Chlorination of bisphenol A in aqueous media: formation of chlorinated bisphenol A congeners and degradation to chlorinated phenolic compounds

The chlorination of bisphenol A (BPA) in aqueous media was investigated in order to describe the degradation profile of this compound and the formation of chlorinated products. Aqueous solutions of BPA (approx. 1 mg/l) were chlorinated by sodium hypochlorite solution at room temperature and under weakly alkaline conditions. Chlorinated compounds were extracted with dichloromethane and determined by gas chromatography/mass spectrometry (GC/MS). BPA was consumed completely within 5 min of chlorination, when the initial chlorine concentration was 10.24 mg/l (molar ratio to BPA, 58.7). On the other hand, when the initial chlorine concentration was 1.03 mg/l (molar ratio, 6.56), 9.3% of BPA still remained after 60 min chlorination. Five chlorinated BPA congeners, 2-chlorobisphenol A (MCBPA), 2,6-dichlorobisphenol A (2,6-D2CBPA), 2,2'-dichlorobisphenol A (2,2'-D2CBPA), 2,2',6-trichlorobisphenol A (T3CBPA) and 2,2', 6,6'-tetrachlorobisphenol A (T4CBPA) were formed in the earlier stages of chlorination. Several chlorinated phenolic compounds, 2,4,6-trichlorophenol (T3CP), 2,6-dichloro-1,4-benzoquinone (D2CBQ), 2,6-dichloro-1,4-hydroquinone (D2CHQ), C9H10Cl2O2, C9H8Cl2O and C10H12Cl2O2, were also formed by further chlorination.     

Oxidative transformations of environmental pharmaceuticals by Cl₂, ClO₂, O₃, and Fe(VI): kinetics assessment

Several pharmaceuticals have been detected globally in surface water and drinking water, which indicate their insufficient removal from water and wastewater using conventional treatment methods. This paper reviews the kinetics of oxidative transformations of pharmaceuticals (antibiotics, lipid regulators, antipyretics, anticonvulsants, and beta-blockers) by Cl(2), ClO(2), O(3), and ferrate(VI) (Fe(VI)O(4)(2-),Fe(VI)) under treatment conditions. In the chlorination of sulfonamide antibiotics, HOCl is the major reactive Cl(2) species whereas in the oxidation by Fe(VI), HFeO(4)(-) is the dominant reactive species. Both oxidation processes can oxidize sulfonamides in seconds at a neutral pH (t(1/2)≤ 220 s; 1 mg L(-1) HOCl or K(2)FeO(4)). The reactivity of O(3) with pharmaceuticals is generally higher than that of HOCl (k(app,pH 7) (O(3))=1-10(7)M(-1)s(-1); k(app,pH 7) (HOCl)=10(-2)-10(5)M(-1)s(-1)). Ozone selectively oxidizes pharmaceuticals and reacts mainly with activated aromatic systems and non-protonated amines. Oxidative transformation of most pharmaceuticals by O(3) occurs in seconds (t(1/2)≤ 100 s; 1 mg L(-1) O(3)) while half-lives for oxidations by HOCl differ by at least two orders of magnitude. Ozone appears to be efficient in oxidizing pharmaceuticals in aquatic environments. The limited work on Fe(VI) shows that it can also potentially transform pharmaceuticals in treatment processes.     

Photodegradation of bisphenol A in simulated lake water containing algae, humic acid and ferric ions

The photodegradation of bisphenol A (BPA), a suspected endocrine disruptor (ED), in simulated lake water containing algae, humic acid and Fe3+ ions was investigated. Algae, humic acid and Fe3+ ions enhanced the photodegradation of BPA. Photodegradation efficiency of BPA was 36% after 4h irradiation in the presence of 6.5 x 10(9) cells L(-1) raw Chlorella vulgaris, 4 mg L(-1) humic acid and 20 micromol L(-1) Fe3+. The photodegradation efficiency of BPA was higher in the presence of algae treated with ultrasonic than that without ultrasonic. The photodegradation efficiency of BPA in the water only containing algae treated with ultrasonic was 37% after 4h irradiation. The algae treated with heating can also enhance the photodegradation of BPA. This work helps environmental scientists to understand the photochemical behavior of BPA in lake water.     

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 and mechanism of nitrite oxidation by hypochlorous acid in the aqueous phase

The rate coefficient for the reaction of nitrite with hypochlorite and hypochlorous acid has been studied using spectrophotometric measurements. The reaction rate has been determined in a wide range of H(+) concentration (5< or =-log[H(+)]< or =11). The kinetics were carried out as a function of NO(2)(-), H(+) and total hypochlorite ([HOCl](total)=[HOCl]+[ClO(-)]+[ClNO(2)]) concentrations. The observed overall rate law is described by: -d[HClO](T)dt=[a[NO(2)(-)](2)+b[NO(2)(-)]][H(+)](2)c+d[H(+)]+e[NO(2)(-)][H(+)](2)[HOCl](total)At T=298 K and in Na(2)SO(4) at an ionic strength (I=1.00 M), we obtained using a nonlinear fitting procedure: a=(1.83+/-0.36)x10(7) s(-1), b=(1.14+/-0.23)x10(5) Ms(-1), c=(1.12+/-0.17)x10(-13) M, d=(1.43+/-0.29)x10(-6) M(2) and e=(1.41+/-0.28)x10(3) M where the errors represent 2sigma. According to the overall rate law, a/b=k(1)/k(3), b/e=k(3), c=K(w), d/c=K(a), d=K(a)K(w) and e=K(1)K(a). In Na(2)SO(4) at an ionic strength (I=1.00 M), the values of K(1) and K(a) are (1.1+/-0.1)x10(-4) and 1.28x10(7) M(-1), respectively. A mechanism is proposed for the NO(2)(-) oxidation which involves the reversible initial step: NO(2)(-)+HOCl left harpoon over right harpoon ClNO(2)+OH(-) (K(1)), while ClNO(2) undergoes the two parallel reactions: attack by NO(2)(-) (k(1)) and hydrolysis (k(3)). ClNO(2) and N(2)O(4) are proposed as important intermediates as they control the mechanism. The rate coefficients k(1) and k(3) have been determined at different ionic strengths in NaCl and Na(2)SO(4). The influence of the ionic strength and ionic environment has been studied in this work.     

Effect of photosensitizer diethylamine on the photodegradation of polychlorinated biphenyls

The objective of this study was to investigate the effect of diethylamine and xenon simulated sunlight on the photodegradation of two forms of PCBs including PCBs in transformer oil and PCB congener 138. The result of GC chromatograms illustrated the shifting pattern of higher chlorinated biphenyls in transformer oil degraded to lower chlorinated biphenyls with the extension of exposure time. The effect of diethylamine and xenon simulated sunlight was significant on the photodegradation of both PCBs in transformer oil and congener 138. The initial degradation rates of congener 138 (1.14 x 10(-9) to 4.47 x 10(-9) mol l(-1) h(-1)) were in direct proportion to the initial concentrations of congener 138 which confirmed the pseudo-first-order reaction of PCB photodegradation. The apparent quantum yields (phi) of congener 138 using diethylamine in xenon photoreactor were ranged between 2.08 x 10(-2) and 9.8 x 10(-4). PCB congeners 123, 97, 70, 67, 33, 29, 17, 12, and 9 were detected as the descendants of the photodegradation of congener 138 through dechlorination. The major pathway of congener 138 photodegradation in this study was via para-dechlorination.     

Estrogenic effects of phenolic compounds on glucose-6-phosphate dehydrogenase in MCF-7 cells and uterine glutathione peroxidase in rats

In this study, we tested phenolic compounds such as bisphenol A (BPA), 4-nonylphenol (NP), 4-octylphenol (OP) and 4-propylphenol (PP) by using glucose-6-phosphate dehydrogenase (G6PD) in estrogen sensitive human breast cancer cells (MCF-7 cells) and glutathione peroxidase (GPx) in female immature Sprague-Dawley (SD) rats. This study was designed to investigate whether phenolic compounds have estrogenic effects in these useful screening methods for endocrine disruptors. We chose 6 h as the incubation period for the G6PD assay through a preliminary experiment using 17beta-estradiol (E2). Above the concentration of 1 x 10(-8) M, BPA significantly increased the G6PD activity in a concentration-dependent manner, relative to the control. NP (over the concentration of 1 x 10(-9) M) also enhanced the G6PD activity by about 1.8 times that of the control. OP produced weaker effects on G6PD than NP, and showed a tendency to increase the G6PD activity. PP did not affect the G6PD activity. These results show that BPA and NP have the effect of enhancing G6PD activities in MCF-7 cells. In the in vivo GPx assay, both BPA and E2 significantly increased the uterus wet weights and dramatically enhanced uterine GPx activities in immature female rats in a dose-dependent manner. Treatment with NP (500 mg/kg/day) increased significantly both the uterine GPx activity and the uterus wet weights in immature female rats. OP (500 mg/kg/day) also caused a significant increase in uterine GPx activity, but had no effect on the uterus wet weights. This finding indicates that the change in uterine GPx activities could be a more sensitive parameter than that of uterus wet weights in immature rats. This study implies that phenolic compounds have a weak estrogenic effects.     

Influence of sorption to dissolved humic substances on transformation reactions of hydrophobic organic compounds in water. Part II: hydrolysis reactions

The effect of dissolved humic acid (HA) on two types of hydrolysis reactions was investigated: (I) dehydrochlorination of gamma-hexachlorocyclohexane (HCH) and 1,1,2,2-tetrachloroethane (TeCA) as a reaction involving hydroxide ions (OH(-)) and (II) hydrolysis of 1-octyl acetate (OA) which is catalyzed by H(+) at the applied pH value (pH 4.5). The rate of TeCA hydrolysis was not affected by addition of 2 g l(-1) of HA at pH 10 (k' = 0.33 h(-1)) but HCH hydrolysis was significantly inhibited (k' = 4.6 x 10(-3) h(-1) without HA and 2.8 x 10(-3)h(-1) at 2 g l(-1) HA). HCH is sorbed by 51% whereas TeCA sorption is insignificant at this HA concentration. Sorbed HCH molecules are effectively protected due to electrostatic repulsion of OH(-) by the net negative charge of the HA molecules. In contrast, OA hydrolysis at pH 4.5 (k' = 1.6 x 10(-5) h(-1)) was drastically accelerated after addition of 2 g l(-1) HA (k' = 1.1 x 10(-3) h(-1)). The ratio of the pseudo-first-order rate constants of the sorbed and the freely dissolved ester fraction is about 70. H(+) accumulation in the microenvironment of the negatively charged HA molecules was suggested to contribute to the higher reaction rate for the sorbed fraction in case of this H(+)-catalyzed reaction. Analogous effects from anionic surfactants are known as micellar catalysis.     

Degradation of terbutylazine (2-chloro-4-ethylamino-6-terbutylamino-1,3,5-triazine), deisopropyl atrazine (2-amino-4-chloro-6-ethylamino-1,3,5-triazine), and chlorinated dimethoxy triazine (2-chloro-4,6-dimethoxy-1,3,5-triazine) by zero valent iron and electrochemical reduction

To help elucidate the mechanism of dechlorination of chlorinated triazines via metallic iron, terbutylazine (TBA: 2-chloro-4-ethylamino-6-terbutylamino-1,3,5-triazine), deisopropyl atrazine (DIA: 2-amino-4-chloro-6-ethylamino-1,3,5-triazine), and chlorinated dimethoxy triazine (CDMT: 2-chloro-4,6-dimethoxy-1,3,5-triazine) were degraded via zero valent iron under controlled pH conditions. The lower the solution pH the faster the degradation, with surface area normalized pseudo first order rate constants ranging from 2 (+/- 1)x10(-3) min(-1) m(-2) l for TBA at pH 2.0 to 4 (+/- 2)x10(-5) min(-1) m(-2) l for CDMT at pH 4.0. Hydrogenolysis (dechlorinated) products were observed for TBA and CDMT. Electrochemical reduction on mercury showed similar behavior for all of the triazines studied; the initial product of CDMT bulk electrolysis was the dechlorinated compound. The iron results are consistent with a mechanism involving the addition of surface hydrogen to the surface associated triazine.     

Multi-generational effects of four selected environmental oestrogens on Daphnia magna

The objective of this study was to determine whether vertebrate-type oestrogens have ecotoxicological effects on a crustacean species. The effects of 17beta-oestradiol (E2), diethylstilbestrol (DES), bisphenol A (BPA) and 4-nonylphenol (4-NP) on the freshwater invertebrate Daphnia magna were assessed over first and second generations. The acute EC(50) 48 h, based on immobilisation, for E2, DES, BPA and 4-NP were 2.87 mg/l, 1.55 mg/l, 7.75 mg/l and 0.13 mg/l, respectively. The impact of the test chemicals on moulting frequency was also assessed. The EC(50) 48 h, based on the inhibition of moult number for E2, DES and 4-NP were 2.04 mg/l, 1.87 mg/l and 0.14 mg/l, respectively. BPA was not observed to impact the moulting frequency of D. magna at concentrations tested. In a series of separate studies, the effects of the four selected test compounds on the survival, moulting frequency and reproduction of first and second generational D. magna were assessed over a period of 21 d. Exposure of D. magna to 4-NP decreased the number of offspring produced in both first and second generation testing. DES proved to have no significant (p0.05) inhibition of fecundity in first generation but when second generation daphnids were exposed to DES, a significant (p0.05) reduction in the number of offspring was recorded. When D. magna were exposed to E2 or BPA, no statistically significant (p0.05) inhibition in the number of moults or offspring produced was observed.     

The effect of inorganic and organic chlorine on formation of highly chlorinated organic compounds during incineration: Laboratory pilot study

Aliphatic liquid as a basic fuel was incinerated in a laboratory scale pilot plant. Inorganic chlorine and organic chlorine mixed with basic fuel were used as additive chemicals. Sodium chloride (NaCl) and tetrachloroethylene (C₂Cl₄) were used as the sources of inorganic and organic chlorine. Combustion parameters were adjusted for optimum combustion and, consequently, the amount of particles in flue gases was low. The concentrations of chlorine in flue gases were high enough for possible formation reactions of organic chlorinated compounds in all of the chlorine input tests. An increase in chlorine input did not significantly increase the amounts of highly chlorinated organic compounds, like PCDD/Fs. The main result was that chlorophenol concentrations increased in parallel with organic chlorine input. Comparing organic chlorine to inorganic chlorine tests showed that more highly substituted PCDD/F congeners were formed when organic chlorine was the additive chlorine source. The formation of highly chlorinated organic compounds such as PCDD/Fs requires not only chlorine and aliphatic fuel to be formed, but some catalysts are also needed.     

Influence of pH on persulfate oxidation of TCE at ambient temperatures

In situ chemical oxidation (ISCO) is a technology used for groundwater remediation. This laboratory study investigated the use of the oxidant sodium persulfate for the chemical oxidation of trichloroethylene (TCE) at near ambient temperatures (10, 20 and 30 degrees C) to determine the influence of pH (pH=4, 7 and 9) on the reaction rate (i.e., pseudo-first-order rate constants) over the range of temperatures utilized. TCE solutions (60 mg l(-1); 0.46 mM) were prepared in phosphate buffered RO water and a fixed persulfate/TCE molar ratio of 50/1 was employed in all tests. Half-lives of TCE degradation at 10, 20 and 30 degrees C (pH 7) were 115.5, 35.0 and 5.5h, respectively. Maximum TCE degradation occurred at pH 7. Lowering system pH resulted in a greater decrease in TCE degradation rates than increasing system pH. Radical scavenging tests used to identify predominant radical species suggested that the sulfate radical (SO(4)(.-)) predominates under acidic conditions and the hydroxyl radical (.OH) predominates under basic conditions. In a side by side comparison of TCE degradation in a groundwater vs. unbuffered RO water it was demonstrated that when the system pH is buffered to near neutral pH conditions due to the presence of natural occurring groundwater constituents that the TCE degradation rate is higher than in unbuffered RO water where the system pH dropped from 5.9 to 2.8. The results of this study suggest that in a field application of ISCO, pH should be monitored and adjusted to near neutral if necessary.     

UV-TiO_2光催化氧化降解双酚A的动力学研究

采用自制光催化氧化反应器,研究了双酚A(BPA)在纳米TiO_2悬浆体系中的光催化氧化特性.结果表明:(1)UV-TiO_2对水中BPA有较强光催化氧化降解作用.在10 W低压汞灯照射下,当纳米TiO_2用量为1.0 g/L、pH为5.5、BPA初始质量浓度为10 mg/L、曝气量为4.0 mL/min、温度为室温、反应时间为120 min时,BPA去除率可达97.1%.当pH≥9.5时,120 min后BPA已经基本光催化氧化降解完全.(2)BPA的光催化氧化降解曲线均很好地符合一级反应动力学方程.其速率常数与纳米TiO_2用量、pH、BPA初始浓度、曝气量有关;促进·OH和电子-空穴对的生成是提高光催化氧化反应速率的重要途径.     

Identification and behavior of reaction products formed by chlorination of ethynylestradiol

Six products were formed by reaction of ethynylestradiol (EE2) with sodium hypochlorite in buffered solutions. 4-Chloroethynylestradiol (4-ClEE2) and 2,4-dichloroethynylestradiol (2,4-diClEE2) were identified as the two major reaction products, using preparative HPLC, MS, and NMR. When EE2 reacted with chlorine at different pHs (pH 5, 7, and 9) or chlorine concentrations (0.2, 1, 2, and 5 mmol/l, corresponding to molar ratios to EE2, 1, 5, 10, and 25, respectively), the formation of 4-ClEE2 and 2,4-diClEE2 was observed under the above conditions, and the highest yields were 20 and 52 mol%, respectively. EE2 was consumed almost completely within 5 min of chlorination by addition of chlorine of more than 1 mmol/l (molar ratio to EE2, 5). On the other hand, the two products existed in highly chlorinated solutions after 60 min (4ClEE2, 1-6 mol%; 2,4-diClEE2, 3-25 mol%). The estrogenic activities of 4-ClEE2 by estrogen receptor alpha or beta binding assay were similar to those of the parent EE2, and the activities of 2,4-diClEE2 were lower about 10 times.     

Endocrine disruptors in freshwater streams of Hesse, Germany: changes in concentration levels in the time span from 2003 to 2005

Four small freshwater streams in the region known as Hessisches Ried in Germany were investigated with respect to the temporal and spatial concentration variations of the endocrine disruptors bisphenol A (BPA), 4-tert-octylphenol (4-tert-OP), and the technical isomer mixture of 4-nonylphenol (tech.-4-NP). Measured concentrations of the target compounds in the river water samples ranged from <20 ng/l to 1927 ng/l, <10 ng/l to 770 ng/l, and <10 ng/l to 420 ng/l for BPA, 4-tert-OP and tech.-4-NP, respectively. BPA levels were, with the exception of two samples, below the predicted no-effect concentration (PNEC) for water organisms. Tech.-4-NP concentrations showed a significant tendency of decreasing concentrations during the sampling period. This is mainly attributed to the implementation of the European Directive 2003/53/EG, which restricts both the marketing and use of nonylphenols. Results from the analysis of additionally collected water samples from sewage treatment plant (STP) effluents indicate that the STPs cannot be the only sources for tech.-4-NP found in the river water.     

Elimination of endocrine disrupting chemicals nonylphenol and bisphenol A and personal care product ingredient triclosan using enzyme preparation from the white rot fungus Coriolopsis polyzona

The biocatalytic elimination of the endocrine disrupting chemicals (EDC) nonylphenol (NP) and bisphenol A (BPA) and the personal care product ingredient triclosan (TCS) by the enzyme preparation from the white rot fungus Coriolopsis polyzona was investigated. Analysis of variance methodology showed that the pH and the temperature are statistically significant factors in the removal of NP, BPA and TCS. The elimination of NP and TCS was best at a temperature of 50 degrees C and the disappearance of BPA at 40 degrees C, whereas the most suitable pH for all three micropollutants was 5. After a 4-h treatment of the three target compounds at concentrations of 5 mg l(-1) all of the NP and BPA were eliminated. In the case of TCS, 65% was removed after either a 4 or an 8-h treatment. The utilisation of 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) in the laccase/mediator system significantly increased the efficiency of the enzymatic treatment. The elimination of NP and BPA was directly associated with the disappearance of the estrogenic activity. Mass spectrometry analysis showed that the enzymatic treatment produced high molecular weight metabolites through a radical polymerization mechanism of NP, BPA and TCS. These oligomers were produced through the formation of C-C or C-O bonds. The polymerization of NP produced dimers, trimers, tetramers and pentamers which had molecular weights of 438, 656, 874 and 1092 amu respectively. The polymerization of BPA produced dimers, trimers and tetramers which had molecular weights of 454, 680 and 906 amu. Finally, the polymerization of TCS produced dimers, trimers and tetramers which had molecular weights of 574, 859 and 1146 amu.     

Biodegradation of coplanar polychlorinated biphenyls by anaerobic microorganisms from estuarine sediments.

In this study, we investigated the biodegradability of biphenyl and 5 congeners (one non-planar and four coplanar) of polychlorinated biphenyl (PCB). Biphenyl, the non-planar congener 2,3',4',5-tetrachlorobiphenyl (25-34 CB), and the four coplanar congeners 3,3',4,4'-tetrachlorobiphenyl (34-34 CB), 3,4,4',5-tetrachlorobiphenyl (345-4 CB), 3,3',4,4',5-pentachlorobiphenyl (345-34 CB), and 3,3',4,4',5,5'-hexachlorobiphenyl (345-345 CB) were amended at a concentration of 10 mg/L into anoxic sediment slurries collected from the estuaries of the Tansui River and the Erjen River. During 2 years' incubation under sulfidogenic conditions, biphenyl was persistent, while all other chlorinated congeners, except for 345-345 CB, were dechlorinated with or without a lag period in sediment slurries collected from both rivers. Dechlorination of coplanar and non-planar congeners began with para chlorine removal. All para chlorines from the mono-, di-, and trichlorobiphenyl groups could be removed by sediment slurries from both rivers. Microbial communities in sediment from the Erjen River additionally fostered meta-dechlorination activity, but only after removal of all the para chlorines. Addition of Tween 20 (0.05%, v/v) into sediment slurries from the Tansui River did not enhance dechlorination rates or extents, but the addition of toluene- or 3-chlorobenzoate-adapted sediments enhanced dechlorination of 34-34 CB and 345-4 CB.     

A simple spectrophotometric method for the determination of cobalt in industrial, environmental, biological and soil samples using bis(salicylaldehyde)orthophenylenediamine

Bis(salicylaldehyde)orthophenylenediamine (BSOPD) has been proposed as new analytical reagent for the direct non-extractive spectrophotometric determination of cobalt. It reacts with cobalt in slightly acidic (0.0002-0.001 M H(2)SO(4)) 50% 1,4-dioxanic medium to form a red-orange chelate with a molar ratio 1:1. The reaction is instantaneous and the maximum absorbance was obtained at 458 nm and remains constant for over 24h. The average molar absorption coefficient and Sandell's sensitivity were found to be 1.109 x 10(4)l mol(-1)cm(-1) and 20 ng cm(-2) of Co(II), respectively. Linear calibration graph was obtained for 0.1-15 mg l(-1) of Co(II) with a correlation coefficient value of 0.995 for Co-BSOPD complex. Large excess of 44 cations, anions and complexing agents do not interfere in the determination. The method was successfully used in the determination of cobalt(II) from synthetic mixture and certified reference materials for the purpose of validating the method and the results of analyses were found to be excellent agreement with those of actual values. This developed method was also used for determination of cobalt in some environmental waters (potable and polluted), biological (blood and urine) and soil samples and solution containing both cobalt(II) and cobalt(III). The results of the proposed method for biological samples were comparable with AAS and were found to be in good agreement. The method has high precision and accuracy (s=+/-0.01 for 0.5 mg l(-1)).     

Study of inclusion complex of beta-cyclodextrin and nitrobenzene

beta-cyclodextrin can react with nitrobenzene to form an inclusion complex which is characterized by (1)H NMR and powder X-ray diffractometry. The ratio of beta-CD to NB in inclusion complex is determined as 1:1. At 25 degrees C, the dissociated constant, K(D), of the inclusion complex is measured as 6.5 x 10(-3) M in neutral solution (pH=7.0), but in alkali (pH=13.5), K(D) is 3.2 x 10(-2) M which is much larger than that measured in neutral.     

Formation of volatile halogenated by-products during chlorination of isoproturon aqueous solutions

The present paper deals with the formation of volatile halogenated by-products (POX) during the chlorination (160 mg/l) of aqueous solutions of the herbicide isoproturon (40 mg/l). Chlorination reactions have been carried out over 48 h, at ambient temperature, at two pHs (6 and 9) and in the presence or not of bromide ions (80 mg/l). The main results obtained have been as follows: (1) in the presence of bromide, isoproturon degradation is rather fast and it results affected by pH, complete isoproturon degradation is achieved within 1 and 15 min at pH 6 and 9, respectively; (2) in the absence of bromide herbicide degradation is slow (complete degradation is achieved within 180 min) and it is not affected by pH; (3) at pH 6, regardless of the presence of bromide, the maximum amount of POX formed is low (approximately 15 micromol X-/l) and remains constant during the reaction; (4) at pH 9 the amount of POX formed is far greater and continuously increases during the reaction, reaching a value of about 110 micromol X-/l after 48 h; (5) two different groups of by-products have been identified by solid phase micro extraction (SPME)-gas chromatography (GC)-mass spectrometry (MS) for the reactions carried out with or without bromide; among them, aliphatic as well as aromatic by-products containing chlorine, bromine or both halogens are present even though the most abundant are halogenated-methane derivatives (haloforms); pH value affects the amount of these by-products but does not modify their chemical nature.