Investigating the chlorination of acidic pharmaceuticals and by-product formation aided by an experimental design methodology

The degradation of seven acidic drugs and two metabolites during chlorination was investigated by liquid chromatography-mass spectrometry (LC-MS). A triple-quadrupole (QqQ) system was used to follow the time course of the pharmaceuticals and by-products, while a quadrupole time-of-flight (Q-TOF) system was also used for the identification of the by-products. Under strong chlorination conditions (10 mg/L Cl₂, 24 h), only four of the target compounds were significantly degraded: salicylic acid, naproxen, diclofenac and indomethacine. The degradation kinetics of these four compounds were investigated at different concentrations of chlorine, bromide and pH by means of a Box-Behnken experimental design. Depending on these factors, measured pseudo-first order half-lives were in the ranges: 23-573 h for salicylic acid, 13-446 min for naproxen, 5-328 min for diclofenac and 0.4-13.4 min for indomethacine. Also, it was observed that chlorine concentration was the overall most significant factor, followed by the bromide concentration (except for indomethacine), resulting in increased degradation kinetics as they are increased. The degradation path of salicylic acid, naproxen and diclofenac consisted of aromatic substitution of one or two hydrogens by chlorine and/or bromide. Moreover, for diclofenac, two other by-products corresponding to a decarboxylation/hydroxylation pathway from the monohalogenated products were also identified. On the other hand, indomethacine degradation did not lead to halogenation products but to oxidation ones. The investigation of these by-products in real samples by LC-MS/MS (QqQ) showed that the halogenated derivates of salicylic acid occurred in all the drinking water and wastewater samples analysed.     

Fate of toxic cyanobacterial cells and disinfection by-products formation after chlorination

Drinking water sources in many regions are subject to proliferation of toxic cyanobacteria (CB). Chlorination of source water containing toxic cyanobacterial cells for diverse treatment purposes might cause cell damage, toxin release and disinfection by-products (DBP) formation. There is limited information available on chlorination of different toxic CB cells and DBP formation potentials. This work: (1) determines the extent of lysis and toxins/taste and odor compound release in chlorinated natural water from CB cells (Anabaena circinalis, Microcystis aeruginosa, Cylindrospermopsis raciborskii, and Aphanizomenon issatsckenka) from laboratory cultures and natural blooms; (2) assesses the rates of oxidation of toxins by free chlorine under environmental conditions; (3) studies the DBP formation associated with the chlorination of CB cell suspensions. With chlorine exposure (CT) value of <4.0 mg min/L >60% cells lost viability causing toxin release. Cell membrane damage occurred faster than oxidation of released toxins. Kinetic analysis of the oxidation of toxins in natural water revealed significant differences in their susceptibility to chlorine, saxitoxins being the easiest to oxidize, followed by cylindrospermopsin and microcystin-LR. Furthermore, concentrations of trihalomethanes and haloacetic acids (<40 μg/L) and N-nitrosodimethylamine (<10 ng/L) as chlorination by-products were lower than the guideline values even at the highest CT value (220 mg min/L). However, the DBP concentrations in environmental bloom conditions with very high cell numbers were over the guideline values.     

Formation of assimilable organic carbon during oxidation of natural waters with ozone, chlorine dioxide, chlorine, permanganate, and ferrate

Five oxidants, ozone, chlorine dioxide, chlorine, permanganate, and ferrate were studied with regard to the formation of assimilable organic carbon (AOC) and oxalate in absence and presence of cyanobacteria in lake water matrices. Ozone and ferrate formed significant amounts of AOC, i.e. more than 100 μg/L AOC were formed with 4.6 mg/L ozone and ferrate in water with 3.8 mg/L dissolved organic carbon. In the same water samples chlorine dioxide, chlorine, and permanganate produced no or only limited AOC. When cyanobacterial cells (Aphanizomenon gracile) were added to the water, an AOC increase was detected with ozone, permanganate, and ferrate, probably due to cell lysis. This was confirmed by the increase of extracellular geosmin, a substance found in the selected cyanobacterial cells. AOC formation by chlorine and chlorine dioxide was not affected by the presence of the cells. The formation of oxalate upon oxidation was found to be a linear function of the oxidant consumption for all five oxidants. The following molar yields were measured in three different water matrices based on oxidant consumed: 2.4-4.4% for ozone, 1.0-2.8% for chlorine dioxide and chlorine, 1.1-1.2% for ferrate, and 11-16% for permanganate. Furthermore, oxalate was formed in similar concentrations as trihalomethanes during chlorination (yield ∼ 1% based on chlorine consumed). Oxalate formation kinetics and stoichiometry did not correspond to the AOC formation. Therefore, oxalate cannot be used as a surrogate for AOC formation during oxidative water treatment.     

Kinetics of aqueous chlorination of some pharmaceuticals and their elimination from water matrices

Apparent rate constants for the reactions of four selected pharmaceutical compounds (metoprolol, naproxen, amoxicillin, and phenacetin) with chlorine in ultra-pure (UP) water were determined as a function of the pH. It was found that amoxicillin (in the whole pH range 3-12), and naproxen (in the low pH range 2-4) presented high reaction rates, while naproxen (in the pH range 5-9), and phenacetin and metoprolol (in the pH range 2.5-12 for phenacetin, and 3-10 for metoprolol) followed intermediate and slow reaction rates. A mechanism is proposed for the chlorination reaction, which allowed the evaluation of the intrinsic rate constants for the elementary reactions of the ionized and un-ionized species of each selected pharmaceutical with chlorine. An excellent agreement is obtained between experimental and calculated rate constants by this mechanism.The elimination of these substances in several waters (a groundwater, a surface water from a public reservoir, and two effluents from municipal wastewater treatment plants) was also investigated at neutral pH. The efficiency of the chlorination process with respect to the pharmaceuticals elimination and the formation THMs was also established. It is generally observed that the increasing presence of organic and inorganic matter in the water matrices demand more oxidant agent (chlorine), and therefore, less chlorine is available for the oxidation of these compounds. Finally, half-life times and oxidant exposures (CT) required for the removal of 99% of the four pharmaceuticals are also evaluated. These parameters are useful for the establishment of safety chlorine doses in oxidation or disinfection stages of pharmaceuticals in treatment plants.     

Synergistic effect of the sequential use of UV irradiation and chlorine to disinfect reclaimed water

The effectiveness of UV and chlorination, used individually and sequentially, was investigated in killing pathogenic microorganisms and inhibiting the formation of disinfection by-products in two different municipal wastewaters for the source water of reclaimed water, which were from a microfilter (W1) and membrane bioreactor (W2) respectively. Heterotrophic plate count (HPC), total bacteria count (TBC), and total coliform (TC) were selected to evaluate the efficiency of different disinfection processes. UV inactivation of the three bacteria followed first-order kinetics in W1 wastewater, but in W2 wastewater, the UV dose-response curve trailed beyond approximately 10 mJ/cm² UV. The higher number of particles in the W2 might have protected the bacteria against UV damage, as UV light alone was not effective in killing HPC in W2 wastewater with higher turbidity. However, chlorine was more effective in W2 than in W1 for the three bacteria inactivation owing to the greater formation of inorganic and organic chloramines in W1 wastewater. Complete inactivation of HPC in W1 wastewater required a chlorine dose higher than 5.5 mg/L, whereas 4.5 mg/L chlorine gave the equivalent result in W2 wastewater. In contrast, sequential UV and chlorine treatment produced a synergistic effect in both wastewater systems and was the most effective option for complete removal of all three bacteria. UV disinfection lowered the required chlorine dose in W1, but not in W2, because of the higher chlorine consumption in W2 wastewater. However, UV irradiation decreased total trihalomethane formation during chlorination in both wastewaters.     

Investigation of the microbial degradation of phenazone-type drugs and their metabolites by natural biofilms derived from river water using liquid chromatography/tandem mass spectrometry (LC-MS/MS)

The degradation of the pharmaceuticals phenazone and metamizole, two pyrazolone-derivates in widespread use, using biofilms created by natural organisms from the national park Unteres Odertal, Germany, were investigated. An analytical method based on LC-MS/MS was optimised to determine the substances phenazone and methylaminoantipyrine (MAA), the hydrolysis product of metamizole (also known as dipyrone), as well as their metabolites 1,5-dimethyl-1,2-dehydro-3-pyrazolone (DP), acetaminoantipyrine (AAA), formylaminoantipyrine (FAA) and 4-aminoantipyrine (AA). Performance characteristics of the method were evaluated in terms of recovery, standard deviation, coefficient of variation, method detection limits (MDL) and method quantification limits (MQL). Degradation studies of phenazone and MAA were conducted using a laboratory-scale continuous flow biofilm reactor fed with different nutrient media and with variable hydraulic retention times of 24 and 32 h. MAA was degraded rapidly to FAA and AA, while phenazone was not degraded under the prevailing conditions even after 32 h. By operating the bioreactor in batch mode to study the phenazone degradation potential of the biofilm under limiting nutrient conditions, an elimination rate of 85% phenazone was observed, but because of the slow elimination rate and aerobic conditions, the metabolite DP was not detected. In additional batch experiments using bacterial isolates from the natural biofilm to decompose phenazone, some bacterial strains were able to form DP from phenazone in marginal concentrations over the sampling period of eight weeks. Obviously, the microorganisms need a reasonably long time to adapt their metabolisms to enable the removal of phenazone from water samples.     

Tertiary amines enhance reactions of organic contaminants with aqueous chlorine

Through various anthropogenic inputs, tertiary amines can readily contaminate wastewater and drinking water sources and can form chlorammonium species (R₃N⁺-Cl) during aqueous chlorine disinfection. This study investigated the less understood concept that these chlorammonium species can potentially enhance organic contaminant loss and increase disinfection byproduct formation to a greater extent than aqueous chlorine. Tertiary amines’ effectiveness was highly dependent on amine structure as trimethylamine (TMA) and 4-morpholineethanesulfonic acid (MES) enhanced organic contaminant loss, while others (nitrilotriacetic acid (NTA) and creatinine (CRE)) were ineffective. MES addition up to 25 μM led to increased organic contaminant chlorination by up to three orders of magnitude while observing pseudo-first order kinetic behavior and a linear amine dose response. TMA addition up to 0.5 μM accelerated organic contaminant chlorination by almost two orders of magnitude, but occasionally deviated from pseudo-first order kinetics with incomplete organic contaminant degradation and a non-linear amine dose response - a result linked to TMA’s rapid auto-decomposition over time. Byproduct formation was identical with and without amine addition, and thus the chlorination mechanisms are likely similar to aqueous chlorine. Results from this study improve the mechanistic understanding behind tertiary amine-enhanced chlorination.     

Aqueous chlorination of carbamazepine: Kinetic study and transformation product identification

Carbamazepine reactivity and fate during chlorination was investigated in this study. From a kinetic standpoint, a third-order reaction (first-order relative to the CBZ concentration and second-order relative to the free chlorine concentration) was observed at neutral and slightly acidic pH, whereas a second-order reaction (first order relative to the CBZ concentration and first order relative to the free chlorine concentration) was noted under alkaline conditions. In order to gain insight into the observed pH-dependence of the reaction order, elementary reactions (i.e. reactions of Cl₂, Cl₂O, HOCl with CBZ and of ClO⁻ with CBZ or of HOCl with the ionized form of CBZ) were highlighted and second order rate constants of each of them were calculated. Close correlations between the experimental and modeled values were obtained under these conditions. Cl₂ and Cl₂O were the main chlorination agents at neutral and acidic pH. These results indicate that, for a 1 mg/L free chlorine concentration and 1–10 mg/L chloride concentration at pH 7, halflives about 52–69 days can be expected. A low reactivity of chlorine with CBZ could thus occur under the chlorination steps used during water treatment. From a mechanistic viewpoint, several transformation products were observed during carbamazepine chlorination. As previously described for the chlorination of polynuclear aromatic or unsaturated compounds, we proposed monohydroxylated, epoxide, diols or chlorinated alcohol derivatives of CBZ for the chemical structures of these degradation products. Most of these compounds seem to accumulate in solution in the presence of excess chlorine.     

Oxidation of pharmaceuticals during water treatment with chlorine dioxide

The potential of chlorine dioxide (ClO2) for the oxidation of pharmaceuticals during water treatment was assessed by determining second-order rate constants for the reaction with selected environmentally relevant pharmaceuticals. Out of 9 pharmaceuticals only the 4 following compounds showed an appreciable reactivity with ClO2 (in brackets apparent second-order rate constants at pH 7 and T = 20 degrees C): the sulfonamide antibiotic sulfamethoxazole (6.7 x 10(3) M(-1) s(-1)), the macrolide antibiotic roxithromycin (2.2 x 10(2) M(-1) s(-1)), the estrogen 17alpha-ethinylestradiol (approximately 2 x 10(5) M(-1) s(-1)), and the antiphlogistic diclofenac (1.05 x 10(4) M(-1) s(-1)). Experiments performed using natural water showed that ClO2 also reacted fast with other sulfonamides and macrolides, the natural hormones estrone and 17beta-estradiol as well as 3 pyrazolone derivatives (phenazone, propylphenazone, and dimethylaminophenazone). However, many compounds in the study were ClO2 refractive. Experiments with lake water and groundwater that were partly performed at microgram/L to nanogram/L levels proved that the rate constants determined in pure water could be applied to predict the oxidation of pharmaceuticals in natural waters. Compared to ozone, ClO2 reacted more slowly and with fewer compounds. However, it reacted faster with the investigated compounds than chlorine. Overall, the results indicate that ClO2 will only be effective to oxidize certain compound classes such as the investigated classes of sulfonamide and macrolide antibiotics, and estrogens.     

Aqueous chlorination of diclofenac: kinetic study and transformation products identification

Diclofenac reactivity and fate during water chlorination was investigated in this work. In the first step, chlorination kinetic of diclofenac (DCF) was studied in the pH range of 4-10 at 20 ± 2 °C and in the presence of an excess of total chlorine. A second-order reaction (first-order relative to DCF concentration and first-order relative to free chlorine concentration) was shown with rate constant about 3.89 ± 1.17 M⁻¹ s⁻¹ at pH 7. The elementary reactions (i.e. reactions of hypochlorous acid (HOCl) with neutral and ionized forms of DCF, and acid-catalysed reaction of HOCl with neutral and ionized forms of DCF) were proposed to explain the pH-dependence of the rate constants and intrinsic constant of each of them were calculated. In the second step, several degradation products formed during chlorination of DCF were identified. These compounds could come from an initial chlorine electrophilic attack on aromatic ring or amine function of DCF. Some of these chlorinated derivatives seem to accumulate in solution in the presence of an excess of chlorine.     

Occurrence and fate of the antidiabetic drug metformin and its metabolite guanylurea in the environment and during drinking water treatment

Metformin, an antidiabetic drug with one of the highest consumption rates of all pharmaceuticals worldwide, is biologically degraded to guanylurea in wastewater treatment plants. Due to high metformin influent concentrations of up to 100 μg/L and its high but incomplete degradation both compounds are released in considerable amounts of up to several tens of μg/L into recipient rivers. This is the first systematic study on their environmental fate and the effectiveness of treatment techniques applied in waterworks to remove metformin and guanylurea from surface water influenced raw waters. The concentrations in surface waters depend strongly on the respective wastewater burden of rivers and creeks and are typically in the range of about 1 μg/L for metformin and several μg/L for guanylurea but can reach elevated average concentrations of more than 3 and 20 μg/L, respectively. Treatment techniques applied in waterworks were investigated by an extended monitoring program in three facilities and accompanied by laboratory-scale batch tests. Flocculation and activated carbon filtration proved to be ineffective for removal of metformin and guanylurea. During ozonation and chlorination experiments with waterworks-relevant ozone and chlorine doses they were partly transformed to yet unknown compounds. The effectiveness of the treatment steps under investigation can be ordered chlorination > ozonation > activated carbon filtration > flocculation. However, most effective for removal of both compounds at the three full-scale waterworks studied proved to be an underground passage (riverbank filtration or artificial groundwater recharge). A biological degradation is most likely as sorption can be neglected. This is based on laboratory batch tests conducted with three different soil materials according to OECD guideline 106. Since such treatment steps were implemented in all three drinking water treatment plants, even traces of metformin and its metabolite guanylurea could not be detected at the end of the treatment trains. Both can only be expected in finished drinking water if surface influenced raw water is used by direct abstraction without underground passage.     

Evaluation of bromine substitution factors of DBPs during chlorination and chloramination

Bromine substitution factor (BSF) was used to quantify the effects of disinfectant dose, reaction time, pH, and temperature on the bromine substitution of disinfection byproducts (DBPs) during chlorination and chloramination. The BSF is defined as the ratio of the bromine incorporated into a given class of DBPs to the total concentration of chlorine and bromine in that class. Four classes of DBPs were evaluated: trihalomethanes (THMs), dihaloacetonitriles (DHANs), dihaloacetic acids (DHAAs) and trihaloacetic acids (THAAs). The results showed that the BSFs of the four classes of DBPs generally decreased with increasing reaction time and temperature during chlorination at neutral pH. The BSFs peaked at a low chlorine dose (1 mg/L) and decreased when the chlorine dose further increased. The BSFs of chlorination DBPs at neutral pH are in the order of DHAN > THM & DHAA > THAA. DHAAs formed by chloramines exhibited distinctly different bromine substitution patterns compared to chlorination DHAAs. Brominated DBP formation was generally less affected by the pH change compared to chlorinated DBP formation.     

Occurrence and formation potential of N-nitrosodimethylamine in ground water and river water in Tokyo

N-nitrosodimethylamine (NDMA), a disinfection byproduct of water and wastewater treatment processes, is a potent carcinogen. We investigated its occurrence and the potential for its formation by chlorination (NDMA-FP_2Cl) and by chloramination (NDMA-FP_2NHCl) in ground water and river water in Tokyo. To characterize NDMA precursors, we revealed their molecular weight distributions in ground water and river water. We collected 23 ground water and 18 river water samples and analyzed NDMA by liquid chromatography-tandem mass spectrometry. NDMA-FP_2Cl was evaluated by chlorinating water samples with free chlorine for 24 h at pH 7.0 while residual free chlorine was kept at 1.0-2.0 mgCl₂/L. NDMA-FP_2NHCl was evaluated by dosing water samples with monochloramine at 140 mgCl₂/L for 10 days at pH 6.8. NDMA precursors and dissolved organic carbon (DOC) were fractionated by filtration through 30-, 3-, and 0.5 kDa membranes. NDMA concentrations were <0.5-5.2 ng/L (median: 0.9 ng/L) in ground water and <0.5-3.4 ng/L (2.2 ng/L) in river water. NDMA concentrations in ground water were slightly lower than or comparable to those in river water. Concentrations of NDMA-FP_2Cl were not much higher than concentrations of NDMA except in samples containing high concentrations of NH₃ and NDMA precursors. The increased NDMA was possibly caused by reactions between NDMA precursors and monochloramine unintentionally formed by the reaction between free chlorine and NH₃ in the samples. NDMA precursors ranged from 4 to 84 ng-NDMA eq./L in ground water and from 11 to 185 ng-NDMA eq./L in river water. Those in ground water were significantly lower than those in river water, suggesting that NDMA precursors were biodegraded, adsorbed, or volatilized during infiltration. The molecular weight of NDMA precursors in river water was dominant in the <0.5 kDa fraction, followed by 0.5-3 kDa. However, their distribution was inconsistent in ground water: one was dominant in the <0.5 kDa fraction, and the other in 0.5-3 kDa. Molecular weight distributions of NDMA precursors were very different from those of DOC. This is the first study to reveal the widespread occurrence and characterization of NDMA precursors in ground water.     

Characterization and identification of antiestrogenic products of phenylalanine chlorination

Recent studies have reported that chlorination increased the antiestrogenic activity of wastewater, suggesting that disinfection by-products (DBPs) formed during chlorination is a potential and important source of endocrine-disruptor. However, antiestrogenic DBPs have not been identified. In this study, the antiestrogenic activity after aqueous chlorination of phenylalanine solution was evaluated by yeast two-hybrid assay and antiestrogenic DBPs were also identified and characterized. For the first time, aqueous chlorination of phenylalanine was found to form antiestrogenic DBPs when the antiestrogenic activity of chlorinated phenylalanine solution (0.5 mmol L^?1) increased from undetectable to 57 μmol-tamoxifen (TAM) L^?1 with the increase in chlorine doses from 0 to 0.5 mmol-Cl₂ L^?1. This level decreased sharply when chlorine addition went over 0.5 mmol-Cl₂ L^?1. By fractionating DBPs of chlorinated phenylalanine solution into different fractions via semipreparative liquid chromatography, a key fraction with high antiestrogenic activity was discovered and collected. Based on analyses of mass spectrometry (MS) and nuclear magnetic resonance (NMR), the compound involved in this fraction (21 mg) was determined to be 2,4-diphenylcrotonaldehyde, which is newly identified as a relatively high antiestrogenic chemical.     

Formation of disinfection by-products after pre-oxidation with chlorine dioxide or ferrate

The effect of pre-oxidation with chlorine dioxide (ClO₂) or ferrate (Fe(VI)) on the formation of disinfection by-products (DBPs) during chlorination or chloramination was tested with natural waters from 12 sources (9 surface waters, 1 groundwater, and 2 wastewater effluents). DBPs investigated included trihalomethanes (THM), chloral hydrate (CH), haloketones (HK), haloacetonitriles (HAN) and trichloronitromethane (TCNM), chlorite and chlorate. Chlorite and chlorate were found in the ClO₂-treated waters. Application of 1 mg/L ClO₂ ahead of chlorination reduced the formation potential for THM by up to 45% and the formation of HK, HAN and TCNM in most of the samples. The CH formation results were mixed. The formation of CH and HK was enhanced with low doses of Fe(VI) (1 mg/L as Fe), but was greatly reduced at higher doses (20 mg/L Fe). Fe(VI) reduced the formation of THM, HAN and TCNM in most of the samples. Reduced potential for the formation of NDMA was observed in most of the samples after both ClO₂ and Fe(VI) pre-oxidation.     

Chlorination kinetics of glyphosate and its by-products: modeling approach

Chlorination reactions of glyphosate, glycine, and sodium cyanate were conducted in well-agitated reactors to generate experimental kinetic measurements for the simulation of chlorination kinetics under the conditions of industrial water purification plants. The contribution of different by-products to the overall degradation of glyphosate during chlorination has been identified. The kinetic rate constants for the chlorination of glyphosate and its main degradation products were either obtained by calculation according to experimental data or taken from published literature. The fit of the kinetic constants with experimental data allowed us to predict consistently the concentration of the majority of the transitory and terminal chlorination products identified in the course of the glyphosate chlorination process. The simulation results conducted at varying aqueous chlorine/glyphosate molar ratios have shown that glyphosate is expected to degrade in fraction of a second under industrial aqueous chlorination conditions. Glyphosate chlorination products are not stable under the conditions of drinking water chlorination and are degraded to small molecules common to the degradation of amino acids and other naturally occurring substances in raw water. The kinetic studies of the chlorination reaction of glyphosate, together with calculations based on kinetic modeling in conditions close to those at real water treatment plants, confirm the reaction mechanism that we have previously suggested for glyphosate chlorination.     

Formation and fate of chlorination by-products in reverse osmosis desalination systems

Chlorination by-products may be formed during pretreatment or posttreatment disinfection in reverse osmosis (RO) desalination systems, potentially posing health, aesthetic and ecological risks. To assess the formation and fate of by-products under different conditions likely to be encountered in desalination systems, trihalomethanes, dihaloacetonitriles, haloacetic acids, and bromophenols were analyzed in water samples from a pilot-scale seawater desalination plant with a chlorine pretreatment system and in benchscale experiments designed to simulate other feed water conditions. In the pilot plant, RO rejection performance as low as 55% was observed for neutral, low-molecular-weight by-products such as chloroform or bromochloroacetonitrile. Benchscale chlorination experiments, conducted on seawater from various locations indicated significant temporal and spatial variability for all by-products, which could not be explained by measured concentrations of organic carbon or bulk parameters such as SUVA₂₅₄. When desalinated water was blended with freshwater, elevated concentrations of bromide in the blended water resulted in dihaloacetonitrile concentrations that were higher than those expected from dilution. In most situations, the concentration of chlorination by-products formed from continuous chlorination of seawater or blending of desalinated water and freshwater will not compromise water quality or pose significant risks to aquatic ecosystems.     

Identification of reaction products from reactions of free chlorine with the lipid-regulator gemfibrozil

High global consumption rates have led to the occurrence of pharmaceutically active compounds (PhACs) in wastewater. The use of chlorine to disinfect wastewater prior to release into the environment may convert PhACs into uncharacterized chlorinated by-products. In this investigation, chlorination of a common pharmaceutical, the antihyperlipidemic agent gemfibrozil, was documented. Gemfibrozil (2,2-dimethyl-5-(2,5-dimethylphenoxy)pentanoic acid) was reacted with sodium hypochlorite and product formation was monitored by gas chromatography-mass spectrometry (GC-MS). The incorporation of one, two or three chlorine atoms into the aromatic region of gemfibrozil was demonstrated using negative-ion electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS/MS). Further analysis using ¹H nuclear magnetic resonance (NMR) spectroscopy identified the reaction products as 4′-ClGem (5-(4-chloro-2,5-dimethylphenoxy)-2,2-dimethylpentanoic acid) 4′,6′-diClGem (5-(4,6-dichloro-2,5-dimethylphenoxy)-2,2-dimethylpentanoic acid), and 3′,4′,6′-triClGem (5-(3,4,6-trichloro-2,5-dimethylphenoxy)-2,2-dimethylpentanoic acid), products consistent with electrophilic aromatic substitution reactions. The rapid reaction of gemfibrozil with free chlorine at pH conditions relevant to water treatment indicates that a mixture of chlorinated gemfibrozils is likely to be found in wastewater disinfected with chlorine.     

Differences in the chlorine reactivity of four microcystin analogues

The presence of microcystin toxins in drinking water is highly undesirable as they have the potential to adversely affect human health. Consequently, effective removal of these toxins from water is a major goal for water authorities. In this study, four microcystin analogues were chlorinated in two treated waters, and two of the analogues were chlorinated in deionised water. The oxidation of the microcystins was related to the chlorine exposure (CT) of the sample waters with the ease of oxidation following the trend: microcystin-YR > microcystin-RR > microcystin-LR > or = microcystin-LA. This trend was in agreement with published data on model compounds and free amino acids. Values of CT of up to 25 mg min L(-1) were required for oxidation of all microcystin analogues to below the World Health Organization guideline value of 1.0 microg L(-1). Results from this study indicate that for some water resources it is important to determine the speciation of the microcystin analogues to optimise chlorination practices.     

Comparison of chlorination and chloramination practices on microbial inactivation efficiencies within a scaled‐up water distribution network using central composite design

Disinfection practices reduce the incidence of water‐borne diseases but may result in formation of disinfection byproducts (DBPs) in raw water that are reported to be carcinogenic. Central composite design (CCD) was employed in the present study for optimization of disinfectant dose and contact time with the rationale to evaluate if an optimal balance could be achieved between minimal DBPs formation and effective microbial inactivation with either free or combined chlorine in treated water within a lab‐scale prototype network to simulate real water distribution network conditions. After a series of experimental runs based upon design of experiments (DoE) by CCD, dose was found to be the most significant factor (P < 0.01) in determining DBPs formation in both disinfectant’s applications. Where, contact time significantly (P < 0.01) affected bacterial inactivation in chlorination experiments, in contrast, dose was effective in chloramination experiments. Thus, it was concluded that the optimal balance may be achieved in the water networks with the help of multifactorial optimization when disinfectant dose was maintained near 3 mg/L as applied chlorine dose in both disinfection cases, while contact time was 62 and 155 min for chlorine and chloramine, respectively.