FTIR evaluation of functional groups involved in the formation of haloacetic acids during the chlorination of raw water

This work investigated the formation potential of haloacetic acid (HAA) compounds in the raw water for the Bangkhen water treatment plant (Bangkok, Thailand). The resin adsorption technique (with three different types of resins, i.e. DAX-8, AG-MP-50 and WA-10) was employed to characterize the organic content in the raw water into six fractions, i.e. hydrophobic neutral (HPON), hydrophobic acid (HPOA), hydrophobic base (HPOB), hydrophilic neutral (HPIN), hydrophilic acid (HPIA) and hydrophilic base (HPIB). Hydrophilic species appeared to be the predominant organic species in this water source (approximately 60%) with the neutral fraction being the most abundant (approximately 40%). Hydrophobic species, on the other hand, played the most important role in the formation of haloacetic acids as they contributed to as much as approximately 56% of total HAA formation potential. Among the three hydrophobic species, the hydrophobic base exhibited the highest specific HAA formation with 208mugHAAs/mg of dissolved organic carbon (DOC). Each organic fraction was examined for its associated functional groups by Fourier transform infrared (FTIR). The investigation of the formation of HAAs was achieved by tracking the changes in the FTIR results of the same water sample before and after the chlorination reaction. Based on the results obtained from this study, carboxylic acids, ketone, amide, amino acids and aromatic characteristic organics seemed to be the main precursors to HAA formation.     

Trihalomethanes formation potential of shrimp farm effluents

Shrimp farm effluents along the Bangpakong River in the Chachoengsao Province of Thailand were evaluated for their trihalomethane formation potential (THMFP) and related parameters. The dissolved organic carbon (DOC), salinity and bromide ion concentrations of shrimp farm effluents were in the ranges of 12-14 mg/L, 0.1-14.5 ppt, and 0-14 mg/L, respectively. The dissolved organic matter was fractionated into hydrophobic and hydrophilic fractions having a range concentration of 3-5 and 8-10mg/L, respectively. The THMFP for all shrimp farm effluents analyzed was in the range of 810-3100 microg/L. The hydrophilic organic fraction was found to be a more active precursor of trihalomethanes (THMs) with 700-966 microg/L THMFP obtained from this fraction, while only 111-363 microg/L THMFP was derived from the hydrophobic fraction. The experimental results showed that salinity and bromide played crucial roles in the formation of THMs. At low salinity and bromide levels, chloroform was the dominant THM species, whereas at high salinity and bromide levels, bromoform became the dominant species. A Fourier Transform Infrared (FTIR) spectrum analysis of the samples before and after chlorination illustrated that the functional groups involved in the THM formation reaction were phenolic compounds, amines, aromatic hydrocarbons, aliphatic bromo-compounds, and aliphatic chloro-compounds.     

Evaluation of disinfection by-products formation during chlorination and chloramination of dissolved natural organic matter fractions isolated from a filtered river water

Dissolved natural organic matter (DOM) in a filtered river water was isolated and fractionated into six different fractions. Trihalomethanes (THMs) and haloacetic acids (HAAs) formed from these isolated DOM fractions during chlorination and chloramination were determined. Results show that the hydrophobic acid, hydrophilic acid, hydrophilic base and hydrophobic neutral are major precursors of THMs and HAAs. There exist good correlations between the values of specific ultraviolet absorbance at 254nm of the individual DOM fractions and their disinfection by-products formation potential, indicating that aromatic moieties are responsible for disinfection by-products formation for both hydrophobic and hydrophilic DOM fractions. Chloramination of the DOM fractions yields much less THMs and HAAs than chlorination. For the dominant DOM fraction (i.e. hydrophobic acid) in the water, the yields of THMs and HAAs increase more significantly in chlorination than those in chloramination with the increase of disinfectant dosage, contact time and dissolved organic carbon content.     

The variation of mass and disinfection by-product formation potential of dissolved organic matter fractions along a conventional surface water treatment plant

Dissolved organic matter (DOM) influences many aspects of water treatment, including the formation of potentially harmful disinfection by-products (DBPs) when disinfectants are applied. DOM from a conventional surface water treatment plant (WTP) in Northern New Jersey was isolated and fractionated using resin adsorption chromatography into six different fractions. These fractions are operationally categorized as hydrophobic acid, hydrophobic neutral, hydrophobic base, hydrophilic acid, hydrophilic neutral and hydrophilic base. The hydrophilic acid fraction was found to be the most abundant fraction in the source water. The hydrophilic neutral, hydrophilic acid and hydrophobic acid fractions had the highest removal efficiency through the WTP (about 65%). The variation and removal effectiveness of each fraction along the WTP was studied. Seven-day chlorine DBP formation potential (FP) tests were performed on all DOM fractions through the WTP. For the source water studied, the hydrophilic acid fraction was found to be the most reactive precursor to the trihalomethane (THM) formation. The hydrophobic neutral fraction was found to be the fraction of concern with respect to the FP of haloacetic acids (HAAs) class of DBPs. The FP of each fraction's class of DBPs was found to be amenable for reduction along the treatment train, specifically by coagulation/sedimentation. The fractionated approach concept showed to be very beneficial in the study of DBP precursors and their effective removal by physical and chemical treatment.     

Seasonal variations of chemical and physical characteristics of dissolved organic matter and trihalomethane precursors in a reservoir: a case study

Dissolved organic matter (DOM) and its potential to form disinfection by-products (DBPs) during water treatment are of great public health concern. Understanding the seasonal changes in DOM composition and their reactivity in DBP formation could lead to a better treatment of drinking water and a more consistent water quality. DOM from the East-Lake, a reservoir in the south-China, was fractionated and characterized by XAD resin adsorption (RA) and ultrafiltration (UF) techniques during different seasons within a year. The properties of chemical fractions (isolated by RA) appeared more stable than those of physical fractions (separated by UF) throughout the sampling period. The relative contribution of each chemical fraction to the total dissolved organic carbon (DOC), UV(254) absorbance and trihalomethane formation potential (THMFP) remained relatively constant across the sampling period. However, the physical (molecular weight) fractions of the DOM exhibited large seasonal changes in UV(254) and THMFP. Compared to the parameter of DOC, the THMFP and specific THMFP (STHMFP) of either chemical or physical fractions were more variable. In terms of DOC concentration, the hydrophobic acids (HoA) and hydrophilic matter (HiM) dominated in the DOM in most of the seasons; while the components with molecular weight of 10-30 kDa and less than 1 kDa were the predominant physical fractions.     

Effect of bromide ion on isolated fractions of dissolved organic matter in secondary effluent during chlorination

The role of bromide ion in the trihalomethane (THM) formation and structure of dissolved organic matter (DOM) during chlorination of the secondary effluent taken from the Wenchang Wastewater Treatment Plant (Harbin, China) was investigated. DOM was fractionated using XAD resins into five fractions: hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N) and hydrophilic fraction (HPI). The patterns of individual THM species with increased bromide concentrations were similar for all DOM fractions. The THM speciation as well as halogen fraction for these five fractions followed similar trends with the Br(-)/Cl(2) ratio. Chlorination resulted in decreased ultraviolet (UV) absorbance across wavelengths from 250 to 280 nm for DOM fractions whether bromide ions existed or not, and bromide addition led to lower differential UV absorbance values. Fourier-transform infrared (FT-IR) results indicated that chlorination, whether bromide ions existed or not, resulted in the near elimination of aromatic CH and amide peaks, increased CO absorption intensity and occurrence of CO and CCl peaks for HPO-A, HPO-N, TPI-A and TPI-N. Furthermore, bromide addition in chlorination led to the occurrence of CBr peak for all four fractions.     

Rapid delineation of humic and non-humic organic matter fractions in water

Dissolved organic matter (DOM) in water is often characterized by aggregate parameters like dissolved organic carbon (DOC). DOM from conventional surface water treatment plant in Northern New Jersey was isolated and fractionated using resin adsorption chromatography into six different fractions, which were operationally categorized as hydrophobic acid, hydrophobic neutral, hydrophobic base, hydrophilic acid, hydrophilic neutral and hydrophilic base. The spectral fluorescent signatures (SFS) technique was developed for the quantitative identification of the six fractions by post-processing analysis that includes a statistical model. The SFS is the total sum of emission spectra of a sample at different excitation wavelengths, recorded as a matrix of fluorescent intensity in coordinates of excitation and emission wavelengths, in a definite spectral window. High sensitivity and rapid identification and quantification of DOM fractions are among the main features of the technique. Since hydrophobic and hydrophilic substances are considered more humic and non-humid in nature, respectively, the technique provided an opportunity to rapidly delineate source waters in terms of such categories.     

Characterization of dissolved organic matter in leachate discharged from final disposal sites which contained municipal solid waste incineration residues

The properties of dissolved organic matter (DOM) in the leachates discharged from lysimeters and landfill sites containing municipal solid waste incineration residues (MSWIRs) were studied. DOM samples were divided into hydrophobic acid, base, neutral (Hpo-A, Hpo-B, Hpo-N) and hydrophilic (Hpi) fractions using the fractionation method employing DAX-8 resin. Hpi was the smallest fraction of all the raw leachate samples. The proportion of Hpo-N increased with increasing operating time. Landfill sites containing abundant non-combustible wastes showed a higher proportion of Hpo-B than Hpo-A. The molecular weights and functional groups of the DOM fractions were studied by using gel permeation chromatography and FTIR, respectively. In addition, the fluorescent properties and binding sites of the DOM fractions were investigated using fluorescence analysis. In the synchronous scan spectra of each DOM fraction, most of DOM fractions showed an emission peak for the main fluorophores at around 300 nm or 350 nm, which are regarded as aromatic amino acid-like fluorophores. The interaction between the DOM fraction and the pollutants (Cu(2+), pyrene and phenanthrene) was investigated using the fluorescence quenching method. It was observed that the aromatic amino acid-like fluorophores in the DOM fractions could be an important factor affecting complexation with the pollutants.     

Fluorescence excitation-emission matrix spectroscopy with regional integration analysis for characterizing composition and transformation of dissolved organic matter in landfill leachates

Dissolved organic matter (DOM) obtained from landfill leachates was separated into hydrophobic base, hydrophilic matter (HIM), hydrophobic acid (HOA), and hydrophobic neutral fractions. The composition and transformation of the DOM and its fractions were investigated. The results show that the DOM isolated from young, intermediate, and old landfill leachates were mainly composed of tyrosine-, tryptophan-, and humic- and fulvic-like substances, respectively. The primary fractions of the DOM in leachates were HOA and HIM. The HOA and HIM fractions from young leachates predominantly contained tryptophan- and tyrosine-like materials, respectively. The HOA fractions in intermediate and old leachates were mainly composed of humic- and fulvic-like materials, whereas the HIM fractions were dominated by tryptophan-like materials and humic- and fulvic-like substances. The hydrophobic organic fractions and humic- and fulvic-like substances increased with time, whereas the HIM and the tyrosine-like materials decreased during the landfill process, rendering biological processing of leachates ineffective.     

Reduction of organic matter and trihalomethane formation potential in reclaimed water from treated industrial estate wastewater by coagulation

Raw water from treated industrial estate wastewater in northern Thailand was used in jar-test coagulation experiments with variations of separate alum and ferric chloride dosages from 10 to 80 mg/L at pH conditions ranging from 5 to 6.5. Natural organic matter (NOM) surrogates and trihalomethane formation potential (THMFP) were determined to study their reduction. The obtained results showed that total organic carbon (TOC) were gradually reduced from the average value of about 6.1 mg/L to a level of about 4.0 mg/L by alum and ferric chloride dosages of approximately 40 mg/L. Moreover, dissolved organic carbon (DOC) were reduced from an average value of 5.1 mg/L to a level of about 4.0 mg/L by alum and ferric chloride dosages of approximately 40 mg/L. Specific ultraviolet absorption (SUVA) were decreased from an average value of approximately 4.7 L/mgm to a level of about 2 L/mgm by alum and ferric chloride dosages of approximately 20 mg/L. In addition, chlorine demands at 1 day reaction were the same as those of 7-day demands with a correlation coefficient of 0.98 (n = 10, correlation significant at the 0.01 level). Interestingly, chloroform of approximately 65 and 60% of total THMFP was found as the predominant THMFP species in treated industrial estate wastewater and reclaimed water, respectively, in comparison with other THM species. Maximum THMFP percentage removal of 25 and 28 by using alum and ferric chloride dosages of about 80 mg/L at pH 5.5 and 5 were obtained, respectively, at the examined conditions.     

Characterization of aquatic humic substances to DBPs formation in advanced treatment processes for conventionally treated water

An advanced water treatment demonstration plant consisted of ozone/granular activated carbon processes was operated to study feasibility of the processes. Natural organic matter (NOM) from raw and process waters at the demonstration plant was isolated into humic and non-humic fractions by physicochemical fractionation method to investigate characteristics of humic fraction (i.e., humic substances, HS) as a predominant haloform reactant. Ozone did not significantly oxidize the carboxylic fraction (from 39.1 to 35.9%), while GAC removed some of the carboxylic fraction (from 35.9 to 29.1%). Formation potential of trihalomethanes (THMs) as compared to haloacetic acids formation potential (HAAFP) was highly influenced by HS. Higher yields of THMs resulted from chlorination of HS with a higher phenolic content and phenolic fraction in the HS gradually decreased from 60.5% to 15.8% through the water treatment. The structural and functional changes of HS were identified by elemental, Fourier-transform infrared (FT-IR) and proton nuclear magnetic resonance ((1)H NMR) analyses, and these results were mutually consistent. The functional distribution data obtained by using A-21 resin could be used to support the interpretation of data obtained from the spectroscopic analyses. Decreases in ratio of UV absorbance at 253 nm and 203 nm (A(253)/A(203)) and DBPFPs/DOC showed consistent trends, therefore, A(253)/A(203) ratio may be a good indicator for the disinfection by-product formation potentials (DBPFPs).     

Characterization of isolated fractions of dissolved organic matter from sewage treatment plant and the related disinfection by-products formation potential

Dissolved organic matter (DOM) in effluent from a conventional sewage treatment plant was isolated using resin adsorbents into six classes: hydrophobic bases (HoB), hydrophobic acids (HoA) and hydrophobic neutrals (HoN); hydrophilic bases (HiB), hydrophilic acids (HiA) and hydrophilic neutrals (HiN). Organic acids were the most abundant fractions of DOM. Hydrophobic organics especially hydrophobic acids were found to have higher overall disinfection by-products formation potential (DBPFP). Moreover, the potential decreased as the sequence of acids, neutrals and bases. Ultraviolet spectrophotometry at 254nm (UV(254)), fluorescence spectroscopy, size exclusion chromatography and Fourier transform infrared spectroscopy (FTIR) were employed to characterize DOM fractions. And the relationship between the characteristics of DOM fractions and the related DBPFP was discussed in detail. It was found that UV(254) to DOC ratio (SUVA) exhibited a positive correlation with haloacetic acids (HAAs) formation potential whereas distinctive linear correlation was not observed between SUVA and trihalomethanes (THMs) formation potential. Of the fluorescence organics contained in DOM, humic acids exhibited higher chlorine reactivity than fulvic acids. Smaller molecules of humic acids produced more DBPs. Furthermore, a combination of aromatic moieties and aliphatic structures with nu(C_O) groups contributed largely to the formation of DBPs.     

Formation of disinfection by-products in the chlorination of ammonia-containing effluents: significance of Cl2/N ratios and the DOM fractions

The presence of ammonia nitrogen (NH(3)-N) in the effluent strongly affected the formation of disinfection by-products (DBPs) during its chlorination. The effect of chlorine (as mg/L Cl(2)) to NH(3)-N (as mg/L N) mass ratios (Cl(2)/N) and the chemical fractions of dissolved organic matter (DOM) in the effluent on the DBPs formation was investigated. Results indicated that the formation of DBPs increased with increasing Cl(2)/N. The concentration and speciation of DBPs varied among different DOM fractions at different zones of chlorination breakpoint curves. The formation rate of total haloacetic acids (THAA) and total trihalomethanes (TTHM) was promoted after the chlorination breakpoint, whereas the reaction of monochloramine with HOCl to dichloramine may cause a decrease in the DBPs formation potential thereafter. Organic acids were found to be the dominant precursors of DBPs with or without the presence of NH(3)-N, which indicated that the CC, CO and C-O structures contributed to the formation of DBPs significantly. In addition, the incorporation of bromine in THMs of the HiA fraction increased with the increasing of Cl(2)/N mass ratios before the chlorination breakpoint, but decreased sharply after the breakpoint. ΔA(280) (absorbance at 280 nm), defined as A(280,initial)-A(280,final), was proved to be linearly related to the TTHM and THAA of wastewater without containing Br(-) during chlorination or chloramination.     

Hydrophilic and hydrophobic interactions in cross-linked chitosan membranes

Chitosan membranes with different cross-linking density were prepared by modifying cross-linking time. Sodium tripolyphosphate was the cross-linking agent. A pulsed nuclear magnetic resonance study was performed on uncross-linked and cross-linked membranes. Different fraction of water molecules were identified in different zones within the membranes. The ratio of water molecules per chitosan repeating unit were calculated. A maximum of twelve water molecules were tightly coordinated to the chitosan repeating unit. Also, a very small water molecule fraction was identified but it was mobile enough as not to contribute to the dipolar interactions. The cross-linking reaction could lead to the formation of hydrophilic and hydrophobic interactions. These two types of interactions could result in the coexistence of a network formed by hydrophilic and hydrophobic micropores. This knowledge could be useful for the interpretation of results of hydrophobic drugs permeation across hydrophilic membranes. For example, the increment of estradiol fluxes across chitosan membranes with an increase in cross-linking density.     

Effects of pH on the chlorination process of phenols in drinking water

Toxic organic compounds detected generally in source water could combine with chlorine and contribute significantly to chlorination disinfection by-products (CDBPs). The effects of pH on species distribution of CDBPs and the kinetics of chlorination were investigated using phenol as a model of ionizable toxic organic compounds in the pH range of 6.0-9.0. It was found that five chlorination products including 2-monochlorophenol (2-MCP), 4-monochlorophenol (4-MCP), 2,6-dichlorophenol (2,6-DCP), 2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (TCP) were produced by successive chlorination substitution. MCP (2-MCP and 4-MCP) were the dominant products and phenol partly remained in acid media, while TCP and DCP (2,6-DCP and 2,4-DCP) were the main components in neutral and alkaline media. A steady equilibrium of phenol and its chlorination products was reached in 20-30 min in acid-, neutral- and slightly alkaline media, and was delayed to 60-180 min in alkaline media. The difference in properties between phenols and phenolates, and those between HOCl and ClO(-) should be considered simultaneously in explaining the effects of pH on the chlorination process with the theory of electrophilic substitution. These results show that pH plays an important regulating role in the species distribution of CDBPs and the kinetics of chlorination for ionizable toxic organic compounds in chlorination.     

Comparison of spectral fluorescent signatures-based models to characterize DOM in treated water samples

Statistical procedures enable a multivariate analysis of the measurements to identify specific characteristics of the dissolved organic matter (DOM) fractions in raw natural water, including the concentrations. In this work, three already established models were used to predict the concentrations of fractions of DOM from spectral fluorescent signatures (SFSs): a general linear regression (GLR), loadings and scores of a principal components analysis (PCA), and a partial least squares regression (PLS). Details about the method undertaken to prepare the fractions were given. Water samples from surface water treatment plants in New Jersey were used for the testing. In all cases, PLS have shown much better biases and accuracies than GLR and PCA models. Hydrophilic neutral, however, showed poor performances (bias 33%) due to the isolation technique used. Recommendations were provided in order to improve the DOM characterization through SFS, which linked to PLS make a powerful and cost-effective surrogate parameter to characterize DOM.     

Self-assembly of hydrophilic homopolymers: a matter of RAFT end groups

Unusual self-assembly behavior is observed for a range of hydrophilic homopolymers. This self-assembly behavior is contrary to the expected behavior of such hydrophilic polymers and instead mimics more commonly reported amphiphilic block copolymers. It is proposed that the unique combination of hydrophobic end groups at both the α and ω chain end accounts for this unusual self-assembly behavior. Complex internal polymer micelles are spontaneously formed when hydrophilic homopolymer polyelectrolytes and neutral polymers (with a weight fraction of the hydrophobic end groups <10 wt%) are directly dissolved in water. The homopolymers, poly[2-(diethylamino)ethyl methacrylate], poly(N-isopropylacrylamide), and poly(ethoxyethylacrylate) are synthesized by reversible addition-fragmentation chain-transfer (RAFT) polymerization using S'-1-dodecyl-(S')-(α,α'-dimethyl-α″-acetic acid) trithiocarbonate (DDMAT) and its derivatives as chain transfer agents (CTAs). A range of polyelectrolyte homopolymers with different terminal groups are designed and synthesized, which under acidic aqueous solution direct the self-assembly to form well-defined nanostructures. This assembly behavior was also observed for neutral polymers, and it was determined that the structure of the hydrophobic end groups (and thus choice of RAFT CTA) are very important in facilitating this unusual self-assembly behavior of hydrophilic homopolymers. It is proposed that the functionality of commonly used CTAs such as DDMAT, can affect the solution association of the resultant homopolymers and can in fact afford ABA' type polymers, which can undergo self-assembly to form higher-order nanostructures.     

Molecular size distribution of dissolved organic matter in water of the Pearl River and trihalomethane formation characteristics with chlorine and chlorine dioxide treatments

River water sample was collected from Guangzhou section of the Pearl River to investigate soluble organic fractions and formation of trihalomethane (THMs) after chlorine and chlorine dioxide treatments. The water sample was passed through Amicon YC-05, YM-1, YM-3, YM-10, YM-30, YM-100 and ZM-500 series membranes after a pre-treatment. The molecular weight distribution and the specific ultra-violet absorbance (SUVA(254)) of each fraction obtained from membrane were analyzed, and these fractions were further disinfected with chlorine and chlorine dioxide. The results showed that reverse osmosis (RO) fraction contained mainly dissolved organic matter (DOM) from the water sample, suggesting that the water has been highly contaminated by anthropogenic activities. Meanwhile, the THMs concentration and SUVA(254) increased gradually as the molecular weight of the obtained fractions reduced, indicating that the low molecular weight DOM was the major THMs precursor in the disinfection process with chlorine and chlorine dioxide. The results suggest that THMs in source water of Pearl River could be effectively reduced when pollution of human activity is greatly controlled. Between the two disinfection processes tested, chlorine dioxide produced less THMs than chlorine in this study.     

Switchable nanoassembly from an azobenzene-containing dye

In this work, we investigated optical properties and the morphology of the amphiphilic azobenzene dye 1 containing hydroxyl azobenzene and C10 alkyl chains. Since the hydroxyl group on 1 has a pKa of 9.38, the deprotonation of the hydroxyl group occurs at pH > pKa (9.38) and thus the 1 nanoparticles are negatively charged. The deprotonated hydroxyl group is hydrophilic relative to the long alkyl chain that is hydrophobic, while the hydrophobic and hydrophilic parts are connected by covalent bonds. When such an azobenzene molecule 1 with both hydrophobic and hydrophilic groups exists in solution, "self-aggregation" may occur due to the hydrophobic interaction between the long alkyl chains. The scattered morphology at pH 7.0 (neutral state) and the aggregated morphology at pH 10.5 (anionic state) of 1 were demostrated by transmission electron microscopy (TEM) and atomic force microscopy (AFM) images. Formation of supramolecular aggregation-induced vesicular-like structures are highly interesting due to the ability to respond to external triggers, pH. The pH value can be reversed by adding acid or base to the system, that is, switching the aggregation "on" and "off" can be repeated.     

Halogenating reaction activity of aromatic organic compounds during disinfection of drinking water

The halogenating reactions of five aromatic organic compounds (AOCs) with aqueous chlorine (HOCl/OCl(-)) and aqueous bromine (HOBr/OBr(-)) were studied with an aim to compare the formation properties of haloacetic acids (HAAs) for the corresponding chlorination or bromination reactions of AOCs, respectively. The experiment results indicated that the HAAs substitution efficiency for the bromination reactions of AOCs was greater than that for the chlorination reactions, and the formation of HAAs had a strong dependence on the chemical structure of AOCs. The chlorination or bromination reaction activities for the AOCs with electron donating functional groups were higher than that for them with electron withdrawing functional groups. The kinetic experiments indicated that the reactions of aqueous bromine with phenol were faster than those of aqueous chlorine with phenol and the halogen consumption exhibited rapid initial and slower consumption stages for the reactions of phenol with aqueous chlorine and bromine, respectively. In addition, the HAAs production for the chlorination reaction of phenol decreased with the increase of pH. These conclusions could provide the valuable information for the effective control of the disinfection by-products during drinking water treatment operation.