Photodegradation of sulfonamides and their N 4-acetylated metabolites in water by simulated sunlight irradiation: kinetics and identification of photoproducts

Once released into the aquatic environment, pharmaceuticals may undergo different degradation processes. Photodegradation, for example, might be an important elimination process for light-sensitive pharmaceuticals, such as antibiotics. In this study, the fate of sulfonamides (sulfamethazine, sulfadiazine, and sulfamethoxazole) and their N ⁴-acetylated metabolites (N ⁴-acetylsulfadiazine, N ⁴-acetylsulfamethazine, and N ⁴-acetylsulfamethoxazole) under simulated sunlight irradiation was investigated. The irradiation resulted in total or almost total degradation (88 to 98 %) of the pharmaceuticals tested, except for sulfamethazine (52 %), during 24 h of irradiation. The photoproducts of all investigated pharmaceuticals have been analyzed using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Structure elucidation performed from photodegradation products of both, sulfonamides and their N ⁴-acetylated metabolites, clearly showed two major formation pathways. These were cleavage of the sulfonamide bond as well as SO₂ extrusion. In total, nine photoproducts were elucidated. Among these photoproducts, the tautomers of sulfamethoxazole and desulfonated products of sulfadiazine and sulfamethazine were also present. Tautomers of sulfadiazine and sulfamethazine have been characterized here for the first time as well as some photoproducts of sulfadiazine, sulfametoxazole, and their metabolites N ⁴-acetylsulfadiazine and N ⁴-acetylsulfametoxazole. The obtained results are an important piece in the complex puzzle for assessing the environmental fate of sulfonamides and their metabolites in the environment.     

Isoprene emission capacity for US tree species

Isoprene emission capacity measurements are presented from 18 North American oak (Quercus) species and species from six other genera previously found to emit significant quantities of isoprene. Sampling was conducted at physiographically diverse locations in North Carolina, Central California, and Northern Oregon. Emissions from several sun leaves of each species were measured at or near standard conditions (leaf temperature of 30°C and photosynthetically active radiation of 1000 μmol m⁻² s⁻¹) using environmentally controlled cuvette systems and gas chromatography with reduction gas detectors. Species mean emission capacity ranged from 39 to 158 μg C g⁻¹ h⁻¹ (mean of 86), or 22 to 79 nmol m⁻² s⁻¹ (mean of 44). These rates are 2–28 times higher than those previously reported from the same species, which were summarized in a recent study where isoprene emission rates were assigned based on published data and taxonomy. These discrepancies were attributed to differences in leaf environment during development, measurement technique (branch or plant enclosure versus leaf enclosure), and lack of environmental measurements associated with some of the earlier branch enclosure measurements. Mass-based emission capacities for 15 of 18 oak species, sweetgum (Liquidambar styraciflua), and poplars (Populus trichocarpa and P. deltoides) were within ranges used in current biogenic volatile organic compound (BVOC) emission models, while measured rates for the remaining three oak species, Nyssa sylvatica, Platanus occidentalis, Robinia pseudoacacia, Salix nigra, and Populus hybrids (Populus trichocarpa × P. deltoides) were considerably higher. In addition, mean specific leaf mass of the oak species was 30% higher than assumed in current emission models. Emission rates reported here and in other recent studies support recent conclusions that isoprene emission capacities for sun leaves of high emitting species may be better represented by a value of 100±50 μg C g⁻¹ h⁻¹ during hot summer conditions. We also find that intermediate isoprene emission rates previously suggested for some tree species may not represent their true emission capacities, and that broadleaf plant species may have either low (<1.0 μg C g⁻¹ h⁻¹) or very high (∼100 μg C g⁻¹ h⁻¹) genetic capacity to emit isoprene when mature foliage is exposed to a high ambient temperature and light environment.     

Photochemical behavior of chlorsulfuronR in water and in adsorbed phase

The photochemistry of the herbicide chlorsulfuron^R (2-chloro-N-[[4-methoxy-6-methyl-1.3.5-triazinyl-2-amino]carbonyl]benzene sulfonamide) was investigated in methanol, distilled water, natural creek-water, on silica gel and on montmorillonit surfaces. The rate of degradation was determined in outdoor and indoor experiments simulating tropospheric conditions (λ>290 nm). Two major photoproducts were identified in all cases.     

Light dependency of VOC emissions from selected Mediterranean plant species

The light, temperature and stomatal conductance dependencies of volatile organic compound (VOC) emissions from ten plant species commonly found in the Mediterranean region were studied using a fully controlled leaf cuvette in the laboratory. At standard conditions of temperature and light (30°C and 1000 μmol m⁻² s⁻¹ PAR), low emitting species (Arbutus unedo, Pinus halepensis, Cistus incanus, Cistus salvifolius, Rosmarinus officinalis and Thymus vulgaris) emitted between 0.1 and 5.0 μg (C) (total VOCs) g⁻¹ dw h⁻¹, a medium emitter (Pinus pinea) emitted between 5 and 10 μg (C) g⁻¹ dw h⁻¹ and high emitters (Cistus monspeliensis, Lavendula stoechas and Quercus sp.) emitted more than 10 μg (C) g⁻¹ dw h⁻¹. VOC emissions from all of the plant species investigated showed some degree of light dependency, which was distinguishable from temperature dependency. Emissions of all compounds from Quercus sp. were light dependent. Ocimene was one of several monoterpene compounds emitted by P. pinea and was strongly correlated to light. Only a fraction of monoterpene emissions from C. incanus exhibited apparent weak light dependency but emissions from this plant species were strongly correlated to temperature. Data presented here are consistent with past studies, which show that emissions are independent of stomatal conductance. These results may allow more accurate predictions of monoterpene emission fluxes from the Mediterranean region to be made.     

Photocatalytic removal of organic pollutants in aqueous solution by Bi(4)Nb(x)Ta((1-x))O(8)I

In this work, Bi₄Nb_xTa_(1−x)O₈I photocatalysts have been synthesized by solid state reaction method and characterized by powder X-ray diffraction, scanning electron microscope and UV-Vis near infrared diffuse reflectance spectroscopy. The photocatalytic activity of these photocatalysts was evaluated by the degradation of methyl orange (MO) in aqueous solutions under visible light, UV light and solar irradiation. The effects of catalyst dosage, initial pH and MO concentration on the removal efficiency were studied, and the photocatalytic reaction kinetics of MO degradation as well. The results indicated that Bi₄Nb_xTa_(1−x)O₈I exhibited high photocatalytic activity for the removal of MO in aqueous solutions. For example, the removal efficiency of MO by Bi₄Nb_0.1Ta_0.9O₈I was as high as 92% within 12 h visible light irradiation under the optimal conditions: initial MO concentration of 5-10 mg L⁻¹, catalyst dosage of 6 g L⁻¹ and natural pH (6-8), the MO molecules could be completely degradated by Bi₄Nb_0.1Ta_0.9O₈I within 40 min under UV light irradiation, and the photodegradation efficiency reaches to 60% after 7 h solar irradiation. Furthermore, the photocatalytic degradation of Bisphenol A (BPA) was also investigated under visible light irradiation. It is found that 99% BPA could be mineralized by Bi₄Nb_0.1Ta_0.9O₈I after 16 h visible light irradiation. Through HPLC/MS, BOD, TOC, UV-Vis measurements, we determined possible degradation products of MO and BPA. The results indicated that MO was degradated into products which are easier to be biodegradable and innocuous treated, and BPA could be mineralized completely. Furthermore, the possibility for the photosensitization effect in the degradation process of MO under visible light irradiation has been excluded.     

Triclosan affects the microbial community in simulated sewage-drain-field soil and slows down xenobiotic degradation

Effects of the common antibacterial agent triclosan on microbial communities and degradation of domestic xenobiotics were studied in simulated sewage-drain-field soil. Cultivable microbial populations decreased 22-fold in the presence of 4 mg kg⁻¹ of triclosan, and triclosan-resistant Pseudomonas strains were strongly enriched. Exposure to triclosan also changed the general metabolic profile (Ecoplate substrate profiling) and the general profile (T-RFLP) of the microbial community. Triclosan degradation was slow at all concentrations tested (0.33-81 mg kg⁻¹) during 50-days of incubation. Mineralization experiments (¹⁴C-tracers) and chemical analyses (LC-MS/MS) showed that the persistence of a linear alkylbenzene sulfonate (LAS) and a common analgesic (ibuprofen) increased with increasing triclosan concentrations (0.16-100 mg kg⁻¹). The largest effect was seen for LAS mineralization which was severely reduced by 0.16 mg kg⁻¹ of triclosan. Our findings indicate that environmentally realistic concentrations of triclosan may affect the efficiency of biodegradation in percolation systems.     

Potential of the TCE-degrading endophyte Pseudomonas putida W619-TCE to improve plant growth and reduce TCE phytotoxicity and evapotranspiration in poplar cuttings

The TCE-degrading poplar endophyte Pseudomonas putida W619-TCE was inoculated in poplar cuttings, exposed to 0, 200 and 400 mg l⁻¹ TCE, that were grown in two different experimental setups. During a short-term experiment, plants were grown hydroponically in half strength Hoagland nutrient solution and exposed to TCE for 3 days. Inoculation with P. putida W619-TCE promoted plant growth, reduced TCE phytotoxicity and reduced the amount of TCE present in the leaves. During a mid-term experiment, plants were grown in potting soil and exposed to TCE for 3 weeks. Here, inoculation with P. putida W619-TCE had a less pronounced positive effect on plant growth and TCE phytotoxicity, but resulted in strongly reduced amounts of TCE in leaves and roots of plants exposed to 400 mg l⁻¹ TCE, accompanied by a lowered evapotranspiration of TCE. Dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA), which are known intermediates of TCE degradation, were not detected.     

Gas-phase reaction of (E)-β-farnesene with ozone: Rate coefficient and carbonyl products

The gas-phase ozonolysis of (E)-β-farnesene was investigated in a 3.91 m³ atmospheric simulation chamber at 296 ± 2 K and relative humidity of around 0.1%. The relative rate method was used to determine the reaction rate coefficient of (4.01 ± 0.17) × 10^?16 cm³ molecule^?1 s^?1, where the indicated errors are two least-squares standard deviations and do not include uncertainties in the rate coefficients for the reference compounds (γ-terpinene, cis-cyclooctene and 1,5-cyclooctadiene). Gas phase carbonyl products were collected using a denuder sampling technique and analyzed with GC/MS following derivatization with O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA). The reaction products detected were acetone, 4-oxopentanal, methylglyoxal, 4-methylenehex-5-enal, 6-methylhept-5-en-2-one, and (E)-4-methyl-8-methylenedeca-4,9-dienal. A detailed mechanism for the gas-phase ozonolysis of (E)-β-farnesene is proposed, which accounts for all of the products observed in this study. The results of this work indicate that the atmospheric reaction of (E)-β-farnesene with ozone has a lifetime of around 1 h and is another possible source of the ubiquitous carbonyls, acetone, 4-oxopentanal and 6-methylhept-5-en-2-one in the atmosphere.     

Degradation of lidocaine,tramadol, venlafaxine and the metabolites O-desmethyltramadol and O-desmethylvenlafaxine in surface waters

The photodegradation and biotic transformation of the pharmaceuticals lidocaine (LDC), tramadol (TRA) and venlafaxine (VEN), and of the metabolites O-desmethyltramadol (ODT) and O-desmethylvenlafaxine (ODV) in the aquatic environmental have been investigated. Photodegradation experiments were carried out using a medium pressure Hg lamp (laboratory experiments) and natural sunlight (field experiments). Degradation of the target compounds followed a first-order kinetic model. Rates of direct photodegradation (light absorption by the compounds itself) at pH 6.9 were very low for all of the target analytes (?0.0059 h^?1 using a Hg lamp and ?0.0027 h^?1 using natural sunlight), while rates of indirect photodegradation (degradation of the compounds through photosensitizers) in river water at pH 7.5 were approximately 59 (LDC), 5 (TRA), 8 (VEN), 15 (ODT) and 13 times (ODV) higher than the rates obtained from the experiments in ultrapure water. The accelerated photodegradation of the target compounds in natural water is attributed mainly to the formation of hydroxyl radicals through photochemical reactions. Biotic (microbial) degradation of the target compounds in surface water has been shown to occur at very low rates (?0.00029 h^?1). The half-life times determined from the field experiments were 31 (LDC), 73 (TRA), 51 (VEN), 21 (ODT) and 18 h (ODV) considering all possible mechanisms of degradation for the target compounds in river water (direct photodegradation, indirect photodegradation and biotic degradation).     

Assessing the transformation kinetics of 2- and 4-nitrophenol in the atmospheric aqueous phase. Implications for the distribution of both nitroisomers in the atmosphere

Different transformation processes for nitrophenols in the atmospheric aqueous phase were considered to assess their relative importance, and their ability to account for the higher occurrence of 4-nitrophenol (4NP) compared to 2-nitrophenol (2NP) in the atmosphere. The importance of the different processes was in the order ^?OH > ^?NO₃ > direct photolysis > nitration to 2,4-dinitrophenol. 2NP is more reactive than 4NP with the hydroxyl radical, but the difference is low. Accordingly, such a process could account for the higher atmospheric occurrence of 4NP only if the observed atmospheric nitrophenols were what was left of an almost complete degradation by ^?OH. This would imply the unlikely scenario that the known nitrophenol sources to the atmosphere were only a limited fraction of the actual ones. A more likely, tentative possibility would be connected with the higher occurrence of 4NP on particles. If the reactivity order of nitrophenols in the atmospheric compartments was water droplets > gas phase > particles, particulate matter could act as a reservoir of 4NP. 2NP would undergo degradation in gas phase or solution at a higher rate than 4NP on particles, which could decrease the atmospheric levels of 2NP below those of 4NP.     

Measurements of JNO3− in snow by nitrate-based actinometry

Chemical actinometry was used to measure nitrate photolysis rate coefficients, J_NO3⁻, on and in snowpack at Summit, Greenland. Sealed glass tubes containing nitrate and a hydroxyl radical trapping system were buried in snow and exposed for between 2 and 24 h. Average J_NO3⁻ values for 2-h midday exposures in early June on surface snow were 10–14×10⁻⁷ s⁻¹. Averages over 24 h were 3.5–4.5×10⁻⁷ s⁻¹. These values reflect the integrated photon flux and also any variation of the nitrate photolysis rate with temperature. Attenuation of J_NO3⁻ within the firn was 0.03–0.04 cm⁻¹ for 24-h exposures and 0.08 cm⁻¹ for a 2-h exposure. Different attenuation coefficients may relate to differential light penetration due to changes in sun angle over the course of 24 h.     

Cross-sections and quantum yields for the atmospheric photolysis of the potent greenhouse gas nitrogen trifluoride

Although NF₃, a trace gas of purely anthropogenic origin with a large global warming potential is accumulating in the Earth's atmosphere, little photochemical data exists from which to calculate its atmospheric removal rate. In this study, photodissociation quantum yields, Φ₁, were derived following 193.3 nm laser photolysis of NF₃, and quantitative conversion of the F-atom photoproducts to OH, which was detected by laser induced fluorescence. Values of Φ₁(P, T) = (1.03 ± 0.05) were determined at pressures between 28 and 100 mBar of He or N₂ and at either room temperature or 255 K. Absorption cross-sections, σ, obtained between 184 and 226 nm were combined with the values of Φ₁(P, T) to confirm a long (≈700 year) photolysis lifetime for NF₃. No evidence for reaction of OH with NF₃ was found, indicating that this process makes little or no contribution to NF₃ removal from the atmosphere. These results underpin recent calculations of an NF₃ atmospheric lifetime τ ≈ 550 years, largely controlled by photolysis in the stratosphere. In the course of this work the rate coefficient k₂(298 K) = (1.3 ± 0.2) × 10^?11 cm³ molecule^?1 s^?1 was obtained for the reaction F + H₂O.     

Light-induced heterogeneous ozone processing on organic coated particles: Kinetics and condensed-phase products

For the first time we investigated the effect of solar irradiation upon the heterogeneous ozonation of adsorbed 3,4,5-trimethoxybenzaldehyde on solid surface. Light-induced heterogeneous reactions between gas-phase ozone and 3,4,5-trimethoxybenzaldehyde adsorbed on silica particles were performed and the consecutive reaction products were identified. At an ozone mixing ratio of 250 ppb, the loss of 3,4,5-trimethoxybenzaldehyde ranged from 1.0 · 10^?6 s^?1 in the dark to 2.9 · 10^?5 s^?1 under light irradiation. Such large enhancement of 29 times clearly shows the importance of light (λ > 300 nm) during the heterogeneous ozonolysis on organic coated particles.The reaction products identified in this study (3,4,5-trimethoxybenzoic acid, syringic acid, methyl 3,4,5-trimethoxybenzoate) absorb light in the spectral window (λ > 300 nm) which implies that light-induced heterogeneous ozone processing can have an influence on the aerosol surfaces by changing their physico-chemical properties.The main identified product of the heterogeneous reactions between gas-phase ozone and 3,4,5-trimethoxybenzaldehyde under dark conditions and in presence of light was 3,4,5-trimethoxybenzoic acid. For this reason we estimated the carbon yield of 3,4,5-trimethoxybenzoic acid. Carbon yields of 3,4,5-trimethoxybenzoic acid decreased with increasing ozone mixing ratio; from 40% at 250 ppb to 15% at ≥2.5 ppm under dark conditions. At ozone mixing ratio (250 ppb–1 ppm), carbon yields of 3,4,5-trimethoxybenzaldehyde are relatively higher in the experiment under dark condition than under simulated solar light.     

Sunlight-induced degradation of soil-adsorbed veterinary antimicrobials Marbofloxacin and Enrofloxacin

Marbofloxacin (MAR) and Enrofloxacin (ENR), two largely employed veterinary Fluoroquinolones (FQs), were found to be present at the micrograms per kilogram level in agricultural soils of South Lombardy (Italy) several months after manuring. Distribution coefficients (K_d) from sorption experiments indicated a strong binding to the soil. Soil samples fortified with environmentally significant FQs amounts (0.5 mg kg⁻¹) were exposed to solar light that promoted extensive degradation (80%) of both drugs in 60-150 h. Thus, photochemistry could be considered a significant depollution path in the soil, although it was two orders of magnitudes slower than in aqueous solution and a fraction of the drug (ca. 20%) remained unaffected. For MAR the photoprocess was the same as in solution, and involved cleavage of the tetrahydrooxadiazine ring. On the contrary, with ENR only some of the photoproducts determined in water (those arising from a stepwise oxidation of the piperazine side chain) were observed. Substitution of the 6-fluoro by a hydroxyl group and reduction did not occur in the soil, supporting the previous contention that such processes required polar solvation of FQs. Consistently with this rationalization, the irradiation of thin layers of solid drugs led to essentially the same products distribution as in the soil. From the environmental point of view it is important to notice that photodegradation mainly affects the side-chains, while the fluoroquinolone ring, to which the biological effect is associated, is conserved up to the later stages of the degradation.     

Photochemical ozone creation potentials for oxygenated volatile organic compounds: sensitivity to variations in kinetic and mechanistic parameters

The sensitivity of Photochemical Ozone Creation Potentials (POCP) to a series of systematic variations in the rates and products of reactions of radical intermediates and oxygenated products is investigated for the C₄ alcohols, 1-butanol (n-butanol) and 2-methyl-1-propanol (i-butanol), using the recently developed Master Chemical Mechanism (MCM) as the base case. The POCP values are determined from the calculated formation of ozone in the boundary layer over a period of approximately five days along an idealised straight line trajectory, using a photochemical trajectory model and methodology described in detail previously. The results allow the relative impacts on calculated ozone formation of various classes of chemical reaction within the degradation chemistry to be assessed. The calculated POCP is found to be very insensitive to many of the changes investigated. However, it is found to be sensitive to variations in the rate coefficient for the initiating reaction with OH (k_OH), although the sensitivity decreases with increasing k_OH. The POCP appears to vary approximately linearly with k_OH at low values (i.e. k_OH less than ca. 4×10^-13 cm³ molecule^-1 s^-1), whereas at high reactivities (i.e. k_OH greater than ca. 4×10^-11 cm³ molecule^-1 s^-1), the calculated POCP value is comparatively insensitive to the precise value of k_OH. The POCP is also very sensitive to mechanistic changes which influence the yields of unreactive oxygenated products (i.e. those with OH reactivities below ca. 10^-12 cm³ molecule^-1 s^-1), for example acetone. The propensity of the organic compound to produce organic nitrates (which act as comparatively unreactive reservoirs for free radicals and NO_x) also appears to have a notable influence on the calculated POCP. Recently reported information relevant to the degradation of oxygenated VOCs is then used to update the chemical schemes for the 17 alcohols and glycols, 10 ethers and glycol ethers, and 8 esters included in the MCM, and new schemes are incorporated for dimethoxy methane (CH₃OCH₂OCH₃) and dimethyl carbonate (CH₃OC(O)OCH₃), which are proposed fuel additives. New or updated POCP values are calculated for all 37 oxygenated VOCs and, where applicable, these are compared with the previous POCP values and reported Maximum Incremental Reactivity (MIR) values.     

Chlorpyrifos causes decreased organic matter decomposition by suppressing earthworm and termite communities in tropical soil

Effects of pesticides on structural and functional properties of ecosystems are rarely studied under tropical conditions. In this study litterbag and earthworm field tests were performed simultaneously at the same tropical field site sprayed with chlorpyrifos (CPF). The recommended dose of CPF (0.6 kg a.i. ha⁻¹) and two higher doses (4.4-8.8 kg a.i. ha⁻¹) significantly decreased litter decomposition during the first 3 months after application, which could be explained from lower earthworm and termite abundances during this period. Species-specific effects of CPF on organism abundance and biomass were observed, with termites being mostly affected followed by the earthworm Perionyx excavatus; the earthworm Megascolex sp. was least affected. Recovery was completed within 6 months. Decomposition in the controls and lowest two treatments was completed within 4 months, which suggests the need for modification of standard test guidelines to comply with faster litter degradation under tropical conditions.     

Development of an improved optical transmission technique for black carbon (BC) analysis

A new optical transmission technique for black carbon (BC) analysis was developed to minimize interferences due to scattering effects in filter samples. A standard thermal analysis method (VDI, 1999) is used to link light attenuation by the filter samples to elemental carbon (EC) concentration. Scattering effects are minimized by immersion of the filters in oil of a similar refractive index, as is often done for microscopy purposes. Light attenuation was measured using both a white light source and a red LED of 650 nm. The usual increase in overestimation of BC concentrations with decreasing BC amount in filter samples was found considerably reduced. Some effects of BC properties (e.g. fractal dimension, microstructure and size distribution) on the specific attenuation coefficient B_ATN, however, are still present for the treated samples. B_ATN was found close to 1 m² g⁻¹ for dry-dispersed industrial BC and 7 m² g⁻¹ for nebulized BC. Good agreement was found between the oil immersion, integrating sphere and a polar photometer technique and Mie calculations. The average specific attenuation coefficient of ambient samples in oil varied between 7 and 11 m² g⁻¹ for white light and 6 and 9 m² g⁻¹ for red light (LED). B_ATN was found to have much less site variation for the treated than for the untreated samples. The oil immersion technique improved also the correlation with thermally analyzed EC. This new immersion technique therefore presents a considerable improvement over conventional optical transmission techniques and may therefore serve as a simple, fast and cost-effective alternative to thermal methods.     

Kinetics and mechanism for omethoate degradation by catalytic ozonation with Fe(III)-loaded activated carbon in water

The kinetics and mechanism for degradation of omethoate (OMT) by catalytic ozonation with Fe(III)-loaded activated carbon (Fe@AC) were investigated in this study with focus on identification of degradation byproducts. The rate constants of OMT reacting with ozone and hydroxyl radical (OH) were determined to be 0.04 and 5.3 × 10⁸ M^?1 s^?1 at pH 7.5 and 20 °C, respectively. OMT was predominantly degraded by OH in the catalytic ozonation with Fe@AC. The high-molecular-weight degradation byproducts identified were O,O,O-trimethyl phosphoric ester (TMP), pyrrolidin-2-one, N-methyl-2-sulfanylacetamide, 2-(methylthio)acetamide, O,O,S-trimethylthiophosphate (STMP), and N-methyl-2-(methylthio)acetamide. Besides, low-molecular-weight organic acids and inorganic anions were also detected and quantified, including formic, acetic and oxalic acids as well as nitrate, sulfate and phosphate ions. In the catalytic ozonation, TMP and phosphate were two major P-containing byproducts resulting from OMT degradation. The toxicity of OMT solution gradually decreased during the catalytic ozonation, indicating that Fe@AC is a safe catalyst for OMT removal by ozone in water.     

Influence of temperature on the chemical removal of 3-methylbutanal,trans-2-methyl-2-butenal,and 3-methyl-2-butenal by OH radicals in the troposphere

Absolute rate coefficients for the gas-phase reactions of OH radical with 3-methylbutanal (k₁), trans-2-methyl-2-butenal (k₂), and 3-methyl-2-butenal (k₃) have been obtained with the pulsed laser photolysis/laser-induced fluorescence technique. Gas-phase concentration of aldehydes was measured by UV absorption spectroscopy at 185 nm. Experiments were performed over the temperature range of 263–353 K at total pressures of helium between 46.2 and 100 Torr. No pressure dependence of all k_i (i = 1–3) was observed at all temperatures. In contrast, a negative temperature dependence of k_i (i.e., k_i increases when temperature decreases) was observed in that T range. The resulting Arrhenius expressions (±2σ) are: k₁(T) = (5.8 ± 1.7)×10^?12 exp{(499 ± 94)/T} cm³ molecule^?1 s^?1, k₂(T)=(6.9 ± 0.9)×10^?12 exp{(526 ± 42)/T} cm³ molecule^?1 s^?1, k₃(T)=(5.6 ± 1.2)×10^?12 exp{(666 ± 54)/T} cm³ molecule^?1 s^?1.The tropospheric lifetimes derived from the above OH-reactivity trend are estimated to be higher for 3-methylbutanal than those for the unsaturated aldehydes. A comparison of the tropospheric removal of these aldehydes by OH radicals with other homogeneous degradation routes leads to the conclusion that this reaction can be the main homogeneous removal pathway. However, photolysis of these aldehydes in the actinic region (λ > 290 nm) could play an important role along the troposphere, particularly for 3-methyl-2-butenal. This process could compete with the OH reaction for 3-methylbutanal or be negligible for trans-2-methyl-2-butenal in the troposphere.     

A photochemical reactor for studies of atmospheric chemistry

A photochemical reactor for studies of atmospheric kinetics and spectroscopy has been built at the Copenhagen Center for Atmospheric Research. The reactor consists of a vacuum FTIR spectrometer coupled to a 100 L quartz cylinder by multipass optics mounted on electropolished stainless steel end flanges, surrounded by UV-A, UV-C and broadband sun lamps in a temperature-controlled housing. The combination of a quartz vessel and UV-C lamps allows higher concentrations of O(¹D) and OH than can be generated by similar chambers. The reactor is able to produce radical concentrations of ca. 8 × 10¹¹ cm^?3 for OH, 3 × 10⁶ cm^?3 for O(¹D), 3.3 × 10¹⁰ cm^?3 for O(³P) and 1.6 × 10¹² cm^?3 for Cl. The reactor can be operated at pressures from 10^?3 to 10³ mbar and temperatures from 240 to 330 K. As a test of the system we have studied the reaction CHCl₃ + Cl using the relative rate technique and find k_CHCl3+Cl/k_CH4+Cl = 1.03 ± 0.11, in good agreement with the accepted value.