Reactions of chlorine and chlorine dioxide with resorcinol in aqueous solution and adsorbed on granular activated carbon

Resorcinol reacted with chlorine and chlorine dioxide at pH 7 in dilute aqueous solution and in the presence of granular activated carbon (GAC) to produce numerous chlorinated compounds. Major products included chlororesorcinols and various chlorinated cyclopentenediones. Few reaction products were found in common to both Cl₂ and ClO₂ when reacted with resorcinol in the absence of GAC. However, both oxidants produced the same major recoverable chlorinated product, a dichlorocyclopentenedione, when reacted with resorcinol preadsorbed on GAC columns. No products were found when aqueous resorcinol was applied to GAC columns following contact of the carbon with Cl₂ or ClO₂ solutions.     

Formation of organic chloramines during water disinfection - chlorination versus chloramination

Many of the available studies on formation of organic chloramines during chlorination or chloramination have involved model organic nitrogen compounds (e.g., amino acids), but not naturally occurring organic nitrogen in water. This study assessed organic chloramine formation during chlorination and chloramination of 16 natural organic matter (NOM) solutions and 16 surface waters which contained dissolved organic nitrogen (DON). Chlorination rapidly formed organic chloramines within 10 min, whereas chloramination formed organic chloramination much more slowly, reaching the maximum concentration between 2 and 120 h after the addition of monochloramine into the solutions containing DON. The average organic chloramine formation upon addition of free chlorine and monochloramine into the NOM solutions were 0.78 mg-Cl₂/mg-DON at 10 min and 0.16 mg-Cl₂/mg-DON at 24 h, respectively. Organic chloramine formation upon chlorination and chloramination increased as the dissolved organic carbon/dissolved organic nitrogen (DOC/DON) ratio decreased (i.e., DON contents increased). Chlorination of molecular weight (10,000 Da) fractionated water showed that molecular weight of DON would not impact the amount of organic chloramines produced. Comparison of three different disinfection schemes at water treatment plants (free chlorine, preformed monochloramine, and chlorine/ammonia additions) indicated organic chloramine formation could lead to a possible overestimation of disinfection capacity in many chloraminated water systems that add chlorine followed by an ammonia addition to form monochloramine.     

Etude physicochimique de la chloration de l'eau de mer artificielle contenant de l'azote ammoniacal

Chlorine added to ammonia-free sea-water gives rise to a fast and quantitative oxidation of bromide to hypobromite and hypobromous acid. However as ammonia nitrogen levels commonly found in coastal and estuarine sea-water are sufficiently high and thus not negligible compared to the chlorine dose introduced formation of monochloramine to compete with oxidation of bromine leading to bromamines. The relative importance of these two reactional pathways is estimated considering both bromine determination and study of the electron absorption spectra of chlorinated seawater. In order to avoid substitution reactions taking place in the presence of organic compounds, preliminary experiments have been carried out in artificial and u.v. photo-oxidized sea-water.The nature of the species formed depends on the molar ratio added chlorine vs ammonia-nitrogen concentration of seawater. With Cl/N larger than 1.5, only bromide derivatives are obtained: dibromamine, tribromamine and bromine(I) (HBrO + BrO⁻). Cl/N smaller than 1.5 leads to a mixture of monochloramine, dibromamine and some monobromamine: monochloramine clearly predominates when ammonium concentrations reach higher values. Stoichiometry of ammonia to nitrogen oxidation by chlorine explains this ratio of 1.5 and a strong decrease of the total oxidant concentration is observed under these conditions. Bromamines decompose within the following 30–60 min; only stable compounds remain: either bromine(I) or monochloramine according to Cl/N values. A similar behaviour is observed in natural seawater previously doped with ammonia as to the nature of the products formed for a given Cl/N ratio; however, bromamines decompose more rapidly due to bromination of organic components.     

Analysis of selected trace organics in advanced wastewater treatment systems

Effluents through four different pilot tertiary wastewater treatment systems were monitored for selected trace organic compounds. The effects of using ozone, free and combined chlorine residuals in these systems were also studied. Advanced treatment of secondary effluent using various combinations of flocculation (alum and polymer), dual media filtration, and carbon adsorption were evaluated for production/removal of volatile halogenated organics, polynuclear aromatics, chlorinated pesticides, and polychlorinated biphenyls. Gas chromatographic methods were used for the analysis of these different classes of compounds: specific techniques and analytical parameters are described. Salient results included: drastic increases in trihalomethane production using free chlorine residuals: disinfection with combined chlorine species does not produce significant levels of trihalomethanes: approximately 90% reduction in trihalomethane levels by carbon adsorption: absence of detectable quantities of polynuclear aromatics: significant decreases in pesticide and PCB levels by carbon adsorption and chlorination. Statistical dependence of trihalomethane production on soluble COD, suspended solids and chloramine levels was evident from multiple linear regression calculations.     

Aqueous chlorination of the antibacterial agent trimethoprim: reaction kinetics and pathways

Trimethoprim (TMP), one of the antibacterials most frequently detected in municipal wastewaters and surface waters, reacts readily with free available chlorine (i.e., HOCl) at pH values between 3 and 9 (e.g., the pH-dependent apparent second-order rate constant, k'(app)=5.6 x 10(1)M(-1)s(-1), at pH 7). Solution pH significantly affects the rate of TMP reaction with HOCl. The reaction kinetics in reagent water systems can be well described by a second-order kinetic model incorporating speciation of both reactants and accounting for acid-mediated halogenation of TMP's 3,4,5-trimethoxybenzyl moiety. Studies with the substructure model compounds 2,4-diamino-5-methylpyrimidine and 3,4,5-trimethoxytoluene show that TMP reacts with HOCl primarily via its 3,4,5-trimethoxybenzyl moiety at acidic pH, and with its 2,4-diaminopyrimidinyl moiety at circumneutral and alkaline pH. LC/MS product analyses indicate that the TMP structure is not substantially degraded upon reactions with HOCl. Instead, a wide variety of (multi)chlorinated and hydroxylated products are formed. Experiments with real drinking water and wastewater matrixes confirmed that substantial TMP transformation can be expected for conditions typical of wastewater and drinking water chlorination.     

Using anion exchange resins to remove THM precursors

This study investigated the control of trihalomethanes (THMs) with ion exchange by comparing the THM formation potentials of the organic fractions in the influent to three column systems. The results showed that the smallest organic fraction, <0.5 K apparent molecular weight (AMW), was most reactive with free available chlorine. With the ion exchange system, the 1--5K-, 0.5K--1K-, and < 0.5-AMW organic fractions produced the majority of THMs, whereas with the granular activated carbon (GAC) and the combined ion exchange-GAC systems, the <0.5-AMW fraction produced most of the THMs. The authors conclude that regeneration of the resin of the ion exchange column at sulfate breakthrough, in combination with a GAC column, will produce a water very low in THM formation potential.     

Model studies in aqueous chlorination: The chlorination of phenols in dilute aqueous solutions

A study of the chlorination of four phenols in dilute aqueous solution at initial pH's of 6.0 and 3.5 is described. Extensive chlorination is observed under these mild reaction conditions. Identification of the products indicates that the reactions occurring involve chlorination to more highly chlorinated phenols, oxidation to chlorinated p-benzoquinones, chlorine addition to the aromatic ring to form chlorinated 2,5-cyclohexadienones, and addition of 2 moles of chlorine or one each of chlorine and hypochlorous acid to give chlorinated cyclohexenones and chlorinated hydroxycyclohexenones.     

Electrochemical oxidation of phenolic wastes with boron-doped diamond anodes

The electrochemical oxidation of several phenolic aqueous wastes has been studied using a bench-scale plant with a single-compartment electrochemical flow cell. Boron-doped diamond materials were used as the anode. Complete mineralization of the waste was obtained in the treatment of phenols not substituted with chlorine or nitrogen. Chlorinated phenolic compounds were transformed into carbon dioxide; volatile organochlorinated compounds and nitro-substituted phenols deal with the formation of polymeric materials. These polymeric materials behave as final products or treatment intermediates depending on the nature of the initial pollutant. The removal of nitro- or the chloro-group from the phenolic molecule seems to be one of the first stages in the treatment. Non-nitrogenated or chlorinated carboxylic acids have been found to be the main intermediates in the electrochemical oxidation of all the phenolic compounds tested. The efficiencies of the process depend strongly on the concentration of organic pollutants and on their nature, and not on the current density, at least in the operation range studied.     

The reactions of chlorine dioxide with aquatic organic materials and their health effects

This review describes the main reactions that have been studied in water between chlorine dioxide and various groups of organic compounds. Although the reactions of ClO₂ with some model organic compounds have also been summarised, special emphasis has been given to the reaction products that were found in actual water plants treated with ClO₂ or under conditions closely related to these.Some conclusions were drawn with respect to the mechanism by which ClO₂ reacts with aquatic organic materials. As a result of the proposed reaction mechanisms a prediction was made as to which main organic products will be formed and which health effects may be expected.The last section of the review deals with the impact of ClO₂ on some kinds of organic micropollutants, such as pesticides and polycyclic aromatic hydrocarbons (PAH) which are often found in surface water sources and thus may also be found in drinking water.     

Chlorine photolysis and subsequent OH radical production during UV treatment of chlorinated water

The photodegradation of chlorine-based disinfectants NH(2)Cl, HOCl, and OCl(-) under UV irradiation from low- (LP) and medium-pressure (MP) Hg lamps was studied. The quantum yields of aqueous chlorine and chloramine under 254nm (LP UV) irradiation were greater than 1.2molEs(-1) for free chlorine in the pH range of 4-10 and 0.4molEs(-1) for monochloramine at pH 9. Quantum yields for MP (200-350nm) ranged from 1.2 to 1.7molEs(-1) at neutral and basic pH to 3.7molEs(-1) at pH 4 for free chlorine, and 0.8molEs(-1) for monochloramine. Degradation of free chlorine was enhanced under acidic water conditions, but water quality negatively impacted the MP Hg lamp degradation of free chlorine, compared to the LP UV source. The production of hydroxyl radical via chlorine photolysis was assessed along with the rate of reaction between ()OH and HOCl using radical scavengers (parachlorobenzoic acid and nitrobenzene) in chlorinated solutions at pH 4. The quantum yield of OH radical production from HOCl at 254nm was found to be 1.4molEs(-1), while the reaction of HOCl with OH radical was measured as 8.5x10(4)M(-1)s(-1). NH(2)Cl was relatively stable in all irradiated solutions, with <0.3mgL(-1) increase in nitrate following a UV dose of 1000mJcm(-2). For water treatment plants, no significant changes in chlorine concentration would be expected under typical pH levels and UV doses; however, the formation of ()OH could have implications for chlorinated byproducts or decay of unwanted chemical contaminants.     

Chlorination of model drinking water biofilm: implications for growth and organic carbon removal

The influence of chlorine on biofilm in low organic carbon environments typical of drinking water or industrial process water was examined by comparing biomass and kinetic parameters for biofilm growth in a chlorinated reactor to those in a non-chlorinated control. Mixed-population heterotrophic biofilms were developed in rotating annular reactors under low concentration, carbon-limited conditions (< 2 mg/L as carbon) using three substrate groups (amino acids, carbohydrates and humic substances). Reactors were operated in parallel under identical conditions with the exception that chlorine was added to one reactor at a dose sufficient to maintain a free chlorine residual of 0.09-0.15 mg/L in the effluent. The presence of free chlorine resulted in development of less biofilm biomass compared to the control for all substrates investigated. However, specific growth and organic carbon removal rates were on the average five times greater for chlorinated biofilm compared to the control. Observed yield values were less for chlorinated biofilm. Although chlorinated biofilm's specific organic carbon removal rate was high, the low observed yield indicated organic carbon was being utilized for purposes other than creating new cell biomass. The impacts of free chlorine on mixed-population biofilms in low-nutrient environments were different depending upon the available substrate. Biofilms grown using amino acids exhibited the least difference between control and chlorinated kinetic parameters; biofilm grown using carbohydrates had the greatest differences. These findings are particularly relevant to the fundamental kinetic parameters used in models of biofilm growth in piping systems that distribute chlorinated, low-carbon-concentration water.     

Persistent chemicals in pulp mill effluents: Occurrence and behaviour in an activated sludge treatment plant

In wastewater effluents of a Swiss pulp mill more than 50 organic chemicals were identified including chlorinated phenols, chloroform, chlorinated terpenoids and chlorinated resin acids. Quantitative determinations were carried out to investigate the behaviour of the most abundant constituents during wastewater treatment in an activated sludge process. In particular, the chlorinated compounds were only partly eliminated. The lipophilic chlorinated phenols were physically absorbed to some extent into the activated sludge biomass. The importance of this nonbiological elimination mechanism was evaluated by applying distribution coefficients between activated sludge particles and water which were determined for a series of chlorinated phenols. Chloroform and other purgeable compounds were removed mainly by transfer into the ambient air. The impact of the persistent wastewater constituents on the water quality in the receiving River Aare was assessed. It was estimated that the concentrations of chlorinated phenols in the river caused by the discharge of the treated pulp mill wastewater are about 10 times lower than the levels of pentachlorophenol which typically occur in Swiss rivers receiving effluents from municipal wastewater treatment plants.     

Mineralization of organic matter and other chemical effects of chlorination

Selected river waters, estuarine waters and effluents from wastewater treatment plants, collected during various seasons, have been treated with 0.14 mM (10 ppm) chlorine in order to determine the reactive components involved in chlorine decay reactions. Mineralization of organic matter, detected by measuring evolved CO₂, was universal and constituted the most significant decay process observed. In most cases, loss of ammonia, primary organic amines and nitrite occurred, but removal of these components was not complete. Nitrate was usually produced, but the increases were small relative to initial concentrations. Ammonia in secondary effluent retards chlorine decay and suppresses carbon mineralization. After a week, renewed microbial growth began in anaerobic river water treated with monochloramine even though residual monochloramine remained. The onset of growth coincided with accelerated decay of the monochloramine residual, suggesting that reducing agents were being produced biologically. The faster decay of residual chlorine in denitrified secondary effluents, with low ammonia, demonstrates an additional environmental benefit of denitrification.     

Cinetiques et mecanismes de la degradation de la creatinine sous l'action de l'hypochloriteKinetics and mechanisms of hypochlorite oxidation of creatinine

An area of substantial interest in current research on chlorination is the formation, stability and nature of chloramines formed by the interaction of chlorine with nitrogen organic compounds of biological origin in natural water or swimming pool water. It is desirable to be able to predict the lifetime of these harmful compounds under various conditions. The research described here constitutes an effort to gather important baseline data regarding the rate of formation of creatinine chloramines, the stabilities of these products and their identities.

Some researchers have studied the effect of the presence of chlorinated creatinine compounds in swimming pool water. Lomas (1967), showed that the presence of urine in water allowed the formation of compounds which reacted with DPD like dichloramine. He reported that the presence of this apparent dichloramine could be due to a chlorine derivative of creatine and creatinine derived from urine. Hamence (1980) confirmed this work and found that urine and particularly creatinine were responsible for the apparent nitrogen trichloride. As a result of this work it was concluded that the DPD-fast titrimetric method of analysis did not determine nitrogen trichloride but other chlorine compounds, particularly those of chlorinated creatinine and creatine. We found it interesting to examine in this study, for a range of hypochlorite creatinine ratios and pHs, the kinetics and mechanisms of formation and decomposition of N-chlorocreatinines.

The hypochlorite oxidation of creatinine in aqueous solution has been investigated in the dark. The following of creatinine and chloramines concentrations by the DPD-fast titrimetric method and by their u.v. spectra confirmed Lomas' and Hamence's works. However we observed dichloramine formation (Fig. 4) when the molar ratio of hypochlorite and creatinine was sufficient to decompose all chlorinated creatinine forms. The creatinine determination (HPLC method) suggested that N-chlorocreatinines were formed rapidly at an initial stage. Then they were decomposed by an apparent first order reaction at pH 8. With equimolar (1:1 mmol) amounts of hypochlorite and creatinine at pH 8, it appeared that N-chlorocreatinines were decomposed by hydrolysis to regenerate creatinine. We observed then the formation of creatine, 1-methylhydantoin, chlorocreatinines and NH₂Cl (Fig. 3). When the molar ratio was greater, the N-chlorocreatinines decomposed completely to form carbon dioxide, chlorite ion and mineral chloramines (see Table 1).

The reaction in the initial stage should be considered as an electrophile substitution followed slowly by hydrolysis when pH remained around 8 (Scheme 2). If the addition of hypochlorite affects the amine group of the molecule, 1-methylhydantoin is produced (Scheme 3) with NH₂Cl. Reaction yield was about 10% of initial creatinine.

In acid aqueous solution, with a molar ratio of 3, we also obtained trichlorocreatinine. This reaction is due to the various form of creatinine after addition of proton on amino of N-H groups of the molecule. In these conditions N-chlororcreatinines remained stable in aqueous solution for many days. However in the presence of free chlorine, we observed the production of carbon dioxide and mineral chloramines. After 4 days the residual concentration of N-chlorocreatinines was half the initial value.

It appears that N-chlorocreatinines formed during the chlorination of natural or swimming pool water were relatively stable, leading to the increase of the combined chlorine level. This stability was a function of the molar ratio of hypochlorite and creatinine, and pH. However, since most of the difference types of water had a pH in the range of 6–9, there would be little effect of pH at ambient temperature.     

Formation of N-nitrosodimethylamine (NDMA) from reaction of monochloramine: a new disinfection by-product

Studies have been conducted specifically to investigate the hypothesis that N-nitrosodimethylamine (NDMA) can be produced by reactions involving monochloramine. Experiments were conducted using dimethylamine (DMA) as a model precursor. NDMA was formed from the reaction between DMA and monochloramine indicating that it should be considered a potential disinfection by-product. The formation of NDMA increased with increased monochloramine concentration and showed maximum in yield when DMA was varied at fixed monochloramine concentrations. The mass spectra of the NDMA formed from DMA and 15N isotope labeled monochloramine (15NH2Cl) showed that the source of one of the nitrogen atoms in the nitroso group in NDMA was from monochloramine. Addition of 0.05 and 0.5 mM of preformed monochloramine to a secondarily treated wastewater at pH 7.2 also resulted in the formation of 3.6 and 111 ng/L of NDMA, respectively, showing that this is indeed an environmentally relevant NDMA formation pathway. The proposed NDMA formation mechanism consists of (i) the formation of 1,1-dimethylhydrazine (UDMH) intermediate from the reaction of DMA with monochloramine followed by, (ii) the oxidation of UDMH by monochloramine to NDMA, and (iii) the reversible chlorine transfer reaction between monochloramine and DMA which is parallel to (i). We conclude that reactions involving monochloramine in addition to classical nitrosation reactions are potentially important pathways for NDMA formation.     

Fractionation of dissolved organic matter from surface waters using macroporous resins

To obtain fractions enriched with biodegradable dissolved organic carbon (BDOC) or with organic compounds responsible for the chlorine demand (CID) and for trihalomethane formation potential (THMFP), Seine river water samples were percolated on various macroporous resins (anionic, cationic and non-ionic) and compared with granulated activated carbon (GAC). In addition, measurement of UV absorbance at 254 nm and the fluorescence index (λ_excitation 320 nm) had allowed to follow up the retention of dissolved organic matter by the different adsorbants. In contrast to cationic and non-ionic resins, anionic resins confirm their excellent retention capacity of organic compounds responsible for UV 254 absorbance and fluorescence index. The relative values of BDOC/DOC ratio (mg-C/mg-C) are slightly increased in the effluents of anionic resins, indicating that they retain a little preferentially the refractory fraction instead of the biodegradable fraction. There is no significant difference between the ratio of CID/DOC (mg-Cl₂/mg-C) in influent and effluent of anionic resins. Cationic resin has a low capacity for retention of DOC, but they seem to retain significantly the organic compounds responsible for CID. The capability of anionic resins to retain THMFP is similar to that of GAC.     

Assessment of organic chlorinated compound removal from aqueous matrices by adsorption on activated carbon

Adsorption on activated carbon is currently the most frequently used technology to remove organic chlorinated pollutants from wastewaters. The present study examines the ability of five commercially available types of activated carbon to remove organic chlorinated compounds from the effluent of a chemical plant. The various types were tested on the basis of Freundlich adsorption isotherms for 14 pure organic chlorinated compounds, of molecular weight ranging from that of dichloromethane (MW=84.93 gmol(-1)) to hexachlorobenzene (MW=284.78 gmol(-1)). The best was selected and used in a laboratory fixed-bed column to assess its removal efficiency with respect to the tested organic chlorinated compounds. Removal efficiency was always higher than 90%. These results provide information necessary to optimize scale-up from the pilot plant to the real one.     

Effect of residual chlorine on the analysis of geosmin, 2-MIB and MTBE in drinking water using the SPME technique

The effect of chlorine on the analysis of three organic compounds (geosmin, 2-methylisoborneol (2-MIB) and methyl tert-butyl ether (MTBE)) in drinking water is elucidated. Three fibers for solid-phase microextraction (SPME) were employed for the extraction of the organic compounds from drinking water samples with and without free residual chlorine present. A gas chromatograph coupled with a mass spectrometer was used to analyze the compounds trapped by the fibers. The presence of chlorine substantially reduces the observed geosmin, 2-MIB, and MTBE concentrations. Depending on the analyte and chlorine concentrations, an experimental error of 10-70% may be observed due to the presence of free residual chlorine. The impact is larger for lower organic compound concentrations, and under higher residual chlorine conditions. To counteract the effect from residual chlorine, sodium thiosulfate was used to dechlorinate the water. After dechlorination the experimental error was less than 10%, suggesting that dechlorination is necessary when applying SPME for the extraction of organic compounds from chlorinated drinking water.     

Application of Granular Activated Carbon in the Water Industry

U ntil the mid 1980s granular activated carbon (GAC) was used in only a small number of water-treatment plants in the UK. Since then the material has been installed in over 30 plants, either as a result of an operational decision to treat the water by GAC or for the purpose of full-scale experiments. GAC is used for a variety of reasons including taste and odour control, removal of a wide range of synthetic organic compounds (for example volatile chlorinated solvents, pesticides, oils) of molecular weight 100–500, and adsorption of trihalomethane precursors (molecular weight 10³-10⁵). The performance of different GACs for a particular duty may vary by a factor of 10, and the best GAC for one application may be the worst for another. Thus, to minimize the cost of GAC treatment, it is essential to identify the purpose for which GAC is being used and then to select, by pilot trials or by more rapid laboratory procedures and mathematical modelling, the most appropriate GAC for that particular application.     

Ozonation of water containing chlorine or chloramines. Reaction products and kinetics

Ozone reacts with free aqueous chlorine when present as hypochlorite ion (OCl⁻) with a second order rate constant of 120 ± 15 M⁻¹ s⁻¹ at 20°C. About 77% of the chlorine reacts to produce Cl⁻ and 23% is oxidized to ClO⁻₃. No ClO⁻₄ is formed. Conversion of chlorine to monochloramine reduces the ozone reaction rate to 26 ± 4 M⁻¹ s⁻¹, independent of pH, NH₂Cl is transformed quantitatively to NO⁻₃ and Cl⁻ by O₃. Rate data for other chloramines are also presented. The direct reaction of ozone with chlorine accounts for a significant amount of the chlorine and ozone demand found when the two oxidants are used in combination under water works conditions.