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.     

Kinetics of the oxidation of sucralose and related carbohydrates by ferrate(VI)

The kinetics of the oxidation of sucralose, an emerging contaminant, and related monosaccharides and disaccharides by ferrate(VI) (Fe(VI)) were studied as a function of pH (6.5-10.1) at 25°C. Reducing sugars (glucose, fructose, and maltose) reacted faster with Fe(VI) than did the non-reducing sugar sucrose or its chlorinated derivative, sucralose. Second-order rate constants of the reactions of Fe(VI) with sucralose and disaccharides decreased with an increase in pH. The pH dependence was modeled by considering the reactivity of species of Fe(VI), (HFeO(4)(-) and FeO(4)(2-)) with the studied substrates. Second-order rate constants for the reaction of Fe(VI) with monosaccharides displayed an unusual variation with pH and were explained by considering the involvement of hydroxide in catalyzing the ring opening of the cyclic form of the carbohydrate at increased pH. The rate constants for the reactions of carbohydrates with Fe(VI) were compared with those for other oxidant species used in water treatment and were briefly discussed.     

Reduction of ferrate(VI) and oxidation of cyanate in a Fe(VI)-TiO2-UV-NCO- system

The aqueous photocatalytic degradation of cyanate (NCO(-)), which is a long-lived neurotoxin formed during the remediation of cyanide in industrial waste streams, was studied in the ferrate(VI)-UV-TiO2-NCO(-) system. Kinetics measurements of the photocatalytic reduction of ferrate(VI) were carried out as a function of [NCO(-)], [ferrate(VI)], [O(2)], light intensity (I(o)), and amount of TiO2 in suspensions at pH 9.0. The photocatalytic reduction rate of ferrate(VI) in the studied system can be expressed as -d[Fe(VI)]/dt=kI(o)(0.5) [NCO(-)] [TiO2]. The rate of photocatalytic oxidation of cyanate with ferrate(VI) was greater than the rate in the analogous system without ferrate(VI). The possibility of involvement of reactive ferrate(V) species for this enhancement was determined by studying the reactivity of ferrate(V) with NCO(-) in a homogeneous solution using a premix pulse radiolysis technique. The rate constant for the reaction of ferrate(V) and NCO(-) in alkaline medium was estimated to be (9.60+/-0.07) x 10(2) M(-1) s(-1), which is much slower than the ferrate(VI) self-decomposition reaction (k approximately 10(7) M(-1) s(-1)). An analysis of the kinetic data in the Fe(VI)-UV-TiO2-NCO(-) system suggests that ferrate(V) is not directly participating in the oxidation of cyanate. Possible reactions in the system are presented to explain results of ferrate(VI) reduction and oxidation of cyanate.     

Ferrate(VI): green chemistry oxidant for degradation of cationic surfactant

Iron in its familiar form exists in the +2 and +3 oxidation states, however, higher oxidation state of iron +6, ferrate(VI) (Fe(VI)O(4)(2-)) can be obtained. The high oxidation power of ferrate(VI) can be utilized in developing cleaner ("greener") technology for remediation processes. This paper demonstrates the unique property of ferrate(VI) to degrade almost completely the cationic surfactant, cetylpyridinium chloride (C(5)H(5)N(+)(CH(2))(15)CH(3).H(2)O Cl(-), CPC). The Rate law for the oxidation of CPC by ferrate(VI) at pH 9.2 was found to be: -d[Fe(VI)]/dt = k[Fe(VI)][CPC](2). Ferrate(VI) oxidizes CPC within minutes and molar consumption of ferrate(VI) was nearly equal to the oxidized CPC. The decrease in total organic carbon (TOC) from CPC was more than 95%; suggesting mineralization of CPC to carbon dioxide. Ammonium ion was the other product of the oxidation. This is the first report in which Fe(VI)O(4)(2-) ion opens the pyridine ring and mineralizes the aliphatic chain of the organic molecule giving inorganic ions.     

The exploration of potassium ferrate(VI) as a disinfectant/coagulant in water and wastewater treatment

This paper aims to explore potassium ferrate(VI) (K2FeO4) as an alternative water treatment chemical for both drinking water and wastewater treatment. The performance of potassium ferrate(VI) was evaluated in comparison with that of sodium hypochlorite (NaOCl) and that of NaOCl plus ferric sulphate (FS) or alum (AS). The dosages of ferrate(VI), NaOCl and FS/AS and sample pH values were varied in order to investigate the effects of these factors on the treatment performance. The study demonstrates that in drinking water treatment, ferrate(VI) can remove 10-20% more UV(254)-abs and DOC than FS for the same dose compared for natural pH range (6 and 8). The THMFP was reduced to less than 100 microg l(-1) by ferrate(VI) at a low dose. In addition to this, ferrate(VI) can achieve the disinfection targets (>6 log10 inactivation of Escherichia coliform (E. coli)) at a very low dose (6 mg l(-1) as Fe) and over wide working pH in comparison with chlorination (10 mg l(-1) as Cl2) plus coagulation (FS, 4 mg l(-1) as Fe). In wastewater treatment, ferrate(VI) can reduce 30% more COD, and kill 3log10 more bacteria compared to AS and FS at a similar or even smaller dose. Also, potassium ferrate(VI) can produce less sludge volume and remove more pollutants, which could make sludge treatment easier.     

Ferrate(VI) oxidation of zinc-cyanide complex

Zinc-cyanide complexes are found in gold mining effluents and in metal finishing rinse water. The effect of Zn(II) on the oxidation of cyanide by ferrate(VI) (Fe(VI)O(4)(2-), Fe(VI)) was thus investigated by studying the kinetics of the reaction of Fe(VI) with cyanide present in a potassium salt of a zinc cyanide complex (K(2)Zn(CN)(4)) and in a mixture of Zn(II) and cyanide solutions as a function of pH (9.0-11.0). The rate-law for the oxidation of Zn(CN)(4)(2-) by Fe(VI) was found to be -d[Fe(VI)]/dt=k[Fe(VI)][Zn(CN)(4)(2-)](0.5). The rate constant, k, decreased with an increase in pH. The effect of temperature (15-45 degrees C) on the oxidation was studied at pH 9.0, which gave an activation energy of 45.7+/-1.5kJmol(-1). The cyanide oxidation rate decreased in the presence of the Zn(II) ions. However, Zn(II) ions had no effect on the cyanide removal efficiency by Fe(VI) and the stoichiometry of Fe(VI) to cyanide was approximately 1:1; similar to the stoichiometry in absence of Zn(II) ions. The destruction of cyanide by Fe(VI) resulted in cyanate. The experiments on removal of cyanide from rinse water using Fe(VI) demonstrated complete conversion of cyanide to cyanate.     

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.     

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.     

Influence of complex reagents on removal of chromium(VI) by zero-valent iron

The removal of Cr(VI) by zero-valent iron (Fe(0)) and the effect of three complex reagents, ethylenediaminetetraacetic acid (EDTA), NaF and 1,10-phenanthroline, on this reaction were investigated using batch reactors at pH values of 4, 5 and 6. The results indicate that the removal of Cr(VI) by Fe(0) is slow at pH 5.0 and that three complex reagents play different roles in the reaction. EDTA and NaF significantly enhance the reaction rate. The zero-order rate constants at pH 5.0 were 5.44 microM min(-1) in the presence of 4mM EDTA and 0.99 micrM min(-1) in the presence of 8 mM NaF, respectively, whereas that of control was only 0.33 micrM min(-1), even at pH=4.0. This enhancement is attributed to the formation of complex compounds between EDTA/NaF and reaction products, such as Cr(III) and Fe(III), which eliminate the precipitates of Cr(III), Fe(III) hydroxides and Cr(x)Fe(1-)(x)(OH)(3) and thus reduce surface passivation of Fe(0). In contrast, 1,10-phenanthroline, a complex reagent for Fe(II), dramatically decreases Cr(VI) reduction by Fe(0). At pH=4.0, the zero-order rate constant in the presence of 1mM of 1,10-phenanthroline was 0.02 micrM min(-1), decreasing by 99.7% and 93.9%, respectively, compared with the results in the presence and absence of EDTA. The results suggest that a pathway of the reduction of Cr(VI) to Cr(III) by Fe(0) may involve dissolution of Fe(0) to produce Fe(II), followed by reduction of Cr(VI) by Fe(II), rather than the direct reaction between Cr(VI) and Fe(0), in which Fe(0) transfers electrons to Cr(VI).     

高铁酸盐对活性及分散染料的脱色研究

采用湿法制备了高铁酸钾(K₂FeO₄)氧化剂，研究了其对染料活性艳红X-3B(X-3B) 和分散蓝2BLN(2BLN)在不同pH条件下的脱色效果，并对Al₂ (SO₄)₃、K₂FeO₄及O₃对活性及分散染料的脱色效果进行了比较。结果表明：高铁酸钾对活性及分散染料的脱色效果明显， X-3B脱色率随pH的增加不断提高，2BLN脱色率在pH 6～10范围内无明显变化，在pH＝5时达到最大值。在X-3B及2BLN浓度同为100 mg／L，pH分别为10、5， K₂FeO₄浓度分别为100 mg／L和200 mg／L时，BLN及X-3B的脱色率分别达到92.3％和87.3％。在相同条件下，K₂FeO₄对活性艳红X-3B的脱色效果好于Al₂(SO₄)₃和O₃； 而K₂FeO₄对分散蓝2BLN的脱色效果虽比Al₂ (SO₄)₃稍差，但比臭氧的脱色效果要好。同时还研究了K₂FeO₄对活性及分散染料的脱色机理，结果表明： 高铁酸钾对X-3B的脱色依赖于K₂FeO₄的氧化作用，而对的2BLN的脱色则以絮凝为主。     

Effectiveness of potassium ferrate (VI) as a green agent in the treatment and disinfection of carwash wastewater

Environmental Science and Pollution Research - Carwash wastewater treatment with potassium ferrate (VI) (K2FeO4) was optimized by response surface methodology. The optimum conditions for chemical...     

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.     

Potential application of highly reactive Fe(0)/Fe3O4 composites for the reduction of Cr(VI) environmental contaminants

We describe the use of highly reactive Fe(0)/Fe3O4 composites for the reduction of Cr(VI) species in aqueous medium. The composites were prepared by simple mechanical alloying of metallic iron and magnetite in different proportions, i.e. Fe(0) 25, 50, 75 and 90wt%. While after 3h of reaction pure Fe(0) and pure Fe3O4 showed only a low reduction efficiency of 15% and 25% Cr(VI) conversion, respectively, the composites, in particular Fe(0)(25wt%)/Fe3O4, showed a remarkable activity with ca. 65% Cr(VI) conversion. Kinetic experiments showed a high reaction rate during the first 3h, which subsequently decreased strongly, probably due to a pH increase from 6 to 8. Experiments with composites based on Fe(0)/alpha-Fe2O3, Fe(0)/gamma-Fe2O3 and Fe(0)/FeOOH showed very low activities, suggesting that Fe(oct)2+ in the magnetite structure plays an important role in the reaction. Scanning and high resolution electron microscopies and M?ssbauer spectra (transmission and conversion electron M?ssbauer spectroscopy) indicated that the mechanical alloying process promotes a strong interaction and interface between the metallic and oxide phases, with the Fe(0) particles completely covered by Fe3O4 particles. The high efficiency of the composite Fe(0)/Fe3O4 for Cr(VI) reduction is discussed in terms of a special mechanism where an electron is transferred from Fe(0) to magnetite to reduce Fe(oct)3+ to Fe(oct)2+, which is active for Cr(VI) reduction.     

Effect of Fe (III) on acid degradation of methylparathion

A study was undertaken to determine the transformation kinetic of methylparathion (O, O, -dimethyl O-4 nitrophenylphosphorotioate) in the presence of Fe(III) between pH 2 and 7. The Fe(III) was not electroactive under the conditions used in this study, and polarographic signals were exhibited by methylparathion and main degradation product only. Data suggest that hydrolysis of methylparathion in an acid medium is catalyzed by Fe(III) and the pesticide did not degrade in this medium without this cation. Methylparathion degradation was observed at all the pHs studied and was independent of the predominant chemical form of Fe(III) in the aqueous medium. The reaction was first-order with pH-dependent rate constant (k) values ranging from 3.3 x 10(- 3) h(- 1) to 7.0 x 10(- 3) h(- 1). The k values increased as pH decreased, suggesting that Fe(III) acted as an electrophile in the reaction mechanism.     

Chlorination of bisphenol A: kinetics and by-products formation

The kinetics of initial chlorination of bisphenol A (BPA) was studied between pH 2 and 11 at room temperature (20 +/- 2 degrees C). pH Profile of the apparent second-order rate constant of the reaction of BPA with chlorine were modeled considering the elementary reactions of HOCl with BPA species and an acid-catalyzed reaction. The predominant reactions at near neutral pH were the reactions of HOCl with the two phenolate species of BPA (k = 3.10 x 10(4) M(-1)s(-1) for BPA- and 6.62 x 10(4) M(-1) s(-1) for BPA(2-)). At near neutral pH, half-life times of BPA were calculated to be less than 1.5 h for chlorine residual higher than 0.2 mg l(-1). Chlorination of synthetic treated waters spiked with BPA showed that BPA disappeared within 4 h and that chlorinated bisphenol A congeners were rapidly formed and remained in solution for up to 10-20 h when low chlorine dosages are applied (0.5-1 mg l(-1)). To limit their presence in drinking water networks, it is then necessary to maintain high chlorine residuals that rapidly produce and decompose chlorinated bisphenol A congeners.     

Surface properties and catalytic performance of La(1-x)Sr(x)FeO(3) perovskite-type oxides for methane combustion

La(1-x)Sr(x)FeO(3) (x=0.0-1.0) perovskites were prepared and tested for the combustion of methane. X-ray diffraction (XRD) patterns revealed the presence of a single perovskite structure for substitutions 0x0.3, however Fe(2)O(3), SrCO(3) and SrFeO(3) phases were observed for substitutions x>0.3. The results of activity test indicate that with La(1-x)Sr(x)FeO(3) as the catalyst, the combustion of methane can take place at low temperatures around 400 degrees C. Partial substitution of La with Sr increases the activity and an optimal substitution fraction (x=0.5) exists in the La(1-x)Sr(x)FeO(3) catalysts. Catalyst activity can be well correlated to the product of the specific surface area and atomic ratio of Fe to La+Sr on the catalyst surface. Experimental results of O(2)-TPD and CH(4)-TPD in the range of 350-500 degrees C indicate that the amount of oxygen desorbed from the La(1-x)Sr(x)FeO(3) catalysts is far larger than that of methane. Therefore, it can be proposed that the catalytic oxidation of CH(4) over these catalysts proceeds with the surface reaction between CH(4) in the gas phase and the adsorbed O(2). Addition of water vapor or CO(2) to the feed inhibited catalyst activity, but the inhibition was reversible and became negligible at high reaction temperature.     

Effect of ferrate on green algae removal

Green algae Cladophora aegagropila, present in cooling water of thermal power plants, causes many problems and complications, especially during summer. However, algae and its metabolites are rarely eliminated by common removal methods. In this work, the elimination efficiency of electrochemically prepared potassium ferrate(VI) on algae from cooling water was investigated. The influence of experimental parameters, such as Fe(VI) dosage, application time, pH of the system, temperature and hydrodynamics of the solution on removal efficiency, was optimized. This study demonstrates that algae C. aegagropila can be effectively removed from cooling water by ferrate. Application of ferrate(VI) at the optimized dosage and under the suitable conditions (temperature, pH) leads to 100% removal of green algae Cladophora from the system. Environmentally friendly reduction products (Fe(III)) and coagulation properties favour the application of ferrate for the treatment of water contaminated with studied microorganisms compared to other methods such as chlorination and use of permanganate, where harmful products are produced.

     

Kinetics of OH radical reactions with dibenzo-p-dioxin and selected chlorinated dibenzo-p-dioxins

The pulsed laser photolysis/pulsed laser-induced fluorescence (PLP/PLIF) technique has been applied to obtain rate coefficients for OH + dioxin (DD) (k1), OH + 2-chlorodibenzo-p-dioxin (2-CDD) (k2), OH + 2,3-dichlorodibenzo-p-dioxin (2,3-DCDD) (k3), OH + 2,7-dichlorodibenzo-p-dioxin (2,7-DCDD) (k4), OH + 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD) (k5), OH + 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD) (k6), and OH + octachlorodibenzo-p-dioxin (OCDD) (k7) over an extended range of temperature. The atmospheric pressure (740 +/- 10 Torr) rate measurements are characterized by the following Arrhenius parameters (in units of cm3 molecule(-1) s(-1), error limits are 1 omega): k1(326-907 K) = (1.70+/-0.22) x 10(-12)exp(979+/-55)/T, k2(346-905 K) = (2.79+/-0.27) x 10(-12)exp(784+/-54)/T, k3(400-927 K) = 10(-12)exp(742+/-67)/T, k4(390-769 K) = (1.10+/-0.10) x 10(-12)exp(569+/-53)/T, k5(379-931 K) = (1.02+/-0.10) x 10(-12)exp(580+/-68)/T, k6(409-936 K) = (1.66+/-0.38) x 10(-12)exp(713+/-114)/T, k7(514-928 K) = (3.18+/-0.54) x 10(-12)exp(-667+/-115)/T. The overall uncertainty in the measurements, taking into account systematic errors dominated by uncertainty in the substrate reactor concentration, range from a factor of 2 for DD, 2-CDD, 2,3-DCDD, 2,7-DCDD, and 2,8-DCDD to +/- a factor of 4 for 1,2,3,4-TCDD and OCDD. Negative activation energies characteristic of an OH addition mechanism were observed for k1-k6. k7 exhibited a positive activation energy. Cl substitution was found to reduce OH reactivity, as observed in prior studies at lower temperatures. At elevated temperatures (500 K < T < 500 K), there was no experimental evidence for a change in reaction mechanism from OH addition to H abstraction. Theoretical calculations suggest that H abstraction will dominate OH reactivity for most if not all dioxins (excluding OCDD) at combustion temperatures (>1000 K). For OCDD, the dominant reaction mechanism at all temperatures is OH addition followed by Cl elimination.     

Electrochemical monitoring of methylparathion degradation in an acid aqueous medium in presence of Cu(II)

A study was undertaken to determine the effect of Cu(II) in degradation of methylparathion (o,o-dimethyl o,4-nitrophenyl phosphoriotioate) in acid medium. Initial electrochemical characterization of Cu(II) and methylparathion was done in an aqueous medium at a pH range of 2-7. Cu(II) was studied in the presence of different anions and it was observed that its electroactivity depends on pH and is independent of the anion used. Methylparathion had two reduction signals at pH < or = 6 and only one at pH > 6. The pesticide's transformation kinetic was then studied in the presence of Cu(II) in acid buffered aqueous medium at pH values of 2, 4, and 7. Paranitrophenol appeared as the only electroactive product at all three pH values. The reaction was first order and had k values of 5.2 x 10(-3) s(-1) at pH 2, 5.5 x 10(-3) s(-1) at pH 4 and 9.0 x 10(-3) s(-1) at pH 7. It is concluded that the principal degradation pathway of methylparathion in acid medium is a Cu(II) catalyzed hydrolysis reaction.