Effects of aluminum sulfate and ferric chloride coagulant residuals on polyamide membrane performance

Pretreatment may constitute up to one-fourth of the total costs of a membrane desalting facility. By using preexisting conventional filtration plants for pretreatment, significant cost savings may be realized. However, coagulant residuals from the pretreatment process may negatively affect reverse osmosis (RO) membrane performance. Various RO membranes were tested at three different treatment plants in southern California, using either aluminum sulfate (alum) or ferric chloride coagulants and chloramines. Repeated testing using alum with multiple RO elements revealed rapid deterioration in specific flux (up to 60% over 100 h of operation), as well as progressive reductions in salt rejection (typically 3-4% over 500 h of operation). Microscopic analysis of the fouled membranes revealed that the foulants were primarily aluminum hydroxide and aluminum silicate materials. In contrast to the RO data for alum coagulation, which showed declining membrane flux, the specific flux data using ferric chloride and chloramines increased over time for all membranes. Salt rejection decreased significantly during testing of each membrane. These data suggest that the RO membranes were physically degrading over time. The RO membranes may have been degraded by residual iron catalyzing a chlorine-amide reaction on the membrane surface, despite the fact that chlorine was present as chloramines.     

Comparison of disinfection byproduct formation from chlorine and alternative disinfectants

Seven diverse natural waters were collected and treated in the laboratory under five oxidation scenarios (chlorine, chloramine, both with and without preozonation, and chlorine dioxide). The impact of these disinfectants on the formation of disinfection byproducts was investigated. Results showed that preozonation decreased the formation of trihalomethanes (THMs), haloacetic acids (HAAs) and total organic halogen (TOX) for most waters during postchlorination. A net increase in THMs, HAAs and TOX was observed for a water of low humic content. Either decreases or increases were observed in dihaloacetic acids and unknown TOX (UTOX) as a result of preozonation when used with chloramination. Chloramines and chlorine dioxide produced a higher percentage of UTOX than free chlorine. They also formed more iodoform and total organic iodine (TOI) than free chlorine in the presence of iodide. Free chlorine produced a much higher level of total organic chlorine (TOCl) and bromine (TOBr) than chloramines and chlorine dioxide in the presence of bromide.     

Evaluation of some halogen biocides using a microbial biofilm system

A simple method for the formation of microbial biofilms of three species, Pseudomonas fluorescens, Pseudomonas aeruginosa, and Klebsiella pneumoniae, on a small glass slide was established, and its suitability for evaluation of disinfectant efficacy was examined. The biofilms formed were observed in situ by confocal laser scanning microscopy (CLSM). Using the biofilms established, biocidal efficacy of several halogen biocides, such as hypochlorite (HOCl), bromochlorodimethylhydantoin (Br, Cl-DMH), ammonia monochloramine (NH2Cl), a stabilized hypobromite biocide named STABREX, and a mixed solution of NH4Br and HOCl, was evaluated. The formation of NHBrCl in the mixed solution was indicated by UV spectra analysis. Biofilm cells were more resistant to these biocides than planktonic cells and the extent of resistance varied with the biocide tested. Among the biocides tested, the biocidal potency of HOCl was the most susceptible to the change brought about by biofilm formation. By CLSM observation, differences in biofilm conformation were revealed between the microbial species. The efficacy of the biocide tested varied with the structure of biofilms formed. The assay method developed in the present study would be useful for further investigation on biofilm disinfection.     

Disinfection efficacy of organic chloramines

The disinfection efficacies of model organic chloramines were investigated. Twenty amino acids and two nucleic acid bases were chlorinated separately with sodium hypochlorite at a Cl:N molar ratio of 0.4:1, and were then used to treat an E. coli suspension for 60 min. DPD/FAS titration was carried out to obtain the concentration of the chlorinated nitrogenous organic compounds as a function of time. In addition, membrane introduction mass spectrometry (MIMS) was used to quantify inorganic chloramines (mono-, di-, and trichloramine). The results of these experiments showed that the organic chloramines examined in this research had little or no effect on the viability of E. coli. MIMS analyses demonstrated that there was no quantifiable formation of inorganic chloramines when the organic nitrogen compounds were chlorinated.     

Validating sample preservation techniques and holding times for the approved compliance monitoring methods for haloacetic acids under the US EPA's stage 1 D/DBP rule

Haloacetic acids (HAAs), which are formed during the disinfection of drinking waters with chlorine, are regulated by the US Environmental Protection Agency (EPA) under the Stage 1 Disinfectant/Disinfection Byproducts (D/DBP) Rule. Recently, three studies have been reported indicating that low concentrations of HAAs can also be formed during disinfection with chloramines. Methods currently approved for compliance monitoring under the Stage 1 Rule arrest the chlorine-mediated formation of HAAs by adding ammonium chloride, which forms chloramines. Studies were undertaken using an in-process water that favored the formation of HAAs with moderate total organic carbon concentration and high levels of chlorine to investigate the potential formation of HAAs under sample storage conditions. The ammonium chloride-quenched sample did form a small amount of HAAs, but total formation over a period equal to the 14-day sample storage time was less than 2 microg/l, whereas the unquenched samples increased 41 microg/l during the same period. Pour plate studies indicated that chlorinated drinking waters quenched with ammonium chloride are protected from microbial growth, which is an important additional advantage to this preservation scheme. The presence of a combined chlorine residual should prevent microbial degradation of HAAs in samples. These studies support the preservation protocols and the sample storage times promulgated for compliance monitoring under the Stage 1 D/DBP Rule.     

Kinetics and products of the Reactions of Ozone with Various forms of Chlorine and Bromine in Water

Ozone reacts with various halogen compounds (chlorine, chloramines , bromine , and bromide) which may be present in water. Chlorine produces Cl^? and ClO^? ₃; chloramines produce NO^? ₃ and Cl^?. Bromide produces bromine , which acts as a secondary disinfectant, but can generate haloforms and interfere in O₃ determinations. Brominepartly regenerates Br causing a catalytic destruction of O₃. The kinetics of these reactions are described and interpreted with respect to their importance in water treatment.     

Impact of halogen based disinfectants in seawater on polyamide RO membranes

The effect of halogen based disinfectants including monochloramines (NH₂Cl), free chlorine (HOCl/OCl⁻), and free oxidants (mixture of HOCl/OCl⁻ and HOBr/OBr) on polyamide membrane was studied in synthetic Ocean seawater. Formation and stability of these oxidants were also examined. Permeability and salt rejection of flat sheet polyamide RO membranes following exposure to the halogen based oxidants were compared to the baseline performance of unexposed membranes. The ratio between free chlorine and free bromine was found to depend on the ratio between the bromides, naturally found in seawater, and the added chlorine. Bromide enhanced the degradation of monochloramines but did not affect the stability of free chlorine. All the oxidants damaged the polyamide membranes studied while the free oxidants appeared to be the most aggressive.     

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.     

Nitrification and potential control mechanisms in simulated premises plumbing

Indigenous drinking water organisms were used to establish nitrification in glass reactors containing copper or polyvinyl chloride (PVC) surfaces. The reactors were fed soil-derived humics as the organic carbon source and ammonium sulfate as the nitrogen source in biologically treated tap water. Water in the reactors was stagnant for 8 h and then flowed for 5 min to simulate conditions in household plumbing. Following the establishment of complete nitrification (conversion of ammonia to nitrate) in both reactor types, various inhibitors of nitrification were tested followed by a period where recovery of nitrification was observed. In one PVC reactor, copper was gradually introduced up to 1.3 ppm. To ensure that most of the copper was in the ionic form, the pH of the influent was then gradually lowered to 6.6. No significant change in nitrification was observed in the presence of copper. Chlorite was introduced into copper and PVC reactors at doses increasing from 0.2 ppm to 20 ppm. There was limited effect on the PVC system and inhibition in the copper reactor only at 20 ppm. Chloramine was tested at chlorine to ammonia ratios ranging from 0.5:1 to 5:1. Nitrification activity was impacted significantly at a 5:1 ratio and ultimately stopped, with the fastest response being in the copper system. Whenever a control mechanism was tested, there was increased release of copper from the reactors with copper coupons. In all cases, nitrification recovered when inhibitors were removed but the rates of recovery differed depending on the treatment method and coupon surface.