Chlorinated phenolics of bleached kraft mill origin : An olfactory evaluation

Biologically treated effluent samples from 9 Canadian bleached softwood kraft mills were analyzed for chlorinated phenolics content. Odour thresholds were determined for selected chlorinated phenolics and for a synthetic mixture of these compounds at concentrations typical of a biologically-treated bleached kraft mill effluent. Results indicate that chlorinated phenolics present in effluent discharged from bleached kraft mills are not expected to contribute an off-odour to recipient waters.     

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.     

An evaluation of the potential toxicity of treated bleached kraft mill effluent to striped bass (Morone saxatilis walbaum) larvae exposed through metamorphosis to the juvenile stage

Twenty-day-old striped bass (Morone saxatilis) larvae were exposed to a range of treated bleached kraft mill effluent (BKME) concentrations from 0 to 20% effluent by volume (v/v) under continuous flow test conditins. The experimental test concentrations in the 2–20% BKME test aquaria had a BOD₅ which ranged from < 1 to 5 mg l⁻¹, TSS 12–17 mg l⁻¹, and true color 35–416 mg l⁻¹. Bleached kraft mill effluent did not kill larvae exposed to it for 20 days through metamorphosis to the juvenile stage. The BKME did not alter growth in length, weight or condition factor in larvae over the 20-day exposure period as determined by multiple regression analysis. A linear regression analysis on the dry weight data at Day 20 only, however, indicated a trend of decreasing weight with increasing BKME concentration. Effluent-exposed larvae also developed normally during the 20-day study. All individuals examined completed the transformation from postlarvae to juveniles by the age of 40 days.     

Fate of wood extractives in wastewater treatment plants at kraft pulp mills and mechanical pulp mills

Extensive environmental effects of the forest industry led to implementation of activated sludge treatment of effluents in the 1980s. Although the existence of chlorinated compounds in the effluents has decreased, a discussion about the possible environmental effects of elemental-chlorine-free (ECF) and total-chlorine-free (TCF) bleached pulp mill effluents has arisen, and chronic effects on aquatic organisms have still been found. Recently, studies have mainly focussed on wood extractives and their role in the effects of effluents. Resin acids and unsaturated fatty acids are found to be toxic, and plant sterols are reported to have adverse endocrine effects on water organisms already at low concentrations. In this study, Finnish wastewater treatment plants of an ECF kraft pulp mill, a paper mill, and an integrated TCF kraft pulp and paper mill were sampled in order to ascertain how wastewater treatment plants, and especially activated sludge treatments, remove wood extractives. Concentrations of extractives in discharged wastewaters varied between 0.4 and 11 g/t kraft or mechanical pulp, and the concentrations decreased over 95% during the treatment processes. Of the wood extractives, 1.1-64% were adsorbed to biosludge and 35-99% were degraded or transformed to other forms during the activated sludge treatment. A major part of these compounds were discharged in particles (74-99%). The removal of extractives was efficient even in the effluent treatment plant, which was highly loaded during the sampling period.     

Reactions of tetracycline antibiotics with chlorine dioxide and free chlorine

Tetracyclines (TCs) are a group of widely used antibiotics that have been frequently found in the aquatic environment. The potential reactions of TCs with common water disinfection oxidants such as chlorine dioxide (ClO₂) and free available chlorine (FAC) have not been studied in depth and are the focus of this study. The oxidation kinetics of tetracycline, oxytetracycline, chlorotetracycline and iso-chlorotetracycline by ClO₂ and FAC are very rapid (with large apparent second-order rate constants k_app = 2.24 × 10⁵-1.26 × 10⁶ M⁻¹ s⁻¹ with ClO₂ and k_app = 1.12 × 10⁴-1.78 × 10⁶ M⁻¹ s⁻¹ with FAC at pH 7.0) and highly dependent on pH. Species-specific rate constants are obtained by kinetic modeling that incorporates pH-speciation of TCs and the oxidants (for FAC), and reveal that TCs primarily react with ClO₂ and FAC by their unprotonated dimethylamino group and deprotonated phenolic-diketone group. The modest difference in reactivity among the four TCs toward the oxidants is consistent with expectation and can be explained by structural influences on the two reactive moieties. Product evaluation shows that oxidation of TCs by ClO₂ leads to (hydr)oxylation and breakage of TC molecules, while oxidation of TCs by FAC leads to chlorinated and (hydr)oxylated products without any substantial ring breakage. Results of this study indicate that rapid transformation of TCs by oxidants such as ClO₂ and FAC under water and wastewater treatment conditions can be expected.     

Disruption of precopulatory behavior in the amphipod Anisogammarus pugettensis upon exposure to bleached kraft pulpmill effluent

Marine amphipods in precopula, Anisogammarus pugettensis (Dana), were used in static 117 h bioassays with neutralized, filtered, bleached kraft pulp mill effluent (BKME) and daily solution replacement. The effluent interfered with precopula behavior; high concentrations (40% of full strength BKME) resulted in rapid release of paired amphipods. A concentration-related time to 50% release of paired individuals was observed. For one batch of BKME, the behavioral threshold concentration (EC₅₀) was estimated at 10–15% of full strength BKME. The estimated 96 h LC₅₀ for underyearling coho salmon (Oncorhynchus kisutch) for the same effluent tested in freshwater was 36% BKME—illustrating a greater sensitivity of the amphipod behavioral bioassay in comparison to the salmonid acute lethal toxicity test. The amphipod precopula bioassay for toxicity testing has some merit in that it is moderately quantitative under given test conditions and does not require elaborate equipment.     

Effects of lignin and chlorolignin in pulp mill effluents on the binding and bioavailability of hydrophobic organic pollutants

The partition coefficients (K_p) of benzo(a)pyrene (BaP), 3,3′,4,4′-tetrachlorobiphenyl (TCB) and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) to dissolved kraft lignin (Indulin AT), chlorolignin isolated from a bleached kraft mill effluent (BKME) and dissolved organic matter (DOM) in a lake receiving BKME were measured by equilibrium dialysis. The K_p values of kraft lignin were 28.2 × 10⁵, 6.5 × 10⁵ and 15.9 × 10⁵ and those of chlorolignin were 8.3 × 10⁵, 2.9 × 10⁵ and 2.2 × 10⁵ for BaP, TCB and TCDD, respectively. In addition, DOM in a series of lake water samples collected from the southern part of Lake Saimaa, SE Finland, receiving BKME revealed higher binding capacities to all of the three model compounds than natural DOM in water upstream from the pulp mill. An important phenomenon related to the environmental transport and fate of xenobiotics was almost the full reversibility of the binding between chlorolignin and model compounds. The obtained K_p values of chlorolignin after a 4 day dissociation period were 12.6 × 10⁵ and 4.6 × 10⁵ for BaP and TCDD, respectively.In short-term (24 h) accumulation experiments with Daphnia magna the effects of kraft lignin and chlorolignin on the bioavailability of three model compounds was very clear. The bioconcentration factors of the xenobiotics in the chlorolignin containing water (DOC = 10 mg C/l) were 20–30 and 25–35% of those organic-free control and upstream reference waters (DOC = 7.2 mg C/l), respectively. The effect of chlorolignin of BKME on the bioavailability of model compounds was also seen in the lake water series of Lake Saimaa.     

Assessing the efficacy of pre-harvest,chlorine-based sanitizers against human pathogen indicator microorganisms and Phytophthora capsici in non-recycled surface irrigation water

Many factors must be considered in order to develop and implement treatment systems to improve the microbial quality of surface water and prevent the accidental introduction of plant and human pathogens into vegetable crops. The efficacy of chlorine gas (Cl_2(g)) and chlorine dioxide (ClO₂) injection systems in combination with rapid sand filtration (RSF) was evaluated in killing fecal indicator microorganisms in irrigation water in a vegetable-intensive production area. The efficacy of ClO₂ and Cl_2(g) was variable throughout the distribution systems and coliform bacteria never dropped below levels required by the United States Environmental Protection Agency for recreational waters. Sampling date and sampling point had a significant effect on the abundance of coliforms in Cl_2(g)- and ClO₂-treated water. Sampling date and sampling point also had a significant effect on the abundance of generic Escherichia coli in Cl_2(g) treated water but only sampling point was significant in ClO₂ treated water. Although the waterborne plant pathogen Phytophthora capsici was detected in five different sources of surface irrigation water using baiting and P. capsici-specific PCR, in vitro studies indicated that ClO₂ at concentrations similar to those used to treat irrigation water did not reduce mycelial growth or direct germination of P. capsici sporangia and reduced zoospore populations by less than 50%. This study concludes that injection of ClO₂ and Cl_2(g) into surface water prior to rapid sand filtration is inadequate in reducing fecal indicator microorganism populations and ClO₂ ineffectively kills infectious propagules of P. capsici. Additional research is needed to design a system that effectively targets and significantly reduces both plant and human pathogens that are present in surface irrigation water. A model for a multiple barrier approach to treating surface water for irrigation is proposed.     

Biological treatment of the effluent from a bleached kraft pulp mill using basidiomycete and zygomycete fungi

Three white-rot fungi (Pleurotus sajor caju, Trametes versicolor and Phanerochaete chrysosporium) and one soft-rot fungi (Rhizopus oryzae) species confirmed their potential for future applications in the biological treatment of effluents derived from the secondary treatment of a bleached kraft pulp mill processing Eucalyptus globulus. Among the four species P. sajor caju and R. oryzae were the most effective in the biodegradation of organic compounds present in the effluent, being responsible for the reduction of relative absorbance (25-46% at 250 nm and 72-74% at 465 nm) and of chemical oxygen demand levels (74 to 81%) after 10 days of incubation. Laccase (Lac), lignin (Lip) and manganese peroxidases (MnP) expression varied among fungal species, where Lac and LiP activities were correlated with the degradation of organic compounds in the effluent treated with P. sajor caju. The first two axes of a principal component analysis explained 88.9% of the total variation among sub-samples treated with the four fungus species, after different incubation periods. All the variables measured contributed positively to the first component except for the MnP enzyme activity which was the only variable contributing negatively to the first component. Absorbances at 465 nm, LiP and Lac enzyme activities were the variables with more weight on the second component. P. sajor caju revealed to be the only species able to perform the biological treatment without promoting an increment in the toxicity of the effluent to the Vibrio fischeri, as it was assessed by the Microtox® assay. The opposite was recorded for the treatments with the other three species of fungus. EC_50-5 min values ranging between 28 and 57% (effluent concentrations) were recorded even after 10 to 13 days of treatment with P. chrysosporium, R. oryzae or with T. versicolor.     

The different reaction mechanisms by which chlorine and chlorine dioxide react with polycyclic aromatic hydrocarbons (PAH) in water

The removal of PAH from surface water by disinfectants like chlorine or chlorine dioxide is important where contamination by these compounds is concerned and no other water treatment processes are available. Our particular interest in these reactions arise from the fact that PAH can be used as an excellent model for the investigation of the different mechanisms by which the two oxidants react with aquatic organics. The vast differences between the rates of Cl₂ and ClO₂ reactions with various PAH, as well as the physical and chemical factors influencing those reactions indicate that chlorine reacts with PAH by several possible mechanisms, e.g. addition, substitution and oxidation. Chlorine dioxide on the other hand reacts mainly as a pure oxidant and a one-electron acceptor. As a consequence, chlorine dioxide reacts much more specifically with those PAH that undergo facile oxidation. Therefore, some PAH that react quite easily with Cl₂, do not react at all with ClO₂, while other PAH react with ClO₂ much more rapidly than with Cl₂. The widespread and highly carcinogenic benzo(a)pyrene and benzo(a)anthracene for example react with ClO₂ much faster than with Cl₂.     

Influence of dilution water on the toxicity of kraft pulp and paper mill effluent, including mechanisms of effect

Ten natural freshwater samples differing widely in pH and other characteristics were collected and examined for their influence as dilution waters on the acute lethality (24-h LC50 values) of a sample of bleached kraft whole mill effluent. When bioassays were conducted at the pH of each dilution water, LC50 values varied by 3.5-fold. These differences were largely accounted for by adjustment of the pH of each test solution to a common value (6.5). The remaining minor differences in LC50 values were attributed to the ionizable inorganic constituents of the dilution waters.A separate study examined the effects of test pH and the involvement of aging of solutions prior to bioassays or of pH overshoots during pH adjustment on the toxicity of a second sample of pulp mill effluent: using a single dilution water. The LC50 values obtained for bioassays conducted at pH 9.5 were significantly higher than those for tests performed at pH 6.5. Neither the adjustment of test solutions to pH 9.5 with immediate readjustment to pH 6.5, nor the prior aging of solutions at pH 9.5 or 6.5 with minimal or no aeration for 6 h, altered the differences due to test pH.The pH-toxicity relationship of the resin acid dehydroabietate and a third sample of bleached kraft whole mill effluent was similar throughout the pH range 5.0–10.5, with test solutions least toxic at pH 9.0–9.5. This pH-toxicity relationship for pulpmill effluents and the influence of dilution water pH on effluent toxicity were attributed mainly to the ionization equilibria of the effluents' resin acid constituents.     

The interaction of treated bleached kraft mill effluent and dissolved oxygen concentration on the survival of the developmental stages of the sheepshead minnow (Cyprinodon variegatus)

The interactions of treated bleached kraft mill effluent (BKME) and dissolved oxygen concentration (DO) on the survival of the embryo, fry, juvenile and adult stages of the sheepshead minnow, Cyprinodon variegatus, were studied under continuous-flow 96 h bioassay conditions. Embryo survival was dependent on effluent concentration only and showed no interaction at nominal DO concentrations of 1.0, 3.0 and 5.0 mg l⁻¹. Survival of the fry was related solely to DO concentration with no interaction with BKME concentrations up to 100%. Juvenile sheepshead minnows showed increased sensitivity to BKME at a nominal DO concentration of 1.0 mg l⁻¹. Adult fish were not affected by BKME at any of the DO concentrations tested. This study shows that the acute toxicity of BKME effluent to sheepshead minnows is a function of the developmental stage of the organism and DO concentration in the receiving stream.     

An investigation of the formation of chlorate and perchlorate during electrolysis using Pt/Ti electrodes: The effects of pH and reactive oxygen species and the results of kinetic studies

The characteristics of chlorate (ClO₃⁻) and perchlorate (ClO₄⁻) formation were studied during the electrolysis of water containing chloride ions (Cl⁻). The experiments were performed using an undivided Pt/Ti plate electrode under different pH conditions (pH 3.6, 5.5, 7.2, 8.0 and 9.0). ClO₃⁻ and ClO₄⁻ were formed during electrolysis in proportion to the Cl⁻ concentration. The generation rates of ClO₃⁻ and ClO₄⁻ under acidic conditions (pH 3.6 and 5.5) were lower than in basic pH conditions (pH 7.2, 8.0 and 9.0). However, the pH of the solution did not influence the conversion of ClO₃⁻ to ClO₄⁻. The effects of intermediately formed oxidants on the production of ClO₃⁻ and ClO₄⁻ were observed using sodium thiosulfate (Na₂S₂O₃) as the active chlorine scavenger and tertiary butyl alcohol (t-BuOH) as the hydroxyl radical (OH) scavenger. The results revealed that electrolysis reactions that involved active chlorine contributed dominantly to ClO₃⁻ production. The direct oxidation reaction rate of Cl⁻ to ClO₃⁻ was 13%. The OH species that were intermediately formed during electrolysis were also found to significantly affect ClO₃⁻ and ClO₄⁻ production. The key formation pathways of ClO₃⁻ and ClO₄⁻ were studied using kinetic model development.     

Nanofiltration removal of chlorinated organic compounds from alkaline bleaching effluents in a pulp and paper plant

Three commercial nanofiltration membranes were used for the removal of chlorinated organic compounds from the first alkaline extraction effluent originated from a kraft mill, using eucalyptus wood as raw material. The assays were carried out at the following operating conditions: pressure = 20 bar, TEMPERATURE = 20°C and circulation VELOCITY = 2 m/s. The results show the nanofiltration feasibility. For the three membranes the rejection factors of chlorinated organic compounds are greater than 95% and two of them present permeate fluxes of approx. 42 kg/hm². Several reference solutes with a wide range of molecular weights and functional groups were also permeated. Their results compared with those of mill effluent allow us to conclude that the effluent tannic compounds are not in a fouling form and that the majority of the organochlorinated matter has a molecular weight greater than 500 Da.     

Trihalomethanes formation in water treated with chlorine dioxide

Formation of trihalomethanes (THMs) was investigated in water treated with chlorine dioxide (ClO₂) and/or chlorine (Cl₂) where humic acid (HA) was used as THMs precursors. When ClO₂ was used as the only disinfectant, no THMs were detected in bromide-free water; while only CHBr₃ was formed in water containing bromide ion because ClO₂ could oxide bromide to form hydrobromous acid which subsequently reacted with HA, and the yield CHBr₃ increased with bromide concentration and ClO₂ dosing. When water was treated with ClO₂ combined with Cl₂, only CHCl₃ was formed in the absence of bromide, however, all four species of THMs were formed in the presence of bromide; the THMs formation potential decreased gradually with an increase in the ratio of ClO₂ to Cl₂ because ClO₂ reacted with HA to render them unreactive or unavailable for THMs production. When water (with or without bromide ion) was irradiated by light, the yield of THMs was increased as a function of irradiation time to a maximum, and thereafter decreased markedly; the possible mechanism is that irradiation could activate the THMs precursors in HA, and at the same time destroy the reactivity of ClO₂ or Cl₂. The same results could be collected from natural water treated by ClO₂ with or without irradiation.     

The effectiveness of a biological treatment with Rhizopus oryzae and of a photo-Fenton oxidation in the mitigation of toxicity of a bleached kraft pulp mill effluent

Huge efforts have been made both in adopting more environmental-friendly bleaching processes, and in developing advanced oxidation processes and more effective biological treatments for the reduction of deleterious impacts of paper mill effluents. Even so, the success of such treatments is frequently reported in terms of chemical parameters without a proper evaluation of the effluent's toxicity mitigation. This is the first study reporting an exhaustive evaluation of the toxicity of a secondary bleached kraft pulp mill effluent, after either tertiary treatment with the soft-rot fungi Rhizopus oryzae or with a photo-Fenton oxidation, using a battery of freshwater species. As it has been reported the photo-Fenton/UV treatment has proved to be the most effective in reducing the colour and the COD (chemical oxygen demand) of the effluent. Nevertheless, extremely low EC₅₀ values were reported for almost all species, after this tertiary treatment. The treatment with R. oryzae was less effective in terms of colour removal and COD reduction, but proved to be the most promising in reducing toxicity.     

Photodecomposition du bioxyde de chlore et des ions chlorite par irradiation u.v. en milieu aqueux-partie II. Etude cinetique

The decomposition of ClO₂ and ClO₂⁻ by u.v. radiation leads to the production of chlorate, chloride and oxygen as end-products via complex reactions which are initiated by the products generated by the primary reactions of photolysis (Buxton and Subhani, 1972a; Mialocq et al., 1973; Karpel Vel Leitner et al., 1992). As far as the rate of decomposition is concerned, Bowen and Cheung (1932) and Zika et al. (1985) have shown that the quantum yield of photodecomposition of chlorine dioxide (overall reaction) increases when the wavelength decreases [Zika et al. (1985): φ = 0.46 at 366 nm and 1.4 at 296.7 nm]. However, the values of the quantum yield of photodecomposition of ClO₂ and ClO₂⁻ at 253.7 nm as well as the quantum yields for the primary reactions of photolysis of ClO₂ and ClO₂⁻ at different wavelengths are not given in the literature.The aim of this work was to study the kinetics of photodecomposition of chlorine dioxide and of chlorite by u.v. irradiation.     

Avoidance of bleached kraft mill effluent by pre-exposed Coregonus albula L.

The ability of vendace (Coregonus albula L.) to avoid different concentrations of bleached kraft mill effluent (BKME) was studied in the laboratory with fish pre-exposed to BKME for 1 week and non-pre-exposed fish. Pre-exposure to BKME in sublethal concentrations reduced the avoidance of BKME by vendace. Throughout the range of exposure concentrations (0.13–4.50 v/v%), pre-exposed fish tended to be observed less in the clean water than non-pre-exposed fish or even to prefer contaminated water. In field conditions, changes in behaviour might lead to a chain reaction: the fish come into contact with concentrations of BKME lower than the threshold level for avoidance and their threshold level increases gradually due to this exposure, which makes exposure to higher concentrations possible and weakens the ability to return to clean water. Desensitization caused by pre-exposure and long distances between pronounced BKME concentration differences in the field together makes it improbable that the vendace can show avoidance responses in the field. Analyses of the various waste-water samples support the conclusion that the most toxic components in BKME, resin acids and chlorophenols, are of minor importance to the avoidance reaction.     

Effectiveness of different oxidizing agents for removing sodium dodecylbenzenesulphonate in aqueous systems

The present study investigates the efficacy of various oxidizing treatments (ClO⁻, ClO₂, KMnO₄, O₃, O₃/H₂O₂, O₃/activated carbon) to remove from waters sodium dodecylbenzenesulphonate (SDBS), considered as model surfactant. Results obtained show that the use of ClO⁻ and ClO₂ does not cause appreciable SDBS degradation. Additionally, in the case of ClO⁻, trihalomethanes are generated, increasing system toxicity. Because the reaction kinetics between SDBS and KMnO₄ is very slow, a decrease in contaminant concentration is not observed, even at very acid pH values. SDBS reactivity with ozone is very low, with a kinetic constant (kO3) of 3.68 M⁻¹ s⁻¹, but its reactivity with HO radicals is very high (k_OH = 1.16 × 10¹⁰ M⁻¹ s⁻¹), therefore O₃/H₂O₂ and O₃/activated carbon, which can also generate HO, appear as promising advanced oxidation processes to remove this contaminant from waters. The method based on ozone and activated carbon was the only process studied that produced both an increase in SDBS removal rate (due to the generation of HO radicals in the O₃-PAC or O₃-GAC interaction) and a considerable reduction in the concentration of dissolved organic carbon in the system due to the PAC adsorbent properties.     

Effects of UV 254 irradiation on residual chlorine and DBPs in chlorination of model organic-N precursors in swimming pools

Ultraviolet (UV) irradiation is commonly applied as a secondary disinfection process in chlorinated pools. UV-based systems have been reported to yield improvements in swimming pool water and air chemistry, but to date these observations have been largely anecdotal. The objectives of this investigation were to evaluate the effects of UV irradiation on chlorination of important organic-N precursors in swimming pools.Creatinine, L-arginine, L-histidine, glycine, and urea, which comprise the majority of the organic-N in human sweat and urine, were selected as precursors for use in conducting batch experiments to examine the time-course behavior of several DBPs and residual chlorine, with and without UV₂₅₄ irradiation. In addition, water samples from two natatoria were subjected to monochromatic UV irradiation at wavelengths of 222 nm and 254 nm to evaluate changes of liquid-phase chemistry. UV₂₅₄ irradiation promoted formation and/or decay of several chlorinated N-DBPs and also increased the rate of free chlorine consumption. UV exposure resulted in loss of inorganic chloramines (e.g., NCl₃) from solution. Dichloromethylamine (CH₃NCl₂) formation from creatinine was promoted by UV exposure, when free chlorine was present in solution; however, when free chlorine was depleted, CH₃NCl₂ photodecay was observed. Dichoroacetonitrile (CNCHCl₂) formation (from L-histidine and L-arginine) was promoted by UV₂₅₄ irradiation, as long as free chlorine was present in solution. Likewise, UV exposure was observed to amplify cyanogen chloride (CNCl) formation from chlorination of L-histidine, L-arginine, and glycine, up to the point of free chlorine depletion. The results from experiments involving UV irradiation of chlorinated swimming pool water were qualitatively consistent with the results of model experiments involving UV/chlorination of precursors in terms of the behavior of residual chlorine and DBPs measured in this study.The results indicate that UV₂₅₄ irradiation promotes several reactions that are involved in the formation and/or destruction of chlorinated N-DBPs in pool settings. Enhancement of DBP formation was consistent with a mechanism whereby a rate-limiting step in DBP formation was promoted by UV exposure. Promotion of these reactions also resulted in increases of free chlorine consumption rates.