Adsorption Studies of Waterborne Trihalomethanes Using Modified Polysaccharide Adsorbents.

The adsorptive removal of trihalomethanes (THMs) from spiked water samples was evaluated with a series of modified polysaccharide adsorbents that contain ß-cylodextrin or chitosan. The uptake properties of these biodegradable polymer adsorbents were evaluated with a mixture of THMs in aqueous solution. Gas chromatography employing a direct aqueous injection (DAI) method with electrolytic conductivity detection enabled quantification of THMs in water at 295 K and at pH 6.5. The adsorption isotherms for the polymer-THMs was evaluated using the Sips model, where the monolayer adsorption capacities ranged between 0.04 and 1.07 mmol THMs/g for respective component THMs. Unique adsorption characteristics were observed that vary according to the polymer structure, composition, and surface chemical properties. The modified polysaccharide adsorbents display variable molecular recognition and selectivity toward component THMs in the mixed systems according to the molecular size and polarizability of the adsorbates.

Response surface methodological (RSM) approach for optimizing the removal of trihalomethanes (THMs) and its precursor's by surfactant modified magnetic nanoadsorbents (sMNP) - An endeavor to diminish probable cancer risk.

Response surface methodology (RSM) approach was used for optimization of the process parameters and identifying the optimal conditions for the removal of both trihalomethanes (THMs) and natural organic matter (NOM) in drinking water supplies. Co-precipitation process was employed for the synthesis of magnetic nano-adsorbent (sMNP), and were characterized by field emission scanning electron microscopy (SEM), trans-emission electron microscopy (TEM), BET (Brunauer-Emmett-Teller), energy dispersive X-ray (EDX) and zeta potential. Box-Behnken experimental design combined with response surface and optimization was used to predict THM and NOM in drinking water supplies. Variables were concentration of sMNP (0.1 g to 5 g), pH (4-10) and reaction time (5 min to 90 min). Statistical analysis of variance (ANOVA) was carried out to identify the adequacy of the developed model, and revealed good agreement between the experimental data and proposed model. The experimentally derived RSM model was validated using t-test and a range of statistical parameters. The observed R2 value, adj. R2, pred. R2 and "F-values" indicates that the developed THM and NOM models are significant. Risk analysis study revealed that under the RSM optimized conditions, a marked reduction in the cancer risk of THMs was observed for both the groups studied. Therefore, the study observed that the developed process and models can be efficiently applied for the removal of both THM and NOM from drinking water supplies.

Resorcinarene Cavitand Polymers for the Remediation of Halomethanes and 1,4-Dioxane.

Disinfection byproducts such as trihalomethanes are commonly found in drinking water. Trihalomethanes are formed upon chlorination of natural organic matter found in many drinking water sources. Inspired by molecular CHCl3⊂cavitand host-guest complexes, we designed porous polymers composed of resorcinarene receptors. These materials show higher affinity for halomethanes than a specialty activated carbon used for trihalomethane removal. The cavitand polymers show similar removal kinetics as activated carbon and have high capacity (49 mg g-1 of CHCl3). These materials maintain their performance in drinking water and can be thermally regenerated. Cavitand polymers also outperform commercial resins for 1,4-dioxane adsorption, which contaminates many water sources. These materials show promise for water treatment and demonstrate the value of using supramolecular receptors to design adsorbents for water purification.

Analytical methods for conventional and emerging disinfection by-products in fresh-cut produce.

The formation of toxic disinfection by-products (DBPs) is among the main concerns in the use of chlorine sanitizers for washing fresh and fresh-cut produce to minimize microbial cross-contamination. Even so, robust analytical methods for measuring various DBPs in produce have been lacking. This study has established two liquid-liquid extraction methods, followed by gas chromatography with electron capture detection, to measure 32 conventional and emerging DBPs in different produce types including lettuce, cabbage and strawberry. Good recoveries (50-130%) were achieved for most DBPs in the different produce. The method detection limits were in the range of 0.3-10 ng/g for trihalomethanes, haloacetic acids, nitrogenous DBPs, and other carbonaceous DBPs. Preliminary screening analysis indicated one-third of the target DBPs were found in unwashed produce, and washing with chlorine significantly promoted DBPs' formation and concentrations in the produce. The developed analytical methods will be useful tools for future research on food DBPs.

A pilot-scale investigation of disinfection by-product precursors and trace organic removal mechanisms in ozone-biologically activated carbon treatment for potable reuse.

Although granular activated carbon (GAC) has been broadly applied in ozone-biologically activated carbon filtration (O3/BAC) systems for potable reuse of municipal wastewater, the mechanisms of various pollutant removal remain largely unknown as the regenerated GAC develops microbial populations resulting in biofiltration but loses significant adsorption capacity as it becomes spent GAC. Therefore, pilot-scale parallel performance comparisons of spent and regenerated GAC, along with a range of pre-oxidant ozone doses, were used to shed light on the mechanisms responsible for the removal of various types of treatment byproduct precursors and trace organic compounds. It was confirmed from this pilot-study that ozone alone can effectively degrade chlorinated trihalomethane (THM) and haloacetic acid (HAA) precursors, chloramine-reactive N-nitrosodimethylamine (NDMA) precursors, and 29 PPCPs. In contrast, biodegradation by microbial population on spent or regenerated GAC can remove NDMA and 22 PPCPs, while the adsorption by regenerated GAC can remove chlorinated THM and HAA precursors, PFAS, flame retardants, and 27 PPCPs. The results of this pilot study are intended to provide those interested in potable reuse with an example of the simultaneous removal capabilities and mechanisms that can be anticipated for treating a complex mixture of organics present in real municipal wastewater effluent.

Formation of trihalomethanes as disinfection byproducts in herbal spa pools.

Herbal spa treatments are favorite recreational activities throughout the world. The water in spas is often disinfected to control pathogenic microorganisms and guarantee hygiene. However, chlorinated water may cause the formation of disinfection byproducts (DBPs). Although there have been many studies on DBP formation in swimming pools, the role of organic matter derived from herbal medicines applied in herbal spa water has been largely neglected. Accordingly, the present study investigated the effect of herbal medicines on the formation of trihalomethanes (THMs) in simulated herbal spa water. Water samples were collected from a spa pool, and then, disinfection and herbal addition experiments were performed in a laboratory. The results showed that the organic molecules introduced by the herbal medicines are significant precursors to the formation of THMs in spa pool water. Since at least 50% of THMs were produced within the first six hours of the reaction time, the presence of herbal medicines in spa water could present a parallel route for THM exposure. Therefore, despite the undeniable benefits of herbal spas, the effect of applied herbs on DBP formation in chlorinated water should be considered to improve the water quality and health benefits of spa facilities.

Overcoming the challenges of conventional dispersive liquid-liquid microextraction: analysis of THMs in chlorinated swimming pools.

A rapid, simple, and sensitive approach to the analysis of trihalomethanes (THMs) in swimming pool water samples has been developed. The main goal of this study was to overcome or to improve the shortcomings of conventional dispersive liquid-liquid microextraction (DLLME) and to maximize the realization of green analytical chemistry principles. The method involves a simple vortex-assisted microextraction step, in the absence of the dispersive solvent, followed by salting-out effect for the elimination of the centrifugation step. A bell-shaped device and a solidifiable solvent were used to simplify the extraction solvent collection after phase separation. Optimization of the independent variables was performed by using chemometric methods in three steps. The method was statistically validated based on authentic guidance documents. The completion time for extraction was less than 8 min, and the limits of detection were in the range between 4 and 72 ng L-1. Using this method, good linearity and precision were achieved. The results of THMs determination in different real samples showed that in some cases the concentration of total THMs was more than threshold values of THMs determined by accredited healthcare organizations. This method indicated satisfactory analytical figures of merit. Graphical Abstract A novel green microextraction technique for overcoming the challenges of conventional DLLME. The proposed procedure complies with the principles of green/sustainable analytical chemistry, comprising decreasing the sample size, making easy automation of the process, reducing organic waste, diminishing energy consumption, replacing toxic reagents with safer reagents, and enhancing operator safety.

Cohort-friendly protocol for a sensitive and fast method for trihalomethanes in urine using gas chromatography-Triple quadrupole mass spectrometry.

A cohort-friendly biomonitoring protocol has been developed for measuring biomarkers of exposure to disinfection by-products (trihalomethanes, THM) in urine using small initial volume (3mL) and short analysis time (∼10min) that facilitates the throughput of a large number of samples. The objective of this study was to optimise a cohort-friendly biomonitoring protocol for the determination of four THM analytes in human urine using gas chromatography coupled with triple quadrupole mass spectrometry (GC-QqQ-MS/MS). The proposed methodology will facilitate the inclusion of such urinary THM measurements into large population health studies.

Wetlands receiving water treated with coagulants improve water quality by removing dissolved organic carbon and disinfection byproduct precursors.

Constructed wetlands are used worldwide to improve water quality while also providing critical wetland habitat. However, wetlands have the potential to negatively impact drinking water quality by exporting dissolved organic carbon (DOC) that upon disinfection can form disinfection byproducts (DBPs) like trihalomethanes (THMs) and haloacetic acids (HAAs). We used a replicated field-scale study located on organic rich soils in California's Sacramento-San Joaquin Delta to test whether constructed flow-through wetlands which receive water high in DOC that is treated with either iron- or aluminum-based coagulants can improve water quality with respect to DBP formation. Coagulation alone removed DOC (66-77%) and THM (67-70%) precursors, and was even more effective at removing HAA precursors (77-90%). Passage of water through the wetlands increased DOC concentrations (1.5-7.5mgL-1), particularly during the warmer summer months, thereby reversing some of the benefits from coagulant addition. Despite this addition, water exiting the wetlands treated with coagulants had lower DOC and DBP precursor concentrations relative to untreated source water. Benefits of the coagulation-wetland systems were greatest during the winter months (approx. 50-70% reduction in DOC and DBP precursor concentrations) when inflow water DOC concentrations were higher and wetland DOC production was lower. Optical properties suggest DOC in this system is predominantly comprised of high molecular weight, aromatic compounds, likely derived from degraded peat soils.

Simultaneous determination of 14 disinfection by-products in meat products using microwave-assisted extraction and static headspace coupled to gas chromatography-mass spectrometry.

This paper described the first analytical method to simultaneously determine 14 disinfection by-products (DBPs) in meat products using microwave-assisted extraction (MAE) and static headspace (SHS) followed by gas chromatography-mass spectrometry (GC-MS). The DBPs included were 4 trihalomethanes, 7 haloacetic acids, 2 haloacetonitriles and trichloronitromethane, which are commonly formed as a consequence of the disinfection process of water. The combination of the MAE and SHS techniques allows meat samples to be analysed in two sequential steps into the same HS vial in spite of the sample's complexity. Detection limits were obtained within the range of 0.06-0.70ng/g, and the average relative standard deviation was 7.4%. Recoveries throughout the whole process were between 86 and 95%. The SHS-GC-MS method was applied to determine DBPs in meat products with different industrial processing which could be contaminated through contact with disinfectants and/or treated water employed in the factory either for washing or for the cooking of meat. Up to 5 DBPs were found at ng/g levels in about 36% of the samples analysed, cooked ham being the most contaminated meat product because of the brine solutions employed in its manufacturing process.

[Removal of Algal Organic Matter and Control of Disinfection By-products by Powder Activated Carbon].

The removal efficiencies of algal organic matter (AOM) and typical nitrogenous and non-nitrogenous disinfection by-products (DBPs) through adsorption with powder activated carbon (PAC) were investigated. Three-dimensional fluorescence spectroscopy confirmed that PAC adsorption changed the composition of AOM. PAC adsorption showed high removal efficiency for humus-like substances in AOM, but limited removal efficiency for aromatic protein-like substances. When the dosage of PAC was 20 mg·L-1 and the adsorption time ranged from 10 to 30 min, the removal rates of 3.30 mg·L-1 dissolved organic carbon were 20.7%-31.9% for intracellular organic matter (IOM) and 12.6%-19.0% for extracellular organic matter (EOM). The highest removal rates of trihalomethanes by PAC in the chlorination of IOM and EOM were 26.6% and 35.8%, respectively. The highest removal rates of haloacetonitriles were 49.6% and 53.6% in the chlorination of IOM and EOM. The removal of dibromoacetonitrile precursors by PAC was significant. In summary, the PAC had a higher efficiency in reducing the generation of DBPs in EOM chlorination than in IOM chlorination.

Comparison of three solid phase extraction sorbents for the isolation of THM precursors from manitoban surface waters.

Three prepackaged solid phase extraction (SPE) cartridges: two modified styrene divinylbenzene, Bond Elut ENV and Bond Elut PPL (Varian), and one N-vinylpyrrolidone (Strata-X, Phenomenex), were assessed for isolation of THM precursors from three surface waters in Manitoba, Canada. The dissolved organic matter (DOM) from the La Salle River (LR), Lake Winnipegosis (LW) and the Waterhen River (WR) were fractionated into hydrophobic (HPO) and hydrophilic (HPI) parts. ENV isolated less DOM (LR = 46.6 ± 1.5%; LW = 36.2 ± 1.4%; WR = 28.6 ± 2.2%) compared to PPL (LR = 50.2 ± 4.4%; LW = 47.9 ± 2.2%; WR = 37.3 ± 2.8%) and Strata (LR = 46.4% ± 1.0; LW = 51.6 ± 0.3%; WR = 31.9 ± 3.9%). The HPO fraction isolated by each SPE was characterized using Fourier Transform Infrared (FTIR) spectrochemical imaging. The FTIR spectra confirmed the HPO fractions were typical of humic-material and largely resembled fulvic acids; however, the PPL and Strata HPO isolates contained slightly more polysaccharides. The THM formation potential (THMFP) confirmed that the HPO fraction formed more THMs than the HPI. The HPO fraction isolated using ENV was found to have the lowest THMFP of all three SPEs in each waterbody; however, the specific THMFP (µgTHM/mgDOM) results indicated that ENV isolated THM precursors more effectively, as the Strata and PPL isolated a greater amount of non-THM forming material. All three SPE showed significant potential for implementation at water treatment plants as a simple tool to monitor THM precursors in source waters, enabling operators to adapt processes to improve drinking water quality.

Ozone regeneration of granular activated carbon for trihalomethane control.

Spatial and temporal variations of trihalomethanes (THMs) in distribution systems have challenged water treatment facilities to comply with disinfection byproduct rules. In this study, granular activated carbon (GAC) and modified GAC (i.e., Ag-GAC and TiO2-GAC) were used to treat chlorinated tap water containing CHCl3 (15-21µg/L), CHBrCl2 (13-16µg/L), CHBr2Cl (13-14µg/L), and CHBr3 (3µg/L). Following breakthrough of dissolved organic carbon (DOC), GAC were regenerated using conventional and novel methods. GAC regeneration efficiency was assessed by measuring adsorptive (DOC, UV absorbance at 254nm, and THMs) and physical (surface area and pore volume) properties. Thermal regeneration resulted in a brief period of additional DOC adsorption (bed volume, BV, ∼6000), while ozone regeneration was ineffective regardless of the GAC type. THM adsorption was restored by either method (e.g., BV for ≥80% breakthrough, CHBr3 ∼44,000>CHBr2Cl ∼35,000>CHBrCl2 ∼31,000>CHCl3 ∼7000). Cellular and attached adenosine triphosphate measurements illustrated the antimicrobial effects of Ag-GAC, which may have allowed for the extended THM adsorption compared to the other GAC types. The results illustrate that ozone regeneration may be a viable in-situ alternative for the adsorption of THMs during localized treatment in drinking water distribution systems.

Molecular dynamics simulations of trihalomethanes removal from water using boron nitride nanosheets.

Molecular dynamics simulations were performed to investigate the separation of trihalomethanes (THMs) from water using boron nitride nanosheets (BNNSs). The studied systems included THM molecules and a functionalized BNNS membrane immersed in an aqueous solution. An external pressure was applied to the z axis of the systems. Two functionalized BNNSs with large fluorinated-hydrogenated pore (F-H-pores) and small hydrogen-hydroxyl pore (H-OH-pores) were used. The pores of the BNNS membrane were obtained by passivating each nitrogen and boron atoms at the pore edges with fluorine and hydrogen atoms in the large pore or with hydroxyl and hydrogen atoms in the small pore. The results show that the BNNS with a small functionalized pore was impermeable to THM molecules, in contrast to the BNNS with a large functionalized pore. Using these membranes, water contaminants can be removed at lower cost.

Probing Coagulation Behavior of Individual Aluminum Species for Removing Corresponding Disinfection Byproduct Precursors: The Role of Specific Ultraviolet Absorbance.

Coagulation behavior of aluminum chloride and polyaluminum chloride (PACl) for removing corresponding disinfection byproduct (DBP) precursors was discussed in this paper. CHCl3, bromine trihalomethanes (THM-Br), dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA) formation potential yields were correlated with specific ultraviolet absorbance (SUVA) values in different molecular weight (MW) fractions of humic substances (HS), respectively. Correlation analyses and principal component analysis were performed to examine the relationships between SUVA and different DBP precursors. To acquire more structural characters of DBP precursors and aluminum speciation, freeze-dried precipitates were analyzed by fourier transform infrared (FTIR) and C 1s, Al 2p X-ray photoelectron spectroscopy (XPS). The results indicated that TCAA precursors (no MW limits), DCAA and CHCl3 precursors in low MW fractions (MW<30 kDa) had a relatively good relations with SUVA values. These DBP precursors were coagulated more easily by in situ Al13 of AlCl3 at pH 5.0. Due to relatively low aromatic content and more aliphatic structures, THM-Br precursors (no MW limits) and CHCl3 precursors in high MW fractions (MW>30 kDa) were preferentially removed by PACl coagulation with preformed Al13 species at pH 5.0. Additionally, for DCAA precursors in high MW fractions (MW>30 kDa) with relatively low aromatic content and more carboxylic structures, the greatest removal occurred at pH 6.0 through PACl coagulation with aggregated Al13 species.

Trihalomethanes (THMs) precursor fractions removal by coagulation and adsorption for bio-treated municipal wastewater: Molecular weight, hydrophobicity/hydrophily and fluorescence.

Due to concerns over health risk of disinfection byproducts (DBPs), removal of trihalomethanes (THMs) precursor from bio-treated wastewater by coagulation and adsorption was investigated in this study. Ultrafiltration (UF) membranes and nonionic resins were applied to fractionate THMs precursor into various molecular weight (MW) fractions and hydrophobic/hydrophilic fractions. Characteristics of coagulated water and adsorbed water were evaluated by the three-dimensional excitation and emission matrix (3DEEM) fluorescence spectroscopy. Results showed that coagulation and adsorption were suitable for removing different hydrophobic/hydrophilic and fluorescent fractions. Coagulation decreased THMs concentration in hydrophobic acids (HoA) fraction from 59 µg/L to 39 µg/L, while the lowest THMs concentration (9 µg/L) in hydrophilic substances (HiS) fraction was obtained in adsorbed water. However, both coagulation and adsorption were ineffective for removing fractions with MW<5 kDa. Although coagulation and adsorption processes could reduce THMs formation, some specific THMs formation potential (STHMFP) in residual dissolved organic matter (DOM) fractions increased in this study. Hydrophobic acid and hydrophilic fractions increased after coagulation treatment, and low MW and hydrophobic fractions increased after adsorption treatment. In addition, active carbon adsorbed more organic matter than coagulant, but brominated disinfection byproducts (Br-DBPs) in adsorbed water turned to the major THMs species after chlorination.

Removal of trihalomethanes from aqueous solution through armchair carbon nanotubes: a molecular dynamics study.

Molecular dynamics simulations were performed to investigate the removal of trihalomethanes (THMs) including CH3Cl, CH2Cl2 and CHCl3 from aqueous solutions by armchair carbon nanotubes (CNTs) under induced pressure. The studied system involved the armchair CNTs embedded between two graphene sheets with an aqueous solution of THMs in the simulation box. An external pressure was applied to the system along the z-axis of the simulation box. Six types of armchair CNTs with different diameter were used in this work, included (4,4), (5,5), (6,6), (7,7), (8,8) and (9,9) CNTs. The results of molecular dynamics simulation display that the armchair CNTs behave differently relative to THMs and water molecules. The permeation of THMs and water molecules through the armchair CNTs was dependent on the diameter of CNTs and the applied pressure.

Reducing THMFP by H2O2/UV oxidation for humic acid of small molecular weight.

In this study, the merits of using H2O2/UV oxidation for reducing trihalomethane formation potential (THMFP), colour, and dissolved organic carbon (DOC) of smaller molecular humic acid were investigated, especially the energy consumption based on EEO. The results show that THMFP decreases by increasing oxidation time, H2O2 dose and UV intensity. The reaction constant in descending order is kColour>kDOC>kTHMFP. Furthermore, EEO shows three trends. First, it decreases as H2O2 dose increases. That is, by increasing the amount of H2O2 dose, the electrical energy efficiency becomes better. Second, EEO,9 W>EEO,13 W, implying that higher UV power would result in a higher electrical energy efficiency. Third, EEO,THMFP>EEO,DOC>EEO,colour. That is, the electric energy efficiency is the best for colour removal, second for DOC removal, and third for THMFP reduction. The operation costs for 90% removal of colour, DOC, and THMFP are from 0.31 to 0.69, from 0.78 to 1.72, and from 1.11 to 2.29 US$/m3, respectively. However, reducing THMs to Taiwan's drinking water standard of 80 µg/L needs only 0.25-0.60 US$/m3. Therefore, the condition with UV of 9 W, H2O2 of 50 mg/L, and oxidation time of 23 min can be applied for THMs reduction as the cost is the smallest of 0.25 US$/m3, even lower than current Taiwan's drinking water price of 0.3 US$/m3.

Simultaneous removal of dissolved organic matter and bromide from drinking water source by anion exchange resins for controlling disinfection by-products.

Anion exchange resins (AERs) with different properties were evaluated for their ability to remove dissolved organic matter (DOM) and bromide, and to reduce disinfection by-product (DBP) formation potentials of water collected from a eutrophic surface water source in Japan. DOM and bromide were simultaneously removed by all selected AERs in batch adsorption experiments. A polyacrylic magnetic ion exchange resin (MIEX®) showed faster dissolved organic carbon (DOC) removal than other AERs because it had the smallest resin bead size. Aromatic DOM fractions with molecular weight larger than 1600 Da and fluorescent organic fractions of fulvic acid- and humic acid-like compounds were efficiently removed by all AERs. Polystyrene AERs were more effective in bromide removal than polyacrylic AERs. This result implied that the properties of AERs, i.e. material and resin size, influenced not only DOM removal but also bromide removal efficiency. MIEX® showed significant chlorinated DBP removal because it had the highest DOC removal within 30 min, whereas polystyrene AERs efficiently removed brominated DBPs, especially brominated trihalomethane species. The results suggested that, depending on source water DOM and bromide concentration, selecting a suitable AER is a key factor in effective control of chlorinated and brominated DBPs in drinking water.

Dissolved organic carbon and trihalomethane precursor removal at a UK upland water treatment works.

The removal of dissolved organic carbon (DOC) during potable water treatment is important for maintaining aesthetic water quality standards, minimising concentrations of micro-pollutants, controlling bacterial regrowth within distribution systems and, crucially, because it contains a sub-component that can act as trihalomethane (THM) precursors. In this study, the concentration and characteristics of raw water DOC and THM formation potential (THMFP) entering an upland potable water treatment works were analysed over twelve months. Correlations between raw water DOC characteristics, standardised THMFP (STHMFP) and % DOC removal were also investigated. DOC and THM precursor removal during a series of treatment stages was examined over this period, as well as potential selectivity in the removal of DOC fractions, to assess the importance of different treatment stages for DOC removal and THM amelioration. Though THMFP removal remained high and fairly stable throughout the study period (83-89%), the data suggest that this was mostly the result of high DOC removal rates rather than the selective removal of THM precursors. Whilst this chemical agnosticism makes DOC removal more robust, it may make the overall process more vulnerable to exceeding permissible THM concentrations under changing climatic conditions. The kinetics of the reaction between DOC and chlorine appeared to vary seasonally, indicating temporal changes in the proportions of fast- and slow-reacting precursors with implications for THM concentrations at the point of delivery to the consumer. The initial treatment stages, comprising coagulation-flocculation and dissolved air floatation (DAF) were by far the most important in terms of bulk DOC removal and the preferential removal of THM precursors, though, surprisingly, DOC quality was also modified following chlorination and secondary rapid gravity filtration (RGF). Though net THM concentration decreased following initial treatment stages, a doubling in the proportion of brominated THMs (BrTHMs), which are reported to be more carcinogenic, was also observed.