOC export via streams of 5.25 kg-DOC ha(-1). DOC transport to surface waters is facilitated by subsurface lateral flow through A horizons during storm events. The majority of DOM and DBP precursors was leached from plant materials in the initial rainfall events and thus may explain the seasonal stream pattern of a DOC pulse early in the rainy season.

Formation of bromoform in irradiated titanium dioxide suspensions with varying photocatalyst, dissolved organic carbon and bromide concentrations.

We report the formation of bromoform in TiO(2) suspensions (P25) under simulated solar UV irradiation at different concentrations of photocatalyst (0.5-1.5 g L(-1)) as well as initial concentrations of bromide ions (1-3mg L(-1)) and 2,4-dihydroxybenzoic acid (2-10mg L(-1)). The extent of bromoform formation (3-17microg L(-1)) was most strongly affected by the amount of photocatalyst present and by the initial bromide concentration, increasing either of which leads to increased bromoform formation. Important interaction effects were observed when simultaneously increasing the concentrations of TiO(2) and bromide as well as of bromide and DHBA. The time it takes for bromoform to appear in measurable concentrations in the irradiated TiO(2) suspensions was between 10 and 90 min and most strongly depended on the initial concentration of dissolved organic carbon present in the suspensions, along with the amount of photocatalyst, also in interaction with the initial bromide concentration.

Cu(II)-catalyzed THM formation during water chlorination and monochloramination: a comparison study.

The catalytic effect of Cu(II) on trihalomethane (THM) formation during chlorination and monochloramination of humic acid (HA) containing water was comparatively investigated under various pH conditions. Results indicate that in the presence of Cu(II), the formation of THMs was significantly promoted as pH decreased in both chlorination and monochloramination. More THMs were formed during Cu(II)-catalyzed monochloramination which was partially due to enhanced hydroxyl radical (OH) generation as demonstrated by electron spin resonance (ESR) analysis. To discriminate the reactive moieties of HA, nine model compounds, which approximately represented the chemical structure of HA, were individually oxidized by chlorine or monochloramine. Results show that Cu(II) could promote THM formation through reacting with citric acid and similar structures in HA. During chlorination and monochloramination of citric acid in the absence of Cu(II), major intermediates including chlorocarboxylic acid, chloroacetone and chloroacetic anhydride were identified. However, the catalysis of Cu(II) did not produce any new intermediate. The complexation of Cu(II) with model compounds was characterized via FTIR analysis. The reaction mechanism for Cu(II)-catalyzed THM formation was proposed to comprise two pathways: (1) indirect catalysis in which OH oxidizes the large molecules of HA into small ones to enhance THM formation; and (2) direct catalysis in which Cu(II) complexes with HA to accelerate the decarboxylation steps for THM formation.

Effect of bromide on the formation of disinfection by-products during wastewater chlorination.

The effect of bromide ion on the formation and speciation of trihalomethanes (THMs) and haloacetic acids (HAAs) during the chlorination of biologically treated wastewaters was investigated. The experimental results showed that the formation of total THMs and total HAAs during chlorine disinfection increased with increasing bromide levels in wastewater. The formation of CHBr(3) increased nearly linearly with increasing bromide ion levels, while CHCl(2)Br and CHClBr(2) increased with increasing bromide concentration from 0 to 3.2 mg L(-1) and thereafter remained constant or slightly decreased. Increasing initial bromide levels up to 12.8mgL(-1) resulted in sharp decrease of the concentration of CHCl(3) and chloro- HAAs. The mixed bromochloro- HAAs and bromo-only species replaced chloro- HAAs as the dominated species of HAA with increasing bromide levels. The distribution of monohalogenated, dihalogenated and trihalogenated species of HAAs in chlorinated wastewater at high concentration of bromide (>2 mg L(-1)) is different from that of drinking/natural water. The values of the bromine incorporation factors, n (Br) and n' (Br), increased with increasing bromide concentration and remained constant or slightly decreased with increasing contact time under the studied range of bromide ion concentrations during chlorination. Moreover, the bromine incorporation into THMs was higher than that of HAAs with bromide levels ranging from 1.0 to 12.8 mg L(-1), indicating the dissimilar formation mechanisms of THMs and HAAs involving bromide.

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.

Wet weather impact on trihalomethane formation potential in tributaries to drinking water reservoirs.

During rain storm events, land surface runoff and resuspension of bottom sediments cause an increase in Trihalomethane (THM) precursors in rivers. These precursors, when chlorinated at water treatment facilities will lead to the formation of THMs and hence impact drinking water resources. In order to evaluate the wet weather impact on the potential formation of THMs, river samples were collected before, during and after three rain storms ranging from 15.2 to 24.9 mm precipitation. The samples were tested for THM formation potential and other indicators including UV254 absorbance, turbidity and volatile suspended solid (VSS). Average levels of THMs increased from 61 microg/l during dry weather to 131 microg/l during wet weather, and then went back to 81 microg/l after rain ended. Wet weather values of THM are well above the maximum contaminant level (MCL) 80 microg/l, set by EPA for drinking water. THM indicators also exhibited similar trends. Average levels increased from 0.6 to 1.8 abs; 2.6 to 6 ntu; and 7.5 to 15 mg/l respectively for UV254, turbidity and VSS. A positive correlation was observed between THM formation and THM indicators. The t-test of significance (p-value) was less than 0.05 for all indicators, and R values ranged from 0.85 to 0.92 between THMs and the indicators, and 0.72 to 0.9 among indicators themselves.