Determination of bromate and chlorinated haloacetic acids in bottled drinking water with chromatographic methods

Disinfection by-products of interest such as bromate, chlorate and chlorinated haloacetic acids in 10 representative brands of bottled drinking water were investigated with ion chromatography. With the developed method, the detection limits of the disinfection by-products were in sub-microgl(-1) level. It was observed that bromate, chlorate and dichloroacetic acid could be detected in some water samples. In the bottled natural water, the concentrations for the three compounds were 0.1, 0.9 and 0.6 microgl(-1), respectively. The total concentration of disinfection by-products in the natural water sample was the highest among all the bottled drinking waters. The concentrations for the sum of disinfection by-products in the four types of bottled drinking water investigated were natural water > mineral water > spring water > purified water. The generation of disinfection by-products was much influenced by the original components and process procedure of the source water. The concentrations of bromate and chlorate in the bottled water samples hardly degraded with the increasing storage time. For dichloroacetic acid, with the prolonging of storage time, the concentration was much decreased.     

Adsorptive separation of cadmium from aqueous solutions and wastewaters by riverbed sand

Application of riverbed sand for the adsorptive separation of cadmium(II) from aqueous solutions has been investigated. Removal increased from 26.8 to 56.4% by decreasing the initial concentration of cadmium from 7.5 x 10(-5) to 1.0 x 10(-5)M at pH 6.5, 25 degrees C temperature, agitation speed of 100 rpm, 100 microm particle size and 1.0 x 10(-2) NaClO4 ionic strength. Process of separation is governed by first order rate kinetics. The value of rate constant of adsorption, k(ad), was found to be 2.30 x 10(-2)per min at 25 degrees C. Values of coefficient of mass transfer, beta L, were calculated and its value at 25 degrees C was found to be 1.92 x 10(-2)cm/s. Values of Langmuir constant were calculated. Values of thermodynamic parameters delta G0, delta H0 and delta S0 were also calculated and were recorded as -0.81 kcal/mol, -9.31 kcal/mol and -28.10 cal/mol at 25 degrees C. pH has been found to affect the removal of cadmium significantly and maximum removal, 58.4%, has been found at pH 8.5. Process can be used for treatment of cadmium(II) rich wastewaters.     

Behavior of bromide in the photoelectrocatalytic process and bromine generation using nanoporous titanium dioxide thin-film electrodes

In this study, the photoelectrocatalytic behavior of bromide and generation of bromine using TiO2 was investigated in the separate anode and cathode reaction chambers. Our results show that the generation of bromine begins around a flatband potential of -0.34 V vs. standard calomel electrode (SCE) at pH 3.0 under UV illumination and increases with an increase in positive potential, finally reaching a steady-state concentration at 1.0 V vs. SCE. Maximum bromine formation occurs over the range of pH 4-6, decreasing sharply at conditions where the pH>7.     

Homogeneous degradation of 1,2,9,10-tetrachlorodecane in aqueous solutions using hydrogen peroxide, iron and UV light

The homogeneous degradation of the polychlorinated n-alkane, 1,2,9,10-tetrachlorodecane (T4C10), was studied in aqueous solutions of hydrogen peroxide, including Fenton and photo-Fenton reaction conditions. All solutions were adjusted to a pH of 2.8 and an ionic strength of 0.1 M NaClO4 prior to photolysis. T4C10 (2 x 10(-6) M) was substantially degraded by the H2O2/UV system (1.0 x 10(-2) M H2O2), with 60% disappearance in 20 min of irradiation in a photoreactor equipped with 300 nm lamps of light intensity 3.6 x 10(-5) Ein L(-1) min(-1) (established by ferrioxalate actinometry). The reaction produced stoichiometric amounts of chloride ion indicating complete dechlorination of the chlorinated n-alkane. T4C10 degraded very slowly under Fenton (Fe2+/H2O2/dark) and Fenton-like (Fe3+/H2O2/dark) conditions. However, when the same solutions were irradiated, T4C10 degraded more rapidly than in the H2O2/UV system, with 61% disappearance in 10 min of exposure. The rapid degradation is related to the enhanced degradation of hydrogen peroxide to oxidizing *OH radicals under photo-Fenton conditions. Degradation was inhibited in both the H2O2/UV and photo-Fenton systems by the addition of KI and tert-butyl alcohol due to *OH scavenging.     

Removal of faecal indicator pathogens from waters and wastewaters by photoelectrocatalytic oxidation on TiO2/Ti films under simulated solar radiation

Purpose

The disinfection efficiency of water and secondary treated wastewater by means of photoelectrocatalytic oxidation (PEC) using reference strains of Enterococcus faecalis and Escherichia coli as faecal indicators was evaluated. Operating parameters such as applied potential (2?C10?V), initial bacterial concentration (10³?C10⁷?CFU/mL), treatment time (up to 90?min) and aqueous matrix (pure water and treated effluent) were assessed concerning their impact on disinfection.

Methods

PEC experiments were carried out using a TiO₂/Ti film anode and a zirconium cathode in the presence of simulated solar radiation. Bacterial inactivation was monitored by the culture method and real-time SYBR green PCR.

Results

A 6.2 log reduction in E. faecalis population was achieved after 15?min of PEC treatment in water at 10?V of applied potential and an initial concentration of 10⁷?CFU/mL; pure photocatalysis (PC) led to only about 4.3 log reduction, whilst negligible inactivation was recorded when the respective electrochemical oxidation process was applied (i.e. without radiation). PEC efficiency was generally improved increasing the applied potential and decreasing initial bacterial concentration. Regarding real wastewater, E. coli was more susceptible than E. faecalis during treatment at a potential of 5?V. Wastewater disinfection was affected by its complex composition and the contained mixed bacterial populations, yielding lower inactivation rates compared to water treatment. Screening the results obtained from both applied techniques (culture method and real-time PCR), there was a discrepancy regarding the recorded time periods of total bacterial inactivation, with qPCR revealing longer periods for complete bacterial reduction.

Conclusions

PEC is superior to PC in terms of E. faecalis inactivation presumably due to a more efficient separation and utilization of the photogenerated charge carriers, and it is mainly affected by the applied potential, initial bacterial concentration and the aqueous matrix.     

Kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE)

The kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE) in aqueous solutions at various pH, temperature, oxidant concentration and ionic strength levels was studied. The MTBE degradation was found to follow a pseudo-first-order decay model. The pseudo-first-order rate constants of MTBE degradation by persulfate (31.5 mM) at pH 7.0 and ionic strength 0.11 M are approximately 0.13 x 10(-4), 0.48 x 10(-4), 2.4 x 10(-4) and 5.8 x 10(-4) S(-1) at 20, 30, 40 and 50 degrees C, respectively. Under the above reaction conditions, the reaction has an activation energy of 24.5 +/- 1.6 kcal/ mol and is influenced by temperature, oxidant concentration, pH and ionic strength. Raising the reaction temperature and persulfate concentration may significantly accelerate the MTBE degradation. However, increasing both pH (over the range of 2.5-11) and ionic strength (over the range of 0.11-0.53 M) will decrease the reaction rate. Reaction intermediates including tert-butyl formate, tert-butyl alcohol, acetone and methyl acetate were observed. These intermediate compounds were also degraded by persulfate under the experimental conditions. Additionally, MTBE degradation by persulfate in a groundwater was much slower than in phosphate-buffer solutions, most likely due to the presence of bicarbonate ions (radical scavengers) in the groundwater.     

Kinetic assessment of the potassium ferrate(VI) oxidation of antibacterial drug sulfamethoxazole

Sulfamethoxazole (SMX), a worldwide-applied antibacterial drug, was recently found in surface waters and in secondary wastewater effluents, which may result in ecotoxical effects in the environment. Herein, removal of SMX by environmentally-friendly oxidant, potassium ferrate(VI) (K(2)FeO(4)), is sought by studying the kinetics of the reaction between Fe(VI) and SMX as a function of pH (6.93-9.50) and temperature (15-45 degrees C). The rate law for the oxidation of SMX by Fe(VI) is first-order with respect to each reactant. The observed second-order rate constant decreased non-linearly from 1.33+/-0.08 x 10(3) M(-1)s(-1) to 1.33+/-0.10 x 10(0) M(-1)s(-1) with an increase of pH from 7.00 to 9.50. This is related to protonation of Fe(VI) (HFeO(4)(-) <==> H(+) + FeO(4)(2-); pK(a,HFeO(4)) = 7.23) and sulfamethoxazole (SH <==> H(+) + S(-); pK(a,SH)=5.7). The estimated rate constants were k(11)(HFeO(4)(-) + SH) = 3.0 x 10(4) M(-1)s(-1), k(12)(HFeO(4)(-) + S(-)) = 1.7 x 10(2) M(-1)s(-1), and k(13) (FeO(4)(2-) + SH) = 1.2 x 10(0) M(-1)s(-1). The energy of activation at pH 7.0 was found to be 1.86+/-0.04 kJ mol(-1). If excess potassium ferrate(VI) concentration (10 microM) is used than the SMX in water, the half-life of the reaction using a rate constant obtained in our study would be approximately 2 min at pH 7. The reaction rates are pH dependent; thus, so are the half-lives of the reactions. The results suggest that K(2)FeO(4) has the potential to serve as an oxidative treatment chemical for removing SMX in water.     

Formation of halogenated acetaldehydes, and occurrence in Canadian drinking water

Controlled laboratory chlorination of acetaldehyde (ACD) under typical drinking water conditions (pH 6.7, 7.6 and 8.8, and temperature 4 degrees C and 21 degrees C) revealed that the formation of chloral hydrate (CH), the most common halogenated acetaldehyde (HAs), increased with contact time (0-10 days). However, at increased pH and temperature, CH reached maximum levels and subsequently broke down partially to chloroform and other unidentified compounds. After 10 days contact time, a maximum of 63% (molar) of the initial ACD consumed were converted into CH or chloroform (TCM). Various surveys of drinking water systems indicated that ACD is not the only precursor of CH. A suite of aldehydes (including ACD), and chlorinated disinfection by-products (including TCM and CH) were found in most distribution systems. The levels of bromide in source water impacted speciation of HAs. In addition to CH, brominated and other mixed (Cl/Br) acetaldehydes were detected in most samples; the speciation of HAs and THMs followed comparable trends. Similar to chloroform for trihalomethanes, CH contributed from as low as 5% to up to 60% of the total HAs. The bromine incorporation factors (BIF) in THMs and HAs were shown to increase with increasing bromide ion concentrations in the source water. Brominated THMs are more readily formed than their HA analogues; in fact, BIF values for THMs were 2-3 times higher than for the HAs. It was found that HAs may be as high as THMs in some drinking waters. As a result, the determination of the other target HAs, in addition to CH, is necessary for a better assessment of the pool of disinfection by-products in drinking water.     

Comparison of Fe(VI) (FeO4(2-)) and ozone in inactivating Bacillus subtilis spores

The protozoan parasites such as Cryptosporidiumparvum and Giardialamblia have been recognized as a frequent cause of recent waterborne disease outbreaks because of their strong resistance against chlorine disinfection. In this study, ozone and Fe(VI) (i.e., FeO(4)(2-)) were compared in terms of inactivation efficiency for Bacillus subtilis spores which are commonly utilized as an indicator of protozoan pathogens. Both oxidants highly depended on water pH and temperature in the spore inactivation. Since redox potential of Fe(VI) is almost the same as that of ozone, spore inactivation efficiency of Fe(VI) was expected to be similar with that of ozone. However, it was found that ozone was definitely superior over Fe(VI): at pH 7 and 20°C, ozone with the product of concentration×contact time (CˉT) of 10mgL(-1)min inactivate the spores more than 99.9% within 10min, while Fe(VI) with CˉT of 30mgL(-1) min could inactivate 90% spores. The large difference between ozone and Fe(VI) in spore inactivation was attributed mainly to Fe(III) produced from Fe(VI) decomposition at the spore coat layer which might coagulate spores and make it difficult for free Fe(VI) to attack live spores.     

Hydrogen peroxide-assisted UV photodegradation of Lindane

Aqueous solutions of gamma-hexachlorocyclohexane (Lindane) were photolyzed (lambda=254 nm) under a variety of solution conditions. The initial concentrations of hydrogen peroxide (H(2)O(2)) and Lindane varied from 0 to 20 mM and 0.21 to 0.22 microM, respectively, the pH ranged from 3 to 11, and several concentration ratios of Suwannee River humic acid and fulvic acid were dissolved in the irradiated solutions. Lindane rapidly reacted, and the maximum reaction rate constant (9.7 x 10(-3) s(-1)) was observed at pH 7 and initial [H(2)O(2)]=1 mM. Thus, 90% of the Lindane is destroyed in approximately 4 min under these conditions. In addition, within 15 min, all chlorine atoms were converted to chloride ion, indicating that chlorinated organic by-products do not accumulate. The reactor was characterized by measuring the photon flux (7.04 x 10(-6) E s(-1)) and the cumulative production of *OH during irradiation. The cumulative *OH production during irradiation was fastest at an initial [H(2)O(2)]=5 mM (k=0.77 micro M s(-1)).     

Kinetics of hydrolysis and cyclization of ethyl 2-(aminosulfonyl)benzoate to saccharin

The cyclization of ethyl 2-(aminosulfonyl)benzoate (ASB) to give saccharin was investigated in aqueous solutions at pH between 5.2 and 9.5 and in the temperature range of 296.2-334.2 K. The initial concentration of the reactant was varied between 1.45 x 10(-5) and 3.86 x 10(-4) M. Ultraviolet spectroscopy was used to obtain the kinetic data. The reaction is acid catalyzed and follows pseudo-first-order kinetics. The experimental rate constant, k(obs), increases with temperature and pH. Its dependence on the temperature and pH is well described by: k(obs) = k1 [OH-] = [(2.52 +/- 0.9) x 10(16) exp(-20.2 +/- 1 kcalmol(-1)/RT) s(-1)][OH-] A mechanism is proposed and the half-life of ethyl ASB is calculated.     

Vapour pressures, aqueous solubilities, Henry's Law constants, and octanol/water partition coefficients of a series of mixed halogenated dimethyl bipyrroles

Basic physical-chemical properties of five bromine and chlorine containing mixed halogenated dimethyl bipyrroles (HDBPs) were determined using established methods. Subcooled liquid vapour pressures (P(o)(L,25)), aqueous solubilities (S(w,25)), and octanol/water partition coefficients (K(ow)) were determined using the gas chromatography-retention time, generator column, and slow-stirring methods, respectively. Henry's Law constants (H25) were estimated using experimentally-derived P(o)(L) and S(w,25) data. Values of all four properties were generally similar to those reported for other polyhalogenated aromatic compounds [P(o)(L,25) = (7.55-191) x 10(-6) Pa; S(w,25) = (1.0-1.9) x 10(-5) g/l; log K(ow) = 6.4-6.7; H25 = 0.0020-0.14 Pa m3/mol]. The effect of replacing a chlorine with a bromine atom significantly decreased P(o)(L,25) (log P(o)(L,25) = -0.4197 (# bromine atoms) - 2.643, p<0.01) and H25 (log H25 = -0.508 (# bromine atoms) + 0.394, p<0.02). There were no significant effects of bromine/chlorine substitution on S(w,25) or K(ow). A simple Level I equilibrium partitioning model predicted the environmental behaviour of HDBPs to be similar to a tetrabrominated diphenyl ether. Only slight differences in behaviour amongst HDBP congeners were predicted since substitution of a bromine for a chlorine (Cl/Br substitution) atom had less effect than H/Cl or H/Br substitution on P(o)(L,25), S(w,25), H25, and K(ow).     

二氧化氯处理中药废水的氧化特性研究

采用稳定性二氧化氯溶液氧化降解中药废水,运用正交设计方法考察了常温、常压(291～298 K,1.013×10~5Pa)下ClO_2起始浓度([ClO_2]:COD)、pH、氧化反应时间等因素对中药废水处理效果的影响。研究表明,(1)当[ClO_2]:COD在1.0～0.4范围时,COD的平均去除率42%;当[ClO_2]:COD大于1.0或小于0.4时,COD平均去除率仅为27%～35%;(2)pH=2～4时,COD去除率可以达到40%以上,且pH≥10时,COD去除率高达59%;(3)COD去除率随着反应时间的延长而升高,氧化反应30 min左右,COD去除率能达到40%以上,105 min后处理效率达到63%;(4)ClO_2处理中药废水的最佳工艺条件是[ClO_2]:COD为0.7:1,反应pH值6,反应时间75 min。     

Effects of copper on spore germination, growth and ultrastructure of Polypodium cambricum L. gametophytes

The effects of different concentrations (10(-5), 5x10(-5) and 10(-4)M) of copper bromide on spore germination, growth and ultrastructure were investigated in Polypodium cambricum L. gametophytes. The inhibitory effect of Cu was observed in spores cultured on medium supplemented with 10(-4)M CuBr(2): germination occurred about 40 days after sowing and was only 25%. Concentrations of 5x10(-5) and 10(-4)M CuBr(2) induced changes in gametophyte development, possibly by re-orientation of growth. Gametophytes treated with 10(-5) and 5x10(-5)M CuBr(2) took up and accumulated a large amount of copper and ultrastructural observations showed that cytoplasmic damage was limited to twisted swollen thylakoids. The ultrastructure of gametophytes treated with 10(-4)M CuBr(2) showed absence of a vacuolar compartment. The present observations suggest that P. cambricum gametophytes could be a suitable material for studying physiological and molecular alterations induced by excess copper.     

Formation potentials of bromate and brominated disinfection by-products in bromide-containing water by ozonation

The ozonation involved in drinking water treatment raises issues of water quality security when the raw water contains bromide (Br^?). Br^? ions may be converted to bromate (BrO₃ ^?) during ozonation and some brominated disinfection by-products (Br-DBPs) in the following chlorination. In this study, the effects of ozone (O₃) dosage, contact time, pH, and Br^? and ammonia (NH₃-N) concentrations on the formation of BrO₃ ^? and Br-DBPs have been investigated. The results show that decreasing the initial Br^? concentration is an effective means of controlling the formation of BrO₃ ^?. When the concentration of Br^? was lower than 100 μg/L, by keeping the ratio of O₃ dosage to dissolved organic carbon (DOC) concentration at less than 1, BrO₃ ^? production was effectively suppressed. The concentration of BrO₃ ^? steadily increased with increasing O₃ dosage at high Br^? concentration (>900 μg/L). Additionally, a longer ozonation time increased the concentrations of BrO₃ ^? and total organic bromine (TOBr), while it had less impact on the formation potentials of brominated trihalomethanes (Br-THMFP) and haloacetic acids (Br-HAAFP). Higher pH value and the presence of ammonia may lead to an increase in the formation potential of BrO₃ ^? and Br-DBPs.     

Disinfection of an advanced primary effluent with peracetic acid and ultraviolet combined treatment: a continuous-flow pilot plant study

Disinfection of an advanced primary effluent using a continuous-flow combined peracetic acid/ultraviolet (PAA/UV) radiation system was evaluated. The purpose was to determine whether the maximum microbial content, established under Mexican standards for treated wastewaters meant for reuse--less than 240 most probable number fecal coliforms (FC)/100 mL--could be feasibly accomplished using either disinfectant individually, or the combined PAA/UV system. This meant achieving reduction of up to 5 logs, considering initial concentrations of 6.4 x 10(+6) to 5.8 x 10(+7) colony forming units/100 mL. During the tests performed under these experiments, total coliforms (TC) were counted because FC, at the most, will be equal to TC. Peracetic acid disinfection achieved less than 1.5 logs TC reduction when the C(t) x t product was less than 2.26 mg x minimum (min)/L; 3.8 logs for C(t) x t 4.40 mg x min/L; and 5.9 logs for C(t) x t 24.2 mg x min/L. In continuous-flow UV irradiation tests, at a low-operating flow (21 L/min; conditions which produced an average UV fluence of 13.0 mJ/cm2), the highest TC reduction was close to 2.5 logs. The only condition that produced a disinfection efficiency of approximately 5 logs, when both disinfection agents were used together, was the combined process dosing 30 mg PAA/L at a pilot plant flow of 21 L/min and contact time of 10 minutes to attain an average C(t) x t product of 24.2 mg x min/L and an average UV fluence of 13 mJ/cm2. There was no conclusive evidence of a synergistic effect when both disinfectants were employed in combination as compared to the individual effects achieved when used separately, but this does not take into account the nonlinearity (tailing-off) of the dose-response curve.     

The effects of pH on fluoxetine in Japanese medaka (Oryzias latipes): acute toxicity in fish larvae and bioaccumulation in juvenile fish

Recent detection of fluoxetine in the aquatic environment and fish suggests a possibly high accumulation of fluoxetine; however, no report is available on the bioaccumulation of fluoxetine in aquatic organisms. Since bioaccumulation of fluoxetine was probably dependent on pH near the pK(a) value of 10.1, experiments were conducted approximately at pH 7, 8, and 9. Distribution coefficients between 1-octanol and water (D(ow)), and those between synthetic membrane vesicles (liposomes) and water (D(lip-wat)) were determined at pH 7, 8, and 9. The D(ow) and D(lip-wat) values increased significantly with increasing pH. Acute toxicity tests were performed using Japanese medaka (Oryzias latipes) prior to the bioaccumulation test, and 96-h LC(50) values were 5.5, 1.3, and 0.20mgl(-1) at pH 7, 8, and 9, respectively. In the bioaccumulation test, concentrations of fluoxetine and its major metabolite, norfluoxetine, in the fish body and liver were measured. The bioconcentration factors (BCF) of fluoxetine for Japanese medaka were 8.8, 3.0x10, and 2.6x10(2) in the body and 3.3x10(2), 5.8x10(2), and 3.1x10(3) in the liver at pH 7, 8, and 9, respectively. The BCF values were lower at pH 7 and higher at pH 9 mainly because of the increase in nonionized species with significantly higher hydrophobicity than the ionized species at pH values closer to pK(a). A similar trend was obtained for the concentration of norfluoxetine in the fish but the pseudo-BCF values (the ratio of the norfluoxetine concentration in the fish and the fluoxetine concentration in test water) were higher than the BCF value of fluoxetine at all pH conditions.     

Degradation of octylphenol and nonylphenol by ozone - part II: indirect reaction

The indirect reaction of octylphenol (OP) and nonylphenol (NP) with hydroxyl radicals (*OH) during ozonation was investigated at pH values ranging from 6 to 9. A parameter Rct, representing the ratio of the *OH-exposure to the ozone-exposure, was measured using a method involving a low concentration of p-chlorobenzoic acid as a *OH-probe compound during the ozonation. By assuming that Rct is a constant value at a given pH, the second order rate constants of the alkylphenol reaction with hydroxyl radicals were determined as 1.4(+/-0.2) x 10(10) and 1.1(+/-0.2) x 10(10) M(-1) s(-1) for OP and NP, respectively. The proportions of each alkylphenol degraded by direct molecular ozone reaction and indirect hydroxyl radical reaction were predicted at different pH values. The contribution of indirect *OH reactions with each AP was found to represent over 50% of the total degradation for pH approximately 7, and the contribution increases substantially with pH>7.     

Ameliorative effect of zinc oxide nanoparticles against potassium bromate-mediated toxicity in Swiss albino rats

Environmental Science and Pollution Research - Potassium bromate (PB) is a commonly used food additive, a prominent water disinfection by-product, and a class IIB carcinogen. It exerts a various...     

Kinetics of photodegradation and ozonation of pentachlorophenol

The oxidation of 2,3,4,5,6-pentachlorophenol (PCP) has been carried out by a photodecomposition process using a polychromatic UV irradiation, and by an ozonation process. In the photodegradation process, the pH accelerated the decomposition rate and the approximate first-order rate constants were evaluated, with values between 0.16+/-0.005 min(-1) at pH=3 and 0.26+/-0.007 min(-1) at pH=9. A more rigorous kinetic study led to the determination of the quantum yields of the reaction, with values of 200+/-7x10(-3) mol/Eins for pH=3 and 22+/-1.1x10(-3) mol/Eins for pH=9. In the ozonation process, the rate constants for the reaction between ozone and PCP were determined by means of a competition kinetics, with values in the range from 0.67x10(5) to 314x10(5) l/mols. The specific rate constants for the un-dissociated and dissociated forms of PCP were also calculated. Finally, in both processes, the intermediate reaction products were identified, the most important being tetrachlorocatechol, tetrachlorohydroquinone and tetra-p-chlorobenzoquinone. Free chloride ion released, which was favored at high pHs, was also followed in both processes.