Dechlorination of polychlorinated dibenzo-p-dioxins catalyzed by noble metal catalysts under mild conditions

Dechlorination of polychlorinated dibenzo-p-dioxins such as 2,7-dichlorodibenzo-p-dioxin (2,7-DCDD) and 1,2,6,7-tetrachlorodibenzo-p-dioxin (1,2,6,7-TCDD) was carried out in a solution of NaOH in 2-propanol in the presence of carbon-supported noble metal catalyst (Pd/C or Rh-Pt/C) at temperatures between 23 and 35 degrees C. At initial concentrations of 140-240 micrograms/ml, 2,7-DCDD and 1,2,6,7-TCDD were efficiently converted to a chlorine-free product, dibenzo-p-dioxin (DD), in high yield (60-80%). The conversion of 2,7-DCDD and 1,2,6,7-TCDD and the yield of DD were hardly affected by the atmosphere (N2 or air). We postulate that the displacement of aromatic chlorines by hydrogen selectively occurs on the catalyst, involving hydrogen-transfer from 2-propanol to the substrates.     

Kinetic studies of the reaction of hydroxyl radicals with trichloroethylene and tetrachloroethylene

Rate coefficients are reported for the gas-phase reaction of the hydroxyl radical (OH) with C2HCl3 (k(1)) and C2Cl4 (k2) over an extended temperature range at 740+/-10 Torr in a He bath gas. These absolute rate measurements were accomplished using a laser photolysis/laser-induced fluorescence (LP/LIF) technique under slow flow conditions. The simple Arrhenius equation adequately describes the low temperature data for k1 (<650 K) and the entire data set for k2 and is given by (in units of cm3 molecule(-1) s(-1)): k1(291 - 650 K) = (9.73+/-1.15) x 10(-13) exp (158.7+/-44.0)/T, k2(293 - 720 K ) = (1.53+/-0.14) x 10(-12) exp (-688.2+/-67.5)/T. Error limits are 2sigma values. The room temperature values for k1 and k2 are within +/-2sigma of previous data using different techniques. The Arrhenius activation energies for k1 and k2 are a factor of 2-3 lower than previously reported values. The experimental measurements for both k1 and k2 in conjunction with transition state and variation transition state theory calculations infer an OH addition mechanism. The lack of a measurable kinetic isotope effect for k1 is consistent with this mechanism. Insight into the subsequent reactions of the chemically activated intermediate are presented in the form of potential energy diagrams derived from ab initio calculations.     

Kinetics of reductive dechlorination of 1,2,3,4-TCDD in the presence of zero-valent zinc

Polychlorinated dibenzo-p-dioxins (PCDDs) are toxic and widespread persistent organic pollutants (POPs). Cost-effective technologies for destroying or detoxifying PCDDs are in high demand. The overall purpose of this study was to develop a zero-valent zinc based technology for transforming toxic PCDDs to less- or non-toxic forms. We measured the dechlorination rates of 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD) in the presence of zero-valent zinc under aqueous conditions, identified the daughter compounds of the reaction, and constructed possible pathways for the reactions. The reaction rates of daughter compounds with zero-valent zinc were also measured independently. Our results showed that the zero-valent zinc is a suitable candidate for reducing PCDDs. Reductive dechlorination of 1,2,3,4-TCDD was stepwise and complete to dibenzo-p-dioxin (DD) mainly via 1,2,4-trichlorodibenzo-p-dioxin (1,2,4-TrCDD), 1,3-dichlorodibenzo-p-dioxin (1,3-DCDD), 1-chlorodibenzo-p-dioxin (1-MCDD) to DD and via 1,2,4-TrCDD, 2,3-dichlorodibenzo-p-dioxin (2,3-DCDD), 2-chlorodibenzo-p-dioxin (2-MCDD) to DD. In each separate system, the observed half-lives of 1,2,3,4-TCDD, 1,2,3-TrCDD, 1,2,4-TrCDD, 1,2-DCDD, 1,3-DCDD, 1,4-DCDD and 2,3-DCDD are 0.56, 2.62, 5.71, 24.93, 41.53, 93.67 and 169.06 h respectively. The tendency of rate constant follows TCDD>TrCDD>DCDD. Our results suggest that zero-valent zinc is a suitable candidate for rapidly reducing highly chlorinated PCDDs to less or non-chlorinated daughter products.     

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.     

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.     

Temperature dependence of Henry's law constants of metolachlor and diazinon

A dynamic system based on the water/air equilibrium at the interface within the length of a microporous tube has been used to determine experimentally the Henry's law constants (HLC) of two pesticides: metolachlor and diazinon. The measurements were conducted over the temperature range 283-301 K. At 293 K, HLCs values are (42.6+/-2.8) x 10(3) (in units of M atm(-1)) for metolachlor and (3.0+/-0.3)x10(3) for diazinon. The obtained data were used to derive the following Arrhenius expressions: HLC=(3.0+/-0.4) x 10(-11) exp((10,200+/-1,000)/T) for metolachlor and (7.2+/-0.5) x 10(-15) exp((11,900+/-700)/T) for diazinon. At a cumulus cloud temperature of 283 K, the fractions of metolachlor and diazinon in the atmospheric aqueous phase are about 57% and 11% respectively. In order to evaluate the impact of a cloud on the atmospheric chemistry of both studied pesticides, we compare also their atmospheric lifetimes under clear sky (tau(gas)), and cloudy conditions (tau(multiphase)). The calculated multiphase lifetimes (in units of hours) are significantly lower than those in gas phase at a cumulus temperature of 283 K (in parentheses): metolachlor, 0.4 (2.9); diazinon, 1.9 (5.0).     

A laser flash photolysis study of the decay of SO4- and Cl2- radical anions in the presence of Cl- in aqueous solutions

The rate constant for the reaction of sulphate radical (SO4-) with Cl- has been determined using laser photolysis, at 248 nm, of peroxodisulphate anions to produce the radicals and time resolved optical absorption of the transient species (at 450 or 480 nm for SO4- and 350 nm for Cl2-) for the kinetic determinations. The experiments were performed, in the absence of added sulphate, as a function of temperature and ionic strength and yielded (at an ionic strength of 0.0157 M): kIV = (9.90+/-0.16) x 10(9) exp((-7.12+/-2.0) kJ mol(-1)/RT) M(-1) s(-1), where the errors reflect the 2sigma statistical error. This reaction produces Cl2-, the formation and decay of which were also monitored allowing a determination of the rate constant of its second-order self-recombination reaction which gave k = (6.50+/-1.40) x 10(8) M(-1) s(-1) at 293 K and zero ionic strength.     

Distribution equilibrium of mercury (II) chloride between water and air applied to flue gas scrubbing

In the literature, different values of the distribution coefficient KH for HgCl2 between water and air are present in a range that spans more than 3 orders of magnitude. In order to determine if a waste incineration scrubber solution could become saturated with regard to HgCl2, an accurate experimental determination of the distribution constant of HgCl2 at elevated temperatures is needed. In this work, the coefficient has been determined at four different temperatures between 10 and 50 degrees C. The Arrhenius expression obtained is 5.5 x 10(5) x exp[-(8060 +/- 2200)/T] with a corresponding enthalpy for the process HgCl2(aq)<==>HgCl2(g) of 67 +/- 20 kJ/mole. KH at 293 K was found to be approximately 5 x 10(-7) atm M-1, which is in almost perfect agreement with an earlier study. Applying the obtained KH values to waste incineration scrubber conditions shows that no major saturation effect will occur.     

Rat metabolism of polychlorinated dibenzo-p-dioxins

In rats, dibenzo-p-dioxin, 1-chlorodibenzo-p-dioxin, 2-chlorodibenzo-p-dioxin, 2,3-dichlorodibenzo-p-dioxin, 2,7-dichlorodibenzo-p-dioxin, 1,2,4-trichlorodibenzo-p-dioxin and 1,2,3,4-tetrachlorodibenzo-p-dioxin are metabolized to mono- and dihydroxy derivatives, whilst in case of dibenzo-p-dioxin and both the two monochloro isomers, also sulphur containing metabolites are excreted. Primary hydroxylation exclusively takes place at the 2-, 3-, 7- or 8-position in the molecule. In none of the experiments metabolites resulting from fission of the C-O bonds (ortho, ortho'-dihydroxychlorodiphenyl ethers, chlorocatechols) or hydroxylated derivatives thereof, were detected. No metabolites were found from octachlorodibenzo-p-dioxin.     

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.     

Enhanced degradation of carbazole and 2,3-dichlorodibenzo-p-dioxin in soils by Pseudomonas resinovorans strain CA10

We studied the degradation of carbazole (CAR) and 2,3-dichlorodibenzo-p-dioxin (2,3-DCDD) in soils inoculated with carbazole- and dioxin-degrader Pseudomonas resinovorans strain CA10. By using Tn5-based transposon delivery systems, this bacterium was chromosomally marked with a tandem green fluorescent protein (gfp) gene. Real-time competitive PCR and direct counting using the (gfp) marker were employed to monitor the total number of carbazole 1,9a-dioxygenase gene (carAa) and survival of CA10 cells in the soil and soil slurry microcosms. Bioaugmentation studies indicated that the survival of the marked CA10 cells in soil microcosms was strongly influenced by pH and organic matter. While the number of the marked CA10 cells decreased rapidly in pH 6 with low organic matter, a high cell density was maintained in pH 7.3 with 2.5% organic matters up to 21 days after inoculation. In pH 7.3 soil, the period needed for complete degradation of CAR (100 microg kg(-1)) was markedly shortened from 21 to 7 days by the inoculation with the CA10 cells. Single inoculation of CA10 cells into the soil slurry system of 2,3-DCDD-contaminated soil enhanced the degradation of 2,3-DCDD from 25.0% to 37.0%. In this system, the population density of CA10 cells and the total number of carAa gene were maintained up to 14 days after inoculation. By repeated inoculation (every 2 days) with CA10 cells each at a density of 10(9) CFU g(-1) of soil, almost all of the 2,3-DCDD (1 microg kg(-1)) was degraded within 14 days. Results of these experiments suggest that P. resinovorans strain CA10 may be an important resource for bioremediation of CAR and chlorinated dibenzo-p-dioxin in contaminated soils.     

Pilot survey monitoring pharmaceuticals and related compounds in a sewage treatment plant located on the Mediterranean coast

A one-year monitoring study was performed to evaluate the occurrence, persistence and fate of a group of 14 organic compounds in a sewage treatment plant (STP) located in the south of Spain. These results are part of a more extensive study, financed by the Spanish Ministry of Research with the aim to evaluate the traceability of new pollutants on the Mediterranean coast and to determine the removal efficiency of sewage treatment plants (STP) for these pollutants. The compounds which have been analyzed include pharmaceuticals of various therapeutic categories (ibuprofen, acetaminophen, dipyrone, diclofenac, carbamazepine and codeine), pesticides (chlorfenvinfos and permethrin), caffeine, triclosan, bisphenol A and three of their more relevant metabolites (1,7-dimethylxanthine, carbamazepine 10,11-epoxide and 2,7/2,8-dichlorodibenzo-p-dioxin). An SPE/GC-MS multi-residue analytical method was developed and validated to facilitate simultaneous determination of these compounds in both influent and effluent wastewater. The method provided mean recoveries higher than 75%, with the exception of 2,7/2,8-dichlorodibenzo-p-dioxin, dipyrone and permethrin which exhibited recoveries lower than 22%. The overall variability of the method was below 14%. The method detection limit (LOD) was between 1 and 100 ng l(-1) and precision, which was calculated as relative standard deviation (RSD), ranged from 1.8% to 11.2%. The application of the proposed method has allowed the identification of all the target compounds at mean concentrations which ranged from 0.12 to 134 microg l(-1) in the influent and from 0.09 to 18.0 microg l(-1) in the effluent. The removal efficiencies of the STP for these compounds varied from 20% (carbamazepine) to 99% (acetaminophen), but in all cases resulted insufficient in order to avoid their presence in treated water and subsequently in the environment.     

Temperature dependence of hydroxyl radical formation in the hv/Fe3+/H2O2 and Fe3+/H2O2 systems

The thermal enhancement of the formation of *OH by the hv/Fe(III)/H2O2 system (including the Fe(III)/H2O2 system) was quantitatively investigated with reaction temperatures ranging from 25 to 50 degrees C. A temperature dependent kinetic model for the hv/Fe(III)/H2O2 system, incorporating 12 major reactions with no fitted rate constants or activation energies, was developed, and successfully explained the experimental measurements. Particularly, the thermal enhancement of Fe(OH)2+ photolysis which is the most significant step in the hv/Fe(III)/H2O2 system was effectively explained by two factors; (1) the variation of the Fe(OH)2+ concentration with temperature, and (2) the temperature dependence of the quantum yield for Fe(OH)2+ photolysis (measured activation energy=11.4 kJ mol(-1)). Although in both the hv/Fe(III)/H2O2 and Fe(III)/H2O2 systems, elevated temperatures enhanced the formation of *OH, the thermal enhancement was much higher in the dark Fe(III)/H2O2 system than the hv/Fe(III)/H2O2 system. Furthermore, it was found that the relative thermal enhancement of the formation of *OH in the presence of *OH scavengers (tert-butyl alcohol) was magnified in the Fe(III)/H2O2 system but was not in the hv/Fe(III)/H2O2 system.     

Dechlorination/hydrogenation and destruction reactions of PCDDs in OCDD-added fly ash heated under vacuum

Octachlorodibenzo-p-dioxin (OCDD)-added, pretreated fly ash was heated under vacuum at sample temperatures ranging from T(s)=450 to 650 K. The fly ash and liquid nitrogen-cooled trap samples were analyzed for DD/DF through OCDD/DF. The total amounts of DD through OCDD decrease with increasing T(s), which indicates that dechlorination/hydrogenation (DCH) reactions are not the only reaction channels. Reduction of toxic equivalent (TEQ) for PCDDs by more than 99% was achieved in the fly ash by the vacuum heat treatment at T(s)=650 K for 4 h. The total amount of PCDDs and DD detected in the liquid nitrogen-cooled trap relative to that of added OCDD was about 17%, i.e., PCDDs and DD which were adsorbed to the fly ash surfaces can evaporate into the gaseous phase. The difference between the evaporation behavior of PCDDs in the present and the previous studies is discussed in the light of their states of existence.     

Photooxidation of naphthalenesulfonic acids: comparison between processes based on O(3), O(3)/activated carbon and UV/H(2)O(2)

The aim of the present study was to analyze and compare the efficacy of UV photodegradation with that of different advanced oxidation processes (O(3), UV/H(2)O(2), O(3)/activated carbon) in the degradation of naphthalenesulfonic acids from aqueous solution and to investigate the kinetics and the mechanism involved in these processes. Results obtained showed that photodegradation with UV radiation (254 nm) of 1-naphthalenesulfonic, 1,5-naphthalendisulfonic and 1,3,6-naphthalentrisulfonic acids is not effective. Presence of duroquinone and 4-carboxybenzophenone during UV irradiation (308-410 nm) of the naphthalenesulfonic acids increased the photodegradation rate. Addition of H(2)O(2) during irradiation of naphthalenesulfonic acids accelerated their elimination, due to the generation of ()OH radicals in the medium. Comparison between UV photodegradation 254 m and the advanced oxidation processes (O(3), O(3)/activated carbon and UV/H(2)O(2)) showed the low-efficacy of the former in the degradation of these compounds from aqueous medium. Thus, among the systems studied, those based on the use of UV/H(2)O(2) and O(3)/activated carbon were the most effective in the oxidation of these contaminants from the medium. This is because of the high-reactivity of naphthalenesulfonic acids with the *OH radicals generated by these two systems. This was confirmed by the values of the reaction rate constant of *OH radicals with these compounds k(OH), obtained by competitive kinetics (5.7 x 10(9) M(-1) s(-1), 5.2 x 10(9) M(-1) s(-1) and 3.7 x 10(9) M(-1) s(-1) for NS, NDS and NTS, respectively).     

UV/ozone degradation of gaseous hexamethyldisilazane (HMDS)

As a carcinogen, hexamethyldisilazane (HMDS) is extensively adopted in life science microscopy, materials science and nanotechnology. However, no appropriate technology has been devised for treating HMDS in gas streams. This investigation evaluated the feasibility and effectiveness of the UV (185+254nm) and UV (254nm)/O(3) processes for degradation of gaseous HMDS. Tests were performed in two batch reactors with initial HMDS concentrations of 32-41mgm(-3) under various initial ozone dosages (O(3) (mg)/HMDS (mg)=1-5), atmospheres (N(2), O(2), and air), temperatures (28, 46, 65 and 80 degrees C), relative humilities (20%, 50%, 65%, 99%) and volumetric UV power inputs (0.87, 1.74, 4.07 and 8.16Wl(-1)) to assess their effects on the HMDS degradation rate. Results indicate that for all conditions, the decomposition rates for the UV (185+254nm) irradiation exceeded those for the UV (254nm)/O(3) process. UV (185+254nm) decompositions of HMDS displayed an apparent first-order kinetics. A process with irradiation of UV (185+254nm) to HMDS in air saturated with water at temperatures of 46-80 degrees C favors the HMDS degradation. With the condition as above and a P/V of around 8Wl(-1), k was approximately 0.20s(-1) and a reaction time of just 12s was required to degrade over 90% of the initial HMDS. The main mechanisms for the HMDS in wet air streams irradiated with UV (185+254nm) were found to be caused by OH free-radical oxidation produced from photolysis of water or O((1)D) produced from photolysis of oxygen. The economic evaluation factors of UV (185+254nm) and UV (254nm)/O(3) processes at different UV power inputs were also estimated.     

Pentachlorophenol association with fulvic acids from recycled wastes

The apparent water solubility of pentachlorophenol was measured at pH=6 and at 25 degrees C in pure water, aqueous solutions of three salts (NaCl, KNO(3) and CaCl(2) at 0.010, 0.10 and 1.0M) and in aqueous solutions of three fulvic acids samples extracted from a natural soil (sFA), composted sewage sludge (csFA) and composted livestock's material (lsFA). A solubility enhancement method was developed for the measurement of partition coefficients (K(oc), L/kg organic carbon). Pentachlorophenol associates strongly with the fulvic acid samples and the calculated K(oc) were the following (averages and standard deviations): (sFA) (211+/-22) x 10(2), (csFA) (253+/-26) x 10(2), (lsFA) (235+/-10) x 10(2). For comparison purposes the K(oc) for pyrene were also calculated for the three FA samples and were the following: (sFA) (119+/-10) x 10(2), (csFA) (239+/-21) x 10(2), (lsFA) (92+/-10) x 10(2). The analysis of variance (one-way ANOVA) of the effect of the type of FA sample on the solubilization of pentachlorophenol and pyrene shows that this factor causes significant differences on the aqueous solubilization of these two organic substances.     

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.     

Cyclooctane tropospheric degradation initiated by reaction with Cl atoms

Goal, Scope and Background Within the non-methane hydrocarbons, alkanes constitute the largest fraction of the anthropogenic emissions of volatile organic compounds. For the case of cyclic alkanes, tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atom reaction rate constants are generally one order of magnitude larger than those of OH. In the present work, the reaction of cyclooctane with Cl atoms has been studied within the temperature range of 279–333 K. Methods The kinetic study has been carried out using the fast flow tube technique coupled to mass spectrometry detection. The reaction has been studied under low pressure conditions, p=1 Torr, with helium as the carrier gas. Results The measured room temperature rate constant is very high, k=(2.63±0.54)×10⁻¹⁰ cm³molecule⁻¹s⁻¹, around 20 times larger than that for the corresponding OH reaction. We also report the results of the rate coefficients obtained at different temperatures: k = (3.5±1.2)×10⁻¹⁰ exp[(−79±110)/T] cm³ molecule⁻¹ s⁻¹ within the range of 279–333 K. This reaction shows an activation energy value close to zero. Discussion Quantitative formation of HCl has been observed, confirming the mechanism through H-atom abstraction. The reactivity of cyclic alkanes towards Cl atoms is clearly dependent on the number of CH₂ groups in the molecule, as is shown by the increase in the rate constant when the length of the organic chain increases. This increase is very high for the small cyclic alkanes and it seems that the reactions are approaching the collision-controlled limit for cyclohexane and cyclooctane. Conclusions These results show that gas-phase reaction with Cl in marine or coastal areas is an efficient sink (competing with the gas phase, OH initiated degradation) for the Earth’s emissions of cyclooctane, with a Cl-based lifetime ranging from 11 to 2000 hours, depending on the location and time of day. Recommendations and Perspectives Cl and OH fast reactions with cyclooctane are expected to define the lifetime of cyclooctane emissions to the atmosphere. The degradation of cyclooctane occurs in a short period of time and consequently (under conditions of low atmospheric mass transport), close to the emission sources enabling a significant contribution to local effects, like the formation of photochemical smog. ESS-Submission Editor: Prof. Dr. Gerhard Lammel (lammel@recetox.muni.cz)     

Kinetics of the Homogeneous Gas Phase Hydrolysis of CCl3COCl,CCl2HCOCl,CH2CICOCl and COCl2

The homogeneous gas phase hydrolysis kinetics of the above compounds has been investigated in the 470° to 620°K temperature range. The following biomolecular rate constants were obtained: k(CCl₃COCl) = 2.54 × 10⁶ exp (?18,350 ± 1750)/RT, k(CClH₂COCl) = 1.14 × 10⁸ exp (?22,630 ± 780)/RT, and fr(COCl₂) = 9192 exp (?14,200 ± 2100)/RT liter mole^?1 sec^?1. Experimental difficulties prevented data being obtained for CHCl₂COCl. The half lives of these species with respect to homogeneous gas phase hydrolysis in the atmosphere have been estimated and it is concluded that this is not an efficient conversion process. Heterogeneous hydrolysis by water droplets may be a more efficient atmospheric scavenging process for these compounds.