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.     

Oxidation of MCPA and 2,4-D by UV radiation, ozone, and the combinations UV/H2O2 and O3/H2O2

The phenoxyalkyl acid derivative herbicides MCPA (4-chloro 2-methylphenoxyacetic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid) were oxidized in ultrapure water by means of a monochromatic UV irradiation and by ozone, as well as by the combinations UV/H2O2 and O3/H2O2. In the direct photolysis of MCPA, the quantum yield at 20 degrees C was directly evaluated and a value of 0.150 mol Eins(-1) was obtained in the pH range 5-9, while a lower value of 0.41 x 10(-2) mol Eins(-1) was determined at pH=3. Similarly, for 2,4-D a value of 0.81 x 10(-2) mol Eins(-1) was deduced, independent of the pH of work. The influence of the additional presence of hydrogen peroxide was established in the combined process UV/H2O2, and the specific contribution of the radical pathway to the global photo-degradation was evaluated. The oxidation by ozone and by the combination O3/H2O2 was also studied, with the determination of the rate constants for the reactions of both herbicides with ozone and hydroxyl radicals at 20 degrees C. These rate constants for the direct reactions with ozone were 47.7 and 21.9 M(-1) s(-1) for MCPA and 2,4-D respectively, while the found values for the rate constants corresponding to the radical reactions were 6.6 x 10(9) and 5.1 x 10(9) M(-1) s(-1).     

Degradation of octylphenol and nonylphenol by ozone - part I: direct reaction

This aqueous reaction between ozone and two alkylphenols (APs), namely octylphenol (OP) and nonylphenol (NP), has been investigated. Both compounds are important endocrine disrupting chemicals, which arise from the biodegradation of alkylphenol ethoxylates and are often found at relatively high concentrations in wastewater effluents. In this paper the results of an experimental study are presented which provide values for the reaction rate constants between molecular ozone and undissociated OP and NP, and overall reaction rate constants for the degradation of the two APs at pH values in the range of 7-9. The kinetic rate constants for OP and NP degradation by molecular ozone were 4.33(+/-0.18) x 10(4) and 3.90(+/-0.10) x 10(4) M(-1) s(-1), and the reaction stoichiometry was similar in both cases and equal to approximately 1.3:1 ([O3]:[AP]). The overall second order reaction rate constants for the two APs increased significantly with increasing pH, which is believed to be mainly due to the increasing influence of indirect radical reaction with increasing pH; this aspect is considered in more detail in a companion paper. A preliminary investigation of the reaction mechanism suggests that an initial product of ozonation is hydroxyl-alkyl phenol.     

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.     

Light-induced disappearance of nitrite in the presence of iron (III)

Understanding of rapid disappearance of nitrite in natural waters and its impact on nitrogen natural cycling has remained limited. We found that NO2- disappeared rapidly in pH 3.2 aqueous Fe(III) solutions both in sunlight and in 356 nm light. Quantum yields of the NO2- loss at 356 nm were 0.049-0.14 for initial levels of 10-80 microns NO2- and 200 microns Fe(III). The NO2- loss (at 356 nm) followed apparent first-order kinetics. The rate constants were 1.3 x 10(-3) (40 microns NO2-) and 4.1 x 10(-4) s-1 (80 microns NO2-) for 100 microns Fe(III), and 2.3 x 10(-3) (40 microns NO2-) and 7.5 x 10(-4) s-1 (80 microns NO2(-1)) for 200 microns Fe(III) (t1/2 = 8.7, 27.9, 5.1, and 15.3 min, respectively). The rate constants were directly proportional to [Fe(III)]0 and inversely proportional to [NO2-]0. Agreement between the rate constants obtained experimentally and those calculated mechanistically supports the hypothesis that NO2- was oxidized to NO2 by .OH radicals from photolysis of FeOH2+ complexes, and at high [NO2-]0 (e.g., 80 microns) relative to [Fe(III)]0, hydrolysis of NO2 or N2O4 to form NO3- and NO2- could be significant. This study showed that light and Fe(III)-induced oxidation of NO2- (rate = approximately 10(-1)-10(-2) microns s-1) was more rapid than its direct photolysis (rate = approximately 10(-4) microns s-1), and the photolysis could be a significant source of .OH radicals only in cases where the Fe(III) level is much lower than the NO2- level ([Fe(III)]/[NO2-] < 1/80). This study suggests that the light and Fe(III)-induced oxidation of NO2- would be one potential important pathway responsible for the rapid transformation of NO2- in acidic surface waters, especially those affected by acid-mine drainage or volcanic activities. This study also may be of interest for modeling certain acidic atmospheric water environments.     

Removal of selected endocrine disrupting chemicals and personal care products in surface waters and secondary wastewater by ozonation

This study investigated the removal of parabens, N,N-diethyl-m-toluamide (DEET), and phthalates by ozonation. The second-order rate constants for the reaction between selected compounds with ozone at pH 7 were of (2.2 +/-0.2) X 10(6) to (2.9 +/-0.3) X 10(6) M 1/s for parabens, (2.1+/- 0.3) to (3.9 +/-0.5) M-1/s for phthalates, and (5.2 +/-0.3) M-1/s for DEET. The rate constants for the reaction between selected compounds with hydroxyl radical ranged from (2.49 +/-0.06) x 10(9) to (8.5 +/-0.2) x 10(9) M-1/s. Ozonation of selected compounds in secondary wastewater and surface waters revealed that ozone dose of 1 and 3 mg/L yielded greater than 99% depletion of parabens and greater than 92% DEET and phthalates, respectively. In addition, parabens were found to transform almost exclusively through the reaction with ozone, while DEET and phthalates were transformed almost entirely by hydroxyl radicals (.OH).     

Anaerobic transformation of chlorophenols in methanogenic sludge unexposed to chlorophenols

Transformation of all 19 chlorophenol (CP) isomers was investigated in a laboratory anaerobic methanogenic sludge that had not been exposed to synthetic chemicals. Concentration of CP was analyzed over time to calculate disappearance rate constants using first-order reaction kinetics and all possible CP degradation pathways were estimated. The rate constants ranged between 0.46 x 10(-3) and 0.161 day(-1). CPs were transformed via dechlorination. The chlorine atom at the ortho-position was the most easily dechlorinated, whereas dechlorination rate at the para-position was lowest. The overall pathways of CP transformation were much less diverse than that we previously found for contaminated sediment. The Dolfing hypothesis of microbial selection of the most thermodynamically favorable pathways was not applicable for CP transformation in this study as well as previous study performed by our group.     

Kinetic studies of endosulfan photochemical degradations by ultraviolet light irradiation in aqueous medium

Kinetic studies of endosulfan photochemical degradation in controlled aqueous systems were carried out by ultraviolet light irradiation at lambda = 254 nm. The photolysis of (alpha + beta: 2 + 1) endosulfan, alpha-endosulfan and beta-endosulfan were first-order kinetics. The observed rate constants obtained from linear least-squares analysis of the data were 1 x 10(-4) s(-1); 1 x 10(-4) s(-1); and 2 x 10(-5) s(-1), respectively, and the calculated quantum yields (phi) were 1, 1 and 1.6, respectively. Preliminary differential pulse polarographic (DPP) analysis allowed to observe the possible endosulfan photochemical degradation pathway. This degradation route involves the formation of the endosulfan diol, its transformation to endosulfan ether and finally the ether's complete degradation by observing the potential shifts.     

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.     

Enhanced chemical oxidation of aromatic hydrocarbons in soil systems

Fenton's destruction of benzene, toluene, ethylbenzene, and xylene (BTEX) was investigated in soil slurry batch reactors. The purpose of the investigation was to quantify the enhancement of oxidation rates and efficiency by varying process conditions such as iron catalyst (Fe(II) or Fe(III); 2, 5, and 10mM), hydrogen peroxide (H2O2; 30, 150, 300 mM), and metal chelating agents (l-ascorbic acid, gallic acid, or N-(2-hydroxyethyl)iminodiacetic acid). Rapid contaminant mass destruction (97% after 3h) occurred in the presence of 300 mM H2O2 and 10 mM Fe(III). An enhanced removal rate (>90% removal after 15 min and 95% removal after 3h) was also observed by combining Fe(III), N-(2-hydroxyethyl)iminodiacetic acid and 300 mM H2O2. The observed BTEX mass removal rate constants (3.6-7.8 x 10(-4)s(-1)) were compared to the estimated rate constants (4.1-10.1 x 10(-3)s(-1)). The influence of non-specific oxidants loss (by reaction with iron hydroxides and soil organic matter) was also explored.     

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.     

Rapid reductive dechlorination of atrazine by zero-valent iron under acidic conditions

The dechlorination of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) via reaction with metallic iron under low-oxygen conditions was studied using reaction mixture pH values of 2.0, 3.0, and 3.8. The pH control was achieved through addition of sulfuric acid throughout the duration of the reaction. The lower the pH of the reaction mixture, the faster the degradation of atrazine. The surface area of the sulfuric acid-treated iron particles was 0.31 (+/- 0.01) m2 g-1 and the surface area normalized initial pseudo-first order rate constants (kSA, where rate = kSA x (surface area/l) x [Atrazine]) at pH values of 2.0, 3.0, and 3.8 were equal to, respectively, 3.0 (+/- 0.4) x 10(-3) min-1 m-2 l, 5 (+/- 3) x 10(-4) min-1 m-2 l, and 1 (+/- 1) x 10(-4) min-1 m-2 l. The observed products of the degradation reaction were dechlorinated atrazine (2-ethylamino-4-isopropylamino-1,3,5-triazine) and possibly hydroxyatrazine (2-ethylamino-4-isopropylamino-6-hydroxy-s-triazine). Triazine ring protonation may account, at least in part, for the observed effect of pH on atrazine dechlorination via metallic iron.     

Biodegradation of haloacetic acids by bacterial enrichment cultures

Haloacetic acids (HAAs) are toxic organic chemicals that are frequently detected in surface waters and in drinking water distribution systems. The aerobic biodegradation of HAAs was investigated in serum bottles containing a single HAA and inoculated with washed microorganisms obtained from enrichment cultures maintained on either monochloroacetic acid (MCAA) or trichloroacetic acid (TCAA) as the sole carbon and energy source. Biodegradation was observed for each of the HAAs tested at concentrations similar to those found in surface waters and in drinking water distribution systems. The MCAA culture was able to degrade both MCAA and monobromoacetic acid (MBAA) with pseudo-first order rate constants of 1.06 x 10(-2) and 1.13 x 10(-2) l(mg protein)(-1) d(-1), respectively, for concentrations ranging from 10(-5) to 2 mM. The pseudo-first order rate constant for TCAA degradation by the TCAA culture was 6.52 x 10(-3) l(mg protein)(-1) d(-1) for concentrations ranging from 5.33 x 10(-5) to 0.72 mM. The TCAA culture was also able to degrade MCAA with the rate accelerating as incubation time increased. Experiments with radiolabeled HAAs indicated that the 14C was primarily converted to 14CO2 with minor incorporation into cell biomass. The community structure of the enrichment cultures was analyzed by both cultivation-dependent and cultivation-independent approaches. Denaturing gradient gel electrophoresis (DGGE) of the PCR-amplified 16S rRNA gene fragments showed that each of the two enrichment cultures had multiple bacterial populations, none of which corresponded to HAA-degrading bacteria cultivated on HAA-supplemented agar plates. This research indicates that biodegradation is a potential loss mechanism for HAAs in surface waters and in drinking water distribution systems.     

Impact of pH buffer capacity of sediment on dechlorination of atrazine using zero valent iron

This research investigated the role of the pH buffer capacity of sediment on the dechlorination of atrazine using zero valent iron (ZVI). The buffer capacity of the sediment was quantified by batch experiments and estimated to be 5.0 cmol OH(-) . pH(-1). The sediments were spiked with atrazine at 7.25-36.23 mg kg(-1) (6.21 x 10(-7)-3.09 x 10(-6) mol atrazine . g(-1) sediment) for the batch experiments. The buffer capacity of the sediment maintained the sediment suspension at neutral pH, thereby enabling continuous dechlorination until the buffer capacity of the sediment was depleted. The pseudo-first order dechlorination constants were estimated to be in the range of 1.19 x 10(-2)-7.04 x 10(-2) d(-1) for the atrazine-spiked sediments.     

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.     

Fractionation of fulvic acids: characteristics and complexation with copper

Two fulvic acid samples isolated from Suwannee river (International Humic Substance Society) and Feeitsuey reservoir were subjected to gel filtration chromatography (GFC) for molecular size fractionation. The GFC-eluted samples were separated into three groups corresponding to the molecular weight ranges: < 220, 220-1000, and 1000-4000. Fluorescence quenching techniques were employed for determining the conditional stability coefficient and kinetic parameters of copper complexation with the three fractions of fulvic acids. Experimental conditions were pH 6, 5 x 10(-5)m total copper and 5 mg C litre(-1) of fulvic acids. The conditional stability coefficients of the fulvic acid fractions were in the order of 0.9-3.3 x 10(5)m(-1), and the forward and reverse rate constants were in the order of 6.9-12.4 x 10(3)m(-1) s(-1) and 3.5-8.0 x 10(-2) s(-1). Information could be useful in modelling copper transport in the hydrosphere.     

Mineralization of C.I. Reactive Yellow 84 in aqueous solution by sonolytic ozonation

The operational parameters and mechanism of mineralization of C.I. Reactive Yellow 84 (RY84), one of the azo dyes, in aqueous solution were investigated using sonolytic ozonation (US/O(3) oxidation). Of the pseudo-first-order degradation rate constants of TOC reduction, 9.0 x 10(-4), 7.3 x 10(-3) and 1.8 x 10(-2)min(-1) were observed with US, O3, and a combination of US and O3, respectively. These results illustrate that ozonation combined with sonolysis for removal of TOC is more efficient than ozonation alone or ultrasonic irradiation alone without considering the operating costs. With the initial pH value at 10.0, the ozone dose at 4.5 g h(-1), the energy density of ultrasound at 176 W l(-1), and the initial concentration of RY84 at 100 mg l(-1), the extent of mineralization measured as TOC loss was maximized. The variation of the concentrations of related ions (oxalate, formate, acetate, NO3(-), NO2(-), NH4(+), Cl(-), and SO4(2-)) during the reaction process was monitored. Other organic intermediates detected by GC/MS were N-methyleneaniline, phthalic acid, 4-hydroxyphthalic acid, isocyanatobenzene, aniline, 4-iminocyclohexa-2,5-dien-1-one, butene diacid and urea. Based on these findings, a tentative degradation pathway was proposed.     

Henry's law constants of phenol and mononitrophenols in water and aqueous sulfuric acid

Phenols are widely present in the atmosphere and nitration probably in the aerosol phase leads to nitrophenols. Nitration by nitric acid in sulfuric acid can be rapid, but little is known of the process under atmospheric conditions. The Henry's law constants K(H)(dagger) of phenol and 2-, 3- and 4-nitrophenol were all measured by a bubble stripping method as: 2820mol kg(-1) atm(-1) (at 298K), 147mol kg(-1) atm(-1) (at 298K), 1.6x10(4)mol kg(-1)atm(-1) (at 308K) and 2.1x10(4)mol kg(-1) atm(-1) (at 308K), respectively. The Henry's law constant of phenol in sulfuric acid systems is lower by more than a factor of two at 1020mol kg(-1) atm(-1) (at 298K) in 40wt% sulfuric acid, which is in line with salting-out of oxygen-containing aromatic compounds in water-sulfuric acid systems. The Henry's law constants of 2- and 4-nitrophenol behave differently and are almost independent of sulfuric acid concentration. The variation of K(H)(dagger) with temperature (T) described in terms of -dln(K(H)(dagger))/d(1/T) does not to vary with sulfuric acid concentration, suggesting enthalpy of dissolution for phenol is independent of sulfuric acid. The series of Henry's law constants measured here can describe the equilibrium situation for phenols in careful determinations of phase partitioning in the atmosphere.     

Aqueous solubility, Henry's law constants and air/water partition coefficients of n-octane and two halogenated octanes

New data on the aqueous solubility of n-octane, 1-chlorooctane and 1-bromooctane are reported between 1 degree C and 45 degrees C. Henry's law constants, K(H), and air/water partition coefficients, K(AW), were calculated by associating the measured solubility values to vapor pressures taken from literature. The mole fraction aqueous solubility varies between (1.13-1.60)x10(-7) for n-octane with a minimum at approximately 23 degrees C, (3.99-5.07)x10(-7) for 1-chlorooctane increasing monotonically with temperature and (1.60-3.44)x10(-7) for 1-bromooctane with a minimum near 18 degrees C. The calculated air-water partition coefficients increase with temperature and are two orders of magnitude lower for the halogenated derivatives compared to octane. The precision of the results, taken as the average absolute deviations of the aqueous solubility, the Henry's law constants, or the air/water partition coefficients, from appropriate smoothing equations as a function of temperature is of 3% for n-octane and of 2% and 4% for 1-chlorooctane and 1-bromooctane, respectively. A new apparatus based on the dynamic saturation column method was used for the solubility measurements. Test measurements with n-octane indicated the capability of measuring solubilities between 10(-6) and 10(-10) in mole fraction, with an estimated accuracy better than +/-10%. A thorough thermodynamic analysis of converting measured data to air/water partition coefficients is presented.     

Evidence for destruction of PCBs by the OH radical in urban atmospheres

Evidence for reaction of polychlorinated biphenyl (PCB) congeners with the hydroxyl (OH) radical in the troposphere was observed in diurnal variations in ambient gas-phase PCB concentrations at three urban sampling sites located in the Chicago, IL; Baltimore, MD; and Jersey City, NJ urban/industrial areas. The magnitude of the depletion of individual PCB congeners decreased by about 10-20% for each additional chlorine substituent, reflecting slower reaction rates for higher MW congeners with the OH radical. Octa- and nonachlorobiphenyls, which are largely unreactive with the OH radical, were used as tracers to investigate the effects of dilution on diurnal variation. The environmental rate constants for disappearance of the PCBs range from about 1.0 day(-1) for trichlorobiphenyls to about 0.3 day(-1) for hexachlorobiphenyls. Assuming a OH radical concentration of 3 x 10(6) molecules cm (-3), the second-order rate constants for reaction of specific congeners with the OH radical are consistent with laboratory measurements. More importantly, the relative reactivity of PCB homologues agrees well with the relationship predicted by other researchers from laboratory measurements, suggesting that losses of PCBs during daytime tropospheric transport are due at least in part to reactions with the OH radical.